3,4-Diaminopyridinium 2-carboxy-4,6-dinitrophenolate.

In the title salt, C(5)H(8)N(3) (+)·C(7)H(3)N(2)O(7) (-), the pyridine N atom of the 3,4-diamino-pyridine mol-ecule is protonated. The 3,5-dinitro-salicylate anion shows whole-mol-ecule disorder over two orientations with a refined occupancy ratio of 0.875 (4): 0.125 (4). In the crystal, the cations and anions are connected by inter-molecular N-H⋯O and C-H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For applications of diamino­pyridine, see: Abu Zuhri & Cox (1989 ▶); Inuzuka & Fujimoto (1990 ▶); El-Mossalamy (2001 ▶). For related structures, see: Rubin-Preminger & Englert (2007 ▶); Koleva et al. (2007 ▶); Koleva et al. (2008 ▶). For reference bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C5H8N3 +·C7H3N2O7 −

M = 337.26

Monoclinic,

a = 9.1187 (4) Å

b = 11.3569 (5) Å

c = 13.1343 (6) Å

β = 98.204 (4)°

V = 1346.27 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.14 mm−1

T = 100 K

0.52 × 0.11 × 0.10 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.931, T max = 0.986

10195 measured reflections

2785 independent reflections

1979 reflections with I > 2σ(I)

R int = 0.064

Refinement

R[F 2 > 2σ(F 2)] = 0.070

wR(F 2) = 0.162

S = 1.12

2785 reflections

287 parameters

526 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.28 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/S1600536810038936/hb5660sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810038936/hb5660Isup2.hkl

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

C5H8N3+·C7H3N2O7−	F(000) = 696
Mr = 337.26	Dx = 1.664 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2307 reflections
a = 9.1187 (4) Å	θ = 2.4–28.6°
b = 11.3569 (5) Å	µ = 0.14 mm−1
c = 13.1343 (6) Å	T = 100 K
β = 98.204 (4)°	Needle, yellow
V = 1346.27 (10) Å3	0.52 × 0.11 × 0.10 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	2785 independent reflections
Radiation source: fine-focus sealed tube	1979 reflections with I > 2σ(I)
graphite	Rint = 0.064
φ and ω scans	θmax = 26.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.931, Tmax = 0.986	k = −14→14
10195 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)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162	H-atom parameters constrained
S = 1.12	w = 1/[σ2(Fo2) + (0.0439P)2 + 2.4565P] where P = (Fo2 + 2Fc2)/3
2785 reflections	(Δ/σ)max < 0.001
279 parameters	Δρmax = 0.46 e Å−3
526 restraints	Δρmin = −0.28 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	Occ. (<1)
N1	0.1346 (3)	0.4299 (2)	−0.0435 (2)	0.0286 (7)
H1N1	0.2282	0.4863	−0.0241	0.034*
N2	0.0269 (3)	0.1468 (3)	0.0541 (2)	0.0370 (8)
H2N2	−0.0550	0.1048	0.0573	0.044*
H1N2	0.1048	0.1417	0.1192	0.044*
N3	−0.1784 (3)	0.1759 (2)	−0.1255 (2)	0.0279 (7)
H1N3	−0.1717	0.1109	−0.0876	0.034*
H2N3	−0.2376	0.1940	−0.1942	0.034*
C1	0.1297 (4)	0.3365 (3)	0.0206 (3)	0.0283 (8)
H1A	0.1953	0.3325	0.0816	0.034*
C2	0.0275 (3)	0.2469 (3)	−0.0045 (3)	0.0274 (8)
C3	−0.0744 (3)	0.2571 (3)	−0.0968 (2)	0.0253 (7)
C4	−0.0643 (4)	0.3579 (3)	−0.1599 (3)	0.0275 (8)
H4A	−0.1299	0.3671	−0.2204	0.033*
C5	0.0411 (4)	0.4406 (3)	−0.1315 (3)	0.0298 (8)
H5A	0.0486	0.5054	−0.1737	0.036*
O1	0.3734 (3)	0.5460 (2)	0.06336 (19)	0.0242 (7)	0.886 (4)
O2	0.5011 (3)	0.4686 (2)	0.2297 (2)	0.0278 (7)	0.886 (4)
H2	0.4413	0.4777	0.1774	0.033*	0.886 (4)
O3	0.6962 (5)	0.5623 (2)	0.3110 (3)	0.0274 (9)	0.886 (4)
O4	0.2470 (6)	0.6533 (5)	−0.1085 (5)	0.0309 (11)	0.886 (4)
O5	0.3768 (6)	0.7848 (5)	−0.1745 (3)	0.0242 (10)	0.886 (4)
O6	0.7238 (3)	1.0170 (3)	0.0450 (3)	0.0246 (7)	0.886 (4)
O7	0.8474 (3)	0.9354 (3)	0.1809 (2)	0.0270 (7)	0.886 (4)
N4	0.3541 (10)	0.7207 (7)	−0.1015 (5)	0.0204 (9)	0.886 (4)
N5	0.7468 (3)	0.9350 (3)	0.1074 (3)	0.0191 (7)	0.886 (4)
C6	0.5497 (8)	0.8229 (5)	0.0041 (4)	0.0177 (14)	0.886 (4)
H6A	0.5442	0.8801	−0.0470	0.021*	0.886 (4)
C7	0.4568 (12)	0.7259 (7)	−0.0067 (6)	0.0182 (12)	0.886 (4)
C8	0.4606 (6)	0.6350 (4)	0.0699 (4)	0.0179 (9)	0.886 (4)
C9	0.5741 (4)	0.6491 (3)	0.1573 (3)	0.0171 (8)	0.886 (4)
C10	0.6650 (4)	0.7456 (3)	0.1681 (3)	0.0162 (7)	0.886 (4)
H10A	0.7364	0.7530	0.2259	0.019*	0.886 (4)
C11	0.6506 (5)	0.8326 (4)	0.0926 (3)	0.0158 (8)	0.886 (4)
C12	0.5956 (4)	0.5570 (3)	0.2394 (3)	0.0210 (8)	0.886 (4)
O1B	0.703 (2)	0.7054 (19)	0.2650 (14)	0.037 (6)*	0.114 (4)
O2B	0.598 (2)	0.512 (2)	0.2943 (15)	0.034 (6)*	0.114 (4)
H2B	0.6584	0.5652	0.2956	0.01 (17)*	0.114 (4)
O3B	0.409 (3)	0.4439 (19)	0.1805 (19)	0.051 (7)*	0.114 (4)
O4B	0.833 (2)	0.892 (2)	0.2101 (17)	0.028 (6)*	0.114 (4)
O5B	0.722 (3)	0.995 (2)	0.0788 (19)	0.013 (6)*	0.114 (4)
O6B	0.375 (7)	0.811 (4)	−0.176 (4)	0.045 (16)*	0.114 (4)
O7B	0.250 (6)	0.660 (5)	−0.132 (4)	0.044 (15)*	0.114 (4)
N4B	0.733 (3)	0.908 (2)	0.138 (2)	0.032 (7)*	0.114 (4)
N5B	0.353 (10)	0.733 (7)	−0.115 (4)	0.032 (7)*	0.114 (4)
C6B	0.537 (6)	0.824 (4)	0.018 (3)	0.011 (6)*	0.114 (4)
H6BA	0.5362	0.8931	−0.0200	0.013*	0.114 (4)
C7B	0.633 (4)	0.811 (3)	0.110 (2)	0.011 (6)*	0.114 (4)
C8B	0.620 (3)	0.714 (2)	0.1781 (16)	0.007 (6)*	0.114 (4)
C9B	0.520 (3)	0.6226 (19)	0.1401 (17)	0.014 (5)*	0.114 (4)
C10B	0.432 (5)	0.633 (3)	0.049 (3)	0.014 (5)*	0.114 (4)
H10B	0.3639	0.5746	0.0275	0.016*	0.114 (4)
C11B	0.442 (12)	0.732 (7)	−0.014 (5)	0.026 (6)*	0.114 (4)
C12B	0.499 (3)	0.521 (2)	0.2106 (18)	0.026 (6)*	0.114 (4)

	U11	U22	U33	U12	U13	U23
N1	0.0268 (15)	0.0294 (15)	0.0305 (16)	0.0010 (13)	0.0071 (13)	−0.0046 (12)
N2	0.0307 (15)	0.0329 (17)	0.0469 (19)	−0.0038 (14)	0.0036 (14)	0.0063 (14)
N3	0.0288 (14)	0.0247 (14)	0.0296 (15)	−0.0042 (12)	0.0017 (12)	0.0005 (12)
C1	0.0268 (17)	0.0239 (17)	0.037 (2)	0.0027 (15)	0.0138 (15)	−0.0011 (15)
C2	0.0254 (17)	0.0312 (18)	0.0262 (17)	0.0103 (15)	0.0055 (14)	−0.0011 (14)
C3	0.0219 (16)	0.0277 (18)	0.0282 (18)	0.0005 (14)	0.0098 (14)	−0.0089 (14)
C4	0.0260 (16)	0.0239 (17)	0.0346 (19)	0.0016 (14)	0.0110 (15)	−0.0036 (14)
C5	0.0318 (18)	0.0268 (18)	0.0319 (19)	0.0035 (15)	0.0089 (15)	0.0015 (14)
O1	0.0243 (13)	0.0203 (13)	0.0282 (14)	−0.0050 (11)	0.0047 (11)	−0.0006 (10)
O2	0.0340 (15)	0.0211 (15)	0.0283 (15)	−0.0031 (12)	0.0053 (12)	0.0083 (12)
O3	0.0300 (15)	0.0260 (19)	0.0258 (16)	0.0037 (12)	0.0021 (15)	0.0078 (11)
O4	0.0240 (18)	0.034 (2)	0.033 (3)	−0.0167 (12)	−0.0016 (18)	0.0034 (19)
O5	0.0281 (19)	0.024 (2)	0.0201 (18)	−0.0091 (18)	0.0016 (11)	0.0047 (15)
O6	0.0303 (16)	0.0173 (15)	0.0266 (18)	−0.0026 (11)	0.0051 (14)	0.0060 (13)
O7	0.0245 (14)	0.0227 (15)	0.0308 (16)	−0.0050 (12)	−0.0065 (12)	−0.0017 (13)
N4	0.0193 (16)	0.023 (3)	0.020 (2)	−0.0003 (18)	0.0050 (17)	−0.0003 (14)
N5	0.0198 (16)	0.0176 (18)	0.0203 (18)	0.0005 (14)	0.0038 (14)	−0.0027 (15)
C6	0.019 (2)	0.0193 (19)	0.016 (2)	0.0018 (15)	0.009 (2)	−0.0020 (16)
C7	0.016 (3)	0.020 (2)	0.020 (2)	0.002 (2)	0.0068 (14)	−0.0020 (14)
C8	0.018 (3)	0.0159 (17)	0.021 (3)	0.0011 (16)	0.0086 (17)	−0.0020 (16)
C9	0.018 (2)	0.0158 (18)	0.0183 (17)	0.0026 (16)	0.0059 (14)	0.0005 (14)
C10	0.0153 (17)	0.0164 (18)	0.0182 (18)	−0.0011 (16)	0.0067 (14)	−0.0041 (14)
C11	0.018 (2)	0.011 (2)	0.020 (2)	−0.0012 (14)	0.0103 (16)	−0.0006 (14)
C12	0.0255 (19)	0.0153 (16)	0.024 (2)	0.0030 (15)	0.0096 (16)	0.0010 (15)

N1—C5	1.341 (4)	C6—C7	1.384 (5)
N1—C1	1.358 (4)	C6—H6A	0.9300
N1—H1N1	1.0684	C7—C8	1.438 (5)
N2—C2	1.373 (4)	C8—C9	1.441 (5)
N2—H2N2	0.8919	C9—C10	1.369 (5)
N2—H1N2	1.0329	C9—C12	1.494 (5)
N3—C3	1.338 (4)	C10—C11	1.393 (5)
N3—H1N3	0.8875	C10—H10A	0.9300
N3—H2N3	1.0043	O1B—C8B	1.281 (16)
C1—C2	1.387 (5)	O2B—C12B	1.322 (16)
C1—H1A	0.9300	O2B—H2B	0.8200
C2—C3	1.423 (4)	O3B—C12B	1.229 (17)
C3—C4	1.424 (5)	O4B—N4B	1.230 (17)
C4—C5	1.357 (5)	O5B—N4B	1.249 (17)
C4—H4A	0.9300	O6B—N5B	1.237 (18)
C5—H5A	0.9300	O7B—N5B	1.246 (18)
O1—C8	1.282 (5)	N4B—C7B	1.445 (16)
O2—C12	1.317 (4)	N5B—C11B	1.454 (17)
O2—H2	0.8200	C6B—C11B	1.386 (18)
O3—C12	1.219 (6)	C6B—C7B	1.388 (18)
O4—N4	1.234 (4)	C6B—H6BA	0.9300
O5—N4	1.244 (5)	C7B—C8B	1.436 (16)
O6—N5	1.239 (5)	C8B—C9B	1.424 (16)
O7—N5	1.233 (4)	C9B—C10B	1.348 (16)
N4—C7	1.449 (5)	C9B—C12B	1.507 (16)
N5—C11	1.453 (5)	C10B—C11B	1.398 (18)
C6—C11	1.381 (5)	C10B—H10B	0.9300
C5—N1—C1	122.1 (3)	C10—C9—C8	121.8 (3)
C5—N1—H1N1	122.6	C10—C9—C12	118.0 (3)
C1—N1—H1N1	114.6	C8—C9—C12	120.2 (3)
C2—N2—H2N2	122.6	C9—C10—C11	120.0 (3)
C2—N2—H1N2	116.9	C9—C10—H10A	120.0
H2N2—N2—H1N2	114.3	C11—C10—H10A	120.0
C3—N3—H1N3	115.2	C6—C11—C10	121.8 (4)
C3—N3—H2N3	112.3	C6—C11—N5	119.6 (4)
H1N3—N3—H2N3	131.3	C10—C11—N5	118.6 (3)
N1—C1—C2	120.4 (3)	O3—C12—O2	121.5 (3)
N1—C1—H1A	119.8	O3—C12—C9	122.0 (3)
C2—C1—H1A	119.8	O2—C12—C9	116.5 (3)
N2—C2—C1	122.0 (3)	C12B—O2B—H2B	109.5
N2—C2—C3	119.4 (3)	O4B—N4B—O5B	126 (2)
C1—C2—C3	118.5 (3)	O4B—N4B—C7B	116.9 (19)
N3—C3—C2	122.3 (3)	O5B—N4B—C7B	116.5 (18)
N3—C3—C4	119.5 (3)	O6B—N5B—O7B	123 (3)
C2—C3—C4	118.3 (3)	O6B—N5B—C11B	119 (2)
C5—C4—C3	119.9 (3)	O7B—N5B—C11B	118 (3)
C5—C4—H4A	120.1	C11B—C6B—C7B	118.0 (19)
C3—C4—H4A	120.1	C11B—C6B—H6BA	121.0
N1—C5—C4	120.8 (3)	C7B—C6B—H6BA	121.0
N1—C5—H5A	119.6	C6B—C7B—C8B	121.6 (17)
C4—C5—H5A	119.6	C6B—C7B—N4B	115.9 (18)
C12—O2—H2	109.5	C8B—C7B—N4B	121.9 (17)
O4—N4—O5	121.5 (4)	O1B—C8B—C9B	121.6 (16)
O4—N4—C7	119.8 (4)	O1B—C8B—C7B	121.6 (17)
O5—N4—C7	118.7 (4)	C9B—C8B—C7B	116.4 (15)
O7—N5—O6	123.5 (3)	C10B—C9B—C8B	120.9 (16)
O7—N5—C11	118.3 (4)	C10B—C9B—C12B	120.2 (17)
O6—N5—C11	118.1 (3)	C8B—C9B—C12B	118.2 (15)
C11—C6—C7	118.3 (4)	C9B—C10B—C11B	121 (2)
C11—C6—H6A	120.9	C9B—C10B—H10B	119.5
C7—C6—H6A	120.9	C11B—C10B—H10B	119.5
C6—C7—C8	123.1 (4)	C6B—C11B—C10B	121.0 (19)
C6—C7—N4	115.5 (4)	C6B—C11B—N5B	121 (2)
C8—C7—N4	121.3 (4)	C10B—C11B—N5B	118 (2)
O1—C8—C7	124.5 (4)	O3B—C12B—O2B	124 (2)
O1—C8—C9	120.6 (4)	O3B—C12B—C9B	119.1 (17)
C7—C8—C9	114.9 (3)	O2B—C12B—C9B	116.2 (17)
C5—N1—C1—C2	1.0 (5)	O6—N5—C11—C10	−173.2 (4)
N1—C1—C2—N2	174.7 (3)	C10—C9—C12—O3	−4.5 (5)
N1—C1—C2—C3	−1.9 (5)	C8—C9—C12—O3	175.3 (4)
N2—C2—C3—N3	4.7 (5)	C10—C9—C12—O2	176.3 (3)
C1—C2—C3—N3	−178.6 (3)	C8—C9—C12—O2	−3.8 (5)
N2—C2—C3—C4	−175.5 (3)	C11B—C6B—C7B—C8B	−10 (11)
C1—C2—C3—C4	1.2 (4)	C11B—C6B—C7B—N4B	178 (8)
N3—C3—C4—C5	−179.8 (3)	O4B—N4B—C7B—C6B	−170 (5)
C2—C3—C4—C5	0.4 (5)	O5B—N4B—C7B—C6B	1(7)
C1—N1—C5—C4	0.7 (5)	O4B—N4B—C7B—C8B	18 (6)
C3—C4—C5—N1	−1.4 (5)	O5B—N4B—C7B—C8B	−171 (4)
C11—C6—C7—C8	0.0 (17)	C6B—C7B—C8B—O1B	−176 (5)
C11—C6—C7—N4	−179.7 (9)	N4B—C7B—C8B—O1B	−5(6)
O4—N4—C7—C6	−164.1 (11)	C6B—C7B—C8B—C9B	10 (7)
O5—N4—C7—C6	16.1 (17)	N4B—C7B—C8B—C9B	−179 (4)
O4—N4—C7—C8	16.2 (18)	O1B—C8B—C9B—C10B	179 (4)
O5—N4—C7—C8	−163.6 (11)	C7B—C8B—C9B—C10B	−7(6)
C6—C7—C8—O1	178.0 (9)	O1B—C8B—C9B—C12B	8(5)
N4—C7—C8—O1	−2.3 (17)	C7B—C8B—C9B—C12B	−178 (3)
C6—C7—C8—C9	−3.0 (16)	C8B—C9B—C10B—C11B	4(10)
N4—C7—C8—C9	176.7 (10)	C12B—C9B—C10B—C11B	175 (8)
O1—C8—C9—C10	−177.5 (4)	C7B—C6B—C11B—C10B	7(16)
C7—C8—C9—C10	3.5 (9)	C7B—C6B—C11B—N5B	−172 (10)
O1—C8—C9—C12	2.7 (7)	C9B—C10B—C11B—C6B	−4(16)
C7—C8—C9—C12	−176.4 (7)	C9B—C10B—C11B—N5B	175 (9)
C8—C9—C10—C11	−1.0 (6)	O6B—N5B—C11B—C6B	9(19)
C12—C9—C10—C11	178.9 (4)	O7B—N5B—C11B—C6B	−167 (12)
C7—C6—C11—C10	2.8 (12)	O6B—N5B—C11B—C10B	−170 (11)
C7—C6—C11—N5	−178.3 (9)	O7B—N5B—C11B—C10B	15 (18)
C9—C10—C11—C6	−2.3 (7)	C10B—C9B—C12B—O3B	6(6)
C9—C10—C11—N5	178.7 (4)	C8B—C9B—C12B—O3B	177 (3)
O7—N5—C11—C6	−171.6 (5)	C10B—C9B—C12B—O2B	175 (4)
O6—N5—C11—C6	7.8 (7)	C8B—C9B—C12B—O2B	−14 (4)
O7—N5—C11—C10	7.3 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1	1.07	1.76	2.753 (4)	153
O2—H2···O1	0.82	1.72	2.485 (4)	154
N2—H2N2···O6i	0.89	2.24	3.120 (4)	171
N2—H1N2···O3ii	1.03	2.11	3.026 (5)	146
N3—H1N3···O6i	0.89	2.36	3.104 (4)	142
N3—H2N3···O5iii	1.00	2.24	3.217 (5)	163
C6—H6A···O3iv	0.93	2.56	3.299 (6)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1	1.07	1.76	2.753 (4)	153
N2—H2N2⋯O6i	0.89	2.24	3.120 (4)	171
N2—H1N2⋯O3ii	1.03	2.11	3.026 (5)	146
N3—H1N3⋯O6i	0.89	2.36	3.104 (4)	142
N3—H2N3⋯O5iii	1.00	2.24	3.217 (5)	163
C6—H6A⋯O3iv	0.93	2.56	3.299 (6)	136

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