2-Amino-5-methyl-pyridinium 3-chloro-benzoate.

The 3-chloro-benzoate anion of the title salt, C(6)H(9)N(2) (+)·C(7)H(4)ClO(2) (-), is nearly planar with a dihedral angle of 2.44 (13)° 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 R(2) (2)(8) ring motif, forming an approximately planar ion pair with a dihedral angle of 7.92 (5)° between the pyridinium and benzene rings. The ion pairs are further connected via N-H⋯O and C-H⋯O hydrogen bonds, forming a two-dimensional network parallel to the bc plane.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For details of hydrogen bonding, see: Jeffrey (1997 ▶); Scheiner (1997 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C6H9N2 +·C7H4ClO2 −

M = 264.70

Monoclinic,

a = 9.0318 (11) Å

b = 11.6590 (14) Å

c = 12.1166 (15) Å

β = 101.521 (2)°

V = 1250.2 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 100 K

0.53 × 0.31 × 0.22 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.856, T max = 0.936

13594 measured reflections

3629 independent reflections

3201 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.115

S = 1.06

3629 reflections

176 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.33 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/S1600536812043231/is5201sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043231/is5201Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812043231/is5201Isup3.cml

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

C6H9N2+·C7H4ClO2−	F(000) = 552
Mr = 264.70	Dx = 1.406 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6768 reflections
a = 9.0318 (11) Å	θ = 2.3–30.1°
b = 11.6590 (14) Å	µ = 0.30 mm−1
c = 12.1166 (15) Å	T = 100 K
β = 101.521 (2)°	Block, colourless
V = 1250.2 (3) Å3	0.53 × 0.31 × 0.22 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	3629 independent reflections
Radiation source: fine-focus sealed tube	3201 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 30.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
Tmin = 0.856, Tmax = 0.936	k = −16→16
13594 measured reflections	l = −17→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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.070P)2 + 0.2814P] where P = (Fo2 + 2Fc2)/3
3629 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

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	1.05016 (3)	0.25195 (2)	0.66489 (3)	0.02535 (11)
O1	0.60056 (10)	0.65207 (8)	0.46906 (7)	0.02385 (19)
O2	0.72588 (10)	0.62484 (8)	0.64581 (7)	0.02350 (19)
N1	0.45310 (10)	0.81988 (8)	0.55172 (8)	0.01776 (19)
N2	0.55220 (12)	0.77783 (10)	0.73908 (9)	0.0219 (2)
C1	0.46396 (12)	0.84318 (9)	0.66248 (10)	0.0179 (2)
C2	0.37858 (13)	0.93693 (10)	0.69173 (10)	0.0210 (2)
H2A	0.3833	0.9561	0.7686	0.025*
C3	0.28968 (13)	0.99913 (10)	0.60827 (11)	0.0218 (2)
H3A	0.2327	1.0615	0.6283	0.026*
C4	0.27996 (12)	0.97334 (10)	0.49275 (10)	0.0204 (2)
C5	0.36421 (12)	0.88246 (10)	0.46891 (10)	0.0190 (2)
H5A	0.3607	0.8624	0.3924	0.023*
C6	0.18156 (14)	1.04262 (11)	0.40224 (11)	0.0262 (3)
H6A	0.1968	1.0170	0.3283	0.039*
H6B	0.2084	1.1239	0.4124	0.039*
H6C	0.0754	1.0321	0.4070	0.039*
C7	0.69320 (12)	0.59788 (9)	0.54401 (9)	0.0175 (2)
C8	0.76799 (11)	0.49160 (9)	0.50805 (9)	0.0159 (2)
C9	0.86515 (12)	0.42923 (9)	0.59063 (9)	0.0172 (2)
H9A	0.8840	0.4537	0.6670	0.021*
C10	0.93380 (12)	0.33117 (9)	0.55982 (10)	0.0180 (2)
C11	0.91118 (13)	0.29472 (10)	0.44867 (10)	0.0212 (2)
H11A	0.9603	0.2280	0.4288	0.025*
C12	0.81496 (13)	0.35797 (10)	0.36693 (10)	0.0224 (2)
H12A	0.7987	0.3345	0.2904	0.027*
C13	0.74215 (12)	0.45553 (10)	0.39638 (9)	0.0198 (2)
H13A	0.6750	0.4973	0.3402	0.024*
H1N1	0.511 (3)	0.7554 (18)	0.526 (2)	0.055 (7)*
H1N2	0.617 (2)	0.7251 (16)	0.7129 (17)	0.037 (5)*
H2N2	0.574 (2)	0.8015 (16)	0.8114 (16)	0.035 (4)*

	U11	U22	U33	U12	U13	U23
Cl1	0.02441 (17)	0.02607 (17)	0.02424 (17)	0.00991 (9)	0.00168 (12)	0.00262 (10)
O1	0.0302 (4)	0.0259 (4)	0.0161 (4)	0.0125 (3)	0.0061 (3)	0.0030 (3)
O2	0.0285 (4)	0.0253 (4)	0.0163 (4)	0.0075 (3)	0.0034 (3)	−0.0021 (3)
N1	0.0183 (4)	0.0195 (4)	0.0156 (4)	0.0034 (3)	0.0037 (3)	−0.0019 (3)
N2	0.0240 (5)	0.0262 (5)	0.0150 (5)	0.0050 (4)	0.0025 (4)	−0.0025 (4)
C1	0.0168 (5)	0.0201 (5)	0.0173 (5)	−0.0003 (4)	0.0047 (4)	−0.0028 (4)
C2	0.0206 (5)	0.0231 (5)	0.0203 (5)	0.0005 (4)	0.0066 (4)	−0.0061 (4)
C3	0.0193 (5)	0.0207 (5)	0.0263 (6)	0.0030 (4)	0.0064 (4)	−0.0047 (4)
C4	0.0183 (5)	0.0202 (5)	0.0230 (5)	0.0024 (4)	0.0045 (4)	0.0000 (4)
C5	0.0189 (5)	0.0215 (5)	0.0166 (5)	0.0021 (4)	0.0038 (4)	−0.0006 (4)
C6	0.0253 (6)	0.0258 (6)	0.0269 (6)	0.0084 (4)	0.0038 (5)	0.0024 (5)
C7	0.0195 (5)	0.0181 (5)	0.0163 (5)	0.0023 (4)	0.0069 (4)	0.0013 (4)
C8	0.0156 (4)	0.0169 (4)	0.0159 (5)	0.0012 (3)	0.0049 (4)	0.0000 (4)
C9	0.0166 (4)	0.0187 (5)	0.0164 (5)	0.0011 (4)	0.0037 (4)	0.0000 (4)
C10	0.0146 (4)	0.0188 (5)	0.0205 (5)	0.0019 (3)	0.0030 (4)	0.0016 (4)
C11	0.0197 (5)	0.0203 (5)	0.0238 (6)	0.0029 (4)	0.0046 (4)	−0.0039 (4)
C12	0.0242 (5)	0.0246 (5)	0.0182 (5)	0.0032 (4)	0.0036 (4)	−0.0047 (4)
C13	0.0208 (5)	0.0223 (5)	0.0160 (5)	0.0033 (4)	0.0029 (4)	−0.0003 (4)

Cl1—C10	1.7447 (11)	C5—H5A	0.9500
O1—C7	1.2729 (13)	C6—H6A	0.9800
O2—C7	1.2498 (14)	C6—H6B	0.9800
N1—C1	1.3535 (14)	C6—H6C	0.9800
N1—C5	1.3645 (14)	C7—C8	1.5163 (15)
N1—H1N1	1.00 (2)	C8—C13	1.3914 (15)
N2—C1	1.3348 (15)	C8—C9	1.3961 (15)
N2—H1N2	0.949 (19)	C9—C10	1.3870 (15)
N2—H2N2	0.90 (2)	C9—H9A	0.9500
C1—C2	1.4227 (15)	C10—C11	1.3878 (16)
C2—C3	1.3671 (17)	C11—C12	1.3914 (16)
C2—H2A	0.9500	C11—H11A	0.9500
C3—C4	1.4171 (17)	C12—C13	1.3955 (16)
C3—H3A	0.9500	C12—H12A	0.9500
C4—C5	1.3686 (15)	C13—H13A	0.9500
C4—C6	1.5019 (16)
C1—N1—C5	122.50 (10)	C4—C6—H6C	109.5
C1—N1—H1N1	121.5 (14)	H6A—C6—H6C	109.5
C5—N1—H1N1	116.0 (14)	H6B—C6—H6C	109.5
C1—N2—H1N2	117.5 (12)	O2—C7—O1	124.84 (10)
C1—N2—H2N2	119.1 (12)	O2—C7—C8	117.27 (9)
H1N2—N2—H2N2	119.4 (17)	O1—C7—C8	117.88 (10)
N2—C1—N1	119.33 (10)	C13—C8—C9	119.93 (10)
N2—C1—C2	122.91 (11)	C13—C8—C7	121.91 (9)
N1—C1—C2	117.75 (10)	C9—C8—C7	118.16 (9)
C3—C2—C1	119.39 (11)	C10—C9—C8	119.15 (10)
C3—C2—H2A	120.3	C10—C9—H9A	120.4
C1—C2—H2A	120.3	C8—C9—H9A	120.4
C2—C3—C4	121.97 (10)	C9—C10—C11	121.77 (10)
C2—C3—H3A	119.0	C9—C10—Cl1	118.45 (9)
C4—C3—H3A	119.0	C11—C10—Cl1	119.77 (8)
C5—C4—C3	116.45 (10)	C10—C11—C12	118.59 (10)
C5—C4—C6	122.35 (11)	C10—C11—H11A	120.7
C3—C4—C6	121.20 (10)	C12—C11—H11A	120.7
N1—C5—C4	121.94 (10)	C11—C12—C13	120.61 (11)
N1—C5—H5A	119.0	C11—C12—H12A	119.7
C4—C5—H5A	119.0	C13—C12—H12A	119.7
C4—C6—H6A	109.5	C8—C13—C12	119.93 (10)
C4—C6—H6B	109.5	C8—C13—H13A	120.0
H6A—C6—H6B	109.5	C12—C13—H13A	120.0
C5—N1—C1—N2	179.47 (10)	O2—C7—C8—C9	1.54 (15)
C5—N1—C1—C2	−0.06 (16)	O1—C7—C8—C9	−177.53 (10)
N2—C1—C2—C3	−179.39 (11)	C13—C8—C9—C10	−0.51 (16)
N1—C1—C2—C3	0.12 (16)	C7—C8—C9—C10	179.45 (9)
C1—C2—C3—C4	−0.16 (18)	C8—C9—C10—C11	1.46 (16)
C2—C3—C4—C5	0.13 (17)	C8—C9—C10—Cl1	−178.02 (8)
C2—C3—C4—C6	179.96 (11)	C9—C10—C11—C12	−1.01 (17)
C1—N1—C5—C4	0.03 (17)	Cl1—C10—C11—C12	178.47 (9)
C3—C4—C5—N1	−0.06 (16)	C10—C11—C12—C13	−0.39 (18)
C6—C4—C5—N1	−179.89 (10)	C9—C8—C13—C12	−0.85 (17)
O2—C7—C8—C13	−178.50 (10)	C7—C8—C13—C12	179.19 (10)
O1—C7—C8—C13	2.43 (16)	C11—C12—C13—C8	1.32 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1	1.00 (2)	1.68 (2)	2.6716 (13)	174 (2)
N2—H1N2···O2	0.946 (19)	1.820 (19)	2.7618 (15)	173.0 (19)
N2—H2N2···O1i	0.90 (2)	1.95 (2)	2.8526 (14)	174.0 (17)
C2—H2A···O2ii	0.95	2.52	3.2104 (15)	130

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1	1.00 (2)	1.68 (2)	2.6716 (13)	174 (2)
N2—H1N2⋯O2	0.946 (19)	1.820 (19)	2.7618 (15)	173.0 (19)
N2—H2N2⋯O1i	0.90 (2)	1.95 (2)	2.8526 (14)	174.0 (17)
C2—H2A⋯O2ii	0.95	2.52	3.2104 (15)	130

Symmetry codes: (i) ; (ii) .