[M_xL_y]_n[M_wX_z]_m Non-Perovskite Hybrid Halides of Coinage Metals Templated by Metal–Organic Cations: Structures and Photocatalytic Properties

Abstract

This review provides an analysis of non-perovskite hybrid halides of coinage metals templated by metal–organic cations (CCDC November 2023). These materials display remarkable structural diversity, from zero-dimensional molecular complexes to intricate three-dimensional frameworks, allowing fine-tuning of their properties. A total of 208 crystal structures, comprising haloargentates, mixed-metal haloargentates, and halocuprates, are categorized and examined. Their potential in photocatalysis is discussed. Special attention is given to the structural adaptability of these materials for the generation of functional interfaces. This review highlights key compounds and aims to inspire further research into optimizing hybrid halides for advanced technological applications.

1. Introduction

The Cheetham classification [1] of organic–inorganic hybrids, particularly hybrid organic–inorganic perovskites (HOIPs), is fundamental to understanding their properties. Organic counterparts in these hybrids are often limited to discrete structural units, whereas the inorganic components exhibit a wide range of dimensionalities, from 0D, through 1D and 2D, to fully 3D frameworks. In this paper, we explore a special case where the organic part is replaced by metal–organic cations [${\mathrm{M}}_x{\mathrm{L}}_y{]}^{m+}$, while the inorganic component spans from discrete 0D clusters to infinite 1D, 2D, and 3D networks [${\mathrm{M}}_w{\mathrm{X}}_z{]}^{n-}$, where X denotes a halide ion.

To date, the Cambridge Crystal Structure Database contains approximately 3500 of these structures. In this study, we have excluded coordination polymers from the metal–organic category to focus on discrete ionic assemblies, or “templating molecules”, which are predominantly cationic. No anions were found in this set of structures. We further classified these structures based on the chemical origin of the organic ligands, which include groups such as DMSO, DMF, DMA, ethylenediamine, bipyridyl, phenanthroline, triethylene tetraamine, glyme, diglyme, crown ethers, aza macrocycles, thia macrocycles, metallocenes, cucurbiturils, bispidines, N,P-donating ligands, carbamates, and lactams.

These organic ligands form hybrid assemblies with halometallates that exhibit a variety of connectivities, ranging from 1D and 2D to 3D, with metals such as silver, lead, copper, bismuth, antimony, tin, and mercury. Other metals, including zinc(II), manganese(II), iron(II), cadmium(II), and gold(III), tend to form discrete halometallate ions, such as tetrahalometallates.

The composition of these hybrid halides leads to varying properties. Depending on the dimensionality of the inorganic subnetwork, they can behave as homogeneous catalysts (reactions of polymerization, such as ATRP) [2], low-melting-point ionic solids exhibiting near-unity quantum yield luminescence as in the case of [M(DMSO${)}_6$][${\mathrm{SbCl}}_6$] [3], or luminescent solids exhibiting 4f—3d sensitization behavior [4]. Starting from discrete assemblies of solvent complexes, they can form metal organic–inorganic hybrid glasses [5]. Then, with a further increase in the nuclearity of discrete halometallate clusters, they can exhibit self-trapped exciton luminescence [6]. However, the rules governing the formation of efficient luminescent solids are not clear, since both luminescent and non-luminescent solids have been reported with established crystal structures. Interestingly, scintillating properties have also been reported for the same solids (internal X-ray to light conversion) [7]. With a further increase in the connectivity of the inorganic part, semiconducting properties and photoelectric properties emerge. These could find application in the photocatalytic degradation of pollutants [8]. Interestingly, photoelectronic effects have also been reported for zero-dimensional systems ([Co(en${)}_3$${]}_2$(${\mathrm{Zr}}_2{\mathrm{F}}_{12}$)(${\mathrm{SiF}}_6$)·4${\mathrm{H}}_2$O compound) [9].

We have limited this review to coinage metal halometallates, specifically those of copper and silver (as gold seems to not form polynuclear halometallates), templated by metalorganic cations. The numbers of members of these groups of compounds represented in the Cambridge Crystal Structure Database are well suited for a mini-review. We have also included mixed-metal haloargentates in our considerations. In total, the numbers of compounds discussed in this work are 83 haloargentates, 25 mixed-metal haloargenatates, and 100 halocuprate compounds. Thus, 208 compounds have been described in 130 research papers.

Table 1. The CSD survey on haloargentates templated with metal–organic cations.

Sum Formula	Nuclearity	Dim.	CCDC Code	Synthesis	Ref.
(${\mathrm{C}}_{24}{\mathrm{H}}_{16}{\mathrm{BrCuN}}_4$${)}_{2n}^{+}$, n(${\mathrm{Ag}}_2{\mathrm{Br}}_4$${)}^{2-}$	2	1D	CEQJAM	RT	[10]
${\mathrm{C}}_{36}{\mathrm{H}}_{24}{{\mathrm{FeN}}_6}^{2+}$, ${\mathrm{C}}_3{\mathrm{H}}_7$NO, ${\mathrm{Ag}}_2{{\mathrm{Br}}_4}^{2-}$	2	0D	CEQJEQ	RT	[10]
${\mathrm{C}}_{26}{\mathrm{H}}_{40}{\mathrm{Ag}}_2{{\mathrm{N}}_8}^{2+}$, ${\mathrm{Ag}}_2{{\mathrm{Br}}_4}^{2-}$	2	0D	CUXWOI	antisolvent	[11]
(${\mathrm{C}}_6{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Zn}}^{2+}$${)}_n$, n(${\mathrm{Ag}}_2{\mathrm{I}}_4$${)}^{2-}$	2	3D	EFATIP	RT	[12]
(${\mathrm{C}}_6{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}$${)}_n$, n(${\mathrm{Ag}}_2{\mathrm{I}}_4$${)}^{2-}$	2	3D	EFATOV	RT	[12]
${\mathrm{C}}_{18}{\mathrm{H}}_{14}{\mathrm{MoN}}_3{\mathrm{O}}_2{\mathrm{S}}^{+}$, 0.5(${\mathrm{Ag}}_2{\mathrm{Br}}_4$${)}^{2-}$	2	0D	EFELIM	RT	[13]
${\mathrm{C}}_{44}{\mathrm{H}}_{40}{\mathrm{Ag}}_2{{\mathrm{N}}_8}^{2+}$, ${\mathrm{Ag}}_2{{\mathrm{Br}}_4}^{2-}$, 4(${\mathrm{C}}_3{\mathrm{H}}_7$NO)	2	0D	GAJLOT	RT	[14]
(${\mathrm{C}}_{10}{\mathrm{H}}_{16}{{\mathrm{AgN}}_4}^{+}$${)}_n$, n(${\mathrm{Ag}}_2{\mathrm{I}}_3$${)}^{-}$	2	1D	IHINES	hot DMSO	[15]
${\mathrm{C}}_{84}{\mathrm{H}}_{96}{\mathrm{Ag}}_2{{\mathrm{N}}_8}^{2+}$, ${\mathrm{Ag}}_2{{\mathrm{Br}}_4}^{2-}$	2	0D	IVODIH	RT	[16]
${\mathrm{C}}_{18}{\mathrm{H}}_{24}{{\mathrm{AuN}}_8}^{3+}$, ${\mathrm{Br}}^{-}$, 0.5(${\mathrm{Ag}}_2{{\mathrm{Br}}_6}^{4-}$)	2	0D	JATLUO	RT	[17]
${\mathrm{C}}_{64}{\mathrm{H}}_{64}{\mathrm{Cl}}_2{\mathrm{N}}_{16}{{\mathrm{Ni}}_2}^{2+}$, ${\mathrm{Ag}}_2{{\mathrm{Cl}}_4}^{2-}$, 2(${\mathrm{C}}_4{\mathrm{H}}_{10}$O)	2	0D	JOHLIC	antisolvent	[18]
${\mathrm{C}}_{37}{\mathrm{H}}_{45}{\mathrm{BrN}}_5{\mathrm{Ni}}^{+}$, 0.5(${\mathrm{Ag}}_2{\mathrm{I}}_4$${)}^{2-}$	2	0D	LIYTUJ	antisolvent	[19]
2(${\mathrm{C}}_{52}{\mathrm{H}}_{50}{\mathrm{AgCl}}_2{{\mathrm{N}}_4}^{+}$), 0.5(${\mathrm{C}}_5{\mathrm{H}}_{12}$), ${\mathrm{Ag}}_2{\mathrm{Cl}}_2{{\mathrm{I}}_2}^{2-}$	2	0D	LUMZIF	RT	[20]
${\mathrm{C}}_{72}{\mathrm{H}}_{88}{\mathrm{Ag}}_2{{\mathrm{N}}_{12}}^{2+}$, ${\mathrm{Ag}}_2{{\mathrm{Br}}_4}^{2-}$, 2(${\mathrm{CHCl}}_3$)	2	0D	MASSIK	antisolvent	[21]
(${\mathrm{C}}_{16}{\mathrm{H}}_{48}{\mathrm{O}}_8{\mathrm{S}}_8{\mathrm{Tb}}^{3+}$${)}_{2n}$, n(${\mathrm{Ag}}_2{\mathrm{I}}_5$${)}^{3-}$, n(${\mathrm{Ag}}_5{\mathrm{I}}_8$${)}^{3-}$	2 and 5	2D	RUNSID	antisolvent	[22]
2(${\mathrm{C}}_6{\mathrm{H}}_{20}{\mathrm{N}}_4{\mathrm{Pb}}^{2+}$), ${\mathrm{Ag}}_2{{\mathrm{Cl}}_6}^{4-}$	2	0D	SAZNEQ	solvothermal	[23]
2(${\mathrm{C}}_{20}{\mathrm{H}}_{32}{\mathrm{AgN}}_4{{\mathrm{O}}_2}^{+}$), ${\mathrm{Ag}}_2{{\mathrm{I}}_4}^{2-}$, ${\mathrm{C}}_2{\mathrm{H}}_3$N	2	0D	SIXLUI	RT	[24]
$2\left({\mathrm{C}}_{42}{\mathrm{H}}_{32}{\mathrm{AuN}}_4^{+}\right),{\mathrm{Ag}}_2{\mathrm{Br}}_4^{2-},2\left(\mathrm{C}{\mathrm{H}}_2{\mathrm{Cl}}_2\right)$	2	0D	VAWRUJ	antisolvent	[25]
${\left({\mathrm{C}}_6{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Zn}}^{2+}\right)}_n,n\left({\mathrm{Ag}}_2{\mathrm{I}}_4^{2-}\right)$	2	3D	VIPFIM	RT	[26]
${\left({\mathrm{C}}_6{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}\right)}_n,n\left({\mathrm{Ag}}_2{\mathrm{I}}_4^{2-}\right)$	2	3D	VIPFUY	RT	[26]
${\mathrm{C}}_{72}{\mathrm{H}}_{72}{\mathrm{Ag}}_2{\mathrm{N}}_8^{2+},{\mathrm{Ag}}_2{\mathrm{Br}}_4^{2-}$	2	0D	VITZEG	RT	[27]
${\left({\mathrm{C}}_{18}{\mathrm{H}}_{16}\mathrm{Ag}{\mathrm{N}}_6^{+}\right)}_n,n\left({\mathrm{Ag}}_2{\mathrm{I}}_3^{-}\right),n\left({\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}\mathrm{S}\right)$	2	1D	VUDKUB	hot DMSO	[28]
$3\left({\mathrm{C}}_{58}{\mathrm{H}}_{44}\mathrm{Ag}{\mathrm{N}}_4^{+}\right),{\mathrm{Ag}}_2{\mathrm{Br}}_5^{3-}$	2	0D	VUZGOO	RT	[29]
${\mathrm{C}}_6{\mathrm{H}}_{24}\mathrm{Mn}{\mathrm{N}}_6^{2+},{\left({\mathrm{Ag}}_2{\mathrm{I}}_4^{2-}\right)}_n$	2	3D	WEKVAM	RT	[30]
${\left({\mathrm{C}}_6{\mathrm{H}}_{24}\mathrm{Mg}{\mathrm{N}}_6^{2+}\right)}_n,n\left({\mathrm{Ag}}_2{\mathrm{I}}_4^{2-}\right)$	2	3D	WEKVEQ	RT	[30]
${\mathrm{C}}_{16}{\mathrm{H}}_{48}{\mathrm{O}}_8{\mathrm{S}}_8{\mathrm{Y}}^{3+},{\mathrm{Ag}}_2{\mathrm{I}}_5^{3-}$	2	0D	XOKQAQ	antisolvent	[31]
$2\left({\mathrm{C}}_{24}{\mathrm{H}}_{18}\mathrm{Mo}{\mathrm{N}}_3{\mathrm{O}}_2{\mathrm{S}}^{+}\right),{\mathrm{Ag}}_2{\mathrm{Br}}_4^{2-}$	2	0D	ZOMCOV	reflux	[13]

and

Table 2. The CSD survey on haloargentates templated with metal–organic cations.

Sum Formula	Nuclearity	Dim.	CCDC Code	Synthesis	Ref.
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Zn}}^{2+}\right)}_n,n\left({\mathrm{Ag}}_3{\mathrm{I}}_5^{2-}\right)$	3	1D	PUNKIU	solvothermal	[32]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Mn}{\mathrm{N}}_6^{2+}\right)}_n,n\left({\mathrm{Ag}}_3{\mathrm{I}}_5^{2-}\right)$	3	1D	PUNKOA	solvothermal	[32]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{FeN}}_6^{2+}\right)}_n,n\left({\mathrm{Ag}}_3{\mathrm{I}}_5^{2-}\right)$	3	1D	PUNKUG	solvothermal	[32]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{CoN}}_6^{2+}\right)}_n,n\left({\mathrm{Ag}}_3{\mathrm{I}}_5^{2-}\right)$	3	1D	PUNLAN	solvothermal	[32]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{NiN}}_6^{2+}\right)}_n,n\left({\mathrm{Ag}}_3{\mathrm{I}}_5^{2-}\right)$	3	1D	PUNLER	solvothermal	[32]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}{\mathrm{FeN}}_6^{2+}\right),{\mathrm{Ag}}_3{\mathrm{I}}_7^{4-}$	3	0D	PUZJUR	solvothermal	[33]
${\mathrm{C}}_{51}{\mathrm{H}}_{60}{\mathrm{AgClN}}_8{\mathrm{Ru}}^{2+},n\left({\mathrm{Ag}}_4{\mathrm{Cl}}_6^{2-}\right),4\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	4	1D	YASYEZ	RT	[34]
$2\left({\mathrm{C}}_{24}{\mathrm{H}}_{32}{\mathrm{Ag}}_2{\mathrm{N}}_8^{2+}\right),{\mathrm{Ag}}_4{\mathrm{I}}_8^{4-},4\left({\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}\mathrm{S}\right)$	4	0D	YIJHIJ	hot DMSO	[35]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{36}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}\right),{\mathrm{Ag}}_5{\mathrm{I}}_9^{4-},4\left({\mathrm{H}}_2\mathrm{O}\right)$	5	0D	CUTZEZ	solvothermal	[36]
${\left({\mathrm{C}}_{24}{\mathrm{H}}_{28}{\mathrm{MnN}}_4{\mathrm{O}}_2{\mathrm{S}}_2^{2+}\right)}_n,n\left({\mathrm{Ag}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	DUQLIN	RT	[37]
${\left({\mathrm{C}}_{26}{\mathrm{H}}_{29}{\mathrm{MnN}}_6{\mathrm{O}}_2^{2+}\right)}_n,n\left({\mathrm{Ag}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	DUQLOT	RT	[37]
${\left({\mathrm{C}}_{26}{\mathrm{H}}_{30}{\mathrm{N}}_6{\mathrm{O}}_2{\mathrm{Zn}}^{2+}\right)}_n,n\left({\mathrm{Ag}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	DUQLUZ	RT	[37]
${\left({\mathrm{C}}_{24}{\mathrm{H}}_{32}{\mathrm{N}}_4{\mathrm{O}}_4{\mathrm{S}}_2{\mathrm{Zn}}^{2+}\right)}_n,2n\left({\mathrm{Ag}}_5{\mathrm{I}}_6^{-}\right),2n\left({\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}\mathrm{S}\right)$	5	1D	DUQMIO	RT	[37]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{CuN}}_6^{2+}\right)}_n,n\left({\mathrm{Ag}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	HUZCIP	RT	[38]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{CoN}}_6^{2+}\right)}_n,n\left({\mathrm{Ag}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	KAMJEQ	solvothermal	[39]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Zn}}^{2+}\right)}_n,n\left({\mathrm{Ag}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	KAMJIU	solvothermal	[39]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}\right)}_n,n\left({\mathrm{Ag}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	KAMJOA	solvothermal	[39]
${\left({\mathrm{C}}_{54}{\mathrm{H}}_{66}{\mathrm{AgO}}_{18}{\mathrm{P}}_2\right)}_{2n}^{+},n\left({\mathrm{Ag}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	KUXDOW	reflux	[40]
$2{\left({\mathrm{C}}_{54}{\mathrm{H}}_{66}{\mathrm{AgO}}_{18}{\mathrm{P}}_2\right)}^{+},{\mathrm{C}}_{10}{\mathrm{H}}_{10}{\mathrm{Ag}}_5{\mathrm{I}}_7{\mathrm{N}}_2^{2-},2\left({\mathrm{C}}_5{\mathrm{H}}_5\mathrm{N}\right)$	5	0D	XAYQOE	RT	[41]
${\left({\mathrm{C}}_{54}{\mathrm{H}}_{66}{\mathrm{AgO}}_{18}{\mathrm{P}}_2\right)}^{+}n,n{\left({\mathrm{C}}_9{\mathrm{H}}_7{\mathrm{Ag}}_5{\mathrm{I}}_6\mathrm{N}\right)}^{-},n\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	5	1D	XAYQUK	RT	[41]
${\mathrm{C}}_{15}{\mathrm{H}}_{31}{\mathrm{KO}}_7^{+},n\left({\mathrm{Ag}}_5{\mathrm{I}}_6^{-}\right),{\mathrm{C}}_3{\mathrm{H}}_7\mathrm{NO}$	5	1D	ZOZDIE	NA	[42]
${\mathrm{C}}_{24}{\mathrm{H}}_{74}{\mathrm{Ba}}_2{\mathrm{O}}_{13}{\mathrm{S}}_{12}^{4+},{\mathrm{Ag}}_6{\mathrm{I}}_{11}^{5-},{\mathrm{H}}_3{\mathrm{O}}^{+},2\left({\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}\mathrm{S}\right)$	6	0D	COZGOP	antisolvent	[43]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{MnN}}_6^{2+}\right),n\left({\mathrm{Ag}}_6{\mathrm{I}}_{11}^{5-}\right),{\mathrm{K}}^{+}$	6	2D	DUYBEG	solvothermal	[44]
${\mathrm{C}}_{52}{\mathrm{H}}_{106}{\mathrm{La}}_2{\mathrm{N}}_{16}{\mathrm{O}}_{16}^{6+},2n\left({\mathrm{Ag}}_6{\mathrm{I}}_9^{3-}\right)$	6	1D	FETCEP	RT	[45]
${\mathrm{C}}_{52}{\mathrm{H}}_{106}{\mathrm{N}}_{16}{\mathrm{O}}_{16}{\mathrm{Sm}}_2^{6+},2n\left({\mathrm{Ag}}_6{\mathrm{I}}_9^{3-}\right)$	6	1D	FETCIT	RT	[45]
$2\left({\mathrm{C}}_{18}{\mathrm{H}}_{18}\mathrm{Ag}{\mathrm{N}}_6^{+}\right),n\left({\mathrm{Ag}}_6{\mathrm{I}}_8^{2-}\right)$	6	2D	JEPJEX	NA	[46]
${\left({\mathrm{Ag}}_6{\mathrm{I}}_9^{3-}\right)}_n,n\left({\mathrm{C}}_{24}{\mathrm{H}}_{56}\mathrm{Er}{\mathrm{N}}_8{\mathrm{O}}_8^{3+}\right)$	6	1D	LAZBIZ	antisolvent	[47]
${\mathrm{Ag}}_6{\mathrm{I}}_8^{2-},{\mathrm{C}}_{74}{\mathrm{H}}_{90}{\mathrm{Ag}}_2{\mathrm{N}}_{10}^{2+},2\left({\mathrm{C}}_4{\mathrm{H}}_{10}\mathrm{O}\right)$	6	0D	LIYVOF	antisolvent	[19]
${\mathrm{C}}_{10}{\mathrm{H}}_{32}{\mathrm{O}}_6{\mathrm{S}}_5{\mathrm{V}}^{2+},n\left({\mathrm{Ag}}_6{\mathrm{I}}_8^{2-}\right)$	6	2D	PUCVAN	solvothermal	[48]
${\mathrm{C}}_{12}{\mathrm{H}}_{36}\mathrm{Fe}{\mathrm{O}}_6{\mathrm{S}}_6^{3+},n\left({\mathrm{Ag}}_6{\mathrm{I}}_9^{3-}\right),{\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}\mathrm{S}$	6	1D	QITJUB	solvothermal	[8]
${\left({\mathrm{C}}_{24}{\mathrm{H}}_{56}{\mathrm{N}}_8{\mathrm{O}}_8{\mathrm{Tb}}^{3+}\right)}_n,n\left({\mathrm{Ag}}_6{\mathrm{I}}_9^{3-}\right)$	6	1D	RUNSOJ	antisolvent	[22]
${\left({\mathrm{C}}_{22}{\mathrm{H}}_{54}{\mathrm{N}}_6{\mathrm{O}}_8{\mathrm{S}}_2{\mathrm{Tb}}^{3+}\right)}_n,n\left({\mathrm{Ag}}_6{\mathrm{I}}_9^{3-}\right)$	6	1D	RUQBIP	antisolvent	[22]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{2+}\right),{\mathrm{Ag}}_6{\mathrm{I}}_{10}^{4-}$	6	0D	RUVYEP	RT	[49]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}\right),{\mathrm{Ag}}_6{\mathrm{I}}_{10}^{4-}$	6	0D	RUVYIT	RT	[49]
${\left({\mathrm{C}}_{24}{\mathrm{H}}_{56}{\mathrm{N}}_8{\mathrm{O}}_8{\mathrm{Y}}^{3+}\right)}_n,n\left({\mathrm{Ag}}_6{\mathrm{I}}_9^{3-}\right)$	6	1D	XOKQEU	antisolvent	[31]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Fe}{\mathrm{N}}_6^{2+}\right),n\left({\mathrm{Ag}}_6{\mathrm{Br}}_{11}^{5-}\right),{\mathrm{H}}_4{\mathrm{N}}^{+}$	6	2D	ZEXMUO	solvothermal	[50]
${\mathrm{C}}_{52}{\mathrm{H}}_{106}{\mathrm{N}}_{16}{\mathrm{Nd}}_2{\mathrm{O}}_{16}^{6+},2n\left({\mathrm{Ag}}_6{\mathrm{I}}_9^{3-}\right)$	6	1D	ZICVUF	RT	[45]
$n\left({\mathrm{C}}_{16}{\mathrm{H}}_{22}\mathrm{Cu}{\mathrm{N}}_4{\mathrm{O}}_2^{2+}\right),n\left({\mathrm{Ag}}_7{\mathrm{I}}_9^{2-}\right)$	7	2D	KAPSOL	RT	[51]
${\mathrm{C}}_{16}{\mathrm{H}}_{48}\mathrm{Dy}{\mathrm{O}}_8{\mathrm{S}}_8^{3+},n\left({\mathrm{Ag}}_7{\mathrm{I}}_{10}^{3-}\right)$	7	2D	MEMPIG	antisolvent	[52]
$2\left({\mathrm{C}}_{13}{\mathrm{H}}_{39}{\mathrm{N}}_9{\mathrm{O}}_3{\mathrm{Pb}}_3^{4+}\right),{\mathrm{Ag}}_8{\mathrm{I}}_{15}^{7-},{\mathrm{I}}^{-}$	8	0D	BIZRIN	solvothermal	[53]
${\left({\mathrm{C}}_{20}{\mathrm{H}}_{44}\mathrm{Ba}{\mathrm{O}}_{10}^{2+}\right)}_{2n},n\left({\mathrm{Ag}}_8{\mathrm{I}}_{12}^{4-}\right),n\left({\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}\right)$	8	1D	COZHIK	antisolvent	[43]
${\mathrm{C}}_{32}{\mathrm{H}}_{72}\mathrm{La}{\mathrm{N}}_8{\mathrm{O}}_8^{3+},n\left({\mathrm{Ag}}_9{\mathrm{I}}_{12}^{3-}\right),2\left({\mathrm{H}}_2\mathrm{O}\right)$	9	1D	AMOZOU	antisolvent	[54]
${\mathrm{C}}_{12}{\mathrm{H}}_{36}\mathrm{Al}{\mathrm{O}}_6{\mathrm{S}}_6^{3+},n\left({\mathrm{Ag}}_9{\mathrm{I}}_{12}^{3-}\right)$	9	2D	LINROS	solvothermal	[45]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{2+}\right)}_n,n\left({\mathrm{Ag}}_{10}{\mathrm{I}}_{11}^{-}\right),n\left(\mathrm{H}{\mathrm{O}}^{-}\right)$	10	1D	CENHUC01	RT	[55]
${\left({\mathrm{C}}_{18}{\mathrm{H}}_{28}{\mathrm{N}}_2\mathrm{Ni}{\mathrm{O}}_4^{2+}\right)}_n,n\left({\mathrm{Ag}}_{10}{\mathrm{I}}_{12}^{2-}\right),2n\left({\mathrm{C}}_3{\mathrm{H}}_7\mathrm{N}\mathrm{O}\right)$	10	1D	HUZCEL	RT	[38]
${\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}\mathrm{Mn}{\mathrm{N}}_6^{2+}\right)}_{2n},n\left({\mathrm{Ag}}_{10}{\mathrm{I}}_{14}^{4-}\right)$	10	2D	PUZKEC	solvothermal	[33]
${\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{2+}\right)}_{2n},n\left({\mathrm{Ag}}_{13}{\mathrm{I}}_{17}^{4-}\right),15n\left({\mathrm{H}}_2\mathrm{O}\right)$	13	3D	QUSNOJ	solvothermal	[56]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}\mathrm{Fe}{\mathrm{N}}_6^{2+}\right),n\left({\mathrm{Ag}}_{13}{\mathrm{Br}}_{17}^{4-}\right),2\left({\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}\mathrm{S}\right)$	13	3D	CEQHIS	RT	[10]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{2+}\right),n\left({\mathrm{Ag}}_{13}{\mathrm{Br}}_{17}^{4-}\right),2\left({\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}\mathrm{S}\right)$	13	3D	CEQHOY	RT	[10]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}\right),n\left({\mathrm{Ag}}_{13}{\mathrm{Br}}_{17}^{4-}\right),2\left({\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}\mathrm{S}\right)$	13	3D	CEQHUE	RT	[10]
$4\left({\mathrm{C}}_{18}{\mathrm{H}}_{42}\mathrm{Co}{\mathrm{N}}_6{\mathrm{O}}_6^{2+}\right),{\mathrm{Ag}}_{14}{\mathrm{I}}_{22}^{8-}$	14	0D	ATAPOC	antisolvent	[57]
$2\left({\mathrm{C}}_{26}{\mathrm{H}}_{78}{\mathrm{Ba}}_2{\mathrm{O}}_{13}{\mathrm{S}}_{13}^{4+}\right),{\mathrm{Ag}}_{14}{\mathrm{I}}_{22}^{8-}$	14	0D	COZGIJ	antisolvent	[43]
${\mathrm{C}}_{28}{\mathrm{H}}_{63}{\mathrm{N}}_7{\mathrm{O}}_7{\mathrm{Pr}}^{3+},0.5n\left({\mathrm{Ag}}_{16}{\mathrm{I}}_{22}^{6-}\right)$	16	1D	AMOZUA	antisolvent	[54]
${\mathrm{C}}_{28}{\mathrm{H}}_{63}{\mathrm{N}}_7{\mathrm{O}}_7{\mathrm{Sm}}^{3+},0.5n\left({\mathrm{Ag}}_{16}{\mathrm{I}}_{22}^{6-}\right)$	16	1D	AMUBAO	antisolvent	[54]
$4\left({\mathrm{C}}_{16}{\mathrm{H}}_{48}{\mathrm{S}}_8{\mathrm{O}}_8{\mathrm{La}}^{3+}\right),{\mathrm{Ag}}_{22}{\mathrm{I}}_{34}^{12-},2\left({\mathrm{H}}_2\mathrm{O}\right)$	22	0D	MEMNOK	antisolvent	[52]
$4\left({\mathrm{C}}_{16}{\mathrm{H}}_{48}{\mathrm{S}}_8{\mathrm{O}}_8{\mathrm{Ce}}^{3+}\right),{\mathrm{Ag}}_{22}{\mathrm{I}}_{34}^{12-},2\left({\mathrm{H}}_2\mathrm{O}\right)$	22	0D	MEMNUQ	antisolvent	[52]

contain the entries associated with haloargentates,

Table 3. The CSD survey on mixed-metal haloargentates templated with metal–organic cations.

Sum Formula	Nuclearity	Dim.	CCDC Code	Synthesis	Ref.
${\mathrm{C}}_{36}{\mathrm{H}}_{24}\mathrm{Fe}{\mathrm{N}}_6^{2+},n\left({\mathrm{Ag}}_2{\mathrm{Br}}_6{\mathrm{Pb}}^{2-}\right)$	3	1D	JAYVEO	solvothermal	[58]
${\mathrm{C}}_{36}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+},n\left({\mathrm{Ag}}_2{\mathrm{Br}}_6{\mathrm{Pb}}^{2-}\right)$	3	1D	JAYVIS	solvothermal	[58]
${\mathrm{C}}_{36}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+},n\left({\mathrm{Ag}}_2{\mathrm{I}}_6{\mathrm{Pb}}^{2-}\right)$	3	1D	JAYVOY	solvothermal	[58]
$2\left({\mathrm{C}}_{20}{\mathrm{H}}_{44}\mathrm{Ba}{\mathrm{O}}_{10}^{2+}\right),{\mathrm{Ag}}_2{\mathrm{I}}_{10}{\mathrm{Pb}}_2^{4-},4\left({\mathrm{C}}_3{\mathrm{H}}_6\mathrm{O}\right)$	4	0D	COZJEI	273 K	[43]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Zn}}^{2+}\right),{\mathrm{Ag}}_2{\mathrm{Bi}}_2{\mathrm{I}}_{12}^{4-}$	4	0D	HEVZOB	solvothermal	[59]
${\mathrm{C}}_{16}{\mathrm{H}}_{48}\mathrm{Nd}{\mathrm{O}}_8{\mathrm{S}}_8^{3+},n\left({\mathrm{Ag}}_2{\mathrm{I}}_9{\mathrm{Pb}}_2^{3-}\right)$	4	1D	KEGDEJ	RT	[60]
${\left({\mathrm{C}}_{16}{\mathrm{H}}_{48}\mathrm{La}{\mathrm{O}}_8{\mathrm{S}}_8^{3+}\right)}_n,n\left({\mathrm{Ag}}_2{\mathrm{I}}_9{\mathrm{Pb}}_2^{3-}\right)$	4	1D	KOBCIP	RT	[61]
${\left({\mathrm{C}}_{16}{\mathrm{H}}_{48}\mathrm{Gd}{\mathrm{O}}_8{\mathrm{S}}_8^{3+}\right)}_n,n\left({\mathrm{Ag}}_2{\mathrm{I}}_9{\mathrm{Pb}}_2^{3-}\right)$	4	1D	KOBCOV	RT	[61]
${\left({\mathrm{C}}_{16}{\mathrm{H}}_{48}{\mathrm{O}}_8{\mathrm{S}}_8{\mathrm{Tm}}^{3+}\right)}_n,n\left({\mathrm{Ag}}_2{\mathrm{I}}_9{\mathrm{Pb}}_2^{3-}\right)$	4	1D	KOBCUB	RT	[61]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Fe}{\mathrm{N}}_6^{2+}\right),{\mathrm{Ag}}_2{\mathrm{Bi}}_2{\mathrm{I}}_{12}^{4-}$	4	0D	LANCOW	solvothermal	[62]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}\right),{\mathrm{Ag}}_2{\mathrm{Bi}}_2{\mathrm{I}}_{12}^{4-}$	4	0D	LANCUC	solvothermal	[62]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Fe}{\mathrm{N}}_6^{2+}\right),{\mathrm{Ag}}_2{\mathrm{Bi}}_2{\mathrm{Br}}_{12}^{4-}$	4	0D	LANDAJ	solvothermal	[62]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}\right),{\mathrm{Ag}}_2{\mathrm{Bi}}_2{\mathrm{Br}}_{12}^{4-}$	4	0D	LANDEN	solvothermal	[62]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}\mathrm{Fe}{\mathrm{N}}_6^{2+}\right),n\left({\mathrm{Ag}}_2{\mathrm{I}}_9{\mathrm{Pb}}_2^{3-}\right),\mathrm{Ag}{\mathrm{I}}_2^{-}$	4	1D	NEHKEU	solvothermal	[63]
${\mathrm{C}}_{10}{\mathrm{H}}_{22}{\mathrm{N}}_6{\mathrm{Ni}}^{2+},n\left({\mathrm{Ag}}_2{\mathrm{I}}_{10}{\mathrm{Pb}}_3^{2-}\right),{\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}$	5	2D	LOWYEE	solvothermal	[64]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{3+}\right),{\mathrm{Ag}}_4{\mathrm{Bi}}_2{\mathrm{Br}}_{16}^{6-}$	6	0D	YEJQUD	solvothermal	[59]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{3+}\right),{\mathrm{Ag}}_4{\mathrm{Bi}}_2{\mathrm{I}}_{16}^{6-}$	6	0D	YEJRAK	solvothermal	[59]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}\right),n\left({\mathrm{Ag}}_6{\mathrm{Br}}_{11}{\mathrm{K}}^{4-}\right)$	7	3D	UBIWIO	solvothermal	[65]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{2+}\right)}_{2n},n\left({\mathrm{Ag}}_6{\mathrm{I}}_{11}{\mathrm{K}}^{4-}\right)$	7	3D	DUYFAG	solvothermal	[44]
${\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}\right)}_{2n},n\left({\mathrm{Ag}}_6{\mathrm{I}}_{11}{\mathrm{K}}^{4-}\right)$	7	3D	DUYFEK	solvothermal	[44]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{2+}\right),n\left({\mathrm{Ag}}_6{\mathrm{Br}}_{11}{\mathrm{K}}^{4-}\right)$	7	3D	UBIWOU	solvothermal	[65]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Zn}}^{2+}\right),n\left({\mathrm{Ag}}_6{\mathrm{Br}}_{11}{\mathrm{K}}^{4-}\right)$	7	3D	UBIWUA	solvothermal	[65]
$2\left({\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Fe}{\mathrm{N}}_6^{2+}\right),n\left({\mathrm{Ag}}_6{\mathrm{Br}}_{11}{\mathrm{K}}^{4-}\right)$	7	3D	UBIXAH	solvothermal	[65]
${\left({\mathrm{C}}_{20}{\mathrm{H}}_{44}\mathrm{Ba}{\mathrm{O}}_{10}^{2+}\right)}_{2n},n\left({\mathrm{Ag}}_7\mathrm{Cu}{\mathrm{I}}_{12}^{4-}\right),n\left({\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}\right)$	8	1D	COZJAE	antisolvent	[43]
$2\left({\mathrm{C}}_{24}{\mathrm{H}}_{56}{\mathrm{N}}_8{\mathrm{O}}_8{\mathrm{Y}}^{3+}\right),n\left({\mathrm{Ag}}_2{\mathrm{I}}_{22}{\mathrm{Pb}}_7^{6-}\right)$	9	1D	MUBSAF	RT	[66]

contains mixed-metal haloargentates, and

Table 4. The CSD survey on halocuprates templated with metal–organic cations.

Sum Formula	Nuclearity	Dim.	CCDC Code	Synthesis	Ref.
$2\left({\mathrm{C}}_{15}{\mathrm{H}}_{23}\mathrm{Cl}\mathrm{Cu}{\mathrm{N}}_3{\mathrm{S}}_2^{+}\right),{\mathrm{Cl}}_6{\mathrm{Cu}}_2^{2-}$	2	0D	ACAROM	reflux	[67]
${\mathrm{C}}_{20}{\mathrm{H}}_{44}\mathrm{Ba}{\mathrm{O}}_{10}^{2+},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}$	2	0D	COZGUV	273 K	[43]
${\mathrm{C}}_{78}{\mathrm{H}}_{72}\mathrm{Mn}{\mathrm{O}}_6{\mathrm{P}}_6^{2+},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}$	2	0D	DEFMEK	RT	[68]
${\mathrm{C}}_{75}{\mathrm{H}}_{66}\mathrm{Mn}{\mathrm{O}}_6{\mathrm{P}}_6^{2+},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-},3\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	2	0D	DEFMIO	RT	[68]
${\left({\mathrm{C}}_4{\mathrm{H}}_{16}\mathrm{Cu}{\mathrm{N}}_4^{2+}\right)}_n,n\left({\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}\right)$	2	1D	ENCUID02	electrochemical	[69]
$2\left({\mathrm{C}}_{33}{\mathrm{H}}_{30}\mathrm{Cu}{\mathrm{N}}_4^{+}\right),{\mathrm{Br}}_4{\mathrm{Cu}}_2^{2-}$	2	0D	FOMTUW	RT	[70]
$2\left({\mathrm{C}}_{33}{\mathrm{H}}_{30}\mathrm{Cu}{\mathrm{N}}_4^{+}\right),{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}$	2	0D	FOMVAE	RT	[70]
$2\left({\mathrm{C}}_{33}{\mathrm{H}}_{30}\mathrm{Cu}{\mathrm{N}}_4^{+}\right),{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-},{\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}$	2	0D	FOMVEI	RT	[70]
$2\left({\mathrm{C}}_{29}{\mathrm{H}}_{27}\mathrm{Cu}\mathrm{N}{\mathrm{O}}_2{\mathrm{S}}_2^{+}\right),{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-},2\left(\mathrm{C}{\mathrm{H}}_2{\mathrm{Cl}}_2\right)$	2	0D	GEKPEU	antisolvent	[71]
${\mathrm{C}}_{80}{\mathrm{H}}_{64}{\mathrm{Br}}_2{\mathrm{Cu}}_2{\mathrm{N}}_{24}^{2+},{\mathrm{Br}}_6{\mathrm{Cu}}_2^{2-},4\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	2	0D	HAXHAS	solvothermal	[72]
${\mathrm{C}}_{69}{\mathrm{H}}_{66}{\mathrm{Cu}}_3{\mathrm{I}}_2{\mathrm{N}}_9{\mathrm{P}}_3^{+},0.5\left({\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}\right),2\left(\mathrm{C}{\mathrm{H}}_2{\mathrm{Cl}}_2\right)$	2	0D	IDALOQ	antisolvent	[73]
$2\left({\mathrm{C}}_{66}{\mathrm{H}}_{60}{\mathrm{Cu}}_3{\mathrm{N}}_{12}^{3+}\right),2\left(\mathrm{Cu}{\mathrm{I}}_3^{2-}\right),{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}$	2	0D	LUDRUX	RT	[74]
$2\left({\mathrm{C}}_{66}{\mathrm{H}}_{60}{\mathrm{Cu}}_3{\mathrm{N}}_{12}^{3+}\right),2\left(\mathrm{Cu}{\mathrm{I}}_3^{2-}\right),{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-},{\mathrm{C}}_6{\mathrm{H}}_6$	2	0D	LUDSAE	RT	[74]
${\mathrm{C}}_{39}{\mathrm{H}}_{43}\mathrm{Cu}{\mathrm{N}}_7^{+},0.5\left({\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}\right),1.5\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	2	0D	MAXYOB	RT	[75]
${\mathrm{C}}_{46}{\mathrm{H}}_{78}{\mathrm{Cl}}_2{\mathrm{Cu}}_2{\mathrm{N}}_6{\mathrm{S}}_4^{2+},{\mathrm{Cl}}_6{\mathrm{Cu}}_2^{2-}$	2	0D	NINFUM	reflux	[76]
${\mathrm{C}}_{19}{\mathrm{H}}_{31}\mathrm{Cl}\mathrm{Cu}{\mathrm{N}}_3{\mathrm{S}}_2^{+},0.5\left({\mathrm{Cl}}_6{\mathrm{Cu}}_2^{2-}\right)$	2	0D	NINGAT	reflux	[76]
$2\left({\mathrm{C}}_{33}{\mathrm{H}}_{43}\mathrm{Br}\mathrm{Cu}{\mathrm{N}}_3^{+}\right),{\mathrm{Br}}_4{\mathrm{Cu}}_2^2$	2	0D	NOFNOL	antisolvent	[77]
${\left({\mathrm{C}}_{10}{\mathrm{H}}_{20}\mathrm{Cs}{\mathrm{O}}_5^{+}\right)}_n,n\left({\mathrm{Cu}}_2{\mathrm{I}}_3^{-}\right)$	2	1D	NOFQOO	RT	[78]
${\left({\mathrm{C}}_{10}{\mathrm{H}}_{20}{\mathrm{O}}_5{\mathrm{Rb}}^{+}\right)}_n,n\left({\mathrm{Cu}}_2{\mathrm{I}}_3^{-}\right)$	2	1D	NOFRAB	RT	[78]
${\left({\mathrm{C}}_{12}{\mathrm{H}}_{24}\mathrm{K}{\mathrm{O}}_6^{+}\right)}_n,n\left({\mathrm{Cu}}_2{\mathrm{I}}_3^{-}\right)$	2	1D	NOFRIJ	RT	[79]
${\mathrm{C}}_{22}{\mathrm{H}}_{18}{\mathrm{Cl}}_2\mathrm{Cu}{\mathrm{N}}_4^{+},0.5\left({\mathrm{Cl}}_4{\mathrm{Cu}}_2^{2-}\right),\mathrm{C}{\mathrm{H}}_2{\mathrm{Cl}}_2$	2	0D	PAPGOD	RT	[80]
${\mathrm{C}}_{16}{\mathrm{H}}_{48}{\mathrm{O}}_8{\mathrm{S}}_8{\mathrm{Tb}}^{3+},{\mathrm{Cu}}_2{\mathrm{I}}_5^{3-}$	2	0D	PARSUY	antisolvent	[81]
$2\left({\mathrm{C}}_{23}{\mathrm{H}}_{23}{\mathrm{Cl}}_2{\mathrm{Cu}}_2{\mathrm{N}}_4{\mathrm{O}}^{+}\right),{\mathrm{Cl}}_6{\mathrm{Cu}}_2^{2-}$	2	0D	PEVBUO	hot MeCN	[82]
${\mathrm{C}}_{16}{\mathrm{H}}_{48}{\mathrm{O}}_8{\mathrm{S}}_8{\mathrm{Y}}^{3+},{\mathrm{Cu}}_2{\mathrm{I}}_5^{3-}$	2	0D	PIXZEC	RT	[83]
${\mathrm{C}}_{28}{\mathrm{H}}_{37}{\mathrm{Cu}}_2\mathrm{I}{\mathrm{N}}_9^{+},{\mathrm{C}}_4{\mathrm{H}}_8\mathrm{O},0.5\left({\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}\right)$	2	0D	POFCAQ	antisolvent	[84]
$4\left({\mathrm{C}}_{33}{\mathrm{H}}_{32}{\mathrm{Cu}}_2{\mathrm{N}}_4{\mathrm{O}}_7\right),4\left(\mathrm{C}{\mathrm{H}}_{10}\mathrm{Li}{\mathrm{O}}_4^{+}\right),{\mathrm{Br}}_4{\mathrm{Cu}}_2^{2-}$	2	0D	PUKNOA	RT	[85]
$2\left({\mathrm{C}}_{40}{\mathrm{H}}_{48}\mathrm{Cl}\mathrm{Fe}{\mathrm{N}}_4^{+}\right),{\mathrm{Cl}}_4{\mathrm{Cu}}_2^{2-},{\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}$	2	0D	QACWEW	RT	[86]
${\mathrm{C}}_{88}{\mathrm{H}}_{56}{\mathrm{Cu}}_4{\mathrm{N}}_{16}^{2+},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}$	2	0D	QADPOD	antisolvent	[87]
${\mathrm{C}}_{72}{\mathrm{H}}_{64}{\mathrm{Cu}}_2{\mathrm{N}}_{12}^{2+},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}$	2	0D	QOWMEW	RT	[88]
${\mathrm{C}}_{40}{\mathrm{H}}_{28}{\mathrm{Cu}}_2{\mathrm{I}}_2{\mathrm{N}}_8^{+},0.5\left({\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}\right)$	2	0D	REQJAZ	hydrothermal	[89]
${\left({\mathrm{C}}_{20}{\mathrm{H}}_{14}\mathrm{Cu}\mathrm{I}{\mathrm{N}}_4^{+}\right)}_n,0.5n\left({\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}\right)$	2	0D	REQJUT	hydrothermal	[89]
$2\left({\mathrm{C}}_{13}{\mathrm{H}}_{33}\mathrm{Cu}\mathrm{I}{\mathrm{N}}_4^{+}\right),0.9\left({\mathrm{Br}}_2{\mathrm{Cu}}_2{\mathrm{I}}_2^{2-}\right),0.2\left({\mathrm{I}}^{-}\right)$	2	0D	ROBXAI	277 K	[90]
${\mathrm{C}}_{44}{\mathrm{H}}_{60}\mathrm{Cu}{\mathrm{N}}_8^{+},0.5\left({\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}\right)$	2	0D	SEYYIH	RT	[91]
${\mathrm{C}}_{32}{\mathrm{H}}_{44}\mathrm{Cu}{\mathrm{N}}_{12}^{2+},{\mathrm{Br}}_6{\mathrm{Cu}}_2^{2-}$	2	0D	SIKSUD	RT	[92]
$2\left({\mathrm{C}}_{16}{\mathrm{H}}_{15}\mathrm{Cu}\mathrm{I}{\mathrm{N}}_3{\mathrm{P}}^{+}\right),{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-},2\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	2	0D	SITWEA	RT	[93]
${\mathrm{C}}_{32}{\mathrm{H}}_{108}{\mathrm{O}}_{27}{\mathrm{S}}_{16}{\mathrm{Y}}_6^{8+},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-},6\left({\mathrm{I}}^{-}\right)$	2	0D	SOCYIT	RT	[94]
${\mathrm{C}}_{114}{\mathrm{H}}_{66}{\mathrm{Cu}}_9{\mathrm{N}}_{54}^{2+},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-},6\left(\mathrm{C}{\mathrm{H}}_4\mathrm{O}\right),4\left({\mathrm{H}}_2\mathrm{O}\right)$	2	0D	TUNDUD	solvothermal	[95]
${\left({\mathrm{C}}_4{\mathrm{H}}_{16}\mathrm{Cu}{\mathrm{N}}_4^{2+}\right)}_n,n\left({\mathrm{Br}}_4{\mathrm{Cu}}_2^{2-}\right)$	2	1D	VAHWAD	hydrothermal	[96]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{22}{\mathrm{Cl}}_5{\mathrm{Cu}}_2{\mathrm{N}}_8{\mathrm{S}}_2^{+}\right),{\mathrm{Cl}}_6{\mathrm{Cu}}_2^{2-}$	2	0D	VECGIU	RT	[97]
${\mathrm{C}}_{48}{\mathrm{H}}_{46}\mathrm{Cl}\mathrm{Cu}{\mathrm{N}}_{10}^{+},0.5\left({\mathrm{Cl}}_6{\mathrm{Cu}}_2^{2-}\right)$	2	0D	WUWWIV	RT	[98]
${\mathrm{C}}_{36}{\mathrm{H}}_{40}\mathrm{Cu}{\mathrm{F}}_2{\mathrm{N}}_6{\mathrm{O}}_8^{2+},{\mathrm{Cl}}_4{\mathrm{Cu}}_2^{2-}$	2	0D	XELPAH	393 K	[99]
$2\left({\mathrm{C}}_{31}{\mathrm{H}}_{31}{\mathrm{Br}}_2{\mathrm{Cu}}_2{\mathrm{N}}_7^{2+}\right),2\left({\mathrm{Br}}^{-}\right),{\mathrm{Br}}_4{\mathrm{Cu}}_2^{2-}$	2	0D	XUPDOB	antisolvent	[100]
${\mathrm{C}}_{32}{\mathrm{H}}_{60}{\mathrm{Cu}}_2{\mathrm{N}}_{12}^{2+},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}$	2	0D	XUZDAZ	NA	[101]
${\left({\mathrm{C}}_8{\mathrm{H}}_{12}\mathrm{Li}{\mathrm{N}}_4^{+}\right)}_n,n\left({\mathrm{Cu}}_2{\mathrm{I}}_3^{-}\right)$	2	1D	YADTUS	RT	[102]
$2\left({\mathrm{C}}_{42}{\mathrm{H}}_{36}\mathrm{Cu}{\mathrm{N}}_8^{+}\right),{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-},2\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	2	0D	YASVAT	RT	[103]
$2\left({\mathrm{C}}_{22}{\mathrm{H}}_{32}\mathrm{Br}\mathrm{Cu}{\mathrm{N}}_8^{+}\right),{\mathrm{Br}}_4{\mathrm{Cu}}_2^{2-}$	2	0D	YEMXUN	antisolvent	[2]
${\mathrm{C}}_{24}{\mathrm{H}}_{48}\mathrm{Cu}{\mathrm{N}}_{12}^{2+},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-},2\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	2	0D	YITXAB	RT	[104]
$2\left({\mathrm{C}}_{25}{\mathrm{H}}_{28}\mathrm{Cl}\mathrm{Cu}{\mathrm{N}}_2{\mathrm{S}}_2^{+}\right),{\mathrm{Cl}}_4{\mathrm{Cu}}_2^{2-},2\left(\mathrm{C}{\mathrm{H}}_4\mathrm{O}\right)$	2	0D	YUDFAE	RT	[105]
${\mathrm{C}}_{24}{\mathrm{H}}_{56}\mathrm{Cu}{\mathrm{N}}_{12}^{2+},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}$	2	0D	YUXBOJ	RT	[106]
${\mathrm{C}}_{26}{\mathrm{H}}_{40}{\mathrm{Cu}}_2\mathrm{I}{\mathrm{N}}_6{\mathrm{S}}_4^{+},0.5\left({\mathrm{Cu}}_2{\mathrm{I}}_4^{2-}\right),{\mathrm{H}}_2\mathrm{O}$	2	0D	ZAJBIY	NA	[107]
${\mathrm{C}}_{32}{\mathrm{H}}_{44}\mathrm{Cu}{\mathrm{N}}_8{\mathrm{S}}_6^{2+},{\mathrm{Cl}}_6{\mathrm{Cu}}_2^{2-},{\mathrm{C}}_7{\mathrm{H}}_8$	2	0D	ZELWOG	NA	[108]
${\left({\mathrm{C}}_{14}{\mathrm{H}}_{16}\mathrm{Cu}{\mathrm{N}}_4{\mathrm{O}}_2^{2+}\right)}_n,n\left({\mathrm{Cl}}_5{\mathrm{Cu}}_3^{2-}\right)$	3	1D	BOHYCU	RT	[109]
${\left({\mathrm{C}}_{24}{\mathrm{H}}_{32}\mathrm{K}{\mathrm{O}}_8^{+}\right)}_n,n\left({\mathrm{Cu}}_3{\mathrm{I}}_4^{-}\right)$	3	1D	CUMWEM	RT	[110]
${\left({\mathrm{C}}_{14}{\mathrm{H}}_{26}\mathrm{Cu}{\mathrm{N}}_2{\mathrm{O}}_5^{2+}\right)}_n,n\left({\mathrm{Cl}}_8{\mathrm{Cu}}_3^{2-}\right)$	3	1D	JIZBUP	RT	[111]
${\left({\mathrm{C}}_{20}{\mathrm{H}}_{16}\mathrm{Br}\mathrm{Cu}{\mathrm{N}}_4^{+}\right)}_n,n\left({\mathrm{Br}}_4{\mathrm{Cu}}_3^{-}\right)$	3	1D	REBDOR	hydrothermal	[112]
$2\left({\mathrm{C}}_8{\mathrm{H}}_{16}\mathrm{Br}\mathrm{Cu}{\mathrm{N}}_6{\mathrm{O}}_2^{+}\right),n\left({\mathrm{Br}}_5{\mathrm{Cu}}_3^{2-}\right)$	3	1D	VOVFOE	RT	[113]

and

Table 5. The CSD survey on halocuprates templated with metal–organic cations.

Sum Formula	Nuclearity	Dim.	CCDC Code	Synthesis	Ref.
${\left({\mathrm{C}}_{36}{\mathrm{H}}_{44}\mathrm{Cu}{\mathrm{F}}_2{\mathrm{N}}_6{\mathrm{O}}_8^{+}\right)}_n,n\left({\mathrm{Br}}_5{\mathrm{Cu}}_3^{-}\right),2n\left({\mathrm{H}}_2\mathrm{O}\right)$	3	1D	WARXAP	NA	[114]
${\left({\mathrm{C}}_{10}{\mathrm{H}}_{30}\mathrm{Cu}{\mathrm{O}}_5{\mathrm{S}}_5^{2+}\right)}_n,n\left({\mathrm{C}}_2{\mathrm{H}}_6{\mathrm{Cu}}_4{\mathrm{I}}_6\mathrm{O}{\mathrm{S}}^{2-}\right)$	4	1D	ATAMIT	antisolvent	[115]
${\left({\mathrm{C}}_{16}{\mathrm{H}}_{32}\mathrm{K}{\mathrm{O}}_8^{+}\right)}_{2n},n\left({\mathrm{Cu}}_4{\mathrm{I}}_6^{2-}\right)$	4	1D	ATUQIP	RT	[116]
$2\left({\mathrm{C}}_{14}{\mathrm{H}}_{22}\mathrm{Li}{\mathrm{O}}_6^{+}\right),2\left({\mathrm{C}}_{14}{\mathrm{H}}_{20}{\mathrm{O}}_5\right),{\mathrm{Cu}}_4{\mathrm{I}}_6^{2-}$	4	0D	BEQREU	RT	[117]
$2\left({\mathrm{C}}_{28}{\mathrm{H}}_{40}\mathrm{Cs}{\mathrm{O}}_{10}^{+}\right),{\mathrm{Cu}}_4{\mathrm{I}}_6^{2-}$	4	0D	BEQRIY	RT	[117]
${\mathrm{C}}_{24}{\mathrm{H}}_{54}{\mathrm{Na}}_2{\mathrm{O}}_{15}^{2+},{\mathrm{Cu}}_4{\mathrm{I}}_6^{2-}$	4	0D	BEQROE	RT	[117]
${\mathrm{C}}_{22}{\mathrm{H}}_{48}\mathrm{Ba}{\mathrm{O}}_{10}^{2+},{\mathrm{Cu}}_4{\mathrm{I}}_6^{2-}$	4	0D	COZHAC	RT	[43]
${\mathrm{C}}_{18}{\mathrm{H}}_{44}\mathrm{Ba}{\mathrm{O}}_{10}^{2+},{\mathrm{Cu}}_4{\mathrm{I}}_6^{2-}$	4	0D	COZHEG	RT	[43]
${\mathrm{C}}_{74}{\mathrm{H}}_{62}\mathrm{Mn}{\mathrm{O}}_6{\mathrm{P}}_6^{2+},{\mathrm{Cu}}_4{\mathrm{I}}_6^{2-}$	4	0D	DEFMAG	RT	[68]
$2\left({\mathrm{C}}_{90}{\mathrm{H}}_{72}\mathrm{Mn}{\mathrm{O}}_6{\mathrm{P}}_6^{2+}\right),{\mathrm{Cu}}_4{\mathrm{I}}_6^{2-},{\mathrm{Cu}}_2{\mathrm{I}}_4^{2-},2\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	2 and 4	0D	DEFPIR	RT	[68]
${\mathrm{Cl}}_8{\mathrm{Cu}}_4^{4-},2\left({\mathrm{C}}_{36}{\mathrm{H}}_{32}{\mathrm{Cu}}_2{\mathrm{N}}_{12}^{2+}\right),{\mathrm{C}}_2{\mathrm{H}}_6\mathrm{O}$	4	0D	LESVIR	353 K	[118]
${\left({\mathrm{C}}_{52}{\mathrm{H}}_{54}\mathrm{Cu}{\mathrm{N}}_6{\mathrm{O}}_2^{2+}\right)}_n,n\left({\mathrm{Cu}}_4{\mathrm{I}}_6^{2-}\right),n\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	4	1D	QINGAY	RT	[119]
${\mathrm{C}}_{34}{\mathrm{H}}_{50}\mathrm{Al}\mathrm{Br}{\mathrm{N}}_4{\mathrm{O}}_2{\mathrm{P}}_2^{+},2\left({\mathrm{C}}_6{\mathrm{H}}_6\right),{\mathrm{Br}}_6{\mathrm{Cu}}_4^{-}$	4	0D	RUJWOL	RT	[120]
${\mathrm{C}}_{12}{\mathrm{H}}_{24}{\mathrm{O}}_6{\mathrm{Rb}}^{+},{\mathrm{C}}_{14}{\mathrm{H}}_{27}\mathrm{N}{\mathrm{O}}_6{\mathrm{Rb}}^{+},{\mathrm{Cu}}_4{\mathrm{I}}_6^{2-}$	4	0D	VEQWUJ	RT	[121]
${\mathrm{Cu}}_4{\mathrm{I}}_6^{2-},{\mathrm{C}}_{12}{\mathrm{H}}_{24}{\mathrm{O}}_6{\mathrm{Rb}}^{+},{\mathrm{C}}_{15}{\mathrm{H}}_{30}{\mathrm{O}}_7{\mathrm{Rb}}^{+}$	4	0D	VIBSEI	254 K	[7]
$3\left({\mathrm{C}}_{46}{\mathrm{H}}_{38}{\mathrm{Cu}}_2\mathrm{I}{\mathrm{N}}_6{\mathrm{O}}_4^{+}\right),{\mathrm{Cu}}_4{\mathrm{I}}_7^{3-},4\left(\mathrm{C}{\mathrm{H}}_2{\mathrm{Cl}}_2\right)$	4	0D	YAFWEK	antisolvent	[122]
${\mathrm{C}}_{24}{\mathrm{H}}_{56}{\mathrm{N}}_8{\mathrm{O}}_8{\mathrm{Y}}^{3+},{\mathrm{Cu}}_4{\mathrm{I}}_7^{3-}$	4	0D	YEWVOM	RT	[123]
$2\left({\mathrm{C}}_{12}{\mathrm{H}}_{24}\mathrm{K}{\mathrm{O}}_6^{+}\right),{\mathrm{Br}}_6{\mathrm{Cu}}_4^{2-}$	4	0D	ZEJWAQ	RT	[6]
$4\left({\mathrm{C}}_{12}{\mathrm{H}}_{24}\mathrm{Na}{\mathrm{O}}_6^{+}\right),{\mathrm{C}}_{12}{\mathrm{H}}_{24}{\mathrm{O}}_6,{\mathrm{Br}}_6{\mathrm{Cu}}_4^{2-},2\left({\mathrm{Br}}_4{\mathrm{In}}^{-}\right)$	4	0D	ZEJWIY	RT	[6]
${\mathrm{C}}_{32}{\mathrm{H}}_{60}{\mathrm{Cu}}_2{\mathrm{N}}_{12}^{2+},{\mathrm{Cu}}_4{\mathrm{I}}_6^{2-}$	4	0D	ZIVMOI	NA	[124]
${\mathrm{C}}_{168}{\mathrm{H}}_{136}\mathrm{Mn}{\mathrm{O}}_{14}{\mathrm{P}}_{12}^{2+},{\mathrm{C}}_2{\mathrm{H}}_3{\mathrm{Cu}}_5{\mathrm{I}}_7{\mathrm{N}}^{2-},7\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	5	0D	BIPSEC	RT	[125]
${\left({\mathrm{C}}_{12}{\mathrm{H}}_{30}\mathrm{Ca}{\mathrm{O}}_9^{2+}\right)}_n,n\left({\mathrm{Cu}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	EKIGIO	RT	[126]
${\left({\mathrm{C}}_{12}{\mathrm{H}}_{30}{\mathrm{O}}_9{\mathrm{Sr}}^{2+}\right)}_n,n\left({\mathrm{Cu}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	EKIGOU	RT	[126]
${\left({\mathrm{C}}_{12}{\mathrm{H}}_{30}{\mathrm{O}}_9{\mathrm{Zn}}^{2+}\right)}_n,n\left({\mathrm{Cu}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	EKIGUA	RT	[126]
${\mathrm{C}}_{38}{\mathrm{H}}_{40}{\mathrm{Cu}}_3{\mathrm{N}}_4{\mathrm{O}}_8^{2+},{\mathrm{Cu}}_5{\mathrm{I}}_7^{2-}$	5	0D	NAZNUZ	RT	[127]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{40}\mathrm{Cu}{\mathrm{N}}_4^{+}\right),{\mathrm{Cu}}_5{\mathrm{I}}_7^{2-}$	5	0D	NENWOU	NA	[128]
${\mathrm{C}}_{15}{\mathrm{H}}_{46}{\mathrm{O}}_8{\mathrm{S}}_7{\mathrm{Tb}}^{3+},n\left({\mathrm{Cu}}_5{\mathrm{I}}_7^{2-}\right),{\mathrm{I}}^{-}$	5	1D	NOCBOZ	RT	[129]
${\left({\mathrm{C}}_4{\mathrm{H}}_{16}\mathrm{Cu}{\mathrm{N}}_4^{2+}\right)}_n,n\left({\mathrm{Br}}_7{\mathrm{Cu}}_5^{2-}\right)$	5	1D	VAHWEH	hydrothermal	[96]
${\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Fe}{\mathrm{N}}_6^{2+},n\left({\mathrm{Cu}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	WUYZOH	solvothermal	[130]
${\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{2+},n\left({\mathrm{Cu}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	WUYZUN	solvothermal	[130]
${\mathrm{C}}_{30}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+},n\left({\mathrm{Cu}}_5{\mathrm{I}}_7^{2-}\right)$	5	1D	WUZBAW	solvothermal	[130]
${\mathrm{C}}_{30}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{2+},n\left({\mathrm{Br}}_8{\mathrm{Cu}}_5^{2-}\right)$	5	1D	WUZBIE	solvothermal	[130]
${\mathrm{C}}_{78}{\mathrm{H}}_{72}\mathrm{Mn}{\mathrm{O}}_6{\mathrm{P}}_6^{2+},0.5\left({\mathrm{Cu}}_6{\mathrm{I}}_{10}^{4-}\right),2\left({\mathrm{C}}_2{\mathrm{H}}_3\mathrm{N}\right)$	6	0D	DEFLOT	RT	[68]
${\left({\mathrm{Cl}}_{16}{\mathrm{Cu}}_7^{2-}\right)}_n,n\left({\mathrm{C}}_{14}{\mathrm{H}}_{24}\mathrm{Cu}{\mathrm{N}}_4^{2+}\right)$	7	2D	LODVEG	RT	[131]
${\left({\mathrm{C}}_4{\mathrm{H}}_{16}\mathrm{Cu}{\mathrm{N}}_4^{2+}\right)}_{2n},n\left({\mathrm{Cl}}_{11}{\mathrm{Cu}}_7^{4-}\right)$	7	3D	NIGNOG	hydrothermal	[132]
$2\left({\mathrm{C}}_{20}{\mathrm{H}}_{16}\mathrm{I}{\mathrm{N}}_4{\mathrm{Ru}}^{+}\right),n\left({\mathrm{Cu}}_7{\mathrm{I}}_9^{2-}\right)$	7	1D	WUYNUB	solvothermal	[130]
${\left({\mathrm{C}}_{20}{\mathrm{H}}_{16}\mathrm{I}\mathrm{Mn}{\mathrm{N}}_4^{+}\right)}_{2n},n\left({\mathrm{Cu}}_7{\mathrm{I}}_9^{2-}\right)$	7	1D	WUZCAX	solvothermal	[130]
${\left({\mathrm{Cu}}_7{\mathrm{I}}_{10}^{3-}\right)}_n,n\left({\mathrm{C}}_{18}{\mathrm{H}}_{46}{\mathrm{N}}_6{\mathrm{O}}_8{\mathrm{Y}}^{3+}\right)$	7	1D	YEWVUS	RT	[123]
${\mathrm{C}}_{20}{\mathrm{H}}_{16}\mathrm{Cu}\mathrm{I}{\mathrm{N}}_4^{+},{\mathrm{C}}_{12}{\mathrm{H}}_{14}{\mathrm{N}}_2^{2+},n\left({\mathrm{Cu}}_8{\mathrm{I}}_{11}^{3-}\right)$	8	1D	WUZBEA	solvothermal	[130]
${\left({\mathrm{Cu}}_9{\mathrm{I}}_{14}^{3-}\right)}_n,n\left({\mathrm{C}}_{18}{\mathrm{H}}_{48}{\mathrm{N}}_6{\mathrm{O}}_9{\mathrm{Tb}}^{3+}\right)$	9	2D	PARTOT	RT	[81]
${\left({\mathrm{Cu}}_9{\mathrm{I}}_{14}^{3-}\right)}_n,n\left({\mathrm{C}}_{18}{\mathrm{H}}_{48}{\mathrm{N}}_6{\mathrm{O}}_9{\mathrm{Y}}^{3+}\right)$	9	2D	YEWWAZ	RT	[123]
${\left({\mathrm{C}}_{48}{\mathrm{H}}_{32}{\mathrm{Cl}}_2{\mathrm{Co}}_2{\mathrm{N}}_8^{2+}\right)}_n,n\left({\mathrm{H}}_2{\mathrm{Cu}}_9{\mathrm{I}}_{11}{\mathrm{O}}^{2-}\right)$	9	1D	UHOWUK	solvothermal	[133]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}{\mathrm{N}}_6{\mathrm{Ni}}^{2+}\right),{\mathrm{H}}_2{\mathrm{Cu}}_{10}{\mathrm{I}}_{15}^{4-}$	10	0D	IWEZEP	hydrothermal	[134]
$2\left({\mathrm{C}}_{36}{\mathrm{H}}_{24}\mathrm{Co}{\mathrm{N}}_6^{2+}\right),{\mathrm{Cu}}_{10}{\mathrm{I}}_{15}^{4-}$	10	0D	SODMUU	solvothermal	[135]

contain entries for halocuprates. We have selected the compounds with two criteria: (A) they must contain metal–organic templating cations and (B) the nuclearity of halometallate must be greater than one and effectively be between 2 and 22, as was found in this study.

2. Discussion

2.1. Haloargentates

There are 29 compounds of dinculear haloargentates, predominantly with 0D structures, with a minority displaying either 1D or 0D characteristics. Only one example (RUNSID) contains an inorganic network of 2D layered structure, but the compound contains both dinuclear [${\mathrm{Ag}}_2{\mathrm{I}}_5{]}^{3-}$ and pentanuclear [${\mathrm{Ag}}_5{\mathrm{I}}_8{]}^{3-}$ iodoargentate clusters. Some characteristic structures of dinuclear haloargentates are presented in Figure 1, while the detailed information on the CSD entries are presented in Table 1 and Table 2.

The structure of CEQJAM contains 1D chains of edge-sharing [${\mathrm{Ag}}_2{\mathrm{Br}}_4{]}^{2-}$ tetrahedra templated by [Cu(Br)(phen${)}_2$${]}^{+}$ complex cations. On the other hand, the structure of EFATIP contains a 3D inorganic substructure, where [Zn(en${)}_3$${]}^{2+}$ cations template a [${\mathrm{Ag}}_2{\mathrm{I}}_4{]}_n^{2-}$ iodoargentate framework of vertex-sharing [${\mathrm{AgI}}_4{]}^{3-}$ tetrahedra. On the contrary, the structure of IHINES contains a one-dimensional iodoargentate inorganic subnetwork stabilized with Ag$\cdots$Ag metallophilic interactions (Ag-Ag distances in the range of 2.9–3.1 Å). In this case, the inorganic subnetwork is templated by N-heterocyclic carbene silver complex cations with coordination number 2, forming $\pi$-$\pi$ stacked dimers. The effect of the shape of the templating metal–organic cation can be effectively contrasted with the structure of VUDKUB, where the one-dimensional iodoargentate subnetwork [${\mathrm{Ag}}_2{\mathrm{I}}_3{]}^{-}$ is made from edge-sharing tetrahedra, but weak argentophilic interactions can be distinguished (Ag-Ag distances 3.3 Å). In this case, the templating cations are formed from potentially tetradenate bis N-heterocyclic carbene silver complex of the general formula [$\mathrm{ML}{]}^{+}$. There are only six examples of trinuclear haloargentates (with one-dimensional inorganic subnetwork), among which only one is a zero-dimensional assembly. The structure of PUNKIU consists of [Zn(bipy${)}_3$${]}^{2+}$ cations templating the 1D iodoargentate chain of the formula [${\mathrm{Ag}}_3{\mathrm{I}}_5{]}_n^{2-}$. As shown in Figure 2, the inorganic subnetwork propagates perpendicularly to the $bc$ plane.

In the iodoargentate, a short Ag$\cdots$Ag contact can be distinguished, 3.2 Å, indicating an argentophilic interaction. The structure of PUZJUR also contains a trinuclear iodoargentate, of the formula [${\mathrm{Ag}}_3{\mathrm{I}}_7{]}^{4-}$; however, it is a discrete assembly with ${\mu }^3$-I connected triangles. In this case, the assembly is templated by the [Fe(phen${)}_3$${]}^{2+}$ cation and no argentophilic interactions are detected. There are only two examples of haloargentates with a nuclearity of four. The structure of YASYEZ contains a 1D inorganic subnetwork of chloroargentate [${\mathrm{Ag}}_4{\mathrm{Cl}}_6{]}_n^{2-}$ templated with a large heteroleptic ruthenium complex. In this case, argentophilic interactions can be distinguished with Ag$\cdots$Ag distances in the range of 2.99–3.10 Å. The second tetranuclear structure, YIJHIJ, is discrete and templated with a di-silver tetra-NHC ligand where a strong argentophilic interaction with a distance of 2.84 Å can be detected. In the iodoargenate, strong argentophilic interactions are also present, with distances below 3.0 Å, in the range of 2.84–2.89 Å. The [${\mathrm{Ag}}_4{\mathrm{I}}_8{]}^{4-}$ iodoargentate possesses a rather irregular shape with each Ag center exhibiting a distorted tetrahedral coordination geometry.

There are only six examples of trinuclear haloargentates (with one-dimensional inorganic subnetwork), among which only one is a zero-dimensional assembly. The structure of PUNKIU consists of [Zn(bipy${)}_3$${]}^{2+}$ cations templating the 1D iodoargentate chain of the formula [${\mathrm{Ag}}_3{\mathrm{I}}_5{]}_n^{2-}$. As shown in Figure 2, the inorganic subnetwork propagates perpendicularly to the $bc$ plane.

The members of the pentanuclear haloargentates templated with metal–organic cations include 13 examples of 0D and 1D dimensionalities of inorganic subnetworks. The structure of DUQMIO contains chains [${\mathrm{Ag}}_5{\mathrm{I}}_6{]}_n^{-}$ propagating perpendicular to the $ac$ plane and possess a cross-section of a ten-armed star. Such a unique assembly is templated with a tetrahedral zinc solvento complex with bis 4,4-bipyridine ligands, which are arranged along the c direction by $\pi$-$\pi$ stacking interactions. One of the nitrogen heteroatoms remains uncoordinated. On the other hand, a structure of DUQLIN contains 1D iodoargentate chains of a composition [${\mathrm{Ag}}_5{\mathrm{I}}_7{]}_n^{2-}$, propagated along the b direction of the unit cell. The structure is templated by bis-bipy manganese(II) solvento complex (DMSO). Argentophilic interactions are present in the structure, with Ag-Ag distances in the range of 3.1–3.3 Å. The octahedral manganese(II) complex molecules are arranged into dimers by T-shape $\pi$-$\pi$ stacking interactions.

The number of hexanuclear haloargentate examples is 16. Among them, 0D, 1D, and 2D inorganic subnetworks can be found. The structure of JEPJEX, shown in Figure 3, contains [${\mathrm{Ag}}_6{\mathrm{I}}_8{]}_n^{2-}$ layers propagating along the $ab$ plane.

The structure is templated by bis-NHC silver complex, and its coordination number is 2. The structure of PUCVAN is also 2D, in terms of the iodoargentate connectivity of [${\mathrm{Ag}}_6{\mathrm{I}}_8{]}_n^{2-}$. In this case, however, there can be distinguished metallophilic interactions with distances in the range of 3.1–3.2 Å. The iodoargentate layers propagate along the $ab$ plane and are templated by the vanadium(II) solvento complex, which is remarkable, because in the synthesis of this compound, a starting material was ${\mathrm{V}}_2{\mathrm{O}}_5$. The structure of ZEXMUO is also an example of 2D layered haloargentate with a formula [${\mathrm{Ag}}_6{\mathrm{I}}_{11}{]}_n^{5-}$. In this case, the templation occurs with the presence of [Fe(bipy${)}_3$${]}^{2+}$ and ${\mathrm{NH}}_4^{+}$ cations. The layers propagate along the $ab$ plane. The argentophilic interactions are also detectable, with a Ag$\cdots$Ag distance of 3.04 Å. On the contrary, the ZICVUF structure has a 1D inorganic subnetwork. The [${\mathrm{Ag}}_6{\mathrm{I}}_9{]}_n^{3-}$ iodoargentate propagates along the $bc$ plane, templated by [Nd(DMF${)}_7$(dpdo)Nd(DMF${)}_7$${]}^{6+}$ with dpdo as $\mu$-4,4’-bipyridine N,N’-dioxide. The argentophilic interactions can be detected in these chains, with distances in the range of 3.1–3.3 Å.

There are only two haloargentates with a nuclearity of eight in the CSD. The structure of BIZRIN contains a discrete self-assembled iodoargentate of the formula [${\mathrm{Ag}}_8{\mathrm{I}}_{15}{]}^{7-}$, templated by the ${\mu }_3$-carbonato-tris(bis(2-aminoethyl)amine)-tri-lead multinuclear complex. In this structure, eight [${\mathrm{AgI}}_4{]}^{3-}$ tetrahedra are connected by sharing edges to give a cluster with $C_3$ symmetry. Interestingly, no metallophilic interactions are detected in this structure. The structure of COZHIK, shown in Figure 4, contains a 1D iodoargentate of the formula [${\mathrm{Ag}}_8{\mathrm{I}}_{12}{]}_n^{4-}$, templated with two barium(II) bis-tetraglyme complexes. Argentophilic interactions can be distinguished with a distance of 3.09 Å. The chains of iodoargentate propagate along the b direction.

There are only two haloargentates with a nuclearity of nine. The structure of AMOZOU contains an iodoargentate of the formula [${\mathrm{Ag}}_9{\mathrm{I}}_{12}{]}_n^{3-}$, which is 1D and is templated by the [La(DMF${)}_8$${]}^{3+}$ solvento complex. Argentophilic interactions can be identified with a distance of 3.14 Å. The chains propagate along the c direction. On the other hand, the structure of LINROS contains an inorganic subnetwork of 2D layered connectivity, despite the same formula of iodoargentate [${\mathrm{Ag}}_9{\mathrm{I}}_{12}{]}_n^{3-}$. In this case, the structure is templated by [Al(DMSO${)}_8$${]}^{3+}$, and argentophilic interactions can be distinguished with distances in the range of 2.99–3.11 Å.

There are only three haloargentates with a nuclearity of 10; two are 1D and one is 2D. The structure of CENHUC01 contains an iodoargentate of the formula [${\mathrm{Ag}}_{10}{\mathrm{I}}_{11}{]}^{-}$ templated by a [Co(bipy${)}_3$${]}^{2+}$ complex cation and the charge is balanced by one hydroxy anion. The crystal data, however, are not of sufficient quality, and level B alerts were reported in the checkcif. The 1D chains propagate along the a direction and no argentophilic interactions were detected. The structure of HUZCEL also contains a decanuclear iodoargentate with 1D connectivity. The iodoargentate of the formula [${\mathrm{Ag}}_{10}{\mathrm{I}}_{12}{]}_n^{2-}$ is templated by a [Ni(bipy)(THF${)}_2$${]}^{2+}$ cation, and 1D chains are propagated along the a direction. The argentophilic interaction can be distinguished with distances in the range of 3.15–3.34 Å. In the structure of PUZKEC, the iodoargentate network is layered, templated with two [Mn(phen${)}_3$${]}^{2+}$ cations. The iodoargentate of the formula [${\mathrm{Ag}}_{10}{\mathrm{I}}_{14}{]}_n^{4-}$ propagates along the $ab$ plane, and argentophilic interactions are detected, with distances in the range of 3.05–3.35 Å.

There are no examples of haloargentate with nuclearities of 11 and 12 in the database. On the other hand, there are four examples of haloargentates with a nuclearity of 13, all of which possess a 3D inorganic subnetwork. The structure of QUSNOJ, shown in Figure 5, contains a $C3$ symmetric iodoargentate of the formula [${\mathrm{Ag}}_{13}{\mathrm{I}}_{17}{]}_n^{4-}$ in which argentophilic interactions can be detected, with distances in the range of 2.92–3.23 Å.

The templation occurs in the presence of two $D3$ symmetric [Co(phen${)}_3$${]}^{2+}$ complex cations in the space group $P{2}_{1}3$. The structures of CEQHIS, CEQHOY, and CEQHUE contain the same motif of bromoargentate of the formula [${\mathrm{Ag}}_{13}{\mathrm{Br}}_{17}{]}_n^{4-}$, which represents a 3D inorganic subnetwork. The structures are templated with [TM(phen${)}_3$${]}^{2+}$ complex cations, where TM = ${\mathrm{Fe}}^{2+}$, ${\mathrm{Co}}^{2+}$, and ${\mathrm{Ni}}^{2+}$. Argentophilic interactions can be distinguished with distances in the range of 2.87–3.24 Å. The three above-mentioned compounds crystallize in the $I{2}_{1}3$ space group.

There are only two haloargentates with a nuclearity of 14 and both are discrete 0D assemblies. The structure of ATAPOC contains an iodoargentate of the formula [${\mathrm{Ag}}_{14}{\mathrm{I}}_{22}{]}^{8-}$, templated with four [Co(DMF${)}_6$${]}^{2+}$ solvento complexes. Argentophilic interactions can be distinguished, with distances in the range: 3.07–3.23 Å. On the other hand, the structure of COZGIJ possesses the same formula of the iodoargentate but a different templating cation, consisting of two dinuclear [${\mathrm{Ba}}_2$(DMSO${)}_{13}$${]}^{4+}$ with two ${\mu }_2$-DMSO bridging molecules. Also, the argentophilic interactions can be distinguished with distances in the range of 3.16–3.35 Å.

No haloargentates with a nuclearity of 15 can be found in the database, which are templated with metal–organic cations. However, there are two iodoargentates with a nuclearity of 16. These are halometallates of the formula [${\mathrm{Ag}}_{16}{\mathrm{I}}_{22}{]}_n^{6-}$ and 1D connectivity. The structure of AMOZUA is templated with two [Pr(DMF${)}_7$${]}^{3+}$ complex cations, while the structure of AMUBAO is its samarium(III) analog. Argentophilic interactions can be also detected in both structures, with distances in the range of 3.05–3.27 Å. The iodoargentate chains propagate along the a direction, and the structures crystallize in the $Pna{2}_1$ space group.

There is a gap in haloargentates with nuclearities between 16 and 22. The last two instances of haloargenatates comprise 0D examples of [${\mathrm{Ag}}_{22}{\mathrm{I}}_{34}{]}^{12-}$ templated with [Ln(DMSO${)}_8$${]}^{3+}$, where ${\mathrm{Ln}}^{3+}$ = ${\mathrm{La}}^{3+}$, ${\mathrm{Ce}}^{3+}$ (the structures of MEMNOK and MEMNUQ). The argentophilic interactions can be distinguished within the linear-type iodoargentate with distances in the range of 2.8–3.2 Å.

2.2. Mixed-Metal Haloargentates

There are 25 examples of mixed-metal haloargentates in the database, presented in Table 3. Only three of them are trinuclear. The structure of JAYVEO, shown in Figure 6, contains 1D inorganic subnetwork of the lead–silver argentometallate of the formula [${\mathrm{Ag}}_2{\mathrm{PbBr}}_6{]}_n^{2-}$.

The halometallate is templated by a [Fe(phen${)}_3$${]}^{2+}$ complex cation, and a short contact between silver and lead(II) occurs, with a distance of 3.55 Å. Additionally, argentophilic interactions can be detected, with a distance of 3.24 Å. The chain propagates along the a direction. The structure of JAYVIS is a ${\mathrm{Ni}}^{2+}$ analog of the structure JAYVEO. On the other hand, the structure of JAYVOY is an example of a lead-substituted iodoargentate of the formula [${\mathrm{Ag}}_2{\mathrm{PbI}}_6{]}_n^{2-}$ and templated by [Ni(phen${)}_3$${]}^{2+}$. The short contact Pb$\cdots$Ag can be detected with a distance of 3.57 Å.

Additionally, argentophilic interactions can be distinguished, with distances in the range of 3.22–3.28 Å. The chains propagate along the direction of a.

There are 11 examples of tetranuclear mixed-metal haloargentates. The structure of COZJEI contains a halometallate of the formula [${\mathrm{Ag}}_2{\mathrm{Pb}}_2{\mathrm{I}}_{10}{]}^{4-}$, templated with a bis(tetra-glyme) barium complex cation. Its structure is discrete and no metallophilic interactions can be detected. The structure of HEVZOB also contains a 0D halometallate, of the formula [${\mathrm{Ag}}_2{\mathrm{Bi}}_2{\mathrm{I}}_{12}{]}^{4-}$, which is templated by a [Zn(phen${)}_3$${]}^{2+}$ metal–organic cation. In the structure of this mixed-metal iodoargentate, argentophilic interactions can be distinguished with a distance of 3.08 Å. The shortest bismuth–silver distance in the structure is 3.63 Å. The structures of KEGDEJ, KOBCIP, KOBCOV, and KOBCUB are isostructural and contain a lead-substituted iodoargentate of the formula [${\mathrm{Ag}}_2{\mathrm{Pb}}_2{\mathrm{I}}_9{]}_n^{3-}$. The iodoargentate has 1D connectivity and is templated by a [Ln(DMSO${)}_8$${]}^{3+}$ complex cation, where Ln = ${\mathrm{Nd}}^{3+}$, ${\mathrm{La}}^{3+}$, ${\mathrm{Gd}}^{3+}$, and ${\mathrm{Tm}}^{3+}$. The chains propagate along the a direction, and the shortest distance Ag$\cdots$Pb is 3.61 Å; no argentophilic interactions can be distinguished. The structures of LANCOW and LANCUC are isostructural and contain the same mixed-metal iodoargentate of the formula [${\mathrm{Ag}}_2{\mathrm{Bi}}_2{\mathrm{I}}_{12}{]}^{4-}$ templated with a [Fe(bipy${)}_3$${]}^{2+}$ complex cation. In the structure of the halometallate, both Ag$\cdots$Bi and Ag$\cdots$Ag short contacts can be detected with distances of 3.54 and 3.03 Å, respectively. The structures LANDAJ and LANDEN are isostructural, containing the same bismuth-substituted bromoargentate of the formula [${\mathrm{Ag}}_2{\mathrm{Bi}}_2{\mathrm{Br}}_{12}{]}^{4-}$, which is a discrete assembly, templated with a [Fe(bipy${)}_3$${]}^{2+}$ complex cation. Similar to KEGDEJ and isostructural compounds, the structure of NEHKEV is a 1D sublattice, with the halometallate of the formula [${\mathrm{Ag}}_2{\mathrm{Pb}}_2{\mathrm{I}}_9{]}_n^{3-}$ together with [${\mathrm{AgI}}_2{]}^{-}$ templated by a [Fe(phen${)}_3$${]}^{2+}$ complex cation. In the structure of this lead-substituted iodoargentate, no argentophilic interactions can be distinguished, and the shortest Ag$\cdots$Pb contact is 3.63 Å. The chains propagate along the a direction. There is only one mixed-metal haloargentate with a nuclearity of 5, templated by metal–organic cations. The halometallate formula is [${\mathrm{Ag}}_2{\mathrm{Pb}}_3{\mathrm{I}}_{10}{]}_n^{2-}$, in the structure of LOWYEE. The connectivity of the inorganic subnetwork in this case is two-dimensional, and the templating cation is [Ni(dien)(MeCN${)}_3$${]}^{2+}$ (where dien is diethylenetriamine). The waved layer propagates along the $bc$ plane, and in the halometallate, no argentophilic interactions can be found.

There are only two examples of mixed-metal haloargentates, templated with metal–organic cations, with a nuclearity of six. Both structures YEJQUD and YEJRAK are 0D bismuth-substituted haloargentates of formulas [${\mathrm{Ag}}_4{\mathrm{Bi}}_2{\mathrm{Br}}_{16}{]}^{6-}$ and [${\mathrm{Ag}}_4{\mathrm{Bi}}_2{\mathrm{I}}_{16}{]}^{6-}$, respectively. Both structures are templated with [Co(bipy${)}_3$${]}^{2+}$ complex cations. In the structure of YEJQUD, there are distinguishable argentophilic interactions in the distance range of 3.01–3.35 Å, along with a short Ag$\cdots$Bi contact at a distance of 3.43 Å. In the structure of YEJRAK, argentophilic interactions are also present, with distances in the range of 2.99–3.33 Å, together with a short Ag$\cdots$Bi contact at a distance of 3.53 Å.

There are six examples of mixed-metal haloargentate hybrids with a nuclearity of seven in the database. All six compounds contain a halometallate motif of the formula [${\mathrm{Ag}}_6{\mathrm{KX}}_{11}{]}_n^{4-}$, where X = ${\mathrm{Br}}^{-}$ or ${\mathrm{I}}^{-}$. The motif has 3D connectivity and is templated with two [TM(bipy${)}_3$${]}^{2+}$ complex cations, where $\mathrm{TM}={\mathrm{Ni}}^{2+}$, ${\mathrm{Co}}^{2+}$, ${\mathrm{Zn}}^{2+}$, and ${\mathrm{Fe}}^{2+}$. For example, in the structure of UBIWIO, argentophilic interactions can be found in the [${\mathrm{Ag}}_6{\mathrm{KBr}}_{11}{]}_n^{4-}$, with distances of 3.07 Å. The 3D connectivity is maintained thanks to K-Br weak bonds, with distances of 3.63 Å.

The structure of COZJAE contains a copper(I)-substituted iodoargentate with a nuclearity of eight, the only example in the database. The halometallate has a formula [${\mathrm{Ag}}_7{\mathrm{CuI}}_{12}{]}_n^{4-}$ and is characterized by overall 1D connectivity. The structure is templated with two bis(tetraglyme) barium(II) complex cations, and argentophilic interactions can be detected with distances in the range of 3.02–3.28 Å. The Ag$\cdots$Cu short contact can be distinguished, with a short distance of 2.99 Å. The chains propagate along the b direction. The structure of MUBSAF contains the only mixed-metal haloargentate with a nuclearity of nine. The formula of the halometallate is [${\mathrm{Ag}}_2{\mathrm{Pb}}_7{\mathrm{I}}_{22}{]}_n^{6-}$ and is templated by a [Y(DMF${)}_8$${]}^{3+}$ complex cation. In the structure of the halometallate, a short Ag$\cdots$Pb contact of 3.39 Å indicates metallophilic interactions. The halometallate forms a 1D zigzag constructed from a [${\mathrm{AgI}}_4{]}^{3-}$ tetrahedron and [${\mathrm{Pb}}_7{\mathrm{I}}_{24}{]}^{10-}$ unit, similar to a fragment commonly observed in the [${\mathrm{PbI}}_3{]}_n^{-}$ chain. The compound exhibits thermochromic behavior.

2.3. Halocuprates

There are 51 halocuprate structures with a nuclearity of two, as shown in Table 4 and Table 5. These are usually 0D structures or 1D structures. The majority of copper compounds gathered in the tables contain monovalent copper; however, divalent copper compounds can also be found. The first example of a structure with divalent copper chlorocuprate is ACAROM, shown in Figure 7.

The [${\mathrm{Cu}}_2{\mathrm{Cl}}_6{]}^{2-}$ anion is built from two edge-sharing [${\mathrm{CuCl}}_4{]}^{3-}$ tetrahedra. The short Cu$\cdots$Cu distance within the cluster is 3.30 Å. The example of structure COZGUV contains [${\mathrm{Cu}}_2{\mathrm{I}}_4{]}^{2-}$ anions, formed by edge sharing of two triangles [${\mathrm{CuI}}_3{]}^{2-}$. The shortest distance Cu$\cdots$Cu is 2.64 Å, in the dimer, templated with a bis(tetraglyme)barium(II) complex cation. The [${\mathrm{Cu}}_2{\mathrm{X}}_4{]}^{2-}$ anion can be also polymeric, as in the structure of VAHWAD, where 1D chains are formed by edge-sharing tetrahedra in [${\mathrm{Cu}}_2{\mathrm{Br}}_4{]}_n^{2-}$. The cuprophilic interaction is weaker than in the [${\mathrm{Cu}}_2{\mathrm{I}}_4{]}^{2-}$ anion, with a distance of 3.04 Å. The chains propagate along the a direction. The structure of YADTUS contains an iodocuprate of the formula [${\mathrm{Cu}}_2{\mathrm{I}}_3{]}_n^{-}$, forming chains by tetrahedra [${\mathrm{CuI}}_4{]}^{3-}$ sharing edges and vertexes. The cuprophilic interaction can be distinguished with a distance of 2.76 Å, and the chains propagate along the a direction. There are only six examples of halocuprates with a nuclearity of three in the database; all of them are 1D structures containing monovalent or divalent copper ions. The structure of BOHYCU is built from [${\mathrm{Cu}}_3{\mathrm{Cl}}_5{]}_n^{2-}$ chlorocuprate templated by a bis-hydrazide copper complex cation. The compound crystallize in the $Pbca$ space group, and the chains are propagated along the a direction. The chain is directly bound to the complex cation by a weak Cu-Cl bond with a distance of 2.76 Å. Additionally, cuprophillic interactions can be distinguished with distances in the range of 2.76–2.89 Å. The structure of CUMWEM contains an iodocuprate of the formula [${\mathrm{Cu}}_3{\mathrm{I}}_4{]}_n^{-}$, templated with a 24-crown-8 potassium complex cation. The chains propagate along the a direction, and cuprophilic interactions can be detected with distances in the range of 2.67–2.80 Å. The structure of JIZBUP contains a chlorocuprate(II) of the formula [${\mathrm{Cu}}_3{\mathrm{Cl}}_8{]}_n^{2-}$ templated with a diacetonitrile-(15-crown-5)-copper(II) complex cation. The shortest distance between copper(II) centers is 3.09 Å. The chains propagate along the (1$\overline{1}$$\overline{1}$) plane.

There are 19 examples of structures containing halocuprate clusters with a nuclearity of four. The majority of them are 0D but there are also 1D systems (three examples only). The structure of ATUQIP contains an iodocuprate of the formula [${\mathrm{Cu}}_4{\mathrm{I}}_6{]}_n^{2-}$, templated by two bis(12-crown-4) potassium complex cations. The iodocuprate forms chains along the (011) plane. In the chains, cuprophilic interactions can be distinguished with Cu$\cdots$Cu distances in the range of 2.51–2.64 Å. On the other hand, the structure of COZHAL contains the same iodocuprate motif [${\mathrm{Cu}}_4{\mathrm{I}}_6{]}^{2-}$, but instead of a polymeric chain, a discrete assembly is formed. The structure is templated with a bis(triglyme)-bis(acetone)-barium(II) complex cation, and cuprophilic interactions can be detected with distances in the range of 2.72–2.86 Å. In the structure of LESVIR, another type of discrete halocuprate can be identified, with the formula [${\mathrm{Cu}}_4{\mathrm{Cl}}_8{]}^{4-}$. In this chlorocuprate, cuprophilic interactions can be distinguished with distances 2.66 and 2.87 Å. The halometallate is templated by a large [${\mathrm{Cu}}_2{\mathrm{L}}_2{]}^{2+}$ bishydrazone complex. On the other hand, the structure of YAFWEK contains an iodocuprate with an odd number of iodine atoms, of the formula [${\mathrm{Cu}}_4{\mathrm{I}}_7{]}^{3-}$. In this iodocuprate, cuprophilic interactions can be detected, with distances in the range of 2.49–2.78 Å. The assembly is templated by three voluminous molecules of the complex cation [${\mathrm{Cu}}_2\mathrm{LI}{]}^{+}$ derived from a phenoxy-oxazolyl-pyridine-type ligand, with a short Cu-Cu distance of 2.57 Å.

There are only 12 examples of pentanuclear halocuprate clusters in the database; the majority of them are characterized by 1D inorganic subnetwork connectivity, while the rest are discrete assemblies. The structure of EKIGIO contains a halometallate of the formula [${\mathrm{Cu}}_5{\mathrm{I}}_7{]}_n^{2-}$, which forms chains templated by a triaqua-(18-crown-6) calcium(II) complex cation. The compound crystallizes in the $Pbcm$ space group and the chains propagate along the b direction of the unit cell. The copper atoms in the halometallate are disordered, so it is difficult to decide upon the Cu-Cu distances in the cuprophilic interactions. On the other hand, the structure of NAZNUZ, shown in Figure 8, contains a halocuprate of the same formula, [${\mathrm{Cu}}_5{\mathrm{I}}_7{]}^{2-}$, but this time, it is a discrete assembly.

In the halometallate, cuprophlic interactions can be detected with distances in the range of 2.50–2.56 Å. The structure is templated by a large trinuclear complex of the formula [${\mathrm{Cu}}_3{\mathrm{L}}_2{]}^{2+}$, where L denotes a salen-type ligand with bridging phenolic oxygen atoms. The structure of WUZBIE contains a halometallate of the formula [${\mathrm{Cu}}_5{\mathrm{Br}}_8{]}^{3-}$ which forms 1D chains. In the structure of this bromocuprate, cuprophilic interactions can be detected, with distances of 2.76 and 2.81 Å. The structure is templated with the [Co(bipy${)}_3$${]}^{2+}$ complex cation, and the chains propagate along the ($\overline{1}$00) plane.

There is only one example of hexanuclear halocuprate in the database. The structure of DEFLOT contains a discrete iodocuprate cluster of the formula [${\mathrm{Cu}}_6{\mathrm{I}}_{10}{]}^{4-}$. The structure is templated with a [${\mathrm{MnL}}_3{]}^{2+}$ complex cation, where L is diphosphine dioxide chelating ligand. Cuprophilic interactions can be distinguished in the halometallate with distances of 2.58 Å. The compounds exhibit dual emission ascribed by the authors to the presence of octahedral ${\mathrm{Mn}}^{2+}$ ions and iodocuprate clusters. High quantum yields of luminescence are reported for these compounds.

There are five examples of heptanuclear halocuprate clusters templated with metal–organic cations in the database. Interestingly, there is no 0D cluster, but there are 1D, 2D, and 3D inorganic sublattice connectivities. The structure of LODVEG contains a halometallate of the formula [${\mathrm{Cu}}_7{\mathrm{Cl}}_{16}{]}_n^{2-}$, composed of entirely copper(II) and templated with [Cu(TIM)${]}^{2+}$, where TIM represents 2,3,9,10-tetramethyl-1,3,8,10-tetraenecyclo-1,4,8,11-tetrazatetradecane. The shortest Cu$\cdots$Cu distances within the halometallate are in the range of 3.33–3.94 Å. The layers propagate along the $ac$ plane. The problem is with the location of two water molecules, because it is not included in CSD data. It seems that one chloride is replaced to form a [${\mathrm{Cu}}_{6.5}{\mathrm{Cl}}_{15}$(${\mathrm{H}}_2$O)${]}^{2-}$ cluster. The structure of NIGNOG is built from the inorganic subnetwork of 3D connectivity. Here, the chlorocuprate of the formula [${\mathrm{Cu}}_7{\mathrm{Cl}}_{11}{]}_n^{4-}$ is templated by a [Cu(en${)}_2$${]}^{2+}$ complex cation. The compound crystallizes in the $P{4}_{2}nm$ space group, and cuprophilic interactions can be detected with distances in the range of 2.68–2.83 Å. The structure of WUZCAX contains a heptanuclear iodocuprate of the formula [${\mathrm{Cu}}_7{\mathrm{I}}_9{]}_n^{2-}$ which forms inorganic chains templated by [Mn(bipy${)}_2$$\mathrm{I}{]}^{+}$ complex cations. The chains propagate along the a direction, and cuprophilic interactions can be distinguished with distances in the range of 2.80–2.84 Å. On the other hand, the structure of YEWVUS contains an iodocuprate of the formula [${\mathrm{Cu}}_7{\mathrm{I}}_{10}{]}_n^{3-}$, forming chains and templated by [Y(DMF${)}_6$(${\mathrm{H}}_2$O${)}_2$${]}^{3+}$ complex cations. The chains are propagated along the b direction, and cuprophilic interactions can be distinguished with distances in the range of 2.83–2.86 Å.

There is only one example of halocuprate with a nuclearity of eight in the database. The structure of WUZBEA contains an iodocuprate of the formula [${\mathrm{Cu}}_8{\mathrm{I}}_{11}{]}_n^{3-}$, forming chains and templated with [Cu(bipy${)}_2$$\mathrm{I}{]}^{+}$ and 1,1’-dimethyl-2,2’-bipyridinium dications together. The chains propagate along the c direction, and cuprophilic interactions can be distinguished with distances in the range of 2.72–2.76 Å. There are only three examples of halocuprates with a nuclearity of nine in the database. The structure of PARTOT contains an iodometallate of the formula [${\mathrm{Cu}}_9{\mathrm{I}}_{14}{]}_n^{3-}$, which contains seven monovalent copper atoms and two divalent copper atoms. This mixed valence system is templated with a [Tb(DMF${)}_6$(${\mathrm{H}}_2$O${)}_3$${]}^{3+}$ complex cation. The layers propagate along the $ab$ plane of the unit cell, and the cuprophilic interactions can be detected with distances in the range of 2.81–2.85 Å. The structure of YEWWAZ is also two-dimensional with the same halocuprate cluster and ytterbium(III) analog of the templating complex cation. On the other hand, the structure of UHOWUK has a one-dimensional inorganic sublattice, composed of a halometallate with the formula [${\mathrm{H}}_2{\mathrm{Cu}}_9{\mathrm{I}}_{11}\mathrm{O}{]}_n^{2-}$, which is claimed to be wrongly determined. The structure is templated by a [${\mathrm{Co}}_2$(phen${)}_4$${\mathrm{Cl}}_2{]}^{2+}$ complex cation. The layers propagate along the $bc$ plane. There seem to be present cuprophilic interactions, but their identification is complicated by the disorder within the halometallate. The structure of IWEZEP also contains a disordered decanuclear halometallate, with a discrete assembly of the formula [${\mathrm{H}}_2{\mathrm{Cu}}_{10}{\mathrm{I}}_{15}{]}^{4-}$, templated by two [Ni(phen${)}_3$${]}^{2+}$ complex cations. On the other hand, the structure of SODMUU contains a decanuclear halocuprate of the formula [${\mathrm{Cu}}_{10}{\mathrm{I}}_{15}{]}^{4-}$, which contains one divalent copper center. The structure is templated with [Co(phen${)}_3$${]}^{2+}$ complex cations, and disorder in the occupations of copper centers can be seen and influences the distinguishability of the cuprophilic interactions.

2.4. Photocatalytic Degradation of Dyes

Non-perovskite hybrid halides are promising candidates for the photocatalytic degradation of dyes such as crystal violet, rhodamine blue, and methylene blue.

Table 6. The photocatalytic degradation of dye by the non-perovskite hybrid halometallates of coinage metals. CV refers to crystal violet, while RhB refers to rhodamine blue.

k [${\min }^{-1}$]	${\mathrm{t}}_{1/2}$ [min]	Dye	Reference
0.0111	62.45	CV	[49]
0.0136	50.97	CV	[49]
0.0207	33.49	CV	[49]
0.0033	210.04	CV	[49]
0.009	77.02	CV	[49]
0.0109	63.59	CV	[49]
0.0062	111.80	CV	[49]
0.0127	54.58	CV	[49]
0.0143	48.47	CV	[49]
0.0107	64.78	RhB	[49]
0.005	138.63	RhB	[49]
0.0213	32.54	RhB	[49]
0.0079	87.74	RhB	[49]
0.0066	105.02	RhB	[49]
0.0107	64.78	RhB	[49]
0.0065	106.64	RhB	[49]
0.0055	126.03	RhB	[49]
0.0077	90.02	RhB	[49]
0.047	14.75	CV	[39]
0.037	18.73	CV	[39]
0.028	24.76	CV	[39]
0.046	15.07	CV	[136]
0.030	23.10	CV	[136]
0.035	19.80	CV	[136]
0.131	5.29	CV	[136]
0.337	2.06	RhB	[65]
0.201	3.45	RhB	[65]
0.255	2.72	RhB	[65]
0.301	2.30	RhB	[65]
0.119	5.82	RhB	[65]
0.239	2.90	RhB	[65]
0.047	14.75	CV	[33]
0.037	18.73	CV	[33]
0.028	24.76	CV	[33]
0.01599	43.35	RhB	[137]
0.0016	433.22	CV	[54]
0.006167	112.40	CV	[54]
0.009017	76.87	CV	[54]
0.004883	141.95	RhB	[54]
0.0011	630.13	RhB	[54]
0.002083	332.76	RhB	[54]
0.0775	8.94	CV	[44]
0.0433	16.01	CV	[44]
0.0135	51.34	CV	[44]
0.0256	27.08	CV	[44]
0.0303	22.88	CV	[44]
0.0209	33.16	CV	[44]
0.1037	6.68	RhB	[44]
0.0249	27.84	RhB	[44]
0.0083	83.51	RhB	[44]
0.0155	44.72	RhB	[44]
0.0185	37.47	RhB	[44]
0.0142	48.81	RhB	[44]

presents key kinetic data, including rate constants and half-lives, from previously published studies. For crystal violet, half-lives range from 5.29 to 433.22 min, depending on the halometallate salt used. The shortest times were observed with mixed-metal silver–lead haloargentates templated with [TM(2,2’-bipy${)}_3$${]}^{2+}$, while the longest were found for iodoargentates templated with [Ln(DMA${)}_n$${]}^{3+}$ cations. Similarly, for rhodamine blue, half-lives range from 2.06 to 630.13 min. The shortest were reported for bromoargentates templated with [TM(2,2’-bipy${)}_3$${]}^{2+}$, while the longest occurred with iodoargentates templated with [Ln(DMA${)}_n$${]}^{3+}$. The longest half-lives for both crystal violet and rhodamine blue come from the same study, while the shortest times for the two dyes are from different studies.

For a complete comparison, experimental conditions must be specified, including the light source, its power, and the initial concentration of the dye. We believe the initial dye concentrations were similar, but light power likely varied across studies. Additionally, the reaction vessel’s geometry could affect light penetration, impacting reaction efficiency. Other factors like mixing rate, photocatalyst grain size, and the quantity of the photocatalyst also likely influence dye degradation efficiency.

In addition to dye degradation experiments, studies on dye adsorption and release have also been conducted. In these experiments, the dye is first adsorbed from a solution onto the hybrid halide. The material is then separated from the solution and immersed in a sodium ion-containing solution, leading to the release of the dye as sodium ions exchange with ions at the hybrid halide interface. This process can be monitored using visible-range absorption spectroscopy [45].

It appears that the interface between the solution and the non-perovskite hybrid halide is negatively charged. Some templating ions from the solid may dissolve, leaving behind a negatively charged inorganic subnetwork. As a result of Coulombic attraction, cations are drawn to the surface, where photocatalytic processes take place. Interestingly, anionic dyes did not adsorb onto the same hybrid halides as cationic dyes in these experiments.

3. Conclusions and Outlook

We have surveyed the structures of coinage metal halometallates templated with metal–organic cations in the Cambridge Structural Database (CSD). A total of 208 compounds were identified and categorized into three groups: haloargentates, mixed-metal haloargentates, and halocuprates. The nuclearity and connectivity of their inorganic subnetworks were analyzed. Additionally, we examined the metallophilic interactions within these structures. Argentophilic interactions were prevalent in both haloargentates and mixed-metal haloargentates, whereas cuprophilic interactions were observed in halocuprates containing monovalent copper.

Several gaps were identified, specifically in haloargentates of various nuclearities and dimensionalities that have yet to be synthesized. While reviewing templating cations, we found no correlation between the cation’s volume and the nuclearity of the halometallate. However, a relationship exists between the symmetry of the templating cation and that of the halometallic sublattice. Notably, rotational symmetry elements are transferred from the templating cation to the inorganic sublattice.

Furthermore, incorporating metal cations of different valencies into these assemblies could advance the chemistry of materials. To date, reports have primarily focused on mixed-metal haloargentates substituted with lead, copper, and bismuth. Expanding this to include other metals would be a valuable area of exploration.

The photocatalytic performance of these hybrid halides is especially promising for environmental applications, such as the degradation of organic pollutants. Their ability to harness visible light and catalyze reactions efficiently is attributed to the synergistic effects between the organic and inorganic components. Studies have shown that hybrids can successfully degrade dyes like crystal violet and methylene blue, with their photocatalytic activity being influenced by factors such as the dimensionality of the inorganic subnetwork, grain size, and surface charge. These properties offer exciting prospects for further optimization in real-world photocatalytic applications, particularly in water treatment and pollution control.

Future research should focus on refining the structural and compositional parameters to enhance the photocatalytic efficiency of these materials. Optimizing light absorption, charge separation, and catalytic reaction pathways will be crucial in improving their performance. The exploration of novel templating agents and mixed-metal systems could open new avenues for hybrid halides in photocatalysis, potentially leading to more sustainable and efficient solutions for environmental remediation.