2-Amino-6-methyl-pyridinium 3-chloro-benzoate.

In the title salt, C6H9N2(+)·C7H4ClO2(-), the 3-chloro-benzoate anion shows a whole-mol-ecule disorder over two positions with a refined occupancy ratio of 0.505 (4):0.495 (4). In the crystal, the cations and anions are linked via N-H⋯O hydrogen bonds, forming a centrosymmetric 2 + 2 aggregate with R2(2)(8) and R4(2)(8) ring motifs. The crystal structure also features a π-π stacking inter-action between the pyridinium rings with a centroid-centroid distance of 3.8339 (9) Å.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For related structures, see: Hemamalini & Fun (2010 ▶); Thanigaimani et al. (2012 ▶); Draguta et al. (2012 ▶). 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 = 22.3118 (15) Å

b = 15.2053 (10) Å

c = 7.4166 (5) Å

β = 100.924 (1)°

V = 2470.5 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.30 mm−1

T = 100 K

0.36 × 0.06 × 0.05 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.898, T max = 0.985

24731 measured reflections

3575 independent reflections

2446 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.128

S = 1.06

3575 reflections

267 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.28 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/S1600536813002559/is5234sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813002559/is5234Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813002559/is5234Isup3.cml

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

C6H9N2+·C7H4ClO2−	F(000) = 1104
Mr = 264.70	Dx = 1.423 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4651 reflections
a = 22.3118 (15) Å	θ = 2.7–29.3°
b = 15.2053 (10) Å	µ = 0.30 mm−1
c = 7.4166 (5) Å	T = 100 K
β = 100.924 (1)°	Needle, colourless
V = 2470.5 (3) Å3	0.36 × 0.06 × 0.05 mm
Z = 8

Bruker SMART APEXII DUO CCD area-detector diffractometer	3575 independent reflections
Radiation source: fine-focus sealed tube	2446 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
φ and ω scans	θmax = 30.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −30→31
Tmin = 0.898, Tmax = 0.985	k = −21→21
24731 measured reflections	l = −10→10

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0584P)2 + 1.2878P] where P = (Fo2 + 2Fc2)/3
3575 reflections	(Δ/σ)max < 0.001
267 parameters	Δρmax = 0.29 e Å−3
5 restraints	Δρmin = −0.28 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	Occ. (<1)
Cl1	0.51442 (12)	0.09433 (16)	0.5251 (4)	0.0377 (5)	0.505 (4)
O1	0.3604 (3)	0.4344 (4)	0.2546 (10)	0.0298 (12)	0.505 (4)
O2	0.3335 (7)	0.2966 (7)	0.1833 (12)	0.0279 (16)	0.505 (4)
C7	0.3716 (3)	0.3536 (4)	0.2547 (8)	0.0223 (11)	0.505 (4)
C8	0.43409 (15)	0.3242 (2)	0.3507 (6)	0.0224 (7)	0.505 (4)
C9	0.4472 (5)	0.2368 (8)	0.3839 (11)	0.0217 (13)	0.505 (4)
H9A	0.4166	0.1945	0.3394	0.026*	0.505 (4)
C10	0.5042 (5)	0.2072 (5)	0.4815 (14)	0.0368 (18)	0.505 (4)
C11	0.54930 (16)	0.2695 (3)	0.5297 (6)	0.0348 (9)	0.505 (4)
H11A	0.5890	0.2515	0.5885	0.042*	0.505 (4)
C12	0.53779 (14)	0.3580 (3)	0.4939 (5)	0.0345 (9)	0.505 (4)
H12A	0.5693	0.4000	0.5301	0.041*	0.505 (4)
C13	0.48029 (14)	0.3853 (2)	0.4052 (5)	0.0286 (8)	0.505 (4)
H13A	0.4725	0.4460	0.3816	0.034*	0.505 (4)
Cl1X	0.52750 (12)	0.11634 (16)	0.5138 (4)	0.0336 (4)	0.495 (4)
O1X	0.3491 (3)	0.4332 (4)	0.3044 (10)	0.0294 (11)	0.495 (4)
O2X	0.3302 (7)	0.2910 (8)	0.2304 (12)	0.0273 (15)	0.495 (4)
C7X	0.3620 (3)	0.3525 (4)	0.3103 (9)	0.0225 (11)	0.495 (4)
C8X	0.42352 (17)	0.3289 (2)	0.4266 (6)	0.0222 (8)	0.495 (4)
C9X	0.4418 (5)	0.2415 (8)	0.4305 (11)	0.0223 (14)	0.495 (4)
H9XA	0.4152	0.1963	0.3748	0.027*	0.495 (4)
C10X	0.5005 (5)	0.2239 (4)	0.5195 (13)	0.0314 (16)	0.495 (4)
C11X	0.53950 (16)	0.2854 (3)	0.6185 (6)	0.0319 (9)	0.495 (4)
H11B	0.5787	0.2691	0.6844	0.038*	0.495 (4)
C12X	0.51893 (15)	0.3713 (2)	0.6175 (5)	0.0303 (8)	0.495 (4)
H12B	0.5445	0.4155	0.6820	0.036*	0.495 (4)
C13X	0.46134 (15)	0.3931 (2)	0.5228 (5)	0.0272 (8)	0.495 (4)
H13B	0.4474	0.4522	0.5233	0.033*	0.495 (4)
N1	0.25283 (5)	0.49267 (8)	0.09853 (17)	0.0197 (3)
N2	0.21460 (7)	0.35423 (9)	0.0235 (2)	0.0337 (4)
C1	0.20717 (6)	0.44124 (10)	0.0094 (2)	0.0211 (3)
C2	0.15454 (7)	0.48210 (10)	−0.0898 (2)	0.0238 (3)
H2A	0.1223	0.4479	−0.1572	0.029*
C3	0.15048 (7)	0.57153 (11)	−0.0877 (2)	0.0307 (4)
H3A	0.1149	0.5996	−0.1533	0.037*
C4	0.19795 (8)	0.62255 (11)	0.0095 (3)	0.0363 (4)
H4A	0.1944	0.6848	0.0121	0.044*
C5	0.24940 (7)	0.58195 (10)	0.1006 (2)	0.0257 (3)
C6	0.30466 (8)	0.62859 (11)	0.2048 (3)	0.0372 (4)
H6A	0.2955	0.6913	0.2136	0.056*
H6B	0.3388	0.6213	0.1402	0.056*
H6C	0.3157	0.6036	0.3284	0.056*
H1N1	0.1883 (11)	0.3210 (14)	−0.050 (3)	0.046 (6)*
H2N2	0.2887 (10)	0.4672 (15)	0.165 (3)	0.050 (6)*
H1N2	0.2487 (11)	0.3311 (14)	0.077 (3)	0.044 (6)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0260 (10)	0.0318 (11)	0.0523 (8)	0.0162 (6)	0.0001 (7)	0.0009 (8)
O1	0.016 (2)	0.0172 (13)	0.051 (4)	−0.0007 (13)	−0.0063 (17)	−0.0018 (18)
O2	0.020 (2)	0.0134 (18)	0.043 (4)	0.0000 (14)	−0.014 (3)	0.000 (3)
C7	0.012 (2)	0.0175 (16)	0.035 (3)	−0.0021 (13)	−0.0015 (19)	0.0004 (19)
C8	0.0103 (15)	0.0277 (16)	0.027 (2)	0.0008 (11)	−0.0011 (13)	−0.0050 (15)
C9	0.014 (2)	0.0240 (19)	0.028 (4)	0.0072 (15)	0.006 (3)	−0.005 (3)
C10	0.013 (2)	0.037 (3)	0.055 (4)	0.016 (2)	−0.006 (2)	−0.016 (2)
C11	0.0138 (16)	0.059 (3)	0.029 (2)	0.0094 (15)	−0.0032 (14)	−0.0084 (17)
C12	0.0134 (15)	0.054 (2)	0.0331 (19)	−0.0063 (14)	−0.0032 (12)	−0.0057 (15)
C13	0.0182 (15)	0.0351 (17)	0.0299 (18)	−0.0033 (12)	−0.0019 (12)	−0.0044 (13)
Cl1X	0.0247 (9)	0.0289 (10)	0.0442 (7)	0.0119 (6)	−0.0011 (6)	0.0025 (7)
O1X	0.021 (3)	0.0190 (14)	0.043 (3)	−0.0005 (14)	−0.0066 (16)	−0.0035 (17)
O2X	0.0172 (18)	0.020 (2)	0.038 (4)	−0.0025 (14)	−0.011 (3)	0.002 (2)
C7X	0.013 (2)	0.0213 (18)	0.032 (3)	−0.0016 (14)	0.0023 (18)	0.002 (2)
C8X	0.0144 (16)	0.0268 (17)	0.0247 (19)	−0.0003 (12)	0.0018 (14)	−0.0018 (15)
C9X	0.010 (2)	0.035 (3)	0.023 (3)	0.0040 (18)	0.005 (2)	−0.003 (3)
C10X	0.021 (2)	0.022 (3)	0.051 (4)	0.016 (2)	0.007 (3)	0.001 (3)
C11X	0.0132 (15)	0.052 (2)	0.0276 (19)	0.0019 (14)	−0.0032 (14)	−0.0008 (17)
C12X	0.0193 (15)	0.0391 (19)	0.0294 (18)	−0.0090 (13)	−0.0031 (13)	−0.0029 (14)
C13X	0.0243 (16)	0.0254 (16)	0.0302 (18)	−0.0062 (12)	0.0011 (13)	−0.0025 (12)
N1	0.0155 (6)	0.0161 (6)	0.0264 (6)	0.0011 (4)	0.0012 (5)	0.0000 (4)
N2	0.0220 (7)	0.0179 (6)	0.0526 (9)	0.0009 (5)	−0.0147 (6)	−0.0074 (6)
C1	0.0171 (7)	0.0200 (7)	0.0251 (7)	0.0015 (5)	0.0012 (5)	−0.0020 (5)
C2	0.0165 (7)	0.0285 (8)	0.0253 (7)	0.0031 (6)	0.0008 (5)	−0.0008 (6)
C3	0.0232 (8)	0.0318 (9)	0.0356 (9)	0.0091 (6)	0.0016 (6)	0.0068 (7)
C4	0.0313 (9)	0.0191 (7)	0.0563 (11)	0.0053 (6)	0.0030 (8)	0.0057 (7)
C5	0.0231 (8)	0.0179 (7)	0.0366 (8)	−0.0001 (6)	0.0068 (6)	0.0006 (6)
C6	0.0254 (9)	0.0189 (7)	0.0652 (12)	−0.0044 (6)	0.0036 (8)	−0.0039 (7)

Cl1—C10	1.753 (7)	C11X—C12X	1.385 (5)
O1—C7	1.253 (6)	C11X—H11B	0.9500
O2—C7	1.258 (14)	C12X—C13X	1.383 (4)
C7—C8	1.509 (8)	C12X—H12B	0.9500
C8—C9	1.372 (12)	C13X—H13B	0.9500
C8—C13	1.390 (5)	N1—C1	1.3530 (18)
C9—C10	1.413 (16)	N1—C5	1.3599 (19)
C9—H9A	0.9500	N1—H2N2	0.94 (2)
C10—C11	1.379 (11)	N2—C1	1.335 (2)
C11—C12	1.385 (6)	N2—H1N1	0.88 (2)
C11—H11A	0.9500	N2—H1N2	0.86 (2)
C12—C13	1.390 (4)	C1—C2	1.4067 (19)
C12—H12A	0.9500	C2—C3	1.363 (2)
C13—H13A	0.9500	C2—H2A	0.9500
Cl1X—C10X	1.747 (6)	C3—C4	1.398 (2)
O1X—C7X	1.259 (7)	C3—H3A	0.9500
O2X—C7X	1.253 (14)	C4—C5	1.365 (2)
C7X—C8X	1.519 (8)	C4—H4A	0.9500
C8X—C9X	1.389 (13)	C5—C6	1.503 (2)
C8X—C13X	1.395 (5)	C6—H6A	0.9800
C9X—C10X	1.377 (17)	C6—H6B	0.9800
C9X—H9XA	0.9500	C6—H6C	0.9800
C10X—C11X	1.388 (12)
O1—C7—O2	123.8 (9)	C10X—C11X—H11B	121.4
O1—C7—C8	117.2 (6)	C13X—C12X—C11X	120.3 (3)
O2—C7—C8	118.9 (8)	C13X—C12X—H12B	119.9
C9—C8—C13	118.3 (6)	C11X—C12X—H12B	119.9
C9—C8—C7	121.2 (6)	C12X—C13X—C8X	120.4 (3)
C13—C8—C7	120.5 (4)	C12X—C13X—H13B	119.8
C8—C9—C10	122.8 (10)	C8X—C13X—H13B	119.8
C8—C9—H9A	118.6	C1—N1—C5	122.95 (13)
C10—C9—H9A	118.6	C1—N1—H2N2	120.4 (14)
C11—C10—C9	117.1 (7)	C5—N1—H2N2	116.7 (14)
C11—C10—Cl1	124.2 (7)	C1—N2—H1N1	117.5 (14)
C9—C10—Cl1	118.7 (8)	C1—N2—H1N2	121.7 (14)
C10—C11—C12	121.2 (4)	H1N1—N2—H1N2	119 (2)
C10—C11—H11A	119.4	N2—C1—N1	117.63 (13)
C12—C11—H11A	119.4	N2—C1—C2	123.89 (14)
C11—C12—C13	120.1 (3)	N1—C1—C2	118.48 (13)
C11—C12—H12A	119.9	C3—C2—C1	119.04 (14)
C13—C12—H12A	119.9	C3—C2—H2A	120.5
C8—C13—C12	120.3 (3)	C1—C2—H2A	120.5
C8—C13—H13A	119.8	C2—C3—C4	120.93 (14)
C12—C13—H13A	119.8	C2—C3—H3A	119.5
O2X—C7X—O1X	127.3 (10)	C4—C3—H3A	119.5
O2X—C7X—C8X	117.5 (8)	C5—C4—C3	119.24 (15)
O1X—C7X—C8X	115.2 (7)	C5—C4—H4A	120.4
C9X—C8X—C13X	120.8 (6)	C3—C4—H4A	120.4
C9X—C8X—C7X	117.9 (6)	N1—C5—C4	119.32 (15)
C13X—C8X—C7X	121.3 (4)	N1—C5—C6	115.76 (13)
C10X—C9X—C8X	116.4 (9)	C4—C5—C6	124.91 (15)
C10X—C9X—H9XA	121.8	C5—C6—H6A	109.5
C8X—C9X—H9XA	121.8	C5—C6—H6B	109.5
C9X—C10X—C11X	124.5 (7)	H6A—C6—H6B	109.5
C9X—C10X—Cl1X	118.1 (8)	C5—C6—H6C	109.5
C11X—C10X—Cl1X	117.3 (7)	H6A—C6—H6C	109.5
C12X—C11X—C10X	117.3 (4)	H6B—C6—H6C	109.5
C12X—C11X—H11B	121.4
O1—C7—C8—C9	169.3 (5)	C7X—C8X—C9X—C10X	172.7 (6)
O2—C7—C8—C9	−9.3 (8)	C8X—C9X—C10X—C11X	6.5 (12)
O1—C7—C8—C13	−11.7 (7)	C8X—C9X—C10X—Cl1X	−175.4 (5)
O2—C7—C8—C13	169.7 (6)	C9X—C10X—C11X—C12X	−4.3 (11)
C13—C8—C9—C10	4.3 (9)	Cl1X—C10X—C11X—C12X	177.7 (4)
C7—C8—C9—C10	−176.7 (6)	C10X—C11X—C12X—C13X	1.0 (7)
C8—C9—C10—C11	−5.7 (11)	C11X—C12X—C13X—C8X	−0.4 (6)
C8—C9—C10—Cl1	177.0 (5)	C9X—C8X—C13X—C12X	2.8 (7)
C9—C10—C11—C12	3.9 (10)	C7X—C8X—C13X—C12X	−175.5 (3)
Cl1—C10—C11—C12	−178.8 (5)	C5—N1—C1—N2	−177.15 (15)
C10—C11—C12—C13	−1.1 (7)	C5—N1—C1—C2	1.9 (2)
C9—C8—C13—C12	−1.2 (6)	N2—C1—C2—C3	176.80 (16)
C7—C8—C13—C12	179.9 (4)	N1—C1—C2—C3	−2.2 (2)
C11—C12—C13—C8	−0.4 (6)	C1—C2—C3—C4	0.7 (3)
O2X—C7X—C8X—C9X	2.7 (9)	C2—C3—C4—C5	1.2 (3)
O1X—C7X—C8X—C9X	−176.6 (5)	C1—N1—C5—C4	0.0 (2)
O2X—C7X—C8X—C13X	−178.9 (6)	C1—N1—C5—C6	−179.36 (14)
O1X—C7X—C8X—C13X	1.8 (6)	C3—C4—C5—N1	−1.5 (3)
C13X—C8X—C9X—C10X	−5.7 (9)	C3—C4—C5—C6	177.75 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2N2···O1	0.94 (2)	1.69 (2)	2.614 (7)	168 (2)
N2—H1N2···O2	0.86 (2)	1.98 (3)	2.832 (14)	170 (2)
N2—H1N1···O2i	0.88 (2)	2.06 (2)	2.853 (11)	150 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2N2⋯O1	0.94 (2)	1.69 (2)	2.614 (7)	168 (2)
N2—H1N2⋯O2	0.86 (2)	1.98 (3)	2.832 (14)	170 (2)
N2—H1N1⋯O2i	0.88 (2)	2.06 (2)	2.853 (11)	150 (2)

Symmetry code: (i) .