三邻氯苄基锡-2-吲哚甲酸酯的合成、谱学性质和晶体结构(英)

The tri(o-chlorobenzyl)tin ester of 2-indolylcarboxylic acid has been synthesized and characterized by elemental analysis, IR and 1H NMR. The crystal structure has been determined by X-ray single crystal diffraction. The crystal belongs to triclinic with space group P1, a=1.020 0(16) nm, b=1.125 9(18) nm, c=1.321(2) nm, α=83.10(2)°, β=67.597(18)°, γ=84.83(2)°, Z=2, V=1.391(4) nm³, D_x=1.565 Mg·m^-3, μ=1.235 mm^-1, F(000)=656, R=0.049 2, wR=0.131 4. In this compound, the central tin atom is rendered four-coordinated in a tetrahedral structure. The resulting structure is a monomer containing Sn-O bond length of 0.205 4(4) nm. CCDC: 236286.     

二茂铁甲酸(三邻氯苄基)锡配合物的合成、结构和量子化学研究

The novel complex tri(o-chlorobenzyl)tin ferrocenecarboxylate have been synthesized.The crystal structure of the complex has been determined by X-ray diffraction.The crystal belong to orthorhombic with space group Pbca with a=0.1242(5), b=1.7242(7), c=3.0583(13)nm, V=5.928(4)nm³,Z=8, D_c=1.623g·cm^-3,μ(MoKα)= 0.1631cm^-1,F(000)=2896,R₁=0.0461,wR₂=0.0931. The bond lengths of Sn-C is 0.2148(4), 0.2152(6) and 0.2176(5)nm, respectively. The Sn-O is 0.2073(4)nm. The tin atom has a distorted tetrahedral geometry. The study on title complex has been performed,with quantum chemistry calculation by means of G98W package and taking Lanl2dz basis set. The stability of the complex, some frontier molecular orbital energies, the populations of the atomic net charges in complex and composition characteristics of some frontier molecular orbitals have been investigated. CCDC: 184267.     

三(3,5-二氟苄基)氯化锡和四(邻氯苄基)锡的合成、晶体结构及量子化学

3,5-二氟苄基氯和邻氯基苄基氯在适当的溶剂中与锡粉反应,合成了三（3,5-二氟苄基）氯化锡（1）和四（邻氯苄基）锡（2）,经X射线衍射方法测定了新化合物的晶体结构。化合物1属单斜晶系,空间群为C2/c,晶体学参数：a=1.858 33（11）nm,b=1.140 98（7）nm,c=2.690 06（16）nm,β=109.288（10）°,V=5.383 6（6）nm³,Z=8,D_c=1.532 g·cm^-3,μ（Mo Kα）=13.61 cm^-1,F（000）=2 480,R₁=0.085 1,wR₂=0.168 1。化合物2属单斜晶系,空间群为P2₁/m,晶体学参数：a=0.585 54（5）nm,b=1.969 74（18）nm,c=0.857 86（8）nm,β=95.204 0（10）°,V=0.985 34（15）nm³,Z=2,D_c=1.805 g·cm^-3,μ（Mo Kα）=14.91 cm^-1,F（000）=524,R₁=0.054 0,wR₂=0.163 9;中心锡原子为畸变四面体构型。对其结构进行量子化学从头计算,探讨了化合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。测定了化合物的热稳定性。     

三(3,5-二氟苄基)氯化锡和四(邻氯苄基)锡的合成、晶体结构及量子化学

3,5-二氟苄基氯和邻氯基苄基氯在适当的溶剂中与锡粉反应,合成了三(3,5-二氟苄基)氯化锡(1)和四(邻氯苄基)锡(2),经X射线衍射方法测定了新化合物的晶体结构。化合物1属单斜晶系,空间群为C2/c,晶体学参数:a=1.858 33(11)nm,b=1.140 98(7)nm,c=2.690 06(16)nm,β=109.288(10)°,V=5.383 6(6)nm3,Z=8,Dc=1.532 g·cm~(-3),μ(Mo Kα)=13.61 cm~(-1),F(000)=2 480,R1=0.085 1,wR~2=0.168 1。化合物2属单斜晶系,空间群为P21/m,晶体学参数:a=0.585 54(5)nm,b=1.969 74(18)nm,c=0.857 86(8)nm,β=95.204 0(10)°,V=0.985 34(15)nm3,Z=2,Dc=1.805 g·cm~(-3),μ(Mo Kα)=14.91 cm-1,F(000)=524,R1=0.054 0,wR_2=0.163 9;中心锡原子为畸变四面体构型。对其结构进行量子化学从头计算,探讨了化合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。测定了化合物的热稳定性。     

一维链状μ-氯(氧)-三苄基锡的合成和结构研究

合成了两种具有新型结构的苄基锡化合物：一维链状μ-氯-三苄基锡(1)和一维链状μ-氧-三苄基锡(2)，经X-射线方法测定了化合物的晶体结构。晶体结构(1)属正交晶系，空间群为P2₁2₁2₁，晶体学参数：a=0.855 3(3) nm，b=1.081 4(4) nm，c=1.968 1(7) nm，V=1.820 4(11) nm³，Z=4，D_c=1.560 g·cm^-3，μ(Mo Kα)=15.47 cm^-1，F(000)=856，R₁=0.059 7，wR₂=0.141 5。晶体结构(2)属正交晶 系，空间群为P2₁2₁2₁，晶体学参数：a=1.982 3(4) nm，b=1.089 1(2) nm，c=0.861 1(17) nm，V=1.859 0(6) nm³，Z=4，D_c=1.458 g·cm^-3， μ(Mo Kα)=13.76 cm^-1，F(000)=820，R₁=0.032 7，wR₂=0.064 8。配合物中锡原子均呈五配位畸变三角双锥构型。     

三邻氯苄基和三邻氟苄基锡吡咯烷氨荒酸酯的合成及晶体结构

Tri(o-chlorbenzyl)tin dithiotetrahydropyrrolocarbamate 1 and tri(o-fluorbenzyl)tin dithiotetrahydropyrrolocar-bamate 2 were synthesized. Their structures were characterized by elementary analysis， IR and ¹H NMR and the crystal structures were determined by X-ray single crystal diffraction. The crystal 1 belongs to triclinic with space group ， a=0.9076(4)nm， b=1.0663(5)nm， c=1.5193(7)nm， α=75.811(6)°，β=89.344(6)°， γ=72.665(6)°， Z=2， V=1.3577(11)nm³， D_c=1.569g·cm^-3， μ=1.406mm^-1， F(000)=644， R=0.0282， wR=0.0617. The crystal 2 belongs to monoclinic with space group P2₁/c， a=1.355(2)nm， b=1.0143(16)nm， c=1.986(3)nm， β=109.94(2)°， Z=4， V=2.565(7)nm³， D_c=1.539g·cm^-3， μ=1.195mm^-1，F(000)=1200， R=0.0467， wR=0.0788. In the crystals of 1 and 2， the structures consist of discrete molecules containing five-coordinate tin atom in a distorted trigonal bipyramidal configuration. CCDC: 1， 213679; 2， 213680.     

μ-氧-双{三[邻氯(氟)苄基]锡}的合成、结构和量子化学研究

The tri(o-chlorobenzyl)tin chloride as well as the tri(o-fluorobenzyl)tin was treated with aqueous solution of NaOH to formed the μ-oxygen-bis[tri(o-chlorobenzyl)tin] and μ-oxygen-bis[tri(o-fluorobenzyl)tin], respectively. The crystal and molecular structures of compound were determined by X-ray diffraction. The crystal(1) belongs to triclinic space group P1 with a=1.0195(5), b=1.0951(6), c=1.0986(6)nm, α=118.250(7), β=104.923(7), γ=99.534(8)°, V=0.9827(9)nm³,Z=1, D_x=1.701g·cm^-3, μ(MoKα)=17.12cm^-1, F(000)=498, R₁=0.0680, wR₂=0.13014. The crystal(2) are triclinic, space group P1 with a=0.9635(3), b=1.0797(4), c=1.0852(3)nm, α =105.807(5), β=90.551(6), γ=116.382(5)°, V=0.9619(6)nm³, Z=2, D_x=1.595g·cm^-3, μ(MoKα)=13.62cm^-1, F(000)=458, R₁=0.0268, wR₂=0.0674. The bond lengths of Sn-C is 0.2128(9)～2.162(12)nm and 0.2155(4)～0.2162(3)nm, and the Sn-O is 0.1901nm and 0.19166(6)nm, respectively. The bond angle Sn-O-Sn is 180.0(0)°. The tin atom has a distorted tetrahedral geometry. The composition characteristics of some frontier molecular orbitals have been investigated by means of G98W package and taking Lanl2dz basis set. (1) CCDC:184751,(2) CCDC:187572.     

μ-氧-双[三(邻溴苄基)锡]的合成和结构研究

The tri(o-bromobenzyl)tin bromide was treated with aqueous solution of NaOH to formed the μ-oxygen-bis[tri(o-bromobenzyl)tin]. The crystal structures of compound was determined by X-ray diffraction. The crystal belongs to triclinic, space group with a=1.0544(4) nm, b=1.1029 (4) nm, c=1.1309 (4) nm, α =117.031(5) °, β=107.685 (6) °, γ=98.523(6) °, V=1.0506(6)nm³, Z=1, D_x=2.013g·cm^-3, μ(MoKα)=69.25cm^-1, F(000)=606, R₁=0.0524, wR₂=0.1196. In the struture the tin atom has a distorted tetrahedral geometry. CCDC: 220514.     

三(邻溴苄基)溴化锡和四(对溴苄基)锡的合成及结构研究

邻溴苄基溴或对溴苄基溴与锡反应合成三(邻溴苄基)溴化锡(1)和四(对溴苄基)锡(2).经X射线方法测定了新化合物的晶体结构.晶体结构1属斜方六面体晶系,空间群为R-3,晶体学参数:a=1.3389(3) nm, b=1.3389(3) nm, c=2.1896(8) nm, V=3.3993(16) nm3, Z=6, Dx=2.077 Mg·m-3, μ(Mo Kα)=81.83 cm-1, F(000)=2004, R1=0.0477, wR2=0.1372;晶体结构2属正交晶系,空间群为Fdd2,晶体学参数:a=2.1027(7) nm, b=2.3034(8) nm, c=1.1431(4) nm, V=5. 536(3) nm3, Z=8, Dx=1.917 Mg·m-3, μ(Mo Kα)=67.11 cm-1, F(000)=3056, R1=0.0358, wR2=0.0659.化合物1中Sn-C键长为0.2160(8) nm, Sn-Br键长为0.2491(3) nm;化合物2中Sn-C键长分别为0.2175和0.2178 nm.中心锡与亚甲基碳(或溴)原子构成畸型四面体.     

三(邻甲基苄基)氯化锡和二(对甲基苄基)二氯化锡的合成和晶体结构

将邻甲基氯苄和对甲基氯苄在适当的溶剂中与锡粉反应，合成了三(邻甲基苄基)氯化锡1和二(对甲基苄基)二氯化锡2，用X射线衍射方法测定了化合物的晶体结构。化合物(1)的晶体属三方晶系，空间群为R3，晶体学参数：a=1.329 36(8) nm，b=1.329 36(8) nm，c=2.147 0(3) nm，α=β=90°，γ=120°，V=3.285 8(5) nm³，Z=6，D_c=1.424 g·cm^-3，μ(Mo Kα)=12.93 cm^-1，F(000)=1 428，R₁=0.037 1，wR=0.110 2。化合物2的晶体属单斜晶系，空间群为C2/c，晶体学参数：a=2.850 4(3) nm，b=0.491 23(5) nm，c=1.215 32(12) nm，β=112.517(2)°，V=1.571 9(3) nm³，Z=4，D_c=1.690 g·cm^-3，μ(Mo Kα)=19.49 cm^-1，F(000)=792，R₁=0.038 0，wR₂=0.109 4；中心锡原子为畸变四面体配位构型。     

三(邻氯苄基)氯化锡的合成、结构和量子化学研究

邻氯苄基氯与锡反应合成三(邻氯苄基)氯化锡，经x射线方法测定了新化合物 的晶体结构，化合物属三方晶系，空间群为R-3，晶体学参数：α=b=1．3583(4) mn，c=2．1147(8)am，v=3．3790(19)nm~3，Z=6，μ(Mo kα)=16．11cm~-1， r (000)：1572，R_1=O．0755；Sn-C键长分别为0．2148(13)和0．220(2)nm，Sn-C1 键为0．2528(15)和0．2477(13)Bill．中心锡原子与亚甲基碳和氯原子构成畸型四 面体．并对其结构进行量子化学从头计算，探讨化合物的稳定性、分子轨道能量、 原子净电荷布居规律以及一些前沿分子轨道的组成特征．     

三(对氰基苄基)氯化锡的合成及晶体结构研究

苄基锡化合物因其具有丰富的反应性、结构特征及抗癌活性而引起人们的兴趣,最近我们合成了一系列的卤代苄基锡化合物,并报导了它们的晶体结构。在研究中我们发现苯环上连有的取     

Synthesis, Spectroscopic Properties and Structural Characterization of Tri（o-chlorobenzyl）tin Ester of 4-Pyridinecarboxylic Acid

The tri(2-chlorobenzyl)tin(IV) complex with 4-pyridinylcarboxylate ligand tri(o-chlorobenzyl)tin ester of 4-pyridinecarboxylic acid has been synthesized by the reaction of tri(2-chlorobenzyl)tin(Ⅳ) chloride with 4-pyridinyl carboxylic acid and characterized by elemental analysis, IR and ^1HNMR, and its crystal structure was determined by X-ray single-crystal diffraction.     

三(对氟苄基)氯化锡和三(对氟苄基)锡N,N-(1,4-亚丁基)氨荒酸酯的合成及晶体结构

合成了三(对氟苄基)氯化锡(1)和三(对氟苄基)锡N,N-(1,4-亚丁基)氨荒酸酯(2).通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征.用X射线单晶衍射测定了这两个化合物的晶体结构.化合物1为单斜晶系,空间群P21, a=0.8403(3) nm, b=0.5958(2) nm, c=2.0016(8) nm, β=97.052(6)°, Z=2, V=0.9945(7) nm3, Dc=1.608 g/cm3, μ=1.447 mm-1, R1=0.0397, wR2=0.0813.化合物2为单斜晶系,空间群P21/n, a=0.8786(9) nm, b=1.993(2) nm, c=1.5039(15) nm, β=103.548(15)°, Z=4, V=2.560(4) nm3, Dc=1.537 g/cm3, μ=1.197 mm-1, R1=0.0363, wR2=0.0796. 在1的晶体中,锡原子呈四配位畸变四面体构型;2的晶体中,锡原子则是五配位畸变三角双锥构型.     

三(邻氟苄基）氯化锡和四(对氟苄基）锡的合成及结构研究

邻氟苄基氯或对氟苄基氯分别与锡反应合成三(邻氟苄基)氯化锡(1)和四(对氟 苄基)锡(2)．经X射线方法测定了新化合物的晶体结构．晶体结构1属单斜晶系，空 间群为P2(1)／n，晶体学参数：a＝0.5896(9)nm,b-1.262(2)nm,c=2.634(4)nm, V=1.959(5)nm^3,Z=4,Dx=1.632g/cm^3,μ（Mo Kα)=14.69cm^-1,F(000)=952, R1=0.0541,wR2=0.1280;晶体结构2属单余晶系，空间群为Cc,晶体学参数：α=1. 0778(6)nm,b=2.3312(14)nm,c=1.0888(7)nm,V=2.460(3)nm^3,Z=4,Dx=1. 499g/cm^2,μ(Mo Kα)=10.82cm^-1,F(000)=1112,R1=0.0302,wR2=0.0590.在化合 物1和2中Sn-C键长分别为0.2136-0.2148和0.2138-0.2180nm,Sn-Cl键长为0.2378 (4)nm,中心锡与亚甲基碳（氯）原子构成畸型四面体。     

二(对氯苄基)锡双吗啉氨荒酸酯和二(对氯苄基)氯化锡N,N-二乙基氨荒酸酯的合成、表征及晶体结构

利用二(对氯苄基)二氯化锡和吗啉氨荒酸钠、N,N-二乙基氨荒酸钠反应,合成了二(对氯苄基)锡双吗啉氨荒酸酯C24H28Cl2N2O2S4Sn (Mr = 694.31) 1和二(对氯苄基)氯化锡N,N-二乙基氨荒酸酯C19H22Cl3NS2Sn (Mr = 553.54) 2。用X-射线单晶衍射测定了这2个化合物的晶体结构,测试结果表明:化合物1的晶体为单斜晶系,空间群C2/c, a = 21.998(9), b = 6.469(3), c = 20.204(8) ,β= 94.444(6)o , Z = 4, V = 2866.3(19) 3, Dc = 1.609 g/cm3, μ(MoKα) = 1.394 mm-1, F(000) = 1400,S = 0.955, (?)max = 0.000,R = 0.0389, wR = 0.0817。化合物2的晶体为单斜晶系,空间群P21/c, a = 13.088(10), b = 9.304(7), c = 19.593(14) ,β = 107.158(10)o, Z = 4, V = 2280(3) 3, Dc = 1.613 g/cm3,μ(MoKα) = 1.660 mm-1, F(000) = 1104,S = 1.010, (?)max = 0.001,R = 0.0290, wR = 0.0651。在化合物1中,锡原子呈六配位畸变八面体构型, 化合物2的锡原子则是五配位畸变三角双锥构型。