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The mol­ecule of the title complex, [(η6-C6H6){PhP(CH2CH=CH2)2}RuCl2], has the classic piano-stool structure. However, it is noted that the Ru—C distances trans to phospho­rus are longer than those trans to chloride. Such a manifestation of the trans-influence is not normally so pronounced in η6-arene complexes of this type. This is the first structure containing the di­allyl­phenyl­phosphine ligand.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015215/ya6059sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015215/ya6059Isup2.hkl
Contains datablock I

CCDC reference: 175374

Key indicators

  • Single-crystal X-ray study
  • T = 123 K
  • Mean [sigma](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








Comment top

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.

Experimental top

[(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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of the title complex showing the atom-numbering scheme and 50% probability displacement ellipsoids.
(I) top
Crystal data top
[RuCl2(C6H6)(C12H15P)]F(000) = 888
Mr = 440.29Dx = 1.611 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.128 (5) ÅCell parameters from 25 reflections
b = 9.995 (5) Åθ = 30.5–38.3°
c = 25.55 (2) ŵ = 1.24 mm1
β = 94.26 (6)°T = 123 K
V = 1815 (2) Å3Prism, dark red
Z = 40.5 × 0.2 × 0.2 mm
Data collection top
Rigaku AFC-7S
diffractometer
3178 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.049
Graphite monochromatorθmax = 27.1°, θmin = 2.6°
ω scans with profile analysish = 09
Absorption correction: ψ scan
(North et al., 1968)
k = 012
Tmin = 0.552, Tmax = 0.780l = 3232
4311 measured reflections3 standard reflections every 150 reflections
3991 independent reflections intensity decay: none
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH 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 = 1.03Δρmax = 0.61 e Å3
3991 reflectionsΔρmin = 0.51 e Å3
223 parameters
Crystal data top
[RuCl2(C6H6)(C12H15P)]V = 1815 (2) Å3
Mr = 440.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.128 (5) ŵ = 1.24 mm1
b = 9.995 (5) ÅT = 123 K
c = 25.55 (2) Å0.5 × 0.2 × 0.2 mm
β = 94.26 (6)°
Data collection top
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 = 0.7803 standard reflections every 150 reflections
4311 measured reflections intensity decay: none
3991 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.61 e Å3
3991 reflectionsΔρmin = 0.51 e Å3
223 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ru11.33428 (3)0.27571 (2)0.938260 (9)0.01928 (8)
Cl11.50940 (11)0.43173 (8)0.88842 (3)0.02801 (17)
Cl21.62223 (10)0.15249 (8)0.95681 (3)0.02799 (17)
P11.29744 (10)0.16320 (8)0.85848 (3)0.02059 (16)
C11.0298 (4)0.2959 (3)0.94254 (12)0.0270 (7)
C21.0935 (4)0.1824 (4)0.97195 (12)0.0270 (7)
C31.2414 (5)0.1943 (4)1.01101 (12)0.0283 (7)
C41.3178 (5)0.3241 (4)1.02402 (12)0.0291 (7)
C51.2560 (4)0.4350 (4)0.99526 (13)0.0289 (7)
C61.1152 (4)0.4202 (3)0.95266 (12)0.0260 (6)
C71.1680 (4)0.0062 (3)0.86180 (12)0.0238 (6)
C81.2302 (5)0.0835 (3)0.90125 (13)0.0305 (7)
H81.33870.06280.92370.037*
C91.1351 (5)0.2025 (3)0.90796 (13)0.0339 (8)
H91.17840.26320.93480.041*
C100.9768 (5)0.2326 (3)0.87541 (13)0.0326 (7)
H100.91180.31430.87990.039*
C110.9133 (5)0.1447 (3)0.83662 (13)0.0308 (7)
H110.80390.16570.81460.037*
C121.0085 (4)0.0251 (3)0.82944 (12)0.0262 (6)
H120.96450.0350.80250.031*
C131.1834 (4)0.2581 (3)0.80334 (11)0.0246 (6)
H13A1.16310.19710.77290.03*
H13B1.27110.3290.79340.03*
C140.9989 (4)0.3224 (3)0.81294 (12)0.0278 (6)
H140.89740.26490.81970.033*
C150.9666 (5)0.4514 (4)0.81275 (13)0.0351 (8)
H15A1.06440.51230.80610.042*
H15B0.84530.4840.81920.042*
C161.5202 (4)0.1136 (4)0.83151 (12)0.0285 (7)
H16A1.58020.04310.85420.034*
H16B1.60570.19170.83290.034*
C171.4997 (4)0.0625 (4)0.77606 (13)0.0328 (7)
H171.43490.01960.76970.039*
C181.5651 (5)0.1233 (4)0.73593 (13)0.0410 (9)
H18A1.63060.20570.74080.049*
H18B1.5470.08520.70190.049*
H10.933 (5)0.287 (4)0.9131 (14)0.030 (9)*
H21.041 (5)0.101 (4)0.9636 (14)0.031 (9)*
H31.297 (5)0.115 (4)1.0280 (14)0.034 (10)*
H41.420 (5)0.325 (4)1.0508 (14)0.028 (9)*
H51.311 (5)0.525 (4)1.0060 (15)0.044 (11)*
H61.082 (4)0.495 (3)0.9321 (12)0.017 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.01837 (12)0.02150 (13)0.01785 (12)0.00173 (9)0.00055 (8)0.00110 (9)
Cl10.0346 (4)0.0272 (4)0.0226 (3)0.0084 (3)0.0044 (3)0.0010 (3)
Cl20.0192 (3)0.0362 (4)0.0281 (4)0.0009 (3)0.0018 (3)0.0060 (3)
P10.0188 (3)0.0229 (4)0.0198 (3)0.0000 (3)0.0003 (3)0.0001 (3)
C10.0210 (14)0.0370 (19)0.0233 (15)0.0010 (13)0.0045 (11)0.0003 (13)
C20.0245 (15)0.0317 (17)0.0256 (15)0.0079 (13)0.0076 (12)0.0013 (13)
C30.0289 (16)0.037 (2)0.0201 (14)0.0003 (14)0.0070 (12)0.0058 (13)
C40.0304 (16)0.0403 (19)0.0168 (14)0.0021 (14)0.0022 (12)0.0028 (13)
C50.0280 (16)0.0323 (18)0.0274 (16)0.0024 (14)0.0092 (12)0.0077 (14)
C60.0239 (15)0.0280 (17)0.0266 (15)0.0052 (13)0.0048 (12)0.0036 (13)
C70.0225 (14)0.0238 (15)0.0251 (14)0.0016 (12)0.0007 (11)0.0041 (12)
C80.0315 (17)0.0292 (17)0.0300 (17)0.0014 (14)0.0038 (13)0.0013 (14)
C90.044 (2)0.0273 (18)0.0299 (17)0.0015 (15)0.0021 (14)0.0043 (14)
C100.0431 (19)0.0231 (16)0.0325 (17)0.0072 (14)0.0082 (14)0.0052 (14)
C110.0314 (17)0.0321 (18)0.0286 (16)0.0063 (14)0.0003 (13)0.0080 (14)
C120.0299 (16)0.0273 (16)0.0211 (14)0.0001 (13)0.0008 (12)0.0008 (12)
C130.0246 (15)0.0288 (17)0.0204 (14)0.0002 (12)0.0001 (11)0.0022 (12)
C140.0239 (15)0.0352 (17)0.0236 (14)0.0017 (14)0.0027 (11)0.0022 (14)
C150.0341 (18)0.041 (2)0.0300 (17)0.0068 (15)0.0028 (14)0.0026 (15)
C160.0224 (14)0.0362 (18)0.0270 (15)0.0019 (13)0.0033 (12)0.0043 (14)
C170.0257 (16)0.0384 (19)0.0340 (17)0.0028 (14)0.0001 (13)0.0149 (15)
C180.0389 (19)0.058 (3)0.0258 (16)0.0070 (18)0.0017 (14)0.0119 (17)
Geometric parameters (Å, º) top
Ru1—C32.177 (3)C2—C31.402 (5)
Ru1—C62.178 (3)C3—C41.437 (5)
Ru1—C22.186 (3)C4—C51.383 (5)
Ru1—C12.190 (3)C5—C61.433 (5)
Ru1—C42.256 (3)C7—C121.391 (4)
Ru1—C52.255 (3)C7—C81.396 (5)
Ru1—P12.3258 (16)C8—C91.386 (5)
Ru1—Cl22.4104 (15)C9—C101.384 (5)
Ru1—Cl12.4182 (14)C10—C111.376 (5)
P1—C71.826 (3)C11—C121.393 (4)
P1—C131.837 (3)C13—C141.500 (4)
P1—C161.845 (3)C14—C151.309 (5)
C1—C61.398 (5)C16—C171.503 (4)
C1—C21.417 (5)C17—C181.307 (5)
C3—Ru1—C680.57 (13)C7—P1—C13106.46 (15)
C3—Ru1—C237.50 (12)C7—P1—C16103.77 (16)
C6—Ru1—C267.82 (13)C13—P1—C16101.33 (15)
C3—Ru1—C168.07 (13)C7—P1—Ru1113.55 (11)
C6—Ru1—C137.33 (12)C13—P1—Ru1115.91 (12)
C2—Ru1—C137.79 (13)C16—P1—Ru1114.40 (11)
C3—Ru1—C437.77 (13)C6—C1—C2119.7 (3)
C6—Ru1—C466.66 (13)C6—C1—Ru170.86 (18)
C2—Ru1—C467.04 (13)C2—C1—Ru170.92 (18)
C1—Ru1—C478.95 (13)C3—C2—C1120.2 (3)
C3—Ru1—C566.86 (14)C3—C2—Ru170.91 (19)
C6—Ru1—C537.66 (12)C1—C2—Ru171.29 (18)
C2—Ru1—C578.93 (13)C2—C3—C4119.6 (3)
C1—Ru1—C566.99 (13)C2—C3—Ru171.59 (19)
C4—Ru1—C535.71 (13)C4—C3—Ru174.10 (18)
C3—Ru1—P1123.10 (10)C5—C4—C3120.0 (3)
C6—Ru1—P1115.65 (10)C5—C4—Ru172.14 (18)
C2—Ru1—P195.62 (10)C3—C4—Ru168.14 (17)
C1—Ru1—P192.33 (10)C4—C5—C6119.9 (3)
C4—Ru1—P1160.83 (10)C4—C5—Ru172.15 (19)
C5—Ru1—P1152.87 (9)C6—C5—Ru168.24 (18)
C3—Ru1—Cl287.12 (11)C1—C6—C5120.2 (3)
C6—Ru1—Cl2156.39 (9)C1—C6—Ru171.81 (19)
C2—Ru1—Cl2112.75 (10)C5—C6—Ru174.10 (19)
C1—Ru1—Cl2150.43 (9)C12—C7—C8119.1 (3)
C4—Ru1—Cl291.36 (10)C12—C7—P1124.0 (2)
C5—Ru1—Cl2118.78 (10)C8—C7—P1116.8 (2)
P1—Ru1—Cl287.96 (6)C9—C8—C7120.5 (3)
C3—Ru1—Cl1153.17 (9)C10—C9—C8119.8 (3)
C6—Ru1—Cl193.79 (10)C11—C10—C9120.3 (3)
C2—Ru1—Cl1159.04 (10)C10—C11—C12120.3 (3)
C1—Ru1—Cl1121.26 (10)C7—C12—C11120.0 (3)
C4—Ru1—Cl1116.07 (10)C14—C13—P1116.0 (2)
C5—Ru1—Cl192.69 (10)C15—C14—C13125.3 (3)
P1—Ru1—Cl183.07 (6)C17—C16—P1114.7 (2)
Cl2—Ru1—Cl188.15 (5)C18—C17—C16124.5 (3)

Experimental details

Crystal data
Chemical formula[RuCl2(C6H6)(C12H15P)]
Mr440.29
Crystal system, space groupMonoclinic, P21/c
Temperature (K)123
a, b, c (Å)7.128 (5), 9.995 (5), 25.55 (2)
β (°) 94.26 (6)
V3)1815 (2)
Z4
Radiation typeMo Kα
µ (mm1)1.24
Crystal size (mm)0.5 × 0.2 × 0.2
Data collection
DiffractometerRigaku AFC-7S
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.552, 0.780
No. of measured, independent and
observed [I > 2σ(I)] reflections
4311, 3991, 3178
Rint0.049
(sin θ/λ)max1)0.641
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.079, 1.03
No. of reflections3991
No. of parameters223
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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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