O-Phenyl (triphenyl­phospho­niometh­yl)­phospho­nate phenol solvate: supra­molecular structure generated by O-H...O, C-H...O and C-H...[pi](arene) hydrogen bonds

The title compound, C₂₅H₂₂O₃P₂·C₆H₆O, has a zwitterionic betaine-like structure and crystallizes as a phenol solvate. The two mol­ecular components are held together by an almost linear inter­molecular O-H...O hydrogen bond. The structure also contains three weak C-H...O and two C-H...[pi](arene) inter­actions.

S1. Comment

Betaine (N,N,N-trimethylglycine) acts as an important biochemical donor of the methyl group for tetrahydrofolic acid (N₅,N₁₀-methylenetetrahydrofoliate synthesis) as well as homocysteinic acid (methionine synthesis) (Stryer, 1995). The phosphonic analogue of betaine – trimethylammoniummethanophosphonic acid – was first synthesized over five decades ago (Medved & Kabachnik, 1951; Kabachnik & Medved, 1953; Myers & Jibril, 1957); more than a decade ago, its biological activity became recognized (Abdel-Ghany et al., 1993).

However, to our best knowledge no example of a betaine analogue containing two P atoms (phosphoniummethylenephosphonic acid or its ester) has been described in the literature. We present here the synthesis and crystal and molecular structures of the first phosphoniophosphonic analogue of betaine, O-phenyl triphenylphosphoniummethylenephosphonate as a phenol solvate, (I).

The first example of phosphoniummethylenephosphonic acid was synthesized in the form of the O-phenyl ester by controlled hydrolysis of [(diphenoxyphosphinyl)methylidene]triphenylphosphorane, (II), and obtained in the crystalline form as the phenol solvate, (I). Its structure was tentatively assigned by MS, NMR and elemental analysis; however, an unequivocal confirmation was obtained from crystallographic analysis.

The molecular structure of (I), with the atom-numbering scheme, is shown in Fig. 1. The C₂₅H₂₂O₃P₂ molecule exists as a zwitterion. The positive charge is located on atom P1, while the negative charge is attributed formally to atom O2. Taking into account the P2—O2 and P2—O3 bond lengths, partial delocalization of the charge between both O atoms within the O2≐ P2≐O3 fragment can be proposed. The P2—O3 bond is slightly shorter than the P2—O2 bond; however, both distances are longer than the P═O linkage within (C,N)(O)₂—P═O systems [1.457 (9) Å; Allen et al., 1987] and close to mean value of 1.483 (8) Å for (C—O)₂P(≐ O)₂^- systems, indicating delocalization of bonds (Allen et al., 1987).

In the molecule of (I), two P atoms are joined through a Csp³ atom. The P1—C1 and P2—C1 distances differ from each other significantly, showing having lengths of 1.7855 (14) and 1.8202 (15) Å, respectively (Table 1).

The coordination around P1 is nearly tetrahedral, with angles varying from 106.98 (7) to 114.31 (7)°, whereas within the phosphonate group the geometry around atom P2 indicates a considerable distortion of the tetrahedron, especially in the O2—P2—O3 and O1—P2—C1 bond angles (Table 1).

The P⁺—C(phenyl) bond lengths are very close to the mean distance of 1.793 (10) Å found for 118 Ph₃P⁺—CH₂(sp³) fragments (3 × 118 = 354 values) in the Cambridge Structural Database (Version 5.27; Allen, 2002); the minimum and maximum distances are 1.752 (3) and 1.854 (3) Å, respectively.

All benzene rings, including the phenol ring, are planar. The C—C bond lengths and bond angles within these rings are typical for aromatic systems [1.384 (13) Å; Allen et al., 1987], hence no detailed discussion is needed. The labelling scheme A–E, applied for phenyl rings, is introduced in Fig. 1. A maximum deviation of -0.010 (2)° is observed, for C12 from the least-squares plane of ring A. The dihedral angles between the mean planes of rings are summarized in Table 3. This spatial arrangement enables the formation of C—H···O and C—H···π(arene) interactions; however, aromatic π–π stacking interactions are absent in the structure.

The title compound crystallizes as a phenol solvate. Two molecular components are linked within the selected asymmetric unit by an almost linear O4—H4···O2 intermolecular hydrogen bond (Fig. 1 and Table 2).

In (I), there are also three short intermolecular C—H···O contacts, which on the basis of observed H···O and C···O distances can be regarded as weak hydrogen-bonding interactions (Table 2; Taylor & Kennard, 1982). Atoms C1 and C12 act as hydrogen-bond donors to atom O3ⁱ [symmetry code: (i) -x + 1, -y + 1, -z + 2], to form a centrosymmetric dimer. The former of these hydrogen bonds generates a graph-set motif of R₂²(8), while the second generates a R₂²(14) ring (Bernstein et al., 1995) (Fig. 2). Such a dimer is additionally stabilized by C1—H1A···π (ring D) hydrogen bonds.

Fig. 3 presents another hydrogen-bonded motif that plays an important role in the supramolecular structure of (I). Atom C35, via atom H35, acts as a hydrogen-bond donor towards atom O3ⁱⁱ [symmetry code: (ii) x + 1, y, z], thereby producing an infinite C(8) chain running parallel to the [100] direction.

In summary, the combination of all three weak C—H···O interactions produces infinite chains of centrosymmetric dimers along the a axis. Aforementioned chains are linked into (010) sheets by C25—H25···πⁱⁱⁱ (ring E) [symmetry code: (iii) -x + 1, -y + 1, -z + 1] (Fig. 4). Every sheet passes through the unit cell in the domain -0.07 < y < 1.07. There are no direction-specific interactions between adjacent sheets.

Related literature

For related literature, see: Abdel-Ghany, Ihnat, Miller, Kunin & Tong (1993); Allen (2002); Allen et al. (1987); Bernstein et al. (1995); Chęcińska et al. (2003); Kabachnik & Medved (1953); Medved & Kabachnik (1951); Myers & Jibril (1957); Stryer (1995); Taylor & Kennard (1982).

S2. Experimental

The title compound, (I), was synthesized from [(diphenoxyphosphinyl)methylidene]triphenylphosphorane, (II), which was prepared exactly as described in our previous paper (Chęcińska et al., 2003). For (II): ³¹P NMR (CD₃CN, p.p.m.): δ 20.98 (d, Ph₃P═), 28.03 [d, (PhO)₂P(O)–], ²J_PP = 46.4 Hz]. The ylide (II) (1.08 g, 1 mmol) was dissolved in 20 ml of acetonitrile containing 2% of water. The solution was kept for 48 h at 323 K in a closed flask and evaporated. The residue was crystallized from ethyl acetate, yielding 0.61 g (58%) of phenol-solvated betaine (I) in the form of colorless crystals. M.p. 476–479 K (Boethius apparatus, uncorrected). ³¹P NMR (CDCl₃, p.p.m.): δ -1.64 [d, (PhO)P(O)O^-], 212.36 (d, Ph₃P⁺), ²J_PP = 10.1 Hz (Bruker AC 200 spectrometer, 81.026 MHz, 85% H₃PO₄ as external standard). ¹H NMR (CDCl₃, p.p.m.): δ 3.565 (dd, 2H, P—CH₂—P, ²J_HP = 15.7 and 17.1 Hz), 6.7–7.2 (m, 10H, PhO H atoms), 7.45–7.8 (m, 15H, Ph₃P H atoms), 9.44 (br s, 1H, OH) (Bruker AC 200 s pectrometer, 200.160 MHz, tetramethylsilane as internal standard). MS FAB (Cs⁺, negative ions): m/z 431 (16%), 355 (100%), 278 (8%), 261 (28%) (Finnigan MAT 95 spectrometer, MW 432.37 Da for protonated betaine without phenol). Elemental analysis found: C 70.49, H 5.25, P 11.58%; calculated for C₃₁H₂₈O₄P₂: 70.72, H 5.36, P 11.77%.

S3. Refinement

Atom H4, involved in the O4—H4 ···O2 hydrogen bond, was located in a difference map and refined isotropically. All C-bound H atoms of methylene and phenyl groups were positioned geometrically (C—H = 0.97 and 0.93 Å, respectively) and constrained to ride on their parent atoms [U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1989); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures

	Fig. 1. The structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a centrosymmetric dimer. [Symmetry code: (i) -x + 1, -y + 1, -z + 2.] For the sake of clarity, C-bound H atoms that are not involved in the motif shown have been omitted.
	Fig. 3. Part of the crystal structure of (I), showing the formation of an infinite C—H···O chain running parallel to the [100] direction. [Symmetry code:s (ii) x + 1, y, z; (iv) x - 1, y, z]. For the sake of clarity, C-bound H atoms that are not involved in the motif shown have been omitted.
	Fig. 4. Part of the crystal structure of (I), showing (010) sheets generated by C—H···π interactions between chains of dimers. [Symmetry code: (iii) -x + 1, -y + 1, -z + 1.] For the sake of clarity, C-bound H atoms that are not involved in the motif shown have been omitted.

O-phenyl triphenylphosphoniummethylenephosphonate phenol solvate

Crystal data

C25H22O3P2·C6H6O	Z = 2
Mr = 526.47	F(000) = 552
Triclinic, P1	Dx = 1.272 Mg m^−3 Dm = 1.271 Mg m^−3 Dm measured by flotation in xylene, bromobenzene, heptane & toluene
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 9.793 (2) Å	Cell parameters from 25 reflections
b = 10.170 (2) Å	θ = 12.6–17.1°
c = 14.374 (2) Å	µ = 0.19 mm^−1
α = 82.78 (2)°	T = 293 K
β = 80.07 (2)°	Plate, colourless
γ = 78.35 (2)°	0.5 × 0.2 × 0.1 mm
V = 1374.9 (5) Å^3

Data collection

Rigaku AFC-5S diffractometer	Rint = 0.013
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 4.1°
Graphite monochromator	h = −12→12
ω scan	k = −13→0
6644 measured reflections	l = −18→18
6293 independent reflections	3 standard reflections every 150 reflections
4137 reflections with I > 2σ(I)	intensity decay: 1.6%

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)] = 0.033	Hydrogen site location: mixed
wR(F^2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	[1.00000exp(2.00(sinθ/λ)^2)]/[σ^2(Fo^2) + (0.041P)^2] where P = 0.33333Fo^2 + 0.66667Fc^2]
6293 reflections	(Δ/σ)max = 0.001
338 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Experimental. M.p. 476–479 K (Boethius apparatus, uncorrected). ³¹P NMR (CDCl₃, p.p.m.): δ -1.64 [d, (PhO)P(O)O^-], 212.36 (d, Ph₃P⁺), ²J_PP = 10.1 Hz (Bruker AC 200 spectrometer, 81.026 MHz, 85% H₃PO₄ as external standard). ¹H NMR (CDCl₃, p.p.m.): δ 3.565 (dd, 2H, P—CH₂—P, ²J_HP = 15.7 and 17.1 Hz), 6.7–7.2 (m, 10H, PhO H atoms), 7.45–7.8 (m, 15H, Ph₃P H atoms), 9.44 (br s, 1H, OH) (Bruker AC 200 s pectrometer, 200.160 MHz, tetramethylsilane as internal standard). MS FAB (Cs⁺, negative ions): m/z 431 (16%), 355 (100%), 278 (8%), 261 (28%) (Finnigan MAT 95 spectrometer, MW 432.37 Da for protonated betaine without phenol).

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	0.76848 (4)	0.57432 (4)	0.78751 (3)	0.03663 (9)
P2	0.56993 (4)	0.36856 (4)	0.86801 (3)	0.04178 (10)
O1	0.68777 (11)	0.26485 (11)	0.92045 (8)	0.0562 (3)
O2	0.59888 (13)	0.33504 (12)	0.76829 (7)	0.0633 (3)
O3	0.42911 (10)	0.37500 (11)	0.92469 (7)	0.0485 (3)
O4	0.54942 (14)	0.14811 (14)	0.67752 (9)	0.0688 (4)
H4	0.561 (2)	0.215 (2)	0.7079 (14)	0.089 (7)*
C1	0.62373 (14)	0.52908 (14)	0.87057 (10)	0.0408 (3)
H1A	0.5423	0.5996	0.8630	0.049*
H1B	0.6456	0.5313	0.9336	0.049*
C11	0.80021 (14)	0.72975 (14)	0.81947 (10)	0.0415 (3)
C12	0.80602 (18)	0.74206 (17)	0.91369 (12)	0.0559 (4)
H12	0.7903	0.6717	0.9598	0.067*
C13	0.83519 (19)	0.85926 (19)	0.93909 (13)	0.0659 (5)
H13	0.8412	0.8668	1.0020	0.079*
C14	0.85535 (19)	0.96491 (17)	0.87084 (15)	0.0658 (5)
H14	0.8752	1.0435	0.8879	0.079*
C15	0.84628 (18)	0.95413 (17)	0.77879 (14)	0.0641 (5)
H15	0.8582	1.0263	0.7335	0.077*
C16	0.81952 (16)	0.83689 (15)	0.75176 (12)	0.0526 (4)
H16	0.8145	0.8301	0.6886	0.063*
C21	0.72522 (15)	0.59906 (14)	0.66961 (10)	0.0417 (3)
C22	0.83189 (18)	0.59330 (18)	0.59240 (11)	0.0618 (5)
H22	0.9257	0.5743	0.6018	0.074*
C23	0.7990 (2)	0.6159 (2)	0.50129 (13)	0.0806 (6)
H23	0.8707	0.6129	0.4495	0.097*
C24	0.6607 (3)	0.6426 (2)	0.48731 (14)	0.0823 (6)
H24	0.6386	0.6561	0.4260	0.099*
C25	0.5564 (2)	0.6495 (2)	0.56262 (14)	0.0785 (6)
H25	0.4628	0.6692	0.5527	0.094*
C26	0.58702 (18)	0.62774 (18)	0.65371 (12)	0.0600 (4)
H26	0.5142	0.6324	0.7048	0.072*
C31	0.92996 (14)	0.45258 (14)	0.78761 (10)	0.0402 (3)
C32	0.94056 (16)	0.32544 (15)	0.75868 (11)	0.0521 (4)
H32	0.8626	0.3008	0.7414	0.062*
C33	1.06683 (18)	0.23563 (18)	0.75555 (13)	0.0650 (5)
H33	1.0734	0.1504	0.7362	0.078*
C34	1.1817 (2)	0.2701 (2)	0.78034 (14)	0.0728 (5)
H34	1.2666	0.2089	0.7774	0.087*
C35	1.1724 (2)	0.3947 (2)	0.80964 (17)	0.0858 (7)
H35	1.2508	0.4178	0.8274	0.103*
C36	1.04739 (18)	0.48623 (19)	0.81299 (14)	0.0685 (5)
H36	1.0420	0.5712	0.8325	0.082*
C41	0.67097 (15)	0.21957 (14)	1.01567 (11)	0.0472 (4)
C42	0.57475 (17)	0.13770 (15)	1.05286 (12)	0.0554 (4)
H42	0.5154	0.1170	1.0150	0.066*
C43	0.5675 (2)	0.08684 (18)	1.14674 (15)	0.0733 (6)
H43	0.5026	0.0318	1.1725	0.088*
C44	0.6552 (3)	0.1169 (2)	1.20224 (16)	0.0902 (7)
H44	0.6504	0.0820	1.2655	0.108*
C45	0.7496 (3)	0.1981 (3)	1.16471 (18)	0.0965 (7)
H45	0.8088	0.2186	1.2028	0.116*
C46	0.7588 (2)	0.2502 (2)	1.07136 (16)	0.0748 (5)
H46	0.8236	0.3055	1.0462	0.090*
C51	0.64748 (17)	0.13224 (16)	0.59910 (11)	0.0512 (4)
C52	0.73821 (19)	0.22069 (19)	0.56740 (12)	0.0622 (4)
H52	0.7349	0.2946	0.6004	0.075*
C53	0.8339 (2)	0.1987 (3)	0.48637 (16)	0.0932 (7)
H53	0.8964	0.2577	0.4653	0.112*
C54	0.8391 (3)	0.0913 (3)	0.43588 (17)	0.1073 (9)
H54	0.9029	0.0785	0.3804	0.129*
C55	0.7496 (3)	0.0041 (3)	0.46832 (16)	0.0949 (7)
H55	0.7537	−0.0698	0.4351	0.114*
C56	0.6536 (2)	0.02276 (19)	0.54879 (13)	0.0708 (5)
H56	0.5925	−0.0376	0.5698	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.03495 (18)	0.03575 (19)	0.03911 (19)	−0.00787 (14)	−0.00430 (14)	−0.00280 (14)
P2	0.0438 (2)	0.0442 (2)	0.0392 (2)	−0.01595 (17)	0.00013 (16)	−0.00707 (16)
O1	0.0465 (6)	0.0518 (6)	0.0595 (7)	−0.0032 (5)	0.0077 (5)	0.0045 (5)
O2	0.0847 (8)	0.0660 (7)	0.0458 (6)	−0.0343 (7)	0.0056 (6)	−0.0190 (5)
O3	0.0407 (5)	0.0613 (7)	0.0464 (6)	−0.0187 (5)	−0.0049 (4)	−0.0036 (5)
O4	0.0823 (9)	0.0780 (9)	0.0546 (7)	−0.0400 (7)	0.0029 (6)	−0.0162 (7)
C1	0.0408 (7)	0.0422 (8)	0.0394 (7)	−0.0104 (6)	0.0002 (6)	−0.0076 (6)
C11	0.0373 (7)	0.0367 (7)	0.0503 (8)	−0.0081 (6)	−0.0024 (6)	−0.0066 (6)
C12	0.0652 (10)	0.0518 (9)	0.0538 (9)	−0.0234 (8)	0.0008 (8)	−0.0093 (7)
C13	0.0712 (12)	0.0689 (12)	0.0633 (11)	−0.0264 (10)	0.0051 (9)	−0.0271 (9)
C14	0.0622 (11)	0.0443 (9)	0.0914 (14)	−0.0156 (8)	0.0059 (10)	−0.0235 (9)
C15	0.0641 (11)	0.0401 (9)	0.0876 (14)	−0.0147 (8)	−0.0097 (10)	0.0022 (9)
C16	0.0549 (9)	0.0425 (8)	0.0607 (10)	−0.0124 (7)	−0.0096 (8)	0.0011 (7)
C21	0.0442 (8)	0.0397 (7)	0.0404 (7)	−0.0067 (6)	−0.0068 (6)	−0.0014 (6)
C22	0.0559 (10)	0.0713 (12)	0.0482 (9)	0.0006 (9)	−0.0003 (7)	0.0025 (8)
C23	0.0965 (16)	0.0850 (14)	0.0432 (10)	0.0078 (12)	0.0026 (10)	0.0010 (9)
C24	0.1152 (18)	0.0804 (14)	0.0503 (11)	−0.0035 (13)	−0.0323 (12)	0.0016 (10)
C25	0.0725 (12)	0.0955 (15)	0.0694 (13)	−0.0126 (11)	−0.0351 (11)	0.0136 (11)
C26	0.0504 (9)	0.0721 (11)	0.0542 (10)	−0.0066 (8)	−0.0127 (8)	0.0047 (8)
C31	0.0370 (7)	0.0416 (8)	0.0407 (7)	−0.0057 (6)	−0.0063 (6)	−0.0007 (6)
C32	0.0423 (8)	0.0483 (9)	0.0637 (10)	−0.0085 (7)	0.0014 (7)	−0.0110 (7)
C33	0.0561 (10)	0.0465 (9)	0.0824 (13)	−0.0009 (8)	0.0081 (9)	−0.0075 (9)
C34	0.0518 (11)	0.0674 (13)	0.0863 (14)	0.0125 (9)	−0.0107 (9)	0.0043 (10)
C35	0.0493 (11)	0.0929 (16)	0.1212 (18)	0.0007 (10)	−0.0388 (11)	−0.0194 (14)
C36	0.0512 (10)	0.0637 (11)	0.0979 (14)	−0.0027 (8)	−0.0307 (10)	−0.0211 (10)
C41	0.0416 (8)	0.0366 (8)	0.0563 (9)	0.0003 (6)	0.0012 (7)	−0.0017 (7)
C42	0.0518 (9)	0.0414 (8)	0.0675 (11)	−0.0068 (7)	0.0012 (8)	−0.0012 (8)
C43	0.0682 (12)	0.0512 (10)	0.0802 (13)	0.0029 (9)	0.0117 (10)	0.0168 (9)
C44	0.0957 (17)	0.0879 (16)	0.0645 (13)	0.0211 (14)	−0.0085 (12)	0.0113 (12)
C45	0.0986 (18)	0.1066 (19)	0.0891 (17)	−0.0080 (15)	−0.0434 (14)	−0.0047 (14)
C46	0.0647 (12)	0.0701 (12)	0.0935 (15)	−0.0186 (10)	−0.0241 (11)	0.0049 (11)
C51	0.0600 (10)	0.0544 (9)	0.0419 (8)	−0.0132 (8)	−0.0146 (7)	−0.0015 (7)
C52	0.0678 (11)	0.0744 (12)	0.0505 (9)	−0.0271 (10)	−0.0092 (8)	−0.0065 (9)
C53	0.0773 (14)	0.134 (2)	0.0744 (14)	−0.0451 (15)	0.0047 (11)	−0.0118 (14)
C54	0.0984 (18)	0.141 (2)	0.0732 (15)	−0.0121 (18)	0.0161 (13)	−0.0311 (17)
C55	0.132 (2)	0.0780 (15)	0.0689 (14)	−0.0016 (15)	−0.0065 (14)	−0.0264 (12)
C56	0.1030 (15)	0.0568 (11)	0.0573 (11)	−0.0210 (10)	−0.0178 (10)	−0.0056 (9)

Geometric parameters (Å, º)

P1—C1	1.7855 (14)	C26—H26	0.9300
P1—C21	1.7923 (14)	C31—C36	1.381 (2)
P1—C11	1.7991 (15)	C31—C32	1.386 (2)
P1—C31	1.8009 (15)	C32—C33	1.378 (2)
P2—O3	1.4695 (10)	C32—H32	0.9300
P2—O2	1.4815 (11)	C33—C34	1.358 (3)
P2—O1	1.6189 (12)	C33—H33	0.9300
P2—C1	1.8202 (15)	C34—C35	1.366 (3)
O1—C41	1.3809 (18)	C34—H34	0.9300
O4—C51	1.3523 (19)	C35—C36	1.378 (2)
O4—H4	0.88 (2)	C35—H35	0.9300
C1—H1A	0.9700	C36—H36	0.9300
C1—H1B	0.9700	C41—C46	1.373 (2)
C11—C16	1.387 (2)	C41—C42	1.378 (2)
C11—C12	1.387 (2)	C42—C43	1.378 (2)
C12—C13	1.385 (2)	C42—H42	0.9300
C12—H12	0.9300	C43—C44	1.369 (3)
C13—C14	1.382 (3)	C43—H43	0.9300
C13—H13	0.9300	C44—C45	1.361 (3)
C14—C15	1.361 (3)	C44—H44	0.9300
C14—H14	0.9300	C45—C46	1.374 (3)
C15—C16	1.385 (2)	C45—H45	0.9300
C15—H15	0.9300	C46—H46	0.9300
C16—H16	0.9300	C51—C52	1.373 (2)
C21—C26	1.378 (2)	C51—C56	1.388 (2)
C21—C22	1.385 (2)	C52—C53	1.375 (3)
C22—C23	1.383 (2)	C52—H52	0.9300
C22—H22	0.9300	C53—C54	1.373 (3)
C23—C24	1.372 (3)	C53—H53	0.9300
C23—H23	0.9300	C54—C55	1.357 (3)
C24—C25	1.352 (3)	C54—H54	0.9300
C24—H24	0.9300	C55—C56	1.366 (3)
C25—C26	1.374 (2)	C55—H55	0.9300
C25—H25	0.9300	C56—H56	0.9300
C1—P1—C21	110.26 (7)	C21—C26—H26	119.9
C1—P1—C11	106.98 (7)	C36—C31—C32	118.75 (14)
C21—P1—C11	109.54 (7)	C36—C31—P1	120.44 (12)
C1—P1—C31	114.31 (7)	C32—C31—P1	120.76 (11)
C21—P1—C31	107.97 (7)	C33—C32—C31	119.87 (16)
C11—P1—C31	107.68 (7)	C33—C32—H32	120.1
O3—P2—O2	121.84 (7)	C31—C32—H32	120.1
O3—P2—O1	111.10 (6)	C34—C33—C32	120.84 (17)
O2—P2—O1	105.09 (7)	C34—C33—H33	119.6
O3—P2—C1	107.50 (7)	C32—C33—H33	119.6
O2—P2—C1	107.85 (7)	C33—C34—C35	119.87 (17)
O1—P2—C1	101.60 (7)	C33—C34—H34	120.1
C41—O1—P2	124.97 (9)	C35—C34—H34	120.1
C51—O4—H4	110.7 (13)	C34—C35—C36	120.26 (18)
P1—C1—P2	120.06 (8)	C34—C35—H35	119.9
P1—C1—H1A	107.3	C36—C35—H35	119.9
P2—C1—H1A	107.3	C35—C36—C31	120.40 (18)
P1—C1—H1B	107.3	C35—C36—H36	119.8
P2—C1—H1B	107.3	C31—C36—H36	119.8
H1A—C1—H1B	106.9	C46—C41—C42	120.47 (17)
C16—C11—C12	119.55 (14)	C46—C41—O1	118.61 (15)
C16—C11—P1	121.27 (12)	C42—C41—O1	120.78 (15)
C12—C11—P1	119.18 (11)	C41—C42—C43	119.24 (18)
C13—C12—C11	119.95 (15)	C41—C42—H42	120.4
C13—C12—H12	120.0	C43—C42—H42	120.4
C11—C12—H12	120.0	C44—C43—C42	120.35 (19)
C14—C13—C12	119.93 (17)	C44—C43—H43	119.8
C14—C13—H13	120.0	C42—C43—H43	119.8
C12—C13—H13	120.0	C45—C44—C43	119.8 (2)
C15—C14—C13	120.13 (16)	C45—C44—H44	120.1
C15—C14—H14	119.9	C43—C44—H44	120.1
C13—C14—H14	119.9	C44—C45—C46	120.9 (2)
C14—C15—C16	120.78 (16)	C44—C45—H45	119.6
C14—C15—H15	119.6	C46—C45—H45	119.6
C16—C15—H15	119.6	C41—C46—C45	119.21 (19)
C15—C16—C11	119.63 (16)	C41—C46—H46	120.4
C15—C16—H16	120.2	C45—C46—H46	120.4
C11—C16—H16	120.2	O4—C51—C52	122.60 (15)
C26—C21—C22	118.84 (14)	O4—C51—C56	117.80 (16)
C26—C21—P1	121.30 (12)	C52—C51—C56	119.59 (17)
C22—C21—P1	119.83 (12)	C51—C52—C53	119.20 (19)
C23—C22—C21	120.06 (17)	C51—C52—H52	120.4
C23—C22—H22	120.0	C53—C52—H52	120.4
C21—C22—H22	120.0	C54—C53—C52	121.3 (2)
C24—C23—C22	120.00 (18)	C54—C53—H53	119.3
C24—C23—H23	120.0	C52—C53—H53	119.3
C22—C23—H23	120.0	C55—C54—C53	118.9 (2)
C25—C24—C23	120.01 (17)	C55—C54—H54	120.5
C25—C24—H24	120.0	C53—C54—H54	120.5
C23—C24—H24	120.0	C54—C55—C56	121.2 (2)
C24—C25—C26	120.82 (18)	C54—C55—H55	119.4
C24—C25—H25	119.6	C56—C55—H55	119.4
C26—C25—H25	119.6	C55—C56—C51	119.7 (2)
C25—C26—C21	120.27 (17)	C55—C56—H56	120.1
C25—C26—H26	119.9	C51—C56—H56	120.1
O3—P2—O1—C41	−18.41 (14)	C22—C21—C26—C25	0.3 (3)
O2—P2—O1—C41	−152.01 (12)	P1—C21—C26—C25	178.45 (15)
C1—P2—O1—C41	95.68 (12)	C1—P1—C31—C36	−116.51 (14)
C21—P1—C1—P2	66.49 (11)	C21—P1—C31—C36	120.40 (14)
C11—P1—C1—P2	−174.46 (8)	C11—P1—C31—C36	2.20 (15)
C31—P1—C1—P2	−55.36 (11)	C1—P1—C31—C32	66.08 (14)
O3—P2—C1—P1	−164.92 (8)	C21—P1—C31—C32	−57.02 (13)
O2—P2—C1—P1	−31.87 (11)	C11—P1—C31—C32	−175.21 (12)
O1—P2—C1—P1	78.33 (10)	C36—C31—C32—C33	−0.1 (2)
C1—P1—C11—C16	−133.32 (13)	P1—C31—C32—C33	177.33 (12)
C21—P1—C11—C16	−13.80 (14)	C31—C32—C33—C34	−0.1 (3)
C31—P1—C11—C16	103.38 (13)	C32—C33—C34—C35	0.6 (3)
C1—P1—C11—C12	46.98 (14)	C33—C34—C35—C36	−0.8 (3)
C21—P1—C11—C12	166.49 (12)	C34—C35—C36—C31	0.6 (3)
C31—P1—C11—C12	−76.33 (13)	C32—C31—C36—C35	−0.1 (3)
C16—C11—C12—C13	−1.9 (2)	P1—C31—C36—C35	−177.57 (16)
P1—C11—C12—C13	177.77 (13)	P2—O1—C41—C46	−117.61 (15)
C11—C12—C13—C14	1.4 (3)	P2—O1—C41—C42	66.76 (17)
C12—C13—C14—C15	0.2 (3)	C46—C41—C42—C43	0.0 (2)
C13—C14—C15—C16	−1.2 (3)	O1—C41—C42—C43	175.60 (14)
C14—C15—C16—C11	0.7 (3)	C41—C42—C43—C44	−0.3 (3)
C12—C11—C16—C15	0.9 (2)	C42—C43—C44—C45	0.4 (3)
P1—C11—C16—C15	−178.82 (12)	C43—C44—C45—C46	−0.3 (4)
C1—P1—C21—C26	21.86 (15)	C42—C41—C46—C45	0.0 (3)
C11—P1—C21—C26	−95.62 (14)	O1—C41—C46—C45	−175.60 (18)
C31—P1—C21—C26	147.39 (13)	C44—C45—C46—C41	0.1 (3)
C1—P1—C21—C22	−160.02 (13)	O4—C51—C52—C53	−179.18 (18)
C11—P1—C21—C22	82.50 (14)	C56—C51—C52—C53	−0.2 (3)
C31—P1—C21—C22	−34.49 (15)	C51—C52—C53—C54	1.0 (3)
C26—C21—C22—C23	−0.1 (3)	C52—C53—C54—C55	−1.4 (4)
P1—C21—C22—C23	−178.29 (15)	C53—C54—C55—C56	1.2 (4)
C21—C22—C23—C24	−0.6 (3)	C54—C55—C56—C51	−0.5 (4)
C22—C23—C24—C25	1.2 (3)	O4—C51—C56—C55	178.99 (19)
C23—C24—C25—C26	−1.1 (3)	C52—C51—C56—C55	0.0 (3)
C24—C25—C26—C21	0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O2	0.89 (2)	1.72 (2)	2.601 (2)	175 (2)
C1—H1B···O3^i	0.97	2.30	3.142 (2)	145
C12—H12···O3^i	0.93	2.57	3.269 (2)	133
C35—H35···O3^ii	0.93	2.36	3.200 (3)	150
C1—H1A···CgD^i	0.93	2.79	3.727 (2)	161
C25—H25···CgE^iii	0.93	2.90	3.667 (2)	141

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