5-(Pyridin-4-yl)isophthalic acid

Zhang, Y.-F.; Zhang, Q.-F.; Jin, J.; Sun, D.-Z.; Wang, D.-Q.

doi:10.1107/S1600536810039474

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2928

https://doi.org/10.1107/S1600536810039474

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5-(Pyridin-4-yl)isophthalic acid

Yong-Fang Zhang,^a Qing-Fu Zhang,^a ^* Juan Jin,^a De-Zhi Sun ^a and Da-Qi Wang ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: zhangqingfu@foxmail.com

(Received 29 September 2010; accepted 3 October 2010; online 23 October 2010)

In the title compound, C₁₃H₉NO₄, the two carboxylic groups and the benzene ring are approximately co-planar with a maximum atomic deviation 0.175 (4) Å, while the pyridine ring is oriented at a dihedral angle of 31.07 (18)° with respect to the benzene ring. In the crystal, molecules are linked by O—H⋯O, O—H⋯N and weak C—H⋯O hydrogen bonds, forming a three-dimensional supramolecular framework.

Related literature

For background to carboxylic acids as supramolecular synthons, see: Desiraju (1995 ); Thalladi et al. (1996 ).

Experimental

Crystal data

C₁₃H₉NO₄
M_r = 243.21
Orthorhombic, F d d 2
a = 15.5362 (16) Å
b = 37.371 (3) Å
c = 7.1716 (9) Å
V = 4163.9 (8) Å³
Z = 16
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.10 mm

Data collection

Siemens SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.966, T_max = 0.988
4224 measured reflections
1004 independent reflections
879 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.107
S = 1.04
1004 reflections
164 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N1ⁱ	0.82	1.78	2.558 (3)	157
O3—H3A⋯O2ⁱⁱ	0.82	1.91	2.620 (3)	144
C10—H10⋯O1ⁱⁱⁱ	0.93	2.57	3.491 (4)	172
Symmetry codes: (i) $[-x+{\script{7\over 4}}, y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (ii) $[x-{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810039474/xu5043sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039474/xu5043Isup2.hkl

checkCIF report

Comment top

Carboxylic acid is an interesting supramolecular synthon, widely used to construct supramolecular array with one to three different dimensions via hydrogen bonds (Desiraju, 1995; Thalladi et al., 1996). In order to explore this area, the structure of the title compound, 5-(pyridin-4-yl)isophthalic acid, is reported herein.

As shown in Fig.1, the two carboxylic groups and the phenyl ring system in the title compound are almost planar with the maximum deviation 0.175Å for atom O₂ in the carboxylic group. However, the pyridine ring and the phenyl ring is not coplanar, with the dihedral angle 31.07°. This may be due to intermolecular O—H···N hydrogen-bonding interactions.

In the crystal structure, the dicarboxylic acid molecules are linked by intermolecular O—H···N, O—H···O and C—H···O hydrogen bonding interactions into a three-dimensional framework (Fig. 2).

Related literature top

For background to carboxylic acids as supramolecular synthons, see: Desiraju (1995); Thalladi et al. (1996).

Experimental top

The commercially available title compound, 5-(pyridin-4-yl)isophthalic acid, was recrystallized from an aqueous solution.

Structure description top

For background to carboxylic acids as supramolecular synthons, see: Desiraju (1995); Thalladi et al. (1996).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids.
	Fig. 2. The packing diagram of the title compound.

5-(Pyridin-4-yl)isophthalic acid top

Crystal data top

C₁₃H₉NO₄	F(000) = 2016
M_r = 243.21	D_x = 1.552 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 1601 reflections
a = 15.5362 (16) Å	θ = 2.8–26.5°
b = 37.371 (3) Å	µ = 0.12 mm⁻¹
c = 7.1716 (9) Å	T = 296 K
V = 4163.9 (8) Å³	Block, colorless
Z = 16	0.30 × 0.20 × 0.10 mm

Data collection top

Siemens SMART 1000 CCD area-detector diffractometer	1004 independent reflections
Radiation source: fine-focus sealed tube	879 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
φ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→8
T_min = 0.966, T_max = 0.988	k = −44→38
4224 measured reflections	l = −8→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0701P)² + 2.9125P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1004 reflections	Δρ_max = 0.33 e Å⁻³
164 parameters	Δρ_min = −0.21 e Å⁻³
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0010 (3)

Crystal data top

C₁₃H₉NO₄	V = 4163.9 (8) Å³
M_r = 243.21	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 15.5362 (16) Å	µ = 0.12 mm⁻¹
b = 37.371 (3) Å	T = 296 K
c = 7.1716 (9) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Siemens SMART 1000 CCD area-detector diffractometer	1004 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	879 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.988	R_int = 0.045
4224 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.107	H-atom parameters constrained
S = 1.04	Δρ_max = 0.33 e Å⁻³
1004 reflections	Δρ_min = −0.21 e Å⁻³
164 parameters

Special details top

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 taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used 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 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	0.70913 (15)	0.16593 (6)	0.0729 (5)	0.0455 (7)
O2	0.81725 (15)	0.13320 (6)	−0.0349 (5)	0.0401 (7)
H2A	0.8354	0.1528	−0.0678	0.060*
O3	0.45574 (15)	0.10618 (6)	0.3114 (4)	0.0450 (8)
H3A	0.4068	0.1054	0.3541	0.068*
O4	0.45297 (14)	0.04779 (6)	0.3757 (4)	0.0451 (8)
N1	0.85168 (17)	−0.05737 (7)	0.1930 (5)	0.0351 (7)
C1	0.74454 (19)	0.13706 (8)	0.0469 (5)	0.0290 (8)
C2	0.4902 (2)	0.07358 (8)	0.3152 (6)	0.0294 (8)
C3	0.70358 (19)	0.10312 (8)	0.1149 (5)	0.0265 (7)
C4	0.74860 (19)	0.07115 (8)	0.1188 (5)	0.0274 (8)
H4	0.8058	0.0707	0.0807	0.033*
C5	0.70940 (18)	0.03966 (8)	0.1790 (5)	0.0257 (7)
C6	0.62393 (19)	0.04072 (8)	0.2376 (5)	0.0283 (8)
H6	0.5966	0.0198	0.2755	0.034*
C7	0.57949 (19)	0.07292 (8)	0.2395 (5)	0.0270 (8)
C8	0.6192 (2)	0.10389 (8)	0.1779 (5)	0.0268 (8)
H8	0.5891	0.1254	0.1788	0.032*
C9	0.7591 (2)	0.00577 (8)	0.1821 (5)	0.0276 (8)
C10	0.8478 (2)	0.00577 (8)	0.2122 (6)	0.0330 (9)
H10	0.8772	0.0272	0.2282	0.040*
C11	0.8915 (2)	−0.02631 (9)	0.2179 (6)	0.0374 (9)
H11	0.9505	−0.0262	0.2399	0.045*
C12	0.7669 (2)	−0.05810 (9)	0.1627 (6)	0.0361 (9)
H12	0.7397	−0.0800	0.1450	0.043*
C13	0.7191 (2)	−0.02726 (8)	0.1570 (5)	0.0319 (8)
H13	0.6601	−0.0284	0.1364	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0389 (14)	0.0232 (12)	0.074 (2)	0.0034 (10)	0.0125 (14)	0.0062 (14)
O2	0.0330 (12)	0.0211 (11)	0.0664 (18)	−0.0048 (10)	0.0166 (13)	0.0045 (11)
O3	0.0301 (12)	0.0342 (13)	0.071 (2)	0.0072 (10)	0.0199 (13)	0.0063 (14)
O4	0.0318 (13)	0.0342 (13)	0.069 (2)	−0.0040 (10)	0.0164 (13)	0.0055 (13)
N1	0.0337 (15)	0.0266 (14)	0.045 (2)	0.0059 (12)	0.0011 (14)	0.0036 (14)
C1	0.0239 (15)	0.0255 (17)	0.037 (2)	−0.0015 (13)	0.0017 (14)	0.0042 (15)
C2	0.0261 (15)	0.0287 (17)	0.033 (2)	−0.0007 (13)	0.0011 (15)	0.0030 (15)
C3	0.0240 (15)	0.0243 (15)	0.031 (2)	−0.0011 (12)	0.0009 (14)	0.0007 (14)
C4	0.0202 (15)	0.0279 (16)	0.034 (2)	0.0013 (12)	0.0025 (14)	−0.0003 (14)
C5	0.0241 (15)	0.0239 (15)	0.0289 (18)	0.0014 (12)	0.0013 (14)	0.0020 (15)
C6	0.0255 (16)	0.0251 (16)	0.034 (2)	−0.0024 (13)	0.0025 (15)	0.0008 (14)
C7	0.0238 (15)	0.0254 (16)	0.032 (2)	0.0003 (12)	−0.0006 (15)	0.0006 (14)
C8	0.0233 (15)	0.0234 (15)	0.034 (2)	0.0032 (12)	0.0020 (14)	0.0008 (15)
C9	0.0275 (16)	0.0253 (16)	0.030 (2)	0.0031 (13)	0.0064 (14)	0.0026 (15)
C10	0.0252 (15)	0.0253 (16)	0.048 (2)	−0.0004 (12)	0.0006 (16)	0.0026 (16)
C11	0.0269 (17)	0.0345 (19)	0.051 (3)	0.0037 (14)	−0.0009 (17)	0.0042 (17)
C12	0.0347 (18)	0.0246 (16)	0.049 (3)	−0.0007 (13)	0.0011 (18)	0.0024 (16)
C13	0.0277 (16)	0.0259 (15)	0.042 (2)	−0.0008 (13)	0.0018 (16)	0.0041 (15)

Geometric parameters (Å, º) top

O1—C1	1.225 (4)	C5—C6	1.393 (4)
O2—C1	1.281 (4)	C5—C9	1.483 (4)
O2—H2A	0.8200	C6—C7	1.387 (4)
O3—C2	1.331 (4)	C6—H6	0.9300
O3—H3A	0.8200	C7—C8	1.384 (4)
O4—C2	1.205 (4)	C8—H8	0.9300
N1—C11	1.327 (4)	C9—C10	1.395 (4)
N1—C12	1.335 (4)	C9—C13	1.394 (5)
C1—C3	1.501 (4)	C10—C11	1.378 (5)
C2—C7	1.489 (4)	C10—H10	0.9300
C3—C4	1.385 (4)	C11—H11	0.9300
C3—C8	1.386 (4)	C12—C13	1.372 (5)
C4—C5	1.394 (4)	C12—H12	0.9300
C4—H4	0.9300	C13—H13	0.9300

C1—O2—H2A	109.5	C8—C7—C6	120.0 (3)
C2—O3—H3A	109.5	C8—C7—C2	121.2 (3)
C11—N1—C12	120.0 (3)	C6—C7—C2	118.8 (3)
O1—C1—O2	124.4 (3)	C7—C8—C3	120.6 (3)
O1—C1—C3	120.3 (3)	C7—C8—H8	119.7
O2—C1—C3	115.3 (3)	C3—C8—H8	119.7
O4—C2—O3	123.1 (3)	C10—C9—C13	117.4 (3)
O4—C2—C7	124.4 (3)	C10—C9—C5	121.1 (3)
O3—C2—C7	112.5 (3)	C13—C9—C5	121.5 (3)
C4—C3—C8	119.3 (3)	C11—C10—C9	119.4 (3)
C4—C3—C1	121.4 (3)	C11—C10—H10	120.3
C8—C3—C1	119.3 (3)	C9—C10—H10	120.3
C3—C4—C5	120.9 (3)	N1—C11—C10	121.8 (3)
C3—C4—H4	119.5	N1—C11—H11	119.1
C5—C4—H4	119.5	C10—C11—H11	119.1
C6—C5—C4	119.1 (3)	N1—C12—C13	121.5 (3)
C6—C5—C9	121.1 (3)	N1—C12—H12	119.3
C4—C5—C9	119.9 (3)	C13—C12—H12	119.3
C7—C6—C5	120.2 (3)	C12—C13—C9	119.9 (3)
C7—C6—H6	119.9	C12—C13—H13	120.0
C5—C6—H6	119.9	C9—C13—H13	120.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1ⁱ	0.82	1.78	2.558 (3)	157
O3—H3A···O2ⁱⁱ	0.82	1.91	2.620 (3)	144
C10—H10···O1ⁱⁱⁱ	0.93	2.57	3.491 (4)	172

Symmetry codes: (i) −x+7/4, y+1/4, z−1/4; (ii) x−1/2, y, z+1/2; (iii) x+1/4, −y+1/4, z+1/4.

Experimental details

Crystal data
Chemical formula	C₁₃H₉NO₄
M_r	243.21
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	296
a, b, c (Å)	15.5362 (16), 37.371 (3), 7.1716 (9)
V (Å³)	4163.9 (8)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Siemens SMART 1000 CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.966, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	4224, 1004, 879
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.107, 1.04
No. of reflections	1004
No. of parameters	164
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.21

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1ⁱ	0.82	1.78	2.558 (3)	157
O3—H3A···O2ⁱⁱ	0.82	1.91	2.620 (3)	144
C10—H10···O1ⁱⁱⁱ	0.93	2.57	3.491 (4)	172

Symmetry codes: (i) −x+7/4, y+1/4, z−1/4; (ii) x−1/2, y, z+1/2; (iii) x+1/4, −y+1/4, z+1/4.

Acknowledgements

We acknowledge the National Natural Science Foundation of China (grant No. 21001061), Liaocheng University Funds for Young Scientists (31805) and the Students Science and Technology Innovation Fund of Liaocheng University, China (SRT10058HX2).

References

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Thalladi, V. R., Goud, B. S., Hoy, V. J., Allen, F. H., Howard, J. A. K. & Desiraju, G. R. (1996). Chem. Commun. pp. 401–402. CSD CrossRef Web of Science Google Scholar