Synthesis and Crystal Structure of [Cu3(dmpzm)4(μ-1,3-dca)2(dca)4]·2H2O (dmpzm = 1,1·-Methylenebis-(3,5-dimethyl-1H-pyrazole), dca = dicyanamide)

The title compound, [Cu3(dmpzm)4(μ-1,3-dca)2(dca)4]·2H2O (dmpzm = 1,1'-methyle- nebis(3,5-dimethyl-1H-pyrazole), dca = dicyanamide) 1·2H2O, was synthesized via the reaction of CuCl2·2H2O with dmpzm and Na(dca), and characterized by elemental analysis and IR spectra. 1·2H2O crystallizes in the monoclinic system, space group C2/m with a = 13.578(3), b = 16.769(3), c = 14.769(3)(A),β=104.10(3)°, V = 3261.4(11)(A)3, Z = 2, Dc = 1.466 g/cm3, T = 153(2) K, C56H68N34O2Cu3, Mr = 1440.09, F(000) = 1490, μ(MoKα) = 1.040 mm(1, S = 1.150, R = 0.0553 and wR = 0.1123 for 2744 observed reflections with I > 2σ(I). The central copper atom is chelated by two dmpzm ligands and coordinated by two bridging dca anions, forming a slightly distorted octahedral geometry. The two external copper atoms adopt a square-pyramidal coordination geometry, coor- dinated by one chelating dmpzm ligand and one bridging and two terminal dca anions. Two inter- molecular hydrogen bonding interactions result in the formation of a 2D (4,4) hydrogen-bonded network.     

Synthesis and Crystal Structure of [Cu3（dmpzm）4（μ-1, 3-dca）2（dca）4]·2H2O （dmpzm = 1,1＇-Methylenebis- （3,5-dimethyl-1H-pyrazole）, dca = dicyanamide）

The title compound, [Cu3（dmpzm）4（μ-1,3-dca）2（dca）4]·2H2O （dmpzm = 1,1＇-methylenebis（3,5-dimethyl-lH-pyrazole）, dca = dicyanamide） 1·2H2O, was synthesized via the reaction of CuCl2·2H2O with dmpzm and Na（dca）, and characterized by elemental analysis and IR spectra. 1·2H2O crystallizes in the monoclinic system, space group C2/m with a = 13.578（3）, b = 16.769（3）, c = 14.769（3） A, β = 104.10（3）° V = 3261.4（11） A^3, Z = 2, Dc = 1.466 g/cm^3, T = 153（2） K, C56H68N34O2Cu3, Mr = 1440.09, F（000） = 1490,μ（MoKa） = 1.040 mm^-1, S = 1.150, R = 0.0553 and wR = 0.1123 for 2744 observed reflections with I 〉 2σ（I）. The central copper atom is chelated by two dmpzm ligands and coordinated by two bridging dca anions, forming a slightly distorted octahedral geometry. The two external copper atoms adopt a square-pyramidal coordination geometry, coordinated by one chelating dmpzm ligand and one bridging and two terminal dca anions. Two intermolecular hydrogen bonding interactions result in the formation of a 2D （4,4） hydrogen-bonded network.     

Synthesis and crystal structure of chain [Cu_2I_2(PPh_3)_2(C_4H_5N_3)]∝

The chain [ Cu2I2(PPh3)2(C4H5N3)] has been synthesized and characterized by X-ray crystallography.It crystallizes in the triclinic system,space group P 1,with a=0.9985(2)nm,b=1.0998(2)nm,c=1.5174(2)nm,a=87.89(1),P=76.73(l),7=77.77(1),V=1.5849(5)nm3,Z=2,Bc=2.095g/cm3 [Gu2I2(PPh3)2(Crh5N3)] has a dimmer unit [Cu2I2(PPh3)2(C4H5N3)].The two N atoms of the phenyl ring of 2-aminopyrimidine bridge two [CuI(PPh3)]2 units,by which a one-dimensional chain is constructed.The van der Waals force makes the molecules arrange in the three-dimensional space.     

三维混合价态铜配位聚合物[Cu(Me_2dtc)_2(CuI)_3]_n的合成与晶体结构(英文)

A new three-dimensional copper dithiocarbamate-copper iodide coordination polymer [Cu(Me2dtc)2(CuI)3]n (Me2dtc=N,N-dimethyldithiocarbamate) was synthesized by reactions of Cu(OAc)2,NaI and Na(Me2dtc) in DMF solution,characterized by elemental analysis,IR spectrum,and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system,space group C2/c with a=1.293 89(17) nm,b=1.077 61(11) nm,c=1.456 05(17) nm,β=115.585 (4)°,V=1.831 1 (4) nm3,Z=4,Dc=3.175 g·cm-3,Mr=875.28,λ (Mo Kα)=0.071 073 nm,μ=10.082 mm-1,F(000)=1 604,the final R=0.029 5 and wR=0.081 7. A total of 2 083 unique reflections were collected,of which 1 918 with I2σ(I) were observed. The Cu atoms are Cu(Ⅰ)/Cu(Ⅱ) mixed-valence and they have two different coordinate geometries,namely planar square and tetrahedron. This three-dimensional structure consists of individual Cu(Me2dtc)2 molecules linking together CuI polymeric chains which run parallel to the [001] direction vis Cu-S bonds.     

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.     

Syntheses and Crystal Structures of Two Nickel(II) Complexes [Ni(dmpzm)2(L)]Cl·nH2O (L = HCO2, OAc; n = 2, 3; dmpzm = 1,1'-Methylenebis(3,5-dimethyl-1H-pyrazole))

Reactions of NiCl2·6H2O with dmpzm and formic or acetic acid at PH = 7 pro- duced the two title compounds, [Ni(dmpzm)2(HCO2)]Cl·2H2O 1 and [Ni(dmpzm)2(Oac)]Cl·3H2O 2 (dmpzm = 1,1'-methylenebis(3,5-dimethyl-1H-pyrazole)). 1 and 2 were characterized by elemental analysis, IR spectra, and thermogravimetric analysis. 1 crystallizes in the orthorhombic system, space group Pcca with a = 18.700(2), b = 8.6843(9), c = 18.098(2)(A), V = 2939.1(5)(A)3, Z = 4, Dc = 1.319 g/cm3, T = 193 K, C23H37ClN8NiO4, Mr = 583.75, F(000) = 1232, μ(MoKα) = 0.792 cm(1, S = 1.079, R = 0.0772 and wR = 0.1958 for 2265 observed reflections with I > 2σ(I). 2 crystallizes in the orthorhombic system, space group Pcca with a = 17.011(3), b = 18.630(4), c = 19.300(4)(A), V = 6117(2)(A)3, Z = 8, Dc = 1.337 g/cm3, T = 193(2) K, C24H41ClN8NiO5, Mr = 615.79, F(000) = 2608, μ(MoKα) = 0.768 cm(1, S = 1.059, R = 0.0518 and wR = 0.1109 for 5124 observed reflections with I > 2σ(I). The Ni atoms in 1 or 2 are chelated by two dmpzm ligands and one formate or acetate anion, forming slightly distorted octahedral geometries. In the crystals of 1 or 2, intermolecular hydrogen bonding interactions result in the formation of 2D hydrogen-bonded frameworks.     

Crystal structure and single crystal EPR of (NH_4)_2(15-crown-5)_3[Cu(mnt)_2] and (NH_4)_2(benzo-15-crown-5)_4[Cu(mnt)_2]·0.5H_2O

The X-ray crystal structures of (NH4)2(15-crown-5)3[Cu(mnt)2] (1) and (NH4)2(benzo-15-crown-5)4- [Cu(mnt)2]·0.5H2O (2) were determined. Two single crystals are composed of distinct structures of ammonium-crown ether supramolecular cation and [Cu(mnt)2]2? anion. The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 were observed. X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carried out at room temperature, which revealed that complex 2 showed a perfect hyperfine structure of Cu whereas that of complex 1 could not be observed. The principal values and direction cosines of the principal axes of the g and A tensors were computed by a least-squares fitting procedure. The spin density of Cu(II) was estimated according to the principal values of the A tensors and compared well with the results calculated based on DFT method.     

Synthesis, Crystal Structure and Photoluminescent Properties of a New Dinuclear Copper(I) Complex [Cu_2(μ_2-dppm)_2(MeCN)_2(μ_2-MeCN)](ClO_4)_2·MeCN

The title compound [Cu_2(μ_2-dppm)_2(MeCN)_2(μ_2-MeCN)](ClO_4)_2·MeCN (dppm = bis(diphenylphosphino)methane) has been prepared and characterized. It crystallizes in the monoclinic system, space group P2_1/n, with a = 11.904(6), b = 20.755(11), c = 24.744(13) (A),β = 98.226(12)°, C_(58)H_(56)Cl_2Cu_2N_4O_8P_4,M_r= 1258.93, V=6051(5) (A)~3, Z = 4,D_c= 1.382 g/cm~3,μ = 9.52 mm~(-1), F(000) = 2592, R = 0.0533 and wR = 0.1295 for 6175 observed reflections with I > 2σ(I). Each Cu(I) center is tetrahedrally coordinated by two phosphine atoms from two bridging dppm ligands, one nitrogen atom from a terminally coordinated acetonitrile molecule, and another nitrogen atom from a μ_2-acetonitrile molecule. The two Cu(I) centers are bridged by two dppm ligands as well as a unique acetonitrile molecule. The full molecule exhibits a 'chair-like' configuration. This dinuclear complex exhibits intense or middle photoluminescence at room temperature in the solid state or actonitrile solution at 486 nm.     

Hydrothermal Syntheses and Structural Characterizations of Two ML-Containing Polyoxomolybdates:[Cu~Ⅱ_2(HL)_3]_2[Mo_8O_(26)]·(H_2O)_4 and [Ni~Ⅱ(HL)_3]_2(Mo_8O_(26))·(H_2O)_3(HL=3-(2-Pyridyl)pyrazole)

Two new polyoxomolybdate compounds,namely CuII2(HL)3]2[Mo8O26]·(H2O)4(1) and [NiII(HL)3]2(Mo8O26)·(H2O)3(2)(HL = 3-(2-pyridyl)pyrazole),were designed and synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that compound 1 consists of one β-Mo8O264-cluster and a Cu2 dimer which is built from two Cu(II) ions linked by three 3-(2-pyridyl)pyrazole ligands.Compound 2 is generated by two kinds of polyoxomolybdate clusters of α-[Mo8O26]4-and β-[Mo8O26]4-.In complexes 1 and 2,the multi-dimensional frameworks are con-structed with the help of hydrogen-bonding links between the terminaloxygen atoms of [Mo8O26]4-,water molecules,and 3-(2-pyridyl)pyrazole ligands.Crystal data of 1:C24H25Cu2Mo4N9O15,Mr = 1190.37,monoclinic,space group P21/c,a = 10.850(2),b = 18.510(4),c = 17.230(3) ,β = 100.57(3)°,V = 3401.6(12) 3,Z = 4,Dc = 2.324 g/cm3,F(000) = 2312,μ = 2.742 mm-1,R = 0.0302 and wR = 0.0775(Ⅰ 2σ(Ⅰ));Crystal data for 2:C48H48Mo8N18Ni2O29,Mr = 2225.98,monoclinic,space group P21/n,a = 20.799(2),b = 14.7970(13),c = 23.141(2) ,β = 91.6180(10)°,V = 7119.0(11) 3,Z = 4,Dc = 2.077 g/cm3,F(000) = 4344,μ = 1.968 mm-1,R = 0.0309 and wR = 0.0696(Ⅰ 2σ(Ⅰ)).     

STRUCTURE STUDIES OF [Et_4N]_4[Cu_8(i-mnt)_6] (i-mnt=S_2C=C(CN)_2) AND [Me_4N]_4[Cu_5Ag_3(i-mnt)_6]·H_2O

<正> [Me4N]6[Ag6(i-mnt)6].H2O(1),[Et4N]4[Cu8(i-mnt)6](2) and [Me4N]4-[Cu5Ag3(i-mnt)6].H2O(3)(i-mnt=S2C=C(CN)2) were synthesized. The crystal and molecular structure of the complex 1 was reported by us.The structure of the complex 2 was determined from single crystal X-ray diffraction data. [Et4N]4[Cu8(i-mnt)s] 2, Mr=1870.46, monoclinic, P21/n, a=14.724(6), b = 17.228(3), c=15.59(1)A,β= 100.75(7)°,V=3886.3A3;Z = 2,Dc= 1.598 g/cm3. Complex 3 has been characterized by ICP elemental analyses and IR spectrum.     

Syntheses and Structures of Two Ruthenium(Ⅲ) Complexes [Ru(PPh_3)_2(S_2CNR_2)Cl_2]·CH_2Cl_2(R=Et and ~iPr)

Oxidation reaction of [Ru(PPh3)3Cl2] with tetraethylthiuram disulfide [Et2NCS2]2 or tetra-iso-propylthiuram disulfide [iPr2NCS2]2 afforded ruthenium(Ⅲ) complexes [Ru(PPh3)2(S2CNR2) Cl2]·CH2Cl2(R=Et 1,iPr 2) which were characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group P with a = 11.5065(6),b = 12.1458(7),c = 18.0034(9) ,α = 109.380(4),β = 95.279(4),γ = 97.969(4)°,V = 2324.8(2) 3 and Z = 2.Complex 2 belongs to the monoclinic system,space group P21/n with a = 12.5752(3),b = 20.7562(5),c = 17.6821(3) ,β = 105.934(1)°,V = 4437.94(17) 3 and Z = 4.Both mononuclear complexes 1 and 2 have an octahedral configuration around the central ruthenium atom which is bonded to one chelated dithiocarbamate ligand,two PPh3 ligands in mutually trans and two chlorides in mutually cis positions.The average Ru-S,Ru-P and Ru-Cl bond lengths are 2.377(2),2.412(2) and 2.369(2)  for 1,and 2.376(2),2.414(1) and 2.383(2)  for 2,respectively.The electrochemical properties of these two complexes were studied in CH2Cl2 solution by cyclic voltammetry.     

Synthesis and characterization of a new Mo-Fe-S cluster compound containing MoO_3S_3 unit and mixed-valent Mo atoms [Et_4N]_2[Mo_2Fe(CO)_4(S,O-C_6H_4-1,2)_3Cl_2]

Reaction of [Mo3(CO)7(S,O-C6H4-1,2)3]2- with FeCl2 in MeCN at 60℃ affords a new Mo-Fe-S cluster complex containing MoO3S3 unit and mixed-valeut Mo atoms, [Et4N]2[Mo2Fe-(CO)4(O,S-C6H4-1,2)aCl2] (1). 1 is characterized by elemental analysis, IR, Mossbauer spectra, X-ray photoelectron spectra and mass spectra. And the structure of 1 is suggested as the structure which contains a [Mo(S,O-C6H4-1,2)3] unit of which the two of three sulfur atoms link to a Mo(CO)4-moiety and the three oxygen atoms are coordinated to a FeCl2 ligand.     

Preparation,Characterization and Thermal Decomposition Kinetics of the Complexes [Dy(p-NBA)_3Phen]_2·3H_2O and [Dy(m-NBA)_3Phen]_2·4H_2O

The title complexes [Dy(p-NBA)3Phen]2·3H2O(I) and [Dy(m-NBA)3Phen]2·4H2O(Ⅱ) were synthesized, in the two molecular formulas of which NBA is nitrobenzoate and Phen is 1,10-phenanthroline. The characterizations of the complexes were carried out by means of elemental analysis, UV, IR, XRD and molar conductivity. The thermal decomposition of the two complexes were studied under the non-isothermal condition by DSC, TG-DTG and IR methods in detail. The kinetic parameters of the dehydration process were also obtai...     

Crystal structure and single crystal EPR of (NH4)2(15-crown-5)3[Cu(mnt)2] and (NH4)2(benzo-15-crown-5)4[Cu(mnt)2]·0.5H2O

The X-ray crystal structures of (NH4)2(15-crown-5)3[Cu(mnt)2] (1) and (NH4)2(benzo-15-crown-5)4- [Cu(mnt)2]·0.5H2O (2) were determined. Two single crystals are composed of distinct structures of ammonium-crown ether supramolecular cation and [Cu(mnt)2]2- anion. The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 were observed. X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carried out at room temperature, which revealed that complex 2 showed a perfect hyperfine structure of Cu whereas that of complex 1 could not be observed. The principal values and direction cosines of the principal axes of the g and A tensors were computed by a least-squares fitting procedure. The spin density of Cu(Ⅱ) was estimated according to the principal values of the A tensors and compared well with the results calculated based on DFT method.     

Syntheses and Structures of Two Ruthenium(III)Complexes [Ru(PPh_3)_2(S_2CNR_2)Cl_2]·CH_2Cl_2(R=Et and ~iPr)

Oxidation reaction of [Ru(PPh_3)_3Cl_2] with tetraethylthiuram disulfide[Et_2NCS_2]_2 or tetra-iso-pmpylthiumm disulfide[~iPr_2NCS_2]_2 afforded mthenium(Ⅲ)complexes[Ru(PPh_3)_2(S_2CNR_2)cl_2]·CH2Cl2(R=Et 1,~iPr 2)which were characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in triclinic,space group Pīwith a=11.5065(6),b=12.1458(7),C=18.0034(9)(A),α=109.380(4),β=95.279(4),γ=97.969(4)°,ν=2324.8(2)(A)~3 and Z=2.Complex 2 belongs to the monoclinic system,space group P21/n with a=12.5752(3),b=20.7562(5),e=17.6821(3)(A),β=105.934(1)°,ν=4437.94(17)(A)~3 and Z=4.Both mononuclear complexes 1 and 2 have an octahedral configuration around the central ruthenium atom which is bonded to one chelated dithiocarbamate ligand,two PPh_3 ligands in mutually tram and two chlorides in mutually cis positions.The average Ru-S,Ru-P and Ru-Cl bond lengths are 2.377(2),2.412(2)and 2.369(2)(A) for 1,and 2.376(2),2.414(1)and 2.383(2)(A) for 2,respectively.The electrochemical properties of these two complexes were studied in CH_2Cl_2 solution by cyclic voltammetry.     

Syntheses and Crystal Structures of Two Nickel(Ⅱ) Complexes [Ni(dmpzm)_2(L)]Cl·nH_2O (L=HCO_2,OAc;n=2,3;dmpzm=1,1'-Methylenebis(3,5-dimethyl-1H-pyrazole))

Reactions of NiCl2·6H2O with dmpzm and formic or acetic acid at PH = 7 pro- duced the two title compounds, [Ni(dmpzm)2(HCO2)]Cl·2H2O 1 and [Ni(dmpzm)2(OAc)]Cl·3H2O 2 (dmpzm = 1,1'-methylenebis(3,5-dimethyl-1H-pyrazole)). 1 and 2 were characterized by elemental analysis, IR spectra, and thermogravimetric analysis. 1 crystallizes in the orthorhombic system, space group Pcca with a = 18.700(2), b = 8.6843(9), c = 18.098(2) , V = 2939.1(5) 3, Z = 4, Dc = 1.319 g/cm3, T = 193 K, C23H37ClN8NiO4, Mr = 583.75, F(000) = 1232, μ(MoKα) = 0.792 cm-1, S = 1.079, R = 0.0772 and wR = 0.1958 for 2265 observed reflections with I > 2σ(I). 2 crystallizes in the orthorhombic system, space group Pcca with a = 17.011(3), b = 18.630(4), c = 19.300(4) , V = 6117(2) 3, Z = 8, Dc = 1.337 g/cm3, T = 193(2) K, C24H41ClN8NiO5, Mr = 615.79, F(000) = 2608, μ(MoKα) = 0.768 cm-1, S = 1.059, R = 0.0518 and wR = 0.1109 for 5124 observed reflections with I > 2σ(I). The Ni atoms in 1 or 2 are chelated by two dmpzm ligands and one formate or acetate anion, forming slightly distorted octahedral geometries. In the crystals of 1 or 2, intermolecular hydrogen bonding interactions result in the formation of 2D hydrogen-bonded frameworks.     

Construction of a Novel 2D Polymer [Co（dmpzm）（dca）2]∞ from Reaction of a Mononuclear Complex [Co（dmpzm）Cl2] with Sodium Dicyanamide （dca） [dmpzm=bis（3,5-dimethylpyrazolyl）methane]

Reaction of COC12.6H20 with equimolar bis（3,5-dimethylpyrazolyl）methane （dmpzm） produced a mononuclear adduct [Co（dmpzm）Cl2] （1）. Treatment of 1 with sodium dicyanamide （dca） afforded a polymeric complex [Co（dmpzm）（μ-dca）2]∞ （2）. 1 and 2 were characterized by elemental analysis, IR spectra, thermogravimetric analysis and single-crystal X-ray diffraction. The cobalt atom in 1 adopts a distorted tetrahedral coordination geometry, bound to two N atoms of one dmpzm and two Cl atoms. Complex 2 has a 2D brick-wall network （extended along the bc plane） in which the { [Co（dmpzm）（μ-dca）]2} n^2n＋ chains are interconnected by pairs of μ-dca anions along the c axis. The magnetic properties of 1 and 2 were also investigated.     

Synthesis, structure and characterization of the trinuclear copper (Ⅰ) complex [Cu_3(μ_3Br)_2(dppm)_3]Br

The novel trinuelear copper(I) complex [Cu3(μ3-Br)2(dppm)3]Br has been obtained by reaction of bis(diphenyl-phosphino)methane (dppm) with cupric bromide. The title complex was characterized by single-crystal X-ray analysis, elemental analysis, molecular weight determination, 31P NMR and its conductivity was also measured. The [Cu3(dppm)3Br2] cation consists of a triangular array of copper atoms, with dppm ligands (Ph2PCH2PPh2) bridging each edge of the triangle and two triply bridging Br groups bound to the two faces of the Cu3 unit. Crystallographic data: monoclinic, space group P21/c, a = 1.4739(4) , b = 1.7708(5), c = 2.8395(8) nm, β= 97.16(3)°, V = 7.353nm3, Z = 4,F(000)= 3296, Dcalc = 1.472 g/cm3, μ= 26.478 cm-1, R = 0.06, Rw = 0.08, 4654 reflections observed with I > 3σ(I).     

Synthesis of a new salt containing polyoxometallate anion and M-Cu-S cluster cation [MS_4Cu_4(γ-MePy)_8][M_6O_19] (M = Mo,W).Crystal structure of [WS_4Cu_4(γ-MePy)_8][W_6O_19]

Reactions of (NH4)2MS4, AgBr and CuBr in r-methylpyridine produced one new compound, [MS4Cu4(r-MePy)8]M6O19] (1, M = W; 2, M = Mo), of which 1 was characterized by single crystal X-ray analysis. The crystal data: orthorhombic, Pbcn, a = 15.434(4),b= 16.732(2), c = 28.657(7) A, V = 7400.8(8) A3, Z = 4, R = 0.072 for 3121 independent data. The compound is the first example which contains both polyoxotnngstate anion and heteropolynuclear cluster cation. In the structure of the cation four edges of the tetrahedral WS42- core are coordinated by four copper atoms, giving a WS4Cu4 aggregate of approximate D2h symmetry. The differences between the reaction of Cu+ with MS42- and that of Ag+ with MS42- in pyridine and its derivatives are discussed.     

A bi-butterfly W-Cu-S cluster compound:Synthesis and crystal structure of(n-Bu_4N)_2[W_2Cu_4S_8(S_2CNC_4H_8)_2]

The compound(n-Bu_4N)_2[W_2Cu_4S_8(S_2CNC_4H_8)_2]was obtained by the reaction of Bu_4NBr,(NH_4)_2WS_4,NaS_2NCC_4H_8 and CuCl in CH_3CN and CH_3OH.It crystallizes in the monoclinicspace group P2_1/c with unit cell parameters:a=21.875(5),b=16.843(4),c=17.745(5),β=101.69(6)°,V=6402(6)~3,Z=4,D_o=1.718 g·cm~(-3).The final R and R_w values converged to 0.055and 0.060 respectively.The structure consists of two‘butterfly’units[WS_4Cu_2]linked togetherby two weak Cu—S bonds and two bridging S_2CNC_4H_8 ligands.Infrared spectra gave charac-teristic absorptions at 495 cm~(-1) for W=S and 450,435,412 cm~(-1) for W—μ-S.