4-Nitro­isophthalic acid

Luo, Y.-H.; Pan, M.-L.

doi:10.1107/S1600536811053797

organic compounds

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Volume 68| Part 1| January 2012| Page o206

doi:10.1107/S1600536811053797

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4-Nitroisophthalic acid

Yang-Hui Luo ^a ^* and Mei-Ling Pan ^a

^aKey Laboratory of Urban and Architectural Heritage Conservation, (Southeast University), Ministry of Education, Nanjing 210096, People's Republic of China, and College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: peluoyh@sina.com

(Received 30 November 2011; accepted 14 December 2011; online 21 December 2011)

In the crystal structure of the title compound, C₈H₅NO₆, both carboxyl groups are involved in intermolecular centrosymmetric cyclic O—H⋯O hydrogen-bonding associations, which give a zigzag chain structure extending along (2 $[\overline{1}]$ 1). Weak π–π stacking interactions are also present [minimum ring centroid separation = 3.893 (4) Å].

Related literature

For 4-nitroisophthalic acid as an intermediate in the synthesis of pharmaceutical drugs and as a ligand in transition metal complexes, see: Birk & Weihe (2009 ); Pan et al. (2011 ).

Experimental

Crystal data

C₈H₅NO₆
M_r = 211.13
Triclinic, $[P \overline 1]$
a = 7.0261 (14) Å
b = 7.4380 (15) Å
c = 8.5775 (17) Å
α = 80.09 (3)°
β = 86.22 (3)°
γ = 75.37 (3)°
V = 427.14 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku SCXmini CCD-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.957, T_max = 0.971
4103 measured reflections
1943 independent reflections
1554 reflections with I > 2σ(I)
R_int = 0.136

Refinement

R[F² > 2σ(F²)] = 0.092
wR(F²) = 0.308
S = 0.86
1943 reflections
136 parameters
8 restraints
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O3ⁱ	0.86	1.76	2.605 (7)	168
O5—H5⋯O6ⁱⁱ	0.87	1.73	2.602 (7)	180
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) -x, -y+2, -z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536811053797/zs2171sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053797/zs2171Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811053797/zs2171Isup3.cml

checkCIF report

Comment top

4-Nitroisophthalic acid is an important chemical material because it is an intermediate in the synthesis of many pharmaceutical drugs and is also an excellent ligand for many transition metal complexes (Pan et al., 2011; Birk & Weihe, 2009). As part of our interest in this compound, we report here the crystal structure of this acid.

The molecular structure of the title compound, C₈H₅NO₆ is shown in Fig. 1. All of the non-H and non-O atoms are approximately coplanar: the maximu r.m.s. deviation being 0.0202 Å. In the crystal structure, both carboxylic acid groups are involved in intermolecular centrosymmetric cyclic O—H···O hydrogen-bonding associations (Table 1) which give a zigzag chain structure extending along (2 -1 1) (Fig. 2). Weak π···π stacking interactions are also present [minimum ring centroid separation = 3.893 (4) Å].

Related literature top

For related literature, see: Birk & Weihe (2009); Pan et al. (2011).

Experimental top

4-Nitroisophthalic acid was obtained commercially from ChemFuture PharmaTech, Ltd (Nanjing, Jiangsu). Crystals of it suitable for X-ray diffraction were obstained by slow evaporation of a methanol solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A packing diagram viewed down the a axis showing the three-dimensional network. Intermolecular hydrogen bonds are shown as dashed lines.

4-nitrobenzene-1,3-dicarboxylic acid top

Crystal data top

C₈H₅NO₆	Z = 2
M_r = 211.13	F(000) = 216
Triclinic, P1	D_x = 1.642 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0261 (14) Å	Cell parameters from 1943 reflections
b = 7.4380 (15) Å	θ = 3.0–27.5°
c = 8.5775 (17) Å	µ = 0.15 mm⁻¹
α = 80.09 (3)°	T = 293 K
β = 86.22 (3)°	Prism, red
γ = 75.37 (3)°	0.30 × 0.25 × 0.20 mm
V = 427.14 (15) Å³

Data collection top

Rigaku SCXmini CCD-detector diffractometer	1943 independent reflections
Radiation source: fine-focus sealed tube	1554 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.136
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD profile–fitting scans	h = −9→9
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)	k = −9→9
T_min = 0.957, T_max = 0.971	l = −11→11
4103 measured reflections

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)] = 0.092	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.308	H-atom parameters constrained
S = 0.86	w = 1/[σ²(F_o²) + (0.1225P)²] where P = (F_o² + 2F_c²)/3
1943 reflections	(Δ/σ)_max = 0.017
136 parameters	Δρ_max = 0.40 e Å⁻³
8 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₈H₅NO₆	γ = 75.37 (3)°
M_r = 211.13	V = 427.14 (15) Å³
Triclinic, P1	Z = 2
a = 7.0261 (14) Å	Mo Kα radiation
b = 7.4380 (15) Å	µ = 0.15 mm⁻¹
c = 8.5775 (17) Å	T = 293 K
α = 80.09 (3)°	0.30 × 0.25 × 0.20 mm
β = 86.22 (3)°

Data collection top

Rigaku SCXmini CCD-detector diffractometer	1943 independent reflections
Absorption correction: multi-scan CrystalClear (Rigaku, 2005)	1554 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.971	R_int = 0.136
4103 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.092	8 restraints
wR(F²) = 0.308	H-atom parameters constrained
S = 0.86	Δρ_max = 0.40 e Å⁻³
1943 reflections	Δρ_min = −0.50 e Å⁻³
136 parameters

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 esds are taken into account in the estimation of distances, angles and torsion angles

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 > σ(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	0.7042 (7)	0.0658 (7)	0.5109 (6)	0.0760 (19)
O2	0.8052 (7)	−0.0122 (8)	0.2874 (6)	0.081 (2)
O3	0.9385 (6)	0.3293 (8)	0.4061 (6)	0.076 (2)
O4	0.7716 (6)	0.6167 (8)	0.4485 (6)	0.074 (2)
O5	0.2226 (6)	0.9309 (7)	0.0974 (5)	0.0637 (18)
O6	0.0288 (6)	0.7626 (7)	0.0224 (6)	0.0706 (18)
N1	0.7089 (7)	0.1015 (8)	0.3680 (6)	0.0470 (19)
C1	0.7884 (8)	0.4702 (9)	0.3938 (7)	0.041 (2)
C2	0.6144 (7)	0.4407 (9)	0.3070 (6)	0.0396 (19)
C3	0.5813 (8)	0.2668 (9)	0.2931 (7)	0.044 (2)
C4	0.4265 (8)	0.2656 (9)	0.2113 (7)	0.0446 (19)
C5	0.2929 (8)	0.4233 (10)	0.1433 (7)	0.049 (2)
C6	0.4838 (7)	0.6123 (9)	0.2397 (6)	0.0397 (19)
C7	0.3223 (7)	0.5954 (10)	0.1615 (6)	0.045 (2)
C8	0.1809 (8)	0.7812 (9)	0.0882 (7)	0.045 (2)
H4	0.87560	0.63520	0.48410	0.0880*
H4A	0.40800	0.14920	0.19970	0.0540*
H5	0.13830	1.03360	0.05700	0.0770*
H5A	0.18720	0.41500	0.08750	0.0590*
H6A	0.50480	0.72900	0.24730	0.0480*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.075 (3)	0.068 (4)	0.066 (3)	0.011 (3)	−0.018 (3)	0.005 (3)
O2	0.098 (4)	0.058 (4)	0.067 (3)	0.017 (3)	−0.008 (3)	−0.006 (3)
O3	0.034 (2)	0.080 (4)	0.105 (4)	0.007 (3)	−0.030 (2)	−0.010 (3)
O4	0.045 (2)	0.097 (4)	0.085 (4)	−0.009 (3)	−0.029 (2)	−0.032 (3)
O5	0.049 (2)	0.067 (4)	0.074 (3)	−0.006 (3)	−0.034 (2)	−0.008 (3)
O6	0.042 (2)	0.086 (4)	0.079 (3)	−0.001 (3)	−0.034 (2)	−0.010 (3)
N1	0.046 (3)	0.053 (4)	0.036 (3)	−0.006 (3)	−0.015 (2)	0.005 (3)
C1	0.035 (3)	0.047 (4)	0.041 (4)	−0.012 (3)	−0.007 (3)	−0.001 (3)
C2	0.025 (3)	0.052 (4)	0.038 (3)	0.000 (3)	−0.012 (2)	−0.007 (3)
C3	0.032 (3)	0.055 (4)	0.043 (4)	−0.002 (3)	−0.012 (3)	−0.012 (3)
C4	0.048 (3)	0.032 (3)	0.060 (4)	−0.017 (3)	−0.011 (3)	−0.010 (3)
C5	0.038 (3)	0.067 (5)	0.044 (4)	−0.010 (4)	−0.016 (3)	−0.011 (3)
C6	0.032 (3)	0.052 (4)	0.036 (3)	−0.011 (3)	−0.012 (2)	−0.004 (3)
C7	0.030 (3)	0.071 (5)	0.032 (3)	−0.004 (3)	−0.009 (2)	−0.010 (3)
C8	0.037 (3)	0.046 (4)	0.054 (4)	−0.006 (3)	−0.013 (3)	−0.012 (3)

Geometric parameters (Å, º) top

O1—N1	1.209 (7)	C2—C6	1.424 (9)
O2—N1	1.225 (8)	C2—C3	1.396 (9)
O3—C1	1.281 (8)	C3—C4	1.335 (8)
O4—C1	1.235 (9)	C4—C5	1.370 (9)
O5—C8	1.237 (8)	C5—C7	1.383 (10)
O6—C8	1.289 (7)	C6—C7	1.398 (7)
O4—H4	0.8600	C7—C8	1.543 (9)
O5—H5	0.8700	C4—H4A	0.9300
N1—C3	1.406 (8)	C5—H5A	0.9300
C1—C2	1.552 (8)	C6—H6A	0.9300

C1—O4—H4	118.00	C4—C5—C7	117.0 (5)
C8—O5—H5	116.00	C2—C6—C7	116.2 (6)
O1—N1—C3	118.7 (5)	C5—C7—C8	120.9 (5)
O2—N1—C3	119.2 (5)	C6—C7—C8	116.3 (6)
O1—N1—O2	121.5 (6)	C5—C7—C6	122.7 (6)
O4—C1—C2	120.2 (6)	O6—C8—C7	115.3 (5)
O3—C1—O4	126.0 (6)	O5—C8—O6	126.5 (6)
O3—C1—C2	113.8 (5)	O5—C8—C7	118.2 (5)
C3—C2—C6	121.0 (5)	C3—C4—H4A	118.00
C1—C2—C6	113.4 (5)	C5—C4—H4A	118.00
C1—C2—C3	125.6 (5)	C4—C5—H5A	122.00
N1—C3—C4	122.9 (6)	C7—C5—H5A	121.00
N1—C3—C2	118.9 (5)	C2—C6—H6A	122.00
C2—C3—C4	118.2 (6)	C7—C6—H6A	122.00
C3—C4—C5	124.8 (6)

O1—N1—C3—C2	69.8 (8)	C3—C2—C6—C7	0.6 (8)
O1—N1—C3—C4	−108.8 (7)	N1—C3—C4—C5	176.5 (6)
O2—N1—C3—C2	−118.3 (6)	C2—C3—C4—C5	−2.1 (9)
O2—N1—C3—C4	63.1 (8)	C3—C4—C5—C7	0.0 (9)
O3—C1—C2—C3	23.2 (8)	C4—C5—C7—C6	2.5 (8)
O3—C1—C2—C6	−157.0 (5)	C4—C5—C7—C8	179.5 (5)
O4—C1—C2—C3	−154.2 (6)	C2—C6—C7—C5	−2.7 (8)
O4—C1—C2—C6	25.5 (8)	C2—C6—C7—C8	−179.9 (5)
C1—C2—C3—N1	2.8 (9)	C5—C7—C8—O5	−174.4 (5)
C1—C2—C3—C4	−178.6 (5)	C5—C7—C8—O6	5.5 (8)
C6—C2—C3—N1	−177.0 (5)	C6—C7—C8—O5	2.8 (8)
C6—C2—C3—C4	1.7 (8)	C6—C7—C8—O6	−177.3 (5)
C1—C2—C6—C7	−179.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ⁱ	0.86	1.76	2.605 (7)	168
O5—H5···O6ⁱⁱ	0.87	1.73	2.602 (7)	180
C5—H5A···O6ⁱⁱⁱ	0.93	2.56	3.423 (8)	154

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

Experimental details

Crystal data
Chemical formula	C₈H₅NO₆
M_r	211.13
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.0261 (14), 7.4380 (15), 8.5775 (17)
α, β, γ (°)	80.09 (3), 86.22 (3), 75.37 (3)
V (Å³)	427.14 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku SCXmini CCD-detector diffractometer
Absorption correction	Multi-scan CrystalClear (Rigaku, 2005)
T_min, T_max	0.957, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	4103, 1943, 1554
R_int	0.136
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.092, 0.308, 0.86
No. of reflections	1943
No. of parameters	136
No. of restraints	8
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.50

Computer programs: CrystalClear (Rigaku, 2005), CrystalClear, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), SHELXL97.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3ⁱ	0.86	1.76	2.605 (7)	168
O5—H5···O6ⁱⁱ	0.87	1.73	2.602 (7)	180

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

References

Birk, T. & Weihe, H. (2009). J. Chem. Crystallogr. 39, 766–771. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Pan, M.-L., Luo, Y.-H. & Mao, S.-L. (2011). Acta Cryst. E67, o2345. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku. (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o206

doi:10.1107/S1600536811053797

Open

access