In the cation of the title compound, C14H13N2S+·Br−, the essentially planar benzimidazole system (r.m.s. deviation = 0.0082 Å) is substituted with a 4-methyl­sulfanylphenyl ring. The dihedral angle between the benzimidazole system and the 4-methyl­sulfanylphenyl ring is 2.133 (2)°. The crystal structure is characterized by strong and highly directional inter­molecular N—H⋯Br hydrogen bonds involving the bromide ion. Moreover, C—H⋯S inter­actions result in chains of mol­ecules along the c axis. The supra­molecular assembly is further stabilized by π–π stacking inter­actions between the benzimidazole system and 4-methyl­sulfanylphenyl rings [centroid–centroid distance = 3.477 (4) Å].

In the title compound, C18H11BrN4OS, the imidazothia­diazole and benzisoxazole rings are individually planar with maximum deviations of 0.025 (3) 0.015 (4) Å, respectively, and are inclined at an angle of 23.51 (7)° with respect to each other. The planes of the imidazothia­diazole and bromo­phenyl rings are inclined at an angle of 27.34 (3)°. In the crystal, inter­molecular C—H⋯N inter­actions result in chains of mol­ecules along the b and c axes. Moreover, C—H⋯O inter­actions result in centrosymmetric head-to-head dimers with R 2 2(24) graph-set motifs. The mol­ecular packing is further stabilized by π–π stacking inter­actions between the imidazole rings with a shortest centroid–centroid distance of 3.492 (3) Å. In addition, C—H⋯π inter­actions are observed in the crystal structure.

In the title compound, C10H12N2S, one of the C atoms of the cyclo­hexene ring (at position 6) and the methyl group attached to it are disordered over two sets of sites in a 0.650 (3):0.350 (3) ratio. The cyclo­hexene ring in both the major and minor occupancy conformers adopts a half-chair conformation. The thio­phene ring is essentially planar (r.m.s. deviation = 0.05 Å). In the crystal, N—H⋯N hydrogen bonds involving the amino groups result in inversion dimers with R 2 2(12) graph-set motif. Further N—H⋯N hydrogen bonds involving the amino and carbonitrile groups generate zigzag chains along the a axis.

The asymmetric unit of the title compound, (C14H13N2S)2[CuBr4]·2H2O, contains two cations, one anion and two solvent water molecules that are connected via O—H...Br, N—H...Br and N—H...O hydrogen bonds into a two-dimensional polymeric structure. The cations are arranged in a head-to-tail fashion and form stacks along [100]. The central CuII atom of the anion is in a distorted tetrahedral environment