Indium-sulfur supertetrahedral polymers integrated with [M(phen)3]2+ cations (M = Ni and Fe)

A series of supertetrahedral polymers of chalcogenometalates (T3 cluster compounds) integrated with M-phen complexes (phen =1,10-phenanthroline; M = Ni, Fe) was prepared by a similar solvothermal technique. Compound [Fe(phen)(3)](4)[H(4)In(20)S(38)]·Hphen·3HDMA·8H(2)O (Mp-InS-4) (DMA = dimethylamine) is a 1-D straight chain. Compounds [M(phen)(3)](4)[In(20)S(37)]·6Hphen·4H(2)O (M = Ni, Mp-InS-5; Fe, Mp-InS-6) are the first reported 2-D Tn polymers integrated with complex cations of [M(phen)(3)](2+). Compound [Ni(phen)(3)](4)[H(4)In(20)S(38)]·2Hphen·2HDMA·3H(2)O (Mp-InS-7) shows a zigzag 1-D structure. We find that the reaction time is an important factor in assembling of the T3 clusters. Prolonging the reaction time seems favorable to the higher condensed phases (from 0-D to 2-D). However, a longer reaction time resulted in the crack of 2-D structure. Integrating M-phen complex cations with the chalcogenido anions can improve absorption of the materials in the visible range due to the charge transfers within the cations or between cations and anions.     

A single-helix coordination polymer with mixed ligands [Zn2(phen)2(e,a-cis-1,4-chdc)2(H2O)2]n (phen=1,10-phenanthroline; chdc=cyclohexanedicarboxylate)

A coordination polymer with mixed ligands [Zn₂(phen)₂(e,a-cis-1,4-chdc)₂(H₂O)₂]_n (chdc=cyclohexanedicarboxylic acid; phen=1,10-phenanthroline) was prepared under hydrothermal conditions and characterized by elemental analyses, IR spectra, TG analysis, and single-crystal X-ray diffraction analysis. X-ray crystal structural analyses reveal that 1 and 2 are isomorphic and belong to the monoclinic system. C₄₀H₃₆Zn₂N₄O₁₀, P2₁/c, a=10.084(2) Å, b=8.9072(18) Å, c=20.276(4) Å, β=99.92(3)°, V=1793.9(6) Å³, Z=1. In the structures of 1, the 1,4-chdc ligand possesses only one kind of e,a-cis-conformation although there are both cis- and trans-conformations in the raw material. Two oxygen atoms of one carboxyl in 1,4-chdc ligand and another oxygen atom of contraposition carboxyl link adjacent Zn atoms into an infinite 1D zigzag chain. The most attractive structural feature of 1 is that it exhibits an infinite chiral chain-like structure with 2₁ helices along the b-axis. In addition, the right- and left-handed chains are alternate. Meanwhile, the adjacent chains of 1 is linked via hydrogen bonds into 2D network structures, which further form 3D frameworks via π-π interactions of 1,10-phen.     

Novel hydrogen-bonded three-dimensional networks encapsulating one-dimensional covalent chains: [M(4,4'-bipy)(H2O)(4)](4-abs)(2).nH2O (4,4'-bipy = 4,4'-bipyridine; 4-abs = 4-aminobenzenesulfonate) (M = Co,n = 1; M = Mn,n = 2)

Two novel compounds, [Co(4,4'-bipy)(H(2)O)(4)](4-abs)(2).H(2)O (1) and [Mn(4,4'-bipy)(H(2)O)(4)](4-abs)(2).2H(2)O (2) (4,4'-bipy = 4,4'-bipyridine; 4-abs = 4-aminobenzenesulfonate), have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses, UV-vis and IR spectra, and TG analysis. X-ray structural analysis revealed that 1 and 2 both possess unusual hydrogen-bonded three-dimensional (3-D) networks encapsulating one-dimensional (1-D) covalently bonded infinite [M(4,4'-bipy)(H(2)O)(4)](2+) (M = Co, Mn) chains. The 4-abs anions in 1 form 1-D zigzag chains through hydrogen bonds. These chains are further extended through crystallization water molecules into 3-D hydrogen-bonded networks with 1-D channels, in which the [Co(4,4'-bipy)(H(2)O)(4)](2+) linear covalently bonded chains are located. Crystal data for 1: C(22)H(30)CoN(4)O(11)S(2), monoclinic P2(1), a = 11.380(2) A, b = 8.0274(16) A, c = 15.670(3) A, alpha = gamma = 90 degrees, beta = 92.82(3) degrees, Z = 2. Compound 2 contains interesting two-dimensional (2-D) honeycomb-like networks formed by 4-abs anions and lattice water molecules via hydrogen bonding, which are extended through other crystallization water molecules into three dimensions with 1-D hexagonal channels. The [Mn(4,4'-bipy)(H(2)O)(4)](2+) linear covalent chains exist in these channels. Crystal data for 2: C(22)H(32)MnN(4)O(12)S(2), monoclinic P2(1)/c, a = 15.0833(14) A, b = 8.2887(4) A, c = 23.2228(15) A, alpha = gamma = 90 degrees, beta = 95.186(3) degrees, Z = 4.     

Synthesis and Crystal Structure of a Ternary Complex: [Ni(phen)2(pmal)]·8H2O

A new ternary complex [Ni(phen)(pmal)]·8H2O (phen = 1,10-phenanthroline,pmal2- = phenethyl malonic acid) has been synthesized by the reaction of nickel acetate, phen and phenethyl malonic acid. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex: triclinic system, space group P1, a = 10.387(5), b = 13.112(6), c = 14.229(6) (A), α = 76.176(7), β =83.778(8), y = 71.770(6)°, C35H42N4O12Ni, Mr= 769.44, Z = 2, F(000) = 808, V = 1786.1 (A)3, Dc =1.431 g/cm3, μ = 0.612 mm-1, the final R = 0.0653 and wR = 0.1033 for 9379 (Rint = 0.0244)independent reflections and 4730 observed reflections (I ＞ 2σ(I)). Structural analysis shows that the coordination geometry of Ni(Ⅱ) is a distorted octahedron. A novel two-dimensional structure is constructed from (H2O)4 and (H2O)12 water clusters, and the complex forms a 3-D network supramolecular structure by hydrogen bonds and π-π stacking of neighboring phens.     

新型邻菲咯啉镁(II)配合物[Mg(H_2O)_4(phen)](phen)[C_6H_4(COO)_2]·H_2O的水热合成和晶体结构

合成了新型邻菲咯啉镁(II)配合物 [Mg(H2O)4(phen)](phen)[C6H4(COO)2]?H2O, 并对其进行了元素分析、IR、TG、X-射线衍射等表征。单晶衍射结果表明, 该配合物晶体属单斜晶系, 空间群为 P21/c, 晶胞参数:a = 11.873(2), b = 31.992(6), c = 8.144(2) ?, β = 93.98(3), V = 3085.9(11)?3, Z = 4, F(000) = 1336, Dc = 1.375 g/cm3, μ(MoKα) = 0.120 mm?1。对于 6889[ Rint = 0.0264]个独立衍射点, 有 3939 个可观测点满足(I≥2σ (I)), 最终的偏离因子 R = 0.0430, wR = 0.1294。标题配合物由 1 个邻菲咯啉合镁阳离子[Mg(H2O)4(phen)]2+、1 个邻苯二甲酸根阴离子C6H4(COO)2)2–、1 个溶剂邻菲咯啉分子和 1 个结晶水分子组成。中心 Mg(II)离子为六配位, 六个配位原子形成畸变的 MgN2O4八面体构型。     

Self-encapsulation of [MII(phen)2(H2O)2]2+ (M=Co, Zn) in one-dimensional nanochannels of [MII(H2O)6(BTC)2]4- (M=Co, Cu, Mn): a high HQ/CAT ratio catalyst for hydroxylation of phenols

Four novel three-dimensional (3D) microporous supramolecular compounds containing nanosized channels, namely, [Co(phen)2(H2O)2]2[Co(H2O)6].2BTC.21.5H2O (1), [Co(phen)2(H2O)2]2[Cu(H2O)6].2BTC.21.5H2O (2), [Co(phen)2(H2O)2]2[Mn(H2O)6].2BTC.18H2O (3), and [Zn(phen)2(H2O)2]2[Mn(H2O)6].2BTC.22.5H2O (4), were synthesized from 1,3,5-benzenetricarboxylate (BTC), 1,10-phenanthroline (phen), and the transition-metal salt(s) by self-assembly. Single-crystal X-ray structural analysis showed that the resulting 3D microporous supramolecular frameworks consist of a two-dimensional (2D) hydrogen-bonded host framework of [MII(H2O)6(BTC)2]4- (M=Co for 1, Cu for 2, Mn for 3, 4) with rectangular-shaped cavities containing [MII(phen)2(H2O)2]2+ (M=Co for 1-3, Zn for 4) guests. The guest complex is encapsulated in the 2D hydrogen-bonded host framework by hydrogen bonding and aromatic pi-pi stacking interactions, forming the 3D hydrogen-bonded framework. The catalytic activities of 1, 2, 3, and 4 were studied using hydroxylation of phenols with 30% aqueous H2O2 as a test reaction. The compounds displayed a good phenol conversion ratio and excellent channel selectivity in the hydroxylation reaction, with a maximum hydroquinone (HQ)/catechol (CAT) ratio of 3.9.     

Hydrothermal syntheses and crystal structures of complex-linked three-Dimensional coordination vanadium selenites: M(4,4'-bipy)(H(2)O)V(2)Se(2)O(10) (M = Co,Ni)

Two inorganic-organic hybrid compounds with the formula M(4,4'-bipy)(H(2)O)V(2)Se(2)O(10) (M = Co, Ni) were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compounds Co(4,4'-bipy)(H(2)O)V(2)Se(2)O(10) (1) and Ni(4,4'-bipy)(H(2)O)V(2)Se(2)O(10) (2), which are structural analogues, crystallize in the triclinic space group Ponemacr; with crystal data a = 7.9665(3) A, b = 8.1974(3) A, c = 13.8096(4) A, alpha = 85.704(2) degrees, beta = 73.5180(10) degrees, gamma = 75.645(2) degrees, V = 837.76(5) A(3), and Z = 2 and a = 7.9489(19) A, b = 8.128(2) A, c = 13.709 A, alpha = 85.838(6) degrees, beta = 73.736(8) degrees, gamma = 75.594(9) degrees, V = 823.5(4) A(3), and Z = 2, respectively. [M(4,4'-bipy)(H(2)O)V(2)Se(2)O(10)] (M = Co, Ni) have a three-dimensional structure and consist of two subunits, [(VO(2))(SeO(3))](-) infinite chains and [M(4,4'-bipy)(H(2)O)](2+) fragments. The [(VO(2))(SeO(3))](-) chains are composed of [V(2)Se(4)O(14)](4)(-) clusters linked by VO(4)N triangular bipyramids. The 4,4'-bipy molecule as a bifunctional organic ligand is directly linked to Co or Ni and V atoms, affording the three-dimensionality. The compounds were characterized by infrared spectroscopy and differential thermal and thermogravimetric analyses.     

Synthesis and Crystal Structure of a Ternary Complex:[Ni(phen)_2(pmal)]·8H_2O

1 INTRODUCTION Molecular structures of metallic complex and intermolecular weak interaction mode have become the focal fields of crystal engineering and supra- molecular chemistry. As we all known, intermole- cular weak interactions include hydrogen bonds[1, 2], π-π staking interaction[3, 4], metal-metal weak inte- raction[5, 6] and chelate-ring-chelate-ring weak inte- raction, et al.[7] Binary, ternary and quaternary car- boxylic acid ligands possess versatile coordination modes with me…     

Hydrothermal synthesis of organic-inorganic hybrid materials: network structures of the bimetallic oxides [M(Hdpa)2V4O12] (M = Co, Ni, dpa = 4,4'-dipyridylamine)

The hydrothermal reactions of MCl(2).6H2O (M = Co, Ni) NaVO3, 4,4'-dipyridylamine (dpa), and H2O yield materials of the type [M(Hdpa)2V4O12] (M = Co (1), Ni (2)). The two-dimensional structures of 1 and 2 are constructed from bimetallic oxide networks (MV4O12)n2n- with monodentate Hdpa projecting the protonated ring into the interlamellar region. The oxide network may be described as ruffled chains of corner-sharing (VO4) tetrahedra linked by (NiO4N2) octahedra into the two-dimensional assembly. Crystal data: C10H10Co0.5N3O6V2(1), monoclinic P2(1)/c, a = 10.388(1) A, b = 7.6749(7) A, c = 16.702(2) A, beta = 102.516(1) degrees, Z = 4. C10H10N3Ni0.5O6V2 (2), monoclinic, P2(1)/c, c = 10.3815(2) A, b = 7.7044(2) A, c = 16.6638(4) A, beta = 102.573(1) degrees, Z = 4.     

A 2D lanthanum coordination polymer with π–π stacking

A 2D lanthanum coordination polymer La₂(1,10-phen)₂(e,a-cis-1,4-chdc)₃ · 2.5H₂O (chdc = cyclohexanedicarboxylic acid; phen = 1,10-phenanthroline) 1 which contains two-dimensional (2-D) lanthanum-organic sheets, was prepared under hydrothermal conditions and characterized by elemental analyses, IR spectra, TG analysis, and single-crystal X-ray diffraction. In the structure of 1, the La site is nine-coordinate by two nitrogen atoms from 1,10-phen and seven oxygen atoms from several 1,4-chdc ligands, connected into a 2-D coordination polymer, with the flexible 1,4-chdc spacers. The 2-D layers are extended into a 3-D framework by π–π interactions between adjacent layers.     

Near-infrared luminescent and magnetic cyano-bridged coordination polymers Nd(phen)n(DMF)m[M(CN)8] (M = Mo, W)

New cyano-bridged coordination polymers [Nd(phen)(2)(DMF)(2)(H(2)O)Mo(CN)(8)]·2H(2)O (1) and [Nd(phen)(DMF)(5)M(CN)(8)]·xH(2)O [M = Mo (2), W (3); phen = 1,10-phenanthroline] have one-dimensional structures with variable number of phenanthroline ligands. Compounds exhibit photoluminescence in the near-infrared region and ferromagnetic Nd(3+)-M(5+) interactions.     

Two novel vanadium tellurites covalently bonded with metal-organic complex moieties: M(phen)V(2)TeO(8) (M = Cu, Ni)

Two novel two-dimensional organic-inorganic hybrid vanadium tellurites M(phen)V(2)TeO(8) (M = Cu (1), Ni (2)) have been hydrothermally synthesized and characterized by the elemental analyses, IR spectra, EPR spectrum, XPS spectra, TG analyses, and single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P2(1)/c, with a = 9.2193(18) A, b = 7.9853(16) A, c = 21.401(4) A, beta = 97.54(3) degrees, and Z = 4. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 9.2163(18) A, b = 7.9897(16) A, c = 21.386(4) A, beta = 97.52(3) degrees, and Z = 4. Compounds 1 and 2 are isostructural, and both exhibit interesting two-dimensional networks with [V(2)TeO(8)]( infinity ) double-chain-like ribbons bridged by metal-organic complex moieties [M(phen)](2+) (M = Cu and Ni). Furthermore, the three-dimensional supramolecular architectures of compounds 1 and 2 are formed by pi-pi stacking interactions of phen groups between adjacent layers.     

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.     

之字链聚合物[Zn(o-bda)(phen)(H2O)]n·nH2O的结构

[Zn(o-bda)(phen)(H₂O)]_n·nH₂O (C22H20N2O6Zn) (1) [where o-bda is o-phenylenediacetic acid dianion and phen is 1,10-phenanthroline] crystallizes in triclinic system, space group P1 with a=0.826 5(4) nm, b=1.042 4(5) nm, c=1.238 1(6) nm, α=76.987(9)°, β=70.987(9)°, γ=78.281(8)°, V=0.9728(8) nm³, Z=2, D_c=1.617 g·cm^-3, μ=1.308 mm^-1 and F(000)=488. Zn(Ⅱ) ion has a distorted trigonal bipyramid coordination geometry formed by two carboxyl O atoms from two different o-bda groups, two N atoms from the phen ligand and one terminal water molecule. Adjacent Zn(Ⅱ) ions are interlinked by o-bda groups into a infinite zigzag chain structure with a Zn…Zn distance of 0.825 6(4) nm. The adjacent zigzag chains may also be paired under direction of supramolecular recognition and attraction through both π-π stacking and hydrogen bonding interactions into molecular zippers, which further interlinked into a three-dimensional supramolecular network by these noncovalent interactions. CCDC: 600935.     

Synthesis and structural and magnetic characterization of {[(phen)(2)Ni](2)(micro-P(2)O(7))} . 27H(2)O and {[(phen)(2)Mn](2)(micro-P(2)O(7))} . 13H(2)O: rare examples of coordination complexes with the pyrophosphate ligand

The reaction in water of M(II) [M = Ni or Mn] with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na4P2O7) in a 2:4:1 stoichiometry resulted in the crystallization of dinuclear complexes featuring the heretofore rare bridging pyrophosphate. Single-crystal X-ray diffraction studies revealed the complexes to be {[(phen)2Ni]2(micro-P2O7)} . 27H2O (1) and {[(phen)2Mn]2(micro-P2O7)} . 13H2O (2) where the asymmetric M(phen)2 units are bridged by bis-bidentate pyrophosphate, each metal ion exhibiting a distorted octahedral geometry. The bridging pyrophosphate places adjacent metal centers at 5.031 A in 1 and 4.700 A in 2, and its conformation also gives rise to an intramolecular pi-pi interaction between two adjacent phen ligands. Intermolecular pi-pi interactions between phen ligands from adjacent dinuclear complexes create an ornate 3D network in 1, whereas a 2D sheet results in 2. The hydrophilic nature of the pyrophosphate ligand leads to heavy hydration with the potential solvent-accessible area for 1 and 2 accounting for 45.7% and 26.4% of their unit cell volumes, respectively. Variable-temperature magnetic susceptibility measurements on polycrystalline samples of 1 and 2 revealed net weak intramolecular antiferromagnetic coupling between metal centers in both compounds with J = -3.77 cm(-1) in 1 and J = -0.88 cm(-1) in 2, the Hamiltonian being defined as H = -JSA.SB. The ability of the bis-bidentate pyrophosphate to mediate magnetic interactions between divalent first row transition metal ions is discussed bearing in mind the number and nature of the interacting magnetic orbitals.     

Crystal Structure and Interaction with DNA of [Ni(phen)(mal)(H2O)2]·3H2O

A new complex [Ni(phen)(mal)(H2O)2]·3H2O (phen = 1,10-phenanthroline,mal2-= malonic acid) has been synthesized by the reaction of nickel nitrate,phen and malonic acid.EA,IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the title complex.Crystal data:monoclinic system,space group P2/c,a =8.937(3),b = 12.163(5),c = 9.725(3)(A),β = 119.36°,C15H19N2O9Ni,Mr= 430.03,Z = 2,F(000) =446,V = 921.3 (A)3,Dc = 1.550 g/cm3,μ = 1.104 mm-1,-10≤h≤ 10,-12≤k≤ 14,-11 ≤l≤7,R =0.0261 and wR = 0.0609 for 4376 (Rint = 0.0203) independent reflections and 1631 observed ones (I＞ 2σ(I)).Ni(Ⅱ) exhibits an octahedral coordination geometry,with hydrogen bonds and π-π interactions stabilizing the whole structure.UV spectrum of the complex interacting with protamine DNA indicates that the title compound interacts with DNA via insertion mode with bonding constant Kb of 1.11 × 104.     

Crystal Structure and Characterization of a Binuclear Cd(II) Quaternary Coordination Complex [Cd2(phen)2Q2(BP)]n (phen = 1,10-Phenanthroline, BP = Biphenyl-4,4--dicarboxylic acid, Q = 8-Hydroxyquinoline Anion)

The structure of a binuclear cadmium(II) quaternary complex, [Cd2(phen)2- Q2(BP)]n 1 (phen = 1,10-phenanthroline, BP = biphenyl-4,4--dicarboxylic acid, Q = 8-hydroxy- quinoline-anion), has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and thermogravimetric analysis.It crystallizes in the monoclinic system, space group P21/n with a = 13.1906(18), b = 10.9623(15), c = 16.947(2) -, β = 111.3430(10)°, V = 2282.5(5) -3, Z = 4, Mr = 556.85, Dc = 1.620 g/cm3, F(000) = 1116, μ = 0.994 mm-1 and S = 1.056.In the structure, 1D chains are connected via biphenyl-4,4--dicarboxylic acid, 8-hydroxy quinoline anion and binuclear cadmium atoms into an infinite 1-D molecular chain architecture.Via aryl ring π-π stacking interactions a supramolecular structure is formed in 1.     

Magneto-structural studies on heterobimetallic malonate-bridged M(II)Re(IV) complexes (M = Mn, Co, Ni and Cu)

The mononuclear Re(IV) compound of formula (PPh(4))(2)[ReBr(4)(mal)] (1) was used as a ligand to obtain the heterobimetallic species [ReBr(4)(μ-mal)Co(dmphen)(2)]· MeCN (2), [ReBr(4)(μ-mal)Ni(dmphen)(2)] (3), [ReBr(4)(μ-mal)Mn(dmphen)(2)] (4a), [ReBr(4)(μ-mal)Mn(dmphen)(H(2)O)(2)]·dmphen·MeCN·H(2)O (4b), [ReBr(4)(μ-mal)Cu(phen)(2)]·1/4H(2)O (5) and [ReBr(4)(μ-mal)Cu(bipy)(2)] (6) (mal = malonate dianion, dmphen = 2,9-dimethyl-1,10-phenanthroline, phen = 1,10-phenanthroline and bipy = 2,2'-bipyridine). The structures of 2 and 5 (single-crystal X-ray diffraction) are made up of neutral [ReBr(4)(μ-mal)M(AA)] dinuclear units [AA = dmphen with M = Co (2) and AA = phen with M = Cu (5)] where the metal ions are connected through a malonate ligand which exhibits simultaneously the bidentate [at the Re(IV)] and monodentate [at the M(II)] coordination modes. The carboxylate-malonate group in them adopts the anti-syn conformation with intramolecular ReM separation of 5.098(8) (2) and 4.947(2) ? (5). The magnetic properties of 1-6 were investigated in the temperature range 1.9-295 K. The magnetic behaviour of 1 is the expected for a magnetically isolated Re(IV) complex with a large value of the zero-field splitting (2D ca. -70 cm(-1)) whereas weak antiferromagnetic interactions between Re(IV) and M(II) are observed in the heterobimetallic compounds 2 (J = -0.63 cm(-1)), 3 (J = -1.37 cm(-1)), 4a (J = -1.29 cm(-1)), 5 (J = -1.83 cm(-1)) and 6 (J = -0.26 cm(-1)). Remarkably, 4b behaves as a ferrimagnetic chain with regular alternating Re(IV) and Mn(II) cations (J = -2.64 cm(-1)).     

高氯酸二水邻菲咯啉合铜配合物的合成和晶体结构

Crystal structure of the title compound， Cu(phen)(H₂O)₂·ClO₄(phen=1，10-phenanthroline)， was deter-mined by X-ray crystallography. It crystallizes in the monoclinic system， space group C2/c with lattice parameters a=1.49071(4)nm， b=1.38594(4)nm， c=0.70292(1)nm， β=108.509(1)° and Z=4; The Cu(Ⅰ) ion is chelated by a phen ligand and two aqua ligands in cis arrangement and assumes a C2 symmetric square-planar geometry with the CuN₂O₂ core. Eight Cu(phen)(H₂O)₂·ClO₄ molecules are interconnected by strong hydrogen bonds between coordinated water molecules and uncoordinated perchlorate anions to form a molecular scale cavities along c axis. The bond distances of Cu-N and Cu-O are 0.2003(4)nm and 0.1973(3)nm， respectively. CCDC： 197600.     

Hydrothermal synthesis, structure and quantum chemistry of transition metal complex supported by metal-oxo cluster [{Ni(phen)2}2(x-Mo8O26)]

A nickel-1,10-phenanthroline complex supported on an octamolybdate, [{Ni(phen)2}2(x- Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2· 6H2O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to monoclinic P21/n space group, a = 1.2952(2), b = 1.6659(10), c = 1.3956(12) nm, b =106.273(8)°, V = 2.8906(5) nm3, Z = 2. 5604 observable reflections (I ＞2s(I)) were used for structure resolution and refinements to converge to final R1 = 0.0414, wR2 = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as x-isomer). The feature of x-[Mo8O26]4- is that it is composed of Mo6O6 ring and two MoO6 octahedra located at cap positions on opposite faces. The Mo6O6 ring contains two octahedral and four trigonal-bipyramidal MoVI atoms. Each x-[Mo8O26]4- unit is bonded with two [Ni(phen)2]2+ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo6O6 ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method.