4-tert-Butyl­amino-3-nitro­benzoic acid

Narendra Babu, S.N.; Abdul Rahim, A.S.; Abd Hamid, S.; Jebas, S.R.; Fun, H.-K.

doi:10.1107/S1600536809015487

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages o1233-o1234

doi:10.1107/S1600536809015487

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4-tert-Butylamino-3-nitrobenzoic acid

Shivanagere Nagojappa Narendra Babu,^a Aisyah Saad Abdul Rahim,^a ‡ Shafida Abd Hamid,^b Samuel Robinson Jebas ^c § and Hoong-Kun Fun ^c ^*¶

^aSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bKulliyyah of Science, International Islamic University Malaysia (IIUM), Jalan Istana, Bandar Indera Mahkota, 25200 Kuantan, Pahang, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 Universiti Sains Malaysia, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 22 April 2009; accepted 25 April 2009; online 7 May 2009)

In the title compound, C₁₁H₁₄N₂O₄, all non-H atoms lie in a mirror plane except for one of the methyl groups which deviates from the mirror plane by 0.919 (3) Å and is twisted by a torsion angle of 62.9 (2)°. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal packing, the molecules are linked together by O—H⋯O hydrogen bonds, forming dimers with graph-set motif R₂²(8) which propagate along the a-axis direction. C—H⋯O contacts link adjacent dimers with a graph-set motif C₂²(7), forming chains along b, and further consolidate the structure into a three-dimensional network. The crystal packing is further strengthened by short intermolecular O⋯O=C [2.655 (4) Å] contacts.

Related literature

Nitro benzoic acid derivatives are important intermediates for the synthesis of various heterocyclic compounds of pharmacological interest, see: Brouillette et al. (1999 ); Williams et al. (1995 ). For the structure of 4-(tert-butylamino)-3-nitrobenzoate, see: Mohd Maidin et al. (2008 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₁H₁₄N₂O₄
M_r = 238.24
Monoclinic, C 2/m
a = 20.8125 (15) Å
b = 6.7412 (5) Å
c = 8.0793 (5) Å
β = 90.863 (6)°
V = 1133.41 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.39 × 0.10 × 0.03 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.959, T_max = 0.997
6267 measured reflections
1418 independent reflections
985 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.153
S = 1.11
1418 reflections
107 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2ⁱ	0.82 (4)	1.83 (4)	2.655 (4)	178 (4)
C1—H1A⋯O3ⁱⁱ	0.93	2.52	3.407 (4)	161
N2—H1N2⋯O4	0.81 (4)	1.97 (4)	2.641 (4)	139 (4)
C9—H9C⋯O2ⁱⁱⁱ	0.96	2.53	3.437 (3)	158
Symmetry codes: (i) -x+1, y, -z+1; (ii) x, y, z-1; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809015487/tk2439sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015487/tk2439Isup2.hkl

checkCIF report

Comment top

Nitro benzoic acid derivatives are important intermediates for the synthesis of various heterocyclic compounds of pharmacological interest (Brouillette et al., 1999; Williams et al., 1995). As a part of our ongoing study on such compounds, in this paper, we present the crystal structure of the title compound (I) which was synthesized as an intermediate.

In the asymmetric unit of (I), all non-hydrogen atoms lie in a mirror plane except the methyl-C9A moiety, which is deviated from the mean plane by 0.919 (3) Å and twisted by a torsion angle C6–N2–C7–C9 of 62.9 (2) Å.

An intramolecular N—H···O hydrogen bond generates a ring of motif S(6) (Bernstein et al., 1995) (Fig. 1). In the crystal packing, the molecules are linked together by O—H···O hydrogen bonds to form dimers with the graph set motif R₂²(8) which propagate along the a-direction (Table 1). C—H···O contacts link adjacent dimers with a graph set motif C₂²(7) (Fig. 2) to form chains along the b-direction and further consolidate the structure into a 3D network. The crystal packing is further strengthened by short intermolecular O···O^i-ii = 2.655 (4)Å contacts; symmetry code: (i) 1-x, y, 1-z; (ii) 1-x, 1-y, 1-z.

Related literature top

Nitro benzoic acid derivatives are important intermediates for the synthesis of various heterocyclic compounds of pharmacological interest, see: Brouillette et al. (1999); Williams et al. (1995). For the structure of 4-(tert-butylamino)-3-nitrobenzoate, see: Mohd Maidin et al. (2008). For hydrogen-bond motifs, see: Bernstein et al. (1995). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

Compound (I) was prepared by refluxing ethyl 4-(tert-butylamino)-3-nitrobenzoate (0.7 g, 0.0026 mol) (Mohd Maidin et al., 2008) and KOH (0.14 g, 0.0026 mol) in aqueous ethanol (10 ml) for 3 h. Ethanol was then removed in vacuo and the reaction mixture was diluted with water (15 ml). The aqueous layer was washed with dichloromethane (10 ml × 2) and acidified with concentrated hydrochloric acid to bring about the precipitation of the desired benzoic acid. Recrystallization of the precipitate with hot ethyl acetate afforded yellow crystals of the title compound (I).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom numbering scheme. Intramolecular hydrogen bonding is shown as a dashed line. [Symmetry code used to generate methyl moiety C9A: x, -y + 1, z]
	Fig. 2. The crystal packing of (I), viewed along the c axis. Dashed lines indicate the hydrogen bonding and C—H···O contacts.

(I) top

Crystal data top

C₁₁H₁₄N₂O₄	F(000) = 504
M_r = 238.24	D_x = 1.396 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 1829 reflections
a = 20.8125 (15) Å	θ = 3.2–30.6°
b = 6.7412 (5) Å	µ = 0.11 mm⁻¹
c = 8.0793 (5) Å	T = 100 K
β = 90.863 (6)°	Plate, yellow
V = 1133.41 (14) Å³	0.39 × 0.10 × 0.03 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1418 independent reflections
Radiation source: fine-focus sealed tube	985 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −26→26
T_min = 0.959, T_max = 0.997	k = −8→8
6267 measured reflections	l = −10→10

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.058P)² + 2.3728P] where P = (F_o² + 2F_c²)/3
1418 reflections	(Δ/σ)_max < 0.001
107 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₁H₁₄N₂O₄	V = 1133.41 (14) Å³
M_r = 238.24	Z = 4
Monoclinic, C2/m	Mo Kα radiation
a = 20.8125 (15) Å	µ = 0.11 mm⁻¹
b = 6.7412 (5) Å	T = 100 K
c = 8.0793 (5) Å	0.39 × 0.10 × 0.03 mm
β = 90.863 (6)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1418 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	985 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.997	R_int = 0.057
6267 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.37 e Å⁻³
1418 reflections	Δρ_min = −0.31 e Å⁻³
107 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O1	0.44372 (12)	0.5000	0.3166 (3)	0.0189 (6)
O2	0.43314 (11)	0.5000	0.5919 (3)	0.0185 (6)
O3	0.22447 (11)	0.5000	0.8193 (3)	0.0198 (6)
O4	0.13560 (11)	0.5000	0.6766 (3)	0.0187 (6)
N1	0.19540 (13)	0.5000	0.6848 (3)	0.0130 (6)
N2	0.13842 (13)	0.5000	0.3497 (4)	0.0131 (6)
C1	0.24626 (16)	0.5000	0.2381 (4)	0.0142 (7)
H1A	0.2298	0.5000	0.1304	0.017*
C2	0.31116 (16)	0.5000	0.2615 (4)	0.0145 (7)
H2A	0.3377	0.5000	0.1700	0.017*
C3	0.33894 (15)	0.5000	0.4217 (4)	0.0122 (7)
C4	0.29869 (16)	0.5000	0.5563 (4)	0.0126 (7)
H4A	0.3163	0.5000	0.6628	0.015*
C5	0.23216 (16)	0.5000	0.5349 (4)	0.0130 (7)
C6	0.20244 (16)	0.5000	0.3726 (4)	0.0129 (7)
C7	0.09935 (16)	0.5000	0.1929 (4)	0.0145 (7)
C8	0.02967 (16)	0.5000	0.2518 (4)	0.0184 (8)
H8B	0.0008	0.5000	0.1581	0.028*
H8C	0.0228	0.3861	0.3206	0.028*
C9	0.11138 (11)	0.3105 (4)	0.0926 (3)	0.0169 (6)
H9A	0.1558	0.3044	0.0627	0.025*
H9B	0.0850	0.3120	−0.0060	0.025*
H9C	0.1008	0.1966	0.1581	0.025*
C10	0.40933 (15)	0.5000	0.4522 (4)	0.0132 (7)
H1N2	0.1189 (18)	0.5000	0.435 (5)	0.015 (10)*
H1O1	0.4804 (19)	0.5000	0.341 (5)	0.010 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0086 (13)	0.0327 (15)	0.0154 (14)	0.000	0.0005 (10)	0.000
O2	0.0121 (12)	0.0293 (14)	0.0142 (13)	0.000	0.0012 (10)	0.000
O3	0.0207 (13)	0.0282 (14)	0.0104 (12)	0.000	0.0002 (10)	0.000
O4	0.0130 (13)	0.0279 (14)	0.0153 (13)	0.000	0.0045 (10)	0.000
N1	0.0154 (15)	0.0119 (14)	0.0117 (15)	0.000	0.0033 (11)	0.000
N2	0.0113 (15)	0.0189 (15)	0.0092 (15)	0.000	0.0029 (12)	0.000
C1	0.0197 (18)	0.0147 (17)	0.0082 (17)	0.000	−0.0002 (14)	0.000
C2	0.0176 (18)	0.0131 (16)	0.0129 (18)	0.000	0.0074 (14)	0.000
C3	0.0155 (17)	0.0082 (15)	0.0128 (17)	0.000	0.0004 (13)	0.000
C4	0.0172 (17)	0.0109 (16)	0.0096 (17)	0.000	−0.0014 (13)	0.000
C5	0.0178 (18)	0.0085 (15)	0.0126 (17)	0.000	0.0016 (13)	0.000
C6	0.0166 (17)	0.0088 (15)	0.0134 (17)	0.000	0.0003 (14)	0.000
C7	0.0132 (17)	0.0158 (17)	0.0142 (17)	0.000	−0.0026 (13)	0.000
C8	0.0173 (18)	0.0215 (18)	0.0164 (18)	0.000	−0.0021 (14)	0.000
C9	0.0184 (12)	0.0163 (12)	0.0160 (12)	−0.0014 (10)	−0.0014 (10)	0.0003 (10)
C10	0.0134 (17)	0.0093 (16)	0.0170 (18)	0.000	0.0027 (14)	0.000

Geometric parameters (Å, º) top

O1—C10	1.318 (4)	C3—C4	1.383 (5)
O1—H1O1	0.79 (4)	C3—C10	1.482 (5)
O2—C10	1.226 (4)	C4—C5	1.393 (5)
O3—N1	1.236 (4)	C4—H4A	0.9300
O4—N1	1.245 (4)	C5—C6	1.441 (5)
N1—C5	1.442 (4)	C7—C8	1.533 (5)
N2—C6	1.343 (4)	C7—C9	1.536 (3)
N2—C7	1.495 (4)	C7—C9ⁱ	1.536 (3)
N2—H1N2	0.80 (4)	C8—H8B	0.9595
C1—C2	1.361 (5)	C8—H8C	0.9600
C1—C6	1.429 (5)	C9—H9A	0.9600
C1—H1A	0.9300	C9—H9B	0.9600
C2—C3	1.409 (5)	C9—H9C	0.9600
C2—H2A	0.9300

C10—O1—H1O1	109 (3)	N2—C6—C1	122.6 (3)
O3—N1—O4	121.5 (3)	N2—C6—C5	122.5 (3)
O3—N1—C5	118.6 (3)	C1—C6—C5	114.9 (3)
O4—N1—C5	119.9 (3)	N2—C7—C8	104.0 (3)
C6—N2—C7	130.0 (3)	N2—C7—C9	110.88 (17)
C6—N2—H1N2	113 (3)	C8—C7—C9	109.04 (18)
C7—N2—H1N2	117 (3)	N2—C7—C9ⁱ	110.88 (17)
C2—C1—C6	122.5 (3)	C8—C7—C9ⁱ	109.04 (18)
C2—C1—H1A	118.7	C9—C7—C9ⁱ	112.6 (3)
C6—C1—H1A	118.7	C7—C8—H8B	109.9
C1—C2—C3	121.4 (3)	C7—C8—H8C	109.3
C1—C2—H2A	119.3	H8B—C8—H8C	111.1
C3—C2—H2A	119.3	C7—C9—H9A	109.5
C4—C3—C2	118.5 (3)	C7—C9—H9B	109.5
C4—C3—C10	118.5 (3)	H9A—C9—H9B	109.5
C2—C3—C10	122.9 (3)	C7—C9—H9C	109.5
C3—C4—C5	121.0 (3)	H9A—C9—H9C	109.5
C3—C4—H4A	119.5	H9B—C9—H9C	109.5
C5—C4—H4A	119.5	O2—C10—O1	123.3 (3)
C4—C5—C6	121.7 (3)	O2—C10—C3	122.6 (3)
C4—C5—N1	115.8 (3)	O1—C10—C3	114.2 (3)
C6—C5—N1	122.5 (3)

C6—C1—C2—C3	0.0	C2—C1—C6—N2	180.0
C1—C2—C3—C4	0.0	C2—C1—C6—C5	0.0
C1—C2—C3—C10	180.0	C4—C5—C6—N2	180.0
C2—C3—C4—C5	0.0	N1—C5—C6—N2	0.0
C10—C3—C4—C5	180.0	C4—C5—C6—C1	0.0
C3—C4—C5—C6	0.0	N1—C5—C6—C1	180.0
C3—C4—C5—N1	180.0	C6—N2—C7—C8	180.0
O3—N1—C5—C4	0.0	C6—N2—C7—C9	62.9 (2)
O4—N1—C5—C4	180.0	C6—N2—C7—C9ⁱ	−62.9 (2)
O3—N1—C5—C6	180.0	C4—C3—C10—O2	0.0
O4—N1—C5—C6	0.0	C2—C3—C10—O2	180.0
C7—N2—C6—C1	0.0	C4—C3—C10—O1	180.0
C7—N2—C6—C5	180.0	C2—C3—C10—O1	0.0

Symmetry code: (i) x, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2ⁱⁱ	0.82 (4)	1.83 (4)	2.655 (4)	178 (4)
C1—H1A···O3ⁱⁱⁱ	0.93	2.52	3.407 (4)	161
N2—H1N2···O4	0.81 (4)	1.97 (4)	2.641 (4)	139 (4)
C9—H9C···O2^iv	0.96	2.53	3.437 (3)	158

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₄N₂O₄
M_r	238.24
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	100
a, b, c (Å)	20.8125 (15), 6.7412 (5), 8.0793 (5)
β (°)	90.863 (6)
V (Å³)	1133.41 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.39 × 0.10 × 0.03

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.959, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	6267, 1418, 985
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.153, 1.11
No. of reflections	1418
No. of parameters	107
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.31

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O2ⁱ	0.82 (4)	1.83 (4)	2.655 (4)	178 (4)
C1—H1A···O3ⁱⁱ	0.93	2.52	3.407 (4)	160.9
N2—H1N2···O4	0.81 (4)	1.97 (4)	2.641 (4)	139 (4)
C9—H9C···O2ⁱⁱⁱ	0.96	2.53	3.437 (3)	158.4

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

Footnotes

‡Additional correspondence author, e-mail: aisyah@usm.my.

§Thomson Reuters ResearcherID: A-5473-2009. Permanent address: Department of Physics, Karunya University, Karunya Nagar, Coimbatore 641 114, India.

¶Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

SNNB, ASAR and SAH are grateful to Universiti Sains Malaysia (USM) for funding the synthetic chemistry work under the University Research Grant (1001/PFARMASI/815026). SNNB thanks USM for a post–doctoral research fellowship. HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

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