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In connection with a research program involving the synthesis, structure determination, reactivity and ability to coordinate to metal centres of chiral bis­phosphine ligands, we have synthesized and structurally characterized, by means of single-crystal X-ray diffraction analysis, the title compound {systematic name: (S,S)-(ethane-1,2-di­yl)bis­[(2-methyl­phen­yl)phenyl­phosphane], abbreviated as o-tolyl-DiPAMP}, C28H28P2. So far, neither the free bisphosphine (DiPAMP) nor analogues that incorporate the ethyl­enebisphosphine frame have had their crystal structures reported. The investigated compound forms crystals which are isostructural with the bis­phosphine dioxide analogue [King et al. (2007). Acta Cryst. E63, o3278], despite the involvement of the dioxide in C—H...O(=P) hydrogen bonds and the lack of similar hydrogen bonds in the investigated crystal structure. In both mol­ecules, the P—C—C—P chain is in a trans conformation, extended further at both ends by one of the two P—Cipso bonds. The planes of the phenyl and o-tolyl rings attached to the same P atom are nearly perpendicular to one another. Both crystal structures are mainly stabilized by dispersive inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S205322961402542X/ku3144sup1.cif
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S205322961402542X/ku3144Isup2.hkl
Contains datablock I

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S205322961402542X/ku3144Isup3.pdf
Supplementary material

CCDC reference: 1035173

Introduction top

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.

Experimental top

Synthesis and crystallization top

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.

Refinement top

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].

Results and discussion top

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.

Related literature top

For related literature, see: Allen (2002); Ansell et al. (1985); Bergin et al. (2007); Cahn et al. (1966); Carey (2014); Etayo & Vidal-Ferran (2013); Fábián & Kálmán (1999); Flack (1983); King et al. (2007); Knížek (2005); Knowles et al. (1975); Kowiel (2011); Macrae et al. (2006); McKinnon et al. (2004); Mohamed et al. (2004); Wolff et al. (2007).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid representation (at the 40% probability level) of o-tolyl-DiPAMP in the crystal structure.
[Figure 2] Fig. 2. (a) Part of the crystal structure of o-tolyl-DIPAMP, showing the formation of a supramolecular motif analogous to (b) the C—H···O hydrogen-bonded dimers present in o-tolyl-DIPAMPO.
[Figure 3] Fig. 3. X-ray powder diffraction patterns calculated from the known crystal structures of o-tolyl-DiPAMP (blue) and o-tolyl-DiPAMPO (red). Both structures were determined at 100 K.
(S,S)-(Ethane-1,2-diyl)bis[(2-methylphenyl)phenylphosphane] top
Crystal data top
C28H28P2F(000) = 904
Mr = 426.44Dx = 1.216 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2abCell parameters from 9393 reflections
a = 5.9725 (1) Åθ = 2.6–76.1°
b = 17.0935 (2) ŵ = 1.77 mm1
c = 22.8179 (3) ÅT = 100 K
V = 2329.50 (6) Å3Needle, colourless
Z = 40.6 × 0.1 × 0.1 mm
Data collection top
Agilent SuperNova Atlas
diffractometer
4101 independent reflections
Radiation source: SuperNova (Cu) X-ray Source4013 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.030
Detector resolution: 10.5357 pixels mm-1θmax = 66.6°, θmin = 4.7°
ω scansh = 75
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2013)
k = 2020
Tmin = 0.383, Tmax = 1.000l = 2527
10411 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-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 reflectionsΔρmax = 0.37 e Å3
273 parametersΔρmin = 0.30 e Å3
0 restraintsAbsolute structure: Flack (1983), 1716 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.007 (17)
Crystal data top
C28H28P2V = 2329.50 (6) Å3
Mr = 426.44Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 5.9725 (1) ŵ = 1.77 mm1
b = 17.0935 (2) ÅT = 100 K
c = 22.8179 (3) Å0.6 × 0.1 × 0.1 mm
Data collection top
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 = 1.000Rint = 0.030
10411 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.091Δρmax = 0.37 e Å3
S = 1.05Δρmin = 0.30 e Å3
4101 reflectionsAbsolute structure: Flack (1983), 1716 Friedel pairs
273 parametersAbsolute structure parameter: 0.007 (17)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.49729 (8)0.94930 (3)0.088442 (19)0.02406 (13)
P20.87215 (8)0.79349 (3)0.21201 (2)0.02412 (13)
C10.5845 (3)0.89767 (10)0.02119 (8)0.0207 (4)
C20.7691 (3)0.84772 (11)0.01890 (8)0.0230 (4)
H20.86480.84470.05100.028*
C30.8128 (3)0.80221 (11)0.03043 (9)0.0265 (4)
H30.93640.76910.03120.032*
C40.6716 (3)0.80655 (11)0.07822 (8)0.0278 (4)
H40.69730.77520.11080.033*
C50.4921 (3)0.85751 (11)0.07762 (8)0.0261 (4)
H50.40070.86120.11050.031*
C60.4453 (3)0.90355 (11)0.02853 (8)0.0226 (4)
C70.2480 (3)0.95806 (12)0.02966 (9)0.0303 (4)
H7A0.16140.94870.06440.045*
H7B0.30001.01120.02960.045*
H7C0.15670.94910.00430.045*
C80.5887 (3)1.05044 (11)0.07285 (8)0.0231 (4)
C90.7971 (4)1.06822 (12)0.04972 (11)0.0385 (5)
H90.89851.02820.04200.046*
C100.8558 (4)1.14527 (13)0.03804 (10)0.0375 (5)
H100.99501.15650.02180.045*
C110.7083 (4)1.20508 (12)0.05037 (9)0.0323 (5)
H110.74841.25680.04320.039*
C120.5015 (4)1.18762 (12)0.07343 (10)0.0368 (5)
H120.40081.22770.08140.044*
C130.4420 (3)1.11081 (12)0.08479 (9)0.0300 (4)
H130.30201.09980.10060.036*
C140.7097 (4)0.91686 (11)0.14227 (8)0.0285 (4)
H14A0.85690.91740.12430.034*
H14B0.71150.95230.17540.034*
C150.6537 (4)0.83361 (11)0.16324 (8)0.0278 (4)
H15A0.63720.79970.12950.033*
H15B0.51190.83440.18400.033*
C160.7597 (3)0.69611 (11)0.22942 (8)0.0244 (4)
C170.5725 (4)0.66581 (13)0.20152 (10)0.0338 (5)
H170.49140.69750.17610.041*
C180.5031 (4)0.58908 (13)0.21064 (11)0.0420 (5)
H180.37670.56990.19160.050*
C190.6229 (5)0.54176 (13)0.24794 (11)0.0438 (6)
H190.57880.49020.25400.053*
C200.8088 (5)0.57098 (13)0.27645 (10)0.0431 (6)
H200.88760.53850.30190.052*
C230.8147 (3)0.84800 (11)0.27976 (8)0.0237 (4)
C240.9765 (3)0.90033 (11)0.29878 (9)0.0301 (4)
H241.10800.90610.27740.036*
C250.9451 (4)0.94440 (13)0.34947 (10)0.0380 (5)
H251.05520.97920.36170.046*
C260.7509 (4)0.93635 (12)0.38142 (10)0.0370 (5)
H260.72970.96540.41540.044*
C270.5871 (4)0.88462 (13)0.36261 (10)0.0371 (5)
H270.45580.87910.38410.045*
C280.6174 (4)0.84099 (13)0.31198 (9)0.0320 (4)
H280.50570.80700.29950.038*
C210.8820 (4)0.64765 (12)0.26830 (9)0.0308 (4)
C221.0821 (5)0.67819 (15)0.30089 (11)0.0474 (6)
H22A1.03380.71400.33070.071*
H22B1.17990.70480.27410.071*
H22C1.16070.63530.31870.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0317 (2)0.0185 (2)0.0220 (2)0.0008 (2)0.0060 (2)0.00025 (17)
P20.0289 (2)0.0238 (2)0.0197 (2)0.0048 (2)0.00220 (19)0.00001 (17)
C10.0270 (9)0.0123 (8)0.0226 (9)0.0016 (7)0.0033 (7)0.0000 (6)
C20.0258 (9)0.0184 (9)0.0248 (9)0.0013 (8)0.0003 (7)0.0015 (7)
C30.0276 (9)0.0207 (9)0.0313 (10)0.0020 (8)0.0061 (8)0.0020 (7)
C40.0346 (10)0.0243 (9)0.0244 (10)0.0052 (8)0.0075 (8)0.0053 (8)
C50.0297 (9)0.0275 (10)0.0211 (9)0.0066 (8)0.0003 (8)0.0008 (7)
C60.0243 (9)0.0169 (9)0.0266 (9)0.0030 (7)0.0026 (7)0.0021 (7)
C70.0273 (10)0.0288 (11)0.0347 (11)0.0039 (9)0.0028 (8)0.0030 (8)
C80.0323 (9)0.0172 (9)0.0197 (8)0.0004 (8)0.0016 (7)0.0013 (7)
C90.0401 (12)0.0230 (11)0.0525 (14)0.0057 (9)0.0163 (11)0.0009 (9)
C100.0377 (12)0.0265 (11)0.0484 (13)0.0034 (9)0.0103 (10)0.0050 (9)
C110.0454 (12)0.0186 (9)0.0328 (10)0.0007 (9)0.0084 (9)0.0038 (8)
C120.0427 (11)0.0248 (10)0.0430 (12)0.0122 (10)0.0003 (11)0.0004 (9)
C130.0317 (10)0.0248 (10)0.0336 (10)0.0051 (8)0.0005 (8)0.0026 (8)
C140.0420 (11)0.0234 (10)0.0202 (9)0.0029 (8)0.0005 (8)0.0010 (7)
C150.0386 (11)0.0246 (10)0.0200 (9)0.0054 (9)0.0019 (8)0.0026 (7)
C160.0314 (10)0.0229 (9)0.0189 (9)0.0008 (8)0.0053 (8)0.0005 (7)
C170.0344 (10)0.0317 (11)0.0353 (11)0.0068 (9)0.0015 (9)0.0005 (8)
C180.0415 (11)0.0306 (11)0.0540 (14)0.0115 (10)0.0122 (12)0.0085 (10)
C190.0600 (15)0.0188 (10)0.0524 (14)0.0029 (11)0.0294 (12)0.0028 (9)
C200.0682 (16)0.0251 (11)0.0361 (12)0.0156 (11)0.0124 (11)0.0020 (9)
C230.0307 (9)0.0186 (9)0.0217 (9)0.0002 (7)0.0021 (7)0.0013 (7)
C240.0299 (9)0.0249 (10)0.0354 (10)0.0023 (9)0.0002 (9)0.0028 (8)
C250.0437 (12)0.0287 (11)0.0415 (12)0.0006 (9)0.0107 (10)0.0116 (9)
C260.0561 (13)0.0271 (11)0.0278 (10)0.0074 (10)0.0034 (10)0.0056 (8)
C270.0457 (12)0.0364 (12)0.0293 (11)0.0009 (10)0.0102 (9)0.0016 (9)
C280.0337 (10)0.0329 (11)0.0294 (10)0.0050 (9)0.0028 (9)0.0022 (8)
C210.0416 (11)0.0271 (10)0.0237 (9)0.0093 (9)0.0038 (9)0.0045 (8)
C220.0580 (15)0.0405 (13)0.0438 (13)0.0205 (12)0.0202 (12)0.0089 (10)
Geometric parameters (Å, º) top
P1—C11.8454 (18)C14—C151.538 (3)
P1—C81.8475 (19)C14—H14A0.9700
P1—C141.851 (2)C14—H14B0.9700
P2—C231.8374 (19)C15—H15A0.9700
P2—C161.8383 (19)C15—H15B0.9700
P2—C151.847 (2)C16—C171.387 (3)
C1—C21.395 (3)C16—C211.416 (3)
C1—C61.410 (3)C17—C181.391 (3)
C2—C31.393 (3)C17—H170.9300
C2—H20.9300C18—C191.375 (4)
C3—C41.381 (3)C18—H180.9300
C3—H30.9300C19—C201.380 (4)
C4—C51.381 (3)C19—H190.9300
C4—H40.9300C20—C211.394 (3)
C5—C61.397 (3)C20—H200.9300
C5—H50.9300C23—C241.387 (3)
C6—C71.502 (3)C23—C281.394 (3)
C7—H7A0.9600C24—C251.393 (3)
C7—H7B0.9600C24—H240.9300
C7—H7C0.9600C25—C261.377 (3)
C8—C131.381 (3)C25—H250.9300
C8—C91.386 (3)C26—C271.387 (3)
C9—C101.389 (3)C26—H260.9300
C9—H90.9300C27—C281.387 (3)
C10—C111.378 (3)C27—H270.9300
C10—H100.9300C28—H280.9300
C11—C121.375 (3)C21—C221.502 (3)
C11—H110.9300C22—H22A0.9600
C12—C131.385 (3)C22—H22B0.9600
C12—H120.9300C22—H22C0.9600
C13—H130.9300
C1—P1—C8101.77 (8)C15—C14—H14B109.8
C1—P1—C14102.42 (9)P1—C14—H14B109.8
C8—P1—C14101.87 (9)H14A—C14—H14B108.2
C23—P2—C16102.08 (8)C14—C15—P2112.18 (14)
C23—P2—C15100.76 (9)C14—C15—H15A109.2
C16—P2—C15102.03 (9)P2—C15—H15A109.2
C2—C1—C6118.65 (17)C14—C15—H15B109.2
C2—C1—P1123.15 (14)P2—C15—H15B109.2
C6—C1—P1117.93 (14)H15A—C15—H15B107.9
C3—C2—C1121.34 (18)C17—C16—C21118.98 (19)
C3—C2—H2119.3C17—C16—P2122.24 (15)
C1—C2—H2119.3C21—C16—P2118.47 (15)
C4—C3—C2119.58 (18)C16—C17—C18121.6 (2)
C4—C3—H3120.2C16—C17—H17119.2
C2—C3—H3120.2C18—C17—H17119.2
C3—C4—C5120.01 (17)C19—C18—C17119.5 (2)
C3—C4—H4120.0C19—C18—H18120.3
C5—C4—H4120.0C17—C18—H18120.3
C4—C5—C6121.22 (18)C18—C19—C20119.8 (2)
C4—C5—H5119.4C18—C19—H19120.1
C6—C5—H5119.4C20—C19—H19120.1
C5—C6—C1119.13 (17)C19—C20—C21122.0 (2)
C5—C6—C7119.50 (17)C19—C20—H20119.0
C1—C6—C7121.37 (17)C21—C20—H20119.0
C6—C7—H7A109.5C24—C23—C28118.67 (18)
C6—C7—H7B109.5C24—C23—P2117.39 (15)
H7A—C7—H7B109.5C28—C23—P2123.92 (15)
C6—C7—H7C109.5C23—C24—C25121.0 (2)
H7A—C7—H7C109.5C23—C24—H24119.5
H7B—C7—H7C109.5C25—C24—H24119.5
C13—C8—C9118.75 (18)C26—C25—C24119.9 (2)
C13—C8—P1118.30 (14)C26—C25—H25120.0
C9—C8—P1122.95 (15)C24—C25—H25120.0
C8—C9—C10120.5 (2)C25—C26—C27119.6 (2)
C8—C9—H9119.7C25—C26—H26120.2
C10—C9—H9119.7C27—C26—H26120.2
C11—C10—C9120.2 (2)C26—C27—C28120.6 (2)
C11—C10—H10119.9C26—C27—H27119.7
C9—C10—H10119.9C28—C27—H27119.7
C12—C11—C10119.40 (19)C27—C28—C23120.2 (2)
C12—C11—H11120.3C27—C28—H28119.9
C10—C11—H11120.3C23—C28—H28119.9
C11—C12—C13120.5 (2)C20—C21—C16118.2 (2)
C11—C12—H12119.7C20—C21—C22120.7 (2)
C13—C12—H12119.7C16—C21—C22121.1 (2)
C8—C13—C12120.60 (19)C21—C22—H22A109.5
C8—C13—H13119.7C21—C22—H22B109.5
C12—C13—H13119.7H22A—C22—H22B109.5
C15—C14—P1109.56 (14)C21—C22—H22C109.5
C15—C14—H14A109.8H22A—C22—H22C109.5
P1—C14—H14A109.8H22B—C22—H22C109.5
C8—P1—C1—C2105.61 (16)C23—P2—C15—C1474.89 (15)
C14—P1—C1—C20.48 (17)C16—P2—C15—C14179.85 (14)
C8—P1—C1—C680.48 (15)C23—P2—C16—C17112.25 (17)
C14—P1—C1—C6174.39 (14)C15—P2—C16—C178.32 (19)
C6—C1—C2—C32.2 (3)C23—P2—C16—C2174.22 (16)
P1—C1—C2—C3171.71 (14)C15—P2—C16—C21178.15 (15)
C1—C2—C3—C40.2 (3)C21—C16—C17—C180.3 (3)
C2—C3—C4—C51.9 (3)P2—C16—C17—C18173.18 (17)
C3—C4—C5—C62.1 (3)C16—C17—C18—C190.3 (3)
C4—C5—C6—C10.0 (3)C17—C18—C19—C200.7 (3)
C4—C5—C6—C7179.84 (17)C18—C19—C20—C210.6 (3)
C2—C1—C6—C52.0 (3)C16—P2—C23—C24141.02 (15)
P1—C1—C6—C5172.15 (13)C15—P2—C23—C24114.05 (16)
C2—C1—C6—C7178.09 (17)C16—P2—C23—C2840.48 (19)
P1—C1—C6—C77.7 (2)C15—P2—C23—C2864.45 (18)
C1—P1—C8—C13134.48 (15)C28—C23—C24—C250.9 (3)
C14—P1—C8—C13119.96 (16)P2—C23—C24—C25179.49 (17)
C1—P1—C8—C945.44 (19)C23—C24—C25—C260.1 (3)
C14—P1—C8—C960.12 (19)C24—C25—C26—C270.4 (3)
C13—C8—C9—C100.9 (3)C25—C26—C27—C280.0 (3)
P1—C8—C9—C10179.03 (19)C26—C27—C28—C230.8 (3)
C8—C9—C10—C111.2 (4)C24—C23—C28—C271.3 (3)
C9—C10—C11—C121.1 (3)P2—C23—C28—C27179.74 (17)
C10—C11—C12—C130.7 (3)C19—C20—C21—C160.0 (3)
C9—C8—C13—C120.5 (3)C19—C20—C21—C22178.8 (2)
P1—C8—C13—C12179.42 (17)C17—C16—C21—C200.5 (3)
C11—C12—C13—C80.4 (3)P2—C16—C21—C20173.27 (15)
C1—P1—C14—C1577.81 (15)C17—C16—C21—C22178.3 (2)
C8—P1—C14—C15177.13 (13)P2—C16—C21—C228.0 (3)
P1—C14—C15—P2174.79 (10)

Experimental details

Crystal data
Chemical formulaC28H28P2
Mr426.44
Crystal system, space groupOrthorhombic, P212121
Temperature (K)100
a, b, c (Å)5.9725 (1), 17.0935 (2), 22.8179 (3)
V3)2329.50 (6)
Z4
Radiation typeCu Kα
µ (mm1)1.77
Crystal size (mm)0.6 × 0.1 × 0.1
Data collection
DiffractometerAgilent SuperNova Atlas
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2013)
Tmin, Tmax0.383, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
10411, 4101, 4013
Rint0.030
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.091, 1.05
No. of reflections4101
No. of parameters273
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.37, 0.30
Absolute structureFlack (1983), 1716 Friedel pairs
Absolute structure parameter0.007 (17)

Computer programs: CrysAlis PRO (Agilent, 2013), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006) and XP (Siemens, 1994).

Selected geometric parameters for o-tolyl-DiPAMP and o-tolyl-DiPAMPO (Å, °). The original numbering scheme in o-tolyl-DiPAMPO has been modified to match that adopted in the reported crystal structure top
o-tolyl-DiPAMPo-tolyl-DiPAMPO
P1—C11.8454 (18)1.820 (2)
P1—C81.8475 (19)1.807 (2)
P1—C141.851 (2)1.810 (2)
P2—C161.8383 (19)1.810 (2)
P2—C231.8374 (19)1.809 (2)
P2—C151.847 (2)1.814 (2)
C1—P1—C8101.77 (8)106.15 (9)
C1—P1—C14102.42 (9)106.51 (9)
C8—P1—C14101.87 (9)105.90 (9)
C23—P2—C16102.08 (8)106.57 (9)
C23—P2—C15100.76 (9)105.93 (9)
C16—P2—C15102.03 (9)106.01 (9)
C2—C1—P1123.15 (14)121.03 (15)
C6—C1—P1117.93 (14)119.68 (14)
C13—C8—P1118.30 (14)118.02 (15)
C9—C8—P1122.95 (15)122.50 (15)
C15—C14—P1109.56 (14)110.90 (13)
C14—C15—P2112.18 (14)111.86 (14)
C17—C16—P2122.24 (15)119.83 (16)
C21—C16—P2118.47 (15)120.29 (16)
C24—C23—P2117.39 (15)117.64 (16)
C28—C23—P2123.92 (15)122.69 (16)
C14—P1—C1—C20.48 (17)-6.35 (18)
C14—P1—C1—C6174.39 (14)168.64 (15)
C14—P1—C8—C13-119.96 (16)-116.62 (17)
C14—P1—C8—C960.12 (19)65.00 (19)
C1—P1—C14—C15-77.81 (15)-73.63 (15)
C8—P1—C14—C15177.13 (13)173.66 (14)
P1—C14—C15—P2174.79 (10)176.78 (11)
C23—P2—C15—C1474.89 (15)71.38 (16)
C16—P2—C15—C14179.85 (14)-175.64 (14)
C15—P2—C16—C178.32 (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—C2864.45 (18)70.29 (19)
 

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