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

Miao, S.-B.; Deng, D.-S.; Liu, X.-M.; Ji, B.-M.

doi:10.1107/S1600536809033790

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2314

doi:10.1107/S1600536809033790

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2,2′-Dimethoxy-6,6′-dinitrobiphenyl

Shao-Bin Miao,^a Dong-Sheng Deng,^a Xian-Ming Liu ^a and Bao-Ming Ji ^a ^*

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: lyhxxjbm@126.com

(Received 28 July 2009; accepted 24 August 2009; online 5 September 2009)

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 ). For asymmetric synthesis using chiral ligands with C₂ symmetry, see: Jiang et al. (2001 ); García et al. (2002 ). For synthetic methods for chiral compounds, see: Brunel (2005 ); Kočovský et al. (2003 ). For related biphenyl structures, see: Fischer et al. (2007 ). For related structural data see: Yang et al. (2005 ).

Experimental

Crystal data

C₁₄H₁₂N₂O₆
M_r = 304.26
Monoclinic, C 2/c
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 ) 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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.097
S = 1.03
1298 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O3ⁱ	0.96	2.48	3.426 (3)	169
Symmetry code: (i) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

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) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

For the synthesis of the title compound, see: Chen et al. (2001). For asymmetric synthesis using chiral ligands with C₂-symmetry, see: Jiang et al. (2001); García et al. (2002). For synthetic methods for chiral compounds, see: Brunel (2005); Kočovský et al. (2003). For related biphenyl structures, see: Fischer et al. (2007). For related literature, see: Yang et al. (2005).

Experimental top

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.

Computing details top

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

Figures top

	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.

2,2'-Dimethoxy-6,6'-dinitrobiphenyl top

Crystal data top

C₁₄H₁₂N₂O₆	F(000) = 632
M_r = 304.26	D_x = 1.441 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1790 reflections
a = 18.236 (3) Å	θ = 2.5–25.7°
b = 7.7826 (12) Å	µ = 0.12 mm⁻¹
c = 10.9079 (17) Å	T = 294 K
β = 115.089 (2)°	Block, yellow
V = 1402.0 (4) Å³	0.30 × 0.18 × 0.18 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1298 independent reflections
Radiation source: fine-focus sealed tube	1009 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→22
T_min = 0.966, T_max = 0.979	k = −9→9
5102 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0401P)² + 0.8036P] where P = (F_o² + 2F_c²)/3
1298 reflections	(Δ/σ)_max < 0.001
101 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₄H₁₂N₂O₆	V = 1402.0 (4) Å³
M_r = 304.26	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.236 (3) Å	µ = 0.12 mm⁻¹
b = 7.7826 (12) Å	T = 294 K
c = 10.9079 (17) Å	0.30 × 0.18 × 0.18 mm
β = 115.089 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1298 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1009 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.979	R_int = 0.019
5102 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.03	Δρ_max = 0.14 e Å⁻³
1298 reflections	Δρ_min = −0.13 e Å⁻³
101 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

	x	y	z	U_iso*/U_eq
C1	0.49134 (9)	0.22562 (19)	0.67636 (14)	0.0387 (4)
C2	0.54245 (9)	0.2962 (2)	0.62577 (15)	0.0434 (4)
C3	0.52777 (12)	0.2896 (2)	0.49065 (17)	0.0546 (5)
H3	0.5639	0.3378	0.4607	0.066*
C4	0.45847 (12)	0.2102 (2)	0.40223 (17)	0.0588 (5)
H4	0.4471	0.2058	0.3107	0.071*
C5	0.40569 (11)	0.1370 (2)	0.44656 (16)	0.0540 (5)
H5	0.3589	0.0835	0.3852	0.065*
C6	0.42203 (9)	0.1426 (2)	0.58296 (15)	0.0444 (4)
C7	0.30000 (13)	−0.0071 (4)	0.5464 (2)	0.0944 (8)
H7A	0.2673	0.0767	0.4817	0.142*
H7B	0.2716	−0.0485	0.5971	0.142*
H7C	0.3110	−0.1012	0.4998	0.142*
N1	0.61559 (9)	0.3880 (2)	0.71661 (15)	0.0557 (4)
O1	0.37432 (7)	0.06986 (18)	0.63620 (11)	0.0594 (4)
O2	0.61327 (8)	0.47507 (17)	0.80791 (13)	0.0615 (4)
O3	0.67594 (9)	0.3739 (3)	0.69543 (17)	0.0967 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0399 (8)	0.0425 (8)	0.0345 (8)	0.0057 (6)	0.0166 (7)	0.0011 (6)
C2	0.0464 (9)	0.0454 (9)	0.0426 (8)	0.0044 (7)	0.0229 (7)	0.0023 (7)
C3	0.0722 (12)	0.0549 (10)	0.0508 (10)	0.0071 (9)	0.0399 (9)	0.0053 (8)
C4	0.0853 (14)	0.0566 (11)	0.0369 (8)	0.0117 (10)	0.0283 (10)	0.0036 (8)
C5	0.0610 (11)	0.0545 (10)	0.0372 (8)	0.0046 (9)	0.0119 (8)	−0.0031 (8)
C6	0.0452 (9)	0.0473 (9)	0.0388 (8)	0.0033 (7)	0.0159 (7)	0.0004 (7)
C7	0.0600 (13)	0.142 (2)	0.0750 (14)	−0.0445 (14)	0.0224 (12)	−0.0253 (15)
N1	0.0500 (8)	0.0679 (10)	0.0571 (9)	−0.0031 (7)	0.0302 (7)	0.0073 (8)
O1	0.0473 (7)	0.0794 (9)	0.0474 (7)	−0.0193 (6)	0.0162 (6)	−0.0058 (6)
O2	0.0612 (8)	0.0665 (8)	0.0570 (7)	−0.0133 (6)	0.0253 (6)	−0.0081 (7)
O3	0.0604 (9)	0.1503 (16)	0.0999 (12)	−0.0197 (10)	0.0538 (9)	−0.0120 (11)

Geometric parameters (Å, º) top

C1—C2	1.383 (2)	C5—C6	1.389 (2)
C1—C6	1.400 (2)	C5—H5	0.9300
C1—C1ⁱ	1.500 (3)	C6—O1	1.3576 (19)
C2—C3	1.383 (2)	C7—O1	1.424 (2)
C2—N1	1.466 (2)	C7—H7A	0.9600
C3—C4	1.370 (3)	C7—H7B	0.9600
C3—H3	0.9300	C7—H7C	0.9600
C4—C5	1.371 (3)	N1—O2	1.2200 (18)
C4—H4	0.9300	N1—O3	1.2217 (18)

C2—C1—C6	116.51 (13)	C6—C5—H5	120.0
C2—C1—C1ⁱ	123.77 (15)	O1—C6—C5	124.06 (15)
C6—C1—C1ⁱ	119.63 (14)	O1—C6—C1	115.19 (13)
C1—C2—C3	123.51 (15)	C5—C6—C1	120.75 (15)
C1—C2—N1	119.86 (13)	O1—C7—H7A	109.5
C3—C2—N1	116.60 (14)	O1—C7—H7B	109.5
C4—C3—C2	118.11 (16)	H7A—C7—H7B	109.5
C4—C3—H3	120.9	O1—C7—H7C	109.5
C2—C3—H3	120.9	H7A—C7—H7C	109.5
C3—C4—C5	121.01 (15)	H7B—C7—H7C	109.5
C3—C4—H4	119.5	O2—N1—O3	123.39 (16)
C5—C4—H4	119.5	O2—N1—C2	119.06 (13)
C4—C5—C6	120.08 (17)	O3—N1—C2	117.55 (16)
C4—C5—H5	120.0	C6—O1—C7	118.46 (14)

C6—C1—C2—C3	0.7 (2)	C2—C1—C6—O1	178.01 (14)
C1ⁱ—C1—C2—C3	177.26 (13)	C1ⁱ—C1—C6—O1	1.26 (19)
C6—C1—C2—N1	178.92 (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—C4	0.6 (3)	C1—C2—N1—O2	−36.5 (2)
N1—C2—C3—C4	−177.73 (16)	C3—C2—N1—O2	141.90 (16)
C2—C3—C4—C5	−0.9 (3)	C1—C2—N1—O3	144.16 (17)
C3—C4—C5—C6	0.0 (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—C1	1.3 (3)	C1—C6—O1—C7	175.90 (18)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O3ⁱⁱ	0.96	2.48	3.426 (3)	169

Symmetry code: (ii) x−1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₆
M_r	304.26
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	18.236 (3), 7.7826 (12), 10.9079 (17)
β (°)	115.089 (2)
V (Å³)	1402.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.18 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.966, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	5102, 1298, 1009
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.097, 1.03
No. of reflections	1298
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.13

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O3ⁱ	0.96	2.48	3.426 (3)	169

Symmetry code: (i) x−1/2, y−1/2, z.

Acknowledgements

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

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