Amirah Faizah Abdul Muthalib

Structural systematics of RSn(S 2CN R′ R″) 2Cl compounds

Abstract Three new organotin(IV) structures of general formula RSn(S 2CN R′ R″) 2Cl, where R′ ≠ R″, namely MeSn · [S 2CN(Me)(Cy)] 2Cl ( 1), MeSn[S 2CN( i-Pr)(CH 2Ph)] 2Cl ( 2) and PhSn[S 2CN(Et)( i-Pr)] 2Cl ( 3) are described. Each structure features tin in a distorted octahedral geometry defined by a C ClS 4donor set as a result of two chelating dithiocarbamate ligands. In all cases the tin-bound carbon and chloride atoms are cis. The shorter Sn–S bond lengths in 3are correlated with the presence of the relatively more electronegative Sn-bound phenyl substituent. The new structures conform to the structural motif adopted by all other compounds with the formula RSn(S 2CN R′ R″) 2Cl, where R′ = R″, suggesting the unsymmetrical substitution pattern of the dithiocarbamate ligands in the present study does not influence the adoption of this structural motif. The homogeneity in the structural motif notwithstanding, non-systematic variations in geometric parameters are found in these structures indicating an overall influence of crystal packing upon molecular geometry.

(N-Benzyl-N-isopropyl­dithio­carbamato)chloridodiphenyl­tin(IV)

The SnIV atom in the title organotin dithiocarbamate, [Sn(C6H5)2(C11H14NS2)Cl], is penta-coordinated by an asymmetrically coordinating dithiocarbamate ligand, a Cl and two ispo-C atoms of the Sn-bound phenyl groups. The resulting C2ClS2 donor set defines a coordination geometry intermediate between square-pyramidal and trigonal-bipyramidal with a slight tendency towards the latter. The formation of close intramolecular C–H⋯Cl and C–H⋯S contacts precludes the Cl and S atoms from forming significant intermolecular contacts. The presence of C–H⋯π contacts leads to the formation of supramolecular arrays that stack along the b axis.

New Dithiocarbamate Compounds from Organotin(IV)

Abstract A series of new organotin(IV) dithiocarbamate compounds of type RnSn (S2CNR′R″)4-n (n = 2, 3; R = dimethyl, dibutyl, diphenyl, triphenyl and tert-butyl; R′ = methyl, ethyl, benzyl; R″ = isopropyl, ethyl, ethanol) have been successfully synthesized. Elemental analysis showed that the percentage of the elements conformed to the general formula of these compounds. The important peaks of the infrared spectra for the stretching mode ν(C˭N), ν(C˭S), and v(Sn-S) for the compounds were observed in the area of 1440–1480 cm−1, 940–1000 cm−1, and 340–90 cm−1, respectively. The 13C NMR spectra showed the most important peak for N13CS2 chemical shifts were observed in the range 190–210 ppm. X-ray single crystal studies for several structures of these compounds showed that the chelating mode of the dithiocarbamate groups to the central tin atoms were either bidentate or anisobidentate. GRAPHICAL ABSTRACT

Crystal structure of n-butyl-chlorido-bis[N-sec-butyl,N-n-propyl-carbamodithioato κ2S,S′]-tin(IV), C20H41ClN2S4Sn

Abstract C20H41ClN2S4Sn, triclinic, P1̅ (no. 2), a = 10.0750(3) Å, b = 10.7593(7) Å, c = 13.3097(6) Å, α = 74.619(5)°, β = 86.861(3)°, γ = 88.582(4)°, V = 1388.93(12) Å3, Z = 2, Rgt(F) = 0.044, wRref(F2) = 0.106, T = 100 K.

New mono-organotin (IV) dithiocarbamate complexes

Eighteen new mono-organotin dithiocarbamate compounds derived each nine from methyltin(IV) and phenyltin(IV) reacted using in-situ method with various type of N-dialkylamine together with carbon disulphide with the ratio of 1:3:3. Elemental and gravimetric analysis showed that the general formula of these compounds were RSnCl[S2CNR′R″]2 (R= Ph, CH3, R′ = CH3, C2H5, C7H7 and R″ = C2H5, C6H11, iC3H7, C7H7). These compounds had been characterized by infrared spectroscopy, ultraviolet spectroscopy, 1H, 13C NMR spectroscopy and single crystal X-ray crystallography. The infrared spectra of these compounds showed three important peaks indicating the formation of dithiocarbamate compounds, ν(C N), ν(C S) and ν(Sn-S) band which present in the region of 1444–1519, 954–1098 and 318–349 cm−1 respectively. The ultraviolet-visible spectra showed an absorption band...

(N-Benzyl-N-ethyl-dithio-carbamato)di-tert-butyl-chloridotin(IV).

The SnIV atom in the title diorganotin dithiocarbamate, [Sn(C4H9)2Cl(C10H12NS2)], is pentacoordinated by an asymmetrically coordinating dithiocarbamate ligand, a Cl and two C atoms of the Sn-bound tert-butyl groups. The resulting C2ClS2 donor set defines a coordination geometry intermediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former. In the crystal structure, C—H⋯π contacts link centrosymmetrically related molecules into dimeric aggregates.

Di-tert-butyl­chlorido(N,N-dibenzyl­dithio­carbamato)tin(IV)

The SnIV atom in the title diorganotin dithiocarbamate, [Sn(C4H9)2(C15H14NS2)Cl], is pentacoordinated by an asymmetrically coordinating dithiocarbamate ligand, a Cl atom and two C atoms of the Sn-bound tert-butyl groups. The resulting C2ClS2 donor set defines a coordination geometry intermediate between square pyramidal and trigonal bipyramidal with a slight tendency towards the former.

Bis(N-isopropyl-N-methyl­dithio­carbamato-κ2S,S′)diphenyl­tin(IV)

The dithiocarbamate anions in the title compound, [Sn(C6H5)2(C5H10NS2)2], chelate to the SnIV atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The molecule lies across a twofold rotation axis.

Bis(N-ethyl-N-methyl­dithio­carbamato-κ2S,S′)diphenyl­tin(IV)

The dithiocarbamate anions in the title compound, [Sn(C6H5)2(C4H8NS2)2], chelate to the SnIV atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The molecule lies across a twofold rotation axis.

Di-tert-butyl­bis(N-isopropyl-N-methyl­dithio­carbamato-κ2S,S′)tin(IV)

The dithiocarbamate anions in the title compound, [Sn(C4H9)2(C5H10NS2)2], chelate to the SnIV atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The molecule lies across a twofold rotation axis. The crystal studied was a non-merohedral twin, the ratio of the twin components being 0.82 (1):0.18 (1).