rac-2,2'-Bis(diphenyl-phosphan-yl)-1,1'-binaphth-yl: a racemic diphosphine ligand.

The asymmetric unit of the title compound, C(44)H(32)P(2), conventionally abbreviated BINAP, is one half of the complete chiral BINAP mol-ecule, which adopts a C2 crystallographic point-group symmetry with a twofold axis splitting the mol-ecule in two identical halves; a center of symmetry between mol-ecules further determines the racemic pairs. There are no obvious supra-molecular inter-actions between adjacent BINAP mol-ecules.

Related literature

For applications of triaryl­phosphine ligands in various catalytic reactions, see: Doherty et al. (2012 ▶); Uemura et al. (2012 ▶); Onodera et al. (2012 ▶); Lin et al. (2012 ▶). For applications of 2,2′-bis­(diphenyl­phosphan­yl)-1,1′-binaphthyl (BINAP) as a chiral catalyst in various asymmetric catalysed reactions, see: Kojima & Mikami (2012 ▶); Aikawa et al. (2011 ▶); Ge & Hartwig (2011 ▶); Moran et al. (2011 ▶). For similar diphosphine ligands, see: Kassube et al. (2008 ▶); Fawcett et al. (2005 ▶); Wu et al. (2004 ▶). For the related crystal structure of the (S)-enanti­omer (S)-(−)-2,2′-bis­(diphenyl­phosphan­yl)-1,1′-binaphthyl, see: Jones et al. (2003 ▶).

Experimental

Crystal data

C44H32P2

M = 622.64

Monoclinic,

a = 19.6120 (8) Å

b = 9.2008 (3) Å

c = 19.1240 (9) Å

β = 107.904 (5)°

V = 3283.7 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.16 mm−1

T = 293 K

0.29 × 0.23 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Gemini ultra diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.954, T max = 0.968

6234 measured reflections

3052 independent reflections

2314 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.099

S = 1.03

3052 reflections

208 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.22 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812025603/bg2467sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025603/bg2467Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812025603/bg2467Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C44H32P2	F(000) = 1304
Mr = 622.64	Dx = 1.259 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -C 2yc	Cell parameters from 2381 reflections
a = 19.6120 (8) Å	θ = 3.5–29.5°
b = 9.2008 (3) Å	µ = 0.16 mm−1
c = 19.1240 (9) Å	T = 293 K
β = 107.904 (5)°	Column, colourless
V = 3283.7 (2) Å3	0.29 × 0.23 × 0.20 mm
Z = 4

Oxford Diffraction Xcalibur Gemini ultra diffractometer	3052 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2314 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 10.3592 pixels mm-1	θmax = 25.5°, θmin = 3.6°
ω scans	h = −19→23
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→11
Tmin = 0.954, Tmax = 0.968	l = −20→23
6234 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0387P)2 + 1.4219P] where P = (Fo2 + 2Fc2)/3
3052 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

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	0.43987 (2)	0.96498 (5)	0.13904 (3)	0.03969 (16)
C1	0.41174 (9)	1.08276 (19)	0.20272 (9)	0.0348 (4)
C2	0.46167 (8)	1.17151 (17)	0.25019 (9)	0.0316 (4)
C3	0.44162 (9)	1.26196 (19)	0.30150 (9)	0.0368 (4)
C4	0.49012 (11)	1.3589 (2)	0.34918 (11)	0.0492 (5)
H4	0.5364	1.3677	0.3463	0.059*
C5	0.47017 (14)	1.4398 (3)	0.39936 (12)	0.0680 (7)
H5	0.5027	1.5037	0.4299	0.082*
C6	0.40094 (15)	1.4271 (3)	0.40508 (13)	0.0718 (7)
H6	0.3882	1.4804	0.4405	0.086*
C7	0.35255 (13)	1.3379 (2)	0.35949 (13)	0.0609 (6)
H7	0.3066	1.3314	0.3636	0.073*
C8	0.37053 (10)	1.2543 (2)	0.30552 (11)	0.0434 (5)
C9	0.32087 (10)	1.1626 (2)	0.25612 (12)	0.0489 (5)
H9	0.2740	1.1582	0.2576	0.059*
C10	0.34033 (9)	1.0807 (2)	0.20647 (11)	0.0450 (5)
H10	0.3063	1.0219	0.1742	0.054*
C11	0.38645 (9)	0.8015 (2)	0.13995 (11)	0.0422 (5)
C12	0.39753 (10)	0.7322 (2)	0.20704 (12)	0.0524 (5)
H12	0.4278	0.7746	0.2494	0.063*
C13	0.36481 (11)	0.6022 (2)	0.21238 (13)	0.0581 (6)
H13	0.3728	0.5583	0.2580	0.070*
C14	0.32063 (12)	0.5375 (2)	0.15075 (15)	0.0634 (6)
H14	0.2987	0.4493	0.1543	0.076*
C15	0.30870 (12)	0.6029 (2)	0.08377 (15)	0.0686 (7)
H15	0.2786	0.5588	0.0418	0.082*
C16	0.34129 (11)	0.7350 (2)	0.07787 (12)	0.0585 (6)
H16	0.3327	0.7787	0.0321	0.070*
C17	0.39622 (9)	1.0482 (2)	0.04936 (10)	0.0404 (4)
C18	0.35445 (10)	1.1731 (2)	0.03891 (11)	0.0472 (5)
H18	0.3428	1.2137	0.0783	0.057*
C19	0.32997 (11)	1.2376 (2)	−0.02968 (12)	0.0573 (6)
H19	0.3017	1.3206	−0.0359	0.069*
C20	0.34691 (12)	1.1805 (3)	−0.08887 (12)	0.0617 (6)
H20	0.3309	1.2253	−0.1346	0.074*
C21	0.38763 (12)	1.0571 (3)	−0.07949 (12)	0.0611 (6)
H21	0.3987	1.0171	−0.1193	0.073*
C22	0.41240 (11)	0.9914 (2)	−0.01138 (12)	0.0529 (5)
H22	0.4403	0.9079	−0.0059	0.063*

	U11	U22	U33	U12	U13	U23
P1	0.0373 (3)	0.0378 (3)	0.0424 (3)	−0.0027 (2)	0.0100 (2)	−0.0060 (2)
C1	0.0349 (9)	0.0343 (9)	0.0348 (10)	0.0003 (8)	0.0099 (8)	0.0037 (8)
C2	0.0341 (9)	0.0289 (9)	0.0321 (10)	0.0028 (7)	0.0106 (7)	0.0057 (7)
C3	0.0449 (10)	0.0330 (9)	0.0338 (10)	0.0092 (8)	0.0139 (8)	0.0087 (8)
C4	0.0547 (12)	0.0490 (12)	0.0414 (12)	0.0092 (10)	0.0112 (9)	−0.0061 (10)
C5	0.0838 (17)	0.0663 (15)	0.0498 (14)	0.0151 (13)	0.0146 (12)	−0.0185 (12)
C6	0.099 (2)	0.0709 (16)	0.0539 (15)	0.0304 (15)	0.0354 (14)	−0.0065 (13)
C7	0.0728 (15)	0.0642 (14)	0.0584 (15)	0.0275 (13)	0.0386 (13)	0.0129 (12)
C8	0.0505 (11)	0.0415 (11)	0.0445 (11)	0.0136 (9)	0.0240 (9)	0.0132 (9)
C9	0.0374 (10)	0.0544 (12)	0.0615 (14)	0.0078 (10)	0.0248 (10)	0.0153 (11)
C10	0.0340 (10)	0.0461 (11)	0.0538 (13)	−0.0030 (9)	0.0120 (9)	0.0049 (10)
C11	0.0372 (10)	0.0371 (10)	0.0491 (12)	0.0027 (8)	0.0086 (9)	−0.0020 (9)
C12	0.0511 (12)	0.0467 (12)	0.0545 (14)	−0.0014 (10)	0.0091 (10)	0.0005 (10)
C13	0.0571 (13)	0.0457 (12)	0.0712 (16)	0.0027 (11)	0.0193 (12)	0.0126 (12)
C14	0.0590 (14)	0.0376 (11)	0.094 (2)	−0.0063 (11)	0.0240 (13)	0.0040 (13)
C15	0.0681 (15)	0.0488 (13)	0.0762 (18)	−0.0184 (12)	0.0035 (13)	−0.0153 (13)
C16	0.0642 (13)	0.0484 (12)	0.0534 (14)	−0.0097 (11)	0.0040 (11)	−0.0036 (11)
C17	0.0399 (10)	0.0405 (10)	0.0417 (11)	−0.0104 (9)	0.0138 (8)	−0.0061 (9)
C18	0.0494 (11)	0.0485 (12)	0.0453 (12)	−0.0019 (10)	0.0168 (9)	0.0004 (10)
C19	0.0561 (12)	0.0542 (13)	0.0612 (15)	−0.0013 (11)	0.0176 (11)	0.0115 (12)
C20	0.0645 (14)	0.0730 (16)	0.0449 (14)	−0.0165 (13)	0.0130 (11)	0.0066 (12)
C21	0.0715 (15)	0.0713 (16)	0.0437 (13)	−0.0170 (13)	0.0223 (11)	−0.0128 (12)
C22	0.0576 (13)	0.0511 (12)	0.0516 (13)	−0.0071 (10)	0.0191 (10)	−0.0106 (10)

P1—C17	1.833 (2)	C11—C12	1.389 (3)
P1—C11	1.8364 (19)	C12—C13	1.376 (3)
P1—C1	1.8370 (18)	C12—H12	0.9300
C1—C2	1.380 (2)	C13—C14	1.366 (3)
C1—C10	1.424 (2)	C13—H13	0.9300
C2—C3	1.431 (2)	C14—C15	1.369 (3)
C2—C2i	1.506 (3)	C14—H14	0.9300
C3—C4	1.414 (3)	C15—C16	1.394 (3)
C3—C8	1.421 (2)	C15—H15	0.9300
C4—C5	1.363 (3)	C16—H16	0.9300
C4—H4	0.9300	C17—C18	1.389 (3)
C5—C6	1.400 (3)	C17—C22	1.397 (3)
C5—H5	0.9300	C18—C19	1.384 (3)
C6—C7	1.351 (3)	C18—H18	0.9300
C6—H6	0.9300	C19—C20	1.378 (3)
C7—C8	1.416 (3)	C19—H19	0.9300
C7—H7	0.9300	C20—C21	1.368 (3)
C8—C9	1.410 (3)	C20—H20	0.9300
C9—C10	1.356 (3)	C21—C22	1.382 (3)
C9—H9	0.9300	C21—H21	0.9300
C10—H10	0.9300	C22—H22	0.9300
C11—C16	1.386 (3)
C17—P1—C11	104.33 (8)	C12—C11—P1	117.20 (14)
C17—P1—C1	102.99 (8)	C13—C12—C11	121.6 (2)
C11—P1—C1	100.87 (8)	C13—C12—H12	119.2
C2—C1—C10	119.00 (16)	C11—C12—H12	119.2
C2—C1—P1	119.23 (12)	C14—C13—C12	120.1 (2)
C10—C1—P1	121.72 (14)	C14—C13—H13	119.9
C1—C2—C3	120.43 (15)	C12—C13—H13	119.9
C1—C2—C2i	120.30 (15)	C13—C14—C15	119.7 (2)
C3—C2—C2i	119.25 (15)	C13—C14—H14	120.1
C4—C3—C8	118.24 (17)	C15—C14—H14	120.1
C4—C3—C2	122.49 (16)	C14—C15—C16	120.6 (2)
C8—C3—C2	119.27 (16)	C14—C15—H15	119.7
C5—C4—C3	121.1 (2)	C16—C15—H15	119.7
C5—C4—H4	119.4	C11—C16—C15	120.2 (2)
C3—C4—H4	119.4	C11—C16—H16	119.9
C4—C5—C6	120.3 (2)	C15—C16—H16	119.9
C4—C5—H5	119.8	C18—C17—C22	117.69 (19)
C6—C5—H5	119.8	C18—C17—P1	124.43 (15)
C7—C6—C5	120.4 (2)	C22—C17—P1	117.50 (15)
C7—C6—H6	119.8	C19—C18—C17	120.55 (19)
C5—C6—H6	119.8	C19—C18—H18	119.7
C6—C7—C8	121.2 (2)	C17—C18—H18	119.7
C6—C7—H7	119.4	C20—C19—C18	120.9 (2)
C8—C7—H7	119.4	C20—C19—H19	119.5
C9—C8—C7	122.56 (19)	C18—C19—H19	119.5
C9—C8—C3	118.73 (17)	C21—C20—C19	119.1 (2)
C7—C8—C3	118.71 (19)	C21—C20—H20	120.4
C10—C9—C8	121.12 (17)	C19—C20—H20	120.4
C10—C9—H9	119.4	C20—C21—C22	120.6 (2)
C8—C9—H9	119.4	C20—C21—H21	119.7
C9—C10—C1	121.37 (18)	C22—C21—H21	119.7
C9—C10—H10	119.3	C21—C22—C17	121.1 (2)
C1—C10—H10	119.3	C21—C22—H22	119.5
C16—C11—C12	117.79 (18)	C17—C22—H22	119.5
C16—C11—P1	124.71 (16)