Main Group Metal Halide Complexes with Sterically Hindered Thioureas X. Complexes of Antimony(V) Chloride and 1,3-dimethyl-2(3H)-imidazolethione


Chemistry and Biochemistry

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Four complexes resulting from the interaction of SbCl5 and dmit (dmit = 1,3-dimethyl-2(3H)-imidazolethione) are synthesized and characterized. Previously reported SbCl5dmit (I) is the dithiouronium disulfide (dmit22+) salt of [Sb2Cl10]2-. Refluxing I in MeCN yielded [dmit2][SbCl4]2 (II) while refluxing I in DMF yielded (dmit)[SbCl6] (III). (Dmit)[Sb2Cl10] (IV) was characterized via x-ray crystallog. in an attempt to det. the structure of I. IV cocrystd. with I in minor proportion. Selection of a nonrepresentative crystal revealed IV also contained the monosulfide dication obsd. in III but in combination with the [Sb2Cl10]2- anion made up of zigzag chains of SbCl6 octahedra sharing disordered Cl vertices and alternating Sb(III) and Sb(V) units with chlorine bridges trans to each other in the latter and cis in the former. Bulk quantities of IV could not be synthesized for further characterization. Crystallog. parameters were detd. for II, III and IV, but only the structure of IV was solved. II crystd. in space group P21/c, Z = 4. III crystd. in space group Cmcm, Z = 8. IV crystd. in space group C2/c, Z = 4, a 16.131(4), b 121.161(3), c 18.862(4) Å, β 92.16.