Abstract
Reaction of [Ru(Tp)Cl(PPh3)2] {where Tp is hydridotripyrazolylborate, BH[C3H3N2)3)]} with NH4[S2P(OEt)2] in methanol afforded the title compound, [Ru(C9H10BN6)(C4H10O2PS2)(C18H15P)], in which the RuII ion is in a slightly disorted octahedral coordination environment. The [S2P(OEt)2]− ligand coordinates in a chelating mode with two similar Ru—S bond lengths and a slightly acute S—Ru—S angle. The atoms of both –OCH2CH3 groups of the diethyl dithiophosphate ligand are disordered over two sites with approximate occupancies of 0.76 and 0.24.
Related literature
For related structures, see: Alock et al. (1992 ▶); Burrows (2001 ▶); Hidai et al. (2000 ▶); Gemel et al. (1996 ▶); Jain & Jakkal (1996 ▶); Meno et al. (1995 ▶); Pavlik et al. (2005 ▶); Sellmann et al. (1999 ▶); Slugovc et al. (1998 ▶); Vit & Zdrazil (1989 ▶).
Experimental
Crystal data
[Ru(C9H10BN6)(C4H10O2PS2)(C18H15P)]
M r = 761.59
Monoclinic,
a = 12.4408 (2) Å
b = 13.7386 (2) Å
c = 20.3775 (3) Å
β = 99.676 (1)°
V = 3433.36 (9) Å3
Z = 4
Mo Kα radiation
μ = 0.71 mm−1
T = 200 (2) K
0.42 × 0.3 × 0.15 mm
Data collection
Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T min = 0.755, T max = 0.901
24009 measured reflections
6265 independent reflections
5601 reflections with I > 2σ(I)
R int = 0.051
Refinement
R[F 2 > 2σ(F 2)] = 0.036
wR(F 2) = 0.093
S = 1.05
6265 reflections
449 parameters
42 restraints
H-atom parameters constrained
Δρmax = 1.43 e Å−3
Δρmin = −0.62 e Å−3
Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).
Supplementary Material
Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680803170X/lh2697sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S160053680803170X/lh2697Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Table 1. Selected geometric parameters (Å, °).
| Ru1—N3 | 2.086 (2) |
| Ru1—N1 | 2.088 (2) |
| Ru1—N5 | 2.144 (3) |
| Ru1—P1 | 2.3171 (8) |
| Ru1—S1 | 2.4540 (8) |
| Ru1—S2 | 2.4635 (8) |
| N3—Ru1—N1 | 90.09 (9) |
| N3—Ru1—N5 | 83.57 (10) |
| N1—Ru1—N5 | 84.88 (10) |
| N3—Ru1—P1 | 90.07 (7) |
| N1—Ru1—P1 | 90.63 (7) |
| N5—Ru1—P1 | 172.20 (7) |
| N3—Ru1—S1 | 170.14 (7) |
| N1—Ru1—S1 | 93.07 (7) |
| N5—Ru1—S1 | 87.41 (7) |
| P1—Ru1—S1 | 99.23 (3) |
| N3—Ru1—S2 | 94.61 (7) |
| N1—Ru1—S2 | 169.78 (7) |
| N5—Ru1—S2 | 86.63 (7) |
| P1—Ru1—S2 | 98.42 (3) |
| S1—Ru1—S2 | 80.86 (3) |
Acknowledgments
This research was supported by the National Science Council, Taiwan (NSC 97-2113-M-036–001-MY2), and in part by the project of the specific research fields in Tatung University, Taiwan (B96-C07-081), and the project of the specific research fields in Chung Yuan Christian University, Taiwan, under grant No. CYCU-97-CR-CH. We also thank Mr Ting Shen Kuo (Department of Chemistry, National Taiwan Normal University) for his assistance in X-ray single-crystal structure analysis.
supplementary crystallographic information
Comment
The chemistry of transition metal sulfur compounds has attracted interest for their importance in the field of catalysts, metalloenzymes, and materialprecursor (Hidai et al.,2000). In recent years there has been an increased interest in ruthenium sulfurcomplexes, in part because of the high catalytic activity of RuS2 in various hydrotreating processes (Vit & Zdrazil, 1989). As a part of this development, many examples of ruthenium thiolate complexes have been reported, however, the ruthenium complexes with dithio ligands are relatively rare (Sellmann et al., 1999). On the other hand, ruthenium(II)hydridotripyrazolylborate complexes, Ru(Tp), are of interest for stoichiometricand catalytic transformations of organic molecules (Pavlik et al., 2005). The complex [Ru(Tp)Cl(PPh3)2] (Alock et al., 1992) has been used as the starting material for the synthesis of several complexes because of its substitutionally labile chloride and phosphines (Burrows, 2001). In order to aquire a better understanding of the coordination chemistry of RuS2,we have studied the ruthenium phosphine complex containing the ligands hydrotris(pyrazolyl)borate (Tp) and [NH4][S2P(OEt)2]. Interaction of [Ru(Tp)Cl(PPh3)2] with [NH4][S2P(OEt)2] in MeOH afforded the title compound {Ru(Tp)(PPh3)[S2P(OEt)2]} (I). The 31P NMRspectrum of (I) in CDCl3 shows two intense singletsat 50.8 and 105.7 p.p.m., assignable to PPh3 and [S2P(OEt)2],respectively. The FAB mass spectrum of (I) shows the molecular ions {Ru(Tp)(PPh3)[S2P(OEt)2]} with the characteristic isotopic distribution patterns. The crystal structure of (I) was established by X-ray crystallography. In the title compound, the environment about the RuII ion is slightly distorted octahedral and the bite angle of the Tp ligand produces an average N—Ru—N angle of ca. 86° only slightly distorted from 90°. The three Ru—N(Tp) bond lengths are slightly longer than the average distance of 2.038 Å in other ruthenium Tp complexes (Gemel et al.1996; Slugovc et al.1998). The [S2P(OEt)2]– ligand chelates the ruthenium centre with two nearly equal Ru—S bonds and the S—Ru—S angle is slightly acute. The Ru—S bond lengths in (I) are comparable to those in [(η6-p-cymene)Ru{S2P(OMe)2}(PPh3)][BPh4][av. 2.4311 (12) Å] with a chelated dithiophosphate ligand (Jain & Jakkal, 1996), but slightly longer than for cis-[Ru(S2CNEt2)2(PPh3)2][av. 2.3952 (5) Å] with chelated dithiocarbamate (Meno et al.., 1995). The Ru—P bond length in (I) agrees well with those in related ruthenium(II) complexes with PPh3 ligands (Jain & Jakkal, 1996, Meno et al., 1995).
Experimental
The synthesis of the title compound (I) was carried out as follows. To a solution of [Ru(Tp)Cl(PPh3)2](3.95 g,4.50 mmol) in MeOH (20 ml), an excess of [NH4][S2P(OEt)2] (1.82 g, 9.00 mmol) were added. The reaction mixture was stirred for a further 8 h at room temperature. The solvent was dried under vacuum and 20 ml of CH2Cl2 was added to the residue. The product was dissolved in CH2Cl2 and other salts such as [NH4][S2P(OEt)2] and NH4Cl precipitated. After filtration, the solvent was dried under vacuum to give the title compound (I) (3.27 g, 95% yield). Spectroscopic analysis: IR (KBr, cm-1): ν(BH)2468 cm-1.1H NMR (CDCl3, 303 K, d,p.p.m.): d 7.92 (d, JH—H = 2.3 Hz, 1H, Tp),7.83 (d, JH—H = 2.3 Hz, 1H, Tp), 7.71 (d, JH—H =2.3 Hz, 1H, Tp), 7.4–6.9 (m, Tp, Ph), 6.83 (d, JH—H = 2.3 Hz,1H, Tp), 5.81 (d, JH—H = 2.2 Hz, 1H, Tp), 5.66 (d, JH—H= 2.2 Hz, 1H, Tp), 5.63 (t, JH—H = 2.2 Hz, 1H, Tp), 5.54(t, JH—H = 2.2 Hz, 1H, Tp), 4.16 (q, JH—H =7.2 Hz, 2H, OCH2), 3.11 (q, JH—H = 7.2 Hz, 2H, OCH2),1.32(t, JH—H = 7.2 Hz, 3H, CH3), 0.79 (t, JH—H= 7.2 Hz, 3H, CH3).13C NMR (CDCl3,303 K, d, p.p.m.): 146.7–104.6 (m, PPh3, Tp), 60.6,61.4 (d, OCH2, 2JP—C = 10 Hz), 15.5,15.9 (d, OCH2CH3, 3JP—C= 8.4 Hz). 31P NMR (CDCl3, 303 K, d,p.p.m.): d 105.7 (PS2), 50.9 (s, PPh3). MS (m/z,Ru102): 762.2 (M+), 500.1(M+ - PPh3). Anal. Calcdfor C31H35BN6O2P2RuS2:C, 48.89; H, 4.63; N, 11.03. Found: C, 48.73; H,4.61; N, 11.02. The bright-yellow crystalsof (I) for X-ray structure analysis were obtained by recrystallization of the crude product from dichloromethane-hexane.
Refinement
H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 - 0.97 Å and Uiso(H) = 1.2 or 1.5Ueq(C), B—H = 0.98 Å and Uiso(H) = 1.2Ueq(C). The atoms of both -OCH2CH3 groups of the diethyldithiophosphato ligand are disordered over two sites with refined occupancies of 0.764 (3) and 0.236 (3).
Figures
Fig. 1.
Molecular structure of (I) showing displacement ellipsoids at the 35% level and H atoms having arbitrary radius. The disorder is not shown.
Crystal data
| [Ru(C9H10BN6)(C4H10O2PS2)(C18H15P)] | F(000) = 1560 |
| Mr = 761.59 | Dx = 1.473 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 32408 reflections |
| a = 12.4408 (2) Å | θ = 2.0–25.4° |
| b = 13.7386 (2) Å | µ = 0.71 mm−1 |
| c = 20.3775 (3) Å | T = 200 K |
| β = 99.676 (1)° | Prism, yellow |
| V = 3433.36 (9) Å3 | 0.42 × 0.3 × 0.15 mm |
| Z = 4 |
Data collection
| Nonius KappaCCD diffractometer | 6265 independent reflections |
| Radiation source: fine-focus sealed tube | 5601 reflections with I > 2σ(I) |
| graphite | Rint = 0.051 |
| Detector resolution: 9 pixels mm-1 | θmax = 25.4°, θmin = 2.4° |
| CCD rotation images, thick slices scans | h = −11→14 |
| Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −16→16 |
| Tmin = 0.755, Tmax = 0.901 | l = −24→24 |
| 24009 measured reflections |
Refinement
| 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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.093 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.0373P)2 + 5.0939P] where P = (Fo2 + 2Fc2)/3 |
| 6265 reflections | (Δ/σ)max = 0.001 |
| 449 parameters | Δρmax = 1.43 e Å−3 |
| 42 restraints | Δρmin = −0.62 e Å−3 |
Special details
| 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Ru1 | 0.685497 (18) | 0.068530 (16) | 0.255762 (11) | 0.02384 (9) | |
| S1 | 0.79384 (7) | 0.17427 (6) | 0.19498 (4) | 0.0388 (2) | |
| S2 | 0.74769 (7) | −0.05385 (6) | 0.18210 (4) | 0.03638 (19) | |
| P1 | 0.81369 (6) | 0.03972 (6) | 0.35016 (4) | 0.02612 (17) | |
| P2 | 0.84695 (7) | 0.05178 (7) | 0.16235 (4) | 0.0369 (2) | |
| N1 | 0.6227 (2) | 0.18566 (18) | 0.30252 (12) | 0.0289 (5) | |
| N2 | 0.5136 (2) | 0.18862 (18) | 0.30454 (13) | 0.0324 (6) | |
| N3 | 0.57667 (19) | −0.02517 (18) | 0.29151 (12) | 0.0272 (5) | |
| N4 | 0.47495 (19) | 0.00904 (18) | 0.29637 (13) | 0.0301 (6) | |
| N5 | 0.5506 (2) | 0.09368 (19) | 0.17715 (13) | 0.0314 (6) | |
| N6 | 0.4510 (2) | 0.11145 (19) | 0.19433 (14) | 0.0339 (6) | |
| C1 | 0.6649 (3) | 0.2667 (2) | 0.33239 (16) | 0.0351 (7) | |
| H1A | 0.7383 | 0.2835 | 0.3384 | 0.042* | |
| C2 | 0.5841 (3) | 0.3225 (3) | 0.35311 (19) | 0.0454 (9) | |
| H2A | 0.5922 | 0.3822 | 0.3749 | 0.054* | |
| C3 | 0.4901 (3) | 0.2709 (2) | 0.33460 (17) | 0.0406 (8) | |
| H3A | 0.4212 | 0.2897 | 0.3417 | 0.049* | |
| C4 | 0.5802 (3) | −0.1169 (2) | 0.31240 (15) | 0.0307 (7) | |
| H4A | 0.6401 | −0.1579 | 0.3140 | 0.037* | |
| C5 | 0.4826 (3) | −0.1432 (2) | 0.33140 (17) | 0.0396 (8) | |
| H5A | 0.4647 | −0.2030 | 0.3480 | 0.048* | |
| C6 | 0.4181 (3) | −0.0622 (2) | 0.32047 (17) | 0.0371 (7) | |
| H6A | 0.3469 | −0.0571 | 0.3284 | 0.045* | |
| C7 | 0.5363 (3) | 0.0975 (3) | 0.11105 (17) | 0.0410 (8) | |
| H7A | 0.5909 | 0.0872 | 0.0858 | 0.049* | |
| C8 | 0.4285 (3) | 0.1189 (3) | 0.08504 (19) | 0.0493 (9) | |
| H8A | 0.3978 | 0.1263 | 0.0405 | 0.059* | |
| C9 | 0.3772 (3) | 0.1267 (3) | 0.13905 (18) | 0.0445 (9) | |
| H9A | 0.3037 | 0.1403 | 0.1378 | 0.053* | |
| C10 | 0.7727 (2) | 0.0899 (2) | 0.42642 (15) | 0.0295 (6) | |
| C11 | 0.8439 (3) | 0.1437 (2) | 0.47297 (15) | 0.0351 (7) | |
| H11A | 0.9154 | 0.1535 | 0.4667 | 0.042* | |
| C12 | 0.8085 (3) | 0.1827 (3) | 0.52858 (17) | 0.0419 (8) | |
| H12A | 0.8566 | 0.2186 | 0.5593 | 0.050* | |
| C13 | 0.7026 (3) | 0.1686 (3) | 0.53855 (17) | 0.0437 (8) | |
| H13A | 0.6789 | 0.1958 | 0.5754 | 0.052* | |
| C14 | 0.6322 (3) | 0.1137 (3) | 0.49359 (17) | 0.0427 (8) | |
| H14A | 0.5614 | 0.1026 | 0.5009 | 0.051* | |
| C15 | 0.6662 (3) | 0.0751 (2) | 0.43786 (16) | 0.0354 (7) | |
| H15A | 0.6177 | 0.0389 | 0.4077 | 0.042* | |
| C16 | 0.8413 (2) | −0.0886 (2) | 0.37420 (16) | 0.0300 (6) | |
| C17 | 0.8813 (3) | −0.1501 (2) | 0.32978 (17) | 0.0389 (8) | |
| H17A | 0.8871 | −0.1272 | 0.2876 | 0.047* | |
| C18 | 0.9128 (3) | −0.2447 (3) | 0.34695 (19) | 0.0441 (8) | |
| H18A | 0.9395 | −0.2845 | 0.3165 | 0.053* | |
| C19 | 0.9043 (3) | −0.2796 (2) | 0.40899 (19) | 0.0446 (9) | |
| H19A | 0.9265 | −0.3427 | 0.4210 | 0.054* | |
| C20 | 0.8628 (3) | −0.2207 (3) | 0.45330 (19) | 0.0464 (9) | |
| H20A | 0.8553 | −0.2448 | 0.4949 | 0.056* | |
| C21 | 0.8320 (3) | −0.1256 (2) | 0.43639 (17) | 0.0387 (8) | |
| H21A | 0.8049 | −0.0863 | 0.4670 | 0.046* | |
| C22 | 0.9557 (2) | 0.0851 (2) | 0.35834 (15) | 0.0314 (7) | |
| C23 | 1.0452 (3) | 0.0291 (3) | 0.38653 (17) | 0.0386 (8) | |
| H23A | 1.0344 | −0.0335 | 0.4015 | 0.046* | |
| C24 | 1.1505 (3) | 0.0660 (3) | 0.39243 (19) | 0.0470 (9) | |
| H24A | 1.2096 | 0.0273 | 0.4102 | 0.056* | |
| C25 | 1.1676 (3) | 0.1587 (3) | 0.37228 (19) | 0.0515 (10) | |
| H25A | 1.2381 | 0.1833 | 0.3767 | 0.062* | |
| C26 | 1.0798 (3) | 0.2161 (3) | 0.34532 (19) | 0.0494 (9) | |
| H26A | 1.0912 | 0.2794 | 0.3318 | 0.059* | |
| C27 | 0.9746 (3) | 0.1791 (3) | 0.33844 (17) | 0.0406 (8) | |
| H27A | 0.9160 | 0.2180 | 0.3202 | 0.049* | |
| O1 | 0.9685 (2) | 0.0388 (3) | 0.20330 (16) | 0.0485 (8) | 0.764 (3) |
| C28 | 1.0361 (4) | −0.0397 (4) | 0.1920 (3) | 0.0657 (16) | 0.764 (3) |
| H28A | 1.0254 | −0.0524 | 0.1446 | 0.079* | 0.764 (3) |
| H28B | 1.0124 | −0.0971 | 0.2134 | 0.079* | 0.764 (3) |
| C29 | 1.1497 (4) | −0.0264 (6) | 0.2152 (5) | 0.079 (2) | 0.764 (3) |
| H29A | 1.1884 | −0.0839 | 0.2059 | 0.118* | 0.764 (3) |
| H29B | 1.1619 | −0.0149 | 0.2623 | 0.118* | 0.764 (3) |
| H29C | 1.1753 | 0.0283 | 0.1929 | 0.118* | 0.764 (3) |
| O1A | 0.9713 (4) | 0.0320 (9) | 0.1572 (5) | 0.0479 (13) | 0.236 (3) |
| C29A | 1.1270 (19) | −0.061 (2) | 0.2317 (18) | 0.079 (2) | 0.236 (3) |
| H29D | 1.1592 | −0.0565 | 0.2779 | 0.118* | 0.236 (3) |
| H29E | 1.1827 | −0.0527 | 0.2047 | 0.118* | 0.236 (3) |
| H29F | 1.0928 | −0.1229 | 0.2229 | 0.118* | 0.236 (3) |
| C28A | 1.0470 (15) | 0.0148 (15) | 0.2162 (8) | 0.0648 (19) | 0.236 (3) |
| H28C | 1.0029 | 0.0108 | 0.2511 | 0.078* | 0.236 (3) |
| H28D | 1.0878 | 0.0750 | 0.2241 | 0.078* | 0.236 (3) |
| O2 | 0.8764 (3) | 0.0499 (3) | 0.08958 (13) | 0.0458 (9) | 0.764 (3) |
| C30 | 0.7920 (4) | 0.0556 (4) | 0.0330 (2) | 0.0476 (13) | 0.764 (3) |
| H30A | 0.7472 | 0.1124 | 0.0366 | 0.057* | 0.764 (3) |
| H30B | 0.7459 | −0.0017 | 0.0311 | 0.057* | 0.764 (3) |
| C31 | 0.8393 (18) | 0.0618 (10) | −0.0271 (6) | 0.068 (3) | 0.764 (3) |
| H31A | 0.7821 | 0.0649 | −0.0650 | 0.102* | 0.764 (3) |
| H31B | 0.8835 | 0.0054 | −0.0305 | 0.102* | 0.764 (3) |
| H31C | 0.8835 | 0.1193 | −0.0255 | 0.102* | 0.764 (3) |
| O2A | 0.8154 (9) | 0.0724 (8) | 0.0839 (2) | 0.0467 (13) | 0.236 (3) |
| C30A | 0.8201 (17) | 0.0081 (12) | 0.0299 (7) | 0.0487 (17) | 0.236 (3) |
| H30C | 0.7493 | −0.0230 | 0.0193 | 0.058* | 0.236 (3) |
| H30D | 0.8721 | −0.0426 | 0.0462 | 0.058* | 0.236 (3) |
| C31A | 0.848 (7) | 0.042 (4) | −0.032 (2) | 0.068 (3) | 0.236 (3) |
| H31D | 0.8431 | −0.0104 | −0.0630 | 0.102* | 0.236 (3) |
| H31E | 0.9207 | 0.0677 | −0.0241 | 0.102* | 0.236 (3) |
| H31F | 0.7979 | 0.0929 | −0.0497 | 0.102* | 0.236 (3) |
| B1 | 0.4383 (3) | 0.1100 (3) | 0.26828 (19) | 0.0346 (8) | |
| H1 | 0.3624 | 0.1224 | 0.2729 | 0.042* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ru1 | 0.01928 (13) | 0.02232 (13) | 0.03081 (14) | 0.00061 (9) | 0.00673 (9) | 0.00169 (9) |
| S1 | 0.0393 (5) | 0.0347 (4) | 0.0454 (5) | −0.0073 (4) | 0.0159 (4) | 0.0054 (4) |
| S2 | 0.0374 (5) | 0.0309 (4) | 0.0439 (4) | 0.0032 (3) | 0.0155 (4) | −0.0018 (3) |
| P1 | 0.0202 (4) | 0.0268 (4) | 0.0319 (4) | 0.0005 (3) | 0.0060 (3) | 0.0010 (3) |
| P2 | 0.0284 (4) | 0.0498 (5) | 0.0346 (4) | −0.0018 (4) | 0.0116 (3) | −0.0028 (4) |
| N1 | 0.0237 (13) | 0.0267 (13) | 0.0369 (13) | 0.0020 (10) | 0.0065 (10) | 0.0017 (11) |
| N2 | 0.0264 (13) | 0.0298 (13) | 0.0422 (14) | 0.0062 (11) | 0.0093 (11) | 0.0007 (11) |
| N3 | 0.0212 (12) | 0.0268 (13) | 0.0352 (13) | 0.0004 (10) | 0.0087 (10) | −0.0018 (10) |
| N4 | 0.0188 (12) | 0.0309 (13) | 0.0418 (14) | −0.0007 (10) | 0.0091 (10) | 0.0009 (11) |
| N5 | 0.0249 (13) | 0.0314 (14) | 0.0374 (14) | 0.0034 (11) | 0.0036 (11) | 0.0022 (11) |
| N6 | 0.0230 (13) | 0.0311 (14) | 0.0460 (15) | 0.0043 (11) | 0.0007 (11) | 0.0036 (12) |
| C1 | 0.0347 (18) | 0.0277 (16) | 0.0428 (18) | −0.0022 (14) | 0.0059 (14) | −0.0026 (14) |
| C2 | 0.050 (2) | 0.0291 (17) | 0.057 (2) | 0.0076 (16) | 0.0108 (17) | −0.0077 (16) |
| C3 | 0.0376 (19) | 0.0357 (18) | 0.050 (2) | 0.0108 (15) | 0.0133 (15) | −0.0032 (15) |
| C4 | 0.0298 (16) | 0.0252 (15) | 0.0382 (16) | −0.0014 (13) | 0.0084 (13) | 0.0010 (13) |
| C5 | 0.0370 (19) | 0.0324 (17) | 0.052 (2) | −0.0065 (15) | 0.0159 (15) | 0.0062 (15) |
| C6 | 0.0289 (17) | 0.0407 (19) | 0.0445 (18) | −0.0050 (14) | 0.0137 (14) | 0.0022 (15) |
| C7 | 0.042 (2) | 0.0434 (19) | 0.0359 (17) | 0.0025 (16) | 0.0016 (15) | 0.0014 (15) |
| C8 | 0.046 (2) | 0.054 (2) | 0.043 (2) | −0.0011 (18) | −0.0077 (17) | 0.0042 (17) |
| C9 | 0.0290 (18) | 0.044 (2) | 0.055 (2) | 0.0008 (15) | −0.0078 (16) | 0.0037 (17) |
| C10 | 0.0292 (16) | 0.0264 (15) | 0.0337 (16) | 0.0032 (13) | 0.0071 (12) | 0.0046 (12) |
| C11 | 0.0312 (17) | 0.0372 (18) | 0.0366 (16) | −0.0011 (14) | 0.0044 (13) | −0.0006 (14) |
| C12 | 0.046 (2) | 0.0407 (19) | 0.0390 (18) | −0.0037 (16) | 0.0087 (15) | −0.0093 (15) |
| C13 | 0.051 (2) | 0.045 (2) | 0.0383 (18) | 0.0001 (17) | 0.0157 (16) | −0.0076 (15) |
| C14 | 0.0345 (19) | 0.052 (2) | 0.0451 (19) | 0.0007 (16) | 0.0173 (15) | −0.0001 (16) |
| C15 | 0.0321 (17) | 0.0408 (18) | 0.0333 (16) | −0.0035 (14) | 0.0059 (13) | −0.0023 (14) |
| C16 | 0.0194 (14) | 0.0302 (16) | 0.0390 (16) | −0.0006 (12) | 0.0008 (12) | 0.0025 (13) |
| C17 | 0.0341 (18) | 0.0380 (18) | 0.0455 (19) | 0.0100 (15) | 0.0091 (15) | 0.0048 (15) |
| C18 | 0.0373 (19) | 0.0357 (18) | 0.059 (2) | 0.0068 (15) | 0.0070 (16) | −0.0009 (16) |
| C19 | 0.0356 (19) | 0.0291 (17) | 0.066 (2) | 0.0029 (15) | −0.0017 (17) | 0.0054 (16) |
| C20 | 0.054 (2) | 0.0369 (19) | 0.047 (2) | −0.0029 (17) | 0.0046 (17) | 0.0127 (16) |
| C21 | 0.0406 (19) | 0.0347 (18) | 0.0403 (18) | −0.0024 (15) | 0.0053 (15) | 0.0012 (14) |
| C22 | 0.0236 (15) | 0.0388 (17) | 0.0331 (16) | −0.0042 (13) | 0.0082 (12) | −0.0025 (13) |
| C23 | 0.0268 (17) | 0.0458 (19) | 0.0428 (18) | 0.0000 (15) | 0.0045 (14) | 0.0017 (15) |
| C24 | 0.0233 (17) | 0.067 (3) | 0.051 (2) | −0.0018 (16) | 0.0071 (15) | −0.0041 (18) |
| C25 | 0.0287 (19) | 0.077 (3) | 0.051 (2) | −0.0171 (19) | 0.0119 (16) | −0.010 (2) |
| C26 | 0.046 (2) | 0.052 (2) | 0.052 (2) | −0.0224 (18) | 0.0136 (17) | −0.0027 (17) |
| C27 | 0.0346 (18) | 0.0390 (19) | 0.0474 (19) | −0.0065 (15) | 0.0049 (15) | −0.0012 (15) |
| O1 | 0.0291 (16) | 0.072 (2) | 0.0457 (19) | 0.0045 (16) | 0.0094 (15) | −0.0087 (18) |
| C28 | 0.053 (3) | 0.060 (4) | 0.080 (4) | 0.007 (3) | 0.001 (3) | −0.006 (3) |
| C29 | 0.034 (3) | 0.103 (7) | 0.103 (6) | 0.015 (4) | 0.018 (3) | −0.009 (5) |
| O1A | 0.029 (2) | 0.070 (3) | 0.046 (3) | 0.005 (2) | 0.012 (2) | −0.007 (3) |
| C29A | 0.034 (3) | 0.103 (7) | 0.103 (6) | 0.015 (4) | 0.018 (3) | −0.009 (5) |
| C28A | 0.053 (4) | 0.059 (4) | 0.079 (5) | 0.008 (4) | −0.001 (4) | −0.008 (4) |
| O2 | 0.0285 (19) | 0.077 (2) | 0.0354 (15) | −0.0102 (19) | 0.0145 (15) | −0.0088 (15) |
| C30 | 0.048 (3) | 0.053 (4) | 0.040 (2) | 0.001 (3) | 0.003 (2) | 0.002 (3) |
| C31 | 0.090 (5) | 0.079 (7) | 0.038 (3) | 0.026 (6) | 0.021 (3) | −0.010 (4) |
| O2A | 0.032 (3) | 0.076 (3) | 0.036 (2) | −0.012 (3) | 0.017 (2) | −0.009 (2) |
| C30A | 0.050 (4) | 0.054 (4) | 0.041 (3) | 0.001 (3) | 0.002 (3) | 0.001 (3) |
| C31A | 0.090 (5) | 0.079 (7) | 0.038 (3) | 0.026 (6) | 0.021 (3) | −0.010 (4) |
| B1 | 0.0216 (17) | 0.0350 (19) | 0.047 (2) | 0.0031 (15) | 0.0065 (15) | 0.0024 (16) |
Geometric parameters (Å, °)
| Ru1—N3 | 2.086 (2) | C15—H15A | 0.9300 |
| Ru1—N1 | 2.088 (2) | C16—C21 | 1.388 (4) |
| Ru1—N5 | 2.144 (3) | C16—C17 | 1.390 (5) |
| Ru1—P1 | 2.3171 (8) | C17—C18 | 1.385 (5) |
| Ru1—S1 | 2.4540 (8) | C17—H17A | 0.9300 |
| Ru1—S2 | 2.4635 (8) | C18—C19 | 1.372 (5) |
| S1—P2 | 1.9643 (13) | C18—H18A | 0.9300 |
| S2—P2 | 1.9899 (12) | C19—C20 | 1.376 (5) |
| P1—C16 | 1.846 (3) | C19—H19A | 0.9300 |
| P1—C10 | 1.848 (3) | C20—C21 | 1.389 (5) |
| P1—C22 | 1.854 (3) | C20—H20A | 0.9300 |
| P2—O2 | 1.587 (3) | C21—H21A | 0.9300 |
| P2—O1A | 1.591 (4) | C22—C27 | 1.386 (5) |
| P2—O2A | 1.607 (4) | C22—C23 | 1.396 (5) |
| P2—O1 | 1.609 (3) | C23—C24 | 1.391 (5) |
| N1—C1 | 1.334 (4) | C23—H23A | 0.9300 |
| N1—N2 | 1.366 (3) | C24—C25 | 1.366 (6) |
| N2—C3 | 1.341 (4) | C24—H24A | 0.9300 |
| N2—B1 | 1.535 (5) | C25—C26 | 1.383 (6) |
| N3—C4 | 1.329 (4) | C25—H25A | 0.9300 |
| N3—N4 | 1.369 (3) | C26—C27 | 1.389 (5) |
| N4—C6 | 1.347 (4) | C26—H26A | 0.9300 |
| N4—B1 | 1.540 (4) | C27—H27A | 0.9300 |
| N5—C7 | 1.330 (4) | O1—C28 | 1.409 (5) |
| N5—N6 | 1.365 (4) | C28—C29 | 1.424 (6) |
| N6—C9 | 1.344 (4) | C28—H28A | 0.9700 |
| N6—B1 | 1.541 (5) | C28—H28B | 0.9700 |
| C1—C2 | 1.384 (5) | C29—H29A | 0.9600 |
| C1—H1A | 0.9300 | C29—H29B | 0.9600 |
| C2—C3 | 1.366 (5) | C29—H29C | 0.9600 |
| C2—H2A | 0.9300 | O1A—C28A | 1.416 (6) |
| C3—H3A | 0.9300 | C29A—C28A | 1.435 (6) |
| C4—C5 | 1.383 (4) | C29A—H29D | 0.9600 |
| C4—H4A | 0.9300 | C29A—H29E | 0.9600 |
| C5—C6 | 1.368 (5) | C29A—H29F | 0.9600 |
| C5—H5A | 0.9300 | C28A—H28C | 0.9700 |
| C6—H6A | 0.9300 | C28A—H28D | 0.9700 |
| C7—C8 | 1.388 (5) | O2—C30 | 1.426 (4) |
| C7—H7A | 0.9300 | C30—C31 | 1.446 (5) |
| C8—C9 | 1.366 (5) | C30—H30A | 0.9700 |
| C8—H8A | 0.9300 | C30—H30B | 0.9700 |
| C9—H9A | 0.9300 | C31—H31A | 0.9600 |
| C10—C11 | 1.396 (4) | C31—H31B | 0.9600 |
| C10—C15 | 1.399 (4) | C31—H31C | 0.9600 |
| C11—C12 | 1.390 (5) | O2A—C30A | 1.420 (6) |
| C11—H11A | 0.9300 | C30A—C31A | 1.438 (6) |
| C12—C13 | 1.380 (5) | C30A—H30C | 0.9700 |
| C12—H12A | 0.9300 | C30A—H30D | 0.9700 |
| C13—C14 | 1.381 (5) | C31A—H31D | 0.9600 |
| C13—H13A | 0.9300 | C31A—H31E | 0.9600 |
| C14—C15 | 1.383 (5) | C31A—H31F | 0.9600 |
| C14—H14A | 0.9300 | B1—H1 | 0.9800 |
| N3—Ru1—N1 | 90.09 (9) | C14—C15—H15A | 119.7 |
| N3—Ru1—N5 | 83.57 (10) | C10—C15—H15A | 119.7 |
| N1—Ru1—N5 | 84.88 (10) | C21—C16—C17 | 117.8 (3) |
| N3—Ru1—P1 | 90.07 (7) | C21—C16—P1 | 123.5 (2) |
| N1—Ru1—P1 | 90.63 (7) | C17—C16—P1 | 118.6 (2) |
| N5—Ru1—P1 | 172.20 (7) | C18—C17—C16 | 121.5 (3) |
| N3—Ru1—S1 | 170.14 (7) | C18—C17—H17A | 119.2 |
| N1—Ru1—S1 | 93.07 (7) | C16—C17—H17A | 119.2 |
| N5—Ru1—S1 | 87.41 (7) | C19—C18—C17 | 119.9 (3) |
| P1—Ru1—S1 | 99.23 (3) | C19—C18—H18A | 120.0 |
| N3—Ru1—S2 | 94.61 (7) | C17—C18—H18A | 120.0 |
| N1—Ru1—S2 | 169.78 (7) | C18—C19—C20 | 119.6 (3) |
| N5—Ru1—S2 | 86.63 (7) | C18—C19—H19A | 120.2 |
| P1—Ru1—S2 | 98.42 (3) | C20—C19—H19A | 120.2 |
| S1—Ru1—S2 | 80.86 (3) | C19—C20—C21 | 120.6 (3) |
| P2—S1—Ru1 | 84.74 (4) | C19—C20—H20A | 119.7 |
| P2—S2—Ru1 | 83.95 (4) | C21—C20—H20A | 119.7 |
| C16—P1—C10 | 101.43 (14) | C16—C21—C20 | 120.6 (3) |
| C16—P1—C22 | 99.51 (14) | C16—C21—H21A | 119.7 |
| C10—P1—C22 | 101.07 (14) | C20—C21—H21A | 119.7 |
| C16—P1—Ru1 | 117.05 (10) | C27—C22—C23 | 118.1 (3) |
| C10—P1—Ru1 | 112.69 (10) | C27—C22—P1 | 119.6 (2) |
| C22—P1—Ru1 | 121.98 (10) | C23—C22—P1 | 122.3 (2) |
| O1A—P2—O2A | 92.4 (6) | C24—C23—C22 | 120.6 (3) |
| O2—P2—O1 | 97.94 (17) | C24—C23—H23A | 119.7 |
| O2A—P2—O1 | 125.9 (4) | C22—C23—H23A | 119.7 |
| O2—P2—S1 | 118.31 (15) | C25—C24—C23 | 120.4 (4) |
| O1A—P2—S1 | 123.7 (4) | C25—C24—H24A | 119.8 |
| O2A—P2—S1 | 98.4 (4) | C23—C24—H24A | 119.8 |
| O1—P2—S1 | 105.05 (13) | C24—C25—C26 | 119.9 (3) |
| O2—P2—S2 | 115.21 (13) | C24—C25—H25A | 120.0 |
| O1A—P2—S2 | 122.1 (4) | C26—C25—H25A | 120.0 |
| O2A—P2—S2 | 105.9 (4) | C25—C26—C27 | 119.9 (4) |
| O1—P2—S2 | 112.03 (14) | C25—C26—H26A | 120.0 |
| S1—P2—S2 | 107.51 (5) | C27—C26—H26A | 120.0 |
| C1—N1—N2 | 106.2 (2) | C22—C27—C26 | 121.0 (3) |
| C1—N1—Ru1 | 134.7 (2) | C22—C27—H27A | 119.5 |
| N2—N1—Ru1 | 119.14 (19) | C26—C27—H27A | 119.5 |
| C3—N2—N1 | 109.4 (3) | C28—O1—P2 | 122.3 (3) |
| C3—N2—B1 | 130.7 (3) | O1—C28—C29 | 115.8 (6) |
| N1—N2—B1 | 119.5 (2) | O1—C28—H28A | 108.3 |
| C4—N3—N4 | 106.5 (2) | C29—C28—H28A | 108.3 |
| C4—N3—Ru1 | 135.1 (2) | O1—C28—H28B | 108.3 |
| N4—N3—Ru1 | 118.39 (18) | C29—C28—H28B | 108.3 |
| C6—N4—N3 | 109.0 (2) | H28A—C28—H28B | 107.4 |
| C6—N4—B1 | 130.5 (3) | C28—C29—H29A | 109.5 |
| N3—N4—B1 | 120.1 (2) | C28—C29—H29B | 109.5 |
| C7—N5—N6 | 106.2 (3) | H29A—C29—H29B | 109.5 |
| C7—N5—Ru1 | 135.9 (2) | C28—C29—H29C | 109.5 |
| N6—N5—Ru1 | 117.86 (19) | H29A—C29—H29C | 109.5 |
| C9—N6—N5 | 109.5 (3) | H29B—C29—H29C | 109.5 |
| C9—N6—B1 | 130.8 (3) | C28A—O1A—P2 | 119.2 (11) |
| N5—N6—B1 | 119.6 (2) | C28A—C29A—H29D | 109.5 |
| N1—C1—C2 | 110.6 (3) | C28A—C29A—H29E | 109.5 |
| N1—C1—H1A | 124.7 | H29D—C29A—H29E | 109.5 |
| C2—C1—H1A | 124.7 | C28A—C29A—H29F | 109.5 |
| C3—C2—C1 | 105.1 (3) | H29D—C29A—H29F | 109.5 |
| C3—C2—H2A | 127.5 | H29E—C29A—H29F | 109.5 |
| C1—C2—H2A | 127.5 | O1A—C28A—C29A | 130 (2) |
| N2—C3—C2 | 108.8 (3) | O1A—C28A—H28C | 104.7 |
| N2—C3—H3A | 125.6 | C29A—C28A—H28C | 104.7 |
| C2—C3—H3A | 125.6 | O1A—C28A—H28D | 104.7 |
| N3—C4—C5 | 110.7 (3) | C29A—C28A—H28D | 104.7 |
| N3—C4—H4A | 124.6 | H28C—C28A—H28D | 105.7 |
| C5—C4—H4A | 124.6 | C30—O2—P2 | 120.1 (3) |
| C6—C5—C4 | 105.1 (3) | O2—C30—C31 | 109.8 (10) |
| C6—C5—H5A | 127.5 | O2—C30—H30A | 109.7 |
| C4—C5—H5A | 127.5 | C31—C30—H30A | 109.7 |
| N4—C6—C5 | 108.7 (3) | O2—C30—H30B | 109.7 |
| N4—C6—H6A | 125.6 | C31—C30—H30B | 109.7 |
| C5—C6—H6A | 125.6 | H30A—C30—H30B | 108.2 |
| N5—C7—C8 | 110.6 (3) | C30—C31—H31A | 109.5 |
| N5—C7—H7A | 124.7 | C30—C31—H31B | 109.5 |
| C8—C7—H7A | 124.7 | H31A—C31—H31B | 109.5 |
| C9—C8—C7 | 105.1 (3) | C30—C31—H31C | 109.5 |
| C9—C8—H8A | 127.4 | H31A—C31—H31C | 109.5 |
| C7—C8—H8A | 127.4 | H31B—C31—H31C | 109.5 |
| N6—C9—C8 | 108.5 (3) | C30A—O2A—P2 | 128.8 (11) |
| N6—C9—H9A | 125.7 | O2A—C30A—C31A | 121 (3) |
| C8—C9—H9A | 125.7 | O2A—C30A—H30C | 107.0 |
| C11—C10—C15 | 118.3 (3) | C31A—C30A—H30C | 107.0 |
| C11—C10—P1 | 122.4 (2) | O2A—C30A—H30D | 107.0 |
| C15—C10—P1 | 119.3 (2) | C31A—C30A—H30D | 107.0 |
| C12—C11—C10 | 120.5 (3) | H30C—C30A—H30D | 106.7 |
| C12—C11—H11A | 119.8 | C30A—C31A—H31D | 109.5 |
| C10—C11—H11A | 119.8 | C30A—C31A—H31E | 109.5 |
| C13—C12—C11 | 120.4 (3) | H31D—C31A—H31E | 109.5 |
| C13—C12—H12A | 119.8 | C30A—C31A—H31F | 109.5 |
| C11—C12—H12A | 119.8 | H31D—C31A—H31F | 109.5 |
| C12—C13—C14 | 119.6 (3) | H31E—C31A—H31F | 109.5 |
| C12—C13—H13A | 120.2 | N2—B1—N4 | 109.7 (3) |
| C14—C13—H13A | 120.2 | N2—B1—N6 | 107.9 (3) |
| C13—C14—C15 | 120.5 (3) | N4—B1—N6 | 107.6 (3) |
| C13—C14—H14A | 119.8 | N2—B1—H1 | 110.5 |
| C15—C14—H14A | 119.8 | N4—B1—H1 | 110.5 |
| C14—C15—C10 | 120.7 (3) | N6—B1—H1 | 110.5 |
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2697).
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680803170X/lh2697sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S160053680803170X/lh2697Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report