Issue 28, 2016

A family of heterotetrameric clusters of chloride species and halomethanes held by two halogen and two hydrogen bonds

Abstract

Two previously reported 1,3,5,7,9-pentaazanona-1,3,6,8-tetraenate (PANT) chloride platinum(II) complexes [PtCl{HN[double bond, length as m-dash]C(R)N[double bond, length as m-dash]CN[C(Ph)[double bond, length as m-dash]C(Ph)]C[double bond, length as m-dash]NC(R)[double bond, length as m-dash]NH}] (R = tBu 1, Ph 2) form solvates with halomethanes 1·1¼CH2Cl2, 1·1⅖CH2Br2, and 2·CHCl3. All these species feature novel complex-solvent heterotetrameric clusters, where the structural units are linked simultaneously by two C–X⋯Cl–Pt (X = Cl, Br) halogen and two C–H⋯Cl–Pt hydrogen bonds. The geometric parameters of these weak interactions were determined using single-crystal XRD, and the natures of the XBs and HBs in the clusters were studied for the isolated model systems (1)2·(CH2Cl2)2, (1)2·(CH2Br2)2, and (2)2·(CHCl3)2 using DFT calculations and Bader's AIM analysis. The evaluated energies of the weak interactions are in the range 0.9–3.0 kcal mol−1. The XBs and HBs in the reported clusters are cooperative. In the cases of (1)2·(CH2Cl2)2 and (1)2·(CH2Br2)2, the contribution of the HBs to the stabilization of the system is dominant, whereas for (2)2·(CHCl3)2 contributions of both types of the non-covalent interactions are almost the same. Crystal packing and other forces such as, e.g. dipole–dipole interactions, also affect the formation of the clusters.

Graphical abstract: A family of heterotetrameric clusters of chloride species and halomethanes held by two halogen and two hydrogen bonds

Supplementary files

Article information

Article type
Paper
Submitted
20 May 2016
Accepted
10 Jun 2016
First published
13 Jun 2016
This article is Open Access
Creative Commons BY-NC license

CrystEngComm, 2016,18, 5278-5286

A family of heterotetrameric clusters of chloride species and halomethanes held by two halogen and two hydrogen bonds

D. M. Ivanov, A. S. Novikov, G. L. Starova, M. Haukka and V. Yu. Kukushkin, CrystEngComm, 2016, 18, 5278 DOI: 10.1039/C6CE01179A

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