Photocrystallography and IR spectroscopy of light-induced linkage NO isomers in [RuBr(NO)₂(PCyp₃)₂]BF₄

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 ν_s(NO) and asymmetric ν_as(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.

Computing details

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

(RuBrNO2PCyp32BF4_GS)

Crystal data

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) Å^3	0.32 × 0.24 × 0.20 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.108	w = 1/[σ^2(Fo^2) + (0.0524P)^2 + 0.1851P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

Crystal data

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) Å^3	0.28 × 0.19 × 0.14 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.111	w = 1/[σ^2(Fo^2) + (0.0575P)^2 + 0.3679P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)