3,4-Di-amino-pyridinium hydrogen malonate.

In the title salt, C5H8N3 (+)·C3H3O4 (-), the 3,4-di-amino-pyridinium cation is almost planar, with an r.m.s. deviation of 0.02 Å. The conformation of the hydrogen malonate anion is stabilized by an intra-molecular O-H⋯O hydrogen bond, which generates an S(6) ring. In the crystal, N-H⋯O hydrogen bonds link cations and anions into layers parallel to the ab plane.

Related literature

For applications of 3,4-di­amino­pyridine, see: Maddison et al. (2001 ▶); Argov (2009 ▶). For related structures, see: De Cires-Mejias et al. (2004 ▶); Koleva et al. (2007 ▶, 2008 ▶); Fun & Balasubramani (2009 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C5H8N3 +·C3H3O4 −

M = 213.20

Monoclinic,

a = 8.7761 (18) Å

b = 5.088 (1) Å

c = 10.636 (2) Å

β = 101.381 (4)°

V = 465.58 (17) Å3

Z = 2

Mo Kα radiation

μ = 0.12 mm−1

T = 296 K

0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.964, T max = 0.976

3498 measured reflections

1248 independent reflections

1066 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.102

S = 1.18

1248 reflections

140 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.19 e Å−3

Δρmin = −0.15 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813008763/cv5392sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008763/cv5392Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813008763/cv5392Isup3.cml

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

C5H8N3+·C3H3O4−	F(000) = 224
Mr = 213.20	Dx = 1.521 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1070 reflections
a = 8.7761 (18) Å	θ = 2.8–27.0°
b = 5.088 (1) Å	µ = 0.12 mm−1
c = 10.636 (2) Å	T = 296 K
β = 101.381 (4)°	Prism, colourless
V = 465.58 (17) Å3	0.30 × 0.20 × 0.20 mm
Z = 2

Bruker APEXII CCD diffractometer	1248 independent reflections
Radiation source: fine-focus sealed tube	1066 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
φ and ω scans	θmax = 28.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −11→11
Tmin = 0.964, Tmax = 0.976	k = −6→6
3498 measured reflections	l = −14→14

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ2(Fo2) + (0.0456P)2 + 0.0455P] where P = (Fo2 + 2Fc2)/3
1248 reflections	(Δ/σ)max < 0.001
140 parameters	Δρmax = 0.19 e Å−3
1 restraint	Δρmin = −0.15 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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
N1	0.3630 (3)	0.6491 (5)	0.2325 (2)	0.0467 (6)
H1A	0.4198	0.5329	0.2052	0.056*
N2	0.0891 (3)	1.1609 (5)	0.09714 (19)	0.0461 (6)
H2A	0.0922	1.1490	0.0170	0.055*
H2B	0.0283	1.2730	0.1225	0.055*
N3	0.0818 (3)	1.1851 (5)	0.3616 (2)	0.0428 (5)
H3A	0.0792	1.1894	0.4420	0.051*
H3B	0.0253	1.2917	0.3094	0.051*
C2	0.2794 (3)	0.8205 (5)	0.1477 (3)	0.0422 (6)
H2	0.2893	0.8147	0.0623	0.051*
C3	0.1811 (3)	1.0013 (5)	0.1844 (2)	0.0333 (5)
C4	0.1737 (3)	1.0129 (5)	0.3178 (2)	0.0335 (5)
C5	0.2662 (3)	0.8383 (6)	0.4014 (3)	0.0423 (6)
H5	0.2649	0.8450	0.4886	0.051*
C6	0.3587 (3)	0.6579 (6)	0.3574 (3)	0.0485 (7)
H6	0.4184	0.5416	0.4142	0.058*
O1	0.8907 (2)	−0.4299 (4)	0.19036 (19)	0.0501 (5)
O2	0.7898 (2)	−0.2740 (5)	0.35111 (17)	0.0536 (6)
O3	0.5470 (2)	0.2937 (4)	0.13031 (19)	0.0483 (5)
O4	0.6154 (3)	0.1047 (4)	0.32045 (18)	0.0494 (5)
H4	0.674 (4)	−0.042 (7)	0.345 (3)	0.044 (9)*
C7	0.8059 (3)	−0.2775 (5)	0.2335 (2)	0.0356 (6)
C8	0.7139 (3)	−0.0761 (5)	0.1443 (2)	0.0340 (5)
H8A	0.7865	0.0192	0.1034	0.041*
H8B	0.6444	−0.1711	0.0774	0.041*
C9	0.6182 (3)	0.1235 (5)	0.1993 (2)	0.0348 (5)

	U11	U22	U33	U12	U13	U23
N1	0.0438 (12)	0.0339 (12)	0.0626 (14)	0.0032 (11)	0.0108 (10)	−0.0094 (12)
N2	0.0563 (13)	0.0490 (14)	0.0309 (10)	0.0087 (12)	0.0035 (9)	0.0022 (10)
N3	0.0515 (12)	0.0438 (13)	0.0325 (10)	0.0068 (11)	0.0071 (9)	−0.0015 (10)
C2	0.0424 (14)	0.0394 (15)	0.0431 (13)	−0.0060 (13)	0.0043 (11)	−0.0061 (12)
C3	0.0334 (12)	0.0334 (13)	0.0324 (11)	−0.0062 (11)	0.0043 (9)	−0.0017 (10)
C4	0.0359 (12)	0.0296 (12)	0.0337 (11)	−0.0025 (11)	0.0039 (9)	−0.0014 (10)
C5	0.0464 (14)	0.0396 (15)	0.0374 (12)	0.0013 (13)	0.0002 (11)	0.0068 (11)
C6	0.0493 (16)	0.0365 (14)	0.0565 (16)	0.0019 (13)	0.0027 (12)	0.0082 (14)
O1	0.0502 (11)	0.0430 (12)	0.0555 (11)	0.0150 (10)	0.0066 (9)	0.0097 (10)
O2	0.0702 (14)	0.0551 (13)	0.0323 (9)	−0.0030 (11)	0.0025 (8)	0.0095 (9)
O3	0.0470 (11)	0.0402 (11)	0.0558 (11)	0.0132 (9)	0.0055 (8)	−0.0025 (9)
O4	0.0606 (12)	0.0508 (13)	0.0380 (10)	0.0003 (12)	0.0129 (9)	−0.0113 (10)
C7	0.0361 (13)	0.0345 (13)	0.0340 (12)	−0.0029 (11)	0.0014 (9)	0.0048 (11)
C8	0.0381 (12)	0.0363 (13)	0.0268 (10)	0.0051 (11)	0.0044 (9)	0.0028 (10)
C9	0.0328 (12)	0.0346 (13)	0.0363 (11)	−0.0054 (11)	0.0053 (9)	−0.0038 (11)

N1—C6	1.337 (4)	C5—C6	1.368 (4)
N1—C2	1.360 (4)	C5—H5	0.9300
N1—H1A	0.8600	C6—H6	0.9300
N2—C3	1.370 (3)	O1—C7	1.225 (3)
N2—H2A	0.8600	O2—C7	1.286 (3)
N2—H2B	0.8600	O3—C9	1.224 (3)
N3—C4	1.335 (3)	O4—C9	1.298 (3)
N3—H3A	0.8600	O4—H4	0.91 (3)
N3—H3B	0.8600	C7—C8	1.517 (3)
C2—C3	1.369 (4)	C8—C9	1.507 (3)
C2—H2	0.9300	C8—H8A	0.9700
C3—C4	1.435 (3)	C8—H8B	0.9700
C4—C5	1.398 (3)
C6—N1—C2	121.3 (3)	C6—C5—H5	119.4
C6—N1—H1A	119.4	C4—C5—H5	119.4
C2—N1—H1A	119.4	N1—C6—C5	119.9 (3)
C3—N2—H2A	120.0	N1—C6—H6	120.1
C3—N2—H2B	120.0	C5—C6—H6	120.1
H2A—N2—H2B	120.0	C9—O4—H4	102.8 (19)
C4—N3—H3A	120.0	O1—C7—O2	124.4 (2)
C4—N3—H3B	120.0	O1—C7—C8	118.7 (2)
H3A—N3—H3B	120.0	O2—C7—C8	116.9 (2)
N1—C2—C3	122.0 (2)	C9—C8—C7	118.75 (19)
N1—C2—H2	119.0	C9—C8—H8A	107.6
C3—C2—H2	119.0	C7—C8—H8A	107.6
C2—C3—N2	121.7 (2)	C9—C8—H8B	107.6
C2—C3—C4	117.6 (2)	C7—C8—H8B	107.6
N2—C3—C4	120.7 (2)	H8A—C8—H8B	107.1
N3—C4—C5	120.7 (2)	O3—C9—O4	122.7 (2)
N3—C4—C3	121.4 (2)	O3—C9—C8	120.1 (2)
C5—C4—C3	118.0 (2)	O4—C9—C8	117.2 (2)
C6—C5—C4	121.2 (2)
C6—N1—C2—C3	−3.3 (4)	C3—C4—C5—C6	−1.4 (4)
N1—C2—C3—N2	−175.4 (3)	C2—N1—C6—C5	1.4 (4)
N1—C2—C3—C4	2.7 (4)	C4—C5—C6—N1	0.9 (4)
C2—C3—C4—N3	179.4 (3)	O1—C7—C8—C9	−175.8 (2)
N2—C3—C4—N3	−2.5 (4)	O2—C7—C8—C9	3.6 (4)
C2—C3—C4—C5	−0.4 (3)	C7—C8—C9—O3	177.5 (2)
N2—C3—C4—C5	177.7 (2)	C7—C8—C9—O4	−2.7 (3)
N3—C4—C5—C6	178.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.86	1.93	2.784 (3)	175
N2—H2A···O1i	0.86	2.28	3.132 (3)	174
N2—H2B···O1ii	0.86	2.15	3.005 (3)	176
N3—H3A···O2iii	0.86	2.28	3.048 (3)	149
N3—H3B···O1ii	0.86	2.10	2.960 (3)	177
O4—H4···O2	0.91 (3)	1.55 (3)	2.442 (3)	164 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3	0.86	1.93	2.784 (3)	175
N2—H2A⋯O1i	0.86	2.28	3.132 (3)	174
N2—H2B⋯O1ii	0.86	2.15	3.005 (3)	176
N3—H3A⋯O2iii	0.86	2.28	3.048 (3)	149
N3—H3B⋯O1ii	0.86	2.10	2.960 (3)	177
O4—H4⋯O2	0.91 (3)	1.55 (3)	2.442 (3)	164 (3)

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