metal-organic compounds
(η6-Benzene)(benzyldiphenylphosphane)dichloridoruthenium(II)
aResearch Centre for Synthesis and Catalysis, Department of Chemistry, University of Johannesburg (APK Campus), PO Box 524, Auckland Park, Johannesburg, 2006, South Africa
*Correspondence e-mail: daviswl24@yahoo.com
In the title compound, [RuCl2(C6H6)(C19H17P)], the RuII atom has a distorted pseudo-octahedral coordination environment with the metrical parameters around the metallic core as Ru—centroid(η6-benzene) = 1.6894 (11) Å, Ru—P = 2.3466 (6), Ru—Cl(avg.) = 2.4127 (7) Å; Cl—Ru—Cl = 88.07 (2) and Cl—Ru—P = 82.77 (2), 87.65 (2)°. The effective cone angle for the benzyldiphenylphosphane was calculated to be 143°. In the crystal C—H⋯Cl and C—H⋯π interactions are observed.
Related literature
For II–arene complexes, see: Chen et al. (2002); De Clercq & Verpoort (2002); Wang et al. (2011); Aydemir et al. (2011). For background to ring-opening metathesis polymerization with Ru–arene complexes, see: Stumpf et al. (1995). For background to cone angles, see: Otto (2001); Tolman (1977). For a description of the Cambridge Structural Database, see: Allen (2002).
studies on RuExperimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2011); cell SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010) and WinGX (Farrugia, 1999).
Supporting information
https://doi.org/10.1107/S1600536812037154/bt6823sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037154/bt6823Isup2.hkl
[(C6H6)RuCl2]2 (50.0 mg, 0.10 mmol) and benzyldiphenylphosphane (60.4 mg, 0.22 mmol) in benzene (25 ml) were refluxed under argon for 4 h. The resulting red solution was filtered, the filtrate concentrated under reduced pressure to ca 5 ml whereby a sample suitable for single-crystal X-ray diffraction was obtained as red plates. Analytical data: 31P {H} NMR (CDCl3, 161.99 MHz): δ (p.p.m.) 30.34 (s). 1H NMR (CDCl3, 400 MHz): δ (p.p.m.) 2.15 (s, 2H, CH2); 5.30 (s, 6H, C6H6); 6.43 (d, 2H, Ar—H of C7H7); 6.85 (t, 2H, Ar—H of C7H7); 6.97 (t, 1H, Ar—H of C7H7); 7.35 (d, 4H, Ar—H of C6H5); 7.44 (t, 2H, Ar—H of C6H5); 7.67 (t, 4H, Ar—H of C6H5).
The aromatic and methylene H atoms were placed in geometrically idealized positions (C—H = 0.95–0.99) and allowed to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
The activity of the half-sandwich Ru(II)-arene complexes are well known in the catalytic transfer hydrogenation of η6-Ru compound containing benzyldiphenylphosphane as part of our ongoing investigation into these type of complexes.
(Chen et al., 2002; De Clercq & Verpoort, 2002; Wang et al., 2011; Aydemir et al., 2011) and for ring-opening metathesis polymerization (Stumpf et al., 1995). Reported here is theMolecules of the title compound packs in the orthorhombic π-bonded η6-benzene ligand is 1.6894 (11) Å and the mean Ru—C bond distance is 2.198 (3) Å. The coordination of the remaining ligands to the Ru atom shows deviation from the typical octahedral geometry with Cl—Ru—Cl = 88.02 (2) and Cl—Ru—P = 82.77 (2), 87.65 (2)°. The bond distances of Ru—P = 2.346 (6) and Ru—Cl(avg.) = 2.412 (6) Å are within normal ranges (Allen, 2002).
Pbca (Z = 8), and reveals the typical piano-stool geometry for these complexes. The coordination sphere of the ruthenium is occupied by a benzene, benzyldiphenylphosphane and two chloride atoms (see Fig. 1). The distance between Ru and the centroid of theTo describe the steric demand of phosphane ligands the Tolman cone angle (Tolman, 1977) is still the most commonly used model. Applying this model to the geometry obtained from the title compound (and adjusting the Ru—P bond distance to 2.28 Å) we calculated an effective cone angle (Otto, 2001) of 143°. The small value for the cone angle can be ascribed to the orientation of the benzylic group of the phosphane ligand, pointing away from the metal core. This orientation is fairly rare as a CSD search shows 5 out of 28 hits with this conformation (Allen, 2002; search conducted on all transition metals with this phosphane ligand). The π interactions associated with it (see Figure 2, Table 1).
of the benzyldiphenylphosphane ligand could be linked to the number of C–H···Cl and C–H···For
studies on RuII–arene complexes, see: Chen et al. (2002); De Clercq & Verpoort (2002); Wang et al. (2011); Aydemir et al. (2011). For background to ring-opening metathesis polymerization with Ru–arene complexes, see: Stumpf et al. (1995). For background to cone angles, see: Otto (2001); Tolman (1977). For a description of the Cambridge Structural Database, see: Allen (2002).Data collection: APEX2 (Bruker, 2011); cell
SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010) and WinGX (Farrugia, 1999).Fig. 1. A view of the title complex, (I) showing the atom-numbering scheme and 50% probability displacement ellipsoids. | |
Fig. 2. Packing diagram of (I) showing the C–H···Cl and C–H···π interactions (indicated by red dashed lines). |
[RuCl2(C6H6)(C19H17P)] | F(000) = 2128 |
Mr = 526.37 | Dx = 1.57 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 5707 reflections |
a = 16.8415 (9) Å | θ = 2.2–28.1° |
b = 14.1497 (7) Å | µ = 1.03 mm−1 |
c = 18.6919 (8) Å | T = 100 K |
V = 4454.3 (4) Å3 | Plate, red |
Z = 8 | 0.09 × 0.03 × 0.01 mm |
Bruker APEX DUO 4K-CCD diffractometer | 5544 independent reflections |
Radiation source: sealed tube | 4056 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
Detector resolution: 8.4 pixels mm-1 | θmax = 28.3°, θmin = 2.2° |
φ and ω scans | h = −10→22 |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | k = −18→18 |
Tmin = 0.429, Tmax = 0.629 | l = −24→24 |
34735 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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.024P)2 + 3.1419P] where P = (Fo2 + 2Fc2)/3 |
5544 reflections | (Δ/σ)max = 0.005 |
262 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.58 e Å−3 |
[RuCl2(C6H6)(C19H17P)] | V = 4454.3 (4) Å3 |
Mr = 526.37 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 16.8415 (9) Å | µ = 1.03 mm−1 |
b = 14.1497 (7) Å | T = 100 K |
c = 18.6919 (8) Å | 0.09 × 0.03 × 0.01 mm |
Bruker APEX DUO 4K-CCD diffractometer | 5544 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 4056 reflections with I > 2σ(I) |
Tmin = 0.429, Tmax = 0.629 | Rint = 0.063 |
34735 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.44 e Å−3 |
5544 reflections | Δρmin = −0.58 e Å−3 |
262 parameters |
Experimental. The intensity data was collected on a Bruker Apex DUO 4 K CCD diffractometer using an exposure time of 40 s/frame. A total of 972 frames were collected with a frame width of 0.5° covering up to θ = 28.3° with 100% completeness accomplished. |
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 | ||
Ru1 | 0.192720 (13) | 0.729519 (13) | 1.097642 (10) | 0.01308 (6) | |
Cl1 | 0.31341 (4) | 0.65099 (4) | 1.13353 (3) | 0.01973 (14) | |
Cl2 | 0.12848 (4) | 0.57711 (4) | 1.09754 (3) | 0.01605 (13) | |
P1 | 0.22367 (4) | 0.68784 (4) | 0.97937 (3) | 0.01223 (14) | |
C1 | 0.1603 (2) | 0.86916 (17) | 1.06111 (14) | 0.0241 (7) | |
H1 | 0.1636 | 0.894 | 1.014 | 0.029* | |
C2 | 0.22515 (19) | 0.87954 (18) | 1.10820 (14) | 0.0240 (7) | |
H2 | 0.2714 | 0.9128 | 1.0935 | 0.029* | |
C3 | 0.22054 (19) | 0.84011 (18) | 1.17715 (14) | 0.0224 (6) | |
H3 | 0.2649 | 0.8444 | 1.2083 | 0.027* | |
C4 | 0.15104 (19) | 0.79438 (18) | 1.20056 (14) | 0.0232 (7) | |
H4 | 0.1474 | 0.7705 | 1.2479 | 0.028* | |
C5 | 0.08725 (19) | 0.78461 (19) | 1.15297 (15) | 0.0260 (7) | |
H5 | 0.0408 | 0.752 | 1.1679 | 0.031* | |
C6 | 0.0910 (2) | 0.82252 (19) | 1.08314 (15) | 0.0264 (7) | |
H6 | 0.0471 | 0.8165 | 1.0515 | 0.032* | |
C7 | 0.26500 (17) | 0.56772 (16) | 0.97117 (12) | 0.0151 (6) | |
H7A | 0.3014 | 0.5571 | 1.012 | 0.018* | |
H7B | 0.2208 | 0.522 | 0.9759 | 0.018* | |
C8 | 0.30938 (17) | 0.54528 (16) | 0.90309 (12) | 0.0151 (5) | |
C9 | 0.26901 (17) | 0.51027 (16) | 0.84315 (13) | 0.0169 (6) | |
H9 | 0.2131 | 0.5017 | 0.8449 | 0.02* | |
C10 | 0.31070 (19) | 0.48790 (17) | 0.78088 (13) | 0.0205 (6) | |
H10 | 0.2833 | 0.4633 | 0.7405 | 0.025* | |
C11 | 0.3918 (2) | 0.50152 (18) | 0.77798 (14) | 0.0231 (7) | |
H11 | 0.4199 | 0.4871 | 0.7353 | 0.028* | |
C12 | 0.43254 (19) | 0.53603 (19) | 0.83694 (15) | 0.0255 (7) | |
H12 | 0.4884 | 0.545 | 0.8348 | 0.031* | |
C13 | 0.39101 (18) | 0.55751 (18) | 0.89933 (14) | 0.0210 (6) | |
H13 | 0.4189 | 0.5808 | 0.9398 | 0.025* | |
C14 | 0.29770 (16) | 0.76094 (16) | 0.93506 (12) | 0.0131 (5) | |
C15 | 0.29935 (17) | 0.76972 (17) | 0.86005 (12) | 0.0169 (6) | |
H15 | 0.2587 | 0.7413 | 0.8321 | 0.02* | |
C16 | 0.35968 (17) | 0.81950 (17) | 0.82660 (13) | 0.0166 (6) | |
H16 | 0.3601 | 0.8257 | 0.776 | 0.02* | |
C17 | 0.41946 (17) | 0.86018 (17) | 0.86719 (14) | 0.0180 (6) | |
H17 | 0.4605 | 0.8949 | 0.8443 | 0.022* | |
C18 | 0.41973 (17) | 0.85044 (17) | 0.94114 (13) | 0.0173 (6) | |
H18 | 0.4615 | 0.8774 | 0.9686 | 0.021* | |
C19 | 0.35912 (17) | 0.80140 (17) | 0.97485 (13) | 0.0170 (6) | |
H19 | 0.3594 | 0.7952 | 1.0255 | 0.02* | |
C20 | 0.13550 (17) | 0.69210 (17) | 0.92313 (12) | 0.0140 (5) | |
C21 | 0.10851 (17) | 0.77773 (17) | 0.89283 (13) | 0.0168 (6) | |
H21 | 0.1402 | 0.8331 | 0.8966 | 0.02* | |
C22 | 0.03634 (18) | 0.78158 (19) | 0.85764 (13) | 0.0203 (6) | |
H22 | 0.0186 | 0.8398 | 0.8381 | 0.024* | |
C23 | −0.01037 (18) | 0.70135 (19) | 0.85061 (13) | 0.0198 (6) | |
H23 | −0.0597 | 0.7044 | 0.8261 | 0.024* | |
C24 | 0.01564 (17) | 0.61655 (18) | 0.87968 (13) | 0.0180 (6) | |
H24 | −0.0158 | 0.5612 | 0.8746 | 0.022* | |
C25 | 0.08700 (17) | 0.61219 (17) | 0.91598 (12) | 0.0154 (6) | |
H25 | 0.1035 | 0.554 | 0.9365 | 0.018* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01380 (12) | 0.01403 (9) | 0.01141 (9) | −0.00318 (9) | 0.00057 (9) | −0.00071 (7) |
Cl1 | 0.0162 (4) | 0.0272 (3) | 0.0158 (3) | −0.0018 (3) | −0.0033 (3) | 0.0008 (2) |
Cl2 | 0.0149 (4) | 0.0154 (3) | 0.0178 (3) | −0.0033 (2) | 0.0016 (3) | 0.0020 (2) |
P1 | 0.0122 (4) | 0.0123 (3) | 0.0122 (3) | −0.0016 (3) | −0.0003 (3) | 0.0001 (2) |
C1 | 0.040 (2) | 0.0133 (12) | 0.0190 (13) | 0.0028 (12) | 0.0008 (13) | −0.0013 (10) |
C2 | 0.0279 (19) | 0.0167 (12) | 0.0275 (14) | −0.0081 (12) | 0.0095 (13) | −0.0051 (10) |
C3 | 0.0247 (19) | 0.0203 (12) | 0.0221 (13) | −0.0020 (12) | −0.0030 (12) | −0.0091 (10) |
C4 | 0.031 (2) | 0.0229 (13) | 0.0159 (12) | −0.0034 (12) | 0.0079 (12) | −0.0042 (10) |
C5 | 0.0194 (18) | 0.0239 (14) | 0.0348 (15) | −0.0010 (13) | 0.0085 (13) | −0.0097 (12) |
C6 | 0.028 (2) | 0.0224 (14) | 0.0291 (15) | 0.0073 (13) | −0.0067 (13) | −0.0119 (11) |
C7 | 0.0163 (17) | 0.0157 (11) | 0.0131 (11) | 0.0017 (10) | −0.0016 (11) | 0.0004 (9) |
C8 | 0.0186 (16) | 0.0118 (10) | 0.0151 (10) | 0.0005 (11) | 0.0002 (12) | 0.0009 (9) |
C9 | 0.0155 (17) | 0.0139 (11) | 0.0212 (12) | −0.0005 (11) | −0.0021 (11) | 0.0003 (9) |
C10 | 0.0289 (19) | 0.0163 (12) | 0.0164 (11) | 0.0036 (12) | −0.0048 (13) | −0.0018 (9) |
C11 | 0.031 (2) | 0.0178 (12) | 0.0207 (13) | 0.0012 (12) | 0.0110 (13) | −0.0011 (10) |
C12 | 0.0176 (18) | 0.0255 (14) | 0.0335 (15) | −0.0042 (13) | 0.0115 (14) | −0.0064 (12) |
C13 | 0.0176 (17) | 0.0218 (13) | 0.0234 (13) | −0.0026 (11) | −0.0003 (13) | −0.0066 (11) |
C14 | 0.0121 (16) | 0.0135 (10) | 0.0137 (10) | 0.0012 (10) | −0.0003 (10) | 0.0007 (9) |
C15 | 0.0182 (17) | 0.0170 (11) | 0.0156 (11) | 0.0012 (11) | −0.0015 (11) | −0.0012 (9) |
C16 | 0.0161 (17) | 0.0188 (12) | 0.0151 (11) | 0.0038 (11) | 0.0032 (11) | 0.0040 (10) |
C17 | 0.0124 (16) | 0.0166 (12) | 0.0248 (13) | 0.0017 (11) | 0.0060 (12) | 0.0040 (10) |
C18 | 0.0132 (16) | 0.0175 (12) | 0.0211 (12) | −0.0015 (11) | −0.0037 (12) | −0.0013 (10) |
C19 | 0.0158 (17) | 0.0199 (12) | 0.0154 (11) | 0.0006 (11) | −0.0013 (11) | 0.0004 (9) |
C20 | 0.0141 (16) | 0.0168 (11) | 0.0111 (10) | −0.0025 (11) | 0.0018 (10) | −0.0023 (9) |
C21 | 0.0157 (16) | 0.0151 (11) | 0.0196 (12) | −0.0020 (11) | −0.0001 (11) | −0.0007 (10) |
C22 | 0.0184 (17) | 0.0208 (13) | 0.0216 (12) | 0.0044 (12) | −0.0030 (12) | 0.0014 (10) |
C23 | 0.0089 (16) | 0.0291 (14) | 0.0213 (13) | 0.0005 (12) | −0.0033 (11) | −0.0032 (10) |
C24 | 0.0143 (17) | 0.0211 (12) | 0.0186 (12) | −0.0035 (11) | 0.0015 (12) | −0.0035 (10) |
C25 | 0.0151 (16) | 0.0156 (11) | 0.0154 (11) | −0.0022 (11) | 0.0011 (11) | −0.0007 (9) |
Ru1—C1 | 2.161 (3) | C9—H9 | 0.95 |
Ru1—C6 | 2.177 (3) | C10—C11 | 1.380 (4) |
Ru1—C5 | 2.198 (3) | C10—H10 | 0.95 |
Ru1—C2 | 2.201 (3) | C11—C12 | 1.387 (4) |
Ru1—C3 | 2.208 (2) | C11—H11 | 0.95 |
Ru1—C4 | 2.244 (3) | C12—C13 | 1.393 (4) |
Ru1—P1 | 2.3466 (6) | C12—H12 | 0.95 |
Ru1—Cl1 | 2.4116 (7) | C13—H13 | 0.95 |
Ru1—Cl2 | 2.4127 (6) | C14—C19 | 1.397 (4) |
P1—C14 | 1.819 (3) | C14—C15 | 1.408 (3) |
P1—C20 | 1.820 (3) | C15—C16 | 1.385 (4) |
P1—C7 | 1.843 (2) | C15—H15 | 0.95 |
C1—C6 | 1.403 (4) | C16—C17 | 1.386 (4) |
C1—C2 | 1.410 (4) | C16—H16 | 0.95 |
C1—H1 | 0.95 | C17—C18 | 1.389 (3) |
C2—C3 | 1.406 (4) | C17—H17 | 0.95 |
C2—H2 | 0.95 | C18—C19 | 1.386 (4) |
C3—C4 | 1.407 (4) | C18—H18 | 0.95 |
C3—H3 | 0.95 | C19—H19 | 0.95 |
C4—C5 | 1.402 (4) | C20—C25 | 1.401 (4) |
C4—H4 | 0.95 | C20—C21 | 1.413 (3) |
C5—C6 | 1.413 (4) | C21—C22 | 1.383 (4) |
C5—H5 | 0.95 | C21—H21 | 0.95 |
C6—H6 | 0.95 | C22—C23 | 1.387 (4) |
C7—C8 | 1.510 (3) | C22—H22 | 0.95 |
C7—H7A | 0.99 | C23—C24 | 1.388 (4) |
C7—H7B | 0.99 | C23—H23 | 0.95 |
C8—C13 | 1.387 (4) | C24—C25 | 1.382 (4) |
C8—C9 | 1.401 (3) | C24—H24 | 0.95 |
C9—C10 | 1.396 (4) | C25—H25 | 0.95 |
C1—Ru1—C6 | 37.73 (11) | C4—C5—H5 | 119.5 |
C1—Ru1—C5 | 67.68 (11) | C6—C5—H5 | 119.5 |
C6—Ru1—C5 | 37.66 (10) | Ru1—C5—H5 | 129.1 |
C1—Ru1—C2 | 37.72 (11) | C1—C6—C5 | 119.1 (3) |
C6—Ru1—C2 | 67.88 (12) | C1—C6—Ru1 | 70.48 (17) |
C5—Ru1—C2 | 79.41 (11) | C5—C6—Ru1 | 71.96 (17) |
C1—Ru1—C3 | 67.56 (10) | C1—C6—H6 | 120.4 |
C6—Ru1—C3 | 79.78 (11) | C5—C6—H6 | 120.4 |
C5—Ru1—C3 | 66.65 (11) | Ru1—C6—H6 | 129.4 |
C2—Ru1—C3 | 37.20 (9) | C8—C7—P1 | 116.81 (16) |
C1—Ru1—C4 | 79.51 (10) | C8—C7—H7A | 108.1 |
C6—Ru1—C4 | 67.26 (11) | P1—C7—H7A | 108.1 |
C5—Ru1—C4 | 36.77 (11) | C8—C7—H7B | 108.1 |
C2—Ru1—C4 | 66.81 (10) | P1—C7—H7B | 108.1 |
C3—Ru1—C4 | 36.84 (10) | H7A—C7—H7B | 107.3 |
C1—Ru1—P1 | 89.32 (7) | C13—C8—C9 | 119.0 (2) |
C6—Ru1—P1 | 102.09 (7) | C13—C8—C7 | 120.5 (2) |
C5—Ru1—P1 | 135.38 (8) | C9—C8—C7 | 120.5 (3) |
C2—Ru1—P1 | 105.77 (7) | C10—C9—C8 | 120.2 (3) |
C3—Ru1—P1 | 139.90 (8) | C10—C9—H9 | 119.9 |
C4—Ru1—P1 | 168.48 (8) | C8—C9—H9 | 119.9 |
C1—Ru1—Cl1 | 136.24 (9) | C11—C10—C9 | 119.9 (2) |
C6—Ru1—Cl1 | 167.51 (7) | C11—C10—H10 | 120 |
C5—Ru1—Cl1 | 135.53 (8) | C9—C10—H10 | 120 |
C2—Ru1—Cl1 | 102.14 (9) | C10—C11—C12 | 120.5 (2) |
C3—Ru1—Cl1 | 87.73 (8) | C10—C11—H11 | 119.7 |
C4—Ru1—Cl1 | 102.33 (8) | C12—C11—H11 | 119.7 |
P1—Ru1—Cl1 | 87.65 (2) | C11—C12—C13 | 119.5 (3) |
C1—Ru1—Cl2 | 134.73 (9) | C11—C12—H12 | 120.2 |
C6—Ru1—Cl2 | 100.79 (8) | C13—C12—H12 | 120.2 |
C5—Ru1—Cl2 | 87.42 (8) | C8—C13—C12 | 120.8 (3) |
C2—Ru1—Cl2 | 166.78 (8) | C8—C13—H13 | 119.6 |
C3—Ru1—Cl2 | 136.81 (7) | C12—C13—H13 | 119.6 |
C4—Ru1—Cl2 | 103.06 (7) | C19—C14—C15 | 118.6 (2) |
P1—Ru1—Cl2 | 82.77 (2) | C19—C14—P1 | 119.88 (18) |
Cl1—Ru1—Cl2 | 88.07 (2) | C15—C14—P1 | 121.1 (2) |
C14—P1—C20 | 106.10 (11) | C16—C15—C14 | 120.6 (3) |
C14—P1—C7 | 103.15 (12) | C16—C15—H15 | 119.7 |
C20—P1—C7 | 106.90 (12) | C14—C15—H15 | 119.7 |
C14—P1—Ru1 | 115.99 (8) | C15—C16—C17 | 119.8 (2) |
C20—P1—Ru1 | 110.77 (8) | C15—C16—H16 | 120.1 |
C7—P1—Ru1 | 113.20 (8) | C17—C16—H16 | 120.1 |
C6—C1—C2 | 120.7 (3) | C16—C17—C18 | 120.4 (3) |
C6—C1—Ru1 | 71.78 (16) | C16—C17—H17 | 119.8 |
C2—C1—Ru1 | 72.68 (15) | C18—C17—H17 | 119.8 |
C6—C1—H1 | 119.7 | C19—C18—C17 | 120.0 (3) |
C2—C1—H1 | 119.7 | C19—C18—H18 | 120 |
Ru1—C1—H1 | 128.1 | C17—C18—H18 | 120 |
C3—C2—C1 | 119.2 (3) | C18—C19—C14 | 120.6 (2) |
C3—C2—Ru1 | 71.69 (15) | C18—C19—H19 | 119.7 |
C1—C2—Ru1 | 69.60 (15) | C14—C19—H19 | 119.7 |
C3—C2—H2 | 120.4 | C25—C20—C21 | 117.8 (2) |
C1—C2—H2 | 120.4 | C25—C20—P1 | 120.25 (19) |
Ru1—C2—H2 | 130.9 | C21—C20—P1 | 121.50 (19) |
C2—C3—C4 | 120.9 (3) | C22—C21—C20 | 120.5 (2) |
C2—C3—Ru1 | 71.11 (15) | C22—C21—H21 | 119.8 |
C4—C3—Ru1 | 72.96 (15) | C20—C21—H21 | 119.8 |
C2—C3—H3 | 119.6 | C21—C22—C23 | 120.7 (2) |
C4—C3—H3 | 119.6 | C21—C22—H22 | 119.6 |
Ru1—C3—H3 | 128.7 | C23—C22—H22 | 119.6 |
C5—C4—C3 | 119.0 (3) | C22—C23—C24 | 119.4 (3) |
C5—C4—Ru1 | 69.83 (15) | C22—C23—H23 | 120.3 |
C3—C4—Ru1 | 70.20 (14) | C24—C23—H23 | 120.3 |
C5—C4—H4 | 120.5 | C25—C24—C23 | 120.4 (2) |
C3—C4—H4 | 120.5 | C25—C24—H24 | 119.8 |
Ru1—C4—H4 | 132.4 | C23—C24—H24 | 119.8 |
C4—C5—C6 | 121.0 (3) | C24—C25—C20 | 121.2 (2) |
C4—C5—Ru1 | 73.40 (18) | C24—C25—H25 | 119.4 |
C6—C5—Ru1 | 70.37 (17) | C20—C25—H25 | 119.4 |
C1—Ru1—P1—C14 | 57.32 (13) | C5—Ru1—C4—C3 | −133.0 (3) |
C6—Ru1—P1—C14 | 93.09 (12) | C2—Ru1—C4—C3 | −29.14 (17) |
C5—Ru1—P1—C14 | 113.77 (14) | P1—Ru1—C4—C3 | −80.7 (5) |
C2—Ru1—P1—C14 | 22.94 (13) | Cl1—Ru1—C4—C3 | 68.93 (17) |
C3—Ru1—P1—C14 | 4.66 (16) | Cl2—Ru1—C4—C3 | 159.82 (16) |
C4—Ru1—P1—C14 | 71.4 (4) | C3—C4—C5—C6 | −2.1 (4) |
Cl1—Ru1—P1—C14 | −79.02 (9) | Ru1—C4—C5—C6 | −54.0 (2) |
Cl2—Ru1—P1—C14 | −167.37 (10) | C3—C4—C5—Ru1 | 51.9 (2) |
C1—Ru1—P1—C20 | −63.67 (12) | C1—Ru1—C5—C4 | −102.74 (18) |
C6—Ru1—P1—C20 | −27.90 (12) | C6—Ru1—C5—C4 | −132.6 (2) |
C5—Ru1—P1—C20 | −7.22 (14) | C2—Ru1—C5—C4 | −65.22 (17) |
C2—Ru1—P1—C20 | −98.05 (12) | C3—Ru1—C5—C4 | −28.53 (16) |
C3—Ru1—P1—C20 | −116.32 (15) | P1—Ru1—C5—C4 | −167.01 (12) |
C4—Ru1—P1—C20 | −49.6 (4) | Cl1—Ru1—C5—C4 | 31.4 (2) |
Cl1—Ru1—P1—C20 | 160.00 (9) | Cl2—Ru1—C5—C4 | 115.99 (15) |
Cl2—Ru1—P1—C20 | 71.65 (9) | C1—Ru1—C5—C6 | 29.85 (16) |
C1—Ru1—P1—C7 | 176.28 (13) | C2—Ru1—C5—C6 | 67.37 (17) |
C6—Ru1—P1—C7 | −147.95 (13) | C3—Ru1—C5—C6 | 104.06 (18) |
C5—Ru1—P1—C7 | −127.27 (15) | C4—Ru1—C5—C6 | 132.6 (2) |
C2—Ru1—P1—C7 | 141.91 (13) | P1—Ru1—C5—C6 | −34.4 (2) |
C3—Ru1—P1—C7 | 123.63 (16) | Cl1—Ru1—C5—C6 | 163.98 (13) |
C4—Ru1—P1—C7 | −169.6 (4) | Cl2—Ru1—C5—C6 | −111.41 (16) |
Cl1—Ru1—P1—C7 | 39.95 (10) | C2—C1—C6—C5 | −1.0 (4) |
Cl2—Ru1—P1—C7 | −48.40 (10) | Ru1—C1—C6—C5 | 55.0 (2) |
C5—Ru1—C1—C6 | −29.80 (15) | C2—C1—C6—Ru1 | −56.0 (2) |
C2—Ru1—C1—C6 | −131.7 (2) | C4—C5—C6—C1 | 1.1 (4) |
C3—Ru1—C1—C6 | −102.70 (17) | Ru1—C5—C6—C1 | −54.3 (2) |
C4—Ru1—C1—C6 | −66.23 (16) | C4—C5—C6—Ru1 | 55.4 (2) |
P1—Ru1—C1—C6 | 110.94 (15) | C5—Ru1—C6—C1 | 131.2 (2) |
Cl1—Ru1—C1—C6 | −163.16 (12) | C2—Ru1—C6—C1 | 29.54 (15) |
Cl2—Ru1—C1—C6 | 31.82 (19) | C3—Ru1—C6—C1 | 66.38 (16) |
C6—Ru1—C1—C2 | 131.7 (2) | C4—Ru1—C6—C1 | 102.65 (17) |
C5—Ru1—C1—C2 | 101.90 (18) | P1—Ru1—C6—C1 | −72.76 (15) |
C3—Ru1—C1—C2 | 29.00 (16) | Cl1—Ru1—C6—C1 | 67.9 (4) |
C4—Ru1—C1—C2 | 65.47 (17) | Cl2—Ru1—C6—C1 | −157.58 (14) |
P1—Ru1—C1—C2 | −117.36 (16) | C1—Ru1—C6—C5 | −131.2 (2) |
Cl1—Ru1—C1—C2 | −31.5 (2) | C2—Ru1—C6—C5 | −101.65 (18) |
Cl2—Ru1—C1—C2 | 163.52 (13) | C3—Ru1—C6—C5 | −64.82 (17) |
C6—C1—C2—C3 | 1.8 (4) | C4—Ru1—C6—C5 | −28.54 (16) |
Ru1—C1—C2—C3 | −53.7 (2) | P1—Ru1—C6—C5 | 156.05 (15) |
C6—C1—C2—Ru1 | 55.5 (2) | Cl1—Ru1—C6—C5 | −63.3 (5) |
C1—Ru1—C2—C3 | 132.2 (3) | Cl2—Ru1—C6—C5 | 71.22 (16) |
C6—Ru1—C2—C3 | 102.62 (19) | C14—P1—C7—C8 | −35.7 (2) |
C5—Ru1—C2—C3 | 65.12 (19) | C20—P1—C7—C8 | 76.0 (2) |
C4—Ru1—C2—C3 | 28.88 (18) | Ru1—P1—C7—C8 | −161.80 (17) |
P1—Ru1—C2—C3 | −160.48 (16) | P1—C7—C8—C13 | 92.6 (3) |
Cl1—Ru1—C2—C3 | −69.50 (18) | P1—C7—C8—C9 | −88.5 (3) |
Cl2—Ru1—C2—C3 | 70.4 (4) | C13—C8—C9—C10 | 0.2 (3) |
C6—Ru1—C2—C1 | −29.55 (17) | C7—C8—C9—C10 | −178.7 (2) |
C5—Ru1—C2—C1 | −67.05 (18) | C8—C9—C10—C11 | −0.9 (4) |
C3—Ru1—C2—C1 | −132.2 (3) | C9—C10—C11—C12 | 1.0 (4) |
C4—Ru1—C2—C1 | −103.30 (19) | C10—C11—C12—C13 | −0.4 (4) |
P1—Ru1—C2—C1 | 67.34 (17) | C9—C8—C13—C12 | 0.4 (4) |
Cl1—Ru1—C2—C1 | 158.33 (16) | C7—C8—C13—C12 | 179.3 (2) |
Cl2—Ru1—C2—C1 | −61.8 (4) | C11—C12—C13—C8 | −0.3 (4) |
C1—C2—C3—C4 | −2.8 (4) | C20—P1—C14—C19 | 155.8 (2) |
Ru1—C2—C3—C4 | −55.6 (2) | C7—P1—C14—C19 | −92.0 (2) |
C1—C2—C3—Ru1 | 52.7 (2) | Ru1—P1—C14—C19 | 32.4 (2) |
C1—Ru1—C3—C2 | −29.38 (19) | C20—P1—C14—C15 | −30.9 (2) |
C6—Ru1—C3—C2 | −66.73 (19) | C7—P1—C14—C15 | 81.3 (2) |
C5—Ru1—C3—C2 | −103.8 (2) | Ru1—P1—C14—C15 | −154.40 (18) |
C4—Ru1—C3—C2 | −132.2 (3) | C19—C14—C15—C16 | −1.6 (4) |
P1—Ru1—C3—C2 | 29.9 (2) | P1—C14—C15—C16 | −174.9 (2) |
Cl1—Ru1—C3—C2 | 113.59 (18) | C14—C15—C16—C17 | 0.7 (4) |
Cl2—Ru1—C3—C2 | −161.65 (15) | C15—C16—C17—C18 | 0.7 (4) |
C1—Ru1—C3—C4 | 102.9 (2) | C16—C17—C18—C19 | −1.3 (4) |
C6—Ru1—C3—C4 | 65.51 (18) | C17—C18—C19—C14 | 0.4 (4) |
C5—Ru1—C3—C4 | 28.48 (17) | C15—C14—C19—C18 | 1.0 (4) |
C2—Ru1—C3—C4 | 132.2 (3) | P1—C14—C19—C18 | 174.4 (2) |
P1—Ru1—C3—C4 | 162.18 (13) | C14—P1—C20—C25 | 144.4 (2) |
Cl1—Ru1—C3—C4 | −114.17 (17) | C7—P1—C20—C25 | 34.8 (2) |
Cl2—Ru1—C3—C4 | −29.4 (2) | Ru1—P1—C20—C25 | −88.9 (2) |
C2—C3—C4—C5 | 3.0 (4) | C14—P1—C20—C21 | −43.5 (2) |
Ru1—C3—C4—C5 | −51.8 (2) | C7—P1—C20—C21 | −153.1 (2) |
C2—C3—C4—Ru1 | 54.7 (2) | Ru1—P1—C20—C21 | 83.2 (2) |
C1—Ru1—C4—C5 | 66.59 (18) | C25—C20—C21—C22 | 0.2 (4) |
C6—Ru1—C4—C5 | 29.19 (17) | P1—C20—C21—C22 | −172.1 (2) |
C2—Ru1—C4—C5 | 103.85 (19) | C20—C21—C22—C23 | −0.9 (4) |
C3—Ru1—C4—C5 | 133.0 (3) | C21—C22—C23—C24 | 0.4 (4) |
P1—Ru1—C4—C5 | 52.3 (5) | C22—C23—C24—C25 | 0.7 (4) |
Cl1—Ru1—C4—C5 | −158.07 (15) | C23—C24—C25—C20 | −1.3 (4) |
Cl2—Ru1—C4—C5 | −67.19 (16) | C21—C20—C25—C24 | 0.9 (4) |
C1—Ru1—C4—C3 | −66.41 (18) | P1—C20—C25—C24 | 173.2 (2) |
C6—Ru1—C4—C3 | −103.80 (19) |
Cg1 and Cg2 are the centroids of the C8–C13 and C20–C25 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···Cl2i | 0.95 | 2.85 | 3.568 (3) | 133 |
C16—H16···Cl1ii | 0.95 | 2.8 | 3.716 (3) | 163 |
C2—H2···Cl2iii | 0.95 | 2.87 | 3.733 (3) | 151 |
C24—H24···Cl2iv | 0.95 | 2.78 | 3.685 (3) | 161 |
C21—H21···Cg1v | 0.95 | 2.89 | 3.673 (3) | 140 |
C4—H4···Cg2vi | 0.95 | 3.00 | 3.789 (3) | 141 |
Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+1/2, y+1/2, z; (iv) −x, −y+1, −z+2; (v) x, −y−3/2, z−1/2; (vi) x−1/2, y, −z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [RuCl2(C6H6)(C19H17P)] |
Mr | 526.37 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 100 |
a, b, c (Å) | 16.8415 (9), 14.1497 (7), 18.6919 (8) |
V (Å3) | 4454.3 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.03 |
Crystal size (mm) | 0.09 × 0.03 × 0.01 |
Data collection | |
Diffractometer | Bruker APEX DUO 4K-CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.429, 0.629 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34735, 5544, 4056 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.069, 1.01 |
No. of reflections | 5544 |
No. of parameters | 262 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.58 |
Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2008), SAINT and XPREP (Bruker, 2008), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), publCIF (Westrip, 2010) and WinGX (Farrugia, 1999).
Cg1 and Cg2 are the centroids of the C8–C13 and C20–C25 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···Cl2i | 0.95 | 2.85 | 3.568 (3) | 133.2 |
C16—H16···Cl1ii | 0.95 | 2.8 | 3.716 (3) | 163.2 |
C2—H2···Cl2iii | 0.95 | 2.87 | 3.733 (3) | 150.9 |
C24—H24···Cl2iv | 0.95 | 2.78 | 3.685 (3) | 160.7 |
C21—H21···Cg1v | 0.95 | 2.89 | 3.673 (3) | 140 |
C4—H4···Cg2vi | 0.95 | 3.00 | 3.789 (3) | 141 |
Symmetry codes: (i) −x+1/2, −y+1, z−1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+1/2, y+1/2, z; (iv) −x, −y+1, −z+2; (v) x, −y−3/2, z−1/2; (vi) x−1/2, y, −z−1/2. |
Acknowledgements
Financial assistance from the Research Fund of the University of Johannesburg is gratefully acknowledged.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The activity of the half-sandwich Ru(II)-arene complexes are well known in the catalytic transfer hydrogenation of carbonyl compounds (Chen et al., 2002; De Clercq & Verpoort, 2002; Wang et al., 2011; Aydemir et al., 2011) and for ring-opening metathesis polymerization (Stumpf et al., 1995). Reported here is the η6-Ru compound containing benzyldiphenylphosphane as part of our ongoing investigation into these type of complexes.
Molecules of the title compound packs in the orthorhombic space group Pbca (Z = 8), and reveals the typical piano-stool geometry for these complexes. The coordination sphere of the ruthenium is occupied by a benzene, benzyldiphenylphosphane and two chloride atoms (see Fig. 1). The distance between Ru and the centroid of the π-bonded η6-benzene ligand is 1.6894 (11) Å and the mean Ru—C bond distance is 2.198 (3) Å. The coordination of the remaining ligands to the Ru atom shows deviation from the typical octahedral geometry with Cl—Ru—Cl = 88.02 (2) and Cl—Ru—P = 82.77 (2), 87.65 (2)°. The bond distances of Ru—P = 2.346 (6) and Ru—Cl(avg.) = 2.412 (6) Å are within normal ranges (Allen, 2002).
To describe the steric demand of phosphane ligands the Tolman cone angle (Tolman, 1977) is still the most commonly used model. Applying this model to the geometry obtained from the title compound (and adjusting the Ru—P bond distance to 2.28 Å) we calculated an effective cone angle (Otto, 2001) of 143°. The small value for the cone angle can be ascribed to the orientation of the benzylic group of the phosphane ligand, pointing away from the metal core. This orientation is fairly rare as a CSD search shows 5 out of 28 hits with this conformation (Allen, 2002; search conducted on all transition metals with this phosphane ligand). The preferred orientation of the benzyldiphenylphosphane ligand could be linked to the number of C–H···Cl and C–H···π interactions associated with it (see Figure 2, Table 1).