4-Nitro­benzyl 2-bromo­acetate

Abstract

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 R ₂ ²(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,

• a = 13.851 (3) Å

• b = 8.1590 (16) Å

• c = 19.201 (4) Å

• β = 109.08 (3)°

• V = 2050.7 (8) ų

• 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[F ² > 2σ(F ²)] = 0.054

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

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 U_iso(H) = 1.2U_eq(C).

Figures

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.

Crystal data

C9H8BrNO4	F(000) = 1088
Mr = 274.07	Dx = 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

Enraf–Nonius CAD-4 diffractometer	1055 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
graphite	θmax = 25.3°, θmin = 2.2°
ω/2θ scans	h = 0→16
Absorption correction: ψ scan (North et al., 1968)	k = −9→9
Tmin = 0.502, Tmax = 0.690	l = −23→21
3739 measured reflections	3 standard reflections every 120 min
1873 independent reflections	intensity decay: 1%

Refinement

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(Fo2) + (0.044P)2] where P = (Fo2 + 2Fc2)/3
1873 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.