2-Amino-5-methyl­pyridinium 1H-pyrazole-3,5-dicarboxyl­ate trihydrate

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

doi:10.1107/S1600536810041644

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages o2876-o2877

https://doi.org/10.1107/S1600536810041644

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2-Amino-5-methylpyridinium 1H-pyrazole-3,5-dicarboxylate trihydrate

Tara Shahani,^a Hoong-Kun Fun ^a ^*‡ and Madhukar Hemamalini ^a

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

(Received 14 October 2010; accepted 15 October 2010; online 20 October 2010)

In the title compound, 2C₆H₉N₂⁺·C₅H₂N₂O₄²⁻·3H₂O, the 1H-pyrazole-3,5-dicarboxylate anion is close to planar [maximum deviation = 0.208 (1) Å]. The two distinct 2-amino-5-methylpyridinium cations are also almost planar, with maximum deviations of 0.018 (2) and 0.014 (2) Å. In the crystal, pairs of intermolecular N—H⋯O and O—H⋯O hydrogen bonds connect neighbouring molecules into dimers, generating R²₂(8) and R²₄(8) ring motifs, respectively. Further intermolecular N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ); Katritzky et al. (1996 ). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ); Jeffrey (1997 ); Scheiner (1997 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For bond-length data, see: Allen et al. (1987 ). For related structures, see; Xia et al. (2007 ); King et al. (2004 ). For details and applications of pyrazole-3,5-dicarboxylic acid, see: Lee et al. (1989 ); Chambers et al. (1985 ); Pan et al. (2000 ); Pan, Ching et al. (2001 ); Pan, Frydel et al. (2001 ).

Experimental

Crystal data

2C₆H₉N₂⁺·C₅H₂N₂O₄²⁻·3H₂O
M_r = 426.44
Triclinic, $[P \overline 1]$
a = 7.8985 (1) Å
b = 9.2195 (1) Å
c = 15.3922 (2) Å
α = 101.942 (1)°
β = 93.883 (1)°
γ = 104.648 (1)°
V = 1052.40 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.47 × 0.24 × 0.21 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.952, T_max = 0.978
26056 measured reflections
6103 independent reflections
5085 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.113
S = 1.07
6103 reflections
325 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O4ⁱ	0.931 (16)	1.871 (16)	2.7912 (12)	169.7 (15)
N4A—H3NA⋯O1Wⁱⁱ	0.861 (18)	2.024 (17)	2.8520 (14)	161.2 (17)
N3B—H1NB⋯O3ⁱⁱⁱ	0.900 (17)	1.755 (17)	2.6483 (12)	171.4 (16)
N4B—H2NB⋯O4ⁱⁱⁱ	0.914 (18)	2.022 (18)	2.9323 (13)	173.8 (16)
N4B—H3NB⋯O3W^iv	0.889 (18)	2.007 (18)	2.8641 (13)	161.6 (17)
N3A—H1NA⋯O2^iv	0.942 (18)	1.732 (18)	2.6686 (12)	172.8 (17)
N4A—H2NA⋯O1^iv	0.907 (18)	2.106 (18)	3.0021 (13)	169.4 (15)
O1W—H1W1⋯O3	0.871 (19)	1.902 (19)	2.7517 (12)	164.8 (17)
O1W—H2W1⋯O3W^iv	0.85 (2)	1.94 (2)	2.7878 (14)	178 (2)
O2W—H1W2⋯O1	0.850 (18)	2.003 (18)	2.8427 (12)	169.8 (17)
O2W—H2W2⋯O1^v	0.858 (18)	1.987 (18)	2.8434 (13)	176.1 (15)
O3W—H1W3⋯O2	0.888 (17)	1.844 (17)	2.7299 (12)	174.8 (15)
O3W—H2W3⋯O2W^vi	0.881 (18)	1.900 (18)	2.7758 (13)	172.1 (17)
C10—H10A⋯O2W	0.93	2.50	3.3986 (15)	164
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y, -z+1; (iii) -x+1, -y, -z; (iv) x, y-1, z; (v) -x+1, -y+1, -z+1; (vi) x, y+1, 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/S1600536810041644/hb5681sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041644/hb5681Isup2.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). Pyrazole-related molecules have attracted considerable attention due to their biological activities (Lee et al., 1989; Chambers et al., 1985). 3,5-Pyrazole dicarboxylic acid (H₂PzDCA) is a multifunctional ligand; it has multiple coordination sites that allow structures of higher dimensions and it also has abstractable protons that allow various acidity-dependent coordination modes (Pan et al., 2000). A variety of H₂PzDCA coordination compounds have been synthesized and reported in the literature (Pan, Ching et al., 2001; Pan, Frydel et al., 2001). 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, (Fig. 1), consists of two 2-amino-5-methylpyridinium cations, a 1H-pyrazole-3-5-dicarboxylate anion and three water molecules. The 1H-pyrazole-3,5-dicarboxylate anion and 2-amino-5-methylpyridinium cations are approximately planar with a maximum deviations of 0.208 (1) Å at atom O2 and 0.018 (2) Å at atoms N4A, C11A and 0.014 (2) Å at atom N4B. The torsion angles (O2/C2/C1/N1), (C1–C3/O1), (C3–C5/O3) and (N2/C4/C5/04) are 8.81 (15), 10.46 (16), 4.89 (15) and 4.60 (16)°, respectively. Bond lengths (Allen et al., 1987) and angles are normal and comparable to those related structures (Xia et al., 2007; King et al., 2004).

In the crystal packing (Fig. 2), intermolecular N2—H1N2···O4, N4A—H3NA···O1W, N3B—H1NB···O3, N4B—H2NB···O4, N4B—H3NB···O3W, N3A—H1NA···O2, N4A—H2NA···O1, O1W—H1W1···O3, O1W—H2W1···O3W, O2W—H1W2···O1, O2W—H2W2···O1, O3W—H1W3···O2, O3W—H2W3···O2W and C10—H10A···O2W hydrogen bonds (Table 1) link the molecules into three-dimensional network. Within this network, pairs of intermolecular N3B—H1NB···O3, N4A—H2NA···O1 and O1—H1W2···O2W, O2W—H1W2···O1 hydrogen bonds connect neighbouring molecules to form dimers, generating R²₂(8) and R²₄(8) (Bernstein et al., 1995) ring motifs, respectively.

Related literature top

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997); Katritzky et al. (1996). For details of hydrogen bonding, see: Jeffrey & Saenger (1991); Jeffrey (1997); Scheiner (1997). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For related structures, see; Xia et al. (2007); King et al. (2004). For details and applications of pyrazole-3,5-dicarboxylic acid, see: Lee et al. (1989); Chambers et al. (1985); Pan et al. (2000); Pan, Ching et al. (2001); Pan, Frydel et al. (2001).

Experimental top

A hot methanol/water solution (10/10 ml) of 2-amino-5-methylpyridine (54 mg, Aldrich) and pyrazole-3,5-dicarboxylic acid (78 mg, Merck) were mixed and warmed over a heating magnetic stirrer for a few minutes. The resulting solution was allowed to cool slowly at room temperature and colourless blocks of (I) 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). For details of hydrogen bonding, see: Jeffrey & Saenger (1991); Jeffrey (1997); Scheiner (1997). For hydrogen-bond motifs, see: Bernstein et al. (1995). For bond-length data, see: Allen et al. (1987). For related structures, see; Xia et al. (2007); King et al. (2004). For details and applications of pyrazole-3,5-dicarboxylic acid, see: Lee et al. (1989); Chambers et al. (1985); Pan et al. (2000); Pan, Ching et al. (2001); Pan, Frydel et al. (2001).

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 molecular structure of the title compound, showing 50% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound, viewed along b axis. Intermolecular hydrogen bonds linked the molecules into three-dimensional network.

2-Amino-5-methylpyridinium 1H-pyrazole-3,5-dicarboxylate trihydrate top

Crystal data top

2C₆H₉N₂⁺·C₅H₂N₂O₄²⁻·3H₂O	Z = 2
M_r = 426.44	F(000) = 452
Triclinic, P1	D_x = 1.346 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8985 (1) Å	Cell parameters from 9892 reflections
b = 9.2195 (1) Å	θ = 2.4–35.1°
c = 15.3922 (2) Å	µ = 0.11 mm⁻¹
α = 101.942 (1)°	T = 100 K
β = 93.883 (1)°	Block, colourless
γ = 104.648 (1)°	0.47 × 0.24 × 0.21 mm
V = 1052.40 (2) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	6103 independent reflections
Radiation source: fine-focus sealed tube	5085 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 30.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
T_min = 0.952, T_max = 0.978	k = −12→12
26056 measured reflections	l = −21→21

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0569P)² + 0.2775P] where P = (F_o² + 2F_c²)/3
6103 reflections	(Δ/σ)_max < 0.001
325 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

2C₆H₉N₂⁺·C₅H₂N₂O₄²⁻·3H₂O	γ = 104.648 (1)°
M_r = 426.44	V = 1052.40 (2) Å³
Triclinic, P1	Z = 2
a = 7.8985 (1) Å	Mo Kα radiation
b = 9.2195 (1) Å	µ = 0.11 mm⁻¹
c = 15.3922 (2) Å	T = 100 K
α = 101.942 (1)°	0.47 × 0.24 × 0.21 mm
β = 93.883 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	6103 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5085 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.978	R_int = 0.026
26056 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.44 e Å⁻³
6103 reflections	Δρ_min = −0.24 e Å⁻³
325 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
O1	0.68720 (11)	0.64094 (9)	0.43780 (5)	0.02004 (16)
O2	0.63845 (11)	0.84955 (9)	0.40067 (5)	0.02212 (17)
O3	0.70719 (11)	0.24170 (9)	0.10667 (5)	0.02152 (17)
O4	0.58424 (10)	0.33899 (9)	0.00540 (5)	0.01827 (16)
N1	0.56503 (12)	0.68973 (10)	0.21937 (6)	0.01756 (18)
N2	0.56444 (12)	0.58634 (10)	0.14333 (6)	0.01631 (17)
C1	0.65092 (14)	0.71292 (12)	0.38074 (7)	0.01627 (19)
C2	0.62433 (13)	0.63055 (11)	0.28462 (6)	0.01510 (19)
C3	0.66147 (13)	0.49037 (11)	0.24972 (6)	0.01555 (19)
H3A	0.7032	0.4279	0.2812	0.019*
C4	0.62226 (13)	0.46589 (11)	0.15823 (6)	0.01420 (18)
C5	0.63753 (13)	0.33966 (11)	0.08394 (6)	0.01463 (18)
N3A	0.80196 (12)	0.03401 (11)	0.55694 (6)	0.01923 (18)
N4A	0.90801 (14)	−0.15177 (12)	0.60538 (7)	0.0248 (2)
C6A	0.89063 (14)	−0.00860 (13)	0.62071 (7)	0.0192 (2)
C7A	0.96163 (15)	0.10318 (14)	0.70158 (7)	0.0226 (2)
H7AA	1.0235	0.0786	0.7475	0.027*
C8A	0.93848 (15)	0.24717 (14)	0.71159 (8)	0.0239 (2)
H8AA	0.9838	0.3193	0.7653	0.029*
C9A	0.84776 (15)	0.29051 (13)	0.64303 (8)	0.0224 (2)
C10	0.78076 (15)	0.17873 (13)	0.56658 (7)	0.0212 (2)
H10A	0.7192	0.2017	0.5199	0.025*
C11A	0.82578 (18)	0.45015 (14)	0.65337 (10)	0.0324 (3)
H11A	0.7779	0.4614	0.5969	0.049*
H11B	0.9384	0.5245	0.6729	0.049*
H11C	0.7470	0.4665	0.6969	0.049*
N3B	0.26714 (12)	0.00202 (10)	0.01212 (6)	0.01689 (17)
N4B	0.37262 (14)	−0.08155 (12)	0.13095 (7)	0.02199 (19)
C6B	0.30472 (14)	0.02005 (12)	0.10101 (7)	0.01719 (19)
C7B	0.26600 (15)	0.14651 (13)	0.15793 (7)	0.0213 (2)
H7BA	0.2909	0.1642	0.2197	0.026*
C8B	0.19158 (15)	0.24211 (12)	0.12087 (8)	0.0214 (2)
H8BA	0.1650	0.3240	0.1585	0.026*
C9B	0.15376 (14)	0.22026 (12)	0.02713 (8)	0.0197 (2)
C10B	0.19410 (14)	0.09771 (12)	−0.02480 (7)	0.0184 (2)
H10B	0.1712	0.0791	−0.0868	0.022*
C11B	0.07429 (16)	0.32759 (14)	−0.01255 (9)	0.0264 (2)
H11D	0.0564	0.2936	−0.0766	0.040*
H11E	0.1526	0.4299	0.0046	0.040*
H11F	−0.0369	0.3278	0.0090	0.040*
O3W	0.52828 (12)	1.04505 (10)	0.31330 (5)	0.02258 (17)
O2W	0.54335 (13)	0.32242 (10)	0.43022 (6)	0.02698 (19)
O1W	0.84767 (12)	0.15951 (12)	0.25161 (6)	0.0291 (2)
H1N2	0.523 (2)	0.6047 (18)	0.0897 (11)	0.027 (4)*
H3NA	0.968 (2)	−0.176 (2)	0.6462 (12)	0.040 (5)*
H1NB	0.286 (2)	−0.080 (2)	−0.0250 (11)	0.033 (4)*
H2NB	0.393 (2)	−0.162 (2)	0.0913 (12)	0.039 (4)*
H3NB	0.409 (2)	−0.063 (2)	0.1891 (12)	0.038 (4)*
H1NA	0.749 (2)	−0.037 (2)	0.5028 (12)	0.040 (4)*
H2NA	0.853 (2)	−0.220 (2)	0.5538 (12)	0.039 (4)*
H1W1	0.820 (2)	0.200 (2)	0.2082 (13)	0.045 (5)*
H2W1	0.751 (3)	0.123 (2)	0.2703 (14)	0.053 (6)*
H1W2	0.591 (2)	0.414 (2)	0.4263 (12)	0.043 (5)*
H2W2	0.470 (2)	0.330 (2)	0.4684 (13)	0.044 (5)*
H1W3	0.558 (2)	0.9771 (19)	0.3403 (11)	0.034 (4)*
H2W3	0.529 (2)	1.128 (2)	0.3540 (12)	0.043 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0295 (4)	0.0177 (4)	0.0135 (3)	0.0084 (3)	0.0007 (3)	0.0032 (3)
O2	0.0349 (4)	0.0168 (4)	0.0150 (3)	0.0118 (3)	−0.0016 (3)	0.0001 (3)
O3	0.0337 (4)	0.0199 (4)	0.0145 (3)	0.0152 (3)	0.0010 (3)	0.0026 (3)
O4	0.0249 (4)	0.0174 (4)	0.0129 (3)	0.0083 (3)	−0.0006 (3)	0.0022 (3)
N1	0.0240 (4)	0.0158 (4)	0.0130 (4)	0.0078 (3)	0.0007 (3)	0.0013 (3)
N2	0.0224 (4)	0.0151 (4)	0.0120 (4)	0.0080 (3)	0.0004 (3)	0.0014 (3)
C1	0.0186 (5)	0.0164 (4)	0.0130 (4)	0.0051 (4)	0.0010 (3)	0.0015 (3)
C2	0.0181 (4)	0.0143 (4)	0.0124 (4)	0.0047 (4)	0.0010 (3)	0.0020 (3)
C3	0.0188 (5)	0.0148 (4)	0.0135 (4)	0.0055 (4)	0.0011 (3)	0.0034 (3)
C4	0.0157 (4)	0.0129 (4)	0.0138 (4)	0.0046 (3)	0.0010 (3)	0.0022 (3)
C5	0.0167 (4)	0.0140 (4)	0.0128 (4)	0.0039 (3)	0.0020 (3)	0.0027 (3)
N3A	0.0224 (4)	0.0195 (4)	0.0143 (4)	0.0057 (3)	−0.0004 (3)	0.0016 (3)
N4A	0.0293 (5)	0.0217 (5)	0.0213 (5)	0.0068 (4)	−0.0069 (4)	0.0037 (4)
C6A	0.0182 (5)	0.0214 (5)	0.0164 (5)	0.0025 (4)	0.0006 (4)	0.0047 (4)
C7A	0.0210 (5)	0.0264 (5)	0.0158 (5)	0.0009 (4)	−0.0030 (4)	0.0037 (4)
C8A	0.0203 (5)	0.0256 (6)	0.0189 (5)	−0.0002 (4)	−0.0002 (4)	−0.0015 (4)
C9A	0.0206 (5)	0.0207 (5)	0.0228 (5)	0.0042 (4)	0.0021 (4)	0.0002 (4)
C10	0.0223 (5)	0.0212 (5)	0.0199 (5)	0.0074 (4)	0.0008 (4)	0.0033 (4)
C11A	0.0317 (6)	0.0207 (6)	0.0391 (7)	0.0074 (5)	−0.0022 (5)	−0.0039 (5)
N3B	0.0194 (4)	0.0146 (4)	0.0160 (4)	0.0062 (3)	0.0015 (3)	0.0005 (3)
N4B	0.0294 (5)	0.0216 (5)	0.0152 (4)	0.0108 (4)	−0.0015 (4)	0.0013 (3)
C6B	0.0168 (4)	0.0158 (5)	0.0168 (5)	0.0028 (4)	0.0016 (3)	0.0012 (4)
C7B	0.0238 (5)	0.0187 (5)	0.0184 (5)	0.0050 (4)	0.0034 (4)	−0.0009 (4)
C8B	0.0209 (5)	0.0152 (5)	0.0260 (5)	0.0047 (4)	0.0065 (4)	−0.0009 (4)
C9B	0.0168 (5)	0.0154 (5)	0.0272 (5)	0.0046 (4)	0.0049 (4)	0.0049 (4)
C10B	0.0184 (5)	0.0174 (5)	0.0194 (5)	0.0048 (4)	0.0021 (4)	0.0048 (4)
C11B	0.0260 (6)	0.0207 (5)	0.0370 (6)	0.0100 (4)	0.0063 (5)	0.0112 (5)
O3W	0.0336 (5)	0.0189 (4)	0.0159 (4)	0.0100 (3)	−0.0003 (3)	0.0032 (3)
O2W	0.0402 (5)	0.0185 (4)	0.0252 (4)	0.0108 (4)	0.0132 (4)	0.0052 (3)
O1W	0.0251 (4)	0.0407 (5)	0.0259 (4)	0.0095 (4)	−0.0003 (3)	0.0182 (4)

Geometric parameters (Å, º) top

O1—C1	1.2637 (12)	C11A—H11A	0.9600
O2—C1	1.2640 (13)	C11A—H11B	0.9600
O3—C5	1.2637 (12)	C11A—H11C	0.9600
O4—C5	1.2511 (12)	N3B—C6B	1.3468 (13)
N1—N2	1.3467 (12)	N3B—C10B	1.3618 (13)
N1—C2	1.3483 (13)	N3B—H1NB	0.897 (17)
N2—C4	1.3572 (12)	N4B—C6B	1.3329 (14)
N2—H1N2	0.929 (16)	N4B—H2NB	0.910 (18)
C1—C2	1.4907 (14)	N4B—H3NB	0.890 (18)
C2—C3	1.4038 (14)	C6B—C7B	1.4193 (14)
C3—C4	1.3798 (13)	C7B—C8B	1.3683 (16)
C3—H3A	0.9300	C7B—H7BA	0.9300
C4—C5	1.4884 (13)	C8B—C9B	1.4153 (16)
N3A—C6A	1.3468 (14)	C8B—H8BA	0.9300
N3A—C10	1.3656 (14)	C9B—C10B	1.3638 (15)
N3A—H1NA	0.943 (18)	C9B—C11B	1.5027 (15)
N4A—C6A	1.3356 (15)	C10B—H10B	0.9300
N4A—H3NA	0.863 (18)	C11B—H11D	0.9600
N4A—H2NA	0.909 (18)	C11B—H11E	0.9600
C6A—C7A	1.4171 (15)	C11B—H11F	0.9600
C7A—C8A	1.3643 (17)	O3W—H1W3	0.889 (18)
C7A—H7AA	0.9300	O3W—H2W3	0.879 (19)
C8A—C9A	1.4155 (17)	O2W—H1W2	0.85 (2)
C8A—H8AA	0.9300	O2W—H2W2	0.86 (2)
C9A—C10	1.3656 (15)	O1W—H1W1	0.87 (2)
C9A—C11A	1.5026 (17)	O1W—H2W1	0.85 (2)
C10—H10A	0.9300

N2—N1—C2	104.08 (8)	N3A—C10—H10A	119.2
N1—N2—C4	112.83 (8)	C9A—C10—H10A	119.2
N1—N2—H1N2	117.6 (9)	C9A—C11A—H11A	109.5
C4—N2—H1N2	129.5 (9)	C9A—C11A—H11B	109.5
O1—C1—O2	123.84 (9)	H11A—C11A—H11B	109.5
O1—C1—C2	117.16 (9)	C9A—C11A—H11C	109.5
O2—C1—C2	119.00 (9)	H11A—C11A—H11C	109.5
N1—C2—C3	111.76 (9)	H11B—C11A—H11C	109.5
N1—C2—C1	121.73 (9)	C6B—N3B—C10B	123.39 (9)
C3—C2—C1	126.47 (9)	C6B—N3B—H1NB	118.8 (11)
C4—C3—C2	104.59 (9)	C10B—N3B—H1NB	117.7 (11)
C4—C3—H3A	127.7	C6B—N4B—H2NB	119.7 (11)
C2—C3—H3A	127.7	C6B—N4B—H3NB	118.8 (11)
N2—C4—C3	106.73 (9)	H2NB—N4B—H3NB	121.1 (16)
N2—C4—C5	122.30 (9)	N4B—C6B—N3B	119.07 (10)
C3—C4—C5	130.96 (9)	N4B—C6B—C7B	123.59 (10)
O4—C5—O3	125.34 (9)	N3B—C6B—C7B	117.33 (10)
O4—C5—C4	118.90 (9)	C8B—C7B—C6B	119.29 (10)
O3—C5—C4	115.76 (9)	C8B—C7B—H7BA	120.4
C6A—N3A—C10	123.07 (10)	C6B—C7B—H7BA	120.4
C6A—N3A—H1NA	120.5 (11)	C7B—C8B—C9B	122.07 (10)
C10—N3A—H1NA	116.5 (11)	C7B—C8B—H8BA	119.0
C6A—N4A—H3NA	118.1 (12)	C9B—C8B—H8BA	119.0
C6A—N4A—H2NA	119.0 (11)	C10B—C9B—C8B	116.49 (10)
H3NA—N4A—H2NA	122.8 (16)	C10B—C9B—C11B	122.09 (10)
N4A—C6A—N3A	119.34 (10)	C8B—C9B—C11B	121.41 (10)
N4A—C6A—C7A	123.26 (10)	N3B—C10B—C9B	121.42 (10)
N3A—C6A—C7A	117.41 (10)	N3B—C10B—H10B	119.3
C8A—C7A—C6A	119.48 (10)	C9B—C10B—H10B	119.3
C8A—C7A—H7AA	120.3	C9B—C11B—H11D	109.5
C6A—C7A—H7AA	120.3	C9B—C11B—H11E	109.5
C7A—C8A—C9A	122.21 (10)	H11D—C11B—H11E	109.5
C7A—C8A—H8AA	118.9	C9B—C11B—H11F	109.5
C9A—C8A—H8AA	118.9	H11D—C11B—H11F	109.5
C10—C9A—C8A	116.20 (10)	H11E—C11B—H11F	109.5
C10—C9A—C11A	121.63 (11)	H1W3—O3W—H2W3	109.1 (15)
C8A—C9A—C11A	122.17 (11)	H1W2—O2W—H2W2	105.7 (17)
N3A—C10—C9A	121.62 (10)	H1W1—O1W—H2W1	105.7 (18)

C2—N1—N2—C4	−0.55 (11)	N4A—C6A—C7A—C8A	179.69 (11)
N2—N1—C2—C3	0.16 (11)	N3A—C6A—C7A—C8A	−0.19 (16)
N2—N1—C2—C1	177.98 (9)	C6A—C7A—C8A—C9A	−1.06 (17)
O1—C1—C2—N1	172.05 (10)	C7A—C8A—C9A—C10	1.43 (17)
O2—C1—C2—N1	−8.81 (15)	C7A—C8A—C9A—C11A	−178.63 (11)
O1—C1—C2—C3	−10.46 (16)	C6A—N3A—C10—C9A	−0.66 (17)
O2—C1—C2—C3	168.68 (10)	C8A—C9A—C10—N3A	−0.58 (16)
N1—C2—C3—C4	0.25 (12)	C11A—C9A—C10—N3A	179.48 (11)
C1—C2—C3—C4	−177.44 (10)	C10B—N3B—C6B—N4B	178.55 (10)
N1—N2—C4—C3	0.72 (12)	C10B—N3B—C6B—C7B	−0.34 (15)
N1—N2—C4—C5	−178.32 (9)	N4B—C6B—C7B—C8B	−178.10 (11)
C2—C3—C4—N2	−0.56 (11)	N3B—C6B—C7B—C8B	0.74 (15)
C2—C3—C4—C5	178.37 (10)	C6B—C7B—C8B—C9B	−0.84 (17)
N2—C4—C5—O4	−4.89 (15)	C7B—C8B—C9B—C10B	0.50 (16)
C3—C4—C5—O4	176.33 (10)	C7B—C8B—C9B—C11B	−179.15 (10)
N2—C4—C5—O3	174.18 (9)	C6B—N3B—C10B—C9B	0.02 (16)
C3—C4—C5—O3	−4.60 (16)	C8B—C9B—C10B—N3B	−0.08 (15)
C10—N3A—C6A—N4A	−178.84 (10)	C11B—C9B—C10B—N3B	179.57 (10)
C10—N3A—C6A—C7A	1.05 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O4ⁱ	0.931 (16)	1.871 (16)	2.7912 (12)	169.7 (15)
N4A—H3NA···O1Wⁱⁱ	0.861 (18)	2.024 (17)	2.8520 (14)	161.2 (17)
N3B—H1NB···O3ⁱⁱⁱ	0.900 (17)	1.755 (17)	2.6483 (12)	171.4 (16)
N4B—H2NB···O4ⁱⁱⁱ	0.914 (18)	2.022 (18)	2.9323 (13)	173.8 (16)
N4B—H3NB···O3W^iv	0.889 (18)	2.007 (18)	2.8641 (13)	161.6 (17)
N3A—H1NA···O2^iv	0.942 (18)	1.732 (18)	2.6686 (12)	172.8 (17)
N4A—H2NA···O1^iv	0.907 (18)	2.106 (18)	3.0021 (13)	169.4 (15)
O1W—H1W1···O3	0.871 (19)	1.902 (19)	2.7517 (12)	164.8 (17)
O1W—H2W1···O3W^iv	0.85 (2)	1.94 (2)	2.7878 (14)	178 (2)
O2W—H1W2···O1	0.850 (18)	2.003 (18)	2.8427 (12)	169.8 (17)
O2W—H2W2···O1^v	0.858 (18)	1.987 (18)	2.8434 (13)	176.1 (15)
O3W—H1W3···O2	0.888 (17)	1.844 (17)	2.7299 (12)	174.8 (15)
O3W—H2W3···O2W^vi	0.881 (18)	1.900 (18)	2.7758 (13)	172.1 (17)
C10—H10A···O2W	0.93	2.50	3.3986 (15)	164

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

Experimental details

Crystal data
Chemical formula	2C₆H₉N₂⁺·C₅H₂N₂O₄²⁻·3H₂O
M_r	426.44
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.8985 (1), 9.2195 (1), 15.3922 (2)
α, β, γ (°)	101.942 (1), 93.883 (1), 104.648 (1)
V (Å³)	1052.40 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.47 × 0.24 × 0.21

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.952, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	26056, 6103, 5085
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.113, 1.07
No. of reflections	6103
No. of parameters	325
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.24

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
N2—H1N2···O4ⁱ	0.931 (16)	1.871 (16)	2.7912 (12)	169.7 (15)
N4A—H3NA···O1Wⁱⁱ	0.861 (18)	2.024 (17)	2.8520 (14)	161.2 (17)
N3B—H1NB···O3ⁱⁱⁱ	0.900 (17)	1.755 (17)	2.6483 (12)	171.4 (16)
N4B—H2NB···O4ⁱⁱⁱ	0.914 (18)	2.022 (18)	2.9323 (13)	173.8 (16)
N4B—H3NB···O3W^iv	0.889 (18)	2.007 (18)	2.8641 (13)	161.6 (17)
N3A—H1NA···O2^iv	0.942 (18)	1.732 (18)	2.6686 (12)	172.8 (17)
N4A—H2NA···O1^iv	0.907 (18)	2.106 (18)	3.0021 (13)	169.4 (15)
O1W—H1W1···O3	0.871 (19)	1.902 (19)	2.7517 (12)	164.8 (17)
O1W—H2W1···O3W^iv	0.85 (2)	1.94 (2)	2.7878 (14)	178 (2)
O2W—H1W2···O1	0.850 (18)	2.003 (18)	2.8427 (12)	169.8 (17)
O2W—H2W2···O1^v	0.858 (18)	1.987 (18)	2.8434 (13)	176.1 (15)
O3W—H1W3···O2	0.888 (17)	1.844 (17)	2.7299 (12)	174.8 (15)
O3W—H2W3···O2W^vi	0.881 (18)	1.900 (18)	2.7758 (13)	172.1 (17)
C10—H10A···O2W	0.93	2.50	3.3986 (15)	164

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HKF and TSH thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). TSH also thanks USM for the award of a research fellowship and MH thanks USM for a post-doctoral research fellowship.

References

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