(S)-(-)-5,5'-Bis­(di­phenyl­phosphino)-2,2,2',2'-tetra­methyl-4,4'-bi-1,3-benzodioxole

The title mol­ecule, C₄₂H₃₆O₄P₂, is a new atropoisomeric bis-phosphine ligand. All bond lengths and angles are normal. In the crystal structure, the mol­ecule possesses a crystallograph­ically imposed C₂ axis. The two benzene rings in the bi­phenyl moiety make a dihedral angle of 84.23 (6)°.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.034
• wR factor = 0.081
• Data-to-parameter ratio = 8.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.83 Ratio
PLAT331_ALERT_2_C Small Average Phenyl C-C Dist.   C10    -C15           1.37 Ang.
PLAT850_ALERT_2_C Check Flack Parameter Exact Value 0.00 and su ..       0.09

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           25.20
           From the CIF: _reflns_number_total               1877
           Count of symmetry unique reflns         1880
           Completeness (_total/calc)             99.84%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present          yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 2002); software used to prepare material for publication: SHELXL97.

(S)-(-)-5,5'-Bis(diphenylphosphino)-2,2,2',2'-tetramethyl-4,4'-bi- 1,3-benzodioxole

Crystal data

C42H36O4P2	F(000) = 700
Mr = 666.65	Dx = 1.232 Mg m^−3
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P22ab	Cell parameters from 2896 reflections
a = 9.7007 (9) Å	θ = 4.6–22.3°
b = 20.774 (2) Å	µ = 0.16 mm^−1
c = 8.9149 (9) Å	T = 298 K
V = 1796.6 (3) Å^3	Block, colorless
Z = 2	0.50 × 0.41 × 0.35 mm

Data collection

Bruker APEX area-detector diffractometer	1877 independent reflections
Radiation source: fine-focus sealed tube	1677 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
φ and ω scans	θmax = 25.2°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→10
Tmin = 0.924, Tmax = 0.946	k = −22→24
9313 measured reflections	l = −10→10

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.035	w = 1/[σ^2(Fo^2) + (0.0487P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.081	(Δ/σ)max = 0.001
S = 0.99	Δρmax = 0.19 e Å^−3
1877 reflections	Δρmin = −0.17 e Å^−3
220 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0085 (14)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983)
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (9)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
P	0.11334 (6)	0.57910 (3)	0.87952 (8)	0.0396 (2)
O1	0.26803 (18)	0.37231 (9)	1.3052 (2)	0.0539 (5)
O2	0.04484 (17)	0.41140 (9)	1.3100 (2)	0.0513 (5)
C1	0.0734 (2)	0.48884 (11)	1.1044 (3)	0.0318 (5)
C2	0.1713 (2)	0.51408 (11)	1.0037 (3)	0.0351 (6)
C3	0.3045 (2)	0.48948 (13)	1.0021 (3)	0.0425 (6)
H3	0.3674	0.5060	0.9334	0.051*
C4	0.3470 (2)	0.44138 (12)	1.0988 (3)	0.0459 (7)
H4	0.4366	0.4255	1.0970	0.055*
C5	0.2515 (2)	0.41836 (12)	1.1967 (3)	0.0399 (6)
C6	0.1186 (2)	0.44177 (11)	1.1998 (3)	0.0358 (5)
C7	0.1314 (3)	0.35966 (14)	1.3657 (3)	0.0520 (7)
C8	0.0815 (3)	0.29695 (15)	1.3065 (5)	0.0822 (11)
H8A	−0.0124	0.2904	1.3370	0.123*
H8B	0.1378	0.2628	1.3454	0.123*
H8C	0.0867	0.2971	1.1990	0.123*
C9	0.1393 (4)	0.3643 (2)	1.5328 (4)	0.0825 (11)
H9A	0.1775	0.4053	1.5604	0.124*
H9B	0.1971	0.3305	1.5707	0.124*
H9C	0.0485	0.3602	1.5745	0.124*
C10	0.2454 (2)	0.58082 (12)	0.7322 (3)	0.0402 (6)
C11	0.2141 (3)	0.55156 (15)	0.5988 (3)	0.0628 (8)
H11	0.1298	0.5307	0.5884	0.075*
C12	0.3046 (4)	0.5523 (2)	0.4799 (4)	0.0875 (12)
H12	0.2809	0.5321	0.3903	0.105*
C13	0.4277 (4)	0.5822 (2)	0.4931 (4)	0.0817 (11)
H13	0.4895	0.5822	0.4134	0.098*
C14	0.4606 (3)	0.61210 (17)	0.6230 (5)	0.0780 (11)
H14	0.5449	0.6331	0.6319	0.094*
C15	0.3703 (3)	0.61181 (15)	0.7426 (4)	0.0607 (8)
H15	0.3941	0.6328	0.8311	0.073*
C16	0.1627 (3)	0.65082 (13)	0.9853 (3)	0.0460 (7)
C17	0.1152 (4)	0.70932 (14)	0.9290 (4)	0.0660 (8)
H17	0.0581	0.7099	0.8453	0.079*
C18	0.1526 (5)	0.76611 (16)	0.9969 (5)	0.0854 (12)
H18	0.1211	0.8049	0.9575	0.103*
C19	0.2344 (5)	0.76666 (18)	1.1200 (5)	0.0903 (13)
H19	0.2597	0.8055	1.1640	0.108*
C20	0.2794 (4)	0.70973 (19)	1.1791 (4)	0.0794 (11)
H20	0.3345	0.7099	1.2645	0.095*
C21	0.2434 (3)	0.65169 (14)	1.1125 (4)	0.0611 (8)
H21	0.2739	0.6132	1.1540	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P	0.0317 (3)	0.0434 (4)	0.0436 (4)	−0.0020 (3)	0.0018 (3)	0.0070 (3)
O1	0.0408 (10)	0.0583 (12)	0.0627 (13)	0.0084 (9)	−0.0054 (10)	0.0186 (10)
O2	0.0402 (9)	0.0614 (12)	0.0523 (11)	0.0091 (9)	0.0074 (9)	0.0223 (10)
C1	0.0273 (11)	0.0324 (11)	0.0357 (13)	−0.0031 (9)	−0.0035 (11)	−0.0039 (11)
C2	0.0314 (13)	0.0328 (13)	0.0410 (14)	−0.0027 (11)	−0.0007 (11)	−0.0030 (11)
C3	0.0282 (13)	0.0461 (15)	0.0533 (17)	−0.0032 (12)	0.0056 (12)	0.0039 (14)
C4	0.0282 (12)	0.0484 (15)	0.0612 (18)	0.0040 (11)	0.0010 (13)	0.0013 (14)
C5	0.0360 (13)	0.0386 (13)	0.0450 (14)	0.0043 (12)	−0.0064 (12)	0.0002 (13)
C6	0.0305 (11)	0.0406 (13)	0.0362 (13)	−0.0027 (11)	−0.0041 (12)	0.0003 (11)
C7	0.0423 (15)	0.0577 (16)	0.0559 (17)	0.0036 (13)	−0.0019 (15)	0.0179 (14)
C8	0.062 (2)	0.063 (2)	0.122 (3)	−0.0037 (17)	−0.013 (2)	0.011 (2)
C9	0.080 (2)	0.109 (3)	0.058 (2)	0.017 (2)	−0.001 (2)	0.028 (2)
C10	0.0382 (13)	0.0407 (13)	0.0418 (14)	−0.0018 (12)	0.0036 (11)	0.0057 (12)
C11	0.0599 (18)	0.0705 (19)	0.058 (2)	−0.0117 (16)	0.0054 (17)	−0.0126 (17)
C12	0.104 (3)	0.101 (3)	0.057 (2)	−0.012 (3)	0.019 (2)	−0.024 (2)
C13	0.083 (3)	0.092 (3)	0.070 (2)	−0.007 (2)	0.039 (2)	−0.007 (2)
C14	0.0562 (19)	0.084 (2)	0.093 (3)	−0.0183 (17)	0.032 (2)	−0.005 (2)
C15	0.0512 (17)	0.073 (2)	0.0585 (19)	−0.0179 (16)	0.0123 (16)	−0.0096 (16)
C16	0.0455 (15)	0.0465 (16)	0.0459 (16)	−0.0003 (12)	0.0133 (14)	0.0018 (13)
C17	0.086 (2)	0.0481 (17)	0.0638 (19)	0.0097 (18)	0.0120 (19)	0.0055 (15)
C18	0.124 (4)	0.043 (2)	0.090 (3)	0.001 (2)	0.031 (3)	0.003 (2)
C19	0.120 (3)	0.059 (2)	0.091 (3)	−0.028 (2)	0.035 (3)	−0.025 (2)
C20	0.084 (2)	0.082 (3)	0.073 (2)	−0.016 (2)	−0.001 (2)	−0.020 (2)
C21	0.0646 (19)	0.0556 (17)	0.063 (2)	−0.0046 (15)	0.0028 (19)	−0.0073 (16)

Geometric parameters (Å, º)

P—C16	1.827 (3)	C9—H9C	0.9600
P—C10	1.835 (2)	C10—C11	1.369 (4)
P—C2	1.835 (3)	C10—C15	1.375 (4)
O1—C5	1.370 (3)	C11—C12	1.376 (4)
O1—C7	1.454 (3)	C11—H11	0.9300
O2—C6	1.369 (3)	C12—C13	1.352 (5)
O2—C7	1.452 (3)	C12—H12	0.9300
C1—C6	1.368 (3)	C13—C14	1.353 (5)
C1—C2	1.408 (3)	C13—H13	0.9300
C1—C1^i	1.498 (4)	C14—C15	1.380 (4)
C2—C3	1.390 (3)	C14—H14	0.9300
C3—C4	1.383 (4)	C15—H15	0.9300
C3—H3	0.9300	C16—C21	1.378 (4)
C4—C5	1.360 (3)	C16—C17	1.393 (4)
C4—H4	0.9300	C17—C18	1.374 (5)
C5—C6	1.378 (3)	C17—H17	0.9300
C7—C8	1.487 (4)	C18—C19	1.354 (6)
C7—C9	1.495 (4)	C18—H18	0.9300
C8—H8A	0.9600	C19—C20	1.366 (5)
C8—H8B	0.9600	C19—H19	0.9300
C8—H8C	0.9600	C20—C21	1.389 (4)
C9—H9A	0.9600	C20—H20	0.9300
C9—H9B	0.9600	C21—H21	0.9300
C16—P—C10	99.81 (12)	H9A—C9—H9C	109.5
C16—P—C2	102.03 (12)	H9B—C9—H9C	109.5
C10—P—C2	103.43 (11)	C11—C10—C15	117.5 (3)
C5—O1—C7	106.30 (18)	C11—C10—P	117.3 (2)
C6—O2—C7	106.51 (18)	C15—C10—P	125.2 (2)
C6—C1—C2	116.5 (2)	C10—C11—C12	121.5 (3)
C6—C1—C1^i	121.7 (2)	C10—C11—H11	119.2
C2—C1—C1^i	121.7 (2)	C12—C11—H11	119.2
C3—C2—C1	119.8 (2)	C13—C12—C11	120.1 (3)
C3—C2—P	123.3 (2)	C13—C12—H12	120.0
C1—C2—P	116.88 (17)	C11—C12—H12	120.0
C4—C3—C2	122.4 (2)	C12—C13—C14	119.6 (3)
C4—C3—H3	118.8	C12—C13—H13	120.2
C2—C3—H3	118.8	C14—C13—H13	120.2
C5—C4—C3	116.8 (2)	C13—C14—C15	120.7 (3)
C5—C4—H4	121.6	C13—C14—H14	119.7
C3—C4—H4	121.6	C15—C14—H14	119.7
C4—C5—O1	128.2 (2)	C10—C15—C14	120.6 (3)
C4—C5—C6	121.7 (2)	C10—C15—H15	119.7
O1—C5—C6	110.0 (2)	C14—C15—H15	119.7
C1—C6—O2	127.4 (2)	C21—C16—C17	118.2 (3)
C1—C6—C5	122.7 (2)	C21—C16—P	125.8 (2)
O2—C6—C5	109.9 (2)	C17—C16—P	116.0 (2)
O2—C7—O1	105.47 (19)	C18—C17—C16	120.2 (3)
O2—C7—C8	109.8 (2)	C18—C17—H17	119.9
O1—C7—C8	108.9 (3)	C16—C17—H17	119.9
O2—C7—C9	108.8 (3)	C19—C18—C17	121.2 (3)
O1—C7—C9	108.1 (3)	C19—C18—H18	119.4
C8—C7—C9	115.3 (3)	C17—C18—H18	119.4
C7—C8—H8A	109.5	C18—C19—C20	119.5 (3)
C7—C8—H8B	109.5	C18—C19—H19	120.2
H8A—C8—H8B	109.5	C20—C19—H19	120.2
C7—C8—H8C	109.5	C19—C20—C21	120.4 (4)
H8A—C8—H8C	109.5	C19—C20—H20	119.8
H8B—C8—H8C	109.5	C21—C20—H20	119.8
C7—C9—H9A	109.5	C16—C21—C20	120.4 (3)
C7—C9—H9B	109.5	C16—C21—H21	119.8
H9A—C9—H9B	109.5	C20—C21—H21	119.8
C7—C9—H9C	109.5

Symmetry code: (i) −x, −y+1, z.