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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2708.
Published online 2010 October 2. doi:  10.1107/S1600536810038742
PMCID: PMC3009323

2-Chloro­ethyl 4-nitro­benzoate

Abstract

The title compound, C9H8ClNO4, crystallizes with two mol­ecules in the asymmetric unit. In each mol­ecule, the carboxyl­ate group is nearly coplanar with the benzene ring, forming dihedral angles of 2.4 (1) and 4.9 (1)°. In the crystal, mol­ecules are linked through weak C—H(...)O and C—H(...)Cl hydrogen bonds. A short O(...)N contact of 2.7660 (19) Å occurs between the nitro groups of adjacent mol­ecules.

Related literature

For benzoates as inter­mediates in the chemistry of pigments and pharmaceuticals, see: Zhang et al. (1995 [triangle], 1990 [triangle]). For a related structure, see: Wu et al. (2009 [triangle]).

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Object name is e-66-o2708-scheme1.jpg

Experimental

Crystal data

  • C9H8ClNO4
  • M r = 229.61
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2708-efi1.jpg
  • a = 4.9404 (10) Å
  • b = 21.618 (5) Å
  • c = 18.325 (4) Å
  • β = 90.441 (3)°
  • V = 1957.0 (7) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.38 mm−1
  • T = 103 K
  • 0.40 × 0.20 × 0.20 mm

Data collection

  • Rigaku SPIDER diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.862, T max = 0.927
  • 18618 measured reflections
  • 4466 independent reflections
  • 3781 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.034
  • wR(F 2) = 0.084
  • S = 1.00
  • 4466 reflections
  • 271 parameters
  • H-atom parameters constrained
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810038742/xu5038sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038742/xu5038Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Science Foundation of the Health Department of Jiangsu Province, China (No. H200934).

supplementary crystallographic information

Comment

Benzoates are important intermediates in the chemistry of pigments and pharmaceuticals, which are widely used all over the world (Zhang et al., 1995; Zhang et al., 1990). The crystall structure of Methyl 4-nitrobenzoate has been reported (Wu et al., 2009). As an extension of our study, we report here the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig.1) contains two crystallographically independent molecules in an asymmetric unit.The crystal data show that the bond lengths and angles are within expected ranges. The ester groups and the benzene rings in the two molecules are almost coplanar, as indicated by the dihedral angles of 2.4 (1)° (O1/O2/C6/C7; C1—C6) and 4.9 (1)° (O1'/O2'/C6'/C7'; C1'—C6'). The dihedral angle between the ring(C1—C6) and the ring(C1'—C6') is 92.7 (1)°.

In the cyrstal structure, adjacent molecules are linked together by the weak C—H···O and C—H···Cl hydrogen bonds (Table 1). Intramolecular C—H···O interactions are also observed. These hydrogen-bonding interactions stabilize the crystal structure.

Experimental

Commercial 2-chloroethyl 4-nitrobenzoate was recrystallized by slow evaporation of methanol/water solution (1:1 v/v). Colourless single crystals were formed after two weeks.

Refinement

H atoms were placed in calculated positions with C–H = 0.99 (methylene) and 0.95 Å (aromatic), and were refined in a riding mode with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
eA view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 50% probability level.

Crystal data

C9H8ClNO4F(000) = 944
Mr = 229.61Dx = 1.559 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5688 reflections
a = 4.9404 (10) Åθ = 3.0–27.5°
b = 21.618 (5) ŵ = 0.38 mm1
c = 18.325 (4) ÅT = 103 K
β = 90.441 (3)°Prism, colorless
V = 1957.0 (7) Å30.40 × 0.20 × 0.20 mm
Z = 8

Data collection

Rigaku SPIDER diffractometer4466 independent reflections
Radiation source: Rotating Anode3781 reflections with I > 2σ(I)
graphiteRint = 0.033
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −6→6
Tmin = 0.862, Tmax = 0.927k = −28→28
18618 measured reflectionsl = −23→20

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0441P)2 + 0.680P] where P = (Fo2 + 2Fc2)/3
4466 reflections(Δ/σ)max = 0.001
271 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = −0.23 e Å3

Special details

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)

xyzUiso*/Ueq
Cl10.58062 (8)0.615621 (18)0.60156 (2)0.02137 (10)
O10.5719 (2)0.70861 (5)0.72719 (6)0.0201 (2)
O20.4652 (2)0.80061 (5)0.77677 (6)0.0230 (3)
O31.4451 (3)0.74075 (6)1.03965 (7)0.0288 (3)
O41.5555 (2)0.65746 (6)0.98123 (7)0.0274 (3)
N11.4158 (3)0.70367 (6)0.98970 (8)0.0203 (3)
C10.8669 (3)0.78260 (7)0.88589 (9)0.0169 (3)
H10.76990.82050.88650.020*
C21.0633 (3)0.77121 (7)0.93827 (9)0.0176 (3)
H21.10250.80070.97520.021*
C31.2012 (3)0.71558 (7)0.93535 (8)0.0163 (3)
C41.1480 (3)0.67097 (7)0.88291 (9)0.0169 (3)
H41.24550.63310.88250.020*
C50.9499 (3)0.68282 (7)0.83117 (8)0.0163 (3)
H50.90900.65280.79490.020*
C60.8102 (3)0.73879 (7)0.83215 (8)0.0143 (3)
C70.5974 (3)0.75381 (7)0.77687 (8)0.0155 (3)
C80.3759 (3)0.71808 (7)0.66929 (9)0.0193 (3)
H8A0.45550.74340.62990.023*
H8B0.21480.73990.68820.023*
C90.2977 (3)0.65561 (7)0.64066 (9)0.0183 (3)
H9A0.15410.66050.60310.022*
H9B0.22310.63050.68100.022*
Cl1'0.09925 (8)0.578510 (18)0.46926 (2)0.02083 (10)
O1'0.0719 (2)0.53366 (5)0.30930 (6)0.0170 (2)
O2'−0.0224 (2)0.45272 (5)0.23673 (6)0.0203 (2)
O3'0.9692 (2)0.56670 (5)0.00593 (7)0.0249 (3)
O4'1.0593 (2)0.63815 (6)0.08520 (6)0.0243 (3)
N1'0.9309 (3)0.59294 (6)0.06415 (7)0.0176 (3)
C1'0.3955 (3)0.49087 (7)0.13991 (8)0.0158 (3)
H1'0.30830.45270.12910.019*
C2'0.5964 (3)0.51288 (7)0.09445 (9)0.0165 (3)
H2'0.64970.49030.05250.020*
C3'0.7174 (3)0.56882 (7)0.11200 (8)0.0150 (3)
C4'0.6481 (3)0.60310 (7)0.17254 (9)0.0170 (3)
H4'0.73660.64110.18310.020*
C5'0.4468 (3)0.58079 (7)0.21743 (8)0.0160 (3)
H5'0.39410.60370.25920.019*
C6'0.3209 (3)0.52453 (7)0.20138 (8)0.0139 (3)
C7'0.1063 (3)0.49883 (7)0.24947 (8)0.0149 (3)
C8'−0.1343 (3)0.51265 (7)0.35872 (8)0.0168 (3)
H8'1−0.07180.47530.38520.020*
H8'2−0.30170.50220.33140.020*
C9'−0.1878 (3)0.56394 (8)0.41134 (9)0.0211 (3)
H9'1−0.34540.55300.44180.025*
H9'2−0.23340.60200.38390.025*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.01863 (19)0.0242 (2)0.0213 (2)−0.00012 (15)0.00069 (15)−0.00381 (16)
O10.0238 (6)0.0183 (5)0.0182 (6)0.0036 (5)−0.0087 (5)−0.0042 (4)
O20.0287 (6)0.0174 (5)0.0228 (6)0.0070 (5)−0.0078 (5)−0.0007 (5)
O30.0304 (7)0.0329 (7)0.0229 (7)−0.0062 (5)−0.0103 (6)0.0002 (5)
O40.0203 (6)0.0359 (7)0.0259 (7)0.0089 (5)0.0000 (5)0.0089 (5)
N10.0156 (6)0.0272 (7)0.0182 (7)−0.0039 (6)−0.0011 (5)0.0071 (6)
C10.0191 (8)0.0141 (7)0.0174 (8)0.0020 (6)0.0006 (6)−0.0007 (6)
C20.0209 (8)0.0178 (7)0.0142 (8)−0.0020 (6)0.0001 (6)−0.0011 (6)
C30.0131 (7)0.0215 (7)0.0144 (7)−0.0020 (6)−0.0004 (6)0.0050 (6)
C40.0165 (7)0.0150 (7)0.0191 (8)0.0026 (6)0.0021 (6)0.0020 (6)
C50.0199 (8)0.0142 (7)0.0148 (7)−0.0005 (6)0.0013 (6)−0.0012 (6)
C60.0157 (7)0.0146 (7)0.0127 (7)−0.0006 (6)0.0015 (6)0.0016 (6)
C70.0179 (7)0.0155 (7)0.0131 (7)−0.0016 (6)0.0009 (6)0.0005 (6)
C80.0217 (8)0.0192 (7)0.0168 (8)0.0010 (6)−0.0071 (6)−0.0008 (6)
C90.0152 (7)0.0209 (7)0.0189 (8)−0.0011 (6)0.0006 (6)−0.0018 (6)
Cl1'0.0243 (2)0.02306 (19)0.01513 (19)−0.00621 (15)0.00131 (15)−0.00093 (15)
O1'0.0212 (6)0.0176 (5)0.0123 (5)−0.0048 (4)0.0038 (4)−0.0015 (4)
O2'0.0235 (6)0.0157 (5)0.0216 (6)−0.0044 (5)0.0024 (5)−0.0019 (5)
O3'0.0313 (7)0.0233 (6)0.0203 (6)0.0061 (5)0.0107 (5)0.0013 (5)
O4'0.0200 (6)0.0302 (6)0.0225 (6)−0.0072 (5)−0.0001 (5)0.0030 (5)
N1'0.0154 (6)0.0206 (7)0.0167 (7)0.0054 (5)0.0004 (5)0.0052 (5)
C1'0.0183 (7)0.0139 (7)0.0153 (8)0.0010 (6)−0.0024 (6)−0.0015 (6)
C2'0.0184 (7)0.0178 (7)0.0134 (7)0.0047 (6)−0.0009 (6)−0.0025 (6)
C3'0.0125 (7)0.0181 (7)0.0144 (7)0.0026 (6)−0.0001 (6)0.0048 (6)
C4'0.0183 (8)0.0164 (7)0.0164 (8)−0.0014 (6)−0.0022 (6)0.0002 (6)
C5'0.0195 (8)0.0154 (7)0.0130 (7)0.0000 (6)0.0002 (6)−0.0021 (6)
C6'0.0146 (7)0.0145 (7)0.0127 (7)0.0014 (6)−0.0021 (6)0.0013 (6)
C7'0.0164 (7)0.0144 (7)0.0138 (7)0.0031 (6)−0.0026 (6)0.0006 (6)
C8'0.0170 (7)0.0200 (7)0.0134 (8)−0.0038 (6)0.0032 (6)0.0012 (6)
C9'0.0172 (8)0.0261 (8)0.0202 (8)0.0018 (6)0.0014 (6)−0.0025 (7)

Geometric parameters (Å, °)

Cl1—C91.7971 (16)Cl1'—C9'1.7927 (17)
O1—C71.3408 (18)O1'—C7'1.3419 (18)
O1—C81.4454 (19)O1'—C8'1.4416 (18)
O2—C71.2043 (18)O2'—C7'1.2041 (18)
O3—N11.2245 (19)O3'—N1'1.2243 (18)
O4—N11.2247 (18)O4'—N1'1.2258 (17)
N1—C31.472 (2)N1'—C3'1.4725 (19)
C1—C21.382 (2)C1'—C2'1.385 (2)
C1—C61.393 (2)C1'—C6'1.393 (2)
C1—H10.9500C1'—H1'0.9500
C2—C31.383 (2)C2'—C3'1.386 (2)
C2—H20.9500C2'—H2'0.9500
C3—C41.385 (2)C3'—C4'1.380 (2)
C4—C51.381 (2)C4'—C5'1.382 (2)
C4—H40.9500C4'—H4'0.9500
C5—C61.393 (2)C5'—C6'1.396 (2)
C5—H50.9500C5'—H5'0.9500
C6—C71.490 (2)C6'—C7'1.491 (2)
C8—C91.498 (2)C8'—C9'1.494 (2)
C8—H8A0.9900C8'—H8'10.9900
C8—H8B0.9900C8'—H8'20.9900
C9—H9A0.9900C9'—H9'10.9900
C9—H9B0.9900C9'—H9'20.9900
C7—O1—C8117.01 (12)C7'—O1'—C8'115.53 (11)
O3—N1—O4124.40 (14)O3'—N1'—O4'124.11 (14)
O3—N1—C3118.16 (14)O3'—N1'—C3'118.11 (13)
O4—N1—C3117.44 (14)O4'—N1'—C3'117.79 (13)
C2—C1—C6120.41 (14)C2'—C1'—C6'120.14 (14)
C2—C1—H1119.8C2'—C1'—H1'119.9
C6—C1—H1119.8C6'—C1'—H1'119.9
C1—C2—C3118.13 (14)C1'—C2'—C3'118.03 (14)
C1—C2—H2120.9C1'—C2'—H2'121.0
C3—C2—H2120.9C3'—C2'—H2'121.0
C2—C3—C4122.76 (14)C4'—C3'—C2'123.12 (14)
C2—C3—N1118.58 (14)C4'—C3'—N1'118.16 (13)
C4—C3—N1118.65 (14)C2'—C3'—N1'118.72 (14)
C5—C4—C3118.48 (14)C3'—C4'—C5'118.36 (14)
C5—C4—H4120.8C3'—C4'—H4'120.8
C3—C4—H4120.8C5'—C4'—H4'120.8
C4—C5—C6120.04 (14)C4'—C5'—C6'120.00 (14)
C4—C5—H5120.0C4'—C5'—H5'120.0
C6—C5—H5120.0C6'—C5'—H5'120.0
C1—C6—C5120.18 (14)C1'—C6'—C5'120.34 (14)
C1—C6—C7118.00 (13)C1'—C6'—C7'118.48 (13)
C5—C6—C7121.83 (14)C5'—C6'—C7'121.17 (14)
O2—C7—O1124.27 (14)O2'—C7'—O1'123.57 (14)
O2—C7—C6124.32 (14)O2'—C7'—C6'124.79 (14)
O1—C7—C6111.41 (12)O1'—C7'—C6'111.64 (12)
O1—C8—C9107.38 (12)O1'—C8'—C9'107.52 (12)
O1—C8—H8A110.2O1'—C8'—H8'1110.2
C9—C8—H8A110.2C9'—C8'—H8'1110.2
O1—C8—H8B110.2O1'—C8'—H8'2110.2
C9—C8—H8B110.2C9'—C8'—H8'2110.2
H8A—C8—H8B108.5H8'1—C8'—H8'2108.5
C8—C9—Cl1111.97 (11)C8'—C9'—Cl1'111.67 (11)
C8—C9—H9A109.2C8'—C9'—H9'1109.3
Cl1—C9—H9A109.2Cl1'—C9'—H9'1109.3
C8—C9—H9B109.2C8'—C9'—H9'2109.3
Cl1—C9—H9B109.2Cl1'—C9'—H9'2109.3
H9A—C9—H9B107.9H9'1—C9'—H9'2107.9
C6—C1—C2—C30.3 (2)C6'—C1'—C2'—C3'−0.3 (2)
C1—C2—C3—C4−0.8 (2)C1'—C2'—C3'—C4'0.4 (2)
C1—C2—C3—N1178.39 (13)C1'—C2'—C3'—N1'−179.86 (13)
O3—N1—C3—C27.2 (2)O3'—N1'—C3'—C4'−171.12 (13)
O4—N1—C3—C2−171.95 (14)O4'—N1'—C3'—C4'8.8 (2)
O3—N1—C3—C4−173.58 (14)O3'—N1'—C3'—C2'9.1 (2)
O4—N1—C3—C47.3 (2)O4'—N1'—C3'—C2'−170.90 (13)
C2—C3—C4—C50.4 (2)C2'—C3'—C4'—C5'−0.6 (2)
N1—C3—C4—C5−178.79 (13)N1'—C3'—C4'—C5'179.68 (13)
C3—C4—C5—C60.5 (2)C3'—C4'—C5'—C6'0.6 (2)
C2—C1—C6—C50.5 (2)C2'—C1'—C6'—C5'0.4 (2)
C2—C1—C6—C7−179.66 (14)C2'—C1'—C6'—C7'−179.20 (13)
C4—C5—C6—C1−0.9 (2)C4'—C5'—C6'—C1'−0.5 (2)
C4—C5—C6—C7179.26 (14)C4'—C5'—C6'—C7'179.00 (14)
C8—O1—C7—O21.3 (2)C8'—O1'—C7'—O2'−0.4 (2)
C8—O1—C7—C6−178.60 (13)C8'—O1'—C7'—C6'179.34 (12)
C1—C6—C7—O2−2.3 (2)C1'—C6'—C7'—O2'−5.3 (2)
C5—C6—C7—O2177.53 (15)C5'—C6'—C7'—O2'175.17 (15)
C1—C6—C7—O1177.65 (13)C1'—C6'—C7'—O1'174.96 (13)
C5—C6—C7—O1−2.5 (2)C5'—C6'—C7'—O1'−4.60 (19)
C7—O1—C8—C9−156.81 (13)C7'—O1'—C8'—C9'−166.85 (12)
O1—C8—C9—Cl1−62.71 (15)O1'—C8'—C9'—Cl1'−66.44 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C1—H1···Cl1'i0.952.793.6234 (18)147
C2'—H2'···O3'ii0.952.503.318 (2)145
C4'—H4'···O2iii0.952.403.223 (2)144
C5—H5···O2'iv0.952.423.205 (2)140
C5'—H5'···O1'0.952.392.7112 (19)100
C9—H9B···O2'v0.992.553.526 (2)167

Symmetry codes: (i) ; (ii) −x+2, −y+1, −z; (iii) ; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5038).

References

  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Rigaku (2004). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wu, H., Xie, M.-H., Zou, P., Liu, Y.-L. & He, Y.-J. (2009). Acta Cryst. E65, o3096. [PMC free article] [PubMed]
  • Zhang, A.-Y., Qian, B., Min, J. & Fang, Q.-X. (1995). J. Shanxi Normal Univ. (Nat. Sci. Ed.), 23, 44–47.
  • Zhang, Z.-S., Wu, J.-G. & Deng, R.-W. (1990). J. Lanzhou Univ. (Nat. Sci. Ed.), 26, 69–75.

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