 | Acta Crystallographica Section E Acta Crystallographica Section E CRYSTALLOGRAPHIC COMMUNICATIONS |
journal menu
organic compounds
| CRYSTALLOGRAPHIC COMMUNICATIONS |
access4-Nitrophenyl 2-chlorobenzoate
aDepartment of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan, and bInstitut fur Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
*Correspondence e-mail: humaira_siddiqi@yahoo.com
The aromatic rings in the title compound, C13H8ClNO4, enclose a dihedral angle of 39.53 (3)°. The nitro group is almost coplanar with the ring to which it is attached [dihedral angle = 4.31 (1)°]. In the crystal, molecules are connected by C—H⋯O hydrogen bonds into chains running along [001].
Related literature
For the use of 4-nitrophenyl-2-chlorobenzoate as a starting material for the synthesis of pain-relieving and anti-inflammatory drugs, see: Selvakumar et al. (2002![[Selvakumar, N., Malar Azhagan, A., Seinivas, D. & Gopi Krishna, G. (2002). Tetrahedron Lett. 43, 9175-9178.]](../../../../../../logos/arrows/e_arr.gif "Selvakumar, N., Malar Azhagan, A., Seinivas, D. & Gopi Krishna, G. (2002). Tetrahedron Lett. 43, 9175-9178.")
); Jefford & Zaslona (1985). For a similar hydrogen-bonding pattern in a related structure, see: Akhter et al. (2012).
![[Scheme 1]](ff2092scheme1.gif)
Experimental
Crystal data
|
Refinement
|
| |||||||||||||||||
Data collection: X-AREA (Stoe & Cie, 2001); cell X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812050362/ff2092sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050362/ff2092Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812050362/ff2092Isup3.cml
2-Chlorobenzoyl chloride was added drop wise to the solution of 4-nitrophenol (in a mixture of dry tetrahydrofuran (THF) and triethyl amine). The reaction mixture was stirred at room temperature for two hours and then was poured into the cold water. The oily product settled down after allowing the solution to stand for two hours, the supernatant liquid was decanted. The product was extracted from the solution by extraction with ethyl acetate, washed with 10% NaHCO3 solution to remove any traces of reactants and recrystallized from methanol. Yield 78%, m.p. 416–418 K.
All H atoms were initially located by difference Fourier synthesis. Subsequently all H atoms were refined using a riding model with C—H = 0.95 Å and with Uiso(H) = 1.2Ueq(C).
The aromatic like 4-Nitrophenyl-2-chlorobenzoate, can be used as starting materials for the synthesis of several pain-relieving and anti-inflammatory drugs (Selvakumar et al., 2002; Jefford & Zaslona, 1985).
The two aromatic rings in the title compound enclose a dihedral angle of 39.53 (3)°. The nitro group is almost coplanar with the phenyl ring to which it is attached [dihedral angle 4.31 (1)°]. In the crystal, the molecules are connected by C—H···O bonds to chains running along [0 0 1].
For the use of 4-nitrophenyl-2-chlorobenzoate as a starting material for the synthesis of pain-relieving and anti-inflammatory drugs, see: Selvakumar et al. (2002); Jefford & Zaslona (1985). For a similar hydrogen-bonding pattern in a related structure, see: Akhter et al. (2012).
Data collection: X-AREA (Stoe & Cie, 2001); cell X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./ff2092fig1thm.gif) | Fig. 1. Perspective view of the title compound with the atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. |
| C13H8ClNO4 | F(000) = 1136 |
| Mr = 277.65 | Dx = 1.592 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 57790 reflections |
| a = 11.4790 (4) Å | θ = 3.2–30.1° |
| b = 14.0461 (5) Å | µ = 0.34 mm−1 |
| c = 14.3702 (7) Å | T = 173 K |
| V = 2316.98 (16) Å3 | Rod, colourless |
| Z = 8 | 0.36 × 0.15 × 0.15 mm |
| Stoe IPDS II two-circle diffractometer | 3251 independent reflections |
| Radiation source: Genix 3D IµS microfocus X-ray source | 3071 reflections with I > 2σ(I) |
| Genix 3D multilayer optics monochromator | Rint = 0.057 |
| ω scans | θmax = 29.7°, θmin = 3.2° |
| Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001) | h = −15→15 |
| Tmin = 0.888, Tmax = 0.951 | k = −19→18 |
| 54293 measured reflections | l = −19→19 |
| 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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.105 | H-atom parameters constrained |
| S = 1.14 | w = 1/[σ2(Fo2) + (0.0411P)2 + 1.2306P] where P = (Fo2 + 2Fc2)/3 |
| 3251 reflections | (Δ/σ)max = 0.001 |
| 172 parameters | Δρmax = 0.32 e Å−3 |
| 0 restraints | Δρmin = −0.41 e Å−3 |
| C13H8ClNO4 | V = 2316.98 (16) Å3 |
| Mr = 277.65 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 11.4790 (4) Å | µ = 0.34 mm−1 |
| b = 14.0461 (5) Å | T = 173 K |
| c = 14.3702 (7) Å | 0.36 × 0.15 × 0.15 mm |
| Stoe IPDS II two-circle diffractometer | 3251 independent reflections |
| Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001) | 3071 reflections with I > 2σ(I) |
| Tmin = 0.888, Tmax = 0.951 | Rint = 0.057 |
| 54293 measured reflections |
| R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
| wR(F2) = 0.105 | H-atom parameters constrained |
| S = 1.14 | Δρmax = 0.32 e Å−3 |
| 3251 reflections | Δρmin = −0.41 e Å−3 |
| 172 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. 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. |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.66372 (3) | 0.20873 (4) | 0.41090 (3) | 0.04536 (14) | |
| N1 | 0.85406 (11) | 0.06742 (9) | 1.00169 (8) | 0.0282 (2) | |
| O1 | 0.93046 (12) | 0.09364 (13) | 1.05429 (8) | 0.0557 (4) | |
| O2 | 0.76471 (11) | 0.02876 (9) | 1.02808 (8) | 0.0417 (3) | |
| O3 | 0.92469 (8) | 0.11781 (8) | 0.62155 (6) | 0.0280 (2) | |
| O4 | 0.76541 (11) | 0.20800 (9) | 0.59665 (7) | 0.0403 (3) | |
| C1 | 0.88309 (12) | 0.15657 (9) | 0.46702 (8) | 0.0236 (2) | |
| C2 | 0.80645 (13) | 0.17488 (10) | 0.39336 (9) | 0.0272 (3) | |
| C3 | 0.84243 (15) | 0.16241 (11) | 0.30152 (10) | 0.0352 (3) | |
| H3 | 0.7894 | 0.1738 | 0.2520 | 0.042* | |
| C4 | 0.95451 (17) | 0.13369 (11) | 0.28236 (10) | 0.0372 (4) | |
| H4 | 0.9786 | 0.1251 | 0.2197 | 0.045* | |
| C5 | 1.03234 (16) | 0.11733 (11) | 0.35436 (10) | 0.0357 (3) | |
| H5 | 1.1102 | 0.0989 | 0.3411 | 0.043* | |
| C6 | 0.99620 (14) | 0.12797 (10) | 0.44555 (9) | 0.0297 (3) | |
| H6 | 1.0496 | 0.1155 | 0.4946 | 0.036* | |
| C7 | 0.84707 (12) | 0.16577 (10) | 0.56623 (9) | 0.0246 (3) | |
| C11 | 0.90125 (11) | 0.10896 (9) | 0.71610 (8) | 0.0219 (2) | |
| C12 | 0.79705 (12) | 0.07089 (9) | 0.74716 (9) | 0.0242 (3) | |
| H12 | 0.7375 | 0.0541 | 0.7043 | 0.029* | |
| C13 | 0.78119 (11) | 0.05777 (9) | 0.84200 (9) | 0.0232 (2) | |
| H13 | 0.7102 | 0.0325 | 0.8655 | 0.028* | |
| C14 | 0.87097 (11) | 0.08221 (9) | 0.90168 (8) | 0.0214 (2) | |
| C15 | 0.97586 (11) | 0.11932 (10) | 0.87098 (9) | 0.0233 (2) | |
| H15 | 1.0360 | 0.1350 | 0.9137 | 0.028* | |
| C16 | 0.99071 (11) | 0.13298 (9) | 0.77635 (9) | 0.0235 (2) | |
| H16 | 1.0615 | 0.1586 | 0.7530 | 0.028* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.02762 (19) | 0.0729 (3) | 0.0356 (2) | −0.00627 (18) | −0.00863 (14) | 0.01702 (19) |
| N1 | 0.0323 (6) | 0.0349 (6) | 0.0174 (5) | −0.0006 (5) | 0.0003 (4) | 0.0019 (4) |
| O1 | 0.0494 (7) | 0.0997 (12) | 0.0180 (5) | −0.0213 (8) | −0.0083 (5) | 0.0016 (6) |
| O2 | 0.0450 (7) | 0.0552 (7) | 0.0251 (5) | −0.0142 (6) | 0.0084 (5) | 0.0051 (5) |
| O3 | 0.0270 (5) | 0.0425 (6) | 0.0144 (4) | 0.0076 (4) | 0.0011 (3) | 0.0034 (4) |
| O4 | 0.0442 (7) | 0.0520 (7) | 0.0246 (5) | 0.0231 (5) | 0.0002 (4) | −0.0003 (5) |
| C1 | 0.0312 (6) | 0.0239 (6) | 0.0155 (5) | −0.0014 (5) | −0.0013 (5) | 0.0006 (4) |
| C2 | 0.0313 (7) | 0.0293 (6) | 0.0209 (6) | −0.0097 (5) | −0.0052 (5) | 0.0051 (5) |
| C3 | 0.0509 (9) | 0.0372 (8) | 0.0174 (6) | −0.0186 (7) | −0.0075 (6) | 0.0062 (5) |
| C4 | 0.0610 (10) | 0.0341 (8) | 0.0166 (6) | −0.0105 (7) | 0.0064 (6) | −0.0017 (5) |
| C5 | 0.0484 (9) | 0.0335 (7) | 0.0251 (7) | 0.0047 (7) | 0.0102 (6) | −0.0009 (5) |
| C6 | 0.0362 (7) | 0.0332 (7) | 0.0196 (6) | 0.0064 (6) | 0.0015 (5) | −0.0004 (5) |
| C7 | 0.0293 (6) | 0.0278 (6) | 0.0167 (5) | 0.0027 (5) | −0.0027 (5) | 0.0002 (5) |
| C11 | 0.0243 (6) | 0.0269 (6) | 0.0146 (5) | 0.0042 (5) | 0.0005 (4) | 0.0009 (4) |
| C12 | 0.0235 (6) | 0.0304 (6) | 0.0187 (5) | −0.0008 (5) | −0.0031 (4) | −0.0040 (5) |
| C13 | 0.0230 (6) | 0.0263 (6) | 0.0204 (5) | −0.0025 (5) | 0.0011 (4) | −0.0008 (5) |
| C14 | 0.0249 (6) | 0.0238 (6) | 0.0155 (5) | 0.0013 (5) | −0.0002 (4) | 0.0005 (4) |
| C15 | 0.0214 (5) | 0.0297 (6) | 0.0189 (5) | −0.0001 (5) | −0.0034 (4) | 0.0004 (5) |
| C16 | 0.0201 (5) | 0.0298 (6) | 0.0204 (5) | 0.0009 (5) | 0.0006 (4) | 0.0031 (5) |
| Cl1—C2 | 1.7245 (16) | C4—H4 | 0.9500 |
| N1—O1 | 1.2149 (17) | C5—C6 | 1.3827 (19) |
| N1—O2 | 1.2210 (16) | C5—H5 | 0.9500 |
| N1—C14 | 1.4650 (16) | C6—H6 | 0.9500 |
| O3—C7 | 1.3710 (16) | C11—C12 | 1.3842 (18) |
| O3—C11 | 1.3906 (14) | C11—C16 | 1.3849 (18) |
| O4—C7 | 1.1923 (17) | C12—C13 | 1.3873 (18) |
| C1—C6 | 1.394 (2) | C12—H12 | 0.9500 |
| C1—C2 | 1.4001 (18) | C13—C14 | 1.3839 (18) |
| C1—C7 | 1.4901 (17) | C13—H13 | 0.9500 |
| C2—C3 | 1.394 (2) | C14—C15 | 1.3842 (18) |
| C3—C4 | 1.376 (3) | C15—C16 | 1.3839 (17) |
| C3—H3 | 0.9500 | C15—H15 | 0.9500 |
| C4—C5 | 1.386 (2) | C16—H16 | 0.9500 |
| O1—N1—O2 | 123.23 (12) | O4—C7—O3 | 122.88 (12) |
| O1—N1—C14 | 118.15 (12) | O4—C7—C1 | 127.74 (12) |
| O2—N1—C14 | 118.63 (12) | O3—C7—C1 | 109.38 (11) |
| C7—O3—C11 | 118.99 (10) | C12—C11—C16 | 122.23 (11) |
| C6—C1—C2 | 118.10 (12) | C12—C11—O3 | 121.12 (11) |
| C6—C1—C7 | 119.68 (12) | C16—C11—O3 | 116.45 (11) |
| C2—C1—C7 | 122.21 (13) | C11—C12—C13 | 118.78 (12) |
| C3—C2—C1 | 120.43 (14) | C11—C12—H12 | 120.6 |
| C3—C2—Cl1 | 117.03 (11) | C13—C12—H12 | 120.6 |
| C1—C2—Cl1 | 122.49 (11) | C14—C13—C12 | 118.56 (12) |
| C4—C3—C2 | 120.22 (14) | C14—C13—H13 | 120.7 |
| C4—C3—H3 | 119.9 | C12—C13—H13 | 120.7 |
| C2—C3—H3 | 119.9 | C13—C14—C15 | 122.93 (11) |
| C3—C4—C5 | 120.12 (13) | C13—C14—N1 | 118.30 (12) |
| C3—C4—H4 | 119.9 | C15—C14—N1 | 118.77 (11) |
| C5—C4—H4 | 119.9 | C16—C15—C14 | 118.20 (11) |
| C6—C5—C4 | 119.75 (15) | C16—C15—H15 | 120.9 |
| C6—C5—H5 | 120.1 | C14—C15—H15 | 120.9 |
| C4—C5—H5 | 120.1 | C15—C16—C11 | 119.28 (12) |
| C5—C6—C1 | 121.36 (14) | C15—C16—H16 | 120.4 |
| C5—C6—H6 | 119.3 | C11—C16—H16 | 120.4 |
| C1—C6—H6 | 119.3 | ||
| C6—C1—C2—C3 | 1.5 (2) | C7—O3—C11—C12 | 54.46 (18) |
| C7—C1—C2—C3 | −177.88 (13) | C7—O3—C11—C16 | −130.52 (13) |
| C6—C1—C2—Cl1 | 178.88 (11) | C16—C11—C12—C13 | 1.0 (2) |
| C7—C1—C2—Cl1 | −0.49 (19) | O3—C11—C12—C13 | 175.74 (12) |
| C1—C2—C3—C4 | −1.2 (2) | C11—C12—C13—C14 | −0.81 (19) |
| Cl1—C2—C3—C4 | −178.77 (12) | C12—C13—C14—C15 | 0.1 (2) |
| C2—C3—C4—C5 | −0.2 (2) | C12—C13—C14—N1 | −179.49 (12) |
| C3—C4—C5—C6 | 1.4 (2) | O1—N1—C14—C13 | −176.12 (15) |
| C4—C5—C6—C1 | −1.1 (2) | O2—N1—C14—C13 | 4.49 (19) |
| C2—C1—C6—C5 | −0.3 (2) | O1—N1—C14—C15 | 4.3 (2) |
| C7—C1—C6—C5 | 179.08 (14) | O2—N1—C14—C15 | −175.11 (13) |
| C11—O3—C7—O4 | 7.1 (2) | C13—C14—C15—C16 | 0.4 (2) |
| C11—O3—C7—C1 | −173.56 (11) | N1—C14—C15—C16 | −179.97 (12) |
| C6—C1—C7—O4 | 162.13 (16) | C14—C15—C16—C11 | −0.3 (2) |
| C2—C1—C7—O4 | −18.5 (2) | C12—C11—C16—C15 | −0.5 (2) |
| C6—C1—C7—O3 | −17.14 (18) | O3—C11—C16—C15 | −175.43 (12) |
| C2—C1—C7—O3 | 162.22 (12) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| C4—H4···O1i | 0.95 | 2.48 | 3.3368 (19) | 150 |
| Symmetry code: (i) x, y, z−1. |
Experimental details
| Crystal data | |
| Chemical formula | C13H8ClNO4 |
| Mr | 277.65 |
| Crystal system, space group | Orthorhombic, Pbca |
| Temperature (K) | 173 |
| a, b, c (Å) | 11.4790 (4), 14.0461 (5), 14.3702 (7) |
| V (Å3) | 2316.98 (16) |
| Z | 8 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.34 |
| Crystal size (mm) | 0.36 × 0.15 × 0.15 |
| Data collection | |
| Diffractometer | Stoe IPDS II two-circle |
| Absorption correction | Multi-scan (X-AREA; Stoe & Cie, 2001) |
| Tmin, Tmax | 0.888, 0.951 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 54293, 3251, 3071 |
| Rint | 0.057 |
| (sin θ/λ)max (Å−1) | 0.697 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.105, 1.14 |
| No. of reflections | 3251 |
| No. of parameters | 172 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.32, −0.41 |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008).
| D—H···A | D—H | H···A | D···A | D—H···A |
| C4—H4···O1i | 0.95 | 2.48 | 3.3368 (19) | 150.1 |
| Symmetry code: (i) x, y, z−1. |
Acknowledgements
The authors acknowledge the Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan, for providing necessary research facilities.
References
Akhter, T., Masood Siddiqi, H., Akhter, Z. & McKee, V. (2012). Acta Cryst. E68, o1912. CSD CrossRef IUCr Journals Google Scholar
Jefford, C. W. & Zaslona, A. (1985). Tetrahedron Lett. 26, 6035–6038. CrossRef CAS Web of Science Google Scholar
Selvakumar, N., Malar Azhagan, A., Seinivas, D. & Gopi Krishna, G. (2002). Tetrahedron Lett. 43, 9175–9178. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
| CRYSTALLOGRAPHIC COMMUNICATIONS |
The aromatic esters, like 4-Nitrophenyl-2-chlorobenzoate, can be used as starting materials for the synthesis of several pain-relieving and anti-inflammatory drugs (Selvakumar et al., 2002; Jefford & Zaslona, 1985).
The two aromatic rings in the title compound enclose a dihedral angle of 39.53 (3)°. The nitro group is almost coplanar with the phenyl ring to which it is attached [dihedral angle 4.31 (1)°]. In the crystal, the molecules are connected by C—H···O bonds to chains running along [0 0 1].