organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

4-Nitro­benzyl 2-chloro­acetate

aCollege of Biotechnology and Pharmaceutical Engineering, Nanjing University of Technology, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
*Correspondence e-mail: hpf@njut.edu.cn

(Received 20 May 2009; accepted 21 May 2009; online 29 May 2009)

In the mol­ecule of the title compound, C9H8ClNO4, the nearly planar acetate moiety [maximum deviation = 0.015 (3) Å for an O atom] is oriented with respect to the plane of the aromatic ring at a dihedral angle of 73.03 (3)°. In the crystal structure, inter­molecular C—H⋯O inter­actions link mol­ecules into a network. ππ contacts between benzene rings [centroid–centroid distance = 4.000 (1) Å] may further stabilize the structure.

Related literature

For a related structure, see: Pyun et al. (2001[Pyun, D. K., Jeong, W. J., Jung, H. J., Kim, J. H., Lee, J. S., Lee, C. H. & Kim, B. J. (2001). Synlett, 12, 1950-1952.]). For bond-length data, see: Allen et al. (1987[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.]).

[Scheme 1]

Experimental

Crystal data
  • C9H8ClNO4

  • Mr = 229.61

  • Monoclinic, C 2/c

  • a = 13.636 (3) Å

  • b = 8.1570 (16) Å

  • c = 18.878 (4) Å

  • β = 108.30 (3)°

  • V = 1993.5 (8) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 0.38 mm−1

  • T = 294 K

  • 0.30 × 0.20 × 0.10 mm

Data collection
  • Enraf–Nonius CAD-4 diffractometer

  • Absorption correction: ψ scan (North et al., 1968[North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351-359.]) Tmin = 0.896, Tmax = 0.963

  • 1892 measured reflections

  • 1814 independent reflections

  • 1132 reflections with I > 2σ(I)

  • Rint = 0.055

  • 3 standard reflections frequency: 120 min intensity decay: 1%

Refinement
  • R[F2 > 2σ(F2)] = 0.068

  • wR(F2) = 0.191

  • S = 1.00

  • 1814 reflections

  • 136 parameters

  • H-atom parameters constrained

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.28 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1B⋯O1i 0.97 2.35 3.275 (5) 160
C3—H3A⋯O1ii 0.97 2.58 3.456 (5) 151
Symmetry codes: (i) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) [-x+1, y, -z+{\script{3\over 2}}].

Data collection: CAD-4 Software (Enraf–Nonius, 1989[Enraf-Nonius (1989). CAD-4 Software. Enraf-Nonius, Delft, The Netherlands.]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995[Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

Some derivatives of p-nitrobenzyl alcohol 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 (C4-C9) is, of course, planar. Atoms N, C3, O3 and O4 are 0.005 (3), 0.027 (3), -0.146 (3) and 0.144 (4) Å away from the ring plane, respectively. On the other hand, (O1/O2/C1-C3) moiety is nearly planar with a maximum deviation of 0.015 (3) Å for atom O2 and it is oriented with respect to ring A at a dihedral angle of 73.03 (3)°.

In the crystal structure, intermolecular C-H···O interactions (Table 1) link the molecules into a network (Fig. 2), in which they may be effective in the stabilization of the structure. The ππ contact between the benzene rings, Cg1—Cg1i [symmetry code: (i) 1 - x, -y, -z, where Cg1 is centroid of the ring A (C4-C9) may further stabilize the structure, with centroid-centroid distance of 4.000 (1) Å.

Related literature top

For a related structure, see: Pyun et al. (2001). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, chloroacetyl chloride (1.1 g) and p-nitrobenzyl alcohol (1.53 g) were added into the mixture of pyridine (15 ml) and dichloromethane (30 ml) at 273–278 K. The gross products were extracted with n-hexane, washed with water, and dried under vaccum, and then recrystallized in dichloromethane (yield; 0.916 g) (Pyun et al., 2001). Crystals suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Refinement top

H atoms were positioned geometrically, with C-H = 0.93 and 0.97 Å for aromatic and methylene H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
4-Nitrobenzyl 2-chloroacetate top
Crystal data top
C9H8ClNO4F(000) = 944
Mr = 229.61Dx = 1.530 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 13.636 (3) Åθ = 9–13°
b = 8.1570 (16) ŵ = 0.38 mm1
c = 18.878 (4) ÅT = 294 K
β = 108.30 (3)°Block, colorless
V = 1993.5 (8) Å30.30 × 0.20 × 0.10 mm
Z = 8
Data collection top
Enraf–Nonius CAD-4
diffractometer
1132 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.055
Graphite monochromatorθmax = 25.3°, θmin = 2.3°
ω/2θ scansh = 160
Absorption correction: ψ scan
(North et al., 1968)
k = 90
Tmin = 0.896, Tmax = 0.963l = 2122
1892 measured reflections3 standard reflections every 120 min
1814 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.068Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.191H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.1P)2 + 2P]
where P = (Fo2 + 2Fc2)/3
1814 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C9H8ClNO4V = 1993.5 (8) Å3
Mr = 229.61Z = 8
Monoclinic, C2/cMo Kα radiation
a = 13.636 (3) ŵ = 0.38 mm1
b = 8.1570 (16) ÅT = 294 K
c = 18.878 (4) Å0.30 × 0.20 × 0.10 mm
β = 108.30 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer
1132 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.055
Tmin = 0.896, Tmax = 0.9633 standard reflections every 120 min
1892 measured reflections intensity decay: 1%
1814 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0680 restraints
wR(F2) = 0.191H-atom parameters constrained
S = 1.00Δρmax = 0.31 e Å3
1814 reflectionsΔρmin = 0.28 e Å3
136 parameters
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
xyzUiso*/Ueq
Cl0.85639 (10)0.10201 (17)0.74171 (7)0.0745 (5)
O10.6449 (2)0.0812 (4)0.75755 (16)0.0561 (8)
O20.6848 (2)0.2403 (4)0.86053 (15)0.0528 (8)
O30.6555 (4)0.3688 (5)1.1134 (2)0.1110 (17)
O40.6159 (3)0.5146 (4)1.0154 (2)0.0854 (11)
N0.6314 (3)0.3823 (5)1.0467 (2)0.0567 (10)
C10.8107 (3)0.2211 (5)0.8028 (3)0.0578 (11)
H1A0.85820.21140.85310.069*
H1B0.80850.33550.78830.069*
C20.7037 (3)0.1679 (5)0.8022 (2)0.0444 (9)
C30.5855 (3)0.2023 (5)0.8709 (2)0.0531 (11)
H3A0.53340.18680.82280.064*
H3B0.56410.29270.89610.064*
C40.5956 (3)0.0483 (5)0.9169 (2)0.0411 (9)
C50.6365 (3)0.0540 (5)0.9945 (2)0.0518 (10)
H5A0.65680.15451.01770.062*
C60.6476 (3)0.0835 (5)1.0369 (2)0.0544 (11)
H6A0.67410.07681.08860.065*
C70.6192 (3)0.2331 (5)1.0024 (2)0.0465 (10)
C80.5789 (3)0.2437 (5)0.9254 (2)0.0505 (10)
H8A0.55960.34460.90230.061*
C90.5679 (3)0.1045 (5)0.8843 (2)0.0507 (10)
H9A0.54110.11160.83260.061*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0709 (9)0.0894 (9)0.0776 (9)0.0099 (7)0.0438 (7)0.0052 (7)
O10.0460 (17)0.0621 (18)0.0581 (17)0.0091 (14)0.0132 (14)0.0194 (15)
O20.0569 (18)0.0581 (17)0.0450 (15)0.0098 (14)0.0182 (13)0.0066 (13)
O30.195 (5)0.079 (3)0.056 (2)0.008 (3)0.036 (3)0.008 (2)
O40.104 (3)0.056 (2)0.097 (3)0.005 (2)0.033 (2)0.009 (2)
N0.055 (2)0.052 (2)0.066 (3)0.0018 (18)0.0231 (19)0.0086 (19)
C10.054 (3)0.061 (3)0.060 (3)0.012 (2)0.020 (2)0.004 (2)
C20.040 (2)0.043 (2)0.046 (2)0.0012 (19)0.0078 (18)0.0066 (19)
C30.045 (2)0.059 (3)0.059 (3)0.0026 (19)0.023 (2)0.004 (2)
C40.036 (2)0.047 (2)0.044 (2)0.0013 (17)0.0165 (16)0.0054 (17)
C50.053 (3)0.048 (2)0.055 (3)0.007 (2)0.018 (2)0.012 (2)
C60.052 (3)0.061 (3)0.046 (2)0.003 (2)0.0091 (19)0.010 (2)
C70.035 (2)0.056 (2)0.051 (2)0.0016 (19)0.0182 (18)0.002 (2)
C80.056 (3)0.044 (2)0.052 (2)0.011 (2)0.019 (2)0.004 (2)
C90.051 (2)0.063 (3)0.039 (2)0.008 (2)0.0163 (18)0.009 (2)
Geometric parameters (Å, º) top
Cl—C11.765 (4)C3—H3B0.9700
O1—C21.195 (5)C4—C91.389 (5)
O2—C21.344 (5)C4—C51.394 (5)
O2—C31.461 (5)C5—C61.359 (6)
N—O31.203 (5)C5—H5A0.9300
N—O41.217 (5)C6—C71.381 (6)
N—C71.457 (5)C6—H6A0.9300
C1—C21.519 (6)C7—C81.385 (6)
C1—H1A0.9700C8—C91.357 (6)
C1—H1B0.9700C8—H8A0.9300
C3—C41.509 (6)C9—H9A0.9300
C3—H3A0.9700
C2—O2—C3116.2 (3)C9—C4—C5117.4 (4)
O3—N—O4122.7 (4)C9—C4—C3121.9 (3)
O3—N—C7118.0 (4)C5—C4—C3120.7 (4)
O4—N—C7119.4 (4)C6—C5—C4121.7 (4)
C2—C1—Cl111.9 (3)C6—C5—H5A119.2
C2—C1—H1A109.2C4—C5—H5A119.2
Cl—C1—H1A109.2C5—C6—C7119.3 (4)
C2—C1—H1B109.2C5—C6—H6A120.4
Cl—C1—H1B109.2C7—C6—H6A120.4
H1A—C1—H1B107.9C6—C7—C8120.7 (4)
O1—C2—O2125.3 (4)C6—C7—N120.2 (4)
O1—C2—C1127.2 (4)C8—C7—N119.1 (4)
O2—C2—C1107.4 (3)C9—C8—C7118.9 (4)
O2—C3—C4109.5 (3)C9—C8—H8A120.5
O2—C3—H3A109.8C7—C8—H8A120.5
C4—C3—H3A109.8C8—C9—C4122.1 (4)
O2—C3—H3B109.8C8—C9—H9A119.0
C4—C3—H3B109.8C4—C9—H9A119.0
H3A—C3—H3B108.2
C3—O2—C2—O12.8 (6)C5—C6—C7—N179.3 (4)
C3—O2—C2—C1178.9 (3)O3—N—C7—C68.3 (6)
Cl—C1—C2—O114.4 (6)O4—N—C7—C6172.6 (4)
Cl—C1—C2—O2167.3 (3)O3—N—C7—C8171.9 (5)
C2—O2—C3—C486.8 (4)O4—N—C7—C87.3 (6)
O2—C3—C4—C996.3 (4)C6—C7—C8—C90.1 (6)
O2—C3—C4—C581.6 (5)N—C7—C8—C9179.7 (4)
C9—C4—C5—C61.1 (6)C7—C8—C9—C40.2 (6)
C3—C4—C5—C6179.1 (4)C5—C4—C9—C80.7 (6)
C4—C5—C6—C71.0 (7)C3—C4—C9—C8178.6 (4)
C5—C6—C7—C80.5 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···O1i0.972.353.275 (5)160
C3—H3A···O1ii0.972.583.456 (5)151
Symmetry codes: (i) x+3/2, y+1/2, z+3/2; (ii) x+1, y, z+3/2.

Experimental details

Crystal data
Chemical formulaC9H8ClNO4
Mr229.61
Crystal system, space groupMonoclinic, C2/c
Temperature (K)294
a, b, c (Å)13.636 (3), 8.1570 (16), 18.878 (4)
β (°) 108.30 (3)
V3)1993.5 (8)
Z8
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.30 × 0.20 × 0.10
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.896, 0.963
No. of measured, independent and
observed [I > 2σ(I)] reflections
1892, 1814, 1132
Rint0.055
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.068, 0.191, 1.00
No. of reflections1814
No. of parameters136
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.28

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···O1i0.972.353.275 (5)160
C3—H3A···O1ii0.972.583.456 (5)151
Symmetry codes: (i) x+3/2, y+1/2, z+3/2; (ii) x+1, y, z+3/2.
 

Acknowledgements

The authors thank the Center for Testing and Analysis, Nanjing University, for support.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationEnraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.  Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationHarms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.  Google Scholar
First citationNorth, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.  CrossRef IUCr Journals Web of Science Google Scholar
First citationPyun, D. K., Jeong, W. J., Jung, H. J., Kim, J. H., Lee, J. S., Lee, C. H. & Kim, B. J. (2001). Synlett, 12, 1950–1952.  CrossRef Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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