Crystal structures of four univalent metal complexes with (phenylthio)acetic acid (PTAH), (2,4-dichloro-5-methylphenylthio)acetic acid (DCMPTAH), and 2-(phenylthio) propionic acid (PTPAH) have been determined using X-ray diffraction. The thallium complex, [Tl(PTA)(PTAH)]n, (1) is orthorhombic, space group Pccn, Z = 4, a = 10.466(6), b = 26.75(1), c = 6.013(2) Å. [Cs(DCMPTA)(DCMPTAH)]n, (2) is triclinic, space group Pl, Z = 1, a = 5.159(3), b = 6.898(3), c = 16.500(8) Å, a = 90.04(4), β = 94.22(4) and γ = 103.27(4)°. PTAH forms an adduct [Cs(PTA)(PTAH)]n, (3) which is monoclinic, space group Cc with Z = 4, a = 35.88(1), b = 7.201(2), c = 6.907(1) Å, β = 91.19(2)°. PTPAH forms a conventional hydrated complex, [Cs(PTPA)(H2O)]n, (4), which is orthorhombic, Pbca, with Z = 8, a = 8.849(4), b = 9.500(3), c = 29.78(1) Å. The structures (1-4) were refined to residuals of 0.078, 0.087, 0.030 and 0.036 for 1353, 1571, 2225, 1807 "observed" reflections, respectively. Both 1 and 2 are examples of acid salts of the type, MHX2, where X- and HX are crystallographically equivalent. The molecules are polymeric and have bonded ligands as well as adducted acid species. 3 is an example of a type B (M+X-·HX) salt with X- and HX crystallographically different. 4 is an example of a normal Cs salt. The Tl compound (1 is disordered with only half the general position sites occupied by the metal atom. Each site is at the centre of a distorted MO5S octahedron with very short bonds to both asymmetric bidentate and bridging carboxylate groups [TlO, 2.22, 2.44(1) Å] and to the thioether S [TlS,2.517(4)Å]. In 2, the Cs atom is at the centre of symmetry of a distorted MO6 octahedron. It has a polymer structure with acetate bridges linking consecutive Cs atoms and carboxylate oxygen also bifurcated between two Cs atoms. The CsO distances are 3.123(10), 3.152(8) and 3.237(8)Å. Complex 3 has an irregular MO8 polyhedron about Cs with bonds from both PTA and PTAH ligands [CsO range, 3.03-3.45(1) Å; mean, 3.23(1) Å], and extends into a 2-D polymer structure. Compound 4 is also polymeric but with distorted octahedral MO6 coordination, bridging through both carboxylate and water oxygens [CsO range, 3.02-3.33(1) Å; mean, 3.20(1) Å].
Scopus Subject Areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry