Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S205322961402542X/ku3144sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S205322961402542X/ku3144Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S205322961402542X/ku3144Isup3.pdf |
CCDC reference: 1035173
Optically active phosphines are known to play an important role in various metal-catalyzed asymmetric reactions (Etayo & Vidal-Ferran, 2013). Undoubtedly the most famous example of this class of chiral phosphine ligand is (R,R)-1,2-bis[(o-methoxyphenyl)phenylphosphanyl]ethane (DiPAMP). The corresponding rhodium-based catalyst was the first asymmetric catalyst employed on an industrial scale for the production of the Parkinson's disease drug L-DOPA (Knowles et al., 1975). Despite this breakthrough discovery, relatively little attention has been paid to this class of molecules for many years (Carey, 2014). Following research work completed in AdvaChemLab, a series of P-chiral phosphine ligands were synthesized and investigated for their hydrogenation capability. To our surprise, neither the free bisphosphine (DiPAMP) nor its analogues that maintain the ethylenebisphosphine frame have had their crystal structures reported. The presented structure of (S,S)-ethylenebis[(2-methylphenyl)phenylphosphine], denoted o-tolyl-DiPAMP, is therefore believed to be the first example of a compound from this family in its enantiomerically pure form.
o-Tolyl-DiPAMP was synthesized using a modified Appel reaction (Bergin et al., 2007). The corresponding racemic monophosphine was reacted under modified Appel conditions to give enantiomerically pure monophosphine oxide. Subsequent reduction using trichlorosilane at an elevated temperature and in situ boronation furnished the monophosphine borane. Copper-mediated coupling gave the bisphosphine borane, which was deprotected under standard conditions using diethylamine to give the target compound, o-tolyl-DiPAMP. More detailed information about the synthetic procedure is provided in supporting Information.
The oxygen sensitivity of bisphosphines complicates the growing and handling a suitable crystal for X-ray analysis. It was found that slow evaporation of a solution of the title compound in tetrahydrofuran under a gentle stream of nitrogen gas gave suitable crystals after two weeks of growth.
Crystal data, data collection and structure refinement details are summarized in Table 1. The positions of all H atoms were calculated geometrically and refined using a riding model, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms, and C—H = 0.93 (phenyl) or 0.97 Å (ethyl), and with Uiso(H) = 1.2Ueq(C) for all other H atoms. The absolute structure was determined on the basis of the Flack parameter [x = -0.007 (17); Flack, 1983].
Crystals of the title compound, o-tolyl-DiPAMP, are chiral on the P atoms and contain solely the S,S enantiomer. In the Cambridge Structural Database (CSD; Version ???; Allen, 2002), we found only two crystal structures of an enantiomerically pure, chiral on P, noncyclic bis(diarylphosphine), namely (S,S)-1,3-bis[(2-aminophenyl)phenylphosphino]propane (CSD refcode CUTZUM; Ansell et al., 1985) and (R,R)-ethylenebis[(2-methylphenyl)phenylphosphine dioxide] (denoted o-tolyl-DiPAMPO; CSD refcode SIHDET; King et al. (2007). The investigated o-tolyl-DiPAMP crystals, possessing the S,S configuration, are isostructural with the latter crystals. The S and R designations has been reversed (according to the Cahn–Ingold–Prelog naming system; Cahn et al., 1966) because in the dioxide the lone electron pair on the chiral phosphorus centre is replaced by an P atom, making it the highest priority, instead of the lowest.
The isostructurality index Id (Fábián & Kálmán, 1999), calculated with the SimMK program (Kowiel, 2011), has a value of 96.7 (2)%. The ability of a phosphine derivative to form solid solutions with its dioxide analogue has been noted previously by Mohamed et al. (2004).
Parameters describing the molecular geometry around the P atoms in o-tolyl-DiPAMP are compared with the analogous data for o-tolyl-DiPAMPO in Table 2. Although in both structures the values of the C—P—C angles are significantly less than the tetrahedral value, they are consistently smaller in o-tolyl-DiPAMP than in o-tolyl-DiPAMPO. Combined with this is a significant lengthening of the P—C bond [average values = 1.844 (4) and 1.812 (4) Å in o-tolyl-DiPAMP and o-tolyl-DiPAMPO, respectively] and a more widely spread distribution of the values of the exocyclic Cortho—Cipso—P valence angles. The described geometrical differences between the two closely related molecules illustrate a space-demanding effect of a lone pair at the P atoms in o-tolyl-DiPAMP.
In both compounds, the P—C—C—P chain adopts an extended trans conformation. Of the two P—Cipso bonds attached to the same P atom, one always forms an extension to the zigzag chain defined by the P—C—C—P atoms. Interestingly, at one end of the molecule this extension is accomplished by the phenyl substituent, while at the other end , it is accomplished by the o-tolyl P—Cipso bond, thus reducing the molecular symmetry from C2 to C1. Moreover, while this o-tolyl ring is nearly parallel to the P—C—C—P plane, the interplanar angle being only 5.4 (2)°; its counterpart at the other P atom (i.e. the phenyl ring) is twisted around this bond and forms an angle of 57.2 (1)° with this plane. The planes of the phenyl and o-tolyl rings attached to the same P atom are nearly perpendicular to one another. The relative orientation of the like-substituents can be described as G+ (phenyl rings), G- (o-tolyl rings) and T (the lone pairs); when viewed along the P1···P2 direction. The investigated compound forms crystals that are isostructural with those of its dioxide, despite an involvement of the dioxide in C—H···O(═P) hydrogen bonds and the lack thereof in the investigated crystal structure, as illustrated in Fig. 2.
Slight differences between the two structures are noticeable on the powder diffraction diagrams shown in Fig. 3. The patterns were calculated using Mecury (Macrae et al., 2006) from the known crystal structures and were stacked with identical scales on the abscissa using the KDif program (Knížek, 2005). Using a Hirshfeld surface analysis (McKinnon et al., 2004) implemented in CrystalExplorer (Wolff et al., 2007), we were able to quantify the amount of molecular surface involved in various interaction types. It appeared that the H···H dispersion interactions involve 68% of the molecular surface area, while in the dioxide analogue this percentage is lower (61%) in favour of C—H···O(═P) hydrogen bonds, which involve almost 9% of the molecular surface area. Second in rank are weak C—H···π interactions nearly equally distributed in both compounds, engaging 29 and 30% of the surface area of the o-tolyl-DiPAMP and o-tolyl-DiPAMPO molecules, respectively. The arrangement of the molecules in both types of crystals is compared in Fig. 2. It can be seen that the resulting structure of o-tolyl-DiPAMP is consistent with directionality of C—H(ethylene)···O(═P) hydrogen bonds observed in the crystals of o-tolyl-DiPAMPO, indicating that in the former crystals, the immediate acceptor of a hydrogen bond from the ethylene H atoms there is some negative charge accumulated in a lone-pair region. However, the molecular surface area engaged in these H···P interactions is very small and amounts to only 2.4%. We are currently investigating the asymmetric catalytic potential of Rh, Ru and Ir complexes of o-tolyl-DiPAMP and o-tolyl-DiPAMPO.
Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006) and XP (Siemens, 1994); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C28H28P2 | F(000) = 904 |
Mr = 426.44 | Dx = 1.216 Mg m−3 |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 9393 reflections |
a = 5.9725 (1) Å | θ = 2.6–76.1° |
b = 17.0935 (2) Å | µ = 1.77 mm−1 |
c = 22.8179 (3) Å | T = 100 K |
V = 2329.50 (6) Å3 | Needle, colourless |
Z = 4 | 0.6 × 0.1 × 0.1 mm |
Agilent SuperNova Atlas diffractometer | 4101 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 4013 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.030 |
Detector resolution: 10.5357 pixels mm-1 | θmax = 66.6°, θmin = 4.7° |
ω scans | h = −7→5 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | k = −20→20 |
Tmin = 0.383, Tmax = 1.000 | l = −25→27 |
10411 measured reflections |
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)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0597P)2 + 0.4488P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
4101 reflections | Δρmax = 0.37 e Å−3 |
273 parameters | Δρmin = −0.30 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 1716 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.007 (17) |
C28H28P2 | V = 2329.50 (6) Å3 |
Mr = 426.44 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 5.9725 (1) Å | µ = 1.77 mm−1 |
b = 17.0935 (2) Å | T = 100 K |
c = 22.8179 (3) Å | 0.6 × 0.1 × 0.1 mm |
Agilent SuperNova Atlas diffractometer | 4101 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | 4013 reflections with I > 2σ(I) |
Tmin = 0.383, Tmax = 1.000 | Rint = 0.030 |
10411 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.091 | Δρmax = 0.37 e Å−3 |
S = 1.05 | Δρmin = −0.30 e Å−3 |
4101 reflections | Absolute structure: Flack (1983), 1716 Friedel pairs |
273 parameters | Absolute structure parameter: −0.007 (17) |
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 | 0.49729 (8) | 0.94930 (3) | 0.088442 (19) | 0.02406 (13) | |
P2 | 0.87215 (8) | 0.79349 (3) | 0.21201 (2) | 0.02412 (13) | |
C1 | 0.5845 (3) | 0.89767 (10) | 0.02119 (8) | 0.0207 (4) | |
C2 | 0.7691 (3) | 0.84772 (11) | 0.01890 (8) | 0.0230 (4) | |
H2 | 0.8648 | 0.8447 | 0.0510 | 0.028* | |
C3 | 0.8128 (3) | 0.80221 (11) | −0.03043 (9) | 0.0265 (4) | |
H3 | 0.9364 | 0.7691 | −0.0312 | 0.032* | |
C4 | 0.6716 (3) | 0.80655 (11) | −0.07822 (8) | 0.0278 (4) | |
H4 | 0.6973 | 0.7752 | −0.1108 | 0.033* | |
C5 | 0.4921 (3) | 0.85751 (11) | −0.07762 (8) | 0.0261 (4) | |
H5 | 0.4007 | 0.8612 | −0.1105 | 0.031* | |
C6 | 0.4453 (3) | 0.90355 (11) | −0.02853 (8) | 0.0226 (4) | |
C7 | 0.2480 (3) | 0.95806 (12) | −0.02966 (9) | 0.0303 (4) | |
H7A | 0.1614 | 0.9487 | −0.0644 | 0.045* | |
H7B | 0.3000 | 1.0112 | −0.0296 | 0.045* | |
H7C | 0.1567 | 0.9491 | 0.0043 | 0.045* | |
C8 | 0.5887 (3) | 1.05044 (11) | 0.07285 (8) | 0.0231 (4) | |
C9 | 0.7971 (4) | 1.06822 (12) | 0.04972 (11) | 0.0385 (5) | |
H9 | 0.8985 | 1.0282 | 0.0420 | 0.046* | |
C10 | 0.8558 (4) | 1.14527 (13) | 0.03804 (10) | 0.0375 (5) | |
H10 | 0.9950 | 1.1565 | 0.0218 | 0.045* | |
C11 | 0.7083 (4) | 1.20508 (12) | 0.05037 (9) | 0.0323 (5) | |
H11 | 0.7484 | 1.2568 | 0.0432 | 0.039* | |
C12 | 0.5015 (4) | 1.18762 (12) | 0.07343 (10) | 0.0368 (5) | |
H12 | 0.4008 | 1.2277 | 0.0814 | 0.044* | |
C13 | 0.4420 (3) | 1.11081 (12) | 0.08479 (9) | 0.0300 (4) | |
H13 | 0.3020 | 1.0998 | 0.1006 | 0.036* | |
C14 | 0.7097 (4) | 0.91686 (11) | 0.14227 (8) | 0.0285 (4) | |
H14A | 0.8569 | 0.9174 | 0.1243 | 0.034* | |
H14B | 0.7115 | 0.9523 | 0.1754 | 0.034* | |
C15 | 0.6537 (4) | 0.83361 (11) | 0.16324 (8) | 0.0278 (4) | |
H15A | 0.6372 | 0.7997 | 0.1295 | 0.033* | |
H15B | 0.5119 | 0.8344 | 0.1840 | 0.033* | |
C16 | 0.7597 (3) | 0.69611 (11) | 0.22942 (8) | 0.0244 (4) | |
C17 | 0.5725 (4) | 0.66581 (13) | 0.20152 (10) | 0.0338 (5) | |
H17 | 0.4914 | 0.6975 | 0.1761 | 0.041* | |
C18 | 0.5031 (4) | 0.58908 (13) | 0.21064 (11) | 0.0420 (5) | |
H18 | 0.3767 | 0.5699 | 0.1916 | 0.050* | |
C19 | 0.6229 (5) | 0.54176 (13) | 0.24794 (11) | 0.0438 (6) | |
H19 | 0.5788 | 0.4902 | 0.2540 | 0.053* | |
C20 | 0.8088 (5) | 0.57098 (13) | 0.27645 (10) | 0.0431 (6) | |
H20 | 0.8876 | 0.5385 | 0.3019 | 0.052* | |
C23 | 0.8147 (3) | 0.84800 (11) | 0.27976 (8) | 0.0237 (4) | |
C24 | 0.9765 (3) | 0.90033 (11) | 0.29878 (9) | 0.0301 (4) | |
H24 | 1.1080 | 0.9061 | 0.2774 | 0.036* | |
C25 | 0.9451 (4) | 0.94440 (13) | 0.34947 (10) | 0.0380 (5) | |
H25 | 1.0552 | 0.9792 | 0.3617 | 0.046* | |
C26 | 0.7509 (4) | 0.93635 (12) | 0.38142 (10) | 0.0370 (5) | |
H26 | 0.7297 | 0.9654 | 0.4154 | 0.044* | |
C27 | 0.5871 (4) | 0.88462 (13) | 0.36261 (10) | 0.0371 (5) | |
H27 | 0.4558 | 0.8791 | 0.3841 | 0.045* | |
C28 | 0.6174 (4) | 0.84099 (13) | 0.31198 (9) | 0.0320 (4) | |
H28 | 0.5057 | 0.8070 | 0.2995 | 0.038* | |
C21 | 0.8820 (4) | 0.64765 (12) | 0.26830 (9) | 0.0308 (4) | |
C22 | 1.0821 (5) | 0.67819 (15) | 0.30089 (11) | 0.0474 (6) | |
H22A | 1.0338 | 0.7140 | 0.3307 | 0.071* | |
H22B | 1.1799 | 0.7048 | 0.2741 | 0.071* | |
H22C | 1.1607 | 0.6353 | 0.3187 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0317 (2) | 0.0185 (2) | 0.0220 (2) | 0.0008 (2) | 0.0060 (2) | −0.00025 (17) |
P2 | 0.0289 (2) | 0.0238 (2) | 0.0197 (2) | −0.0048 (2) | 0.00220 (19) | 0.00001 (17) |
C1 | 0.0270 (9) | 0.0123 (8) | 0.0226 (9) | −0.0016 (7) | 0.0033 (7) | 0.0000 (6) |
C2 | 0.0258 (9) | 0.0184 (9) | 0.0248 (9) | −0.0013 (8) | −0.0003 (7) | 0.0015 (7) |
C3 | 0.0276 (9) | 0.0207 (9) | 0.0313 (10) | 0.0020 (8) | 0.0061 (8) | −0.0020 (7) |
C4 | 0.0346 (10) | 0.0243 (9) | 0.0244 (10) | −0.0052 (8) | 0.0075 (8) | −0.0053 (8) |
C5 | 0.0297 (9) | 0.0275 (10) | 0.0211 (9) | −0.0066 (8) | 0.0003 (8) | 0.0008 (7) |
C6 | 0.0243 (9) | 0.0169 (9) | 0.0266 (9) | −0.0030 (7) | 0.0026 (7) | 0.0021 (7) |
C7 | 0.0273 (10) | 0.0288 (11) | 0.0347 (11) | 0.0039 (9) | −0.0028 (8) | 0.0030 (8) |
C8 | 0.0323 (9) | 0.0172 (9) | 0.0197 (8) | −0.0004 (8) | 0.0016 (7) | 0.0013 (7) |
C9 | 0.0401 (12) | 0.0230 (11) | 0.0525 (14) | 0.0057 (9) | 0.0163 (11) | 0.0009 (9) |
C10 | 0.0377 (12) | 0.0265 (11) | 0.0484 (13) | −0.0034 (9) | 0.0103 (10) | 0.0050 (9) |
C11 | 0.0454 (12) | 0.0186 (9) | 0.0328 (10) | −0.0007 (9) | −0.0084 (9) | 0.0038 (8) |
C12 | 0.0427 (11) | 0.0248 (10) | 0.0430 (12) | 0.0122 (10) | −0.0003 (11) | 0.0004 (9) |
C13 | 0.0317 (10) | 0.0248 (10) | 0.0336 (10) | 0.0051 (8) | −0.0005 (8) | 0.0026 (8) |
C14 | 0.0420 (11) | 0.0234 (10) | 0.0202 (9) | −0.0029 (8) | 0.0005 (8) | −0.0010 (7) |
C15 | 0.0386 (11) | 0.0246 (10) | 0.0200 (9) | −0.0054 (9) | −0.0019 (8) | 0.0026 (7) |
C16 | 0.0314 (10) | 0.0229 (9) | 0.0189 (9) | −0.0008 (8) | 0.0053 (8) | −0.0005 (7) |
C17 | 0.0344 (10) | 0.0317 (11) | 0.0353 (11) | −0.0068 (9) | −0.0015 (9) | 0.0005 (8) |
C18 | 0.0415 (11) | 0.0306 (11) | 0.0540 (14) | −0.0115 (10) | 0.0122 (12) | −0.0085 (10) |
C19 | 0.0600 (15) | 0.0188 (10) | 0.0524 (14) | −0.0029 (11) | 0.0294 (12) | −0.0028 (9) |
C20 | 0.0682 (16) | 0.0251 (11) | 0.0361 (12) | 0.0156 (11) | 0.0124 (11) | 0.0020 (9) |
C23 | 0.0307 (9) | 0.0186 (9) | 0.0217 (9) | −0.0002 (7) | −0.0021 (7) | 0.0013 (7) |
C24 | 0.0299 (9) | 0.0249 (10) | 0.0354 (10) | −0.0023 (9) | −0.0002 (9) | −0.0028 (8) |
C25 | 0.0437 (12) | 0.0287 (11) | 0.0415 (12) | −0.0006 (9) | −0.0107 (10) | −0.0116 (9) |
C26 | 0.0561 (13) | 0.0271 (11) | 0.0278 (10) | 0.0074 (10) | −0.0034 (10) | −0.0056 (8) |
C27 | 0.0457 (12) | 0.0364 (12) | 0.0293 (11) | 0.0009 (10) | 0.0102 (9) | −0.0016 (9) |
C28 | 0.0337 (10) | 0.0329 (11) | 0.0294 (10) | −0.0050 (9) | 0.0028 (9) | −0.0022 (8) |
C21 | 0.0416 (11) | 0.0271 (10) | 0.0237 (9) | 0.0093 (9) | 0.0038 (9) | −0.0045 (8) |
C22 | 0.0580 (15) | 0.0405 (13) | 0.0438 (13) | 0.0205 (12) | −0.0202 (12) | −0.0089 (10) |
P1—C1 | 1.8454 (18) | C14—C15 | 1.538 (3) |
P1—C8 | 1.8475 (19) | C14—H14A | 0.9700 |
P1—C14 | 1.851 (2) | C14—H14B | 0.9700 |
P2—C23 | 1.8374 (19) | C15—H15A | 0.9700 |
P2—C16 | 1.8383 (19) | C15—H15B | 0.9700 |
P2—C15 | 1.847 (2) | C16—C17 | 1.387 (3) |
C1—C2 | 1.395 (3) | C16—C21 | 1.416 (3) |
C1—C6 | 1.410 (3) | C17—C18 | 1.391 (3) |
C2—C3 | 1.393 (3) | C17—H17 | 0.9300 |
C2—H2 | 0.9300 | C18—C19 | 1.375 (4) |
C3—C4 | 1.381 (3) | C18—H18 | 0.9300 |
C3—H3 | 0.9300 | C19—C20 | 1.380 (4) |
C4—C5 | 1.381 (3) | C19—H19 | 0.9300 |
C4—H4 | 0.9300 | C20—C21 | 1.394 (3) |
C5—C6 | 1.397 (3) | C20—H20 | 0.9300 |
C5—H5 | 0.9300 | C23—C24 | 1.387 (3) |
C6—C7 | 1.502 (3) | C23—C28 | 1.394 (3) |
C7—H7A | 0.9600 | C24—C25 | 1.393 (3) |
C7—H7B | 0.9600 | C24—H24 | 0.9300 |
C7—H7C | 0.9600 | C25—C26 | 1.377 (3) |
C8—C13 | 1.381 (3) | C25—H25 | 0.9300 |
C8—C9 | 1.386 (3) | C26—C27 | 1.387 (3) |
C9—C10 | 1.389 (3) | C26—H26 | 0.9300 |
C9—H9 | 0.9300 | C27—C28 | 1.387 (3) |
C10—C11 | 1.378 (3) | C27—H27 | 0.9300 |
C10—H10 | 0.9300 | C28—H28 | 0.9300 |
C11—C12 | 1.375 (3) | C21—C22 | 1.502 (3) |
C11—H11 | 0.9300 | C22—H22A | 0.9600 |
C12—C13 | 1.385 (3) | C22—H22B | 0.9600 |
C12—H12 | 0.9300 | C22—H22C | 0.9600 |
C13—H13 | 0.9300 | ||
C1—P1—C8 | 101.77 (8) | C15—C14—H14B | 109.8 |
C1—P1—C14 | 102.42 (9) | P1—C14—H14B | 109.8 |
C8—P1—C14 | 101.87 (9) | H14A—C14—H14B | 108.2 |
C23—P2—C16 | 102.08 (8) | C14—C15—P2 | 112.18 (14) |
C23—P2—C15 | 100.76 (9) | C14—C15—H15A | 109.2 |
C16—P2—C15 | 102.03 (9) | P2—C15—H15A | 109.2 |
C2—C1—C6 | 118.65 (17) | C14—C15—H15B | 109.2 |
C2—C1—P1 | 123.15 (14) | P2—C15—H15B | 109.2 |
C6—C1—P1 | 117.93 (14) | H15A—C15—H15B | 107.9 |
C3—C2—C1 | 121.34 (18) | C17—C16—C21 | 118.98 (19) |
C3—C2—H2 | 119.3 | C17—C16—P2 | 122.24 (15) |
C1—C2—H2 | 119.3 | C21—C16—P2 | 118.47 (15) |
C4—C3—C2 | 119.58 (18) | C16—C17—C18 | 121.6 (2) |
C4—C3—H3 | 120.2 | C16—C17—H17 | 119.2 |
C2—C3—H3 | 120.2 | C18—C17—H17 | 119.2 |
C3—C4—C5 | 120.01 (17) | C19—C18—C17 | 119.5 (2) |
C3—C4—H4 | 120.0 | C19—C18—H18 | 120.3 |
C5—C4—H4 | 120.0 | C17—C18—H18 | 120.3 |
C4—C5—C6 | 121.22 (18) | C18—C19—C20 | 119.8 (2) |
C4—C5—H5 | 119.4 | C18—C19—H19 | 120.1 |
C6—C5—H5 | 119.4 | C20—C19—H19 | 120.1 |
C5—C6—C1 | 119.13 (17) | C19—C20—C21 | 122.0 (2) |
C5—C6—C7 | 119.50 (17) | C19—C20—H20 | 119.0 |
C1—C6—C7 | 121.37 (17) | C21—C20—H20 | 119.0 |
C6—C7—H7A | 109.5 | C24—C23—C28 | 118.67 (18) |
C6—C7—H7B | 109.5 | C24—C23—P2 | 117.39 (15) |
H7A—C7—H7B | 109.5 | C28—C23—P2 | 123.92 (15) |
C6—C7—H7C | 109.5 | C23—C24—C25 | 121.0 (2) |
H7A—C7—H7C | 109.5 | C23—C24—H24 | 119.5 |
H7B—C7—H7C | 109.5 | C25—C24—H24 | 119.5 |
C13—C8—C9 | 118.75 (18) | C26—C25—C24 | 119.9 (2) |
C13—C8—P1 | 118.30 (14) | C26—C25—H25 | 120.0 |
C9—C8—P1 | 122.95 (15) | C24—C25—H25 | 120.0 |
C8—C9—C10 | 120.5 (2) | C25—C26—C27 | 119.6 (2) |
C8—C9—H9 | 119.7 | C25—C26—H26 | 120.2 |
C10—C9—H9 | 119.7 | C27—C26—H26 | 120.2 |
C11—C10—C9 | 120.2 (2) | C26—C27—C28 | 120.6 (2) |
C11—C10—H10 | 119.9 | C26—C27—H27 | 119.7 |
C9—C10—H10 | 119.9 | C28—C27—H27 | 119.7 |
C12—C11—C10 | 119.40 (19) | C27—C28—C23 | 120.2 (2) |
C12—C11—H11 | 120.3 | C27—C28—H28 | 119.9 |
C10—C11—H11 | 120.3 | C23—C28—H28 | 119.9 |
C11—C12—C13 | 120.5 (2) | C20—C21—C16 | 118.2 (2) |
C11—C12—H12 | 119.7 | C20—C21—C22 | 120.7 (2) |
C13—C12—H12 | 119.7 | C16—C21—C22 | 121.1 (2) |
C8—C13—C12 | 120.60 (19) | C21—C22—H22A | 109.5 |
C8—C13—H13 | 119.7 | C21—C22—H22B | 109.5 |
C12—C13—H13 | 119.7 | H22A—C22—H22B | 109.5 |
C15—C14—P1 | 109.56 (14) | C21—C22—H22C | 109.5 |
C15—C14—H14A | 109.8 | H22A—C22—H22C | 109.5 |
P1—C14—H14A | 109.8 | H22B—C22—H22C | 109.5 |
C8—P1—C1—C2 | 105.61 (16) | C23—P2—C15—C14 | 74.89 (15) |
C14—P1—C1—C2 | 0.48 (17) | C16—P2—C15—C14 | 179.85 (14) |
C8—P1—C1—C6 | −80.48 (15) | C23—P2—C16—C17 | 112.25 (17) |
C14—P1—C1—C6 | 174.39 (14) | C15—P2—C16—C17 | 8.32 (19) |
C6—C1—C2—C3 | −2.2 (3) | C23—P2—C16—C21 | −74.22 (16) |
P1—C1—C2—C3 | 171.71 (14) | C15—P2—C16—C21 | −178.15 (15) |
C1—C2—C3—C4 | 0.2 (3) | C21—C16—C17—C18 | −0.3 (3) |
C2—C3—C4—C5 | 1.9 (3) | P2—C16—C17—C18 | 173.18 (17) |
C3—C4—C5—C6 | −2.1 (3) | C16—C17—C18—C19 | −0.3 (3) |
C4—C5—C6—C1 | 0.0 (3) | C17—C18—C19—C20 | 0.7 (3) |
C4—C5—C6—C7 | −179.84 (17) | C18—C19—C20—C21 | −0.6 (3) |
C2—C1—C6—C5 | 2.0 (3) | C16—P2—C23—C24 | 141.02 (15) |
P1—C1—C6—C5 | −172.15 (13) | C15—P2—C23—C24 | −114.05 (16) |
C2—C1—C6—C7 | −178.09 (17) | C16—P2—C23—C28 | −40.48 (19) |
P1—C1—C6—C7 | 7.7 (2) | C15—P2—C23—C28 | 64.45 (18) |
C1—P1—C8—C13 | 134.48 (15) | C28—C23—C24—C25 | 0.9 (3) |
C14—P1—C8—C13 | −119.96 (16) | P2—C23—C24—C25 | 179.49 (17) |
C1—P1—C8—C9 | −45.44 (19) | C23—C24—C25—C26 | −0.1 (3) |
C14—P1—C8—C9 | 60.12 (19) | C24—C25—C26—C27 | −0.4 (3) |
C13—C8—C9—C10 | −0.9 (3) | C25—C26—C27—C28 | 0.0 (3) |
P1—C8—C9—C10 | 179.03 (19) | C26—C27—C28—C23 | 0.8 (3) |
C8—C9—C10—C11 | 1.2 (4) | C24—C23—C28—C27 | −1.3 (3) |
C9—C10—C11—C12 | −1.1 (3) | P2—C23—C28—C27 | −179.74 (17) |
C10—C11—C12—C13 | 0.7 (3) | C19—C20—C21—C16 | 0.0 (3) |
C9—C8—C13—C12 | 0.5 (3) | C19—C20—C21—C22 | 178.8 (2) |
P1—C8—C13—C12 | −179.42 (17) | C17—C16—C21—C20 | 0.5 (3) |
C11—C12—C13—C8 | −0.4 (3) | P2—C16—C21—C20 | −173.27 (15) |
C1—P1—C14—C15 | −77.81 (15) | C17—C16—C21—C22 | −178.3 (2) |
C8—P1—C14—C15 | 177.13 (13) | P2—C16—C21—C22 | 8.0 (3) |
P1—C14—C15—P2 | 174.79 (10) |
Experimental details
Crystal data | |
Chemical formula | C28H28P2 |
Mr | 426.44 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 5.9725 (1), 17.0935 (2), 22.8179 (3) |
V (Å3) | 2329.50 (6) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 1.77 |
Crystal size (mm) | 0.6 × 0.1 × 0.1 |
Data collection | |
Diffractometer | Agilent SuperNova Atlas diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2013) |
Tmin, Tmax | 0.383, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10411, 4101, 4013 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.091, 1.05 |
No. of reflections | 4101 |
No. of parameters | 273 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.30 |
Absolute structure | Flack (1983), 1716 Friedel pairs |
Absolute structure parameter | −0.007 (17) |
Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006) and XP (Siemens, 1994).
o-tolyl-DiPAMP | o-tolyl-DiPAMPO | |
P1—C1 | 1.8454 (18) | 1.820 (2) |
P1—C8 | 1.8475 (19) | 1.807 (2) |
P1—C14 | 1.851 (2) | 1.810 (2) |
P2—C16 | 1.8383 (19) | 1.810 (2) |
P2—C23 | 1.8374 (19) | 1.809 (2) |
P2—C15 | 1.847 (2) | 1.814 (2) |
C1—P1—C8 | 101.77 (8) | 106.15 (9) |
C1—P1—C14 | 102.42 (9) | 106.51 (9) |
C8—P1—C14 | 101.87 (9) | 105.90 (9) |
C23—P2—C16 | 102.08 (8) | 106.57 (9) |
C23—P2—C15 | 100.76 (9) | 105.93 (9) |
C16—P2—C15 | 102.03 (9) | 106.01 (9) |
C2—C1—P1 | 123.15 (14) | 121.03 (15) |
C6—C1—P1 | 117.93 (14) | 119.68 (14) |
C13—C8—P1 | 118.30 (14) | 118.02 (15) |
C9—C8—P1 | 122.95 (15) | 122.50 (15) |
C15—C14—P1 | 109.56 (14) | 110.90 (13) |
C14—C15—P2 | 112.18 (14) | 111.86 (14) |
C17—C16—P2 | 122.24 (15) | 119.83 (16) |
C21—C16—P2 | 118.47 (15) | 120.29 (16) |
C24—C23—P2 | 117.39 (15) | 117.64 (16) |
C28—C23—P2 | 123.92 (15) | 122.69 (16) |
C14—P1—C1—C2 | 0.48 (17) | -6.35 (18) |
C14—P1—C1—C6 | 174.39 (14) | 168.64 (15) |
C14—P1—C8—C13 | -119.96 (16) | -116.62 (17) |
C14—P1—C8—C9 | 60.12 (19) | 65.00 (19) |
C1—P1—C14—C15 | -77.81 (15) | -73.63 (15) |
C8—P1—C14—C15 | 177.13 (13) | 173.66 (14) |
P1—C14—C15—P2 | 174.79 (10) | 176.78 (11) |
C23—P2—C15—C14 | 74.89 (15) | 71.38 (16) |
C16—P2—C15—C14 | 179.85 (14) | -175.64 (14) |
C15—P2—C16—C17 | 8.32 (19) | 0.1 (2) |
C15—P2—C16—C21 | -178.15 (15) | 177.22 (17) |
C15—P2—C23—C24 | -114.05 (16) | -109.26 (18) |
C15—P2—C23—C28 | 64.45 (18) | 70.29 (19) |