Supramolecular Assemblies in Pyridine- and Pyrazole-Based Coordination Compounds of Co(II) and Ni(II): Characterization, Hirshfeld Analysis and Theoretical Studies
Source abstract
Abstract
Two new Ni(II) and Co(II) coordination compounds, viz., [Ni(H2O)5(DMAP)](IPhth)·2H2O (1) and [Co(Hdmpz)4(H2O)2]Cl2 (2) (where DMAP = 4-dimethylaminopyridine, IPhth = Isophthalate, Hdmpz = 3,5-dimethylpyrazole),were synthesized and characterized using elemental analysis, TGA, spectroscopic (FTIR and electronic) and single-crystal X-ray diffraction techniques. Compound 1 crystallizes as a co-crystal hydrate of Ni(II), whereas compound 2 is a mononuclear compound of Co(II). The crystal structure analysis of compound 1 reveals the presence of various non-covalent interactions such as anion–π, π–π, C–H∙∙∙π, C–H∙∙∙C, etc., which stabilize the layered assembly of the compound. In compound 2, enclathration of counter chloride ions within the supramolecular trimeric host cavity plays a crucial role in the stabilization of the compound. The non-covalent interactions observed in the crystal structures were further studied theoretically, focusing on the cooperative π-stacking interactions between the DMAP and IPhth counter-ions in 1. To identify the non-covalent interactions of the compounds, Hirshfeld surfaces and their associated two-dimensional fingerprint regions were analyzed. Theoretical calculations confirm that H-bonding interactions combined with the π-stacking contacts are crucial synthons for the solid-state stability of compound 1.
Source: crossref · Quality: baseline
Research context
OpenAlex topics: Crystal structures of chemical compounds · Crystallography and molecular interactions · Metal-Organic Frameworks: Synthesis and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Chemistry, Cotton University, Assam 781001, India
Department de Química, Universitat de les IllesBalears, Crta de Valldemossa km 7.7, 07122 Palma de Mallorca, Spain
INBIOFAL (CONICET—UNT), Instituto de Química Orgánica, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471, San Miguel de Tucumán T4000CAN, Argentina
Funding
ASTEC, DST, Govt. of Assam · Gobierno de España, Ministerio de Ciencia e Innovacion
References (71)
Show source-provided references
1. Crystal engineering: A holistic view10.1002/anie.200700534 ↗
2. Cobalt(II) coordination polymers assembled from unexplored pyridine-carboxylic acids: Structural diversity and catalytic oxidation of alcohols10.1021/acs.inorgchem.9b00242 ↗
3. Metal and ligand effects on the stability and electronic properties of crystalline two-dimensional metal-benzenehexathiolate coordination compounds10.1088/1361-648X/aae618 ↗
4. Facile synthesis, X-Ray structure of new multi-substituted aryl imidazole ligand, biological screening and DNA binding of its Cr(III), Fe(III) and Cu(II) coordination compounds as potential antibiotic and anticancer drugs10.1016/j.molstruc.2019.127034 ↗
5. Self-assembly of catalytically active supramolecular coordination compounds within metal-organic frameworks10.1021/jacs.9b03914 ↗
6. Bringing 5-(3,4-dicarboxylphenyl)picolinic acid to crystal engineering research: Hydrothermal assembly, structural features and photocatalytic activity of Mn, Ni, Cu, and Zn coordination polymers10.1039/C7CE02009K ↗
7. A survey of co-crystals reported prior to 200010.1021/cg900873t ↗
8. Spectroscopic, structural, DFT and molecular docking studies on novel cocrystal salt hydrate of chromotropic acid and its antibiofilm activity10.1007/s13369-020-04822-x ↗
9. Recent progress in coordination chemistry, photo-physical properties, and applications of pyridine-based Cu(I) complexes10.1080/00958972.2018.1509070 ↗
10. Self-healing polymeric hydrogel formed by metal-ligand coordination assembly: Design, fabrication, and biomedical applications10.1002/marc.201800837 ↗
11. Mogensen, S.B., Taylor, M.K., and Lee, J. (2020). Homocoupling reactions of azoles and their applications in coordination chemistry. Molecules, 25.10.3390/molecules25245950 ↗
12. Silva, V.L.M., and Silva, A.M.S. (2021). Recent advances in the synthesis, functionalization and applications of pyrazole-type compounds. Molecules, 26.10.3390/molecules26164989 ↗
13. Chemical, physical, and biological properties of Pd(II), V(IV)O, and Ag(I) complexes of N3 tridentate pyridine-based Schiff base ligand10.1080/00958972.2020.1842378 ↗
14. Charge assisted hydrogen bonded assemblies and unconventional O∙∙∙O dichalcogen bonding interactions in pyrazole-based isostructural Ni(II) and Mn(II) compounds involving anthraquinonedisulfonate: Antiproliferative evaluation and theoretical studies10.1016/j.molstruc.2021.131883 ↗
15. Coordination compounds of copper(II) with schiff bases based on aromatic carbonyl compounds and hydrazides of carboxylic acids: Synthesis, structures, and properties10.1134/S1070328420090018 ↗
16. H-Bonded and metal(II)-organic architectures assembled from an unexplored aromatic tricarboxylic acid: Structural variety and functional properties10.1039/D0DT01261K ↗
17. Anti-cancer and anti-inflammatory activities of a new family of coordination compounds based on divalent transition metal ions and indazole-3-carboxylic acid10.1016/j.jinorgbio.2020.111308 ↗
18. Gemifloxacin-transition metal complexes as therapeutic candidates: Antimicrobial, antifungal, anti-enzymatic, and docking studies of newly synthesized complexes10.1016/j.heliyon.2022.e10378 ↗
19. Scheiner, S. (2015). Non-Covalent Forces, Springer.10.1007/978-3-319-14163-3 ↗
20. Maharramov, A.M., Mahmudov, M.T., Kopylovich, M.N., and Pombeiro, A.J.L. (2016). Non-Covalent Interactions in the Synthesis and Design of New Compounds, John Wiley & Sons, Inc.10.1002/9781119113874 ↗
21. Chemistry beyond the molecule10.1038/35086640 ↗
22. Hypervalency, secondary bonding and hydrogen bonding: Siblings under the skin10.1039/C6CS00688D ↗
23. Non-covalent carbon-bonding interactions in proteins10.1002/anie.201811171 ↗
24. Steed, J.W., and Atwood, J.L. (2009). Supramolecular Chemistry, John Wiley & Sons Ltd.. [2nd ed.].10.1002/9780470740880 ↗
25. The Cambridge structural database10.1107/S2052520616003954 ↗
26. Phenanthroline-based Ni(II) coordination compounds involving unconventional discrete fumarate-water-nitrate clusters and energetically significant cooperative ternary π-stacked assemblies: Antiproliferative evaluation and theoretical studies10.1016/j.molstruc.2021.131424 ↗
27. Benzoato bridged dinuclear Mn(II) and Cu(II) compounds involving guest chlorobenzoates and dimeric paddle wheel supramolecular assemblies: Antiproliferative evaluation and theoretical studies10.1016/j.poly.2021.115409 ↗
28. Bruker (2015). APEX3 User Manual, Bruker AXS Inc.
29. Bruker (1999). SADABS, V2.05, Bruker AXS Inc.
30. Crystal structure refinement with SHELXL10.1107/S0108767307043930 ↗
31. WinGX and ORTEP for Windows: An update10.1107/S0021889899006020 ↗
32. Brandenburg, K. (2008). Diamond 3.1f, Crystal Impact GbR.
33. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu10.1063/1.3382344 ↗
34. Accurate Coulomb-fitting basis sets for H to Rn10.1039/b515623h ↗
35. Electronic structure calculations on workstation computers: The program system turbomole10.1016/0009-2614(89)85118-8 ↗
36. NCIPLOT: A program for plotting non-covalent interaction regions10.1021/ct100641a ↗
37. Atoms in molecules10.1021/cr00005a013 ↗
38. Multiwfn: A multifunctional wavefunction analyzer10.1002/jcc.22885 ↗
39. VMD: Visual molecular dynamics10.1016/0263-7855(96)00018-5 ↗
40. Novel tools for visualizing and exploring intermolecular interactions in molecular crystals10.1107/S0108768104020300 ↗
41. Hirshfeld surface analysis10.1039/B818330A ↗
42. Molecular electric moments from X-ray diffraction data10.1021/cr00016a005 ↗
43. CrystalExplorer: A program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals10.1107/S1600576721002910 ↗
44. Synthesis, structure and properties of a fumarate bridged Ni(II) coordination polymer10.1016/j.molstruc.2011.05.039 ↗
45. Supramolecular association in Cu(II) and Co(II) coordination complexes of 3,5-dimethylpyrazole: Experimental and theoretical studies10.1016/j.ica.2018.09.035 ↗
46. Solid and solution structures and DNA binding properties of [MII(4-CNpy)2(SO4)(H2O)3]·H2O for M = Cu, Co, Ni10.1016/j.poly.2011.12.038 ↗
47. Energetically significant cooperative π-stacked ternary assemblies in Ni(II) phenanthroline compounds involving discrete water clusters: Anticancer activities and theoretical studies10.1016/j.molstruc.2020.129486 ↗
48. Supramolecular assemblies involving anion-π and lone pair-π interactions: Experimental observation and theoretical analysis10.1039/c0ce00593b ↗
49. A critical account on π-π stacking in metal complexes with aromatic nitrogen-containing ligands10.1039/b003010o ↗
50. Synthesis and structure of the pyrazolate-bridged cobalt(II) benzoate Co2(μ-dmpz)2(Hdmpz)2(OOCPh)210.1134/S003602361009010X ↗
51. Supramolecular assemblies involving unconventional non-covalent contacts in pyrazole-based coordination compounds of Co(II) and Cu(II) pyridinedicarboxylates: Antiproliferative evaluation and theoretical studies10.1016/j.poly.2022.116025 ↗
52. Coordination complexes of copper(II) with herbicide-trichlorophenoxyacetate: Syntheses, characterization, single crystal X-ray structure and packing analyses of monomeric [Cu(γ-pic)3(2,4,5-trichlorophenoxyacetate)]·H2O, [trans-Cu(en)2(2,4,5-trichlorophenoxyacetate)2]·2H2O and dimeric [Cu2(H2tea)2(2,4,5-trichlorophenoxyacetate)2]·2H2O10.1016/j.ica.2016.12.008 ↗
53. A rare supramolecular assembly involving ion pairs of coordination complexes with a host–guest relationship: Synthesis, crystal structure, photoluminescence and thermal study10.1039/c2ce25916h ↗
54. Synthesis and characterization of a cobalt-2,6-pyridinedicarboxylate MOF with potential application in electrochemical sensing10.1016/j.poly.2017.08.030 ↗
55. Thermochemical study of 4-(dimethylamino)pyridine complexes of some bivalent metal bromides10.1016/j.jct.2013.06.010 ↗
56. 4-Cyanopyridine complexes [MX2(4-CNpy)x]n (with X = Cl, Br and x = 1, 2): Crystal structures, thermal properties and a comparison with [MX2(3-CNpy)x]n complexes10.1039/C9CE02012H ↗
57. Octahedral group 4 metal complexes that contain amine, amido, and aminopyridinato ligands: Synthesis, structure, and application in α-olefin oligo-and polymerization10.1021/ic960182r ↗
58. Structural topology of weak non-covalent interactions in a layered supramolecular coordination solid of zinc involving 3-aminopyridine and benzoate: Experimental and theoretical studies10.1007/s10870-018-0723-5 ↗
59. Constructions of a set of hydrogen-bonded supramolecules from reactions of transition metals with 3,5-dimethylpyrazole and different dicarboxylate ligands10.1016/j.ica.2008.12.022 ↗
60. Synthesis of novel Cl2Co4L6 cluster using 1-hydroxymethyl-3,5-dimethylpyrazole (LH) ligand: Crystal structure, spectral, thermal, Hirschfeld surface analysis and catalytic oxidation evaluation10.1016/j.molstruc.2019.126995 ↗
61. Trans-dichlorotetrakis (1H-pyrazole-κN2) copper(II): Synthesis, crystal structure, hydrogen bonding graph-sets, vibrational and DFT studies10.1016/j.molstruc.2015.03.068 ↗
62. Synthesis and characterization of five new thiocyanato-and cyanato-metal(II) complexes with 4-azidopyridine as co-ligand10.1016/j.poly.2014.08.031 ↗
63. Energetically significant antiparallel π-stacking contacts in Co(II), Ni(II) and Cu(II) coordination solids of pyridine-2,6-dicarboxylates: Antiproliferative evaluation and theoretical studies10.1016/j.ica.2019.119233 ↗
64. Synthesis, and characterization of low- and high-spin manganese(II) complexes of polyfunctionaladipoyldihydrazone: Effect of coordination of N-donor ligands on stereo-redox chemistry10.1016/j.molstruc.2015.02.070 ↗
65. Structures, photoresponse properties and DNA binding abilities of 4-(4-pyridinyl)-2-pyridone salts
66. Synthesis, characterization and density functional calculations on dichloro-bis(4-dimethylaminopyridine) cobalt(II) complex [Co(II)(C7H10N2)2Cl2]10.1080/00958970701389997 ↗
67. R-Isophthalate (R = –H, –NO2 and –COOH) as modular building blocks for mixed-ligand coordination polymers incorporated with a versatile connector 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole10.1039/B711447H ↗
68. Two Mn(II) chloride complexes containing guest molecules10.1007/s10973-006-7602-6 ↗
69. Bivalent transition metal complexes of coumarin-3-yl thiosemicarbazone derivatives: Spectroscopic, antibacterial activity and thermogravimetric studies10.1016/j.molstruc.2008.10.059 ↗
70. Energetically significant unconventional π-π contacts involving fumarate in a novel coordination polymer of Zn(II): In-vitro anticancer evaluation and theoretical studies10.1016/j.ica.2019.04.047 ↗
71. Intermolecular hydrogen bond energies in crystals evaluated using electron density properties: DFT computations with periodic boundary conditions10.1002/jcc.23062 ↗