固固反应合成三碘化锑、三碘化铋与硫脲配合物

通过三碘化锑和三碘化铋与硫脲间的室温固固反应合成了三碘化锑、三碘化铋的硫脲配合物 ,其组成为 :M[CS( NH2 ) 2 ]3 I3 ( M=Sb,Bi)。两种配合物的晶体结构均属于单斜晶系 ,锑配合物 Sb[CS( NH2 ) 2 ]3 I3 的晶胞参数为 :a=1 .4 772 nm,b=1 .6 5 82 nm,c=2 .0 6 74 nm,β=90 .81°,铋配合物 Bi[CS( NH2 ) 2 ]3 I3 的晶胞参数为 :a=1 .4 0 1 0 nm,b=2 .0 1 6 8nm,c=2 .0 397nm,β=90 .84°。远红外光谱表明硫脲中的 N原子而非硫原子参与了配位     

氨基酸锑(Ⅲ)双核配合物的固相合成与表征

采用室温固相反应法合成了甘氨酸锑和苯丙氨酸锑双核配合物 ,用元素分析、远红外光谱、热重差热分析及X射线粉末衍射进行了表征 .两种配合物Sb2 L5X·2 5H2 O(L =gly ,phe;X =Cl或I)的晶体结构均属于单斜晶系 ,甘氨酸锑配合物的晶胞参数为 :a =0 6 5 2 6nm ,b =1.2 2 2 7nm ,c=1.3877nm ,β=97.88°,V =1.0 96 8nm3 ,苯丙氨酸锑配合物的晶胞参数为 :a =1.0 6 17nm ,b =0 .7839nm ,c =1.5 72 5nm ,β =92 .32°,V =1.30 77nm3 .远红外光谱表明O ,N ,Cl或I原子参与配位     

配合物[Cu_2(TS)(H_2O)]·H_2O的自组装制备、晶体结构和电化学性质

利用单核配合物Na2 CuTS·H2 O在溶剂中的不稳定性质 ,自分解并重新组装得到了双核配合物 [Cu2 (TS)(H2 O) ]·H2 O .配合物为单斜晶系 ,空间群P2 1/C ,晶胞参数为a =0 .80 830 (16 )nm ,b =1.70 79(3)nm ,c =1.4 0 73(3)nm ,β =10 5 .0 8(3)° ,V =1.86 5 4 (6 )nm3 ,Z =4 ,最终一致性因子R =0 .0 6 4 4 .该分子结构为双核单元 ,金属原子通过两个酚氧原子桥联在一起 .结合晶体结构对配合物作了电化学研究     

二烷基荒酸砷(Ⅲ)、铋(Ⅲ)配合物的合成、晶体结构及抑菌活性

合成了二丁基二硫代氨基甲酸砷[(C9H18NS2)3As(Ⅲ)](1)和二甲基二硫代氨基甲酸铋[(C3H6NS2)3Bi(Ⅲ)](2)两种配合物。通过元素分析、红外光谱、1HNMR、热重对其进行表征,并用X-射线单晶衍射测定了晶体结构。配合物1属于三斜晶系,P 空间群,晶胞参数为：a = 1.075 0(15) nm,b = 1.214 3(16) nm,c = 1.621(3) nm,α = 69.15(2)°, β = 75.36(3)°, γ = 88.17(2)°;配合物2也属于三斜晶系,P 空间群,晶胞参数为：a = 0.992 9(3) nm,b = 0.993 0(3) nm,c = 1.142 7(3) nm,α = 64.495(4)°, β = 80.400(4)°, γ = 64.772(4)°。利用琼脂扩散法测试了配合物的抑菌活性, 结果表明配合物1对5种受试菌株具有较强的抑菌活性,配合物2则仅有弱的拟菌活性。     

氨荒酸配合物([M(MeBnNCS_2)_3],M=Sb(Ⅲ),Bi(Ⅲ))的合成、晶体结构及抑菌活性

合成了2种新的N-甲基-N-苄基二硫代氨基甲酸锑[Sb(MeBnNCS2)3](1)和铋[Bi(MeBnNCS2)3](2)配合物。通过元素分析、红外光谱、1H NMR、热重对其进行表征,并用X-射线单晶衍射测定了晶体结构。配合物1和2均属于单斜晶系,P21/c空间群。配合物1的晶胞参数为:a=0.955 1(7)nm,b=1.357 5(10)nm,c=2.468 1(17)nm,β=104.01(2)°,Z=4,V=3.105(4)nm3,Dc=1.520 g·cm-3,F(000)=1 440,μ=1.314 mm-1,最终偏离因子R1=0.033 9,wR2=0.083 2,S=1.010;配合物2的晶胞参数为:a=1.339 0(6)nm,b=0.997 5(5)nm,c=2.426 1(5)nm,β=98.433(7)°,Z=4,V=3.205(2)nm3,Dc=1.653 g·cm-3,F(000)=1 568,μ=5.912 mm-1,最终偏离因子R1=0.039 8,wR2=0.086 4,S=1.089。在这2个配合物中,中心金属离子M(Ⅲ)与来自3个配体中的6个硫原子配位,配合物1形成6配位的畸变的八面体构型;配合物2则形成6配位的畸变的五角锥构型。在配合物2中,分子之间又通过Bi…S弱相互作用构成二聚体结构。利用琼脂扩散法测试了配合物的抑菌活性,结果表明配合物1对4种受试菌株具有较强的抑菌活性。     

固固相反应合成牛磺酸水杨醛钾与锑、铋的配合物

合成了牛磺酸水杨醛钾,并采用室温固固相反应法合成了牛磺酸水杨醛钾与三氯化锑和三氯化铋的配合物,其组成为:K2MC18H20O8N2S2 (M = Sb, Bi)。两种配合物的晶体结构均属于单斜晶系,锑配合物的晶胞参数为:a = 1.2869 nm, b = 1.7636 nm, c = 1.9917 nm, β= 93.79埃活榕浜衔锏木О问篴 = 1.4770 nm, b = 2.0334 nm, c = 2.0149 nm, β= 94.05。红外光谱表明N、Cl原子参与了配位,中心离子的配位数为5。     

烯唑醇锌盐配合物的合成与结构表征

合成了 2个新配合物ZnL4 Cl2 和ZnL4 (H2 O) 2 ·(NO3 ) 2 (L =烯唑醇 ) ,通过元素分析、IR光谱和核磁共振谱表征了配合物的结构 .X射线单晶衍射结构分析表明 :ZnL4 Cl2 晶体属三斜晶系 ,空间群P墿,晶胞参数 :a =0 882 80(7)nm ,b =1 370 94(11)nm ,c=1.5 182 9(13)nm ,α =91.0 72 (10 )°,β =98 5 97(10 )°,γ =10 6 .779(8)° ,V =1.735 8(2 )nm3 ,Z =1;ZnL4 (H2 O) 2 ·(NO3 ) 2 晶体属单斜晶系 ,空间群Cc,晶胞参数 :a =1.5 2 430 (13)nm ,b =1.5 85 4(2 )nm ,c =3.336 1(4 )nm ,α =90 0 0 0° ,β =10 0 .2 2 7(8)° ,γ =90 0 0 0°,V =7 934 (2 )nm3 ,Z =1     

二烷基二硫代氨基甲酸砷(Ⅲ)、铋(Ⅲ)配合物的合成、晶体结构及抑菌活性

合成了二丁基二硫代氨基甲酸砷[(C9H18NS2)3As(Ⅲ)](1)和二甲基二硫代氨基甲酸铋[(C3H6NS2)3Bi(Ⅲ)](2)两种配合物。通过元素分析、红外光谱、1H NMR、热重对其进行表征,并用X-射线单晶衍射测定了晶体结构。配合物1属于三斜晶系,P 1-空间群,晶胞参数为:a=1.075 0(15)nm,b=1.2143(16)nm,c=1.621(3)nm,α=69.15(2)°,β=75.36(3)°,γ=88.17(2)°,Z=2,V=1.910(5)nm3,Dc=1.197 g.cm-3;配合物2也属于三斜晶系,P 1-空间群,晶胞参数为:a=0.992 9(3)nm,b=0.993 0(3)nm,c=1.142 7(3)nm,α=64.495(4)°,β=80.400(4)°,γ=64.772(4)°,Z=2,V=0.914 7(4)nm3,Dc=2.068 g.cm-3。配合物1中的As(Ⅲ)与来自3个配体中的6个硫原子配位,形成6配位畸变八面体构型;配合物2则形成6配位畸变五角锥构型,其分子之间又通过Bi···S弱相互作用构成二聚体结构。利用琼脂扩散法测试了配合物的抑菌活性,结果表明配合物1对5种受试菌株具有较强的抑菌活性,配合物2则仅有弱的抑菌性。     

铋（Ⅲ）苯乙酸-1,10-邻菲罗啉三元配合物[Bi2（PPA）6·（Phen）2]的合成、晶体结构及抑菌活性

合成了铋(III)苯乙酸-1,10-邻菲罗啉[Bi2(PPA)6·(Phen)2](HPPA=苯乙酸(C8H7O2),Phen=l,10-邻菲罗啉(C12H8N2))三元配合物,并通过元素分析和红外(IR)光谱对其进行了表征,用单晶X-射线衍射测定了配合物的晶体结构.配合物属于三斜晶系,P-1空间群,a=0.9100(6)nm,b=1.2617(8)nm,c=1.3324(9)nm,α=89.757(8)°,β=87.277(8)°,γ=81.155(8)°,V=1.5099(17)nm3,Dc=1.748g·cm-3,μ=5.890mm-1,Z=1,F(000)=780,残差因子R1=0.0484,wR2=0.1090[I>2σ(I)],S=1.002.标题化合物为双核铋(III)配合物,金属中心Bi(III)原子与三个苯乙酸根(PPA)中的6个氧原子、一个1,10-邻菲罗啉分子中的两个氮原子和一个桥连氧原子进行配位,形成九配位的扭曲三帽三方柱配位十四面体,围绕铋原子的价键总数VBi(1)=2.897,两个Bi(III)原子通过两个桥连氧原子连结成中心对称的分子,Bi…Bi间距离为0.4469(2)nm.初步抑菌试验结果显示,配合物对大肠杆菌(E.Coli)、金黄色葡萄球菌(S.Aureus)、枯草芽孢杆菌(B.Subtilis)表现出相似且良好的抑菌效果.     

亚乙基硫脲配位聚合物[Cu3(etu)3 Br3]n的合成与晶体结构

CuB r2和亚乙基硫脲反应生成Cu(I)配位聚合物[Cu3(etu)3B r3]n(etu=亚乙基硫脲),单晶X射线衍射测得该晶体为三斜晶系,Pī空间群.晶胞参数:a=0.762 46(6)nm,b=1.198 48(10)nm,c=1.224 52(7)nm,α=68.202(5),°β=74.607(6),°γ=87.652(7)°,V=0.999 61(13)nm3,Z=2,Mr=736.82,Dc=2.448 g.cm-3,μ=9.477 mm-1,F(000)=708,偏差因子R1=0.030 6,wR2=0.071 0.配合物由环状[Cu(etu)B r]3单元聚合而成,形成Cu4S2B r2和Cu2S4B r2聚合体,两聚合体通过μ2-S桥键交替连接,形成平行于晶胞b轴的[Cu3(μ3-etu)(μ2-etu)2(μ2-B r)2B r]n一维链.Cu(I)均为变形四面体配位,亚乙基硫脲以S原子与Cu(I)结合,形成μ2-S和μ3-S两种配位方式.     

Synthesis, characterization and thermal decomposition of thiourea complexes of antimony and bismuth triiodide

The thiourea complexes of antimony and bismuth triiodide were synthesized by a direct reaction of antimony and bismuth triiodide with thiourea powder at room temperature. The formula of the complex is MI₃[SC(NH₂)₂]₃(M=Sb, Bi). The crystal structure of the complexes belongs to monoclinic system and the lattice parameters are a=1.4772 nm, b=1.6582 nm, c=2.0674 nm and β=90.81° for SbI₃(SC(NH₂)₂)₃ and a=1.4009 nm, b=2.0170 nm, c=2.0397 nm and β=90.84° for BiI₃[SC(NH₂)₂]₃. The infrared spectra reveal that the trivalent antimony or bismuth ion is coordinated by the nitrogen atom, not the sulfur atom of the thiourea. Thermal analysis shows that there are two times structure rearrangements or phase transformation in the complexes from 100 to 170°C.     

[Sb(12-Krone-4)2(CH3CN)][SbCl6]3 und [Bi(12-Krone-4)2(CH3CN)][SbCl6]3, die ersten Trikationen von Antimon(III) und Bismut(III)

[Sb(12-Crown-4)₂(CH₃CN)][SbCl₆]₃ and [Bi(12-Crown-4)₂(CH₃CN)][SbCl₆]₃, first Trications of Antimony(III) and Bismuth(III) The crown ether complexes [M(12-crown-4)₂(CH₃CN)][SbCl₆]₃ with M = Sb and Bi are formed by the reaction of antimony trichloride and bismuth trichloride, respectively, with antimony pentachloride in acetonitrile solution in the presence of 12-crown-4. They form colourless, moisture sensitive crystals, which were characterized by X-ray structure determinations and by IR spectroscopy. The complex with M = Sb was also characterized by ¹²¹Sb Mössbauer spectroscopy. Both complexes crystallize isotypically in the orthorhombic space group Pbcn with four formula units per unit cell. M = Sb: 3 483 observed unique reflections, R = 0.038. M = Bi: 2 958 observed unique reflections, R = 0.036. The compounds consist of SbCl₆^? ions and trications [M(12-crown-4)₂(CH₃CN)]³⁺, in which the M³⁺ ions are ninefold coordinated by the eight oxygen atoms of the crown ether molecules and by the nitrogen atom of the acetonitrile molecule. The lone pair of the M³⁺ ions has no steric effect.     

Organic-inorganic perovskites containing trivalent metal halide layers: the templating influence of the organic cation layer

Thin sheetlike crystals of the metal-deficient perovskites (H2AEQT)M2/3I4 [M = Bi or Sb; AEQT = 5,5"'-bis-(aminoethyl)-2,2':5',2':5',2'-quaterthiophene] were formed from slowly cooled ethylene glycol/2-butanol solutions containing the bismuth(III) or antimony(III) iodide and AEQT.2HI salts. Each structure was refined in a monoclinic (C2/m) subcell, with the lattice parameters a = 39.712(13) A, b = 5.976(2) A, c = 6.043(2) A, beta = 92.238(5) degrees, and Z = 2 for M = Bi and a = 39.439(7) A, b = 5.952(1) A, c = 6.031(1) A, beta = 92.245(3) degrees, and Z = 2 for M = Sb. The trivalent metal cations locally adopt a distorted octahedral coordination, with M-I bond lengths ranging from 3.046(1) to 3.218(3) A (3.114 A average) for M = Bi and 3.012(1) to 3.153(2) A (3.073 A average) for M = Sb. The new organic-inorganic hybrids are the first members of a metal-deficient perovskite family consisting of (Mn+)2/nV(n-2)/nX4(2-) sheets, where V represents a vacancy (generally left out of the formula) and the metal cation valence, n, is greater than 2. The organic layers in the AEQT-based organic-inorganic hybrids feature edge-to-face aromatic interactions among the rigid, rodlike quaterthiophene moieties, which may help to stabilize the unusual metal-deficient layered structures.     

New bonding modes for boraamidinate ligands in heavy group 15 complexes: fluxional behavior of the 1:2 complexes, LiM[PhB(NtBu)2]2 (M = As, Sb, Bi)

The reactions of MCl3 with Li2[PhB(NtBu)2] in 1:1, 1:1.5, and 1:2 molar ratios in diethyl ether produced the monoboraamidinates ClM[PhB(NtBu)2] (1a, M = As; 1b, M = Sb; 1c, M = Bi), the novel 2:3 boraamidinate complexes [PhB(NtBu)2]M-micro-N(tBu)B(Ph)N(tBu)M[PhB(NtBu)2] (2b, M = Sb; 2c, M = Bi), and the bisboraamidinates LiM[PhB(NtBu)2]2 (3a, 3a.OEt2, M = As; 3b, M = Sb; 3c.OEt2, M = Bi), respectively. The 2:3 complexes 2b and 2c were also observed in the reactions carried out in a 1:2 molar ratio at room temperature. All complexes have been characterized by multinuclear NMR spectroscopy (1H, 7Li, 11B, and 13C) and by single-crystal X-ray structural determinations. The molecular units of the mono-boraamidinates 1a-c are isostructural, but their crystal packing is distinct as a result of stronger intermolecular close contacts going from 1a to 1c. In the novel 2:3 bam complexes 2b and 2c, each metal center is N,N'-chelated by a bam ligand and these two [M(bam)]+ units are bridged by the third [bam]2- ligand. The structures of the unsolvated bis-boraaminidate complexes 3a and 3b consist of [Li(bam)]- and [M(bam)]+ monomeric units linked by Li-N and M-N bonds to give a tricyclic structure. Solvation of the Li+ ion by diethyl ether results in a bicyclic structure composed of four-membered BN2As and six-membered BN3AsLi rings in 3a.OEt2. In contrast, the analogous bismuth complex 3c.OEt2 exhibits a tetracyclic structure. Variable-temperature NMR studies reveal that the nature of the fluxional behavior of 3a-c in solution is dependent on the group 15 center.     

Lower main-group element complexes with a soft scorpionate ligand: the structural influence of stereochemically active lone pairs

The syntheses and structures of complexes of the fifth period elements indium and antimony, and the sixth period element bismuth with the soft scorpionate ligand, hydrotris(methimazolyl)borate (Tm(Me)) are reported. A considerable variety of structural motifs were obtained by reaction of the main-group element halide and NaTm(Me). The indium(III) complexes took the form [In(kappa(3)-Tm(Me))(2)](+). This motif could not, however, be isolated for antimony(III), the dominant product being [Sb(kappa(3)-Tm(Me))(kappa(1)-Tm(Me))X] (X = Br, I). An iodo-bridged species [Sb(kappa(3)-Tm(Me))I(mu(2)-I)](2), analogous to a previously reported bismuth complex, was also isolated. Reaction of antimony(III) acetate with NaTm(Me) results in a remarkable species in which three different ligand binding modes are observed. In each antimony complex the influence of the nonbonded electron pair is observed in the structure. Bismuth halides form complexes analogous to those of antimony, with directional lone pairs, but in addition, reaction of Bi(NO(3))(3) with NaTm(Me) results in a complex with a regular S(6) coordination sphere and a nonstereochemically active lone pair. Comparisons are drawn with known Tm(Me) complexes of As, Sn, and Bi in which the stereochemical influence of the lone pairs is negligible and with Tm(Me) complexes of Te and Bi in which the lone pairs are stereochemically active. This study highlights the ability of Tm(Me) to coordinate in a variety of modes as dictated by the metal centre with no adverse effects on the stability of the complexes formed.     

Solid Phase Synthesis, Characterization of Hexamethylenetetramine Complexes of Antimony and Bismuth Trichloride

New hexamethylenetetramine complexes of antimony and bismuth trichloride were synthesized through a solid phase reaction of hexamethylenetetramine and antimony or bismuth trichloride. The formula of the complex is MCl₃(C₆H₁₂N₄)₂⋅H₂O (M=Sb, Bi).The crystal structure of the complexes belongs to monoclinic system and the lattice parameters: a=1.249 nm, b=1.4583 nm, c=1.6780 nm andβ=91.78° for SbCl₃(C₆H₁₂N₄)₂⋅H₂O and a=1.3250 nm, b=1.3889 nm, c=1.7449 nm and β=98.94° for BiCl₃(C₆H₁₂N₄)₂⋅H₂O. Far-infrared spectra reveal that the antimony or bismuth ion is coordinated by the nitrogen atom of the hexamethylenetetramine. The thermal analysis also demonstrates the complex formation between the antimony or bismuth ion and hexamethylenetetramine. The intermediate and final residues in the thermal decomposition process have been analyzed to check the pyrolysis reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Simultaneous determination of antimony and bismuth by beta-correction spectrophotometry and an artificial neural network algorithm

Simultaneous determinations of antimony and bismuth were done by β-correction spectrophotometry and a feed forward neural network algorithm with back propagation of error. The sensitivity was improved using β-correction spectrophotometry. The determination of trace amounts of mixtures of Sb and Bi in various matrices (river, tap and industrial wastewater) were investigated by neural network and β-correction spectrophotometry using the complexes formed between pyrogallol red, Sb and Bi. The results showed that measurement is possible in the ranges of 0.05-5.0 and 0.2-3.2 μg ml⁻¹ for Sb(III) and Bi(III), respectively. The results also show very good agreement between true and predicted concentration values and have the ability to use in routine analysis.