Three hydrates of the bisphosphonate risedronate, consisting of one molecular and two ionic structures

Three different hydrates of risedronate were obtained by varying the pH of a solution containing the compound. At the pH values used, the N atom of the pyridine group is protonated and the compounds are zwitterionic. Crystals obtained directly from the synthesis resulted in risedronate monohydrate, or [1-hydroxy-1-phosphono-2-(pyridinium-3-yl)­ethyl]phosphonate monohydrate, C₇H₁₁NO₇P₂·H₂O, (I), in which just one phosphonate group is negatively charged. Recrystallizations at pH values of 2 and 4 yielded risedronate dihydrate, or sodium [1-hydroxy-2-(pyridinium-3-yl)­ethane-1,2-diyl]­bis­(phosphonate) dihydrate, Na⁺·C₇H₁₀NO₇P₂^-·2H₂O, (II). Finally, recrystallizations at pH values of 7 and 8 produced risedronate 2.5-­hydrate, or sodium [1-hydroxy-2-(pyridinium-3-yl)­ethane-1,2-diyl]­bis­(phosphonate) 2.5-hydrate, Na⁺·C₇H₁₀NO₇P₂^-·­2.5H₂O, (III). At these four pH values, both phosphonate groups in (II) and (III) are negatively charged and coordinated to an Na⁺ ion. Crystals of (II), i.e. those grown at pH values of 2 and 4, have isomorphous polymeric ion aggregate structures with geminal phosphonate and alcohol groups coordinated to the same Na⁺ ion. On the other hand, crystals of (III), i.e. those grown at pH values of 7 and 8, have isomorphism polymeric ion aggregate structures with geminal phosphonate and alcohol groups coordinated to different Na⁺ ions.

S1. Comment

Risedronate (Actonel; Procter & Gamble) is a potent inhibitor of osteoclast-mediated bone resorption and has found widespread use in the treatment of osteoporosis. More recently, risedronate has also been shown to have antiparasitic properties, in particular against the organisms which cause sleeping sickness, Chagas' disease, leishmanasis, toxoplasmosis and cryptosporidiosis (Martin et al., 2001; Urbina et al., 1999; Moreno et al., 2001). With the knowledge that several million people contract these diseases worldwide each year, it is of interest to explore the structural origins of bisphosphonate activity against these parasites. Only one structural form for risedronate, one of the most potent antiparasitic and antiresorptive agents, has been published to date (Barbey & Lecouvey, 2002). Here, the structures of three different forms of risedronate, (I), (II) and (III), are reported. \sch

All three hydrates exist as zwitterions, a common characteristic of bisphosphonates (Vega et al., 1996, 1998). The monohydrate, (I) (Fig. 1), has an overall charge of zero, with one positively charged N atom and one negatively charged phosphonate group (Barbey & Lecouvey, 2002). The dihydrate, (II) (Fig. 2), and the 2.5-hydrate, (III) (Fig. 3), both have an overall charge of −1, again with a positively charged N atom but with two negatively charged phosphonates. These protonation states are correlated with the P—O bond lengths.

Fig. 4 shows a histogram of the P—O bond distances observed in these three hydrates, along with those in two other bisphosphonate structures (isozoledronate and incadronate) recently explored (Gossman et al., 2002; Van Brussel et al., 2003), together with values found in 62 three-dimensional X-ray crystal structures of similar phosphonate-containing compounds that are listed in the Cambridge Structural Database (Version?; Allen, 2002). The two histograms are very similar, and show a clear bimodal distribution. P—O bonds in which the O atom is unprotonated are between 1.47 and 1.53 Å long, but this increases to 1.54–1.60 Å if the O atom is protonated.

Using this description to inspect the P—O bond lengths in the three hydrates studied here, compound (I), with P1—O1 1.548 (2), P1—O2 1.524 (2) and P1—O3 1.494 (2) Å, and P2—O4 1.480 (2), P2—O5 1.555 (2) and P2—O6 1.562 (2) Å, shows three protonated O atoms on the phosphonate groups, namely O1, O5 and O6, and three unprotonated O atoms, namely O2, O3, and O4, leading to the conclusion that atom P1 is negatively charged, while atom P2 is neutral. Inspection of (II), with P1—O1 1.513 (2), P1—O2 1.514 (2) and P1—O3 1.579 (2) Å, and P2—O4 1.515 (2), P2—O5 1.495 (2) and P2—O6 1.600 (2) Å, results in only two protonated O atoms, namely O3 and O6, and four unprotonated, namely O1, O2, O4 and O5, showing that both phosphonate groups in (II) carry a −1 charge, unlike (I). Analysis of (III), with P1—O1 1.510 (1), P1—O2 1.510 (1) and P1—O3 1.566 (1) Å, and P2—O4 1.498 (1), P2—O5 1.509 (1) and P2—O6 1.581 (1) Å, shows that the phosphonate groups have the same protonation state as in (II).

The conformation of risedronate in all three of these hydrates is very similar. The P1—C1—P2 angles are nearly identical [113.2 (2), 113.2 (2) and 111.8 (1)° in (I), (II) and (III), respectively], and the P1—C1—C2—C3 torsion angles between the phosphonate group and the ring are also similar [57.6 (3), 61.8 (3) and 53.8 (1)° in (I), (II) and (III), respectively]. One noticeable difference found in the structures is a nearly 180° rotation of the ring in the dihydrate compared with the mono- and 2.5-hydrates, as reflected in the C1—C2—C3—C4 torsion angles of the C atom closest to the N atom [82.9 (4), −97.2 (3) and 68.2 (1)° in (I), (II) and (III), respectively].

The main distinguishing structural feature between these three hydrates lies in ion aggregate propagation. In the monohydrate, only the hydrogen-bonding network interconnects the host bisphosphonate molecules, forming the crystals of (I). In the dihydrate, (II), atoms O1, O5 and O7 coordinate to Na1, atom O5 coordinates to a site on an inversion related Na1, and atom O2 bridges another Na1 through a different inversion centre. The ion aggregate propagates along the a axis. In the 2.5-hydrate, (III), atoms O1 and O5 coordinate to Na1, atom O7 coordinates to the terminal site on a c-glide related Na atom, and water ligand O8 bridges two Na atoms related by an inversion centre. The ion aggregate propagates parallel to the b,c plane. All three conformations show an extensive hydrogen-bonding network, with each structure having at least ten hydrogen bonds.

S2. Experimental

For (I), crystals were grown from ethanol-water (Ratio?). For (II), crystals were grown by vapour diffusion of ethanol into a buffered (glycine-HCl, pH 2 or 4) aqueous solution. For (III), crystals were grown by vapour diffusion of ethanol into a buffered (Tris-HCl, pH 7 or 8) aqueous solution.

S3. Refinement

In (I), the solvate water molecule was disordered over two general positions. Owing to high correlations, donor H-atom positions were refined under restraint to idealized O—H and N—H distances, with a standard uncertainty of 0.03 Å, and H—R distances for the water molecules were also restrained (s.u. 0.06 Å). The remaining C—H H atoms were included as riding atoms, with U_iso(H) = 1.2U_eq of their parent atoms. Disordered O—H distances were restrained to equivalent idealized values, with an effective standard deviation of 0.03 Å. The highest peaks in the final difference Fourier maps were located along the C—P bonds.

For (II), owing to high correlations, O—H distances were restrained to equivalent idealized values, with a standard uncertainty of 0.04 Å, and H—R distances for the water molecules were also restrained (s.u. 0.04 Å). The remaining H-atom parameters were independently refined. The highest peaks in the final difference Fourier map were located along the C—P bonds and in the vicinity of the terminal water ligand.

For (III), the uncoordinated solvate water molecule was disordered about the twofold axis. The proposed model also includes two disordered positions for the Na⁺ cation, in addition to the bridging and terminal water ligands. Owing to high correlations, O—H distances and angles for the disordered water molecules were restrained to equivalent idealized values, with standard uncertainties of 0.03 Å and 0.04 Å Should this be °?, respectively. Displacement parameters for H atoms bound to the same disordered O atom were restrained to be similar (s.u. 0.01 Ų). The remaining H-atom parameters were independently refined without restraints. The highest peaks in the final difference Fourier map were located along the C—P bonds and in the vicinity of the disordered terminal water ligand.

Computing details

For all compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: CIFTAB in SHELXL97-2 (Sheldrick, 2001).

Figures

	Fig. 1. A view of the molecule of (I), with 35% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii. Secondary sites for the disordered water molecule, O9, have been omitted for clarity.
	Fig. 2. A view of the molecule of (II), with 35% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. A view of the molecule of (III), with 35% probability displacement ellipsoids and the atom-numbering scheme. H atoms are shown as small spheres of arbitrary radii. Secondary sites for the disordered positions O10, O11, O12 and Na2 have been omitted for clarity.
	Fig. 4. Histograms of P—O bond lengths in compounds on the Cambridge Structural Database (black; see text for details), and those measured in the bisphosphonates (white).

(I) [1-hydroxy-1-phosphono-2-(pyridinium-3-yl)ethyl] phosphonate monohydrate

Crystal data

C7H11NO7P2·H2O	F(000) = 624
Mr = 301.12	Dx = 1.825 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 940 reflections
a = 7.1219 (15) Å	θ = 3.4–27.4°
b = 10.694 (2) Å	µ = 0.43 mm^−1
c = 14.710 (3) Å	T = 193 K
β = 101.996 (4)°	Plate, colourless
V = 1095.9 (4) Å^3	0.15 × 0.08 × 0.02 mm
Z = 4

Data collection

Bruker Platform CCD area-detector diffractometer	2236 independent reflections
Radiation source: normal-focus sealed tube	1534 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
profile data from ω scans	θmax = 26.4°, θmin = 2.4°
Absorption correction: integration (XPREP in SHELXTL; Bruker, 2001)	h = −8→8
Tmin = 0.936, Tmax = 0.991	k = −13→13
8978 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0469P)^2 + 0.5123P] where P = (Fo^2 + 2Fc^2)/3
2236 reflections	(Δ/σ)max < 0.001
200 parameters	Δρmax = 0.46 e Å^−3
20 restraints	Δρmin = −0.37 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.7711 (4)	0.9039 (3)	0.79317 (19)	0.0116 (6)
C2	0.6223 (4)	0.9471 (3)	0.70585 (19)	0.0139 (7)
H2A	0.4998	0.9033	0.7060	0.017*
H2B	0.5990	1.0376	0.7125	0.017*
C3	0.6720 (4)	0.9268 (3)	0.6121 (2)	0.0141 (7)
C4	0.6395 (5)	0.8117 (3)	0.5685 (2)	0.0182 (7)
H4	0.5938	0.7439	0.5996	0.022*
C5	0.7377 (5)	0.8859 (3)	0.4357 (2)	0.0209 (8)
H5	0.7598	0.8704	0.3752	0.025*
C6	0.7730 (5)	1.0016 (3)	0.4753 (2)	0.0195 (8)
H6	0.8196	1.0672	0.4425	0.023*
C7	0.7400 (4)	1.0219 (3)	0.5636 (2)	0.0168 (7)
H7	0.7644	1.1021	0.5914	0.020*
N1	0.6718 (4)	0.7950 (3)	0.48312 (18)	0.0204 (7)
H1	0.653 (5)	0.718 (3)	0.456 (2)	0.025*
O1	1.0795 (3)	0.9335 (2)	0.71323 (14)	0.0162 (5)
H1A	1.101 (5)	0.856 (3)	0.714 (2)	0.019*
O2	1.1424 (3)	0.9378 (2)	0.88740 (13)	0.0146 (5)
O3	0.9781 (3)	1.11895 (19)	0.79189 (14)	0.0169 (5)
O4	0.6117 (3)	1.0746 (2)	0.89900 (14)	0.0183 (5)
O5	0.8071 (3)	0.8922 (2)	0.98008 (15)	0.0196 (5)
H5A	0.814 (5)	0.944 (3)	1.020 (3)	0.023*
O6	0.4873 (3)	0.8498 (2)	0.87814 (15)	0.0186 (5)
H6A	0.392 (5)	0.880 (3)	0.878 (2)	0.022*
O7	0.8111 (3)	0.7734 (2)	0.79271 (15)	0.0163 (5)
H7A	0.720 (5)	0.733 (3)	0.774 (2)	0.020*
P1	1.00565 (12)	0.98053 (7)	0.79897 (5)	0.0120 (2)
P2	0.66224 (12)	0.94106 (8)	0.89331 (5)	0.0134 (2)
O8	0.1666 (6)	0.7079 (5)	0.7084 (5)	0.0239 (14)	0.799 (19)
H8A	0.278 (4)	0.687 (4)	0.704 (3)	0.029*	0.799 (19)
H8B	0.084 (5)	0.662 (4)	0.674 (3)	0.029*	0.799 (19)
O9	0.169 (3)	0.7380 (19)	0.662 (3)	0.039 (6)	0.201 (19)
H9A	0.277 (11)	0.706 (15)	0.655 (9)	0.047*	0.201 (19)
H9B	0.077 (15)	0.695 (12)	0.628 (9)	0.047*	0.201 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0121 (16)	0.0093 (17)	0.0117 (14)	0.0003 (12)	−0.0016 (12)	−0.0006 (11)
C2	0.0126 (16)	0.0168 (18)	0.0106 (14)	0.0018 (13)	−0.0018 (12)	−0.0003 (12)
C3	0.0105 (16)	0.0175 (19)	0.0115 (14)	0.0027 (13)	−0.0039 (12)	−0.0004 (13)
C4	0.0193 (18)	0.0165 (19)	0.0165 (15)	0.0028 (15)	−0.0016 (13)	0.0018 (13)
C5	0.0221 (19)	0.027 (2)	0.0123 (16)	0.0062 (16)	0.0010 (14)	0.0008 (14)
C6	0.0135 (18)	0.026 (2)	0.0168 (16)	0.0012 (14)	−0.0015 (13)	0.0075 (14)
C7	0.0148 (17)	0.0179 (18)	0.0142 (15)	−0.0020 (14)	−0.0053 (13)	−0.0021 (13)
N1	0.0273 (17)	0.0153 (17)	0.0161 (13)	0.0031 (13)	−0.0014 (12)	−0.0047 (11)
O1	0.0171 (12)	0.0166 (13)	0.0145 (11)	0.0003 (11)	0.0020 (9)	0.0006 (9)
O2	0.0133 (11)	0.0147 (12)	0.0137 (11)	0.0009 (9)	−0.0020 (9)	0.0005 (8)
O3	0.0146 (12)	0.0133 (13)	0.0212 (12)	0.0011 (9)	−0.0003 (10)	0.0018 (9)
O4	0.0183 (12)	0.0145 (13)	0.0211 (11)	0.0015 (10)	0.0016 (10)	−0.0029 (9)
O5	0.0223 (13)	0.0217 (14)	0.0115 (11)	0.0042 (11)	−0.0038 (10)	−0.0017 (9)
O6	0.0135 (13)	0.0161 (14)	0.0258 (12)	−0.0008 (10)	0.0032 (10)	−0.0017 (10)
O7	0.0167 (13)	0.0088 (13)	0.0209 (12)	−0.0019 (9)	−0.0019 (10)	−0.0023 (9)
P1	0.0121 (4)	0.0110 (4)	0.0111 (4)	−0.0002 (3)	−0.0014 (3)	−0.0002 (3)
P2	0.0132 (4)	0.0142 (5)	0.0114 (4)	0.0006 (4)	−0.0008 (3)	−0.0002 (3)
O8	0.0139 (18)	0.018 (3)	0.038 (3)	0.0023 (16)	0.0000 (18)	−0.008 (2)
O9	0.032 (9)	0.014 (9)	0.067 (15)	0.000 (7)	0.001 (10)	−0.005 (9)

Geometric parameters (Å, º)

C1—P1	1.846 (3)	C7—H7	0.9500
C1—P2	1.845 (3)	N1—H1	0.91 (3)
C1—O7	1.424 (4)	O1—P1	1.548 (2)
C1—C2	1.556 (4)	O1—H1A	0.84 (3)
C2—C3	1.509 (4)	O2—P1	1.524 (2)
C2—H2A	0.9900	O3—P1	1.494 (2)
C2—H2B	0.9900	O4—P2	1.479 (2)
C3—C4	1.385 (4)	O5—P2	1.555 (2)
C3—C7	1.386 (4)	O5—H5A	0.80 (4)
C4—N1	1.335 (4)	O6—P2	1.562 (2)
C4—H4	0.9500	O6—H6A	0.76 (4)
C5—N1	1.337 (4)	O7—H7A	0.78 (3)
C5—C6	1.367 (5)	O8—H8A	0.84 (3)
C5—H5	0.9500	O8—H8B	0.85 (3)
C6—C7	1.386 (4)	O9—H9A	0.87 (3)
C6—H6	0.9500	O9—H9B	0.87 (3)
P1—C1—P2	113.20 (15)	C6—C7—C3	120.9 (3)
C1—C2—C3	117.6 (2)	C6—C7—H7	119.6
O7—C1—P1	104.8 (2)	C3—C7—H7	119.6
O7—C1—P2	109.41 (19)	C4—N1—C5	122.8 (3)
O7—C1—C2	112.9 (2)	C4—N1—H1	120 (2)
C2—C1—P1	111.2 (2)	C5—N1—H1	117 (2)
C2—C1—P2	105.5 (2)	P1—O1—H1A	113 (2)
C3—C2—H2A	107.9	P2—O5—H5A	107 (3)
C1—C2—H2A	107.9	P2—O6—H6A	115 (3)
C3—C2—H2B	107.9	C1—O7—H7A	113 (3)
C1—C2—H2B	107.9	O3—P1—O2	114.05 (12)
H2A—C2—H2B	107.2	O3—P1—O1	109.09 (13)
C4—C3—C7	117.1 (3)	O2—P1—O1	109.46 (12)
C4—C3—C2	120.2 (3)	O3—P1—C1	109.40 (13)
C7—C3—C2	122.5 (3)	O2—P1—C1	108.54 (13)
N1—C4—C3	120.7 (3)	O1—P1—C1	105.99 (13)
N1—C4—H4	119.7	O4—P2—O5	113.92 (13)
C3—C4—H4	119.7	O4—P2—O6	114.53 (13)
N1—C5—C6	119.3 (3)	O5—P2—O6	106.30 (13)
N1—C5—H5	120.4	O4—P2—C1	113.62 (13)
C6—C5—H5	120.4	O5—P2—C1	105.42 (13)
C5—C6—C7	119.3 (3)	O6—P2—C1	101.92 (13)
C5—C6—H6	120.4	H8A—O8—H8B	110 (4)
C7—C6—H6	120.4	H9A—O9—H9B	108 (7)
O7—C1—C2—C3	−59.8 (4)	O7—C1—P1—O2	−59.6 (2)
P2—C1—C2—C3	−179.3 (2)	C2—C1—P1—O2	178.10 (19)
P1—C1—C2—C3	57.6 (3)	P2—C1—P1—O2	59.51 (19)
C1—C2—C3—C4	82.9 (4)	O7—C1—P1—O1	57.9 (2)
C1—C2—C3—C7	−101.0 (4)	C2—C1—P1—O1	−64.4 (2)
C7—C3—C4—N1	−0.5 (5)	P2—C1—P1—O1	177.00 (15)
C2—C3—C4—N1	175.8 (3)	O7—C1—P2—O4	−178.88 (18)
N1—C5—C6—C7	0.1 (5)	C2—C1—P2—O4	−57.1 (2)
C5—C6—C7—C3	0.0 (5)	P1—C1—P2—O4	64.68 (19)
C4—C3—C7—C6	0.2 (5)	O7—C1—P2—O5	55.7 (2)
C2—C3—C7—C6	−176.0 (3)	C2—C1—P2—O5	177.45 (19)
C3—C4—N1—C5	0.6 (5)	P1—C1—P2—O5	−60.75 (19)
C6—C5—N1—C4	−0.4 (5)	O7—C1—P2—O6	−55.1 (2)
O7—C1—P1—O3	175.34 (16)	C2—C1—P2—O6	66.6 (2)
C2—C1—P1—O3	53.1 (2)	P1—C1—P2—O6	−171.59 (15)
P2—C1—P1—O3	−65.51 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.91 (3)	1.94 (4)	2.847 (4)	172 (3)
O1—H1A···O8^ii	0.84 (3)	1.66 (4)	2.496 (6)	172 (4)
O1—H1A···O9^ii	0.84 (3)	1.61 (4)	2.355 (18)	147 (4)
O5—H5A···O2^iii	0.80 (4)	1.84 (4)	2.634 (3)	174 (4)
O6—H6A···O2^iv	0.76 (4)	1.91 (4)	2.661 (3)	172 (4)
O7—H7A···O3^v	0.78 (3)	1.96 (4)	2.730 (3)	168 (3)
O8—H8A···O3^v	0.84 (3)	1.87 (3)	2.704 (5)	170 (5)
O8—H8B···O4^vi	0.85 (3)	1.83 (3)	2.675 (5)	174 (5)

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

(II) sodium [1-hydroxy-2-(pyridinium-3-yl)ethane-1,2-diyl]bis(phosphonate) dihydrate

Crystal data

[Na(C7H10NO7P2)]·2H2O	Z = 2
Mr = 341.12	F(000) = 352
Triclinic, P1	Dx = 1.729 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.663 (4) Å	Cell parameters from 914 reflections
b = 8.039 (4) Å	θ = 3.1–27.5°
c = 10.770 (5) Å	µ = 0.41 mm^−1
α = 93.655 (8)°	T = 193 K
β = 95.277 (9)°	Tabular, colourless
γ = 96.017 (8)°	0.20 × 0.16 × 0.06 mm
V = 655.2 (6) Å^3

Data collection

Bruker Platform CCD area-detector diffractometer	2586 independent reflections
Radiation source: normal-focus sealed tube	2007 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
profile data from ω scans	θmax = 26.3°, θmin = 1.9°
Absorption correction: integration (XPREP in SHELXTL; Bruker, 2001)	h = −9→9
Tmin = 0.935, Tmax = 0.976	k = −9→9
4297 measured reflections	l = −13→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	All H-atom parameters refined
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0513P)^2 + 0.2778P] where P = (Fo^2 + 2Fc^2)/3
2586 reflections	(Δ/σ)max < 0.001
237 parameters	Δρmax = 0.50 e Å^−3
10 restraints	Δρmin = −0.31 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3232 (3)	0.2678 (3)	0.8179 (2)	0.0139 (5)
C2	0.4124 (4)	0.1367 (4)	0.7389 (2)	0.0180 (6)
H2A	0.356 (4)	0.017 (4)	0.754 (3)	0.028 (8)*
H2B	0.532 (4)	0.150 (3)	0.767 (3)	0.018 (8)*
C3	0.3988 (4)	0.1580 (3)	0.6000 (2)	0.0168 (6)
H3	0.317 (5)	−0.018 (4)	1.006 (4)	0.047 (12)*
C4	0.2684 (4)	0.0634 (4)	0.5190 (3)	0.0180 (6)
H4	0.189 (4)	−0.020 (4)	0.543 (3)	0.026 (8)*
C5	0.3625 (4)	0.1961 (4)	0.3453 (3)	0.0224 (6)
H5	0.349 (4)	0.204 (4)	0.260 (3)	0.020 (8)*
C6	0.4970 (4)	0.2925 (4)	0.4189 (3)	0.0237 (7)
H6	0.571 (4)	0.364 (4)	0.384 (3)	0.026 (9)*
C7	0.5154 (4)	0.2731 (4)	0.5473 (3)	0.0208 (6)
H7	0.609 (4)	0.336 (4)	0.599 (3)	0.020 (8)*
N1	0.2524 (3)	0.0835 (3)	0.3953 (2)	0.0197 (5)
H1	0.157 (5)	0.016 (4)	0.343 (3)	0.049 (11)*
O1	0.3249 (2)	0.3736 (2)	1.06585 (16)	0.0168 (4)
O2	0.5749 (2)	0.2091 (2)	1.00145 (16)	0.0164 (4)
O3	0.2663 (3)	0.0629 (2)	1.00848 (18)	0.0180 (4)
O4	0.0077 (3)	0.0739 (2)	0.75170 (18)	0.0225 (5)
O5	0.0033 (2)	0.3670 (2)	0.86649 (18)	0.0216 (4)
O6	0.0666 (3)	0.3298 (3)	0.63889 (18)	0.0231 (5)
H6A	0.071 (5)	0.429 (4)	0.633 (4)	0.050 (12)*
O7	0.3878 (3)	0.4381 (2)	0.79510 (17)	0.0197 (4)
H7A	0.474 (4)	0.477 (4)	0.840 (3)	0.030 (9)*
O8	0.9942 (3)	0.2415 (3)	1.1526 (2)	0.0259 (5)
H8A	1.105 (4)	0.276 (5)	1.139 (4)	0.061 (13)*
H8B	0.981 (6)	0.132 (4)	1.116 (5)	0.12 (2)*
P1	0.38048 (9)	0.23113 (8)	0.98527 (6)	0.01261 (18)
P2	0.08085 (9)	0.25709 (9)	0.77387 (6)	0.01525 (19)
Na1	0.81703 (14)	0.40337 (13)	1.02371 (10)	0.0197 (3)
O9	0.0864 (3)	0.6585 (3)	0.6179 (2)	0.0332 (5)
H9A	0.041 (7)	0.696 (7)	0.688 (3)	0.12 (2)*
H9B	0.016 (5)	0.666 (5)	0.555 (3)	0.067 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0160 (14)	0.0119 (13)	0.0145 (12)	0.0034 (10)	0.0016 (10)	0.0022 (10)
C2	0.0187 (16)	0.0230 (15)	0.0132 (13)	0.0072 (12)	0.0024 (11)	−0.0002 (11)
C3	0.0203 (15)	0.0169 (14)	0.0148 (13)	0.0078 (12)	0.0043 (11)	−0.0008 (11)
C4	0.0182 (15)	0.0183 (14)	0.0182 (14)	0.0038 (12)	0.0045 (11)	0.0003 (12)
C5	0.0248 (16)	0.0299 (16)	0.0141 (14)	0.0094 (13)	0.0031 (11)	0.0027 (12)
C6	0.0248 (17)	0.0226 (16)	0.0257 (15)	0.0033 (13)	0.0089 (13)	0.0075 (13)
C7	0.0182 (15)	0.0216 (15)	0.0219 (15)	0.0026 (12)	0.0013 (12)	−0.0029 (12)
N1	0.0188 (13)	0.0243 (13)	0.0156 (11)	0.0039 (10)	0.0002 (10)	−0.0025 (10)
O1	0.0191 (10)	0.0173 (10)	0.0143 (9)	0.0050 (8)	0.0005 (7)	−0.0011 (8)
O2	0.0155 (10)	0.0151 (9)	0.0185 (9)	0.0023 (8)	−0.0001 (7)	0.0023 (8)
O3	0.0171 (10)	0.0133 (10)	0.0242 (10)	0.0022 (8)	0.0033 (8)	0.0042 (8)
O4	0.0221 (11)	0.0181 (10)	0.0249 (10)	−0.0015 (8)	−0.0047 (8)	−0.0002 (8)
O5	0.0169 (10)	0.0241 (11)	0.0233 (10)	0.0037 (8)	0.0009 (8)	−0.0039 (8)
O6	0.0291 (12)	0.0238 (12)	0.0169 (10)	0.0086 (10)	−0.0032 (8)	0.0039 (9)
O7	0.0228 (12)	0.0172 (10)	0.0170 (10)	−0.0044 (9)	−0.0035 (8)	0.0042 (8)
O8	0.0227 (12)	0.0273 (12)	0.0291 (12)	0.0057 (10)	0.0051 (9)	0.0055 (9)
P1	0.0142 (4)	0.0127 (3)	0.0110 (3)	0.0021 (3)	0.0006 (2)	0.0009 (3)
P2	0.0155 (4)	0.0153 (4)	0.0146 (3)	0.0028 (3)	−0.0010 (3)	−0.0001 (3)
Na1	0.0165 (6)	0.0187 (6)	0.0238 (6)	0.0019 (4)	0.0011 (4)	0.0020 (5)
O9	0.0390 (14)	0.0341 (13)	0.0277 (13)	0.0111 (11)	−0.0003 (11)	0.0054 (11)

Geometric parameters (Å, º)

C1—P1	1.865 (3)	O1—Na1^i	2.401 (2)
C1—P2	1.866 (3)	O2—P1	1.514 (2)
C1—O7	1.450 (3)	O2—Na1	2.281 (2)
C1—C2	1.564 (4)	O3—P1	1.579 (2)
C2—C3	1.512 (4)	O3—H3	0.79 (3)
C2—H2A	1.04 (3)	O4—P2	1.515 (2)
C2—H2B	0.93 (3)	O5—P2	1.495 (2)
C3—C4	1.390 (4)	O5—Na1^ii	2.337 (2)
C3—C7	1.401 (4)	O5—Na1^i	2.364 (2)
C4—N1	1.348 (4)	O6—P2	1.600 (2)
C4—H4	0.92 (3)	O6—H6A	0.80 (3)
C5—N1	1.344 (4)	O7—Na1^i	2.926 (2)
C5—C6	1.377 (4)	O7—H7A	0.81 (3)
C5—H5	0.92 (3)	O8—Na1	2.391 (2)
C6—C7	1.398 (4)	O8—H8A	0.89 (3)
C6—H6	0.89 (3)	O8—H8B	0.93 (3)
C7—H7	0.95 (3)	O9—H9A	0.90 (3)
N1—H1	0.97 (4)	O9—H9B	0.84 (3)
O1—P1	1.5134 (19)
O7—C1—C2	111.4 (2)	P2—O6—H6A	120 (3)
O7—C1—P1	109.70 (16)	C1—O7—Na1^i	95.03 (14)
C2—C1—P1	106.48 (17)	C1—O7—H7A	114 (2)
O7—C1—P2	103.45 (16)	Na1^i—O7—H7A	86 (2)
C2—C1—P2	112.70 (18)	Na1—O8—H8A	104 (2)
P1—C1—P2	113.21 (14)	Na1—O8—H8B	108 (3)
C3—C2—C1	114.8 (2)	H8A—O8—H8B	101 (3)
C3—C2—H2A	109.1 (17)	O1—P1—O2	115.54 (10)
C1—C2—H2A	108.4 (17)	O1—P1—O3	109.01 (12)
C3—C2—H2B	106.9 (17)	O2—P1—O3	110.28 (11)
C1—C2—H2B	106.9 (17)	O1—P1—C1	108.46 (11)
H2A—C2—H2B	111 (3)	O2—P1—C1	107.40 (11)
C4—C3—C7	117.2 (2)	O3—P1—C1	105.67 (11)
C4—C3—C2	120.9 (3)	O5—P2—O4	119.07 (12)
C7—C3—C2	121.9 (3)	O5—P2—O6	110.73 (12)
N1—C4—C3	121.6 (3)	O4—P2—O6	105.29 (11)
N1—C4—H4	114.4 (19)	O5—P2—C1	108.75 (11)
C3—C4—H4	124.0 (19)	O4—P2—C1	108.09 (11)
N1—C5—C6	120.8 (3)	O6—P2—C1	103.81 (12)
N1—C5—H5	118.7 (19)	O2—Na1—O5^iii	112.52 (8)
C6—C5—H5	120.4 (19)	O2—Na1—O5^i	151.92 (8)
C5—C6—C7	118.7 (3)	O5^iii—Na1—O5^i	95.50 (8)
C5—C6—H6	120 (2)	O2—Na1—O8	94.91 (9)
C7—C6—H6	121 (2)	O5^iii—Na1—O8	88.77 (8)
C6—C7—C3	120.5 (3)	O5^i—Na1—O8	83.45 (9)
C6—C7—H7	119.8 (18)	O2—Na1—O1^i	96.68 (8)
C3—C7—H7	119.7 (17)	O5^iii—Na1—O1^i	96.26 (8)
C5—N1—C4	121.2 (3)	O5^i—Na1—O1^i	81.47 (8)
C5—N1—H1	121 (2)	O8—Na1—O1^i	164.48 (8)
C4—N1—H1	118 (2)	O2—Na1—O7^i	81.75 (7)
P1—O1—Na1^i	121.73 (10)	O5^iii—Na1—O7^i	161.48 (8)
P1—O2—Na1	130.52 (11)	O5^i—Na1—O7^i	71.30 (7)
P1—O3—H3	115 (3)	O8—Na1—O7^i	102.14 (8)
P2—O5—Na1^ii	150.98 (13)	O1^i—Na1—O7^i	69.49 (7)
P2—O5—Na1^i	119.39 (12)	H9A—O9—H9B	110 (4)
Na1^ii—O5—Na1^i	84.50 (8)
O7—C1—C2—C3	−53.9 (3)	C2—C1—P1—O2	44.6 (2)
P1—C1—C2—C3	−173.5 (2)	P2—C1—P1—O2	169.00 (12)
P2—C1—C2—C3	61.8 (3)	O7—C1—P1—O3	166.27 (16)
C1—C2—C3—C4	−97.2 (3)	C2—C1—P1—O3	−73.1 (2)
C1—C2—C3—C7	82.6 (3)	P2—C1—P1—O3	51.28 (16)
C7—C3—C4—N1	−1.2 (4)	Na1^ii—O5—P2—O4	8.1 (3)
C2—C3—C4—N1	178.6 (2)	Na1^i—O5—P2—O4	150.12 (11)
N1—C5—C6—C7	−1.1 (4)	Na1^ii—O5—P2—O6	130.3 (2)
C5—C6—C7—C3	−0.1 (4)	Na1^i—O5—P2—O6	−87.66 (14)
C4—C3—C7—C6	1.2 (4)	Na1^ii—O5—P2—C1	−116.3 (2)
C2—C3—C7—C6	−178.6 (3)	Na1^i—O5—P2—C1	25.80 (16)
C6—C5—N1—C4	1.1 (4)	O7—C1—P2—O5	−68.25 (18)
C3—C4—N1—C5	0.0 (4)	C2—C1—P2—O5	171.35 (18)
C2—C1—O7—Na1^i	−177.37 (17)	P1—C1—P2—O5	50.42 (17)
P1—C1—O7—Na1^i	−59.75 (15)	O7—C1—P2—O4	161.15 (15)
P2—C1—O7—Na1^i	61.32 (13)	C2—C1—P2—O4	40.8 (2)
Na1^i—O1—P1—O2	121.61 (12)	P1—C1—P2—O4	−80.17 (15)
Na1^i—O1—P1—O3	−113.58 (13)	O7—C1—P2—O6	49.68 (17)
Na1^i—O1—P1—C1	1.02 (16)	C2—C1—P2—O6	−70.7 (2)
Na1—O2—P1—O1	−41.36 (17)	P1—C1—P2—O6	168.36 (12)
Na1—O2—P1—O3	−165.52 (12)	P1—O2—Na1—O5^iii	−120.70 (14)
Na1—O2—P1—C1	79.80 (15)	P1—O2—Na1—O5^i	63.3 (2)
O7—C1—P1—O1	49.5 (2)	P1—O2—Na1—O8	148.59 (14)
C2—C1—P1—O1	170.13 (17)	P1—O2—Na1—O1^i	−21.07 (15)
P2—C1—P1—O1	−65.48 (16)	P1—O2—Na1—O7^i	47.00 (14)
O7—C1—P1—O2	−76.01 (18)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2^iv	0.79 (3)	1.82 (3)	2.613 (3)	177 (4)
N1—H1···O4^v	0.97 (4)	1.63 (4)	2.592 (3)	173 (3)
O6—H6A···O9	0.80 (3)	1.86 (3)	2.656 (3)	178 (4)
O7—H7A···O1^i	0.81 (3)	2.00 (3)	2.791 (3)	166 (3)
O8—H8A···O1^iii	0.89 (3)	2.03 (3)	2.902 (3)	165 (3)
O8—H8A···O3^iii	0.89 (3)	2.63 (4)	3.124 (3)	116 (3)
O8—H8B···O4^iv	0.93 (3)	2.25 (4)	2.797 (3)	116 (4)
O8—H8B···O3^iv	0.93 (3)	2.55 (4)	3.283 (3)	136 (4)
O9—H9A···O8^i	0.90 (3)	1.81 (3)	2.696 (3)	165 (5)
O9—H9B···O6^vi	0.84 (3)	2.13 (3)	2.914 (3)	156 (4)

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

(III) sodium [1-hydroxy-2-(pyridinium-3-yl)ethane-1,2-diyl]bis(phosphonate) 2.5-hydrate

Crystal data

[Na(C7H10NO7P2)]·2.5H2O	F(000) = 1448
Mr = 350.13	Dx = 1.750 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 963 reflections
a = 21.664 (7) Å	θ = 2.5–28.2°
b = 8.930 (3) Å	µ = 0.41 mm^−1
c = 15.123 (5) Å	T = 193 K
β = 114.692 (5)°	Plate, colourless
V = 2658.3 (14) Å^3	0.30 × 0.20 × 0.06 mm
Z = 8

Data collection

Bruker Platform CCD area-detector diffractometer	2435 independent reflections
Radiation source: normal-focus sealed tube	2142 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
profile data from ω scans	θmax = 25.4°, θmin = 2.1°
Absorption correction: integration (XPREP in SHELXTL; Bruker, 2001)	h = −26→26
Tmin = 0.886, Tmax = 0.977	k = −10→10
13009 measured reflections	l = −18→18

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0468P)^2 + 2.844P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.043
2435 reflections	Δρmax = 0.37 e Å^−3
298 parameters	Δρmin = −0.35 e Å^−3
33 restraints

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.18418 (3)	0.17780 (8)	0.13259 (5)	0.01594 (18)
C2	0.16365 (3)	0.20481 (8)	0.02299 (5)	0.01806 (19)
H2A	0.1770 (4)	0.3038 (9)	0.0141 (6)	0.021 (2)*
H2B	0.1891 (4)	0.1347 (9)	0.0046 (5)	0.022 (2)*
C3	0.08923 (3)	0.19088 (8)	−0.04326 (5)	0.01867 (19)
C4	0.05589 (4)	0.05430 (8)	−0.06006 (5)	0.0215 (2)
H4	0.0777 (4)	−0.0377 (10)	−0.0288 (6)	0.032 (2)*
C5	−0.04662 (4)	0.16229 (10)	−0.16919 (6)	0.0328 (3)
H5	−0.0920 (4)	0.1423 (10)	−0.2120 (6)	0.031 (2)*
C6	−0.01629 (4)	0.30027 (9)	−0.15586 (7)	0.0355 (3)
H6	−0.0420 (5)	0.3858 (12)	−0.1913 (7)	0.051 (3)*
C7	0.05160 (4)	0.31445 (9)	−0.09327 (6)	0.0255 (2)
H7	0.0752 (4)	0.4067 (10)	−0.0834 (6)	0.027 (2)*
N1	−0.01021 (3)	0.04412 (7)	−0.12154 (4)	0.02509 (18)
H1	−0.0284 (4)	−0.0458 (10)	−0.1303 (6)	0.031 (2)*
O1	0.17452 (2)	0.33081 (6)	0.28632 (3)	0.02135 (14)
O2	0.06638 (2)	0.22480 (6)	0.15299 (4)	0.02562 (15)
O3	0.12315 (2)	0.44818 (5)	0.12027 (3)	0.02050 (14)
H3	0.1500 (4)	0.5060 (11)	0.1493 (6)	0.039 (3)*
O4	0.29017 (2)	0.37352 (5)	0.18174 (3)	0.01967 (13)
O5	0.29920 (2)	0.16274 (5)	0.30063 (3)	0.01915 (14)
O6	0.30941 (2)	0.10793 (6)	0.14425 (3)	0.02028 (13)
H6A	0.3173 (4)	0.0324 (10)	0.1656 (6)	0.035 (3)*
O7	0.17200 (2)	0.02148 (5)	0.14404 (3)	0.01952 (13)
H7A	0.1885 (4)	−0.0050 (11)	0.2017 (6)	0.040 (3)*
P1	0.134467 (9)	0.29890 (2)	0.179316 (12)	0.01704 (5)
P2	0.276249 (8)	0.213258 (19)	0.196487 (12)	0.01546 (5)
O8	0.20512 (6)	0.11753 (12)	0.42805 (7)	0.0354 (3)	0.5295 (8)
H8A	0.1719 (6)	0.1699 (13)	0.3865 (11)	0.033 (2)*	0.5295 (8)
H8B	0.2001 (7)	0.0338 (11)	0.3997 (10)	0.035 (2)*	0.5295 (8)
O9	0.39181 (6)	0.19818 (13)	0.51643 (8)	0.0412 (4)	0.5295 (8)
H9A	0.4059 (7)	0.1303 (15)	0.4931 (8)	0.047 (2)*	0.5295 (8)
H9B	0.4046 (8)	0.1929 (19)	0.5764 (7)	0.046 (3)*	0.5295 (8)
Na1	0.28640 (3)	0.30120 (6)	0.42011 (4)	0.02034 (15)	0.5295 (8)
O10	−0.02274 (5)	0.36128 (13)	0.20791 (8)	0.0302 (3)	0.50
H10A	0.0065 (5)	0.3064 (17)	0.2012 (9)	0.052 (4)*	0.50
H10B	−0.0279 (6)	0.3211 (19)	0.2552 (8)	0.054 (4)*	0.50
O11	0.20852 (10)	0.11342 (16)	0.43226 (10)	0.0628 (6)	0.4705 (8)
H11A	0.2261 (7)	0.0448 (13)	0.4124 (11)	0.037 (2)*	0.4705 (8)
H11B	0.1925 (8)	0.1749 (13)	0.3839 (10)	0.034 (2)*	0.4705 (8)
O12	0.42451 (7)	0.19805 (14)	0.51646 (10)	0.0365 (4)	0.4705 (8)
H12A	0.4249 (9)	0.1268 (15)	0.4778 (9)	0.050 (3)*	0.4705 (8)
H12B	0.4666 (6)	0.199 (2)	0.5528 (12)	0.045 (2)*	0.4705 (8)
Na2	0.30391 (4)	0.29778 (8)	0.43197 (5)	0.0284 (2)	0.4705 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0198 (3)	0.0117 (3)	0.0171 (3)	−0.0022 (3)	0.0085 (2)	−0.0006 (2)
C2	0.0190 (3)	0.0179 (3)	0.0179 (3)	−0.0008 (3)	0.0083 (2)	0.0005 (3)
C3	0.0205 (3)	0.0207 (3)	0.0162 (3)	−0.0029 (3)	0.0090 (2)	−0.0039 (3)
C4	0.0229 (3)	0.0206 (4)	0.0199 (3)	−0.0029 (3)	0.0079 (2)	−0.0007 (3)
C5	0.0169 (3)	0.0310 (4)	0.0444 (4)	−0.0017 (3)	0.0066 (3)	−0.0057 (4)
C6	0.0228 (4)	0.0237 (4)	0.0494 (5)	0.0063 (3)	0.0046 (3)	−0.0005 (4)
C7	0.0230 (3)	0.0189 (4)	0.0322 (4)	−0.0011 (3)	0.0089 (3)	−0.0039 (3)
N1	0.0234 (3)	0.0219 (3)	0.0302 (3)	−0.0065 (2)	0.0114 (2)	−0.0049 (3)
O1	0.0308 (2)	0.0166 (2)	0.0195 (2)	0.0000 (2)	0.01335 (16)	−0.00105 (19)
O2	0.0262 (2)	0.0193 (3)	0.0368 (2)	−0.0051 (2)	0.01850 (17)	−0.0064 (2)
O3	0.0223 (2)	0.0132 (2)	0.0224 (2)	−0.00152 (19)	0.00568 (16)	−0.00198 (19)
O4	0.0224 (2)	0.0147 (2)	0.0205 (2)	−0.00070 (19)	0.00753 (16)	0.00074 (19)
O5	0.0226 (2)	0.0173 (2)	0.0167 (2)	0.00288 (19)	0.00730 (16)	0.00066 (18)
O6	0.0258 (2)	0.0171 (2)	0.0208 (2)	0.00398 (19)	0.01261 (15)	0.00237 (19)
O7	0.0278 (2)	0.0123 (2)	0.0189 (2)	−0.00207 (19)	0.01019 (16)	0.00026 (18)
P1	0.02007 (7)	0.01364 (8)	0.01976 (7)	−0.00119 (6)	0.01065 (5)	−0.00167 (6)
P2	0.01788 (7)	0.01310 (8)	0.01540 (7)	0.00019 (6)	0.00696 (5)	0.00006 (6)
O8	0.0687 (6)	0.0204 (5)	0.0144 (4)	0.0208 (5)	0.0148 (4)	0.0028 (4)
O9	0.0491 (6)	0.0325 (6)	0.0299 (5)	0.0106 (5)	0.0044 (5)	−0.0055 (5)
Na1	0.0254 (2)	0.0201 (3)	0.0160 (2)	−0.0024 (2)	0.00914 (17)	−0.00226 (19)
O10	0.0279 (4)	0.0334 (6)	0.0344 (5)	0.0071 (4)	0.0180 (3)	0.0057 (4)
O11	0.1445 (11)	0.0202 (7)	0.0489 (6)	−0.0159 (8)	0.0652 (6)	−0.0015 (6)
O12	0.0361 (7)	0.0257 (6)	0.0367 (6)	0.0014 (5)	0.0043 (5)	−0.0078 (5)
Na2	0.0403 (3)	0.0245 (3)	0.0250 (3)	−0.0049 (3)	0.0181 (2)	−0.0031 (3)

Geometric parameters (Å, º)

C1—P1	1.8613 (9)	O5—P2	1.5089 (7)
C1—P2	1.8445 (8)	O5—Na2	2.2891 (11)
C1—O7	1.4445 (9)	O5—Na1	2.2997 (9)
C1—C2	1.5451 (11)	O6—P2	1.5808 (6)
C2—C3	1.5064 (10)	O6—H6A	0.736 (9)
C2—H2A	0.957 (8)	O7—Na2^i	2.4668 (11)
C2—H2B	0.949 (9)	O7—Na1^i	2.5205 (9)
C3—C4	1.3858 (11)	O7—H7A	0.827 (9)
C3—C7	1.3924 (10)	O8—Na1^ii	2.3413 (14)
C4—N1	1.3457 (9)	O8—Na1	2.4458 (15)
C4—H4	0.967 (9)	O8—H8A	0.868 (11)
C5—N1	1.3342 (11)	O8—H8B	0.846 (11)
C5—C6	1.3711 (13)	O9—Na1	2.3246 (14)
C5—H5	0.941 (8)	O9—H9A	0.822 (13)
C6—C7	1.3828 (11)	O9—H9B	0.832 (10)
C6—H6	0.965 (10)	O10—H10A	0.841 (13)
C7—H7	0.949 (9)	O10—H10B	0.848 (13)
N1—H1	0.880 (9)	O11—Na2	2.644 (2)
O1—P1	1.5098 (6)	O11—H11A	0.841 (14)
O1—Na1	2.4375 (9)	O11—H11B	0.863 (12)
O1—Na2	2.7636 (10)	O12—Na2	2.5422 (16)
O2—P1	1.5104 (7)	O12—H12A	0.867 (14)
O3—P1	1.5657 (6)	O12—H12B	0.845 (11)
O3—H3	0.765 (9)	Na2—O11^ii	2.319 (2)
O4—P2	1.4983 (7)
O7—C1—C2	107.12 (5)	O5—P2—C1	107.95 (3)
O7—C1—P2	108.35 (4)	O6—P2—C1	104.70 (3)
C2—C1—P2	107.39 (5)	Na1^ii—O8—Na1	94.43 (4)
O7—C1—P1	110.64 (5)	Na1^ii—O8—H8A	104.2 (11)
C2—C1—P1	111.32 (5)	Na1—O8—H8A	89.9 (9)
P2—C1—P1	111.84 (4)	Na1^ii—O8—H8B	135.3 (11)
C3—C2—C1	116.69 (7)	Na1—O8—H8B	120.7 (12)
C3—C2—H2A	106.5 (4)	H8A—O8—H8B	102.6 (12)
C1—C2—H2A	109.1 (5)	Na1—O9—H9A	117.9 (8)
C3—C2—H2B	110.0 (4)	Na1—O9—H9B	119.9 (12)
C1—C2—H2B	105.6 (5)	H9A—O9—H9B	114.3 (14)
H2A—C2—H2B	108.8 (8)	O5—Na1—O9	82.55 (4)
C4—C3—C7	117.12 (6)	O5—Na1—O8^ii	162.08 (4)
C4—C3—C2	121.71 (6)	O9—Na1—O8^ii	81.61 (5)
C7—C3—C2	121.12 (6)	O5—Na1—O1	79.08 (3)
N1—C4—C3	120.58 (6)	O9—Na1—O1	159.89 (4)
N1—C4—H4	116.2 (5)	O8^ii—Na1—O1	115.08 (4)
C3—C4—H4	123.2 (5)	O5—Na1—O8	90.21 (4)
N1—C5—C6	119.50 (7)	O9—Na1—O8	104.05 (5)
N1—C5—H5	115.7 (5)	O8^ii—Na1—O8	85.57 (4)
C6—C5—H5	124.8 (5)	O1—Na1—O8	68.09 (3)
C5—C6—C7	119.36 (7)	O5—Na1—O7^iii	86.41 (3)
C5—C6—H6	120.0 (6)	O9—Na1—O7^iii	97.73 (5)
C7—C6—H6	120.6 (6)	O8^ii—Na1—O7^iii	103.97 (4)
C6—C7—C3	120.87 (7)	O1—Na1—O7^iii	89.27 (3)
C6—C7—H7	122.5 (4)	O8—Na1—O7^iii	157.33 (3)
C3—C7—H7	116.6 (4)	H10A—O10—H10B	103.1 (14)
C5—N1—C4	122.56 (7)	Na2^ii—O11—Na2	99.70 (6)
C5—N1—H1	121.0 (5)	Na2^ii—O11—H11A	143.5 (10)
C4—N1—H1	116.5 (5)	Na2—O11—H11A	88.9 (10)
P1—O1—Na1	142.77 (4)	Na2^ii—O11—H11B	112.3 (11)
P1—O1—Na2	140.50 (4)	Na2—O11—H11B	68.9 (11)
P1—O3—H3	110.3 (7)	H11A—O11—H11B	104.0 (15)
P2—O5—Na2	128.60 (4)	Na2—O12—H12A	102.4 (10)
P2—O5—Na1	124.33 (4)	Na2—O12—H12B	157.8 (12)
P2—O6—H6A	113.4 (8)	H12A—O12—H12B	97.8 (16)
C1—O7—Na2^i	129.94 (5)	O5—Na2—O11^ii	165.62 (6)
C1—O7—Na1^i	126.56 (5)	O5—Na2—O7^iii	87.92 (4)
C1—O7—H7A	112.5 (6)	O11^ii—Na2—O7^iii	105.13 (5)
Na2^i—O7—H7A	100.2 (7)	O5—Na2—O12	85.16 (5)
Na1^i—O7—H7A	96.7 (7)	O11^ii—Na2—O12	98.62 (6)
O1—P1—O2	115.22 (3)	O7^iii—Na2—O12	98.33 (5)
O1—P1—O3	109.48 (3)	O5—Na2—O11	85.52 (5)
O2—P1—O3	108.64 (3)	O11^ii—Na2—O11	80.30 (6)
O1—P1—C1	110.60 (3)	O7^iii—Na2—O11	145.36 (4)
O2—P1—C1	107.55 (4)	O12—Na2—O11	114.90 (6)
O3—P1—C1	104.82 (4)	O5—Na2—O1	72.66 (3)
O4—P2—O5	116.22 (3)	O11^ii—Na2—O1	102.41 (6)
O4—P2—O6	109.40 (4)	O7^iii—Na2—O1	83.32 (3)
O5—P2—O6	108.86 (3)	O12—Na2—O1	157.71 (5)
O4—P2—C1	109.07 (3)	O11—Na2—O1	62.26 (4)
O7—C1—C2—C3	67.23 (8)	O7—C1—P2—O4	177.58 (5)
P2—C1—C2—C3	−176.57 (5)	C2—C1—P2—O4	62.19 (5)
P1—C1—C2—C3	−53.84 (7)	P1—C1—P2—O4	−60.22 (5)
C1—C2—C3—C4	−68.20 (10)	O7—C1—P2—O5	−55.30 (5)
C1—C2—C3—C7	114.33 (8)	C2—C1—P2—O5	−170.69 (4)
C7—C3—C4—N1	−0.69 (12)	P1—C1—P2—O5	66.89 (5)
C2—C3—C4—N1	−178.26 (8)	O7—C1—P2—O6	60.57 (6)
N1—C5—C6—C7	0.06 (16)	C2—C1—P2—O6	−54.82 (5)
C5—C6—C7—C3	−0.48 (16)	P1—C1—P2—O6	−177.23 (3)
C4—C3—C7—C6	0.78 (13)	P2—O5—Na1—O9	−143.08 (5)
C2—C3—C7—C6	178.37 (9)	P2—O5—Na1—O8^ii	−171.10 (13)
C6—C5—N1—C4	0.03 (15)	P2—O5—Na1—O1	45.15 (4)
C3—C4—N1—C5	0.30 (13)	P2—O5—Na1—O8	112.77 (4)
C2—C1—O7—Na2^i	42.50 (7)	P2—O5—Na1—O7^iii	−44.80 (4)
P2—C1—O7—Na2^i	−73.07 (6)	P1—O1—Na1—O5	−7.66 (6)
P1—C1—O7—Na2^i	164.00 (3)	P1—O1—Na1—O9	−32.05 (17)
C2—C1—O7—Na1^i	51.56 (6)	P1—O1—Na1—O8^ii	−176.07 (5)
P2—C1—O7—Na1^i	−64.01 (6)	P1—O1—Na1—O8	−102.33 (6)
P1—C1—O7—Na1^i	173.06 (2)	P1—O1—Na1—O7^iii	78.83 (6)
Na1—O1—P1—O2	130.44 (6)	Na1^ii—O8—Na1—O5	162.57 (4)
Na2—O1—P1—O2	132.43 (5)	Na1^ii—O8—Na1—O9	80.19 (5)
Na1—O1—P1—O3	−106.79 (6)	Na1^ii—O8—Na1—O8^ii	0.0
Na2—O1—P1—O3	−104.80 (5)	Na1^ii—O8—Na1—O1	−119.30 (5)
Na1—O1—P1—C1	8.22 (6)	Na1^ii—O8—Na1—O7^iii	−116.28 (10)
Na2—O1—P1—C1	10.22 (6)	P2—O5—Na2—O11^ii	123.8 (2)
O7—C1—P1—O1	88.82 (5)	P2—O5—Na2—O7^iii	−31.73 (5)
C2—C1—P1—O1	−152.20 (5)	P2—O5—Na2—O12	−130.28 (5)
P2—C1—P1—O1	−32.06 (5)	P2—O5—Na2—O11	114.23 (5)
O7—C1—P1—O2	−37.78 (5)	P2—O5—Na2—O1	51.92 (4)
C2—C1—P1—O2	81.20 (5)	Na2^ii—O11—Na2—O5	177.61 (6)
P2—C1—P1—O2	−158.66 (3)	Na2^ii—O11—Na2—O11^ii	0.0
O7—C1—P1—O3	−153.28 (4)	Na2^ii—O11—Na2—O7^iii	−102.61 (9)
C2—C1—P1—O3	−34.29 (5)	Na2^ii—O11—Na2—O12	95.06 (7)
P2—C1—P1—O3	85.84 (4)	Na2^ii—O11—Na2—O1	−109.65 (7)
Na2—O5—P2—O4	32.91 (6)	P1—O1—Na2—O5	−10.68 (6)
Na1—O5—P2—O4	42.29 (5)	P1—O1—Na2—O11^ii	−176.69 (6)
Na2—O5—P2—O6	156.94 (4)	P1—O1—Na2—O7^iii	79.23 (6)
Na1—O5—P2—O6	166.32 (3)	P1—O1—Na2—O12	−16.46 (15)
Na2—O5—P2—C1	−89.94 (5)	P1—O1—Na2—O11	−104.79 (7)
Na1—O5—P2—C1	−80.56 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^iv	0.880 (9)	1.765 (9)	2.6440 (11)	177.7 (8)
O3—H3···O5^iii	0.765 (9)	1.745 (9)	2.5002 (8)	168.9 (9)
O6—H6A···O1^i	0.736 (9)	1.922 (9)	2.6538 (10)	172.5 (9)
O7—H7A···O4^i	0.827 (9)	1.954 (9)	2.7487 (10)	161.0 (9)
O8—H8B···O4^i	0.85 (1)	1.96 (1)	2.7671 (13)	160 (2)
O8—H8A···O1	0.87 (1)	2.11 (2)	2.7339 (13)	129 (1)
O9—H9A···O3^i	0.82 (1)	2.25 (1)	2.9671 (15)	145 (1)
O9—H9B···O10^v	0.83 (1)	2.01 (1)	2.7596 (16)	149 (2)
O10—H10A···O2	0.84 (1)	1.88 (1)	2.6914 (15)	162 (2)
O10—H10B···O2^vi	0.85 (1)	2.08 (1)	2.9097 (15)	166 (1)
O11—H11A···O4^i	0.84 (1)	2.02 (1)	2.7575 (18)	146 (1)
O11—H11B···O1	0.86 (1)	1.95 (1)	2.7972 (17)	169 (2)
O12—H12A···O3^i	0.87 (1)	2.13 (1)	2.9219 (15)	152 (2)
O12—H12B···O2^v	0.85 (1)	2.17 (1)	2.9804 (15)	161 (2)

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