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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2314.
Published online 2009 September 5. doi:  10.1107/S1600536809033790
PMCID: PMC2970430

2,2′-Dimeth­oxy-6,6′-dinitro­biphen­yl

Abstract

In the title compound, C14H12N2O6, the half mol­ecule in the asymmetric unit of the cell is completed by a crystallographic twofold rotation axis, and the two benzene rings of the complete mol­ecule make a dihedral angle of 60.5 (3)°. Furthermore, inter­molecular weak C—H(...)O hydrogen bonds link adjacent mol­ecules, forming a two-dimensional sheet. These sheets are stablized by face-to-face weak π–π contacts [centroid–centroid distance = 3.682 (1) Å] between the nearly parallel [dihedral angle = 0.12 (7)°] benzene rings of the neighboring mol­ecules, resulting in a three-dimensional network.

Related literature

For the synthesis of the title compound, see: Chen et al. (2001 [triangle]). For asymmetric synthesis using chiral ligands with C 2 symmetry, see: Jiang et al. (2001 [triangle]); García et al. (2002 [triangle]). For synthetic methods for chiral compounds, see: Brunel (2005 [triangle]); Kočovský et al. (2003 [triangle]). For related biphenyl structures, see: Fischer et al. (2007 [triangle]). For related structural data see: Yang et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2314-scheme1.jpg

Experimental

Crystal data

  • C14H12N2O6
  • M r = 304.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2314-efi1.jpg
  • a = 18.236 (3) Å
  • b = 7.7826 (12) Å
  • c = 10.9079 (17) Å
  • β = 115.089 (2)°
  • V = 1402.0 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 294 K
  • 0.30 × 0.18 × 0.18 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.966, T max = 0.979
  • 5102 measured reflections
  • 1298 independent reflections
  • 1009 reflections with I > 2σ(I)
  • R int = 0.019

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.097
  • S = 1.03
  • 1298 reflections
  • 101 parameters
  • H-atom parameters constrained
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.13 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97 and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033790/si2193sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033790/si2193Isup2.hkl

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

Acknowledgments

This work was supported by the Youth Foundation of Luoyang Normal University (No. 10000409).

supplementary crystallographic information

Comment

A large number of chiral compounds with C2-symmetry are widely used as chiral auxiliaries and ligands in asymmetric synthesis and have shown high stereocontrol properties in a wide range of asymmetric transformations (Jiang et al. 2001; García et al. 2002). Design and synthesis of such compounds play a very important role in the development of highly enantioselective asymmetric reactions. Thus, it is not surprising that a lot of methods have been developed to obtain these chiral compounds (Brunel 2005; Kočovský et al. 2003). In this paper, we report the synthesis and crystal structure of the title compound with C2-symmetry.

A view of the molecular structure of the title compound is given in Fig.1. All bond lengths and angles are in the expected range and in good agreement with those reported previously (Yang et al. 2005). The dihedral angle between two benzene rings is 60.5 (3)°, which is considerable larger than those found in other biphenyls (Fischer et al. 2007), possibly due to the concomitant effects of the steric hindrance of adjacent methoxy and nitro groups.

In the crystal structure, each molecule is connected by four adjacent molecules through intermolecular C—H···O hydrogen bonds (Table 1), between methoxy groups and O atoms of the adjacent nitro groups, leading to the formation of a two-dimensional sheet in the ac plane. The sheets are further connected into a three-dimensional network(Fig.2) by the face-to-face weak π–π contacts between nearly parallel benzene rings of the neighboring title molecules. The Cg1···Cg1iii distance is 3.6823 (11) Å, the perpendicular distance between the rings is 3.410 Å, and the slippage between the rings is 1.389 Å. Cg1 is the centroid of the benzene ring C1 - C6, the symmetry code iii = 1 - x, -y, 1 - z.

Experimental

The title compound was synthesized by a reported method (Chen, et al. 2001),namely, a mixture of 2-iodo-3-nitroanisol (14 g, 0.05 mol) and activated copper brone (9.5 g, 0.15 mol), 50 ml of dimethylformamide was stirried at 140°C for 4 h under nitrogen atmosphere. Yellow crystals suitable for X-ray diffraction study were obtained from a solution in acetic ester.

Refinement

All of the non-hydrogen atoms were refined anisotropically. The hydrogen atoms were assigned with common isotropic displacement factors Uiso(H) = 1.2 times Ueq(C,N) and 1.5 times Ueq(O), respectively, and included in the final refinement by using geometrical restraints, with C–H distances of 0.93 Å.

Figures

Fig. 1.
ORTEP drawing (30% probability displacement ellipsoids) of a single molecule of the title compound.
Fig. 2.
three-dimensional structures of the title compound.

Crystal data

C14H12N2O6F(000) = 632
Mr = 304.26Dx = 1.441 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1790 reflections
a = 18.236 (3) Åθ = 2.5–25.7°
b = 7.7826 (12) ŵ = 0.12 mm1
c = 10.9079 (17) ÅT = 294 K
β = 115.089 (2)°Block, yellow
V = 1402.0 (4) Å30.30 × 0.18 × 0.18 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer1298 independent reflections
Radiation source: fine-focus sealed tube1009 reflections with I > 2σ(I)
graphiteRint = 0.019
[var phi] and ω scansθmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −22→22
Tmin = 0.966, Tmax = 0.979k = −9→9
5102 measured reflectionsl = −13→13

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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0401P)2 + 0.8036P] where P = (Fo2 + 2Fc2)/3
1298 reflections(Δ/σ)max < 0.001
101 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = −0.13 e Å3

Special details

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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)

xyzUiso*/Ueq
C10.49134 (9)0.22562 (19)0.67636 (14)0.0387 (4)
C20.54245 (9)0.2962 (2)0.62577 (15)0.0434 (4)
C30.52777 (12)0.2896 (2)0.49065 (17)0.0546 (5)
H30.56390.33780.46070.066*
C40.45847 (12)0.2102 (2)0.40223 (17)0.0588 (5)
H40.44710.20580.31070.071*
C50.40569 (11)0.1370 (2)0.44656 (16)0.0540 (5)
H50.35890.08350.38520.065*
C60.42203 (9)0.1426 (2)0.58296 (15)0.0444 (4)
C70.30000 (13)−0.0071 (4)0.5464 (2)0.0944 (8)
H7A0.26730.07670.48170.142*
H7B0.2716−0.04850.59710.142*
H7C0.3110−0.10120.49980.142*
N10.61559 (9)0.3880 (2)0.71661 (15)0.0557 (4)
O10.37432 (7)0.06986 (18)0.63620 (11)0.0594 (4)
O20.61327 (8)0.47507 (17)0.80791 (13)0.0615 (4)
O30.67594 (9)0.3739 (3)0.69543 (17)0.0967 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0399 (8)0.0425 (8)0.0345 (8)0.0057 (6)0.0166 (7)0.0011 (6)
C20.0464 (9)0.0454 (9)0.0426 (8)0.0044 (7)0.0229 (7)0.0023 (7)
C30.0722 (12)0.0549 (10)0.0508 (10)0.0071 (9)0.0399 (9)0.0053 (8)
C40.0853 (14)0.0566 (11)0.0369 (8)0.0117 (10)0.0283 (10)0.0036 (8)
C50.0610 (11)0.0545 (10)0.0372 (8)0.0046 (9)0.0119 (8)−0.0031 (8)
C60.0452 (9)0.0473 (9)0.0388 (8)0.0033 (7)0.0159 (7)0.0004 (7)
C70.0600 (13)0.142 (2)0.0750 (14)−0.0445 (14)0.0224 (12)−0.0253 (15)
N10.0500 (8)0.0679 (10)0.0571 (9)−0.0031 (7)0.0302 (7)0.0073 (8)
O10.0473 (7)0.0794 (9)0.0474 (7)−0.0193 (6)0.0162 (6)−0.0058 (6)
O20.0612 (8)0.0665 (8)0.0570 (7)−0.0133 (6)0.0253 (6)−0.0081 (7)
O30.0604 (9)0.1503 (16)0.0999 (12)−0.0197 (10)0.0538 (9)−0.0120 (11)

Geometric parameters (Å, °)

C1—C21.383 (2)C5—C61.389 (2)
C1—C61.400 (2)C5—H50.9300
C1—C1i1.500 (3)C6—O11.3576 (19)
C2—C31.383 (2)C7—O11.424 (2)
C2—N11.466 (2)C7—H7A0.9600
C3—C41.370 (3)C7—H7B0.9600
C3—H30.9300C7—H7C0.9600
C4—C51.371 (3)N1—O21.2200 (18)
C4—H40.9300N1—O31.2217 (18)
C2—C1—C6116.51 (13)C6—C5—H5120.0
C2—C1—C1i123.77 (15)O1—C6—C5124.06 (15)
C6—C1—C1i119.63 (14)O1—C6—C1115.19 (13)
C1—C2—C3123.51 (15)C5—C6—C1120.75 (15)
C1—C2—N1119.86 (13)O1—C7—H7A109.5
C3—C2—N1116.60 (14)O1—C7—H7B109.5
C4—C3—C2118.11 (16)H7A—C7—H7B109.5
C4—C3—H3120.9O1—C7—H7C109.5
C2—C3—H3120.9H7A—C7—H7C109.5
C3—C4—C5121.01 (15)H7B—C7—H7C109.5
C3—C4—H4119.5O2—N1—O3123.39 (16)
C5—C4—H4119.5O2—N1—C2119.06 (13)
C4—C5—C6120.08 (17)O3—N1—C2117.55 (16)
C4—C5—H5120.0C6—O1—C7118.46 (14)
C6—C1—C2—C30.7 (2)C2—C1—C6—O1178.01 (14)
C1i—C1—C2—C3177.26 (13)C1i—C1—C6—O11.26 (19)
C6—C1—C2—N1178.92 (14)C2—C1—C6—C5−1.6 (2)
C1i—C1—C2—N1−4.5 (2)C1i—C1—C6—C5−178.36 (13)
C1—C2—C3—C40.6 (3)C1—C2—N1—O2−36.5 (2)
N1—C2—C3—C4−177.73 (16)C3—C2—N1—O2141.90 (16)
C2—C3—C4—C5−0.9 (3)C1—C2—N1—O3144.16 (17)
C3—C4—C5—C60.0 (3)C3—C2—N1—O3−37.5 (2)
C4—C5—C6—O1−178.25 (16)C5—C6—O1—C7−4.5 (3)
C4—C5—C6—C11.3 (3)C1—C6—O1—C7175.90 (18)

Symmetry codes: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7B···O3ii0.962.483.426 (3)169

Symmetry codes: (ii) x−1/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SI2193).

References

  • Bruker (2004). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
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