Thiosemicarbazone Derivatives of Copper(I): Influence of Substituents ( R ) at N 1 Atom of [(C 5 H 4 N)HC 2 =N 3 N 2 H‐C 1 (=S)N 1 H R ] in the Formation of 1D or 2D Networks of Copper(I) Complexes

Copper(I) halides with N 1 ‐substituted pyridine‐2‐carbaldehyde thiosemicarbazones [(C 5 H 4 N)HC 2 =N 3 N 2 H‐C 1 (=S)N 1 H R ] in the presence of Ph 3 P have formed complexes of stoichiometry, [Cu X (Hpytsc‐N 1 H R )(Ph 3 P) 2 ] [ X , R ; Br, Me ( 1 ); Br, Et ( 2 ), Cl, Ph ( 3· CH 3 CN)]. All these complexes are characterised by elemental analysis, IR and NMR ( 1 H, 31 P) spectroscopy and X‐ray crystallography. The role of substituents at N 1 atom of pyridine‐2‐carbaldehyde thiosemicarbazones in intermolecular interactions in copper(I) complexes is described. A 1D polymer of compound 1 is formed by intermolecular CH (methyl) ··· π (py) interactions. The hydrogen atoms of EtN 1 H and ethyl group interact with the phenyl ring of PPh 3 {via EtN 1 H ··· π (Ph) , H 2 CH (Et) ··· π (Ph) } to form a 1D polymer of 2 . A 2D sheet arrangement of compound 3 is formed by pyridyl–phenyl (CH (py) ··· π (Ph) ) interactions along the a axis and phenyl–phenyl [CH (Ph) ··· π (Ph) ] interactions (phenyl at N 1 with phenyl of PPh 3 ) along the b axis.