2-Carboxyl­atopyridinium–4-nitro­phenol (1/1)

Sankar, A.; Ambalatharasu, S.; Peramaiyan, G.; Chakkaravarthi, G.; Kanagadurai, R.

doi:10.1107/S1600536814005650

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 4| April 2014| Page o450

doi:10.1107/S1600536814005650

Open

access

2-Carboxylatopyridinium–4-nitrophenol (1/1)

A. Sankar,^a S. Ambalatharasu,^a G. Peramaiyan,^a G. Chakkaravarthi ^b ^* and R. Kanagadurai ^a ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, and ^bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, srkanagadurai@yahoo.co.in

(Received 11 March 2014; accepted 12 March 2014; online 15 March 2014)

In the title 1:1 adduct, C₆H₅NO₃·C₆H₅NO₂, both molecules are almost planar (r.m.s. deviations for the non-H atoms = 0.027 and 0.023 Å for 4-nitrophenol and 2-carboxylatopyridinium, respectively). The pyridine molecule crystallizes as a zwitterion (nominal proton transfer from the carboxylic acid group to the N atom in the ring). In the crystal, inversion dimers of the zwitterions linked by pairs of N—H⋯O hydrogen bonds generate R₂²(10) loops; two 4-nitrophenol molecules link to the dimer by O—H⋯O hydrogen bonds, generating a four-molecule aggregate. These are linked by C—H⋯O interactions, forming a three-dimensional network.

CCDC reference: 991427

Related literature

For a related structure, see: Pandi et al. (2012 ).

Experimental

Crystal data

C₆H₅NO₃·C₆H₅NO₂
M_r = 262.22
Triclinic, $[P \overline 1]$
a = 6.1743 (4) Å
b = 7.0512 (3) Å
c = 14.2222 (8) Å
α = 101.727 (3)°
β = 92.191 (2)°
γ = 104.758 (4)°
V = 583.60 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 295 K
0.32 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.963, T_max = 0.977
13952 measured reflections
3486 independent reflections
2327 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.130
S = 1.04
3486 reflections
180 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O5ⁱ	0.84 (1)	1.77 (1)	2.5929 (15)	165 (2)
N2—H2⋯O4ⁱⁱ	0.87 (1)	1.88 (1)	2.6693 (15)	151 (2)
C5—H5⋯O3ⁱⁱⁱ	0.93	2.56	3.3570 (17)	143
C9—H9⋯O2^iv	0.93	2.57	3.2009 (18)	126
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x, -y+1, -z+1; (iii) -x+2, -y+1, -z; (iv) -x, -y, -z.

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 991427

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814005650/hb7209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814005650/hb7209Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814005650/hb7209Isup3.cml

checkCIF report

Comment top

We herin report the crystal structure of (I), (Fig. 1). The bond lengths are comparable with those in a similar structure (Pandi et al., 2012).

The pyridine ring is almost planar, with the maximum deviation of 0.005 (2) Å. The carboxy group is twisted at an angle of 2.9 (1)° with the pyridine ring. The nitro group is oriented at an angle of 1.8 (1)° with the benzene ring. The crystal structure features O—H···O, N—H···O and C—H···O (Fig. 2 & Table 1) interactions to form a three dimensional network.

Related literature top

For a related structure, see: Pandi et al. (2012).

Experimental top

The title material was synthesized by taking 2-carboxypyridine (1.2331 g) and p-nitrophenol (1.3911 g) in an equimolar ratio. 2-carboxypyridine was added gradually in the saturated solution of p-nitrophenol using methanol with continuous stirring for one hour and white precipitate was obtained. Then, the precipitate was dissolved using the same solvent. The prepared solution was allowed for slow evaporation at room temperature to yield colourless blocks after 10 days.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of (I), viewed down a axis. Intermolecular Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

2-Carboxylatopyridinium–4-nitrophenol (1/1) top

Crystal data top

C₆H₅NO₃·C₆H₅NO₂	Z = 2
M_r = 262.22	F(000) = 272
Triclinic, P1	D_x = 1.492 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1743 (4) Å	Cell parameters from 4728 reflections
b = 7.0512 (3) Å	θ = 2.9–27.7°
c = 14.2222 (8) Å	µ = 0.12 mm⁻¹
α = 101.727 (3)°	T = 295 K
β = 92.191 (2)°	Block, colourless
γ = 104.758 (4)°	0.32 × 0.24 × 0.20 mm
V = 583.60 (6) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	3486 independent reflections
Radiation source: fine-focus sealed tube	2327 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and ϕ scan	θ_max = 30.4°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→8
T_min = 0.963, T_max = 0.977	k = −10→9
13952 measured reflections	l = −17→20

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0602P)² + 0.0686P] where P = (F_o² + 2F_c²)/3
3486 reflections	(Δ/σ)_max < 0.001
180 parameters	Δρ_max = 0.14 e Å⁻³
2 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₆H₅NO₃·C₆H₅NO₂	γ = 104.758 (4)°
M_r = 262.22	V = 583.60 (6) Å³
Triclinic, P1	Z = 2
a = 6.1743 (4) Å	Mo Kα radiation
b = 7.0512 (3) Å	µ = 0.12 mm⁻¹
c = 14.2222 (8) Å	T = 295 K
α = 101.727 (3)°	0.32 × 0.24 × 0.20 mm
β = 92.191 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3486 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2327 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.977	R_int = 0.028
13952 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	2 restraints
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.14 e Å⁻³
3486 reflections	Δρ_min = −0.24 e Å⁻³
180 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.3865 (2)	0.38442 (18)	0.19001 (9)	0.0451 (3)
C2	0.2381 (2)	0.2646 (2)	0.11160 (10)	0.0498 (3)
H2A	0.0853	0.2230	0.1187	0.060*
C3	0.3152 (2)	0.20783 (19)	0.02422 (9)	0.0474 (3)
H3	0.2155	0.1288	−0.0281	0.057*
C4	0.5424 (2)	0.26918 (17)	0.01464 (9)	0.0414 (3)
C5	0.6929 (2)	0.38640 (18)	0.09160 (9)	0.0459 (3)
H5	0.8455	0.4274	0.0840	0.055*
C6	0.6153 (2)	0.44171 (18)	0.17923 (9)	0.0474 (3)
H6	0.7161	0.5179	0.2317	0.057*
C7	0.1820 (2)	0.19479 (19)	0.45093 (8)	0.0429 (3)
C8	−0.1051 (2)	0.1161 (2)	0.32506 (10)	0.0512 (3)
H8	−0.2284	0.1462	0.2981	0.061*
C9	−0.0352 (3)	−0.0443 (2)	0.27958 (10)	0.0550 (3)
H9	−0.1090	−0.1236	0.2211	0.066*
C10	0.1445 (3)	−0.0868 (2)	0.32101 (10)	0.0589 (4)
H10	0.1930	−0.1968	0.2912	0.071*
C11	0.2543 (3)	0.0336 (2)	0.40725 (9)	0.0529 (3)
H11	0.3772	0.0051	0.4356	0.063*
C12	0.2879 (2)	0.3378 (2)	0.54544 (9)	0.0477 (3)
N1	0.6252 (2)	0.21159 (16)	−0.07787 (8)	0.0501 (3)
N2	0.00405 (19)	0.22997 (16)	0.40848 (7)	0.0452 (3)
O1	0.29906 (19)	0.44091 (17)	0.27221 (8)	0.0619 (3)
O2	0.4895 (2)	0.11237 (18)	−0.14600 (7)	0.0689 (3)
O3	0.82814 (19)	0.26305 (17)	−0.08431 (8)	0.0714 (3)
O4	0.2047 (2)	0.47818 (17)	0.57395 (7)	0.0701 (3)
O5	0.44519 (18)	0.29715 (16)	0.58610 (7)	0.0666 (3)
H2	−0.039 (3)	0.3351 (18)	0.4342 (11)	0.066 (5)*
H1	0.400 (3)	0.524 (2)	0.3119 (12)	0.085 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0519 (7)	0.0382 (6)	0.0449 (6)	0.0139 (5)	−0.0003 (5)	0.0071 (5)
C2	0.0394 (6)	0.0514 (7)	0.0550 (7)	0.0101 (5)	−0.0036 (5)	0.0075 (6)
C3	0.0460 (7)	0.0433 (6)	0.0476 (7)	0.0104 (5)	−0.0116 (5)	0.0030 (5)
C4	0.0478 (7)	0.0346 (6)	0.0427 (6)	0.0150 (5)	−0.0034 (5)	0.0066 (5)
C5	0.0404 (6)	0.0410 (6)	0.0525 (7)	0.0091 (5)	−0.0041 (5)	0.0054 (5)
C6	0.0476 (7)	0.0409 (6)	0.0469 (6)	0.0078 (5)	−0.0091 (5)	0.0019 (5)
C7	0.0500 (7)	0.0472 (7)	0.0334 (5)	0.0184 (5)	0.0041 (5)	0.0067 (5)
C8	0.0550 (8)	0.0496 (7)	0.0459 (7)	0.0160 (6)	−0.0074 (6)	0.0034 (5)
C9	0.0678 (9)	0.0471 (7)	0.0443 (7)	0.0161 (6)	−0.0051 (6)	−0.0021 (5)
C10	0.0792 (10)	0.0547 (8)	0.0458 (7)	0.0334 (7)	0.0042 (7)	−0.0016 (6)
C11	0.0617 (8)	0.0616 (8)	0.0412 (6)	0.0335 (7)	0.0005 (6)	0.0039 (6)
C12	0.0572 (8)	0.0530 (7)	0.0350 (5)	0.0238 (6)	0.0008 (5)	0.0034 (5)
N1	0.0602 (7)	0.0435 (6)	0.0477 (6)	0.0192 (5)	−0.0009 (5)	0.0071 (5)
N2	0.0544 (6)	0.0435 (6)	0.0386 (5)	0.0206 (5)	−0.0001 (4)	0.0024 (4)
O1	0.0611 (7)	0.0658 (7)	0.0513 (6)	0.0141 (5)	0.0066 (5)	−0.0004 (5)
O2	0.0762 (7)	0.0787 (7)	0.0460 (6)	0.0263 (6)	−0.0106 (5)	−0.0033 (5)
O3	0.0627 (7)	0.0734 (7)	0.0691 (7)	0.0119 (6)	0.0161 (5)	0.0013 (6)
O4	0.0938 (8)	0.0667 (7)	0.0520 (6)	0.0483 (6)	−0.0173 (5)	−0.0117 (5)
O5	0.0763 (7)	0.0785 (7)	0.0471 (5)	0.0448 (6)	−0.0138 (5)	−0.0082 (5)

Geometric parameters (Å, º) top

C1—O1	1.3363 (16)	C8—N2	1.3349 (16)
C1—C6	1.3902 (19)	C8—C9	1.3626 (19)
C1—C2	1.3934 (18)	C8—H8	0.9300
C2—C3	1.3679 (19)	C9—C10	1.364 (2)
C2—H2A	0.9300	C9—H9	0.9300
C3—C4	1.3796 (18)	C10—C11	1.3801 (19)
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.3813 (17)	C11—H11	0.9300
C4—N1	1.4482 (17)	C12—O4	1.2325 (16)
C5—C6	1.3705 (19)	C12—O5	1.2356 (15)
C5—H5	0.9300	N1—O2	1.2222 (15)
C6—H6	0.9300	N1—O3	1.2252 (15)
C7—N2	1.3352 (16)	N2—H2	0.866 (9)
C7—C11	1.3676 (18)	O1—H1	0.838 (9)
C7—C12	1.5156 (17)

O1—C1—C6	123.25 (12)	N2—C8—H8	120.1
O1—C1—C2	117.49 (12)	C9—C8—H8	120.1
C6—C1—C2	119.25 (12)	C8—C9—C10	119.09 (13)
C3—C2—C1	120.57 (12)	C8—C9—H9	120.5
C3—C2—H2A	119.7	C10—C9—H9	120.5
C1—C2—H2A	119.7	C9—C10—C11	119.88 (13)
C2—C3—C4	119.23 (12)	C9—C10—H10	120.1
C2—C3—H3	120.4	C11—C10—H10	120.1
C4—C3—H3	120.4	C7—C11—C10	119.84 (13)
C3—C4—C5	121.20 (12)	C7—C11—H11	120.1
C3—C4—N1	119.62 (11)	C10—C11—H11	120.1
C5—C4—N1	119.18 (12)	O4—C12—O5	127.49 (12)
C6—C5—C4	119.40 (12)	O4—C12—C7	116.64 (11)
C6—C5—H5	120.3	O5—C12—C7	115.84 (11)
C4—C5—H5	120.3	O2—N1—O3	122.83 (12)
C5—C6—C1	120.31 (12)	O2—N1—C4	118.51 (12)
C5—C6—H6	119.8	O3—N1—C4	118.65 (11)
C1—C6—H6	119.8	C8—N2—C7	123.02 (11)
N2—C7—C11	118.38 (11)	C8—N2—H2	117.9 (11)
N2—C7—C12	116.75 (11)	C7—N2—H2	119.0 (11)
C11—C7—C12	124.87 (12)	C1—O1—H1	109.5 (14)
N2—C8—C9	119.78 (13)

O1—C1—C2—C3	177.46 (13)	C12—C7—C11—C10	179.96 (13)
C6—C1—C2—C3	−1.60 (19)	C9—C10—C11—C7	0.2 (2)
C1—C2—C3—C4	0.5 (2)	N2—C7—C12—O4	−1.96 (19)
C2—C3—C4—C5	0.09 (19)	C11—C7—C12—O4	178.60 (14)
C2—C3—C4—N1	−179.33 (11)	N2—C7—C12—O5	176.51 (12)
C3—C4—C5—C6	0.42 (19)	C11—C7—C12—O5	−2.9 (2)
N1—C4—C5—C6	179.84 (11)	C3—C4—N1—O2	1.36 (18)
C4—C5—C6—C1	−1.53 (19)	C5—C4—N1—O2	−178.07 (11)
O1—C1—C6—C5	−176.89 (12)	C3—C4—N1—O3	−178.10 (12)
C2—C1—C6—C5	2.11 (19)	C5—C4—N1—O3	2.47 (18)
N2—C8—C9—C10	0.7 (2)	C9—C8—N2—C7	0.0 (2)
C8—C9—C10—C11	−0.8 (2)	C11—C7—N2—C8	−0.6 (2)
N2—C7—C11—C10	0.5 (2)	C12—C7—N2—C8	179.91 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5ⁱ	0.84 (1)	1.77 (1)	2.5929 (15)	165 (2)
N2—H2···O4ⁱⁱ	0.87 (1)	1.88 (1)	2.6693 (15)	151 (2)
C5—H5···O3ⁱⁱⁱ	0.93	2.56	3.3570 (17)	143
C9—H9···O2^iv	0.93	2.57	3.2009 (18)	126

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O5ⁱ	0.838 (9)	1.773 (11)	2.5929 (15)	165 (2)
N2—H2···O4ⁱⁱ	0.866 (9)	1.880 (12)	2.6693 (15)	151 (2)
C5—H5···O3ⁱⁱⁱ	0.93	2.56	3.3570 (17)	143
C9—H9···O2^iv	0.93	2.57	3.2009 (18)	126

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

Acknowledgements

The authors thank the SAIF, IIT, Madras, for the data collection.

References

Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Pandi, P., Peramaiyan, G., Akilan, R., Chakkaravarthi, G. & Mohankumar, R. (2012). Acta Cryst. E68, o3081. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar