2-Amino-4-methyl-pyridinium 3-chloro-benzoate.

In the title salt, C(6)H(9)N(2) (+)·C(7)H(4)ClO(2) (-), the 2-amino-4-methyl-pyridinium cation is almost planar, with a maximum deviation of 0.010 (1) Å. 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, forming an R(2) (2)(8) ring motif. 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 details of non-covalent inter­actions, see: Remenar et al. (2003 ▶); Aakeroÿ et al. (2001 ▶); Sokolov et al. (2006 ▶). For related structures, see: Kvick & Noordik (1977 ▶); Shen et al. (2008 ▶); Hemamalini & Fun (2010 ▶). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶). 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 in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C6H9N2 +·C7H4ClO2 −

M = 264.70

Monoclinic,

a = 7.9930 (6) Å

b = 6.8608 (5) Å

c = 11.2148 (9) Å

β = 93.526 (2)°

V = 613.84 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.31 mm−1

T = 100 K

0.28 × 0.17 × 0.10 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.919, T max = 0.971

9325 measured reflections

4207 independent reflections

4076 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.117

S = 1.22

4207 reflections

164 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.64 e Å−3

Δρmin = −0.54 e Å−3

Absolute structure: Flack (1983 ▶), 1860 Friedel pairs

Flack parameter: −0.01 (4)

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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681002444X/hb5503sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002444X/hb5503Isup2.hkl

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

C6H9N2+·C7H4ClO2−	F(000) = 276
Mr = 264.70	Dx = 1.432 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 6601 reflections
a = 7.9930 (6) Å	θ = 3.9–35.1°
b = 6.8608 (5) Å	µ = 0.31 mm−1
c = 11.2148 (9) Å	T = 100 K
β = 93.526 (2)°	Needle, colourless
V = 613.84 (8) Å3	0.28 × 0.17 × 0.10 mm
Z = 2

Bruker APEXII DUO CCD diffractometer	4207 independent reflections
Radiation source: fine-focus sealed tube	4076 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 32.5°, θmin = 3.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→12
Tmin = 0.919, Tmax = 0.971	k = −10→10
9325 measured reflections	l = −16→16

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)] = 0.029	H-atom parameters constrained
wR(F2) = 0.117	w = 1/[σ2(Fo2) + (0.0801P)2] where P = (Fo2 + 2Fc2)/3
S = 1.22	(Δ/σ)max < 0.001
4207 reflections	Δρmax = 0.64 e Å−3
164 parameters	Δρmin = −0.54 e Å−3
1 restraint	Absolute structure: Flack (1983), 1860 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.01 (4)

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 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 > 2σ(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	0.03584 (4)	1.13218 (6)	0.91629 (3)	0.02460 (10)
O1	0.36548 (12)	0.41445 (16)	0.66474 (7)	0.01744 (18)
O2	0.36855 (12)	0.47553 (16)	0.86099 (7)	0.01876 (19)
C7	0.18473 (15)	0.7570 (2)	0.61091 (10)	0.0158 (2)
H7A	0.2131	0.6782	0.5478	0.019*
C8	0.09543 (15)	0.9288 (2)	0.58796 (11)	0.0197 (2)
H8A	0.0654	0.9648	0.5096	0.024*
C9	0.05103 (16)	1.0466 (2)	0.68188 (12)	0.0195 (2)
H9A	−0.0078	1.1618	0.6671	0.023*
C10	0.09626 (15)	0.9890 (2)	0.79852 (10)	0.0159 (2)
C11	0.18604 (14)	0.8195 (2)	0.82290 (10)	0.0148 (2)
H11A	0.2155	0.7838	0.9014	0.018*
C12	0.23182 (14)	0.70259 (19)	0.72825 (10)	0.01258 (19)
C13	0.32902 (14)	0.51628 (19)	0.75345 (10)	0.0131 (2)
N1	0.53373 (13)	1.07928 (17)	0.70756 (8)	0.01350 (18)
H1A	0.4786	1.1863	0.6979	0.016*
N2	0.53701 (13)	1.1268 (3)	0.91147 (8)	0.0185 (2)
H2B	0.4837	1.2344	0.8986	0.022*
H2C	0.5638	1.0902	0.9835	0.022*
C1	0.57797 (14)	1.01721 (19)	0.82012 (10)	0.0133 (2)
C2	0.66378 (14)	0.8378 (2)	0.83484 (10)	0.0144 (2)
H2A	0.6936	0.7919	0.9112	0.017*
C3	0.70348 (14)	0.73057 (19)	0.73661 (10)	0.0141 (2)
C4	0.65921 (14)	0.8046 (2)	0.62099 (10)	0.0152 (2)
H4A	0.6878	0.7364	0.5535	0.018*
C5	0.57458 (14)	0.9762 (2)	0.60956 (9)	0.0143 (2)
H5A	0.5441	1.0239	0.5337	0.017*
C6	0.79035 (16)	0.5371 (2)	0.75110 (12)	0.0195 (2)
H6A	0.9016	0.5472	0.7239	0.029*
H6B	0.7286	0.4404	0.7048	0.029*
H6C	0.7964	0.5002	0.8338	0.029*

	U11	U22	U33	U12	U13	U23
Cl1	0.02597 (15)	0.02386 (18)	0.02371 (15)	0.00755 (12)	−0.00058 (10)	−0.00950 (12)
O1	0.0271 (4)	0.0139 (4)	0.0114 (3)	0.0054 (3)	0.0016 (3)	−0.0014 (3)
O2	0.0299 (4)	0.0157 (5)	0.0104 (3)	0.0044 (4)	−0.0002 (3)	0.0000 (3)
C7	0.0166 (4)	0.0184 (6)	0.0123 (4)	0.0012 (4)	0.0013 (3)	0.0016 (4)
C8	0.0203 (5)	0.0227 (7)	0.0160 (5)	0.0047 (5)	0.0006 (4)	0.0050 (5)
C9	0.0189 (5)	0.0184 (7)	0.0213 (5)	0.0041 (4)	0.0007 (4)	0.0019 (5)
C10	0.0147 (4)	0.0158 (6)	0.0173 (4)	0.0005 (4)	0.0016 (3)	−0.0023 (4)
C11	0.0159 (4)	0.0148 (6)	0.0135 (4)	0.0000 (4)	0.0007 (3)	−0.0009 (4)
C12	0.0131 (4)	0.0126 (5)	0.0121 (4)	−0.0009 (4)	0.0013 (3)	0.0007 (4)
C13	0.0175 (4)	0.0108 (5)	0.0109 (4)	−0.0016 (4)	0.0013 (3)	0.0000 (4)
N1	0.0177 (4)	0.0123 (5)	0.0106 (4)	−0.0005 (3)	0.0009 (3)	0.0017 (3)
N2	0.0292 (5)	0.0162 (5)	0.0100 (4)	0.0049 (4)	0.0009 (3)	−0.0003 (4)
C1	0.0164 (4)	0.0130 (5)	0.0104 (4)	−0.0015 (4)	0.0017 (3)	0.0018 (4)
C2	0.0175 (4)	0.0135 (6)	0.0123 (4)	0.0005 (4)	0.0012 (3)	0.0027 (4)
C3	0.0138 (4)	0.0133 (6)	0.0152 (4)	−0.0010 (4)	0.0016 (3)	0.0007 (4)
C4	0.0161 (4)	0.0164 (6)	0.0130 (4)	−0.0008 (4)	0.0012 (3)	−0.0014 (4)
C5	0.0169 (4)	0.0161 (6)	0.0099 (4)	−0.0021 (4)	0.0012 (3)	0.0001 (4)
C6	0.0199 (5)	0.0158 (6)	0.0228 (5)	0.0032 (4)	0.0024 (4)	0.0010 (4)

Cl1—C10	1.7383 (13)	N1—H1A	0.8600
O1—C13	1.2643 (14)	N2—C1	1.3280 (18)
O2—C13	1.2593 (14)	N2—H2B	0.8600
C7—C8	1.3934 (19)	N2—H2C	0.8600
C7—C12	1.3972 (16)	C1—C2	1.4138 (18)
C7—H7A	0.9300	C2—C3	1.3779 (16)
C8—C9	1.3909 (19)	C2—H2A	0.9300
C8—H8A	0.9300	C3—C4	1.4170 (16)
C9—C10	1.3927 (17)	C3—C6	1.5019 (19)
C9—H9A	0.9300	C4—C5	1.3599 (18)
C10—C11	1.3849 (19)	C4—H4A	0.9300
C11—C12	1.3968 (17)	C5—H5A	0.9300
C11—H11A	0.9300	C6—H6A	0.9600
C12—C13	1.5134 (18)	C6—H6B	0.9600
N1—C1	1.3582 (14)	C6—H6C	0.9600
N1—C5	1.3636 (15)
C8—C7—C12	120.35 (12)	C1—N2—H2B	120.0
C8—C7—H7A	119.8	C1—N2—H2C	120.0
C12—C7—H7A	119.8	H2B—N2—H2C	120.0
C9—C8—C7	120.21 (11)	N2—C1—N1	118.49 (12)
C9—C8—H8A	119.9	N2—C1—C2	122.93 (11)
C7—C8—H8A	119.9	N1—C1—C2	118.57 (11)
C8—C9—C10	118.87 (12)	C3—C2—C1	120.36 (10)
C8—C9—H9A	120.6	C3—C2—H2A	119.8
C10—C9—H9A	120.6	C1—C2—H2A	119.8
C11—C10—C9	121.68 (12)	C2—C3—C4	118.91 (11)
C11—C10—Cl1	119.30 (9)	C2—C3—C6	120.86 (11)
C9—C10—Cl1	119.01 (10)	C4—C3—C6	120.22 (11)
C10—C11—C12	119.26 (11)	C5—C4—C3	119.42 (11)
C10—C11—H11A	120.4	C5—C4—H4A	120.3
C12—C11—H11A	120.4	C3—C4—H4A	120.3
C11—C12—C7	119.63 (12)	C4—C5—N1	121.04 (11)
C11—C12—C13	119.90 (10)	C4—C5—H5A	119.5
C7—C12—C13	120.47 (11)	N1—C5—H5A	119.5
O2—C13—O1	125.07 (12)	C3—C6—H6A	109.5
O2—C13—C12	117.52 (10)	C3—C6—H6B	109.5
O1—C13—C12	117.41 (10)	H6A—C6—H6B	109.5
C1—N1—C5	121.66 (11)	C3—C6—H6C	109.5
C1—N1—H1A	119.2	H6A—C6—H6C	109.5
C5—N1—H1A	119.2	H6B—C6—H6C	109.5
C12—C7—C8—C9	−0.62 (19)	C11—C12—C13—O1	179.10 (11)
C7—C8—C9—C10	−0.5 (2)	C7—C12—C13—O1	0.27 (16)
C8—C9—C10—C11	0.9 (2)	C5—N1—C1—N2	178.68 (11)
C8—C9—C10—Cl1	−178.18 (10)	C5—N1—C1—C2	−2.06 (17)
C9—C10—C11—C12	−0.32 (18)	N2—C1—C2—C3	−179.79 (12)
Cl1—C10—C11—C12	178.81 (9)	N1—C1—C2—C3	0.98 (17)
C10—C11—C12—C7	−0.79 (17)	C1—C2—C3—C4	0.97 (17)
C10—C11—C12—C13	−179.62 (10)	C1—C2—C3—C6	−178.29 (10)
C8—C7—C12—C11	1.26 (18)	C2—C3—C4—C5	−1.91 (17)
C8—C7—C12—C13	−179.91 (11)	C6—C3—C4—C5	177.35 (11)
C11—C12—C13—O2	−1.50 (17)	C3—C4—C5—N1	0.90 (17)
C7—C12—C13—O2	179.67 (11)	C1—N1—C5—C4	1.13 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.86	1.83	2.6921 (16)	175
N2—H2B···O2i	0.86	1.93	2.786 (2)	177
N2—H2C···O2ii	0.86	1.96	2.8146 (14)	173
C5—H5A···O1iii	0.93	2.50	3.1707 (13)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.86	1.83	2.6921 (16)	175
N2—H2B⋯O2i	0.86	1.93	2.786 (2)	177
N2—H2C⋯O2ii	0.86	1.96	2.8146 (14)	173
C5—H5A⋯O1iii	0.93	2.50	3.1707 (13)	129

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