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
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.005 Å
- Disorder in solvent or counterion
- R factor = 0.053
- wR factor = 0.147
- Data-to-parameter ratio = 18.4
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) . 3.88 Ratio PLAT241_ALERT_2_B Check High U(eq) as Compared to Neighbors .. C47 PLAT242_ALERT_2_B Check Low U(eq) as Compared to Neighbors .. C45 PLAT331_ALERT_2_B Small Av. Phenyl C-C Dist. C51 - C56 = 1.36 Ang.
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ..... ? PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) . 3.01 Ratio PLAT241_ALERT_2_C Check High U(eq) as Compared to Neighbors .. C21 PLAT241_ALERT_2_C Check High U(eq) as Compared to Neighbors .. C55 PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .. C19 PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .. C48 PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .. C51 PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .. C9 PLAT244_ALERT_4_C Low Solvent U(eq) as Compared to Neighbors .. C57 PLAT302_ALERT_4_C Anion/Solvent Disorder ....................... 33.00 Perc. PLAT331_ALERT_2_C Small Av. Phenyl C-C Dist. C1 - C6 = 1.36 Ang. PLAT331_ALERT_2_C Small Av. Phenyl C-C Dist. C45 - C50 = 1.37 Ang. PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang.. 5 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.# 3 C H Cl3
Alert level G ABSTY01_ALERT_1_G Extra text has been found in the _exptl_absorpt_correction_type field, which should be only a single keyword. A literature citation should be included in the _exptl_absorpt_process_details field. REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.50 From the CIF: _reflns_number_total 13342 Count of symmetry unique reflns 7355 Completeness (_total/calc) 181.40% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 5987 Fraction of Friedel pairs measured 0.814 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 15 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 12 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion
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.