3-Diphenyl­phosphino-1,2:5,6-di-O-isopropyl­idene-4-O-methyl-1D-chiro-inositol

The novel title compound, C₂₅H₃₁O₆P, contains rigid fused rings which are shown to be similar to the precursor structures. Weak C-H...O inter­molecular inter­actions produce two-dimensional sheets composed of R₄⁴(28) rings.

S1. Comment

This study is part of a programme aimed at generating new hydrogenation catalyst ligands (Gainsford et al., 2005). No monophosphinite ligands based on isopropylideneinositols have been reported previously.

The asymmetric unit of the title compound, (I), contains one independent 1-D-3-(diphenylphosphino)-1,2:5,6-di-O-isopropylidene-4-O-methyl-chiro-inositol molecule (Fig. 1). The chemically determined absolute configuration (S, R, R and S for C2, C3, C4 and C5, respectively) was confirmed by the refinement. There are two reported di-O-isopropylidene-chiro-inositol structures [Cambridge Structural Database (CSD; Allen, 2002); another D enantiomer (CSD refcode HOFLOD; Falshaw et al., 1999) and a substituted L entantiomer (IPRTIN; McConnell et al., 1972)]. Two other isoprolylidene myo-inositols structures, PINMII (Chung et al., 1994) and NAGZOL (Sureshan et al., 2004), are known, while another 1-D-1,2:5:6-di-O-isopropylidene-4-methyl-chiro-inositol, hereafter (II), has also been resolved by us (Falshaw et al., 2006).

The P—O bond length (Table 1) is similar to that found in two diphenylphosphinite ephedrine compounds [DERLEQ and DERKIU; 1.666 (6) and 1.640 (2) Å; Brunet et al., 1999], while the P—O—C angle is larger than that of the closest ring analogue (MUKREP; Nazarov et al., 2002), which has a P—O—C angle of 117.24 (10)° and a P—O distance of 1.6617 (12) Å. The torsion angles involving the Ph₂PO link [e.g. C14—P1—O3—C3 = −124.59 (12)°] are also similar to those of the latter compound [−129.40 (11)°]. Other dimensions are normal.

The inositol ring adopts a twist-boat conformation with Q = 0.6739 (17) Å, θ = 93.86 (15)° and ϕ = 340.19 (15)° (Cremer & Pople, 1975). This is quite different from the skew-boat found for the tosylated (L) derivative (IPRTIN). The two isopropylidene rings have slightly different conformations; C1/O1/C7/O2/C2 is best described as an envelope on C2, while the puckered C5/O5/C10/O6/C6 adopts a twisted form on C10—O5 (Evans & Boeyens, 1989). Comparison with (II) and HOFLOD shows that the 5,6-di-O-isopropylidene-chiro-inositol ring structure is quite rigid with only some minor changes in the interplanar angles of the average mean planes through the rings and the twist about O1—C1 (Table 3).

The packing is stabilized mainly by two weak C—H···O interactions described according to Bernstein et al. (1995) (see Table 2), viz. entry 1, which forms a C(6) chain running parallel to the a axis, and entry 2, which forms a C(10) chain running parallel to the c axis, generated by the screw axis at (3/4, 1/2, z). Together these interactions form two-dimensional sheets composed of R⁴₄(28) rings (Fig. 2). One weak C—H···π interaction provides a possible interaction in the third dimension (entry 3, Table 2, where Cg1 is the centroid of the phenyl ring atoms C20–C25). Other weaker intra- and intermolecular interactions (entries 4–6) are listed for completeness.

S2. Experimental

A solution of Ph₂PCl (468 mg, 2.12 mmol) in tetrahydrofuran (5 ml) was added dropwise to a magnetically stirred solution of 1-D-3-O-methyl-1,2:5,6-O-isopropylidene-chiro-inositol (582 mg, 2.12 mmol) and pyridine (0.32 g, 4 mmol) dissolved in tetrahydrofuran (10 ml) at room temperature. The reaction mixture was stirred for 1 h at room temperature. The solvent was removed under high vacuum. Toluene (10 ml) was added and the mixture filtered through neutral alumina. Removal of the solvents under high vacuum yielded (I) (0.84 g, 1.83 mmol, 87%) as a white solid. [α]_D = +12.2°(c 1/2, CHCl₃). Analysis calculated for C₂₅H₃₁O₆P: C 65.49, H 6.82%; found: C 66.06, H 6.78%.

S3. Refinement

All H atoms were constrained to their expected geometries (C—H = 0.95, 0.98 and 1.0 Å) and refined with U_iso(H) values of 1.2U_eq of their parent atom.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996) and SADABS (Sheldrick, 1996); 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 PLUTON (Spek, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids at the 30% probability level.
	Fig. 2. The main intermolecular packing interactions in (I), viewed down the b axis. Only H atoms and labels of one set of atoms in the the R^44(28) rings are shown (see text). Symmetry designations are as in Table 2.

1D-3-(Diphenylphosphino)-1,2:5,6-di-O-isopropylidene-4-O-methyl-chiro-inositol

Crystal data

C25H31O6P	F(000) = 976
Mr = 458.47	Dx = 1.238 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 8226 reflections
a = 5.7381 (5) Å	θ = 2.3–22.5°
b = 19.5148 (16) Å	µ = 0.15 mm^−1
c = 21.9735 (18) Å	T = 166 K
V = 2460.5 (4) Å^3	Needle, colourless
Z = 4	0.81 × 0.25 × 0.12 mm

Data collection

Siemens P4 CCD area-detector diffractometer	5014 independent reflections
Radiation source: fine-focus sealed tube	3486 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
Detector resolution: 8.192 pixels mm^-1	θmax = 26.4°, θmin = 1.9°
ϕ and ω scans	h = −3→7
Absorption correction: multi-scan (Blessing, 1995)	k = −24→24
Tmin = 0.743, Tmax = 0.979	l = −27→27
31585 measured reflections

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)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.059	w = 1/[σ^2(Fo^2) + (0.0293P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.87	(Δ/σ)max = 0.001
5014 reflections	Δρmax = 0.19 e Å^−3
294 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Absolute structure: Flack (1983), 2109 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (7)

Special details

Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 1.0 mm diameter collimator was used.

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
P1	1.19157 (8)	0.39609 (2)	0.34708 (2)	0.02716 (12)
O1	0.48207 (19)	0.42809 (6)	0.55032 (5)	0.0329 (3)
O2	0.76527 (19)	0.36592 (6)	0.50148 (5)	0.0309 (3)
O3	0.95934 (19)	0.43317 (6)	0.37715 (5)	0.0292 (3)
O4	1.2004 (2)	0.54672 (6)	0.41831 (5)	0.0378 (3)
O5	0.8992 (2)	0.62220 (6)	0.51530 (6)	0.0466 (4)
O6	0.6738 (3)	0.56835 (7)	0.58258 (7)	0.0740 (5)
C1	0.6152 (3)	0.47463 (8)	0.51400 (7)	0.0272 (4)
H1	0.5074	0.5071	0.4928	0.033*
C2	0.7282 (3)	0.42758 (8)	0.46724 (7)	0.0236 (4)
H2	0.6151	0.4183	0.4336	0.028*
C3	0.9571 (3)	0.45218 (8)	0.44034 (7)	0.0238 (4)
H3	1.0897	0.4294	0.4618	0.029*
C4	0.9824 (3)	0.52964 (8)	0.44541 (7)	0.0283 (4)
H4	0.8540	0.5523	0.4221	0.034*
C5	0.9715 (3)	0.55235 (8)	0.51178 (8)	0.0312 (4)
H5	1.1290	0.5474	0.5308	0.037*
C6	0.7905 (3)	0.51494 (8)	0.55080 (7)	0.0340 (5)
H6	0.8707	0.4840	0.5804	0.041*
C7	0.5768 (3)	0.35928 (9)	0.54339 (8)	0.0280 (4)
C8	0.3869 (3)	0.31366 (9)	0.51884 (8)	0.0334 (5)
H8A	0.3430	0.3290	0.4779	0.040*
H8B	0.2507	0.3160	0.5457	0.040*
H8C	0.4433	0.2663	0.5169	0.040*
C9	0.6748 (4)	0.33430 (10)	0.60320 (8)	0.0426 (5)
H9A	0.7472	0.2893	0.5974	0.051*
H9B	0.5489	0.3305	0.6331	0.051*
H9C	0.7920	0.3668	0.6179	0.051*
C10	0.7840 (4)	0.63150 (9)	0.57212 (9)	0.0422 (5)
C11	0.9502 (4)	0.64793 (12)	0.62296 (10)	0.0726 (8)
H11A	0.8641	0.6511	0.6614	0.087*
H11B	1.0272	0.6918	0.6146	0.087*
H11C	1.0678	0.6117	0.6260	0.087*
C12	0.6001 (5)	0.68586 (13)	0.56399 (12)	0.0948 (10)
H12A	0.4924	0.6720	0.5316	0.114*
H12B	0.6746	0.7293	0.5529	0.114*
H12C	0.5138	0.6916	0.6021	0.114*
C13	1.2134 (5)	0.61290 (11)	0.39445 (12)	0.0847 (9)
H13A	1.0950	0.6185	0.3627	0.102*
H13B	1.3684	0.6204	0.3770	0.102*
H13C	1.1858	0.6463	0.4270	0.102*
C14	1.2537 (3)	0.45410 (8)	0.28376 (7)	0.0269 (4)
C15	1.0963 (3)	0.46542 (9)	0.23665 (8)	0.0326 (5)
H15	0.9543	0.4404	0.2357	0.039*
C16	1.1437 (3)	0.51273 (9)	0.19096 (8)	0.0387 (5)
H16	1.0342	0.5204	0.1593	0.046*
C17	1.3503 (4)	0.54825 (9)	0.19213 (8)	0.0403 (5)
H17	1.3831	0.5808	0.1611	0.048*
C18	1.5097 (4)	0.53726 (10)	0.23760 (9)	0.0448 (5)
H18	1.6523	0.5620	0.2379	0.054*
C19	1.4624 (3)	0.48964 (9)	0.28354 (9)	0.0376 (5)
H19	1.5740	0.4817	0.3147	0.045*
C20	1.0411 (3)	0.32695 (9)	0.30656 (7)	0.0278 (4)
C21	1.1526 (3)	0.29412 (9)	0.25831 (8)	0.0358 (5)
H21	1.2990	0.3105	0.2444	0.043*
C22	1.0508 (4)	0.23752 (10)	0.23049 (9)	0.0481 (6)
H22	1.1287	0.2154	0.1978	0.058*
C23	0.8384 (4)	0.21333 (10)	0.24998 (9)	0.0482 (6)
H23	0.7695	0.1747	0.2308	0.058*
C24	0.7259 (4)	0.24553 (10)	0.29751 (9)	0.0450 (5)
H24	0.5790	0.2291	0.3111	0.054*
C25	0.8273 (3)	0.30208 (9)	0.32560 (8)	0.0356 (5)
H25	0.7486	0.3239	0.3583	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0267 (2)	0.0313 (3)	0.0234 (2)	0.0034 (2)	0.0010 (2)	0.0014 (2)
O1	0.0364 (7)	0.0264 (7)	0.0359 (8)	−0.0029 (6)	0.0140 (6)	−0.0044 (6)
O2	0.0314 (7)	0.0236 (7)	0.0377 (7)	0.0024 (5)	0.0078 (6)	0.0023 (6)
O3	0.0280 (7)	0.0388 (8)	0.0207 (7)	0.0046 (6)	−0.0008 (6)	−0.0009 (6)
O4	0.0350 (7)	0.0360 (8)	0.0425 (7)	−0.0038 (7)	0.0067 (7)	0.0098 (6)
O5	0.0649 (10)	0.0220 (7)	0.0529 (9)	−0.0018 (7)	0.0181 (8)	−0.0041 (6)
O6	0.0949 (12)	0.0474 (10)	0.0798 (11)	−0.0350 (10)	0.0539 (10)	−0.0384 (9)
C1	0.0289 (10)	0.0241 (10)	0.0285 (10)	0.0028 (9)	0.0035 (8)	0.0035 (8)
C2	0.0247 (10)	0.0238 (9)	0.0223 (9)	0.0022 (8)	−0.0048 (8)	−0.0012 (8)
C3	0.0247 (10)	0.0285 (10)	0.0181 (9)	0.0037 (8)	−0.0020 (8)	−0.0007 (8)
C4	0.0246 (10)	0.0271 (11)	0.0333 (11)	0.0019 (9)	0.0004 (9)	0.0053 (8)
C5	0.0312 (10)	0.0258 (10)	0.0366 (11)	0.0022 (9)	−0.0021 (9)	−0.0044 (9)
C6	0.0474 (12)	0.0266 (10)	0.0279 (10)	−0.0036 (10)	0.0041 (10)	−0.0055 (8)
C7	0.0297 (10)	0.0257 (11)	0.0287 (11)	−0.0004 (9)	0.0039 (9)	−0.0014 (8)
C8	0.0308 (11)	0.0295 (11)	0.0399 (11)	0.0004 (9)	−0.0016 (9)	−0.0014 (9)
C9	0.0498 (13)	0.0412 (12)	0.0368 (12)	−0.0115 (11)	−0.0054 (11)	0.0072 (9)
C10	0.0440 (12)	0.0295 (12)	0.0532 (13)	−0.0019 (11)	0.0085 (11)	−0.0143 (10)
C11	0.0729 (17)	0.0705 (18)	0.0743 (17)	−0.0014 (15)	−0.0027 (15)	−0.0349 (14)
C12	0.100 (2)	0.081 (2)	0.104 (2)	0.0426 (17)	−0.0091 (18)	−0.0379 (17)
C13	0.0898 (19)	0.0525 (16)	0.112 (2)	0.0014 (15)	0.0489 (17)	0.0412 (14)
C14	0.0270 (11)	0.0298 (10)	0.0238 (9)	0.0038 (8)	0.0032 (8)	−0.0017 (8)
C15	0.0319 (11)	0.0315 (11)	0.0345 (11)	−0.0071 (9)	−0.0026 (9)	0.0035 (9)
C16	0.0476 (14)	0.0363 (12)	0.0322 (11)	−0.0015 (11)	−0.0052 (10)	0.0063 (9)
C17	0.0479 (14)	0.0340 (12)	0.0389 (12)	0.0062 (11)	0.0159 (11)	0.0088 (10)
C18	0.0340 (12)	0.0441 (13)	0.0562 (14)	−0.0092 (11)	0.0125 (11)	0.0037 (11)
C19	0.0296 (11)	0.0451 (13)	0.0379 (11)	−0.0029 (10)	0.0002 (10)	0.0027 (10)
C20	0.0346 (11)	0.0262 (10)	0.0225 (10)	0.0036 (9)	−0.0025 (9)	0.0039 (8)
C21	0.0414 (12)	0.0360 (12)	0.0299 (10)	0.0002 (10)	0.0057 (10)	0.0024 (9)
C22	0.0734 (16)	0.0418 (13)	0.0290 (12)	0.0014 (13)	0.0013 (12)	−0.0056 (10)
C23	0.0691 (17)	0.0368 (13)	0.0387 (12)	−0.0114 (13)	−0.0133 (13)	0.0023 (10)
C24	0.0416 (13)	0.0415 (13)	0.0520 (13)	−0.0105 (11)	−0.0083 (11)	0.0096 (11)
C25	0.0356 (11)	0.0330 (11)	0.0383 (11)	0.0013 (10)	0.0005 (10)	0.0030 (9)

Geometric parameters (Å, º)

P1—O3	1.6541 (12)	C10—C11	1.504 (3)
P1—C14	1.8286 (17)	C10—C12	1.507 (3)
P1—C20	1.8329 (18)	C11—H11A	0.9800
O1—C1	1.4299 (18)	C11—H11B	0.9800
O1—C7	1.4567 (19)	C11—H11C	0.9800
O2—C7	1.4265 (19)	C12—H12A	0.9800
O2—C2	1.4350 (18)	C12—H12B	0.9800
O3—C3	1.4372 (18)	C12—H12C	0.9800
O4—C13	1.396 (2)	C13—H13A	0.9800
O4—C4	1.425 (2)	C13—H13B	0.9800
O5—C10	1.425 (2)	C13—H13C	0.9800
O5—C5	1.4269 (19)	C14—C19	1.384 (2)
O6—C10	1.404 (2)	C14—C15	1.391 (2)
O6—C6	1.422 (2)	C15—C16	1.391 (2)
C1—C6	1.512 (2)	C15—H15	0.9500
C1—C2	1.523 (2)	C16—C17	1.373 (2)
C1—H1	1.0000	C16—H16	0.9500
C2—C3	1.518 (2)	C17—C18	1.371 (3)
C2—H2	1.0000	C17—H17	0.9500
C3—C4	1.523 (2)	C18—C19	1.399 (2)
C3—H3	1.0000	C18—H18	0.9500
C4—C5	1.526 (2)	C19—H19	0.9500
C4—H4	1.0000	C20—C25	1.384 (2)
C5—C6	1.532 (2)	C20—C21	1.394 (2)
C5—H5	1.0000	C21—C22	1.391 (2)
C6—H6	1.0000	C21—H21	0.9500
C7—C8	1.507 (2)	C22—C23	1.376 (3)
C7—C9	1.510 (2)	C22—H22	0.9500
C8—H8A	0.9800	C23—C24	1.379 (3)
C8—H8B	0.9800	C23—H23	0.9500
C8—H8C	0.9800	C24—C25	1.392 (2)
C9—H9A	0.9800	C24—H24	0.9500
C9—H9B	0.9800	C25—H25	0.9500
C9—H9C	0.9800
O3—P1—C14	100.97 (7)	H9B—C9—H9C	109.5
O3—P1—C20	97.85 (7)	O6—C10—O5	103.92 (13)
C14—P1—C20	100.25 (8)	O6—C10—C11	110.56 (18)
C1—O1—C7	109.14 (11)	O5—C10—C11	112.56 (17)
C7—O2—C2	107.60 (11)	O6—C10—C12	108.80 (18)
C3—O3—P1	120.41 (10)	O5—C10—C12	108.12 (18)
C13—O4—C4	114.84 (15)	C11—C10—C12	112.47 (17)
C10—O5—C5	107.71 (13)	C10—C11—H11A	109.5
C10—O6—C6	110.55 (14)	C10—C11—H11B	109.5
O1—C1—C6	112.80 (13)	H11A—C11—H11B	109.5
O1—C1—C2	102.78 (12)	C10—C11—H11C	109.5
C6—C1—C2	113.03 (14)	H11A—C11—H11C	109.5
O1—C1—H1	109.3	H11B—C11—H11C	109.5
C6—C1—H1	109.3	C10—C12—H12A	109.5
C2—C1—H1	109.3	C10—C12—H12B	109.5
O2—C2—C3	109.95 (12)	H12A—C12—H12B	109.5
O2—C2—C1	102.40 (12)	C10—C12—H12C	109.5
C3—C2—C1	116.14 (14)	H12A—C12—H12C	109.5
O2—C2—H2	109.4	H12B—C12—H12C	109.5
C3—C2—H2	109.4	O4—C13—H13A	109.5
C1—C2—H2	109.4	O4—C13—H13B	109.5
O3—C3—C2	107.60 (13)	H13A—C13—H13B	109.5
O3—C3—C4	109.03 (13)	O4—C13—H13C	109.5
C2—C3—C4	111.60 (14)	H13A—C13—H13C	109.5
O3—C3—H3	109.5	H13B—C13—H13C	109.5
C2—C3—H3	109.5	C19—C14—C15	118.64 (16)
C4—C3—H3	109.5	C19—C14—P1	118.79 (13)
O4—C4—C3	106.59 (13)	C15—C14—P1	122.54 (13)
O4—C4—C5	111.58 (14)	C16—C15—C14	121.05 (17)
C3—C4—C5	110.76 (14)	C16—C15—H15	119.5
O4—C4—H4	109.3	C14—C15—H15	119.5
C3—C4—H4	109.3	C17—C16—C15	119.35 (18)
C5—C4—H4	109.3	C17—C16—H16	120.3
O5—C5—C4	109.96 (14)	C15—C16—H16	120.3
O5—C5—C6	103.17 (13)	C18—C17—C16	120.70 (18)
C4—C5—C6	115.12 (14)	C18—C17—H17	119.7
O5—C5—H5	109.5	C16—C17—H17	119.7
C4—C5—H5	109.5	C17—C18—C19	120.02 (18)
C6—C5—H5	109.5	C17—C18—H18	120.0
O6—C6—C1	109.32 (15)	C19—C18—H18	120.0
O6—C6—C5	104.17 (13)	C14—C19—C18	120.23 (18)
C1—C6—C5	113.57 (13)	C14—C19—H19	119.9
O6—C6—H6	109.9	C18—C19—H19	119.9
C1—C6—H6	109.9	C25—C20—C21	118.40 (17)
C5—C6—H6	109.9	C25—C20—P1	121.93 (14)
O2—C7—O1	105.46 (12)	C21—C20—P1	119.43 (14)
O2—C7—C8	111.77 (13)	C22—C21—C20	120.42 (19)
O1—C7—C8	108.19 (13)	C22—C21—H21	119.8
O2—C7—C9	107.98 (14)	C20—C21—H21	119.8
O1—C7—C9	110.22 (14)	C23—C22—C21	120.5 (2)
C8—C7—C9	112.97 (15)	C23—C22—H22	119.7
C7—C8—H8A	109.5	C21—C22—H22	119.7
C7—C8—H8B	109.5	C22—C23—C24	119.60 (19)
H8A—C8—H8B	109.5	C22—C23—H23	120.2
C7—C8—H8C	109.5	C24—C23—H23	120.2
H8A—C8—H8C	109.5	C23—C24—C25	120.10 (19)
H8B—C8—H8C	109.5	C23—C24—H24	119.9
C7—C9—H9A	109.5	C25—C24—H24	119.9
C7—C9—H9B	109.5	C20—C25—C24	120.95 (18)
H9A—C9—H9B	109.5	C20—C25—H25	119.5
C7—C9—H9C	109.5	C24—C25—H25	119.5
H9A—C9—H9C	109.5
C14—P1—O3—C3	−124.59 (12)	C4—C5—C6—C1	−14.1 (2)
C20—P1—O3—C3	133.30 (12)	C2—O2—C7—O1	−21.61 (15)
C7—O1—C1—C6	−100.61 (15)	C2—O2—C7—C8	95.73 (15)
C7—O1—C1—C2	21.43 (16)	C2—O2—C7—C9	−139.44 (13)
C7—O2—C2—C3	158.37 (13)	C1—O1—C7—O2	−1.05 (16)
C7—O2—C2—C1	34.34 (15)	C1—O1—C7—C8	−120.77 (14)
O1—C1—C2—O2	−33.59 (15)	C1—O1—C7—C9	115.26 (15)
C6—C1—C2—O2	88.30 (15)	C6—O6—C10—O5	24.5 (2)
O1—C1—C2—C3	−153.39 (13)	C6—O6—C10—C11	−96.48 (19)
C6—C1—C2—C3	−31.50 (19)	C6—O6—C10—C12	139.53 (18)
P1—O3—C3—C2	−133.05 (11)	C5—O5—C10—O6	−33.38 (19)
P1—O3—C3—C4	105.76 (13)	C5—O5—C10—C11	86.28 (18)
O2—C2—C3—O3	101.96 (14)	C5—O5—C10—C12	−148.88 (17)
C1—C2—C3—O3	−142.41 (14)	O3—P1—C14—C19	116.78 (14)
O2—C2—C3—C4	−138.47 (13)	C20—P1—C14—C19	−143.06 (14)
C1—C2—C3—C4	−22.84 (19)	O3—P1—C14—C15	−61.31 (15)
C13—O4—C4—C3	153.18 (17)	C20—P1—C14—C15	38.85 (16)
C13—O4—C4—C5	−85.8 (2)	C19—C14—C15—C16	−1.7 (3)
O3—C3—C4—O4	−60.63 (16)	P1—C14—C15—C16	176.40 (13)
C2—C3—C4—O4	−179.35 (12)	C14—C15—C16—C17	0.7 (3)
O3—C3—C4—C5	177.82 (13)	C15—C16—C17—C18	0.3 (3)
C2—C3—C4—C5	59.10 (18)	C16—C17—C18—C19	−0.2 (3)
C10—O5—C5—C4	151.94 (15)	C15—C14—C19—C18	1.8 (3)
C10—O5—C5—C6	28.65 (17)	P1—C14—C19—C18	−176.41 (14)
O4—C4—C5—O5	85.32 (17)	C17—C18—C19—C14	−0.8 (3)
C3—C4—C5—O5	−156.11 (13)	O3—P1—C20—C25	−26.30 (15)
O4—C4—C5—C6	−158.69 (14)	C14—P1—C20—C25	−129.01 (14)
C3—C4—C5—C6	−40.1 (2)	O3—P1—C20—C21	159.38 (13)
C10—O6—C6—C1	−128.73 (16)	C14—P1—C20—C21	56.67 (15)
C10—O6—C6—C5	−7.0 (2)	C25—C20—C21—C22	−0.4 (3)
O1—C1—C6—O6	−77.50 (17)	P1—C20—C21—C22	174.14 (14)
C2—C1—C6—O6	166.43 (14)	C20—C21—C22—C23	0.3 (3)
O1—C1—C6—C5	166.65 (13)	C21—C22—C23—C24	−0.1 (3)
C2—C1—C6—C5	50.59 (19)	C22—C23—C24—C25	−0.1 (3)
O5—C5—C6—O6	−13.12 (18)	C21—C20—C25—C24	0.2 (3)
C4—C5—C6—O6	−132.92 (16)	P1—C20—C25—C24	−174.16 (13)
O5—C5—C6—C1	105.72 (16)	C23—C24—C25—C20	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4^i	1.00	2.53	3.474 (2)	158
C16—H16···O1^ii	0.95	2.60	3.377 (2)	139
C9—H9B···Cg1^iii	0.98	2.84	3.573 (2)	133
C16—H16···O6^ii	0.95	2.70	3.391 (2)	131
C13—H13C···O5	0.98	2.59	3.215 (3)	122
C25—H25···O3	0.95	2.49	2.899 (2)	106

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