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The asymmetric unit of the title compound, [Zn(NCS)(C 12 H 7 ClN 2 ) 2 ][Zn(NCS) 3 (C 12 H 7 ClN 2 )], contains two cations and two anions. In the cations, the Zn II  ions have distorted trigonal–bipyramidal environments formed by four N atoms from two 2-chloro-1,10-phenanthroline (cphen) ligands and one N atom from a thio­cyanate ligand. The Zn II  atoms in the complex anions also have distorted trigonal–bipyramidal environments, formed by two N atoms from a cphen ligand and three N atoms from three thio­cyanato ligands. The crystal packing exhibits π–π inter­actions between the rings of the cphen ligands [shortest centroid–centroid distance = 3.586 (5) Å] and short inter­molecular S⋯Cl [3.395 (5) Å] and S⋯S [3.440 (4) Å] contacts.

acta crystallographica. section e

Bis(2-chloro-1,10-phenanthroline-κ2N,N′)(thiocyanato-κN)zinc (2-chloro-1,10-phenanthroline-κ2N,N′)tris(thiocyanato-κN)zincate