A potassium-18-crown-6 salt of a cyclic myo-inositol phosphate

The six-membered phosphorinane ring in (1,4,7,10,13,16-hexaoxa­cyclo­octa­decane)­potassium 2-O-benzoyl-1,3,5-O-methyl­idyne-myo-in­osi­tol 4,6-cyclo­phosphate trihydrate, [K(C₁₂H₂₄O₆)](C₁₄H₁₂O₉P)·3H₂O, has a boat rather than a chair conformation. The K⁺ ion is eight-coordinate and is connected to one of the phosphate O atoms, one of the O atoms of the myo-inositol residue and the six O atoms of the crown ether.

S1. Comment

Inositol phosphates have attracted the attention of a large number of chemists as a result of the role of some of these compounds as secondary messengers in signal transduction (Potter & Lampe, 1995). Our interest lies mainly in cyclic phosphorus compounds (Kumara Swamy et al., 1998; Muthiah & Kumara Swamy, 1999) and in this connection we felt that various cyclic phosphates could be generated from suitably protected inositol derivatives. It should be noted that, despite so much interest in inositol phosphates, few cyclic derivatives have been structurally characterized, although the crystal structures of two cyclic phosphates derived from inositol have been reported recently (Dietrich et al., 1999; Neidle et al., 1998). In the present paper, we report the structure of a cyclic inositol phosphate as a trihydrate of its potassium-18-crown-6 salt, viz. [K(18-crown-6)]⁺[myo-C₆H₆-2-{OC(O)Ph}-1,3,5-(O₃CH)-{O₂P(O)O}]^-. 3H₂O, (I).

An ellipsoid plot of (I), excluding the O atoms of the water molecules, is shown in Fig. 1. Apart from the six O atoms of the crown ether, potassium is coordinated to O2 of the inositol residue and to O7 of the phosphate residue in the neighbouring cell along b, leading to a chain structure (Fig. 2).

The K—O7 distance [2.771 (4) Å] is the shortest of all the K—O distances in this compound. The P—O bond distances involving the inositol residue [P—O1 1.608 (3) Å and P—O5 1.627 (3) Å] are normal but longer than the mean value of 1.580 (2) Å found by Neidle et al. (1998) in C₆H₆(OH)₃[O₃P(O)], (II).

Interestingly, in (I), the six-membered 1,3,2-dioxaphosphorinane ring adopts a boat conformation (Fig. 3) with P and C6 (the prow and stern of the boat) on the same side at distances of 0.608 and 0.675 Å, respectively, from the mean plane through C1, C5, O1 and O5 (the maximum deviation from this mean plane is 0.004 Å). This is different from (II) where all three six-membered 1,3,2-dioxaphosphorinane rings have a chair conformation (Neidle et al., 1998). It should also be noted that a chair conformation is normally found for 1,3,2-dioxaphosphorinane rings containing tri- or tetracoordinate phosphorus (Maryanoff et al., 1979). A boat conformation is found mainly for pentacoordinate phosphorus in which the 1,3,2-dioxaphosphorinane ring bridges one apical and one equatorial site of a trigonal-bipyramidal arrangement (Said et al., 1997). However, in these compounds, an apical O atom and the C atom opposite it lie at the prow and stern of the boat. It is likely that in (I), steric interactions involving the phosphorus and the C3 H atom are greater in the alternative chair conformation.

Hydrogen-bonding interactions involving O7, O8, O9 and the water O atoms are present in (I). While O7 is within hydrogen-bonding distance of O16A and O16B of a second molecule, atom O8 has intermolecular hydrogen-bonded contacts to O17A, O17B and O18A. The carbonyl O9 atom is rather weakly hydrogen bonded to O16B, judging by the long O···O distance [3.033 (9) Å]. Since it was not possible to locate or fix the water H atoms, no discussion of this aspect is possible.

S2. Experimental

The crude phosphate (0.070 g, 0.20 mmol), prepared by adding PCl₃ to 2-O-benzoyl-myo-inositol 1,3,5-orthoformate (Ozaki et al., 1994) followed by oxidation and hydrolysis (I₂/ water), was added to a mixture of 18-crown-6 (0.061 g, 0.23 mmol) and KF (0.022 g, 0.38 mmol)in tetrahydrofuran (5 ml). The mixture was refluxed for 2 h, stirred overnight, then filtered to remove undissolved KF and left to crystallize. Needle-shaped crystals of (I) were obtained. M.p. 377–379 K. ¹H NMR (CDCl₃, p.p.m.): γ 2.40 (br s, ca 6H, H₂O), 3.65 (s, 24H, CH₂ of 18-crown-6), 4.55–4.58 (m, 2H, CH), 4.85–4.91 (m, 2H, CH), 5.50–5.55 (m, 2H, CH), 5.81–5.83 (m, 1H, CH), 7.35–7.65 (m, 3H, Ar—H), 8.11–8.60 (m, 2H, Ar—H). ³¹P NMR: -11.1.

S3. Refinement

H atoms were placed geometrically and refined using a riding model with C—H constrained to 0.93–0.98 Å and U_iso(H) = 1.2U_eq(C). The water O16A, O16B, O17A, O17B, O18A and O18B atoms were refined isotropically and H atoms on these O atoms are not included in the refinement. There are three positionally disordered lattice water molecules; the O atoms of each of these were assigned two positions and refined isotropically using free variable restraints with total occupancy for each pair of disordered O-atom positions set to unity. H atoms on these O atoms could not be located and so were not included in the refinement model.

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: SDP (Frenz, 1985); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I) showing the atom-numbering scheme. Atoms are represented by 25% probability displacement ellipsoids. Water O atoms and all H atoms have been omitted.
	Fig. 2. A diagram showing the eight-coordination at potassium and the chain structure. Water O atoms have been omitted. [Symmetry code: (i) x, y - 1, z.]
	Fig. 3. A diagram showing the boat conformation of the six-membered 1,3,2-dioxaphosphorinane ring.

2-benzoyl-1,3,5-O-methylidyneinositol 4,6-cyclophosphate, potassium- 18-crown-6 salt

Crystal data

[K(C12H24O6)](C14H12O9P)·3H2O	F(000) = 1504
Mr = 712.67	Dx = 1.416 Mg m^−3
Monoclinic, P21/c	Melting point: 377–379K K
Hall symbol: -P_2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 17.146 (2) Å	Cell parameters from 25 reflections
b = 10.9380 (16) Å	θ = 9.5–12.0°
c = 18.965 (9) Å	µ = 0.28 mm^−1
β = 109.96 (2)°	T = 293 K
V = 3343.1 (18) Å^3	Block cut from needle, colourless
Z = 4	0.30 × 0.30 × 0.20 mm

Data collection

Enraf-Nonius MACH3 diffractometer	Rint = 0.0
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.2°
Graphite monochromator	h = 0→20
Profile data from ω scans	k = 0→12
5867 measured reflections	l = −22→21
5867 independent reflections	3 standard reflections every 90 min
2662 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.059	See text
wR(F^2) = 0.198	w 1/[σ^2(Fo^2) + (0.075P)^2 + 3.92P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
5867 reflections	Δρmax = 0.53 e Å^−3
416 parameters	Δρmin = −0.31 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (5)

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 > 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)
K	0.70547 (7)	0.02638 (10)	0.25207 (6)	0.0579 (3)
P	0.67571 (10)	0.68220 (12)	0.19374 (8)	0.0606 (4)
O1	0.6559 (2)	0.5538 (3)	0.22529 (17)	0.0551 (8)
O2	0.7699 (2)	0.2671 (3)	0.23963 (16)	0.0535 (8)
O3	0.8805 (2)	0.4057 (3)	0.36145 (15)	0.0530 (8)
O4	0.8761 (2)	0.3669 (3)	0.21442 (17)	0.0556 (8)
O5	0.7703 (2)	0.6600 (3)	0.19574 (17)	0.0581 (9)
O6	0.7481 (2)	0.3467 (3)	0.12242 (16)	0.0582 (9)
O7	0.6800 (3)	0.7761 (3)	0.2505 (2)	0.0800 (12)
O8	0.6195 (3)	0.6983 (4)	0.1157 (2)	0.0860 (12)
O9	0.8043 (2)	0.4444 (3)	0.43470 (17)	0.0620 (9)
O10	0.8786 (2)	0.0008 (3)	0.31345 (19)	0.0620 (9)
O11	0.8105 (2)	0.0033 (3)	0.15589 (19)	0.0645 (10)
O12	0.6388 (3)	0.0435 (4)	0.0945 (2)	0.0780 (11)
O13	0.5589 (2)	0.1627 (4)	0.1829 (2)	0.0822 (12)
O14	0.6233 (3)	0.1467 (4)	0.3384 (2)	0.0878 (13)
O15	0.7952 (2)	0.1242 (3)	0.40056 (17)	0.0691 (10)
C1	0.6788 (3)	0.4403 (4)	0.1996 (2)	0.0469 (11)
H1	0.6299	0.3878	0.1795	0.056*
C2	0.7429 (3)	0.3780 (4)	0.2656 (2)	0.0485 (12)
H2	0.7181	0.3581	0.3038	0.058*
C3	0.8163 (3)	0.4610 (4)	0.2989 (2)	0.0451 (11)
H3	0.7985	0.5389	0.3141	0.054*
C4	0.8549 (3)	0.4819 (4)	0.2394 (3)	0.0518 (12)
H4	0.9047	0.5327	0.2595	0.062*
C5	0.7918 (3)	0.5455 (4)	0.1713 (2)	0.0480 (11)
H5	0.8173	0.5600	0.1330	0.058*
C6	0.7190 (3)	0.4605 (4)	0.1401 (2)	0.0494 (11)
H6	0.6786	0.4960	0.0950	0.059*
C7	0.8054 (3)	0.2937 (4)	0.1852 (3)	0.0552 (13)
H7	0.8229	0.2161	0.1695	0.066*
C8	0.8672 (3)	0.4064 (4)	0.4279 (2)	0.0527 (12)
C9	0.9400 (3)	0.3561 (4)	0.4890 (2)	0.0519 (12)
C10	0.9307 (4)	0.3362 (5)	0.5578 (3)	0.0616 (14)
H10	0.8804	0.3528	0.5644	0.074*
C11	0.9968 (4)	0.2916 (5)	0.6161 (3)	0.0686 (15)
H11	0.9904	0.2759	0.6620	0.082*
C12	1.0715 (4)	0.2701 (5)	0.6078 (3)	0.0695 (15)
H12	1.1160	0.2418	0.6481	0.083*
C13	1.0806 (3)	0.2904 (5)	0.5391 (3)	0.0662 (14)
H13	1.1313	0.2752	0.5330	0.079*
C14	1.0145 (3)	0.3334 (4)	0.4795 (3)	0.0593 (13)
H14	1.0204	0.3469	0.4332	0.071*
C15	0.9275 (3)	−0.0028 (5)	0.2667 (3)	0.0717 (16)
H15A	0.9791	−0.0456	0.2919	0.086*
H15B	0.9408	0.0797	0.2558	0.086*
C16	0.8807 (4)	−0.0665 (5)	0.1960 (3)	0.0734 (17)
H16A	0.9159	−0.0775	0.1659	0.088*
H16B	0.8635	−0.1465	0.2072	0.088*
C17	0.7597 (4)	−0.0517 (5)	0.0883 (3)	0.0738 (17)
H17A	0.7380	−0.1288	0.0989	0.089*
H17B	0.7917	−0.0676	0.0559	0.089*
C18	0.6919 (4)	0.0315 (6)	0.0517 (3)	0.0746 (17)
H18A	0.7141	0.1110	0.0460	0.090*
H18B	0.6606	0.0008	0.0022	0.090*
C19	0.5731 (4)	0.1283 (7)	0.0646 (3)	0.0847 (18)
H19A	0.5430	0.1094	0.0123	0.102*
H19B	0.5952	0.2105	0.0674	0.102*
C20	0.5164 (4)	0.1203 (7)	0.1088 (3)	0.093 (2)
H20A	0.4674	0.1699	0.0855	0.112*
H20B	0.4988	0.0363	0.1103	0.112*
C21	0.5072 (4)	0.1644 (8)	0.2271 (4)	0.112 (3)
H21A	0.4907	0.0817	0.2341	0.134*
H21B	0.4575	0.2114	0.2020	0.134*
C22	0.5529 (4)	0.2198 (8)	0.3005 (4)	0.105 (2)
H22A	0.5705	0.3017	0.2933	0.126*
H22B	0.5170	0.2254	0.3303	0.126*
C23	0.6693 (4)	0.1913 (7)	0.4113 (3)	0.097 (2)
H23A	0.6352	0.1889	0.4429	0.116*
H23B	0.6857	0.2754	0.4080	0.116*
C24	0.7436 (4)	0.1149 (6)	0.4443 (3)	0.087 (2)
H24A	0.7735	0.1418	0.4952	0.104*
H24B	0.7273	0.0304	0.4463	0.104*
C25	0.8683 (4)	0.0549 (6)	0.4308 (3)	0.0811 (18)
H25A	0.8543	−0.0300	0.4352	0.097*
H25B	0.8999	0.0848	0.4806	0.097*
C26	0.9187 (4)	0.0647 (5)	0.3816 (3)	0.0762 (16)
H26A	0.9255	0.1500	0.3710	0.091*
H26B	0.9733	0.0300	0.4066	0.091*
O16A	0.2743 (8)	0.3018 (15)	0.1048 (7)	0.161 (7)*	0.491 (13)
O16B	0.2908 (5)	0.1835 (8)	0.1004 (4)	0.087 (4)*	0.509 (13)
O17A	0.3739 (8)	0.3504 (9)	0.0200 (5)	0.121 (5)*	0.582 (18)
O17B	0.3101 (11)	0.3334 (12)	0.0010 (7)	0.113 (6)*	0.418 (18)
O18A	0.5105 (9)	0.0607 (13)	0.4710 (8)	0.202 (7)*	0.579 (13)
O18B	0.5220 (12)	−0.0380 (17)	0.4008 (10)	0.184 (9)*	0.421 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K	0.0691 (8)	0.0560 (7)	0.0579 (6)	−0.0058 (6)	0.0337 (6)	−0.0056 (5)
P	0.0765 (10)	0.0481 (8)	0.0661 (9)	0.0036 (7)	0.0359 (8)	0.0037 (7)
O1	0.067 (2)	0.0489 (19)	0.0607 (19)	0.0010 (17)	0.0359 (18)	0.0007 (16)
O2	0.076 (2)	0.0430 (18)	0.0490 (17)	−0.0028 (17)	0.0311 (17)	0.0021 (15)
O3	0.062 (2)	0.064 (2)	0.0368 (16)	0.0017 (17)	0.0219 (16)	−0.0018 (15)
O4	0.067 (2)	0.054 (2)	0.0586 (19)	0.0022 (18)	0.0374 (18)	−0.0034 (16)
O5	0.076 (2)	0.0408 (18)	0.068 (2)	−0.0023 (17)	0.0390 (19)	0.0016 (16)
O6	0.084 (2)	0.053 (2)	0.0423 (17)	0.0060 (18)	0.0273 (18)	−0.0065 (15)
O7	0.116 (3)	0.046 (2)	0.097 (3)	−0.001 (2)	0.061 (3)	−0.011 (2)
O8	0.097 (3)	0.086 (3)	0.071 (2)	0.022 (2)	0.024 (2)	0.021 (2)
O9	0.068 (2)	0.076 (2)	0.0504 (19)	0.008 (2)	0.0305 (18)	−0.0025 (17)
O10	0.067 (2)	0.057 (2)	0.067 (2)	−0.0028 (18)	0.0295 (19)	−0.0010 (17)
O11	0.092 (3)	0.052 (2)	0.059 (2)	0.003 (2)	0.039 (2)	−0.0021 (17)
O12	0.103 (3)	0.082 (3)	0.058 (2)	−0.007 (3)	0.040 (2)	0.003 (2)
O13	0.058 (2)	0.120 (3)	0.074 (2)	−0.011 (2)	0.030 (2)	−0.019 (2)
O14	0.083 (3)	0.120 (4)	0.076 (3)	−0.012 (3)	0.047 (2)	−0.026 (3)
O15	0.089 (3)	0.079 (3)	0.0469 (19)	−0.001 (2)	0.032 (2)	0.0079 (18)
C1	0.051 (3)	0.047 (3)	0.048 (2)	−0.012 (2)	0.023 (2)	−0.007 (2)
C2	0.068 (3)	0.042 (3)	0.049 (3)	−0.001 (2)	0.038 (3)	0.002 (2)
C3	0.050 (3)	0.048 (3)	0.041 (2)	0.002 (2)	0.021 (2)	0.002 (2)
C4	0.067 (3)	0.045 (3)	0.057 (3)	−0.006 (2)	0.037 (3)	−0.004 (2)
C5	0.066 (3)	0.040 (3)	0.047 (3)	−0.003 (2)	0.032 (2)	0.005 (2)
C6	0.065 (3)	0.048 (3)	0.040 (2)	−0.003 (2)	0.023 (2)	0.000 (2)
C7	0.079 (4)	0.044 (3)	0.051 (3)	0.002 (3)	0.034 (3)	−0.004 (2)
C8	0.069 (3)	0.050 (3)	0.043 (3)	−0.009 (3)	0.025 (3)	−0.010 (2)
C9	0.069 (3)	0.044 (3)	0.043 (2)	−0.010 (2)	0.019 (2)	−0.001 (2)
C10	0.081 (4)	0.062 (3)	0.049 (3)	0.007 (3)	0.030 (3)	−0.002 (2)
C11	0.093 (4)	0.062 (3)	0.048 (3)	0.005 (3)	0.020 (3)	0.006 (3)
C12	0.088 (4)	0.050 (3)	0.058 (3)	−0.003 (3)	0.010 (3)	0.004 (3)
C13	0.061 (3)	0.055 (3)	0.078 (4)	−0.009 (3)	0.017 (3)	−0.006 (3)
C14	0.068 (4)	0.057 (3)	0.052 (3)	−0.011 (3)	0.019 (3)	0.002 (2)
C15	0.070 (4)	0.065 (4)	0.094 (4)	0.014 (3)	0.048 (3)	0.011 (3)
C16	0.099 (5)	0.058 (3)	0.087 (4)	0.006 (3)	0.063 (4)	0.005 (3)
C17	0.114 (5)	0.060 (3)	0.061 (3)	−0.018 (4)	0.048 (4)	−0.014 (3)
C18	0.095 (4)	0.087 (4)	0.047 (3)	−0.021 (4)	0.031 (3)	−0.008 (3)
C19	0.094 (5)	0.100 (5)	0.050 (3)	−0.016 (4)	0.012 (3)	−0.004 (3)
C20	0.065 (4)	0.123 (6)	0.082 (4)	−0.015 (4)	0.012 (3)	−0.019 (4)
C21	0.063 (4)	0.163 (7)	0.123 (6)	−0.013 (5)	0.050 (4)	−0.027 (6)
C22	0.076 (5)	0.154 (7)	0.105 (5)	−0.009 (5)	0.057 (4)	−0.039 (5)
C23	0.119 (6)	0.128 (6)	0.069 (4)	−0.037 (5)	0.067 (4)	−0.038 (4)
C24	0.121 (6)	0.102 (5)	0.054 (3)	−0.027 (4)	0.051 (4)	−0.004 (3)
C25	0.115 (5)	0.068 (4)	0.052 (3)	0.001 (4)	0.019 (4)	0.004 (3)
C26	0.073 (4)	0.072 (4)	0.072 (4)	−0.001 (3)	0.009 (3)	−0.012 (3)

Geometric parameters (Å, º)

K—O2	2.896 (3)	C6—H6	0.9800
K—O7^i	2.771 (4)	C7—H7	0.9800
K—O10	2.808 (4)	C8—C9	1.489 (7)
K—O11	2.979 (3)	C9—C14	1.372 (7)
K—O12	2.818 (4)	C9—C10	1.384 (6)
K—O13	2.830 (4)	C10—C11	1.374 (7)
K—O14	2.823 (4)	C10—H10	0.9300
K—O15	2.913 (4)	C11—C12	1.364 (8)
P—O1	1.608 (3)	C11—H11	0.9300
P—O5	1.627 (3)	C12—C13	1.383 (7)
P—O7	1.472 (4)	C12—H12	0.9300
P—O8	1.476 (4)	C13—C14	1.382 (7)
O1—C1	1.437 (5)	C13—H13	0.9300
O2—C7	1.395 (5)	C14—H14	0.9300
O2—C2	1.444 (5)	C15—C16	1.480 (8)
O3—C8	1.355 (5)	C15—H15A	0.9700
O3—C3	1.447 (5)	C15—H15B	0.9700
O4—C7	1.401 (6)	C16—H16A	0.9700
O4—C4	1.434 (5)	C16—H16B	0.9700
O5—C5	1.427 (5)	C17—C18	1.452 (8)
O6—C7	1.386 (6)	C17—H17A	0.9700
O6—C6	1.423 (5)	C17—H17B	0.9700
O7—K^ii	2.771 (4)	C18—H18A	0.9700
O9—C8	1.203 (5)	C18—H18B	0.9700
O10—C15	1.415 (5)	C19—C20	1.488 (8)
O10—C26	1.423 (6)	C19—H19A	0.9700
O11—C16	1.409 (6)	C19—H19B	0.9700
O11—C17	1.415 (6)	C20—H20A	0.9700
O12—C18	1.418 (6)	C20—H20B	0.9700
O12—C19	1.419 (7)	C21—C22	1.474 (9)
O13—C21	1.412 (6)	C21—H21A	0.9700
O13—C20	1.422 (6)	C21—H21B	0.9700
O14—C22	1.422 (8)	C22—H22A	0.9700
O14—C23	1.424 (7)	C22—H22B	0.9700
O15—C24	1.409 (6)	C23—C24	1.472 (9)
O15—C25	1.409 (7)	C23—H23A	0.9700
C1—C2	1.517 (6)	C23—H23B	0.9700
C1—C6	1.525 (5)	C24—H24A	0.9700
C1—H1	0.9800	C24—H24B	0.9700
C2—C3	1.505 (6)	C25—C26	1.477 (8)
C2—H2	0.9800	C25—H25A	0.9700
C3—C4	1.509 (5)	C25—H25B	0.9700
C3—H3	0.9800	C26—H26A	0.9700
C4—C5	1.540 (7)	C26—H26B	0.9700
C4—H4	0.9800	O16A—O16B	1.334 (15)
C5—C6	1.506 (6)	O17A—O17B	1.045 (13)
C5—H5	0.9800	O18A—O18B	1.78 (2)
O7^i—K—O10	92.66 (12)	O6—C7—O4	111.3 (4)
O7^i—K—O12	92.81 (12)	O2—C7—O4	111.3 (4)
O10—K—O12	115.80 (11)	O6—C7—H7	107.5
O7^i—K—O14	111.02 (12)	O2—C7—H7	107.5
O10—K—O14	118.17 (12)	O4—C7—H7	107.5
O12—K—O14	118.80 (14)	O9—C8—O3	122.9 (5)
O7^i—K—O13	113.81 (13)	O9—C8—C9	126.0 (4)
O10—K—O13	152.94 (12)	O3—C8—C9	111.1 (4)
O12—K—O13	59.92 (12)	C14—C9—C10	120.6 (5)
O14—K—O13	58.88 (12)	C14—C9—C8	122.3 (4)
O7^i—K—O2	163.85 (10)	C10—C9—C8	117.1 (5)
O10—K—O2	75.27 (10)	C11—C10—C9	119.0 (5)
O12—K—O2	83.16 (10)	C11—C10—H10	120.5
O14—K—O2	84.44 (11)	C9—C10—H10	120.5
O13—K—O2	77.67 (11)	C12—C11—C10	121.1 (5)
O7^i—K—O15	113.74 (12)	C12—C11—H11	119.4
O10—K—O15	60.08 (10)	C10—C11—H11	119.4
O12—K—O15	152.88 (11)	C11—C12—C13	119.6 (5)
O14—K—O15	58.09 (12)	C11—C12—H12	120.2
O13—K—O15	110.30 (12)	C13—C12—H12	120.2
O2—K—O15	69.79 (9)	C14—C13—C12	120.0 (5)
O7^i—K—O11	92.05 (10)	C14—C13—H13	120.0
O10—K—O11	58.07 (11)	C12—C13—H13	120.0
O12—K—O11	57.83 (12)	C9—C14—C13	119.6 (5)
O14—K—O11	156.92 (12)	C9—C14—H14	120.2
O13—K—O11	112.81 (11)	C13—C14—H14	120.2
O2—K—O11	72.54 (9)	O10—C15—C16	109.1 (4)
O15—K—O11	113.14 (11)	O10—C15—H15A	109.9
O1—P—O5	101.31 (17)	C16—C15—H15A	109.9
O1—P—O7	107.57 (19)	O10—C15—H15B	109.9
O1—P—O8	109.2 (2)	C16—C15—H15B	109.9
O5—P—O7	106.7 (2)	H15A—C15—H15B	108.3
O5—P—O8	110.2 (2)	O11—C16—C15	109.5 (4)
O7—P—O8	120.2 (2)	O11—C16—H16A	109.8
C1—O1—P	120.8 (2)	C15—C16—H16A	109.8
C7—O2—C2	110.4 (3)	O11—C16—H16B	109.8
C7—O2—K	121.6 (2)	C15—C16—H16B	109.8
C2—O2—K	124.1 (2)	H16A—C16—H16B	108.2
C8—O3—C3	115.9 (4)	O11—C17—C18	108.1 (4)
C7—O4—C4	110.5 (3)	O11—C17—H17A	110.1
C5—O5—P	119.3 (3)	C18—C17—H17A	110.1
C7—O6—C6	111.4 (3)	O11—C17—H17B	110.1
P—O7—K^ii	131.7 (2)	C18—C17—H17B	110.1
C15—O10—C26	112.1 (4)	H17A—C17—H17B	108.4
C15—O10—K	120.8 (3)	O12—C18—C17	110.5 (4)
C26—O10—K	116.3 (3)	O12—C18—H18A	109.5
C16—O11—C17	114.0 (4)	C17—C18—H18A	109.5
C16—O11—K	107.4 (3)	O12—C18—H18B	109.5
C17—O11—K	106.1 (3)	C17—C18—H18B	109.5
C18—O12—C19	114.1 (4)	H18A—C18—H18B	108.1
C18—O12—K	119.5 (3)	O12—C19—C20	108.5 (5)
C19—O12—K	116.6 (3)	O12—C19—H19A	110.0
C21—O13—C20	112.1 (5)	C20—C19—H19A	110.0
C21—O13—K	111.7 (4)	O12—C19—H19B	110.0
C20—O13—K	111.1 (4)	C20—C19—H19B	110.0
C22—O14—C23	113.1 (5)	H19A—C19—H19B	108.4
C22—O14—K	118.3 (3)	O13—C20—C19	109.0 (5)
C23—O14—K	120.1 (4)	O13—C20—H20A	109.9
C24—O15—C25	111.8 (4)	C19—C20—H20A	109.9
C24—O15—K	108.2 (3)	O13—C20—H20B	109.9
C25—O15—K	107.4 (3)	C19—C20—H20B	109.9
O1—C1—C2	108.2 (3)	H20A—C20—H20B	108.3
O1—C1—C6	111.8 (3)	O13—C21—C22	109.0 (5)
C2—C1—C6	107.0 (4)	O13—C21—H21A	109.9
O1—C1—H1	109.9	C22—C21—H21A	109.9
C2—C1—H1	109.9	O13—C21—H21B	109.9
C6—C1—H1	109.9	C22—C21—H21B	109.9
O2—C2—C3	109.3 (4)	H21A—C21—H21B	108.3
O2—C2—C1	108.7 (3)	O14—C22—C21	109.4 (6)
C3—C2—C1	110.0 (4)	O14—C22—H22A	109.8
O2—C2—H2	109.6	C21—C22—H22A	109.8
C3—C2—H2	109.6	O14—C22—H22B	109.8
C1—C2—H2	109.6	C21—C22—H22B	109.8
O3—C3—C2	112.6 (4)	H22A—C22—H22B	108.2
O3—C3—C4	105.7 (3)	O14—C23—C24	109.3 (5)
C2—C3—C4	107.2 (4)	O14—C23—H23A	109.8
O3—C3—H3	110.4	C24—C23—H23A	109.8
C2—C3—H3	110.4	O14—C23—H23B	109.8
C4—C3—H3	110.4	C24—C23—H23B	109.8
O4—C4—C3	109.8 (4)	H23A—C23—H23B	108.3
O4—C4—C5	107.7 (4)	O15—C24—C23	109.5 (5)
C3—C4—C5	109.5 (4)	O15—C24—H24A	109.8
O4—C4—H4	109.9	C23—C24—H24A	109.8
C3—C4—H4	109.9	O15—C24—H24B	109.8
C5—C4—H4	109.9	C23—C24—H24B	109.8
O5—C5—C6	113.5 (4)	H24A—C24—H24B	108.2
O5—C5—C4	108.0 (3)	O15—C25—C26	109.6 (5)
C6—C5—C4	107.5 (4)	O15—C25—H25A	109.8
O5—C5—H5	109.2	C26—C25—H25A	109.8
C6—C5—H5	109.2	O15—C25—H25B	109.8
C4—C5—H5	109.2	C26—C25—H25B	109.8
O6—C6—C5	108.8 (4)	H25A—C25—H25B	108.2
O6—C6—C1	109.4 (3)	O10—C26—C25	109.4 (5)
C5—C6—C1	108.8 (3)	O10—C26—H26A	109.8
O6—C6—H6	109.9	C25—C26—H26A	109.8
C5—C6—H6	109.9	O10—C26—H26B	109.8
C1—C6—H6	109.9	C25—C26—H26B	109.8
O6—C7—O2	111.3 (4)	H26A—C26—H26B	108.2

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

Hydrogen-bond geometry (Å)

D—H···A	D···A
O16A···O7^iii	2.600 (14)
O16B···O7^iii	2.883 (9)
O16B···O9^iii	3.033 (9)
O17A···O8^iv	2.668 (10)
O17B···O8^iv	2.880 (13)
O18A···O8^iii	2.726 (15)
O16B···O17B	2.603 (15)

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