Bis(di-n-propyl­amine-κN)bis­(tri-tert-butoxy­silanethiol­ato-κS)chromium(II)

Anna Ciborska; Katarzyna Baranowska; Wiesław Wojnowski

doi:10.1107/S1600536807050283

. 2007 Dec 6;64(Pt 1):m46. doi: 10.1107/S1600536807050283

Bis(di-n-propylamine-κN)bis(tri-tert-butoxysilanethiolato-κS)chromium(II)

Anna Ciborska ^a, Katarzyna Baranowska ^a,^*, Wiesław Wojnowski ^a

PMCID: PMC2914930 PMID: 21200617

Abstract

The title compound, [Cr(C₁₂H₂₇O₃SSi)₂(C₆H₁₅N)₂], is a molecular chromium(II) thiolate that is coordinated by two dipropylamine ligands in a square-planar environment. The molecule lies on an inversion site.

Related literature

For (tetrahydrofuran)bis(tri-tert-butoxysilanethiolato)chromium(II), see: Ciborska et al. (2007 ▶). For the synthetic procedures, see: Perrin & Armarego (1988 ▶); Piękoś & Wojnowski (1962 ▶); Wojnowska & Wojnowski (1974 ▶). For comparison of Cr—S bond lengths, see: Okura et al. (1985 ▶); Ito (2002 ▶); Ciborska et al. (2007 ▶).

Experimental

Crystal data

[Cr(C₁₂H₂₇O₃SSi)₂(C₆H₁₅N)₂]
M _r = 813.35
Monoclinic,
a = 9.3573 (8) Å
b = 15.6328 (12) Å
c = 16.4333 (12) Å
β = 93.296 (7)°
V = 2399.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 120 (2) K
0.52 × 0.27 × 0.22 mm

Data collection

Oxford Diffraction KM-4 CCDdiffractometer
Absorption correction: none
15205 measured reflections
4230 independent reflections
3916 reflections with I > 2σ(I)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.139
S = 1.07
4230 reflections
234 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2005 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807050283/ng2337sup1.cif

e-64-00m46-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807050283/ng2337Isup2.hkl

e-64-00m46-Isup2.hkl^{(203.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was carried out with financial support from the Polish State Committee (grant No. 3 T09A 12028).

supplementary crystallographic information

Comment

We present here the crystal structure of the title compound (I), which is the first example of square-planar chromium(II) complex (Fig.1). It was obtained in the reaction of anhydrous Cr(II) chloride with sodium tri-tert-butoxysilanethiolate and dipropylamine. The Cr(II) ion is coordinated by two S atoms of the tri-tert-butoxysilanethiolate ligand, and two N atoms of the amine. The central Cr atom sits on an inversion centre at Wyckoff position a (1/2, 1/2, 1/2). The amine ligand forms intramolecular hydrogen bonds of the N–H···O type. The trans angles of the square base are then described by S–Cr–S and N–Cr–N. The Cr–S bond lengths are typical of Cr-thiolate complexes (Okura et al., 1985; Ito 2002; Ciborska et al., 2007). Selected data on important bond lengths and angles are compared in Table.1. Molecules of (I) pack in the crystal structure as discrete entities with no interactions other than von der Waals. Compound (I) is one of the few structurally defined planar, four-coordinate Cr(II) thiolate complexes.

Experimental

All manipulations were conducted under an atmosphere of nitrogen using standard Schlenk techniques. Solvents and the amine were purified and dried by standard methods (Perrin & Armarego, 1988). The substrate (^tBuO)₃SiSNa was prepared according to literature methods (Piękoś & Wojnowski, 1962; Wojnowska & Wojnowski, 1974). The compound was synthesized by addition of the CrCl₂ solution (0.26 g, 2.13 mmol) in tetrahydrofuran (20 ml) to (^tBuO)₃SiSNa solution (1.24 g, 4.12 mmol) in toluene (15 ml) and stirring for 1 h. Then, to the pale-green solution dipropylamine (0.55 ml, 0.4 g, 4 mmol) was added and stirred for next 12 h. After that the mixture was filtered. The dark blue filtrate was concentrated and cooled (250 K) afford blue crystals.