Versatility of heterocyclic thioamides in the construction of a trinuclear cluster [Cu3I3(dppe)3 (SC5H4NH)] and Cu(I) linear polymers {Cu6(SC5H4NH)6I6}n x 2nCH3CN and {Cu(I)6 (SC3H6N2)6X6}n (X = Br, I)

Reaction of copper(I) iodide with pyridine-2-thione (2-SC5H4NH) and 1,2-bis(diphenylphosphino)ethane (dppe) in a CH3CN-CHCl3 mixture yielded a triangular cluster, [Cu3I3(mu2-P,P-dppe)3 (eta1-SC5H4NH)], 1. Similar reaction with 2-SC5H4NH and a series of diphosphanes, Ph2P-X-Ph2P {X = -CH2- (dppm), -(CH2)3- (dppp), -(CH2)4- (dppb), -CH=CH- (dppen)}, gave a novel iodo-bridged hexanuclear Cu(I) linear polymer,{Cu6(mu3-SC5H4NH)4 (mu2-SC5H4NH)2 (I4)(mu-I)2-}n x 2nCH3CN, 2. Reactions of copper(I) iodide/copper(I) bromide with 1,3-imidazolidine-2-thione (SC3H6N2) in a CH3CN-CHCl3 mixture yielded hexanuclear Cu(I) linear chain polymers, [{Cu6(mu3-SC3H6N2)2 (mu2-SC3H6N2)4X2 (mu-X)4}n] (X = Br, 4; I, 5). In compound 1, two iodide atoms and one dppe form the dinuclear Cu(mu2-I)2 (mu2-dppe)Cu core, and two dppe ligands bridge this core with the third Cu(I) center coordinated to 2-SC5H4NH via the S atom. The chain polymer 2 has a centrosymmetric hexanuclear central core, Cu6S6I4 (mu-I)2--, formed by dimerization of six-membered trinuclear motifs, Cu3(mu2-SC3H6N2)3I3 via (mu3-S) bonding modes of the thione ligand, and has four terminal and two bridging iodine atoms in trans-orientations. Linear chains are separated by the nonbonded acetonitrile molecules. In 4 and 5, three copper(I) bromide or copper(I) iodide moieties and three SC3H6N2 ligands combined via bridging S donor atoms to form the six-membered trinuclear Cu3(mu2-SC3H6N2)3I3 cores which polymerized via S and X atoms in a side-on fashion to form linear chain polymers, [{Cu6(mu3-SC3H6N2)2 (mu2-SC3H6N2)4X2(mu-X)4}n]. The (mu3-S) modes of bonding of neutral heterocyclic thioamides are first examples, as are trinuclear cluster and linear polymers rare examples in copper chemistry.     

Zn7{(2-C5H4N)CH(OH)PO3}6 (H2O)6]SO4 x 4H2O: a zinc phosphonate cluster with a drum-like cage structure

Direct reaction of hydroxy(2-pyridyl)methylphosphonic acid with zinc sulfate under hydrothermal conditions results in the formation of the novel heptanuclear cluster compound [Zn7{(2-C5H4N)CH(OH)PO3}6 (H2O)6]SO4 x 4H2O (1). The inorganic core of the cluster can be described as a cylindrical drum made up of six Zn atoms bridged by six {CPO3} units that is centered by a seventh Zn atom. Crystal data: monoclinic, C2/c, a = 22.690(2) A, b = 16.675(2) A, c = 18.151(2) A, beta = 93.390(2) degrees.     

Construction of a novel copper(I) chain polymer of hexanuclear Cu6(2-SC5H4NH)6I6 cores with a new (mu 3-S) mode of bonding of pyridine-2-thione and of an unusual triangular Cu3I3(dppe)3(2-SC5H4NH) cluster

The reactions of copper(I) iodide with pyridine-2-thione (2-SC(5)H(4)NH) in the presence of a series of diphosphane ligands, Ph(2)P[bond]X[bond]Ph(2)P [X = [bond](CH(2))(m)[bond], m = 1(dppm), 2 (dppe), 3 (dppp), 4 (dppb); [bond]CH[double bond]CH[bond] (dppen)], yielded an iodo-bridged hexanuclear Cu(I) linear polymer, [Cu(6)(mu(3)-SC(5)H(4)NH)(4)(mu(2)-SC(5)H(4)NH)(2)(I(4))(mu-I)(2)-](n).2nCH(3)CN (1). A similar reaction with 1,2-bis(diphenylphosphino)ethane (dppe) and 2-SC(5)H(4)NH yielded a triangular cluster, Cu(3)I(3)(dppe)(3)(2-SC(5)H(4)NH), 2. In the chain polymer 1, three Cu(I) iodide and three 2-SC(5)H(4)NH ligands combined via bridging S donor atoms to form a boat-shaped trinuclear Cu(3)S(3)I(3) core, and two such cores combined in an inverse manner via four S-donor atoms (mu(3)-S) to form a centrosymmetric hexanuclear repeat unit, Cu(6)S(6)I(4)(mu-I)(2-), which finally formed the iodo-bridged infinite linear chain polymer 1. Linear chains are separated by the nonbonded acetonitrile molecules. Polymer 1 is the first such example of a linear chain formed by the hexanuclear Cu(6)S(6)I(6) core in copper chemistry as well as in metal-heterocyclic thioamide chemistry. In addition, it has the first mu(3)-S mode of neutral pyridine-2-thione ever reported. In the moiety Cu(3)I(3)(dppe)(3) of 2, two copper(I) centers are bridged by the iodide ligands forming a Cu(mu-I)(2)Cu core, while a third copper(I) center is terminally bonded to another iodide ligand. Polymer 2 is also rare, and the first triangular cluster of Cu(I) with an heterocyclic thioamide.     

{[(n-C_4H_9)_4N]_2Ag_(4.95)Cu(Ⅰ)_(1.05)I_8}_n聚合物的合成和晶体结构

标题化合物由AgI、CuI和(n-C4H9)4NI在DMF溶剂中直接反应而得。晶体结.构通过单晶X-射线衍射法确定,其晶体属于单斜晶系,空间群P21/c,a=9.4342(4),b=15.7638(7),c=18.877(1)??=100.65(1)?V=2758.9(2)3,化学式C32H72N2Ag4.95Cu1.05I8,Mr=2100.79,Dc=2.529g/cm3,Z=2,(MoK?=6.618cm-1,F(000)=1930。在1.70≤?≤27.46范围内收集到22473个衍射点,独立衍射点6175(Rint=0.0753),其中可观测衍射点4158个(I>2(I))。晶体结构用直接法和差傅立叶合成方法找出初步结构模型,再分别对Ag和Cu的坐标进行修正,最后用全矩阵最小二乘法对266个变量进行精修,最终偏离因子R=0.0476,wR=0.1315。标题化合物的结构由[(M6I8)-]阴离子链和链间的n-Bu4N+阳离子组成。     

Influence of hydrogen bonding on the assembly of six-membered vanadium borophosphate cluster anions: synthesis and structures of (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12](6)10H2O, (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12](6)17H2O, and (NH4)3(C4H14N2)4 5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O

Three new strontium vanadium borophosphate compounds, (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O (Sr-VBPO1) (1), (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O (Sr-VBPO2) (2), and (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O (Sr-VBPO3) (3) have been synthesized by interdiffusion methods in the presence of diprotonated ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane. Compound 1 has a chain structure, whereas 2 and 3 have layered structures with different arrangements of [(NH4) [symbol: see text] [V2P2BO12]6] cluster anions within the layers. Crystal data: (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 21.552(1) A, b = 27.694(2) A, c = 20.552(1) A, beta = 113.650(1) degrees, Z = 4; (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O, monoclinic, space group I2/m (no. 12), a = 15.7618(9) A, b = 16.4821(9) A, c = 21.112(1) A, beta = 107.473(1) degrees, Z = 2; (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4] [V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 39.364(2) A, b = 14.0924(7) A, c = 25.342(1) A, beta = 121.259(1) degrees, Z = 4. The differences in the three structures arise from the different steric requirements of the amines that lead to different amine-cluster hydrogen bonds.     

Dinuclear and layered copper 2-pyridylphosphonates with weak ferromagnetism observed in layer compound Cu(C5H4NPO3)

This paper reports the syntheses and structures of three new copper phosphonates based on 2-pyridylphosphonate, namely, Cu(C(5)H(4)NPO(3)H)2 (1), Cu3(OH)2(C(5)H(4)NPO(3))2.2H2O (2) and Cu(C(5)H(4)NPO(3)) (3). Compound 1 has a discrete dimeric structure in which the {CuO(4)N} square pyramids are linked by the {CPO(3)} tetrahedra through corner-sharing. The dimers are further connected into a chain through hydrogen bonds. In compound 2, edge-sharing {Cu(1)O(4)N} square pyramids and {Cu(2)O(4)} planes are found to form an infinite chain with composition {Cu(3)(mu-OH)(2)(mu-O)(4)}. Neighboring chains are linked by the phosphonate groups of the 2-pyridylphosphonate ligands, resulting in inorganic layers containing 4-, 8- and 12-membered rings. The pyridyl groups and the lattice water molecules occupy the inter-layer space. In compound 3, the {Cu(1)O(4)} and {Cu(2)O(2)N(2)} planes are each corner-shared with the {CPO(3)} tetrahedra, forming an inorganic layer containing 8- and 16-membered rings. The pyridyl groups reside between the layers. Crystal data for 1: space group P(-)1, a = 8.4045(19), b = 8.751(2), c = 10.632(2) A, alpha = 66.673(4), beta = 72.566(4), gamma = 70.690(4) degrees , V = 664.7(2) A(3), Z = 2. Crystal data for 2: space group P2(1)/c, a = 7.9544(17), b = 21.579(4), c = 5.0243(10) A, beta = 105.332(3) degrees , V = 831.7(3) A(3), Z = 2. Crystal data for 3: space group P2(1)/c, a = 4.7793(11), b = 15.319(3), c = 8.6022(19) A, beta = 97.156(4) degrees , V = 624.9(2) A(3), Z = 4. Magnetic measurements reveal that dominant antiferromagnetic interactions are propagated between the copper centers in compounds 1-3. For 3, spin canting is observed with a ferromagnetic transition occurring at 9 K.     

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.     

Synthesis and Crystal Structure of the Copper Complex {[Cu（CH3COO）2（bbtz）]（H2O）2}n

1 INTRODUCTION The design and synthesis of metal-organic frame- work structures have been extensively studied due to their unexpected properties for potential applications as functional materials as well as the intriguing ar- chitectures and topologies[1～4]. When rigid bifunc- tional ligands are used to connect metal centers, to- pology of the network is usually determined by the coordination geometry of the central metal prefer- ence. Contrary to rigid ligands, the bifunctional fle- xib…     

Hydrothermal Synthesis and Crystal Structure of a New Phosphonate： {[Cu（1,10-phen）]2-（H2O3PCH2C6H4C6H4CH2PO3H）2-（HO3PCH2C6H4C6H4CH2PO3H） }n

1 INTRODUCTION Metal organophosphonates have attracted considerable attention for over three decades due to their potential or practical applications, include- ing ion exchanges[1, 2], molecular sensors[3] and optics[4, 5]. Recently, a number of porous m…     

Combination of lacunary polyoxometalates and high-nuclear transition metal clusters under hydrothermal conditions. 3. Structure and characterization of [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}.4H2O

A novel sandwich-type polyoxometalate incorporating a unique hybrid hexanuclear copper cluster, [Cu(enMe)2]2{[Cu(enMe)2(H2O)]2[Cu6(enMe)2(B-a-SiW9O34)2]}.4H2O (1, enMe=1,2-diaminopropane), has been hydrothermally synthesized and structurally characterized by the elemental analyses, IR spectroscopy, TG analysis, magnetic properties, and single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, P; a=12.5105(2), b=14.3710(2), c=17.2687(2) A; alpha=98.834(1), beta=110.744(1), gamma=104.711(1) degrees; V=2704.57(7) A3; rho=3.646 g/cm3; Z=1. X-ray crystallographic study shows that the molecular structure of 1 contains 10 copper ions: Six of them form an unprecedented inorganic-organic hybrid Cu6 cluster via edge-sharing combination of two CuO6 octahedra, two CuO5, and two CuO3N2 square pyramids and are encapsulated between two {B-a-SiW9O34} units. Two of them form two [Cu(enMe)2(H2O)]2+ complexes and further attach to the two {B-a-SiW9O34} units via two Cu-O=W bridges, acting as a decorated role. The remaining two form isolated [Cu(enMe)2]2+ complexes playing roles of charge-compensation and space-fillers. Magnetization measurement reveals that the hexanuclear copper cluster exhibits overall ferromagnetic interactions.     

Dinitrosyl iron complexes (DNICs) containing S/N/O ligation: transformation of Roussin's red ester into the neutral {Fe(NO)2}10 DNICs

Addition of the Lewis base [OPh]- to the THF solution of Roussin's red ester [Fe(mu-SC6H4-o-NHCOPh)(NO)2]2 (1) and [Fe(mu-SC6H4-o-COOH)(NO)2]2 (2), respectively, yielded the EPR-active, anionic {Fe(NO)2}9, [(SC6H4-o-NCOPh)Fe(NO)2]- (3) with the anionic [SC6H4-o-NCOPh]2- ligand bound to the {Fe(NO)2} core in a bidentate manner (S,N-bonded) and [(SC6H4-o-COO)Fe(NO)2]- (4) with the anionic [SC6H4-o-COO]2- ligand bound to the {Fe(NO)2} core in a bidentate manner (S,O-bonded), characterized by IR, UV-vis, EPR, and single-crystal X-ray diffraction. In contrast to the bridged-thiolate cleavage yielding the neutral {Fe(NO)2}9, [(SC6H4-o-NHCOPh)(Im)Fe(NO)2] (Im=imidazole), by addition of 2 equiv of imidazole to complex 1 observed in the previous study, the addition of the stronger sigma-donating and pi-accepting PPh3 ligand triggered the reductive elimination of bridged thiolates of complex 1 to yield the neutral {Fe(NO)2}10, [(PPh3)2Fe(NO)2]. These results unambiguously illustrate one aspect of how the nucleophile L (L=imidazole, PPh3, [OPh]-) functions to control the reaction pathways (bridged-thiolate cleavage, reductive elimination, and deprotonation) upon the reaction of complex 1 and the nucleophile L. The EPR-active, dimeric {Fe(NO)2}9 dinitrosyl iron complex (DNIC) [Fe(mu-SC7H4SN)(NO)2]2 (6), with S and N atoms of the anionic [-SC7H4SN-]- (2-benzothiozolyl thiolate) ligands bound to two separate {Fe(NO)2}9 cores, was also synthesized from reaction of bis(2-benzothiozolyl) disulfide and [(NO)2Fe(PPh3)2]. A straightforward reaction of complex 6 and 4 equiv of [N3]- conducted in THF led to the anionic {Fe(NO)2}9, [(N3)2Fe(NO)2]- (7). Conclusively, the EPR-active, {Fe(NO)2}9 DNICs can be classified into the anionic {Fe(NO)2}9 DNICs with S/N/O ligation, the neutral {Fe(NO)2}9 DNIC with one thiolate and one neutral imidazole ligation, and the cationic {Fe(NO)2}9 DNICs with the neutral N-/P-containing coordinated ligands.     

The synthesis and characterization of compounds of the type Hg[1-C(6)H(4)-2-C(H)=NC(6)H(5-n)R(n)](2)

The organomercurial compounds Hg[1-C(6)H(4)-2-C(H)=NC(6)H(5-n)R(n)](2) (R = 4-NMe(2), 6a; 4-Me, 6b; 4-I, 6c; 4-NO(2), 6d; 2-(i)Pr, 6e; 2-Me, 6f; 2,6-(i)Pr(2), 6g; 2,6-Me(2), 6h) have been prepared in good overall yield from 2-bromobenzaldehyde. All of the compounds have been characterized by elemental analysis, (1)H NMR, (13)C[(1)H] NMR, and infrared spectroscopy. In addition, compounds 6a [C(30)H(30)HgN(4), triclinic, P, a = 6.20000(10) A, b = 9.2315(2) A, c = 10.9069(3) A, alpha = 85.8510(10) degrees, beta = 89.3570(10) degrees, gamma = 87.206(2) degrees, Z = 1], 6b [C(28)H(24)HgN(2), monoclinic, P2(1)/c, a = 12.8260(5) A, b = 14.0675(4) A, c = 6.1032(2) A, beta = 90.0990(10) degrees, Z = 2], 6g [C(38)H(44)HgN(2), triclinic, P, a = 8.2626(2) A, b = 9.8317(2) A, c = 11.8873(3) A, alpha = 103.6650(10) degrees, beta = 109.3350(10) degrees, gamma = 104.627(2) degrees, Z = 1], and 6h [C(30)H(28)HgN(2), monoclinic, P2(1)/c, a = 12.5307(2) A, b = 10.9852(2) A, c = 18.2112(2) A, beta = 104.0190(10) degrees, gamma = 87.206(2) degrees, Z = 4] have been characterized by low-temperature single-crystal X-ray diffraction studies, and two different molecular geometries about the central mercury atom have been observed; intramolecular contacts suggest a van der Waals radius for Hg of 2.1-2.2 A.     

New framework connectivity patterns in templated networks: the creatinine zinc phosphites C4N3OH7.ZnHPO3, C4N3OH7.Zn(H2O)HPO3, and (C4N3OH7)2.ZnHPO3.H2O

The syntheses, crystal structures, and properties of C(4)N(3)OH(7).ZnHPO(3), C(4)N(3)OH(7).Zn(H(2)O)HPO(3), and (C(4)N(3)OH(7))(2).ZnHPO(3).H(2)O are reported. These new creatinine zinc phosphites are built up from networks of vertex-sharing HPO(3) pseudopyramids and various types of ZnO(2)N(2), ZnO(3)N, and ZnO(2)N(H(2)O) tetrahedra, resulting in extended structures of different dimensionalities (as sheets, clusters, and chains, respectively). They demonstrate the structural effect of incorporating "terminal" (nonnetworking) Zn-N and Zn-OH(2) moieties into zinc centers. Crystal data: C(4)N(3)OH(7).ZnHPO(3), triclinic, P1 (No. 2), a = 8.9351(4) A, b = 9.5011(4) A, c = 9.9806(4) A, alpha = 87.451(1) degrees, beta = 85.686(1) degrees, gamma = 89.551(1) degrees, Z = 4; C(4)N(3)OH(7).Zn(H(2)O)HPO(3), monoclinic, P2(1)/c (No. 14), a = 10.1198(7) A, b = 7.2996(5) A, c = 13.7421(9) A, beta = 107.522(1) degrees, Z = 4; (C(4)N(3)OH(7))(2).ZnHPO(3).H(2)O, triclinic, P1 (No. 2), a = 10.7289(6) A, b = 10.9051(6)A, c = 13.9881(8) A, alpha = 89.508(1) degrees, beta = 74.995(1) degrees, gamma = 74.932(1) degrees, Z = 4.     

Synthesis and characterization of diverse coordination polymers. Linear and zigzag chains involving their structural transformation via intermolecular hydrogen-bonded, interpenetrating ladders polycatenane, and noninterpenetrating square grid from long, rigid N,N'-bidentate ligands: 1,4-bis[(x-pyridyl)ethynyl]benzene (x = 3 and 4)

The long, rigid ligands 1,4-bis[(3-pyridyl)ethynyl]benzene (L1) and 1,4-bis[(4-pyridyl)ethynyl]benzene (L2) were used in the synthesis of 10 new organic-inorganic coordination frameworks, each of them adopting different structural motifs. Synthesis, single-crystal X-ray structure determination, and spectroscopic and thermogravimetric analyses are presented. The reactions between M(NO3)2 x xH2O; M = Cd(II), Cu(II), and Co(II); x = 3-6 and Cu(hfac)2 x H2O [hfac = bis(hexafluoroacetylacetonato)] with L1 afforded the following one-dimensional zigzag chain structures: [Cd(C20H12N2)0.5(NO3)(CH3OH)]n (1, monoclinic, C2/c; a = 7.586(1) A, b = 23.222(1) A, c = 13.572(1) A, beta = 92.824(1), Z = 4); [{Cu(C20H12N2)(NO3)2(CH3OH)} x CH3OH]n (2, orthorhombic, P2(1)2(1)2(1); a = 8.589(1) A, b = 15.766(1) A, c = 17.501(1) A, Z = 4); [Co(C20H12N2)2(NO3)2(H2O)2] (5, triclinic, P1; a = 7.493(1) A, b = 8.948(1) A, c = 14.854(1) A, alpha = 100.427(1), beta = 97.324(1), gamma = 110.901(1), Z = 1); [Cu(C20H12N2)(hfac)2]n (4, monoclinic, C2/c, a = 18.828(1) A, b = 14.671(1) A, c = 13.427(1) A, beta = 90.447(1) degrees, Z = 4). Moreover, the minority phase compound formed from Cu(NO3)2 x 3H2O and L1 yielded a metallocyclic chain structure, [Cu(C20H12N2)(NO3)]n (3, triclinic, P; a = 8.728(1) A, b = 10.018(1) A, c = 11.893(1) A, alpha = 109.991(1), beta = 97.109(1), gamma = 115.542(1), Z = 1). In addition to the dinuclear coordination complex 5, all other polymeric structures (1-4) from L1 are composed of interpenetrating 2D and 3D cross-linked zigzag chains via hydrogen-bonding interactions. The reactions between M(NO3)2 x xH2O; M = Cd(II), Cu(II), and Co(II); x = 3-6 and Cu(hfac)2 x H2O [hfac = bis(hexafluoroacetylacetonato)] and L2 were dependent on the nature of the metal center and resulted in the formation of four different interpenetrating and noninterpenetrating compounds (6-10): [Co(C20H12N2)1.5(NO3)2]n (6, triclinic, P; a = 14.172(1) A, b = 15.795(1) A, c = 18.072(1) A, alpha = 115.380(1), beta = 101.319(1), gamma = 93.427(2), Z = 4), which consists of T-shaped building blocks assembled into three-dimensional interpenetrating polycatenated ladders; [Cd(C20H12N2)2(NO3)2]n (7, monoclinic, I2/a; a = 11.371(1) A, b = 20.311(2) A, c = 15.240(2) A, beta = 100.201(2) degrees, Z = 4), which adopts a two-dimensional noninterpenetrating square-grid motif; [Cu(C20H12N2)(hfac)2]n (8, monoclinic, I2/a; a = 11.371(1) A, b = 20.311(2) A, c = 15.240(2) A, beta = 100.201(2) degrees, Z = 4), composed of three sets of distinct one-dimensional linear chains; [Cu(C20H12N2)(EtOH)(NO3)2] [Cu(C20H12N2)1.5(NO3)2] x 2EtOH (9, triclinic, P; a = 12.248(2) A, b = 13.711(3) A, c = 18.257(4) A, alpha = 108.078(4) degrees, beta = 97.890(4) degrees, gamma = 103.139(5) degrees, Z = 2) and [Cu(C20H12N2)(MeOH)(NO3)2] [Cu(C20H12N2)1.5(NO3)2] x 2MeOH (10, triclinic, P; a = 12.136(1) A, b = 13.738(2) A, c = 17.563(3) A, alpha = 107.663(3) degrees, beta = 94.805(4) degrees, gamma = 104.021(4) degrees, Z = 2). Both 9 and 10 stack into infinite interpenetrating ladders through bundles of infinite chains and are described in our preliminary communication.     

Synthesis and Crystal Structure of Dinuclear Copper Complex[Cu（CH2O（C6H4）N=C（C6H4）O）（Py]2

1 INTRODUCTION Synthesis of transition metal complexes with Schiff-base has been a subject of considerable importance [1,2]. They are not only good complexing agents for Schiff-base, but also good bactericide and antitumour agent [3,4]. At present, there is a spectacular growth in this field. Recently, some bridged binuclear complexes have received much attention on account of their biological relevance and condensed-phase magnetic properties[5,6]. Especially, the complexes containin…     

Der erste Metallkomplex mit neutralem 1,2-Bis(phenyltriazeno)benzol als Ligand: Synthese und Struktur von [Cd{PhN3(H)C6H4N3(H)Ph}{PhN3C6H4N3(H)Ph}2]

The First Metal Complex with Neutral 1,2-Bis(phenyltriazeno)-benzene as Ligand: Synthesis and Crystal Structure of [Cd{PhN₃(H)C₆H₄N₃(H)Ph}{PhN₃C₆H₄N₃(H)Ph}₂] [Cd{PhN₃(H)C₆H₄N₃(H)Ph}{PhN₃C₆H₄N₃(H)Ph}₂] is obtained in aqueous ammonia by the reaction of CdSO₄ with an excess of 1,2-bis(phenyltriazeno)benzene. It forms orange red, air stable prismatic crystals with the monoclinic space group P2₁/c and a = 1217.7(2); b = 2161.8(6); c = 2008.3(5) pm; β = 100.07(6)º; Z = 4. The compound is composed of mononuclear complexes in which the Cd atom is coordinated by one chelating bis(phenyltriazeno)benzene and two monodentate 1-phenyltriazenido-2-phenyltriazeno benzene anions in a distorted tetrahedral arrangement. The Cd—N distances are in the range of 220.7 to 239.7 pm.     

Synthesis and structures of polymeric Mn, Co, Cu, and Zn complexes of 3-diphenylamino-4-hydroxycyclobut-3-ene-1,2-dione (diphenylaminosquarate) and of the salt [Ni(H2O)6][(C6H5)2NC4O3]2.2H2O

Reaction of M(NO3)2.xH2O (M = Mn, Co, Ni, Cu, Zn) with 3-diphenylamino-4-hydroxycyclobut-3-ene-1,2-dione (diphenylaminosquarate) produces the neutral polymeric species (M[mu-(C6H5)2NC4O3]2[H2O]2)n [M = Mn (1), Cu (2)]; (M[mu-(C6H5)2NC4O3][(C6H5)2NC4O3][H2O]3)n [M = Co (3), Zn (4)]; and in the case of Ni, the salt [Ni(H2O)6][(C6H5)2NC4O3]2.2H2O (5). Complexes 1 and 2 are isomorphous and crystallize in the monoclinic space group P2(1)/c with, for 1, a = 13.138(1) A, b = 10.900(2) A, c = 9.269(2) A, beta = 96.07(1) degrees, and Z = 2. Complexes 3 and 4 are also isomorphous and crystallize in the space group P2(1)/c with, for 3, a = 13.211(1) A, b = 11.038(1) A, c = 18.748(1) A, beta = 97.75(1) degrees, and Z = 4. The nickel salt, 5, crystallizes in the triclinic space group P1 with a = 6.181(1) A, b = 9.417(1) A, c = 15.486(1) A, alpha = 101.37(1) degrees, beta = 95.51(1) degrees, gamma = 107.57(1) degrees, and Z = 1. In 1 and 2, the metal coordination is octahedral, comprising four mu-1,3-bridging diphenylaminosquarate ligands and two trans aqua ligands. In 3 and 4, the metal coordination is again octahedral, comprising two mu-1,3-bridging and one pendant diphenylaminosquarate ligands, the octahedron being completed by three aqua ligands in a meridional configuration. In 5, the hexaaquanickel(II) ion is linked by O-H...O hydrogen bonds to a pair of diphenylaminosquarate anions. These anion-cation units are linked via included water molecules to form hydrogen-bonded chains. The diphenylaminosquarate ligands in the polymeric complexes 1-4 display multiple-bond localization, a feature which is absent in 5. Complex 1 exhibits weak antiferromagnetic coupling, whereas 2 shows no significant magnetic interactions.     

A hydrothermal investigation of the 1/2V2O5-H2C2O4/H3PO4/NH4OH system: synthesis and structures of (NH4)VOPO(4).1.5H2O, (NH4)0.5VOPO(4).1.5H2O, (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2](2).3H2O, and (NH4)2[VO(HPO4)]2(C2O4).5H2O

The 1/2V2O5-H2C2O4/H3PO4/NH4OH system was investigated using hydrothermal techniques. Four new phases, (NH4)VOPO(4).1.5H2O (1), (NH4)0.5VOPO(4).1.5H2O (2), (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O (3), and (NH4)2[VO(HPO4)]2(C2O4).H2O (4), have been prepared and structurally characterized. Compounds 1 and 2 have layered structures closely related to VOPO(4).2H2O and A0.5VOPO4.yH2O (A = mono- or divalent metals), whereas 3 has a 3D open-framework structure. Compound 4 has a layered structure and contains both oxalate and phosphate anions coordinated to vanadium cations. Crystal data: (NH4)VOPO(4).1.5H2O, tetragonal (I), space group I4/mmm (No. 139), a = 6.3160(5) A, c = 13.540(2) A, Z = 4; (NH4)0.5VOPO(4).1.5H2O, monoclinic, space group P2(1)/m (No. 11), a = 6.9669(6) A, b = 17.663(2) A, c = 8.9304(8) A, beta = 105.347(1) degrees, Z = 8; (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O, triclinic, space group P1 (No. 2), a = 10.2523(9) A, b = 12.263(1) A, c = 12.362(1) A, alpha = 69.041(2) degrees, beta = 65.653(2) degrees, gamma = 87.789(2) degrees, Z = 2; (NH4)2[VO(HPO4)]2(C2O4).5H2O, monoclinic (C), space group C2/m (No. 12), a = 17.735(2) A, b = 6.4180(6) A, c = 22.839(2) A, beta = 102.017(2) degrees, Z = 6.     

Synthesis and characterization of new coordination polymers generated from bent bis(cyanophenyl)oxadiazole ligands and Ag(I) salts

Two new bent bis(cyanophenyl)oxadiazole ligands, 2,5-bis(4-cyanophenyl)-1,3,4-oxadiazole (L7) and 2,5-bis(3-cyanophenyl)-1,3,4-oxadiazole (L8), were synthesized. The coordination chemistry of these ligands with various Ag(I) salts has been investigated. Seven new coordination polymers, namely, {[Ag(L7)(H2O)]ClO4}n) (1) (triclinic, P1, a = 9.342(4) A, b = 9.889(4) A, c = 10.512(4) A, alpha = 68.978(6) degrees, beta = 78.217(6) degrees, gamma = 81.851(7) degrees, Z = 2), {[Ag(L7)]SO3CF3}n (2) (monoclinic, P2(1)/n, a = 7.559(2) A, b = 23.739(6) A, c = 10.426(3) A, beta = 108.071(4) degrees, Z = 4), {[Ag(L8)]BF4 x 0.5(C6H6) x H2O}n (3) (triclinic, P1, a = 7.498(3) A, b = 10.649(4) A, c = 13.673(5) A, alpha = 98.602(5) degrees, beta = 100.004(5) degrees, gamma =110.232(5) degrees, Z = 2), {[Ag(L8)SbF6] x H2O}n (4) (triclinic, P1, a = 8.2621(9) A, b = 10.6127(12) A, c = 13.3685(15) A, alpha = 98.012(2) degrees, beta = 106.259(2) degrees, gamma = 112.362(2) degrees, Z = 2), {[Ag2(L8)2(SO3CF3)] x H2O}n (5) (triclinic, P1, a = 10.713(4) A, b = 13.449(5) A, c = 15.423(5) A, alpha = 65.908(5) degrees, beta = 74.231(5) degrees, gamma = 83.255(5) degrees, Z = 2), {[Ag2(L8)(C6H6)(ClO4)] x ClO4}n (6) (monoclinic, P2(1)/n, a = 6.9681(17) A, b = 20.627(5) A, c = 17.437(4) A, beta = 95.880(4) degrees, Z = 4), and {[Ag2(L8)(H2PO4)2]}n (7) (triclinic, P1, a = 7.956(2) A, b = 9.938(3) A, c = 14.242(4) A, alpha = 106.191(4) degrees, beta = 97.322(4) degrees, gamma = 107.392(4) degrees, Z = 1), were obtained by the combination of L7 and L8 with Ag(I) salts in a benzene/methylene chloride mixed-solvent system and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. In addition, the luminescence and electrical conductance properties of compounds 1-6 and the host-guest chemistry of compound 3 were investigated.     

Synthesis and Characterization of a One-dimensional Chain Polymer {[Cu(4-CPOA)(3-PyOH)2(H2O)2](H2O}n

A novel one-dimensional copper(II) coordination polymer of {[Cu(4-CPOA)(3- PyOH)2(H2O)2]·H2O}n (4-CPOA2- = 4-carboxyphenoxyacetate dianion, 3-PyOH = 3-hydroxypyri- dine) has been synthesized and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The complex C19H22N2O10Cu crystallizes in triclinic system, space group P-1with a = 7.672(2), b = 18.490(4), c = 13.271(3) (A), α = 72.81(3), β ＝ 84.64(3), γ = 87.28(3)°, V = 1026.3(4) (A)3, Z = 2, Mr = 501.94, Dc = 1.624 g/cm3, μ = 1.126 mm-1, F(000) = 518, the final R = 0.0580 and wR = 0.1310 for 3364 observed reflections with I > 2σ(I). Each Cu(II) ion is coordinated with two different carboxyl O atoms from two 4-carboxyphenoxyacetate groups, two N atoms from two 3-PyOH ligands and two water molecules, residing in a distorted octahedral environment. Adjacent Cu(II) atoms are linked by bi-monodentate 4-CPOA2- groups into an one-dimensional chain along the b axis. A three-dimensional supramolecular network is constructed by O-H…O hydrogen bonds.