STRUCTURAL DIVERSITY IN THALLIUM CHEMISTRY - STRUCTURES OF 4 CHLOROTHALLATE(III) SALTS INCLUDING A NOVEL COMPOUND CONTAINING 3 GEOMETRICALLY DIFFERENT ANIONS
Ma. James et al., STRUCTURAL DIVERSITY IN THALLIUM CHEMISTRY - STRUCTURES OF 4 CHLOROTHALLATE(III) SALTS INCLUDING A NOVEL COMPOUND CONTAINING 3 GEOMETRICALLY DIFFERENT ANIONS, Canadian journal of chemistry, 74(8), 1996, pp. 1490-1502
Four new thallium-containing salts with different alkyl ammonium catio
ns have been prepared and characterized by X-ray crystallography: 1: b
is(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] [TlC
l5], M = 485.83, orthorhombic, P2(1)2(1)2(1), a = 13.226(2), b = 13.59
5(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: penta
kis(2-adamantaneammonium) bistetrachlorothallate(III) hexachlorothalla
te(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) deca
chlorodithallate(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 ca
ses, high coordination numbers at thallium were observed (CN = 6), and
these can be achieved via formation of anionic chains or through dime
rization, giving [Tl2Cl10](4-). Of particular interest is the solid st
ate structure of salt 3 in which there are three geometrically differe
nt chlorothallate ions. Extensive hydrogen-bonding networks are observ
ed in each structure.