organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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2,2′-Di­nitro­di­benzyl

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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[link]), 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[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) 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[link]), 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)°.[link]

[Scheme 1]
[Figure 1]
Figure 1
Molecular configuration and atom-numbering scheme for (I[link]). 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

  • Mr = 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

  • Dx = 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[Sheldrick, G. M. (2003). SADABS. Version 2.10. Bruker AXS Inc., Madison, USA.]) Tmin = 0.962, Tmax = 0.996

  • 5201 measured reflections

  • 1092 independent reflections

  • 730 reflections with I > 2σ(I)

  • Rint = 0.128

  • θmax = 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(Fo2) + (0.0865P)2] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.26 e Å−3

  • Δρmin = −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 Uiso(H) = 1.25Ueq(carrier atom). The high Rint is the result of weak high-angle data.

Data collection: COLLECT (Hooft, 1998[Hooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; data reduction: DENZO, SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON97 (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97.

Supporting information


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
C14H12N2O4F(000) = 284
Mr = 272.26Dx = 1.452 Mg m3
Monoclinic, P21/cMelting point: 404 K K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.5678 (8) ÅCell parameters from 1390 reflections
b = 14.4964 (16) Åθ = 2.9–27.5°
c = 5.9874 (5) ŵ = 0.11 mm1
β = 108.607 (6)°T = 120 K
V = 622.52 (11) Å3Plate, colourless
Z = 20.36 × 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 anode730 reflections with I > 2σ(I)
10 cm confocal mirrors monochromatorRint = 0.128
Detector resolution: 9.091 pixels mm-1θmax = 25.0°, θmin = 3.2°
φ and ω scansh = 88
Absorption correction: multi-scan
SADABS (Sheldrick, 2003)
k = 1717
Tmin = 0.962, Tmax = 0.996l = 77
5201 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.165 w = 1/[σ2(Fo2) + (0.0865P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1092 reflectionsΔρmax = 0.26 e Å3
92 parametersΔρmin = 0.28 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.033 (12)
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.1601 (5)0.40796 (18)0.4314 (5)0.0213 (8)
C110.0148 (5)0.44779 (18)0.5294 (5)0.0261 (8)
H110.05560.43920.70240.033*
H120.10460.41460.46100.033*
C20.1235 (5)0.36536 (18)0.2106 (5)0.0221 (8)
N210.0685 (4)0.35474 (16)0.0517 (4)0.0257 (7)
O210.1838 (3)0.41516 (16)0.0476 (4)0.0381 (7)
O220.1050 (3)0.28615 (13)0.0754 (3)0.0347 (7)
C30.2630 (5)0.32949 (18)0.1317 (5)0.0243 (8)
H30.23230.30090.01870.030*
C40.4460 (5)0.3356 (2)0.2727 (5)0.0273 (8)
H40.54320.31250.21960.034*
C50.4868 (5)0.37598 (19)0.4939 (5)0.0290 (8)
H50.61260.37960.59370.036*
C60.3460 (5)0.41086 (19)0.5695 (5)0.0254 (8)
H60.37760.43790.72180.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.029 (2)0.0130 (14)0.0240 (14)0.0009 (13)0.0122 (15)0.0019 (10)
C110.036 (2)0.0198 (16)0.0261 (15)0.0012 (14)0.0143 (15)0.0002 (11)
C20.027 (2)0.0165 (14)0.0222 (14)0.0010 (13)0.0076 (15)0.0042 (10)
N210.0283 (19)0.0263 (14)0.0233 (13)0.0035 (13)0.0094 (12)0.0022 (10)
O210.0335 (17)0.0363 (14)0.0411 (13)0.0104 (11)0.0071 (11)0.0096 (10)
O220.0413 (18)0.0302 (13)0.0305 (12)0.0026 (11)0.0084 (11)0.0090 (9)
C30.033 (2)0.0182 (15)0.0249 (14)0.0005 (14)0.0141 (16)0.0010 (11)
C40.029 (2)0.0233 (16)0.0327 (16)0.0004 (14)0.0144 (16)0.0004 (12)
C50.028 (2)0.0237 (16)0.0334 (16)0.0041 (14)0.0077 (15)0.0033 (12)
C60.034 (2)0.0190 (15)0.0244 (14)0.0039 (14)0.0105 (16)0.0015 (11)
Geometric parameters (Å, º) top
C1—C61.386 (4)N21—O221.229 (3)
C1—C21.405 (4)C3—C41.376 (5)
C1—C111.516 (4)C3—H30.95
C11—C11i1.554 (5)C4—C51.390 (4)
C11—H110.99C4—H40.95
C11—H120.99C5—C61.380 (4)
C2—C31.388 (4)C5—H50.95
C2—N211.469 (4)C6—H60.95
N21—O211.231 (3)
C6—C1—C2115.6 (2)O22—N21—C2117.8 (3)
C6—C1—C11118.8 (2)C4—C3—C2119.5 (3)
C2—C1—C11125.6 (3)C4—C3—H3120.2
C1—C11—C11i110.7 (3)C2—C3—H3120.2
C1—C11—H11109.5C3—C4—C5119.1 (3)
C11i—C11—H11109.5C3—C4—H4120.5
C1—C11—H12109.5C5—C4—H4120.5
C11i—C11—H12109.5C6—C5—C4120.5 (3)
H11—C11—H12108.1C6—C5—H5119.8
C3—C2—C1122.9 (3)C4—C5—H5119.8
C3—C2—N21116.3 (2)C5—C6—C1122.4 (3)
C1—C2—N21120.8 (2)C5—C6—H6118.8
O21—N21—O22123.1 (3)C1—C6—H6118.8
O21—N21—C2119.1 (2)
C6—C1—C11—C11i88.7 (4)C1—C2—N21—O22147.1 (2)
C2—C1—C11—C11i92.9 (4)C1—C2—C3—C40.3 (4)
C6—C1—C2—C31.0 (4)N21—C2—C3—C4179.0 (2)
C11—C1—C2—C3179.5 (2)C2—C3—C4—C51.3 (4)
C6—C1—C2—N21177.6 (2)C3—C4—C5—C61.0 (4)
C11—C1—C2—N210.9 (4)C4—C5—C6—C10.3 (4)
C3—C2—N21—O21146.8 (2)C2—C1—C6—C51.3 (4)
C1—C2—N21—O2134.5 (3)C11—C1—C6—C5179.9 (2)
C3—C2—N21—O2231.6 (3)
Symmetry code: (i) x, y+1, z1.
 

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

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationHooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2003). SADABS. Version 2.10. Bruker AXS Inc., Madison, USA.  Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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