(N,N-Diallyldithiocarbamato-κ² S,S′)triphenyltin(IV) and bis(N,N-diallyldithiocarbamato-κ² S,S′)diphenyltin(IV): crystal structure, Hirshfeld surface analysis and computational study

Abstract

The crystal and molecular structures of the title organotin dithiocarbamate compounds, [Sn(C6H5)3(C7H10NS2)] (I) and [Sn(C6H5)2(C7H10NS2)2] (II), present very distinct tin atom coordination geometries. In (I), the dithiocarbamate ligand is asymmetrically coordinating with the resulting C3S2 donor set defining a coordination geometry intermediate between square-pyramidal and trigonal–bipyramidal. In (II), two independent molecules comprise the asymmetric unit, which differ in the conformations of the allyl substituents and in the relative orientations of the tin-bound phenyl rings. The dithiocarbamate ligands in (II) coordinate in an asymmetric mode but the Sn—S bonds are more symmetric than observed in (I). The resulting C2S4 donor set approximates an octahedral coordination geometry with a cis-disposition of the ipso-carbon atoms and with the more tightly bound sulfur atoms approximately trans. The only directional intermolecular contacts in the crystals of (I) and (II) are of the type phenyl-C—H...π(phenyl) and vinylidene-C—H...π(phenyl), respectively, with each leading to a supramolecular chain propagating along the a-axis direction. The calculated Hirshfeld surfaces emphasize the importance of H...H contacts in the crystal of (I), i.e. contributing 62.2% to the overall surface. The only other two significant contacts also involve hydrogen, i.e. C...H/H...C (28.4%) and S...H/H...S (8.6%). Similar observations pertain to the individual molecules of (II), which are clearly distinguishable in their surface contacts, with H...H being clearly dominant (59.9 and 64.9%, respectively) along with C...H/H...C (24.3 and 20.1%) and S...H/H...S (14.4 and 13.6%) contacts. The calculations of energies of interaction suggest dispersive forces make a significant contribution to the stabilization of the crystals. The exception is for the C—H...π contacts in (II) where, in addition to the dispersive contribution, significant contributions are made by the electrostatic forces.

Synthesis and cytotoxic activity of organotin(IV) diallyldithiocarbamate compounds as anticancer agent towards colon adenocarcinoma cells (HT-29)

“…While for compound 2 , it was found that the results for the bond length of Sn-S1 are 2.4749 (4) Å, while the bond length of Sn-S2 is 2.9456 (7)Å ( Haezam et al, 2020 ). The short Sn-S bond distance falls in the range of 2.45–2.48 Å, while the long Sn-S bond distance falls in the range of 2.92–3.24 Å ( Tiekink 2008 ).…”

“…The parameters of compound crystal units 4 are a = 9.6160 (1) Å, b = 30.4216 (2) Å, c = 19.1928 (1) Å, and β = 100.019 (1) o . Whereas, a = 8.0650 (1) Å, b = 11.4490 (1) Å, c = 25.8875 (2) Å, and β = 98.282 (1) o are the case parameters for compound 2 ( Haezam et al, 2020 ).…”

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Fig. 1 The chemical structure of Compound 1 and Compound 2 ( Haezam et al, 2020 ).

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A Structural Survey of Poly-Functional Dithiocarbamate Ligands and the Aggregation Patterns They Sustain

“…In each of (Ph 2 Sn) 2 (L 21 ) 2 (65) and (Ph 2 Sn) 2 (L 32 ) 2 in (66), as shown in Figure 15d, more symmetric modes of coordination of the dithiocarbamate residues are apparent, so the cis-C 2 S 4 coordination geometries are distorted octahedral. Such perplexing coordination flexibility has been long recognised [91], especially as mono-nuclear diphenyltin bis(dithiocarbamate) molecules which are known to adopt both skew-trapezoidal bipyramidal and octahedral geometries in a ratio of 1:2, and therefore, the study of their structural characteristics continues to attract attention [92]. (65) and (Ph2Sn)2(L 32 )2 in (66), as shown in Figure 15d, more symmetric modes of coordination of the dithiocarbamate residues are apparent, so the cis-C2S4 coordination geometries are distorted octahedral.…”

“…(65) and (Ph2Sn)2(L 32 )2 in (66), as shown in Figure 15d, more symmetric modes of coordination of the dithiocarbamate residues are apparent, so the cis-C2S4 coordination geometries are distorted octahedral. Such perplexing coordination flexibility has been long recognised [91], especially as mono-nuclear diphenyltin bis(dithiocarbamate) molecules which are known to adopt both skew-trapezoidal bipyramidal and octahedral geometries in a ratio of 1:2, and therefore, the study of their structural characteristics continues to attract attention [92]. Despite having a different general formula to the preceding class of compounds, molecules of composition (R2SnX)2(S2CN-spacer-NCS2) adopt very similar structural motifs in their crystals: (Me2SnCl)2(L 1 ) in the crystal of 67 [68] Figure 16b, and 72 are generated by 2-fold symmetry, whereas compounds 69, 70, and 73, as shown in Figure 16c, and 76 are disposed about a centre of inversion; molecules related to 73 attract interest as sensors for anions [71].…”