Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009395/ob6241sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009395/ob6241Isup2.hkl |
CCDC reference: 214769
The mother liquor from the recrystallization of the cis(Cl,Namino)- and trans(Cl,Namino)- mixture of [RuCl(dimethyl sulfoxide){tris(2-pyridylmethyl)amine}]Cl (Yamaguchi et al., 1997) was evaporated. The residue was redissolved in a mixture of methanol and ethyl acetate (1:9 v/v). The solution was stored at room temperature for a month. A yellow crystal of (I) deposited and was chosed for X-ray crystallographic analysis.
All H atoms bonded to C atoms were included in calculated positions, with C—H distances of 0.95 Å for aromatic H atoms, 0.99 Å for benzyl (picolinic) H atoms, and 0.98 Å for methyl.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. ORTEP-3 diagram (Farrugia, 1997) of the title compound, showing 50% displacement ellipsoids for non-H atoms. |
[RuCl(C18H18N4)(C2H6OS)][RuCl3(C2H6OS)3] | Z = 2 |
Mr = 946.82 | F(000) = 956 |
Triclinic, P1 | Dx = 1.749 Mg m−3 |
a = 10.1817 (18) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.221 (2) Å | Cell parameters from 965 reflections |
c = 14.664 (3) Å | θ = 3.0–23.3° |
α = 114.362 (3)° | µ = 1.41 mm−1 |
β = 96.804 (3)° | T = 173 K |
γ = 105.610 (3)° | Block, yellow |
V = 1798.1 (5) Å3 | 0.2 × 0.1 × 0.08 mm |
Bruker SMART CCD area-detector diffractometer | 4463 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 23.3°, θmin = 1.7° |
Detector resolution: 66 pixels mm-1 | h = −11→11 |
ϕ and ω scans | k = −15→14 |
8007 measured reflections | l = −9→16 |
5113 independent 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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0351P)2] where P = (Fo2 + 2Fc2)/3 |
5113 reflections | (Δ/σ)max = 0.001 |
405 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[RuCl(C18H18N4)(C2H6OS)][RuCl3(C2H6OS)3] | γ = 105.610 (3)° |
Mr = 946.82 | V = 1798.1 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.1817 (18) Å | Mo Kα radiation |
b = 14.221 (2) Å | µ = 1.41 mm−1 |
c = 14.664 (3) Å | T = 173 K |
α = 114.362 (3)° | 0.2 × 0.1 × 0.08 mm |
β = 96.804 (3)° |
Bruker SMART CCD area-detector diffractometer | 4463 reflections with I > 2σ(I) |
8007 measured reflections | Rint = 0.017 |
5113 independent reflections | θmax = 23.3° |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.066 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.61 e Å−3 |
5113 reflections | Δρmin = −0.41 e Å−3 |
405 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 | 0.94404 (3) | 0.26718 (2) | 0.19393 (2) | 0.01765 (9) | |
Ru2 | 0.64713 (3) | 0.77621 (2) | 0.27378 (2) | 0.02115 (9) | |
Cl1 | 0.99931 (10) | 0.43392 (7) | 0.17406 (7) | 0.0280 (2) | |
Cl2 | 0.87081 (10) | 0.89068 (7) | 0.27084 (8) | 0.0301 (2) | |
Cl3 | 0.57378 (10) | 0.70663 (8) | 0.08719 (7) | 0.0337 (2) | |
Cl4 | 0.55015 (10) | 0.92113 (8) | 0.29152 (8) | 0.0347 (2) | |
S1 | 0.95539 (9) | 0.17457 (7) | 0.03095 (7) | 0.0219 (2) | |
S2 | 0.43425 (10) | 0.65979 (7) | 0.25802 (8) | 0.0276 (2) | |
S3 | 0.71379 (10) | 0.86161 (7) | 0.44985 (7) | 0.0286 (2) | |
S4 | 0.74849 (10) | 0.64883 (7) | 0.25982 (7) | 0.0251 (2) | |
N1 | 1.1529 (3) | 0.2938 (2) | 0.2560 (2) | 0.0183 (6) | |
N2 | 0.9007 (3) | 0.3445 (2) | 0.3380 (2) | 0.0185 (6) | |
N3 | 0.7268 (3) | 0.2039 (2) | 0.1430 (2) | 0.0217 (7) | |
N4 | 0.9127 (3) | 0.1408 (2) | 0.2340 (2) | 0.0192 (6) | |
O1 | 0.8887 (3) | 0.05295 (18) | −0.02215 (18) | 0.0289 (6) | |
O2 | 0.4046 (3) | 0.6436 (2) | 0.3474 (2) | 0.0371 (7) | |
O3 | 0.7967 (3) | 0.8213 (2) | 0.5049 (2) | 0.0395 (7) | |
O4 | 0.6809 (3) | 0.5612 (2) | 0.2865 (2) | 0.0400 (7) | |
C1 | 1.2675 (4) | 0.3843 (3) | 0.2914 (3) | 0.0224 (8) | |
H1 | 1.2570 | 0.4473 | 0.2880 | 0.027* | |
C2 | 1.4001 (4) | 0.3905 (3) | 0.3328 (3) | 0.0300 (9) | |
H2 | 1.4796 | 0.4560 | 0.3566 | 0.036* | |
C3 | 1.4146 (4) | 0.3001 (3) | 0.3388 (3) | 0.0344 (10) | |
H3 | 1.5048 | 0.3020 | 0.3670 | 0.041* | |
C4 | 1.2976 (4) | 0.2065 (3) | 0.3036 (3) | 0.0289 (9) | |
H4 | 1.3066 | 0.1436 | 0.3081 | 0.035* | |
C5 | 1.1686 (4) | 0.2041 (3) | 0.2623 (3) | 0.0205 (8) | |
C6 | 1.0357 (4) | 0.1031 (3) | 0.2176 (3) | 0.0224 (8) | |
H6A | 1.0238 | 0.0581 | 0.1426 | 0.027* | |
H6B | 1.0420 | 0.0573 | 0.2525 | 0.027* | |
C7 | 0.8652 (4) | 0.4347 (3) | 0.3703 (3) | 0.0247 (8) | |
H7 | 0.8818 | 0.4780 | 0.3350 | 0.030* | |
C8 | 0.8056 (4) | 0.4677 (3) | 0.4527 (3) | 0.0278 (9) | |
H8 | 0.7851 | 0.5338 | 0.4753 | 0.033* | |
C9 | 0.7766 (4) | 0.4028 (3) | 0.5015 (3) | 0.0298 (9) | |
H9 | 0.7340 | 0.4230 | 0.5576 | 0.036* | |
C10 | 0.8099 (4) | 0.3082 (3) | 0.4679 (3) | 0.0273 (9) | |
H10 | 0.7912 | 0.2626 | 0.5009 | 0.033* | |
C11 | 0.8710 (3) | 0.2806 (3) | 0.3858 (3) | 0.0204 (8) | |
C12 | 0.9146 (4) | 0.1819 (3) | 0.3467 (3) | 0.0243 (8) | |
H12A | 0.8496 | 0.1225 | 0.3557 | 0.029* | |
H12B | 1.0110 | 0.2012 | 0.3878 | 0.029* | |
C13 | 0.6383 (4) | 0.2505 (3) | 0.1193 (3) | 0.0265 (9) | |
H13 | 0.6770 | 0.3179 | 0.1170 | 0.032* | |
C14 | 0.4936 (4) | 0.2042 (3) | 0.0981 (3) | 0.0298 (9) | |
H14 | 0.4337 | 0.2375 | 0.0787 | 0.036* | |
C15 | 0.4375 (4) | 0.1092 (3) | 0.1054 (3) | 0.0295 (9) | |
H15 | 0.3382 | 0.0767 | 0.0927 | 0.035* | |
C16 | 0.5273 (4) | 0.0610 (3) | 0.1317 (3) | 0.0246 (8) | |
H16 | 0.4903 | −0.0039 | 0.1386 | 0.030* | |
C17 | 0.6703 (4) | 0.1079 (3) | 0.1477 (3) | 0.0209 (8) | |
C18 | 0.7732 (4) | 0.0544 (3) | 0.1653 (3) | 0.0231 (8) | |
H18A | 0.7354 | 0.0081 | 0.1980 | 0.028* | |
H18B | 0.7859 | 0.0063 | 0.0980 | 0.028* | |
C19 | 1.1303 (4) | 0.2057 (3) | 0.0150 (3) | 0.0311 (9) | |
H19A | 1.1841 | 0.1764 | 0.0496 | 0.047* | |
H19B | 1.1767 | 0.2858 | 0.0458 | 0.047* | |
H19C | 1.1263 | 0.1720 | −0.0590 | 0.047* | |
C20 | 0.8780 (5) | 0.2169 (3) | −0.0542 (3) | 0.0407 (11) | |
H20A | 0.8891 | 0.1768 | −0.1237 | 0.061* | |
H20B | 0.9251 | 0.2963 | −0.0283 | 0.061* | |
H20C | 0.7773 | 0.2009 | −0.0572 | 0.061* | |
C21 | 0.3902 (4) | 0.5250 (3) | 0.1532 (3) | 0.0373 (10) | |
H21A | 0.4479 | 0.4872 | 0.1716 | 0.056* | |
H21B | 0.4084 | 0.5308 | 0.0912 | 0.056* | |
H21C | 0.2900 | 0.4831 | 0.1391 | 0.056* | |
C22 | 0.2927 (4) | 0.6932 (4) | 0.2111 (4) | 0.0542 (13) | |
H22A | 0.2024 | 0.6380 | 0.2002 | 0.081* | |
H22B | 0.3003 | 0.6938 | 0.1453 | 0.081* | |
H22C | 0.2976 | 0.7662 | 0.2620 | 0.081* | |
C23 | 0.5703 (4) | 0.8760 (3) | 0.5071 (3) | 0.0373 (10) | |
H23A | 0.5147 | 0.8050 | 0.5015 | 0.056* | |
H23B | 0.5100 | 0.8999 | 0.4707 | 0.056* | |
H23C | 0.6074 | 0.9310 | 0.5803 | 0.056* | |
C24 | 0.8108 (5) | 1.0056 (3) | 0.4998 (3) | 0.0449 (11) | |
H24A | 0.8408 | 1.0404 | 0.5757 | 0.067* | |
H24B | 0.7505 | 1.0402 | 0.4785 | 0.067* | |
H24C | 0.8941 | 1.0149 | 0.4725 | 0.067* | |
C25 | 0.7701 (5) | 0.5813 (3) | 0.1329 (3) | 0.0432 (11) | |
H25A | 0.8282 | 0.5363 | 0.1326 | 0.065* | |
H25B | 0.8167 | 0.6365 | 0.1124 | 0.065* | |
H25C | 0.6773 | 0.5339 | 0.0839 | 0.065* | |
C26 | 0.9288 (4) | 0.7058 (3) | 0.3312 (3) | 0.0351 (10) | |
H26A | 0.9354 | 0.7422 | 0.4056 | 0.053* | |
H26B | 0.9822 | 0.7598 | 0.3117 | 0.053* | |
H26C | 0.9681 | 0.6468 | 0.3157 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01933 (17) | 0.01801 (16) | 0.02149 (17) | 0.00828 (13) | 0.00947 (13) | 0.01239 (13) |
Ru2 | 0.02429 (18) | 0.02137 (17) | 0.02435 (18) | 0.00811 (14) | 0.00873 (13) | 0.01590 (14) |
Cl1 | 0.0309 (5) | 0.0255 (5) | 0.0403 (6) | 0.0135 (4) | 0.0167 (4) | 0.0229 (5) |
Cl2 | 0.0286 (5) | 0.0267 (5) | 0.0422 (6) | 0.0076 (4) | 0.0125 (4) | 0.0230 (5) |
Cl3 | 0.0358 (6) | 0.0466 (6) | 0.0275 (5) | 0.0129 (5) | 0.0100 (4) | 0.0256 (5) |
Cl4 | 0.0400 (6) | 0.0363 (5) | 0.0487 (6) | 0.0217 (5) | 0.0218 (5) | 0.0310 (5) |
S1 | 0.0229 (5) | 0.0245 (5) | 0.0226 (5) | 0.0091 (4) | 0.0094 (4) | 0.0136 (4) |
S2 | 0.0272 (5) | 0.0295 (5) | 0.0327 (6) | 0.0079 (4) | 0.0106 (4) | 0.0209 (5) |
S3 | 0.0364 (6) | 0.0264 (5) | 0.0247 (5) | 0.0112 (5) | 0.0089 (4) | 0.0131 (4) |
S4 | 0.0296 (5) | 0.0220 (5) | 0.0281 (5) | 0.0098 (4) | 0.0074 (4) | 0.0153 (4) |
N1 | 0.0219 (17) | 0.0181 (15) | 0.0159 (16) | 0.0061 (14) | 0.0076 (13) | 0.0085 (13) |
N2 | 0.0170 (16) | 0.0172 (15) | 0.0192 (16) | 0.0038 (13) | 0.0052 (13) | 0.0078 (13) |
N3 | 0.0228 (17) | 0.0252 (16) | 0.0208 (17) | 0.0100 (14) | 0.0091 (13) | 0.0122 (14) |
N4 | 0.0202 (17) | 0.0180 (15) | 0.0243 (17) | 0.0080 (13) | 0.0087 (13) | 0.0126 (14) |
O1 | 0.0293 (15) | 0.0252 (14) | 0.0273 (15) | 0.0059 (12) | 0.0104 (12) | 0.0092 (12) |
O2 | 0.0477 (18) | 0.0333 (15) | 0.0301 (16) | 0.0061 (14) | 0.0182 (14) | 0.0173 (13) |
O3 | 0.0516 (19) | 0.0447 (17) | 0.0269 (16) | 0.0223 (15) | 0.0064 (13) | 0.0185 (14) |
O4 | 0.0423 (18) | 0.0350 (16) | 0.058 (2) | 0.0143 (14) | 0.0147 (15) | 0.0348 (15) |
C1 | 0.026 (2) | 0.0186 (19) | 0.022 (2) | 0.0044 (17) | 0.0095 (17) | 0.0098 (16) |
C2 | 0.021 (2) | 0.029 (2) | 0.028 (2) | −0.0037 (18) | 0.0014 (17) | 0.0112 (19) |
C3 | 0.023 (2) | 0.048 (3) | 0.037 (3) | 0.011 (2) | 0.0022 (18) | 0.025 (2) |
C4 | 0.029 (2) | 0.038 (2) | 0.035 (2) | 0.0154 (19) | 0.0122 (18) | 0.028 (2) |
C5 | 0.026 (2) | 0.0240 (19) | 0.019 (2) | 0.0112 (17) | 0.0119 (16) | 0.0137 (17) |
C6 | 0.023 (2) | 0.0199 (19) | 0.028 (2) | 0.0115 (16) | 0.0095 (17) | 0.0117 (17) |
C7 | 0.023 (2) | 0.023 (2) | 0.031 (2) | 0.0091 (17) | 0.0079 (17) | 0.0144 (18) |
C8 | 0.027 (2) | 0.023 (2) | 0.028 (2) | 0.0103 (18) | 0.0116 (18) | 0.0057 (18) |
C9 | 0.030 (2) | 0.032 (2) | 0.022 (2) | 0.0100 (19) | 0.0117 (18) | 0.0066 (18) |
C10 | 0.029 (2) | 0.030 (2) | 0.024 (2) | 0.0060 (18) | 0.0099 (18) | 0.0155 (18) |
C11 | 0.0172 (19) | 0.0207 (19) | 0.020 (2) | 0.0030 (16) | 0.0031 (16) | 0.0097 (17) |
C12 | 0.030 (2) | 0.027 (2) | 0.026 (2) | 0.0137 (18) | 0.0134 (17) | 0.0178 (18) |
C13 | 0.030 (2) | 0.030 (2) | 0.031 (2) | 0.0142 (18) | 0.0117 (18) | 0.0208 (19) |
C14 | 0.022 (2) | 0.043 (2) | 0.036 (2) | 0.0182 (19) | 0.0107 (18) | 0.024 (2) |
C15 | 0.018 (2) | 0.042 (2) | 0.027 (2) | 0.0085 (19) | 0.0077 (17) | 0.016 (2) |
C16 | 0.021 (2) | 0.027 (2) | 0.021 (2) | 0.0018 (17) | 0.0072 (16) | 0.0096 (17) |
C17 | 0.025 (2) | 0.0216 (19) | 0.018 (2) | 0.0086 (17) | 0.0084 (16) | 0.0099 (16) |
C18 | 0.025 (2) | 0.0234 (19) | 0.028 (2) | 0.0102 (17) | 0.0132 (17) | 0.0159 (18) |
C19 | 0.026 (2) | 0.035 (2) | 0.027 (2) | 0.0054 (18) | 0.0130 (18) | 0.0112 (19) |
C20 | 0.051 (3) | 0.050 (3) | 0.031 (2) | 0.025 (2) | 0.010 (2) | 0.024 (2) |
C21 | 0.038 (3) | 0.036 (2) | 0.027 (2) | −0.001 (2) | 0.0063 (19) | 0.013 (2) |
C22 | 0.024 (3) | 0.065 (3) | 0.092 (4) | 0.013 (2) | 0.011 (2) | 0.055 (3) |
C23 | 0.050 (3) | 0.041 (2) | 0.032 (2) | 0.023 (2) | 0.022 (2) | 0.020 (2) |
C24 | 0.055 (3) | 0.028 (2) | 0.038 (3) | 0.005 (2) | 0.009 (2) | 0.009 (2) |
C25 | 0.055 (3) | 0.044 (3) | 0.031 (3) | 0.031 (2) | 0.012 (2) | 0.010 (2) |
C26 | 0.030 (2) | 0.033 (2) | 0.046 (3) | 0.0136 (19) | 0.0057 (19) | 0.022 (2) |
Ru1—N3 | 2.060 (3) | C7—H7 | 0.9500 |
Ru1—N4 | 2.070 (3) | C8—C9 | 1.378 (5) |
Ru1—N1 | 2.078 (3) | C8—H8 | 0.9500 |
Ru1—N2 | 2.106 (3) | C9—C10 | 1.382 (5) |
Ru1—S1 | 2.2385 (10) | C9—H9 | 0.9500 |
Ru1—Cl1 | 2.4321 (9) | C10—C11 | 1.382 (5) |
Ru2—S2 | 2.2643 (10) | C10—H10 | 0.9500 |
Ru2—S4 | 2.2668 (9) | C11—C12 | 1.493 (5) |
Ru2—S3 | 2.2707 (11) | C12—H12A | 0.9900 |
Ru2—Cl3 | 2.4307 (11) | C12—H12B | 0.9900 |
Ru2—Cl2 | 2.4341 (9) | C13—C14 | 1.379 (5) |
Ru2—Cl4 | 2.4503 (10) | C13—H13 | 0.9500 |
S1—O1 | 1.480 (2) | C14—C15 | 1.372 (5) |
S1—C19 | 1.784 (3) | C14—H14 | 0.9500 |
S1—C20 | 1.784 (4) | C15—C16 | 1.388 (5) |
S2—O2 | 1.472 (2) | C15—H15 | 0.9500 |
S2—C22 | 1.783 (4) | C16—C17 | 1.373 (5) |
S2—C21 | 1.784 (4) | C16—H16 | 0.9500 |
S3—O3 | 1.474 (3) | C17—C18 | 1.507 (5) |
S3—C23 | 1.786 (4) | C18—H18A | 0.9900 |
S3—C24 | 1.791 (4) | C18—H18B | 0.9900 |
S4—O4 | 1.478 (2) | C19—H19A | 0.9800 |
S4—C26 | 1.780 (4) | C19—H19B | 0.9800 |
S4—C25 | 1.780 (4) | C19—H19C | 0.9800 |
N1—C1 | 1.336 (4) | C20—H20A | 0.9800 |
N1—C5 | 1.366 (4) | C20—H20B | 0.9800 |
N2—C7 | 1.338 (4) | C20—H20C | 0.9800 |
N2—C11 | 1.355 (4) | C21—H21A | 0.9800 |
N3—C13 | 1.344 (4) | C21—H21B | 0.9800 |
N3—C17 | 1.365 (4) | C21—H21C | 0.9800 |
N4—C6 | 1.497 (4) | C22—H22A | 0.9800 |
N4—C18 | 1.497 (4) | C22—H22B | 0.9800 |
N4—C12 | 1.503 (4) | C22—H22C | 0.9800 |
C1—C2 | 1.377 (5) | C23—H23A | 0.9800 |
C1—H1 | 0.9500 | C23—H23B | 0.9800 |
C2—C3 | 1.370 (5) | C23—H23C | 0.9800 |
C2—H2 | 0.9500 | C24—H24A | 0.9800 |
C3—C4 | 1.375 (5) | C24—H24B | 0.9800 |
C3—H3 | 0.9500 | C24—H24C | 0.9800 |
C4—C5 | 1.366 (5) | C25—H25A | 0.9800 |
C4—H4 | 0.9500 | C25—H25B | 0.9800 |
C5—C6 | 1.514 (5) | C25—H25C | 0.9800 |
C6—H6A | 0.9900 | C26—H26A | 0.9800 |
C6—H6B | 0.9900 | C26—H26B | 0.9800 |
C7—C8 | 1.382 (5) | C26—H26C | 0.9800 |
N3—Ru1—N4 | 82.90 (11) | N2—C7—C8 | 122.8 (3) |
N3—Ru1—N1 | 163.45 (10) | N2—C7—H7 | 118.6 |
N4—Ru1—N1 | 80.55 (10) | C8—C7—H7 | 118.6 |
N3—Ru1—N2 | 82.12 (10) | C9—C8—C7 | 118.7 (3) |
N4—Ru1—N2 | 80.75 (10) | C9—C8—H8 | 120.7 |
N1—Ru1—N2 | 95.40 (10) | C7—C8—H8 | 120.7 |
N3—Ru1—S1 | 89.39 (8) | C8—C9—C10 | 119.3 (3) |
N4—Ru1—S1 | 98.48 (8) | C8—C9—H9 | 120.4 |
N1—Ru1—S1 | 92.81 (7) | C10—C9—H9 | 120.4 |
N2—Ru1—S1 | 171.51 (8) | C11—C10—C9 | 119.1 (3) |
N3—Ru1—Cl1 | 101.71 (8) | C11—C10—H10 | 120.4 |
N4—Ru1—Cl1 | 171.41 (8) | C9—C10—H10 | 120.4 |
N1—Ru1—Cl1 | 94.73 (7) | N2—C11—C10 | 121.8 (3) |
N2—Ru1—Cl1 | 92.62 (7) | N2—C11—C12 | 115.4 (3) |
S1—Ru1—Cl1 | 88.87 (3) | C10—C11—C12 | 122.7 (3) |
S2—Ru2—S4 | 91.39 (4) | C11—C12—N4 | 111.2 (3) |
S2—Ru2—S3 | 95.66 (4) | C11—C12—H12A | 109.4 |
S4—Ru2—S3 | 93.37 (4) | N4—C12—H12A | 109.4 |
S2—Ru2—Cl3 | 86.94 (3) | C11—C12—H12B | 109.4 |
S4—Ru2—Cl3 | 93.32 (3) | N4—C12—H12B | 109.4 |
S3—Ru2—Cl3 | 172.76 (3) | H12A—C12—H12B | 108.0 |
S2—Ru2—Cl2 | 173.93 (4) | N3—C13—C14 | 122.6 (3) |
S4—Ru2—Cl2 | 87.57 (3) | N3—C13—H13 | 118.7 |
S3—Ru2—Cl2 | 90.37 (4) | C14—C13—H13 | 118.7 |
Cl3—Ru2—Cl2 | 87.15 (3) | C15—C14—C13 | 118.9 (3) |
S2—Ru2—Cl4 | 91.61 (4) | C15—C14—H14 | 120.6 |
S4—Ru2—Cl4 | 176.96 (3) | C13—C14—H14 | 120.6 |
S3—Ru2—Cl4 | 85.81 (3) | C14—C15—C16 | 119.3 (3) |
Cl3—Ru2—Cl4 | 87.37 (3) | C14—C15—H15 | 120.4 |
Cl2—Ru2—Cl4 | 89.51 (3) | C16—C15—H15 | 120.4 |
O1—S1—C19 | 106.78 (15) | C17—C16—C15 | 119.5 (3) |
O1—S1—C20 | 104.51 (17) | C17—C16—H16 | 120.3 |
C19—S1—C20 | 99.28 (19) | C15—C16—H16 | 120.3 |
O1—S1—Ru1 | 118.17 (10) | N3—C17—C16 | 121.4 (3) |
C19—S1—Ru1 | 113.86 (13) | N3—C17—C18 | 115.9 (3) |
C20—S1—Ru1 | 112.22 (14) | C16—C17—C18 | 122.7 (3) |
O2—S2—C22 | 106.60 (19) | N4—C18—C17 | 110.1 (3) |
O2—S2—C21 | 105.86 (16) | N4—C18—H18A | 109.6 |
C22—S2—C21 | 97.8 (2) | C17—C18—H18A | 109.6 |
O2—S2—Ru2 | 119.96 (12) | N4—C18—H18B | 109.6 |
C22—S2—Ru2 | 111.67 (14) | C17—C18—H18B | 109.6 |
C21—S2—Ru2 | 112.47 (13) | H18A—C18—H18B | 108.2 |
O3—S3—C23 | 106.77 (17) | S1—C19—H19A | 109.5 |
O3—S3—C24 | 106.23 (19) | S1—C19—H19B | 109.5 |
C23—S3—C24 | 97.19 (19) | H19A—C19—H19B | 109.5 |
O3—S3—Ru2 | 119.97 (11) | S1—C19—H19C | 109.5 |
C23—S3—Ru2 | 113.30 (15) | H19A—C19—H19C | 109.5 |
C24—S3—Ru2 | 110.79 (14) | H19B—C19—H19C | 109.5 |
O4—S4—C26 | 105.20 (17) | S1—C20—H20A | 109.5 |
O4—S4—C25 | 106.55 (18) | S1—C20—H20B | 109.5 |
C26—S4—C25 | 98.76 (19) | H20A—C20—H20B | 109.5 |
O4—S4—Ru2 | 118.54 (11) | S1—C20—H20C | 109.5 |
C26—S4—Ru2 | 114.13 (13) | H20A—C20—H20C | 109.5 |
C25—S4—Ru2 | 111.56 (14) | H20B—C20—H20C | 109.5 |
C1—N1—C5 | 118.2 (3) | S2—C21—H21A | 109.5 |
C1—N1—Ru1 | 129.5 (2) | S2—C21—H21B | 109.5 |
C5—N1—Ru1 | 112.3 (2) | H21A—C21—H21B | 109.5 |
C7—N2—C11 | 118.2 (3) | S2—C21—H21C | 109.5 |
C7—N2—Ru1 | 124.9 (2) | H21A—C21—H21C | 109.5 |
C11—N2—Ru1 | 114.5 (2) | H21B—C21—H21C | 109.5 |
C13—N3—C17 | 118.3 (3) | S2—C22—H22A | 109.5 |
C13—N3—Ru1 | 128.8 (2) | S2—C22—H22B | 109.5 |
C17—N3—Ru1 | 112.3 (2) | H22A—C22—H22B | 109.5 |
C6—N4—C18 | 113.8 (2) | S2—C22—H22C | 109.5 |
C6—N4—C12 | 108.2 (3) | H22A—C22—H22C | 109.5 |
C18—N4—C12 | 111.3 (2) | H22B—C22—H22C | 109.5 |
C6—N4—Ru1 | 105.68 (18) | S3—C23—H23A | 109.5 |
C18—N4—Ru1 | 106.7 (2) | S3—C23—H23B | 109.5 |
C12—N4—Ru1 | 111.10 (19) | H23A—C23—H23B | 109.5 |
N1—C1—C2 | 123.0 (3) | S3—C23—H23C | 109.5 |
N1—C1—H1 | 118.5 | H23A—C23—H23C | 109.5 |
C2—C1—H1 | 118.5 | H23B—C23—H23C | 109.5 |
C3—C2—C1 | 118.4 (3) | S3—C24—H24A | 109.5 |
C3—C2—H2 | 120.8 | S3—C24—H24B | 109.5 |
C1—C2—H2 | 120.8 | H24A—C24—H24B | 109.5 |
C2—C3—C4 | 119.6 (3) | S3—C24—H24C | 109.5 |
C2—C3—H3 | 120.2 | H24A—C24—H24C | 109.5 |
C4—C3—H3 | 120.2 | H24B—C24—H24C | 109.5 |
C5—C4—C3 | 119.8 (3) | S4—C25—H25A | 109.5 |
C5—C4—H4 | 120.1 | S4—C25—H25B | 109.5 |
C3—C4—H4 | 120.1 | H25A—C25—H25B | 109.5 |
N1—C5—C4 | 121.1 (3) | S4—C25—H25C | 109.5 |
N1—C5—C6 | 115.5 (3) | H25A—C25—H25C | 109.5 |
C4—C5—C6 | 123.3 (3) | H25B—C25—H25C | 109.5 |
N4—C6—C5 | 108.1 (3) | S4—C26—H26A | 109.5 |
N4—C6—H6A | 110.1 | S4—C26—H26B | 109.5 |
C5—C6—H6A | 110.1 | H26A—C26—H26B | 109.5 |
N4—C6—H6B | 110.1 | S4—C26—H26C | 109.5 |
C5—C6—H6B | 110.1 | H26A—C26—H26C | 109.5 |
H6A—C6—H6B | 108.4 | H26B—C26—H26C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | [RuCl(C18H18N4)(C2H6OS)][RuCl3(C2H6OS)3] |
Mr | 946.82 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 10.1817 (18), 14.221 (2), 14.664 (3) |
α, β, γ (°) | 114.362 (3), 96.804 (3), 105.610 (3) |
V (Å3) | 1798.1 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.41 |
Crystal size (mm) | 0.2 × 0.1 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8007, 5113, 4463 |
Rint | 0.017 |
θmax (°) | 23.3 |
(sin θ/λ)max (Å−1) | 0.556 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.066, 0.98 |
No. of reflections | 5113 |
No. of parameters | 405 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −0.41 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Ru1—N3 | 2.060 (3) | Ru2—S2 | 2.2643 (10) |
Ru1—N4 | 2.070 (3) | Ru2—S4 | 2.2668 (9) |
Ru1—N1 | 2.078 (3) | Ru2—S3 | 2.2707 (11) |
Ru1—N2 | 2.106 (3) | Ru2—Cl3 | 2.4307 (11) |
Ru1—S1 | 2.2385 (10) | Ru2—Cl2 | 2.4341 (9) |
Ru1—Cl1 | 2.4321 (9) | Ru2—Cl4 | 2.4503 (10) |
N3—Ru1—N4 | 82.90 (11) | S2—Ru2—S4 | 91.39 (4) |
N3—Ru1—N1 | 163.45 (10) | S2—Ru2—S3 | 95.66 (4) |
N4—Ru1—N1 | 80.55 (10) | S4—Ru2—S3 | 93.37 (4) |
N3—Ru1—N2 | 82.12 (10) | S2—Ru2—Cl3 | 86.94 (3) |
N4—Ru1—N2 | 80.75 (10) | S4—Ru2—Cl3 | 93.32 (3) |
N1—Ru1—N2 | 95.40 (10) | S3—Ru2—Cl3 | 172.76 (3) |
N3—Ru1—S1 | 89.39 (8) | S2—Ru2—Cl2 | 173.93 (4) |
N4—Ru1—S1 | 98.48 (8) | S4—Ru2—Cl2 | 87.57 (3) |
N1—Ru1—S1 | 92.81 (7) | S3—Ru2—Cl2 | 90.37 (4) |
N2—Ru1—S1 | 171.51 (8) | Cl3—Ru2—Cl2 | 87.15 (3) |
N3—Ru1—Cl1 | 101.71 (8) | S2—Ru2—Cl4 | 91.61 (4) |
N4—Ru1—Cl1 | 171.41 (8) | S4—Ru2—Cl4 | 176.96 (3) |
N1—Ru1—Cl1 | 94.73 (7) | S3—Ru2—Cl4 | 85.81 (3) |
N2—Ru1—Cl1 | 92.62 (7) | Cl3—Ru2—Cl4 | 87.37 (3) |
S1—Ru1—Cl1 | 88.87 (3) | Cl2—Ru2—Cl4 | 89.51 (3) |
With regard to the interest in oxidation by non-heam enzymes containing iron, which is a congenerous atom of ruthenium, ruthenium complexes with polypyridyl ligands have been extensively studied. Since polydentate polypyridyl ligands were found to be useful biomimicing ligands (Yan et al., 1989), tris(2-pyridylmethyl)amine (TPA) and modified TPA have been applied to the preparation of ruthenium complexes toward redox and substrate-oxidizing agent by several groups including us (Kojima, 1996; Yamaguchi et al., 1997; Kojima & Hayashi et al., 2000; Kojima & Matsuo et al., 2000; Sugimoto et al., 2001; Jitsukawa et al., 2001).
In the course of constructing new ruthenium complexes for alkane-oxidizing catalysis, we have already reported that the combination of TPA with chloride and dimethyl sulfoxide in the ruthenium complex affords two isomers, Cl located cis and trans to the amine-N atom. The former complex was structurally determined by X-ray diffraction as a PF6− salt, but the structure of the latter, which showed higher oxidizing activity, has been confirmed only by the chemical shift of 1H NMR (Yamaguchi et al., 1997). Fortunately, we could find in situ formation of the title compound, trans(Namino,Cl)-[RuCl(dmso)(TPA)][RuCl3(dmso)3], (I), and the structure was determined.
The structure of the cation of (I) shows that the four N atoms of TPA, a chloride ligand and the S atom of dmso configure a distorted octahedron around the Ru1 atom (Fig. 1 and Table 1). The Ru1—S1 distance of 2.2385 (10) Å is slightly shorter than that in the cis-isomer of 2.264 (1) Å, whereas both isomers have similar Ru—Cl distances; cf. 2.4321 (9) and 2.433 (1) Å, respectively. The structure of the anion also shows an octahedral configuration around the Ru2 atom, formed by three chlorides and three dmso S atoms. The two chlorides and the dmso ligands occupy facial three-coordination sites, respectively. The three Ru—Cl distances range from 2.4307 (11) to 2.4503 (10) Å, and the three Ru—S distances from 2.2643 (10) to 2.2707 (11) Å. These Ru—Cl distances are slightly longer than those of the already reported for the same anion [2.420 (2)–2.438 (2) Å; Yamamoto et al., 1999], while the Ru—S distances are comparable [2.263 (2)–2.276 (2) Å].