Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031479/hb2462sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031479/hb2462Isup2.hkl |
CCDC reference: 657653
To a solution of (R)-3,3'-diphenyl-5,6,7,8,5',6',7',8'-octahydro-[1,1'] binaphthalenyl-2,2'-diol (2 mmol) in pyridine (5 ml) was added phosphorus oxychloride (4.0 mmol) at room temperature under nitrogen. The mixture was stirred at 343 K for 3 h. The solvent was then removed and the product purified by column chromatography on silica gel. Colorless blocks of (I) were obtained by recrystallization from ethanol.
The aliphatic portion of one of the two ten-membered fused rings is disordered over two sites. Its carbon-carbon distances were restrained to within 1.50±0.01 Å, and the Uij values were restrained to nearly isotropic behaviour. As the disorder refined to nearly 50:50, the ratio was fixed as 50:50.
The carbon-bound H-atoms were generated geometrically (C–H 0.93 – 0.97 Å), and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C,O).
The configuration in the studied crystal is the R-enantiomer.
3,3'-Diphenyl-5,6,7,8,5',6',7',8'-octahydro-[1,1']-binaphthalenyl-2,2'-phosphate is a highly enantioselective catalyst (Chen et al., 2006) as is starting reactant 3,3'-diphenyl-5,6,7,8,5',6',7',8'-octahydro-[1,1']-binaphthalenyl-2,2'-diol (McDougal & Schaus, 2003). The reaction of the diol with phosphorus oxychloride has yielded the title chlorophosphate, (I), (Fig. 1) which is also expected to exhibit such activity.
For a report on the enantioselective catalytic property of the related 3,3'-diphenyl-5,6,7,8,5',6',7',8'-octahydro-[1,1']-binaphthalenyl-2,2'-phosphate, see Chen et al. (2006). For a report on the synthesis of the 3,3'-diphenyl-5,6,7,8,5',6',7',8'-octahydro-[1,1']-binaphthalenyl-2,2'-diol reactant, see McDougal & Schaus (2003).
Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006 or??2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).
Fig. 1. View of the molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level (H atoms as spheres of arbitrary radius). The disorder is not shown. |
C32H28ClO3P | F(000) = 1104 |
Mr = 526.96 | Dx = 1.320 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac ab | Cell parameters from 7841 reflections |
a = 12.6642 (8) Å | θ = 2.2–23.6° |
b = 13.1613 (8) Å | µ = 0.24 mm−1 |
c = 15.9097 (9) Å | T = 295 K |
V = 2651.8 (3) Å3 | Block, colorless |
Z = 4 | 0.32 × 0.17 × 0.07 mm |
Bruker APEX CCD diffractometer | 4949 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 27.5°, θmin = 2.2° |
φ and ω scans | h = −16→16 |
33491 measured reflections | k = −17→16 |
6089 independent reflections | l = −20→20 |
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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0547P)2 + 0.1321P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
6089 reflections | Δρmax = 0.16 e Å−3 |
370 parameters | Δρmin = −0.23 e Å−3 |
52 restraints | Absolute structure: Flack (1983), 2674 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.02 (6) |
C32H28ClO3P | V = 2651.8 (3) Å3 |
Mr = 526.96 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 12.6642 (8) Å | µ = 0.24 mm−1 |
b = 13.1613 (8) Å | T = 295 K |
c = 15.9097 (9) Å | 0.32 × 0.17 × 0.07 mm |
Bruker APEX CCD diffractometer | 4949 reflections with I > 2σ(I) |
33491 measured reflections | Rint = 0.032 |
6089 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.099 | Δρmax = 0.16 e Å−3 |
S = 1.03 | Δρmin = −0.23 e Å−3 |
6089 reflections | Absolute structure: Flack (1983), 2674 Friedel pairs |
370 parameters | Absolute structure parameter: 0.02 (6) |
52 restraints |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.69670 (4) | 0.39625 (5) | 0.93762 (4) | 0.06273 (16) | |
P1 | 0.82905 (4) | 0.40064 (4) | 0.87055 (3) | 0.04711 (13) | |
O1 | 0.88918 (10) | 0.30781 (10) | 0.91181 (8) | 0.0459 (3) | |
O2 | 0.89086 (10) | 0.49825 (10) | 0.89966 (8) | 0.0464 (3) | |
O3 | 0.81117 (12) | 0.39828 (14) | 0.78038 (9) | 0.0666 (4) | |
C1 | 0.99403 (18) | 0.15174 (17) | 0.81908 (14) | 0.0541 (5) | |
C2 | 1.0106 (2) | 0.0517 (2) | 0.84163 (17) | 0.0743 (7) | |
H2 | 1.0603 | 0.0361 | 0.8827 | 0.089* | |
C3 | 0.9543 (3) | −0.0251 (2) | 0.8038 (2) | 0.0937 (9) | |
H3 | 0.9651 | −0.0921 | 0.8205 | 0.112* | |
C4 | 0.8838 (3) | −0.0043 (3) | 0.7430 (2) | 0.0931 (10) | |
H4 | 0.8458 | −0.0568 | 0.7181 | 0.112* | |
C5 | 0.8675 (3) | 0.0940 (3) | 0.71751 (18) | 0.0898 (9) | |
H5 | 0.8198 | 0.1078 | 0.6746 | 0.108* | |
C6 | 0.9218 (2) | 0.1723 (2) | 0.75553 (16) | 0.0727 (7) | |
H6 | 0.9100 | 0.2390 | 0.7386 | 0.087* | |
C7 | 1.05299 (14) | 0.37665 (14) | 0.96221 (11) | 0.0398 (4) | |
C8 | 1.00118 (14) | 0.30754 (15) | 0.91088 (11) | 0.0420 (4) | |
C9 | 1.05190 (15) | 0.23363 (15) | 0.86370 (12) | 0.0456 (4) | |
C10 | 1.16196 (16) | 0.23720 (16) | 0.86518 (13) | 0.0497 (5) | |
H10 | 1.1995 | 0.1878 | 0.8360 | 0.060* | |
C11 | 1.21748 (15) | 0.31100 (17) | 0.90821 (12) | 0.0477 (5) | |
C12 | 1.16399 (14) | 0.38174 (15) | 0.95733 (11) | 0.0445 (4) | |
C13 | 1.33695 (16) | 0.3147 (2) | 0.89788 (15) | 0.0648 (6) | |
H13A | 1.3655 | 0.2481 | 0.9108 | 0.078* | |
H13B | 1.3531 | 0.3292 | 0.8395 | 0.078* | |
C14 | 1.39153 (16) | 0.3922 (2) | 0.95210 (17) | 0.0703 (7) | |
H14A | 1.4026 | 0.3639 | 1.0077 | 0.084* | |
H14B | 1.4602 | 0.4075 | 0.9282 | 0.084* | |
C15 | 1.32899 (18) | 0.4890 (2) | 0.95974 (18) | 0.0704 (7) | |
H15A | 1.3185 | 0.5185 | 0.9045 | 0.085* | |
H15B | 1.3677 | 0.5376 | 0.9937 | 0.085* | |
C16 | 1.22350 (17) | 0.46740 (19) | 0.99976 (16) | 0.0612 (6) | |
H16A | 1.1807 | 0.5285 | 0.9978 | 0.073* | |
H16B | 1.2344 | 0.4501 | 1.0584 | 0.073* | |
C17 | 1.0695 (7) | 0.3533 (7) | 1.1426 (6) | 0.050 (2) | 0.50 |
H17A | 1.0431 | 0.2891 | 1.1214 | 0.059* | 0.50 |
H17B | 1.1425 | 0.3604 | 1.1251 | 0.059* | 0.50 |
C18 | 1.0632 (9) | 0.3543 (9) | 1.2377 (6) | 0.126 (5) | 0.50 |
H18A | 1.1287 | 0.3832 | 1.2583 | 0.152* | 0.50 |
H18B | 1.0614 | 0.2841 | 1.2562 | 0.152* | 0.50 |
C19 | 0.9729 (7) | 0.4097 (7) | 1.2819 (5) | 0.092 (2) | 0.50 |
H19A | 0.9066 | 0.3754 | 1.2707 | 0.111* | 0.50 |
H19B | 0.9846 | 0.4098 | 1.3422 | 0.111* | 0.50 |
C20 | 0.9683 (8) | 0.5169 (7) | 1.2499 (5) | 0.068 (3) | 0.50 |
H20A | 1.0353 | 0.5512 | 1.2585 | 0.081* | 0.50 |
H20B | 0.9132 | 0.5550 | 1.2782 | 0.081* | 0.50 |
C17' | 1.0817 (8) | 0.3751 (8) | 1.1556 (6) | 0.067 (3) | 0.50 |
H17C | 1.1062 | 0.3204 | 1.1197 | 0.081* | 0.50 |
H17D | 1.1425 | 0.4161 | 1.1706 | 0.081* | 0.50 |
C18' | 1.0346 (6) | 0.3299 (5) | 1.2351 (4) | 0.0596 (18) | 0.50 |
H18C | 0.9663 | 0.2989 | 1.2249 | 0.072* | 0.50 |
H18D | 1.0814 | 0.2808 | 1.2611 | 0.072* | 0.50 |
C19' | 1.0257 (6) | 0.4258 (5) | 1.2857 (4) | 0.078 (2) | 0.50 |
H19C | 1.0103 | 0.4092 | 1.3438 | 0.094* | 0.50 |
H19D | 1.0922 | 0.4623 | 1.2840 | 0.094* | 0.50 |
C20' | 0.9400 (7) | 0.4909 (8) | 1.2510 (5) | 0.068 (3) | 0.50 |
H20C | 0.9433 | 0.5568 | 1.2781 | 0.081* | 0.50 |
H20D | 0.8725 | 0.4606 | 1.2653 | 0.081* | 0.50 |
C21 | 0.99091 (14) | 0.44335 (15) | 1.01926 (12) | 0.0407 (4) | |
C22 | 0.91440 (14) | 0.50784 (14) | 0.98597 (12) | 0.0424 (4) | |
C23 | 0.85660 (15) | 0.57704 (15) | 1.03315 (14) | 0.0490 (5) | |
C24 | 0.87462 (17) | 0.57417 (18) | 1.11978 (15) | 0.0592 (6) | |
H24 | 0.8384 | 0.6195 | 1.1541 | 0.071* | |
C25 | 0.94419 (17) | 0.50649 (18) | 1.15635 (12) | 0.0585 (6) | |
C26 | 1.00400 (15) | 0.44054 (16) | 1.10670 (12) | 0.0484 (5) | |
C27 | 0.77742 (17) | 0.64701 (16) | 0.99610 (17) | 0.0581 (6) | |
C28 | 0.6822 (2) | 0.6646 (2) | 1.0379 (2) | 0.0778 (8) | |
H28 | 0.6687 | 0.6319 | 1.0886 | 0.093* | |
C29 | 0.6082 (2) | 0.7297 (3) | 1.0048 (3) | 0.1066 (12) | |
H29 | 0.5449 | 0.7405 | 1.0331 | 0.128* | |
C30 | 0.6273 (3) | 0.7787 (3) | 0.9303 (3) | 0.1088 (13) | |
H30 | 0.5763 | 0.8215 | 0.9076 | 0.131* | |
C31 | 0.7210 (3) | 0.7649 (2) | 0.8894 (2) | 0.0928 (10) | |
H31 | 0.7350 | 0.8002 | 0.8399 | 0.111* | |
C32 | 0.7958 (2) | 0.69762 (18) | 0.92191 (18) | 0.0714 (7) | |
H32 | 0.8587 | 0.6869 | 0.8931 | 0.086* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0366 (2) | 0.0759 (4) | 0.0756 (3) | 0.0012 (3) | 0.0016 (2) | 0.0015 (3) |
P1 | 0.0374 (2) | 0.0571 (3) | 0.0468 (3) | 0.0049 (2) | −0.0062 (2) | −0.0003 (2) |
O1 | 0.0359 (6) | 0.0487 (8) | 0.0532 (8) | 0.0021 (6) | −0.0048 (6) | −0.0029 (6) |
O2 | 0.0410 (7) | 0.0504 (8) | 0.0476 (7) | 0.0046 (6) | −0.0005 (5) | 0.0040 (6) |
O3 | 0.0625 (9) | 0.0863 (11) | 0.0510 (8) | 0.0101 (9) | −0.0140 (7) | −0.0041 (8) |
C1 | 0.0601 (12) | 0.0541 (13) | 0.0482 (12) | 0.0031 (10) | 0.0055 (10) | −0.0119 (10) |
C2 | 0.0904 (19) | 0.0542 (15) | 0.0783 (18) | 0.0092 (13) | −0.0051 (14) | −0.0167 (13) |
C3 | 0.128 (3) | 0.0570 (16) | 0.096 (2) | 0.0008 (18) | 0.003 (2) | −0.0223 (15) |
C4 | 0.108 (2) | 0.082 (2) | 0.089 (2) | −0.0242 (18) | 0.0082 (19) | −0.0389 (17) |
C5 | 0.099 (2) | 0.097 (2) | 0.0735 (17) | −0.0095 (19) | −0.0192 (15) | −0.0266 (17) |
C6 | 0.0865 (18) | 0.0690 (16) | 0.0626 (15) | −0.0006 (14) | −0.0148 (13) | −0.0146 (12) |
C7 | 0.0365 (8) | 0.0427 (10) | 0.0403 (9) | 0.0039 (7) | −0.0010 (7) | 0.0008 (7) |
C8 | 0.0359 (9) | 0.0480 (11) | 0.0421 (10) | 0.0041 (8) | −0.0029 (7) | −0.0002 (8) |
C9 | 0.0485 (10) | 0.0461 (11) | 0.0423 (10) | 0.0068 (8) | −0.0019 (9) | −0.0021 (8) |
C10 | 0.0509 (11) | 0.0513 (11) | 0.0470 (11) | 0.0162 (9) | 0.0059 (9) | −0.0005 (9) |
C11 | 0.0387 (9) | 0.0582 (12) | 0.0463 (10) | 0.0090 (9) | 0.0007 (8) | 0.0103 (9) |
C12 | 0.0354 (8) | 0.0522 (11) | 0.0458 (10) | 0.0026 (8) | −0.0010 (7) | 0.0024 (8) |
C13 | 0.0395 (10) | 0.0830 (17) | 0.0720 (15) | 0.0167 (11) | 0.0080 (10) | 0.0097 (13) |
C14 | 0.0356 (10) | 0.0850 (17) | 0.0901 (17) | 0.0012 (12) | −0.0020 (10) | 0.0225 (15) |
C15 | 0.0482 (12) | 0.0728 (16) | 0.0902 (18) | −0.0076 (11) | −0.0053 (12) | 0.0125 (13) |
C16 | 0.0432 (11) | 0.0640 (14) | 0.0763 (14) | −0.0081 (10) | −0.0002 (10) | −0.0099 (12) |
C17 | 0.041 (3) | 0.065 (4) | 0.043 (4) | 0.001 (3) | −0.008 (2) | −0.003 (3) |
C18 | 0.166 (9) | 0.137 (8) | 0.076 (5) | 0.039 (7) | −0.013 (6) | −0.010 (5) |
C19 | 0.108 (5) | 0.121 (6) | 0.048 (3) | −0.048 (5) | −0.002 (4) | 0.003 (3) |
C20 | 0.069 (5) | 0.089 (6) | 0.045 (3) | −0.006 (4) | 0.006 (3) | −0.016 (3) |
C17' | 0.072 (5) | 0.085 (6) | 0.045 (4) | 0.011 (4) | −0.012 (3) | −0.001 (4) |
C18' | 0.075 (3) | 0.058 (3) | 0.046 (3) | −0.021 (3) | −0.015 (3) | 0.014 (2) |
C19' | 0.081 (4) | 0.099 (5) | 0.053 (3) | −0.017 (4) | −0.010 (3) | −0.012 (3) |
C20' | 0.071 (5) | 0.084 (6) | 0.048 (4) | −0.010 (4) | 0.005 (3) | −0.016 (3) |
C21 | 0.0337 (8) | 0.0426 (10) | 0.0459 (10) | −0.0023 (8) | 0.0018 (7) | −0.0036 (8) |
C22 | 0.0345 (8) | 0.0467 (11) | 0.0459 (10) | −0.0032 (8) | 0.0018 (7) | −0.0008 (8) |
C23 | 0.0385 (9) | 0.0420 (11) | 0.0664 (13) | 0.0006 (8) | 0.0041 (9) | −0.0078 (9) |
C24 | 0.0507 (11) | 0.0632 (14) | 0.0636 (13) | 0.0060 (10) | 0.0095 (10) | −0.0188 (11) |
C25 | 0.0500 (11) | 0.0778 (16) | 0.0477 (12) | 0.0016 (11) | 0.0022 (9) | −0.0139 (11) |
C26 | 0.0415 (10) | 0.0582 (13) | 0.0456 (11) | 0.0005 (9) | 0.0002 (8) | −0.0038 (9) |
C27 | 0.0485 (11) | 0.0443 (11) | 0.0814 (16) | 0.0058 (9) | −0.0034 (11) | −0.0111 (11) |
C28 | 0.0533 (13) | 0.0681 (16) | 0.112 (2) | 0.0156 (12) | 0.0060 (14) | −0.0163 (14) |
C29 | 0.0623 (17) | 0.091 (2) | 0.166 (4) | 0.0345 (17) | −0.009 (2) | −0.033 (2) |
C30 | 0.083 (2) | 0.069 (2) | 0.175 (4) | 0.0355 (17) | −0.043 (2) | −0.025 (2) |
C31 | 0.101 (2) | 0.0539 (16) | 0.123 (3) | 0.0139 (15) | −0.030 (2) | 0.0059 (16) |
C32 | 0.0642 (14) | 0.0524 (14) | 0.0977 (19) | 0.0071 (12) | −0.0093 (13) | 0.0046 (13) |
Cl1—P1 | 1.9878 (7) | C17—H17B | 0.9700 |
P1—O3 | 1.4526 (15) | C18—C19 | 1.528 (8) |
P1—O2 | 1.5741 (14) | C18—H18A | 0.9700 |
P1—O1 | 1.5822 (14) | C18—H18B | 0.9700 |
O1—C8 | 1.418 (2) | C19—C20 | 1.501 (8) |
O2—C22 | 1.411 (2) | C19—H19A | 0.9700 |
C1—C2 | 1.381 (3) | C19—H19B | 0.9700 |
C1—C6 | 1.390 (3) | C20—C25 | 1.525 (7) |
C1—C9 | 1.484 (3) | C20—H20A | 0.9700 |
C2—C3 | 1.376 (4) | C20—H20B | 0.9700 |
C2—H2 | 0.9300 | C17'—C18' | 1.520 (8) |
C3—C4 | 1.346 (5) | C17'—C26 | 1.522 (8) |
C3—H3 | 0.9300 | C17'—H17C | 0.9700 |
C4—C5 | 1.371 (5) | C17'—H17D | 0.9700 |
C4—H4 | 0.9300 | C18'—C19' | 1.502 (7) |
C5—C6 | 1.379 (4) | C18'—H18C | 0.9700 |
C5—H5 | 0.9300 | C18'—H18D | 0.9700 |
C6—H6 | 0.9300 | C19'—C20' | 1.489 (8) |
C7—C8 | 1.387 (3) | C19'—H19C | 0.9700 |
C7—C12 | 1.410 (2) | C19'—H19D | 0.9700 |
C7—C21 | 1.487 (2) | C20'—C25 | 1.521 (7) |
C8—C9 | 1.386 (3) | C20'—H20C | 0.9700 |
C9—C10 | 1.395 (3) | C20'—H20D | 0.9700 |
C10—C11 | 1.381 (3) | C21—C22 | 1.393 (3) |
C10—H10 | 0.9300 | C21—C26 | 1.401 (3) |
C11—C12 | 1.391 (3) | C22—C23 | 1.389 (3) |
C11—C13 | 1.523 (3) | C23—C24 | 1.398 (3) |
C12—C16 | 1.515 (3) | C23—C27 | 1.484 (3) |
C13—C14 | 1.505 (4) | C24—C25 | 1.381 (3) |
C13—H13A | 0.9700 | C24—H24 | 0.9300 |
C13—H13B | 0.9700 | C25—C26 | 1.397 (3) |
C14—C15 | 1.505 (3) | C27—C32 | 1.375 (4) |
C14—H14A | 0.9700 | C27—C28 | 1.396 (3) |
C14—H14B | 0.9700 | C28—C29 | 1.375 (4) |
C15—C16 | 1.507 (3) | C28—H28 | 0.9300 |
C15—H15A | 0.9700 | C29—C30 | 1.371 (5) |
C15—H15B | 0.9700 | C29—H29 | 0.9300 |
C16—H16A | 0.9700 | C30—C31 | 1.367 (5) |
C16—H16B | 0.9700 | C30—H30 | 0.9300 |
C17—C18 | 1.514 (8) | C31—C32 | 1.396 (4) |
C17—C26 | 1.528 (7) | C31—H31 | 0.9300 |
C17—H17A | 0.9700 | C32—H32 | 0.9300 |
O3—P1—O2 | 112.68 (9) | C19—C18—H18B | 107.3 |
O3—P1—O1 | 117.92 (9) | H18A—C18—H18B | 106.9 |
O2—P1—O1 | 105.59 (7) | C20—C19—C18 | 108.7 (8) |
O3—P1—Cl1 | 113.46 (7) | C20—C19—H19A | 110.0 |
O2—P1—Cl1 | 106.56 (6) | C18—C19—H19A | 110.0 |
O1—P1—Cl1 | 99.24 (6) | C20—C19—H19B | 110.0 |
C8—O1—P1 | 118.61 (13) | C18—C19—H19B | 110.0 |
C22—O2—P1 | 117.68 (12) | H19A—C19—H19B | 108.3 |
C2—C1—C6 | 118.3 (2) | C19—C20—C25 | 104.8 (6) |
C2—C1—C9 | 119.5 (2) | C19—C20—H20A | 110.8 |
C6—C1—C9 | 122.1 (2) | C25—C20—H20A | 110.8 |
C3—C2—C1 | 120.5 (3) | C19—C20—H20B | 110.8 |
C3—C2—H2 | 119.7 | C25—C20—H20B | 110.8 |
C1—C2—H2 | 119.7 | H20A—C20—H20B | 108.9 |
C4—C3—C2 | 120.6 (3) | C18'—C17'—C26 | 113.1 (7) |
C4—C3—H3 | 119.7 | C18'—C17'—H17C | 109.0 |
C2—C3—H3 | 119.7 | C26—C17'—H17C | 109.0 |
C3—C4—C5 | 120.3 (3) | C18'—C17'—H17D | 109.0 |
C3—C4—H4 | 119.8 | C26—C17'—H17D | 109.0 |
C5—C4—H4 | 119.8 | H17C—C17'—H17D | 107.8 |
C4—C5—C6 | 120.1 (3) | C19'—C18'—C17' | 98.4 (7) |
C4—C5—H5 | 120.0 | C19'—C18'—H18C | 112.1 |
C6—C5—H5 | 120.0 | C17'—C18'—H18C | 112.1 |
C5—C6—C1 | 120.1 (3) | C19'—C18'—H18D | 112.1 |
C5—C6—H6 | 120.0 | C17'—C18'—H18D | 112.1 |
C1—C6—H6 | 120.0 | H18C—C18'—H18D | 109.7 |
C8—C7—C12 | 118.06 (17) | C20'—C19'—C18' | 109.8 (7) |
C8—C7—C21 | 119.75 (15) | C20'—C19'—H19C | 109.7 |
C12—C7—C21 | 122.19 (16) | C18'—C19'—H19C | 109.7 |
C9—C8—C7 | 124.03 (16) | C20'—C19'—H19D | 109.7 |
C9—C8—O1 | 118.08 (17) | C18'—C19'—H19D | 109.7 |
C7—C8—O1 | 117.72 (16) | H19C—C19'—H19D | 108.2 |
C8—C9—C10 | 115.48 (18) | C19'—C20'—C25 | 114.8 (7) |
C8—C9—C1 | 122.66 (17) | C19'—C20'—H20C | 108.6 |
C10—C9—C1 | 121.74 (18) | C25—C20'—H20C | 108.6 |
C11—C10—C9 | 122.75 (18) | C19'—C20'—H20D | 108.6 |
C11—C10—H10 | 118.6 | C25—C20'—H20D | 108.6 |
C9—C10—H10 | 118.6 | H20C—C20'—H20D | 107.5 |
C10—C11—C12 | 120.08 (17) | C22—C21—C26 | 118.42 (17) |
C10—C11—C13 | 118.4 (2) | C22—C21—C7 | 119.69 (16) |
C12—C11—C13 | 121.5 (2) | C26—C21—C7 | 121.84 (17) |
C11—C12—C7 | 118.99 (18) | C23—C22—C21 | 124.11 (18) |
C11—C12—C16 | 120.40 (17) | C23—C22—O2 | 118.26 (17) |
C7—C12—C16 | 120.46 (17) | C21—C22—O2 | 117.55 (16) |
C14—C13—C11 | 114.6 (2) | C22—C23—C24 | 115.42 (19) |
C14—C13—H13A | 108.6 | C22—C23—C27 | 123.27 (19) |
C11—C13—H13A | 108.6 | C24—C23—C27 | 121.26 (19) |
C14—C13—H13B | 108.6 | C25—C24—C23 | 122.48 (19) |
C11—C13—H13B | 108.6 | C25—C24—H24 | 118.8 |
H13A—C13—H13B | 107.6 | C23—C24—H24 | 118.8 |
C15—C14—C13 | 112.25 (19) | C24—C25—C26 | 120.55 (19) |
C15—C14—H14A | 109.2 | C24—C25—C20' | 118.8 (4) |
C13—C14—H14A | 109.2 | C26—C25—C20' | 119.7 (4) |
C15—C14—H14B | 109.2 | C24—C25—C20 | 118.7 (4) |
C13—C14—H14B | 109.2 | C26—C25—C20 | 119.9 (5) |
H14A—C14—H14B | 107.9 | C25—C26—C21 | 118.74 (18) |
C14—C15—C16 | 109.9 (2) | C25—C26—C17' | 114.4 (4) |
C14—C15—H15A | 109.7 | C21—C26—C17' | 126.8 (4) |
C16—C15—H15A | 109.7 | C25—C26—C17 | 123.4 (4) |
C14—C15—H15B | 109.7 | C21—C26—C17 | 117.1 (4) |
C16—C15—H15B | 109.7 | C32—C27—C28 | 118.3 (2) |
H15A—C15—H15B | 108.2 | C32—C27—C23 | 121.8 (2) |
C15—C16—C12 | 113.2 (2) | C28—C27—C23 | 119.8 (2) |
C15—C16—H16A | 108.9 | C29—C28—C27 | 120.7 (3) |
C12—C16—H16A | 108.9 | C29—C28—H28 | 119.7 |
C15—C16—H16B | 108.9 | C27—C28—H28 | 119.7 |
C12—C16—H16B | 108.9 | C28—C29—C30 | 120.3 (3) |
H16A—C16—H16B | 107.8 | C28—C29—H29 | 119.9 |
C18—C17—C26 | 109.8 (7) | C30—C29—H29 | 119.9 |
C18—C17—H17A | 109.7 | C31—C30—C29 | 120.2 (3) |
C26—C17—H17A | 109.7 | C31—C30—H30 | 119.9 |
C18—C17—H17B | 109.7 | C29—C30—H30 | 119.9 |
C26—C17—H17B | 109.7 | C30—C31—C32 | 119.8 (3) |
H17A—C17—H17B | 108.2 | C30—C31—H31 | 120.1 |
C17—C18—C19 | 120.3 (9) | C32—C31—H31 | 120.1 |
C17—C18—H18A | 107.3 | C27—C32—C31 | 120.7 (3) |
C19—C18—H18A | 107.3 | C27—C32—H32 | 119.6 |
C17—C18—H18B | 107.3 | C31—C32—H32 | 119.6 |
O3—P1—O1—C8 | 84.18 (16) | C12—C7—C21—C26 | −61.5 (3) |
O2—P1—O1—C8 | −42.76 (15) | C26—C21—C22—C23 | 6.4 (3) |
Cl1—P1—O1—C8 | −152.95 (12) | C7—C21—C22—C23 | −176.17 (17) |
O3—P1—O2—C22 | −178.91 (13) | C26—C21—C22—O2 | −170.31 (17) |
O1—P1—O2—C22 | −48.85 (13) | C7—C21—C22—O2 | 7.1 (2) |
Cl1—P1—O2—C22 | 56.04 (13) | P1—O2—C22—C23 | −105.79 (17) |
C6—C1—C2—C3 | −2.1 (4) | P1—O2—C22—C21 | 71.10 (18) |
C9—C1—C2—C3 | 177.0 (2) | C21—C22—C23—C24 | −4.2 (3) |
C1—C2—C3—C4 | 1.5 (5) | O2—C22—C23—C24 | 172.50 (17) |
C2—C3—C4—C5 | 0.3 (5) | C21—C22—C23—C27 | 178.32 (19) |
C3—C4—C5—C6 | −1.5 (5) | O2—C22—C23—C27 | −5.0 (3) |
C4—C5—C6—C1 | 0.8 (5) | C22—C23—C24—C25 | −0.7 (3) |
C2—C1—C6—C5 | 1.0 (4) | C27—C23—C24—C25 | 176.9 (2) |
C9—C1—C6—C5 | −178.1 (2) | C23—C24—C25—C26 | 3.2 (3) |
C12—C7—C8—C9 | 9.3 (3) | C23—C24—C25—C20' | −165.5 (5) |
C21—C7—C8—C9 | −171.49 (18) | C23—C24—C25—C20 | 173.0 (4) |
C12—C7—C8—O1 | −175.67 (17) | C19'—C20'—C25—C24 | −173.4 (5) |
C21—C7—C8—O1 | 3.6 (3) | C19'—C20'—C25—C26 | 17.8 (9) |
P1—O1—C8—C9 | −113.98 (17) | C19'—C20'—C25—C20 | −78 (2) |
P1—O1—C8—C7 | 70.7 (2) | C19—C20—C25—C24 | 140.2 (6) |
C7—C8—C9—C10 | −5.0 (3) | C19—C20—C25—C26 | −49.9 (8) |
O1—C8—C9—C10 | 179.97 (17) | C19—C20—C25—C20' | 45 (2) |
C7—C8—C9—C1 | 171.05 (19) | C24—C25—C26—C21 | −0.9 (3) |
O1—C8—C9—C1 | −4.0 (3) | C20'—C25—C26—C21 | 167.7 (4) |
C2—C1—C9—C8 | −117.0 (3) | C20—C25—C26—C21 | −170.7 (4) |
C6—C1—C9—C8 | 62.0 (3) | C24—C25—C26—C17' | 176.5 (5) |
C2—C1—C9—C10 | 58.8 (3) | C20'—C25—C26—C17' | −14.9 (7) |
C6—C1—C9—C10 | −122.2 (3) | C20—C25—C26—C17' | 6.7 (7) |
C8—C9—C10—C11 | −2.1 (3) | C24—C25—C26—C17 | −170.4 (5) |
C1—C9—C10—C11 | −178.14 (18) | C20'—C25—C26—C17 | −1.8 (7) |
C9—C10—C11—C12 | 4.5 (3) | C20—C25—C26—C17 | 19.9 (7) |
C9—C10—C11—C13 | −173.4 (2) | C22—C21—C26—C25 | −3.6 (3) |
C10—C11—C12—C7 | 0.0 (3) | C7—C21—C26—C25 | 179.01 (18) |
C13—C11—C12—C7 | 177.81 (19) | C22—C21—C26—C17' | 179.4 (6) |
C10—C11—C12—C16 | −175.7 (2) | C7—C21—C26—C17' | 2.0 (6) |
C13—C11—C12—C16 | 2.2 (3) | C22—C21—C26—C17 | 166.5 (5) |
C8—C7—C12—C11 | −6.5 (3) | C7—C21—C26—C17 | −10.9 (5) |
C21—C7—C12—C11 | 174.34 (17) | C18'—C17'—C26—C25 | 44.0 (9) |
C8—C7—C12—C16 | 169.16 (19) | C18'—C17'—C26—C21 | −138.8 (5) |
C21—C7—C12—C16 | −10.0 (3) | C18'—C17'—C26—C17 | −87 (3) |
C10—C11—C13—C14 | −175.55 (19) | C18—C17—C26—C25 | −2.9 (10) |
C12—C11—C13—C14 | 6.6 (3) | C18—C17—C26—C21 | −172.5 (6) |
C11—C13—C14—C15 | −38.1 (3) | C18—C17—C26—C17' | 53 (3) |
C13—C14—C15—C16 | 61.0 (3) | C22—C23—C27—C32 | −42.4 (3) |
C14—C15—C16—C12 | −51.5 (3) | C24—C23—C27—C32 | 140.2 (2) |
C11—C12—C16—C15 | 20.8 (3) | C22—C23—C27—C28 | 139.1 (2) |
C7—C12—C16—C15 | −154.8 (2) | C24—C23—C27—C28 | −38.3 (3) |
C26—C17—C18—C19 | 20.1 (14) | C32—C27—C28—C29 | 1.0 (4) |
C17—C18—C19—C20 | −53.2 (13) | C23—C27—C28—C29 | 179.6 (3) |
C18—C19—C20—C25 | 62.4 (9) | C27—C28—C29—C30 | −0.3 (5) |
C26—C17'—C18'—C19' | −70.3 (8) | C28—C29—C30—C31 | −1.4 (5) |
C17'—C18'—C19'—C20' | 71.4 (8) | C29—C30—C31—C32 | 2.4 (5) |
C18'—C19'—C20'—C25 | −48.8 (10) | C28—C27—C32—C31 | 0.0 (4) |
C8—C7—C21—C22 | −58.1 (2) | C23—C27—C32—C31 | −178.5 (2) |
C12—C7—C21—C22 | 121.1 (2) | C30—C31—C32—C27 | −1.8 (4) |
C8—C7—C21—C26 | 119.3 (2) |
Experimental details
Crystal data | |
Chemical formula | C32H28ClO3P |
Mr | 526.96 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 295 |
a, b, c (Å) | 12.6642 (8), 13.1613 (8), 15.9097 (9) |
V (Å3) | 2651.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.32 × 0.17 × 0.07 |
Data collection | |
Diffractometer | Bruker APEX CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 33491, 6089, 4949 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.099, 1.03 |
No. of reflections | 6089 |
No. of parameters | 370 |
No. of restraints | 52 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.23 |
Absolute structure | Flack (1983), 2674 Friedel pairs |
Absolute structure parameter | 0.02 (6) |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006 or??2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).
3,3'-Diphenyl-5,6,7,8,5',6',7',8'-octahydro-[1,1']-binaphthalenyl-2,2'-phosphate is a highly enantioselective catalyst (Chen et al., 2006) as is starting reactant 3,3'-diphenyl-5,6,7,8,5',6',7',8'-octahydro-[1,1']-binaphthalenyl-2,2'-diol (McDougal & Schaus, 2003). The reaction of the diol with phosphorus oxychloride has yielded the title chlorophosphate, (I), (Fig. 1) which is also expected to exhibit such activity.