1,2-Bis(3,5-di­methyl­phen­yl)ethane

Brieger, L.; Unkelbach, C.; Strohmann, C.

doi:10.1107/S2414314618006363

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 4| April 2018| x180636

https://doi.org/10.1107/S2414314618006363

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1,2-Bis(3,5-dimethylphenyl)ethane

Lukas Brieger,^a Christian Unkelbach ^a and Carsten Strohmann ^a ^*

^aTechnische Universität Dortmund, Anorganische Chemie, Otto-Hahn-Strasse 6, D-44227 Dortmund, Germany
^*Correspondence e-mail: carsten.strohmann@tu-dortmund.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 4 April 2018; accepted 25 April 2018; online 27 April 2018)

The title compound, C₁₈H₂₂, is a coupling product of two metallated mesitylene molecules. The dihedral angle between the aromatic rings is 11.10 (5)° and the C_ar—C_m—C_m—C_ar (ar = aromatic and m = methylene) torsion angle is 179.60 (14)°. No directional interactions beyond normal van der Waals contacts could be identified in the crystal. To our best knowledge, it is the first known coupling product of metallated mesitylene.

Keywords: crystal structure; mesitylene; dimethylphenylethane; lithiation.

CCDC reference: 1816412

Structure description

In the presence of Lochmann–Schlosser's base, a metallation of the methyl group of mesitylene (1,3,5-trimethyl benzene) takes place (Schlosser, 1988 ). Trapping the reaction mixture with dibromoethane leads to the title compound (Fig. 1) after distillation. The dihedral angle between the aromatic rings is 11.10 (5)° and the C_ar—C_methyl distances lie between 1.505 (2)-1.5100 (2) Å. For the benzene rings, normal bond length between 1.387 (2)–1.395 (2) Å are observed and the C—C—C angles range from 118.33 (14)–121.74 (14)°. No directional interactions beyond normal van der Waals' contacts could be observed in the crystal (Fig. 2).

Figure 1
Molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Figure 2
Unit-cell packing viewed along the b-axis direction.

The basic building unit, mesitylene, has been known for a long time and has been well characterized (Ladenburg 1874 ; Hewlett 1922 ). Derivatives of it have been crystallized and their structures determined (e.g. Trotter, 1959 ). The related compound nitromesitylene (Powell & Johnson, 1934 ) shows typical C_ar—C_ar and C_ar—C_methyl distances of 1.383 and 1.509 Å, respectively.

Synthesis and crystallization

The title compound was obtained by treating 11.60 ml (87.05 mmol, 1.0 eq.) mesitylene (1,3,5-trimethyl benzene) with 38.30 ml (95.76 mmol, 1.1 eq.) n-butyllithium and 10.75 g (95.76 mmol, 1.1 eq.) potassium-tert-butoxide at −78°C in 200 ml THF. Then, 8.25 ml (95.76 mmol, 1.1 eq.) dibromoethane were added after stirring the solution for 1 h. The solution was quenched with water, extracted with diethyl ether and the organic phase was dried with sodium sulfate and distilled. The title compound crystallized as colourless plates. The yield was not determined.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₈H₂₂
M_r	238.35
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	7.9315 (5), 8.2047 (5), 12.3474 (8)
α, β, γ (°)	108.513 (6), 98.090 (5), 103.805 (5)
V (Å³)	719.18 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.06
Crystal size (mm)	0.3 × 0.3 × 0.1

Data collection
Diffractometer	Agilent Xcalibur, Sapphire3
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2014 )
T_min, T_max	0.984, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	22466, 3471, 2598
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.161, 1.05
No. of reflections	3471
No. of parameters	167
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.23
Computer programs: CrysAlis PRO (Agilent, 2014), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1816412

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618006363/hb4226sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618006363/hb4226Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618006363/hb4226Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

1,2-Bis(3,5-dimethylphenyl)ethane top

Crystal data top

C₁₈H₂₂	Z = 2
M_r = 238.35	F(000) = 260
Triclinic, P1	D_x = 1.101 Mg m⁻³
a = 7.9315 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2047 (5) Å	Cell parameters from 4159 reflections
c = 12.3474 (8) Å	θ = 2.7–29.5°
α = 108.513 (6)°	µ = 0.06 mm⁻¹
β = 98.090 (5)°	T = 150 K
γ = 103.805 (5)°	Plate, colourless
V = 719.18 (8) Å³	0.3 × 0.3 × 0.1 mm

Data collection top

Agilent Xcalibur, Sapphire3 diffractometer	3471 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2598 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 16.0560 pixels mm^-1	θ_max = 28.0°, θ_min = 2.7°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −10→10
T_min = 0.984, T_max = 1.000	l = −16→16
22466 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	All H-atom parameters refined
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.069P)² + 0.3054P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
3471 reflections	Δρ_max = 0.28 e Å⁻³
167 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints

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. The C-bound H atoms were included in calculated positions and treated as riding atoms, with C—H = 0.98 A° , U_iso(H) = 1.5U_eq(C) for methyl hydrogen atoms and C—H = 0.99 A° , U_iso(H) = 1.2U_eq(C) for methylene hydrogen atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.8890 (2)	0.0999 (2)	0.66953 (14)	0.0257 (3)
C2	0.9788 (2)	0.2551 (2)	0.76669 (14)	0.0251 (3)
H2	1.0541	0.2470	0.8305	0.030*
C3	0.9614 (2)	0.4226 (2)	0.77288 (13)	0.0248 (3)
C4	0.8487 (2)	0.4313 (2)	0.67960 (14)	0.0249 (3)
H4	0.8344	0.5445	0.6832	0.030*
C5	0.7558 (2)	0.2784 (2)	0.58078 (13)	0.0238 (3)
C6	0.7782 (2)	0.1138 (2)	0.57672 (13)	0.0254 (3)
H6	0.7168	0.0086	0.5094	0.030*
C7	0.6240 (2)	0.55118 (19)	0.29547 (13)	0.0225 (3)
H7	0.7017	0.6579	0.3560	0.027*
C8	0.5160 (2)	0.5651 (2)	0.20159 (13)	0.0238 (3)
C9	0.4034 (2)	0.4081 (2)	0.11365 (13)	0.0252 (3)
H9	0.3307	0.4159	0.0486	0.030*
C10	0.3946 (2)	0.2390 (2)	0.11882 (13)	0.0255 (3)
C11	0.5039 (2)	0.2301 (2)	0.21364 (13)	0.0245 (3)
H11	0.4989	0.1156	0.2180	0.029*
C12	0.62052 (19)	0.3845 (2)	0.30250 (13)	0.0225 (3)
C13	0.7396 (2)	0.3707 (2)	0.40370 (14)	0.0273 (4)
H13A	0.8214	0.4922	0.4531	0.033*
H13B	0.8134	0.2934	0.3723	0.033*
C14	0.6356 (2)	0.2929 (2)	0.48025 (14)	0.0288 (4)
H14A	0.5625	0.3707	0.5123	0.035*
H14B	0.5533	0.1717	0.4309	0.035*
C15	0.5176 (2)	0.7475 (2)	0.19759 (15)	0.0321 (4)
H15A	0.4313	0.7907	0.2395	0.048*
H15B	0.4851	0.7373	0.1156	0.048*
H15C	0.6373	0.8330	0.2351	0.048*
C16	0.2699 (2)	0.0688 (2)	0.02401 (15)	0.0371 (4)
H16A	0.3388	0.0067	−0.0255	0.056*
H16B	0.1826	0.0994	−0.0243	0.056*
H16C	0.2073	−0.0103	0.0602	0.056*
C17	0.9095 (3)	−0.0809 (2)	0.66367 (17)	0.0386 (4)
H17A	0.9959	−0.0651	0.7341	0.058*
H17B	0.9521	−0.1329	0.5937	0.058*
H17C	0.7937	−0.1619	0.6595	0.058*
C18	1.0642 (2)	0.5910 (2)	0.87696 (15)	0.0340 (4)
H18A	1.0235	0.5841	0.9472	0.051*
H18B	1.0443	0.6963	0.8623	0.051*
H18C	1.1919	0.6022	0.8892	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0263 (8)	0.0231 (8)	0.0334 (8)	0.0104 (6)	0.0123 (7)	0.0135 (7)
C2	0.0226 (7)	0.0296 (8)	0.0269 (8)	0.0088 (6)	0.0067 (6)	0.0144 (7)
C3	0.0238 (7)	0.0231 (8)	0.0276 (8)	0.0048 (6)	0.0107 (6)	0.0090 (6)
C4	0.0283 (8)	0.0197 (7)	0.0320 (8)	0.0085 (6)	0.0124 (7)	0.0134 (6)
C5	0.0223 (7)	0.0275 (8)	0.0271 (8)	0.0075 (6)	0.0099 (6)	0.0154 (6)
C6	0.0271 (8)	0.0217 (7)	0.0263 (8)	0.0049 (6)	0.0088 (6)	0.0083 (6)
C7	0.0243 (7)	0.0197 (7)	0.0228 (7)	0.0044 (6)	0.0092 (6)	0.0067 (6)
C8	0.0267 (8)	0.0232 (8)	0.0281 (8)	0.0103 (6)	0.0136 (6)	0.0130 (6)
C9	0.0256 (8)	0.0287 (8)	0.0259 (8)	0.0115 (6)	0.0074 (6)	0.0131 (6)
C10	0.0250 (8)	0.0234 (8)	0.0260 (8)	0.0050 (6)	0.0080 (6)	0.0072 (6)
C11	0.0278 (8)	0.0196 (7)	0.0295 (8)	0.0081 (6)	0.0092 (6)	0.0119 (6)
C12	0.0216 (7)	0.0253 (8)	0.0244 (7)	0.0080 (6)	0.0088 (6)	0.0118 (6)
C13	0.0242 (8)	0.0317 (8)	0.0298 (8)	0.0075 (6)	0.0067 (6)	0.0166 (7)
C14	0.0260 (8)	0.0357 (9)	0.0298 (8)	0.0096 (7)	0.0077 (7)	0.0180 (7)
C15	0.0411 (10)	0.0251 (8)	0.0388 (9)	0.0141 (7)	0.0157 (8)	0.0173 (7)
C16	0.0384 (10)	0.0289 (9)	0.0332 (9)	0.0009 (8)	0.0015 (8)	0.0068 (7)
C17	0.0438 (10)	0.0268 (9)	0.0504 (11)	0.0167 (8)	0.0107 (9)	0.0166 (8)
C18	0.0350 (9)	0.0278 (9)	0.0316 (9)	0.0037 (7)	0.0087 (7)	0.0048 (7)

Geometric parameters (Å, º) top

C1—C2	1.388 (2)	C11—H11	0.9500
C1—C6	1.395 (2)	C11—C12	1.392 (2)
C1—C17	1.510 (2)	C12—C13	1.508 (2)
C2—H2	0.9500	C13—H13A	0.9900
C2—C3	1.393 (2)	C13—H13B	0.9900
C3—C4	1.387 (2)	C13—C14	1.527 (2)
C3—C18	1.505 (2)	C14—H14A	0.9900
C4—H4	0.9500	C14—H14B	0.9900
C4—C5	1.393 (2)	C15—H15A	0.9800
C5—C6	1.390 (2)	C15—H15B	0.9800
C5—C14	1.510 (2)	C15—H15C	0.9800
C6—H6	0.9500	C16—H16A	0.9800
C7—H7	0.9500	C16—H16B	0.9800
C7—C8	1.393 (2)	C16—H16C	0.9800
C7—C12	1.391 (2)	C17—H17A	0.9800
C8—C9	1.388 (2)	C17—H17B	0.9800
C8—C15	1.510 (2)	C17—H17C	0.9800
C9—H9	0.9500	C18—H18A	0.9800
C9—C10	1.395 (2)	C18—H18B	0.9800
C10—C11	1.388 (2)	C18—H18C	0.9800
C10—C16	1.508 (2)

C2—C1—C6	118.55 (13)	C12—C13—H13A	109.0
C2—C1—C17	121.12 (15)	C12—C13—H13B	109.0
C6—C1—C17	120.33 (15)	C12—C13—C14	113.08 (13)
C1—C2—H2	119.2	H13A—C13—H13B	107.8
C1—C2—C3	121.61 (14)	C14—C13—H13A	109.0
C3—C2—H2	119.2	C14—C13—H13B	109.0
C2—C3—C18	121.13 (15)	C5—C14—C13	112.70 (13)
C4—C3—C2	118.33 (14)	C5—C14—H14A	109.1
C4—C3—C18	120.53 (14)	C5—C14—H14B	109.1
C3—C4—H4	119.1	C13—C14—H14A	109.1
C3—C4—C5	121.72 (14)	C13—C14—H14B	109.1
C5—C4—H4	119.1	H14A—C14—H14B	107.8
C4—C5—C14	120.34 (14)	C8—C15—H15A	109.5
C6—C5—C4	118.48 (14)	C8—C15—H15B	109.5
C6—C5—C14	121.18 (14)	C8—C15—H15C	109.5
C1—C6—H6	119.3	H15A—C15—H15B	109.5
C5—C6—C1	121.30 (14)	H15A—C15—H15C	109.5
C5—C6—H6	119.3	H15B—C15—H15C	109.5
C8—C7—H7	119.3	C10—C16—H16A	109.5
C12—C7—H7	119.3	C10—C16—H16B	109.5
C12—C7—C8	121.48 (14)	C10—C16—H16C	109.5
C7—C8—C15	120.62 (14)	H16A—C16—H16B	109.5
C9—C8—C7	118.62 (13)	H16A—C16—H16C	109.5
C9—C8—C15	120.74 (14)	H16B—C16—H16C	109.5
C8—C9—H9	119.3	C1—C17—H17A	109.5
C8—C9—C10	121.40 (14)	C1—C17—H17B	109.5
C10—C9—H9	119.3	C1—C17—H17C	109.5
C9—C10—C16	121.23 (15)	H17A—C17—H17B	109.5
C11—C10—C9	118.45 (14)	H17A—C17—H17C	109.5
C11—C10—C16	120.32 (14)	H17B—C17—H17C	109.5
C10—C11—H11	119.1	C3—C18—H18A	109.5
C10—C11—C12	121.74 (14)	C3—C18—H18B	109.5
C12—C11—H11	119.1	C3—C18—H18C	109.5
C7—C12—C11	118.31 (13)	H18A—C18—H18B	109.5
C7—C12—C13	121.10 (14)	H18A—C18—H18C	109.5
C11—C12—C13	120.59 (13)	H18B—C18—H18C	109.5

Funding information

We acknowledge financial support by Deutsche Forschungsgemeinschaft and Technische Universität Dortmund/TU Dortmund Technical University within the funding programme Open Access Publishing.

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