Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199014651/bm1358sup1.cif | |
Structure factor file (SHELXL table format) https://doi.org/10.1107/S0108270199014651/bm1358Isup2.sft |
CCDC reference: 142777
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).
The H atom on N3 was located in a difference Fourier synthesis. It was allowed to refine positionally with Uiso = 1.2Ueq(N3). The phenyl H atoms were placed geometrically and thereafter refined using a riding model with Uiso(H) = 1.2Ueq(C)
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.
Fig. 1. View of (I) showing the atom-numbering scheme and ellipsoids at the 50% probability level. |
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) Å3 | 0.55 × 0.2 × 0.2 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.145 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0735P)2 + 0.1533P] where P = (Fo2 + 2Fc2)/3 |
2452 reflections | (Δ/σ)max = 0.001 |
220 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C14H7ClN4O5 | γ = 88.12 (8)° |
Mr = 346.69 | V = 695 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.804 (13) Å | Mo Kα radiation |
b = 12.931 (6) Å | µ = 0.31 mm−1 |
c = 7.49 (4) Å | T = 293 K |
α = 91.59 (16)° | 0.55 × 0.2 × 0.2 mm |
β = 112.9 (2)° |
Rigaku four-circle AFC6 diffractometer | 2453 independent reflections |
Absorption correction: empirical (using intensity measurements) via ψ scans (north et al., 1968) ? | 1747 reflections with I > 2σ(I) |
Tmin = 0.782, Tmax = 0.940 | 3 standard reflections every 150 reflections |
2453 measured reflections | intensity decay: variation 0.5% |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.145 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.24 e Å−3 |
2452 reflections | Δρmin = −0.31 e Å−3 |
220 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
Experimental details
Crystal data | |
Chemical formula | C14H7ClN4O5 |
Mr | 346.69 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.804 (13), 12.931 (6), 7.49 (4) |
α, β, γ (°) | 91.59 (16), 112.9 (2), 88.12 (8) |
V (Å3) | 695 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.55 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Rigaku four-circle AFC6 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scans (North et al., 1968) |
Tmin, Tmax | 0.782, 0.940 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2453, 2453, 1747 |
Rint | ? |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.145, 1.05 |
No. of reflections | 2452 |
No. of parameters | 220 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.31 |
Computer programs: TEXSAN (Molecular Structure Corporation, 1993), TEXSAN, SHELXS86 (Sheldrick, 1985), SHELXL93 (Sheldrick, 1993), ORTEP (Johnson, 1965), SHELXL93.
Cl1—C12 | 1.724 (3) | O5—N4 | 1.219 (6) |
O1—N2 | 1.225 (4) | N1—C1 | 1.147 (4) |
O2—N2 | 1.234 (3) | N2—C6 | 1.465 (4) |
N3—C8 | 1.377 (5) | O3—C8 | 1.210 (4) |
N3—C5 | 1.409 (4) | N4—C11 | 1.472 (4) |
O4—N4 | 1.213 (5) | C1—C2 | 1.445 (4) |
C8—N3—C5 | 125.4 (3) | O5—N4—C11 | 117.7 (3) |
O1—N2—O2 | 122.5 (2) | N1—C1—C2 | 177.8 (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) |
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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.