Xiao-Yan Tang

Binding of a coordinatively unsaturated mercury(II) thiolate compound by carboxylate anions.

Reactions of [Hg(Tab)2](PF6)2 (TabH = 4-(trimethylammonio)benzenethiol) (1) with acetic acid (HAc), propanoic acid (HPro), salicylic acid (HSal), benzoic acid (HBez), malonic acid (H2Mal), oxalic acid (H2Oxa), adipic acid (H2Adi), or methylimindiacetic acid (H2Meida) in the presence of Et3N gave rise to a family of mercury(II)-thiolate-carboxylate compounds, [Hg(Tab)2(Ac)](PF6) · 0.5H2O (2 · 0.5H2O), [Hg(Tab)2(Pro)](PF6) (3), [Hg(Tab)2(Sal)](PF6) · MeOH (4 · MeOH), [Hg(Tab)2(Sal)](Sal) · MeOH (5 · MeOH), [Hg(Tab)2(Bez)](PF6) · H2O (6 · H2O), [Hg(Tab)2(HMal)](Mal)0.5 H2O (7 · H2O), [{Hg(Tab)2}2(μ-Oxa)](PF6)2 H2O (8·2H2O), [{Hg(Tab)2}2(μ-Adi)](PF6)2 (9), [Hg(μ-Tab)(μ-Adi)]2n (10), and [Hg(Tab)2(Meida)] · 2.5H2O (11 · 2.5H2O). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra, (1)H NMR, and single-crystal X-ray crystallography. Each mercury(II) atom in [Hg(Tab)2](2+) dication of 2-7 is further coordinated by two oxygen atoms from one Ac(-), Pro(-), Sal(-), Bez(-), Mal(2-) or HMal(-) anion, forming a unique seesaw-shaped coordination geometry. In 8 or 9, two [Hg(Tab)2](2+) dications are connected by one bridging oxalate or adipate dianion to generate a dimeric structure with each mercury(II) center adopting a seesaw-shaped geometry. In 10, a pair of octahedrally coordinated mercury(II) atoms are bridged by two sulfur atoms of two Tab ligands to form a [Hg(μ-Tab)2Hg](4+) fragment, which is further connected to its equivalent ones via four adipate dianions, thereby forming a rare two-dimensional network. In 11, the mercury(II) atom in the [Hg(Tab)2](2+) dication is coordinated by one nitrogen and two oxygen atoms from one Meida(2-) dianion to have a rare square pyramidal geometry. The formation of 2-11 from 1 may be applicable to mimicking the interactions of the mercury(II) sites of Hg-MerR and Hg-MT with various amino acids encountered in nature.

[Bis(3,5‐dimethylpyrazol‐1‐yl‐κN2)dithioacetato‐κS](triphenylphosphine‐κP)copper(I)

In the title compound, [Cu(C(12)H(15)N(4)S(2))(C(18)H(15)P)], the copper(I) center is tetrahedrally coordinated by one S atom and two N atoms from one bis(3,5-dimethylpyrazol-1-yl)dithioacetate ligand and one P atom from a triphenylphosphine ligand. In the crystal structure, adjacent pyrazole rings are involved in weak pi-pi interactions, thereby forming a one-dimensional zigzag chain running along the b axis.

Bis[4-(trimethylammonio)phenyl] disulfide diiodide acetone solvate.

The title compound, C(18)H(26)N(2)S(2)(2+).2I(-).2C(3)H(6)O, is an intermediate in the design of the zwitterionic thiolate 4-(trimethylammonio)benzenethiolate (Tab), in which a pair of aryl-substituted S atoms are linked by a covalent bond. The central S-S bond length is 2.020 (3) A and the C(ar)-S-S-C(ar) torsion angle is -84.1 (2) degrees . The crystal structure is stabilized by nonclassical hydrogen bonds which occur as intramolecular C-H...I interactions and intermolecular C-H...S and C-H...O contacts. In the crystal structure, both the dication and the two symmetrically independent iodide counter-anions are located on twofold crystallographic axes, whereas the acetone solvent molecule occupies a general position.

CCDC 604372: Experimental Crystal Structure Determination

Related Article: Jin-Xiang Chen, Wen-Hua Zhang, Xiao-Yan Tang, Zhi-Gang Ren, Yong Zhang, Jian-Ping Lang|2006|Inorg.Chem.|45|2568|doi:10.1021/ic051875n

Bis[bis­(3,5-dimethyl­pyrazol-1-yl)­methane]bis­(isothio­cyanato)­cadmium(II) and catena-poly[[di-μ-dicyan­amidato-bis­{[bis­(3,5-dimethyl­pyrazol-1­yl)­methane]­cadmium(II)}]-di-μ-di­cyan­amidato]

The Cd atom in bis[bis(3,5-dimethylpyrazol-1-yl)methane]bis(isothiocyanato)cadmium(II), [Cd(NCS)2(C11H16N4)2], is octahedrally coordinated by four N atoms from two bis(3,5-dimethylpyrazolyl)methane (dmpzm) ligands and two isothiocyanate ligands. The molecule has a crystallographic center of symmetry located at the Cd atom. There are two intramolecular C-H...N interactions, each of which is formed between the methylene group of a dmpzm ligand and the N atom of an isothiocyanate ligand. On the other hand, in catena-poly[[di-mu-dicyanamidato-bis{[bis(3,5-dimethylpyrazol-1-yl)methane]cadmium(II)}]-di-mu-dicyanamidato], [Cd2(C2N3)4(C11H16N4)2]n, each Cd atom is octahedrally coordinated by two N atoms from one dmpzm ligand and four N atoms from four bridging dicyanamide (dca) anions. Two Cd atoms are bridged by a pair of dca anions, forming a dimeric [Cd2(mu-dca)2(dmpzm)2] unit. Another two pairs of dca anions further link this unit with neighboring units to form a brick-wall layer parallel to (100). A C-H...N interaction between the methylene group of one dmpzm ligand in one layer and a coordinating N atom of a dca ligand in an adjacent layer completes a three-dimensional network.