A new monoclinic polymorph of N-(3-methyl-phen-yl)eth-oxy-carbo-thio-amide: crystal structure and Hirshfeld surface analysis

The title compound, C10H13NOS, is a second monoclinic polymorph (space group P21/c, Z' = 2) of the previously reported C2/c (Z = 1) polymorph [Tadbuppa & Tiekink (2005 ▸). Z. Kristallogr. New Cryst. Struct. 220, 395-396]. Two independent mol-ecules comprise the asymmetric unit of the new polymorph and each of these exists as a thioamide-thione tautomer. In each molecule, the central CNOS chromophore is strictly planar [r.m.s. deviations = 0.0003 and 0.0015 Å] and forms dihedral angles of 6.17 (5) and 20.78 (5)° with the N-bound 3-tolyl rings, thereby representing the major difference between the mol-ecules. The thione-S and thio-amide-N-H atoms are syn in each mol-ecule and this facilitates the formation of an eight-membered thio-amide {⋯SCNH}2 synthon between them; the dimeric aggregates are consolidated by pairwise 3-tolyl-C-H⋯S inter-actions. In the extended structure, supra-molecular layers parallel to (102) are formed via a combination of 3-tolyl-C-H⋯π(3-tol-yl) and weak π-π inter-actions [inter-centroid distance between 3-tolyl rings = 3.8535 (12) Å]. An analysis of the Hirshfeld surfaces calculated for both polymorphs reveals the near equivalence of one of the independent mol-ecules of the P21/c form to that in the C2/c form.