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1.
A new cobalt(II) cyanato complex, [Co(NCO)2(H2O)2(hmt)] (I) where hmt is hexamethylenetetramine, has been synthesized and structurally characterized. The electronic spectra of the solid compound suggest octahedral cobalt and IR spectra revealed monodentate N-cyanato groups and aqua ligands, while hmt is a bridging N, N′-bidentate leading to a 1-D infinite polymeric chain. The structure has been confirmed from single crystal X-ray diffraction. Crystal data for I : Fw 319.20, a = 9.234(2), b = 11.252(2), c = 12.576(3) Å, β = 107.75(3)°, V = 1244.5(4) Å3, Z = 4, T = 100 K. Crystal system : monoclinic, space group : C2/c. Hydrogen bonds of the type O–H ··· O and O–H ··· N between aqua molecules and O atom of the terminal N-cyanato groups or an N atom of hmt ligands consolidate and extend the structure to a 3-D network. The thermal properties of I are reported.  相似文献   

2.
A cobalt(II) coordination polymer [Co(4-TZBA2?)(H2O)2] (1) was obtained by treatment of Co(ClO4)2 · 6H2O with 4-(1H-tetrazol-5-yl)benzoic acid [H2(4-TZBA)] under hydrothermal conditions. The X-ray single crystal diffraction analysis reveals that 1 crystallizes in monoclinic P21/c, with a = 10.503(2) Å, b = 9.0860(18) Å, c = 10.179(2) Å, β = 96.75(3)° and Z = 4. In 1, adjacent cobalt(II) atoms are bridged by two 4-TZBA2? ligands to form a dimer, which is linked with six dimers to result in a 3-D structure. 1 exhibits strong luminescence at room temperature in the solid state.  相似文献   

3.
The three‐dimensional (3D) porous cobalt(II) metal‐organic framework (MOF), [Co3(L)2(DMA)2(MeOH)2 · 4(DMA) · 6(MeOH)]n ( 1 ) [L = fully deprotonated 2,7‐bis(4‐benzoic acid)‐N‐(4‐benzoic acid) carbazole, DMA = N,N‐dimethylacetamide], was synthesized by hydrothermal reaction. Based on X‐ray single‐crystal diffraction, structural analysis indicates that complex 1 crystallizes in the monoclinic C2/c space group. Complex 1 possesses a 3,6‐connected three‐dimensional (3D) topological structure with a point symbol of {42 · 6}2{44 · 62 · 87 · 102} when a trinuclear CoII cluster was regarded as 6‐connected node and the organic ligands could be regarded as 3‐connected linkers between the 6‐connected nodes. The framework structure exhibits a one‐dimension (1D) channel with an accessible void of 4223.0 Å3, amounting to 42.8 % of the total unit‐cell volume (9862.0 Å3). Moreover, the magnetic properties of complex 1 were studied.  相似文献   

4.
A cobalt(II) compound, [Co4(L)2(OH)2(phen)2(H2O)4] · 6H2O (1), and a copper(II) compound, [Cu2(L)2(H2O)2][Cu(H2O)6] · 6H2O (2) [where H3L is 2-hydroxy-3-[(2-sulfoethylimino)-methyl]-benzoic acid and phen is O-phenanthroline], were prepared and characterized. The tetranuclear cobalt complex 1, C44H62N6O28S2Co4, crystallizes in the monoclinic space group P21/c, with a = 11.847(10) Å, b = 19.061(15) Å, c = 12.635(10) Å, β = 105.483(9)°, and Z = 2; R 1 for 4821 observed reflections [I > 2σ(I)] was 0.0679. Complex 1 is a centrosymmetric tetranuclear cobalt complex with all cobalts having distorted octahedral geometry. The molecule can be viewed as two planar [Co2(OH)(L)(Phen)H2O] units tied together by two terminal water molecules. The framework of 1 has the appearance of two connected face-sharing cubes, each with one vertex missing. The trinuclear copper complex 2, C20H44Cu3N2O26S2, crystallizes in the triclinic space group P1, with a = 7.524(1) Å, b = 7.902(2) Å, c = 16.885(4) Å, α = 88.993(6)°, β = 80.725(7)°, γ = 66.725(4)° and Z = 1; R 1 for 4298 observed reflections [I > 2σ (I)] was 0.0360. Complex 2 is an ionic compound, in which the three Cu(II) centers have two coordination modes. The molecule has a centrosymmetric dinuclear copper coordinated anion and a hexa-aqua-copper cation. The sulfonic acid group has less coordination ability than carboxylate oxygen.  相似文献   

5.
New Co(II), Ni(II), and Cu(II) complexes with 4-(3-hydroxyphenyl)-1,2,4-triazole (L) with the compositions [Co3L6(H2O)5(C2H5OH)](NO3)6 · 2H2O · C2H5OH (I), [Ni3L6(H2O)6](NO3)6 · 2H2O (II), and [M3L6(H2O)6](ClO4)6 · nH2O (M = Co2+, n = 2 (III); Ni2+, n = 2 (IV); Cu2+, n = 0 (V)) are synthesized. The complexes are studied by X-ray structure analysis, X-ray diffraction analysis, UV and IR spectroscopy, and the statistical magnetic susceptibility method. All compounds have the linear trinuclear structure. Ligand L is coordinated to the metal ions by the N(1) and N(2) atoms of the heterocycle according to the bidentate bridging mode. In all compounds the coordination polyhedron of the metal atom is a distorted octahedron. The molecular and crystal structures of compound I, [Co3L6(H2O)6](ClO4)6 · 8C2H5OH (IIIa), and [Ni3L6(H2O)6](ClO4)6 · 8C2H5OH (IVa) are determined.  相似文献   

6.
7.
Coordination polymers, {[Cd(2-mBIM)3](ClO4)2} n (1) and [Cd(BIM)2(NO3)2] n (2), have been prepared from the reaction of bis(2-methylimidazol-1-yl)methane(2-mBIM) with Cd(ClO4)2 and bis(imidazol-1-yl)methane (BIM) with Cd(NO3)2 in ethanol and water, respectively. Their structures were characterized by single crystal X-ray diffraction and IR spectroscopy. Compound 1 crystallizes in the rhombohedral space group R-3c with a = b = 12.3617(5) Å, c = 38.896(3) Å, γ = 120°, V = 5147.5(5) Å3, z = 6. The CdII occupies a crystallographic inversion center and is coordinated by six N atoms from six distinct 2-mBIM ligands to form a slightly distorted octahedral geometry. Each 2-mBIM is coordinated to two CdII cations, linking alternatively four CdII cations, resulting in a 32-membered M4L4 macrometallacycle. Compound 2 crystallizes in the monoclinic space group C2/m with a = 14.400(3) Å, b = 9.3894(18) Å, c = 8.6926(17) Å, β = 123.499(2)°, V = 980.1(3) Å3, z = 2. The Cd coordinates to four nitrogen atoms from four different BIM and two nitrates to form a slightly distorted octahedral geometry. The BIM ligands bridge to form a 1-D infinite double-bridged chain structure with 16-membered M2L2 macrometallacyclic structural units.  相似文献   

8.
The heterovalent trinuclear cobalt complexes [Co2IIIL4 i · CoII(H2O)4] · nXmY (L i are deprotonated Schiff bases derived from substituted salicylaldehydes and β-alanine; i = 1–3) were obtained and characterized. An X-ray diffraction study of the trinuclear cobalt complex with N-(2-carboxyethyl)salicylaldimine showed that the central Co(II) ion and the terminal Co(III) ions are linked by bridging carboxylate groups. Either terminal Co(III) atom is coordinated to two ligand molecules. They form an octahedral environment consisting of two azomethine N atoms, two phenolate O atoms, and two O atoms of two carboxylate groups. The central Co(II) atom is coordinated to four water molecules and to two O atoms of two bridging carboxylate ligands involved in the coordination sphere of the terminal Co(III) atoms.  相似文献   

9.
Reactions of fresh M(OH)2 (M = Zn2+, Cd2+) precipitate and (RS)-2-methylglutaric acid (H2MGL), 2,2′-bipyridine (bipy), or 1,10-phenanthroline (phen) in aqueous solution at 50°C afforded four new metal–organic complexes [Zn2(bipy)2(H2O)2(MGL)2] (1), [Zn2(phen)2(H2O)(MGL)2] (2), [Cd(bipy)(H2O)(MGL)] · 3H2O (3), and [Cd(phen)(H2O)(MGL)] · 2H2O (4), which were characterized by single crystal X-ray diffraction, IR spectra, TG/DTA analysis as well as fluorescence spectra. In 1, the [Zn(bipy)(H2O)]2+ moieties are linked by R- and S-2-methylglutarate anions to build up the centrosymmetric dinuclear [Zn2(bipy)2(H2O)2(MGL)2] molecules. In 2, the 1-D ribbon-like chains [Zn2(phen)2(H2O)(MGL)2] n can be visualized as from centrosymmetric dinuclear [Zn2(phen)2(H2O)2(MGL)2] units sharing common aqua ligands. Both 3 and 4 exhibit 1-D chains resulting from [Cd(bipy)(H2O)]2+ and [Cd(phen)(H2O)]2+, respectively, bridged alternately by R- and S-2-methylglutarate anions in bis-chelating fashion. The intermolecular and interchain π···π stacking interactions form supramolecular assemblies in 1 and 1-D chains in 24 into 2-D layers. The hydrogen bonded lattice H2O molecules are sandwiched between 2-D layers in 3 and 4. Fluorescence spectra of 14 exhibit LLCT π → π* transitions.  相似文献   

10.
The syntheses of homo‐ and heteropentanuclear coordination compounds with the molecular formulae [MZn4(L)4(L′)6] (M = CoII or Zn; L = chloride or acac; L′ = 1,2,3‐benzotriazolate) are reported. These compounds display a highly symmetric coordination unit consisting of a central metal ion (M = CoII or Zn) which is octahedrally coordinated by 6 tridentate benzotriazolate‐type ligands via their N(2) donor atom. The benzotriazolate ligands span the edges of an imaginary tetrahedron thus providing four coordination sites at the corners of the tetrahedron, which are then filled by four zinc ions. The coordination shell of the latter are completed by bidentate acetylacetonate (acac) ligands or by chloride anions, respectively. The solid state structures of two homopentanuclear metal complexes, namely [Zn5(acac)4(bta)6]·4C6H12 ( 1 ) (acacH = acetylacetone; btaH = 1,2,3‐benzotriazole), and [Zn5Cl4(Me2bta)6]·2DMF ( 2 ) (Me2btaH = 5,6‐dimethyl‐1,2,3‐benzotriazole) were determined by single crystal X‐ray structure analysis. The heteropentanuclear metal complex [CoIIZn4Cl4(Me2bta)6]·2DMF ( 3 ) is isostructural with compound 2 . Compound 1 was synthesized from stoichiometric amounts of Zn(acac)2 and btaH employing dichloromethane as solvent. The synthesis of compound 2 requires addition of an auxiliary base to the DMF solution of anhydrous ZnCl2 and Me2btaH. For compound 3 a stoichiometric ratio of Co(NO3)2·6H2O, anhydrous ZnCl2 and Me2btaH was employed during synthesis. Phase purity of all compounds was proved by X‐ray powder diffraction (XRPD) analysis, IR spectroscopy, and elemental analysis. Crystal data: for 1 (C80H100N18O8Zn5): monoclinic, space group P21/c with a = 23.781(5) Å, b = 16.000(3) Å, c = 25.170(5) Å, β = 115.29(3)°, V = 8659(3) Å3, Z = 4, ρ = 1.357 g cm?3. For 2 (C54H62Cl4N20O2Zn5): cubic, space group with a = 23.367(3) Å, V = 12759(3) Å3, Z = 8, ρ = 1.553 g cm?3. For 3 (C54H62Cl4CoN20O2Zn4): cubic, space group with a = 23.443(3) Å, V = 12884(3) Å3, Z = 8, ρ = 1.532 g cm?3.  相似文献   

11.
12.
The title compound, [Co(C7H6NO2)2(H2O)4]·4H2O, contains a CoII ion lying on a crystallographic inversion centre. The CoII ion is octahedrally coordinated by two 6‐methylpyridine‐3‐carboxylate ligands in axial positions [Co—O = 2.0621 (9) Å] and by four water molecules in the equatorial plane [Co—O = 2.1169 (9) and 2.1223 (11) Å]. There are also four uncoordinated water molecules. The 6‐methylpyridine‐3‐carboxylate ligands are bound to the CoII ion in a monodentate manner through a carboxylate O atom. There is one strong intramolecular O—H...O hydrogen bond, and six strong intermolecular hydrogen bonds of type O—H...O and one of type O—H...N in the packing, resulting in a complex three‐dimensional supramolecular structure.  相似文献   

13.
One binuclear complex [Co(bpm*)2(dca)]2(ClO4)2 ( 1 ) and two 1D chain CoII complexes, {[Co(bpm)2(dca)](ClO4)}n ( 2 ) and [Co(dmf)2(dca)2]n ( 3 ), (bpm*: bis[(3, 5‐dimethyl)pyrazolyl]methane; bpm: bis(pyrazolyl)methane; dca: dicyanamide; dmf: N, N‐dimethyl formamide) have been prepared and structurally characterized. The cobalt atoms are hexa‐coordinated forming a slightly distorted octahedral coordination. Compound 1 crystallizes in the monoclinic system, space group P21/c, a = 9.849(3)Å, b = 21.944(7)Å, c = 13.814(5)Å, β = 94.824(6), Z = 4, R1 = 0.0672, wR2 = 0.1395. 1 is a binuclear complex linked by two dca ligands, and each CoII ion is coordinated by two terminal bpm* ligands. Compound 2 crystallizes in the orthorhombic system, space group Cmcm, a = 10.377(4)Å, b = 13.594(5)Å, c = 15.999(6)Å, Z = 4, R1 = 0.0609, wR2 = 0.1328. The structure of 2 can be described as a one‐dimensional zigzag chain of CoII ions bridged by one dca ligand. Each CoII ion in the chain is coordinated by two bpm ligands. Compound 3 crystallizes in the monoclinic system, space group C2, a = 13.559(15)Å, b = 7.393(8)Å, c = 8.110(9)Å, β = 112.228(15), Z = 2, R1 = 0.0260, wR2 = 0.0760. 3 has a one‐dimensional linear chain of CoII ions bridged by two dca ligands, in which each CoII ion is coordinated with two dmf molecules.  相似文献   

14.
New hexanuclear complexes of lanthanum and neodymium iodides, [La6(H2O)23(OH)10]I8 · 8H2O (I) and [Nd6(H2O)23(OH)10]I8 · 8H2O (II), are synthesized and studied by X-ray diffraction analysis. The isostructural crystals of complexes I and II are orthorhombic: a = 13.197(4) Å, b = 15.152(3) Å, c = 15.302(4) Å and a = 13.060(4) Å, b = 14.967(5) Å, c = 15.098(4) Å, respectively; Z = 2, space group Pnnm. The lanthanum (neodymium) atoms coordinate the aqua and hydroxo ligands and enter the composition of the Ln6 -containing complex cations. The coordination polyhedron (ignoring the central oxygen atom) of each atom of the complexing agent is somewhat distorted square antiprism with the aqua and hydroxo ligands being in the vertices. Four bridging ligands link this atom of the complexing agent with the four adjacent atoms.  相似文献   

15.
Reactions of Zn(II) salts, 5-(4-(1H-imidazol-1-yl)phenyl)-1H-tetrazolate (HIPT) and 2-mercaptobenzoic acid or 2-propyl-1H-imidazole-4,5-dicarboxylic acid (H3PrIDC), result in two mixed-ligand coordination polymers (CPs), [Zn2(IPT)(DSDB)(OH)]n (H2DSDB = 2,2′-disulfanediyldibenzoic acid, 1) and [Zn2(IPT)(PrIDC)(H2O)]n (H3PrIDC = 2-propyl-1H-imidazole-4,5-dicarboxylic acid, 2). Compound 1 possesses a 2-D structure built by 1-D [Zn(IPT)]n chains and DSDB2? connectors, in which the DSDB2? is generated via in situ reaction from 2-mercaptobenzoic acid. It displays a new intricate 4-nodal {3·4·6·7·8·9}{3·6·7·8·9·10}{3·8·9}{4·6·8} topology. Compound 2 displays a 3-D framework with new 3-connected topology with Schläfli symbol of (4·8·10) (8·122), in which the 1-D Zn-carboxylate chains were bridged by 3-connected IPT? ligands. The thermal stabilities and luminescence properties of 1 and 2 have also been studied. The compounds exhibit intense solid-state fluorescent emissions at room temperature.  相似文献   

16.
A new coordination polymer, [Co2(μ-H2O)(4,3-pybz)4] n (1), has been hydrothermally synthesized from Co(NO3)2 · 6H2O and an unsymmetrical 4-pyridin-3-yl-benzoic acid (4,3-Hpybz), which is characterized by IR, elemental analysis, thermogravimetric analysis, and single crystal X-ray diffraction. This compound crystallizes in monoclinic, space group C2/c with a = 11.876(3) Å, b = 15.462(3) Å, c = 21.545(4) Å, β = 94.873(5)°, V = 3942.0(15) Å3, Z = 4, Dc = 1.565 g cm?3, F(000) = 1904, GOF = 1.025, μ = 0.910 mm?1, R 1 = 0.0456, wR 2 = 0.0983. Compound 1 shows a 3-D (3,6)-connected coordination framework with (3.4.5)(32.44.55.62.72) topology, in which cobalt is a six-connected node, and the 4,3-Hpybz ligands serve as two-connected spacers and three-connected nodes. In addition, the magnetic and thermal properties of 1 have also been investigated.  相似文献   

17.
In the isostructural title complexes, [M(C9H6N3O2)2(H2O)2] [M = CoII, (I), CdII, (II), and CuII, (III); the metal centres reside on a twofold axis in the space group C2/c for (I) and (II)], the metal centres are surrounded by four O atoms from two O,O′‐bidentate carboxyl­ate groups and by two trans‐coordinated aqua ligands, forming a distorted octa­hedral environment. The mol­ecules possess four hydrogen‐bond donor (two aqua ligands) and four hydrogen‐bond acceptor sites (two triazole groups), and aggregate by self‐association, forming two‐dimensional hydrogen‐bonded frameworks [via O—H⋯N inter­actions; O⋯N = 2.749 (3)–2.872 (3) Å]. The layers are parallel and are tightly packed with short inter­layer distances of 4.93, 4.95 and 5.01 Å for (I), (II) and (III), respectively.  相似文献   

18.
A new mononuclear complex Mn(bbbi)2(H2O)4(ClO4)2·(bbbi)2·(H2O)2 1 (bbbi = 1,4-bis(benzimidazol-1-yl)-2-butene) is synthesized under hydrothermal conditions and characterized by IR spectroscopy, elemental analysis, and single crystal X-ray structural analysis. Crystal data for 1: triclinic, , a = 8.8478(7) ?, b = 15.0550(11) ?, c = 16.4310(12) ?, α = 108.657(7)°, β = 104.044(7)°, Γ = 99.317(7)°, V = 1942.2(3) ?3, Z = 1, final R = 0.0621. Each manganese atom is octahedrally coordinated by four aqua ligands and two nitrogen atoms of two distinct bbbi ligands. The molecule is stabilized by hydrogen bonding and π…π interactions.  相似文献   

19.
Four CuII and CoII complexes–[Cu(L1)Cl2(H2O)]3/2H2O · 1/2EtOH, [Cu(L1)2Cl2]6H2O, [Co(L1)Cl2]3H2O · EtOH, and [Co2(L1)(H2O)Cl4]1.5H2O · EtOH (L1 = 2,4,6-tri(2-pyridyl)-1,3,5-triazine; TPT)–were synthesized by conventional chemical method and used to synthesize another four metal complexes–[Cu(L1)I2(H2O)]6H2O, [Cu(L1)2I2]6H2O, [Co(L1)I(H2O)2]I · 2H2O, and [Co2(L1)I4(H2O)3]–using tribochemical reaction, by grinding it with KI. Substitution of chloride by iodide occurred, but no reduction for CuII or oxidation of CoII. Oxidation of CoII to CoIII complexes was only observed on the dissolution of CoII complexes in d6-DMSO in air while warming. The isolated solid complexes (CuII and CoII) have been characterized by elemental analyses, conductivities, spectral (IR, UV-Vis, 1H-NMR), thermal measurements (TGA), and magnetic measurements. The values of molar conductivities suggest non-electrolytes in DMF. The metal complexes are paramagnetic. IR spectra indicate that TPT is tridentate coordinating via the two pyridyl nitrogens and one triazine nitrogen forming two five-membered rings around the metal in M : L complexes and bidentate via one triazine nitrogen and one pyridyl nitrogen in ML2 complexes. In binuclear complexes, L is tridentate toward one CoII and bidentate toward the second CoII in [Co2(L1)Cl4]2.5H2O · EtOH and [Co2(L1)I4(H2O)3]. Electronic spectra and magnetic measurements suggest a distorted-octahedral around CuII and high-spin octahedral and square-pyramidal geometry around CoII.  相似文献   

20.
Two new coordination polymers, [M(sac)2(μ–pyz)(H2O)2] n [M=ZnII(1), CdII(2), pyz =?pyrazine, and sac =?saccharinate], have been prepared and characterized by elemental analysis, FTIR spectroscopy, thermal analysis and single crystal X-ray diffraction. Both complexes are isomorphous and crystallize in the triclinic P 1 space group. The metal(II) ions are octahedrally coordinated by two sac, two aqua and two pyz ligands. The sac ligands are N-coordinated, while the pyz ligands are bridges between the metal centers, leading to one-dimensional linear chains. Intra-chain M–M separations in 1 and 2 are 7.218 and 7.498 Å, respectively. The individual chains are linked by strong OW–H ··· O(sac) hydrogen bonds into two–dimensional layers, which are further assembled into three–dimensional supramolecular networks by aromatic π(sac) ··· π(sac) stackings interactions.  相似文献   

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