2-Amino-3-ammonio-pyridinium dichloride.

The asymmetric unit of the title compound, C(5)H(9)N(3) (2+)·2Cl(-), contains two diprotonated 2,3-diamino-pyridine cations and four chloride anions. In the crystal structure, the anions and cations are connected by inter-molecular N-H⋯Cl and C-H⋯Cl hydrogen bonds, forming a three-dimensional network. The crystal structure is further stabilized by π-π inter-actions between pyridinium rings [centroid-centroid distance = 3.695 (1) Å].

Related literature

For background to the chemistry of substituted pyridines and chloride anions, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶); Abu Zuhri & Cox (1989 ▶); De Cires-Mejias et al. (2004 ▶); Sessler et al. (2003 ▶). For related structures, see: Fun & Balasubramani (2009 ▶); Balasubramani & Fun (2009a ▶,b ▶). 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+·2Cl−

M = 182.05

Monoclinic,

a = 10.9770 (2) Å

b = 12.5175 (2) Å

c = 11.6520 (2) Å

β = 98.979 (1)°

V = 1581.42 (5) Å3

Z = 8

Mo Kα radiation

μ = 0.75 mm−1

T = 100 K

0.34 × 0.32 × 0.13 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.787, T max = 0.907

22610 measured reflections

5736 independent reflections

4042 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.109

S = 1.03

5736 reflections

253 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.22 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/S1600536810003624/wn2374sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003624/wn2374Isup2.hkl

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

C5H9N32+·2Cl−	F(000) = 752
Mr = 182.05	Dx = 1.529 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4939 reflections
a = 10.9770 (2) Å	θ = 2.4–31.0°
b = 12.5175 (2) Å	µ = 0.75 mm−1
c = 11.6520 (2) Å	T = 100 K
β = 98.979 (1)°	Block, brown
V = 1581.42 (5) Å3	0.34 × 0.32 × 0.13 mm
Z = 8

Bruker APEX DUO CCD area-detector diffractometer	5736 independent reflections
Radiation source: fine-focus sealed tube	4042 reflections with I > 2σ(I)
graphite	Rint = 0.035
φ and ω scans	θmax = 32.6°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −16→15
Tmin = 0.787, Tmax = 0.907	k = −18→18
22610 measured reflections	l = −17→17

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0489P)2 + 0.1879P] where P = (Fo2 + 2Fc2)/3
5736 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.22 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
Cl1	0.28885 (4)	0.19696 (4)	0.71503 (3)	0.03796 (11)
Cl2	1.04311 (4)	0.14551 (4)	0.94363 (3)	0.03993 (12)
Cl3	0.78343 (4)	0.38414 (4)	0.69663 (3)	0.04112 (12)
Cl4	0.47897 (4)	0.81032 (4)	0.52864 (3)	0.04069 (12)
N1	0.77439 (14)	−0.16705 (12)	0.55300 (12)	0.0311 (3)
N2	0.89490 (15)	−0.10343 (15)	0.77888 (13)	0.0415 (4)
N3	0.94910 (13)	0.05666 (13)	0.70138 (12)	0.0364 (3)
C1	0.94453 (17)	0.13025 (16)	0.61525 (17)	0.0413 (4)
C2	0.88294 (17)	0.10955 (15)	0.50822 (16)	0.0408 (4)
C3	0.82455 (15)	0.01104 (14)	0.48808 (13)	0.0323 (3)
C4	0.82915 (13)	−0.06214 (12)	0.57545 (12)	0.0255 (3)
C5	0.89151 (13)	−0.03864 (13)	0.68821 (12)	0.0279 (3)
N4	0.49075 (14)	0.64395 (13)	0.29409 (13)	0.0327 (3)
N5	0.62585 (16)	0.59088 (15)	0.52171 (13)	0.0409 (4)
N6	0.70640 (13)	0.44374 (12)	0.44118 (12)	0.0345 (3)
C6	0.71801 (16)	0.37487 (15)	0.35421 (16)	0.0384 (4)
C7	0.65521 (16)	0.39087 (15)	0.24616 (15)	0.0366 (4)
C8	0.57784 (15)	0.48000 (14)	0.22721 (13)	0.0315 (3)
C9	0.56779 (13)	0.54973 (13)	0.31554 (12)	0.0269 (3)
C10	0.63317 (13)	0.53062 (13)	0.42861 (12)	0.0276 (3)
H1A	0.9841 (18)	0.1899 (18)	0.6438 (18)	0.054 (6)*
H2A	0.8819 (18)	0.1582 (18)	0.4467 (18)	0.051 (6)*
H3A	0.7863 (16)	−0.0052 (15)	0.4205 (15)	0.032 (5)*
H6A	0.7766 (17)	0.3164 (17)	0.3824 (17)	0.051 (6)*
H7A	0.6660 (17)	0.3404 (17)	0.1831 (16)	0.045 (5)*
H8A	0.5334 (16)	0.4917 (14)	0.1540 (14)	0.031 (4)*
H1N1	0.8271 (19)	−0.2160 (18)	0.5682 (17)	0.048 (6)*
H2N1	0.744 (2)	−0.1729 (19)	0.480 (2)	0.063 (7)*
H3N1	0.705 (2)	−0.1742 (19)	0.5822 (19)	0.063 (7)*
H1N2	0.845 (2)	−0.160 (2)	0.779 (2)	0.058 (7)*
H2N2	0.9324 (19)	−0.0897 (18)	0.8401 (18)	0.051 (6)*
H1N3	0.9858 (19)	0.0747 (18)	0.7650 (18)	0.051 (6)*
H1N4	0.414 (2)	0.6363 (17)	0.3130 (17)	0.053 (6)*
H2N4	0.531 (2)	0.700 (2)	0.336 (2)	0.080 (8)*
H3N4	0.4843 (19)	0.6587 (18)	0.224 (2)	0.055 (6)*
H1N5	0.578 (2)	0.650 (2)	0.5188 (19)	0.057 (7)*
H2N5	0.6724 (18)	0.5757 (16)	0.5834 (17)	0.042 (5)*
H1N6	0.7491 (19)	0.4214 (18)	0.5080 (19)	0.055 (6)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0468 (2)	0.0417 (3)	0.02393 (17)	−0.00571 (18)	0.00127 (15)	−0.00426 (15)
Cl2	0.0490 (2)	0.0429 (3)	0.02580 (18)	−0.00792 (19)	−0.00072 (16)	−0.00412 (16)
Cl3	0.0343 (2)	0.0577 (3)	0.02968 (19)	−0.00126 (19)	−0.00008 (15)	0.00466 (17)
Cl4	0.0431 (2)	0.0488 (3)	0.02839 (19)	0.0020 (2)	−0.00015 (15)	−0.00488 (17)
N1	0.0352 (7)	0.0293 (8)	0.0280 (7)	−0.0041 (6)	0.0027 (6)	−0.0052 (5)
N2	0.0442 (8)	0.0546 (11)	0.0233 (7)	−0.0027 (8)	−0.0026 (6)	0.0061 (6)
N3	0.0359 (7)	0.0422 (9)	0.0292 (7)	−0.0067 (6)	−0.0008 (6)	−0.0108 (6)
C1	0.0418 (10)	0.0318 (10)	0.0498 (10)	−0.0081 (8)	0.0052 (8)	−0.0057 (8)
C2	0.0479 (10)	0.0317 (10)	0.0419 (9)	0.0011 (8)	0.0043 (8)	0.0066 (7)
C3	0.0362 (8)	0.0341 (9)	0.0243 (7)	0.0026 (7)	−0.0023 (6)	0.0007 (6)
C4	0.0270 (7)	0.0254 (8)	0.0235 (6)	0.0011 (6)	0.0026 (5)	−0.0035 (5)
C5	0.0255 (7)	0.0347 (9)	0.0230 (6)	0.0019 (6)	0.0027 (5)	−0.0032 (6)
N4	0.0298 (7)	0.0355 (8)	0.0310 (7)	0.0013 (6)	−0.0010 (6)	0.0030 (6)
N5	0.0486 (9)	0.0462 (10)	0.0264 (7)	−0.0019 (8)	0.0008 (6)	−0.0056 (6)
N6	0.0358 (7)	0.0369 (8)	0.0282 (6)	0.0015 (6)	−0.0027 (5)	0.0064 (6)
C6	0.0371 (9)	0.0325 (10)	0.0448 (9)	0.0042 (8)	0.0043 (7)	0.0038 (7)
C7	0.0433 (9)	0.0323 (10)	0.0347 (8)	−0.0041 (8)	0.0079 (7)	−0.0036 (7)
C8	0.0343 (8)	0.0340 (9)	0.0250 (7)	−0.0056 (7)	0.0007 (6)	0.0004 (6)
C9	0.0255 (7)	0.0286 (8)	0.0256 (6)	−0.0034 (6)	0.0012 (5)	0.0041 (6)
C10	0.0276 (7)	0.0302 (8)	0.0242 (6)	−0.0045 (6)	0.0021 (5)	0.0021 (6)

N1—C4	1.451 (2)	N4—C9	1.450 (2)
N1—H1N1	0.84 (2)	N4—H1N4	0.91 (2)
N1—H2N1	0.87 (2)	N4—H2N4	0.93 (3)
N1—H3N1	0.89 (2)	N4—H3N4	0.83 (2)
N2—C5	1.328 (2)	N5—C10	1.334 (2)
N2—H1N2	0.89 (2)	N5—H1N5	0.90 (2)
N2—H2N2	0.78 (2)	N5—H2N5	0.84 (2)
N3—C5	1.348 (2)	N6—C10	1.347 (2)
N3—C1	1.357 (2)	N6—C6	1.351 (2)
N3—H1N3	0.82 (2)	N6—H1N6	0.89 (2)
C1—C2	1.348 (3)	C6—C7	1.353 (2)
C1—H1A	0.90 (2)	C6—H6A	1.00 (2)
C2—C3	1.393 (3)	C7—C8	1.399 (2)
C2—H2A	0.94 (2)	C7—H7A	0.99 (2)
C3—C4	1.365 (2)	C8—C9	1.367 (2)
C3—H3A	0.857 (17)	C8—H8A	0.926 (16)
C4—C5	1.4145 (19)	C9—C10	1.4188 (19)
C4—N1—H1N1	111.6 (14)	C9—N4—H1N4	114.2 (14)
C4—N1—H2N1	109.7 (16)	C9—N4—H2N4	108.0 (15)
H1N1—N1—H2N1	106.9 (19)	H1N4—N4—H2N4	110 (2)
C4—N1—H3N1	112.3 (16)	C9—N4—H3N4	107.9 (15)
H1N1—N1—H3N1	117 (2)	H1N4—N4—H3N4	108.9 (18)
H2N1—N1—H3N1	98.5 (19)	H2N4—N4—H3N4	108 (2)
C5—N2—H1N2	122.6 (15)	C10—N5—H1N5	122.7 (14)
C5—N2—H2N2	122.3 (16)	C10—N5—H2N5	117.7 (14)
H1N2—N2—H2N2	114 (2)	H1N5—N5—H2N5	119 (2)
C5—N3—C1	123.65 (14)	C10—N6—C6	123.92 (14)
C5—N3—H1N3	120.3 (16)	C10—N6—H1N6	125.0 (14)
C1—N3—H1N3	116.0 (16)	C6—N6—H1N6	110.9 (14)
C2—C1—N3	120.59 (17)	N6—C6—C7	120.63 (17)
C2—C1—H1A	130.1 (14)	N6—C6—H6A	110.7 (12)
N3—C1—H1A	109.2 (14)	C7—C6—H6A	128.7 (12)
C1—C2—C3	118.52 (17)	C6—C7—C8	118.28 (16)
C1—C2—H2A	121.7 (13)	C6—C7—H7A	119.6 (11)
C3—C2—H2A	119.7 (13)	C8—C7—H7A	122.1 (11)
C4—C3—C2	120.41 (15)	C9—C8—C7	120.58 (14)
C4—C3—H3A	118.8 (13)	C9—C8—H8A	120.0 (11)
C2—C3—H3A	120.8 (13)	C7—C8—H8A	119.4 (11)
C3—C4—C5	120.64 (14)	C8—C9—C10	120.20 (15)
C3—C4—N1	120.47 (13)	C8—C9—N4	120.20 (13)
C5—C4—N1	118.84 (13)	C10—C9—N4	119.61 (14)
N2—C5—N3	119.72 (15)	N5—C10—N6	118.62 (15)
N2—C5—C4	124.16 (16)	N5—C10—C9	125.02 (16)
N3—C5—C4	116.12 (14)	N6—C10—C9	116.36 (14)
C5—N3—C1—C2	−1.9 (3)	C10—N6—C6—C7	0.6 (3)
N3—C1—C2—C3	−0.2 (3)	N6—C6—C7—C8	−0.3 (3)
C1—C2—C3—C4	0.5 (3)	C6—C7—C8—C9	1.0 (2)
C2—C3—C4—C5	1.0 (2)	C7—C8—C9—C10	−1.9 (2)
C2—C3—C4—N1	−176.49 (16)	C7—C8—C9—N4	177.80 (15)
C1—N3—C5—N2	−176.12 (17)	C6—N6—C10—N5	177.71 (16)
C1—N3—C5—C4	3.3 (2)	C6—N6—C10—C9	−1.4 (2)
C3—C4—C5—N2	176.56 (16)	C8—C9—C10—N5	−177.02 (15)
N1—C4—C5—N2	−5.9 (2)	N4—C9—C10—N5	3.3 (2)
C3—C4—C5—N3	−2.8 (2)	C8—C9—C10—N6	2.0 (2)
N1—C4—C5—N3	174.72 (14)	N4—C9—C10—N6	−177.64 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···Cl2i	0.84 (2)	2.26 (2)	3.081 (2)	164.4 (18)
N1—H2N1···Cl1ii	0.87 (2)	2.27 (2)	3.114 (1)	167 (2)
N1—H3N1···Cl4iii	0.89 (2)	2.47 (2)	3.223 (2)	143.2 (18)
N2—H1N2···Cl1iv	0.90 (2)	2.32 (2)	3.219 (2)	177.6 (16)
N2—H2N2···Cl2v	0.79 (2)	2.59 (2)	3.242 (2)	142 (2)
N3—H1N3···Cl2	0.82 (2)	2.26 (2)	3.060 (2)	166 (2)
N4—H1N4···Cl3vi	0.91 (2)	2.17 (2)	3.049 (2)	163.2 (17)
N4—H2N4···Cl4	0.93 (2)	2.77 (2)	3.454 (2)	131.5 (17)
N4—H2N4···Cl1vi	0.93 (2)	2.51 (2)	3.148 (2)	126.4 (18)
N4—H3N4···Cl4vii	0.83 (2)	2.30 (2)	3.128 (2)	175 (2)
N5—H1N5···Cl4	0.91 (2)	2.29 (2)	3.193 (2)	172.0 (18)
N5—H2N5···Cl1viii	0.84 (2)	2.77 (2)	3.340 (2)	126.6 (17)
N6—H1N6···Cl3	0.89 (2)	2.22 (2)	3.057 (1)	156.6 (19)
C7—H7A···Cl4ix	0.99 (2)	2.745 (19)	3.459 (2)	129.4 (14)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯Cl2i	0.84 (2)	2.26 (2)	3.081 (2)	164.4 (18)
N1—H2N1⋯Cl1ii	0.87 (2)	2.27 (2)	3.114 (1)	167 (2)
N1—H3N1⋯Cl4iii	0.89 (2)	2.47 (2)	3.223 (2)	143.2 (18)
N2—H1N2⋯Cl1iv	0.90 (2)	2.32 (2)	3.219 (2)	177.6 (16)
N2—H2N2⋯Cl2v	0.79 (2)	2.59 (2)	3.242 (2)	142 (2)
N3—H1N3⋯Cl2	0.82 (2)	2.26 (2)	3.060 (2)	166 (2)
N4—H1N4⋯Cl3vi	0.91 (2)	2.17 (2)	3.049 (2)	163.2 (17)
N4—H2N4⋯Cl4	0.93 (2)	2.77 (2)	3.454 (2)	131.5 (17)
N4—H2N4⋯Cl1vi	0.93 (2)	2.51 (2)	3.148 (2)	126.4 (18)
N4—H3N4⋯Cl4vii	0.83 (2)	2.30 (2)	3.128 (2)	175 (2)
N5—H1N5⋯Cl4	0.91 (2)	2.29 (2)	3.193 (2)	172.0 (18)
N5—H2N5⋯Cl1viii	0.84 (2)	2.77 (2)	3.340 (2)	126.6 (17)
N6—H1N6⋯Cl3	0.89 (2)	2.22 (2)	3.057 (1)	156.6 (19)
C7—H7A⋯Cl4ix	0.99 (2)	2.745 (19)	3.459 (2)	129.4 (14)

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