Dimethyl 5-nitro­isophthalate

Xie, M.-H.; Zou, P.; He, Y.-J.; Liu, Y.-L.; Huang, B.

doi:10.1107/S1600536808024938

organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1736

doi:10.1107/S1600536808024938

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Dimethyl 5-nitroisophthalate

Min-Hao Xie,^a Pei Zou,^a Yong-Jun He,^a Ya-Ling Liu ^a and Biao Huang ^a ^*

^aJiangsu Institute of Nuclear Medicine, Wuxi 214063, People's Republic of China
^*Correspondence e-mail: xiemh0704@sina.com

(Received 9 July 2008; accepted 3 August 2008; online 9 August 2008)

The nitro group in the title compound, C₁₀H₉NO₆, is rotated by 10.9 (5)° out of the plane of the benzene ring.

Related literature

For related literature, see: Bjorsvik et al. (2001 ); Cutroneo et al. (2007 ); Enzweiler et al. (2006 ).

Experimental

Crystal data

C₁₀H₉NO₆
M_r = 239.18
Triclinic, $[P \overline 1]$
a = 4.0130 (8) Å
b = 10.660 (2) Å
c = 12.643 (3) Å
α = 106.11 (3)°
β = 93.74 (3)°
γ = 91.46 (3)°
V = 517.97 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 (2) K
0.40 × 0.05 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 )) T_min = 0.950, T_max = 0.994
2178 measured reflections
1885 independent reflections
1144 reflections with I > 2σ(I)
R_int = 0.041
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.172
S = 1.01
1885 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808024938/cs2086sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808024938/cs2086Isup2.hkl

checkCIF report

Comment top

The title molecule (Fig.1), is useful as an important intermediate for the preparation of iodinated X-ray contrast media, in particular non-ionic ones such as Iopamidol, Iohexol and Ioversol, being used clinically all over the world (Cutroneo et al., 2007; Bjorsvik et al., 2001; Enzweiler et al., 2006). This crystal structure shows that the benzene ring and the nitro group are only slightly inclined, as shown by the torsion angles of O5—N—C7—C6 -10.6 (5)° and of O6—N—C7—C8 -11.2 (5)°.

Related literature top

For related literature, see: Bjorsvik et al. (2001); Cutroneo et al. (2007); Enzweiler et al. (2006).

Experimental top

5-nitroisophthalic acid (0.5 mmol,100.6 mg) was dissolved in hot methanol (5 ml), then a drop of concentrated sulfuric acid was added and refluxed for 4 h. The precipitate was filtered off, washed with water and dissolved in 95% ethanol(20 mL). The solution was evaporated in air affording colourless needle crystals suitable for X-ray analysis (yield: 85.2%).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

Dimethyl 5-nitrobenzene-1,3-dicarboxylate top

Crystal data top

C₁₀H₉NO₆	Z = 2
M_r = 239.18	F(000) = 248
Triclinic, P1	D_x = 1.534 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.0130 (8) Å	Cell parameters from 25 reflections
b = 10.660 (2) Å	θ = 8–12°
c = 12.643 (3) Å	µ = 0.13 mm⁻¹
α = 106.11 (3)°	T = 293 K
β = 93.74 (3)°	Needle, colourless
γ = 91.46 (3)°	0.40 × 0.05 × 0.05 mm
V = 517.97 (18) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	1144 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.041
Graphite monochromator	θ_max = 25.3°, θ_min = 1.7°
ω/2θ scans	h = −4→4
Absorption correction: ψ scan (North et al., 1968))	k = −12→12
T_min = 0.950, T_max = 0.994	l = 0→15
2178 measured reflections	3 standard reflections every 200 reflections
1885 independent reflections	intensity decay: none

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.05P)² + 0.6P] where P = (F_o² + 2F_c²)/3
1885 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₀H₉NO₆	γ = 91.46 (3)°
M_r = 239.18	V = 517.97 (18) Å³
Triclinic, P1	Z = 2
a = 4.0130 (8) Å	Mo Kα radiation
b = 10.660 (2) Å	µ = 0.13 mm⁻¹
c = 12.643 (3) Å	T = 293 K
α = 106.11 (3)°	0.40 × 0.05 × 0.05 mm
β = 93.74 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1144 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968))	R_int = 0.041
T_min = 0.950, T_max = 0.994	3 standard reflections every 200 reflections
2178 measured reflections	intensity decay: none
1885 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.01	Δρ_max = 0.28 e Å⁻³
1885 reflections	Δρ_min = −0.18 e Å⁻³
154 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N	0.5209 (9)	0.7040 (3)	0.8012 (3)	0.0572 (8)
O1	0.7307 (7)	0.1642 (2)	0.5059 (2)	0.0642 (8)
C1	0.8443 (12)	0.0907 (4)	0.4027 (3)	0.0717 (13)
H1A	0.8215	−0.0010	0.3965	0.108*
H1B	1.0748	0.1145	0.3992	0.108*
H1C	0.7126	0.1094	0.3431	0.108*
O2	0.8638 (9)	0.3487 (3)	0.4668 (2)	0.0825 (10)
C2	0.7532 (9)	0.2943 (3)	0.5284 (3)	0.0480 (9)
O3	0.2103 (7)	0.1601 (2)	0.8322 (2)	0.0608 (8)
C3	0.0691 (12)	0.0824 (4)	0.8961 (4)	0.0703 (12)
H3A	0.0833	−0.0086	0.8583	0.105*
H3B	−0.1610	0.1022	0.9054	0.105*
H3C	0.1906	0.1016	0.9671	0.105*
O4	0.1018 (8)	0.3426 (3)	0.9595 (2)	0.0739 (9)
C4	0.2108 (9)	0.2883 (3)	0.8735 (3)	0.0482 (9)
C5	0.3639 (8)	0.3588 (3)	0.8013 (3)	0.0424 (8)
O5	0.3683 (10)	0.7593 (3)	0.8783 (3)	0.0957 (12)
C6	0.3703 (9)	0.4947 (3)	0.8341 (3)	0.0465 (9)
H6A	0.2839	0.5401	0.8996	0.056*
O6	0.6840 (9)	0.7614 (3)	0.7524 (3)	0.0910 (11)
C7	0.5090 (8)	0.5598 (3)	0.7663 (3)	0.0445 (8)
C8	0.6352 (8)	0.4972 (3)	0.6687 (3)	0.0457 (8)
H8A	0.7276	0.5447	0.6254	0.055*
C9	0.6236 (9)	0.3612 (3)	0.6351 (3)	0.0448 (8)
C10	0.4871 (8)	0.2942 (3)	0.7022 (3)	0.0450 (8)
H10A	0.4781	0.2033	0.6802	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N	0.065 (2)	0.0474 (18)	0.061 (2)	0.0053 (16)	0.0112 (17)	0.0155 (16)
O1	0.091 (2)	0.0508 (15)	0.0511 (15)	0.0022 (14)	0.0238 (14)	0.0100 (12)
C1	0.099 (4)	0.062 (2)	0.054 (2)	0.013 (2)	0.027 (2)	0.009 (2)
O2	0.124 (3)	0.0604 (17)	0.0677 (19)	−0.0108 (17)	0.0448 (18)	0.0181 (15)
C2	0.049 (2)	0.0464 (19)	0.050 (2)	−0.0043 (16)	0.0047 (17)	0.0156 (17)
O3	0.085 (2)	0.0465 (14)	0.0549 (16)	0.0031 (13)	0.0257 (14)	0.0166 (12)
C3	0.089 (3)	0.057 (2)	0.072 (3)	−0.002 (2)	0.027 (2)	0.025 (2)
O4	0.105 (2)	0.0593 (17)	0.0644 (18)	0.0145 (16)	0.0411 (17)	0.0209 (14)
C4	0.049 (2)	0.049 (2)	0.048 (2)	0.0061 (16)	0.0103 (17)	0.0131 (17)
C5	0.0417 (19)	0.0443 (18)	0.0420 (19)	0.0034 (15)	0.0021 (15)	0.0139 (15)
O5	0.134 (3)	0.0523 (17)	0.107 (3)	0.0219 (18)	0.057 (2)	0.0198 (17)
C6	0.050 (2)	0.0473 (19)	0.0437 (19)	0.0042 (16)	0.0029 (16)	0.0145 (16)
O6	0.131 (3)	0.0527 (17)	0.089 (2)	−0.0210 (18)	0.036 (2)	0.0148 (16)
C7	0.0388 (19)	0.0405 (17)	0.054 (2)	0.0001 (15)	−0.0011 (16)	0.0137 (16)
C8	0.045 (2)	0.0507 (19)	0.0432 (19)	−0.0005 (16)	0.0012 (16)	0.0174 (16)
C9	0.047 (2)	0.0464 (19)	0.0412 (18)	0.0013 (16)	0.0028 (16)	0.0127 (15)
C10	0.044 (2)	0.0449 (18)	0.046 (2)	−0.0032 (15)	0.0042 (16)	0.0130 (16)

Geometric parameters (Å, º) top

N—O6	1.194 (4)	C3—H3B	0.9600
N—O5	1.204 (4)	C3—H3C	0.9600
N—C7	1.475 (4)	O4—C4	1.198 (4)
O1—C2	1.336 (4)	C4—C5	1.485 (5)
O1—C1	1.433 (4)	C5—C10	1.381 (4)
C1—H1A	0.9600	C5—C6	1.391 (5)
C1—H1B	0.9600	C6—C7	1.378 (5)
C1—H1C	0.9600	C6—H6A	0.9300
O2—C2	1.193 (4)	C7—C8	1.366 (5)
C2—C9	1.475 (5)	C8—C9	1.392 (5)
O3—C4	1.320 (4)	C8—H8A	0.9300
O3—C3	1.438 (4)	C9—C10	1.381 (5)
C3—H3A	0.9600	C10—H10A	0.9300

O6—N—O5	122.5 (3)	O4—C4—C5	123.3 (3)
O6—N—C7	118.6 (3)	O3—C4—C5	112.4 (3)
O5—N—C7	118.9 (3)	C10—C5—C6	119.7 (3)
C2—O1—C1	116.9 (3)	C10—C5—C4	122.3 (3)
O1—C1—H1A	109.5	C6—C5—C4	117.9 (3)
O1—C1—H1B	109.5	C7—C6—C5	117.8 (3)
H1A—C1—H1B	109.5	C7—C6—H6A	121.1
O1—C1—H1C	109.5	C5—C6—H6A	121.1
H1A—C1—H1C	109.5	C8—C7—C6	123.1 (3)
H1B—C1—H1C	109.5	C8—C7—N	118.7 (3)
O2—C2—O1	122.5 (3)	C6—C7—N	118.2 (3)
O2—C2—C9	124.5 (3)	C7—C8—C9	119.0 (3)
O1—C2—C9	112.9 (3)	C7—C8—H8A	120.5
C4—O3—C3	116.9 (3)	C9—C8—H8A	120.5
O3—C3—H3A	109.5	C10—C9—C8	118.7 (3)
O3—C3—H3B	109.5	C10—C9—C2	122.6 (3)
H3A—C3—H3B	109.5	C8—C9—C2	118.7 (3)
O3—C3—H3C	109.5	C5—C10—C9	121.6 (3)
H3A—C3—H3C	109.5	C5—C10—H10A	119.2
H3B—C3—H3C	109.5	C9—C10—H10A	119.2
O4—C4—O3	124.3 (3)

C1—O1—C2—O2	−0.4 (6)	O6—N—C7—C6	168.8 (4)
C1—O1—C2—C9	178.7 (3)	O5—N—C7—C6	−10.6 (5)
C3—O3—C4—O4	−0.1 (6)	C6—C7—C8—C9	0.2 (5)
C3—O3—C4—C5	179.7 (3)	N—C7—C8—C9	−179.7 (3)
O4—C4—C5—C10	−179.8 (4)	C7—C8—C9—C10	−0.6 (5)
O3—C4—C5—C10	0.4 (5)	C7—C8—C9—C2	178.6 (3)
O4—C4—C5—C6	−2.1 (5)	O2—C2—C9—C10	177.7 (4)
O3—C4—C5—C6	178.1 (3)	O1—C2—C9—C10	−1.4 (5)
C10—C5—C6—C7	−1.5 (5)	O2—C2—C9—C8	−1.4 (6)
C4—C5—C6—C7	−179.3 (3)	O1—C2—C9—C8	179.5 (3)
C5—C6—C7—C8	0.8 (5)	C6—C5—C10—C9	1.2 (5)
C5—C6—C7—N	−179.2 (3)	C4—C5—C10—C9	178.9 (3)
O6—N—C7—C8	−11.2 (5)	C8—C9—C10—C5	−0.1 (5)
O5—N—C7—C8	169.4 (4)	C2—C9—C10—C5	−179.3 (3)

Experimental details

Crystal data
Chemical formula	C₁₀H₉NO₆
M_r	239.18
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	4.0130 (8), 10.660 (2), 12.643 (3)
α, β, γ (°)	106.11 (3), 93.74 (3), 91.46 (3)
V (Å³)	517.97 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.40 × 0.05 × 0.05

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968))
T_min, T_max	0.950, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	2178, 1885, 1144
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.172, 1.01
No. of reflections	1885
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.18

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Acknowledgements

The Key Laboratory of Nuclear Medicine of the Ministry Health of China is thanked for supporting this work.

References

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