title: Influence of the Homopolar Dihydrogen Bonding C-H⋅⋅⋅H-C on Coordination Geometry: Experimental and Theoretical Studies.
abstract: The reaction of the N-thiophosphorylated thiourea (HOCH2 )(Me)2 CNHC(S)NHP(S)(OiPr)2 (HL), deprotonated by the thiophosphorylamide group, with NiCl2 leads to green needles of the pseudotetrahedral complex [Ni(L-1,5-S,S')2 ]⋅0.5 (n-C6 H14 ) or pale green blocks of the trans square-planar complex trans-[Ni(L-1,5-S,S')2 ]. The former complex is stabilized by homopolar dihydrogen C-H⋅⋅⋅H-C interactions formed by n-hexane solvent molecules with the [Ni(L-1,5-S,S')2 ] unit. Furthermore, the dispersion-dominated C-H⋅⋅⋅ H-C interactions are, together with other noncovalent interactions (C-H⋅⋅⋅N, C-H⋅⋅⋅Ni, C-H⋅⋅⋅S), responsible for pseudotetrahedral coordination around the Ni(II) center in [Ni(L-1,5-S,S')2 ]⋅0.5 (n-C6 H14 ).
authors.affiliation: Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve (Belgium). damir.a.safin@gmail.com.
authors.forename: Damir A
authors.initials: DA
authors.lastname: Safin
authors.affiliation: Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve (Belgium).
authors.forename: Maria G
authors.initials: MG
authors.lastname: Babashkina
authors.affiliation: Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve (Belgium).
authors.forename: Koen
authors.initials: K
authors.lastname: Robeyns
authors.affiliation: Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakow (Poland). mitoraj@chemia.uj.edu.pl.
authors.forename: Mariusz P
authors.initials: MP
authors.lastname: Mitoraj
authors.affiliation: Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakow (Poland).
authors.forename: Piotr
authors.initials: P
authors.lastname: Kubisiak
authors.affiliation: Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST), Université catholique de Louvain, Place L. Pasteur 1, 1348 Louvain-la-Neuve (Belgium).
authors.forename: Yann
authors.initials: Y
authors.lastname: Garcia
keywords: crystal growth; density functional calculations; hydrogen bonds; nickel; noncovalent interactions