hree Inorganic-organic Composite Polyoxotungstates:Syntheses, Characterization and Structures of [Cu(2,2'-bpy)2]5[α-PW11.5Cu0.5O40]·2H2O,[Co(2,2'-bpy)2(N3)2]4H3[α-PW12O40]·3H2O and [Cu(2,2'-bpy)2(4,4'-bpy)]2[α-GeW12O40]·4H2O

Three new inorganic-organic composite polyoxotungstates [Cu(2,2'- bpy)2]5[α- PW11.5Cu0.5O40]·2H2O 1, [Co(2,2'-bp3)2(N3)2]4H3[α-PW12O40]·3H2O 2 and [Cu(2,2'-bpy)2(4,4'- bpy)]2[α-GeW12O40].4H2O 3 (2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the orthorhombie space group Pna21 with α = 27.847(3), b = 21.597(2), c = 20.1179(19) A, V = 12099(2) A3, Z = 4, GOF= 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1 with a= 12.31150(10), b = 16.1954(4), c = 19.36290(10) A, α = 99.366(11), β=105.168(8),γ = 111.836(8)°, V = 3309.98(9) A3, Z = 1, GOF = 1.024, R = 0.0739 and wR = 0.2216; and 3 crystallizes in the monoclinic space group P21/n with a = 12.858(4), b = 20.943(6), c = 15.598(5) A, β = 102.338(5)°, V = 4103(2) A3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1～3 are that their molecular structures all consist of a saturated a-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.     

Hydrothermal Synthesis, Crystal Structure and Fluorescent Property of a Keggin Polyoxometalate [CuI(2,2''-bipy)2]3[PWⅥ12O40]

A Keggin-type tungstohosphate compound [CuI(2,2'-bipy)2]3[PWVI12O40] 1 (bipy = bipyridine) was prepared by the hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 (C60H48Cu3N12O40PW12) crystallizes in the monoclinic system, space group P21/c with a = 16.9837(10), b = 17.9732(13) c = 27.8701(13)(A), β = 96.1039(10)°, V = 8459.2(9)(A)3, Mr = 4004.89, Z = 4, Dc = 3.145 g/cm3, μ = 17.089 mm-1, F(000) = 7208, S = 1.005, the final R = 0.0469 and wR = 0.0827 for 10807 observed reflections (I > 2σ(I)). Compound 1 consists of one discrete normal Keggin polyanion [PWVI12O40]3- and three isolated coordinated cat- ions [CuI(2,2'-bipy)2]+. Significantly, there exist three crystallographically independent asymmetric reduced copper (I) centers in 1. Furthermore, the compound shows strong photoluminescence property in solid state at room temperature.     

Hydrothermal Synthesis and Crystal Structure of a Keggin Polyoxometalate [CoⅡ(2,2'-bipy)2(H2O)]2[SiWVI12O40]·2H2O

A Keggin-type tungstosilicate compound [CoII(2,2'-bipy)2(H2O)]2[SiWVI12O40]·2H2O1 (bipy = bipyridine) was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 (C4H40Co2N8O44SiW12) crystallizes in the triclinic system, space group P1 with a = 10.4979(6), b = 13.3946(7), c = 13.5756(8) (A°), α= 70.0769(18), β= 68.910(3), y = 74.186(4)°,V =1649.84(16) (A°)3, M, = 3688.95, Z =1, Dc= 3.713 mg.m-3,μ= 21.432 mm-1, F(000) = 1644, S =1.058, the final R = 0.0511 and wR = 0.1023 for 6523 observed reflections (I> 2σ(I)). Compound 1 consists of two coordinated cation fragments [CoII(2,2'-bipy)2(H2O)]2+, one normal Keggin polyanion unit [SiWVI12O40]4- and two lattice water molecules. To be noted, each polyanion unit is linked to two cation fragments by its two surface terminal oxygen atoms and two cobalt atoms of two cation fragments forming an organic-inorganic hybrid unit in 1. Furthermore, the compound shows strong photo-luminescence property in the solid state at room temperature.     

Synthesis, Structure and Characterization of [Cu(2,2''-bpy)2][{Cu(2,2''-bpy)2}2W12O40(H2)]·4H2O

An organic-inorganic compound [Cu(2,2'-bpy)2][{Cu(2,2'-bpy)2}2W12O4o(H2)]·4H2O (Mr = 4048.00) was prepared from the hydrothermal reaction of Na2WO4·2H2O, CuCl2·2H2O,2,2'-bipyridine (2,2'-bpy) and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196(8), b = 20.4212(8), c = 21.8129(9)(A), β=96.992(3)°, V= 8365.0(6) (A)3, Dc= 3.214 g/cm3, Z = 4,μ(MoKα) = 17.269 mm-1 and F(000) = 7324.Of the 119837 total reflections, 17315 were unique (Rint = 0.0489). The final R = 0.0385 and wR =0.0770 for 11142 observed reflections with I ＞ 2σ(I). Single-crystal X-ray diffraction reveals that the structure is composed of [{Cu(2,2'-bpy)2}2W12O40(H2)]2- anions, discrete [Cu(2,2'-bpy)2]2 cations and lattice water molecules, and the anion is made up of a {W12O40(H2)}6- α-Keggin core decorated with two {Cu(2,2'-bpy)2}2 groups through bridging oxygen atoms.     

{(n-Bu4N)2[Mo2O2S6Cu6Br4(4,4'-bipy)3]·0.5H2O}n的合成与晶体结构

Cluster coordination polymer {(n-Bu4N)2[Mo2O2S6Cu6Br4(4,4'-bipy)3]·0.5H2O)}n (4,4'-bipy=4,4'-bipyridine),has been synthesized and characterized by X-ray crystallography. The polymeric anion {[Mo2O2S6Cu6Br4(4,4'-bipy)3]2-}n is composed of secondary building units (SBUs) [MoOS3Cu3], Br atoms and 4,4'-bipy ligands. Two secondary building units [MoOS3Cu3] and a double parallel 4,4'-bipy ligands form an octanuclear rectangular metallamacrocycle with the dimension of 1.13×0.39 nm2, which is further connected by single bridging 4,4'-bipy ligands to form a 1D zigzag structure. Crystal data for compound 1: C62H97N8O2.50S6Br4Cu6Mo2,M=2 079.68, Triclinic, P1, a=0.982 40 (10) nm, b=1.293 70(10) nm, c=1.737 4(2) nm, α=97.810(10)°,β=101.390(10)°,γ=108.520(10)°, V=2.005 1(4) nm3, Z=2, Dc=1.722 g·cm-3, F(000)= 1039,μ (Mo Kα)=4.055 mm-1, the final R=0.040 7, wR2=0.097 2. CCDC: 236407.     

Synthesis,Structure and Characterization of [Cu(2,2′-bpy)_2][{Cu(2,2′-bpy)_2}_2W_(12)O_(40)(H_2)]·4H_2O

An organic-inorganic compound [Cu(2,2′-bpy)2][{Cu(2,2′-bpy)2}2W12O40(H2)]·4H2O (Mr = 4048.00) was prepared from the hydrothermal reaction of Na2WO4·2H2O, CuCl2·2H2O, 2,2′-bipyridine (2,2′-bpy) and H2O at 160 ℃ for 4 days. The compound crystallizes in the monoclinic system, space group P21/n with a = 18.9196(8), b = 20.4212(8), c = 21.8129(9) , β = 96.992(3)°, V = 8365.0(6) 3, Dc = 3.214 g/cm3, Z = 4, μ(MoKα) = 17.269 mm-1 and F(000) = 7324. Of the 119837 total reflections, 17315 were unique (Rint = 0.0489). The final R = 0.0385 and wR = 0.0770 for 11142 observed reflections with I > 2σ(I). Single-crystal X-ray diffraction reveals that the structure is composed of [{Cu(2,2′-bpy)2}2W12O40(H2)]2- anions, discrete [Cu(2,2′-bpy)2]2+ cations and lattice water molecules, and the anion is made up of a {W12O40(H2)}6- α-Keggin core decorated with two {Cu(2,2′-bpy)2}2+ groups through bridging oxygen atoms.     

Hexacyanocobaltate(III) anions as precursors of Co(II)-Ni(II) cyano-bridged multidimensional assemblies: hydrothermal syntheses, crystal and powder X-ray structures, and magnetic properties

Three novel cyanide-bridged heterobimetallic coordination polymers have been synthesized by hydrothermal routes, in superheated water solutions, by using K3[Co(CN)6], NiCl2.6H2O, and alpha-diimine ligands: [Ni(CN)4Co(phen)] (1; phen = 1,10-phenanthroline), [Ni(CN)4Co(2,2'-bipy)] (2; 2,2'-bipy = 2,2'-bipyiridine), and [Ni(CN)4Co(2,2'-bipy)2] (3). The isostructural compounds 1 and 2 contain a two-dimensional network with Co(II) centers octahedrally coordinated by one chelating 2,2'-bipy ligand and four cyanide groups of four distinct [Ni(CN)4]2-, through crystallographically equivalent, bridging units. Compound 3 contains one-dimensional zigzag chains in which the Co(II) ion is coordinated by two chelating 2,2'-bipy ligands and two cyanides from two different [Ni(CN)4]2- units cis to each other. These compounds have been fully characterized by single-crystal or unconventional powder X-ray diffraction analyses and variable-temperature magnetic measurements.     

Hydrothermal Synthesis,Crystal Structure and Characterization of a New Keggin Polyoxometalate {[Ag~I(4,4’-bipy)]_3[PW_(12)O_(40)]}·(4,4’-bipy)

A novel polyoxometalate {[AgI(4,4'-bipy)]3[PW12O40]}·(4,4'-bipy)·4H2O 1 has been synthesized hydrothermally and characterized by elemental analysis, IR and single-crystal X-ray diffraction. The crystal of 1 belongs to the triclinic system, space group P1 with a = 11.3710(17), b = 12.0701(16), c = 13.1061(12) , α = 112.838(3), β = 94.545(6), γ = 99.526(4)°, V = 1614.4(4) 3, Mr = 3825.40, Z = 1, Dc = 3.935, μ = 22.289mm-1, F(000) = 1692, the final R = 0.0507 and wR = 0.1054. X-ray diffraction analysis reveals that the molecular structure of 1 consists of three coordinated cations [AgI(4,4'-bipy)]+, a polyanion unit [PW12O40]3-, and a discrete 4,4′-bipy molecule. Significantly, there exist two crystallographically independent silver(I) centers in 1 and all [AgI(4,4'-bipy)]+ cations are linked with each other to form a one-dimensional Ag-4,4'-bipy polymer chain. The neighboring polymer chains are further interconnected to form a 3D framework by the covalent effect of silver atoms and terminal oxygen atoms of the polyanion. The electrochemical behaviors of 1 have also been studied in detail by cyclic voltammograms.     

Incorporation of a new type of transition metal complex into the thioarsenate anion: syntheses, structures, and properties of two novel compounds [Mn3(2,2'-bipy)3(AsVS4)2]n.nH2O and Mn2(2,2'-bipy)As2IIIS5

The incorporation of [Mn(2,2'-bipy)2]2+ with thioarsenate resulted in the formation of two novel compounds, [Mn3(2,2'-bipy)3(As(V)S4)2]n.nH2O (1) and Mn2(2,2'-bipy)As2(III)S5 (2), in which the main-group chalcogenide framework is incorporated with a [tm(2,2'-bipy)m]n+ complex. Meanwhile, the tetrathioarsenate(V) anion acts as a new mu3-1kappaS:1,2kappaS':2,3kappaS":3kappaS'" ligand in 1, in which all four S atoms of the [As(V)S4]3- anion are coordinating to metal. As a result, the two compounds exhibit semiconducting properties (Eg = 2.18 eV (1) and 1.83 eV (2)) and strong blue photoluminescence, with the emission maximum occurring at about 440 nm. Magnetic measurements show that both compounds have AF ordered states with Néel temperatures of 19 and 24 K for 1 and 2, respectively.     

Hydrothermal Synthesis and Crystal Structure of a Hybrid Compound Based on β-Octamolybdate [Mn(2,2’-bipy)_3]_2[β-Mo_8O_(26)]·4H_2O

1 INTRODUCTION Polyoxometalates (POMs) are one of the most widely used inorganic components due to their at- tractive electronic and molecular properties with va- rious applications in catalysis, medicine, materials science[1～3] and so on. Exploration of transition me- tal complex cations as well as organic component which functions as ligand as building blocks in the construction of metal oxide composite materials is a fruitful strategy[4, 5]. Among the polyoxometalates studied to dat…     

Zero- and One-dimensional Organic-inorganic Hybrid Compounds Based on Monovacant Keggin Polyoxotungstatesa

Two new organic-inorganic hybrid mono-transition-metal-substituted polyoxometalates [Ni(2,2'-bipy)3]3[Ni(H2O)SiW11O39]·11H2O 1 and [Cu(dien)(H2O)][Cu(dien)(H2O)2]2-[CuSiW11O39]·5.5H2O 2 (2,2'-bipy = 2,2'-bipyridine, dien = diethylenetriamine) have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, magnetic properties, and IR spectrum. Crystal data for 1: monoclinic, space group P21/n, a = 17.492(3), b = 33.481(5), c = 20.493(3) A, β = 101.894(3)°, Dc = 2.563 mg/A3, F(000) = 8440,μ = 11.454 mm-1 and Z = 4; and those for 2: monoclinic, space group P21/n, a = 11.114(3), b = 22.803(7), c = 22.468(7) A, β = 97.896(6)°, Dc = 4.036 mg/A3, F(000) = 6140,μ = 23.942 mm-1 and Z = 4. The study on the magnetic susceptibility of 2 demonstrates the presence of ferromagnetic interaction.     

二苯乙醇酸铜配合物的合成、晶体结构、电化学和荧光性质

以二苯乙醇酸为配体合成了1个新的化合物[Cu(2,2′-bipy)(BAA)][Cu(2,2′-bipy)(BAA)(H2O)]2.(H2O)3(BAA=二苯乙醇酸阴离子,2,2′-bipy=2,2′-联吡啶)。该化合物晶体属三斜晶系,空间群P1,晶胞参数:a=1.121 7(5)nm,b=1.360 2(6)nm,c=2.335 2(10)nm,α=99.260(6)°,β=101.223(8)°,γ=94.805(8)°,V=3.425(3)nm3,Dc=1.385 g.cm-3,Z=6,μ(Mo Kα)=0.992 mm-1,F(000)=1 474,最终偏离因子R1=0.0561,wR2=0.1128。在标题化合物的不对称单元中有3个单核铜(Ⅱ)配合物,且3个中心铜(Ⅱ)离子的配位数不完全相同,如Cu(1)离子的配位数是4,而Cu(2)和Cu(3)离子的配位数都是5。本文还测定了标题化合物的电化学性能和荧光性能,结果表明:在电化学过程中配合物的电子转移是准可逆的,电子转移数为2个;配合物在478 nm的光激发下可发射荧光。     

Synthesis, Crystal Structure and Properties of a Europium Complex with 3-Iodobenzoic Acid and 2,2′-Bipyridine

The complex [Eu(3-IBA)3·2,2'-bipy]2 was synthesized from 3-iodobenzoic acid (3-HIBA), 2,2'-bipyridine (2,2'-bipy) and EuCl3·6H2O by hydrothermal synthesis, and its crystal structure was determined by X-ray single-crystal diffraction. It is of triclinic, space group P, with a = 10.958(2), b = 12.311(3), c = 12.556(3) (A), α = 81.549(3), β = 82.404(4), γ = 78.348(3)°, Mr = 1049.15, V = 1631.7(6) (A)3, Z = 1, Dc = 2.135 g/cm3, F(000) = 980, λ(MoKα) = 0.71073 A, μ(MoKα) = 4.804 mm-1, the final R = 0.0329 and wR = 0.0723 for 4640 observed reflections with I ＞ 2σ(I). The Eu(Ⅲ) ion is eight-coordinated and two Eu(Ⅲ) ions are held together by four 3-iodobenzoate groups in the bidentate bridging mode. The complex was characterized by DTA-TG, IR, UV and fluorescence spectra.     

Synthesis, Crystal Structure and Properties of a Europium Complex with 3-Iodobenzoic Acid and 2,2'-Bipyridine

The complex [Eu(3-IBA)3·2,2'-bipy]2 was synthesized from 3-iodobenzoic acid (3-HIBA), 2,2'-bipyridine (2,2'-bipy) and EuCl3·6H2O by hydrothermal synthesis, and its crystal structure was determined by X-ray single-crystal diffraction. It is of triclinic, space group P1, with a = 10.958(2), b = 12.311(3), c = 12.556(3) A, α = 81.549(3), β = 82.404(4), γ = 78.348(3)°, Mr = 1049.15, V = 1631.7(6) 3, Z = 1, Dc = 2.135 g/cm3, F(000) = 980, λ(MoKα) = 0.71073 , μ(MoKα) = 4.804 mm-1, the final R = 0.0329 and wR = 0.0723 for 4640 observed reflections with I > 2σ(I). The Eu(Ⅲ) ion is eight-coordinated and two Eu(Ⅲ) ions are held together by four 3-iodobenzoate groups in the bidentate bridging mode. The complex was characterized by DTA-TG, IR, UV and fluorescence spectra.     

Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co(4,4'-bipy)_2(H_2O)_4]· [Co_2(4,4'-bipy)3O(H_2O)_8]·2TST·2(4,4'-bipy)·4H_2 and [Co(4,4'-bipy)_2(H_2O)_4]DSNT'4,4'-bipy

Two new cobalt(Ⅱ) supramolecular complexes [Co(4,4'-bipy)_2(H_2O) _4]·[Co_2(4,4'-bipy)3-(H_2O) _8]·2TST-2(4,4'-bipy)·4H_2O 1 and [Co(4,4'-bipy) _2(H_2O) _4]DSNT·4,4'-bipy 2 based upon the assembly of Co(Ⅱ), 4,4'-bipyridine (4,4'-bipy) and two new multifunctional organic ligands, 2,4,6-tris(4-sulfophenyl-amino)-1,3,5-triazine (H_3TST) and 2,4-bis(p-sulfanilato)-6-diethylamino-1,3,5-triazine (H_2DSNT), have been prepared by hydrothermal method and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal structure of 1 is of monoclinic, space group P2_(1/n) with α= 13.599(4), b = 18.988(6), c = 22.995(7) A, β = 90.273(6)°, V= 5938(3) A~3, Z = 4, C_(56)H_(59)CO_(1.5)N_(13)O_(17)S_3, M_r = 1370.74, D_c = 1.533 g/cm~3,μ = 0.613 mm~(-1), F(000) = 2842, GOOF = 1.018, the final R = 0.0796 and wR = 0.1498 for 9019 observed reflections with I > 2o(I). The crystal structure of 2 belongs to the monoclinic system, space group C2/c with α = 18.864(6), b = 14.283(5), c = 20.246(7) A, β = 107.799(6)°, V = 5194(3) A~3, Z = 4, C_(49)H_(52)CoN_(12)O_(10)S_2, M_r = 1092.08, D_c = 1.397 g/cm~3, μ= 0.480 mm~(-1), F(000) = 2276, GOOF = 1.059, the final R = 0.0665 and wR = 0.1900 for 4887 observed reflections with I> 2σ(I). The results of X-ray crystal structure analysis revealed that complexes 1 and 2 exhibit layered supramolecular frameworks stabilized by electrostatic interactions, π-π interactions and hydrogen bonds.     

Synthesis and Structure of a Novel Supramolecular Compound [Co(2,2''-bipy)(H2 O)4 ][trans-1,4-chdc] and Separation of Isomer of 1,4-Cyclohexanedicarboxylic Acid

A supramolecular compound, [Co(2,2'-bipy)(H2O)4][trans-1,4-chdc] (compound 1) (2,2'-bipy=2,2'-bipyridine, 1,4-chdcH2=1,4-cyclohexanedicarboxylic acid), was synthesized and characterized by single-crystal X-ray diffraction analysis, IR spectrometry, TG analysis, and elemental analyses. Single-crystal X-ray diffraction analysis revealed that [Co(2,2'-bipy)(H2O)4]2 units and adjacent 1,4-chdc2- formed a single layer by hydrogen bonding and electrostatic interactions along the ac-plane, and two symmetry-related single layers interacted with each other by hydrogen bonding, resulting in a double layer, which further formed a 3-D structure by π-π stacking. The most attractive structural feature of compound 1 is that 1,4-chdc2- possesses only trans-conformation although there are both cis- and trans-conformations in the raw material.     

Hydrothermal Synthesis and Crystal Structure of a New Manganese(Ⅱ) Complex with 2,4-Pyridine-dicarboxylic Acid and 2,2'-Bipyridine Ligands

A new metal-organic complex [Mn_2(PDC)_2(bipy)_2(H_2O)_2] (H_2PDC=2,4-pyridinedicarboxylic acid,bipy=2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,TG and single-crystal X-ray diffraction. The compound crystallizes in triclinic,space group P~(-)1 with α=7.376(3),b=9.990(4),c=11.950(5)(A),α=75.217(5),β=78.052(5),γ=70.655(5)°,V=796.0(5)(A)~3,C_(34)H_(26)Mn_2N_(6O)O_(10),M_r=788.49,D_c= 1.645 g/cm~3,μ(MoKa) = 0.866 mm~(-1),F(000)=235,Z=1,the final R=0.0425 and wR=0.0700 for 1971 observed reflections (Ⅰ > 2σ(Ⅰ)). In the crystal structure,the manganese atom is six-coordinated by two carboxylate oxygen atoms from two different PDC ligands,one aqua ligand,and three nitrogen atoms from 2,2'-bipy and PDC ligands,giving a distorted octahedral geometry. It exhibits a three-dimensional supramolecular network defined by O-H…O hydrogen-bonding interactions.     

Modified polyoxometalates: Hydrothermal syntheses and crystal structures of three novel reduced and capped Keggin derivatives decorated by transition metal complexes

Three novel polyoxometalate derivatives decorated by transition metal complexes have been hydrothermally synthesized. Compound 1 consists of [PMo(VI)(6)Mo(V)(2)V(IV)(8)O(44)[Co (2,2'-bipy)(2)(H(2)O)](4)](3+) polyoxocations and [PMo(VI)(4-)Mo(V)(4)V(IV)(8)O(44)[Co(2,2'-bipy)(2)(H(2)O)](2)](3-) polyoxoanions, which are both built on mixed-metal tetracapped [PMo(8)V(8)O(44)] subunits covalently bonded to four or two [Co(2,2'-bpy)(2)(H(2)O)](2+) clusters via terminal oxo groups of the capping V atoms. Compound 2 is built on [PMo(VI)(8)V(IV)(6)O(42)[Cu(I)(phen)](2)](5-) clusters constructed from mixed-metal bicapped [PMo(VI)(8)V(IV)(6)O(42)](7-) subunits covalently bonded to two [Cu(phen)](+) fragments in the similar way to 1. The structure of 3 is composed of [PMo(VI)(9)Mo(V)(3)O(40)](6-) units capped by two divalent Ni atoms via four bridging oxo groups. The crystal data for these are the following: C(120)H(126)Co(6)Mo(16)N(24)O(103)P(2)V(16) (1), triclinic P1, a = 15.6727(2) A, b = 17.3155(3) A, c = 19.5445(2) A, alpha = 86.1520(1) degrees, beta = 81.2010(1) degrees, gamma = 63.5970(1) degrees, Z = 1; C(120)H(85)Cu(6-)Mo(8)N(20)O(44)PV(6) (2), triclinic P1, a = 14.565(4) A, b = 15.899(3) A, c = 16.246(4) A, alpha = 116.289(2) degrees, beta = 103.084(2) degrees, gamma = 94.796(2) degrees, Z = 1; C(60)H(40)Mo(12)N(10)Ni(3)O(40)P (3), monoclinic P2(1)/c, a = 14.804(3) A, b = 22.137(4) A, c = 25.162(5) A, alpha = 90 degrees, beta = 98.59(3) degrees, gamma = 90 degrees, Z = 4.     

Syntheses and Crystal Structures of Four Cobalt Supramolecular Architectures with Hmtyaa Ligand

Four cobalt supramolecular architectures with Hmtyaa(2-(5-methyl-1,3,4-thiadiazol-2-ylthio)acetic acid) ligand have been synthesized.[Co(mtyaa)2(H2O)4]·4(H2O)(1):triclinic,space group P1 with a = 6.7537(18),b = 8.591(2),c = 10.615(3) ,α = 96.495(4),β = 99.955(5),γ = 103.615(5)°,V = 581.9(3) 3,Z = 1,Mr = 581.52,Dc = 1.659 g/m3,μ = 1.158 mm-1,F(000) = 301,Rint = 0.0557,R = 0.0377 and wR = 0.1056 for 1854 observed reflections with Ⅰ 2σ(Ⅰ);{[Co(4,4'-bipy)(H2O)4]·2(mtyaa)·2(H2O)}n(2):triclinic,space group P1 with a = 7.669(2),b = 8.840(3),c = 11.521(4) ,α = 79.912(5),β = 73.954(5),γ = 86.612(6)°,V = 738.9(4) 3,Z = 1,Mr = 701.67,Dc = 1.577 g/m3,μ = 0.924 mm-1,F(000) = 363,Rint = 0.0636,R = 0.0498 and wR = 0.1311 for 2155 observed reflections with Ⅰ 2σ(Ⅰ);{[Co(4,4'-bipy)(mtyaa)(H2O)3](mtyaa)·2(H2O)}(3):monoclinic,space group Pc with a = 7.7832(17),b = 11.527(3),c = 31.483(7) ,β = 91.952(4)°,V = 2822.9(11) 3,Z = 4,Mr = 683.65,Dc = 1.609 g/m3,μ = 0.963 mm-1,F(000) = 1412,Rint = 0.0758,R = 0.0609 and wR = 0.1095 for 5841 observed reflections with I 2σ(I);{[Co(bpe)(mtyaa)2(H2O)2]}n(4):monoclinic,space group C2/c with a = 19.290(11),b = 12.027(7),c = 14.865(8) ,β = 125.648(8)°,V = 2802(3)3,Z = 4,Mr = 657.66,Dc = 1.559 g/m3,μ = 0.959 mm-1,F(000) = 1356,Rint = 0.0456,R = 0.0332 and wR = 0.0985 for 2299 observed reflections with Ⅰ 2σ(Ⅰ).     

Hydrothermal Synthesis and Crystal Structure of a Polyoxometalate- based Complex [Cu^I（phen）2]4（SiW12O40）

A new hybrid polyoxometalate-based complex, [Cu^I（phen）214（SiW12O40） （phen = 1,10-phenanthroline）, has been synthesized by hydrothermal method and characterized with the aid of elemental analysis, IR, UV spectra and thermal analysis studies. The result of X-ray crystallography analysis exhibits that the title compound crystallizes in the orthorhombic space group P212121, and the formula is C96H64N16Cu4SiW12O40. Crystal data： a = 18.3574（14）, b = 21.1952（16）, c = 27.992（2）A, Mr = 4570.08, V = 10891.4（14）A^3, Z = 4, Dc = 2.787 g/cm^3,μ = 13.478 mm^-1, R = 0.0364, wR = 0.0638 （I 〉 2σ（I）） and F（000） = 8360. The complex consists of one α-Keggin anion [SIW12O40]^4- and four discrete [Cu^I（phen）2]^＋ cations. The valence sum calculations for the Cu atoms suggest that all four Cu atoms are in the ＋1 oxidation state.