2-Amino-5-methyl-pyridinium 2-hy-droxy-5-chloro-benzoate.

In the 5-chloro-salicylate anion of the title salt, C6H9N2(+)·C7H4ClO3(-), an intra-molecular O-H⋯O hydrogen bond with an S(6) graph-set motif is observed and the dihedral angle between the benzene ring and the -CO2 group is 1.6 (6)°. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms via a pair of N-H⋯O hydrogen bonds, forming an R2(2)(8) ring motif. The crystal structure also features N-H⋯O and weak C-H⋯O inter-actions, resulting in a layer parallel to (10-1).

Related literature

For details of non-covalent inter­actions, see: Desiraju (2007 ▶); Aakeroy & Seddon (1993 ▶). For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For related structures, see: Nahringbauer & Kvick (1977 ▶); Raza et al. (2010 ▶); Thanigaimani et al. (2012a ▶,b ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C6H9N2 +·C7H4ClO3 −

M = 280.70

Monoclinic,

a = 9.004 (7) Å

b = 5.767 (5) Å

c = 12.617 (10) Å

β = 90.415 (16)°

V = 655.2 (9) Å3

Z = 2

Mo Kα radiation

μ = 0.30 mm−1

T = 100 K

0.46 × 0.18 × 0.07 mm

Data collection

Bruker SMART APEXII Duo CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.877, T max = 0.979

4785 measured reflections

2204 independent reflections

1539 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.073

wR(F 2) = 0.201

S = 1.01

2204 reflections

189 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.47 e Å−3

Δρmin = −0.44 e Å−3

Absolute structure: Flack (1983 ▶), 941 Friedel pairs

Flack parameter: 0.09 (16)

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/S160053681205101X/is5232sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681205101X/is5232Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S160053681205101X/is5232Isup3.cml

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

C6H9N2+·C7H4ClO3−	F(000) = 292
Mr = 280.70	Dx = 1.423 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1722 reflections
a = 9.004 (7) Å	θ = 2.8–29.7°
b = 5.767 (5) Å	µ = 0.30 mm−1
c = 12.617 (10) Å	T = 100 K
β = 90.415 (16)°	Block, colourless
V = 655.2 (9) Å3	0.46 × 0.18 × 0.07 mm
Z = 2

Bruker SMART APEXII Duo CCD area-detector diffractometer	2204 independent reflections
Radiation source: fine-focus sealed tube	1539 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
φ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.877, Tmax = 0.979	k = −6→6
4785 measured reflections	l = −14→15

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)] = 0.073	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.201	w = 1/[σ2(Fo2) + (0.1249P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.001
2204 reflections	Δρmax = 0.47 e Å−3
189 parameters	Δρmin = −0.44 e Å−3
2 restraints	Absolute structure: Flack (1983), 941 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.09 (16)

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	0.49320 (17)	0.7884 (3)	0.59756 (12)	0.0882 (6)
O1	0.1352 (4)	0.0724 (8)	0.6317 (2)	0.0718 (11)
O2	0.1487 (4)	−0.0555 (7)	0.7972 (2)	0.0665 (10)
O3	0.3088 (5)	0.1483 (9)	0.9319 (3)	0.0809 (13)
N1	0.9568 (5)	0.6055 (9)	0.7468 (3)	0.0581 (11)
N2	0.9360 (7)	0.7221 (10)	0.5745 (4)	0.0730 (15)
C1	0.8976 (5)	0.5709 (10)	0.6496 (3)	0.0555 (13)
C2	0.8031 (5)	0.3909 (10)	0.6344 (4)	0.0613 (15)
H2A	0.7593	0.3646	0.5667	0.074*
C3	0.7716 (6)	0.2485 (12)	0.7170 (4)	0.0724 (17)
H3A	0.7049	0.1232	0.7056	0.087*
C4	0.8336 (6)	0.2786 (13)	0.8183 (4)	0.0683 (14)
C5	0.9247 (6)	0.4608 (11)	0.8286 (4)	0.0622 (14)
H5A	0.9688	0.4902	0.8959	0.075*
C6	0.8003 (8)	0.1215 (15)	0.9103 (5)	0.093 (2)
H6A	0.8451	0.1854	0.9750	0.139*
H6B	0.8416	−0.0328	0.8966	0.139*
H6C	0.6925	0.1096	0.9191	0.139*
C7	0.3500 (5)	0.2962 (12)	0.8536 (3)	0.0604 (13)
C8	0.4479 (6)	0.4684 (11)	0.8751 (4)	0.0681 (16)
H8A	0.4865	0.4834	0.9450	0.082*
C9	0.4933 (6)	0.6238 (11)	0.7977 (4)	0.0666 (15)
H9A	0.5615	0.7446	0.8138	0.080*
C10	0.4360 (5)	0.5971 (11)	0.6960 (4)	0.0620 (13)
C11	0.3378 (6)	0.4262 (11)	0.6724 (4)	0.0581 (13)
H11A	0.3005	0.4116	0.6021	0.070*
C12	0.2916 (5)	0.2732 (11)	0.7495 (3)	0.0507 (11)
C13	0.1848 (5)	0.0861 (11)	0.7244 (3)	0.0579 (13)
H1N1	1.019 (6)	0.735 (11)	0.754 (4)	0.070 (17)*
H1N2	0.985 (6)	0.846 (7)	0.587 (5)	0.09 (3)*
H2N2	0.888 (7)	0.705 (14)	0.517 (5)	0.09 (2)*
H1O3	0.225 (7)	0.071 (13)	0.909 (5)	0.083 (19)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0888 (9)	0.0908 (11)	0.0850 (10)	−0.0173 (9)	0.0112 (7)	0.0067 (10)
O1	0.076 (2)	0.099 (3)	0.0404 (16)	−0.016 (2)	−0.0140 (14)	−0.001 (2)
O2	0.076 (2)	0.080 (3)	0.0430 (16)	−0.011 (2)	−0.0066 (14)	0.0066 (19)
O3	0.103 (3)	0.103 (4)	0.0371 (17)	−0.013 (3)	−0.0145 (17)	0.0037 (19)
N1	0.066 (2)	0.068 (3)	0.0402 (19)	−0.005 (2)	−0.0016 (16)	−0.002 (2)
N2	0.095 (3)	0.082 (4)	0.042 (2)	−0.012 (3)	−0.009 (2)	−0.009 (2)
C1	0.058 (3)	0.070 (4)	0.038 (2)	0.004 (3)	0.0016 (19)	−0.005 (3)
C2	0.067 (3)	0.073 (4)	0.044 (2)	−0.004 (3)	−0.003 (2)	−0.010 (3)
C3	0.070 (3)	0.077 (5)	0.070 (3)	−0.010 (3)	0.004 (2)	−0.014 (3)
C4	0.067 (3)	0.079 (4)	0.059 (3)	0.004 (3)	0.007 (2)	−0.002 (3)
C5	0.076 (3)	0.072 (4)	0.038 (2)	0.003 (3)	0.001 (2)	0.002 (2)
C6	0.108 (5)	0.098 (5)	0.072 (3)	−0.003 (4)	0.014 (3)	0.017 (4)
C7	0.058 (3)	0.083 (4)	0.040 (2)	0.003 (3)	−0.0017 (18)	−0.006 (3)
C8	0.070 (3)	0.087 (5)	0.047 (2)	−0.002 (3)	−0.007 (2)	−0.016 (3)
C9	0.063 (3)	0.068 (4)	0.069 (3)	0.000 (3)	0.003 (2)	−0.018 (3)
C10	0.053 (2)	0.075 (4)	0.058 (3)	−0.005 (3)	0.005 (2)	−0.004 (3)
C11	0.064 (3)	0.069 (3)	0.042 (2)	0.003 (3)	0.0054 (19)	−0.008 (2)
C12	0.048 (2)	0.068 (3)	0.036 (2)	0.010 (3)	−0.0010 (15)	−0.009 (3)
C13	0.060 (3)	0.069 (4)	0.044 (2)	0.000 (3)	−0.0012 (19)	0.005 (3)

Cl1—C10	1.742 (6)	C4—C5	1.339 (9)
O1—C13	1.251 (5)	C4—C6	1.504 (9)
O2—C13	1.273 (6)	C5—H5A	0.9500
O3—C7	1.359 (7)	C6—H6A	0.9800
O3—H1O3	0.92 (7)	C6—H6B	0.9800
N1—C1	1.349 (6)	C6—H6C	0.9800
N1—C5	1.359 (7)	C7—C8	1.354 (9)
N1—H1N1	0.94 (6)	C7—C12	1.417 (6)
N2—C1	1.335 (7)	C8—C9	1.389 (8)
N2—H1N2	0.853 (10)	C8—H8A	0.9500
N2—H2N2	0.85 (7)	C9—C10	1.388 (7)
C1—C2	1.355 (8)	C9—H9A	0.9500
C2—C3	1.358 (8)	C10—C11	1.356 (8)
C2—H2A	0.9500	C11—C12	1.380 (8)
C3—C4	1.403 (8)	C11—H11A	0.9500
C3—H3A	0.9500	C12—C13	1.478 (8)
C7—O3—H1O3	107 (4)	C4—C6—H6C	109.5
C1—N1—C5	120.9 (5)	H6A—C6—H6C	109.5
C1—N1—H1N1	116 (3)	H6B—C6—H6C	109.5
C5—N1—H1N1	123 (3)	C8—C7—O3	119.7 (4)
C1—N2—H1N2	124 (4)	C8—C7—C12	119.4 (5)
C1—N2—H2N2	114 (5)	O3—C7—C12	120.9 (5)
H1N2—N2—H2N2	121 (7)	C7—C8—C9	121.8 (4)
N2—C1—N1	116.5 (5)	C7—C8—H8A	119.1
N2—C1—C2	124.5 (4)	C9—C8—H8A	119.1
N1—C1—C2	119.0 (5)	C10—C9—C8	118.0 (5)
C1—C2—C3	119.3 (5)	C10—C9—H9A	121.0
C1—C2—H2A	120.4	C8—C9—H9A	121.0
C3—C2—H2A	120.4	C11—C10—C9	121.4 (5)
C2—C3—C4	122.7 (6)	C11—C10—Cl1	120.0 (4)
C2—C3—H3A	118.6	C9—C10—Cl1	118.6 (5)
C4—C3—H3A	118.6	C10—C11—C12	120.6 (4)
C5—C4—C3	115.1 (5)	C10—C11—H11A	119.7
C5—C4—C6	121.6 (5)	C12—C11—H11A	119.7
C3—C4—C6	123.3 (6)	C11—C12—C7	118.8 (5)
C4—C5—N1	122.9 (5)	C11—C12—C13	121.0 (4)
C4—C5—H5A	118.6	C7—C12—C13	120.2 (5)
N1—C5—H5A	118.6	O1—C13—O2	122.9 (5)
C4—C6—H6A	109.5	O1—C13—C12	118.3 (4)
C4—C6—H6B	109.5	O2—C13—C12	118.8 (4)
H6A—C6—H6B	109.5
C5—N1—C1—N2	−179.9 (5)	C8—C9—C10—Cl1	−179.3 (4)
C5—N1—C1—C2	1.0 (7)	C9—C10—C11—C12	0.2 (8)
N2—C1—C2—C3	−179.7 (5)	Cl1—C10—C11—C12	179.9 (4)
N1—C1—C2—C3	−0.7 (8)	C10—C11—C12—C7	−0.8 (7)
C1—C2—C3—C4	−0.3 (9)	C10—C11—C12—C13	−179.9 (5)
C2—C3—C4—C5	1.0 (9)	C8—C7—C12—C11	0.8 (7)
C2—C3—C4—C6	−179.7 (6)	O3—C7—C12—C11	−179.4 (5)
C3—C4—C5—N1	−0.7 (8)	C8—C7—C12—C13	179.9 (5)
C6—C4—C5—N1	180.0 (5)	O3—C7—C12—C13	−0.3 (7)
C1—N1—C5—C4	−0.3 (8)	C11—C12—C13—O1	−1.3 (7)
O3—C7—C8—C9	180.0 (5)	C7—C12—C13—O1	179.6 (5)
C12—C7—C8—C9	−0.2 (8)	C11—C12—C13—O2	177.8 (4)
C7—C8—C9—C10	−0.4 (8)	C7—C12—C13—O2	−1.2 (7)
C8—C9—C10—C11	0.4 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O3···O2	0.92 (6)	1.73 (7)	2.512 (6)	141 (6)
N1—H1N1···O2i	0.94 (6)	1.76 (6)	2.683 (7)	166 (5)
N2—H1N2···O1i	0.85 (5)	1.96 (5)	2.793 (8)	165 (4)
N2—H2N2···O1ii	0.85 (6)	2.04 (7)	2.811 (6)	152 (7)
C8—H8A···O3iii	0.95	2.58	3.425 (7)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1O3⋯O2	0.92 (6)	1.73 (7)	2.512 (6)	141 (6)
N1—H1N1⋯O2i	0.94 (6)	1.76 (6)	2.683 (7)	166 (5)
N2—H1N2⋯O1i	0.85 (5)	1.96 (5)	2.793 (8)	165 (4)
N2—H2N2⋯O1ii	0.85 (6)	2.04 (7)	2.811 (6)	152 (7)
C8—H8A⋯O3iii	0.95	2.58	3.425 (7)	148

Symmetry codes: (i) ; (ii) ; (iii) .