organic compounds
Tetrakis(2,3,5,5-tetramethylhexen-2-yl)silane
aInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
*Correspondence e-mail: bolte@chemie.uni-frankfurt.de
In the title compound, C40H76Si, the Si atom is located on a special position of -4. Thus, there is just a quarter of a molecule in the The C=C double bonds exhibit a trans configuration. The Si atom and the tert-butyl group are located on the same side of the plane formed by the C=C double bond and its four substituents. The crystal packing shows no short contacts between the molecules and despite the low crystal density (0.980 Mg m−3), there are no significant voids in the structure.
CCDC reference: 988679
Related literature
For information on the chemical background, see: Meyer-Wegner et al. (2011, 2014).
Experimental
Crystal data
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Data collection: X-AREA (Stoe & Cie, 2001); cell X-RED32 (Stoe & Cie, 2001); data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 988679
10.1107/S1600536814004322/zs2287sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814004322/zs2287Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814004322/zs2287Isup3.cml
To Si2Cl6 (0.3 ml, 0.47 g, 1.74 mmol) in DMB (1.2 ml, 0.86 g, 10 mmol) a catalytic amount of NMe2Et (0.012 g, 0.2 mmol) was added. Subsequent treatment of this mixture with a solution of tBuLi (16 mmol) in 10 ml of pentane yielded a colorless precipitate. After filtration all volatiles were removed in vacuo. The obtained residue was dissolved in benzene. This solution was stored at ambient temperature for a period of two days yielding single crystals of the title compound.
H atoms were geometrically positioned and refined using a riding model with fixed individual displacement parameters [U(H) = 1.2 Ueq(C) or U(H) = 1.5 Ueq(Cmethyl)] and with Cmethyl—H = 0.98 Å and Cmethylene—H = 0.99 Å. The methyl groups attached to the double bond were allowed to rotate but not to tip.
Data collection: X-AREA (Stoe & Cie, 2001); cell
X-AREA (Stoe & Cie, 2001); data reduction: X-RED32 (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).C40H76Si | Dx = 0.980 Mg m−3 |
Mr = 585.10 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 4399 reflections |
Hall symbol: -I 4ad | θ = 3.7–25.9° |
a = 12.5780 (11) Å | µ = 0.08 mm−1 |
c = 25.053 (3) Å | T = 173 K |
V = 3963.5 (7) Å3 | Block, colourless |
Z = 4 | 0.32 × 0.28 × 0.16 mm |
F(000) = 1320 |
Stoe IPDS-II two-circle diffractometer | 1742 independent reflections |
Radiation source: fine-focus sealed tube | 1301 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ω scans | θmax = 25.0°, θmin = 3.6° |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | h = −8→14 |
Tmin = 0.963, Tmax = 0.988 | k = −14→14 |
5117 measured reflections | l = −25→29 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0654P)2 + 0.753P] where P = (Fo2 + 2Fc2)/3 |
1742 reflections | (Δ/σ)max = 0.001 |
95 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C40H76Si | Z = 4 |
Mr = 585.10 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.08 mm−1 |
a = 12.5780 (11) Å | T = 173 K |
c = 25.053 (3) Å | 0.32 × 0.28 × 0.16 mm |
V = 3963.5 (7) Å3 |
Stoe IPDS-II two-circle diffractometer | 1742 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2009; Blessing, 1995) | 1301 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.988 | Rint = 0.045 |
5117 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.25 e Å−3 |
1742 reflections | Δρmin = −0.17 e Å−3 |
95 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Si1 | 0.5000 | 0.7500 | 0.1250 | 0.0457 (3) | |
C1 | 0.52419 (16) | 0.62670 (16) | 0.08358 (7) | 0.0522 (5) | |
H1A | 0.5766 | 0.6452 | 0.0556 | 0.063* | |
H1B | 0.5581 | 0.5731 | 0.1070 | 0.063* | |
C2 | 0.43057 (17) | 0.57385 (17) | 0.05637 (8) | 0.0564 (5) | |
C3 | 0.38412 (17) | 0.48729 (17) | 0.07519 (8) | 0.0595 (6) | |
C4 | 0.29391 (17) | 0.42817 (18) | 0.04703 (8) | 0.0588 (5) | |
H4A | 0.3062 | 0.3510 | 0.0518 | 0.071* | |
H4B | 0.2996 | 0.4432 | 0.0084 | 0.071* | |
C5 | 0.17836 (18) | 0.45239 (19) | 0.06442 (8) | 0.0628 (6) | |
C21 | 0.3961 (2) | 0.62822 (18) | 0.00476 (8) | 0.0652 (6) | |
H21A | 0.4590 | 0.6459 | −0.0165 | 0.098* | |
H21B | 0.3570 | 0.6935 | 0.0133 | 0.098* | |
H21C | 0.3500 | 0.5802 | −0.0156 | 0.098* | |
C31 | 0.4258 (2) | 0.43428 (18) | 0.12553 (9) | 0.0695 (6) | |
H31A | 0.3791 | 0.3750 | 0.1353 | 0.104* | |
H31B | 0.4274 | 0.4862 | 0.1547 | 0.104* | |
H31C | 0.4979 | 0.4075 | 0.1191 | 0.104* | |
C51 | 0.1061 (2) | 0.3674 (2) | 0.03927 (11) | 0.0833 (8) | |
H51A | 0.1139 | 0.3691 | 0.0004 | 0.125* | |
H51B | 0.0320 | 0.3818 | 0.0488 | 0.125* | |
H51C | 0.1266 | 0.2970 | 0.0526 | 0.125* | |
C52 | 0.1662 (2) | 0.4487 (3) | 0.12469 (10) | 0.0881 (8) | |
H52A | 0.0924 | 0.4648 | 0.1343 | 0.132* | |
H52B | 0.2136 | 0.5013 | 0.1410 | 0.132* | |
H52C | 0.1848 | 0.3775 | 0.1376 | 0.132* | |
C53 | 0.1450 (2) | 0.5620 (2) | 0.04480 (11) | 0.0825 (7) | |
H53A | 0.1528 | 0.5654 | 0.0059 | 0.124* | |
H53B | 0.1902 | 0.6162 | 0.0614 | 0.124* | |
H53C | 0.0707 | 0.5749 | 0.0545 | 0.124* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.0476 (4) | 0.0476 (4) | 0.0418 (5) | 0.000 | 0.000 | 0.000 |
C1 | 0.0517 (11) | 0.0526 (11) | 0.0524 (10) | 0.0025 (9) | −0.0010 (8) | −0.0013 (8) |
C2 | 0.0612 (12) | 0.0571 (12) | 0.0508 (11) | 0.0073 (10) | 0.0031 (9) | −0.0075 (9) |
C3 | 0.0636 (13) | 0.0606 (13) | 0.0543 (11) | 0.0055 (10) | −0.0024 (9) | −0.0053 (9) |
C4 | 0.0644 (13) | 0.0599 (12) | 0.0520 (10) | −0.0025 (10) | −0.0035 (9) | −0.0116 (9) |
C5 | 0.0613 (13) | 0.0744 (15) | 0.0528 (11) | −0.0074 (11) | −0.0035 (10) | −0.0120 (10) |
C21 | 0.0841 (16) | 0.0659 (14) | 0.0457 (10) | 0.0062 (12) | −0.0018 (10) | 0.0016 (9) |
C31 | 0.0832 (15) | 0.0641 (13) | 0.0613 (12) | −0.0020 (12) | −0.0165 (11) | 0.0081 (11) |
C51 | 0.0674 (15) | 0.0991 (19) | 0.0833 (16) | −0.0160 (14) | −0.0095 (12) | −0.0227 (14) |
C52 | 0.0807 (17) | 0.122 (2) | 0.0618 (13) | −0.0206 (16) | 0.0092 (12) | −0.0160 (14) |
C53 | 0.0744 (16) | 0.0910 (19) | 0.0821 (16) | 0.0154 (14) | −0.0009 (12) | −0.0141 (13) |
Si1—C1i | 1.8906 (19) | C5—C51 | 1.538 (3) |
Si1—C1ii | 1.8906 (19) | C21—H21A | 0.9800 |
Si1—C1 | 1.8907 (19) | C21—H21B | 0.9800 |
Si1—C1iii | 1.8907 (19) | C21—H21C | 0.9800 |
C1—C2 | 1.514 (3) | C31—H31A | 0.9800 |
C1—H1A | 0.9900 | C31—H31B | 0.9800 |
C1—H1B | 0.9900 | C31—H31C | 0.9800 |
C2—C3 | 1.323 (3) | C51—H51A | 0.9800 |
C2—C21 | 1.526 (3) | C51—H51B | 0.9800 |
C3—C31 | 1.520 (3) | C51—H51C | 0.9800 |
C3—C4 | 1.529 (3) | C52—H52A | 0.9800 |
C4—C5 | 1.548 (3) | C52—H52B | 0.9800 |
C4—H4A | 0.9900 | C52—H52C | 0.9800 |
C4—H4B | 0.9900 | C53—H53A | 0.9800 |
C5—C52 | 1.518 (3) | C53—H53B | 0.9800 |
C5—C53 | 1.522 (4) | C53—H53C | 0.9800 |
C1i—Si1—C1ii | 107.53 (6) | C2—C21—H21A | 109.5 |
C1i—Si1—C1 | 113.43 (12) | C2—C21—H21B | 109.5 |
C1ii—Si1—C1 | 107.53 (6) | H21A—C21—H21B | 109.5 |
C1i—Si1—C1iii | 107.53 (6) | C2—C21—H21C | 109.5 |
C1ii—Si1—C1iii | 113.43 (12) | H21A—C21—H21C | 109.5 |
C1—Si1—C1iii | 107.53 (6) | H21B—C21—H21C | 109.5 |
C2—C1—Si1 | 118.82 (14) | C3—C31—H31A | 109.5 |
C2—C1—H1A | 107.6 | C3—C31—H31B | 109.5 |
Si1—C1—H1A | 107.6 | H31A—C31—H31B | 109.5 |
C2—C1—H1B | 107.6 | C3—C31—H31C | 109.5 |
Si1—C1—H1B | 107.6 | H31A—C31—H31C | 109.5 |
H1A—C1—H1B | 107.0 | H31B—C31—H31C | 109.5 |
C3—C2—C1 | 122.99 (19) | C5—C51—H51A | 109.5 |
C3—C2—C21 | 123.0 (2) | C5—C51—H51B | 109.5 |
C1—C2—C21 | 113.95 (18) | H51A—C51—H51B | 109.5 |
C2—C3—C31 | 120.3 (2) | C5—C51—H51C | 109.5 |
C2—C3—C4 | 124.31 (19) | H51A—C51—H51C | 109.5 |
C31—C3—C4 | 115.20 (19) | H51B—C51—H51C | 109.5 |
C3—C4—C5 | 118.12 (16) | C5—C52—H52A | 109.5 |
C3—C4—H4A | 107.8 | C5—C52—H52B | 109.5 |
C5—C4—H4A | 107.8 | H52A—C52—H52B | 109.5 |
C3—C4—H4B | 107.8 | C5—C52—H52C | 109.5 |
C5—C4—H4B | 107.8 | H52A—C52—H52C | 109.5 |
H4A—C4—H4B | 107.1 | H52B—C52—H52C | 109.5 |
C52—C5—C53 | 108.7 (2) | C5—C53—H53A | 109.5 |
C52—C5—C51 | 109.1 (2) | C5—C53—H53B | 109.5 |
C53—C5—C51 | 109.6 (2) | H53A—C53—H53B | 109.5 |
C52—C5—C4 | 111.62 (19) | C5—C53—H53C | 109.5 |
C53—C5—C4 | 110.24 (19) | H53A—C53—H53C | 109.5 |
C51—C5—C4 | 107.60 (18) | H53B—C53—H53C | 109.5 |
C1i—Si1—C1—C2 | −75.32 (15) | C1—C2—C3—C4 | −176.17 (18) |
C1ii—Si1—C1—C2 | 165.92 (18) | C21—C2—C3—C4 | 2.6 (3) |
C1iii—Si1—C1—C2 | 43.44 (12) | C2—C3—C4—C5 | −96.9 (3) |
Si1—C1—C2—C3 | −101.5 (2) | C31—C3—C4—C5 | 88.3 (2) |
Si1—C1—C2—C21 | 79.6 (2) | C3—C4—C5—C52 | −48.5 (3) |
C1—C2—C3—C31 | −1.6 (3) | C3—C4—C5—C53 | 72.4 (2) |
C21—C2—C3—C31 | 177.2 (2) | C3—C4—C5—C51 | −168.2 (2) |
Symmetry codes: (i) −x+1, −y+3/2, z; (ii) −y+5/4, x+1/4, −z+1/4; (iii) y−1/4, −x+5/4, −z+1/4. |
Experimental details
Crystal data | |
Chemical formula | C40H76Si |
Mr | 585.10 |
Crystal system, space group | Tetragonal, I41/a |
Temperature (K) | 173 |
a, c (Å) | 12.5780 (11), 25.053 (3) |
V (Å3) | 3963.5 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.32 × 0.28 × 0.16 |
Data collection | |
Diffractometer | Stoe IPDS-II two-circle diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 2009; Blessing, 1995) |
Tmin, Tmax | 0.963, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5117, 1742, 1301 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.136, 1.08 |
No. of reflections | 1742 |
No. of parameters | 95 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.17 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-RED32 (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
Acknowledgements
This work was supported by the Beilstein Institute as part of the NanoBiC research cooperative (project eNet).
References
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Very recently, we have investigated the reaction of Si2Cl6 with NR3 (R = Me, Et) and we have been able to show that amine-complexed dichlorosilylenes represent the key intermediates in this disproportionation reaction (Meyer-Wegner et al., 2011). In the course of these studies we isolated along with SiCl4 the [4 + 1] cycloadduct of dichlorosilylene SiCl2 with 2,3-dimethyl-1,3-butadiene (DMB) in good yield upon treatment of Si2Cl6 with catalytic amounts of NMe3 or NMe2Et in neat DMB (Meyer-Wegner et al., 2014). In this study we report on the reaction of Si2Cl6 with catalytic amounts of NMe2Et in the presence of DMB. Subsequent treatment of this reaction mixture with tBuLi yielded the title compound (I) which could be isolated (Fig. 1).
In the title compound (Fig. 2), the Si centre is located on a special position of site symmtry 4. Thus, there is just a quarter of a molecule in the asymmetric unit. The C=C double bonds show a trans configuration. It is interesting to note, that the Si centre and the t-butyl group are located on the same side of the plane formed by the C=C double bond and its four substituents. The crystal packing (Fig. 3) shows no short contacts between the molecules and despite the fact that the crystal density is rather low [0.980 g/cm3], there are no significant voids in the structure.