A room-temperature redetermination of the crystal structure of [Cu(SC(NHCH2)2)3]2 (SOs) has been carried out. The original determination, recorded in communication format in space group Ic, Z = 4, seemingly with the full formula as the asymmetric unit, is a t variance with our findings which describe the structure in space group R3c, a 12.741(7), c 35.59(1) A (hexagonal setting), Z = 6, with one-third of each of two independent cations, each lying on a threefold axis, comprising the asymmetric unit. The sulfate ion also lies on a threefold axis in proximity to only one of the two cations, the S-0 axial bond approaching the copper atom normal to the planar CuS3 array [Cu-S, 0 2.269(2), 2.834(8) A]; in the other cation, unperturbed by any sulfate approach, Cu-S is appreciably shorter [2.246(2) A]. R was 0.029 for 905 'observed' reflections. A redetermination of the structure of tetrakis(ethylenethiourea)copper(~) nitrate is also recorded; crystals are triclinic, Pi, a 13.211(2), b 11.2167(4), c 7.566(3) A, a: 81.93(2), / 3 78.35(3), y 87.22(1)', 2 = 2, R being 0.031 for 3861 independent 'observed' reflections. The copper environment is quasi-tetrahedral, Cu-S ranging between 2.3322(9) and 2.3658(12) A, and S-Cu-S 98.76(3)-117.83(3)'.The vibrational (far-infrared and Raman) spectra are recorded for these CuS, systems, and discussed and assigned in the light of the structural results.

Key indicators: single-crystal X-ray study; T = 293 K; mean (C-C) = 0.004 Å; R factor = 0.032; wR factor = 0.088; data-to-parameter ratio = 20.9.The dinuclear title complex, [Ag 2 (C 6 H 7 N 2 S) 2 (C 18 H 15 P) 2 ], comprises two inversion-related [Ag(C 6 H 7 N 2 S)(C 18 H 15 P)] units. The pyrimidinethiolate anion acts both as a bridging and a chelating ligand. The Ag I ions are linked via two 2 -S donor atoms, which generate a strictly planar Ag 2 S 2 core with an AgÁ Á ÁAg separation of 2.9569 (4) Å . The Ag I ion presents a distorted tetrahedral coordination geometry. In the crystal, weak C-HÁ Á ÁN and C-HÁ Á ÁS hydrogen bonds link the complex molecules into a two-dimensional network parallel to (010). Related literature

Copper(I) and silver(I) chloride complexes containing triphenylphosphine (PPh 3 ) and 4-phenylthiosemicarbazide (4-PTSC) ligands were prepared and structurally analyzed, namely [CuCl(4-PTSC)(PPh 3 ) 2 ] (1) and [AgCl(4-PTSC)(PPh 3 ) 2 ]CH 3 CN (2). Both compounds (1) and (2) exhibit a distorted tetrahedral metal coordination environment with two P atoms from two PPh 3 ligands, one terminal S atom from the 4-PTSC ligand and a chloride ion. Intramolecular N−H • • • Cl and N−H • • • N hydrogen bonds are observed (graph set motifs S(6) and S(5), respectively). In the crystals of both complexes, molecules are linked to form dimers via bifurcated N−H • • • Cl hydrogen bonds involving the amine and chloride units. For compound (2), a solvate acetonitrile molecule acts as a hydrogen bond donor and acceptor via C−H(CH 3 CN) • • • Cl and C−H • • • N(CH 3 CN) interactions, leading to the formation of 1D chains along [010].

In the mononuclear title complex, [CuI(C6H8N2S)(C18H15P)2], the CuI ion is in a slightly distorted tetra­hedral coordination geometry formed by two P atoms from two triphenyl­phosphane ligands, one S atom from a 4,6-dimethyl­pyrimidine-2(1H)-thione ligand and one iodide ion. There is an intra­molecular N—H⋯I hydrogen bond. In the crystal, π–π stacking inter­actions [centroid–centroid distance = 3.594 (1) Å] are observed.

In the mononuclear title complex, [Ag(C5H12N2S)(C18H15P)3](CH3COO)·CH3OH, the AgI ion is in a distorted tetra­hedral coordination geometry formed by three P atoms from three tri­phenyl­phosphane ligands and one S atom from an N,N′-di­ethyl­thio­urea ligand. In the crystal, the acetate anion is connected to the complex mol­ecule via a pair of N—H⋯O hydrogen bonds [graph-set motif R 2 2(8)] and the solvent methanol mol­ecule is connected to the anion via an O—H⋯O hydrogen bond. This aggregate is further connected through a weak C—H⋯O hydrogen bond, forming a chain along [100]. In addition, sixfold phenyl embraces with inter­molecular distances of 6.6463 (13)–6.667 (2) Å are arranged in a chain along [001]. The combination of hydrogen bonding and phen­yl⋯phenyl inter­actions leads to the formation of a two-dimensional network parallel to (010).