Structural diversity in thallium chemistry: Structures of four chlorothallate(III) salts including a novel compound containing three geometrically different anions

Four new thallium-containing salts with different alkyl ammonium cations have been prepared and characterized by X-ray crystallography: 1: bis(p-toluidinium) pentachlorothallate(III), [CH3C6H4NH3](2) [TlCl5], M = 597.9, monoclinic, P2(l)/c, a = 7.515(2), b = 21.376(6), c = 12.769(2) Angstrom, beta = 92.13(2)degrees, V = 2050(1) Angstrom(3), Z = 4, D-calc= 1.937 Mg m(-3), mu = 8.512 mm(-1), T = 293(1) K, R = 0.046; 2: 1,5-pentanediammonium pentachlorothallate(III), [NH3(CH2)(5)NH3] [TlCl5], M = 485.83, orthorhombic, P2(1)2(1)2(1), a = 13.226(2), b = 13.595(2), c = 7.628(2) Angstrom, V = 1371.6(3) Angstrom(3), Z = 4, D-calc = 2.352 Mg m(-3), mu = 12.84 mm(-1), T = 173(1) K, R = 0.025; 3: pentakis(2-adamantaneammonium) bistetrachlorothallate(III) hexachlorothallate(III), [C(1)0H(18)N](5) [TlCl4](2)[TlCl6], M = 1870.75, monoclinic, P2(l), a = 16.466(5), b = 25.985(2), c = 7.724(3) Angstrom, beta = 90.14(3)degrees, V = 3305(2) Angstrom(3), Z = 2, D-calc = 1.880 Mg m(-3), mu = 7.978 mm(-1), T = 173(1) K, R = 0.056; 4: bis(piperazinium) decachlorodithallate(III) trihydrate, [NH2C4H8NH2](2) [Tl2Cl10]. 3H(2)O, M = 993.62, monoclinic, C2/c, a = 14.154(3), b = 15.445(3), c = 13.228(3) Angstrom, beta = 114.44(1)degrees, V = 2632.7(9) Angstrom(3), Z = 4, D-calc = 2.506 Mg m(-3), mu = 13.39 mm(-1), T = 173(1) K, R = 0.026. For most of the salts examined, formation of [Tl2Cl5](2-) is possible; however, no isolated [TlCl5](2-) anions were observed ed. In most cases, high coordination numbers at thallium were observed (CN = 6), and these can be achieved via formation of anionic chains or through dimerization, giving [Tl2Cl10](4-). Of particular interest is the solid state structure of salt 3 in which there are three geometrically different chlorothallate ions. Extensive hydrogen-bonding networks are observed in each structure.