2,2′-Di­nitro­di­benzyl

Yathirajan, H.S.; Nagaraj, B.; Nagaraja, P.; Lynch, D.E.

doi:10.1107/S1600536804030326

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 60| Part 12| December 2004| Pages o2455-o2456

https://doi.org/10.1107/S1600536804030326

2,2′-Dinitrodibenzyl

Hemmige S. Yathirajan,^a Basavegowda Nagaraj,^a Padmarajaiah Nagaraja ^a and Daniel E. Lynch ^b ^*

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^bSchool of Science and the Environment, Coventry University, Coventry CV1 5FB, England
^*Correspondence e-mail: apx106@coventry.ac.uk

(Received 18 November 2004; accepted 22 November 2004; online 27 November 2004)

In the title compound, C₁₄H₁₂N₂O₄, there is an inversion centre at the mid-point of the ethylene bridge. The nitro group is inclined at an angle of 33 (2)° to the plane of the phenyl ring. The benzene rings in each molecule are coplanar, but the dihedral angle between the benzene rings in neighbouring molecules is 55.2 (1)°.

Comment

The title compound, (I), is an intermediate in the syntheses of the anticonvulsant drugs carbamazepine and oxcarbazepine, and also the antidepressant drugs imipramine and desipramine. The Cambridge Structural Database (Version of Aptil 2004; Allen, 2002 ) reveals that there are currently eight known crystal structures of 2,2′-disubstituted dibenzyls, including derivatives with substituents such as bromo, methyl and methoxy groups, but not nitro. In the title compound (Fig. 1), there is an inversion centre at the mid-point of the ethylene bridge. Thus, the molecule adopts a stepped trans conformation with respect to the benzene rings and nitro groups, respectively. The nitro group is inclined at an angle of 33 (2)° to the plane of the benzene ring. The benzene rings in each molecule are coplanar, but the dihedral angle between the benzene rings in neighbouring molecules is 55.2 (1)°.

Figure 1
Molecular configuration and atom-numbering scheme for (I

). Displacement ellipsoids are drawn at the 50% probability level and H atoms as spheres of arbitrary radius. [Symmetry code: (a) −x, 1 − y, 1 − z.]

Experimental

The title compound was obtained from Max India Ltd and crystals were grown from ethanol.

Crystal data

C₁₄H₁₂N₂O₄
M_r = 272.26
Monoclinic, P2₁/c
a = 7.5678 (8) Å
b = 14.4964 (16) Å
c = 5.9874 (5) Å
β = 108.607 (6)°
V = 622.52 (11) Å³
Z = 2
D_x = 1.452 Mg m⁻³
Mo Kα radiation
Cell parameters from 1390 reflections
θ = 2.9–27.5°
μ = 0.11 mm⁻¹
T = 120 (2) K
Plate, colourless
0.36 × 0.10 × 0.04 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan SADABS (Sheldrick, 2003 ) T_min = 0.962, T_max = 0.996
5201 measured reflections
1092 independent reflections
730 reflections with I > 2σ(I)
R_int = 0.128
θ_max = 25.0°
h = −8 → 8
k = −17 → 17
l = −7 → 7

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.165
S = 1.03
1092 reflections
92 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0865P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Extinction correction: SHELXL
Extinction coefficient: 0.033 (12)

All H atoms were included in the refinement at calculated positions, with C—H distances of 0.95 (aromatic H atoms) and 0.99 Å (CH₂ H atoms), and refined as riding, with U_iso(H) = 1.25U_eq(carrier atom). The high R_int is the result of weak high-angle data.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO, SCALEPACK (Otwinowski & Minor, 1997) and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON97 (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, default. DOI: https://doi.org/10.1107/S1600536804030326/sj6030sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804030326/sj6030Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO, SCALEPACK (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON97 (Spek, 2003); software used to prepare material for publication: SHELXL97.

2,2'-dinitrodibenzyl top

Crystal data top

C₁₄H₁₂N₂O₄	F(000) = 284
M_r = 272.26	D_x = 1.452 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 404 K K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.5678 (8) Å	Cell parameters from 1390 reflections
b = 14.4964 (16) Å	θ = 2.9–27.5°
c = 5.9874 (5) Å	µ = 0.11 mm⁻¹
β = 108.607 (6)°	T = 120 K
V = 622.52 (11) Å³	Plate, colourless
Z = 2	0.36 × 0.10 × 0.04 mm

Data collection top

Bruker Nonius 95 mm CCD camera on κ-goniostat diffractometer	1092 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	730 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.128
Detector resolution: 9.091 pixels mm^-1	θ_max = 25.0°, θ_min = 3.2°
φ and ω scans	h = −8→8
Absorption correction: multi-scan SADABS (Sheldrick, 2003)	k = −17→17
T_min = 0.962, T_max = 0.996	l = −7→7
5201 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.061	H-atom parameters constrained
wR(F²) = 0.165	w = 1/[σ²(F_o²) + (0.0865P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1092 reflections	Δρ_max = 0.26 e Å⁻³
92 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.033 (12)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.1601 (5)	0.40796 (18)	−0.4314 (5)	0.0213 (8)
C11	−0.0148 (5)	0.44779 (18)	−0.5294 (5)	0.0261 (8)
H11	−0.0556	0.4392	−0.7024	0.033*
H12	0.1046	0.4146	−0.4610	0.033*
C2	−0.1235 (5)	0.36536 (18)	−0.2106 (5)	0.0221 (8)
N21	0.0685 (4)	0.35474 (16)	−0.0517 (4)	0.0257 (7)
O21	0.1838 (3)	0.41516 (16)	−0.0476 (4)	0.0381 (7)
O22	0.1050 (3)	0.28615 (13)	0.0754 (3)	0.0347 (7)
C3	−0.2630 (5)	0.32949 (18)	−0.1317 (5)	0.0243 (8)
H3	−0.2323	0.3009	0.0187	0.030*
C4	−0.4460 (5)	0.3356 (2)	−0.2727 (5)	0.0273 (8)
H4	−0.5432	0.3125	−0.2196	0.034*
C5	−0.4868 (5)	0.37598 (19)	−0.4939 (5)	0.0290 (8)
H5	−0.6126	0.3796	−0.5937	0.036*
C6	−0.3460 (5)	0.41086 (19)	−0.5695 (5)	0.0254 (8)
H6	−0.3776	0.4379	−0.7218	0.032*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.029 (2)	0.0130 (14)	0.0240 (14)	0.0009 (13)	0.0122 (15)	−0.0019 (10)
C11	0.036 (2)	0.0198 (16)	0.0261 (15)	−0.0012 (14)	0.0143 (15)	−0.0002 (11)
C2	0.027 (2)	0.0165 (14)	0.0222 (14)	0.0010 (13)	0.0076 (15)	−0.0042 (10)
N21	0.0283 (19)	0.0263 (14)	0.0233 (13)	0.0035 (13)	0.0094 (12)	0.0022 (10)
O21	0.0335 (17)	0.0363 (14)	0.0411 (13)	−0.0104 (11)	0.0071 (11)	0.0096 (10)
O22	0.0413 (18)	0.0302 (13)	0.0305 (12)	0.0026 (11)	0.0084 (11)	0.0090 (9)
C3	0.033 (2)	0.0182 (15)	0.0249 (14)	−0.0005 (14)	0.0141 (16)	−0.0010 (11)
C4	0.029 (2)	0.0233 (16)	0.0327 (16)	0.0004 (14)	0.0144 (16)	−0.0004 (12)
C5	0.028 (2)	0.0237 (16)	0.0334 (16)	0.0041 (14)	0.0077 (15)	−0.0033 (12)
C6	0.034 (2)	0.0190 (15)	0.0244 (14)	0.0039 (14)	0.0105 (16)	0.0015 (11)

Geometric parameters (Å, º) top

C1—C6	1.386 (4)	N21—O22	1.229 (3)
C1—C2	1.405 (4)	C3—C4	1.376 (5)
C1—C11	1.516 (4)	C3—H3	0.95
C11—C11ⁱ	1.554 (5)	C4—C5	1.390 (4)
C11—H11	0.99	C4—H4	0.95
C11—H12	0.99	C5—C6	1.380 (4)
C2—C3	1.388 (4)	C5—H5	0.95
C2—N21	1.469 (4)	C6—H6	0.95
N21—O21	1.231 (3)

C6—C1—C2	115.6 (2)	O22—N21—C2	117.8 (3)
C6—C1—C11	118.8 (2)	C4—C3—C2	119.5 (3)
C2—C1—C11	125.6 (3)	C4—C3—H3	120.2
C1—C11—C11ⁱ	110.7 (3)	C2—C3—H3	120.2
C1—C11—H11	109.5	C3—C4—C5	119.1 (3)
C11ⁱ—C11—H11	109.5	C3—C4—H4	120.5
C1—C11—H12	109.5	C5—C4—H4	120.5
C11ⁱ—C11—H12	109.5	C6—C5—C4	120.5 (3)
H11—C11—H12	108.1	C6—C5—H5	119.8
C3—C2—C1	122.9 (3)	C4—C5—H5	119.8
C3—C2—N21	116.3 (2)	C5—C6—C1	122.4 (3)
C1—C2—N21	120.8 (2)	C5—C6—H6	118.8
O21—N21—O22	123.1 (3)	C1—C6—H6	118.8
O21—N21—C2	119.1 (2)

C6—C1—C11—C11ⁱ	88.7 (4)	C1—C2—N21—O22	−147.1 (2)
C2—C1—C11—C11ⁱ	−92.9 (4)	C1—C2—C3—C4	−0.3 (4)
C6—C1—C2—C3	−1.0 (4)	N21—C2—C3—C4	−179.0 (2)
C11—C1—C2—C3	−179.5 (2)	C2—C3—C4—C5	1.3 (4)
C6—C1—C2—N21	177.6 (2)	C3—C4—C5—C6	−1.0 (4)
C11—C1—C2—N21	−0.9 (4)	C4—C5—C6—C1	−0.3 (4)
C3—C2—N21—O21	−146.8 (2)	C2—C1—C6—C5	1.3 (4)
C1—C2—N21—O21	34.5 (3)	C11—C1—C6—C5	179.9 (2)
C3—C2—N21—O22	31.6 (3)

Symmetry code: (i) −x, −y+1, −z−1.

Acknowledgements

The authors thank the EPSRC National Crystallography Service (Southampton, England) and acknowledge the use of the EPSRC's Chemical Database Service at Daresbury.

References

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