2,3-Diamino-pyridinium (2E,4E)-hexa-2,4-dienoate.

In the title salt, C(5)H(8)N(3) (+)·C(6)H(7)O(2) (-), the pyridine N atom of the 2,3-diamino-pyridine mol-ecule is protonated. The 2,3-diamino-pyridinium cation is essentially planar, with a maximum deviation of 0.068 (2) Å for one of the amino N atoms. The sorbate anion adopts an extended conformation. In the crystal structure, the protonated N atom and one of the two amino-group H atoms are hydrogen bonded to the sorbate anion through a pair of N-H⋯O hydrogen bonds, forming an R(2) (2)(8) ring motif. The ion pairs are further connected via inter-molecular N-H⋯O and C-H⋯O hydrogen bonds, forming two-dimensional networks parallel to (100).

Related literature

For details of non-covalent inter­actions, see: Desiraju (1995 ▶); Moulton & Zaworotko (2001 ▶); Biradha & Fujita (2002 ▶). For applications of sorbic acid, see: Martindale (1996 ▶); Richards (1972 ▶). For related structures, see: Cox (1994 ▶); Thanigaimani et al. (2007 ▶); Raj et al. (2003 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C5H8N3 +·C6H7O2 −

M = 221.26

Monoclinic,

a = 9.0440 (3) Å

b = 10.6964 (3) Å

c = 12.4632 (4) Å

β = 94.947 (2)°

V = 1201.18 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.15 × 0.15 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.987, T max = 0.993

8260 measured reflections

2736 independent reflections

1794 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.111

S = 1.02

2736 reflections

205 parameters

All H-atom parameters refined

Δρmax = 0.22 e Å−3

Δρmin = −0.22 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/S1600536810032617/lh5118sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032617/lh5118Isup2.hkl

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

C5H8N3+·C6H7O2−	F(000) = 472
Mr = 221.26	Dx = 1.224 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1444 reflections
a = 9.0440 (3) Å	θ = 3.3–28.9°
b = 10.6964 (3) Å	µ = 0.09 mm−1
c = 12.4632 (4) Å	T = 296 K
β = 94.947 (2)°	Block, red
V = 1201.18 (6) Å3	0.15 × 0.15 × 0.09 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	2736 independent reflections
Radiation source: fine-focus sealed tube	1794 reflections with I > 2σ(I)
graphite	Rint = 0.053
φ and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→8
Tmin = 0.987, Tmax = 0.993	k = −13→11
8260 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111	All H-atom parameters refined
S = 1.02	w = 1/[σ2(Fo2) + (0.0417P)2 + 0.1735P] where P = (Fo2 + 2Fc2)/3
2736 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.22 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
O1	−0.19667 (13)	0.14636 (12)	0.53361 (8)	0.0233 (3)
O2	−0.04642 (13)	0.18916 (12)	0.40526 (8)	0.0241 (3)
C6	−0.14500 (18)	0.12200 (17)	0.44625 (11)	0.0180 (4)
H7	−0.148 (2)	−0.0069 (18)	0.3182 (13)	0.026 (5)*
H8	−0.364 (2)	−0.0391 (18)	0.4703 (14)	0.030 (5)*
H9	−0.317 (2)	−0.1811 (18)	0.2736 (14)	0.028 (5)*
H10	−0.545 (2)	−0.2085 (19)	0.4233 (15)	0.037 (6)*
H11A	−0.672 (3)	−0.307 (2)	0.2669 (16)	0.050 (6)*
H11B	−0.556 (2)	−0.407 (2)	0.3260 (14)	0.031 (5)*
H11C	−0.507 (2)	−0.3389 (19)	0.2230 (15)	0.034 (5)*
C7	−0.1975 (2)	0.01064 (18)	0.38280 (12)	0.0224 (4)
C8	−0.3120 (2)	−0.06038 (18)	0.40571 (12)	0.0209 (4)
C9	−0.3730 (2)	−0.16160 (17)	0.33880 (13)	0.0219 (4)
C10	−0.4924 (2)	−0.22749 (18)	0.35940 (14)	0.0252 (4)
C11	−0.5606 (2)	−0.3280 (2)	0.28818 (17)	0.0309 (5)
H2N3	0.224 (2)	0.516 (2)	0.8425 (15)	0.035 (6)*
N1	0.09874 (16)	0.36086 (15)	0.52745 (10)	0.0212 (4)
N2	0.00087 (17)	0.28443 (16)	0.67865 (12)	0.0236 (4)
N3	0.1886 (2)	0.44680 (19)	0.80698 (11)	0.0286 (4)
C1	0.1867 (2)	0.43933 (19)	0.47441 (14)	0.0278 (5)
C2	0.2698 (2)	0.5265 (2)	0.52935 (15)	0.0324 (5)
C3	0.2682 (2)	0.53273 (19)	0.64186 (14)	0.0276 (5)
C4	0.18421 (19)	0.45140 (18)	0.69625 (12)	0.0222 (4)
C5	0.09207 (18)	0.36429 (17)	0.63493 (12)	0.0193 (4)
H1	0.178 (2)	0.4288 (18)	0.3983 (14)	0.027 (5)*
H2	0.324 (2)	0.586 (2)	0.4933 (15)	0.038 (6)*
H3	0.326 (2)	0.599 (2)	0.6825 (14)	0.032 (5)*
H1N1	0.039 (2)	0.297 (2)	0.4839 (15)	0.037 (6)*
H1N2	−0.021 (2)	0.291 (2)	0.7442 (17)	0.038 (6)*
H2N2	−0.065 (2)	0.236 (2)	0.6330 (16)	0.036 (6)*
H1N3	0.113 (3)	0.407 (2)	0.8330 (16)	0.049 (7)*

	U11	U22	U33	U12	U13	U23
O1	0.0270 (7)	0.0241 (8)	0.0191 (5)	−0.0026 (6)	0.0040 (5)	−0.0010 (5)
O2	0.0274 (7)	0.0258 (8)	0.0193 (5)	−0.0058 (6)	0.0023 (5)	0.0002 (5)
C6	0.0193 (9)	0.0172 (11)	0.0170 (7)	0.0011 (8)	−0.0020 (6)	0.0033 (7)
C7	0.0238 (10)	0.0241 (12)	0.0190 (7)	0.0022 (9)	0.0005 (7)	−0.0010 (7)
C8	0.0206 (9)	0.0205 (12)	0.0211 (7)	0.0050 (8)	−0.0006 (7)	0.0010 (7)
C9	0.0237 (10)	0.0191 (12)	0.0225 (8)	0.0016 (8)	0.0002 (7)	−0.0009 (7)
C10	0.0243 (10)	0.0218 (12)	0.0295 (9)	0.0013 (9)	0.0023 (7)	0.0001 (8)
C11	0.0272 (11)	0.0276 (14)	0.0373 (10)	−0.0041 (10)	−0.0007 (9)	−0.0009 (10)
N1	0.0237 (8)	0.0201 (9)	0.0197 (6)	−0.0022 (7)	0.0010 (6)	−0.0009 (6)
N2	0.0252 (9)	0.0272 (11)	0.0187 (7)	−0.0052 (8)	0.0034 (6)	−0.0046 (7)
N3	0.0309 (10)	0.0300 (11)	0.0246 (7)	−0.0088 (8)	0.0012 (7)	−0.0094 (7)
C1	0.0320 (11)	0.0280 (13)	0.0235 (8)	−0.0025 (9)	0.0033 (8)	0.0042 (8)
C2	0.0346 (12)	0.0280 (14)	0.0351 (9)	−0.0075 (10)	0.0053 (9)	0.0068 (9)
C3	0.0293 (11)	0.0183 (12)	0.0346 (9)	−0.0039 (9)	−0.0001 (8)	−0.0032 (8)
C4	0.0207 (9)	0.0206 (11)	0.0249 (8)	0.0029 (8)	0.0003 (7)	−0.0029 (8)
C5	0.0185 (9)	0.0167 (11)	0.0223 (7)	0.0030 (8)	0.0006 (6)	−0.0012 (7)

O1—C6	1.2488 (18)	N1—C1	1.366 (2)
O2—C6	1.285 (2)	N1—H1N1	1.00 (2)
C6—C7	1.485 (2)	N2—C5	1.336 (2)
C7—C8	1.335 (2)	N2—H1N2	0.86 (2)
C7—H7	0.974 (17)	N2—H2N2	0.95 (2)
C8—C9	1.446 (2)	N3—C4	1.378 (2)
C8—H8	0.993 (18)	N3—H2N3	0.91 (2)
C9—C10	1.333 (3)	N3—H1N3	0.89 (3)
C9—H9	1.017 (18)	C1—C2	1.347 (3)
C10—C11	1.493 (3)	C1—H1	0.952 (16)
C10—H10	0.982 (19)	C2—C3	1.405 (2)
C11—H11A	1.04 (2)	C2—H2	0.94 (2)
C11—H11B	0.97 (2)	C3—C4	1.372 (3)
C11—H11C	0.99 (2)	C3—H3	0.99 (2)
N1—C5	1.3466 (19)	C4—C5	1.427 (2)
O1—C6—O2	123.69 (16)	C1—N1—H1N1	117.8 (11)
O1—C6—C7	120.34 (15)	C5—N2—H1N2	122.4 (14)
O2—C6—C7	115.97 (14)	C5—N2—H2N2	119.2 (12)
C8—C7—C6	124.12 (15)	H1N2—N2—H2N2	115.5 (18)
C8—C7—H7	119.4 (11)	C4—N3—H2N3	116.1 (12)
C6—C7—H7	116.4 (11)	C4—N3—H1N3	115.1 (14)
C7—C8—C9	124.52 (16)	H2N3—N3—H1N3	117.3 (19)
C7—C8—H8	118.2 (11)	C2—C1—N1	120.15 (16)
C9—C8—H8	117.1 (11)	C2—C1—H1	125.5 (12)
C10—C9—C8	124.02 (16)	N1—C1—H1	114.3 (12)
C10—C9—H9	121.0 (11)	C1—C2—C3	119.12 (19)
C8—C9—H9	114.9 (11)	C1—C2—H2	121.0 (12)
C9—C10—C11	124.47 (17)	C3—C2—H2	119.8 (12)
C9—C10—H10	120.1 (12)	C4—C3—C2	121.12 (19)
C11—C10—H10	115.3 (12)	C4—C3—H3	119.4 (11)
C10—C11—H11A	109.4 (13)	C2—C3—H3	119.5 (11)
C10—C11—H11B	110.0 (11)	C3—C4—N3	123.23 (17)
H11A—C11—H11B	108.2 (17)	C3—C4—C5	118.16 (15)
C10—C11—H11C	111.7 (11)	N3—C4—C5	118.57 (17)
H11A—C11—H11C	110.2 (16)	N2—C5—N1	118.07 (16)
H11B—C11—H11C	107.3 (16)	N2—C5—C4	123.47 (15)
C5—N1—C1	122.86 (16)	N1—C5—C4	118.45 (16)
C5—N1—H1N1	119.3 (11)
O1—C6—C7—C8	8.5 (3)	C2—C3—C4—N3	174.29 (19)
O2—C6—C7—C8	−171.14 (16)	C2—C3—C4—C5	−3.3 (3)
C6—C7—C8—C9	173.77 (16)	C1—N1—C5—N2	179.13 (17)
C7—C8—C9—C10	−176.15 (18)	C1—N1—C5—C4	−1.8 (3)
C8—C9—C10—C11	176.92 (18)	C3—C4—C5—N2	−177.03 (18)
C5—N1—C1—C2	−1.2 (3)	N3—C4—C5—N2	5.3 (3)
N1—C1—C2—C3	2.0 (3)	C3—C4—C5—N1	4.0 (3)
C1—C2—C3—C4	0.3 (3)	N3—C4—C5—N1	−173.69 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	1.00 (2)	1.66 (2)	2.6591 (19)	174.7 (18)
N2—H1N2···O2i	0.86 (2)	2.05 (2)	2.9065 (18)	173.1 (17)
N2—H2N2···O1	0.94 (2)	1.90 (2)	2.8432 (19)	176.2 (18)
N3—H1N3···O2i	0.89 (2)	2.04 (2)	2.930 (2)	174 (2)
N3—H2N3···O1ii	0.91 (2)	2.11 (2)	2.913 (2)	146.9 (16)
C10—H10···O1iii	0.983 (19)	2.531 (18)	3.330 (2)	138.2 (14)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	1.00 (2)	1.66 (2)	2.6591 (19)	174.7 (18)
N2—H1N2⋯O2	0.86 (2)	2.05 (2)	2.9065 (18)	173.1 (17)
N2—H2N2⋯O1	0.94 (2)	1.90 (2)	2.8432 (19)	176.2 (18)
N3—H1N3⋯O2	0.89 (2)	2.04 (2)	2.930 (2)	174 (2)
N3—H2N3⋯O1i	0.91 (2)	2.11 (2)	2.913 (2)	146.9 (16)
C10—H10⋯O1ii	0.983 (19)	2.531 (18)	3.330 (2)	138.2 (14)

Symmetry codes: (i) ; (ii) .