4-Chloro-N-(4-cyano-2-nitro­phenyl)-3-nitro­benz­amide

The structure of the title compound, C₁₄H₇ClN₄O₅, comprises two nearly coplanar phenyl rings connected via an amido moiety.

S1. Comment

In the course of an investigation of the effect of water on the fluorodenitration of substituted benzonitriles, it was observed that hydrolysis of the –CN moiety was possible. In an attempted fluorination of 4-chloro-3-nitrobenzonitrile, the title compound, (I), was observed as a previously uncharacterized product in such reactions (Adams et al., 1999).

In (I) (Fig. 1), the amido unit is planar with an O3—C8—N3—H3A torsion angle of 171 (2)°. However, the C10—C9—C8—O3 and C4—C5—N3—C8 torsion angles of 22.3 (4) and −28.0 (4)°, respectively, indicate significant deviation from planarity with the amido group. In the chlorine-containing ring, the nitro group is twisted out of the plane of the phenyl ring [the O4—N4—C11—C10 torsion angle is 53.3 (4)°]. This is presumably due to the steric clash between the Cl atom and nitro group. In contrast, the nitro group ortho to the amido group on the other phenyl ring is more coplanar with the ring [the O2—N2—C6—C5 torsion angle is −14.5 (4)°]. This conformation may be stabilized, at least in part, by a hydrogen-bond interaction between the N—H of the amido group and an O atom of the nitro group [N3···O2 2.662 (5) Å, N3—H3A···O2 2.06 (3) Å and N3—H3A···O2 125 (3)°]. The planes of the phenyl rings are inclined to each other at an angle of 3.2 (3)°. Examination of the packing of the molecules reveals a head-to-tail phenyl–phenyl interaction between adjacently stacked molecules of 3.77 (1) Å, indicating a weak intermolecular π-stacking interaction.

S2. Experimental

4-Chloro-3-nitrobenzonitrile (0.182 g, 1 mmol) was placed in a round-bottomed flask. Dimethyl sulfoxide (10 ml, distilled and stored under argon) was added and the solution heated to 353 K under argon. Tetramethylammonium fluoride (0.20 g, 1.70 mmol; TMAF^.4/3H₂O, prepared by drying the tetrahydrate under vacuum at 333 K for 2 d) was added to the solution. After 1 h the reaction mixture was cooled in an ice bath. The organics were extracted into ether and washed well with water, dried (magnesium sulfate) and the ether removed on a rotary evaporator. The crude mixture was then recrystallized from acetonitrile to give yellow needles (Adams et al., 1999).

S3. Refinement

The H atom on N3 was located in a difference Fourier synthesis. It was allowed to refine positionally with U_iso = 1.2U_eq(N3). The phenyl H atoms were placed geometrically and thereafter refined using a riding model with U_iso(H) = 1.2U_eq(C)

Computing details

Data collection: TEXSAN (Molecular Structure Corporation, 1993); cell refinement: TEXSAN; data reduction: TEXSAN; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: ORTEP (Johnson, 1965); software used to prepare material for publication: SHELXL93.

Figures

Fig. 1. View of (I) showing the atom-numbering scheme and ellipsoids at the 50% probability level.

4-Chloro-N-(4-cyano-2-nitrophenyl)-3-nitrobenzamide

Crystal data

C14H7ClN4O5	Z = 2
Mr = 346.69	F(000) = 352
Triclinic, P1	Dx = 1.656 Mg m^−3
a = 7.804 (13) Å	Mo Kα radiation, λ = 0.71069 Å
b = 12.931 (6) Å	Cell parameters from 20 reflections
c = 7.49 (4) Å	θ = 9–15°
α = 91.59 (16)°	µ = 0.31 mm^−1
β = 112.9 (2)°	T = 293 K
γ = 88.12 (8)°	Needle, yellow
V = 695 (4) Å^3	0.55 × 0.2 × 0.2 mm

Data collection

Rigaku four-circle AFC6 diffractometer	1747 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.8°
Graphite monochromator	h = 0→9
ω–2θ scans	k = −15→15
Absorption correction: empirical (using intensity measurements) via ψ scans (north et al., 1968) ?	l = −8→8
Tmin = 0.782, Tmax = 0.940	3 standard reflections every 150 reflections
2453 measured reflections	intensity decay: variation 0.5%
2453 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0735P)^2 + 0.1533P] where P = (Fo^2 + 2Fc^2)/3
2452 reflections	(Δ/σ)max = 0.001
220 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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. 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. The observed criterion of F² > σ(F²) is used only for calculating R factor obs 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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.72328 (11)	0.44652 (6)	0.42411 (13)	0.0512 (3)
O1	−0.1103 (3)	−0.1416 (2)	0.0668 (3)	0.0491 (6)
O2	0.0890 (3)	−0.02284 (14)	0.2026 (3)	0.0420 (5)
N3	0.4317 (3)	−0.0462 (2)	0.2098 (4)	0.0355 (6)
H3A	0.342 (4)	−0.000 (3)	0.183 (5)	0.043*
O4	1.0909 (3)	0.2578 (2)	0.3301 (4)	0.0663 (7)
O5	1.0947 (3)	0.3336 (2)	0.5918 (4)	0.0673 (8)
N1	0.2131 (4)	−0.5540 (2)	0.0408 (5)	0.0554 (8)
N2	0.0499 (3)	−0.1114 (2)	0.1366 (3)	0.0323 (5)
O3	0.7448 (3)	−0.0701 (2)	0.3766 (3)	0.0476 (6)
N4	1.0199 (3)	0.2826 (2)	0.4435 (4)	0.0395 (6)
C1	0.2418 (4)	−0.4673 (2)	0.0663 (5)	0.0393 (7)
C2	0.2846 (4)	−0.3588 (2)	0.0977 (4)	0.0320 (6)
C3	0.4616 (4)	−0.3275 (2)	0.1227 (4)	0.0370 (7)
H3	0.5493 (4)	−0.3762 (2)	0.1161 (4)	0.044*
C4	0.5077 (4)	−0.2251 (2)	0.1570 (4)	0.0345 (7)
H4	0.6258 (4)	−0.2052 (2)	0.1710 (4)	0.041*
C5	0.3797 (4)	−0.1504 (2)	0.1712 (4)	0.0294 (6)
C6	0.1997 (3)	−0.1832 (2)	0.1383 (4)	0.0276 (6)
C7	0.1522 (4)	−0.2861 (2)	0.1031 (4)	0.0318 (6)
H7	0.0327 (4)	−0.3063 (2)	0.0832 (4)	0.038*
C8	0.6100 (4)	−0.0128 (2)	0.3105 (4)	0.0308 (6)
C9	0.6280 (3)	0.1029 (2)	0.3345 (4)	0.0289 (6)
C10	0.8037 (4)	0.1412 (2)	0.3704 (4)	0.0308 (6)
H10	0.9006 (4)	0.0967 (2)	0.3731 (4)	0.037*
C11	0.8316 (3)	0.2456 (2)	0.4015 (4)	0.0301 (6)
C12	0.6897 (4)	0.3150 (2)	0.3955 (4)	0.0312 (6)
C13	0.5151 (4)	0.2765 (2)	0.3598 (4)	0.0361 (7)
H13	0.4180 (4)	0.3214 (2)	0.3554 (4)	0.043*
C14	0.4857 (4)	0.1714 (2)	0.3307 (4)	0.0318 (6)
H14	0.3687 (4)	0.1462 (2)	0.3082 (4)	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0491 (5)	0.0239 (4)	0.0773 (6)	−0.0052 (3)	0.0208 (4)	−0.0003 (3)
O1	0.0259 (11)	0.0422 (12)	0.079 (2)	−0.0052 (9)	0.0198 (11)	−0.0050 (11)
O2	0.0403 (12)	0.0245 (10)	0.0609 (14)	−0.0026 (8)	0.0197 (10)	−0.0075 (9)
N3	0.0268 (12)	0.0234 (12)	0.054 (2)	−0.0042 (9)	0.0134 (11)	−0.0017 (11)
O4	0.0384 (13)	0.094 (2)	0.074 (2)	−0.0077 (13)	0.0292 (13)	0.0130 (15)
O5	0.0384 (13)	0.0551 (15)	0.089 (2)	−0.0173 (11)	0.0040 (13)	−0.0209 (14)
N1	0.047 (2)	0.0302 (15)	0.088 (2)	−0.0057 (12)	0.0249 (15)	−0.0093 (14)
N2	0.0298 (13)	0.0288 (13)	0.0395 (14)	−0.0009 (10)	0.0148 (10)	0.0015 (10)
O3	0.0301 (11)	0.0308 (11)	0.0652 (15)	0.0013 (9)	0.0010 (10)	−0.0040 (10)
N4	0.0279 (13)	0.0341 (14)	0.053 (2)	−0.0061 (10)	0.0114 (12)	0.0050 (12)
C1	0.035 (2)	0.028 (2)	0.056 (2)	−0.0021 (12)	0.0180 (14)	−0.0045 (13)
C2	0.036 (2)	0.0237 (14)	0.035 (2)	−0.0040 (11)	0.0134 (12)	−0.0028 (11)
C3	0.035 (2)	0.0287 (14)	0.046 (2)	0.0013 (12)	0.0148 (13)	−0.0037 (12)
C4	0.0243 (14)	0.0316 (15)	0.048 (2)	−0.0046 (11)	0.0142 (13)	−0.0042 (12)
C5	0.0290 (14)	0.0259 (13)	0.032 (2)	−0.0044 (11)	0.0103 (11)	−0.0004 (11)
C6	0.0259 (13)	0.0256 (13)	0.0306 (14)	−0.0018 (10)	0.0103 (11)	−0.0009 (11)
C7	0.0316 (15)	0.0267 (14)	0.038 (2)	−0.0061 (11)	0.0140 (12)	−0.0020 (11)
C8	0.0268 (14)	0.0288 (14)	0.037 (2)	−0.0055 (11)	0.0128 (12)	−0.0018 (12)
C9	0.0270 (14)	0.0275 (14)	0.0308 (15)	−0.0037 (11)	0.0096 (11)	−0.0003 (11)
C10	0.0243 (14)	0.0298 (14)	0.038 (2)	−0.0001 (11)	0.0125 (12)	−0.0007 (12)
C11	0.0238 (14)	0.0304 (14)	0.035 (2)	−0.0056 (11)	0.0104 (12)	0.0029 (12)
C12	0.0318 (15)	0.0243 (14)	0.036 (2)	−0.0036 (11)	0.0113 (12)	0.0006 (11)
C13	0.0274 (15)	0.034 (2)	0.048 (2)	0.0040 (12)	0.0152 (13)	0.0031 (13)
C14	0.0246 (14)	0.0300 (14)	0.041 (2)	−0.0045 (11)	0.0125 (12)	0.0029 (12)

Geometric parameters (Å, º)

Cl1—C12	1.724 (3)	C2—C3	1.392 (4)
O1—N2	1.225 (4)	C3—C4	1.374 (4)
O2—N2	1.234 (3)	C4—C5	1.399 (4)
N3—C8	1.377 (5)	C5—C6	1.406 (4)
N3—C5	1.409 (4)	C6—C7	1.383 (4)
O4—N4	1.213 (5)	C8—C9	1.506 (4)
O5—N4	1.219 (6)	C9—C14	1.390 (4)
N1—C1	1.147 (4)	C9—C10	1.396 (4)
N2—C6	1.465 (4)	C10—C11	1.373 (4)
O3—C8	1.210 (4)	C11—C12	1.390 (4)
N4—C11	1.472 (4)	C12—C13	1.389 (4)
C1—C2	1.445 (4)	C13—C14	1.382 (4)
C2—C7	1.385 (4)
C8—N3—C5	125.4 (3)	C5—C6—N2	122.6 (2)
O1—N2—O2	122.5 (2)	C6—C7—C2	119.2 (3)
O1—N2—C6	118.3 (2)	O3—C8—N3	123.9 (3)
O2—N2—C6	119.2 (2)	O3—C8—C9	121.1 (3)
O4—N4—O5	124.9 (3)	N3—C8—C9	114.9 (3)
O4—N4—C11	117.3 (3)	C14—C9—C10	119.1 (3)
O5—N4—C11	117.7 (3)	C14—C9—C8	124.7 (2)
N1—C1—C2	177.8 (3)	C10—C9—C8	116.2 (2)
C7—C2—C3	119.9 (3)	C11—C10—C9	119.2 (3)
C7—C2—C1	120.9 (3)	C10—C11—C12	122.2 (2)
C3—C2—C1	119.2 (3)	C10—C11—N4	117.5 (2)
C4—C3—C2	120.5 (3)	C12—C11—N4	120.3 (3)
C3—C4—C5	120.9 (3)	C13—C12—C11	118.4 (3)
C4—C5—C6	117.4 (2)	C13—C12—Cl1	119.7 (2)
C4—C5—N3	119.8 (3)	C11—C12—Cl1	121.9 (2)
C6—C5—N3	122.7 (2)	C14—C13—C12	120.0 (3)
C7—C6—C5	121.8 (3)	C13—C14—C9	121.1 (3)
C7—C6—N2	115.6 (2)