Metal dithiocarbamate precursors for the preparation of a binary sulfide and a pyrochlore: Synthesis, structure, continuous shape measure and bond valence sum analysis of antimony(III) dithiocarbamates

The antimony(III) complexes [Sb(chmdtc) 3 ] (1), [Sb(chedtc) 3 ] (2) and [Sb(dchdtc) 3 ] 0.5 C 7 H 8 (3) (where chmdtc = cyclohexylmethyldithiocarbamate, chedtc = cyclohexylethyldithiocarbamate and dchdtc = dicyclohexyldithiocarbamate) have been prepared and characterized by electronic, IR and NMR ( 1 H and 13 C) spectra and single crystal X-ray diffraction. Electronic spectra of the complexes show charge transfer transitions. The characteristic thioureide bands occur at 1468, 1479 and 1445 cm ?1 for (1), (2) and (3) respectively. The single crystal X-ray structures of (1), (2) and (3) reveal anisobidentate binding of the dithiocarbamates. Short CAH???S contacts are observed along the ‘a’ axis in (2) and (3). CShM calculations on the SbS 6 chromophores support the distorted octahedral geometry in (1) and (2), and the distorted pentagonal pyramidal geometry in (3), clearly quantifying the extent of deviation from the ideal geom- etries. The nature of the substituents and the lone pair of electrons present in antimony are responsible for the shift of the metal atom position from the geometrical center of the six sulfur atoms. BVS of the compounds show the highly covalent nature of the SbAS bonds. Nano Sb 2 S 3 and (Tl + 2/3?2d )[Tl 3+ 1?y Sb 3+ y ] Sb 2 O 6 O 0 1/3?d , a pyrochlore, have been prepared from the precursors and have been characterized by PXRD, FESEM, EDX, HRTEM and SAED.