(R)-(+)-2,2'-Bis­(di­phenyl­phosphinoyl)-1,1'-bi­naphthyl

The title compound, BINAP oxide, C₄₄H₃₂O₂P₂, (I), was synthesized by direct oxidation of (R)-(+)-2,2'-bis­(di­phenyl­phosphino)-1,1'-bi­naphthyl (BINAP) with tert-butyl hydro­peroxide in toluene solution. The angle between the naphthyl planes of the bi­naphthyl group is 94.17 (3)°.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

(R)-(+)-2,2'-bis(diphenylphosphinoyl)-1,1'-binaphthyl

Crystal data

C44H32O2P2	F(000) = 684
Mr = 654.64	Dx = 1.279 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 9.0719 (2) Å	Cell parameters from 16714 reflections
b = 18.9903 (8) Å	θ = 2.6–32.0°
c = 10.1528 (3) Å	µ = 0.17 mm^−1
β = 103.620 (2)°	T = 150 K
V = 1699.92 (10) Å^3	Block cut from neeedle, colourless
Z = 2	0.34 × 0.30 × 0.20 mm

Data collection

Nonius KappaCDD diffractometer	10057 independent reflections
Radiation source: fine-focus sealed tube	7746 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans with κ offsets	θmax = 32.0°, θmin = 2.6°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −13→13
Tmin = 0.946, Tmax = 0.968	k = −25→28
16714 measured reflections	l = −15→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0192P)^2 + 0.3419P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
10057 reflections	Δρmax = 0.32 e Å^−3
434 parameters	Δρmin = −0.37 e Å^−3
1 restraint	Absolute structure: Flack (1983); 4058 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (6)

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
P1	0.38718 (6)	0.11271 (3)	0.09531 (5)	0.02064 (11)
P2	0.46092 (6)	0.25701 (3)	0.43790 (5)	0.02034 (11)
O1	0.39653 (15)	0.08055 (9)	0.23009 (14)	0.0262 (3)
O2	0.39496 (15)	0.28703 (8)	0.30197 (13)	0.0254 (3)
C1	0.6220 (2)	0.20572 (11)	0.21129 (18)	0.0187 (4)
C2	0.5082 (2)	0.18876 (12)	0.09794 (19)	0.0196 (4)
C3	0.4856 (2)	0.23184 (12)	−0.01941 (19)	0.0218 (4)
H3A	0.4102	0.2192	−0.0977	0.026*
C4	0.5700 (2)	0.29108 (12)	−0.0221 (2)	0.0238 (4)
H4A	0.5499	0.3201	−0.1006	0.029*
C5	0.6872 (2)	0.30965 (12)	0.0912 (2)	0.0225 (4)
C6	0.7771 (2)	0.37096 (13)	0.0916 (2)	0.0284 (5)
H6A	0.7557	0.4018	0.0157	0.034*
C7	0.8946 (3)	0.38616 (14)	0.2005 (3)	0.0382 (6)
H7A	0.9540	0.4273	0.1997	0.046*
C8	0.9271 (3)	0.34084 (15)	0.3134 (2)	0.0375 (6)
H8A	1.0106	0.3507	0.3872	0.045*
C9	0.8398 (2)	0.28302 (13)	0.3177 (2)	0.0290 (5)
H9A	0.8618	0.2537	0.3957	0.035*
C10	0.7166 (2)	0.26566 (12)	0.20790 (18)	0.0211 (4)
C11	0.6484 (2)	0.16290 (11)	0.33892 (18)	0.0188 (4)
C12	0.5825 (2)	0.18048 (12)	0.44404 (19)	0.0199 (4)
C13	0.6046 (2)	0.13633 (12)	0.56012 (19)	0.0226 (4)
H13A	0.5603	0.1489	0.6328	0.027*
C14	0.6887 (2)	0.07609 (12)	0.56889 (19)	0.0230 (4)
H14A	0.6990	0.0465	0.6460	0.028*
C15	0.7602 (2)	0.05723 (12)	0.4647 (2)	0.0237 (4)
C16	0.8472 (2)	−0.00510 (13)	0.4718 (2)	0.0314 (5)
H16A	0.8557	−0.0359	0.5470	0.038*
C17	0.9197 (3)	−0.02172 (15)	0.3709 (3)	0.0400 (6)
H17A	0.9785	−0.0635	0.3768	0.048*
C18	0.9062 (3)	0.02348 (15)	0.2593 (2)	0.0379 (6)
H18A	0.9570	0.0121	0.1902	0.046*
C19	0.8213 (2)	0.08342 (13)	0.2484 (2)	0.0290 (5)
H19A	0.8140	0.1133	0.1721	0.035*
C20	0.7435 (2)	0.10180 (12)	0.34986 (19)	0.0214 (4)
C21	0.1953 (2)	0.13983 (13)	0.01918 (19)	0.0236 (4)
C22	0.1457 (2)	0.20685 (14)	0.0442 (2)	0.0304 (5)
H22A	0.2161	0.2411	0.0892	0.036*
C23	−0.0077 (3)	0.22327 (16)	0.0030 (2)	0.0394 (6)
H23A	−0.0417	0.2692	0.0181	0.047*
C24	−0.1110 (3)	0.17319 (17)	−0.0599 (2)	0.0400 (7)
H24A	−0.2156	0.1849	−0.0877	0.048*
C25	−0.0634 (3)	0.10659 (18)	−0.0826 (2)	0.0408 (7)
H25A	−0.1348	0.0721	−0.1247	0.049*
C26	0.0910 (2)	0.08985 (14)	−0.0434 (2)	0.0319 (5)
H26A	0.1244	0.0440	−0.0598	0.038*
C31	0.4421 (2)	0.05061 (13)	−0.0201 (2)	0.0264 (5)
C32	0.3958 (3)	0.05595 (14)	−0.1612 (2)	0.0331 (5)
H32A	0.3332	0.0940	−0.2016	0.040*
C33	0.4419 (3)	0.00526 (15)	−0.2422 (3)	0.0416 (6)
H33A	0.4089	0.0082	−0.3381	0.050*
C34	0.5357 (3)	−0.04938 (15)	−0.1837 (3)	0.0470 (7)
H34A	0.5659	−0.0842	−0.2392	0.056*
C35	0.5854 (3)	−0.05318 (15)	−0.0438 (3)	0.0437 (7)
H35A	0.6535	−0.0894	−0.0037	0.052*
C36	0.5360 (2)	−0.00430 (13)	0.0374 (3)	0.0325 (5)
H36A	0.5668	−0.0084	0.1333	0.039*
C41	0.3149 (2)	0.22762 (13)	0.52049 (19)	0.0245 (4)
C42	0.2696 (2)	0.26796 (15)	0.6187 (2)	0.0324 (6)
H42A	0.3207	0.3106	0.6501	0.039*
C43	0.1476 (3)	0.24489 (18)	0.6708 (2)	0.0429 (7)
H43A	0.1148	0.2725	0.7365	0.051*
C44	0.0756 (3)	0.18276 (18)	0.6274 (2)	0.0436 (7)
H44A	−0.0053	0.1670	0.6648	0.052*
C45	0.1198 (3)	0.14301 (17)	0.5300 (3)	0.0423 (7)
H45A	0.0687	0.1003	0.4997	0.051*
C46	0.2394 (2)	0.16534 (14)	0.4759 (2)	0.0323 (5)
H46A	0.2693	0.1379	0.4084	0.039*
C51	0.5729 (2)	0.32112 (12)	0.55000 (19)	0.0220 (4)
C52	0.7075 (2)	0.30618 (13)	0.6440 (2)	0.0268 (5)
H52A	0.7469	0.2596	0.6520	0.032*
C53	0.7844 (3)	0.35944 (14)	0.7260 (2)	0.0314 (5)
H53A	0.8773	0.3493	0.7889	0.038*
C54	0.7267 (2)	0.42708 (13)	0.7169 (2)	0.0305 (5)
H54A	0.7789	0.4630	0.7746	0.037*
C55	0.5933 (3)	0.44237 (14)	0.6238 (2)	0.0362 (6)
H55A	0.5539	0.4889	0.6169	0.043*
C56	0.5172 (3)	0.38986 (13)	0.5407 (2)	0.0315 (5)
H56A	0.4257	0.4007	0.4764	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0222 (2)	0.0189 (3)	0.0204 (2)	0.0001 (2)	0.00404 (18)	0.0013 (2)
P2	0.0231 (2)	0.0192 (3)	0.0193 (2)	0.0008 (2)	0.00613 (18)	−0.0002 (2)
O1	0.0300 (8)	0.0234 (8)	0.0243 (7)	−0.0027 (7)	0.0047 (6)	0.0064 (7)
O2	0.0311 (8)	0.0238 (9)	0.0208 (7)	0.0040 (7)	0.0053 (6)	0.0027 (6)
C1	0.0203 (9)	0.0196 (11)	0.0171 (9)	0.0037 (8)	0.0059 (7)	0.0023 (8)
C2	0.0210 (9)	0.0180 (11)	0.0206 (9)	0.0001 (8)	0.0063 (7)	0.0012 (8)
C3	0.0228 (10)	0.0233 (11)	0.0187 (9)	0.0020 (9)	0.0037 (7)	0.0022 (8)
C4	0.0278 (10)	0.0227 (12)	0.0212 (9)	0.0035 (9)	0.0065 (8)	0.0058 (9)
C5	0.0260 (10)	0.0203 (11)	0.0231 (10)	0.0011 (9)	0.0096 (8)	0.0020 (9)
C6	0.0327 (12)	0.0221 (12)	0.0308 (11)	−0.0008 (10)	0.0084 (9)	0.0044 (9)
C7	0.0409 (14)	0.0272 (14)	0.0447 (14)	−0.0130 (11)	0.0064 (11)	0.0045 (11)
C8	0.0389 (14)	0.0344 (16)	0.0335 (13)	−0.0104 (12)	−0.0029 (10)	0.0010 (11)
C9	0.0304 (11)	0.0289 (13)	0.0258 (10)	−0.0059 (10)	0.0027 (8)	0.0018 (9)
C10	0.0232 (9)	0.0193 (11)	0.0215 (9)	0.0001 (9)	0.0068 (7)	0.0004 (8)
C11	0.0197 (9)	0.0162 (10)	0.0194 (9)	−0.0034 (8)	0.0025 (7)	0.0016 (8)
C12	0.0212 (10)	0.0177 (11)	0.0201 (9)	−0.0015 (8)	0.0034 (7)	0.0008 (8)
C13	0.0258 (10)	0.0241 (12)	0.0177 (9)	−0.0027 (9)	0.0045 (8)	0.0012 (8)
C14	0.0235 (10)	0.0224 (11)	0.0209 (9)	−0.0004 (9)	0.0010 (7)	0.0070 (9)
C15	0.0198 (9)	0.0243 (12)	0.0256 (10)	−0.0016 (9)	0.0029 (8)	0.0048 (9)
C16	0.0286 (11)	0.0274 (13)	0.0383 (12)	0.0069 (10)	0.0084 (9)	0.0109 (11)
C17	0.0394 (13)	0.0334 (15)	0.0492 (15)	0.0181 (12)	0.0143 (11)	0.0059 (12)
C18	0.0357 (13)	0.0419 (17)	0.0391 (13)	0.0158 (12)	0.0148 (10)	0.0041 (12)
C19	0.0274 (11)	0.0338 (14)	0.0267 (10)	0.0061 (10)	0.0084 (8)	0.0067 (10)
C20	0.0183 (9)	0.0206 (12)	0.0236 (9)	0.0013 (8)	0.0015 (7)	0.0019 (8)
C21	0.0224 (10)	0.0280 (12)	0.0202 (9)	0.0002 (9)	0.0046 (8)	0.0027 (9)
C22	0.0259 (11)	0.0330 (14)	0.0331 (12)	0.0015 (10)	0.0087 (9)	0.0021 (10)
C23	0.0328 (12)	0.0463 (17)	0.0418 (13)	0.0139 (12)	0.0141 (10)	0.0106 (13)
C24	0.0232 (11)	0.069 (2)	0.0292 (12)	0.0089 (13)	0.0082 (9)	0.0107 (13)
C25	0.0281 (11)	0.065 (2)	0.0278 (11)	−0.0072 (13)	0.0037 (9)	−0.0009 (13)
C26	0.0297 (11)	0.0376 (15)	0.0275 (11)	−0.0011 (10)	0.0051 (9)	−0.0038 (10)
C31	0.0269 (10)	0.0218 (12)	0.0325 (11)	−0.0031 (9)	0.0110 (9)	−0.0023 (9)
C32	0.0425 (13)	0.0303 (14)	0.0308 (11)	−0.0039 (11)	0.0172 (10)	−0.0024 (10)
C33	0.0565 (16)	0.0364 (16)	0.0404 (14)	−0.0114 (13)	0.0288 (12)	−0.0110 (12)
C34	0.0571 (17)	0.0310 (15)	0.0651 (18)	−0.0071 (13)	0.0388 (14)	−0.0174 (14)
C35	0.0402 (14)	0.0272 (15)	0.0696 (19)	0.0016 (12)	0.0249 (13)	−0.0057 (14)
C36	0.0299 (12)	0.0237 (13)	0.0452 (14)	0.0010 (10)	0.0112 (10)	0.0003 (11)
C41	0.0220 (9)	0.0305 (12)	0.0202 (9)	0.0021 (9)	0.0037 (7)	0.0060 (9)
C42	0.0318 (11)	0.0418 (16)	0.0243 (10)	0.0069 (11)	0.0083 (8)	0.0026 (10)
C43	0.0344 (12)	0.069 (2)	0.0283 (12)	0.0155 (14)	0.0142 (9)	0.0094 (13)
C44	0.0260 (12)	0.070 (2)	0.0371 (13)	0.0040 (13)	0.0123 (10)	0.0242 (14)
C45	0.0248 (12)	0.0510 (18)	0.0483 (15)	−0.0053 (12)	0.0030 (10)	0.0153 (13)
C46	0.0249 (11)	0.0382 (15)	0.0331 (12)	−0.0014 (10)	0.0057 (9)	0.0076 (11)
C51	0.0252 (10)	0.0206 (11)	0.0215 (9)	−0.0018 (9)	0.0083 (8)	−0.0017 (8)
C52	0.0271 (11)	0.0217 (12)	0.0314 (11)	0.0024 (9)	0.0064 (9)	−0.0023 (9)
C53	0.0264 (11)	0.0356 (15)	0.0316 (12)	−0.0035 (10)	0.0055 (9)	−0.0041 (10)
C54	0.0364 (12)	0.0261 (13)	0.0302 (11)	−0.0072 (11)	0.0105 (9)	−0.0082 (10)
C55	0.0480 (15)	0.0235 (13)	0.0367 (13)	0.0017 (12)	0.0093 (11)	−0.0063 (11)
C56	0.0352 (12)	0.0267 (13)	0.0301 (11)	0.0058 (10)	0.0028 (9)	−0.0014 (10)

Geometric parameters (Å, º)

P1—O1	1.4824 (14)	C17—C18	1.404 (3)
P1—C21	1.806 (2)	C18—C19	1.364 (3)
P1—C2	1.811 (2)	C19—C20	1.422 (3)
P1—C31	1.813 (2)	C21—C26	1.384 (3)
P2—O2	1.4828 (14)	C21—C22	1.393 (3)
P2—C51	1.807 (2)	C22—C23	1.391 (3)
P2—C41	1.814 (2)	C23—C24	1.381 (4)
P2—C12	1.817 (2)	C24—C25	1.373 (4)
C1—C2	1.391 (3)	C25—C26	1.399 (3)
C1—C10	1.430 (3)	C31—C36	1.386 (3)
C1—C11	1.501 (3)	C31—C32	1.399 (3)
C2—C3	1.420 (3)	C32—C33	1.393 (3)
C3—C4	1.365 (3)	C33—C34	1.384 (4)
C4—C5	1.415 (3)	C34—C35	1.387 (4)
C5—C6	1.421 (3)	C35—C36	1.385 (3)
C5—C10	1.423 (3)	C41—C46	1.388 (3)
C6—C7	1.374 (3)	C41—C42	1.394 (3)
C7—C8	1.408 (3)	C42—C43	1.404 (3)
C8—C9	1.360 (3)	C43—C44	1.370 (4)
C9—C10	1.419 (3)	C44—C45	1.377 (4)
C11—C12	1.382 (3)	C45—C46	1.392 (3)
C11—C20	1.435 (3)	C51—C52	1.390 (3)
C12—C13	1.422 (3)	C51—C56	1.395 (3)
C13—C14	1.366 (3)	C52—C53	1.389 (3)
C14—C15	1.412 (3)	C53—C54	1.382 (3)
C15—C16	1.415 (3)	C54—C55	1.379 (3)
C15—C20	1.420 (3)	C55—C56	1.382 (3)
C16—C17	1.378 (3)
O1—P1—C21	110.64 (9)	C16—C15—C20	119.41 (19)
O1—P1—C2	114.34 (9)	C17—C16—C15	120.8 (2)
C21—P1—C2	107.40 (10)	C16—C17—C18	119.6 (2)
O1—P1—C31	111.34 (10)	C19—C18—C17	121.1 (2)
C21—P1—C31	107.03 (10)	C18—C19—C20	120.9 (2)
C2—P1—C31	105.69 (9)	C15—C20—C19	118.25 (19)
O2—P2—C51	111.77 (10)	C15—C20—C11	119.44 (17)
O2—P2—C41	111.71 (8)	C19—C20—C11	122.30 (18)
C51—P2—C41	106.23 (10)	C26—C21—C22	119.66 (19)
O2—P2—C12	116.63 (9)	C26—C21—P1	119.12 (18)
C51—P2—C12	105.70 (9)	C22—C21—P1	120.19 (17)
C41—P2—C12	103.97 (10)	C23—C22—C21	119.5 (2)
C2—C1—C10	119.79 (17)	C24—C23—C22	120.4 (3)
C2—C1—C11	121.69 (18)	C25—C24—C23	120.4 (2)
C10—C1—C11	118.52 (16)	C24—C25—C26	119.7 (3)
C1—C2—C3	119.56 (19)	C21—C26—C25	120.3 (2)
C1—C2—P1	121.76 (15)	C36—C31—C32	119.5 (2)
C3—C2—P1	118.69 (15)	C36—C31—P1	116.91 (17)
C4—C3—C2	121.39 (18)	C32—C31—P1	123.57 (19)
C3—C4—C5	120.47 (19)	C33—C32—C31	119.7 (2)
C4—C5—C6	121.83 (19)	C34—C33—C32	120.3 (2)
C4—C5—C10	119.22 (19)	C33—C34—C35	119.8 (2)
C6—C5—C10	118.95 (19)	C36—C35—C34	120.2 (3)
C7—C6—C5	120.7 (2)	C35—C36—C31	120.4 (2)
C6—C7—C8	120.1 (2)	C46—C41—C42	119.7 (2)
C9—C8—C7	120.5 (2)	C46—C41—P2	118.01 (17)
C8—C9—C10	121.3 (2)	C42—C41—P2	122.13 (19)
C9—C10—C5	118.43 (19)	C41—C42—C43	119.3 (3)
C9—C10—C1	122.12 (18)	C44—C43—C42	120.4 (2)
C5—C10—C1	119.45 (17)	C43—C44—C45	120.4 (2)
C12—C11—C20	119.84 (18)	C44—C45—C46	120.1 (3)
C12—C11—C1	121.75 (18)	C41—C46—C45	120.1 (2)
C20—C11—C1	118.41 (16)	C52—C51—C56	118.9 (2)
C11—C12—C13	119.70 (19)	C52—C51—P2	124.57 (18)
C11—C12—P2	122.45 (15)	C56—C51—P2	116.54 (16)
C13—C12—P2	117.81 (15)	C53—C52—C51	119.9 (2)
C14—C13—C12	121.06 (18)	C54—C53—C52	120.5 (2)
C13—C14—C15	120.79 (19)	C55—C54—C53	119.9 (2)
C14—C15—C16	121.6 (2)	C54—C55—C56	119.9 (2)
C14—C15—C20	119.0 (2)	C55—C56—C51	120.9 (2)