2-Nitro­benzyl 2-chloro­acetate

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

doi:10.1107/S1600536809031444

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2319

doi:10.1107/S1600536809031444

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2-Nitrobenzyl 2-chloroacetate

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

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

(Received 6 August 2009; accepted 10 August 2009; online 5 September 2009)

In the molecule of the title compound, C₉H₈ClNO₄, an intramolecular C—H⋯O interaction results in the formation of a near-planar (r.m.s. deviation 0.002 Å) five-membered ring, which is oriented at a dihedral angle of 4.07 (4)° with respect to the adjacent aromatic ring. In the crystal structure, intermolecular C—H⋯O interactions link the molecules into a two-dimensional network.

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, P 2₁ /c
a = 8.0270 (16) Å
b = 6.7530 (14) Å
c = 19.266 (4) Å
β = 92.52 (3)°
V = 1043.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.36 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 = 0.900, T_max = 0.965
2036 measured reflections
1893 independent reflections
891 reflections with I > 2σ(I)
R_int = 0.025
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.195
S = 1.00
1893 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O3ⁱ	0.97	2.43	3.372 (6)	166
C7—H7A⋯O1ⁱⁱ	0.93	2.58	3.374 (6)	143
Symmetry codes: (i) x-1, y, z; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031444/hk2752sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809031444/hk2752Isup2.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. Intramolecular C-H···O interaction (Table 1) results in the formation of a planar five-membered ring B (O2/C3/C4/C9/H9A), which is oriented with respect to the adjacent ring A at a dihedral angle of A/B = 4.07 (4)°.

In the crystal structure, intermolecular C-H···O interactions (Table 1) link the molecules into a two dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure.

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 2-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 vacuum, and then recrystallized from dichloromethane. Finally the title compound was obtained (yield; 0.61 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) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

2-Nitrobenzyl 2-chloroacetate top

Crystal data top

C₉H₈ClNO₄	F(000) = 472
M_r = 229.61	D_x = 1.462 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.0270 (16) Å	θ = 9–13°
b = 6.7530 (14) Å	µ = 0.36 mm⁻¹
c = 19.266 (4) Å	T = 294 K
β = 92.52 (3)°	Block, yellow
V = 1043.3 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	891 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.025
Graphite monochromator	θ_max = 25.3°, θ_min = 2.1°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
T_min = 0.900, T_max = 0.965	l = −23→23
2036 measured reflections	3 standard reflections every 120 min
1893 independent reflections	intensity decay: 1%

Refinement top

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)] = 0.067	H-atom parameters constrained
wR(F²) = 0.195	w = 1/[σ²(F_o²) + (0.07P)² + 0.84P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1893 reflections	Δρ_max = 0.29 e Å⁻³
137 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.031 (4)

Crystal data top

C₉H₈ClNO₄	V = 1043.3 (4) Å³
M_r = 229.61	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.0270 (16) Å	µ = 0.36 mm⁻¹
b = 6.7530 (14) Å	T = 294 K
c = 19.266 (4) Å	0.30 × 0.20 × 0.10 mm
β = 92.52 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	891 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.025
T_min = 0.900, T_max = 0.965	3 standard reflections every 120 min
2036 measured reflections	intensity decay: 1%
1893 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.195	H-atom parameters constrained
S = 1.00	Δρ_max = 0.29 e Å⁻³
1893 reflections	Δρ_min = −0.23 e Å⁻³
137 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	−0.3781 (2)	0.3294 (4)	0.19943 (9)	0.1458 (10)
O1	−0.0286 (4)	0.3868 (6)	0.25207 (18)	0.0985 (12)
O2	−0.0679 (3)	0.2382 (5)	0.35365 (15)	0.0743 (9)
O3	0.4281 (5)	0.3113 (9)	0.3977 (2)	0.151 (2)
O4	0.5546 (5)	0.2492 (8)	0.4935 (3)	0.161 (2)
N	0.4264 (5)	0.2744 (8)	0.4576 (3)	0.1028 (16)
C1	−0.2908 (6)	0.2341 (10)	0.2755 (2)	0.1002 (18)
H1A	−0.3577	0.2745	0.3137	0.120*
H1B	−0.2939	0.0906	0.2730	0.120*
C2	−0.1141 (6)	0.2988 (7)	0.2904 (2)	0.0722 (13)
C3	0.1048 (5)	0.2696 (7)	0.3759 (2)	0.0722 (13)
H3A	0.1424	0.3976	0.3600	0.087*
H3B	0.1746	0.1680	0.3566	0.087*
C4	0.1165 (5)	0.2610 (6)	0.4535 (2)	0.0559 (10)
C5	0.2673 (5)	0.2629 (7)	0.4927 (2)	0.0706 (13)
C6	0.2753 (7)	0.2548 (8)	0.5642 (3)	0.0889 (15)
H6A	0.3780	0.2567	0.5885	0.107*
C7	0.1300 (8)	0.2440 (7)	0.5994 (3)	0.0874 (15)
H7A	0.1332	0.2379	0.6477	0.105*
C8	−0.0187 (6)	0.2423 (7)	0.5624 (2)	0.0735 (13)
H8A	−0.1173	0.2364	0.5859	0.088*
C9	−0.0259 (5)	0.2491 (6)	0.4913 (2)	0.0599 (11)
H9A	−0.1294	0.2456	0.4677	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.1014 (12)	0.224 (2)	0.1105 (13)	0.0086 (13)	−0.0150 (9)	0.0395 (14)
O1	0.101 (3)	0.116 (3)	0.080 (2)	−0.014 (2)	0.0205 (19)	0.024 (2)
O2	0.0632 (18)	0.096 (2)	0.0641 (19)	−0.0135 (17)	0.0092 (14)	0.0080 (17)
O3	0.074 (2)	0.267 (7)	0.115 (3)	−0.035 (3)	0.041 (2)	−0.036 (4)
O4	0.055 (2)	0.222 (6)	0.205 (5)	0.002 (3)	0.001 (3)	0.003 (4)
N	0.049 (3)	0.122 (4)	0.138 (4)	−0.010 (3)	0.013 (3)	−0.032 (4)
C1	0.077 (3)	0.148 (5)	0.076 (3)	−0.006 (4)	0.004 (2)	0.008 (3)
C2	0.080 (3)	0.075 (3)	0.064 (3)	0.004 (3)	0.018 (2)	0.000 (3)
C3	0.062 (3)	0.080 (3)	0.076 (3)	−0.008 (2)	0.021 (2)	−0.005 (3)
C4	0.051 (2)	0.050 (2)	0.068 (2)	0.000 (2)	0.0161 (19)	−0.005 (2)
C5	0.057 (2)	0.071 (3)	0.086 (3)	−0.005 (2)	0.016 (2)	−0.007 (3)
C6	0.081 (3)	0.091 (4)	0.093 (4)	0.003 (3)	−0.015 (3)	0.004 (3)
C7	0.114 (4)	0.080 (4)	0.069 (3)	−0.001 (4)	0.015 (3)	0.001 (3)
C8	0.078 (3)	0.064 (3)	0.080 (3)	−0.003 (3)	0.028 (3)	0.001 (3)
C9	0.056 (2)	0.056 (3)	0.070 (3)	−0.001 (2)	0.0164 (19)	−0.001 (2)

Geometric parameters (Å, º) top

Cl—C1	1.721 (5)	C3—H3B	0.9700
O1—C2	1.189 (5)	C4—C9	1.385 (5)
O2—C2	1.324 (5)	C4—C5	1.398 (6)
O2—C3	1.448 (5)	C5—C6	1.378 (6)
N—O3	1.181 (6)	C6—C7	1.377 (7)
N—O4	1.227 (6)	C6—H6A	0.9300
N—C5	1.472 (6)	C7—C8	1.363 (7)
C1—C2	1.499 (7)	C7—H7A	0.9300
C1—H1A	0.9700	C8—C9	1.369 (6)
C1—H1B	0.9700	C8—H8A	0.9300
C3—C4	1.494 (6)	C9—H9A	0.9300
C3—H3A	0.9700

C2—O2—C3	117.0 (3)	C9—C4—C5	115.6 (4)
O3—N—O4	122.3 (5)	C9—C4—C3	120.8 (4)
O3—N—C5	120.5 (5)	C5—C4—C3	123.7 (4)
O4—N—C5	117.2 (6)	C6—C5—C4	122.7 (4)
C2—C1—Cl	113.6 (4)	C6—C5—N	117.2 (5)
C2—C1—H1A	108.8	C4—C5—N	120.0 (4)
Cl—C1—H1A	108.8	C7—C6—C5	119.5 (5)
C2—C1—H1B	108.8	C7—C6—H6A	120.3
Cl—C1—H1B	108.8	C5—C6—H6A	120.3
H1A—C1—H1B	107.7	C8—C7—C6	119.0 (5)
O1—C2—O2	125.4 (5)	C8—C7—H7A	120.5
O1—C2—C1	126.5 (5)	C6—C7—H7A	120.5
O2—C2—C1	108.1 (4)	C7—C8—C9	121.4 (4)
O2—C3—C4	107.9 (3)	C7—C8—H8A	119.3
O2—C3—H3A	110.1	C9—C8—H8A	119.3
C4—C3—H3A	110.1	C8—C9—C4	121.9 (4)
O2—C3—H3B	110.1	C8—C9—H9A	119.0
C4—C3—H3B	110.1	C4—C9—H9A	119.0
H3A—C3—H3B	108.4

C3—O2—C2—O1	−4.6 (7)	O3—N—C5—C6	−168.6 (6)
C3—O2—C2—C1	174.4 (4)	O4—N—C5—C6	9.6 (8)
Cl—C1—C2—O1	−9.0 (8)	O3—N—C5—C4	11.2 (8)
Cl—C1—C2—O2	172.1 (3)	O4—N—C5—C4	−170.6 (5)
C2—O2—C3—C4	159.9 (4)	C4—C5—C6—C7	0.2 (8)
O2—C3—C4—C9	−7.0 (6)	N—C5—C6—C7	180.0 (5)
O2—C3—C4—C5	172.5 (4)	C5—C6—C7—C8	−0.3 (8)
C9—C4—C5—C6	−0.4 (7)	C6—C7—C8—C9	0.7 (8)
C3—C4—C5—C6	−180.0 (5)	C7—C8—C9—C4	−1.0 (7)
C9—C4—C5—N	179.8 (4)	C5—C4—C9—C8	0.8 (6)
C3—C4—C5—N	0.2 (7)	C3—C4—C9—C8	−179.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O3ⁱ	0.97	2.43	3.372 (6)	166
C7—H7A···O1ⁱⁱ	0.93	2.58	3.374 (6)	143
C9—H9A···O2	0.93	2.27	2.660 (5)	104

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

Experimental details

Crystal data
Chemical formula	C₉H₈ClNO₄
M_r	229.61
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	8.0270 (16), 6.7530 (14), 19.266 (4)
β (°)	92.52 (3)
V (Å³)	1043.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
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	0.900, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	2036, 1893, 891
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.067, 0.195, 1.00
No. of reflections	1893
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.23

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O3ⁱ	0.97	2.43	3.372 (6)	166
C7—H7A···O1ⁱⁱ	0.93	2.58	3.374 (6)	143
C9—H9A···O2	0.93	2.27	2.660 (5)	104

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

Acknowledgements

The authors thank the Innovation Fund for doctoral theses (BSCX200811), Nanjing University of Technology, for support.

References

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