supplementary materials
4-Chloro-3-nitrobenzonitrile
For the preparation of the title compound, 4-chloro-3-nitrobenzamide (33.9 g,
0.17 mol) was suspended in phosphorus oxychloride (150 ml). The temperature
was controlled at 333 K for 6 h, and then it was put into ice water (500 ml).
It was filtered and the colorless precipitate was washed (yield; 28.2 g)
(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 C-H = 0.93 Å for aromatic H
and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
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-nitrobenzonitrile
top
Crystal data top
| C7H3ClN2O2 | Z = 2 |
| Mr = 182.56 | F(000) = 184 |
| Triclinic, P1 | Dx = 1.565 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.2260 (14) Å | Cell parameters from 25 reflections |
| b = 7.7610 (16) Å | θ = 9–12° |
| c = 7.7970 (16) Å | µ = 0.45 mm−1 |
| α = 110.27 (3)° | T = 294 K |
| β = 91.86 (3)° | Block, colorless |
| γ = 107.22 (3)° | 0.30 × 0.20 × 0.10 mm |
| V = 387.32 (18) Å3 | |
Data collection top
Enraf–Nonius CAD-4
diffractometer | 1000 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.052 |
| graphite | θmax = 25.3°, θmin = 2.8° |
| ω/2θ scans | h = −8→8 |
Absorption correction: ψ scan
(North et al., 1968) | k = −9→8 |
| Tmin = 0.878, Tmax = 0.957 | l = 0→9 |
| 1540 measured reflections | 3 standard reflections every 120 min |
| 1418 independent reflections | intensity decay: none |
Refinement top
| 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)] = 0.073 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.182 | H-atom parameters constrained |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.060P)2 + 0.880P]
where P = (Fo2 + 2Fc2)/3 |
| 1418 reflections | (Δ/σ)max < 0.001 |
| 103 parameters | Δρmax = 0.27 e Å−3 |
| 0 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
| C7H3ClN2O2 | γ = 107.22 (3)° |
| Mr = 182.56 | V = 387.32 (18) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.2260 (14) Å | Mo Kα radiation |
| b = 7.7610 (16) Å | µ = 0.45 mm−1 |
| c = 7.7970 (16) Å | T = 294 K |
| α = 110.27 (3)° | 0.30 × 0.20 × 0.10 mm |
| β = 91.86 (3)° | |
Data collection top
Enraf–Nonius CAD-4
diffractometer | 1000 reflections with I > 2σ(I) |
Absorption correction: ψ scan
(North et al., 1968) | Rint = 0.052 |
| Tmin = 0.878, Tmax = 0.957 | θmax = 25.3° |
| 1540 measured reflections | 3 standard reflections every 120 min |
| 1418 independent reflections | intensity decay: none |
Refinement top
| R[F2 > 2σ(F2)] = 0.073 | H-atom parameters constrained |
| wR(F2) = 0.182 | Δρmax = 0.27 e Å−3 |
| S = 1.00 | Δρmin = −0.33 e Å−3 |
| 1418 reflections | Absolute structure: ? |
| 103 parameters | Flack parameter: ? |
| 0 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 | 0.08801 (17) | 0.32257 (19) | 0.5711 (2) | 0.0767 (5) | |
| O1 | 0.3498 (8) | 0.0413 (6) | 0.7577 (7) | 0.1159 (19) | |
| O2 | 0.2991 (5) | 0.0203 (5) | 0.4775 (6) | 0.0819 (12) | |
| N1 | 0.3567 (5) | 0.1130 (5) | 0.6413 (6) | 0.0590 (10) | |
| N2 | 1.0736 (7) | 0.7724 (7) | 1.0090 (8) | 0.0942 (17) | |
| C1 | 0.6103 (7) | 0.7170 (6) | 0.8157 (7) | 0.0652 (12) | |
| H1A | 0.6681 | 0.8512 | 0.8556 | 0.077* | |
| C2 | 0.4139 (6) | 0.6306 (6) | 0.7290 (7) | 0.0602 (12) | |
| H2A | 0.3418 | 0.7057 | 0.7106 | 0.072* | |
| C3 | 0.3307 (6) | 0.4305 (6) | 0.6717 (6) | 0.0560 (12) | |
| C4 | 0.4384 (6) | 0.3252 (6) | 0.7025 (6) | 0.0502 (11) | |
| C5 | 0.6290 (6) | 0.4094 (6) | 0.7883 (6) | 0.0581 (12) | |
| H5A | 0.7001 | 0.3352 | 0.8108 | 0.070* | |
| C6 | 0.7137 (6) | 0.6118 (6) | 0.8413 (6) | 0.0478 (10) | |
| C7 | 0.9133 (7) | 0.7033 (7) | 0.9310 (8) | 0.0718 (15) | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cl | 0.0388 (6) | 0.0651 (8) | 0.1075 (11) | 0.0117 (5) | 0.0161 (6) | 0.0143 (7) |
| O1 | 0.187 (5) | 0.048 (2) | 0.111 (4) | 0.028 (3) | 0.076 (3) | 0.031 (2) |
| O2 | 0.064 (2) | 0.047 (2) | 0.098 (3) | 0.0060 (16) | 0.015 (2) | −0.007 (2) |
| N1 | 0.046 (2) | 0.038 (2) | 0.078 (3) | 0.0103 (16) | 0.027 (2) | 0.005 (2) |
| N2 | 0.059 (3) | 0.068 (3) | 0.110 (4) | −0.004 (2) | −0.001 (3) | −0.001 (3) |
| C1 | 0.062 (2) | 0.034 (3) | 0.078 (3) | 0.005 (2) | 0.031 (2) | 0.004 (2) |
| C2 | 0.046 (2) | 0.048 (3) | 0.079 (3) | 0.018 (2) | 0.022 (2) | 0.011 (2) |
| C3 | 0.037 (2) | 0.047 (2) | 0.068 (3) | 0.0102 (19) | 0.027 (2) | 0.003 (2) |
| C4 | 0.044 (2) | 0.032 (2) | 0.065 (3) | 0.0098 (17) | 0.033 (2) | 0.0069 (19) |
| C5 | 0.043 (2) | 0.042 (2) | 0.071 (3) | 0.0143 (19) | 0.020 (2) | −0.001 (2) |
| C6 | 0.047 (2) | 0.039 (2) | 0.053 (2) | 0.0128 (18) | 0.0204 (19) | 0.0112 (18) |
| C7 | 0.050 (3) | 0.048 (3) | 0.088 (4) | 0.004 (2) | 0.016 (3) | 0.001 (3) |
Geometric parameters (Å, °) top
| Cl—C3 | 1.726 (4) | C4—C3 | 1.354 (6) |
| N1—O1 | 1.213 (6) | C4—C5 | 1.370 (6) |
| N1—O2 | 1.214 (5) | C5—C6 | 1.406 (6) |
| C1—H1A | 0.9300 | C5—H5A | 0.9300 |
| C2—C1 | 1.407 (7) | C6—C1 | 1.316 (6) |
| C2—C3 | 1.386 (6) | C6—C7 | 1.434 (7) |
| C2—H2A | 0.9300 | C7—N2 | 1.166 (6) |
| C4—N1 | 1.466 (5) | | |
| | | |
| O1—N1—O2 | 124.2 (4) | C2—C3—Cl | 118.9 (4) |
| O1—N1—C4 | 117.9 (4) | C4—C3—Cl | 121.5 (3) |
| O2—N1—C4 | 117.9 (4) | C4—C3—C2 | 119.5 (4) |
| C1—C2—H2A | 120.9 | C3—C4—N1 | 121.1 (4) |
| C1—C6—C5 | 120.8 (4) | C3—C4—C5 | 122.2 (4) |
| C1—C6—C7 | 120.3 (4) | C5—C4—N1 | 116.6 (4) |
| C2—C1—H1A | 119.4 | C4—C5—C6 | 117.8 (4) |
| C6—C1—C2 | 121.3 (4) | C4—C5—H5A | 121.1 |
| C6—C1—H1A | 119.4 | C6—C5—H5A | 121.1 |
| C3—C2—C1 | 118.3 (4) | C5—C6—C7 | 118.8 (4) |
| C3—C2—H2A | 120.9 | N2—C7—C6 | 176.8 (6) |
| | | |
| C3—C2—C1—C6 | 0.4 (7) | C5—C4—C3—Cl | −177.5 (4) |
| C1—C2—C3—C4 | 0.9 (7) | N1—C4—C3—Cl | 3.8 (6) |
| C1—C2—C3—Cl | 178.2 (4) | C3—C4—C5—C6 | −1.4 (7) |
| C3—C4—N1—O1 | −120.7 (5) | N1—C4—C5—C6 | 177.3 (4) |
| C5—C4—N1—O1 | 60.6 (6) | C4—C5—C6—C1 | 2.6 (7) |
| C3—C4—N1—O2 | 58.9 (5) | C4—C5—C6—C7 | −179.8 (4) |
| C5—C4—N1—O2 | −119.8 (5) | C5—C6—C1—C2 | −2.1 (7) |
| C5—C4—C3—C2 | −0.3 (7) | C7—C6—C1—C2 | −179.6 (5) |
| N1—C4—C3—C2 | −179.0 (4) | | |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2A···O1i | 0.93 | 2.48 | 3.288 (7) | 145 |
| C5—H5A···N2ii | 0.93 | 2.61 | 3.497 (7) | 159 |
| Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y+1, −z+2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2A···O1i | 0.93 | 2.48 | 3.288 (7) | 145 |
| C5—H5A···N2ii | 0.93 | 2.61 | 3.497 (7) | 159 |
| Symmetry codes: (i) x, y+1, z; (ii) −x+2, −y+1, −z+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]](./hk2597fig1thm.gif)
![[Figure 2]](./hk2597fig2thm.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, C7, N1 and N2 are -0.040 (3), -0.049 (3), 0.005 (3) and 0.036 (3) Å away from the plane of the benzene ring.
In the crystal structure, weak intermolecular C-H···O and C-H···N 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) 1 - x, 1 - y, -z, where Cg1 is centroid of the ring A (C1-C6)] may further stabilize the structure, with centroid-centroid distance of 3.912 (3) Å.