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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520615018132/eb5042sup1.cif
Contains datablocks RuBrNO2PCyp32BF4_GS, RuBrNO2PCyp32BF4_PLI

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520615018132/eb5042RuBrNO2PCyp32BF4_GSsup2.hkl
Contains datablock RuBrNO2PCyp32BF4_GS

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2052520615018132/eb5042RuBrNO2PCyp32BF4_PLIsup3.hkl
Contains datablock RuBrNO2PCyp32BF4_PLI

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2052520615018132/eb5042sup4.pdf
Structure refinement and IR spectroscopy details

CCDC references: 1427938; 1427939

Computing details top

For both structures, program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014).

(RuBrNO2PCyp32BF4_GS) top
Crystal data top
C30H54BrN2O2P2Ru·BF4Z = 2
Mr = 804.48F(000) = 828
Triclinic, P1Dx = 1.613 Mg m3
a = 10.7965 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.2449 (3) ÅCell parameters from 31048 reflections
c = 13.7452 (5) Åθ = 3.1–34.3°
α = 104.778 (3)°µ = 1.83 mm1
β = 91.462 (3)°T = 10 K
γ = 108.350 (3)°Block, orange
V = 1656.57 (10) Å30.32 × 0.24 × 0.20 mm
Data collection top
SuperNova Microfocus
diffractometer
11572 reflections with I > 2σ(I)
Radiation source: D8 Venture (Mo) X-ray SourceRint = 0.046
ω scansθmax = 34.3°, θmin = 3.1°
Absorption correction: empirical (using intensity measurements)
Absorption correction were performed using empirical (using intensity measurements) methods
h = 1617
Tmin = 0.596, Tmax = 0.694k = 1917
31048 measured reflectionsl = 1921
13859 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-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 reflectionsΔρmax = 2.67 e Å3
388 parametersΔρmin = 2.37 e Å3
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
xyzUiso*/Ueq
Ru10.30045 (2)0.39556 (2)0.23791 (2)0.00487 (4)
N10.43014 (16)0.43127 (14)0.16139 (12)0.0072 (3)
O10.49804 (15)0.44867 (13)0.09919 (11)0.0102 (3)
N20.13524 (17)0.33404 (14)0.17847 (13)0.0080 (3)
O20.03961 (14)0.29535 (13)0.12290 (11)0.0104 (3)
Br10.33196 (2)0.42758 (2)0.43020 (2)0.00636 (4)
P10.29954 (5)0.60106 (4)0.29117 (4)0.00584 (9)
P20.31749 (5)0.20130 (4)0.23838 (4)0.00580 (9)
C10.17282 (18)0.61259 (16)0.37593 (15)0.0071 (3)
H10.20680.60820.44270.008*
C20.13675 (19)0.72770 (16)0.39736 (15)0.0086 (3)
H2A0.20950.79770.43880.010*
H2B0.11300.74420.33380.010*
C30.0182 (2)0.69610 (17)0.45595 (15)0.0093 (3)
H3A0.03330.75040.45700.011*
H3B0.04610.70090.52650.011*
C40.0624 (2)0.56641 (17)0.39660 (16)0.0099 (3)
H4A0.13010.56550.34610.012*
H4B0.10640.52060.44310.012*
C50.03831 (19)0.51197 (17)0.34326 (15)0.0085 (3)
H5A0.03870.44100.36510.010*
H5B0.01680.48780.26880.010*
C60.27202 (19)0.66681 (17)0.19079 (14)0.0077 (3)
H60.27770.75130.22390.009*
C70.36901 (19)0.67035 (17)0.11028 (15)0.0085 (3)
H7A0.45710.72870.13890.010*
H7B0.37690.59040.08090.010*
C80.3039 (2)0.71010 (18)0.03132 (15)0.0099 (3)
H8A0.33020.68190.03650.012*
H8B0.32920.79850.04980.012*
C90.1545 (2)0.65248 (19)0.03177 (16)0.0114 (4)
H9A0.11650.58650.03080.014*
H9B0.10990.71270.03630.014*
C100.13803 (19)0.60417 (17)0.12588 (15)0.0092 (3)
H10A0.06740.62460.16320.011*
H10B0.11670.51610.10610.011*
C110.45478 (19)0.69941 (16)0.36843 (14)0.0070 (3)
H110.44800.68780.43780.008*
C120.57949 (19)0.67373 (17)0.33275 (15)0.0088 (3)
H12A0.57810.65920.25840.011*
H12B0.58720.60280.35110.011*
C130.69455 (19)0.78789 (17)0.38862 (15)0.0098 (3)
H13A0.75550.81540.34050.012*
H13B0.74400.77190.44190.012*
C140.6312 (2)0.88352 (17)0.43608 (15)0.0102 (3)
H14A0.62980.89370.50980.012*
H14B0.68040.96170.42500.012*
C150.4912 (2)0.83496 (16)0.38156 (15)0.0090 (3)
H15A0.48930.85260.31530.011*
H15B0.43140.86860.42320.011*
C160.19458 (19)0.12569 (16)0.31071 (15)0.0074 (3)
H160.22680.16590.38400.009*
C170.16598 (19)0.00948 (16)0.29536 (15)0.0085 (3)
H17A0.14540.05420.22270.010*
H17B0.24100.02530.32490.010*
C180.04572 (19)0.04195 (17)0.35281 (15)0.0094 (3)
H18A0.07270.02150.42640.011*
H18B0.00490.12850.32810.011*
C190.03644 (19)0.03333 (16)0.33077 (15)0.0088 (3)
H19A0.07150.06710.39300.011*
H19B0.11110.01670.27820.011*
C200.05680 (19)0.13499 (17)0.29315 (15)0.0084 (3)
H20A0.03230.12350.22040.010*
H20B0.05400.21400.33220.010*
C210.47739 (18)0.22097 (16)0.30337 (14)0.0068 (3)
H210.47330.25420.37720.008*
C220.51453 (19)0.10683 (17)0.29346 (15)0.0087 (3)
H22A0.46770.06020.33860.010*
H22B0.49430.05520.22280.010*
C230.6625 (2)0.15720 (18)0.32612 (16)0.0107 (3)
H23A0.70410.09500.30320.013*
H23B0.68180.19000.40060.013*
C240.7098 (2)0.25651 (18)0.27305 (16)0.0109 (3)
H24A0.72430.22300.20240.013*
H24B0.79300.31770.30940.013*
C250.59910 (19)0.31173 (17)0.27506 (15)0.0090 (3)
H25A0.57930.32210.20790.011*
H25B0.62480.39070.32620.011*
C260.29947 (19)0.09500 (16)0.11446 (14)0.0073 (3)
H260.31280.02190.12610.009*
C270.39806 (19)0.13858 (17)0.04280 (15)0.0085 (3)
H27A0.39750.21650.03480.010*
H27B0.48820.14640.06750.010*
C280.3471 (2)0.03900 (18)0.05673 (15)0.0098 (3)
H28A0.38460.02570.05930.012*
H28B0.37070.07100.11550.012*
C290.1961 (2)0.00830 (18)0.05721 (15)0.0104 (3)
H29A0.16420.09640.06950.012*
H29B0.15220.01190.11090.012*
C300.16710 (19)0.05365 (17)0.04865 (15)0.0091 (3)
H30A0.13900.12260.04650.011*
H30B0.09800.00320.07450.011*
B10.8188 (2)0.71333 (19)0.11620 (17)0.0094 (4)
F10.72033 (13)0.76430 (11)0.14169 (10)0.0131 (2)
F20.93409 (12)0.80387 (11)0.10982 (10)0.0122 (2)
F40.77852 (13)0.62736 (11)0.02226 (10)0.0144 (3)
F30.84265 (13)0.66087 (11)0.19040 (10)0.0133 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.00427 (7)0.00350 (6)0.00537 (7)0.00083 (5)0.00125 (5)0.00131 (5)
N10.0073 (7)0.0055 (6)0.0075 (7)0.0002 (5)0.0022 (5)0.0023 (5)
O10.0108 (7)0.0091 (6)0.0110 (6)0.0020 (5)0.0063 (5)0.0045 (5)
N20.0080 (7)0.0048 (6)0.0102 (7)0.0007 (5)0.0022 (6)0.0023 (5)
O20.0076 (6)0.0087 (6)0.0120 (6)0.0008 (5)0.0018 (5)0.0024 (5)
Br10.00709 (9)0.00479 (8)0.00580 (8)0.00001 (6)0.00130 (6)0.00151 (6)
P10.0051 (2)0.00425 (18)0.0068 (2)0.00061 (15)0.00171 (15)0.00185 (15)
P20.0052 (2)0.00458 (18)0.0060 (2)0.00060 (15)0.00118 (15)0.00151 (15)
C10.0055 (8)0.0057 (7)0.0092 (8)0.0007 (6)0.0016 (6)0.0020 (6)
C20.0095 (8)0.0063 (7)0.0103 (8)0.0022 (6)0.0035 (6)0.0033 (6)
C30.0093 (8)0.0085 (8)0.0090 (8)0.0015 (6)0.0028 (6)0.0023 (6)
C40.0074 (8)0.0091 (8)0.0115 (8)0.0014 (6)0.0029 (6)0.0014 (7)
C50.0055 (8)0.0073 (7)0.0103 (8)0.0004 (6)0.0019 (6)0.0014 (6)
C60.0068 (8)0.0073 (7)0.0074 (7)0.0000 (6)0.0002 (6)0.0024 (6)
C70.0085 (8)0.0092 (7)0.0087 (8)0.0029 (6)0.0032 (6)0.0039 (6)
C80.0083 (8)0.0103 (8)0.0113 (8)0.0008 (7)0.0018 (6)0.0058 (7)
C90.0084 (8)0.0152 (9)0.0095 (8)0.0007 (7)0.0001 (6)0.0058 (7)
C100.0072 (8)0.0093 (8)0.0097 (8)0.0003 (6)0.0009 (6)0.0039 (6)
C110.0066 (8)0.0053 (7)0.0075 (7)0.0000 (6)0.0012 (6)0.0018 (6)
C120.0075 (8)0.0066 (7)0.0115 (8)0.0016 (6)0.0023 (6)0.0020 (6)
C130.0062 (8)0.0083 (8)0.0108 (8)0.0015 (6)0.0002 (6)0.0004 (6)
C140.0082 (8)0.0074 (7)0.0111 (8)0.0017 (6)0.0005 (6)0.0016 (6)
C150.0088 (8)0.0044 (7)0.0118 (8)0.0001 (6)0.0003 (6)0.0015 (6)
C160.0059 (8)0.0065 (7)0.0083 (8)0.0004 (6)0.0017 (6)0.0026 (6)
C170.0083 (8)0.0066 (7)0.0098 (8)0.0005 (6)0.0024 (6)0.0032 (6)
C180.0082 (8)0.0079 (7)0.0111 (8)0.0002 (6)0.0026 (6)0.0046 (6)
C190.0076 (8)0.0062 (7)0.0111 (8)0.0009 (6)0.0027 (6)0.0040 (6)
C200.0051 (8)0.0077 (7)0.0111 (8)0.0000 (6)0.0014 (6)0.0029 (6)
C210.0061 (8)0.0065 (7)0.0069 (7)0.0008 (6)0.0022 (6)0.0020 (6)
C220.0075 (8)0.0072 (7)0.0112 (8)0.0013 (6)0.0025 (6)0.0037 (6)
C230.0082 (8)0.0111 (8)0.0127 (9)0.0023 (7)0.0015 (7)0.0043 (7)
C240.0069 (8)0.0096 (8)0.0152 (9)0.0006 (6)0.0028 (7)0.0045 (7)
C250.0071 (8)0.0071 (7)0.0114 (8)0.0001 (6)0.0024 (6)0.0033 (6)
C260.0083 (8)0.0058 (7)0.0066 (7)0.0006 (6)0.0019 (6)0.0015 (6)
C270.0082 (8)0.0066 (7)0.0088 (8)0.0002 (6)0.0027 (6)0.0021 (6)
C280.0094 (8)0.0103 (8)0.0087 (8)0.0016 (7)0.0034 (6)0.0028 (6)
C290.0103 (8)0.0096 (8)0.0072 (8)0.0000 (7)0.0013 (6)0.0006 (6)
C300.0077 (8)0.0093 (8)0.0078 (8)0.0003 (6)0.0009 (6)0.0013 (6)
B10.0092 (9)0.0080 (8)0.0088 (9)0.0008 (7)0.0027 (7)0.0027 (7)
F10.0117 (6)0.0142 (6)0.0158 (6)0.0055 (5)0.0047 (5)0.0065 (5)
F20.0097 (6)0.0102 (5)0.0131 (6)0.0018 (4)0.0026 (4)0.0033 (4)
F40.0149 (6)0.0116 (5)0.0103 (6)0.0016 (5)0.0005 (5)0.0005 (4)
F30.0153 (6)0.0138 (6)0.0129 (6)0.0053 (5)0.0023 (5)0.0065 (5)
Geometric parameters (Å, º) top
Ru1—N21.7838 (17)C14—H14A0.9900
Ru1—N11.7839 (16)C14—H14B0.9900
Ru1—P12.4381 (5)C15—H15A0.9900
Ru1—P22.4444 (5)C15—H15B0.9900
Ru1—Br12.5684 (3)C16—C171.542 (3)
N1—O11.158 (2)C16—C201.545 (3)
N2—O21.158 (2)C16—H161.0000
P1—C61.827 (2)C17—C181.535 (3)
P1—C11.8352 (19)C17—H17A0.9900
P1—C111.8366 (19)C17—H17B0.9900
P2—C261.8238 (19)C18—C191.540 (3)
P2—C161.8357 (19)C18—H18A0.9900
P2—C211.840 (2)C18—H18B0.9900
C1—C21.538 (3)C19—C201.548 (3)
C1—C51.545 (3)C19—H19A0.9900
C1—H11.0000C19—H19B0.9900
C2—C31.528 (3)C20—H20A0.9900
C2—H2A0.9900C20—H20B0.9900
C2—H2B0.9900C21—C221.546 (3)
C3—C41.542 (3)C21—C251.562 (3)
C3—H3A0.9900C21—H211.0000
C3—H3B0.9900C22—C231.529 (3)
C4—C51.553 (3)C22—H22A0.9900
C4—H4A0.9900C22—H22B0.9900
C4—H4B0.9900C23—C241.534 (3)
C5—H5A0.9900C23—H23A0.9900
C5—H5B0.9900C23—H23B0.9900
C6—C101.537 (3)C24—C251.545 (3)
C6—C71.542 (3)C24—H24A0.9900
C6—H61.0000C24—H24B0.9900
C7—C81.535 (3)C25—H25A0.9900
C7—H7A0.9900C25—H25B0.9900
C7—H7B0.9900C26—C271.534 (3)
C8—C91.544 (3)C26—C301.537 (3)
C8—H8A0.9900C26—H261.0000
C8—H8B0.9900C27—C281.533 (3)
C9—C101.546 (3)C27—H27A0.9900
C9—H9A0.9900C27—H27B0.9900
C9—H9B0.9900C28—C291.548 (3)
C10—H10A0.9900C28—H28A0.9900
C10—H10B0.9900C28—H28B0.9900
C11—C121.541 (3)C29—C301.549 (3)
C11—C151.541 (3)C29—H29A0.9900
C11—H111.0000C29—H29B0.9900
C12—C131.548 (3)C30—H30A0.9900
C12—H12A0.9900C30—H30B0.9900
C12—H12B0.9900B1—F31.394 (3)
C13—C141.550 (3)B1—F41.398 (3)
C13—H13A0.9900B1—F11.403 (3)
C13—H13B0.9900B1—F21.404 (2)
C14—C151.533 (3)
N2—Ru1—N1118.52 (8)C15—C14—H14B110.8
N2—Ru1—P194.84 (5)C13—C14—H14B110.8
N1—Ru1—P192.96 (5)H14A—C14—H14B108.8
N2—Ru1—P294.26 (5)C14—C15—C11102.07 (16)
N1—Ru1—P295.27 (5)C14—C15—H15A111.4
P1—Ru1—P2162.995 (18)C11—C15—H15A111.4
N2—Ru1—Br1116.49 (5)C14—C15—H15B111.4
N1—Ru1—Br1124.98 (5)C11—C15—H15B111.4
P1—Ru1—Br181.971 (13)H15A—C15—H15B109.2
P2—Ru1—Br181.117 (13)C17—C16—C20103.30 (15)
O1—N1—Ru1168.92 (16)C17—C16—P2117.84 (13)
O2—N2—Ru1166.64 (16)C20—C16—P2114.72 (14)
C6—P1—C1106.57 (9)C17—C16—H16106.8
C6—P1—C11107.93 (9)C20—C16—H16106.8
C1—P1—C11104.62 (9)P2—C16—H16106.8
C6—P1—Ru1116.64 (6)C18—C17—C16101.91 (15)
C1—P1—Ru1110.37 (6)C18—C17—H17A111.4
C11—P1—Ru1109.98 (6)C16—C17—H17A111.4
C26—P2—C16106.59 (9)C18—C17—H17B111.4
C26—P2—C21106.76 (9)C16—C17—H17B111.4
C16—P2—C21105.20 (9)H17A—C17—H17B109.3
C26—P2—Ru1116.02 (7)C17—C18—C19104.79 (16)
C16—P2—Ru1111.23 (6)C17—C18—H18A110.8
C21—P2—Ru1110.38 (6)C19—C18—H18A110.8
C2—C1—C5103.37 (15)C17—C18—H18B110.8
C2—C1—P1117.24 (13)C19—C18—H18B110.8
C5—C1—P1115.79 (13)H18A—C18—H18B108.9
C2—C1—H1106.6C18—C19—C20106.58 (16)
C5—C1—H1106.6C18—C19—H19A110.4
P1—C1—H1106.6C20—C19—H19A110.4
C3—C2—C1101.49 (15)C18—C19—H19B110.4
C3—C2—H2A111.5C20—C19—H19B110.4
C1—C2—H2A111.5H19A—C19—H19B108.6
C3—C2—H2B111.5C16—C20—C19104.67 (16)
C1—C2—H2B111.5C16—C20—H20A110.8
H2A—C2—H2B109.3C19—C20—H20A110.8
C2—C3—C4103.80 (15)C16—C20—H20B110.8
C2—C3—H3A111.0C19—C20—H20B110.8
C4—C3—H3A111.0H20A—C20—H20B108.9
C2—C3—H3B111.0C22—C21—C25105.05 (15)
C4—C3—H3B111.0C22—C21—P2116.88 (13)
H3A—C3—H3B109.0C25—C21—P2115.62 (14)
C3—C4—C5105.56 (16)C22—C21—H21106.2
C3—C4—H4A110.6C25—C21—H21106.2
C5—C4—H4A110.6P2—C21—H21106.2
C3—C4—H4B110.6C23—C22—C21102.83 (15)
C5—C4—H4B110.6C23—C22—H22A111.2
H4A—C4—H4B108.8C21—C22—H22A111.2
C1—C5—C4105.30 (15)C23—C22—H22B111.2
C1—C5—H5A110.7C21—C22—H22B111.2
C4—C5—H5A110.7H22A—C22—H22B109.1
C1—C5—H5B110.7C22—C23—C24102.99 (16)
C4—C5—H5B110.7C22—C23—H23A111.2
H5A—C5—H5B108.8C24—C23—H23A111.2
C10—C6—C7102.47 (15)C22—C23—H23B111.2
C10—C6—P1115.16 (13)C24—C23—H23B111.2
C7—C6—P1116.58 (14)H23A—C23—H23B109.1
C10—C6—H6107.4C23—C24—C25105.55 (16)
C7—C6—H6107.4C23—C24—H24A110.6
P1—C6—H6107.4C25—C24—H24A110.6
C8—C7—C6102.03 (16)C23—C24—H24B110.6
C8—C7—H7A111.4C25—C24—H24B110.6
C6—C7—H7A111.4H24A—C24—H24B108.8
C8—C7—H7B111.4C24—C25—C21105.50 (15)
C6—C7—H7B111.4C24—C25—H25A110.6
H7A—C7—H7B109.2C21—C25—H25A110.6
C7—C8—C9105.53 (16)C24—C25—H25B110.6
C7—C8—H8A110.6C21—C25—H25B110.6
C9—C8—H8A110.6H25A—C25—H25B108.8
C7—C8—H8B110.6C27—C26—C30102.40 (15)
C9—C8—H8B110.6C27—C26—P2115.20 (13)
H8A—C8—H8B108.8C30—C26—P2117.04 (13)
C8—C9—C10106.02 (16)C27—C26—H26107.2
C8—C9—H9A110.5C30—C26—H26107.2
C10—C9—H9A110.5P2—C26—H26107.2
C8—C9—H9B110.5C28—C27—C26102.66 (15)
C10—C9—H9B110.5C28—C27—H27A111.2
H9A—C9—H9B108.7C26—C27—H27A111.2
C6—C10—C9104.45 (15)C28—C27—H27B111.2
C6—C10—H10A110.9C26—C27—H27B111.2
C9—C10—H10A110.9H27A—C27—H27B109.1
C6—C10—H10B110.9C27—C28—C29105.28 (15)
C9—C10—H10B110.9C27—C28—H28A110.7
H10A—C10—H10B108.9C29—C28—H28A110.7
C12—C11—C15102.77 (15)C27—C28—H28B110.7
C12—C11—P1115.83 (13)C29—C28—H28B110.7
C15—C11—P1117.38 (14)H28A—C28—H28B108.8
C12—C11—H11106.7C28—C29—C30106.24 (15)
C15—C11—H11106.7C28—C29—H29A110.5
P1—C11—H11106.7C30—C29—H29A110.5
C11—C12—C13104.88 (15)C28—C29—H29B110.5
C11—C12—H12A110.8C30—C29—H29B110.5
C13—C12—H12A110.8H29A—C29—H29B108.7
C11—C12—H12B110.8C26—C30—C29103.42 (16)
C13—C12—H12B110.8C26—C30—H30A111.1
H12A—C12—H12B108.8C29—C30—H30A111.1
C12—C13—C14106.03 (16)C26—C30—H30B111.1
C12—C13—H13A110.5C29—C30—H30B111.1
C14—C13—H13A110.5H30A—C30—H30B109.0
C12—C13—H13B110.5F3—B1—F4110.22 (17)
C14—C13—H13B110.5F3—B1—F1109.78 (17)
H13A—C13—H13B108.7F4—B1—F1109.18 (18)
C15—C14—C13104.94 (15)F3—B1—F2109.53 (18)
C15—C14—H14A110.8F4—B1—F2109.33 (17)
C13—C14—H14A110.8F1—B1—F2108.77 (17)
(RuBrNO2PCyp32BF4_PLI) top
Crystal data top
C30H54BrN2O2P2Ru·BF4Z = 2
Mr = 804.48F(000) = 828
Triclinic, P1Dx = 1.611 Mg m3
a = 10.7862 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 12.2712 (5) ÅCell parameters from 25540 reflections
c = 13.7402 (5) Åθ = 3.1–33.1°
α = 104.562 (3)°µ = 1.83 mm1
β = 91.987 (3)°T = 10 K
γ = 108.301 (3)°Block, orange
V = 1658.37 (11) Å30.28 × 0.19 × 0.14 mm
Data collection top
SuperNova Microfocus
diffractometer
10545 reflections with I > 2σ(I)
Radiation source: D8 Venture (Mo) X-ray SourceRint = 0.037
ω scansθmax = 33.1°, θmin = 3.1°
Absorption correction: empirical (using intensity measurements)
Absorption correction were performed using empirical (using intensity measurements) methods
h = 1616
Tmin = 0.666, Tmax = 0.774k = 1817
25540 measured reflectionsl = 1821
12568 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-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 reflectionsΔρmax = 2.31 e Å3
381 parametersΔρmin = 2.28 e Å3
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
xyzUiso*/UeqOcc. (<1)
N2B0.1363 (6)0.3310 (6)0.1429 (5)0.0088 (5)*0.316 (3)
O2B0.0391 (5)0.3057 (5)0.1820 (4)0.0113 (4)*0.316 (3)
O1B0.4845 (8)0.4454 (8)0.0913 (6)0.0090 (4)*0.316 (3)
N1B0.4004 (7)0.4213 (6)0.1402 (5)0.0096 (5)*0.316 (3)
N2A0.1359 (3)0.3335 (3)0.1779 (2)0.0088 (5)*0.684 (3)
O2A0.0399 (2)0.2945 (2)0.12268 (19)0.0113 (4)*0.684 (3)
Ru10.30181 (2)0.39638 (2)0.23861 (2)0.00516 (4)
N1A0.4322 (3)0.4316 (3)0.1623 (2)0.0096 (5)*0.684 (3)
O1A0.5015 (3)0.4497 (3)0.1028 (3)0.0090 (4)*0.684 (3)
Br10.32809 (3)0.42636 (2)0.42896 (2)0.01642 (6)
P10.29916 (5)0.60102 (5)0.29033 (4)0.00593 (9)
P20.31831 (5)0.20192 (5)0.23841 (4)0.00566 (9)
C10.1729 (2)0.61341 (18)0.37513 (16)0.0078 (3)
H10.20750.60880.44190.009*
C20.1377 (2)0.72845 (19)0.39669 (17)0.0095 (4)
H2A0.21100.79800.43830.011*
H2B0.11330.74520.33320.011*
C30.0194 (2)0.6968 (2)0.45531 (17)0.0109 (4)
H3A0.03270.75040.45540.013*
H3B0.04840.70290.52620.013*
C40.0613 (2)0.5673 (2)0.39782 (18)0.0117 (4)
H4A0.13160.56510.34840.014*
H4B0.10210.52210.44550.014*
C50.0378 (2)0.51340 (19)0.34262 (16)0.0098 (4)
H5A0.03870.44190.36320.012*
H5B0.01440.49050.26820.012*
C60.2715 (2)0.66719 (18)0.18975 (16)0.0078 (3)
H60.27630.75110.22290.009*
C70.3686 (2)0.6720 (2)0.11023 (16)0.0099 (4)
H7A0.45660.73060.13960.012*
H7B0.37710.59260.08090.012*
C80.3028 (2)0.7116 (2)0.03067 (17)0.0107 (4)
H8A0.33060.68530.03670.013*
H8B0.32620.79960.05000.013*
C90.1536 (2)0.6508 (2)0.02898 (18)0.0134 (4)
H9A0.11770.58420.03350.016*
H9B0.10670.70890.03150.016*
C100.1372 (2)0.6037 (2)0.12371 (16)0.0100 (4)
H10A0.06630.62390.16010.012*
H10B0.11620.51590.10470.012*
C110.4552 (2)0.69959 (18)0.36824 (16)0.0074 (3)
H110.44930.68790.43760.009*
C120.5793 (2)0.67344 (19)0.33201 (17)0.0092 (4)
H12A0.57700.65930.25770.011*
H12B0.58710.60250.35010.011*
C130.6953 (2)0.7874 (2)0.38826 (17)0.0119 (4)
H13A0.74480.77130.44190.014*
H13B0.75640.81450.34040.014*
C140.6331 (2)0.88344 (19)0.43514 (17)0.0113 (4)
H14A0.63320.89460.50910.014*
H14B0.68200.96090.42300.014*
C150.4914 (2)0.83446 (18)0.38105 (16)0.0089 (4)
H15A0.43220.86800.42300.011*
H15B0.48790.85180.31460.011*
C160.19697 (19)0.12566 (18)0.31078 (16)0.0070 (3)
H160.23030.16570.38410.008*
C170.1681 (2)0.00935 (18)0.29557 (17)0.0090 (4)
H17A0.14630.05400.22290.011*
H17B0.24370.02520.32480.011*
C180.0490 (2)0.0416 (2)0.35352 (17)0.0107 (4)
H18A0.07730.02060.42710.013*
H18B0.00150.12800.32930.013*
C190.0346 (2)0.03289 (19)0.33131 (17)0.0104 (4)
H19A0.06930.06640.39340.013*
H19B0.10960.01720.27870.013*
C200.0581 (2)0.13424 (19)0.29382 (16)0.0085 (4)
H20A0.05560.21300.33310.010*
H20B0.03240.12300.22120.010*
C210.47942 (19)0.22272 (18)0.30409 (16)0.0070 (3)
H210.47610.25650.37780.008*
C220.5173 (2)0.10939 (19)0.29523 (16)0.0088 (4)
H22A0.47250.06410.34160.011*
H22B0.49510.05660.22500.011*
C230.6662 (2)0.1602 (2)0.32603 (18)0.0127 (4)
H23A0.70740.09810.30340.015*
H23B0.68770.19430.40040.015*
C240.7112 (2)0.2576 (2)0.27121 (19)0.0144 (4)
H24A0.72260.22290.20020.017*
H24B0.79560.31870.30600.017*
C250.6000 (2)0.31307 (19)0.27500 (17)0.0099 (4)
H25A0.57820.32380.20820.012*
H25B0.62700.39170.32630.012*
C260.29980 (19)0.09514 (18)0.11458 (15)0.0068 (3)
H260.31360.02260.12680.008*
C270.3980 (2)0.13838 (19)0.04295 (16)0.0091 (4)
H27B0.48840.14610.06790.011*
H27A0.39740.21610.03470.011*
C280.3457 (2)0.03852 (19)0.05672 (16)0.0097 (4)
H28A0.38270.02620.05890.012*
H28B0.36910.07010.11570.012*
C290.1945 (2)0.0080 (2)0.05753 (16)0.0107 (4)
H29A0.16200.09590.07040.013*
H29B0.15050.01300.11100.013*
C300.1667 (2)0.05319 (19)0.04845 (16)0.0091 (4)
H30A0.13790.12170.04640.011*
H30B0.09820.00390.07420.011*
B10.8193 (2)0.7113 (2)0.11824 (19)0.0100 (4)
F10.72096 (13)0.76338 (13)0.14121 (11)0.0131 (3)
F20.93351 (13)0.79959 (13)0.10722 (11)0.0149 (3)
F40.77602 (16)0.62142 (16)0.02706 (13)0.0288 (4)
F30.84602 (15)0.66577 (14)0.19605 (12)0.0191 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ru10.00540 (7)0.00233 (7)0.00698 (8)0.00021 (5)0.00079 (5)0.00186 (5)
Br10.03744 (15)0.00718 (10)0.00909 (10)0.01085 (10)0.00854 (9)0.00491 (8)
P10.0054 (2)0.0033 (2)0.0083 (2)0.00013 (16)0.00074 (17)0.00224 (17)
P20.0056 (2)0.0030 (2)0.0076 (2)0.00001 (16)0.00046 (17)0.00209 (17)
C10.0079 (8)0.0052 (8)0.0092 (9)0.0008 (7)0.0009 (7)0.0019 (7)
C20.0090 (9)0.0081 (9)0.0123 (9)0.0027 (7)0.0026 (7)0.0042 (7)
C30.0099 (9)0.0122 (9)0.0109 (9)0.0035 (7)0.0027 (7)0.0040 (8)
C40.0073 (9)0.0122 (9)0.0141 (10)0.0012 (7)0.0022 (7)0.0039 (8)
C50.0078 (8)0.0087 (9)0.0104 (9)0.0008 (7)0.0011 (7)0.0027 (7)
C60.0068 (8)0.0056 (8)0.0101 (9)0.0000 (7)0.0016 (7)0.0032 (7)
C70.0084 (9)0.0103 (9)0.0105 (9)0.0017 (7)0.0013 (7)0.0037 (7)
C80.0097 (9)0.0115 (9)0.0117 (9)0.0017 (7)0.0019 (7)0.0068 (8)
C90.0088 (9)0.0191 (11)0.0136 (10)0.0027 (8)0.0010 (7)0.0094 (9)
C100.0071 (8)0.0106 (9)0.0112 (9)0.0005 (7)0.0010 (7)0.0046 (7)
C110.0069 (8)0.0051 (8)0.0090 (9)0.0004 (6)0.0009 (7)0.0019 (7)
C120.0065 (8)0.0077 (8)0.0130 (9)0.0018 (7)0.0007 (7)0.0034 (7)
C130.0075 (9)0.0123 (9)0.0133 (10)0.0003 (7)0.0008 (7)0.0030 (8)
C140.0098 (9)0.0079 (9)0.0130 (10)0.0014 (7)0.0006 (7)0.0030 (7)
C150.0090 (9)0.0061 (8)0.0106 (9)0.0009 (7)0.0003 (7)0.0030 (7)
C160.0056 (8)0.0050 (8)0.0092 (9)0.0004 (6)0.0012 (6)0.0026 (7)
C170.0089 (8)0.0054 (8)0.0119 (9)0.0003 (7)0.0002 (7)0.0037 (7)
C180.0092 (9)0.0094 (9)0.0146 (10)0.0014 (7)0.0021 (7)0.0074 (8)
C190.0082 (9)0.0089 (9)0.0127 (9)0.0006 (7)0.0023 (7)0.0044 (7)
C200.0064 (8)0.0076 (8)0.0103 (9)0.0003 (7)0.0004 (7)0.0032 (7)
C210.0053 (8)0.0058 (8)0.0098 (9)0.0012 (6)0.0005 (6)0.0029 (7)
C220.0089 (9)0.0079 (8)0.0116 (9)0.0029 (7)0.0014 (7)0.0061 (7)
C230.0088 (9)0.0130 (10)0.0158 (10)0.0045 (8)0.0001 (8)0.0023 (8)
C240.0093 (9)0.0108 (9)0.0212 (11)0.0017 (8)0.0025 (8)0.0032 (8)
C250.0066 (8)0.0070 (8)0.0145 (10)0.0001 (7)0.0014 (7)0.0033 (7)
C260.0070 (8)0.0038 (8)0.0086 (8)0.0005 (6)0.0004 (6)0.0019 (6)
C270.0082 (8)0.0059 (8)0.0111 (9)0.0001 (7)0.0005 (7)0.0019 (7)
C280.0115 (9)0.0079 (8)0.0091 (9)0.0029 (7)0.0017 (7)0.0019 (7)
C290.0101 (9)0.0090 (9)0.0096 (9)0.0003 (7)0.0006 (7)0.0004 (7)
C300.0066 (8)0.0084 (8)0.0100 (9)0.0003 (7)0.0011 (7)0.0019 (7)
B10.0088 (10)0.0082 (10)0.0103 (10)0.0007 (8)0.0016 (8)0.0008 (8)
F10.0119 (6)0.0129 (6)0.0174 (7)0.0053 (5)0.0037 (5)0.0074 (5)
F20.0099 (6)0.0148 (7)0.0191 (7)0.0003 (5)0.0021 (5)0.0080 (6)
F40.0184 (8)0.0244 (9)0.0266 (9)0.0010 (6)0.0027 (6)0.0140 (7)
F30.0187 (7)0.0199 (7)0.0277 (8)0.0100 (6)0.0080 (6)0.0172 (6)
Geometric parameters (Å, º) top
N2B—O2B1.184 (8)C14—C151.539 (3)
O1B—N1B1.155 (10)C14—H14A0.9900
N2A—O2A1.153 (4)C14—H14B0.9900
N2A—Ru11.789 (3)C15—H15A0.9900
Ru1—N1A1.792 (3)C15—H15B0.9900
Ru1—P12.4415 (5)C16—C171.544 (3)
Ru1—P22.4473 (6)C16—C201.548 (3)
Ru1—Br12.5408 (3)C16—H161.0000
N1A—O1A1.142 (5)C17—C181.534 (3)
P1—C61.829 (2)C17—H17A0.9900
P1—C11.840 (2)C17—H17B0.9900
P1—C111.841 (2)C18—C191.542 (3)
P2—C261.828 (2)C18—H18A0.9900
P2—C161.835 (2)C18—H18B0.9900
P2—C211.843 (2)C19—C201.545 (3)
C1—C21.536 (3)C19—H19A0.9900
C1—C51.545 (3)C19—H19B0.9900
C1—H11.0000C20—H20A0.9900
C2—C31.531 (3)C20—H20B0.9900
C2—H2A0.9900C21—C221.547 (3)
C2—H2B0.9900C21—C251.560 (3)
C3—C41.536 (3)C21—H211.0000
C3—H3A0.9900C22—C231.528 (3)
C3—H3B0.9900C22—H22A0.9900
C4—C51.550 (3)C22—H22B0.9900
C4—H4A0.9900C23—C241.531 (4)
C4—H4B0.9900C23—H23A0.9900
C5—H5A0.9900C23—H23B0.9900
C5—H5B0.9900C24—C251.550 (3)
C6—C71.538 (3)C24—H24A0.9900
C6—C101.541 (3)C24—H24B0.9900
C6—H61.0000C25—H25A0.9900
C7—C81.538 (3)C25—H25B0.9900
C7—H7A0.9900C26—C271.534 (3)
C7—H7B0.9900C26—C301.536 (3)
C8—C91.544 (3)C26—H261.0000
C8—H8A0.9900C27—C281.537 (3)
C8—H8B0.9900C27—H27B0.9900
C9—C101.546 (3)C27—H27A0.9900
C9—H9A0.9900C28—C291.548 (3)
C9—H9B0.9900C28—H28A0.9900
C10—H10A0.9900C28—H28B0.9900
C10—H10B0.9900C29—C301.548 (3)
C11—C151.538 (3)C29—H29A0.9900
C11—C121.542 (3)C29—H29B0.9900
C11—H111.0000C30—H30A0.9900
C12—C131.552 (3)C30—H30B0.9900
C12—H12A0.9900B1—F31.385 (3)
C12—H12B0.9900B1—F41.395 (3)
C13—C141.549 (3)B1—F21.404 (3)
C13—H13A0.9900B1—F11.407 (3)
C13—H13B0.9900
O2A—N2A—Ru1167.3 (3)C15—C14—H14B110.8
N2A—Ru1—N1A118.46 (15)C13—C14—H14B110.8
N2A—Ru1—P194.83 (9)H14A—C14—H14B108.8
N1A—Ru1—P193.34 (10)C11—C15—C14102.15 (17)
N2A—Ru1—P293.52 (10)C11—C15—H15A111.3
N1A—Ru1—P294.87 (10)C14—C15—H15A111.3
P1—Ru1—P2163.78 (2)C11—C15—H15B111.3
N2A—Ru1—Br1115.32 (10)C14—C15—H15B111.3
N1A—Ru1—Br1126.22 (10)H15A—C15—H15B109.2
P1—Ru1—Br182.287 (15)C17—C16—C20102.91 (16)
P2—Ru1—Br181.579 (15)C17—C16—P2118.32 (14)
O1A—N1A—Ru1170.4 (3)C20—C16—P2114.84 (15)
C6—P1—C1106.54 (10)C17—C16—H16106.7
C6—P1—C11107.66 (10)C20—C16—H16106.7
C1—P1—C11104.30 (9)P2—C16—H16106.7
C6—P1—Ru1117.20 (7)C18—C17—C16101.98 (16)
C1—P1—Ru1110.80 (7)C18—C17—H17A111.4
C11—P1—Ru1109.51 (7)C16—C17—H17A111.4
C26—P2—C16106.35 (9)C18—C17—H17B111.4
C26—P2—C21106.74 (9)C16—C17—H17B111.4
C16—P2—C21104.92 (10)H17A—C17—H17B109.2
C26—P2—Ru1116.67 (7)C17—C18—C19104.91 (18)
C16—P2—Ru1111.68 (7)C17—C18—H18A110.8
C21—P2—Ru1109.72 (7)C19—C18—H18A110.8
C2—C1—C5103.43 (16)C17—C18—H18B110.8
C2—C1—P1117.47 (15)C19—C18—H18B110.8
C5—C1—P1115.80 (14)H18A—C18—H18B108.8
C2—C1—H1106.4C18—C19—C20106.24 (17)
C5—C1—H1106.4C18—C19—H19A110.5
P1—C1—H1106.4C20—C19—H19A110.5
C3—C2—C1101.31 (17)C18—C19—H19B110.5
C3—C2—H2A111.5C20—C19—H19B110.5
C1—C2—H2A111.5H19A—C19—H19B108.7
C3—C2—H2B111.5C19—C20—C16105.18 (17)
C1—C2—H2B111.5C19—C20—H20A110.7
H2A—C2—H2B109.3C16—C20—H20A110.7
C2—C3—C4104.35 (17)C19—C20—H20B110.7
C2—C3—H3A110.9C16—C20—H20B110.7
C4—C3—H3A110.9H20A—C20—H20B108.8
C2—C3—H3B110.9C22—C21—C25105.15 (16)
C4—C3—H3B110.9C22—C21—P2116.91 (14)
H3A—C3—H3B108.9C25—C21—P2115.33 (15)
C3—C4—C5105.70 (17)C22—C21—H21106.2
C3—C4—H4A110.6C25—C21—H21106.2
C5—C4—H4A110.6P2—C21—H21106.2
C3—C4—H4B110.6C23—C22—C21102.86 (17)
C5—C4—H4B110.6C23—C22—H22A111.2
H4A—C4—H4B108.7C21—C22—H22A111.2
C1—C5—C4105.22 (17)C23—C22—H22B111.2
C1—C5—H5A110.7C21—C22—H22B111.2
C4—C5—H5A110.7H22A—C22—H22B109.1
C1—C5—H5B110.7C22—C23—C24103.20 (18)
C4—C5—H5B110.7C22—C23—H23A111.1
H5A—C5—H5B108.8C24—C23—H23A111.1
C7—C6—C10102.45 (17)C22—C23—H23B111.1
C7—C6—P1116.75 (15)C24—C23—H23B111.1
C10—C6—P1114.86 (14)H23A—C23—H23B109.1
C7—C6—H6107.4C23—C24—C25105.11 (18)
C10—C6—H6107.4C23—C24—H24A110.7
P1—C6—H6107.4C25—C24—H24A110.7
C8—C7—C6102.11 (17)C23—C24—H24B110.7
C8—C7—H7A111.3C25—C24—H24B110.7
C6—C7—H7A111.3H24A—C24—H24B108.8
C8—C7—H7B111.3C24—C25—C21105.63 (17)
C6—C7—H7B111.3C24—C25—H25A110.6
H7A—C7—H7B109.2C21—C25—H25A110.6
C7—C8—C9105.15 (18)C24—C25—H25B110.6
C7—C8—H8A110.7C21—C25—H25B110.6
C9—C8—H8A110.7H25A—C25—H25B108.7
C7—C8—H8B110.7C27—C26—C30102.50 (17)
C9—C8—H8B110.7C27—C26—P2115.22 (14)
H8A—C8—H8B108.8C30—C26—P2116.96 (14)
C8—C9—C10106.17 (17)C27—C26—H26107.2
C8—C9—H9A110.5C30—C26—H26107.2
C10—C9—H9A110.5P2—C26—H26107.2
C8—C9—H9B110.5C26—C27—C28102.55 (16)
C10—C9—H9B110.5C26—C27—H27B111.3
H9A—C9—H9B108.7C28—C27—H27B111.3
C6—C10—C9104.52 (17)C26—C27—H27A111.3
C6—C10—H10A110.8C28—C27—H27A111.3
C9—C10—H10A110.8H27B—C27—H27A109.2
C6—C10—H10B110.8C27—C28—C29105.31 (16)
C9—C10—H10B110.8C27—C28—H28A110.7
H10A—C10—H10B108.9C29—C28—H28A110.7
C15—C11—C12103.00 (16)C27—C28—H28B110.7
C15—C11—P1117.33 (15)C29—C28—H28B110.7
C12—C11—P1115.25 (14)H28A—C28—H28B108.8
C15—C11—H11106.9C28—C29—C30106.19 (16)
C12—C11—H11106.9C28—C29—H29A110.5
P1—C11—H11106.9C30—C29—H29A110.5
C11—C12—C13104.58 (16)C28—C29—H29B110.5
C11—C12—H12A110.8C30—C29—H29B110.5
C13—C12—H12A110.8H29A—C29—H29B108.7
C11—C12—H12B110.8C26—C30—C29103.78 (16)
C13—C12—H12B110.8C26—C30—H30A111.0
H12A—C12—H12B108.9C29—C30—H30A111.0
C14—C13—C12106.25 (17)C26—C30—H30B111.0
C14—C13—H13A110.5C29—C30—H30B111.0
C12—C13—H13A110.5H30A—C30—H30B109.0
C14—C13—H13B110.5F3—B1—F4110.9 (2)
C12—C13—H13B110.5F3—B1—F2109.56 (19)
H13A—C13—H13B108.7F4—B1—F2109.23 (19)
C15—C14—C13104.87 (17)F3—B1—F1109.79 (18)
C15—C14—H14A110.8F4—B1—F1108.74 (19)
C13—C14—H14A110.8F2—B1—F1108.58 (19)
 

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