(S)-2,2'-Bis[bis(3,5-dimethylphenyl)phosphinoyl]-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802001010/ob6106sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802001010/ob6106Isup2.hkl |
CCDC reference: 182616
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.004 Å
- R factor = 0.049
- wR factor = 0.128
- Data-to-parameter ratio = 20.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.55 From the CIF: _reflns_number_total 5134 Count of symmetry unique reflns 2918 Completeness (_total/calc) 175.94% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2216 Fraction of Friedel pairs measured 0.759 Are heavy atom types Z>Si present yes 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.
All reactions were carried out under N2 using Schlenk techniques. (S)-2,2'-Dihydroxy-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (0.30 g, 1.0 mmol) and 4-N,N-dimethylaminopyridine (15 mg) were added in a 50 ml round-bottomed Schlenk flask with a stir bar. The atmosphere was replaced with N2 several times, and 0.8 ml dry Et3N and 30 ml dry Et2O were added. The mixture cooled to 273 K with ice-bath, followed by dropping in bis(3,5-dimethylphenyl)phosphine chloride (0.6 ml, 2.5 mmol) within 20 min. The solvent was removed under vacuum after stirring at room temperature for another 3 h. The residues were dissolved in 15 ml toluene and purified with flash silica-gel column (30 ml toluene as eluent). Toluene was removed and 670 mg white solid obtained (yield: 87%). Colorless crystals suitable for X-ray diffraction were obtained by recrystallization of a solution in Et2O/CH2Cl2 (5:1). 31P NMR (CDCl3): δ 109.7. 13C NMR (CDCl3): δ 21.39, 21.48, 23.22, 23.30, 27.80, 29.76, 115.28, 115.41, 127.36, 127.54, 127.65, 127.84, 129.09, 130.85, 131.01, 131.33, 137.03, 137.59, 142.11, 142.26. 1H NMR (500 MHz, CDCl3): δ 1.52–1.68 (m, 8H), 2.21 (s, 12H), 2.19 (s, 12H), 2.14–2.23 (m, 2H), 2.38–2.42 (m, 2H), 2.60–2.64 (m, 2H), 2.69–2.75 (m, 2H).
Data collection: SMART (Bruker, 1995); cell refinement: SMART; data reduction: SHELXTL-NT (Bruker, 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.
C52H56O2P2 | Dx = 1.159 Mg m−3 |
Mr = 774.91 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P21212 | Cell parameters from 5442 reflections |
a = 13.1983 (18) Å | θ = 1–27.5° |
b = 19.015 (3) Å | µ = 0.14 mm−1 |
c = 8.8486 (12) Å | T = 294 K |
V = 2220.7 (5) Å3 | Block, colorless |
Z = 2 | 0.34 × 0.28 × 0.26 mm |
F(000) = 828 |
Bruker CCD area-detector diffractometer | 5134 independent reflections |
Radiation source: fine-focus sealed tube | 3079 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ϕ and ω scans | θmax = 27.6°, θmin = 1.9° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −17→11 |
Tmin = 0.955, Tmax = 0.965 | k = −24→24 |
15328 measured reflections | l = −11→11 |
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)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.128 | w = 1/[σ2(Fo2) + (0.0656P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.93 | (Δ/σ)max < 0.001 |
5134 reflections | Δρmax = 0.27 e Å−3 |
253 parameters | Δρmin = −0.28 e Å−3 |
3 restraints | Absolute structure: Flack (1983), 2216 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (12) |
C52H56O2P2 | V = 2220.7 (5) Å3 |
Mr = 774.91 | Z = 2 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 13.1983 (18) Å | µ = 0.14 mm−1 |
b = 19.015 (3) Å | T = 294 K |
c = 8.8486 (12) Å | 0.34 × 0.28 × 0.26 mm |
Bruker CCD area-detector diffractometer | 5134 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 3079 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.965 | Rint = 0.045 |
15328 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.128 | Δρmax = 0.27 e Å−3 |
S = 0.93 | Δρmin = −0.28 e Å−3 |
5134 reflections | Absolute structure: Flack (1983), 2216 Friedel pairs |
253 parameters | Absolute structure parameter: −0.03 (12) |
3 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. The crystal structure of the compound was determined by the direct method (or Patterson function) which yielded the positions of part of non-hydrogen atoms and subsequent difference Fourier syntheses were employed to locate all of the remaining non-hydrogen atoms which did not show up in the initial structure. Hydrogen atoms were located basing on Difference Fourier Syntheses connecting geometrical analysis. All of non-hydrogen atoms were refined anisotropically. All of hydrogen atoms were refined with fixed individual displacement parameters. All experiment and computation were performed on a Bruker CCD Area Detector Diffractomrter and PC computer with program of Bruker Smart and Bruker SHELXTL packages. 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 | ||
P1 | 0.25399 (5) | 0.04515 (3) | 0.63295 (8) | 0.04504 (19) | |
O1 | 0.37731 (12) | 0.03915 (9) | 0.6105 (2) | 0.0479 (5) | |
C1 | 0.44142 (18) | 0.07676 (13) | 0.7069 (3) | 0.0388 (6) | |
C2 | 0.50291 (17) | 0.03932 (12) | 0.8033 (3) | 0.0357 (6) | |
C3 | 0.57059 (17) | 0.07564 (13) | 0.8971 (3) | 0.0395 (6) | |
C4 | 0.57599 (19) | 0.14848 (13) | 0.8897 (3) | 0.0452 (7) | |
C5 | 0.5118 (2) | 0.18387 (14) | 0.7915 (4) | 0.0551 (8) | |
H5A | 0.5142 | 0.2327 | 0.7880 | 0.066* | |
C6 | 0.4453 (2) | 0.14923 (14) | 0.7000 (4) | 0.0551 (8) | |
H6A | 0.4034 | 0.1740 | 0.6343 | 0.066* | |
C7 | 0.6382 (2) | 0.03482 (14) | 1.0038 (3) | 0.0531 (8) | |
H7A | 0.5972 | 0.0008 | 1.0580 | 0.064* | |
H7B | 0.6877 | 0.0090 | 0.9449 | 0.064* | |
C8 | 0.6920 (3) | 0.07922 (18) | 1.1146 (5) | 0.0989 (14) | |
H8A | 0.6475 | 0.0870 | 1.2002 | 0.119* | |
H8B | 0.7504 | 0.0533 | 1.1511 | 0.119* | |
C9 | 0.7263 (3) | 0.14666 (16) | 1.0607 (5) | 0.1041 (15) | |
H9A | 0.7535 | 0.1728 | 1.1456 | 0.125* | |
H9B | 0.7812 | 0.1391 | 0.9897 | 0.125* | |
C10 | 0.6488 (2) | 0.18970 (14) | 0.9872 (4) | 0.0638 (9) | |
H10A | 0.6820 | 0.2248 | 0.9250 | 0.077* | |
H10B | 0.6105 | 0.2143 | 1.0644 | 0.077* | |
C11 | 0.22009 (19) | −0.04828 (14) | 0.6221 (3) | 0.0469 (6) | |
C12 | 0.2805 (2) | −0.09767 (14) | 0.5532 (3) | 0.0517 (7) | |
H12A | 0.3411 | −0.0839 | 0.5087 | 0.062* | |
C13 | 0.2518 (3) | −0.16836 (14) | 0.5493 (3) | 0.0603 (8) | |
C14 | 0.1611 (3) | −0.18645 (16) | 0.6172 (4) | 0.0699 (10) | |
H14A | 0.1411 | −0.2333 | 0.6151 | 0.084* | |
C15 | 0.0987 (2) | −0.13820 (18) | 0.6881 (4) | 0.0643 (9) | |
C16 | 0.1307 (2) | −0.06902 (16) | 0.6912 (3) | 0.0565 (8) | |
H16A | 0.0913 | −0.0356 | 0.7408 | 0.068* | |
C17 | 0.3180 (3) | −0.22299 (16) | 0.4754 (5) | 0.0879 (12) | |
H17A | 0.2862 | −0.2682 | 0.4833 | 0.132* | |
H17B | 0.3826 | −0.2242 | 0.5251 | 0.132* | |
H17C | 0.3273 | −0.2113 | 0.3708 | 0.132* | |
C18 | 0.0027 (3) | −0.1618 (2) | 0.7629 (5) | 0.1041 (14) | |
H18A | −0.0060 | −0.2114 | 0.7477 | 0.156* | |
H18B | −0.0537 | −0.1370 | 0.7199 | 0.156* | |
H18C | 0.0064 | −0.1521 | 0.8693 | 0.156* | |
C19 | 0.21828 (19) | 0.07338 (12) | 0.4439 (3) | 0.0438 (7) | |
C20 | 0.1160 (2) | 0.07499 (14) | 0.4076 (3) | 0.0532 (8) | |
H20A | 0.0688 | 0.0594 | 0.4782 | 0.064* | |
C21 | 0.0828 (2) | 0.09904 (15) | 0.2698 (4) | 0.0612 (9) | |
C22 | 0.1542 (2) | 0.12326 (14) | 0.1666 (4) | 0.0613 (9) | |
H22A | 0.1326 | 0.1392 | 0.0726 | 0.074* | |
C23 | 0.2572 (2) | 0.12426 (13) | 0.2001 (3) | 0.0537 (7) | |
C24 | 0.2871 (2) | 0.09915 (13) | 0.3400 (3) | 0.0471 (7) | |
H24A | 0.3556 | 0.0996 | 0.3648 | 0.057* | |
C25 | −0.0300 (2) | 0.1007 (2) | 0.2327 (5) | 0.0970 (14) | |
H25A | −0.0677 | 0.0819 | 0.3162 | 0.146* | |
H25B | −0.0426 | 0.0728 | 0.1442 | 0.146* | |
H25C | −0.0507 | 0.1483 | 0.2145 | 0.146* | |
C26 | 0.3327 (3) | 0.15355 (16) | 0.0901 (4) | 0.0719 (10) | |
H26A | 0.3997 | 0.1495 | 0.1316 | 0.108* | |
H26B | 0.3177 | 0.2022 | 0.0712 | 0.108* | |
H26C | 0.3291 | 0.1277 | −0.0030 | 0.108* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0420 (4) | 0.0433 (3) | 0.0498 (4) | 0.0021 (4) | −0.0049 (4) | 0.0002 (3) |
O1 | 0.0413 (9) | 0.0471 (10) | 0.0554 (12) | 0.0041 (9) | −0.0095 (9) | −0.0049 (10) |
C1 | 0.0364 (13) | 0.0346 (13) | 0.0454 (16) | −0.0021 (11) | −0.0025 (12) | −0.0012 (12) |
C2 | 0.0340 (13) | 0.0309 (12) | 0.0423 (14) | −0.0009 (11) | 0.0028 (11) | −0.0006 (11) |
C3 | 0.0340 (13) | 0.0385 (13) | 0.0461 (16) | −0.0026 (11) | 0.0027 (12) | −0.0028 (12) |
C4 | 0.0400 (14) | 0.0371 (14) | 0.0586 (18) | −0.0027 (12) | 0.0067 (14) | −0.0063 (14) |
C5 | 0.0606 (19) | 0.0305 (14) | 0.074 (2) | −0.0027 (14) | −0.0019 (17) | −0.0033 (14) |
C6 | 0.0556 (18) | 0.0422 (16) | 0.068 (2) | 0.0070 (14) | −0.0066 (16) | 0.0076 (15) |
C7 | 0.0494 (17) | 0.0507 (16) | 0.059 (2) | −0.0009 (14) | −0.0105 (15) | −0.0018 (14) |
C8 | 0.110 (3) | 0.084 (2) | 0.103 (3) | −0.023 (2) | −0.062 (3) | 0.007 (2) |
C9 | 0.093 (3) | 0.073 (2) | 0.146 (4) | −0.002 (2) | −0.059 (3) | −0.036 (3) |
C10 | 0.059 (2) | 0.0508 (17) | 0.082 (3) | −0.0116 (16) | −0.0077 (18) | −0.0160 (17) |
C11 | 0.0459 (14) | 0.0498 (14) | 0.0448 (15) | −0.0048 (13) | −0.0101 (12) | 0.0092 (15) |
C12 | 0.0565 (19) | 0.0470 (16) | 0.0516 (17) | −0.0060 (14) | −0.0030 (14) | 0.0024 (14) |
C13 | 0.077 (2) | 0.0453 (15) | 0.0583 (18) | −0.0033 (18) | −0.018 (2) | 0.0002 (14) |
C14 | 0.086 (3) | 0.0542 (19) | 0.069 (2) | −0.0280 (19) | −0.016 (2) | 0.0134 (18) |
C15 | 0.062 (2) | 0.065 (2) | 0.065 (2) | −0.0183 (18) | −0.0073 (17) | 0.0180 (17) |
C16 | 0.0520 (17) | 0.0593 (18) | 0.058 (2) | −0.0034 (15) | −0.0019 (15) | 0.0111 (15) |
C17 | 0.120 (3) | 0.0550 (19) | 0.089 (3) | 0.002 (2) | −0.009 (3) | −0.0100 (19) |
C18 | 0.085 (3) | 0.104 (3) | 0.123 (4) | −0.036 (2) | 0.022 (3) | 0.015 (3) |
C19 | 0.0417 (15) | 0.0309 (12) | 0.0589 (17) | 0.0006 (11) | −0.0051 (13) | 0.0025 (13) |
C20 | 0.0444 (16) | 0.0483 (15) | 0.067 (2) | −0.0081 (13) | −0.0099 (14) | 0.0153 (15) |
C21 | 0.0536 (18) | 0.0512 (17) | 0.079 (2) | −0.0046 (15) | −0.0190 (17) | 0.0127 (17) |
C22 | 0.072 (2) | 0.0481 (17) | 0.063 (2) | −0.0026 (15) | −0.0194 (18) | 0.0115 (15) |
C23 | 0.065 (2) | 0.0373 (14) | 0.0584 (18) | 0.0095 (15) | 0.0057 (17) | 0.0019 (12) |
C24 | 0.0421 (14) | 0.0422 (14) | 0.0570 (19) | 0.0055 (12) | 0.0009 (13) | −0.0004 (14) |
C25 | 0.062 (2) | 0.107 (3) | 0.123 (4) | −0.022 (2) | −0.043 (2) | 0.040 (3) |
C26 | 0.083 (2) | 0.0602 (19) | 0.072 (2) | 0.0107 (18) | 0.015 (2) | 0.0082 (17) |
P1—O1 | 1.6437 (18) | C13—C14 | 1.383 (5) |
P1—C19 | 1.819 (3) | C13—C17 | 1.506 (5) |
P1—C11 | 1.834 (3) | C14—C15 | 1.384 (5) |
O1—C1 | 1.398 (3) | C14—H14A | 0.9300 |
C1—C2 | 1.376 (3) | C15—C16 | 1.382 (4) |
C1—C6 | 1.380 (4) | C15—C18 | 1.498 (5) |
C2—C3 | 1.402 (3) | C16—H16A | 0.9300 |
C2—C2i | 1.497 (4) | C17—H17A | 0.9600 |
C3—C4 | 1.389 (3) | C17—H17B | 0.9600 |
C3—C7 | 1.513 (4) | C17—H17C | 0.9600 |
C4—C5 | 1.387 (4) | C18—H18A | 0.9600 |
C4—C10 | 1.510 (4) | C18—H18B | 0.9600 |
C5—C6 | 1.364 (4) | C18—H18C | 0.9600 |
C5—H5A | 0.9300 | C19—C24 | 1.382 (4) |
C6—H6A | 0.9300 | C19—C20 | 1.388 (4) |
C7—C8 | 1.476 (3) | C20—C21 | 1.374 (4) |
C7—H7A | 0.9700 | C20—H20A | 0.9300 |
C7—H7B | 0.9700 | C21—C22 | 1.391 (5) |
C8—C9 | 1.441 (3) | C21—C25 | 1.524 (4) |
C8—H8A | 0.9700 | C22—C23 | 1.391 (4) |
C8—H8B | 0.9700 | C22—H22A | 0.9300 |
C9—C10 | 1.463 (3) | C23—C24 | 1.384 (4) |
C9—H9A | 0.9700 | C23—C26 | 1.500 (4) |
C9—H9B | 0.9700 | C24—H24A | 0.9300 |
C10—H10A | 0.9700 | C25—H25A | 0.9600 |
C10—H10B | 0.9700 | C25—H25B | 0.9600 |
C11—C12 | 1.374 (4) | C25—H25C | 0.9600 |
C11—C16 | 1.387 (4) | C26—H26A | 0.9600 |
C12—C13 | 1.397 (4) | C26—H26B | 0.9600 |
C12—H12A | 0.9300 | C26—H26C | 0.9600 |
O1—P1—C19 | 99.55 (11) | C14—C13—C17 | 121.2 (3) |
O1—P1—C11 | 99.67 (11) | C12—C13—C17 | 121.2 (3) |
C19—P1—C11 | 100.04 (12) | C15—C14—C13 | 123.2 (3) |
C1—O1—P1 | 119.36 (16) | C15—C14—H14A | 118.4 |
C2—C1—C6 | 121.5 (2) | C13—C14—H14A | 118.4 |
C2—C1—O1 | 118.1 (2) | C16—C15—C14 | 117.3 (3) |
C6—C1—O1 | 120.4 (2) | C16—C15—C18 | 122.3 (4) |
C1—C2—C3 | 119.2 (2) | C14—C15—C18 | 120.4 (3) |
C1—C2—C2i | 119.1 (2) | C15—C16—C11 | 121.5 (3) |
C3—C2—C2i | 121.6 (2) | C15—C16—H16A | 119.3 |
C4—C3—C2 | 119.7 (2) | C11—C16—H16A | 119.3 |
C4—C3—C7 | 120.7 (2) | C13—C17—H17A | 109.5 |
C2—C3—C7 | 119.5 (2) | C13—C17—H17B | 109.5 |
C5—C4—C3 | 118.8 (2) | H17A—C17—H17B | 109.5 |
C5—C4—C10 | 119.6 (2) | C13—C17—H17C | 109.5 |
C3—C4—C10 | 121.6 (3) | H17A—C17—H17C | 109.5 |
C6—C5—C4 | 122.0 (2) | H17B—C17—H17C | 109.5 |
C6—C5—H5A | 119.0 | C15—C18—H18A | 109.5 |
C4—C5—H5A | 119.0 | C15—C18—H18B | 109.5 |
C5—C6—C1 | 118.7 (3) | H18A—C18—H18B | 109.5 |
C5—C6—H6A | 120.7 | C15—C18—H18C | 109.5 |
C1—C6—H6A | 120.7 | H18A—C18—H18C | 109.5 |
C8—C7—C3 | 113.9 (2) | H18B—C18—H18C | 109.5 |
C8—C7—H7A | 108.8 | C24—C19—C20 | 118.5 (3) |
C3—C7—H7A | 108.8 | C24—C19—P1 | 123.1 (2) |
C8—C7—H7B | 108.8 | C20—C19—P1 | 118.1 (2) |
C3—C7—H7B | 108.8 | C21—C20—C19 | 121.5 (3) |
H7A—C7—H7B | 107.7 | C21—C20—H20A | 119.2 |
C9—C8—C7 | 116.1 (3) | C19—C20—H20A | 119.2 |
C9—C8—H8A | 108.3 | C20—C21—C22 | 118.5 (3) |
C7—C8—H8A | 108.3 | C20—C21—C25 | 120.6 (3) |
C9—C8—H8B | 108.3 | C22—C21—C25 | 120.9 (3) |
C7—C8—H8B | 108.3 | C21—C22—C23 | 121.8 (3) |
H8A—C8—H8B | 107.4 | C21—C22—H22A | 119.1 |
C10—C9—C8 | 115.2 (3) | C23—C22—H22A | 119.1 |
C10—C9—H9A | 108.5 | C24—C23—C22 | 117.7 (3) |
C8—C9—H9A | 108.5 | C24—C23—C26 | 121.3 (3) |
C10—C9—H9B | 108.5 | C22—C23—C26 | 121.0 (3) |
C8—C9—H9B | 108.5 | C19—C24—C23 | 122.0 (3) |
H9A—C9—H9B | 107.5 | C19—C24—H24A | 119.0 |
C9—C10—C4 | 114.1 (2) | C23—C24—H24A | 119.0 |
C9—C10—H10A | 108.7 | C21—C25—H25A | 109.5 |
C4—C10—H10A | 108.7 | C21—C25—H25B | 109.5 |
C9—C10—H10B | 108.7 | H25A—C25—H25B | 109.5 |
C4—C10—H10B | 108.7 | C21—C25—H25C | 109.5 |
H10A—C10—H10B | 107.6 | H25A—C25—H25C | 109.5 |
C12—C11—C16 | 119.7 (3) | H25B—C25—H25C | 109.5 |
C12—C11—P1 | 122.9 (2) | C23—C26—H26A | 109.5 |
C16—C11—P1 | 117.4 (2) | C23—C26—H26B | 109.5 |
C11—C12—C13 | 120.8 (3) | H26A—C26—H26B | 109.5 |
C11—C12—H12A | 119.6 | C23—C26—H26C | 109.5 |
C13—C12—H12A | 119.6 | H26A—C26—H26C | 109.5 |
C14—C13—C12 | 117.6 (3) | H26B—C26—H26C | 109.5 |
C19—P1—O1—C1 | 124.38 (19) | O1—P1—C11—C16 | 155.9 (2) |
C11—P1—O1—C1 | −133.61 (19) | C19—P1—C11—C16 | −102.5 (2) |
P1—O1—C1—C2 | 114.1 (2) | C16—C11—C12—C13 | 1.3 (4) |
P1—O1—C1—C6 | −68.5 (3) | P1—C11—C12—C13 | 179.3 (2) |
C6—C1—C2—C3 | 0.4 (4) | C11—C12—C13—C14 | −0.1 (4) |
O1—C1—C2—C3 | 177.7 (2) | C11—C12—C13—C17 | −179.4 (3) |
C6—C1—C2—C2i | −178.6 (2) | C12—C13—C14—C15 | −0.2 (5) |
O1—C1—C2—C2i | −1.3 (3) | C17—C13—C14—C15 | 179.1 (3) |
C1—C2—C3—C4 | −1.2 (4) | C13—C14—C15—C16 | −0.7 (5) |
C2i—C2—C3—C4 | 177.8 (2) | C13—C14—C15—C18 | −178.3 (3) |
C1—C2—C3—C7 | 179.8 (2) | C14—C15—C16—C11 | 2.0 (5) |
C2i—C2—C3—C7 | −1.3 (3) | C18—C15—C16—C11 | 179.6 (3) |
C2—C3—C4—C5 | 1.7 (4) | C12—C11—C16—C15 | −2.3 (4) |
C7—C3—C4—C5 | −179.3 (3) | P1—C11—C16—C15 | 179.6 (2) |
C2—C3—C4—C10 | −179.2 (3) | O1—P1—C19—C24 | −15.2 (2) |
C7—C3—C4—C10 | −0.1 (4) | C11—P1—C19—C24 | −116.9 (2) |
C3—C4—C5—C6 | −1.4 (4) | O1—P1—C19—C20 | 170.8 (2) |
C10—C4—C5—C6 | 179.4 (3) | C11—P1—C19—C20 | 69.1 (2) |
C4—C5—C6—C1 | 0.6 (4) | C24—C19—C20—C21 | 2.4 (4) |
C2—C1—C6—C5 | −0.1 (4) | P1—C19—C20—C21 | 176.7 (2) |
O1—C1—C6—C5 | −177.4 (2) | C19—C20—C21—C22 | −1.1 (5) |
C4—C3—C7—C8 | 11.3 (4) | C19—C20—C21—C25 | −179.7 (3) |
C2—C3—C7—C8 | −169.6 (3) | C20—C21—C22—C23 | −0.6 (5) |
C3—C7—C8—C9 | −36.9 (5) | C25—C21—C22—C23 | 178.0 (3) |
C7—C8—C9—C10 | 52.0 (6) | C21—C22—C23—C24 | 1.0 (4) |
C8—C9—C10—C4 | −38.5 (5) | C21—C22—C23—C26 | −177.2 (3) |
C5—C4—C10—C9 | −167.6 (3) | C20—C19—C24—C23 | −2.0 (4) |
C3—C4—C10—C9 | 13.3 (5) | P1—C19—C24—C23 | −176.03 (19) |
O1—P1—C11—C12 | −22.1 (3) | C22—C23—C24—C19 | 0.4 (4) |
C19—P1—C11—C12 | 79.5 (2) | C26—C23—C24—C19 | 178.6 (3) |
Symmetry code: (i) −x+1, −y, z. |
Experimental details
Crystal data | |
Chemical formula | C52H56O2P2 |
Mr | 774.91 |
Crystal system, space group | Orthorhombic, P21212 |
Temperature (K) | 294 |
a, b, c (Å) | 13.1983 (18), 19.015 (3), 8.8486 (12) |
V (Å3) | 2220.7 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.34 × 0.28 × 0.26 |
Data collection | |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.955, 0.965 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15328, 5134, 3079 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.128, 0.93 |
No. of reflections | 5134 |
No. of parameters | 253 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.28 |
Absolute structure | Flack (1983), 2216 Friedel pairs |
Absolute structure parameter | −0.03 (12) |
Computer programs: SMART (Bruker, 1995), SMART, SHELXTL-NT (Bruker, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-NT.
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The phosphinite ligands exhibit good to excellent enantioselectivity and high reactivity in the hydrogenation of prochiral olefines (Zhang et al., 1998; Chan et al., 1997). The phosphinite (I) can be conveniently obtained by reacting (S)-2,2'-dihydroxy-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (H8-BINOL) with bis(3,5-dimethylphenyl)phosphine chloride. Recent research shows that the phosphinite ligands derived from bis(3,5-dimethylphenyl)phosphine chloride exhibit higher enantioselectivity in the catalytic hydrogenation reaction than that derived from chlorodiphenylphosphine, due to the steric and electronic modulation of the substitute groups on the P atom (Trabesinger et al., 1997; RajanBabu et al., 1997). As part of our efforts investigating this phenomenon, we present the crystal structure of (I).
As shown in Fig. 1, the title molecule has crystallographic twofold rotation symmetry. The lengths of the Csp3—Csp3 bonds C7—C8, C8—C9 and C9—C10 [1.476 (3), 1.441 (3) and 1.463 (3) Å, respectively] are shorter than the normal Csp3—Csp3 bond (1.51–1.55 Å) and differ significantly from the Csp3—Csp2 bonds C3—-C7 and C4–C10 [1.513 (4) and 1.510 (4) Å, respectively] in the H8-naphthyl unit. The disorder is persumed to be due to the puckering of the ring, which is suggested by the high Ueq values of the C8 and C9 atoms.