Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104008492/sk1717sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104008492/sk1717Isup2.hkl |
CCDC reference: 243605
For the synthesis of (I), a solution of diisopropylamine (0.182 ml, 1.29 mmol) in THF (6 ml) was cooled to 213 K, and n-butyllithium (0.471 ml, 1.18 mmol) was added. To this solution was added the diazaphosphole oxide (1.18 mmol) dissolved in thf (3 ml), previously prepared as reported elsewhere (Moreno et al., 2004). The resulting solution was maintained at 213 K for 1 h, and benzaldehyde (1.29 mmol) was added. After an additional reaction time of 4.5 h at 213 K, the reaction mixture was quenched with aqueous ammonium chloride (0.5 ml) and diluted with CHCl3 (60 ml). The solution was washed with water (2 × 25 ml), dried over Na2SO4 and concentrated in vacuo to give the crude product (yield 65%). Single crystals of (I) were obtained by repeated slow evaporation of an AcOEt solution of the crude. M.p. 467 K. [α]D = 13.10 (c 1, CHCl3); 31P NMR (in CHCl3, referenced to external 85% H3PO4): δ 36.3 (Cα-R isomer) and 34.7 (Cα-S isomer). To a crop of crystals of (I) (0.38 g, 0.93 mmol) dissolved in dioxane (2 ml) was added aqueous 4 N HCl (1 ml). After 2 h, the suspension had dissolved completely. The solution was stirred at room temperature, and the reaction progress was monitored by 31P NMR spectroscopy until completion (ca 12 h). The solution was then concentrated in vacuo and the residue was passed through an ion exchange column (Amberite IR-120+) eluted with water. The first 50 ml fraction was evaporated to yield the diastereoisomeric mixture of α-hydroxy-phosphonic acid resulting from the hydrolysis of (I). The phosphonic acid was dissolved in ethanol and cyclohexylamine was added. The solution was cooled to 263 K for 12 h and the precipitated cyclohexylammonium salt was collected by filtration (50% yield). M.p. 483 K (decomposed). [α]D = − 4.42 (c 0.77, MeOH:H2O 50% v/v), e.e. = 31%.
Atoms O21 and O71 belonging to the hydroxy groups bonded to atoms C23 and C73 were found to be disordered with, respectively, atoms O22 and O72. The coordination of atoms C23 and C73 is completed by disordered H atoms, placed at idealized positions. Site-occupancy factors (SOFs) were refined in two parts, independently for each molecule, with the sum of the SOFs for the two disordered components in each molecule constrained to 1. H atoms of the hydroxy groups were found in difference maps and were included in the disorder model with SOFs corresponding to those of parent the O atoms. Finally, all other H atoms were placed at idealized positions. All H atoms were treated using a riding model, with constrained distances and Uiso(H) values fixed to xUeq(parent) [C—H = 0.98 Å and x = 1.2 for methine H atoms, C—H = 0.97 Å and x = 1.2 for methylene H atoms, C—H = 0.96 Å and x = 1.5 for methyl H atoms, and C—H = 0.93 Å and x = 1.2 for aromatic H atoms]. O—H distances were fixed at the values found from difference maps (x = 1.5).
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL-Plus (Sheldrick, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1998); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 1998).
C29H35N2O2P | F(000) = 1016 |
Mr = 474.56 | Dx = 1.189 Mg m−3 |
Monoclinic, P21 | Melting point: 467 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6413 (11) Å | Cell parameters from 85 reflections |
b = 17.3888 (11) Å | θ = 4.7–13.0° |
c = 15.8778 (11) Å | µ = 0.13 mm−1 |
β = 95.373 (8)° | T = 300 K |
V = 2650.2 (4) Å3 | Irregular, colorless |
Z = 4 | 0.60 × 0.55 × 0.45 mm |
Bruker P4 diffractometer | 5554 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube, FN4 | Rint = 0.028 |
Graphite monochromator | θmax = 29.0°, θmin = 1.7° |
2θ/ω scans | h = −13→11 |
Absorption correction: ψ scan ψ scans (XSCANS; Siemens, 1996) | k = −1→23 |
Tmin = 0.926, Tmax = 0.942 | l = −21→21 |
15139 measured reflections | 3 standard reflections every 97 reflections |
7715 independent reflections | intensity decay: 1.5% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: See text |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.0681P)2 + 0.0908P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
7715 reflections | Δρmax = 0.28 e Å−3 |
633 parameters | Δρmin = −0.21 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 446 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (8) |
C29H35N2O2P | V = 2650.2 (4) Å3 |
Mr = 474.56 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.6413 (11) Å | µ = 0.13 mm−1 |
b = 17.3888 (11) Å | T = 300 K |
c = 15.8778 (11) Å | 0.60 × 0.55 × 0.45 mm |
β = 95.373 (8)° |
Bruker P4 diffractometer | 5554 reflections with I > 2σ(I) |
Absorption correction: ψ scan ψ scans (XSCANS; Siemens, 1996) | Rint = 0.028 |
Tmin = 0.926, Tmax = 0.942 | 3 standard reflections every 97 reflections |
15139 measured reflections | intensity decay: 1.5% |
7715 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.129 | Δρmax = 0.28 e Å−3 |
S = 1.03 | Δρmin = −0.21 e Å−3 |
7715 reflections | Absolute structure: Flack (1983), 446 Friedel pairs |
633 parameters | Absolute structure parameter: −0.02 (8) |
1 restraint |
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) | |
P1 | 0.66156 (7) | 0.52220 (4) | 0.14767 (4) | 0.04806 (17) | |
N1 | 0.7150 (2) | 0.47541 (15) | 0.06674 (14) | 0.0533 (6) | |
N2 | 0.5074 (2) | 0.47915 (15) | 0.14649 (13) | 0.0501 (5) | |
O1 | 0.7542 (2) | 0.51962 (15) | 0.22760 (12) | 0.0636 (5) | |
O21 | 0.5579 (3) | 0.6556 (2) | 0.19133 (19) | 0.0685 (11) | 0.703 (6) |
H21 | 0.6233 | 0.6802 | 0.2186 | 0.103* | 0.703 (6) |
O22 | 0.7570 (7) | 0.6618 (4) | 0.1191 (4) | 0.061 (2) | 0.297 (6) |
H22 | 0.7726 | 0.6808 | 0.1741 | 0.091* | 0.297 (6) |
C1 | 0.5928 (3) | 0.44083 (18) | 0.01737 (16) | 0.0517 (6) | |
H1B | 0.5489 | 0.4823 | −0.0174 | 0.062* | |
C2 | 0.4916 (3) | 0.41987 (18) | 0.08053 (17) | 0.0513 (6) | |
H2A | 0.5232 | 0.3711 | 0.1068 | 0.062* | |
C3 | 0.3489 (3) | 0.4061 (2) | 0.0358 (2) | 0.0683 (9) | |
H3A | 0.3133 | 0.4534 | 0.0097 | 0.082* | |
H3B | 0.2856 | 0.3897 | 0.0763 | 0.082* | |
C4 | 0.3579 (4) | 0.3442 (2) | −0.0317 (2) | 0.0707 (9) | |
H4A | 0.3723 | 0.2948 | −0.0040 | 0.085* | |
H4B | 0.2695 | 0.3420 | −0.0663 | 0.085* | |
C5 | 0.4718 (4) | 0.3568 (2) | −0.0884 (2) | 0.0783 (10) | |
H5A | 0.4451 | 0.3988 | −0.1267 | 0.094* | |
H5B | 0.4806 | 0.3110 | −0.1223 | 0.094* | |
C6 | 0.6127 (4) | 0.3750 (2) | −0.0422 (2) | 0.0702 (9) | |
H6A | 0.6489 | 0.3304 | −0.0107 | 0.084* | |
H6B | 0.6783 | 0.3893 | −0.0822 | 0.084* | |
C7 | 0.8561 (3) | 0.4653 (2) | 0.0416 (2) | 0.0617 (7) | |
H7A | 0.8492 | 0.4663 | −0.0204 | 0.074* | |
C8 | 0.9184 (3) | 0.3886 (2) | 0.0691 (3) | 0.0685 (9) | |
C9 | 0.9185 (4) | 0.3640 (3) | 0.1516 (3) | 0.0917 (12) | |
H9A | 0.8769 | 0.3940 | 0.1907 | 0.110* | |
C10 | 0.9812 (5) | 0.2937 (3) | 0.1767 (4) | 0.1134 (17) | |
H10A | 0.9793 | 0.2768 | 0.2322 | 0.136* | |
C11 | 1.0455 (5) | 0.2498 (3) | 0.1195 (5) | 0.132 (3) | |
H11A | 1.0896 | 0.2039 | 0.1361 | 0.159* | |
C12 | 1.0432 (5) | 0.2748 (3) | 0.0380 (5) | 0.121 (2) | |
H12A | 1.0849 | 0.2449 | −0.0011 | 0.145* | |
C13 | 0.9815 (4) | 0.3425 (3) | 0.0124 (3) | 0.0917 (13) | |
H13A | 0.9817 | 0.3580 | −0.0437 | 0.110* | |
C14 | 0.9531 (3) | 0.5315 (2) | 0.0730 (3) | 0.0778 (10) | |
H14A | 0.9117 | 0.5797 | 0.0549 | 0.117* | |
H14B | 1.0412 | 0.5258 | 0.0500 | 0.117* | |
H14C | 0.9670 | 0.5303 | 0.1336 | 0.117* | |
C15 | 0.4451 (3) | 0.4689 (2) | 0.22828 (18) | 0.0606 (8) | |
H15A | 0.5006 | 0.5008 | 0.2698 | 0.073* | |
C16 | 0.4618 (4) | 0.3868 (2) | 0.25939 (18) | 0.0637 (8) | |
C17 | 0.5935 (4) | 0.3611 (3) | 0.2895 (2) | 0.0792 (10) | |
H17A | 0.6679 | 0.3954 | 0.2921 | 0.095* | |
C18 | 0.6169 (5) | 0.2867 (3) | 0.3157 (2) | 0.0935 (13) | |
H18A | 0.7061 | 0.2713 | 0.3360 | 0.112* | |
C19 | 0.5115 (6) | 0.2360 (3) | 0.3119 (2) | 0.0938 (13) | |
H19A | 0.5284 | 0.1852 | 0.3282 | 0.113* | |
C20 | 0.3788 (5) | 0.2589 (3) | 0.2839 (3) | 0.0950 (14) | |
H20A | 0.3056 | 0.2240 | 0.2831 | 0.114* | |
C21 | 0.3531 (5) | 0.3349 (3) | 0.2566 (2) | 0.0813 (11) | |
H21B | 0.2635 | 0.3501 | 0.2368 | 0.098* | |
C22 | 0.2963 (4) | 0.5007 (3) | 0.2234 (3) | 0.0922 (13) | |
H22B | 0.2956 | 0.5527 | 0.2032 | 0.138* | |
H22C | 0.2635 | 0.4995 | 0.2787 | 0.138* | |
H22D | 0.2366 | 0.4697 | 0.1854 | 0.138* | |
C23 | 0.6242 (3) | 0.62387 (18) | 0.12136 (19) | 0.0572 (7) | |
H231 | 0.7126 | 0.6508 | 0.1171 | 0.069* | 0.703 (6) |
H232 | 0.5769 | 0.6465 | 0.1674 | 0.069* | 0.297 (6) |
C24 | 0.5337 (4) | 0.63508 (19) | 0.0407 (2) | 0.0625 (8) | |
C25 | 0.5907 (5) | 0.6340 (2) | −0.0365 (2) | 0.0746 (10) | |
H25A | 0.6862 | 0.6270 | −0.0376 | 0.090* | |
C26 | 0.5087 (7) | 0.6429 (3) | −0.1110 (3) | 0.1087 (16) | |
H26A | 0.5486 | 0.6415 | −0.1621 | 0.130* | |
C27 | 0.3688 (8) | 0.6539 (4) | −0.1106 (4) | 0.1190 (19) | |
H27A | 0.3139 | 0.6609 | −0.1614 | 0.143* | |
C28 | 0.3102 (6) | 0.6548 (3) | −0.0374 (4) | 0.1124 (17) | |
H28A | 0.2144 | 0.6617 | −0.0381 | 0.135* | |
C29 | 0.3916 (4) | 0.6453 (3) | 0.0413 (3) | 0.0809 (11) | |
H29A | 0.3503 | 0.6460 | 0.0920 | 0.097* | |
P51 | 0.84661 (7) | 0.74500 (4) | 0.33839 (4) | 0.05075 (19) | |
N51 | 0.9885 (2) | 0.79776 (15) | 0.35503 (14) | 0.0547 (6) | |
N52 | 0.7646 (2) | 0.78184 (15) | 0.41630 (14) | 0.0511 (5) | |
O51 | 0.7715 (2) | 0.74788 (16) | 0.25253 (11) | 0.0687 (6) | |
O71 | 0.7506 (3) | 0.60746 (19) | 0.36671 (19) | 0.0717 (10) | 0.779 (6) |
H71 | 0.7532 | 0.5776 | 0.3150 | 0.108* | 0.779 (6) |
O72 | 0.9494 (13) | 0.6073 (8) | 0.3006 (8) | 0.088 (4) | 0.221 (6) |
H72 | 0.9005 | 0.5779 | 0.2850 | 0.131* | 0.221 (6) |
C51 | 0.9963 (3) | 0.82818 (19) | 0.44201 (18) | 0.0547 (7) | |
H51B | 1.0321 | 0.7863 | 0.4792 | 0.066* | |
C52 | 0.8487 (3) | 0.84222 (18) | 0.46154 (17) | 0.0526 (6) | |
H52A | 0.8198 | 0.8913 | 0.4350 | 0.063* | |
C53 | 0.8406 (4) | 0.8517 (2) | 0.5547 (2) | 0.0732 (9) | |
H53A | 0.8694 | 0.8045 | 0.5839 | 0.088* | |
H53B | 0.7455 | 0.8629 | 0.5659 | 0.088* | |
C54 | 0.9359 (4) | 0.9174 (2) | 0.5863 (2) | 0.0761 (10) | |
H54A | 0.8947 | 0.9655 | 0.5656 | 0.091* | |
H54B | 0.9411 | 0.9187 | 0.6476 | 0.091* | |
C55 | 1.0814 (4) | 0.9122 (2) | 0.5598 (2) | 0.0809 (11) | |
H55A | 1.1303 | 0.8710 | 0.5912 | 0.097* | |
H55B | 1.1301 | 0.9598 | 0.5748 | 0.097* | |
C56 | 1.0866 (4) | 0.8977 (2) | 0.4656 (2) | 0.0732 (9) | |
H56A | 1.0519 | 0.9423 | 0.4334 | 0.088* | |
H56B | 1.1817 | 0.8881 | 0.4533 | 0.088* | |
C57 | 1.0938 (3) | 0.8155 (2) | 0.2966 (2) | 0.0641 (8) | |
H57A | 1.1842 | 0.8185 | 0.3302 | 0.077* | |
C58 | 1.0679 (4) | 0.8928 (2) | 0.25314 (19) | 0.0650 (8) | |
C59 | 0.9345 (4) | 0.9152 (3) | 0.2208 (2) | 0.0820 (11) | |
H59A | 0.8599 | 0.8825 | 0.2274 | 0.098* | |
C60 | 0.9101 (6) | 0.9842 (3) | 0.1795 (3) | 0.1043 (15) | |
H60A | 0.8197 | 0.9979 | 0.1594 | 0.125* | |
C61 | 1.0153 (8) | 1.0312 (3) | 0.1682 (3) | 0.1175 (18) | |
H61A | 0.9982 | 1.0770 | 0.1389 | 0.141* | |
C62 | 1.1533 (7) | 1.0126 (3) | 0.2004 (3) | 0.119 (2) | |
H62A | 1.2266 | 1.0461 | 0.1934 | 0.142* | |
C63 | 1.1767 (5) | 0.9416 (3) | 0.2434 (2) | 0.0922 (13) | |
H63A | 1.2664 | 0.9281 | 0.2651 | 0.111* | |
C64 | 1.1050 (5) | 0.7530 (3) | 0.2298 (3) | 0.0935 (12) | |
H64A | 1.1214 | 0.7042 | 0.2572 | 0.140* | |
H64B | 1.1809 | 0.7647 | 0.1969 | 0.140* | |
H64C | 1.0198 | 0.7508 | 0.1934 | 0.140* | |
C65 | 0.6095 (3) | 0.7853 (2) | 0.4069 (2) | 0.0627 (8) | |
H65A | 0.5797 | 0.7637 | 0.3511 | 0.075* | |
C66 | 0.5577 (3) | 0.8682 (2) | 0.4053 (2) | 0.0629 (8) | |
C67 | 0.5752 (4) | 0.9135 (3) | 0.3355 (3) | 0.0778 (10) | |
H67A | 0.6176 | 0.8930 | 0.2903 | 0.093* | |
C68 | 0.5297 (4) | 0.9900 (3) | 0.3325 (4) | 0.1029 (15) | |
H68A | 0.5426 | 1.0206 | 0.2858 | 0.123* | |
C69 | 0.4656 (4) | 1.0193 (3) | 0.3996 (4) | 0.1050 (15) | |
H69A | 0.4350 | 1.0700 | 0.3975 | 0.126* | |
C70 | 0.4462 (4) | 0.9766 (3) | 0.4676 (4) | 0.1007 (15) | |
H70A | 0.4027 | 0.9974 | 0.5122 | 0.121* | |
C71 | 0.4920 (4) | 0.9007 (3) | 0.4706 (3) | 0.0830 (11) | |
H71B | 0.4782 | 0.8710 | 0.5178 | 0.100* | |
C72 | 0.5490 (4) | 0.7330 (3) | 0.4716 (3) | 0.0980 (14) | |
H72B | 0.5874 | 0.6823 | 0.4680 | 0.147* | |
H72C | 0.4496 | 0.7307 | 0.4601 | 0.147* | |
H72D | 0.5722 | 0.7532 | 0.5275 | 0.147* | |
C73 | 0.8834 (3) | 0.64337 (19) | 0.3659 (2) | 0.0604 (7) | |
H731 | 0.9327 | 0.6199 | 0.3211 | 0.072* | 0.779 (6) |
H732 | 0.7939 | 0.6175 | 0.3698 | 0.072* | 0.221 (6) |
C74 | 0.9696 (4) | 0.63264 (18) | 0.4495 (2) | 0.0662 (9) | |
C75 | 1.1139 (4) | 0.6314 (2) | 0.4532 (3) | 0.0866 (12) | |
H75A | 1.1574 | 0.6369 | 0.4037 | 0.104* | |
C76 | 1.1948 (6) | 0.6220 (3) | 0.5299 (4) | 0.1175 (19) | |
H76A | 1.2915 | 0.6219 | 0.5317 | 0.141* | |
C77 | 1.1304 (7) | 0.6127 (3) | 0.6030 (4) | 0.119 (2) | |
H77A | 1.1840 | 0.6053 | 0.6542 | 0.143* | |
C78 | 0.9899 (7) | 0.6143 (3) | 0.6010 (3) | 0.1100 (17) | |
H78A | 0.9477 | 0.6084 | 0.6509 | 0.132* | |
C79 | 0.9059 (5) | 0.6247 (2) | 0.5232 (2) | 0.0830 (11) | |
H79A | 0.8093 | 0.6261 | 0.5222 | 0.100* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0485 (4) | 0.0479 (4) | 0.0460 (3) | −0.0044 (3) | −0.0057 (3) | −0.0060 (3) |
N1 | 0.0426 (11) | 0.0590 (15) | 0.0571 (13) | −0.0018 (11) | −0.0016 (9) | −0.0127 (11) |
N2 | 0.0510 (12) | 0.0526 (14) | 0.0460 (11) | −0.0038 (11) | 0.0001 (9) | −0.0051 (10) |
O1 | 0.0642 (12) | 0.0688 (13) | 0.0538 (10) | −0.0062 (12) | −0.0166 (9) | −0.0098 (11) |
O21 | 0.073 (2) | 0.063 (2) | 0.0673 (19) | 0.0007 (17) | −0.0074 (15) | −0.0196 (16) |
O22 | 0.069 (5) | 0.048 (4) | 0.065 (4) | −0.020 (3) | 0.003 (3) | −0.010 (3) |
C1 | 0.0554 (15) | 0.0523 (16) | 0.0466 (13) | −0.0113 (13) | 0.0001 (11) | −0.0042 (12) |
C2 | 0.0518 (15) | 0.0504 (16) | 0.0508 (14) | −0.0058 (12) | −0.0007 (11) | −0.0058 (12) |
C3 | 0.0605 (18) | 0.072 (2) | 0.0698 (19) | −0.0187 (16) | −0.0073 (14) | −0.0065 (17) |
C4 | 0.075 (2) | 0.062 (2) | 0.0706 (19) | −0.0185 (17) | −0.0181 (16) | −0.0090 (17) |
C5 | 0.107 (3) | 0.068 (2) | 0.0563 (17) | −0.013 (2) | −0.0112 (18) | −0.0190 (17) |
C6 | 0.075 (2) | 0.073 (2) | 0.0626 (18) | −0.0089 (18) | 0.0064 (15) | −0.0221 (17) |
C7 | 0.0531 (15) | 0.067 (2) | 0.0659 (17) | −0.0060 (15) | 0.0121 (13) | −0.0028 (15) |
C8 | 0.0414 (14) | 0.066 (2) | 0.098 (3) | −0.0026 (15) | 0.0050 (15) | −0.0074 (19) |
C9 | 0.073 (2) | 0.084 (3) | 0.116 (3) | 0.012 (2) | −0.003 (2) | 0.013 (3) |
C10 | 0.091 (3) | 0.089 (4) | 0.154 (5) | 0.006 (3) | −0.019 (3) | 0.032 (3) |
C11 | 0.074 (3) | 0.056 (3) | 0.260 (8) | −0.003 (2) | −0.020 (4) | 0.016 (4) |
C12 | 0.074 (3) | 0.068 (3) | 0.222 (7) | 0.003 (2) | 0.020 (4) | −0.034 (4) |
C13 | 0.0543 (19) | 0.078 (3) | 0.146 (4) | −0.0033 (19) | 0.025 (2) | −0.027 (3) |
C14 | 0.0536 (17) | 0.076 (2) | 0.103 (3) | −0.0115 (17) | 0.0045 (17) | 0.004 (2) |
C15 | 0.0590 (17) | 0.070 (2) | 0.0533 (15) | −0.0037 (15) | 0.0106 (13) | −0.0054 (15) |
C16 | 0.077 (2) | 0.073 (2) | 0.0418 (13) | −0.0081 (18) | 0.0110 (13) | 0.0002 (14) |
C17 | 0.087 (2) | 0.084 (3) | 0.0639 (19) | −0.007 (2) | −0.0037 (17) | 0.0148 (19) |
C18 | 0.115 (3) | 0.089 (3) | 0.073 (2) | 0.000 (3) | −0.012 (2) | 0.021 (2) |
C19 | 0.137 (4) | 0.078 (3) | 0.065 (2) | −0.006 (3) | 0.008 (2) | 0.009 (2) |
C20 | 0.118 (3) | 0.087 (3) | 0.082 (2) | −0.037 (3) | 0.025 (2) | −0.004 (2) |
C21 | 0.089 (2) | 0.091 (3) | 0.065 (2) | −0.014 (2) | 0.0149 (18) | 0.001 (2) |
C22 | 0.072 (2) | 0.103 (3) | 0.106 (3) | 0.016 (2) | 0.034 (2) | 0.005 (2) |
C23 | 0.0624 (17) | 0.0471 (17) | 0.0605 (16) | −0.0070 (14) | −0.0028 (14) | −0.0106 (14) |
C24 | 0.075 (2) | 0.0404 (17) | 0.0687 (19) | −0.0061 (15) | −0.0076 (16) | 0.0008 (14) |
C25 | 0.099 (3) | 0.057 (2) | 0.067 (2) | −0.007 (2) | 0.0013 (18) | 0.0078 (17) |
C26 | 0.162 (5) | 0.088 (3) | 0.072 (3) | −0.001 (3) | −0.010 (3) | 0.020 (2) |
C27 | 0.158 (5) | 0.097 (4) | 0.092 (3) | 0.000 (4) | −0.043 (3) | 0.017 (3) |
C28 | 0.101 (3) | 0.092 (3) | 0.134 (4) | 0.011 (3) | −0.045 (3) | 0.006 (3) |
C29 | 0.074 (2) | 0.074 (2) | 0.091 (3) | 0.009 (2) | −0.0097 (19) | 0.008 (2) |
P51 | 0.0585 (4) | 0.0482 (4) | 0.0442 (3) | −0.0088 (3) | −0.0023 (3) | −0.0045 (3) |
N51 | 0.0581 (13) | 0.0534 (14) | 0.0523 (12) | −0.0134 (11) | 0.0035 (10) | −0.0044 (11) |
N52 | 0.0499 (12) | 0.0521 (13) | 0.0504 (12) | −0.0077 (11) | −0.0007 (9) | −0.0046 (11) |
O51 | 0.0856 (14) | 0.0712 (14) | 0.0459 (10) | −0.0125 (13) | −0.0119 (9) | −0.0047 (11) |
O71 | 0.080 (2) | 0.0625 (19) | 0.0710 (18) | −0.0206 (16) | 0.0010 (15) | −0.0107 (15) |
O72 | 0.090 (8) | 0.077 (8) | 0.097 (9) | −0.009 (7) | 0.016 (6) | −0.037 (7) |
C51 | 0.0521 (15) | 0.0542 (17) | 0.0558 (15) | −0.0076 (13) | −0.0061 (12) | −0.0093 (13) |
C52 | 0.0556 (15) | 0.0500 (16) | 0.0506 (14) | −0.0083 (13) | −0.0037 (11) | −0.0066 (12) |
C53 | 0.082 (2) | 0.079 (2) | 0.0571 (17) | −0.0022 (19) | −0.0015 (15) | −0.0171 (18) |
C54 | 0.097 (3) | 0.069 (2) | 0.0586 (18) | −0.003 (2) | −0.0114 (17) | −0.0190 (17) |
C55 | 0.088 (3) | 0.061 (2) | 0.086 (2) | −0.0129 (19) | −0.031 (2) | −0.0168 (19) |
C56 | 0.075 (2) | 0.063 (2) | 0.080 (2) | −0.0190 (18) | −0.0039 (17) | −0.0131 (17) |
C57 | 0.0539 (16) | 0.070 (2) | 0.0694 (18) | 0.0017 (15) | 0.0109 (14) | 0.0052 (16) |
C58 | 0.076 (2) | 0.067 (2) | 0.0538 (15) | −0.0171 (17) | 0.0174 (15) | −0.0018 (15) |
C59 | 0.089 (3) | 0.074 (2) | 0.083 (2) | −0.002 (2) | 0.0070 (19) | 0.022 (2) |
C60 | 0.134 (4) | 0.081 (3) | 0.097 (3) | −0.001 (3) | 0.005 (3) | 0.025 (3) |
C61 | 0.190 (6) | 0.081 (3) | 0.082 (3) | −0.022 (4) | 0.013 (3) | 0.009 (3) |
C62 | 0.172 (5) | 0.091 (4) | 0.099 (3) | −0.069 (4) | 0.043 (3) | −0.001 (3) |
C63 | 0.098 (3) | 0.102 (3) | 0.080 (2) | −0.036 (3) | 0.030 (2) | −0.006 (2) |
C64 | 0.114 (3) | 0.084 (3) | 0.089 (3) | 0.015 (3) | 0.043 (2) | 0.000 (2) |
C65 | 0.0505 (15) | 0.072 (2) | 0.0647 (17) | −0.0140 (15) | 0.0030 (13) | −0.0010 (16) |
C66 | 0.0437 (15) | 0.072 (2) | 0.0720 (18) | −0.0080 (14) | 0.0000 (13) | −0.0034 (17) |
C67 | 0.0595 (19) | 0.087 (3) | 0.085 (2) | −0.0006 (19) | −0.0030 (16) | 0.015 (2) |
C68 | 0.076 (3) | 0.103 (4) | 0.127 (4) | −0.003 (3) | −0.005 (3) | 0.036 (3) |
C69 | 0.067 (2) | 0.077 (3) | 0.173 (5) | −0.002 (2) | 0.019 (3) | 0.000 (4) |
C70 | 0.070 (2) | 0.094 (4) | 0.142 (4) | −0.002 (2) | 0.029 (3) | −0.027 (3) |
C71 | 0.063 (2) | 0.093 (3) | 0.095 (3) | −0.011 (2) | 0.0183 (18) | −0.004 (2) |
C72 | 0.083 (3) | 0.087 (3) | 0.128 (4) | −0.018 (2) | 0.030 (2) | 0.016 (3) |
C73 | 0.0682 (19) | 0.0473 (17) | 0.0645 (17) | −0.0086 (15) | 0.0005 (15) | −0.0095 (14) |
C74 | 0.082 (2) | 0.0323 (15) | 0.081 (2) | −0.0052 (15) | −0.0132 (18) | −0.0015 (15) |
C75 | 0.083 (3) | 0.062 (2) | 0.111 (3) | 0.000 (2) | −0.017 (2) | 0.008 (2) |
C76 | 0.094 (3) | 0.091 (3) | 0.157 (5) | −0.010 (3) | −0.046 (3) | 0.027 (4) |
C77 | 0.142 (5) | 0.089 (3) | 0.114 (4) | −0.020 (3) | −0.055 (4) | 0.023 (3) |
C78 | 0.152 (5) | 0.091 (3) | 0.079 (3) | −0.017 (3) | −0.033 (3) | 0.018 (2) |
C79 | 0.104 (3) | 0.070 (2) | 0.071 (2) | −0.010 (2) | −0.011 (2) | 0.0096 (19) |
P1—O1 | 1.4823 (18) | P51—O51 | 1.4833 (19) |
P1—N1 | 1.644 (2) | P51—N51 | 1.648 (2) |
P1—N2 | 1.663 (2) | P51—N52 | 1.658 (2) |
P1—C23 | 1.844 (3) | P51—C73 | 1.847 (4) |
N1—C7 | 1.464 (4) | N51—C57 | 1.471 (4) |
N1—C1 | 1.480 (3) | N51—C51 | 1.474 (4) |
N2—C2 | 1.467 (4) | N52—C52 | 1.472 (4) |
N2—C15 | 1.491 (4) | N52—C65 | 1.490 (4) |
O21—C23 | 1.443 (4) | O71—C73 | 1.426 (4) |
O21—H21 | 0.8475 | O71—H71 | 0.9738 |
O22—C23 | 1.444 (7) | O72—C73 | 1.412 (12) |
O22—H22 | 0.9332 | O72—H72 | 0.7227 |
C1—C6 | 1.508 (4) | C51—C52 | 1.505 (4) |
C1—C2 | 1.508 (4) | C51—C56 | 1.516 (4) |
C1—H1B | 0.9800 | C51—H51B | 0.9800 |
C2—C3 | 1.506 (4) | C52—C53 | 1.498 (4) |
C2—H2A | 0.9800 | C52—H52A | 0.9800 |
C3—C4 | 1.528 (5) | C53—C54 | 1.522 (5) |
C3—H3A | 0.9700 | C53—H53A | 0.9700 |
C3—H3B | 0.9700 | C53—H53B | 0.9700 |
C4—C5 | 1.500 (5) | C54—C55 | 1.504 (6) |
C4—H4A | 0.9700 | C54—H54A | 0.9700 |
C4—H4B | 0.9700 | C54—H54B | 0.9700 |
C5—C6 | 1.516 (5) | C55—C56 | 1.522 (5) |
C5—H5A | 0.9700 | C55—H55A | 0.9700 |
C5—H5B | 0.9700 | C55—H55B | 0.9700 |
C6—H6A | 0.9700 | C56—H56A | 0.9700 |
C6—H6B | 0.9700 | C56—H56B | 0.9700 |
C7—C8 | 1.511 (5) | C57—C58 | 1.522 (5) |
C7—C14 | 1.536 (5) | C57—C64 | 1.529 (5) |
C7—H7A | 0.9800 | C57—H57A | 0.9800 |
C8—C9 | 1.377 (6) | C58—C63 | 1.368 (5) |
C8—C13 | 1.387 (5) | C58—C59 | 1.395 (5) |
C9—C10 | 1.405 (7) | C59—C60 | 1.378 (6) |
C9—H9A | 0.9300 | C59—H59A | 0.9300 |
C10—C11 | 1.378 (8) | C60—C61 | 1.328 (8) |
C10—H10A | 0.9300 | C60—H60A | 0.9300 |
C11—C12 | 1.363 (8) | C61—C62 | 1.417 (8) |
C11—H11A | 0.9300 | C61—H61A | 0.9300 |
C12—C13 | 1.365 (8) | C62—C63 | 1.420 (8) |
C12—H12A | 0.9300 | C62—H62A | 0.9300 |
C13—H13A | 0.9300 | C63—H63A | 0.9300 |
C14—H14A | 0.9600 | C64—H64A | 0.9600 |
C14—H14B | 0.9600 | C64—H64B | 0.9600 |
C14—H14C | 0.9600 | C64—H64C | 0.9600 |
C15—C16 | 1.514 (5) | C65—C66 | 1.524 (5) |
C15—C22 | 1.533 (5) | C65—C72 | 1.528 (5) |
C15—H15A | 0.9800 | C65—H65A | 0.9800 |
C16—C21 | 1.381 (5) | C66—C67 | 1.383 (5) |
C16—C17 | 1.388 (5) | C66—C71 | 1.385 (5) |
C17—C18 | 1.372 (7) | C67—C68 | 1.400 (7) |
C17—H17A | 0.9300 | C67—H67A | 0.9300 |
C18—C19 | 1.342 (7) | C68—C69 | 1.379 (7) |
C18—H18A | 0.9300 | C68—H68A | 0.9300 |
C19—C20 | 1.374 (7) | C69—C70 | 1.338 (7) |
C19—H19A | 0.9300 | C69—H69A | 0.9300 |
C20—C21 | 1.405 (7) | C70—C71 | 1.390 (7) |
C20—H20A | 0.9300 | C70—H70A | 0.9300 |
C21—H21B | 0.9300 | C71—H71B | 0.9300 |
C22—H22B | 0.9600 | C72—H72B | 0.9600 |
C22—H22C | 0.9600 | C72—H72C | 0.9600 |
C22—H22D | 0.9600 | C72—H72D | 0.9600 |
C23—C24 | 1.494 (4) | C73—C74 | 1.511 (4) |
C23—H231 | 0.9800 | C73—H731 | 0.9800 |
C23—H232 | 0.9800 | C73—H732 | 0.9800 |
C24—C29 | 1.382 (5) | C74—C79 | 1.380 (6) |
C24—C25 | 1.390 (5) | C74—C75 | 1.387 (6) |
C25—C26 | 1.369 (6) | C75—C76 | 1.394 (6) |
C25—H25A | 0.9300 | C75—H75A | 0.9300 |
C26—C27 | 1.363 (8) | C76—C77 | 1.375 (9) |
C26—H26A | 0.9300 | C76—H76A | 0.9300 |
C27—C28 | 1.340 (8) | C77—C78 | 1.353 (8) |
C27—H27A | 0.9300 | C77—H77A | 0.9300 |
C28—C29 | 1.422 (6) | C78—C79 | 1.423 (6) |
C28—H28A | 0.9300 | C78—H78A | 0.9300 |
C29—H29A | 0.9300 | C79—H79A | 0.9300 |
O1—P1—N1 | 116.53 (12) | O51—P51—N51 | 117.07 (13) |
O1—P1—N2 | 117.52 (12) | O51—P51—N52 | 116.53 (13) |
N1—P1—N2 | 96.51 (12) | N51—P51—N52 | 96.44 (12) |
O1—P1—C23 | 108.18 (14) | O51—P51—C73 | 108.41 (15) |
N1—P1—C23 | 111.47 (14) | N51—P51—C73 | 110.89 (14) |
N2—P1—C23 | 105.89 (13) | N52—P51—C73 | 106.73 (14) |
C7—N1—C1 | 121.4 (2) | C57—N51—C51 | 122.6 (2) |
C7—N1—P1 | 129.76 (19) | C57—N51—P51 | 128.8 (2) |
C1—N1—P1 | 108.86 (17) | C51—N51—P51 | 108.58 (18) |
C2—N2—C15 | 121.0 (2) | C52—N52—C65 | 121.5 (2) |
C2—N2—P1 | 110.93 (18) | C52—N52—P51 | 111.10 (17) |
C15—N2—P1 | 118.42 (18) | C65—N52—P51 | 119.03 (19) |
C23—O21—H21 | 103.0 | C73—O71—H71 | 97.5 |
C23—O22—H22 | 101.8 | C73—O72—H72 | 104.0 |
N1—C1—C6 | 119.9 (3) | N51—C51—C52 | 106.6 (2) |
N1—C1—C2 | 106.2 (2) | N51—C51—C56 | 119.7 (3) |
C6—C1—C2 | 111.2 (3) | C52—C51—C56 | 110.6 (3) |
N1—C1—H1B | 106.2 | N51—C51—H51B | 106.4 |
C6—C1—H1B | 106.2 | C52—C51—H51B | 106.4 |
C2—C1—H1B | 106.2 | C56—C51—H51B | 106.4 |
N2—C2—C3 | 118.5 (3) | N52—C52—C53 | 118.9 (3) |
N2—C2—C1 | 105.9 (2) | N52—C52—C51 | 105.8 (2) |
C3—C2—C1 | 110.1 (2) | C53—C52—C51 | 111.1 (2) |
N2—C2—H2A | 107.3 | N52—C52—H52A | 106.8 |
C3—C2—H2A | 107.3 | C53—C52—H52A | 106.8 |
C1—C2—H2A | 107.3 | C51—C52—H52A | 106.8 |
C2—C3—C4 | 109.5 (3) | C52—C53—C54 | 108.8 (3) |
C2—C3—H3A | 109.8 | C52—C53—H53A | 109.9 |
C4—C3—H3A | 109.8 | C54—C53—H53A | 109.9 |
C2—C3—H3B | 109.8 | C52—C53—H53B | 109.9 |
C4—C3—H3B | 109.8 | C54—C53—H53B | 109.9 |
H3A—C3—H3B | 108.2 | H53A—C53—H53B | 108.3 |
C5—C4—C3 | 114.3 (3) | C55—C54—C53 | 114.3 (3) |
C5—C4—H4A | 108.7 | C55—C54—H54A | 108.7 |
C3—C4—H4A | 108.7 | C53—C54—H54A | 108.7 |
C5—C4—H4B | 108.7 | C55—C54—H54B | 108.7 |
C3—C4—H4B | 108.7 | C53—C54—H54B | 108.7 |
H4A—C4—H4B | 107.6 | H54A—C54—H54B | 107.6 |
C4—C5—C6 | 114.4 (3) | C54—C55—C56 | 113.7 (3) |
C4—C5—H5A | 108.7 | C54—C55—H55A | 108.8 |
C6—C5—H5A | 108.7 | C56—C55—H55A | 108.8 |
C4—C5—H5B | 108.7 | C54—C55—H55B | 108.8 |
C6—C5—H5B | 108.7 | C56—C55—H55B | 108.8 |
H5A—C5—H5B | 107.6 | H55A—C55—H55B | 107.7 |
C1—C6—C5 | 107.6 (3) | C51—C56—C55 | 107.7 (3) |
C1—C6—H6A | 110.2 | C51—C56—H56A | 110.2 |
C5—C6—H6A | 110.2 | C55—C56—H56A | 110.2 |
C1—C6—H6B | 110.2 | C51—C56—H56B | 110.2 |
C5—C6—H6B | 110.2 | C55—C56—H56B | 110.2 |
H6A—C6—H6B | 108.5 | H56A—C56—H56B | 108.5 |
N1—C7—C8 | 112.5 (3) | N51—C57—C58 | 112.2 (3) |
N1—C7—C14 | 112.0 (3) | N51—C57—C64 | 112.7 (3) |
C8—C7—C14 | 110.7 (3) | C58—C57—C64 | 109.4 (3) |
N1—C7—H7A | 107.1 | N51—C57—H57A | 107.4 |
C8—C7—H7A | 107.1 | C58—C57—H57A | 107.4 |
C14—C7—H7A | 107.1 | C64—C57—H57A | 107.4 |
C9—C8—C13 | 118.5 (4) | C63—C58—C59 | 118.4 (4) |
C9—C8—C7 | 120.9 (3) | C63—C58—C57 | 120.3 (4) |
C13—C8—C7 | 120.6 (4) | C59—C58—C57 | 121.3 (3) |
C8—C9—C10 | 120.2 (5) | C60—C59—C58 | 121.9 (4) |
C8—C9—H9A | 119.9 | C60—C59—H59A | 119.1 |
C10—C9—H9A | 119.9 | C58—C59—H59A | 119.1 |
C11—C10—C9 | 120.2 (6) | C61—C60—C59 | 120.1 (5) |
C11—C10—H10A | 119.9 | C61—C60—H60A | 119.9 |
C9—C10—H10A | 119.9 | C59—C60—H60A | 119.9 |
C12—C11—C10 | 118.7 (5) | C60—C61—C62 | 120.9 (5) |
C12—C11—H11A | 120.6 | C60—C61—H61A | 119.5 |
C10—C11—H11A | 120.6 | C62—C61—H61A | 119.5 |
C11—C12—C13 | 121.8 (5) | C61—C62—C63 | 118.3 (5) |
C11—C12—H12A | 119.1 | C61—C62—H62A | 120.9 |
C13—C12—H12A | 119.1 | C63—C62—H62A | 120.9 |
C12—C13—C8 | 120.6 (5) | C58—C63—C62 | 120.3 (5) |
C12—C13—H13A | 119.7 | C58—C63—H63A | 119.9 |
C8—C13—H13A | 119.7 | C62—C63—H63A | 119.9 |
C7—C14—H14A | 109.5 | C57—C64—H64A | 109.5 |
C7—C14—H14B | 109.5 | C57—C64—H64B | 109.5 |
H14A—C14—H14B | 109.5 | H64A—C64—H64B | 109.5 |
C7—C14—H14C | 109.5 | C57—C64—H64C | 109.5 |
H14A—C14—H14C | 109.5 | H64A—C64—H64C | 109.5 |
H14B—C14—H14C | 109.5 | H64B—C64—H64C | 109.5 |
N2—C15—C16 | 110.9 (3) | N52—C65—C66 | 111.4 (2) |
N2—C15—C22 | 111.4 (3) | N52—C65—C72 | 110.5 (3) |
C16—C15—C22 | 115.2 (3) | C66—C65—C72 | 115.4 (3) |
N2—C15—H15A | 106.2 | N52—C65—H65A | 106.3 |
C16—C15—H15A | 106.2 | C66—C65—H65A | 106.3 |
C22—C15—H15A | 106.2 | C72—C65—H65A | 106.3 |
C21—C16—C17 | 117.9 (4) | C67—C66—C71 | 117.8 (4) |
C21—C16—C15 | 123.3 (3) | C67—C66—C65 | 119.1 (3) |
C17—C16—C15 | 118.8 (3) | C71—C66—C65 | 123.1 (3) |
C18—C17—C16 | 121.8 (4) | C66—C67—C68 | 120.5 (4) |
C18—C17—H17A | 119.1 | C66—C67—H67A | 119.8 |
C16—C17—H17A | 119.1 | C68—C67—H67A | 119.8 |
C19—C18—C17 | 120.3 (4) | C69—C68—C67 | 119.1 (5) |
C19—C18—H18A | 119.9 | C69—C68—H68A | 120.4 |
C17—C18—H18A | 119.9 | C67—C68—H68A | 120.4 |
C18—C19—C20 | 120.1 (5) | C70—C69—C68 | 121.7 (5) |
C18—C19—H19A | 119.9 | C70—C69—H69A | 119.2 |
C20—C19—H19A | 119.9 | C68—C69—H69A | 119.2 |
C19—C20—C21 | 120.3 (4) | C69—C70—C71 | 119.1 (5) |
C19—C20—H20A | 119.9 | C69—C70—H70A | 120.5 |
C21—C20—H20A | 119.9 | C71—C70—H70A | 120.5 |
C16—C21—C20 | 119.6 (4) | C66—C71—C70 | 121.9 (5) |
C16—C21—H21B | 120.2 | C66—C71—H71B | 119.1 |
C20—C21—H21B | 120.2 | C70—C71—H71B | 119.1 |
C15—C22—H22B | 109.5 | C65—C72—H72B | 109.5 |
C15—C22—H22C | 109.5 | C65—C72—H72C | 109.5 |
H22B—C22—H22C | 109.5 | H72B—C72—H72C | 109.5 |
C15—C22—H22D | 109.5 | C65—C72—H72D | 109.5 |
H22B—C22—H22D | 109.5 | H72B—C72—H72D | 109.5 |
H22C—C22—H22D | 109.5 | H72C—C72—H72D | 109.5 |
O21—C23—O22 | 107.6 (4) | O72—C73—O71 | 106.2 (6) |
O21—C23—C24 | 110.2 (3) | O72—C73—C74 | 109.9 (6) |
O22—C23—C24 | 111.6 (4) | O71—C73—C74 | 111.0 (3) |
O21—C23—P1 | 106.5 (2) | O72—C73—P51 | 110.0 (6) |
O22—C23—P1 | 106.8 (4) | O71—C73—P51 | 105.6 (2) |
C24—C23—P1 | 113.9 (2) | C74—C73—P51 | 113.8 (2) |
O21—C23—H231 | 108.7 | O71—C73—H731 | 108.8 |
C24—C23—H231 | 108.7 | C74—C73—H731 | 108.8 |
P1—C23—H231 | 108.7 | P51—C73—H731 | 108.8 |
O22—C23—H232 | 108.1 | O72—C73—H732 | 107.6 |
C24—C23—H232 | 108.1 | C74—C73—H732 | 107.6 |
P1—C23—H232 | 108.1 | P51—C73—H732 | 107.6 |
H231—C23—H232 | 109.2 | H731—C73—H732 | 110.2 |
C29—C24—C25 | 118.9 (3) | C79—C74—C75 | 119.1 (4) |
C29—C24—C23 | 120.7 (3) | C79—C74—C73 | 120.4 (3) |
C25—C24—C23 | 120.4 (3) | C75—C74—C73 | 120.4 (4) |
C26—C25—C24 | 121.1 (5) | C74—C75—C76 | 121.1 (5) |
C26—C25—H25A | 119.5 | C74—C75—H75A | 119.5 |
C24—C25—H25A | 119.5 | C76—C75—H75A | 119.5 |
C27—C26—C25 | 120.3 (5) | C77—C76—C75 | 119.5 (5) |
C27—C26—H26A | 119.9 | C77—C76—H76A | 120.3 |
C25—C26—H26A | 119.9 | C75—C76—H76A | 120.3 |
C28—C27—C26 | 120.2 (5) | C78—C77—C76 | 120.5 (5) |
C28—C27—H27A | 119.9 | C78—C77—H77A | 119.8 |
C26—C27—H27A | 119.9 | C76—C77—H77A | 119.8 |
C27—C28—C29 | 121.3 (5) | C77—C78—C79 | 120.7 (5) |
C27—C28—H28A | 119.4 | C77—C78—H78A | 119.6 |
C29—C28—H28A | 119.4 | C79—C78—H78A | 119.6 |
C24—C29—C28 | 118.3 (5) | C74—C79—C78 | 119.1 (5) |
C24—C29—H29A | 120.9 | C74—C79—H79A | 120.4 |
C28—C29—H29A | 120.9 | C78—C79—H79A | 120.4 |
O1—P1—N1—C7 | −36.0 (3) | O51—P51—N51—C57 | −35.3 (3) |
N2—P1—N1—C7 | −161.2 (3) | N52—P51—N51—C57 | −159.5 (3) |
C23—P1—N1—C7 | 88.9 (3) | C73—P51—N51—C57 | 89.8 (3) |
O1—P1—N1—C1 | 143.7 (2) | O51—P51—N51—C51 | 143.8 (2) |
N2—P1—N1—C1 | 18.5 (2) | N52—P51—N51—C51 | 19.6 (2) |
C23—P1—N1—C1 | −91.5 (2) | C73—P51—N51—C51 | −91.1 (2) |
O1—P1—N2—C2 | −122.0 (2) | O51—P51—N52—C52 | −123.7 (2) |
N1—P1—N2—C2 | 2.5 (2) | N51—P51—N52—C52 | 1.0 (2) |
C23—P1—N2—C2 | 117.1 (2) | C73—P51—N52—C52 | 115.1 (2) |
O1—P1—N2—C15 | 24.5 (3) | O51—P51—N52—C65 | 25.0 (3) |
N1—P1—N2—C15 | 149.0 (2) | N51—P51—N52—C65 | 149.6 (2) |
C23—P1—N2—C15 | −96.5 (2) | C73—P51—N52—C65 | −96.3 (2) |
C7—N1—C1—C6 | 19.5 (4) | C57—N51—C51—C52 | 145.4 (3) |
P1—N1—C1—C6 | −160.3 (2) | P51—N51—C51—C52 | −33.8 (3) |
C7—N1—C1—C2 | 146.4 (3) | C57—N51—C51—C56 | 19.1 (5) |
P1—N1—C1—C2 | −33.3 (3) | P51—N51—C51—C56 | −160.1 (3) |
C15—N2—C2—C3 | 68.4 (4) | C65—N52—C52—C53 | 66.1 (4) |
P1—N2—C2—C3 | −146.2 (2) | P51—N52—C52—C53 | −146.1 (3) |
C15—N2—C2—C1 | −167.4 (2) | C65—N52—C52—C51 | −168.2 (3) |
P1—N2—C2—C1 | −22.0 (3) | P51—N52—C52—C51 | −20.5 (3) |
N1—C1—C2—N2 | 34.2 (3) | N51—C51—C52—N52 | 33.6 (3) |
C6—C1—C2—N2 | 166.2 (2) | C56—C51—C52—N52 | 165.2 (3) |
N1—C1—C2—C3 | 163.4 (3) | N51—C51—C52—C53 | 163.9 (3) |
C6—C1—C2—C3 | −64.5 (4) | C56—C51—C52—C53 | −64.5 (4) |
N2—C2—C3—C4 | 178.2 (3) | N52—C52—C53—C54 | −179.8 (3) |
C1—C2—C3—C4 | 56.1 (4) | C51—C52—C53—C54 | 57.1 (4) |
C2—C3—C4—C5 | −48.9 (4) | C52—C53—C54—C55 | −50.2 (4) |
C3—C4—C5—C6 | 48.5 (5) | C53—C54—C55—C56 | 49.7 (5) |
N1—C1—C6—C5 | −175.3 (3) | N51—C51—C56—C55 | −176.3 (3) |
C2—C1—C6—C5 | 60.1 (4) | C52—C51—C56—C55 | 59.3 (4) |
C4—C5—C6—C1 | −52.1 (4) | C54—C55—C56—C51 | −52.3 (4) |
C1—N1—C7—C8 | −80.6 (4) | C51—N51—C57—C58 | −82.3 (4) |
P1—N1—C7—C8 | 99.1 (3) | P51—N51—C57—C58 | 96.7 (3) |
C1—N1—C7—C14 | 154.0 (3) | C51—N51—C57—C64 | 153.5 (3) |
P1—N1—C7—C14 | −26.4 (4) | P51—N51—C57—C64 | −27.4 (4) |
N1—C7—C8—C9 | −50.9 (4) | N51—C57—C58—C63 | 137.8 (3) |
C14—C7—C8—C9 | 75.3 (4) | C64—C57—C58—C63 | −96.3 (4) |
N1—C7—C8—C13 | 131.5 (3) | N51—C57—C58—C59 | −43.6 (4) |
C14—C7—C8—C13 | −102.4 (4) | C64—C57—C58—C59 | 82.3 (4) |
C13—C8—C9—C10 | −0.1 (6) | C63—C58—C59—C60 | 0.3 (6) |
C7—C8—C9—C10 | −177.8 (3) | C57—C58—C59—C60 | −178.3 (4) |
C8—C9—C10—C11 | 1.3 (7) | C58—C59—C60—C61 | 1.0 (7) |
C9—C10—C11—C12 | −1.9 (7) | C59—C60—C61—C62 | −1.8 (8) |
C10—C11—C12—C13 | 1.2 (8) | C60—C61—C62—C63 | 1.3 (8) |
C11—C12—C13—C8 | 0.0 (7) | C59—C58—C63—C62 | −0.8 (6) |
C9—C8—C13—C12 | −0.6 (6) | C57—C58—C63—C62 | 177.9 (4) |
C7—C8—C13—C12 | 177.1 (3) | C61—C62—C63—C58 | 0.0 (7) |
C2—N2—C15—C16 | 40.1 (3) | C52—N52—C65—C66 | 29.5 (4) |
P1—N2—C15—C16 | −102.9 (3) | P51—N52—C65—C66 | −115.8 (3) |
C2—N2—C15—C22 | −89.7 (4) | C52—N52—C65—C72 | −100.2 (4) |
P1—N2—C15—C22 | 127.3 (3) | P51—N52—C65—C72 | 114.6 (3) |
N2—C15—C16—C21 | −106.4 (3) | N52—C65—C66—C67 | 70.6 (4) |
C22—C15—C16—C21 | 21.3 (4) | C72—C65—C66—C67 | −162.4 (3) |
N2—C15—C16—C17 | 71.3 (3) | N52—C65—C66—C71 | −110.0 (3) |
C22—C15—C16—C17 | −161.0 (3) | C72—C65—C66—C71 | 17.0 (5) |
C21—C16—C17—C18 | 0.3 (5) | C71—C66—C67—C68 | 1.0 (5) |
C15—C16—C17—C18 | −177.5 (3) | C65—C66—C67—C68 | −179.5 (3) |
C16—C17—C18—C19 | 0.6 (6) | C66—C67—C68—C69 | −0.8 (6) |
C17—C18—C19—C20 | −1.7 (7) | C67—C68—C69—C70 | 0.2 (7) |
C18—C19—C20—C21 | 2.0 (6) | C68—C69—C70—C71 | 0.0 (7) |
C17—C16—C21—C20 | 0.0 (5) | C67—C66—C71—C70 | −0.8 (5) |
C15—C16—C21—C20 | 177.6 (3) | C65—C66—C71—C70 | 179.8 (3) |
C19—C20—C21—C16 | −1.1 (6) | C69—C70—C71—C66 | 0.2 (6) |
O1—P1—C23—O21 | −59.6 (2) | O51—P51—C73—O72 | 51.7 (6) |
N1—P1—C23—O21 | 171.04 (19) | N51—P51—C73—O72 | −78.1 (6) |
N2—P1—C23—O21 | 67.2 (2) | N52—P51—C73—O72 | 178.0 (6) |
O1—P1—C23—O22 | 55.2 (4) | O51—P51—C73—O71 | −62.4 (2) |
N1—P1—C23—O22 | −74.2 (3) | N51—P51—C73—O71 | 167.7 (2) |
N2—P1—C23—O22 | −178.0 (3) | N52—P51—C73—O71 | 63.8 (2) |
O1—P1—C23—C24 | 178.8 (2) | O51—P51—C73—C74 | 175.6 (2) |
N1—P1—C23—C24 | 49.4 (3) | N51—P51—C73—C74 | 45.7 (3) |
N2—P1—C23—C24 | −54.4 (3) | N52—P51—C73—C74 | −58.2 (3) |
O21—C23—C24—C29 | −23.2 (5) | O72—C73—C74—C79 | −146.0 (7) |
O22—C23—C24—C29 | −142.6 (5) | O71—C73—C74—C79 | −28.8 (4) |
P1—C23—C24—C29 | 96.4 (4) | P51—C73—C74—C79 | 90.1 (4) |
O21—C23—C24—C25 | 158.0 (3) | O72—C73—C74—C75 | 34.6 (7) |
O22—C23—C24—C25 | 38.6 (5) | O71—C73—C74—C75 | 151.8 (3) |
P1—C23—C24—C25 | −82.4 (4) | P51—C73—C74—C75 | −89.3 (4) |
C29—C24—C25—C26 | 0.1 (6) | C79—C74—C75—C76 | 0.2 (6) |
C23—C24—C25—C26 | 178.9 (4) | C73—C74—C75—C76 | 179.6 (4) |
C24—C25—C26—C27 | 0.7 (8) | C74—C75—C76—C77 | 0.9 (8) |
C25—C26—C27—C28 | −1.1 (9) | C75—C76—C77—C78 | −1.4 (9) |
C26—C27—C28—C29 | 0.8 (10) | C76—C77—C78—C79 | 0.7 (9) |
C25—C24—C29—C28 | −0.4 (6) | C75—C74—C79—C78 | −0.9 (6) |
C23—C24—C29—C28 | −179.2 (4) | C73—C74—C79—C78 | 179.7 (4) |
C27—C28—C29—C24 | −0.1 (8) | C77—C78—C79—C74 | 0.5 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O21—H21···O51 | 0.85 | 1.89 | 2.718 (4) | 165 |
O22—H22···O51 | 0.93 | 1.71 | 2.587 (7) | 156 |
O71—H71···O1 | 0.97 | 1.72 | 2.688 (4) | 176 |
O72—H72···O1 | 0.72 | 1.90 | 2.608 (12) | 167 |
Experimental details
Crystal data | |
Chemical formula | C29H35N2O2P |
Mr | 474.56 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 300 |
a, b, c (Å) | 9.6413 (11), 17.3888 (11), 15.8778 (11) |
β (°) | 95.373 (8) |
V (Å3) | 2650.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.60 × 0.55 × 0.45 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan ψ scans (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.926, 0.942 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15139, 7715, 5554 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.129, 1.03 |
No. of reflections | 7715 |
No. of parameters | 633 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.21 |
Absolute structure | Flack (1983), 446 Friedel pairs |
Absolute structure parameter | −0.02 (8) |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL-Plus (Sheldrick, 1998), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
P1—O1 | 1.4823 (18) | C23—C24 | 1.494 (4) |
P1—N1 | 1.644 (2) | P51—O51 | 1.4833 (19) |
P1—N2 | 1.663 (2) | P51—N51 | 1.648 (2) |
P1—C23 | 1.844 (3) | P51—N52 | 1.658 (2) |
O21—C23 | 1.443 (4) | P51—C73 | 1.847 (4) |
O21—H21 | 0.8475 | O71—C73 | 1.426 (4) |
O22—C23 | 1.444 (7) | O72—C73 | 1.412 (12) |
O22—H22 | 0.9332 | C73—C74 | 1.511 (4) |
O1—P1—N1 | 116.53 (12) | O51—P51—N51 | 117.07 (13) |
O1—P1—N2 | 117.52 (12) | O51—P51—N52 | 116.53 (13) |
N1—P1—N2 | 96.51 (12) | N51—P51—N52 | 96.44 (12) |
O1—P1—C23 | 108.18 (14) | O51—P51—C73 | 108.41 (15) |
N1—P1—C23 | 111.47 (14) | N51—P51—C73 | 110.89 (14) |
N2—P1—C23 | 105.89 (13) | N52—P51—C73 | 106.73 (14) |
O21—C23—O22 | 107.6 (4) | O72—C73—O71 | 106.2 (6) |
O21—C23—C24 | 110.2 (3) | O72—C73—C74 | 109.9 (6) |
O22—C23—C24 | 111.6 (4) | O71—C73—C74 | 111.0 (3) |
O21—C23—P1 | 106.5 (2) | O72—C73—P51 | 110.0 (6) |
O22—C23—P1 | 106.8 (4) | O71—C73—P51 | 105.6 (2) |
C24—C23—P1 | 113.9 (2) | C74—C73—P51 | 113.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O21—H21···O51 | 0.85 | 1.89 | 2.718 (4) | 165 |
O22—H22···O51 | 0.93 | 1.71 | 2.587 (7) | 156 |
O71—H71···O1 | 0.97 | 1.72 | 2.688 (4) | 176 |
O72—H72···O1 | 0.72 | 1.90 | 2.608 (12) | 167 |
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There are many examples in the literature of biologically active α-hydroxy phosphonates and phosphonic acids (e.g. Engel, 1977; Hilderbrand, 1983; De Clercq et al., 1986; Kitamura et al., 1995). Interest for this class of compounds has been motivated by the need to access a variety of phosphorous derivatives, particularly with substitutions at the Cα position, since such derivatives display required physiological properties (Yokomatsu & Shibuya, 1992; Öhler & Kotzinger, 1993; Berkowitz & Smith, 1995; Bennani & Hanessian, 1997).
In this area, the Pudovik reaction is a well known phosphonylation process that involves the addition of organophosphorous compounds containing a labile P—H bond to unsaturated systems (Pudovik & Konovalova, 1979). During the past decade, enantioselective syntheses of α-hydroxyphosphonates through the asymmetric Pudovik reaction of aldehydes have been reported. These reactions take place in the presence of chiral diols, amino alcohols and diamines as catalysts or using chiral auxiliaries (Davies et al., 1998; Groaning et al., 1998; Duxbury et al., 1999; Yamagishi et al., 1999; Rowe & Spilling, 2001). In this context, we recently obtained moderate diastereoselectivities for the carbonyl phosphonylation of aldehydes using N,N'-bis-[(S)-α-phenylethyl]-bicyclic phosphorous acid diamides (Moreno et al., 2004). When attempting to crystallize the adduct between a deprotonated chiral diazophosphole and benzaldehyde (see the scheme below), we observed an unexpected diastereoisomeric enrichment in the solid state. We now report the crystal structure of this compound, (I).
The asymmetric unit of (I) contains two independent molecules (Z'=2), with all atoms in general positions. Stereogenic Cα atoms C23 and C73, incorporated during the condensation reaction, have disordered OH and H substituents, while the phenyl (C24 and C74) and P-containing moieties (P1 and P51) do not exhibit disorder (Fig. 1 and 2). Positions and site-occupancy factors for the disordered groups were refined (see Experimental), converging to similar models for both independent molecules. Merging of site-occupancy factors results in a stereochemistry for Cα corresponding to a mixture of 0.741 (6)-S and 0.259 (6)-R molecules, randomly distributed in the whole crystal, with remaining chiral C centers as follows: 1S, 2S, 7S, 15S; 51S, 52S, 57S, 65S.
Some comments in relation to the unusual disorder observed in (I) are worthwhile: (i) Chiral centers C1, C2, C7 and C15 (and corresponding chiral C atoms for the second molecule) exhibit the same absolute configuration as in the starting material, as expected from the synthetic route. This fact confirms the assignment of the configurations at atoms C23 and C73. (ii) Although of limited reliability in the present case, because of the relatively low anomalous dispersion of P atoms and the polar character of the space group, the refinement of the Flack (1983) parameter is in agreement with the assigned absolute configuration. An attempt to refine the inverted structure leads to a Flack parameter close to 1. Finally, no symptoms of twinning appeared during data collection and structure refinement. (iii) In order to check the reproducibility of the observed absolute configuration, a single-crystal obtained from another batch was studied; on the basis of 6129 collected reflections (2θmax = 50°, R1 = 0.04 for 634 refined parameters and 4493 independent data), the absolute configuration for Cα converged to 0.746 (6)-S mixed with 0.254 (6)-R, with a Flack parameter of 0.01 (10), a result very close to that obtained for the refinement reported here.
The three above-mentioned accounts provide strong evidence that the absolute configuration of (I) has been assigned correctly. However, the diastereoisomeric enhancement of ca 50% observed in the solid state does not agree with that found in solution. Diastereoiomers were easily distinguishable by 31P NMR spectroscopy; for the crude of the reaction, an isomeric R:S ratio of 1.8:1.0 was estimated, in contrast to the 1.0:1.9 ratio observed in the solid state. Hence, we assume that this enrichment in the minor diastereoisomer probably occurs via a thermodynamically controlled epimerization at the Cα atom, during the crystallization process, while the major isomer in solution corresponds to the kinetic product of the condensation reaction. In order to check this hypothesis, a chemical correlation was carried out. Compound (I) was hydrolyzed to give the corresponding phosphonic acid, which was purified by ion exchange chromatography and then converted to the monocyclohexylammonium salt, using a classical procedure (see Experimental). A comparison with the reported [α]D values for the enantiomerically pure salts (Smaardijk et al., 1985), indicated that the major isomer for (I) in solution is Cα-R.
The two independent molecules in (I) have similar geometry (Table 1). A fit between the two molecules, carried out on non-H atoms, gives an r.m.s deviation of 0.23 Å, mainly becuase of a degree of free rotation for the phenyl groups. The bicyclic ring system consists of a six-membered chair cycle fused with a five-membered envelope ring, a conformation observed in numerous perhydrobenzodiazophosphole-based molecules (e.g. Koeller et al., 1993; Blazis et al., 1995; Wyatt et al., 1999). The crystal packing of (I) is dominated by hydrogen bonds within the asymmetric unit, which are favored by the Z'>1 value and disorder at Cα atoms (Table 2 and Fig. 3). Each oxide group forms a bifurcated hydrogen bond with the H atoms belonging to the disordered hydroxy groups of the other independent molecule. This symmetric arrangement generates a non-crystallographic inversion center, positioned close to the centroid of the O1···O51 line. However, there is no doubt that the space group of (I) is actually non-centrosymmetric, in agreement with the chiral character of the molecules. The emulated space group, P21/c, does not fit the diffraction pattern, for which 255 intensities are above a 3σ threshold in the set of 432 reflections corresponding to the extinction expected for a c glide plane.
In conclusion, we have established, using both chemical and crystallographic evidence, that the title compound can undergo epimerization at Cα, which has been shown previously to be an important chiral center for biological activity for these P-containing molecules. To the best of our knowledge, epimerization processes involved in the Pudovik condensation reaction have not been well documented util now. This potential complication probably deserves more attention when using this valuable synthetic tool.