Synthesis,Crystal Structure and Quantum Chemical Study of the Ladder Organotin Compound {[（C6H5CH2）2Sn]2（O）（Cl2）}2

The title compound {[（C6H5CH2）2Sn]2（O）（Cl2）}2 has been synthesized by the reaction of bisbenzyltin dichloride with NaOH dilute solution, and its structure was determined by X-ray diffraction. The crystal belongs to monoclinic, space group C2/c, with a = 2.5081（17）, b = 1.0089（7）, c = 2.0909（14） nm, β = 94.267（8）°, V= 5.276（6） nm^3, Z = 4, De= 1.734 g/cm^3,μ（MoKa） = 21.55 cm^-1, F（000） = 2704, R = 0.0398 and Rw = 0.1024. According to structural analysis, the tin atom adopts a distorted five-coordinate trigonal bipyramidal geometry, and the ladder-like structure is shaped by one planar four-membered Sn2O2 ring together with two planar four-membered Sn2OCl rings.     

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.     

{Cu（Ⅱ）（Me6[14]-4，11-二烯N4）}（ClO4）2的晶体结构和从头算研究

Me6[14]4,11 dieneN4与Cu2+配合形成大环配合物,经X射线衍射测定其晶体结构,并用量子化学从 头算方法研究配合物的电子结构及分子轨道组成.该晶体属于单斜晶系,空间群为P21/c,晶胞参数:a= 1.0483(4),b=1.6956(2),c=1.3838(2)nm,β=105.11(2)°,V=2.37479(10)nm3,Z=4,Dc=1.518g/cm3, μ=11.92cm 1,F(000)=1132,R1=0.042.大环配体的N与Cu配合分别形成椅式六员环和半椅式五员环, N-Cu-N键角差异使中心金属原子与配基原子构成畸形四方形,两个甲基位于大环同侧形成大环的“旗杆”碳 的结构特征.     

三(3,5-二甲基苄基)氯化锡和四(间氰基苄基)锡的合成、晶体结构和量子化学研究

以3,5-二甲基苄基氯和间氰基苄基氯在适当的溶剂中与锡粉反应,合成了三(3,5-二甲基苄基)氯化锡(1)和四(间氰基苄基)锡(2),经X射线衍射方法测定了化合物的晶体结构。化合物1属单斜晶系,空间群为P21/m,晶体学参数:a=0.584 03(4)nm,b=1.966 37(14)nm,c=0.856 46(5)nm,β=95.138(3),V=0.979 62(11)nm3,Z=2,Dc=1.735 g·cm-3,μ(Mo Kα)=14.53 cm-1,F(000)=524,R1=0.043 7,w R2=0.123 2。化合物2属单斜晶系,空间群为C2/c,晶体学参数:a=1.692 21(12)nm,b=1.167 41(8)nm,c=1.539 41(11)nm,β=116.615(10)°,V=2.718 9(3)nm3,Z=4,Dc=1.424 g·cm-3,μ(Mo Kα)=9.67cm-1,F(000)=1 176,R1=0.017 5,w R2=0.046 1;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,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。     

四(对氯苄基)锡的合成、结构和量子化学研究

The tetra(p-chlorobenzyl)tin has been synthesized via reaction of p-chlorobenzyl chloride with Sn and struc-turally determined by X-ray diffraction method. The crystal belongs to orthorhombic space group Fdd2 with a=2.1243(6), b=2.2136(6), c=1.1242(3)nm,V=5.286(2)nm³, Z=8, D_x=1.560Mg·m^-3, μ(MoKα)=13.86cm^-1,F(000)=2480,find R=0.0331 for 2191 unique reflection [I >2σ(I)]. The bond lengths of Sn-C is 0.2167,0.2183nm,respectively.The tin atom has a distorted tetrahedral geometry. The study on title compound has been performed,with ab initio calculation by means of G98W package and taking Lanl2dz basis set.The sta-bilities of the compound,some frontier molecular orbital energies,the populations of the atomic net charges in compound and composition characteristics of some frontier molecular orbitals have been investigated. CCDC:180868.     

水合二(对叔丁基苄基)二氯化锡的合成及晶体结构

The organotin hydration di(p-tert-butylbenzyl)tin dichloride has been synthesized. The crystal structure of complex has been determined by X-ray diffraction. The crystal belongs to orthorhombic space group Pmma with a=1.108 4(2) nm, b=3.492 0(7) nm, c=0.626 36(12) nm, V=2.424 3(8) nm³, Z=4, D_c=1.376 g·cm^-3, μ(Mo Kα)=12.82 cm^-1, F(000)=1 024, R₁=0.085 9, wR=0.225 7. The bond lengths of Sn-Cl are 0.236 0(2) nm and 0.250 8(4) nm, the Sn-C is 0.212 1(11) nm, the Sn-O is 0.233 2(12) nm. The tin rendered five-coordinate in a distorted trigonal bipyramidal configuration. CCDC: 648618.     

茂名颗粒油页岩的干燥与崩碎

我国广东省茂名油页岩的孔隙率大,毛细孔发达,含水量高达13—22%(一般为18%)。在干馏过程中,耗热多,并发生崩碎现象,致使干馏炉阻力增加,操作困难。因此,茂名油页岩的干燥与崩碎问题与生产关系重大,但至今尚未发现有关文献报导。本文应用LCT-1型热重仪,对粒径为5—11mm 的茂名油页岩进行了干燥试验,以恒速升温方法取得干燥动力学数据,得出干燥速度与粒径、干燥温度及时间的关系。还考察了油页岩的崩碎现象,并对崩碎原因作了初步探讨。     

三(邻氯苄基)锡3-吲哚乙酸酯的合成和结构研究

μ-氧-双[三(邻氯苄基)锡]与3-吲哚乙酸反应合成三(邻氯苄基)锡3-吲哚乙酸酯,经X射线衍射方法测定了新化合物的晶体结构.配合物属三斜晶系,空间群为P-1,晶体学参数:a=0.8376(3)nm,b=1.1118(3)nm,c=1.6557(5)nm,α=102.747(5)°,β=101.238(5)°,γ=107.683(5)°,V=1.4382(8)nm3,Z=2,Dc=1.549g/cm3,μ(Mo Ka)=11.96cm-1,F(000)=674,R1= 0.0369,Rw=0.0785;在配合物中Sn-C键长分别为0.2143(4),0.2153(4)和0.2161(4)um,Sn-O键为0.2072(3)nm.中心锡与亚甲基碳和氧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。     

二(2-吡啶甲酸)二(邻氟苄基)锡和一维链状4-吡啶甲酸三(邻氟苄基)锡的合成和晶体结构

μ-氧-双[三(邻氟苄基)锡]与2-吡啶甲酸或4-吡啶甲酸在苯溶剂中反应合成有机锡配合物二(2-吡啶甲酸)二(邻氟苄基)锡(1)和一维链状4-吡啶甲酸三(邻氟苄基)锡(2)，经X射线衍射方法测定了新化合物的晶体结构。配合物(1)属四方晶系，空间 群为I4₁/a，晶体学参数：a=1.562 0(3) nm，b=1.562 0(3) nm，c=1.984 7(4) nm，α=β=γ=90°，V=4.842 4(16) nm³，Z=8,D_c=1.594 Mg·m^-3， μ(Mo Kα)=11.06 cm^-1，F(000)=2 320，R₁=0.024 3，wR=0.062 5。配合物(2)属单斜晶系，空间群为P2₁/n，晶体学参数：a=0.869 8(3) nm，b=1.880 5(7) nm，c=1.475 1(5) nm，β=90.937(6)°，V=2.412 3(15) nm³，Z=4，D_c=1.564 Mg·m^-3，μ(Mo Kα)=11.07 cm^-1，F(000)=1 136，R₁=0.028 8，wR₂=0.057 9；配合物1为单体结构，中心锡为六配位畸变八面体构型。配合物2通过4-吡啶甲酸配体氮原子的桥联，形成五配位三角双锥型的链状结构。