Hydro-nium (3-oxo-1-phosphono-1,3-dihydro-isobenzofuran-1-yl)phospho-nate.

In the title compound, H(3)O(+)·C(8)H(7)O(8)P(2) (-), the anions form inversion dimmers by way of pairs of O-H⋯O hydrogen bonds involving the phospho-nic functions and via the hydro-nium cation. Further O-H⋯O links involving the hydronium cation play a prominant part in the cohesion of the crystal structure by building bridges between bis-phospho-nate pairs, forming infinite ribbons along the b-axis direction and by cross-linking these ribbons perpendicularly along the a-axis direction, forming an infinite three-dimensional hydrogen-bond network. The benzene ring and the C=O atoms of the furan ring are disordered over two sets of positions of equal occupancy.

Related literature

For the pharmacological applications of bis­phospho­nates, see Heymann et al. (2004 ▶); Rodan & Martin (2000 ▶); Fournier et al. (2002 ▶); Hamma-Kourbali et al. (2003 ▶); Wood et al. (2002 ▶); Martin et al. (2001 ▶, 2002 ▶); Sanders et al. (2003 ▶). For general background, see Lecouvey et al. (2003a ▶,b ▶); Monteil et al. (2005 ▶); Guénin et al. (2004 ▶); Lecouvey & Leroux (2000 ▶); Vachal et al. (2006 ▶). For related structures, see Sylvestre et al. (2001 ▶); Lecouvey et al. (2002 ▶).

Experimental

Crystal data

H3O+·C8H7O8P2 −

M = 312.10

Monoclinic,

a = 26.2271 (9) Å

b = 7.2913 (3) Å

c = 15.2621 (6) Å

β = 124.103 (2)°

V = 2416.66 (16) Å3

Z = 8

Mo Kα radiation

μ = 0.40 mm−1

T = 293 (2) K

0.30 × 0.10 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: none

14205 measured reflections

2139 independent reflections

1627 reflections with I > 2σ(I)

R int = 0.071

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.126

S = 1.05

2139 reflections

229 parameters

21 restraints

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.37 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: HKL (Otwinowski & Minor, 1997 ▶); data reduction: HKL; 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 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and CrystalBuilder (Welter, 2006 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000907/dn2420sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000907/dn2420Isup2.hkl

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

H3O+·C8H7O8P2−	F(000) = 1280
Mr = 312.10	Dx = 1.716 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 2338 reflections
a = 26.2271 (9) Å	θ = 0.4–25.4°
b = 7.2913 (3) Å	µ = 0.40 mm−1
c = 15.2621 (6) Å	T = 293 K
β = 124.103 (2)°	Parallelepipedic, colourless
V = 2416.66 (16) Å3	0.30 × 0.10 × 0.10 mm
Z = 8

Nonius KappaCCD diffractometer	1627 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.071
graphite	θmax = 25.4°, θmin = 3.0°
Detector resolution: 9 pixels mm-1	h = −31→30
φ and ω scans	k = −8→8
14205 measured reflections	l = −18→17
2139 independent reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0625P)2 + 4.0148P] where P = (Fo2 + 2Fc2)/3
2139 reflections	(Δ/σ)max = 0.001
229 parameters	Δρmax = 0.33 e Å−3
21 restraints	Δρmin = −0.37 e Å−3

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 > 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	Occ. (<1)
P1	0.81092 (4)	0.03803 (12)	0.41201 (6)	0.0268 (3)
O11	0.79680 (10)	−0.0117 (3)	0.49420 (18)	0.0338 (6)
H11	0.7615	0.0191	0.4721	0.051*
O12	0.75192 (9)	0.0932 (3)	0.30772 (17)	0.0338 (6)
H12	0.7528	0.0541	0.2582	0.051*
O13	0.84830 (10)	−0.1086 (3)	0.40406 (18)	0.0339 (6)
P2	0.82143 (3)	0.45428 (11)	0.46825 (6)	0.0250 (3)
O23	0.80619 (9)	0.4158 (3)	0.54732 (17)	0.0316 (5)
O22	0.76507 (9)	0.5004 (3)	0.36019 (17)	0.0323 (6)
O21	0.87289 (10)	0.5997 (3)	0.50941 (18)	0.0339 (6)
H21	0.8605	0.6856	0.4676	0.051*
C1	0.85893 (13)	0.2462 (4)	0.4606 (2)	0.0252 (7)
O1	0.90991 (9)	0.2067 (3)	0.57008 (15)	0.0329 (6)
C2A	0.9660 (4)	0.2436 (17)	0.5830 (7)	0.030 (3)	0.50
O2A	1.0134 (4)	0.2317 (14)	0.6679 (7)	0.058 (3)	0.50
C3A	0.9536 (4)	0.2866 (17)	0.4802 (7)	0.032 (3)	0.50
C4	0.89030 (14)	0.2748 (5)	0.4041 (2)	0.0295 (7)
C5	0.86705 (16)	0.3115 (5)	0.2986 (3)	0.0373 (8)
H5	0.8250	0.3067	0.2467	0.045*
C6A	0.9093 (5)	0.356 (2)	0.2737 (11)	0.037 (4)	0.50
H6A	0.8947	0.3890	0.2046	0.045*	0.50
C7A	0.9732 (6)	0.3515 (19)	0.3495 (10)	0.056 (4)	0.50
H7A	1.0003	0.3736	0.3296	0.068*	0.50
C8A	0.9952 (5)	0.3150 (15)	0.4523 (9)	0.050 (3)	0.50
H8A	1.0374	0.3092	0.5032	0.060*	0.50
C2B	0.9639 (5)	0.1751 (16)	0.5743 (9)	0.038 (4)	0.50
O2B	1.0105 (4)	0.1345 (12)	0.6576 (8)	0.053 (2)	0.50
C3B	0.9517 (4)	0.2220 (17)	0.4728 (8)	0.030 (3)	0.50
C6B	0.9075 (6)	0.297 (3)	0.2668 (12)	0.045 (5)	0.50
H6B	0.8922	0.3094	0.1955	0.055*	0.50
C7B	0.9703 (6)	0.264 (2)	0.3393 (11)	0.062 (5)	0.50
H7B	0.9971	0.2723	0.3177	0.074*	0.50
C8B	0.9926 (5)	0.2211 (16)	0.4419 (10)	0.052 (3)	0.50
H8B	1.0339	0.1918	0.4897	0.062*	0.50
O1W	0.85750 (13)	−0.1636 (4)	0.2188 (2)	0.0646 (9)
H1W	0.8473	−0.1639	0.2690	0.097*
H2W	0.8410	−0.2545	0.1654	0.097*
H3W	0.9009	−0.1544	0.2575	0.097*

	U11	U22	U33	U12	U13	U23
P1	0.0238 (4)	0.0260 (5)	0.0315 (5)	0.0011 (3)	0.0160 (4)	0.0003 (3)
O11	0.0267 (12)	0.0395 (14)	0.0395 (13)	0.0046 (10)	0.0212 (11)	0.0068 (11)
O12	0.0250 (11)	0.0408 (14)	0.0277 (11)	0.0002 (10)	0.0099 (10)	−0.0051 (10)
O13	0.0351 (12)	0.0286 (13)	0.0461 (14)	0.0040 (10)	0.0277 (12)	−0.0010 (10)
P2	0.0219 (4)	0.0269 (5)	0.0268 (4)	−0.0013 (3)	0.0141 (4)	0.0004 (3)
O23	0.0298 (11)	0.0380 (13)	0.0329 (12)	0.0034 (10)	0.0211 (11)	0.0044 (10)
O22	0.0224 (11)	0.0385 (14)	0.0311 (12)	0.0041 (10)	0.0120 (10)	0.0051 (10)
O21	0.0259 (11)	0.0296 (13)	0.0391 (13)	−0.0050 (10)	0.0138 (11)	0.0014 (10)
C1	0.0174 (14)	0.0338 (18)	0.0203 (14)	0.0011 (13)	0.0081 (13)	0.0012 (12)
O1	0.0210 (11)	0.0494 (15)	0.0257 (11)	0.0043 (10)	0.0116 (10)	0.0059 (10)
C2A	0.012 (4)	0.046 (9)	0.026 (5)	0.000 (4)	0.007 (4)	−0.008 (4)
O2A	0.022 (4)	0.111 (8)	0.032 (4)	−0.004 (5)	0.009 (3)	−0.001 (5)
C3A	0.024 (4)	0.033 (9)	0.038 (5)	−0.008 (4)	0.016 (4)	−0.005 (4)
C4	0.0237 (16)	0.0341 (19)	0.0338 (16)	0.0004 (14)	0.0180 (15)	0.0002 (14)
C5	0.0329 (18)	0.046 (2)	0.0331 (18)	0.0081 (16)	0.0186 (16)	0.0073 (16)
C6A	0.046 (6)	0.032 (11)	0.039 (5)	0.008 (5)	0.027 (5)	0.006 (5)
C7A	0.050 (6)	0.086 (12)	0.057 (6)	−0.004 (7)	0.045 (6)	0.005 (7)
C8A	0.032 (5)	0.074 (9)	0.048 (5)	−0.016 (6)	0.026 (4)	−0.010 (6)
C2B	0.033 (6)	0.035 (8)	0.043 (6)	−0.005 (4)	0.019 (5)	−0.010 (5)
O2B	0.020 (3)	0.083 (7)	0.038 (4)	0.008 (4)	0.005 (3)	−0.002 (5)
C3B	0.024 (4)	0.028 (8)	0.039 (5)	−0.006 (4)	0.019 (4)	−0.009 (4)
C6B	0.073 (8)	0.036 (12)	0.053 (7)	0.017 (6)	0.051 (7)	0.014 (6)
C7B	0.050 (7)	0.091 (12)	0.070 (8)	0.011 (7)	0.049 (7)	0.024 (8)
C8B	0.029 (5)	0.074 (9)	0.061 (6)	−0.001 (6)	0.030 (5)	0.007 (7)
O1W	0.0470 (16)	0.081 (2)	0.0599 (18)	0.0001 (16)	0.0266 (15)	−0.0147 (16)

P1—O13	1.501 (2)	C4—C3B	1.395 (9)
P1—O12	1.526 (2)	C5—C6A	1.397 (11)
P1—O11	1.537 (2)	C5—C6B	1.397 (11)
P1—C1	1.842 (3)	C5—H5	0.9300
O11—H11	0.8200	C6A—C7A	1.405 (11)
O12—H12	0.8200	C6A—H6A	0.9300
P2—O23	1.495 (2)	C7A—C8A	1.360 (11)
P2—O22	1.511 (2)	C7A—H7A	0.9300
P2—O21	1.546 (2)	C8A—H8A	0.9300
P2—C1	1.847 (3)	C2B—O2B	1.207 (10)
O21—H21	0.8200	C2B—C3B	1.437 (11)
C1—O1	1.469 (3)	C3B—C8B	1.393 (10)
C1—C4	1.503 (4)	C6B—C7B	1.396 (12)
O1—C2A	1.397 (9)	C6B—H6B	0.9300
O1—C2B	1.399 (10)	C7B—C8B	1.366 (11)
C2A—O2A	1.193 (9)	C7B—H7B	0.9300
C2A—C3A	1.447 (10)	C8B—H8B	0.9300
C3A—C8A	1.390 (10)	O1W—H1W	0.9423
C3A—C4	1.397 (9)	O1W—H2W	0.9469
C4—C5	1.391 (4)	O1W—H3W	0.9450
O13—P1—O12	115.47 (13)	C3A—C4—C1	108.0 (5)
O13—P1—O11	111.42 (13)	C4—C5—C6A	117.4 (6)
O12—P1—O11	110.24 (12)	C4—C5—C6B	117.6 (7)
O13—P1—C1	106.83 (13)	C6A—C5—C6B	18.0 (14)
O12—P1—C1	105.50 (13)	C4—C5—H5	121.3
O11—P1—C1	106.80 (13)	C6A—C5—H5	121.3
P1—O11—H11	109.5	C6B—C5—H5	118.0
P1—O12—H12	109.5	C5—C6A—C7A	122.2 (10)
O23—P2—O22	112.47 (12)	C5—C6A—H6A	118.9
O23—P2—O21	111.60 (13)	C7A—C6A—H6A	118.9
O22—P2—O21	112.81 (13)	C8A—C7A—C6A	119.5 (11)
O23—P2—C1	106.84 (13)	C8A—C7A—H7A	120.3
O22—P2—C1	110.08 (13)	C6A—C7A—H7A	120.3
O21—P2—C1	102.39 (13)	C7A—C8A—C3A	119.0 (10)
P2—O21—H21	109.5	C7A—C8A—H8A	120.5
O1—C1—C4	103.8 (2)	C3A—C8A—H8A	120.5
O1—C1—P1	106.1 (2)	O2B—C2B—O1	119.4 (10)
C4—C1—P1	110.7 (2)	O2B—C2B—C3B	132.5 (10)
O1—C1—P2	105.48 (18)	O1—C2B—C3B	107.6 (8)
C4—C1—P2	113.9 (2)	C8B—C3B—C4	122.0 (8)
P1—C1—P2	115.74 (15)	C8B—C3B—C2B	128.0 (9)
C2A—O1—C2B	21.1 (7)	C4—C3B—C2B	110.0 (7)
C2A—O1—C1	109.7 (4)	C7B—C6B—C5	121.7 (11)
C2B—O1—C1	109.7 (5)	C7B—C6B—H6B	119.2
O2A—C2A—O1	120.8 (9)	C5—C6B—H6B	119.2
O2A—C2A—C3A	131.1 (9)	C8B—C7B—C6B	120.3 (11)
O1—C2A—C3A	108.1 (7)	C8B—C7B—H7B	119.9
C8A—C3A—C4	121.7 (8)	C6B—C7B—H7B	119.9
C8A—C3A—C2A	128.8 (9)	C7B—C8B—C3B	118.1 (10)
C4—C3A—C2A	109.1 (7)	C7B—C8B—H8B	120.9
C5—C4—C3B	119.7 (5)	C3B—C8B—H8B	120.9
C5—C4—C3A	119.7 (5)	H1W—O1W—H2W	119.8
C3B—C4—C3A	19.8 (8)	H1W—O1W—H3W	106.4
C5—C4—C1	131.7 (3)	H2W—O1W—H3W	113.4
C3B—C4—C1	107.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O23i	0.82	1.69	2.504 (3)	168
O12—H12···O22ii	0.82	1.64	2.438 (3)	164
O21—H21···O13iii	0.82	1.72	2.522 (3)	167
O1W—H1W···O13	0.94	2.09	2.996 (4)	162
O1W—H2W···O23iv	0.95	1.90	2.845 (4)	174
O1W—H3W···O2Bv	0.94	1.93	2.875 (10)	177
O1W—H3W···O2Av	0.94	1.95	2.853 (9)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11⋯O23i	0.82	1.69	2.504 (3)	168
O12—H12⋯O22ii	0.82	1.64	2.438 (3)	164
O21—H21⋯O13iii	0.82	1.72	2.522 (3)	167
O1W—H1W⋯O13	0.94	2.09	2.996 (4)	162
O1W—H2W⋯O23iv	0.95	1.90	2.845 (4)	174
O1W—H3W⋯O2Bv	0.94	1.93	2.875 (10)	177
O1W—H3W⋯O2Av	0.94	1.95	2.853 (9)	159

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