organic compounds
Methyl 2-(4-chloro-3,5-dinitrobenzamido)acetate
aHenan University of Traditional Medicine, Zhengzhou 450008, People's Republic of China, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
*Correspondence e-mail: Edward.Tiekink@gmail.com
The title molecule, C10H8ClN3O7, is twisted with the dihedral angle between the amide and benzene ring being 38.75 (11)°. The C—N—C—C torsion angle between the amide and acetyl groups is −150.1 (2)°. Finally, each nitro group is twisted out of the plane of the benzene ring to which it is connected [O—N—C—C torsion angles = 34.0 (3) and −64.5 (3)°]. Linear supramolecular chains along [010] and mediated by N—H⋯O hydrogen bonds between successive amide groups dominate the crystal packing. The chains are consolidated into the three-dimensional structure by C—H⋯O contacts.
Related literature
For biological and crystal engineering studies of related compounds, see: Liu et al. (2009); Eissmann & Weber (2011).
Experimental
Crystal data
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Data collection: CrysAlis PRO (Agilent, 2010); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536811050446/hg5145sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811050446/hg5145Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811050446/hg5145Isup3.cml
To a solution of 4-chloro-3,5-dinitrobenzoic acid (0.48 g, 2 mmol) in dichloromethane (30 ml) was added 1-ethyl-3-(3-dimethylaminopropyl)carbodiimidehydrochloride (0.40 g, 2.1 mmol) and N,N-dimethylaminopyridine (25 mg, 0.2 mmol). The mixture was stirred at room temperature for an hour. Methyl 2-aminoacetate (178 mg, 2 mmol) in chloroform (20 ml) along with several drops of triethylamine were added. After another six hours, the mixture was subjected to
(petroleum ether/acetone 4:1) to provide the product as a yellow solid (501.5 mg, 80% yield). Crystals were grown from a mixture of dichloromethane and n-hexane (1:1 v/v).Carbon-bound H-atoms were placed in calculated positions [C—H 0.95 to 0.99 Å, Uiso(H) 1.2 to 1.5Ueq(C)] and were included in the
in the riding model approximation. The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint of N—H 0.88±0.01 Å, and with free Uiso.Molecules related to the title compound, (I), attract interest for their biological properties (Liu et al., 2009) and also in terms of crystal engineering endeavours (Eissmann & Weber, 2011). In (I), Fig. 1, the dihedral angle between the amide (O3,N1,C4) atoms and the benzene ring is 38.75 (11)°. The acetyl group is also twisted out of the plane of the amide group with the C4—N1—C3—C2 torsion angle being -150.1 (2)°. Each nitro group is twisted out of the plane of the benzene ring to which it is connected with the O4—N2—C7—C6 torsion angle = 34.0 (3)° and with O6—N3—C9—C8 = -64.5 (3)°.
The crystal packing is dominated by the formation of linear supramolecular chains along the b axis and mediated by N—H···O hydrogen bonds involving the amide group, Fig. 2 and Table 1. Chains are consolidated in the crystal packing by C—H···O interactions, Fig. 3 and Table 1.
For biological and crystal engineering studies of related compounds, see: Liu et al. (2009); Eissmann & Weber (2011).
Data collection: CrysAlis PRO (Agilent, 2010); cell
CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).C10H8ClN3O7 | F(000) = 648 |
Mr = 317.64 | Dx = 1.635 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 2633 reflections |
a = 14.5219 (5) Å | θ = 2.6–27.5° |
b = 4.7949 (2) Å | µ = 0.34 mm−1 |
c = 18.5368 (6) Å | T = 100 K |
V = 1290.74 (8) Å3 | Prism, yellow |
Z = 4 | 0.30 × 0.20 × 0.10 mm |
Agilent SuperNova Dual diffractometer with Atlas detector | 2258 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 2134 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.030 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 27.6°, θmin = 2.8° |
ω scan | h = −13→18 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −6→5 |
Tmin = 0.906, Tmax = 0.967 | l = −17→24 |
4743 measured reflections |
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)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.074 | w = 1/[σ2(Fo2) + (0.0367P)2 + 0.1422P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
2258 reflections | Δρmax = 0.22 e Å−3 |
194 parameters | Δρmin = −0.25 e Å−3 |
2 restraints | Absolute structure: Flack (1983), 725 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.05 (6) |
C10H8ClN3O7 | V = 1290.74 (8) Å3 |
Mr = 317.64 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 14.5219 (5) Å | µ = 0.34 mm−1 |
b = 4.7949 (2) Å | T = 100 K |
c = 18.5368 (6) Å | 0.30 × 0.20 × 0.10 mm |
Agilent SuperNova Dual diffractometer with Atlas detector | 2258 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | 2134 reflections with I > 2σ(I) |
Tmin = 0.906, Tmax = 0.967 | Rint = 0.030 |
4743 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.074 | Δρmax = 0.22 e Å−3 |
S = 1.08 | Δρmin = −0.25 e Å−3 |
2258 reflections | Absolute structure: Flack (1983), 725 Friedel pairs |
194 parameters | Absolute structure parameter: −0.05 (6) |
2 restraints |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.97666 (4) | 0.68297 (13) | 0.49982 (3) | 0.02449 (14) | |
O1 | 0.46196 (11) | 0.5789 (4) | 0.87399 (9) | 0.0214 (4) | |
O2 | 0.51448 (12) | 0.8605 (3) | 0.78629 (9) | 0.0232 (4) | |
O3 | 0.73214 (11) | 0.1135 (3) | 0.76810 (9) | 0.0212 (4) | |
O4 | 1.03518 (12) | 0.0525 (4) | 0.65033 (11) | 0.0278 (4) | |
O5 | 1.09547 (11) | 0.4311 (4) | 0.60728 (11) | 0.0282 (4) | |
O6 | 0.81733 (12) | 1.0984 (3) | 0.50745 (10) | 0.0286 (4) | |
O7 | 0.71827 (12) | 0.7754 (4) | 0.48417 (10) | 0.0329 (5) | |
N1 | 0.67321 (13) | 0.5506 (4) | 0.77382 (11) | 0.0154 (4) | |
N2 | 1.03014 (12) | 0.2929 (4) | 0.62781 (11) | 0.0188 (4) | |
N3 | 0.78247 (13) | 0.8709 (4) | 0.51797 (10) | 0.0179 (4) | |
C1 | 0.37848 (17) | 0.7447 (6) | 0.87927 (14) | 0.0260 (5) | |
H1A | 0.3379 | 0.6641 | 0.9160 | 0.039* | |
H1B | 0.3469 | 0.7454 | 0.8326 | 0.039* | |
H1C | 0.3944 | 0.9363 | 0.8928 | 0.039* | |
C2 | 0.52388 (15) | 0.6648 (5) | 0.82581 (12) | 0.0152 (5) | |
C3 | 0.60829 (15) | 0.4829 (5) | 0.83024 (12) | 0.0180 (5) | |
H3A | 0.6381 | 0.5085 | 0.8778 | 0.022* | |
H3B | 0.5899 | 0.2847 | 0.8259 | 0.022* | |
C4 | 0.72913 (14) | 0.3572 (5) | 0.74666 (12) | 0.0144 (4) | |
C5 | 0.79056 (16) | 0.4510 (5) | 0.68634 (11) | 0.0141 (5) | |
C6 | 0.87941 (15) | 0.3419 (5) | 0.68295 (12) | 0.0144 (5) | |
H6 | 0.9001 | 0.2141 | 0.7186 | 0.017* | |
C7 | 0.93716 (15) | 0.4205 (5) | 0.62750 (12) | 0.0148 (4) | |
C8 | 0.90958 (15) | 0.6012 (5) | 0.57315 (12) | 0.0154 (5) | |
C9 | 0.81934 (15) | 0.6983 (5) | 0.57707 (12) | 0.0148 (4) | |
C10 | 0.76008 (15) | 0.6285 (4) | 0.63220 (12) | 0.0150 (4) | |
H10 | 0.6992 | 0.7008 | 0.6332 | 0.018* | |
H1 | 0.688 (2) | 0.722 (3) | 0.7627 (15) | 0.034 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0208 (2) | 0.0329 (3) | 0.0197 (3) | −0.0005 (2) | 0.0067 (3) | 0.0055 (3) |
O1 | 0.0187 (8) | 0.0221 (9) | 0.0235 (9) | 0.0055 (7) | 0.0068 (7) | 0.0057 (8) |
O2 | 0.0229 (9) | 0.0218 (9) | 0.0250 (9) | 0.0052 (7) | 0.0007 (7) | 0.0080 (8) |
O3 | 0.0222 (8) | 0.0118 (8) | 0.0296 (9) | 0.0021 (6) | 0.0050 (8) | 0.0042 (7) |
O4 | 0.0222 (9) | 0.0231 (10) | 0.0381 (11) | 0.0077 (7) | 0.0013 (8) | 0.0099 (9) |
O5 | 0.0127 (8) | 0.0264 (9) | 0.0455 (11) | −0.0055 (7) | 0.0033 (8) | 0.0016 (9) |
O6 | 0.0452 (10) | 0.0165 (8) | 0.0239 (9) | −0.0042 (8) | −0.0027 (9) | 0.0078 (8) |
O7 | 0.0313 (10) | 0.0340 (11) | 0.0334 (11) | −0.0022 (8) | −0.0180 (9) | 0.0075 (9) |
N1 | 0.0197 (9) | 0.0095 (9) | 0.0171 (9) | 0.0005 (7) | 0.0019 (8) | 0.0020 (8) |
N2 | 0.0140 (10) | 0.0219 (11) | 0.0206 (10) | −0.0005 (8) | −0.0006 (8) | 0.0001 (9) |
N3 | 0.0220 (9) | 0.0187 (10) | 0.0129 (9) | 0.0047 (8) | 0.0004 (8) | −0.0007 (8) |
C1 | 0.0173 (11) | 0.0303 (13) | 0.0305 (13) | 0.0060 (11) | 0.0032 (11) | −0.0036 (13) |
C2 | 0.0167 (10) | 0.0155 (11) | 0.0133 (11) | 0.0003 (9) | −0.0011 (9) | −0.0038 (9) |
C3 | 0.0195 (11) | 0.0176 (12) | 0.0171 (11) | 0.0029 (9) | 0.0023 (9) | 0.0044 (9) |
C4 | 0.0133 (9) | 0.0149 (12) | 0.0150 (10) | −0.0016 (8) | −0.0039 (9) | 0.0012 (9) |
C5 | 0.0152 (10) | 0.0128 (11) | 0.0142 (10) | −0.0023 (9) | −0.0013 (8) | −0.0019 (9) |
C6 | 0.0158 (11) | 0.0112 (11) | 0.0161 (10) | 0.0023 (9) | −0.0031 (9) | 0.0005 (9) |
C7 | 0.0111 (10) | 0.0131 (10) | 0.0201 (11) | 0.0018 (9) | −0.0011 (9) | −0.0035 (9) |
C8 | 0.0148 (10) | 0.0163 (12) | 0.0149 (10) | −0.0029 (9) | 0.0026 (9) | −0.0019 (9) |
C9 | 0.0186 (11) | 0.0106 (11) | 0.0151 (10) | 0.0000 (9) | −0.0016 (9) | 0.0011 (9) |
C10 | 0.0154 (10) | 0.0113 (10) | 0.0185 (11) | 0.0002 (9) | 0.0001 (9) | −0.0029 (9) |
Cl1—C8 | 1.718 (2) | C1—H1B | 0.9800 |
O1—C2 | 1.333 (3) | C1—H1C | 0.9800 |
O1—C1 | 1.453 (3) | C2—C3 | 1.507 (3) |
O2—C2 | 1.198 (3) | C3—H3A | 0.9900 |
O3—C4 | 1.235 (3) | C3—H3B | 0.9900 |
O4—N2 | 1.228 (3) | C4—C5 | 1.499 (3) |
O5—N2 | 1.218 (2) | C5—C10 | 1.388 (3) |
O6—N3 | 1.218 (2) | C5—C6 | 1.394 (3) |
O7—N3 | 1.213 (2) | C6—C7 | 1.379 (3) |
N1—C4 | 1.331 (3) | C6—H6 | 0.9500 |
N1—C3 | 1.445 (3) | C7—C8 | 1.388 (3) |
N1—H1 | 0.875 (10) | C8—C9 | 1.393 (3) |
N2—C7 | 1.482 (3) | C9—C10 | 1.377 (3) |
N3—C9 | 1.474 (3) | C10—H10 | 0.9500 |
C1—H1A | 0.9800 | ||
C2—O1—C1 | 116.05 (18) | C2—C3—H3B | 109.4 |
C4—N1—C3 | 121.01 (19) | H3A—C3—H3B | 108.0 |
C4—N1—H1 | 115 (2) | O3—C4—N1 | 124.0 (2) |
C3—N1—H1 | 123 (2) | O3—C4—C5 | 120.2 (2) |
O5—N2—O4 | 124.78 (19) | N1—C4—C5 | 115.9 (2) |
O5—N2—C7 | 118.92 (19) | C10—C5—C6 | 119.5 (2) |
O4—N2—C7 | 116.30 (18) | C10—C5—C4 | 122.2 (2) |
O7—N3—O6 | 125.1 (2) | C6—C5—C4 | 118.15 (19) |
O7—N3—C9 | 116.80 (19) | C7—C6—C5 | 119.6 (2) |
O6—N3—C9 | 118.10 (19) | C7—C6—H6 | 120.2 |
O1—C1—H1A | 109.5 | C5—C6—H6 | 120.2 |
O1—C1—H1B | 109.5 | C6—C7—C8 | 122.43 (19) |
H1A—C1—H1B | 109.5 | C6—C7—N2 | 115.99 (19) |
O1—C1—H1C | 109.5 | C8—C7—N2 | 121.56 (19) |
H1A—C1—H1C | 109.5 | C7—C8—C9 | 116.3 (2) |
H1B—C1—H1C | 109.5 | C7—C8—Cl1 | 123.59 (17) |
O2—C2—O1 | 125.1 (2) | C9—C8—Cl1 | 119.92 (18) |
O2—C2—C3 | 125.4 (2) | C10—C9—C8 | 123.1 (2) |
O1—C2—C3 | 109.49 (19) | C10—C9—N3 | 117.46 (19) |
N1—C3—C2 | 111.18 (18) | C8—C9—N3 | 119.4 (2) |
N1—C3—H3A | 109.4 | C9—C10—C5 | 119.1 (2) |
C2—C3—H3A | 109.4 | C9—C10—H10 | 120.5 |
N1—C3—H3B | 109.4 | C5—C10—H10 | 120.5 |
C1—O1—C2—O2 | −1.9 (3) | O4—N2—C7—C8 | −144.0 (2) |
C1—O1—C2—C3 | 176.48 (19) | C6—C7—C8—C9 | −0.6 (3) |
C4—N1—C3—C2 | −150.1 (2) | N2—C7—C8—C9 | 177.3 (2) |
O2—C2—C3—N1 | −7.6 (3) | C6—C7—C8—Cl1 | −174.96 (18) |
O1—C2—C3—N1 | 174.00 (19) | N2—C7—C8—Cl1 | 3.0 (3) |
C3—N1—C4—O3 | −2.2 (3) | C7—C8—C9—C10 | 1.7 (3) |
C3—N1—C4—C5 | 177.61 (19) | Cl1—C8—C9—C10 | 176.32 (18) |
O3—C4—C5—C10 | 139.5 (2) | C7—C8—C9—N3 | −174.6 (2) |
N1—C4—C5—C10 | −40.3 (3) | Cl1—C8—C9—N3 | −0.1 (3) |
O3—C4—C5—C6 | −36.8 (3) | O7—N3—C9—C10 | −59.9 (3) |
N1—C4—C5—C6 | 143.4 (2) | O6—N3—C9—C10 | 118.9 (2) |
C10—C5—C6—C7 | 2.6 (3) | O7—N3—C9—C8 | 116.6 (2) |
C4—C5—C6—C7 | 179.0 (2) | O6—N3—C9—C8 | −64.5 (3) |
C5—C6—C7—C8 | −1.6 (3) | C8—C9—C10—C5 | −0.7 (3) |
C5—C6—C7—N2 | −179.6 (2) | N3—C9—C10—C5 | 175.76 (19) |
O5—N2—C7—C6 | −144.8 (2) | C6—C5—C10—C9 | −1.5 (3) |
O4—N2—C7—C6 | 34.0 (3) | C4—C5—C10—C9 | −177.75 (19) |
O5—N2—C7—C8 | 37.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.88 (1) | 1.99 (1) | 2.833 (3) | 163 (3) |
C1—H1a···O7ii | 0.98 | 2.59 | 3.460 (3) | 148 |
C3—H3a···O6iii | 0.99 | 2.53 | 3.502 (3) | 169 |
C3—H3b···O2iv | 0.99 | 2.42 | 3.380 (3) | 162 |
C10—H10···O5v | 0.95 | 2.37 | 3.223 (3) | 149 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, z+1/2; (iii) −x+3/2, y−1/2, z+1/2; (iv) x, y−1, z; (v) x−1/2, −y+3/2, z. |
Experimental details
Crystal data | |
Chemical formula | C10H8ClN3O7 |
Mr | 317.64 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 100 |
a, b, c (Å) | 14.5219 (5), 4.7949 (2), 18.5368 (6) |
V (Å3) | 1290.74 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Agilent SuperNova Dual diffractometer with Atlas detector |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2010) |
Tmin, Tmax | 0.906, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4743, 2258, 2134 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.074, 1.08 |
No. of reflections | 2258 |
No. of parameters | 194 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.25 |
Absolute structure | Flack (1983), 725 Friedel pairs |
Absolute structure parameter | −0.05 (6) |
Computer programs: CrysAlis PRO (Agilent, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O3i | 0.88 (1) | 1.99 (1) | 2.833 (3) | 163 (3) |
C1—H1a···O7ii | 0.98 | 2.59 | 3.460 (3) | 148 |
C3—H3a···O6iii | 0.99 | 2.53 | 3.502 (3) | 169 |
C3—H3b···O2iv | 0.99 | 2.42 | 3.380 (3) | 162 |
C10—H10···O5v | 0.95 | 2.37 | 3.223 (3) | 149 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, z+1/2; (iii) −x+3/2, y−1/2, z+1/2; (iv) x, y−1, z; (v) x−1/2, −y+3/2, z. |
Acknowledgements
We thank Henan University of Traditional Medicine and the University of Malaya for supporting this study.
References
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Molecules related to the title compound, (I), attract interest for their biological properties (Liu et al., 2009) and also in terms of crystal engineering endeavours (Eissmann & Weber, 2011). In (I), Fig. 1, the dihedral angle between the amide (O3,N1,C4) atoms and the benzene ring is 38.75 (11)°. The acetyl group is also twisted out of the plane of the amide group with the C4—N1—C3—C2 torsion angle being -150.1 (2)°. Each nitro group is twisted out of the plane of the benzene ring to which it is connected with the O4—N2—C7—C6 torsion angle = 34.0 (3)° and with O6—N3—C9—C8 = -64.5 (3)°.
The crystal packing is dominated by the formation of linear supramolecular chains along the b axis and mediated by N—H···O hydrogen bonds involving the amide group, Fig. 2 and Table 1. Chains are consolidated in the crystal packing by C—H···O interactions, Fig. 3 and Table 1.