2,3-Diamino-pyridinium hydrogen malonate.

In the title mol-ecular salt, C5H8N3(+)·C3H3O4(-), the cation is essentially planar, with a maximum deviation of 0.005 (1) Å for all non-H atoms. In the anion, an intra-molecular O-H⋯O hydrogen bond generates an S(6) ring. In the crystal, the cations and anions are connected via N-H⋯O hydrogen bonds and a weak C-H⋯O inter-action, forming layers parallel to the ab plane.

Related literature

For backgroup to the chemistry of substituted pyridines, see: Amr et al. (2006 ▶); Bart et al. (2001 ▶); Shinkai et al. (2000 ▶). For related structures, see: Betz et al. (2011 ▶); Hemamalini et al. (2011 ▶); Balasubramani & Fun (2009 ▶); Fun & Balasubramani (2009 ▶). For the conformation of the malonate ion, see: Djinović et al. (1990 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C5H8N3 +·C3H3O4 −

M = 213.20

Monoclinic,

a = 5.0843 (1) Å

b = 8.0771 (1) Å

c = 11.1928 (2) Å

β = 91.214 (1)°

V = 459.55 (1) Å3

Z = 2

Mo Kα radiation

μ = 0.13 mm−1

T = 100 K

0.28 × 0.25 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.966, T max = 0.983

6631 measured reflections

1778 independent reflections

1695 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.094

S = 1.07

1778 reflections

160 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.26 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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812050386/is5228sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812050386/is5228Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812050386/is5228Isup3.cml

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

C5H8N3+·C3H3O4−	F(000) = 224
Mr = 213.20	Dx = 1.541 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3153 reflections
a = 5.0843 (1) Å	θ = 3.1–32.6°
b = 8.0771 (1) Å	µ = 0.13 mm−1
c = 11.1928 (2) Å	T = 100 K
β = 91.214 (1)°	Block, brown
V = 459.55 (1) Å3	0.28 × 0.25 × 0.14 mm
Z = 2

Bruker SMART APEXII CCD area-detector diffractometer	1778 independent reflections
Radiation source: fine-focus sealed tube	1695 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 32.7°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
Tmin = 0.966, Tmax = 0.983	k = −10→12
6631 measured reflections	l = −17→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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0564P)2 + 0.057P] where P = (Fo2 + 2Fc2)/3
1778 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.35 e Å−3
1 restraint	Δρmin = −0.26 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 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
O1	0.4162 (2)	0.50089 (15)	0.24888 (10)	0.0139 (2)
O2	0.3017 (2)	0.50412 (15)	0.44060 (10)	0.0139 (2)
O3	0.7878 (2)	0.31758 (17)	0.18357 (11)	0.0209 (3)
O4	1.0228 (2)	0.17757 (17)	0.31863 (13)	0.0222 (3)
N1	0.9986 (2)	0.70786 (17)	0.18711 (12)	0.0123 (2)
N2	0.8913 (3)	0.75149 (17)	0.38452 (12)	0.0136 (3)
N3	0.4668 (3)	0.95043 (19)	0.30805 (14)	0.0163 (3)
C1	0.8441 (3)	0.78141 (18)	0.26789 (13)	0.0107 (3)
C2	0.6311 (3)	0.88272 (18)	0.22541 (14)	0.0119 (3)
C3	0.5946 (3)	0.8991 (2)	0.10331 (14)	0.0142 (3)
H3A	0.4551	0.9663	0.0730	0.017*
C4	0.7607 (3)	0.8179 (2)	0.02293 (14)	0.0161 (3)
H4A	0.7326	0.8294	−0.0608	0.019*
C5	0.9617 (3)	0.7228 (2)	0.06655 (14)	0.0153 (3)
H5A	1.0754	0.6673	0.0135	0.018*
C6	0.4477 (3)	0.45888 (19)	0.35774 (14)	0.0112 (3)
C7	0.6803 (3)	0.34858 (19)	0.39221 (14)	0.0129 (3)
H7A	0.7997	0.4142	0.4448	0.016*
H7B	0.6122	0.2564	0.4410	0.016*
C8	0.8449 (3)	0.27351 (19)	0.29470 (15)	0.0148 (3)
H2N3	0.343 (5)	1.013 (4)	0.276 (2)	0.023 (6)*
H2N2	0.814 (5)	0.817 (4)	0.434 (2)	0.026 (6)*
H1N1	1.136 (6)	0.645 (4)	0.218 (3)	0.044 (8)*
H1N2	1.043 (5)	0.703 (4)	0.401 (2)	0.029 (6)*
H1N3	0.534 (5)	0.963 (3)	0.380 (2)	0.018 (5)*
H1O3	0.654 (6)	0.395 (5)	0.190 (3)	0.048 (9)*

	U11	U22	U33	U12	U13	U23
O1	0.0137 (4)	0.0153 (5)	0.0126 (5)	0.0024 (4)	−0.0005 (4)	0.0011 (4)
O2	0.0129 (4)	0.0152 (5)	0.0136 (5)	0.0025 (4)	0.0018 (3)	0.0004 (4)
O3	0.0217 (5)	0.0231 (6)	0.0183 (6)	0.0068 (5)	0.0060 (4)	−0.0012 (5)
O4	0.0143 (5)	0.0164 (6)	0.0360 (8)	0.0056 (4)	0.0016 (4)	−0.0008 (5)
N1	0.0115 (5)	0.0135 (6)	0.0119 (6)	0.0010 (4)	0.0004 (4)	0.0006 (5)
N2	0.0134 (5)	0.0160 (6)	0.0114 (6)	0.0024 (4)	−0.0001 (4)	0.0004 (5)
N3	0.0115 (5)	0.0211 (6)	0.0162 (6)	0.0053 (5)	0.0001 (4)	−0.0023 (5)
C1	0.0096 (5)	0.0114 (6)	0.0112 (6)	−0.0005 (4)	0.0006 (4)	0.0001 (5)
C2	0.0099 (5)	0.0112 (6)	0.0147 (7)	−0.0001 (5)	−0.0005 (4)	0.0005 (5)
C3	0.0124 (5)	0.0154 (6)	0.0148 (7)	0.0012 (5)	−0.0022 (5)	0.0026 (6)
C4	0.0168 (6)	0.0201 (7)	0.0114 (7)	0.0012 (5)	−0.0011 (5)	0.0021 (6)
C5	0.0165 (6)	0.0184 (7)	0.0111 (6)	0.0015 (6)	0.0022 (5)	0.0002 (6)
C6	0.0089 (5)	0.0101 (6)	0.0145 (6)	−0.0006 (5)	−0.0007 (4)	0.0002 (5)
C7	0.0118 (5)	0.0130 (6)	0.0140 (6)	0.0028 (5)	−0.0007 (4)	0.0012 (5)
C8	0.0113 (6)	0.0114 (6)	0.0219 (8)	−0.0008 (5)	0.0032 (5)	−0.0019 (6)

O1—C6	1.2716 (19)	N3—H1N3	0.87 (2)
O2—C6	1.2542 (17)	C1—C2	1.4305 (19)
O3—C8	1.320 (2)	C2—C3	1.382 (2)
O3—H1O3	0.93 (4)	C3—C4	1.409 (2)
O4—C8	1.2168 (19)	C3—H3A	0.9500
N1—C1	1.3482 (18)	C4—C5	1.361 (2)
N1—C5	1.3638 (19)	C4—H4A	0.9500
N1—H1N1	0.92 (3)	C5—H5A	0.9500
N2—C1	1.344 (2)	C6—C7	1.524 (2)
N2—H2N2	0.87 (3)	C7—C8	1.516 (2)
N2—H1N2	0.88 (3)	C7—H7A	0.9900
N3—C2	1.3731 (19)	C7—H7B	0.9900
N3—H2N3	0.88 (3)
C8—O3—H1O3	104.9 (19)	C5—C4—C3	119.31 (14)
C1—N1—C5	123.70 (13)	C5—C4—H4A	120.3
C1—N1—H1N1	116.0 (18)	C3—C4—H4A	120.3
C5—N1—H1N1	120.3 (18)	C4—C5—N1	119.42 (14)
C1—N2—H2N2	115.8 (16)	C4—C5—H5A	120.3
C1—N2—H1N2	114.6 (16)	N1—C5—H5A	120.3
H2N2—N2—H1N2	123 (2)	O2—C6—O1	124.51 (13)
C2—N3—H2N3	113.0 (16)	O2—C6—C7	116.82 (13)
C2—N3—H1N3	115.7 (15)	O1—C6—C7	118.66 (12)
H2N3—N3—H1N3	125 (2)	C8—C7—C6	119.27 (13)
N2—C1—N1	118.52 (13)	C8—C7—H7A	107.5
N2—C1—C2	122.95 (13)	C6—C7—H7A	107.5
N1—C1—C2	118.48 (13)	C8—C7—H7B	107.5
N3—C2—C3	123.85 (13)	C6—C7—H7B	107.5
N3—C2—C1	118.10 (13)	H7A—C7—H7B	107.0
C3—C2—C1	117.95 (12)	O4—C8—O3	121.78 (15)
C2—C3—C4	121.14 (13)	O4—C8—C7	121.03 (16)
C2—C3—H3A	119.4	O3—C8—C7	117.19 (13)
C4—C3—H3A	119.4
C5—N1—C1—N2	176.82 (14)	C2—C3—C4—C5	−0.5 (2)
C5—N1—C1—C2	−0.8 (2)	C3—C4—C5—N1	0.0 (2)
N2—C1—C2—N3	−0.7 (2)	C1—N1—C5—C4	0.7 (2)
N1—C1—C2—N3	176.80 (14)	O2—C6—C7—C8	172.90 (13)
N2—C1—C2—C3	−177.26 (15)	O1—C6—C7—C8	−8.2 (2)
N1—C1—C2—C3	0.3 (2)	C6—C7—C8—O4	−175.86 (14)
N3—C2—C3—C4	−175.92 (16)	C6—C7—C8—O3	4.6 (2)
C1—C2—C3—C4	0.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1O3···O1	0.93 (4)	1.63 (3)	2.5208 (16)	159 (3)
N3—H2N3···O4i	0.88 (3)	2.16 (3)	2.9133 (19)	143 (2)
N2—H2N2···O2ii	0.87 (3)	2.15 (3)	3.0066 (18)	168 (2)
N1—H1N1···O1iii	0.92 (3)	1.87 (3)	2.7782 (16)	168 (3)
N2—H1N2···O2iii	0.88 (3)	2.12 (3)	2.9470 (18)	157 (3)
N3—H1N3···O2ii	0.87 (2)	2.18 (2)	3.0574 (19)	178 (3)
C7—H7B···O2iv	0.99	2.46	3.3532 (19)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H1O3⋯O1	0.93 (4)	1.63 (3)	2.5208 (16)	159 (3)
N3—H2N3⋯O4i	0.88 (3)	2.16 (3)	2.9133 (19)	143 (2)
N2—H2N2⋯O2ii	0.87 (3)	2.15 (3)	3.0066 (18)	168 (2)
N1—H1N1⋯O1iii	0.92 (3)	1.87 (3)	2.7782 (16)	168 (3)
N2—H1N2⋯O2iii	0.88 (3)	2.12 (3)	2.9470 (18)	157 (3)
N3—H1N3⋯O2ii	0.87 (2)	2.18 (2)	3.0574 (19)	178 (3)
C7—H7B⋯O2iv	0.99	2.46	3.3532 (19)	149

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