supplementary materials


hy2625 scheme

Acta Cryst. (2013). E69, m340    [ doi:10.1107/S1600536813014128 ]

Tris(acetonitrile-[kappa]N)dichlorido(triphenylphosphane-[kappa]P)ruthenium(II) acetonitrile monosolvate

X.-F. Yin, Y. Qin, H.-T. Shi, Q. Chen and Q.-F. Zhang

Abstract top

In the title complex, [RuCl2(CH3CN)3(C18H15P)]·CH3CN, the coordination geometry of the RuII atom is distorted octahedral, defined by one P atom from a triphenylphosphane ligand, three N atoms from three acetonitrile ligands and two Cl atoms. The three acetronitile ligands linearly bind to the RuII atom, with Ru-N-C angles of 172.6 (2), 179.9 (2) and 171.4 (2)°.

Comment top

The structural and reactivity studies of coordinatively unsaturated ruthenium complexes have received much attention due to their versatile and diverse applications in organic transformation (Jansen et al., 2000; Trost et al., 2001). Since Stephenson & Wilkinson (1966) reported [RuCl2(PPh3)3], it has been found that such five-coordinated ruthenium(II) complex readily loses one triphenylphosphane ligand in solution to give a six-coordinated ruthenium(II) complex with a [Ru(PPh3)2] moiety (Caulton, 1974). For example, two isomers of [RuCl2(CH3CN)2(PPh3)2] were easily obtained upon refluxing [RuCl2(PPh3)3] in a mixed solution with acetonitrile as both co-solvent and ligand (Al-Far & Slaughter, 2008; Gilbert & Wilkinson, 1969), which were firstly characterized by infrared spectroscopy (Hallman et al., 1970) and later confirmed by X-ray crystallography (Al-Far & Slaughter, 2008). We found that a similar reaction of [RuCl2(PPh3)3] in the presence of equal equivalent of hydrogen peroxide resulted in loss of two triphenylphosphane ligands and coordination of three acetonitrile ligands. In this paper, we report the synthesis and crystal structure of a new ruthenium(II) complex [RuCl2(CH3CN)3(PPh3)].CH3CN with a [Ru(PPh3)] species.

In the title complex, the coordination geometry of the RuII atom is a distorted octahedral with one triphenylphosphane, three acetonitriles and two chlorides (Fig. 1). The average Ru—N bond distance value, 2.014 (2) Å, is similar to that found in cis-[RuCl2(CH3CN)2(PPh3)2] [av. 2.010 (2) Å] (Al-Far & Slaughter, 2008). The Ru—N bond distance of the CH3CN ligand trans to the chloride ligand is not extended (Jansen et al., 2000; Naskar & Bhattacharjee, 2005). Three CH3CN ligands are coordinated linearly to the RuII atom with average Ru—N—C and N—C—C angles of 174.6 (2)° and 177.3 (2)°, respectively. Average Ru—Cl bond distance [2.4542 (6) Å] is as expected (Al-Far & Slaughter, 2008; Jansen et al., 2000). The Ru—P bond length of 2.2754 (6) Å in the title complex is slightly shorter than those of 2.3688 (7) and 2.3887 (7) Å in the complex cis-[RuCl2(CH3CN)2(PPh3)2]. It is interesting to note that the Ru1—Cl2 bond [2.5007 (6) Å] trans to the PPh3 ligand is ca. 0.1 Å longer than the Ru1—Cl1 bond [2.4080 (6)Å] trans to the CH3CN ligand. The elongation of the Ru—Cl bond trans to the phosphane ligand is probably due to a relatively strong σ back-bonding from phosphrous to ruthenium.

Related literature top

For background to ruthenium complexes, see: Caulton (1974); Gilbert & Wilkinson (1969); Hallman et al. (1970); Jansen et al. (2000); Stephenson & Wilkinson (1966); Trost et al. (2001). For related structures, see: Al-Far & Slaughter (2008); Naskar & Bhattacharjee (2005).

Experimental top

[RuCl2(PPh3)3] (191 mg, 0.2 mmol) was dissolved in a freshly distilled CH3CN (10 ml), with stirring at room temperature for 30 min. During this time, the color of the solution was changed from dark brown to orange. Hydrogen peroxide (30%, 6.8 ml, 0.2 mmol) was added to the solution and then the reaction mixture was stirred at reflux for 15 min, developing a yellow. The solvent was evaporated in vacuo and the yellow residue was washed with diethyl ether. Recrystallization from CH3CN/Et2O afforded yellow crystals of the title complex within five days. Yield: 127 mg, 69% (based on Ru). Analysis, calculated for C26H27Cl2N4PRu: C 52.18, H 4.55, N 9.36%; found C 52.13, H 4.51, N 9.39%.

Refinement top

H atoms were placed in geometrically idealized positions and refined as riding atoms, with C—H = 0.93 (aromatic) and 0.96 (methyl) Å and with Uiso(H) = 1.2(1.5 for methyl)Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
Tris(acetonitrile-κN)dichlorido(triphenylphosphane-κP)ruthenium(II) acetonitrile monosolvate top
Crystal data top
[RuCl2(C2H3N)3(C18H15P)]·C2H3NF(000) = 1216
Mr = 598.46Dx = 1.439 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7259 reflections
a = 15.1133 (13) Åθ = 2.4–29.4°
b = 13.9144 (12) ŵ = 0.84 mm1
c = 13.3121 (12) ÅT = 296 K
β = 99.275 (2)°Block, yellow
V = 2762.8 (4) Å30.15 × 0.13 × 0.10 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
5403 independent reflections
Radiation source: fine-focus sealed tube4544 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
φ and ω scansθmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1816
Tmin = 0.884, Tmax = 0.921k = 1717
16271 measured reflectionsl = 1615
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.063H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0223P)2 + 1.1432P]
where P = (Fo2 + 2Fc2)/3
5403 reflections(Δ/σ)max = 0.001
311 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
[RuCl2(C2H3N)3(C18H15P)]·C2H3NV = 2762.8 (4) Å3
Mr = 598.46Z = 4
Monoclinic, P21/cMo Kα radiation
a = 15.1133 (13) ŵ = 0.84 mm1
b = 13.9144 (12) ÅT = 296 K
c = 13.3121 (12) Å0.15 × 0.13 × 0.10 mm
β = 99.275 (2)°
Data collection top
Bruker APEXII CCD
diffractometer
5403 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
4544 reflections with I > 2σ(I)
Tmin = 0.884, Tmax = 0.921Rint = 0.031
16271 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.063Δρmax = 0.33 e Å3
S = 1.04Δρmin = 0.33 e Å3
5403 reflectionsAbsolute structure: ?
311 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Ru10.392694 (11)0.357317 (12)0.697216 (12)0.02730 (6)
Cl10.34706 (4)0.31895 (4)0.52005 (4)0.04156 (14)
Cl20.55085 (4)0.30921 (4)0.68935 (5)0.04180 (14)
P10.25036 (4)0.40373 (4)0.70896 (4)0.03124 (13)
N10.42461 (13)0.49189 (14)0.65831 (14)0.0346 (4)
N20.36584 (12)0.22009 (13)0.72988 (14)0.0329 (4)
N30.43047 (12)0.37894 (12)0.84685 (14)0.0309 (4)
N40.0609 (3)0.6282 (3)0.1682 (4)0.1235 (15)
C10.43654 (16)0.56570 (17)0.62675 (17)0.0371 (5)
C20.4461 (2)0.66014 (18)0.5837 (2)0.0536 (7)
H2A0.39510.67330.53250.080*
H2B0.49970.66200.55360.080*
H2C0.44980.70770.63640.080*
C30.35075 (16)0.14273 (17)0.74815 (18)0.0380 (5)
C40.3303 (2)0.04378 (19)0.7712 (2)0.0600 (8)
H4A0.32350.03880.84150.090*
H4B0.37820.00270.75840.090*
H4C0.27550.02450.72900.090*
C50.44268 (16)0.38452 (16)0.93285 (18)0.0361 (5)
C60.4521 (2)0.3943 (2)1.04268 (18)0.0560 (8)
H6A0.39520.41081.06110.084*
H6B0.49480.44391.06520.084*
H6C0.47250.33461.07430.084*
C70.1151 (3)0.6798 (3)0.1963 (3)0.0899 (12)
C80.1863 (4)0.7457 (3)0.2315 (4)0.1292 (19)
H8A0.24040.71040.25470.194*
H8B0.17070.78320.28660.194*
H8C0.19560.78750.17680.194*
C110.17380 (15)0.30216 (17)0.70816 (19)0.0391 (5)
C120.12238 (18)0.27311 (19)0.6177 (2)0.0520 (7)
H120.12140.30980.55910.062*
C130.0722 (2)0.1892 (2)0.6144 (3)0.0728 (10)
H130.03760.16990.55360.087*
C140.0735 (2)0.1349 (2)0.7002 (4)0.0794 (11)
H140.03890.07940.69780.095*
C150.1253 (2)0.1616 (2)0.7894 (3)0.0686 (10)
H150.12670.12370.84720.082*
C160.17586 (18)0.2451 (2)0.7941 (2)0.0516 (7)
H160.21130.26290.85500.062*
C210.23964 (16)0.47418 (18)0.82343 (18)0.0399 (6)
C220.1735 (2)0.4603 (2)0.8828 (2)0.0654 (9)
H220.13230.41060.86820.078*
C230.1694 (3)0.5217 (3)0.9650 (3)0.0909 (13)
H230.12500.51271.00500.109*
C240.2298 (3)0.5948 (3)0.9876 (3)0.0882 (12)
H240.22710.63431.04340.106*
C250.2941 (2)0.6099 (2)0.9282 (2)0.0675 (9)
H250.33460.66030.94270.081*
C260.29900 (18)0.55016 (19)0.8468 (2)0.0483 (6)
H260.34300.56090.80660.058*
C310.19006 (16)0.48562 (16)0.61322 (18)0.0374 (5)
C320.22665 (18)0.51600 (19)0.53028 (19)0.0466 (6)
H320.28190.49200.51980.056*
C330.1818 (2)0.5820 (2)0.4623 (2)0.0635 (8)
H330.20710.60150.40640.076*
C340.1014 (2)0.6185 (2)0.4766 (3)0.0709 (9)
H340.07210.66350.43140.085*
C350.0644 (2)0.5885 (3)0.5579 (3)0.0785 (11)
H350.00900.61280.56750.094*
C360.10779 (19)0.5228 (2)0.6261 (2)0.0609 (8)
H360.08150.50320.68130.073*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.03176 (10)0.02563 (10)0.02496 (10)0.00084 (7)0.00587 (7)0.00132 (7)
Cl10.0517 (4)0.0445 (3)0.0275 (3)0.0104 (3)0.0035 (2)0.0018 (2)
Cl20.0371 (3)0.0440 (3)0.0454 (3)0.0047 (3)0.0098 (3)0.0021 (3)
P10.0319 (3)0.0319 (3)0.0300 (3)0.0012 (2)0.0053 (2)0.0004 (2)
N10.0382 (11)0.0327 (11)0.0341 (10)0.0009 (8)0.0092 (8)0.0015 (9)
N20.0377 (11)0.0326 (11)0.0291 (10)0.0022 (8)0.0074 (8)0.0001 (8)
N30.0336 (10)0.0278 (10)0.0306 (10)0.0005 (8)0.0037 (8)0.0012 (8)
N40.119 (3)0.112 (3)0.143 (4)0.016 (3)0.032 (3)0.026 (3)
C10.0415 (13)0.0381 (13)0.0330 (12)0.0016 (11)0.0098 (10)0.0002 (11)
C20.0728 (19)0.0377 (14)0.0508 (16)0.0087 (13)0.0116 (14)0.0101 (12)
C30.0416 (13)0.0354 (13)0.0379 (13)0.0009 (11)0.0090 (10)0.0009 (11)
C40.072 (2)0.0343 (14)0.076 (2)0.0049 (14)0.0177 (16)0.0093 (14)
C50.0438 (14)0.0269 (11)0.0365 (14)0.0040 (10)0.0029 (10)0.0004 (10)
C60.091 (2)0.0459 (15)0.0293 (13)0.0197 (15)0.0056 (13)0.0005 (12)
C70.123 (4)0.072 (3)0.076 (3)0.001 (3)0.019 (3)0.005 (2)
C80.182 (5)0.092 (3)0.104 (4)0.038 (4)0.009 (3)0.002 (3)
C110.0309 (12)0.0373 (13)0.0499 (14)0.0019 (10)0.0092 (10)0.0027 (11)
C120.0465 (15)0.0428 (15)0.0629 (18)0.0015 (12)0.0027 (13)0.0038 (13)
C130.0510 (18)0.0516 (18)0.109 (3)0.0075 (15)0.0077 (18)0.020 (2)
C140.055 (2)0.0468 (18)0.141 (4)0.0130 (16)0.031 (2)0.000 (2)
C150.060 (2)0.0530 (18)0.101 (3)0.0012 (15)0.038 (2)0.0203 (18)
C160.0469 (16)0.0522 (16)0.0596 (17)0.0006 (13)0.0198 (13)0.0093 (14)
C210.0419 (14)0.0425 (14)0.0364 (13)0.0090 (11)0.0097 (10)0.0020 (11)
C220.072 (2)0.068 (2)0.0646 (19)0.0030 (17)0.0352 (17)0.0113 (16)
C230.119 (3)0.095 (3)0.075 (2)0.002 (3)0.065 (2)0.021 (2)
C240.121 (3)0.081 (3)0.070 (2)0.001 (2)0.039 (2)0.033 (2)
C250.081 (2)0.0577 (18)0.065 (2)0.0018 (17)0.0141 (17)0.0229 (16)
C260.0512 (16)0.0458 (15)0.0493 (15)0.0056 (12)0.0127 (12)0.0085 (12)
C310.0378 (13)0.0335 (12)0.0387 (13)0.0056 (10)0.0003 (10)0.0023 (10)
C320.0465 (15)0.0497 (15)0.0435 (14)0.0150 (12)0.0067 (11)0.0074 (12)
C330.073 (2)0.069 (2)0.0502 (17)0.0246 (17)0.0128 (15)0.0207 (15)
C340.069 (2)0.072 (2)0.069 (2)0.0335 (17)0.0036 (17)0.0239 (17)
C350.0556 (19)0.097 (3)0.084 (2)0.0408 (19)0.0133 (17)0.023 (2)
C360.0456 (16)0.074 (2)0.0648 (19)0.0170 (15)0.0137 (14)0.0158 (16)
Geometric parameters (Å, º) top
Ru1—N12.0218 (19)C12—C131.389 (4)
Ru1—N22.0141 (19)C12—H120.9300
Ru1—N32.0044 (18)C13—C141.367 (5)
Ru1—P12.2754 (6)C13—H130.9300
Ru1—Cl12.4080 (6)C14—C151.365 (5)
Ru1—Cl22.5007 (6)C14—H140.9300
P1—C111.825 (2)C15—C161.386 (4)
P1—C311.838 (2)C15—H150.9300
P1—C211.841 (2)C16—H160.9300
N1—C11.135 (3)C21—C221.384 (3)
N2—C31.135 (3)C21—C261.389 (4)
N3—C51.133 (3)C22—C231.398 (4)
N4—C71.108 (5)C22—H220.9300
C1—C21.450 (3)C23—C241.368 (5)
C2—H2A0.9600C23—H230.9300
C2—H2B0.9600C24—C251.363 (5)
C2—H2C0.9600C24—H240.9300
C3—C41.455 (3)C25—C261.377 (4)
C4—H4A0.9600C25—H250.9300
C4—H4B0.9600C26—H260.9300
C4—H4C0.9600C31—C321.379 (3)
C5—C61.452 (3)C31—C361.383 (4)
C6—H6A0.9600C32—C331.387 (4)
C6—H6B0.9600C32—H320.9300
C6—H6C0.9600C33—C341.358 (4)
C7—C81.434 (6)C33—H330.9300
C8—H8A0.9600C34—C351.361 (5)
C8—H8B0.9600C34—H340.9300
C8—H8C0.9600C35—C361.379 (4)
C11—C121.384 (4)C35—H350.9300
C11—C161.389 (4)C36—H360.9300
N3—Ru1—N287.87 (7)C12—C11—P1119.8 (2)
N3—Ru1—N194.25 (7)C16—C11—P1120.5 (2)
N2—Ru1—N1176.40 (7)C11—C12—C13120.0 (3)
N3—Ru1—P190.58 (5)C11—C12—H12120.0
N2—Ru1—P191.64 (5)C13—C12—H12120.0
N1—Ru1—P191.26 (5)C14—C13—C12120.3 (3)
N3—Ru1—Cl1175.81 (5)C14—C13—H13119.9
N2—Ru1—Cl188.02 (5)C12—C13—H13119.9
N1—Ru1—Cl189.82 (6)C15—C14—C13120.3 (3)
P1—Ru1—Cl190.31 (2)C15—C14—H14119.8
N3—Ru1—Cl287.75 (5)C13—C14—H14119.8
N2—Ru1—Cl289.00 (5)C14—C15—C16120.2 (3)
N1—Ru1—Cl288.17 (5)C14—C15—H15119.9
P1—Ru1—Cl2178.19 (2)C16—C15—H15119.9
Cl1—Ru1—Cl291.40 (2)C15—C16—C11120.2 (3)
C11—P1—C31103.47 (11)C15—C16—H16119.9
C11—P1—C21106.07 (11)C11—C16—H16119.9
C31—P1—C2198.27 (11)C22—C21—C26118.6 (2)
C11—P1—Ru1112.66 (8)C22—C21—P1124.5 (2)
C31—P1—Ru1119.79 (8)C26—C21—P1116.80 (18)
C21—P1—Ru1114.73 (8)C21—C22—C23119.3 (3)
C1—N1—Ru1172.6 (2)C21—C22—H22120.4
C3—N2—Ru1179.9 (2)C23—C22—H22120.4
C5—N3—Ru1171.40 (18)C24—C23—C22120.9 (3)
N1—C1—C2176.5 (3)C24—C23—H23119.5
C1—C2—H2A109.5C22—C23—H23119.5
C1—C2—H2B109.5C25—C24—C23120.0 (3)
H2A—C2—H2B109.5C25—C24—H24120.0
C1—C2—H2C109.5C23—C24—H24120.0
H2A—C2—H2C109.5C24—C25—C26119.8 (3)
H2B—C2—H2C109.5C24—C25—H25120.1
N2—C3—C4179.3 (3)C26—C25—H25120.1
C3—C4—H4A109.5C25—C26—C21121.4 (3)
C3—C4—H4B109.5C25—C26—H26119.3
H4A—C4—H4B109.5C21—C26—H26119.3
C3—C4—H4C109.5C32—C31—C36118.0 (2)
H4A—C4—H4C109.5C32—C31—P1121.83 (18)
H4B—C4—H4C109.5C36—C31—P1120.1 (2)
N3—C5—C6176.0 (3)C31—C32—C33120.6 (2)
C5—C6—H6A109.5C31—C32—H32119.7
C5—C6—H6B109.5C33—C32—H32119.7
H6A—C6—H6B109.5C34—C33—C32120.7 (3)
C5—C6—H6C109.5C34—C33—H33119.7
H6A—C6—H6C109.5C32—C33—H33119.7
H6B—C6—H6C109.5C33—C34—C35119.2 (3)
N4—C7—C8178.9 (6)C33—C34—H34120.4
C7—C8—H8A109.5C35—C34—H34120.4
C7—C8—H8B109.5C34—C35—C36120.9 (3)
H8A—C8—H8B109.5C34—C35—H35119.5
C7—C8—H8C109.5C36—C35—H35119.5
H8A—C8—H8C109.5C35—C36—C31120.5 (3)
H8B—C8—H8C109.5C35—C36—H36119.7
C12—C11—C16119.0 (2)C31—C36—H36119.7
Selected bond lengths (Å) top
Ru1—N12.0218 (19)Ru1—P12.2754 (6)
Ru1—N22.0141 (19)Ru1—Cl12.4080 (6)
Ru1—N32.0044 (18)Ru1—Cl22.5007 (6)
Acknowledgements top

This project was supported by the Natural Science Foundation of China (grant No. 20771003).

references
References top

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