1,4-Bis[4-(dimethyl­silyl)phen­yl]benzene

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

doi:10.1107/S1600536810010883

organic compounds

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Volume 66| Part 4| April 2010| Page o971

doi:10.1107/S1600536810010883

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1,4-Bis[4-(dimethylsilyl)phenyl]benzene

Lei Fang,^a,^b Rui Wang,^a,^b Li-Min Chen,^b Cai-Hong Xu ^b ^* 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 24 February 2010; accepted 23 March 2010; online 27 March 2010)

The complete molecule of the title compound, C₂₂H₂₆Si₂, is generated by a crystallographic centre of symmetry. The central benzene ring makes a dihedral angle of 26.7 (4)° with the 4-(dimethylsilyl)phenyl ring. There are weak C—H⋯π interactions in the crystal structure.

Related literature

For applications of p-terphenyl derivatives as laser dyes, see: Craig et al. (1992 ), as light-emitting materials, see: Spiliopoulos et al. (2002 ) and as liquid crystalline materials, see: Yam et al. (1993 ). For a description of the Cambridge Structural Database, see: Allen (2002 ); Although p-terphenyls containing silyl groups have been reported (Feng et al., 2007 ), their crystal structures have not yet been determined.

Experimental

Crystal data

C₂₂H₂₆Si₂
M_r = 346.61
Monoclinic, P 2₁ /c
a = 15.143 (3) Å
b = 7.7263 (15) Å
c = 9.1285 (18) Å
β = 107.52 (3)°
V = 1018.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 173 K
0.20 × 0.18 × 0.08 mm

Data collection

Rigaku Saturn724+ CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.966, T_max = 0.986
7661 measured reflections
2218 independent reflections
1937 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.071
wR(F²) = 0.133
S = 1.21
2218 reflections
115 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8b⋯Cg1ⁱ	0.98	2.86	3.826 (3)	171
C10—H10a⋯Cg1ⁱⁱ	0.95	2.98	3.788 (3)	143
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810010883/fb2186sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010883/fb2186Isup2.hkl

checkCIF report

Comment top

p-Terphenyl derivatives have attracted considerable attention due to their extensive applications. Among others, they may be used as laser dyes (Craig et al., 1992), light-emitting materials (Spiliopoulos et al., 2002), liquid crystalline materials (Yam et al., 1993). Although p-terphenyls containing silyl groups have been reported (Feng et al., 2007), their crystal structures have not been given yet.

The title molecules are situated on the crystallographic centres of symmetry (Fig. 1). Two dimethylsilylphenyl-rings are linked to the central benzene ring in its 1,4 (para) positions. The rings are not coplanar; the dihedral angle between the dimethylsilylphenyl-ring and the central benzene ring equals to 26.7 (4)°. There are C-H···π-electron ring interactions in the structure (Tab. 1).

The distance Si1-H1 (1.39 (3)Å) is in a fair accordance to the structures with the R-factor < 0.06 that have been retrieved from the Cambridge Crystallographic Database (version 5.31 from December 2009 with updates up to February 2010). (Allen, 2002). The average retrieved distance is 1.419 (14) Å for 21 observations. [The searched structures contained Si-fragment as it is in the title structure: 2 C atoms in sp³ state, 1 in sp² state, 1 H. The structures with extensively deviated distances (ROLDIF, ROLDIF01, POZNEX, CODVOH, YOYBOD) have been suppressed.]

Related literature top

For applications of p-terphenyl derivatives as laser dyes, see: Craig et al. (1992), as light-emitting materials, see: Spiliopoulos et al. (2002) and as liquid crystalline materials, see: Yam et al. (1993). For a description of the Cambridge Structural Database, see: Allen (2002); Although p-terphenyls containing silyl groups have been reported (Feng et al., 2007), their crystal structures have not yet been determined.

Experimental top

The reaction scheme is shown in Fig. 2. A solution of n-BuLi in hexane (1.6 M, 0.88 ml) was added dropwise to a solution of 1,4-bis(4-iodophenyl)benzene (192 mg, 0.40 mmol) in anhydrous tetrahydrofuran (THF) (80 ml) at -78 °C. After the solution having been stirred for 1 h, dimethylchlorosilane (152 mg, 1.60 mmol), also cooled to the same temperature, was added by syringe. The mixture was allowed to warm to room temperature and it was stirred overnight. After it had been 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 recrystallized from ethanol to give 92 mg of the title product in 67% yield. The crystals were colourless needles with the average length of about 3 mm.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The title molecule, showing 50% probability displacement ellipsoids and the atom-numbering scheme. The atoms without labels are related to the labelled ones by -x, -y+1, -z+2.
	Fig. 2. Reaction scheme for the synthesis of 1,4-bis(4-dimethylsilylphenyl)benzene

1,4-Bis[4-(dimethylsilyl)phenyl]benzene top

Crystal data top

C₂₂H₂₆Si₂	F(000) = 372
M_r = 346.61	D_x = 1.130 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 347 reflections
a = 15.143 (3) Å	θ = 2.2–27.5°
b = 7.7263 (15) Å	µ = 0.18 mm⁻¹
c = 9.1285 (18) Å	T = 173 K
β = 107.52 (3)°	Plate, colorless
V = 1018.5 (3) Å³	0.20 × 0.18 × 0.08 mm
Z = 2

Data collection top

Rigaku Saturn724+ CCD diffractometer	2218 independent reflections
Radiation source: fine-focus sealed tube	1937 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans at fixed χ = 45°	θ_max = 27.0°, θ_min = 2.8°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	h = −19→19
T_min = 0.966, T_max = 0.986	k = −9→9
7661 measured reflections	l = −7→11

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)] = 0.071	Hydrogen site location: difference Fourier map
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ²(F_o²) + (0.0276P)² + 0.8805P] where P = (F_o² + 2F_c²)/3
2218 reflections	(Δ/σ)_max < 0.001
115 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³
46 constraints

Crystal data top

C₂₂H₂₆Si₂	V = 1018.5 (3) Å³
M_r = 346.61	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.143 (3) Å	µ = 0.18 mm⁻¹
b = 7.7263 (15) Å	T = 173 K
c = 9.1285 (18) Å	0.20 × 0.18 × 0.08 mm
β = 107.52 (3)°

Data collection top

Rigaku Saturn724+ CCD diffractometer	2218 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	1937 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.986	R_int = 0.043
7661 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.071	0 restraints
wR(F²) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	Δρ_max = 0.31 e Å⁻³
2218 reflections	Δρ_min = −0.22 e Å⁻³
115 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 > 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

	x	y	z	U_iso*/U_eq
Si1	0.35065 (5)	0.48948 (10)	0.54899 (8)	0.0361 (2)
C1	0.26293 (17)	0.4896 (3)	0.6572 (3)	0.0312 (5)
C2	0.17225 (18)	0.4309 (3)	0.5939 (3)	0.0341 (6)
H2A	0.1533	0.3895	0.4911	0.041*
C3	0.10866 (17)	0.4313 (3)	0.6768 (3)	0.0338 (6)
H3A	0.0474	0.3906	0.6299	0.041*
C4	0.13394 (16)	0.4907 (3)	0.8282 (3)	0.0288 (5)
C5	0.22485 (18)	0.5474 (4)	0.8935 (3)	0.0357 (6)
H5A	0.2441	0.5869	0.9968	0.043*
C6	0.28736 (18)	0.5469 (4)	0.8098 (3)	0.0365 (6)
H6A	0.3487	0.5866	0.8572	0.044*
C7	0.4368 (2)	0.3127 (5)	0.6203 (4)	0.0660 (11)
H7A	0.4832	0.3164	0.5651	0.099*
H7B	0.4051	0.2006	0.6028	0.099*
H7C	0.4674	0.3283	0.7305	0.099*
C8	0.2933 (2)	0.4691 (4)	0.3401 (3)	0.0468 (7)
H8A	0.2475	0.5617	0.3060	0.070*
H8B	0.2624	0.3565	0.3182	0.070*
H8C	0.3398	0.4785	0.2854	0.070*
C9	0.06529 (16)	0.4952 (3)	0.9166 (3)	0.0292 (5)
C10	0.07421 (17)	0.6139 (3)	1.0364 (3)	0.0319 (6)
H10A	0.1249	0.6924	1.0622	0.038*
C11	0.01023 (17)	0.6186 (3)	1.1179 (3)	0.0322 (6)
H11A	0.0178	0.7004	1.1985	0.039*
H1	0.3948 (17)	0.649 (3)	0.578 (3)	0.036 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0341 (4)	0.0455 (5)	0.0312 (4)	−0.0040 (3)	0.0137 (3)	0.0030 (3)
C1	0.0319 (13)	0.0320 (13)	0.0314 (12)	0.0010 (11)	0.0119 (10)	0.0015 (11)
C2	0.0384 (14)	0.0381 (14)	0.0266 (12)	−0.0009 (12)	0.0113 (11)	−0.0023 (11)
C3	0.0295 (13)	0.0366 (14)	0.0345 (14)	−0.0019 (11)	0.0085 (11)	−0.0027 (11)
C4	0.0300 (12)	0.0265 (12)	0.0298 (12)	0.0007 (10)	0.0086 (9)	−0.0002 (10)
C5	0.0359 (14)	0.0432 (16)	0.0281 (13)	−0.0026 (12)	0.0100 (10)	−0.0044 (11)
C6	0.0308 (13)	0.0426 (15)	0.0364 (14)	−0.0037 (12)	0.0106 (11)	−0.0023 (12)
C7	0.0479 (19)	0.094 (3)	0.065 (2)	0.0250 (19)	0.0313 (17)	0.026 (2)
C8	0.0528 (18)	0.0535 (19)	0.0370 (15)	−0.0004 (15)	0.0178 (13)	−0.0022 (13)
C9	0.0294 (12)	0.0298 (13)	0.0280 (11)	0.0030 (11)	0.0079 (9)	0.0045 (10)
C10	0.0295 (12)	0.0337 (13)	0.0319 (13)	−0.0033 (11)	0.0082 (10)	−0.0032 (10)
C11	0.0351 (14)	0.0331 (14)	0.0287 (12)	−0.0025 (11)	0.0101 (11)	−0.0037 (10)

Geometric parameters (Å, º) top

Si1—C8	1.848 (3)	C6—H6A	0.9500
Si1—C7	1.865 (3)	C7—H7A	0.9800
Si1—C1	1.879 (2)	C7—H7B	0.9800
Si1—H1	1.39 (3)	C7—H7C	0.9800
C1—C2	1.395 (3)	C8—H8A	0.9800
C1—C6	1.401 (3)	C8—H8B	0.9800
C2—C3	1.393 (3)	C8—H8C	0.9800
C2—H2A	0.9500	C9—C11ⁱ	1.401 (3)
C3—C4	1.396 (3)	C9—C10	1.402 (3)
C3—H3A	0.9500	C10—C11	1.388 (3)
C4—C5	1.396 (3)	C10—H10A	0.9500
C4—C9	1.496 (3)	C11—C9ⁱ	1.401 (3)
C5—C6	1.384 (3)	C11—H11A	0.9500
C5—H5A	0.9500

C8—Si1—C7	111.07 (16)	C1—C6—H6A	119.0
C8—Si1—C1	110.83 (12)	Si1—C7—H7A	109.5
C7—Si1—C1	110.34 (13)	Si1—C7—H7B	109.5
C8—Si1—H1	108.8 (10)	H7A—C7—H7B	109.5
C7—Si1—H1	109.7 (10)	Si1—C7—H7C	109.5
C1—Si1—H1	106.0 (10)	H7A—C7—H7C	109.5
C2—C1—C6	116.6 (2)	H7B—C7—H7C	109.5
C2—C1—Si1	123.04 (18)	Si1—C8—H8A	109.5
C6—C1—Si1	120.39 (19)	Si1—C8—H8B	109.5
C3—C2—C1	122.0 (2)	H8A—C8—H8B	109.5
C3—C2—H2A	119.0	Si1—C8—H8C	109.5
C1—C2—H2A	119.0	H8A—C8—H8C	109.5
C2—C3—C4	120.7 (2)	H8B—C8—H8C	109.5
C2—C3—H3A	119.7	C11ⁱ—C9—C10	117.8 (2)
C4—C3—H3A	119.7	C11ⁱ—C9—C4	121.1 (2)
C5—C4—C3	117.8 (2)	C10—C9—C4	121.1 (2)
C5—C4—C9	121.3 (2)	C11—C10—C9	121.1 (2)
C3—C4—C9	120.9 (2)	C11—C10—H10A	119.5
C6—C5—C4	121.0 (2)	C9—C10—H10A	119.5
C6—C5—H5A	119.5	C10—C11—C9ⁱ	121.1 (2)
C4—C5—H5A	119.5	C10—C11—H11A	119.4
C5—C6—C1	122.0 (2)	C9ⁱ—C11—H11A	119.4
C5—C6—H6A	119.0

C8—Si1—C1—C2	17.6 (3)	C4—C5—C6—C1	−0.2 (4)
C7—Si1—C1—C2	−105.9 (3)	C2—C1—C6—C5	−0.7 (4)
C8—Si1—C1—C6	−163.7 (2)	Si1—C1—C6—C5	−179.4 (2)
C7—Si1—C1—C6	72.8 (3)	C5—C4—C9—C11ⁱ	−154.1 (2)
C6—C1—C2—C3	0.8 (4)	C3—C4—C9—C11ⁱ	26.7 (4)
Si1—C1—C2—C3	179.6 (2)	C5—C4—C9—C10	26.2 (4)
C1—C2—C3—C4	−0.2 (4)	C3—C4—C9—C10	−153.1 (2)
C2—C3—C4—C5	−0.7 (4)	C11ⁱ—C9—C10—C11	−0.1 (4)
C2—C3—C4—C9	178.6 (2)	C4—C9—C10—C11	179.7 (2)
C3—C4—C5—C6	0.9 (4)	C9—C10—C11—C9ⁱ	0.1 (4)
C9—C4—C5—C6	−178.4 (2)

Symmetry code: (i) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8b···Cg1ⁱⁱ	0.98	2.86	3.826 (3)	171
C10—H10a···Cg1ⁱⁱⁱ	0.95	2.98	3.788 (3)	143

Symmetry codes: (ii) x, −y+1/2, z−1/2; (iii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₆Si₂
M_r	346.61
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	15.143 (3), 7.7263 (15), 9.1285 (18)
β (°)	107.52 (3)
V (Å³)	1018.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.20 × 0.18 × 0.08

Data collection
Diffractometer	Rigaku Saturn724+ CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.966, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	7661, 2218, 1937
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.071, 0.133, 1.21
No. of reflections	2218
No. of parameters	115
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.22

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996).

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8b···Cg1ⁱ	0.98	2.86	3.826 (3)	171
C10—H10a···Cg1ⁱⁱ	0.95	2.98	3.788 (3)	143

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+3/2, z+1/2.

Acknowledgements

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

References

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Feng, X., Pisula, W. & Müllen, K. (2007). J. Am. Chem. Soc. 129, 14116–14117. Web of Science CrossRef PubMed CAS Google Scholar
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doi:10.1107/S1600536810010883

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