2-Amino-4-methyl-pyridinium (E)-3-carb-oxy-prop-2-enoate.

In the title salt, C(6)H(9)N(2) (+)·C(4)H(3)O(4) (-), the dihedral angle between the pyridine ring and the plane formed by the hydrogen fumarate anion is 85.67 (6)°. Excluding the amino and methyl groups, the atoms of the cation are coplanar, with a maximum deviation of 0.005 (1) Å. In the crystal structure, 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. These motifs are further connected through N-H⋯O and C-H⋯O hydrogen bonds, leading to a supra-molecular chain along the c axis. These chains are further cross-linked via a pair of O-H⋯O hydrogen bonds involving centrosymmetrically related hydrogen fumarate anions, forming a two-dimensional network parallel to (101). These planes are further interconnected by O-H⋯O interactions into a three-dimensional network.

Related literature

For applications of inter­molecular inter­actions, see: Lam & Mak (2000 ▶). For related structures, see: Büyükgüngör & Odabąsoğlu (2006 ▶); Hosomi et al. (2000 ▶); Smith et al. (2007 ▶); Cao et al. (2004 ▶); Natarajan et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For reference 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 +·C4H3O4 −

M = 224.22

Monoclinic,

a = 5.0058 (16) Å

b = 19.814 (7) Å

c = 11.286 (4) Å

β = 108.332 (13)°

V = 1062.6 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.36 × 0.10 × 0.07 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.962, T max = 0.992

12900 measured reflections

3387 independent reflections

2573 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.168

S = 1.07

3387 reflections

181 parameters

All H-atom parameters refined

Δρmax = 0.51 e Å−3

Δρmin = −0.32 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/S1600536810026292/wn2399sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026292/wn2399Isup2.hkl

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

C6H9N2+·C4H3O4−	F(000) = 472
Mr = 224.22	Dx = 1.402 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2803 reflections
a = 5.0058 (16) Å	θ = 2.8–31.0°
b = 19.814 (7) Å	µ = 0.11 mm−1
c = 11.286 (4) Å	T = 100 K
β = 108.332 (13)°	Needle, colourless
V = 1062.6 (6) Å3	0.36 × 0.10 × 0.07 mm
Z = 4

Bruker APEXII DUO CCD area-detector diffractometer	3387 independent reflections
Radiation source: fine-focus sealed tube	2573 reflections with I > 2σ(I)
graphite	Rint = 0.041
φ and ω scans	θmax = 31.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
Tmin = 0.962, Tmax = 0.992	k = −22→28
12900 measured reflections	l = −16→16

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.168	All H-atom parameters refined
S = 1.07	w = 1/[σ2(Fo2) + (0.106P)2 + 0.0446P] where P = (Fo2 + 2Fc2)/3
3387 reflections	(Δ/σ)max = 0.001
181 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.32 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 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	−0.1142 (2)	0.80864 (6)	0.55566 (10)	0.0138 (2)
N2	0.0376 (2)	0.76324 (6)	0.75413 (11)	0.0166 (2)
C1	0.0731 (3)	0.80768 (7)	0.67234 (11)	0.0129 (3)
C2	0.2978 (3)	0.85492 (7)	0.70188 (12)	0.0143 (3)
C3	0.3220 (3)	0.90042 (7)	0.61461 (12)	0.0153 (3)
C4	0.1210 (3)	0.89903 (7)	0.49325 (12)	0.0176 (3)
C5	−0.0911 (3)	0.85296 (7)	0.46726 (12)	0.0159 (3)
C6	0.5539 (3)	0.95182 (8)	0.64658 (13)	0.0198 (3)
O1	0.4413 (2)	0.77430 (5)	−0.00598 (9)	0.0167 (2)
O2	0.5841 (2)	0.82660 (5)	0.17910 (9)	0.0187 (2)
O3	−0.33328 (19)	0.94128 (5)	−0.04434 (9)	0.0170 (2)
O4	−0.2087 (2)	0.98609 (5)	0.14785 (9)	0.0184 (2)
C7	0.4153 (3)	0.81746 (7)	0.07303 (11)	0.0129 (3)
C8	0.1559 (3)	0.86036 (7)	0.03171 (12)	0.0144 (3)
C9	0.0841 (3)	0.90251 (7)	0.10791 (12)	0.0150 (3)
C10	−0.1721 (3)	0.94438 (7)	0.06278 (12)	0.0132 (3)
H1O4	−0.368 (4)	1.0119 (9)	0.1114 (16)	0.020*
H1N1	−0.278 (4)	0.7781 (9)	0.5333 (16)	0.016*
H1N2	−0.124 (4)	0.7315 (9)	0.7264 (16)	0.016*
H2N2	0.141 (4)	0.7622 (9)	0.8262 (17)	0.016*
H2A	0.428 (4)	0.8529 (9)	0.7855 (16)	0.016*
H4A	0.137 (4)	0.9308 (9)	0.4299 (16)	0.016*
H5A	−0.244 (3)	0.8495 (9)	0.3834 (15)	0.016*
H6A	0.655 (4)	0.9509 (10)	0.5852 (16)	0.020*
H6B	0.683 (4)	0.9461 (9)	0.7285 (17)	0.020*
H6C	0.457 (4)	0.9960 (10)	0.6385 (16)	0.020*
H8A	0.029 (4)	0.8563 (9)	−0.0593 (16)	0.016*
H9A	0.198 (4)	0.9063 (9)	0.1949 (16)	0.016*

	U11	U22	U33	U12	U13	U23
N1	0.0130 (5)	0.0153 (6)	0.0118 (5)	−0.0028 (4)	0.0020 (4)	−0.0010 (4)
N2	0.0164 (5)	0.0181 (6)	0.0123 (5)	−0.0050 (4)	0.0004 (4)	0.0012 (4)
C1	0.0126 (5)	0.0137 (6)	0.0119 (5)	−0.0010 (4)	0.0031 (4)	−0.0015 (4)
C2	0.0145 (5)	0.0156 (6)	0.0127 (5)	−0.0027 (4)	0.0039 (4)	−0.0025 (5)
C3	0.0161 (6)	0.0164 (6)	0.0146 (6)	−0.0032 (5)	0.0064 (5)	−0.0024 (5)
C4	0.0206 (6)	0.0197 (7)	0.0135 (6)	−0.0038 (5)	0.0065 (5)	−0.0001 (5)
C5	0.0167 (6)	0.0184 (7)	0.0115 (5)	−0.0012 (5)	0.0029 (4)	−0.0011 (5)
C6	0.0208 (6)	0.0206 (7)	0.0188 (6)	−0.0082 (5)	0.0074 (5)	−0.0024 (5)
O1	0.0160 (4)	0.0174 (5)	0.0143 (4)	0.0045 (3)	0.0013 (3)	−0.0027 (4)
O2	0.0155 (4)	0.0238 (6)	0.0132 (4)	0.0066 (4)	−0.0007 (3)	−0.0031 (4)
O3	0.0152 (4)	0.0195 (5)	0.0144 (4)	0.0052 (3)	0.0019 (4)	−0.0021 (4)
O4	0.0167 (5)	0.0194 (5)	0.0169 (5)	0.0057 (4)	0.0022 (4)	−0.0046 (4)
C7	0.0121 (5)	0.0129 (6)	0.0131 (5)	0.0014 (4)	0.0033 (4)	0.0014 (4)
C8	0.0127 (5)	0.0150 (6)	0.0147 (6)	0.0027 (4)	0.0030 (4)	−0.0002 (5)
C9	0.0131 (5)	0.0166 (6)	0.0141 (6)	0.0028 (4)	0.0023 (4)	−0.0003 (5)
C10	0.0121 (5)	0.0134 (6)	0.0143 (6)	−0.0001 (4)	0.0043 (4)	−0.0009 (4)

N1—C1	1.3553 (16)	C6—H6A	0.977 (18)
N1—C5	1.3611 (17)	C6—H6B	0.953 (19)
N1—H1N1	0.987 (18)	C6—H6C	0.991 (19)
N2—C1	1.3276 (17)	O1—C7	1.2714 (15)
N2—H1N2	0.994 (18)	O2—C7	1.2424 (16)
N2—H2N2	0.816 (19)	O3—C10	1.2259 (16)
C1—C2	1.4202 (18)	O4—C10	1.3224 (15)
C2—C3	1.3683 (18)	O4—H1O4	0.93 (2)
C2—H2A	0.964 (17)	C7—C8	1.4987 (18)
C3—C4	1.4219 (19)	C8—C9	1.3269 (18)
C3—C6	1.5006 (19)	C8—H8A	1.027 (17)
C4—C5	1.3604 (19)	C9—C10	1.4769 (18)
C4—H4A	0.976 (17)	C9—H9A	0.970 (18)
C5—H5A	1.015 (17)
C1—N1—C5	121.94 (11)	N1—C5—H5A	115.3 (10)
C1—N1—H1N1	120.4 (10)	C3—C6—H6A	110.5 (11)
C5—N1—H1N1	117.6 (10)	C3—C6—H6B	112.9 (11)
C1—N2—H1N2	118.4 (10)	H6A—C6—H6B	110.0 (16)
C1—N2—H2N2	121.9 (13)	C3—C6—H6C	105.0 (11)
H1N2—N2—H2N2	119.7 (16)	H6A—C6—H6C	107.3 (15)
N2—C1—N1	118.80 (11)	H6B—C6—H6C	110.9 (15)
N2—C1—C2	122.92 (12)	C10—O4—H1O4	108.6 (11)
N1—C1—C2	118.27 (11)	O2—C7—O1	125.82 (12)
C3—C2—C1	120.53 (12)	O2—C7—C8	118.51 (11)
C3—C2—H2A	123.2 (11)	O1—C7—C8	115.67 (11)
C1—C2—H2A	116.3 (11)	C9—C8—C7	122.70 (12)
C2—C3—C4	119.00 (12)	C9—C8—H8A	119.2 (10)
C2—C3—C6	120.72 (12)	C7—C8—H8A	118.1 (10)
C4—C3—C6	120.28 (12)	C8—C9—C10	120.85 (12)
C5—C4—C3	119.24 (12)	C8—C9—H9A	120.8 (11)
C5—C4—H4A	121.0 (10)	C10—C9—H9A	118.3 (11)
C3—C4—H4A	119.7 (11)	O3—C10—O4	123.28 (12)
C4—C5—N1	121.02 (12)	O3—C10—C9	122.87 (11)
C4—C5—H5A	123.7 (10)	O4—C10—C9	113.83 (11)
C5—N1—C1—N2	179.79 (12)	C3—C4—C5—N1	0.3 (2)
C5—N1—C1—C2	0.38 (18)	C1—N1—C5—C4	−0.8 (2)
N2—C1—C2—C3	−178.88 (12)	O2—C7—C8—C9	−7.3 (2)
N1—C1—C2—C3	0.51 (19)	O1—C7—C8—C9	172.67 (13)
C1—C2—C3—C4	−1.0 (2)	C7—C8—C9—C10	179.34 (11)
C1—C2—C3—C6	178.11 (12)	C8—C9—C10—O3	2.0 (2)
C2—C3—C4—C5	0.5 (2)	C8—C9—C10—O4	−177.01 (12)
C6—C3—C4—C5	−178.53 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1O4···O3i	0.928 (19)	1.720 (19)	2.6472 (17)	179 (2)
N1—H1N1···O1ii	0.987 (18)	1.689 (18)	2.6761 (16)	179.5 (17)
N2—H1N2···O2ii	0.994 (18)	1.804 (18)	2.7979 (16)	179.0 (16)
N2—H2N2···O1iii	0.816 (19)	2.028 (19)	2.8320 (18)	168.5 (18)
C2—H2A···O3iv	0.964 (18)	2.596 (18)	3.349 (2)	135.1 (14)
C5—H5A···O2v	1.015 (16)	2.239 (16)	3.189 (2)	155.0 (13)
C6—H6B···O3iv	0.954 (19)	2.592 (19)	3.360 (2)	137.8 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H1O4⋯O3i	0.928 (19)	1.720 (19)	2.6472 (17)	179 (2)
N1—H1N1⋯O1ii	0.987 (18)	1.689 (18)	2.6761 (16)	179.5 (17)
N2—H1N2⋯O2ii	0.994 (18)	1.804 (18)	2.7979 (16)	179.0 (16)
N2—H2N2⋯O1iii	0.816 (19)	2.028 (19)	2.8320 (18)	168.5 (18)
C2—H2A⋯O3iv	0.964 (18)	2.596 (18)	3.349 (2)	135.1 (14)
C5—H5A⋯O2v	1.015 (16)	2.239 (16)	3.189 (2)	155.0 (13)
C6—H6B⋯O3iv	0.954 (19)	2.592 (19)	3.360 (2)	137.8 (16)

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