4-Amino-3-ammonio-pyridinium dinitrate.

In the crystal structure of the title compound, C(5)H(9)N(3) (2+)·2NO(3) (-), the cations and anions are connected by inter-molecular N-H⋯O and C-H⋯O hydrogen bonds, forming a three-dimensional network. The crystal structure is further stabilized by π⋯π inter-actions between pyridinium rings [centroid-centroid distance = 3.775 (4) Å].

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶); Abu Zuhri & Cox (1989 ▶). For related structures, see: Fun & Balasubramani (2009 ▶); Rubin-Preminger & Englert (2007 ▶); Qin & Wang (2009 ▶). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶). 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

C5H9N3 2+·2NO3 −

M = 235.17

Monoclinic,

a = 12.3008 (5) Å

b = 10.5086 (5) Å

c = 7.1411 (3) Å

β = 97.546 (1)°

V = 915.09 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.16 mm−1

T = 100 K

0.65 × 0.37 × 0.28 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.906, T max = 0.958

18234 measured reflections

4796 independent reflections

4129 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.096

S = 1.06

4796 reflections

181 parameters

All H-atom parameters refined

Δρmax = 0.66 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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810005556/rz2419sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005556/rz2419Isup2.hkl

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

C5H9N32+·2NO3−	F(000) = 488
Mr = 235.17	Dx = 1.707 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9066 reflections
a = 12.3008 (5) Å	θ = 3.3–37.5°
b = 10.5086 (5) Å	µ = 0.16 mm−1
c = 7.1411 (3) Å	T = 100 K
β = 97.546 (1)°	Block, colourless
V = 915.09 (7) Å3	0.65 × 0.37 × 0.28 mm
Z = 4

Bruker APEX DUO CCD area-detector diffractometer	4796 independent reflections
Radiation source: fine-focus sealed tube	4129 reflections with I > 2σ(I)
graphite	Rint = 0.024
φ and ω scans	θmax = 37.6°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −21→20
Tmin = 0.906, Tmax = 0.958	k = −17→17
18234 measured reflections	l = −10→12

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	All H-atom parameters refined
S = 1.06	w = 1/[σ2(Fo2) + (0.0545P)2 + 0.1242P] where P = (Fo2 + 2Fc2)/3
4796 reflections	(Δ/σ)max = 0.001
181 parameters	Δρmax = 0.66 e Å−3
0 restraints	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 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	0.18671 (4)	0.78615 (5)	0.42895 (7)	0.01262 (9)
N2	0.17802 (4)	0.43778 (5)	0.39491 (7)	0.01067 (8)
N3	0.39285 (4)	0.50229 (5)	0.29631 (9)	0.01537 (10)
C1	0.21985 (4)	0.56747 (5)	0.39298 (8)	0.00969 (9)
C2	0.15309 (5)	0.66472 (5)	0.43549 (8)	0.01097 (9)
C3	0.28652 (5)	0.81587 (6)	0.38180 (9)	0.01366 (10)
C4	0.35654 (5)	0.72296 (6)	0.33967 (9)	0.01302 (10)
C5	0.32559 (5)	0.59285 (5)	0.34337 (8)	0.01084 (9)
N4	0.07181 (4)	0.08353 (5)	0.36523 (7)	0.01101 (8)
O1	0.03294 (4)	0.19166 (5)	0.37605 (8)	0.01831 (10)
O2	0.12811 (4)	0.03373 (5)	0.50656 (7)	0.01704 (9)
O3	0.05534 (4)	0.02013 (5)	0.21333 (7)	0.01419 (8)
N5	0.34927 (4)	0.17325 (5)	0.27032 (7)	0.01208 (9)
O4	0.41357 (4)	0.23657 (5)	0.38374 (8)	0.01818 (9)
O5	0.25728 (4)	0.21885 (5)	0.20404 (8)	0.01714 (9)
O6	0.37509 (4)	0.06465 (4)	0.21848 (7)	0.01541 (9)
H2	0.0849 (9)	0.6508 (11)	0.4677 (16)	0.015 (2)*
H3	0.3044 (10)	0.9065 (11)	0.3781 (17)	0.019 (3)*
H4	0.4245 (10)	0.7452 (11)	0.3072 (17)	0.018 (2)*
H1N1	0.1431 (11)	0.8483 (12)	0.4515 (19)	0.024 (3)*
H1N2	0.1923 (12)	0.3916 (14)	0.289 (2)	0.036 (3)*
H2N2	0.1064 (11)	0.4422 (13)	0.393 (2)	0.030 (3)*
H1N3	0.3832 (12)	0.4256 (15)	0.325 (2)	0.036 (4)*
H2N3	0.4547 (10)	0.5255 (11)	0.2771 (18)	0.022 (3)*
H3N2	0.2027 (10)	0.3986 (12)	0.4994 (17)	0.022 (3)*

	U11	U22	U33	U12	U13	U23
N1	0.0158 (2)	0.00975 (18)	0.01202 (19)	0.00126 (15)	0.00078 (15)	−0.00025 (14)
N2	0.01164 (19)	0.00934 (17)	0.01122 (19)	−0.00130 (14)	0.00219 (15)	−0.00007 (14)
N3	0.0131 (2)	0.0132 (2)	0.0209 (2)	0.00103 (16)	0.00640 (18)	0.00051 (17)
C1	0.01061 (19)	0.00874 (19)	0.00967 (19)	−0.00068 (14)	0.00112 (15)	0.00042 (15)
C2	0.0119 (2)	0.0106 (2)	0.0102 (2)	0.00047 (15)	0.00092 (16)	0.00022 (15)
C3	0.0177 (2)	0.0110 (2)	0.0120 (2)	−0.00248 (17)	0.00083 (18)	0.00069 (17)
C4	0.0137 (2)	0.0124 (2)	0.0130 (2)	−0.00291 (17)	0.00193 (17)	0.00085 (16)
C5	0.0109 (2)	0.0114 (2)	0.0102 (2)	−0.00046 (15)	0.00145 (16)	0.00062 (16)
N4	0.01104 (18)	0.01129 (18)	0.01079 (18)	0.00072 (14)	0.00182 (14)	−0.00057 (14)
O1	0.0205 (2)	0.01273 (19)	0.0212 (2)	0.00626 (15)	0.00077 (17)	−0.00324 (15)
O2	0.0227 (2)	0.0157 (2)	0.01131 (18)	0.00386 (16)	−0.00316 (16)	0.00055 (14)
O3	0.01560 (19)	0.01632 (19)	0.01055 (17)	0.00110 (14)	0.00129 (14)	−0.00395 (14)
N5	0.01301 (19)	0.01063 (18)	0.0129 (2)	−0.00098 (14)	0.00270 (15)	−0.00080 (14)
O4	0.0181 (2)	0.0161 (2)	0.0189 (2)	−0.00316 (15)	−0.00271 (16)	−0.00424 (16)
O5	0.01401 (19)	0.0165 (2)	0.0200 (2)	0.00356 (15)	−0.00103 (15)	−0.00464 (16)
O6	0.0170 (2)	0.00960 (17)	0.0202 (2)	0.00105 (13)	0.00446 (16)	−0.00208 (14)

N1—C2	1.3442 (7)	C2—H2	0.910 (11)
N1—C3	1.3516 (8)	C3—C4	1.3615 (9)
N1—H1N1	0.873 (13)	C3—H3	0.978 (12)
N2—C1	1.4575 (7)	C4—C5	1.4205 (8)
N2—H1N2	0.934 (15)	C4—H4	0.926 (12)
N2—H2N2	0.881 (14)	N4—O1	1.2392 (7)
N2—H3N2	0.871 (13)	N4—O2	1.2603 (7)
N3—C5	1.3327 (8)	N4—O3	1.2664 (7)
N3—H1N3	0.844 (16)	N5—O4	1.2474 (7)
N3—H2N3	0.827 (13)	N5—O6	1.2534 (7)
C1—C2	1.3698 (8)	N5—O5	1.2623 (7)
C1—C5	1.4176 (8)
C2—N1—C3	121.45 (5)	C1—C2—H2	122.4 (7)
C2—N1—H1N1	120.3 (9)	N1—C3—C4	120.74 (5)
C3—N1—H1N1	118.3 (9)	N1—C3—H3	116.5 (7)
C1—N2—H1N2	111.9 (9)	C4—C3—H3	122.7 (7)
C1—N2—H2N2	107.7 (9)	C3—C4—C5	120.48 (5)
H1N2—N2—H2N2	108.1 (13)	C3—C4—H4	119.5 (7)
C1—N2—H3N2	111.5 (8)	C5—C4—H4	120.1 (7)
H1N2—N2—H3N2	111.5 (12)	N3—C5—C1	123.30 (5)
H2N2—N2—H3N2	105.8 (12)	N3—C5—C4	120.39 (5)
C5—N3—H1N3	120.6 (10)	C1—C5—C4	116.28 (5)
C5—N3—H2N3	116.5 (8)	O1—N4—O2	120.45 (5)
H1N3—N3—H2N3	118.9 (13)	O1—N4—O3	121.07 (5)
C2—C1—C5	120.77 (5)	O2—N4—O3	118.47 (5)
C2—C1—N2	118.22 (5)	O4—N5—O6	120.92 (5)
C5—C1—N2	120.99 (5)	O4—N5—O5	120.11 (5)
N1—C2—C1	120.29 (5)	O6—N5—O5	118.97 (5)
N1—C2—H2	117.3 (7)
C3—N1—C2—C1	−0.36 (9)	N2—C1—C5—N3	−0.09 (9)
C5—C1—C2—N1	0.63 (9)	C2—C1—C5—C4	−0.38 (8)
N2—C1—C2—N1	−177.64 (5)	N2—C1—C5—C4	177.85 (5)
C2—N1—C3—C4	−0.16 (9)	C3—C4—C5—N3	177.88 (6)
N1—C3—C4—C5	0.40 (9)	C3—C4—C5—C1	−0.13 (9)
C2—C1—C5—N3	−178.32 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2i	0.874 (13)	2.001 (13)	2.7750 (7)	147.0 (12)
N2—H1N2···O5	0.935 (14)	2.105 (15)	2.9070 (8)	143.1 (12)
N2—H1N2···O2ii	0.935 (14)	2.211 (14)	2.7767 (7)	118.1 (11)
N2—H2N2···O3iii	0.881 (14)	2.193 (14)	3.0006 (7)	152.3 (12)
N2—H2N2···O3iv	0.881 (14)	2.482 (14)	2.9231 (7)	111.6 (11)
N3—H1N3···O4	0.844 (16)	2.054 (16)	2.8653 (8)	161.0 (14)
N3—H2N3···O6v	0.827 (12)	2.130 (12)	2.9442 (7)	168.0 (12)
N2—H3N2···O5iv	0.871 (12)	1.963 (12)	2.8227 (8)	169.0 (12)
N2—H3N2···O6iv	0.871 (12)	2.494 (12)	3.1217 (7)	129.5 (10)
C2—H2···O3iii	0.910 (11)	2.439 (11)	3.0489 (8)	124.6 (9)
C2—H2···O1vi	0.910 (11)	2.552 (11)	3.1834 (8)	127.0 (9)
C2—H2···O3iv	0.910 (11)	2.570 (11)	3.1277 (8)	120.2 (9)
C3—H3···O6i	0.979 (12)	2.253 (12)	3.1170 (8)	146.6 (10)
C4—H4···O4v	0.926 (12)	2.559 (12)	3.4274 (8)	156.3 (10)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2i	0.874 (13)	2.001 (13)	2.7750 (7)	147.0 (12)
N2—H1N2⋯O5	0.935 (14)	2.105 (15)	2.9070 (8)	143.1 (12)
N2—H1N2⋯O2ii	0.935 (14)	2.211 (14)	2.7767 (7)	118.1 (11)
N2—H2N2⋯O3iii	0.881 (14)	2.193 (14)	3.0006 (7)	152.3 (12)
N2—H2N2⋯O3iv	0.881 (14)	2.482 (14)	2.9231 (7)	111.6 (11)
N3—H1N3⋯O4	0.844 (16)	2.054 (16)	2.8653 (8)	161.0 (14)
N3—H2N3⋯O6v	0.827 (12)	2.130 (12)	2.9442 (7)	168.0 (12)
N2—H3N2⋯O5iv	0.871 (12)	1.963 (12)	2.8227 (8)	169.0 (12)
N2—H3N2⋯O6iv	0.871 (12)	2.494 (12)	3.1217 (7)	129.5 (10)
C2—H2⋯O3iii	0.910 (11)	2.439 (11)	3.0489 (8)	124.6 (9)
C2—H2⋯O1vi	0.910 (11)	2.552 (11)	3.1834 (8)	127.0 (9)
C2—H2⋯O3iv	0.910 (11)	2.570 (11)	3.1277 (8)	120.2 (9)
C3—H3⋯O6i	0.979 (12)	2.253 (12)	3.1170 (8)	146.6 (10)
C4—H4⋯O4v	0.926 (12)	2.559 (12)	3.4274 (8)	156.3 (10)

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