Acta Crystallographica Section C

Crystal Structure Communications

Volume 69, Part 9 (September 2013)

organic compounds

Acta Cryst. (2013). C69, 1034-1038    [ doi:10.1107/S0108270113019665 ]

Mol­ecular cocrystals of 5-(4-bromo­phenyl)-1,3,4-thia­diazol-2-amine: hydrogen bonding in the structures of the 1:1 adduct with 2-(naphthalen-2-yl­oxy)acetic acid and the salt with 3,5-di­nitro­benzoic acid

G. Smith and D. E. Lynch

Abstract: The crystal structures of the anhydrous products from the inter­action of 5-(4-bromo­phenyl)-1,3,4-thia­diazol-2-amine with 2-(naphthalen-2-yl­oxy)acetic acid, viz. the 1:1 adduct C8H6BrN3S·C12H10O3, (I), and with 3,5-di­nitro­benzoic acid, viz. the salt 2-amino-5-(4-bromo­phenyl)-1,2,4-thia­diazol-3-ium 3,5-di­nitro­benzoate, C8H7BrN3S+·C7H3N2O6-, (II), have been determined. In adduct (I), a heterodimer is formed through a cyclic hydrogen-bonding motif [graph set R22(8)], involving carb­oxy­lic acid-heteroatom O-H...N and amine-carb­oxy­lic acid N-H...O inter­actions. The heterodimers are essentially planar, with a thia­diazole-to-naphthalene ring dihedral angle of 15.9 (2)° and an intra­molecular thia­diazole-to-benzene ring angle of 4.7 (2)°. An amine-heteroatom N-H...N hydrogen bond between the heterodimers generates a one-dimensional chain structure extending down [001]. Also present are weak benzene-benzene and naphthalene-naphthalene [pi]-[pi] stacking inter­actions down the b axis [minimum ring-centroid separation = 3.936 (3) Å]. With salt (II), the cation-anion association is also through a cyclic R22(8) motif but involving duplex N-H...Ocarboxylate hydrogen bonds, giving a heterodimer that is close to planar [dihedral angles between the thia­diazole ring and the two benzene rings = 5.00 (16) (intra) and 7.23 (15)° (inter)]. A secondary centrosymmetric cyclic R_{4}^{2}(8) N-H...Ocarbox­ylate hydrogen-bonding association involving the second amino H atom generates a hetero­tetra­mer. Also present in the crystal structure are weak [pi]-[pi] inter­actions between thia­diazo­lium rings [minimum ring-centroid separation = 3.9466 (18) Å], as well as a short Br...Onitro inter­action [3.314 (4) Å]. The two structures reported here now provide a total of three crystallographically characterized examples of cocrystalline products from the inter­action of 5-(4-bromo­phen­yl)-1,3,4-thia­diazol-2-amine with carb­oxy­lic acids, of which only one involves proton transfer.

Formula: C8H6BrN3S·C12H10O3 and C8H7BrN3S+·C7H3N2O6-

Keywords: crystal structure; organic salts; molecular cocrystals; 1,3,4-thiadiazol-2-amines.

hkldisplay filedownload file

Structure factor file (CIF format) (162.3 kbytes)
[ doi:10.1107/S0108270113019665/fg3301Isup2.hkl ]
Contains datablock I

hkldisplay filedownload file

Structure factor file (CIF format) (165.9 kbytes)
[ doi:10.1107/S0108270113019665/fg3301IIsup3.hkl ]
Contains datablock II


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