Crystal structure and supramolecular assembly of a hydrogen-bonded cocrystal of 2-fluoro-N-(pyrrolidine-1-carbonothioyl)benzamide and 1,3,5-triazinane-2,4,6-trithione

Abstract

An unexpected 1:1 cocrystal of 2-fluoro-N-(pyrrolidine-1-carbonothioyl)benzamide and 1,3,5-triazinane-2,4,6-trithione (trithiocyanuric acid, TTCA) was isolated during an attempted synthesis of the single-component benzoylthiourea derivative and characterized by single-crystal X-ray diffraction. The compound crystallizes in the triclinic space group P-1 with one molecule of each component in the asymmetric unit. The fluorinated benzamide derivative adopts a non-planar conformation in which the carbonyl-bearing fragment is twisted relative to the aromatic ring, while the pyrrolidine ring is puckered. The trithione component is nearly planar and displays narrow ranges of C-S and C-N distances, consistent with delocalization within the heterocyclic framework. A nearly linear N3-H3···O1 hydrogen bond [N···O = 2.932(3) Å, N-H···O = 171(3)°] forms a heteromolecular associate. Further N-H···S contacts connect symmetry-related components, producing an extended hydrogen-bonded arrangement supplemented by weaker C-H···S and C-H···F contacts. The crystal packing is governed by cooperative N-H···O and N-H···S interactions.