(S)-(−)-5,5′-Bis(diphenyl­phosphino)-4,4′-bi-1,3-benzodioxole

Jian, L.-Y.; He, X.-J.; Sun, Y.-X.; Jiang, Q.-H.; Zhu, X.

doi:10.1107/S1600536809015335

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1153

doi:10.1107/S1600536809015335

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(S)-(−)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Ling-Yan Jian,^a ^* Xiao-Jing He,^a Ya-Xin Sun,^a Qing-Hua Jiang ^a and Xu Zhu ^a

^aShengjing Hospital of China Medical University, Shenyang 110004, People's Republic of China
^*Correspondence e-mail: jianlingyan09@126.com

(Received 15 April 2009; accepted 24 April 2009; online 30 April 2009)

In the chiral title compound, C₃₈H₂₈O₄P₂, the intramolecular P⋯P separation is 3.671 (2) Å and the dihedral angle between the two benzene rings in the biphenyl unit is 77.9 (2)°.

Related literature

For background on asymmetric synthesis and catalysis using this type of chiral ligand, see: Horner et al. (1968 ); Aikawa et al. (2004 ). For the synthesis, see: Saito et al. (2001 ). For a related structure, see: Jones et al. (2003 ).

Experimental

Crystal data

C₃₈H₂₈O₄P₂
M_r = 610.54
Orthorhombic, P 2₁ 2₁ 2₁
a = 10.4735 (10) Å
b = 15.8362 (15) Å
c = 18.7349 (17) Å
V = 3107.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 295 K
0.22 × 0.20 × 0.17 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Siemens, 1996 ) T_min = 0.961, T_max = 0.970
16522 measured reflections
5515 independent reflections
4665 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.083
S = 1.03
5515 reflections
397 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 2403 Friedel pairs
Flack parameter: 0.06 (8)

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809015335/hb2954sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015335/hb2954Isup2.hkl

checkCIF report

Comment top

The ability to selectively form one enantiomer in preference to the other (asymmetric catalysis) is undoubtedly one of the major advances in modern drug design and synthesis. Since 1968, when a chiral phosphine was first utilized in asymmetric hydrogenation (Horner et al., 1968), much effort has been devoted to the design and synthesis of chiral phosphine ligands. The synthesis of the title compound has been reported in literature (Saito et al., 2001). However, this is the first time that the crystal structure is being reported. This ligand has been used on palladium for the catalysis of ketone-ene reactions (Aikawa et al., 2004). All bond lengths and angles in (I) are normal and are comparable to those in the related compound (S)-(–)-2,2'-Bis(diphenylphosphino) -1,1'-binaphthyl (Jones et al., 2003). The key feature of (I) is the intramolecular P···P distance of 3.671 (2) Å and the two benzene rings in the biphenyl moiety make a dihedral angle of 77.9 (2)°.

Related literature top

For background on asymmetric synthesis and catalysis using this type of chiral ligand, see: Horner et al. (1968); Aikawa et al. (2004). For the synthesis, see: Saito et al. (2001). For a related structure, see: Jones et al. (2003).

Experimental top

The title compound was synthesized by the literature route of Saito et al. (2001). Colourless blocks of (I) were grown by slow evaporation of a solution of the compound in a acetone-ethanol (1:1 v/v) mixture.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted for clarity.

(S)-(-)-5,5'-Bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole top

Crystal data top

C₃₈H₂₈O₄P₂	F(000) = 1272
M_r = 610.54	D_x = 1.305 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 4758 reflections
a = 10.4735 (10) Å	θ = 2.2–23.5°
b = 15.8362 (15) Å	µ = 0.18 mm⁻¹
c = 18.7349 (17) Å	T = 295 K
V = 3107.4 (5) Å³	Block, colourless
Z = 4	0.22 × 0.20 × 0.17 mm

Data collection top

Siemens SMART CCD diffractometer	5515 independent reflections
Radiation source: fine-focus sealed tube	4665 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 25.1°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −12→8
T_min = 0.961, T_max = 0.970	k = −18→18
16522 measured reflections	l = −20→22

Refinement top

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) = 0.083	w = 1/[σ²(F_o²) + (0.0405P)² + 0.2496P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
5515 reflections	Δρ_max = 0.25 e Å⁻³
397 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2403 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (8)

Crystal data top

C₃₈H₂₈O₄P₂	V = 3107.4 (5) Å³
M_r = 610.54	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 10.4735 (10) Å	µ = 0.18 mm⁻¹
b = 15.8362 (15) Å	T = 295 K
c = 18.7349 (17) Å	0.22 × 0.20 × 0.17 mm

Data collection top

Siemens SMART CCD diffractometer	5515 independent reflections
Absorption correction: multi-scan (SADABS; Siemens, 1996)	4665 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.970	R_int = 0.031
16522 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.083	Δρ_max = 0.25 e Å⁻³
S = 1.03	Δρ_min = −0.16 e Å⁻³
5515 reflections	Absolute structure: Flack (1983), 2403 Friedel pairs
397 parameters	Absolute structure parameter: 0.06 (8)
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

	x	y	z	U_iso*/U_eq
P1	0.58912 (6)	0.58094 (4)	0.84832 (3)	0.04188 (15)
P2	0.59298 (6)	0.53283 (4)	0.65667 (3)	0.04263 (15)
O1	0.13104 (16)	0.70954 (11)	0.69648 (11)	0.0662 (5)
O2	0.33097 (16)	0.74812 (10)	0.65651 (9)	0.0569 (4)
O3	0.57161 (16)	0.83894 (9)	0.76483 (9)	0.0518 (4)
O4	0.76116 (17)	0.88509 (10)	0.71511 (10)	0.0597 (5)
C1	0.4390 (2)	0.61654 (13)	0.80753 (11)	0.0355 (5)
C2	0.3188 (2)	0.59414 (14)	0.83092 (12)	0.0432 (5)
H2	0.3117	0.5596	0.8709	0.052*
C3	0.2068 (2)	0.62152 (15)	0.79677 (14)	0.0499 (6)
H3	0.1262	0.6048	0.8122	0.060*
C4	0.2228 (2)	0.67396 (15)	0.73985 (13)	0.0461 (6)
C5	0.1990 (3)	0.77173 (19)	0.65656 (17)	0.0694 (8)
H5A	0.1885	0.8269	0.6783	0.083*
H5B	0.1668	0.7742	0.6081	0.083*
C6	0.3422 (2)	0.69712 (13)	0.71610 (12)	0.0402 (5)
C7	0.4530 (2)	0.66937 (13)	0.74655 (11)	0.0359 (5)
C8	0.5330 (2)	0.51007 (14)	0.91959 (11)	0.0406 (5)
C9	0.5239 (3)	0.42500 (15)	0.90265 (13)	0.0541 (6)
H9	0.5446	0.4071	0.8568	0.065*
C10	0.4845 (3)	0.36647 (17)	0.95267 (16)	0.0665 (8)
H10	0.4774	0.3098	0.9404	0.080*
C11	0.4561 (3)	0.39259 (18)	1.02055 (15)	0.0652 (8)
H11	0.4300	0.3534	1.0545	0.078*
C12	0.4660 (2)	0.47679 (18)	1.03892 (13)	0.0589 (7)
H12	0.4472	0.4942	1.0852	0.071*
C13	0.5039 (2)	0.53493 (16)	0.98843 (12)	0.0478 (6)
H13	0.5099	0.5916	1.0008	0.057*
C14	0.6373 (2)	0.67684 (15)	0.89654 (12)	0.0440 (6)
C15	0.5534 (3)	0.73889 (16)	0.91921 (13)	0.0544 (7)
H15	0.4665	0.7325	0.9107	0.065*
C16	0.5973 (3)	0.81080 (17)	0.95458 (15)	0.0649 (7)
H16	0.5395	0.8516	0.9699	0.078*
C17	0.7256 (3)	0.82148 (19)	0.96687 (16)	0.0703 (8)
H17	0.7552	0.8691	0.9907	0.084*
C18	0.8092 (3)	0.7612 (2)	0.94363 (17)	0.0736 (9)
H18	0.8962	0.7686	0.9514	0.088*
C19	0.7667 (3)	0.68914 (17)	0.90862 (14)	0.0608 (7)
H19	0.8252	0.6489	0.8932	0.073*
C20	0.6520 (2)	0.64110 (13)	0.67129 (12)	0.0419 (5)
C21	0.5790 (2)	0.69450 (13)	0.71579 (11)	0.0360 (5)
C22	0.6264 (2)	0.77484 (14)	0.72645 (12)	0.0400 (5)
C23	0.6690 (3)	0.90246 (15)	0.76970 (14)	0.0581 (7)
H23A	0.6323	0.9581	0.7628	0.070*
H23B	0.7091	0.9008	0.8163	0.070*
C24	0.7386 (2)	0.80219 (14)	0.69604 (13)	0.0463 (6)
C25	0.8098 (2)	0.75234 (15)	0.65207 (15)	0.0568 (7)
H25	0.8847	0.7716	0.6309	0.068*
C26	0.7641 (2)	0.67079 (15)	0.64068 (14)	0.0538 (6)
H26	0.8106	0.6347	0.6114	0.065*
C27	0.7379 (2)	0.46870 (14)	0.66098 (12)	0.0443 (5)
C28	0.8398 (3)	0.48831 (17)	0.70534 (13)	0.0580 (7)
H28	0.8393	0.5391	0.7303	0.070*
C29	0.9414 (3)	0.4341 (2)	0.71318 (14)	0.0687 (8)
H29	1.0092	0.4491	0.7427	0.082*
C30	0.9438 (3)	0.3586 (2)	0.67796 (15)	0.0732 (9)
H30	1.0125	0.3220	0.6838	0.088*
C31	0.8450 (3)	0.33712 (17)	0.63417 (16)	0.0689 (8)
H31	0.8466	0.2859	0.6099	0.083*
C32	0.7425 (3)	0.39115 (15)	0.62571 (14)	0.0580 (7)
H32	0.6754	0.3755	0.5960	0.070*
C33	0.5558 (2)	0.53725 (14)	0.56069 (12)	0.0433 (5)
C34	0.4283 (2)	0.55116 (16)	0.54330 (14)	0.0575 (7)
H34	0.3679	0.5560	0.5795	0.069*
C35	0.3904 (3)	0.55778 (19)	0.47284 (15)	0.0703 (8)
H35	0.3053	0.5683	0.4619	0.084*
C36	0.4780 (3)	0.54888 (18)	0.41902 (14)	0.0660 (8)
H36	0.4523	0.5530	0.3716	0.079*
C37	0.6031 (3)	0.53395 (17)	0.43509 (13)	0.0596 (7)
H37	0.6621	0.5272	0.3984	0.072*
C38	0.6431 (2)	0.52869 (16)	0.50546 (12)	0.0526 (6)
H38	0.7289	0.5194	0.5157	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0382 (3)	0.0438 (3)	0.0437 (3)	0.0045 (3)	0.0006 (3)	0.0023 (3)
P2	0.0426 (3)	0.0394 (3)	0.0459 (3)	−0.0018 (3)	0.0061 (3)	−0.0014 (3)
O1	0.0412 (10)	0.0677 (12)	0.0899 (14)	0.0021 (9)	−0.0192 (9)	0.0103 (11)
O2	0.0532 (10)	0.0582 (11)	0.0592 (10)	0.0064 (8)	−0.0073 (9)	0.0185 (9)
O3	0.0507 (10)	0.0390 (9)	0.0656 (11)	−0.0013 (8)	0.0148 (8)	−0.0060 (8)
O4	0.0539 (11)	0.0432 (10)	0.0821 (12)	−0.0109 (8)	0.0146 (10)	−0.0049 (9)
C1	0.0357 (12)	0.0337 (11)	0.0373 (11)	0.0005 (9)	0.0019 (9)	−0.0017 (9)
C2	0.0429 (13)	0.0415 (13)	0.0450 (13)	−0.0033 (10)	0.0062 (11)	0.0020 (11)
C3	0.0339 (13)	0.0518 (15)	0.0640 (16)	−0.0072 (11)	0.0047 (12)	0.0000 (13)
C4	0.0353 (13)	0.0432 (13)	0.0599 (15)	0.0029 (11)	−0.0070 (11)	−0.0050 (12)
C5	0.0551 (17)	0.0711 (18)	0.082 (2)	0.0082 (14)	−0.0180 (16)	0.0153 (17)
C6	0.0420 (13)	0.0360 (12)	0.0427 (12)	0.0032 (10)	−0.0004 (11)	−0.0010 (10)
C7	0.0352 (11)	0.0319 (11)	0.0406 (11)	−0.0014 (10)	0.0023 (10)	−0.0035 (9)
C8	0.0400 (13)	0.0379 (13)	0.0438 (12)	0.0033 (10)	−0.0059 (10)	0.0017 (10)
C9	0.0653 (17)	0.0457 (14)	0.0514 (14)	0.0057 (13)	−0.0047 (13)	−0.0014 (12)
C10	0.087 (2)	0.0408 (14)	0.0721 (19)	−0.0049 (14)	−0.0048 (17)	0.0085 (14)
C11	0.0703 (19)	0.0642 (18)	0.0612 (17)	−0.0080 (14)	−0.0057 (15)	0.0241 (15)
C12	0.0607 (17)	0.0720 (19)	0.0439 (14)	−0.0015 (14)	−0.0014 (12)	0.0045 (14)
C13	0.0515 (14)	0.0477 (13)	0.0442 (13)	0.0031 (12)	−0.0024 (11)	−0.0005 (12)
C14	0.0413 (13)	0.0462 (13)	0.0444 (13)	−0.0037 (11)	−0.0049 (10)	0.0084 (11)
C15	0.0477 (16)	0.0526 (15)	0.0631 (16)	−0.0027 (12)	−0.0066 (12)	−0.0030 (13)
C16	0.0681 (19)	0.0528 (15)	0.0737 (18)	−0.0040 (15)	−0.0105 (16)	−0.0095 (14)
C17	0.080 (2)	0.0600 (17)	0.0712 (19)	−0.0237 (17)	−0.0169 (17)	−0.0010 (15)
C18	0.0518 (18)	0.086 (2)	0.083 (2)	−0.0229 (18)	−0.0204 (16)	0.0056 (18)
C19	0.0469 (15)	0.0660 (18)	0.0694 (18)	−0.0028 (13)	−0.0099 (14)	0.0054 (15)
C20	0.0418 (13)	0.0382 (12)	0.0459 (13)	−0.0038 (10)	0.0028 (11)	0.0011 (10)
C21	0.0336 (11)	0.0405 (12)	0.0339 (11)	0.0006 (10)	0.0012 (10)	0.0059 (9)
C22	0.0368 (13)	0.0385 (12)	0.0447 (13)	0.0018 (10)	0.0017 (10)	0.0042 (11)
C23	0.0644 (17)	0.0405 (14)	0.0695 (17)	−0.0057 (13)	0.0094 (14)	−0.0018 (13)
C24	0.0414 (13)	0.0397 (13)	0.0577 (15)	−0.0038 (11)	0.0036 (12)	0.0022 (11)
C25	0.0441 (14)	0.0530 (16)	0.0734 (17)	−0.0072 (12)	0.0185 (14)	−0.0015 (14)
C26	0.0488 (14)	0.0477 (14)	0.0648 (16)	−0.0005 (12)	0.0209 (13)	−0.0060 (13)
C27	0.0494 (13)	0.0410 (12)	0.0427 (12)	0.0027 (11)	0.0052 (11)	0.0049 (11)
C28	0.0612 (17)	0.0672 (17)	0.0457 (14)	0.0074 (14)	−0.0004 (13)	−0.0052 (13)
C29	0.0667 (19)	0.091 (2)	0.0487 (15)	0.0180 (17)	−0.0089 (14)	−0.0006 (15)
C30	0.074 (2)	0.083 (2)	0.0626 (18)	0.0319 (17)	0.0057 (16)	0.0224 (16)
C31	0.085 (2)	0.0463 (15)	0.075 (2)	0.0162 (15)	0.0055 (17)	0.0044 (14)
C32	0.0641 (17)	0.0459 (15)	0.0639 (16)	0.0037 (13)	−0.0066 (14)	0.0035 (13)
C33	0.0415 (14)	0.0377 (12)	0.0507 (13)	0.0012 (10)	0.0002 (11)	−0.0044 (11)
C34	0.0472 (15)	0.0657 (17)	0.0596 (15)	0.0099 (13)	0.0031 (13)	−0.0031 (13)
C35	0.0551 (17)	0.085 (2)	0.0706 (19)	0.0149 (15)	−0.0136 (15)	−0.0028 (15)
C36	0.079 (2)	0.0689 (19)	0.0498 (15)	0.0104 (16)	−0.0144 (15)	0.0018 (13)
C37	0.0664 (19)	0.0635 (16)	0.0489 (14)	0.0081 (16)	0.0090 (13)	0.0026 (13)
C38	0.0444 (14)	0.0623 (15)	0.0511 (14)	0.0081 (13)	0.0030 (11)	0.0020 (13)

Geometric parameters (Å, º) top

P1—C1	1.837 (2)	C16—C17	1.374 (4)
P1—C14	1.838 (2)	C16—H16	0.9300
P1—C8	1.841 (2)	C17—C18	1.367 (4)
P2—C27	1.828 (2)	C17—H17	0.9300
P2—C33	1.841 (2)	C18—C19	1.390 (4)
P2—C20	1.843 (2)	C18—H18	0.9300
O1—C4	1.379 (3)	C19—H19	0.9300
O1—C5	1.427 (3)	C20—C26	1.389 (3)
O2—C6	1.383 (3)	C20—C21	1.412 (3)
O2—C5	1.432 (3)	C21—C22	1.380 (3)
O3—C22	1.370 (3)	C22—C24	1.375 (3)
O3—C23	1.435 (3)	C23—H23A	0.9700
O4—C24	1.381 (3)	C23—H23B	0.9700
O4—C23	1.433 (3)	C24—C25	1.363 (3)
C1—C2	1.379 (3)	C25—C26	1.394 (3)
C1—C7	1.424 (3)	C25—H25	0.9300
C2—C3	1.405 (3)	C26—H26	0.9300
C2—H2	0.9300	C27—C28	1.388 (3)
C3—C4	1.362 (3)	C27—C32	1.395 (3)
C3—H3	0.9300	C28—C29	1.375 (4)
C4—C6	1.377 (3)	C28—H28	0.9300
C5—H5A	0.9700	C29—C30	1.367 (4)
C5—H5B	0.9700	C29—H29	0.9300
C6—C7	1.366 (3)	C30—C31	1.364 (4)
C7—C21	1.494 (3)	C30—H30	0.9300
C8—C13	1.382 (3)	C31—C32	1.382 (4)
C8—C9	1.387 (3)	C31—H31	0.9300
C9—C10	1.381 (4)	C32—H32	0.9300
C9—H9	0.9300	C33—C38	1.388 (3)
C10—C11	1.370 (4)	C33—C34	1.392 (3)
C10—H10	0.9300	C34—C35	1.382 (4)
C11—C12	1.381 (4)	C34—H34	0.9300
C11—H11	0.9300	C35—C36	1.371 (4)
C12—C13	1.378 (3)	C35—H35	0.9300
C12—H12	0.9300	C36—C37	1.365 (4)
C13—H13	0.9300	C36—H36	0.9300
C14—C15	1.385 (3)	C37—C38	1.386 (3)
C14—C19	1.388 (3)	C37—H37	0.9300
C15—C16	1.395 (3)	C38—H38	0.9300
C15—H15	0.9300

C1—P1—C14	100.70 (10)	C17—C18—H18	119.4
C1—P1—C8	102.44 (10)	C19—C18—H18	119.4
C14—P1—C8	103.58 (10)	C14—C19—C18	120.4 (3)
C27—P2—C33	103.89 (10)	C14—C19—H19	119.8
C27—P2—C20	103.41 (11)	C18—C19—H19	119.8
C33—P2—C20	100.41 (10)	C26—C20—C21	119.9 (2)
C4—O1—C5	104.07 (19)	C26—C20—P2	122.49 (18)
C6—O2—C5	103.55 (19)	C21—C20—P2	117.62 (16)
C22—O3—C23	104.76 (18)	C22—C21—C20	116.30 (19)
C24—O4—C23	104.59 (18)	C22—C21—C7	120.49 (19)
C2—C1—C7	120.04 (19)	C20—C21—C7	123.10 (19)
C2—C1—P1	124.75 (16)	O3—C22—C24	109.99 (19)
C7—C1—P1	115.19 (15)	O3—C22—C21	127.47 (19)
C1—C2—C3	122.6 (2)	C24—C22—C21	122.5 (2)
C1—C2—H2	118.7	O4—C23—O3	107.39 (18)
C3—C2—H2	118.7	O4—C23—H23A	110.2
C4—C3—C2	116.2 (2)	O3—C23—H23A	110.2
C4—C3—H3	121.9	O4—C23—H23B	110.2
C2—C3—H3	121.9	O3—C23—H23B	110.2
C3—C4—C6	121.8 (2)	H23A—C23—H23B	108.5
C3—C4—O1	128.6 (2)	C25—C24—C22	122.4 (2)
C6—C4—O1	109.5 (2)	C25—C24—O4	127.8 (2)
O1—C5—O2	107.6 (2)	C22—C24—O4	109.8 (2)
O1—C5—H5A	110.2	C24—C25—C26	116.2 (2)
O2—C5—H5A	110.2	C24—C25—H25	121.9
O1—C5—H5B	110.2	C26—C25—H25	121.9
O2—C5—H5B	110.2	C20—C26—C25	122.8 (2)
H5A—C5—H5B	108.5	C20—C26—H26	118.6
C7—C6—C4	123.4 (2)	C25—C26—H26	118.6
C7—C6—O2	126.7 (2)	C28—C27—C32	117.0 (2)
C4—C6—O2	109.8 (2)	C28—C27—P2	122.72 (18)
C6—C7—C1	115.87 (19)	C32—C27—P2	119.78 (19)
C6—C7—C21	120.25 (19)	C29—C28—C27	121.3 (2)
C1—C7—C21	123.88 (18)	C29—C28—H28	119.3
C13—C8—C9	118.3 (2)	C27—C28—H28	119.3
C13—C8—P1	125.00 (17)	C30—C29—C28	120.6 (3)
C9—C8—P1	116.62 (18)	C30—C29—H29	119.7
C10—C9—C8	121.1 (2)	C28—C29—H29	119.7
C10—C9—H9	119.4	C31—C30—C29	119.6 (3)
C8—C9—H9	119.4	C31—C30—H30	120.2
C11—C10—C9	119.5 (3)	C29—C30—H30	120.2
C11—C10—H10	120.3	C30—C31—C32	120.3 (3)
C9—C10—H10	120.3	C30—C31—H31	119.9
C10—C11—C12	120.4 (2)	C32—C31—H31	119.9
C10—C11—H11	119.8	C31—C32—C27	121.2 (3)
C12—C11—H11	119.8	C31—C32—H32	119.4
C13—C12—C11	119.7 (2)	C27—C32—H32	119.4
C13—C12—H12	120.1	C38—C33—C34	118.3 (2)
C11—C12—H12	120.1	C38—C33—P2	125.78 (18)
C12—C13—C8	120.9 (2)	C34—C33—P2	115.96 (18)
C12—C13—H13	119.6	C35—C34—C33	120.7 (2)
C8—C13—H13	119.6	C35—C34—H34	119.6
C15—C14—C19	118.0 (2)	C33—C34—H34	119.6
C15—C14—P1	124.29 (18)	C36—C35—C34	120.2 (3)
C19—C14—P1	117.7 (2)	C36—C35—H35	119.9
C14—C15—C16	121.1 (3)	C34—C35—H35	119.9
C14—C15—H15	119.5	C37—C36—C35	119.9 (3)
C16—C15—H15	119.5	C37—C36—H36	120.1
C17—C16—C15	120.1 (3)	C35—C36—H36	120.1
C17—C16—H16	119.9	C36—C37—C38	120.7 (3)
C15—C16—H16	119.9	C36—C37—H37	119.7
C18—C17—C16	119.2 (3)	C38—C37—H37	119.7
C18—C17—H17	120.4	C37—C38—C33	120.3 (2)
C16—C17—H17	120.4	C37—C38—H38	119.9
C17—C18—C19	121.2 (3)	C33—C38—H38	119.9

C14—P1—C1—C2	−104.4 (2)	C27—P2—C20—C21	−138.78 (17)
C8—P1—C1—C2	2.2 (2)	C33—P2—C20—C21	114.08 (18)
C14—P1—C1—C7	77.10 (17)	C26—C20—C21—C22	−0.4 (3)
C8—P1—C1—C7	−176.25 (15)	P2—C20—C21—C22	179.22 (16)
C7—C1—C2—C3	0.0 (3)	C26—C20—C21—C7	175.6 (2)
P1—C1—C2—C3	−178.44 (18)	P2—C20—C21—C7	−4.7 (3)
C1—C2—C3—C4	−1.8 (3)	C6—C7—C21—C22	75.5 (3)
C2—C3—C4—C6	1.5 (4)	C1—C7—C21—C22	−104.6 (2)
C2—C3—C4—O1	179.4 (2)	C6—C7—C21—C20	−100.4 (3)
C5—O1—C4—C3	168.0 (3)	C1—C7—C21—C20	79.5 (3)
C5—O1—C4—C6	−14.0 (3)	C23—O3—C22—C24	−12.2 (3)
C4—O1—C5—O2	22.8 (3)	C23—O3—C22—C21	169.9 (2)
C6—O2—C5—O1	−22.8 (3)	C20—C21—C22—O3	177.4 (2)
C3—C4—C6—C7	0.7 (4)	C7—C21—C22—O3	1.2 (3)
O1—C4—C6—C7	−177.6 (2)	C20—C21—C22—C24	−0.3 (3)
C3—C4—C6—O2	178.0 (2)	C7—C21—C22—C24	−176.4 (2)
O1—C4—C6—O2	−0.2 (3)	C24—O4—C23—O3	−17.8 (3)
C5—O2—C6—C7	−168.5 (2)	C22—O3—C23—O4	18.5 (3)
C5—O2—C6—C4	14.2 (3)	O3—C22—C24—C25	−176.8 (2)
C4—C6—C7—C1	−2.5 (3)	C21—C22—C24—C25	1.2 (4)
O2—C6—C7—C1	−179.40 (19)	O3—C22—C24—O4	1.1 (3)
C4—C6—C7—C21	177.4 (2)	C21—C22—C24—O4	179.2 (2)
O2—C6—C7—C21	0.5 (3)	C23—O4—C24—C25	−171.8 (3)
C2—C1—C7—C6	2.1 (3)	C23—O4—C24—C22	10.4 (3)
P1—C1—C7—C6	−179.30 (16)	C22—C24—C25—C26	−1.4 (4)
C2—C1—C7—C21	−177.8 (2)	O4—C24—C25—C26	−178.9 (2)
P1—C1—C7—C21	0.8 (3)	C21—C20—C26—C25	0.3 (4)
C1—P1—C8—C13	−89.2 (2)	P2—C20—C26—C25	−179.4 (2)
C14—P1—C8—C13	15.2 (2)	C24—C25—C26—C20	0.6 (4)
C1—P1—C8—C9	93.1 (2)	C33—P2—C27—C28	138.3 (2)
C14—P1—C8—C9	−162.46 (19)	C20—P2—C27—C28	33.8 (2)
C13—C8—C9—C10	1.2 (4)	C33—P2—C27—C32	−50.1 (2)
P1—C8—C9—C10	179.0 (2)	C20—P2—C27—C32	−154.56 (19)
C8—C9—C10—C11	−1.1 (4)	C32—C27—C28—C29	1.0 (4)
C9—C10—C11—C12	0.3 (4)	P2—C27—C28—C29	172.9 (2)
C10—C11—C12—C13	0.5 (4)	C27—C28—C29—C30	−0.9 (4)
C11—C12—C13—C8	−0.4 (4)	C28—C29—C30—C31	0.6 (4)
C9—C8—C13—C12	−0.4 (4)	C29—C30—C31—C32	−0.4 (4)
P1—C8—C13—C12	−178.04 (19)	C30—C31—C32—C27	0.5 (4)
C1—P1—C14—C15	24.7 (2)	C28—C27—C32—C31	−0.8 (4)
C8—P1—C14—C15	−81.1 (2)	P2—C27—C32—C31	−172.9 (2)
C1—P1—C14—C19	−152.86 (19)	C27—P2—C33—C38	−25.8 (2)
C8—P1—C14—C19	101.4 (2)	C20—P2—C33—C38	81.0 (2)
C19—C14—C15—C16	−1.4 (4)	C27—P2—C33—C34	154.78 (19)
P1—C14—C15—C16	−178.93 (19)	C20—P2—C33—C34	−98.5 (2)
C14—C15—C16—C17	0.7 (4)	C38—C33—C34—C35	−1.2 (4)
C15—C16—C17—C18	0.4 (4)	P2—C33—C34—C35	178.3 (2)
C16—C17—C18—C19	−0.7 (5)	C33—C34—C35—C36	1.4 (4)
C15—C14—C19—C18	1.1 (4)	C34—C35—C36—C37	−0.4 (5)
P1—C14—C19—C18	178.8 (2)	C35—C36—C37—C38	−0.8 (5)
C17—C18—C19—C14	−0.1 (4)	C36—C37—C38—C33	1.0 (4)
C27—P2—C20—C26	40.9 (2)	C34—C33—C38—C37	0.0 (4)
C33—P2—C20—C26	−66.3 (2)	P2—C33—C38—C37	−179.5 (2)

Experimental details

Crystal data
Chemical formula	C₃₈H₂₈O₄P₂
M_r	610.54
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	10.4735 (10), 15.8362 (15), 18.7349 (17)
V (Å³)	3107.4 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.22 × 0.20 × 0.17

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Siemens, 1996)
T_min, T_max	0.961, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	16522, 5515, 4665
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.083, 1.03
No. of reflections	5515
No. of parameters	397
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.16
Absolute structure	Flack (1983), 2403 Friedel pairs
Absolute structure parameter	0.06 (8)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Aikawa, K., Kainuma, S., Hatano, M. & Mikami, K. (2004). Tetrahedron Lett. 45, 183–185. Web of Science CSD CrossRef CAS Google Scholar
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Horner, L., Siegel, H. & Buthe, H. (1968). Angew. Chem. Int. Ed. Engl. 7, 942–944. CrossRef CAS Web of Science Google Scholar
Jones, M. D., Almeida Paz, F. A., Davies, J. E. & Johnson, B. F. G. (2003). Acta Cryst. E59, o535–o537. Web of Science CSD CrossRef IUCr Journals Google Scholar
Saito, T., Yokozawa, T., Ishizaki, T., Moroi, T., Sayo, N., Miura, T. & Kumobayashi, H. (2001). Adv. Synth. Catal 343, 264–267. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar