supplementary materials
3,5-Dinitrobenzoyl chloride
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.
A sample of commercial 3,5-dinitrobenzoylchloride (Aldrich) was crystallized by
slow evaporation of a solution in carbon tetrachloride.
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).
Data collection: RAPID-AUTO (Rigaku 2004); cell refinement: RAPID-AUTO (Rigaku 2004); data reduction: RAPID-AUTO (Rigaku 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
3,5-Dinitrobenzoyl chloride
top
Crystal data top
| C7H3ClN2O5 | F(000) = 464 |
| Mr = 230.56 | Dx = 1.739 Mg m−3 |
| Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: P 2c -2n | Cell parameters from 2915 reflections |
| a = 18.295 (4) Å | θ = 3.3–27.5° |
| b = 8.3924 (19) Å | µ = 0.44 mm−1 |
| c = 5.7362 (13) Å | T = 93 K |
| V = 880.7 (3) Å3 | Block, colourless |
| Z = 4 | 0.37 × 0.33 × 0.27 mm |
Data collection top
Rigaku SPIDER
diffractometer | 1835 reflections with I > 2σ(I) |
| Radiation source: Rotating Anode | Rint = 0.025 |
| graphite | θmax = 27.5°, θmin = 3.3° |
| ω scans | h = −23→22 |
| 6904 measured reflections | k = −10→10 |
| 2011 independent reflections | l = −7→7 |
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)] = 0.038 | H-atom parameters constrained |
| wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0626P)2]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max = 0.001 |
| 2011 reflections | Δρmax = 0.40 e Å−3 |
| 164 parameters | Δρmin = −0.21 e Å−3 |
| 29 restraints | Absolute structure: Flack (1983), 905 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.08 (9) |
Crystal data top
| C7H3ClN2O5 | V = 880.7 (3) Å3 |
| Mr = 230.56 | Z = 4 |
| Orthorhombic, Pna21 | Mo Kα radiation |
| a = 18.295 (4) Å | µ = 0.44 mm−1 |
| b = 8.3924 (19) Å | T = 93 K |
| c = 5.7362 (13) Å | 0.37 × 0.33 × 0.27 mm |
Data collection top
Rigaku SPIDER
diffractometer | Rint = 0.025 |
| 6904 measured reflections | θmax = 27.5° |
| 2011 independent reflections | Standard reflections: 0 |
| 1835 reflections with I > 2σ(I) | |
Refinement top
| R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
| wR(F2) = 0.097 | Δρmax = 0.40 e Å−3 |
| S = 1.03 | Δρmin = −0.21 e Å−3 |
| 2011 reflections | Absolute structure: Flack (1983), 905 Friedel pairs |
| 164 parameters | Flack parameter: 0.08 (9) |
| 29 restraints | |
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 | Uiso*/Ueq | Occ. (<1) |
| Cl1 | 0.43221 (12) | 0.5812 (3) | 0.3714 (5) | 0.0418 (5) | 0.505 (5) |
| C7 | 0.3864 (3) | 0.4499 (11) | 0.5519 (12) | 0.0289 (16) | 0.505 (5) |
| O1 | 0.3635 (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) |
| C1 | 0.38140 (12) | 0.2885 (3) | 0.4413 (4) | 0.0325 (5) | |
| C2 | 0.41455 (11) | 0.2335 (3) | 0.2394 (4) | 0.0324 (5) | |
| H2 | 0.4468 | 0.2995 | 0.1526 | 0.039* | |
| C3 | 0.39917 (11) | 0.0787 (2) | 0.1677 (4) | 0.0277 (4) | |
| C4 | 0.35290 (10) | −0.0199 (2) | 0.2878 (4) | 0.0276 (4) | |
| H4 | 0.3428 | −0.1251 | 0.2355 | 0.033* | |
| C5 | 0.32173 (11) | 0.0400 (2) | 0.4872 (4) | 0.0288 (4) | |
| C6 | 0.33439 (11) | 0.1924 (2) | 0.5677 (4) | 0.0320 (5) | |
| H6 | 0.3115 | 0.2303 | 0.7057 | 0.038* | |
| N1 | 0.43482 (9) | 0.0200 (2) | −0.0448 (3) | 0.0308 (4) | |
| N2 | 0.27342 (10) | −0.0636 (2) | 0.6268 (3) | 0.0361 (4) | |
| O2 | 0.47388 (8) | 0.10880 (19) | −0.1549 (3) | 0.0384 (4) | |
| O3 | 0.42041 (8) | −0.1304 (2) | −0.1076 (3) | 0.0426 (4) | |
| O4 | 0.25855 (9) | −0.19494 (18) | 0.5508 (3) | 0.0396 (4) | |
| O5 | 0.25255 (10) | −0.0136 (3) | 0.8142 (4) | 0.0579 (6) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cl1 | 0.0443 (8) | 0.0269 (9) | 0.0541 (9) | −0.0110 (6) | 0.0055 (7) | −0.0027 (8) |
| C7 | 0.033 (3) | 0.026 (2) | 0.028 (3) | 0.006 (3) | 0.003 (3) | −0.008 (3) |
| O1 | 0.108 (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) |
| C1 | 0.0386 (11) | 0.0261 (10) | 0.0328 (11) | 0.0017 (8) | −0.0118 (9) | −0.0037 (9) |
| C2 | 0.0353 (11) | 0.0284 (10) | 0.0336 (11) | −0.0030 (8) | −0.0078 (9) | 0.0027 (10) |
| C3 | 0.0295 (10) | 0.0283 (10) | 0.0253 (10) | 0.0033 (7) | −0.0041 (8) | −0.0008 (8) |
| C4 | 0.0286 (9) | 0.0258 (9) | 0.0286 (11) | 0.0003 (7) | −0.0061 (8) | −0.0030 (8) |
| C5 | 0.0280 (9) | 0.0315 (10) | 0.0268 (10) | −0.0007 (8) | −0.0032 (8) | −0.0012 (9) |
| C6 | 0.0352 (11) | 0.0325 (10) | 0.0283 (10) | 0.0055 (9) | −0.0061 (9) | −0.0048 (9) |
| N1 | 0.0333 (9) | 0.0310 (9) | 0.0281 (9) | 0.0011 (7) | −0.0009 (7) | −0.0007 (8) |
| N2 | 0.0370 (10) | 0.0394 (10) | 0.0320 (10) | −0.0078 (8) | 0.0004 (9) | −0.0085 (9) |
| O2 | 0.0372 (8) | 0.0431 (9) | 0.0348 (9) | −0.0005 (6) | 0.0045 (7) | 0.0076 (7) |
| O3 | 0.0345 (8) | 0.0728 (12) | 0.0205 (7) | 0.0114 (7) | 0.0055 (6) | −0.0008 (9) |
| O4 | 0.0452 (9) | 0.0383 (8) | 0.0355 (8) | −0.0115 (7) | −0.0003 (7) | −0.0075 (7) |
| O5 | 0.0665 (12) | 0.0637 (13) | 0.0435 (12) | −0.0216 (10) | 0.0226 (9) | −0.0250 (10) |
Geometric parameters (Å, °) top
| Cl1—C7 | 1.728 (8) | C3—N1 | 1.468 (3) |
| C7—O1 | 1.182 (9) | C4—C5 | 1.374 (3) |
| C7—C1 | 1.499 (9) | C4—H4 | 0.95 |
| Cl1'—C7' | 1.720 (9) | C5—C6 | 1.380 (3) |
| C7'—O1' | 1.190 (8) | C5—N2 | 1.476 (3) |
| C7'—C1 | 1.491 (11) | C6—H6 | 0.95 |
| C1—C6 | 1.384 (3) | N1—O2 | 1.210 (2) |
| C1—C2 | 1.387 (3) | N1—O3 | 1.339 (3) |
| C2—C3 | 1.391 (3) | N2—O5 | 1.216 (3) |
| C2—H2 | 0.95 | N2—O4 | 1.216 (2) |
| C3—C4 | 1.370 (3) | | |
| | | |
| O1—C7—C1 | 127.5 (9) | C2—C3—N1 | 117.96 (19) |
| O1—C7—Cl1 | 121.9 (9) | C3—C4—C5 | 117.00 (19) |
| C1—C7—Cl1 | 110.6 (4) | C3—C4—H4 | 121.5 |
| O1'—C7'—C1 | 127.1 (9) | C5—C4—H4 | 121.5 |
| O1'—C7'—Cl1' | 121.3 (10) | C4—C5—C6 | 123.3 (2) |
| C1—C7'—Cl1' | 111.6 (5) | C4—C5—N2 | 118.99 (18) |
| C6—C1—C2 | 121.02 (19) | C6—C5—N2 | 117.72 (19) |
| C6—C1—C7' | 128.4 (3) | C5—C6—C1 | 118.0 (2) |
| C2—C1—C7' | 110.5 (3) | C5—C6—H6 | 121.0 |
| C6—C1—C7 | 110.1 (3) | C1—C6—H6 | 121.0 |
| C2—C1—C7 | 128.9 (3) | O2—N1—O3 | 123.80 (18) |
| C1—C2—C3 | 118.0 (2) | O2—N1—C3 | 119.29 (18) |
| C1—C2—H2 | 121.0 | O3—N1—C3 | 116.89 (16) |
| C3—C2—H2 | 121.0 | O5—N2—O4 | 124.1 (2) |
| C4—C3—C2 | 122.7 (2) | O5—N2—C5 | 117.64 (18) |
| C4—C3—N1 | 119.31 (18) | O4—N2—C5 | 118.26 (18) |
| | | |
| O1'—C7'—C1—C6 | −174.9 (4) | C2—C3—C4—C5 | −0.4 (3) |
| Cl1'—C7'—C1—C6 | 5.2 (4) | N1—C3—C4—C5 | 179.13 (17) |
| O1'—C7'—C1—C2 | 7.5 (3) | C3—C4—C5—C6 | 0.6 (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—C7 | 18.3 (8) | N2—C5—C6—C1 | 178.06 (18) |
| O1—C7—C1—C6 | 10.2 (3) | C2—C1—C6—C5 | 0.3 (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—C5 | 178.4 (2) |
| Cl1—C7—C1—C2 | 8.1 (4) | C4—C3—N1—O2 | 177.70 (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—C3 | 0.0 (3) | C2—C3—N1—O3 | 178.60 (18) |
| C7'—C1—C2—C3 | 177.8 (2) | C4—C5—N2—O5 | 172.6 (2) |
| C7—C1—C2—C3 | −177.8 (3) | C6—C5—N2—O5 | −6.1 (3) |
| C1—C2—C3—C4 | 0.1 (3) | C4—C5—N2—O4 | −5.4 (3) |
| C1—C2—C3—N1 | −179.43 (17) | C6—C5—N2—O4 | 175.9 (2) |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H6···O4i | 0.95 | 2.44 | 3.386 (3) | 173 |
| Symmetry codes: (i) −x+1/2, y+1/2, z+1/2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C6—H6···O4i | 0.95 | 2.44 | 3.386 (3) | 173 |
| Symmetry codes: (i) −x+1/2, y+1/2, z+1/2. |
The authors acknowledge financial support from Jiangsu Institute of Nuclear
Medicine.
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.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./ci2867fig1thm.gif)
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).