3,4-Dimeth­oxy-4′-nitro-1,1′-biphen­yl

Xin-Min Li; Yan-Jun Hou; Wen-Yi Chu; Zhi-Zhong Sun

doi:10.1107/S1600536812013657

. 2012 Apr 4;68(Pt 5):o1292. doi: 10.1107/S1600536812013657

3,4-Dimethoxy-4′-nitro-1,1′-biphenyl

Xin-Min Li ^a, Yan-Jun Hou ^a,^*, Wen-Yi Chu ^a, Zhi-Zhong Sun ^a

PMCID: PMC3344440 PMID: 22590202

Abstract

The title compound, C₁₄H₁₃NO₄, was prepared through a palladium-catalysed Suzuki–Miyaura coupling reaction. The asymmetric unit comprises two molecules related by pseudo-inversion symmetry. The dihedral angles between the benzene rings in the two molecules are 44.30 (6) and 48.50 (6)° while those between the benzene ring and the nitro group are 6.54 (13) and 5.73 (10)°. The crystal packing is defined only by Van der Waals interactions.

Related literature

For general background to the synthesis and properties of 3,4-dimethoxy-4′-nitro-1,1′-biphenyl, see: Suzuki (1999 ▶); Razler et al. (2009 ▶); Hou et al. (2011 ▶); Li et al. (2012 ▶). For the biological activity of biphenyl derivatives, see: Kimpe et al. (1996 ▶).

Experimental

Crystal data

C₁₄H₁₃NO₄
M _r = 259.25
Monoclinic,
a = 16.2714 (14) Å
b = 7.6529 (7) Å
c = 20.2448 (18) Å
β = 91.691 (1)°
V = 2519.9 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.28 × 0.24 × 0.22 mm

Data collection

Bruker APEXII CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) ▶ T _min = 0.972, T _max = 0.978
15429 measured reflections
4401 independent reflections
3201 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.104
S = 1.05
4401 reflections
348 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812013657/kp2400sup1.cif

e-68-o1292-sup1.cif^{(24.1KB, cif)}

Supplementary material file. DOI: 10.1107/S1600536812013657/kp2400Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812013657/kp2400Isup3.hkl

e-68-o1292-Isup3.hkl^{(215.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812013657/kp2400Isup4.cml

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

Acknowledgments

We thank the Foundation of Heilongjiang Education Committee (Nos. 12521413 and 12511383), the Key Laboratory of Chemical Engineering Processes and Technology for High-Efficiency Conversion, College of Heilongjiang Province and Heilongjiang University, China, for supporting this study.

supplementary crystallographic information

Comment

The palladium-catalyzed Suzuki-Miyaura coupling reaction attracts a considerable interest. The biological activity of biphenyl derivatives (Suzuki, 1999; Razler et al., 2009; Kimpe et al., 1996; Hou et al., 2011; Li et al., 2012) has been described in the literature. We have prepared 3,4-dimethoxy-4'-nitro-1,1'-biphenyl as a potentially active antiviral compound. In the title compound there are two molecules in an asymmetric unit ( Fig. 1). The dihedral angle between the benzene rings (C1-C2-C3-C4-C5-C6) and (C7-C8-C9-C10-C11-C12) is 44.30 (6)°; (C15-C16-C17-C18-C19-C20) and (C21-C22-C23-C24-C25-C26) is 48.50 (6)°. The dihedral angle between the benzene ring (C1-C2-C3-C4-C5-C6) and nitro group (N1-O1-O2) is 6.54 (13)°. The dihedral angle between the benzene ring (C15-C16-C17-C18 C19-C20) and nitro group (N2-O5-O6) is 5.73 (10)°. Van der Waals interactions dominate the crystal packing (Fig. 2).

Experimental

To a solution of 1-bromo-4-nitrobenzene (5 mmol) and 3,4-dimethoxyphenylboronic acid (6 mmol) in 20 mL water and 20 mL methanol, Pd(OAc)₂ (5 mmol) and K₂CO₃ (10 mmol) were added. After stirring the reaction mixture for 6 h at 323 K, the aqueous phases were extracted with 100 mL ethyl acetate. The organic extracts were washed with 200 mL saturated aqueous sodium chlorid, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting crude material was purified via silica gel chromatography (petroleum ether) to afford a translucent solid in a yield of 63%. Crystals suitable for single-crystal X-ray diffraction were obtained by recrystallisation from methanol at room temperature in a total yield of 44%. Analysis found: C 64.9, H 5.2, N 5.5%; C₁₄H₁₃NO₄ requires: 64.9, H 5.1, N 5.4%. ¹H NMR (400 MHz, CDCl₃) 8.34 - 8.23 (m, 2H), 7.77 - 7.66 (m, 2H), 7.21 (dd, J = 8.3, 2.2 Hz, 1H), 7.13 (d, J = 2.2 Hz, 1H), 6.99 (d, J = 8.3 Hz, 1H), 3.97 (s, 3H), 3.95 (s, 3H).