4-Nitro­benzyl 2-bromo­acetate

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

doi:10.1107/S1600536809021187

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1522

doi:10.1107/S1600536809021187

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4-Nitrobenzyl 2-bromoacetate

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 31 May 2009; accepted 4 June 2009; online 6 June 2009)

In the molecule of the title compound, C₉H₈BrNO₄, the acetate group is close to planar [maximum deviation = 0.042 (3) Å] and is oriented at a dihedral angle of 73.24 (3)° with respect to the aromatic ring. In the crystal structure, intermolecular C—H⋯O interactions link the molecules into a three-dimensional network, forming R₂²(10) ring motifs.

Related literature

For a related structure, see: Pyun et al. (2001 ). For bond-length data, see: Allen et al. (1987 ). For ring motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₉H₈BrNO₄
M_r = 274.07
Monoclinic, C 2/c
a = 13.851 (3) Å
b = 8.1590 (16) Å
c = 19.201 (4) Å
β = 109.08 (3)°
V = 2050.7 (8) Å³
Z = 8
Mo Kα radiation
μ = 4.00 mm⁻¹
T = 294 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.502, T_max = 0.690
3739 measured reflections
1873 independent reflections
1055 reflections with I > 2σ(I)
R_int = 0.043
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.131
S = 1.00
1873 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O4ⁱ	0.97	2.59	3.486 (7)	153
C9—H9B⋯O4ⁱⁱ	0.97	2.47	3.376 (8)	155
Symmetry codes: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021187/hk2706sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809021187/hk2706Isup2.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 (C1-C6) is, of course, planar. Atoms O1, O2, N, and C7 are 0.119 (3), -0.161 (3), -0.015 (3) and -0.042 (3) Å away from the plane of ring A, respectively. The moiety (O3/O4/C7-C9) is planar with a maximum deviation of -0.042 (3) Å for atom C7, and it is oriented with respect to ring A at a dihedral angle of 73.24 (3)°.

In the crystal structure, intermolecular C-H···O interactions (Table 1) link the molecules into a three-dimensional network forming R₂²(10) ring motifs (Bernstein et al., 1995) (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). For ring motifs, see: Bernstein et al. (1995).

Experimental top

For the preparation of the title compound, bromoacetyl bromide (2.01 g) and p-nitrobenzyl alcohol (1.53 g) were added into dichloromethane (30 ml) in pyridine (15 ml) at 273-278 K. The gross products were extracted with n-hexane, washed with water, dried under vaccum, and then recrystallized from dichloromethane (yield; 0.503 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) 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-bromoacetate top

Crystal data top

C₉H₈BrNO₄	F(000) = 1088
M_r = 274.07	D_x = 1.775 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 13.851 (3) Å	θ = 10–14°
b = 8.1590 (16) Å	µ = 4.00 mm⁻¹
c = 19.201 (4) Å	T = 294 K
β = 109.08 (3)°	Block, colorless
V = 2050.7 (8) Å³	0.20 × 0.10 × 0.10 mm
Z = 8

Data collection top

Enraf–Nonius CAD-4 diffractometer	1055 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.043
Graphite monochromator	θ_max = 25.3°, θ_min = 2.2°
ω/2θ scans	h = 0→16
Absorption correction: ψ scan (North et al., 1968)	k = −9→9
T_min = 0.502, T_max = 0.690	l = −23→21
3739 measured reflections	3 standard reflections every 120 min
1873 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.044P)²] where P = (F_o² + 2F_c²)/3
1873 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₉H₈BrNO₄	V = 2050.7 (8) Å³
M_r = 274.07	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 13.851 (3) Å	µ = 4.00 mm⁻¹
b = 8.1590 (16) Å	T = 294 K
c = 19.201 (4) Å	0.20 × 0.10 × 0.10 mm
β = 109.08 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1055 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.043
T_min = 0.502, T_max = 0.690	3 standard reflections every 120 min
3739 measured reflections	intensity decay: 1%
1873 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.00	Δρ_max = 0.49 e Å⁻³
1873 reflections	Δρ_min = −0.46 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
Br	0.14001 (5)	0.10006 (10)	0.25541 (4)	0.0690 (3)
O1	0.3414 (6)	−0.3704 (8)	−0.1100 (3)	0.114 (2)
O2	0.3855 (4)	−0.5164 (7)	−0.0136 (3)	0.0823 (16)
O3	0.3187 (3)	0.2414 (5)	0.1386 (2)	0.0474 (10)
O4	0.3549 (3)	0.0826 (5)	0.2389 (2)	0.0550 (11)
N	0.3685 (4)	−0.3840 (8)	−0.0450 (4)	0.0628 (16)
C1	0.3826 (4)	−0.2328 (8)	0.0002 (3)	0.0436 (15)
C2	0.4247 (4)	−0.2437 (8)	0.0752 (3)	0.0485 (16)
H2A	0.4448	−0.3443	0.0980	0.058*
C3	0.4364 (5)	−0.1024 (8)	0.1156 (3)	0.0508 (15)
H3A	0.4656	−0.1081	0.1666	0.061*
C4	0.4064 (4)	0.0471 (8)	0.0832 (3)	0.0428 (15)
C5	0.3638 (4)	0.0536 (8)	0.0067 (3)	0.0482 (16)
H5A	0.3430	0.1538	−0.0164	0.058*
C6	0.3524 (4)	−0.0851 (8)	−0.0343 (3)	0.0515 (17)
H6A	0.3243	−0.0801	−0.0854	0.062*
C7	0.4165 (4)	0.1993 (8)	0.1284 (3)	0.0483 (15)
H7A	0.4681	0.1828	0.1762	0.058*
H7B	0.4384	0.2893	0.1041	0.058*
C8	0.2977 (4)	0.1691 (8)	0.1950 (3)	0.0429 (14)
C9	0.1933 (4)	0.2229 (8)	0.1920 (3)	0.0540 (16)
H9A	0.1474	0.2124	0.1417	0.065*
H9B	0.1957	0.3377	0.2055	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0593 (4)	0.0744 (5)	0.0828 (5)	0.0128 (4)	0.0362 (4)	0.0107 (5)
O1	0.189 (6)	0.076 (5)	0.065 (3)	0.000 (5)	0.028 (4)	−0.022 (3)
O2	0.102 (4)	0.036 (3)	0.100 (4)	−0.008 (3)	0.021 (3)	−0.004 (3)
O3	0.044 (2)	0.045 (3)	0.051 (2)	0.010 (2)	0.0132 (18)	0.003 (2)
O4	0.044 (2)	0.056 (3)	0.061 (2)	0.010 (2)	0.012 (2)	0.020 (3)
N	0.059 (3)	0.056 (5)	0.070 (4)	−0.008 (3)	0.018 (3)	−0.011 (4)
C1	0.033 (3)	0.037 (4)	0.060 (4)	0.000 (3)	0.015 (3)	−0.002 (3)
C2	0.049 (3)	0.039 (4)	0.055 (4)	0.004 (3)	0.014 (3)	0.007 (3)
C3	0.057 (3)	0.044 (4)	0.047 (3)	0.005 (4)	0.011 (3)	0.002 (4)
C4	0.029 (3)	0.046 (4)	0.054 (4)	−0.003 (3)	0.015 (3)	−0.002 (3)
C5	0.054 (4)	0.035 (4)	0.052 (4)	0.005 (3)	0.012 (3)	0.008 (3)
C6	0.049 (4)	0.053 (4)	0.047 (3)	0.001 (3)	0.008 (3)	0.003 (4)
C7	0.040 (3)	0.044 (4)	0.060 (4)	−0.004 (3)	0.017 (3)	0.001 (4)
C8	0.032 (3)	0.042 (4)	0.050 (3)	−0.006 (3)	0.008 (3)	−0.010 (3)
C9	0.046 (3)	0.041 (4)	0.075 (4)	0.005 (3)	0.019 (3)	0.001 (4)

Geometric parameters (Å, º) top

Br—C9	1.903 (6)	C3—H3A	0.9300
O3—C7	1.470 (6)	C4—C5	1.393 (8)
O3—C8	1.346 (7)	C4—C7	1.496 (8)
O4—C8	1.183 (7)	C5—C6	1.359 (8)
N—O1	1.185 (7)	C5—H5A	0.9300
N—O2	1.222 (7)	C6—H6A	0.9300
N—C1	1.485 (8)	C7—H7A	0.9700
C1—C2	1.367 (8)	C7—H7B	0.9700
C1—C6	1.373 (8)	C8—C9	1.494 (8)
C2—C3	1.370 (8)	C9—H9A	0.9700
C2—H2A	0.9300	C9—H9B	0.9700
C3—C4	1.371 (8)

C8—O3—C7	117.1 (5)	C5—C6—C1	119.4 (5)
O1—N—O2	123.1 (7)	C5—C6—H6A	120.3
O1—N—C1	118.3 (7)	C1—C6—H6A	120.3
O2—N—C1	118.6 (6)	O3—C7—C4	110.8 (4)
C2—C1—C6	121.6 (6)	O3—C7—H7A	109.5
C2—C1—N	119.4 (6)	C4—C7—H7A	109.5
C6—C1—N	119.0 (6)	O3—C7—H7B	109.5
C1—C2—C3	118.2 (6)	C4—C7—H7B	109.5
C1—C2—H2A	120.9	H7A—C7—H7B	108.1
C3—C2—H2A	120.9	O4—C8—O3	124.3 (5)
C2—C3—C4	121.9 (5)	O4—C8—C9	128.1 (6)
C2—C3—H3A	119.0	O3—C8—C9	107.5 (6)
C4—C3—H3A	119.0	C8—C9—Br	113.2 (5)
C3—C4—C5	118.3 (6)	C8—C9—H9A	108.9
C3—C4—C7	121.2 (5)	Br—C9—H9A	108.9
C5—C4—C7	120.5 (6)	C8—C9—H9B	108.9
C6—C5—C4	120.6 (6)	Br—C9—H9B	108.9
C6—C5—H5A	119.7	H9A—C9—H9B	107.8
C4—C5—H5A	119.7

O1—N—C1—C2	−172.7 (6)	C4—C5—C6—C1	0.5 (9)
O2—N—C1—C2	7.3 (8)	C2—C1—C6—C5	−0.5 (9)
O1—N—C1—C6	7.6 (9)	N—C1—C6—C5	179.2 (5)
O2—N—C1—C6	−172.4 (6)	C8—O3—C7—C4	85.8 (6)
C6—C1—C2—C3	−0.1 (8)	C3—C4—C7—O3	−98.5 (6)
N—C1—C2—C3	−179.8 (5)	C5—C4—C7—O3	79.9 (6)
C1—C2—C3—C4	0.6 (9)	C7—O3—C8—O4	4.6 (8)
C2—C3—C4—C5	−0.6 (9)	C7—O3—C8—C9	−177.1 (5)
C2—C3—C4—C7	177.8 (5)	O4—C8—C9—Br	−13.4 (8)
C3—C4—C5—C6	0.1 (8)	O3—C8—C9—Br	168.3 (4)
C7—C4—C5—C6	−178.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O4ⁱ	0.97	2.59	3.486 (7)	153
C9—H9B···O4ⁱⁱ	0.97	2.47	3.376 (8)	155

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

Experimental details

Crystal data
Chemical formula	C₉H₈BrNO₄
M_r	274.07
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	13.851 (3), 8.1590 (16), 19.201 (4)
β (°)	109.08 (3)
V (Å³)	2050.7 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	4.00
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.502, 0.690
No. of measured, independent and observed [I > 2σ(I)] reflections	3739, 1873, 1055
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.131, 1.00
No. of reflections	1873
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.46

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), 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
C7—H7A···O4ⁱ	0.97	2.59	3.486 (7)	153
C9—H9B···O4ⁱⁱ	0.97	2.47	3.376 (8)	155

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

Acknowledgements

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

References

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