Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102021042/de1193sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102021042/de1193Isup2.hkl |
CCDC reference: 204048
The preparation of (I) proceeded as follows. A solution of (R)-(6,6'-methoxybiphenyl-2,2'-diyl)bis(diphenylphosphine oxide) (1 g, 1.6 mmol) in CH2Cl2 (20 ml) was cooled to 195 K. To this solution, BBr3 (1.6 g, 6.4 mmol) was added via a syringe over 30 min. The mixture was stirred at 195 K for 1 hr, and then slowly warmed to room temperature and reacted overnight. After cooling the mixture to 273 K, water was added slowly and the aqueous layer was removed via a cannula. The organic layer was mixed with methanol and dichloromethane (Ratio?). The resulting solution was dried over Na2SO4 and evaporated to dryness to give the raw product, which was purified by silica-gel column chromatography with CHCl3 and CH3OH (Ratio?). Spectroscopic analysis: 1H NMR (DMSO, 500 MHz, δ, p.p.m.): 6.5–6.7 (dd, 2H, J = 7.5 Hz,), 6.6–6.8 (d, 2H, J = 8 Hz), 7.0–7.1 (m, 2H), 7.3–7.7 (m, 20H); 31P NMR (DMSO, δ, p.p.m.): 29.2; high-resolution MS: 586.1439; calculated for C36H28P2O4: 586.1463.
H atoms were placed in their geometrically calculated positions and included in the final refinement in the riding model approximation, with O—H distances of 0.82 Å and C—H distances in the range 0.93–0.98 Å. Is this added text correct?
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL-NT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.
C36H28O4P2·CH4O | Dx = 1.326 Mg m−3 |
Mr = 618.57 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 5948 reflections |
a = 9.9351 (16) Å | θ = 1.0–27.5° |
b = 11.1490 (17) Å | µ = 0.18 mm−1 |
c = 27.977 (4) Å | T = 294 K |
V = 3098.9 (8) Å3 | Plate, colourless |
Z = 4 | 0.26 × 0.24 × 0.10 mm |
F(000) = 1296 |
Bruker Model CCD area-detector diffractometer | 7141 independent reflections |
Radiation source: fine-focus sealed tube | 3814 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: empirical (using intensity measurements) (SAINT; Siemens, 1995) | h = −12→12 |
Tmin = 0.954, Tmax = 0.982 | k = −14→10 |
21252 measured reflections | l = −35→36 |
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)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.83 | (Δ/σ)max = 0.001 |
7141 reflections | Δρmax = 0.25 e Å−3 |
400 parameters | Δρmin = −0.24 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with 3113 Friedel pairs Is this correct |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.06 (8) |
C36H28O4P2·CH4O | V = 3098.9 (8) Å3 |
Mr = 618.57 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.9351 (16) Å | µ = 0.18 mm−1 |
b = 11.1490 (17) Å | T = 294 K |
c = 27.977 (4) Å | 0.26 × 0.24 × 0.10 mm |
Bruker Model CCD area-detector diffractometer | 7141 independent reflections |
Absorption correction: empirical (using intensity measurements) (SAINT; Siemens, 1995) | 3814 reflections with I > 2σ(I) |
Tmin = 0.954, Tmax = 0.982 | Rint = 0.066 |
21252 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.075 | Δρmax = 0.25 e Å−3 |
S = 0.83 | Δρmin = −0.24 e Å−3 |
7141 reflections | Absolute structure: Flack (1983), with 3113 Friedel pairs Is this correct |
400 parameters | Absolute structure parameter: −0.06 (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 | ||
P1 | 0.28454 (7) | 0.93328 (7) | 0.80954 (2) | 0.03429 (18) | |
P2 | 0.52558 (8) | 1.07782 (8) | 0.95518 (2) | 0.0418 (2) | |
O1 | 0.24160 (19) | 1.27489 (17) | 0.93534 (6) | 0.0511 (6) | |
H1 | 0.1957 | 1.2943 | 0.9584 | 0.077* | |
O2 | 0.30313 (19) | 1.25192 (18) | 0.79898 (6) | 0.0506 (5) | |
H2B | 0.3157 | 1.3067 | 0.7799 | 0.076* | |
O3 | 0.41916 (19) | 0.97721 (16) | 0.79465 (6) | 0.0423 (5) | |
O4 | 0.5903 (2) | 1.15499 (18) | 0.99192 (6) | 0.0571 (6) | |
C1 | 0.1984 (3) | 1.0284 (2) | 0.85186 (8) | 0.0298 (6) | |
C2 | 0.0626 (3) | 1.0025 (2) | 0.85959 (9) | 0.0374 (7) | |
H2A | 0.0209 | 0.9433 | 0.8415 | 0.045* | |
C3 | −0.0106 (3) | 1.0634 (3) | 0.89371 (8) | 0.0423 (7) | |
H3A | −0.1004 | 1.0439 | 0.8988 | 0.051* | |
C4 | 0.0488 (3) | 1.1532 (3) | 0.92028 (9) | 0.0409 (7) | |
H4A | −0.0001 | 1.1931 | 0.9437 | 0.049* | |
C5 | 0.1807 (3) | 1.1831 (2) | 0.91184 (9) | 0.0351 (7) | |
C6 | 0.2595 (2) | 1.1215 (2) | 0.87798 (8) | 0.0273 (6) | |
C7 | 0.3981 (3) | 1.1681 (2) | 0.86871 (9) | 0.0308 (7) | |
C8 | 0.4137 (3) | 1.2389 (2) | 0.82709 (9) | 0.0317 (7) | |
C9 | 0.5337 (3) | 1.2933 (2) | 0.81631 (9) | 0.0394 (7) | |
H9A | 0.5414 | 1.3395 | 0.7888 | 0.047* | |
C10 | 0.6433 (3) | 1.2796 (3) | 0.84625 (10) | 0.0452 (8) | |
H10A | 0.7249 | 1.3160 | 0.8389 | 0.054* | |
C11 | 0.6305 (3) | 1.2118 (2) | 0.88690 (9) | 0.0410 (8) | |
H11A | 0.7046 | 1.2021 | 0.9068 | 0.049* | |
C12 | 0.5089 (3) | 1.1568 (2) | 0.89915 (8) | 0.0330 (7) | |
C13 | 0.1708 (3) | 0.9193 (3) | 0.75935 (8) | 0.0356 (7) | |
C14 | 0.1599 (3) | 1.0161 (3) | 0.72887 (10) | 0.0521 (9) | |
H14A | 0.2087 | 1.0857 | 0.7350 | 0.063* | |
C15 | 0.0765 (4) | 1.0103 (3) | 0.68903 (11) | 0.0634 (10) | |
H15A | 0.0688 | 1.0761 | 0.6688 | 0.076* | |
C16 | 0.0056 (3) | 0.9076 (3) | 0.67959 (10) | 0.0591 (9) | |
H16A | −0.0494 | 0.9034 | 0.6527 | 0.071* | |
C17 | 0.0155 (3) | 0.8117 (3) | 0.70946 (10) | 0.0545 (9) | |
H17A | −0.0333 | 0.7423 | 0.7030 | 0.065* | |
C18 | 0.0985 (3) | 0.8169 (3) | 0.74974 (10) | 0.0448 (8) | |
H18A | 0.1049 | 0.7511 | 0.7700 | 0.054* | |
C19 | 0.2971 (3) | 0.7846 (2) | 0.83587 (9) | 0.0422 (8) | |
C20 | 0.2041 (3) | 0.7330 (3) | 0.86620 (10) | 0.0510 (8) | |
H20A | 0.1272 | 0.7759 | 0.8744 | 0.061* | |
C21 | 0.2220 (4) | 0.6202 (3) | 0.88450 (11) | 0.0635 (10) | |
H21A | 0.1583 | 0.5880 | 0.9052 | 0.076* | |
C22 | 0.3334 (4) | 0.5547 (3) | 0.87240 (13) | 0.0793 (12) | |
H22A | 0.3446 | 0.4775 | 0.8843 | 0.095* | |
C23 | 0.4277 (4) | 0.6030 (3) | 0.84282 (14) | 0.0826 (12) | |
H23A | 0.5044 | 0.5593 | 0.8350 | 0.099* | |
C24 | 0.4098 (3) | 0.7183 (3) | 0.82406 (11) | 0.0617 (9) | |
H24A | 0.4741 | 0.7505 | 0.8035 | 0.074* | |
C25 | 0.3697 (3) | 1.0198 (3) | 0.97765 (9) | 0.0408 (8) | |
C26 | 0.3126 (3) | 1.0775 (3) | 1.01647 (10) | 0.0617 (9) | |
H26A | 0.3554 | 1.1433 | 1.0301 | 0.074* | |
C27 | 0.1912 (4) | 1.0371 (3) | 1.03490 (11) | 0.0724 (11) | |
H27A | 0.1527 | 1.0763 | 1.0609 | 0.087* | |
C28 | 0.1276 (3) | 0.9405 (3) | 1.01538 (11) | 0.0631 (10) | |
H28A | 0.0461 | 0.9141 | 1.0279 | 0.076* | |
C29 | 0.1843 (3) | 0.8829 (3) | 0.97741 (10) | 0.0527 (9) | |
H29A | 0.1410 | 0.8170 | 0.9640 | 0.063* | |
C30 | 0.3048 (3) | 0.9212 (3) | 0.95875 (9) | 0.0423 (7) | |
H30A | 0.3429 | 0.8804 | 0.9331 | 0.051* | |
C31 | 0.6339 (3) | 0.9540 (2) | 0.94028 (9) | 0.0398 (7) | |
C32 | 0.6311 (3) | 0.8975 (3) | 0.89636 (11) | 0.0562 (9) | |
H32A | 0.5686 | 0.9216 | 0.8735 | 0.067* | |
C33 | 0.7196 (4) | 0.8060 (3) | 0.88585 (12) | 0.0695 (10) | |
H33A | 0.7164 | 0.7686 | 0.8562 | 0.083* | |
C34 | 0.8122 (4) | 0.7701 (3) | 0.91921 (14) | 0.0705 (10) | |
H34A | 0.8711 | 0.7077 | 0.9124 | 0.085* | |
C35 | 0.8176 (3) | 0.8258 (3) | 0.96211 (13) | 0.0679 (11) | |
H35A | 0.8817 | 0.8022 | 0.9844 | 0.081* | |
C36 | 0.7292 (3) | 0.9175 (3) | 0.97322 (10) | 0.0546 (8) | |
H36A | 0.7338 | 0.9546 | 1.0029 | 0.066* | |
O5 | 0.6678 (2) | 0.9158 (2) | 0.76975 (8) | 0.0618 (6) | |
H5 | 0.5917 | 0.9376 | 0.7771 | 0.150* | |
C37 | 0.7566 (4) | 1.0118 (3) | 0.77421 (12) | 0.0755 (11) | |
H37A | 0.7396 | 1.0661 | 0.7483 | 0.091* | |
H37B | 0.8488 | 0.9803 | 0.7711 | 0.120* | |
H37C | 0.7652 | 1.0581 | 0.8038 | 0.120* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0323 (4) | 0.0352 (4) | 0.0353 (4) | 0.0000 (4) | 0.0001 (3) | −0.0050 (4) |
P2 | 0.0446 (5) | 0.0492 (5) | 0.0316 (4) | −0.0078 (4) | −0.0057 (4) | −0.0040 (4) |
O1 | 0.0561 (15) | 0.0477 (13) | 0.0494 (13) | −0.0101 (11) | 0.0190 (10) | −0.0252 (11) |
O2 | 0.0407 (13) | 0.0553 (14) | 0.0558 (13) | −0.0060 (11) | −0.0063 (11) | 0.0220 (11) |
O3 | 0.0302 (11) | 0.0482 (13) | 0.0485 (11) | 0.0006 (9) | 0.0052 (9) | −0.0118 (10) |
O4 | 0.0619 (15) | 0.0714 (15) | 0.0382 (11) | −0.0172 (12) | −0.0132 (11) | −0.0136 (11) |
C1 | 0.0277 (17) | 0.0341 (16) | 0.0275 (13) | −0.0016 (13) | 0.0007 (13) | 0.0016 (12) |
C2 | 0.0317 (19) | 0.0397 (18) | 0.0409 (16) | −0.0041 (13) | −0.0036 (14) | −0.0046 (14) |
C3 | 0.0288 (17) | 0.053 (2) | 0.0450 (16) | 0.0005 (17) | 0.0097 (14) | 0.0022 (17) |
C4 | 0.0350 (19) | 0.044 (2) | 0.0434 (17) | −0.0016 (15) | 0.0104 (15) | −0.0048 (15) |
C5 | 0.0385 (19) | 0.0363 (18) | 0.0305 (15) | −0.0021 (15) | 0.0064 (14) | −0.0036 (14) |
C6 | 0.0260 (16) | 0.0303 (15) | 0.0258 (14) | −0.0010 (12) | 0.0023 (12) | 0.0019 (12) |
C7 | 0.0323 (18) | 0.0309 (16) | 0.0292 (15) | −0.0006 (13) | 0.0051 (13) | −0.0078 (13) |
C8 | 0.0300 (18) | 0.0293 (16) | 0.0359 (16) | −0.0008 (14) | −0.0002 (14) | −0.0046 (14) |
C9 | 0.0394 (18) | 0.0405 (18) | 0.0383 (16) | −0.0038 (15) | 0.0083 (16) | 0.0042 (14) |
C10 | 0.0373 (19) | 0.048 (2) | 0.0500 (18) | −0.0083 (16) | 0.0076 (16) | −0.0084 (17) |
C11 | 0.0330 (19) | 0.049 (2) | 0.0412 (17) | −0.0036 (15) | −0.0082 (14) | −0.0024 (16) |
C12 | 0.0317 (18) | 0.0352 (17) | 0.0320 (14) | −0.0065 (14) | 0.0002 (14) | −0.0063 (13) |
C13 | 0.0318 (16) | 0.0358 (16) | 0.0391 (15) | −0.0008 (15) | 0.0026 (13) | −0.0066 (16) |
C14 | 0.063 (2) | 0.042 (2) | 0.0512 (19) | −0.0020 (17) | −0.0045 (18) | −0.0014 (17) |
C15 | 0.075 (3) | 0.063 (2) | 0.051 (2) | 0.009 (2) | −0.017 (2) | 0.0053 (19) |
C16 | 0.052 (2) | 0.076 (3) | 0.0493 (19) | 0.012 (2) | −0.0189 (17) | −0.009 (2) |
C17 | 0.042 (2) | 0.064 (2) | 0.057 (2) | −0.0043 (18) | −0.0075 (17) | −0.0146 (19) |
C18 | 0.041 (2) | 0.046 (2) | 0.0475 (19) | −0.0011 (16) | 0.0015 (16) | −0.0022 (16) |
C19 | 0.045 (2) | 0.0396 (18) | 0.0424 (17) | 0.0060 (17) | −0.0082 (15) | −0.0103 (15) |
C20 | 0.063 (2) | 0.041 (2) | 0.0490 (18) | −0.0006 (18) | −0.0035 (18) | 0.0039 (16) |
C21 | 0.089 (3) | 0.049 (2) | 0.052 (2) | −0.012 (2) | −0.005 (2) | 0.0049 (18) |
C22 | 0.103 (4) | 0.046 (3) | 0.089 (3) | −0.008 (3) | −0.026 (3) | 0.005 (2) |
C23 | 0.074 (3) | 0.049 (3) | 0.125 (3) | 0.026 (2) | −0.017 (3) | −0.005 (2) |
C24 | 0.060 (3) | 0.047 (2) | 0.078 (2) | 0.0075 (19) | 0.000 (2) | −0.0014 (19) |
C25 | 0.045 (2) | 0.047 (2) | 0.0305 (16) | −0.0049 (15) | −0.0062 (14) | −0.0007 (14) |
C26 | 0.074 (3) | 0.061 (2) | 0.0499 (19) | −0.021 (2) | 0.0144 (18) | −0.0167 (19) |
C27 | 0.078 (3) | 0.080 (3) | 0.058 (2) | −0.012 (2) | 0.023 (2) | −0.020 (2) |
C28 | 0.056 (2) | 0.072 (3) | 0.061 (2) | −0.015 (2) | 0.0128 (18) | 0.000 (2) |
C29 | 0.057 (2) | 0.051 (2) | 0.0507 (19) | −0.0099 (18) | −0.0035 (18) | −0.0016 (17) |
C30 | 0.049 (2) | 0.0412 (18) | 0.0370 (15) | −0.0005 (17) | −0.0032 (15) | −0.0024 (16) |
C31 | 0.0363 (18) | 0.044 (2) | 0.0388 (16) | −0.0051 (15) | −0.0059 (14) | 0.0015 (15) |
C32 | 0.054 (2) | 0.055 (2) | 0.059 (2) | 0.0056 (18) | −0.0076 (17) | −0.0063 (18) |
C33 | 0.071 (3) | 0.059 (2) | 0.079 (3) | 0.007 (2) | 0.001 (2) | −0.016 (2) |
C34 | 0.056 (3) | 0.054 (2) | 0.101 (3) | 0.0078 (19) | 0.003 (2) | 0.011 (2) |
C35 | 0.048 (2) | 0.078 (3) | 0.077 (3) | −0.004 (2) | −0.013 (2) | 0.027 (2) |
C36 | 0.049 (2) | 0.066 (2) | 0.0490 (18) | −0.004 (2) | −0.0054 (16) | 0.0135 (18) |
O5 | 0.0444 (13) | 0.0692 (15) | 0.0719 (14) | 0.0036 (13) | 0.0100 (12) | −0.0297 (13) |
C37 | 0.057 (3) | 0.079 (3) | 0.091 (3) | −0.009 (2) | 0.002 (2) | −0.025 (2) |
P1—O3 | 1.4839 (19) | C17—H17A | 0.9300 |
P1—C1 | 1.805 (3) | C18—H18A | 0.9300 |
P1—C13 | 1.809 (3) | C19—C20 | 1.381 (4) |
P1—C19 | 1.818 (3) | C19—C24 | 1.382 (4) |
P2—O4 | 1.4866 (18) | C20—C21 | 1.369 (4) |
P2—C25 | 1.792 (3) | C20—H20A | 0.9300 |
P2—C31 | 1.800 (3) | C21—C22 | 1.369 (4) |
P2—C12 | 1.806 (3) | C21—H21A | 0.9300 |
O1—C5 | 1.359 (3) | C22—C23 | 1.362 (5) |
O1—H1 | 0.8200 | C22—H22A | 0.9300 |
O2—C8 | 1.359 (3) | C23—C24 | 1.400 (4) |
O2—H2B | 0.8200 | C23—H23A | 0.9300 |
C1—C2 | 1.397 (3) | C24—H24A | 0.9300 |
C1—C6 | 1.407 (3) | C25—C30 | 1.379 (4) |
C2—C3 | 1.379 (3) | C25—C26 | 1.384 (4) |
C2—H2A | 0.9300 | C26—C27 | 1.387 (4) |
C3—C4 | 1.379 (3) | C26—H26A | 0.9300 |
C3—H3A | 0.9300 | C27—C28 | 1.362 (4) |
C4—C5 | 1.373 (4) | C27—H27A | 0.9300 |
C4—H4A | 0.9300 | C28—C29 | 1.363 (4) |
C5—C6 | 1.407 (3) | C28—H28A | 0.9300 |
C6—C7 | 1.495 (3) | C29—C30 | 1.375 (4) |
C7—C12 | 1.397 (3) | C29—H29A | 0.9300 |
C7—C8 | 1.415 (3) | C30—H30A | 0.9300 |
C8—C9 | 1.371 (3) | C31—C32 | 1.381 (3) |
C9—C10 | 1.382 (4) | C31—C36 | 1.382 (3) |
C9—H9A | 0.9300 | C32—C33 | 1.379 (4) |
C10—C11 | 1.372 (3) | C32—H32A | 0.9300 |
C10—H10A | 0.9300 | C33—C34 | 1.370 (4) |
C11—C12 | 1.397 (3) | C33—H33A | 0.9300 |
C11—H11A | 0.9300 | C34—C35 | 1.353 (4) |
C13—C18 | 1.376 (3) | C34—H34A | 0.9300 |
C13—C14 | 1.380 (3) | C35—C36 | 1.383 (4) |
C14—C15 | 1.391 (4) | C35—H35A | 0.9300 |
C14—H14A | 0.9300 | C36—H36A | 0.9300 |
C15—C16 | 1.370 (4) | O5—C37 | 1.393 (3) |
C15—H15A | 0.9300 | O5—H5 | 0.8200 |
C16—C17 | 1.361 (4) | C37—H37A | 0.9599 |
C16—H16A | 0.9300 | C37—H37B | 0.9845 |
C17—C18 | 1.398 (4) | C37—H37C | 0.9802 |
O3—P1—C1 | 114.67 (12) | C13—C18—C17 | 120.0 (3) |
O3—P1—C13 | 111.93 (11) | C13—C18—H18A | 120.0 |
C1—P1—C13 | 105.29 (12) | C17—C18—H18A | 120.0 |
O3—P1—C19 | 110.66 (13) | C20—C19—C24 | 117.8 (3) |
C1—P1—C19 | 107.59 (12) | C20—C19—P1 | 125.7 (2) |
C13—P1—C19 | 106.20 (13) | C24—C19—P1 | 116.5 (2) |
O4—P2—C25 | 109.90 (12) | C21—C20—C19 | 121.7 (3) |
O4—P2—C31 | 110.21 (13) | C21—C20—H20A | 119.1 |
C25—P2—C31 | 108.72 (13) | C19—C20—H20A | 119.1 |
O4—P2—C12 | 110.95 (12) | C22—C21—C20 | 120.2 (3) |
C25—P2—C12 | 113.65 (12) | C22—C21—H21A | 119.9 |
C31—P2—C12 | 103.19 (12) | C20—C21—H21A | 119.9 |
C5—O1—H1 | 109.5 | C23—C22—C21 | 119.7 (4) |
C8—O2—H2B | 109.5 | C23—C22—H22A | 120.1 |
C2—C1—C6 | 119.2 (2) | C21—C22—H22A | 120.1 |
C2—C1—P1 | 116.0 (2) | C22—C23—C24 | 120.3 (4) |
C6—C1—P1 | 124.7 (2) | C22—C23—H23A | 119.9 |
C3—C2—C1 | 121.0 (3) | C24—C23—H23A | 119.9 |
C3—C2—H2A | 119.5 | C19—C24—C23 | 120.3 (3) |
C1—C2—H2A | 119.5 | C19—C24—H24A | 119.9 |
C4—C3—C2 | 120.3 (3) | C23—C24—H24A | 119.9 |
C4—C3—H3A | 119.8 | C30—C25—C26 | 118.7 (3) |
C2—C3—H3A | 119.8 | C30—C25—P2 | 123.9 (2) |
C5—C4—C3 | 119.5 (3) | C26—C25—P2 | 117.5 (2) |
C5—C4—H4A | 120.3 | C25—C26—C27 | 119.8 (3) |
C3—C4—H4A | 120.3 | C25—C26—H26A | 120.1 |
O1—C5—C4 | 121.6 (2) | C27—C26—H26A | 120.1 |
O1—C5—C6 | 116.5 (2) | C28—C27—C26 | 120.7 (3) |
C4—C5—C6 | 121.9 (3) | C28—C27—H27A | 119.6 |
C1—C6—C5 | 118.0 (2) | C26—C27—H27A | 119.6 |
C1—C6—C7 | 124.3 (2) | C27—C28—C29 | 119.6 (3) |
C5—C6—C7 | 117.3 (2) | C27—C28—H28A | 120.2 |
C12—C7—C8 | 117.7 (2) | C29—C28—H28A | 120.2 |
C12—C7—C6 | 126.1 (2) | C28—C29—C30 | 120.6 (3) |
C8—C7—C6 | 116.0 (2) | C28—C29—H29A | 119.7 |
O2—C8—C9 | 121.9 (2) | C30—C29—H29A | 119.7 |
O2—C8—C7 | 116.6 (2) | C29—C30—C25 | 120.6 (3) |
C9—C8—C7 | 121.5 (2) | C29—C30—H30A | 119.7 |
C8—C9—C10 | 120.2 (3) | C25—C30—H30A | 119.7 |
C8—C9—H9A | 119.9 | C32—C31—C36 | 118.2 (3) |
C10—C9—H9A | 119.9 | C32—C31—P2 | 122.9 (2) |
C11—C10—C9 | 119.4 (3) | C36—C31—P2 | 118.7 (2) |
C11—C10—H10A | 120.3 | C33—C32—C31 | 120.9 (3) |
C9—C10—H10A | 120.3 | C33—C32—H32A | 119.5 |
C10—C11—C12 | 121.7 (3) | C31—C32—H32A | 119.5 |
C10—C11—H11A | 119.2 | C34—C33—C32 | 119.9 (3) |
C12—C11—H11A | 119.2 | C34—C33—H33A | 120.0 |
C11—C12—C7 | 119.5 (2) | C32—C33—H33A | 120.0 |
C11—C12—P2 | 110.3 (2) | C35—C34—C33 | 119.8 (3) |
C7—C12—P2 | 130.2 (2) | C35—C34—H34A | 120.1 |
C18—C13—C14 | 119.2 (2) | C33—C34—H34A | 120.1 |
C18—C13—P1 | 123.3 (2) | C34—C35—C36 | 120.9 (3) |
C14—C13—P1 | 117.5 (2) | C34—C35—H35A | 119.6 |
C13—C14—C15 | 120.4 (3) | C36—C35—H35A | 119.6 |
C13—C14—H14A | 119.8 | C31—C36—C35 | 120.2 (3) |
C15—C14—H14A | 119.8 | C31—C36—H36A | 119.9 |
C16—C15—C14 | 120.0 (3) | C35—C36—H36A | 119.9 |
C16—C15—H15A | 120.0 | C37—O5—H5 | 109.5 |
C14—C15—H15A | 120.0 | O5—C37—H37A | 107.7 |
C17—C16—C15 | 120.1 (3) | O5—C37—H37B | 107.9 |
C17—C16—H16A | 120.0 | H37A—C37—H37B | 108.8 |
C15—C16—H16A | 120.0 | O5—C37—H37C | 122.4 |
C16—C17—C18 | 120.3 (3) | H37A—C37—H37C | 108.8 |
C16—C17—H17A | 119.8 | H37B—C37—H37C | 100.5 |
C18—C17—H17A | 119.8 | ||
O3—P1—C1—C2 | 168.16 (18) | C18—C13—C14—C15 | 0.2 (4) |
C13—P1—C1—C2 | 44.7 (2) | P1—C13—C14—C15 | 178.6 (2) |
C19—P1—C1—C2 | −68.3 (2) | C13—C14—C15—C16 | −0.7 (5) |
O3—P1—C1—C6 | −14.1 (2) | C14—C15—C16—C17 | 0.7 (5) |
C13—P1—C1—C6 | −137.6 (2) | C15—C16—C17—C18 | −0.4 (5) |
C19—P1—C1—C6 | 109.4 (2) | C14—C13—C18—C17 | 0.1 (4) |
C6—C1—C2—C3 | −2.7 (4) | P1—C13—C18—C17 | −178.2 (2) |
P1—C1—C2—C3 | 175.1 (2) | C16—C17—C18—C13 | 0.0 (4) |
C1—C2—C3—C4 | 1.3 (4) | O3—P1—C19—C20 | 158.7 (2) |
C2—C3—C4—C5 | 1.3 (4) | C1—P1—C19—C20 | 32.7 (3) |
C3—C4—C5—O1 | 176.6 (2) | C13—P1—C19—C20 | −79.7 (2) |
C3—C4—C5—C6 | −2.5 (4) | O3—P1—C19—C24 | −21.6 (3) |
C2—C1—C6—C5 | 1.4 (3) | C1—P1—C19—C24 | −147.6 (2) |
P1—C1—C6—C5 | −176.17 (19) | C13—P1—C19—C24 | 100.1 (2) |
C2—C1—C6—C7 | −171.9 (2) | C24—C19—C20—C21 | 0.4 (4) |
P1—C1—C6—C7 | 10.5 (3) | P1—C19—C20—C21 | −179.8 (2) |
O1—C5—C6—C1 | −178.0 (2) | C19—C20—C21—C22 | −0.9 (5) |
C4—C5—C6—C1 | 1.1 (4) | C20—C21—C22—C23 | 1.3 (5) |
O1—C5—C6—C7 | −4.2 (3) | C21—C22—C23—C24 | −1.2 (6) |
C4—C5—C6—C7 | 174.9 (2) | C20—C19—C24—C23 | −0.4 (4) |
C1—C6—C7—C12 | −112.7 (3) | P1—C19—C24—C23 | 179.9 (2) |
C5—C6—C7—C12 | 73.9 (3) | C22—C23—C24—C19 | 0.8 (5) |
C1—C6—C7—C8 | 73.1 (3) | O4—P2—C25—C30 | −161.1 (2) |
C5—C6—C7—C8 | −100.2 (3) | C31—P2—C25—C30 | −40.4 (3) |
C12—C7—C8—O2 | −177.8 (2) | C12—P2—C25—C30 | 73.9 (3) |
C6—C7—C8—O2 | −3.1 (3) | O4—P2—C25—C26 | 18.5 (3) |
C12—C7—C8—C9 | 1.0 (4) | C31—P2—C25—C26 | 139.2 (2) |
C6—C7—C8—C9 | 175.7 (2) | C12—P2—C25—C26 | −106.5 (2) |
O2—C8—C9—C10 | 178.9 (2) | C30—C25—C26—C27 | −1.2 (4) |
C7—C8—C9—C10 | 0.1 (4) | P2—C25—C26—C27 | 179.3 (3) |
C8—C9—C10—C11 | −0.4 (4) | C25—C26—C27—C28 | 0.3 (5) |
C9—C10—C11—C12 | −0.6 (4) | C26—C27—C28—C29 | 0.2 (5) |
C10—C11—C12—C7 | 1.8 (4) | C27—C28—C29—C30 | 0.1 (5) |
C10—C11—C12—P2 | −178.6 (2) | C28—C29—C30—C25 | −0.9 (4) |
C8—C7—C12—C11 | −2.0 (4) | C26—C25—C30—C29 | 1.5 (4) |
C6—C7—C12—C11 | −176.0 (2) | P2—C25—C30—C29 | −179.0 (2) |
C8—C7—C12—P2 | 178.6 (2) | O4—P2—C31—C32 | −152.7 (2) |
C6—C7—C12—P2 | 4.5 (4) | C25—P2—C31—C32 | 86.8 (3) |
O4—P2—C12—C11 | 48.3 (2) | C12—P2—C31—C32 | −34.2 (3) |
C25—P2—C12—C11 | 172.76 (19) | O4—P2—C31—C36 | 23.8 (3) |
C31—P2—C12—C11 | −69.7 (2) | C25—P2—C31—C36 | −96.7 (2) |
O4—P2—C12—C7 | −132.2 (2) | C12—P2—C31—C36 | 142.3 (2) |
C25—P2—C12—C7 | −7.8 (3) | C36—C31—C32—C33 | 0.9 (5) |
C31—P2—C12—C7 | 109.8 (3) | P2—C31—C32—C33 | 177.5 (2) |
O3—P1—C13—C18 | 128.7 (2) | C31—C32—C33—C34 | −0.2 (5) |
C1—P1—C13—C18 | −106.1 (2) | C32—C33—C34—C35 | −0.9 (5) |
C19—P1—C13—C18 | 7.8 (3) | C33—C34—C35—C36 | 1.2 (5) |
O3—P1—C13—C14 | −49.6 (2) | C32—C31—C36—C35 | −0.7 (4) |
C1—P1—C13—C14 | 75.6 (2) | P2—C31—C36—C35 | −177.3 (2) |
C19—P1—C13—C14 | −170.5 (2) | C34—C35—C36—C31 | −0.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4i | 0.82 | 1.83 | 2.648 (2) | 177 |
O2—H2B···O5ii | 0.82 | 1.85 | 2.669 (3) | 172 |
O5—H5···O3 | 0.82 | 1.84 | 2.656 (3) | 177 |
CgA—CgB | ? | ? | 3.568 (6) | 14 |
CgC—CgD | ? | ? | 4.912 (6) | 180 |
CgE—CgF | ? | ? | 4.339 (8) | 162 |
Symmetry codes: (i) x−1/2, −y+5/2, −z+2; (ii) −x+1, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C36H28O4P2·CH4O |
Mr | 618.57 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 294 |
a, b, c (Å) | 9.9351 (16), 11.1490 (17), 27.977 (4) |
V (Å3) | 3098.9 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.26 × 0.24 × 0.10 |
Data collection | |
Diffractometer | Bruker Model CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SAINT; Siemens, 1995) |
Tmin, Tmax | 0.954, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21252, 7141, 3814 |
Rint | 0.066 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.075, 0.83 |
No. of reflections | 7141 |
No. of parameters | 400 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.24 |
Absolute structure | Flack (1983), with 3113 Friedel pairs Is this correct |
Absolute structure parameter | −0.06 (8) |
Computer programs: SMART (Siemens, 1995), SMART, SHELXTL-NT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-NT.
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4i | 0.82 | 1.83 | 2.648 (2) | 176.8 |
O2—H2B···O5ii | 0.82 | 1.85 | 2.669 (3) | 171.6 |
O5—H5···O3 | 0.82 | 1.84 | 2.656 (3) | 176.6 |
CgA—CgB | ? | ? | 3.568 (6) | 13.7 |
CgC—CgD | ? | ? | 4.912 (6) | 179.9 |
CgE—CgF | ? | ? | 4.339 (8) | 162.1 |
Symmetry codes: (i) x−1/2, −y+5/2, −z+2; (ii) −x+1, y+1/2, −z+3/2. |
Chiral bidentate phosphines are among the most important auxiliaries in enantioselective homogeneous catalysis. The atropisomeric diphosphine ligands, such as Noyori's BINAP (Noyori, 1989; Noyori & Takaya, 1990) and Schmid's BIPHEP classes (Schmid et al., 1988, 1991, 1996) have been widely applied in asymmetric catalysis, especially in hydrogenation, and excellent results have been achieved.
The theories of supramolecular chemistry and crystal engineering inspire the design of microporous layers employing self-assembly of molecular subunits (tectons), driven by non-covalent interactions as the synthetic tool (Moulton & Zaworotko, 2001). In this paper, the synthesis of the title compound, (I), a derivative of (R)-(6,6'-methoxybiphenyl-2,2'-diyl)bis(diphenylphosphine oxide), MeO-BIPHEPO, is described. The compound can be used as a building block for the synthesis of new diphosphine ligands. \sch
In the crystal of (I), there are three kinds of hydrogen bonds (Fig. 1). In the first, the O1—H1 group of one molecule of (I) interacts with atom O4 of a phosphine oxide group in an adjacent molecule, with O1—H1···O4A 2.648 Å. In the second, the O2—H2B group in (I) with atom O5B in the CH3OH solvate, with O2—H2B···O5B 2.669 Å. In the third, atom O3 of the phosphine oxide group interacts with H5—O5 in the CH3OH solvate, with O3···H5—O5 2.656 Å.
In addition to these hydrogen bonds, there are intra- and intermolecular π–π interactions between the phenyl rings of (I). The distance between the centroid of ring C1—C6 (CgA) and that of ring C25—C30 (CgB) is 3.568 Å, and the angle between the two ring planes of this intramolecular π–π stacking interaction is 13.7°. The phenyl rings C7—C12 (CgC) and C31—C36 (CgD) are also involved in a weak intramolecular π–π stacking interaction, with CgC···CgD 4.912 Å and with the angle between the two planes being 179.9°. There are also π–π stacking interactions between the phenyl rings of the Ph2PO groups and the equivalent phenyl rings in an adjacent molecule. The shortest of these has a distance between the two symmetry-related phenyl rings of 4.339 Å and an angle of 162.1° (Table 1 and Fig. 1).
Through these rich hydrogen-bonding interactions, every molecule of (I) is linked to four adjacent molecules. Furthermore, a three-dimensional supramolecular chiral parallelogram channel (cavity demension ca 9.2 × 6.7 Å2) along the crystallographic a axis, having the empirical formula C36H28O4P2·CH3OH, is constructed via self-assembly (Figs. 2 and 3). These channels are divided into mini compartments by the phenyl groups linked to the P atoms. This result suggests a novel approach to the design of chiral microporous structures containing P atoms.