1,4-Bis(dimethyl­silyl)-2,5-diphenyl­benzene

Fang, L.; Wang, R.; Chen, L.-M.; Xu, C.-H.; Li, S.-H.

doi:10.1107/S1600536810010913

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o970

doi:10.1107/S1600536810010913

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1,4-Bis(dimethylsilyl)-2,5-diphenylbenzene

Lei Fang,^a,^b Rui Wang,^a,^b Li-Min Chen,^a Cai-Hong Xu ^a ^* and Shu-Hong Li ^c

^aBeijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China, ^bGraduate School of the Chinese Academy of Sciences, Beijing 100049, People's Republic of China, and ^cSchool of Chemical and Environmental Engineering, Beijing Technology and Business University, Beijing 100037, People's Republic of China
^*Correspondence e-mail: caihong@iccas.ac.cn

(Received 23 February 2010; accepted 23 March 2010; online 27 March 2010)

The molecule of the title compound, C₂₂H₂₆Si₂, is centrosymmetric. The dihedral angle between the central benzene ring and its phenyl substituents is 67.7 (2)°. The crystal packing is stabilized by van der Waals forces.

Related literature

For investigations on the effect of silyl substituents on the photophysics of p-terphenyls, see: Feng et al. (2007 ).

Experimental

Crystal data

C₂₂H₂₆Si₂
M_r = 346.61
Monoclinic, C 2/c
a = 14.8966 (3) Å
b = 6.0132 (1) Å
c = 26.1211 (6) Å
β = 123.166 (1)°
V = 1958.64 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 173 K
0.56 × 0.39 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.905, T_max = 0.980
4032 measured reflections
2220 independent reflections
2009 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.118
S = 1.22
2220 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2001 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810010913/gk2260sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010913/gk2260Isup2.hkl

checkCIF report

Comment top

As part of our ongoing investigation on the effect of silyl substituents on the photophysics of p-terphenyls, we present the title compound bearing silyl substituents at the central phenyl ring (2,5-positions). Though analogues of the title compound were reported elsewhere (Feng et al., 2007), their structures were not fully studied. The molecular structure of the title compound is shown in Fig.1. It is centrosymmetric, the centroid of the central benzene ring is located on an inversion center at 0,1,0. The dihedral angle between the benzene ring and phenyl substituents is 67.7 (2)°. The crystal packing is mainly stabilized by van der Waals forces.

Related literature top

For our ongoing investigation on the effect of silyl substituents on the photophysics of p-terphenyls, see: Feng et al. (2007).

Experimental top

A solution of 2,5-dibromo-1,4-diphenylbenzene (120 mg, 0.31 mmol) in anhydrous THF (10 ml) was added dropwise to a hexane solution of n-BuLi (2.5 M, 0.44 ml, 1.08 mmol) dropwise at -78 °C. The reaction mixture was stirred for 1 h and dimethylchlorosilane (118 mg, 1.24 mmol) was added via syringe at the same temperature and the mixture was allowed to warm to room temperature and stirred overnight. After being quenched with saturated NaHCO₃ solution, the mixture was extracted with Et₂O. The organic layer was washed with brine, dried over anhydrous MgSO₄, filtered, and concentrated under reduced pressure. The mixture was passed through a silica gel column with hexane as an eluent, followed by further purification by recrystallization from ethanol to give 98 mg of the white product in 91% yield.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme. The unlabelled atoms can be generated by the symmetry operation -x, -y+2, -z.

1,4-Bis(dimethylsilyl)-2,5-diphenylbenzene top

Crystal data top

C₂₂H₂₆Si₂	F(000) = 744
M_r = 346.61	D_x = 1.175 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4032 reflections
a = 14.8966 (3) Å	θ = 2.7–27.5°
b = 6.0132 (1) Å	µ = 0.18 mm⁻¹
c = 26.1211 (6) Å	T = 173 K
β = 123.166 (1)°	Plate, colorless
V = 1958.64 (7) Å³	0.56 × 0.39 × 0.11 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	2220 independent reflections
Radiation source: rotating anode	2009 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans at fixed χ = 45°	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −19→19
T_min = 0.905, T_max = 0.980	k = −7→7
4032 measured reflections	l = −33→33

Refinement top

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.22	w = 1/[σ²(F_o²) + (0.0432P)² + 2.0232P] where P = (F_o² + 2F_c²)/3
2220 reflections	(Δ/σ)_max < 0.001
111 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₂H₂₆Si₂	V = 1958.64 (7) Å³
M_r = 346.61	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.8966 (3) Å	µ = 0.18 mm⁻¹
b = 6.0132 (1) Å	T = 173 K
c = 26.1211 (6) Å	0.56 × 0.39 × 0.11 mm
β = 123.166 (1)°

Data collection top

Rigaku R-AXIS RAPID IP area-detector diffractometer	2220 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2009 reflections with I > 2σ(I)
T_min = 0.905, T_max = 0.980	R_int = 0.028
4032 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.22	Δρ_max = 0.40 e Å⁻³
2220 reflections	Δρ_min = −0.22 e Å⁻³
111 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2σ(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

	x	y	z	U_iso*/U_eq
Si1	−0.03046 (4)	0.64331 (9)	0.08538 (2)	0.02208 (16)
H1	0.0590	0.5194	0.1223	0.026*
C1	−0.00698 (14)	0.8349 (3)	0.03690 (8)	0.0207 (4)
C2	−0.09110 (15)	0.8753 (3)	−0.02358 (8)	0.0220 (4)
H2	−0.1545	0.7887	−0.0403	0.026*
C3	0.08631 (14)	0.9637 (3)	0.06040 (8)	0.0202 (4)
C4	0.18299 (14)	0.9316 (3)	0.12353 (8)	0.0208 (4)
C5	0.21644 (16)	1.0962 (3)	0.16753 (9)	0.0276 (4)
H5	0.1762	1.2298	0.1578	0.033*
C6	0.30788 (17)	1.0685 (4)	0.22563 (9)	0.0314 (5)
H6	0.3292	1.1819	0.2555	0.038*
C7	0.36813 (15)	0.8762 (4)	0.24023 (8)	0.0285 (4)
H7	0.4314	0.8582	0.2798	0.034*
C8	0.33562 (16)	0.7103 (4)	0.19677 (9)	0.0310 (5)
H8	0.3763	0.5773	0.2067	0.037*
C9	0.24395 (16)	0.7377 (3)	0.13896 (8)	0.0261 (4)
H9	0.2223	0.6231	0.1094	0.031*
C10	−0.0605 (2)	0.8174 (4)	0.13337 (10)	0.0375 (5)
H10A	−0.1249	0.9065	0.1068	0.056*
H10B	0.0002	0.9164	0.1592	0.056*
H10C	−0.0726	0.7209	0.1593	0.056*
C11	−0.14236 (19)	0.4490 (4)	0.03752 (10)	0.0377 (5)
H11A	−0.1565	0.3595	0.0637	0.057*
H11B	−0.1230	0.3509	0.0151	0.057*
H11C	−0.2068	0.5338	0.0084	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0233 (3)	0.0233 (3)	0.0197 (3)	0.0028 (2)	0.0118 (2)	0.0051 (2)
C1	0.0221 (9)	0.0217 (9)	0.0194 (8)	0.0021 (7)	0.0120 (7)	0.0018 (7)
C2	0.0213 (9)	0.0241 (9)	0.0199 (8)	−0.0012 (7)	0.0110 (7)	−0.0005 (7)
C3	0.0208 (9)	0.0228 (9)	0.0162 (8)	0.0024 (7)	0.0096 (7)	0.0009 (7)
C4	0.0190 (8)	0.0251 (9)	0.0170 (8)	0.0005 (7)	0.0090 (7)	0.0016 (7)
C5	0.0268 (10)	0.0246 (10)	0.0242 (9)	0.0041 (8)	0.0094 (8)	−0.0009 (8)
C6	0.0315 (11)	0.0333 (11)	0.0202 (9)	0.0000 (9)	0.0082 (8)	−0.0051 (8)
C7	0.0202 (9)	0.0406 (12)	0.0174 (8)	0.0028 (8)	0.0056 (7)	0.0015 (8)
C8	0.0259 (10)	0.0365 (11)	0.0242 (9)	0.0115 (9)	0.0096 (8)	0.0038 (9)
C9	0.0276 (10)	0.0274 (10)	0.0199 (9)	0.0051 (8)	0.0108 (8)	−0.0020 (8)
C10	0.0482 (13)	0.0381 (12)	0.0341 (11)	0.0045 (10)	0.0275 (11)	0.0008 (10)
C11	0.0454 (13)	0.0356 (12)	0.0367 (12)	−0.0103 (10)	0.0254 (11)	−0.0035 (10)

Geometric parameters (Å, º) top

Si1—C11	1.851 (2)	C6—C7	1.383 (3)
Si1—C10	1.866 (2)	C6—H6	0.9500
Si1—C1	1.8812 (19)	C7—C8	1.385 (3)
Si1—H1	1.3623	C7—H7	0.9500
C1—C2	1.400 (2)	C8—C9	1.384 (3)
C1—C3	1.405 (3)	C8—H8	0.9500
C2—C3ⁱ	1.394 (3)	C9—H9	0.9500
C2—H2	0.9500	C10—H10A	0.9800
C3—C2ⁱ	1.394 (3)	C10—H10B	0.9800
C3—C4	1.494 (2)	C10—H10C	0.9800
C4—C5	1.386 (3)	C11—H11A	0.9800
C4—C9	1.395 (3)	C11—H11B	0.9800
C5—C6	1.387 (3)	C11—H11C	0.9800
C5—H5	0.9500

C11—Si1—C10	110.47 (11)	C5—C6—H6	119.9
C11—Si1—C1	111.24 (9)	C6—C7—C8	119.55 (17)
C10—Si1—C1	108.04 (10)	C6—C7—H7	120.2
C11—Si1—H1	107.7	C8—C7—H7	120.2
C10—Si1—H1	109.4	C9—C8—C7	120.16 (19)
C1—Si1—H1	110.0	C9—C8—H8	119.9
C2—C1—C3	117.29 (16)	C7—C8—H8	119.9
C2—C1—Si1	118.99 (14)	C8—C9—C4	120.83 (18)
C3—C1—Si1	123.17 (13)	C8—C9—H9	119.6
C3ⁱ—C2—C1	123.17 (17)	C4—C9—H9	119.6
C3ⁱ—C2—H2	118.4	Si1—C10—H10A	109.5
C1—C2—H2	118.4	Si1—C10—H10B	109.5
C2ⁱ—C3—C1	119.54 (16)	H10A—C10—H10B	109.5
C2ⁱ—C3—C4	117.97 (16)	Si1—C10—H10C	109.5
C1—C3—C4	122.47 (16)	H10A—C10—H10C	109.5
C5—C4—C9	118.37 (16)	H10B—C10—H10C	109.5
C5—C4—C3	121.00 (17)	Si1—C11—H11A	109.5
C9—C4—C3	120.59 (17)	Si1—C11—H11B	109.5
C4—C5—C6	120.91 (18)	H11A—C11—H11B	109.5
C4—C5—H5	119.5	Si1—C11—H11C	109.5
C6—C5—H5	119.5	H11A—C11—H11C	109.5
C7—C6—C5	120.18 (19)	H11B—C11—H11C	109.5
C7—C6—H6	119.9

C11—Si1—C1—C2	23.44 (19)	C1—C3—C4—C5	−114.5 (2)
C10—Si1—C1—C2	−97.97 (17)	C2ⁱ—C3—C4—C9	−110.8 (2)
C11—Si1—C1—C3	−165.30 (16)	C1—C3—C4—C9	67.7 (2)
C10—Si1—C1—C3	73.29 (18)	C9—C4—C5—C6	−0.4 (3)
C3—C1—C2—C3ⁱ	−0.6 (3)	C3—C4—C5—C6	−178.25 (18)
Si1—C1—C2—C3ⁱ	171.16 (14)	C4—C5—C6—C7	0.9 (3)
C2—C1—C3—C2ⁱ	0.6 (3)	C5—C6—C7—C8	−1.0 (3)
Si1—C1—C3—C2ⁱ	−170.81 (14)	C6—C7—C8—C9	0.6 (3)
C2—C1—C3—C4	−177.92 (17)	C7—C8—C9—C4	0.0 (3)
Si1—C1—C3—C4	10.7 (3)	C5—C4—C9—C8	0.0 (3)
C2ⁱ—C3—C4—C5	67.0 (2)	C3—C4—C9—C8	177.82 (19)

Symmetry code: (i) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₆Si₂
M_r	346.61
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	14.8966 (3), 6.0132 (1), 26.1211 (6)
β (°)	123.166 (1)
V (Å³)	1958.64 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.56 × 0.39 × 0.11

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP area-detector diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.905, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	4032, 2220, 2009
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.118, 1.22
No. of reflections	2220
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.22

Computer programs: RAPID-AUTO (Rigaku, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the National Science Foundation of China (NSFC, Nos. 50673094 and 20774102).

References

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