Department of Chemistry and Biochemistry, Ludwig-Maximilian University of Munich, Butenandtstr. 5-13 (D), 81377 Munich, Germany.
Nat Chem. 2009 Jun;1(3):229-35. doi: 10.1038/nchem.179. Epub 2009 May 3.
Compounds that deviate from the normal range of bonding can help to assess the strengths and weaknesses of the models currently used to describe chemical bonds. Furthermore, computer simulations of molecules require experimental data to describe accurately the energies and forces between interacting molecules. Compounds that contain the trinitromethyl group, with three nitro groups bonded to one carbon atom, show remarkable inter- and intramolecular effects. In this paper, we report the structural features of chlorotrinitromethane in the solid state and present the first reliable solid-state geometry parameters of an α-halogen derivative of the trinitromethyl pseudohalogen. We found several intriguing geometrical features in terms of intra- and intermolecular interactions, as well as an exceptionally short carbon-chlorine bond (1.694(1) Å). Using a combined crystallographic and computational approach, we show that these effects can be described in terms of the computed electrostatic potential of the molecular surface.
偏离正常键合范围的化合物有助于评估当前用于描述化学键的模型的优缺点。此外，分子的计算机模拟需要实验数据来准确描述相互作用分子之间的能量和力。含有三硝基甲基基团的化合物，即三个硝基基团与一个碳原子键合，表现出显著的分子间和分子内效应。在本文中，我们报告了固态氯代三硝基甲烷的结构特征，并提出了三硝甲基拟卤代物的第一个可靠的固态几何参数。我们发现了一些有趣的几何特征，包括分子内和分子间相互作用，以及异常短的碳-氯键（1.694(1) Å）。使用组合晶体学和计算方法，我们表明可以根据分子表面的计算静电势来描述这些效应。
