Molecular crystals of 2-amino-1,3,4-thiadiazole with inorganic oxyacids – crystal engineering, phase transformations and NLO properties

Abstract

Eight inorganic salts of 2-amino-1,3,4-thiadiazole (2-athd) with hydrochloric, perchloric, nitric, sulphuric, selenic, phosphorous and phosphoric acids were prepared, and their crystal structures were determined. Seven of the compounds crystallise in monoclinic space groups – i.e., 2-athd(1+) chloride monohydrate (P2₁/c), 2-athd(1+) selenate monohydrate (Pc), 2-athd(1+) dihydrogen phosphate (Cc), 2-athd(1+) phosphite (P2₁/a), 2-athd(1+) nitrate (P2₁/c), 2-athd(1+) 2-athd perchlorate (P2₁/n) and 2-athd(1+) perchlorate (P2₁/c) – and one crystallises in an orthorhombic space group – 2-athd(1+) hydrogen sulphate (P2₁2₁2₁). The thermal behaviours of the materials were studied (DSC) down to liquid nitrogen temperature, and the properties of the perchlorate, hydrogen sulphate and selenate monohydrate crystals were discussed with respect to the results of high or low-temperature X-ray diffraction, IR and Raman spectroscopic studies. Quantitative measurements of the second harmonic generation of the powdered non-centrosymmetric samples at 1064 and 800 nm were performed and a relative efficiency compared to KDP is presented.