S. M. Zemskova

Synthesis and crystal structure of ZnPhen(i-Pr2NCS2)2 and molecule packing types in complexes ZnPhen(R2NCS2)2 (R=Me, Et, i-Pr, n-Pr, i-Bu, n-Bu)

Abstract A novel mixed-ligand complex ZnPhen(i-Pr2NCS2)2 has been synthesized and its single crystals grown. We have determined its crystal structure from X-ray diffraction data. The structure consists of monomeric molecules; a zinc atom surrounded by two nitrogen and four sulfur atoms making a distorted octahedron. Various packing modes of molecules forming isolated ‘dimers’, ribbons (chains), columns and layers have emerged from the study of the spatial molecule arrangement in the complexes ZnPhen(R2NCS2)2 (R=Me, Et, i-Pr, n-Pr, i-Bu, n-Bu). The interactions between the Phen molecules have also been studied for these complexes.

The preparation, structures and thermal properties of [Men3][Cd(S2CNEt2)3]2 [M = zinc(II), cadmium(II)] complexes

Abstract New complexes of the general formula [MEn3][CdL3]2 [M = Cd (I), Zn (II), En = NH2CH2CH2NH2, L = Et2NCS2−) have been prepared and their crystal structures have been determined. Complexes I and II are isostructural. In the [MEn3]2+ cation, the metal atom is six-coordinated by the nitrogen atoms of three ethylenediamines forming a distorted octahedron, while in the [CdL3]− anion the metal atom is six-coordinated by the sulphur atoms of three bidentate L ligands forming a distorted trigonal prism. The thermal behaviour investigation of complexes I and II has shown that the final products of their thermolysis are CdSwur and Zn0.25Cd0.75Swur, respectively.

Structure and properties of mono- and heterometallic cadmium, zinc, and nickel complexes containing diethyldithiocarbamate ions and ethylenediamine molecules

The crystal structure of the mono- and heterometallic complexes [MEn3]L2 (M = Zn2+,M2+) and [MEn3 ][CdL3]2 (M = Cd2+, Zn2+, Ni2+) containing ethylenediamine (En) molecules and diethyldithio-carbamate ions (L = (C2H5)2NCS2−) is investigated. The three heterometallic complexes are isostructural; their structure consists of discrete mononuclear ions. In the [MEn3]2+ cation, the central M atom lies on the twofold axis; therefore, two of the three metallocycles MN2C2 of the [MEn3]2+ cation are independent. One of the two has a gosh-configuration. In the coordinated En molecules, the N-M-N chelate angles are 77.0 and 82.9‡ (M = Cd2+); 80.0 and 80.5‡ (M = Zn2+); 79.7 and 80.8‡ (M = Ni2+). The nitrogen atoms form a distorted octahedron around M. The average M-N bond lengths for the complexes are 2.35, 2.19, and 2.16 å for M = Cd2+, Zn2+, and Ni2+, respectively. All the atoms of the [CdL3]− complex anion are in the general position; the central atom coordinates three cyclic bidentate L− ligands. The S atoms form a distorted trigonal prism, where the S...S distances in the vertical edges are nearly the same in all the complexes (2.94(1)-3.00(2) å). It was shown by1H,14N, and113Cd NMR that the ionic complexes [ZnEn3]L2 and [CdEn3][CdL3]2 in solution are transformed into nonelectrolyte type mixed-ligand complexes.

X-ray spectral study of the nature of electronic interactions in transition metal dithiocarbamates

SKβ spectra are studied for a series of nickel(II), zinc(II), and cadmium(II) dithiocarbamate complexes. Model quantum chemical calculations of the electronic structure of planar chelate rings are reported. It is shown that the metal-ligand interaction forming a coordination bond between the dithiocarbamate ligand and the metal mainly involves the nonbonding n-electrons and the weakly bonding π-electrons localized on the sulfur atoms.

Molecular and crystal structure of cadmium(II) diisobutyldithiocarbamate Cd[(i-C4H9)2NCS2]2 2

i-Bu2NH ( 17 ml, 0.1 mole) was mixed with 17 ml of MeOH. and the mixture was placed in a flask cooled with an ice-NaCl mixture. CS 2 (6.0 ml, 0.1 mole) was added with vigorous stirring. Then a solution of NaOH (4.0 g, 0.I mole) in 100 ml of MeOH was dropped into the reaction mixture with cooling and stirring. The resulting clear yellowish solution was poured in portions to the solution of CdCi 2- 2.5H-,O ( 11.4 g, 0.05 mole) with stirring and cooling. A white substance precipitated in abundance from solution: it was filtered off, washed with water, and dried in air until dry to the powder state. The compound was recrystallized from a CHCI3:EtOH = 1:1 (v/v) mixture, Yield 24.4 g (94%), mp 172~ The metal content was measured (by trilonometric titration) to be 21.6% (calculated 21.6%). The single crystals of [Cd(i-Bu2NCS2)2] 2 were ~own by slowly cooling the hot saturated solution in toluene and subsequently evaporating it at room temperature. Transparent light yellow crystals were selected for X-ray diffraction analysis. One of the single crystals, sized ().Ix 0.2x 0.2 ram, was used for data collection (5226 reflections). The intensities were measured on a CAD-4 Enraf-Nonius automatic diffractometer using the standard procedure (~r m 0/20 scan mode, variable scan speed, ~aphite monochromator, maximal 20= 50~ The data were corrected for empirical (azimuthal q~ scan) absorption, /a(MoKc0 = 11.87 cm-1. The crystals are monoclinic with unit cell parameters a= 50.087(11), b= 9.613(2), c= 23,708(8) ,A, [3= 116.51(2)~ V= 10,215 A3 Z = 18; dcatc= 1.355 ~cm 3. The space group C2/c was determined by analyzing the extinctions in Fhk I and confirmed by further calculations. The structure was solved by direct methods with the SHELXS-86 pro~am [2] and refined by the full-matrix least-squares procedure anisotropically tor nonhydrogens with the SHELXL-93 program complex [3]. All hydrogen atoms were placed geometrically and included in the refinement in the isotropic approximation. The final R value (H atoms included) is 0.0466 for 5156 independent F,~t! with I > 20(1) (495 refined parameters). The corresponding positional and equivalent thermal isotropic parameters of basic atoms are given in Table 1; selected bond lengths and angles, in Table 2. The

Crystal Structure of the Mixed-Ligand Compound [HgPhen{(C2H5)2NCS2}2] and the Character of Intermolecular Interactions in [MPhen{(C2H5)2NCS2}2] (M = Zn, Cd, Hg)

AbstractSingle crystals of the mixed-ligand complex compound [HgPhen(Et2NCS2)2] were obtained. The crystal structure of the compound was determined by X-ray diffraction analysis (CAD-4 diffractometer, Mo

Investigation of complexes of zinc(II) and cadmium(II)DI-n-butyldithiocarbamates with 2,2′-bipyridyl

K_\alpha

Crystal and molecular structure of the volatile mixed-ligand complex Zn(S2CN(i-C4H9)2)2Phen

radiation, 3640 Fhkl, R = 0.0280). Triclinic crystals with cell parameters a = 10.308(2), b = 11.171(3), c = 11.552(2) Å, α = 94.16(2), β = 96.66(1), γ = 105.17(2)°, V = 1267.8(5) Å3, Z = 2, dcalc = 1.774 g/cm3, space group