3,4-Diamino-pyridinium hydrogen succinate.

In the title compound, C(5)H(8)N(3) (+)·C(4)H(5)O(4) (-), the pyridine N atom of the 3,4-diamino-pyridine mol-ecule is protonated. The protonated N atom participates in an N-H⋯O hydrogen bond to a succinate O atom of the singly deprotonated succinate anion. Each of the two amino groups are hydrogen-bonded to the O atoms of two different sets of succinate groups.. The crystal structure is further stabilized by O-H⋯O and C-H⋯O hydrogen bonds.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For the use of 3,4-diamino­pyridine in Schiff base reactions, see: Opozda et al. (2006 ▶). For related structures, see: Opozda et al. (2006 ▶); Rubin-Preminger & Englert (2007 ▶); Koleva et al. (2007 ▶, 2008 ▶). For bond-length data, see: Allen et al. (1987 ▶) and 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 +·n class="Chemical">C4H5O4 −

M = 227.22

Monoclinic,

a = 4.9862 (2) Å

b = 9.5028 (3) Å

c = 10.4775 (3) Å

β = 93.653 (2)°

V = 495.45 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 100 K

0.41 × 0.13 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.929, T max = 0.991

9518 measured reflections

2280 independent reflections

2119 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.104

S = 1.18

2280 reflections

197 parameters

1 restraint

All H-atom parameters refined

Δρmax = 0.41 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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/S1600536809021205/sj2630sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021205/sj2630Isup2.hkl

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

C5H8N3+·C4H5O4−	F(000) = 240
Mr = 227.22	Dx = 1.523 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4153 reflections
a = 4.9862 (2) Å	θ = 2.9–38.4°
b = 9.5028 (3) Å	µ = 0.12 mm−1
c = 10.4775 (3) Å	T = 100 K
β = 93.653 (2)°	Block, colourless
V = 495.45 (3) Å3	0.41 × 0.13 × 0.08 mm
Z = 2

Bruker APEXII CCD area-detector diffractometer	2280 independent reflections
Radiation source: fine-focus sealed tube	2119 reflections with I > 2σ(I)
graphite	Rint = 0.028
φ and ω scans	θmax = 35.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
Tmin = 0.929, Tmax = 0.991	k = −15→15
9518 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	All H-atom parameters refined
S = 1.18	w = 1/[σ2(Fo2) + (0.0624P)2 + 0.022P] where P = (Fo2 + 2Fc2)/3
2280 reflections	(Δ/σ)max < 0.001
197 parameters	Δρmax = 0.41 e Å−3
1 restraint	Δρmin = −0.24 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 > 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
O1	0.2865 (2)	−0.15266 (13)	0.23443 (10)	0.0166 (2)
O2	0.2994 (2)	−0.04711 (12)	0.04363 (10)	0.0145 (2)
O3	1.0339 (2)	0.20905 (12)	0.27633 (10)	0.0148 (2)
O4	1.0369 (2)	0.31053 (11)	0.08455 (10)	0.01284 (19)
C6	0.3844 (3)	−0.06666 (14)	0.16351 (13)	0.0109 (2)
C7	0.6179 (3)	0.02567 (15)	0.20940 (13)	0.0127 (2)
C8	0.7020 (3)	0.13495 (15)	0.11407 (13)	0.0120 (2)
C9	0.9402 (3)	0.22422 (14)	0.16284 (12)	0.0100 (2)
N1	0.4164 (2)	0.40451 (13)	0.33423 (12)	0.0123 (2)
N2	0.8257 (3)	0.65927 (15)	0.17427 (12)	0.0172 (2)
N3	1.0198 (3)	0.68665 (15)	0.43411 (12)	0.0148 (2)
C1	0.5088 (3)	0.41464 (15)	0.45697 (13)	0.0128 (2)
C2	0.7131 (3)	0.50705 (15)	0.49097 (13)	0.0123 (2)
C3	0.8247 (3)	0.59224 (14)	0.39891 (13)	0.0108 (2)
C4	0.7264 (3)	0.57828 (14)	0.26856 (13)	0.0113 (2)
C5	0.5199 (3)	0.48313 (15)	0.24195 (13)	0.0121 (2)
H9	0.149 (6)	−0.108 (4)	0.012 (3)	0.059 (11)*
H1N1	0.270 (6)	0.343 (4)	0.329 (3)	0.039 (8)*
H1N2	0.801 (5)	0.635 (3)	0.105 (3)	0.026 (7)*
H2N2	0.992 (6)	0.706 (4)	0.202 (3)	0.036 (7)*
H1N3	1.097 (5)	0.734 (3)	0.382 (2)	0.019 (6)*
H2N3	1.073 (4)	0.697 (3)	0.520 (2)	0.018 (6)*
H1A	0.426 (4)	0.362 (3)	0.516 (2)	0.020 (6)*
H2A	0.770 (4)	0.517 (3)	0.574 (2)	0.018 (5)*
H5A	0.458 (5)	0.465 (3)	0.167 (2)	0.015 (5)*
H7A	0.570 (5)	0.073 (3)	0.304 (3)	0.029 (7)*
H7B	0.758 (6)	−0.037 (4)	0.247 (3)	0.043 (8)*
H8A	0.757 (5)	0.094 (3)	0.043 (3)	0.025 (6)*
H8B	0.570 (4)	0.203 (3)	0.097 (2)	0.017 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0190 (5)	0.0174 (5)	0.0134 (4)	−0.0080 (4)	0.0009 (4)	0.0021 (4)
O2	0.0170 (4)	0.0147 (4)	0.0111 (4)	−0.0043 (4)	−0.0033 (3)	0.0011 (3)
O3	0.0168 (4)	0.0152 (5)	0.0118 (4)	−0.0047 (4)	−0.0039 (3)	0.0026 (4)
O4	0.0121 (4)	0.0130 (4)	0.0132 (4)	−0.0020 (3)	−0.0006 (3)	0.0040 (3)
C6	0.0115 (5)	0.0107 (5)	0.0107 (5)	−0.0012 (4)	0.0015 (4)	−0.0015 (4)
C7	0.0130 (5)	0.0131 (5)	0.0116 (5)	−0.0046 (4)	−0.0015 (4)	0.0019 (4)
C8	0.0113 (5)	0.0129 (5)	0.0113 (5)	−0.0038 (4)	−0.0020 (4)	0.0006 (4)
C9	0.0094 (5)	0.0095 (5)	0.0109 (5)	0.0000 (4)	−0.0006 (4)	0.0004 (4)
N1	0.0129 (5)	0.0114 (5)	0.0124 (5)	−0.0025 (4)	−0.0001 (4)	0.0000 (4)
N2	0.0227 (6)	0.0187 (6)	0.0103 (5)	−0.0088 (5)	0.0012 (4)	0.0007 (4)
N3	0.0164 (5)	0.0160 (5)	0.0119 (5)	−0.0066 (4)	0.0002 (4)	−0.0018 (4)
C1	0.0143 (5)	0.0130 (5)	0.0112 (5)	−0.0027 (4)	0.0016 (4)	0.0014 (4)
C2	0.0142 (5)	0.0128 (5)	0.0100 (5)	−0.0015 (4)	0.0005 (4)	0.0003 (4)
C3	0.0110 (5)	0.0105 (5)	0.0108 (5)	−0.0013 (4)	0.0000 (4)	−0.0013 (4)
C4	0.0129 (5)	0.0105 (5)	0.0104 (5)	−0.0016 (4)	0.0003 (4)	−0.0005 (4)
C5	0.0127 (5)	0.0130 (5)	0.0105 (5)	−0.0022 (4)	−0.0004 (4)	−0.0003 (4)

O1—C6	1.2265 (18)	N1—H1N1	0.93 (3)
O2—C6	1.3130 (17)	N2—C4	1.3695 (19)
O2—H9	0.99 (4)	N2—H1N2	0.77 (3)
O3—C9	1.2578 (16)	N2—H2N2	0.97 (3)
O4—C9	1.2760 (16)	N3—C3	1.3569 (18)
C6—C7	1.5118 (19)	N3—H1N3	0.82 (3)
C7—C8	1.5183 (19)	N3—H2N3	0.93 (2)
C7—H7A	1.13 (3)	C1—C2	1.3749 (19)
C7—H7B	0.98 (3)	C1—H1A	0.91 (2)
C8—C9	1.5213 (18)	C2—C3	1.4013 (19)
C8—H8A	0.90 (3)	C2—H2A	0.91 (2)
C8—H8B	0.93 (2)	C3—C4	1.4275 (18)
N1—C1	1.3414 (18)	C4—C5	1.3853 (18)
N1—C5	1.3501 (18)	C5—H5A	0.84 (2)
C6—O2—H9	116 (2)	C4—N2—H1N2	118 (2)
O1—C6—O2	123.87 (13)	C4—N2—H2N2	112.4 (17)
O1—C6—C7	121.47 (12)	H1N2—N2—H2N2	121 (2)
O2—C6—C7	114.66 (12)	C3—N3—H1N3	122.4 (17)
C6—C7—C8	115.28 (11)	C3—N3—H2N3	119.1 (16)
C6—C7—H7A	107.9 (14)	H1N3—N3—H2N3	119 (2)
C8—C7—H7A	113.1 (15)	N1—C1—C2	119.84 (13)
C6—C7—H7B	107 (2)	N1—C1—H1A	117.7 (15)
C8—C7—H7B	117.4 (18)	C2—C1—H1A	122.4 (15)
H7A—C7—H7B	94 (2)	C1—C2—C3	120.72 (12)
C7—C8—C9	113.76 (10)	C1—C2—H2A	119.8 (16)
C7—C8—H8A	111.0 (18)	C3—C2—H2A	119.4 (16)
C9—C8—H8A	104.5 (17)	N3—C3—C2	120.27 (12)
C7—C8—H8B	112.4 (14)	N3—C3—C4	121.19 (12)
C9—C8—H8B	101.8 (15)	C2—C3—C4	118.54 (11)
H8A—C8—H8B	113 (2)	N2—C4—C5	121.32 (12)
O3—C9—O4	123.29 (12)	N2—C4—C3	121.34 (12)
O3—C9—C8	119.24 (12)	C5—C4—C3	117.30 (12)
O4—C9—C8	117.47 (11)	N1—C5—C4	122.02 (12)
C1—N1—C5	121.56 (12)	N1—C5—H5A	114.7 (16)
C1—N1—H1N1	108.8 (17)	C4—C5—H5A	123.1 (16)
C5—N1—H1N1	129.4 (17)
O1—C6—C7—C8	−175.22 (13)	C1—C2—C3—C4	−1.6 (2)
O2—C6—C7—C8	5.09 (18)	N3—C3—C4—N2	0.2 (2)
C6—C7—C8—C9	−179.08 (12)	C2—C3—C4—N2	179.47 (13)
C7—C8—C9—O3	−4.90 (18)	N3—C3—C4—C5	−177.55 (14)
C7—C8—C9—O4	174.38 (12)	C2—C3—C4—C5	1.74 (19)
C5—N1—C1—C2	0.1 (2)	C1—N1—C5—C4	0.0 (2)
N1—C1—C2—C3	0.7 (2)	N2—C4—C5—N1	−178.70 (13)
C1—C2—C3—N3	177.65 (14)	C3—C4—C5—N1	−1.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H9···O4i	0.99 (4)	1.53 (4)	2.4815 (14)	159 (3)
N1—H1N1···O3ii	0.93 (3)	1.80 (3)	2.7036 (16)	163 (3)
N2—H1N2···O2iii	0.77 (3)	2.36 (3)	3.0440 (17)	150 (3)
N2—H2N2···O1iv	0.97 (3)	2.00 (3)	2.9473 (17)	164 (3)
N3—H1N3···O1iv	0.82 (3)	2.15 (3)	2.9720 (18)	176 (2)
N3—H2N3···O3v	0.93 (2)	2.23 (2)	3.0699 (17)	149.7 (18)
C2—H2A···O3v	0.91 (2)	2.56 (3)	3.2907 (17)	138 (2)
C5—H5A···O2iii	0.84 (2)	2.59 (2)	3.1923 (18)	129.7 (19)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H9⋯O4i	0.99 (4)	1.53 (4)	2.4815 (14)	159 (3)
N1—H1N1⋯O3ii	0.93 (3)	1.80 (3)	2.7036 (16)	163 (3)
N2—H1N2⋯O2iii	0.77 (3)	2.36 (3)	3.0440 (17)	150 (3)
N2—H2N2⋯O1iv	0.97 (3)	2.00 (3)	2.9473 (17)	164 (3)
N3—H1N3⋯O1iv	0.82 (3)	2.15 (3)	2.9720 (18)	176 (2)
N3—H2N3⋯O3v	0.93 (2)	2.23 (2)	3.0699 (17)	149.7 (18)
C2—H2A⋯O3v	0.91 (2)	2.56 (3)	3.2907 (17)	138 (2)
C5—H5A⋯O2iii	0.84 (2)	2.59 (2)	3.1923 (18)	129.7 (19)

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