Bis(2-amino-3-nitro­pyridinium) dihydrogen­diphosphate

Toumi Akriche, S.; Rzaigui, M.; Elothman, Z.A.; Mahfouz, R.M.

doi:10.1107/S1600536810000942

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page o358

https://doi.org/10.1107/S1600536810000942

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Bis(2-amino-3-nitropyridinium) dihydrogendiphosphate

Samah Toumi Akriche,^a ^* Mohamed Rzaigui,^a Zeid Abdellah Elothman ^b and Refaat Mohamed Mahfouz ^b

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and ^bChemistry Department, Faculty of Science, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia
^*Correspondence e-mail: toumiakriche@yahoo.fr

(Received 5 January 2010; accepted 7 January 2010; online 16 January 2010)

The structure of the title compound, 2C₅H₆N₃O₂⁺·H₂P₂O₇²⁻, contains infinite (H₂P₂O₇²⁻)_n layers stacked perpendicular to the a axis. The 2-amino-3-nitropyridinium cations are arranged in pairs and are anchored between these layers, linking them by N—H⋯O and C—H⋯O hydrogen-bonding and electrostatic interactions between anionic and cationic species to form a three-dimensional network.

Related literature

For related structures of 2-amino-3-nitropyridinium, see: Akriche & Rzaigui (2000 , 2009a ,b ,c ); Nicoud et al. (1997 ). For bond lengths in related structures, see: Aakeröy et al. (1998 ). For related structures of diphosphate anions, see: Akriche & Rzaigui (2005 ); Charfi & Jouini (2005 ); Brodski et al. (2004 ); Mrad et al. (2006 ); Soumhi et al. (1998 ).

Experimental

Crystal data

2C₅H₆N₃O₂⁺·H₂O₇P₂²⁻
M_r = 456.21
Orthorhombic, P c a 2₁
a = 34.250 (5) Å
b = 5.763 (2) Å
c = 8.991 (3) Å
V = 1774.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 298 K
0.29 × 0.25 × 0.19 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
2726 measured reflections
2724 independent reflections
2279 reflections with I > 2σ(I)
R_int = 0.008
2 standard reflections every 120 min intensity decay: 3%

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.091
S = 1.09
2724 reflections
265 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), 443 Friedel pairs
Flack parameter: −0.15 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O5ⁱ	0.82	1.73	2.549 (3)	178
O7—H7⋯O1ⁱⁱ	0.82	1.73	2.537 (3)	166
N1—H1⋯O1	0.86	1.87	2.706 (3)	165
N2—H2A⋯O3	0.86	1.88	2.726 (4)	168
N2—H2B⋯O9	0.86	2.05	2.645 (4)	126
N4—H4⋯O6	0.86	1.72	2.582 (4)	174
N5—H5A⋯O5	0.86	1.95	2.786 (4)	165
N5—H5B⋯O10	0.86	2.07	2.669 (5)	126
N5—H5B⋯O3ⁱⁱⁱ	0.86	2.22	2.843 (4)	130
C2—H2C⋯O7^iv	0.93	2.46	3.280 (4)	147
C3—H3⋯O6^iv	0.93	2.34	3.208 (4)	155
C8—H8⋯O9^v	0.93	2.52	3.097 (4)	120
Symmetry codes: (i) x, y+1, z; (ii) $[-x, -y+1, z-{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) x, y-1, z+1; (v) $[-x+{\script{1\over 2}}, y, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810000942/dn2529sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000942/dn2529Isup2.hkl

checkCIF report

Comment top

In the framework of our systematic research using the 2-amino-3-nitropyridine (2 A3NP) molecule, we report here the new non-centrosymetric compound, 2(C₅H₆N₃O₂)⁺, H₂P₂O₇^2- (I) obtained by the interaction of the 2 A3NP molecule and diphosphoric acid.

The asymmetric unit of the title compound is built up from one anion H₂P₂O₇^2- and two (C₅H₆N₃O₂)⁺ cations as shown in Fig. 1.

The dihydrogendiphosphate anions are connected through strong hydrogen bonds characterized by relatively short distances (with distances O2···O5 = 2.549 (3) Å and O7···O1 = 2.537 (3) Å (Table 1)), to form corrugated layers parallel to bc plane at x = 0 and x= 1/2 (Fig. 2). Two crystallographically independent cations coexist in this structure. They are arranged in pairs and anchored onto both adjacent anionic layers via N—H···O and C—H···O hydrogen bonds to keep up the three-dimensionel network cohesion.

As expected, the H₂P₂O₇^2- group with bent configuration shows its standard geometry, the longest bonds length P2–O4 = 1.592 (2) Å and P1–O4 = 1.613 (2) Å, correspond to the bridging oxygen atom, the intermediate ones, P1–O2 = 1.552 (2) Å and P2–O7 = 1.545 (2) Å, correspond to the P–OH bonding and the shortest ones spreading between 1.481 (2) Å and 1.515 (2) Å, correspond to the external oxygen atoms. The average values of the P–O distances and O–P–O angles are 1.536 Å and 109.3°. The P–P distance is 2.898 (1) Å and the P–O–P angle is close to 129.4 (1) °. All these distances and angles are similar to those commonly observed in others diphosphate anions (Akriche & Rzaigui, 2005; Charfi & Jouini, 2005; Brodski, et al., 2004; Mrad, et al., 2006). Despite the limited number of organic cation diphosphates (about twenty seven related structures of diphosphate anions), we can distinguish only one non-centrosymmetric structure (Soumhi, et al., 1998) such as the title compound (I).

In this atomic arrangement, one can distinguish the inter-cation contact C8—H8···O9 (H8···O9 = 2.52 Å) which induces the aggregation of the two independent organic cations in pairs (2 A3NP⁺)₂. This kind of arrangement is also observed in the related structure of 2-amino-3-nitropyridinium hydrogenselenate (Akriche & Rzaigui, 2009b). These pairs are located between the anionic layers to link them by manifesting different interactions (Fig. 2). The geometric features of organic cations are usual and comparable with values of other 2-amino-3-nitropyridinium compounds (Akriche & Rzaigui, 2000; Nicoud et al.,1997; Akriche & Rzaigui, 2009a, 2009b, 2009c). It is worth noticing, the C—NH₂ (1.316 (4) Å) and C—NO₂ (1.440 (4) and 1.454 (5) Å) distances in the 2 A3NP cations are respectively shortened and lengthened with respect to the C—NH₂ (1.337 (4) Å) and C—NO₂ (1.429 (4) Å) observed in the 2-amino-3-nitropyridine molecular crystal (Aakeröy, et al., 1998). All the 2-amino-3-nitropyridinium cations encapsulated in various anionic subnetworks show the same changes in C—NH₂ and C—NO₂ distances, revealing a weak increase of pi bond character in C—NH₂ and a decrease in C—NO₂.

Related literature top

For related structures of 2-amino-3-nitropyridinium, see: Akriche & Rzaigui (2000); Akriche & Rzaigui (2009a,b,c); Nicoud et al. (1997). For bond lengths in related structures, see: Aakeröy et al. (1998). For related structures of diphosphate anions, see: Akriche & Rzaigui (2005); Charfi & Jouini (2005); Brodski et al. (2004); Mrad et al. (2006); Soumhi et al. (1998).

Experimental top

Single crystals of the title compound were prepared at room temperature by slow evaporation of a mixture of an aqueous solution (20 ml) of diphosphoric acid (5 mmol) and an ethanolic solution (10 ml) of 2-amino-3-nitropyridine (4 mmol, 354 mg). The diphosphoric acid was produced from Na₄P₂O₇ by using a cation-exchange resin (Amberlite IR 120). The resulting solution was evaporated slowly at room temperature for several days until the formation of good quality of prismatic single crystals.

Structure description top

The asymmetric unit of the title compound is built up from one anion H₂P₂O₇^2- and two (C₅H₆N₃O₂)⁺ cations as shown in Fig. 1.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. An ORTEP view of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are represented as dashed lines.
	Fig. 2. Projection of (I) along the b axis. The H-atoms not involved in H-bonding are omitted.

Bis(2-amino-3-nitropyridinium) dihydrogendiphosphate top

Crystal data top

2C₅H₆N₃O₂⁺·H₂O₇P₂²⁻	F(000) = 936
M_r = 456.21	D_x = 1.707 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 25 reflections
a = 34.250 (5) Å	θ = 10–12°
b = 5.763 (2) Å	µ = 0.32 mm⁻¹
c = 8.991 (3) Å	T = 298 K
V = 1774.8 (9) Å³	Prism, yellow
Z = 4	0.29 × 0.25 × 0.19 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.008
Radiation source: fine-focus sealed tube	θ_max = 30.0°, θ_min = 3.3°
Graphite monochromator	h = −48→0
non–profiled ω scans	k = 0→8
2726 measured reflections	l = −12→0
2724 independent reflections	2 standard reflections every 120 min
2279 reflections with I > 2σ(I)	intensity decay: 3%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0391P)² + 0.7964P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.091	(Δ/σ)_max = 0.001
S = 1.09	Δρ_max = 0.53 e Å⁻³
2724 reflections	Δρ_min = −0.28 e Å⁻³
265 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0192 (12)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.15 (11)

Crystal data top

2C₅H₆N₃O₂⁺·H₂O₇P₂²⁻	V = 1774.8 (9) Å³
M_r = 456.21	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 34.250 (5) Å	µ = 0.32 mm⁻¹
b = 5.763 (2) Å	T = 298 K
c = 8.991 (3) Å	0.29 × 0.25 × 0.19 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.008
2726 measured reflections	2 standard reflections every 120 min
2724 independent reflections	intensity decay: 3%
2279 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.091	Δρ_max = 0.53 e Å⁻³
S = 1.09	Δρ_min = −0.28 e Å⁻³
2724 reflections	Absolute structure: Flack (1983)
265 parameters	Absolute structure parameter: −0.15 (11)
1 restraint

Special details top

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
P1	0.05181 (2)	0.76331 (12)	0.64677 (9)	0.02939 (15)
P2	0.06740 (2)	0.49228 (13)	0.38188 (9)	0.02940 (15)
O1	0.02869 (6)	0.6068 (4)	0.7473 (3)	0.0388 (5)
O2	0.03160 (6)	1.0043 (4)	0.6468 (3)	0.0380 (5)
H2	0.0432	1.0916	0.5898	0.057*
O3	0.09419 (6)	0.7686 (4)	0.6795 (3)	0.0406 (5)
O4	0.04503 (6)	0.6839 (4)	0.4767 (2)	0.0349 (4)
O5	0.06725 (7)	0.2687 (4)	0.4645 (3)	0.0442 (6)
O6	0.10798 (6)	0.5779 (4)	0.3433 (3)	0.0381 (5)
O7	0.04355 (6)	0.4892 (4)	0.2361 (2)	0.0367 (5)
H7	0.0207	0.4592	0.2548	0.055*
O8	0.17007 (11)	0.0987 (8)	1.2413 (5)	0.0996 (14)
O9	0.17848 (8)	0.4036 (7)	1.1115 (4)	0.0796 (12)
O10	0.17870 (9)	−0.0306 (6)	0.8224 (4)	0.0689 (9)
O11	0.23687 (9)	0.0861 (7)	0.8703 (5)	0.0899 (12)
N1	0.07030 (7)	0.3161 (5)	0.9226 (3)	0.0334 (5)
H1	0.0606	0.4078	0.8567	0.040*
N2	0.12502 (8)	0.5449 (5)	0.9194 (3)	0.0445 (7)
H2A	0.1139	0.6299	0.8532	0.053*
H2B	0.1481	0.5788	0.9499	0.053*
N3	0.15874 (9)	0.2373 (7)	1.1479 (5)	0.0578 (9)
N4	0.16725 (8)	0.4967 (5)	0.5130 (4)	0.0396 (6)
H4	0.1465	0.5191	0.4608	0.048*
N5	0.13779 (8)	0.1725 (6)	0.6059 (4)	0.0522 (8)
H5A	0.1184	0.1998	0.5479	0.063*
H5B	0.1374	0.0536	0.6637	0.063*
N6	0.20652 (10)	0.1031 (6)	0.8028 (4)	0.0548 (8)
C1	0.04851 (9)	0.1383 (5)	0.9672 (4)	0.0374 (6)
H1A	0.0236	0.1196	0.9281	0.045*
C2	0.06201 (11)	−0.0169 (6)	1.0689 (4)	0.0450 (8)
H2C	0.0469	−0.1431	1.0978	0.054*
C3	0.09860 (10)	0.0180 (6)	1.1278 (4)	0.0453 (8)
H3	0.1084	−0.0843	1.1986	0.054*
C4	0.12081 (9)	0.2041 (6)	1.0822 (4)	0.0404 (7)
C5	0.10672 (8)	0.3631 (5)	0.9740 (4)	0.0350 (6)
C6	0.19675 (10)	0.6453 (6)	0.4979 (5)	0.0470 (8)
H6	0.1943	0.7678	0.4312	0.056*
C7	0.23056 (10)	0.6223 (7)	0.5778 (5)	0.0550 (10)
H7C	0.2512	0.7255	0.5652	0.066*
C8	0.23302 (9)	0.4406 (7)	0.6779 (4)	0.0511 (9)
H8	0.2554	0.4221	0.7352	0.061*
C9	0.20255 (9)	0.2872 (6)	0.6933 (4)	0.0417 (7)
C10	0.16813 (9)	0.3125 (6)	0.6061 (4)	0.0389 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0326 (3)	0.0309 (3)	0.0247 (3)	−0.0046 (3)	−0.0008 (3)	0.0044 (3)
P2	0.0323 (3)	0.0269 (3)	0.0291 (3)	−0.0007 (3)	0.0004 (3)	0.0045 (3)
O1	0.0377 (10)	0.0429 (12)	0.0357 (11)	−0.0058 (9)	−0.0001 (9)	0.0130 (10)
O2	0.0473 (11)	0.0334 (10)	0.0333 (11)	−0.0004 (9)	0.0047 (10)	0.0004 (11)
O3	0.0373 (10)	0.0474 (12)	0.0371 (13)	−0.0090 (10)	−0.0036 (9)	0.0097 (10)
O4	0.0379 (10)	0.0374 (10)	0.0293 (10)	0.0054 (9)	−0.0045 (9)	0.0000 (9)
O5	0.0461 (13)	0.0321 (11)	0.0544 (15)	−0.0020 (9)	0.0013 (11)	0.0162 (11)
O6	0.0336 (10)	0.0412 (11)	0.0394 (12)	−0.0049 (9)	0.0003 (9)	0.0102 (10)
O7	0.0357 (10)	0.0457 (12)	0.0288 (10)	−0.0050 (10)	−0.0004 (9)	−0.0028 (10)
O8	0.072 (2)	0.126 (3)	0.101 (3)	0.007 (2)	−0.035 (2)	0.058 (3)
O9	0.0414 (14)	0.108 (3)	0.089 (3)	−0.0142 (16)	−0.0172 (16)	0.035 (2)
O10	0.0647 (18)	0.073 (2)	0.069 (2)	−0.0055 (16)	−0.0033 (15)	0.0349 (18)
O11	0.0635 (19)	0.114 (3)	0.092 (3)	0.0031 (19)	−0.025 (2)	0.045 (3)
N1	0.0393 (13)	0.0353 (13)	0.0257 (11)	0.0034 (10)	−0.0001 (9)	0.0036 (10)
N2	0.0426 (14)	0.0462 (16)	0.0447 (17)	−0.0056 (12)	−0.0057 (12)	0.0137 (13)
N3	0.0423 (15)	0.079 (2)	0.0518 (17)	0.0116 (17)	−0.0067 (16)	0.018 (2)
N4	0.0325 (11)	0.0423 (14)	0.0440 (15)	0.0013 (11)	−0.0029 (11)	0.0083 (13)
N5	0.0423 (15)	0.0524 (17)	0.062 (2)	−0.0119 (13)	−0.0101 (15)	0.0222 (16)
N6	0.0492 (16)	0.066 (2)	0.0494 (18)	0.0083 (16)	0.0005 (15)	0.0154 (17)
C1	0.0393 (15)	0.0418 (16)	0.0309 (14)	−0.0026 (13)	0.0037 (13)	−0.0027 (14)
C2	0.0549 (19)	0.0353 (16)	0.0447 (18)	−0.0021 (15)	0.0087 (16)	0.0062 (15)
C3	0.0535 (17)	0.0414 (16)	0.0411 (19)	0.0132 (14)	0.0058 (15)	0.0119 (16)
C4	0.0373 (15)	0.0488 (18)	0.0350 (16)	0.0079 (13)	−0.0004 (13)	0.0054 (15)
C5	0.0372 (14)	0.0390 (16)	0.0288 (13)	0.0054 (12)	0.0018 (12)	0.0035 (13)
C6	0.0419 (17)	0.0463 (18)	0.053 (2)	−0.0023 (14)	0.0041 (15)	0.0086 (17)
C7	0.0374 (17)	0.061 (2)	0.066 (3)	−0.0102 (16)	0.0042 (18)	0.008 (2)
C8	0.0303 (14)	0.072 (2)	0.051 (2)	0.0006 (16)	−0.0028 (15)	0.0070 (19)
C9	0.0329 (13)	0.0520 (18)	0.0404 (15)	0.0050 (13)	0.0030 (12)	0.0089 (16)
C10	0.0345 (14)	0.0408 (16)	0.0412 (16)	0.0024 (13)	0.0042 (13)	0.0041 (13)

Geometric parameters (Å, º) top

P1—O3	1.481 (2)	N4—C6	1.331 (4)
P1—O1	1.503 (2)	N4—C10	1.353 (4)
P1—O2	1.552 (2)	N4—H4	0.8600
P1—O4	1.613 (2)	N5—C10	1.316 (4)
P2—O5	1.487 (2)	N5—H5A	0.8600
P2—O6	1.515 (2)	N5—H5B	0.8600
P2—O7	1.545 (2)	N6—C9	1.454 (5)
P2—O4	1.592 (2)	C1—C2	1.360 (5)
O2—H2	0.8200	C1—H1A	0.9300
O7—H7	0.8200	C2—C3	1.375 (5)
O8—N3	1.222 (5)	C2—H2C	0.9300
O9—N3	1.217 (5)	C3—C4	1.377 (5)
O10—N6	1.238 (4)	C3—H3	0.9300
O11—N6	1.208 (4)	C4—C5	1.420 (4)
N1—C1	1.330 (4)	C6—C7	1.369 (5)
N1—C5	1.358 (4)	C6—H6	0.9300
N1—H1	0.8600	C7—C8	1.383 (5)
N2—C5	1.316 (4)	C7—H7C	0.9300
N2—H2A	0.8600	C8—C9	1.375 (5)
N2—H2B	0.8600	C8—H8	0.9300
N3—C4	1.440 (4)	C9—C10	1.423 (5)

O3—P1—O1	114.15 (13)	O10—N6—C9	118.6 (3)
O3—P1—O2	114.74 (13)	N1—C1—C2	121.2 (3)
O1—P1—O2	107.60 (13)	N1—C1—H1A	119.4
O3—P1—O4	109.59 (13)	C2—C1—H1A	119.4
O1—P1—O4	108.93 (14)	C1—C2—C3	118.2 (3)
O2—P1—O4	100.93 (13)	C1—C2—H2C	120.9
O5—P2—O6	113.55 (13)	C3—C2—H2C	120.9
O5—P2—O7	114.34 (15)	C2—C3—C4	120.2 (3)
O6—P2—O7	107.14 (13)	C2—C3—H3	119.9
O5—P2—O4	109.41 (14)	C4—C3—H3	119.9
O6—P2—O4	109.76 (13)	C3—C4—C5	121.2 (3)
O7—P2—O4	101.99 (12)	C3—C4—N3	118.7 (3)
P1—O2—H2	109.5	C5—C4—N3	120.1 (3)
P2—O4—P1	129.43 (14)	N2—C5—N1	118.0 (3)
P2—O7—H7	109.5	N2—C5—C4	127.4 (3)
C1—N1—C5	124.5 (3)	N1—C5—C4	114.6 (3)
C1—N1—H1	117.7	N4—C6—C7	121.7 (4)
C5—N1—H1	117.7	N4—C6—H6	119.1
C5—N2—H2A	120.0	C7—C6—H6	119.1
C5—N2—H2B	120.0	C6—C7—C8	117.8 (3)
H2A—N2—H2B	120.0	C6—C7—H7C	121.1
O9—N3—O8	121.5 (4)	C8—C7—H7C	121.1
O9—N3—C4	119.7 (3)	C9—C8—C7	120.4 (3)
O8—N3—C4	118.8 (4)	C9—C8—H8	119.8
C6—N4—C10	123.4 (3)	C7—C8—H8	119.8
C6—N4—H4	118.3	C8—C9—C10	120.5 (3)
C10—N4—H4	118.3	C8—C9—N6	117.8 (3)
C10—N5—H5A	120.0	C10—C9—N6	121.7 (3)
C10—N5—H5B	120.0	N5—C10—N4	117.6 (3)
H5A—N5—H5B	120.0	N5—C10—C9	126.3 (3)
O11—N6—O10	122.7 (4)	N4—C10—C9	116.1 (3)
O11—N6—C9	118.7 (3)

O5—P2—O4—P1	53.0 (2)	N3—C4—C5—N2	1.9 (6)
O6—P2—O4—P1	−72.2 (2)	C3—C4—C5—N1	0.4 (5)
O7—P2—O4—P1	174.45 (18)	N3—C4—C5—N1	−178.7 (3)
O3—P1—O4—P2	39.2 (2)	C10—N4—C6—C7	−0.5 (6)
O1—P1—O4—P2	−86.3 (2)	N4—C6—C7—C8	−1.1 (6)
O2—P1—O4—P2	160.61 (18)	C6—C7—C8—C9	1.2 (6)
C5—N1—C1—C2	−1.3 (5)	C7—C8—C9—C10	0.2 (6)
N1—C1—C2—C3	1.6 (5)	C7—C8—C9—N6	−178.6 (4)
C1—C2—C3—C4	−0.9 (5)	O11—N6—C9—C8	−3.4 (6)
C2—C3—C4—C5	−0.1 (5)	O10—N6—C9—C8	177.0 (4)
C2—C3—C4—N3	179.0 (4)	O11—N6—C9—C10	177.8 (4)
O9—N3—C4—C3	−178.4 (4)	O10—N6—C9—C10	−1.8 (5)
O8—N3—C4—C3	0.5 (6)	C6—N4—C10—N5	−176.9 (4)
O9—N3—C4—C5	0.7 (6)	C6—N4—C10—C9	1.9 (5)
O8—N3—C4—C5	179.6 (4)	C8—C9—C10—N5	177.0 (4)
C1—N1—C5—N2	179.7 (3)	N6—C9—C10—N5	−4.2 (6)
C1—N1—C5—C4	0.2 (4)	C8—C9—C10—N4	−1.7 (5)
C3—C4—C5—N2	−179.0 (3)	N6—C9—C10—N4	177.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O5ⁱ	0.82	1.73	2.549 (3)	178
O7—H7···O1ⁱⁱ	0.82	1.73	2.537 (3)	166
N1—H1···O1	0.86	1.87	2.706 (3)	165
N2—H2A···O3	0.86	1.88	2.726 (4)	168
N2—H2B···O9	0.86	2.05	2.645 (4)	126
N4—H4···O6	0.86	1.72	2.582 (4)	174
N5—H5A···O5	0.86	1.95	2.786 (4)	165
N5—H5B···O10	0.86	2.07	2.669 (5)	126
N5—H5B···O3ⁱⁱⁱ	0.86	2.22	2.843 (4)	130
C2—H2C···O7^iv	0.93	2.46	3.280 (4)	147
C3—H3···O6^iv	0.93	2.34	3.208 (4)	155
C8—H8···O9^v	0.93	2.52	3.097 (4)	120

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

Experimental details

Crystal data
Chemical formula	2C₅H₆N₃O₂⁺·H₂O₇P₂²⁻
M_r	456.21
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	298
a, b, c (Å)	34.250 (5), 5.763 (2), 8.991 (3)
V (Å³)	1774.8 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.29 × 0.25 × 0.19

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2726, 2724, 2279
R_int	0.008
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.091, 1.09
No. of reflections	2724
No. of parameters	265
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.28
Absolute structure	Flack (1983)
Absolute structure parameter	−0.15 (11)

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O5ⁱ	0.82	1.73	2.549 (3)	177.9
O7—H7···O1ⁱⁱ	0.82	1.73	2.537 (3)	165.9
N1—H1···O1	0.86	1.87	2.706 (3)	165.1
N2—H2A···O3	0.86	1.88	2.726 (4)	167.5
N2—H2B···O9	0.86	2.05	2.645 (4)	125.5
N4—H4···O6	0.86	1.72	2.582 (4)	174.2
N5—H5A···O5	0.86	1.95	2.786 (4)	165.4
N5—H5B···O10	0.86	2.07	2.669 (5)	126.4
N5—H5B···O3ⁱⁱⁱ	0.86	2.22	2.843 (4)	129.8
C2—H2C···O7^iv	0.93	2.46	3.280 (4)	147.3
C3—H3···O6^iv	0.93	2.34	3.208 (4)	154.9
C8—H8···O9^v	0.93	2.52	3.097 (4)	120.1

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

References

Aakeröy, C. B., Beatty, A. M., Nieuwenhuyzen, M. & Zou, M. (1998). J. Mater. Chem. pp. 1385–1389. Google Scholar
Akriche, S. & Rzaigui, M. (2000). Z. Kristallogr. New Cryst. Struct. 215, 617–618. CAS Google Scholar
Akriche, S. & Rzaigui, M. (2005). Acta Cryst. E61, o2607–o2609. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Akriche, S. & Rzaigui, M. (2009a). Acta Cryst. E65, m123. Web of Science CSD CrossRef IUCr Journals Google Scholar
Akriche, S. & Rzaigui, M. (2009b). Acta Cryst. E65, o1648. Web of Science CSD CrossRef IUCr Journals Google Scholar
Akriche, S. & Rzaigui, M. (2009c). Acta Cryst. E65, o793. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brodski, V., Peschar, R., Schenk, H., Brinkmann, A., Van Eck, E. R. H., Kentgens, A. P. M., Coussens, B. & Braam, A. (2004). J. Phys. Chem. B, 108, 15069–15076. Web of Science CSD CrossRef CAS Google Scholar
Charfi, M. & Jouini, A. (2005). Cryst. Res. Technol. 40, 615–621. Web of Science CSD CrossRef CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Mrad, M. L., Nasr, C. B., Rzaigui, M. & Lefebvre, F. (2006). Phosphorus Sulfur Silicon Relat. Elem. 181, 1625–1635. Web of Science CSD CrossRef CAS Google Scholar
Nicoud, J. F., Masse, R., Bourgogne, C. & Evans, C. (1997). J. Mater. Chem. 7, 35–39. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Soumhi, E. H., Saadoune, I., Driss, A. & Jouini, T. (1998). Eur. J. Solid State Inorg. Chem. 35, 699—706. Google Scholar

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