Crystal Structure of Tetrakis(dimethyl N-cyanodithioiminocarbonate) Bis[(aqua)-µ2-hydroxy-n-butyldichloridotin(IV)]

Abstract

The reaction between two equivalents of dimethyl N-cyanodithioiminocarbonate, [(MeS)₂C=N–C≡N] (1), one equivalent of n-butyltin trichloride, Sn(n-Bu)Cl₃ and one equivalent of sodium hydroxide, NaOH led to isolation of a dinuclear complex {[Sn(n-Bu)Cl₂(OH)(H₂O)]₂} (2) which co-crystallized with four [(MeS)₂C=N–C≡N] molecules, {[Sn(n-Bu)Cl₂(OH)(H₂O)]₂[(CH₃S)₂C=N–C≡N]₄} (3). The compound was investigated by single-crystal X-ray diffraction analysis and infrared spectroscopy. Compound 3 crystallizes in the triclinic space group P \(\overline{1 }\) with a = 9.8208(15), b = 11.2664(17), c = 12.0446(18) Å, α = 106.236(5), β = 111.510(5), γ = 97.710(6)°, V = 1147.9(3) ų, Z = 1 and Z′ = 0.5. In the complex, two aqua-n-butyltinhydroxide dichloride moieties, [Sn(n-Bu)Cl₂(OH)(H₂O)], are bridged by the hydroxides. The hydroxide bridges bond lengths describe a static trans effect yielding a dissymmetry in Sn–O bonding. Two inner O2–H2D⋯Cl1 hydrogen bonds strengthen the dinuclear component. The dimethyl N-cyanodithioiminocarbonate molecules are linked to the dinuclear component through the hydroxide bridges and the water molecules by O1–H1⋯N2A and O2–H2C⋯N2B hydrogen bonding patterns of D type, respectively. The [(MeS)₂C=N–C≡N] molecules exhibit a positional disorder. These hydrogen bonding interactions lead to cyclic patterns generating \({R}_{1}^{1}\)(6) and \({R}_{2}^{2}\)(8) rings. Additional C–H⋯Cl and C–H⋯N hydrogen bond patterns also contribute to the crystal structure framework: they give rise to a 3D structure.

Graphical Abstract

Reacting with n-BuSnCl₃ and NaOH in an aqueous mixed solvent, dimethyl N-cyanodithioiminocarbonate, (MeS)₂C=N–C≡N forms a co-crystalline 4:1 assembly with the bimetallic organotin(IV) complex, [Sn(n-Bu)Cl₂(OH)(H₂O)]₂, whose single crystal XRD analysis exhibits a 3D hydrogen bonded structure.