Ethyl 3-carb-oxy-5-nitro-benzoate.

In the title compound, C(10)H(9)NO(6), the carb-oxy, ethoxy-carbonyl and nitro groups form dihedral angles of 3.8 (1), 4.5 (1) and 164.8 (1)°, respectively, with the mean plane of the benzene ring. In the crystal structure, mol-ecules lying about inversion centers are linked through O-H⋯O hydrogen bonds. C-H⋯O inter-actions are also present.

Related literature

The title compound is an important inter­mediate for the preparation of iodinated X-ray contrast media, such as iotalamic acid, ioxitalamic acid, and ioxilan, which are used clinically all over the world (Morin et al., 1987 ▶; Singh & Rathore, 1980 ▶; Stacul, 2001 ▶). For a related structure, see: Zou et al. (2009 ▶).

Experimental

Crystal data

C10H9NO6

M = 239.18

Monoclinic,

a = 14.249 (3) Å

b = 4.6450 (9) Å

c = 16.536 (4) Å

β = 108.401 (3)°

V = 1038.5 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.13 mm−1

T = 93 K

0.40 × 0.23 × 0.23 mm

Data collection

Rigaku SPIDER diffractometer

Absorption correction: none

6542 measured reflections

2355 independent reflections

1967 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.087

S = 0.99

2355 reflections

159 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.21 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2004 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901558X/pv2153sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901558X/pv2153Isup2.hkl

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

C10H9NO6	F(000) = 496
Mr = 239.18	Dx = 1.530 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3010 reflections
a = 14.249 (3) Å	θ = 3.0–27.5°
b = 4.6450 (9) Å	µ = 0.13 mm−1
c = 16.536 (4) Å	T = 93 K
β = 108.401 (3)°	Prism, colorless
V = 1038.5 (4) Å3	0.40 × 0.23 × 0.23 mm
Z = 4

Rigaku SPIDER diffractometer	1967 reflections with I > 2σ(I)
Radiation source: Rotating Anode	Rint = 0.024
graphite	θmax = 27.5°, θmin = 3.0°
ω scans	h = −18→16
6542 measured reflections	k = −5→5
2355 independent reflections	l = −21→20

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ2(Fo2) + (0.018P)2 + 0.9P] where P = (Fo2 + 2Fc2)/3
2355 reflections	(Δ/σ)max < 0.001
159 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon 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	0.13780 (9)	0.1168 (3)	0.34968 (7)	0.0298 (3)
O2	0.03728 (8)	0.0126 (3)	0.42538 (7)	0.0276 (3)
O3	0.08919 (8)	0.5402 (3)	0.69486 (7)	0.0264 (3)
O4	0.18028 (8)	0.9233 (3)	0.71824 (7)	0.0254 (3)
O5	0.42632 (9)	1.0386 (3)	0.57257 (8)	0.0295 (3)
O6	0.41511 (9)	0.7677 (3)	0.45857 (8)	0.0372 (3)
N1	0.14799 (9)	0.7034 (3)	0.67837 (8)	0.0204 (3)
C1	0.16237 (11)	0.3639 (3)	0.47870 (9)	0.0191 (3)
C2	0.24472 (11)	0.5011 (4)	0.46934 (10)	0.0212 (3)
H2	0.2662	0.4570	0.4219	0.025*
C3	0.29609 (11)	0.7032 (4)	0.52916 (10)	0.0207 (3)
C4	0.26459 (11)	0.7719 (3)	0.59811 (10)	0.0202 (3)
H4	0.2985	0.9114	0.6389	0.024*
C5	0.18231 (11)	0.6311 (3)	0.60566 (9)	0.0186 (3)
C6	0.13113 (11)	0.4266 (3)	0.54859 (9)	0.0188 (3)
H6	0.0759	0.3304	0.5566	0.023*
C7	0.10519 (11)	0.1465 (4)	0.41636 (9)	0.0207 (3)
C8	0.08258 (14)	−0.0899 (5)	0.28589 (11)	0.0362 (5)
H8A	0.0140	−0.0217	0.2590	0.043*
H8B	0.0802	−0.2788	0.3129	0.043*
C9	0.13330 (17)	−0.1176 (6)	0.22150 (14)	0.0530 (6)
H9A	0.1328	0.0686	0.1935	0.064*
H9B	0.0991	−0.2611	0.1789	0.064*
H9C	0.2018	−0.1787	0.2491	0.064*
C10	0.38474 (12)	0.8391 (4)	0.51701 (10)	0.0242 (4)
H5O	0.4809 (18)	1.103 (5)	0.5597 (14)	0.064 (8)*

	U11	U22	U33	U12	U13	U23
O1	0.0321 (6)	0.0351 (7)	0.0270 (6)	−0.0129 (6)	0.0161 (5)	−0.0098 (5)
O2	0.0262 (6)	0.0316 (7)	0.0261 (6)	−0.0117 (5)	0.0098 (5)	−0.0031 (5)
O3	0.0269 (6)	0.0273 (7)	0.0288 (6)	−0.0054 (5)	0.0143 (5)	0.0005 (5)
O4	0.0235 (6)	0.0245 (6)	0.0282 (6)	−0.0031 (5)	0.0080 (5)	−0.0077 (5)
O5	0.0227 (6)	0.0336 (7)	0.0357 (7)	−0.0122 (5)	0.0140 (5)	−0.0083 (6)
O6	0.0312 (7)	0.0485 (9)	0.0394 (7)	−0.0200 (6)	0.0218 (6)	−0.0161 (6)
N1	0.0171 (6)	0.0220 (7)	0.0220 (6)	0.0000 (5)	0.0057 (5)	0.0014 (6)
C1	0.0181 (7)	0.0184 (8)	0.0202 (7)	−0.0002 (6)	0.0052 (6)	0.0026 (6)
C2	0.0193 (7)	0.0234 (9)	0.0219 (7)	−0.0006 (6)	0.0079 (6)	0.0019 (7)
C3	0.0158 (7)	0.0212 (8)	0.0248 (7)	−0.0020 (6)	0.0060 (6)	0.0030 (7)
C4	0.0171 (7)	0.0189 (8)	0.0229 (7)	−0.0010 (6)	0.0040 (6)	0.0014 (6)
C5	0.0176 (7)	0.0194 (8)	0.0191 (7)	0.0018 (6)	0.0062 (6)	0.0032 (6)
C6	0.0155 (7)	0.0188 (8)	0.0219 (7)	−0.0003 (6)	0.0056 (6)	0.0051 (6)
C7	0.0200 (7)	0.0217 (9)	0.0209 (7)	−0.0010 (6)	0.0074 (6)	0.0024 (6)
C8	0.0397 (10)	0.0404 (12)	0.0311 (9)	−0.0145 (9)	0.0147 (8)	−0.0134 (8)
C9	0.0542 (14)	0.0675 (17)	0.0422 (12)	−0.0140 (12)	0.0224 (10)	−0.0208 (11)
C10	0.0197 (8)	0.0254 (9)	0.0272 (8)	−0.0044 (7)	0.0070 (6)	−0.0007 (7)

O1—C7	1.3320 (19)	C2—H2	0.9500
O1—C8	1.460 (2)	C3—C4	1.388 (2)
O2—C7	1.1986 (19)	C3—C10	1.481 (2)
O3—N1	1.2230 (17)	C4—C5	1.382 (2)
O4—N1	1.2242 (17)	C4—H4	0.9500
O5—C10	1.308 (2)	C5—C6	1.375 (2)
O5—H5O	0.92 (3)	C6—H6	0.9500
O6—C10	1.223 (2)	C8—C9	1.469 (3)
N1—C5	1.4726 (19)	C8—H8A	0.9900
C1—C2	1.386 (2)	C8—H8B	0.9900
C1—C6	1.394 (2)	C9—H9A	0.9800
C1—C7	1.488 (2)	C9—H9B	0.9800
C2—C3	1.392 (2)	C9—H9C	0.9800
C7—O1—C8	114.65 (13)	C5—C6—H6	120.8
C10—O5—H5O	107.3 (15)	C1—C6—H6	120.8
O3—N1—O4	124.39 (13)	O2—C7—O1	123.74 (15)
O3—N1—C5	117.92 (13)	O2—C7—C1	123.56 (14)
O4—N1—C5	117.69 (13)	O1—C7—C1	112.70 (13)
C2—C1—C6	119.97 (14)	O1—C8—C9	107.75 (16)
C2—C1—C7	122.15 (14)	O1—C8—H8A	110.2
C6—C1—C7	117.88 (14)	C9—C8—H8A	110.2
C1—C2—C3	120.29 (14)	O1—C8—H8B	110.2
C1—C2—H2	119.9	C9—C8—H8B	110.2
C3—C2—H2	119.9	H8A—C8—H8B	108.5
C4—C3—C2	120.32 (14)	C8—C9—H9A	109.5
C4—C3—C10	121.61 (14)	C8—C9—H9B	109.5
C2—C3—C10	118.07 (14)	H9A—C9—H9B	109.5
C5—C4—C3	117.97 (14)	C8—C9—H9C	109.5
C5—C4—H4	121.0	H9A—C9—H9C	109.5
C3—C4—H4	121.0	H9B—C9—H9C	109.5
C6—C5—C4	123.11 (14)	O6—C10—O5	123.54 (15)
C6—C5—N1	118.49 (13)	O6—C10—C3	121.42 (15)
C4—C5—N1	118.40 (14)	O5—C10—C3	115.04 (14)
C5—C6—C1	118.31 (14)
C6—C1—C2—C3	−0.5 (2)	C2—C1—C6—C5	1.7 (2)
C7—C1—C2—C3	179.98 (14)	C7—C1—C6—C5	−178.76 (13)
C1—C2—C3—C4	−0.8 (2)	C8—O1—C7—O2	1.3 (2)
C1—C2—C3—C10	178.79 (14)	C8—O1—C7—C1	−178.77 (14)
C2—C3—C4—C5	0.9 (2)	C2—C1—C7—O2	175.54 (15)
C10—C3—C4—C5	−178.73 (14)	C6—C1—C7—O2	−4.0 (2)
C3—C4—C5—C6	0.4 (2)	C2—C1—C7—O1	−4.3 (2)
C3—C4—C5—N1	−179.71 (13)	C6—C1—C7—O1	176.11 (14)
O3—N1—C5—C6	14.8 (2)	C7—O1—C8—C9	−174.64 (17)
O4—N1—C5—C6	−165.20 (13)	C4—C3—C10—O6	176.32 (16)
O3—N1—C5—C4	−165.12 (14)	C2—C3—C10—O6	−3.3 (2)
O4—N1—C5—C4	14.9 (2)	C4—C3—C10—O5	−4.1 (2)
C4—C5—C6—C1	−1.7 (2)	C2—C3—C10—O5	176.29 (14)
N1—C5—C6—C1	178.44 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5O···O6i	0.92 (3)	1.71 (3)	2.630 (2)	176.7 (17)
C6—H6···O2ii	0.95	2.35	3.280 (2)	165
C9—H9A···O6iii	0.98	2.56	3.354 (3)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5O⋯O6i	0.92 (3)	1.71 (3)	2.630 (2)	176.7 (17)
C6—H6⋯O2ii	0.95	2.35	3.280 (2)	165
C9—H9A⋯O6iii	0.98	2.56	3.354 (3)	138

Symmetry codes: (i) ; (ii) ; (iii) .