4-Nitro­phenyl 2-bromo-2-methyl­propano­ate

Rizzoli, C.; Marku, E.; Greci, L.

doi:10.1107/S1600536811005988

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o698

doi:10.1107/S1600536811005988

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4-Nitrophenyl 2-bromo-2-methylpropanoate

Corrado Rizzoli,^a ^* Elda Marku ^b and Lucedio Greci ^c

^aDipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universitá degli Studi di Parma, Viale G. P. Usberti 17/A, I-43124 Parma, Italy, ^bFakulteti i Shkencave të Natyrës, Departamenti i Kimise, Universiteti i Tiranes, Bulevardi "Zogu I", Tirana, Albania, and ^cDipartimento ISAC, Universitá Politecnica delle Marche, Via Brecce Bianche, I-60131 Ancona, Italy
^*Correspondence e-mail: corrado.rizzoli@unipr.it

(Received 16 February 2011; accepted 17 February 2011; online 23 February 2011)

In the title compound, C₁₀H₁₀BrNO₄, the planes of the carboxylate and nitro groups are rotated by 60.53 (13) and 6.4 (3)°, respectively, to the benzene ring. In the crystal, intermolecular C—H⋯O hydrogen bonds link the molecules into zigzag chains parallel to the c axis.

Related literature

For the synthesis and biological properties of the title compound and analogues, see: Bischoff (1907 ); Kaeriyama et al. (1976 ). For the use of the title compound in organic synthesis, see: Haddleton & Waterson (1999 ); Edeleva et al. (2009 ); Guillaneuf et al. (2007 ).

Experimental

Crystal data

C₁₀H₁₀BrNO₄
M_r = 288.10
Orthorhombic, P b c n
a = 11.4128 (16) Å
b = 14.450 (2) Å
c = 14.539 (2) Å
V = 2397.7 (6) Å³
Z = 8
Mo Kα radiation
μ = 3.43 mm⁻¹
T = 295 K
0.45 × 0.15 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.625, T_max = 0.720
18926 measured reflections
2177 independent reflections
1086 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.132
S = 1.00
2177 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O3ⁱ	0.93	2.59	3.385 (4)	144
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and SCHAKAL97 (Keller, 1997 ); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005988/tk2722sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005988/tk2722Isup2.hkl

checkCIF report

Comment top

The synthesis of the title compound and analogues was originally reported in the early part of last century (Bischoff, 1907), and in the seventies several of these compounds were found to possess useful miticidal, insecticidal, nematocidal or fungicidal activities (Kaeriyama et al., 1976). More recently, the title compound was prepared (Haddleton & Waterson, 1999) and used as initiator for H-atom transfer polymerization. The same compound was also used in the preparation of new alkoxyamines derived from imadaziline-, imidazoline- and pyrrolidine-1-oxyl nitroxides (Edeleva et al., 2009) and, within our group, for the synthesis of phenyl- and 4-nitrophenyl- 2-(2,2-diphenyl-3-(phenylimino)-indolin-1-yloxy)-2-methylpropionate (Guillaneuf et al., 2007). In order to obtain structural parameters for molecular mechanics calculations for the above mentioned alkoxyamines, the X-ray crystal structure of the title compound has been determined and the results are reported herein.

In the molecule of the title compound (Fig. 1), the plane of the nitro group is approximately coplanar with the benzene ring (dihedral angle 6.4 (3) °), whereas the plane of the carboxylic group is tilted by 60.53 (13) °. All bond lengths and angles are unexceptional. In the crystal structure (Fig. 2), the molecules are linked by intermolecular C—H···O hydrogen bonds (Table 1) into zigzag chains running parallel to the c axis.

Related literature top

For the synthesis and biological properties of the title compound and analogues, see: Bischoff (1907); Kaeriyama et al. (1976). For the use of the title compound in organic synthesis, see: Haddleton & Waterson (1999); Edeleva et al. (2009); Guillaneuf et al. (2007).

Experimental top

The title compound was prepared according to the literature method (Haddleton & Waterson, 1999). Crystals suitable for X-ray analysis were obtained by slow evaporation of its n-pentane solution (m. p. 342–343 K). IR data, ν, cm^-1: 1753 (C═O), 1615 and 1592 (benzene ring), 1521 (NO₂). ¹H NMR spectrum, δ in CDCl₃: 2.08 (s, 6H); 7.3 (2H, d, J = 9.2 Hz); 8.31 (2H, d, J = 9.2 Hz). The ESI-MS obtained with 3200 QTRAP spectrometer does not give the molecular ion peak. The melting point was measured by an electrothermal apparatus and is uncorrected. The ¹H NMR spectrum was recorded with a Varian 400 MHz spectrometer. The IR spectrum was recorded with a Perkin-Elmer MGX1 spectrophotometer.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and SCHAKAL97 (Keller, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PARST95 (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 40% probability level.
	Fig. 2. Partial crystal packing of the title compound viewed approximately along the a axis. Intermolecular C—H···O hydrogen bonds are shown as dashed lines.

4-Nitrophenyl 2-bromo-2-methylpropanoate top

Crystal data top

C₁₀H₁₀BrNO₄	F(000) = 1152
M_r = 288.10	D_x = 1.596 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 877 reflections
a = 11.4128 (16) Å	θ = 5.6–21.3°
b = 14.450 (2) Å	µ = 3.43 mm⁻¹
c = 14.539 (2) Å	T = 295 K
V = 2397.7 (6) Å³	Needle, colourless
Z = 8	0.45 × 0.15 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	2177 independent reflections
Radiation source: fine-focus sealed tube	1086 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ω scans	θ_max = 25.3°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→13
T_min = 0.625, T_max = 0.720	k = −15→17
18926 measured reflections	l = −17→17

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0685P)²] where P = (F_o² + 2F_c²)/3
2177 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.84 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

C₁₀H₁₀BrNO₄	V = 2397.7 (6) Å³
M_r = 288.10	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 11.4128 (16) Å	µ = 3.43 mm⁻¹
b = 14.450 (2) Å	T = 295 K
c = 14.539 (2) Å	0.45 × 0.15 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	2177 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1086 reflections with I > 2σ(I)
T_min = 0.625, T_max = 0.720	R_int = 0.049
18926 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.132	H-atom parameters constrained
S = 1.00	Δρ_max = 0.84 e Å⁻³
2177 reflections	Δρ_min = −0.51 e Å⁻³
145 parameters

Special details top

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
Br1	−0.00330 (6)	0.10818 (4)	0.62160 (4)	0.1233 (3)
O1	−0.0531 (2)	0.33291 (18)	0.53800 (18)	0.0757 (8)
O2	0.1275 (2)	0.30016 (16)	0.58917 (16)	0.0639 (7)
O3	0.1600 (3)	0.6175 (2)	0.8793 (2)	0.1042 (11)
O4	0.1583 (4)	0.6983 (2)	0.7567 (2)	0.1188 (13)
N1	0.1583 (3)	0.6243 (3)	0.7961 (3)	0.0724 (9)
C1	0.0266 (3)	0.1820 (2)	0.5074 (2)	0.0603 (10)
C2	0.1417 (3)	0.1512 (2)	0.4701 (3)	0.0783 (12)
H2A	0.2016	0.1614	0.5154	0.117*
H2B	0.1597	0.1859	0.4156	0.117*
H2C	0.1380	0.0865	0.4554	0.117*
C3	−0.0733 (4)	0.1656 (3)	0.4429 (4)	0.1049 (17)
H3A	−0.1451	0.1849	0.4714	0.157*
H3B	−0.0777	0.1009	0.4283	0.157*
H3C	−0.0612	0.2005	0.3875	0.157*
C4	0.0267 (3)	0.2799 (3)	0.5452 (2)	0.0603 (10)
C5	0.1339 (3)	0.3821 (2)	0.6389 (3)	0.0551 (9)
C6	0.1295 (3)	0.4663 (3)	0.5954 (2)	0.0628 (10)
H6	0.1207	0.4695	0.5319	0.075*
C8	0.1531 (3)	0.5392 (3)	0.7411 (2)	0.0556 (9)
C7	0.1381 (3)	0.5461 (3)	0.6467 (3)	0.0626 (10)
H7	0.1339	0.6038	0.6184	0.075*
C9	0.1598 (3)	0.4549 (3)	0.7842 (2)	0.0618 (10)
H9	0.1699	0.4515	0.8476	0.074*
C10	0.1515 (3)	0.3756 (3)	0.7324 (3)	0.0623 (10)
H10	0.1576	0.3179	0.7604	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1760 (7)	0.0961 (5)	0.0979 (5)	−0.0278 (3)	0.0319 (3)	0.0105 (3)
O1	0.0642 (16)	0.0717 (18)	0.091 (2)	0.0147 (14)	−0.0123 (15)	−0.0147 (15)
O2	0.0549 (15)	0.0642 (17)	0.0727 (16)	0.0074 (13)	−0.0079 (13)	−0.0145 (14)
O3	0.153 (3)	0.095 (2)	0.064 (2)	−0.023 (2)	−0.0036 (18)	−0.0151 (16)
O4	0.198 (4)	0.061 (2)	0.097 (2)	−0.017 (2)	−0.004 (2)	−0.0031 (19)
N1	0.084 (2)	0.071 (3)	0.062 (2)	−0.0081 (19)	0.0088 (19)	−0.009 (2)
C1	0.058 (2)	0.062 (2)	0.061 (2)	0.0014 (18)	−0.0044 (18)	−0.0028 (19)
C2	0.080 (3)	0.062 (3)	0.093 (3)	0.014 (2)	0.012 (2)	−0.005 (2)
C3	0.097 (3)	0.087 (3)	0.131 (4)	0.018 (3)	−0.043 (3)	−0.047 (3)
C4	0.053 (2)	0.070 (3)	0.058 (2)	0.006 (2)	−0.0084 (19)	−0.007 (2)
C5	0.0414 (19)	0.060 (2)	0.064 (2)	0.0041 (17)	0.0010 (17)	−0.006 (2)
C6	0.069 (2)	0.075 (3)	0.045 (2)	−0.001 (2)	0.0076 (18)	−0.001 (2)
C8	0.046 (2)	0.064 (3)	0.056 (2)	−0.0086 (18)	0.0046 (16)	−0.007 (2)
C7	0.071 (2)	0.059 (3)	0.057 (2)	−0.003 (2)	0.0135 (19)	0.003 (2)
C9	0.062 (2)	0.073 (3)	0.050 (2)	−0.002 (2)	−0.0102 (18)	0.005 (2)
C10	0.058 (2)	0.055 (2)	0.074 (3)	0.0015 (19)	−0.0109 (19)	0.0033 (19)

Geometric parameters (Å, º) top

Br1—C1	2.002 (4)	C3—H3A	0.9600
O1—C4	1.195 (4)	C3—H3B	0.9600
O2—C4	1.348 (4)	C3—H3C	0.9600
O2—C5	1.390 (4)	C5—C6	1.372 (5)
O3—N1	1.214 (4)	C5—C10	1.378 (5)
O4—N1	1.214 (4)	C6—C7	1.376 (5)
N1—C8	1.467 (5)	C6—H6	0.9300
C1—C2	1.489 (5)	C8—C9	1.372 (5)
C1—C3	1.496 (5)	C8—C7	1.388 (5)
C1—C4	1.518 (5)	C7—H7	0.9300
C2—H2A	0.9600	C9—C10	1.375 (5)
C2—H2B	0.9600	C9—H9	0.9300
C2—H2C	0.9600	C10—H10	0.9300

C4—O2—C5	118.5 (3)	O1—C4—O2	123.6 (4)
O4—N1—O3	122.8 (4)	O1—C4—C1	124.4 (3)
O4—N1—C8	118.8 (3)	O2—C4—C1	112.0 (3)
O3—N1—C8	118.4 (4)	C6—C5—C10	121.4 (4)
C2—C1—C3	113.4 (3)	C6—C5—O2	121.0 (3)
C2—C1—C4	114.2 (3)	C10—C5—O2	117.6 (3)
C3—C1—C4	112.0 (3)	C5—C6—C7	119.4 (3)
C2—C1—Br1	107.1 (2)	C5—C6—H6	120.3
C3—C1—Br1	107.8 (3)	C7—C6—H6	120.3
C4—C1—Br1	101.3 (2)	C9—C8—C7	121.5 (3)
C1—C2—H2A	109.5	C9—C8—N1	119.5 (4)
C1—C2—H2B	109.5	C7—C8—N1	118.9 (3)
H2A—C2—H2B	109.5	C6—C7—C8	119.0 (4)
C1—C2—H2C	109.5	C6—C7—H7	120.5
H2A—C2—H2C	109.5	C8—C7—H7	120.5
H2B—C2—H2C	109.5	C8—C9—C10	119.1 (4)
C1—C3—H3A	109.5	C8—C9—H9	120.4
C1—C3—H3B	109.5	C10—C9—H9	120.4
H3A—C3—H3B	109.5	C9—C10—C5	119.5 (4)
C1—C3—H3C	109.5	C9—C10—H10	120.2
H3A—C3—H3C	109.5	C5—C10—H10	120.2
H3B—C3—H3C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3ⁱ	0.93	2.59	3.385 (4)	144

Symmetry code: (i) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀BrNO₄
M_r	288.10
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	295
a, b, c (Å)	11.4128 (16), 14.450 (2), 14.539 (2)
V (Å³)	2397.7 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.43
Crystal size (mm)	0.45 × 0.15 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.625, 0.720
No. of measured, independent and observed [I > 2σ(I)] reflections	18926, 2177, 1086
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.132, 1.00
No. of reflections	2177
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.51

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SIR97 (Altomare et al., 1999), ORTEP-3 for Windows (Farrugia, 1997) and SCHAKAL97 (Keller, 1997), SHELXL97 (Sheldrick, 2008) and PARST95 (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3ⁱ	0.93	2.59	3.385 (4)	144

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

Financial support from the Universitá Politecnica delle Marche and the Universitá degli Studi di Parma is gratefully acknowledged.

References

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