Heterocyclic Thiones Research Articles

Silver(I) complexes with heterocyclic thiones and tertiary phosphines as ligands. Part 4. Dinuclear complexes of silver(I) bromide: the crystal structure of bis[bromo-(pyrimidine-2-thione)(triphenylphosphine)silver(I)

Mixed-ligand complexes of the formula [Ag(PPh 3)(L)Br] 2 were obtained by treatment of various heterocyclic thiones L {L=pyridine-2-thione (py2SH), pyrimidine-2-thione (pymtH), benz-1,3-imidazoline-2-thione (bzimtH 2), benz-1,3-thiazoline-2-thione (bztztH), 1-methyl-1,3-imidazoline-2-thione (meimtH) and 5-methoxy-benz-1,3-imidazoline-2-thione (5MeObzimtH 2)} with equivalent quantities of silver(I) bromide and triphenylphosphine in dry acetone. The compounds were characterized by their IR, far-IR, UV–Vis and 1H NMR spectroscopic data. The crystal structure of [Ag(PPh 3)(pymtH)Br] 2 was determined by single-crystal X-ray diffraction methods. The complex exhibits a planar Ag 2Br 2 moiety in which each of the doubly bromine-bridged Ag(I) centres is further bonded to one phosphine P and one thione S atom.

Binuclear copper(I) complexes containing bis(diphenylphosphino)ethane bridges: the crystal structure of bis[{μ-bis(diphenylphosphino)ethane}(pyridine-2-thione)copper(I)bromide

Treatment of copper(I) bromide with one equivalent of 1,2-bis(diphenylphosphino)ethane (dppe), followed by the addition of one equivalent of heterocyclic thione L {L=pyridine-2-thione (py2SH), pyrimidine-2-thione (pymtH), imidazole-2-thione (imtH), benz-1,3-imidazoline-2-thione (bzimtH 2), benz-1,3-thiazoline-2-thione (bztztH), 2-mercapto-1-methylimidazole (meimtH), 4,6-dimethylpyrimidine-2-thione (dmpymtH), and 6-ethoxybenz-1,3-thiazoline-2-thione (etObztztH) in dry acetone affords the dinuclear complexes [CuBr(dppe)(L)] 2 in ca. 60–80% yield. These compounds have been characterized by their IR, far-IR, UV–Vis and 1H NMR spectroscopic data. The crystal structure of [CuBr(dppe)(py2SH)] 2 has been determined by single-crystal X-ray diffraction methods. In the dinuclear complex in which the two monomers are related by inversion, each Cu(I) centre exhibits a tetrahedral coordination sphere involving, besides the bromine, the exocyclic sulfur of one thione molecule and two phosphor atoms from two different diphosphine units. Vibrational, electronic and 1H NMR spectral data of the complexes are discussed in relation to the structure.

Synthesis of condensed heterocycles containing a pyrimido[5,4-e][1,3]-thiazine fragment

The cyclocondensation of 4,6-dichloro-2-methylthiopyridine-5-carbaldehyde and heterocyclic thiones such as 1,2,4-triazole-5-thione, imidazolidine-2-thione, imidazole-2-thione, and 4,5-diphenylimidazole-2-thione in dimethylformamide gave tricyclic heterocycles containing a pyrimido[5,4-e][1,3]thiazine fragment. The reaction of 6-chloro-8-methylthio-5H-pyrimido[5,4-e][1,2,4]triazolo[5,1-b][1,3]thiazin-5-ol with diethylamine, pyrrolidine, and morpholine gave the corresponding 6-dialkylaminopyrimidotriazolothiazines.

Complexes of heterocyclic thiones and Group 12 metals: Part 3. Preparation and characterisation of 1:2 complexes of mercury(II) halides with 1-methylimidazoline-2(3 H)-thione: the crystal structures of [(HgX 2)(1-methylimidazoline-2(3 H)-thione) 2] (X=Cl, Br, I) at 160 K

The stoichiometric addition (1:2 metal–ligand) of aqueous alcoholic solutions of the metal salts to similar solutions of 1-methyl-imidazoline-2(3 H)-thione (1-meimz2SH) generated crystalline complexes of general formula, [HgX 2(1-meimz2SH) 2] (X=Cl, Br, I), in good yield. The chemical formulae of the complexes have been characterised by elemental chemical analysis. Infrared and 13C NMR spectra indicated the presence of the thione form of the heterocyclic ligands in the complexes, as well as their thione–sulfur ligating character. X-ray crystal structure analyses have been performed on the three complexes. The metal in the chloro complex occupies a crystallographic two-fold axis which bisects the SHgS angle. The bromo and iodo complexes occupy general positions, but one of the ligands is disordered in the bromo complex. All of the complexes are mononuclear with the four-coordinate metals possessing distorted tetrahedral geometry. The extent of the distortion is indicated by the angles at the metal which range from 93.71(7) to 127.73(7)°. Metal–sulfur distances range from 2.4514(14) to 2.571(3) Å. Metal–halogen distances range from 2.5984(13) Å (chloro) through 2.641(3) and 2.647(3) Å (bromo) to 2.7866(11) and 2.8047(9) Å (iodo). Hydrogen bonds, involving the thioamide hydrogen (NH) and halogen atoms are exclusively intramolecular in the chloro complex, but both intramolecular and intermolecular in the bromo and iodo complexes.

Solution multinuclear (31P,111Cd,77Se) magnetic resonance studies of cadmium complexes of heterocyclic aromatic thiones and the structure of [tetrakis(2(1H)-pyridinethione)cadmium] nitrate, [Cd(C5H5NS)4](NO3)2

The complex salts CdL4(O3SCF3)2 (L = 2(1H)-pyridinethione (Py2SH), 4(1H)-pyridinethione (Py4SH), or 2(1H)-quinolinethione (Q2SH)) have been synthesized by the stoichiometric reaction of Cd(O3SCF3)2 and the appropriate thione. Both ambient-temperature 13C and reduced-temperature 111Cd NMR of CdL4(O3SCF3)2 in solution are consistent with L being bound through sulfur. Reduced-temperature NMR (31P, 77Se, 111Cd, as appropriate) of mixtures of CdL4(O3SCF3)2 and Cd(EPCy3)4(O3SCF3)2 (E = Se, Cy = c-C6H11) and of Cd(EPCy3)4(O3SCF3)2 (E = S, Se) and L in solution provides evidence for various [CdLn(EPCy3)4-n]2+. Similarly, reduced-temperature metal NMR of [CdL4]2+ and [CdL'4]2+ (L, L' = Py2SH, Py4SH, Q2SH; L not equal L') in solution shows the formation of [CdLnL'4-n]2+. Thus it has been demonstrated that at reduced temperature [CdL4]2+ is intact in solution and exchange of L is slow on the timescale of the metal chemical shift differences. From the NMR studies of Cd(EPCy3)4(O3SCF3)2 (E = S, Se):L mixtures, the binding preferences are found to be L > EPCy3 in solution. Similarly, from the reduced temperature metal NMR spectra of mixtures where L and L' compete for Cd(II) in solution, the binding preferences are Py4SH > Py2SH > Q2SH. The structure of Cd(Py2SH)4(NO3)2 (4) has been determined by single crystal X-ray analysis. Colorless crystals of 4 are tetragonal, I4(1)/acd with 8 molecules per unit cell of dimensions a = 18.660(3), c = 15.215(3) Å. The structure is comprised of recognizable NO3- anions and [Cd(Py2SH)4]2+ cations. In the cations, which have S4 symmetry, the ligands are S-bound. A network of NH···O hydrogen bonds links the cations and anions.Key words: aromatic heterocyclic thiones, cadmium complexes, phosphine chalcogenides, 111Cd, 31P, 77Se NMR, X-ray crystallography.

Synthesis and characterisation of cobalt(III), nickel(II), copper(I) and silver(I) complexes of silylated pyridine-2-thione

The electrochemical oxidation of anodic metal (cobalt, nickel, copper and silver) in acetonitrile solutions of the appropriate heterocyclic thione, RMe2SipySH (3-ButMe2SipySH, 3-ThexMe2SipySH, 6-ThexMe2SipySH) gave complexes of general formula [M(RMe2SipyS)] (M = Cu, Ag) and [M(RMe2SipyS)n] (when M = Co, n = 3; M = Ni, n = 2). When the oxidation was repeated in the presence of 2,2′-bipyridine (bipy), the mixed complexes [M(RMe2SipyS)2(bipy)] were obtained only in the case of M = Ni. The reaction between copper complexes, [M(RMe2SipyS)], and 1,2-bis(diphenylphosphino)ethane (dppe) and bis(diphenylphosphino)methane (dppm) in acetonitrile yielded [Cu2(RMe2SipyS)2(dppe)3] and [Cu2(RMe2SipyS)2(dppm)2]. The molecular structures of [Cu6(3-ButMe2SipyS)6], 1, [Cu6(6-ThexMe2SipyS)6], 2, and [3-ButMe2SipyS-Spy-3-ButSiMe2], 3, were determined by X-ray diffraction. Compounds 1 and 2 are hexanuclear with the six copper atoms arranged in a distorted octahedral geometry and each copper atom in a distorted trigonal planar [CuS2N] environment, each ligand adopting the N,S-bidentate S-bridging mode. The electronic, vibrational and 1H and 13C NMR spectra of the complexes are discussed and related to the structure.

ChemInform Abstract: Synthesis of Symmetrical N,N′‐Disubstituted Thioureas and Heterocyclic Thiones from Amines and CS2 over a ZnO/Al2O3 Composite as Heterogeneous and Reusable Catalyst.

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Synthesis of Symmetrical N,N'-Disubstituted Thioureas and Heterocyclic Thiones from Amines and CS(2) over a ZnO/Al(2)O(3) Composite as Heterogeneous and Reusable Catalyst.

Synthesis of Symmetrical N,N'-Disubstituted Thioureas and Heterocyclic Thiones from Amines and CS(2) over a ZnO/Al(2)O(3) Composite as Heterogeneous and Reusable Catalyst.

Reactivity of [NBu 4] 2[{(C 6X 5) 2M(μ-OH)} 2] (X=F or Cl; M=Pd or Pt) towards heterocyclic thiones: crystal structure of [NBu 4] 2[{(C 6F 5) 2Pd( μ- ν2-LL′)} 2] (LL′=methylimidazole-2-thiolate)

The di-μ-hydroxo complexes [NBu 4] 2[{(C 6X 5) 2M(μ-OH) 2} 2] (M=Pd or Pt; X=F or Cl) react with heterocyclic thiones H(LL′) (1:2 molar ratio) to give the heterocyclic-2-thiolate complexes NBu 4][C 6X 5) 2M( ν 2-LL′)](LL′=pyridine-2-thiolate (pyS), pyrimidine-2-thiolate (ϱyrimS). 2,6-dimethyl-5-oxo-1,2,4,-triazine-3-thiolate (Me 2tazS). 6-methyl-5-oxo-1,2,4,-triazine-3-thiolate (MetazS)) or [NBu 4] 2[{(C 6F 5) 2M( μ- η 2-MeimidS)} 2] (MeimidS=methylimidazole-2-thiolate). The variable-temperature 1H NMR spectra of the complexes [NBu 4] 2[{(C 6F 5) 2M( μ- ν 2-MeimidS)} 2] (M=Pd and Pt) suggest the existence of dynamic methylimidazole-2-thiolate complexes [NBu 4][(C 6X 5) 2M( ν 2-LL′)] over the range −50 to +60°C are all static, but those of the chemical processes involving both dimeric and monomeric species. Crystallization of [NBu 4] 2[{(C 6F 5) 2Pd( μ- ν 2-MeimidS)} 2] from wet dichloromethane-hexane-etherafforded the mixed complex [NBu 4] 2[{(C 6F 5) 2Pd} 2( μ-OH)( μ- ν 2-MeimidS)]. The analogous mixed platinum complex [NBu 4] 2[{(C 6F 5) 2Pt} 2( μ-OH( μ- ν 2-MeimidS)] was prepared by reaction of [NBu 4] 2[{(C 6X 5) 2Pt(μ-OH) 2} 2] with the corresponding heterocyclic thione H(LL′) in 1:1 molar ratio. The crystal structure of [NBu 4] 2[{(C 6F 5) 2Pd( μ- ν 2-MeimidS)} 2], determined by X-ray diffraction, confirmed the dimeric structure with a head-to-tail arrangement. C 64H 82F 20N 6Pd 2S 2, orthorhombic Pca2 1, a=19.552(8), b=25.160(3), c=14.727(3) A ̊ , Z=4 .

Silver(I) complexes with heterocyclic thiones and tertiary phosphines as ligands. Part 3. Solution behaviour of mononuclear complexes of silver(I) nitrate. The crystal structure of bis(triphenylphosphino)bis(benzoxazoline-2-thione)silver(I) nitrate

The preparation of a series of mononuclear mixed-ligand silver(I) nitrate complexes of the general formula [Ag(PPh 3) 2(thione) n ][NO 3] ( n = 1,2; thione = pyridine-2-thione (py2tH), pyrimidine-2-thione (pymtH), 4-methylpyrimidine-2-thione (MepymtH) 4-aminopyrimidine- 2-thione (NH 2pymtH), 4-hydroxypyrimidine-2-thione (OHpymtH), quinoline-2-thione (quintH), benz-1,3-thiazolidine-2-thione (btzdtH). and benz-1,3-oxazoline-2-thione (boztH) is described and their solid state and solution spectroscopic data reported. The crystal structure of [Ag(PPh 3) 2(boztH) 2][NO 3] is also reported and discussed with respect to analogous complexes. The coordination geometry about the silver atom is distorted tetrahedral with mean AgS and AgP bond lengths of 2.67 and 2.49 Å respectively and a nitrate ion forming hydrogen bridge with one of the thione NH-groups of the complex ion. The inequality of the AgS bonds together with the bulk of the thione account for the observed solution 31P NMR spectra.

Synthesis and characterization of copper(I) complexes with triphenylphosphine and heterocyclic thione ligands: the crystal structure of (thiazolidine-2-thione)(bis-triphenylphosphine) copper(I) chloride

Reactions of [Cu(PPh 3) 3Cl] with heterocyclic thiones (L) (L = pyridine-2-thione (py2SH), 1,3-thiazolidine-2-thione (tzdtH), benz-1,3-imidazoline-2-thione (bzimtH 2), bens-1,3,-thiazoline-2-thione (bzimtH), 4,5-diphenyl-imidazol-2-thione (dpimtH), 3-methylbenz-1,3-thiazoline-2-thione (mbztztH), 6-ethoxybenz-1,3-thiazoline-2-thione (etbztztH). 4-hydroxy-5-methyl-pyridine-2-thione (hympmtH), 4,6-dimethyl-pyrimidine-2-thione (dmpmtH), 4-mercapto-1H-pyrazolo[3,4 d] pyrimidine (pyrpmtH) and quinoline-2-thione (quintH)) yield mononuclear complexes of the general formula [Cu(PPh 3) 2(L)Cl]. The complexes were characterized by various physicochemical methods. The crystal structure of [Cu(PPh 3) 2(tzdtH)Cl] was determined by single-crystal X-ray diffraction methods. The yellow crystals are monoclinic, space group P2 1/c with a = 14.31(2), b = 10.099(10), c = 24.52(2) A ̊ , β = 93.53(7)° and Z = 4 . The copper atom has a pseudotetrahedral geometry with the bond lengths CuS = 2.418(5), CuCl = 2.344(3), CuP(1) = 2.287(3) and CuP(2) = 2.298(2) A ̊ . The structure was solved by direct methods with a final R value of 0.0562.

Complexes of copper(I), silver(I), nickel(II) and cadmium(II) with 6-tert-butyldimethylsilylpyridine-2-thionate (6-Bu tSidmepyS −): crystal structure of [Cu 2(6-Bu tSidmepyS) 2dppm 2

Complexes of general formulae [M(6-Bu tSidmepyS)] (M = Cu, Ag] or [ M(6- Bu t SidmepyS) 2] (M = Ni, Cd) were prepared by electrochemical oxidation of the appropriate metal in an acetonitrile solution of the neutral heterocyclic thione (6-Bu tSidmepySH): with a solution of the thione and 2,2′-bipyridine (bipy) this method gives [Ni(6-Bu tSidmepyS) 2bipy]. The reaction between [Cu(6-Bu tSidmepyS)] and 1,2-bis(diphenylphosphino)ethane (dppe) or bis(diphenylphosphino)methane (dppm) in acetonitrile yielded [Cu 2(6-Bu tSidmepyS) 2 (dppe) 2] and [Cu 2(6-Bu tSidmepyS) 2(dppm) 2]: the latter exhibits a dinuclear structure with one dppm and two thione ligands acting as bridges between the copper atoms. Vibrational and 1H and 13C NMR spectra of the complexes are discussed and related to the structure.

Silver(I) complexes with heterocyclic thiones and tertiary phosphines as ligands Part 2. Mononuclear complexes of silver(I) nitrate. The crystal structures of [Ag(PPh 3) 2(pytH) 2]NO 3 and [Ag(PPh 3) 2(pymtH)]NO 3

The preparation and characterization of mononuclear silver(I) nitrate complexes with various heterocyclic thiones (pytH = pyridine-2-thione, pymtH = pyridine-2-thione, quin2tH = quinoline-2-thione, izdtH = thiazolidine-2-thione, mbzimtH 2 = N=methyl-benzimidazoline-2thione, pur6tH = purine-6-thione) and triphenylphosphine as ligands are described. The X-ray determination of the crystal structures of [Ag(PPh 3) 2(pytH) 2]NO 3 ( I) and [Ag(PPh 3) 2(pymtH)]NO 3 ( II) is also reported. Compound I crystallizes in the monoclinic system, space group P2 1/ c, with a = 12.588(3), b = 18.234(5), c = 18.527(5) A ̊ , β = 96.29(2)°, V = 4227 A ̊ 3 and Z = 4 , while crystals of II are triclinic, space group P 1 , with a = 10.084(2), b = 13.508(3), c = 14.326(3) A ̊ , α = 77.43(2), β = 78.14(2)°, V = 1646 A ̊ 3 and Z = 2 . The coordination geometry about the silver atom is distorted tetrahedral in I, with one nitrate ion bridging two adjacent complex molecules via strong hydrogen bonds with the thione NH groups. The structure of II consists of almost trigonal-planar AgP 2S units and strongly distorted nitrate ions hydrogen bonded to the protonated nitrogen atoms of the heterocyclic thione ligands. The electronic factors imposing the above difference in coordinating behavior are investigated by means of semi-empirical molecular orbital considerations.

Electrochemical synthesis and crystal structure of silver(I) complexes with some heterocyclic thiones

Two silver(I) complexes, [{Ag(SR)}6][R1SH = 6-(tert-butyldimethylsilyl)pyridine-2-thione 1, R2SH = 3,6-bis(tert-butyldimethylsilyl)pyridine-2-thione 2], have been synthesized by electrochemical oxidation of the metal in an acetonitrile solution of the neutral heterocyclic thiones. The reaction of equimolar amounts of dppm [bis(diphenylphosphino)methane] with complexes 1 and 2 in dichloromethane resulted in the formation of [Ag4Cl4(dppm)2]3 and the elimination of RSCH2SR. Single-crystal X-ray analyses were performed for compounds 1, 3 and R2SCH2SR2.

Electrochemical reduction of dinuclear copper(I) mixed ligand complexes with tri- m-tolylphosphine and heterocyclic thiones

The electrochemical studies on a glassy carbon electrode in acetonitrile solutions of dinuclear copper(I) complexes with the general formula [Cu(tmtp)(L)Br] 2, where tmtp = tri- m-tolylphosphine and L = pyridine-2-thione (pyridine-2-thione (py2SH), 1,3-thiazolidine-2-thione (tzdtH), benz-1,3-imidazoline-2-thione (bzimtH 2) and quinoline-2-thione (quintH) have been carried out. The monitoring of the peak position versus scan rate combined with semi-empirical calculations on model compounds provide a suitable method for the characterization of the nature of the bridge formed between the two copper atoms, which may be either sulphur or halogen.

Magnetic Properties and Crystal Structures of Binuclear Copper(II) Complexes with Heterocyclic Thione Donors of 1,3-Bis(hydroxymethyl)-2-imidazolidinethione and 1-Hydroxymethyl-3-methyl-2-imidazolidinethione

Abstract A new series of binuclear copper(II) complexes with 1,3-bis(hydroxymethyl)-2-imidazolidinethione, [Cu(RCOO)(HL1)]2 (where R = CH3 (1), C6H5 (2), 2-CH3C6H4 (3), 4-CH3C6H4 (4), 2-ClC6H4 (5), and 2-BrC6H4 (6)), and with 1-hydroxymethyl-3-methyl-2-imidazolidinethione, [Cu(RCOO)(L2)]2 (where R = CH3 (7), 2-CH3C6H4 (8), and 4-CH3C6H4 (9)), have been prepared. The magnetic susceptibility data of complexes 1—9 conform to the usual dimer equation with the −2J values ranging from 227 to 992 cm−1. Crystal structure analyses of 3, 4, 7, and 9 revealed that two copper atoms are linked by two alkoxo-bridges with separations of 3.015(3)—3.069(3) Å in each complex. The coordination around each copper atom of the complexes is essentially a square planar configuration with one sulfur and two alkoxo-oxygen atoms of HL1 or L2 and one oxygen atom of carboxylates. Each alkoxo-group asymmetrically bridges with the Cu1–O1 bonds (1.90—1.92 Å), which are shorter than the Cu1′–O1 bonds (1.93—1.97 Å). The −2J values for complexes 3, 4, 7, and 9 are much better correlated with the Cu1′–O1 bond distances than with the alkoxo-bridging Cu1–O1–Cu1′ angles.

Electrochemical synthesis of mercury(II) complexes with some heterocyclic thiones : The crystal and molecular structures of bis(6-Tertbutyldimethylsilyl)2-Pyridyl disulphide (6-Bu tSidmepyS-Spy-6-BuSidme) and Hg(6-Bu tSidmepyS) 2

A series of complexes of the type Hg(SR) 2 have been obtained by oxidation of the metal in an acetonitrile solution of the neutral heterocyclic thiones (RSH). The crystal and molecular structures of bis(6-tertbutyldimethylsilyl)2-pyridyI disulphide (6-Bu t SidmepyS-Spy-6-Bu t Sidme) and of bis[(6-tertbutyldimethylsilyl) pyridyl-2-thionato] mercury(II), (Hg(6-Bu t SidmepyS( 2) have been determined by single crystal X-ray diffraction. The structure the mercury complex consists of individual centrosymmetric monomeric molecules with linear two coordination, SHgS and weak intramolecular HgN interactions. Vibrational and 1H, 13C and 199Hg NMR spectral data of the complexes are discussed and related to the structure.

Preparation and spectral studies of dinuclear mixed-ligand copper(I) complexes. The crystal structure of bis[μ-s(pyridine-2-thione)(tmtp) copper(I) bromide

[Cu(tmtp)Br] n (tmtp = tri- m-tolylphosphine) reacts with heterocyclic thiones (L) [L = pyridine-2-thione (py2SH), 1,3-thiazolidine-2-thione (tzdtH), benz-1,3-imidazoline-2-thione (bzimtH 2), benz-1,3-thiazoline-2-thione (bztzdtH), imidazoline-2-thione (imtH), benz-1,3-oxazoline-2-thione (bzoxtH 2), 5-nitrobenz-1,3-imidazoline-2-thione (nbzimtH 2), and 5-methyl-benz-1,3-imidazoline-2-thione (mebzimtH 2)] to give binuclear complexes of the general formula [Cu(tmtp)(L)Br] 2. These complexes have been characterized by various spectroscopic methods. The crystal structure of the pyridine-2-thione complex has been determined by single-crystal X-ray diffraction methods. The molecule contains a planar Cu 2S 2 moiety with CuS bond lengths of 2.3348(9) and 2.4879(7) Å. The CuBr and CuP distances are 2.4929(1) and 2.2525(4) Å, respectively, whereas the Cu⋯Cu separation is 2.6906(1) Å.

MIXED LIGAND COORDINATION COMPOUNDS OF COPPER(I) WITH HETEROCYCLIC THIONES AND TERTIARY PHOSPHINES. THE CRYSTAL STRUCTURE OF BIS (QUINOLINE-2-THIONE) BISTRIPHENYLPHOSPHINO COPPER(I) ETHYLSULFATE HEMIHYDRATE

Abstract Copper(II) sulfate is reduced in alcoholic media in the presence of heterocyclic thiones (i.e. pyridine-2-thione or quinoline-2-thione) and triphenylphosphine. The resulting coordination compounds consist of Cu(thione)2(PPh3)2 cationic units; the counteranions are alkyl sulfate monoanions. The crystal structure of the compound prepared using quinoline-2-thione in ethanol reveals that the tetrahedal cationic units and the counteranions are arranged in rows cross-linked through hydrogen bonds formed between the oxygen atoms of the anion and water molecules. The compound crystallizes in the triclinic space group P 1, a = 10.69 (1), b = 13.47 (2), c = 18.75 (2) A, α = 75.9 (1), β=85.6 (1), γ=74.7 (1)°, V = 2525.5 A3, Z = 2. The local copper environment is distorted tetrahedal with unequal Cu-S (2.380(2), and 2.341(2) A) and Cu-P (2.301(2) and 2.316(2) A) bonds; angles around copper range from 96.37(7) to 121.16(0)°.

On the molecular structure of gold(I) complexes with heterocyclic thiones. The structure of bis(1,3-thiazolidine-2-thione) gold(I) chloride hydrate

The preparation of a seies of gold(I) coordination compounds with heterocyclic thiones is reported. The crystal structure of the coordination compound with 1,3-thiazolidine-2-thione (tztH) was determined. The S—Au—S angle is 176.52(2)° and the two Au—S distances are 2.281(5) and 2.288(5) Å, respectively, giving rise to the usual linear gold(I) environment. Extended Hückel computations on both the model and the observed Au(thione) 2 cationic unit are used in an attempt to unravel the factors influencing the local and overall molecular structure observed, which is determined by an extended hydrogen-bond network. On the grounds of these computations and the existing strutural evidence, it is concluded that hydrogen bonds formed by the coordinated thione ligands determine the geometry adopted by these and analogous compounds.