TY - JOUR

T1 - Identification and H(D)-bond energies of C-H(D)⋯Cl interactions in chloride-haloalkane clusters

T2 - A combined X-ray crystallographic, spectroscopic, and theoretical study

AU - Serebryanskaya, Tatiyana V.

AU - Novikov, Alexander S.

AU - Gushchin, Pavel V.

AU - Haukka, Matti

AU - Asfin, Ruslan E.

AU - Tolstoy, Peter M.

AU - Kukushkin, Vadim Yu

N1 - Funding Information: TVS is grateful to Saint Petersburg State University for the postdoctoral fellowship (12.50.1560.2013). PVG, ASN, and VYK thank Russian Foundation for Basic Research for support of their studies (grants 15-03-01563, 16-33-60063, and 16-03-00441). ATRFTIR studies were performed at the Center for Geo-Environmental Research and Modeling (GEOMODEL) of Research Park of Saint Petersburg State University within the framework of Russian Foundation for Basic Research grant 14-03-00111 (PMT and REA). The authors are grateful to Prof. Dr A. G. Starikov (Southern Scientific Center of Russian Academy of Sciences, Rostov-on-Don, Russian Federation) for providing computational facilities and also for valuable comments. We also thank Prof. Dr E. S. Shubina for useful advices and helpful discussion. Publisher Copyright: © The Owner Societies 2016. Copyright: Copyright 2016 Elsevier B.V., All rights reserved.

PY - 2016

Y1 - 2016

N2 - The cationic (1,3,5-triazapentadiene)PtII complex [Pt{NHC(N(CH2)5)N(Ph)C(NH2)NPh}2]Cl2 ([1]Cl2) was crystallized from four haloalkane solvents giving [1][Cl2(CDCl3)4], [1][Cl2(CHBr3)4], [1][Cl2(CH2Cl2)2], and [1][Cl2(C2H4Cl2)2] solvates that were studied by X-ray diffraction. In the crystal structures of [1][Cl2(CDCl3)4] and [1][Cl2(CHBr3)4], the Cl- ion interacts with two haloform molecules via C-D⋯Cl- and C-H⋯Cl- contacts, thus forming the negatively charged isostructural clusters [Cl(CDCl3)2]- and [Cl(CHBr3)2]-. In the structures of [1][Cl2(CH2Cl2)2] and [1][Cl2(C2H4Cl2)2], cations [1]2+ 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-H⋯Cl- hydrogen bonds ranged from 1 to 6 kcal mol-1. An exponential correlation (R2 > 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-H⋯Cl- bond estimated using ATRFTIR spectroscopy (2.7 kcal mol-1).

AB - The cationic (1,3,5-triazapentadiene)PtII complex [Pt{NHC(N(CH2)5)N(Ph)C(NH2)NPh}2]Cl2 ([1]Cl2) was crystallized from four haloalkane solvents giving [1][Cl2(CDCl3)4], [1][Cl2(CHBr3)4], [1][Cl2(CH2Cl2)2], and [1][Cl2(C2H4Cl2)2] solvates that were studied by X-ray diffraction. In the crystal structures of [1][Cl2(CDCl3)4] and [1][Cl2(CHBr3)4], the Cl- ion interacts with two haloform molecules via C-D⋯Cl- and C-H⋯Cl- contacts, thus forming the negatively charged isostructural clusters [Cl(CDCl3)2]- and [Cl(CHBr3)2]-. In the structures of [1][Cl2(CH2Cl2)2] and [1][Cl2(C2H4Cl2)2], cations [1]2+ 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-H⋯Cl- hydrogen bonds ranged from 1 to 6 kcal mol-1. An exponential correlation (R2 > 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-H⋯Cl- bond estimated using ATRFTIR spectroscopy (2.7 kcal mol-1).

UR - http://www.scopus.com/inward/record.url?scp=84969915684&partnerID=8YFLogxK

U2 - 10.1039/c6cp00861e

DO - 10.1039/c6cp00861e

M3 - Article

VL - 18

SP - 14104

EP - 14112

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 20

ER -