2-Amino-5-methyl-pyridinium nicotinate.

In the title compound, C(6)H(9)N(2) (+)·C(6)H(4)NO(2) (-), the 2-amino-5-methyl-pyridinium cation is essentially planar, with a maximum deviation of 0.023 (2) Å. In the crystal, the cations and anions are linked via strong N-H⋯O hydrogen bonds, forming a two dimensional network parallel to (100). In addition, π⋯π inter-actions involving the pyridinium and pyridine rings, with centroid-centroid distances of 3.6383 (8) Å, are observed.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For nicotinic acid, see: Athimoolam & Rajaram (2005 ▶); Lorenzen et al. (2001 ▶); Gielen et al. (1992 ▶); Kim et al. (2004 ▶). For a related structure, see: Nahringbauer & Kvick (1977 ▶). 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 ▶).

Experimental

Crystal data

C6H9N2 +·C6H4NO2 −

M = 231.25

Monoclinic,

a = 9.4877 (3) Å

b = 11.1403 (3) Å

c = 11.7611 (3) Å

β = 110.113 (2)°

V = 1167.29 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.63 × 0.11 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.944, T max = 0.990

14482 measured reflections

3870 independent reflections

2240 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.144

S = 1.05

3870 reflections

195 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.20 e Å−3

Δρmin = −0.20 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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810005970/sj2728sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005970/sj2728Isup2.hkl

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

C6H9N2+·C6H4NO2−	F(000) = 488
Mr = 231.25	Dx = 1.316 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4062 reflections
a = 9.4877 (3) Å	θ = 2.6–26.7°
b = 11.1403 (3) Å	µ = 0.09 mm−1
c = 11.7611 (3) Å	T = 296 K
β = 110.113 (2)°	Needle, colourless
V = 1167.29 (6) Å3	0.63 × 0.11 × 0.11 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	3870 independent reflections
Radiation source: fine-focus sealed tube	2240 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 31.6°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→13
Tmin = 0.944, Tmax = 0.990	k = −15→16
14482 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0668P)2 + 0.0299P] where P = (Fo2 + 2Fc2)/3
3870 reflections	(Δ/σ)max < 0.001
195 parameters	Δρmax = 0.20 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

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
N1	0.02188 (12)	0.19316 (10)	0.05859 (9)	0.0442 (3)
N2	−0.10328 (14)	0.22434 (12)	0.19337 (12)	0.0585 (3)
C1	−0.00012 (14)	0.16474 (11)	0.16305 (10)	0.0442 (3)
C2	0.08966 (14)	0.07300 (12)	0.23423 (12)	0.0491 (3)
C3	0.19225 (14)	0.01646 (12)	0.19651 (12)	0.0503 (3)
C4	0.21339 (13)	0.04715 (12)	0.08710 (11)	0.0478 (3)
C5	0.12592 (14)	0.13727 (12)	0.02171 (11)	0.0459 (3)
C6	0.33142 (17)	−0.01226 (17)	0.04856 (14)	0.0688 (4)
H6A	0.3313	0.0225	−0.0262	0.103*
H6B	0.3105	−0.0966	0.0373	0.103*
H6C	0.4280	−0.0007	0.1098	0.103*
O1	0.72673 (12)	0.39748 (10)	1.02919 (8)	0.0659 (3)
O2	0.86277 (12)	0.36701 (9)	0.91118 (8)	0.0617 (3)
N3	0.68920 (14)	0.67197 (11)	0.70931 (11)	0.0599 (3)
C7	0.58423 (16)	0.73306 (14)	0.73619 (15)	0.0627 (4)
C8	0.53402 (17)	0.70341 (14)	0.82858 (16)	0.0661 (4)
C9	0.59378 (16)	0.60379 (13)	0.89864 (14)	0.0559 (4)
C10	0.70147 (13)	0.53689 (11)	0.87228 (11)	0.0434 (3)
C11	0.74469 (15)	0.57565 (12)	0.77763 (12)	0.0514 (3)
C12	0.76845 (14)	0.42525 (11)	0.94349 (11)	0.0462 (3)
H2A	0.0757 (14)	0.0528 (11)	0.3103 (13)	0.053 (4)*
H3A	0.2576 (15)	−0.0480 (13)	0.2476 (13)	0.059 (4)*
H5A	0.1359 (14)	0.1651 (11)	−0.0511 (12)	0.047 (3)*
H7A	0.5424 (18)	0.8056 (15)	0.6832 (15)	0.076 (5)*
H8A	0.458 (2)	0.7512 (15)	0.8436 (15)	0.082 (5)*
H9A	0.5651 (16)	0.5825 (13)	0.9650 (15)	0.069 (5)*
H11A	0.8211 (16)	0.5323 (13)	0.7567 (12)	0.061 (4)*
H1N1	−0.0397 (17)	0.2561 (14)	0.0051 (14)	0.069 (4)*
H1N2	−0.1231 (16)	0.1988 (13)	0.2573 (15)	0.065 (4)*
H2N2	−0.159 (2)	0.2841 (16)	0.1413 (16)	0.081 (5)*

	U11	U22	U33	U12	U13	U23
N1	0.0485 (5)	0.0474 (6)	0.0391 (5)	0.0001 (5)	0.0180 (4)	0.0027 (5)
N2	0.0715 (8)	0.0654 (8)	0.0503 (6)	0.0121 (6)	0.0358 (6)	0.0098 (6)
C1	0.0494 (6)	0.0474 (7)	0.0389 (6)	−0.0066 (5)	0.0191 (5)	−0.0013 (5)
C2	0.0515 (7)	0.0553 (8)	0.0425 (6)	−0.0048 (6)	0.0186 (5)	0.0082 (6)
C3	0.0462 (7)	0.0532 (8)	0.0502 (7)	−0.0018 (6)	0.0150 (6)	0.0085 (6)
C4	0.0437 (6)	0.0549 (8)	0.0461 (7)	−0.0036 (6)	0.0171 (5)	−0.0009 (6)
C5	0.0468 (7)	0.0558 (8)	0.0380 (6)	−0.0039 (6)	0.0183 (5)	0.0002 (6)
C6	0.0611 (8)	0.0880 (11)	0.0618 (9)	0.0186 (8)	0.0268 (7)	0.0076 (8)
O1	0.0818 (7)	0.0743 (7)	0.0557 (6)	0.0160 (5)	0.0417 (5)	0.0135 (5)
O2	0.0788 (6)	0.0671 (6)	0.0499 (5)	0.0249 (5)	0.0358 (5)	0.0115 (4)
N3	0.0668 (7)	0.0543 (7)	0.0576 (7)	0.0011 (6)	0.0199 (6)	0.0071 (6)
C7	0.0590 (8)	0.0479 (8)	0.0726 (10)	−0.0014 (7)	0.0117 (7)	0.0052 (7)
C8	0.0556 (8)	0.0504 (8)	0.0954 (12)	0.0041 (7)	0.0299 (8)	−0.0050 (8)
C9	0.0571 (8)	0.0506 (8)	0.0680 (9)	−0.0019 (6)	0.0318 (7)	−0.0043 (7)
C10	0.0427 (6)	0.0455 (7)	0.0425 (6)	−0.0028 (5)	0.0154 (5)	−0.0048 (5)
C11	0.0545 (7)	0.0530 (8)	0.0495 (7)	0.0018 (6)	0.0214 (6)	0.0005 (6)
C12	0.0519 (7)	0.0514 (8)	0.0376 (6)	0.0001 (6)	0.0185 (5)	−0.0050 (5)

N1—C1	1.3526 (14)	C6—H6B	0.9600
N1—C5	1.3582 (16)	C6—H6C	0.9600
N1—H1N1	0.988 (16)	O1—C12	1.2420 (14)
N2—C1	1.3289 (17)	O2—C12	1.2650 (15)
N2—H1N2	0.883 (16)	N3—C7	1.331 (2)
N2—H2N2	0.936 (19)	N3—C11	1.3354 (17)
C1—C2	1.4073 (18)	C7—C8	1.368 (2)
C2—C3	1.3558 (18)	C7—H7A	1.015 (17)
C2—H2A	0.974 (14)	C8—C9	1.382 (2)
C3—C4	1.4108 (18)	C8—H8A	0.964 (18)
C3—H3A	1.002 (14)	C9—C10	1.3832 (18)
C4—C5	1.3598 (18)	C9—H9A	0.941 (16)
C4—C6	1.4989 (19)	C10—C11	1.3812 (17)
C5—H5A	0.946 (13)	C10—C12	1.5121 (18)
C6—H6A	0.9600	C11—H11A	0.970 (15)
C1—N1—C5	122.61 (11)	H6A—C6—H6B	109.5
C1—N1—H1N1	120.1 (8)	C4—C6—H6C	109.5
C5—N1—H1N1	117.3 (8)	H6A—C6—H6C	109.5
C1—N2—H1N2	117.4 (10)	H6B—C6—H6C	109.5
C1—N2—H2N2	119.0 (10)	C7—N3—C11	116.12 (13)
H1N2—N2—H2N2	123.2 (14)	N3—C7—C8	123.94 (14)
N2—C1—N1	118.99 (12)	N3—C7—H7A	115.3 (9)
N2—C1—C2	123.65 (11)	C8—C7—H7A	120.7 (9)
N1—C1—C2	117.35 (11)	C7—C8—C9	118.93 (14)
C3—C2—C1	119.90 (12)	C7—C8—H8A	120.1 (10)
C3—C2—H2A	122.2 (7)	C9—C8—H8A	120.9 (10)
C1—C2—H2A	117.9 (7)	C8—C9—C10	118.82 (14)
C2—C3—C4	121.95 (13)	C8—C9—H9A	121.4 (9)
C2—C3—H3A	120.2 (8)	C10—C9—H9A	119.8 (9)
C4—C3—H3A	117.9 (8)	C11—C10—C9	117.33 (13)
C5—C4—C3	116.37 (12)	C11—C10—C12	121.26 (11)
C5—C4—C6	121.94 (12)	C9—C10—C12	121.41 (12)
C3—C4—C6	121.61 (12)	N3—C11—C10	124.84 (13)
N1—C5—C4	121.81 (12)	N3—C11—H11A	114.9 (8)
N1—C5—H5A	116.7 (8)	C10—C11—H11A	120.2 (8)
C4—C5—H5A	121.5 (8)	O1—C12—O2	124.88 (12)
C4—C6—H6A	109.5	O1—C12—C10	117.64 (11)
C4—C6—H6B	109.5	O2—C12—C10	117.48 (10)
C5—N1—C1—N2	179.41 (11)	N3—C7—C8—C9	−0.5 (2)
C5—N1—C1—C2	−0.22 (18)	C7—C8—C9—C10	−0.5 (2)
N2—C1—C2—C3	179.87 (12)	C8—C9—C10—C11	1.1 (2)
N1—C1—C2—C3	−0.52 (18)	C8—C9—C10—C12	−178.48 (12)
C1—C2—C3—C4	0.4 (2)	C7—N3—C11—C10	−0.3 (2)
C2—C3—C4—C5	0.46 (19)	C9—C10—C11—N3	−0.7 (2)
C2—C3—C4—C6	177.42 (13)	C12—C10—C11—N3	178.87 (12)
C1—N1—C5—C4	1.14 (19)	C11—C10—C12—O1	178.34 (12)
C3—C4—C5—N1	−1.21 (18)	C9—C10—C12—O1	−2.15 (19)
C6—C4—C5—N1	−178.16 (12)	C11—C10—C12—O2	−1.73 (19)
C11—N3—C7—C8	0.9 (2)	C9—C10—C12—O2	177.79 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2i	0.988 (16)	1.703 (16)	2.6899 (15)	176.8 (16)
N2—H1N2···O2ii	0.883 (16)	1.999 (16)	2.8756 (17)	171.7 (15)
N2—H2N2···O1i	0.936 (18)	1.878 (18)	2.8122 (17)	176.6 (17)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2i	0.988 (16)	1.703 (16)	2.6899 (15)	176.8 (16)
N2—H1N2⋯O2ii	0.883 (16)	1.999 (16)	2.8756 (17)	171.7 (15)
N2—H2N2⋯O1i	0.936 (18)	1.878 (18)	2.8122 (17)	176.6 (17)

Symmetry codes: (i) ; (ii) .