3-Bromo-4-(di­cyclo­hexyl­phosphinoyl)-2,6-di­methoxy­pyridine

The crystal structure of the title compound, C₁₉H₂₉BrNO₃P, contains one pyridyl ring and two cyclo­hexyl rings in chair forms. There are two molecules per asymmetric unit, and the overall molecular organization is stabilized by well defined intermolecular weak interactions.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.052
• wR factor = 0.116
• Data-to-parameter ratio = 20.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The search for new chiral ligands is an ongoing process in the field of asymmetric synthesis. Over the past two decades, tremendous success has been achieved in the use of chiral arylphosphine ligands such as BINAP, BIPHEP, DuPhos, and so on, in Rh- or Ru-catalyzed asymmetric hydrogenation reactions (Lin et al., 2001). As an effort to expand the scope of the arylphosphine ligands and their application in homogeneous asymmetric catalysis, we have recently developed a class of novel dipyridylphosphine ligands P-Phos (Pai et al., 2000) and Tol-P-Phos (Wu et al., 2001), and found their Ru^II complexes to be highly effective in the catalytic asymmetric hydrogenation of 2-(6-methoxy-2-naphthyl)propenoic acid and keto esters. [Please define BINAP, BIPHEP, DuPhos, P-Phos and Tol-P-Phos]

In this study, we attempt to synthesize another new P-Phos derivative, namely 2,2',6,6'-tetramethoxy-4,4'-bis(dicyclohexylphosphino)-3,3'-bipyridine, (II), by replacing the four phenyl rings in P-Phos with four cyclohexyl rings as a means to tune its electronic and steric properties. In the synthesis of the target product, the title compound, (I), is the important intermediate, which was obtained by the ortho-lithiation of 3-bromo-2,6-dimethoxypyridine with lithium diisopropylamide (LDA), followed by the addition of dicyclohexylphosphine chloride and then by oxidation of resulted phosphine with hydrogen peroxide.

Among these procedures, the ortho-lithiation reaction deserves further comment. Regioselective lithiation of halopyridines always occurred lithium–halogen exchange, halogen-dancing reaction or deprotonation reaction. The choice of lithium reagent (i.e. n-Bu—Li or LDA) is also very important (Rocca et al., 1993). The relative kinetic acidity of pyridine (C-4 > C-3 > C-2; Zoltewica et al., 1969) combined with the greatly increased kinetic acidity of the ortho H atom in halobenzenes suggested that it would be feasible to metalate regioselectively the C-4 position of 3-halopyridines. The X-ray crystallographic analysis of (I) unambiguously showed that the ortho-lithiation reaction proceeds with high chemo- and regioselectivity and is almost avoid the formation of by-products. By well defined intermolecular weak interactions, molecules of (I) (as building blocks) were finally assemblied into three-dimensional network. As part of our efforts investigating this domain, we present the crystal structure of (I). The synthesis of chiral ligand (II) and its application in the Ru- or Rh-catalyzed asymmetric hydrogenation reactions are underway.

S2. Experimental

The title compound, (I), was prepared according to the following procedures under a nitrogen atmosphere unless otherwise stated. To a magnetically stirred solution of 2.26 ml (4.5 mmol) of LDA (2.0 M solution in THF) was added a solution of 3-bromo-2,6-dimethoxypyridine (0.988 g, 4.5 mmol) in dried THF (5 ml) at 195 K over a period of 15 min. The reaction mixture was stirred for another 15 min and to the resulting red–brown suspension was added a solution of dicyclohexylphosphine chloride in 10 ml dried THF. The reaction was allowed to stir and reach ambient temperature overnight. 25 ml water was added to the reaction mixture and the solvent was removed under reduced pressure. The organic product was extracted with dichloromethane. The combined extract was dried with anhydrous sodium sulfate and was concentrated in vacuo to give a crude product. To the crude product in acetone solution (20 ml), 35% hydrogen peroxide (10 ml) was added slowly and the reaction was monitored by thin-layer chromatography. The product was extracted with dichloromethane. The crude product was purified by column chromatography (silica gel, hexane–ethyl acetate 6:1) to give the pure product (I) (50% yield). The crystal used for the data collection was obtained by slow evaporation from a hexane–dichloromethane (1:1) saturated solution at room temperature. Found: C 52.63, H 6.90, N 2.96%; calculated for C₁₉H₂₉BrNO₃P: C 53.03, H 7.53, N 3.25%.

S3. Refinement

The C-bound H atoms were placed in geometrically calculated positions and included in the final refinement in the riding-model approximation.

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. The olecular structure of (I), showing ellipsoids at the 30% probability level (Siemens, 1995).

3-Bromo-4-(dicyclohexylphosphinoyl)-2,6-dimethoxypyridine

Crystal data

C19H29BrNO3P	F(000) = 1792
Mr = 430.31	Dx = 1.394 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8624 reflections
a = 9.2025 (12) Å	θ = 1–27.5°
b = 18.759 (2) Å	µ = 2.10 mm^−1
c = 23.761 (3) Å	T = 294 K
β = 92.009 (3)°	Prism, colorless
V = 4099.3 (9) Å^3	0.30 × 0.26 × 0.24 mm
Z = 8

Data collection

Siemens SMART CCD area-detector diffractometer	9427 independent reflections
Radiation source: fine-focus sealed tube	3936 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.061
ϕ and ω scans	θmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.571, Tmax = 0.633	k = −19→24
27403 measured reflections	l = −30→27

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.035P)^2] where P = (Fo^2 + 2Fc^2)/3
9427 reflections	(Δ/σ)max = 0.002
451 parameters	Δρmax = 0.91 e Å^−3
0 restraints	Δρmin = −0.60 e Å^−3

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
Br1	0.37202 (5)	0.30717 (3)	0.55442 (2)	0.06490 (18)
P1	0.22148 (13)	0.35103 (7)	0.41928 (5)	0.0532 (3)
O1	0.1201 (3)	0.36109 (17)	0.37024 (11)	0.0722 (10)
O2	0.1533 (3)	0.22404 (17)	0.61400 (13)	0.0655 (9)
O3	−0.2073 (4)	0.20364 (19)	0.47620 (12)	0.0770 (10)
N1	−0.0290 (4)	0.21495 (19)	0.54593 (14)	0.0493 (10)
C1	0.3831 (5)	0.2989 (2)	0.40401 (18)	0.0543 (12)
H1A	0.4315	0.2889	0.4405	0.065*
C2	0.4918 (6)	0.3365 (3)	0.3703 (2)	0.0870 (18)
H2A	0.5296	0.3769	0.3918	0.104*
H2B	0.4439	0.3550	0.3364	0.104*
C3	0.6155 (6)	0.2907 (3)	0.3543 (3)	0.0944 (19)
H3A	0.6778	0.2825	0.3875	0.113*
H3B	0.6722	0.3163	0.3272	0.113*
C4	0.5727 (7)	0.2203 (3)	0.3297 (3)	0.107 (2)
H4A	0.5306	0.2275	0.2921	0.128*
H4B	0.6587	0.1909	0.3266	0.128*
C5	0.4682 (7)	0.1835 (3)	0.3639 (3)	0.118 (2)
H5A	0.5180	0.1668	0.3981	0.142*
H5B	0.4327	0.1419	0.3434	0.142*
C6	0.3402 (6)	0.2279 (3)	0.3798 (2)	0.0917 (19)
H6A	0.2774	0.2353	0.3467	0.110*
H6B	0.2850	0.2021	0.4073	0.110*
C7	0.2827 (5)	0.4360 (2)	0.44960 (16)	0.0450 (11)
H7A	0.3785	0.4286	0.4680	0.054*
C8	0.1816 (5)	0.4673 (3)	0.49314 (19)	0.0656 (14)
H8A	0.0846	0.4720	0.4763	0.079*
H8B	0.1765	0.4348	0.5247	0.079*
C9	0.2329 (5)	0.5393 (3)	0.51426 (19)	0.0683 (14)
H9A	0.1632	0.5581	0.5401	0.082*
H9B	0.3252	0.5338	0.5348	0.082*
C10	0.2508 (6)	0.5915 (3)	0.4669 (2)	0.0839 (17)
H10A	0.2910	0.6357	0.4818	0.101*
H10B	0.1565	0.6018	0.4492	0.101*
C11	0.3509 (6)	0.5613 (3)	0.4233 (2)	0.0799 (17)
H11A	0.3556	0.5944	0.3920	0.096*
H11B	0.4482	0.5566	0.4400	0.096*
C12	0.3001 (5)	0.4890 (2)	0.40137 (18)	0.0641 (14)
H12A	0.3701	0.4706	0.3755	0.077*
H12B	0.2078	0.4945	0.3809	0.077*
C13	0.1291 (5)	0.2984 (2)	0.47399 (16)	0.0440 (11)
C14	0.1844 (4)	0.2811 (2)	0.52684 (18)	0.0479 (12)
C15	0.1003 (5)	0.2396 (2)	0.56209 (18)	0.0498 (12)
C16	−0.0792 (5)	0.2307 (3)	0.4938 (2)	0.0539 (12)
C17	−0.0032 (5)	0.2738 (2)	0.45722 (19)	0.0572 (13)
H17A	−0.0430	0.2855	0.4219	0.069*
C18	0.0722 (5)	0.1757 (3)	0.64868 (19)	0.0787 (17)
H18A	0.1228	0.1696	0.6844	0.118*
H18B	0.0627	0.1304	0.6301	0.118*
H18C	−0.0227	0.1951	0.6545	0.118*
C19	−0.2789 (6)	0.1560 (3)	0.5116 (2)	0.101 (2)
H19A	−0.3690	0.1412	0.4936	0.151*
H19B	−0.2981	0.1792	0.5466	0.151*
H19C	−0.2185	0.1150	0.5187	0.151*
Br2	0.85647 (5)	0.04305 (3)	0.747128 (18)	0.06861 (19)
P2	0.49520 (12)	0.07662 (7)	0.69441 (4)	0.0456 (3)
O4	0.3660 (3)	0.08126 (16)	0.65554 (11)	0.0575 (8)
O5	1.0107 (3)	−0.03275 (18)	0.65904 (12)	0.0719 (10)
O6	0.6551 (4)	−0.04846 (18)	0.51877 (12)	0.0789 (11)
N2	0.8342 (4)	−0.04124 (19)	0.58850 (15)	0.0533 (10)
C20	0.4615 (5)	0.0253 (2)	0.75805 (16)	0.0527 (12)
H20A	0.5261	0.0436	0.7884	0.063*
C21	0.4891 (6)	−0.0536 (2)	0.75249 (19)	0.0708 (15)
H21A	0.5902	−0.0611	0.7439	0.085*
H21B	0.4296	−0.0722	0.7213	0.085*
C22	0.4556 (7)	−0.0946 (3)	0.8055 (2)	0.0893 (18)
H22A	0.5215	−0.0796	0.8359	0.107*
H22B	0.4708	−0.1451	0.7992	0.107*
C23	0.3000 (7)	−0.0823 (3)	0.8222 (2)	0.104 (2)
H23A	0.2337	−0.1029	0.7939	0.125*
H23B	0.2837	−0.1057	0.8578	0.125*
C24	0.2700 (7)	−0.0042 (4)	0.8275 (2)	0.116 (2)
H24A	0.3274	0.0146	0.8592	0.139*
H24B	0.1682	0.0025	0.8354	0.139*
C25	0.3048 (6)	0.0376 (3)	0.7749 (2)	0.0874 (18)
H25A	0.2899	0.0880	0.7817	0.105*
H25B	0.2390	0.0232	0.7442	0.105*
C26	0.5657 (4)	0.1628 (2)	0.71600 (16)	0.0457 (11)
H26A	0.6390	0.1547	0.7462	0.055*
C27	0.4483 (5)	0.2098 (2)	0.73966 (19)	0.0647 (14)
H27A	0.4069	0.1862	0.7717	0.078*
H27B	0.3712	0.2164	0.7112	0.078*
C28	0.5077 (6)	0.2828 (3)	0.7581 (2)	0.0740 (16)
H28A	0.4287	0.3121	0.7710	0.089*
H28B	0.5775	0.2767	0.7893	0.089*
C29	0.5806 (6)	0.3203 (3)	0.7099 (2)	0.0833 (17)
H29A	0.6225	0.3649	0.7231	0.100*
H29B	0.5088	0.3309	0.6802	0.100*
C30	0.6997 (6)	0.2730 (3)	0.6867 (2)	0.0864 (17)
H30A	0.7418	0.2964	0.6547	0.104*
H30B	0.7760	0.2664	0.7153	0.104*
C31	0.6401 (5)	0.2011 (2)	0.66855 (19)	0.0635 (14)
H31A	0.7191	0.1717	0.6557	0.076*
H31B	0.5710	0.2076	0.6372	0.076*
C32	0.6408 (5)	0.0305 (2)	0.65661 (15)	0.0415 (11)
C33	0.7819 (5)	0.0158 (2)	0.67508 (16)	0.0469 (11)
C34	0.8745 (5)	−0.0190 (2)	0.63953 (19)	0.0512 (12)
C35	0.6992 (6)	−0.0269 (2)	0.57106 (18)	0.0546 (13)
C36	0.5997 (5)	0.0085 (2)	0.60255 (17)	0.0502 (12)
H36A	0.5065	0.0176	0.5879	0.060*
C37	1.1078 (5)	−0.0689 (3)	0.6223 (2)	0.0925 (19)
H37A	1.2005	−0.0754	0.6414	0.139*
H37B	1.1198	−0.0408	0.5890	0.139*
H37C	1.0678	−0.1145	0.6121	0.139*
C38	0.7538 (6)	−0.0878 (3)	0.4870 (2)	0.0947 (19)
H38A	0.7090	−0.0999	0.4512	0.142*
H38B	0.7804	−0.1307	0.5069	0.142*
H38C	0.8392	−0.0597	0.4814	0.142*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0548 (3)	0.0821 (4)	0.0573 (3)	−0.0078 (3)	−0.0040 (2)	0.0054 (3)
P1	0.0562 (8)	0.0582 (9)	0.0455 (7)	−0.0041 (7)	0.0065 (6)	0.0029 (7)
O1	0.081 (2)	0.083 (3)	0.0513 (18)	−0.006 (2)	−0.0153 (17)	0.0075 (18)
O2	0.054 (2)	0.079 (3)	0.063 (2)	−0.0047 (18)	−0.0001 (17)	0.0187 (19)
O3	0.060 (2)	0.104 (3)	0.066 (2)	−0.031 (2)	−0.0047 (18)	0.017 (2)
N1	0.043 (2)	0.053 (3)	0.053 (2)	0.000 (2)	0.0125 (19)	0.006 (2)
C1	0.061 (3)	0.053 (3)	0.050 (3)	−0.004 (3)	0.016 (2)	−0.005 (3)
C2	0.075 (4)	0.066 (4)	0.123 (5)	0.002 (3)	0.044 (4)	0.002 (4)
C3	0.075 (4)	0.075 (5)	0.136 (5)	0.005 (4)	0.049 (4)	0.013 (4)
C4	0.101 (5)	0.091 (5)	0.130 (5)	0.032 (4)	0.035 (4)	−0.017 (5)
C5	0.144 (6)	0.071 (4)	0.146 (6)	−0.011 (4)	0.091 (5)	−0.023 (4)
C6	0.099 (5)	0.071 (4)	0.109 (4)	−0.024 (4)	0.048 (4)	−0.034 (4)
C7	0.049 (3)	0.041 (3)	0.045 (2)	0.003 (2)	0.008 (2)	0.005 (2)
C8	0.073 (4)	0.060 (4)	0.065 (3)	0.005 (3)	0.016 (3)	0.001 (3)
C9	0.073 (4)	0.061 (4)	0.071 (3)	0.002 (3)	0.005 (3)	−0.013 (3)
C10	0.106 (5)	0.050 (4)	0.096 (4)	0.010 (3)	0.002 (4)	−0.006 (3)
C11	0.116 (5)	0.046 (4)	0.079 (4)	−0.008 (3)	0.013 (3)	0.016 (3)
C12	0.088 (4)	0.055 (3)	0.050 (3)	−0.002 (3)	0.006 (3)	0.008 (3)
C13	0.048 (3)	0.042 (3)	0.042 (2)	0.005 (2)	0.009 (2)	0.006 (2)
C14	0.041 (3)	0.048 (3)	0.055 (3)	−0.004 (2)	0.006 (2)	−0.002 (2)
C15	0.050 (3)	0.053 (3)	0.047 (3)	0.010 (3)	0.008 (2)	0.004 (3)
C16	0.049 (3)	0.057 (3)	0.056 (3)	−0.005 (3)	0.008 (3)	0.004 (3)
C17	0.053 (3)	0.062 (3)	0.056 (3)	−0.002 (3)	0.003 (3)	−0.001 (3)
C18	0.065 (4)	0.110 (5)	0.062 (3)	0.003 (3)	0.014 (3)	0.032 (3)
C19	0.075 (4)	0.154 (6)	0.072 (4)	−0.051 (4)	0.003 (3)	0.025 (4)
Br2	0.0607 (3)	0.0930 (4)	0.0515 (3)	0.0121 (3)	−0.0075 (2)	−0.0178 (3)
P2	0.0424 (7)	0.0519 (8)	0.0427 (6)	0.0027 (6)	0.0061 (5)	−0.0041 (6)
O4	0.0463 (19)	0.071 (2)	0.0546 (17)	0.0099 (16)	−0.0003 (15)	−0.0143 (17)
O5	0.051 (2)	0.098 (3)	0.067 (2)	0.022 (2)	0.0063 (17)	−0.018 (2)
O6	0.094 (3)	0.092 (3)	0.0496 (19)	0.033 (2)	−0.0078 (18)	−0.0273 (19)
N2	0.063 (3)	0.055 (3)	0.043 (2)	0.009 (2)	0.014 (2)	−0.003 (2)
C20	0.058 (3)	0.056 (3)	0.045 (3)	−0.009 (3)	0.014 (2)	−0.004 (2)
C21	0.084 (4)	0.053 (4)	0.076 (3)	0.000 (3)	0.023 (3)	0.005 (3)
C22	0.111 (5)	0.066 (4)	0.092 (4)	−0.015 (4)	0.019 (4)	0.021 (3)
C23	0.116 (6)	0.097 (6)	0.101 (5)	−0.035 (4)	0.042 (4)	0.017 (4)
C24	0.113 (6)	0.137 (7)	0.102 (5)	−0.012 (5)	0.067 (4)	0.013 (5)
C25	0.086 (4)	0.080 (4)	0.100 (4)	0.009 (3)	0.059 (4)	0.008 (3)
C26	0.043 (3)	0.047 (3)	0.047 (2)	0.009 (2)	0.001 (2)	0.002 (2)
C27	0.072 (4)	0.060 (4)	0.064 (3)	0.003 (3)	0.022 (3)	−0.011 (3)
C28	0.091 (4)	0.061 (4)	0.070 (3)	0.013 (3)	0.003 (3)	−0.015 (3)
C29	0.091 (4)	0.045 (4)	0.114 (5)	0.001 (3)	0.004 (4)	−0.002 (3)
C30	0.070 (4)	0.062 (4)	0.129 (5)	−0.009 (3)	0.029 (4)	0.004 (4)
C31	0.065 (3)	0.058 (3)	0.070 (3)	0.004 (3)	0.023 (3)	0.008 (3)
C32	0.051 (3)	0.039 (3)	0.035 (2)	−0.001 (2)	0.008 (2)	−0.003 (2)
C33	0.048 (3)	0.049 (3)	0.044 (2)	0.005 (2)	0.007 (2)	−0.004 (2)
C34	0.048 (3)	0.052 (3)	0.054 (3)	0.010 (3)	0.008 (2)	0.008 (3)
C35	0.071 (4)	0.052 (3)	0.041 (3)	0.008 (3)	0.006 (3)	−0.004 (2)
C36	0.049 (3)	0.055 (3)	0.047 (3)	0.009 (2)	0.002 (2)	−0.004 (2)
C37	0.057 (4)	0.130 (5)	0.091 (4)	0.035 (4)	0.014 (3)	−0.016 (4)
C38	0.125 (5)	0.107 (5)	0.052 (3)	0.048 (4)	0.008 (3)	−0.023 (3)

Geometric parameters (Å, º)

Br1—C14	1.890 (4)	Br2—C33	1.892 (4)
P1—O1	1.479 (3)	P2—O4	1.482 (3)
P1—C1	1.826 (4)	P2—C26	1.810 (4)
P1—C7	1.830 (4)	P2—C20	1.828 (4)
P1—C13	1.861 (4)	P2—C32	1.853 (4)
O2—C15	1.342 (5)	O5—C34	1.347 (5)
O2—C18	1.450 (5)	O5—C37	1.440 (5)
O3—C16	1.337 (5)	O6—C35	1.355 (5)
O3—C19	1.407 (5)	O6—C38	1.410 (5)
N1—C15	1.322 (5)	N2—C35	1.323 (5)
N1—C16	1.340 (5)	N2—C34	1.323 (5)
C1—C2	1.482 (6)	C20—C21	1.509 (6)
C1—C6	1.498 (6)	C20—C25	1.527 (6)
C1—H1A	0.9800	C20—H20A	0.9800
C2—C3	1.487 (7)	C21—C22	1.516 (6)
C2—H2A	0.9700	C21—H21A	0.9700
C2—H2B	0.9700	C21—H21B	0.9700
C3—C4	1.491 (7)	C22—C23	1.517 (7)
C3—H3A	0.9700	C22—H22A	0.9700
C3—H3B	0.9700	C22—H22B	0.9700
C4—C5	1.455 (7)	C23—C24	1.497 (8)
C4—H4A	0.9700	C23—H23A	0.9700
C4—H4B	0.9700	C23—H23B	0.9700
C5—C6	1.503 (7)	C24—C25	1.519 (7)
C5—H5A	0.9700	C24—H24A	0.9700
C5—H5B	0.9700	C24—H24B	0.9700
C6—H6A	0.9700	C25—H25A	0.9700
C6—H6B	0.9700	C25—H25B	0.9700
C7—C12	1.530 (5)	C26—C27	1.518 (5)
C7—C8	1.532 (5)	C26—C31	1.520 (5)
C7—H7A	0.9800	C26—H26A	0.9800
C8—C9	1.511 (6)	C27—C28	1.533 (6)
C8—H8A	0.9700	C27—H27A	0.9700
C8—H8B	0.9700	C27—H27B	0.9700
C9—C10	1.505 (6)	C28—C29	1.520 (6)
C9—H9A	0.9700	C28—H28A	0.9700
C9—H9B	0.9700	C28—H28B	0.9700
C10—C11	1.520 (6)	C29—C30	1.528 (6)
C10—H10A	0.9700	C29—H29A	0.9700
C10—H10B	0.9700	C29—H29B	0.9700
C11—C12	1.521 (6)	C30—C31	1.512 (6)
C11—H11A	0.9700	C30—H30A	0.9700
C11—H11B	0.9700	C30—H30B	0.9700
C12—H12A	0.9700	C31—H31A	0.9700
C12—H12B	0.9700	C31—H31B	0.9700
C13—C17	1.349 (5)	C32—C33	1.384 (5)
C13—C14	1.378 (5)	C32—C36	1.389 (5)
C14—C15	1.396 (6)	C33—C34	1.385 (5)
C16—C17	1.393 (6)	C35—C36	1.374 (5)
C17—H17A	0.9300	C36—H36A	0.9300
C18—H18A	0.9600	C37—H37A	0.9600
C18—H18B	0.9600	C37—H37B	0.9600
C18—H18C	0.9600	C37—H37C	0.9600
C19—H19A	0.9600	C38—H38A	0.9600
C19—H19B	0.9600	C38—H38B	0.9600
C19—H19C	0.9600	C38—H38C	0.9600
O1—P1—C1	114.03 (19)	O4—P2—C26	113.32 (19)
O1—P1—C7	112.1 (2)	O4—P2—C20	113.00 (19)
C1—P1—C7	107.6 (2)	C26—P2—C20	107.78 (19)
O1—P1—C13	109.1 (2)	O4—P2—C32	107.65 (17)
C1—P1—C13	104.5 (2)	C26—P2—C32	107.23 (19)
C7—P1—C13	109.19 (18)	C20—P2—C32	107.56 (19)
C15—O2—C18	118.7 (4)	C34—O5—C37	118.1 (4)
C16—O3—C19	118.8 (4)	C35—O6—C38	117.9 (4)
C15—N1—C16	118.0 (4)	C35—N2—C34	116.9 (4)
C2—C1—C6	113.0 (4)	C21—C20—C25	109.5 (4)
C2—C1—P1	115.0 (3)	C21—C20—P2	114.2 (3)
C6—C1—P1	110.3 (3)	C25—C20—P2	109.1 (3)
C2—C1—H1A	105.9	C21—C20—H20A	107.9
C6—C1—H1A	105.9	C25—C20—H20A	107.9
P1—C1—H1A	105.9	P2—C20—H20A	107.9
C1—C2—C3	113.6 (4)	C20—C21—C22	112.7 (4)
C1—C2—H2A	108.8	C20—C21—H21A	109.1
C3—C2—H2A	108.8	C22—C21—H21A	109.1
C1—C2—H2B	108.8	C20—C21—H21B	109.1
C3—C2—H2B	108.8	C22—C21—H21B	109.1
H2A—C2—H2B	107.7	H21A—C21—H21B	107.8
C2—C3—C4	114.7 (5)	C21—C22—C23	111.2 (5)
C2—C3—H3A	108.6	C21—C22—H22A	109.4
C4—C3—H3A	108.6	C23—C22—H22A	109.4
C2—C3—H3B	108.6	C21—C22—H22B	109.4
C4—C3—H3B	108.6	C23—C22—H22B	109.4
H3A—C3—H3B	107.6	H22A—C22—H22B	108.0
C5—C4—C3	111.9 (5)	C24—C23—C22	110.4 (5)
C5—C4—H4A	109.2	C24—C23—H23A	109.6
C3—C4—H4A	109.2	C22—C23—H23A	109.6
C5—C4—H4B	109.2	C24—C23—H23B	109.6
C3—C4—H4B	109.2	C22—C23—H23B	109.6
H4A—C4—H4B	107.9	H23A—C23—H23B	108.1
C4—C5—C6	114.6 (5)	C23—C24—C25	113.0 (5)
C4—C5—H5A	108.6	C23—C24—H24A	109.0
C6—C5—H5A	108.6	C25—C24—H24A	109.0
C4—C5—H5B	108.6	C23—C24—H24B	109.0
C6—C5—H5B	108.6	C25—C24—H24B	109.0
H5A—C5—H5B	107.6	H24A—C24—H24B	107.8
C1—C6—C5	113.0 (5)	C24—C25—C20	111.5 (4)
C1—C6—H6A	109.0	C24—C25—H25A	109.3
C5—C6—H6A	109.0	C20—C25—H25A	109.3
C1—C6—H6B	109.0	C24—C25—H25B	109.3
C5—C6—H6B	109.0	C20—C25—H25B	109.3
H6A—C6—H6B	107.8	H25A—C25—H25B	108.0
C12—C7—C8	109.8 (4)	C27—C26—C31	110.2 (4)
C12—C7—P1	108.1 (3)	C27—C26—P2	111.8 (3)
C8—C7—P1	114.4 (3)	C31—C26—P2	112.2 (3)
C12—C7—H7A	108.1	C27—C26—H26A	107.4
C8—C7—H7A	108.1	C31—C26—H26A	107.4
P1—C7—H7A	108.1	P2—C26—H26A	107.5
C9—C8—C7	112.1 (4)	C26—C27—C28	111.9 (4)
C9—C8—H8A	109.2	C26—C27—H27A	109.2
C7—C8—H8A	109.2	C28—C27—H27A	109.2
C9—C8—H8B	109.2	C26—C27—H27B	109.2
C7—C8—H8B	109.2	C28—C27—H27B	109.2
H8A—C8—H8B	107.9	H27A—C27—H27B	107.9
C10—C9—C8	112.0 (4)	C29—C28—C27	111.1 (4)
C10—C9—H9A	109.2	C29—C28—H28A	109.4
C8—C9—H9A	109.2	C27—C28—H28A	109.4
C10—C9—H9B	109.2	C29—C28—H28B	109.4
C8—C9—H9B	109.2	C27—C28—H28B	109.4
H9A—C9—H9B	107.9	H28A—C28—H28B	108.0
C9—C10—C11	110.6 (4)	C28—C29—C30	110.2 (4)
C9—C10—H10A	109.5	C28—C29—H29A	109.6
C11—C10—H10A	109.5	C30—C29—H29A	109.6
C9—C10—H10B	109.5	C28—C29—H29B	109.6
C11—C10—H10B	109.5	C30—C29—H29B	109.6
H10A—C10—H10B	108.1	H29A—C29—H29B	108.1
C12—C11—C10	112.3 (4)	C31—C30—C29	111.3 (4)
C12—C11—H11A	109.1	C31—C30—H30A	109.4
C10—C11—H11A	109.1	C29—C30—H30A	109.4
C12—C11—H11B	109.1	C31—C30—H30B	109.4
C10—C11—H11B	109.1	C29—C30—H30B	109.4
H11A—C11—H11B	107.9	H30A—C30—H30B	108.0
C11—C12—C7	111.2 (3)	C30—C31—C26	112.2 (4)
C11—C12—H12A	109.4	C30—C31—H31A	109.2
C7—C12—H12A	109.4	C26—C31—H31A	109.2
C11—C12—H12B	109.4	C30—C31—H31B	109.2
C7—C12—H12B	109.4	C26—C31—H31B	109.2
H12A—C12—H12B	108.0	H31A—C31—H31B	107.9
C17—C13—C14	119.3 (4)	C33—C32—C36	117.1 (4)
C17—C13—P1	113.9 (3)	C33—C32—P2	128.7 (3)
C14—C13—P1	126.8 (4)	C36—C32—P2	114.1 (3)
C13—C14—C15	118.9 (4)	C32—C33—C34	119.4 (4)
C13—C14—Br1	124.0 (3)	C32—C33—Br2	122.7 (3)
C15—C14—Br1	117.1 (3)	C34—C33—Br2	117.9 (3)
N1—C15—O2	119.0 (4)	N2—C34—O5	118.9 (4)
N1—C15—C14	122.2 (4)	N2—C34—C33	123.3 (4)
O2—C15—C14	118.8 (4)	O5—C34—C33	117.7 (4)
O3—C16—N1	118.4 (4)	N2—C35—O6	118.3 (4)
O3—C16—C17	118.8 (4)	N2—C35—C36	124.3 (4)
N1—C16—C17	122.7 (4)	O6—C35—C36	117.3 (5)
C13—C17—C16	118.8 (4)	C35—C36—C32	118.8 (4)
C13—C17—H17A	120.6	C35—C36—H36A	120.6
C16—C17—H17A	120.6	C32—C36—H36A	120.6
O2—C18—H18A	109.5	O5—C37—H37A	109.5
O2—C18—H18B	109.5	O5—C37—H37B	109.5
H18A—C18—H18B	109.5	H37A—C37—H37B	109.5
O2—C18—H18C	109.5	O5—C37—H37C	109.5
H18A—C18—H18C	109.5	H37A—C37—H37C	109.5
H18B—C18—H18C	109.5	H37B—C37—H37C	109.5
O3—C19—H19A	109.5	O6—C38—H38A	109.5
O3—C19—H19B	109.5	O6—C38—H38B	109.5
H19A—C19—H19B	109.5	H38A—C38—H38B	109.5
O3—C19—H19C	109.5	O6—C38—H38C	109.5
H19A—C19—H19C	109.5	H38A—C38—H38C	109.5
H19B—C19—H19C	109.5	H38B—C38—H38C	109.5
O1—P1—C1—C2	73.2 (4)	O4—P2—C20—C21	88.4 (4)
C7—P1—C1—C2	−51.8 (4)	C26—P2—C20—C21	−145.6 (3)
C13—P1—C1—C2	−167.8 (4)	C32—P2—C20—C21	−30.3 (4)
O1—P1—C1—C6	−55.9 (4)	O4—P2—C20—C25	−34.5 (4)
C7—P1—C1—C6	179.1 (3)	C26—P2—C20—C25	91.5 (4)
C13—P1—C1—C6	63.1 (4)	C32—P2—C20—C25	−153.2 (3)
C6—C1—C2—C3	−47.0 (7)	C25—C20—C21—C22	−55.6 (6)
P1—C1—C2—C3	−174.8 (4)	P2—C20—C21—C22	−178.2 (3)
C1—C2—C3—C4	48.5 (7)	C20—C21—C22—C23	56.5 (6)
C2—C3—C4—C5	−49.2 (8)	C21—C22—C23—C24	−54.4 (7)
C3—C4—C5—C6	49.6 (8)	C22—C23—C24—C25	54.5 (7)
C2—C1—C6—C5	47.2 (7)	C23—C24—C25—C20	−55.0 (7)
P1—C1—C6—C5	177.5 (4)	C21—C20—C25—C24	54.0 (6)
C4—C5—C6—C1	−49.6 (8)	P2—C20—C25—C24	179.6 (4)
O1—P1—C7—C12	−36.3 (4)	O4—P2—C26—C27	52.7 (3)
C1—P1—C7—C12	89.9 (3)	C20—P2—C26—C27	−73.1 (3)
C13—P1—C7—C12	−157.3 (3)	C32—P2—C26—C27	171.4 (3)
O1—P1—C7—C8	86.4 (3)	O4—P2—C26—C31	−71.7 (3)
C1—P1—C7—C8	−147.5 (3)	C20—P2—C26—C31	162.5 (3)
C13—P1—C7—C8	−34.6 (4)	C32—P2—C26—C31	47.0 (3)
C12—C7—C8—C9	−55.0 (5)	C31—C26—C27—C28	−54.6 (5)
P1—C7—C8—C9	−176.7 (3)	P2—C26—C27—C28	179.9 (3)
C7—C8—C9—C10	55.9 (5)	C26—C27—C28—C29	56.0 (5)
C8—C9—C10—C11	−54.7 (6)	C27—C28—C29—C30	−55.7 (6)
C9—C10—C11—C12	55.0 (6)	C28—C29—C30—C31	56.1 (6)
C10—C11—C12—C7	−55.6 (6)	C29—C30—C31—C26	−56.3 (6)
C8—C7—C12—C11	54.5 (5)	C27—C26—C31—C30	55.0 (5)
P1—C7—C12—C11	180.0 (4)	P2—C26—C31—C30	−179.7 (3)
O1—P1—C13—C17	6.2 (4)	O4—P2—C32—C33	177.9 (4)
C1—P1—C13—C17	−116.1 (3)	C26—P2—C32—C33	55.7 (4)
C7—P1—C13—C17	129.0 (3)	C20—P2—C32—C33	−60.0 (4)
O1—P1—C13—C14	−176.4 (4)	O4—P2—C32—C36	−2.0 (4)
C1—P1—C13—C14	61.3 (4)	C26—P2—C32—C36	−124.2 (3)
C7—P1—C13—C14	−53.6 (4)	C20—P2—C32—C36	120.1 (3)
C17—C13—C14—C15	−1.4 (6)	C36—C32—C33—C34	0.4 (6)
P1—C13—C14—C15	−178.6 (3)	P2—C32—C33—C34	−179.5 (3)
C17—C13—C14—Br1	176.4 (3)	C36—C32—C33—Br2	179.2 (3)
P1—C13—C14—Br1	−0.9 (6)	P2—C32—C33—Br2	−0.7 (6)
C16—N1—C15—O2	−179.5 (4)	C35—N2—C34—O5	179.7 (4)
C16—N1—C15—C14	0.1 (6)	C35—N2—C34—C33	1.9 (7)
C18—O2—C15—N1	5.2 (6)	C37—O5—C34—N2	2.2 (6)
C18—O2—C15—C14	−174.4 (4)	C37—O5—C34—C33	−179.9 (4)
C13—C14—C15—N1	1.8 (7)	C32—C33—C34—N2	−1.8 (7)
Br1—C14—C15—N1	−176.1 (3)	Br2—C33—C34—N2	179.3 (3)
C13—C14—C15—O2	−178.6 (4)	C32—C33—C34—O5	−179.7 (4)
Br1—C14—C15—O2	3.5 (5)	Br2—C33—C34—O5	1.4 (6)
C19—O3—C16—N1	−4.2 (7)	C34—N2—C35—O6	179.5 (4)
C19—O3—C16—C17	175.4 (5)	C34—N2—C35—C36	−0.6 (7)
C15—N1—C16—O3	177.3 (4)	C38—O6—C35—N2	2.9 (7)
C15—N1—C16—C17	−2.4 (7)	C38—O6—C35—C36	−177.0 (4)
C14—C13—C17—C16	−0.8 (7)	N2—C35—C36—C32	−0.8 (7)
P1—C13—C17—C16	176.8 (3)	O6—C35—C36—C32	179.2 (4)
O3—C16—C17—C13	−176.9 (4)	C33—C32—C36—C35	0.8 (6)
N1—C16—C17—C13	2.8 (7)	P2—C32—C36—C35	−179.3 (3)