Bis(2-amino-3-nitro-pyridinium) dihydrogen-diphosphate.

The structure of the title compound, 2C(5)H(6)N(3)O(2) (+)·H(2)P(2)O(7) (2-), contains infinite (H(2)P(2)O(7) (2-))(n) layers stacked perpendicular to the a axis. The 2-amino-3-nitro-pyridinium 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 inter-actions 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 +·H2O7P2 2−

M = 456.21

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.091

S = 1.09

2724 reflections

265 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.53 e Å−3

Δρmin = −0.28 e Å−3

Absolute structure: Flack (1983 ▶), 443 Friedel pairs

Flack parameter: −0.15 (11)

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 ▶).

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810000942/dn2529Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

2C5H6N3O2+·H2O7P22−	F(000) = 936
Mr = 456.21	Dx = 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

Enraf–Nonius CAD-4 diffractometer	Rint = 0.008
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 3.3°
graphite	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 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(Fo2) + (0.0391P)2 + 0.7964P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.091	(Δ/σ)max = 0.001
S = 1.09	Δρmax = 0.53 e Å−3
2724 reflections	Δρmin = −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	Flack parameter: −0.15 (11)

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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···O7iv	0.93	2.46	3.280 (4)	147
C3—H3···O6iv	0.93	2.34	3.208 (4)	155
C8—H8···O9v	0.93	2.52	3.097 (4)	120

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⋯O7iv	0.93	2.46	3.280 (4)	147
C3—H3⋯O6iv	0.93	2.34	3.208 (4)	155
C8—H8⋯O9v	0.93	2.52	3.097 (4)	120

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .