Coordination chemistry in the solid state: reactivity of manganese and cadmium chlorides with imidazole and pyrazole and their hydrochlorides.

Crystalline coordination compounds [MnCl(2)(Hpz)(2)] 3, [CdCl(2)(Hpz)(2)] 5, [MnCl(2)(Him)(2)] 9, and [CdCl(2)(Him)(2)] 13 (Him = imidazole; Hpz = pyrazole) can be synthesized in solid state reactions by grinding together the appropriate metal chloride and 2 equiv of the neutral ligand. Similarly, grinding together the metal chlorides with the ligand hydrochloride salts produces the halometallate salts [H(2)pz][MnCl(3)(OH(2))] 1, [H(2)pz][CdCl(4)] 4, [H(2)im](6)[MnCl(6)][MnCl(4)] 8, and [H(2)im](6)[CdCl(6)][CdCl(4)] 11. In contrast, reacting the metal chloride salt with the ligand in concentrated HCl solution yields a second set of salts [H(2)pz][MnCl(3)] 2, [H(2)im][MnCl(3)(OH(2))(2)] 7, and [H(2)im][CdCl(3)(OH(2))]·H(2)O 12. Compound 5 can be partly dehydrochlorinated by grinding with KOH to form an impure sample of the pyrazolate compound [Cd(pz)(2)] 6, while recrystallizing 9 from ethanol yielded crystals of solvated [Mn(4)Cl(8)(Him)(8)] 10. The crystal structure determinations of 1, 2, 4, 11, and 12 are reported.