Structure-Directing Interplay between Tetrel and Halogen Bonding in Co-Crystal of Lead(II) Diethyldithiocarbamate with Tetraiodoethylene

四碘乙烯与铅(II)二乙基二硫代氨基甲酸酯共晶体中四氟乙烯键和卤键之间的结构导向相互作用

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Abstract

The co-crystallization of the lead(II) complex [Pb(S(2)CNEt(2))(2)] with tetraiodoethylene (C(2)I(4)) gave the co-crystal, [Pb(S(2)CNEt(2))(2)]∙½C(2)I(4), whose X-ray structure exhibits only a small change of the crystal parameters than those in the parent [Pb(S(2)CNEt(2))(2)]. The supramolecular organization of the co-crystal is largely determined by an interplay between Pb⋯S tetrel bonding (TeB) and I⋯S halogen bonding (HaB) with comparable contributions from these non-covalent contacts; the TeBs observed in the parent complex, [Pb(S(2)CNEt(2))(2)], remain unchanged in the co-crystal. An analysis of the theoretical calculation data, performed for the crystal and cluster models of [Pb(S(2)CNEt(2))(2)]∙½C(2)I(4), revealed the non-covalent nature of the Pb⋯S TeB (-5.41 and -7.78 kcal/mol) and I⋯S HaB (-7.26 and -11.37 kcal/mol) interactions and indicate that in the co-crystal these non-covalent forces are similar in energy.

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