1-oxa-4,6-dithia-5-arsocane and 1,3,6-trithia-2-arsocane dithiocarbamates competition between transannular and exocyclic secondary bonding to arsenic

Abstract

1-oxa-4,6-dithia-5-arsocane morpholinyldithiocarbamate (1) and 1,3,6-trithia-2-arsocane 2-diethyldithiocarbamate (2) have been prepared by reacting the corresponding sodium dithiocarbamates with 1-oxa-4,6-dithia-5-arsocane or 1,3,6-trithia-2-arsocane. (1) and (2) were characterized by elemental analyses, IR, MS, H-1 and C-13 NMR. The X-ray single-crystal molecular structures of (1) [monoclinic, a = 9.931(5), b = 18.253(5), c = 8.076(3) Angstrom

beta = 92.56(2)degrees

V = 1462.5(7) Angstrom(3)

space group P2(1)/c

Z = 4

R = 4.33%] and (2) [monoclinic, a = 7.830(2), b = 10.465(2), c = 19.025(6) Angstrom

beta = 95.82(2)degrees

V = 1550.8(10) Angstrom(3)

space group P2(1)/c

Z = 4

R = 3.41%], show that the compounds are monomeric and contain an asymmetric monometallic biconnective dithiocarbamate ligand with a large distortion in the geometry around the As and a weak heterocyclic arsocane transannular secondary interaction.