Synthesis of an Unprecedented Cu I Polymer with Alternate Cu(μ‐S) 2 Cu and Cu(μ‐Cl) 2 Cu Cores Bridged by Pyridine‐2‐carbaldehyde Thiosemicarbazone

Pyridine‐2‐carbaldehyde thiosemicarbazone {(C 5 H 5 N)(H)C 2 =N–NH–C 1 (=S)NH 2 ; Hpytsc} formes an unprecedented 1D copper(I) coordination polymer, {Cu 4 Cl 4 (μ 3 ‐S,N 4 ‐Hpytsc) 2 (PPh 3 ) 4 } n ( 1 ) in which pyridyl nitrogen binds to Cu(μ‐Cl) 2 Cu core and sulfur bridges two CuCl units, to form alternate Cu(μ‐S) 2 Cu and Cu(μ‐Cl) 2 Cu cores in the polymer. The Cu···Cu contact in Cu(μ‐Cl) 2 Cu core [3.0877(6) Å] is shorter than in Cu(μ‐S) 2 Cu core [3.1826(6) Å].