Abstract: | Crystal Structures of ?Supramolecular”? Benzo‐18‐crown‐6 Potassium Tetrathiocyanato Metallates: A Dimeric Complex {K(Benzo‐18‐crown‐6)]2Hg(SCN)4]}2 and Two Isomeric Complexes K(Benzo‐18‐crown‐6)]Cd(SCN)3] Containing Trithiocyanato Cadmate Anions with Chain Structures By reaction of potassium thiocyanatomercurate(II) complexes with benzo‐18‐crown‐6 (2,3‐benzo‐1,4,7,10,13,16‐hexaoxacyclooctadec‐2‐ene) crystals of {K(benzo‐18‐crown‐6)]2Hg(SCN4)]}2 ( 1 ) were obtained. 1 crystallizes monoclinic, space group P21/n (non‐standard setting of P21/c), a = 1737.35(2), b = 1377.16(2), c = 1984.12(3) pm, β = 100.637(1)°, Z = 2. With potassium tetrathiocyanatocadmate(II) two modifications of a complex K(benzo‐18‐crown‐6)]Cd(SCN)3] ( 2 , 3 ), of different symmetry were formed. 2 crystallizes monoclinic, P21/c, a = 1158,31(3), b = 1096,55(2), c = 2028,46(2) pm, β = 99,5261(2)°, Z = 4, 3 orthorhombic, P21cn, a = 1105,95(3), b = 1413,07(4), c = 1617,10(5) pm, Z = 4. 1 has a dimeric structure, built up from a dication K2(benzo‐18‐crown‐6)2]2+ and two K(benzo‐18‐crown‐6)]+ cations, which are bridged by two Hg(SCN)4]2– anions. In 2 and 3 triply bridged infinite {Cd(SCN)3–}n] zigzag chains, stretching along screw axes, are to be found as anions. In 2 these chains exist in two conformations related by inversion symmetry, whereas in 3 only one form can be found. K(benzo‐18‐crown‐6)]+ cations are linked to the anion chains via K · · · S interactions of different lengths. |