Next Article in Journal
Ageing and Langmuir Behavior of the Cage Occupancy in the Nitrogen Gas Hydrate
Previous Article in Journal
Thermodynamic Picture of Dimer-Mott Organic Superconductors Revealed by Heat Capacity Measurements with External and Chemical Pressure Control
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Crystals
Volume 8
Issue 4
10.3390/cryst8040144
crystals-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
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Communication

Unprecedented Hexanuclear Cobalt(II) Nonsymmetrical Salamo-Based Coordination Compound: Synthesis, Crystal Structure, and Photophysical Properties

by
Zong-Li Ren
,
Fei Wang
,
Ling-Zhi Liu
,
Bo-Xian Jin
and
Wen-Kui Dong
*
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China
*
Author to whom correspondence should be addressed.
Crystals 2018, 8(4), 144; https://doi.org/10.3390/cryst8040144
Submission received: 26 February 2018 / Revised: 16 March 2018 / Accepted: 20 March 2018 / Published: 22 March 2018
(This article belongs to the Section Crystal Engineering)
Browse Figures
Versions Notes

Abstract

:
A novel hexanuclear Co(II) coordination compound with a nonsymmetrical Salamo-type bisoxime ligandH4L, namely [{Co3(HL)(MeO)(MeOH)2(OAc)2}2]·2MeOH, was prepared and characterized by elemental analyses, UV–vis, IR and fluorescence spectra, and X-ray single-crystal diffraction analysis. Each Co(II) is hexacoordinated, and possesses a distorted CoO6 or CoO4N2 octahedrons. The Co(II) coordination compound possesses a self-assembled infinite 2D supramolecular structure with the help of the intermolecular C–H···O interactions. Meanwhile, the photophysical properties of the Co(II) coordination compound were studied.

Graphical Abstract

1. Introduction

Salen (N,N′-Disalicylideneethylenediamine) and its derivatives play an important role in inorganic chemistry [1,2,3,4,5,6,7,8,9,10], which are gained via the condensation reaction of diamines with salicylaldehyde or its analogues, and can coordinate to transition metal ions in a tetradentate chelating mode to form a neutral metal coordination compound [11,12,13,14,15,16,17,18]. Such coordination compounds have been extensively investigated as nonlinear optical materials [19], catalysts [20,21], strong activities with DNA, and so on [22,23,24,25,26,27,28,29]. In addition, some of these coordination compounds possess interesting magnetic properties [30,31,32]. Meanwhile, supramolecular chemistry has recognized Salen-type coordination compounds because of intermolecular hydrogen bonding interactions, C–H···π and π···π stacking interactions consist in chelate rings and the associated aromatic rings [33,34,35,36,37,38,39,40,41,42]. In recent years, our focus switched to the syntheses, structures, and properties of metal coordination compounds with Salamo (2,2′-[Ethylenedioxybis(nitrilomethyli-dyne)]diphenol) and its various derivatives derived from its constitutional units with different substituent groups [43,44,45,46,47,48,49]. The structural motifs of these coordination compound molecules may be affected by several factors, such as the performance of the ligands, the property of the central atoms, anion effects, solvent effects, and so on[50,51,52,53,54,55,56,57,58,59]. Transition metal Salamo-type coordination compounds have aroused widespread concerns for their photophysical properties [60,61,62,63,64,65,66]. Previous studies have been carried out on the mononuclear coordination compounds [67,68]. However, there are relatively few studies on multinuclear Salamo-type bisoxime coordination compounds. Though mono-, di-, and trinuclear Co(II) coordination compounds have been reported [69,70,71], the study of the synthesis and corresponding properties of multinuclear Co(II) coordination compounds are relatively few [72,73,74].
The purpose of the present work is the structural characterization of polynuclear Co(II) coordination compounds derived of nonsymmetrical Salamo-type bisoxime ligands. Here, the ligand H4L and its corresponding hexanuclear Co(II) coordination compound ([{Co3(HL)(MeO)(MeOH)2(OAc)2}2]·2MeOH) was gained. In addition, the supramolecular buildings and photophysical behaviors of the Co(II) coordination compound are discussed.

2. Experimental

2.1. Materials and Physical Measurements

All chemicals were of analytical reagent grade. Elemental analyses for C, H, and N were gained using a GmbH VarioEL V3.00 automatic elemental analysis instrument (Berlin, Germany), elemental analysis for Co was detected by an IRIS ER/S·WP-1 ICP atomic emission spectrometer (Berlin, Germany). UV–vis and fluorescence spectra were measured on a Shimadzu UV-2550 spectrometer (Shimadzu, Japan) and F-7000 FL spectrometer (Hitachi, Tokyo, Japan), respectively. Infrared (IR) spectra were performed on a VERTEX-70 FT-IR spectrophotometer (Bruker, Billerica, MA, USA), with samples prepared as KBr (500–4000 cm−1). 1H-NMR spectra were carried out via German Bruker AVANCE DRX-400 spectroscopy (Bruker AVANCE, Billerica, MA, USA). Single-crystal X-ray structure determination was performed on a SuperNova Dual (Cu at zero) Eos four-circle diffractometer. Melting points were measured via a microscopic melting point apparatus (Beijing Taike Instrument Limited Company, Beijing, China).

2.2. Preparations and Characterizations

2.2.1. Preparation and Characterization of H4L

1,2-Bis(aminooxy)ethane was obtained by an early reported method [75,76,77]. Yield: 85.2%. Anal. Calcd for C2H8N2O2 (%): C, 26.08; H, 8.76; N, 30.42. Found: C, 25.98; H, 8.90; N, 30.38. The synthetic route to H4L is depicted in Scheme 1.
Monooxime compound was obtained by a modified method [32]. After purification by column chromatography, single condensation product of ethylene oxide single condensing 1,2-diamine-2,4-dihydroxyacetophenone was obtained. Reaction of ethylene oxide single condensing 1,2-diamine-2,4-dihydroxyacetophenone with 2,3-dihydroxybenzaldehyde provided one nonsymmetrical Salamo-type compound H4L. Yield: 88.7%. Anal. Calcd. for C17H18N2O6 (%): C, 58.89; H, 4.82; N, 8.17. Found: C, 59.23; H, 4.91; N, 8.01. 1H-NMR (400MHz, CDCl3): δ = 2.28(s, 3H, –CH3), 4.45–4.53(m, 4H, –CH2–CH2–), 5.12(s, 1H, O–H), 5.59(s, 1H, O–H), 6.42(m, 2H, Ar–H), 6.75(dd, J = 1.52, 1.28Hz, 1H, Ar–H), 6.85(t, J = 1.36, 1.20, 1.16Hz, 1H, Ar–H), 6.97(dd, J = 1.56, 1.68Hz, 1H, Ar–H), 7.28(d, J = 9.12Hz, 1H, Ar–H), 8.22(s, 1H, N=C–H), 9.91(s, 1H, O–H), 11.38(s, 1H, O–H) ppm.

2.2.2. Preparation and Characterizationof the Co(II) Coordination Compound

A methanol solution (3 mL) of Co(OAc)2·4H2O (37.3 mg, 0.150 mmol) was added dropwise to a methanol solution (4 mL)of H4L (17.3 mg, 0.050 mmol). The color of the mixed solution immediately turned to brown, and then continuing stirring for 2 h. The resultant solution was allowed to slowly evaporate at room temperature. Brown diamond single crystals suitable for X-ray diffraction studies were obtained after four weeks. Yield: 68.5%. Anal. Calcd. for C50H72Co6N4O28 (%): C, 39.23; H, 4.74; N, 3.66; Co, 26.10. Found: C, 39.62; H, 4.57; N, 3.38; Co, 25.78.

2.3. X-ray Structure Determination of the Co(II) Coordination Compound

X-ray diffraction data were collected on a SuperNova Dual (Cu at zero) Eos four-circle diffractometer via graphite monochromatized Mo-Kα radiation (λ = 0.71073 Å) at 298(2) K. Unit cell parameters were determined by least squares analysis. The LP factor and semi-empirical absorption corrections were applied to the intensity data. The structure was solved by the direct method (SHELXS-97), and all hydrogen atoms were added theoretically. All non-hydrogen atoms were refined anisotropically using a full-matrix least-squares procedure on F2 with SHELXL-97. Anisotropic thermal parameters were assigned to all non-hydrogen atoms. The hydrogen atoms were generated geometrically. Some reflections with high intensities, which made the detector overflow, were automatically omitted by the diffractometer. So some reflections were missing. The crystallographic and structural refinement data for the Co(II) coordination compound are summed in Table 1. Supplementary crystallographic data for this paper have been deposited at the Cambridge Crystallographic Data Centre (1519431) and can be obtained free of charge viawww.ccdc.cam.ac.uk/conts/retrieving.html.

3. Results and Discussion

3.1. Description of the Crystal Structure

Asdepicted in Figure 1, the centrosymmetric neutral homomultinuclear Co(II) coordination compound has been revealedby single crystal X-raydiffraction (Table 2). It crystallizes in the monoclinic crystal system, space group C2/c, and consists of six Co(II) atoms, two (HL)3‒ units, two μ2-acetato ions, two bidentate chelating acetate ions, two coordinated deprotonated methanol molecules, four coordinated methanol molecules, and two crystallizing methanol molecules. This 6:2 (Co(II) atom: Ligand) type of Co(II) coordination compound is unprecedented in the early reported Salamo-based Co(II) coordination compounds bearing the structures of 1:1 [44,58], 3:2 [44,47,74], 4:2 [15] and 8:4 [78]. (Figure 1) The whole coordination compound molecule is symmetrical and therefore only shows Co1, Co2, and Co3 coordination situation can explain the structure of the whole coordination compound. The terminal Co1 atom is located in the N2O2 coordination sphere, the axial position is occupied by two oxygen atoms from two coordinated methanol molecules. The Co2 atom is surrounded by quadruple phenol oxygen atoms (O1, O5, O7 and O7#1) from two (HL)3‒ moieties, one μ2-acetato oxygen atom (O2) and one deprotonated methanol oxygen atom (O6). Meanwhile, the Co3 atom coordinates with one phenol oxygen atom (O7) from one (HL)3‒ moiety, one μ2-acetato oxygen atom (O13), two oxygen atoms (O6 and O6#1) of two coordinated deprotonated methanol molecules and two bidentate chelate acetato oxygen atoms (O11 and O12) which adopt a familiar Co–O–C–O–Co fashion. Each Co(II) atom bears a hexacoordinate sphere and possesses distorted CoO6 or CoO4N2 octahedrons.The hydrogen atoms of two μ2-acetato ions (H10B, H10C, H10D and H10B#1, H10C#1, H10D#1; H22A, H22B, H22C and H22A#1, H22B#1, H22C#1) are disordered equally over two different positions, which were allowed for during refinement.
In the crystal structure of the Co(II) coordination compound, there are five significant intramolecular hydrogen bonds (O9–H9···O2, O10–H10···O11, C2–H2···O11, C17–H17C···O3 and C8–H8B···O9) and two intermolecular C12–H12···O13 and O14–H14A···O12 interactions (Figure 2). In addition, there is a pair of π···π interactions Cg1···Cg1 (Cg1=C1–C2–C3–C4–C5–C6) (Figure 3) in the Co(II) coordination compound [79]. Meanwhile, the hydrogen bonds interactions existing in the Co(II) coordination compound are described in graph sets (Figure 4) [80]. Furthermore, the molecules are linked by intermolecular interactions form a 2D infinite planar (Figure 5). Putative hydrogen bonds for the Co(II) coordination compoundare listed in Table 3.

3.2. IR Spectroscopy

IR spectra (Table 4) of H4L and its corresponding Co(II) coordination compound exhibit different bands in the region of 400–4000 cm−1. H4L shows a characteristic C=N stretching band at 1630 cm−1, while the C=N stretching band of the Co(II) coordination compound appears at 1592cm−1 [64]. For the ligand H4L, the Ar–O stretching band appears at 1260 cm−1, which is observed at 1255 cm−1 for the Co(II) coordination compound. The characteristic C=N and Ar–O stretching frequencies are shifted to lower frequencies, exhibiting that the Co–N and Co–O bonds are formed [69,71]. The O–H stretching frequency of H4L appears at 3373 cm−1, whereas the Co(II) coordination compound shows a stretching band at 3421 cm−1, which is attributed to vibrations of the coordinated methanol molecules. For the Co(II) coordination compound, the ν(Co–O) and ν(Co–N) frequencies are observed at 463 and 519 cm−1, respectively [74,81].

3.3. UV–Vis Spectroscopy

The UV–vis spectra of H4L and its Co(II) coordination compound were measured in 1×10−6 mol·L−1 CH2Cl2 solution. It is noteworthy that the absorption peaks of the Co(II) coordination compound are evidently different from those of H4L (Figure 6). Electronic absorption spectrum of H4L composes of two relatively intense peaks centered at 275 and 299 nm, attributed to the intra-ligand π–π* transitions of the benzene rings and the C=N bonds, respectively. Compared with H4L, the absorption peaks of the Co(II) coordination compound appears at 277 and 311 nm, which are bathochromically shifted by ca. 2 and 12 nm, exhibiting the Co(II) ions have coordinated with H4L. The new peak of the Co(II) coordination compound appears at ca. 385 nm, attributed to L→M charge-transfer transition [82,83].

3.4. Fluorescence Properties

The fluorescence properties of H4L and its corresponding Co(II) coordination compound were studied are depicted in Figure 7. H4L displays strong emission peak at ca. 412 nm upon excitation at 271 nm, and it should be attributed to the intra-ligand π–π* transition. The Co(II) coordination compound displays lower photoluminescence with maximum emission at ca. 360 nm. Compared with H4L, emission intensity of the Co(II) coordination compound evidently reduces, showing that the Co(II) ions possess a certain degree of fluorescence quenching, which makes the conjugated system larger, and also indicates it may be a purple device. The solid-state fluorescence spectra of the ligand H4L and its Co(II) coordination compound are depicted in Figure 8. Compared to liquid fluorescence spectroscopy, the ligand H4L and its corresponding Co(II) coordination compound have strong fluorescence in solid-state fluorescence spectroscopy.

4. Conclusions

In summary, we have synthesized and characterized a nonsymmetrical Salamo-type N2O2 ligand, and obtained an unprecedented hexanuclear Co(II) coordination compound, [{Co3(HL)(MeO)(MeOH)2(OAc)2}2]·2MeOH. X-ray crystal structure analysis of the Co(II) coordination compound revealed that each Co(II) is hexacoordinated, and possesses distorted CoO6 or CoO4N2 octahedrons. The Co(II) coordination compound possesses a 2D layered structure through intermolecular C–H···O interactions. In addition, the fluorescence properties indicate that coordinated Co(II) ions resulted to the fluorescence quenching of H4L.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (21761018) and the Program for Excellent Team of Scientific Research in Lanzhou Jiaotong University (201706), which is gratefully acknowledged.

Author Contributions

Wen-Kui Dong and Fei Wang conceived and designed the experiments; Bo-Xian Jin performed the experiments; Ling-Zhi Liu analyzed the data; Wen-Kui Dong contributed reagents/materials/analysis tools; Zong-Li Ren wrote the paper.

Conflicts of Interest

The authors declare no competing financial interests.

References

  1. Zhou, J.J.; Song, X.Q.; Liu, Y.A.; Wang, X.L. Substituent-tuned structure and luminescence sensitizing towards Al3+ based on phenoxy bridged dinuclear EuIII complexes. RSC Adv. 2017, 7, 25549–25559. [Google Scholar] [CrossRef]
  2. Xu, L.; Zhu, L.C.; Ma, J.C.; Zhang, Y.; Zhang, J.; Dong, W.K. Syntheses, structures and spectral properties of mononuclear CuII and dimeric ZnII complexes based on an asymmetric Salamo-type N2O2 ligand. Z. Anorg. Allg. Chem. 2015, 641, 2520–2524. [Google Scholar] [CrossRef]
  3. Dong, X.Y.; Li, X.Y.; Liu, L.Z.; Zhang, H.; Ding, Y.J.; Dong, W.K. Tri- and hexanuclear heterometallic Ni(II)–M(II) (M = Ca, Sr and Ba) bis(Salamo)-type complexes: Synthesis, structure and fluorescence properties. RSC Adv. 2017, 7, 48394–48403. [Google Scholar] [CrossRef]
  4. Yang, Y.H.; Hao, J.; Dong, Y.J.; Wang, G. Two znic(II) complexes constructed from a bis(Salamo)-type tetraoxime ligand: Syntheses, crystal structures and luminescence properties. Chin. J. Inorg. Chem. 2017, 33, 1280–1292. [Google Scholar]
  5. Chai, L.Q.; Huang, J.J.; Zhang, H.S. An unexpected cobalt (III) complex containing a schiff base ligand: Synthesis, crystal structure, spectroscopic behavior, electrochemical property and SOD-like activity. Spectrochim. Acta Part A 2014, 131, 526–530. [Google Scholar] [CrossRef] [PubMed]
  6. Chai, L.Q.; Tang, L.J.; Chen, L.C.; Huang, J.J. Structural, spectral, electrochemical and DFT studies of two mononuclear manganese(II) and zinc(II) complexes. Polyhedron 2017, 122, 228–240. [Google Scholar] [CrossRef]
  7. Chai, L.Q.; Huang, J.J.; Zhang, J.Y.; Li, Y.X. Two 1-D and 2-D cobalt(II) complexes: Synthesis, crystal structures, spectroscopic and electrochemical properties. J. Coord. Chem. 2015, 68, 1224–1237. [Google Scholar] [CrossRef]
  8. Chai, L.Q.; Zhang, K.Y.; Tang, L.J.; Zhang, J.Y.; Zhang, H.S. Two mono- and dinuclear Ni(II) complexes constructed from quinazoline-type ligands: Synthesis, x-ray structures, spectroscopic, electrochemical, thermal, and antimicrobial studies. Polyhedron 2017, 130, 100–107. [Google Scholar] [CrossRef]
  9. Dong, Y.J.; Dong, X.Y.; Dong, W.K.; Zhang, Y.; Zhang, L.S. Three asymmetric Salamo-type copper(II) and cobalt(II) complexes: Syntheses, structures, fluorescent properties. Polyhedron 2017, 123, 305–315. [Google Scholar] [CrossRef]
  10. Dong, W.K.; Ma, J.C.; Dong, Y.J.; Zhao, L.; Zhu, L.C.; Sun, Y.X.; Zhang, Y. Two hetero-trinuclear Zn(II)-M(II) (M = Sr, Ba) complexes based on metallohost of mononuclear Zn(II) complex: Syntheses, structures and fluorescence properties. J. Coord. Chem. 2016, 69, 3231–3240. [Google Scholar] [CrossRef]
  11. Dong, Y.J.; Ma, J.C.; Zhu, L.C.; Dong, W.K.; Zhang, Y. Four 3d–4f heteromultinuclear zinc(II)–lanthanide(III) complexes constructed from a distinct hexadentate N2O2-type ligand: Syntheses, structures and photophysical properties. J. Coord. Chem. 2017, 70, 103–115. [Google Scholar] [CrossRef]
  12. Dong, W.K.; Akogun, S.F.; Zhang, Y.; Dong, X.Y. A reversible “turn-on” fluorescent sensor for selective detection of Zn2+. Sens. Actuators B 2017, 238, 723–734. [Google Scholar] [CrossRef]
  13. Dong, W.K.; Ma, J.C.; Zhu, L.C.; Zhang, Y.; Li, X.L. Four new nickel(II) complexes based on an asymmetric Salamo-type ligand: Synthesis, structure, solvent effect and electrochemical property. Inorg. Chim. Acta 2016, 445, 140–148. [Google Scholar] [CrossRef]
  14. Dong, W.K.; Zhu, L.C.; Dong, Y.J.; Ma, J.C.; Zhang, Y. Mono, di and heptanuclear metal(II) complexes based on symmetric and asymmetric tetradentate Salamo-type ligands: Syntheses, structures and spectroscopic properties. Polyhedron 2016, 117, 148–154. [Google Scholar] [CrossRef]
  15. Ma, J.C.; Dong, X.Y.; Dong, W.K.; Zhang, Y.; Zhu, L.C.; Zhang, J.T. A new application of Salamo-type bisoximes: As a relay–sensor for Zn2+/Cu2+ and its novel complexes for successive sensing of H+/OH−. J. Coord. Chem. 2016, 69, 149–159. [Google Scholar] [CrossRef]
  16. Chai, L.Q.; Liu, G.; Zhang, Y.L.; Huang, J.J.; Tong, J.F. Synthesis, crystal structure, fluorescence, electrochemical property, and SOD-like activity of an unexpected nickel(II) complex with a quinazoline-type ligand. J. Coord. Chem. 2013, 66, 3926–3938. [Google Scholar] [CrossRef]
  17. Chai, L.Q.; Wang, G.; Sun, Y.X.; Dong, W.K.; Zhao, L.; Gao, X.H. Synthesis, crystal structure, and fluorescence of an unexpected dialkoxo-bridged dinuclear copper(II) complex with bis(Salen)-type tetraoxime. J. Coord. Chem. 2012, 65, 1621–1631. [Google Scholar] [CrossRef]
  18. Chai, L.Q.; Zhang, H.S.; Dong, W.K.; Zhao, Y.L. Synthesis of unsymmetrical ureas with coumarin and thiadiazole ring under microwave irradiation. Phosphorus Sulfur Silicon 2010, 185, 1332–1337. [Google Scholar] [CrossRef]
  19. Bella, S.D.; Fragalà, I. Chem Inform abstract: Synthesis and second-order nonlinear optical properties of bis(salicylaldiminato) M(II) metalloorganic materials. Synth. Met. 2000, 115, 191–196. [Google Scholar] [CrossRef]
  20. Li, L.H.; Dong, W.K.; Zhang, Y.; Akogun, S.F.; Xu, L. Syntheses, structures and catecholase activities of homo- and hetero-trinuclear cobalt(II) complexes constructed from an acyclic naphthalenediol-based bis(Salamo)-type ligand. Appl. Organomet. Chem. 2017, 31, e3818. [Google Scholar] [CrossRef]
  21. Li, X.Y.; Chen, L.; Gao, L.; Zhang, Y.; Akogun, S.F.; Dong, W.K. Syntheses, crystal structures and catalytic activities of two solvent-induced homotrinuclear Co(II) complexes with a naphthalenediol-based bis(Salamo)-type tetraoxime ligand. RSC Adv. 2017, 7, 35905–35916. [Google Scholar] [CrossRef]
  22. Wu, H.L.; Pan, G.L.; Bai, Y.C.; Wang, H.; Kong, J. Synthesis, structure, antioxidation, and DNA-bindingstudies of a binuclear ytterbium(III) complex with bis(N-salicylidene)-3-oxapentane-1,5-diamine. Res. Chem. Intermed. 2015, 41, 3375–3388. [Google Scholar] [CrossRef]
  23. Wu, H.L.; Bai, Y.C.; Zhang, Y.H.; Pan, G.L.; Kong, J.; Shi, F.; Wang, X.L. Two lanthanide(III) complexes based on the schiff base N,N-Bis(salicylidene)-1,5-diamino-3-oxapentane: Synthesis, characterization, DNA-binding properties, and antioxidation. Z. Anorg. Allg. Chem. 2014, 640, 2062–2071. [Google Scholar] [CrossRef]
  24. Chen, C.Y.; Zhang, J.W.; Zhang, Y.H.; Yang, Z.H.; Wu, H.L. Gadolinium(III) and dysprosium(III) complexes with a schiff base bis(N-salicylidene)-3-oxapentane-1,5-diamine: Synthesis, characterization, antioxidation, and DNA-binding studies. J. Coord. Chem. 2015, 68, 1054–1071. [Google Scholar] [CrossRef]
  25. Wu, H.L.; Bai, Y.C.; Zhang, Y.H.; Li, Z.; Wu, M.C.; Chen, C.Y.; Zhang, J.W. Synthesis, crystal structure, antioxidation and DNA-binding properties of a dinuclear copper(II) complex with bis(N-salicylidene)-3-oxapentane-1,5-diamine. J. Coord. Chem. 2014, 67, 3054–3066. [Google Scholar] [CrossRef]
  26. Wu, H.L.; Pan, G.L.; Bai, Y.C.; Zhang, Y.H.; Wang, H.; Shi, F.R.; Wang, X.L.; Kong, J. Study on synthesis, crystal structure, antioxidant and DNA-binding of mono-, di-and poly-nuclear lanthanides complexes with bis (N-salicylidene)-3-oxapentane-1, 5-diamine. J. Photochem. Photobiol. B 2014, 135, 33–43. [Google Scholar] [CrossRef] [PubMed]
  27. Wu, H.L.; Pan, G.L.; Bai, Y.C.; Wang, H.; Kong, J.; Shi, F.R.; Zhang, Y.H.; Wang, X.L. Preparation, structure, DNA-binding properties, and antioxidant activities of a homodinuclear erbium(III) complex with a pentadentate schiff base ligand. J. Chem. Res. 2014, 38, 211–217. [Google Scholar] [CrossRef]
  28. Wu, H.L.; Wang, C.P.; Wang, F.; Peng, H.P.; Zhang, H.; Bai, Y.C. A new manganese(III) complex from bis(5-methylsalicylaldehyde)-3-oxapentane-1,5-diamine: Synthesis, characterization, antioxidant activity and luminescence. J. Chin. Chem. Soc. 2015, 62, 1028–1034. [Google Scholar] [CrossRef]
  29. Wu, H.L.; Bai, Y.; Yuan, J.K.; Wang, H.; Pan, G.L.; Fan, X.Y.; Kong, J. A zinc(II) complex with tris(2-(N-methyl)benzimidazlylmethyl)amine and salicylate: Synthesis, crystal structure, and DNA-binding. J. Coord. Chem. 2012, 65, 2839–2851. [Google Scholar] [CrossRef]
  30. Song, X.Q.; Liu, P.P.; Wang, C.Y.; Liu, Y.A.; Liu, W.S.; Zhang, M. Three sandwich-type zinc(II)–lanthanide(III) clusters: Structures, luminescence and magnetic properties. RSC Adv. 2017, 7, 22692–22698. [Google Scholar] [CrossRef]
  31. Zheng, S.S.; Dong, W.K.; Zhang, Y.; Chen, L.; Ding, Y.J. Four Salamo-type 3d–4f hetero-bimetallic [ZnIILnIII] complexes: Syntheses, crystal structures, and luminescent and magnetic properties. New J. Chem. 2017, 41, 4966–4973. [Google Scholar] [CrossRef]
  32. Dong, W.K.; Ma, J.C.; Zhu, L.C.; Zhang, Y. Nine self–assembled nickel(II)–lanthanide(III) heterometallic complexes constructed from a Salamo–type bisoxime and bearing N- or O-donor auxiliary ligand: Syntheses, structures and magnetic properties. New J. Chem. 2016, 40, 6998–7010. [Google Scholar] [CrossRef]
  33. Sun, Y.X.; Wang, L.; Dong, X.Y.; Ren, Z.L.; Meng, W.S. Synthesis, characterization, and crystal structure of a supramolecular CoII complex containing Salen-type bisoxime. Synth. React. Inorg. Met.-Org. Nano Met. Chem. 2013, 43, 599–603. [Google Scholar] [CrossRef]
  34. Sun, Y.X.; Xu, L.; Zhao, T.H.; Liu, S.H.; Dong, X.T. Synthesis and crystal structure of a 3D supramolecular copper(II) complex with 1-(3-{[(E)-3-bromo-5-chloro-2-hydroxybenzylidene]amino}phenyl) ethanoneoxime. Synth. React. Inorg. Met.-Org. Nano Met. Chem. 2013, 43, 509–513. [Google Scholar] [CrossRef]
  35. Sun, Y.X.; Zhang, S.T.; Ren, Z.L.; Dong, X.Y.; Wang, L. Synthesis, characterization, and crystal structure of a new supramolecular CdII complex with halogen-substituted Salen-type bisoxime. Synth. React. Inorg. Met.-Org. Nano Met. Chem. 2013, 43, 995–1000. [Google Scholar] [CrossRef]
  36. Sun, Y.X.; Gao, X.H. Synthesis, characterization, and crystal structure of a new CuII complex with Salen-type ligand. Synth. React. Inorg. Met.-Org. Nano Met. Chem. 2011, 41, 973–978. [Google Scholar] [CrossRef]
  37. Song, X.Q.; Liu, P.P.; Xiao, Z.R.; Li, X.; Liu, Y.A. Four polynuclear complexes based on a versatile salicylamide Salen-like ligand: Synthesis, structural variations and magnetic properties. Inorg. Chim. Acta 2015, 438, 232–244. [Google Scholar] [CrossRef]
  38. Liu, Y.A.; Wang, C.Y.; Zhang, M.; Song, X.Q. Structures and magnetic properties of cyclic heterometallic tetranuclear clusters. Polyhedron 2017, 127, 278–286. [Google Scholar] [CrossRef]
  39. Liu, P.P.; Wang, C.Y.; Zhang, M.; Song, X.Q. Pentanuclear sandwich-type ZnII-LnIII clusters based on a new Salen-like salicylamide ligand: Structure, near-infrared emission and magnetic properties. Polyhedron 2017, 129, 133–140. [Google Scholar] [CrossRef]
  40. Liu, P.P.; Sheng, L.; Song, X.Q.; Xu, W.Y.; Liu, Y.A. Synthesis, structure and magnetic properties of a new one dimensional manganese coordination polymer constructed by a new asymmetrical ligand. Inorg. Chim. Acta 2015, 434, 252–257. [Google Scholar] [CrossRef]
  41. Song, X.Q.; Peng, Y.J.; Chen, G.Q.; Wang, X.R.; Liu, P.P.; Xu, W.Y. Substituted group-directed assembly of Zn(II) coordination complexes based on two new structural related pyrazolone based Salen ligands: Syntheses, structures and fluorescence properties. Inorg. Chim. Acta 2015, 427, 13–21. [Google Scholar] [CrossRef]
  42. Song, X.Q.; Liu, P.P.; Liu, Y.A.; Zhou, J.J.; Wang, X.L. Two dodecanuclearheterometallic [Zn6Ln6] clusters constructed by a multidentate salicylamide Salen-like ligand: Synthesis, structure, luminescence and magnetic properties. Dalton. Trans. 2016, 45, 8154–8163. [Google Scholar] [CrossRef] [PubMed]
  43. Wang, L.; Hao, J.; Zhai, L.X.; Zhang, Y.; Dong, W.K. Synthesis, crystal structure, luminescence, electrochemical and antimicrobial properties of bis(Salamo)-based Co(II) complex. Crystals 2017, 7, 277. [Google Scholar] [CrossRef]
  44. Akine, S. Novel ion recognition systems based on cyclic and acyclic oligo(Salen)-type ligands. J. Incl. Phenom. Macrocycl. Chem. 2012, 72, 25–54. [Google Scholar] [CrossRef]
  45. Zhang, H.; Dong, W.K.; Zhang, Y.; Akogun, S.F. Naphthalenediol-based bis(Salamo)-type homo- and heterotrinuclear cobalt(II) complexes: Syntheses, structures and magnetic properties. Polyhedron 2017, 133, 279–293. [Google Scholar] [CrossRef]
  46. Li, X.Y.; Kang, Q.P.; Liu, L.Z.; Ma, J.C.; Dong, W.K. Trinuclear Co(II) and mononuclear Ni(II) Salamo-type bisoxime coordination compounds. Crystals 2018, 8, 43. [Google Scholar] [CrossRef]
  47. Dong, W.K.; Li, G.; Wang, Z.K.; Dong, X.Y. A novel trinuclear cobalt(II) complex derived from an asymmetric Salamo-type N2O3bisoxime chelate ligand: Synthesis, structure and optical properties. Spectrochim. Acta Part A 2014, 133, 340–347. [Google Scholar] [CrossRef] [PubMed]
  48. Dong, X.Y.; Akogun, S.F.; Zhou, W.M.; Dong, W.K. Tetranuclear Zn(II) complex based on an asymmetrical Salamo-type chelating ligand: Synthesis, structural characterization, and fluorescence property. J. Chin. Chem. Soc. 2017, 64, 412–419. [Google Scholar] [CrossRef]
  49. Dong, W.K.; Ma, J.C.; Zhu, L.C.; Zhang, Y. Self-assembled zinc(II)-lanthanide(III) heteromultinuclear complexes constructed from 3-MeO Salamo ligand: Syntheses, structures and luminescent properties. Cryst. Growth Des. 2016, 16, 6903–6914. [Google Scholar] [CrossRef]
  50. Zhao, L.; Dang, X.T.; Chen, Q.; Zhao, J.X.; Wang, L. Synthesis, crystal structure and spectral properties of a 2D supramolecular copper(II) complex with 1-(4-{[(E)-3-ethoxyl-2-hydroxybenzylidene]amino}phenyl)ethanoneoxime. Synth. React. Inorg. Met.-Org. Nano Met. Chem. 2013, 43, 1241–1246. [Google Scholar] [CrossRef]
  51. Zhao, L.; Wang, L.; Sun, Y.X.; Dong, W.K.; Tang, X.L.; Gao, X.H. A supramolecular copper(II) complex bearing Salen-type bisoxime ligand: Synthesis, structural characterization, and thermal property. Synth. React. Inorg. Met.-Org. Nano Met. Chem. 2012, 42, 1303–1308. [Google Scholar] [CrossRef]
  52. Wang, P.; Zhao, L. An infinite 2D supramolecular cobalt(II) complex based on an asymmetric Salamo-type ligand: Synthesis, crystal structure, and spectral properties. Synth. React. Inorg. Met.-Org. Nano Met. Chem. 2016, 46, 1095–1101. [Google Scholar] [CrossRef]
  53. Wang, P.; Zhao, L. Synthesis, structure and spectroscopic properties of the trinuclear cobalt(II) and nickel(II) complexes based on 2-hydroxynaphthaldehyde and bis(aminooxy)alkane. Spectrochim. Acta Part A 2015, 135, 342–350. [Google Scholar] [CrossRef] [PubMed]
  54. Wang, L.; Ma, J.C.; Dong, W.K.; Zhu, L.C.; Zhang, Y. A novel self–assembled nickel(II)–cerium(III) heterotetranuclear dimer constructed from N2O2-type bisoxime and terephthalic acid: Synthesis, structure and photophysical properties. Z. Anorg. Allg. Chem. 2016, 642, 834–839. [Google Scholar] [CrossRef]
  55. Dong, W.K.; Li, X.L.; Wang, L.; Zhang, Y.; Ding, Y.J. A new application of Salamo-type bisoximes: As a relay-sensor for Zn2+/Cu2+ and its novel complexes for successive sensing of H+/OH−. Sens. Actuators B 2016, 229, 370–378. [Google Scholar] [CrossRef]
  56. Dong, W.K.; Zhang, J.T.; Dong, Y.J.; Zhang, Y.; Wang, Z.K. Construction of mononuclear copper(II) and trinuclear cobalt(II) complexes based on asymmetric Salamo-type ligands. Z. Anorg. Allg. Chem. 2016, 642, 189–196. [Google Scholar] [CrossRef]
  57. Dong, W.K.; Sun, Y.X.; He, X.N.; Tong, J.F.; Wu, J.C. Trinuclear and mononuclear copper(II) complexes incorporating tetradentate 2,2′-[1,1′-(ethylenedioxydinitrilo)diethylidyne]diphenol ligand: Syntheses, crystal structures, spectral and thermal behaviors. Spectrochim. Acta Part A 2010, 76, 476–483. [Google Scholar] [CrossRef] [PubMed]
  58. Dong, W.K.; Li, X.; Yang, C.J.; Zhao, M.M.; Li, G.; Dong, X.Y. Syntheses and crystal structures of 5-methoxy-6′-hydroxy-2,2′ -[ethylenedioxybis(nitrilomethylidyne)]diphenol and its tetranuclear zinc(II) complex. Chin. J. Inorg. Chem. 2014, 30, 710–716. [Google Scholar]
  59. Dong, W.K.; Zhang, F.; Li, N.; Xu, L.; Zhang, Y.; Zhang, J.; Zhu, L.C. Trinuclear cobalt(II) and zinc(II) Salamo-type complexes: Syntheses, crystal structures, and fluorescent properties. Z. Anorg. Allg. Chem. 2016, 642, 532–538. [Google Scholar] [CrossRef]
  60. Chen, L.; Dong, W.K.; Zhang, H.; Zhang, Y.; Sun, Y.X. Structural variation and luminescence properties of trianddinuclear CuII and ZnII complexes constructed from a naphthalenediol-based bis(Salamo)-type ligand. Cryst. Growth Des. 2017, 17, 3636–3648. [Google Scholar] [CrossRef]
  61. Wang, F.; Gao, L.; Zhao, Q.; Zhang, Y.; Dong, W.K.; Ding, Y.J. A highly selective fluorescent chemosensor for CN− based on a novel bis(Salamo)-type tetraoxime ligand. Spectrochim. Acta Part A 2018, 190, 111–115. [Google Scholar] [CrossRef] [PubMed]
  62. Dong, X.Y.; Gao, L.; Wang, F.; Zhang, Y.; Dong, W.K. Tri- and mono-nuclear zinc(II) complexes based onhalf- and mono-Salamo chelating ligands. Crystals 2017, 7, 267. [Google Scholar] [CrossRef]
  63. Peng, Y.D.; Li, X.Y.; Kang, Q.P.; An, G.X.; Zhang, Y.; Dong, W.K. Synthesis and fluorescence properties of asymmetrical Salamo-type tetranuclear zinc(II) complex. Crystals 2018, 8, 107. [Google Scholar] [CrossRef]
  64. Hao, J.; Liu, L.Z.; Dong, W.K.; Zhang, J.; Zhang, Y. Three multinuclear Co(II), Zn(II) and Cd(II) complexes based on a single-armed Salamo-type bisoxime: Syntheses, structural characterizations and fluorescent properties. J. Coord. Chem. 2017, 70, 1936–1952. [Google Scholar] [CrossRef]
  65. Wang, L.; Li, X.Y.; Zhao, Q.; Li, L.H.; Dong, W.K. Fluorescence properties of heterotrinuclear Zn(II)-M(II) (M = Ca, Sr and Ba) bis(Salamo)-type complexes. RSC Adv. 2017, 7, 48730–48737. [Google Scholar] [CrossRef]
  66. Akine, S.; Morita, Y.; Utsuno, F.; Nabeshima, T. Multiple folding structures mediated by metal coordination of acyclic multidentate ligand. Inorg. Chem. 2009, 48, 10670–10678. [Google Scholar] [CrossRef] [PubMed]
  67. Gao, L.; Liu, C.; Wang, F.; Dong, W.K. Tetra-, penta- and hexa-coordinated transition metal complexes constructed from coumarin-containing N2O2 ligand. Crystals 2018, 8, 77. [Google Scholar] [CrossRef]
  68. Li, G.; Hao, J.; Liu, L.Z.; Zhou, W.M.; Dong, W.K. Syntheses, crystal structures and thermal behaviors of two supramolecular Salamo-type cobalt(II) and zinc(II) complexes. Crystals 2017, 7, 217. [Google Scholar]
  69. Gao, L.; Wang, F.; Zhao, Q.; Zhang, Y.; Dong, W.K. Mononuclear Zn(II) and trinuclear Ni(II) complexes derived from a coumarin-containing N2O2 ligand: Syntheses, crystal structures and fluorescence properties. Polyhedron 2018, 139, 7–16. [Google Scholar] [CrossRef]
  70. Hao, J.; Li, L.H.; Zhang, J.T.; Akogun, S.F.; Wang, L.; Dong, W.K. Four homo- and hetero-bismetallic 3d/3d-2s complexes constructed from a naphthalenediol-based acyclic bis(Salamo)-type tetraoxime ligand. Polyhedron 2017, 134, 1–10. [Google Scholar] [CrossRef]
  71. Dong, X.Y.; Sun, Y.X.; Wang, L.; Li, L. Synthesis and structure of a penta- and hexa-coordinated tri-nuclear cobalt(II) complex. J. Chem. Res. 2012, 36, 387–390. [Google Scholar] [CrossRef]
  72. Dong, W.K.; Zhang, J.; Zhang, Y.; Li, N. Novel multinuclear transition metal(II) complexes based on an asymmetric Salamo-type ligand: Syntheses, structure characterizations and fluorescent properties. Inorg. Chim. Acta 2016, 444, 95–102. [Google Scholar] [CrossRef]
  73. Dong, X.Y.; Kang, Q.P.; Li, X.Y.; Ma, J.C.; Dong, W.K. Structurally characterized solvent-induced homotrinuclear cobalt(II) N2O2-donor bisoxime-type complexes. Crystals 2018, 8, 139. [Google Scholar] [CrossRef]
  74. Dong, W.K.; Sun, Y.X.; Zhao, C.Y.; Dong, X.Y.; Xu, L. Synthesis, structure and properties of supramolecular MnII, CoII, NiII and ZnII complexes containing Salen-type bisoxime ligands. Polyhedron 2010, 29, 2087–2097. [Google Scholar] [CrossRef]
  75. Wang, B.J.; Dong, W.K.; Zhang, Y.; Akogun, S.F. A novel relay-sensor for highly sensitive and selective detection of Zn2+/Pic− and fluorescence on/off switch response of H+/OH−. Sens. Actuators B 2017, 247, 254–264. [Google Scholar] [CrossRef]
  76. Dong, W.K.; Du, W.; Zhang, X.Y.; Li, G.; Dong, X.Y. Synthesis, crystal structure and spectral properties of a supramolecular trinuclear nickel(II) complex with 5-methoxy-4′-bromo-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol. Spectrochim. Acta Part A 2014, 132, 588–593. [Google Scholar] [CrossRef] [PubMed]
  77. Dong, Y.J.; Li, X.L.; Zhang, Y.; Dong, W.K. A highly selective visual and fluorescent sensor for Pb2+ and Zn2+ and crystal structure of Cu2+ complex based-on a novel single-armed Salamo-type bisoxime. Supramol. Chem. 2017, 29, 518–527. [Google Scholar] [CrossRef]
  78. Akine, S.; Dong, W.K.; Nabeshima, T. Octanuclearzinc(II) and cobalt(II) clusters produced by cooperative tetrameric assembling of oxime chelate ligands. Inorg. Chem. 2006, 45, 4677–4684. [Google Scholar] [CrossRef] [PubMed]
  79. Kruszynski, R.; Siera´nski, T. Can stacking interactions exist beyond the commonly accepted limits? Cryst. Growth Des. 2016, 16, 587–595. [Google Scholar] [CrossRef]
  80. Bernstein, J.; Davis, R.E.; Shimoni, L.; Chang, N.L. Patterns in hydrogen bonding: Functionality and graph set analysis in crystals. Angew. Chem. Int. Ed. Engl. 1995, 34, 1555–1573. [Google Scholar] [CrossRef]
  81. Percy, G.; Thornton, D. Infrared spectra of N-aryl salicylaldimine complexes substituted in both aryl rings. J. Inorg. Nucl. Chem. 1973, 35, 2319–2327. [Google Scholar] [CrossRef]
  82. Song, X.Q.; Wang, L.; Zheng, Q.F.; Liu, W.S. Synthesis, crystal structure and luminescence properties of lanthanide complexes with a new semirigid bridging furfurylsalicylamide ligand. Inorg. Chim. Acta 2013, 391, 171–178. [Google Scholar] [CrossRef]
  83. Song, X.Q.; Cheng, G.Q.; Wang, X.R.; Xu, W.Y.; Liu, P.P. Structure-based description of a step-by-step synthesis of heterodinuclear ZnIILnIII complexes and their luminescence properties. Inorg. Chim. Acta 2015, 425, 145–153. [Google Scholar] [CrossRef]
Crystals 08 00144 sch001 550
Scheme 1. Synthetic route to H4L.
Scheme 1. Synthetic route to H4L.
Crystals 08 00144 sch001
Crystals 08 00144 g001 550
Figure 1. (a) Crystal structure and atom numberings of the Co(II) coordination compound; (b) Coordination polyhedrons for Co(II) atoms.
Figure 1. (a) Crystal structure and atom numberings of the Co(II) coordination compound; (b) Coordination polyhedrons for Co(II) atoms.
Crystals 08 00144 g001
Crystals 08 00144 g002 550
Figure 2. View of the intramolecular (a) and intermolecular (b) interactions of the Co(II) coordination compound.
Figure 2. View of the intramolecular (a) and intermolecular (b) interactions of the Co(II) coordination compound.
Crystals 08 00144 g002
Crystals 08 00144 g003 550
Figure 3. π···π stacking interactions of the Co(II) coordination compound.
Figure 3. π···π stacking interactions of the Co(II) coordination compound.
Crystals 08 00144 g003
Crystals 08 00144 g004 550
Figure 4. Graph set assignments for the Co(II) coordination compound.
Figure 4. Graph set assignments for the Co(II) coordination compound.
Crystals 08 00144 g004
Crystals 08 00144 g005 550
Figure 5. View of the 2D layered structure of the Co(II) coordination compound.
Figure 5. View of the 2D layered structure of the Co(II) coordination compound.
Crystals 08 00144 g005
Crystals 08 00144 g006 550
Figure 6. UV–vis spectra of H4L and its Co(II) coordination compound in CH2Cl2 (1 ×10−6M).
Figure 6. UV–vis spectra of H4L and its Co(II) coordination compound in CH2Cl2 (1 ×10−6M).
Crystals 08 00144 g006
Crystals 08 00144 g007 550
Figure 7. Fluorescence spectra of H4L and its Co(II) coordination compound in dilute CH2Cl2 solutions (c = 1 ×10−6M, λex = 271 nm).
Figure 7. Fluorescence spectra of H4L and its Co(II) coordination compound in dilute CH2Cl2 solutions (c = 1 ×10−6M, λex = 271 nm).
Crystals 08 00144 g007
Crystals 08 00144 g008 550
Figure 8. Fluorescence spectra of the ligand H4L and its Co(II) coordination compound in the solid state.
Figure 8. Fluorescence spectra of the ligand H4L and its Co(II) coordination compound in the solid state.
Crystals 08 00144 g008
Table
Table 1. Crystallographic and structural refinement data for the Co(II) coordination compound.
Table 1. Crystallographic and structural refinement data for the Co(II) coordination compound.
Molecular formulaC50H72Co6N4O28
Molecular weight/g·mol–11530.63
ColorLight-brown
HabitBlock-shaped
Crystal size (mm)0.21 × 0.23 × 0.31
Crystal systemMonoclinic
Space groupC2/c
Unit cell dimension
a (Å)17.9738(8)
b (Å)15.0717(8)
c (Å)24.5022(14)
α (°)90
β (°)102.627(5)
γ (°)90
V (Å3)6477.0(6)
Z4
Dc(g·cm–3)1.570
μ(mm–1)1.585
F(000)3144
θ range for data collection (°)3.2–26.0
Index ranges−22 ≤ h ≤ 22, −18 ≤ k ≤ 18, −29 ≤ l ≤ 30
Reflections collected14,114
Completeness to θ = 25.00 (%)99.7
Data/restraints/parameters6381/0/415
Final Rindices(I > 2σ(I))R1 = 0.0504, wR2 = 0.1227
R indices(all data)R1 = 0.0694, wR2 = 0.1111
Largest diff. peak and hole (e·Å–3)0.51 and −0.43
Table
Table 2. Selected bond lengths (Å) and angles (°) for the Co(II) coordination compound.
Table 2. Selected bond lengths (Å) and angles (°) for the Co(II) coordination compound.
BondDist.BondDist.BondDist.
Co2–O12.117(3)Co3–O62.061(2)Co1–O12.019(3)
Co2–O22.141(3)Co3–O6#12.089(3)Co1–O52.025(2)
Co2–O52.029(2)Co3–O72.150(2)Co1–O82.112(3)
Co2–O62.067(3)Co3–O112.208(3)Co1–O92.214(3)
Co2–O72.073(2)Co3–O122.116(3)Co1–N182.165(3)
Co2–O7#12.209(2)Co3–O132.041(3)Co1–N252.113(4)
Co3–Co3#12.9071(10)Co3–C182.511(4)Co3#1–O62.089(3)
Co2#1–O72.209(2)
BondAnglesBondAnglesBondAngles
O1–Co2–O290.80(11)O11–Co3–C1830.08(12)Co3–O6–Co2101.80(10)
O1–Co2–O7#1153.79(9)O12–Co3–Co3#1146.40(9)Co3–O6–Co3#188.94(11)
O2–Co2–O7#188.85(10)O13–Co3–O691.72(11)C20–O6–Co2121.2(3)
O5–Co2–O176.15(10)O13–Co3–O6#193.82(14)C20–O6–Co3122.4(2)
O5–Co2–O286.34(10)O13–Co3–O7170.00(10)C20–O6–Co3#1115.2(3)
O5–Co2–O6101.62(10)O13–Co3–O1192.80(13)Co2–O7–Co2#192.10(9)
O5–Co2–O7#177.67(9)O13–Co3–O1298.46(11)Co2–O7–Co398.68(9)
O5–Co2–O7163.15(10)O13–Co3–C1897.74(13)Co3–O7–Co2#194.82(9)
O6–Co2–O1102.51(11)C18–Co3–Co3#1176.17(11)C15–O7#1–Co2#1105.67(19)
O6–Co2–O2165.75(10)O1–Co1–O578.47(10)C15–O7–Co2#1133.1(2)
O6–Co2–O780.59(9)O1–Co1–O898.60(14)C15–O7–Co3#1121.9(2)
O6–Co2–O7#181.45(10)O1–Co1–O987.35(11)Co1–O8–H8111(4)
O7–Co2–O1119.97(10)O1–Co1–N18161.07(12)C24–O8–Co1132.9(3)
O7–Co2–O288.43(10)O1–Co1–N2586.34(13)Co1–O9–H998(4)
O7–Co2–O7#186.23(9)O5–Co1–O891.60(11)C23–O9–Co1122.5(3)
O6#1–Co3–Co3#145.14(7)O5–Co1–O990.46(11)C18–O11–Co388.4(3)
O6–Co3–Co3#145.92(8)O5–Co1–N1883.09(11)C18–O12–Co392.5(2)
O6–Co3–O6#187.96(11)O5–Co1–N25164.65(13)C10–O13–Co3126.2(4)
O6–Co3–O7#182.40(10)O8–Co1–O9173.99(13)O4–N18–Co1124.2(2)
O6–Co3–O778.93(9)O8–Co1–N1886.09(14)C10–N18–Co1127.3(3)
O6–Co3–O11#1161.75(10)O8–Co1–N2592.93(14)O3–N25–Co1120.9(3)
O6–Co3–O11108.83(11)N18–Co1–O988.55(13)C7–N25–Co1128.9(3)
O6–Co3–O12#1101.92(11)N25–Co1–O986.53(14)Co1–O5–Co2103.33(11)
O6–Co3–O12165.23(11)N25–Co1–N18111.85(14)C16–O5–Co2112.6(2)
O6–Co3–C18137.80(13)Co1–O1–Co2100.48(11)C16–O5–Co1132.1(2)
O6–Co3#1–C18131.87(12)C1–O1–Co2128.5(3)Co2–O6–Co3#1101.10(11)
O7–Co3–Co3#190.21(6)C1–O1–Co1129.0(2)O12–Co3–O791.39(10)
O7–Co3–O1193.59(11)C21–O2–Co2128.6(3)O12–Co3–O1160.23(11)
O7–Co3–C1891.63(12)O12–Co3–O791.39(10)O12–Co3–O1160.23(11)
O11–Co3–Co3#1153.05(8)
Symmetry transformations used to generate equivalent atoms: #1‒x+1, ‒y+1, ‒z+1.
Table
Table 3. Putative hydrogen bondings (Å), (°) in the Co(II) coordination compound.
Table 3. Putative hydrogen bondings (Å), (°) in the Co(II) coordination compound.
D–H···Ad(D–H)d(H···A)d(D···A)∠D–H···ASymmetry Code
C12–H12···O130.932.353.275(5)171−1/2+x,–1/2+y,z
O9–H9···O20.851.772.616(4)171
O10–H10···O110.821.992.759(5)157
O14–H14A···O120.821.902.718(5)175−x,y,1/2 − z
C2–H2···O110.932.463.191(5)135
C8–H8B···O90.972.453.291(6)145
C17–H17C···O30.962.192.543(8)100
Table
Table 4. Major IR bands for H4L and its Co(II) coordination compound(cm−1).
Table 4. Major IR bands for H4L and its Co(II) coordination compound(cm−1).
Compoundν(O–H)ν(C=N)ν(Ar–O)ν(Co–O)ν(Co–N)
H4L337316301260––
Co(II)342115921255463519

Share and Cite

MDPI and ACS Style

Ren, Z.-L.; Wang, F.; Liu, L.-Z.; Jin, B.-X.; Dong, W.-K. Unprecedented Hexanuclear Cobalt(II) Nonsymmetrical Salamo-Based Coordination Compound: Synthesis, Crystal Structure, and Photophysical Properties. Crystals 2018, 8, 144. https://doi.org/10.3390/cryst8040144

AMA Style

Ren Z-L, Wang F, Liu L-Z, Jin B-X, Dong W-K. Unprecedented Hexanuclear Cobalt(II) Nonsymmetrical Salamo-Based Coordination Compound: Synthesis, Crystal Structure, and Photophysical Properties. Crystals. 2018; 8(4):144. https://doi.org/10.3390/cryst8040144

Chicago/Turabian Style

Ren, Zong-Li, Fei Wang, Ling-Zhi Liu, Bo-Xian Jin, and Wen-Kui Dong. 2018. "Unprecedented Hexanuclear Cobalt(II) Nonsymmetrical Salamo-Based Coordination Compound: Synthesis, Crystal Structure, and Photophysical Properties" Crystals 8, no. 4: 144. https://doi.org/10.3390/cryst8040144

APA Style

Ren, Z.-L., Wang, F., Liu, L.-Z., Jin, B.-X., & Dong, W.-K. (2018). Unprecedented Hexanuclear Cobalt(II) Nonsymmetrical Salamo-Based Coordination Compound: Synthesis, Crystal Structure, and Photophysical Properties. Crystals, 8(4), 144. https://doi.org/10.3390/cryst8040144

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