2,6 Di­nitro­toluene

Acta Cryst.(2001). E57, o827±o828 DOI: 10.1107/S1600536801013022 Nie, Xu, Li and Chiang C₇H₆N₂O₄

o827

organic papers

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

2,6-Dinitrotoluene

Jing-Jing Nie,a_{Duan-Jun Xu,}a_*

Zhen-Yu Lia_{and Michael Y.}

Chiangb

a_{Department of Chemistry, Zhejiang University,}

Hangzhou, Zhejiang, China, andb_Department

of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 293 K

Mean(C±C) = 0.004 AÊ Rfactor = 0.046 wRfactor = 0.133 Data-to-parameter ratio = 8.9

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved

Crystals of 2,6-dinitrotoluene, C7H6N2O4, were obtained from

a methanol solution of the mixture of 2,6- and 2,4-dinitro-toluene. The P212121 space group shows the compound is

chiral, but the absolute con®guration was not determined reliably. The nitro group planes are inclined to the benzene plane with dihedral angles of 53.1 (1) and 38.1 (1)_,

respec-tively. The repulsion between methyl and nitro groups results

in a rather small CÐCÐC angle of 112.6 (2) _{within the}

benzene ring.

Experimental

Single crystals of the title chiral compound were obtained from a methanol solution containing 2,6- and 2,4-dinitrotoluene when we tried to separate the isomers.

Crystal data C7H6N2O4

Mr= 182.14

Orthorhombic,P212121

a= 7.830 (2) AÊ

b= 13.683 (3) AÊ

c= 7.296 (2) AÊ

V= 781.7 (3) AÊ3

Z= 4

Dx= 1.548 Mg mÿ3

Dmnot measured

MoKradiation Cell parameters from 20

re¯ections

= 11.7±21.5

= 0.13 mmÿ1

T= 293 (2) K Prismatic, yellow 0.300.240.20 mm Data collection

Rigaku AFC-7Rdiffractometer

!/2scans

Absorption correction: scan (Northet al., 1968)

Tmin= 0.963,Tmax= 0.974

1061 measured re¯ections 1061 independent re¯ections 906 re¯ections withI> 2(I)

max= 27.5

h= 0!10

k= 0!17

l= 0!9

3 standard re¯ections every 100 re¯ections intensity decay: 0.3%

Re®nement Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.046}

wR(F2_{) = 0.133}

S= 1.05 1061 re¯ections 119 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0748P)2

+ 0.2426P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.27 e AÊÿ3

min=ÿ0.23 e AÊÿ3

Extinction correction:SHELXL93 Extinction coef®cient: 0.0719 (109)

Table 1

Selected geometric parameters (AÊ,_).

O1ÐN1 1.216 (3) O2ÐN1 1.213 (4) O3ÐN2 1.221 (3)

O4ÐN2 1.206 (4) N1ÐC2 1.482 (3) N2ÐC6 1.476 (3)

O1ÐN1ÐO2 124.8 (2) O1ÐN1ÐC2 117.5 (3) O2ÐN1ÐC2 117.6 (3) O4ÐN2ÐO3 124.0 (3)

O4ÐN2ÐC6 117.4 (3) O3ÐN2ÐC6 118.7 (2) C2ÐC1ÐC6 112.6 (2)

H atoms were located in calculated positions and constrained to ride on their parent C atoms during re®nement. The absolute con®guration could not be reliably determined.

Data collection: MSC/AFC Diffractometer Control Software

(Molecular Structure Corporation, 1985a, 1992a); cell re®nement:

MSC/AFC Diffractometer Control Software; data reduction:

TEXSAN (Molecular Structure Corporation, 1985b, 1992b); program(s) used to solve structure: SHELXS93 (Sheldrick, 1993); program(s) used to re®ne structure:SHELXL93; molecular graphics:

XP(Siemens, 1994).

The project was supported by the National Natural Science Foundation of China (29973036).

References

Molecular Structure Corporation (1985a, 1992a).MSC/AFC Diffractometer Control Software. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.

Molecular Structure Corporation (1985b, 1992b). TEXSAN. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.

Sheldrick, G. M. (1993). SHELXS93 and SHELXL93. University of GoÈttingen, Germany.

Siemens (1994).XP. Version 5.03. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Figure 1

supporting information

sup-1

supporting information

Acta Cryst. (2001). E57, o827–o828 [doi:10.1107/S1600536801013022]

2,6-Dinitrotoluene

Jing-Jing Nie, Duan-Jun Xu, Zhen-Yu Li and Michael Y. Chiang

S1. Comment

no comment!

S2. Experimental

Single crystals of the title chiral compound were obtained from a methanol solution containing 2,6- and

2,4-dinitro-toluene when we tried to separate the isomers.

S3. Refinement

H atoms were located in calculated positions and ridden on parent C atoms during refinements. The absolute

Figure 1

View of the crystal packing of the title compound with 30% probability displacement ellipsoids, showing the overlap of

adjacent benzene rings. H atoms have been omitted for clarity.

2,6-Dinitrotoluene

Crystal data

C7H6N2O4 Mr = 182.14

Orthorhombic, P212121 a = 7.830 (2) Å

b = 13.683 (3) Å

c = 7.296 (2) Å

V = 781.7 (3) Å3 Z = 4

F(000) = 376

Dx = 1.548 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 20 reflections

θ = 11.7–21.5°

supporting information

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Data collection

Rigaku AFC-7R diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

Absorption correction: psi scan (North et al., 1968)

Tmin = 0.963, Tmax = 0.974 1061 measured reflections

1061 independent reflections 906 reflections with I > 2σ(I)

Rint = 0.000

θmax = 27.5°, θmin = 3.0°

h = 0→10

k = 0→17

l = 0→9

3 standard reflections every 100 reflections intensity decay: 0.3%

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.046} wR(F2_{) = 0.133} S = 1.05 1061 reflections 119 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0748P)2 + 0.2426P]

where P = (Fo2 _{+ 2Fc}2_)/3

(Δ/σ)max < 0.001

Δρmax = 0.27 e Å−3

Δρmin = −0.23 e Å−3

Extinction correction: SHELXL93, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.0719 (109)

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 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 on F2 _{for ALL reflections except for 0 with very negative F}2 _{or flagged by the user for potential}

systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2_{, conventional R-factors R are based}

on F, with F set to zero for negative F2_{. R-factors based on F}2 _{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₎

x y z Uiso*/Ueq

H5 0.8401 (4) −0.1759 (2) 0.9188 (5) 0.057* C6 0.6635 (3) −0.0686 (2) 0.9191 (4) 0.0400 (6) C7 0.4516 (4) 0.0738 (2) 0.8999 (6) 0.0528 (8) H7A 0.3695 (4) 0.0218 (2) 0.9067 (6) 0.079* H7B 0.4392 (4) 0.1075 (2) 0.7853 (6) 0.079* H7C 0.4330 (4) 0.1187 (2) 0.9990 (6) 0.079*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

O1 0.0618 (13) 0.0413 (10) 0.089 (2) −0.0103 (11) −0.0006 (14) 0.0130 (12) O2 0.078 (2) 0.0411 (12) 0.094 (2) 0.0051 (12) 0.013 (2) −0.0150 (12) O3 0.0462 (12) 0.0585 (13) 0.095 (2) −0.0100 (10) 0.0075 (13) 0.0034 (14) O4 0.078 (2) 0.0458 (12) 0.130 (3) −0.0177 (13) 0.001 (2) −0.027 (2) N1 0.0455 (12) 0.0305 (10) 0.070 (2) −0.0027 (9) −0.0062 (14) 0.0001 (12) N2 0.0430 (12) 0.0389 (11) 0.069 (2) −0.0069 (10) −0.0044 (13) 0.0003 (13) C1 0.0363 (12) 0.0333 (12) 0.0489 (13) 0.0032 (10) 0.0002 (13) 0.0006 (12) C2 0.0407 (13) 0.0298 (11) 0.053 (2) −0.0001 (10) 0.0006 (15) −0.0022 (12) C3 0.0378 (13) 0.0425 (14) 0.062 (2) −0.0053 (11) −0.004 (2) 0.0046 (15) C4 0.0345 (12) 0.0471 (14) 0.065 (2) 0.0072 (11) 0.000 (2) 0.0036 (15) C5 0.0461 (14) 0.0340 (12) 0.061 (2) 0.0068 (11) −0.001 (2) −0.0013 (13) C6 0.0379 (12) 0.0299 (11) 0.0523 (15) −0.0041 (10) −0.0014 (14) −0.0009 (12) C7 0.0397 (13) 0.0395 (13) 0.079 (2) 0.0081 (12) 0.002 (2) 0.005 (2)

Geometric parameters (Å, º)

O1—N1 1.216 (3) C3—C4 1.386 (4)

O2—N1 1.213 (4) C3—H3 0.93

O3—N2 1.221 (3) C4—C5 1.372 (4)

O4—N2 1.206 (4) C4—H4 0.93

N1—C2 1.482 (3) C5—C6 1.382 (4)

N2—C6 1.476 (3) C5—H5 0.93

C1—C2 1.389 (4) C7—H7A 0.96

C1—C6 1.404 (3) C7—H7B 0.96

C1—C7 1.505 (4) C7—H7C 0.96

C2—C3 1.380 (4)

O1—N1—O2 124.8 (2) C5—C4—C3 119.5 (3)

O1—N1—C2 117.5 (3) C5—C4—H4 120.3

O2—N1—C2 117.6 (3) C3—C4—H4 120.3

O4—N2—O3 124.0 (3) C4—C5—C6 119.5 (2)

O4—N2—C6 117.4 (3) C4—C5—H5 120.2

O3—N2—C6 118.7 (2) C6—C5—H5 120.24

C2—C1—C6 112.6 (2) C5—C6—C1 124.3 (2)

C2—C1—C7 123.7 (2) C5—C6—N2 115.7 (2)

C6—C1—C7 123.5 (2) C1—C6—N2 120.0 (2)

C3—C2—C1 125.4 (2) C1—C7—H7A 109.47

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C1—C2—N1 118.8 (2) H7A—C7—H7B 109.5

C2—C3—C4 118.6 (3) C1—C7—H7C 109.5

C2—C3—H3 120.7 H7A—C7—H7C 109.5