2-Amino-3-ammonio­pyridinium dichloride

Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536810003624

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages o513-o514

doi:10.1107/S1600536810003624

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2-Amino-3-ammoniopyridinium dichloride

Madhukar Hemamalini ^a and Hoong-Kun Fun ^a ^*‡

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 26 January 2010; accepted 29 January 2010; online 3 February 2010)

The asymmetric unit of the title compound, C₅H₉N₃²⁺·2Cl⁻, contains two diprotonated 2,3-diaminopyridine cations and four chloride anions. In the crystal structure, the anions and cations are connected by intermolecular N—H⋯Cl and C—H⋯Cl hydrogen bonds, forming a three-dimensional network. The crystal structure is further stabilized by π–π interactions 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

C₅H₉N₃²⁺·2Cl⁻
M_r = 182.05
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.045
wR(F²) = 0.109
S = 1.03
5736 reflections
253 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.22 e Å⁻³

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⋯Cl1^iv	0.90 (2)	2.32 (2)	3.219 (2)	177.6 (16)
N2—H2N2⋯Cl2^v	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⋯Cl3^vi	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⋯Cl1^vi	0.93 (2)	2.51 (2)	3.148 (2)	126.4 (18)
N4—H3N4⋯Cl4^vii	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⋯Cl1^viii	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⋯Cl4^ix	0.99 (2)	2.745 (19)	3.459 (2)	129.4 (14)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) x, y-1, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) -x+2, -y, -z+2; (vi) -x+1, -y+1, -z+1; (vii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (viii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ix) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810003624/wn2374sup1.cif

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

checkCIF report

Comment top

Pyridine and its derivatives play an important role in heterocyclic chemistry (Pozharski et al., 1997; Katritzky et al., 1996). In particular, diaminopyridines play an important role in the preparation of aromatic azo dyes, the subject of many polarographic investigations (Abu Zuhri & Cox, 1989). The coordination chemistry of anions is a fast-growing area of supramolecular chemistry. Moreover, Cl anions have been successfully used to assemble double-helical motifs of various molecules containing aromatic groups, with stacking within the helices (Sessler et al., 2003). Pyridine and its substituted derivatives are often involved in hydrogen-bond interactions (Jeffrey & Saenger, 1991; Jeffrey, 1997; Scheiner, 1997). The crystal structures of 2,3-diaminopyridinium 4-hydroxybenzoate (Fun & Balasubramani, 2009), 2,3-diaminopyridinium 4-nitrobenzoate (Balasubramani & Fun, 2009a) and 2,3-diaminopyridinium benzoate (Balasubramani & Fun, 2009b) have recently been reported by us. In the hope of studying some interesting hydrogen-bonding interactions, the title compound was synthesized. Its molecular and crystal structure is presented here.

The asymmetric unit of the title compound (Fig. 1) consists of two diprotonated 2,3-diaminopyridine cations and four chloride anions. In the 2,3-diaminopyridinium cations, protonation at atoms N3 and N6 has led to slight increases in the C1—N3—C5 and C6—N6—C10 angles to 123.65 (14)° and 123.92 (14)°, respectively, compared to those of an unprotonated structure (De Cires-Mejias et al., 2004). The bond lengths (Allen et al., 1987) and angles are normal .

In the crystal structure (Fig. 2), the anions and cations are connected by intermolecular N—H···Cl and C—H···Cl hydrogen bonds, forming a three-dimensional network. The crystal structure is further stabilized by π···π interactions between the pyridinium rings (N3/C1–C5) [centroid-to-centroid (2-x, -y, 1-z) distance = 3.695 (1) Å].

Related literature top

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 top

To a hot methanol solution (20 ml) of 2,3-diaminopyridine (27 mg, Aldrich) was added a few drops of hydrochloric acid. The solution was warmed over a water bath for a few minutes. The resulting solution was allowed to cool slowly to room temperature. Crystals of the title compound appeared from the mother liquor after a few days.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.
	Fig. 2. The crystal packing of the title compound, showing the hydrogen-bonded (dashed lines) networks.

2-Amino-3-ammoniopyridinium dichloride top

Crystal data top

C₅H₉N₃²⁺·2Cl⁻	F(000) = 752
M_r = 182.05	D_x = 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

Data collection top

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

Refinement top

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 = 1.03	w = 1/[σ²(F_o²) + (0.0489P)² + 0.1879P] where P = (F_o² + 2F_c²)/3
5736 reflections	(Δ/σ)_max = 0.001
253 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₅H₉N₃²⁺·2Cl⁻	V = 1581.42 (5) Å³
M_r = 182.05	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.9770 (2) Å	µ = 0.75 mm⁻¹
b = 12.5175 (2) Å	T = 100 K
c = 11.6520 (2) Å	0.34 × 0.32 × 0.13 mm
β = 98.979 (1)°

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	5736 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4042 reflections with I > 2σ(I)
T_min = 0.787, T_max = 0.907	R_int = 0.035
22610 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.44 e Å⁻³
5736 reflections	Δρ_min = −0.22 e Å⁻³
253 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Cl1^iv	0.90 (2)	2.32 (2)	3.219 (2)	177.6 (16)
N2—H2N2···Cl2^v	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···Cl3^vi	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···Cl1^vi	0.93 (2)	2.51 (2)	3.148 (2)	126.4 (18)
N4—H3N4···Cl4^vii	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···Cl1^viii	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···Cl4^ix	0.99 (2)	2.745 (19)	3.459 (2)	129.4 (14)

Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+1, −y, −z+1; (iii) x, y−1, z; (iv) −x+1, y−1/2, −z+3/2; (v) −x+2, −y, −z+2; (vi) −x+1, −y+1, −z+1; (vii) x, −y+3/2, z−1/2; (viii) −x+1, y+1/2, −z+3/2; (ix) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₉N₃²⁺·2Cl⁻
M_r	182.05
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	10.9770 (2), 12.5175 (2), 11.6520 (2)
β (°)	98.979 (1)
V (Å³)	1581.42 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.34 × 0.32 × 0.13

Data collection
Diffractometer	Bruker APEX DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.787, 0.907
No. of measured, independent and observed [I > 2σ(I)] reflections	22610, 5736, 4042
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.757

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.109, 1.03
No. of reflections	5736
No. of parameters	253
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.22

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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···Cl1^iv	0.90 (2)	2.32 (2)	3.219 (2)	177.6 (16)
N2—H2N2···Cl2^v	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···Cl3^vi	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···Cl1^vi	0.93 (2)	2.51 (2)	3.148 (2)	126.4 (18)
N4—H3N4···Cl4^vii	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···Cl1^viii	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···Cl4^ix	0.99 (2)	2.745 (19)	3.459 (2)	129.4 (14)

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

MH and HKF thank the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. MH thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

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