Five new antimony(III) complexes with the heterocyclic thiones 2-mercapto-benzimidazole (MBZIM), 5-ethoxy-2-mercapto-benzimidazole (EtMBZIM), and 2-mercapto-thiazolidine (MTZD) of formulas {[SbCl(2)(MBZIM)4]+.Cl-.2H(2)O. (CH(3)OH)} (1), {[SbCl(2)(MBZIM)4]+.Cl-.3H(2)O.(CH3CN)} (2), [SbCl(3)(MBZIM)2] (3), [SbCl(3)(EtMBZIM)(2)] (4), and [SbCl(3)(MTZD)2] (5) have been synthesized and characterized by elemental analysis, FT-IR, far-FT-IR, differential thermal analysis-thermogravimetry, X-ray diffraction, and conductivity measurements. Complex {[SbCl2(tHPMT)(2)]+Cl-}, (tHPMT = 2-mercapto-3,4,5,6-tetrahydro-pyrimidine), already known, was also prepared, and its X-ray crystal structure was solved. It is shown that the complex is better described as {[SbCl3(tHPMT)(2)]} (6). Crystal structures of all other complexes (1-5) have also been determined by X-ray diffraction at ambient conditions. The crystal structure of the hydrated ligand, EtMBZIM.H2O is also reported. Compound [C(28)H(24)Cl(2)N(8)S(4)Sb.2H(2)O.Cl.(CH(3)OH)] (1) crystallizes in space group P2(1), with a = 7.7398(8) A, b = 16.724(3) A, c = 13.717(2) A, beta = 98.632(11) degrees, and Z = 2. Complex [C(28)H(24)Cl(2)N(8)S(4)S(b).Cl.3H(2)O.(CH(3)CN)] (2) corresponds to space group P2(1), with a = 7.8216(8) A, b = 16.7426(17) A, c = 13.9375(16) A, beta = 99.218(10) degrees , and Z = 2. In both 1 and 2 complexes, four sulfur atoms from thione ligands and two chloride ions form an octahedral (Oh) cationic [SbS(4)Cl(2)]+ complex ion, where chlorides lie at axial positions. A third chloride counteranion neutralizes it. Complexes 1 and 2 are the first examples of antimony(III) compounds with positively charged Oh geometries. Compound [C(14)H(12)Cl(3)N(4)S(2)S(b)] (3) crystallizes in space group P, with a = 7.3034(5) A, b = 11.2277(7) A, c = 12.0172(8) A, alpha = 76.772(5) degrees, beta = 77.101(6) degrees, gamma = 87.450(5) degrees, and Z = 2. Complex [C(18)H(20)Cl(3)N(4)O(2)S(2)S(b)] (4) crystallizes in space group P1, with a = 8.6682(6) A, b = 10.6005(7) A, c = 13.0177(9) A, alpha = 84.181(6) degrees, beta = 79.358(6) degrees, gamma = 84.882(6) degrees, and Z = 2, while complex [C(6)H(10)Cl(3)N(2)S(4)S(b)] (5) in space group P2(1)/c shows a = 8.3659(10) A, b = 14.8323(19) A, c = 12.0218(13) A, beta = 99.660(12) degrees, and Z = 4 and complex [C(8)H(16)Cl(3)N(4)S(2)S(b)] (6) in space group P1 shows a = 7.4975(6) A, b = 10.3220(7) A, c = 12.1094(11) A, alpha = 71.411(7) degrees, beta = 84.244(7) degrees, gamma = 73.588(6) degrees, and Z = 2. Crystals of complexes 3-6 grown from acetonitrile solutions adopt a square-pyramidal (SP) geometry, with two sulfur atoms from thione ligands and three chloride anions around Sb(III). The equatorial plane is formed by two sulfur and two chloride atoms in complexes 3-5, in a cis-S, cis-Cl arrangement in 3 and 5 and a trans-S, trans-Cl arrangement in 4. Finally, in the case of 6, the equatorial plane is formed by three chloride ions and one sulfur from the thione ligand while the second sulfur atom takes an axial position leading to a ...

New antimony(III) bromide complexes with the heterocyclic thioamides, thiourea (TU), 2-mercapto-1-methylimidazole (MMI), 2-mercapto-benzimidazole (MBZIM), 2-mercapto-5-methyl-benzimidazole (MMBZIM), 5-ethoxy-2-mercapto-benzimidazole (EtMBZIM), 2-mercapto-3,4,5,6-tetrahydro-pyrimidine (tHPMT), 2-mercaptopyridine (PYT), 2-mercapto-thiazolidine (MTZD), 3-methyl-2-mercaptobenzothiazole (MMBZT), and 2-mercaptopyrimidine (PMTH) of formulas [SbBr(3)(TU)(2)] (1), [SbBr(3)(MMI)(2)] (2), {[SbBr(2)(MBZIM)(4)](+) [Br](-) H(2)O} (3), {[SbBr(2)(mu(2)-Br)(MMBZIM)(2)](2)} (4), {[SbBr(2)(mu(2)-Br)(EtMBZIM)(2)](2) MeOH} (5), {[SbBr(3)(mu(2)-S-tHPMT)(tHPMT)](n)} (6), {[SbBr(2)(mu(2)-Br)(PYT)(2))(n)} (7), {[SbBr(2)(mu(2)-Br)(MTZD)(2)](n)} (8), [SbBr(3)(MMBZT)(2)] (9), and {[SbBr(5)](2-)[(PMTH(2)(+))(2)]} (10) have been synthesized and characterized by elemental analysis, conductivity measurements, FTIR spectroscopy, FT-Raman spectroscopy, TG-DTA analysis, and X-ray powder diffraction. The crystal structures of 3, 4, 5, 6, 7, 8, and 10 were also determined by X-ray diffraction. In 3, four sulfur atoms from thione ligands and two bromide ions form an octahedral (O(h)) cationic [SbS(4)Br(2)](+) species in which the two bromide anions lie at axial positions. A third bromide counteranion neutralizes the whole complex. 4 and 5 are dimers, whereas 6, 7 and 8 are polymers, built up by monomeric units of square pyramidal (SP) geometry around the metal center, which were formed by two sulfur atoms of thioamide ligands and three bromide ions. Finally, 10 is ionic salt containing 1D polymeric network of {[SbBr(5)](2-)}(n) anions and (-)[(PMTH(2)(+))2] counter cations in the lattice. The complexes showed mostly a moderate cytostatic activity against a variety of tumor cell lines.