ABSTRACT
The asymmetric unit of the title compound, [Pd(C22H26N2O2S3)]2·CH3CN, contains two complex mol-ecules and a single uncoordinated lattice aceto-nitrile solvent mol-ecule. The Pd(II) cations have a trans-N2O2 square-planar geometry and the superposition of the two crystallographically independent Pd(II) complexes yields an overall r.m.s. deviation of 0.292â Å. The Pdâ¯Pd separation in the asymmetric unit is 3.3776â (3)â Å, while the PdN2O2 plane-plane fold angle is 1.62â (7)°. A short inter-molecular Sâ¯S contact between the central S atom of one complex and its inversion-related symmetry equivalent of 3.663â (2)â Å is observed. Part of the ligand chain (S-C-C-S) in each complex mol-ecule is disordered over two orientations and refined occupancies that converged to 0.450â (10) and 0.550â (10) for the one complex mol-ecule, and 0.789â (9) and 0.211â (9) for the other.
ABSTRACT
In the title complex, [PdCl2(C12H22S3)]·0.8CH3CN, a potentially tridentate thioether ligand coordinates in a cis-bidentate manner to yield a square-planar environment for the Pd(II) cation [mean deviation of the Pd from the Cl2S2 plane = 0.0406â (7)â Å]. Each square-planar entity packs in an inverse face-to-face manner, giving pairs with plane-to-plane separations of 3.6225â (12)â Å off-set by 1.1263â (19)â Å, with a Pd···Pd separation of 3.8551â (8)â Å. A partial acetonitrile solvent molecule is present. The occupancy of this molecule was allowed to refine, and converged to 0.794â (10). The synthesis of the previously unreported 3,6,9-trithiabicyclo[9.3.1]pentadecane ligand is also outlined.
ABSTRACT
The ligand 2,5-bis(4-hydroxy-2-thiabutyl)thiophene (L) and its polymeric complex (CuCl(2).L)(n)() have been prepared. The complex (C(10)H(16)Cl(2)CuO(2)S(3))(n)() crystallizes in the orthorhombic system, space group P2(1)2(1)2(1), with a = 6.8096(4) Å, b = 9.4542(5) Å, c = 22.899(3) Å, Z = 4. Each copper atom is six-coordinate with cis chlorines and trans sulfurs. One bond to chlorine and one to oxygen are elongated, and each copper is part of a zigzag (Cu-Cl)(n)() chain. The chains are cross-linked by the organic ligand, which coordinates through each of its arms to different coppers by using thioether sulfur and hydroxyl oxygen. Electrical neutrality is achieved by the remaining chlorine required by stoichiometry being present as an isolated Cl(-) ion in empty spaces in the structure. The complex has been investigated by cyclic voltammetry, IR, and UV/vis spectroscopy, and the polymer structure has been observed to be destroyed upon dissolving. Magnetic susceptibility measurements (5-302 K) have been fitted to a uniform chain model with molecular field and paramagnetic "impurity" corrections. Intrachain (-2J = 26.4 cm(-)(1)) and interchain (J' = -8.46 cm(-)(1)) couplings were found to be small and antiferromagnetic.
ABSTRACT
The ligand 1-oxa-4,7-dithiacyclononane (L) and its complexes [Pd(L)Cl(2)], [Cu(L)(2)][ClO(4)].CH(3)CN, [Cu(L)Br](2), and [Co(L)(2)][ClO(4)](2).2CH(3)NO(2) have been prepared. Crystal data are as follows. For monoclinic [Pd(L)Cl(2)], C(6)H(12)Cl(2)OPdS(2): space group P2(1)/n; a = 8.464(2), b = 12.199(2), c = 10.384(2) Å; beta = 105.09(1) degrees; Z = 4; R = 0.024, R(w) = 0.033 for 1721 reflections. For monoclinic [Cu(L)(2)][ClO(4)].CH(3)CN, C(14)H(27)ClCuNO(6)S(4): space group P2(1)/n; a = 7.743(2), b = 19.515(5), c = 15.017(2) Å; beta = 102.85(2) degrees; Z = 4; R = 0.036, R(w) = 0.038 for 3124 reflections. For triclinic [Cu(L)Br](2), (C(6)H(12)BrCuOS(2))(2): space group P&onemacr;; a = 7.809(5), b = 8.880(3), c = 7.567(2) Å; alpha = 92.44(3), beta = 102.85(2), gamma = 99.30(4) degrees; Z = 2; R = 0.027, R(w) = 0.027 for 1494 reflections. For monoclinic [Co(L)(2)][ClO(4)](2).2CH(3)NO(2), C(14)H(30)Cl(2)CoN(2)O(14)S(4): space group P2(1)/c; a = 10.333(3), b = 14.293(6), c = 9.365(4) Å; beta = 100.89(3) degrees; Z = 2; R = 0.067, R(w) = 0.058 for 1517 reflections. The ligand displays a variety of conformations in these structures. The palladium complex does not undergo 1,4-heteroatom binding site fluxional processes but does dissociate in dimethyl sulfoxide. An apical Pd.O (2.968(3) Å) interaction has been detected by both NMR and X-ray studies. The Cu(I) cation is tetrahedral with a [2+2] mode of ligand coordination. [Cu(L)Br](2) involves two Br bridges between coppers and two thioether sulfurs from a ligand to complete each copper's tetrahedral coordination sphere. Surprisingly, the cyclic voltammetric behavior of the copper complexes is similar to that of 1,4,7-trithiacyclononane complexes. The cation [Co(L)(2)](2+) is pseudooctahedral with nearly regular angles at cobalt but a long (2.235(6) Å) Co-O bond due to Jahn-Teller distortion. The complex [Co(L)(2)][ClO(4)](2) is magnetically dilute and low-spin over the temperature range 5-292 K.
