Solvothermal Syntheses and Crystal Structures of Two New Nonmetal Borates: C4H10N2·B6O8(OH)2 and (NH3CH2CH2NH3)B5O8(OH)

Two new borate compounds, C4H10N2·B6O8(OH)2 1 and (NH3CH2CH2NH3)B5O8(OH)2, have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, elemental analysis and thermal analysis. Compound 1 crystallizes in the monoclinic system, space group P21/c, with a = 8.3318(17), b = 6.2118(12), c = 12.479(3) (A), β = 108.96(3)°, V = 610.8(2) (A)3, Mr = 313.02, Z = 2, Dc= 1.702 g/cm3, μ = 0.150 mm-1, F(000) = 320, R = 0.0387and wR = 0.0924. Its layered structure is linked by infinite covalently coordinated neutral sheets with 3,20-membered window system, which are built up from alternative B6O8(OH)2 subunits donated by two piperzazine nitrogen donors. 2 crystallizes in monoclinic, space group Cc, with a =6.7207(13), b = 11.481(2), c = 12.564(3) (A),β = 95.25(3)°, V= 965.4(3) (A)3, Mr= 261.18, Z= 4, Dc=1.797 g/cm3, μ = 0.164 mm-1, F(000) = 536, R = 0.0396 and wR = 0.0752. Its oxoborate structure is generated from the sheets of 3,9-membered boron rings bonded diamine molecules through electrostatic and H-bonding interactions to form a two-dimensional layered network.     

Synthesis,Crystal Structure,Vibrational Spectroscopy,and Thermal Behavior of Y[B_2O_3（OH）]_3

The hydroxy yttrium hexaborate,Y[B2O3(OH)]3,has been synthesized under mild hydrothermal conditions at 458 K.The crystal structure was solved and refined from single-crystal X-ray diffraction.It adopts a trigonal space group R3c(No.161) with a = 8.3942(4),c = 20.6484(12) ,V = 1260.03(12) 3,YB6H3O12,Mr = 348.79,Z = 6,Dc = 2.758 g/cm3,F(000) = 1008,μ = 7.015 mm-1,R = 0.0321 and wR = 0.0772.Its crystal structure is made up of six-membered rings,alternating three-connected [BO3(OH)] tetrahedra and planar [BO3] trigonal groups,which are interconnected with each other by sharing their common oxygen corners to form a three-dimensional framework structure with six-membered ring channels that are occupied by the yttrium atoms and run along the c axis.FT-IR,Raman,and TG-DTA results are also presented.     

Syntheses and Crystal Structures of Two Novel Cobalt(Ⅱ) Complexes with 2-Amino-5-substituted-1,3,4-thiadiazole as Ligands

Two novel cobalt(Ⅱ) compounds were obtained and characterized by X-ray single-crystal diffraction,IR,1H NMR and elemental analysis.Compound 1 crystallizes in monoclinic,space group P21/n,with a = 18.046(4),b = 11.335(3),c = 19.157(5) ,β = 92.707(3)o,Z = 4,V = 3914.4(16) 3,Mr = 968.56,Dc = 1.644 g/cm3,μ = 1.378 mm-1,F(000) = 1960,the final R = 0.0367 and wR = 0.0895.The crystal of compound 2 is of monoclinic,space group P21/c with a = 8.7253(10),b = 10.9031(13),c = 18.235(2) ,β = 93.2210(10)o,Z = 4,V = 1732.0(3) 3,Mr = 464.21,Dc = 1.780 g/cm3,μ = 1.560 mm-1,F(000) = 932,the final R = 0.0322 and wR = 0.0743.     

Synthesis and Crystal Structure of 3,3'-Bis(5-(N-(4-hydroxylphenyl)imidomethyl)- pyrrol-2-yl)pentane·2CH_3OH

3,3'-Bis(5-(N-(4-hydroxylphenyl)imidomethyl)pyrrol-2-yl)pentane 1 has been synthesized and characterized. The crystal of its methanol complex, 1·(CH3OH)2, belongs to the orthorhombic system, space group Pccn with a = 18.094(2), b = 11.6890(16), c = 13.3629(19) , V = 2826.3(7) 3, Z = 8, C14.5H18N2O2, Mr = 252.31, Dc = 1.186 g/cm3, F(000) = 1080 and μ(MoKα) = 0.080 mm-1. The final R = 0.0662 and wR = 0.1801 for 1908 observed reflections with I 2σ(I), and R = 0.0800 and wR = 0.1948 for all reflections. In the solid state, bridged by included methanol molecules, the molecules of compound 1 form interpenetrated grid structure through N–H···O and O–H···O hydrogen bonds.     

Syntheses,Crystal Structures and Properties of Three New Complexes [Ni（C9N2O2H7）2（CH3OH）2],[Zn（C9N2O2H7）2（H2O）2] and [Cd（C9N2O2H7）2（CH3OH）2]

Three novel metal-organic complexes with formulas [Ni(C9N2O2H7)2(CH3OH)2](1),[Zn(C9N2O2H7)2(H2O)2](2) and [Cd(C9N2O2H7)2(CH3OH)2](3) were synthesized by the reactions of Ni,Zn and Cd salts with ethyl 2-benzimidazolylacetate under hydrothermal conditions or layering technique,and characterized by single-crystal X-ray diffraction analysis,IR spec-troscopy,solid-state luminescent properties and thermogravimetric(TG) analysis.The crystal data for these three complexes are as follows:for 1,monoclinic,space group P21/c,a = 9.384(3),b = 9.634(3),c = 11.292(3) ,β = 95.787(5)°,V = 1015.7(5) 3,Z = 2,F(000) = 492,Dc = 1.547 Kg/m3,μ = 1.002 mm-1,the final R = 0.0451 and wR = 0.0900 for 1833 observed reflections with Ⅰ 2σ(Ⅰ);for 2,orthorhombic,space group Pbca,a = 10.031(4),b = 10.379(4),c = 17.525(7),V = 1824.6(12) 3,Z = 4,F(000) = 928,Dc = 1.645 Kg/m3,μ = 1.392 mm-1,the final R = 0.0452 and wR = 0.0996 for 1661 observed reflections with Ⅰ 2σ(Ⅰ);for 3,monoclinic,space group P21/c,a = 9.9114(13),b =10.4852(15),c = 10.4120(14) ,β = 108.453(5)°,V = 1026.4(2) 3,Z = 2,F(000) = 532,Dc = 1.705 Kg/m3,μ = 1.110 mm-1,the final R = 0.0322 and wR = 0.0805 for 1822 observed reflections with Ⅰ 2σ(Ⅰ).In the three complexes,the ethyl 2-benzimidazolylacetate shows the same chelating mode,and the adjacent units are interlinked into a two-dimensional layer through hydrogen-bonds(O-H···O,N-H···O).     

Synthesis and Crystal Structure of a Novel Compound:[Nd_3(OH)_7(O_2CC_6H_4SO_3)(H_2O)]_n·nH_2O with a Pillar-layered Structure

A novel Nd(Ⅲ) compound,[Nd3(OH)7(O2CC6H4SO3)(H2O)]n·nH2O 1,has been synthesized by the hydrothermal reaction of Nd2O3 and 3-sulfobenzoic acid monosodium salt. It was characterized by IR spectroscopy,elemental analysis,thermogravimetric analysis and single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 13.024(3),b = 10.961(2),c = 12.792(3) ,β = 91.271(3)°,V = 1825.6(7) 3,Z = 4,Mr = 787.97,Dc = 2.867 g/cm3,μ = 8.584 mm-1,F(000) = 1460,S = 1.035,R = 0.0442 and wR = 0.1166 (I 2σ(I)). In this compound,the cross-linkage of Nd atoms by bridging hydroxy groups results in a Nd-O inorganic 200 layer,and such layers are linked by the 3-O3S-C6H4-CO2 dianions into a pillar-layered structure. The lattice water molecules are located in the cavity.     

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)).     

Synthesis and Crystal Structure of （E）-N,N＇- dicyclohexyl- 1-（3-（3,4-dihydroxyphenyl）acryloyl）urea

The title compound, (E)-N,N′-dicyclohexyl-1-(3-(3,4-dihydroxyphenyl)acryloyl)- urea (DDA), has been synthesized and characterized by FT-IR and 1H-NMR spectroscopy, ESI- MS, and X-ray single-crystal diffraction. Its crystallizes in monoclinic, space group C2/c with a = 20.483(12), b = 11.153(6), c = 21.134(12) , β = 117.098(7), V = 4298(4) 3, Z = 8, F(000) = 1664, Dc = 1.195 Mg/m3, Mr = 386.48, μ= 0.082 mm-1, the final R = 0.0474 and wR = 0.1370 for 4853 observed reflections with I > 2σ(I).     

A Pseudo-Keggin Compound: Hydrothermal Synthesis and Crystal Structure of (DETAH)(DETAH_3)_3[V_(18)O_(42)(PO_4)]·(PO_4)·2H_2O

The novel vanadophosphate (DETAH)(DETAH3)3[V18O42(PO4)]·(PO4)·2H2O has been synthesized under hydrothermal conditions and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic, space group C2/c with a = 23.857(3), b = 12.9619(18), c = 20.204(3) , β = 105.692(2)°, V = 6015.0(14) 3, Z = 4, Dc = 2.473 g/cm3, Mr = 2239.68, F(000) = 4432, R = 0.0725, wR = 0.1524 and GOOF = 1.095. The metaloxo cluster contains a novel six-capped pesudo-Keggin structure unit which encloses a disorder PO43- guest.     

Synthesis and Characterization of a Reduced Molybdenum(V) Phosphate, (H_3dien)_2(H_2dien)_2[NaMo_(12)O_(24)(OH)_6-(H_2PO_4)(HPO_4)_5(PO_4)_2]·nH_2O (n = 10.92)

A new reduced molybdenum(V) phosphate (H3dien)2(H2dien)2[NaMo12O24 (OH)6 (H2PO4)(HPO4)5(PO4)2]·nH2O (n = 10.92, dien = diethylenetriamine) has been synthesized under hydrothermal conditions and characterized by elemental analyses, IR and X-ray diffraction. C16H96.84Mo12N12NaO72.92P8 (Mr = 3046.73) crystallizes in the monoclinic system, space group P21/c with a = 13.3575(18), b = 21.907(3), c = 15.654(2) , β = 110.22(2)°, V = 4298.4(10) 3, Dc = 2.354 g/cm3, Z = 2, μ(MoKα) = 1.966 mm-1, F(000) = 2990.4, the final R = 0.0357 and wR = 0.1086 for 8739 observed reflections with I > 2σ(I). It consists of sandwich-shaped cluster anions [Na{Mo6P4}2]10- held together into a three-dimensional supramolecular framework through intermolecular hydrogen-bonding contacts. A probe reaction of the oxidation of acetaldehyde with H2O2 showed that this compound has high catalytic activity in the reaction.     

Synthesis and Crystal Structure of μ_(1,1,3) Formic Bridging 3D Microporous Ni(II) Complex

A μ1,1,3 formic bridging Ni2+ complex [Ni3(HCOO)6·H2O]]n 1 has been synthesi- zed under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 exhibits a 3D open microporous tube formed by covalent and coordination bonds. Complex 1 crystallizes in the monoclinic system, space group P21/c with a = 11.1487(13), b = 9.7763(11), c =17.9685(17) , β = 126.948(6)o, C6H6Ni3O13, Mr = 462.02, V = 1565.2(3) 3, Z = 4, Dc = 1.961 g/cm3, μ = 3.630 mm-1, F(000) = 917.7, Rint = 0.0234, the final R = 0.0234 and wR = 0.0734 for 3469 observed reflections (I>2σ(I)).     

Synthesis,Structure and Photoluminescence of （CH_3-4,4＇-H_2bipy）-（HgCl_4） with CH_3-4,4＇-H_2bipy Generated in Situ

A novel viologen(4,4'bipyridinium)-based complex (CH3-4,4'-H2bipy)(HgCl4) (1),in which the CH3-4,4'-H2bipy (MQ2+) was generated in situ,has been synthesized via hydrothermal reaction and structurally characterized. Complex 1 crystallizes in the space group P21/c of monoclinic system with four formula units in a cell:a = 8.1848(6),b = 21.809(2),c = 9.0285(6) ,β = 107.377(1)°,V = 1538.0(2) 3,C11H11Cl4HgN2,Mr = 513.61,Dc = 2.218 g/cm3,S = 1.009,μ(MoKα) = 10.685 mm-1,F(000) = 956,R = 0.0360 and wR = 0.0812. The crystal structure analysis reveals that the title complex features an isolated structure based on a CH3-4,4'-H2bipy moiety and a mercury atom terminally bound by four chlorine atoms. Photoluminescence investigation reveals a strong emission in blue region,which may originate from π→π* charge-transfer interaction of the CH3-4,4'-H2bipy moiety.     

Synthesis and Crystal Structure of Dimethyl-3-（4-bromophenyl）-1-phenyl-4,5-dihydro-1H-pyrazole-4,5-dicarboxylate

The title compound (C19H17BrN2O4) was synthesized via a one-pot procedure starting from 4-bromobenzaldehyde, dimethyl acetylenedicarboxylate (DMAD) and phenylhydrazine with pyridine as the catalyst. Its structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 11.115(3), b = 8.090(2), c = 20.211(5) , β = 97.032(5)°, V = 1803.7(8) 3, Z = 4, Mr = 417.25, Dc = 1.536 g/cm3, μ = 2.306 mm-1, F(000) = 852, the final R = 0.0403 and wR = 0.0895 for 2215 observed reflections with I 2σ(I).     

Two 3-D Neutral Zn(Ⅱ)-MOFs Generated from the Asymmetric Schiff-base Ligand

Two new Zn(Ⅱ)-MOFs were synthesized based on an asymmetric Schiff-base ligand LH, which is obtained by the condensation of 5-formyl-8-hydroxyquinoline and 3-pyridinecarboxylic acid hydrazide. In different mixed solvents, we get two new isomorphism compounds, [Zn(L)2]·C4H8O2·2MeOH(1) and [Zn(L)2]·CH2Cl2·2MeOH(2). Compounds 1 and 2 have been characterized by single-crystal X-ray diffraction, elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a = 13.856(4), b = 14.156(4), c = 9.620(3) , β = 110.167(5)°, V = 1771.3(9) 3, Dc = 1.500 g/cm3, C38H38N8O8 Zn, Mr = 800.13, F(000) = 832, μ(MoKα) = 0.761 mm-1, Z = 2, the final R = 0.0596 and wR = 0.1221 for 2112 observed reflections(I 2σ(I)). Compound 2 belongs to monoclinic, space group P21/c, with a = 13.575(3), b = 14.130(3), c = 9.485(2) , β = 107.908(3)°, V = 1731.2(6) 3, Dc = 1.529 g/cm3, C35H32Cl2N8O6 Zn, Mr = 796.96, F(000) = 820, μ(MoKα) = 0.926 mm-1, Z = 2, the final R = 0.0527 and wR = 0.1395 for 2501 observed reflections(I 2σ(I)). The Zn(Ⅱ) centers in both 1 and 2 display a distorted octahedral coordination geometry. The octahedral Zn(Ⅱ) nodes and L linkages build up 2-D nets consisting of parallelogram-like grids in the ab plane. The neighboring nets stack through hydrogen bonds to generate 3-D rhombic channels. In 1, the 1,4-dioxane and MeOH guests alternatively arrange in the channels and effectively take up the free space; while in 2, the CH2Cl2 guests are arranged in the channels. In addition, the encapsulated MeOH molecules are bonded to the framework by hydrogen bonds.     

Synthesis and Crystal Structure of the First Diaza-spirobifluorene：2-（Spirobifluorene-2-yl）-3,4-diaza-spirobifluorene

The title compound 2-(spirobifluorene-2-yl)-3,4-diaza-spirobifluorene(C48H28N2,Mr = 632.72) has been synthesized and characterized by 1H NMR,13C NMR and single-crystal X-ray diffraction.The crystal crystallizes in the monoclinic system,space group Cc with a = 13.8523(6),b = 29.3297(13),c = 8.6397(4) ,β = 111.8760(10)°,V = 3257.4(3) 3,Z = 4,Dc = 1.290 mg/m3,μ = 0.075 mm-1,F(000) = 1320,the final R = 0.0425 and wR = 0.1110 for 5288 observed reflections(Ⅰ 2σ(Ⅰ)).     

Synthesis and Crystal Structure of a New Tetracopper Complex [Cu(H_2O)_3Cu(HCDTA)]_2(ClO_4)_2·H_2O

A new tetracopper complex [Cu(H2O)3Cu(HCDTA)]2(ClO4)2·H2O (CDTA = transcyclohexane-1,2-diamine-N,N,N′,N′-tetraacetate) has been prepared and characterized by singlecrystal X-ray diffraction analysis. The crystal adopts space group C2/c with a = 16.990(10), b = 9.150(5), c = 29.318(17) , β = 104.289(9)°, V = 4417(4) 3, Z = 4, C28H52Cl2Cu4N4O31, Mr = 1265.80, Dc = 1.904 g/cm3, μ = 2.130 mm-1, F(000) = 2584, T = 293(2) K, the final R = 0.0328 and wR = 0.0809 for 4938 observed reflections (I 2σ(I)). The tetracopper units are interconnected by weak covalent bonds into a layered structure.     

Syntheses, Crystal Structures and Magnetism of Two New Coordination Polymers [Ni（bix）2Cl2]n and [Co（bix）Cl2]n

The self-assembly reactions of MIICl2 (M = Ni, Co) with the flexible bix ligand [bix = 1,4-bis(imidazole-1-ylmethyl)benzene] yielded a 2D network [NiII(bix)2Cl2]n 1 and a 1D chain [CoII(bix)Cl2]n 2. Their crystal structures have been determined by X-ray single-crystal diffraction analysis. Complex 1 characters a two-dimensional grid-type structure and crystallizes in monoclinic, space group P21/c with a = 7.7231(7), b = 12.7787(9), c = 13.9374(13) , β = 105.419(4)o, C28H28Cl2N8Ni, Mr = 606.19, Ζ = 2, V = 1326.0(2) 3, Dc = 1.518 g/cm3, μ = 0.969 mm-1, F(000) = 628, R = 0.0429 and wR = 0.0783 for 2503 observed reflections (I > 2σ(I)). Compound 2 is a one-dimensional chain and crystallizes in orthorhombic, space group Pbca with a = 11.3696(6), b = 10.2128(6), c = 14.4943(9) , C14H14Cl2CoN4, Mr = 368.12, Z = 4, V = 1683.01(17) 3, Dc = 1.453 g/cm3, μ = 1.334 mm-1, F(000) = 748, R = 0.0317 and wR = 0.0800 for 1778 observed reflections (I > 2σ(I)). Magnetic properties of the title complexes were also investigated.     

Synthesis and Crystal Structure of a Heterometallic Chain Coordination Polymer:{[Ni_2Mn_2L_2(CH_3CH_2OH)(H_2O)]·CH_3OH·2H_2O}_n

A chain-like coordination polymer with the chemical formula of {[Ni2Mn2L2(CH3CH2OH)-(H2O)]·CH3OH·2H2O}n has been synthesized by the assembly reaction of K2NiL·H2O and Mn(OAC)2·4H2O with a 1:1 mole ratio in methanol,where OAC-=CH3COO-and H4L=2-hydroxy-3-[(E)-({2-[(2-hydroxybenzoyl)imino]ethyl}imino)methyl]benzoic acid.The crystal structure was determined by single-crystal X-ray diffraction analysis.It belongs to the triclinic system,space group P1,with a=9.9464(8),b=13.4718(11),c=14.3877(12),α=87.1930(10),β=85.4280(10),γ=74.6470(10)°,V=1852.4(3)3,Z=2,Dc=1.807g/cm3,Mr=1008.03,λ(MoKα)=0.71073,μ(MoKα)=1.794 mm-1,F(000)=1032,R=0.0527 and wR=0.1284(Ⅰ2σ(Ⅰ)).The compound exhibits a chain-like structure formed by dissymmetrical tetranuclear units.     

A Zn(II) 5-Aminoisophthalate Coordination Polymer

The title compound, [Zn(AIP)(4,4-bipy)0.5(H2O)]n·0.75nH2O 1, was synthesized via the hydrothermal reaction of Zn(OAc)2 with 5-aminoisophthalic acid (H2AIP) and characterized by elemental analysis and infrared spectra. The complex crystallizes in monoclinic system, space group P21/c with a = 12.672(1), b = 7.6557(4), c = 16.181(1) , β = 109.187(2)o, V = 1482.6(2) 3, Z = 1, C52H52N8O23Zn4, Mr = 1418.58, Dc = 1.589 g/cm3, F(000) = 724 and μ(MoKα) = 1.685mm-1. The final R = 0.0702 and wR = 0.1524 for 1847 observed reflections with I > 2σ(I), and R = 0.0873 and wR = 0.1664 for all data. X-ray diffraction studies reveal that the title compound has an interesting 2D microporous architecture with guest water molecules inside the channel.     

Synthesis,Crystal Structure,and Magnetic and Water-induced Reversible Transformation Properties of {[Ni(IBG)(μ-H_2O)(H_2O)_2]·2H_2O}_n

A novel NiⅡ complex {[Ni(IBG)(μ-H2O)(H2O)2]·2H2O}n 1(H2IBG = isophthaloylbisglycine) has been synthesized and characterized by single-crystal X-ray diffraction,elemental analysis,IR spectra,and thermogravimetric analysis.It crystallizes in monoclinic,space group P2/c with a = 15.40(2),b = 6.960(10),c = 7.865(11) ,β = 90.32(3)o,V = 843(2) 3,Z = 2,C12H18NiN2O11,Mr = 424.99,Dc = 1.675 g/cm3,F(000) = 440,μ(MoKα) = 1.214 mm-1,the final R = 0.0514 and wR = 0.1247 for 1078 observed reflections with I 2σ(I).In the structure,each NiⅡcenter is situated in the center of a rather regular octahedron.Moreover,thermal stability has been studied and magnetic measurements show antiferromagnetic interactions for this complex.