Methyl 2-amino-5-bromo­benzoate

Khan, I.U.; Khan, M.H.; Akkurt, M.

doi:10.1107/S1600536811025165

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1887

doi:10.1107/S1600536811025165

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Methyl 2-amino-5-bromobenzoate

Islam Ullah Khan,^a ^* Muneeb Hayat Khan ^a and Mehmet Akkurt ^b ^*

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan, and ^bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey
^*Correspondence e-mail: iukhan@gcu.edu.pk, akkurt@erciyes.edu.tr

(Received 23 June 2011; accepted 27 June 2011; online 2 July 2011)

In the title compound, C₈H₈BrNO₂, the dihedral angle between the aromatic ring and the methyl acetate side chain is 5.73 (12)°. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond, generating an S(6) ring. In the crystal, molecules are connected by N—H⋯O interactions, generating zigzag chains running along the b-axis direction.

Related literature

For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₈BrNO₂
M_r = 230.05
Monoclinic, P 2₁
a = 3.9852 (2) Å
b = 9.1078 (5) Å
c = 12.1409 (7) Å
β = 95.238 (3)°
V = 438.83 (4) Å³
Z = 2
Mo Kα radiation
μ = 4.64 mm⁻¹
T = 296 K
0.21 × 0.19 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
3878 measured reflections
1822 independent reflections
1570 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.045
S = 0.94
1822 reflections
116 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 655 Freidel pairs
Flack parameter: 0.022 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1	0.84 (2)	2.08 (3)	2.717 (3)	133 (3)
N1—H2N⋯O1ⁱ	0.85 (2)	2.22 (3)	3.039 (3)	162 (2)
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811025165/hb5930sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025165/hb5930Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025165/hb5930Isup3.cml

checkCIF report

Comment top

The title compound is an intermediate for the synthesis of benzothiazines.

In the title compound (I), (Fig. 1), except H atoms, all atoms are almost coplanar with the maximum deviations of -0.122 (2) Å for O1, 0.077 (2) Å for O2, -0.050 (1) Å for Br1 and 0.048 (3) Å for C8. The C5—C6—C7—O1, C5—C6—C7—O2, C6—C7—O2—C8 and O1—C7—O2—C8 torsion angles are 174.3 (2), -5.2 (3), -178.9 (2) and 0.6 (3)°, respectively.

The molecular conformation is stabilized by intramolecular N—H···O hydrogen bond (Table 1, Fig. 1) forming S(6) ring (Bernstein et al., 1995). In the crystal structure, intermolecular N—H···O interactions link the neighbouring molecules to each other, producing a zigzag chain along the b axis (Table 1). Figures 2 and 3 show the packing and hydrogen bonding of the title compound viewing down the a and b-axes, respectively.

Related literature top

For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The title compound was purchased from Sigma-Aldrich and recrystalized in methanol to yield light yellow blocks.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The title molecule with displacement ellipsoids for non-H atoms drawn at the 50% probability level.
	Fig. 2. The packing and hydrogen bonding of the title compound viewing down the a axis. Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 3. The packing and hydrogen bonding of the title compound viewing down the b axis. Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

Methyl 2-amino-5-bromobenzoate top

Crystal data top

C₈H₈BrNO₂	F(000) = 228
M_r = 230.05	D_x = 1.741 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2303 reflections
a = 3.9852 (2) Å	θ = 2.8–26.3°
b = 9.1078 (5) Å	µ = 4.64 mm⁻¹
c = 12.1409 (7) Å	T = 296 K
β = 95.238 (3)°	Block, light yellow
V = 438.83 (4) Å³	0.21 × 0.19 × 0.15 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1570 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.021
Graphite monochromator	θ_max = 28.3°, θ_min = 3.4°
ϕ and ω scans	h = −3→5
3878 measured reflections	k = −12→10
1822 independent reflections	l = −15→15

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)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.045	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
S = 0.94	(Δ/σ)_max < 0.001
1822 reflections	Δρ_max = 0.29 e Å⁻³
116 parameters	Δρ_min = −0.24 e Å⁻³
3 restraints	Absolute structure: Flack (1983), 655 Freidel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.022 (9)

Crystal data top

C₈H₈BrNO₂	V = 438.83 (4) Å³
M_r = 230.05	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 3.9852 (2) Å	µ = 4.64 mm⁻¹
b = 9.1078 (5) Å	T = 296 K
c = 12.1409 (7) Å	0.21 × 0.19 × 0.15 mm
β = 95.238 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1570 reflections with I > 2σ(I)
3878 measured reflections	R_int = 0.021
1822 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.045	Δρ_max = 0.29 e Å⁻³
S = 0.94	Δρ_min = −0.24 e Å⁻³
1822 reflections	Absolute structure: Flack (1983), 655 Freidel pairs
116 parameters	Absolute structure parameter: 0.022 (9)
3 restraints

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.60353 (6)	0.04286 (5)	0.06725 (2)	0.0596 (1)
O1	−0.0244 (5)	0.5400 (3)	0.36497 (11)	0.0619 (6)
O2	0.1200 (4)	0.5450 (3)	0.19255 (11)	0.0510 (5)
N1	0.1618 (6)	0.3011 (2)	0.48993 (17)	0.0516 (8)
C1	0.2591 (6)	0.2478 (2)	0.39185 (18)	0.0377 (8)
C2	0.3968 (6)	0.1064 (2)	0.3901 (2)	0.0434 (8)
C3	0.4990 (5)	0.0477 (4)	0.29613 (16)	0.0435 (7)
C4	0.4676 (6)	0.1276 (2)	0.19848 (18)	0.0403 (8)
C5	0.3422 (6)	0.2668 (2)	0.19724 (18)	0.0378 (7)
C6	0.2343 (6)	0.3290 (2)	0.29357 (17)	0.0348 (7)
C7	0.0988 (6)	0.4787 (2)	0.28974 (19)	0.0394 (8)
C8	−0.0137 (8)	0.6915 (3)	0.1821 (2)	0.0596 (10)
H1N	0.039 (8)	0.376 (2)	0.484 (3)	0.0710*
H2	0.41870	0.05150	0.45500	0.0520*
H2N	0.147 (7)	0.240 (3)	0.5425 (19)	0.0710*
H3	0.59020	−0.04640	0.29710	0.0520*
H5	0.32810	0.32100	0.13200	0.0450*
H8A	−0.24790	0.69040	0.19480	0.0900*
H8B	0.01050	0.72780	0.10900	0.0900*
H8C	0.10720	0.75420	0.23550	0.0900*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0709 (2)	0.0566 (2)	0.0534 (2)	0.0159 (2)	0.0178 (1)	−0.0131 (2)
O1	0.1002 (13)	0.0407 (8)	0.0489 (9)	0.0161 (15)	0.0288 (8)	−0.0031 (12)
O2	0.0743 (10)	0.0373 (8)	0.0435 (8)	0.0152 (14)	0.0164 (7)	0.0039 (11)
N1	0.0771 (17)	0.0435 (13)	0.0359 (12)	−0.0050 (11)	0.0151 (11)	−0.0012 (10)
C1	0.0446 (14)	0.0347 (13)	0.0338 (12)	−0.0104 (10)	0.0036 (10)	−0.0033 (10)
C2	0.0526 (16)	0.0379 (13)	0.0396 (13)	−0.0011 (10)	0.0042 (10)	0.0078 (10)
C3	0.0469 (12)	0.0305 (11)	0.0528 (12)	0.0054 (16)	0.0035 (9)	−0.0033 (17)
C4	0.0432 (14)	0.0403 (14)	0.0378 (13)	0.0010 (10)	0.0059 (10)	−0.0076 (10)
C5	0.0468 (14)	0.0342 (12)	0.0333 (12)	0.0032 (10)	0.0089 (9)	0.0008 (10)
C6	0.0397 (14)	0.0317 (12)	0.0334 (12)	−0.0024 (9)	0.0050 (9)	−0.0032 (9)
C7	0.0482 (15)	0.0304 (11)	0.0400 (13)	−0.0016 (9)	0.0058 (10)	−0.0035 (10)
C8	0.080 (2)	0.0332 (14)	0.0659 (18)	0.0172 (13)	0.0088 (14)	0.0075 (12)

Geometric parameters (Å, º) top

Br1—C4	1.893 (2)	C3—C4	1.387 (3)
O1—C7	1.212 (3)	C4—C5	1.362 (3)
O2—C7	1.335 (3)	C5—C6	1.402 (3)
O2—C8	1.438 (4)	C6—C7	1.466 (3)
N1—C1	1.374 (3)	C2—H2	0.9300
N1—H1N	0.84 (2)	C3—H3	0.9300
N1—H2N	0.85 (2)	C5—H5	0.9300
C1—C6	1.400 (3)	C8—H8A	0.9600
C1—C2	1.401 (3)	C8—H8B	0.9600
C2—C3	1.356 (3)	C8—H8C	0.9600

C7—O2—C8	116.41 (18)	O1—C7—O2	121.4 (2)
C1—N1—H1N	115 (2)	O1—C7—C6	125.3 (2)
C1—N1—H2N	117.5 (18)	O2—C7—C6	113.3 (2)
H1N—N1—H2N	121 (3)	C1—C2—H2	119.00
C2—C1—C6	118.0 (2)	C3—C2—H2	119.00
N1—C1—C2	118.68 (19)	C2—C3—H3	120.00
N1—C1—C6	123.27 (18)	C4—C3—H3	120.00
C1—C2—C3	121.6 (2)	C4—C5—H5	120.00
C2—C3—C4	120.1 (3)	C6—C5—H5	120.00
Br1—C4—C3	119.67 (17)	O2—C8—H8A	110.00
Br1—C4—C5	120.19 (16)	O2—C8—H8B	109.00
C3—C4—C5	120.1 (2)	O2—C8—H8C	109.00
C4—C5—C6	120.46 (19)	H8A—C8—H8B	109.00
C5—C6—C7	119.32 (18)	H8A—C8—H8C	109.00
C1—C6—C5	119.64 (18)	H8B—C8—H8C	109.00
C1—C6—C7	121.05 (19)

C8—O2—C7—C6	178.9 (2)	C2—C3—C4—C5	1.7 (4)
C8—O2—C7—O1	−0.6 (3)	Br1—C4—C5—C6	178.61 (18)
C6—C1—C2—C3	−1.1 (3)	C3—C4—C5—C6	−1.9 (4)
N1—C1—C2—C3	−179.7 (2)	C4—C5—C6—C7	−179.7 (2)
C2—C1—C6—C5	0.8 (3)	C4—C5—C6—C1	0.7 (3)
C2—C1—C6—C7	−178.8 (2)	C1—C6—C7—O1	−6.0 (4)
N1—C1—C6—C5	179.4 (2)	C5—C6—C7—O2	−5.2 (3)
N1—C1—C6—C7	−0.2 (4)	C1—C6—C7—O2	174.5 (2)
C1—C2—C3—C4	−0.2 (4)	C5—C6—C7—O1	174.3 (2)
C2—C3—C4—Br1	−178.82 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.84 (2)	2.08 (3)	2.717 (3)	133 (3)
N1—H2N···O1ⁱ	0.85 (2)	2.22 (3)	3.039 (3)	162 (2)

Symmetry code: (i) −x, y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₈H₈BrNO₂
M_r	230.05
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	3.9852 (2), 9.1078 (5), 12.1409 (7)
β (°)	95.238 (3)
V (Å³)	438.83 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.64
Crystal size (mm)	0.21 × 0.19 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3878, 1822, 1570
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.045, 0.94
No. of reflections	1822
No. of parameters	116
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24
Absolute structure	Flack (1983), 655 Freidel pairs
Absolute structure parameter	0.022 (9)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.84 (2)	2.08 (3)	2.717 (3)	133 (3)
N1—H2N···O1ⁱ	0.85 (2)	2.22 (3)	3.039 (3)	162 (2)

Symmetry code: (i) −x, y−1/2, −z+1.

Acknowledgements

The authors are grateful to Mr Shahzad Shrif for his assistance and the Higher Education Commission (HEC), Pakistan, for financial support under the project to strengthen the Materials Chemistry Laboratory at GCUL.

References

Bernstein, J., Davies, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar