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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 8| August 2010| Page o1915
https://doi.org/10.1107/S1600536810024980

1-Methyl-3,5-bis­­(3-methyl­phen­yl)benzene

Dong-Guo Xia,a Ke-Wei Lei,a* Jie Lia and Zheng-Yu Sua

aState Key Lab. Base of Novel Functional Materials and Preparation Science Institute of Solid Materials Chemistry, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
*Correspondence e-mail: leikeweipublic@hotmail.com

(Received 15 June 2010; accepted 25 June 2010; online 3 July 2010)

In the title compound, C21H20, the dihedral angles formed by the central benzene ring with the outer benzene rings are 21.43 (6) and 31.70 (4)°. The crystal packing is stabilized by a weak π–π stacking inter­action, with a centroid–centroid distance of 3.843 (3) Å.

Related literature

For conformational studies on terphenyls, see: Amorim da Costa et al. (1997[Amorim da Costa, A. M., Karger, N., Amado, A. M. & Becucci, M. (1997). Solid State Ionics, 97, 115-121.]); Stanciu et al. (2006[Stanciu, C., Richards, A. F., Fettinger, J. C., Brynda, M. & Power, P. P. (2006). J. Organomet. Chem. 691, 2540-2545]).

[Scheme 1]

Experimental

Crystal data

  • C21H20

  • Mr = 272.37

  • Orthorhombic, P b c a

  • a = 7.6406 (7) Å

  • b = 12.0326 (11) Å

  • c = 32.797 (3) Å

  • V = 3015.3 (5) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.07 mm−1

  • T = 296 K

  • 0.43 × 0.26 × 0.22 mm
Data collection

  • Bruker SMART APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2000[Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany.]) Tmin = 0.979, Tmax = 0.985

  • 20126 measured reflections

  • 2644 independent reflections

  • 2278 reflections with I > 2σ(I)

  • Rint = 0.036
Refinement

  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.112

  • S = 1.05

  • 2644 reflections

  • 193 parameters

  • H-atom parameters constrained

  • Δρmax = 0.27 e Å−3

  • Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810024980/fj2321sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810024980/fj2321Isup2.hkl

checkCIF report


Comment top

Sterically crowding ligands have been used with remarkable success in inorganic and organometallic chemistry over the past three decades. They have allowed the first syntheses of molecules featuring previously unknown bonding types, geometries, electron configurations or oxidation states.Recent work has also described the use of m-terphenyls that allowed the synthesis of several new compound classes that were not accessible by using other bulky ligands(Corneliu Stanciu et al., 2006). The use of the m-terphenyl substituent has facilitated the synthesis of numerous unusual molecules containing main group elements;because these molecules are formed by three phenyl rings connected by two C—C bonds, characteristic conformational changes occur with the rotations around the C—C bonds (Amorim da Costa et al., 1997). Herein we report the synthesis and crystal structure of a new terphenyl compound.

The molecular structure of the title compound is illustrated in Fig. 1. Bond lengths and bond angles are within normal ranges.The dihedral angle formed by the peripheral C8—C13 and C15—C20 benzene rings with the central C2—C7 benzene ring are 21.43 (6) and 31.70 (4)° respectively. The mean centroid-to-centroid distance of 3.843 (3)Å between the planes of adjacent C15—C20 benzene rings in the crystal packing, suggests that the molecules are engaged in offset face-to-face π-π stacking interactions(Fig. 2).

Related literature top

For conformational studies on terphenyls, see: Amorim da Costa et al. (1997); Stanciu et al. (2006).

Experimental top

1,3-dibromo-5-methylbenzene(88.1 mmol,22.02 g), 3-methylphenylboronic acid (211.6 mmol, 28.77 g)and triphenylphosphine (17.62 mmol, 4.62 g) were dissolved in 1,2-dimethoxyethoxyethane (120 ml).240 ml of a 2M K2CO3 (480 mmol)aqueous solution were added and the mixture was purged with nitrogen. Palladium acetate (0.988 g;0.025eq.)was added and the mixture was refluxed for 18 h.The two phases were then separated and the aqueous phase was extracted with ethyl acetate(3 X 250 ml).The combined organic phases were washed with water (250 ml) and were dried over MgSO4.After evaporation of the solvent,the oily residue was purified by bulb-to-bulb distillation to afford the crude title compound. Recrystallization from ethyl acetate gave colourless crystal after 3 days.Yield:83.7%.Calcd.for C21H20:C,92.65; H,7.35;Found:C,91.78;H,7.08%.

Refinement top

All H atoms were placed in geometrically idealized positions and treated as riding on their parent atoms, with C—H = 0.93–0.96 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.

Structure description top

Sterically crowding ligands have been used with remarkable success in inorganic and organometallic chemistry over the past three decades. They have allowed the first syntheses of molecules featuring previously unknown bonding types, geometries, electron configurations or oxidation states.Recent work has also described the use of m-terphenyls that allowed the synthesis of several new compound classes that were not accessible by using other bulky ligands(Corneliu Stanciu et al., 2006). The use of the m-terphenyl substituent has facilitated the synthesis of numerous unusual molecules containing main group elements;because these molecules are formed by three phenyl rings connected by two C—C bonds, characteristic conformational changes occur with the rotations around the C—C bonds (Amorim da Costa et al., 1997). Herein we report the synthesis and crystal structure of a new terphenyl compound.

The molecular structure of the title compound is illustrated in Fig. 1. Bond lengths and bond angles are within normal ranges.The dihedral angle formed by the peripheral C8—C13 and C15—C20 benzene rings with the central C2—C7 benzene ring are 21.43 (6) and 31.70 (4)° respectively. The mean centroid-to-centroid distance of 3.843 (3)Å between the planes of adjacent C15—C20 benzene rings in the crystal packing, suggests that the molecules are engaged in offset face-to-face π-π stacking interactions(Fig. 2).

For conformational studies on terphenyls, see: Amorim da Costa et al. (1997); Stanciu et al. (2006).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Packing diagram of the title compound.
1-Methyl-3,5-bis(3-methylphenyl)benzene top
Crystal data top
C21H20F(000) = 1168
Mr = 272.37Dx = 1.200 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 6268 reflections
a = 7.6406 (7) Åθ = 2.5–27.4°
b = 12.0326 (11) ŵ = 0.07 mm−1
c = 32.797 (3) ÅT = 296 K
V = 3015.3 (5) Å3Block, colourless
Z = 80.43 × 0.26 × 0.22 mm
Data collection top
Bruker SMART APEXII
diffractometer		2644 independent reflections
Radiation source: fine-focus sealed tube2278 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.036
φ and ω scansθmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		h = −9→9
Tmin = 0.979, Tmax = 0.985k = −14→14
20126 measured reflectionsl = −39→38
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.053P)2 + 1.5497P]
where P = (Fo2 + 2Fc2)/3
2644 reflections(Δ/σ)max < 0.001
193 parametersΔρmax = 0.27 e Å−3
0 restraintsΔρmin = −0.28 e Å−3
Crystal data top
C21H20V = 3015.3 (5) Å3
Mr = 272.37Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 7.6406 (7) ŵ = 0.07 mm−1
b = 12.0326 (11) ÅT = 296 K
c = 32.797 (3) Å0.43 × 0.26 × 0.22 mm
Data collection top
Bruker SMART APEXII
diffractometer		2644 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		2278 reflections with I > 2σ(I)
Tmin = 0.979, Tmax = 0.985Rint = 0.036
20126 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.112H-atom parameters constrained
S = 1.05Δρmax = 0.27 e Å−3
2644 reflectionsΔρmin = −0.28 e Å−3
193 parameters
Special details top

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) top
xyzUiso*/Ueq
C10.0076 (2)0.05890 (13)0.14273 (5)0.0304 (4)
H1A0.05500.05060.16970.046*
H1B0.07310.01380.12400.046*
H1C−0.11260.03570.14270.046*
C20.01904 (19)0.17904 (12)0.12994 (5)0.0237 (3)
C3−0.01589 (19)0.26372 (13)0.15779 (5)0.0243 (3)
H3A−0.04530.24520.18440.029*
C4−0.00781 (19)0.37595 (12)0.14669 (4)0.0221 (3)
C50.03488 (19)0.40135 (12)0.10636 (4)0.0222 (3)
H5A0.03880.47550.09840.027*
C60.07185 (19)0.31898 (12)0.07760 (4)0.0214 (3)
C70.06397 (19)0.20792 (12)0.09019 (4)0.0231 (3)
H7A0.08940.15200.07150.028*
C8−0.1845 (2)0.53195 (14)0.23846 (5)0.0312 (4)
H8A−0.25100.51740.26160.037*
C9−0.1251 (2)0.63898 (14)0.23108 (5)0.0301 (4)
H9A−0.15240.69560.24930.036*
C10−0.0250 (2)0.66247 (13)0.19661 (5)0.0263 (4)
C110.0137 (2)0.57517 (13)0.17008 (4)0.0243 (3)
H11A0.08180.58970.14720.029*
C12−0.04596 (19)0.46664 (13)0.17657 (4)0.0229 (3)
C13−0.1455 (2)0.44670 (14)0.21164 (4)0.0274 (4)
H13A−0.18590.37530.21700.033*
C140.0387 (2)0.77826 (13)0.18766 (5)0.0346 (4)
H14A0.04590.81970.21260.052*
H14B−0.04140.81430.16940.052*
H14C0.15240.77470.17530.052*
C150.1183 (2)0.34962 (12)0.03493 (4)0.0226 (3)
C160.07320 (19)0.28196 (12)0.00195 (4)0.0229 (3)
H16A0.01140.21670.00670.027*
C170.1186 (2)0.30979 (13)−0.03800 (4)0.0251 (4)
C180.2084 (2)0.40874 (13)−0.04463 (5)0.0289 (4)
H18A0.23930.4289−0.07100.035*
C190.2521 (2)0.47750 (13)−0.01241 (5)0.0319 (4)
H19A0.31110.5438−0.01730.038*
C200.2085 (2)0.44820 (13)0.02705 (5)0.0285 (4)
H20A0.23960.49460.04850.034*
C210.0716 (2)0.23510 (15)−0.07326 (5)0.0342 (4)
H21A0.17640.2128−0.08720.051*
H21B−0.00330.2745−0.09180.051*
H21C0.01190.1705−0.06320.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0354 (9)0.0265 (8)0.0292 (9)−0.0017 (7)−0.0011 (7)0.0040 (7)
C20.0204 (7)0.0242 (8)0.0266 (8)−0.0010 (6)−0.0030 (6)0.0027 (6)
C30.0235 (8)0.0291 (8)0.0203 (8)−0.0007 (6)−0.0013 (6)0.0038 (6)
C40.0187 (7)0.0258 (8)0.0219 (8)0.0004 (6)−0.0023 (6)−0.0004 (6)
C50.0227 (7)0.0207 (7)0.0233 (8)−0.0004 (6)−0.0013 (6)0.0009 (6)
C60.0194 (7)0.0236 (8)0.0213 (8)−0.0004 (6)−0.0009 (6)0.0002 (6)
C70.0228 (8)0.0228 (8)0.0237 (8)0.0005 (6)−0.0009 (6)−0.0025 (6)
C80.0308 (9)0.0412 (10)0.0217 (8)0.0059 (7)0.0034 (6)0.0008 (7)
C90.0328 (9)0.0351 (9)0.0225 (8)0.0109 (7)−0.0030 (7)−0.0064 (7)
C100.0265 (8)0.0289 (8)0.0233 (8)0.0062 (7)−0.0056 (6)−0.0024 (6)
C110.0241 (8)0.0281 (8)0.0208 (8)0.0037 (6)−0.0003 (6)0.0008 (6)
C120.0207 (7)0.0282 (8)0.0197 (7)0.0034 (6)−0.0037 (6)0.0006 (6)
C130.0273 (8)0.0318 (9)0.0231 (8)0.0000 (7)−0.0001 (6)0.0020 (6)
C140.0411 (10)0.0293 (9)0.0333 (9)0.0036 (7)−0.0005 (8)−0.0058 (7)
C150.0232 (8)0.0208 (7)0.0239 (8)0.0035 (6)0.0025 (6)0.0018 (6)
C160.0238 (7)0.0206 (8)0.0241 (8)0.0020 (6)0.0017 (6)0.0008 (6)
C170.0230 (8)0.0287 (8)0.0237 (8)0.0092 (6)0.0005 (6)0.0013 (6)
C180.0297 (9)0.0308 (9)0.0261 (8)0.0073 (7)0.0069 (6)0.0091 (7)
C190.0349 (9)0.0253 (9)0.0353 (9)−0.0024 (7)0.0075 (7)0.0058 (7)
C200.0325 (9)0.0240 (8)0.0291 (8)−0.0019 (7)0.0028 (7)−0.0018 (7)
C210.0396 (10)0.0403 (10)0.0228 (8)0.0038 (8)−0.0007 (7)−0.0001 (7)
Geometric parameters (Å, º) top
C1—C21.508 (2)C11—C121.399 (2)
C1—H1A0.9600C11—H11A0.9300
C1—H1B0.9600C12—C131.399 (2)
C1—H1C0.9600C13—H13A0.9300
C2—C71.392 (2)C14—H14A0.9600
C2—C31.394 (2)C14—H14B0.9600
C3—C41.400 (2)C14—H14C0.9600
C3—H3A0.9300C15—C201.396 (2)
C4—C51.396 (2)C15—C161.397 (2)
C4—C121.495 (2)C16—C171.396 (2)
C5—C61.397 (2)C16—H16A0.9300
C5—H5A0.9300C17—C181.391 (2)
C6—C71.400 (2)C17—C211.508 (2)
C6—C151.490 (2)C18—C191.383 (2)
C7—H7A0.9300C18—H18A0.9300
C8—C131.384 (2)C19—C201.382 (2)
C8—C91.387 (2)C19—H19A0.9300
C8—H8A0.9300C20—H20A0.9300
C9—C101.394 (2)C21—H21A0.9600
C9—H9A0.9300C21—H21B0.9600
C10—C111.396 (2)C21—H21C0.9600
C10—C141.505 (2)
C2—C1—H1A109.5C11—C12—C13117.51 (14)
C2—C1—H1B109.5C11—C12—C4121.19 (13)
H1A—C1—H1B109.5C13—C12—C4121.28 (14)
C2—C1—H1C109.5C8—C13—C12120.82 (15)
H1A—C1—H1C109.5C8—C13—H13A119.6
H1B—C1—H1C109.5C12—C13—H13A119.6
C7—C2—C3118.57 (14)C10—C14—H14A109.5
C7—C2—C1120.93 (14)C10—C14—H14B109.5
C3—C2—C1120.50 (14)H14A—C14—H14B109.5
C2—C3—C4121.77 (14)C10—C14—H14C109.5
C2—C3—H3A119.1H14A—C14—H14C109.5
C4—C3—H3A119.1H14B—C14—H14C109.5
C5—C4—C3117.88 (14)C20—C15—C16118.27 (14)
C5—C4—C12120.44 (13)C20—C15—C6120.11 (13)
C3—C4—C12121.68 (13)C16—C15—C6121.63 (13)
C4—C5—C6122.12 (14)C17—C16—C15121.71 (14)
C4—C5—H5A118.9C17—C16—H16A119.1
C6—C5—H5A118.9C15—C16—H16A119.1
C5—C6—C7117.99 (13)C18—C17—C16118.33 (14)
C5—C6—C15120.45 (13)C18—C17—C21120.49 (14)
C7—C6—C15121.56 (13)C16—C17—C21121.18 (14)
C2—C7—C6121.66 (14)C19—C18—C17120.77 (14)
C2—C7—H7A119.2C19—C18—H18A119.6
C6—C7—H7A119.2C17—C18—H18A119.6
C13—C8—C9120.46 (15)C20—C19—C18120.31 (15)
C13—C8—H8A119.8C20—C19—H19A119.8
C9—C8—H8A119.8C18—C19—H19A119.8
C8—C9—C10120.63 (14)C19—C20—C15120.60 (15)
C8—C9—H9A119.7C19—C20—H20A119.7
C10—C9—H9A119.7C15—C20—H20A119.7
C9—C10—C11117.98 (15)C17—C21—H21A109.5
C9—C10—C14121.56 (14)C17—C21—H21B109.5
C11—C10—C14120.46 (14)H21A—C21—H21B109.5
C10—C11—C12122.60 (14)C17—C21—H21C109.5
C10—C11—H11A118.7H21A—C21—H21C109.5
C12—C11—H11A118.7H21B—C21—H21C109.5

Experimental details

Crystal data
Chemical formulaC21H20
Mr272.37
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)7.6406 (7), 12.0326 (11), 32.797 (3)
V (Å3)3015.3 (5)
Z8
Radiation typeMo Kα
µ (mm−1)0.07
Crystal size (mm)0.43 × 0.26 × 0.22
Data collection
DiffractometerBruker SMART APEXII
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000)
Tmin, Tmax0.979, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections		20126, 2644, 2278
Rint0.036
(sin θ/λ)max (Å−1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.112, 1.05
No. of reflections2644
No. of parameters193
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.27, −0.28

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

This project was supported by the Talent Fund of Ningbo University (grant No. 2008087) and sponsored by the K. C. Wong Magna Fund in Ningbo University.

References

First citationAmorim da Costa, A. M., Karger, N., Amado, A. M. & Becucci, M. (1997). Solid State Ionics, 97, 115–121.  CrossRef CAS Google Scholar
 First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationSheldrick, G. M. (2000). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationStanciu, C., Richards, A. F., Fettinger, J. C., Brynda, M. & Power, P. P. (2006). J. Organomet. Chem. 691, 2540–2545  Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 8| August 2010| Page o1915
https://doi.org/10.1107/S1600536810024980
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