supplementary materials
4-Chloro-3-nitrobenzamide
For the preparation of the title compound, 4-chloro-3-nitrobenzoic acid
(60.3 g, 0.32 mol) was suspended in thionyl chloride (180 ml) and heated
at reflux for 5 h, then concentrated in vacuum as far as possible, the
oily substance obtained. Added ice ammonia water (300 ml) to the oil,
cooling to room temperature, a precipitate formed, which was collected by
filtration and washed with water. Pure title compound was obtained by
crystallizing from methanol (Sun et al., 2006). Crystals suitable for
X-ray analysis were obtained by slow evaporation of a methanol solution.
H atoms were positioned geometrically, with N-H = 0.86 (for NH2) and C-H =
0.93 Å for aromatic H and constrained to ride on their parent atoms, with
Uiso(H) = 1.2Ueq(C,N).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).
4-Chloro-3-nitrobenzamide
top
Crystal data top
| C7H5ClN2O3 | F(000) = 408 |
| Mr = 200.58 | Dx = 1.643 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 25 reflections |
| a = 8.8490 (18) Å | θ = 10–13° |
| b = 7.5470 (15) Å | µ = 0.44 mm−1 |
| c = 12.374 (3) Å | T = 294 K |
| β = 101.18 (3)° | Block, colorless |
| V = 810.7 (3) Å3 | 0.30 × 0.20 × 0.10 mm |
| Z = 4 | |
Data collection top
Enraf–Nonius CAD-4
diffractometer | 1085 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.061 |
| graphite | θmax = 25.3°, θmin = 2.6° |
| ω/2θ scans | h = −10→10 |
Absorption correction: ψ scan
(North et al., 1968) | k = 0→9 |
| Tmin = 0.879, Tmax = 0.957 | l = 0→14 |
| 1555 measured reflections | 3 standard reflections every 120 min |
| 1459 independent reflections | intensity decay: none |
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)] = 0.078 | H-atom parameters constrained |
| wR(F2) = 0.198 | w = 1/[σ2(Fo2) + (0.060P)2 + 4.5P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max < 0.001 |
| 1459 reflections | Δρmax = 0.41 e Å−3 |
| 112 parameters | Δρmin = −0.50 e Å−3 |
| Primary atom site location: structure-invariant direct methods | |
Crystal data top
| C7H5ClN2O3 | V = 810.7 (3) Å3 |
| Mr = 200.58 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 8.8490 (18) Å | µ = 0.44 mm−1 |
| b = 7.5470 (15) Å | T = 294 K |
| c = 12.374 (3) Å | 0.30 × 0.20 × 0.10 mm |
| β = 101.18 (3)° | |
Data collection top
Enraf–Nonius CAD-4
diffractometer | 1085 reflections with I > 2σ(I) |
Absorption correction: ψ scan
(North et al., 1968) | Rint = 0.061 |
| Tmin = 0.879, Tmax = 0.957 | θmax = 25.3° |
| 1555 measured reflections | 3 standard reflections every 120 min |
| 1459 independent reflections | intensity decay: none |
Refinement top
| R[F2 > 2σ(F2)] = 0.078 | H-atom parameters constrained |
| wR(F2) = 0.198 | Δρmax = 0.41 e Å−3 |
| S = 1.01 | Δρmin = −0.50 e Å−3 |
| 1459 reflections | Absolute structure: ? |
| 112 parameters | Flack parameter: ? |
| ? restraints | Rogers parameter: ? |
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 | |
| Cl | 0.65545 (17) | 0.0416 (2) | 0.36001 (13) | 0.0618 (5) | |
| O1 | 0.7053 (5) | 0.1130 (7) | 0.5888 (4) | 0.0749 (14) | |
| O2 | 0.8610 (5) | 0.3068 (6) | 0.6677 (3) | 0.0554 (11) | |
| O3 | 1.3178 (4) | 0.4669 (5) | 0.5500 (2) | 0.0390 (9) | |
| N1 | 0.8103 (5) | 0.2076 (5) | 0.5896 (3) | 0.0385 (10) | |
| N2 | 1.3809 (5) | 0.3507 (7) | 0.3985 (4) | 0.0502 (12) | |
| H2B | 1.4701 | 0.4002 | 0.4120 | 0.060* | |
| H2C | 1.3546 | 0.2856 | 0.3409 | 0.060* | |
| C1 | 0.8373 (6) | 0.1359 (7) | 0.3967 (4) | 0.0378 (11) | |
| C2 | 0.9221 (6) | 0.1454 (7) | 0.3143 (4) | 0.0401 (12) | |
| H2A | 0.8819 | 0.1004 | 0.2448 | 0.048* | |
| C3 | 1.0637 (6) | 0.2201 (7) | 0.3346 (4) | 0.0424 (12) | |
| H3A | 1.1188 | 0.2260 | 0.2779 | 0.051* | |
| C4 | 1.1312 (5) | 0.2902 (6) | 0.4397 (3) | 0.0295 (10) | |
| C5 | 1.0412 (5) | 0.2840 (6) | 0.5196 (3) | 0.0316 (10) | |
| H5A | 1.0790 | 0.3319 | 0.5888 | 0.038* | |
| C6 | 0.8958 (5) | 0.2076 (6) | 0.4985 (4) | 0.0308 (10) | |
| C7 | 1.2837 (6) | 0.3746 (7) | 0.4668 (4) | 0.0435 (10) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cl | 0.0584 (9) | 0.0679 (10) | 0.0626 (10) | −0.0058 (7) | 0.0208 (7) | −0.0114 (8) |
| O1 | 0.079 (3) | 0.088 (3) | 0.074 (3) | −0.027 (3) | 0.057 (3) | −0.007 (3) |
| O2 | 0.072 (3) | 0.068 (3) | 0.035 (2) | −0.016 (2) | 0.0311 (18) | −0.007 (2) |
| O3 | 0.0454 (18) | 0.052 (2) | 0.0267 (16) | −0.0091 (16) | 0.0254 (14) | −0.0091 (15) |
| N1 | 0.054 (2) | 0.038 (2) | 0.036 (2) | 0.000 (2) | 0.0375 (19) | 0.0044 (19) |
| N2 | 0.051 (2) | 0.070 (3) | 0.042 (2) | −0.007 (2) | 0.038 (2) | −0.018 (2) |
| C1 | 0.049 (3) | 0.035 (3) | 0.035 (2) | 0.008 (2) | 0.020 (2) | 0.004 (2) |
| C2 | 0.063 (3) | 0.042 (3) | 0.019 (2) | 0.001 (2) | 0.018 (2) | −0.004 (2) |
| C3 | 0.068 (3) | 0.044 (3) | 0.024 (2) | 0.002 (2) | 0.031 (2) | 0.002 (2) |
| C4 | 0.043 (2) | 0.030 (2) | 0.022 (2) | −0.0015 (19) | 0.0245 (18) | −0.0009 (18) |
| C5 | 0.050 (3) | 0.032 (2) | 0.020 (2) | 0.002 (2) | 0.0234 (18) | −0.0002 (18) |
| C6 | 0.046 (2) | 0.028 (2) | 0.027 (2) | 0.0066 (19) | 0.0275 (19) | 0.0056 (18) |
| C7 | 0.061 (2) | 0.038 (2) | 0.038 (2) | 0.009 (19) | 0.034 (19) | 0.006 (18) |
Geometric parameters (Å, °) top
| Cl—C1 | 1.737 (5) | C1—C6 | 1.377 (7) |
| O3—C7 | 1.231 (6) | C2—C3 | 1.352 (7) |
| N1—O1 | 1.170 (6) | C2—H2A | 0.9300 |
| N1—O2 | 1.236 (5) | C3—C4 | 1.424 (7) |
| N1—C6 | 1.474 (5) | C3—H3A | 0.9300 |
| N2—C7 | 1.329 (6) | C4—C5 | 1.386 (6) |
| N2—H2B | 0.8600 | C4—C7 | 1.471 (7) |
| N2—H2C | 0.8600 | C5—C6 | 1.388 (7) |
| C1—C2 | 1.380 (6) | C5—H5A | 0.9300 |
| | | |
| O1—N1—O2 | 122.9 (4) | C4—C3—H3A | 118.9 |
| O1—N1—C6 | 121.2 (4) | C3—C4—C7 | 124.9 (4) |
| O2—N1—C6 | 115.8 (4) | C5—C4—C3 | 116.2 (4) |
| C7—N2—H2B | 120.0 | C5—C4—C7 | 118.8 (4) |
| C7—N2—H2C | 120.0 | C4—C5—C6 | 121.3 (4) |
| H2B—N2—H2C | 120.0 | C4—C5—H5A | 119.3 |
| C2—C1—Cl | 115.9 (4) | C6—C5—H5A | 119.3 |
| C6—C1—Cl | 124.4 (4) | C1—C6—C5 | 120.4 (4) |
| C6—C1—C2 | 119.6 (5) | C1—C6—N1 | 122.8 (4) |
| C1—C2—H2A | 119.9 | C5—C6—N1 | 116.8 (4) |
| C3—C2—C1 | 120.1 (5) | O3—C7—N2 | 121.7 (5) |
| C3—C2—H2A | 119.9 | O3—C7—C4 | 120.0 (4) |
| C2—C3—C4 | 122.3 (4) | N2—C7—C4 | 118.3 (5) |
| C2—C3—H3A | 118.9 | | |
| | | |
| O1—N1—C6—C1 | 17.6 (7) | C2—C3—C4—C5 | −2.5 (7) |
| O2—N1—C6—C1 | −165.6 (5) | C2—C3—C4—C7 | −179.3 (5) |
| O1—N1—C6—C5 | −162.2 (5) | C3—C4—C5—C6 | 2.3 (7) |
| O2—N1—C6—C5 | 14.6 (6) | C7—C4—C5—C6 | 179.3 (4) |
| C6—C1—C2—C3 | 2.0 (8) | C5—C4—C7—O3 | −13.8 (7) |
| Cl—C1—C2—C3 | 178.6 (4) | C3—C4—C7—O3 | 163.0 (5) |
| C2—C1—C6—C5 | −2.2 (7) | C5—C4—C7—N2 | 167.3 (5) |
| Cl—C1—C6—C5 | −178.5 (4) | C3—C4—C7—N2 | −15.9 (8) |
| C2—C1—C6—N1 | 178.1 (4) | C4—C5—C6—C1 | 0.0 (7) |
| Cl—C1—C6—N1 | 1.8 (7) | C4—C5—C6—N1 | 179.7 (4) |
| C1—C2—C3—C4 | 0.4 (8) | | |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2B···O3i | 0.86 | 2.10 | 2.958 (6) | 177 |
| N2—H2C···O2ii | 0.86 | 2.26 | 3.067 (6) | 155 |
| C2—H2A···O3iii | 0.93 | 2.42 | 3.331 (6) | 166 |
| C5—H5A···O2 | 0.93 | 2.33 | 2.658 (6) | 100 |
| Symmetry codes: (i) −x+3, −y+1, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) 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 |
| N2—H2B···O3i | 0.86 | 2.10 | 2.958 (6) | 177 |
| N2—H2C···O2ii | 0.86 | 2.26 | 3.067 (6) | 155 |
| C2—H2A···O3iii | 0.93 | 2.42 | 3.331 (6) | 166 |
| C5—H5A···O2 | 0.93 | 2.33 | 2.658 (6) | 100 |
| Symmetry codes: (i) −x+3, −y+1, −z+1; (ii) x+1/2, −y+1/2, z−1/2; (iii) x−1/2, −y+1/2, z−1/2. |
The authors thank the Center of Testing and Analysis, Nanjing University, for
support.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft. The Netherlands.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Sun, Y. W. & Wang, J. W. (2006). Hua Xue Shi Ji, 28, 124–125.
O and C-H![[pi]](/logos/entities/pi_rmgif.gif)
-![[Figure 1]](./hk2596fig1thm.gif)
![[Figure 2]](./hk2596fig2thm.gif)
Some derivatives of pyridine are important chemical materials. We report herein the crystal structure of the title compound.
In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C1-C6) is, of course, planar. Atoms Cl, N1 and C7 are 0.021 (3), 0.029 (3) and -0.001 (3) Å away from the plane of the benzene ring. The intramolecular C-H···O hydrogen bond results in the formation of a five-membered ring B (O2/N1/C5/C6/H5A), having envelope conformation with O2 atom displaced by 0.278 (3) Å from the plane of the other ring atoms.
In the crystal structure, intermolecular N-H···O and C-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The π-π contact between the benzene rings, Cg1—Cg1i [symmetry code: (i) -x, -y, 1 - z, where Cg1 is centroid of the ring A (C1-C6)] may further stabilize the structure, with centroid-centroid distance of 3.803 (3) Å.