Ammonium 1-hydroxy-2-(2-pyridinio)ethane-1,1-diyldiphosphonate dihydrate and potassium 1-hydroxy-2-(2-pyridinio)ethane-1,1-diyldiphosphonate dihydrate

The crystal structures of the title compounds, ammonium risedronate dihydrate, NH₄⁺·C₇H₁₀NO₇P₂⁻·2H₂O, (I), and potassium risedronate dihydrate, K⁺·C₇H₁₀NO₇P₂⁻·2H₂O, (II), have been determined from single-crystal X-ray data collected at 120 K. Compound (I) forms a three-dimensional hydrogen-bonded network which connects the ammonium and risedronate ions and the water mol­ecules. In compound (II), the K⁺ ions are seven-coordinated in a capped distorted trigonal prism. The coordination polyhedra form chains by corner-sharing, and these chains are connected by phosphon­ate groups into layers in the ac plane. The layers are stacked and connected by hydrogen bonds in the b direction. The risedronate conformation is determined by intra­molecular inter­actions fine-tuned by crystal packing effects. All H-atom donors in both structures are involved in hydrogen bonding, with D...A distances between 2.510 (2) and 3.009 (2) Å.

S1. Comment

Many bisphosphonates are effective drugs for a number of bone disorders, for example osteoporosis (Rodan & Martin, 2000). In addition, bisphosphonates have shown promising antiparasitic activity (Martin et al., 2001). In a search for stable salts suitable for pharmaceutical preparations, the title compounds, (I) and (II), were synthesized and their crystal structures are presented here.

The bond distances and angles of the risedronate anions in (I) and (II) are very similar and also compare well with the values previously obtained for other crystal structures containing risedronate (risedronate monohydrate, sodium risedronate dihydrate and sodium risedronate 2.5-hydrate; Barbey & Lecouvey, 2002; Gossman et al., 2003). As noted earlier (Gossman et al., 2003), the P1—O3 and P2—O6 bonds are significantly longer [1.5614 (15)–1.5839 (15) Å] than the remaining P—O distances [1.4967 (13)–1.5168 (13) Å] because of the H atoms bonded to O3 and O6. A comparison of the O7—C1—C2—C3 and C1—C2—C3—C4 torsion angles gives additional information on the risedronate conformations (Table 5). In all the previously known structures, the ring plane is oriented approximately perpendicular to the phosphonate group (C1—C2—C3—C4 ≈ ±90°). This suggests that this general conformation is independent of crystal packing forces, although if the pyridinium ring is rotated by 180° atom N1 can still be positioned in the direction most favourable for hydrogen bonding. In the structure of (I) and risedronate monohydrate, this rotation is opposite to what is observed in the structures containing alkali metal ions. The O7—C1—C2—C3 torsion angles also fall into two distinct groups, with values of ±60°. In this conformation, one of the bulky phosphonate groups will always be opposite to the pyridinium ring. The sign of O7—C1—C2—C3 is probably governed by the hydrogen-bonding pattern in the crystal, as suggested for C1—C2—C3—C4, but there is no obvious correlation between them.

In both structures, the hydrogen bonds formed by the H atoms of the phosphonate groups and H1 (bonded to the pyridinium atom N1) are much stronger [D···A 2.510 (2)–2.690 (2) Å] than the remaining O—H···O bonds [D···A 2.6454 (19)–2.867 (2) Å]. The N—H···O bonds formed by the ammonium ion in (I) are even weaker [D···A 2.768 (2)–3.009 (2) Å]. While all hydrogen donors are involved in hydrogen bonds, the potential acceptors O3, O6 and O7 are not. This can be understood from the lack of hydrogen donors and the fact that forming few shorter bonds is, in general, energetically favourable to forming more bonds of average length.

In (I), the ammonium ions are connected via hydrogen bonds to water and phosponate O atoms (Table 2). The ammonium coordination tetrahedra are connected through the phosphonate groups into a three-dimensional network (Fig. 3). The intramolecular O6—H6A···O2 hydrogen bond found in (I) is not present in any of the known risedronate structures. This interaction locks the relative rotation of the two phosphonate groups without affecting the overall conformation. Although atom O7 is not an acceptor for conventional hydrogen bonds, it takes part in three very weak interactions [D···A 2.997 (2)–3.077 (2) Å and D—H···A 113 (2)–118°]. The C2—H2B···O3^vii [symmetry code: (vii) −x, 2 − y, −z] interaction with H···A = 2.27 Å and D—H···A = 161° is potentially an interesting weak hydrogen bond.

In (II), the K⁺ cation is seven-coordinated (Table 3) by water and phosphonate O atoms in a distorted capped trigonal prism. The coordination polyhedra are corner-sharing through O2, forming chains in the [101] direction. The chains are further connected through the phosphonate groups and hydrogen bonding into layers in the ac plane. Both water molecules are coordinated by K⁺ and involved in hydrogen bonding within and between the polyhedral chains. The layers are separated by the protruding pyridinium groups, which also connect the layers by N1—H11···O4ⁱ [symmetry code: (i) −x, −y, 1 − z] hydrogen bonds (Fig. 4). As observed for (I), no conventional hydrogen bonds are found to atom O3. However, this atom forms a very weak intramolecular O7—H7A···O3 hydrogen bond [D···A = 2.9725 (18) Å and D—H···A = 111.5 (17)°].

S2. Experimental

Compound (I) was prepared as follows. Risedronic acid (602.26 g) was stirred in water (1200 ml) and ammonia was added (600 ml, 16 M). The mixture was heated under reflux until all material had dissolved. Ethanol (1000 ml) and water (750 ml) were added, and the mixture was stirred overnight at room temperature. The precipitate which formed was recovered by filtration, rinsed with water–ethanol (Ratio?) and dried at 333 K under a vacuum.

Compound (II) was prepared as follows. Risedronic acid (6 g) was stirred in water (12 ml) at approximately 333 K. KOH (19.5 ml, 1 N) was added and the mixture was refluxed until a clear solution was obtained. The solution was cooled to room temperature with stirring and finally cooled to 273 K. The precipitate which formed was recovered by filtration and rinsed with water–ethanol (Ratio?) and ethanol, and dried at 333 K under a vacuum.

Crystals for data collection were prepared in the following way. Compound (I) or (II) (1 g) was dissolved in sterilized water (15 ml) and heated under reflux until dissolved. Slow cooling yielded small crystals which were then used to nucleate a repeated recrystallization. The crystals obtained were dried in a vacuum at 313 K for 24 h.

S3. Refinement

The N atoms in the pyridinium rings were initially assigned based on thermal parameters, and later confirmed by the C—N bond lengths and hydrogen bonding. All H-atom parameters were initially refined freely. In the final cycles, the H atoms of CH₂, CH and NH groups were placed in calculated positions, with C—H = 0.98 (CH₂) or 0.93 (CH) and with N—H = 0.86 Å, and refined as riding atoms. For the OH groups and water molecules, the O—H distances were restrained to 0.82 (2) Å, and for NH₄⁺ the N—H distances were restrained to 0.89 (2) Å. The displacement parameters were set to 1.2 (CH₂, CH and NH) or 1.5 (OH and NH₄) times U_eq of the parent C, O or N atoms.

Computing details

For both compounds, data collection: SMART (Bruker, 1997–1999); cell refinement: SAINT-Plus (Bruker, 1997–1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 2000); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of ammonium risedronate dihydrate, (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 75% probability level.
	Fig. 2. A view of potassium risedronate dihydrate, (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 75% probability level.
	Fig. 3. The crystal packing of (I), viewed along the a axis, showing the ammonium coordination tetrahedra. H atoms have been omitted for clarity.
	Fig. 4. The crystal packing of (II), viewed along the c diagonal, showing the layers of K^+ coordination polyhedra connected by N1—H11···O4 hydrogen bonds (single lines). H atoms have been omitted for clarity.

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

Crystal data

NH4^+·C7H10NO7P2^−·2H2O	F(000) = 704
Mr = 336.17	Dx = 1.666 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5685 reflections
a = 10.0911 (6) Å	θ = 2.4–30.8°
b = 12.2790 (7) Å	µ = 0.37 mm^−1
c = 11.1598 (7) Å	T = 118 K
β = 104.240 (1)°	Plate, colourless
V = 1340.31 (14) Å^3	0.28 × 0.14 × 0.04 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	3279 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.076
Graphite monochromator	θmax = 31.0°, θmin = 2.4°
ω scan, frame data integration	h = −14→14
17561 measured reflections	k = −17→16
3965 independent reflections	l = −15→15

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 0.1262P] where P = (Fo^2 + 2Fc^2)/3
3965 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.69 e Å^−3
11 restraints	Δρmin = −0.33 e Å^−3

Special details

Experimental. Oxford Cryosystem liquid nitrogen cryostream cooler

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 > 2σ(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
P1	0.10983 (5)	0.80069 (4)	−0.03272 (4)	0.00903 (12)
P2	0.15912 (5)	0.65558 (4)	0.19432 (5)	0.00888 (12)
O1	0.24627 (14)	0.85740 (11)	−0.01361 (13)	0.0125 (3)
O2	0.09620 (15)	0.69201 (11)	−0.09891 (13)	0.0138 (3)
O3	−0.00384 (15)	0.88178 (12)	−0.09911 (14)	0.0149 (3)
H3	−0.066 (2)	0.860 (2)	−0.1571 (19)	0.022*
O4	0.10409 (14)	0.62244 (11)	0.30300 (13)	0.0129 (3)
O5	0.30956 (14)	0.67993 (12)	0.22075 (13)	0.0157 (3)
O6	0.11492 (16)	0.56205 (12)	0.09475 (14)	0.0162 (3)
H6A	0.102 (3)	0.586 (2)	0.0246 (17)	0.024*
O7	−0.07230 (14)	0.75371 (11)	0.09794 (13)	0.0116 (3)
H7A	−0.121 (2)	0.809 (2)	0.070 (2)	0.017*
O8	0.22054 (15)	0.58698 (12)	0.54314 (14)	0.0146 (3)
H8A	0.242 (3)	0.5230 (14)	0.544 (2)	0.022*
H8B	0.194 (3)	0.608 (2)	0.4709 (17)	0.022*
O9	0.32192 (16)	0.89092 (13)	0.76991 (14)	0.0186 (3)
H9A	0.3998 (19)	0.870 (2)	0.777 (3)	0.028*
H9B	0.305 (3)	0.873 (2)	0.8372 (19)	0.028*
C1	0.07073 (19)	0.77769 (15)	0.11929 (17)	0.0088 (3)
C2	0.1102 (2)	0.88079 (15)	0.20077 (18)	0.0111 (4)
H2A	0.2084	0.8937	0.2132	0.013*
H2B	0.0620	0.9436	0.1561	0.013*
C3	0.0778 (2)	0.87403 (15)	0.32546 (19)	0.0109 (4)
C4	0.1822 (2)	0.86570 (16)	0.43179 (18)	0.0131 (4)
H4	0.2724	0.8636	0.4257	0.016*
C5	0.0269 (2)	0.86081 (17)	0.5578 (2)	0.0208 (5)
H5	0.0112	0.8558	0.6363	0.025*
C6	−0.0809 (2)	0.86850 (17)	0.4561 (2)	0.0204 (5)
H6	−0.1702	0.8680	0.4649	0.025*
C7	−0.0556 (2)	0.87706 (17)	0.3390 (2)	0.0164 (4)
H7	−0.1281	0.8848	0.2697	0.020*
N1	0.15506 (19)	0.86055 (14)	0.54411 (17)	0.0169 (4)
H1	0.2220	0.8570	0.6088	0.025*
N2	0.49123 (18)	0.90088 (14)	0.17132 (17)	0.0130 (3)
H2C	0.414 (2)	0.874 (2)	0.120 (2)	0.019*
H2D	0.560 (2)	0.903 (2)	0.134 (2)	0.019*
H2E	0.468 (2)	0.9684 (14)	0.188 (2)	0.019*
H2F	0.518 (2)	0.8633 (19)	0.2477 (17)	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0100 (2)	0.0088 (2)	0.0078 (2)	−0.00154 (18)	0.00133 (17)	0.00021 (18)
P2	0.0087 (2)	0.0086 (2)	0.0092 (2)	0.00117 (17)	0.00190 (18)	0.00091 (18)
O1	0.0113 (7)	0.0144 (7)	0.0119 (7)	−0.0032 (5)	0.0029 (5)	−0.0001 (5)
O2	0.0198 (7)	0.0111 (7)	0.0101 (7)	−0.0020 (5)	0.0031 (6)	−0.0016 (5)
O3	0.0157 (7)	0.0116 (7)	0.0136 (7)	−0.0001 (5)	−0.0039 (6)	0.0020 (6)
O4	0.0148 (7)	0.0126 (7)	0.0116 (7)	0.0002 (5)	0.0038 (6)	0.0028 (5)
O5	0.0090 (7)	0.0214 (8)	0.0156 (7)	0.0020 (6)	0.0012 (6)	0.0047 (6)
O6	0.0244 (8)	0.0098 (7)	0.0129 (7)	0.0035 (6)	0.0018 (6)	−0.0003 (6)
O7	0.0059 (6)	0.0111 (7)	0.0172 (7)	0.0007 (5)	0.0018 (5)	0.0018 (5)
O8	0.0186 (7)	0.0121 (7)	0.0126 (7)	0.0021 (6)	0.0029 (6)	0.0018 (6)
O9	0.0134 (7)	0.0289 (9)	0.0151 (8)	0.0009 (6)	0.0065 (6)	0.0001 (7)
C1	0.0065 (8)	0.0093 (8)	0.0100 (9)	0.0010 (6)	0.0009 (7)	0.0008 (7)
C2	0.0117 (9)	0.0100 (8)	0.0124 (9)	−0.0011 (7)	0.0043 (7)	0.0002 (7)
C3	0.0137 (9)	0.0059 (8)	0.0148 (10)	−0.0013 (7)	0.0065 (8)	−0.0017 (7)
C4	0.0177 (10)	0.0094 (9)	0.0139 (10)	0.0000 (7)	0.0073 (8)	−0.0009 (7)
C5	0.0345 (13)	0.0132 (10)	0.0209 (11)	−0.0016 (9)	0.0184 (10)	0.0008 (8)
C6	0.0202 (11)	0.0138 (10)	0.0339 (13)	−0.0034 (8)	0.0193 (10)	−0.0059 (9)
C7	0.0148 (10)	0.0140 (10)	0.0217 (11)	−0.0018 (8)	0.0068 (8)	−0.0042 (8)
N1	0.0249 (10)	0.0131 (8)	0.0131 (9)	0.0014 (7)	0.0052 (7)	0.0016 (7)
N2	0.0123 (8)	0.0127 (8)	0.0137 (9)	0.0012 (7)	0.0028 (7)	0.0000 (7)

Geometric parameters (Å, º)

P1—O1	1.5105 (14)	C2—H2A	0.9800
P1—O2	1.5150 (15)	C2—H2B	0.9800
P1—O3	1.5614 (15)	C3—C4	1.383 (3)
P1—C1	1.8554 (19)	C3—C7	1.391 (3)
P2—O5	1.5036 (14)	C4—N1	1.348 (3)
P2—O4	1.5087 (14)	C4—H4	0.9300
P2—O6	1.5839 (15)	C5—N1	1.339 (3)
P2—C1	1.8378 (19)	C5—C6	1.369 (3)
O3—H3	0.826 (16)	C5—H5	0.9300
O6—H6A	0.816 (16)	C6—C7	1.396 (3)
O7—C1	1.434 (2)	C6—H6	0.9300
O7—H7A	0.85 (3)	C7—H7	0.9300
O8—H8A	0.815 (16)	N1—H1	0.8600
O8—H8B	0.824 (16)	N2—H2C	0.906 (16)
O9—H9A	0.810 (17)	N2—H2D	0.885 (16)
O9—H9B	0.841 (17)	N2—H2E	0.896 (16)
C1—C2	1.552 (3)	N2—H2F	0.948 (16)
C2—C3	1.508 (3)
O1—P1—O2	116.43 (8)	C1—C2—H2B	108.7
O1—P1—O3	108.10 (8)	H2A—C2—H2B	107.6
O2—P1—O3	111.24 (8)	C4—C3—C7	117.51 (18)
O1—P1—C1	109.42 (8)	C4—C3—C2	120.23 (17)
O2—P1—C1	107.30 (8)	C7—C3—C2	122.26 (18)
O3—P1—C1	103.55 (8)	N1—C4—C3	121.01 (19)
O5—P2—O4	116.71 (8)	N1—C4—H4	119.5
O5—P2—O6	112.23 (9)	C3—C4—H4	119.5
O4—P2—O6	105.82 (8)	N1—C5—C6	119.9 (2)
O5—P2—C1	106.29 (8)	N1—C5—H5	120.0
O4—P2—C1	110.67 (8)	C6—C5—H5	120.0
O6—P2—C1	104.51 (8)	C5—C6—C7	119.3 (2)
P1—O3—H3	119.2 (18)	C5—C6—H6	120.3
P2—O6—H6A	111.3 (19)	C7—C6—H6	120.3
C1—O7—H7A	111.4 (16)	C3—C7—C6	120.3 (2)
H8A—O8—H8B	109 (3)	C3—C7—H7	119.8
H9A—O9—H9B	104 (3)	C6—C7—H7	119.8
O7—C1—C2	111.54 (15)	C5—N1—C4	121.9 (2)
O7—C1—P2	105.31 (12)	C5—N1—H1	119.1
C2—C1—P2	111.88 (13)	C4—N1—H1	119.1
O7—C1—P1	108.12 (12)	H2C—N2—H2D	111 (2)
C2—C1—P1	109.26 (12)	H2C—N2—H2E	104 (2)
P2—C1—P1	110.62 (9)	H2D—N2—H2E	110 (2)
C3—C2—C1	114.40 (15)	H2C—N2—H2F	114 (2)
C3—C2—H2A	108.7	H2D—N2—H2F	110 (2)
C1—C2—H2A	108.7	H2E—N2—H2F	107 (2)
C3—C2—H2B	108.7
O7—C1—C2—C3	58.1 (2)	C1—C2—C3—C4	109.7 (2)
P1—C1—C2—C3	177.59 (13)	C1—C2—C3—C7	−71.0 (2)
P2—C1—C2—C3	−59.55 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5^i	0.83 (2)	1.68 (2)	2.510 (2)	177 (3)
O6—H6A···O2	0.82 (2)	1.89 (2)	2.656 (2)	157 (3)
O7—H7A···O8^i	0.85 (3)	2.01 (3)	2.818 (2)	158 (2)
N1—H1···O9	0.86	1.88	2.690 (2)	157
N2—H2C···O1	0.91 (2)	1.98 (2)	2.854 (2)	163 (2)
N2—H2D···O8^ii	0.89 (2)	2.12 (2)	3.009 (2)	178 (2)
N2—H2E···O4^iii	0.90 (2)	2.04 (2)	2.923 (2)	171 (2)
N2—H2F···O2^iv	0.95 (2)	1.83 (2)	2.768 (2)	170 (2)
O8—H8A···O1^v	0.82 (2)	2.07 (2)	2.867 (2)	166 (3)
O8—H8B···O4	0.82 (2)	1.88 (2)	2.684 (2)	165 (3)
O9—H9A···O4^iv	0.81 (2)	2.01 (2)	2.785 (2)	159 (3)
O9—H9B···O1^vi	0.84 (2)	1.91 (2)	2.738 (2)	169 (3)

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

(II) monopotassium [1-hydroxy-1-phosphono-2-(pyridinum-3-yl)ethyl]phosphonate dihydrate

Crystal data

K^+·C7H10NO7P2^−·2H2O	F(000) = 736
Mr = 357.23	Dx = 1.862 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4900 reflections
a = 6.5356 (4) Å	θ = 2.9–28.0°
b = 28.1606 (17) Å	µ = 0.71 mm^−1
c = 6.9636 (4) Å	T = 118 K
β = 95.993 (1)°	Tabular, colourless
V = 1274.62 (13) Å^3	0.18 × 0.12 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	2644 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
Graphite monochromator	θmax = 28.0°, θmin = 1.5°
ω scan, frame data integration	h = −8→8
9075 measured reflections	k = −34→37
3052 independent reflections	l = −8→9

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0496P)^2] where P = (Fo^2 + 2Fc^2)/3
3052 reflections	(Δ/σ)max < 0.001
202 parameters	Δρmax = 0.76 e Å^−3
7 restraints	Δρmin = −0.47 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.

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 > 2σ(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
K	0.69496 (6)	0.239806 (14)	0.88778 (6)	0.01217 (11)
P1	0.24087 (7)	0.177225 (16)	0.87208 (6)	0.00835 (12)
P2	−0.03296 (7)	0.141948 (16)	0.50669 (6)	0.00838 (12)
O1	0.42836 (18)	0.16194 (5)	1.00110 (17)	0.0115 (3)
O2	0.26947 (19)	0.22005 (5)	0.74986 (17)	0.0113 (3)
O3	0.05627 (19)	0.18658 (5)	0.99547 (18)	0.0113 (3)
H3	0.075 (4)	0.1751 (8)	1.100 (2)	0.017*
O4	−0.14134 (19)	0.09669 (4)	0.43510 (18)	0.0125 (3)
O5	0.07269 (19)	0.16763 (5)	0.35678 (17)	0.0124 (3)
O6	−0.18954 (19)	0.17523 (5)	0.60046 (18)	0.0130 (3)
H6A	−0.285 (3)	0.1836 (8)	0.526 (3)	0.019*
O7	0.07289 (19)	0.08995 (4)	0.82602 (18)	0.0108 (3)
H7A	−0.020 (3)	0.1007 (8)	0.882 (3)	0.016*
O8	−0.2488 (2)	0.09762 (5)	0.04058 (19)	0.0143 (3)
H8A	−0.342 (3)	0.1169 (7)	0.034 (3)	0.021*
H8B	−0.207 (3)	0.0981 (9)	0.155 (2)	0.021*
O9	0.54096 (19)	0.20723 (5)	1.33856 (18)	0.0122 (3)
H9A	0.604 (3)	0.2306 (7)	1.305 (3)	0.018*
H9B	0.513 (4)	0.1913 (8)	1.240 (3)	0.018*
C1	0.1551 (3)	0.12665 (6)	0.7137 (2)	0.0081 (3)
C2	0.3496 (3)	0.10569 (6)	0.6385 (3)	0.0108 (4)
H2A	0.4218	0.1313	0.5781	0.013*
H2B	0.4409	0.0942	0.7493	0.013*
C3	0.3134 (3)	0.06566 (6)	0.4951 (3)	0.0104 (3)
C4	0.2587 (3)	0.02066 (7)	0.5511 (3)	0.0117 (4)
H4	0.2412	0.0149	0.6799	0.014*
C5	0.2560 (3)	−0.00876 (7)	0.2362 (3)	0.0138 (4)
H5	0.2368	−0.0341	0.1507	0.017*
C6	0.3108 (3)	0.03519 (7)	0.1713 (3)	0.0144 (4)
H6	0.3290	0.0398	0.0419	0.017*
C7	0.3385 (3)	0.07252 (7)	0.3011 (3)	0.0124 (4)
H7	0.3741	0.1024	0.2582	0.015*
N1	0.2307 (2)	−0.01481 (5)	0.4229 (2)	0.0109 (3)
H1	0.1953	−0.0423	0.4617	0.013*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K	0.01021 (19)	0.0124 (2)	0.0141 (2)	−0.00048 (13)	0.00189 (15)	−0.00141 (14)
P1	0.0079 (2)	0.0083 (2)	0.0087 (2)	−0.00003 (16)	0.00014 (17)	−0.00057 (16)
P2	0.0083 (2)	0.0089 (2)	0.0078 (2)	−0.00024 (16)	0.00011 (17)	0.00022 (15)
O1	0.0098 (6)	0.0125 (6)	0.0116 (6)	0.0014 (5)	−0.0015 (5)	−0.0017 (5)
O2	0.0123 (6)	0.0112 (6)	0.0105 (6)	−0.0010 (5)	0.0020 (5)	−0.0002 (5)
O3	0.0108 (6)	0.0147 (7)	0.0083 (6)	0.0025 (5)	0.0014 (5)	0.0013 (5)
O4	0.0126 (6)	0.0126 (6)	0.0114 (6)	−0.0026 (5)	−0.0024 (5)	0.0003 (5)
O5	0.0139 (6)	0.0138 (6)	0.0095 (6)	−0.0018 (5)	0.0010 (5)	0.0009 (5)
O6	0.0098 (6)	0.0165 (7)	0.0120 (6)	0.0048 (5)	−0.0018 (5)	−0.0004 (5)
O7	0.0114 (6)	0.0096 (6)	0.0118 (6)	0.0005 (5)	0.0034 (5)	0.0023 (5)
O8	0.0128 (6)	0.0175 (7)	0.0123 (6)	0.0030 (5)	0.0006 (5)	−0.0016 (5)
O9	0.0126 (6)	0.0111 (6)	0.0124 (7)	−0.0017 (5)	−0.0011 (5)	−0.0017 (5)
C1	0.0086 (8)	0.0089 (8)	0.0070 (8)	−0.0007 (6)	0.0014 (6)	0.0000 (6)
C2	0.0080 (8)	0.0114 (9)	0.0129 (9)	0.0002 (6)	0.0010 (7)	−0.0018 (7)
C3	0.0062 (8)	0.0122 (9)	0.0129 (8)	0.0021 (6)	0.0011 (7)	−0.0006 (7)
C4	0.0072 (8)	0.0157 (9)	0.0123 (9)	0.0018 (7)	0.0014 (6)	−0.0001 (7)
C5	0.0119 (8)	0.0138 (9)	0.0151 (9)	0.0004 (7)	−0.0008 (7)	−0.0044 (7)
C6	0.0134 (9)	0.0185 (10)	0.0114 (9)	0.0018 (7)	0.0020 (7)	0.0002 (7)
C7	0.0118 (8)	0.0120 (9)	0.0134 (9)	0.0000 (7)	0.0018 (7)	0.0013 (7)
N1	0.0082 (7)	0.0096 (7)	0.0150 (8)	−0.0005 (5)	0.0022 (6)	0.0008 (6)

Geometric parameters (Å, º)

K—O5^i	2.7283 (13)	C1—C2	1.542 (2)
K—O2^i	2.7598 (13)	C2—H2A	0.9800
K—O9^ii	2.7599 (14)	C2—H2B	0.9800
K—O3^iii	2.8311 (13)	C2—C3	1.508 (2)
K—O6^iii	2.8627 (14)	C3—C4	1.384 (3)
K—O2	2.8996 (13)	C4—H4	0.9300
K—O1	2.9588 (13)	C4—N1	1.339 (2)
P1—O1	1.5048 (12)	N1—H1	0.8600
P1—O2	1.4989 (13)	N1—C5	1.338 (2)
P1—O3	1.5747 (13)	C5—H5	0.9300
P2—O4	1.5168 (13)	C5—C6	1.378 (3)
P2—O5	1.4967 (13)	C6—H6	0.9300
P2—O6	1.5785 (14)	C6—C7	1.386 (3)
P1—C1	1.8522 (17)	C7—H7	0.9300
P2—C1	1.8447 (16)	C3—C7	1.391 (2)
O3—H3	0.792 (15)	O8—H8A	0.813 (16)
O6—H6A	0.803 (16)	O8—H8B	0.817 (16)
C1—O7	1.434 (2)	O9—H9A	0.824 (16)
O7—H7A	0.810 (15)	O9—H9B	0.825 (16)
O5^i—K—O2^i	72.73 (4)	O4—P2—O6	109.52 (7)
O5^i—K—O9^ii	73.20 (4)	O5—P2—C1	109.85 (7)
O2^i—K—O9^ii	79.83 (4)	O4—P2—C1	108.10 (7)
O5^i—K—O3^iii	139.12 (4)	O6—P2—C1	102.90 (7)
O2^i—K—O3^iii	84.96 (4)	P2—O6—H6A	113.7 (17)
O9^ii—K—O3^iii	69.36 (4)	O7—C1—C2	106.16 (14)
O5^i—K—O6^iii	130.39 (4)	O7—C1—P2	109.74 (11)
O2^i—K—O6^iii	149.83 (4)	C2—C1—P2	109.26 (11)
O9^ii—K—O6^iii	88.69 (4)	O7—C1—P1	109.67 (11)
O3^iii—K—O6^iii	64.87 (4)	C2—C1—P1	106.70 (11)
O5^i—K—O2	83.93 (4)	P2—C1—P1	114.92 (9)
O2^i—K—O2	116.93 (5)	C3—C2—C1	115.64 (14)
O9^ii—K—O2	146.35 (4)	C3—C2—H2A	108.4
O3^iii—K—O2	136.94 (4)	C1—C2—H2A	108.4
O6^iii—K—O2	87.73 (4)	C3—C2—H2B	108.4
O5^i—K—O1	123.60 (4)	C1—C2—H2B	108.4
O2^i—K—O1	96.47 (4)	H2A—C2—H2B	107.4
O9^ii—K—O1	161.18 (4)	C4—C3—C7	117.46 (16)
O3^iii—K—O1	92.01 (4)	C4—C3—C2	121.69 (16)
O6^iii—K—O1	85.48 (4)	C7—C3—C2	120.84 (16)
O2—K—O1	51.32 (3)	N1—C4—C3	121.09 (17)
O5^i—K—H9A	94.2 (4)	N1—C4—H4	119.5
O2^i—K—H9A	36.3 (3)	C3—C4—H4	119.5
O9^ii—K—H9A	114.1 (4)	C5—N1—C4	122.02 (16)
O3^iii—K—H9A	86.7 (4)	C5—N1—H1	119.0
O6^iii—K—H9A	134.9 (4)	C4—N1—H1	119.0
O2—K—H9A	91.4 (4)	N1—C5—C6	119.73 (17)
O1—K—H9A	60.2 (3)	N1—C5—H5	120.1
O2—P1—O1	115.29 (7)	C6—C5—H5	120.1
O2—P1—O3	108.86 (7)	C5—C6—C7	119.22 (17)
O1—P1—O3	110.16 (7)	C5—C6—H6	120.4
O2—P1—C1	109.17 (7)	C7—C6—H6	120.4
O1—P1—C1	108.22 (7)	C6—C7—C3	120.48 (17)
O3—P1—C1	104.60 (7)	C6—C7—H7	119.8
P1—O1—K	95.41 (6)	C3—C7—H7	119.8
P1—O2—K	97.96 (6)	C1—O7—H7A	109.3 (16)
P1—O3—H3	112.0 (17)	H8A—O8—H8B	103 (2)
O5—P2—O4	114.23 (7)	H9A—O9—H9B	106 (2)
O5—P2—O6	111.58 (8)
O7—C1—C2—C3	66.90 (18)	C1—C2—C3—C4	−73.4 (2)
P1—C1—C2—C3	−176.18 (12)	C1—C2—C3—C7	108.02 (19)
P2—C1—C2—C3	−51.38 (18)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^iv	0.86	1.74	2.599 (2)	173
O3—H3···O5^v	0.79 (2)	1.81 (2)	2.5633 (17)	160 (2)
O6—H6A···O9^vi	0.80 (2)	1.77 (2)	2.5631 (17)	169 (2)
O7—H7A···O8^v	0.81 (2)	1.96 (2)	2.712 (2)	155 (2)
O8—H8A···O1^vi	0.81 (2)	1.96 (2)	2.7725 (18)	176 (2)
O8—H8B···O4	0.82 (2)	1.95 (2)	2.7638 (18)	173 (2)
O9—H9A···O2^i	0.82 (2)	1.83 (2)	2.6454 (19)	174 (2)
O9—H9B···O1	0.83 (2)	1.89 (2)	2.7074 (17)	172 (2)

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