metal-organic compounds
cis,trans-Dicarbonyldichlorido[2-(2-pyridyl)-1,8-naphthyridine-κN1,N2]ruthenium(II)
aDepartment of Industrial Systems Engineering, Cluster of Science and Technology, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan, and bDepartment of Science Education, Faculty of Education, Fukushima University, 1 Kanayagawa, Fukushima 960-1296, Japan
*Correspondence e-mail: daio@sss.fukushima-u.ac.jp
The 2(C13H9N3)(CO)2], consists of four crystallographically independent RuII complexes. Each RuII atom is in a distorted octahedral environment coordinated by two carbonyl ligands, two Cl atoms and a chelating 2-(2-pyridyl)-1,8-naphthyridine (pynp) ligand. The carbonyl ligands are cis to each other, while the Cl atoms are trans. Relatively short interatomic distances (2.60–2.67 Å) between the uncoordinated N atom of pynp and the C atom of the carbonyl imply a donor–acceptor interaction between the pynp and carbonyl ligands.
of the title compound, [RuClRelated literature
For related synthetic details, see: Anderson et al. (1995); Campos-Fernandez et al. (2002). For related structures, see: Haukka et al. (1995); Tomon et al. (2005). For related literature on the redox behavior of ruthenium polypyridyl complexes with a 1,8-naphthyridine ligand, see: Nakajima & Tanaka (1995); Mizukawa et al. (1999); Tomon et al. (2005). For general background on the photochemical reduction of CO2, see: Lehn & Ziesel (1990).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: CrystalClear (Rigaku/MSC, 2001); cell CrystalClear; data reduction: TEXSAN (Rigaku/MSC, 2000); program(s) used to solve structure: DIRDIF94 (Beurskens et al., 1994); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).
Supporting information
10.1107/S1600536808003188/is2275sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808003188/is2275Isup2.hkl
A methanol solution (10 ml) containing [Ru(CO)2Cl2]n (31 mg) and pynp (30 mg) was refluxed for 1.5 h. The reaction mixture was then concentrated to 2 ml under reduced pressure. The yellow-green color precipitate was collected by filtration and washed with methanol and diethyl ether, and then dried under vacuum. Single crystals suitable for X-ray diffraction were prepared by the diffusion of diethyl ether into an acetonitrile solution of the complex over a week.
All H atoms were positioned geometrically (C—H = 0.95 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C). σ(F2).
was carried out using reflections with F2 > 0.0Data collection: CrystalClear (Rigaku/MSC, 2001); cell
CrystalClear (Rigaku/MSC, 2001); data reduction: TEXSAN (Rigaku/MSC, 2000); program(s) used to solve structure: DIRDIF94 (Beurskens et al., 1994); program(s) used to refine structure: TEXSAN (Rigaku/MSC, 2000); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004).Fig. 1. The molecular structure of the title compound, with atom labels and 50% probability displacement ellipsoids for non-H atoms. H atoms have been omitted for clarity. |
[RuCl2(C13H9N3)(CO)2] | F(000) = 3424.00 |
Mr = 435.23 | Dx = 1.850 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71070 Å |
Hall symbol: -P 2yn | Cell parameters from 13888 reflections |
a = 16.6297 (14) Å | θ = 3.1–27.5° |
b = 21.6048 (14) Å | µ = 1.36 mm−1 |
c = 19.0585 (16) Å | T = 173 K |
β = 114.082 (3)° | Prism, yellow–green |
V = 6251.4 (9) Å3 | 0.20 × 0.20 × 0.20 mm |
Z = 16 |
Rigaku/MSC Mercury CCD diffractometer | Rint = 0.063 |
Detector resolution: 14.62 pixels mm-1 | θmax = 27.5° |
ω scans | h = −21→21 |
49009 measured reflections | k = −26→28 |
14039 independent reflections | l = −24→24 |
12059 reflections with F2 > 2σ(F2) |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.078 | w = 1/[0.001Fo2 + 3σ(Fo2) + 0.5]/(4Fo2) |
wR(F2) = 0.152 | (Δ/σ)max = 0.001 |
S = 1.50 | Δρmax = 1.43 e Å−3 |
14038 reflections | Δρmin = −1.40 e Å−3 |
829 parameters |
[RuCl2(C13H9N3)(CO)2] | V = 6251.4 (9) Å3 |
Mr = 435.23 | Z = 16 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.6297 (14) Å | µ = 1.36 mm−1 |
b = 21.6048 (14) Å | T = 173 K |
c = 19.0585 (16) Å | 0.20 × 0.20 × 0.20 mm |
β = 114.082 (3)° |
Rigaku/MSC Mercury CCD diffractometer | 12059 reflections with F2 > 2σ(F2) |
49009 measured reflections | Rint = 0.063 |
14039 independent reflections |
R[F2 > 2σ(F2)] = 0.078 | 829 parameters |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.50 | Δρmax = 1.43 e Å−3 |
14038 reflections | Δρmin = −1.40 e Å−3 |
Refinement. Refinement using reflections with F2 > 2.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
Ru1 | 0.17626 (3) | 0.20501 (2) | 0.48235 (2) | 0.02146 (12) | |
Ru2 | 0.26702 (3) | 0.52889 (2) | 0.25696 (2) | 0.02210 (12) | |
Ru3 | 0.17269 (3) | 0.18945 (2) | −0.02197 (2) | 0.02201 (12) | |
Ru4 | 0.24140 (3) | 0.52453 (2) | −0.23420 (2) | 0.02233 (12) | |
Cl1 | 0.06386 (9) | 0.19503 (6) | 0.35501 (8) | 0.0272 (3) | |
Cl2 | 0.29508 (9) | 0.22208 (6) | 0.60516 (8) | 0.0303 (3) | |
Cl3 | 0.37956 (10) | 0.49259 (7) | 0.37431 (8) | 0.0325 (4) | |
Cl4 | 0.15511 (10) | 0.55566 (7) | 0.13358 (8) | 0.0313 (4) | |
Cl5 | 0.06215 (9) | 0.17790 (7) | −0.15037 (8) | 0.0315 (4) | |
Cl6 | 0.29082 (9) | 0.20463 (6) | 0.10162 (8) | 0.0272 (3) | |
Cl7 | 0.13015 (10) | 0.55219 (6) | −0.35724 (8) | 0.0315 (3) | |
Cl8 | 0.34896 (9) | 0.48759 (7) | −0.11404 (8) | 0.0309 (3) | |
O1 | 0.0528 (3) | 0.1442 (2) | 0.5419 (2) | 0.0419 (14) | |
O2 | 0.2435 (3) | 0.07537 (19) | 0.4855 (2) | 0.0370 (13) | |
O3 | 0.1594 (3) | 0.5568 (2) | 0.3487 (2) | 0.0390 (13) | |
O4 | 0.3353 (3) | 0.6589 (2) | 0.2864 (2) | 0.0458 (15) | |
O5 | 0.0451 (3) | 0.1371 (2) | 0.0398 (2) | 0.0490 (15) | |
O6 | 0.2341 (3) | 0.0586 (2) | −0.0194 (2) | 0.0459 (14) | |
O7 | 0.1349 (3) | 0.5783 (2) | −0.1535 (2) | 0.0466 (15) | |
O8 | 0.3278 (3) | 0.6493 (2) | −0.2133 (2) | 0.0496 (15) | |
N1 | 0.2545 (2) | 0.2500 (2) | 0.4331 (2) | 0.0235 (12) | |
N2 | 0.1470 (2) | 0.3014 (2) | 0.4864 (2) | 0.0217 (12) | |
N3 | 0.0393 (3) | 0.2824 (2) | 0.5304 (2) | 0.0273 (13) | |
N4 | 0.3478 (2) | 0.5031 (2) | 0.1998 (2) | 0.0242 (12) | |
N5 | 0.2342 (3) | 0.4342 (2) | 0.2289 (2) | 0.0221 (12) | |
N6 | 0.1209 (3) | 0.4358 (2) | 0.2691 (2) | 0.0270 (13) | |
N7 | 0.2548 (2) | 0.2286 (2) | −0.0705 (2) | 0.0229 (12) | |
N8 | 0.1508 (2) | 0.2878 (2) | −0.0192 (2) | 0.0225 (12) | |
N9 | 0.0415 (3) | 0.2756 (2) | 0.0245 (2) | 0.0338 (15) | |
N10 | 0.3154 (3) | 0.4833 (2) | −0.2900 (2) | 0.0299 (14) | |
N11 | 0.1944 (3) | 0.4317 (2) | −0.2534 (2) | 0.0237 (12) | |
N12 | 0.0846 (3) | 0.4522 (2) | −0.2121 (2) | 0.0300 (14) | |
C1 | 0.0986 (4) | 0.1699 (2) | 0.5221 (3) | 0.0287 (16) | |
C2 | 0.2171 (3) | 0.1240 (2) | 0.4817 (3) | 0.0265 (16) | |
C3 | 0.3024 (3) | 0.2213 (2) | 0.4009 (3) | 0.0275 (16) | |
C4 | 0.3575 (3) | 0.2538 (3) | 0.3755 (3) | 0.0328 (17) | |
C5 | 0.3647 (3) | 0.3165 (3) | 0.3837 (3) | 0.0314 (17) | |
C6 | 0.3145 (3) | 0.3469 (2) | 0.4158 (3) | 0.0286 (16) | |
C7 | 0.2584 (3) | 0.3125 (2) | 0.4388 (3) | 0.0251 (15) | |
C8 | 0.1980 (3) | 0.3408 (2) | 0.4695 (3) | 0.0255 (15) | |
C9 | 0.1934 (4) | 0.4047 (2) | 0.4771 (3) | 0.0298 (16) | |
C10 | 0.1364 (4) | 0.4294 (2) | 0.5042 (3) | 0.0312 (16) | |
C11 | 0.0804 (3) | 0.3891 (2) | 0.5228 (3) | 0.0262 (15) | |
C12 | 0.0190 (4) | 0.4090 (2) | 0.5517 (3) | 0.0319 (16) | |
C13 | −0.0312 (3) | 0.3665 (3) | 0.5673 (3) | 0.0322 (17) | |
C14 | −0.0183 (3) | 0.3038 (3) | 0.5565 (3) | 0.0317 (17) | |
C15 | 0.0888 (3) | 0.3250 (2) | 0.5135 (3) | 0.0212 (14) | |
C16 | 0.1963 (4) | 0.5453 (2) | 0.3120 (3) | 0.0285 (16) | |
C17 | 0.3079 (4) | 0.6102 (2) | 0.2762 (3) | 0.0301 (17) | |
C18 | 0.3990 (3) | 0.5412 (2) | 0.1807 (3) | 0.0274 (15) | |
C19 | 0.4506 (3) | 0.5218 (3) | 0.1436 (3) | 0.0340 (17) | |
C20 | 0.4517 (4) | 0.4605 (3) | 0.1271 (3) | 0.0390 (19) | |
C21 | 0.3998 (4) | 0.4196 (2) | 0.1471 (3) | 0.0357 (18) | |
C22 | 0.3472 (3) | 0.4423 (2) | 0.1825 (3) | 0.0272 (15) | |
C23 | 0.2847 (3) | 0.4038 (2) | 0.2001 (3) | 0.0228 (14) | |
C24 | 0.2748 (4) | 0.3405 (2) | 0.1839 (3) | 0.0289 (16) | |
C25 | 0.2118 (4) | 0.3078 (2) | 0.1962 (3) | 0.0316 (17) | |
C26 | 0.1582 (4) | 0.3375 (2) | 0.2271 (3) | 0.0280 (16) | |
C27 | 0.0924 (4) | 0.3081 (2) | 0.2431 (3) | 0.0364 (18) | |
C28 | 0.0434 (4) | 0.3433 (3) | 0.2707 (3) | 0.0383 (19) | |
C29 | 0.0595 (4) | 0.4064 (3) | 0.2827 (3) | 0.0351 (18) | |
C30 | 0.1705 (3) | 0.4018 (2) | 0.2417 (3) | 0.0247 (15) | |
C31 | 0.0923 (4) | 0.1593 (2) | 0.0177 (3) | 0.0315 (17) | |
C32 | 0.2082 (4) | 0.1082 (2) | −0.0216 (3) | 0.0285 (16) | |
C33 | 0.2991 (4) | 0.1963 (3) | −0.1035 (3) | 0.0320 (17) | |
C34 | 0.3558 (4) | 0.2241 (3) | −0.1298 (3) | 0.041 (2) | |
C35 | 0.3681 (4) | 0.2869 (3) | −0.1227 (3) | 0.042 (2) | |
C36 | 0.3212 (4) | 0.3214 (3) | −0.0905 (3) | 0.0381 (19) | |
C37 | 0.2633 (3) | 0.2914 (2) | −0.0657 (3) | 0.0244 (15) | |
C38 | 0.2055 (3) | 0.3238 (2) | −0.0365 (3) | 0.0254 (15) | |
C39 | 0.2083 (4) | 0.3883 (2) | −0.0276 (3) | 0.0358 (18) | |
C40 | 0.1516 (4) | 0.4168 (2) | −0.0026 (3) | 0.043 (2) | |
C41 | 0.0926 (4) | 0.3805 (3) | 0.0156 (3) | 0.0371 (18) | |
C42 | 0.0311 (5) | 0.4049 (3) | 0.0423 (3) | 0.047 (2) | |
C43 | −0.0223 (4) | 0.3649 (4) | 0.0575 (3) | 0.052 (2) | |
C44 | −0.0142 (4) | 0.3012 (3) | 0.0495 (3) | 0.045 (2) | |
C45 | 0.0930 (3) | 0.3147 (2) | 0.0063 (3) | 0.0261 (15) | |
C46 | 0.1725 (3) | 0.5554 (2) | −0.1843 (3) | 0.0277 (16) | |
C47 | 0.2939 (4) | 0.6024 (3) | −0.2205 (3) | 0.0332 (17) | |
C48 | 0.3730 (4) | 0.5126 (3) | −0.3110 (3) | 0.041 (2) | |
C49 | 0.4207 (4) | 0.4819 (4) | −0.3452 (3) | 0.051 (2) | |
C50 | 0.4124 (4) | 0.4188 (4) | −0.3541 (4) | 0.058 (2) | |
C51 | 0.3538 (4) | 0.3882 (3) | −0.3325 (3) | 0.049 (2) | |
C52 | 0.3036 (4) | 0.4213 (3) | −0.3025 (3) | 0.0336 (17) | |
C53 | 0.2367 (3) | 0.3931 (2) | −0.2814 (3) | 0.0265 (15) | |
C54 | 0.2144 (4) | 0.3291 (2) | −0.2920 (3) | 0.0367 (18) | |
C55 | 0.1492 (4) | 0.3065 (2) | −0.2738 (4) | 0.0398 (19) | |
C56 | 0.1030 (4) | 0.3463 (2) | −0.2453 (3) | 0.0337 (17) | |
C57 | 0.0326 (4) | 0.3282 (3) | −0.2259 (4) | 0.047 (2) | |
C58 | −0.0097 (4) | 0.3712 (3) | −0.2026 (4) | 0.045 (2) | |
C59 | 0.0205 (4) | 0.4325 (3) | −0.1949 (3) | 0.0374 (19) | |
C60 | 0.1265 (3) | 0.4096 (2) | −0.2367 (3) | 0.0260 (15) | |
H1 | 0.2985 | 0.1775 | 0.3952 | 0.033* | |
H2 | 0.3903 | 0.2323 | 0.3524 | 0.039* | |
H3 | 0.4034 | 0.3390 | 0.3677 | 0.038* | |
H4 | 0.3182 | 0.3906 | 0.4222 | 0.034* | |
H5 | 0.2302 | 0.4311 | 0.4632 | 0.036* | |
H6 | 0.1341 | 0.4729 | 0.5106 | 0.037* | |
H7 | 0.0129 | 0.4518 | 0.5601 | 0.038* | |
H8 | −0.0743 | 0.3789 | 0.5852 | 0.039* | |
H9 | −0.0531 | 0.2744 | 0.5687 | 0.038* | |
H10 | 0.3999 | 0.5838 | 0.1933 | 0.033* | |
H11 | 0.4847 | 0.5507 | 0.1298 | 0.041* | |
H12 | 0.4874 | 0.4459 | 0.1024 | 0.047* | |
H13 | 0.4002 | 0.3766 | 0.1367 | 0.043* | |
H14 | 0.3120 | 0.3203 | 0.1643 | 0.035* | |
H15 | 0.2040 | 0.2649 | 0.1839 | 0.038* | |
H16 | 0.0821 | 0.2649 | 0.2349 | 0.044* | |
H17 | −0.0018 | 0.3246 | 0.2817 | 0.046* | |
H18 | 0.0241 | 0.4296 | 0.3017 | 0.042* | |
H19 | 0.2909 | 0.1528 | −0.1089 | 0.038* | |
H20 | 0.3863 | 0.2000 | −0.1528 | 0.049* | |
H21 | 0.4081 | 0.3066 | −0.1395 | 0.050* | |
H22 | 0.3286 | 0.3650 | −0.0854 | 0.046* | |
H23 | 0.2495 | 0.4121 | −0.0390 | 0.043* | |
H24 | 0.1519 | 0.4606 | 0.0024 | 0.051* | |
H25 | 0.0275 | 0.4482 | 0.0494 | 0.056* | |
H26 | −0.0656 | 0.3802 | 0.0736 | 0.063* | |
H27 | −0.0511 | 0.2745 | 0.0629 | 0.054* | |
H28 | 0.3815 | 0.5558 | −0.3021 | 0.050* | |
H29 | 0.4586 | 0.5042 | −0.3624 | 0.062* | |
H30 | 0.4469 | 0.3965 | −0.3749 | 0.070* | |
H31 | 0.3476 | 0.3446 | −0.3381 | 0.059* | |
H32 | 0.2453 | 0.3021 | −0.3118 | 0.044* | |
H33 | 0.1348 | 0.2637 | −0.2803 | 0.048* | |
H34 | 0.0155 | 0.2860 | −0.2292 | 0.056* | |
H35 | −0.0588 | 0.3603 | −0.1917 | 0.054* | |
H36 | −0.0079 | 0.4620 | −0.1758 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.0231 (2) | 0.0193 (2) | 0.0243 (2) | 0.00155 (18) | 0.0120 (2) | 0.00087 (18) |
Ru2 | 0.0253 (2) | 0.0177 (2) | 0.0249 (2) | 0.00077 (18) | 0.0119 (2) | −0.00137 (18) |
Ru3 | 0.0232 (2) | 0.0202 (2) | 0.0247 (2) | 0.00118 (18) | 0.0120 (2) | 0.00049 (19) |
Ru4 | 0.0232 (2) | 0.0211 (2) | 0.0242 (2) | −0.00135 (18) | 0.0112 (2) | −0.00071 (18) |
Cl1 | 0.0265 (7) | 0.0283 (7) | 0.0276 (7) | −0.0001 (5) | 0.0117 (6) | 0.0016 (6) |
Cl2 | 0.0304 (8) | 0.0308 (7) | 0.0272 (7) | 0.0050 (6) | 0.0094 (6) | −0.0026 (6) |
Cl3 | 0.0310 (8) | 0.0315 (7) | 0.0306 (8) | −0.0013 (6) | 0.0080 (6) | 0.0037 (6) |
Cl4 | 0.0304 (8) | 0.0338 (8) | 0.0299 (8) | 0.0044 (6) | 0.0125 (6) | 0.0054 (6) |
Cl5 | 0.0285 (7) | 0.0334 (7) | 0.0306 (8) | −0.0013 (6) | 0.0099 (6) | 0.0015 (6) |
Cl6 | 0.0270 (7) | 0.0267 (7) | 0.0276 (7) | 0.0037 (5) | 0.0107 (6) | −0.0029 (5) |
Cl7 | 0.0298 (7) | 0.0307 (7) | 0.0301 (8) | 0.0007 (6) | 0.0084 (6) | 0.0035 (6) |
Cl8 | 0.0280 (7) | 0.0340 (7) | 0.0285 (8) | −0.0010 (6) | 0.0093 (6) | 0.0036 (6) |
O1 | 0.045 (2) | 0.035 (2) | 0.059 (3) | −0.001 (2) | 0.036 (2) | 0.013 (2) |
O2 | 0.048 (2) | 0.022 (2) | 0.043 (2) | 0.011 (2) | 0.021 (2) | 0.0034 (19) |
O3 | 0.050 (2) | 0.033 (2) | 0.050 (2) | −0.005 (2) | 0.036 (2) | −0.012 (2) |
O4 | 0.073 (3) | 0.024 (2) | 0.058 (3) | −0.013 (2) | 0.044 (2) | −0.009 (2) |
O5 | 0.040 (2) | 0.057 (3) | 0.061 (3) | −0.004 (2) | 0.031 (2) | 0.023 (2) |
O6 | 0.061 (3) | 0.027 (2) | 0.042 (2) | 0.012 (2) | 0.012 (2) | 0.001 (2) |
O7 | 0.043 (2) | 0.049 (3) | 0.055 (3) | −0.004 (2) | 0.028 (2) | −0.024 (2) |
O8 | 0.064 (3) | 0.034 (2) | 0.050 (3) | −0.021 (2) | 0.022 (2) | −0.001 (2) |
N1 | 0.020 (2) | 0.027 (2) | 0.026 (2) | 0.000 (2) | 0.011 (2) | 0.000 (2) |
N2 | 0.021 (2) | 0.020 (2) | 0.025 (2) | 0.0022 (18) | 0.010 (2) | −0.0024 (19) |
N3 | 0.028 (2) | 0.028 (2) | 0.027 (2) | 0.003 (2) | 0.012 (2) | −0.001 (2) |
N4 | 0.024 (2) | 0.023 (2) | 0.028 (2) | 0.002 (2) | 0.013 (2) | −0.001 (2) |
N5 | 0.026 (2) | 0.018 (2) | 0.021 (2) | 0.0011 (19) | 0.008 (2) | 0.0019 (19) |
N6 | 0.025 (2) | 0.027 (2) | 0.031 (2) | −0.001 (2) | 0.012 (2) | −0.000 (2) |
N7 | 0.019 (2) | 0.031 (2) | 0.017 (2) | 0.003 (2) | 0.006 (2) | −0.000 (2) |
N8 | 0.019 (2) | 0.023 (2) | 0.023 (2) | 0.0040 (19) | 0.007 (2) | −0.0005 (19) |
N9 | 0.022 (2) | 0.049 (3) | 0.032 (2) | 0.004 (2) | 0.012 (2) | −0.007 (2) |
N10 | 0.017 (2) | 0.049 (3) | 0.025 (2) | 0.007 (2) | 0.011 (2) | 0.002 (2) |
N11 | 0.027 (2) | 0.023 (2) | 0.021 (2) | −0.001 (2) | 0.009 (2) | −0.0041 (19) |
N12 | 0.030 (2) | 0.029 (2) | 0.036 (2) | −0.002 (2) | 0.019 (2) | 0.002 (2) |
C1 | 0.035 (3) | 0.027 (3) | 0.028 (3) | 0.008 (2) | 0.018 (2) | 0.006 (2) |
C2 | 0.025 (3) | 0.031 (3) | 0.022 (3) | −0.002 (2) | 0.008 (2) | 0.004 (2) |
C3 | 0.022 (3) | 0.032 (3) | 0.031 (3) | 0.003 (2) | 0.014 (2) | 0.001 (2) |
C4 | 0.024 (3) | 0.048 (4) | 0.030 (3) | 0.008 (2) | 0.015 (2) | 0.002 (2) |
C5 | 0.017 (2) | 0.050 (3) | 0.025 (3) | −0.004 (2) | 0.007 (2) | 0.009 (2) |
C6 | 0.025 (3) | 0.034 (3) | 0.024 (3) | −0.001 (2) | 0.007 (2) | 0.003 (2) |
C7 | 0.023 (3) | 0.025 (2) | 0.029 (3) | −0.000 (2) | 0.012 (2) | 0.002 (2) |
C8 | 0.023 (3) | 0.028 (3) | 0.025 (3) | −0.003 (2) | 0.009 (2) | 0.002 (2) |
C9 | 0.033 (3) | 0.023 (3) | 0.033 (3) | −0.003 (2) | 0.014 (2) | 0.001 (2) |
C10 | 0.038 (3) | 0.020 (2) | 0.033 (3) | 0.003 (2) | 0.013 (3) | −0.003 (2) |
C11 | 0.020 (2) | 0.029 (3) | 0.025 (3) | 0.004 (2) | 0.004 (2) | −0.000 (2) |
C12 | 0.033 (3) | 0.030 (3) | 0.027 (3) | 0.013 (2) | 0.006 (2) | −0.002 (2) |
C13 | 0.026 (3) | 0.041 (3) | 0.032 (3) | 0.004 (2) | 0.013 (2) | −0.005 (2) |
C14 | 0.024 (3) | 0.042 (3) | 0.032 (3) | −0.003 (2) | 0.016 (2) | −0.004 (2) |
C15 | 0.017 (2) | 0.024 (2) | 0.020 (2) | 0.004 (2) | 0.005 (2) | 0.000 (2) |
C16 | 0.035 (3) | 0.020 (2) | 0.025 (3) | −0.004 (2) | 0.007 (2) | −0.003 (2) |
C17 | 0.037 (3) | 0.026 (3) | 0.036 (3) | 0.001 (2) | 0.024 (3) | −0.003 (2) |
C18 | 0.025 (3) | 0.024 (2) | 0.031 (3) | 0.000 (2) | 0.008 (2) | 0.003 (2) |
C19 | 0.021 (3) | 0.040 (3) | 0.044 (3) | −0.002 (2) | 0.017 (2) | 0.004 (3) |
C20 | 0.030 (3) | 0.049 (4) | 0.046 (4) | −0.003 (3) | 0.024 (3) | −0.011 (3) |
C21 | 0.036 (3) | 0.031 (3) | 0.046 (4) | 0.003 (2) | 0.023 (3) | −0.002 (3) |
C22 | 0.027 (3) | 0.025 (3) | 0.026 (3) | −0.000 (2) | 0.009 (2) | −0.003 (2) |
C23 | 0.031 (3) | 0.019 (2) | 0.018 (2) | 0.006 (2) | 0.010 (2) | −0.000 (2) |
C24 | 0.034 (3) | 0.023 (2) | 0.028 (3) | 0.001 (2) | 0.011 (2) | −0.002 (2) |
C25 | 0.043 (3) | 0.022 (3) | 0.026 (3) | −0.004 (2) | 0.009 (3) | −0.003 (2) |
C26 | 0.035 (3) | 0.024 (2) | 0.021 (3) | 0.000 (2) | 0.008 (2) | 0.005 (2) |
C27 | 0.040 (3) | 0.027 (3) | 0.041 (3) | −0.007 (2) | 0.015 (3) | 0.002 (2) |
C28 | 0.032 (3) | 0.042 (3) | 0.044 (4) | −0.006 (3) | 0.018 (3) | 0.006 (3) |
C29 | 0.034 (3) | 0.036 (3) | 0.039 (3) | −0.003 (2) | 0.018 (3) | 0.006 (2) |
C30 | 0.025 (3) | 0.027 (3) | 0.020 (3) | 0.001 (2) | 0.008 (2) | 0.003 (2) |
C31 | 0.028 (3) | 0.035 (3) | 0.026 (3) | 0.001 (2) | 0.005 (2) | 0.005 (2) |
C32 | 0.034 (3) | 0.027 (3) | 0.021 (3) | −0.002 (2) | 0.007 (2) | 0.000 (2) |
C33 | 0.029 (3) | 0.043 (3) | 0.024 (3) | 0.011 (2) | 0.010 (2) | −0.000 (2) |
C34 | 0.026 (3) | 0.071 (5) | 0.027 (3) | 0.020 (3) | 0.013 (2) | 0.007 (3) |
C35 | 0.028 (3) | 0.065 (5) | 0.042 (4) | −0.001 (3) | 0.023 (3) | 0.015 (3) |
C36 | 0.023 (3) | 0.052 (4) | 0.037 (3) | −0.007 (2) | 0.010 (3) | 0.010 (3) |
C37 | 0.022 (2) | 0.031 (3) | 0.018 (2) | −0.001 (2) | 0.005 (2) | 0.003 (2) |
C38 | 0.023 (3) | 0.025 (2) | 0.025 (3) | −0.003 (2) | 0.007 (2) | −0.002 (2) |
C39 | 0.038 (3) | 0.029 (3) | 0.036 (3) | 0.002 (2) | 0.009 (3) | 0.002 (2) |
C40 | 0.054 (4) | 0.024 (3) | 0.043 (4) | 0.010 (3) | 0.013 (3) | −0.002 (3) |
C41 | 0.037 (3) | 0.037 (3) | 0.030 (3) | 0.014 (3) | 0.006 (3) | −0.005 (2) |
C42 | 0.051 (4) | 0.052 (4) | 0.031 (3) | 0.028 (3) | 0.010 (3) | −0.004 (3) |
C43 | 0.036 (4) | 0.085 (6) | 0.031 (4) | 0.033 (4) | 0.008 (3) | −0.006 (3) |
C44 | 0.024 (3) | 0.078 (5) | 0.031 (3) | 0.005 (3) | 0.009 (3) | −0.013 (3) |
C45 | 0.021 (2) | 0.031 (3) | 0.024 (3) | 0.008 (2) | 0.007 (2) | −0.004 (2) |
C46 | 0.030 (3) | 0.021 (2) | 0.031 (3) | −0.004 (2) | 0.011 (2) | −0.002 (2) |
C47 | 0.031 (3) | 0.041 (3) | 0.023 (3) | 0.001 (2) | 0.006 (2) | 0.004 (2) |
C48 | 0.029 (3) | 0.065 (4) | 0.029 (3) | 0.005 (3) | 0.012 (3) | 0.011 (3) |
C49 | 0.030 (3) | 0.100 (7) | 0.029 (3) | 0.009 (4) | 0.017 (3) | 0.013 (4) |
C50 | 0.035 (4) | 0.106 (7) | 0.035 (4) | 0.021 (4) | 0.015 (3) | −0.009 (4) |
C51 | 0.044 (4) | 0.067 (5) | 0.041 (4) | 0.015 (3) | 0.021 (3) | −0.009 (3) |
C52 | 0.026 (3) | 0.044 (3) | 0.026 (3) | 0.011 (2) | 0.005 (2) | −0.008 (2) |
C53 | 0.030 (3) | 0.026 (3) | 0.020 (3) | 0.011 (2) | 0.007 (2) | 0.002 (2) |
C54 | 0.045 (4) | 0.028 (3) | 0.025 (3) | 0.014 (2) | 0.002 (3) | −0.009 (2) |
C55 | 0.035 (3) | 0.024 (3) | 0.049 (4) | −0.003 (2) | 0.005 (3) | −0.006 (3) |
C56 | 0.038 (3) | 0.017 (2) | 0.035 (3) | −0.006 (2) | 0.004 (3) | 0.002 (2) |
C57 | 0.034 (4) | 0.034 (3) | 0.060 (4) | −0.007 (3) | 0.006 (3) | 0.020 (3) |
C58 | 0.031 (3) | 0.044 (4) | 0.065 (5) | 0.002 (3) | 0.024 (3) | 0.024 (3) |
C59 | 0.030 (3) | 0.041 (3) | 0.046 (4) | 0.003 (2) | 0.020 (3) | 0.012 (3) |
C60 | 0.029 (3) | 0.022 (2) | 0.021 (3) | −0.005 (2) | 0.004 (2) | −0.000 (2) |
Ru1—Cl1 | 2.3933 (12) | C20—C21 | 1.392 (10) |
Ru1—Cl2 | 2.3968 (13) | C21—C22 | 1.394 (10) |
Ru1—N1 | 2.124 (5) | C22—C23 | 1.474 (9) |
Ru1—N2 | 2.148 (4) | C23—C24 | 1.398 (7) |
Ru1—C1 | 1.901 (7) | C24—C25 | 1.361 (10) |
Ru1—C2 | 1.880 (6) | C25—C26 | 1.408 (10) |
Ru2—Cl3 | 2.3883 (13) | C26—C27 | 1.401 (10) |
Ru2—Cl4 | 2.3992 (13) | C26—C30 | 1.416 (8) |
Ru2—N4 | 2.121 (5) | C27—C28 | 1.365 (11) |
Ru2—N5 | 2.129 (4) | C28—C29 | 1.390 (9) |
Ru2—C16 | 1.903 (7) | C33—C34 | 1.375 (11) |
Ru2—C17 | 1.865 (6) | C34—C35 | 1.369 (11) |
Ru3—Cl5 | 2.3996 (13) | C35—C36 | 1.389 (11) |
Ru3—Cl6 | 2.3955 (12) | C36—C37 | 1.394 (10) |
Ru3—N7 | 2.113 (5) | C37—C38 | 1.469 (9) |
Ru3—N8 | 2.160 (4) | C38—C39 | 1.403 (8) |
Ru3—C31 | 1.900 (7) | C39—C40 | 1.365 (11) |
Ru3—C32 | 1.851 (6) | C40—C41 | 1.406 (11) |
Ru4—Cl7 | 2.3955 (13) | C41—C42 | 1.416 (12) |
Ru4—Cl8 | 2.3953 (13) | C41—C45 | 1.434 (9) |
Ru4—N10 | 2.124 (5) | C42—C43 | 1.352 (12) |
Ru4—N11 | 2.128 (4) | C43—C44 | 1.396 (12) |
Ru4—C46 | 1.884 (7) | C48—C49 | 1.383 (12) |
Ru4—C47 | 1.863 (6) | C49—C50 | 1.375 (14) |
O1—C1 | 1.126 (9) | C50—C51 | 1.372 (13) |
O2—C2 | 1.129 (7) | C51—C52 | 1.387 (11) |
O3—C16 | 1.129 (9) | C52—C53 | 1.462 (10) |
O4—C17 | 1.131 (7) | C53—C54 | 1.425 (8) |
O5—C31 | 1.136 (9) | C54—C55 | 1.358 (11) |
O6—C32 | 1.150 (7) | C55—C56 | 1.401 (10) |
O7—C46 | 1.132 (9) | C56—C57 | 1.419 (11) |
O8—C47 | 1.140 (8) | C56—C60 | 1.415 (8) |
N1—C3 | 1.340 (9) | C57—C58 | 1.344 (11) |
N1—C7 | 1.354 (7) | C58—C59 | 1.402 (9) |
N2—C8 | 1.331 (8) | C3—H1 | 0.950 |
N2—C15 | 1.368 (8) | C4—H2 | 0.950 |
N3—C14 | 1.329 (9) | C5—H3 | 0.950 |
N3—C15 | 1.357 (8) | C6—H4 | 0.950 |
N4—C18 | 1.337 (8) | C9—H5 | 0.950 |
N4—C22 | 1.352 (7) | C10—H6 | 0.950 |
N5—C23 | 1.345 (8) | C12—H7 | 0.950 |
N5—C30 | 1.373 (8) | C13—H8 | 0.950 |
N6—C29 | 1.314 (9) | C14—H9 | 0.950 |
N6—C30 | 1.357 (8) | C18—H10 | 0.950 |
N7—C33 | 1.344 (9) | C19—H11 | 0.950 |
N7—C37 | 1.363 (7) | C20—H12 | 0.950 |
N8—C38 | 1.335 (8) | C21—H13 | 0.950 |
N8—C45 | 1.372 (8) | C24—H14 | 0.950 |
N9—C44 | 1.324 (10) | C25—H15 | 0.950 |
N9—C45 | 1.344 (9) | C27—H16 | 0.950 |
N10—C48 | 1.339 (10) | C28—H17 | 0.950 |
N10—C52 | 1.360 (8) | C29—H18 | 0.950 |
N11—C53 | 1.336 (8) | C33—H19 | 0.950 |
N11—C60 | 1.377 (9) | C34—H20 | 0.950 |
N12—C59 | 1.308 (10) | C35—H21 | 0.950 |
N12—C60 | 1.348 (8) | C36—H22 | 0.950 |
C3—C4 | 1.389 (10) | C39—H23 | 0.950 |
C4—C5 | 1.364 (9) | C40—H24 | 0.950 |
C5—C6 | 1.386 (10) | C42—H25 | 0.950 |
C6—C7 | 1.396 (9) | C43—H26 | 0.950 |
C7—C8 | 1.485 (9) | C44—H27 | 0.950 |
C8—C9 | 1.392 (8) | C48—H28 | 0.950 |
C9—C10 | 1.359 (10) | C49—H29 | 0.950 |
C10—C11 | 1.422 (9) | C50—H30 | 0.950 |
C11—C12 | 1.411 (10) | C51—H31 | 0.950 |
C11—C15 | 1.412 (8) | C54—H32 | 0.950 |
C12—C13 | 1.354 (10) | C55—H33 | 0.950 |
C13—C14 | 1.400 (9) | C57—H34 | 0.950 |
C18—C19 | 1.380 (10) | C58—H35 | 0.950 |
C19—C20 | 1.364 (9) | C59—H36 | 0.950 |
Cl1—Ru1—Cl2 | 174.66 (6) | C25—C26—C30 | 117.7 (6) |
Cl1—Ru1—N1 | 87.63 (11) | C27—C26—C30 | 117.7 (6) |
Cl1—Ru1—N2 | 91.66 (10) | C26—C27—C28 | 118.2 (5) |
Cl1—Ru1—C1 | 89.55 (16) | C27—C28—C29 | 120.3 (7) |
Cl1—Ru1—C2 | 92.51 (15) | N6—C29—C28 | 123.6 (7) |
Cl2—Ru1—N1 | 87.24 (11) | N5—C30—N6 | 115.4 (5) |
Cl2—Ru1—N2 | 85.67 (10) | N5—C30—C26 | 121.7 (6) |
Cl2—Ru1—C1 | 95.47 (16) | N6—C30—C26 | 123.0 (6) |
Cl2—Ru1—C2 | 89.65 (15) | Ru3—C31—O5 | 175.1 (6) |
N1—Ru1—N2 | 76.2 (2) | Ru3—C32—O6 | 176.9 (5) |
N1—Ru1—C1 | 175.1 (2) | N7—C33—C34 | 122.2 (6) |
N1—Ru1—C2 | 97.7 (2) | C33—C34—C35 | 119.5 (7) |
N2—Ru1—C1 | 99.9 (2) | C34—C35—C36 | 119.2 (7) |
N2—Ru1—C2 | 172.5 (2) | C35—C36—C37 | 119.3 (6) |
C1—Ru1—C2 | 86.4 (2) | N7—C37—C36 | 120.5 (6) |
Cl3—Ru2—Cl4 | 174.31 (5) | N7—C37—C38 | 115.7 (5) |
Cl3—Ru2—N4 | 88.64 (11) | C36—C37—C38 | 123.8 (5) |
Cl3—Ru2—N5 | 86.68 (10) | N8—C38—C37 | 115.6 (5) |
Cl3—Ru2—C16 | 88.23 (16) | N8—C38—C39 | 122.8 (6) |
Cl3—Ru2—C17 | 92.39 (16) | C37—C38—C39 | 121.6 (6) |
Cl4—Ru2—N4 | 87.73 (11) | C38—C39—C40 | 119.8 (6) |
Cl4—Ru2—N5 | 88.21 (11) | C39—C40—C41 | 119.1 (6) |
Cl4—Ru2—C16 | 95.10 (16) | C40—C41—C42 | 124.1 (6) |
Cl4—Ru2—C17 | 92.31 (16) | C40—C41—C45 | 118.9 (7) |
N4—Ru2—N5 | 76.7 (2) | C42—C41—C45 | 117.0 (6) |
N4—Ru2—C16 | 175.2 (2) | C41—C42—C43 | 118.2 (7) |
N4—Ru2—C17 | 95.3 (2) | C42—C43—C44 | 120.3 (8) |
N5—Ru2—C16 | 99.5 (2) | N9—C44—C43 | 124.3 (7) |
N5—Ru2—C17 | 171.9 (2) | N8—C45—N9 | 115.9 (5) |
C16—Ru2—C17 | 88.6 (3) | N8—C45—C41 | 120.3 (6) |
Cl5—Ru3—Cl6 | 175.22 (6) | N9—C45—C41 | 123.7 (6) |
Cl5—Ru3—N7 | 87.61 (11) | Ru4—C46—O7 | 174.4 (5) |
Cl5—Ru3—N8 | 93.47 (10) | Ru4—C47—O8 | 177.7 (7) |
Cl5—Ru3—C31 | 89.95 (16) | N10—C48—C49 | 122.1 (7) |
Cl5—Ru3—C32 | 90.91 (16) | C48—C49—C50 | 119.0 (8) |
Cl6—Ru3—N7 | 87.61 (11) | C49—C50—C51 | 119.2 (8) |
Cl6—Ru3—N8 | 85.42 (10) | C50—C51—C52 | 119.8 (7) |
Cl6—Ru3—C31 | 94.82 (16) | N10—C52—C51 | 120.7 (6) |
Cl6—Ru3—C32 | 89.63 (15) | N10—C52—C53 | 115.7 (6) |
N7—Ru3—N8 | 76.2 (2) | C51—C52—C53 | 123.6 (6) |
N7—Ru3—C31 | 175.4 (2) | N11—C53—C52 | 115.8 (5) |
N7—Ru3—C32 | 96.8 (2) | N11—C53—C54 | 120.9 (6) |
N8—Ru3—C31 | 100.1 (2) | C52—C53—C54 | 123.3 (6) |
N8—Ru3—C32 | 171.6 (2) | C53—C54—C55 | 120.1 (6) |
C31—Ru3—C32 | 87.1 (3) | C54—C55—C56 | 120.0 (5) |
Cl7—Ru4—Cl8 | 174.97 (5) | C55—C56—C57 | 125.0 (5) |
Cl7—Ru4—N10 | 89.32 (12) | C55—C56—C60 | 118.0 (6) |
Cl7—Ru4—N11 | 89.08 (11) | C57—C56—C60 | 116.9 (6) |
Cl7—Ru4—C46 | 91.14 (16) | C56—C57—C58 | 119.7 (6) |
Cl7—Ru4—C47 | 92.41 (16) | C57—C58—C59 | 118.2 (7) |
Cl8—Ru4—N10 | 88.85 (12) | N12—C59—C58 | 125.1 (7) |
Cl8—Ru4—N11 | 85.94 (11) | N11—C60—N12 | 115.6 (5) |
Cl8—Ru4—C46 | 90.35 (16) | N11—C60—C56 | 121.5 (6) |
Cl8—Ru4—C47 | 92.45 (16) | N12—C60—C56 | 122.9 (6) |
N10—Ru4—N11 | 76.5 (2) | N1—C3—H1 | 119.1 |
N10—Ru4—C46 | 175.9 (2) | C4—C3—H1 | 119.1 |
N10—Ru4—C47 | 96.6 (2) | C3—C4—H2 | 119.9 |
N11—Ru4—C46 | 99.4 (2) | C5—C4—H2 | 119.9 |
N11—Ru4—C47 | 172.9 (2) | C4—C5—H3 | 120.6 |
C46—Ru4—C47 | 87.5 (3) | C6—C5—H3 | 120.6 |
Ru1—N1—C3 | 125.2 (4) | C5—C6—H4 | 120.4 |
Ru1—N1—C7 | 116.0 (4) | C7—C6—H4 | 120.4 |
C3—N1—C7 | 118.7 (5) | C8—C9—H5 | 119.8 |
Ru1—N2—C8 | 115.8 (4) | C10—C9—H5 | 119.8 |
Ru1—N2—C15 | 125.5 (3) | C9—C10—H6 | 120.6 |
C8—N2—C15 | 118.2 (4) | C11—C10—H6 | 120.6 |
C14—N3—C15 | 116.9 (5) | C11—C12—H7 | 120.3 |
Ru2—N4—C18 | 125.8 (4) | C13—C12—H7 | 120.4 |
Ru2—N4—C22 | 115.9 (4) | C12—C13—H8 | 120.7 |
C18—N4—C22 | 118.3 (5) | C14—C13—H8 | 120.7 |
Ru2—N5—C23 | 115.6 (3) | N3—C14—H9 | 117.7 |
Ru2—N5—C30 | 125.6 (4) | C13—C14—H9 | 117.7 |
C23—N5—C30 | 118.7 (4) | N4—C18—H10 | 118.3 |
C29—N6—C30 | 117.3 (5) | C19—C18—H10 | 118.3 |
Ru3—N7—C33 | 124.9 (4) | C18—C19—H11 | 120.6 |
Ru3—N7—C37 | 115.9 (4) | C20—C19—H11 | 120.6 |
C33—N7—C37 | 119.1 (5) | C19—C20—H12 | 120.5 |
Ru3—N8—C38 | 115.4 (4) | C21—C20—H12 | 120.5 |
Ru3—N8—C45 | 125.1 (4) | C20—C21—H13 | 120.3 |
C38—N8—C45 | 119.1 (5) | C22—C21—H13 | 120.3 |
C44—N9—C45 | 116.3 (6) | C23—C24—H14 | 120.0 |
Ru4—N10—C48 | 125.7 (4) | C25—C24—H14 | 120.0 |
Ru4—N10—C52 | 115.4 (4) | C24—C25—H15 | 120.1 |
C48—N10—C52 | 118.9 (6) | C26—C25—H15 | 120.1 |
Ru4—N11—C53 | 116.1 (4) | C26—C27—H16 | 120.9 |
Ru4—N11—C60 | 124.4 (4) | C28—C27—H16 | 120.9 |
C53—N11—C60 | 119.4 (4) | C27—C28—H17 | 119.9 |
C59—N12—C60 | 117.0 (5) | C29—C28—H17 | 119.8 |
Ru1—C1—O1 | 173.4 (5) | N6—C29—H18 | 118.2 |
Ru1—C2—O2 | 176.3 (5) | C28—C29—H18 | 118.2 |
N1—C3—C4 | 121.7 (5) | N7—C33—H19 | 118.9 |
C3—C4—C5 | 120.1 (6) | C34—C33—H19 | 118.9 |
C4—C5—C6 | 118.7 (6) | C33—C34—H20 | 120.2 |
C5—C6—C7 | 119.1 (5) | C35—C34—H20 | 120.2 |
N1—C7—C6 | 121.5 (6) | C34—C35—H21 | 120.4 |
N1—C7—C8 | 115.2 (5) | C36—C35—H21 | 120.4 |
C6—C7—C8 | 123.3 (5) | C35—C36—H22 | 120.3 |
N2—C8—C7 | 115.5 (5) | C37—C36—H22 | 120.3 |
N2—C8—C9 | 122.8 (6) | C38—C39—H23 | 120.1 |
C7—C8—C9 | 121.7 (6) | C40—C39—H23 | 120.1 |
C8—C9—C10 | 120.4 (6) | C39—C40—H24 | 120.5 |
C9—C10—C11 | 118.9 (5) | C41—C40—H24 | 120.4 |
C10—C11—C12 | 124.3 (5) | C41—C42—H25 | 120.9 |
C10—C11—C15 | 117.5 (6) | C43—C42—H25 | 120.9 |
C12—C11—C15 | 118.2 (6) | C42—C43—H26 | 119.8 |
C11—C12—C13 | 119.3 (5) | C44—C43—H26 | 119.8 |
C12—C13—C14 | 118.6 (6) | N9—C44—H27 | 117.9 |
N3—C14—C13 | 124.6 (6) | C43—C44—H27 | 117.9 |
N2—C15—N3 | 115.4 (5) | N10—C48—H28 | 118.9 |
N2—C15—C11 | 122.3 (5) | C49—C48—H28 | 118.9 |
N3—C15—C11 | 122.3 (6) | C48—C49—H29 | 120.5 |
Ru2—C16—O3 | 175.1 (4) | C50—C49—H29 | 120.5 |
Ru2—C17—O4 | 177.0 (7) | C49—C50—H30 | 120.4 |
N4—C18—C19 | 123.4 (5) | C51—C50—H30 | 120.4 |
C18—C19—C20 | 118.8 (6) | C50—C51—H31 | 120.1 |
C19—C20—C21 | 119.0 (7) | C52—C51—H31 | 120.1 |
C20—C21—C22 | 119.4 (6) | C53—C54—H32 | 119.9 |
N4—C22—C21 | 121.1 (6) | C55—C54—H32 | 119.9 |
N4—C22—C23 | 115.3 (6) | C54—C55—H33 | 120.0 |
C21—C22—C23 | 123.5 (5) | C56—C55—H33 | 120.0 |
N5—C23—C22 | 115.7 (4) | C56—C57—H34 | 120.2 |
N5—C23—C24 | 122.0 (6) | C58—C57—H34 | 120.2 |
C22—C23—C24 | 122.2 (6) | C57—C58—H35 | 120.9 |
C23—C24—C25 | 120.0 (6) | C59—C58—H35 | 120.9 |
C24—C25—C26 | 119.9 (5) | N12—C59—H36 | 117.4 |
C25—C26—C27 | 124.6 (5) | C58—C59—H36 | 117.4 |
Cl1—Ru1—N1—C3 | −81.7 (3) | C45—N8—C38—C37 | −178.1 (4) |
Cl1—Ru1—N1—C7 | 101.7 (3) | C45—N8—C38—C39 | 1.9 (7) |
Cl1—Ru1—N2—C8 | −97.1 (3) | C44—N9—C45—N8 | 179.7 (4) |
Cl1—Ru1—N2—C15 | 91.4 (3) | C44—N9—C45—C41 | 2.7 (7) |
Cl2—Ru1—N1—C3 | 99.8 (3) | C45—N9—C44—C43 | 0.2 (6) |
Cl2—Ru1—N1—C7 | −76.8 (3) | Ru4—N10—C48—C49 | 178.0 (4) |
Cl2—Ru1—N2—C8 | 78.3 (3) | Ru4—N10—C52—C51 | −174.5 (4) |
Cl2—Ru1—N2—C15 | −93.3 (3) | Ru4—N10—C52—C53 | 4.7 (5) |
N1—Ru1—N2—C8 | −10.0 (3) | C48—N10—C52—C51 | 3.5 (7) |
N1—Ru1—N2—C15 | 178.5 (3) | C48—N10—C52—C53 | −177.2 (4) |
N2—Ru1—N1—C3 | −174.0 (4) | C52—N10—C48—C49 | 0.2 (7) |
N2—Ru1—N1—C7 | 9.4 (3) | Ru4—N11—C53—C52 | −6.1 (5) |
C2—Ru1—N1—C3 | 10.5 (4) | Ru4—N11—C53—C54 | 176.1 (3) |
C2—Ru1—N1—C7 | −166.1 (3) | Ru4—N11—C60—N12 | 5.2 (6) |
C1—Ru1—N2—C8 | 173.1 (3) | Ru4—N11—C60—C56 | −175.1 (3) |
C1—Ru1—N2—C15 | 1.5 (4) | C53—N11—C60—N12 | −177.0 (4) |
Cl3—Ru2—N4—C18 | −99.1 (3) | C53—N11—C60—C56 | 2.8 (7) |
Cl3—Ru2—N4—C22 | 80.1 (3) | C60—N11—C53—C52 | 175.9 (4) |
Cl3—Ru2—N5—C23 | −81.4 (3) | C60—N11—C53—C54 | −1.9 (7) |
Cl3—Ru2—N5—C30 | 94.7 (3) | C59—N12—C60—N11 | −179.3 (4) |
Cl4—Ru2—N4—C18 | 85.3 (3) | C59—N12—C60—C56 | 0.9 (7) |
Cl4—Ru2—N4—C22 | −95.5 (3) | C60—N12—C59—C58 | −2.2 (8) |
Cl4—Ru2—N5—C23 | 96.0 (3) | N1—C3—C4—C5 | 0.6 (7) |
Cl4—Ru2—N5—C30 | −87.8 (3) | C3—C4—C5—C6 | −1.6 (7) |
N4—Ru2—N5—C23 | 7.9 (3) | C4—C5—C6—C7 | 0.0 (6) |
N4—Ru2—N5—C30 | −175.9 (4) | C5—C6—C7—N1 | 2.6 (7) |
N5—Ru2—N4—C18 | 174.0 (4) | C5—C6—C7—C8 | −176.2 (4) |
N5—Ru2—N4—C22 | −6.8 (3) | N1—C7—C8—N2 | −0.9 (6) |
C17—Ru2—N4—C18 | −6.8 (4) | N1—C7—C8—C9 | −178.6 (4) |
C17—Ru2—N4—C22 | 172.3 (3) | C6—C7—C8—N2 | 177.9 (4) |
C16—Ru2—N5—C23 | −169.1 (3) | C6—C7—C8—C9 | 0.3 (6) |
C16—Ru2—N5—C30 | 7.1 (4) | N2—C8—C9—C10 | 1.4 (7) |
Cl5—Ru3—N7—C33 | −78.0 (3) | C7—C8—C9—C10 | 178.9 (4) |
Cl5—Ru3—N7—C37 | 103.2 (3) | C8—C9—C10—C11 | −1.6 (7) |
Cl5—Ru3—N8—C38 | −96.3 (3) | C9—C10—C11—C12 | 179.7 (5) |
Cl5—Ru3—N8—C45 | 91.0 (3) | C9—C10—C11—C15 | 1.4 (7) |
Cl6—Ru3—N7—C33 | 101.9 (3) | C10—C11—C12—C13 | 179.9 (3) |
Cl6—Ru3—N7—C37 | −76.8 (3) | C10—C11—C15—N2 | −1.2 (7) |
Cl6—Ru3—N8—C38 | 79.1 (3) | C10—C11—C15—N3 | 179.2 (4) |
Cl6—Ru3—N8—C45 | −93.7 (3) | C12—C11—C15—N2 | −179.5 (4) |
N7—Ru3—N8—C38 | −9.6 (3) | C12—C11—C15—N3 | 0.8 (7) |
N7—Ru3—N8—C45 | 177.7 (3) | C15—C11—C12—C13 | −1.8 (7) |
N8—Ru3—N7—C33 | −172.2 (4) | C11—C12—C13—C14 | 2.0 (7) |
N8—Ru3—N7—C37 | 9.1 (3) | C12—C13—C14—N3 | −1.2 (8) |
C32—Ru3—N7—C33 | 12.6 (4) | N4—C18—C19—C20 | −1.8 (8) |
C32—Ru3—N7—C37 | −166.2 (3) | C18—C19—C20—C21 | 1.0 (8) |
C31—Ru3—N8—C38 | 173.2 (3) | C19—C20—C21—C22 | 0.8 (8) |
C31—Ru3—N8—C45 | 0.4 (4) | C20—C21—C22—N4 | −2.0 (7) |
Cl7—Ru4—N10—C48 | 87.0 (4) | C20—C21—C22—C23 | 174.9 (4) |
Cl7—Ru4—N10—C52 | −95.1 (3) | N4—C22—C23—N5 | 2.0 (6) |
Cl7—Ru4—N11—C53 | 96.0 (3) | N4—C22—C23—C24 | 178.4 (4) |
Cl7—Ru4—N11—C60 | −86.1 (3) | C21—C22—C23—N5 | −175.0 (4) |
Cl8—Ru4—N10—C48 | −97.7 (4) | C21—C22—C23—C24 | 1.4 (7) |
Cl8—Ru4—N10—C52 | 80.2 (3) | N5—C23—C24—C25 | 0.9 (7) |
Cl8—Ru4—N11—C53 | −83.3 (3) | C22—C23—C24—C25 | −175.3 (4) |
Cl8—Ru4—N11—C60 | 94.6 (3) | C23—C24—C25—C26 | −1.6 (7) |
N10—Ru4—N11—C53 | 6.5 (3) | C24—C25—C26—C27 | −179.0 (5) |
N10—Ru4—N11—C60 | −175.6 (4) | C24—C25—C26—C30 | 2.2 (7) |
N11—Ru4—N10—C48 | 176.2 (4) | C25—C26—C27—C28 | −177.9 (5) |
N11—Ru4—N10—C52 | −5.9 (3) | C25—C26—C30—N5 | −2.1 (7) |
C47—Ru4—N10—C48 | −5.4 (4) | C25—C26—C30—N6 | 177.8 (4) |
C47—Ru4—N10—C52 | 172.5 (3) | C27—C26—C30—N5 | 179.0 (4) |
C46—Ru4—N11—C53 | −173.0 (3) | C27—C26—C30—N6 | −1.1 (7) |
C46—Ru4—N11—C60 | 4.9 (4) | C30—C26—C27—C28 | 0.9 (7) |
Ru1—N1—C3—C4 | −174.6 (3) | C26—C27—C28—C29 | −0.3 (7) |
Ru1—N1—C7—C6 | 173.3 (3) | C27—C28—C29—N6 | −0.2 (7) |
Ru1—N1—C7—C8 | −7.7 (5) | N7—C33—C34—C35 | −0.2 (6) |
C3—N1—C7—C6 | −3.5 (6) | C33—C34—C35—C36 | −1.5 (8) |
C3—N1—C7—C8 | 175.4 (4) | C34—C35—C36—C37 | 0.4 (8) |
C7—N1—C3—C4 | 1.9 (7) | C35—C36—C37—N7 | 2.2 (7) |
Ru1—N2—C8—C7 | 9.1 (5) | C35—C36—C37—C38 | −175.0 (4) |
Ru1—N2—C8—C9 | −173.3 (3) | N7—C37—C38—N8 | −0.9 (6) |
Ru1—N2—C15—N3 | −7.9 (5) | N7—C37—C38—C39 | 179.1 (4) |
Ru1—N2—C15—C11 | 172.4 (3) | C36—C37—C38—N8 | 176.5 (4) |
C8—N2—C15—N3 | −179.3 (4) | C36—C37—C38—C39 | −3.5 (7) |
C8—N2—C15—C11 | 1.0 (6) | N8—C38—C39—C40 | −2.1 (8) |
C15—N2—C8—C7 | −178.7 (4) | C37—C38—C39—C40 | 177.9 (5) |
C15—N2—C8—C9 | −1.1 (7) | C38—C39—C40—C41 | 1.6 (8) |
C14—N3—C15—N2 | −179.7 (4) | C39—C40—C41—C42 | 179.8 (5) |
C14—N3—C15—C11 | 0.1 (5) | C39—C40—C41—C45 | −1.0 (8) |
C15—N3—C14—C13 | 0.2 (6) | C40—C41—C42—C43 | 179.6 (5) |
Ru2—N4—C18—C19 | 179.8 (3) | C40—C41—C45—N8 | 0.8 (7) |
Ru2—N4—C22—C21 | −178.0 (3) | C40—C41—C45—N9 | 177.7 (5) |
Ru2—N4—C22—C23 | 5.0 (5) | C42—C41—C45—N8 | −179.9 (3) |
C18—N4—C22—C21 | 1.3 (7) | C42—C41—C45—N9 | −3.0 (7) |
C18—N4—C22—C23 | −175.8 (4) | C45—C41—C42—C43 | 0.4 (7) |
C22—N4—C18—C19 | 0.6 (7) | C41—C42—C43—C44 | 2.3 (8) |
Ru2—N5—C23—C22 | −7.9 (5) | C42—C43—C44—N9 | −2.8 (9) |
Ru2—N5—C23—C24 | 175.6 (3) | N10—C48—C49—C50 | −3.7 (8) |
Ru2—N5—C30—N6 | 5.5 (5) | C48—C49—C50—C51 | 3.3 (9) |
Ru2—N5—C30—C26 | −174.6 (3) | C49—C50—C51—C52 | 0.3 (7) |
C23—N5—C30—N6 | −178.5 (4) | C50—C51—C52—N10 | −3.8 (8) |
C23—N5—C30—C26 | 1.4 (6) | C50—C51—C52—C53 | 177.0 (5) |
C30—N5—C23—C22 | 175.7 (4) | N10—C52—C53—N11 | 0.9 (6) |
C30—N5—C23—C24 | −0.8 (6) | N10—C52—C53—C54 | 178.7 (4) |
C29—N6—C30—N5 | −179.5 (4) | C51—C52—C53—N11 | −179.9 (3) |
C29—N6—C30—C26 | 0.5 (7) | C51—C52—C53—C54 | −2.1 (8) |
C30—N6—C29—C28 | 0.1 (6) | N11—C53—C54—C55 | 0.2 (6) |
Ru3—N7—C33—C34 | −175.9 (3) | C52—C53—C54—C55 | −177.4 (5) |
Ru3—N7—C37—C36 | 175.0 (3) | C53—C54—C55—C56 | 0.7 (8) |
Ru3—N7—C37—C38 | −7.6 (5) | C54—C55—C56—C57 | 178.7 (5) |
C33—N7—C37—C36 | −3.9 (6) | C54—C55—C56—C60 | 0.1 (6) |
C33—N7—C37—C38 | 173.6 (4) | C55—C56—C57—C58 | −176.7 (6) |
C37—N7—C33—C34 | 2.9 (7) | C55—C56—C60—N11 | −1.9 (7) |
Ru3—N8—C38—C37 | 8.7 (5) | C55—C56—C60—N12 | 177.9 (5) |
Ru3—N8—C38—C39 | −171.3 (3) | C57—C56—C60—N11 | 179.4 (5) |
Ru3—N8—C45—N9 | −5.9 (6) | C57—C56—C60—N12 | −0.8 (8) |
Ru3—N8—C45—C41 | 171.2 (3) | C60—C56—C57—C58 | 1.9 (8) |
C38—N8—C45—N9 | −178.3 (4) | C56—C57—C58—C59 | −3.0 (9) |
C38—N8—C45—C41 | −1.2 (6) | C57—C58—C59—N12 | 3.3 (9) |
Experimental details
Crystal data | |
Chemical formula | [RuCl2(C13H9N3)(CO)2] |
Mr | 435.23 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 16.6297 (14), 21.6048 (14), 19.0585 (16) |
β (°) | 114.082 (3) |
V (Å3) | 6251.4 (9) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 1.36 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku/MSC Mercury CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 49009, 14039, 12059 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.078, 0.152, 1.50 |
No. of reflections | 14038 |
No. of parameters | 829 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.43, −1.40 |
Computer programs: CrystalClear (Rigaku/MSC, 2001), TEXSAN (Rigaku/MSC, 2000), DIRDIF94 (Beurskens et al., 1994), ORTEP-3 for Windows (Farrugia, 1997), CrystalStructure (Rigaku/MSC, 2004).
Ru1—Cl1 | 2.3933 (12) | Ru3—Cl5 | 2.3996 (13) |
Ru1—Cl2 | 2.3968 (13) | Ru3—Cl6 | 2.3955 (12) |
Ru1—N1 | 2.124 (5) | Ru3—N7 | 2.113 (5) |
Ru1—N2 | 2.148 (4) | Ru3—N8 | 2.160 (4) |
Ru1—C1 | 1.901 (7) | Ru3—C31 | 1.900 (7) |
Ru1—C2 | 1.880 (6) | Ru3—C32 | 1.851 (6) |
Ru2—Cl3 | 2.3883 (13) | Ru4—Cl7 | 2.3955 (13) |
Ru2—Cl4 | 2.3992 (13) | Ru4—Cl8 | 2.3953 (13) |
Ru2—N4 | 2.121 (5) | Ru4—N10 | 2.124 (5) |
Ru2—N5 | 2.129 (4) | Ru4—N11 | 2.128 (4) |
Ru2—C16 | 1.903 (7) | Ru4—C46 | 1.884 (7) |
Ru2—C17 | 1.865 (6) | Ru4—C47 | 1.863 (6) |
Acknowledgements
The authors thank Dr K. Shiren of the Institute for Molecular Science for his help with the X-ray measurements.
References
Anderson, P. A., Deacon, G. B., Haarmann, K. H., Keene, F. R., Meyer, T. J., Reitsma, D. A., Skelton, B. W., Strouse, G. F., Thomas, N. C., Treadway, J. A. & White, A. H. (1995). Inorg. Chem. 34, 6145–6157. CrossRef CAS Web of Science Google Scholar
Beurskens, P. T., Admiraal, G., Beurskens, G., Bosman, W. P., de Gelder, R., Israel, R. & Smits, J. M. M. (1994). DIRDIF94. Technical Report of the Crystallography Laboratory, University of Nijmengen, The Netherlands. Google Scholar
Campos-Fernandez, C. S., Thomson, L. M., Galan-Mascaros, J. R., Ouyang, X. & Dunbar, K. (2002). Inorg. Chem. 41, 1523–1533. Web of Science CSD CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Haukka, M., Kiviaho, J., Ahlgren, M. & Pakkanen, T. A. (1995). Organomatallics, 14, 825–833. CSD CrossRef CAS Web of Science Google Scholar
Lehn, J.-M. & Ziesel, R. (1990). J. Organomet. Chem. 382, 157–173. CrossRef CAS Web of Science Google Scholar
Mizukawa, T., Tsuge, K., Nakajima, H. & Tanaka, K. (1999). Angew. Chem. Int. Ed. 38, 362–363. CrossRef CAS Google Scholar
Nakajima, H. & Tanaka, K. (1995). Chem. Lett. pp. 891–892. CrossRef Web of Science Google Scholar
Rigaku/MSC (2000). TEXSAN. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Rigaku/MSC (2001). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Tomon, T., Koizumi, T. & Tanaka, K. (2005). Angew. Chem. Int. Ed. 44, 2229–2232. Web of Science CSD CrossRef CAS Google Scholar
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.
[Ru(bpy)(CO)2Cl2] (bpy = 2,2'-bipyridine) is known as an excellent catalyst for the photochemical reduction of CO2 into formate (Lehn & Ziesel, 1990). On the other hand, some interesting redox properties of ruthenium polypyridyl complexes with a 1,8-naphthyridine (napy) as a redox active ligand have been reported so far (Nakajima & Tanaka, 1995; Mizukawa et al., 1999; Tomon et al., 2005). In the present work, [Ru(pynp)(CO)2Cl2] [pynp = 2-(2-pyridyl)-1,8-naphthyridine] was newly prepared. Pynp (Campos-Fernandez et al., 2002) is a ligand which has the combined properties of 2,2'-bipyridine and 1,8-naphthyridine.
The crystal structure of the title compound contains four [Ru(pynp)(CO)2Cl2] complexes of crystallization in the asymmetric unit. The ruthenium(II) complex displays a cis orientation of the carbonyl ligands and a trans orientation of the chloro ligands (Fig. 1). Two Ru—C—O bond angles of the complex [173.4 (5)–177.7 (7)°] are nearly linear, and the C—O [1.126 (9)–1.150 (7) Å], Ru—Cl [2.3883 (13)–2.3996 (13) Å], Ru—N [2.113 (5)–2.160 (4) Å] distances are in the expected ranges (Table 1). On the other hand, the Ru—C bond distances [1.851 (6)–1.903 (7) Å] are longer than those of [Ru(bpy)(CO)2Cl2] [1.817 (8), 1.835 (17) Å; Haukka et al., 1995]. The naphthyridine moiety of the pynp ligand is directed toward the adjacent terminal carbonyl ligand. The relatively short interatomic distances between the non-bonded nitrogen atom of pynp and the carbon atom of one of carbonyls [2.60—2.67 Å] are comparable to that of [Ru(bpy)2(napy)(CO)]2+ [2.765 (7) Å; Tomon et al., 2005], which exhibits intramolecular metallacyclization between the non-bonded nitrogen atom of the napy ligand and the carbonyl carbon atom driven by the napy-based redox reaction.