Synthesis and Crystal Structure of a New Iron Complex with Cyclic Water Hexamers [Fe(CDTA)(H_2O)]·[Fe(1,10-phen)_3]·10H_2O·2OH

The title complex [Fe(CDTA)(H2O)]·[Fe(1,10-phen)3]·10H2O·2OH (CDTA = transcyclohexane-1,2-diamine-N,N,N,N′-tetraacetate) has been prepared and characterized by single-crystal X-ray diffraction analysis. The crystal adopts space group P with a = 12.793(4), b = 14.104(5), c = 17.880(5), V = 2792.2(1)3, Dc = 1.459 g/cm3, C50H66Fe2N8O21, Mr = 1226.81, F(000) = 1284, μ = 0.604 mm-1, Z = 2, R = 0.1055 and wR = 0.2581 for 8675 observed reflections (I > 2σ(I)). X-ray crystallography analysis exhibits that the title compound consists of two crystallographically independent molecules [Fe(CDTA)(H2O)] and [Fe(1,10-phen)3], and they are connected through O-H···O hydrogen bonds and π···π stacking interactions forming a 3D supramolecular structure. Interestingly, there is a cyclic water hexamer with chair conformation in this complex.     

Synthesis,Characterization and Crystal Structure of an Inorganic-organic Composite Metatungstate:[Co(4,4′-bipy)_2(H_2O)_4](4,4′-H_2bipy)_2[H_2W_(12)O_(40)]·5.5H_2O

A novel hybrid compound [Co(4,4'-bipy)2(H2O)4](4,4'-H2bipy)2[H2W12O40]·5.5H2O has been synthesized from an acidified aqueous solution and characterized by elemental and thermal analyses,IR and UV spectroscopy,and single-crystal X-ray structure determination. Structure analysis indicates that the title compound is of monoclinic,space group C2/c,with a=21.315(9),b=15.303 (7),c=24.139(10),β=105.170(5)o,V=7599(6)3,Mr=3706.99,Z=4,F(000)=6616,Dc=3.231,μ=18.395 mm-1,R=0.0652 and wR=0.1594. X-ray crystallographic study shows that the title compound consists of one [Co(4,4'-bipy)2(H2O)4]2+ cation,two diprotonated 4,4'-bipyridine molecules,5.5 water molecules of crystallization,and one metatungstate polyoxoanion [H2W12O40]6-,which approaches an effective Td point symmetry. TG-DTA analysis indicates that the framework of the metatungstate polyoxoanion is collapsed at 587.0 ℃.     

Hydrothermal Synthesis and Crystal Structure of a Keggin Polyoxometalate [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O

A Keggin-type tungstosilicate compound [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O 1 （bipy = bipyridine） was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 （C40H40Co2N8O44SiW12） crystallizes in the triclinic system, space group P1 with a = 10.4979（6）, b = 13.3946（7）, c = 13.5756（8）A, α= 70.0769（18）, β = 68.910（3）, γ = 74.186（4）°, V = 1649.84（16）A^3, Mr = 3688.95, Z = 1, Dc = 3.713 mg·m^-3, μ = 21.432 mm^-1, F（000） = 1644, S = 1.058, the final R = 0.0511 and wR =0.1023 for 6523 observed reflections （I 〉 2σ（I））. Compound 1 consists of two coordinated cation fragments [Co^Ⅱ（2,2′-bipy）2（H2O）]^2＋, one normal Keggin polyanion unit [SiW^Ⅵ12O40]^4- and two lattice water molecules. To be noted, each polyanion unit is linked to two cation fragments by its two surface terminal oxygen atoms and two cobalt atoms of two cation fragments forming an organic-inorganic hybrid unit in 1. Furthermore, the compound shows strong photoluminescence property in the solid state at room temperature.     

Synthesis and Crystal Structure of a Two-dimensional Cadmium Complex Based on Terephthalate and 1-Methyl-2,2'-bibenzimidazole

The title complex, Cd(MeHbibzim)(1,4-bdc)n (1, MeHbibzim = 1-methyl-2,2'- bibenzimidazole, 1,4-bdc = terephthalate), was synthesized with hydrothermal reactions. The compound crystallizes in monoclinic, space group C2/c with a = 9.822(4), b = 18.510(7), c = 22.372(9), β = 98.359(6)°, C23H16CdN4O4 , Mr = 524.81, V = 4024(3)3 , Z = 8, Dc = 1.733 g/cm3 , μ(MoKα) = 1.126 mm-1 , F(000) = 2096, the final R = 0.0597 and wR = 0.1374 for 3906 observed reflections (Ⅰ > 2σ(Ⅰ)). X-ray diffraction analysis reveals that the Cd atom is coordinated by two nitrogen atoms from the chelating MeHbibzim and three carboxyl oxygen atoms from three terephthalate ligands, thus forming a distorted square pyramidal coordination sphere, CdN2O3. Every two Cd atoms are linked together via two carboxyl groups into a dinuclear unit with Cd···Cd separation of 3.806(4). The dinuclear building units are linked by terephthalate ligands into two-dimensional layers, which are further aggregated into a 3D framework via hydrogen bonding interactions.     

[Co(enMe)_3]_2[As_8V_(14)O_(42)(H_2O)]·10H_2O的水热合成、性质和晶体结构

合成了一种新的砷-钒-氧簇合物[Co(enMe)3]2[As8V14O42(H2O)]10H2O(enMe为1,2-丙二胺),用元素分析、IR和TGA-DTA等进行了表征,并用X射线衍射法测定了晶体结构。结果表明,该晶体属单斜晶系,C2/c空间群,晶胞参数a=28.990(7),b=15.540(6),c=22.77(1),b=131.24(4),Mr=2744.68,V=7714(7)3,Z=4,F(000)=5232,m(MoKa)=7.239mm-1,Dc=2.363g/cm3,R=0.069,Rw=0.073。结构测定表明,结构中簇阴离子[As8V14O42(H2O)]4-与配位阳离子[Co(enMe)3]2+之间靠静电作用相结合,同时通过氢键构成无限的三维骨架结构。     

Synthesis and Crystal Structure of a Novel 1D Coordination Polymer:[Pr(BYBA)_3(H_2O)_2]·[Pr(BYBA)_3(H_2O)]

The novel coordination polymer [Pr(BYBA)3(H2O)2]·[Pr(BYBA)3(H2O)] (BYBAH=2-benzoylbenzoic acid) was yielded by hydrothermal synthesis,determined by single-crystal X-ray diffraction,and characterized by FT-IR and UV-Vis spectra. The crystal crystallizes in the triclinic system,space group P1 with a=9.112(3),b=14.644(5),c=27.076(11),α=84.223(3),β= 87.816(4),γ=88.902(4)o,V=3592(2)3,C84H60O21Pr2,Mr=1687.14,Z=2,F(000)=1700,Dc= 1.560 g/cm3,μ=1.419 mm-1,the final R=0.0485 and wR=0.1258 for 13035 observed reflections with I > 2σ(I). The compound contains two different building units,[Pr2(BYBA)6(H2O)4] and [Pr2(BYBA)6(H2O)2]. It is noticeable that [Pr2(BYBA)6(H2O)4] is an isolated binuclear building block,in which the Pr3+ ion centers are both located in an eight-coordinated environment. However,in [Pr2(BYBA)6(H2O)2] the Pr3+ ion centers are located in a nine-coordinated environment and connected by BYBA ligands to form 1D chains.     

Synthesis, Structure, and Magnetic Properties of One Polyoxometalate (W/Mo) Compound: H_8K{[Ni(H_2O)_5]_2(H_2Mo_(1.80)W_(10.20)O_(42))}Cl_3·16H_2O

One new polyoxometalate compound connected via nickel/potassium cations, H8K{[Ni(H2O)5]2(H2Mo1.80W10.20O42)}Cl3·16H2O 1, was prepared and characterized by elemental analysis and IR spectroscopy. Single-crystal X-ray diffraction analysis results reveal that clusters of [Ni(H2O)5]2(H2Mo1.80W10.20O42)}6-in compound 1 are linked by potassium cations to form one- dimiensional chains, based on which a three-dimensional network is further constructed via the hydrogen bonds of O…O and O…Cl. Magnetic measurements show that compound 1 has para- magnetic properties. Crystal data: H62Cl3KMo1.80Ni2O68W10.20, Mr = 3461.33, monoclinic, space group C2/c, a = 18.9291(19), b = 16.6758(17), c = 19.1064(19), β = 106.6880(10)°, V = 5777.1(10)3, Z = 4, Dc = 3.980 g/cm3, F(000) = 6250, μ = 21.574 mm?1, R = 0.0579 and wR = 0.1623 (I > 2σ(I)).     

Synthesis and Crystal Structure of （E）-ethyl 6-benzyl-2-[（cyclopropylmethylamino）（4-fluorophenylamino）-methyleneamino]-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate ethanol monosolvate

The crystal structure of the new title compound (E)-ethyl 6-benzyl-2-[(cyclopropylmethylamino)(4-fluorophenylamino)methyleneamino]-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate ethanol monosolvate (C28H31FN 4O2S·C2H6O, Mr=552.70) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P21/c with a=13.806(10), b=10.850(7), c=19.938(14), β=98.842(9)° , V=2951(4)3 , Z=4, Dc=1.244g/cm 3 , F(000)=1176, μ=0.153 mm-1 , MoKα radiation (λ=0.71073), R=0.0758 and wR=0.2234 for 4262 observed reflections with I > 2σ(I). Intramolecular N-H…S and C-H…N interactions as well as intermolecular N-H…O and O-H…N hydrogen bonds help to stabilize the crystal structure. X-ray diffraction analysis reveals that the asymmetric unit contains one title molecule and one ethanol molecule.     

CRYSTAL STRUCTURE OF [Sm(CCl_3COO)_3(H_2O)_2]·2H_2O

<正> Biaqua-trichloroacetate-samarium dihydrate, [Sm(CCl3COO)3(H2O)2]-2H2O, Mr=707.54, orthorhombic, space group Pnne, with a = 19.158(5), b = 22.176(4), c= 9.798(4)A, Z= 8, V= 4162.7A3.F{000)= 2696,λ(MoKα)=0.71069A, Dx = 2.258 g/cm3, final R=0.061. The title compound has non-molecular structural character, and its structural units Sm(μ-CCl3COO)s/2-(H2O>2 constitute 2-dinensional infinite chains of Sm(μ-CCl3COO)4Sm(μ-CCl3-COO)2Sm.The Sa(Ⅲ) atom in each unit is bound to two O atoms from aqua-molecules and six 0 atoms from six bridging CCl3COO groups (four of which are shared with the SB atom of another unit, two shared with the Sm atom of a third unit) forming a square antiprism.     

Synthesis,Crystal Structure,and Biological Activity of Naphthalen-2-yl4-methyl-1,2,3-thiadiazole-5-carboxylate

The title compound naphthalen-2-yl-4-methyl-1,2,3-thiadiazole-5-carboxylate (C 14 H 10 N 2 O 2 S,M r=270.31) was synthesized by the reaction of 4-methyl-1,2,3-thiadiazole-5-carbonyl chloride with 2-naphthol,and its structure was characterized by IR,1 H NMR,high-resolution mass spectrometry and single-crystal X-ray diffraction.The crystal belongs to orthorhombic,space group Pbcn with a=23.475(5),b=9.6640(19),c=10.814(2),β=90.00°,Z=8,V=2453.2(9) 3,M r=270.30,D c=1.464 g/cm 3,μ=0.262 mm-1,F(000)=1120,R=0.0444 and wR=0.1099.X-ray analysis revealed that the thiadiazole and naphthalene rings were non-planar,while the thiadiazole ring and the ester group were essentially planar,and two intermolecular hydrogen bonds C(6) H(6)···O(1) and C(14) H(14)···O(1) were observed.The preliminary biological test showed that the title compound had antifungal and antivirus activities against tobacco mosaic virus.     

Synthesis, Crystal Structure and Antibacterial Activity of Two Hydrazones Derived from 2-Fluorobenzhydrazide

Two new Schiff base benzoyl hydrazone compounds, C14H10FN3O3 (Ⅰ) and C14H10F2N2O (Ⅱ), have been synthesized and characterized by elemental analysis, IR, UV and X-ray single-crystal diffraction. Both compounds crystallize in monoclinic, space group P21/c with a = 7.0514(14), b = 25.928(5), c = 7.7099(15), β = 111.823(2)°, V = 1308.6(4)3, Z = 4, C14H10FN3O3, Mr = 287.25, Dc = 1.458 g/cm3, μ(MoKα) = 0.115 mm-1, F(000) = 592, the final R = 0.0841 and wR = 0.2489 for 1901 observed reflections (I > 2σ(I)) for I; a = 11.232(3), b =12.735(4), c = 8.612(2) , β = 90.869(3)°, V = 1231.7(6)3, Z = 4, C14H10F2N2O, Mr = 260.24, Dc = 1.403 g/cm3, μ(MoKα) = 0.111 mm-1, F(000) = 536, the final R = 0.0453 and wR = 0.1085 for 1317 observed reflections (I > 2σ(I)) for Ⅱ. The antibacterial activities of both compounds against two bacteria were first studied and one compound showed considerable antibacterial activity against K. Pneumonia and S. aureus.     

Synthesis and Crystal Structure of a New [Mn_2Ni_2] Cubane Complex

A new Mn2Ni2 cubane complex has been synthesized and characterized by single-crystal X-ray diffraction,FT IR spectra and elemental analysis.The title compound [MnIII2NiII2(hmp)4(N3)4(O2CR)2](hmp-is the anion of 2-pyridinemethanol and O2CR-is α-na-phthaleneacetate)crystallizes in the monoclinic system,space group P21/c with a = 10.519(5),b = 22.109(10),c = 23.235(9),β = 106.096(17)o,C48H42Mn2N16Ni2O8,Mr = 1198.28,V = 5192(4)3,Dc = 1.533 g/cm3,F(000)= 2448,μ = 1.258 cm1,Z = 4,the final R = 0.0875 and wR = 0.2020 for 3398 reflections with I > 2σ(I).X-ray diffraction analysis reveals that each Mn(III)center is octahedrally coordinated by two nitrogen atoms of azide anions and three oxygen atoms from three 2-pyridinemethanol anion ligands together with one oxygen atom from naphthaleneacetate.Each Ni(II)is octahedrally coordinated by two nitrogen atoms of 2-pyridinemethanol anion ligands as well as three oxygen atoms from three 2-pyridinemethanol anion ligands and one oxygen atom from naphthaleneacetate.     

A New Sandwich Type Transition Metal Substituted Polyoxotungstate under Hydrothermal Conditions： [NH3（CH2）4NH3]6[Co4（H2O）2（B-α-GeW9O34）2]}·7H2O

A new sandwich transition metal substituted polyoxotungstate, [NH3（CH2）4NH3]6[Co4（H2O）2（B-α-GeW9O34）2]}·7H2O 1, was hydrothermaUy synthesized and characterized by IR spectra and single-crystal X-ray diffraction. The single-crystal X-ray analysis reveals that the crystal crystallizes in monoclinic system, space group P21/c with a = 16.6073（6）, b = 15.3333（5）, c = 19.9869（7） A, β = 103.41（1）°, Mr = 5481.38, V = 4950.8（3） A3, Z = 2, Dc = 3.677 g/cm^3, F（000） = 4900, μ（MoKa） = 22.165 mm^-1, GOOF = 1.005, the final R = 0.0228 and wR = 0.0527. The crystal structure indicates that the [Co4（H2O）2（B-α-GeW9O34）2]^12- polyoxoanion contains two trivacant Keggin [B-α-GeW9O34]^10- fragments in a staggered fashion linked via a rhomb-like Co4O16 group in a centrosymmetric arrangement （C2h symmetry） leading to a sandwich-type structure.     

Synthesis and Crystal Structur of (4,4′-H_2bipy)[CdBr_4]·H_2O

The title compound (4,4′-H2bipy)[CdBr4]·H2O 1 has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The crystal belongs to monoclinic,space group P21/c with a=8.260(3),b=23.926(7),c=9.774(2),β=106.777(9)o,C10H12Br4CdN2O,Mr=608.26,V=1849.4(9)3,Z=4,Dc=2.185 g/cm3,S=1.005,μ(MoKα) =9.814 mm–1,F(000)=1128,R=0.0646 and wR=0.0989. The crystal structure analysis of 1 reveals that the title compound features an isolated structure,based on discrete 4,4′-H2bipy moieties and lattice water molecules which are linked by hydrogen bonds together with tetra-hedral cadmium atoms terminally coordinated by four bromine atoms.     

Hydrothermal Synthesis,Crystal Structure and Magnetic Properties of a Novel Cobalt Complex Based on Biphenyl-3,3＇,4,4＇-tetracarboxylate

A novel cobalt complex,[Co2(bptc)(bix)1.5](1,H4bptc=3,3',4,4'-biphenyltetra-carboxylic acid,bix = 1,4-bis(imidazol-1-ylmethyl)benzene),has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.770(7),b=12.245(8),c=13.514(9),α=102.829(8),β=107.734(8),γ=98.833(9)°,C37H27N6O8Co2,Mr=801.51,V=1607.5(18)3,Dc=1.656g/cm3,F(000)=818,μ=1.100mm-1,Z=2,the final R = 0.0694 and wR = 0.1543 for 3034 observed reflections(I2σ(I)).In the title complex,the two Co(Ⅱ) ions are in different coordination environments with distorted octahedral and trigonal bipyramidal geometries,respectively.The Co atoms are linked together through hexadentate bptc ligands,giving rise to 2D layers which are bridged by the bix ligands into a 3-D supramolecular network.Magnetic susceptibilities of 1 reveal weak antiferromagnetic exchange interactions between the adjacent Co(Ⅱ) ions.     

Synthesis and Structure of a Novel Cobalt(Ⅱ)Complex with the Tertiary Carbinol Derivative of Di-4-pyridinylmethanone

The title complex [Co[(4-C5H4N)2C(OH)(NHC3H7)]2(NO3)2]∞ was obtained and characterized through elemental analysis, FT-IR and X-ray crystallography. The complex crystallizes in space group P3(2)21 with a=10.2480(11), b=10.2480(11), c=26.943(6), β=120.00°, [Co[(4-C5H4N)2C(OH)(NHC3H7)]2(NO3)2]∞, C28H34CoN8O8 , Mr=669.56, Z=3, V=2450.5(7)3 , Dc=1.361 g·cm-3 , μ=0.584 mm-1 , F(000)=1047, R=0.0498 and wR=0.1301. The Co(Ⅱ) center exhibits a N4O2-octahedral coordination geometry surrounded by a pair of nitrates at the axial positions and four pyridyl N atoms at the equatorial sites. An infinite double-bridged chain structure with μ2-bridging (4-C5H4N)2C(OH)(NHC3H7) ligands is formed, which is the in situ product of metal-promoted nucleophilic addition reaction of propan-1-amine with di-4-pyridinylmethanone ((4-C5H4N)2CO) in the presence of Co(NO3)2·6H2O. It is the first tertiary carbinol metal complex derived from di-4-pyridinylmethanone so far, and also the rare example of tertiary carbinol derivative of dipyridylmethanone family. The nucleophilic reaction at the carbonyl of dipyridylmethanone in the presence of metal salt will be discussed.     

金属配位聚合物[Mn2（C8H3NO6）2(C12H8N2)2]n的合成及其催化氧化性能

以5-硝基间苯二甲酸,1,10-邻菲啰啉,硫酸锰(MnSO4.H2O)为原料合成了一种结构新颖的金属配位聚合物——[Mn2(C8H3NO6)2(C12H8N2)2]n(1),其结构经IR,XRD,TG-DTG和元素分析表征。X-射线单晶衍射测试结果表明,1属三斜晶系,空间群Pī,晶胞参数a=10.060 2(1),b=14.343 5(2),c=14.663 7(2),α=104.052(1)°,β=102.633(1)°,γ=110.460(1)°,Mr=888.52,V=1 812.69(4)3,Z=2,Dc=1.628 g.cm-3,F(000)=900。以30%H2O2为氧化剂,初步研究了1在苯乙烯氧化反应中的催化氧化性能。     

Hydrothermal Synthesis and Crystal Structure of a Novel Polymolybdate with Two Kinds of Organonitrogen Ligands

A novel inorganic-organic compound (C4N2H12)(C2N2H10)2[Mo5P2O23] (1) has been synthesized by the reaction of (NH4)2MoO4, H3PO4, C2N2H8 (ethylenediaminium), C4N2H10·6H2O (piperazine hexahydrate) and water in aqueous solution under mild hydrothermal conditions. Single-crystal X-ray analysis reveals that the title compound is crystallized in the triclinic system, space group P1 with a = 9.258(19), b = 9.382(19), c = 17.681(4), α = 76.28(3), β = 84.48(3), γ = 70.82(3)o, V = 1408.9(6)3, Mr = 1122.04, Z = 2, Dc = 2.645 g/cm3, μ = 2.384 mm-1, F(000) = 1092.0, the final R = 0.0391, wR = 0.1185 and S = 1.006 for 6169 observed reflections with I > 2σ(I). The crystal packing is stabilized by intra- and intermolecular N-H···O hydrogen bonds to form an infinite 3D network.     

席夫碱钴(Ⅱ)配位聚合物的合成及其晶体结构

乙酰丙酮与1,2-二(邻氨基苯氧基)乙烷缩合制得Schiff碱配体L;L与CoCl2.6H2O反应合成了席夫碱钴(Ⅱ)配位聚合物[CoLCl2]n(1),其结构经IR,XRD和元素分析表征。1属单斜晶系,空间群P2/n,晶胞参数a=9.923(8),b=12.362(9),c=11.736(8),β=94.583(12)°,V=1 434.9(17)3,Z=2,Dc=1.246g.cm-3,R1=0.049 5,wR2=0.152 3。1中每个Co(Ⅱ)的配位环境均为扭曲四面体,每个配体L通过其两臂乙酰丙酮亚胺单元的端基氧原子同两个金属离子配位桥联形成一维链结构。     

pH-Dependent Assembly of Molecular Capsule,2D and 3D Coordination Polymers

Three lanthanum/4-sulfocalix[4]arene complexes,namely,H2[(H4CAS)La(H2O)7]2· H2[(H4CAS)La(H2O)7]2·2C2H5OH·12H2O(1),[H(H4CAS)La(H2O)5]·5H2O(2)and [(H4CAS)La-(H2O)4(NO3)La(H2O)5]·7H2O(3),have been synthesized at different pH conditions.Complex 1,which exhibits the structure of "molecular capsule" containing the guest of C2H5OH molecule,is formed at pH = 1.At pH = 2～3,a two-dimensional(2D)coordination polymer of 2 is formed.Further increase of the pH value to 5 leads to the three-dimensional(3D)coordination polymer of 3.Crystal data for 1:monoclinic,space group P21/n,a = 10.8743(16),b = 25.957(4),c = 15.863(2),β = 94.763(2)°,V = 4462.1(11)3,Mr = 1160.87,Z = 4,F(000)= 2376,R = 0.0370 and wR = 0.0936;Crystal data for 2:tetragonal,space group P4/n,a = 11.6593(16),c = 14.069(4),V = 1912.5(6)3,Mr = 1114.81,Z = 2,F(000)= 1136,R = 0.0849 and wR = 0.1906;and those for 3:triclinic,space group P1,a = 10.4588(16),b = 14.995(2),c = 16.699(3),α = 65.446(3),β = 83.487(3),γ = 73.305(3)°,V = 2281.6(6)3,Mr = 1367.76,Z = 2,F(000)= 1368,R = 0.0423 and wR = 0.1183.