双（取代环戊二烯基）二氯化锆的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了双［１－苄基－１－乙基丙基环戊二烯基］二氯化锆［η５－Ｃ５Ｈ４Ｃ（Ｃ２Ｈ５）２ＣＨ２Ｃ６Ｈ５］２ＺｒＣｌ２（Ｉ）及（１，２－二异丁基－１，２－甲基－乙基桥联）双环戊二烯基二氯化锆［η５－Ｃ５Ｈ４Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ５Ｈ４－η５］ＺｒＣｌ２（Ⅱ）的结构。二者皆为单斜晶系，（Ｉ）的空间群为Ｐ２／ｎ，ａ＝１２．５８２（３），ｂ＝７．９９２（２），ｃ＝１４．９７９（３）Ａ，β＝１０１．６８（１）°，Ｖ＝１４７４．９（９）Ａ３，Ｍｒ＝６１２．８４，Ｚ＝２，Ｄｘ＝１．３８ｇ／ｃｍ３，μ＝５．６９ｃｍ（－１），Ｆ（０００）＝６４０，Ｒ＝０．０３３，Ｒω＝０．０３６。（Ⅱ）的空间群为Ｃｃ，ａ＝１３．３０９（３），ｂ＝９．５９１（１），ｃ＝１６．４４９（８）Ａ。β＝４．８３（３）°，Ｖ＝２０９．２（２）Ａ３，Ｍｒ＝４５８．６３，Ｚ＝４，Ｄｘ＝１．４５６ｇ／ｃｍ３，μ＝７．７７ｃｍ（－１），Ｆ（０００）＝９５２，Ｒ＝０．０５１，Ｒω＝０．０６１。化合物（Ｉ）以重叠式存在，两个苄基处于反式。晶体（Ⅱ）以交叉式存在，甲基、异丁基以反式构象存在。

Crystal Structure Analyses of Bis(substituted-cyclopentadienyl) zironium Dichlorides

The crystal and molecular structures of bis (1-benzyl-1-ethyl-propanylcyclopentadienyl)zironium dichloride [η5-C5H4C(C2H5)2CH2C6H5]2ZrCl2(I) and [1, 2-diisobutyl-1, 2-dimethyl-ethenedicyclopentadienyl]zironium dichloride [η5-C5H3C(CH3) (C4H9-i)C(CH3)(C4H9-i) C5H4-η5]ZrCl2 (Ⅱ) are reported. They are both monoclinic. The crystallographic data are as follows: (I),space group P2/n, a=12. 582{3) ,b=7. 992(2) , c=14.979(3) ,β= 101. 68(1)°, V=1474. 9(9) A3, M.= 612- 84, Z=2 , Dx=1. 380 g/cm3, μ= 5. 69cm-1, F(000) = 640, R=0. 033, Rω=0. 036; (Ⅱ) , space group Cc, a=13. 309(3) , b=9.591(1) , c=16. 449(8) ,β=94. 83(3) , V=2092(2) A3, M.=458. 63 , Z=4 , Dx= 1. 456 g/cm3, μ= 7. 77 cm-1, F(000)=952 , R=0. 051 , Rω= 0.061. The substituents are exactly eclipsed above and below the ZrCl2 group in compound(I). The benzyl groups are directed away from each other on opposite side of the molecule. The cyclopentadienyl rings are slightly staggered in projection on the ZrCl2 plane in compound(Ⅱ). The methyl group and iso-butyl groups are in opposite configuration.