3,5-Dinitro­benzoyl chloride

Wang, H.-Y.; Xie, M.-H.; Luo, S.-N.; Zou, P.; Liu, Y.-L.

doi:10.1107/S1600536809036228

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2460

doi:10.1107/S1600536809036228

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3,5-Dinitrobenzoyl chloride

Hong-Yong Wang,^a Min-Hao Xie,^a ^* Shi-Neng Luo,^a Pei Zou ^a and Ya-Ling Liu ^a

^aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: wywhy007@yahoo.com.cn

(Received 27 July 2009; accepted 8 September 2009; online 12 September 2009)

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 ); Liu & Wang (2000 ); Saunders & Stacey (1942 ).

Experimental

Crystal data

C₇H₃ClN₂O₅
M_r = 230.56
Orthorhombic, P n a 2₁
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[F² > 2σ(F²)] = 0.038
wR(F²) = 0.097
S = 1.03
2011 reflections
164 parameters
29 restraints
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ), 905 Friedel pairs
Flack parameter: 0.08 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O4ⁱ	0.95	2.44	3.386 (3)	173
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku 2004 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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.

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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

Computing details top

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).

Figures top

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.

3,5-Dinitrobenzoyl chloride top

Crystal data top

C₇H₃ClN₂O₅	F(000) = 464
M_r = 230.56	D_x = 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	R_int = 0.025
Graphite monochromator	θ_max = 27.5°, θ_min = 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(F_o²) + (0.0626P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
2011 reflections	Δρ_max = 0.40 e Å⁻³
164 parameters	Δρ_min = −0.22 e Å⁻³
29 restraints	Absolute structure: Flack (1983), 905 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (9)

Crystal data top

C₇H₃ClN₂O₅	V = 880.7 (3) Å³
M_r = 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	1835 reflections with I > 2σ(I)
6904 measured reflections	R_int = 0.025
2011 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.097	Δρ_max = 0.40 e Å⁻³
S = 1.03	Δρ_min = −0.22 e Å⁻³
2011 reflections	Absolute structure: Flack (1983), 905 Friedel pairs
164 parameters	Absolute structure 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	U_iso*/U_eq	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, º) 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, º) 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 code: (i) −x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₃ClN₂O₅
M_r	230.56
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	93
a, b, c (Å)	18.295 (4), 8.3924 (19), 5.7362 (13)
V (Å³)	880.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.44
Crystal size (mm)	0.37 × 0.33 × 0.27

Data collection
Diffractometer	Rigaku SPIDER diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6904, 2011, 1835
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.097, 1.03
No. of reflections	2011
No. of parameters	164
No. of restraints	29
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.22
Absolute structure	Flack (1983), 905 Friedel pairs
Absolute structure parameter	0.08 (9)

Computer programs: RAPID-AUTO (Rigaku 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) 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 code: (i) −x+1/2, y+1/2, z+1/2.

Acknowledgements

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

References

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