Torubaev Yury, Skabitskiy Ivan
N.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, Leninsky prospect 31, Moscow 119991, Russian Federation.
Acta Crystallogr C Struct Chem. 2022 Nov 1;78(Pt 11):591-596. doi: 10.1107/S2053229622009949. Epub 2022 Oct 19.
Two new cocrystals of 1,4-diazabicyclo[2.2.2]octane (DABCO, CHN) with 1,2-diiodoethene (1,2-CHI) and 1,2-diiodoethane (1,2-CHI) complete a series of halogen-bond-assisted cocrystals which started with DABCO·CI [Perkins et al. (2012). CrystEngComm, 14, 3033-3038]. The structural and computational analysis of this series illustrate the correlation between the polarization of the I atom and the hybridization of the C atom bound to it. The formation of a rather stable halogen bond by the alkylic iodide of saturated 1,2-CHI was unusual and respective cocrystals are formed only in nonpolar solvents, while, in the polar medium of acetonitrile, a very intense reaction of DABCO quaternization takes place resulting in 1-(2-iodoethyl)-4-aza-1-azoniabicyclo[2.2.2]octane triiodide, CHIN·I or [N(CHCH)N-CHCHI][I].
1,4 - 二氮杂双环[2.2.2]辛烷（DABCO，C₆H₁₂N₂）与1,2 - 二碘乙烯（1,2 - C₂H₂I₂）和1,2 - 二碘乙烷（1,2 - C₂H₄I₂）形成的两种新共晶体完善了一系列以DABCO·Cl [Perkins等人（2012年）。《晶体工程通讯》，14，3033 - 3038] 开始的卤素键辅助共晶体。该系列的结构和计算分析说明了碘原子的极化与与其相连的碳原子的杂化之间的相关性。饱和的1,2 - C₂H₄I₂的烷基碘形成相当稳定的卤素键是不寻常的，相应的共晶体仅在非极性溶剂中形成，而在乙腈的极性介质中，DABCO会发生非常强烈的季铵化反应，生成1 - (2 - 碘乙基)-4 - 氮杂 - 1 - 氮鎓双环[2.2.2]辛烷三碘化物，C₆H₁₅IN₃·I₃或[N(CH₂CH₂)₂N - CH₂CH₂I][I₃]。
