PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o971.
Published online 2010 March 27. doi:  10.1107/S1600536810010883
PMCID: PMC2984042

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

Abstract

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

An external file that holds a picture, illustration, etc.
Object name is e-66-0o971-scheme1.jpg

Experimental

Crystal data

  • C22H26Si2
  • M r = 346.61
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o971-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.071
  • wR(F 2) = 0.133
  • S = 1.21
  • 2218 reflections
  • 115 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.22 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.]

Experimental

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.

Refinement

All the hydrogens were discernible in the difference electron density maps. Nevertheless, all the hydrogens except the hydrogen attached to Si that was refined freely, were constrained by the riding-hydrogen formalism with Uiso(H)=1.2Ueq(Caryl) or Uiso(H)=1.5Ueq(Cmethyl). The C-H distances were constrained to 0.95 and 0.98 Å for the aryl and the methyl hydrogens, respectively.

Figures

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

Crystal data

C22H26Si2F(000) = 372
Mr = 346.61Dx = 1.130 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 347 reflections
a = 15.143 (3) Åθ = 2.2–27.5°
b = 7.7263 (15) ŵ = 0.18 mm1
c = 9.1285 (18) ÅT = 173 K
β = 107.52 (3)°Plate, colorless
V = 1018.5 (3) Å30.20 × 0.18 × 0.08 mm
Z = 2

Data collection

Rigaku Saturn724+ CCD diffractometer2218 independent reflections
Radiation source: fine-focus sealed tube1937 reflections with I > 2σ(I)
graphiteRint = 0.043
ω scans at fixed χ = 45°θmax = 27.0°, θmin = 2.8°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)h = −19→19
Tmin = 0.966, Tmax = 0.986k = −9→9
7661 measured reflectionsl = −7→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.071Hydrogen site location: difference Fourier map
wR(F2) = 0.133H atoms treated by a mixture of independent and constrained refinement
S = 1.21w = 1/[σ2(Fo2) + (0.0276P)2 + 0.8805P] where P = (Fo2 + 2Fc2)/3
2218 reflections(Δ/σ)max < 0.001
115 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = −0.21 e Å3
46 constraints

Special details

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)

xyzUiso*/Ueq
Si10.35065 (5)0.48948 (10)0.54899 (8)0.0361 (2)
C10.26293 (17)0.4896 (3)0.6572 (3)0.0312 (5)
C20.17225 (18)0.4309 (3)0.5939 (3)0.0341 (6)
H2A0.15330.38950.49110.041*
C30.10866 (17)0.4313 (3)0.6768 (3)0.0338 (6)
H3A0.04740.39060.62990.041*
C40.13394 (16)0.4907 (3)0.8282 (3)0.0288 (5)
C50.22485 (18)0.5474 (4)0.8935 (3)0.0357 (6)
H5A0.24410.58690.99680.043*
C60.28736 (18)0.5469 (4)0.8098 (3)0.0365 (6)
H6A0.34870.58660.85720.044*
C70.4368 (2)0.3127 (5)0.6203 (4)0.0660 (11)
H7A0.48320.31640.56510.099*
H7B0.40510.20060.60280.099*
H7C0.46740.32830.73050.099*
C80.2933 (2)0.4691 (4)0.3401 (3)0.0468 (7)
H8A0.24750.56170.30600.070*
H8B0.26240.35650.31820.070*
H8C0.33980.47850.28540.070*
C90.06529 (16)0.4952 (3)0.9166 (3)0.0292 (5)
C100.07421 (17)0.6139 (3)1.0364 (3)0.0319 (6)
H10A0.12490.69241.06220.038*
C110.01023 (17)0.6186 (3)1.1179 (3)0.0322 (6)
H11A0.01780.70041.19850.039*
H10.3948 (17)0.649 (3)0.578 (3)0.036 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Si10.0341 (4)0.0455 (5)0.0312 (4)−0.0040 (3)0.0137 (3)0.0030 (3)
C10.0319 (13)0.0320 (13)0.0314 (12)0.0010 (11)0.0119 (10)0.0015 (11)
C20.0384 (14)0.0381 (14)0.0266 (12)−0.0009 (12)0.0113 (11)−0.0023 (11)
C30.0295 (13)0.0366 (14)0.0345 (14)−0.0019 (11)0.0085 (11)−0.0027 (11)
C40.0300 (12)0.0265 (12)0.0298 (12)0.0007 (10)0.0086 (9)−0.0002 (10)
C50.0359 (14)0.0432 (16)0.0281 (13)−0.0026 (12)0.0100 (10)−0.0044 (11)
C60.0308 (13)0.0426 (15)0.0364 (14)−0.0037 (12)0.0106 (11)−0.0023 (12)
C70.0479 (19)0.094 (3)0.065 (2)0.0250 (19)0.0313 (17)0.026 (2)
C80.0528 (18)0.0535 (19)0.0370 (15)−0.0004 (15)0.0178 (13)−0.0022 (13)
C90.0294 (12)0.0298 (13)0.0280 (11)0.0030 (11)0.0079 (9)0.0045 (10)
C100.0295 (12)0.0337 (13)0.0319 (13)−0.0033 (11)0.0082 (10)−0.0032 (10)
C110.0351 (14)0.0331 (14)0.0287 (12)−0.0025 (11)0.0101 (11)−0.0037 (10)

Geometric parameters (Å, °)

Si1—C81.848 (3)C6—H6A0.9500
Si1—C71.865 (3)C7—H7A0.9800
Si1—C11.879 (2)C7—H7B0.9800
Si1—H11.39 (3)C7—H7C0.9800
C1—C21.395 (3)C8—H8A0.9800
C1—C61.401 (3)C8—H8B0.9800
C2—C31.393 (3)C8—H8C0.9800
C2—H2A0.9500C9—C11i1.401 (3)
C3—C41.396 (3)C9—C101.402 (3)
C3—H3A0.9500C10—C111.388 (3)
C4—C51.396 (3)C10—H10A0.9500
C4—C91.496 (3)C11—C9i1.401 (3)
C5—C61.384 (3)C11—H11A0.9500
C5—H5A0.9500
C8—Si1—C7111.07 (16)C1—C6—H6A119.0
C8—Si1—C1110.83 (12)Si1—C7—H7A109.5
C7—Si1—C1110.34 (13)Si1—C7—H7B109.5
C8—Si1—H1108.8 (10)H7A—C7—H7B109.5
C7—Si1—H1109.7 (10)Si1—C7—H7C109.5
C1—Si1—H1106.0 (10)H7A—C7—H7C109.5
C2—C1—C6116.6 (2)H7B—C7—H7C109.5
C2—C1—Si1123.04 (18)Si1—C8—H8A109.5
C6—C1—Si1120.39 (19)Si1—C8—H8B109.5
C3—C2—C1122.0 (2)H8A—C8—H8B109.5
C3—C2—H2A119.0Si1—C8—H8C109.5
C1—C2—H2A119.0H8A—C8—H8C109.5
C2—C3—C4120.7 (2)H8B—C8—H8C109.5
C2—C3—H3A119.7C11i—C9—C10117.8 (2)
C4—C3—H3A119.7C11i—C9—C4121.1 (2)
C5—C4—C3117.8 (2)C10—C9—C4121.1 (2)
C5—C4—C9121.3 (2)C11—C10—C9121.1 (2)
C3—C4—C9120.9 (2)C11—C10—H10A119.5
C6—C5—C4121.0 (2)C9—C10—H10A119.5
C6—C5—H5A119.5C10—C11—C9i121.1 (2)
C4—C5—H5A119.5C10—C11—H11A119.4
C5—C6—C1122.0 (2)C9i—C11—H11A119.4
C5—C6—H6A119.0
C8—Si1—C1—C217.6 (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—C672.8 (3)C5—C4—C9—C11i−154.1 (2)
C6—C1—C2—C30.8 (4)C3—C4—C9—C11i26.7 (4)
Si1—C1—C2—C3179.6 (2)C5—C4—C9—C1026.2 (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—C9178.6 (2)C4—C9—C10—C11179.7 (2)
C3—C4—C5—C60.9 (4)C9—C10—C11—C9i0.1 (4)
C9—C4—C5—C6−178.4 (2)

Symmetry codes: (i) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
C8—H8b···Cg1ii0.982.863.826 (3)171
C10—H10a···Cg1iii0.952.983.788 (3)143

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FB2186).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.
  • Craig, C. J. & Hartmut, S. (1992). Appl. Opt.31, 7012–7021. [PubMed]
  • Feng, X., Pisula, W. & Müllen, K. (2007). J. Am. Chem. Soc.129, 14116–14117. [PubMed]
  • Rigaku (2008). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spiliopoulos, I. K. & Mikroyannidis, J. A. (2002). J. Polym. Sci. Part A Polym. Chem.40, 2591–2600.
  • Yam, R. & Berkovic, G. (1993). Langmuir, 9, 2109–2211.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography