2,3-Diamino-pyridinium sorbate-sorbic acid (1/1).

In the title mol-ecular salt-adduct, C(5)H(8)N(3) (+)·C(6)H(7)O(2) (-)·C(6)H(8)O(2), the 2,3-diamino-pyridinium cation is essentially planar, with a maximum deviation of 0.013 (2) Å, and is protanated at its pyridine N atom. The sorbate anion and sorbic acid mol-ecules exist in extended conformations. In the crystal, 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(1) (2)(6) ring motif. The carboxyl groups of the sorbic acid mol-ecules and the carboxyl-ate groups of the sorbate anions are connected via O-H⋯O hydrogen bonds. Furthermore, the ion pairs and neutral mol-ecules are connected via inter-molecular N-H⋯O hydrogen bonds, forming sheets lying parallel to (100).

Related literature

For a different crystal structure arising from the same synthesis conditions, see: Hemamalini & Fun (2010 ▶). For background to amino­pyridines, see: Peng et al. (2001 ▶); Leung et al. (2002 ▶); Banerjee & Murugavel (2004 ▶); Lautie & Belabbes (1996 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C5H8N3 +·C6H7O2 −·C6H8O2

M = 333.38

Monoclinic,

a = 16.1636 (17) Å

b = 9.6538 (10) Å

c = 12.6887 (13) Å

β = 112.844 (2)°

V = 1824.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.47 × 0.25 × 0.06 mm

Data collection

Bruker APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.960, T max = 0.994

27805 measured reflections

5345 independent reflections

2898 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.152

S = 1.02

5345 reflections

239 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 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: SHELXTLand PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811053025/hb6558sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053025/hb6558Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811053025/hb6558Isup3.cml

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

C5H8N3+·C6H7O2−·C6H8O2	F(000) = 712
Mr = 333.38	Dx = 1.214 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4699 reflections
a = 16.1636 (17) Å	θ = 2.5–23.6°
b = 9.6538 (10) Å	µ = 0.09 mm−1
c = 12.6887 (13) Å	T = 100 K
β = 112.844 (2)°	Plate, brown
V = 1824.6 (3) Å3	0.47 × 0.25 × 0.06 mm
Z = 4

Bruker APEXII DUO CCD diffractometer	5345 independent reflections
Radiation source: fine-focus sealed tube	2898 reflections with I > 2σ(I)
graphite	Rint = 0.045
φ and ω scans	θmax = 30.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −22→22
Tmin = 0.960, Tmax = 0.994	k = −13→13
27805 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0631P)2 + 0.2243P] where P = (Fo2 + 2Fc2)/3
5345 reflections	(Δ/σ)max < 0.001
239 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.22 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	0.52439 (11)	0.20084 (17)	0.03419 (12)	0.0703 (4)
N2	0.45891 (11)	0.1854 (2)	0.16546 (18)	0.0778 (5)
N3	0.59685 (10)	0.00896 (17)	0.29774 (14)	0.0713 (4)
C1	0.52362 (10)	0.14816 (17)	0.13081 (13)	0.0563 (4)
C2	0.59314 (9)	0.05457 (16)	0.19419 (13)	0.0522 (4)
C3	0.65504 (10)	0.02052 (18)	0.14930 (15)	0.0642 (4)
H3A	0.7001	−0.0427	0.1878	0.077*
C4	0.65219 (12)	0.0785 (2)	0.04688 (16)	0.0771 (5)
H4A	0.6950	0.0548	0.0179	0.093*
C5	0.58688 (14)	0.1688 (2)	−0.00887 (16)	0.0808 (5)
H5A	0.5844	0.2092	−0.0766	0.097*
O1B	0.20615 (8)	0.22997 (14)	0.43760 (10)	0.0701 (3)
O2B	0.26440 (7)	0.21636 (13)	0.62722 (10)	0.0698 (3)
C6B	0.20207 (10)	0.24501 (15)	0.53806 (14)	0.0541 (4)
C7B	0.11588 (10)	0.29993 (16)	0.53419 (14)	0.0560 (4)
H7BA	0.0703	0.3165	0.4631	0.067*
C8B	0.10027 (10)	0.32670 (15)	0.62678 (13)	0.0536 (4)
H8BA	0.1460	0.3066	0.6969	0.064*
C9B	0.01845 (10)	0.38450 (16)	0.62879 (14)	0.0569 (4)
H9BA	−0.0277	0.4038	0.5588	0.068*
C10B	0.00417 (13)	0.41200 (19)	0.72185 (16)	0.0688 (5)
H10A	0.0505	0.3925	0.7916	0.083*
C11B	−0.07969 (15)	0.4715 (3)	0.7250 (2)	0.0929 (7)
H11A	−0.1059	0.4066	0.7604	0.139*
H11B	−0.1213	0.4904	0.6485	0.139*
H11C	−0.0660	0.5560	0.7683	0.139*
O1A	0.35766 (7)	0.14675 (14)	0.44960 (11)	0.0747 (4)
H1A	0.3058	0.1418	0.4452	0.112*
O2A	0.43810 (7)	0.06465 (17)	0.35977 (11)	0.0830 (4)
C6A	0.36773 (10)	0.06657 (18)	0.37630 (13)	0.0588 (4)
C7A	0.29051 (10)	−0.02288 (17)	0.31033 (13)	0.0571 (4)
H7AA	0.2396	−0.0174	0.3273	0.068*
C8A	0.28871 (10)	−0.10933 (17)	0.22971 (13)	0.0571 (4)
H8AA	0.3407	−0.1171	0.2153	0.069*
C9A	0.21322 (11)	−0.19332 (17)	0.16161 (14)	0.0592 (4)
H9AA	0.1603	−0.1820	0.1733	0.071*
C10A	0.21248 (13)	−0.28488 (19)	0.08416 (16)	0.0716 (5)
H10B	0.2656	−0.2947	0.0726	0.086*
C11A	0.13681 (15)	−0.3735 (2)	0.01381 (18)	0.0891 (6)
H11G	0.1245	−0.3584	−0.0657	0.134*
H11D	0.0846	−0.3507	0.0288	0.134*
H11E	0.1521	−0.4690	0.0325	0.134*
H1N1	0.4814 (17)	0.260 (3)	−0.006 (2)	0.112 (8)*
H1N2	0.4194 (16)	0.234 (2)	0.1193 (19)	0.093 (7)*
H2N2	0.4547 (15)	0.148 (3)	0.225 (2)	0.098 (9)*
H1N3	0.5524 (13)	0.0094 (18)	0.3168 (15)	0.066 (5)*
H2N3	0.6417 (15)	−0.055 (3)	0.3295 (19)	0.104 (7)*

	U11	U22	U33	U12	U13	U23
N1	0.0674 (9)	0.0770 (10)	0.0511 (8)	0.0190 (8)	0.0062 (7)	0.0022 (7)
N2	0.0622 (9)	0.0905 (12)	0.0739 (11)	0.0316 (9)	0.0190 (8)	−0.0020 (10)
N3	0.0521 (8)	0.0816 (11)	0.0848 (11)	0.0154 (8)	0.0314 (8)	0.0260 (9)
C1	0.0475 (8)	0.0591 (9)	0.0528 (9)	0.0076 (7)	0.0093 (6)	−0.0078 (7)
C2	0.0435 (7)	0.0516 (8)	0.0558 (9)	0.0029 (6)	0.0132 (6)	0.0003 (7)
C3	0.0476 (8)	0.0699 (10)	0.0708 (11)	0.0105 (7)	0.0181 (7)	−0.0003 (9)
C4	0.0663 (11)	0.1024 (15)	0.0656 (11)	0.0092 (10)	0.0288 (9)	−0.0031 (11)
C5	0.0818 (13)	0.1025 (15)	0.0527 (10)	0.0082 (11)	0.0203 (9)	0.0028 (10)
O1B	0.0584 (7)	0.0927 (9)	0.0518 (6)	0.0105 (6)	0.0133 (5)	−0.0043 (6)
O2B	0.0546 (6)	0.0833 (8)	0.0586 (7)	0.0206 (6)	0.0077 (5)	0.0004 (6)
C6B	0.0472 (8)	0.0474 (8)	0.0572 (9)	0.0013 (6)	0.0087 (7)	−0.0020 (7)
C7B	0.0465 (8)	0.0593 (9)	0.0530 (9)	0.0042 (7)	0.0091 (6)	0.0043 (7)
C8B	0.0484 (8)	0.0488 (8)	0.0542 (9)	0.0001 (6)	0.0097 (6)	0.0031 (7)
C9B	0.0530 (8)	0.0559 (9)	0.0571 (9)	0.0014 (7)	0.0163 (7)	0.0059 (7)
C10B	0.0731 (11)	0.0684 (11)	0.0661 (11)	0.0056 (9)	0.0283 (9)	0.0067 (9)
C11B	0.0984 (15)	0.0950 (15)	0.1081 (17)	0.0154 (12)	0.0648 (13)	0.0127 (13)
O1A	0.0507 (6)	0.0923 (9)	0.0765 (8)	−0.0053 (6)	0.0195 (6)	−0.0293 (7)
O2A	0.0473 (6)	0.1230 (11)	0.0829 (9)	−0.0019 (7)	0.0299 (6)	−0.0065 (8)
C6A	0.0473 (8)	0.0721 (10)	0.0563 (9)	0.0017 (7)	0.0194 (7)	−0.0026 (8)
C7A	0.0488 (8)	0.0681 (10)	0.0578 (9)	0.0007 (7)	0.0245 (7)	−0.0049 (8)
C8A	0.0536 (8)	0.0649 (9)	0.0525 (8)	0.0105 (7)	0.0201 (7)	0.0031 (7)
C9A	0.0641 (10)	0.0571 (9)	0.0553 (9)	0.0064 (7)	0.0218 (7)	−0.0006 (7)
C10A	0.0771 (12)	0.0684 (11)	0.0646 (10)	0.0135 (9)	0.0222 (9)	−0.0041 (9)
C11A	0.1050 (16)	0.0634 (11)	0.0814 (14)	0.0037 (11)	0.0172 (12)	−0.0159 (10)

N1—C1	1.332 (2)	C9B—C10B	1.315 (2)
N1—C5	1.358 (2)	C9B—H9BA	0.9300
N1—H1N1	0.89 (3)	C10B—C11B	1.487 (3)
N2—C1	1.332 (2)	C10B—H10A	0.9300
N2—H1N2	0.83 (2)	C11B—H11A	0.9600
N2—H2N2	0.86 (2)	C11B—H11B	0.9600
N3—C2	1.365 (2)	C11B—H11C	0.9600
N3—H1N3	0.843 (18)	O1A—C6A	1.2682 (19)
N3—H2N3	0.92 (2)	O1A—H1A	0.8200
C1—C2	1.423 (2)	O2A—C6A	1.2341 (18)
C2—C3	1.370 (2)	C6A—C7A	1.481 (2)
C3—C4	1.399 (3)	C7A—C8A	1.312 (2)
C3—H3A	0.9300	C7A—H7AA	0.9300
C4—C5	1.339 (3)	C8A—C9A	1.440 (2)
C4—H4A	0.9300	C8A—H8AA	0.9300
C5—H5A	0.9300	C9A—C10A	1.318 (2)
O1B—C6B	1.310 (2)	C9A—H9AA	0.9300
O2B—C6B	1.2192 (17)	C10A—C11A	1.475 (3)
C6B—C7B	1.474 (2)	C10A—H10B	0.9300
C7B—C8B	1.319 (2)	C11A—H11G	0.9600
C7B—H7BA	0.9300	C11A—H11D	0.9600
C8B—C9B	1.445 (2)	C11A—H11E	0.9600
C8B—H8BA	0.9300
C1—N1—C5	123.90 (16)	C10B—C9B—H9BA	117.5
C1—N1—H1N1	119.1 (16)	C8B—C9B—H9BA	117.5
C5—N1—H1N1	117.0 (16)	C9B—C10B—C11B	125.59 (18)
C1—N2—H1N2	114.2 (15)	C9B—C10B—H10A	117.2
C1—N2—H2N2	120.9 (16)	C11B—C10B—H10A	117.2
H1N2—N2—H2N2	124 (2)	C10B—C11B—H11A	109.5
C2—N3—H1N3	123.5 (12)	C10B—C11B—H11B	109.5
C2—N3—H2N3	111.8 (14)	H11A—C11B—H11B	109.5
H1N3—N3—H2N3	119.6 (19)	C10B—C11B—H11C	109.5
N2—C1—N1	119.33 (16)	H11A—C11B—H11C	109.5
N2—C1—C2	122.29 (17)	H11B—C11B—H11C	109.5
N1—C1—C2	118.38 (15)	C6A—O1A—H1A	109.5
N3—C2—C3	123.83 (15)	O2A—C6A—O1A	121.53 (16)
N3—C2—C1	118.61 (14)	O2A—C6A—C7A	121.69 (15)
C3—C2—C1	117.49 (15)	O1A—C6A—C7A	116.77 (13)
C2—C3—C4	121.61 (16)	C8A—C7A—C6A	124.78 (14)
C2—C3—H3A	119.2	C8A—C7A—H7AA	117.6
C4—C3—H3A	119.2	C6A—C7A—H7AA	117.6
C5—C4—C3	119.07 (17)	C7A—C8A—C9A	125.68 (15)
C5—C4—H4A	120.5	C7A—C8A—H8AA	117.2
C3—C4—H4A	120.5	C9A—C8A—H8AA	117.2
C4—C5—N1	119.52 (19)	C10A—C9A—C8A	125.81 (17)
C4—C5—H5A	120.2	C10A—C9A—H9AA	117.1
N1—C5—H5A	120.2	C8A—C9A—H9AA	117.1
O2B—C6B—O1B	122.84 (14)	C9A—C10A—C11A	127.25 (19)
O2B—C6B—C7B	122.85 (15)	C9A—C10A—H10B	116.4
O1B—C6B—C7B	114.30 (13)	C11A—C10A—H10B	116.4
C8B—C7B—C6B	123.09 (14)	C10A—C11A—H11G	109.5
C8B—C7B—H7BA	118.5	C10A—C11A—H11D	109.5
C6B—C7B—H7BA	118.5	H11G—C11A—H11D	109.5
C7B—C8B—C9B	125.75 (14)	C10A—C11A—H11E	109.5
C7B—C8B—H8BA	117.1	H11G—C11A—H11E	109.5
C9B—C8B—H8BA	117.1	H11D—C11A—H11E	109.5
C10B—C9B—C8B	125.09 (16)
C5—N1—C1—N2	−179.49 (19)	O2B—C6B—C7B—C8B	2.3 (2)
C5—N1—C1—C2	1.2 (3)	O1B—C6B—C7B—C8B	−177.53 (15)
N2—C1—C2—N3	−4.5 (3)	C6B—C7B—C8B—C9B	177.96 (14)
N1—C1—C2—N3	174.80 (15)	C7B—C8B—C9B—C10B	−179.26 (17)
N2—C1—C2—C3	178.37 (17)	C8B—C9B—C10B—C11B	179.96 (18)
N1—C1—C2—C3	−2.3 (2)	O2A—C6A—C7A—C8A	−0.6 (3)
N3—C2—C3—C4	−174.93 (17)	O1A—C6A—C7A—C8A	178.42 (16)
C1—C2—C3—C4	2.0 (2)	C6A—C7A—C8A—C9A	−177.50 (15)
C2—C3—C4—C5	−0.5 (3)	C7A—C8A—C9A—C10A	−176.71 (18)
C3—C4—C5—N1	−0.8 (3)	C8A—C9A—C10A—C11A	179.34 (18)
C1—N1—C5—C4	0.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···O1B	0.82	1.79	2.5252 (19)	148
N1—H1N1···O1Ai	0.89 (3)	2.06 (3)	2.887 (2)	153 (3)
N1—H1N1···O2Ai	0.89 (3)	2.31 (3)	3.094 (2)	147 (2)
N2—H1N2···O1Ai	0.83 (2)	2.30 (2)	3.054 (2)	152 (2)
N2—H1N2···O2Bi	0.83 (2)	2.59 (3)	3.136 (2)	125 (2)
N2—H2N2···O2A	0.86 (2)	2.00 (3)	2.863 (2)	177 (2)
N3—H1N3···O2A	0.84 (2)	2.19 (2)	3.010 (2)	166.1 (16)
N3—H2N3···O2Bii	0.92 (3)	2.09 (3)	3.002 (2)	170 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1A⋯O1B	0.82	1.79	2.5252 (19)	148
N1—H1N1⋯O1Ai	0.89 (3)	2.06 (3)	2.887 (2)	153 (3)
N1—H1N1⋯O2Ai	0.89 (3)	2.31 (3)	3.094 (2)	147 (2)
N2—H1N2⋯O1Ai	0.83 (2)	2.30 (2)	3.054 (2)	152 (2)
N2—H1N2⋯O2Bi	0.83 (2)	2.59 (3)	3.136 (2)	125 (2)
N2—H2N2⋯O2A	0.86 (2)	2.00 (3)	2.863 (2)	177 (2)
N3—H1N3⋯O2A	0.84 (2)	2.19 (2)	3.010 (2)	166.1 (16)
N3—H2N3⋯O2Bii	0.92 (3)	2.09 (3)	3.002 (2)	170 (2)

Symmetry codes: (i) ; (ii) .