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Acta Cryst. (2008). E64, m46    [ doi:10.1107/S1600536807050283 ]

Bis(di-n-propylamine-[kappa]N)bis(tri-tert-butoxysilanethiolato-[kappa]S)chromium(II)

A. Ciborska, K. Baranowska and W. Wojnowski

Abstract top

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.

Comment top

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.

Related literature top

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 top

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.

Refinement top

All H atoms were refined as riding on C atoms with methyl C—H = 0.98 Å, methylene C—H = 0.99 Å, N–H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for CH2 and amino groups and 1.5Ueq(C) for CH3 groups.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); 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).

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. C-bound H atoms have been omitted.
[Figure 2] Fig. 2. The crystal packing of the title compound, viewed along the a-axis.
Bis(di-n-propylamine-κN)bis(tri-tert- butoxysilanethiolato-κS)chromium(II) top
Crystal data top
[Cr(C12H27O3SSi)2(C6H15N)2]F000 = 892
Mr = 813.35Dx = 1.126 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 8752 reflections
a = 9.3573 (8) Åθ = 2.9–32.5º
b = 15.6328 (12) ŵ = 0.41 mm−1
c = 16.4333 (12) ÅT = 120 (2) K
β = 93.296 (7)ºPrism, blue
V = 2399.9 (3) Å30.52 × 0.27 × 0.22 mm
Z = 2
Data collection top
Oxford Diffraction KM-4 CCD
diffractometer		3916 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.056
Detector resolution: 8.1883 pixels mm-1θmax = 25.1º
T = 120(2) Kθmin = 2.8º
ω (0.75° width) scansh = −11→11
Absorption correction: nonek = −18→16
15205 measured reflectionsl = −19→14
4230 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H-atom parameters constrained
wR(F2) = 0.139  w = 1/[σ2(Fo2) + (0.0625P)2 + 4.3543P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
4230 reflectionsΔρmax = 0.59 e Å−3
234 parametersΔρmin = −0.37 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cr(C12H27O3SSi)2(C6H15N)2]V = 2399.9 (3) Å3
Mr = 813.35Z = 2
Monoclinic, P21/nMo Kα
a = 9.3573 (8) ŵ = 0.41 mm−1
b = 15.6328 (12) ÅT = 120 (2) K
c = 16.4333 (12) Å0.52 × 0.27 × 0.22 mm
β = 93.296 (7)º
Data collection top
Oxford Diffraction KM-4 CCD
diffractometer		4230 independent reflections
Absorption correction: none3916 reflections with I > 2σ(I)
15205 measured reflectionsRint = 0.056
Refinement top
R[F2 > 2σ(F2)] = 0.057234 parameters
wR(F2) = 0.139H-atom parameters constrained
S = 1.07Δρmax = 0.59 e Å−3
4230 reflectionsΔρmin = −0.37 e Å−3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8592 (3)0.30282 (17)0.12476 (17)0.0227 (6)
C20.8284 (3)0.25962 (19)0.20505 (17)0.0282 (6)
H2A0.7750.20660.19390.042*
H2B0.77150.29810.23740.042*
H2C0.91890.24640.23540.042*
C30.7208 (3)0.31714 (19)0.07329 (19)0.0300 (7)
H3A0.74280.34220.02080.045*
H3B0.65880.35620.10190.045*
H3C0.67170.26230.06410.045*
C40.9378 (3)0.38698 (18)0.14046 (17)0.0264 (6)
H4A1.02920.3760.17080.04*
H4B0.87910.42490.17230.04*
H4C0.95580.41430.08830.04*
C51.2379 (3)0.35502 (17)−0.01745 (16)0.0212 (6)
C61.1047 (3)0.35943 (19)−0.07507 (17)0.0288 (6)
H6A1.07550.3014−0.09140.043*
H6B1.12580.3926−0.12350.043*
H6C1.0270.3871−0.04740.043*
C71.2852 (4)0.44407 (18)0.00984 (18)0.0310 (7)
H7A1.20780.4720.03750.046*
H7B1.30840.478−0.03780.046*
H7C1.37010.43970.04740.046*
C81.3579 (3)0.30911 (19)−0.05804 (18)0.0292 (6)
H8A1.44010.3025−0.01880.044*
H8B1.38640.3426−0.10480.044*
H8C1.32460.2526−0.07670.044*
C91.2921 (3)0.1975 (2)0.22075 (18)0.0282 (6)
C101.3575 (4)0.2848 (2)0.2355 (2)0.0414 (8)
H10A1.38280.30950.18350.062*
H10B1.44380.27940.27180.062*
H10C1.28830.3220.26070.062*
C111.3932 (4)0.1416 (3)0.1761 (3)0.0706 (15)
H11A1.35110.08460.16820.106*
H11B1.48440.13680.20830.106*
H11C1.40980.16710.1230.106*
C121.2512 (4)0.1601 (3)0.3016 (2)0.0618 (13)
H12A1.17540.19490.32360.093*
H12B1.33510.15980.34010.093*
H12C1.21670.10140.29310.093*
C130.8096 (3)0.02560 (17)0.14156 (15)0.0203 (5)
H13A0.7703−0.0330.1360.024*
H13B0.73940.0610.16930.024*
C140.9489 (3)0.02298 (18)0.19315 (16)0.0233 (6)
H14A0.98980.08130.19730.028*
H14B1.018−0.0140.16640.028*
C150.9268 (3)−0.0110 (2)0.27823 (17)0.0311 (7)
H15A0.85850.02560.30490.047*
H15B1.0184−0.0110.31030.047*
H15C0.8893−0.06950.27440.047*
C160.6911 (3)0.06510 (17)0.01127 (16)0.0203 (5)
H16A0.6220.09870.04160.024*
H16B0.65250.00640.00420.024*
C170.7052 (3)0.10509 (19)−0.07170 (17)0.0254 (6)
H17A0.77430.0717−0.10230.03*
H17B0.74250.1641−0.0650.03*
C180.5605 (3)0.1073 (2)−0.12003 (19)0.0324 (7)
H18A0.5290.0487−0.13250.049*
H18B0.57010.1389−0.1710.049*
H18C0.48980.1358−0.08760.049*
N10.8296 (2)0.06135 (14)0.05944 (13)0.0187 (5)
H10.85810.11780.06770.022*
O10.94135 (19)0.24496 (11)0.07689 (11)0.0196 (4)
O21.2078 (2)0.31042 (11)0.05632 (11)0.0209 (4)
O31.15806 (19)0.20698 (12)0.17357 (11)0.0217 (4)
Si11.11443 (7)0.22632 (4)0.07776 (4)0.01703 (19)
S11.14306 (7)0.12779 (4)−0.00428 (4)0.02372 (19)
Cr11000.01522 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0202 (13)0.0198 (13)0.0281 (14)0.0042 (11)0.0011 (11)−0.0043 (11)
C20.0295 (15)0.0251 (15)0.0303 (15)0.0039 (12)0.0060 (12)−0.0023 (12)
C30.0247 (15)0.0274 (15)0.0374 (16)0.0083 (12)−0.0041 (12)−0.0095 (13)
C40.0271 (15)0.0223 (14)0.0299 (15)0.0012 (11)0.0033 (11)−0.0072 (11)
C50.0239 (14)0.0159 (13)0.0234 (13)−0.0055 (11)−0.0009 (10)0.0030 (10)
C60.0293 (16)0.0282 (15)0.0280 (14)0.0020 (12)−0.0056 (12)0.0024 (12)
C70.0415 (18)0.0208 (14)0.0306 (15)−0.0107 (13)0.0018 (13)0.0018 (12)
C80.0266 (15)0.0293 (15)0.0321 (15)−0.0011 (12)0.0057 (12)0.0033 (12)
C90.0190 (14)0.0318 (16)0.0327 (15)0.0001 (12)−0.0083 (11)0.0045 (12)
C100.0363 (18)0.047 (2)0.0396 (18)−0.0114 (16)−0.0104 (14)−0.0010 (15)
C110.040 (2)0.081 (3)0.087 (3)0.033 (2)−0.028 (2)−0.038 (3)
C120.040 (2)0.090 (3)0.052 (2)−0.025 (2)−0.0263 (17)0.041 (2)
C130.0223 (13)0.0174 (13)0.0218 (13)−0.0021 (10)0.0066 (10)−0.0014 (10)
C140.0236 (14)0.0256 (14)0.0212 (13)−0.0027 (11)0.0044 (10)0.0032 (11)
C150.0342 (17)0.0349 (17)0.0243 (14)−0.0046 (13)0.0021 (12)0.0041 (12)
C160.0152 (12)0.0195 (13)0.0265 (13)0.0034 (10)0.0041 (10)−0.0005 (10)
C170.0240 (14)0.0258 (14)0.0260 (14)−0.0004 (11)−0.0016 (11)0.0027 (11)
C180.0288 (16)0.0348 (17)0.0330 (15)0.0069 (13)−0.0036 (12)0.0028 (13)
N10.0197 (11)0.0154 (11)0.0211 (11)0.0002 (9)0.0034 (8)0.0000 (8)
O10.0179 (9)0.0176 (9)0.0231 (9)0.0021 (7)−0.0002 (7)−0.0033 (7)
O20.0230 (10)0.0175 (9)0.0220 (9)−0.0046 (7)0.0002 (7)0.0003 (7)
O30.0159 (9)0.0234 (10)0.0253 (10)−0.0014 (8)−0.0023 (7)0.0034 (8)
Si10.0162 (4)0.0147 (4)0.0202 (4)−0.0003 (3)0.0011 (3)−0.0008 (3)
S10.0239 (4)0.0162 (3)0.0321 (4)−0.0046 (3)0.0113 (3)−0.0061 (3)
Cr10.0152 (3)0.0136 (3)0.0171 (3)−0.0002 (2)0.0027 (2)−0.0008 (2)
Geometric parameters (Å, °) top
C1—O11.448 (3)C11—H11B0.98
C1—C31.522 (4)C11—H11C0.98
C1—C41.522 (4)C12—H12A0.98
C1—C21.524 (4)C12—H12B0.98
C2—H2A0.98C12—H12C0.98
C2—H2B0.98C13—N11.482 (3)
C2—H2C0.98C13—C141.514 (4)
C3—H3A0.98C13—H13A0.99
C3—H3B0.98C13—H13B0.99
C3—H3C0.98C14—C151.521 (4)
C4—H4A0.98C14—H14A0.99
C4—H4B0.98C14—H14B0.99
C4—H4C0.98C15—H15A0.98
C5—O21.440 (3)C15—H15B0.98
C5—C81.519 (4)C15—H15C0.98
C5—C71.521 (4)C16—N11.480 (3)
C5—C61.523 (4)C16—C171.513 (4)
C6—H6A0.98C16—H16A0.99
C6—H6B0.98C16—H16B0.99
C6—H6C0.98C17—C181.530 (4)
C7—H7A0.98C17—H17A0.99
C7—H7B0.98C17—H17B0.99
C7—H7C0.98C18—H18A0.98
C8—H8A0.98C18—H18B0.98
C8—H8B0.98C18—H18C0.98
C8—H8C0.98N1—Cr12.144 (2)
C9—O31.444 (3)N1—H10.93
C9—C111.508 (5)O1—Si11.6448 (19)
C9—C101.509 (4)O2—Si11.6283 (19)
C9—C121.520 (4)O3—Si11.6320 (19)
C10—H10A0.98Si1—S12.0744 (9)
C10—H10B0.98S1—Cr12.4080 (7)
C10—H10C0.98Cr1—N1i2.144 (2)
C11—H11A0.98Cr1—S1i2.4080 (7)
O1—C1—C3104.6 (2)H11B—C11—H11C109.5
O1—C1—C4111.4 (2)C9—C12—H12A109.5
C3—C1—C4110.8 (2)C9—C12—H12B109.5
O1—C1—C2109.0 (2)H12A—C12—H12B109.5
C3—C1—C2110.4 (2)C9—C12—H12C109.5
C4—C1—C2110.5 (2)H12A—C12—H12C109.5
C1—C2—H2A109.5H12B—C12—H12C109.5
C1—C2—H2B109.5N1—C13—C14111.8 (2)
H2A—C2—H2B109.5N1—C13—H13A109.3
C1—C2—H2C109.5C14—C13—H13A109.3
H2A—C2—H2C109.5N1—C13—H13B109.3
H2B—C2—H2C109.5C14—C13—H13B109.3
C1—C3—H3A109.5H13A—C13—H13B107.9
C1—C3—H3B109.5C13—C14—C15111.5 (2)
H3A—C3—H3B109.5C13—C14—H14A109.3
C1—C3—H3C109.5C15—C14—H14A109.3
H3A—C3—H3C109.5C13—C14—H14B109.3
H3B—C3—H3C109.5C15—C14—H14B109.3
C1—C4—H4A109.5H14A—C14—H14B108
C1—C4—H4B109.5C14—C15—H15A109.5
H4A—C4—H4B109.5C14—C15—H15B109.5
C1—C4—H4C109.5H15A—C15—H15B109.5
H4A—C4—H4C109.5C14—C15—H15C109.5
H4B—C4—H4C109.5H15A—C15—H15C109.5
O2—C5—C8109.0 (2)H15B—C15—H15C109.5
O2—C5—C7105.2 (2)N1—C16—C17112.3 (2)
C8—C5—C7110.6 (2)N1—C16—H16A109.1
O2—C5—C6110.6 (2)C17—C16—H16A109.1
C8—C5—C6110.3 (2)N1—C16—H16B109.1
C7—C5—C6110.9 (2)C17—C16—H16B109.1
C5—C6—H6A109.5H16A—C16—H16B107.9
C5—C6—H6B109.5C16—C17—C18110.9 (2)
H6A—C6—H6B109.5C16—C17—H17A109.5
C5—C6—H6C109.5C18—C17—H17A109.5
H6A—C6—H6C109.5C16—C17—H17B109.5
H6B—C6—H6C109.5C18—C17—H17B109.5
C5—C7—H7A109.5H17A—C17—H17B108
C5—C7—H7B109.5C17—C18—H18A109.5
H7A—C7—H7B109.5C17—C18—H18B109.5
C5—C7—H7C109.5H18A—C18—H18B109.5
H7A—C7—H7C109.5C17—C18—H18C109.5
H7B—C7—H7C109.5H18A—C18—H18C109.5
C5—C8—H8A109.5H18B—C18—H18C109.5
C5—C8—H8B109.5C16—N1—C13110.5 (2)
H8A—C8—H8B109.5C16—N1—Cr1115.17 (15)
C5—C8—H8C109.5C13—N1—Cr1112.46 (16)
H8A—C8—H8C109.5C16—N1—H1106
H8B—C8—H8C109.5C13—N1—H1106
O3—C9—C11110.4 (3)Cr1—N1—H1106
O3—C9—C10109.0 (2)C1—O1—Si1131.23 (16)
C11—C9—C10110.0 (3)C5—O2—Si1134.93 (16)
O3—C9—C12104.7 (2)C9—O3—Si1134.30 (17)
C11—C9—C12113.5 (4)O2—Si1—O3104.52 (10)
C10—C9—C12109.1 (3)O2—Si1—O1113.29 (10)
C9—C10—H10A109.5O3—Si1—O1103.46 (9)
C9—C10—H10B109.5O2—Si1—S1111.60 (7)
H10A—C10—H10B109.5O3—Si1—S1117.06 (8)
C9—C10—H10C109.5O1—Si1—S1106.85 (7)
H10A—C10—H10C109.5Si1—S1—Cr1120.28 (3)
H10B—C10—H10C109.5N1i—Cr1—N1180.00 (15)
C9—C11—H11A109.5N1i—Cr1—S185.90 (6)
C9—C11—H11B109.5N1—Cr1—S194.10 (6)
H11A—C11—H11B109.5N1i—Cr1—S1i94.10 (6)
C9—C11—H11C109.5N1—Cr1—S1i85.90 (6)
H11A—C11—H11C109.5S1—Cr1—S1i180.000 (17)
Symmetry codes: (i) −x+2, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.932.143.063 (3)174
Acknowledgements top

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

references
References top

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