title: Identification and H(D)-bond energies of C-H(D)Cl interactions in chloride-haloalkane clusters: a combined X-ray crystallographic, spectroscopic, and theoretical study.
abstract: 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 [](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-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)).
authors.affiliation: Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., 199034 Saint Petersburg, Russian Federation. v.kukushkin@spbu.ru.
authors.forename: Tatiyana V
authors.initials: TV
authors.lastname: Serebryanskaya
authors.affiliation: Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., 199034 Saint Petersburg, Russian Federation. v.kukushkin@spbu.ru.
authors.forename: Alexander S
authors.initials: AS
authors.lastname: Novikov
authors.affiliation: Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., 199034 Saint Petersburg, Russian Federation. v.kukushkin@spbu.ru.
authors.forename: Pavel V
authors.initials: PV
authors.lastname: Gushchin
authors.affiliation: Department of Chemistry, University of Jyväskylä, P.O. Box 35, FI-40014 Jyväskylä, Finland.
authors.forename: Matti
authors.initials: M
authors.lastname: Haukka
authors.affiliation: Department of Physics, Saint Petersburg State University, 7/9 Universitetskaya Nab., 199034 Saint Petersburg, Russian Federation.
authors.forename: Ruslan E
authors.initials: RE
authors.lastname: Asfin
authors.affiliation: Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., 199034 Saint Petersburg, Russian Federation. v.kukushkin@spbu.ru.
authors.forename: Peter M
authors.initials: PM
authors.lastname: Tolstoy
authors.affiliation: Institute of Chemistry, Saint Petersburg State University, 7/9 Universitetskaya Nab., 199034 Saint Petersburg, Russian Federation. v.kukushkin@spbu.ru and Institute of Macromolecular Compounds of Russian Academy of Sciences, Bolshoii Pr. 31, 199004 Saint Petersburg, Russian Federation.
authors.forename: Vadim Yu
authors.initials: VY
authors.lastname: Kukushkin