(R)-(6,6′-Dihydroxybiphenyl-2,2′-diyl)bis(diphenylphosphine oxide) methanol solvate

The title compound, C₃₆H₂₈O₄P₂·CH₄O, was synthesized directly from the methoxy analogue. The crystal structure shows that one OH group interacts with an O atom of a phosphine oxide group in an adjacent mol­ecule, while the other OH group complexes with the methanol solvent molecule via intermolecular hydrogen bonds. An O atom of one phosphine oxide group interacts with the hydroxy H atom of methanol via a hydrogen bond. There are intra- and intermolecular π–π interactions between the phenyl rings. All these interactions result in the formation of supramolecular chiral parallelogram channels via self-assembly.

S1. Comment

Chiral bidentate phosphines are among the most important auxiliaries in enantioselective homogeneous catalysis. The atropisomeric diphosphine ligands, such as Noyori's BINAP (Noyori, 1989; Noyori & Takaya, 1990) and Schmid's BIPHEP classes (Schmid et al., 1988, 1991, 1996) have been widely applied in asymmetric catalysis, especially in hydrogenation, and excellent results have been achieved.

The theories of supramolecular chemistry and crystal engineering inspire the design of microporous layers employing self-assembly of molecular subunits (tectons), driven by non-covalent interactions as the synthetic tool (Moulton & Zaworotko, 2001). In this paper, the synthesis of the title compound, (I), a derivative of (R)-(6,6'-methoxybiphenyl-2,2'-diyl)bis(diphenylphosphine oxide), MeO-BIPHEPO, is described. The compound can be used as a building block for the synthesis of new diphosphine ligands. \sch

In the crystal of (I), there are three kinds of hydrogen bonds (Fig. 1). In the first, the O1—H1 group of one molecule of (I) interacts with atom O4 of a phosphine oxide group in an adjacent molecule, with O1—H1···O4A 2.648 Å. In the second, the O2—H2B group in (I) with atom O5B in the CH₃OH solvate, with O2—H2B···O5B 2.669 Å. In the third, atom O3 of the phosphine oxide group interacts with H5—O5 in the CH₃OH solvate, with O3···H5—O5 2.656 Å.

In addition to these hydrogen bonds, there are intra- and intermolecular π–π interactions between the phenyl rings of (I). The distance between the centroid of ring C1—C6 (CgA) and that of ring C25—C30 (CgB) is 3.568 Å, and the angle between the two ring planes of this intramolecular π–π stacking interaction is 13.7°. The phenyl rings C7—C12 (CgC) and C31—C36 (CgD) are also involved in a weak intramolecular π–π stacking interaction, with CgC···CgD 4.912 Å and with the angle between the two planes being 179.9°. There are also π–π stacking interactions between the phenyl rings of the Ph₂PO groups and the equivalent phenyl rings in an adjacent molecule. The shortest of these has a distance between the two symmetry-related phenyl rings of 4.339 Å and an angle of 162.1° (Table 1 and Fig. 1).

Through these rich hydrogen-bonding interactions, every molecule of (I) is linked to four adjacent molecules. Furthermore, a three-dimensional supramolecular chiral parallelogram channel (cavity demension ca 9.2 × 6.7 Ų) along the crystallographic a axis, having the empirical formula C₃₆H₂₈O₄P₂·CH₃OH, is constructed via self-assembly (Figs. 2 and 3). These channels are divided into mini compartments by the phenyl groups linked to the P atoms. This result suggests a novel approach to the design of chiral microporous structures containing P atoms.

S2. Experimental

The preparation of (I) proceeded as follows. A solution of (R)-(6,6'-methoxybiphenyl-2,2'-diyl)bis(diphenylphosphine oxide) (1 g, 1.6 mmol) in CH₂Cl₂ (20 ml) was cooled to 195 K. To this solution, BBr₃ (1.6 g, 6.4 mmol) was added via a syringe over 30 min. The mixture was stirred at 195 K for 1 hr, and then slowly warmed to room temperature and reacted overnight. After cooling the mixture to 273 K, water was added slowly and the aqueous layer was removed via a cannula. The organic layer was mixed with methanol and dichloromethane (Ratio?). The resulting solution was dried over Na₂SO₄ and evaporated to dryness to give the raw product, which was purified by silica-gel column chromatography with CHCl₃ and CH₃OH (Ratio?). Spectroscopic analysis: ¹H NMR (DMSO, 500 MHz, δ, p.p.m.): 6.5–6.7 (dd, 2H, J = 7.5 Hz,), 6.6–6.8 (d, 2H, J = 8 Hz), 7.0–7.1 (m, 2H), 7.3–7.7 (m, 20H); ³¹P NMR (DMSO, δ, p.p.m.): 29.2; high-resolution MS: 586.1439; calculated for C₃₆H₂₈P₂O₄: 586.1463.

S3. Refinement

H atoms were placed in their geometrically calculated positions and included in the final refinement in the riding model approximation, with O—H distances of 0.82 Å and C—H distances in the range 0.93–0.98 Å. Is this added text correct?

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL-NT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.

Figures

	Fig. 1. A view of the molecular structure of (I), with displacement ellipsoids at the 30% probability level. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing of the crystal of (I) along the a axis. For clarity, the four phenyl rings connected to the P atoms have been omitted.
	Fig. 3. The packing of the crystal of (I) along the (111) direction. For clarity, the four phenyl rings connected to the P atoms have been omitted.

(R)-(6,6'-dihydroxybiphenyl-2,2'-diyl)bis(diphenylphosphine oxide)

Crystal data

C36H28O4P2·CH4O	Dx = 1.326 Mg m^−3
Mr = 618.57	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 5948 reflections
a = 9.9351 (16) Å	θ = 1.0–27.5°
b = 11.1490 (17) Å	µ = 0.18 mm^−1
c = 27.977 (4) Å	T = 294 K
V = 3098.9 (8) Å^3	Plate, colourless
Z = 4	0.26 × 0.24 × 0.10 mm
F(000) = 1296

Data collection

Bruker Model CCD area-detector diffractometer	7141 independent reflections
Radiation source: fine-focus sealed tube	3814 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
ϕ and ω scans	θmax = 27.5°, θmin = 1.5°
Absorption correction: empirical (using intensity measurements) (SAINT; Siemens, 1995)	h = −12→12
Tmin = 0.954, Tmax = 0.982	k = −14→10
21252 measured reflections	l = −35→36

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)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.05P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.83	(Δ/σ)max = 0.001
7141 reflections	Δρmax = 0.25 e Å^−3
400 parameters	Δρmin = −0.24 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 3113 Friedel pairs Is this correct
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.06 (8)

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
P1	0.28454 (7)	0.93328 (7)	0.80954 (2)	0.03429 (18)
P2	0.52558 (8)	1.07782 (8)	0.95518 (2)	0.0418 (2)
O1	0.24160 (19)	1.27489 (17)	0.93534 (6)	0.0511 (6)
H1	0.1957	1.2943	0.9584	0.077*
O2	0.30313 (19)	1.25192 (18)	0.79898 (6)	0.0506 (5)
H2B	0.3157	1.3067	0.7799	0.076*
O3	0.41916 (19)	0.97721 (16)	0.79465 (6)	0.0423 (5)
O4	0.5903 (2)	1.15499 (18)	0.99192 (6)	0.0571 (6)
C1	0.1984 (3)	1.0284 (2)	0.85186 (8)	0.0298 (6)
C2	0.0626 (3)	1.0025 (2)	0.85959 (9)	0.0374 (7)
H2A	0.0209	0.9433	0.8415	0.045*
C3	−0.0106 (3)	1.0634 (3)	0.89371 (8)	0.0423 (7)
H3A	−0.1004	1.0439	0.8988	0.051*
C4	0.0488 (3)	1.1532 (3)	0.92028 (9)	0.0409 (7)
H4A	−0.0001	1.1931	0.9437	0.049*
C5	0.1807 (3)	1.1831 (2)	0.91184 (9)	0.0351 (7)
C6	0.2595 (2)	1.1215 (2)	0.87798 (8)	0.0273 (6)
C7	0.3981 (3)	1.1681 (2)	0.86871 (9)	0.0308 (7)
C8	0.4137 (3)	1.2389 (2)	0.82709 (9)	0.0317 (7)
C9	0.5337 (3)	1.2933 (2)	0.81631 (9)	0.0394 (7)
H9A	0.5414	1.3395	0.7888	0.047*
C10	0.6433 (3)	1.2796 (3)	0.84625 (10)	0.0452 (8)
H10A	0.7249	1.3160	0.8389	0.054*
C11	0.6305 (3)	1.2118 (2)	0.88690 (9)	0.0410 (8)
H11A	0.7046	1.2021	0.9068	0.049*
C12	0.5089 (3)	1.1568 (2)	0.89915 (8)	0.0330 (7)
C13	0.1708 (3)	0.9193 (3)	0.75935 (8)	0.0356 (7)
C14	0.1599 (3)	1.0161 (3)	0.72887 (10)	0.0521 (9)
H14A	0.2087	1.0857	0.7350	0.063*
C15	0.0765 (4)	1.0103 (3)	0.68903 (11)	0.0634 (10)
H15A	0.0688	1.0761	0.6688	0.076*
C16	0.0056 (3)	0.9076 (3)	0.67959 (10)	0.0591 (9)
H16A	−0.0494	0.9034	0.6527	0.071*
C17	0.0155 (3)	0.8117 (3)	0.70946 (10)	0.0545 (9)
H17A	−0.0333	0.7423	0.7030	0.065*
C18	0.0985 (3)	0.8169 (3)	0.74974 (10)	0.0448 (8)
H18A	0.1049	0.7511	0.7700	0.054*
C19	0.2971 (3)	0.7846 (2)	0.83587 (9)	0.0422 (8)
C20	0.2041 (3)	0.7330 (3)	0.86620 (10)	0.0510 (8)
H20A	0.1272	0.7759	0.8744	0.061*
C21	0.2220 (4)	0.6202 (3)	0.88450 (11)	0.0635 (10)
H21A	0.1583	0.5880	0.9052	0.076*
C22	0.3334 (4)	0.5547 (3)	0.87240 (13)	0.0793 (12)
H22A	0.3446	0.4775	0.8843	0.095*
C23	0.4277 (4)	0.6030 (3)	0.84282 (14)	0.0826 (12)
H23A	0.5044	0.5593	0.8350	0.099*
C24	0.4098 (3)	0.7183 (3)	0.82406 (11)	0.0617 (9)
H24A	0.4741	0.7505	0.8035	0.074*
C25	0.3697 (3)	1.0198 (3)	0.97765 (9)	0.0408 (8)
C26	0.3126 (3)	1.0775 (3)	1.01647 (10)	0.0617 (9)
H26A	0.3554	1.1433	1.0301	0.074*
C27	0.1912 (4)	1.0371 (3)	1.03490 (11)	0.0724 (11)
H27A	0.1527	1.0763	1.0609	0.087*
C28	0.1276 (3)	0.9405 (3)	1.01538 (11)	0.0631 (10)
H28A	0.0461	0.9141	1.0279	0.076*
C29	0.1843 (3)	0.8829 (3)	0.97741 (10)	0.0527 (9)
H29A	0.1410	0.8170	0.9640	0.063*
C30	0.3048 (3)	0.9212 (3)	0.95875 (9)	0.0423 (7)
H30A	0.3429	0.8804	0.9331	0.051*
C31	0.6339 (3)	0.9540 (2)	0.94028 (9)	0.0398 (7)
C32	0.6311 (3)	0.8975 (3)	0.89636 (11)	0.0562 (9)
H32A	0.5686	0.9216	0.8735	0.067*
C33	0.7196 (4)	0.8060 (3)	0.88585 (12)	0.0695 (10)
H33A	0.7164	0.7686	0.8562	0.083*
C34	0.8122 (4)	0.7701 (3)	0.91921 (14)	0.0705 (10)
H34A	0.8711	0.7077	0.9124	0.085*
C35	0.8176 (3)	0.8258 (3)	0.96211 (13)	0.0679 (11)
H35A	0.8817	0.8022	0.9844	0.081*
C36	0.7292 (3)	0.9175 (3)	0.97322 (10)	0.0546 (8)
H36A	0.7338	0.9546	1.0029	0.066*
O5	0.6678 (2)	0.9158 (2)	0.76975 (8)	0.0618 (6)
H5	0.5917	0.9376	0.7771	0.150*
C37	0.7566 (4)	1.0118 (3)	0.77421 (12)	0.0755 (11)
H37A	0.7396	1.0661	0.7483	0.091*
H37B	0.8488	0.9803	0.7711	0.120*
H37C	0.7652	1.0581	0.8038	0.120*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0323 (4)	0.0352 (4)	0.0353 (4)	0.0000 (4)	0.0001 (3)	−0.0050 (4)
P2	0.0446 (5)	0.0492 (5)	0.0316 (4)	−0.0078 (4)	−0.0057 (4)	−0.0040 (4)
O1	0.0561 (15)	0.0477 (13)	0.0494 (13)	−0.0101 (11)	0.0190 (10)	−0.0252 (11)
O2	0.0407 (13)	0.0553 (14)	0.0558 (13)	−0.0060 (11)	−0.0063 (11)	0.0220 (11)
O3	0.0302 (11)	0.0482 (13)	0.0485 (11)	0.0006 (9)	0.0052 (9)	−0.0118 (10)
O4	0.0619 (15)	0.0714 (15)	0.0382 (11)	−0.0172 (12)	−0.0132 (11)	−0.0136 (11)
C1	0.0277 (17)	0.0341 (16)	0.0275 (13)	−0.0016 (13)	0.0007 (13)	0.0016 (12)
C2	0.0317 (19)	0.0397 (18)	0.0409 (16)	−0.0041 (13)	−0.0036 (14)	−0.0046 (14)
C3	0.0288 (17)	0.053 (2)	0.0450 (16)	0.0005 (17)	0.0097 (14)	0.0022 (17)
C4	0.0350 (19)	0.044 (2)	0.0434 (17)	−0.0016 (15)	0.0104 (15)	−0.0048 (15)
C5	0.0385 (19)	0.0363 (18)	0.0305 (15)	−0.0021 (15)	0.0064 (14)	−0.0036 (14)
C6	0.0260 (16)	0.0303 (15)	0.0258 (14)	−0.0010 (12)	0.0023 (12)	0.0019 (12)
C7	0.0323 (18)	0.0309 (16)	0.0292 (15)	−0.0006 (13)	0.0051 (13)	−0.0078 (13)
C8	0.0300 (18)	0.0293 (16)	0.0359 (16)	−0.0008 (14)	−0.0002 (14)	−0.0046 (14)
C9	0.0394 (18)	0.0405 (18)	0.0383 (16)	−0.0038 (15)	0.0083 (16)	0.0042 (14)
C10	0.0373 (19)	0.048 (2)	0.0500 (18)	−0.0083 (16)	0.0076 (16)	−0.0084 (17)
C11	0.0330 (19)	0.049 (2)	0.0412 (17)	−0.0036 (15)	−0.0082 (14)	−0.0024 (16)
C12	0.0317 (18)	0.0352 (17)	0.0320 (14)	−0.0065 (14)	0.0002 (14)	−0.0063 (13)
C13	0.0318 (16)	0.0358 (16)	0.0391 (15)	−0.0008 (15)	0.0026 (13)	−0.0066 (16)
C14	0.063 (2)	0.042 (2)	0.0512 (19)	−0.0020 (17)	−0.0045 (18)	−0.0014 (17)
C15	0.075 (3)	0.063 (2)	0.051 (2)	0.009 (2)	−0.017 (2)	0.0053 (19)
C16	0.052 (2)	0.076 (3)	0.0493 (19)	0.012 (2)	−0.0189 (17)	−0.009 (2)
C17	0.042 (2)	0.064 (2)	0.057 (2)	−0.0043 (18)	−0.0075 (17)	−0.0146 (19)
C18	0.041 (2)	0.046 (2)	0.0475 (19)	−0.0011 (16)	0.0015 (16)	−0.0022 (16)
C19	0.045 (2)	0.0396 (18)	0.0424 (17)	0.0060 (17)	−0.0082 (15)	−0.0103 (15)
C20	0.063 (2)	0.041 (2)	0.0490 (18)	−0.0006 (18)	−0.0035 (18)	0.0039 (16)
C21	0.089 (3)	0.049 (2)	0.052 (2)	−0.012 (2)	−0.005 (2)	0.0049 (18)
C22	0.103 (4)	0.046 (3)	0.089 (3)	−0.008 (3)	−0.026 (3)	0.005 (2)
C23	0.074 (3)	0.049 (3)	0.125 (3)	0.026 (2)	−0.017 (3)	−0.005 (2)
C24	0.060 (3)	0.047 (2)	0.078 (2)	0.0075 (19)	0.000 (2)	−0.0014 (19)
C25	0.045 (2)	0.047 (2)	0.0305 (16)	−0.0049 (15)	−0.0062 (14)	−0.0007 (14)
C26	0.074 (3)	0.061 (2)	0.0499 (19)	−0.021 (2)	0.0144 (18)	−0.0167 (19)
C27	0.078 (3)	0.080 (3)	0.058 (2)	−0.012 (2)	0.023 (2)	−0.020 (2)
C28	0.056 (2)	0.072 (3)	0.061 (2)	−0.015 (2)	0.0128 (18)	0.000 (2)
C29	0.057 (2)	0.051 (2)	0.0507 (19)	−0.0099 (18)	−0.0035 (18)	−0.0016 (17)
C30	0.049 (2)	0.0412 (18)	0.0370 (15)	−0.0005 (17)	−0.0032 (15)	−0.0024 (16)
C31	0.0363 (18)	0.044 (2)	0.0388 (16)	−0.0051 (15)	−0.0059 (14)	0.0015 (15)
C32	0.054 (2)	0.055 (2)	0.059 (2)	0.0056 (18)	−0.0076 (17)	−0.0063 (18)
C33	0.071 (3)	0.059 (2)	0.079 (3)	0.007 (2)	0.001 (2)	−0.016 (2)
C34	0.056 (3)	0.054 (2)	0.101 (3)	0.0078 (19)	0.003 (2)	0.011 (2)
C35	0.048 (2)	0.078 (3)	0.077 (3)	−0.004 (2)	−0.013 (2)	0.027 (2)
C36	0.049 (2)	0.066 (2)	0.0490 (18)	−0.004 (2)	−0.0054 (16)	0.0135 (18)
O5	0.0444 (13)	0.0692 (15)	0.0719 (14)	0.0036 (13)	0.0100 (12)	−0.0297 (13)
C37	0.057 (3)	0.079 (3)	0.091 (3)	−0.009 (2)	0.002 (2)	−0.025 (2)

Geometric parameters (Å, º)

P1—O3	1.4839 (19)	C17—H17A	0.9300
P1—C1	1.805 (3)	C18—H18A	0.9300
P1—C13	1.809 (3)	C19—C20	1.381 (4)
P1—C19	1.818 (3)	C19—C24	1.382 (4)
P2—O4	1.4866 (18)	C20—C21	1.369 (4)
P2—C25	1.792 (3)	C20—H20A	0.9300
P2—C31	1.800 (3)	C21—C22	1.369 (4)
P2—C12	1.806 (3)	C21—H21A	0.9300
O1—C5	1.359 (3)	C22—C23	1.362 (5)
O1—H1	0.8200	C22—H22A	0.9300
O2—C8	1.359 (3)	C23—C24	1.400 (4)
O2—H2B	0.8200	C23—H23A	0.9300
C1—C2	1.397 (3)	C24—H24A	0.9300
C1—C6	1.407 (3)	C25—C30	1.379 (4)
C2—C3	1.379 (3)	C25—C26	1.384 (4)
C2—H2A	0.9300	C26—C27	1.387 (4)
C3—C4	1.379 (3)	C26—H26A	0.9300
C3—H3A	0.9300	C27—C28	1.362 (4)
C4—C5	1.373 (4)	C27—H27A	0.9300
C4—H4A	0.9300	C28—C29	1.363 (4)
C5—C6	1.407 (3)	C28—H28A	0.9300
C6—C7	1.495 (3)	C29—C30	1.375 (4)
C7—C12	1.397 (3)	C29—H29A	0.9300
C7—C8	1.415 (3)	C30—H30A	0.9300
C8—C9	1.371 (3)	C31—C32	1.381 (3)
C9—C10	1.382 (4)	C31—C36	1.382 (3)
C9—H9A	0.9300	C32—C33	1.379 (4)
C10—C11	1.372 (3)	C32—H32A	0.9300
C10—H10A	0.9300	C33—C34	1.370 (4)
C11—C12	1.397 (3)	C33—H33A	0.9300
C11—H11A	0.9300	C34—C35	1.353 (4)
C13—C18	1.376 (3)	C34—H34A	0.9300
C13—C14	1.380 (3)	C35—C36	1.383 (4)
C14—C15	1.391 (4)	C35—H35A	0.9300
C14—H14A	0.9300	C36—H36A	0.9300
C15—C16	1.370 (4)	O5—C37	1.393 (3)
C15—H15A	0.9300	O5—H5	0.8200
C16—C17	1.361 (4)	C37—H37A	0.9599
C16—H16A	0.9300	C37—H37B	0.9845
C17—C18	1.398 (4)	C37—H37C	0.9802
O3—P1—C1	114.67 (12)	C13—C18—C17	120.0 (3)
O3—P1—C13	111.93 (11)	C13—C18—H18A	120.0
C1—P1—C13	105.29 (12)	C17—C18—H18A	120.0
O3—P1—C19	110.66 (13)	C20—C19—C24	117.8 (3)
C1—P1—C19	107.59 (12)	C20—C19—P1	125.7 (2)
C13—P1—C19	106.20 (13)	C24—C19—P1	116.5 (2)
O4—P2—C25	109.90 (12)	C21—C20—C19	121.7 (3)
O4—P2—C31	110.21 (13)	C21—C20—H20A	119.1
C25—P2—C31	108.72 (13)	C19—C20—H20A	119.1
O4—P2—C12	110.95 (12)	C22—C21—C20	120.2 (3)
C25—P2—C12	113.65 (12)	C22—C21—H21A	119.9
C31—P2—C12	103.19 (12)	C20—C21—H21A	119.9
C5—O1—H1	109.5	C23—C22—C21	119.7 (4)
C8—O2—H2B	109.5	C23—C22—H22A	120.1
C2—C1—C6	119.2 (2)	C21—C22—H22A	120.1
C2—C1—P1	116.0 (2)	C22—C23—C24	120.3 (4)
C6—C1—P1	124.7 (2)	C22—C23—H23A	119.9
C3—C2—C1	121.0 (3)	C24—C23—H23A	119.9
C3—C2—H2A	119.5	C19—C24—C23	120.3 (3)
C1—C2—H2A	119.5	C19—C24—H24A	119.9
C4—C3—C2	120.3 (3)	C23—C24—H24A	119.9
C4—C3—H3A	119.8	C30—C25—C26	118.7 (3)
C2—C3—H3A	119.8	C30—C25—P2	123.9 (2)
C5—C4—C3	119.5 (3)	C26—C25—P2	117.5 (2)
C5—C4—H4A	120.3	C25—C26—C27	119.8 (3)
C3—C4—H4A	120.3	C25—C26—H26A	120.1
O1—C5—C4	121.6 (2)	C27—C26—H26A	120.1
O1—C5—C6	116.5 (2)	C28—C27—C26	120.7 (3)
C4—C5—C6	121.9 (3)	C28—C27—H27A	119.6
C1—C6—C5	118.0 (2)	C26—C27—H27A	119.6
C1—C6—C7	124.3 (2)	C27—C28—C29	119.6 (3)
C5—C6—C7	117.3 (2)	C27—C28—H28A	120.2
C12—C7—C8	117.7 (2)	C29—C28—H28A	120.2
C12—C7—C6	126.1 (2)	C28—C29—C30	120.6 (3)
C8—C7—C6	116.0 (2)	C28—C29—H29A	119.7
O2—C8—C9	121.9 (2)	C30—C29—H29A	119.7
O2—C8—C7	116.6 (2)	C29—C30—C25	120.6 (3)
C9—C8—C7	121.5 (2)	C29—C30—H30A	119.7
C8—C9—C10	120.2 (3)	C25—C30—H30A	119.7
C8—C9—H9A	119.9	C32—C31—C36	118.2 (3)
C10—C9—H9A	119.9	C32—C31—P2	122.9 (2)
C11—C10—C9	119.4 (3)	C36—C31—P2	118.7 (2)
C11—C10—H10A	120.3	C33—C32—C31	120.9 (3)
C9—C10—H10A	120.3	C33—C32—H32A	119.5
C10—C11—C12	121.7 (3)	C31—C32—H32A	119.5
C10—C11—H11A	119.2	C34—C33—C32	119.9 (3)
C12—C11—H11A	119.2	C34—C33—H33A	120.0
C11—C12—C7	119.5 (2)	C32—C33—H33A	120.0
C11—C12—P2	110.3 (2)	C35—C34—C33	119.8 (3)
C7—C12—P2	130.2 (2)	C35—C34—H34A	120.1
C18—C13—C14	119.2 (2)	C33—C34—H34A	120.1
C18—C13—P1	123.3 (2)	C34—C35—C36	120.9 (3)
C14—C13—P1	117.5 (2)	C34—C35—H35A	119.6
C13—C14—C15	120.4 (3)	C36—C35—H35A	119.6
C13—C14—H14A	119.8	C31—C36—C35	120.2 (3)
C15—C14—H14A	119.8	C31—C36—H36A	119.9
C16—C15—C14	120.0 (3)	C35—C36—H36A	119.9
C16—C15—H15A	120.0	C37—O5—H5	109.5
C14—C15—H15A	120.0	O5—C37—H37A	107.7
C17—C16—C15	120.1 (3)	O5—C37—H37B	107.9
C17—C16—H16A	120.0	H37A—C37—H37B	108.8
C15—C16—H16A	120.0	O5—C37—H37C	122.4
C16—C17—C18	120.3 (3)	H37A—C37—H37C	108.8
C16—C17—H17A	119.8	H37B—C37—H37C	100.5
C18—C17—H17A	119.8
O3—P1—C1—C2	168.16 (18)	C18—C13—C14—C15	0.2 (4)
C13—P1—C1—C2	44.7 (2)	P1—C13—C14—C15	178.6 (2)
C19—P1—C1—C2	−68.3 (2)	C13—C14—C15—C16	−0.7 (5)
O3—P1—C1—C6	−14.1 (2)	C14—C15—C16—C17	0.7 (5)
C13—P1—C1—C6	−137.6 (2)	C15—C16—C17—C18	−0.4 (5)
C19—P1—C1—C6	109.4 (2)	C14—C13—C18—C17	0.1 (4)
C6—C1—C2—C3	−2.7 (4)	P1—C13—C18—C17	−178.2 (2)
P1—C1—C2—C3	175.1 (2)	C16—C17—C18—C13	0.0 (4)
C1—C2—C3—C4	1.3 (4)	O3—P1—C19—C20	158.7 (2)
C2—C3—C4—C5	1.3 (4)	C1—P1—C19—C20	32.7 (3)
C3—C4—C5—O1	176.6 (2)	C13—P1—C19—C20	−79.7 (2)
C3—C4—C5—C6	−2.5 (4)	O3—P1—C19—C24	−21.6 (3)
C2—C1—C6—C5	1.4 (3)	C1—P1—C19—C24	−147.6 (2)
P1—C1—C6—C5	−176.17 (19)	C13—P1—C19—C24	100.1 (2)
C2—C1—C6—C7	−171.9 (2)	C24—C19—C20—C21	0.4 (4)
P1—C1—C6—C7	10.5 (3)	P1—C19—C20—C21	−179.8 (2)
O1—C5—C6—C1	−178.0 (2)	C19—C20—C21—C22	−0.9 (5)
C4—C5—C6—C1	1.1 (4)	C20—C21—C22—C23	1.3 (5)
O1—C5—C6—C7	−4.2 (3)	C21—C22—C23—C24	−1.2 (6)
C4—C5—C6—C7	174.9 (2)	C20—C19—C24—C23	−0.4 (4)
C1—C6—C7—C12	−112.7 (3)	P1—C19—C24—C23	179.9 (2)
C5—C6—C7—C12	73.9 (3)	C22—C23—C24—C19	0.8 (5)
C1—C6—C7—C8	73.1 (3)	O4—P2—C25—C30	−161.1 (2)
C5—C6—C7—C8	−100.2 (3)	C31—P2—C25—C30	−40.4 (3)
C12—C7—C8—O2	−177.8 (2)	C12—P2—C25—C30	73.9 (3)
C6—C7—C8—O2	−3.1 (3)	O4—P2—C25—C26	18.5 (3)
C12—C7—C8—C9	1.0 (4)	C31—P2—C25—C26	139.2 (2)
C6—C7—C8—C9	175.7 (2)	C12—P2—C25—C26	−106.5 (2)
O2—C8—C9—C10	178.9 (2)	C30—C25—C26—C27	−1.2 (4)
C7—C8—C9—C10	0.1 (4)	P2—C25—C26—C27	179.3 (3)
C8—C9—C10—C11	−0.4 (4)	C25—C26—C27—C28	0.3 (5)
C9—C10—C11—C12	−0.6 (4)	C26—C27—C28—C29	0.2 (5)
C10—C11—C12—C7	1.8 (4)	C27—C28—C29—C30	0.1 (5)
C10—C11—C12—P2	−178.6 (2)	C28—C29—C30—C25	−0.9 (4)
C8—C7—C12—C11	−2.0 (4)	C26—C25—C30—C29	1.5 (4)
C6—C7—C12—C11	−176.0 (2)	P2—C25—C30—C29	−179.0 (2)
C8—C7—C12—P2	178.6 (2)	O4—P2—C31—C32	−152.7 (2)
C6—C7—C12—P2	4.5 (4)	C25—P2—C31—C32	86.8 (3)
O4—P2—C12—C11	48.3 (2)	C12—P2—C31—C32	−34.2 (3)
C25—P2—C12—C11	172.76 (19)	O4—P2—C31—C36	23.8 (3)
C31—P2—C12—C11	−69.7 (2)	C25—P2—C31—C36	−96.7 (2)
O4—P2—C12—C7	−132.2 (2)	C12—P2—C31—C36	142.3 (2)
C25—P2—C12—C7	−7.8 (3)	C36—C31—C32—C33	0.9 (5)
C31—P2—C12—C7	109.8 (3)	P2—C31—C32—C33	177.5 (2)
O3—P1—C13—C18	128.7 (2)	C31—C32—C33—C34	−0.2 (5)
C1—P1—C13—C18	−106.1 (2)	C32—C33—C34—C35	−0.9 (5)
C19—P1—C13—C18	7.8 (3)	C33—C34—C35—C36	1.2 (5)
O3—P1—C13—C14	−49.6 (2)	C32—C31—C36—C35	−0.7 (4)
C1—P1—C13—C14	75.6 (2)	P2—C31—C36—C35	−177.3 (2)
C19—P1—C13—C14	−170.5 (2)	C34—C35—C36—C31	−0.4 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4^i	0.82	1.83	2.648 (2)	177
O2—H2B···O5^ii	0.82	1.85	2.669 (3)	172
O5—H5···O3	0.82	1.84	2.656 (3)	177
CgA—CgB	?	?	3.568 (6)	14
CgC—CgD	?	?	4.912 (6)	180
CgE—CgF	?	?	4.339 (8)	162

Symmetry codes: (i) x−1/2, −y+5/2, −z+2; (ii) −x+1, y+1/2, −z+3/2.