Crystal structures of three (trichloromethyl)(carbamoyl)disulfanes

The present paper reports crystallographic studies on three related compounds that were of inter­est as precursors for synthetic and mechanistic work in organosulfur chemistry, as well as to model nitro­gen-protecting groups: (N-methyl­carbamo­yl)(tri­chloro­meth­yl)disulfane, C(3)H(4)Cl(3)NOS(2), (1), (N-benzyl­carbamo­yl)(tri­chloro­meth­yl)disulfane, C(9)H(8)Cl(3)NOS(2), (2), and (N-methyl-N-phenyl­carbamo­yl)(tri­chloro­meth­yl)disulfane, C(9)H(8)Cl(3)NOS(2), (3). Their mol­ecular structures, with similar bond lengths and angles for the CCl(3)SS(C=O)N moieties, are confirmed. Compounds (1) and (3) both crystallized with two independent mol­ecules in the asymmetric unit. Classical hydrogen bonding, as well as chlorine-dense regions, are evident in the crystal packing for (1) and (2). In the crystal of (1), mol­ecules are linked via N—H⋯O hydrogen bonds forming chains along [110], which are linked by short Cl⋯Cl and S⋯O contacts forming sheets parallel to (001). In the crystal of (2), mol­ecules are linked via N—H⋯O hydrogen bonds forming chains along [001], which in turn are linked by pairs of short O⋯Cl contacts forming ribbons along the c-axis direction. In the crystal of (3), there are no classical hydrogen bonds present and the chlorine-dense regions observed in (1) and (2) are lacking.