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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2460.
Published online 2009 September 12. doi:  10.1107/S1600536809036228
PMCID: PMC2970283

3,5-Dinitro­benzoyl chloride

Abstract

The carbonyl chloride group in the title compound, C7H3ClN2O5, is disordered over two orientations with occupancies of 0.505 (5) and 0.495 (5). The mol­ecule is approximately planar, the dihedral angle between the carbonyl chloride plane and benzene ring being 9.6 (4)° in the major disorder component and 7.1 (4)° in the minor component. The nitro group at the 5-position is twisted, forming a dihedral angle of 6.7 (4)°. The crystal packing is stabilized by C—H(...)O hydrogen bonds.

Related literature

For general background to 3,5-dinitro­benzoyl chloride, see: Gennaro et al. (1993 [triangle]); Liu & Wang (2000 [triangle]); Saunders & Stacey (1942 [triangle]).

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Object name is e-65-o2460-scheme1.jpg

Experimental

Crystal data

  • C7H3ClN2O5
  • M r = 230.56
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2460-efi1.jpg
  • a = 18.295 (4) Å
  • b = 8.3924 (19) Å
  • c = 5.7362 (13) Å
  • V = 880.7 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.44 mm−1
  • T = 93 K
  • 0.37 × 0.33 × 0.27 mm

Data collection

  • Rigaku SPIDER diffractometer
  • Absorption correction: none
  • 6904 measured reflections
  • 2011 independent reflections
  • 1835 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.038
  • wR(F 2) = 0.097
  • S = 1.03
  • 2011 reflections
  • 164 parameters
  • 29 restraints
  • H-atom parameters constrained
  • Δρmax = 0.40 e Å−3
  • Δρmin = −0.22 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 905 Friedel pairs
  • Flack parameter: 0.08 (9)

Data collection: RAPID-AUTO (Rigaku 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809036228/ci2867sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036228/ci2867Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge financial support from the Jiangsu Institute of Nuclear Medicine.

supplementary crystallographic information

Comment

3,5-Dinitrobenzoyl chloride is a useful disinfectant and preservative (Saunders et al., 1942; Liu et al., 2000). It was also used as a derivatization reagent for azide determination by capillary electrophoresis (Gennaro et al., 1993). We report here the crystal structure of the title compound.

The carbonyl chloride group is disordered over two orientations (Fig. 1). Except for a long N1—O3 distance [1.339 (3) Å] all other bond lengths and angles are within expected ranges. The molecule is approximately planar. The plane of the carbonyl chloride group forms a dihedral angle of 9.6 (4)° with the benzene ring in the major component [7.1 (4)° in the minor component]. The N1/O2/O3 and N2/O4/O5 nitro groups form dihedral angles of 1.9 (3) and 6.7 (4)°, respectively, with the benzene ring.

The crystal packing is stabilized by C—H···O hydrogen bonds (Table 1).

Experimental

A sample of commercial 3,5-dinitrobenzoylchloride (Aldrich) was crystallized by slow evaporation of a solution in carbon tetrachloride.

Refinement

The carbonyl chloride group is disordered over two orientations with occupancies of 0.505 (5) and 0.495 (5). The CO distance involving disordered atoms was restrained to 1.22 (1) Å and in each disorder component and the carbonyl chloride group was restrained to be planar. The displacement parameters of atoms CL1', O1', O1 and O3 were restrained to an approximate isotropic behaviour. H atoms were positioned geometrically (C—H = 0.95 Å) and were allowed to ride on the C atoms to which they are bonded, with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Both disorder components are shown.

Crystal data

C7H3ClN2O5F(000) = 464
Mr = 230.56Dx = 1.739 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 2915 reflections
a = 18.295 (4) Åθ = 3.3–27.5°
b = 8.3924 (19) ŵ = 0.44 mm1
c = 5.7362 (13) ÅT = 93 K
V = 880.7 (3) Å3Block, colourless
Z = 40.37 × 0.33 × 0.27 mm

Data collection

Rigaku SPIDER diffractometer1835 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.025
graphiteθmax = 27.5°, θmin = 3.3°
ω scansh = −23→22
6904 measured reflectionsk = −10→10
2011 independent reflectionsl = −7→7

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.097w = 1/[σ2(Fo2) + (0.0626P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
2011 reflectionsΔρmax = 0.40 e Å3
164 parametersΔρmin = −0.21 e Å3
29 restraintsAbsolute structure: Flack (1983), 905 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.08 (9)

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 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)

xyzUiso*/UeqOcc. (<1)
Cl10.43221 (12)0.5812 (3)0.3714 (5)0.0418 (5)0.505 (5)
C70.3864 (3)0.4499 (11)0.5519 (12)0.0289 (16)0.505 (5)
O10.3635 (5)0.4892 (13)0.7358 (18)0.098 (5)0.505 (5)
Cl1'0.37524 (15)0.5156 (3)0.7640 (4)0.0442 (5)0.495 (5)
C7'0.4064 (3)0.4534 (13)0.4960 (13)0.035 (2)0.495 (5)
O1'0.4432 (5)0.5374 (11)0.377 (2)0.083 (3)0.495 (5)
C10.38140 (12)0.2885 (3)0.4413 (4)0.0325 (5)
C20.41455 (11)0.2335 (3)0.2394 (4)0.0324 (5)
H20.44680.29950.15260.039*
C30.39917 (11)0.0787 (2)0.1677 (4)0.0277 (4)
C40.35290 (10)−0.0199 (2)0.2878 (4)0.0276 (4)
H40.3428−0.12510.23550.033*
C50.32173 (11)0.0400 (2)0.4872 (4)0.0288 (4)
C60.33439 (11)0.1924 (2)0.5677 (4)0.0320 (5)
H60.31150.23030.70570.038*
N10.43482 (9)0.0200 (2)−0.0448 (3)0.0308 (4)
N20.27342 (10)−0.0636 (2)0.6268 (3)0.0361 (4)
O20.47388 (8)0.10880 (19)−0.1549 (3)0.0384 (4)
O30.42041 (8)−0.1304 (2)−0.1076 (3)0.0426 (4)
O40.25855 (9)−0.19494 (18)0.5508 (3)0.0396 (4)
O50.25255 (10)−0.0136 (3)0.8142 (4)0.0579 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0443 (8)0.0269 (9)0.0541 (9)−0.0110 (6)0.0055 (7)−0.0027 (8)
C70.033 (3)0.026 (2)0.028 (3)0.006 (3)0.003 (3)−0.008 (3)
O10.108 (7)0.085 (6)0.100 (7)0.003 (4)−0.004 (5)−0.006 (4)
Cl1'0.0540 (9)0.0372 (8)0.0414 (9)−0.0016 (7)0.0034 (7)0.0000 (8)
C7'0.029 (3)0.044 (3)0.034 (4)0.001 (3)0.005 (3)−0.014 (3)
O1'0.104 (6)0.056 (5)0.088 (5)−0.021 (4)0.030 (4)−0.030 (4)
C10.0386 (11)0.0261 (10)0.0328 (11)0.0017 (8)−0.0118 (9)−0.0037 (9)
C20.0353 (11)0.0284 (10)0.0336 (11)−0.0030 (8)−0.0078 (9)0.0027 (10)
C30.0295 (10)0.0283 (10)0.0253 (10)0.0033 (7)−0.0041 (8)−0.0008 (8)
C40.0286 (9)0.0258 (9)0.0286 (11)0.0003 (7)−0.0061 (8)−0.0030 (8)
C50.0280 (9)0.0315 (10)0.0268 (10)−0.0007 (8)−0.0032 (8)−0.0012 (9)
C60.0352 (11)0.0325 (10)0.0283 (10)0.0055 (9)−0.0061 (9)−0.0048 (9)
N10.0333 (9)0.0310 (9)0.0281 (9)0.0011 (7)−0.0009 (7)−0.0007 (8)
N20.0370 (10)0.0394 (10)0.0320 (10)−0.0078 (8)0.0004 (9)−0.0085 (9)
O20.0372 (8)0.0431 (9)0.0348 (9)−0.0005 (6)0.0045 (7)0.0076 (7)
O30.0345 (8)0.0728 (12)0.0205 (7)0.0114 (7)0.0055 (6)−0.0008 (9)
O40.0452 (9)0.0383 (8)0.0355 (8)−0.0115 (7)−0.0003 (7)−0.0075 (7)
O50.0665 (12)0.0637 (13)0.0435 (12)−0.0216 (10)0.0226 (9)−0.0250 (10)

Geometric parameters (Å, °)

Cl1—C71.728 (8)C3—N11.468 (3)
C7—O11.182 (9)C4—C51.374 (3)
C7—C11.499 (9)C4—H40.95
Cl1'—C7'1.720 (9)C5—C61.380 (3)
C7'—O1'1.190 (8)C5—N21.476 (3)
C7'—C11.491 (11)C6—H60.95
C1—C61.384 (3)N1—O21.210 (2)
C1—C21.387 (3)N1—O31.339 (3)
C2—C31.391 (3)N2—O51.216 (3)
C2—H20.95N2—O41.216 (2)
C3—C41.370 (3)
O1—C7—C1127.5 (9)C2—C3—N1117.96 (19)
O1—C7—Cl1121.9 (9)C3—C4—C5117.00 (19)
C1—C7—Cl1110.6 (4)C3—C4—H4121.5
O1'—C7'—C1127.1 (9)C5—C4—H4121.5
O1'—C7'—Cl1'121.3 (10)C4—C5—C6123.3 (2)
C1—C7'—Cl1'111.6 (5)C4—C5—N2118.99 (18)
C6—C1—C2121.02 (19)C6—C5—N2117.72 (19)
C6—C1—C7'128.4 (3)C5—C6—C1118.0 (2)
C2—C1—C7'110.5 (3)C5—C6—H6121.0
C6—C1—C7110.1 (3)C1—C6—H6121.0
C2—C1—C7128.9 (3)O2—N1—O3123.80 (18)
C1—C2—C3118.0 (2)O2—N1—C3119.29 (18)
C1—C2—H2121.0O3—N1—C3116.89 (16)
C3—C2—H2121.0O5—N2—O4124.1 (2)
C4—C3—C2122.7 (2)O5—N2—C5117.64 (18)
C4—C3—N1119.31 (18)O4—N2—C5118.26 (18)
O1'—C7'—C1—C6−174.9 (4)C2—C3—C4—C5−0.4 (3)
Cl1'—C7'—C1—C65.2 (4)N1—C3—C4—C5179.13 (17)
O1'—C7'—C1—C27.5 (3)C3—C4—C5—C60.6 (3)
Cl1'—C7'—C1—C2−172.4 (2)C3—C4—C5—N2−177.98 (18)
O1'—C7'—C1—C7−161.7 (9)C4—C5—C6—C1−0.6 (3)
Cl1'—C7'—C1—C718.3 (8)N2—C5—C6—C1178.06 (18)
O1—C7—C1—C610.2 (3)C2—C1—C6—C50.3 (3)
Cl1—C7—C1—C6−169.9 (2)C7'—C1—C6—C5−177.1 (3)
O1—C7—C1—C2−171.9 (4)C7—C1—C6—C5178.4 (2)
Cl1—C7—C1—C28.1 (4)C4—C3—N1—O2177.70 (19)
O1—C7—C1—C7'−158.9 (9)C2—C3—N1—O2−2.7 (3)
Cl1—C7—C1—C7'21.1 (8)C4—C3—N1—O3−1.0 (3)
C6—C1—C2—C30.0 (3)C2—C3—N1—O3178.60 (18)
C7'—C1—C2—C3177.8 (2)C4—C5—N2—O5172.6 (2)
C7—C1—C2—C3−177.8 (3)C6—C5—N2—O5−6.1 (3)
C1—C2—C3—C40.1 (3)C4—C5—N2—O4−5.4 (3)
C1—C2—C3—N1−179.43 (17)C6—C5—N2—O4175.9 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···O4i0.952.443.386 (3)173

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2867).

References

  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Gennaro, M. C., Abrigo, C., Marengo, E. & Liberatori, A. (1993). J. Liq. Chromatogr.16, 2715–2730.
  • Liu, X. J. & Wang, S. Q. (2000). Chin. J. Pharm.31, 471–472.
  • Rigaku (2004). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Saunders, B. C. & Stacey, G. L. (1942). J. Biochem.34, 368–375. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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