Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803006640/ww6066sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803006640/ww6066Isup2.hkl |
CCDC reference: 214593
All reaction was carried out under N2 with Schlenk skill. To a cooled solution (213 K) of PCl3 (270 ml, 3.0 mmol), EtN3(860 ml, 6.0 mmol), and toluene (5 ml) was added a warm solution (333 K) of (R)-2,2'-binaphthol (860 mg, 3.0 mmol) in toluene (25 ml) in 25 min. After stirring for 2 h, the reaction mixture was warmed up to room temperature and filtered under a nitrogen atmosphere. The filtrate was a solution of chlorophosphite. The title compound was prepared by the reaction of the chlorophosphite and 2.9 mmol of the benzyl-2-pyridine compounds at 233 K in the presence of Et3N (410 ml, 2.9 mmol) and 4-dimethylaminopyridine. The crude products were purified by flash silica-gel chromatography. 1185 mg of white solid was obtained (yield: 82%). A colorless crystal suitable for X-ray diffraction was obtained by recrystallization from a solution in CH2Cl2 and ether. 31P NMR (CD2Cl2): δ 144.47 p.p.m.
H atoms were included in the riding-model approximation, with Uiso values equal to the Ueq of the atom to which they were bound.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I), showing ellipsoids at the 50% probability level (Bruker, 1995). |
C32H23N2O2P | F(000) = 1040 |
Mr = 498.49 | Dx = 1.318 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3922 reflections |
a = 9.5168 (11) Å | θ = 1–27.5° |
b = 10.3952 (11) Å | µ = 0.14 mm−1 |
c = 25.398 (3) Å | T = 294 K |
V = 2512.6 (5) Å3 | Block, colorless |
Z = 4 | 0.36 × 0.32 × 0.30 mm |
Siemens CCD area-detector diffractometer | 5805 independent reflections |
Radiation source: fine-focus sealed tube | 2424 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.075 |
ϕ and ω scans | θmax = 27.6°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.950, Tmax = 0.958 | k = −13→13 |
17396 measured reflections | l = −22→33 |
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)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.002P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.90 | (Δ/σ)max < 0.001 |
5805 reflections | Δρmax = 0.17 e Å−3 |
334 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 0000 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.15 (9) |
C32H23N2O2P | V = 2512.6 (5) Å3 |
Mr = 498.49 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.5168 (11) Å | µ = 0.14 mm−1 |
b = 10.3952 (11) Å | T = 294 K |
c = 25.398 (3) Å | 0.36 × 0.32 × 0.30 mm |
Siemens CCD area-detector diffractometer | 5805 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2424 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.958 | Rint = 0.075 |
17396 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.058 | Δρmax = 0.17 e Å−3 |
S = 0.90 | Δρmin = −0.21 e Å−3 |
5805 reflections | Absolute structure: Flack (1983), 0000 Friedel pairs |
334 parameters | Absolute structure parameter: 0.15 (9) |
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 | 0.66445 (9) | 0.61190 (8) | 0.36427 (3) | 0.0541 (2) | |
O1 | 0.76541 (18) | 0.57650 (17) | 0.41530 (7) | 0.0509 (5) | |
O2 | 0.50965 (18) | 0.56757 (17) | 0.38756 (6) | 0.0504 (5) | |
N1 | 0.7194 (2) | 0.4796 (2) | 0.32824 (9) | 0.0508 (7) | |
N2 | 0.5646 (3) | 0.5582 (2) | 0.26716 (10) | 0.0574 (7) | |
C1 | 0.7180 (3) | 0.6057 (3) | 0.46575 (11) | 0.0481 (8) | |
C2 | 0.7870 (3) | 0.7062 (3) | 0.49163 (13) | 0.0563 (9) | |
H2A | 0.8582 | 0.7515 | 0.4748 | 0.068* | |
C3 | 0.7491 (4) | 0.7369 (3) | 0.54130 (14) | 0.0670 (10) | |
H3A | 0.7977 | 0.8013 | 0.5591 | 0.080* | |
C4 | 0.6381 (4) | 0.6736 (3) | 0.56656 (13) | 0.0579 (10) | |
C5 | 0.5882 (4) | 0.7115 (3) | 0.61673 (15) | 0.0882 (13) | |
H5A | 0.6338 | 0.7775 | 0.6346 | 0.106* | |
C6 | 0.4770 (5) | 0.6546 (4) | 0.63892 (15) | 0.0978 (16) | |
H6A | 0.4472 | 0.6810 | 0.6721 | 0.117* | |
C7 | 0.4045 (4) | 0.5555 (3) | 0.61301 (14) | 0.0824 (12) | |
H7A | 0.3259 | 0.5181 | 0.6285 | 0.099* | |
C8 | 0.4508 (3) | 0.5140 (3) | 0.56437 (12) | 0.0612 (10) | |
H8A | 0.4036 | 0.4476 | 0.5474 | 0.073* | |
C9 | 0.5692 (3) | 0.5714 (3) | 0.54004 (12) | 0.0493 (8) | |
C10 | 0.6160 (3) | 0.5325 (2) | 0.48892 (11) | 0.0423 (8) | |
C11 | 0.5537 (3) | 0.4233 (3) | 0.45931 (11) | 0.0416 (7) | |
C12 | 0.5526 (3) | 0.2947 (3) | 0.47914 (11) | 0.0458 (8) | |
C13 | 0.6151 (3) | 0.2591 (3) | 0.52724 (12) | 0.0547 (9) | |
H13A | 0.6588 | 0.3214 | 0.5478 | 0.066* | |
C14 | 0.6126 (3) | 0.1335 (3) | 0.54441 (13) | 0.0717 (10) | |
H14A | 0.6554 | 0.1116 | 0.5761 | 0.086* | |
C15 | 0.5457 (4) | 0.0382 (3) | 0.51422 (15) | 0.0801 (12) | |
H15A | 0.5430 | −0.0461 | 0.5265 | 0.096* | |
C16 | 0.4858 (4) | 0.0674 (3) | 0.46800 (14) | 0.0739 (10) | |
H16A | 0.4421 | 0.0029 | 0.4486 | 0.089* | |
C17 | 0.4875 (3) | 0.1964 (3) | 0.44780 (13) | 0.0534 (8) | |
C18 | 0.4289 (3) | 0.2278 (3) | 0.39870 (12) | 0.0667 (10) | |
H18A | 0.3841 | 0.1643 | 0.3791 | 0.080* | |
C19 | 0.4365 (3) | 0.3493 (3) | 0.37947 (12) | 0.0632 (10) | |
H19A | 0.3998 | 0.3689 | 0.3465 | 0.076* | |
C20 | 0.5010 (3) | 0.4453 (3) | 0.41031 (12) | 0.0485 (8) | |
C21 | 0.8067 (3) | 0.3748 (3) | 0.34823 (10) | 0.0588 (9) | |
H21A | 0.7548 | 0.2949 | 0.3451 | 0.071* | |
H21B | 0.8247 | 0.3895 | 0.3853 | 0.071* | |
C22 | 0.9451 (3) | 0.3603 (3) | 0.32018 (11) | 0.0491 (8) | |
C23 | 1.0182 (3) | 0.4652 (3) | 0.30047 (11) | 0.0611 (9) | |
H23A | 0.9808 | 0.5475 | 0.3037 | 0.073* | |
C24 | 1.1463 (4) | 0.4476 (3) | 0.27607 (12) | 0.0746 (10) | |
H24A | 1.1945 | 0.5187 | 0.2632 | 0.090* | |
C25 | 1.2042 (3) | 0.3277 (4) | 0.27040 (13) | 0.0725 (11) | |
H25A | 1.2897 | 0.3176 | 0.2532 | 0.087* | |
C26 | 1.1352 (4) | 0.2233 (3) | 0.29017 (13) | 0.0723 (11) | |
H26A | 1.1741 | 0.1416 | 0.2871 | 0.087* | |
C27 | 1.0071 (4) | 0.2401 (3) | 0.31473 (11) | 0.0655 (9) | |
H27A | 0.9608 | 0.1684 | 0.3281 | 0.079* | |
C28 | 0.6557 (3) | 0.4649 (3) | 0.27951 (12) | 0.0492 (8) | |
C29 | 0.6813 (3) | 0.3612 (3) | 0.24616 (13) | 0.0636 (9) | |
H29A | 0.7476 | 0.2988 | 0.2547 | 0.076* | |
C30 | 0.6050 (4) | 0.3540 (3) | 0.20010 (14) | 0.0726 (10) | |
H30A | 0.6179 | 0.2845 | 0.1776 | 0.087* | |
C31 | 0.5108 (4) | 0.4478 (4) | 0.18723 (13) | 0.0741 (10) | |
H31A | 0.4587 | 0.4436 | 0.1563 | 0.089* | |
C32 | 0.4958 (3) | 0.5490 (3) | 0.22190 (14) | 0.0675 (10) | |
H32A | 0.4337 | 0.6146 | 0.2130 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0581 (5) | 0.0525 (5) | 0.0517 (5) | 0.0052 (5) | 0.0089 (5) | 0.0073 (5) |
O1 | 0.0466 (13) | 0.0578 (13) | 0.0485 (13) | −0.0003 (11) | 0.0043 (11) | 0.0001 (11) |
O2 | 0.0456 (12) | 0.0594 (13) | 0.0463 (12) | 0.0073 (11) | 0.0027 (10) | 0.0073 (10) |
N1 | 0.0547 (18) | 0.0509 (16) | 0.0469 (16) | 0.0148 (13) | 0.0115 (13) | 0.0048 (13) |
N2 | 0.0604 (19) | 0.0614 (19) | 0.0503 (18) | 0.0016 (15) | 0.0014 (14) | 0.0115 (15) |
C1 | 0.053 (2) | 0.0418 (19) | 0.049 (2) | 0.0063 (17) | −0.0060 (17) | −0.0004 (18) |
C2 | 0.059 (3) | 0.041 (2) | 0.070 (2) | 0.0011 (17) | −0.0074 (19) | 0.0027 (18) |
C3 | 0.074 (3) | 0.050 (2) | 0.077 (3) | 0.010 (2) | −0.021 (2) | −0.013 (2) |
C4 | 0.075 (3) | 0.054 (2) | 0.045 (2) | 0.023 (2) | −0.007 (2) | −0.0074 (18) |
C5 | 0.120 (4) | 0.081 (3) | 0.064 (3) | 0.030 (3) | −0.018 (3) | −0.010 (2) |
C6 | 0.144 (5) | 0.101 (4) | 0.048 (3) | 0.045 (3) | 0.007 (3) | 0.005 (3) |
C7 | 0.101 (3) | 0.081 (3) | 0.065 (3) | 0.036 (3) | 0.035 (2) | 0.031 (2) |
C8 | 0.075 (3) | 0.055 (2) | 0.054 (2) | 0.0206 (19) | 0.0083 (19) | 0.0085 (18) |
C9 | 0.051 (2) | 0.050 (2) | 0.047 (2) | 0.0104 (17) | 0.0010 (17) | 0.0095 (17) |
C10 | 0.042 (2) | 0.0386 (18) | 0.046 (2) | 0.0012 (15) | −0.0003 (15) | 0.0044 (16) |
C11 | 0.0407 (19) | 0.0395 (19) | 0.0445 (19) | −0.0010 (15) | 0.0032 (15) | 0.0019 (16) |
C12 | 0.0334 (19) | 0.050 (2) | 0.054 (2) | 0.0000 (16) | 0.0081 (16) | 0.0009 (18) |
C13 | 0.047 (2) | 0.049 (2) | 0.068 (3) | −0.0041 (17) | −0.0040 (18) | 0.0044 (18) |
C14 | 0.055 (2) | 0.065 (2) | 0.095 (3) | −0.001 (2) | −0.0054 (19) | 0.018 (2) |
C15 | 0.074 (3) | 0.049 (2) | 0.117 (4) | −0.007 (2) | 0.005 (2) | 0.014 (2) |
C16 | 0.069 (3) | 0.054 (2) | 0.098 (3) | −0.013 (2) | 0.011 (2) | −0.007 (2) |
C17 | 0.049 (2) | 0.050 (2) | 0.061 (2) | −0.0057 (18) | 0.0108 (18) | −0.0034 (19) |
C18 | 0.063 (3) | 0.080 (3) | 0.057 (3) | −0.021 (2) | 0.0062 (19) | −0.016 (2) |
C19 | 0.059 (2) | 0.080 (3) | 0.051 (2) | −0.014 (2) | 0.0033 (17) | −0.001 (2) |
C20 | 0.0423 (19) | 0.052 (2) | 0.051 (2) | 0.0024 (17) | 0.0120 (17) | −0.0002 (18) |
C21 | 0.064 (2) | 0.056 (2) | 0.057 (2) | 0.0081 (19) | 0.0107 (17) | 0.0077 (18) |
C22 | 0.053 (2) | 0.049 (2) | 0.0451 (19) | 0.0059 (18) | 0.0058 (16) | −0.0008 (17) |
C23 | 0.056 (2) | 0.056 (2) | 0.072 (2) | 0.0005 (19) | 0.002 (2) | −0.0014 (19) |
C24 | 0.056 (3) | 0.081 (3) | 0.086 (3) | −0.003 (2) | 0.006 (2) | 0.013 (2) |
C25 | 0.043 (2) | 0.108 (3) | 0.067 (3) | 0.011 (2) | −0.0079 (18) | −0.012 (2) |
C26 | 0.067 (3) | 0.070 (3) | 0.080 (3) | 0.013 (2) | 0.001 (2) | −0.016 (2) |
C27 | 0.068 (3) | 0.051 (2) | 0.077 (3) | −0.001 (2) | 0.006 (2) | 0.0047 (19) |
C28 | 0.044 (2) | 0.055 (2) | 0.049 (2) | −0.0068 (19) | 0.0085 (18) | 0.0125 (18) |
C29 | 0.062 (2) | 0.058 (2) | 0.070 (2) | 0.0003 (19) | 0.003 (2) | −0.008 (2) |
C30 | 0.067 (3) | 0.071 (3) | 0.080 (3) | −0.004 (2) | 0.006 (2) | −0.014 (2) |
C31 | 0.072 (3) | 0.089 (3) | 0.061 (3) | −0.010 (2) | −0.002 (2) | −0.007 (2) |
C32 | 0.056 (2) | 0.077 (3) | 0.069 (3) | 0.000 (2) | 0.004 (2) | 0.019 (2) |
P1—O2 | 1.6530 (18) | C14—C15 | 1.405 (4) |
P1—O1 | 1.6549 (18) | C14—H14A | 0.9300 |
P1—N1 | 1.733 (2) | C15—C16 | 1.340 (4) |
O1—C1 | 1.392 (3) | C15—H15A | 0.9300 |
O2—C20 | 1.399 (3) | C16—C17 | 1.436 (4) |
N1—C28 | 1.387 (3) | C16—H16A | 0.9300 |
N1—C21 | 1.460 (3) | C17—C18 | 1.405 (3) |
N2—C32 | 1.326 (3) | C18—C19 | 1.356 (3) |
N2—C28 | 1.338 (3) | C18—H18A | 0.9300 |
C1—C10 | 1.367 (3) | C19—C20 | 1.409 (3) |
C1—C2 | 1.398 (3) | C19—H19A | 0.9300 |
C2—C3 | 1.350 (4) | C21—C22 | 1.505 (3) |
C2—H2A | 0.9300 | C21—H21A | 0.9700 |
C3—C4 | 1.401 (4) | C21—H21B | 0.9700 |
C3—H3A | 0.9300 | C22—C23 | 1.387 (3) |
C4—C5 | 1.416 (4) | C22—C27 | 1.389 (3) |
C4—C9 | 1.418 (4) | C23—C24 | 1.380 (4) |
C5—C6 | 1.337 (4) | C23—H23A | 0.9300 |
C5—H5A | 0.9300 | C24—C25 | 1.370 (4) |
C6—C7 | 1.403 (4) | C24—H24A | 0.9300 |
C6—H6A | 0.9300 | C25—C26 | 1.364 (4) |
C7—C8 | 1.381 (4) | C25—H25A | 0.9300 |
C7—H7A | 0.9300 | C26—C27 | 1.380 (4) |
C8—C9 | 1.417 (4) | C26—H26A | 0.9300 |
C8—H8A | 0.9300 | C27—H27A | 0.9300 |
C9—C10 | 1.431 (4) | C28—C29 | 1.393 (3) |
C10—C11 | 1.485 (3) | C29—C30 | 1.379 (4) |
C11—C20 | 1.361 (3) | C29—H29A | 0.9300 |
C11—C12 | 1.428 (3) | C30—C31 | 1.364 (4) |
C12—C13 | 1.408 (3) | C30—H30A | 0.9300 |
C12—C17 | 1.436 (3) | C31—C32 | 1.379 (4) |
C13—C14 | 1.376 (3) | C31—H31A | 0.9300 |
C13—H13A | 0.9300 | C32—H32A | 0.9300 |
O2—P1—O1 | 100.09 (9) | C15—C16—C17 | 121.3 (3) |
O2—P1—N1 | 103.69 (10) | C15—C16—H16A | 119.3 |
O1—P1—N1 | 93.54 (11) | C17—C16—H16A | 119.3 |
C1—O1—P1 | 118.97 (16) | C18—C17—C16 | 122.0 (3) |
C20—O2—P1 | 116.99 (17) | C18—C17—C12 | 119.9 (3) |
C28—N1—C21 | 118.5 (2) | C16—C17—C12 | 118.1 (3) |
C28—N1—P1 | 115.2 (2) | C19—C18—C17 | 121.0 (3) |
C21—N1—P1 | 125.45 (19) | C19—C18—H18A | 119.5 |
C32—N2—C28 | 118.1 (3) | C17—C18—H18A | 119.5 |
C10—C1—O1 | 120.3 (3) | C18—C19—C20 | 118.8 (3) |
C10—C1—C2 | 123.2 (3) | C18—C19—H19A | 120.6 |
O1—C1—C2 | 116.3 (3) | C20—C19—H19A | 120.6 |
C3—C2—C1 | 119.4 (3) | C11—C20—O2 | 120.5 (3) |
C3—C2—H2A | 120.3 | C11—C20—C19 | 123.4 (3) |
C1—C2—H2A | 120.3 | O2—C20—C19 | 116.1 (3) |
C2—C3—C4 | 121.2 (3) | N1—C21—C22 | 114.1 (2) |
C2—C3—H3A | 119.4 | N1—C21—H21A | 108.7 |
C4—C3—H3A | 119.4 | C22—C21—H21A | 108.7 |
C3—C4—C5 | 122.3 (4) | N1—C21—H21B | 108.7 |
C3—C4—C9 | 118.9 (3) | C22—C21—H21B | 108.7 |
C5—C4—C9 | 118.8 (4) | H21A—C21—H21B | 107.6 |
C6—C5—C4 | 121.4 (4) | C23—C22—C27 | 117.3 (3) |
C6—C5—H5A | 119.3 | C23—C22—C21 | 122.1 (3) |
C4—C5—H5A | 119.3 | C27—C22—C21 | 120.6 (3) |
C5—C6—C7 | 121.1 (4) | C24—C23—C22 | 120.1 (3) |
C5—C6—H6A | 119.5 | C24—C23—H23A | 120.0 |
C7—C6—H6A | 119.5 | C22—C23—H23A | 120.0 |
C8—C7—C6 | 119.5 (4) | C25—C24—C23 | 121.5 (3) |
C8—C7—H7A | 120.3 | C25—C24—H24A | 119.2 |
C6—C7—H7A | 120.3 | C23—C24—H24A | 119.2 |
C7—C8—C9 | 120.8 (3) | C26—C25—C24 | 119.5 (3) |
C7—C8—H8A | 119.6 | C26—C25—H25A | 120.3 |
C9—C8—H8A | 119.6 | C24—C25—H25A | 120.3 |
C8—C9—C4 | 118.4 (3) | C25—C26—C27 | 119.4 (3) |
C8—C9—C10 | 121.6 (3) | C25—C26—H26A | 120.3 |
C4—C9—C10 | 119.9 (3) | C27—C26—H26A | 120.3 |
C1—C10—C9 | 117.0 (3) | C26—C27—C22 | 122.3 (3) |
C1—C10—C11 | 119.4 (3) | C26—C27—H27A | 118.9 |
C9—C10—C11 | 123.5 (3) | C22—C27—H27A | 118.9 |
C20—C11—C12 | 118.4 (3) | N2—C28—N1 | 114.4 (3) |
C20—C11—C10 | 118.8 (3) | N2—C28—C29 | 122.1 (3) |
C12—C11—C10 | 122.7 (3) | N1—C28—C29 | 123.5 (3) |
C13—C12—C11 | 123.3 (3) | C30—C29—C28 | 117.7 (3) |
C13—C12—C17 | 118.4 (3) | C30—C29—H29A | 121.1 |
C11—C12—C17 | 118.3 (3) | C28—C29—H29A | 121.1 |
C14—C13—C12 | 121.1 (3) | C31—C30—C29 | 120.7 (3) |
C14—C13—H13A | 119.4 | C31—C30—H30A | 119.6 |
C12—C13—H13A | 119.4 | C29—C30—H30A | 119.6 |
C13—C14—C15 | 120.2 (3) | C30—C31—C32 | 117.4 (3) |
C13—C14—H14A | 119.9 | C30—C31—H31A | 121.3 |
C15—C14—H14A | 119.9 | C32—C31—H31A | 121.3 |
C16—C15—C14 | 120.7 (3) | N2—C32—C31 | 123.9 (3) |
C16—C15—H15A | 119.6 | N2—C32—H32A | 118.1 |
C14—C15—H15A | 119.6 | C31—C32—H32A | 118.1 |
O2—P1—O1—C1 | −41.8 (2) | C12—C13—C14—C15 | −0.7 (5) |
N1—P1—O1—C1 | −146.4 (2) | C13—C14—C15—C16 | 1.2 (5) |
O1—P1—O2—C20 | −49.4 (2) | C14—C15—C16—C17 | −0.1 (6) |
N1—P1—O2—C20 | 46.8 (2) | C15—C16—C17—C18 | 178.0 (3) |
O2—P1—N1—C28 | 76.7 (2) | C15—C16—C17—C12 | −1.5 (5) |
O1—P1—N1—C28 | 178.00 (19) | C13—C12—C17—C18 | −177.6 (3) |
O2—P1—N1—C21 | −92.7 (2) | C11—C12—C17—C18 | 0.9 (4) |
O1—P1—N1—C21 | 8.6 (2) | C13—C12—C17—C16 | 1.9 (4) |
P1—O1—C1—C10 | 74.9 (3) | C11—C12—C17—C16 | −179.6 (3) |
P1—O1—C1—C2 | −109.3 (2) | C16—C17—C18—C19 | −177.4 (3) |
C10—C1—C2—C3 | −2.4 (4) | C12—C17—C18—C19 | 2.1 (5) |
O1—C1—C2—C3 | −178.0 (3) | C17—C18—C19—C20 | −1.8 (5) |
C1—C2—C3—C4 | −2.8 (5) | C12—C11—C20—O2 | −175.0 (2) |
C2—C3—C4—C5 | −174.2 (3) | C10—C11—C20—O2 | 2.2 (4) |
C2—C3—C4—C9 | 3.0 (5) | C12—C11—C20—C19 | 4.5 (4) |
C3—C4—C5—C6 | 176.2 (3) | C10—C11—C20—C19 | −178.3 (3) |
C9—C4—C5—C6 | −1.0 (5) | P1—O2—C20—C11 | 76.0 (3) |
C4—C5—C6—C7 | −0.6 (6) | P1—O2—C20—C19 | −103.5 (2) |
C5—C6—C7—C8 | 1.6 (6) | C18—C19—C20—C11 | −1.6 (5) |
C6—C7—C8—C9 | −0.9 (5) | C18—C19—C20—O2 | 178.0 (3) |
C7—C8—C9—C4 | −0.8 (4) | C28—N1—C21—C22 | 72.2 (3) |
C7—C8—C9—C10 | −178.0 (3) | P1—N1—C21—C22 | −118.7 (2) |
C3—C4—C9—C8 | −175.6 (3) | N1—C21—C22—C23 | 33.8 (4) |
C5—C4—C9—C8 | 1.7 (4) | N1—C21—C22—C27 | −148.5 (3) |
C3—C4—C9—C10 | 1.6 (4) | C27—C22—C23—C24 | 0.7 (4) |
C5—C4—C9—C10 | 179.0 (3) | C21—C22—C23—C24 | 178.5 (3) |
O1—C1—C10—C9 | −177.8 (2) | C22—C23—C24—C25 | 0.3 (5) |
C2—C1—C10—C9 | 6.8 (4) | C23—C24—C25—C26 | −1.3 (5) |
O1—C1—C10—C11 | −1.4 (4) | C24—C25—C26—C27 | 1.1 (5) |
C2—C1—C10—C11 | −176.8 (2) | C25—C26—C27—C22 | 0.0 (5) |
C8—C9—C10—C1 | 170.9 (2) | C23—C22—C27—C26 | −0.9 (5) |
C4—C9—C10—C1 | −6.3 (4) | C21—C22—C27—C26 | −178.7 (3) |
C8—C9—C10—C11 | −5.4 (4) | C32—N2—C28—N1 | −177.8 (3) |
C4—C9—C10—C11 | 177.5 (3) | C32—N2—C28—C29 | 1.1 (4) |
C1—C10—C11—C20 | −52.8 (4) | C21—N1—C28—N2 | 172.3 (2) |
C9—C10—C11—C20 | 123.4 (3) | P1—N1—C28—N2 | 2.1 (3) |
C1—C10—C11—C12 | 124.2 (3) | C21—N1—C28—C29 | −6.6 (4) |
C9—C10—C11—C12 | −59.6 (4) | P1—N1—C28—C29 | −176.8 (2) |
C20—C11—C12—C13 | 174.4 (3) | N2—C28—C29—C30 | −2.5 (4) |
C10—C11—C12—C13 | −2.7 (4) | N1—C28—C29—C30 | 176.3 (3) |
C20—C11—C12—C17 | −4.0 (4) | C28—C29—C30—C31 | 1.9 (5) |
C10—C11—C12—C17 | 178.9 (3) | C29—C30—C31—C32 | 0.1 (5) |
C11—C12—C13—C14 | −179.3 (3) | C28—N2—C32—C31 | 1.1 (5) |
C17—C12—C13—C14 | −0.9 (4) | C30—C31—C32—N2 | −1.7 (5) |
Experimental details
Crystal data | |
Chemical formula | C32H23N2O2P |
Mr | 498.49 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 294 |
a, b, c (Å) | 9.5168 (11), 10.3952 (11), 25.398 (3) |
V (Å3) | 2512.6 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.36 × 0.32 × 0.30 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.950, 0.958 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17396, 5805, 2424 |
Rint | 0.075 |
(sin θ/λ)max (Å−1) | 0.652 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.058, 0.90 |
No. of reflections | 5805 |
No. of parameters | 334 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.21 |
Absolute structure | Flack (1983), 0000 Friedel pairs |
Absolute structure parameter | 0.15 (9) |
Computer programs: SMART (Siemens, 1995), SMART, SHELXTL (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
P1—N1 | 1.733 (2) | C1—C2 | 1.398 (3) |
O1—C1 | 1.392 (3) | C2—C3 | 1.350 (4) |
N1—C28 | 1.387 (3) | C4—C5 | 1.416 (4) |
N1—C21 | 1.460 (3) | C4—C9 | 1.418 (4) |
N2—C28 | 1.338 (3) | C5—C6 | 1.337 (4) |
O2—P1—O1 | 100.09 (9) | C3—C2—C1 | 119.4 (3) |
O2—P1—N1 | 103.69 (10) | C2—C3—C4 | 121.2 (3) |
O1—P1—N1 | 93.54 (11) | C6—C5—C4 | 121.4 (4) |
C1—O1—P1 | 118.97 (16) | C7—C8—C9 | 120.8 (3) |
C10—C1—C2 | 123.2 (3) | C8—C9—C10 | 121.6 (3) |
N1—P1—O2—C20 | 46.8 (2) | P1—O1—C1—C10 | 74.9 (3) |
O2—P1—N1—C28 | 76.7 (2) | C1—C10—C11—C20 | −52.8 (4) |
O2—P1—N1—C21 | −92.7 (2) | C9—C10—C11—C12 | −59.6 (4) |
Recently, some striking results have been obtained in the Cu-catalyzed enantioselective conjugate addition of organometallic reagents. In particular, diorganozinc reagents, to α,β-unsaturated esters, acyclic and cyclic enones by using chiral phosphoramidite ligands (Feringa et al., 1997). Our research shows that the phosphoramidite ligands derived from 2-aminopyridine and binaphthol is an efficient ligand in 1,4-conjugate addition of diphenyzinc to cyclic enones. Herein, as part of our investigation, we report the crystal structure of the title compound, (I). The crystal structure (Fig. 1) showed that both bond lengths and angles are within normal range (Table 1).