Differences/similarities of supramolecular motifs are discussed in two new thiophosphoramide structures and their Ni molecular complexes: (CHO)P(S)(NHC(S)NHCHCHX) and [{(CHO)P(S)(NC(S)NHCHCHX)}Ni] (X = Cl/CHI/II and III/IV). The structures have equal numbers of donor/acceptor sites contributing to classical hydrogen bonds (PS/CS and 2 × NH in ligands and 2 × PS and 2 × NH in the complexes). However, these donor and acceptor sites contribute to inter/intramolecular hydrogen bonding in ligands and intramolecular hydrogen bonding in complexes.
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