4-tert-Butyl-amino-3-nitro-benzoic acid.

In the title compound, C(11)H(14)N(2)O(4), 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 intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal packing, the mol-ecules are linked together by O-H⋯O hydrogen bonds, forming dimers with graph-set motif R(2) (2)(8) which propagate along the a-axis direction. C-H⋯O contacts link adjacent dimers with a graph-set motif C(2) (2)(7), forming chains along b, and further consolidate the structure into a three-dimensional network. The crystal packing is further strengthened by short inter-molecular 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 = 238.24

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.065

wR(F 2) = 0.153

S = 1.11

1418 reflections

107 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.37 e Å−3

Δρmin = −0.31 e Å−3

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 ▶).

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

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

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

C11H14N2O4	F(000) = 504
Mr = 238.24	Dx = 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

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

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(Fo2) + (0.058P)2 + 2.3728P] where P = (Fo2 + 2Fc2)/3
1418 reflections	(Δ/σ)max < 0.001
107 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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

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

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···O2iv	0.96	2.53	3.437 (3)	158

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) ; (ii) ; (iii) .