Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803016623/tk6106sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803016623/tk6106Isup2.hkl |
CCDC reference: 222846
To a boiling solution of racemic (II) (Pai et al., 2000) (1.87 g, 2.76 mmol) in chloroform (28 ml) was added a solution of (-)-DBT, (II), in ethyl acetate (28 ml). The mixture was refluxed until a white solid formed and then allowed to stand at ambient temperature overnight. The solid product was dried at room temperature under vacuum to give a 1:1 complex of (R)-(II) and (-)-DBT (93% yield). The mother liquor, which contained the (S)-(II)–(+)-DBT complex, was concentrated to dryness to give a solid material. This was dissolved in chloroform (10 ml) and then treated with 10% aqueous NaOH (10 ml). The mixture was extracted with two portions of chloroform (25 ml). Evaporation of the solvent gave crude (S)-(II), which was dissolved in refluxing chloroform (15 ml), and to this solution was added a solution of (+)-DBT in ethyl acetate (20 ml). The mixture was stirred at reflux temperature until the white precipitate formed and was then allowed to stand at room temperature overnight. The white precipitate was dried to give the pure (S)-(II)–(+)-DBT complex (92% yield). The crystal used for the data collection was obtained by slow evaporation from chloroform–ethyl acetate (1:1) saturated solution at room temperature.
H atoms were included in the riding model approximation, with Uiso(H) equal to Ueq of the atom to which they were bound. Two of the Cl atoms in the solvent CHCl3 molecule are disordered and were each modelled over two positions with site occupancies of 0.587 (2) and 0.413 (2).
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL).
Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level (Bruker, 1995). | |
Fig. 2. Packing diagram for (I). |
C38H34N2O6P2·C18H14O8·CHCl3 | Dx = 1.320 Mg m−3 |
Mr = 1154.27 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 6132 reflections |
a = 10.0967 (10) Å | θ = 1–27.5° |
b = 21.000 (2) Å | µ = 0.28 mm−1 |
c = 27.390 (3) Å | T = 294 K |
V = 5807.6 (10) Å3 | Block, colorless |
Z = 4 | 0.28 × 0.28 × 0.20 mm |
F(000) = 2392 |
Siemens CCD area-detector diffractometer | 13342 independent reflections |
Radiation source: fine-focus sealed tube | 8576 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scans (SADABS; Sheldrick, 1996) | h = −13→11 |
Tmin = 0.926, Tmax = 0.947 | k = −23→27 |
39041 measured reflections | l = −30→35 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.147 | w = 1/[σ2(Fo2) + (0.08P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.014 |
13342 reflections | Δρmax = 0.32 e Å−3 |
725 parameters | Δρmin = −0.38 e Å−3 |
80 restraints | Absolute structure: Flack (1983), 0000 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.05 (8) |
C38H34N2O6P2·C18H14O8·CHCl3 | V = 5807.6 (10) Å3 |
Mr = 1154.27 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.0967 (10) Å | µ = 0.28 mm−1 |
b = 21.000 (2) Å | T = 294 K |
c = 27.390 (3) Å | 0.28 × 0.28 × 0.20 mm |
Siemens CCD area-detector diffractometer | 13342 independent reflections |
Absorption correction: multi-scans (SADABS; Sheldrick, 1996) | 8576 reflections with I > 2σ(I) |
Tmin = 0.926, Tmax = 0.947 | Rint = 0.043 |
39041 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.147 | Δρmax = 0.32 e Å−3 |
S = 1.01 | Δρmin = −0.38 e Å−3 |
13342 reflections | Absolute structure: Flack (1983), 0000 Friedel pairs |
725 parameters | Absolute structure parameter: 0.05 (8) |
80 restraints |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.3805 (3) | 0.55217 (10) | 0.63658 (9) | 0.0991 (7) | |
O2 | 0.44452 (16) | 0.45185 (8) | 0.62542 (6) | 0.0600 (4) | |
O3 | 0.5037 (2) | 0.45131 (14) | 0.72252 (7) | 0.1026 (8) | |
O4 | 0.7157 (2) | 0.47059 (10) | 0.70609 (6) | 0.0777 (6) | |
H4 | 0.7372 | 0.4630 | 0.7344 | 0.093* | |
O5 | 0.5867 (2) | 0.37045 (10) | 0.53949 (7) | 0.0870 (6) | |
O6 | 0.66929 (19) | 0.46893 (8) | 0.54002 (6) | 0.0641 (5) | |
H6 | 0.6555 | 0.4676 | 0.5105 | 0.096* | |
O7 | 0.63254 (17) | 0.35689 (8) | 0.63706 (6) | 0.0598 (4) | |
O8 | 0.8171 (2) | 0.31478 (11) | 0.60587 (9) | 0.0926 (7) | |
C1 | 0.1271 (3) | 0.5199 (2) | 0.59568 (12) | 0.1042 (12) | |
H1A | 0.1373 | 0.5615 | 0.6066 | 0.125* | |
C2 | 0.0109 (4) | 0.5016 (2) | 0.57382 (15) | 0.1169 (15) | |
H2A | −0.0589 | 0.5302 | 0.5711 | 0.140* | |
C3 | −0.0014 (4) | 0.4423 (2) | 0.55642 (15) | 0.1299 (18) | |
H3A | −0.0791 | 0.4306 | 0.5405 | 0.156* | |
C4 | 0.0970 (3) | 0.3989 (2) | 0.56163 (16) | 0.1219 (15) | |
H4A | 0.0862 | 0.3576 | 0.5499 | 0.146* | |
C5 | 0.2126 (3) | 0.41609 (18) | 0.58426 (13) | 0.0925 (10) | |
H5A | 0.2803 | 0.3865 | 0.5879 | 0.111* | |
C6 | 0.2287 (3) | 0.47658 (15) | 0.60142 (9) | 0.0724 (8) | |
C7 | 0.3561 (3) | 0.49931 (15) | 0.62368 (9) | 0.0653 (7) | |
C8 | 0.5770 (2) | 0.46591 (12) | 0.63959 (8) | 0.0550 (6) | |
H8A | 0.6013 | 0.5087 | 0.6284 | 0.066* | |
C9 | 0.5932 (3) | 0.46152 (13) | 0.69510 (9) | 0.0627 (7) | |
C10 | 0.6628 (2) | 0.41686 (12) | 0.61447 (8) | 0.0547 (6) | |
H10A | 0.7564 | 0.4271 | 0.6198 | 0.066* | |
C11 | 0.6347 (3) | 0.41456 (14) | 0.55988 (9) | 0.0576 (6) | |
C12 | 0.7197 (3) | 0.30898 (14) | 0.63152 (10) | 0.0648 (7) | |
C13 | 0.6840 (3) | 0.25199 (13) | 0.65916 (10) | 0.0677 (7) | |
C14 | 0.5778 (3) | 0.25204 (14) | 0.69159 (10) | 0.0719 (8) | |
H14A | 0.5277 | 0.2888 | 0.6960 | 0.086* | |
C15 | 0.5469 (4) | 0.19720 (16) | 0.71729 (12) | 0.0881 (10) | |
H15A | 0.4764 | 0.1974 | 0.7392 | 0.106* | |
C16 | 0.6186 (5) | 0.14293 (17) | 0.71083 (13) | 0.1031 (12) | |
H16A | 0.5973 | 0.1066 | 0.7286 | 0.124* | |
C17 | 0.7192 (4) | 0.14131 (17) | 0.67929 (16) | 0.1044 (12) | |
H17A | 0.7653 | 0.1035 | 0.6743 | 0.125* | |
C18 | 0.7555 (4) | 0.19620 (15) | 0.65381 (13) | 0.0882 (10) | |
H18A | 0.8284 | 0.1953 | 0.6331 | 0.106* | |
P1 | 0.25641 (7) | 1.05372 (3) | 0.59321 (2) | 0.05236 (15) | |
P2 | 0.11799 (6) | 0.88060 (3) | 0.68866 (2) | 0.04946 (15) | |
O9 | 0.17698 (17) | 1.02580 (8) | 0.55299 (5) | 0.0567 (4) | |
O10 | 0.2136 (3) | 1.14949 (12) | 0.76243 (8) | 0.1064 (8) | |
O11 | −0.10346 (19) | 1.00073 (10) | 0.72040 (6) | 0.0704 (5) | |
O12 | −0.10600 (18) | 1.05418 (9) | 0.58546 (6) | 0.0653 (5) | |
O13 | −0.1001 (3) | 0.85143 (11) | 0.52157 (7) | 0.0909 (7) | |
O14 | 0.20482 (17) | 0.92923 (8) | 0.71128 (6) | 0.0593 (4) | |
N1 | 0.0509 (2) | 1.07623 (11) | 0.74167 (7) | 0.0658 (6) | |
N2 | −0.1035 (2) | 0.95351 (10) | 0.55315 (7) | 0.0556 (5) | |
C19 | 0.3154 (3) | 1.13159 (13) | 0.57680 (10) | 0.0701 (8) | |
C20 | 0.2224 (5) | 1.17436 (15) | 0.55988 (19) | 0.1336 (18) | |
H20A | 0.1332 | 1.1633 | 0.5602 | 0.160* | |
C21 | 0.2599 (5) | 1.23308 (19) | 0.5425 (2) | 0.173 (2) | |
H21A | 0.1971 | 1.2614 | 0.5305 | 0.208* | |
C22 | 0.3908 (5) | 1.24914 (19) | 0.54317 (18) | 0.154 (2) | |
H22A | 0.4160 | 1.2893 | 0.5323 | 0.185* | |
C23 | 0.4852 (5) | 1.20848 (18) | 0.55920 (13) | 0.1180 (15) | |
H23A | 0.5741 | 1.2201 | 0.5590 | 0.142* | |
C24 | 0.4462 (3) | 1.14937 (16) | 0.57590 (11) | 0.0874 (10) | |
H24A | 0.5101 | 1.1209 | 0.5868 | 0.105* | |
C25 | 0.3986 (3) | 1.00518 (13) | 0.60725 (8) | 0.0593 (7) | |
C26 | 0.4589 (3) | 1.00151 (15) | 0.65229 (10) | 0.0748 (8) | |
H26A | 0.4244 | 1.0244 | 0.6784 | 0.090* | |
C27 | 0.5698 (3) | 0.96424 (17) | 0.65900 (11) | 0.0872 (10) | |
H27A | 0.6099 | 0.9623 | 0.6895 | 0.105* | |
C28 | 0.6208 (3) | 0.93032 (19) | 0.62107 (11) | 0.0985 (11) | |
H28A | 0.6971 | 0.9062 | 0.6256 | 0.118* | |
C29 | 0.5601 (3) | 0.9314 (2) | 0.57577 (12) | 0.1106 (13) | |
H29A | 0.5933 | 0.9070 | 0.5502 | 0.133* | |
C30 | 0.4502 (3) | 0.96897 (18) | 0.56901 (10) | 0.0929 (11) | |
H30A | 0.4096 | 0.9703 | 0.5385 | 0.111* | |
C31 | 0.1649 (3) | 1.06377 (11) | 0.65001 (8) | 0.0523 (6) | |
C32 | 0.2153 (3) | 1.10768 (13) | 0.68393 (10) | 0.0686 (8) | |
H32A | 0.2856 | 1.1344 | 0.6760 | 0.082* | |
C33 | 0.1569 (3) | 1.10955 (14) | 0.72920 (10) | 0.0721 (8) | |
C34 | 0.1654 (5) | 1.1453 (2) | 0.81149 (12) | 0.1236 (15) | |
H34A | 0.0722 | 1.1543 | 0.8119 | 0.185* | |
H34B | 0.2111 | 1.1757 | 0.8316 | 0.185* | |
H34C | 0.1805 | 1.1032 | 0.8239 | 0.185* | |
C35 | 0.0035 (3) | 1.03613 (12) | 0.70902 (8) | 0.0549 (6) | |
C36 | −0.1524 (4) | 1.00470 (19) | 0.76961 (11) | 0.0948 (11) | |
H36A | −0.0864 | 0.9889 | 0.7918 | 0.142* | |
H36B | −0.2314 | 0.9796 | 0.7726 | 0.142* | |
H36C | −0.1722 | 1.0483 | 0.7773 | 0.142* | |
C37 | 0.0575 (2) | 1.02631 (11) | 0.66235 (8) | 0.0458 (5) | |
C38 | 0.0055 (2) | 0.97544 (11) | 0.62965 (7) | 0.0446 (5) | |
C39 | −0.0690 (2) | 0.99299 (12) | 0.58846 (8) | 0.0493 (6) | |
C40 | −0.1728 (3) | 1.07385 (16) | 0.54199 (11) | 0.0854 (10) | |
H40A | −0.1154 | 1.0680 | 0.5144 | 0.128* | |
H40B | −0.1965 | 1.1180 | 0.5447 | 0.128* | |
H40C | −0.2514 | 1.0488 | 0.5377 | 0.128* | |
C41 | −0.0705 (3) | 0.89319 (14) | 0.55802 (8) | 0.0610 (7) | |
C42 | −0.1514 (5) | 0.8782 (2) | 0.47710 (11) | 0.1156 (14) | |
H42A | −0.2373 | 0.8961 | 0.4831 | 0.173* | |
H42B | −0.1584 | 0.8454 | 0.4528 | 0.173* | |
H42C | −0.0926 | 0.9109 | 0.4657 | 0.173* | |
C43 | −0.0046 (3) | 0.86866 (12) | 0.59801 (8) | 0.0577 (7) | |
H43A | 0.0132 | 0.8253 | 0.6006 | 0.069* | |
C44 | 0.0342 (2) | 0.91122 (11) | 0.63451 (7) | 0.0462 (5) | |
C45 | 0.2119 (3) | 0.81221 (11) | 0.67053 (9) | 0.0586 (7) | |
C46 | 0.3406 (4) | 0.82231 (17) | 0.65534 (19) | 0.1272 (16) | |
H46A | 0.3745 | 0.8635 | 0.6544 | 0.153* | |
C47 | 0.4184 (5) | 0.77211 (19) | 0.6417 (2) | 0.166 (2) | |
H47A | 0.5011 | 0.7803 | 0.6282 | 0.199* | |
C48 | 0.3795 (4) | 0.71099 (18) | 0.64712 (14) | 0.1117 (13) | |
H48A | 0.4366 | 0.6775 | 0.6400 | 0.134* | |
C49 | 0.2550 (4) | 0.69997 (17) | 0.66314 (17) | 0.1165 (15) | |
H49A | 0.2243 | 0.6584 | 0.6661 | 0.140* | |
C50 | 0.1735 (4) | 0.75024 (14) | 0.67517 (16) | 0.1005 (12) | |
H50A | 0.0890 | 0.7416 | 0.6869 | 0.121* | |
C51 | −0.0102 (3) | 0.85161 (13) | 0.72909 (8) | 0.0601 (7) | |
C52 | −0.1397 (3) | 0.84408 (18) | 0.71651 (11) | 0.0896 (10) | |
H52A | −0.1662 | 0.8532 | 0.6848 | 0.108* | |
C53 | −0.2315 (4) | 0.8234 (2) | 0.74950 (13) | 0.1100 (13) | |
H53A | −0.3201 | 0.8204 | 0.7404 | 0.132* | |
C54 | −0.1945 (4) | 0.8073 (2) | 0.79530 (13) | 0.1159 (14) | |
H54A | −0.2558 | 0.7909 | 0.8173 | 0.139* | |
C55 | −0.0681 (4) | 0.8153 (3) | 0.80842 (14) | 0.145 (2) | |
H55A | −0.0424 | 0.8058 | 0.8402 | 0.174* | |
C56 | 0.0242 (4) | 0.8372 (2) | 0.77582 (10) | 0.1167 (15) | |
H56A | 0.1116 | 0.8424 | 0.7858 | 0.140* | |
C57 | −0.6853 (6) | 0.7958 (3) | 0.4693 (2) | 0.1631 (17) | |
H57 | −0.6627 | 0.7622 | 0.4926 | 0.196* | |
Cl1 | −0.5416 (3) | 0.81617 (11) | 0.44082 (11) | 0.2404 (11) | |
Cl2 | −0.7971 (4) | 0.76482 (17) | 0.43153 (12) | 0.2098 (15) | 0.587 (2) |
Cl3 | −0.7441 (6) | 0.8565 (3) | 0.5022 (2) | 0.313 (2) | 0.587 (2) |
Cl2' | −0.8010 (5) | 0.8625 (4) | 0.4446 (2) | 0.283 (4) | 0.413 (2) |
Cl3' | −0.7003 (7) | 0.8022 (2) | 0.52905 (13) | 0.203 (3) | 0.413 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.1106 (17) | 0.0727 (13) | 0.1139 (17) | 0.0227 (14) | −0.0159 (15) | −0.0060 (13) |
O2 | 0.0532 (9) | 0.0667 (10) | 0.0600 (9) | 0.0019 (9) | −0.0065 (8) | 0.0091 (8) |
O3 | 0.0825 (14) | 0.174 (2) | 0.0516 (10) | 0.0113 (16) | 0.0075 (10) | 0.0223 (13) |
O4 | 0.0769 (13) | 0.1094 (15) | 0.0467 (9) | −0.0174 (11) | −0.0176 (9) | 0.0124 (10) |
O5 | 0.1129 (16) | 0.0855 (13) | 0.0626 (11) | −0.0377 (13) | −0.0210 (11) | 0.0016 (10) |
O6 | 0.0765 (11) | 0.0779 (11) | 0.0378 (8) | −0.0127 (10) | −0.0063 (8) | 0.0063 (8) |
O7 | 0.0589 (10) | 0.0657 (10) | 0.0549 (9) | 0.0062 (9) | 0.0036 (8) | 0.0136 (8) |
O8 | 0.0772 (13) | 0.1006 (15) | 0.0999 (15) | 0.0171 (12) | 0.0264 (12) | 0.0000 (13) |
C1 | 0.075 (2) | 0.151 (3) | 0.087 (2) | 0.040 (2) | 0.0062 (18) | 0.032 (2) |
C2 | 0.069 (2) | 0.176 (4) | 0.106 (3) | 0.047 (3) | −0.005 (2) | 0.029 (3) |
C3 | 0.065 (2) | 0.228 (6) | 0.098 (3) | −0.006 (3) | 0.005 (2) | 0.029 (3) |
C4 | 0.061 (2) | 0.167 (4) | 0.138 (3) | −0.018 (2) | −0.015 (2) | −0.006 (3) |
C5 | 0.0631 (19) | 0.115 (3) | 0.099 (2) | −0.0013 (19) | −0.0021 (18) | 0.005 (2) |
C6 | 0.0572 (15) | 0.115 (2) | 0.0451 (13) | 0.0212 (16) | 0.0072 (12) | 0.0218 (14) |
C7 | 0.0712 (17) | 0.0783 (18) | 0.0464 (13) | 0.0212 (15) | 0.0042 (13) | 0.0134 (13) |
C8 | 0.0539 (13) | 0.0631 (14) | 0.0479 (12) | −0.0049 (12) | −0.0085 (11) | 0.0101 (11) |
C9 | 0.0672 (17) | 0.0773 (17) | 0.0435 (12) | 0.0074 (14) | −0.0046 (12) | 0.0096 (12) |
C10 | 0.0501 (13) | 0.0674 (15) | 0.0465 (12) | −0.0068 (12) | −0.0032 (10) | 0.0098 (11) |
C11 | 0.0505 (14) | 0.0715 (16) | 0.0508 (13) | −0.0069 (13) | −0.0029 (11) | 0.0058 (12) |
C12 | 0.0607 (16) | 0.0796 (18) | 0.0541 (14) | 0.0129 (14) | −0.0016 (13) | −0.0017 (13) |
C13 | 0.0748 (17) | 0.0652 (16) | 0.0631 (16) | 0.0120 (14) | −0.0132 (14) | −0.0007 (13) |
C14 | 0.0812 (19) | 0.0680 (17) | 0.0663 (16) | 0.0035 (15) | 0.0015 (15) | 0.0025 (14) |
C15 | 0.102 (2) | 0.082 (2) | 0.080 (2) | −0.005 (2) | −0.0040 (18) | 0.0137 (17) |
C16 | 0.144 (3) | 0.074 (2) | 0.091 (2) | 0.004 (2) | −0.030 (2) | 0.0181 (18) |
C17 | 0.121 (3) | 0.072 (2) | 0.120 (3) | 0.035 (2) | −0.022 (3) | 0.000 (2) |
C18 | 0.093 (2) | 0.079 (2) | 0.093 (2) | 0.0248 (18) | −0.0101 (19) | −0.0016 (17) |
P1 | 0.0571 (3) | 0.0603 (4) | 0.0397 (3) | −0.0099 (3) | −0.0014 (3) | 0.0026 (3) |
P2 | 0.0547 (3) | 0.0560 (3) | 0.0377 (3) | 0.0027 (3) | −0.0068 (3) | 0.0012 (3) |
O9 | 0.0608 (10) | 0.0696 (10) | 0.0396 (8) | −0.0113 (8) | 0.0004 (7) | 0.0022 (8) |
O10 | 0.143 (2) | 0.1101 (16) | 0.0664 (12) | −0.0255 (16) | −0.0056 (13) | −0.0403 (12) |
O11 | 0.0662 (11) | 0.0945 (13) | 0.0505 (9) | −0.0026 (10) | 0.0140 (9) | −0.0057 (9) |
O12 | 0.0677 (11) | 0.0703 (11) | 0.0581 (9) | 0.0186 (9) | −0.0112 (9) | 0.0075 (8) |
O13 | 0.1265 (18) | 0.0947 (14) | 0.0514 (10) | −0.0049 (14) | −0.0340 (11) | −0.0155 (10) |
O14 | 0.0646 (10) | 0.0673 (10) | 0.0458 (8) | 0.0007 (8) | −0.0152 (8) | −0.0012 (8) |
N1 | 0.0771 (15) | 0.0706 (13) | 0.0497 (11) | 0.0121 (12) | 0.0007 (11) | −0.0132 (10) |
N2 | 0.0534 (11) | 0.0722 (13) | 0.0411 (9) | −0.0057 (11) | −0.0095 (8) | 0.0050 (9) |
C19 | 0.0854 (19) | 0.0715 (18) | 0.0534 (14) | −0.0208 (15) | −0.0156 (13) | 0.0047 (13) |
C20 | 0.136 (4) | 0.070 (2) | 0.195 (5) | −0.015 (2) | −0.066 (3) | 0.032 (3) |
C21 | 0.183 (5) | 0.074 (3) | 0.263 (6) | −0.035 (3) | −0.106 (5) | 0.049 (3) |
C22 | 0.238 (6) | 0.091 (3) | 0.133 (3) | −0.084 (3) | −0.054 (4) | 0.028 (2) |
C23 | 0.147 (3) | 0.124 (3) | 0.083 (2) | −0.075 (3) | −0.014 (2) | 0.018 (2) |
C24 | 0.095 (2) | 0.096 (2) | 0.0707 (18) | −0.0383 (19) | −0.0078 (17) | 0.0193 (17) |
C25 | 0.0578 (15) | 0.0709 (16) | 0.0491 (13) | −0.0078 (13) | 0.0053 (11) | 0.0097 (12) |
C26 | 0.0736 (18) | 0.094 (2) | 0.0568 (15) | 0.0052 (17) | −0.0034 (14) | 0.0040 (15) |
C27 | 0.0713 (19) | 0.127 (3) | 0.0631 (17) | 0.007 (2) | −0.0074 (15) | 0.0107 (18) |
C28 | 0.0607 (17) | 0.142 (3) | 0.093 (2) | 0.015 (2) | 0.0125 (18) | 0.033 (2) |
C29 | 0.093 (2) | 0.162 (3) | 0.077 (2) | 0.053 (3) | 0.0120 (19) | −0.003 (2) |
C30 | 0.080 (2) | 0.146 (3) | 0.0527 (16) | 0.022 (2) | −0.0002 (15) | −0.0061 (18) |
C31 | 0.0615 (14) | 0.0528 (13) | 0.0426 (11) | 0.0048 (12) | −0.0082 (10) | −0.0048 (10) |
C32 | 0.0791 (18) | 0.0634 (16) | 0.0634 (16) | −0.0122 (14) | −0.0059 (14) | −0.0088 (13) |
C33 | 0.095 (2) | 0.0707 (17) | 0.0508 (14) | 0.0036 (16) | −0.0116 (14) | −0.0220 (13) |
C34 | 0.156 (4) | 0.146 (3) | 0.069 (2) | −0.007 (3) | 0.008 (2) | −0.061 (2) |
C35 | 0.0619 (15) | 0.0596 (14) | 0.0431 (12) | 0.0113 (12) | −0.0024 (11) | −0.0048 (11) |
C36 | 0.100 (2) | 0.124 (3) | 0.0610 (16) | −0.005 (2) | 0.0309 (17) | −0.0095 (18) |
C37 | 0.0493 (12) | 0.0489 (12) | 0.0392 (11) | 0.0073 (11) | −0.0036 (10) | 0.0019 (9) |
C38 | 0.0398 (11) | 0.0599 (14) | 0.0340 (10) | 0.0002 (10) | 0.0010 (9) | 0.0004 (10) |
C39 | 0.0421 (11) | 0.0656 (15) | 0.0402 (11) | 0.0012 (11) | 0.0016 (10) | 0.0052 (11) |
C40 | 0.086 (2) | 0.095 (2) | 0.0745 (18) | 0.0153 (18) | −0.0258 (16) | 0.0212 (17) |
C41 | 0.0667 (15) | 0.0758 (18) | 0.0404 (12) | −0.0111 (14) | −0.0082 (11) | −0.0065 (12) |
C42 | 0.166 (4) | 0.127 (3) | 0.0531 (16) | 0.004 (3) | −0.045 (2) | −0.0201 (19) |
C43 | 0.0727 (16) | 0.0567 (15) | 0.0436 (12) | −0.0051 (13) | −0.0110 (12) | −0.0029 (11) |
C44 | 0.0495 (12) | 0.0565 (13) | 0.0327 (10) | 0.0003 (10) | −0.0049 (9) | 0.0024 (10) |
C45 | 0.0752 (17) | 0.0534 (14) | 0.0472 (13) | 0.0065 (13) | −0.0067 (12) | 0.0051 (11) |
C46 | 0.119 (3) | 0.071 (2) | 0.192 (4) | 0.018 (2) | 0.079 (3) | 0.017 (2) |
C47 | 0.139 (4) | 0.106 (3) | 0.252 (6) | 0.029 (3) | 0.106 (4) | −0.006 (4) |
C48 | 0.138 (3) | 0.094 (3) | 0.103 (3) | 0.051 (3) | 0.002 (3) | −0.009 (2) |
C49 | 0.134 (3) | 0.060 (2) | 0.156 (4) | 0.011 (2) | −0.022 (3) | −0.009 (2) |
C50 | 0.089 (2) | 0.067 (2) | 0.146 (3) | −0.0004 (18) | 0.000 (2) | −0.004 (2) |
C51 | 0.0576 (15) | 0.0754 (17) | 0.0473 (13) | 0.0035 (13) | −0.0032 (12) | 0.0072 (12) |
C52 | 0.070 (2) | 0.131 (3) | 0.0683 (18) | −0.012 (2) | −0.0055 (16) | 0.0292 (19) |
C53 | 0.067 (2) | 0.161 (4) | 0.102 (3) | −0.027 (2) | 0.005 (2) | 0.024 (3) |
C54 | 0.085 (2) | 0.173 (4) | 0.090 (3) | −0.019 (3) | 0.016 (2) | 0.033 (3) |
C55 | 0.099 (3) | 0.269 (6) | 0.067 (2) | −0.027 (4) | −0.005 (2) | 0.065 (3) |
C56 | 0.079 (2) | 0.218 (4) | 0.0533 (17) | −0.013 (3) | −0.0058 (16) | 0.039 (2) |
C57 | 0.200 | 0.161 (4) | 0.128 (4) | −0.033 (5) | 0.030 (4) | 0.013 (4) |
Cl1 | 0.210 (2) | 0.2053 (19) | 0.306 (3) | −0.0297 (18) | 0.043 (2) | 0.0024 (19) |
Cl2 | 0.237 (3) | 0.193 (3) | 0.200 (3) | −0.030 (3) | −0.119 (2) | −0.014 (2) |
Cl3 | 0.298 (5) | 0.342 (6) | 0.299 (6) | −0.095 (5) | 0.129 (4) | −0.160 (4) |
Cl2' | 0.166 (4) | 0.430 (9) | 0.254 (5) | 0.053 (5) | 0.053 (4) | 0.190 (6) |
Cl3' | 0.323 (7) | 0.190 (4) | 0.097 (2) | −0.008 (5) | −0.008 (3) | −0.020 (2) |
O1—C7 | 1.191 (4) | C21—H21A | 0.9300 |
O2—C7 | 1.339 (3) | C22—C23 | 1.353 (5) |
O2—C8 | 1.424 (3) | C22—H22A | 0.9300 |
O3—C9 | 1.194 (3) | C23—C24 | 1.380 (4) |
O4—C9 | 1.287 (3) | C23—H23A | 0.9300 |
O4—H4 | 0.8200 | C24—H24A | 0.9300 |
O5—C11 | 1.185 (3) | C25—C26 | 1.378 (3) |
O6—C11 | 1.312 (3) | C25—C30 | 1.395 (4) |
O6—H6 | 0.8200 | C26—C27 | 1.379 (4) |
O7—C12 | 1.346 (3) | C26—H26A | 0.9300 |
O7—C10 | 1.436 (3) | C27—C28 | 1.361 (4) |
O8—C12 | 1.215 (3) | C27—H27A | 0.9300 |
C1—C2 | 1.371 (5) | C28—C29 | 1.384 (4) |
C1—C6 | 1.380 (4) | C28—H28A | 0.9300 |
C1—H1A | 0.9300 | C29—C30 | 1.375 (4) |
C2—C3 | 1.339 (5) | C29—H29A | 0.9300 |
C2—H2A | 0.9300 | C30—H30A | 0.9300 |
C3—C4 | 1.357 (5) | C31—C37 | 1.381 (3) |
C3—H3A | 0.9300 | C31—C32 | 1.405 (4) |
C4—C5 | 1.370 (4) | C32—C33 | 1.374 (4) |
C4—H4A | 0.9300 | C32—H32A | 0.9300 |
C5—C6 | 1.364 (4) | C34—H34A | 0.9600 |
C5—H5A | 0.9300 | C34—H34B | 0.9600 |
C6—C7 | 1.501 (4) | C34—H34C | 0.9600 |
C8—C10 | 1.511 (4) | C35—C37 | 1.405 (3) |
C8—C9 | 1.532 (3) | C36—H36A | 0.9600 |
C8—H8A | 0.9800 | C36—H36B | 0.9600 |
C10—C11 | 1.523 (3) | C36—H36C | 0.9600 |
C10—H10A | 0.9800 | C37—C38 | 1.490 (3) |
C12—C13 | 1.461 (4) | C38—C44 | 1.386 (3) |
C13—C18 | 1.384 (4) | C38—C39 | 1.405 (3) |
C13—C14 | 1.393 (4) | C40—H40A | 0.9600 |
C14—C15 | 1.385 (4) | C40—H40B | 0.9600 |
C14—H14A | 0.9300 | C40—H40C | 0.9600 |
C15—C16 | 1.362 (5) | C41—C43 | 1.381 (3) |
C15—H15A | 0.9300 | C42—H42A | 0.9600 |
C16—C17 | 1.334 (6) | C42—H42B | 0.9600 |
C16—H16A | 0.9300 | C42—H42C | 0.9600 |
C17—C18 | 1.396 (5) | C43—C44 | 1.397 (3) |
C17—H17A | 0.9300 | C43—H43A | 0.9300 |
C18—H18A | 0.9300 | C45—C50 | 1.364 (4) |
P1—O9 | 1.4835 (17) | C45—C46 | 1.380 (4) |
P1—C19 | 1.797 (3) | C46—C47 | 1.367 (4) |
P1—C25 | 1.802 (3) | C46—H46A | 0.9300 |
P1—C31 | 1.822 (2) | C47—C48 | 1.350 (5) |
P2—O14 | 1.4816 (18) | C47—H47A | 0.9300 |
P2—C45 | 1.791 (3) | C48—C49 | 1.351 (5) |
P2—C51 | 1.809 (3) | C48—H48A | 0.9300 |
P2—C44 | 1.825 (2) | C49—C50 | 1.379 (4) |
O10—C33 | 1.364 (3) | C49—H49A | 0.9300 |
O10—C34 | 1.432 (4) | C50—H50A | 0.9300 |
O11—C35 | 1.347 (3) | C51—C56 | 1.360 (3) |
O11—C36 | 1.438 (3) | C51—C52 | 1.361 (4) |
O12—C39 | 1.341 (3) | C52—C53 | 1.366 (4) |
O12—C40 | 1.429 (3) | C52—H52A | 0.9300 |
O13—C41 | 1.362 (3) | C53—C54 | 1.352 (4) |
O13—C42 | 1.438 (4) | C53—H53A | 0.9300 |
N1—C35 | 1.318 (3) | C54—C55 | 1.336 (5) |
N1—C33 | 1.324 (4) | C54—H54A | 0.9300 |
N2—C41 | 1.317 (3) | C55—C56 | 1.371 (4) |
N2—C39 | 1.321 (3) | C55—H55A | 0.9300 |
C19—C24 | 1.372 (4) | C56—H56A | 0.9300 |
C19—C20 | 1.380 (4) | C57—Cl2 | 1.664 (7) |
C20—C21 | 1.375 (5) | C57—Cl3 | 1.670 (7) |
C20—H20A | 0.9300 | C57—Cl1 | 1.702 (6) |
C21—C22 | 1.364 (5) | C57—H57 | 0.9800 |
C7—O2—C8 | 118.8 (2) | C28—C27—H27A | 119.9 |
C9—O4—H4 | 116.5 | C26—C27—H27A | 119.9 |
C11—O6—H6 | 109.5 | C27—C28—C29 | 120.6 (3) |
C12—O7—C10 | 117.9 (2) | C27—C28—H28A | 119.7 |
C2—C1—C6 | 120.1 (4) | C29—C28—H28A | 119.7 |
C2—C1—H1A | 120.0 | C30—C29—C28 | 119.2 (3) |
C6—C1—H1A | 120.0 | C30—C29—H29A | 120.4 |
C3—C2—C1 | 119.7 (4) | C28—C29—H29A | 120.4 |
C3—C2—H2A | 120.1 | C29—C30—C25 | 120.9 (3) |
C1—C2—H2A | 120.1 | C29—C30—H30A | 119.6 |
C2—C3—C4 | 121.3 (4) | C25—C30—H30A | 119.6 |
C2—C3—H3A | 119.4 | C37—C31—C32 | 119.8 (2) |
C4—C3—H3A | 119.4 | C37—C31—P1 | 122.75 (17) |
C3—C4—C5 | 119.6 (4) | C32—C31—P1 | 117.2 (2) |
C3—C4—H4A | 120.2 | C33—C32—C31 | 117.4 (3) |
C5—C4—H4A | 120.2 | C33—C32—H32A | 121.3 |
C6—C5—C4 | 120.2 (4) | C31—C32—H32A | 121.3 |
C6—C5—H5A | 119.9 | N1—C33—O10 | 119.5 (3) |
C4—C5—H5A | 119.9 | N1—C33—C32 | 124.4 (2) |
C5—C6—C1 | 119.0 (3) | O10—C33—C32 | 116.1 (3) |
C5—C6—C7 | 122.6 (3) | O10—C34—H34A | 109.5 |
C1—C6—C7 | 118.3 (3) | O10—C34—H34B | 109.5 |
O1—C7—O2 | 123.0 (3) | H34A—C34—H34B | 109.5 |
O1—C7—C6 | 126.5 (3) | O10—C34—H34C | 109.5 |
O2—C7—C6 | 110.4 (3) | H34A—C34—H34C | 109.5 |
O2—C8—C10 | 105.86 (19) | H34B—C34—H34C | 109.5 |
O2—C8—C9 | 111.0 (2) | N1—C35—O11 | 119.1 (2) |
C10—C8—C9 | 110.5 (2) | N1—C35—C37 | 124.7 (2) |
O2—C8—H8A | 109.8 | O11—C35—C37 | 116.1 (2) |
C10—C8—H8A | 109.8 | O11—C36—H36A | 109.5 |
C9—C8—H8A | 109.8 | O11—C36—H36B | 109.5 |
O3—C9—O4 | 127.3 (2) | H36A—C36—H36B | 109.5 |
O3—C9—C8 | 123.7 (2) | O11—C36—H36C | 109.5 |
O4—C9—C8 | 109.0 (2) | H36A—C36—H36C | 109.5 |
O7—C10—C8 | 106.22 (18) | H36B—C36—H36C | 109.5 |
O7—C10—C11 | 110.8 (2) | C31—C37—C35 | 116.3 (2) |
C8—C10—C11 | 111.2 (2) | C31—C37—C38 | 122.54 (19) |
O7—C10—H10A | 109.5 | C35—C37—C38 | 121.0 (2) |
C8—C10—H10A | 109.5 | C44—C38—C39 | 116.4 (2) |
C11—C10—H10A | 109.5 | C44—C38—C37 | 124.52 (19) |
O5—C11—O6 | 126.4 (2) | C39—C38—C37 | 118.9 (2) |
O5—C11—C10 | 124.3 (2) | N2—C39—O12 | 118.9 (2) |
O6—C11—C10 | 109.3 (2) | N2—C39—C38 | 124.4 (2) |
O8—C12—O7 | 121.3 (3) | O12—C39—C38 | 116.7 (2) |
O8—C12—C13 | 125.6 (3) | O12—C40—H40A | 109.5 |
O7—C12—C13 | 113.1 (2) | O12—C40—H40B | 109.5 |
C18—C13—C14 | 118.0 (3) | H40A—C40—H40B | 109.5 |
C18—C13—C12 | 120.6 (3) | O12—C40—H40C | 109.5 |
C14—C13—C12 | 121.3 (3) | H40A—C40—H40C | 109.5 |
C15—C14—C13 | 119.8 (3) | H40B—C40—H40C | 109.5 |
C15—C14—H14A | 120.1 | N2—C41—O13 | 119.3 (2) |
C13—C14—H14A | 120.1 | N2—C41—C43 | 124.1 (2) |
C16—C15—C14 | 120.6 (4) | O13—C41—C43 | 116.5 (2) |
C16—C15—H15A | 119.7 | O13—C42—H42A | 109.5 |
C14—C15—H15A | 119.7 | O13—C42—H42B | 109.5 |
C17—C16—C15 | 120.7 (3) | H42A—C42—H42B | 109.5 |
C17—C16—H16A | 119.6 | O13—C42—H42C | 109.5 |
C15—C16—H16A | 119.6 | H42A—C42—H42C | 109.5 |
C16—C17—C18 | 120.2 (3) | H42B—C42—H42C | 109.5 |
C16—C17—H17A | 119.9 | C41—C43—C44 | 117.6 (2) |
C18—C17—H17A | 119.9 | C41—C43—H43A | 121.2 |
C13—C18—C17 | 120.6 (3) | C44—C43—H43A | 121.2 |
C13—C18—H18A | 119.7 | C38—C44—C43 | 119.7 (2) |
C17—C18—H18A | 119.7 | C38—C44—P2 | 121.19 (16) |
O9—P1—C19 | 110.67 (11) | C43—C44—P2 | 119.10 (18) |
O9—P1—C25 | 111.44 (11) | C50—C45—C46 | 116.3 (3) |
C19—P1—C25 | 107.70 (13) | C50—C45—P2 | 126.0 (2) |
O9—P1—C31 | 113.93 (11) | C46—C45—P2 | 117.3 (2) |
C19—P1—C31 | 106.04 (12) | C47—C46—C45 | 120.3 (3) |
C25—P1—C31 | 106.70 (11) | C47—C46—H46A | 119.8 |
O14—P2—C45 | 110.81 (11) | C45—C46—H46A | 119.8 |
O14—P2—C51 | 113.54 (11) | C48—C47—C46 | 122.4 (4) |
C45—P2—C51 | 106.19 (12) | C48—C47—H47A | 118.8 |
O14—P2—C44 | 111.80 (10) | C46—C47—H47A | 118.8 |
C45—P2—C44 | 107.62 (11) | C49—C48—C47 | 118.0 (4) |
C51—P2—C44 | 106.52 (11) | C49—C48—H48A | 121.0 |
C33—O10—C34 | 116.5 (3) | C47—C48—H48A | 121.0 |
C35—O11—C36 | 117.4 (2) | C48—C49—C50 | 120.1 (4) |
C39—O12—C40 | 117.4 (2) | C48—C49—H49A | 119.9 |
C41—O13—C42 | 116.7 (3) | C50—C49—H49A | 119.9 |
C35—N1—C33 | 117.2 (2) | C45—C50—C49 | 122.6 (4) |
C41—N2—C39 | 117.6 (2) | C45—C50—H50A | 118.7 |
C24—C19—C20 | 118.2 (3) | C49—C50—H50A | 118.7 |
C24—C19—P1 | 124.8 (2) | C56—C51—C52 | 117.2 (3) |
C20—C19—P1 | 116.8 (2) | C56—C51—P2 | 117.9 (2) |
C21—C20—C19 | 120.8 (4) | C52—C51—P2 | 124.8 (2) |
C21—C20—H20A | 119.6 | C51—C52—C53 | 121.4 (3) |
C19—C20—H20A | 119.6 | C51—C52—H52A | 119.3 |
C22—C21—C20 | 119.0 (4) | C53—C52—H52A | 119.3 |
C22—C21—H21A | 120.5 | C54—C53—C52 | 120.4 (3) |
C20—C21—H21A | 120.5 | C54—C53—H53A | 119.8 |
C23—C22—C21 | 122.1 (4) | C52—C53—H53A | 119.8 |
C23—C22—H22A | 119.0 | C55—C54—C53 | 118.9 (3) |
C21—C22—H22A | 119.0 | C55—C54—H54A | 120.6 |
C22—C23—C24 | 118.3 (4) | C53—C54—H54A | 120.6 |
C22—C23—H23A | 120.9 | C54—C55—C56 | 121.1 (3) |
C24—C23—H23A | 120.9 | C54—C55—H55A | 119.5 |
C19—C24—C23 | 121.7 (4) | C56—C55—H55A | 119.5 |
C19—C24—H24A | 119.2 | C51—C56—C55 | 121.0 (3) |
C23—C24—H24A | 119.2 | C51—C56—H56A | 119.5 |
C26—C25—C30 | 118.5 (3) | C55—C56—H56A | 119.5 |
C26—C25—P1 | 125.1 (2) | Cl2—C57—Cl3 | 113.1 (5) |
C30—C25—P1 | 116.5 (2) | Cl2—C57—Cl1 | 113.1 (4) |
C25—C26—C27 | 120.7 (3) | Cl3—C57—Cl1 | 111.1 (4) |
C25—C26—H26A | 119.7 | Cl2—C57—H57 | 106.3 |
C27—C26—H26A | 119.7 | Cl3—C57—H57 | 106.3 |
C28—C27—C26 | 120.2 (3) | Cl1—C57—H57 | 106.3 |
C6—C1—C2—C3 | −2.6 (6) | C37—C31—C32—C33 | 2.3 (4) |
C1—C2—C3—C4 | 2.6 (7) | P1—C31—C32—C33 | −171.8 (2) |
C2—C3—C4—C5 | −1.3 (7) | C35—N1—C33—O10 | −176.9 (3) |
C3—C4—C5—C6 | −0.1 (6) | C35—N1—C33—C32 | 3.9 (4) |
C4—C5—C6—C1 | 0.1 (5) | C34—O10—C33—N1 | 9.1 (5) |
C4—C5—C6—C7 | −176.1 (3) | C34—O10—C33—C32 | −171.6 (3) |
C2—C1—C6—C5 | 1.2 (5) | C31—C32—C33—N1 | −5.1 (5) |
C2—C1—C6—C7 | 177.6 (3) | C31—C32—C33—O10 | 175.7 (3) |
C8—O2—C7—O1 | −5.2 (4) | C33—N1—C35—O11 | 179.3 (2) |
C8—O2—C7—C6 | 172.09 (19) | C33—N1—C35—C37 | 0.2 (4) |
C5—C6—C7—O1 | 174.9 (3) | C36—O11—C35—N1 | −5.6 (4) |
C1—C6—C7—O1 | −1.3 (4) | C36—O11—C35—C37 | 173.5 (3) |
C5—C6—C7—O2 | −2.3 (4) | C32—C31—C37—C35 | 1.3 (3) |
C1—C6—C7—O2 | −178.5 (2) | P1—C31—C37—C35 | 175.00 (17) |
C7—O2—C8—C10 | −151.6 (2) | C32—C31—C37—C38 | −175.2 (2) |
C7—O2—C8—C9 | 88.5 (3) | P1—C31—C37—C38 | −1.5 (3) |
O2—C8—C9—O3 | −4.1 (4) | N1—C35—C37—C31 | −2.6 (4) |
C10—C8—C9—O3 | −121.2 (3) | O11—C35—C37—C31 | 178.2 (2) |
O2—C8—C9—O4 | 176.0 (2) | N1—C35—C37—C38 | 173.9 (2) |
C10—C8—C9—O4 | 58.9 (3) | O11—C35—C37—C38 | −5.2 (3) |
C12—O7—C10—C8 | −161.6 (2) | C31—C37—C38—C44 | 99.0 (3) |
C12—O7—C10—C11 | 77.5 (3) | C35—C37—C38—C44 | −77.3 (3) |
O2—C8—C10—O7 | −68.3 (2) | C31—C37—C38—C39 | −75.4 (3) |
C9—C8—C10—O7 | 51.9 (3) | C35—C37—C38—C39 | 108.3 (2) |
O2—C8—C10—C11 | 52.3 (2) | C41—N2—C39—O12 | −177.3 (2) |
C9—C8—C10—C11 | 172.5 (2) | C41—N2—C39—C38 | 3.0 (3) |
O7—C10—C11—O5 | 4.3 (4) | C40—O12—C39—N2 | −4.6 (3) |
C8—C10—C11—O5 | −113.7 (3) | C40—O12—C39—C38 | 175.2 (2) |
O7—C10—C11—O6 | −177.0 (2) | C44—C38—C39—N2 | −5.3 (3) |
C8—C10—C11—O6 | 65.1 (3) | C37—C38—C39—N2 | 169.6 (2) |
C10—O7—C12—O8 | −4.4 (4) | C44—C38—C39—O12 | 174.9 (2) |
C10—O7—C12—C13 | 175.4 (2) | C37—C38—C39—O12 | −10.2 (3) |
O8—C12—C13—C18 | −6.7 (5) | C39—N2—C41—O13 | −177.6 (2) |
O7—C12—C13—C18 | 173.5 (3) | C39—N2—C41—C43 | 1.3 (4) |
O8—C12—C13—C14 | 173.2 (3) | C42—O13—C41—N2 | 7.6 (4) |
O7—C12—C13—C14 | −6.6 (4) | C42—O13—C41—C43 | −171.4 (3) |
C18—C13—C14—C15 | 0.0 (4) | N2—C41—C43—C44 | −2.9 (4) |
C12—C13—C14—C15 | −179.8 (3) | O13—C41—C43—C44 | 176.1 (2) |
C13—C14—C15—C16 | −0.6 (5) | C39—C38—C44—C43 | 3.5 (3) |
C14—C15—C16—C17 | −0.7 (6) | C37—C38—C44—C43 | −171.1 (2) |
C15—C16—C17—C18 | 2.5 (6) | C39—C38—C44—P2 | −174.83 (16) |
C14—C13—C18—C17 | 1.8 (5) | C37—C38—C44—P2 | 10.6 (3) |
C12—C13—C18—C17 | −178.3 (3) | C41—C43—C44—C38 | 0.2 (4) |
C16—C17—C18—C13 | −3.1 (6) | C41—C43—C44—P2 | 178.6 (2) |
O9—P1—C19—C24 | −122.5 (3) | O14—P2—C44—C38 | −28.3 (2) |
C25—P1—C19—C24 | −0.5 (3) | C45—P2—C44—C38 | −150.20 (19) |
C31—P1—C19—C24 | 113.5 (3) | C51—P2—C44—C38 | 96.3 (2) |
O9—P1—C19—C20 | 51.6 (3) | O14—P2—C44—C43 | 153.41 (19) |
C25—P1—C19—C20 | 173.6 (3) | C45—P2—C44—C43 | 31.5 (2) |
C31—P1—C19—C20 | −72.5 (3) | C51—P2—C44—C43 | −82.0 (2) |
C24—C19—C20—C21 | 0.2 (7) | O14—P2—C45—C50 | 139.9 (3) |
P1—C19—C20—C21 | −174.3 (4) | C51—P2—C45—C50 | 16.2 (3) |
C19—C20—C21—C22 | −1.4 (8) | C44—P2—C45—C50 | −97.6 (3) |
C20—C21—C22—C23 | 1.8 (9) | O14—P2—C45—C46 | −32.6 (3) |
C21—C22—C23—C24 | −0.9 (7) | C51—P2—C45—C46 | −156.3 (3) |
C20—C19—C24—C23 | 0.8 (5) | C44—P2—C45—C46 | 89.9 (3) |
P1—C19—C24—C23 | 174.8 (3) | C50—C45—C46—C47 | 5.8 (7) |
C22—C23—C24—C19 | −0.4 (6) | P2—C45—C46—C47 | 179.0 (4) |
O9—P1—C25—C26 | −151.8 (2) | C45—C46—C47—C48 | −7.1 (9) |
C19—P1—C25—C26 | 86.6 (3) | C46—C47—C48—C49 | 5.2 (9) |
C31—P1—C25—C26 | −26.9 (3) | C47—C48—C49—C50 | −2.4 (7) |
O9—P1—C25—C30 | 28.3 (3) | C46—C45—C50—C49 | −3.2 (6) |
C19—P1—C25—C30 | −93.3 (3) | P2—C45—C50—C49 | −175.8 (3) |
C31—P1—C25—C30 | 153.2 (2) | C48—C49—C50—C45 | 1.6 (7) |
C30—C25—C26—C27 | 1.8 (5) | O14—P2—C51—C56 | −44.4 (3) |
P1—C25—C26—C27 | −178.1 (2) | C45—P2—C51—C56 | 77.6 (3) |
C25—C26—C27—C28 | −0.3 (5) | C44—P2—C51—C56 | −167.9 (3) |
C26—C27—C28—C29 | −1.8 (6) | O14—P2—C51—C52 | 134.4 (3) |
C27—C28—C29—C30 | 2.3 (6) | C45—P2—C51—C52 | −103.6 (3) |
C28—C29—C30—C25 | −0.8 (6) | C44—P2—C51—C52 | 10.9 (3) |
C26—C25—C30—C29 | −1.2 (5) | C56—C51—C52—C53 | 0.5 (6) |
P1—C25—C30—C29 | 178.7 (3) | P2—C51—C52—C53 | −178.3 (3) |
O9—P1—C31—C37 | 26.6 (2) | C51—C52—C53—C54 | −2.8 (7) |
C19—P1—C31—C37 | 148.6 (2) | C52—C53—C54—C55 | 3.6 (8) |
C25—P1—C31—C37 | −96.8 (2) | C53—C54—C55—C56 | −2.3 (9) |
O9—P1—C31—C32 | −159.48 (19) | C52—C51—C56—C55 | 0.9 (7) |
C19—P1—C31—C32 | −37.5 (2) | P2—C51—C56—C55 | 179.8 (4) |
C25—P1—C31—C32 | 77.1 (2) | C54—C55—C56—C51 | 0.1 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O14i | 0.82 | 1.75 | 2.554 (2) | 166 |
O6—H6···O9ii | 0.82 | 1.76 | 2.551 (2) | 162 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x+1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C38H34N2O6P2·C18H14O8·CHCl3 |
Mr | 1154.27 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 294 |
a, b, c (Å) | 10.0967 (10), 21.000 (2), 27.390 (3) |
V (Å3) | 5807.6 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.28 |
Crystal size (mm) | 0.28 × 0.28 × 0.20 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Multi-scans (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.926, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 39041, 13342, 8576 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.147, 1.01 |
No. of reflections | 13342 |
No. of parameters | 725 |
No. of restraints | 80 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.38 |
Absolute structure | Flack (1983), 0000 Friedel pairs |
Absolute structure parameter | 0.05 (8) |
Computer programs: SMART (Siemens, 1995), SMART, SHELXTL (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL).
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O14i | 0.82 | 1.75 | 2.554 (2) | 166 |
O6—H6···O9ii | 0.82 | 1.76 | 2.551 (2) | 162 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x+1/2, −y+3/2, −z+1. |
Transition metal-catalyzed asymmetric hydrogenation reactions are one of the most efficient methods for preparing a wide range of enantiomerically pure compounds. The possibility of discovering catalysts with improved utility, activity and selectivity by designing new ligands plays a crucial role in this research area. Consequently, the number of novel chiral ligands for catalytic asymmetric hydrogenation is growing rapidly. In this context, chiral bisphosphines (e.g. Dipamp, BINAP, DIOP, DuPhos etc.) are among the most useful and versatile ligands (Lin et al., 2001). In contrast to the tremendous success achieved in the use of chiral arylphosphine ligands in the Rh- and Ru-catalyzed asymmetric reactions, chiral phosphine ligands containing heterocyclic moieties, such as pyridyl groups, have been relatively unexplored.
Recently, we have developed a chiral dipyridylphosphine ligand, namely 2,2'6,6'- tetramethoxy-4,4'-bis(diphenylphosphino)-3,3'-bipyridine, (II) (P-Phos; Pai et al., 2000), which was found to be very effective in the Ru-catalyzed asymmetric hydrogenation of 2-(6'-methoxy-2'-naphthyl)propenoic acid and β-ketoesters (Pai et al., 2000).
The key step of synthesis of P-Phos is the optical resolution of racemate (II) with optically active (+)-dibenzoyl-L-tartaric acid [(+)-DBT], (III), as a resolving reagent (Takaya et al., 1988), which is remarkably efficient and highly selective. After several trials with our experimental modifications, the optically pure dipyridylphosphine oxides (R)-(II) and (S)-(II) were obtained in high enantiopurity. Thus, when a solution of (2S,3S)-(+)-DBT in ethyl acetate was added to a boiling solution of racemic (II) in dichloromethane, a 1:1 complex of (-)-(II) and (+)-DBT [(-)–(II)-(+)-DBT, (I)] precipitated as a crystalline solid. From internal comparison with (2S,3S)-(+)-DBT, the absolute configuration of (-)-II was determined to be S.
The crystal structure of (I) (Fig. 1) also contains a disordered chloroform molecule in the lattice. The dihedral angle between the least-squares planes of two pyridyl rings is 75.9(0.1)°. Crystals are built up of infinite chains in which equimolar amounts of (-)-(II) and (+)-DBT are connected in an alternating manner through two intermolecular hydrogen bonds formed between O9 and O14 of the P═O groups of (-)-(II) and H atoms of the COOH groups of (+)-DBT. The O6···O9i and O4···O14ii distances are 2.551 (2) and 2.554 (2) Å, respectively [symmetry codes: (i) 1/2 + x, 3/2 − y, 1 − z; (ii) 1 − x, −1/2 + y, 3/2 − z; Fig. 2 and Table 1]. The low solubility of (I) is attributable to the observed polymeric structure.