3,5-Dimeth­oxy-4′-methyl­biphen­yl

Manu Lahtinen; Kalle Nättinen; Sami Nummelin

doi:10.1107/S1600536813006053

. 2013 Mar 9;69(Pt 4):o510–o511. doi: 10.1107/S1600536813006053

3,5-Dimethoxy-4′-methylbiphenyl

Manu Lahtinen ^a, Kalle Nättinen ^b, Sami Nummelin ^c,^*

PMCID: PMC3629539 PMID: 23634057

Abstract

The title compound, C₁₅H₁₆O₂, crystallizes with three independent molecules in the asymmetric unit. The intramolecular torsion angle between the aromatic rings of each molecule are −36.4 (3), 41.3 (3) and −37.8 (3)°. In the crystal, the complicated packing of the molecules forms wave-like layers along the b and c axes. The molecules are connected via extensive methoxy–phenyl C—H⋯π interactions. A weak C—H⋯O hydrogen-bonding network also exists between methoxy O atoms and aromatic or methoxy H atoms.

Related literature

For discussion of hydrogen bonding, see: Steiner (2002 ▶). For similar structures, see: Nakagawa et al. (1984 ▶); Pandi et al. (2000 ▶); Lahtinen et al. (2013a ▶,b ▶). For details of the synthesis, see: Dol et al. (1998 ▶); Percec et al. (2006 ▶). The Suzuki–Miyaura cross-coupling reaction (Miyaura & Suzuki, 1995 ▶) is widely used for the synthesis of biphenyls and related biaryl structures in organic, polymer, and supramolecular chemistry. Such structures are frequently used as building blocks for e.g. precursors to liquid crystals (Solladié & Zimmermann 1984 ▶), supramolecular polymers (Brunsveld et al. 2001 ▶), dendritic molecules (Nummelin et al. 2000 ▶) as well as Percec-type self-assembling biphenyl dendrons (Percec et al., 2006 ▶, 2007 ▶; Rosen et al., 2009 ▶, 2010 ▶). graphic file with name e-69-0o510-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₆O₂
M _r = 228.28
Orthorhombic,
a = 7.16505 (18) Å
b = 15.3511 (4) Å
c = 33.3834 (8) Å
V = 3671.88 (16) Å³
Z = 12
Cu Kα radiation
μ = 0.64 mm⁻¹
T = 123 K
0.31 × 0.07 × 0.04 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: analytical (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.900, T _max = 0.979
8494 measured reflections
5862 independent reflections
5181 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.094
S = 1.04
5862 reflections
470 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ▶), 2062 Friedel pairs
Flack parameter: 0.09 (19)

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Click here for additional data file.^{(44.1KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813006053/fj2619sup1.cif

e-69-0o510-sup1.cif^{(44.1KB, cif)}

Click here for additional data file.^{(287KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006053/fj2619Isup2.hkl

e-69-0o510-Isup2.hkl^{(287KB, hkl)}

Click here for additional data file.^{(5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813006053/fj2619Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1–Cg6 are the centroids of C26–C31, C2–C7, C33–C38, C20–C25, C8–C13 and C26–C31 aromatic rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C29—H29⋯O15ⁱ	0.95	2.40	3.321 (2)	164
C25—H25⋯O51ⁱⁱ	0.95	2.84	3.459 (3)	124
C24—H24⋯O17ⁱⁱⁱ	0.95	2.91	3.703 (3)	141
C16—H16A⋯O34^iv	0.98	2.68	3.521 (3)	143
C52—H52A⋯O17^v	0.98	2.63	3.398 (3)	136
C18—H18A⋯Cg1ⁱⁱⁱ	0.98	2.89	3.686 (3)	142
C16—H16C⋯Cg2^iv	0.98	2.62	3.366 (3)	139
C33—H33B⋯Cg3ⁱⁱⁱ	0.98	3.05	3.476 (3)	115
C52—H52B⋯Cg4^v	0.98	2.77	3.424 (3)	134
C35—H35C⋯Cg5ⁱⁱⁱ	0.98	2.77	3.639 (3)	146
C35—H35B⋯Cg5	0.98	2.78	3.563 (3)	143
C18—H18C⋯Cg6^vi	0.98	2.75	3.663 (3)	148

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

SN acknowledges the Academy of Finland for financial support (No. 138850).

supplementary crystallographic information

Comment

The Suzuki-Miyaura cross-coupling reaction (Miyaura & Suzuki 1995) is widely used for the synthesis of biphenyls and related biaryl structures in organic, polymer, and supramolecular chemistry. Such structures are frequently used as building blocks for e.g precursors to liquid crystals (Solladié & Zimmermann 1984), supramolecular polymers (Brunsveld et al. 2001), dendritic molecules (Nummelin et al. 2000), and recently, Percec-type self-assembling supramolecular dendrimers (Percec et al. 2006, 2007; Rosen et al. 2009, 2010). Herein we report the crystal structure of title compound 3,5-dimethoxy-4'-methylbiphenyl (I) as a contribution to a structural study of biphenyl derivatives.

The compound (I) crystallizes in orthorhombic P2₁2₁2₁ (No. 19) spacegroup without any solvent molecules. The asymmetric unit is consisted of three crystallographically independent but conformationally quite similar molecules (Figure 1). Major difference in conformation can be found in the orientation of one of the methoxy groups as can be seen in Figure 2. The intramolecular dihedral angles between the phenyl rings are -36.4 (3)° [C(4)–C(5)–C(8)–C(9)], 41.3 (3)° [C(22)–C(23)–C(26)–C(27)], and -37.8 (3)° [C(39)–C(40)–C(43)–C(44)], respectively. The complicated packing scheme of molecules form wave-like layers (layer on b- and c-axes) that are packed along a-axis (Figure 3). On each wave-like layer, molecules are orientated by 90° turns in a sequence of three crystallographically independent molecules (Figure 4). Extensive network of C–H···π and π–π interactions occur between methoxy groups and neighboring phenyl groups and between the phenyl rings (Figure 5) with distances varying from 3.366 (3) to 3.686 (3) Å and from 4.8418 (11) to 4.9137 (12) Å, respectively (Table 1). Also weak C–H···O hydrogen bond networks (Steiner 2002) exist between the methoxy groups of 3,5-dimethoxyphenyl rings and neighbouring hydrogen atoms located either on methoxy groups or in aromatic rings with D···A distances varying from 3.321 (2) to 3.703 (3) Å.

Experimental

A flame dried Schlenk-tube was charged with 4-methylphenylboronic acid (6.00 g, 44.13 mmol), potassium fluoride (5.13 g, 88.30 mmol), 1-chloro-3,5-dimethoxybenzene (5.08 g, 29.43 mmol), Pd(OAc)₂ (66 mg, 0.29 mmol, 1.0 mol%) and 2-(di-tert-butylphosphino)biphenyl (176 mg, 0.59 mmol, 2.0 mol%). The flask was sealed with a teflon screwcap, evacuated/backfilled with argon five times. Then dry, degassed THF (40 ml) was added via syringe. The reaction mixture was stirred at ambient temperature until the aryl chloride had been completely consumed as judged by GC analysis. The mixture was diluted with ether, filtered, and washed with 1 M NaOH. The aqueous layer was extracted with ether, the combined organic layer was washed with brine and dried with MgSO₄. After evaporation the crude material was purified by flash column chromatography: silica gel/CH₂Cl₂. The solvent was evaporated and the product was re-crystallized from EtOH affording 6.40 g (95%) of a white crystalline solid. Crystals suitable for a single-crystal structure determination were obtained from a slow evaporation of ethanol.