Serebryanskaya Tatiyana V, Novikov Alexander S, Gushchin Pavel V, Haukka Matti, Asfin Ruslan E, Tolstoy Peter M, Kukushkin Vadim Yu
Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., 199034 Saint Petersburg, Russian Federation.
Department of Chemistry, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland.
Phys Chem Chem Phys. 2016 May 18;18(20):14104-12. doi: 10.1039/c6cp00861e.
The cationic (1,3,5-triazapentadiene)Pt(II) complex [Pt{NH[double bond, length as m-dash]C(N(CH2)5)N(Ph)C(NH2)[double bond, length as m-dash]NPh}2]Cl2 ([]Cl2) was crystallized from four haloalkane solvents giving [][Cl2(CDCl3)4], [][Cl2(CHBr3)4], [][Cl2(CH2Cl2)2], and [][Cl2(C2H4Cl2)2] solvates that were studied by X-ray diffraction. In the crystal structures of [][Cl2(CDCl3)4] and [][Cl2(CHBr3)4], the Cl(-) ion interacts with two haloform molecules via C-DCl(-) and C-HCl(-) contacts, thus forming the negatively charged isostructural clusters Cl(CDCl3)2 and Cl(CHBr3)2. In the structures of [][Cl2(CH2Cl2)2] and [][Cl2(C2H4Cl2)2], cations are linked to a 3D-network by a system of H-bondings including one formed by each Cl(-) ion with CH2Cl2 or C2H4Cl2 molecules. The lengths and energies of these H-bonds in the chloride-haloalkane clusters were analyzed by DFT calculations (M06 functional) including AIM analysis. The crystal packing noticeably affected the geometry of the clusters, and energy of C-HCl(-) hydrogen bonds ranged from 1 to 6 kcal mol(-1). An exponential correlation (R(2) > 0.98) between the calculated Cl(-)H distances and the energies of the corresponding contacts was found and used to calculate hydrogen bond energies from the experimental Cl(-)H distances. Predicted energy values (3.3-3.9 kcal mol(-1) for the Cl(CHCl3)2 cluster) are in a reasonable agreement with the energy of the Cl3C-HCl(-) bond estimated using ATRFTIR spectroscopy (2.7 kcal mol(-1)).
阳离子（1,3,5 - 三氮杂戊二烯）铂（II）配合物[Pt{NH[双键，长度如m - 破折号]C(N(CH2)5)N(Ph)C(NH2)[双键，长度如m - 破折号]NPh}2]Cl2（[ ]Cl2）从四种卤代烷溶剂中结晶得到[ ][Cl2(CDCl3)4]、[ ][Cl2(CHBr3)4]、[ ][Cl2(CH2Cl2)2]和[ ][Cl2(C2H4Cl2)2]溶剂化物，并通过X射线衍射进行了研究。在[ ][Cl2(CDCl3)4]和[ ][Cl2(CHBr3)4]的晶体结构中，Cl(-)离子通过C - DCl(-)和C - HCl(-)接触与两个卤仿分子相互作用，从而形成带负电荷的同构簇Cl(CDCl3)2和Cl(CHBr3)2。在[ ][Cl2(CH2Cl2)2]和[ ][Cl2(C2H4Cl2)2]的结构中，阳离子 通过包括每个Cl(-)离子与CH2Cl2或C2H4Cl2分子形成的一个氢键在内的氢键体系连接成三维网络。通过包括AIM分析的DFT计算（M06泛函）分析了氯化物 - 卤代烷簇中这些氢键的长度和能量。晶体堆积显著影响了簇的几何形状，C - HCl(-)氢键的能量范围为1至6 kcal mol(-1)。发现计算得到的Cl(-)H距离与相应接触的能量之间存在指数相关性（R(2) > 0.98），并用于根据实验测得的Cl(-)H距离计算氢键能量。预测的能量值（对于Cl(CHCl3)2簇为3.3 - 3.9 kcal mol(-1)）与使用ATRFTIR光谱估计的Cl3C - HCl(-)键的能量（2.7 kcal mol(-1)）合理一致。
