(3aS,7aS)-1-{2-Oxo-1,3-bis­[(S)-1-phen­ylethyl]­per­hydro-1,3,2[lambda]⁵-benzodi­aza­phosphol-2-yl}-1-phenylmethanol: a mixture of dia­stereoiso­mers in a disordered crystal

In the title compound, C₂₉H₃₅N₂O₂P, the stereogenic C center [alpha] to the P atom, formed during the Pudovik condensation reaction between a deprotonated chiral diaza­phosphole and benz­aldehyde, has disordered substituents, giving a mixture of C[alpha]-R and C[alpha]-S diastereoisomers. Moreover, this compound crystallizes with two independent mol­ecules in the asymmetric unit. The observed configuration at the C[alpha] atom is 0.741 (6)-S mixed with 0.259 (6)-R, indicating diastereoisomeric enrichment during crystallization. Data from solution and solid-state studies consistently point to an epimerization process at the C[alpha] atom.

S1. Comment

There are many examples in the literature of biologically active α-hydroxy phosphonates and phosphonic acids (e.g. Engel, 1977; Hilderbrand, 1983; De Clercq et al., 1986; Kitamura et al., 1995). Interest for this class of compounds has been motivated by the need to access a variety of phosphorous derivatives, particularly with substitutions at the Cα position, since such derivatives display required physiological properties (Yokomatsu & Shibuya, 1992; Öhler & Kotzinger, 1993; Berkowitz & Smith, 1995; Bennani & Hanessian, 1997).

In this area, the Pudovik reaction is a well known phosphonylation process that involves the addition of organophosphorous compounds containing a labile P—H bond to unsaturated systems (Pudovik & Konovalova, 1979). During the past decade, enantioselective syntheses of α-hydroxyphosphonates through the asymmetric Pudovik reaction of aldehydes have been reported. These reactions take place in the presence of chiral diols, amino alcohols and diamines as catalysts or using chiral auxiliaries (Davies et al., 1998; Groaning et al., 1998; Duxbury et al., 1999; Yamagishi et al., 1999; Rowe & Spilling, 2001). In this context, we recently obtained moderate diastereoselectivities for the carbonyl phosphonylation of aldehydes using N,N'-bis-[(S)-α-phenylethyl]-bicyclic phosphorous acid diamides (Moreno et al., 2004). When attempting to crystallize the adduct between a deprotonated chiral diazophosphole and benzaldehyde (see the scheme below), we observed an unexpected diastereoisomeric enrichment in the solid state. We now report the crystal structure of this compound, (I).

The asymmetric unit of (I) contains two independent molecules (Z'=2), with all atoms in general positions. Stereogenic Cα atoms C23 and C73, incorporated during the condensation reaction, have disordered OH and H substituents, while the phenyl (C24 and C74) and P-containing moieties (P1 and P51) do not exhibit disorder (Fig. 1 and 2). Positions and site-occupancy factors for the disordered groups were refined (see Experimental), converging to similar models for both independent molecules. Merging of site-occupancy factors results in a stereochemistry for Cα corresponding to a mixture of 0.741 (6)-S and 0.259 (6)-R molecules, randomly distributed in the whole crystal, with remaining chiral C centers as follows: 1S, 2S, 7S, 15S; 51S, 52S, 57S, 65S.

Some comments in relation to the unusual disorder observed in (I) are worthwhile: (i) Chiral centers C1, C2, C7 and C15 (and corresponding chiral C atoms for the second molecule) exhibit the same absolute configuration as in the starting material, as expected from the synthetic route. This fact confirms the assignment of the configurations at atoms C23 and C73. (ii) Although of limited reliability in the present case, because of the relatively low anomalous dispersion of P atoms and the polar character of the space group, the refinement of the Flack (1983) parameter is in agreement with the assigned absolute configuration. An attempt to refine the inverted structure leads to a Flack parameter close to 1. Finally, no symptoms of twinning appeared during data collection and structure refinement. (iii) In order to check the reproducibility of the observed absolute configuration, a single-crystal obtained from another batch was studied; on the basis of 6129 collected reflections (2θ_max = 50°, R₁ = 0.04 for 634 refined parameters and 4493 independent data), the absolute configuration for Cα converged to 0.746 (6)-S mixed with 0.254 (6)-R, with a Flack parameter of 0.01 (10), a result very close to that obtained for the refinement reported here.

The three above-mentioned accounts provide strong evidence that the absolute configuration of (I) has been assigned correctly. However, the diastereoisomeric enhancement of ca 50% observed in the solid state does not agree with that found in solution. Diastereoiomers were easily distinguishable by ³¹P NMR spectroscopy; for the crude of the reaction, an isomeric R:S ratio of 1.8:1.0 was estimated, in contrast to the 1.0:1.9 ratio observed in the solid state. Hence, we assume that this enrichment in the minor diastereoisomer probably occurs via a thermodynamically controlled epimerization at the Cα atom, during the crystallization process, while the major isomer in solution corresponds to the kinetic product of the condensation reaction. In order to check this hypothesis, a chemical correlation was carried out. Compound (I) was hydrolyzed to give the corresponding phosphonic acid, which was purified by ion exchange chromatography and then converted to the monocyclohexylammonium salt, using a classical procedure (see Experimental). A comparison with the reported [α]_D values for the enantiomerically pure salts (Smaardijk et al., 1985), indicated that the major isomer for (I) in solution is Cα-R.

The two independent molecules in (I) have similar geometry (Table 1). A fit between the two molecules, carried out on non-H atoms, gives an r.m.s deviation of 0.23 Å, mainly becuase of a degree of free rotation for the phenyl groups. The bicyclic ring system consists of a six-membered chair cycle fused with a five-membered envelope ring, a conformation observed in numerous perhydrobenzodiazophosphole-based molecules (e.g. Koeller et al., 1993; Blazis et al., 1995; Wyatt et al., 1999). The crystal packing of (I) is dominated by hydrogen bonds within the asymmetric unit, which are favored by the Z'>1 value and disorder at Cα atoms (Table 2 and Fig. 3). Each oxide group forms a bifurcated hydrogen bond with the H atoms belonging to the disordered hydroxy groups of the other independent molecule. This symmetric arrangement generates a non-crystallographic inversion center, positioned close to the centroid of the O1···O51 line. However, there is no doubt that the space group of (I) is actually non-centrosymmetric, in agreement with the chiral character of the molecules. The emulated space group, P2₁/c, does not fit the diffraction pattern, for which 255 intensities are above a 3σ threshold in the set of 432 reflections corresponding to the extinction expected for a c glide plane.

In conclusion, we have established, using both chemical and crystallographic evidence, that the title compound can undergo epimerization at Cα, which has been shown previously to be an important chiral center for biological activity for these P-containing molecules. To the best of our knowledge, epimerization processes involved in the Pudovik condensation reaction have not been well documented util now. This potential complication probably deserves more attention when using this valuable synthetic tool.

S2. Experimental

For the synthesis of (I), a solution of diisopropylamine (0.182 ml, 1.29 mmol) in THF (6 ml) was cooled to 213 K, and n-butyllithium (0.471 ml, 1.18 mmol) was added. To this solution was added the diazaphosphole oxide (1.18 mmol) dissolved in thf (3 ml), previously prepared as reported elsewhere (Moreno et al., 2004). The resulting solution was maintained at 213 K for 1 h, and benzaldehyde (1.29 mmol) was added. After an additional reaction time of 4.5 h at 213 K, the reaction mixture was quenched with aqueous ammonium chloride (0.5 ml) and diluted with CHCl₃ (60 ml). The solution was washed with water (2 × 25 ml), dried over Na₂SO₄ and concentrated in vacuo to give the crude product (yield 65%). Single crystals of (I) were obtained by repeated slow evaporation of an AcOEt solution of the crude. M.p. 467 K. [α]_D = 13.10 (c 1, CHCl₃); ³¹P NMR (in CHCl₃, referenced to external 85% H₃PO₄): δ 36.3 (Cα-R isomer) and 34.7 (Cα-S isomer). To a crop of crystals of (I) (0.38 g, 0.93 mmol) dissolved in dioxane (2 ml) was added aqueous 4 N HCl (1 ml). After 2 h, the suspension had dissolved completely. The solution was stirred at room temperature, and the reaction progress was monitored by ³¹P NMR spectroscopy until completion (ca 12 h). The solution was then concentrated in vacuo and the residue was passed through an ion exchange column (Amberite IR-120+) eluted with water. The first 50 ml fraction was evaporated to yield the diastereoisomeric mixture of α-hydroxy-phosphonic acid resulting from the hydrolysis of (I). The phosphonic acid was dissolved in ethanol and cyclohexylamine was added. The solution was cooled to 263 K for 12 h and the precipitated cyclohexylammonium salt was collected by filtration (50% yield). M.p. 483 K (decomposed). [α]_D = − 4.42 (c 0.77, MeOH:H₂O 50% v/v), e.e. = 31%.

S3. Refinement

Atoms O21 and O71 belonging to the hydroxy groups bonded to atoms C23 and C73 were found to be disordered with, respectively, atoms O22 and O72. The coordination of atoms C23 and C73 is completed by disordered H atoms, placed at idealized positions. Site-occupancy factors (SOFs) were refined in two parts, independently for each molecule, with the sum of the SOFs for the two disordered components in each molecule constrained to 1. H atoms of the hydroxy groups were found in difference maps and were included in the disorder model with SOFs corresponding to those of parent the O atoms. Finally, all other H atoms were placed at idealized positions. All H atoms were treated using a riding model, with constrained distances and U_iso(H) values fixed to xU_eq(parent) [C—H = 0.98 Å and x = 1.2 for methine H atoms, C—H = 0.97 Å and x = 1.2 for methylene H atoms, C—H = 0.96 Å and x = 1.5 for methyl H atoms, and C—H = 0.93 Å and x = 1.2 for aromatic H atoms]. O—H distances were fixed at the values found from difference maps (x = 1.5).

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL-Plus (Sheldrick, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1998); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 1998).

Figures

	Fig. 1. The structure of the first independent molecule in (I), with displacement ellipsoids at the 20% probability level. The minor component of the disorder for substituents at C23 has been omitted (i.e. O22, H22 and H232), so that the Cα-S major isomer in the solid state is shown. For clarity, H atoms, except atoms H21 and H231, have been omitted.
	Fig. 2. The structure of the second independent molecule in (I), with displacement ellipsoids at the 20% probability level. The major component of the disorder for substituents at C73 has been omitted (i.e. O71, H71 and H731), so that the Cα-R minor isomer in the solid state is shown. For clarity, H atoms, except atoms H72 and H732, have been omitted.
	Fig. 3. Hydrogen bonds (dashed lines) observed in the asymmetric unit of the title compound. H atoms other than the disordered hydroxy H atoms have been omitted. The major disorder component is represented by atoms O21 and O71.

(3aS,7aS)-1-{2-Oxo-1,3-bis[(S)-1-phenylethyl]perhydro-1,3,2λ⁵– benzodiazaphosphol-2-yl]-1-phenylmethanol:

Crystal data

C29H35N2O2P	F(000) = 1016
Mr = 474.56	Dx = 1.189 Mg m^−3
Monoclinic, P21	Melting point: 467 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 9.6413 (11) Å	Cell parameters from 85 reflections
b = 17.3888 (11) Å	θ = 4.7–13.0°
c = 15.8778 (11) Å	µ = 0.13 mm^−1
β = 95.373 (8)°	T = 300 K
V = 2650.2 (4) Å^3	Irregular, colorless
Z = 4	0.60 × 0.55 × 0.45 mm

Data collection

Bruker P4 diffractometer	5554 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube, FN4	Rint = 0.028
Graphite monochromator	θmax = 29.0°, θmin = 1.7°
2θ/ω scans	h = −13→11
Absorption correction: ψ scan ψ scans (XSCANS; Siemens, 1996)	k = −1→23
Tmin = 0.926, Tmax = 0.942	l = −21→21
15139 measured reflections	3 standard reflections every 97 reflections
7715 independent reflections	intensity decay: 1.5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: See text
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.129	w = 1/[σ^2(Fo^2) + (0.0681P)^2 + 0.0908P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
7715 reflections	Δρmax = 0.28 e Å^−3
633 parameters	Δρmin = −0.21 e Å^−3
1 restraint	Absolute structure: Flack (1983), 446 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (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	Occ. (<1)
P1	0.66156 (7)	0.52220 (4)	0.14767 (4)	0.04806 (17)
N1	0.7150 (2)	0.47541 (15)	0.06674 (14)	0.0533 (6)
N2	0.5074 (2)	0.47915 (15)	0.14649 (13)	0.0501 (5)
O1	0.7542 (2)	0.51962 (15)	0.22760 (12)	0.0636 (5)
O21	0.5579 (3)	0.6556 (2)	0.19133 (19)	0.0685 (11)	0.703 (6)
H21	0.6233	0.6802	0.2186	0.103*	0.703 (6)
O22	0.7570 (7)	0.6618 (4)	0.1191 (4)	0.061 (2)	0.297 (6)
H22	0.7726	0.6808	0.1741	0.091*	0.297 (6)
C1	0.5928 (3)	0.44083 (18)	0.01737 (16)	0.0517 (6)
H1B	0.5489	0.4823	−0.0174	0.062*
C2	0.4916 (3)	0.41987 (18)	0.08053 (17)	0.0513 (6)
H2A	0.5232	0.3711	0.1068	0.062*
C3	0.3489 (3)	0.4061 (2)	0.0358 (2)	0.0683 (9)
H3A	0.3133	0.4534	0.0097	0.082*
H3B	0.2856	0.3897	0.0763	0.082*
C4	0.3579 (4)	0.3442 (2)	−0.0317 (2)	0.0707 (9)
H4A	0.3723	0.2948	−0.0040	0.085*
H4B	0.2695	0.3420	−0.0663	0.085*
C5	0.4718 (4)	0.3568 (2)	−0.0884 (2)	0.0783 (10)
H5A	0.4451	0.3988	−0.1267	0.094*
H5B	0.4806	0.3110	−0.1223	0.094*
C6	0.6127 (4)	0.3750 (2)	−0.0422 (2)	0.0702 (9)
H6A	0.6489	0.3304	−0.0107	0.084*
H6B	0.6783	0.3893	−0.0822	0.084*
C7	0.8561 (3)	0.4653 (2)	0.0416 (2)	0.0617 (7)
H7A	0.8492	0.4663	−0.0204	0.074*
C8	0.9184 (3)	0.3886 (2)	0.0691 (3)	0.0685 (9)
C9	0.9185 (4)	0.3640 (3)	0.1516 (3)	0.0917 (12)
H9A	0.8769	0.3940	0.1907	0.110*
C10	0.9812 (5)	0.2937 (3)	0.1767 (4)	0.1134 (17)
H10A	0.9793	0.2768	0.2322	0.136*
C11	1.0455 (5)	0.2498 (3)	0.1195 (5)	0.132 (3)
H11A	1.0896	0.2039	0.1361	0.159*
C12	1.0432 (5)	0.2748 (3)	0.0380 (5)	0.121 (2)
H12A	1.0849	0.2449	−0.0011	0.145*
C13	0.9815 (4)	0.3425 (3)	0.0124 (3)	0.0917 (13)
H13A	0.9817	0.3580	−0.0437	0.110*
C14	0.9531 (3)	0.5315 (2)	0.0730 (3)	0.0778 (10)
H14A	0.9117	0.5797	0.0549	0.117*
H14B	1.0412	0.5258	0.0500	0.117*
H14C	0.9670	0.5303	0.1336	0.117*
C15	0.4451 (3)	0.4689 (2)	0.22828 (18)	0.0606 (8)
H15A	0.5006	0.5008	0.2698	0.073*
C16	0.4618 (4)	0.3868 (2)	0.25939 (18)	0.0637 (8)
C17	0.5935 (4)	0.3611 (3)	0.2895 (2)	0.0792 (10)
H17A	0.6679	0.3954	0.2921	0.095*
C18	0.6169 (5)	0.2867 (3)	0.3157 (2)	0.0935 (13)
H18A	0.7061	0.2713	0.3360	0.112*
C19	0.5115 (6)	0.2360 (3)	0.3119 (2)	0.0938 (13)
H19A	0.5284	0.1852	0.3282	0.113*
C20	0.3788 (5)	0.2589 (3)	0.2839 (3)	0.0950 (14)
H20A	0.3056	0.2240	0.2831	0.114*
C21	0.3531 (5)	0.3349 (3)	0.2566 (2)	0.0813 (11)
H21B	0.2635	0.3501	0.2368	0.098*
C22	0.2963 (4)	0.5007 (3)	0.2234 (3)	0.0922 (13)
H22B	0.2956	0.5527	0.2032	0.138*
H22C	0.2635	0.4995	0.2787	0.138*
H22D	0.2366	0.4697	0.1854	0.138*
C23	0.6242 (3)	0.62387 (18)	0.12136 (19)	0.0572 (7)
H231	0.7126	0.6508	0.1171	0.069*	0.703 (6)
H232	0.5769	0.6465	0.1674	0.069*	0.297 (6)
C24	0.5337 (4)	0.63508 (19)	0.0407 (2)	0.0625 (8)
C25	0.5907 (5)	0.6340 (2)	−0.0365 (2)	0.0746 (10)
H25A	0.6862	0.6270	−0.0376	0.090*
C26	0.5087 (7)	0.6429 (3)	−0.1110 (3)	0.1087 (16)
H26A	0.5486	0.6415	−0.1621	0.130*
C27	0.3688 (8)	0.6539 (4)	−0.1106 (4)	0.1190 (19)
H27A	0.3139	0.6609	−0.1614	0.143*
C28	0.3102 (6)	0.6548 (3)	−0.0374 (4)	0.1124 (17)
H28A	0.2144	0.6617	−0.0381	0.135*
C29	0.3916 (4)	0.6453 (3)	0.0413 (3)	0.0809 (11)
H29A	0.3503	0.6460	0.0920	0.097*
P51	0.84661 (7)	0.74500 (4)	0.33839 (4)	0.05075 (19)
N51	0.9885 (2)	0.79776 (15)	0.35503 (14)	0.0547 (6)
N52	0.7646 (2)	0.78184 (15)	0.41630 (14)	0.0511 (5)
O51	0.7715 (2)	0.74788 (16)	0.25253 (11)	0.0687 (6)
O71	0.7506 (3)	0.60746 (19)	0.36671 (19)	0.0717 (10)	0.779 (6)
H71	0.7532	0.5776	0.3150	0.108*	0.779 (6)
O72	0.9494 (13)	0.6073 (8)	0.3006 (8)	0.088 (4)	0.221 (6)
H72	0.9005	0.5779	0.2850	0.131*	0.221 (6)
C51	0.9963 (3)	0.82818 (19)	0.44201 (18)	0.0547 (7)
H51B	1.0321	0.7863	0.4792	0.066*
C52	0.8487 (3)	0.84222 (18)	0.46154 (17)	0.0526 (6)
H52A	0.8198	0.8913	0.4350	0.063*
C53	0.8406 (4)	0.8517 (2)	0.5547 (2)	0.0732 (9)
H53A	0.8694	0.8045	0.5839	0.088*
H53B	0.7455	0.8629	0.5659	0.088*
C54	0.9359 (4)	0.9174 (2)	0.5863 (2)	0.0761 (10)
H54A	0.8947	0.9655	0.5656	0.091*
H54B	0.9411	0.9187	0.6476	0.091*
C55	1.0814 (4)	0.9122 (2)	0.5598 (2)	0.0809 (11)
H55A	1.1303	0.8710	0.5912	0.097*
H55B	1.1301	0.9598	0.5748	0.097*
C56	1.0866 (4)	0.8977 (2)	0.4656 (2)	0.0732 (9)
H56A	1.0519	0.9423	0.4334	0.088*
H56B	1.1817	0.8881	0.4533	0.088*
C57	1.0938 (3)	0.8155 (2)	0.2966 (2)	0.0641 (8)
H57A	1.1842	0.8185	0.3302	0.077*
C58	1.0679 (4)	0.8928 (2)	0.25314 (19)	0.0650 (8)
C59	0.9345 (4)	0.9152 (3)	0.2208 (2)	0.0820 (11)
H59A	0.8599	0.8825	0.2274	0.098*
C60	0.9101 (6)	0.9842 (3)	0.1795 (3)	0.1043 (15)
H60A	0.8197	0.9979	0.1594	0.125*
C61	1.0153 (8)	1.0312 (3)	0.1682 (3)	0.1175 (18)
H61A	0.9982	1.0770	0.1389	0.141*
C62	1.1533 (7)	1.0126 (3)	0.2004 (3)	0.119 (2)
H62A	1.2266	1.0461	0.1934	0.142*
C63	1.1767 (5)	0.9416 (3)	0.2434 (2)	0.0922 (13)
H63A	1.2664	0.9281	0.2651	0.111*
C64	1.1050 (5)	0.7530 (3)	0.2298 (3)	0.0935 (12)
H64A	1.1214	0.7042	0.2572	0.140*
H64B	1.1809	0.7647	0.1969	0.140*
H64C	1.0198	0.7508	0.1934	0.140*
C65	0.6095 (3)	0.7853 (2)	0.4069 (2)	0.0627 (8)
H65A	0.5797	0.7637	0.3511	0.075*
C66	0.5577 (3)	0.8682 (2)	0.4053 (2)	0.0629 (8)
C67	0.5752 (4)	0.9135 (3)	0.3355 (3)	0.0778 (10)
H67A	0.6176	0.8930	0.2903	0.093*
C68	0.5297 (4)	0.9900 (3)	0.3325 (4)	0.1029 (15)
H68A	0.5426	1.0206	0.2858	0.123*
C69	0.4656 (4)	1.0193 (3)	0.3996 (4)	0.1050 (15)
H69A	0.4350	1.0700	0.3975	0.126*
C70	0.4462 (4)	0.9766 (3)	0.4676 (4)	0.1007 (15)
H70A	0.4027	0.9974	0.5122	0.121*
C71	0.4920 (4)	0.9007 (3)	0.4706 (3)	0.0830 (11)
H71B	0.4782	0.8710	0.5178	0.100*
C72	0.5490 (4)	0.7330 (3)	0.4716 (3)	0.0980 (14)
H72B	0.5874	0.6823	0.4680	0.147*
H72C	0.4496	0.7307	0.4601	0.147*
H72D	0.5722	0.7532	0.5275	0.147*
C73	0.8834 (3)	0.64337 (19)	0.3659 (2)	0.0604 (7)
H731	0.9327	0.6199	0.3211	0.072*	0.779 (6)
H732	0.7939	0.6175	0.3698	0.072*	0.221 (6)
C74	0.9696 (4)	0.63264 (18)	0.4495 (2)	0.0662 (9)
C75	1.1139 (4)	0.6314 (2)	0.4532 (3)	0.0866 (12)
H75A	1.1574	0.6369	0.4037	0.104*
C76	1.1948 (6)	0.6220 (3)	0.5299 (4)	0.1175 (19)
H76A	1.2915	0.6219	0.5317	0.141*
C77	1.1304 (7)	0.6127 (3)	0.6030 (4)	0.119 (2)
H77A	1.1840	0.6053	0.6542	0.143*
C78	0.9899 (7)	0.6143 (3)	0.6010 (3)	0.1100 (17)
H78A	0.9477	0.6084	0.6509	0.132*
C79	0.9059 (5)	0.6247 (2)	0.5232 (2)	0.0830 (11)
H79A	0.8093	0.6261	0.5222	0.100*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0485 (4)	0.0479 (4)	0.0460 (3)	−0.0044 (3)	−0.0057 (3)	−0.0060 (3)
N1	0.0426 (11)	0.0590 (15)	0.0571 (13)	−0.0018 (11)	−0.0016 (9)	−0.0127 (11)
N2	0.0510 (12)	0.0526 (14)	0.0460 (11)	−0.0038 (11)	0.0001 (9)	−0.0051 (10)
O1	0.0642 (12)	0.0688 (13)	0.0538 (10)	−0.0062 (12)	−0.0166 (9)	−0.0098 (11)
O21	0.073 (2)	0.063 (2)	0.0673 (19)	0.0007 (17)	−0.0074 (15)	−0.0196 (16)
O22	0.069 (5)	0.048 (4)	0.065 (4)	−0.020 (3)	0.003 (3)	−0.010 (3)
C1	0.0554 (15)	0.0523 (16)	0.0466 (13)	−0.0113 (13)	0.0001 (11)	−0.0042 (12)
C2	0.0518 (15)	0.0504 (16)	0.0508 (14)	−0.0058 (12)	−0.0007 (11)	−0.0058 (12)
C3	0.0605 (18)	0.072 (2)	0.0698 (19)	−0.0187 (16)	−0.0073 (14)	−0.0065 (17)
C4	0.075 (2)	0.062 (2)	0.0706 (19)	−0.0185 (17)	−0.0181 (16)	−0.0090 (17)
C5	0.107 (3)	0.068 (2)	0.0563 (17)	−0.013 (2)	−0.0112 (18)	−0.0190 (17)
C6	0.075 (2)	0.073 (2)	0.0626 (18)	−0.0089 (18)	0.0064 (15)	−0.0221 (17)
C7	0.0531 (15)	0.067 (2)	0.0659 (17)	−0.0060 (15)	0.0121 (13)	−0.0028 (15)
C8	0.0414 (14)	0.066 (2)	0.098 (3)	−0.0026 (15)	0.0050 (15)	−0.0074 (19)
C9	0.073 (2)	0.084 (3)	0.116 (3)	0.012 (2)	−0.003 (2)	0.013 (3)
C10	0.091 (3)	0.089 (4)	0.154 (5)	0.006 (3)	−0.019 (3)	0.032 (3)
C11	0.074 (3)	0.056 (3)	0.260 (8)	−0.003 (2)	−0.020 (4)	0.016 (4)
C12	0.074 (3)	0.068 (3)	0.222 (7)	0.003 (2)	0.020 (4)	−0.034 (4)
C13	0.0543 (19)	0.078 (3)	0.146 (4)	−0.0033 (19)	0.025 (2)	−0.027 (3)
C14	0.0536 (17)	0.076 (2)	0.103 (3)	−0.0115 (17)	0.0045 (17)	0.004 (2)
C15	0.0590 (17)	0.070 (2)	0.0533 (15)	−0.0037 (15)	0.0106 (13)	−0.0054 (15)
C16	0.077 (2)	0.073 (2)	0.0418 (13)	−0.0081 (18)	0.0110 (13)	0.0002 (14)
C17	0.087 (2)	0.084 (3)	0.0639 (19)	−0.007 (2)	−0.0037 (17)	0.0148 (19)
C18	0.115 (3)	0.089 (3)	0.073 (2)	0.000 (3)	−0.012 (2)	0.021 (2)
C19	0.137 (4)	0.078 (3)	0.065 (2)	−0.006 (3)	0.008 (2)	0.009 (2)
C20	0.118 (3)	0.087 (3)	0.082 (2)	−0.037 (3)	0.025 (2)	−0.004 (2)
C21	0.089 (2)	0.091 (3)	0.065 (2)	−0.014 (2)	0.0149 (18)	0.001 (2)
C22	0.072 (2)	0.103 (3)	0.106 (3)	0.016 (2)	0.034 (2)	0.005 (2)
C23	0.0624 (17)	0.0471 (17)	0.0605 (16)	−0.0070 (14)	−0.0028 (14)	−0.0106 (14)
C24	0.075 (2)	0.0404 (17)	0.0687 (19)	−0.0061 (15)	−0.0076 (16)	0.0008 (14)
C25	0.099 (3)	0.057 (2)	0.067 (2)	−0.007 (2)	0.0013 (18)	0.0078 (17)
C26	0.162 (5)	0.088 (3)	0.072 (3)	−0.001 (3)	−0.010 (3)	0.020 (2)
C27	0.158 (5)	0.097 (4)	0.092 (3)	0.000 (4)	−0.043 (3)	0.017 (3)
C28	0.101 (3)	0.092 (3)	0.134 (4)	0.011 (3)	−0.045 (3)	0.006 (3)
C29	0.074 (2)	0.074 (2)	0.091 (3)	0.009 (2)	−0.0097 (19)	0.008 (2)
P51	0.0585 (4)	0.0482 (4)	0.0442 (3)	−0.0088 (3)	−0.0023 (3)	−0.0045 (3)
N51	0.0581 (13)	0.0534 (14)	0.0523 (12)	−0.0134 (11)	0.0035 (10)	−0.0044 (11)
N52	0.0499 (12)	0.0521 (13)	0.0504 (12)	−0.0077 (11)	−0.0007 (9)	−0.0046 (11)
O51	0.0856 (14)	0.0712 (14)	0.0459 (10)	−0.0125 (13)	−0.0119 (9)	−0.0047 (11)
O71	0.080 (2)	0.0625 (19)	0.0710 (18)	−0.0206 (16)	0.0010 (15)	−0.0107 (15)
O72	0.090 (8)	0.077 (8)	0.097 (9)	−0.009 (7)	0.016 (6)	−0.037 (7)
C51	0.0521 (15)	0.0542 (17)	0.0558 (15)	−0.0076 (13)	−0.0061 (12)	−0.0093 (13)
C52	0.0556 (15)	0.0500 (16)	0.0506 (14)	−0.0083 (13)	−0.0037 (11)	−0.0066 (12)
C53	0.082 (2)	0.079 (2)	0.0571 (17)	−0.0022 (19)	−0.0015 (15)	−0.0171 (18)
C54	0.097 (3)	0.069 (2)	0.0586 (18)	−0.003 (2)	−0.0114 (17)	−0.0190 (17)
C55	0.088 (3)	0.061 (2)	0.086 (2)	−0.0129 (19)	−0.031 (2)	−0.0168 (19)
C56	0.075 (2)	0.063 (2)	0.080 (2)	−0.0190 (18)	−0.0039 (17)	−0.0131 (17)
C57	0.0539 (16)	0.070 (2)	0.0694 (18)	0.0017 (15)	0.0109 (14)	0.0052 (16)
C58	0.076 (2)	0.067 (2)	0.0538 (15)	−0.0171 (17)	0.0174 (15)	−0.0018 (15)
C59	0.089 (3)	0.074 (2)	0.083 (2)	−0.002 (2)	0.0070 (19)	0.022 (2)
C60	0.134 (4)	0.081 (3)	0.097 (3)	−0.001 (3)	0.005 (3)	0.025 (3)
C61	0.190 (6)	0.081 (3)	0.082 (3)	−0.022 (4)	0.013 (3)	0.009 (3)
C62	0.172 (5)	0.091 (4)	0.099 (3)	−0.069 (4)	0.043 (3)	−0.001 (3)
C63	0.098 (3)	0.102 (3)	0.080 (2)	−0.036 (3)	0.030 (2)	−0.006 (2)
C64	0.114 (3)	0.084 (3)	0.089 (3)	0.015 (3)	0.043 (2)	0.000 (2)
C65	0.0505 (15)	0.072 (2)	0.0647 (17)	−0.0140 (15)	0.0030 (13)	−0.0010 (16)
C66	0.0437 (15)	0.072 (2)	0.0720 (18)	−0.0080 (14)	0.0000 (13)	−0.0034 (17)
C67	0.0595 (19)	0.087 (3)	0.085 (2)	−0.0006 (19)	−0.0030 (16)	0.015 (2)
C68	0.076 (3)	0.103 (4)	0.127 (4)	−0.003 (3)	−0.005 (3)	0.036 (3)
C69	0.067 (2)	0.077 (3)	0.173 (5)	−0.002 (2)	0.019 (3)	0.000 (4)
C70	0.070 (2)	0.094 (4)	0.142 (4)	−0.002 (2)	0.029 (3)	−0.027 (3)
C71	0.063 (2)	0.093 (3)	0.095 (3)	−0.011 (2)	0.0183 (18)	−0.004 (2)
C72	0.083 (3)	0.087 (3)	0.128 (4)	−0.018 (2)	0.030 (2)	0.016 (3)
C73	0.0682 (19)	0.0473 (17)	0.0645 (17)	−0.0086 (15)	0.0005 (15)	−0.0095 (14)
C74	0.082 (2)	0.0323 (15)	0.081 (2)	−0.0052 (15)	−0.0132 (18)	−0.0015 (15)
C75	0.083 (3)	0.062 (2)	0.111 (3)	0.000 (2)	−0.017 (2)	0.008 (2)
C76	0.094 (3)	0.091 (3)	0.157 (5)	−0.010 (3)	−0.046 (3)	0.027 (4)
C77	0.142 (5)	0.089 (3)	0.114 (4)	−0.020 (3)	−0.055 (4)	0.023 (3)
C78	0.152 (5)	0.091 (3)	0.079 (3)	−0.017 (3)	−0.033 (3)	0.018 (2)
C79	0.104 (3)	0.070 (2)	0.071 (2)	−0.010 (2)	−0.011 (2)	0.0096 (19)

Geometric parameters (Å, º)

P1—O1	1.4823 (18)	P51—O51	1.4833 (19)
P1—N1	1.644 (2)	P51—N51	1.648 (2)
P1—N2	1.663 (2)	P51—N52	1.658 (2)
P1—C23	1.844 (3)	P51—C73	1.847 (4)
N1—C7	1.464 (4)	N51—C57	1.471 (4)
N1—C1	1.480 (3)	N51—C51	1.474 (4)
N2—C2	1.467 (4)	N52—C52	1.472 (4)
N2—C15	1.491 (4)	N52—C65	1.490 (4)
O21—C23	1.443 (4)	O71—C73	1.426 (4)
O21—H21	0.8475	O71—H71	0.9738
O22—C23	1.444 (7)	O72—C73	1.412 (12)
O22—H22	0.9332	O72—H72	0.7227
C1—C6	1.508 (4)	C51—C52	1.505 (4)
C1—C2	1.508 (4)	C51—C56	1.516 (4)
C1—H1B	0.9800	C51—H51B	0.9800
C2—C3	1.506 (4)	C52—C53	1.498 (4)
C2—H2A	0.9800	C52—H52A	0.9800
C3—C4	1.528 (5)	C53—C54	1.522 (5)
C3—H3A	0.9700	C53—H53A	0.9700
C3—H3B	0.9700	C53—H53B	0.9700
C4—C5	1.500 (5)	C54—C55	1.504 (6)
C4—H4A	0.9700	C54—H54A	0.9700
C4—H4B	0.9700	C54—H54B	0.9700
C5—C6	1.516 (5)	C55—C56	1.522 (5)
C5—H5A	0.9700	C55—H55A	0.9700
C5—H5B	0.9700	C55—H55B	0.9700
C6—H6A	0.9700	C56—H56A	0.9700
C6—H6B	0.9700	C56—H56B	0.9700
C7—C8	1.511 (5)	C57—C58	1.522 (5)
C7—C14	1.536 (5)	C57—C64	1.529 (5)
C7—H7A	0.9800	C57—H57A	0.9800
C8—C9	1.377 (6)	C58—C63	1.368 (5)
C8—C13	1.387 (5)	C58—C59	1.395 (5)
C9—C10	1.405 (7)	C59—C60	1.378 (6)
C9—H9A	0.9300	C59—H59A	0.9300
C10—C11	1.378 (8)	C60—C61	1.328 (8)
C10—H10A	0.9300	C60—H60A	0.9300
C11—C12	1.363 (8)	C61—C62	1.417 (8)
C11—H11A	0.9300	C61—H61A	0.9300
C12—C13	1.365 (8)	C62—C63	1.420 (8)
C12—H12A	0.9300	C62—H62A	0.9300
C13—H13A	0.9300	C63—H63A	0.9300
C14—H14A	0.9600	C64—H64A	0.9600
C14—H14B	0.9600	C64—H64B	0.9600
C14—H14C	0.9600	C64—H64C	0.9600
C15—C16	1.514 (5)	C65—C66	1.524 (5)
C15—C22	1.533 (5)	C65—C72	1.528 (5)
C15—H15A	0.9800	C65—H65A	0.9800
C16—C21	1.381 (5)	C66—C67	1.383 (5)
C16—C17	1.388 (5)	C66—C71	1.385 (5)
C17—C18	1.372 (7)	C67—C68	1.400 (7)
C17—H17A	0.9300	C67—H67A	0.9300
C18—C19	1.342 (7)	C68—C69	1.379 (7)
C18—H18A	0.9300	C68—H68A	0.9300
C19—C20	1.374 (7)	C69—C70	1.338 (7)
C19—H19A	0.9300	C69—H69A	0.9300
C20—C21	1.405 (7)	C70—C71	1.390 (7)
C20—H20A	0.9300	C70—H70A	0.9300
C21—H21B	0.9300	C71—H71B	0.9300
C22—H22B	0.9600	C72—H72B	0.9600
C22—H22C	0.9600	C72—H72C	0.9600
C22—H22D	0.9600	C72—H72D	0.9600
C23—C24	1.494 (4)	C73—C74	1.511 (4)
C23—H231	0.9800	C73—H731	0.9800
C23—H232	0.9800	C73—H732	0.9800
C24—C29	1.382 (5)	C74—C79	1.380 (6)
C24—C25	1.390 (5)	C74—C75	1.387 (6)
C25—C26	1.369 (6)	C75—C76	1.394 (6)
C25—H25A	0.9300	C75—H75A	0.9300
C26—C27	1.363 (8)	C76—C77	1.375 (9)
C26—H26A	0.9300	C76—H76A	0.9300
C27—C28	1.340 (8)	C77—C78	1.353 (8)
C27—H27A	0.9300	C77—H77A	0.9300
C28—C29	1.422 (6)	C78—C79	1.423 (6)
C28—H28A	0.9300	C78—H78A	0.9300
C29—H29A	0.9300	C79—H79A	0.9300
O1—P1—N1	116.53 (12)	O51—P51—N51	117.07 (13)
O1—P1—N2	117.52 (12)	O51—P51—N52	116.53 (13)
N1—P1—N2	96.51 (12)	N51—P51—N52	96.44 (12)
O1—P1—C23	108.18 (14)	O51—P51—C73	108.41 (15)
N1—P1—C23	111.47 (14)	N51—P51—C73	110.89 (14)
N2—P1—C23	105.89 (13)	N52—P51—C73	106.73 (14)
C7—N1—C1	121.4 (2)	C57—N51—C51	122.6 (2)
C7—N1—P1	129.76 (19)	C57—N51—P51	128.8 (2)
C1—N1—P1	108.86 (17)	C51—N51—P51	108.58 (18)
C2—N2—C15	121.0 (2)	C52—N52—C65	121.5 (2)
C2—N2—P1	110.93 (18)	C52—N52—P51	111.10 (17)
C15—N2—P1	118.42 (18)	C65—N52—P51	119.03 (19)
C23—O21—H21	103.0	C73—O71—H71	97.5
C23—O22—H22	101.8	C73—O72—H72	104.0
N1—C1—C6	119.9 (3)	N51—C51—C52	106.6 (2)
N1—C1—C2	106.2 (2)	N51—C51—C56	119.7 (3)
C6—C1—C2	111.2 (3)	C52—C51—C56	110.6 (3)
N1—C1—H1B	106.2	N51—C51—H51B	106.4
C6—C1—H1B	106.2	C52—C51—H51B	106.4
C2—C1—H1B	106.2	C56—C51—H51B	106.4
N2—C2—C3	118.5 (3)	N52—C52—C53	118.9 (3)
N2—C2—C1	105.9 (2)	N52—C52—C51	105.8 (2)
C3—C2—C1	110.1 (2)	C53—C52—C51	111.1 (2)
N2—C2—H2A	107.3	N52—C52—H52A	106.8
C3—C2—H2A	107.3	C53—C52—H52A	106.8
C1—C2—H2A	107.3	C51—C52—H52A	106.8
C2—C3—C4	109.5 (3)	C52—C53—C54	108.8 (3)
C2—C3—H3A	109.8	C52—C53—H53A	109.9
C4—C3—H3A	109.8	C54—C53—H53A	109.9
C2—C3—H3B	109.8	C52—C53—H53B	109.9
C4—C3—H3B	109.8	C54—C53—H53B	109.9
H3A—C3—H3B	108.2	H53A—C53—H53B	108.3
C5—C4—C3	114.3 (3)	C55—C54—C53	114.3 (3)
C5—C4—H4A	108.7	C55—C54—H54A	108.7
C3—C4—H4A	108.7	C53—C54—H54A	108.7
C5—C4—H4B	108.7	C55—C54—H54B	108.7
C3—C4—H4B	108.7	C53—C54—H54B	108.7
H4A—C4—H4B	107.6	H54A—C54—H54B	107.6
C4—C5—C6	114.4 (3)	C54—C55—C56	113.7 (3)
C4—C5—H5A	108.7	C54—C55—H55A	108.8
C6—C5—H5A	108.7	C56—C55—H55A	108.8
C4—C5—H5B	108.7	C54—C55—H55B	108.8
C6—C5—H5B	108.7	C56—C55—H55B	108.8
H5A—C5—H5B	107.6	H55A—C55—H55B	107.7
C1—C6—C5	107.6 (3)	C51—C56—C55	107.7 (3)
C1—C6—H6A	110.2	C51—C56—H56A	110.2
C5—C6—H6A	110.2	C55—C56—H56A	110.2
C1—C6—H6B	110.2	C51—C56—H56B	110.2
C5—C6—H6B	110.2	C55—C56—H56B	110.2
H6A—C6—H6B	108.5	H56A—C56—H56B	108.5
N1—C7—C8	112.5 (3)	N51—C57—C58	112.2 (3)
N1—C7—C14	112.0 (3)	N51—C57—C64	112.7 (3)
C8—C7—C14	110.7 (3)	C58—C57—C64	109.4 (3)
N1—C7—H7A	107.1	N51—C57—H57A	107.4
C8—C7—H7A	107.1	C58—C57—H57A	107.4
C14—C7—H7A	107.1	C64—C57—H57A	107.4
C9—C8—C13	118.5 (4)	C63—C58—C59	118.4 (4)
C9—C8—C7	120.9 (3)	C63—C58—C57	120.3 (4)
C13—C8—C7	120.6 (4)	C59—C58—C57	121.3 (3)
C8—C9—C10	120.2 (5)	C60—C59—C58	121.9 (4)
C8—C9—H9A	119.9	C60—C59—H59A	119.1
C10—C9—H9A	119.9	C58—C59—H59A	119.1
C11—C10—C9	120.2 (6)	C61—C60—C59	120.1 (5)
C11—C10—H10A	119.9	C61—C60—H60A	119.9
C9—C10—H10A	119.9	C59—C60—H60A	119.9
C12—C11—C10	118.7 (5)	C60—C61—C62	120.9 (5)
C12—C11—H11A	120.6	C60—C61—H61A	119.5
C10—C11—H11A	120.6	C62—C61—H61A	119.5
C11—C12—C13	121.8 (5)	C61—C62—C63	118.3 (5)
C11—C12—H12A	119.1	C61—C62—H62A	120.9
C13—C12—H12A	119.1	C63—C62—H62A	120.9
C12—C13—C8	120.6 (5)	C58—C63—C62	120.3 (5)
C12—C13—H13A	119.7	C58—C63—H63A	119.9
C8—C13—H13A	119.7	C62—C63—H63A	119.9
C7—C14—H14A	109.5	C57—C64—H64A	109.5
C7—C14—H14B	109.5	C57—C64—H64B	109.5
H14A—C14—H14B	109.5	H64A—C64—H64B	109.5
C7—C14—H14C	109.5	C57—C64—H64C	109.5
H14A—C14—H14C	109.5	H64A—C64—H64C	109.5
H14B—C14—H14C	109.5	H64B—C64—H64C	109.5
N2—C15—C16	110.9 (3)	N52—C65—C66	111.4 (2)
N2—C15—C22	111.4 (3)	N52—C65—C72	110.5 (3)
C16—C15—C22	115.2 (3)	C66—C65—C72	115.4 (3)
N2—C15—H15A	106.2	N52—C65—H65A	106.3
C16—C15—H15A	106.2	C66—C65—H65A	106.3
C22—C15—H15A	106.2	C72—C65—H65A	106.3
C21—C16—C17	117.9 (4)	C67—C66—C71	117.8 (4)
C21—C16—C15	123.3 (3)	C67—C66—C65	119.1 (3)
C17—C16—C15	118.8 (3)	C71—C66—C65	123.1 (3)
C18—C17—C16	121.8 (4)	C66—C67—C68	120.5 (4)
C18—C17—H17A	119.1	C66—C67—H67A	119.8
C16—C17—H17A	119.1	C68—C67—H67A	119.8
C19—C18—C17	120.3 (4)	C69—C68—C67	119.1 (5)
C19—C18—H18A	119.9	C69—C68—H68A	120.4
C17—C18—H18A	119.9	C67—C68—H68A	120.4
C18—C19—C20	120.1 (5)	C70—C69—C68	121.7 (5)
C18—C19—H19A	119.9	C70—C69—H69A	119.2
C20—C19—H19A	119.9	C68—C69—H69A	119.2
C19—C20—C21	120.3 (4)	C69—C70—C71	119.1 (5)
C19—C20—H20A	119.9	C69—C70—H70A	120.5
C21—C20—H20A	119.9	C71—C70—H70A	120.5
C16—C21—C20	119.6 (4)	C66—C71—C70	121.9 (5)
C16—C21—H21B	120.2	C66—C71—H71B	119.1
C20—C21—H21B	120.2	C70—C71—H71B	119.1
C15—C22—H22B	109.5	C65—C72—H72B	109.5
C15—C22—H22C	109.5	C65—C72—H72C	109.5
H22B—C22—H22C	109.5	H72B—C72—H72C	109.5
C15—C22—H22D	109.5	C65—C72—H72D	109.5
H22B—C22—H22D	109.5	H72B—C72—H72D	109.5
H22C—C22—H22D	109.5	H72C—C72—H72D	109.5
O21—C23—O22	107.6 (4)	O72—C73—O71	106.2 (6)
O21—C23—C24	110.2 (3)	O72—C73—C74	109.9 (6)
O22—C23—C24	111.6 (4)	O71—C73—C74	111.0 (3)
O21—C23—P1	106.5 (2)	O72—C73—P51	110.0 (6)
O22—C23—P1	106.8 (4)	O71—C73—P51	105.6 (2)
C24—C23—P1	113.9 (2)	C74—C73—P51	113.8 (2)
O21—C23—H231	108.7	O71—C73—H731	108.8
C24—C23—H231	108.7	C74—C73—H731	108.8
P1—C23—H231	108.7	P51—C73—H731	108.8
O22—C23—H232	108.1	O72—C73—H732	107.6
C24—C23—H232	108.1	C74—C73—H732	107.6
P1—C23—H232	108.1	P51—C73—H732	107.6
H231—C23—H232	109.2	H731—C73—H732	110.2
C29—C24—C25	118.9 (3)	C79—C74—C75	119.1 (4)
C29—C24—C23	120.7 (3)	C79—C74—C73	120.4 (3)
C25—C24—C23	120.4 (3)	C75—C74—C73	120.4 (4)
C26—C25—C24	121.1 (5)	C74—C75—C76	121.1 (5)
C26—C25—H25A	119.5	C74—C75—H75A	119.5
C24—C25—H25A	119.5	C76—C75—H75A	119.5
C27—C26—C25	120.3 (5)	C77—C76—C75	119.5 (5)
C27—C26—H26A	119.9	C77—C76—H76A	120.3
C25—C26—H26A	119.9	C75—C76—H76A	120.3
C28—C27—C26	120.2 (5)	C78—C77—C76	120.5 (5)
C28—C27—H27A	119.9	C78—C77—H77A	119.8
C26—C27—H27A	119.9	C76—C77—H77A	119.8
C27—C28—C29	121.3 (5)	C77—C78—C79	120.7 (5)
C27—C28—H28A	119.4	C77—C78—H78A	119.6
C29—C28—H28A	119.4	C79—C78—H78A	119.6
C24—C29—C28	118.3 (5)	C74—C79—C78	119.1 (5)
C24—C29—H29A	120.9	C74—C79—H79A	120.4
C28—C29—H29A	120.9	C78—C79—H79A	120.4
O1—P1—N1—C7	−36.0 (3)	O51—P51—N51—C57	−35.3 (3)
N2—P1—N1—C7	−161.2 (3)	N52—P51—N51—C57	−159.5 (3)
C23—P1—N1—C7	88.9 (3)	C73—P51—N51—C57	89.8 (3)
O1—P1—N1—C1	143.7 (2)	O51—P51—N51—C51	143.8 (2)
N2—P1—N1—C1	18.5 (2)	N52—P51—N51—C51	19.6 (2)
C23—P1—N1—C1	−91.5 (2)	C73—P51—N51—C51	−91.1 (2)
O1—P1—N2—C2	−122.0 (2)	O51—P51—N52—C52	−123.7 (2)
N1—P1—N2—C2	2.5 (2)	N51—P51—N52—C52	1.0 (2)
C23—P1—N2—C2	117.1 (2)	C73—P51—N52—C52	115.1 (2)
O1—P1—N2—C15	24.5 (3)	O51—P51—N52—C65	25.0 (3)
N1—P1—N2—C15	149.0 (2)	N51—P51—N52—C65	149.6 (2)
C23—P1—N2—C15	−96.5 (2)	C73—P51—N52—C65	−96.3 (2)
C7—N1—C1—C6	19.5 (4)	C57—N51—C51—C52	145.4 (3)
P1—N1—C1—C6	−160.3 (2)	P51—N51—C51—C52	−33.8 (3)
C7—N1—C1—C2	146.4 (3)	C57—N51—C51—C56	19.1 (5)
P1—N1—C1—C2	−33.3 (3)	P51—N51—C51—C56	−160.1 (3)
C15—N2—C2—C3	68.4 (4)	C65—N52—C52—C53	66.1 (4)
P1—N2—C2—C3	−146.2 (2)	P51—N52—C52—C53	−146.1 (3)
C15—N2—C2—C1	−167.4 (2)	C65—N52—C52—C51	−168.2 (3)
P1—N2—C2—C1	−22.0 (3)	P51—N52—C52—C51	−20.5 (3)
N1—C1—C2—N2	34.2 (3)	N51—C51—C52—N52	33.6 (3)
C6—C1—C2—N2	166.2 (2)	C56—C51—C52—N52	165.2 (3)
N1—C1—C2—C3	163.4 (3)	N51—C51—C52—C53	163.9 (3)
C6—C1—C2—C3	−64.5 (4)	C56—C51—C52—C53	−64.5 (4)
N2—C2—C3—C4	178.2 (3)	N52—C52—C53—C54	−179.8 (3)
C1—C2—C3—C4	56.1 (4)	C51—C52—C53—C54	57.1 (4)
C2—C3—C4—C5	−48.9 (4)	C52—C53—C54—C55	−50.2 (4)
C3—C4—C5—C6	48.5 (5)	C53—C54—C55—C56	49.7 (5)
N1—C1—C6—C5	−175.3 (3)	N51—C51—C56—C55	−176.3 (3)
C2—C1—C6—C5	60.1 (4)	C52—C51—C56—C55	59.3 (4)
C4—C5—C6—C1	−52.1 (4)	C54—C55—C56—C51	−52.3 (4)
C1—N1—C7—C8	−80.6 (4)	C51—N51—C57—C58	−82.3 (4)
P1—N1—C7—C8	99.1 (3)	P51—N51—C57—C58	96.7 (3)
C1—N1—C7—C14	154.0 (3)	C51—N51—C57—C64	153.5 (3)
P1—N1—C7—C14	−26.4 (4)	P51—N51—C57—C64	−27.4 (4)
N1—C7—C8—C9	−50.9 (4)	N51—C57—C58—C63	137.8 (3)
C14—C7—C8—C9	75.3 (4)	C64—C57—C58—C63	−96.3 (4)
N1—C7—C8—C13	131.5 (3)	N51—C57—C58—C59	−43.6 (4)
C14—C7—C8—C13	−102.4 (4)	C64—C57—C58—C59	82.3 (4)
C13—C8—C9—C10	−0.1 (6)	C63—C58—C59—C60	0.3 (6)
C7—C8—C9—C10	−177.8 (3)	C57—C58—C59—C60	−178.3 (4)
C8—C9—C10—C11	1.3 (7)	C58—C59—C60—C61	1.0 (7)
C9—C10—C11—C12	−1.9 (7)	C59—C60—C61—C62	−1.8 (8)
C10—C11—C12—C13	1.2 (8)	C60—C61—C62—C63	1.3 (8)
C11—C12—C13—C8	0.0 (7)	C59—C58—C63—C62	−0.8 (6)
C9—C8—C13—C12	−0.6 (6)	C57—C58—C63—C62	177.9 (4)
C7—C8—C13—C12	177.1 (3)	C61—C62—C63—C58	0.0 (7)
C2—N2—C15—C16	40.1 (3)	C52—N52—C65—C66	29.5 (4)
P1—N2—C15—C16	−102.9 (3)	P51—N52—C65—C66	−115.8 (3)
C2—N2—C15—C22	−89.7 (4)	C52—N52—C65—C72	−100.2 (4)
P1—N2—C15—C22	127.3 (3)	P51—N52—C65—C72	114.6 (3)
N2—C15—C16—C21	−106.4 (3)	N52—C65—C66—C67	70.6 (4)
C22—C15—C16—C21	21.3 (4)	C72—C65—C66—C67	−162.4 (3)
N2—C15—C16—C17	71.3 (3)	N52—C65—C66—C71	−110.0 (3)
C22—C15—C16—C17	−161.0 (3)	C72—C65—C66—C71	17.0 (5)
C21—C16—C17—C18	0.3 (5)	C71—C66—C67—C68	1.0 (5)
C15—C16—C17—C18	−177.5 (3)	C65—C66—C67—C68	−179.5 (3)
C16—C17—C18—C19	0.6 (6)	C66—C67—C68—C69	−0.8 (6)
C17—C18—C19—C20	−1.7 (7)	C67—C68—C69—C70	0.2 (7)
C18—C19—C20—C21	2.0 (6)	C68—C69—C70—C71	0.0 (7)
C17—C16—C21—C20	0.0 (5)	C67—C66—C71—C70	−0.8 (5)
C15—C16—C21—C20	177.6 (3)	C65—C66—C71—C70	179.8 (3)
C19—C20—C21—C16	−1.1 (6)	C69—C70—C71—C66	0.2 (6)
O1—P1—C23—O21	−59.6 (2)	O51—P51—C73—O72	51.7 (6)
N1—P1—C23—O21	171.04 (19)	N51—P51—C73—O72	−78.1 (6)
N2—P1—C23—O21	67.2 (2)	N52—P51—C73—O72	178.0 (6)
O1—P1—C23—O22	55.2 (4)	O51—P51—C73—O71	−62.4 (2)
N1—P1—C23—O22	−74.2 (3)	N51—P51—C73—O71	167.7 (2)
N2—P1—C23—O22	−178.0 (3)	N52—P51—C73—O71	63.8 (2)
O1—P1—C23—C24	178.8 (2)	O51—P51—C73—C74	175.6 (2)
N1—P1—C23—C24	49.4 (3)	N51—P51—C73—C74	45.7 (3)
N2—P1—C23—C24	−54.4 (3)	N52—P51—C73—C74	−58.2 (3)
O21—C23—C24—C29	−23.2 (5)	O72—C73—C74—C79	−146.0 (7)
O22—C23—C24—C29	−142.6 (5)	O71—C73—C74—C79	−28.8 (4)
P1—C23—C24—C29	96.4 (4)	P51—C73—C74—C79	90.1 (4)
O21—C23—C24—C25	158.0 (3)	O72—C73—C74—C75	34.6 (7)
O22—C23—C24—C25	38.6 (5)	O71—C73—C74—C75	151.8 (3)
P1—C23—C24—C25	−82.4 (4)	P51—C73—C74—C75	−89.3 (4)
C29—C24—C25—C26	0.1 (6)	C79—C74—C75—C76	0.2 (6)
C23—C24—C25—C26	178.9 (4)	C73—C74—C75—C76	179.6 (4)
C24—C25—C26—C27	0.7 (8)	C74—C75—C76—C77	0.9 (8)
C25—C26—C27—C28	−1.1 (9)	C75—C76—C77—C78	−1.4 (9)
C26—C27—C28—C29	0.8 (10)	C76—C77—C78—C79	0.7 (9)
C25—C24—C29—C28	−0.4 (6)	C75—C74—C79—C78	−0.9 (6)
C23—C24—C29—C28	−179.2 (4)	C73—C74—C79—C78	179.7 (4)
C27—C28—C29—C24	−0.1 (8)	C77—C78—C79—C74	0.5 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21···O51	0.85	1.89	2.718 (4)	165
O22—H22···O51	0.93	1.71	2.587 (7)	156
O71—H71···O1	0.97	1.72	2.688 (4)	176
O72—H72···O1	0.72	1.90	2.608 (12)	167