Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107001266/sk3081sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107001266/sk3081IIsup2.hkl |
CCDC reference: 638311
For related literature, see: Agterberg et al. (1998); Begley et al. (1985); Bennett & Smith (1974); Bernstein et al. (1995); Bianchini & Lee (2000); Bown & Hockless (1996); Britovsek et al. (1999); Carreón et al. (1997); Chisholm et al. (1996); Dayan & Çetinkaya (2005); Dias et al. (2000); Gemel et al. (1999); Gibson & Spitzmesser (2003); Holligan et al. (1992); Humphries et al. (2005); Libby et al. (1993); Nakayama et al. (2005); Nishiyama et al. (1995); Seçkin et al. (2004); Sheldrick (1997); Small & Brookhart (1998, 1999); Spek (2003); Çetinkaya et al. (1999).
All manipulations were performed under argon using standard Schlenk techniques. Melting points were determined in open capillary tubes on a digital Electrothermal 9100 melting-point apparatus. IR spectra (KBr pellets) were recorded in the range 400–4000 cm-1 on an ATI UNICAM 2000 spectrophotometer. 1H and 13C NMR spectra were obtained on a Varian AS 400 MHz s pectrometer operating at 399.883 and 100.561 MHz. Elemental analyses were carried out by the analytical service of TÜBİTAK (the Scientific and Technical Research Council of Turkey) using a Carlo Erba 1106 apparatus. RuCl3·3H2O (Johnson Matthey), α-phellandrene (Acros), diacetylpyridine (Fluka) and 2-ethyl-6-methylaniline (Avacado) were used as received. [RuCl2(p-cymene)]2 was synthesized according to the procedure of Bennett & Smith (1974).
Compound (I) was prepared using a modification of Çetinkaya's method (Çetinkaya et al., 1999; Dayan & Çetinkaya; 2005). Solvents were of analytical grade and were distilled after drying. An ethanolic solution (15 ml) of 1.10 equivalents of (I) (437 mg, 1.10 mmol) was mixed with [RuCl2(p-cymene)]2 (306 mg, 0.5 mmol). The reaction mixture was heated under reflux for 10 h. The resulting deep-purple solution was cooled to room temperature. The ethanol was removed by distillation, and the residue was dissolved in dichloromethane (15 ml) with acetonitrile (1 ml, excess mmol) and precipitated by the addition of diethyl ether (30 ml). The microcrystalline solid was then washed with diethyl ether (30 ml) and pentane (30 ml). The desired product was dried in a vacuum at 323 K for 1 h. X-ray quality crystals were grown from CH2Cl2–Et2O (30 ml, 1:2 v/v) [yield 425 mg, 70%; m.p. 421 K (decomposition)]. Analysis, calculated for C29H34Cl2N4Ru: C 57.05, H 5.61, N 9.18%; found: C 57.45, H 5.34, N 8.76%. Spectroscopic analysis: 1H NMR (CDCl3, δ, p.p.m.): 1.09 [t, 6H, J = 7.2 Hz, 2-Me-6-(CH2Me)—Ph], 2.24 [s, 6H, 2-Me-6-(CH2Me)—Ph], 2.30 (s, 3H, MeCN), 2.65 (s, 6H, N═ CMe), 2.72 [m, 4H, 2-Me-6-(CH2Me)—Ph], 5.28 (s, 1H, CH2Cl2), 7.13 (m, 6H, Ph—H), 7.62 (t, 1H, J = 7.8 Hz, py—Hp), 7.87 (d, 2H, J = 7.6 Hz, py—Hm); 13C NMR (CDCl3, δ, p.p.m.): 11.14, 11.52, 14.68, 17.20, 21.82, 119.83, 122.23, 122.64, 124.67, 127.85, 133.91, 134.22, 142.00, 143.23, 159.29, 169.16; IR (KBr): ν(C═N) 1601 cm-1.
H atoms were positioned geometrically and treated using a riding model, fixing the bond lengths at 0.96, 0.97 and 0.93 Å for CH3, CH2 and aromatic CH groups, respectively. The displacement parameters of the H atoms were constrained at Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for methyl H atoms. Riding methyl H atoms were allowed to rotate freely during refinement using the AFIX 137 command of SHELXL97 (Sheldrick, 1997). Examination of the refined structure using PLATON (Spek, 2003) revealed the presence of void spaces having a total volume of 224.6 Å3 (3.5%) per unit cell, the volume of the individual voids being 28 Å3. The maximum peak in the final difference Fourier map is 0.77 e Å-3 at a distance of 0.42 Å from atom H16C, and the minimum peak is -0.48 e Å-3 at a distance of 0.82 Å from atom Ru1. Even though the structure contains solvent-accessible voids, both the minimum and maximum residual electron-density peaks were smaller than 1 e Å-3, indicating that no molecular fragments remain unaccounted for.
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
[RuCl2(C2H3N)(C27H31N3)]·0.5CH2Cl2 | F(000) = 2680 |
Mr = 653.04 | Dx = 1.364 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 35511 reflections |
a = 31.385 (2) Å | θ = 1.8–27.1° |
b = 12.4151 (7) Å | µ = 0.77 mm−1 |
c = 16.5874 (11) Å | T = 296 K |
β = 100.246 (6)° | Prism, black |
V = 6360.2 (7) Å3 | 0.73 × 0.47 × 0.24 mm |
Z = 8 |
Stoe IPDS II diffractometer | 6268 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 3804 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.091 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 1.8° |
ω scans | h = −38→38 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −15→15 |
Tmin = 0.691, Tmax = 0.865 | l = −20→20 |
43963 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.159 | w = 1/[σ2(Fo2) + (0.0844P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
6268 reflections | Δρmax = 0.77 e Å−3 |
347 parameters | Δρmin = −0.48 e Å−3 |
318 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.000167 (7) |
[RuCl2(C2H3N)(C27H31N3)]·0.5CH2Cl2 | V = 6360.2 (7) Å3 |
Mr = 653.04 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 31.385 (2) Å | µ = 0.77 mm−1 |
b = 12.4151 (7) Å | T = 296 K |
c = 16.5874 (11) Å | 0.73 × 0.47 × 0.24 mm |
β = 100.246 (6)° |
Stoe IPDS II diffractometer | 6268 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 3804 reflections with I > 2σ(I) |
Tmin = 0.691, Tmax = 0.865 | Rint = 0.091 |
43963 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 318 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.77 e Å−3 |
6268 reflections | Δρmin = −0.48 e Å−3 |
347 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. |
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 | 0.130153 (16) | 0.92026 (3) | 0.12096 (3) | 0.06680 (19) | |
Cl1 | 0.06129 (5) | 0.89819 (13) | 0.16233 (10) | 0.0881 (4) | |
Cl2 | 0.19650 (6) | 0.94179 (13) | 0.07172 (10) | 0.0860 (4) | |
Cl3 | −0.04105 (16) | 0.6212 (4) | 0.1924 (3) | 0.264 (2) | |
N1 | 0.15191 (15) | 0.8835 (4) | 0.2328 (3) | 0.0704 (10) | |
N2 | 0.13636 (16) | 0.7533 (4) | 0.1129 (3) | 0.0743 (10) | |
N3 | 0.13870 (17) | 1.0728 (4) | 0.1748 (3) | 0.0788 (11) | |
N4 | 0.09834 (17) | 0.9644 (4) | 0.0051 (3) | 0.0770 (11) | |
C1 | 0.1569 (2) | 0.9635 (5) | 0.2899 (3) | 0.0770 (12) | |
C2 | 0.1664 (2) | 0.9372 (6) | 0.3730 (4) | 0.0872 (15) | |
H2 | 0.1710 | 0.9910 | 0.4126 | 0.105* | |
C3 | 0.1688 (2) | 0.8312 (6) | 0.3951 (4) | 0.0952 (16) | |
H3 | 0.1754 | 0.8130 | 0.4503 | 0.114* | |
C4 | 0.1615 (2) | 0.7504 (6) | 0.3369 (3) | 0.0890 (15) | |
H4 | 0.1620 | 0.6784 | 0.3525 | 0.107* | |
C5 | 0.1535 (2) | 0.7788 (5) | 0.2554 (3) | 0.0774 (12) | |
C6 | 0.1448 (2) | 0.7060 (5) | 0.1846 (4) | 0.0790 (13) | |
C7 | 0.1469 (3) | 0.5868 (5) | 0.1984 (4) | 0.105 (2) | |
H7A | 0.1382 | 0.5503 | 0.1471 | 0.157* | |
H7B | 0.1279 | 0.5672 | 0.2353 | 0.157* | |
H7C | 0.1760 | 0.5665 | 0.2217 | 0.157* | |
C8 | 0.1501 (2) | 1.0694 (5) | 0.2540 (4) | 0.0827 (13) | |
C9 | 0.1553 (3) | 1.1691 (6) | 0.3078 (4) | 0.106 (2) | |
H9A | 0.1426 | 1.2299 | 0.2766 | 0.159* | |
H9B | 0.1855 | 1.1825 | 0.3271 | 0.159* | |
H9C | 0.1410 | 1.1580 | 0.3537 | 0.159* | |
C10 | 0.1366 (3) | 0.6918 (4) | 0.0395 (4) | 0.0864 (13) | |
C11 | 0.0994 (3) | 0.6732 (5) | −0.0141 (5) | 0.1065 (16) | |
C12 | 0.1008 (3) | 0.6205 (6) | −0.0901 (5) | 0.1198 (19) | |
H12 | 0.0757 | 0.6058 | −0.1275 | 0.144* | |
C13 | 0.1403 (4) | 0.5928 (6) | −0.1051 (5) | 0.120 (2) | |
H13 | 0.1414 | 0.5610 | −0.1554 | 0.144* | |
C14 | 0.1778 (3) | 0.6069 (5) | −0.0545 (5) | 0.1131 (18) | |
H14 | 0.2037 | 0.5831 | −0.0685 | 0.136* | |
C15 | 0.1774 (3) | 0.6594 (5) | 0.0213 (4) | 0.0974 (15) | |
C16 | 0.2188 (3) | 0.6685 (6) | 0.0788 (5) | 0.115 (2) | |
H16A | 0.2144 | 0.7074 | 0.1267 | 0.173* | |
H16B | 0.2394 | 0.7063 | 0.0528 | 0.173* | |
H16C | 0.2297 | 0.5978 | 0.0944 | 0.173* | |
C17 | 0.0574 (3) | 0.7005 (7) | 0.0054 (6) | 0.127 (2) | |
H17A | 0.0605 | 0.7633 | 0.0408 | 0.153* | |
H17B | 0.0379 | 0.7195 | −0.0447 | 0.153* | |
C18 | 0.0392 (4) | 0.6192 (11) | 0.0432 (9) | 0.192 (4) | |
H18A | 0.0115 | 0.6419 | 0.0537 | 0.288* | |
H18B | 0.0577 | 0.6018 | 0.0940 | 0.288* | |
H18C | 0.0357 | 0.5569 | 0.0084 | 0.288* | |
C19 | 0.1371 (3) | 1.1759 (5) | 0.1321 (4) | 0.0925 (14) | |
C20 | 0.0980 (3) | 1.2180 (6) | 0.0962 (5) | 0.1138 (17) | |
C21 | 0.0982 (4) | 1.3154 (6) | 0.0498 (5) | 0.131 (2) | |
H21 | 0.0724 | 1.3466 | 0.0242 | 0.157* | |
C22 | 0.1359 (4) | 1.3601 (7) | 0.0441 (6) | 0.139 (2) | |
H22 | 0.1355 | 1.4230 | 0.0136 | 0.167* | |
C23 | 0.1737 (4) | 1.3215 (6) | 0.0788 (5) | 0.129 (2) | |
H23 | 0.1990 | 1.3569 | 0.0723 | 0.155* | |
C24 | 0.1759 (3) | 1.2265 (6) | 0.1257 (4) | 0.1086 (17) | |
C25 | 0.2195 (3) | 1.1866 (7) | 0.1652 (6) | 0.132 (2) | |
H25A | 0.2375 | 1.1789 | 0.1245 | 0.197* | |
H25B | 0.2165 | 1.1180 | 0.1904 | 0.197* | |
H25C | 0.2325 | 1.2371 | 0.2061 | 0.197* | |
C26 | 0.0563 (3) | 1.1721 (7) | 0.1060 (6) | 0.131 (2) | |
H26A | 0.0590 | 1.0948 | 0.1135 | 0.157* | |
H26B | 0.0349 | 1.1860 | 0.0573 | 0.157* | |
C27 | 0.0425 (4) | 1.2219 (11) | 0.1783 (7) | 0.180 (4) | |
H27A | 0.0160 | 1.1892 | 0.1872 | 0.270* | |
H27B | 0.0380 | 1.2977 | 0.1690 | 0.270* | |
H27C | 0.0646 | 1.2111 | 0.2258 | 0.270* | |
C28 | 0.0782 (2) | 0.9954 (6) | −0.0531 (4) | 0.0892 (16) | |
C29 | 0.0516 (3) | 1.0370 (9) | −0.1278 (5) | 0.144 (3) | |
H29A | 0.0486 | 1.1136 | −0.1232 | 0.215* | |
H29B | 0.0236 | 1.0038 | −0.1355 | 0.215* | |
H29C | 0.0653 | 1.0210 | −0.1739 | 0.215* | |
C30 | 0.0000 | 0.6887 (13) | 0.2500 | 0.175 (5) | |
H30 | 0.0125 | 0.7353 | 0.2135 | 0.210* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.0810 (3) | 0.0628 (3) | 0.0557 (3) | 0.0025 (2) | 0.0099 (2) | 0.00075 (19) |
Cl1 | 0.0833 (10) | 0.0986 (11) | 0.0838 (10) | −0.0005 (8) | 0.0192 (8) | 0.0016 (8) |
Cl2 | 0.0933 (11) | 0.0896 (10) | 0.0775 (9) | 0.0004 (8) | 0.0216 (8) | 0.0067 (7) |
Cl3 | 0.235 (4) | 0.290 (5) | 0.283 (5) | −0.107 (4) | 0.093 (4) | −0.122 (4) |
N1 | 0.078 (3) | 0.075 (2) | 0.058 (2) | 0.005 (2) | 0.011 (2) | −0.0015 (17) |
N2 | 0.097 (3) | 0.065 (2) | 0.061 (2) | 0.001 (2) | 0.014 (2) | 0.0021 (17) |
N3 | 0.098 (3) | 0.069 (2) | 0.069 (2) | 0.003 (2) | 0.016 (2) | −0.0039 (18) |
N4 | 0.090 (3) | 0.076 (3) | 0.065 (2) | 0.003 (2) | 0.014 (2) | 0.004 (2) |
C1 | 0.084 (3) | 0.089 (3) | 0.058 (2) | −0.002 (3) | 0.014 (2) | −0.005 (2) |
C2 | 0.094 (4) | 0.107 (3) | 0.058 (3) | 0.001 (3) | 0.009 (3) | −0.006 (2) |
C3 | 0.108 (4) | 0.119 (4) | 0.057 (3) | 0.006 (3) | 0.010 (3) | 0.008 (3) |
C4 | 0.104 (4) | 0.098 (3) | 0.064 (3) | 0.008 (3) | 0.014 (3) | 0.014 (2) |
C5 | 0.089 (3) | 0.081 (2) | 0.062 (2) | 0.008 (3) | 0.013 (2) | 0.008 (2) |
C6 | 0.097 (4) | 0.072 (2) | 0.068 (2) | 0.005 (3) | 0.015 (3) | 0.009 (2) |
C7 | 0.155 (6) | 0.076 (3) | 0.083 (4) | −0.002 (4) | 0.018 (4) | 0.019 (3) |
C8 | 0.095 (3) | 0.083 (3) | 0.069 (3) | 0.003 (3) | 0.010 (3) | −0.013 (2) |
C9 | 0.131 (6) | 0.099 (4) | 0.086 (4) | −0.004 (4) | 0.015 (4) | −0.027 (3) |
C10 | 0.131 (3) | 0.056 (2) | 0.071 (3) | 0.000 (3) | 0.012 (3) | 0.001 (2) |
C11 | 0.149 (4) | 0.066 (3) | 0.095 (3) | 0.001 (3) | −0.005 (3) | −0.004 (3) |
C12 | 0.180 (5) | 0.075 (3) | 0.091 (4) | −0.006 (4) | −0.011 (4) | 0.000 (3) |
C13 | 0.196 (6) | 0.074 (3) | 0.089 (4) | −0.005 (4) | 0.019 (4) | −0.001 (3) |
C14 | 0.177 (5) | 0.075 (3) | 0.094 (4) | −0.001 (4) | 0.043 (3) | 0.000 (3) |
C15 | 0.151 (4) | 0.065 (3) | 0.082 (3) | 0.003 (3) | 0.037 (3) | −0.003 (2) |
C16 | 0.129 (5) | 0.108 (5) | 0.117 (5) | 0.002 (4) | 0.042 (4) | −0.007 (4) |
C17 | 0.138 (5) | 0.098 (4) | 0.131 (5) | −0.006 (4) | −0.017 (4) | −0.009 (4) |
C18 | 0.172 (9) | 0.194 (9) | 0.216 (10) | −0.001 (8) | 0.052 (7) | 0.031 (8) |
C19 | 0.137 (4) | 0.067 (3) | 0.075 (3) | −0.003 (3) | 0.020 (3) | −0.011 (2) |
C20 | 0.159 (4) | 0.075 (3) | 0.104 (4) | 0.022 (3) | 0.013 (4) | −0.003 (3) |
C21 | 0.192 (6) | 0.085 (4) | 0.113 (4) | 0.024 (4) | 0.015 (4) | −0.003 (3) |
C22 | 0.213 (6) | 0.087 (4) | 0.117 (5) | −0.008 (4) | 0.029 (5) | −0.008 (4) |
C23 | 0.193 (6) | 0.090 (4) | 0.110 (4) | −0.036 (4) | 0.041 (4) | −0.016 (3) |
C24 | 0.165 (4) | 0.078 (3) | 0.087 (4) | −0.028 (3) | 0.034 (3) | −0.018 (3) |
C25 | 0.140 (5) | 0.127 (6) | 0.129 (6) | −0.049 (5) | 0.030 (5) | −0.020 (4) |
C26 | 0.143 (5) | 0.103 (4) | 0.140 (5) | 0.034 (4) | 0.005 (5) | −0.002 (4) |
C27 | 0.172 (8) | 0.202 (9) | 0.172 (8) | 0.014 (8) | 0.049 (7) | −0.006 (7) |
C28 | 0.089 (4) | 0.112 (4) | 0.066 (3) | 0.005 (3) | 0.013 (3) | 0.017 (3) |
C29 | 0.100 (6) | 0.222 (8) | 0.104 (5) | 0.027 (6) | 0.004 (4) | 0.065 (6) |
C30 | 0.152 (9) | 0.159 (10) | 0.220 (12) | 0.000 | 0.051 (8) | 0.000 |
Ru1—N1 | 1.914 (4) | C14—C15 | 1.418 (9) |
Ru1—N4 | 2.076 (5) | C14—H14 | 0.9300 |
Ru1—N2 | 2.088 (4) | C15—C16 | 1.474 (11) |
Ru1—N3 | 2.090 (4) | C16—H16A | 0.9600 |
Ru1—Cl2 | 2.3833 (17) | C16—H16B | 0.9600 |
Ru1—Cl1 | 2.3967 (17) | C16—H16C | 0.9600 |
Cl3—C30 | 1.685 (9) | C17—C18 | 1.364 (13) |
N1—C5 | 1.353 (7) | C17—H17A | 0.9700 |
N1—C1 | 1.362 (7) | C17—H17B | 0.9700 |
N2—C6 | 1.311 (7) | C18—H18A | 0.9600 |
N2—C10 | 1.438 (7) | C18—H18B | 0.9600 |
N3—C8 | 1.299 (8) | C18—H18C | 0.9600 |
N3—C19 | 1.459 (8) | C19—C20 | 1.367 (11) |
N4—C28 | 1.123 (7) | C19—C24 | 1.392 (11) |
C1—C2 | 1.397 (8) | C20—C21 | 1.434 (11) |
C1—C8 | 1.443 (8) | C20—C26 | 1.463 (12) |
C2—C3 | 1.364 (9) | C21—C22 | 1.324 (14) |
C2—H2 | 0.9300 | C21—H21 | 0.9300 |
C3—C4 | 1.383 (9) | C22—C23 | 1.315 (13) |
C3—H3 | 0.9300 | C22—H22 | 0.9300 |
C4—C5 | 1.376 (7) | C23—C24 | 1.408 (11) |
C4—H4 | 0.9300 | C23—H23 | 0.9300 |
C5—C6 | 1.469 (8) | C24—C25 | 1.492 (12) |
C6—C7 | 1.497 (8) | C25—H25A | 0.9600 |
C7—H7A | 0.9600 | C25—H25B | 0.9600 |
C7—H7B | 0.9600 | C25—H25C | 0.9600 |
C7—H7C | 0.9600 | C26—C27 | 1.482 (13) |
C8—C9 | 1.518 (8) | C26—H26A | 0.9700 |
C9—H9A | 0.9600 | C26—H26B | 0.9700 |
C9—H9B | 0.9600 | C27—H27A | 0.9600 |
C9—H9C | 0.9600 | C27—H27B | 0.9600 |
C10—C11 | 1.356 (10) | C27—H27C | 0.9600 |
C10—C15 | 1.424 (10) | C28—C29 | 1.460 (10) |
C11—C12 | 1.428 (10) | C29—H29A | 0.9600 |
C11—C17 | 1.453 (12) | C29—H29B | 0.9600 |
C12—C13 | 1.353 (12) | C29—H29C | 0.9600 |
C12—H12 | 0.9300 | C30—Cl3i | 1.685 (9) |
C13—C14 | 1.330 (12) | C30—H30 | 0.9700 |
C13—H13 | 0.9300 | ||
N1—Ru1—N4 | 171.93 (19) | C13—C14—C15 | 118.2 (9) |
N1—Ru1—N2 | 78.73 (18) | C13—C14—H14 | 120.9 |
N4—Ru1—N2 | 103.73 (18) | C15—C14—H14 | 120.9 |
N1—Ru1—N3 | 78.78 (19) | C14—C15—C10 | 118.0 (8) |
N4—Ru1—N3 | 99.23 (19) | C14—C15—C16 | 117.5 (8) |
N2—Ru1—N3 | 156.96 (19) | C10—C15—C16 | 124.3 (6) |
N1—Ru1—Cl2 | 100.13 (14) | C15—C16—H16A | 109.5 |
N4—Ru1—Cl2 | 87.63 (14) | C15—C16—H16B | 109.5 |
N2—Ru1—Cl2 | 89.55 (14) | H16A—C16—H16B | 109.5 |
N3—Ru1—Cl2 | 89.49 (15) | C15—C16—H16C | 109.5 |
N1—Ru1—Cl1 | 83.10 (14) | H16A—C16—H16C | 109.5 |
N4—Ru1—Cl1 | 89.17 (14) | H16B—C16—H16C | 109.5 |
N2—Ru1—Cl1 | 90.23 (14) | C18—C17—C11 | 113.6 (9) |
N3—Ru1—Cl1 | 92.01 (15) | C18—C17—H17A | 108.9 |
Cl2—Ru1—Cl1 | 176.65 (6) | C11—C17—H17A | 108.9 |
C5—N1—C1 | 120.9 (5) | C18—C17—H17B | 108.9 |
C5—N1—Ru1 | 119.2 (4) | C11—C17—H17B | 108.9 |
C1—N1—Ru1 | 118.5 (4) | H17A—C17—H17B | 107.7 |
C6—N2—C10 | 119.9 (5) | C17—C18—H18A | 109.5 |
C6—N2—Ru1 | 113.1 (4) | C17—C18—H18B | 109.5 |
C10—N2—Ru1 | 126.6 (3) | H18A—C18—H18B | 109.5 |
C8—N3—C19 | 119.9 (5) | C17—C18—H18C | 109.5 |
C8—N3—Ru1 | 113.2 (4) | H18A—C18—H18C | 109.5 |
C19—N3—Ru1 | 126.6 (4) | H18B—C18—H18C | 109.5 |
C28—N4—Ru1 | 172.1 (5) | C20—C19—C24 | 121.6 (7) |
N1—C1—C2 | 119.6 (6) | C20—C19—N3 | 119.9 (7) |
N1—C1—C8 | 112.8 (5) | C24—C19—N3 | 118.5 (7) |
C2—C1—C8 | 127.6 (6) | C19—C20—C21 | 117.9 (9) |
C3—C2—C1 | 118.9 (6) | C19—C20—C26 | 123.6 (7) |
C3—C2—H2 | 120.5 | C21—C20—C26 | 118.5 (9) |
C1—C2—H2 | 120.5 | C22—C21—C20 | 118.7 (10) |
C2—C3—C4 | 121.2 (6) | C22—C21—H21 | 120.6 |
C2—C3—H3 | 119.4 | C20—C21—H21 | 120.6 |
C4—C3—H3 | 119.4 | C23—C22—C21 | 124.4 (10) |
C5—C4—C3 | 118.6 (6) | C23—C22—H22 | 117.8 |
C5—C4—H4 | 120.7 | C21—C22—H22 | 117.8 |
C3—C4—H4 | 120.7 | C22—C23—C24 | 119.9 (10) |
N1—C5—C4 | 120.7 (6) | C22—C23—H23 | 120.1 |
N1—C5—C6 | 112.1 (5) | C24—C23—H23 | 120.1 |
C4—C5—C6 | 127.2 (6) | C19—C24—C23 | 117.6 (9) |
N2—C6—C5 | 115.4 (5) | C19—C24—C25 | 124.3 (7) |
N2—C6—C7 | 125.3 (6) | C23—C24—C25 | 118.1 (9) |
C5—C6—C7 | 119.2 (5) | C24—C25—H25A | 109.5 |
C6—C7—H7A | 109.5 | C24—C25—H25B | 109.5 |
C6—C7—H7B | 109.5 | H25A—C25—H25B | 109.5 |
H7A—C7—H7B | 109.5 | C24—C25—H25C | 109.5 |
C6—C7—H7C | 109.5 | H25A—C25—H25C | 109.5 |
H7A—C7—H7C | 109.5 | H25B—C25—H25C | 109.5 |
H7B—C7—H7C | 109.5 | C20—C26—C27 | 108.9 (9) |
N3—C8—C1 | 116.1 (5) | C20—C26—H26A | 109.9 |
N3—C8—C9 | 123.4 (6) | C27—C26—H26A | 109.9 |
C1—C8—C9 | 120.5 (6) | C20—C26—H26B | 109.9 |
C8—C9—H9A | 109.5 | C27—C26—H26B | 109.9 |
C8—C9—H9B | 109.5 | H26A—C26—H26B | 108.3 |
H9A—C9—H9B | 109.5 | C26—C27—H27A | 109.5 |
C8—C9—H9C | 109.5 | C26—C27—H27B | 109.5 |
H9A—C9—H9C | 109.5 | H27A—C27—H27B | 109.5 |
H9B—C9—H9C | 109.5 | C26—C27—H27C | 109.5 |
C11—C10—C15 | 121.0 (7) | H27A—C27—H27C | 109.5 |
C11—C10—N2 | 120.8 (7) | H27B—C27—H27C | 109.5 |
C15—C10—N2 | 118.0 (6) | N4—C28—C29 | 178.9 (8) |
C10—C11—C12 | 119.9 (9) | C28—C29—H29A | 109.5 |
C10—C11—C17 | 121.6 (7) | C28—C29—H29B | 109.5 |
C12—C11—C17 | 118.3 (8) | H29A—C29—H29B | 109.5 |
C13—C12—C11 | 116.8 (9) | C28—C29—H29C | 109.5 |
C13—C12—H12 | 121.6 | H29A—C29—H29C | 109.5 |
C11—C12—H12 | 121.6 | H29B—C29—H29C | 109.5 |
C14—C13—C12 | 126.1 (9) | Cl3i—C30—Cl3 | 120.3 (11) |
C14—C13—H13 | 116.9 | Cl3i—C30—H30 | 107.3 |
C12—C13—H13 | 116.9 | Cl3—C30—H30 | 107.3 |
N2—Ru1—N1—C5 | −10.9 (4) | C4—C5—C6—C7 | −3.9 (10) |
N3—Ru1—N1—C5 | 174.2 (5) | C19—N3—C8—C1 | −171.4 (6) |
Cl2—Ru1—N1—C5 | −98.4 (4) | Ru1—N3—C8—C1 | 3.0 (7) |
Cl1—Ru1—N1—C5 | 80.7 (4) | C19—N3—C8—C9 | 10.0 (10) |
N2—Ru1—N1—C1 | −177.6 (5) | Ru1—N3—C8—C9 | −175.6 (5) |
N3—Ru1—N1—C1 | 7.4 (4) | N1—C1—C8—N3 | 2.8 (8) |
Cl2—Ru1—N1—C1 | 94.9 (4) | C2—C1—C8—N3 | −175.5 (6) |
Cl1—Ru1—N1—C1 | −86.0 (4) | N1—C1—C8—C9 | −178.5 (6) |
N1—Ru1—N2—C6 | 9.7 (4) | C2—C1—C8—C9 | 3.2 (11) |
N4—Ru1—N2—C6 | −162.5 (4) | C6—N2—C10—C11 | 111.7 (7) |
N3—Ru1—N2—C6 | 22.4 (7) | Ru1—N2—C10—C11 | −75.4 (7) |
Cl2—Ru1—N2—C6 | 110.1 (4) | C6—N2—C10—C15 | −73.8 (7) |
Cl1—Ru1—N2—C6 | −73.3 (4) | Ru1—N2—C10—C15 | 99.0 (6) |
N1—Ru1—N2—C10 | −163.6 (6) | C15—C10—C11—C12 | 0.0 (10) |
N4—Ru1—N2—C10 | 24.3 (6) | N2—C10—C11—C12 | 174.3 (6) |
N3—Ru1—N2—C10 | −150.8 (6) | C15—C10—C11—C17 | 176.6 (7) |
Cl2—Ru1—N2—C10 | −63.2 (5) | N2—C10—C11—C17 | −9.1 (10) |
Cl1—Ru1—N2—C10 | 113.5 (5) | C10—C11—C12—C13 | −1.0 (10) |
N1—Ru1—N3—C8 | −5.6 (5) | C17—C11—C12—C13 | −177.7 (7) |
N4—Ru1—N3—C8 | 166.5 (4) | C11—C12—C13—C14 | 2.4 (12) |
N2—Ru1—N3—C8 | −18.3 (8) | C12—C13—C14—C15 | −2.6 (12) |
Cl2—Ru1—N3—C8 | −106.0 (4) | C13—C14—C15—C10 | 1.3 (10) |
Cl1—Ru1—N3—C8 | 77.0 (4) | C13—C14—C15—C16 | 176.4 (7) |
N1—Ru1—N3—C19 | 168.3 (6) | C11—C10—C15—C14 | −0.1 (9) |
N4—Ru1—N3—C19 | −19.6 (6) | N2—C10—C15—C14 | −174.6 (5) |
N2—Ru1—N3—C19 | 155.6 (5) | C11—C10—C15—C16 | −174.8 (6) |
Cl2—Ru1—N3—C19 | 67.9 (5) | N2—C10—C15—C16 | 10.7 (9) |
Cl1—Ru1—N3—C19 | −109.1 (5) | C10—C11—C17—C18 | −89.7 (11) |
C5—N1—C1—C2 | 3.9 (9) | C12—C11—C17—C18 | 86.9 (12) |
Ru1—N1—C1—C2 | 170.4 (5) | C8—N3—C19—C20 | −111.0 (8) |
C5—N1—C1—C8 | −174.5 (5) | Ru1—N3—C19—C20 | 75.5 (8) |
Ru1—N1—C1—C8 | −8.0 (7) | C8—N3—C19—C24 | 72.1 (8) |
N1—C1—C2—C3 | −2.6 (10) | Ru1—N3—C19—C24 | −101.4 (6) |
C8—C1—C2—C3 | 175.5 (7) | C24—C19—C20—C21 | 1.3 (11) |
C1—C2—C3—C4 | −0.7 (11) | N3—C19—C20—C21 | −175.5 (6) |
C2—C3—C4—C5 | 2.7 (10) | C24—C19—C20—C26 | −175.4 (7) |
C1—N1—C5—C4 | −1.9 (9) | N3—C19—C20—C26 | 7.8 (11) |
Ru1—N1—C5—C4 | −168.3 (5) | C19—C20—C21—C22 | −0.2 (12) |
C1—N1—C5—C6 | 176.6 (5) | C26—C20—C21—C22 | 176.7 (8) |
Ru1—N1—C5—C6 | 10.2 (7) | C20—C21—C22—C23 | −0.4 (15) |
C3—C4—C5—N1 | −1.4 (10) | C21—C22—C23—C24 | −0.1 (15) |
C3—C4—C5—C6 | −179.6 (6) | C20—C19—C24—C23 | −1.8 (10) |
C10—N2—C6—C5 | 166.6 (6) | N3—C19—C24—C23 | 175.1 (6) |
Ru1—N2—C6—C5 | −7.2 (7) | C20—C19—C24—C25 | 178.3 (7) |
C10—N2—C6—C7 | −12.3 (10) | N3—C19—C24—C25 | −4.8 (10) |
Ru1—N2—C6—C7 | 173.9 (6) | C22—C23—C24—C19 | 1.1 (11) |
N1—C5—C6—N2 | −1.1 (8) | C22—C23—C24—C25 | −179.0 (8) |
C4—C5—C6—N2 | 177.2 (6) | C19—C20—C26—C27 | 89.7 (10) |
N1—C5—C6—C7 | 177.8 (6) | C21—C20—C26—C27 | −87.0 (10) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C26—H26A···Cl1 | 0.97 | 2.57 | 3.523 (9) | 168 |
C17—H17A···Cl1 | 0.97 | 2.62 | 3.563 (9) | 165 |
C30—H30···Cl1 | 0.97 | 2.76 | 3.684 (12) | 160 |
C2—H2···Cl2ii | 0.93 | 2.75 | 3.593 (6) | 152 |
Symmetry code: (ii) x, −y+2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [RuCl2(C2H3N)(C27H31N3)]·0.5CH2Cl2 |
Mr | 653.04 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 31.385 (2), 12.4151 (7), 16.5874 (11) |
β (°) | 100.246 (6) |
V (Å3) | 6360.2 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.77 |
Crystal size (mm) | 0.73 × 0.47 × 0.24 |
Data collection | |
Diffractometer | Stoe IPDS II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.691, 0.865 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 43963, 6268, 3804 |
Rint | 0.091 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.159, 1.03 |
No. of reflections | 6268 |
No. of parameters | 347 |
No. of restraints | 318 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.77, −0.48 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
Ru1—N2 | 2.088 (4) | Ru1—Cl2 | 2.3833 (17) |
Ru1—N3 | 2.090 (4) | Ru1—Cl1 | 2.3967 (17) |
N1—Ru1—N2 | 78.73 (18) | N3—Ru1—Cl2 | 89.49 (15) |
N4—Ru1—N2 | 103.73 (18) | N1—Ru1—Cl1 | 83.10 (14) |
N1—Ru1—N3 | 78.78 (19) | N4—Ru1—Cl1 | 89.17 (14) |
N4—Ru1—N3 | 99.23 (19) | N2—Ru1—Cl1 | 90.23 (14) |
N1—Ru1—Cl2 | 100.13 (14) | N3—Ru1—Cl1 | 92.01 (15) |
N4—Ru1—Cl2 | 87.63 (14) | Cl2—Ru1—Cl1 | 176.65 (6) |
N2—Ru1—Cl2 | 89.55 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C26—H26A···Cl1 | 0.97 | 2.57 | 3.523 (9) | 168 |
C17—H17A···Cl1 | 0.97 | 2.62 | 3.563 (9) | 165 |
C30—H30···Cl1 | 0.97 | 2.76 | 3.684 (12) | 160 |
C2—H2···Cl2i | 0.93 | 2.75 | 3.593 (6) | 152 |
Symmetry code: (i) x, −y+2, z+1/2. |
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Although many pydim-based transition metal complexes have been reported (pydim is ? Please define; Small & Brookhart, 1998, 1999; Britovsek et al., 1999; Gibson & Spitzmesser, 2003; Nakayama et al., 2005; Humphries et al., 2005, and references therein), examples of the related Ru complexes are scarce (Çetinkaya et al., 1999; Bianchini & Lee, 2000; Dias et al., 2000; Seçkin et al., 2004; Dayan & Çetinkaya; 2005). The structural feature of five-coordination results in the formation of coordinatively unsaturated RuII complexes containing the pydim ligand and makes these complexes interesting from the viewpoint of potential application in homogeneously RuII-catalyzed reactions. The presence of a labile ligand makes these complexes potentially interesting as precursors for the synthesis of a variety of RuII complexes of the type [RuCl2(pydim)L], where L is a neutral ligand. For example, [RuCl2(pydim)CH3CN] compounds (Ar = 2,6-Me2C6H3) exhibit efficient activity for the epoxidation of cyclohexane (Çetinkaya et al., 1999).
In the present study, the title compound, (II), was synthesized in good yield (70%) by the reaction sequences depicted in the scheme. The composition of this complex has been confirmed by CHN analysis and IR and NMR spectroscopies. In order to establish the coordination geometry about the metal atom and to examine the structural parameters in this case, we present here the synthesis and crystal structure of compound (II).
The molecular structure of complex (II) and the atom-labelling scheme are shown in Fig. 1. Selected geometric parameters for (II) are summarized in Table 1. The mononuclear pydim molecule contains an (N,N'E,N,N'E)-N,N'-[1,1'-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidene)]bis(2-ethyl-6-methylaniline) ligand, (I), with a RuII metal centre, one acetonitrile ligand and two Cl ligands. Complex (II) crystallizes with half of a dichloromethane solvent molecule in the asymmetric unit and the ligand, (I), with its two imine groups in ortho positions with respect to the pyridine N atom, behaves as a symmetrical N,N',N-tridentate chelate. The RuII ion is six-coordinated by two imino N atoms, one pyridine N atom, one acetonitrile N atom and two Cl atoms (Fig. 1). The five-membered chelate rings formed by atoms Ru1/N1/C1/C8/N3 and atoms Ru1/N1/C5/C6/N2 are planar and the maximum deviations from their planes are 0.054 (3) and 0.076 (3) Å, respectively, for atom N1. These two chelate rings make a small dihedral angle of 1.59 (8)° with one another, indicating that they are nearly coplanar.
The asymmetric unit of (II) comprises one mononuclear pydim molecule and one-half of a dichloromethane solvent molecule lying on a twofold axis. The local structure around the RuII ion is that of an octahedron, of which the equatorial plane (N1/N2/N3/N4) is formed by three N atoms from ligand (I) (N1, N2 and N3) and one N atom of the acetonitrile ligand (N4). The axial positions in the octahedron are occupied by two Cl atoms (Cl1 and Cl2). As can be seen from the trans angles, which vary from 156.99 (19) to 176.65 (6)°, and the cis angles, which vary from 78.73 (18) to 103.73 (18)°, the coordination octahedra around the RuII ion can be visualized as being distorted, with the major distortion arising via the N2—Ru1—N3 angle, at 156.96 (19)°. This angle is considerably smaller than the ideal angle of 180° and there is no steric barrier to coordination of a fourth ligand in the equatorial plane trans to the pyridine moiety. The N1—Ru—N4 angle, involving the acetonitrile and pyridine N atoms, is normal, at 171.93 (19)°. The Ru—N2 and Ru—N3 bond lengths are comparable with the reported values for [RuCl2(pybox-dihydro)(C2H4)] (pybox-dihydro is ? Please define; Nishiyama et al., 1995). However, the M—N(pyridine) bond [1.914 (4) Å] is somewhat shorter than the M—N(imino) and M—N(acetonitrile) bonds, with the formal double-bond character of the imino linkages N2—C6 and N3—C8 having been retained [C═N distances are 1.311 (7) and 1.299 (8) Å, respectively]. This coordination environment is similar to that observed in [RuCl2(pydim)CH3CN] (Ar = 4-MeOC6H4; Çetinkaya et al., 1999).
The title complex possesses approximate non-crystallographic Cs symmetry about a plane bisecting the central pyridine ring and containing the metal atom, the acetonitrile N atom and the two halogen atoms. The planes of the phenyl rings substituted on the bis(imino)pyridine ligand backbone are, as usual for bis(imino)pyridine ligands, inclined almost orthogonally to the plane of the backbone [77.75 (18) and 77.28 (20)° for rings C10–C15 and C19–C24, respectively], while the dihedral angle between these two planes is 84.64 (18)°. The geometries at the imino N centres are all trigonal planar, the sums of the three bond angles around these centres being 359.6 and 359.7°, and none of them is more than ca 0.04 Å out of its associated (C2Ru) plane.
There are several structures reported in the literature containing various transition metal complexes of pydim-based ligands (Britovsek et al., 1999; Dias et al., 2000; Nakayama et al., 2005; Humphries et al., 2005). Inspection of the the M—N bond distances in (II) and in these examples indicates that the two M—N(imino) bonds are ca 0.1–0.2 Å longer than the corresponding M—N(pyridine) bond within each metal–tridentate chelate unit. Furthermore, it is observed that the N(imino)—M—N(pyridine) bond angle for the five-membered chelate rings of pydim complexes is inversely related to the magnitude of the M—N(pyridine) bond. As the M—N(pyridine) distance increases from 1.833 (3) Å for [CoMe(pydim)] (Ar = 2,6-iPr2C6H3; Humphries et al., 2005) to 1.911 (3) Å for [RhMe(pydim)](OTf)2 (Ar = 2,6-iPr2C6H3; Dias et al., 2000) to 1.914 (4) for (II) to 2.001 (3) Å for [CrCl3(pydim)] (Ar = C6F5; Nakayama et al., 2005) to 2.110 (6) Å for [FeCl2(pydim)] (Ar = 2,4,6-Me3C6H2; Britovsek et al., 1999), the corresponding inner `bite' angle decreases continuously from 81.17 (average) to 79.8 (average) to 78.76 (average) to 76.6 (average) to 72.8° (average), respectively.
The Ru—Nacetonitrile distance is 2.076 (5) Å and this is noticeably longer than the Ru—Nacetonitrile distances in [Ru(C5H8)(C10H15)(C2H3N)](CF3SO3) [2.059 (3) Å; Gemel et al., 1999], [Ru(C5H5)(C2H3N)(C18H15P)2]BF4 [2.040 (3) Å; Carreón et al., 1997] and [RuCl2(C2H3N)4] [2.021 (3) and 2.020 (3) Å; Bown & Hockless, 1996]. This enlargement can be attributed to the different coodination enviroments of the metal atoms. As expected, the acetonitrile ligand is in an almost perfectly linear configuration [N4—C28—C29 = 178.9 (8)°], but with a slightly bent coordination to the RuII ion [Ru1—N4—C28 = 172.1 (5)°]. Such coordination has been observed in [RuCl2(pydim)CH3CN] [Ar = 4-MeOC6H4; 173.3 (9)°; Çetinkaya et al., 1999]. A bent metal–acetonitrile coordination is indeed quite common, with angles from 145.2 to 176.9°, and an average of 167°, having been reported (Agterberg et al., 1998; Begley et al., 1985; Chisholm et al., 1996; Holligan et al., 1992; Libby et al., 1993). This average is somewhat lowered by the two extremely low values for nickel(II) (145.2°; Holligan et al., 1992) and manganese(III) (149.1°; Libby et al., 1993) complexes, which have been attributed to hydrogen-bonding and steric effects, respectively.
In the molecular structure of (II), two intramolecular interactions are observed between the methylene H atom substituted on the phenyl rings and the Cl atom coordinated to the metal atom (Table 2), which lead to the formation of seven-membered rings with graph-set descriptor S(7) (Bernstein et al., 1995). Each of these intramolecular hydrogen bonds is fused with both the phenyl ring and the five-membered chelate ring. Examination of the structure with PLATON (Spek, 2003) reveals that there are intermolecular interactions between atom Cl1 coordinated to the metal atom and atom H30 of the dichloromethane molecule. These interactions are probably responsible for stabilizing the dichloromethane molecule in the observed position. Another interaction is observed between atom Cl2 coordinated to the metal atom and atom H2 on atom C2 of the pyridine ring. Together, these intermolecular interactions form an R66(24) ring. Propagation of this hydrogen-bonding motif generates a chain of edge-fused rings running parallel to the [001] direction (Fig. 2). The full geometry of the intra- and intermolecular interactions is given in Table 2.