Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020259/nc2035sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020259/nc2035Isup2.hkl |
CCDC reference: 650520
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.
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.
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.
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).
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).
[Ru(C21H13Br2N3)2](PF6)2·2C2H3N | Z = 1 |
Mr = 1407.45 | F(000) = 686 |
Triclinic, P1 | Dx = 1.895 Mg m−3 |
Hall symbol: P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 8.3158 (1) Å | Cell parameters from 17454 reflections |
b = 9.2087 (1) Å | θ = 2.7–67.3° |
c = 16.2114 (1) Å | µ = 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 |
Bruker APEX II diffractometer | 7003 independent reflections |
Radiation source: Micro source | 6901 reflections with I > 2σ(I) |
Helios optics monochromator | Rint = 0.027 |
Detector resolution: 5.5 pixels mm-1 | θmax = 67.9°, θmin = 2.7° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | k = −10→10 |
Tmin = 0.601, Tmax = 0.857 | l = −19→19 |
19475 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.025 | H-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 reflections | Δρmax = 1.01 e Å−3 |
661 parameters | Δρmin = −0.39 e Å−3 |
3 restraints | Absolute structure: Flack (1983), 2532 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.041 (5) |
[Ru(C21H13Br2N3)2](PF6)2·2C2H3N | γ = 83.6367 (5)° |
Mr = 1407.45 | V = 1233.47 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.3158 (1) Å | Cu Kα radiation |
b = 9.2087 (1) Å | µ = 7.78 mm−1 |
c = 16.2114 (1) Å | T = 100 K |
α = 89.7346 (5)° | 0.10 × 0.05 × 0.02 mm |
β = 88.7088 (4)° |
Bruker APEX II diffractometer | 7003 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 6901 reflections with I > 2σ(I) |
Tmin = 0.601, Tmax = 0.857 | Rint = 0.027 |
19475 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.062 | Δρmax = 1.01 e Å−3 |
S = 1.06 | Δρmin = −0.39 e Å−3 |
7003 reflections | Absolute structure: Flack (1983), 2532 Friedel pairs |
661 parameters | Absolute structure parameter: 0.041 (5) |
3 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Ru1 | 0.05928 (2) | 0.69668 (2) | 0.094352 (15) | 0.01474 (8) | |
Br1 | 0.11826 (6) | 0.33373 (6) | −0.45785 (3) | 0.03716 (14) | |
Br2 | 0.36580 (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) | |
N1 | 0.1580 (3) | 0.4799 (4) | 0.08447 (18) | 0.0148 (7) | |
N2 | 0.1171 (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) | |
N6 | 0.2574 (4) | 0.7774 (4) | 0.14697 (17) | 0.0159 (7) | |
C1 | 0.1713 (4) | 0.3783 (5) | 0.1444 (2) | 0.0202 (9) | |
H1A | 0.1343 | 0.4050 | 0.1986 | 0.024* | |
C2 | 0.2378 (5) | 0.2349 (5) | 0.1295 (2) | 0.0223 (10) | |
H2A | 0.2472 | 0.1658 | 0.1733 | 0.027* | |
C3 | 0.2899 (5) | 0.1938 (5) | 0.0510 (3) | 0.0243 (11) | |
H3A | 0.3366 | 0.0967 | 0.0399 | 0.029* | |
C4 | 0.2726 (4) | 0.2984 (5) | −0.0125 (2) | 0.0216 (10) | |
H4A | 0.3064 | 0.2726 | −0.0674 | 0.026* | |
C5 | 0.2056 (4) | 0.4398 (5) | 0.0057 (2) | 0.0180 (9) | |
C6 | 0.1790 (4) | 0.5557 (4) | −0.0570 (2) | 0.0160 (9) | |
C7 | 0.2061 (4) | 0.5403 (5) | −0.1414 (2) | 0.0211 (10) | |
H7A | 0.2489 | 0.4486 | −0.1638 | 0.025* | |
C8 | 0.1696 (4) | 0.6614 (5) | −0.1934 (2) | 0.0186 (9) | |
C9 | 0.1080 (4) | 0.7944 (5) | −0.1582 (2) | 0.0180 (9) | |
H9A | 0.0845 | 0.8782 | −0.1920 | 0.022* | |
C10 | 0.0811 (4) | 0.8038 (4) | −0.0736 (2) | 0.0161 (9) | |
C11 | 0.0059 (4) | 0.9314 (5) | −0.0274 (2) | 0.0180 (9) | |
C12 | −0.0388 (5) | 1.0661 (5) | −0.0633 (2) | 0.0213 (9) | |
H12A | −0.0180 | 1.0809 | −0.1204 | 0.026* | |
C13 | −0.1141 (5) | 1.1788 (5) | −0.0155 (3) | 0.0270 (11) | |
H13A | −0.1461 | 1.2718 | −0.0393 | 0.032* | |
C14 | −0.1418 (5) | 1.1539 (5) | 0.0673 (3) | 0.0240 (11) | |
H14A | −0.1948 | 1.2295 | 0.1010 | 0.029* | |
C15 | −0.0926 (4) | 1.0195 (5) | 0.1010 (2) | 0.0235 (10) | |
H15A | −0.1100 | 1.0047 | 0.1584 | 0.028* | |
C16 | 0.1939 (5) | 0.6439 (5) | −0.2841 (2) | 0.0193 (10) | |
C17 | 0.1538 (5) | 0.5204 (5) | −0.3221 (2) | 0.0239 (11) | |
H17A | 0.1091 | 0.4470 | −0.2904 | 0.029* | |
C18 | 0.1779 (5) | 0.5020 (5) | −0.4065 (2) | 0.0267 (11) | |
C19 | 0.2426 (5) | 0.6077 (6) | −0.4544 (2) | 0.0278 (12) | |
H19A | 0.2613 | 0.5949 | −0.5121 | 0.033* | |
C20 | 0.2782 (5) | 0.7315 (5) | −0.4150 (2) | 0.0246 (11) | |
C21 | 0.2569 (5) | 0.7536 (5) | −0.3312 (2) | 0.0229 (10) | |
H21A | 0.2839 | 0.8405 | −0.3061 | 0.027* | |
C22 | −0.2399 (4) | 0.5796 (5) | 0.0228 (2) | 0.0221 (10) | |
H22A | −0.1986 | 0.6031 | −0.0302 | 0.027* | |
C23 | −0.3754 (5) | 0.5068 (5) | 0.0280 (3) | 0.0238 (10) | |
H23A | −0.4259 | 0.4791 | −0.0207 | 0.029* | |
C24 | −0.4375 (4) | 0.4742 (5) | 0.1052 (2) | 0.0221 (10) | |
H24A | −0.5301 | 0.4227 | 0.1101 | 0.027* | |
C25 | −0.3635 (4) | 0.5174 (5) | 0.1743 (2) | 0.0200 (9) | |
H25A | −0.4056 | 0.4968 | 0.2275 | 0.024* | |
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 | −0.2878 | 0.6088 | 0.3360 | 0.024* | |
C29 | −0.0949 (5) | 0.7034 (5) | 0.3772 (2) | 0.0197 (10) | |
C30 | 0.0507 (4) | 0.7544 (5) | 0.3518 (2) | 0.0192 (9) | |
H30A | 0.1183 | 0.7920 | 0.3911 | 0.023* | |
C31 | 0.0957 (4) | 0.7498 (4) | 0.2689 (2) | 0.0168 (9) | |
C32 | 0.2446 (4) | 0.7949 (4) | 0.2308 (2) | 0.0182 (9) | |
C33 | 0.3628 (4) | 0.8516 (5) | 0.2746 (2) | 0.0180 (9) | |
H33A | 0.3527 | 0.8599 | 0.3329 | 0.022* | |
C34 | 0.4973 (5) | 0.8969 (5) | 0.2333 (2) | 0.0220 (10) | |
H34A | 0.5797 | 0.9367 | 0.2627 | 0.026* | |
C35 | 0.5078 (4) | 0.8823 (5) | 0.1480 (2) | 0.0181 (10) | |
H35A | 0.5970 | 0.9138 | 0.1179 | 0.022* | |
C36 | 0.3880 (4) | 0.8219 (4) | 0.1076 (2) | 0.0156 (9) | |
H36A | 0.3975 | 0.8110 | 0.0494 | 0.019* | |
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 | −0.2384 | 0.5175 | 0.4754 | 0.028* | |
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 | −0.2621 | 0.7428 | 0.6910 | 0.035* | |
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 | −0.0703 | 0.9170 | 0.4844 | 0.027* | |
P1 | 0.91524 (12) | 0.18925 (13) | 0.33410 (6) | 0.0245 (3) | |
F1 | 1.0258 (3) | 0.3206 (3) | 0.33116 (16) | 0.0376 (7) | |
F2 | 1.0441 (3) | 0.0963 (3) | 0.27442 (16) | 0.0386 (7) | |
F3 | 1.0125 (3) | 0.1216 (3) | 0.41140 (15) | 0.0366 (7) | |
F4 | 0.8200 (4) | 0.2540 (4) | 0.25552 (18) | 0.0533 (9) | |
F5 | 0.7874 (3) | 0.2803 (4) | 0.39307 (17) | 0.0442 (8) | |
F6 | 0.8064 (3) | 0.0552 (3) | 0.33533 (18) | 0.0391 (7) | |
P2 | 0.56414 (12) | 0.89525 (16) | 0.87713 (6) | 0.0317 (3) | |
F7 | 0.6287 (4) | 1.0460 (5) | 0.85268 (18) | 0.0663 (12) | |
F8 | 0.7329 (3) | 0.8074 (5) | 0.85077 (17) | 0.0654 (12) | |
F9 | 0.6294 (3) | 0.9084 (4) | 0.96895 (14) | 0.0413 (8) | |
F10 | 0.4985 (3) | 0.8787 (4) | 0.78624 (15) | 0.0465 (9) | |
F11 | 0.3941 (3) | 0.9816 (4) | 0.90451 (17) | 0.0424 (7) | |
F12 | 0.4954 (3) | 0.7446 (4) | 0.90392 (17) | 0.0412 (7) | |
N50 | 0.1777 (8) | 0.1734 (7) | 0.7721 (3) | 0.0651 (17) | |
C50 | 0.2877 (11) | 0.1696 (9) | 0.7375 (5) | 0.071 (2) | |
C51 | 0.4432 (10) | 0.1555 (10) | 0.6881 (5) | 0.084 (3) | |
H51A | 0.5311 | 0.1806 | 0.7227 | 0.126* | |
H51B | 0.4327 | 0.2219 | 0.6406 | 0.126* | |
H51C | 0.4675 | 0.0547 | 0.6686 | 0.126* | |
N52 | 0.4003 (6) | 0.4943 (6) | 0.3489 (3) | 0.0504 (14) | |
C52 | 0.4083 (6) | 0.3754 (7) | 0.3625 (3) | 0.0398 (14) | |
C53 | 0.4195 (7) | 0.2178 (6) | 0.3814 (4) | 0.0566 (18) | |
H53A | 0.4618 | 0.2003 | 0.4369 | 0.085* | |
H53B | 0.4924 | 0.1639 | 0.3410 | 0.085* | |
H53C | 0.3118 | 0.1846 | 0.3787 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ru1 | 0.01455 (11) | 0.01488 (17) | 0.01510 (12) | −0.00285 (11) | −0.00092 (9) | −0.00290 (11) |
Br1 | 0.0492 (3) | 0.0331 (3) | 0.0302 (2) | −0.0078 (3) | −0.00386 (19) | −0.0148 (2) |
Br2 | 0.0558 (3) | 0.0436 (3) | 0.0207 (2) | −0.0183 (3) | −0.00158 (19) | 0.0046 (2) |
Br3 | 0.0552 (3) | 0.0416 (4) | 0.0379 (3) | −0.0145 (3) | 0.0142 (2) | 0.0083 (2) |
Br4 | 0.0549 (3) | 0.0346 (3) | 0.0258 (2) | −0.0057 (2) | 0.00264 (19) | −0.0093 (2) |
N1 | 0.0155 (13) | 0.0097 (19) | 0.0208 (14) | −0.0075 (13) | −0.0038 (11) | −0.0051 (13) |
N2 | 0.0155 (14) | 0.016 (2) | 0.0180 (14) | −0.0017 (14) | −0.0017 (11) | −0.0023 (14) |
N3 | 0.0167 (14) | 0.021 (2) | 0.0184 (14) | −0.0060 (14) | −0.0023 (11) | −0.0051 (14) |
N4 | 0.0214 (15) | 0.017 (2) | 0.0223 (15) | −0.0001 (15) | −0.0015 (12) | −0.0021 (14) |
N5 | 0.0186 (15) | 0.014 (2) | 0.0189 (14) | −0.0036 (14) | −0.0005 (12) | −0.0047 (13) |
N6 | 0.0203 (15) | 0.0107 (19) | 0.0165 (13) | −0.0015 (14) | 0.0009 (11) | −0.0032 (13) |
C1 | 0.0181 (16) | 0.022 (3) | 0.0208 (17) | −0.0028 (17) | −0.0010 (14) | −0.0005 (17) |
C2 | 0.0220 (19) | 0.019 (3) | 0.028 (2) | −0.0082 (18) | −0.0046 (15) | 0.0034 (18) |
C3 | 0.0250 (18) | 0.018 (3) | 0.030 (2) | −0.0006 (18) | 0.0004 (15) | −0.0017 (18) |
C4 | 0.027 (2) | 0.018 (2) | 0.0205 (17) | −0.0033 (18) | −0.0007 (15) | −0.0053 (16) |
C5 | 0.0146 (15) | 0.020 (2) | 0.0198 (17) | −0.0053 (16) | −0.0009 (13) | −0.0006 (16) |
C6 | 0.0136 (15) | 0.015 (2) | 0.0208 (17) | −0.0059 (16) | −0.0050 (13) | −0.0030 (16) |
C7 | 0.0232 (17) | 0.020 (2) | 0.0196 (17) | 0.0006 (17) | 0.0014 (14) | −0.0054 (16) |
C8 | 0.0208 (18) | 0.018 (2) | 0.0178 (17) | −0.0062 (17) | −0.0026 (14) | −0.0021 (17) |
C9 | 0.0187 (16) | 0.017 (2) | 0.0189 (16) | −0.0034 (16) | −0.0025 (13) | −0.0010 (16) |
C10 | 0.0152 (16) | 0.011 (2) | 0.0235 (17) | −0.0086 (16) | −0.0046 (13) | −0.0030 (16) |
C11 | 0.0161 (15) | 0.020 (2) | 0.0189 (17) | −0.0047 (17) | −0.0035 (13) | −0.0058 (16) |
C12 | 0.0227 (17) | 0.020 (3) | 0.0213 (17) | −0.0040 (17) | −0.0041 (14) | −0.0029 (17) |
C13 | 0.0302 (19) | 0.016 (3) | 0.034 (2) | 0.0014 (19) | −0.0078 (16) | −0.0019 (19) |
C14 | 0.0218 (19) | 0.020 (3) | 0.031 (2) | −0.0014 (19) | −0.0041 (16) | −0.0133 (19) |
C15 | 0.0151 (16) | 0.034 (3) | 0.0214 (17) | −0.0014 (18) | −0.0015 (13) | −0.0055 (18) |
C16 | 0.0237 (18) | 0.014 (3) | 0.0201 (17) | −0.0032 (18) | −0.0006 (14) | −0.0075 (18) |
C17 | 0.0259 (19) | 0.027 (3) | 0.0188 (17) | −0.0011 (19) | −0.0027 (15) | −0.0031 (19) |
C18 | 0.033 (2) | 0.027 (3) | 0.0196 (18) | 0.001 (2) | −0.0074 (15) | −0.0116 (18) |
C19 | 0.030 (2) | 0.033 (3) | 0.0199 (18) | −0.001 (2) | −0.0031 (15) | −0.007 (2) |
C20 | 0.0258 (19) | 0.024 (3) | 0.0251 (18) | −0.006 (2) | −0.0051 (15) | −0.002 (2) |
C21 | 0.0258 (18) | 0.026 (3) | 0.0176 (17) | −0.0032 (18) | −0.0043 (14) | 0.0003 (17) |
C22 | 0.0180 (17) | 0.025 (3) | 0.0236 (18) | −0.0029 (18) | −0.0016 (14) | −0.0007 (18) |
C23 | 0.021 (2) | 0.020 (3) | 0.030 (2) | −0.0011 (19) | −0.0072 (16) | −0.0098 (18) |
C24 | 0.0176 (17) | 0.017 (2) | 0.033 (2) | −0.0048 (17) | −0.0024 (14) | −0.0045 (18) |
C25 | 0.0150 (15) | 0.017 (2) | 0.0276 (18) | −0.0021 (16) | −0.0011 (14) | −0.0013 (17) |
C26 | 0.0178 (16) | 0.011 (2) | 0.0206 (16) | 0.0003 (16) | −0.0013 (13) | −0.0048 (15) |
C27 | 0.0157 (16) | 0.011 (2) | 0.0227 (17) | −0.0043 (16) | −0.0037 (13) | −0.0027 (16) |
C28 | 0.0176 (16) | 0.021 (2) | 0.0211 (17) | −0.0017 (17) | 0.0028 (14) | −0.0011 (16) |
C29 | 0.0211 (18) | 0.018 (2) | 0.0193 (18) | −0.0001 (18) | 0.0002 (14) | −0.0036 (17) |
C30 | 0.0197 (17) | 0.018 (2) | 0.0191 (17) | −0.0003 (17) | −0.0007 (14) | −0.0043 (16) |
C31 | 0.0159 (16) | 0.015 (2) | 0.0200 (17) | −0.0021 (16) | −0.0041 (13) | 0.0010 (16) |
C32 | 0.0182 (16) | 0.015 (2) | 0.0206 (17) | 0.0002 (16) | 0.0009 (14) | −0.0005 (16) |
C33 | 0.0206 (17) | 0.017 (2) | 0.0169 (16) | −0.0048 (17) | −0.0036 (14) | −0.0048 (16) |
C34 | 0.0201 (17) | 0.020 (2) | 0.0275 (19) | −0.0063 (18) | −0.0069 (15) | −0.0006 (18) |
C35 | 0.0156 (17) | 0.010 (2) | 0.0288 (19) | −0.0019 (17) | 0.0012 (15) | −0.0023 (17) |
C36 | 0.0181 (16) | 0.012 (2) | 0.0177 (16) | −0.0040 (16) | −0.0006 (13) | 0.0004 (16) |
C37 | 0.0226 (19) | 0.024 (3) | 0.0199 (18) | −0.0016 (18) | 0.0032 (15) | 0.0018 (19) |
C38 | 0.0266 (19) | 0.021 (3) | 0.0241 (18) | −0.0052 (19) | −0.0002 (15) | −0.0042 (18) |
C39 | 0.030 (2) | 0.029 (3) | 0.027 (2) | −0.003 (2) | 0.0072 (16) | 0.006 (2) |
C40 | 0.033 (2) | 0.034 (3) | 0.0181 (18) | 0.000 (2) | 0.0025 (16) | −0.001 (2) |
C41 | 0.027 (2) | 0.026 (3) | 0.0241 (19) | −0.0038 (19) | 0.0002 (15) | −0.0045 (19) |
C42 | 0.0236 (18) | 0.021 (3) | 0.0225 (18) | −0.0034 (19) | 0.0012 (15) | −0.0021 (19) |
P1 | 0.0310 (5) | 0.0211 (7) | 0.0215 (4) | −0.0018 (5) | −0.0035 (4) | −0.0038 (4) |
F1 | 0.0522 (15) | 0.0246 (16) | 0.0377 (13) | −0.0128 (13) | 0.0051 (12) | 0.0019 (12) |
F2 | 0.0396 (13) | 0.0349 (18) | 0.0399 (14) | 0.0016 (13) | 0.0039 (11) | −0.0082 (13) |
F3 | 0.0489 (14) | 0.0327 (17) | 0.0317 (12) | −0.0180 (13) | −0.0144 (11) | 0.0082 (12) |
F4 | 0.0711 (19) | 0.045 (2) | 0.0407 (14) | 0.0144 (17) | −0.0275 (14) | −0.0030 (14) |
F5 | 0.0421 (14) | 0.042 (2) | 0.0490 (15) | −0.0054 (14) | 0.0066 (12) | −0.0238 (14) |
F6 | 0.0328 (12) | 0.0324 (18) | 0.0536 (15) | −0.0086 (13) | −0.0081 (11) | −0.0102 (13) |
P2 | 0.0220 (5) | 0.0555 (9) | 0.0197 (5) | −0.0134 (5) | −0.0003 (4) | −0.0055 (5) |
F7 | 0.073 (2) | 0.100 (3) | 0.0369 (15) | −0.055 (2) | −0.0173 (14) | 0.0220 (19) |
F8 | 0.0231 (12) | 0.135 (4) | 0.0355 (14) | 0.0025 (18) | 0.0015 (11) | −0.0110 (17) |
F9 | 0.0375 (13) | 0.069 (2) | 0.0221 (11) | −0.0276 (14) | −0.0040 (10) | 0.0018 (13) |
F10 | 0.0344 (13) | 0.083 (3) | 0.0232 (11) | −0.0109 (15) | −0.0071 (10) | −0.0110 (14) |
F11 | 0.0390 (14) | 0.045 (2) | 0.0430 (14) | −0.0045 (14) | 0.0005 (11) | −0.0157 (13) |
F12 | 0.0399 (14) | 0.0401 (19) | 0.0450 (15) | −0.0084 (13) | −0.0095 (11) | −0.0051 (14) |
N50 | 0.092 (4) | 0.058 (4) | 0.044 (3) | −0.004 (3) | 0.009 (3) | 0.011 (3) |
C50 | 0.100 (6) | 0.054 (5) | 0.060 (4) | −0.014 (4) | −0.010 (4) | 0.011 (4) |
C51 | 0.091 (5) | 0.082 (6) | 0.082 (5) | −0.018 (5) | 0.002 (4) | 0.020 (5) |
N52 | 0.057 (3) | 0.044 (3) | 0.048 (2) | 0.002 (2) | 0.024 (2) | 0.010 (2) |
C52 | 0.042 (3) | 0.044 (4) | 0.032 (2) | −0.004 (2) | 0.016 (2) | −0.006 (2) |
C53 | 0.038 (3) | 0.033 (4) | 0.097 (5) | −0.003 (3) | 0.020 (3) | −0.006 (3) |
Ru1—N5 | 1.983 (3) | C22—C23 | 1.375 (7) |
Ru1—N2 | 1.988 (3) | C22—H22a | 0.95 |
Ru1—N4 | 2.067 (4) | C23—C24 | 1.387 (6) |
Ru1—N1 | 2.078 (3) | C23—H23a | 0.95 |
Ru1—N6 | 2.082 (4) | C24—C25 | 1.371 (6) |
Ru1—N3 | 2.089 (3) | C24—H24a | 0.95 |
Br1—C18 | 1.882 (5) | C25—C26 | 1.383 (6) |
Br2—C20 | 1.914 (4) | C25—H25a | 0.95 |
Br3—C39 | 1.913 (5) | C26—C27 | 1.463 (6) |
Br4—C41 | 1.899 (5) | C27—C28 | 1.398 (5) |
N1—C1 | 1.343 (5) | C28—C29 | 1.385 (7) |
N1—C5 | 1.368 (5) | C28—H28a | 0.95 |
N2—C6 | 1.342 (5) | C29—C30 | 1.399 (6) |
N2—C10 | 1.355 (5) | C29—C37 | 1.502 (5) |
N3—C15 | 1.342 (5) | C30—C31 | 1.385 (5) |
N3—C11 | 1.374 (4) | C30—H30a | 0.95 |
N4—C22 | 1.341 (6) | C31—C32 | 1.471 (5) |
N4—C26 | 1.372 (5) | C32—C33 | 1.376 (6) |
N5—C27 | 1.351 (5) | C33—C34 | 1.393 (6) |
N5—C31 | 1.357 (6) | C33—H33a | 0.95 |
N6—C36 | 1.349 (5) | C34—C35 | 1.390 (6) |
N6—C32 | 1.370 (5) | C34—H34a | 0.95 |
C1—C2 | 1.394 (6) | C35—C36 | 1.374 (6) |
C1—H1a | 0.95 | C35—H35a | 0.95 |
C2—C3 | 1.376 (6) | C36—H36a | 0.95 |
C2—H2a | 0.95 | C37—C42 | 1.394 (7) |
C3—C4 | 1.405 (5) | C37—C38 | 1.398 (6) |
C3—H3a | 0.95 | C38—C39 | 1.380 (6) |
C4—C5 | 1.389 (6) | C38—H38a | 0.95 |
C4—H4a | 0.95 | C39—C40 | 1.368 (8) |
C5—C6 | 1.473 (5) | C40—C41 | 1.385 (7) |
C6—C7 | 1.386 (5) | C40—H40a | 0.95 |
C7—C8 | 1.406 (5) | C41—C42 | 1.390 (6) |
C7—H7a | 0.95 | C42—H42a | 0.95 |
C8—C9 | 1.394 (6) | P1—F5 | 1.585 (3) |
C8—C16 | 1.485 (5) | P1—F3 | 1.593 (2) |
C9—C10 | 1.386 (5) | P1—F4 | 1.594 (3) |
C9—H9a | 0.95 | P1—F1 | 1.599 (3) |
C10—C11 | 1.469 (6) | P1—F2 | 1.605 (3) |
C11—C12 | 1.384 (5) | P1—F6 | 1.609 (4) |
C12—C13 | 1.382 (6) | P2—F7 | 1.588 (4) |
C12—H12a | 0.95 | P2—F8 | 1.591 (3) |
C13—C14 | 1.381 (6) | P2—F10 | 1.597 (3) |
C13—H13a | 0.95 | P2—F11 | 1.598 (3) |
C14—C15 | 1.375 (6) | P2—F9 | 1.606 (3) |
C14—H14a | 0.95 | P2—F12 | 1.612 (4) |
C15—H15a | 0.95 | N50—C50 | 1.060 (9) |
C16—C17 | 1.373 (7) | C50—C51 | 1.499 (12) |
C16—C21 | 1.404 (6) | C51—H51a | 0.98 |
C17—C18 | 1.387 (5) | C51—H51b | 0.98 |
C17—H17a | 0.95 | C51—H51c | 0.98 |
C18—C19 | 1.389 (7) | N52—C52 | 1.111 (7) |
C19—C20 | 1.373 (8) | C52—C53 | 1.475 (8) |
C19—H19a | 0.95 | C53—H53a | 0.98 |
C20—C21 | 1.380 (6) | C53—H53b | 0.98 |
C21—H21a | 0.95 | C53—H53c | 0.98 |
N5—Ru1—N2 | 176.91 (17) | C25—C24—C23 | 119.2 (4) |
N5—Ru1—N4 | 79.20 (13) | C25—C24—H24A | 120.4 |
N2—Ru1—N4 | 98.47 (13) | C23—C24—H24A | 120.4 |
N5—Ru1—N1 | 98.77 (12) | C24—C25—C26 | 120.0 (3) |
N2—Ru1—N1 | 78.99 (12) | C24—C25—H25A | 120 |
N4—Ru1—N1 | 86.33 (12) | C26—C25—H25A | 120 |
N5—Ru1—N6 | 78.44 (13) | N4—C26—C25 | 120.4 (4) |
N2—Ru1—N6 | 103.89 (13) | N4—C26—C27 | 115.3 (3) |
N4—Ru1—N6 | 157.64 (11) | C25—C26—C27 | 124.3 (3) |
N1—Ru1—N6 | 97.48 (12) | N5—C27—C28 | 119.6 (4) |
N5—Ru1—N3 | 103.40 (12) | N5—C27—C26 | 113.1 (3) |
N2—Ru1—N3 | 78.78 (12) | C28—C27—C26 | 127.3 (4) |
N4—Ru1—N3 | 95.84 (12) | C29—C28—C27 | 119.6 (4) |
N1—Ru1—N3 | 157.75 (11) | C29—C28—H28A | 120.2 |
N6—Ru1—N3 | 88.91 (12) | C27—C28—H28A | 120.2 |
C1—N1—C5 | 118.8 (3) | C28—C29—C30 | 119.4 (3) |
C1—N1—RU1 | 127.6 (3) | C28—C29—C37 | 121.6 (4) |
C5—N1—RU1 | 113.5 (2) | C30—C29—C37 | 119.0 (4) |
C6—N2—C10 | 121.7 (3) | C31—C30—C29 | 119.6 (4) |
C6—N2—RU1 | 118.9 (2) | C31—C30—H30A | 120.2 |
C10—N2—RU1 | 119.2 (3) | C29—C30—H30A | 120.2 |
C15—N3—C11 | 118.6 (3) | N5—C31—C30 | 119.7 (3) |
C15—N3—RU1 | 127.9 (2) | N5—C31—C32 | 112.8 (3) |
C11—N3—RU1 | 113.6 (3) | C30—C31—C32 | 127.6 (4) |
C22—N4—C26 | 119.1 (4) | N6—C32—C33 | 121.6 (3) |
C22—N4—RU1 | 127.3 (2) | N6—C32—C31 | 114.9 (4) |
C26—N4—RU1 | 113.2 (3) | C33—C32—C31 | 123.5 (3) |
C27—N5—C31 | 122.1 (3) | C32—C33—C34 | 119.9 (3) |
C27—N5—RU1 | 118.4 (3) | C32—C33—H33A | 120 |
C31—N5—RU1 | 119.5 (2) | C34—C33—H33A | 120 |
C36—N6—C32 | 118.0 (4) | C35—C34—C33 | 118.3 (4) |
C36—N6—RU1 | 127.5 (2) | C35—C34—H34A | 120.9 |
C32—N6—RU1 | 114.4 (2) | C33—C34—H34A | 120.9 |
N1—C1—C2 | 122.1 (3) | C36—C35—C34 | 119.4 (4) |
N1—C1—H1A | 118.9 | C36—C35—H35A | 120.3 |
C2—C1—H1A | 118.9 | C34—C35—H35A | 120.3 |
C3—C2—C1 | 119.7 (3) | N6—C36—C35 | 122.8 (3) |
C3—C2—H2A | 120.2 | N6—C36—H36A | 118.6 |
C1—C2—H2A | 120.2 | C35—C36—H36A | 118.6 |
C2—C3—C4 | 118.6 (4) | C42—C37—C38 | 120.6 (4) |
C2—C3—H3A | 120.7 | C42—C37—C29 | 119.3 (4) |
C4—C3—H3A | 120.7 | C38—C37—C29 | 120.1 (4) |
C5—C4—C3 | 119.4 (3) | C39—C38—C37 | 117.4 (5) |
C5—C4—H4A | 120.3 | C39—C38—H38A | 121.3 |
C3—C4—H4A | 120.3 | C37—C38—H38A | 121.3 |
N1—C5—C4 | 121.3 (3) | C40—C39—C38 | 124.2 (4) |
N1—C5—C6 | 115.4 (3) | C40—C39—BR3 | 118.0 (3) |
C4—C5—C6 | 123.2 (3) | C38—C39—BR3 | 117.7 (4) |
N2—C6—C7 | 120.4 (3) | C39—C40—C41 | 116.9 (4) |
N2—C6—C5 | 113.0 (3) | C39—C40—H40A | 121.5 |
C7—C6—C5 | 126.5 (4) | C41—C40—H40A | 121.5 |
C6—C7—C8 | 119.5 (4) | C40—C41—C42 | 122.1 (5) |
C6—C7—H7A | 120.3 | C40—C41—BR4 | 120.0 (3) |
C8—C7—H7A | 120.3 | C42—C41—BR4 | 117.9 (4) |
C9—C8—C7 | 118.6 (3) | C41—C42—C37 | 118.7 (4) |
C9—C8—C16 | 121.9 (3) | C41—C42—H42A | 120.7 |
C7—C8—C16 | 119.5 (4) | C37—C42—H42A | 120.7 |
C10—C9—C8 | 119.7 (3) | F5—P1—F3 | 91.04 (15) |
C10—C9—H9A | 120.1 | F5—P1—F4 | 90.19 (16) |
C8—C9—H9A | 120.1 | F3—P1—F4 | 178.70 (18) |
N2—C10—C9 | 120.1 (3) | F5—P1—F1 | 90.91 (17) |
N2—C10—C11 | 113.1 (3) | F3—P1—F1 | 89.85 (15) |
C9—C10—C11 | 126.8 (3) | F4—P1—F1 | 90.55 (18) |
N3—C11—C12 | 121.1 (3) | F5—P1—F2 | 179.7 (2) |
N3—C11—C10 | 115.4 (3) | F3—P1—F2 | 88.94 (14) |
C12—C11—C10 | 123.5 (3) | F4—P1—F2 | 89.82 (15) |
C13—C12—C11 | 119.6 (3) | F1—P1—F2 | 89.43 (16) |
C13—C12—H12A | 120.2 | F5—P1—F6 | 90.37 (17) |
C11—C12—H12A | 120.2 | F3—P1—F6 | 90.41 (15) |
C14—C13—C12 | 118.7 (4) | F4—P1—F6 | 89.17 (18) |
C14—C13—H13A | 120.6 | F1—P1—F6 | 178.69 (16) |
C12—C13—H13A | 120.6 | F2—P1—F6 | 89.29 (17) |
C15—C14—C13 | 119.9 (4) | F7—P2—F8 | 91.2 (2) |
C15—C14—H14A | 120 | F7—P2—F10 | 90.82 (18) |
C13—C14—H14A | 120 | F8—P2—F10 | 90.54 (15) |
N3—C15—C14 | 122.1 (3) | F7—P2—F11 | 89.6 (2) |
N3—C15—H15A | 119 | F8—P2—F11 | 179.2 (2) |
C14—C15—H15A | 119 | F10—P2—F11 | 89.81 (15) |
C17—C16—C21 | 119.8 (4) | F7—P2—F9 | 90.38 (18) |
C17—C16—C8 | 120.0 (4) | F8—P2—F9 | 89.23 (15) |
C21—C16—C8 | 120.3 (4) | F10—P2—F9 | 178.8 (2) |
C16—C17—C18 | 120.5 (4) | F11—P2—F9 | 90.40 (15) |
C16—C17—H17A | 119.8 | F7—P2—F12 | 178.4 (2) |
C18—C17—H17A | 119.8 | F8—P2—F12 | 90.2 (2) |
C17—C18—C19 | 121.0 (5) | F10—P2—F12 | 89.99 (18) |
C17—C18—BR1 | 119.8 (4) | F11—P2—F12 | 89.01 (16) |
C19—C18—BR1 | 119.2 (3) | F9—P2—F12 | 88.81 (16) |
C20—C19—C18 | 117.2 (4) | N50—C50—C51 | 176.9 (10) |
C20—C19—H19A | 121.4 | C50—C51—H51A | 109.5 |
C18—C19—H19A | 121.4 | C50—C51—H51B | 109.5 |
C19—C20—C21 | 123.6 (4) | H51A—C51—H51B | 109.5 |
C19—C20—BR2 | 118.8 (3) | C50—C51—H51C | 109.5 |
C21—C20—BR2 | 117.6 (4) | H51A—C51—H51C | 109.5 |
C20—C21—C16 | 117.9 (5) | H51B—C51—H51C | 109.5 |
C20—C21—H21A | 121 | N52—C52—C53 | 179.4 (7) |
C16—C21—H21A | 121 | C52—C53—H53A | 109.5 |
N4—C22—C23 | 122.2 (3) | C52—C53—H53B | 109.5 |
N4—C22—H22A | 118.9 | H53A—C53—H53B | 109.5 |
C23—C22—H22A | 118.9 | C52—C53—H53C | 109.5 |
C22—C23—C24 | 119.1 (4) | H53A—C53—H53C | 109.5 |
C22—C23—H23A | 120.5 | H53B—C53—H53C | 109.5 |
C24—C23—H23A | 120.5 | ||
N5—RU1—N1—C1 | −0.2 (4) | RU1—N3—C11—C10 | 1.5 (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—N3 | 174.0 (4) |
N6—RU1—N1—C1 | 79.1 (3) | N2—C10—C11—C12 | 178.8 (4) |
N3—RU1—N1—C1 | −175.2 (3) | C9—C10—C11—C12 | −4.8 (7) |
N5—RU1—N1—C5 | 176.2 (3) | N3—C11—C12—C13 | −1.1 (6) |
N2—RU1—N1—C5 | −1.6 (3) | C10—C11—C12—C13 | 177.8 (4) |
N4—RU1—N1—C5 | 97.7 (3) | C11—C12—C13—C14 | 0.4 (7) |
N6—RU1—N1—C5 | −104.4 (3) | C12—C13—C14—C15 | 0.9 (7) |
N3—RU1—N1—C5 | 1.3 (5) | C11—N3—C15—C14 | 0.9 (6) |
N4—RU1—N2—C6 | −81.4 (3) | RU1—N3—C15—C14 | −179.1 (3) |
N1—RU1—N2—C6 | 3.2 (3) | C13—C14—C15—N3 | −1.6 (7) |
N6—RU1—N2—C6 | 98.3 (3) | C9—C8—C16—C17 | −138.5 (4) |
N3—RU1—N2—C6 | −175.7 (3) | C7—C8—C16—C17 | 40.2 (5) |
N4—RU1—N2—C10 | 93.4 (3) | C9—C8—C16—C21 | 41.1 (5) |
N1—RU1—N2—C10 | 177.9 (3) | C7—C8—C16—C21 | −140.3 (4) |
N6—RU1—N2—C10 | −87.0 (3) | C21—C16—C17—C18 | 1.3 (5) |
N3—RU1—N2—C10 | −0.9 (3) | C8—C16—C17—C18 | −179.2 (3) |
N5—RU1—N3—C15 | 1.9 (4) | C16—C17—C18—C19 | −0.2 (6) |
N2—RU1—N3—C15 | 179.7 (4) | C16—C17—C18—BR1 | −178.8 (3) |
N4—RU1—N3—C15 | 82.1 (4) | C17—C18—C19—C20 | −1.2 (5) |
N1—RU1—N3—C15 | 176.7 (3) | BR1—C18—C19—C20 | 177.4 (3) |
N6—RU1—N3—C15 | −76.0 (4) | C18—C19—C20—C21 | 1.6 (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—C11 | 104.0 (3) | C8—C16—C21—C20 | 179.5 (3) |
N5—RU1—N4—C22 | 179.8 (3) | C26—N4—C22—C23 | −3.0 (5) |
N2—RU1—N4—C22 | −2.2 (3) | RU1—N4—C22—C23 | 169.1 (3) |
N1—RU1—N4—C22 | −80.5 (3) | N4—C22—C23—C24 | 1.0 (6) |
N6—RU1—N4—C22 | 178.7 (3) | C22—C23—C24—C25 | 0.9 (6) |
N3—RU1—N4—C22 | 77.3 (3) | C23—C24—C25—C26 | −0.8 (5) |
N5—RU1—N4—C26 | −7.7 (2) | C22—N4—C26—C25 | 3.1 (5) |
N2—RU1—N4—C26 | 170.2 (2) | RU1—N4—C26—C25 | −170.0 (3) |
N1—RU1—N4—C26 | 91.9 (2) | C22—N4—C26—C27 | −176.9 (3) |
N6—RU1—N4—C26 | −8.9 (5) | RU1—N4—C26—C27 | 10.0 (4) |
N3—RU1—N4—C26 | −110.3 (2) | C24—C25—C26—N4 | −1.3 (5) |
N4—RU1—N5—C27 | 4.3 (3) | C24—C25—C26—C27 | 178.8 (3) |
N1—RU1—N5—C27 | −80.2 (3) | C31—N5—C27—C28 | 3.0 (5) |
N6—RU1—N5—C27 | −176.2 (3) | RU1—N5—C27—C28 | −178.8 (3) |
N3—RU1—N5—C27 | 97.8 (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—C31 | 98.0 (3) | N4—C26—C27—N5 | −6.6 (4) |
N6—RU1—N5—C31 | 2.1 (3) | C25—C26—C27—N5 | 173.3 (3) |
N3—RU1—N5—C31 | −84.0 (3) | N4—C26—C27—C28 | 171.9 (3) |
N5—RU1—N6—C36 | −177.3 (3) | C25—C26—C27—C28 | −8.2 (6) |
N2—RU1—N6—C36 | 4.7 (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—C36 | 85.2 (3) | C27—C28—C29—C30 | −1.7 (5) |
N3—RU1—N6—C36 | −73.4 (3) | C27—C28—C29—C37 | 176.8 (3) |
N5—RU1—N6—C32 | −2.0 (2) | C28—C29—C30—C31 | 1.3 (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—C30 | 178.4 (3) |
N3—RU1—N6—C32 | 101.9 (2) | C27—N5—C31—C32 | 176.4 (3) |
C5—N1—C1—C2 | 2.6 (6) | RU1—N5—C31—C32 | −1.8 (4) |
RU1—N1—C1—C2 | 178.8 (3) | C29—C30—C31—N5 | 1.2 (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—C5 | 0.7 (6) | RU1—N6—C32—C33 | −177.8 (3) |
C1—N1—C5—C4 | −2.5 (6) | C36—N6—C32—C31 | 177.5 (3) |
RU1—N1—C5—C4 | −179.3 (3) | RU1—N6—C32—C31 | 1.6 (4) |
C1—N1—C5—C6 | 176.9 (3) | N5—C31—C32—N6 | 0.0 (4) |
RU1—N1—C5—C6 | 0.1 (4) | C30—C31—C32—N6 | 179.8 (3) |
C3—C4—C5—N1 | 0.9 (6) | N5—C31—C32—C33 | 179.5 (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—C34 | 1.9 (5) |
RU1—N2—C6—C7 | 173.8 (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—N2 | 2.4 (5) | C32—N6—C36—C35 | 0.5 (5) |
C4—C5—C6—N2 | −178.2 (4) | RU1—N6—C36—C35 | 175.7 (3) |
N1—C5—C6—C7 | −175.2 (4) | C34—C35—C36—N6 | 1.1 (5) |
C4—C5—C6—C7 | 4.2 (6) | C28—C29—C37—C42 | −139.9 (4) |
N2—C6—C7—C8 | 0.6 (6) | C30—C29—C37—C42 | 38.6 (5) |
C5—C6—C7—C8 | 178.0 (4) | C28—C29—C37—C38 | 40.8 (5) |
C6—C7—C8—C9 | 0.5 (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—C39 | 178.4 (3) |
C16—C8—C9—C10 | 177.4 (4) | C37—C38—C39—C40 | 0.3 (6) |
C6—N2—C10—C9 | 0.0 (6) | C37—C38—C39—BR3 | −177.1 (3) |
RU1—N2—C10—C9 | −174.6 (3) | C38—C39—C40—C41 | 0.3 (6) |
C6—N2—C10—C11 | 176.6 (3) | BR3—C39—C40—C41 | 177.7 (3) |
RU1—N2—C10—C11 | 2.0 (4) | C39—C40—C41—C42 | −0.5 (6) |
C8—C9—C10—N2 | 1.1 (6) | C39—C40—C41—BR4 | −179.2 (3) |
C8—C9—C10—C11 | −175.0 (4) | C40—C41—C42—C37 | 0.0 (6) |
C15—N3—C11—C12 | 0.4 (6) | BR4—C41—C42—C37 | 178.8 (3) |
RU1—N3—C11—C12 | −179.6 (3) | C38—C37—C42—C41 | 0.7 (5) |
C15—N3—C11—C10 | −178.5 (4) | C29—C37—C42—C41 | −178.6 (3) |
Experimental details
Crystal data | |
Chemical formula | [Ru(C21H13Br2N3)2](PF6)2·2C2H3N |
Mr | 1407.45 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 8.3158 (1), 9.2087 (1), 16.2114 (1) |
α, β, γ (°) | 89.7346 (5), 88.7088 (4), 83.6367 (5) |
V (Å3) | 1233.47 (2) |
Z | 1 |
Radiation type | Cu Kα |
µ (mm−1) | 7.78 |
Crystal size (mm) | 0.10 × 0.05 × 0.02 |
Data collection | |
Diffractometer | Bruker APEX II |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.601, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19475, 7003, 6901 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.062, 1.06 |
No. of reflections | 7003 |
No. of parameters | 661 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.01, −0.39 |
Absolute structure | Flack (1983), 2532 Friedel pairs |
Absolute structure parameter | 0.041 (5) |
Computer programs: APEX2 (Bruker, 2004), APEX2, SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), UdMX (local program).
Ru1—N5 | 1.983 (3) | Ru1—N1 | 2.078 (3) |
Ru1—N2 | 1.988 (3) | Ru1—N6 | 2.082 (4) |
Ru1—N4 | 2.067 (4) | Ru1—N3 | 2.089 (3) |
N5—Ru1—N2 | 176.91 (17) | N4—Ru1—N6 | 157.64 (11) |
N5—Ru1—N4 | 79.20 (13) | N1—Ru1—N6 | 97.48 (12) |
N2—Ru1—N4 | 98.47 (13) | N5—Ru1—N3 | 103.40 (12) |
N5—Ru1—N1 | 98.77 (12) | N2—Ru1—N3 | 78.78 (12) |
N2—Ru1—N1 | 78.99 (12) | N4—Ru1—N3 | 95.84 (12) |
N4—Ru1—N1 | 86.33 (12) | N1—Ru1—N3 | 157.75 (11) |
N5—Ru1—N6 | 78.44 (13) | N6—Ru1—N3 | 88.91 (12) |
N2—Ru1—N6 | 103.89 (13) |
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.