Multiple intra­molecular hydrogen bonds in 2,4-di-tert-butyl-6-[N-(2,6-diisopropyl­phenyl)-P,P-diphenyl­phosphor­imidoyl]­phenol

The title compound, C₃₈H₄₈NOP, isolated from the reaction of (2-diphenyl­phosphanyl-4,6-di-tert-butyl)phenol with 2,6-di­iso­propyl­phenyl ­azide at 273 K, can act as an N,O-bidentate ligand. Crystal structure analysis shows a deviation from ideal tetra­hedral symmetry around the P atom. The mol­ecule exists as a monomer in the solid state, whose conformation is stabilized via multiple intra­molecular hydrogen bonds. Geometric parameters from both experimental and theoretical calculations are compared.

S1. Comment

The search for non-metallocene transition metal complexes to catalyse olefin polymerization has resulted in a wide range of new catalysts based on new or known ancillary ligands (Hlatky, 2000; Gibson & Spitzmesser, 2003). In recent years, there has been considerable and growing interest in the coordination chemistry of sterically hindered phosphinimine and phosphiniminate complexes (Masuda et al., 2003; Cristau et al., 2002; Said et al., 2001). Among these, titanium complexes bearing phosphinimide ligands have been shown by Stephan et al. (2003) to be highly active ethylene polymerization catalysts. At the same time, Fujita and co-workers (Mitani et al., 2002, 2003) developed a series of group IV metal complexes containing bis(phenoxyimine) ligands, and these complexes have proved to be excellent precatalysts for olefin polymerization. Subsequently, Zhang and co-workers (Qi et al., 2005; Qi & Zhang, 2006) reported that group IV metal complexes with phenoxy–phosphinimine ligands reacted similarly. Intrigued by the possibility that increasing the bulk of the N-containing substituents could improve catalytic activity, we investigated the use of the title compound, (I), containing the bulky 2,6-diisopropylphenyl group on atom N1 and tert-butyl groups on the phenol unit. As part of our efforts in the development and structural studies of these molecules, we report the synthesis and X-ray crystal structure of (I), supported by density functional theory (DFT) calculations.

As shown in Fig. 1 and Table 1, compound (I) has five intramolecular hydrogen bonds. The strong O1—H1···N1 hydrogen-bond distance of 2.601 (2) Å is in good agreement with the values of 2.580 (6) and 2.619 (6) Å reported for (1Z,3Z)-1,4-di(pyridin-2-yl)buta-1,3-diene-2,3-diol (Ośmiałowski et al., 2002), and 2.600 (2) and 2.540 (2) Å in bis[2-(2-hydroxy-3-methoxybenzylideneamino)phenolato-κO]dimethylsilane (Böhme & Fels, 2010). The six-membered N1/P1/C2/C1/O1/H1 ring, containing the phosphinimine unit and the O1—H1···N1 hydrogen bond, is planar to within 0.041 (1) Å and nearly coplanar with the phenoxy ring, with a dihedral angle of 3.05 (3)°. The remainder of the hydrogen bonds are weak, between the heteroatoms (O1 and N1) and the alkyl substituents [C—H of C(CH₃)₃ and CH(CH₃)₂] of the aromatic rings, with bond lengths varying from 2.912 (3) to 3.021 (3) Å. These hydrogen bonds appear to play an important role in controlling the molecular conformation of (I). Presumably, the additional steric requirement of the bulky 2,6-diisopropylphenyl substituent prevents the formation of intermolecular hydrogen bonds. In fact, the closest intermolecular contact the closest intermolecular contact [O1···H10Aⁱ = 2.883 Å; symmetry code: (i) x + 1, y, z] suggests that the molecular packing of (I) is governed only by van der Waals forces. Examination of the structure with PLATON (Spek, 2009) showed that there are no obvious space-group changes needed and no solvent-accessible voids in the crystal structure.

The P1═N1 bond distance in (I) [1.5836 (17) Å] is similar to the values of 1.592 (2) Å in 2-methoxy-3-methyl-6-[(triphenylphosphoranylidene)amino]pyrimidin-4(3H)-one and 1.588 (2) Å in 3-methyl-2-methylthio-6-[(triphenylphosphoranylidene)amino]pyrimidin-4(3H)-one (Low et al., 1998). Recently, however, Hayes and co-workers reported a 4,6-bis[N-(2,4,6-trimethylphenyl)-P,P-diphenylphosphorimidoyl]dibenzofuran system, and this compound displayed a significant difference in the P═N bond distances [1.549 (1) and 1.565 (1) Å; Ireland et al., 2010]. In comparison with the structure of (I), the P═N bonds of the dibenzofuran system are shortened as a result of sterically less hindered methyl groups instead of isopropyl groups on the phenyl ring attached to the phosphinimine N atom. As shown in Table 2 and Fig. 1, the range of angles around the P1 atom [104.92 (9)-115.89 (9)°] in (I) is distorted tetrahedral geometry. These values are similar to the range of 105.50 (9)–118.22 (13)° observed in the pyrimidinone compounds (Low et al., 1998). The dibenzofuran compound also shows comparable bond angles [100.54 (7)-116.31 (7)°; Ireland et al., 2010] around the P center in a strain-free manner with those found in (I).

All four aromatic rings of (I) are planar, with a maximum deviation of 0.027 (2) Å from the least-squares plane defined by C27–C32. The phenoxy ring is almost perpendicular to the C21–C26 phenyl ring attached to atom P1, with a maximum dihedral angle of 89.48 (7)°, and the dihedral angle between the C15–C20 phenyl ring attached to atom P1 and the C27–C32 phenyl ring attached to atom N1 is 42.21 (10)°.

A molecular orbital calculation was performed using the GAUSSIAN03 package (Frisch et al., 2004). The geometries obtained from the X-ray analysis were used in the input file for the calculation of total energy. The calculations were carried out using the B3LYP/6-31+G(d) level of theory. As shown in Table 2, the atomic bond lengths including P calculated by DFT are slightly longer than those from the X-ray data, and it may safely be said that all the rest are similar. However, improved agreement might be obtained if still higher level basis sets were used, at the expense of additional computational time.

Related literature

For related literature, see: Böhme & Fels (2010); Cristau et al. (2002); Frisch (2004); Gibson & Spitzmesser (2003); Hlatky (2000); Ireland et al. (2010); Low et al. (1998); Masuda et al. (2003); Mitani et al. (2002, 2003); Ośmiałowski et al. (2002); Qi & Zhang (2006); Qi et al. (2005); Said et al. (2001); Sheldrick (2008); Spek (2009); Stephan et al. (2003).

S2. Experimental

2,4-Di-tert-butyl-6-[N-(2,6-diisopropylphenyl)-P,P-diphenylphosphorimidoyl]phenol, (I), was obtained in a two-step synthesis, as indicated in the reaction scheme in the Comment.

For the preparation of (I), a solution of 2,6-diisopropylphenyl azide (0.61 g, 3 mmol) in tetrahydrofuran (THF, 10 ml) was added dropwise to a solution of 4,6-di-tert-butyl-2-(diphenylphosphanyl)phenol (1.17 g, 3 mmol) in THF (10 ml) at 273 K and stirred for 12 h at room temperature. The solvent was evaporated and the crude product obtained. Pure pale-yellow crystals of (I) were obtained after recrystallization from toluene at 263 K and dried in vacuo (yield 87%). Analysis, found: C 80.69, H 8.54, N 2.51%; calculated for C₃₈H₄₈NOP: C 80.67, H 8.55, N 2.48%.

S3. Refinement

Each of atoms C8, C9, and C10 of the tert-butyl group in the phenoxy unit was modeled as being disordered over two sites. The disorder caused two distinct orientations of the tert-butyl group, so all methyl groups belonging to the same orientation should have the same occupation factors. Therefore, the methyl groups were refined with only one free variable for their occupation factors keeping the atoms with the suffix `A' as the major component using the PART instruction in SHELXL97 (Sheldrick, 2008). In addition, the bond lengths around atom C7 to the disordered six C atoms were restrained to be equal with the s.u. value of 0.005 Å.

Aromatic H atoms were included in the model in idealized sp² geometries, with C—H = 0.93 Å and with U_iso(H) = 1.2U_eq(C). Methyl H atoms were included in the model in sp³ geometries found from difference Fourier syntheses, with C—H = 0.96 Å and with U_iso(H) = 1.5U_eq(C). The remaining H atoms (H1, H33 and H36) were found in an electron-density difference map and were allowed to refine both positionally and isotropically. The final difference map was essentially free of any chemically significant features, with the highest electron-density 0.70 Å from atom N1 and the deepest hole 0.83 Å from atom P1.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level, and H atoms (except for H1, H12C, H14C, H33 and H36) and the minor component of the disordered tert-butyl group have been omitted for clarity. Dashed lines indicate intramolecular hydrogen bonds.
	Fig. 2. The geometry of the closest intermolecular parallel phenyl rings C21–C26 and C21–C26(-x + 1, -y + 1, -z + 1) [denoted (i)]. H atoms and intramolecular hydrogen bonds have been omitted for clarity.

2,4-di-tert-butyl-6-[N-(2,6-diisopropylphenyl)- P,P-diphenylphosphorimidoyl]phenol

Crystal data

C38H48NOP	Z = 2
Mr = 565.74	F(000) = 612
Triclinic, P1	Dx = 1.116 Mg m^−3
Hall symbol: -P1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4999 (15) Å	Cell parameters from 3108 reflections
b = 11.9323 (19) Å	θ = 2.2–23.0°
c = 15.247 (3) Å	µ = 0.11 mm^−1
α = 88.658 (3)°	T = 293 K
β = 76.925 (3)°	Block, colourless
γ = 89.380 (3)°	0.40 × 0.10 × 0.10 mm
V = 1683.0 (5) Å^3

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	8349 independent reflections
Radiation source: fine-focus sealed tube	4194 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
ω scans	θmax = 28.4°, θmin = 1.4°
Absorption correction: integration (SADABS; Sheldrick, 2008)	h = −12→12
Tmin = 0.957, Tmax = 0.989	k = −15→15
22883 measured reflections	l = −20→20

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)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.160	w = 1/[σ^2(Fo^2) + (0.0664P)^2 + 0.0612P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
8349 reflections	Δρmax = 0.24 e Å^−3
423 parameters	Δρmin = −0.38 e Å^−3
15 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0084 (16)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.55467 (6)	0.76769 (4)	0.30304 (4)	0.03753 (17)
O1	0.73466 (16)	0.93933 (14)	0.16868 (11)	0.0568 (5)
H1	0.749 (3)	0.866 (2)	0.1994 (19)	0.087 (9)*
N1	0.72381 (18)	0.75666 (14)	0.26630 (12)	0.0424 (4)
C1	0.5923 (2)	0.96457 (17)	0.19583 (14)	0.0387 (5)
C2	0.4992 (2)	0.89707 (16)	0.26000 (13)	0.0361 (5)
C3	0.3545 (2)	0.92945 (16)	0.28992 (14)	0.0394 (5)
H3	0.2944	0.8854	0.3336	0.047*
C4	0.2978 (2)	1.02436 (17)	0.25694 (14)	0.0411 (5)
C5	0.3941 (2)	1.08704 (18)	0.19158 (14)	0.0451 (5)
H5	0.3582	1.1510	0.1681	0.054*
C6	0.5386 (2)	1.06146 (17)	0.15916 (14)	0.0414 (5)
C7	0.1393 (3)	1.05712 (19)	0.28934 (16)	0.0566 (6)
C8A	0.0918 (7)	1.0426 (7)	0.3904 (3)	0.095 (3)	0.619 (12)
H8A1	−0.0070	1.0661	0.4099	0.142*	0.619 (12)
H8A2	0.1517	1.0872	0.4187	0.142*	0.619 (12)
H8A3	0.1007	0.9651	0.4069	0.142*	0.619 (12)
C9A	0.1049 (7)	1.1746 (5)	0.2638 (7)	0.121 (5)	0.619 (12)
H9A1	0.0051	1.1908	0.2895	0.181*	0.619 (12)
H9A2	0.1227	1.1821	0.1994	0.181*	0.619 (12)
H9A3	0.1647	1.2261	0.2860	0.181*	0.619 (12)
C10A	0.0500 (6)	0.9744 (6)	0.2499 (6)	0.106 (3)	0.619 (12)
H10A	−0.0502	0.9951	0.2667	0.158*	0.619 (12)
H10B	0.0628	0.9002	0.2728	0.158*	0.619 (12)
H10C	0.0814	0.9757	0.1855	0.158*	0.619 (12)
C8B	0.0428 (12)	0.9733 (12)	0.3494 (16)	0.175 (13)	0.381 (12)
H8B1	−0.0560	0.9977	0.3584	0.262*	0.381 (12)
H8B2	0.0694	0.9675	0.4065	0.262*	0.381 (12)
H8B3	0.0536	0.9014	0.3215	0.262*	0.381 (12)
C9B	0.1351 (10)	1.1646 (10)	0.3421 (12)	0.125 (7)	0.381 (12)
H9B1	0.0383	1.1937	0.3563	0.187*	0.381 (12)
H9B2	0.1983	1.2189	0.3063	0.187*	0.381 (12)
H9B3	0.1663	1.1487	0.3968	0.187*	0.381 (12)
C10B	0.0734 (11)	1.0892 (17)	0.2105 (5)	0.126 (7)	0.381 (12)
H10D	−0.0262	1.1094	0.2324	0.190*	0.381 (12)
H10E	0.0801	1.0268	0.1712	0.190*	0.381 (12)
H10F	0.1247	1.1518	0.1781	0.190*	0.381 (12)
C11	0.6377 (3)	1.13446 (19)	0.08631 (15)	0.0515 (6)
C12	0.7549 (3)	1.1880 (2)	0.1255 (2)	0.0809 (9)
H12A	0.7109	1.2379	0.1725	0.121*
H12B	0.8201	1.2292	0.0789	0.121*
H12C	0.8074	1.1304	0.1498	0.121*
C13	0.5522 (3)	1.2292 (2)	0.0521 (2)	0.0852 (10)
H13A	0.5125	1.2782	0.1007	0.128*
H13B	0.4752	1.1978	0.0293	0.128*
H13C	0.6154	1.2709	0.0048	0.128*
C14	0.7069 (3)	1.0647 (2)	0.00444 (17)	0.0740 (8)
H14A	0.7653	1.1123	−0.0408	0.111*
H14B	0.6324	1.0314	−0.0195	0.111*
H14C	0.7661	1.0068	0.0224	0.111*
C15	0.4531 (2)	0.65518 (17)	0.27075 (14)	0.0408 (5)
C16	0.3608 (3)	0.6714 (2)	0.21265 (15)	0.0523 (6)
H16	0.3458	0.7432	0.1914	0.063*
C17	0.2914 (3)	0.5815 (2)	0.18633 (18)	0.0657 (7)
H17	0.2276	0.5934	0.1489	0.079*
C18	0.3157 (3)	0.4752 (2)	0.21476 (19)	0.0677 (7)
H18	0.2692	0.4151	0.1960	0.081*
C19	0.4083 (3)	0.4566 (2)	0.27081 (18)	0.0633 (7)
H19	0.4253	0.3840	0.2896	0.076*
C20	0.4762 (3)	0.54603 (18)	0.29939 (16)	0.0527 (6)
H20	0.5379	0.5333	0.3381	0.063*
C21	0.4927 (2)	0.77569 (17)	0.42412 (14)	0.0410 (5)
C22	0.3791 (3)	0.7144 (2)	0.47494 (16)	0.0613 (7)
H22	0.3308	0.6638	0.4469	0.074*
C23	0.3366 (4)	0.7277 (3)	0.56702 (19)	0.0881 (10)
H23	0.2604	0.6857	0.6006	0.106*
C24	0.4064 (4)	0.8022 (3)	0.6087 (2)	0.0891 (10)
H24	0.3775	0.8107	0.6707	0.107*
C25	0.5179 (4)	0.8641 (2)	0.5602 (2)	0.0725 (8)
H25	0.5648	0.9148	0.5890	0.087*
C26	0.5616 (3)	0.8515 (2)	0.46773 (16)	0.0551 (6)
H26	0.6376	0.8941	0.4347	0.066*
C27	0.7982 (2)	0.65161 (17)	0.25213 (15)	0.0444 (5)
C28	0.8104 (2)	0.59760 (19)	0.16918 (17)	0.0516 (6)
C29	0.8779 (3)	0.4939 (2)	0.1580 (2)	0.0683 (8)
H29	0.8856	0.4571	0.1040	0.082*
C30	0.9339 (3)	0.4443 (2)	0.2249 (2)	0.0783 (9)
H30	0.9757	0.3733	0.2168	0.094*
C31	0.9282 (3)	0.4989 (2)	0.3034 (2)	0.0698 (8)
H31	0.9692	0.4654	0.3474	0.084*
C32	0.8623 (2)	0.60359 (19)	0.31893 (17)	0.0507 (6)
C33	0.7565 (3)	0.6515 (2)	0.09237 (17)	0.0626 (7)
H33	0.674 (3)	0.709 (2)	0.1164 (16)	0.068 (7)*
C34	0.6938 (4)	0.5668 (3)	0.0379 (2)	0.1012 (11)
H34A	0.7682	0.5151	0.0107	0.152*
H34B	0.6573	0.6057	−0.0082	0.152*
H34C	0.6167	0.5265	0.0771	0.152*
C35	0.8785 (4)	0.7192 (3)	0.0317 (2)	0.1086 (12)
H35A	0.9109	0.7756	0.0664	0.163*
H35B	0.8435	0.7545	−0.0165	0.163*
H35C	0.9576	0.6700	0.0072	0.163*
C36	0.8630 (3)	0.6626 (2)	0.40519 (18)	0.0575 (7)
H36	0.820 (2)	0.7353 (19)	0.4045 (15)	0.055 (7)*
C37	1.0168 (3)	0.6786 (3)	0.4186 (2)	0.0801 (9)
H37A	1.0604	0.6066	0.4243	0.120*
H37B	1.0130	0.7202	0.4722	0.120*
H37C	1.0732	0.7189	0.3676	0.120*
C38	0.7698 (3)	0.6020 (3)	0.4875 (2)	0.0852 (9)
H38A	0.6720	0.5980	0.4807	0.128*
H38B	0.7722	0.6424	0.5409	0.128*
H38C	0.8069	0.5275	0.4926	0.128*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0396 (3)	0.0341 (3)	0.0390 (3)	0.0022 (2)	−0.0095 (2)	0.0024 (2)
O1	0.0389 (9)	0.0552 (10)	0.0706 (11)	0.0024 (8)	−0.0028 (8)	0.0190 (9)
N1	0.0371 (10)	0.0400 (10)	0.0488 (11)	0.0065 (8)	−0.0077 (8)	0.0039 (8)
C1	0.0385 (12)	0.0379 (12)	0.0399 (12)	−0.0014 (9)	−0.0092 (10)	−0.0014 (9)
C2	0.0373 (12)	0.0356 (11)	0.0363 (11)	0.0001 (9)	−0.0106 (9)	0.0005 (9)
C3	0.0418 (12)	0.0364 (11)	0.0399 (12)	0.0012 (9)	−0.0093 (10)	0.0010 (9)
C4	0.0438 (12)	0.0376 (11)	0.0425 (12)	0.0048 (10)	−0.0110 (10)	−0.0011 (9)
C5	0.0533 (14)	0.0386 (12)	0.0452 (13)	0.0062 (10)	−0.0155 (11)	0.0050 (10)
C6	0.0512 (14)	0.0365 (11)	0.0373 (12)	0.0004 (10)	−0.0119 (10)	0.0016 (9)
C7	0.0457 (14)	0.0579 (15)	0.0650 (17)	0.0138 (12)	−0.0110 (12)	0.0021 (13)
C8A	0.065 (4)	0.122 (7)	0.080 (4)	0.037 (4)	0.014 (3)	0.020 (4)
C9A	0.075 (4)	0.083 (5)	0.176 (11)	0.046 (4)	0.022 (6)	0.063 (6)
C10A	0.044 (3)	0.131 (7)	0.144 (7)	0.010 (4)	−0.026 (4)	−0.022 (6)
C8B	0.058 (8)	0.109 (12)	0.30 (3)	0.025 (7)	0.063 (13)	0.092 (17)
C9B	0.070 (6)	0.131 (12)	0.171 (15)	0.052 (7)	−0.017 (8)	−0.065 (12)
C10B	0.068 (7)	0.22 (2)	0.101 (8)	0.058 (9)	−0.039 (6)	0.000 (9)
C11	0.0614 (16)	0.0458 (13)	0.0441 (13)	−0.0034 (11)	−0.0063 (12)	0.0094 (11)
C12	0.088 (2)	0.078 (2)	0.074 (2)	−0.0407 (17)	−0.0115 (16)	0.0110 (15)
C13	0.098 (2)	0.0683 (18)	0.078 (2)	0.0069 (17)	−0.0011 (17)	0.0382 (16)
C14	0.094 (2)	0.0712 (18)	0.0485 (16)	−0.0038 (16)	0.0017 (15)	0.0020 (13)
C15	0.0453 (13)	0.0382 (12)	0.0368 (12)	−0.0005 (10)	−0.0050 (10)	−0.0005 (9)
C16	0.0623 (16)	0.0490 (14)	0.0485 (14)	−0.0033 (12)	−0.0179 (12)	−0.0031 (11)
C17	0.0763 (19)	0.0667 (18)	0.0599 (17)	−0.0096 (15)	−0.0261 (14)	−0.0102 (14)
C18	0.079 (2)	0.0532 (16)	0.0717 (19)	−0.0153 (14)	−0.0157 (16)	−0.0143 (14)
C19	0.0781 (19)	0.0384 (13)	0.0690 (18)	−0.0043 (13)	−0.0071 (15)	−0.0021 (12)
C20	0.0599 (16)	0.0432 (13)	0.0562 (15)	−0.0011 (11)	−0.0160 (12)	−0.0002 (11)
C21	0.0437 (13)	0.0388 (12)	0.0418 (12)	0.0070 (10)	−0.0132 (10)	0.0011 (9)
C22	0.0607 (16)	0.0726 (17)	0.0476 (15)	−0.0106 (14)	−0.0056 (13)	0.0029 (13)
C23	0.097 (2)	0.111 (3)	0.0459 (17)	−0.019 (2)	0.0054 (16)	0.0047 (17)
C24	0.123 (3)	0.100 (3)	0.0418 (16)	0.009 (2)	−0.0130 (19)	−0.0050 (17)
C25	0.097 (2)	0.0685 (18)	0.0614 (19)	0.0115 (17)	−0.0359 (17)	−0.0209 (15)
C26	0.0644 (16)	0.0507 (14)	0.0532 (15)	0.0026 (12)	−0.0193 (13)	−0.0051 (12)
C27	0.0367 (12)	0.0399 (12)	0.0536 (14)	0.0021 (10)	−0.0048 (10)	0.0054 (10)
C28	0.0442 (13)	0.0484 (14)	0.0577 (15)	0.0055 (11)	−0.0022 (11)	−0.0028 (11)
C29	0.0618 (17)	0.0563 (16)	0.086 (2)	0.0127 (14)	−0.0151 (15)	−0.0173 (15)
C30	0.073 (2)	0.0474 (16)	0.117 (3)	0.0199 (14)	−0.0266 (19)	−0.0154 (17)
C31	0.0640 (18)	0.0483 (15)	0.101 (2)	0.0094 (13)	−0.0285 (16)	0.0103 (15)
C32	0.0435 (13)	0.0449 (13)	0.0636 (16)	0.0004 (11)	−0.0128 (11)	0.0098 (11)
C33	0.0683 (18)	0.0680 (17)	0.0463 (15)	0.0152 (15)	−0.0024 (13)	−0.0049 (13)
C34	0.137 (3)	0.100 (3)	0.080 (2)	0.029 (2)	−0.051 (2)	−0.0286 (19)
C35	0.109 (3)	0.104 (3)	0.086 (2)	0.017 (2)	0.032 (2)	0.022 (2)
C36	0.0573 (16)	0.0540 (16)	0.0642 (17)	0.0071 (13)	−0.0213 (13)	0.0109 (13)
C37	0.0699 (19)	0.080 (2)	0.099 (2)	0.0010 (16)	−0.0378 (17)	0.0044 (17)
C38	0.088 (2)	0.093 (2)	0.073 (2)	0.0020 (18)	−0.0175 (17)	0.0218 (17)

Geometric parameters (Å, º)

P1—N1	1.5826 (18)	C14—H14C	0.9600
P1—C2	1.784 (2)	C15—C16	1.390 (3)
P1—C15	1.803 (2)	C15—C20	1.395 (3)
P1—C21	1.811 (2)	C16—C17	1.379 (3)
O1—C1	1.355 (2)	C16—H16	0.9300
O1—H1	1.00 (3)	C17—C18	1.365 (4)
N1—C27	1.429 (3)	C17—H17	0.9300
C1—C2	1.406 (3)	C18—C19	1.371 (4)
C1—C6	1.413 (3)	C18—H18	0.9300
C2—C3	1.399 (3)	C19—C20	1.382 (3)
C3—C4	1.381 (3)	C19—H19	0.9300
C3—H3	0.9300	C20—H20	0.9300
C4—C5	1.399 (3)	C21—C22	1.382 (3)
C4—C7	1.525 (3)	C21—C26	1.388 (3)
C5—C6	1.383 (3)	C22—C23	1.383 (4)
C5—H5	0.9300	C22—H22	0.9300
C6—C11	1.542 (3)	C23—C24	1.365 (4)
C7—C9A	1.499 (3)	C23—H23	0.9300
C7—C8B	1.509 (4)	C24—C25	1.360 (4)
C7—C8A	1.511 (4)	C24—H24	0.9300
C7—C10B	1.515 (4)	C25—C26	1.388 (4)
C7—C9B	1.524 (4)	C25—H25	0.9300
C7—C10A	1.527 (4)	C26—H26	0.9300
C8A—H8A1	0.9600	C27—C32	1.408 (3)
C8A—H8A2	0.9600	C27—C28	1.414 (3)
C8A—H8A3	0.9600	C28—C29	1.384 (3)
C9A—H9A1	0.9600	C28—C33	1.509 (3)
C9A—H9A2	0.9600	C29—C30	1.374 (4)
C9A—H9A3	0.9600	C29—H29	0.9300
C10A—H10A	0.9600	C30—C31	1.365 (4)
C10A—H10B	0.9600	C30—H30	0.9300
C10A—H10C	0.9600	C31—C32	1.393 (3)
C8B—H8B1	0.9600	C31—H31	0.9300
C8B—H8B2	0.9600	C32—C36	1.508 (4)
C8B—H8B3	0.9600	C33—C34	1.530 (4)
C9B—H9B1	0.9600	C33—C35	1.534 (4)
C9B—H9B2	0.9600	C33—H33	1.04 (2)
C9B—H9B3	0.9600	C34—H34A	0.9600
C10B—H10D	0.9600	C34—H34B	0.9600
C10B—H10E	0.9600	C34—H34C	0.9600
C10B—H10F	0.9600	C35—H35A	0.9600
C11—C12	1.530 (3)	C35—H35B	0.9600
C11—C14	1.532 (3)	C35—H35C	0.9600
C11—C13	1.535 (3)	C36—C37	1.534 (4)
C12—H12A	0.9600	C36—C38	1.534 (4)
C12—H12B	0.9600	C36—H36	0.96 (2)
C12—H12C	0.9600	C37—H37A	0.9600
C13—H13A	0.9600	C37—H37B	0.9600
C13—H13B	0.9600	C37—H37C	0.9600
C13—H13C	0.9600	C38—H38A	0.9600
C14—H14A	0.9600	C38—H38B	0.9600
C14—H14B	0.9600	C38—H38C	0.9600
N1—P1—C2	107.42 (9)	H14A—C14—H14B	109.5
N1—P1—C15	113.93 (10)	C11—C14—H14C	109.5
C2—P1—C15	108.95 (10)	H14A—C14—H14C	109.5
N1—P1—C21	115.89 (10)	H14B—C14—H14C	109.5
C2—P1—C21	104.92 (9)	C16—C15—C20	118.3 (2)
C15—P1—C21	105.24 (10)	C16—C15—P1	122.61 (17)
C1—O1—H1	106.2 (16)	C20—C15—P1	118.86 (17)
C27—N1—P1	123.48 (14)	C17—C16—C15	120.3 (2)
O1—C1—C2	121.15 (18)	C17—C16—H16	119.8
O1—C1—C6	118.69 (19)	C15—C16—H16	119.8
C2—C1—C6	120.15 (19)	C18—C17—C16	120.5 (3)
C3—C2—C1	119.35 (18)	C18—C17—H17	119.7
C3—C2—P1	117.59 (15)	C16—C17—H17	119.7
C1—C2—P1	123.02 (16)	C17—C18—C19	120.3 (2)
C4—C3—C2	122.5 (2)	C17—C18—H18	119.8
C4—C3—H3	118.8	C19—C18—H18	119.8
C2—C3—H3	118.8	C18—C19—C20	119.8 (2)
C3—C4—C5	115.9 (2)	C18—C19—H19	120.1
C3—C4—C7	121.6 (2)	C20—C19—H19	120.1
C5—C4—C7	122.46 (19)	C19—C20—C15	120.6 (2)
C6—C5—C4	125.19 (19)	C19—C20—H20	119.7
C6—C5—H5	117.4	C15—C20—H20	119.7
C4—C5—H5	117.4	C22—C21—C26	118.3 (2)
C5—C6—C1	116.90 (19)	C22—C21—P1	124.44 (18)
C5—C6—C11	122.08 (19)	C26—C21—P1	117.20 (18)
C1—C6—C11	121.03 (19)	C21—C22—C23	120.7 (3)
C9A—C7—C8B	128.8 (5)	C21—C22—H22	119.7
C9A—C7—C8A	108.7 (5)	C23—C22—H22	119.7
C8B—C7—C8A	47.1 (9)	C24—C23—C22	120.1 (3)
C9A—C7—C10B	55.1 (6)	C24—C23—H23	120.0
C8B—C7—C10B	109.2 (10)	C22—C23—H23	120.0
C8A—C7—C10B	138.5 (5)	C25—C24—C23	120.5 (3)
C9A—C7—C9B	50.6 (6)	C25—C24—H24	119.8
C8B—C7—C9B	107.4 (10)	C23—C24—H24	119.8
C8A—C7—C9B	65.0 (7)	C24—C25—C26	120.0 (3)
C10B—C7—C9B	104.8 (9)	C24—C25—H25	120.0
C9A—C7—C4	114.1 (3)	C26—C25—H25	120.0
C8B—C7—C4	116.8 (5)	C21—C26—C25	120.5 (3)
C8A—C7—C4	110.6 (3)	C21—C26—H26	119.8
C10B—C7—C4	110.9 (4)	C25—C26—H26	119.8
C9B—C7—C4	107.0 (4)	C32—C27—C28	120.1 (2)
C9A—C7—C10A	109.7 (5)	C32—C27—N1	120.5 (2)
C8B—C7—C10A	59.3 (9)	C28—C27—N1	119.3 (2)
C8A—C7—C10A	105.9 (4)	C29—C28—C27	118.5 (2)
C10B—C7—C10A	58.3 (7)	C29—C28—C33	119.6 (2)
C9B—C7—C10A	145.2 (4)	C27—C28—C33	121.9 (2)
C4—C7—C10A	107.5 (3)	C30—C29—C28	121.3 (3)
C7—C8A—H8A1	109.5	C30—C29—H29	119.3
C7—C8A—H8A2	109.5	C28—C29—H29	119.3
C7—C8A—H8A3	109.5	C31—C30—C29	120.1 (2)
C7—C9A—H9A1	109.5	C31—C30—H30	119.9
C7—C9A—H9A2	109.5	C29—C30—H30	119.9
C7—C9A—H9A3	109.5	C30—C31—C32	121.5 (3)
C7—C10A—H10A	109.5	C30—C31—H31	119.3
C7—C10A—H10B	109.5	C32—C31—H31	119.3
C7—C10A—H10C	109.5	C31—C32—C27	118.3 (2)
C7—C8B—H8B1	109.5	C31—C32—C36	119.7 (2)
C7—C8B—H8B2	109.5	C27—C32—C36	122.1 (2)
H8B1—C8B—H8B2	109.5	C28—C33—C34	112.9 (2)
C7—C8B—H8B3	109.5	C28—C33—C35	109.6 (2)
H8B1—C8B—H8B3	109.5	C34—C33—C35	111.1 (3)
H8B2—C8B—H8B3	109.5	C28—C33—H33	110.6 (13)
C7—C9B—H9B1	109.5	C34—C33—H33	106.4 (13)
C7—C9B—H9B2	109.5	C35—C33—H33	106.0 (13)
H9B1—C9B—H9B2	109.5	C33—C34—H34A	109.5
C7—C9B—H9B3	109.5	C33—C34—H34B	109.5
H9B1—C9B—H9B3	109.5	H34A—C34—H34B	109.5
H9B2—C9B—H9B3	109.5	C33—C34—H34C	109.5
C7—C10B—H10D	109.5	H34A—C34—H34C	109.5
C7—C10B—H10E	109.5	H34B—C34—H34C	109.5
H10D—C10B—H10E	109.5	C33—C35—H35A	109.5
C7—C10B—H10F	109.5	C33—C35—H35B	109.5
H10D—C10B—H10F	109.5	H35A—C35—H35B	109.5
H10E—C10B—H10F	109.5	C33—C35—H35C	109.5
C12—C11—C14	110.1 (2)	H35A—C35—H35C	109.5
C12—C11—C13	107.9 (2)	H35B—C35—H35C	109.5
C14—C11—C13	106.8 (2)	C32—C36—C37	112.0 (2)
C12—C11—C6	109.85 (19)	C32—C36—C38	112.0 (2)
C14—C11—C6	110.91 (19)	C37—C36—C38	110.2 (2)
C13—C11—C6	111.2 (2)	C32—C36—H36	110.1 (13)
C11—C12—H12A	109.5	C37—C36—H36	107.6 (13)
C11—C12—H12B	109.5	C38—C36—H36	104.6 (14)
H12A—C12—H12B	109.5	C36—C37—H37A	109.5
C11—C12—H12C	109.5	C36—C37—H37B	109.5
H12A—C12—H12C	109.5	H37A—C37—H37B	109.5
H12B—C12—H12C	109.5	C36—C37—H37C	109.5
C11—C13—H13A	109.5	H37A—C37—H37C	109.5
C11—C13—H13B	109.5	H37B—C37—H37C	109.5
H13A—C13—H13B	109.5	C36—C38—H38A	109.5
C11—C13—H13C	109.5	C36—C38—H38B	109.5
H13A—C13—H13C	109.5	H38A—C38—H38B	109.5
H13B—C13—H13C	109.5	C36—C38—H38C	109.5
C11—C14—H14A	109.5	H38A—C38—H38C	109.5
C11—C14—H14B	109.5	H38B—C38—H38C	109.5
C2—P1—N1—C27	−152.14 (17)	C21—P1—C15—C20	−66.24 (19)
C15—P1—N1—C27	−31.4 (2)	C20—C15—C16—C17	1.7 (3)
C21—P1—N1—C27	90.98 (19)	P1—C15—C16—C17	176.58 (19)
O1—C1—C2—C3	176.49 (18)	C15—C16—C17—C18	−2.0 (4)
C6—C1—C2—C3	−2.7 (3)	C16—C17—C18—C19	0.8 (4)
O1—C1—C2—P1	−5.9 (3)	C17—C18—C19—C20	0.6 (4)
C6—C1—C2—P1	174.90 (15)	C18—C19—C20—C15	−0.9 (4)
N1—P1—C2—C3	−174.74 (15)	C16—C15—C20—C19	−0.3 (3)
C15—P1—C2—C3	61.40 (18)	P1—C15—C20—C19	−175.36 (19)
C21—P1—C2—C3	−50.88 (18)	N1—P1—C21—C22	−133.5 (2)
N1—P1—C2—C1	7.6 (2)	C2—P1—C21—C22	108.2 (2)
C15—P1—C2—C1	−116.28 (18)	C15—P1—C21—C22	−6.6 (2)
C21—P1—C2—C1	131.44 (17)	N1—P1—C21—C26	48.78 (19)
C1—C2—C3—C4	1.8 (3)	C2—P1—C21—C26	−69.49 (18)
P1—C2—C3—C4	−175.96 (16)	C15—P1—C21—C26	175.62 (16)
C2—C3—C4—C5	−0.2 (3)	C26—C21—C22—C23	−0.7 (4)
C2—C3—C4—C7	178.98 (19)	P1—C21—C22—C23	−178.4 (2)
C3—C4—C5—C6	−0.5 (3)	C21—C22—C23—C24	0.4 (5)
C7—C4—C5—C6	−179.7 (2)	C22—C23—C24—C25	0.1 (5)
C4—C5—C6—C1	−0.4 (3)	C23—C24—C25—C26	−0.2 (5)
C4—C5—C6—C11	179.5 (2)	C22—C21—C26—C25	0.7 (3)
O1—C1—C6—C5	−177.19 (18)	P1—C21—C26—C25	178.56 (19)
C2—C1—C6—C5	2.1 (3)	C24—C25—C26—C21	−0.2 (4)
O1—C1—C6—C11	2.9 (3)	P1—N1—C27—C32	−95.2 (2)
C2—C1—C6—C11	−177.88 (19)	P1—N1—C27—C28	86.5 (2)
C3—C4—C7—C9A	166.1 (6)	C32—C27—C28—C29	4.2 (3)
C5—C4—C7—C9A	−14.7 (6)	N1—C27—C28—C29	−177.6 (2)
C3—C4—C7—C8B	−8.0 (13)	C32—C27—C28—C33	−173.8 (2)
C5—C4—C7—C8B	171.1 (13)	N1—C27—C28—C33	4.5 (3)
C3—C4—C7—C8A	43.3 (5)	C27—C28—C29—C30	−0.8 (4)
C5—C4—C7—C8A	−137.6 (4)	C33—C28—C29—C30	177.2 (3)
C3—C4—C7—C10B	−133.9 (9)	C28—C29—C30—C31	−2.4 (4)
C5—C4—C7—C10B	45.2 (9)	C29—C30—C31—C32	2.1 (4)
C3—C4—C7—C9B	112.3 (8)	C30—C31—C32—C27	1.3 (4)
C5—C4—C7—C9B	−68.6 (8)	C30—C31—C32—C36	−177.9 (3)
C3—C4—C7—C10A	−71.9 (5)	C28—C27—C32—C31	−4.4 (3)
C5—C4—C7—C10A	107.2 (5)	N1—C27—C32—C31	177.3 (2)
C5—C6—C11—C12	115.0 (2)	C28—C27—C32—C36	174.8 (2)
C1—C6—C11—C12	−65.1 (3)	N1—C27—C32—C36	−3.5 (3)
C5—C6—C11—C14	−123.0 (2)	C29—C28—C33—C34	37.3 (3)
C1—C6—C11—C14	56.9 (3)	C27—C28—C33—C34	−144.8 (3)
C5—C6—C11—C13	−4.4 (3)	C29—C28—C33—C35	−87.1 (3)
C1—C6—C11—C13	175.6 (2)	C27—C28—C33—C35	90.8 (3)
N1—P1—C15—C16	−113.08 (19)	C31—C32—C36—C37	56.5 (3)
C2—P1—C15—C16	6.8 (2)	C27—C32—C36—C37	−122.7 (2)
C21—P1—C15—C16	118.89 (19)	C31—C32—C36—C38	−67.9 (3)
N1—P1—C15—C20	61.8 (2)	C27—C32—C36—C38	112.9 (3)
C2—P1—C15—C20	−178.31 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	1.00 (3)	1.63 (3)	2.600 (2)	163 (2)
C12—H12C···O1	0.96	2.38	3.023 (3)	124
C14—H14C···O1	0.96	2.31	2.949 (3)	123
C33—H33···N1	1.04 (2)	2.52 (2)	2.912 (3)	101.8 (15)
C36—H36···N1	0.96 (2)	2.49 (2)	2.935 (3)	108.7 (15)