Benzodithiazolium‐Chlorooxomolybdate(V): Darstellung und Kristallstruktur von (C 6 H 4 NS 2 )[MoOCl 4 ] und (C 6 H 4 NS 2 )[MoOCl 4 ·H 2 O]

Benzodithiazolium Chlorooxomolybdate(V): Preparation and Crystal Structure of (C 6 H 4 NS 2 )[MoOCl 4 ] and (C 6 H 4 NS 2 )[MoOCl 4 ·H 2 O] Red benzo‐1,3,2‐dithiazolium‐chlorooxomolybdate(V) (C 6 H 4 NS 2 )[MoOCl 4 ] ( 1 ) was obtained by the reaction of benzo‐1,3,2‐dithiazoliumchloride and molybdenum(V)chloride oxide in dichlormethane under solvothermal conditions at 70 °C. In the presence of small amounts of concentrated hydrochloric acid the yellow compound (C 6 H 4 NS 2 )[MoOCl 4 ·H 2 O] ( 2 ) is formed under analogue conditions. Both crystal structures ( 1 : monoclinic, C 2/ c , a = 799.2(1), b = 2091.5(2), c = 791.5(1) pm, β = 102.2(1)°, Z = 4; 2 : monoclinic, Cc , a = 953.7(1), b = 2468.9(3), c = 608.1(1) pm, β = 112.5(1)°, Z = 4) contain the planar benzo‐1,3,2‐dithiazolium ion. Within the structure of 1 the molybdenum atoms in the [MoOCl 4 ] − ions are coordinated in a square pyramidal fashion with an oxygen atom in apical position and the basal plane formed by chlorine atoms. The nitrogen atom of the cation, which bears a partial negativ charge, expands the coordination to a distorted octahedron. The structure therefore is made up of ionic pairs {(C 6 H 4 NS 2 ) + [MoOCl 4 ] − } with a Mo–N distance of 266 pm. 1 is paramagnetic with a magnetic moment of 1.7 B.M. corresponding to one unpaired electron per formula unit. In the structure of 2 the coordination of the [MoOCl 4 ] − ion is expanded by the oxygen atom of a coordinating water molecule. The structure is dominated by hydrogen bonds between the oxygen atoms of the [MoOCl 4 ·H 2 O] − ions which cause the concatenation of the anions to infinite chains.