Two New Salts Based on Bis(1,2,5-thiadiazole-3,4-dithiolate)nickelate Anion with Substituted Benzyl 4-ethylpyridinium: Syntheses, Crystal Structures and Properties

Abstract

Two new salts based on [Ni(tdas) 2 ] 2-(tdas 2-= 1,2,5-thiadiazole-3,4-dithiolate) anion, [Bz4EtPy] 2 [Ni(tdas) 2 ] (1) and [4ClBz4EtPy] 2 [Ni(tdas) 2 ] (2), have been prepared by reaction of Na 2 tdas, NiCl 2 Á6H 2 O, and [Bz4EtPy]Br ([Bz4EtPy] ?and characterized by elemental analyses, UV, IR, MS spectrum, molar conductivity and single crystal X-ray diffraction. Single-crystal X-ray diffraction analyses indicate that the two salts crystallize in a triclinic system with space group P-1. The unit cell contains two [Bz4EtPy] ? /[4ClBz4EtPy] ? and one [Ni(tdas) 2 ] 2-anion in which the anion exhibits a quasiplanar structure. The crystals of 1 and 2 are stabilized through C-HÁÁÁS and C-HÁÁÁNi hydrogen bonds, pÁÁÁp stacking interactions and SÁÁÁCl short interactions.

Synthesis, Characterization, Weak Interactions, and 3D Crystal Structures of Two New Salts Based on Bis(1,2,5-thiadiazole-3,4-dithiolate)nickelate Anion with 4-Substituted Benzyl 4-Ethylpyridinium Derivatives

“…The UV-Vis absorption spectra of 1 and 2 in acetone from 200 to 900 nm are attributed to [Ni(tdas) 2 [15,20] The negative-ion …”

“…[20] The relevant bond lengths and angles are listed in Table 2. The [4FBz-4EtPz] C cation adopts a conformation where both the phenyl ring and pyridine ring are twisted to the C(8)¡C(9)¡N(3) reference plane, with the dihedral angles to that plane of 80.1 (u 1 ) and 90.0 (u 2 ), respectively.…”

“…Comparison with the crystal structures of [4RBz-4EtPy] 2 [Ni(tdas 2 ](R D H, [20] F, Cl, [20] and Br), it is seen that the change of R results in the change of the dihedral angles u 1 , u 2 , and u 3 of the cations although the coordination geometry of nickel(II) ion of [Ni(tdas) 2 ] 2¡ anion. When R is H, F or Cl atom, the compound crystallizes in the triclinic system with space group P-1, while when R is Br atom, the compound crystallizes in the monoclinic system with space group C2/c and the [Ni(tdas) 2 ] 2¡ anions form a 1D chain through intermolecular short S¢¢¢S interactions.…”