Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102003797/bm1490sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102003797/bm1490Isup2.hkl |
CCDC reference: 187901
A mixture of trans-[Ru(dmso)4Cl2] (200 mg, 0.41 mmol) and 2-acetylpyridine (0.14 ml, 1.25 mmol) in methanol (30 ml) was refluxed for 8 h. The clear purple reaction mixture was evaporated to dryness. The dark solid obtained was dissolved in a minimum volume of dichloromethane, followed by the addition of excess hexane. The complex which precipitated was collected by filtration. Purification was performed on a neutral alumina Query column. The first purple band was eluted with a dichloromethane-methanol (50:1) mixture. This eluent Query was collected and evaporated to dryness. The yield of the title complex, (I), thus obtained was 60 mg (32%). Single crystals of (I) were grown by slow evaporation of a dichloromethane-hexane (1:1) solution. Analysis: calculated for C11H19NO3Cl2S2Ru: C 29.40, H 4.26, N 3.12%; found: C 29.17, H 4.39, N 2.91%; selected IR bands (cm-1): 3017 (m), 1591 (w), 1561 (w), 1410 (m), 1371 (m), 1329 (m), 1310 (m), 1254 (m), 1175 (w), 1092 (s), 1045 (w), 1011 (s), 974 (m), 918 (w), 789 (s), 719 (m), 681 (s), 637 (w), 600 (w), 426 (s); electronic spectroscopic data in CH2Cl2 (nm, dm3 mol-1 cm-1): 537 (2140), 341 (1410), 282 (6970); 1H NMR (200 MHz, CDCl3, δ, p.p.m.): 3.06 [s, 3H, C(CH3)], 3.53 [s, 6H, S(CH3)2], 3.55 [s, 6H, S(CH3)2], 7.83 (t, 1H), 8.07 (t, 1H), 8.26 (d, 1H), 10.56 (d, 1H); cyclic voltammetric data (versus Fc+/Fc) at a Pt electrode in CH2Cl2 (E1/2/V, ΔEp/mV): 0.69 (260), -1.53 (140).
The H atoms of the methyl groups were located from difference Fourier syntheses and refined as part of rigid rotating groups, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C). The remaining aromatic H atoms were placed geometrically and refined using a riding model, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: WinGX (Farrugia, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX6a (McArdle, 1995); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I) with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. |
[Ru(C7H7NO)(C2H6OS)2Cl2] | Z = 2 |
Mr = 449.36 | F(000) = 452 |
Triclinic, P1 | Dx = 1.738 Mg m−3 |
a = 8.177 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.214 (3) Å | Cell parameters from 25 reflections |
c = 14.456 (6) Å | θ = 9.6–10.7° |
α = 84.69 (3)° | µ = 1.47 mm−1 |
β = 81.13 (4)° | T = 298 K |
γ = 63.53 (5)° | Rectangular block, dark brown |
V = 858.6 (7) Å3 | 0.48 × 0.44 × 0.28 mm |
Enraf-Nonius MACH-3 four-circle diffractometer | 3300 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.003 |
Graphite monochromator | θmax = 27.5°, θmin = 1.4° |
ω scans | h = 0→10 |
Absorption correction: ψ scan (WinGX; Farrugia, 1999) | k = −9→10 |
Tmin = 0.386, Tmax = 0.662 | l = −18→18 |
4006 measured reflections | 3 standard reflections every 90 min |
3934 independent reflections | intensity decay: none |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.071P)2 + 1.433P] where P = (Fo2 + 2Fc2)/3 |
3934 reflections | (Δ/σ)max = 0.001 |
186 parameters | Δρmax = 1.22 e Å−3 |
0 restraints | Δρmin = −0.91 e Å−3 |
[Ru(C7H7NO)(C2H6OS)2Cl2] | γ = 63.53 (5)° |
Mr = 449.36 | V = 858.6 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.177 (5) Å | Mo Kα radiation |
b = 8.214 (3) Å | µ = 1.47 mm−1 |
c = 14.456 (6) Å | T = 298 K |
α = 84.69 (3)° | 0.48 × 0.44 × 0.28 mm |
β = 81.13 (4)° |
Enraf-Nonius MACH-3 four-circle diffractometer | 3300 reflections with I > 2σ(I) |
Absorption correction: ψ scan (WinGX; Farrugia, 1999) | Rint = 0.003 |
Tmin = 0.386, Tmax = 0.662 | 3 standard reflections every 90 min |
4006 measured reflections | intensity decay: none |
3934 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.118 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.22 e Å−3 |
3934 reflections | Δρmin = −0.91 e Å−3 |
186 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 | ||
Ru | 0.31554 (4) | 0.33029 (4) | 0.25515 (2) | 0.02843 (12) | |
Cl1 | 0.50587 (19) | 0.47984 (17) | 0.20563 (10) | 0.0535 (3) | |
Cl2 | 0.12909 (17) | 0.18202 (17) | 0.32330 (8) | 0.0465 (3) | |
S1 | 0.17551 (16) | 0.41105 (15) | 0.12458 (7) | 0.0378 (2) | |
S2 | 0.53627 (15) | 0.06717 (14) | 0.20067 (7) | 0.0370 (2) | |
O1 | 0.1159 (4) | 0.5782 (4) | 0.3084 (2) | 0.0390 (7) | |
N1 | 0.3801 (5) | 0.3254 (4) | 0.3923 (2) | 0.0324 (7) | |
O3 | 0.6682 (5) | −0.0469 (5) | 0.2643 (3) | 0.0580 (10) | |
O2 | 0.2271 (6) | 0.2893 (5) | 0.0457 (2) | 0.0583 (10) | |
C1 | 0.5106 (6) | 0.1945 (6) | 0.4364 (3) | 0.0407 (10) | |
H1 | 0.5940 | 0.0917 | 0.4034 | 0.049* | |
C2 | 0.5280 (7) | 0.2040 (6) | 0.5288 (3) | 0.0451 (11) | |
H2 | 0.6216 | 0.1089 | 0.5569 | 0.054* | |
C3 | 0.4089 (7) | 0.3515 (7) | 0.5786 (3) | 0.0464 (11) | |
H3 | 0.4178 | 0.3585 | 0.6414 | 0.056* | |
C4 | 0.2733 (7) | 0.4921 (6) | 0.5340 (3) | 0.0409 (10) | |
H4 | 0.1906 | 0.5963 | 0.5661 | 0.049* | |
C5 | 0.2629 (6) | 0.4749 (5) | 0.4411 (3) | 0.0331 (8) | |
C6 | 0.1235 (6) | 0.6139 (6) | 0.3878 (3) | 0.0348 (8) | |
C7 | −0.0035 (7) | 0.7959 (6) | 0.4244 (3) | 0.0474 (11) | |
H7A | 0.0660 | 0.8595 | 0.4345 | 0.071* | |
H7B | −0.0718 | 0.7829 | 0.4825 | 0.071* | |
H7C | −0.0873 | 0.8635 | 0.3799 | 0.071* | |
C8 | 0.1775 (12) | 0.6157 (8) | 0.0752 (5) | 0.081 (2) | |
H8A | 0.3019 | 0.5948 | 0.0530 | 0.122* | |
H8B | 0.1261 | 0.7071 | 0.1220 | 0.122* | |
H8C | 0.1055 | 0.6563 | 0.0239 | 0.122* | |
C9 | −0.0629 (7) | 0.4888 (11) | 0.1579 (4) | 0.0729 (19) | |
H9A | −0.1264 | 0.5379 | 0.1039 | 0.109* | |
H9B | −0.1050 | 0.5817 | 0.2034 | 0.109* | |
H9C | −0.0874 | 0.3893 | 0.1846 | 0.109* | |
C10 | 0.6662 (8) | 0.0939 (8) | 0.0948 (4) | 0.0610 (15) | |
H10A | 0.7376 | 0.1540 | 0.1072 | 0.092* | |
H10B | 0.5841 | 0.1657 | 0.0503 | 0.092* | |
H10C | 0.7472 | −0.0234 | 0.0696 | 0.092* | |
C11 | 0.4511 (8) | −0.0738 (6) | 0.1603 (4) | 0.0538 (13) | |
H11A | 0.5516 | −0.1768 | 0.1299 | 0.081* | |
H11B | 0.3655 | −0.0060 | 0.1166 | 0.081* | |
H11C | 0.3898 | −0.1151 | 0.2124 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru | 0.03304 (18) | 0.02725 (17) | 0.02383 (17) | −0.01049 (13) | −0.00832 (12) | −0.00178 (11) |
Cl1 | 0.0623 (8) | 0.0494 (6) | 0.0621 (8) | −0.0359 (6) | −0.0107 (6) | 0.0003 (6) |
Cl2 | 0.0461 (6) | 0.0539 (7) | 0.0416 (6) | −0.0253 (5) | −0.0023 (5) | 0.0003 (5) |
S1 | 0.0436 (6) | 0.0367 (5) | 0.0284 (5) | −0.0110 (5) | −0.0127 (4) | −0.0002 (4) |
S2 | 0.0399 (6) | 0.0304 (5) | 0.0336 (5) | −0.0081 (4) | −0.0056 (4) | −0.0050 (4) |
O1 | 0.0384 (16) | 0.0295 (14) | 0.0373 (16) | −0.0008 (12) | −0.0140 (13) | −0.0044 (12) |
N1 | 0.0348 (17) | 0.0314 (16) | 0.0292 (16) | −0.0106 (14) | −0.0106 (14) | −0.0023 (13) |
O3 | 0.056 (2) | 0.0433 (19) | 0.053 (2) | 0.0021 (17) | −0.0166 (17) | −0.0099 (16) |
O2 | 0.073 (2) | 0.0497 (19) | 0.0339 (17) | −0.0038 (18) | −0.0203 (17) | −0.0117 (14) |
C1 | 0.046 (2) | 0.034 (2) | 0.038 (2) | −0.0097 (19) | −0.0175 (19) | −0.0053 (17) |
C2 | 0.055 (3) | 0.043 (2) | 0.039 (2) | −0.018 (2) | −0.024 (2) | 0.0058 (19) |
C3 | 0.064 (3) | 0.058 (3) | 0.028 (2) | −0.034 (3) | −0.019 (2) | 0.0035 (19) |
C4 | 0.050 (3) | 0.043 (2) | 0.032 (2) | −0.021 (2) | −0.0054 (18) | −0.0082 (17) |
C5 | 0.033 (2) | 0.0311 (19) | 0.034 (2) | −0.0118 (17) | −0.0079 (16) | −0.0019 (15) |
C6 | 0.034 (2) | 0.033 (2) | 0.035 (2) | −0.0122 (17) | −0.0061 (17) | −0.0037 (16) |
C7 | 0.050 (3) | 0.036 (2) | 0.044 (3) | −0.006 (2) | −0.009 (2) | −0.0082 (19) |
C8 | 0.127 (6) | 0.057 (3) | 0.076 (4) | −0.047 (4) | −0.056 (4) | 0.036 (3) |
C9 | 0.038 (3) | 0.112 (5) | 0.051 (3) | −0.012 (3) | −0.019 (2) | −0.006 (3) |
C10 | 0.058 (3) | 0.055 (3) | 0.054 (3) | −0.016 (3) | 0.016 (3) | −0.010 (2) |
C11 | 0.071 (4) | 0.034 (2) | 0.056 (3) | −0.019 (2) | −0.014 (3) | −0.010 (2) |
Ru—O1 | 2.084 (3) | C3—H3 | 0.9300 |
Ru—N1 | 2.122 (3) | C4—C5 | 1.384 (6) |
Ru—S1 | 2.2520 (15) | C4—H4 | 0.9300 |
Ru—S2 | 2.225 (2) | C5—C6 | 1.464 (6) |
Ru—Cl1 | 2.3753 (16) | C6—C7 | 1.478 (6) |
Ru—Cl2 | 2.3977 (16) | C7—H7A | 0.9600 |
S2—O3 | 1.461 (4) | C7—H7B | 0.9600 |
S2—C11 | 1.771 (5) | C7—H7C | 0.9600 |
S2—C10 | 1.779 (5) | C8—H8A | 0.9600 |
S1—O2 | 1.472 (3) | C8—H8B | 0.9600 |
S1—C9 | 1.760 (6) | C8—H8C | 0.9600 |
S1—C8 | 1.771 (6) | C9—H9A | 0.9600 |
O1—C6 | 1.228 (5) | C9—H9B | 0.9600 |
N1—C1 | 1.327 (5) | C9—H9C | 0.9600 |
N1—C5 | 1.351 (5) | C10—H10A | 0.9600 |
C1—C2 | 1.378 (6) | C10—H10B | 0.9600 |
C1—H1 | 0.9300 | C10—H10C | 0.9600 |
C2—C3 | 1.353 (7) | C11—H11A | 0.9600 |
C2—H2 | 0.9300 | C11—H11B | 0.9600 |
C3—C4 | 1.386 (7) | C11—H11C | 0.9600 |
O1—Ru—N1 | 76.59 (13) | C5—C4—C3 | 118.9 (4) |
O1—Ru—S1 | 86.62 (10) | C5—C4—H4 | 120.5 |
O1—Ru—S2 | 177.91 (9) | C3—C4—H4 | 120.5 |
O1—Ru—Cl1 | 87.16 (11) | N1—C5—C4 | 122.3 (4) |
O1—Ru—Cl2 | 90.69 (11) | N1—C5—C6 | 114.4 (4) |
N1—Ru—S1 | 163.12 (10) | C4—C5—C6 | 123.4 (4) |
N1—Ru—S2 | 101.85 (11) | O1—C6—C5 | 118.1 (4) |
N1—Ru—Cl1 | 87.05 (10) | O1—C6—C7 | 119.1 (4) |
N1—Ru—Cl2 | 86.33 (10) | C5—C6—C7 | 122.9 (4) |
S1—Ru—S2 | 94.98 (6) | C6—C7—H7A | 109.5 |
S1—Ru—Cl1 | 93.94 (6) | C6—C7—H7B | 109.5 |
S1—Ru—Cl2 | 92.21 (6) | H7A—C7—H7B | 109.5 |
S2—Ru—Cl1 | 91.38 (6) | C6—C7—H7C | 109.5 |
S2—Ru—Cl2 | 90.60 (6) | H7A—C7—H7C | 109.5 |
Cl1—Ru—Cl2 | 173.35 (4) | H7B—C7—H7C | 109.5 |
O3—S2—C11 | 106.0 (2) | S1—C8—H8A | 109.5 |
O3—S2—C10 | 107.0 (3) | S1—C8—H8B | 109.5 |
C11—S2—C10 | 99.1 (3) | H8A—C8—H8B | 109.5 |
O3—S2—Ru | 116.79 (15) | S1—C8—H8C | 109.5 |
C11—S2—Ru | 113.4 (2) | H8A—C8—H8C | 109.5 |
C10—S2—Ru | 112.85 (19) | H8B—C8—H8C | 109.5 |
O2—S1—C9 | 107.0 (3) | S1—C9—H9A | 109.5 |
O2—S1—C8 | 105.9 (3) | S1—C9—H9B | 109.5 |
C9—S1—C8 | 99.4 (4) | H9A—C9—H9B | 109.5 |
O2—S1—Ru | 123.42 (16) | S1—C9—H9C | 109.5 |
C9—S1—Ru | 108.3 (2) | H9A—C9—H9C | 109.5 |
C8—S1—Ru | 110.2 (2) | H9B—C9—H9C | 109.5 |
C6—O1—Ru | 117.4 (3) | S2—C10—H10A | 109.5 |
C1—N1—C5 | 117.5 (4) | S2—C10—H10B | 109.5 |
C1—N1—Ru | 129.1 (3) | H10A—C10—H10B | 109.5 |
C5—N1—Ru | 113.3 (3) | S2—C10—H10C | 109.5 |
N1—C1—C2 | 122.9 (4) | H10A—C10—H10C | 109.5 |
N1—C1—H1 | 118.6 | H10B—C10—H10C | 109.5 |
C2—C1—H1 | 118.6 | S2—C11—H11A | 109.5 |
C3—C2—C1 | 120.0 (4) | S2—C11—H11B | 109.5 |
C3—C2—H2 | 120.0 | H11A—C11—H11B | 109.5 |
C1—C2—H2 | 120.0 | S2—C11—H11C | 109.5 |
C2—C3—C4 | 118.5 (4) | H11A—C11—H11C | 109.5 |
C2—C3—H3 | 120.8 | H11B—C11—H11C | 109.5 |
C4—C3—H3 | 120.8 |
Experimental details
Crystal data | |
Chemical formula | [Ru(C7H7NO)(C2H6OS)2Cl2] |
Mr | 449.36 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.177 (5), 8.214 (3), 14.456 (6) |
α, β, γ (°) | 84.69 (3), 81.13 (4), 63.53 (5) |
V (Å3) | 858.6 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.47 |
Crystal size (mm) | 0.48 × 0.44 × 0.28 |
Data collection | |
Diffractometer | Enraf-Nonius MACH-3 four-circle diffractometer |
Absorption correction | ψ scan (WinGX; Farrugia, 1999) |
Tmin, Tmax | 0.386, 0.662 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4006, 3934, 3300 |
Rint | 0.003 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.118, 1.03 |
No. of reflections | 3934 |
No. of parameters | 186 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.22, −0.91 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, WinGX (Farrugia, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX6a (McArdle, 1995), SHELXL97.
Ru—O1 | 2.084 (3) | Ru—S2 | 2.225 (2) |
Ru—N1 | 2.122 (3) | Ru—Cl1 | 2.3753 (16) |
Ru—S1 | 2.2520 (15) | Ru—Cl2 | 2.3977 (16) |
O1—Ru—N1 | 76.59 (13) | N1—Ru—Cl2 | 86.33 (10) |
O1—Ru—S1 | 86.62 (10) | S1—Ru—S2 | 94.98 (6) |
O1—Ru—S2 | 177.91 (9) | S1—Ru—Cl1 | 93.94 (6) |
O1—Ru—Cl1 | 87.16 (11) | S1—Ru—Cl2 | 92.21 (6) |
O1—Ru—Cl2 | 90.69 (11) | S2—Ru—Cl1 | 91.38 (6) |
N1—Ru—S1 | 163.12 (10) | S2—Ru—Cl2 | 90.60 (6) |
N1—Ru—S2 | 101.85 (11) | Cl1—Ru—Cl2 | 173.35 (4) |
N1—Ru—Cl1 | 87.05 (10) |
Dimethyl sulfoxide (dmso) is an ambidentate ligand, in that it can bind a metal ion via the O or the S atom. Interest in complexes with this ligand is primarily directed towards gaining an understanding of the nature of the bond between the metal and the coordinating atom (Calligaris & Carugo, 1996; Sano & Taube, 1994). In general, coordination via O is preferred by harder high-valent metal ions, while S-coordination is favoured by softer low-valent ones. Although dmso-containing ruthenium complexes have been known for some time (Evans et al., 1973), the recent discovery of anticancer activity (Smith et al., 1996) displayed by haloruthenium(sulfoxide) species has revived interest in such complexes (Rack & Gray, 1999; Cingi et al., 2000) and prompted further scrutiny of the bonding of dmso to Ru. Here, we report the synthesis, characterization data and molecular structure of a relevant new complex, [RuCl2(apy)(dmso)2], (I), containing 2-acetylpyridine (apy) as the ancillary ligand. \sch
The molecular structure of (I) is depicted in Fig. 1. The bond parameters associated with the RuII centre indicate a distorted octahedral NOCl2S2 coordination sphere around the metal ion. The two S-coordinated dmso molecules and the two Cl- ions in the coordination sphere are found to be cis and trans pairs, respectively. The two remaining cis sites are occupied by the chelating N,O-donor 2-acetylpyridine, with a chelate bite angle of 76.59 (13)°.
The Ru—O [2.084 (3) Å] and Ru—N [2.122 (3) Å] bond lengths in (I) are similar to those of known RuII to keto-O (Basuli et al., 2000) and pyridine-N bonds (Bellachioma et al., 1998; Sengupta et al., 2001). The Ru—Cl distances of 2.3753 (16) and 2.3977 (16) Å are unexceptional (Cingi et al., 2000; Alessio et al., 2000).
The Cl1—Ru—Cl2 bond angle of 173.35 (4)° deviates noticeably from the ideal value of 180°. The deviation of the S1—Ru—S2 bond angle [94.98 (6)°] from 90° is most probably due to the steric repulsion between the dmso molecules, with the larger angle being accommodated by the small chelate angle of apy.
The Ru—S bond lengths are significantly different: Ru—S1 2.2520 (15) and Ru—S2 2.225 (2) Å. The longer value is possibly the consequence of the better trans-directing ability of the pyridine N atom compared with that of the keto O atom. However, in the coordinated dmso molecules of (I), the corresponding S—O bond lengths [1.472 (3) and 1.461 (4) Å] are comparable. In general, the Ru—S and S—O bond lengths in (I) are well within the range reported for other RuII complexes containing S-coordinated dmso (Alessio et al., 1988, 2000; Cingi et al., 2000).