4,4′-Dibromo-2-nitro­biphen­yl

Novina, J.J.; Vasuki, G.; Kumar, S.; Thomas, K.R.J.

doi:10.1107/S1600536812000347

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o319

doi:10.1107/S1600536812000347

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4,4′-Dibromo-2-nitrobiphenyl

J. Josephine Novina,^a G. Vasuki,^b ^* Sushil Kumar ^c and K. R. Justin Thomas ^c

^aDepartment of Physics, Idhaya College for Women, Kumbakonam-1, India, ^bDepartment of Physics, Kunthavai Naachiar Govt. Arts College (W) (Autonomous), Thanjavur-7, India, and ^cOrganic Materials Lab, Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667, India
^*Correspondence e-mail: vasuki.arasi@yahoo.com

(Received 27 December 2011; accepted 4 January 2012; online 11 January 2012)

The title compound, C₁₂H₇Br₂NO₂, a biphenyl derivative, displays a twisted conformation with the two benzene rings making a dihedral angle of 55.34 (14)°. The dihedral angle between the nitro group and its parent benzene ring is 26.8 (2)°. The crystal structure is stabilized by intermolecular C—H⋯Br and C—H⋯O interactions, which lead to the formation of chains propagating along the c-axis direction.

Related literature

For the use of dibromo-2-nitro-biphenyl as a crucial precursor in the formation of 2,7-disubstituted carbazole derivatives, see: Dierschke et al. (2003 ); Blouin et al. (2007 ). For details concerning 3,6-disubstituted analogs, see: Thomas et al. (2001 ). For related structures, see: Akhter et al. (2009 ); Hou et al. (2011 ); Kia et al. (2009 ); Rajnikant et al. (1995 ); Sim (1986 ).

Experimental

Crystal data

C₁₂H₇Br₂NO₂
M_r = 357.01
Orthorhombic, P b c n
a = 15.8761 (14) Å
b = 7.4350 (7) Å
c = 20.7517 (13) Å
V = 2449.5 (4) Å³
Z = 8
Mo Kα radiation
μ = 6.61 mm⁻¹
T = 293 K
0.40 × 0.35 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.089, T_max = 0.138
13009 measured reflections
2607 independent reflections
1521 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.095
S = 1.00
2607 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.70 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Br2ⁱ	0.93	2.89	3.798 (3)	165
C9—H9⋯O2ⁱⁱ	0.93	2.57	3.454 (5)	159
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812000347/su2358sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812000347/su2358Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812000347/su2358Isup3.cml

checkCIF report

Comment top

Biphenyl and its derivatives are important industrial intermediates used in the production of heat transfer fluids, formulations for dye carriers used in textile dyeing and polychlorinated biphenyls used in insecticides. The C—Br bond in certain biphenyl derivatives is labile and the compound can be used for the preparation of carboxylic acid functionalized biphenyl derivatives. 4,4'-Dibromo-2-nitro-biphenyl is used as an crucial precursor in the formation of 2,7-disubstituted carbazole derivatives (Dierschke et al., 2003; Blouin et al., 2007), which have been found to display unusual electronic properties when compared to the 3,6-disubstituted analogs (Thomas et al., 2001).

Structures of biphenyl and its derivatives have been studied extensively in the past and even now, because of the differences found in the inter–ring torsion angle ϕ in the solid state (Rajnikant et al., 1995), which alters the electronic properties. In a continuation of our on-going research program aimed at investigating the trends in crystallization and crystal growth of some substituted biphenyl derivatives, the crystal and molecular structure of the title compound is presented herein.

The title compound (Fig. 1) displays a twisted conformation with the two benzene rings making a dihedral angle of 55.34 (14)°. The dihedral angle between the nitro group and its parent benzene ring is 26.76 (20)°. The length of the bond connecting the phenyl rings, 1.483 (5) Å, is close to the standard value of 1.48 Å for a Csp²—Csp² single bond, and to that observed in similar structures, for example 2-Bromo-4'-phenylacetophenone (II) [Sim, 1986], 4-Methoxy-2-nitro-4'-(trifluoromethyl)-biphenyl (III) [Hou et al., 2011], and N-[1-(Biphenyl-4-yl)ethylidene]-N'-(2,4-dinitrophenyl)hydrazine (IV) [Kia et al., 2009]. All the bond lengths and angles are comparable to those obserbed in related structures. The distribution of bond angles around atom C4 is quite similar to that reported for 2-substituted biphenyls with angle C3—C4—C5 considerably less than 120° and angle C3—C4—C10 greater than 120°, as observed in the related structures, Biphenyl-2-methanol (V) [Rajnikant et al., 1995], and 4-(4-Nitrophenoxy) biphenyl (VI) [Akhter et al., 2009]. The two bromine atoms and the nitro group are in antiperiplanar positions with respect to the benzene rings to which they are attached.

In the crystal, there are no classical hydrogen bonds and the crystal structure is stabilized by intermolecular C—H···Br and C—H···O interactions (Table 1 and Fig. 2), which lead to the formation of one-dimensional chains propagating along the c axis direction.

Related literature top

For the use of dibromo-2-nitro-biphenyl as a crucial precursor in the formation of 2,7-disubstituted carbazole derivatives, see: Dierschke et al. (2003); Blouin et al. (2007). For details concerning 3,6-disubstituted analogs, see: Thomas et al. (2001). For related structures, see: Akhter et al. (2009); Hou et al. (2011); Kia et al. (2009); Rajnikant et al. (1995); Sim (1986).

Experimental top

The title compound was synthesized by following a protocol reported in literature (Dierschke et al., 2003), in which the expensive fuming nitric acid was replaced by a potassium nitrate and sulfuric acid mixture. 4,4,-Dibromobiphenyl (25 g) was suspended in 120 ml of glacial acetic acid and heated to 363 K for 45 min. with efficient stirring. A preformed mixture of KNO₃ (18 g) and H₂SO₄ (36 ml) was added drop wise maintaining the temperature at 363 K. After the addition was complete the mixture was heated and stirred for further 30 min. On completion of the reaction, the mixture was cooled and poured into water. The yellow precipitate formed was filtered and recrystallized from ethanol [Yield: 82%]. The spectral data matched with those reported in the literature (Dierschke et al., 2003).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom numbering and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Crystal packing of the title compound viewed along the b axis, showing the C-H···Br and C-H···O interactions as dashed lines (see Table 1 for details).

4,4'-Dibromo-2-nitrobiphenyl top

Crystal data top

C₁₂H₇Br₂NO₂	F(000) = 1376
M_r = 357.01	D_x = 1.936 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 25 reflections
a = 15.8761 (14) Å	θ = 20–30°
b = 7.4350 (7) Å	µ = 6.61 mm⁻¹
c = 20.7517 (13) Å	T = 293 K
V = 2449.5 (4) Å³	Needle, yellow
Z = 8	0.40 × 0.35 × 0.30 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2607 independent reflections
Radiation source: fine-focus sealed tube	1521 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
ω and ϕ scan	θ_max = 27.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −18→20
T_min = 0.089, T_max = 0.138	k = −9→9
13009 measured reflections	l = −16→26

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.041P)² + 1.6705P] where P = (F_o² + 2F_c²)/3
2607 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.70 e Å⁻³

Crystal data top

C₁₂H₇Br₂NO₂	V = 2449.5 (4) Å³
M_r = 357.01	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 15.8761 (14) Å	µ = 6.61 mm⁻¹
b = 7.4350 (7) Å	T = 293 K
c = 20.7517 (13) Å	0.40 × 0.35 × 0.30 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2607 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1521 reflections with I > 2σ(I)
T_min = 0.089, T_max = 0.138	R_int = 0.045
13009 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.00	Δρ_max = 0.40 e Å⁻³
2607 reflections	Δρ_min = −0.70 e Å⁻³
154 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
Br1	0.03710 (3)	0.09619 (7)	0.65877 (2)	0.05528 (18)
Br2	0.15585 (3)	0.40559 (8)	0.15916 (2)	0.06048 (19)
C7	0.1445 (2)	0.3592 (6)	0.24826 (17)	0.0382 (10)
C9	0.1668 (2)	0.1683 (6)	0.33822 (18)	0.0410 (10)
H9	0.1880	0.0618	0.3552	0.049*
C1	0.0668 (2)	0.1609 (5)	0.57419 (16)	0.0321 (9)
O1	0.30721 (17)	0.1125 (4)	0.51041 (14)	0.0524 (8)
C11	0.0974 (3)	0.4456 (6)	0.35168 (19)	0.0438 (11)
H11	0.0702	0.5287	0.3779	0.053*
N	0.26111 (19)	0.2075 (5)	0.47864 (15)	0.0342 (8)
C5	0.0275 (2)	0.2556 (5)	0.46893 (18)	0.0343 (10)
H5	−0.0144	0.2906	0.4403	0.041*
O2	0.28561 (16)	0.3083 (5)	0.43688 (14)	0.0518 (8)
C4	0.1106 (2)	0.2495 (5)	0.44718 (16)	0.0289 (9)
C2	0.1493 (2)	0.1555 (5)	0.55524 (17)	0.0329 (9)
H2	0.1910	0.1212	0.5842	0.039*
C10	0.1272 (2)	0.2897 (5)	0.37828 (16)	0.0292 (9)
C6	0.0050 (2)	0.2116 (5)	0.53120 (17)	0.0362 (10)
H6	−0.0511	0.2162	0.5440	0.043*
C8	0.1752 (2)	0.2031 (7)	0.27314 (19)	0.0467 (12)
H8	0.2018	0.1201	0.2465	0.056*
C3	0.1701 (2)	0.2011 (5)	0.49318 (17)	0.0280 (9)
C12	0.1067 (3)	0.4826 (6)	0.28703 (19)	0.0476 (11)
H12	0.0873	0.5908	0.2701	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0631 (3)	0.0675 (4)	0.0352 (3)	−0.0030 (3)	0.01363 (19)	0.0059 (2)
Br2	0.0541 (3)	0.0981 (5)	0.0293 (2)	0.0006 (3)	0.00445 (18)	0.0110 (3)
C7	0.034 (2)	0.056 (3)	0.025 (2)	−0.002 (2)	−0.0014 (17)	0.002 (2)
C9	0.046 (3)	0.042 (3)	0.034 (2)	0.011 (2)	0.0008 (17)	0.003 (2)
C1	0.035 (2)	0.036 (3)	0.0254 (19)	−0.0034 (18)	0.0028 (16)	−0.0055 (18)
O1	0.0363 (16)	0.074 (2)	0.0470 (19)	0.0164 (17)	−0.0024 (13)	0.0104 (17)
C11	0.054 (3)	0.045 (3)	0.033 (2)	0.015 (2)	0.0106 (18)	0.001 (2)
N	0.0308 (18)	0.042 (2)	0.0297 (18)	−0.0003 (17)	−0.0018 (14)	−0.0033 (17)
C5	0.032 (2)	0.039 (3)	0.031 (2)	0.0032 (19)	−0.0054 (15)	−0.0030 (19)
O2	0.0366 (18)	0.066 (2)	0.0530 (19)	−0.0062 (15)	0.0047 (13)	0.0157 (18)
C4	0.031 (2)	0.029 (2)	0.027 (2)	0.0010 (17)	−0.0027 (15)	−0.0020 (17)
C2	0.031 (2)	0.037 (3)	0.030 (2)	0.0020 (18)	−0.0052 (16)	−0.0032 (18)
C10	0.029 (2)	0.035 (3)	0.0239 (18)	0.0014 (18)	−0.0032 (15)	−0.0006 (19)
C6	0.028 (2)	0.040 (3)	0.040 (2)	0.0018 (19)	0.0046 (17)	−0.005 (2)
C8	0.049 (3)	0.059 (3)	0.032 (2)	0.010 (2)	0.0054 (17)	−0.012 (2)
C3	0.024 (2)	0.032 (2)	0.029 (2)	0.0016 (17)	0.0005 (13)	−0.0016 (18)
C12	0.057 (3)	0.049 (3)	0.037 (2)	0.012 (2)	0.0012 (19)	0.013 (2)

Geometric parameters (Å, º) top

Br1—C1	1.880 (3)	N—O2	1.210 (4)
Br2—C7	1.890 (4)	N—C3	1.477 (4)
C7—C8	1.361 (6)	C5—C6	1.380 (5)
C7—C12	1.361 (6)	C5—C4	1.395 (5)
C9—C10	1.378 (5)	C5—H5	0.9300
C9—C8	1.382 (5)	C4—C3	1.390 (5)
C9—H9	0.9300	C4—C10	1.484 (5)
C1—C2	1.368 (5)	C2—C3	1.372 (5)
C1—C6	1.380 (5)	C2—H2	0.9300
O1—N	1.212 (4)	C6—H6	0.9300
C11—C10	1.369 (5)	C8—H8	0.9300
C11—C12	1.377 (5)	C12—H12	0.9300
C11—H11	0.9300

C8—C7—C12	120.6 (4)	C5—C4—C10	118.2 (3)
C8—C7—Br2	119.5 (3)	C1—C2—C3	119.5 (3)
C12—C7—Br2	119.8 (3)	C1—C2—H2	120.2
C10—C9—C8	120.7 (4)	C3—C2—H2	120.2
C10—C9—H9	119.6	C11—C10—C9	118.0 (3)
C8—C9—H9	119.6	C11—C10—C4	119.8 (3)
C2—C1—C6	120.3 (3)	C9—C10—C4	122.0 (4)
C2—C1—Br1	120.1 (3)	C1—C6—C5	119.0 (3)
C6—C1—Br1	119.7 (3)	C1—C6—H6	120.5
C10—C11—C12	121.7 (4)	C5—C6—H6	120.5
C10—C11—H11	119.2	C7—C8—C9	119.7 (4)
C12—C11—H11	119.2	C7—C8—H8	120.1
O2—N—O1	123.8 (3)	C9—C8—H8	120.1
O2—N—C3	118.7 (3)	C2—C3—C4	123.1 (3)
O1—N—C3	117.5 (3)	C2—C3—N	115.8 (3)
C6—C5—C4	122.7 (3)	C4—C3—N	121.1 (3)
C6—C5—H5	118.6	C7—C12—C11	119.2 (4)
C4—C5—H5	118.6	C7—C12—H12	120.4
C3—C4—C5	115.4 (3)	C11—C12—H12	120.4
C3—C4—C10	126.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Br2ⁱ	0.93	2.89	3.798 (3)	165
C9—H9···O2ⁱⁱ	0.93	2.57	3.454 (5)	159

Symmetry codes: (i) −x+1/2, −y+1/2, z+1/2; (ii) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₇Br₂NO₂
M_r	357.01
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	15.8761 (14), 7.4350 (7), 20.7517 (13)
V (Å³)	2449.5 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	6.61
Crystal size (mm)	0.40 × 0.35 × 0.30

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.089, 0.138
No. of measured, independent and observed [I > 2σ(I)] reflections	13009, 2607, 1521
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.095, 1.00
No. of reflections	2607
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.70

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Br2ⁱ	0.93	2.89	3.798 (3)	165
C9—H9···O2ⁱⁱ	0.93	2.57	3.454 (5)	159

Symmetry codes: (i) −x+1/2, −y+1/2, z+1/2; (ii) −x+1/2, y−1/2, z.

Acknowledgements

GV thanks the UGC, India, for financial assistance under the Minor Research Project (2010–2011). The authors also thank the Sophisticated Analytical Instrument Facility, IIT Madras, Chennai, for the single crystal X-ray data collection.

References

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