Syntheses and Crystal Structures of Two 3D Zinc(II) Compounds Involving Coordination and Hydrogen Bonds

1 INTRODUCTION Self-assembly through coordination and hydrogen bonds has been proved to be a powerful tool for con- structing functional organic crystalline materials[1~4]. Except for the important role of H-bonds in the sta- bilization of structures, hydrogen bonding groups namely hydroxyl, amide groups in adjacent coor- dination polymeric chains or discrete lamellas can form hydrogen bonds, which allow for the assembly of well-formed crystalline solid[5, 6]. Our recent inte- rest is foc…     

Cluster-type basic lanthanide iodides [M6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 (M = Nd, Eu, Tb, Dy)

Ln6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)(8) (Ln = Nd, Eu, Tb, Dy) compounds are obtained as the final hydrolysis products of lanthanide triiodides in an aqueous solution. Their X-ray crystal structure features a body-centered arrangement of oxygen-centered {Ln6X8}8+ cluster cores: [Nd6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1310.4(3) pm, b = 1502.1(3) pm, c = 1514.9(3) pm, 3384 reflections with I0 > 2sigma(I0), R1 = 0.0340, wR2 = 0.0764, GOF = 1.022, T = 298(2) K], [Eu6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1306.6(2) pm, b = 1498.15(19) pm, c = 1499.41(18) pm, 4262 reflections with I0 > 2sigma(I0), R1 = 0.0540, wR2 = 0.0860, GOF = 0.910, T = 298(2) K], [Tb6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1296.34(5) pm, b = 1486.13(7) pm, c = 1491.88(6) pm, 4182 reflections with I0 > 2sigma(I0), R1 = 0.0395, wR2 = 0.0924, GOF = 1.000, T = 298(2) K], and [Dy6(mu6-O)(mu3-OH)8(H2O)24]I8(H2O)8 [Pearson code oP156, orthorhombic, Pnnm (No. 58), Z = 2, a = 1296.34(5) pm, b = 1486.13(7) pm, c = 1491.88(6) pm, 3329 reflections with I0 > 2sigma(I0), R1 = 0.0389, wR2 = 0.0801, GOF = 0.992, T = 298(2) K.     

One-dimensional Inclusion Polymers of Calix[4]arene Monomethoxycarboxylic Acid

X-ray crystal structures of the inclusion complexes of calix[4]arene monomethoxycarboxylic acid 1 （C30H2606） with acetontrile and acetone are reported. The crystal of C30H26O6·CH3CN is of monoclinic, space group P2 1/c with a = 11.691（5）, b = 13.753（5）, c = 17.072（7）A, β = 100.104（7）°, C32H29NO6, Mr = 523.56, V = 2702.4（18）A^3, Z = 4, De= 1.287 g/cm^3, μ（MoKα） = 0.089 mm^-1, T = 293（2） K, 5570 independent reflections with 3220 observed ones （1 〉 2σ（I））, R = 0.0521 and wR = 0.1132 with GOF = 1.042 （R = 0.1055 and wR = 0.1350 for all data）. The data for C30H26O6·CH3COCH3： monoclinic, space group P2 1/c, α = 12.366（4）, b = 12.119（4）, c = 18.796（6） A, β = 90.871（6）°, C33H32O7, Mr = 540.59, V = 2816.6（16）A^3, Z = 4, Dc = 1.275 g/cm^3, μ（MoKα） = 0.089 mm^-1, T = 293（2） K, 5783 independent reflections including 2580 observed ones （I 〉 2σ（I））, R = 0.0555 and wR = 0.1424 with GOF= 0.975 （R = 0.1601 and wR = 0.1884 for all data）. Their architectures exhibit one-dimensional inclusion polymers which are mediated head-to-tail by the guests.     

From Chain to Layer Structure: ZnⅡ Coordination Polymers Derived from Diphenic Acid

Three ZnⅡ coordination polymers, [Zn(py)(H2O)(dpa)]n 1, [Zn2(4,4'-bipy)2(dpa)2]n 2 and [Zn(bpe)(H2O)2(Hdpa)2]n 3 (py = pyridine, H2dpa = diphenic acid, 4,4'-bipy = 4,4'-bipyridine,bpe = 1,2-bis(4-pyridyl)ethane), were synthesized and characterized by X-ray single-crystal structure determination. 1 crystallizes in monoclinic, space group C2/c with a = 23.014(3), b = 8.7184(13), c = 18.091(3) (A), β = 95.964(3)°, V = 3610.2(9) (A)3, Z = 8, C19H15NO5Zn, Mr = 402.69,Dc= 1.482 g/cm3, F(000) = 1648, μ(MoKα) = 1.389 mm-1, the final R = 0.0431 and wR = 0.1120 for 4239 observed reflections with I ＞ 2σ(Ⅰ). 2 crystallizes in orthorhombic, space group Fddd with a = 23.1613(5), b = 24.0324(6), c = 29.4785(1) (A), V= 16408.4(5) (A)3, Z = 32, C24H16N2O4Zn, Mr = 461.76, Dc= 1.495 g/cm3, F(000) = 7552, μ(MoKα) = 1.232 mm-1, the final R = 0.0542 and wR = 0.1724 for 3632 observed reflections with I ＞ 2σ(Ⅰ). 3 crystallizes in orthorhombic, space group C2/c with a = 19.142(4), b = 13.862(3), c = 15.625(3) (A), β = 122.404(3)°, V = 3500.3(11) (A)3, Z = 8,C20H17NO5Zn0.50, Mr = 384.03, Dc= 1.457 g/cm3, F(000) = 1592,μ(MoKα) = 0.766 mm-1, the final R = 0.0400 and wR = 0.1210 for 4024 observed reflections with I ＞ 2σ(Ⅰ).     

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.     

ZnTPP Axially Coordinated with a Novel Dipyridylamine Ligand: Hydrothermal Synthesis and Crystal Structure

A novel complex ZnTPPL1·3DMF 1(TPP = tetraphenylporphyrin,L1 = N-(4-(9-carbazolyl) phenyl)-N,N-di(4-pyridyl)amine) was prepared by a hydrothermal method and characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.Compound 1 crystallizes in triclinic,space group P1 with a = 13.3082(2),b = 14.3276(2),c = 18.6120(3) ,α = 109.853(1),β = 95.054(1),γ = 98.832(1)°,V = 3260.57(9) 3,Z = 2,Dc = 1.334 g/cm3,C81H69N11O3Zn,Mr = 1309.84,μ(MoKα) = 0.438 mm-1,F(000) = 1372,GOF = 1.159,the final R = 0.0482 and wR = 0.1479 for 12091 observed reflections(Ⅰ 2σ(Ⅰ)).Crystal structure analyses revealed that L1 utilizes one pyridyl N atom to bind Zn via axial coordination,affording a 1:1 complex.The binding constant was estimated to be 1.74(7) × 104 M-1 from electronic spectra measurements.     

二维纳米空洞方格:诺氟沙星锰(Ⅱ)配合物

The reactions of norfloxacin (H-Norf) with Mn(ClO₄)₂·6H₂O and Mn(OH)₂ yield Mn(H-Norf)(ClO₄)₂·2H₂O (1) and [Mn(Norf)₂·4H₂O]_n (2) , respectively. 1 is monomeric while 2 has a novel 2D neutral square grid with an antibacterial drug as building block. Crystal data for 1: triclinic, space group P1 (No.2), a=9.0939(3), b=9.4395(3), c=12.7182(3)?, α=111.447(2), β=90.340(2), γ=112.357(1)°, V=926.34(5)?³, Z=1, ρ_cacl=1.664g·cm^-3. MoKα radiation (λ=0.71073?), T=293(2)K, μ=0.595mm^-1, R₁=0.0692, wR₂=0.1482 for 2320 observed reflections from 4390 independent reflections, GOF=0.940; Crystal data for 2: Monoclinic, P2₁/c, a=5.7530(12), b=21.865(4), c=13.343(3)?, β=98.25(3)°, V=1661.1(6)?³, Z=2, ρ_cacl=1.527g·cm^-3, T=293(2)K, μ=0.477mm^-1, R₁=0.0531, wR₂=0.1552 for 2070 observed reflections from 2870 independent reflections, GOF=1.384. CCDC: 140819; 151063.     

Synthesis, characterization, and structure of macrocyclic mono- and C2-symmetric, binuclear nickel calixsalen complexes

Mono- (3a,b) and binuclear (4a,b) tetradentate NiII complexes of a series of 26-membered macrocyclic salen dimers, [salen(CH2)]2, are prepared in good yield by solvent-controlled reaction with Ni(OAc)2. The mononuclear complex 3b crystallizes in the trigonal space group 3P1(#144), a = 18.2566(2) A, c = 15.9244(2) A, V = 4596.57(8) A3, and Z = 3. Refinement converged with R = 0.054 and Rw = 0.049 for 6852 reflections with I > 2.003 sigma(I). The NiII in complex 3b coordinates in an approximate square planar geometry to one of the two available tetradentate salen sites. Complex 4b crystallizes in the orthorhombic space group P2(1)2(1)2(1)(#19), a = 19.531(2) A, b = 22.891(3), c = 13.373(1) A, V = 5960(1) A3, and Z = 4. The refinement converged with R = 0.067 and Rw = 0.065 for 3752 reflections with I > 2.003 sigma(I). Complex 4b coordinates two distorted square planar, cofacially oriented NiII-salen units held 7.1 A apart by a rigid, syn-folded macrocyclic structure. The solution spectroscopic data and solid-state crystallographic data of 3b and 4b demonstrate the presence of a molecular-sized cavity which shows host-guest properties. Reaction of the flexible 32-membered disalen macrocycle [salen(OCH2CH2O)]2 with Ni(OAc)2 resulted in formation of a binuclear complex, 5. Complex 5 crystallizes in the triclinic space group P1(#1), a = 10.366(4) A, b = 12.170(3) A, c = 10.021(2) A, alpha = 106.29(2) degrees, beta = 91.69(2) degrees, gamma = 68.63(2) degrees, V = 1126.3(5) A3, and Z = 1. The refinement converged with R = 0.052 and Rw = 0.053 for 2385 reflections with I > 2.003 sigma(I). The binuclear complex 5 contains two cofacially oriented, square planar NiII-salen groups lying 3.5 A apart in an anti-folded macrocyclic structure.     

Synthesis, structure, and reactivity of ruthenium carboxylato and 2-oxocarboxylato complexes bearing the bis(3,5-dimethylpyrazol-1-yl)acetato ligand

A series of ruthenium(II) acetonitrile, pyridine (py), carbonyl, SO2, and nitrosyl complexes [Ru(bdmpza)(O2CR)(L)(PPh3)] (L = NCMe, py, CO, SO2) and [Ru(bdmpza)(O2CR)(L)(PPh3)]BF4 (L = NO) containing the bis(3,5-dimethylpyrazol-1-yl)acetato (bdmpza) ligand, a N,N,O heteroscorpionate ligand, have been prepared. Starting from ruthenium chlorido, carboxylato, or 2-oxocarboxylato complexes, a variety of acetonitrile complexes [Ru(bdmpza)Cl(NCMe)(PPh3)] (4) and [Ru(bdmpza)(O2CR)(NCMe)(PPh3)] (R = Me (5a), R = Ph (5b)), as well as the pyridine complexes [Ru(bdmpza)Cl(PPh3)(py)] (6) and [Ru(bdmpza)(O2CR)(PPh3)(py)] (R = Me (7a), R = Ph (7b), R = (CO)Me (8a), R = (CO)Et (8b), R = (CO)Ph) (8c)), have been synthesized. Treatment of various carboxylato complexes [Ru(bdmpza)(O2CR)(PPh3)2] (R = Me (2a), Ph (2b)) with CO afforded carbonyl complexes [Ru(bdmpza)(O2CR)(CO)(PPh3)] (9a, 9b). In the same way, the corresponding sulfur dioxide complexes [Ru(bdmpza)(O2CMe)(PPh3)(SO2)] (10a) and [Ru(bdmpza)(O2CPh)(PPh3)(SO2)] (10b) were formed in a reaction of the carboxylato complexes with gaseous SO2. None of the 2-oxocarboxylato complexes [Ru(bdmpza)(O2C(CO)R)(PPh3)2] (R = Me (3a), Et (3b), Ph (3c)) showed any reactivity toward CO or SO2, whereas the nitrosyl complex cations [Ru(bdmpza)(O2CMe)(NO)(PPh3)](+) (11) and [Ru(bdmpza)(O2C(CO)Ph)(NO)(PPh3)](+) (12) were formed in a reaction of the acetato 2a or the benzoylformato complex 3c with an excess of nitric oxide. Similar cationic carboxylato nitrosyl complexes [Ru(bdmpza)(O2CR)(NO)(PPh3)]BF4 (R = Me (13a), R = Ph (13b)) and 2-oxocarboxylato nitrosyl complexes [Ru(bdmpza)(O2C(CO)R)(NO)(PPh3)]BF4 (R = Me (14a), R = Et (14b), R = Ph (14c)) are also accessible via a reaction with NO[BF4]. X-ray crystal structures of the chlorido acetonitrile complex [Ru(bdmpza)Cl(NCMe)(PPh3)] (4), the pyridine complexes [Ru(bdmpza)(O2CMe)(PPh3)(py)] (7a) and [Ru(bdmpza)(O2CC(O)Et)(PPh3)(py)] (8b), the carbonyl complex [Ru(bdmpza)(O2CPh)(CO)(PPh3)] (9b), the sulfur dioxide complex [Ru(bdmpza)(O2CPh)(PPh3)(SO2)] (10b), as well as the nitrosyl complex [Ru(bdmpza)(O2C(CO)Me)(NO)(PPh3)]BF4 (14a), are reported. The molecular structure of the sulfur dioxide complex [Ru(bdmpza)(O2CPh)(PPh3)(SO2)] (10b) revealed a rather unusual intramolecular SO2-O2CPh Lewis acid-base adduct.     

From Chain to Layer Structure: Zn~(II) Coordination Polymers Derived from Diphenic Acid

1 INTRODUCTION The rational design and synthesis of metal-organic coordination polymers have generated considerable interest in supramolecular chemistry and material science owing to their intriguing structural diver- sities and potential applications as functional mate- rials[1～3]. Up to now, some structural motifs with specific topologies and functions have been con- structed through rational combination of organic li- gands containing appropriate coordination sites and metal ions beari…     

Hydrothermal Synthesis,Structure and Magnetic Property of a Novel Hexa-Ni~Ⅱ Substituted Polyoxometalate

A novel hexa-NiⅡ substituted trilacunary Keggin polyoxometalate [{Ni6（μ3- OH）3（en）3（H2O）6}（B-α-PW9O34）]-6H2O 1 （en = ethylenediamine） has been hydrothermally synthesized and characterized by IR spectra, elemental analysis, thermogravimetric analysis （TGA）, single-crystal X-ray diffraction and magnetic property. Compound 1 crystallizes in the hexagonal space R3c with a = 20.4124（5）, c = 21.4427（4）A, γ = 120.000°, V = 7737.5（3）A3, Z = 6, GOF = 1.083, R （wR） = 0.0317 （0.0610）. Single-crystal X-ray diffraction indicates that 1 contains a hexa-Nin substituted trivacant Keggin [{Ni6（μ3-OH）3（en）3（H2O）6}（B-α-PW9O34）] unit. The magnetic study shows the presence of ferromagnetic coupling interactions within hexa-Nin clusters with J1 = 0.69 cm-1 and J2 = 0.92 cm^-1 for 1.     

Synthesis,Crystal Structure and Fluorescence Properties of a 3D Framework Based on Hexanuclear Lanthanum 5-Nitroisophthalate Entities

The reaction of lanthanum(Ⅲ) nitrate and 5-nitroisophthalic acid in isopropanol/H2O under hydrothermal conditions leads to a 3D lanthanum-containing coordination polymer with the general chemical formula {[La6(Nip)9(H2O)4 ]·(H2O)4 }∞(1,Nip=5-nitroisophthalate).The single-crystal X-ray analyses show that this compound crystallizes in the orthorhombic system,space group Ima2 with a=9.7769(12),b=28.239(3),c=21.149(2),V=5839.1(11)3,Z=2,Mr=2859.61,Dc =1.626 g/cm 3,F(000)=2752.14040 reflections are collected,of which 5275 are unique (R int=0.0241).Final GOOF=1.083,R=0.0406 and wR=0.1182,R indices based on 5183 reflections with I>2σ(I)(refinement on F2),443 parameters,1 restraint.Lp and absorption corrections were applied,=2.242mm-1.Absolute structure parameter x=0.08(3).The crystal structure can be described as the butterfly-liked hexanuclear lanthanum entities {La6O6(CO2)8 } covalently linked to each other by nitroisophthalate ligands into an intricate three-dimensional structure.The fluorescence spectroscopy of compound 1 has been investigated.     

A New 3D Supramolecular Network Formed by [Zn_3（2,6-Pyridinedicarboxylate）_3Cl_4]~（4-）and 4-Carboxypyridinium

A new compound [Zn3(C7NO4H3)3Cl4]·[C6NO2H6]4·4H2O (I) has been synthesized and structurally characterized by X-ray crystallography.It crystallizes in monoclinic,space group C2/c with a=16.9018(14),b=12.6902(10),c=25.1170(2),β=90.54°,V=5387.0(8)3,Z=4,Zn3C45H41Cl4N7O24,Mr=1401.76,Dc=1.728 g/cm3,F(000)=2840,μ(MoKa)=1.615 mm-1,the R= 0.0758 and wR=0.2060 for 3468 observed reflections (I 2σ(I)).Analysis of single-crystal X-ray diffraction data shows that compound I displays an interesting example of 3D supramolecular networks with perfect neutral and ionic hydrogen bonding array.     

Synthesis and Crystal Structure of a Zinc(Ⅱ) Complex Salt with the Schiff Base of Picolinaldehyde N-oxide and Semicarbazone

The title zinc(Ⅱ) complex salt [Zn(H2O)6](ClO4)2·(PNOS)4, where PNOS is derived from picolinaldehyde N-oxide with semicarbazone, has been prepared and structurally characterized by X-ray single-crystal analysis. It crystallizes in triclinic, space group P1 with a = 7.529(3),b = 10.206(4), c = 14.678(6) A, α = 86.293(6), β = 87.686(7), γ= 81.382(6)°, C28H44Cl2N16O22Zn,Mr = 1093.06, V= 1112.3(8) A3, Z = 1, Dc = 1.632 g/cm3, S = 1.089,μ(MoKα) = 0.773 mm-1 ,F(000) = 564, the final R = 0.0438 and wR = 0.1076 for 3888 independent reflections with Rint =0.0224. The crystal structure possesses a [Zn(H2O)6]2+ cation, two ClO4- anions and four PNOSs.In the crystal structure, Zn2+ cation is located at the symcenter and coordinated by six water molecules. In [Zn(H2O)6]2+, an elongate octahedral complex cation, the average Zn-O bond length is 2.087(2) A. There exist a lot of H bonds in the structure, linking the cation [Zn(H2O)6]2+, anion ClO4-and PNOS to form a 3D network.     

Syntheses and Crystal Structures of Ternary Complexes of Zinc(Ⅱ) and Cadmium(Ⅱ) with 3-Aminobenzoic Acid and 1,10-Phenanthroline

Two new ternary complexes [Zn(3-aba)2(phen)](2.58H2O 1 and {[Cd(3-aba)- (phen)2]·(NO3)·(1.5H2O)}n 2 (3-aba = 3-aminobenzoic acid anion, phen = 1,10-phenanthroline) were synthesized and characterized by elemental analysis, IR, UV spectrum and X-ray diffraction. Complex 1 crystallizes in the rhombohedral system, space group R with a = 3.5733(3), b = 3.5733(3), c = 1.1231(2) nm, V = 12.419(3) nm3, C26H25.17N4O6.58Zn, Mr = 564.37, Z = 18, F(000) = 5253, μ = 0.937 mm-1, Dc = 1.358 g/cm3, R = 0.0668 and wR = 0.1690 for 2424 observed reflections (I > 2σ(I)). Complex 2 belongs to the tetragonal system, space group P4/ncc with a = 2.88451(10), b = 2.88451(10), c = 1.55571(11) nm, V = 12.9441(11) nm3, C31H25CdN6O6.50, Mr = 697.97, Z = 16, F(000) = 5648, μ = 0.727 mm-1, Dc = 1.433 g/cm3, R = 0.0607 and wR = 0.1742 for 3468 observed reflections (I > 2σ(I)). Complex 1 displays a mononuclear structure. The carboxylate group of 3-aminobenzoic acid anion coordinates to Zn(Ⅱ) in a chelating bidentate mode, and the nitrogen atom of the ligand does not involve in coordination. Complex 2 exhibits a one-dimensional chain structure with 3-aminobenzoic acid anion coordinating to Cd(Ⅱ) in a μ2-bridging mode through its nitrogen atom and one of its oxygen atoms.     

Synthesis and Crystal Structure of a New One-dimensional Double Helical-chain Polymer, {Zn（O2CC12H8CO2）（H2O）}n

1 INTRODUCTION Pronounced interest has been put in the field of coordination polymeric complexes owing to their fas- cinating molecular topologies[1～3] along with poten- tial applications as functional materials[4～6]. In par- ticular, complexes with helical structures attract much attention of scientists[7, 8] mainly due to their simi- larity to the structure of DNA molecule. To obtain new complexes, solv- and hydrothermal routes are currently used. In this way, the organic ligand act…     

Design,Synthesis and Crystal Structure of Two One-dimensional Zigzag Chain-like Compounds

Two one-dimensional chain-like cyanide-bridged compounds, [Fe（Phen）2（CN）2Ni（Cyclam）]（ClO4）2·DMF-2H2O 1 （Cyclam = 1,4,8,11-tetraaza-cyclotetradecane, Phen = 1,10-phenanthroline, and DMF = N,N-dimethylformamide） and [Fe（Phen）2（CN）2Zn（Cyclam）]（PF6）2·CH3CN 2, were prepared by the reaction of [Fe（Phen）2（CN）2]·2H2O with M（Cyclam）^2＋ （M = Ni, Zn）. In complexes 1 and 2, the metal atoms are connected alternatively with CN groups. X-ray structure and IR analyses for 1 and 2 were performed. Structure analysis revealed that both complexes are centrosymmetric and the geometry around each metal atom is an octahedron. The two complexes crystallize in triclinic with space group of P^1-. For 1, a = 10.439（4）, b = 14.976（7）, c = 15.914（8）A,α = 83.168（15）, β = 74.338（15）, γ = 78.023（15）°, V = 2338.3（18）A^3, Z = 2, Mr = 1035.37, Dc = 1.471 g/cm^3, F（000） = 1076,μ = 0.895 mm^-1, the final R = 0.0616 and wR = 0.1414 for 5849 observed reflections （1 〉 2σ（I））. For 2, a = 9.656（6）, b = 15.404（9）, c = 15.822（10）A, α = 78.68（2）, β= 78.917（19）, γ = 77.15（2）°, V = 2223（2）A^3, Z = 2, Mr = 1064.87, Dc = 1.587 g/cm^3, F（000） = 1078,μ = 1.032 mm^-1, the final R = 0.0672 and wR = 0.1595 for 6819 observed reflections （I 〉 2σ（I））.     

Hydrothermal Synthesis and Crystal Structure of a Novel Composite Keggin-type Arsenotungstate： [Ni（phen）2] [Hphen] （AsW12O40）

A novel polyoxometalate-based composite compound [Ni(phen)2][Hphen](AsW12O40) (phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TGA, ESR spectroscopy and single-crystal X-ray diffraction. Each structure unit of 1 consists of one polyoxoanion AsW12O403-, one free phenanthroline molecule and one coordination cation [Ni(phen)2]2+. The title compound crystallizes in the orthorhombic system, space group P212121, with a = 12.2383(7), b = 21.0884(11), c = 22.3237(12) , V = 5761.4(5) 3, Mr = 3520.44, Z = 4, Dc = 4.059 g/cm3, F(000) = 6204, μ(MoKα) = 24.844 mm-1, GOF = 1.022, the final R = 0.0376 and wR = 0.0742 (I > 2σ(I)) for 865 parameters and 9637 observed reflections with I > 2σ(I).     

Synthesis and Uncommon Structural Characterization of Novel Zinc and Cadmium Complexes with Imino Nitroxide Radical

Two novel complexes {[Zn(IM4py)2(tp)(H2O)]·2H2O}n 1 and {[Cd(IM4py)2(tp)- (H2O)]·1.25H2O}n 2 (IM4py = 2-(4'-pyridinyl)-4,4,5,5-tetramethylimidazoline-1-oxyl and tp = terephthalate dianion) have been synthesized and characterized by elemental analyses, IR spectrum and single-crystal X-ray diffraction. Crystal data for complex 1: monoclinic, space group C2/c, a = 20.648(7), b = 12.130(4), c = 14.036(4) , β = 106.351(5)o, C32H42N6O9Zn, Mr = 720.09, V = 3373.3(2) 3, Z = 4, Dc = 1.418 g/cm3, μ(MoKα) = 0.790 mm-1, F(000) = 1512, the final R = 0.0407 and wR = 0.0894 for 3480 independent reflections with Rint = 0.0432. Crystal data for complex 2: monoclinic, space group C2/c, a = 21.332(6), b = 12.063(3), c = 14.246(4) , β = 106.704(4)o, C32H40.50N6O8.25Cd, Mr = 753.60, V = 3511.2(2) 3, Z = 4, Dc = 1.426 g/cm3, μ(MoKα) = 0.679 mm-1, F(000) = 1554, the final R = 0.0419 and wR = 0.0961 for 3627 independent reflections with Rint = 0.0440. The framework structures of complexes 1 and 2 are 3-D networks via the hydrogen bonds among 1-D chains. The notable characteristics of the two complexes are that the coordination polyhedron of Zn(II) adopts a rare distorted five-coordinate square pyramidal geometry in 1, and the Cd(II) complex exhibits an unusual distorted seven-coordinate pentagonal bipyramid in 2.     

两个镉的配位聚合物的原位水热合成、晶体结构与荧光性质

在水热条件下, 以3-氨基-1,2,4-三唑-5-甲酸(AmTHZAC)为配体, 原位反应得到了两个镉的配位聚合物 Cd(AmTAZ)Cl(1)和[Cd(AmTAZ)(BDC)(H2O)2]·1.25H2O(2)(AmTAZH=3-amino-1,2,4-triazole, H2BDC=benzene-1,4-dicarboxylic acid), 采用红外光谱、差热-热重、CHN元素分析及单晶X射线衍射等手段对晶体结构进行了表征, 并研究了化合物1和2的荧光性质. 化合物1属正交晶系, P2(1)2(1)2(1)空间群, a=0.6452(3) nm, b=0.7848(5) nm, c=1.0449(6) nm, V=0.5291(5) nm3, Z=4, 最后一致性因子[I＞2σ(I)], R1=0.0226, wR2=0.0377, GOF=1.087. 化合物2属正交晶系, Pmc2(1)空间群, a=0.7100 nm, b=0.9920 nm, c=1.2561 nm, V=0.8847 nm3, Z=8, 最后一致性因子[I＞2σ(I)], R1=0.0934, wR2=0.2456, GOF=1.031.