Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015215/ya6059sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015215/ya6059Isup2.hkl |
CCDC reference: 175374
Key indicators
- Single-crystal X-ray study
- T = 123 K
- Mean (C-C) = 0.005 Å
- R factor = 0.030
- wR factor = 0.079
- Data-to-parameter ratio = 17.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
[(η6-C6H6)RuCl2]2 (0.35 g, 1.4 mmol) and excess diallylphenyl phosphine (2.26 g, 11.9 mmol) in toluene (25 ml) were refluxed under N2 for 4 h. The resulting red solid was filtered off and washed with hexane. Yield 0.42 g, 69%. A sample suitable for X-ray diffraction was obtained as red prisms by slow diffusion of n-hexane into a dichloromethane solution of the product.
The benzene H atoms were refined isotropically. All remaining H atoms were included in the riding motion approximation with isotropic displacement parameters equal to 1.2Ueq of the carrier atom.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. View of the title complex showing the atom-numbering scheme and 50% probability displacement ellipsoids. |
[RuCl2(C6H6)(C12H15P)] | F(000) = 888 |
Mr = 440.29 | Dx = 1.611 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.128 (5) Å | Cell parameters from 25 reflections |
b = 9.995 (5) Å | θ = 30.5–38.3° |
c = 25.55 (2) Å | µ = 1.24 mm−1 |
β = 94.26 (6)° | T = 123 K |
V = 1815 (2) Å3 | Prism, dark red |
Z = 4 | 0.5 × 0.2 × 0.2 mm |
Rigaku AFC-7S diffractometer | 3178 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.049 |
Graphite monochromator | θmax = 27.1°, θmin = 2.6° |
ω scans with profile analysis | h = 0→9 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→12 |
Tmin = 0.552, Tmax = 0.780 | l = −32→32 |
4311 measured reflections | 3 standard reflections every 150 reflections |
3991 independent reflections | intensity decay: none |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.030 | w = 1/[σ2(Fo2) + (0.035P)2 + 0.8253P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.079 | (Δ/σ)max = 0.003 |
S = 1.03 | Δρmax = 0.61 e Å−3 |
3991 reflections | Δρmin = −0.51 e Å−3 |
223 parameters |
[RuCl2(C6H6)(C12H15P)] | V = 1815 (2) Å3 |
Mr = 440.29 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.128 (5) Å | µ = 1.24 mm−1 |
b = 9.995 (5) Å | T = 123 K |
c = 25.55 (2) Å | 0.5 × 0.2 × 0.2 mm |
β = 94.26 (6)° |
Rigaku AFC-7S diffractometer | 3178 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.049 |
Tmin = 0.552, Tmax = 0.780 | 3 standard reflections every 150 reflections |
4311 measured reflections | intensity decay: none |
3991 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.61 e Å−3 |
3991 reflections | Δρmin = −0.51 e Å−3 |
223 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ru1 | 1.33428 (3) | −0.27571 (2) | 0.938260 (9) | 0.01928 (8) | |
Cl1 | 1.50940 (11) | −0.43173 (8) | 0.88842 (3) | 0.02801 (17) | |
Cl2 | 1.62223 (10) | −0.15249 (8) | 0.95681 (3) | 0.02799 (17) | |
P1 | 1.29744 (10) | −0.16320 (8) | 0.85848 (3) | 0.02059 (16) | |
C1 | 1.0298 (4) | −0.2959 (3) | 0.94254 (12) | 0.0270 (7) | |
C2 | 1.0935 (4) | −0.1824 (4) | 0.97195 (12) | 0.0270 (7) | |
C3 | 1.2414 (5) | −0.1943 (4) | 1.01101 (12) | 0.0283 (7) | |
C4 | 1.3178 (5) | −0.3241 (4) | 1.02402 (12) | 0.0291 (7) | |
C5 | 1.2560 (4) | −0.4350 (4) | 0.99526 (13) | 0.0289 (7) | |
C6 | 1.1152 (4) | −0.4202 (3) | 0.95266 (12) | 0.0260 (6) | |
C7 | 1.1680 (4) | −0.0062 (3) | 0.86180 (12) | 0.0238 (6) | |
C8 | 1.2302 (5) | 0.0835 (3) | 0.90125 (13) | 0.0305 (7) | |
H8 | 1.3387 | 0.0628 | 0.9237 | 0.037* | |
C9 | 1.1351 (5) | 0.2025 (3) | 0.90796 (13) | 0.0339 (8) | |
H9 | 1.1784 | 0.2632 | 0.9348 | 0.041* | |
C10 | 0.9768 (5) | 0.2326 (3) | 0.87541 (13) | 0.0326 (7) | |
H10 | 0.9118 | 0.3143 | 0.8799 | 0.039* | |
C11 | 0.9133 (5) | 0.1447 (3) | 0.83662 (13) | 0.0308 (7) | |
H11 | 0.8039 | 0.1657 | 0.8146 | 0.037* | |
C12 | 1.0085 (4) | 0.0251 (3) | 0.82944 (12) | 0.0262 (6) | |
H12 | 0.9645 | −0.035 | 0.8025 | 0.031* | |
C13 | 1.1834 (4) | −0.2581 (3) | 0.80334 (11) | 0.0246 (6) | |
H13A | 1.1631 | −0.1971 | 0.7729 | 0.03* | |
H13B | 1.2711 | −0.329 | 0.7934 | 0.03* | |
C14 | 0.9989 (4) | −0.3224 (3) | 0.81294 (12) | 0.0278 (6) | |
H14 | 0.8974 | −0.2649 | 0.8197 | 0.033* | |
C15 | 0.9666 (5) | −0.4514 (4) | 0.81275 (13) | 0.0351 (8) | |
H15A | 1.0644 | −0.5123 | 0.8061 | 0.042* | |
H15B | 0.8453 | −0.484 | 0.8192 | 0.042* | |
C16 | 1.5202 (4) | −0.1136 (4) | 0.83151 (12) | 0.0285 (7) | |
H16A | 1.5802 | −0.0431 | 0.8542 | 0.034* | |
H16B | 1.6057 | −0.1917 | 0.8329 | 0.034* | |
C17 | 1.4997 (4) | −0.0625 (4) | 0.77606 (13) | 0.0328 (7) | |
H17 | 1.4349 | 0.0196 | 0.7697 | 0.039* | |
C18 | 1.5651 (5) | −0.1233 (4) | 0.73593 (13) | 0.0410 (9) | |
H18A | 1.6306 | −0.2057 | 0.7408 | 0.049* | |
H18B | 1.547 | −0.0852 | 0.7019 | 0.049* | |
H1 | 0.933 (5) | −0.287 (4) | 0.9131 (14) | 0.030 (9)* | |
H2 | 1.041 (5) | −0.101 (4) | 0.9636 (14) | 0.031 (9)* | |
H3 | 1.297 (5) | −0.115 (4) | 1.0280 (14) | 0.034 (10)* | |
H4 | 1.420 (5) | −0.325 (4) | 1.0508 (14) | 0.028 (9)* | |
H5 | 1.311 (5) | −0.525 (4) | 1.0060 (15) | 0.044 (11)* | |
H6 | 1.082 (4) | −0.495 (3) | 0.9321 (12) | 0.017 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01837 (12) | 0.02150 (13) | 0.01785 (12) | 0.00173 (9) | 0.00055 (8) | −0.00110 (9) |
Cl1 | 0.0346 (4) | 0.0272 (4) | 0.0226 (3) | 0.0084 (3) | 0.0044 (3) | −0.0010 (3) |
Cl2 | 0.0192 (3) | 0.0362 (4) | 0.0281 (4) | −0.0009 (3) | −0.0018 (3) | −0.0060 (3) |
P1 | 0.0188 (3) | 0.0229 (4) | 0.0198 (3) | 0.0000 (3) | −0.0003 (3) | −0.0001 (3) |
C1 | 0.0210 (14) | 0.0370 (19) | 0.0233 (15) | 0.0010 (13) | 0.0045 (11) | 0.0003 (13) |
C2 | 0.0245 (15) | 0.0317 (17) | 0.0256 (15) | 0.0079 (13) | 0.0076 (12) | −0.0013 (13) |
C3 | 0.0289 (16) | 0.037 (2) | 0.0201 (14) | −0.0003 (14) | 0.0070 (12) | −0.0058 (13) |
C4 | 0.0304 (16) | 0.0403 (19) | 0.0168 (14) | 0.0021 (14) | 0.0022 (12) | 0.0028 (13) |
C5 | 0.0280 (16) | 0.0323 (18) | 0.0274 (16) | 0.0024 (14) | 0.0092 (12) | 0.0077 (14) |
C6 | 0.0239 (15) | 0.0280 (17) | 0.0266 (15) | −0.0052 (13) | 0.0048 (12) | −0.0036 (13) |
C7 | 0.0225 (14) | 0.0238 (15) | 0.0251 (14) | 0.0016 (12) | 0.0007 (11) | 0.0041 (12) |
C8 | 0.0315 (17) | 0.0292 (17) | 0.0300 (17) | 0.0014 (14) | −0.0038 (13) | −0.0013 (14) |
C9 | 0.044 (2) | 0.0273 (18) | 0.0299 (17) | 0.0015 (15) | −0.0021 (14) | −0.0043 (14) |
C10 | 0.0431 (19) | 0.0231 (16) | 0.0325 (17) | 0.0072 (14) | 0.0082 (14) | 0.0052 (14) |
C11 | 0.0314 (17) | 0.0321 (18) | 0.0286 (16) | 0.0063 (14) | 0.0003 (13) | 0.0080 (14) |
C12 | 0.0299 (16) | 0.0273 (16) | 0.0211 (14) | 0.0001 (13) | −0.0008 (12) | 0.0008 (12) |
C13 | 0.0246 (15) | 0.0288 (17) | 0.0204 (14) | 0.0002 (12) | 0.0001 (11) | −0.0022 (12) |
C14 | 0.0239 (15) | 0.0352 (17) | 0.0236 (14) | −0.0017 (14) | −0.0027 (11) | −0.0022 (14) |
C15 | 0.0341 (18) | 0.041 (2) | 0.0300 (17) | −0.0068 (15) | 0.0028 (14) | −0.0026 (15) |
C16 | 0.0224 (14) | 0.0362 (18) | 0.0270 (15) | −0.0019 (13) | 0.0033 (12) | 0.0043 (14) |
C17 | 0.0257 (16) | 0.0384 (19) | 0.0340 (17) | −0.0028 (14) | −0.0001 (13) | 0.0149 (15) |
C18 | 0.0389 (19) | 0.058 (3) | 0.0258 (16) | −0.0070 (18) | 0.0017 (14) | 0.0119 (17) |
Ru1—C3 | 2.177 (3) | C2—C3 | 1.402 (5) |
Ru1—C6 | 2.178 (3) | C3—C4 | 1.437 (5) |
Ru1—C2 | 2.186 (3) | C4—C5 | 1.383 (5) |
Ru1—C1 | 2.190 (3) | C5—C6 | 1.433 (5) |
Ru1—C4 | 2.256 (3) | C7—C12 | 1.391 (4) |
Ru1—C5 | 2.255 (3) | C7—C8 | 1.396 (5) |
Ru1—P1 | 2.3258 (16) | C8—C9 | 1.386 (5) |
Ru1—Cl2 | 2.4104 (15) | C9—C10 | 1.384 (5) |
Ru1—Cl1 | 2.4182 (14) | C10—C11 | 1.376 (5) |
P1—C7 | 1.826 (3) | C11—C12 | 1.393 (4) |
P1—C13 | 1.837 (3) | C13—C14 | 1.500 (4) |
P1—C16 | 1.845 (3) | C14—C15 | 1.309 (5) |
C1—C6 | 1.398 (5) | C16—C17 | 1.503 (4) |
C1—C2 | 1.417 (5) | C17—C18 | 1.307 (5) |
C3—Ru1—C6 | 80.57 (13) | C7—P1—C13 | 106.46 (15) |
C3—Ru1—C2 | 37.50 (12) | C7—P1—C16 | 103.77 (16) |
C6—Ru1—C2 | 67.82 (13) | C13—P1—C16 | 101.33 (15) |
C3—Ru1—C1 | 68.07 (13) | C7—P1—Ru1 | 113.55 (11) |
C6—Ru1—C1 | 37.33 (12) | C13—P1—Ru1 | 115.91 (12) |
C2—Ru1—C1 | 37.79 (13) | C16—P1—Ru1 | 114.40 (11) |
C3—Ru1—C4 | 37.77 (13) | C6—C1—C2 | 119.7 (3) |
C6—Ru1—C4 | 66.66 (13) | C6—C1—Ru1 | 70.86 (18) |
C2—Ru1—C4 | 67.04 (13) | C2—C1—Ru1 | 70.92 (18) |
C1—Ru1—C4 | 78.95 (13) | C3—C2—C1 | 120.2 (3) |
C3—Ru1—C5 | 66.86 (14) | C3—C2—Ru1 | 70.91 (19) |
C6—Ru1—C5 | 37.66 (12) | C1—C2—Ru1 | 71.29 (18) |
C2—Ru1—C5 | 78.93 (13) | C2—C3—C4 | 119.6 (3) |
C1—Ru1—C5 | 66.99 (13) | C2—C3—Ru1 | 71.59 (19) |
C4—Ru1—C5 | 35.71 (13) | C4—C3—Ru1 | 74.10 (18) |
C3—Ru1—P1 | 123.10 (10) | C5—C4—C3 | 120.0 (3) |
C6—Ru1—P1 | 115.65 (10) | C5—C4—Ru1 | 72.14 (18) |
C2—Ru1—P1 | 95.62 (10) | C3—C4—Ru1 | 68.14 (17) |
C1—Ru1—P1 | 92.33 (10) | C4—C5—C6 | 119.9 (3) |
C4—Ru1—P1 | 160.83 (10) | C4—C5—Ru1 | 72.15 (19) |
C5—Ru1—P1 | 152.87 (9) | C6—C5—Ru1 | 68.24 (18) |
C3—Ru1—Cl2 | 87.12 (11) | C1—C6—C5 | 120.2 (3) |
C6—Ru1—Cl2 | 156.39 (9) | C1—C6—Ru1 | 71.81 (19) |
C2—Ru1—Cl2 | 112.75 (10) | C5—C6—Ru1 | 74.10 (19) |
C1—Ru1—Cl2 | 150.43 (9) | C12—C7—C8 | 119.1 (3) |
C4—Ru1—Cl2 | 91.36 (10) | C12—C7—P1 | 124.0 (2) |
C5—Ru1—Cl2 | 118.78 (10) | C8—C7—P1 | 116.8 (2) |
P1—Ru1—Cl2 | 87.96 (6) | C9—C8—C7 | 120.5 (3) |
C3—Ru1—Cl1 | 153.17 (9) | C10—C9—C8 | 119.8 (3) |
C6—Ru1—Cl1 | 93.79 (10) | C11—C10—C9 | 120.3 (3) |
C2—Ru1—Cl1 | 159.04 (10) | C10—C11—C12 | 120.3 (3) |
C1—Ru1—Cl1 | 121.26 (10) | C7—C12—C11 | 120.0 (3) |
C4—Ru1—Cl1 | 116.07 (10) | C14—C13—P1 | 116.0 (2) |
C5—Ru1—Cl1 | 92.69 (10) | C15—C14—C13 | 125.3 (3) |
P1—Ru1—Cl1 | 83.07 (6) | C17—C16—P1 | 114.7 (2) |
Cl2—Ru1—Cl1 | 88.15 (5) | C18—C17—C16 | 124.5 (3) |
Experimental details
Crystal data | |
Chemical formula | [RuCl2(C6H6)(C12H15P)] |
Mr | 440.29 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 123 |
a, b, c (Å) | 7.128 (5), 9.995 (5), 25.55 (2) |
β (°) | 94.26 (6) |
V (Å3) | 1815 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.24 |
Crystal size (mm) | 0.5 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.552, 0.780 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4311, 3991, 3178 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.641 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.079, 1.03 |
No. of reflections | 3991 |
No. of parameters | 223 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.61, −0.51 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1985, 1992), SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997a), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
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Allyl and vinyl phosphines are important precursors for the preparation of more complex phosphine containing ligands (e.g. King & Cloyd, 1975). The title compound, (I), was prepared as part of a study on the use of allyl and vinyl phosphines in metal templated additions to secondary phosphines. This compound is an important intermediate and we undertook the X-ray study in an effort to understand aspects of the reactivity of this compound.
This is the first structural study of a complex with the diallylphosphine ligand. It reveals a classical piano-stool geometry (Fig. 1). The Ru—Cl and Ru—P distances are typical of such a species. The angles subtended at the Ru atom by P and the two Cl atoms are less than 90° [88.15 (5), 83.07 (6) and 87.96 (6)° for Cl1—-Ru1–Cl2, Cl1—Ru1—P1 and Cl2—Ru1—P1, respectively], and the remaining coordination sites are occupied by the η6-benzene ligand. The Ru—C distances reveal a distortion in the π-arene ligand. The distances trans to phosphorus at 2.255 (3) and 2.256 (3) Å are markedly longer than the others (2.177–2.190 Å) which are trans to Cl, a manifestation of the trans-effect. The result is a folding of the arene about the C3—C6 vector with a dihedral angle of 5.1 (4)°, the largest observed in these systems, compared with 5.0° in [(η6-benzene)Ru(PMePh2)Cl2], 2.0° in [(η6-p-cymene)Ru(PMePh2)Cl2] (Bennett et al., 1972), 1.9° in [{η6-o-C6H4(Me)(CO2Me)}Ru(PPh2Neomenthyl)Cl2] (Bennett et al., 1989). In the complex [(η6-benzene)Ru(PPh3)Cl2] (Elsegood & Tocher, 1995), no discernable pattern of distortion in the arene can be found.
Despite the asymmetric disposition of the ligand in the solid state with regard to the metal centre, the sharp NMR spectrum, in which both allyl groups are equivalent, suggests that in solution the conformation is on average symmetrical indicating that the allyl groups should both be able to react with a secondary phosphine coordinated to the metal centre, as we desired.