2-Methyl­pyridinium 2-carb­oxy­benzoate–benzene-1,2-di­carb­oxy­lic acid (2/1)

Sivakumar, P.; Sudhahar, S.; Gunasekaran, B.; Israel, S.; Chakkaravarthi, G.

doi:10.1107/S2414314616008178

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160817

doi:10.1107/S2414314616008178

Open

access

2-Methylpyridinium 2-carboxybenzoate–benzene-1,2-dicarboxylic acid (2/1)

P. Sivakumar,^a,^b S. Sudhahar,^c B. Gunasekaran,^d S. Israel ^e ^* and G. Chakkaravarthi ^b ^*

^aResearch and Development Centre, Bharathiar University, Coimbatore 641 046, India, ^bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, ^cDepartment of Physics, Alagappa University, Karaikkudi 630 003, India, ^dDepartment of Physics and Nanotechnology, SRM University, Kattankulathur, Tamil Nadu, India, and ^eDepartment of Physics, The American College, Madurai 625 002, India
^*Correspondence e-mail: , chakkaravarthi_2005@yahoo.com

Edited by J. Simpson, University of Otago, New Zealand (Received 17 May 2016; accepted 19 May 2016; online 24 May 2016)

The asymmetric unit of the title compound, C₆H₈N⁺·C₈H₅O₄⁻·0.5C₈H₆O₄, contains a 2-methylpyridinium cation, a 2-carboxybenzoate monoanion and half of the co-crystallized benzene-1,2-dicarboxylic acid molecule, which lies on a mirror plane. The N atom of the pyridine ring is protonated, while the anion of this salt is generated by deprotonation of the OH group of one of the carboxylic acid substituents of the benzene-1,2-dicarboxylic acid molecule. The pyridine ring of the cation is inclined to the benzene ring of the anion at an angle of 2.27 (11)°. The benzene ring of the anion makes dihedral angles of 2.8 (2) and 6.0 (2)° with the carboxylate and carboxyl substituents, respectively. An intramolecular O—H⋯O hydrogen bond in the anion closes an S(7) ring. In the crystal, weak N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds lead to the formation of a three-dimensional network. Weak offset π–π contacts [centroid-to-centroid distance = 3.852 (1) Å] are also observed.

Keywords: crystal structure; molecular salt; hydrogen bonding.

CCDC reference: 1480869

3D view (loading...)

Chemical scheme

Structure description

Pyridine derivatives exhibit anti-inflammatory (Abdel-Alim et al., 2005 ) and anticancer (Girgis et al. 2006 ) activities. We report herein the synthesis and the crystal structure of a co-crystal of the 2-methylpyridinium 2-carboxybenzoate salt and a benzene-1,2-dicarboxylic acid molecule (Fig. 1). The asymmetric unit contains a 2-methylpyridinium cation, a 2-carboxybenzoate anion and half of a benzene-1,2-dicarboxylic acid molecule, which lies on a mirror plane. The N atom of the pyridine ring is protonated while the OH group of one of the carboxylic acid substituents of a benzene-1,2-dicarboxylic acid molecule is deprotonated to form the monoanion.

Figure 1
The structure of the title co-crystal, showing the atom labelling and 30% probability displacement ellipsoids. Atoms labelled with the suffix `a′ are generated by the symmetry operation (−x + 1, y, −z + $[{1\over 2}]$ ).

The N1/C1–C5 pyridinium ring and the C7–C12 benzene ring of the 2-carboxybenzoate monoanion are inclined at an angle of 2.27 (11)° to one another. The co-crystallized benzene-1,2-dicarboxylic acid molecule lies on a mirror plane. The C7–C12 benzene ring of the anion makes dihedral angles of 2.8 (2) and 6.0 (2)° with the attached carboxylate (C13/O1/O2) and carboxyl (C14/O3/O4) groups, respectively.

An intramolecular O3—H2A⋯O2 hydrogen bond in the anion (Fig. 1) forms an S(7) graph-set motif. The crystal structure features N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds (Fig. 2, Table 1), which generate a three-dimensional network. Weak offset π–π contacts are also observed in the crystal structure [Cg2⋯Cg3^iv = 3.852 (1), Cg3⋯Cg2^v = 3.852 (1) Å; symmetry codes: (iv) $[{1\over 2}]$ + x, − $[{1\over 2}]$ + y, z; (v) − $[{1\over 2}]$ + x, $[{1\over 2}]$ + y,z; Cg2 and Cg3 are the centroids of the C7–C12 and N1/C1–C5, rings respectively].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H2A⋯O2	0.84 (1)	1.52 (1)	2.365 (2)	178 (4)
N1—H1⋯O1ⁱ	0.86	1.84	2.697 (2)	176
N1—H1⋯O2ⁱ	0.86	2.59	3.194 (2)	128
O6—H6⋯O4ⁱⁱ	0.83 (1)	1.84 (1)	2.640 (2)	162 (3)
C2—H2⋯O5ⁱⁱⁱ	0.93	2.44	3.244 (3)	144
C5—H5⋯O2ⁱ	0.93	2.60	3.207 (3)	124
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y-1, z; (iii) $[-x+1, y+1, -z+{\script{1\over 2}}]$ .

Figure 2
Crystal packing of the title compound viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1

). C-bound H atoms have been omitted for clarity.

Synthesis and crystallization

2-Picoline (0.93 g) and phthalic acid (1.66 g) dissolved in 20 ml of methanol were magnetically stirred for 3 hr in a round-bottomed flask. The solvent was allowed to evaporate slowly at room temperature. Over 15 days, crystals suitable for X-ray diffraction were obtained.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₈N⁺·C₈H₅O₄⁻·0.5C₈H₆O₄
M_r	342.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	13.0967 (8), 8.1049 (4), 30.3013 (18)
β (°)	97.543 (3)
V (Å³)	3188.6 (3)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.975, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	25680, 3706, 1961
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.654

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.139, 1.00
No. of reflections	3706
No. of parameters	243
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.25
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1480869

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616008178/sj4037sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616008178/sj4037Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616008178/sj4037Isup3.cml

checkCIF report

Synthesis and crystallization top

2-Picoline (0.93 g) and phthalic acid (1.66 g) dissolved in 20 ml of methanol were magnetically stirred for 3 hr in a round bottomed flask. The solvent was allowed to slowly evaporate at room temperature. Over 15 days, crystals suitable for X-ray diffraction were obtained.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1

Experimental top

Structure description top

Pyridine derivatives exhibit anti-inflammatory (Abdel-Alim et al., 2005) and anticancer (Girgis et al. 2006) activities. We report herein the synthesis and the crystal structure of a co-crystal of the 2-methylpyridinium 2-carboxybenzoate salt and a benzene-1,2-dicarboxylic acid molecule (Fig. 1). The asymmetric unit contains a 2-methylpyridinium cation, a 2-carboxybenzoate anion and half of a benzene-1,2-dicarboxylic acid molecule, which lies on a mirror plane. The N atom of the pyridine ring is protonated while the OH group of one of the carboxylic acid substituents of a benzene-1,2-dicarboxylic acid molecule is deprotonated to form the monoanion.

The (N1/C1–C5) pyridinium ring and the (C7–C12) benzene ring of the 2-carboxybenzoate monoanion are inclined at an angle of 2.27 (11)° to one another. The co-crystallized benzene-1,2-dicarboxylic acid molecule lies on a mirror plane. The C7–C12 benzene ring of the anion makes dihedral angles of 2.8 (2) and 6.0 (2)° with the attached carboxylate (C13/O1/O2) and carboxyl (C14/O3/O4) groups, respectively.

An intramolecular O3—H2A···O2 hydrogen bond in the anion (Fig. 1) forms an S(7) graph-set motif. The crystal structure features N—H···O, O—H···O and C—H···O hydrogen bonds (Fig. 2, Table 1), which generate a three-dimensional network. Weak offset π–π contacts are also observed in the crystal structure [Cg2···Cg3^iv = 3.852 (1), Cg3···Cg2^v = 3.852 (1) Å; symmetry codes: (iv) 1/2 + x, -1/2 + y, z; (v) -1/2 + x, 1/2 + y,z; Cg2 and Cg3 are the centroids of the C7–C12 and N1/C1–C5, rings respectively].

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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The structure of the title co-crystal, showing the atom labelling and 30% probability displacement ellipsoids. Atoms labelled with the suffix `a' are generated by the symmetry operation (-x + 1, y, -z + 1/2).
	Fig. 2. Crystal packing of the title compound viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1). C-bound H atoms have been omitted for clarity.

2-Methylpyridinium 2-carboxybenzoate–benzene-1,2-dicarboxylic acid (2/1) top

Crystal data top

C₆H₈N⁺·C₈H₅O₄⁻·0.5C₈H₆O₄	F(000) = 1432
M_r = 342.32	D_x = 1.426 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2963 reflections
a = 13.0967 (8) Å	θ = 2.7–22.6°
b = 8.1049 (4) Å	µ = 0.11 mm⁻¹
c = 30.3013 (18) Å	T = 295 K
β = 97.543 (3)°	Block, colourless
V = 3188.6 (3) Å³	0.24 × 0.20 × 0.18 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	3706 independent reflections
Radiation source: fine-focus sealed tube	1961 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ω and φ scan	θ_max = 27.7°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −17→17
T_min = 0.975, T_max = 0.981	k = −10→10
25680 measured reflections	l = −39→39

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.061P)² + 0.7843P] where P = (F_o² + 2F_c²)/3
3706 reflections	(Δ/σ)_max < 0.001
243 parameters	Δρ_max = 0.29 e Å⁻³
6 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₆H₈N⁺·C₈H₅O₄⁻·0.5C₈H₆O₄	V = 3188.6 (3) Å³
M_r = 342.32	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 13.0967 (8) Å	µ = 0.11 mm⁻¹
b = 8.1049 (4) Å	T = 295 K
c = 30.3013 (18) Å	0.24 × 0.20 × 0.18 mm
β = 97.543 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3706 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	1961 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.981	R_int = 0.059
25680 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	6 restraints
wR(F²) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.29 e Å⁻³
3706 reflections	Δρ_min = −0.25 e Å⁻³
243 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.

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 > 2sigma(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
C1	0.41428 (15)	0.4797 (3)	0.11616 (7)	0.0442 (5)
C2	0.41880 (18)	0.3486 (3)	0.14524 (8)	0.0548 (6)
H2	0.4318	0.3671	0.1757	0.066*
C3	0.40426 (19)	0.1908 (3)	0.12937 (8)	0.0602 (7)
H3	0.4078	0.1025	0.1491	0.072*
C4	0.38447 (18)	0.1628 (3)	0.08442 (8)	0.0553 (6)
H4	0.3740	0.0563	0.0733	0.066*
C5	0.38050 (18)	0.2941 (3)	0.05662 (8)	0.0538 (6)
H5	0.3675	0.2778	0.0260	0.065*
C6	0.42957 (18)	0.6547 (3)	0.12976 (8)	0.0565 (6)
H6A	0.5018	0.6761	0.1375	0.085*
H6B	0.3943	0.6762	0.1550	0.085*
H6C	0.4025	0.7251	0.1055	0.085*
C7	0.66307 (14)	0.2220 (2)	0.10324 (6)	0.0354 (5)
C8	0.66764 (16)	0.0815 (2)	0.12987 (7)	0.0432 (5)
H8	0.6837	0.0933	0.1605	0.052*
C9	0.64932 (17)	−0.0741 (2)	0.11253 (8)	0.0489 (6)
H9	0.6533	−0.1657	0.1312	0.059*
C10	0.62521 (18)	−0.0921 (3)	0.06759 (8)	0.0533 (6)
H10	0.6108	−0.1961	0.0554	0.064*
C11	0.62217 (17)	0.0433 (2)	0.04044 (7)	0.0474 (5)
H11	0.6071	0.0285	0.0098	0.057*
C12	0.64073 (15)	0.2021 (2)	0.05690 (6)	0.0364 (5)
C13	0.63393 (17)	0.3339 (3)	0.02139 (7)	0.0465 (5)
C14	0.68093 (16)	0.3795 (2)	0.12974 (7)	0.0423 (5)
C15	0.54949 (19)	0.1071 (2)	0.24500 (8)	0.0543 (6)
C16	0.59899 (19)	−0.0401 (2)	0.23966 (7)	0.0471 (6)
C17	0.54999 (15)	−0.1893 (2)	0.24464 (6)	0.0394 (5)
C18	0.60728 (19)	−0.3451 (3)	0.23892 (7)	0.0500 (6)
N1	0.39510 (13)	0.4462 (2)	0.07275 (6)	0.0476 (5)
H1	0.3920	0.5270	0.0542	0.057*
O1	0.61695 (14)	0.29077 (18)	−0.01781 (5)	0.0679 (5)
O2	0.64605 (15)	0.48431 (18)	0.03183 (5)	0.0704 (5)
O3	0.67044 (15)	0.51902 (18)	0.11001 (6)	0.0637 (5)
O4	0.70341 (14)	0.37269 (17)	0.17001 (5)	0.0642 (5)
O5	0.6114 (2)	−0.4596 (2)	0.26340 (7)	0.1240 (10)
O6	0.65490 (14)	−0.34266 (19)	0.20419 (5)	0.0592 (5)
H6	0.679 (2)	−0.434 (2)	0.1988 (10)	0.099 (11)*
H15	0.5865 (15)	0.2030 (17)	0.2412 (7)	0.064 (7)*
H16	0.6671 (7)	−0.040 (2)	0.2337 (7)	0.044 (6)*
H2A	0.661 (3)	0.509 (4)	0.0821 (4)	0.109 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0380 (12)	0.0578 (13)	0.0367 (12)	−0.0011 (10)	0.0047 (9)	0.0053 (10)
C2	0.0593 (15)	0.0656 (16)	0.0387 (13)	0.0028 (12)	0.0031 (11)	0.0082 (11)
C3	0.0664 (16)	0.0583 (15)	0.0568 (16)	0.0037 (12)	0.0115 (13)	0.0155 (12)
C4	0.0596 (15)	0.0534 (14)	0.0535 (15)	−0.0029 (11)	0.0100 (12)	−0.0006 (11)
C5	0.0611 (15)	0.0591 (15)	0.0414 (13)	−0.0041 (12)	0.0072 (11)	−0.0009 (11)
C6	0.0592 (15)	0.0588 (14)	0.0498 (14)	−0.0067 (12)	0.0005 (12)	−0.0012 (11)
C7	0.0365 (11)	0.0327 (10)	0.0381 (11)	0.0001 (8)	0.0096 (9)	−0.0014 (8)
C8	0.0501 (13)	0.0413 (12)	0.0392 (12)	0.0003 (10)	0.0098 (10)	0.0050 (9)
C9	0.0600 (15)	0.0349 (11)	0.0531 (14)	−0.0008 (10)	0.0129 (12)	0.0069 (10)
C10	0.0663 (16)	0.0331 (11)	0.0609 (16)	−0.0060 (10)	0.0103 (12)	−0.0055 (10)
C11	0.0603 (15)	0.0417 (12)	0.0402 (12)	−0.0039 (10)	0.0066 (11)	−0.0054 (9)
C12	0.0397 (11)	0.0330 (10)	0.0370 (11)	−0.0007 (8)	0.0060 (9)	0.0015 (8)
C13	0.0544 (14)	0.0439 (13)	0.0414 (13)	−0.0008 (10)	0.0068 (10)	0.0053 (10)
C14	0.0454 (13)	0.0390 (12)	0.0442 (13)	0.0021 (9)	0.0128 (10)	−0.0036 (10)
C15	0.0856 (18)	0.0320 (11)	0.0456 (13)	−0.0115 (11)	0.0102 (13)	0.0003 (10)
C16	0.0615 (16)	0.0401 (12)	0.0409 (13)	−0.0085 (11)	0.0106 (11)	0.0011 (9)
C17	0.0573 (13)	0.0323 (10)	0.0292 (10)	0.0017 (9)	0.0085 (10)	0.0004 (8)
C18	0.0746 (16)	0.0412 (12)	0.0366 (12)	0.0079 (11)	0.0159 (11)	0.0045 (10)
N1	0.0504 (11)	0.0546 (12)	0.0373 (10)	−0.0022 (9)	0.0039 (8)	0.0084 (8)
O1	0.1035 (14)	0.0600 (10)	0.0367 (9)	−0.0097 (9)	−0.0034 (9)	0.0063 (8)
O2	0.1260 (16)	0.0365 (9)	0.0489 (10)	−0.0010 (9)	0.0125 (10)	0.0090 (7)
O3	0.1106 (15)	0.0334 (9)	0.0496 (11)	−0.0058 (8)	0.0203 (10)	−0.0023 (8)
O4	0.0962 (13)	0.0516 (9)	0.0418 (10)	0.0133 (9)	−0.0025 (9)	−0.0093 (7)
O5	0.230 (3)	0.0662 (12)	0.0978 (16)	0.0684 (15)	0.1034 (18)	0.0428 (11)
O6	0.0841 (12)	0.0502 (10)	0.0482 (10)	0.0138 (9)	0.0267 (9)	0.0016 (8)

Geometric parameters (Å, º) top

C1—N1	1.334 (3)	C10—C11	1.369 (3)
C1—C2	1.377 (3)	C10—H10	0.9300
C1—C6	1.483 (3)	C11—C12	1.390 (3)
C2—C3	1.371 (3)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.511 (3)
C3—C4	1.371 (3)	C13—O1	1.230 (2)
C3—H3	0.9300	C13—O2	1.264 (2)
C4—C5	1.354 (3)	C14—O4	1.218 (2)
C4—H4	0.9300	C14—O3	1.278 (2)
C5—N1	1.330 (3)	C15—C15ⁱ	1.370 (5)
C5—H5	0.9300	C15—C16	1.378 (3)
C6—H6A	0.9600	C15—H15	0.931 (7)
C6—H6B	0.9600	C16—C17	1.387 (3)
C6—H6C	0.9600	C16—H16	0.933 (7)
C7—C8	1.392 (3)	C17—C17ⁱ	1.390 (4)
C7—C12	1.406 (3)	C17—C18	1.490 (3)
C7—C14	1.510 (3)	C18—O5	1.185 (3)
C8—C9	1.375 (3)	C18—O6	1.292 (3)
C8—H8	0.9300	N1—H1	0.8600
C9—C10	1.365 (3)	O3—H2A	0.842 (10)
C9—H9	0.9300	O6—H6	0.830 (10)

N1—C1—C2	117.4 (2)	C9—C10—H10	120.0
N1—C1—C6	118.05 (19)	C11—C10—H10	120.0
C2—C1—C6	124.6 (2)	C10—C11—C12	122.4 (2)
C3—C2—C1	120.2 (2)	C10—C11—H11	118.8
C3—C2—H2	119.9	C12—C11—H11	118.8
C1—C2—H2	119.9	C11—C12—C7	117.93 (17)
C2—C3—C4	120.1 (2)	C11—C12—C13	114.09 (18)
C2—C3—H3	119.9	C7—C12—C13	127.98 (17)
C4—C3—H3	119.9	O1—C13—O2	121.09 (19)
C5—C4—C3	118.4 (2)	O1—C13—C12	118.23 (19)
C5—C4—H4	120.8	O2—C13—C12	120.68 (19)
C3—C4—H4	120.8	O4—C14—O3	120.38 (19)
N1—C5—C4	120.5 (2)	O4—C14—C7	119.62 (18)
N1—C5—H5	119.8	O3—C14—C7	119.98 (19)
C4—C5—H5	119.8	C15ⁱ—C15—C16	119.98 (14)
C1—C6—H6A	109.5	C15ⁱ—C15—H15	123.4 (14)
C1—C6—H6B	109.5	C16—C15—H15	116.6 (14)
H6A—C6—H6B	109.5	C15—C16—C17	120.7 (2)
C1—C6—H6C	109.5	C15—C16—H16	119.9 (12)
H6A—C6—H6C	109.5	C17—C16—H16	119.3 (12)
H6B—C6—H6C	109.5	C16—C17—C17ⁱ	119.28 (13)
C8—C7—C12	118.19 (17)	C16—C17—C18	118.61 (19)
C8—C7—C14	113.06 (17)	C17ⁱ—C17—C18	122.10 (12)
C12—C7—C14	128.73 (17)	O5—C18—O6	122.3 (2)
C9—C8—C7	122.46 (19)	O5—C18—C17	124.9 (2)
C9—C8—H8	118.8	O6—C18—C17	112.71 (17)
C7—C8—H8	118.8	C5—N1—C1	123.41 (19)
C10—C9—C8	119.0 (2)	C5—N1—H1	118.3
C10—C9—H9	120.5	C1—N1—H1	118.3
C8—C9—H9	120.5	C14—O3—H2A	112 (2)
C9—C10—C11	119.9 (2)	C18—O6—H6	112 (2)

N1—C1—C2—C3	0.2 (3)	C7—C12—C13—O1	177.4 (2)
C6—C1—C2—C3	−179.5 (2)	C11—C12—C13—O2	177.9 (2)
C1—C2—C3—C4	−0.4 (4)	C7—C12—C13—O2	−2.2 (3)
C2—C3—C4—C5	0.4 (4)	C8—C7—C14—O4	4.5 (3)
C3—C4—C5—N1	−0.3 (4)	C12—C7—C14—O4	−177.2 (2)
C12—C7—C8—C9	−1.2 (3)	C8—C7—C14—O3	−174.1 (2)
C14—C7—C8—C9	177.23 (19)	C12—C7—C14—O3	4.1 (3)
C7—C8—C9—C10	−0.3 (3)	C15ⁱ—C15—C16—C17	−0.5 (4)
C8—C9—C10—C11	1.7 (3)	C15—C16—C17—C17ⁱ	−0.3 (4)
C9—C10—C11—C12	−1.4 (3)	C15—C16—C17—C18	−179.4 (2)
C10—C11—C12—C7	−0.2 (3)	C16—C17—C18—O5	133.3 (3)
C10—C11—C12—C13	179.8 (2)	C17ⁱ—C17—C18—O5	−45.8 (4)
C8—C7—C12—C11	1.4 (3)	C16—C17—C18—O6	−45.6 (3)
C14—C7—C12—C11	−176.75 (19)	C17ⁱ—C17—C18—O6	135.3 (3)
C8—C7—C12—C13	−178.55 (19)	C4—C5—N1—C1	0.1 (3)
C14—C7—C12—C13	3.3 (3)	C2—C1—N1—C5	−0.1 (3)
C11—C12—C13—O1	−2.6 (3)	C6—C1—N1—C5	179.7 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H2A···O2	0.84 (1)	1.52 (1)	2.365 (2)	178 (4)
N1—H1···O1ⁱⁱ	0.86	1.84	2.697 (2)	176
N1—H1···O2ⁱⁱ	0.86	2.59	3.194 (2)	128
O6—H6···O4ⁱⁱⁱ	0.83 (1)	1.84 (1)	2.640 (2)	162 (3)
C2—H2···O5^iv	0.93	2.44	3.244 (3)	144
C5—H5···O2ⁱⁱ	0.93	2.60	3.207 (3)	124

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H2A···O2	0.842 (10)	1.524 (10)	2.365 (2)	178 (4)
N1—H1···O1ⁱ	0.86	1.84	2.697 (2)	176
N1—H1···O2ⁱ	0.86	2.59	3.194 (2)	128
O6—H6···O4ⁱⁱ	0.830 (10)	1.840 (14)	2.640 (2)	162 (3)
C2—H2···O5ⁱⁱⁱ	0.93	2.44	3.244 (3)	144
C5—H5···O2ⁱ	0.93	2.60	3.207 (3)	124

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

Experimental details

Crystal data
Chemical formula	C₆H₈N⁺·C₈H₅O₄⁻·0.5C₈H₆O₄
M_r	342.32
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	13.0967 (8), 8.1049 (4), 30.3013 (18)
β (°)	97.543 (3)
V (Å³)	3188.6 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.975, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	25680, 3706, 1961
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.654

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.139, 1.00
No. of reflections	3706
No. of parameters	243
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.25

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

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

References

Abdel-Alim, A. M., El-Shorbagi, A. A., Abdel-Moty, S. G. & Abdel-Allah, H. H. M. (2005). Arch. Pharm. Res. 28, 637–647. Web of Science PubMed CAS Google Scholar
Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Girgis, A. S., Hosni, H. M. & Barsoum, F. F. (2006). Bioorg. Med. Chem. 14, 4466–4476. Web of Science CrossRef PubMed CAS 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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160817

doi:10.1107/S2414314616008178

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text
		Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2-Methyl­pyridinium 2-carb­­oxy­benzoate–benzene-1,2-di­carb­­oxy­lic acid (2/1)

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

2-Methylpyridinium 2-carboxybenzoate–benzene-1,2-dicarboxylic acid (2/1)