2-Amino-5-methyl-pyridinium 4-chloro-benzoate.

The 4-chloro-benzoate anion of the title salt, C6H9N2(+)·C7H4ClO2(-), is nearly planar with a dihedral angle of 5.14 (16)° between the benzene ring and the carboxyl-ate group. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms of the anion via a pair of N-H⋯O hydrogen bonds with an R2(2)(8) ring motif. The ion pairs are further connected via N-H⋯O and weak C-H⋯O hydrogen bonds, forming a two-dimensional network parallel to the bc plane. The crystal structure also features a π-π stacking inter-action between the pyridinium and benzene rings with a centroid-centroid distance of 3.7948 (9) Å.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For 4-chloro­benzoic acid, see: Dionysiou et al. (2000 ▶). For details of hydrogen-bonded supra­molecular compounds, see: Aakeroy et al. (2002 ▶). For related structures, see: Nahringbauer & Kvick (1977 ▶); Thanigaimani et al. (2012a ▶,b ▶,c ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C6H9N2 +·C7H4ClO2 −

M = 264.70

Monoclinic,

a = 9.8510 (6) Å

b = 10.7707 (8) Å

c = 12.2123 (7) Å

β = 102.335 (2)°

V = 1265.84 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 297 K

0.46 × 0.25 × 0.13 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.876, T max = 0.963

17572 measured reflections

4628 independent reflections

2976 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.139

S = 1.04

4628 reflections

176 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812051021/is5231sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051021/is5231Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812051021/is5231Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C6H9N2+·C7H4ClO2−	F(000) = 552
Mr = 264.70	Dx = 1.389 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3497 reflections
a = 9.8510 (6) Å	θ = 2.6–26.9°
b = 10.7707 (8) Å	µ = 0.30 mm−1
c = 12.2123 (7) Å	T = 297 K
β = 102.335 (2)°	Plate, colourless
V = 1265.84 (14) Å3	0.46 × 0.25 × 0.13 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	4628 independent reflections
Radiation source: fine-focus sealed tube	2976 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 32.8°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→15
Tmin = 0.876, Tmax = 0.963	k = −16→16
17572 measured reflections	l = −18→17

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0608P)2 + 0.1513P] where P = (Fo2 + 2Fc2)/3
4628 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	−0.02173 (5)	0.82984 (4)	0.23669 (4)	0.07093 (17)
O1	0.41482 (11)	0.36071 (10)	0.43150 (8)	0.0468 (2)
O2	0.29316 (12)	0.37788 (10)	0.56405 (8)	0.0521 (3)
N1	0.54982 (12)	0.32374 (10)	0.06443 (9)	0.0384 (2)
N2	0.44920 (16)	0.28252 (14)	0.21480 (12)	0.0534 (3)
C1	0.53584 (14)	0.34947 (12)	0.16960 (11)	0.0393 (3)
C2	0.61705 (15)	0.44688 (14)	0.22692 (12)	0.0462 (3)
H2A	0.6104	0.4672	0.2996	0.055*
C3	0.70468 (15)	0.51067 (14)	0.17600 (13)	0.0490 (3)
H3A	0.7581	0.5743	0.2148	0.059*
C4	0.71723 (14)	0.48309 (13)	0.06545 (12)	0.0452 (3)
C5	0.63774 (14)	0.38868 (13)	0.01390 (11)	0.0416 (3)
H5A	0.6435	0.3675	−0.0588	0.050*
C6	0.81460 (18)	0.55543 (18)	0.01020 (17)	0.0643 (4)
H6A	0.8137	0.5209	−0.0624	0.096*
H6B	0.9070	0.5510	0.0555	0.096*
H6C	0.7853	0.6406	0.0022	0.096*
C7	0.14475 (15)	0.57790 (14)	0.46421 (12)	0.0449 (3)
H7A	0.1323	0.5510	0.5338	0.054*
C8	0.06266 (16)	0.67279 (15)	0.40995 (14)	0.0530 (4)
H8A	−0.0053	0.7091	0.4420	0.064*
C9	0.08322 (14)	0.71276 (13)	0.30744 (12)	0.0452 (3)
C10	0.18420 (16)	0.66134 (13)	0.25949 (12)	0.0452 (3)
H10A	0.1978	0.6902	0.1909	0.054*
C11	0.26556 (14)	0.56587 (12)	0.31472 (11)	0.0399 (3)
H11A	0.3344	0.5309	0.2830	0.048*
C12	0.24526 (12)	0.52207 (11)	0.41692 (10)	0.0336 (2)
C13	0.32454 (13)	0.41235 (11)	0.47546 (10)	0.0356 (3)
H1N1	0.4981 (19)	0.2561 (18)	0.0206 (15)	0.067 (5)*
H2N2	0.393 (2)	0.227 (2)	0.1687 (17)	0.075 (6)*
H1N2	0.4328 (19)	0.3062 (17)	0.2770 (17)	0.060 (5)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0665 (3)	0.0571 (3)	0.0817 (3)	0.02362 (19)	−0.0011 (2)	0.0172 (2)
O1	0.0589 (6)	0.0468 (5)	0.0353 (5)	0.0185 (4)	0.0114 (4)	0.0030 (4)
O2	0.0713 (7)	0.0503 (6)	0.0373 (5)	0.0150 (5)	0.0171 (5)	0.0093 (4)
N1	0.0453 (6)	0.0363 (5)	0.0330 (5)	0.0000 (4)	0.0069 (4)	−0.0063 (4)
N2	0.0695 (8)	0.0554 (8)	0.0388 (6)	−0.0138 (7)	0.0196 (6)	−0.0123 (6)
C1	0.0468 (7)	0.0369 (6)	0.0332 (6)	0.0043 (5)	0.0063 (5)	−0.0056 (5)
C2	0.0529 (8)	0.0457 (7)	0.0384 (7)	0.0010 (6)	0.0060 (6)	−0.0134 (6)
C3	0.0460 (7)	0.0418 (7)	0.0564 (8)	−0.0020 (6)	0.0050 (6)	−0.0140 (6)
C4	0.0424 (7)	0.0400 (7)	0.0532 (8)	0.0028 (5)	0.0102 (6)	−0.0018 (6)
C5	0.0457 (7)	0.0415 (7)	0.0380 (6)	0.0048 (5)	0.0101 (5)	−0.0026 (5)
C6	0.0588 (9)	0.0611 (10)	0.0768 (12)	−0.0101 (8)	0.0231 (8)	−0.0026 (9)
C7	0.0498 (7)	0.0446 (7)	0.0428 (7)	0.0064 (6)	0.0157 (6)	0.0043 (6)
C8	0.0503 (8)	0.0513 (8)	0.0608 (9)	0.0148 (6)	0.0195 (7)	0.0036 (7)
C9	0.0414 (7)	0.0365 (6)	0.0533 (8)	0.0052 (5)	−0.0001 (6)	0.0030 (6)
C10	0.0534 (8)	0.0405 (7)	0.0408 (7)	0.0040 (6)	0.0083 (6)	0.0073 (5)
C11	0.0442 (6)	0.0379 (6)	0.0389 (6)	0.0053 (5)	0.0117 (5)	0.0023 (5)
C12	0.0365 (6)	0.0295 (5)	0.0330 (6)	−0.0017 (4)	0.0036 (4)	−0.0022 (4)
C13	0.0453 (6)	0.0314 (6)	0.0280 (5)	0.0013 (5)	0.0029 (5)	−0.0029 (4)

Cl1—C9	1.7390 (14)	C5—H5A	0.9300
O1—C13	1.2619 (16)	C6—H6A	0.9600
O2—C13	1.2436 (16)	C6—H6B	0.9600
N1—C1	1.3495 (16)	C6—H6C	0.9600
N1—C5	1.3596 (18)	C7—C8	1.382 (2)
N1—H1N1	0.98 (2)	C7—C12	1.3856 (18)
N2—C1	1.3245 (19)	C7—H7A	0.9300
N2—H2N2	0.92 (2)	C8—C9	1.379 (2)
N2—H1N2	0.85 (2)	C8—H8A	0.9300
C1—C2	1.4113 (19)	C9—C10	1.374 (2)
C2—C3	1.354 (2)	C10—C11	1.3870 (18)
C2—H2A	0.9300	C10—H10A	0.9300
C3—C4	1.413 (2)	C11—C12	1.3881 (18)
C3—H3A	0.9300	C11—H11A	0.9300
C4—C5	1.3539 (19)	C12—C13	1.5097 (16)
C4—C6	1.503 (2)
C1—N1—C5	122.05 (12)	C4—C6—H6C	109.5
C1—N1—H1N1	121.7 (10)	H6A—C6—H6C	109.5
C5—N1—H1N1	116.2 (10)	H6B—C6—H6C	109.5
C1—N2—H2N2	117.2 (12)	C8—C7—C12	121.22 (13)
C1—N2—H1N2	118.2 (13)	C8—C7—H7A	119.4
H2N2—N2—H1N2	122.3 (17)	C12—C7—H7A	119.4
N2—C1—N1	119.39 (13)	C9—C8—C7	118.80 (13)
N2—C1—C2	123.06 (13)	C9—C8—H8A	120.6
N1—C1—C2	117.55 (13)	C7—C8—H8A	120.6
C3—C2—C1	119.92 (13)	C10—C9—C8	121.41 (13)
C3—C2—H2A	120.0	C10—C9—Cl1	119.23 (12)
C1—C2—H2A	120.0	C8—C9—Cl1	119.36 (11)
C2—C3—C4	121.78 (13)	C9—C10—C11	119.16 (13)
C2—C3—H3A	119.1	C9—C10—H10A	120.4
C4—C3—H3A	119.1	C11—C10—H10A	120.4
C5—C4—C3	116.24 (13)	C10—C11—C12	120.66 (12)
C5—C4—C6	122.81 (14)	C10—C11—H11A	119.7
C3—C4—C6	120.95 (14)	C12—C11—H11A	119.7
C4—C5—N1	122.46 (13)	C7—C12—C11	118.71 (12)
C4—C5—H5A	118.8	C7—C12—C13	119.06 (11)
N1—C5—H5A	118.8	C11—C12—C13	122.18 (11)
C4—C6—H6A	109.5	O2—C13—O1	124.56 (12)
C4—C6—H6B	109.5	O2—C13—C12	116.49 (11)
H6A—C6—H6B	109.5	O1—C13—C12	118.93 (11)
C5—N1—C1—N2	−179.57 (13)	C7—C8—C9—Cl1	178.64 (12)
C5—N1—C1—C2	−0.37 (19)	C8—C9—C10—C11	1.0 (2)
N2—C1—C2—C3	179.28 (15)	Cl1—C9—C10—C11	−178.43 (11)
N1—C1—C2—C3	0.1 (2)	C9—C10—C11—C12	0.3 (2)
C1—C2—C3—C4	0.4 (2)	C8—C7—C12—C11	2.0 (2)
C2—C3—C4—C5	−0.6 (2)	C8—C7—C12—C13	−175.35 (13)
C2—C3—C4—C6	179.69 (15)	C10—C11—C12—C7	−1.8 (2)
C3—C4—C5—N1	0.3 (2)	C10—C11—C12—C13	175.48 (12)
C6—C4—C5—N1	−179.95 (14)	C7—C12—C13—O2	0.45 (17)
C1—N1—C5—C4	0.1 (2)	C11—C12—C13—O2	−176.81 (12)
C12—C7—C8—C9	−0.7 (2)	C7—C12—C13—O1	179.13 (12)
C7—C8—C9—C10	−0.8 (2)	C11—C12—C13—O1	1.87 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1	0.85 (2)	2.02 (2)	2.8654 (18)	174.1 (19)
N1—H1N1···O1i	0.98 (2)	1.75 (2)	2.7255 (14)	174.1 (16)
N2—H2N2···O2i	0.92 (2)	1.83 (2)	2.7437 (17)	172.7 (18)
C2—H2A···O2ii	0.93	2.40	3.1459 (18)	137

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1	0.85 (2)	2.02 (2)	2.8654 (18)	174.1 (19)
N1—H1N1⋯O1i	0.98 (2)	1.75 (2)	2.7255 (14)	174.1 (16)
N2—H2N2⋯O2i	0.92 (2)	1.83 (2)	2.7437 (17)	172.7 (18)
C2—H2A⋯O2ii	0.93	2.40	3.1459 (18)	137

Symmetry codes: (i) ; (ii) .