Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002398/na6138sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002398/na6138Isup2.hkl |
CCDC reference: 182615
Compound I was prepared by adding triisopropyl phosphite to one equivalent of phenanthraquinone at room temperature, according to the method of Hamilton et al. (1967).
H atoms were positioned geometrically and refined using a riding model. Cyclohexyl ring C11–16 is disordered over two positions with a relative occupancy of ca 9:1. The minor component was refined isotropically with an appropriate system of restraints.
Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecule of the title compound in the crystal. The minor disorder component of the ring C11–C16 has been omitted. Ellipsoids represent 50% probability levels. |
C32H41O5P | F(000) = 1152 |
Mr = 536.62 | Dx = 1.251 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.665 (2) Å | Cell parameters from 50 reflections |
b = 15.394 (3) Å | θ = 10–11.5° |
c = 19.200 (4) Å | µ = 0.14 mm−1 |
β = 93.92 (2)° | T = 143 K |
V = 2850.1 (10) Å3 | Prism, colourless |
Z = 4 | 0.65 × 0.30 × 0.30 mm |
Stoe STADI-4 diffractometer | Rint = 0.024 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 3.2° |
Graphite monochromator | h = −11→0 |
ω/θ scans | k = −18→1 |
5588 measured reflections | l = −22→22 |
5037 independent reflections | 3 standard reflections every 60 min |
3708 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0447P)2 + 1.4014P] where P = (Fo2 + 2Fc2)/3 |
5037 reflections | (Δ/σ)max < 0.001 |
368 parameters | Δρmax = 0.21 e Å−3 |
18 restraints | Δρmin = −0.31 e Å−3 |
C32H41O5P | V = 2850.1 (10) Å3 |
Mr = 536.62 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.665 (2) Å | µ = 0.14 mm−1 |
b = 15.394 (3) Å | T = 143 K |
c = 19.200 (4) Å | 0.65 × 0.30 × 0.30 mm |
β = 93.92 (2)° |
Stoe STADI-4 diffractometer | Rint = 0.024 |
5588 measured reflections | 3 standard reflections every 60 min |
5037 independent reflections | intensity decay: none |
3708 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.048 | 18 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.21 e Å−3 |
5037 reflections | Δρmin = −0.31 e Å−3 |
368 parameters |
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. The cyclohexyl ring C11–16 is disordered over two positions with relative occupancy ca 9:1. The minor component was refined isotropically with an appropriate system of restraints. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
P | 0.22024 (6) | 0.74534 (4) | 0.55113 (3) | 0.02318 (16) | |
O1 | 0.29440 (15) | 0.65883 (10) | 0.50841 (8) | 0.0240 (4) | |
O2 | 0.06583 (16) | 0.70951 (10) | 0.52199 (8) | 0.0257 (4) | |
O3 | 0.28511 (17) | 0.81751 (10) | 0.50470 (8) | 0.0313 (4) | |
O4 | 0.31223 (16) | 0.71164 (10) | 0.61744 (8) | 0.0267 (4) | |
O5 | 0.14331 (16) | 0.81665 (10) | 0.59740 (8) | 0.0270 (4) | |
C1 | −0.1855 (2) | 0.63593 (16) | 0.44820 (12) | 0.0288 (6) | |
H1 | −0.1989 | 0.6857 | 0.4762 | 0.035* | |
C2 | −0.2968 (3) | 0.59791 (17) | 0.41217 (13) | 0.0333 (6) | |
H2 | −0.3869 | 0.6220 | 0.4144 | 0.040* | |
C3 | −0.2776 (3) | 0.52407 (18) | 0.37239 (13) | 0.0359 (6) | |
H3 | −0.3553 | 0.4978 | 0.3478 | 0.043* | |
C4 | −0.1483 (3) | 0.48844 (16) | 0.36806 (12) | 0.0306 (6) | |
H4 | −0.1380 | 0.4376 | 0.3408 | 0.037* | |
C4A | −0.0308 (2) | 0.52600 (15) | 0.40342 (11) | 0.0240 (5) | |
C4B | 0.1088 (2) | 0.49048 (15) | 0.39978 (11) | 0.0243 (5) | |
C5 | 0.1354 (3) | 0.41236 (16) | 0.36529 (12) | 0.0312 (6) | |
H5 | 0.0604 | 0.3818 | 0.3420 | 0.037* | |
C6 | 0.2667 (3) | 0.37925 (17) | 0.36439 (13) | 0.0362 (6) | |
H6 | 0.2811 | 0.3261 | 0.3409 | 0.043* | |
C7 | 0.3794 (3) | 0.42243 (16) | 0.39744 (12) | 0.0315 (6) | |
H7 | 0.4700 | 0.3986 | 0.3970 | 0.038* | |
C8 | 0.3586 (2) | 0.49965 (15) | 0.43068 (12) | 0.0260 (5) | |
H8 | 0.4356 | 0.5301 | 0.4522 | 0.031* | |
C8A | 0.2248 (2) | 0.53416 (15) | 0.43322 (11) | 0.0230 (5) | |
C9 | 0.1970 (2) | 0.61038 (14) | 0.47159 (11) | 0.0219 (5) | |
C10 | 0.0683 (2) | 0.63887 (14) | 0.47787 (11) | 0.0225 (5) | |
C10A | −0.0516 (2) | 0.60151 (15) | 0.44393 (11) | 0.0235 (5) | |
C11 | 0.3657 (4) | 0.8104 (2) | 0.4430 (2) | 0.0326 (9) | 0.892 (4) |
H11 | 0.3532 | 0.7515 | 0.4215 | 0.039* | 0.892 (4) |
C12 | 0.5167 (3) | 0.8257 (3) | 0.46510 (17) | 0.0506 (10) | 0.892 (4) |
H12A | 0.5519 | 0.7772 | 0.4952 | 0.061* | 0.892 (4) |
H12B | 0.5260 | 0.8800 | 0.4927 | 0.061* | 0.892 (4) |
C13 | 0.6031 (4) | 0.8327 (3) | 0.4016 (2) | 0.0684 (13) | 0.892 (4) |
H13A | 0.6999 | 0.8475 | 0.4174 | 0.082* | 0.892 (4) |
H13B | 0.6039 | 0.7757 | 0.3777 | 0.082* | 0.892 (4) |
C14 | 0.5463 (6) | 0.9011 (4) | 0.3506 (2) | 0.0570 (16) | 0.892 (4) |
H14A | 0.5555 | 0.9592 | 0.3726 | 0.068* | 0.892 (4) |
H14B | 0.6009 | 0.9010 | 0.3088 | 0.068* | 0.892 (4) |
C15 | 0.3956 (4) | 0.8838 (3) | 0.32889 (17) | 0.0539 (10) | 0.892 (4) |
H15A | 0.3873 | 0.8283 | 0.3029 | 0.065* | 0.892 (4) |
H15B | 0.3593 | 0.9307 | 0.2975 | 0.065* | 0.892 (4) |
C16 | 0.3103 (3) | 0.8792 (2) | 0.39259 (15) | 0.0416 (9) | 0.892 (4) |
H16A | 0.3127 | 0.9363 | 0.4163 | 0.050* | 0.892 (4) |
H16B | 0.2126 | 0.8660 | 0.3775 | 0.050* | 0.892 (4) |
C11' | 0.397 (3) | 0.811 (2) | 0.4615 (12) | 0.024 (9)* | 0.108 (4) |
H11' | 0.4573 | 0.7601 | 0.4747 | 0.028* | 0.108 (4) |
C12' | 0.476 (2) | 0.8951 (15) | 0.4707 (11) | 0.037 (6)* | 0.108 (4) |
H12C | 0.5240 | 0.8971 | 0.5179 | 0.044* | 0.108 (4) |
H12D | 0.4111 | 0.9447 | 0.4661 | 0.044* | 0.108 (4) |
C13' | 0.582 (3) | 0.903 (3) | 0.4162 (16) | 0.086 (12)* | 0.108 (4) |
H13C | 0.6265 | 0.9606 | 0.4201 | 0.103* | 0.108 (4) |
H13D | 0.6556 | 0.8585 | 0.4259 | 0.103* | 0.108 (4) |
C14' | 0.520 (6) | 0.890 (3) | 0.3423 (16) | 0.072 (18)* | 0.108 (4) |
H14C | 0.5948 | 0.8919 | 0.3095 | 0.086* | 0.108 (4) |
H14D | 0.4555 | 0.9389 | 0.3301 | 0.086* | 0.108 (4) |
C15' | 0.443 (3) | 0.8049 (18) | 0.3343 (12) | 0.053 (8)* | 0.108 (4) |
H15C | 0.5081 | 0.7558 | 0.3420 | 0.064* | 0.108 (4) |
H15D | 0.3977 | 0.7999 | 0.2865 | 0.064* | 0.108 (4) |
C16' | 0.332 (2) | 0.8021 (17) | 0.3884 (12) | 0.043 (7)* | 0.108 (4) |
H16C | 0.2651 | 0.8498 | 0.3788 | 0.051* | 0.108 (4) |
H16D | 0.2814 | 0.7464 | 0.3841 | 0.051* | 0.108 (4) |
C21 | 0.3493 (2) | 0.75975 (15) | 0.68163 (11) | 0.0264 (5) | |
H21 | 0.2657 | 0.7904 | 0.6973 | 0.032* | |
C22 | 0.4611 (3) | 0.82569 (16) | 0.66786 (13) | 0.0330 (6) | |
H22A | 0.4221 | 0.8709 | 0.6355 | 0.040* | |
H22B | 0.5377 | 0.7965 | 0.6454 | 0.040* | |
C23 | 0.5171 (3) | 0.86798 (17) | 0.73597 (13) | 0.0379 (6) | |
H23A | 0.5948 | 0.9072 | 0.7264 | 0.045* | |
H23B | 0.4432 | 0.9034 | 0.7551 | 0.045* | |
C24 | 0.5672 (3) | 0.80077 (18) | 0.78938 (13) | 0.0362 (6) | |
H24A | 0.5992 | 0.8301 | 0.8335 | 0.043* | |
H24B | 0.6467 | 0.7686 | 0.7721 | 0.043* | |
C25 | 0.4515 (3) | 0.73754 (18) | 0.80306 (12) | 0.0373 (6) | |
H25A | 0.3747 | 0.7691 | 0.8234 | 0.045* | |
H25B | 0.4866 | 0.6931 | 0.8372 | 0.045* | |
C26 | 0.3978 (3) | 0.69311 (16) | 0.73545 (11) | 0.0299 (6) | |
H26A | 0.4726 | 0.6575 | 0.7172 | 0.036* | |
H26B | 0.3200 | 0.6540 | 0.7449 | 0.036* | |
C31 | 0.0388 (3) | 0.87665 (16) | 0.56970 (13) | 0.0357 (6) | |
H31 | 0.0307 | 0.8733 | 0.5176 | 0.043* | |
C32 | −0.0980 (3) | 0.8529 (2) | 0.59833 (16) | 0.0509 (8) | |
H32A | −0.1222 | 0.7923 | 0.5850 | 0.061* | |
H32B | −0.1717 | 0.8914 | 0.5775 | 0.061* | |
C33 | −0.0918 (3) | 0.8612 (2) | 0.67717 (17) | 0.0601 (9) | |
H33A | −0.1843 | 0.8486 | 0.6939 | 0.072* | |
H33B | −0.0254 | 0.8181 | 0.6983 | 0.072* | |
C34 | −0.0470 (4) | 0.9517 (2) | 0.70027 (17) | 0.0666 (11) | |
H34A | −0.0378 | 0.9542 | 0.7519 | 0.080* | |
H34B | −0.1188 | 0.9942 | 0.6837 | 0.080* | |
C35 | 0.0903 (3) | 0.9757 (2) | 0.67149 (16) | 0.0544 (9) | |
H35A | 0.1139 | 1.0365 | 0.6844 | 0.065* | |
H35B | 0.1643 | 0.9377 | 0.6928 | 0.065* | |
C36 | 0.0849 (3) | 0.96641 (17) | 0.59272 (15) | 0.0484 (8) | |
H36A | 0.0198 | 1.0099 | 0.5712 | 0.058* | |
H36B | 0.1779 | 0.9782 | 0.5763 | 0.058* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P | 0.0236 (3) | 0.0221 (3) | 0.0236 (3) | −0.0006 (3) | −0.0005 (2) | −0.0011 (3) |
O1 | 0.0207 (8) | 0.0250 (8) | 0.0259 (8) | −0.0037 (7) | −0.0005 (7) | −0.0047 (7) |
O2 | 0.0221 (9) | 0.0264 (9) | 0.0283 (8) | 0.0004 (7) | 0.0001 (7) | −0.0059 (7) |
O3 | 0.0386 (10) | 0.0255 (9) | 0.0307 (9) | −0.0025 (8) | 0.0080 (8) | −0.0007 (7) |
O4 | 0.0300 (9) | 0.0251 (9) | 0.0243 (8) | 0.0028 (7) | −0.0031 (7) | −0.0049 (7) |
O5 | 0.0278 (9) | 0.0256 (9) | 0.0272 (9) | 0.0047 (7) | −0.0012 (7) | −0.0014 (7) |
C1 | 0.0276 (13) | 0.0312 (14) | 0.0276 (12) | −0.0008 (11) | 0.0023 (10) | 0.0055 (11) |
C2 | 0.0232 (13) | 0.0374 (15) | 0.0389 (14) | −0.0027 (11) | −0.0009 (11) | 0.0079 (12) |
C3 | 0.0281 (14) | 0.0415 (16) | 0.0372 (15) | −0.0135 (12) | −0.0049 (11) | 0.0058 (12) |
C4 | 0.0331 (14) | 0.0329 (14) | 0.0256 (12) | −0.0104 (12) | −0.0001 (11) | 0.0018 (11) |
C4A | 0.0259 (13) | 0.0271 (12) | 0.0190 (11) | −0.0058 (10) | 0.0002 (9) | 0.0056 (10) |
C4B | 0.0294 (13) | 0.0268 (13) | 0.0166 (11) | −0.0046 (10) | 0.0016 (10) | 0.0011 (9) |
C5 | 0.0363 (15) | 0.0308 (14) | 0.0264 (13) | −0.0073 (12) | 0.0020 (11) | −0.0075 (11) |
C6 | 0.0421 (16) | 0.0290 (14) | 0.0382 (15) | −0.0015 (12) | 0.0076 (12) | −0.0128 (12) |
C7 | 0.0303 (14) | 0.0325 (14) | 0.0325 (13) | 0.0025 (11) | 0.0076 (11) | −0.0031 (11) |
C8 | 0.0256 (13) | 0.0284 (13) | 0.0242 (12) | −0.0038 (10) | 0.0025 (10) | −0.0016 (10) |
C8A | 0.0262 (13) | 0.0229 (12) | 0.0198 (11) | −0.0036 (10) | 0.0017 (9) | 0.0011 (9) |
C9 | 0.0254 (13) | 0.0223 (12) | 0.0176 (11) | −0.0031 (10) | −0.0015 (9) | 0.0025 (9) |
C10 | 0.0259 (13) | 0.0214 (12) | 0.0202 (11) | 0.0004 (10) | 0.0013 (10) | 0.0003 (9) |
C10A | 0.0244 (13) | 0.0265 (12) | 0.0197 (11) | −0.0041 (10) | 0.0014 (9) | 0.0054 (10) |
C11 | 0.039 (2) | 0.0306 (19) | 0.029 (2) | −0.0031 (15) | 0.0083 (19) | −0.0003 (15) |
C12 | 0.0333 (19) | 0.069 (3) | 0.050 (2) | 0.0115 (17) | 0.0041 (15) | 0.0207 (18) |
C13 | 0.046 (2) | 0.079 (3) | 0.084 (3) | 0.016 (2) | 0.024 (2) | 0.032 (2) |
C14 | 0.051 (3) | 0.057 (3) | 0.068 (3) | 0.002 (2) | 0.034 (2) | 0.024 (2) |
C15 | 0.062 (2) | 0.064 (2) | 0.0377 (18) | −0.0020 (19) | 0.0137 (17) | 0.0117 (17) |
C16 | 0.0314 (17) | 0.054 (2) | 0.0389 (17) | −0.0004 (15) | 0.0005 (13) | 0.0122 (15) |
C21 | 0.0268 (13) | 0.0299 (13) | 0.0222 (11) | 0.0024 (11) | −0.0017 (10) | −0.0066 (10) |
C22 | 0.0365 (15) | 0.0305 (14) | 0.0316 (14) | −0.0008 (12) | −0.0014 (11) | −0.0029 (11) |
C23 | 0.0378 (15) | 0.0355 (15) | 0.0398 (15) | −0.0032 (13) | −0.0006 (12) | −0.0123 (12) |
C24 | 0.0310 (14) | 0.0484 (17) | 0.0281 (13) | 0.0039 (13) | −0.0046 (11) | −0.0134 (12) |
C25 | 0.0408 (16) | 0.0481 (17) | 0.0228 (12) | 0.0071 (13) | 0.0007 (11) | −0.0035 (12) |
C26 | 0.0328 (14) | 0.0324 (14) | 0.0242 (12) | 0.0009 (11) | 0.0009 (11) | −0.0003 (11) |
C31 | 0.0406 (16) | 0.0315 (14) | 0.0336 (14) | 0.0140 (12) | −0.0068 (12) | −0.0043 (11) |
C32 | 0.0329 (16) | 0.0533 (19) | 0.065 (2) | 0.0136 (14) | −0.0069 (14) | −0.0176 (16) |
C33 | 0.0445 (19) | 0.076 (2) | 0.062 (2) | 0.0071 (17) | 0.0219 (16) | −0.0102 (18) |
C34 | 0.069 (2) | 0.083 (3) | 0.0474 (19) | 0.036 (2) | −0.0006 (17) | −0.0202 (18) |
C35 | 0.065 (2) | 0.0374 (17) | 0.0587 (19) | 0.0122 (16) | −0.0117 (17) | −0.0212 (15) |
C36 | 0.062 (2) | 0.0275 (15) | 0.0547 (18) | 0.0104 (14) | −0.0015 (16) | −0.0024 (13) |
P—O3 | 1.581 (2) | C2—H2 | 0.9500 |
P—O4 | 1.589 (2) | C3—H3 | 0.9500 |
P—O5 | 1.624 (2) | C4—H4 | 0.9500 |
P—O2 | 1.652 (2) | C5—H5 | 0.9500 |
P—O1 | 1.744 (2) | C6—H6 | 0.9500 |
O1—C9 | 1.361 (3) | C7—H7 | 0.9500 |
O2—C10 | 1.380 (3) | C8—H8 | 0.9500 |
O3—C11' | 1.41 (3) | C11—H11 | 1.0000 |
O3—C11 | 1.466 (4) | C12—H12A | 0.9900 |
O4—C21 | 1.461 (3) | C12—H12B | 0.9900 |
O5—C31 | 1.443 (3) | C13—H13A | 0.9900 |
C1—C2 | 1.370 (3) | C13—H13B | 0.9900 |
C1—C10A | 1.406 (3) | C14—H14A | 0.9900 |
C2—C3 | 1.389 (4) | C14—H14B | 0.9900 |
C3—C4 | 1.373 (4) | C15—H15A | 0.9900 |
C4—C4A | 1.408 (3) | C15—H15B | 0.9900 |
C4A—C10A | 1.421 (3) | C16—H16A | 0.9900 |
C4A—C4B | 1.462 (3) | C16—H16B | 0.9900 |
C4B—C5 | 1.405 (3) | C11'—H11' | 1.0000 |
C4B—C8A | 1.422 (3) | C12'—H12C | 0.9900 |
C5—C6 | 1.369 (4) | C12'—H12D | 0.9900 |
C6—C7 | 1.392 (4) | C13'—H13C | 0.9900 |
C7—C8 | 1.370 (3) | C13'—H13D | 0.9900 |
C8—C8A | 1.402 (3) | C14'—H14C | 0.9900 |
C8A—C9 | 1.421 (3) | C14'—H14D | 0.9900 |
C9—C10 | 1.332 (3) | C15'—H15C | 0.9900 |
C10—C10A | 1.413 (3) | C15'—H15D | 0.9900 |
C11—C16 | 1.508 (5) | C16'—H16C | 0.9900 |
C11—C12 | 1.510 (5) | C16'—H16D | 0.9900 |
C12—C13 | 1.527 (5) | C21—H21 | 1.0000 |
C13—C14 | 1.515 (6) | C22—H22A | 0.9900 |
C14—C15 | 1.511 (7) | C22—H22B | 0.9900 |
C15—C16 | 1.523 (4) | C23—H23A | 0.9900 |
C11'—C16' | 1.502 (18) | C23—H23B | 0.9900 |
C11'—C12' | 1.507 (19) | C24—H24A | 0.9900 |
C12'—C13' | 1.518 (19) | C24—H24B | 0.9900 |
C13'—C14' | 1.515 (19) | C25—H25A | 0.9900 |
C14'—C15' | 1.52 (2) | C25—H25B | 0.9900 |
C15'—C16' | 1.539 (18) | C26—H26A | 0.9900 |
C21—C26 | 1.508 (3) | C26—H26B | 0.9900 |
C21—C22 | 1.518 (3) | C31—H31 | 1.0000 |
C22—C23 | 1.527 (3) | C32—H32A | 0.9900 |
C23—C24 | 1.513 (4) | C32—H32B | 0.9900 |
C24—C25 | 1.519 (4) | C33—H33A | 0.9900 |
C25—C26 | 1.527 (3) | C33—H33B | 0.9900 |
C31—C36 | 1.509 (4) | C34—H34A | 0.9900 |
C31—C32 | 1.511 (4) | C34—H34B | 0.9900 |
C32—C33 | 1.516 (4) | C35—H35A | 0.9900 |
C33—C34 | 1.516 (5) | C35—H35B | 0.9900 |
C34—C35 | 1.518 (5) | C36—H36A | 0.9900 |
C35—C36 | 1.516 (4) | C36—H36B | 0.9900 |
C1—H1 | 0.9500 | ||
O3—P—O4 | 117.35 (9) | C12—C13—H13B | 109.3 |
O3—P—O5 | 92.73 (9) | H13A—C13—H13B | 107.9 |
O4—P—O5 | 91.98 (8) | C15—C14—H14A | 109.5 |
O3—P—O2 | 115.31 (9) | C13—C14—H14A | 109.5 |
O4—P—O2 | 127.24 (9) | C15—C14—H14B | 109.5 |
O5—P—O2 | 88.52 (8) | C13—C14—H14B | 109.5 |
O3—P—O1 | 94.57 (8) | H14A—C14—H14B | 108.1 |
O4—P—O1 | 84.38 (8) | C14—C15—H15A | 109.5 |
O5—P—O1 | 172.69 (9) | C16—C15—H15A | 109.5 |
O2—P—O1 | 88.66 (8) | C14—C15—H15B | 109.5 |
C9—O1—P | 111.78 (14) | C16—C15—H15B | 109.5 |
C10—O2—P | 114.68 (14) | H15A—C15—H15B | 108.1 |
C11'—O3—P | 129.2 (13) | C11—C16—H16A | 109.4 |
C11—O3—P | 131.06 (18) | C15—C16—H16A | 109.4 |
C21—O4—P | 126.99 (14) | C11—C16—H16B | 109.4 |
C31—O5—P | 124.48 (14) | C15—C16—H16B | 109.4 |
C2—C1—C10A | 120.2 (2) | H16A—C16—H16B | 108.0 |
C1—C2—C3 | 119.9 (2) | O3—C11'—H11' | 111.2 |
C4—C3—C2 | 121.1 (2) | C16'—C11'—H11' | 111.2 |
C3—C4—C4A | 121.0 (2) | C12'—C11'—H11' | 111.2 |
C4—C4A—C10A | 117.4 (2) | C11'—C12'—H12C | 109.6 |
C4—C4A—C4B | 122.7 (2) | C13'—C12'—H12C | 109.6 |
C10A—C4A—C4B | 119.9 (2) | C11'—C12'—H12D | 109.6 |
C5—C4B—C8A | 117.0 (2) | C13'—C12'—H12D | 109.6 |
C5—C4B—C4A | 122.8 (2) | H12C—C12'—H12D | 108.1 |
C8A—C4B—C4A | 120.2 (2) | C14'—C13'—H13C | 109.0 |
C6—C5—C4B | 121.6 (2) | C12'—C13'—H13C | 109.0 |
C5—C6—C7 | 120.9 (2) | C14'—C13'—H13D | 109.0 |
C8—C7—C6 | 119.4 (2) | C12'—C13'—H13D | 109.0 |
C7—C8—C8A | 120.7 (2) | H13C—C13'—H13D | 107.8 |
C8—C8A—C9 | 122.6 (2) | C13'—C14'—H14C | 109.4 |
C8—C8A—C4B | 120.4 (2) | C15'—C14'—H14C | 109.4 |
C9—C8A—C4B | 117.0 (2) | C13'—C14'—H14D | 109.4 |
C10—C9—O1 | 112.9 (2) | C15'—C14'—H14D | 109.4 |
C10—C9—C8A | 122.0 (2) | H14C—C14'—H14D | 108.0 |
O1—C9—C8A | 125.0 (2) | C14'—C15'—H15C | 110.0 |
C9—C10—O2 | 111.76 (19) | C16'—C15'—H15C | 110.0 |
C9—C10—C10A | 124.5 (2) | C14'—C15'—H15D | 110.0 |
O2—C10—C10A | 123.8 (2) | C16'—C15'—H15D | 110.0 |
C1—C10A—C10 | 123.3 (2) | H15C—C15'—H15D | 108.4 |
C1—C10A—C4A | 120.4 (2) | C11'—C16'—H16C | 109.3 |
C10—C10A—C4A | 116.3 (2) | C15'—C16'—H16C | 109.3 |
O3—C11—C16 | 106.4 (3) | C11'—C16'—H16D | 109.3 |
O3—C11—C12 | 108.5 (3) | C15'—C16'—H16D | 109.3 |
C16—C11—C12 | 111.4 (3) | H16C—C16'—H16D | 108.0 |
C11—C12—C13 | 110.9 (3) | O4—C21—H21 | 109.6 |
C14—C13—C12 | 111.8 (3) | C26—C21—H21 | 109.6 |
C15—C14—C13 | 110.8 (4) | C22—C21—H21 | 109.6 |
C14—C15—C16 | 110.6 (3) | C21—C22—H22A | 109.5 |
C11—C16—C15 | 111.1 (3) | C23—C22—H22A | 109.5 |
O3—C11'—C16' | 106 (2) | C21—C22—H22B | 109.5 |
O3—C11'—C12' | 106 (2) | C23—C22—H22B | 109.5 |
C16'—C11'—C12' | 111.3 (19) | H22A—C22—H22B | 108.1 |
C11'—C12'—C13' | 110.3 (19) | C24—C23—H23A | 109.3 |
C14'—C13'—C12' | 113 (2) | C22—C23—H23A | 109.3 |
C13'—C14'—C15' | 111 (2) | C24—C23—H23B | 109.3 |
C14'—C15'—C16' | 108 (2) | C22—C23—H23B | 109.3 |
C11'—C16'—C15' | 111.4 (19) | H23A—C23—H23B | 108.0 |
O4—C21—C26 | 106.26 (18) | C23—C24—H24A | 109.6 |
O4—C21—C22 | 109.17 (18) | C25—C24—H24A | 109.6 |
C26—C21—C22 | 112.5 (2) | C23—C24—H24B | 109.6 |
C21—C22—C23 | 110.5 (2) | C25—C24—H24B | 109.6 |
C24—C23—C22 | 111.6 (2) | H24A—C24—H24B | 108.1 |
C23—C24—C25 | 110.5 (2) | C24—C25—H25A | 109.5 |
C24—C25—C26 | 110.6 (2) | C26—C25—H25A | 109.5 |
C21—C26—C25 | 110.5 (2) | C24—C25—H25B | 109.5 |
O5—C31—C36 | 107.0 (2) | C26—C25—H25B | 109.5 |
O5—C31—C32 | 108.6 (2) | H25A—C25—H25B | 108.1 |
C36—C31—C32 | 111.3 (2) | C21—C26—H26A | 109.6 |
C31—C32—C33 | 111.5 (2) | C25—C26—H26A | 109.6 |
C34—C33—C32 | 111.2 (3) | C21—C26—H26B | 109.6 |
C33—C34—C35 | 110.9 (3) | C25—C26—H26B | 109.6 |
C36—C35—C34 | 111.6 (3) | H26A—C26—H26B | 108.1 |
C31—C36—C35 | 111.6 (2) | O5—C31—H31 | 110.0 |
C2—C1—H1 | 119.9 | C36—C31—H31 | 110.0 |
C10A—C1—H1 | 119.9 | C32—C31—H31 | 110.0 |
C1—C2—H2 | 120.1 | C31—C32—H32A | 109.3 |
C3—C2—H2 | 120.1 | C33—C32—H32A | 109.3 |
C4—C3—H3 | 119.5 | C31—C32—H32B | 109.3 |
C2—C3—H3 | 119.5 | C33—C32—H32B | 109.3 |
C3—C4—H4 | 119.5 | H32A—C32—H32B | 108.0 |
C4A—C4—H4 | 119.5 | C34—C33—H33A | 109.4 |
C6—C5—H5 | 119.2 | C32—C33—H33A | 109.4 |
C4B—C5—H5 | 119.2 | C34—C33—H33B | 109.4 |
C5—C6—H6 | 119.5 | C32—C33—H33B | 109.4 |
C7—C6—H6 | 119.5 | H33A—C33—H33B | 108.0 |
C8—C7—H7 | 120.3 | C33—C34—H34A | 109.5 |
C6—C7—H7 | 120.3 | C35—C34—H34A | 109.5 |
C7—C8—H8 | 119.7 | C33—C34—H34B | 109.5 |
C8A—C8—H8 | 119.7 | C35—C34—H34B | 109.5 |
O3—C11—H11 | 110.2 | H34A—C34—H34B | 108.1 |
C16—C11—H11 | 110.2 | C36—C35—H35A | 109.3 |
C12—C11—H11 | 110.2 | C34—C35—H35A | 109.3 |
C11—C12—H12A | 109.5 | C36—C35—H35B | 109.3 |
C13—C12—H12A | 109.5 | C34—C35—H35B | 109.3 |
C11—C12—H12B | 109.5 | H35A—C35—H35B | 108.0 |
C13—C12—H12B | 109.5 | C31—C36—H36A | 109.3 |
H12A—C12—H12B | 108.0 | C35—C36—H36A | 109.3 |
C14—C13—H13A | 109.3 | C31—C36—H36B | 109.3 |
C12—C13—H13A | 109.3 | C35—C36—H36B | 109.3 |
C14—C13—H13B | 109.3 | H36A—C36—H36B | 108.0 |
O3—P—O1—C9 | −112.19 (15) | C2—C1—C10A—C10 | 178.0 (2) |
O4—P—O1—C9 | 130.72 (15) | C2—C1—C10A—C4A | −1.3 (3) |
O2—P—O1—C9 | 3.09 (14) | C9—C10—C10A—C1 | −176.1 (2) |
O3—P—O2—C10 | 90.33 (16) | O2—C10—C10A—C1 | 4.1 (3) |
O4—P—O2—C10 | −85.99 (16) | C9—C10—C10A—C4A | 3.2 (3) |
O5—P—O2—C10 | −177.35 (15) | O2—C10—C10A—C4A | −176.57 (19) |
O1—P—O2—C10 | −4.09 (15) | C4—C4A—C10A—C1 | 0.4 (3) |
O4—P—O3—C11' | 68.5 (13) | C4B—C4A—C10A—C1 | −179.6 (2) |
O5—P—O3—C11' | 162.2 (13) | C4—C4A—C10A—C10 | −178.9 (2) |
O2—P—O3—C11' | −108.2 (13) | C4B—C4A—C10A—C10 | 1.1 (3) |
O1—P—O3—C11' | −17.5 (13) | C11'—O3—C11—C16 | −131 (4) |
O4—P—O3—C11 | 91.9 (3) | P—O3—C11—C16 | 137.5 (2) |
O5—P—O3—C11 | −174.4 (3) | C11'—O3—C11—C12 | −11 (4) |
O2—P—O3—C11 | −84.8 (3) | P—O3—C11—C12 | −102.6 (3) |
O1—P—O3—C11 | 5.9 (3) | O3—C11—C12—C13 | −171.5 (3) |
O3—P—O4—C21 | 70.2 (2) | C16—C11—C12—C13 | −54.8 (4) |
O5—P—O4—C21 | −23.95 (19) | C11—C12—C13—C14 | 54.3 (5) |
O2—P—O4—C21 | −113.59 (18) | C12—C13—C14—C15 | −55.3 (6) |
O1—P—O4—C21 | 162.40 (18) | C13—C14—C15—C16 | 56.4 (5) |
O3—P—O5—C31 | 61.73 (19) | O3—C11—C16—C15 | 174.6 (3) |
O4—P—O5—C31 | 179.24 (19) | C12—C11—C16—C15 | 56.6 (4) |
O2—P—O5—C31 | −53.54 (19) | C14—C15—C16—C11 | −57.2 (5) |
C10A—C1—C2—C3 | 1.3 (4) | C11—O3—C11'—C16' | −3 (3) |
C1—C2—C3—C4 | −0.4 (4) | P—O3—C11'—C16' | 101 (2) |
C2—C3—C4—C4A | −0.5 (4) | C11—O3—C11'—C12' | 115 (5) |
C3—C4—C4A—C10A | 0.5 (3) | P—O3—C11'—C12' | −141.3 (14) |
C3—C4—C4A—C4B | −179.5 (2) | O3—C11'—C12'—C13' | −169 (2) |
C4—C4A—C4B—C5 | −5.1 (3) | C16'—C11'—C12'—C13' | −55 (3) |
C10A—C4A—C4B—C5 | 174.9 (2) | C11'—C12'—C13'—C14' | 53 (4) |
C4—C4A—C4B—C8A | 176.2 (2) | C12'—C13'—C14'—C15' | −55 (5) |
C10A—C4A—C4B—C8A | −3.8 (3) | C13'—C14'—C15'—C16' | 56 (5) |
C8A—C4B—C5—C6 | 0.6 (3) | O3—C11'—C16'—C15' | 174 (2) |
C4A—C4B—C5—C6 | −178.1 (2) | C12'—C11'—C16'—C15' | 59 (3) |
C4B—C5—C6—C7 | −0.4 (4) | C14'—C15'—C16'—C11' | −59 (3) |
C5—C6—C7—C8 | −0.7 (4) | P—O4—C21—C26 | 163.00 (16) |
C6—C7—C8—C8A | 1.7 (4) | P—O4—C21—C22 | −75.4 (2) |
C7—C8—C8A—C9 | 175.0 (2) | O4—C21—C22—C23 | −171.86 (19) |
C7—C8—C8A—C4B | −1.6 (3) | C26—C21—C22—C23 | −54.2 (3) |
C5—C4B—C8A—C8 | 0.4 (3) | C21—C22—C23—C24 | 54.5 (3) |
C4A—C4B—C8A—C8 | 179.1 (2) | C22—C23—C24—C25 | −56.9 (3) |
C5—C4B—C8A—C9 | −176.4 (2) | C23—C24—C25—C26 | 57.8 (3) |
C4A—C4B—C8A—C9 | 2.3 (3) | O4—C21—C26—C25 | 174.94 (19) |
P—O1—C9—C10 | −1.4 (2) | C22—C21—C26—C25 | 55.5 (3) |
P—O1—C9—C8A | −177.88 (17) | C24—C25—C26—C21 | −56.9 (3) |
C8—C8A—C9—C10 | −174.9 (2) | P—O5—C31—C36 | −127.2 (2) |
C4B—C8A—C9—C10 | 1.8 (3) | P—O5—C31—C32 | 112.5 (2) |
C8—C8A—C9—O1 | 1.3 (3) | O5—C31—C32—C33 | 62.4 (3) |
C4B—C8A—C9—O1 | 178.00 (19) | C36—C31—C32—C33 | −55.2 (3) |
O1—C9—C10—O2 | −1.6 (3) | C31—C32—C33—C34 | 55.8 (3) |
C8A—C9—C10—O2 | 175.00 (18) | C32—C33—C34—C35 | −55.4 (4) |
O1—C9—C10—C10A | 178.6 (2) | C33—C34—C35—C36 | 54.9 (4) |
C8A—C9—C10—C10A | −4.8 (3) | O5—C31—C36—C35 | −63.9 (3) |
P—O2—C10—C9 | 4.2 (2) | C32—C31—C36—C35 | 54.6 (3) |
P—O2—C10—C10A | −176.06 (17) | C34—C35—C36—C31 | −54.7 (3) |
Experimental details
Crystal data | |
Chemical formula | C32H41O5P |
Mr | 536.62 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 143 |
a, b, c (Å) | 9.665 (2), 15.394 (3), 19.200 (4) |
β (°) | 93.92 (2) |
V (Å3) | 2850.1 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.65 × 0.30 × 0.30 |
Data collection | |
Diffractometer | Stoe STADI-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5588, 5037, 3708 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.119, 1.04 |
No. of reflections | 5037 |
No. of parameters | 368 |
No. of restraints | 18 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.31 |
Computer programs: DIF4 (Stoe & Cie, 1992), DIF4, REDU4 (Stoe & Cie, 1992), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1994), SHELXL97.
P—O3 | 1.581 (2) | P—O2 | 1.652 (2) |
P—O4 | 1.589 (2) | P—O1 | 1.744 (2) |
P—O5 | 1.624 (2) | ||
O3—P—O4 | 117.35 (9) | O5—P—O2 | 88.52 (8) |
O3—P—O5 | 92.73 (9) | O3—P—O1 | 94.57 (8) |
O4—P—O5 | 91.98 (8) | O4—P—O1 | 84.38 (8) |
O3—P—O2 | 115.31 (9) | O5—P—O1 | 172.69 (9) |
O4—P—O2 | 127.24 (9) | O2—P—O1 | 88.66 (8) |
We are interested in the correlation between structure and reactivity (see e.g. Amos et al., 1992). The structure of the title compound, (I), the adduct of tricyclohexyl phosphite and phenanthraquinone, was determined as part of a combined crystallographic and theoretical investigation of pKa values of pentaoxyphosphoranes (Davies et al., 2002).
The structure is shown in Fig. 1; a minor (11%) disorder component of the ring C11–16 is not shown. Of the three cyclohexyloxy groups, one is axial (O5, C31 etc.) and the other two are equatorial. This is reflected in the normal bond-length pattern for trigonal–bipyramidal geometry (axial bonds longer than equatorial), as was also observed in pentakis(cyclohexyloxy)phosphorane (Davies et al., 2001; average values in four independent molecules 1.662 Å for axial and 1.606 Å for equatorial P—O bonds). The triisopropyloxy analogue of the title compound was subjected to structure analysis in 1967. There were two modifications, of which the more precisely determined modification (Spratley et al., 1967) displayed a similar P—O bond-length pattern to the title compound: ring apical 1.751 (7) Å, equatorial 1.633 (7) Å; iPr apical 1.638 (6) Å, and equatorial 1.588 (7) and 1.574 (7) Å.