Influence of the homopolar dihydrogen bonding C-H...H-C on coordination geometry: experimental and theoretical studies
(2015) Chemistry: A European Journal — Vol. 21, n° 46, p. 16679-16687 (2015)
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Safin-InfluenceoftheHomopolarDihydrogenBondingC-HH-ConCoordinationGeometryExperimentalandTheoreticalStudies.pdf
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- (en) The reaction of the N-thiophosphorylated thiourea (HOCH2)(Me)2CNHC(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-C6H14) 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 NiII center in [Ni(L-1,5-S,S′)2] 0.5 (n-C6H14). Hidden attraction: Dispersion-dominated homopolar C-H⋯H-C interactions not only stabilize the crystal structures of pseudotetrahedral NiII units interacting with n-hexane molecules, but can also facilitate crystallization (see figure). In addition, they are also responsible, together with other noncovalent interactions (C-H⋯N, C-H⋯Ni, C-H⋯S), for deviation from planarity around the metal center
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Safin, D., Babashkina, M., Robeyns, K., Mitoraj, M. P. A., Kubisiak, P., & Garcia, Y. (2015). Influence of the homopolar dihydrogen bonding C-H...H-C on coordination geometry: experimental and theoretical studies. Chemistry: A European Journal, 21(46), 16679-16687. https://doi.org/10.1002/chem.201501499 (Original work published 2015)