One single photo-induced linkage NO isomer (PLI) is detected and characterized in the dinitrosyl pentacoordinated compound [RuBr(NO)2(PCyp3)2]BF4 by a combination of photocrystallographic and IR analysis. In the ground state, the molecule adopts a trigonal–bipyramidal structure with the two NO ligands almost linear with angles Ru—N1—O1 = 168.92 (16), Ru—N2—O2 = 166.64 (16)°, and exactly equal distances of Ru—N = 1.7838 (17) and O—N = 1.158 (2) Å. After light irradiation of 405 nm at T = 10 K, the angle of Ru—N2—O2 changes to 114.2 (6)° by rotation of the O atom towards the Br ligand with increased distances of Ru—N2 = 1.992 (6) and N2—O2 = 1.184 (8) Å, forming a bent κN bonded configuration. Using IR spectroscopy, the optimal wavelength and maximum population of 39 (1)% of the PLI is determined. In the ground state (GS), the two symmetric νs(NO) and asymmetric νas(NO) vibrations are measured at 1820 and 1778 cm−1, respectively. Upon photo-irradiation, the detection of only one new vibrational ν(NO) stretching band at 1655 cm−1, assigned to the antisymmetric coupled vibration mode and shifted to lower wavenumbers by −123 cm−1, supports the photocrystallographic result. These experimental results are supported by additional DFT calculations, which reproduce the structural parameters and vibrational properties of both the ground state and the photo-induced linkage isomer well. Especially the experimentally characterized molecular structure of the PLI state corresponds to an energy minimum in the calculations; the stabilization of the bent κN bonded configuration of the PLI state originates from specific intramolecular orbital overlap.
Supporting information
CCDC references: 1427938; 1427939
For both structures, program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014).
(RuBrNO2PCyp32BF4_GS)
top
Crystal data top
C30H54BrN2O2P2Ru·BF4 | Z = 2 |
Mr = 804.48 | F(000) = 828 |
Triclinic, P1 | Dx = 1.613 Mg m−3 |
a = 10.7965 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.2449 (3) Å | Cell parameters from 31048 reflections |
c = 13.7452 (5) Å | θ = 3.1–34.3° |
α = 104.778 (3)° | µ = 1.83 mm−1 |
β = 91.462 (3)° | T = 10 K |
γ = 108.350 (3)° | Block, orange |
V = 1656.57 (10) Å3 | 0.32 × 0.24 × 0.20 mm |
Data collection top
SuperNova Microfocus diffractometer | 11572 reflections with I > 2σ(I) |
Radiation source: D8 Venture (Mo) X-ray Source | Rint = 0.046 |
ω scans | θmax = 34.3°, θmin = 3.1° |
Absorption correction: empirical (using intensity measurements) Absorption correction were performed using empirical (using intensity measurements) methods | h = −16→17 |
Tmin = 0.596, Tmax = 0.694 | k = −19→17 |
31048 measured reflections | l = −19→21 |
13859 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0524P)2 + 0.1851P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
13859 reflections | Δρmax = 2.67 e Å−3 |
388 parameters | Δρmin = −2.37 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Ru1 | 0.30045 (2) | 0.39556 (2) | 0.23791 (2) | 0.00487 (4) | |
N1 | 0.43014 (16) | 0.43127 (14) | 0.16139 (12) | 0.0072 (3) | |
O1 | 0.49804 (15) | 0.44867 (13) | 0.09919 (11) | 0.0102 (3) | |
N2 | 0.13524 (17) | 0.33404 (14) | 0.17847 (13) | 0.0080 (3) | |
O2 | 0.03961 (14) | 0.29535 (13) | 0.12290 (11) | 0.0104 (3) | |
Br1 | 0.33196 (2) | 0.42758 (2) | 0.43020 (2) | 0.00636 (4) | |
P1 | 0.29954 (5) | 0.60106 (4) | 0.29117 (4) | 0.00584 (9) | |
P2 | 0.31749 (5) | 0.20130 (4) | 0.23838 (4) | 0.00580 (9) | |
C1 | 0.17282 (18) | 0.61259 (16) | 0.37593 (15) | 0.0071 (3) | |
H1 | 0.2068 | 0.6082 | 0.4427 | 0.008* | |
C2 | 0.13675 (19) | 0.72770 (16) | 0.39736 (15) | 0.0086 (3) | |
H2A | 0.2095 | 0.7977 | 0.4388 | 0.010* | |
H2B | 0.1130 | 0.7442 | 0.3338 | 0.010* | |
C3 | 0.0182 (2) | 0.69610 (17) | 0.45595 (15) | 0.0093 (3) | |
H3A | −0.0333 | 0.7504 | 0.4570 | 0.011* | |
H3B | 0.0461 | 0.7009 | 0.5265 | 0.011* | |
C4 | −0.0624 (2) | 0.56641 (17) | 0.39660 (16) | 0.0099 (3) | |
H4A | −0.1301 | 0.5655 | 0.3461 | 0.012* | |
H4B | −0.1064 | 0.5206 | 0.4431 | 0.012* | |
C5 | 0.03831 (19) | 0.51197 (17) | 0.34326 (15) | 0.0085 (3) | |
H5A | 0.0387 | 0.4410 | 0.3651 | 0.010* | |
H5B | 0.0168 | 0.4878 | 0.2688 | 0.010* | |
C6 | 0.27202 (19) | 0.66681 (17) | 0.19079 (14) | 0.0077 (3) | |
H6 | 0.2777 | 0.7513 | 0.2239 | 0.009* | |
C7 | 0.36901 (19) | 0.67035 (17) | 0.11028 (15) | 0.0085 (3) | |
H7A | 0.4571 | 0.7287 | 0.1389 | 0.010* | |
H7B | 0.3769 | 0.5904 | 0.0809 | 0.010* | |
C8 | 0.3039 (2) | 0.71010 (18) | 0.03132 (15) | 0.0099 (3) | |
H8A | 0.3302 | 0.6819 | −0.0365 | 0.012* | |
H8B | 0.3292 | 0.7985 | 0.0498 | 0.012* | |
C9 | 0.1545 (2) | 0.65248 (19) | 0.03177 (16) | 0.0114 (4) | |
H9A | 0.1165 | 0.5865 | −0.0308 | 0.014* | |
H9B | 0.1099 | 0.7127 | 0.0363 | 0.014* | |
C10 | 0.13803 (19) | 0.60417 (17) | 0.12588 (15) | 0.0092 (3) | |
H10A | 0.0674 | 0.6246 | 0.1632 | 0.011* | |
H10B | 0.1167 | 0.5161 | 0.1061 | 0.011* | |
C11 | 0.45478 (19) | 0.69941 (16) | 0.36843 (14) | 0.0070 (3) | |
H11 | 0.4480 | 0.6878 | 0.4378 | 0.008* | |
C12 | 0.57949 (19) | 0.67373 (17) | 0.33275 (15) | 0.0088 (3) | |
H12A | 0.5781 | 0.6592 | 0.2584 | 0.011* | |
H12B | 0.5872 | 0.6028 | 0.3511 | 0.011* | |
C13 | 0.69455 (19) | 0.78789 (17) | 0.38862 (15) | 0.0098 (3) | |
H13A | 0.7555 | 0.8154 | 0.3405 | 0.012* | |
H13B | 0.7440 | 0.7719 | 0.4419 | 0.012* | |
C14 | 0.6312 (2) | 0.88352 (17) | 0.43608 (15) | 0.0102 (3) | |
H14A | 0.6298 | 0.8937 | 0.5098 | 0.012* | |
H14B | 0.6804 | 0.9617 | 0.4250 | 0.012* | |
C15 | 0.4912 (2) | 0.83496 (16) | 0.38156 (15) | 0.0090 (3) | |
H15A | 0.4893 | 0.8526 | 0.3153 | 0.011* | |
H15B | 0.4314 | 0.8686 | 0.4232 | 0.011* | |
C16 | 0.19458 (19) | 0.12569 (16) | 0.31071 (15) | 0.0074 (3) | |
H16 | 0.2268 | 0.1659 | 0.3840 | 0.009* | |
C17 | 0.16598 (19) | −0.00948 (16) | 0.29536 (15) | 0.0085 (3) | |
H17A | 0.1454 | −0.0542 | 0.2227 | 0.010* | |
H17B | 0.2410 | −0.0253 | 0.3249 | 0.010* | |
C18 | 0.04572 (19) | −0.04195 (17) | 0.35281 (15) | 0.0094 (3) | |
H18A | 0.0727 | −0.0215 | 0.4264 | 0.011* | |
H18B | −0.0049 | −0.1285 | 0.3281 | 0.011* | |
C19 | −0.03644 (19) | 0.03333 (16) | 0.33077 (15) | 0.0088 (3) | |
H19A | −0.0715 | 0.0671 | 0.3930 | 0.011* | |
H19B | −0.1111 | −0.0167 | 0.2782 | 0.011* | |
C20 | 0.05680 (19) | 0.13499 (17) | 0.29315 (15) | 0.0084 (3) | |
H20A | 0.0323 | 0.1235 | 0.2204 | 0.010* | |
H20B | 0.0540 | 0.2140 | 0.3322 | 0.010* | |
C21 | 0.47739 (18) | 0.22097 (16) | 0.30337 (14) | 0.0068 (3) | |
H21 | 0.4733 | 0.2542 | 0.3772 | 0.008* | |
C22 | 0.51453 (19) | 0.10683 (17) | 0.29346 (15) | 0.0087 (3) | |
H22A | 0.4677 | 0.0602 | 0.3386 | 0.010* | |
H22B | 0.4943 | 0.0552 | 0.2228 | 0.010* | |
C23 | 0.6625 (2) | 0.15720 (18) | 0.32612 (16) | 0.0107 (3) | |
H23A | 0.7041 | 0.0950 | 0.3032 | 0.013* | |
H23B | 0.6818 | 0.1900 | 0.4006 | 0.013* | |
C24 | 0.7098 (2) | 0.25651 (18) | 0.27305 (16) | 0.0109 (3) | |
H24A | 0.7243 | 0.2230 | 0.2024 | 0.013* | |
H24B | 0.7930 | 0.3177 | 0.3094 | 0.013* | |
C25 | 0.59910 (19) | 0.31173 (17) | 0.27506 (15) | 0.0090 (3) | |
H25A | 0.5793 | 0.3221 | 0.2079 | 0.011* | |
H25B | 0.6248 | 0.3907 | 0.3262 | 0.011* | |
C26 | 0.29947 (19) | 0.09500 (16) | 0.11446 (14) | 0.0073 (3) | |
H26 | 0.3128 | 0.0219 | 0.1261 | 0.009* | |
C27 | 0.39806 (19) | 0.13858 (17) | 0.04280 (15) | 0.0085 (3) | |
H27A | 0.3975 | 0.2165 | 0.0348 | 0.010* | |
H27B | 0.4882 | 0.1464 | 0.0675 | 0.010* | |
C28 | 0.3471 (2) | 0.03900 (18) | −0.05673 (15) | 0.0098 (3) | |
H28A | 0.3846 | −0.0257 | −0.0593 | 0.012* | |
H28B | 0.3707 | 0.0710 | −0.1155 | 0.012* | |
C29 | 0.1961 (2) | −0.00830 (18) | −0.05721 (15) | 0.0104 (3) | |
H29A | 0.1642 | −0.0964 | −0.0695 | 0.012* | |
H29B | 0.1522 | 0.0119 | −0.1109 | 0.012* | |
C30 | 0.16710 (19) | 0.05365 (17) | 0.04865 (15) | 0.0091 (3) | |
H30A | 0.1390 | 0.1226 | 0.0465 | 0.011* | |
H30B | 0.0980 | −0.0032 | 0.0745 | 0.011* | |
B1 | 0.8188 (2) | 0.71333 (19) | 0.11620 (17) | 0.0094 (4) | |
F1 | 0.72033 (13) | 0.76430 (11) | 0.14169 (10) | 0.0131 (2) | |
F2 | 0.93409 (12) | 0.80387 (11) | 0.10982 (10) | 0.0122 (2) | |
F4 | 0.77852 (13) | 0.62736 (11) | 0.02226 (10) | 0.0144 (3) | |
F3 | 0.84265 (13) | 0.66087 (11) | 0.19040 (10) | 0.0133 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ru1 | 0.00427 (7) | 0.00350 (6) | 0.00537 (7) | −0.00083 (5) | 0.00125 (5) | 0.00131 (5) |
N1 | 0.0073 (7) | 0.0055 (6) | 0.0075 (7) | −0.0002 (5) | 0.0022 (5) | 0.0023 (5) |
O1 | 0.0108 (7) | 0.0091 (6) | 0.0110 (6) | 0.0020 (5) | 0.0063 (5) | 0.0045 (5) |
N2 | 0.0080 (7) | 0.0048 (6) | 0.0102 (7) | 0.0007 (5) | 0.0022 (6) | 0.0023 (5) |
O2 | 0.0076 (6) | 0.0087 (6) | 0.0120 (6) | −0.0008 (5) | −0.0018 (5) | 0.0024 (5) |
Br1 | 0.00709 (9) | 0.00479 (8) | 0.00580 (8) | −0.00001 (6) | 0.00130 (6) | 0.00151 (6) |
P1 | 0.0051 (2) | 0.00425 (18) | 0.0068 (2) | −0.00061 (15) | 0.00171 (15) | 0.00185 (15) |
P2 | 0.0052 (2) | 0.00458 (18) | 0.0060 (2) | −0.00060 (15) | 0.00118 (15) | 0.00151 (15) |
C1 | 0.0055 (8) | 0.0057 (7) | 0.0092 (8) | 0.0007 (6) | 0.0016 (6) | 0.0020 (6) |
C2 | 0.0095 (8) | 0.0063 (7) | 0.0103 (8) | 0.0022 (6) | 0.0035 (6) | 0.0033 (6) |
C3 | 0.0093 (8) | 0.0085 (8) | 0.0090 (8) | 0.0015 (6) | 0.0028 (6) | 0.0023 (6) |
C4 | 0.0074 (8) | 0.0091 (8) | 0.0115 (8) | 0.0014 (6) | 0.0029 (6) | 0.0014 (7) |
C5 | 0.0055 (8) | 0.0073 (7) | 0.0103 (8) | −0.0004 (6) | 0.0019 (6) | 0.0014 (6) |
C6 | 0.0068 (8) | 0.0073 (7) | 0.0074 (7) | 0.0000 (6) | 0.0002 (6) | 0.0024 (6) |
C7 | 0.0085 (8) | 0.0092 (7) | 0.0087 (8) | 0.0029 (6) | 0.0032 (6) | 0.0039 (6) |
C8 | 0.0083 (8) | 0.0103 (8) | 0.0113 (8) | 0.0008 (7) | 0.0018 (6) | 0.0058 (7) |
C9 | 0.0084 (8) | 0.0152 (9) | 0.0095 (8) | 0.0007 (7) | 0.0001 (6) | 0.0058 (7) |
C10 | 0.0072 (8) | 0.0093 (8) | 0.0097 (8) | −0.0003 (6) | 0.0009 (6) | 0.0039 (6) |
C11 | 0.0066 (8) | 0.0053 (7) | 0.0075 (7) | 0.0000 (6) | 0.0012 (6) | 0.0018 (6) |
C12 | 0.0075 (8) | 0.0066 (7) | 0.0115 (8) | 0.0016 (6) | 0.0023 (6) | 0.0020 (6) |
C13 | 0.0062 (8) | 0.0083 (8) | 0.0108 (8) | −0.0015 (6) | 0.0002 (6) | 0.0004 (6) |
C14 | 0.0082 (8) | 0.0074 (7) | 0.0111 (8) | −0.0017 (6) | 0.0005 (6) | 0.0016 (6) |
C15 | 0.0088 (8) | 0.0044 (7) | 0.0118 (8) | 0.0001 (6) | −0.0003 (6) | 0.0015 (6) |
C16 | 0.0059 (8) | 0.0065 (7) | 0.0083 (8) | −0.0004 (6) | 0.0017 (6) | 0.0026 (6) |
C17 | 0.0083 (8) | 0.0066 (7) | 0.0098 (8) | 0.0005 (6) | 0.0024 (6) | 0.0032 (6) |
C18 | 0.0082 (8) | 0.0079 (7) | 0.0111 (8) | −0.0002 (6) | 0.0026 (6) | 0.0046 (6) |
C19 | 0.0076 (8) | 0.0062 (7) | 0.0111 (8) | −0.0009 (6) | 0.0027 (6) | 0.0040 (6) |
C20 | 0.0051 (8) | 0.0077 (7) | 0.0111 (8) | 0.0000 (6) | 0.0014 (6) | 0.0029 (6) |
C21 | 0.0061 (8) | 0.0065 (7) | 0.0069 (7) | 0.0008 (6) | 0.0022 (6) | 0.0020 (6) |
C22 | 0.0075 (8) | 0.0072 (7) | 0.0112 (8) | 0.0013 (6) | 0.0025 (6) | 0.0037 (6) |
C23 | 0.0082 (8) | 0.0111 (8) | 0.0127 (9) | 0.0023 (7) | 0.0015 (7) | 0.0043 (7) |
C24 | 0.0069 (8) | 0.0096 (8) | 0.0152 (9) | 0.0006 (6) | 0.0028 (7) | 0.0045 (7) |
C25 | 0.0071 (8) | 0.0071 (7) | 0.0114 (8) | −0.0001 (6) | 0.0024 (6) | 0.0033 (6) |
C26 | 0.0083 (8) | 0.0058 (7) | 0.0066 (7) | 0.0006 (6) | 0.0019 (6) | 0.0015 (6) |
C27 | 0.0082 (8) | 0.0066 (7) | 0.0088 (8) | −0.0002 (6) | 0.0027 (6) | 0.0021 (6) |
C28 | 0.0094 (8) | 0.0103 (8) | 0.0087 (8) | 0.0016 (7) | 0.0034 (6) | 0.0028 (6) |
C29 | 0.0103 (8) | 0.0096 (8) | 0.0072 (8) | 0.0000 (7) | 0.0013 (6) | −0.0006 (6) |
C30 | 0.0077 (8) | 0.0093 (8) | 0.0078 (8) | 0.0003 (6) | 0.0009 (6) | 0.0013 (6) |
B1 | 0.0092 (9) | 0.0080 (8) | 0.0088 (9) | −0.0008 (7) | 0.0027 (7) | 0.0027 (7) |
F1 | 0.0117 (6) | 0.0142 (6) | 0.0158 (6) | 0.0055 (5) | 0.0047 (5) | 0.0065 (5) |
F2 | 0.0097 (6) | 0.0102 (5) | 0.0131 (6) | −0.0018 (4) | 0.0026 (4) | 0.0033 (4) |
F4 | 0.0149 (6) | 0.0116 (5) | 0.0103 (6) | −0.0016 (5) | 0.0005 (5) | −0.0005 (4) |
F3 | 0.0153 (6) | 0.0138 (6) | 0.0129 (6) | 0.0053 (5) | 0.0023 (5) | 0.0065 (5) |
Geometric parameters (Å, º) top
Ru1—N2 | 1.7838 (17) | C14—H14A | 0.9900 |
Ru1—N1 | 1.7839 (16) | C14—H14B | 0.9900 |
Ru1—P1 | 2.4381 (5) | C15—H15A | 0.9900 |
Ru1—P2 | 2.4444 (5) | C15—H15B | 0.9900 |
Ru1—Br1 | 2.5684 (3) | C16—C17 | 1.542 (3) |
N1—O1 | 1.158 (2) | C16—C20 | 1.545 (3) |
N2—O2 | 1.158 (2) | C16—H16 | 1.0000 |
P1—C6 | 1.827 (2) | C17—C18 | 1.535 (3) |
P1—C1 | 1.8352 (19) | C17—H17A | 0.9900 |
P1—C11 | 1.8366 (19) | C17—H17B | 0.9900 |
P2—C26 | 1.8238 (19) | C18—C19 | 1.540 (3) |
P2—C16 | 1.8357 (19) | C18—H18A | 0.9900 |
P2—C21 | 1.840 (2) | C18—H18B | 0.9900 |
C1—C2 | 1.538 (3) | C19—C20 | 1.548 (3) |
C1—C5 | 1.545 (3) | C19—H19A | 0.9900 |
C1—H1 | 1.0000 | C19—H19B | 0.9900 |
C2—C3 | 1.528 (3) | C20—H20A | 0.9900 |
C2—H2A | 0.9900 | C20—H20B | 0.9900 |
C2—H2B | 0.9900 | C21—C22 | 1.546 (3) |
C3—C4 | 1.542 (3) | C21—C25 | 1.562 (3) |
C3—H3A | 0.9900 | C21—H21 | 1.0000 |
C3—H3B | 0.9900 | C22—C23 | 1.529 (3) |
C4—C5 | 1.553 (3) | C22—H22A | 0.9900 |
C4—H4A | 0.9900 | C22—H22B | 0.9900 |
C4—H4B | 0.9900 | C23—C24 | 1.534 (3) |
C5—H5A | 0.9900 | C23—H23A | 0.9900 |
C5—H5B | 0.9900 | C23—H23B | 0.9900 |
C6—C10 | 1.537 (3) | C24—C25 | 1.545 (3) |
C6—C7 | 1.542 (3) | C24—H24A | 0.9900 |
C6—H6 | 1.0000 | C24—H24B | 0.9900 |
C7—C8 | 1.535 (3) | C25—H25A | 0.9900 |
C7—H7A | 0.9900 | C25—H25B | 0.9900 |
C7—H7B | 0.9900 | C26—C27 | 1.534 (3) |
C8—C9 | 1.544 (3) | C26—C30 | 1.537 (3) |
C8—H8A | 0.9900 | C26—H26 | 1.0000 |
C8—H8B | 0.9900 | C27—C28 | 1.533 (3) |
C9—C10 | 1.546 (3) | C27—H27A | 0.9900 |
C9—H9A | 0.9900 | C27—H27B | 0.9900 |
C9—H9B | 0.9900 | C28—C29 | 1.548 (3) |
C10—H10A | 0.9900 | C28—H28A | 0.9900 |
C10—H10B | 0.9900 | C28—H28B | 0.9900 |
C11—C12 | 1.541 (3) | C29—C30 | 1.549 (3) |
C11—C15 | 1.541 (3) | C29—H29A | 0.9900 |
C11—H11 | 1.0000 | C29—H29B | 0.9900 |
C12—C13 | 1.548 (3) | C30—H30A | 0.9900 |
C12—H12A | 0.9900 | C30—H30B | 0.9900 |
C12—H12B | 0.9900 | B1—F3 | 1.394 (3) |
C13—C14 | 1.550 (3) | B1—F4 | 1.398 (3) |
C13—H13A | 0.9900 | B1—F1 | 1.403 (3) |
C13—H13B | 0.9900 | B1—F2 | 1.404 (2) |
C14—C15 | 1.533 (3) | | |
| | | |
N2—Ru1—N1 | 118.52 (8) | C15—C14—H14B | 110.8 |
N2—Ru1—P1 | 94.84 (5) | C13—C14—H14B | 110.8 |
N1—Ru1—P1 | 92.96 (5) | H14A—C14—H14B | 108.8 |
N2—Ru1—P2 | 94.26 (5) | C14—C15—C11 | 102.07 (16) |
N1—Ru1—P2 | 95.27 (5) | C14—C15—H15A | 111.4 |
P1—Ru1—P2 | 162.995 (18) | C11—C15—H15A | 111.4 |
N2—Ru1—Br1 | 116.49 (5) | C14—C15—H15B | 111.4 |
N1—Ru1—Br1 | 124.98 (5) | C11—C15—H15B | 111.4 |
P1—Ru1—Br1 | 81.971 (13) | H15A—C15—H15B | 109.2 |
P2—Ru1—Br1 | 81.117 (13) | C17—C16—C20 | 103.30 (15) |
O1—N1—Ru1 | 168.92 (16) | C17—C16—P2 | 117.84 (13) |
O2—N2—Ru1 | 166.64 (16) | C20—C16—P2 | 114.72 (14) |
C6—P1—C1 | 106.57 (9) | C17—C16—H16 | 106.8 |
C6—P1—C11 | 107.93 (9) | C20—C16—H16 | 106.8 |
C1—P1—C11 | 104.62 (9) | P2—C16—H16 | 106.8 |
C6—P1—Ru1 | 116.64 (6) | C18—C17—C16 | 101.91 (15) |
C1—P1—Ru1 | 110.37 (6) | C18—C17—H17A | 111.4 |
C11—P1—Ru1 | 109.98 (6) | C16—C17—H17A | 111.4 |
C26—P2—C16 | 106.59 (9) | C18—C17—H17B | 111.4 |
C26—P2—C21 | 106.76 (9) | C16—C17—H17B | 111.4 |
C16—P2—C21 | 105.20 (9) | H17A—C17—H17B | 109.3 |
C26—P2—Ru1 | 116.02 (7) | C17—C18—C19 | 104.79 (16) |
C16—P2—Ru1 | 111.23 (6) | C17—C18—H18A | 110.8 |
C21—P2—Ru1 | 110.38 (6) | C19—C18—H18A | 110.8 |
C2—C1—C5 | 103.37 (15) | C17—C18—H18B | 110.8 |
C2—C1—P1 | 117.24 (13) | C19—C18—H18B | 110.8 |
C5—C1—P1 | 115.79 (13) | H18A—C18—H18B | 108.9 |
C2—C1—H1 | 106.6 | C18—C19—C20 | 106.58 (16) |
C5—C1—H1 | 106.6 | C18—C19—H19A | 110.4 |
P1—C1—H1 | 106.6 | C20—C19—H19A | 110.4 |
C3—C2—C1 | 101.49 (15) | C18—C19—H19B | 110.4 |
C3—C2—H2A | 111.5 | C20—C19—H19B | 110.4 |
C1—C2—H2A | 111.5 | H19A—C19—H19B | 108.6 |
C3—C2—H2B | 111.5 | C16—C20—C19 | 104.67 (16) |
C1—C2—H2B | 111.5 | C16—C20—H20A | 110.8 |
H2A—C2—H2B | 109.3 | C19—C20—H20A | 110.8 |
C2—C3—C4 | 103.80 (15) | C16—C20—H20B | 110.8 |
C2—C3—H3A | 111.0 | C19—C20—H20B | 110.8 |
C4—C3—H3A | 111.0 | H20A—C20—H20B | 108.9 |
C2—C3—H3B | 111.0 | C22—C21—C25 | 105.05 (15) |
C4—C3—H3B | 111.0 | C22—C21—P2 | 116.88 (13) |
H3A—C3—H3B | 109.0 | C25—C21—P2 | 115.62 (14) |
C3—C4—C5 | 105.56 (16) | C22—C21—H21 | 106.2 |
C3—C4—H4A | 110.6 | C25—C21—H21 | 106.2 |
C5—C4—H4A | 110.6 | P2—C21—H21 | 106.2 |
C3—C4—H4B | 110.6 | C23—C22—C21 | 102.83 (15) |
C5—C4—H4B | 110.6 | C23—C22—H22A | 111.2 |
H4A—C4—H4B | 108.8 | C21—C22—H22A | 111.2 |
C1—C5—C4 | 105.30 (15) | C23—C22—H22B | 111.2 |
C1—C5—H5A | 110.7 | C21—C22—H22B | 111.2 |
C4—C5—H5A | 110.7 | H22A—C22—H22B | 109.1 |
C1—C5—H5B | 110.7 | C22—C23—C24 | 102.99 (16) |
C4—C5—H5B | 110.7 | C22—C23—H23A | 111.2 |
H5A—C5—H5B | 108.8 | C24—C23—H23A | 111.2 |
C10—C6—C7 | 102.47 (15) | C22—C23—H23B | 111.2 |
C10—C6—P1 | 115.16 (13) | C24—C23—H23B | 111.2 |
C7—C6—P1 | 116.58 (14) | H23A—C23—H23B | 109.1 |
C10—C6—H6 | 107.4 | C23—C24—C25 | 105.55 (16) |
C7—C6—H6 | 107.4 | C23—C24—H24A | 110.6 |
P1—C6—H6 | 107.4 | C25—C24—H24A | 110.6 |
C8—C7—C6 | 102.03 (16) | C23—C24—H24B | 110.6 |
C8—C7—H7A | 111.4 | C25—C24—H24B | 110.6 |
C6—C7—H7A | 111.4 | H24A—C24—H24B | 108.8 |
C8—C7—H7B | 111.4 | C24—C25—C21 | 105.50 (15) |
C6—C7—H7B | 111.4 | C24—C25—H25A | 110.6 |
H7A—C7—H7B | 109.2 | C21—C25—H25A | 110.6 |
C7—C8—C9 | 105.53 (16) | C24—C25—H25B | 110.6 |
C7—C8—H8A | 110.6 | C21—C25—H25B | 110.6 |
C9—C8—H8A | 110.6 | H25A—C25—H25B | 108.8 |
C7—C8—H8B | 110.6 | C27—C26—C30 | 102.40 (15) |
C9—C8—H8B | 110.6 | C27—C26—P2 | 115.20 (13) |
H8A—C8—H8B | 108.8 | C30—C26—P2 | 117.04 (13) |
C8—C9—C10 | 106.02 (16) | C27—C26—H26 | 107.2 |
C8—C9—H9A | 110.5 | C30—C26—H26 | 107.2 |
C10—C9—H9A | 110.5 | P2—C26—H26 | 107.2 |
C8—C9—H9B | 110.5 | C28—C27—C26 | 102.66 (15) |
C10—C9—H9B | 110.5 | C28—C27—H27A | 111.2 |
H9A—C9—H9B | 108.7 | C26—C27—H27A | 111.2 |
C6—C10—C9 | 104.45 (15) | C28—C27—H27B | 111.2 |
C6—C10—H10A | 110.9 | C26—C27—H27B | 111.2 |
C9—C10—H10A | 110.9 | H27A—C27—H27B | 109.1 |
C6—C10—H10B | 110.9 | C27—C28—C29 | 105.28 (15) |
C9—C10—H10B | 110.9 | C27—C28—H28A | 110.7 |
H10A—C10—H10B | 108.9 | C29—C28—H28A | 110.7 |
C12—C11—C15 | 102.77 (15) | C27—C28—H28B | 110.7 |
C12—C11—P1 | 115.83 (13) | C29—C28—H28B | 110.7 |
C15—C11—P1 | 117.38 (14) | H28A—C28—H28B | 108.8 |
C12—C11—H11 | 106.7 | C28—C29—C30 | 106.24 (15) |
C15—C11—H11 | 106.7 | C28—C29—H29A | 110.5 |
P1—C11—H11 | 106.7 | C30—C29—H29A | 110.5 |
C11—C12—C13 | 104.88 (15) | C28—C29—H29B | 110.5 |
C11—C12—H12A | 110.8 | C30—C29—H29B | 110.5 |
C13—C12—H12A | 110.8 | H29A—C29—H29B | 108.7 |
C11—C12—H12B | 110.8 | C26—C30—C29 | 103.42 (16) |
C13—C12—H12B | 110.8 | C26—C30—H30A | 111.1 |
H12A—C12—H12B | 108.8 | C29—C30—H30A | 111.1 |
C12—C13—C14 | 106.03 (16) | C26—C30—H30B | 111.1 |
C12—C13—H13A | 110.5 | C29—C30—H30B | 111.1 |
C14—C13—H13A | 110.5 | H30A—C30—H30B | 109.0 |
C12—C13—H13B | 110.5 | F3—B1—F4 | 110.22 (17) |
C14—C13—H13B | 110.5 | F3—B1—F1 | 109.78 (17) |
H13A—C13—H13B | 108.7 | F4—B1—F1 | 109.18 (18) |
C15—C14—C13 | 104.94 (15) | F3—B1—F2 | 109.53 (18) |
C15—C14—H14A | 110.8 | F4—B1—F2 | 109.33 (17) |
C13—C14—H14A | 110.8 | F1—B1—F2 | 108.77 (17) |
(RuBrNO2PCyp32BF4_PLI)
top
Crystal data top
C30H54BrN2O2P2Ru·BF4 | Z = 2 |
Mr = 804.48 | F(000) = 828 |
Triclinic, P1 | Dx = 1.611 Mg m−3 |
a = 10.7862 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.2712 (5) Å | Cell parameters from 25540 reflections |
c = 13.7402 (5) Å | θ = 3.1–33.1° |
α = 104.562 (3)° | µ = 1.83 mm−1 |
β = 91.987 (3)° | T = 10 K |
γ = 108.301 (3)° | Block, orange |
V = 1658.37 (11) Å3 | 0.28 × 0.19 × 0.14 mm |
Data collection top
SuperNova Microfocus diffractometer | 10545 reflections with I > 2σ(I) |
Radiation source: D8 Venture (Mo) X-ray Source | Rint = 0.037 |
ω scans | θmax = 33.1°, θmin = 3.1° |
Absorption correction: empirical (using intensity measurements) Absorption correction were performed using empirical (using intensity measurements) methods | h = −16→16 |
Tmin = 0.666, Tmax = 0.774 | k = −18→17 |
25540 measured reflections | l = −18→21 |
12568 independent reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.0575P)2 + 0.3679P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
12568 reflections | Δρmax = 2.31 e Å−3 |
381 parameters | Δρmin = −2.28 e Å−3 |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
N2B | 0.1363 (6) | 0.3310 (6) | 0.1429 (5) | 0.0088 (5)* | 0.316 (3) |
O2B | 0.0391 (5) | 0.3057 (5) | 0.1820 (4) | 0.0113 (4)* | 0.316 (3) |
O1B | 0.4845 (8) | 0.4454 (8) | 0.0913 (6) | 0.0090 (4)* | 0.316 (3) |
N1B | 0.4004 (7) | 0.4213 (6) | 0.1402 (5) | 0.0096 (5)* | 0.316 (3) |
N2A | 0.1359 (3) | 0.3335 (3) | 0.1779 (2) | 0.0088 (5)* | 0.684 (3) |
O2A | 0.0399 (2) | 0.2945 (2) | 0.12268 (19) | 0.0113 (4)* | 0.684 (3) |
Ru1 | 0.30181 (2) | 0.39638 (2) | 0.23861 (2) | 0.00516 (4) | |
N1A | 0.4322 (3) | 0.4316 (3) | 0.1623 (2) | 0.0096 (5)* | 0.684 (3) |
O1A | 0.5015 (3) | 0.4497 (3) | 0.1028 (3) | 0.0090 (4)* | 0.684 (3) |
Br1 | 0.32809 (3) | 0.42636 (2) | 0.42896 (2) | 0.01642 (6) | |
P1 | 0.29916 (5) | 0.60102 (5) | 0.29033 (4) | 0.00593 (9) | |
P2 | 0.31831 (5) | 0.20192 (5) | 0.23841 (4) | 0.00566 (9) | |
C1 | 0.1729 (2) | 0.61341 (18) | 0.37513 (16) | 0.0078 (3) | |
H1 | 0.2075 | 0.6088 | 0.4419 | 0.009* | |
C2 | 0.1377 (2) | 0.72845 (19) | 0.39669 (17) | 0.0095 (4) | |
H2A | 0.2110 | 0.7980 | 0.4383 | 0.011* | |
H2B | 0.1133 | 0.7452 | 0.3332 | 0.011* | |
C3 | 0.0194 (2) | 0.6968 (2) | 0.45531 (17) | 0.0109 (4) | |
H3A | −0.0327 | 0.7504 | 0.4554 | 0.013* | |
H3B | 0.0484 | 0.7029 | 0.5262 | 0.013* | |
C4 | −0.0613 (2) | 0.5673 (2) | 0.39782 (18) | 0.0117 (4) | |
H4A | −0.1316 | 0.5651 | 0.3484 | 0.014* | |
H4B | −0.1021 | 0.5221 | 0.4455 | 0.014* | |
C5 | 0.0378 (2) | 0.51340 (19) | 0.34262 (16) | 0.0098 (4) | |
H5A | 0.0387 | 0.4419 | 0.3632 | 0.012* | |
H5B | 0.0144 | 0.4905 | 0.2682 | 0.012* | |
C6 | 0.2715 (2) | 0.66719 (18) | 0.18975 (16) | 0.0078 (3) | |
H6 | 0.2763 | 0.7511 | 0.2229 | 0.009* | |
C7 | 0.3686 (2) | 0.6720 (2) | 0.11023 (16) | 0.0099 (4) | |
H7A | 0.4566 | 0.7306 | 0.1396 | 0.012* | |
H7B | 0.3771 | 0.5926 | 0.0809 | 0.012* | |
C8 | 0.3028 (2) | 0.7116 (2) | 0.03067 (17) | 0.0107 (4) | |
H8A | 0.3306 | 0.6853 | −0.0367 | 0.013* | |
H8B | 0.3262 | 0.7996 | 0.0500 | 0.013* | |
C9 | 0.1536 (2) | 0.6508 (2) | 0.02898 (18) | 0.0134 (4) | |
H9A | 0.1177 | 0.5842 | −0.0335 | 0.016* | |
H9B | 0.1067 | 0.7089 | 0.0315 | 0.016* | |
C10 | 0.1372 (2) | 0.6037 (2) | 0.12371 (16) | 0.0100 (4) | |
H10A | 0.0663 | 0.6239 | 0.1601 | 0.012* | |
H10B | 0.1162 | 0.5159 | 0.1047 | 0.012* | |
C11 | 0.4552 (2) | 0.69959 (18) | 0.36824 (16) | 0.0074 (3) | |
H11 | 0.4493 | 0.6879 | 0.4376 | 0.009* | |
C12 | 0.5793 (2) | 0.67344 (19) | 0.33201 (17) | 0.0092 (4) | |
H12A | 0.5770 | 0.6593 | 0.2577 | 0.011* | |
H12B | 0.5871 | 0.6025 | 0.3501 | 0.011* | |
C13 | 0.6953 (2) | 0.7874 (2) | 0.38826 (17) | 0.0119 (4) | |
H13A | 0.7448 | 0.7713 | 0.4419 | 0.014* | |
H13B | 0.7564 | 0.8145 | 0.3404 | 0.014* | |
C14 | 0.6331 (2) | 0.88344 (19) | 0.43514 (17) | 0.0113 (4) | |
H14A | 0.6332 | 0.8946 | 0.5091 | 0.014* | |
H14B | 0.6820 | 0.9609 | 0.4230 | 0.014* | |
C15 | 0.4914 (2) | 0.83446 (18) | 0.38105 (16) | 0.0089 (4) | |
H15A | 0.4322 | 0.8680 | 0.4230 | 0.011* | |
H15B | 0.4879 | 0.8518 | 0.3146 | 0.011* | |
C16 | 0.19697 (19) | 0.12566 (18) | 0.31078 (16) | 0.0070 (3) | |
H16 | 0.2303 | 0.1657 | 0.3841 | 0.008* | |
C17 | 0.1681 (2) | −0.00935 (18) | 0.29557 (17) | 0.0090 (4) | |
H17A | 0.1463 | −0.0540 | 0.2229 | 0.011* | |
H17B | 0.2437 | −0.0252 | 0.3248 | 0.011* | |
C18 | 0.0490 (2) | −0.0416 (2) | 0.35352 (17) | 0.0107 (4) | |
H18A | 0.0773 | −0.0206 | 0.4271 | 0.013* | |
H18B | −0.0015 | −0.1280 | 0.3293 | 0.013* | |
C19 | −0.0346 (2) | 0.03289 (19) | 0.33131 (17) | 0.0104 (4) | |
H19A | −0.0693 | 0.0664 | 0.3934 | 0.013* | |
H19B | −0.1096 | −0.0172 | 0.2787 | 0.013* | |
C20 | 0.0581 (2) | 0.13424 (19) | 0.29382 (16) | 0.0085 (4) | |
H20A | 0.0556 | 0.2130 | 0.3331 | 0.010* | |
H20B | 0.0324 | 0.1230 | 0.2212 | 0.010* | |
C21 | 0.47942 (19) | 0.22272 (18) | 0.30409 (16) | 0.0070 (3) | |
H21 | 0.4761 | 0.2565 | 0.3778 | 0.008* | |
C22 | 0.5173 (2) | 0.10939 (19) | 0.29523 (16) | 0.0088 (4) | |
H22A | 0.4725 | 0.0641 | 0.3416 | 0.011* | |
H22B | 0.4951 | 0.0566 | 0.2250 | 0.011* | |
C23 | 0.6662 (2) | 0.1602 (2) | 0.32603 (18) | 0.0127 (4) | |
H23A | 0.7074 | 0.0981 | 0.3034 | 0.015* | |
H23B | 0.6877 | 0.1943 | 0.4004 | 0.015* | |
C24 | 0.7112 (2) | 0.2576 (2) | 0.27121 (19) | 0.0144 (4) | |
H24A | 0.7226 | 0.2229 | 0.2002 | 0.017* | |
H24B | 0.7956 | 0.3187 | 0.3060 | 0.017* | |
C25 | 0.6000 (2) | 0.31307 (19) | 0.27500 (17) | 0.0099 (4) | |
H25A | 0.5782 | 0.3238 | 0.2082 | 0.012* | |
H25B | 0.6270 | 0.3917 | 0.3263 | 0.012* | |
C26 | 0.29980 (19) | 0.09514 (18) | 0.11458 (15) | 0.0068 (3) | |
H26 | 0.3136 | 0.0226 | 0.1268 | 0.008* | |
C27 | 0.3980 (2) | 0.13838 (19) | 0.04295 (16) | 0.0091 (4) | |
H27B | 0.4884 | 0.1461 | 0.0679 | 0.011* | |
H27A | 0.3974 | 0.2161 | 0.0347 | 0.011* | |
C28 | 0.3457 (2) | 0.03852 (19) | −0.05672 (16) | 0.0097 (4) | |
H28A | 0.3827 | −0.0262 | −0.0589 | 0.012* | |
H28B | 0.3691 | 0.0701 | −0.1157 | 0.012* | |
C29 | 0.1945 (2) | −0.0080 (2) | −0.05753 (16) | 0.0107 (4) | |
H29A | 0.1620 | −0.0959 | −0.0704 | 0.013* | |
H29B | 0.1505 | 0.0130 | −0.1110 | 0.013* | |
C30 | 0.1667 (2) | 0.05319 (19) | 0.04845 (16) | 0.0091 (4) | |
H30A | 0.1379 | 0.1217 | 0.0464 | 0.011* | |
H30B | 0.0982 | −0.0039 | 0.0742 | 0.011* | |
B1 | 0.8193 (2) | 0.7113 (2) | 0.11824 (19) | 0.0100 (4) | |
F1 | 0.72096 (13) | 0.76338 (13) | 0.14121 (11) | 0.0131 (3) | |
F2 | 0.93351 (13) | 0.79959 (13) | 0.10722 (11) | 0.0149 (3) | |
F4 | 0.77602 (16) | 0.62142 (16) | 0.02706 (13) | 0.0288 (4) | |
F3 | 0.84602 (15) | 0.66577 (14) | 0.19605 (12) | 0.0191 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ru1 | 0.00540 (7) | 0.00233 (7) | 0.00698 (8) | −0.00021 (5) | 0.00079 (5) | 0.00186 (5) |
Br1 | 0.03744 (15) | 0.00718 (10) | 0.00909 (10) | 0.01085 (10) | 0.00854 (9) | 0.00491 (8) |
P1 | 0.0054 (2) | 0.0033 (2) | 0.0083 (2) | −0.00013 (16) | 0.00074 (17) | 0.00224 (17) |
P2 | 0.0056 (2) | 0.0030 (2) | 0.0076 (2) | −0.00001 (16) | 0.00046 (17) | 0.00209 (17) |
C1 | 0.0079 (8) | 0.0052 (8) | 0.0092 (9) | 0.0008 (7) | 0.0009 (7) | 0.0019 (7) |
C2 | 0.0090 (9) | 0.0081 (9) | 0.0123 (9) | 0.0027 (7) | 0.0026 (7) | 0.0042 (7) |
C3 | 0.0099 (9) | 0.0122 (9) | 0.0109 (9) | 0.0035 (7) | 0.0027 (7) | 0.0040 (8) |
C4 | 0.0073 (9) | 0.0122 (9) | 0.0141 (10) | 0.0012 (7) | 0.0022 (7) | 0.0039 (8) |
C5 | 0.0078 (8) | 0.0087 (9) | 0.0104 (9) | −0.0008 (7) | 0.0011 (7) | 0.0027 (7) |
C6 | 0.0068 (8) | 0.0056 (8) | 0.0101 (9) | 0.0000 (7) | 0.0016 (7) | 0.0032 (7) |
C7 | 0.0084 (9) | 0.0103 (9) | 0.0105 (9) | 0.0017 (7) | 0.0013 (7) | 0.0037 (7) |
C8 | 0.0097 (9) | 0.0115 (9) | 0.0117 (9) | 0.0017 (7) | 0.0019 (7) | 0.0068 (8) |
C9 | 0.0088 (9) | 0.0191 (11) | 0.0136 (10) | 0.0027 (8) | 0.0010 (7) | 0.0094 (9) |
C10 | 0.0071 (8) | 0.0106 (9) | 0.0112 (9) | 0.0005 (7) | −0.0010 (7) | 0.0046 (7) |
C11 | 0.0069 (8) | 0.0051 (8) | 0.0090 (9) | 0.0004 (6) | 0.0009 (7) | 0.0019 (7) |
C12 | 0.0065 (8) | 0.0077 (8) | 0.0130 (9) | 0.0018 (7) | 0.0007 (7) | 0.0034 (7) |
C13 | 0.0075 (9) | 0.0123 (9) | 0.0133 (10) | 0.0003 (7) | 0.0008 (7) | 0.0030 (8) |
C14 | 0.0098 (9) | 0.0079 (9) | 0.0130 (10) | −0.0014 (7) | −0.0006 (7) | 0.0030 (7) |
C15 | 0.0090 (9) | 0.0061 (8) | 0.0106 (9) | 0.0009 (7) | 0.0003 (7) | 0.0030 (7) |
C16 | 0.0056 (8) | 0.0050 (8) | 0.0092 (9) | −0.0004 (6) | 0.0012 (6) | 0.0026 (7) |
C17 | 0.0089 (8) | 0.0054 (8) | 0.0119 (9) | 0.0003 (7) | −0.0002 (7) | 0.0037 (7) |
C18 | 0.0092 (9) | 0.0094 (9) | 0.0146 (10) | 0.0014 (7) | 0.0021 (7) | 0.0074 (8) |
C19 | 0.0082 (9) | 0.0089 (9) | 0.0127 (9) | −0.0006 (7) | 0.0023 (7) | 0.0044 (7) |
C20 | 0.0064 (8) | 0.0076 (8) | 0.0103 (9) | 0.0003 (7) | 0.0004 (7) | 0.0032 (7) |
C21 | 0.0053 (8) | 0.0058 (8) | 0.0098 (9) | 0.0012 (6) | 0.0005 (6) | 0.0029 (7) |
C22 | 0.0089 (9) | 0.0079 (8) | 0.0116 (9) | 0.0029 (7) | 0.0014 (7) | 0.0061 (7) |
C23 | 0.0088 (9) | 0.0130 (10) | 0.0158 (10) | 0.0045 (8) | −0.0001 (8) | 0.0023 (8) |
C24 | 0.0093 (9) | 0.0108 (9) | 0.0212 (11) | 0.0017 (8) | 0.0025 (8) | 0.0032 (8) |
C25 | 0.0066 (8) | 0.0070 (8) | 0.0145 (10) | −0.0001 (7) | 0.0014 (7) | 0.0033 (7) |
C26 | 0.0070 (8) | 0.0038 (8) | 0.0086 (8) | 0.0005 (6) | 0.0004 (6) | 0.0019 (6) |
C27 | 0.0082 (8) | 0.0059 (8) | 0.0111 (9) | −0.0001 (7) | 0.0005 (7) | 0.0019 (7) |
C28 | 0.0115 (9) | 0.0079 (8) | 0.0091 (9) | 0.0029 (7) | 0.0017 (7) | 0.0019 (7) |
C29 | 0.0101 (9) | 0.0090 (9) | 0.0096 (9) | 0.0003 (7) | 0.0006 (7) | 0.0004 (7) |
C30 | 0.0066 (8) | 0.0084 (8) | 0.0100 (9) | 0.0003 (7) | −0.0011 (7) | 0.0019 (7) |
B1 | 0.0088 (10) | 0.0082 (10) | 0.0103 (10) | 0.0007 (8) | 0.0016 (8) | 0.0008 (8) |
F1 | 0.0119 (6) | 0.0129 (6) | 0.0174 (7) | 0.0053 (5) | 0.0037 (5) | 0.0074 (5) |
F2 | 0.0099 (6) | 0.0148 (7) | 0.0191 (7) | 0.0003 (5) | 0.0021 (5) | 0.0080 (6) |
F4 | 0.0184 (8) | 0.0244 (9) | 0.0266 (9) | 0.0010 (6) | −0.0027 (6) | −0.0140 (7) |
F3 | 0.0187 (7) | 0.0199 (7) | 0.0277 (8) | 0.0100 (6) | 0.0080 (6) | 0.0172 (6) |
Geometric parameters (Å, º) top
N2B—O2B | 1.184 (8) | C14—C15 | 1.539 (3) |
O1B—N1B | 1.155 (10) | C14—H14A | 0.9900 |
N2A—O2A | 1.153 (4) | C14—H14B | 0.9900 |
N2A—Ru1 | 1.789 (3) | C15—H15A | 0.9900 |
Ru1—N1A | 1.792 (3) | C15—H15B | 0.9900 |
Ru1—P1 | 2.4415 (5) | C16—C17 | 1.544 (3) |
Ru1—P2 | 2.4473 (6) | C16—C20 | 1.548 (3) |
Ru1—Br1 | 2.5408 (3) | C16—H16 | 1.0000 |
N1A—O1A | 1.142 (5) | C17—C18 | 1.534 (3) |
P1—C6 | 1.829 (2) | C17—H17A | 0.9900 |
P1—C1 | 1.840 (2) | C17—H17B | 0.9900 |
P1—C11 | 1.841 (2) | C18—C19 | 1.542 (3) |
P2—C26 | 1.828 (2) | C18—H18A | 0.9900 |
P2—C16 | 1.835 (2) | C18—H18B | 0.9900 |
P2—C21 | 1.843 (2) | C19—C20 | 1.545 (3) |
C1—C2 | 1.536 (3) | C19—H19A | 0.9900 |
C1—C5 | 1.545 (3) | C19—H19B | 0.9900 |
C1—H1 | 1.0000 | C20—H20A | 0.9900 |
C2—C3 | 1.531 (3) | C20—H20B | 0.9900 |
C2—H2A | 0.9900 | C21—C22 | 1.547 (3) |
C2—H2B | 0.9900 | C21—C25 | 1.560 (3) |
C3—C4 | 1.536 (3) | C21—H21 | 1.0000 |
C3—H3A | 0.9900 | C22—C23 | 1.528 (3) |
C3—H3B | 0.9900 | C22—H22A | 0.9900 |
C4—C5 | 1.550 (3) | C22—H22B | 0.9900 |
C4—H4A | 0.9900 | C23—C24 | 1.531 (4) |
C4—H4B | 0.9900 | C23—H23A | 0.9900 |
C5—H5A | 0.9900 | C23—H23B | 0.9900 |
C5—H5B | 0.9900 | C24—C25 | 1.550 (3) |
C6—C7 | 1.538 (3) | C24—H24A | 0.9900 |
C6—C10 | 1.541 (3) | C24—H24B | 0.9900 |
C6—H6 | 1.0000 | C25—H25A | 0.9900 |
C7—C8 | 1.538 (3) | C25—H25B | 0.9900 |
C7—H7A | 0.9900 | C26—C27 | 1.534 (3) |
C7—H7B | 0.9900 | C26—C30 | 1.536 (3) |
C8—C9 | 1.544 (3) | C26—H26 | 1.0000 |
C8—H8A | 0.9900 | C27—C28 | 1.537 (3) |
C8—H8B | 0.9900 | C27—H27B | 0.9900 |
C9—C10 | 1.546 (3) | C27—H27A | 0.9900 |
C9—H9A | 0.9900 | C28—C29 | 1.548 (3) |
C9—H9B | 0.9900 | C28—H28A | 0.9900 |
C10—H10A | 0.9900 | C28—H28B | 0.9900 |
C10—H10B | 0.9900 | C29—C30 | 1.548 (3) |
C11—C15 | 1.538 (3) | C29—H29A | 0.9900 |
C11—C12 | 1.542 (3) | C29—H29B | 0.9900 |
C11—H11 | 1.0000 | C30—H30A | 0.9900 |
C12—C13 | 1.552 (3) | C30—H30B | 0.9900 |
C12—H12A | 0.9900 | B1—F3 | 1.385 (3) |
C12—H12B | 0.9900 | B1—F4 | 1.395 (3) |
C13—C14 | 1.549 (3) | B1—F2 | 1.404 (3) |
C13—H13A | 0.9900 | B1—F1 | 1.407 (3) |
C13—H13B | 0.9900 | | |
| | | |
O2A—N2A—Ru1 | 167.3 (3) | C15—C14—H14B | 110.8 |
N2A—Ru1—N1A | 118.46 (15) | C13—C14—H14B | 110.8 |
N2A—Ru1—P1 | 94.83 (9) | H14A—C14—H14B | 108.8 |
N1A—Ru1—P1 | 93.34 (10) | C11—C15—C14 | 102.15 (17) |
N2A—Ru1—P2 | 93.52 (10) | C11—C15—H15A | 111.3 |
N1A—Ru1—P2 | 94.87 (10) | C14—C15—H15A | 111.3 |
P1—Ru1—P2 | 163.78 (2) | C11—C15—H15B | 111.3 |
N2A—Ru1—Br1 | 115.32 (10) | C14—C15—H15B | 111.3 |
N1A—Ru1—Br1 | 126.22 (10) | H15A—C15—H15B | 109.2 |
P1—Ru1—Br1 | 82.287 (15) | C17—C16—C20 | 102.91 (16) |
P2—Ru1—Br1 | 81.579 (15) | C17—C16—P2 | 118.32 (14) |
O1A—N1A—Ru1 | 170.4 (3) | C20—C16—P2 | 114.84 (15) |
C6—P1—C1 | 106.54 (10) | C17—C16—H16 | 106.7 |
C6—P1—C11 | 107.66 (10) | C20—C16—H16 | 106.7 |
C1—P1—C11 | 104.30 (9) | P2—C16—H16 | 106.7 |
C6—P1—Ru1 | 117.20 (7) | C18—C17—C16 | 101.98 (16) |
C1—P1—Ru1 | 110.80 (7) | C18—C17—H17A | 111.4 |
C11—P1—Ru1 | 109.51 (7) | C16—C17—H17A | 111.4 |
C26—P2—C16 | 106.35 (9) | C18—C17—H17B | 111.4 |
C26—P2—C21 | 106.74 (9) | C16—C17—H17B | 111.4 |
C16—P2—C21 | 104.92 (10) | H17A—C17—H17B | 109.2 |
C26—P2—Ru1 | 116.67 (7) | C17—C18—C19 | 104.91 (18) |
C16—P2—Ru1 | 111.68 (7) | C17—C18—H18A | 110.8 |
C21—P2—Ru1 | 109.72 (7) | C19—C18—H18A | 110.8 |
C2—C1—C5 | 103.43 (16) | C17—C18—H18B | 110.8 |
C2—C1—P1 | 117.47 (15) | C19—C18—H18B | 110.8 |
C5—C1—P1 | 115.80 (14) | H18A—C18—H18B | 108.8 |
C2—C1—H1 | 106.4 | C18—C19—C20 | 106.24 (17) |
C5—C1—H1 | 106.4 | C18—C19—H19A | 110.5 |
P1—C1—H1 | 106.4 | C20—C19—H19A | 110.5 |
C3—C2—C1 | 101.31 (17) | C18—C19—H19B | 110.5 |
C3—C2—H2A | 111.5 | C20—C19—H19B | 110.5 |
C1—C2—H2A | 111.5 | H19A—C19—H19B | 108.7 |
C3—C2—H2B | 111.5 | C19—C20—C16 | 105.18 (17) |
C1—C2—H2B | 111.5 | C19—C20—H20A | 110.7 |
H2A—C2—H2B | 109.3 | C16—C20—H20A | 110.7 |
C2—C3—C4 | 104.35 (17) | C19—C20—H20B | 110.7 |
C2—C3—H3A | 110.9 | C16—C20—H20B | 110.7 |
C4—C3—H3A | 110.9 | H20A—C20—H20B | 108.8 |
C2—C3—H3B | 110.9 | C22—C21—C25 | 105.15 (16) |
C4—C3—H3B | 110.9 | C22—C21—P2 | 116.91 (14) |
H3A—C3—H3B | 108.9 | C25—C21—P2 | 115.33 (15) |
C3—C4—C5 | 105.70 (17) | C22—C21—H21 | 106.2 |
C3—C4—H4A | 110.6 | C25—C21—H21 | 106.2 |
C5—C4—H4A | 110.6 | P2—C21—H21 | 106.2 |
C3—C4—H4B | 110.6 | C23—C22—C21 | 102.86 (17) |
C5—C4—H4B | 110.6 | C23—C22—H22A | 111.2 |
H4A—C4—H4B | 108.7 | C21—C22—H22A | 111.2 |
C1—C5—C4 | 105.22 (17) | C23—C22—H22B | 111.2 |
C1—C5—H5A | 110.7 | C21—C22—H22B | 111.2 |
C4—C5—H5A | 110.7 | H22A—C22—H22B | 109.1 |
C1—C5—H5B | 110.7 | C22—C23—C24 | 103.20 (18) |
C4—C5—H5B | 110.7 | C22—C23—H23A | 111.1 |
H5A—C5—H5B | 108.8 | C24—C23—H23A | 111.1 |
C7—C6—C10 | 102.45 (17) | C22—C23—H23B | 111.1 |
C7—C6—P1 | 116.75 (15) | C24—C23—H23B | 111.1 |
C10—C6—P1 | 114.86 (14) | H23A—C23—H23B | 109.1 |
C7—C6—H6 | 107.4 | C23—C24—C25 | 105.11 (18) |
C10—C6—H6 | 107.4 | C23—C24—H24A | 110.7 |
P1—C6—H6 | 107.4 | C25—C24—H24A | 110.7 |
C8—C7—C6 | 102.11 (17) | C23—C24—H24B | 110.7 |
C8—C7—H7A | 111.3 | C25—C24—H24B | 110.7 |
C6—C7—H7A | 111.3 | H24A—C24—H24B | 108.8 |
C8—C7—H7B | 111.3 | C24—C25—C21 | 105.63 (17) |
C6—C7—H7B | 111.3 | C24—C25—H25A | 110.6 |
H7A—C7—H7B | 109.2 | C21—C25—H25A | 110.6 |
C7—C8—C9 | 105.15 (18) | C24—C25—H25B | 110.6 |
C7—C8—H8A | 110.7 | C21—C25—H25B | 110.6 |
C9—C8—H8A | 110.7 | H25A—C25—H25B | 108.7 |
C7—C8—H8B | 110.7 | C27—C26—C30 | 102.50 (17) |
C9—C8—H8B | 110.7 | C27—C26—P2 | 115.22 (14) |
H8A—C8—H8B | 108.8 | C30—C26—P2 | 116.96 (14) |
C8—C9—C10 | 106.17 (17) | C27—C26—H26 | 107.2 |
C8—C9—H9A | 110.5 | C30—C26—H26 | 107.2 |
C10—C9—H9A | 110.5 | P2—C26—H26 | 107.2 |
C8—C9—H9B | 110.5 | C26—C27—C28 | 102.55 (16) |
C10—C9—H9B | 110.5 | C26—C27—H27B | 111.3 |
H9A—C9—H9B | 108.7 | C28—C27—H27B | 111.3 |
C6—C10—C9 | 104.52 (17) | C26—C27—H27A | 111.3 |
C6—C10—H10A | 110.8 | C28—C27—H27A | 111.3 |
C9—C10—H10A | 110.8 | H27B—C27—H27A | 109.2 |
C6—C10—H10B | 110.8 | C27—C28—C29 | 105.31 (16) |
C9—C10—H10B | 110.8 | C27—C28—H28A | 110.7 |
H10A—C10—H10B | 108.9 | C29—C28—H28A | 110.7 |
C15—C11—C12 | 103.00 (16) | C27—C28—H28B | 110.7 |
C15—C11—P1 | 117.33 (15) | C29—C28—H28B | 110.7 |
C12—C11—P1 | 115.25 (14) | H28A—C28—H28B | 108.8 |
C15—C11—H11 | 106.9 | C28—C29—C30 | 106.19 (16) |
C12—C11—H11 | 106.9 | C28—C29—H29A | 110.5 |
P1—C11—H11 | 106.9 | C30—C29—H29A | 110.5 |
C11—C12—C13 | 104.58 (16) | C28—C29—H29B | 110.5 |
C11—C12—H12A | 110.8 | C30—C29—H29B | 110.5 |
C13—C12—H12A | 110.8 | H29A—C29—H29B | 108.7 |
C11—C12—H12B | 110.8 | C26—C30—C29 | 103.78 (16) |
C13—C12—H12B | 110.8 | C26—C30—H30A | 111.0 |
H12A—C12—H12B | 108.9 | C29—C30—H30A | 111.0 |
C14—C13—C12 | 106.25 (17) | C26—C30—H30B | 111.0 |
C14—C13—H13A | 110.5 | C29—C30—H30B | 111.0 |
C12—C13—H13A | 110.5 | H30A—C30—H30B | 109.0 |
C14—C13—H13B | 110.5 | F3—B1—F4 | 110.9 (2) |
C12—C13—H13B | 110.5 | F3—B1—F2 | 109.56 (19) |
H13A—C13—H13B | 108.7 | F4—B1—F2 | 109.23 (19) |
C15—C14—C13 | 104.87 (17) | F3—B1—F1 | 109.79 (18) |
C15—C14—H14A | 110.8 | F4—B1—F1 | 108.74 (19) |
C13—C14—H14A | 110.8 | F2—B1—F1 | 108.58 (19) |