2-Amino-5-methyl­pyridinium picolinate 0.63-hydrate

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

doi:10.1107/S1600536810018180

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Pages o1420-o1421

https://doi.org/10.1107/S1600536810018180

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2-Amino-5-methylpyridinium picolinate 0.63-hydrate

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 13 May 2010; accepted 17 May 2010; online 22 May 2010)

The asymmetric unit of the title compound, C₆H₉N₂⁺·C₆H₄NO₂⁻·0.63H₂O, contains two crystallographically independent 2-amino-5-methylpyridinium cations, a pair of picolinate anions and two water molecules, one with an occupancy of 0.25. Both the 2-amino-5-methylpyridine molecules are protonated at the pyridine N atoms. In the crystal structure, the cations, anions and water molecules are linked via N—H⋯O, N—H⋯N and O—H⋯O hydrogen bonds, as well as by C—H⋯O contacts, forming a chain along the b axis. In addition, weak π–π interactions are observed between pyridinium rings, with centroid–centroid distances of 3.5306 (13) Å.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ); Katritzky et al. (1996 ); Navarro Ranninger et al. (1985 ); Luque et al. (1997 ); Qin et al. (1999 ); Yip et al. (1999 ); Ren et al. (2002 ); Rivas et al. (2003 ); Jin et al. (2001 ); Albrecht et al. (2003 ); Nahringbauer & Kvick (1977 ). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ); Jeffrey (1997 ); Scheiner (1997 ). For details of picolinic acid, see: Mahler & Cordes (1971 ); Ogata et al. (2000 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For 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

C₆H₉N₂⁺·C₆H₄NO₂⁻·0.63H₂O
M_r = 242.51
Orthorhombic, P 2₁ 2₁ 2₁
a = 12.126 (3) Å
b = 13.842 (3) Å
c = 14.318 (3) Å
V = 2403.4 (10) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.28 × 0.20 × 0.09 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.973, T_max = 0.991
50363 measured reflections
3955 independent reflections
3119 reflections with I > 2σ(I)
R_int = 0.068

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.141
S = 1.09
3955 reflections
353 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2W—H2W2⋯O2Aⁱ	0.82	2.00	2.812 (2)	170
N1A—H1NA⋯O2Bⁱⁱ	0.99 (2)	1.69 (2)	2.669 (2)	170 (2)
N2A—H2NA⋯O1Bⁱⁱ	0.94 (3)	1.89 (3)	2.829 (2)	178 (3)
N2A—H3NA⋯N3A	0.94 (3)	2.08 (3)	3.019 (3)	177 (2)
N1B—H1NB⋯O2Aⁱ	0.96 (3)	1.68 (3)	2.642 (2)	173 (3)
N2B—H2NB⋯N3B	0.83 (3)	2.22 (3)	3.040 (2)	173 (2)
N2B—H3NB⋯O1Aⁱ	0.93 (2)	1.90 (2)	2.831 (3)	175 (2)
C5A—H5AA⋯O2Wⁱⁱⁱ	0.93	2.39	3.319 (3)	175
C7A—H7AA⋯O2B^iv	0.93	2.42	3.217 (3)	144
C8A—H8AA⋯O2W^v	0.93	2.50	3.339 (3)	151
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z; (iii) x+1, y+1, z; (iv) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

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: https://doi.org/10.1107/S1600536810018180/sj5005sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810018180/sj5005Isup2.hkl

checkCIF report

Comment top

Pyridine and its derivatives play an important role in heterocyclic chemistry (Pozharski et al., 1997; Katritzky et al., 1996). They are often involved in hydrogen-bond interactions (Jeffrey & Saenger, 1991; Jeffrey, 1997; Scheiner, 1997). There are numerous examples of 2-amino-substituted pyridine compounds in which the 2-aminopyridines act as neutral ligands (Navarro Ranninger et al., 1985; Luque et al., 1997; Qin et al., 1999; Yip et al., 1999; Ren et al., 2002; Rivas et al., 2003) or as protonated cations (Luque et al., 1997; Jin et al., 2001; Albrecht et al., 2003). Picolinic acid (pyridine-2-carboxylic acid) is a well known terminal tryptophan metabolite (Mahler & Cordes, 1971). It induces apoptosis in leukaemia HL-60 cells (Ogata et al., 2000). Since our aim is to study some interesting hydrogen bonding interactions, the crystal structure of the title compound is presented here.

The asymmetric unit of the title compound consists of two crystallographically independent 2-amino-5-methylpyridinium cations (A and B), two picolinate anions (A and B) and two water molecules, O1W and O2W (with occupancies 0.25 and 1.0, respectively), (Fig. 1). Each 2-amino-5-methylpyridinium cation is planar, with a maximum deviation of 0.024 (2) Å for atom C6A in cation A and 0.005 (2) Å for atom C1B in cation B. In the cations, protonation at atoms N1A and N1B lead to a slight increase in the C1A—N1A—C5A [123.2 (2)°] and C1B—N1B—C5B [123.0 (2)°] angles compared to those observed in an unprotonated structure (Nahringbauer & Kvick, 1977). The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal structure (Fig. 2), the carboxylate groups of each picolinate anion interact with the corresponding 2-amino-5-methylpyridinium cations via a pair of N—H···O hydrogen bonds forming an R²₂(8) ring motif (Bernstein et al., 1995). The ionic units are linked by N—H···N, N—H···O, O—H···O and C—H···O (Table 1) hydrogen bonds, forming a one-dimensional chain along the b-axis. The crystal structure is further stabilized by π–π interactions involving the pyridinium (N1A/C1A–C5A) and pyridinium (N1B/C1B–C5B) rings, with centroid-to-centroid distance of 3.5306 (13) Å [symmetry code: 1-x, 1/2+y, 1/2-z].

Related literature top

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996); Navarro Ranninger et al. (1985); Luque et al. (1997); Qin et al. (1999); Yip et al. (1999); Ren et al. (2002); Rivas et al. (2003)); Luque et al. (1997); Jin et al. (2001); Albrecht et al. (2003); Nahringbauer & Kvick (1977). For details of hydrogen bonding, see: Jeffrey & Saenger (1991); Jeffrey (1997); Scheiner (1997). For details of picolinic acid, see: Mahler & Cordes (1971); Ogata et al. (2000). For hydrogen-bond motifs, see: Bernstein et al. (1995). For 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

Hot methanol solutions (20 ml) of 2-amino-5-methylpyridine (54 mg, Aldrich) and picolinic acid (62 mg, Merck) were mixed and warmed over a a magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound appeared after a few days.

Structure description top

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996); Navarro Ranninger et al. (1985); Luque et al. (1997); Qin et al. (1999); Yip et al. (1999); Ren et al. (2002); Rivas et al. (2003)); Luque et al. (1997); Jin et al. (2001); Albrecht et al. (2003); Nahringbauer & Kvick (1977). For details of hydrogen bonding, see: Jeffrey & Saenger (1991); Jeffrey (1997); Scheiner (1997). For details of picolinic acid, see: Mahler & Cordes (1971); Ogata et al. (2000). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

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.
	Fig. 2. The crystal packing of the title compound, showing hydrogen-bonded (dashed lines) networks. H atoms not involved in hydrogen bond interactions are omitted for clarity.

2-Amino-5-methylpyridinium pyridine-2-carboxylate 0.63-hydrate top

Crystal data top

C₆H₉N₂⁺·C₆H₄NO₂⁻·0.63H₂O	F(000) = 1026
M_r = 242.51	D_x = 1.340 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7433 reflections
a = 12.126 (3) Å	θ = 2.2–29.8°
b = 13.842 (3) Å	µ = 0.10 mm⁻¹
c = 14.318 (3) Å	T = 100 K
V = 2403.4 (10) Å³	Block, colourless
Z = 8	0.28 × 0.20 × 0.09 mm

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3955 independent reflections
Radiation source: fine-focus sealed tube	3119 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
φ and ω scans	θ_max = 30.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −17→17
T_min = 0.973, T_max = 0.991	k = −19→19
50363 measured reflections	l = −20→20

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0779P)² + 0.4137P] where P = (F_o² + 2F_c²)/3
3955 reflections	(Δ/σ)_max = 0.001
353 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₆H₉N₂⁺·C₆H₄NO₂⁻·0.63H₂O	V = 2403.4 (10) Å³
M_r = 242.51	Z = 8
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 12.126 (3) Å	µ = 0.10 mm⁻¹
b = 13.842 (3) Å	T = 100 K
c = 14.318 (3) Å	0.28 × 0.20 × 0.09 mm

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3955 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3119 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.991	R_int = 0.068
50363 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.33 e Å⁻³
3955 reflections	Δρ_min = −0.35 e Å⁻³
353 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	Occ. (<1)
N1A	0.97657 (16)	0.86544 (15)	0.09594 (13)	0.0235 (4)
N2A	0.98590 (18)	0.69933 (17)	0.08274 (15)	0.0291 (5)
C1A	0.93479 (19)	0.78196 (18)	0.06311 (15)	0.0231 (4)
C2A	0.83756 (19)	0.78782 (18)	0.00781 (17)	0.0253 (5)
H2AA	0.8060	0.7319	−0.0162	0.030*
C3A	0.79046 (19)	0.87571 (18)	−0.01001 (17)	0.0257 (5)
H3AA	0.7273	0.8789	−0.0467	0.031*
C4A	0.83615 (19)	0.96169 (17)	0.02636 (17)	0.0247 (5)
C5A	0.92944 (19)	0.95332 (17)	0.07947 (16)	0.0238 (5)
H5AA	0.9613	1.0085	0.1048	0.029*
C6A	0.7824 (2)	1.05808 (19)	0.01044 (19)	0.0306 (5)
H6AA	0.8170	1.1058	0.0493	0.046*
H6AB	0.7055	1.0539	0.0258	0.046*
H6AC	0.7904	1.0761	−0.0539	0.046*
O1A	1.0576 (2)	0.51193 (14)	0.1466 (2)	0.0585 (8)
O2A	1.06051 (16)	0.35162 (13)	0.15326 (14)	0.0349 (4)
N3A	0.8965 (2)	0.50822 (17)	0.01507 (19)	0.0407 (6)
C7A	0.8132 (2)	0.5040 (2)	−0.0465 (2)	0.0425 (7)
H7AA	0.7946	0.5602	−0.0785	0.051*
C8A	0.7533 (2)	0.4213 (2)	−0.0653 (2)	0.0373 (6)
H8AA	0.6959	0.4219	−0.1084	0.045*
C9A	0.7809 (2)	0.3379 (2)	−0.0184 (2)	0.0332 (6)
H9AA	0.7420	0.2811	−0.0288	0.040*
C10A	0.8683 (2)	0.34009 (19)	0.04496 (18)	0.0280 (5)
H10A	0.8890	0.2846	0.0771	0.034*
C11A	0.9239 (2)	0.42690 (18)	0.05917 (18)	0.0282 (5)
C12A	1.0218 (2)	0.43223 (19)	0.1257 (2)	0.0319 (5)
N1B	0.24603 (16)	0.35896 (15)	0.24965 (14)	0.0233 (4)
N2B	0.25938 (19)	0.52545 (16)	0.24544 (15)	0.0271 (4)
C1B	0.29982 (19)	0.44099 (17)	0.27328 (16)	0.0230 (4)
C2B	0.39853 (18)	0.43069 (17)	0.32614 (17)	0.0251 (5)
H2BA	0.4384	0.4851	0.3438	0.030*
C3B	0.4344 (2)	0.34168 (19)	0.35063 (18)	0.0280 (5)
H3BA	0.4989	0.3362	0.3853	0.034*
C4B	0.3767 (2)	0.25626 (18)	0.32509 (17)	0.0276 (5)
C5B	0.2821 (2)	0.26944 (17)	0.27415 (17)	0.0251 (5)
H5BA	0.2415	0.2157	0.2559	0.030*
C6B	0.4152 (3)	0.15790 (19)	0.3523 (2)	0.0392 (7)
H6BA	0.3732	0.1102	0.3191	0.059*
H6BB	0.4052	0.1491	0.4182	0.059*
H6BC	0.4919	0.1511	0.3371	0.059*
O1B	0.16897 (15)	0.71003 (12)	0.20473 (13)	0.0300 (4)
O2B	0.16686 (15)	0.87068 (13)	0.18961 (13)	0.0310 (4)
N3B	0.35568 (17)	0.71727 (15)	0.30874 (15)	0.0279 (4)
C7B	0.4429 (2)	0.72461 (19)	0.3658 (2)	0.0358 (6)
H7BA	0.4767	0.6679	0.3857	0.043*
C8B	0.4858 (2)	0.8121 (2)	0.3969 (2)	0.0373 (6)
H8BA	0.5458	0.8134	0.4373	0.045*
C9B	0.4378 (2)	0.89624 (19)	0.36688 (19)	0.0332 (6)
H9BA	0.4650	0.9558	0.3860	0.040*
C10B	0.3477 (2)	0.89054 (18)	0.30724 (17)	0.0271 (5)
H10B	0.3142	0.9465	0.2851	0.033*
C11B	0.30822 (18)	0.80070 (17)	0.28102 (16)	0.0227 (4)
C12B	0.20592 (18)	0.79216 (17)	0.21971 (16)	0.0222 (4)
O1W	0.1654 (5)	0.0578 (4)	0.2767 (5)	0.0227 (12)	0.25
H1W1	0.1196	0.0966	0.2937	0.034*	0.25
H2W1	0.1398	0.0069	0.2582	0.034*	0.25
O2W	0.0279 (3)	0.15220 (18)	0.17835 (19)	0.0758 (10)
H1W2	−0.0219	0.1402	0.2150	0.114*
H2W2	0.0312	0.2103	0.1667	0.114*
H1NA	1.044 (3)	0.858 (3)	0.131 (3)	0.050 (10)*
H2NA	1.049 (3)	0.702 (3)	0.124 (3)	0.060 (11)*
H3NA	0.959 (3)	0.638 (2)	0.064 (2)	0.034 (8)*
H1NB	0.177 (3)	0.359 (3)	0.219 (3)	0.061 (11)*
H2NB	0.292 (3)	0.574 (2)	0.263 (2)	0.037 (9)*
H3NB	0.193 (3)	0.525 (3)	0.212 (2)	0.045 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.0208 (9)	0.0264 (10)	0.0232 (9)	0.0005 (8)	−0.0022 (8)	0.0015 (8)
N2A	0.0295 (10)	0.0258 (11)	0.0318 (11)	0.0013 (9)	−0.0059 (9)	0.0014 (9)
C1A	0.0233 (10)	0.0254 (11)	0.0206 (10)	0.0000 (9)	0.0007 (9)	0.0010 (9)
C2A	0.0242 (10)	0.0245 (11)	0.0274 (11)	−0.0028 (9)	−0.0029 (9)	−0.0013 (9)
C3A	0.0205 (10)	0.0314 (12)	0.0253 (11)	−0.0022 (9)	−0.0019 (9)	0.0026 (9)
C4A	0.0231 (10)	0.0248 (11)	0.0263 (11)	0.0013 (9)	0.0032 (9)	0.0031 (9)
C5A	0.0240 (10)	0.0217 (11)	0.0257 (11)	−0.0007 (9)	0.0002 (9)	−0.0008 (9)
C6A	0.0275 (11)	0.0281 (12)	0.0361 (13)	0.0001 (10)	−0.0007 (10)	0.0047 (11)
O1A	0.0586 (14)	0.0248 (10)	0.0922 (19)	−0.0069 (10)	−0.0532 (14)	0.0083 (11)
O2A	0.0308 (9)	0.0263 (9)	0.0475 (11)	−0.0005 (7)	−0.0147 (8)	0.0024 (8)
N3A	0.0420 (13)	0.0305 (12)	0.0495 (14)	−0.0023 (10)	−0.0252 (12)	0.0033 (11)
C7A	0.0435 (16)	0.0355 (15)	0.0483 (16)	0.0052 (13)	−0.0225 (14)	0.0034 (13)
C8A	0.0311 (13)	0.0435 (16)	0.0373 (14)	0.0067 (12)	−0.0122 (11)	−0.0120 (12)
C9A	0.0267 (12)	0.0338 (14)	0.0392 (14)	−0.0009 (10)	−0.0045 (11)	−0.0136 (11)
C10A	0.0242 (11)	0.0293 (12)	0.0305 (12)	0.0010 (10)	0.0006 (9)	−0.0032 (10)
C11A	0.0265 (11)	0.0263 (12)	0.0318 (12)	−0.0001 (10)	−0.0057 (10)	−0.0009 (10)
C12A	0.0298 (12)	0.0253 (12)	0.0407 (14)	−0.0018 (10)	−0.0125 (11)	0.0017 (11)
N1B	0.0228 (9)	0.0216 (10)	0.0255 (9)	0.0017 (8)	−0.0028 (8)	−0.0009 (8)
N2B	0.0292 (10)	0.0215 (10)	0.0305 (11)	0.0005 (9)	−0.0057 (9)	0.0004 (8)
C1B	0.0225 (10)	0.0235 (11)	0.0230 (10)	0.0006 (9)	0.0019 (8)	0.0003 (9)
C2B	0.0209 (10)	0.0249 (11)	0.0294 (12)	−0.0010 (9)	−0.0036 (9)	−0.0018 (9)
C3B	0.0246 (11)	0.0298 (13)	0.0295 (12)	0.0024 (9)	−0.0051 (9)	0.0019 (10)
C4B	0.0300 (12)	0.0246 (11)	0.0281 (11)	0.0028 (10)	−0.0030 (10)	0.0016 (9)
C5B	0.0277 (11)	0.0208 (11)	0.0268 (11)	−0.0004 (9)	−0.0017 (9)	−0.0001 (9)
C6B	0.0436 (15)	0.0250 (12)	0.0490 (16)	0.0054 (12)	−0.0147 (13)	0.0054 (12)
O1B	0.0288 (8)	0.0233 (8)	0.0378 (10)	0.0010 (7)	−0.0088 (8)	−0.0037 (7)
O2B	0.0280 (8)	0.0267 (9)	0.0382 (10)	−0.0038 (7)	−0.0098 (8)	0.0084 (8)
N3B	0.0256 (10)	0.0254 (10)	0.0327 (10)	−0.0018 (8)	−0.0074 (8)	0.0038 (8)
C7B	0.0348 (13)	0.0256 (13)	0.0470 (15)	−0.0031 (11)	−0.0183 (12)	0.0069 (11)
C8B	0.0367 (13)	0.0322 (14)	0.0432 (15)	−0.0102 (12)	−0.0176 (12)	0.0065 (12)
C9B	0.0376 (14)	0.0236 (12)	0.0385 (14)	−0.0115 (10)	−0.0126 (12)	0.0055 (11)
C10B	0.0294 (12)	0.0200 (11)	0.0320 (12)	−0.0043 (9)	−0.0048 (10)	0.0048 (9)
C11B	0.0207 (10)	0.0246 (11)	0.0227 (10)	−0.0032 (9)	0.0004 (8)	0.0026 (9)
C12B	0.0206 (9)	0.0237 (11)	0.0222 (10)	−0.0007 (9)	0.0007 (8)	0.0016 (9)
O1W	0.018 (3)	0.017 (3)	0.032 (3)	0.000 (2)	0.005 (3)	−0.001 (3)
O2W	0.122 (3)	0.0424 (13)	0.0626 (15)	−0.0350 (16)	0.0451 (17)	−0.0191 (12)

Geometric parameters (Å, º) top

N1A—C1A	1.347 (3)	N1B—H1NB	0.95 (4)
N1A—C5A	1.365 (3)	N2B—C1B	1.329 (3)
N1A—H1NA	0.97 (4)	N2B—H2NB	0.82 (3)
N2A—C1A	1.331 (3)	N2B—H3NB	0.93 (3)
N2A—H2NA	0.96 (4)	C1B—C2B	1.423 (3)
N2A—H3NA	0.94 (3)	C2B—C3B	1.353 (3)
C1A—C2A	1.423 (3)	C2B—H2BA	0.9300
C2A—C3A	1.368 (3)	C3B—C4B	1.421 (4)
C2A—H2AA	0.9300	C3B—H3BA	0.9300
C3A—C4A	1.412 (3)	C4B—C5B	1.371 (3)
C3A—H3AA	0.9300	C4B—C6B	1.491 (3)
C4A—C5A	1.368 (3)	C5B—H5BA	0.9300
C4A—C6A	1.502 (3)	C6B—H6BA	0.9600
C5A—H5AA	0.9300	C6B—H6BB	0.9600
C6A—H6AA	0.9600	C6B—H6BC	0.9600
C6A—H6AB	0.9600	O1B—C12B	1.241 (3)
C6A—H6AC	0.9600	O2B—C12B	1.262 (3)
O1A—C12A	1.223 (3)	N3B—C7B	1.340 (3)
O2A—C12A	1.273 (3)	N3B—C11B	1.350 (3)
N3A—C11A	1.333 (3)	C7B—C8B	1.391 (4)
N3A—C7A	1.343 (3)	C7B—H7BA	0.9300
C7A—C8A	1.382 (4)	C8B—C9B	1.372 (4)
C7A—H7AA	0.9300	C8B—H8BA	0.9300
C8A—C9A	1.376 (4)	C9B—C10B	1.389 (3)
C8A—H8AA	0.9300	C9B—H9BA	0.9300
C9A—C10A	1.395 (3)	C10B—C11B	1.384 (3)
C9A—H9AA	0.9300	C10B—H10B	0.9300
C10A—C11A	1.393 (3)	C11B—C12B	1.524 (3)
C10A—H10A	0.9300	O1W—H1W1	0.8098
C11A—C12A	1.523 (3)	O1W—H2W1	0.8148
N1B—C1B	1.353 (3)	O2W—H1W2	0.8172
N1B—C5B	1.360 (3)	O2W—H2W2	0.8226

C1A—N1A—C5A	123.2 (2)	C1B—N1B—H1NB	123 (2)
C1A—N1A—H1NA	114 (2)	C5B—N1B—H1NB	114 (2)
C5A—N1A—H1NA	122 (2)	C1B—N2B—H2NB	117 (2)
C1A—N2A—H2NA	118 (2)	C1B—N2B—H3NB	117 (2)
C1A—N2A—H3NA	123.3 (19)	H2NB—N2B—H3NB	126 (3)
H2NA—N2A—H3NA	119 (3)	N2B—C1B—N1B	119.1 (2)
N2A—C1A—N1A	119.2 (2)	N2B—C1B—C2B	123.9 (2)
N2A—C1A—C2A	123.5 (2)	N1B—C1B—C2B	117.0 (2)
N1A—C1A—C2A	117.2 (2)	C3B—C2B—C1B	119.9 (2)
C3A—C2A—C1A	120.0 (2)	C3B—C2B—H2BA	120.0
C3A—C2A—H2AA	120.0	C1B—C2B—H2BA	120.0
C1A—C2A—H2AA	120.0	C2B—C3B—C4B	122.2 (2)
C2A—C3A—C4A	121.1 (2)	C2B—C3B—H3BA	118.9
C2A—C3A—H3AA	119.4	C4B—C3B—H3BA	118.9
C4A—C3A—H3AA	119.4	C5B—C4B—C3B	116.0 (2)
C5A—C4A—C3A	117.3 (2)	C5B—C4B—C6B	121.5 (2)
C5A—C4A—C6A	121.2 (2)	C3B—C4B—C6B	122.6 (2)
C3A—C4A—C6A	121.5 (2)	N1B—C5B—C4B	121.8 (2)
N1A—C5A—C4A	121.2 (2)	N1B—C5B—H5BA	119.1
N1A—C5A—H5AA	119.4	C4B—C5B—H5BA	119.1
C4A—C5A—H5AA	119.4	C4B—C6B—H6BA	109.5
C4A—C6A—H6AA	109.5	C4B—C6B—H6BB	109.5
C4A—C6A—H6AB	109.5	H6BA—C6B—H6BB	109.5
H6AA—C6A—H6AB	109.5	C4B—C6B—H6BC	109.5
C4A—C6A—H6AC	109.5	H6BA—C6B—H6BC	109.5
H6AA—C6A—H6AC	109.5	H6BB—C6B—H6BC	109.5
H6AB—C6A—H6AC	109.5	C7B—N3B—C11B	116.8 (2)
C11A—N3A—C7A	117.5 (2)	N3B—C7B—C8B	123.8 (2)
N3A—C7A—C8A	124.0 (3)	N3B—C7B—H7BA	118.1
N3A—C7A—H7AA	118.0	C8B—C7B—H7BA	118.1
C8A—C7A—H7AA	118.0	C9B—C8B—C7B	118.7 (2)
C9A—C8A—C7A	118.1 (2)	C9B—C8B—H8BA	120.7
C9A—C8A—H8AA	120.9	C7B—C8B—H8BA	120.7
C7A—C8A—H8AA	120.9	C8B—C9B—C10B	118.6 (2)
C8A—C9A—C10A	119.0 (2)	C8B—C9B—H9BA	120.7
C8A—C9A—H9AA	120.5	C10B—C9B—H9BA	120.7
C10A—C9A—H9AA	120.5	C11B—C10B—C9B	119.3 (2)
C11A—C10A—C9A	118.8 (2)	C11B—C10B—H10B	120.3
C11A—C10A—H10A	120.6	C9B—C10B—H10B	120.3
C9A—C10A—H10A	120.6	N3B—C11B—C10B	122.8 (2)
N3A—C11A—C10A	122.6 (2)	N3B—C11B—C12B	116.7 (2)
N3A—C11A—C12A	116.7 (2)	C10B—C11B—C12B	120.5 (2)
C10A—C11A—C12A	120.7 (2)	O1B—C12B—O2B	126.5 (2)
O1A—C12A—O2A	125.7 (2)	O1B—C12B—C11B	117.7 (2)
O1A—C12A—C11A	118.3 (2)	O2B—C12B—C11B	115.8 (2)
O2A—C12A—C11A	116.0 (2)	H1W1—O1W—H2W1	114.2
C1B—N1B—C5B	123.0 (2)	H1W2—O2W—H2W2	111.4

C5A—N1A—C1A—N2A	−179.8 (2)	C5B—N1B—C1B—N2B	179.2 (2)
C5A—N1A—C1A—C2A	0.8 (3)	C5B—N1B—C1B—C2B	0.1 (3)
N2A—C1A—C2A—C3A	−179.4 (2)	N2B—C1B—C2B—C3B	−179.2 (2)
N1A—C1A—C2A—C3A	0.0 (3)	N1B—C1B—C2B—C3B	−0.2 (3)
C1A—C2A—C3A—C4A	−0.6 (4)	C1B—C2B—C3B—C4B	0.2 (4)
C2A—C3A—C4A—C5A	0.4 (3)	C2B—C3B—C4B—C5B	−0.1 (4)
C2A—C3A—C4A—C6A	−177.5 (2)	C2B—C3B—C4B—C6B	−179.6 (3)
C1A—N1A—C5A—C4A	−1.0 (3)	C1B—N1B—C5B—C4B	0.0 (4)
C3A—C4A—C5A—N1A	0.4 (3)	C3B—C4B—C5B—N1B	0.0 (4)
C6A—C4A—C5A—N1A	178.3 (2)	C6B—C4B—C5B—N1B	179.5 (2)
C11A—N3A—C7A—C8A	1.3 (5)	C11B—N3B—C7B—C8B	0.0 (4)
N3A—C7A—C8A—C9A	−0.3 (5)	N3B—C7B—C8B—C9B	−1.1 (5)
C7A—C8A—C9A—C10A	−0.6 (4)	C7B—C8B—C9B—C10B	0.6 (4)
C8A—C9A—C10A—C11A	0.6 (4)	C8B—C9B—C10B—C11B	0.9 (4)
C7A—N3A—C11A—C10A	−1.4 (4)	C7B—N3B—C11B—C10B	1.6 (4)
C7A—N3A—C11A—C12A	177.5 (3)	C7B—N3B—C11B—C12B	−177.3 (2)
C9A—C10A—C11A—N3A	0.5 (4)	C9B—C10B—C11B—N3B	−2.1 (4)
C9A—C10A—C11A—C12A	−178.3 (2)	C9B—C10B—C11B—C12B	176.8 (2)
N3A—C11A—C12A—O1A	11.8 (4)	N3B—C11B—C12B—O1B	4.8 (3)
C10A—C11A—C12A—O1A	−169.3 (3)	C10B—C11B—C12B—O1B	−174.2 (2)
N3A—C11A—C12A—O2A	−166.9 (3)	N3B—C11B—C12B—O2B	−175.6 (2)
C10A—C11A—C12A—O2A	12.0 (4)	C10B—C11B—C12B—O2B	5.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2W2···O2Aⁱ	0.82	2.00	2.812 (2)	170
N1A—H1NA···O2Bⁱⁱ	0.99 (2)	1.69 (2)	2.669 (2)	170 (2)
N2A—H2NA···O1Bⁱⁱ	0.94 (3)	1.89 (3)	2.829 (2)	178 (3)
N2A—H3NA···N3A	0.94 (3)	2.08 (3)	3.019 (3)	177 (2)
N1B—H1NB···O2Aⁱ	0.96 (3)	1.68 (3)	2.642 (2)	173 (3)
N2B—H2NB···N3B	0.83 (3)	2.22 (3)	3.040 (2)	173 (2)
N2B—H3NB···O1Aⁱ	0.93 (2)	1.90 (2)	2.831 (3)	175 (2)
C5A—H5AA···O2Wⁱⁱⁱ	0.93	2.39	3.319 (3)	175
C7A—H7AA···O2B^iv	0.93	2.42	3.217 (3)	144
C8A—H8AA···O2W^v	0.93	2.50	3.339 (3)	151

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

Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·C₆H₄NO₂⁻·0.63H₂O
M_r	242.51
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	12.126 (3), 13.842 (3), 14.318 (3)
V (Å³)	2403.4 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.28 × 0.20 × 0.09

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	50363, 3955, 3119
R_int	0.068
(sin θ/λ)_max (Å⁻¹)	0.708

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.141, 1.09
No. of reflections	3955
No. of parameters	353
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.35

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
O2W—H2W2···O2Aⁱ	0.8200	2.0000	2.812 (2)	170.00
N1A—H1NA···O2Bⁱⁱ	0.99 (2)	1.69 (2)	2.669 (2)	170 (2)
N2A—H2NA···O1Bⁱⁱ	0.94 (3)	1.89 (3)	2.829 (2)	178 (3)
N2A—H3NA···N3A	0.94 (3)	2.08 (3)	3.019 (3)	177 (2)
N1B—H1NB···O2Aⁱ	0.96 (3)	1.68 (3)	2.642 (2)	173 (3)
N2B—H2NB···N3B	0.83 (3)	2.22 (3)	3.040 (2)	173 (2)
N2B—H3NB···O1Aⁱ	0.93 (2)	1.90 (2)	2.831 (3)	175 (2)
C5A—H5AA···O2Wⁱⁱⁱ	0.9300	2.3900	3.319 (3)	175.00
C7A—H7AA···O2B^iv	0.9300	2.4200	3.217 (3)	144.00
C8A—H8AA···O2W^v	0.9300	2.5000	3.339 (3)	151.00

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

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 also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

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