钴配合物[Co_2(H_2O)_8(C_(10)H_8N_2)_2]·(HO_3PCH_2CH_2SO_3)(SO_4)(H_2O)_4的合成与晶体结构研究

用硫酸钴、4,4'-联吡啶和2-磺酸基乙基膦酸合成了一个新颖的钴化合物:[Co_2(H_2O)_8(C_(10)H_8N_2)_2]·(HO_3PCH_2CH_2SO_3)(SO_4)(H_2O)_4,并对其进行了红外.元素分析、热重测试,通过单晶衍射仪测定了其晶体结构.结果表明,配合物属单斜晶系C2/c空间群,分子式为C_(22)H_(45)Co_2N_4O_(22)PS_2,分子量为930.57,晶胞参数为a=19.8456(18),b=11.2957(10),c=34.719(3)(A),β=106.095(3)°,晶胞体积为7477.9(12)(A)~3,Z=8,Dc=1.653 g/cm~3,F(000)=3856,μ=1.131 mm~(-1),最终残差因子R_1=0.0726,wR_2= 0.1719(相对于5612个I>2σ(I)的可观测衍射点).在这个化合物中,二齿配体4,4'-联吡啶把Co(II)桥连成[Co(4,4'-bipy)]~(2+)链.化合物中的[Co(4,4'-bipy)]~(2+)链有三个不同的朝向.2-磺酸基乙基膦酸没有参与配位而是做为一个有机模板剂填充在[Co(4,4'-bipy)]~(2+)链形成的空隙中.     

水溶性单乙氧基刺芒柄花素磺酸镁的合成及晶体结构研究

以异黄酮化合物刺芒柄花素为先导化合物,合成了水溶性的单乙氧基刺芒柄花素磺酸镁,并通过红外、氢谱、碳谱、元素分析和X射线单晶衍射表征了其结构.标题化合物的分子组成为[Mg(H_2O)_6](C_(18)H_(15)O_(4 )SO_3)_2·4H_2O,[Mg(H_2O)_6]~(2+),C_(18)H_(15)O_4SO_3~-和H_2O之间存在多种氢键作用;此外,其晶体结构中还存在着分子间π…π及C—H…π芳环堆积作用.氢键、芳环堆积作用和阴、阳离子之间的静电引力共同将标题化合物组装成三维网络结构.     

Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co(4,4'-bipy)_2(H_2O)_4]· [Co_2(4,4'-bipy)3O(H_2O)_8]·2TST·2(4,4'-bipy)·4H_2 and [Co(4,4'-bipy)_2(H_2O)_4]DSNT'4,4'-bipy

Two new cobalt(Ⅱ) supramolecular complexes [Co(4,4'-bipy)_2(H_2O) _4]·[Co_2(4,4'-bipy)3-(H_2O) _8]·2TST-2(4,4'-bipy)·4H_2O 1 and [Co(4,4'-bipy) _2(H_2O) _4]DSNT·4,4'-bipy 2 based upon the assembly of Co(Ⅱ), 4,4'-bipyridine (4,4'-bipy) and two new multifunctional organic ligands, 2,4,6-tris(4-sulfophenyl-amino)-1,3,5-triazine (H_3TST) and 2,4-bis(p-sulfanilato)-6-diethylamino-1,3,5-triazine (H_2DSNT), have been prepared by hydrothermal method and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal structure of 1 is of monoclinic, space group P2_(1/n) with α= 13.599(4), b = 18.988(6), c = 22.995(7) A, β = 90.273(6)°, V= 5938(3) A~3, Z = 4, C_(56)H_(59)CO_(1.5)N_(13)O_(17)S_3, M_r = 1370.74, D_c = 1.533 g/cm~3,μ = 0.613 mm~(-1), F(000) = 2842, GOOF = 1.018, the final R = 0.0796 and wR = 0.1498 for 9019 observed reflections with I > 2o(I). The crystal structure of 2 belongs to the monoclinic system, space group C2/c with α = 18.864(6), b = 14.283(5), c = 20.246(7) A, β = 107.799(6)°, V = 5194(3) A~3, Z = 4, C_(49)H_(52)CoN_(12)O_(10)S_2, M_r = 1092.08, D_c = 1.397 g/cm~3, μ= 0.480 mm~(-1), F(000) = 2276, GOOF = 1.059, the final R = 0.0665 and wR = 0.1900 for 4887 observed reflections with I> 2σ(I). The results of X-ray crystal structure analysis revealed that complexes 1 and 2 exhibit layered supramolecular frameworks stabilized by electrostatic interactions, π-π interactions and hydrogen bonds.     

Hydrothermal Synthesis and Crystal Structure of a New Manganese(Ⅱ) Complex with 2,4-Pyridine-dicarboxylic Acid and 2,2'-Bipyridine Ligands

A new metal-organic complex [Mn_2(PDC)_2(bipy)_2(H_2O)_2] (H_2PDC=2,4-pyridinedicarboxylic acid,bipy=2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,TG and single-crystal X-ray diffraction. The compound crystallizes in triclinic,space group P~(-)1 with α=7.376(3),b=9.990(4),c=11.950(5)(A),α=75.217(5),β=78.052(5),γ=70.655(5)°,V=796.0(5)(A)~3,C_(34)H_(26)Mn_2N_(6O)O_(10),M_r=788.49,D_c= 1.645 g/cm~3,μ(MoKa) = 0.866 mm~(-1),F(000)=235,Z=1,the final R=0.0425 and wR=0.0700 for 1971 observed reflections (Ⅰ > 2σ(Ⅰ)). In the crystal structure,the manganese atom is six-coordinated by two carboxylate oxygen atoms from two different PDC ligands,one aqua ligand,and three nitrogen atoms from 2,2'-bipy and PDC ligands,giving a distorted octahedral geometry. It exhibits a three-dimensional supramolecular network defined by O-H…O hydrogen-bonding interactions.     

一种新型稀土苯甲酸铽配合物的合成、表征及其晶体结构

本文报道一种新型稀土苯甲酸配合物,[Tb(C_7H_5O_2)_3(C_7H_6O_2)(H_2O)]_2的合成。用元素分析、DTA、TG、DTG和IR光谱对其性质进行了表征,并测定了其晶体结构。晶体属三斜晶系,空间群为P1,Z=1。晶胞参数为:a=9.148(1),b=11.460(2),c=13.506(2)A;α=112.76(1),β=91.83(1),γ=91.99(1)°;V=1303.3(4)A~3。稀土离子形成九配位的单帽正方反棱柱型配合物,稍有崎变。     

双(正-丙基亚砜)乙烷钴(Ⅱ)配合物的研究Ⅱ

本文合成了硝酸钴(Ⅱ),氯化钴(Ⅱ),硫氰酸钴(Ⅱ)与内、外消旋的双(正-丙基亚砜)乙烷(以A表示)六个固体配合物:[Co_2(α-A)_3Cl_4]·H_2O、[Co(β-A)_2(NO_3)_2)·H_2O、[Co(β-A)_2(NO_3)_2]、[Co_2(α-A)_2(SCN)_4]·2H_2O和[Co(β-A)_2(SCN)_2](α-A和β-A各是外、内消旋的C_3H_7S(O)(CH_2)S(O)C_3H_7)。由元素分析、红外光谱、磁化率、电导及离子交换等研究结果表明配体A以二个氧原子与Co(Ⅱ)配位形成七元环的配合物。并确定Co_2(α-A)_3Cl_4为[Co(α-A)_3][CoCl_4]的配合物。初步认为[Co(α-A)(NO_3)]NO_3·H_2O为畸变的四面体配合物。其余四个配合物均为高自旋、畸变八面体,它们的结构可能是:及[Co(β-A)_2(SCN)_2]。对[Co(β-A)_2(NO_3)_2、[Co(β-A)_2(H_2O)_2](ClO_4)_2·H_2O及[Co(β-A)_2(SCN)_2]的Dq值计算结果表明NO_3~-、H_2O和SCN~-与Co(Ⅱ)配位符合配合物的光化序。     

苯甲酰羟胺—钼酰螯合物的分子结构及晶体结构

继苯甲酰羟胺—钨酰螯合物WO_2(C_7H_6O_2N)_2的晶体结构测定后,本文报导了整合物MoO_2(C_7H_6O_2N)_2·C_6H_(13)OH的结构和特性,并初步提出了酰羟胺类试剂用于钨钼分离的可能性。苯甲酰羟胺—钼酰螯合物的分子及晶体结构已由四园衍射仪测定,晶体属空间群C_(2h)~5—P2_1/c,晶胞参数a=9.142(1),b=21.591(3),c=11.662(3)A,β=90.31(1)°,Z=4,最终吻合因子R=0.079.虽然结构中结合的已醇分子无法定位,但它与螯合物分子间强烈的氢键键合作用,则是十分明显的,这很可能是影响苯甲酰羟胺对钨钼分离效果的重要因素之一。     

Hydrothermal Synthesis and Crystal Structure of a Novel Dinuclear Co(Ⅱ) Complex: [Co2(2,2(')-bpy)2((-L)2(L)2(μ-H2O)] (HL = 4-Chlorobenzoic Acid)

A new 4-chlorobenzoic acid bridge Co(Ⅱ) complex [Co2(2,2(')-bpy)2(μ-L)2(L)2(μ- H2O)] (HL = 4-chlorobenzoic acid) has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group C2/c with a = 22.537(5), b = 16.212(3),c = 15.306(3)(A), β= 124.37(3)°, V = 4616.1(16) (A)3, Mr = 1070.45, Dc = 1.540 g/cm3, Z = 4, μ = 1.012 mm-1, F(000) = 2176, the final R = 0.0338 and Wr = 0.0810. The title complex is composed of dinuclear [Co2(2,2(')-bpy)2(μ-L)2(L)2(μ-H2O)] molecules. Each Co(Ⅱ) atom is coordinated by two nitrogen atoms from one 2,2'-bipyridine ligand, three oxygen atoms from three 4-chlorobenzoic ions and another oxygen atom from one water molecule. The two Co(Ⅱ) atoms are connected by two 4-chlorobenzoic ions and one bridged water molecule. The dinuclear molecules are interlinked by hydrogen bond and π-π stacking interactions into a three-dimensional supramolecular network.     

三氟醋酸钆的晶体结构

测定了[Gd(CFCOO)_3·3H_2O]_2的晶体结构属单斜晶系,空间群为P2_1/c.Z=2.晶胞参数a=9.192(3),b=18.890(1),c=9.785(3);β=113.84(2)°.[Eu_(0.1)Gd_(0.9)(CF_3COO))3·3H_2O]_2的光谱构分析表明稀土离子周围的局部对称性可能是C_2(C_s)和C_2h。     

基于柔性多羧酸配体H3TCOPM构筑的Co(Ⅱ)配合物的合成与结构

以三苯甲烷-4,4′,4″-三羧酸(H_3TCOPM)为主配体,以含氮二齿配体4,4′-bipyridine(4,4′-bipy)为辅助配体,与Co(NO_3)_2·6H_2O通过溶剂热反应得到了2个配位聚合物{[Co_2(α-OH-TCOPM)(OH)(H_2O)_4]·DMF}_n(1)(α-OH-H_3TCOPM=三苯甲醇-4,4′,4″-三羧酸)和{[Co_3(α-OH-TCOPM)_2(4,4′-bipy)_3(H_2O)_6]·2H_2O}_n(2)。晶体结构分析表明,配合物1为四边形的二维层状结构,而配合物2为二维网状结构。采用红外光谱、粉末X射线衍射对配合物进行了表征,用热重分析仪研究了其热稳定性。     

硫尿、L-酒石酸根和水为主体晶格的四乙基铵层状包合物的合成及晶体结构

合成了一种新的硫尿-阳离子主体晶格包合物[(C_2H_5)_4N~+]_2C_4H_4O_6~ (2-)·2(NH_2)_2CS·2H_2O，并通过单晶X射线衍射法对其进行了晶体结构测定。 结果表明该晶体属单斜晶系，P2_1空间群，晶胞参数a = 0.7727(2) nm，b = 1. 4707(4) nm，c = 1.4645(4) nm，β = 95.161(5)°，Z = 2，R_1 = 0.0488。晶 体为“三明治”式夹层结构，波形平面主体氢键网状结构由[酒石酸根-硫尿_2]三 聚体形成的双纽带，在两个水分子的桥连氢键连接下形成的。酒石酸根在主体晶格 的氢键形成中起到重要作用。     

水合苯并—15—冠—5四溴合铟(Ⅲ)酸钠(NaInBr_4)_2(C_(14)H_(20)O_5)_3·2H_2O的晶体结构

本文报道了在乙醇—氯仿混合溶剂中首次获得组份为(NaInBr_4)_2(C_(14)H_(20)O_5)_3·2H_2O的晶体配合物.用元素分析确定了其组份.通过红外光谱的研究证实配合物晶体中的阳离子与醚氧原子及水分子发生了配合作用。 用X-射线衍射法测定了配合物的晶体结构,晶体属单斜晶系,M=1755.3,a=14.393(8)A,b=28.494(9)A,c=15.191(8)A,β=96.63(5)°,V=6189A~3’,D_c=1.88g·cm~(-3),Z=4,空间群为C_(2h)~5——P2_1/n。晶体结构研究表明不对称单位中包含两个配阳离子Na~(+)(B15C5)(B15C5)代表C_(14)H_(20)O_5分子)。两个配阴离子InBr_4~-、两个H_2O分子和一个未被金属离子配合的B15C5分子。配合物的晶体结构测定结果对于阐明与该晶体相对应的萃取体系In(Ⅲ)/NaBr/B15C5—1,2C_2H_4Cl_2的萃取机理提供了理论依据。     

苦味酸锂与二苯并18-冠-6的缔合结构

培养了苦味酸锂与二苯并18-冠-6缔合物的单晶体[Li(pic)(H_2O)]_2·[C_(20)H_(24)O_6],化学式为C_(32)H_(32)Li_2N_6O_(22),用X射线法测定了缔合物的晶体结构,证明该晶体属单斜晶系,空间群为P2_1/m,晶胞参数:a=8.299(2),b=25.216(3),c=9.158(2)(?),β=100.34(2)°,V=1885.4(?)~3,Z=2。     

若干含氧桥双核钼(Ⅴ)原子簇化合物的研究

本文在测定了五个新颖双核钼(Ⅴ)簇合物的晶体结构(QH)_4[Mo_2O_4(NCS)_6](1),H(PyH)_3·[Mo_2O_4(C_2O_4)_2(H_2O)_2]_2·2H_2O(2),(QH)_3[Mo_2O_4(C_4H_3OCOO)(NCS)_4](3),(QH)_3[Mo_2O_4·(CH_3OH)(NCS)_5](4)和(PyH)_4[Mo_2O_3(SO_4)(NCS)_6](5)以及文献报道该类型化合物结构数据的基础上,综述了含氧桥双核钼(Ⅴ)簇合物的结构特征,并应用SCC-EHMO方法探讨了该类型化合物的电子结构和成簇机理,最后用简正坐标分析法,研究了含氧桥双核钼(Ⅴ)化合物簇胳单元[Mo_2O_4]~(2 )和[Mo_2O_3SO_4]~(2 )的振动结构及其红外谱带归属。     

Co(Ⅱ)与甜菜碱类衍生物形成的两种配合物的结构和磁性特征

合成了2种新的Co(Ⅱ)的配合物{[Co(L1)2(H2O)2](Cl O4)2·4H2O}n(1)和{[Co(L2)2(H2O)4](Cl O4)2·8H2O·L2}n(2)(L1=1,1′-(4,4′-二亚甲基联苯)二(1-吡啶鎓-3-羧酸盐),L2=1,1′-(4,4′-二亚甲基联苯)二(1-吡啶鎓-4-羧酸盐)),并且分别用红外光谱、热差分析、X射线粉末衍射和X射线单晶衍射表征了这两种化合物。晶体结构分析表明L1,L2,1和2分别属于P21/c,P21/c,P1和P1空间群。化合物1中的Co(Ⅱ)与L1配位形成二维的配位聚合物,2中的Co(Ⅱ)与L2配位形成独立的阳离子。二者的晶体结构都含有大量的氢键作用或者配位键形成的孔状结构。此外,磁性研究表明,1和2中都存在反铁磁性相互作用。     

硫氰酸铈(Ⅲ)与三缩四乙二醇配合物[Ce(C_8H_(18)O_5)(NCS)_3(H_2O)]的合成及晶体结构

合成了硫氰酸铈(Ⅲ)与三缩四乙醇配合物[Ce(C_8H_(18)O_5)(NCS)_3(H_(2)O)].晶体结构分析表明,该配合物晶体属三斜晶系,P(?)空间群.晶胞参数:a=0.8816(3)nm,b=1.0465(2)nm,c=1.2490(2)nm,α=86.46(1)°,β=70.90(2)°,γ=66.37(2)°,ν=0.9943nm~(3),Z=2.D_(计算)=1.769cm~(3),最终偏差因子R=0.049.     

5-磺基水杨酸二钠的晶体结构

应用X射线衍射方法测定了三水合磺基水杨酸二钠的晶体结构。晶体属正交晶系,晶胞参数为:a=23.010,b=9.314,c=5.461,Z=4,空间群Pca2_1。由重原子法和直接法解出结构,并经全矩阵最小二乘法修正,最后的R=0.067。从晶体结构的测定得出其分子式应为(Na+(H_2O)_3]·C_6H_3(COO-)(OH)-(SO_3Na)。水杨酸分子基本上呈平面型,分子中的两个Na~+离子都成扭歪的八面体配位。其中的Na~+(2)离子又与三个水分子形成链状[Na~+(H_2O)_3],并由于链间的氢键的相互交联而成为层状结构。     

新型双核Co（Ⅱ）聚合物{[Co2L（MeOH）（H2O）4]n·nH2O}的合成及其晶体结构

采用溶剂热法,丁烷四羧酸(H4L)与水合乙酸钴经配位聚合反应合成了一个新型的双核Co(Ⅱ)聚合物[Co2L(MeOH)(H2O)4]n.nH2O(1),其结构经元素分析和单晶X-射线衍射表征。1属单斜晶系,C2/c空间群,晶胞参数a=2.802 6(3)nm,b=0.816 32(11)nm,c=1.630 1(2)nm,β=119.793(2)°,V=3.236 5(7)nm3,Z=8,Dc=1.925 Mg.cm-3,R1=0.097 5,wR2=0.223 1。1通过H4L桥联形成一维链,通过O-H┈O氢键作用形成了无限延伸的二维网络结构;在1中存在的分子内及分子间氢键使1具有三维网络结构。     

中药白头翁配基G(C_(30)H_(48)O_4)的晶体和分子结构

白头翁配基G(C_(30)H_(48)O_4)晶体的空间群是P2_12_12_1,晶胞参数为:a=12.5925(2),b=13.245(2),c=15.923(2);Z=4(Dobs=1.12,Dcalc=1.182g·cm~(-3))。晶体结构用直接法和电子密度函数解出。在这个不对称分子中,四个六元环构型均属椅式,并且彼此间通过ee键稠合。晶体中存在三种O-H…O分子间氢键。     

Synthesis,Structure,and Luminescent and Dielectric Properties of Two Novel 1D Chains Based on a T-Shaped Tripodal Ligand 4-(4,5-Dicarboxy-1H-imidazol-2-yl)pyridine Loxide

Two 1D chain metal-organic framework complexes, {Co[(C_(10)H_5N_3O_5)-(H_2O)_2·H_2O]}n(1) and {Cd[(C_(10)H_5N_3O_5)(H_2O)_2]}_n(2), based on a T-shaped tripodal ligand 4-(4,5-dicarboxy- 1H-imidazol-2-yl) pyridine 1-oxide(H3DCImP y O) have been reacted under hydrothermal conditions, and were characterized by single-crystal X-ray structure analysis, fluorescent analysis and thermal gravimetric analysis. According to single-crystal X-ray determination, complex 1 crystallizes in the monoclinic system, space group P21/n with a = 9.4930(13), b = 13.2024(18), c = 10.5203(14) ?, β = 98.402(2)°, Z = 4, V = 1304.4(3) ?3; and complex 2 crystallizes in the monoclinic system, space group C2/c with a = 13.557(3), b = 13.568(3), c = 6.7804(13) ?, β = 105.095(2)°, Z = 4 and V = 1204.2(4) ?3. Fluorescent analysis of complex 2 showed an intense emission band at 466 nm when the exciting radiation was set at 360 nm. Dielectric constants of complexes 1 and 2 were measured at different frequencies with temperature variation.