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★声明：本文仅代表个人观点，笔者学识有限，资料整理过程中难免存在疏漏谬误，请不吝指正。 环戊基锂和环己基锂晶体结构 ★信源★ Galen Stucky课题组在期刊《美国化学会志》（Journal of the American Chemical Society）报道了环己基锂晶体结构，论文为“J. Am. Chem. Soc. 1974, 96, 6048–6055. DOI [1]: 10.1021/ja00826a015.”；Paul G. Williard课题组在期刊《美国化学会志》报道了环戊基锂晶体结构，论文为“J. Am. Chem. Soc. 2013, 135, 12400–12406. DOI: 10.1021/ja4059102.”。 ★基本信息★ 中文名称：环戊基锂 英文名称：Cyclopentyllithium 化学简式：C5H9Li或LiC5H9 简写形式：c-PenLi或Li(c-Pen) CAS：23473-12-3(c-PenLi), 1449688-32-7([c-PenLi]6) CCDC [2]：944702 DOI：10.5517/cc10q181 中文名称：环己基锂 英文名称：Cyclohexyllithium 化学简式：C6H11Li或LiC6H11 简写形式：CyLi或LiCy CAS：10074-42-7(LiCy), 53620-58-9([LiCy]6), 53620-59-0([LiCy]6·C6H6) CCDC：1124648 ★晶体制备和培养★ 如图1所示（由ChemBioDraw [3]绘制），环己基锂和环戊基锂由相应氯代烃和金属锂反应制备。环己基锂在苯（C6H6, benzene, CAS: 71-43-2）中重结晶得到[LiCy]6·C6H6晶体，取决于浓度，得到无色针状或双锥形晶体。环戊基锂在庚烷（C7H16, heptane, CAS: 142-82-5）中结晶，或者在甲苯（C7H8, toluene, CAS: 108-88-3）中于–20 ℃下静置数天结晶。 ▲图1 环己基锂和环戊基锂合成 ★晶体结构★ 其结构示意图如图2所示，其晶体结构图如图3–4所示（由Diamond[4]绘制）。晶体结构表明环戊基锂/环己基锂是一个六聚体，六个金属锂构成一个八面体，该八面体的六个面上各有一个环戊基/环己基，环戊基/环己基的亚甲基碳桥联三个锂金属，因此其结构式可写为[Li(μ3-η1:η1:η1-c-Pen)]6/[Li(μ3-η1:η1:η1-Cy)]6，如果不写异丙基与金属之间的键合模式，则可写为[c-PenLi]6/[CyLi]6，其中[Li(μ3-η1:η1:η1-c-Pen)]6与四氢呋喃（THF, tetrahydrofuran, CAS: 109-99-9）反应会变成四聚体，环戊基仍然桥联三个锂金属，每个锂上有一个四氢呋喃配位，其晶体结构如图5所示。 ▲图2 环己基锂和环戊基锂结构示意图 ▲图3 环己基锂晶体结构图（球棍模型，隐藏溶剂分子苯） ▲图4 环戊基锂晶体结构图，椭球率为10% ▲图5 [c-PenLi(THF)]4晶体结构图，椭球率为10% 论文和晶体数据可从期刊主页下载，也可以从以下链接下载： 提取码: x67w 参考文献 [1] (a)International Organization for Standardization (2012). ISO 26324:2012. Information and Documentation – DigitalObject Identifier System. http://www.iso.org/iso/catalogue_detail.htm?csnumber=43506. (b) McDonald J. D.;Levine-Clark, M. Encyclopedia of Libraryand Information Sciences. Fourth Edition, CRC Press, 2017. DOI: 10.1081/e-elis4. (c) Liu, J. Digital ObjectIdentifier (DOI) and DOI Services: An Overview. Libri 2021, 71, 349‒360. DOI:10.1515/libri-2020-0018. (d) International Organization forStandardization (2022). ISO 26324:2022. Informationand Documentation – Digital Object Identifier System. https://www.iso.org/standard/81599.html[2] (a)Allen, F. H. The Cambridge Structural Database: A Quarter of a Million CrystalStructures and Rising. Acta Cryst. 2002, B58, 380–388. DOI:10.1107/S0108768102003890. (b) Groom, C. R.; Bruno, I. J.; Lightfoot, M.P.; Ward, S. C. The Cambridge Structural Database. Acta Cryst. 2016, B72, 171–179. DOI:10.1107/S2052520616003954. (c) Mitchell, J.; Robertson, J. H.; Raithby,P. R. Cambridge Crystallographic Data Centre (CCDC). Comprehensive Coordination Chemistry III 2021, 413–437. [3] (a)Klein, F. M. CS ChemDraw Pro,1 Version 3.1 for Windows. J. Chem. Inf. Comput. Sci. 1995, 35, 166–167. DOI: 10.1021/ci00023a026. (b)Cousins, K. R. ChemDraw 6.0 Ultra CambridgeSoft Corporation, 100 Cambridge ParkDrive, Cambridge, MA 02140. http://www.camsoft.com. Commercial Price: $1395.Academic Price: $699. J. Am. Chem. Soc. 2000, 122, 10257–10258. DOI: 10.1021/ja0047572.(c) Buntrock, R. E. ChemOffice Ultra 7.0. J. Chem. Inf. Comput. Sci. 2002, 42, 1505–1506. DOI: 10.1021/ci025575p. (d) Li, Z.; Wan, H.; Shi, Y.;Ouyang, P. Personal Experience with Four Kinds of Chemical Structure DrawingSoftware: Review on ChemDraw, ChemWindow, ISIS/Draw, and ChemSketch. J. Chem. Inf. Comput. Sci. 2004, 44, 1886–1890. DOI: 10.1021/ci049794h.(e) Mendelsohn, L. D. ChemDraw8 Ultra, Windows and Macintosh Versions. J. Chem. Inf. Comput. Sci. 2004, 44, 2225–2226. DOI: 10.1021/ci040123t. (f) Cousins, K. R. ChemDrawUltra 9.0. CambridgeSoft, 100 CambridgePark Drive, Cambridge, MA 02140. www.cambridgesoft.com. See Web site for pricing options. J. Am. Chem. Soc. 2005, 127, 4115–4116. DOI:10.1021/ja0410237. (g) Zielesny, A. Chemistry Software PackageChemOffice Ultra 2005. J. Chem. Inf.Model. 2005, 45, 1474–1477. DOI:10.1021/ci050273j. (h) Mills, N. ChemDraw Ultra 10.0 CambridgeSoft, 100CambridgePark Drive, Cambridge, MA 02140. www.cambridgesoft.com. CommercialPrice: $1910 for download, $2150 for CD-ROM; Academic Price: $710 fordownload, $800 for CD-ROM. J. Am. Chem. Soc. 2006, 128, 13649–13650. DOI: 10.1021/ja0697875. (i) Kerwin, S. M.ChemBioOffice Ultra 2010 Suite. J. Am. Chem. Soc. 2010, 132, 2466–2467. DOI: 10.1021/ja1005306. (j) Milne, G. W. A. SoftwareReview of ChemBioDraw 12.0. J. Chem. Inf.Model. 2010, 50, 2053. DOI:10.1021/ci100385n. (k) Narayanaswamy, V. K.; Rissdörfer, M.; Odhav, B.Review on CambridgeSoft ChemBioDraw Ultra 13.0v. Int. J. Theor. Appl. Sci. 2013, 5, 43–49. [4] Brandenburg,K.; Putz, H. DIAMOND – Visual Crystal Structure Information System.Ver. 4.6.1; Crystal Impact: Bonn, Germany, 2019.
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