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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m46.
Published online 2007 December 6. doi:  10.1107/S1600536807050283
PMCID: PMC2914930

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

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 [triangle]). For the synthetic procedures, see: Perrin & Armarego (1988 [triangle]); Piękoś & Wojnowski (1962 [triangle]); Wojnowska & Wojnowski (1974 [triangle]). For comparison of Cr—S bond lengths, see: Okura et al. (1985 [triangle]); Ito (2002 [triangle]); Ciborska et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-00m46-scheme1.jpg

Experimental

Crystal data

  • [Cr(C12H27O3SSi)2(C6H15N)2]
  • M r = 813.35
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00m46-efi1.jpg
  • 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
  • Δρmax = 0.59 e Å−3
  • Δρmin = −0.37 e Å−3

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

Supplementary Material

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

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

Refinement

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.

Figures

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.
Fig. 2.
The crystal packing of the title compound, viewed along the a-axis.

Crystal data

[Cr(C12H27O3SSi)2(C6H15N)2]F000 = 892
Mr = 813.35Dx = 1.126 Mg m3
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 mm1
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

Oxford Diffraction KM-4 CCD diffractometer3916 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

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 Å3
234 parametersΔρmin = −0.37 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

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)

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, °)

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, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O10.932.143.063 (3)174

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2337).

References

  • Ciborska, A., Baranowska, K. & Wojnowski, W. (2007). Acta Cryst. E63, m1239–m1241.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Ito, T. (2002). Acta Cryst. E58, m517–m518.
  • Okura, I., Kaji, N., Aono, S., Kita, T. & Yamada, A. (1985). Inorg. Chem.24, 453–454.
  • Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED Version 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
  • Perrin, D. D. & Armarego, W. L. F. (1988). Purification of Laboratory Chemicals. Oxford: Pergamon Press.
  • Piękoś, R. & Wojnowski, W. (1962). Z. Anorg. Allg. Chem.318, 212–216.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Wojnowska, M. & Wojnowski, W. (1974). Z. Anorg. Allg. Chem.403, 179–185.

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