4-Nitro­benzyl 2-chloro­acetate

Zhu, K.; Wang, Y.-H.; Liu, H.; Han, P.-F.; Wei, P.

doi:10.1107/S1600536809019278

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1423

doi:10.1107/S1600536809019278

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4-Nitrobenzyl 2-chloroacetate

Kai Zhu,^a Yan-Hua Wang,^a Hui Liu,^a Ping-Fang Han ^a ^* and Ping Wei ^a

^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. π–π 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 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₉H₈ClNO₄
M_r = 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 ) T_min = 0.896, T_max = 0.963
1892 measured reflections
1814 independent reflections
1132 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: CAD-4 Software; 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809019278/hk2695sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019278/hk2695Isup2.hkl

checkCIF report

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 π–π 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.

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

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	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

C₉H₈ClNO₄	F(000) = 944
M_r = 229.61	D_x = 1.530 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 13.636 (3) Å	θ = 9–13°
b = 8.1570 (16) Å	µ = 0.38 mm⁻¹
c = 18.878 (4) Å	T = 294 K
β = 108.30 (3)°	Block, colorless
V = 1993.5 (8) Å³	0.30 × 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 tube	R_int = 0.055
Graphite monochromator	θ_max = 25.3°, θ_min = 2.3°
ω/2θ scans	h = −16→0
Absorption correction: ψ scan (North et al., 1968)	k = −9→0
T_min = 0.896, T_max = 0.963	l = −21→22
1892 measured reflections	3 standard reflections every 120 min
1814 independent reflections	intensity decay: 1%

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1P)² + 2P] where P = (F_o² + 2F_c²)/3
1814 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₉H₈ClNO₄	V = 1993.5 (8) Å³
M_r = 229.61	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 13.636 (3) Å	µ = 0.38 mm⁻¹
b = 8.1570 (16) Å	T = 294 K
c = 18.878 (4) Å	0.30 × 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)	R_int = 0.055
T_min = 0.896, T_max = 0.963	3 standard reflections every 120 min
1892 measured reflections	intensity decay: 1%
1814 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.191	H-atom parameters constrained
S = 1.00	Δρ_max = 0.31 e Å⁻³
1814 reflections	Δρ_min = −0.28 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Cl	0.85639 (10)	0.10201 (17)	0.74171 (7)	0.0745 (5)
O1	0.6449 (2)	0.0812 (4)	0.75755 (16)	0.0561 (8)
O2	0.6848 (2)	0.2403 (4)	0.86053 (15)	0.0528 (8)
O3	0.6555 (4)	−0.3688 (5)	1.1134 (2)	0.1110 (17)
O4	0.6159 (3)	−0.5146 (4)	1.0154 (2)	0.0854 (11)
N	0.6314 (3)	−0.3823 (5)	1.0467 (2)	0.0567 (10)
C1	0.8107 (3)	0.2211 (5)	0.8028 (3)	0.0578 (11)
H1A	0.8582	0.2114	0.8531	0.069*
H1B	0.8085	0.3355	0.7883	0.069*
C2	0.7037 (3)	0.1679 (5)	0.8022 (2)	0.0444 (9)
C3	0.5855 (3)	0.2023 (5)	0.8709 (2)	0.0531 (11)
H3A	0.5334	0.1868	0.8228	0.064*
H3B	0.5641	0.2927	0.8961	0.064*
C4	0.5956 (3)	0.0483 (5)	0.9169 (2)	0.0411 (9)
C5	0.6365 (3)	0.0540 (5)	0.9945 (2)	0.0518 (10)
H5A	0.6568	0.1545	1.0177	0.062*
C6	0.6476 (3)	−0.0835 (5)	1.0369 (2)	0.0544 (11)
H6A	0.6741	−0.0768	1.0886	0.065*
C7	0.6192 (3)	−0.2331 (5)	1.0024 (2)	0.0465 (10)
C8	0.5789 (3)	−0.2437 (5)	0.9254 (2)	0.0505 (10)
H8A	0.5596	−0.3446	0.9023	0.061*
C9	0.5679 (3)	−0.1045 (5)	0.8843 (2)	0.0507 (10)
H9A	0.5411	−0.1116	0.8326	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0709 (9)	0.0894 (9)	0.0776 (9)	−0.0099 (7)	0.0438 (7)	−0.0052 (7)
O1	0.0460 (17)	0.0621 (18)	0.0581 (17)	−0.0091 (14)	0.0132 (14)	−0.0194 (15)
O2	0.0569 (18)	0.0581 (17)	0.0450 (15)	−0.0098 (14)	0.0182 (13)	−0.0066 (13)
O3	0.195 (5)	0.079 (3)	0.056 (2)	−0.008 (3)	0.036 (3)	0.008 (2)
O4	0.104 (3)	0.056 (2)	0.097 (3)	0.005 (2)	0.033 (2)	0.009 (2)
N	0.055 (2)	0.052 (2)	0.066 (3)	0.0018 (18)	0.0231 (19)	0.0086 (19)
C1	0.054 (3)	0.061 (3)	0.060 (3)	−0.012 (2)	0.020 (2)	−0.004 (2)
C2	0.040 (2)	0.043 (2)	0.046 (2)	−0.0012 (19)	0.0078 (18)	0.0066 (19)
C3	0.045 (2)	0.059 (3)	0.059 (3)	0.0026 (19)	0.023 (2)	−0.004 (2)
C4	0.036 (2)	0.047 (2)	0.044 (2)	−0.0013 (17)	0.0165 (16)	−0.0054 (17)
C5	0.053 (3)	0.048 (2)	0.055 (3)	−0.007 (2)	0.018 (2)	−0.012 (2)
C6	0.052 (3)	0.061 (3)	0.046 (2)	−0.003 (2)	0.0091 (19)	−0.010 (2)
C7	0.035 (2)	0.056 (2)	0.051 (2)	0.0016 (19)	0.0182 (18)	0.002 (2)
C8	0.056 (3)	0.044 (2)	0.052 (2)	−0.011 (2)	0.019 (2)	−0.004 (2)
C9	0.051 (2)	0.063 (3)	0.039 (2)	−0.008 (2)	0.0163 (18)	−0.009 (2)

Geometric parameters (Å, º) top

Cl—C1	1.765 (4)	C3—H3B	0.9700
O1—C2	1.195 (5)	C4—C9	1.389 (5)
O2—C2	1.344 (5)	C4—C5	1.394 (5)
O2—C3	1.461 (5)	C5—C6	1.359 (6)
N—O3	1.203 (5)	C5—H5A	0.9300
N—O4	1.217 (5)	C6—C7	1.381 (6)
N—C7	1.457 (5)	C6—H6A	0.9300
C1—C2	1.519 (6)	C7—C8	1.385 (6)
C1—H1A	0.9700	C8—C9	1.357 (6)
C1—H1B	0.9700	C8—H8A	0.9300
C3—C4	1.509 (6)	C9—H9A	0.9300
C3—H3A	0.9700

C2—O2—C3	116.2 (3)	C9—C4—C5	117.4 (4)
O3—N—O4	122.7 (4)	C9—C4—C3	121.9 (3)
O3—N—C7	118.0 (4)	C5—C4—C3	120.7 (4)
O4—N—C7	119.4 (4)	C6—C5—C4	121.7 (4)
C2—C1—Cl	111.9 (3)	C6—C5—H5A	119.2
C2—C1—H1A	109.2	C4—C5—H5A	119.2
Cl—C1—H1A	109.2	C5—C6—C7	119.3 (4)
C2—C1—H1B	109.2	C5—C6—H6A	120.4
Cl—C1—H1B	109.2	C7—C6—H6A	120.4
H1A—C1—H1B	107.9	C6—C7—C8	120.7 (4)
O1—C2—O2	125.3 (4)	C6—C7—N	120.2 (4)
O1—C2—C1	127.2 (4)	C8—C7—N	119.1 (4)
O2—C2—C1	107.4 (3)	C9—C8—C7	118.9 (4)
O2—C3—C4	109.5 (3)	C9—C8—H8A	120.5
O2—C3—H3A	109.8	C7—C8—H8A	120.5
C4—C3—H3A	109.8	C8—C9—C4	122.1 (4)
O2—C3—H3B	109.8	C8—C9—H9A	119.0
C4—C3—H3B	109.8	C4—C9—H9A	119.0
H3A—C3—H3B	108.2

C3—O2—C2—O1	2.8 (6)	C5—C6—C7—N	179.3 (4)
C3—O2—C2—C1	−178.9 (3)	O3—N—C7—C6	8.3 (6)
Cl—C1—C2—O1	−14.4 (6)	O4—N—C7—C6	−172.6 (4)
Cl—C1—C2—O2	167.3 (3)	O3—N—C7—C8	−171.9 (5)
C2—O2—C3—C4	86.8 (4)	O4—N—C7—C8	7.3 (6)
O2—C3—C4—C9	−96.3 (4)	C6—C7—C8—C9	0.1 (6)
O2—C3—C4—C5	81.6 (5)	N—C7—C8—C9	−179.7 (4)
C9—C4—C5—C6	−1.1 (6)	C7—C8—C9—C4	−0.2 (6)
C3—C4—C5—C6	−179.1 (4)	C5—C4—C9—C8	0.7 (6)
C4—C5—C6—C7	1.0 (7)	C3—C4—C9—C8	178.6 (4)
C5—C6—C7—C8	−0.5 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+3/2, y+1/2, −z+3/2; (ii) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₉H₈ClNO₄
M_r	229.61
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	13.636 (3), 8.1570 (16), 18.878 (4)
β (°)	108.30 (3)
V (Å³)	1993.5 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.896, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	1892, 1814, 1132
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.191, 1.00
No. of reflections	1814
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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+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

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