4-Methyl­pyridinium 4-hy­droxy­benzoate

Sudhahar, S.; Krishnakumar, M.; Sornamurthy, B.M.; Chakkaravarthi, G.; Mohankumar, R.

doi:10.1107/S1600536813001785

organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o279

doi:10.1107/S1600536813001785

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4-Methylpyridinium 4-hydroxybenzoate

S. Sudhahar,^a M. Krishnakumar,^a B. M. Sornamurthy,^a G. Chakkaravarthi ^b ^* and R. Mohankumar ^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, mohan66@hotmail.com

(Received 24 December 2012; accepted 17 January 2013; online 23 January 2013)

In the crystal structure of the title salt, C₆H₈N⁺·C₇H₅O₃⁻, the anions and cations are linked by classical N—H⋯O hydrogen bonds. The anions are connected by pairs of C—H⋯O hydrogen bonds into inversion dimers and further linked by classical O—H⋯O hydrogen bonds. Weak π–π interactions [centroid–centroid distances = 3.740 (3) and 3.855 (3) Å] also occur. The dihedral angle between the CO₂⁻ group and the benzene ring to which it is attached is 20.95 (8)°.

Related literature

For biological applications of picolinium-containing compounds, see: Butler & Walker (1993 ); Roy et al. (2001 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₆H₈N⁺·C₇H₅O₃⁻
M_r = 231.24
Monoclinic, P 2₁ /c
a = 7.479 (5) Å
b = 11.671 (4) Å
c = 13.520 (5) Å
β = 100.217 (5)°
V = 1161.4 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.978, T_max = 0.983
11741 measured reflections
2564 independent reflections
1939 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.128
S = 1.06
2564 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.85	2.6707 (19)	176
N1—H1A⋯O3ⁱⁱ	0.86	1.73	2.5889 (19)	173
C2—H2⋯O1ⁱⁱⁱ	0.93	2.60	3.485 (2)	160
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) -x+1, -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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813001785/rk2392sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813001785/rk2392Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813001785/rk2392Isup3.cml

checkCIF report

Comment top

Picolinium compounds are valuable intermediates in organic synthesis and they have been used widely in industrially important products and biologically active substrates as antitumor, antifungal, antibacterial, antineoplastic and antviral (Butler & Walker, 1993; Roy et al., 2001) activities.

The asymmetric unit of the title salt, I, (Fig. 1), contains C₆H₈N⁺ cation and C₇H₅O₃^- anion. The bond lengths and angles in both anion and cation are within normal range (Allen et al., 1987). The crystal structure exhibit weak intermolecular classical N—H···O, O—H···O and non–classical C—H···O interactions (Table 1 & Fig. 2). The π–π interactions are found in crystal structure: Cg1···Cg2^iv = 3.740 (3)Å; Cg1···Cg2^v = 3.855 (3)Å, where Cg1 and Cg2 are the centroids of the rings (C1–C6) and (N1/C8–C12), respectively. Symmetry codes: (iv) x, -y+1/2, z+1/2); (v) x+1, y, z;

Related literature top

For biological applications of picolinium-containing compounds, see: Butler & Walker (1993); Roy et al. (2001). For bond-length data, see: Allen et al. (1987).

Experimental top

4-Picolinium 4-hydroxybenzoate compound was synthesized by using the starting materials of 4-picoline (1.66 g) and 4-hydroxybenzoic acid (1.12 g) in methanol and the single crystals suitable for X-ray diffraction were grown by slow evaporation.

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 title compound with the atom numbering scheme. Displacement ellipsoids are drawn at 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
	Fig. 2. The crystal 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 for clarity.

4-Methylpyridinium 4-hydroxybenzoate top

Crystal data top

C₆H₈N⁺·C₇H₅O₃⁻	F(000) = 488
M_r = 231.24	D_x = 1.322 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 470.4–481.2 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.479 (5) Å	Cell parameters from 7082 reflections
b = 11.671 (4) Å	θ = 2.3–27.1°
c = 13.520 (5) Å	µ = 0.10 mm⁻¹
β = 100.217 (5)°	T = 295 K
V = 1161.4 (10) Å³	Block, colourless
Z = 4	0.24 × 0.20 × 0.18 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2564 independent reflections
Radiation source: fine–focus sealed tube	1939 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and ϕ scans	θ_max = 27.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.978, T_max = 0.983	k = −14→8
11741 measured reflections	l = −17→17

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)] = 0.043	H-atom parameters constrained
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.058P)² + 0.3003P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2564 reflections	Δρ_max = 0.38 e Å⁻³
156 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.010 (2)

Crystal data top

C₆H₈N⁺·C₇H₅O₃⁻	V = 1161.4 (10) Å³
M_r = 231.24	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.479 (5) Å	µ = 0.10 mm⁻¹
b = 11.671 (4) Å	T = 295 K
c = 13.520 (5) Å	0.24 × 0.20 × 0.18 mm
β = 100.217 (5)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2564 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1939 reflections with I > 2σ(I)
T_min = 0.978, T_max = 0.983	R_int = 0.029
11741 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.06	Δρ_max = 0.38 e Å⁻³
2564 reflections	Δρ_min = −0.34 e Å⁻³
156 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	0.55020 (18)	0.18454 (10)	0.02055 (8)	0.0578 (4)
H1	0.5981	0.2464	0.0131	0.087*
O2	0.7215 (2)	0.11967 (10)	0.49538 (9)	0.0599 (4)
O3	0.71511 (18)	−0.05893 (9)	0.44053 (8)	0.0563 (4)
C1	0.5832 (2)	0.15548 (13)	0.11952 (11)	0.0396 (4)
C2	0.5407 (2)	0.04549 (13)	0.14510 (11)	0.0435 (4)
H2	0.4883	−0.0056	0.0955	0.052*
C3	0.5761 (2)	0.01174 (12)	0.24435 (11)	0.0394 (4)
H3	0.5492	−0.0628	0.2612	0.047*
C4	0.6512 (2)	0.08716 (12)	0.31929 (10)	0.0356 (3)
C5	0.6894 (2)	0.19833 (12)	0.29287 (11)	0.0394 (4)
H5	0.7375	0.2503	0.3427	0.047*
C6	0.6571 (2)	0.23261 (13)	0.19390 (11)	0.0397 (4)
H6	0.6846	0.3070	0.1769	0.048*
C7	0.6972 (2)	0.05049 (13)	0.42610 (11)	0.0412 (4)
N1	0.18709 (19)	0.10699 (12)	0.37067 (10)	0.0475 (4)
H1A	0.2170	0.0966	0.4344	0.057*
C8	0.2266 (2)	0.20451 (14)	0.32853 (13)	0.0490 (4)
H8	0.2872	0.2617	0.3692	0.059*
C9	0.1813 (2)	0.22368 (14)	0.22732 (12)	0.0473 (4)
H9	0.2099	0.2933	0.2005	0.057*
C10	0.0932 (2)	0.13982 (14)	0.16510 (11)	0.0446 (4)
C11	0.0517 (2)	0.03949 (14)	0.20988 (13)	0.0480 (4)
H11	−0.0091	−0.0190	0.1709	0.058*
C12	0.1000 (2)	0.02581 (14)	0.31174 (13)	0.0478 (4)
H12	0.0710	−0.0424	0.3407	0.057*
C13	0.0475 (3)	0.15746 (19)	0.05391 (14)	0.0686 (6)
H13A	0.0259	0.2374	0.0398	0.103*
H13B	−0.0596	0.1145	0.0272	0.103*
H13C	0.1469	0.1318	0.0234	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0913 (9)	0.0446 (7)	0.0328 (6)	−0.0132 (6)	−0.0014 (6)	0.0060 (5)
O2	0.1019 (10)	0.0430 (7)	0.0334 (6)	0.0124 (6)	0.0079 (6)	−0.0037 (5)
O3	0.0980 (10)	0.0342 (6)	0.0363 (6)	0.0073 (6)	0.0106 (6)	0.0038 (5)
C1	0.0502 (9)	0.0365 (8)	0.0309 (7)	0.0008 (6)	0.0040 (6)	0.0032 (6)
C2	0.0561 (9)	0.0357 (8)	0.0363 (8)	−0.0062 (7)	0.0014 (7)	−0.0028 (6)
C3	0.0509 (9)	0.0283 (7)	0.0391 (8)	−0.0019 (6)	0.0081 (7)	0.0025 (6)
C4	0.0440 (8)	0.0316 (7)	0.0320 (7)	0.0046 (6)	0.0091 (6)	0.0012 (6)
C5	0.0520 (9)	0.0325 (8)	0.0339 (8)	−0.0003 (6)	0.0085 (6)	−0.0050 (6)
C6	0.0537 (9)	0.0282 (7)	0.0383 (8)	−0.0022 (6)	0.0106 (7)	0.0016 (6)
C7	0.0554 (9)	0.0357 (8)	0.0343 (8)	0.0052 (7)	0.0123 (7)	−0.0005 (6)
N1	0.0592 (9)	0.0506 (8)	0.0323 (7)	0.0066 (6)	0.0073 (6)	0.0070 (6)
C8	0.0561 (10)	0.0450 (9)	0.0441 (9)	−0.0015 (7)	0.0036 (7)	−0.0009 (7)
C9	0.0550 (10)	0.0417 (9)	0.0454 (9)	−0.0008 (7)	0.0089 (7)	0.0087 (7)
C10	0.0468 (9)	0.0502 (10)	0.0365 (8)	0.0059 (7)	0.0068 (7)	0.0045 (7)
C11	0.0544 (10)	0.0446 (9)	0.0440 (9)	−0.0011 (7)	0.0057 (7)	−0.0018 (7)
C12	0.0563 (10)	0.0415 (9)	0.0474 (9)	0.0016 (7)	0.0138 (8)	0.0070 (7)
C13	0.0898 (15)	0.0731 (13)	0.0400 (10)	0.0027 (11)	0.0039 (9)	0.0092 (9)

Geometric parameters (Å, º) top

O1—C1	1.3599 (18)	N1—C8	1.329 (2)
O1—H1	0.8200	N1—C12	1.331 (2)
O2—C7	1.2255 (19)	N1—H1A	0.8600
O3—C7	1.2953 (19)	C8—C9	1.369 (2)
C1—C2	1.381 (2)	C8—H8	0.9300
C1—C6	1.389 (2)	C9—C10	1.379 (2)
C2—C3	1.378 (2)	C9—H9	0.9300
C2—H2	0.9300	C10—C11	1.379 (2)
C3—C4	1.384 (2)	C10—C13	1.496 (2)
C3—H3	0.9300	C11—C12	1.370 (2)
C4—C5	1.389 (2)	C11—H11	0.9300
C4—C7	1.487 (2)	C12—H12	0.9300
C5—C6	1.376 (2)	C13—H13A	0.9600
C5—H5	0.9300	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600

C1—O1—H1	109.5	C8—N1—H1A	120.8
O1—C1—C2	117.94 (13)	C12—N1—H1A	120.8
O1—C1—C6	122.02 (14)	N1—C8—C9	122.28 (16)
C2—C1—C6	120.05 (14)	N1—C8—H8	118.9
C3—C2—C1	119.75 (14)	C9—C8—H8	118.9
C3—C2—H2	120.1	C8—C9—C10	120.04 (15)
C1—C2—H2	120.1	C8—C9—H9	120.0
C2—C3—C4	120.93 (14)	C10—C9—H9	120.0
C2—C3—H3	119.5	C11—C10—C9	117.07 (15)
C4—C3—H3	119.5	C11—C10—C13	121.95 (16)
C3—C4—C5	118.77 (13)	C9—C10—C13	120.97 (16)
C3—C4—C7	121.46 (13)	C12—C11—C10	120.06 (16)
C5—C4—C7	119.74 (13)	C12—C11—H11	120.0
C6—C5—C4	120.85 (14)	C10—C11—H11	120.0
C6—C5—H5	119.6	N1—C12—C11	122.17 (15)
C4—C5—H5	119.6	N1—C12—H12	118.9
C5—C6—C1	119.62 (14)	C11—C12—H12	118.9
C5—C6—H6	120.2	C10—C13—H13A	109.5
C1—C6—H6	120.2	C10—C13—H13B	109.5
O2—C7—O3	122.48 (15)	H13A—C13—H13B	109.5
O2—C7—C4	122.01 (14)	C10—C13—H13C	109.5
O3—C7—C4	115.47 (13)	H13A—C13—H13C	109.5
C8—N1—C12	118.37 (14)	H13B—C13—H13C	109.5

O1—C1—C2—C3	178.41 (14)	C5—C4—C7—O2	20.1 (2)
C6—C1—C2—C3	−1.7 (2)	C3—C4—C7—O3	20.0 (2)
C1—C2—C3—C4	1.1 (2)	C5—C4—C7—O3	−157.84 (15)
C2—C3—C4—C5	0.4 (2)	C12—N1—C8—C9	−0.1 (2)
C2—C3—C4—C7	−177.46 (14)	N1—C8—C9—C10	−0.7 (3)
C3—C4—C5—C6	−1.4 (2)	C8—C9—C10—C11	1.2 (2)
C7—C4—C5—C6	176.54 (14)	C8—C9—C10—C13	−178.06 (16)
C4—C5—C6—C1	0.8 (2)	C9—C10—C11—C12	−0.9 (2)
O1—C1—C6—C5	−179.34 (14)	C13—C10—C11—C12	178.39 (17)
C2—C1—C6—C5	0.7 (2)	C8—N1—C12—C11	0.5 (2)
C3—C4—C7—O2	−162.01 (16)	C10—C11—C12—N1	0.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.85	2.6707 (19)	176
N1—H1A···O3ⁱⁱ	0.86	1.73	2.5889 (19)	173
C2—H2···O1ⁱⁱⁱ	0.93	2.60	3.485 (2)	160

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

Experimental details

Crystal data
Chemical formula	C₆H₈N⁺·C₇H₅O₃⁻
M_r	231.24
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	7.479 (5), 11.671 (4), 13.520 (5)
β (°)	100.217 (5)
V (Å³)	1161.4 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.978, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	11741, 2564, 1939
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.128, 1.06
No. of reflections	2564
No. of parameters	156
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.34

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.85	2.6707 (19)	176
N1—H1A···O3ⁱⁱ	0.86	1.73	2.5889 (19)	173
C2—H2···O1ⁱⁱⁱ	0.93	2.60	3.485 (2)	160

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

Acknowledgements

MK would like to thank Council of Scientific and Industrial Research, New Delhi, India, for providing financial support [project No. 03 (1200)/11/EMR–II].

References

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