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Acta Cryst. (2007). E63, m2344    [ doi:10.1107/S1600536807039529 ]

(R)-(+)-[[mu]-2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene-[kappa]2P:P']bis[chloridogold(I)] dichloromethane solvate

J. W. Bats, M. Hamzic and A. S. K. Hashmi

Abstract top

In the crystal structure of the title compound, [Au2Cl2(C44H32P2)]·CH2Cl2, the molecule is located on a twofold axis. The naphthyl group is slightly bent; the angle between the planes of the two six-membered rings is 3.5 (5)°. The angle between the mean planes of the two symmetry-related naphthyl groups is 84.4 (1)°. The P-Au-Cl group is almost linear, with an angle of 175.5 (1)°. The dichloromethane solvent molecule lies on a twofold axis and connects the AuCl groups of two symmetry-related molecules via intermolecular C-H...Cl hydrogen bonding.

Comment top

The molecule has twofold symmetry and there is a crystallographic twofold axis passing through the midpoint of the C10—C10 bond. The naphthyl group is slightly bend: the angle between the planes of the two six-membered rings is 3.5 (5)°. Moreover atom C10 deviates 0.064 (5)Å from the plane through C1/C2/C3/C4/C9. The angle between the best planes of the two symmetry-related naphthyl groups is 84.4 (1)°. Both phenyl groups attached to P1 are essentially planar. The P—Au—Cl bond is almost linear with a bond angle of 175.5 (1)°. The dichloromethane solvate group also lies on a twofold axis. Its H atoms donate weak hydrogen bonds to Cl atoms of two symmetry-related Au—Cl groups (see Table). The crystal packing also shows a number of additional intermolecular C—H···Cl contacts with H···Cl distances between 3.00 and 3.15Å and a number of weak intermolecular C—H···π(benzene) interactions (Cg1, Cg2 and Cg3 are the centroids of the benzene rings labeled C1/C2/C3/C4/C9/C10, C4/C5/C6/C7/C8/C9 and C11/C12/C13/C14/C15/C16 respectively). The crystal structure of the corresponding bis(ditolylphosphino) compound has been reported by Muñoz et al. (2005). The conformation of that molecule, however, differs considerably from the conformation of the title compound.

Related literature top

Gold catalysis is becoming increasingly important (Hashmi & Hutchings, 2006) and the use of chiral gold complexes for enantioselective catalysis is one of the latest hot topics (Hashmi, 2005). In this context detailed structural information about these gold complexes is of high importance. Thus we conducted a crystal structure analysis of the title compound, which was prepared in analogy to related compounds (King & Eisch, 1986). The structure of a closely related molecule has been reported by Muñoz et al. (2005).

Experimental top

The title compound was prepared in analogy to related compounds in the literature (King & Eisch, 1986). Single crystals were obtained by recrystallization from dichloromethane.

Refinement top

H atoms were geometrically positioned using fixed distances: C(sp2)-H = 0.95 Å, Csecondary—H = 0.99 Å and Uiso(H) = 1.2Ueq(C). The absolute configuration of the molecule was determined from the value of the Flack x parameter (Flack, 1983) using 2122 Friedel pairs. The maximum and minimum difference peaks are within 1Å from the Au atom.

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1996); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) with atomic numbering scheme and displacement ellipsoids are drawn at the 50% probability level. The H atoms are drawn as small spheres of arbitrary radius and the C—H···Cl hydrogen bonding is shown as a dotted lines. Symmetry codes: i = −x, y, −z,
(R)-(+)-[µ-2,2'-Bis(diphenylphosphino)-1,1'-binaphthalene-\ κ2P:P']bis[chloridogold(I)] dichloromethane solvate top
Crystal data top
[Au2Cl2(C44H32P2)]·CH2Cl2F000 = 1120
Mr = 1172.40Dx = 1.933 Mg m−3
Monoclinic, C2Mo Kα radiation
λ = 0.71073 Å
Hall symbol: C 2yCell parameters from 124 reflections
a = 19.480 (3) Åθ = 3–23º
b = 8.6889 (13) ŵ = 7.65 mm−1
c = 14.085 (2) ÅT = 165 (2) K
β = 122.361 (15)ºRod, colourless
V = 2013.8 (6) Å30.55 × 0.08 × 0.06 mm
Z = 2
Data collection top
Siemens SMART 1K CCD
diffractometer		4750 independent reflections
Radiation source: normal-focus sealed tube3716 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.051
T = 165(2) Kθmax = 28.6º
ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		h = −26→25
Tmin = 0.459, Tmax = 0.632k = −11→11
15554 measured reflectionsl = −18→18
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038  w = 1/[σ2(Fo2) + (0.03P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.077(Δ/σ)max = 0.001
S = 1.01Δρmax = 1.40 e Å−3
4750 reflectionsΔρmin = −1.33 e Å−3
240 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: heavy-atom methodFlack parameter: 0.003 (9)
Secondary atom site location: difference Fourier map
Crystal data top
[Au2Cl2(C44H32P2)]·CH2Cl2V = 2013.8 (6) Å3
Mr = 1172.40Z = 2
Monoclinic, C2Mo Kα
a = 19.480 (3) ŵ = 7.65 mm−1
b = 8.6889 (13) ÅT = 165 (2) K
c = 14.085 (2) Å0.55 × 0.08 × 0.06 mm
β = 122.361 (15)º
Data collection top
Siemens SMART 1K CCD
diffractometer		4750 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		3716 reflections with I > 2σ(I)
Tmin = 0.459, Tmax = 0.632Rint = 0.051
15554 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.077Δρmax = 1.40 e Å−3
S = 1.01Δρmin = −1.33 e Å−3
4750 reflectionsAbsolute structure: Flack (1983)
240 parametersFlack parameter: 0.003 (9)
1 restraint
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
Au10.030660 (16)0.00085 (4)0.21397 (2)0.03045 (9)
Cl1−0.06153 (14)−0.0668 (3)0.2601 (2)0.0431 (6)
Cl2−0.0766 (2)0.2910 (6)0.4864 (3)0.1173 (16)
P10.12613 (12)0.0508 (2)0.17702 (16)0.0231 (5)
C10.1051 (5)0.1638 (9)0.0544 (7)0.0165 (18)
C20.1626 (5)0.1598 (9)0.0248 (7)0.0254 (18)
H2A0.20950.09730.06700.030*
C30.1532 (5)0.2451 (9)−0.0654 (7)0.030 (2)
H3A0.19330.2392−0.08410.036*
C40.0855 (5)0.3389 (8)−0.1280 (6)0.0230 (17)
C50.0773 (6)0.4282 (9)−0.2159 (7)0.034 (2)
H5A0.11610.4195−0.23690.041*
C60.0126 (6)0.5296 (11)−0.2726 (7)0.038 (3)
H6A0.00800.5922−0.33100.046*
C7−0.0463 (5)0.5400 (8)−0.2439 (7)0.034 (2)
H7A−0.09080.6087−0.28380.041*
C8−0.0399 (5)0.4501 (8)−0.1575 (6)0.0238 (18)
H8A−0.07960.4586−0.13820.029*
C90.0256 (4)0.3467 (8)−0.0985 (6)0.0205 (16)
C100.0334 (4)0.2521 (8)−0.0094 (6)0.0188 (16)
C110.1655 (5)−0.1328 (8)0.1610 (7)0.0244 (17)
C120.1319 (5)−0.1978 (10)0.0548 (8)0.028 (2)
H12A0.0926−0.1418−0.00960.033*
C130.1546 (5)−0.3407 (9)0.0421 (7)0.034 (2)
H13A0.1310−0.3831−0.03110.041*
C140.2102 (5)−0.4225 (9)0.1318 (7)0.032 (2)
H14A0.2257−0.52190.12190.039*
C150.2445 (5)−0.3616 (10)0.2380 (8)0.039 (2)
H15A0.2840−0.41860.30170.047*
C160.2207 (5)−0.2143 (9)0.2517 (7)0.033 (2)
H16A0.2436−0.17240.32490.040*
C170.2116 (5)0.1490 (9)0.2941 (6)0.0265 (19)
C180.2862 (6)0.1502 (11)0.3116 (8)0.045 (2)
H18A0.29580.09330.26220.053*
C190.3532 (7)0.2352 (12)0.4034 (9)0.058 (3)
H19A0.40560.23410.41390.069*
C200.3388 (6)0.3176 (12)0.4750 (8)0.052 (3)
H20A0.38140.37430.53570.063*
C210.2618 (8)0.3168 (12)0.4574 (8)0.059 (3)
H21A0.25170.37400.50630.071*
C220.1985 (6)0.2331 (10)0.3689 (7)0.039 (2)
H22A0.14620.23280.35890.047*
C230.00000.178 (2)0.50000.073 (5)
H23A−0.02120.11070.43300.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Au10.03470 (15)0.02825 (14)0.03155 (14)0.0041 (2)0.01983 (12)0.0057 (3)
Cl10.0461 (13)0.0405 (12)0.0593 (15)0.0033 (10)0.0393 (12)0.0099 (11)
Cl20.061 (2)0.208 (5)0.073 (2)0.008 (3)0.029 (2)−0.049 (3)
P10.0270 (11)0.0210 (11)0.0246 (10)0.0053 (7)0.0160 (9)0.0023 (7)
C10.025 (5)0.011 (4)0.019 (4)−0.010 (3)0.016 (4)−0.005 (3)
C20.015 (4)0.027 (4)0.032 (5)0.004 (3)0.011 (4)−0.006 (4)
C30.035 (5)0.026 (4)0.050 (5)−0.015 (4)0.037 (5)−0.022 (4)
C40.031 (5)0.013 (4)0.030 (4)−0.008 (3)0.020 (4)−0.006 (3)
C50.055 (6)0.027 (4)0.039 (5)−0.009 (4)0.038 (5)−0.007 (4)
C60.079 (6)0.021 (8)0.035 (4)−0.007 (5)0.045 (5)−0.001 (4)
C70.049 (5)0.014 (6)0.035 (5)0.001 (3)0.020 (4)0.002 (3)
C80.029 (4)0.021 (4)0.030 (4)−0.003 (3)0.022 (4)0.000 (3)
C90.024 (4)0.017 (4)0.021 (4)−0.013 (3)0.013 (3)−0.008 (3)
C100.024 (4)0.018 (4)0.014 (4)−0.003 (3)0.010 (3)−0.002 (3)
C110.023 (4)0.018 (4)0.037 (5)0.001 (3)0.019 (4)−0.004 (3)
C120.029 (6)0.016 (5)0.037 (5)−0.001 (4)0.017 (5)−0.005 (4)
C130.036 (5)0.023 (4)0.043 (5)−0.010 (4)0.020 (5)−0.007 (4)
C140.032 (5)0.019 (4)0.053 (6)−0.007 (4)0.028 (5)−0.004 (4)
C150.042 (5)0.034 (5)0.048 (6)0.009 (4)0.029 (5)0.020 (4)
C160.046 (6)0.024 (5)0.038 (5)0.009 (4)0.028 (5)0.007 (4)
C170.034 (5)0.021 (4)0.021 (4)0.003 (3)0.013 (4)0.003 (3)
C180.042 (6)0.047 (6)0.041 (6)−0.004 (5)0.020 (5)−0.020 (4)
C190.052 (7)0.058 (7)0.048 (7)0.001 (5)0.017 (6)0.010 (5)
C200.053 (7)0.064 (7)0.028 (5)−0.023 (5)0.014 (5)−0.003 (5)
C210.099 (9)0.051 (7)0.033 (6)−0.010 (6)0.039 (6)−0.005 (5)
C220.039 (5)0.056 (6)0.026 (5)0.000 (4)0.021 (4)0.006 (4)
C230.072 (12)0.076 (11)0.102 (14)0.0000.067 (11)0.000
Geometric parameters (Å, °) top
Au1—P12.226 (2)C11—C121.392 (12)
Au1—Cl12.290 (2)C12—C131.362 (11)
Cl2—C231.712 (10)C12—H12A0.9500
P1—C171.811 (8)C13—C141.345 (11)
P1—C11.833 (8)C13—H13A0.9500
P1—C111.835 (7)C14—C151.376 (12)
C1—C21.388 (11)C14—H14A0.9500
C1—C101.416 (11)C15—C161.409 (11)
C2—C31.395 (12)C15—H15A0.9500
C2—H2A0.9500C16—H16A0.9500
C3—C41.393 (11)C17—C181.338 (12)
C3—H3A0.9500C17—C221.413 (11)
C4—C51.396 (11)C18—C191.454 (13)
C4—C91.434 (10)C18—H18A0.9500
C5—C61.386 (12)C19—C201.383 (14)
C5—H5A0.9500C19—H19A0.9500
C6—C71.409 (12)C20—C211.384 (14)
C6—H6A0.9500C20—H20A0.9500
C7—C81.394 (10)C21—C221.400 (13)
C7—H7A0.9500C21—H21A0.9500
C8—C91.410 (10)C22—H22A0.9500
C8—H8A0.9500C23—Cl2ii1.712 (10)
C9—C101.439 (10)C23—H23A0.9900
C10—C10i1.459 (14)C23—H23Aii0.9900
C11—C161.349 (11)
P1—Au1—Cl1175.47 (8)C13—C12—C11120.8 (8)
C17—P1—C1103.8 (4)C13—C12—H12A119.6
C17—P1—C11106.3 (4)C11—C12—H12A119.6
C1—P1—C11104.3 (4)C14—C13—C12120.9 (8)
C17—P1—Au1110.8 (3)C14—C13—H13A119.6
C1—P1—Au1122.1 (3)C12—C13—H13A119.6
C11—P1—Au1108.4 (2)C13—C14—C15119.8 (8)
C2—C1—C10120.3 (7)C13—C14—H14A120.1
C2—C1—P1117.4 (6)C15—C14—H14A120.1
C10—C1—P1122.3 (6)C14—C15—C16119.6 (8)
C1—C2—C3121.8 (7)C14—C15—H15A120.2
C1—C2—H2A119.1C16—C15—H15A120.2
C3—C2—H2A119.1C11—C16—C15120.1 (8)
C4—C3—C2120.3 (7)C11—C16—H16A119.9
C4—C3—H3A119.8C15—C16—H16A119.9
C2—C3—H3A119.8C18—C17—C22118.1 (8)
C3—C4—C5120.4 (8)C18—C17—P1123.3 (7)
C3—C4—C9119.1 (7)C22—C17—P1118.5 (7)
C5—C4—C9120.4 (7)C17—C18—C19122.5 (9)
C6—C5—C4120.1 (8)C17—C18—H18A118.8
C6—C5—H5A120.0C19—C18—H18A118.8
C4—C5—H5A120.0C20—C19—C18118.5 (10)
C5—C6—C7120.2 (8)C20—C19—H19A120.8
C5—C6—H6A119.9C18—C19—H19A120.8
C7—C6—H6A119.9C19—C20—C21119.4 (10)
C8—C7—C6120.6 (8)C19—C20—H20A120.3
C8—C7—H7A119.7C21—C20—H20A120.3
C6—C7—H7A119.7C20—C21—C22121.0 (10)
C7—C8—C9120.1 (7)C20—C21—H21A119.5
C7—C8—H8A120.0C22—C21—H21A119.5
C9—C8—H8A120.0C21—C22—C17120.6 (9)
C8—C9—C4118.6 (7)C21—C22—H22A119.7
C8—C9—C10121.2 (7)C17—C22—H22A119.7
C4—C9—C10120.2 (7)Cl2—C23—Cl2ii109.7 (10)
C1—C10—C9118.1 (7)Cl2—C23—H23A109.7
C1—C10—C10i123.9 (7)Cl2ii—C23—H23A109.7
C9—C10—C10i118.0 (7)Cl2—C23—H23Aii109.7
C16—C11—C12118.9 (7)Cl2ii—C23—H23Aii109.7
C16—C11—P1120.9 (6)H23A—C23—H23Aii108.2
C12—C11—P1119.8 (6)
C17—P1—C1—C268.2 (6)C4—C9—C10—C10i−173.6 (6)
C11—P1—C1—C2−43.0 (6)C17—P1—C11—C1639.3 (8)
Au1—P1—C1—C2−166.0 (5)C1—P1—C11—C16148.6 (7)
C17—P1—C1—C10−112.1 (6)Au1—P1—C11—C16−79.9 (7)
C11—P1—C1—C10136.7 (6)C17—P1—C11—C12−147.8 (7)
Au1—P1—C1—C1013.7 (7)C1—P1—C11—C12−38.5 (7)
C10—C1—C2—C32.1 (11)Au1—P1—C11—C1293.1 (7)
P1—C1—C2—C3−178.3 (6)C16—C11—C12—C13−0.6 (13)
C1—C2—C3—C40.6 (11)P1—C11—C12—C13−173.6 (7)
C2—C3—C4—C5177.9 (7)C11—C12—C13—C140.0 (14)
C2—C3—C4—C90.1 (10)C12—C13—C14—C150.1 (13)
C3—C4—C5—C6−175.4 (7)C13—C14—C15—C160.4 (12)
C9—C4—C5—C62.4 (11)C12—C11—C16—C151.1 (12)
C4—C5—C6—C7−1.7 (12)P1—C11—C16—C15174.1 (6)
C5—C6—C7—C80.8 (12)C14—C15—C16—C11−1.0 (13)
C6—C7—C8—C9−0.6 (11)C1—P1—C17—C18−69.1 (8)
C7—C8—C9—C41.3 (10)C11—P1—C17—C1840.6 (9)
C7—C8—C9—C10−179.6 (6)Au1—P1—C17—C18158.1 (7)
C3—C4—C9—C8175.6 (6)C1—P1—C17—C22108.7 (7)
C5—C4—C9—C8−2.2 (10)C11—P1—C17—C22−141.6 (6)
C3—C4—C9—C10−3.5 (10)Au1—P1—C17—C22−24.0 (7)
C5—C4—C9—C10178.7 (7)C22—C17—C18—C19−0.5 (14)
C2—C1—C10—C9−5.3 (10)P1—C17—C18—C19177.3 (7)
P1—C1—C10—C9175.0 (5)C17—C18—C19—C200.0 (15)
C2—C1—C10—C10i174.3 (6)C18—C19—C20—C210.0 (15)
P1—C1—C10—C10i−5.4 (9)C19—C20—C21—C220.4 (15)
C8—C9—C10—C1−173.0 (6)C20—C21—C22—C17−0.9 (14)
C4—C9—C10—C16.0 (10)C18—C17—C22—C211.0 (13)
C8—C9—C10—C10i7.4 (9)P1—C17—C22—C21−177.0 (7)
Symmetry codes: (i) −x, y, −z; (ii) −x, y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6A···Cl1iii0.953.123.614 (10)114
C15—H15A···Cl2iv0.953.153.618 (11)113
C16—H16A···Cl2iv0.953.003.542 (10)118
C19—H19A···Cl1v0.953.103.658 (14)120
C23—H23A···Cl10.992.623.611 (11)174
C3—H3A···Cg3vi0.952.893.837179
C8—H8A···Cg3iii0.953.073.792134
C13—H13A···Cg2vii0.952.613.447147
C14—H14A···Cg1vii0.953.053.612119
Symmetry codes: (iii) −x, y+1, −z; (iv) x+1/2, y−1/2, z; (v) x+1/2, y+1/2, z; (vi) −x+1/2, y+1/2, −z; (vii) x, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C23—H23A···Cl10.992.623.611 (11)174
references
References top

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