Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029479/wk2065sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029479/wk2065Isup2.hkl |
CCDC reference: 655007
The title compound was synthesized by our recently developed method for the generation of P-stereogenic phosphorus compounds (Bergin et al., 2007). The corresponding monophosphine oxide was produced in good ee (80%) from the reaction of the racemic phosphine with (-)-menthol in the presence of hexachloroacetone. It was subsequently oxidatively coupled to yield the bisphosphine oxide in 98% ee. X-ray quality crystals were obtained by crystallizing from benzene. To the best of our knowledge this is the first crystal structure of an enantiomerically pure DiPAMPO analogue.
This crystal structure establishes that in our recently developed method for the construction of P-stereogenic phosphine oxides (Bergin et al., 2007), the use of (-)-menthol gives rise to the R-configured phosphine oxide.
The PO and PC bond lengths are both at the high ends of the ranges expected for phosphine oxides, (147.5–149) and (179–181) pm respectively (Gilheany, 1992). The bond angles at phosphorus (CPO 111–113.5° and CPC 106–106.5°) show the expected deviation from the tetrahedral values consistent with the shorter PO distance (Gilheany, 1992).
For related literature, see: Bergin et al. (2007); Gilheany (1992).
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-hydrogen atoms. |
C28H28O2P2 | Dx = 1.324 Mg m−3 |
Mr = 458.44 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 5179 reflections |
a = 5.7941 (5) Å | θ = 2.5–30.8° |
b = 17.2455 (15) Å | µ = 0.21 mm−1 |
c = 23.012 (2) Å | T = 100 K |
V = 2299.4 (3) Å3 | Lath, colourless |
Z = 4 | 0.50 × 0.50 × 0.05 mm |
F(000) = 968 |
Bruker APEX CCD area-detector diffractometer | 6693 independent reflections |
Radiation source: fine-focus sealed tube | 5820 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
φ and ω scans | θmax = 30.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
Tmin = 0.717, Tmax = 0.989 | k = −24→24 |
24918 measured reflections | l = −32→32 |
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)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0596P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
6693 reflections | Δρmax = 0.56 e Å−3 |
289 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (8) |
C28H28O2P2 | V = 2299.4 (3) Å3 |
Mr = 458.44 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.7941 (5) Å | µ = 0.21 mm−1 |
b = 17.2455 (15) Å | T = 100 K |
c = 23.012 (2) Å | 0.50 × 0.50 × 0.05 mm |
Bruker APEX CCD area-detector diffractometer | 6693 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 5820 reflections with I > 2σ(I) |
Tmin = 0.717, Tmax = 0.989 | Rint = 0.054 |
24918 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.113 | Δρmax = 0.56 e Å−3 |
S = 1.09 | Δρmin = −0.23 e Å−3 |
6693 reflections | Absolute structure: Flack (1983) |
289 parameters | Absolute structure parameter: −0.02 (8) |
0 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 | ||
P1 | 0.33886 (9) | 0.29398 (3) | 0.21588 (2) | 0.01480 (11) | |
O1 | 0.5851 (3) | 0.29881 (9) | 0.19807 (6) | 0.0211 (3) | |
C1 | 0.2408 (4) | 0.19598 (11) | 0.22940 (9) | 0.0171 (4) | |
C2 | 0.0501 (4) | 0.16736 (13) | 0.19982 (10) | 0.0265 (5) | |
H2A | −0.0349 | 0.2006 | 0.1748 | 0.032* | |
C3 | −0.0176 (5) | 0.09058 (14) | 0.20643 (12) | 0.0350 (6) | |
H3A | −0.1479 | 0.0714 | 0.1859 | 0.042* | |
C4 | 0.1036 (4) | 0.04265 (13) | 0.24256 (11) | 0.0318 (6) | |
H4A | 0.0591 | −0.0101 | 0.2465 | 0.038* | |
C5 | 0.2907 (5) | 0.07055 (13) | 0.27351 (10) | 0.0308 (6) | |
H5A | 0.3714 | 0.0369 | 0.2991 | 0.037* | |
C6 | 0.3631 (4) | 0.14753 (12) | 0.26775 (9) | 0.0223 (4) | |
C7 | 0.5636 (5) | 0.17576 (14) | 0.30295 (11) | 0.0333 (6) | |
H7A | 0.6237 | 0.1331 | 0.3267 | 0.050* | |
H7B | 0.5132 | 0.2181 | 0.3283 | 0.050* | |
H7C | 0.6851 | 0.1945 | 0.2769 | 0.050* | |
C8 | 0.2867 (3) | 0.34813 (11) | 0.28190 (9) | 0.0174 (4) | |
C9 | 0.4561 (4) | 0.39914 (12) | 0.30008 (10) | 0.0251 (5) | |
H9A | 0.5929 | 0.4052 | 0.2778 | 0.030* | |
C10 | 0.4266 (5) | 0.44147 (14) | 0.35085 (12) | 0.0338 (6) | |
H10A | 0.5431 | 0.4766 | 0.3631 | 0.041* | |
C11 | 0.2307 (5) | 0.43278 (14) | 0.38321 (11) | 0.0315 (6) | |
H11A | 0.2124 | 0.4612 | 0.4183 | 0.038* | |
C12 | 0.0594 (5) | 0.38282 (13) | 0.36513 (10) | 0.0303 (5) | |
H12A | −0.0768 | 0.3772 | 0.3877 | 0.036* | |
C13 | 0.0843 (4) | 0.34061 (13) | 0.31418 (10) | 0.0244 (5) | |
H13A | −0.0352 | 0.3069 | 0.3014 | 0.029* | |
C14 | 0.1437 (4) | 0.33385 (12) | 0.16196 (9) | 0.0185 (4) | |
H14A | 0.1397 | 0.2991 | 0.1277 | 0.022* | |
H14B | −0.0140 | 0.3362 | 0.1784 | 0.022* | |
C15 | 0.2170 (4) | 0.41508 (11) | 0.14268 (9) | 0.0161 (4) | |
H15A | 0.3778 | 0.4134 | 0.1282 | 0.019* | |
H15B | 0.2120 | 0.4507 | 0.1764 | 0.019* | |
P2 | 0.02887 (8) | 0.45118 (3) | 0.08600 (2) | 0.01335 (11) | |
O2 | −0.2200 (2) | 0.44574 (9) | 0.10142 (6) | 0.0188 (3) | |
C16 | 0.1036 (3) | 0.39833 (11) | 0.02016 (8) | 0.0141 (4) | |
C17 | 0.2915 (3) | 0.34797 (11) | 0.01890 (9) | 0.0169 (4) | |
H17A | 0.3940 | 0.3461 | 0.0511 | 0.020* | |
C18 | 0.3312 (4) | 0.30052 (12) | −0.02873 (9) | 0.0209 (4) | |
H18A | 0.4604 | 0.2666 | −0.0291 | 0.025* | |
C19 | 0.1830 (4) | 0.30256 (12) | −0.07545 (9) | 0.0224 (4) | |
H19A | 0.2045 | 0.2681 | −0.1072 | 0.027* | |
C20 | 0.0026 (4) | 0.35514 (12) | −0.07596 (9) | 0.0204 (4) | |
H20A | −0.0940 | 0.3581 | −0.1093 | 0.024* | |
C21 | −0.0409 (3) | 0.40357 (11) | −0.02912 (9) | 0.0171 (4) | |
C22 | −0.2408 (4) | 0.45922 (12) | −0.03249 (9) | 0.0212 (4) | |
H22A | −0.3182 | 0.4535 | −0.0701 | 0.032* | |
H22B | −0.1839 | 0.5125 | −0.0284 | 0.032* | |
H22C | −0.3503 | 0.4479 | −0.0012 | 0.032* | |
C23 | 0.1147 (3) | 0.55056 (11) | 0.07362 (8) | 0.0151 (4) | |
C24 | 0.3295 (4) | 0.57026 (12) | 0.05179 (10) | 0.0236 (4) | |
H24A | 0.4410 | 0.5310 | 0.0448 | 0.028* | |
C25 | 0.3826 (4) | 0.64718 (13) | 0.04011 (10) | 0.0265 (5) | |
H25A | 0.5286 | 0.6603 | 0.0241 | 0.032* | |
C26 | 0.2232 (4) | 0.70479 (13) | 0.05178 (10) | 0.0253 (5) | |
H26A | 0.2609 | 0.7574 | 0.0442 | 0.030* | |
C27 | 0.0107 (4) | 0.68623 (12) | 0.07428 (11) | 0.0281 (5) | |
H27A | −0.0982 | 0.7260 | 0.0823 | 0.034* | |
C28 | −0.0452 (4) | 0.60876 (12) | 0.08534 (10) | 0.0225 (4) | |
H28A | −0.1923 | 0.5958 | 0.1008 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0144 (2) | 0.0150 (2) | 0.0149 (2) | −0.00059 (19) | −0.00002 (19) | 0.0026 (2) |
O1 | 0.0179 (7) | 0.0223 (7) | 0.0233 (7) | −0.0003 (6) | 0.0016 (6) | 0.0029 (6) |
C1 | 0.0193 (9) | 0.0163 (9) | 0.0155 (9) | −0.0014 (8) | 0.0032 (7) | −0.0003 (7) |
C2 | 0.0242 (11) | 0.0252 (11) | 0.0302 (12) | −0.0040 (9) | −0.0034 (10) | −0.0015 (9) |
C3 | 0.0314 (13) | 0.0284 (12) | 0.0452 (15) | −0.0101 (10) | 0.0038 (12) | −0.0093 (11) |
C4 | 0.0398 (14) | 0.0168 (10) | 0.0387 (13) | −0.0074 (10) | 0.0160 (11) | −0.0048 (10) |
C5 | 0.0485 (15) | 0.0187 (10) | 0.0253 (12) | 0.0056 (10) | 0.0111 (11) | 0.0037 (9) |
C6 | 0.0302 (12) | 0.0193 (9) | 0.0175 (9) | 0.0037 (9) | 0.0033 (9) | 0.0000 (8) |
C7 | 0.0459 (15) | 0.0262 (11) | 0.0279 (12) | 0.0052 (11) | −0.0154 (11) | 0.0025 (9) |
C8 | 0.0189 (9) | 0.0139 (8) | 0.0194 (9) | 0.0021 (7) | −0.0022 (8) | 0.0031 (8) |
C9 | 0.0210 (10) | 0.0240 (10) | 0.0302 (11) | −0.0036 (9) | −0.0033 (9) | −0.0046 (9) |
C10 | 0.0341 (13) | 0.0286 (12) | 0.0386 (13) | 0.0017 (10) | −0.0104 (11) | −0.0124 (11) |
C11 | 0.0479 (15) | 0.0266 (12) | 0.0200 (11) | 0.0101 (11) | −0.0042 (10) | −0.0051 (9) |
C12 | 0.0393 (14) | 0.0255 (11) | 0.0261 (12) | 0.0032 (11) | 0.0099 (10) | 0.0017 (9) |
C13 | 0.0277 (12) | 0.0181 (9) | 0.0274 (11) | −0.0025 (8) | 0.0056 (9) | −0.0001 (9) |
C14 | 0.0206 (10) | 0.0187 (9) | 0.0161 (9) | −0.0008 (8) | −0.0015 (8) | 0.0049 (7) |
C15 | 0.0182 (10) | 0.0147 (9) | 0.0153 (9) | −0.0005 (7) | −0.0011 (7) | 0.0016 (7) |
P2 | 0.0129 (2) | 0.0126 (2) | 0.0145 (2) | 0.00024 (18) | 0.00076 (18) | 0.00101 (18) |
O2 | 0.0156 (7) | 0.0192 (7) | 0.0217 (7) | 0.0000 (6) | 0.0028 (5) | −0.0001 (6) |
C16 | 0.0153 (9) | 0.0119 (8) | 0.0151 (9) | −0.0020 (7) | 0.0023 (7) | 0.0012 (7) |
C17 | 0.0175 (9) | 0.0155 (9) | 0.0177 (9) | 0.0004 (7) | 0.0007 (7) | 0.0018 (8) |
C18 | 0.0192 (9) | 0.0186 (9) | 0.0250 (10) | 0.0026 (8) | 0.0057 (9) | −0.0016 (8) |
C19 | 0.0261 (11) | 0.0217 (10) | 0.0192 (10) | −0.0036 (9) | 0.0067 (8) | −0.0044 (8) |
C20 | 0.0214 (10) | 0.0245 (10) | 0.0152 (9) | −0.0056 (8) | 0.0004 (8) | −0.0005 (8) |
C21 | 0.0151 (9) | 0.0173 (8) | 0.0188 (9) | −0.0019 (7) | 0.0016 (8) | 0.0024 (7) |
C22 | 0.0187 (10) | 0.0248 (10) | 0.0202 (10) | 0.0020 (8) | −0.0026 (8) | 0.0033 (9) |
C23 | 0.0190 (9) | 0.0128 (8) | 0.0133 (8) | −0.0011 (8) | −0.0022 (7) | 0.0005 (7) |
C24 | 0.0227 (10) | 0.0186 (9) | 0.0296 (11) | 0.0007 (9) | 0.0045 (9) | −0.0008 (8) |
C25 | 0.0269 (12) | 0.0216 (10) | 0.0309 (12) | −0.0042 (9) | 0.0025 (9) | 0.0022 (9) |
C26 | 0.0310 (12) | 0.0143 (9) | 0.0307 (11) | −0.0020 (9) | −0.0093 (9) | 0.0051 (9) |
C27 | 0.0281 (12) | 0.0177 (9) | 0.0384 (13) | 0.0069 (9) | −0.0040 (10) | −0.0009 (9) |
C28 | 0.0179 (9) | 0.0198 (9) | 0.0296 (11) | 0.0026 (8) | 0.0002 (9) | 0.0002 (9) |
P1—O1 | 1.4870 (15) | C15—P2 | 1.810 (2) |
P1—C8 | 1.809 (2) | C15—H15A | 0.9900 |
P1—C1 | 1.810 (2) | C15—H15B | 0.9900 |
P1—C14 | 1.814 (2) | P2—O2 | 1.4878 (14) |
C1—C2 | 1.388 (3) | P2—C16 | 1.820 (2) |
C1—C6 | 1.407 (3) | P2—C23 | 1.807 (2) |
C2—C3 | 1.389 (3) | C16—C17 | 1.393 (3) |
C2—H2A | 0.9500 | C16—C21 | 1.413 (3) |
C3—C4 | 1.367 (4) | C17—C18 | 1.387 (3) |
C3—H3A | 0.9500 | C17—H17A | 0.9500 |
C4—C5 | 1.383 (4) | C18—C19 | 1.376 (3) |
C4—H4A | 0.9500 | C18—H18A | 0.9500 |
C5—C6 | 1.398 (3) | C19—C20 | 1.384 (3) |
C5—H5A | 0.9500 | C19—H19A | 0.9500 |
C6—C7 | 1.498 (3) | C20—C21 | 1.387 (3) |
C7—H7A | 0.9800 | C20—H20A | 0.9500 |
C7—H7B | 0.9800 | C21—C22 | 1.506 (3) |
C7—H7C | 0.9800 | C22—H22A | 0.9800 |
C8—C13 | 1.394 (3) | C22—H22B | 0.9800 |
C8—C9 | 1.383 (3) | C22—H22C | 0.9800 |
C9—C10 | 1.388 (3) | C23—C24 | 1.384 (3) |
C9—H9A | 0.9500 | C23—C28 | 1.392 (3) |
C10—C11 | 1.366 (4) | C24—C25 | 1.388 (3) |
C10—H10A | 0.9500 | C24—H24A | 0.9500 |
C11—C12 | 1.379 (4) | C25—C26 | 1.383 (3) |
C11—H11A | 0.9500 | C25—H25A | 0.9500 |
C12—C13 | 1.387 (3) | C26—C27 | 1.374 (3) |
C12—H12A | 0.9500 | C26—H26A | 0.9500 |
C13—H13A | 0.9500 | C27—C28 | 1.398 (3) |
C14—C15 | 1.530 (3) | C27—H27A | 0.9500 |
C14—H14A | 0.9900 | C28—H28A | 0.9500 |
C14—H14B | 0.9900 | ||
O1—P1—C8 | 111.28 (9) | C14—C15—P2 | 110.90 (13) |
O1—P1—C1 | 113.64 (9) | C14—C15—H15A | 109.5 |
C8—P1—C1 | 106.57 (9) | P2—C15—H15A | 109.5 |
O1—P1—C14 | 112.86 (9) | C14—C15—H15B | 109.5 |
C8—P1—C14 | 105.93 (9) | P2—C15—H15B | 109.5 |
C1—P1—C14 | 106.01 (9) | H15A—C15—H15B | 108.0 |
C2—C1—C6 | 119.8 (2) | O2—P2—C15 | 112.96 (9) |
C2—C1—P1 | 119.83 (16) | O2—P2—C16 | 113.42 (9) |
C6—C1—P1 | 120.29 (16) | C15—P2—C16 | 106.51 (9) |
C1—C2—C3 | 120.7 (2) | O2—P2—C23 | 111.36 (9) |
C1—C2—H2A | 119.7 | C15—P2—C23 | 105.90 (9) |
C3—C2—H2A | 119.7 | C16—P2—C23 | 106.15 (9) |
C4—C3—C2 | 119.9 (2) | C17—C16—C21 | 119.10 (18) |
C4—C3—H3A | 120.1 | C17—C16—P2 | 121.03 (15) |
C2—C3—H3A | 120.1 | C21—C16—P2 | 119.68 (14) |
C3—C4—C5 | 120.4 (2) | C18—C17—C16 | 120.91 (19) |
C3—C4—H4A | 119.8 | C18—C17—H17A | 119.5 |
C5—C4—H4A | 119.8 | C16—C17—H17A | 119.5 |
C4—C5—C6 | 121.1 (2) | C19—C18—C17 | 119.9 (2) |
C4—C5—H5A | 119.5 | C19—C18—H18A | 120.0 |
C6—C5—H5A | 119.5 | C17—C18—H18A | 120.0 |
C5—C6—C1 | 118.2 (2) | C20—C19—C18 | 119.64 (19) |
C5—C6—C7 | 119.3 (2) | C20—C19—H19A | 120.2 |
C1—C6—C7 | 122.5 (2) | C18—C19—H19A | 120.2 |
C6—C7—H7A | 109.5 | C19—C20—C21 | 121.68 (19) |
C6—C7—H7B | 109.5 | C19—C20—H20A | 119.2 |
H7A—C7—H7B | 109.5 | C21—C20—H20A | 119.2 |
C6—C7—H7C | 109.5 | C20—C21—C16 | 118.55 (18) |
H7A—C7—H7C | 109.5 | C20—C21—C22 | 118.90 (18) |
H7B—C7—H7C | 109.5 | C16—C21—C22 | 122.55 (18) |
C13—C8—C9 | 119.7 (2) | C21—C22—H22A | 109.5 |
C13—C8—P1 | 122.69 (16) | C21—C22—H22B | 109.5 |
C9—C8—P1 | 117.64 (16) | H22A—C22—H22B | 109.5 |
C8—C9—C10 | 120.1 (2) | C21—C22—H22C | 109.5 |
C8—C9—H9A | 119.9 | H22A—C22—H22C | 109.5 |
C10—C9—H9A | 119.9 | H22B—C22—H22C | 109.5 |
C11—C10—C9 | 120.2 (2) | C24—C23—C28 | 119.46 (18) |
C11—C10—H10A | 119.9 | C24—C23—P2 | 122.50 (15) |
C9—C10—H10A | 119.9 | C28—C23—P2 | 118.02 (15) |
C10—C11—C12 | 120.2 (2) | C23—C24—C25 | 120.3 (2) |
C10—C11—H11A | 119.9 | C23—C24—H24A | 119.9 |
C12—C11—H11A | 119.9 | C25—C24—H24A | 119.9 |
C11—C12—C13 | 120.5 (2) | C26—C25—C24 | 120.1 (2) |
C11—C12—H12A | 119.7 | C26—C25—H25A | 120.0 |
C13—C12—H12A | 119.7 | C24—C25—H25A | 120.0 |
C8—C13—C12 | 119.3 (2) | C25—C26—C27 | 120.3 (2) |
C8—C13—H13A | 120.4 | C25—C26—H26A | 119.8 |
C12—C13—H13A | 120.4 | C27—C26—H26A | 119.8 |
C15—C14—P1 | 111.86 (14) | C26—C27—C28 | 119.9 (2) |
C15—C14—H14A | 109.2 | C26—C27—H27A | 120.0 |
P1—C14—H14A | 109.2 | C28—C27—H27A | 120.0 |
C15—C14—H14B | 109.2 | C23—C28—C27 | 120.0 (2) |
P1—C14—H14B | 109.2 | C23—C28—H28A | 120.0 |
H14A—C14—H14B | 107.9 | C27—C28—H28A | 120.0 |
O1—P1—C1—C2 | −124.41 (18) | C14—C15—P2—O2 | 51.52 (16) |
C8—P1—C1—C2 | 112.66 (18) | C14—C15—P2—C16 | −73.63 (15) |
C14—P1—C1—C2 | 0.1 (2) | C14—C15—P2—C23 | 173.66 (14) |
O1—P1—C1—C6 | 52.70 (19) | O2—P2—C16—C17 | −131.23 (16) |
C8—P1—C1—C6 | −70.23 (19) | C15—P2—C16—C17 | −6.35 (18) |
C14—P1—C1—C6 | 177.22 (17) | C23—P2—C16—C17 | 106.19 (16) |
C6—C1—C2—C3 | −1.8 (3) | O2—P2—C16—C21 | 43.77 (17) |
P1—C1—C2—C3 | 175.28 (19) | C15—P2—C16—C21 | 168.64 (15) |
C1—C2—C3—C4 | 0.3 (4) | C23—P2—C16—C21 | −78.82 (16) |
C2—C3—C4—C5 | 1.3 (4) | C21—C16—C17—C18 | −3.2 (3) |
C3—C4—C5—C6 | −1.3 (4) | P2—C16—C17—C18 | 171.82 (15) |
C4—C5—C6—C1 | −0.2 (3) | C16—C17—C18—C19 | −0.3 (3) |
C4—C5—C6—C7 | 178.8 (2) | C17—C18—C19—C20 | 3.6 (3) |
C2—C1—C6—C5 | 1.8 (3) | C18—C19—C20—C21 | −3.3 (3) |
P1—C1—C6—C5 | −175.33 (16) | C19—C20—C21—C16 | −0.2 (3) |
C2—C1—C6—C7 | −177.2 (2) | C19—C20—C21—C22 | −179.76 (19) |
P1—C1—C6—C7 | 5.7 (3) | C17—C16—C21—C20 | 3.4 (3) |
O1—P1—C8—C13 | −166.69 (16) | P2—C16—C21—C20 | −171.66 (15) |
C1—P1—C8—C13 | −42.30 (19) | C17—C16—C21—C22 | −177.02 (18) |
C14—P1—C8—C13 | 70.29 (19) | P2—C16—C21—C22 | 7.9 (3) |
O1—P1—C8—C9 | 13.8 (2) | O2—P2—C23—C24 | −171.85 (16) |
C1—P1—C8—C9 | 138.15 (17) | C15—P2—C23—C24 | 65.00 (19) |
C14—P1—C8—C9 | −109.26 (18) | C16—P2—C23—C24 | −47.96 (19) |
C13—C8—C9—C10 | 1.3 (3) | O2—P2—C23—C28 | 6.53 (18) |
P1—C8—C9—C10 | −179.16 (18) | C15—P2—C23—C28 | −116.62 (17) |
C8—C9—C10—C11 | 0.2 (4) | C16—P2—C23—C28 | 130.42 (16) |
C9—C10—C11—C12 | −1.0 (4) | C28—C23—C24—C25 | −1.8 (3) |
C10—C11—C12—C13 | 0.3 (4) | P2—C23—C24—C25 | 176.51 (18) |
C9—C8—C13—C12 | −2.0 (3) | C23—C24—C25—C26 | 1.8 (4) |
P1—C8—C13—C12 | 178.48 (17) | C24—C25—C26—C27 | −0.8 (4) |
C11—C12—C13—C8 | 1.2 (3) | C25—C26—C27—C28 | −0.1 (4) |
O1—P1—C14—C15 | −50.63 (17) | C24—C23—C28—C27 | 0.9 (3) |
C8—P1—C14—C15 | 71.38 (16) | P2—C23—C28—C27 | −177.55 (17) |
C1—P1—C14—C15 | −175.64 (14) | C26—C27—C28—C23 | 0.1 (3) |
P1—C14—C15—P2 | 176.78 (11) |
Experimental details
Crystal data | |
Chemical formula | C28H28O2P2 |
Mr | 458.44 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 5.7941 (5), 17.2455 (15), 23.012 (2) |
V (Å3) | 2299.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.50 × 0.50 × 0.05 |
Data collection | |
Diffractometer | Bruker APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.717, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24918, 6693, 5820 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.113, 1.09 |
No. of reflections | 6693 |
No. of parameters | 289 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.56, −0.23 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.02 (8) |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
This crystal structure establishes that in our recently developed method for the construction of P-stereogenic phosphine oxides (Bergin et al., 2007), the use of (-)-menthol gives rise to the R-configured phosphine oxide.
The PO and PC bond lengths are both at the high ends of the ranges expected for phosphine oxides, (147.5–149) and (179–181) pm respectively (Gilheany, 1992). The bond angles at phosphorus (CPO 111–113.5° and CPC 106–106.5°) show the expected deviation from the tetrahedral values consistent with the shorter PO distance (Gilheany, 1992).