Bis(2,6-diamino­pyridinium) tartrate monohydrate

Al-Dajani, M.T.M.; Abdallah, H.H.; Mohamed, N.; Goh, J.H.; Fun, H.-K.

doi:10.1107/S1600536809044663

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages o2939-o2940

https://doi.org/10.1107/S1600536809044663

Open

access

Bis(2,6-diaminopyridinium) tartrate monohydrate

Mohammad T. M. Al-Dajani,^a Hassan H. Abdallah,^b Nornisah Mohamed,^a ^* Jia Hao Goh ^c ‡ and Hoong-Kun Fun ^c ^*§

^aSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: nornisah@usm.my, hkfun@usm.my

(Received 26 October 2009; accepted 27 October 2009; online 31 October 2009)

In the title compound, 2C₅H₈N₃⁺·C₄H₄O₆²⁻·H₂O, the two cations are essentially planar [maximum deviations = 0.023 (1) and 0.026 (1) Å]. In one of the cations, the protonated N atom and one of the amino group H atoms are hydrogen bonded to one of the carboxyl groups of the dianion through a pair of N—H⋯O hydrogen bonds, forming an R₂²(8) ring motif. In the crystal structure, the tartrate anions and water molecules are linked into chains along the c axis by intermolecular O—H⋯O and C—H⋯O hydrogen bonds. The cations further link the anions and water molecules into a three-dimensional extended structure by a network of N—H⋯O hydrogen bonds. The crystal structure is also stabilized by weak intermolecular π–π interactions [centroid–centroid distance = 3.6950 (6) Å].

Related literature

For related structures, see: Al-Dajani, Abdallah et al. (2009 ); Al-Dajani, Salhin et al. (2009 ). 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 for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

2C₅H₈N₃⁺·C₄H₄O₆²⁻·H₂O
M_r = 386.38
Monoclinic, P 2₁ /c
a = 14.4722 (2) Å
b = 15.7270 (2) Å
c = 7.8419 (1) Å
β = 96.916 (1)°
V = 1771.86 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.44 × 0.33 × 0.26 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.950, T_max = 0.970
55803 measured reflections
8384 independent reflections
5761 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.137
S = 1.04
8384 reflections
332 parameters
All H-atom parameters refined
Δρ_max = 0.33 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
O1—H1O1⋯O4ⁱ	0.900 (16)	1.840 (16)	2.7315 (10)	170.9 (15)
O2—H1O2⋯O4ⁱ	0.871 (17)	1.957 (17)	2.8260 (11)	175.6 (15)
N1—H1N1⋯O5	0.933 (13)	1.740 (13)	2.6660 (11)	171.4 (13)
N2—H1N2⋯O2ⁱⁱ	0.882 (17)	2.369 (17)	3.2254 (13)	163.7 (14)
N2—H1N2⋯O6ⁱⁱ	0.882 (17)	2.461 (17)	3.0531 (13)	125.0 (13)
N2—H2N2⋯O6	0.884 (14)	2.048 (14)	2.9306 (13)	176.7 (12)
N3—H1N3⋯O5	0.908 (16)	2.552 (16)	3.2431 (12)	133.4 (13)
N3—H1N3⋯O4ⁱⁱⁱ	0.908 (16)	2.519 (17)	3.1842 (13)	130.5 (13)
N3—H2N3⋯O6^iv	0.860 (16)	2.122 (16)	2.9499 (12)	161.3 (16)
N4—H1N4⋯O3^v	0.924 (17)	1.810 (17)	2.7294 (12)	172.5 (15)
N5—H1N5⋯O1W^vi	0.827 (19)	2.114 (19)	2.9265 (15)	167.7 (15)
N5—H2N5⋯O1^v	0.888 (17)	2.243 (17)	3.0557 (14)	152.0 (14)
N5—H2N5⋯O3^v	0.888 (17)	2.503 (16)	3.2154 (15)	137.8 (13)
N6—H1N6⋯O1W^vii	0.901 (17)	2.127 (17)	3.0131 (18)	167.5 (14)
N6—H2N6⋯O1	0.87 (2)	2.189 (19)	2.9851 (15)	152 (2)
O1W—H1W1⋯O3ⁱⁱⁱ	0.85 (2)	2.37 (3)	2.9371 (13)	125 (2)
O1W—H1W1⋯O4ⁱⁱⁱ	0.85 (2)	2.42 (2)	3.1642 (13)	146 (2)
O1W—H2W1⋯O5	0.89 (2)	1.93 (2)	2.8153 (13)	175 (2)
C2—H2A⋯O3ⁱⁱⁱ	0.963 (11)	2.490 (11)	3.3232 (12)	144.8 (9)
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x, y, z+1; (v) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) -x, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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/S1600536809044663/hb5185sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809044663/hb5185Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title compound, (I) (Fig. 1), comprises of two 2,6-diaminopyridinium cations, a tartrate dianion and a water molecule. Two intermolecular protons transfer from the carboxylic groups of tartaric acid to atoms N1 & N4 of the 2,6-diaminopyridine moiety has resulted in the formation of ions. The protonated N1 atom and the N2 atom of the amino group are hydrogen bonded to the carboxyl group (atoms O5 & O6) via a pair of N—H···O hydrogen bonds forming an R²₂(8) ring motif (Fig. 1, Bernstein et al., 1995). The two 2,6-diaminopyridinium cations (N1–N3/C5–C9) and (N4–N6/C10–C14) are essentially planar, with maximum devations of 0.023 (1) and 0.026 (1) Å, respectively, for atoms C6 and C11. Comparing with the unprotonated structure (De cires-Mejias et al., 2004), protonation of atoms N1 & N4 have widened the C—N—C angles to 123.51 (8) and 123.92 (9)°, respectively, for angles of C5—N1—C9 and C10—N4—C14. The bond lengths (Allen et al., 1987) and angles observed are within normal ranges and are consistent with those related structures (Al-Dajani, Abdallah et al., 2009; Al-Dajani, Salhin et al., 2009).

The crystal structure of (I) is mainly stabilized by a network of N—H···O and C—H···O hydrogen bonds. Each N atom in the cations participates in intermolecular hydrogen bonds. In the crystal structure (Fig. 2), the tartrate anions and water molecules are linked into chains along the c axis by intermolecular O1—H1O1···O4, O2—H1O2···O4, O1W—H1W1···O3, O1W—H1W1···O4, O1W—H2W1···O5 and C2—H2A···O3 hydrogen bonds (Table 1). The 2,6-diaminopyridinium cations further linked the anions and water molecules into a three-dimensional extended structure by a network of N—H···O hydrogen bonds (Table 1). The crystal structure is further stabilized by weak intermolecular π–π interactions [Cg1···Cg1 = 3.6950 (6) Å; Cg1 is the centroid of the N1/C5–C9 pyridine ring].

Related literature top

For related structures, see: Al-Dajani, Abdallah et al. (2009); Al-Dajani, Salhin et al. (2009). 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 for the data collection, see: Cosier & Glazer (1986).

Experimental top

Tartaric acid (0.01 mol, 1.5 g) was dissolved in 50 ml of methanol in a round bottom flask. 2,6-Diaminopyridine (0.02 mol, 2.2 g) was added in small portions to the flask with stirring. The reaction mixture was left stirring for 3 h at room temperature. Brown blocks of (I) were separated, washed with methanol and dried at 353 K.

Structure description top

For related structures, see: Al-Dajani, Abdallah et al. (2009); Al-Dajani, Salhin et al. (2009). 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 for the data collection, see: Cosier & Glazer (1986).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 (I), showing 30% probability displacement ellipsoids for non-H atoms. Intermolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. The crystal structure of (I), viewed along the c axis, showing the three-dimensional network. H atoms not involved in intermolecular interactions (dashed lines) have been omitted for clarity.

Bis(2,6-diaminopyridinium) tartrate monohydrate top

Crystal data top

2C₅H₈N₃⁺·C₄H₄O₆²⁻·H₂O	F(000) = 816
M_r = 386.38	D_x = 1.448 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9979 reflections
a = 14.4722 (2) Å	θ = 2.6–33.1°
b = 15.7270 (2) Å	µ = 0.12 mm⁻¹
c = 7.8419 (1) Å	T = 296 K
β = 96.916 (1)°	Block, brown
V = 1771.86 (4) Å³	0.44 × 0.33 × 0.26 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	8384 independent reflections
Radiation source: fine-focus sealed tube	5761 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
φ and ω scans	θ_max = 36.1°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −23→23
T_min = 0.950, T_max = 0.970	k = −25→24
55803 measured reflections	l = −12→12

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	All H-atom parameters refined
S = 1.04	w = 1/[σ²(F_o²) + (0.0645P)² + 0.1774P] where P = (F_o² + 2F_c²)/3
8384 reflections	(Δ/σ)_max < 0.001
332 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

2C₅H₈N₃⁺·C₄H₄O₆²⁻·H₂O	V = 1771.86 (4) Å³
M_r = 386.38	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.4722 (2) Å	µ = 0.12 mm⁻¹
b = 15.7270 (2) Å	T = 296 K
c = 7.8419 (1) Å	0.44 × 0.33 × 0.26 mm
β = 96.916 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	8384 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5761 reflections with I > 2σ(I)
T_min = 0.950, T_max = 0.970	R_int = 0.029
55803 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.137	All H-atom parameters refined
S = 1.04	Δρ_max = 0.33 e Å⁻³
8384 reflections	Δρ_min = −0.24 e Å⁻³
332 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.14121 (5)	0.62179 (5)	0.37307 (9)	0.03748 (15)
O2	0.33130 (5)	0.69021 (5)	0.36761 (10)	0.03834 (16)
O3	0.09223 (6)	0.78743 (6)	0.35992 (11)	0.0505 (2)
O4	0.19983 (6)	0.82535 (5)	0.57216 (9)	0.04158 (17)
O5	0.28815 (5)	0.55133 (5)	0.71274 (9)	0.04001 (16)
O6	0.36515 (6)	0.53101 (5)	0.48798 (9)	0.04409 (18)
C1	0.15720 (6)	0.77090 (6)	0.47338 (11)	0.03144 (17)
C2	0.18625 (6)	0.67770 (6)	0.49999 (10)	0.02824 (15)
C3	0.29147 (6)	0.66622 (6)	0.51725 (10)	0.02834 (15)
C4	0.31696 (6)	0.57521 (6)	0.57453 (10)	0.02985 (16)
N1	0.39658 (5)	0.44405 (5)	0.90954 (9)	0.02900 (14)
N2	0.47289 (7)	0.39813 (7)	0.68421 (11)	0.0423 (2)
N3	0.31436 (7)	0.50158 (7)	1.11702 (12)	0.0429 (2)
C5	0.46341 (6)	0.39419 (6)	0.85246 (11)	0.03136 (17)
C6	0.51647 (7)	0.34231 (7)	0.97048 (14)	0.0404 (2)
C7	0.49815 (8)	0.34277 (7)	1.13904 (14)	0.0427 (2)
C8	0.43089 (8)	0.39418 (7)	1.19503 (12)	0.0395 (2)
C9	0.38033 (6)	0.44752 (6)	1.07627 (10)	0.03057 (16)
N4	0.07411 (6)	0.29439 (6)	0.34459 (12)	0.03809 (18)
N5	0.05279 (8)	0.15005 (7)	0.31936 (18)	0.0562 (3)
N6	0.07972 (10)	0.44052 (8)	0.3524 (2)	0.0649 (3)
C10	0.10707 (7)	0.21441 (7)	0.37940 (14)	0.0394 (2)
C11	0.19414 (8)	0.20559 (8)	0.47490 (18)	0.0504 (3)
C12	0.24392 (8)	0.27782 (10)	0.52373 (19)	0.0564 (3)
C13	0.20988 (9)	0.35831 (9)	0.48473 (18)	0.0534 (3)
C14	0.12190 (8)	0.36637 (7)	0.39441 (15)	0.0426 (2)
O1W	0.11303 (7)	0.52769 (6)	0.82780 (15)	0.0559 (2)
H1O1	0.1548 (11)	0.6424 (10)	0.272 (2)	0.057 (4)*
H1O2	0.2904 (13)	0.6826 (10)	0.278 (2)	0.067 (5)*
H1N1	0.3619 (9)	0.4801 (8)	0.8319 (18)	0.044 (3)*
H1N2	0.5253 (12)	0.3800 (10)	0.650 (2)	0.062 (4)*
H2N2	0.4425 (9)	0.4390 (9)	0.6238 (18)	0.045 (3)*
H1N3	0.2911 (11)	0.5406 (11)	1.038 (2)	0.065 (5)*
H2N3	0.3161 (12)	0.5144 (10)	1.224 (2)	0.067 (5)*
H1N4	0.0176 (12)	0.2971 (10)	0.276 (2)	0.059 (4)*
H1N5	0.0716 (12)	0.1009 (12)	0.338 (2)	0.068 (5)*
H2N5	−0.0001 (12)	0.1605 (10)	0.253 (2)	0.059 (4)*
H1N6	0.0204 (12)	0.4416 (10)	0.302 (2)	0.060 (4)*
H2N6	0.1102 (14)	0.4860 (12)	0.389 (3)	0.079 (5)*
H2A	0.1657 (8)	0.6614 (7)	0.6076 (14)	0.030 (3)*
H3A	0.3165 (9)	0.7015 (7)	0.6120 (16)	0.034 (3)*
H6A	0.5634 (12)	0.3070 (10)	0.937 (2)	0.063 (4)*
H7A	0.5370 (10)	0.3053 (9)	1.2187 (18)	0.050 (4)*
H8A	0.4196 (10)	0.3943 (9)	1.3120 (19)	0.051 (4)*
H11A	0.2168 (12)	0.1515 (11)	0.498 (2)	0.067 (5)*
H12A	0.3045 (13)	0.2700 (11)	0.588 (2)	0.075 (5)*
H13A	0.2436 (12)	0.4097 (11)	0.514 (2)	0.069 (5)*
H1W1	0.1128 (16)	0.5645 (16)	0.907 (3)	0.102 (7)*
H2W1	0.1669 (15)	0.5349 (13)	0.785 (3)	0.087 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0370 (3)	0.0357 (4)	0.0381 (3)	−0.0092 (3)	−0.0024 (3)	−0.0016 (3)
O2	0.0333 (3)	0.0438 (4)	0.0384 (3)	−0.0046 (3)	0.0061 (3)	0.0108 (3)
O3	0.0395 (4)	0.0544 (5)	0.0547 (5)	0.0125 (3)	−0.0065 (3)	0.0098 (4)
O4	0.0576 (4)	0.0305 (3)	0.0367 (3)	0.0000 (3)	0.0057 (3)	−0.0021 (3)
O5	0.0451 (4)	0.0428 (4)	0.0335 (3)	0.0128 (3)	0.0100 (3)	0.0117 (3)
O6	0.0569 (4)	0.0413 (4)	0.0360 (3)	0.0153 (3)	0.0133 (3)	0.0013 (3)
C1	0.0326 (4)	0.0333 (4)	0.0292 (3)	0.0048 (3)	0.0066 (3)	0.0038 (3)
C2	0.0298 (4)	0.0285 (4)	0.0261 (3)	−0.0009 (3)	0.0020 (3)	0.0011 (3)
C3	0.0292 (4)	0.0281 (4)	0.0269 (3)	−0.0014 (3)	−0.0002 (3)	0.0004 (3)
C4	0.0315 (4)	0.0315 (4)	0.0257 (3)	0.0023 (3)	−0.0001 (3)	0.0008 (3)
N1	0.0305 (3)	0.0292 (4)	0.0266 (3)	0.0036 (3)	0.0006 (2)	0.0020 (2)
N2	0.0456 (5)	0.0480 (5)	0.0346 (4)	0.0104 (4)	0.0100 (3)	0.0000 (4)
N3	0.0471 (5)	0.0488 (5)	0.0331 (4)	0.0141 (4)	0.0064 (3)	−0.0019 (4)
C5	0.0311 (4)	0.0300 (4)	0.0325 (4)	0.0013 (3)	0.0018 (3)	−0.0028 (3)
C6	0.0396 (5)	0.0367 (5)	0.0431 (5)	0.0124 (4)	−0.0028 (4)	−0.0020 (4)
C7	0.0485 (5)	0.0359 (5)	0.0398 (5)	0.0078 (4)	−0.0106 (4)	0.0039 (4)
C8	0.0483 (5)	0.0411 (5)	0.0274 (4)	0.0037 (4)	−0.0022 (3)	0.0033 (3)
C9	0.0322 (4)	0.0317 (4)	0.0270 (3)	−0.0004 (3)	0.0004 (3)	−0.0007 (3)
N4	0.0290 (4)	0.0349 (4)	0.0485 (4)	0.0013 (3)	−0.0029 (3)	−0.0015 (3)
N5	0.0403 (5)	0.0351 (5)	0.0901 (9)	0.0016 (4)	−0.0046 (5)	−0.0084 (5)
N6	0.0575 (7)	0.0332 (5)	0.0982 (10)	−0.0015 (5)	−0.0145 (6)	0.0028 (5)
C10	0.0319 (4)	0.0352 (5)	0.0508 (5)	0.0024 (4)	0.0031 (4)	−0.0024 (4)
C11	0.0376 (5)	0.0459 (7)	0.0651 (7)	0.0093 (5)	−0.0048 (5)	0.0021 (5)
C12	0.0339 (5)	0.0639 (8)	0.0670 (8)	0.0027 (5)	−0.0123 (5)	−0.0004 (6)
C13	0.0413 (6)	0.0490 (7)	0.0661 (8)	−0.0081 (5)	−0.0095 (5)	−0.0043 (5)
C14	0.0388 (5)	0.0365 (5)	0.0512 (6)	−0.0026 (4)	−0.0003 (4)	−0.0007 (4)
O1W	0.0539 (5)	0.0414 (5)	0.0734 (6)	−0.0122 (4)	0.0114 (4)	−0.0059 (4)

Geometric parameters (Å, º) top

O1—C2	1.4257 (11)	C6—H6A	0.938 (17)
O1—H1O1	0.901 (16)	C7—C8	1.3773 (16)
O2—C3	1.4194 (10)	C7—H7A	0.984 (15)
O2—H1O2	0.868 (19)	C8—C9	1.3937 (13)
O3—C1	1.2418 (12)	C8—H8A	0.951 (14)
O4—C1	1.2644 (12)	N4—C14	1.3591 (14)
O5—C4	1.2643 (10)	N4—C10	1.3613 (13)
O6—C4	1.2426 (11)	N4—H1N4	0.923 (17)
C1—C2	1.5322 (13)	N5—C10	1.3319 (15)
C2—C3	1.5231 (12)	N5—H1N5	0.827 (18)
C2—H2A	0.962 (11)	N5—H2N5	0.888 (17)
C3—C4	1.5318 (12)	N6—C14	1.3390 (16)
C3—H3A	0.962 (12)	N6—H1N6	0.901 (18)
N1—C9	1.3572 (11)	N6—H2N6	0.87 (2)
N1—C5	1.3620 (11)	C10—C11	1.3930 (16)
N1—H1N1	0.933 (14)	C11—C12	1.3747 (19)
N2—C5	1.3443 (12)	C11—H11A	0.922 (18)
N2—H1N2	0.881 (17)	C12—C13	1.379 (2)
N2—H2N2	0.884 (14)	C12—H12A	0.963 (19)
N3—C9	1.3453 (13)	C13—C14	1.3862 (16)
N3—H1N3	0.907 (17)	C13—H13A	0.959 (17)
N3—H2N3	0.859 (18)	O1W—H1W1	0.85 (3)
C5—C6	1.3931 (13)	O1W—H2W1	0.89 (2)
C6—C7	1.3790 (15)

C2—O1—H1O1	105.3 (10)	C8—C7—C6	122.24 (9)
C3—O2—H1O2	108.9 (11)	C8—C7—H7A	121.3 (8)
O3—C1—O4	124.66 (9)	C6—C7—H7A	116.4 (8)
O3—C1—C2	118.00 (9)	C7—C8—C9	118.34 (9)
O4—C1—C2	117.31 (8)	C7—C8—H8A	121.2 (9)
O1—C2—C3	110.92 (7)	C9—C8—H8A	120.4 (9)
O1—C2—C1	113.58 (7)	N3—C9—N1	117.68 (8)
C3—C2—C1	112.37 (7)	N3—C9—C8	123.52 (9)
O1—C2—H2A	106.5 (7)	N1—C9—C8	118.79 (8)
C3—C2—H2A	107.6 (7)	C14—N4—C10	123.92 (9)
C1—C2—H2A	105.4 (7)	C14—N4—H1N4	120.8 (10)
O2—C3—C2	113.34 (7)	C10—N4—H1N4	115.1 (10)
O2—C3—C4	112.54 (7)	C10—N5—H1N5	118.6 (12)
C2—C3—C4	109.86 (7)	C10—N5—H2N5	119.8 (11)
O2—C3—H3A	109.4 (7)	H1N5—N5—H2N5	121.5 (16)
C2—C3—H3A	106.2 (7)	C14—N6—H1N6	120.4 (11)
C4—C3—H3A	104.9 (7)	C14—N6—H2N6	115.8 (13)
O6—C4—O5	124.53 (9)	H1N6—N6—H2N6	123.2 (17)
O6—C4—C3	119.58 (8)	N5—C10—N4	116.98 (10)
O5—C4—C3	115.86 (8)	N5—C10—C11	124.84 (11)
C9—N1—C5	123.51 (8)	N4—C10—C11	118.18 (10)
C9—N1—H1N1	117.5 (8)	C12—C11—C10	118.51 (11)
C5—N1—H1N1	118.9 (8)	C12—C11—H11A	123.0 (11)
C5—N2—H1N2	118.3 (11)	C10—C11—H11A	118.4 (11)
C5—N2—H2N2	117.2 (9)	C11—C12—C13	122.37 (11)
H1N2—N2—H2N2	117.8 (13)	C11—C12—H12A	116.9 (11)
C9—N3—H1N3	118.8 (10)	C13—C12—H12A	120.7 (11)
C9—N3—H2N3	116.2 (11)	C12—C13—C14	118.61 (11)
H1N3—N3—H2N3	118.1 (15)	C12—C13—H13A	124.2 (10)
N2—C5—N1	117.16 (8)	C14—C13—H13A	117.1 (10)
N2—C5—C6	124.46 (9)	N6—C14—N4	116.97 (10)
N1—C5—C6	118.38 (8)	N6—C14—C13	124.67 (11)
C7—C6—C5	118.65 (9)	N4—C14—C13	118.36 (11)
C7—C6—H6A	119.9 (10)	H1W1—O1W—H2W1	106 (2)
C5—C6—H6A	121.5 (10)

O3—C1—C2—O1	7.58 (11)	C5—C6—C7—C8	−1.59 (17)
O4—C1—C2—O1	−174.21 (7)	C6—C7—C8—C9	−0.26 (17)
O3—C1—C2—C3	134.52 (9)	C5—N1—C9—N3	177.76 (9)
O4—C1—C2—C3	−47.27 (10)	C5—N1—C9—C8	−3.54 (14)
O1—C2—C3—O2	65.36 (10)	C7—C8—C9—N3	−178.63 (10)
C1—C2—C3—O2	−62.99 (9)	C7—C8—C9—N1	2.75 (15)
O1—C2—C3—C4	−61.50 (9)	C14—N4—C10—N5	−178.83 (11)
C1—C2—C3—C4	170.15 (7)	C14—N4—C10—C11	1.42 (17)
O2—C3—C4—O6	−2.16 (12)	N5—C10—C11—C12	177.88 (13)
C2—C3—C4—O6	125.14 (9)	N4—C10—C11—C12	−2.39 (19)
O2—C3—C4—O5	176.12 (8)	C10—C11—C12—C13	1.4 (2)
C2—C3—C4—O5	−56.57 (10)	C11—C12—C13—C14	0.6 (2)
C9—N1—C5—N2	−178.91 (9)	C10—N4—C14—N6	−179.17 (12)
C9—N1—C5—C6	1.66 (14)	C10—N4—C14—C13	0.63 (17)
N2—C5—C6—C7	−178.45 (10)	C12—C13—C14—N6	178.15 (14)
N1—C5—C6—C7	0.93 (15)	C12—C13—C14—N4	−1.64 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O4ⁱ	0.900 (16)	1.840 (16)	2.7315 (10)	170.9 (15)
O2—H1O2···O4ⁱ	0.871 (17)	1.957 (17)	2.8260 (11)	175.6 (15)
N1—H1N1···O5	0.933 (13)	1.740 (13)	2.6660 (11)	171.4 (13)
N2—H1N2···O2ⁱⁱ	0.882 (17)	2.369 (17)	3.2254 (13)	163.7 (14)
N2—H1N2···O6ⁱⁱ	0.882 (17)	2.461 (17)	3.0531 (13)	125.0 (13)
N2—H2N2···O6	0.884 (14)	2.048 (14)	2.9306 (13)	176.7 (12)
N3—H1N3···O5	0.908 (16)	2.552 (16)	3.2431 (12)	133.4 (13)
N3—H1N3···O4ⁱⁱⁱ	0.908 (16)	2.519 (17)	3.1842 (13)	130.5 (13)
N3—H2N3···O6^iv	0.860 (16)	2.122 (16)	2.9499 (12)	161.3 (16)
N4—H1N4···O3^v	0.924 (17)	1.810 (17)	2.7294 (12)	172.5 (15)
N5—H1N5···O1W^vi	0.827 (19)	2.114 (19)	2.9265 (15)	167.7 (15)
N5—H2N5···O1^v	0.888 (17)	2.243 (17)	3.0557 (14)	152.0 (14)
N5—H2N5···O3^v	0.888 (17)	2.503 (16)	3.2154 (15)	137.8 (13)
N6—H1N6···O1W^vii	0.901 (17)	2.127 (17)	3.0131 (18)	167.5 (14)
N6—H2N6···O1	0.87 (2)	2.189 (19)	2.9851 (15)	152 (2)
O1W—H1W1···O3ⁱⁱⁱ	0.85 (2)	2.37 (3)	2.9371 (13)	125 (2)
O1W—H1W1···O4ⁱⁱⁱ	0.85 (2)	2.42 (2)	3.1642 (13)	146 (2)
O1W—H2W1···O5	0.89 (2)	1.93 (2)	2.8153 (13)	175 (2)
C2—H2A···O3ⁱⁱⁱ	0.963 (11)	2.490 (11)	3.3232 (12)	144.8 (9)

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

Experimental details

Crystal data
Chemical formula	2C₅H₈N₃⁺·C₄H₄O₆²⁻·H₂O
M_r	386.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	14.4722 (2), 15.7270 (2), 7.8419 (1)
β (°)	96.916 (1)
V (Å³)	1771.86 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.44 × 0.33 × 0.26

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.950, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	55803, 8384, 5761
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.829

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.137, 1.04
No. of reflections	8384
No. of parameters	332
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.24

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), 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
O1—H1O1···O4ⁱ	0.900 (16)	1.840 (16)	2.7315 (10)	170.9 (15)
O2—H1O2···O4ⁱ	0.871 (17)	1.957 (17)	2.8260 (11)	175.6 (15)
N1—H1N1···O5	0.933 (13)	1.740 (13)	2.6660 (11)	171.4 (13)
N2—H1N2···O2ⁱⁱ	0.882 (17)	2.369 (17)	3.2254 (13)	163.7 (14)
N2—H1N2···O6ⁱⁱ	0.882 (17)	2.461 (17)	3.0531 (13)	125.0 (13)
N2—H2N2···O6	0.884 (14)	2.048 (14)	2.9306 (13)	176.7 (12)
N3—H1N3···O5	0.908 (16)	2.552 (16)	3.2431 (12)	133.4 (13)
N3—H1N3···O4ⁱⁱⁱ	0.908 (16)	2.519 (17)	3.1842 (13)	130.5 (13)
N3—H2N3···O6^iv	0.860 (16)	2.122 (16)	2.9499 (12)	161.3 (16)
N4—H1N4···O3^v	0.924 (17)	1.810 (17)	2.7294 (12)	172.5 (15)
N5—H1N5···O1W^vi	0.827 (19)	2.114 (19)	2.9265 (15)	167.7 (15)
N5—H2N5···O1^v	0.888 (17)	2.243 (17)	3.0557 (14)	152.0 (14)
N5—H2N5···O3^v	0.888 (17)	2.503 (16)	3.2154 (15)	137.8 (13)
N6—H1N6···O1W^vii	0.901 (17)	2.127 (17)	3.0131 (18)	167.5 (14)
N6—H2N6···O1	0.87 (2)	2.189 (19)	2.9851 (15)	152 (2)
O1W—H1W1···O3ⁱⁱⁱ	0.85 (2)	2.37 (3)	2.9371 (13)	125 (2)
O1W—H1W1···O4ⁱⁱⁱ	0.85 (2)	2.42 (2)	3.1642 (13)	146 (2)
O1W—H2W1···O5	0.89 (2)	1.93 (2)	2.8153 (13)	175 (2)
C2—H2A···O3ⁱⁱⁱ	0.963 (11)	2.490 (11)	3.3232 (12)	144.8 (9)

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

Footnotes

‡Thomson Reuters ResearcherID: C-7576-2009.

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

This research was supported by Universiti Sains Malaysia (USM) under grant No. 1001/PFARMASI/815025. HKF and JHG thank USM for the Research University Golden Goose grant No. 1001/PFIZIK/811012. JHG also thanks USM for the award of a USM fellowship.

References

Al-Dajani, M. T. M., Abdallah, H. H., Mohamed, N., Goh, J. H. & Fun, H.-K. (2009). Acta Cryst. E65, o2508–o2509. Web of Science CSD CrossRef IUCr Journals Google Scholar
Al-Dajani, M. T. M., Salhin, A., Mohamed, N., Loh, W.-S. & Fun, H.-K. (2009). Acta Cryst. E65, o2931–o2932. Web of Science CSD CrossRef IUCr Journals Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar