Next Article in Journal
A Ti/Pt/Co Multilayer Stack for Transfer Function Based Magnetic Force Microscopy Calibrations
Next Article in Special Issue
Influence of the Size and Shape of Halopyridines Guest Molecules G on the Crystal Structure and Conducting Properties of Molecular (Super)Conductors of (BEDT-TTF)4A+[M3+(C2O4)3]·G Family
Previous Article in Journal
Reciprocating Thermal Behavior in Multichannel Relaxation of Cobalt(II) Based Single Ion Magnets
Previous Article in Special Issue
Solvent-Induced Hysteresis Loop in Anionic Spin Crossover (SCO) Isomorph Complexes
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Magnetochemistry
Volume 7
Issue 6
10.3390/magnetochemistry7060077
magnetochemistry-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Crystal-to-Crystal Transformation from K2[Co(C2O4)2(H2O)2]·4H2O to K2[Co(μ-C2O4)(C2O4)]

by
Bin Zhang
1,*,
Yan Zhang
2,
Guangcai Chang
3,
Zheming Wang
4 and
Daoben Zhu
1
1
Organic Solid Laboratory, BNLMS, CMS & Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
2
Department of Physics, Institute of Condensed Matter and Material Physics, Peking University, Beijing 100871, China
3
BSRF, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100047, China
4
State Key Laboratory of Rare Earth Materials Chemistry and Applications, BNLMS, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
*
Author to whom correspondence should be addressed.
Magnetochemistry 2021, 7(6), 77; https://doi.org/10.3390/magnetochemistry7060077
Submission received: 28 April 2021 / Revised: 21 May 2021 / Accepted: 24 May 2021 / Published: 28 May 2021
(This article belongs to the Special Issue Perspectives on Molecular Materials—A Tribute to Professor Peter Day)
Browse Figures
Versions Notes

Abstract

:
Crystal-to-crystal transformation is a path to obtain crystals with different crystal structures and physical properties. K2[Co(C2O4)2(H2O)2]·4H2O (1) is obtained from K2C2O4·2H2O, CoCl2·6H2O in H2O with a yield of 60%. It is crystallized in the triclinic with space group P1 and cell parameters: a = 7.684(1) Å, b = 9.011(1) Å, c = 10.874(1) Å, α = 72.151(2)°, β = 70.278(2)°, γ = 80.430(2)°, V = 670.0(1) Å3, Z = 2 at 100 K. 1 is composed of K+, mononuclear anion [Co(C2O4)2(H2O)22−] and H2O. Co2+ is coordinated by two bidentated oxalate anion and two H2O in an octahedron environment. There is a hydrogen bond between mononuclear anion [Co(C2O4)2(H2O)22−] and H2O. K2[Co(μ-C2O4)(C2O4)] (2) is obtained from 1 by dehydration. The cell parameters of 2 are a = 8.460(5) Å, b = 6.906 (4) Å, c = 14.657(8) Å, β = 93.11(1)°, V = 855.0(8) Å3 at 100 K, with space group in P2/c. It is composed of K+ and zigzag [Co(μ-C2O4)(C2O42−]n chain. Co2+ is coordinated by two bisbendentate oxalate and one bidentated oxalate anion in trigonal-prism. 1 is an antiferromagnetic molecular crystal. The antiferromagnetic ordering at 8.2 K is observed in 2.

Graphical Abstract

1. Introduction

The change of the weak interaction of guest molecules, coordination geometry distortion, and coordination number in coordination compounds can effectively modulate the physical properties as magnetism, absorption, and chirality, so the dynamic molecular crystals have received great attention for their potential applications in molecular devices, as molecular sensors and switches become a powerful method for obtaining a specific compound with the yield of 100% by crystal-to-crystal transformation in crystal engineering [1,2,3,4,5,6,7]. The crystal-to-crystal transformations were observed between different dimensional coordination units as zero-dimensional (0D), one-dimensional chain (1D), two-dimensional (2D) layer, and three-dimensional (3D) coordination frameworks [8,9,10]. We are interested in dynamic crystals of MX2–(1,4-dioxane)–H2O system, and 0D to 2D, 1D to 2D, 1D to 3D crystal-to-crystal transformations were found [11,12,13]. Oxalate (C2O42−) is one of most popular used three-atoms ligands in the study of molecular-based magnet, its versatile abilities and intermediating efficient magnetic coupling among transition atoms have constructed 1D, 2D, and 3D magnetic materials [14,15,16,17,18,19,20,21]. However, the research on oxalate-based dynamic crystal is limited. Herein, we present a crystal-to-crystal transformation from 0D mononuclear compound K2[Co(C2O4)2(H2O)2]·4H2O (1) into a reported 1D coordination compound K2[Co(μ-C2O4)(C2O4)] (2) accompanied by changes in crystal color, cell parameters, space group, coordination environment, crystal structure, and magnetic property.

2. Experiment and Discussion

1 was obtained from K2C2O4·2H2O, Co(NO3)2·6H2O in H2O with yield of 60%.
When 1 was heated at an elevated temperature (at 120 °C for three minutes), it transferred to 2 after dehydration with a mass loss of 25.7%, crystal structure changed from mononuclear to one-dimensional chain (Scheme 1) and the crystal color changed from orange to pink. 2 remained stable until 300 °C (Figure 1). This is the second method to obtain 2 except the solvothermal method. The IR bands (Figure S1) between 1 and 2 is the strong broad band above 3000 cm−1 υ(O-H) as from H2O in 1. The existence weak broad band above 3000 cm−1 means 2 is unstable to air as reported [17].
1 crystallizes in triclinic with space group of P1: a = 7.684(1) Å, b = 9.011(1) Å, c = 10.874(1) Å, α = 72.151(2)°, β = 70.278(2)°, γ = 80.430(2)°, V = 670.0(1) Å3, Z = 2. 1 is composed of K+, mononuclear coordination anion Co(C2O4)2(H2O)22− and H2O (Figure 2a). There are two K+, one Co2+, two oxalate (C2O42−), and six H2O in an independent unit. K1 is surrounded by five O from three oxalato and four H2O, K2 is surrounded by five O from three oxalato and four H2O. K column formed by K1 and K2 host the vacancy of H-bond network formed by oxalate and H2O along the b axis. K1⋯K2 distances are 3.872(2) Å and 5.630(2) Å alternatively, and K1⋯K1 and K2⋯K2 distances are 9.011(1) Å. Each Co2+ is coordinated by two oxalate anions with Co-O 2.078(2)~2.099(2) Å on the equatorial plane, and two H2O with Co-O 2.114(4) Å~2.120(3) Å to fulfill the octahedron environment. O-Co-O angles are among 88.4(2)~92.3(1)° from H2O to equatorial plane and 176(1)° between two H2O atoms. Viewed along the b axis, Co⋯Co distances are of 9.011(1) Å and 7.684(2) Å alternatively along the a axis. There are hydrogen bonds between anions and coordinated H2O: O9-H1⋯O8(-x,1-y,1-z) 2.839(5) Å/170°, O10-H4⋯O1(-x,2-y,-z) 3.178(5) Å/127°; between anions and solvent H2O: O14-H12⋯O1 2.795 Å/163°, O13-H9⋯O6(1-x,y,z) 2.740 Å/169°, O9-H2⋯O14(-x,1-y,-z) 2.760 Å/179°, O12-H8⋯O2(1-x,1-y,z) 2.820 Å/167°, O11-H5⋯O8(-x,1-y,1-z) 2.826 Å/156°, O10-H3⋯O12(-x,1-y,z) 2.755 Å/176°, O11-H6⋯O3(-x,1-y,-z) 2.709 Å/178°, O13-H10⋯O7 2.803 Å/164°.
The crystal structure of 2 is the same as reported isostructural of K2[Fe(μ-C2O4)(C2O4)] [17]. It consists of K+ and zigzag chain [Co(μ-C2O4)(C2O4)2−]n (Figure 2b). There are one and two half K+, one Co2+, one and two half oxalato in an independent unit. Co2+ is trigonal-prismatic coordinated by three oxalate anions with Co-O distance 2.058(3)~2.151(4) Å. K+ is in the vacant formed by Co(C2O4)22− chain.
Depending on the extensive hydrogen bonds in 1 and zigzag chained structure of 2, the magnetic properties of them were investigated. The transformation from 1 to 2 is irreversible. The sample was checked and remained the same before and after magnetic experiments.
1: χT is 3.41 cm3 K mol−1 at 300 K. It is significantly larger than the value of 1.875 cm3 K mol−1 expected for an isolated, spin-only ion with S = 3/2 and g = 2.00. This suggests a strong spin-orbit coupling. [20,21,22] The χT value decreased upon cooling and reached 1.30 cm3 K mol−1 at 2 K. The susceptibility data above 50 K fit the Curie–Weiss law well, giving Curie and Weiss constants of C = 3.613(6) cm3 K mol−1 and θ = −21.2(2) K, respectively, with R = 3.74 × 10−5 (Figure 3). The negative Weiss constant means the antiferromagnetic interaction between Co2+ ions through hydrogen bonds. At 2 K, the isothermal magnetization is 2.24 Nβ at 65 kOe (Figure 4). No long-range magnetic ordering was observed in 1.
2: On χ versus T plot, a broad maximum of 0.031 cm3 mol−1 was observed around 50 K, which is similar to reported oxalate-bridged one-dimensional compounds [15,17,20]. Then χ value decreased upon cooling smoothly, it is 0.0070 cm3 mol−1 at 2 K. At 300 K, χT is 3.24 cm3 K mol−1, this means a strong spin-orbit coupling of Co2+ as 1. The χT value decrease upon cooling and reach 0.014 cm3 K mol−1 at 2 K. The data above 120 K were fitted with Curie–Weiss law, giving Curie and Weiss constant C = 3.66(2) cm3 K mol−1, θ = −35(1) K, R = 4.96 × 10−5. Field-cooled magnetization (FCM) and zero-field-cooled magnetization (ZFCM) measurements under a field of 10 Oe show a magnetic ordering at 8.2 K (Figure 3, inset). At 2 K, the isothermal magnetization increases smoothly and reaches 0.072 Nβ at 65 kOe. The Hysteresis loop (Hc) is 500 Oe.

3. Conclusions

Orange 1 transfer to pink 2 by dehydration. 1 is composed of K+, mononuclear coordination anion Co(C2O4)2(H2O)2− and H2O with extensive hydrogen bond between anion and H2O, H2O, and H2O. 2 is consisted of K+ and zigzag chain anion [Co(μ-C2O4)(C2O4)2−]n. The antiferromagnetic interaction in 1 from hydrogen bonds is weaker than oxalate-bridge in 2 [23]. 2 shows antiferromagnetic ordering at 8.2 K.

Supplementary Materials

The following are available online at https://www.mdpi.com/article/10.3390/magnetochemistry7060077/s1, sample preparation and characterization, Figure S1: IR spectra of 1 and 2, Figure S2: Powder X-ray diffraction patterns of 1 and 2.

Author Contributions

Conceptualization, B.Z.; data curation, Y.Z.; G.C.; investigation, Z.W.; D.Z. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Natural Science Foundation of China (Grant Nos. 21172230, 21573242, and 22073106), Chinese Ministry of Science and Technology (Grant Nos. 2011CB932302 and 2013CB933402) and the Strategic Priority Research Program (B) of the Chinese Academy of Sciences (Grant No. XDB12030100).

Data Availability Statement

Sample preparation, characterization, IR spectra and powder X-ray diffraction pattern of 1 and 2 are available on Supplementary Materials via. www.mdpi.com/xxx/s1.

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 21172230, 21573242, and 22073106).

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Lim, S.H.; Olmstead, M.M.; Balch, A.L. Molecular accordion: Vapoluminescence and molecular flexibilityin the orange and green luminescent crystals of the dimer, Au2(μ-bis-(diphenylphosphino)ethane)2Br2. J. Am. Chem. Soc. 2011, 133, 10229–10238. [Google Scholar] [CrossRef] [PubMed]
  2. Huang, Y.; Schoenecker, B.; Mu, P.; Carson, C.G.; Karra, J.R.; Cai, Y.; Walton, K.S. A porous flexible homochiral SrSi2 array of single-stranded helical nanotubes exhibiting single-crystal-to-single-crystal oxidation transformation. Angew. Chem. Int. Ed. 2011, 50, 436–440. [Google Scholar] [CrossRef] [PubMed]
  3. Chatterjee, P.B.; Audhya, A.; Bhattacharya, S.; Abtab, S.M.T.; Bhattacherya, K.; Chaudhury, M. Single crystal-to-single crystal irreversible transformation from a discrete Vanadium(V)-Alcoholate to an Aldehydic-Vanadium(IV) oligomer. J. Am. Chem. Soc. 2010, 132, 15842–15845. [Google Scholar] [CrossRef]
  4. Huang, Z.; White, P.S.; Brookhart, M. Ligand exchanges and selective catalytic hydrogenation in molecular single crystals. Nature 2010, 465, 598–601. [Google Scholar] [CrossRef]
  5. Kawasaki, T.; Hakoda, Y.; Mineki, H.; Suzuki, K.; Soai, K. Generation of absolute controlled crystal chirality by the removal of crystal water from achiral crystal of nucleobase cytosine. J. Am. Chem. Soc. 2010, 132, 2874–2875. [Google Scholar] [CrossRef]
  6. Allan, P.K.; Xiao, B.; Teat, S.J.; Knight, J.W.; Morris, R.E. In situ single-crystal diffraction studies of the structural transition of metal-organic framework copper 5-sulfoisophthalate, Cu-SIP-3. J. Am. Chem. Soc. 2010, 132, 3605–3611. [Google Scholar] [CrossRef]
  7. Thorarinsdottir, A.E.; Harris, T.D. Metal-Organic framework magnets. Chem. Rev. 2020, 120, 8716–8789. [Google Scholar] [CrossRef]
  8. Kaneko, W.; Ohba, M.; Kitagawa, S. A flexible coordination polymer crystal providing reversible structural and magnetic conversions. J. Am. Chem. Soc. 2007, 129, 13706–13712. [Google Scholar] [CrossRef]
  9. Zhang, Y.; Liu, T.; Kanegawa, S.; Sato, O. Reversible single-crystal-to-single-crystal transformation from achiral antiferromagnetic hexanuclears to a chiral ferrimagnetic double zigzag chain. J. Am. Chem. Soc. 2009, 131, 7942–7943. [Google Scholar] [CrossRef] [PubMed]
  10. Zhang, Y.; Liu, T.; Kanegawa, S.; Sato, O. Interconversion between a nonporous nanocluster and a microporous coordination polymer showing selective gas adsorption. J. Am. Chem. Soc. 2010, 132, 912–913. [Google Scholar] [CrossRef]
  11. Duan, Z.; Zhang, Y.; Zhang, B.; Zhu, D. Crystal-to-Crystal transformation from antiferromagnetic chains into a ferromagnetic diamondoid framework. J. Am. Chem. Soc. 2009, 131, 6934–6935. [Google Scholar] [CrossRef]
  12. Zhang, B.; Zhu, D.; Zhang, Y. Crystal-to-Crystal transformation from a mononuclear compound in a hydrogen-bonded three-dimensional framework to a layered coordination polymer. Chem. Eur. J. 2010, 16, 9994–9997. [Google Scholar] [CrossRef]
  13. Shi, J.; Zhang, Y.; Zhang, B.; Zhu, D. Crystal-to-crystal transformation from a chain compound to a layered coordination polymer. Dalton Trans. 2016, 45, 89–92. [Google Scholar] [CrossRef]
  14. Mathoniere, C.; Carling, S.G.; Yusheng, D.; Day, P. Molecular-based Mixed Valency Ferrimagnets (XR4)FeIIFeIII(C2O4)3 (X = N, P; R = n-propyle, n-butyl, phenyl): Anomalous negative magnetisation in the tetra-n-butylammonium derivative. J. Chem. Soc. Chem. Commun. 1994, 1551–1552. [Google Scholar] [CrossRef]
  15. Clemente-Leon, M.; Coronado, E.; Marti-Gastaldo, C.; Romero, F.M. Multifunctionality in hybrid magnetic materials based on bimetallic oxalate complexes. Chem. Soc. Rev. 2011, 40, 473–497. [Google Scholar] [CrossRef]
  16. Hernandez-Molina, M.; Lloret, F.; Ruiz-Perez, C.; Julve, M. Weak ferromagnetism in chiral 3-dimensional oxalate-bridged Cobalt(II) compounds. crystal structure of [Co(bpy)3][Co2Ox3]ClO4. Inorg. Chem. 1998, 37, 4131–4135. [Google Scholar] [CrossRef]
  17. Hursthouse, M.B.; Light, M.E.; Price, D.J. One-dimensional magnetism in new anhydrous iron and cobalt ternary oxalates with rare trigonal prismatic metal coordination. Angew. Chem. Int. Ed. 2004, 43, 472–475. [Google Scholar] [CrossRef]
  18. Coronado, E.; Galan-Mascaros, J.R.; Marti-Gastalo, C. Single chain magnets based on the oxalate ligand. J. Am. Chem. Soc. 2008, 130, 14987–14989. [Google Scholar] [CrossRef]
  19. Glerup, J.; Goodson, P.A.; Hodgson, D.J.; Michelsen, K. Magnetic Exchange through Oxalate Bridges: Synthesis and Characterization of (μ-Oxalato)dimetal (II) Complexes of Magnanese, Iron, Cobalt, Nickel, Copper and Zinc. Inorg. Chem. 1995, 34, 6255–6264. [Google Scholar] [CrossRef]
  20. Garcia-Couceiro, U.; Castillo, O.; Luque, A. A new hydrated phase of cobalt(II) oxalate: Crystal structure, thermal behavior and magnetic properties of {[Co(-Ox)(H2O)2]·2H2O}n. Inorg. Chim. Acta 2004, 357, 339–344. [Google Scholar] [CrossRef]
  21. Duan, Z.; Zhang, Y.; Zhang, B.; Zhu, D. Co(C2O4)(HO(CH2)3OH): An antiferromagnetic neutral zigzag chain compound showing long-range-ordering of spin canting. Inorg. Chem. 2008, 47, 9152–9154. [Google Scholar] [CrossRef]
  22. Duan, D.; Zhang, Y.; Zhang, B.; Pratt, F. Two homometallic antiferromagnets based on oxalato-bridged honeycomb assemblies: (A)2[MII2C2O4)3] (A = ammonium salt derived from diethylenetriamine; MII = Fe2+, Co2+). Inorg. Chem. 2009, 48, 2140–2146. [Google Scholar] [CrossRef]
  23. Desplanches, C.; Ruiz, E.; Rodrigue-Fortea, A.; Alvarez, S. Exchange coupling of transition-metal ions through hydrogen bonding: A theoretical investigation. J. Am. Chem. Soc. 2002, 124, 5197–5205. [Google Scholar] [CrossRef]
Magnetochemistry 07 00077 g001 550
Figure 1. TGA plot of 1 (black) and 2 (red).
Figure 1. TGA plot of 1 (black) and 2 (red).
Magnetochemistry 07 00077 g001
Magnetochemistry 07 00077 g002 550
Figure 2. Crystal structure and appearance of 1 (a) and 2 (b). Color code: K, dark green; Co, cyan; C, light grey; O, red.; H, grey. Blue dashed lines are hydrogen bonds.
Figure 2. Crystal structure and appearance of 1 (a) and 2 (b). Color code: K, dark green; Co, cyan; C, light grey; O, red.; H, grey. Blue dashed lines are hydrogen bonds.
Magnetochemistry 07 00077 g002
Magnetochemistry 07 00077 g003 550
Figure 3. Magnetic susceptibility of 1 (black square) and 2 (red circle) under 1000 Oe. Inset: ZFCM/FCM/RM at 10 Oe of 2. Red line: Curie-Weiss fitting.
Figure 3. Magnetic susceptibility of 1 (black square) and 2 (red circle) under 1000 Oe. Inset: ZFCM/FCM/RM at 10 Oe of 2. Red line: Curie-Weiss fitting.
Magnetochemistry 07 00077 g003
Magnetochemistry 07 00077 g004 550
Figure 4. Isothermal magnetization of 1 (empty black square) and 2 (empty red circle) at 2 K.
Figure 4. Isothermal magnetization of 1 (empty black square) and 2 (empty red circle) at 2 K.
Magnetochemistry 07 00077 g004
Magnetochemistry 07 00077 sch001 550
Scheme 1. Schematic drawing of the possible route of crystal-to-crystal transformation from 1 to 2.
Scheme 1. Schematic drawing of the possible route of crystal-to-crystal transformation from 1 to 2.
Magnetochemistry 07 00077 sch001
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Zhang, B.; Zhang, Y.; Chang, G.; Wang, Z.; Zhu, D. Crystal-to-Crystal Transformation from K2[Co(C2O4)2(H2O)2]·4H2O to K2[Co(μ-C2O4)(C2O4)]. Magnetochemistry 2021, 7, 77. https://doi.org/10.3390/magnetochemistry7060077

AMA Style

Zhang B, Zhang Y, Chang G, Wang Z, Zhu D. Crystal-to-Crystal Transformation from K2[Co(C2O4)2(H2O)2]·4H2O to K2[Co(μ-C2O4)(C2O4)]. Magnetochemistry. 2021; 7(6):77. https://doi.org/10.3390/magnetochemistry7060077

Chicago/Turabian Style

Zhang, Bin, Yan Zhang, Guangcai Chang, Zheming Wang, and Daoben Zhu. 2021. "Crystal-to-Crystal Transformation from K2[Co(C2O4)2(H2O)2]·4H2O to K2[Co(μ-C2O4)(C2O4)]" Magnetochemistry 7, no. 6: 77. https://doi.org/10.3390/magnetochemistry7060077

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop