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Acta Cryst. (2007). E63, m1561    [ doi:10.1107/S1600536807020259 ]

Bis[4'-(3,5-dibromophenyl)-2,2':6',2''-terpyridine]ruthenium(II) bis(hexafluorophosphate) acetonitrile disolvate

D. Chartrand, I. Theobald and G. S. Hanan

Abstract top

The title compound, [Ru(C21H13Br2N3)2](PF6)2·2CH2CN, was synthesized to investigate its photophysical properties. The molecule and the crystal structure are both non-centrosymmetric. The Ru atom is in a distorted octahedral coordination geometry. Intermolecular interactions are dominated by [pi]-stacking interactions between aromatic rings, with centroid-centroid distances between 3.7 and 3.9 Å. No bromine-bromine interactions are observed.

Comment top

The title compound crystallizes in the chiral space group (P1) although the molecule itself is not chiral in solution. Both dibromophenyl rings are almost parallel with a tilt angle of only 5° preventing a S2 axis which can pass through the molecule when the pendant rings are oriented perpendicular to each other.

There are 3 distinct intermolecular π stacking interactions present. The outer pyridyl groups coordinated to the metal atoms interact with their opposite pair forming two distinct stacking interactions 90° apart(Fig 2). The distance between the ring centroids are about 3.9 Å, with a perpendicular (centroid-to-plane) distance of about 3.4 Å. The third stacking interaction occurs between opposite dibromophenyl groups of molecules along the c axis. The centroid distance between both phenyl rings is 3.7Å and the perpendicular distance amount to 3.5 Å.

The Br···Br distances varying from 4.2Å to 4.6Å and are much longer than the expected Br···Br short contact distances of 3.4Å to 3.6Å (Medlycott et al., 2007, 2005) (Reddy et al., 2006). Therefore, no intermolecular bromine-bromine interactions occur. There is one Br···F short contact, between Br1 and F3 of 3.1 Å, showing a weak interaction with the hexafluorophosphate anion.

Related literature top

More details on bromine-bromine interactions in related compounds, such as bis(4-para-bromophenylterpyridine) metal complexes, are described by Medlycott et al. (2005, 2007) and Reddy et al.(2006).

Experimental top

The title compound was synthesized by heating at reflux overnight two equivalents of the 4'-(3,5-dibromophenyl)2,2':6',2"-terpyridine ligand (0.467 g), one equivalent of RuCl3 (0.104 g) and four equivalents of silver nitrate (0.340 g) in ethanol (50 ml). The crude product was filtered over celite and purified by flash chromatography (silica gel, eluant (v/v): 4 acetone, 8 acetonitrile and 1 saturated aqueous solution of KNO3). The complex was precipitated with KPF6 and dried under vacuum for a final yield of 51% (0.338 g). The title compound crystallized by isopropyl ether diffusion to an acetonitrile solution of the complex.

Refinement top

The H atoms were generated with idealized geometry (sp2 C—H 0.95 Å, sp3 C—H 0.98 Å) and were included in the refinement in the riding model approximation; their temperature factors were set to 1.5 times those of the equivalent isotropic temperature factors of the parent site (methyl) and 1.2 times for others. The H atoms of the methyl groups of the acetonitrile molecules were positioned with idealized geometry allowed to rotate but not to tip. The maximum density peak of 1.01 e Å-3) is located 0.878 Å from Br4.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (local program).

Figures top
[Figure 1] Fig. 1. ORTEP view of the title compound. Thermal ellipsoids of non-hydrogen are shown at 50% probability levels.
[Figure 2] Fig. 2. The packing of the compound, viewed along the c axis, showing the π stacking of the pyridyl groups. H atoms, anions and solvent molecules have been omitted for clarity.
Bis[4'-(3,5-dibromophenyl)-2,2':6',2''-terpyridine]ruthenium(II) bis(hexafluorophosphate) acetonitrile disolvate top
Crystal data top
[Ru(C21H13Br2N3)2](PF6)2·2C2H3NZ = 1
Mr = 1407.45F(000) = 686
Triclinic, P1Dx = 1.895 Mg m−3
Hall symbol: P 1Cu Kα radiation, λ = 1.54178 Å
a = 8.3158 (1) ÅCell parameters from 17454 reflections
b = 9.2087 (1) Åθ = 2.7–67.3°
c = 16.2114 (1) ŵ = 7.78 mm−1
α = 89.7346 (5)°T = 100 K
β = 88.7088 (4)°Needle-like, red
γ = 83.6367 (5)°0.10 × 0.05 × 0.02 mm
V = 1233.47 (2) Å3
Data collection top
Bruker APEX II
diffractometer		7003 independent reflections
Radiation source: Micro source6901 reflections with I > 2σ(I)
Helios opticsRint = 0.027
Detector resolution: 5.5 pixels mm-1θmax = 67.9°, θmin = 2.7°
ω scansh = −9→9
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		k = −10→10
Tmin = 0.601, Tmax = 0.857l = −19→19
19475 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.062 w = 1/[σ2(Fo2) + (0.0341P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
7003 reflectionsΔρmax = 1.01 e Å−3
661 parametersΔρmin = −0.39 e Å−3
3 restraintsAbsolute structure: Flack (1983), 2532 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.041 (5)
Crystal data top
[Ru(C21H13Br2N3)2](PF6)2·2C2H3Nγ = 83.6367 (5)°
Mr = 1407.45V = 1233.47 (2) Å3
Triclinic, P1Z = 1
a = 8.3158 (1) ÅCu Kα radiation
b = 9.2087 (1) ŵ = 7.78 mm−1
c = 16.2114 (1) ÅT = 100 K
α = 89.7346 (5)°0.10 × 0.05 × 0.02 mm
β = 88.7088 (4)°
Data collection top
Bruker APEX II
diffractometer		7003 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		6901 reflections with I > 2σ(I)
Tmin = 0.601, Tmax = 0.857Rint = 0.027
19475 measured reflectionsθmax = 67.9°
Refinement top
R[F2 > 2σ(F2)] = 0.025H-atom parameters constrained
wR(F2) = 0.062Δρmax = 1.01 e Å−3
S = 1.06Δρmin = −0.39 e Å−3
7003 reflectionsAbsolute structure: Flack (1983), 2532 Friedel pairs
661 parametersFlack parameter: 0.041 (5)
3 restraints
Special details top

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 > 2σ(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.

All remaining electron density larger then 0.5 is located less then 0.9 Å from an heavy atom (Br or Ru). Higher symmetry solution, using whole data and only the main molecule, were searched with PLATON but none were found.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ru10.05928 (2)0.69668 (2)0.094352 (15)0.01474 (8)
Br10.11826 (6)0.33373 (6)−0.45785 (3)0.03716 (14)
Br20.36580 (6)0.88101 (6)−0.47857 (3)0.03908 (14)
Br3−0.34776 (6)0.45920 (6)0.64229 (3)0.04448 (16)
Br4−0.12003 (6)1.01619 (6)0.65312 (3)0.03841 (14)
N10.1580 (3)0.4799 (4)0.08447 (18)0.0148 (7)
N20.1171 (4)0.6848 (4)−0.02525 (18)0.0166 (8)
N3−0.0208 (3)0.9084 (4)0.05537 (18)0.0183 (8)
N4−0.1640 (4)0.6186 (4)0.08997 (19)0.0202 (8)
N5−0.0031 (4)0.6983 (4)0.21318 (18)0.0170 (8)
N60.2574 (4)0.7774 (4)0.14697 (17)0.0159 (7)
C10.1713 (4)0.3783 (5)0.1444 (2)0.0202 (9)
H1A0.13430.40500.19860.024*
C20.2378 (5)0.2349 (5)0.1295 (2)0.0223 (10)
H2A0.24720.16580.17330.027*
C30.2899 (5)0.1938 (5)0.0510 (3)0.0243 (11)
H3A0.33660.09670.03990.029*
C40.2726 (4)0.2984 (5)−0.0125 (2)0.0216 (10)
H4A0.30640.2726−0.06740.026*
C50.2056 (4)0.4398 (5)0.0057 (2)0.0180 (9)
C60.1790 (4)0.5557 (4)−0.0570 (2)0.0160 (9)
C70.2061 (4)0.5403 (5)−0.1414 (2)0.0211 (10)
H7A0.24890.4486−0.16380.025*
C80.1696 (4)0.6614 (5)−0.1934 (2)0.0186 (9)
C90.1080 (4)0.7944 (5)−0.1582 (2)0.0180 (9)
H9A0.08450.8782−0.19200.022*
C100.0811 (4)0.8038 (4)−0.0736 (2)0.0161 (9)
C110.0059 (4)0.9314 (5)−0.0274 (2)0.0180 (9)
C12−0.0388 (5)1.0661 (5)−0.0633 (2)0.0213 (9)
H12A−0.01801.0809−0.12040.026*
C13−0.1141 (5)1.1788 (5)−0.0155 (3)0.0270 (11)
H13A−0.14611.2718−0.03930.032*
C14−0.1418 (5)1.1539 (5)0.0673 (3)0.0240 (11)
H14A−0.19481.22950.10100.029*
C15−0.0926 (4)1.0195 (5)0.1010 (2)0.0235 (10)
H15A−0.11001.00470.15840.028*
C160.1939 (5)0.6439 (5)−0.2841 (2)0.0193 (10)
C170.1538 (5)0.5204 (5)−0.3221 (2)0.0239 (11)
H17A0.10910.4470−0.29040.029*
C180.1779 (5)0.5020 (5)−0.4065 (2)0.0267 (11)
C190.2426 (5)0.6077 (6)−0.4544 (2)0.0278 (12)
H19A0.26130.5949−0.51210.033*
C200.2782 (5)0.7315 (5)−0.4150 (2)0.0246 (11)
C210.2569 (5)0.7536 (5)−0.3312 (2)0.0229 (10)
H21A0.28390.8405−0.30610.027*
C22−0.2399 (4)0.5796 (5)0.0228 (2)0.0221 (10)
H22A−0.19860.6031−0.03020.027*
C23−0.3754 (5)0.5068 (5)0.0280 (3)0.0238 (10)
H23A−0.42590.4791−0.02070.029*
C24−0.4375 (4)0.4742 (5)0.1052 (2)0.0221 (10)
H24A−0.53010.42270.11010.027*
C25−0.3635 (4)0.5174 (5)0.1743 (2)0.0200 (9)
H25A−0.40560.49680.22750.024*
C26−0.2277 (4)0.5909 (4)0.1665 (2)0.0166 (9)
C27−0.1418 (4)0.6440 (4)0.2361 (2)0.0162 (9)
C28−0.1902 (4)0.6463 (5)0.3193 (2)0.0200 (9)
H28A−0.28780.60880.33600.024*
C29−0.0949 (5)0.7034 (5)0.3772 (2)0.0197 (10)
C300.0507 (4)0.7544 (5)0.3518 (2)0.0192 (9)
H30A0.11830.79200.39110.023*
C310.0957 (4)0.7498 (4)0.2689 (2)0.0168 (9)
C320.2446 (4)0.7949 (4)0.2308 (2)0.0182 (9)
C330.3628 (4)0.8516 (5)0.2746 (2)0.0180 (9)
H33A0.35270.85990.33290.022*
C340.4973 (5)0.8969 (5)0.2333 (2)0.0220 (10)
H34A0.57970.93670.26270.026*
C350.5078 (4)0.8823 (5)0.1480 (2)0.0181 (10)
H35A0.59700.91380.11790.022*
C360.3880 (4)0.8219 (4)0.1076 (2)0.0156 (9)
H36A0.39750.81100.04940.019*
C37−0.1458 (5)0.7154 (5)0.4666 (2)0.0223 (11)
C38−0.2180 (5)0.6020 (5)0.5051 (2)0.0237 (10)
H38A−0.23840.51750.47540.028*
C39−0.2583 (5)0.6177 (5)0.5879 (3)0.0290 (12)
C40−0.2329 (5)0.7366 (6)0.6340 (2)0.0288 (12)
H40A−0.26210.74280.69100.035*
C41−0.1627 (5)0.8477 (5)0.5939 (2)0.0257 (11)
C42−0.1183 (5)0.8395 (5)0.5107 (2)0.0223 (11)
H42A−0.07030.91700.48440.027*
P10.91524 (12)0.18925 (13)0.33410 (6)0.0245 (3)
F11.0258 (3)0.3206 (3)0.33116 (16)0.0376 (7)
F21.0441 (3)0.0963 (3)0.27442 (16)0.0386 (7)
F31.0125 (3)0.1216 (3)0.41140 (15)0.0366 (7)
F40.8200 (4)0.2540 (4)0.25552 (18)0.0533 (9)
F50.7874 (3)0.2803 (4)0.39307 (17)0.0442 (8)
F60.8064 (3)0.0552 (3)0.33533 (18)0.0391 (7)
P20.56414 (12)0.89525 (16)0.87713 (6)0.0317 (3)
F70.6287 (4)1.0460 (5)0.85268 (18)0.0663 (12)
F80.7329 (3)0.8074 (5)0.85077 (17)0.0654 (12)
F90.6294 (3)0.9084 (4)0.96895 (14)0.0413 (8)
F100.4985 (3)0.8787 (4)0.78624 (15)0.0465 (9)
F110.3941 (3)0.9816 (4)0.90451 (17)0.0424 (7)
F120.4954 (3)0.7446 (4)0.90392 (17)0.0412 (7)
N500.1777 (8)0.1734 (7)0.7721 (3)0.0651 (17)
C500.2877 (11)0.1696 (9)0.7375 (5)0.071 (2)
C510.4432 (10)0.1555 (10)0.6881 (5)0.084 (3)
H51A0.53110.18060.72270.126*
H51B0.43270.22190.64060.126*
H51C0.46750.05470.66860.126*
N520.4003 (6)0.4943 (6)0.3489 (3)0.0504 (14)
C520.4083 (6)0.3754 (7)0.3625 (3)0.0398 (14)
C530.4195 (7)0.2178 (6)0.3814 (4)0.0566 (18)
H53A0.46180.20030.43690.085*
H53B0.49240.16390.34100.085*
H53C0.31180.18460.37870.085*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.01455 (11)0.01488 (17)0.01510 (12)−0.00285 (11)−0.00092 (9)−0.00290 (11)
Br10.0492 (3)0.0331 (3)0.0302 (2)−0.0078 (3)−0.00386 (19)−0.0148 (2)
Br20.0558 (3)0.0436 (3)0.0207 (2)−0.0183 (3)−0.00158 (19)0.0046 (2)
Br30.0552 (3)0.0416 (4)0.0379 (3)−0.0145 (3)0.0142 (2)0.0083 (2)
Br40.0549 (3)0.0346 (3)0.0258 (2)−0.0057 (2)0.00264 (19)−0.0093 (2)
N10.0155 (13)0.0097 (19)0.0208 (14)−0.0075 (13)−0.0038 (11)−0.0051 (13)
N20.0155 (14)0.016 (2)0.0180 (14)−0.0017 (14)−0.0017 (11)−0.0023 (14)
N30.0167 (14)0.021 (2)0.0184 (14)−0.0060 (14)−0.0023 (11)−0.0051 (14)
N40.0214 (15)0.017 (2)0.0223 (15)−0.0001 (15)−0.0015 (12)−0.0021 (14)
N50.0186 (15)0.014 (2)0.0189 (14)−0.0036 (14)−0.0005 (12)−0.0047 (13)
N60.0203 (15)0.0107 (19)0.0165 (13)−0.0015 (14)0.0009 (11)−0.0032 (13)
C10.0181 (16)0.022 (3)0.0208 (17)−0.0028 (17)−0.0010 (14)−0.0005 (17)
C20.0220 (19)0.019 (3)0.028 (2)−0.0082 (18)−0.0046 (15)0.0034 (18)
C30.0250 (18)0.018 (3)0.030 (2)−0.0006 (18)0.0004 (15)−0.0017 (18)
C40.027 (2)0.018 (2)0.0205 (17)−0.0033 (18)−0.0007 (15)−0.0053 (16)
C50.0146 (15)0.020 (2)0.0198 (17)−0.0053 (16)−0.0009 (13)−0.0006 (16)
C60.0136 (15)0.015 (2)0.0208 (17)−0.0059 (16)−0.0050 (13)−0.0030 (16)
C70.0232 (17)0.020 (2)0.0196 (17)0.0006 (17)0.0014 (14)−0.0054 (16)
C80.0208 (18)0.018 (2)0.0178 (17)−0.0062 (17)−0.0026 (14)−0.0021 (17)
C90.0187 (16)0.017 (2)0.0189 (16)−0.0034 (16)−0.0025 (13)−0.0010 (16)
C100.0152 (16)0.011 (2)0.0235 (17)−0.0086 (16)−0.0046 (13)−0.0030 (16)
C110.0161 (15)0.020 (2)0.0189 (17)−0.0047 (17)−0.0035 (13)−0.0058 (16)
C120.0227 (17)0.020 (3)0.0213 (17)−0.0040 (17)−0.0041 (14)−0.0029 (17)
C130.0302 (19)0.016 (3)0.034 (2)0.0014 (19)−0.0078 (16)−0.0019 (19)
C140.0218 (19)0.020 (3)0.031 (2)−0.0014 (19)−0.0041 (16)−0.0133 (19)
C150.0151 (16)0.034 (3)0.0214 (17)−0.0014 (18)−0.0015 (13)−0.0055 (18)
C160.0237 (18)0.014 (3)0.0201 (17)−0.0032 (18)−0.0006 (14)−0.0075 (18)
C170.0259 (19)0.027 (3)0.0188 (17)−0.0011 (19)−0.0027 (15)−0.0031 (19)
C180.033 (2)0.027 (3)0.0196 (18)0.001 (2)−0.0074 (15)−0.0116 (18)
C190.030 (2)0.033 (3)0.0199 (18)−0.001 (2)−0.0031 (15)−0.007 (2)
C200.0258 (19)0.024 (3)0.0251 (18)−0.006 (2)−0.0051 (15)−0.002 (2)
C210.0258 (18)0.026 (3)0.0176 (17)−0.0032 (18)−0.0043 (14)0.0003 (17)
C220.0180 (17)0.025 (3)0.0236 (18)−0.0029 (18)−0.0016 (14)−0.0007 (18)
C230.021 (2)0.020 (3)0.030 (2)−0.0011 (19)−0.0072 (16)−0.0098 (18)
C240.0176 (17)0.017 (2)0.033 (2)−0.0048 (17)−0.0024 (14)−0.0045 (18)
C250.0150 (15)0.017 (2)0.0276 (18)−0.0021 (16)−0.0011 (14)−0.0013 (17)
C260.0178 (16)0.011 (2)0.0206 (16)0.0003 (16)−0.0013 (13)−0.0048 (15)
C270.0157 (16)0.011 (2)0.0227 (17)−0.0043 (16)−0.0037 (13)−0.0027 (16)
C280.0176 (16)0.021 (2)0.0211 (17)−0.0017 (17)0.0028 (14)−0.0011 (16)
C290.0211 (18)0.018 (2)0.0193 (18)−0.0001 (18)0.0002 (14)−0.0036 (17)
C300.0197 (17)0.018 (2)0.0191 (17)−0.0003 (17)−0.0007 (14)−0.0043 (16)
C310.0159 (16)0.015 (2)0.0200 (17)−0.0021 (16)−0.0041 (13)0.0010 (16)
C320.0182 (16)0.015 (2)0.0206 (17)0.0002 (16)0.0009 (14)−0.0005 (16)
C330.0206 (17)0.017 (2)0.0169 (16)−0.0048 (17)−0.0036 (14)−0.0048 (16)
C340.0201 (17)0.020 (2)0.0275 (19)−0.0063 (18)−0.0069 (15)−0.0006 (18)
C350.0156 (17)0.010 (2)0.0288 (19)−0.0019 (17)0.0012 (15)−0.0023 (17)
C360.0181 (16)0.012 (2)0.0177 (16)−0.0040 (16)−0.0006 (13)0.0004 (16)
C370.0226 (19)0.024 (3)0.0199 (18)−0.0016 (18)0.0032 (15)0.0018 (19)
C380.0266 (19)0.021 (3)0.0241 (18)−0.0052 (19)−0.0002 (15)−0.0042 (18)
C390.030 (2)0.029 (3)0.027 (2)−0.003 (2)0.0072 (16)0.006 (2)
C400.033 (2)0.034 (3)0.0181 (18)0.000 (2)0.0025 (16)−0.001 (2)
C410.027 (2)0.026 (3)0.0241 (19)−0.0038 (19)0.0002 (15)−0.0045 (19)
C420.0236 (18)0.021 (3)0.0225 (18)−0.0034 (19)0.0012 (15)−0.0021 (19)
P10.0310 (5)0.0211 (7)0.0215 (4)−0.0018 (5)−0.0035 (4)−0.0038 (4)
F10.0522 (15)0.0246 (16)0.0377 (13)−0.0128 (13)0.0051 (12)0.0019 (12)
F20.0396 (13)0.0349 (18)0.0399 (14)0.0016 (13)0.0039 (11)−0.0082 (13)
F30.0489 (14)0.0327 (17)0.0317 (12)−0.0180 (13)−0.0144 (11)0.0082 (12)
F40.0711 (19)0.045 (2)0.0407 (14)0.0144 (17)−0.0275 (14)−0.0030 (14)
F50.0421 (14)0.042 (2)0.0490 (15)−0.0054 (14)0.0066 (12)−0.0238 (14)
F60.0328 (12)0.0324 (18)0.0536 (15)−0.0086 (13)−0.0081 (11)−0.0102 (13)
P20.0220 (5)0.0555 (9)0.0197 (5)−0.0134 (5)−0.0003 (4)−0.0055 (5)
F70.073 (2)0.100 (3)0.0369 (15)−0.055 (2)−0.0173 (14)0.0220 (19)
F80.0231 (12)0.135 (4)0.0355 (14)0.0025 (18)0.0015 (11)−0.0110 (17)
F90.0375 (13)0.069 (2)0.0221 (11)−0.0276 (14)−0.0040 (10)0.0018 (13)
F100.0344 (13)0.083 (3)0.0232 (11)−0.0109 (15)−0.0071 (10)−0.0110 (14)
F110.0390 (14)0.045 (2)0.0430 (14)−0.0045 (14)0.0005 (11)−0.0157 (13)
F120.0399 (14)0.0401 (19)0.0450 (15)−0.0084 (13)−0.0095 (11)−0.0051 (14)
N500.092 (4)0.058 (4)0.044 (3)−0.004 (3)0.009 (3)0.011 (3)
C500.100 (6)0.054 (5)0.060 (4)−0.014 (4)−0.010 (4)0.011 (4)
C510.091 (5)0.082 (6)0.082 (5)−0.018 (5)0.002 (4)0.020 (5)
N520.057 (3)0.044 (3)0.048 (2)0.002 (2)0.024 (2)0.010 (2)
C520.042 (3)0.044 (4)0.032 (2)−0.004 (2)0.016 (2)−0.006 (2)
C530.038 (3)0.033 (4)0.097 (5)−0.003 (3)0.020 (3)−0.006 (3)
Geometric parameters (Å, °) top
Ru1—N51.983 (3)C22—C231.375 (7)
Ru1—N21.988 (3)C22—H22a0.95
Ru1—N42.067 (4)C23—C241.387 (6)
Ru1—N12.078 (3)C23—H23a0.95
Ru1—N62.082 (4)C24—C251.371 (6)
Ru1—N32.089 (3)C24—H24a0.95
Br1—C181.882 (5)C25—C261.383 (6)
Br2—C201.914 (4)C25—H25a0.95
Br3—C391.913 (5)C26—C271.463 (6)
Br4—C411.899 (5)C27—C281.398 (5)
N1—C11.343 (5)C28—C291.385 (7)
N1—C51.368 (5)C28—H28a0.95
N2—C61.342 (5)C29—C301.399 (6)
N2—C101.355 (5)C29—C371.502 (5)
N3—C151.342 (5)C30—C311.385 (5)
N3—C111.374 (4)C30—H30a0.95
N4—C221.341 (6)C31—C321.471 (5)
N4—C261.372 (5)C32—C331.376 (6)
N5—C271.351 (5)C33—C341.393 (6)
N5—C311.357 (6)C33—H33a0.95
N6—C361.349 (5)C34—C351.390 (6)
N6—C321.370 (5)C34—H34a0.95
C1—C21.394 (6)C35—C361.374 (6)
C1—H1a0.95C35—H35a0.95
C2—C31.376 (6)C36—H36a0.95
C2—H2a0.95C37—C421.394 (7)
C3—C41.405 (5)C37—C381.398 (6)
C3—H3a0.95C38—C391.380 (6)
C4—C51.389 (6)C38—H38a0.95
C4—H4a0.95C39—C401.368 (8)
C5—C61.473 (5)C40—C411.385 (7)
C6—C71.386 (5)C40—H40a0.95
C7—C81.406 (5)C41—C421.390 (6)
C7—H7a0.95C42—H42a0.95
C8—C91.394 (6)P1—F51.585 (3)
C8—C161.485 (5)P1—F31.593 (2)
C9—C101.386 (5)P1—F41.594 (3)
C9—H9a0.95P1—F11.599 (3)
C10—C111.469 (6)P1—F21.605 (3)
C11—C121.384 (5)P1—F61.609 (4)
C12—C131.382 (6)P2—F71.588 (4)
C12—H12a0.95P2—F81.591 (3)
C13—C141.381 (6)P2—F101.597 (3)
C13—H13a0.95P2—F111.598 (3)
C14—C151.375 (6)P2—F91.606 (3)
C14—H14a0.95P2—F121.612 (4)
C15—H15a0.95N50—C501.060 (9)
C16—C171.373 (7)C50—C511.499 (12)
C16—C211.404 (6)C51—H51a0.98
C17—C181.387 (5)C51—H51b0.98
C17—H17a0.95C51—H51c0.98
C18—C191.389 (7)N52—C521.111 (7)
C19—C201.373 (8)C52—C531.475 (8)
C19—H19a0.95C53—H53a0.98
C20—C211.380 (6)C53—H53b0.98
C21—H21a0.95C53—H53c0.98
N5—Ru1—N2176.91 (17)C25—C24—C23119.2 (4)
N5—Ru1—N479.20 (13)C25—C24—H24A120.4
N2—Ru1—N498.47 (13)C23—C24—H24A120.4
N5—Ru1—N198.77 (12)C24—C25—C26120.0 (3)
N2—Ru1—N178.99 (12)C24—C25—H25A120
N4—Ru1—N186.33 (12)C26—C25—H25A120
N5—Ru1—N678.44 (13)N4—C26—C25120.4 (4)
N2—Ru1—N6103.89 (13)N4—C26—C27115.3 (3)
N4—Ru1—N6157.64 (11)C25—C26—C27124.3 (3)
N1—Ru1—N697.48 (12)N5—C27—C28119.6 (4)
N5—Ru1—N3103.40 (12)N5—C27—C26113.1 (3)
N2—Ru1—N378.78 (12)C28—C27—C26127.3 (4)
N4—Ru1—N395.84 (12)C29—C28—C27119.6 (4)
N1—Ru1—N3157.75 (11)C29—C28—H28A120.2
N6—Ru1—N388.91 (12)C27—C28—H28A120.2
C1—N1—C5118.8 (3)C28—C29—C30119.4 (3)
C1—N1—RU1127.6 (3)C28—C29—C37121.6 (4)
C5—N1—RU1113.5 (2)C30—C29—C37119.0 (4)
C6—N2—C10121.7 (3)C31—C30—C29119.6 (4)
C6—N2—RU1118.9 (2)C31—C30—H30A120.2
C10—N2—RU1119.2 (3)C29—C30—H30A120.2
C15—N3—C11118.6 (3)N5—C31—C30119.7 (3)
C15—N3—RU1127.9 (2)N5—C31—C32112.8 (3)
C11—N3—RU1113.6 (3)C30—C31—C32127.6 (4)
C22—N4—C26119.1 (4)N6—C32—C33121.6 (3)
C22—N4—RU1127.3 (2)N6—C32—C31114.9 (4)
C26—N4—RU1113.2 (3)C33—C32—C31123.5 (3)
C27—N5—C31122.1 (3)C32—C33—C34119.9 (3)
C27—N5—RU1118.4 (3)C32—C33—H33A120
C31—N5—RU1119.5 (2)C34—C33—H33A120
C36—N6—C32118.0 (4)C35—C34—C33118.3 (4)
C36—N6—RU1127.5 (2)C35—C34—H34A120.9
C32—N6—RU1114.4 (2)C33—C34—H34A120.9
N1—C1—C2122.1 (3)C36—C35—C34119.4 (4)
N1—C1—H1A118.9C36—C35—H35A120.3
C2—C1—H1A118.9C34—C35—H35A120.3
C3—C2—C1119.7 (3)N6—C36—C35122.8 (3)
C3—C2—H2A120.2N6—C36—H36A118.6
C1—C2—H2A120.2C35—C36—H36A118.6
C2—C3—C4118.6 (4)C42—C37—C38120.6 (4)
C2—C3—H3A120.7C42—C37—C29119.3 (4)
C4—C3—H3A120.7C38—C37—C29120.1 (4)
C5—C4—C3119.4 (3)C39—C38—C37117.4 (5)
C5—C4—H4A120.3C39—C38—H38A121.3
C3—C4—H4A120.3C37—C38—H38A121.3
N1—C5—C4121.3 (3)C40—C39—C38124.2 (4)
N1—C5—C6115.4 (3)C40—C39—BR3118.0 (3)
C4—C5—C6123.2 (3)C38—C39—BR3117.7 (4)
N2—C6—C7120.4 (3)C39—C40—C41116.9 (4)
N2—C6—C5113.0 (3)C39—C40—H40A121.5
C7—C6—C5126.5 (4)C41—C40—H40A121.5
C6—C7—C8119.5 (4)C40—C41—C42122.1 (5)
C6—C7—H7A120.3C40—C41—BR4120.0 (3)
C8—C7—H7A120.3C42—C41—BR4117.9 (4)
C9—C8—C7118.6 (3)C41—C42—C37118.7 (4)
C9—C8—C16121.9 (3)C41—C42—H42A120.7
C7—C8—C16119.5 (4)C37—C42—H42A120.7
C10—C9—C8119.7 (3)F5—P1—F391.04 (15)
C10—C9—H9A120.1F5—P1—F490.19 (16)
C8—C9—H9A120.1F3—P1—F4178.70 (18)
N2—C10—C9120.1 (3)F5—P1—F190.91 (17)
N2—C10—C11113.1 (3)F3—P1—F189.85 (15)
C9—C10—C11126.8 (3)F4—P1—F190.55 (18)
N3—C11—C12121.1 (3)F5—P1—F2179.7 (2)
N3—C11—C10115.4 (3)F3—P1—F288.94 (14)
C12—C11—C10123.5 (3)F4—P1—F289.82 (15)
C13—C12—C11119.6 (3)F1—P1—F289.43 (16)
C13—C12—H12A120.2F5—P1—F690.37 (17)
C11—C12—H12A120.2F3—P1—F690.41 (15)
C14—C13—C12118.7 (4)F4—P1—F689.17 (18)
C14—C13—H13A120.6F1—P1—F6178.69 (16)
C12—C13—H13A120.6F2—P1—F689.29 (17)
C15—C14—C13119.9 (4)F7—P2—F891.2 (2)
C15—C14—H14A120F7—P2—F1090.82 (18)
C13—C14—H14A120F8—P2—F1090.54 (15)
N3—C15—C14122.1 (3)F7—P2—F1189.6 (2)
N3—C15—H15A119F8—P2—F11179.2 (2)
C14—C15—H15A119F10—P2—F1189.81 (15)
C17—C16—C21119.8 (4)F7—P2—F990.38 (18)
C17—C16—C8120.0 (4)F8—P2—F989.23 (15)
C21—C16—C8120.3 (4)F10—P2—F9178.8 (2)
C16—C17—C18120.5 (4)F11—P2—F990.40 (15)
C16—C17—H17A119.8F7—P2—F12178.4 (2)
C18—C17—H17A119.8F8—P2—F1290.2 (2)
C17—C18—C19121.0 (5)F10—P2—F1289.99 (18)
C17—C18—BR1119.8 (4)F11—P2—F1289.01 (16)
C19—C18—BR1119.2 (3)F9—P2—F1288.81 (16)
C20—C19—C18117.2 (4)N50—C50—C51176.9 (10)
C20—C19—H19A121.4C50—C51—H51A109.5
C18—C19—H19A121.4C50—C51—H51B109.5
C19—C20—C21123.6 (4)H51A—C51—H51B109.5
C19—C20—BR2118.8 (3)C50—C51—H51C109.5
C21—C20—BR2117.6 (4)H51A—C51—H51C109.5
C20—C21—C16117.9 (5)H51B—C51—H51C109.5
C20—C21—H21A121N52—C52—C53179.4 (7)
C16—C21—H21A121C52—C53—H53A109.5
N4—C22—C23122.2 (3)C52—C53—H53B109.5
N4—C22—H22A118.9H53A—C53—H53B109.5
C23—C22—H22A118.9C52—C53—H53C109.5
C22—C23—C24119.1 (4)H53A—C53—H53C109.5
C22—C23—H23A120.5H53B—C53—H53C109.5
C24—C23—H23A120.5
N5—RU1—N1—C1−0.2 (4)RU1—N3—C11—C101.5 (4)
N2—RU1—N1—C1−178.1 (4)N2—C10—C11—N3−2.3 (5)
N4—RU1—N1—C1−78.7 (3)C9—C10—C11—N3174.0 (4)
N6—RU1—N1—C179.1 (3)N2—C10—C11—C12178.8 (4)
N3—RU1—N1—C1−175.2 (3)C9—C10—C11—C12−4.8 (7)
N5—RU1—N1—C5176.2 (3)N3—C11—C12—C13−1.1 (6)
N2—RU1—N1—C5−1.6 (3)C10—C11—C12—C13177.8 (4)
N4—RU1—N1—C597.7 (3)C11—C12—C13—C140.4 (7)
N6—RU1—N1—C5−104.4 (3)C12—C13—C14—C150.9 (7)
N3—RU1—N1—C51.3 (5)C11—N3—C15—C140.9 (6)
N4—RU1—N2—C6−81.4 (3)RU1—N3—C15—C14−179.1 (3)
N1—RU1—N2—C63.2 (3)C13—C14—C15—N3−1.6 (7)
N6—RU1—N2—C698.3 (3)C9—C8—C16—C17−138.5 (4)
N3—RU1—N2—C6−175.7 (3)C7—C8—C16—C1740.2 (5)
N4—RU1—N2—C1093.4 (3)C9—C8—C16—C2141.1 (5)
N1—RU1—N2—C10177.9 (3)C7—C8—C16—C21−140.3 (4)
N6—RU1—N2—C10−87.0 (3)C21—C16—C17—C181.3 (5)
N3—RU1—N2—C10−0.9 (3)C8—C16—C17—C18−179.2 (3)
N5—RU1—N3—C151.9 (4)C16—C17—C18—C19−0.2 (6)
N2—RU1—N3—C15179.7 (4)C16—C17—C18—BR1−178.8 (3)
N4—RU1—N3—C1582.1 (4)C17—C18—C19—C20−1.2 (5)
N1—RU1—N3—C15176.7 (3)BR1—C18—C19—C20177.4 (3)
N6—RU1—N3—C15−76.0 (4)C18—C19—C20—C211.6 (6)
N5—RU1—N3—C11−178.1 (3)C18—C19—C20—BR2−179.5 (3)
N2—RU1—N3—C11−0.4 (3)C19—C20—C21—C16−0.6 (5)
N4—RU1—N3—C11−97.9 (3)BR2—C20—C21—C16−179.5 (3)
N1—RU1—N3—C11−3.3 (5)C17—C16—C21—C20−0.9 (5)
N6—RU1—N3—C11104.0 (3)C8—C16—C21—C20179.5 (3)
N5—RU1—N4—C22179.8 (3)C26—N4—C22—C23−3.0 (5)
N2—RU1—N4—C22−2.2 (3)RU1—N4—C22—C23169.1 (3)
N1—RU1—N4—C22−80.5 (3)N4—C22—C23—C241.0 (6)
N6—RU1—N4—C22178.7 (3)C22—C23—C24—C250.9 (6)
N3—RU1—N4—C2277.3 (3)C23—C24—C25—C26−0.8 (5)
N5—RU1—N4—C26−7.7 (2)C22—N4—C26—C253.1 (5)
N2—RU1—N4—C26170.2 (2)RU1—N4—C26—C25−170.0 (3)
N1—RU1—N4—C2691.9 (2)C22—N4—C26—C27−176.9 (3)
N6—RU1—N4—C26−8.9 (5)RU1—N4—C26—C2710.0 (4)
N3—RU1—N4—C26−110.3 (2)C24—C25—C26—N4−1.3 (5)
N4—RU1—N5—C274.3 (3)C24—C25—C26—C27178.8 (3)
N1—RU1—N5—C27−80.2 (3)C31—N5—C27—C283.0 (5)
N6—RU1—N5—C27−176.2 (3)RU1—N5—C27—C28−178.8 (3)
N3—RU1—N5—C2797.8 (3)C31—N5—C27—C26−178.4 (3)
N4—RU1—N5—C31−177.5 (3)RU1—N5—C27—C26−0.2 (4)
N1—RU1—N5—C3198.0 (3)N4—C26—C27—N5−6.6 (4)
N6—RU1—N5—C312.1 (3)C25—C26—C27—N5173.3 (3)
N3—RU1—N5—C31−84.0 (3)N4—C26—C27—C28171.9 (3)
N5—RU1—N6—C36−177.3 (3)C25—C26—C27—C28−8.2 (6)
N2—RU1—N6—C364.7 (3)N5—C27—C28—C29−0.4 (5)
N4—RU1—N6—C36−176.2 (3)C26—C27—C28—C29−178.8 (3)
N1—RU1—N6—C3685.2 (3)C27—C28—C29—C30−1.7 (5)
N3—RU1—N6—C36−73.4 (3)C27—C28—C29—C37176.8 (3)
N5—RU1—N6—C32−2.0 (2)C28—C29—C30—C311.3 (5)
N2—RU1—N6—C32−179.9 (2)C37—C29—C30—C31−177.3 (3)
N4—RU1—N6—C32−0.8 (4)C27—N5—C31—C30−3.4 (5)
N1—RU1—N6—C32−99.5 (2)RU1—N5—C31—C30178.4 (3)
N3—RU1—N6—C32101.9 (2)C27—N5—C31—C32176.4 (3)
C5—N1—C1—C22.6 (6)RU1—N5—C31—C32−1.8 (4)
RU1—N1—C1—C2178.8 (3)C29—C30—C31—N51.2 (5)
N1—C1—C2—C3−1.0 (7)C29—C30—C31—C32−178.6 (4)
C1—C2—C3—C4−0.7 (7)C36—N6—C32—C33−2.0 (5)
C2—C3—C4—C50.7 (6)RU1—N6—C32—C33−177.8 (3)
C1—N1—C5—C4−2.5 (6)C36—N6—C32—C31177.5 (3)
RU1—N1—C5—C4−179.3 (3)RU1—N6—C32—C311.6 (4)
C1—N1—C5—C6176.9 (3)N5—C31—C32—N60.0 (4)
RU1—N1—C5—C60.1 (4)C30—C31—C32—N6179.8 (3)
C3—C4—C5—N10.9 (6)N5—C31—C32—C33179.5 (3)
C3—C4—C5—C6−178.5 (4)C30—C31—C32—C33−0.8 (6)
C10—N2—C6—C7−0.9 (6)N6—C32—C33—C341.9 (5)
RU1—N2—C6—C7173.8 (3)C31—C32—C33—C34−177.5 (3)
C10—N2—C6—C5−178.6 (3)C32—C33—C34—C35−0.3 (6)
RU1—N2—C6—C5−4.0 (4)C33—C34—C35—C36−1.2 (5)
N1—C5—C6—N22.4 (5)C32—N6—C36—C350.5 (5)
C4—C5—C6—N2−178.2 (4)RU1—N6—C36—C35175.7 (3)
N1—C5—C6—C7−175.2 (4)C34—C35—C36—N61.1 (5)
C4—C5—C6—C74.2 (6)C28—C29—C37—C42−139.9 (4)
N2—C6—C7—C80.6 (6)C30—C29—C37—C4238.6 (5)
C5—C6—C7—C8178.0 (4)C28—C29—C37—C3840.8 (5)
C6—C7—C8—C90.5 (6)C30—C29—C37—C38−140.6 (4)
C6—C7—C8—C16−178.2 (4)C42—C37—C38—C39−0.8 (5)
C7—C8—C9—C10−1.3 (6)C29—C37—C38—C39178.4 (3)
C16—C8—C9—C10177.4 (4)C37—C38—C39—C400.3 (6)
C6—N2—C10—C90.0 (6)C37—C38—C39—BR3−177.1 (3)
RU1—N2—C10—C9−174.6 (3)C38—C39—C40—C410.3 (6)
C6—N2—C10—C11176.6 (3)BR3—C39—C40—C41177.7 (3)
RU1—N2—C10—C112.0 (4)C39—C40—C41—C42−0.5 (6)
C8—C9—C10—N21.1 (6)C39—C40—C41—BR4−179.2 (3)
C8—C9—C10—C11−175.0 (4)C40—C41—C42—C370.0 (6)
C15—N3—C11—C120.4 (6)BR4—C41—C42—C37178.8 (3)
RU1—N3—C11—C12−179.6 (3)C38—C37—C42—C410.7 (5)
C15—N3—C11—C10−178.5 (4)C29—C37—C42—C41−178.6 (3)
Table 1
Selected geometric parameters (Å, °) top
Ru1—N51.983 (3)Ru1—N12.078 (3)
Ru1—N21.988 (3)Ru1—N62.082 (4)
Ru1—N42.067 (4)Ru1—N32.089 (3)
N5—Ru1—N2176.91 (17)N4—Ru1—N6157.64 (11)
N5—Ru1—N479.20 (13)N1—Ru1—N697.48 (12)
N2—Ru1—N498.47 (13)N5—Ru1—N3103.40 (12)
N5—Ru1—N198.77 (12)N2—Ru1—N378.78 (12)
N2—Ru1—N178.99 (12)N4—Ru1—N395.84 (12)
N4—Ru1—N186.33 (12)N1—Ru1—N3157.75 (11)
N5—Ru1—N678.44 (13)N6—Ru1—N388.91 (12)
N2—Ru1—N6103.89 (13)
Acknowledgements top

We are grateful to the Natural Sciences and Engineering Research Council of Canada, Ministère de l'Education du Québec and the Université de Montréal for financial support. Johnson Matthey PLC is thanked for a loan of RuCl3.

references
References top

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