Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111043447/ov3008sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111043447/ov3008XVsup2.hkl |
CCDC reference: 855953
For related literature, see: Alcaraz & Sabo-Etienne (2010); Alcaraz, Chaplin, Stevens, Clot, Vendier, Weller & Sabo-Etienne (2010); Alcaraz, Vendier, Clot & Sabo-Etienne (2010); Chaplin & Weller (2010); Douglas et al. (2008, 2009); Friedrich et al. (2009); Jaska et al. (2003); Johnson et al. (2011); Nöth & Thomas (1999); Sheldrick (2008); Shimoi et al. (1999); Staubitz et al. (2010); Stevens et al. (2011); Tang et al. (2010a, 2010b).
All manipulations, unless otherwise stated, were performed under an atmosphere of argon, using standard Schlenk and glove-box techniques. Reagents and solvents were prepared and purified as previously described (Chaplin & Weller, 2010). NMR spectra were recorded on a Varian Unity or a Bruker AVC 500 MHz spectrometer.
For the reaction of [Rh(PiPr3)2(C6H5F)][BArF4] with H3B.NMe2H, 1,2-C6H4F2 (0.4 ml) was added to a J. Young NMR tube charged with [Rh(PiPr3)2(C6H5F)][BArF4] (0.010 g, 0.0072 mmol) and H3B.NMe2H (0.0009 g, 0.015 mmol, 2 equivalents). The reaction was then monitored by NMR spectroscopy, indicating the quantitative formation of the organometallic species [Rh(H)2(η2-H3B.NMe2H)(PiPr3)2][BArF4]. Layering the solution with pentane and holding at 278 K resulted in the crystallization of a mixture of colourless crystals of [Rh(H)2(η2-H3B.NMe2H)(PiPr3)2][BArF4] and [Rh(H)2(η2-H3B.NMe2BH2.NMe2H)(PiPr3)2][BArF4] [(XV), ratio 2:1, yield 0.005 g]. Single crystals of the latter were serendipitously picked from solution and placed into the cooling stream on the diffractometer. Spectroscopic data for (XV): 1H NMR (CD2Cl2, 500 MHz, 298 K, δ, p.p.m.): 7.70–7.73 (m, 8H, BArF4), 7.56 (br, 4H, BArF4), 4.03 (br, 1H, NH), 2.68 (d, 3JHH = 5.8 Hz, 3H, NHMe2), 2.46 (s, 3H, NMe2), 2.15–2.24 (m, 6H, PCH), 1.20–1.25 (obscured, 36H, PCMe), -0.70 (vbr obscured, 3H, RhH3B), -19.6 (approximately q, J = 17 Hz, 2H, RhH); 31P{1H} NMR (CD2Cl2, 202 MHz, δ, p.p.m.): 64.7 (d, 1JRhP = 111 Hz).
The hydride (H0A and H0B) and BH3 (H1A, H1B and H1C) H atoms were located in a Fourier difference map and refined as riding, with Uiso(H) = 1.2Ueq(Rh,B).
The BH2 H atoms were placed geometrically, with the B—H distance free to refine, using the AFIX 24 command (SHELXL97; Sheldrick, 2008), and refined as riding, with Uiso(H) = 1.2Ueq(B). The B—H distance was refined to equal length across the disordered components (s.u. 0.001 Å).
The methyl [C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C)], methenyl [C—H = 1.00 Å and Uiso(H) = 1.2Ueq(C)], aromatic [C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C)] and NH [N—H = 0.93 Å and Uiso(H) = 1.2Ueq(N)] H atoms were placed in calculated positions.
Disorder in the structure was treated by modelling the appropriate atom groups independently over two sites, such that the occupancies of the major and minor components were summed to unity. Disordered groups included part of the diborazine ligand (B2/N2 and B12/N12), one of the phosphane ligands (P1 and P11) and a number of CF3 groups of the anion; the F atoms or the entire CF3 group were modelled over two sites. In each case, the geometries of the components were restrained by allowing bond distances to be the same with a small chemically sensible variation (0.01 Å).
Restraints on displacement parameters for atoms within the disordered groups were applied, in order to maintain sensible values for isotropic behaviour (s.u. 0.007 Å2) and Uij similarity (s.u. 0.0 Å21). The displacement parameters of atoms B2/B12, N2/N12, P1/P11 and C232/C332 were constrained to be identical.
Full details of the restraints are given in the supporting information under the headings _refine_special_details and _iucr_refine_instructions_details in the archived CIF.
Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).
[RhH2(C9H21P)2(C4H18B2N2)](C32H12BF24) | Z = 2 |
Mr = 1404.43 | F(000) = 1436 |
Triclinic, P1 | Dx = 1.449 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.8309 (2) Å | Cell parameters from 12596 reflections |
b = 14.0813 (2) Å | θ = 2.9–27.5° |
c = 19.1638 (3) Å | µ = 0.42 mm−1 |
α = 73.0175 (6)° | T = 150 K |
β = 76.4127 (5)° | Block, colourless |
γ = 86.6877 (6)° | 0.22 × 0.10 × 0.10 mm |
V = 3218.56 (8) Å3 |
Nonius KappaCCD area-detector diffractometer | 14566 independent reflections |
Radiation source: fine-focus sealed tube | 11987 reflections with I > 2σ(I) |
Horizonally mounted graphite crystal monochromator | Rint = 0.018 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
CCD scans | h = −16→15 |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | k = −17→18 |
Tmin = 0.92, Tmax = 1.0 | l = −24→24 |
24556 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0589P)2 + 3.3702P] where P = (Fo2 + 2Fc2)/3 |
14566 reflections | (Δ/σ)max < 0.001 |
1069 parameters | Δρmax = 0.80 e Å−3 |
1142 restraints | Δρmin = −0.69 e Å−3 |
[RhH2(C9H21P)2(C4H18B2N2)](C32H12BF24) | γ = 86.6877 (6)° |
Mr = 1404.43 | V = 3218.56 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.8309 (2) Å | Mo Kα radiation |
b = 14.0813 (2) Å | µ = 0.42 mm−1 |
c = 19.1638 (3) Å | T = 150 K |
α = 73.0175 (6)° | 0.22 × 0.10 × 0.10 mm |
β = 76.4127 (5)° |
Nonius KappaCCD area-detector diffractometer | 14566 independent reflections |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | 11987 reflections with I > 2σ(I) |
Tmin = 0.92, Tmax = 1.0 | Rint = 0.018 |
24556 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 1142 restraints |
wR(F2) = 0.129 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.80 e Å−3 |
14566 reflections | Δρmin = −0.69 e Å−3 |
1069 parameters |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Restraints and constraints used during refinement: SIMU 0.01 P1 P11 C5 > C113 N1 > C104 C232 C332 = F1 > F103 F10 > F112 F13 > F115 F16 > F118 F22 > F124 ISOR 0.007 P1 P11 C5 > C113 N1 > C104 C232 C332 = F1 > F103 F10 > F112 F13 > F115 F16 > F118 F22 > F124 SADI 0.01 Rh1 P1 Rh1 P11 SADI 0.01 P1 C5 P11 C105 P1 C8 P11 C108 P1 C11 P11 C111 SADI 0.01 C5 C8 C8 C11 C11 C5 C105 C108 C108 C111 C111 C105 SADI 0.01 N2 C3 N2 C4 N12 C103 N12 C104 SADI 0.01 C3 C4 C103 C104 SADI 0.01 B2 C3 B2 C4 B12 C103 B12 C104 SADI 0.005 N1 B2 N1 B12 SADI 0.005 B2 N2 B12 N12 SADI 0.001 B2 H2D B2 H2E B12 H12A B12 H12B EADP B2 B12 EADP N2 N12 EADP P1 P11 EADP C232 C332 SADI 0.005 C207 F1 C207 F2 C207 F3 C207 F101 C207 F102 C207 F103 SADI 0.01 F1 F2 F2 F3 F3 F1 F101 F102 F102 F103 F103 F101 SADI 0.01 C203 F1 C203 F2 C203 F3 C203 F101 C203 F102 C203 F103 SADI 0.005 C216 F10 C216 F11 C216 F12 C216 F110 C216 F111 C216 F112 SADI 0.01 F10 F11 F11 F12 F12 F10 F110 F111 F111 F112 F112 F110 SADI 0.01 C213 F10 C213 F11 C213 F12 C213 F110 C213 F111 C213 F112 SADI 0.005 C223 F13 C223 F14 C223 F15 C223 F113 C223 F114 C223 F115 SADI 0.01 F13 F14 F14 F15 F15 F13 F113 F114 F114 F115 F115 F113 SADI 0.01 C219 F13 C219 F14 C219 F15 C219 F113 C219 F114 C219 F115 SADI 0.005 C224 F16 C224 F17 C224 F18 C224 F116 C224 F117 C224 F118 SADI 0.01 F16 F17 F17 F18 F18 F16 F116 F117 F117 F118 F118 F116 SADI 0.01 C221 F16 C221 F17 C221 F18 C221 F116 C221 F117 C221 F118 SADI 0.01 C229 C232 C229 C332 SADI 0.005 C232 F22 C232 F23 C232 F24 C332 F122 C332 F123 C332 F124 SADI 0.01 F22 F23 F23 F24 F24 F22 F122 F123 F123 F124 F124 F122 SADI 0.01 C229 F22 C229 F23 C229 F24 C229 F122 C229 F123 C229 F124 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Rh1 | 0.618741 (18) | 0.159111 (17) | 0.275124 (14) | 0.03371 (8) | |
H0A | 0.533 (3) | 0.177 (3) | 0.2364 (19) | 0.040* | |
H0B | 0.537 (3) | 0.085 (3) | 0.3167 (19) | 0.040* | |
P2 | 0.67735 (6) | 0.04327 (6) | 0.20967 (5) | 0.03365 (17) | |
B1 | 0.7940 (3) | 0.2021 (3) | 0.2659 (2) | 0.0422 (8) | |
H1A | 0.739 (3) | 0.141 (3) | 0.318 (2) | 0.051* | |
H1B | 0.736 (3) | 0.251 (3) | 0.231 (2) | 0.051* | |
H1C | 0.858 (3) | 0.171 (3) | 0.228 (2) | 0.051* | |
N1 | 0.8572 (3) | 0.2666 (2) | 0.2986 (2) | 0.0548 (8) | |
C1 | 0.7951 (4) | 0.2921 (4) | 0.3637 (3) | 0.0678 (12) | |
H1D | 0.7695 | 0.2312 | 0.4037 | 0.102* | |
H1E | 0.7336 | 0.3321 | 0.3507 | 0.102* | |
H1F | 0.8400 | 0.3303 | 0.3810 | 0.102* | |
C2 | 0.9463 (5) | 0.2042 (5) | 0.3247 (4) | 0.1007 (18) | |
H2A | 0.9916 | 0.2438 | 0.3405 | 0.151* | |
H2B | 0.9894 | 0.1808 | 0.2836 | 0.151* | |
H2C | 0.9164 | 0.1471 | 0.3670 | 0.151* | |
B2 | 0.8991 (11) | 0.3719 (5) | 0.2448 (6) | 0.0646 (17) | 0.511 (14) |
H2D | 0.9560 (16) | 0.4049 (9) | 0.2687 (8) | 0.077* | 0.511 (14) |
H2E | 0.8298 (18) | 0.4243 (12) | 0.2369 (6) | 0.077* | 0.511 (14) |
N2 | 0.9603 (8) | 0.3539 (8) | 0.1661 (6) | 0.0707 (17) | 0.511 (14) |
H2 | 0.9304 | 0.2985 | 0.1608 | 0.085* | 0.511 (14) |
C3 | 0.9464 (14) | 0.4443 (10) | 0.1018 (6) | 0.113 (4) | 0.511 (14) |
H3A | 0.9958 | 0.4974 | 0.0975 | 0.170* | 0.511 (14) |
H3B | 0.8725 | 0.4676 | 0.1117 | 0.170* | 0.511 (14) |
H3C | 0.9622 | 0.4260 | 0.0548 | 0.170* | 0.511 (14) |
C4 | 1.0795 (8) | 0.3391 (11) | 0.1582 (9) | 0.099 (4) | 0.511 (14) |
H4A | 1.1130 | 0.3388 | 0.1067 | 0.148* | 0.511 (14) |
H4B | 1.0925 | 0.2756 | 0.1931 | 0.148* | 0.511 (14) |
H4C | 1.1103 | 0.3933 | 0.1696 | 0.148* | 0.511 (14) |
B12 | 0.8890 (12) | 0.3688 (6) | 0.2356 (6) | 0.0646 (17) | 0.489 (14) |
H12A | 0.9497 (17) | 0.4082 (10) | 0.2520 (7) | 0.077* | 0.489 (14) |
H12B | 0.815 (2) | 0.4166 (12) | 0.2348 (6) | 0.077* | 0.489 (14) |
N12 | 0.9380 (8) | 0.3619 (9) | 0.1520 (6) | 0.0707 (17) | 0.489 (14) |
H12 | 0.9292 | 0.2965 | 0.1527 | 0.085* | 0.489 (14) |
C103 | 0.8781 (14) | 0.4264 (12) | 0.0964 (7) | 0.120 (5) | 0.489 (14) |
H10A | 0.8762 | 0.4947 | 0.0997 | 0.180* | 0.489 (14) |
H10B | 0.8047 | 0.4009 | 0.1079 | 0.180* | 0.489 (14) |
H10C | 0.9147 | 0.4255 | 0.0456 | 0.180* | 0.489 (14) |
C104 | 1.0555 (9) | 0.3869 (12) | 0.1226 (8) | 0.092 (4) | 0.489 (14) |
H10D | 1.0974 | 0.3263 | 0.1344 | 0.139* | 0.489 (14) |
H10E | 1.0754 | 0.4342 | 0.1461 | 0.139* | 0.489 (14) |
H10F | 1.0704 | 0.4165 | 0.0682 | 0.139* | 0.489 (14) |
P1 | 0.50761 (12) | 0.26357 (13) | 0.33150 (10) | 0.0334 (3) | 0.775 (4) |
C5 | 0.5124 (6) | 0.2502 (5) | 0.4310 (3) | 0.0416 (13) | 0.775 (4) |
H5 | 0.5715 | 0.2954 | 0.4282 | 0.050* | 0.775 (4) |
C6 | 0.4113 (8) | 0.2820 (7) | 0.4805 (4) | 0.051 (2) | 0.775 (4) |
H6A | 0.3516 | 0.2369 | 0.4881 | 0.076* | 0.775 (4) |
H6B | 0.3927 | 0.3499 | 0.4556 | 0.076* | 0.775 (4) |
H6C | 0.4255 | 0.2793 | 0.5291 | 0.076* | 0.775 (4) |
C7 | 0.5455 (10) | 0.1448 (10) | 0.4702 (5) | 0.056 (2) | 0.775 (4) |
H7A | 0.5559 | 0.1426 | 0.5197 | 0.084* | 0.775 (4) |
H7B | 0.6125 | 0.1275 | 0.4399 | 0.084* | 0.775 (4) |
H7C | 0.4890 | 0.0973 | 0.4760 | 0.084* | 0.775 (4) |
C8 | 0.5381 (4) | 0.3972 (3) | 0.2834 (2) | 0.0426 (10) | 0.775 (4) |
H8 | 0.6057 | 0.4103 | 0.2966 | 0.051* | 0.775 (4) |
C9 | 0.4576 (5) | 0.4715 (4) | 0.3094 (3) | 0.0651 (15) | 0.775 (4) |
H9A | 0.4828 | 0.5393 | 0.2811 | 0.098* | 0.775 (4) |
H9B | 0.4510 | 0.4622 | 0.3630 | 0.098* | 0.775 (4) |
H9C | 0.3876 | 0.4606 | 0.3007 | 0.098* | 0.775 (4) |
C10 | 0.5659 (5) | 0.4225 (4) | 0.1987 (3) | 0.0607 (14) | 0.775 (4) |
H10G | 0.5000 | 0.4262 | 0.1806 | 0.091* | 0.775 (4) |
H10H | 0.6121 | 0.3709 | 0.1832 | 0.091* | 0.775 (4) |
H10I | 0.6037 | 0.4867 | 0.1774 | 0.091* | 0.775 (4) |
C11 | 0.3632 (3) | 0.2470 (4) | 0.3371 (3) | 0.0473 (11) | 0.775 (4) |
H11 | 0.3231 | 0.2909 | 0.3667 | 0.057* | 0.775 (4) |
C12 | 0.3242 (5) | 0.1400 (5) | 0.3806 (4) | 0.0669 (16) | 0.775 (4) |
H12C | 0.2457 | 0.1382 | 0.3950 | 0.100* | 0.775 (4) |
H12D | 0.3530 | 0.1174 | 0.4257 | 0.100* | 0.775 (4) |
H12E | 0.3491 | 0.0962 | 0.3487 | 0.100* | 0.775 (4) |
C13 | 0.3328 (5) | 0.2789 (5) | 0.2612 (4) | 0.0701 (16) | 0.775 (4) |
H13A | 0.3792 | 0.2456 | 0.2273 | 0.105* | 0.775 (4) |
H13B | 0.3419 | 0.3510 | 0.2398 | 0.105* | 0.775 (4) |
H13C | 0.2579 | 0.2605 | 0.2678 | 0.105* | 0.775 (4) |
P11 | 0.4855 (4) | 0.2354 (4) | 0.3514 (3) | 0.0334 (3) | 0.225 (4) |
C105 | 0.5122 (19) | 0.2333 (16) | 0.4434 (8) | 0.035 (4) | 0.225 (4) |
H105 | 0.5699 | 0.2841 | 0.4316 | 0.042* | 0.225 (4) |
C106 | 0.418 (3) | 0.264 (2) | 0.4989 (16) | 0.039 (5) | 0.225 (4) |
H10J | 0.3572 | 0.2179 | 0.5114 | 0.058* | 0.225 (4) |
H10K | 0.3954 | 0.3315 | 0.4757 | 0.058* | 0.225 (4) |
H10L | 0.4402 | 0.2626 | 0.5446 | 0.058* | 0.225 (4) |
C107 | 0.554 (3) | 0.138 (3) | 0.4864 (17) | 0.039 (5) | 0.225 (4) |
H10M | 0.5898 | 0.1517 | 0.5226 | 0.058* | 0.225 (4) |
H10N | 0.6057 | 0.1098 | 0.4517 | 0.058* | 0.225 (4) |
H10O | 0.4946 | 0.0915 | 0.5131 | 0.058* | 0.225 (4) |
C108 | 0.4693 (13) | 0.3703 (7) | 0.3047 (8) | 0.046 (3) | 0.225 (4) |
H108 | 0.3932 | 0.3862 | 0.3247 | 0.055* | 0.225 (4) |
C109 | 0.5360 (16) | 0.4408 (14) | 0.3198 (11) | 0.059 (4) | 0.225 (4) |
H10P | 0.6115 | 0.4331 | 0.2967 | 0.088* | 0.225 (4) |
H10Q | 0.5272 | 0.4270 | 0.3741 | 0.088* | 0.225 (4) |
H10R | 0.5137 | 0.5088 | 0.2988 | 0.088* | 0.225 (4) |
C110 | 0.4816 (17) | 0.3884 (14) | 0.2199 (11) | 0.062 (4) | 0.225 (4) |
H11A | 0.4552 | 0.4546 | 0.1982 | 0.092* | 0.225 (4) |
H11B | 0.4401 | 0.3381 | 0.2115 | 0.092* | 0.225 (4) |
H11C | 0.5575 | 0.3840 | 0.1960 | 0.092* | 0.225 (4) |
C111 | 0.3451 (8) | 0.1858 (11) | 0.3768 (9) | 0.041 (3) | 0.225 (4) |
H111 | 0.3016 | 0.2267 | 0.4076 | 0.049* | 0.225 (4) |
C112 | 0.3332 (14) | 0.0816 (15) | 0.4261 (11) | 0.055 (4) | 0.225 (4) |
H11D | 0.2595 | 0.0701 | 0.4562 | 0.083* | 0.225 (4) |
H11E | 0.3830 | 0.0704 | 0.4594 | 0.083* | 0.225 (4) |
H11F | 0.3493 | 0.0358 | 0.3952 | 0.083* | 0.225 (4) |
C113 | 0.2956 (16) | 0.2010 (16) | 0.3102 (12) | 0.063 (4) | 0.225 (4) |
H11G | 0.3291 | 0.1562 | 0.2809 | 0.094* | 0.225 (4) |
H11H | 0.3072 | 0.2699 | 0.2788 | 0.094* | 0.225 (4) |
H11I | 0.2185 | 0.1866 | 0.3278 | 0.094* | 0.225 (4) |
C14 | 0.7635 (3) | −0.0602 (2) | 0.2504 (2) | 0.0478 (8) | |
H14 | 0.7423 | −0.1208 | 0.2398 | 0.057* | |
C15 | 0.8840 (3) | −0.0460 (3) | 0.2182 (3) | 0.0646 (11) | |
H15A | 0.9083 | 0.0133 | 0.2271 | 0.097* | |
H15B | 0.8996 | −0.0377 | 0.1642 | 0.097* | |
H15C | 0.9215 | −0.1043 | 0.2426 | 0.097* | |
C16 | 0.7409 (5) | −0.0831 (3) | 0.3358 (3) | 0.0722 (13) | |
H16A | 0.7722 | −0.1472 | 0.3569 | 0.108* | |
H16B | 0.6633 | −0.0858 | 0.3563 | 0.108* | |
H16C | 0.7729 | −0.0309 | 0.3488 | 0.108* | |
C17 | 0.7548 (3) | 0.0979 (3) | 0.11206 (19) | 0.0464 (8) | |
H17 | 0.8290 | 0.1101 | 0.1159 | 0.056* | |
C18 | 0.7666 (4) | 0.0274 (4) | 0.0624 (2) | 0.0687 (12) | |
H18A | 0.6974 | 0.0202 | 0.0511 | 0.103* | |
H18B | 0.7903 | −0.0377 | 0.0889 | 0.103* | |
H18C | 0.8197 | 0.0550 | 0.0155 | 0.103* | |
C19 | 0.7134 (4) | 0.1989 (3) | 0.0738 (2) | 0.0658 (11) | |
H19A | 0.7626 | 0.2277 | 0.0253 | 0.099* | |
H19B | 0.7090 | 0.2431 | 0.1055 | 0.099* | |
H19C | 0.6421 | 0.1907 | 0.0660 | 0.099* | |
C20 | 0.5673 (3) | −0.0294 (3) | 0.2012 (2) | 0.0528 (9) | |
H20 | 0.6016 | −0.0737 | 0.1701 | 0.063* | |
C21 | 0.5080 (4) | −0.0974 (4) | 0.2765 (3) | 0.0774 (15) | |
H21A | 0.4766 | −0.0573 | 0.3101 | 0.116* | |
H21B | 0.5584 | −0.1447 | 0.2989 | 0.116* | |
H21C | 0.4509 | −0.1337 | 0.2687 | 0.116* | |
C22 | 0.4871 (3) | 0.0337 (4) | 0.1607 (3) | 0.0758 (14) | |
H22A | 0.4345 | −0.0096 | 0.1550 | 0.114* | |
H22B | 0.5251 | 0.0739 | 0.1111 | 0.114* | |
H22C | 0.4502 | 0.0775 | 0.1898 | 0.114* | |
B200 | 0.1581 (2) | 0.7010 (2) | 0.24233 (17) | 0.0290 (6) | |
C201 | 0.2582 (2) | 0.6848 (2) | 0.17602 (15) | 0.0283 (5) | |
C202 | 0.2516 (2) | 0.6121 (2) | 0.14003 (17) | 0.0344 (6) | |
H202 | 0.1876 | 0.5738 | 0.1542 | 0.041* | |
C203 | 0.3353 (2) | 0.5943 (2) | 0.08461 (18) | 0.0380 (7) | |
C204 | 0.4318 (2) | 0.6450 (2) | 0.06453 (18) | 0.0388 (7) | |
H204 | 0.4893 | 0.6322 | 0.0271 | 0.047* | |
C205 | 0.4421 (2) | 0.7147 (2) | 0.10034 (17) | 0.0350 (6) | |
C206 | 0.3567 (2) | 0.7347 (2) | 0.15439 (16) | 0.0315 (6) | |
H206 | 0.3660 | 0.7841 | 0.1772 | 0.038* | |
C207 | 0.3204 (2) | 0.5203 (2) | 0.04475 (18) | 0.0540 (9) | |
F1 | 0.3969 (5) | 0.5288 (5) | −0.0180 (3) | 0.0629 (15) | 0.662 (16) |
F2 | 0.3181 (7) | 0.4273 (3) | 0.0869 (3) | 0.0769 (18) | 0.662 (16) |
F3 | 0.2288 (3) | 0.5353 (4) | 0.0210 (3) | 0.0536 (15) | 0.662 (16) |
F101 | 0.2177 (4) | 0.4986 (13) | 0.0527 (11) | 0.110 (5) | 0.338 (16) |
F102 | 0.3673 (12) | 0.5437 (9) | −0.0273 (3) | 0.085 (4) | 0.338 (16) |
F103 | 0.3618 (13) | 0.4326 (5) | 0.0768 (6) | 0.079 (4) | 0.338 (16) |
C208 | 0.5447 (3) | 0.7715 (3) | 0.0802 (2) | 0.0514 (9) | |
F4 | 0.6184 (2) | 0.7477 (3) | 0.02651 (19) | 0.0953 (11) | |
F5 | 0.58848 (19) | 0.7581 (2) | 0.13937 (17) | 0.0769 (7) | |
F6 | 0.5324 (2) | 0.86972 (19) | 0.05635 (16) | 0.0742 (7) | |
C209 | 0.1750 (2) | 0.6187 (2) | 0.31914 (15) | 0.0287 (5) | |
C210 | 0.1212 (2) | 0.5276 (2) | 0.35342 (15) | 0.0303 (6) | |
H210 | 0.0705 | 0.5087 | 0.3307 | 0.036* | |
C211 | 0.1396 (2) | 0.4632 (2) | 0.42036 (16) | 0.0319 (6) | |
C212 | 0.2133 (2) | 0.4870 (2) | 0.45516 (16) | 0.0327 (6) | |
H212 | 0.2242 | 0.4444 | 0.5014 | 0.039* | |
C213 | 0.2710 (2) | 0.5755 (2) | 0.42022 (15) | 0.0331 (6) | |
C214 | 0.2523 (2) | 0.6387 (2) | 0.35421 (16) | 0.0316 (6) | |
H214 | 0.2936 | 0.6982 | 0.3316 | 0.038* | |
C215 | 0.0779 (3) | 0.3678 (2) | 0.45479 (18) | 0.0394 (7) | |
F7 | 0.0891 (3) | 0.3215 (2) | 0.52305 (16) | 0.1057 (13) | |
F8 | 0.1056 (2) | 0.30367 (17) | 0.41512 (16) | 0.0749 (8) | |
F9 | −0.02664 (17) | 0.37837 (17) | 0.45962 (18) | 0.0765 (8) | |
C216 | 0.3515 (2) | 0.6066 (2) | 0.45483 (14) | 0.0442 (8) | |
F10 | 0.3949 (6) | 0.5281 (4) | 0.4960 (4) | 0.0507 (17) | 0.55 (2) |
F11 | 0.3049 (6) | 0.6566 (9) | 0.5025 (6) | 0.077 (2) | 0.55 (2) |
F12 | 0.4304 (6) | 0.6619 (8) | 0.4060 (4) | 0.077 (2) | 0.55 (2) |
F110 | 0.3268 (8) | 0.6926 (7) | 0.4705 (9) | 0.079 (3) | 0.45 (2) |
F111 | 0.4472 (5) | 0.6260 (10) | 0.4068 (4) | 0.057 (2) | 0.45 (2) |
F112 | 0.3692 (10) | 0.5427 (8) | 0.5162 (6) | 0.076 (3) | 0.45 (2) |
C217 | 0.0433 (2) | 0.6923 (2) | 0.22117 (15) | 0.0274 (5) | |
C218 | 0.0343 (2) | 0.7232 (2) | 0.14634 (15) | 0.0314 (6) | |
H218 | 0.0973 | 0.7441 | 0.1079 | 0.038* | |
C219 | −0.0627 (2) | 0.7247 (2) | 0.12616 (16) | 0.0340 (6) | |
C220 | −0.1572 (2) | 0.6942 (2) | 0.18000 (17) | 0.0346 (6) | |
H220 | −0.2236 | 0.6937 | 0.1662 | 0.042* | |
C221 | −0.1510 (2) | 0.6647 (2) | 0.25455 (16) | 0.0314 (6) | |
C222 | −0.0537 (2) | 0.6645 (2) | 0.27477 (15) | 0.0298 (6) | |
H222 | −0.0527 | 0.6451 | 0.3264 | 0.036* | |
C223 | −0.0639 (2) | 0.7602 (2) | 0.04464 (18) | 0.0476 (8) | |
F13 | −0.1609 (3) | 0.7639 (9) | 0.0320 (3) | 0.079 (2) | 0.64 (2) |
F14 | −0.0239 (7) | 0.8516 (4) | 0.0119 (3) | 0.0679 (18) | 0.64 (2) |
F15 | −0.0035 (8) | 0.7042 (7) | 0.0061 (3) | 0.083 (2) | 0.64 (2) |
F113 | 0.0217 (6) | 0.7335 (11) | 0.0006 (4) | 0.059 (3) | 0.36 (2) |
F114 | −0.1472 (7) | 0.7240 (12) | 0.0305 (5) | 0.064 (3) | 0.36 (2) |
F115 | −0.0662 (16) | 0.8581 (3) | 0.0190 (5) | 0.081 (4) | 0.36 (2) |
C224 | −0.2501 (2) | 0.6301 (2) | 0.31406 (16) | 0.0420 (7) | |
F16 | −0.3379 (3) | 0.6760 (6) | 0.2924 (2) | 0.0621 (18) | 0.629 (16) |
F17 | −0.2684 (7) | 0.5339 (3) | 0.3336 (5) | 0.085 (2) | 0.629 (16) |
F18 | −0.2516 (4) | 0.6553 (5) | 0.3763 (2) | 0.0439 (12) | 0.629 (16) |
F116 | −0.2339 (8) | 0.5367 (4) | 0.3558 (5) | 0.056 (3) | 0.371 (16) |
F117 | −0.2721 (9) | 0.6806 (7) | 0.3641 (5) | 0.059 (3) | 0.371 (16) |
F118 | −0.3364 (5) | 0.6204 (13) | 0.2905 (4) | 0.080 (3) | 0.371 (16) |
C225 | 0.1562 (2) | 0.8125 (2) | 0.25379 (15) | 0.0285 (5) | |
C226 | 0.1811 (2) | 0.8990 (2) | 0.19371 (15) | 0.0300 (6) | |
H226 | 0.2041 | 0.8931 | 0.1443 | 0.036* | |
C227 | 0.1733 (2) | 0.9930 (2) | 0.20406 (16) | 0.0324 (6) | |
C228 | 0.1408 (3) | 1.0047 (2) | 0.27537 (17) | 0.0378 (7) | |
H228 | 0.1378 | 1.0688 | 0.2827 | 0.045* | |
C229 | 0.1128 (3) | 0.9206 (2) | 0.33553 (17) | 0.0402 (7) | |
C230 | 0.1198 (2) | 0.8273 (2) | 0.32487 (16) | 0.0355 (6) | |
H230 | 0.0991 | 0.7711 | 0.3672 | 0.043* | |
C231 | 0.1944 (3) | 1.0842 (2) | 0.13884 (17) | 0.0395 (7) | |
F19 | 0.10172 (19) | 1.12938 (19) | 0.12701 (13) | 0.0688 (7) | |
F20 | 0.2515 (2) | 1.15254 (15) | 0.14931 (12) | 0.0575 (6) | |
F21 | 0.2444 (2) | 1.06703 (16) | 0.07525 (11) | 0.0657 (7) | |
C232 | 0.0607 (4) | 0.9297 (3) | 0.4129 (3) | 0.0506 (12) | 0.608 (8) |
F22 | 0.0784 (6) | 1.0187 (4) | 0.4189 (4) | 0.061 (2) | 0.608 (8) |
F23 | −0.0442 (4) | 0.9130 (4) | 0.4339 (3) | 0.0739 (16) | 0.608 (8) |
F24 | 0.1015 (6) | 0.8637 (4) | 0.4646 (2) | 0.0830 (19) | 0.608 (8) |
C332 | 0.0942 (6) | 0.9306 (5) | 0.4144 (3) | 0.0506 (12) | 0.392 (8) |
F122 | 0.0161 (9) | 0.8690 (6) | 0.4599 (3) | 0.077 (3) | 0.392 (8) |
F123 | 0.1775 (7) | 0.9101 (7) | 0.4460 (4) | 0.082 (3) | 0.392 (8) |
F124 | 0.0624 (10) | 1.0214 (6) | 0.4168 (6) | 0.066 (4) | 0.392 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh1 | 0.03203 (13) | 0.03519 (13) | 0.04272 (15) | 0.00454 (9) | −0.01111 (10) | −0.02335 (10) |
P2 | 0.0299 (4) | 0.0347 (4) | 0.0421 (4) | −0.0004 (3) | −0.0046 (3) | −0.0225 (3) |
B1 | 0.0394 (19) | 0.0428 (19) | 0.054 (2) | −0.0030 (15) | −0.0116 (16) | −0.0265 (18) |
N1 | 0.0475 (16) | 0.0601 (18) | 0.071 (2) | −0.0044 (14) | −0.0145 (14) | −0.0380 (16) |
C1 | 0.062 (2) | 0.074 (3) | 0.086 (3) | 0.001 (2) | −0.022 (2) | −0.050 (2) |
C2 | 0.083 (3) | 0.105 (4) | 0.152 (5) | 0.027 (3) | −0.066 (3) | −0.068 (4) |
B2 | 0.063 (3) | 0.065 (2) | 0.077 (3) | −0.016 (2) | −0.006 (2) | −0.042 (2) |
N2 | 0.072 (3) | 0.072 (2) | 0.075 (3) | −0.028 (2) | −0.005 (2) | −0.035 (2) |
C3 | 0.112 (7) | 0.116 (6) | 0.104 (6) | 0.002 (5) | −0.027 (5) | −0.018 (5) |
C4 | 0.079 (6) | 0.095 (6) | 0.106 (7) | 0.011 (5) | 0.006 (5) | −0.028 (5) |
B12 | 0.063 (3) | 0.065 (2) | 0.077 (3) | −0.016 (2) | −0.006 (2) | −0.042 (2) |
N12 | 0.072 (3) | 0.072 (2) | 0.075 (3) | −0.028 (2) | −0.005 (2) | −0.035 (2) |
C103 | 0.116 (7) | 0.116 (7) | 0.120 (7) | −0.015 (6) | −0.012 (6) | −0.029 (6) |
C104 | 0.082 (5) | 0.099 (6) | 0.094 (6) | −0.021 (5) | −0.006 (5) | −0.032 (5) |
P1 | 0.0271 (6) | 0.0374 (8) | 0.0434 (9) | 0.0032 (5) | −0.0080 (5) | −0.0239 (7) |
C5 | 0.042 (2) | 0.044 (3) | 0.045 (3) | 0.009 (2) | −0.011 (2) | −0.024 (2) |
C6 | 0.055 (3) | 0.059 (4) | 0.042 (4) | 0.014 (3) | −0.005 (3) | −0.027 (3) |
C7 | 0.066 (4) | 0.060 (4) | 0.045 (4) | 0.015 (3) | −0.013 (3) | −0.020 (4) |
C8 | 0.038 (2) | 0.041 (2) | 0.050 (2) | 0.0072 (17) | −0.0051 (18) | −0.0193 (19) |
C9 | 0.063 (3) | 0.047 (3) | 0.076 (3) | 0.013 (2) | 0.005 (3) | −0.022 (2) |
C10 | 0.069 (3) | 0.053 (3) | 0.053 (3) | 0.020 (2) | −0.007 (2) | −0.012 (2) |
C11 | 0.0320 (19) | 0.062 (3) | 0.060 (3) | 0.0042 (18) | −0.0096 (18) | −0.037 (2) |
C12 | 0.044 (3) | 0.068 (4) | 0.092 (4) | −0.013 (3) | 0.001 (3) | −0.040 (3) |
C13 | 0.048 (3) | 0.107 (4) | 0.079 (4) | 0.015 (3) | −0.032 (3) | −0.051 (3) |
P11 | 0.0271 (6) | 0.0374 (8) | 0.0434 (9) | 0.0032 (5) | −0.0080 (5) | −0.0239 (7) |
C105 | 0.039 (5) | 0.040 (6) | 0.032 (5) | −0.003 (5) | −0.004 (4) | −0.023 (4) |
C106 | 0.034 (6) | 0.043 (7) | 0.040 (8) | 0.005 (5) | −0.011 (5) | −0.013 (6) |
C107 | 0.042 (7) | 0.040 (7) | 0.037 (8) | 0.005 (5) | −0.013 (6) | −0.014 (6) |
C108 | 0.045 (5) | 0.043 (5) | 0.052 (5) | 0.006 (4) | −0.013 (4) | −0.017 (4) |
C109 | 0.058 (6) | 0.049 (6) | 0.062 (6) | 0.006 (5) | −0.010 (5) | −0.010 (5) |
C110 | 0.066 (7) | 0.056 (6) | 0.059 (6) | 0.007 (5) | −0.015 (5) | −0.010 (5) |
C111 | 0.029 (5) | 0.047 (6) | 0.055 (5) | 0.005 (5) | −0.011 (4) | −0.028 (5) |
C112 | 0.044 (6) | 0.058 (7) | 0.065 (7) | −0.008 (5) | −0.009 (5) | −0.021 (5) |
C113 | 0.060 (6) | 0.071 (6) | 0.070 (6) | 0.003 (5) | −0.021 (5) | −0.033 (5) |
C14 | 0.052 (2) | 0.0323 (16) | 0.063 (2) | 0.0057 (14) | −0.0136 (17) | −0.0210 (16) |
C15 | 0.048 (2) | 0.051 (2) | 0.105 (4) | 0.0151 (17) | −0.028 (2) | −0.033 (2) |
C16 | 0.105 (4) | 0.043 (2) | 0.068 (3) | 0.017 (2) | −0.029 (3) | −0.011 (2) |
C17 | 0.0460 (19) | 0.054 (2) | 0.0406 (18) | −0.0021 (15) | −0.0011 (14) | −0.0230 (16) |
C18 | 0.069 (3) | 0.091 (3) | 0.056 (2) | −0.005 (2) | 0.004 (2) | −0.049 (2) |
C19 | 0.081 (3) | 0.070 (3) | 0.041 (2) | 0.003 (2) | −0.0092 (19) | −0.0118 (19) |
C20 | 0.0393 (18) | 0.060 (2) | 0.074 (3) | −0.0061 (15) | −0.0037 (17) | −0.048 (2) |
C21 | 0.063 (3) | 0.070 (3) | 0.103 (4) | −0.031 (2) | 0.014 (2) | −0.051 (3) |
C22 | 0.046 (2) | 0.104 (4) | 0.112 (4) | 0.006 (2) | −0.033 (2) | −0.074 (3) |
B200 | 0.0261 (15) | 0.0365 (16) | 0.0251 (14) | 0.0013 (12) | −0.0063 (11) | −0.0096 (13) |
C201 | 0.0263 (13) | 0.0335 (14) | 0.0264 (13) | 0.0035 (10) | −0.0078 (10) | −0.0097 (11) |
C202 | 0.0292 (14) | 0.0388 (15) | 0.0399 (16) | 0.0013 (11) | −0.0089 (12) | −0.0178 (13) |
C203 | 0.0360 (16) | 0.0418 (16) | 0.0444 (17) | 0.0071 (12) | −0.0107 (13) | −0.0248 (14) |
C204 | 0.0307 (15) | 0.0501 (18) | 0.0413 (17) | 0.0083 (13) | −0.0054 (12) | −0.0253 (15) |
C205 | 0.0259 (14) | 0.0459 (17) | 0.0368 (15) | 0.0035 (12) | −0.0065 (11) | −0.0185 (13) |
C206 | 0.0284 (14) | 0.0388 (15) | 0.0313 (14) | 0.0014 (11) | −0.0077 (11) | −0.0156 (12) |
C207 | 0.0394 (19) | 0.058 (2) | 0.073 (3) | 0.0037 (16) | −0.0053 (17) | −0.039 (2) |
F1 | 0.057 (2) | 0.085 (3) | 0.061 (2) | −0.002 (2) | −0.001 (2) | −0.051 (2) |
F2 | 0.109 (4) | 0.044 (2) | 0.089 (4) | −0.006 (2) | −0.037 (3) | −0.025 (2) |
F3 | 0.055 (2) | 0.064 (3) | 0.059 (3) | −0.0016 (16) | −0.0229 (17) | −0.035 (2) |
F101 | 0.100 (6) | 0.123 (7) | 0.137 (8) | −0.004 (5) | −0.026 (5) | −0.084 (6) |
F102 | 0.114 (8) | 0.098 (6) | 0.069 (5) | 0.026 (5) | −0.045 (5) | −0.050 (4) |
F103 | 0.119 (7) | 0.052 (5) | 0.069 (5) | −0.013 (4) | 0.001 (5) | −0.039 (4) |
C208 | 0.0318 (17) | 0.069 (2) | 0.059 (2) | −0.0024 (15) | 0.0010 (15) | −0.0364 (19) |
F4 | 0.0446 (13) | 0.129 (2) | 0.124 (2) | −0.0284 (14) | 0.0348 (14) | −0.091 (2) |
F5 | 0.0436 (13) | 0.104 (2) | 0.099 (2) | −0.0080 (12) | −0.0310 (13) | −0.0401 (16) |
F6 | 0.0588 (15) | 0.0629 (15) | 0.0946 (19) | −0.0204 (12) | −0.0013 (13) | −0.0215 (14) |
C209 | 0.0265 (13) | 0.0361 (14) | 0.0257 (13) | 0.0045 (11) | −0.0068 (10) | −0.0123 (11) |
C210 | 0.0272 (13) | 0.0367 (14) | 0.0298 (14) | 0.0029 (11) | −0.0078 (11) | −0.0135 (12) |
C211 | 0.0303 (14) | 0.0348 (14) | 0.0307 (14) | 0.0041 (11) | −0.0052 (11) | −0.0116 (12) |
C212 | 0.0338 (15) | 0.0374 (15) | 0.0259 (13) | 0.0049 (11) | −0.0071 (11) | −0.0083 (12) |
C213 | 0.0312 (14) | 0.0421 (16) | 0.0287 (14) | 0.0030 (12) | −0.0103 (11) | −0.0121 (12) |
C214 | 0.0299 (14) | 0.0375 (15) | 0.0287 (14) | −0.0010 (11) | −0.0078 (11) | −0.0104 (12) |
C215 | 0.0375 (16) | 0.0389 (16) | 0.0390 (17) | −0.0001 (13) | −0.0075 (13) | −0.0080 (14) |
F7 | 0.159 (3) | 0.086 (2) | 0.0642 (17) | −0.071 (2) | −0.0574 (19) | 0.0308 (15) |
F8 | 0.0725 (16) | 0.0495 (13) | 0.0972 (19) | −0.0140 (11) | 0.0156 (14) | −0.0374 (13) |
F9 | 0.0364 (11) | 0.0532 (13) | 0.121 (2) | −0.0062 (10) | 0.0038 (12) | −0.0121 (14) |
C216 | 0.0477 (19) | 0.053 (2) | 0.0374 (17) | −0.0012 (15) | −0.0214 (14) | −0.0113 (15) |
F10 | 0.040 (3) | 0.064 (3) | 0.053 (3) | 0.006 (2) | −0.028 (2) | −0.011 (2) |
F11 | 0.086 (4) | 0.101 (5) | 0.084 (4) | 0.025 (3) | −0.050 (3) | −0.066 (4) |
F12 | 0.087 (4) | 0.081 (4) | 0.065 (3) | −0.047 (3) | −0.045 (3) | 0.009 (3) |
F110 | 0.093 (5) | 0.091 (5) | 0.094 (6) | 0.022 (4) | −0.061 (4) | −0.058 (4) |
F111 | 0.041 (3) | 0.081 (5) | 0.054 (4) | −0.020 (3) | −0.004 (2) | −0.026 (3) |
F112 | 0.071 (5) | 0.102 (5) | 0.047 (4) | −0.028 (4) | −0.036 (4) | 0.015 (3) |
C217 | 0.0268 (13) | 0.0323 (13) | 0.0236 (13) | 0.0034 (10) | −0.0056 (10) | −0.0093 (11) |
C218 | 0.0273 (13) | 0.0416 (15) | 0.0245 (13) | 0.0017 (11) | −0.0050 (10) | −0.0090 (12) |
C219 | 0.0316 (14) | 0.0440 (16) | 0.0267 (14) | 0.0042 (12) | −0.0094 (11) | −0.0093 (12) |
C220 | 0.0269 (14) | 0.0440 (16) | 0.0364 (15) | 0.0029 (12) | −0.0100 (11) | −0.0152 (13) |
C221 | 0.0262 (13) | 0.0363 (15) | 0.0312 (14) | 0.0019 (11) | −0.0037 (11) | −0.0113 (12) |
C222 | 0.0314 (14) | 0.0344 (14) | 0.0238 (13) | 0.0034 (11) | −0.0051 (10) | −0.0098 (11) |
C223 | 0.0400 (18) | 0.072 (2) | 0.0317 (16) | 0.0029 (16) | −0.0139 (13) | −0.0127 (16) |
F13 | 0.042 (2) | 0.132 (5) | 0.046 (3) | −0.008 (3) | −0.0247 (18) | 0.014 (3) |
F14 | 0.058 (3) | 0.092 (3) | 0.036 (2) | −0.025 (2) | −0.0164 (19) | 0.017 (2) |
F15 | 0.096 (4) | 0.122 (4) | 0.046 (3) | 0.020 (4) | −0.026 (3) | −0.044 (3) |
F113 | 0.037 (4) | 0.110 (6) | 0.029 (3) | −0.001 (4) | −0.009 (2) | −0.018 (4) |
F114 | 0.053 (4) | 0.108 (6) | 0.036 (4) | −0.020 (4) | −0.025 (3) | −0.014 (4) |
F115 | 0.106 (7) | 0.074 (5) | 0.062 (5) | 0.024 (4) | −0.032 (5) | −0.013 (4) |
C224 | 0.0327 (16) | 0.0525 (19) | 0.0389 (17) | −0.0022 (13) | −0.0012 (13) | −0.0151 (15) |
F16 | 0.0241 (17) | 0.094 (4) | 0.054 (2) | −0.0024 (18) | −0.0029 (14) | −0.005 (2) |
F17 | 0.085 (4) | 0.054 (2) | 0.101 (4) | −0.036 (2) | 0.039 (3) | −0.039 (2) |
F18 | 0.036 (2) | 0.057 (3) | 0.0339 (18) | 0.0115 (19) | 0.0004 (15) | −0.0149 (18) |
F116 | 0.055 (4) | 0.042 (3) | 0.058 (4) | −0.019 (3) | 0.020 (3) | −0.015 (3) |
F117 | 0.051 (5) | 0.048 (4) | 0.063 (5) | 0.015 (3) | 0.017 (3) | −0.018 (3) |
F118 | 0.045 (4) | 0.123 (7) | 0.064 (4) | −0.040 (4) | −0.013 (3) | −0.009 (4) |
C225 | 0.0243 (13) | 0.0372 (14) | 0.0246 (13) | 0.0018 (10) | −0.0053 (10) | −0.0102 (11) |
C226 | 0.0271 (13) | 0.0414 (15) | 0.0225 (13) | 0.0014 (11) | −0.0057 (10) | −0.0107 (11) |
C227 | 0.0315 (14) | 0.0386 (15) | 0.0264 (13) | −0.0003 (11) | −0.0064 (11) | −0.0082 (12) |
C228 | 0.0474 (18) | 0.0359 (15) | 0.0308 (15) | −0.0003 (13) | −0.0065 (13) | −0.0125 (13) |
C229 | 0.0525 (19) | 0.0401 (16) | 0.0268 (14) | −0.0012 (14) | −0.0014 (13) | −0.0134 (13) |
C230 | 0.0402 (16) | 0.0388 (16) | 0.0253 (14) | −0.0003 (12) | −0.0030 (11) | −0.0092 (12) |
C231 | 0.0454 (18) | 0.0412 (17) | 0.0317 (15) | −0.0018 (13) | −0.0104 (13) | −0.0085 (13) |
F19 | 0.0599 (14) | 0.0749 (16) | 0.0552 (13) | 0.0092 (12) | −0.0230 (11) | 0.0127 (12) |
F20 | 0.0786 (15) | 0.0419 (11) | 0.0508 (12) | −0.0169 (10) | −0.0211 (11) | −0.0032 (9) |
F21 | 0.1049 (19) | 0.0483 (12) | 0.0295 (10) | −0.0120 (12) | 0.0094 (11) | −0.0064 (9) |
C232 | 0.069 (3) | 0.0465 (18) | 0.0348 (17) | −0.005 (2) | 0.000 (2) | −0.0182 (15) |
F22 | 0.089 (4) | 0.054 (3) | 0.042 (3) | −0.022 (3) | 0.006 (3) | −0.030 (3) |
F23 | 0.068 (3) | 0.098 (3) | 0.054 (3) | −0.022 (2) | 0.021 (2) | −0.044 (2) |
F24 | 0.130 (5) | 0.088 (3) | 0.0289 (19) | 0.034 (3) | −0.016 (3) | −0.020 (2) |
C332 | 0.069 (3) | 0.0465 (18) | 0.0348 (17) | −0.005 (2) | 0.000 (2) | −0.0182 (15) |
F122 | 0.114 (5) | 0.061 (4) | 0.043 (3) | −0.037 (4) | 0.027 (4) | −0.026 (3) |
F123 | 0.113 (5) | 0.102 (5) | 0.043 (3) | 0.015 (4) | −0.032 (3) | −0.028 (3) |
F124 | 0.092 (6) | 0.059 (6) | 0.044 (5) | −0.001 (4) | 0.002 (4) | −0.026 (4) |
Rh1—P1 | 2.3078 (12) | C15—H15A | 0.9800 |
Rh1—B1 | 2.316 (4) | C15—H15B | 0.9800 |
Rh1—P2 | 2.3259 (7) | C15—H15C | 0.9800 |
Rh1—P11 | 2.397 (5) | C16—H16A | 0.9800 |
Rh1—H0A | 1.44 (3) | C16—H16B | 0.9800 |
Rh1—H0B | 1.44 (3) | C16—H16C | 0.9800 |
Rh1—H1A | 1.88 (4) | C17—C19 | 1.525 (6) |
Rh1—H1B | 1.91 (4) | C17—C18 | 1.544 (5) |
P2—C20 | 1.855 (3) | C17—H17 | 1.0000 |
P2—C17 | 1.858 (3) | C18—H18A | 0.9800 |
P2—C14 | 1.874 (4) | C18—H18B | 0.9800 |
B1—N1 | 1.591 (4) | C18—H18C | 0.9800 |
B1—H1A | 1.22 (4) | C19—H19A | 0.9800 |
B1—H1B | 1.18 (4) | C19—H19B | 0.9800 |
B1—H1C | 1.12 (4) | C19—H19C | 0.9800 |
N1—C1 | 1.443 (5) | C20—C22 | 1.523 (6) |
N1—C2 | 1.492 (6) | C20—C21 | 1.530 (6) |
N1—B2 | 1.577 (7) | C20—H20 | 1.0000 |
N1—B12 | 1.585 (7) | C21—H21A | 0.9800 |
C1—H1D | 0.9800 | C21—H21B | 0.9800 |
C1—H1E | 0.9800 | C21—H21C | 0.9800 |
C1—H1F | 0.9800 | C22—H22A | 0.9800 |
C2—H2A | 0.9800 | C22—H22B | 0.9800 |
C2—H2B | 0.9800 | C22—H22C | 0.9800 |
C2—H2C | 0.9800 | B200—C217 | 1.637 (4) |
B2—N2 | 1.611 (7) | B200—C209 | 1.638 (4) |
B2—H2D | 1.1317 | B200—C201 | 1.639 (4) |
B2—H2E | 1.1317 | B200—C225 | 1.646 (4) |
N2—C4 | 1.509 (9) | C201—C206 | 1.396 (4) |
N2—C3 | 1.528 (9) | C201—C202 | 1.407 (4) |
N2—H2 | 0.9300 | C202—C203 | 1.390 (4) |
C3—H3A | 0.9800 | C202—H202 | 0.9500 |
C3—H3B | 0.9800 | C203—C204 | 1.381 (4) |
C3—H3C | 0.9800 | C203—C207 | 1.504 (5) |
C4—H4A | 0.9800 | C204—C205 | 1.380 (4) |
C4—H4B | 0.9800 | C204—H204 | 0.9500 |
C4—H4C | 0.9800 | C205—C206 | 1.398 (4) |
B12—N12 | 1.607 (7) | C205—C208 | 1.492 (5) |
B12—H12A | 1.1317 | C206—H206 | 0.9500 |
B12—H12B | 1.1317 | C207—F102 | 1.320 (4) |
N12—C104 | 1.504 (9) | C207—F2 | 1.320 (4) |
N12—C103 | 1.513 (9) | C207—F101 | 1.333 (4) |
N12—H12 | 0.9300 | C207—F1 | 1.340 (4) |
C103—H10A | 0.9800 | C207—F3 | 1.342 (4) |
C103—H10B | 0.9800 | C207—F103 | 1.349 (4) |
C103—H10C | 0.9800 | C208—F4 | 1.332 (4) |
C104—H10D | 0.9800 | C208—F6 | 1.336 (5) |
C104—H10E | 0.9800 | C208—F5 | 1.340 (5) |
C104—H10F | 0.9800 | C209—C210 | 1.397 (4) |
P1—C11 | 1.855 (4) | C209—C214 | 1.404 (4) |
P1—C8 | 1.857 (4) | C210—C211 | 1.401 (4) |
P1—C5 | 1.877 (5) | C210—H210 | 0.9500 |
C5—C7 | 1.540 (13) | C211—C212 | 1.384 (4) |
C5—C6 | 1.544 (12) | C211—C215 | 1.492 (4) |
C5—H5 | 1.0000 | C212—C213 | 1.391 (4) |
C6—H6A | 0.9800 | C212—H212 | 0.9500 |
C6—H6B | 0.9800 | C213—C214 | 1.382 (4) |
C6—H6C | 0.9800 | C213—C216 | 1.497 (4) |
C7—H7A | 0.9800 | C214—H214 | 0.9500 |
C7—H7B | 0.9800 | C215—F7 | 1.317 (4) |
C7—H7C | 0.9800 | C215—F8 | 1.325 (4) |
C8—C10 | 1.514 (7) | C215—F9 | 1.326 (4) |
C8—C9 | 1.531 (6) | C216—F112 | 1.314 (4) |
C8—H8 | 1.0000 | C216—F12 | 1.315 (4) |
C9—H9A | 0.9800 | C216—F11 | 1.326 (4) |
C9—H9B | 0.9800 | C216—F10 | 1.334 (4) |
C9—H9C | 0.9800 | C216—F110 | 1.334 (4) |
C10—H10G | 0.9800 | C216—F111 | 1.338 (4) |
C10—H10H | 0.9800 | C217—C218 | 1.402 (4) |
C10—H10I | 0.9800 | C217—C222 | 1.406 (4) |
C11—C13 | 1.529 (7) | C218—C219 | 1.386 (4) |
C11—C12 | 1.541 (8) | C218—H218 | 0.9500 |
C11—H11 | 1.0000 | C219—C220 | 1.390 (4) |
C12—H12C | 0.9800 | C219—C223 | 1.498 (4) |
C12—H12D | 0.9800 | C220—C221 | 1.387 (4) |
C12—H12E | 0.9800 | C220—H220 | 0.9500 |
C13—H13A | 0.9800 | C221—C222 | 1.392 (4) |
C13—H13B | 0.9800 | C221—C224 | 1.490 (4) |
C13—H13C | 0.9800 | C222—H222 | 0.9500 |
P11—C105 | 1.865 (8) | C223—F13 | 1.318 (4) |
P11—C108 | 1.871 (8) | C223—F115 | 1.323 (4) |
P11—C111 | 1.873 (8) | C223—F114 | 1.325 (4) |
C105—C107 | 1.50 (4) | C223—F113 | 1.326 (4) |
C105—C106 | 1.55 (4) | C223—F14 | 1.330 (4) |
C105—H105 | 1.0000 | C223—F15 | 1.330 (4) |
C106—H10J | 0.9800 | C224—F17 | 1.315 (4) |
C106—H10K | 0.9800 | C224—F118 | 1.319 (4) |
C106—H10L | 0.9800 | C224—F117 | 1.323 (4) |
C107—H10M | 0.9800 | C224—F18 | 1.335 (3) |
C107—H10N | 0.9800 | C224—F16 | 1.356 (3) |
C107—H10O | 0.9800 | C224—F116 | 1.358 (4) |
C108—C109 | 1.48 (2) | C225—C226 | 1.401 (4) |
C108—C110 | 1.54 (2) | C225—C230 | 1.405 (4) |
C108—H108 | 1.0000 | C226—C227 | 1.389 (4) |
C109—H10P | 0.9800 | C226—H226 | 0.9500 |
C109—H10Q | 0.9800 | C227—C228 | 1.388 (4) |
C109—H10R | 0.9800 | C227—C231 | 1.493 (4) |
C110—H11A | 0.9800 | C228—C229 | 1.385 (4) |
C110—H11B | 0.9800 | C228—H228 | 0.9500 |
C110—H11C | 0.9800 | C229—C230 | 1.382 (4) |
C111—C112 | 1.49 (2) | C229—C232 | 1.516 (5) |
C111—C113 | 1.51 (2) | C229—C332 | 1.521 (7) |
C111—H111 | 1.0000 | C230—H230 | 0.9500 |
C112—H11D | 0.9800 | C231—F21 | 1.320 (4) |
C112—H11E | 0.9800 | C231—F20 | 1.330 (4) |
C112—H11F | 0.9800 | C231—F19 | 1.351 (4) |
C113—H11G | 0.9800 | C232—F23 | 1.325 (4) |
C113—H11H | 0.9800 | C232—F22 | 1.328 (4) |
C113—H11I | 0.9800 | C232—F24 | 1.330 (4) |
C14—C15 | 1.525 (6) | C332—F123 | 1.325 (4) |
C14—C16 | 1.531 (6) | C332—F122 | 1.329 (4) |
C14—H14 | 1.0000 | C332—F124 | 1.329 (4) |
P1—Rh1—B1 | 107.65 (10) | C14—C16—H16C | 109.5 |
P1—Rh1—P2 | 160.86 (4) | H16A—C16—H16C | 109.5 |
B1—Rh1—P2 | 90.98 (9) | H16B—C16—H16C | 109.5 |
P1—Rh1—P11 | 12.16 (12) | C19—C17—C18 | 110.9 (3) |
B1—Rh1—P11 | 114.78 (16) | C19—C17—P2 | 113.2 (3) |
P2—Rh1—P11 | 153.57 (14) | C18—C17—P2 | 113.8 (3) |
P1—Rh1—H0A | 77.0 (14) | C19—C17—H17 | 106.1 |
B1—Rh1—H0A | 143.9 (14) | C18—C17—H17 | 106.1 |
P2—Rh1—H0A | 85.3 (14) | P2—C17—H17 | 106.1 |
P11—Rh1—H0A | 77.2 (14) | C17—C18—H18A | 109.5 |
P1—Rh1—H0B | 85.0 (14) | C17—C18—H18B | 109.5 |
B1—Rh1—H0B | 142.3 (14) | H18A—C18—H18B | 109.5 |
P2—Rh1—H0B | 82.7 (14) | C17—C18—H18C | 109.5 |
P11—Rh1—H0B | 73.3 (14) | H18A—C18—H18C | 109.5 |
H0A—Rh1—H0B | 72.8 (19) | H18B—C18—H18C | 109.5 |
P1—Rh1—H1A | 105.0 (11) | C17—C19—H19A | 109.5 |
B1—Rh1—H1A | 31.6 (12) | C17—C19—H19B | 109.5 |
P2—Rh1—H1A | 93.1 (11) | H19A—C19—H19B | 109.5 |
P11—Rh1—H1A | 105.7 (12) | C17—C19—H19C | 109.5 |
H0A—Rh1—H1A | 175.3 (18) | H19A—C19—H19C | 109.5 |
H0B—Rh1—H1A | 111.4 (18) | H19B—C19—H19C | 109.5 |
P1—Rh1—H1B | 95.4 (11) | C22—C20—C21 | 109.8 (4) |
B1—Rh1—H1B | 30.5 (12) | C22—C20—P2 | 113.9 (3) |
P2—Rh1—H1B | 98.7 (11) | C21—C20—P2 | 113.0 (3) |
P11—Rh1—H1B | 106.5 (11) | C22—C20—H20 | 106.6 |
H0A—Rh1—H1B | 114.8 (18) | C21—C20—H20 | 106.6 |
H0B—Rh1—H1B | 172.3 (18) | P2—C20—H20 | 106.6 |
H1A—Rh1—H1B | 61.1 (16) | C20—C21—H21A | 109.5 |
C20—P2—C17 | 105.18 (17) | C20—C21—H21B | 109.5 |
C20—P2—C14 | 100.08 (17) | H21A—C21—H21B | 109.5 |
C17—P2—C14 | 104.15 (17) | C20—C21—H21C | 109.5 |
C20—P2—Rh1 | 113.80 (11) | H21A—C21—H21C | 109.5 |
C17—P2—Rh1 | 114.08 (11) | H21B—C21—H21C | 109.5 |
C14—P2—Rh1 | 117.83 (12) | C20—C22—H22A | 109.5 |
N1—B1—Rh1 | 138.7 (2) | C20—C22—H22B | 109.5 |
N1—B1—H1A | 108.2 (18) | H22A—C22—H22B | 109.5 |
Rh1—B1—H1A | 54.2 (18) | C20—C22—H22C | 109.5 |
N1—B1—H1B | 111.6 (19) | H22A—C22—H22C | 109.5 |
Rh1—B1—H1B | 55.3 (19) | H22B—C22—H22C | 109.5 |
H1A—B1—H1B | 107 (3) | C217—B200—C209 | 114.8 (2) |
N1—B1—H1C | 105 (2) | C217—B200—C201 | 110.7 (2) |
Rh1—B1—H1C | 116 (2) | C209—B200—C201 | 105.2 (2) |
H1A—B1—H1C | 115 (3) | C217—B200—C225 | 103.9 (2) |
H1B—B1—H1C | 109 (3) | C209—B200—C225 | 109.0 (2) |
C1—N1—C2 | 105.2 (4) | C201—B200—C225 | 113.5 (2) |
C1—N1—B2 | 101.6 (5) | C206—C201—C202 | 115.1 (2) |
C2—N1—B2 | 111.6 (7) | C206—C201—B200 | 124.3 (2) |
C1—N1—B12 | 106.0 (5) | C202—C201—B200 | 120.5 (2) |
C2—N1—B12 | 117.2 (7) | C203—C202—C201 | 122.5 (3) |
B2—N1—B12 | 9.3 (11) | C203—C202—H202 | 118.7 |
C1—N1—B1 | 114.6 (3) | C201—C202—H202 | 118.7 |
C2—N1—B1 | 107.0 (3) | C204—C203—C202 | 120.9 (3) |
B2—N1—B1 | 116.3 (6) | C204—C203—C207 | 119.3 (3) |
B12—N1—B1 | 107.1 (6) | C202—C203—C207 | 119.8 (3) |
N1—C1—H1D | 109.5 | C205—C204—C203 | 118.1 (3) |
N1—C1—H1E | 109.5 | C205—C204—H204 | 121.0 |
H1D—C1—H1E | 109.5 | C203—C204—H204 | 121.0 |
N1—C1—H1F | 109.5 | C204—C205—C206 | 120.9 (3) |
H1D—C1—H1F | 109.5 | C204—C205—C208 | 119.9 (3) |
H1E—C1—H1F | 109.5 | C206—C205—C208 | 119.1 (3) |
N1—C2—H2A | 109.5 | C201—C206—C205 | 122.4 (3) |
N1—C2—H2B | 109.5 | C201—C206—H206 | 118.8 |
H2A—C2—H2B | 109.5 | C205—C206—H206 | 118.8 |
N1—C2—H2C | 109.5 | F102—C207—F101 | 108.3 (5) |
H2A—C2—H2C | 109.5 | F2—C207—F1 | 108.0 (4) |
H2B—C2—H2C | 109.5 | F2—C207—F3 | 106.9 (4) |
N1—B2—N2 | 106.1 (6) | F1—C207—F3 | 104.1 (4) |
N1—B2—H2D | 110.5 | F102—C207—F103 | 106.2 (5) |
N1—B2—H2E | 110.5 | F101—C207—F103 | 103.7 (5) |
C4—N2—C3 | 106.5 (8) | F102—C207—C203 | 115.5 (5) |
C4—N2—B2 | 113.8 (6) | F2—C207—C203 | 113.3 (4) |
C3—N2—B2 | 109.5 (6) | F101—C207—C203 | 113.2 (5) |
C4—N2—H2 | 109.0 | F1—C207—C203 | 112.2 (3) |
C3—N2—H2 | 109.0 | F3—C207—C203 | 111.7 (3) |
B2—N2—H2 | 109.0 | F103—C207—C203 | 109.1 (5) |
N1—B12—N12 | 116.3 (7) | F4—C208—F6 | 106.3 (3) |
N1—B12—H12A | 108.2 | F4—C208—F5 | 107.4 (3) |
N12—B12—H12A | 108.2 | F6—C208—F5 | 104.3 (3) |
N1—B12—H12B | 108.2 | F4—C208—C205 | 113.2 (3) |
N12—B12—H12B | 108.2 | F6—C208—C205 | 113.1 (3) |
H12A—B12—H12B | 107.4 | F5—C208—C205 | 112.0 (3) |
C104—N12—C103 | 108.2 (9) | C210—C209—C214 | 115.5 (3) |
C104—N12—B12 | 115.0 (6) | C210—C209—B200 | 126.3 (2) |
C103—N12—B12 | 112.0 (7) | C214—C209—B200 | 118.2 (2) |
C104—N12—H12 | 107.1 | C209—C210—C211 | 121.9 (3) |
C103—N12—H12 | 107.1 | C209—C210—H210 | 119.1 |
B12—N12—H12 | 107.1 | C211—C210—H210 | 119.1 |
N12—C103—H10A | 109.5 | C212—C211—C210 | 121.1 (3) |
N12—C103—H10B | 109.5 | C212—C211—C215 | 119.7 (3) |
H10A—C103—H10B | 109.5 | C210—C211—C215 | 119.2 (3) |
N12—C103—H10C | 109.5 | C211—C212—C213 | 117.8 (3) |
H10A—C103—H10C | 109.5 | C211—C212—H212 | 121.1 |
H10B—C103—H10C | 109.5 | C213—C212—H212 | 121.1 |
N12—C104—H10D | 109.5 | C214—C213—C212 | 120.8 (3) |
N12—C104—H10E | 109.5 | C214—C213—C216 | 118.4 (3) |
H10D—C104—H10E | 109.5 | C212—C213—C216 | 120.8 (2) |
N12—C104—H10F | 109.5 | C213—C214—C209 | 122.8 (3) |
H10D—C104—H10F | 109.5 | C213—C214—H214 | 118.6 |
H10E—C104—H10F | 109.5 | C209—C214—H214 | 118.6 |
C11—P1—C8 | 105.8 (2) | F7—C215—F8 | 106.4 (3) |
C11—P1—C5 | 103.5 (3) | F7—C215—F9 | 106.1 (3) |
C8—P1—C5 | 103.7 (2) | F8—C215—F9 | 103.7 (3) |
C11—P1—Rh1 | 114.03 (15) | F7—C215—C211 | 113.5 (3) |
C8—P1—Rh1 | 113.35 (15) | F8—C215—C211 | 112.8 (3) |
C5—P1—Rh1 | 115.3 (3) | F9—C215—C211 | 113.4 (3) |
C7—C5—C6 | 110.4 (6) | F12—C216—F11 | 107.8 (4) |
C7—C5—P1 | 111.5 (6) | F12—C216—F10 | 107.5 (4) |
C6—C5—P1 | 116.4 (5) | F11—C216—F10 | 104.9 (4) |
C7—C5—H5 | 105.9 | F112—C216—F110 | 106.9 (5) |
C6—C5—H5 | 105.9 | F112—C216—F111 | 105.9 (5) |
P1—C5—H5 | 105.9 | F110—C216—F111 | 102.9 (5) |
C10—C8—C9 | 110.5 (4) | F112—C216—C213 | 116.3 (4) |
C10—C8—P1 | 113.9 (3) | F12—C216—C213 | 114.0 (4) |
C9—C8—P1 | 116.7 (3) | F11—C216—C213 | 110.8 (4) |
C10—C8—H8 | 104.8 | F10—C216—C213 | 111.4 (3) |
C9—C8—H8 | 104.8 | F110—C216—C213 | 112.4 (4) |
P1—C8—H8 | 104.8 | F111—C216—C213 | 111.3 (4) |
C13—C11—C12 | 110.6 (5) | C218—C217—C222 | 115.3 (2) |
C13—C11—P1 | 114.0 (4) | C218—C217—B200 | 120.6 (2) |
C12—C11—P1 | 111.7 (4) | C222—C217—B200 | 123.7 (2) |
C13—C11—H11 | 106.7 | C219—C218—C217 | 122.6 (3) |
C12—C11—H11 | 106.7 | C219—C218—H218 | 118.7 |
P1—C11—H11 | 106.7 | C217—C218—H218 | 118.7 |
C105—P11—C108 | 103.9 (6) | C218—C219—C220 | 121.1 (3) |
C105—P11—C111 | 103.6 (6) | C218—C219—C223 | 118.5 (2) |
C108—P11—C111 | 102.7 (5) | C220—C219—C223 | 120.4 (2) |
C105—P11—Rh1 | 115.6 (9) | C221—C220—C219 | 117.5 (3) |
C108—P11—Rh1 | 112.4 (5) | C221—C220—H220 | 121.2 |
C111—P11—Rh1 | 117.0 (5) | C219—C220—H220 | 121.2 |
C107—C105—C106 | 106.6 (19) | C220—C221—C222 | 121.3 (3) |
C107—C105—P11 | 116.5 (18) | C220—C221—C224 | 119.3 (2) |
C106—C105—P11 | 115.7 (16) | C222—C221—C224 | 119.4 (2) |
C107—C105—H105 | 105.7 | C221—C222—C217 | 122.1 (3) |
C106—C105—H105 | 105.7 | C221—C222—H222 | 119.0 |
P11—C105—H105 | 105.7 | C217—C222—H222 | 119.0 |
C105—C106—H10J | 109.5 | F115—C223—F114 | 107.7 (5) |
C105—C106—H10K | 109.5 | F115—C223—F113 | 105.0 (5) |
H10J—C106—H10K | 109.5 | F114—C223—F113 | 105.3 (5) |
C105—C106—H10L | 109.5 | F13—C223—F14 | 105.1 (4) |
H10J—C106—H10L | 109.5 | F13—C223—F15 | 108.3 (4) |
H10K—C106—H10L | 109.5 | F14—C223—F15 | 105.0 (4) |
C105—C107—H10M | 109.5 | F13—C223—C219 | 113.5 (3) |
C105—C107—H10N | 109.5 | F115—C223—C219 | 112.7 (5) |
H10M—C107—H10N | 109.5 | F114—C223—C219 | 111.9 (4) |
C105—C107—H10O | 109.5 | F113—C223—C219 | 113.6 (4) |
H10M—C107—H10O | 109.5 | F14—C223—C219 | 112.6 (3) |
H10N—C107—H10O | 109.5 | F15—C223—C219 | 111.9 (3) |
C109—C108—C110 | 111.3 (14) | F118—C224—F117 | 110.5 (5) |
C109—C108—P11 | 116.6 (11) | F17—C224—F18 | 107.7 (4) |
C110—C108—P11 | 110.2 (10) | F17—C224—F16 | 107.2 (4) |
C109—C108—H108 | 106.0 | F18—C224—F16 | 102.7 (3) |
C110—C108—H108 | 106.0 | F118—C224—F116 | 103.5 (4) |
P11—C108—H108 | 106.0 | F117—C224—F116 | 103.1 (4) |
C108—C109—H10P | 109.5 | F17—C224—C221 | 114.5 (3) |
C108—C109—H10Q | 109.5 | F118—C224—C221 | 115.9 (4) |
H10P—C109—H10Q | 109.5 | F117—C224—C221 | 114.0 (4) |
C108—C109—H10R | 109.5 | F18—C224—C221 | 112.9 (3) |
H10P—C109—H10R | 109.5 | F16—C224—C221 | 111.1 (3) |
H10Q—C109—H10R | 109.5 | F116—C224—C221 | 108.6 (4) |
C108—C110—H11A | 109.5 | C226—C225—C230 | 115.5 (3) |
C108—C110—H11B | 109.5 | C226—C225—B200 | 122.9 (2) |
H11A—C110—H11B | 109.5 | C230—C225—B200 | 121.3 (2) |
C108—C110—H11C | 109.5 | C227—C226—C225 | 122.2 (2) |
H11A—C110—H11C | 109.5 | C227—C226—H226 | 118.9 |
H11B—C110—H11C | 109.5 | C225—C226—H226 | 118.9 |
C112—C111—C113 | 112.5 (13) | C228—C227—C226 | 120.7 (3) |
C112—C111—P11 | 113.2 (10) | C228—C227—C231 | 118.1 (3) |
C113—C111—P11 | 113.7 (12) | C226—C227—C231 | 121.1 (3) |
C112—C111—H111 | 105.5 | C229—C228—C227 | 118.2 (3) |
C113—C111—H111 | 105.5 | C229—C228—H228 | 120.9 |
P11—C111—H111 | 105.5 | C227—C228—H228 | 120.9 |
C111—C112—H11D | 109.5 | C230—C229—C228 | 120.8 (3) |
C111—C112—H11E | 109.5 | C230—C229—C232 | 118.3 (3) |
H11D—C112—H11E | 109.5 | C228—C229—C232 | 120.5 (3) |
C111—C112—H11F | 109.5 | C230—C229—C332 | 119.7 (3) |
H11D—C112—H11F | 109.5 | C228—C229—C332 | 118.6 (3) |
H11E—C112—H11F | 109.5 | C232—C229—C332 | 16.6 (3) |
C111—C113—H11G | 109.5 | C229—C230—C225 | 122.5 (3) |
C111—C113—H11H | 109.5 | C229—C230—H230 | 118.8 |
H11G—C113—H11H | 109.5 | C225—C230—H230 | 118.8 |
C111—C113—H11I | 109.5 | F21—C231—F20 | 107.2 (3) |
H11G—C113—H11I | 109.5 | F21—C231—F19 | 106.4 (3) |
H11H—C113—H11I | 109.5 | F20—C231—F19 | 105.1 (3) |
C15—C14—C16 | 109.2 (4) | F21—C231—C227 | 113.8 (3) |
C15—C14—P2 | 115.9 (3) | F20—C231—C227 | 113.0 (3) |
C16—C14—P2 | 111.1 (3) | F19—C231—C227 | 110.9 (3) |
C15—C14—H14 | 106.7 | F23—C232—F22 | 107.6 (5) |
C16—C14—H14 | 106.7 | F23—C232—F24 | 105.3 (4) |
P2—C14—H14 | 106.7 | F22—C232—F24 | 106.6 (5) |
C14—C15—H15A | 109.5 | F23—C232—C229 | 114.9 (4) |
C14—C15—H15B | 109.5 | F22—C232—C229 | 111.6 (4) |
H15A—C15—H15B | 109.5 | F24—C232—C229 | 110.4 (4) |
C14—C15—H15C | 109.5 | F123—C332—F122 | 105.8 (6) |
H15A—C15—H15C | 109.5 | F123—C332—F124 | 107.1 (6) |
H15B—C15—H15C | 109.5 | F122—C332—F124 | 106.2 (6) |
C14—C16—H16A | 109.5 | F123—C332—C229 | 115.7 (5) |
C14—C16—H16B | 109.5 | F122—C332—C229 | 109.9 (5) |
H16A—C16—H16B | 109.5 | F124—C332—C229 | 111.6 (5) |
P1—Rh1—P2—C20 | −16.6 (2) | C202—C203—C207—F103 | −97.5 (8) |
B1—Rh1—P2—C20 | 176.50 (19) | C204—C205—C208—F4 | 0.6 (5) |
P11—Rh1—P2—C20 | 9.1 (4) | C206—C205—C208—F4 | −178.0 (3) |
P1—Rh1—P2—C17 | 104.1 (2) | C204—C205—C208—F6 | 121.5 (3) |
B1—Rh1—P2—C17 | −62.79 (17) | C206—C205—C208—F6 | −57.1 (4) |
P11—Rh1—P2—C17 | 129.8 (4) | C204—C205—C208—F5 | −121.0 (3) |
P1—Rh1—P2—C14 | −133.3 (2) | C206—C205—C208—F5 | 60.4 (4) |
B1—Rh1—P2—C14 | 59.80 (17) | C217—B200—C209—C210 | 21.5 (4) |
P11—Rh1—P2—C14 | −107.6 (4) | C201—B200—C209—C210 | −100.5 (3) |
P1—Rh1—B1—N1 | 13.9 (4) | C225—B200—C209—C210 | 137.5 (3) |
P2—Rh1—B1—N1 | −170.6 (4) | C217—B200—C209—C214 | −160.0 (2) |
P11—Rh1—B1—N1 | 3.3 (5) | C201—B200—C209—C214 | 78.0 (3) |
Rh1—B1—N1—C1 | 16.1 (6) | C225—B200—C209—C214 | −44.0 (3) |
Rh1—B1—N1—C2 | 132.3 (5) | C214—C209—C210—C211 | 3.1 (4) |
Rh1—B1—N1—B2 | −102.2 (6) | B200—C209—C210—C211 | −178.4 (3) |
Rh1—B1—N1—B12 | −101.2 (6) | C209—C210—C211—C212 | −0.6 (4) |
C1—N1—B2—N2 | −174.3 (7) | C209—C210—C211—C215 | 178.9 (3) |
C2—N1—B2—N2 | 74.0 (9) | C210—C211—C212—C213 | −2.0 (4) |
B12—N1—B2—N2 | −55 (5) | C215—C211—C212—C213 | 178.4 (3) |
B1—N1—B2—N2 | −49.2 (9) | C211—C212—C213—C214 | 2.1 (4) |
N1—B2—N2—C4 | −93.8 (11) | C211—C212—C213—C216 | 179.5 (2) |
N1—B2—N2—C3 | 147.2 (10) | C212—C213—C214—C209 | 0.6 (4) |
C1—N1—B12—N12 | −167.9 (8) | C216—C213—C214—C209 | −176.9 (2) |
C2—N1—B12—N12 | 75.1 (11) | C210—C209—C214—C213 | −3.1 (4) |
B2—N1—B12—N12 | 129 (5) | B200—C209—C214—C213 | 178.3 (3) |
B1—N1—B12—N12 | −45.1 (10) | C212—C211—C215—F7 | 10.0 (4) |
N1—B12—N12—C104 | −109.5 (12) | C210—C211—C215—F7 | −169.5 (3) |
N1—B12—N12—C103 | 126.5 (12) | C212—C211—C215—F8 | −111.1 (3) |
B1—Rh1—P1—C11 | 175.4 (2) | C210—C211—C215—F8 | 69.3 (4) |
P2—Rh1—P1—C11 | 9.2 (3) | C212—C211—C215—F9 | 131.3 (3) |
P11—Rh1—P1—C11 | −56.9 (8) | C210—C211—C215—F9 | −48.2 (4) |
B1—Rh1—P1—C8 | 54.3 (2) | C214—C213—C216—F112 | −177.8 (9) |
P2—Rh1—P1—C8 | −111.9 (2) | C212—C213—C216—F112 | 4.7 (9) |
P11—Rh1—P1—C8 | −178.0 (9) | C214—C213—C216—F12 | −31.3 (7) |
B1—Rh1—P1—C5 | −65.0 (3) | C212—C213—C216—F12 | 151.2 (7) |
P2—Rh1—P1—C5 | 128.7 (2) | C214—C213—C216—F11 | 90.5 (7) |
P11—Rh1—P1—C5 | 62.6 (8) | C212—C213—C216—F11 | −87.0 (7) |
C11—P1—C5—C7 | 98.3 (7) | C214—C213—C216—F10 | −153.2 (5) |
C8—P1—C5—C7 | −151.4 (6) | C212—C213—C216—F10 | 29.3 (6) |
Rh1—P1—C5—C7 | −26.9 (7) | C214—C213—C216—F110 | 58.5 (8) |
C11—P1—C5—C6 | −29.5 (6) | C212—C213—C216—F110 | −119.0 (8) |
C8—P1—C5—C6 | 80.7 (6) | C214—C213—C216—F111 | −56.4 (7) |
Rh1—P1—C5—C6 | −154.7 (5) | C212—C213—C216—F111 | 126.1 (7) |
C11—P1—C8—C10 | −85.7 (4) | C209—B200—C217—C218 | −151.6 (3) |
C5—P1—C8—C10 | 165.7 (4) | C201—B200—C217—C218 | −32.7 (4) |
Rh1—P1—C8—C10 | 39.9 (4) | C225—B200—C217—C218 | 89.5 (3) |
C11—P1—C8—C9 | 45.0 (4) | C209—B200—C217—C222 | 35.5 (4) |
C5—P1—C8—C9 | −63.5 (5) | C201—B200—C217—C222 | 154.4 (3) |
Rh1—P1—C8—C9 | 170.7 (4) | C225—B200—C217—C222 | −83.4 (3) |
C8—P1—C11—C13 | 57.3 (4) | C222—C217—C218—C219 | −1.2 (4) |
C5—P1—C11—C13 | 166.0 (4) | B200—C217—C218—C219 | −174.7 (3) |
Rh1—P1—C11—C13 | −67.9 (4) | C217—C218—C219—C220 | −0.6 (5) |
C8—P1—C11—C12 | −176.4 (4) | C217—C218—C219—C223 | 179.4 (3) |
C5—P1—C11—C12 | −67.6 (4) | C218—C219—C220—C221 | 1.5 (4) |
Rh1—P1—C11—C12 | 58.4 (4) | C223—C219—C220—C221 | −178.4 (3) |
P1—Rh1—P11—C105 | −102.1 (10) | C219—C220—C221—C222 | −0.6 (4) |
B1—Rh1—P11—C105 | −45.9 (6) | C219—C220—C221—C224 | −179.2 (3) |
P2—Rh1—P11—C105 | 120.2 (6) | C220—C221—C222—C217 | −1.3 (4) |
P1—Rh1—P11—C108 | 17.0 (8) | C224—C221—C222—C217 | 177.3 (2) |
B1—Rh1—P11—C108 | 73.2 (5) | C218—C217—C222—C221 | 2.1 (4) |
P2—Rh1—P11—C108 | −120.7 (5) | B200—C217—C222—C221 | 175.4 (3) |
P1—Rh1—P11—C111 | 135.4 (11) | C218—C219—C223—F13 | −176.3 (7) |
B1—Rh1—P11—C111 | −168.3 (6) | C220—C219—C223—F13 | 3.6 (7) |
P2—Rh1—P11—C111 | −2.2 (7) | C218—C219—C223—F115 | −82.5 (10) |
C108—P11—C105—C107 | −166 (2) | C220—C219—C223—F115 | 97.4 (10) |
C111—P11—C105—C107 | 87 (2) | C218—C219—C223—F114 | 155.9 (8) |
Rh1—P11—C105—C107 | −42 (2) | C220—C219—C223—F114 | −24.2 (9) |
C108—P11—C105—C106 | 67.4 (17) | C218—C219—C223—F113 | 36.7 (8) |
C111—P11—C105—C106 | −39.6 (18) | C220—C219—C223—F113 | −143.3 (8) |
Rh1—P11—C105—C106 | −168.9 (15) | C218—C219—C223—F14 | −57.2 (5) |
C105—P11—C108—C109 | 34.4 (16) | C220—C219—C223—F14 | 122.7 (5) |
C111—P11—C108—C109 | 142.0 (13) | C218—C219—C223—F15 | 60.8 (7) |
Rh1—P11—C108—C109 | −91.4 (13) | C220—C219—C223—F15 | −119.3 (7) |
C105—P11—C108—C110 | 162.5 (13) | C220—C221—C224—F17 | 91.1 (6) |
C111—P11—C108—C110 | −89.8 (13) | C222—C221—C224—F17 | −87.5 (7) |
Rh1—P11—C108—C110 | 36.7 (13) | C220—C221—C224—F118 | 6.8 (9) |
C105—P11—C111—C112 | −62.7 (14) | C222—C221—C224—F118 | −171.7 (9) |
C108—P11—C111—C112 | −170.7 (12) | C220—C221—C224—F117 | −123.1 (7) |
Rh1—P11—C111—C112 | 65.8 (13) | C222—C221—C224—F117 | 58.3 (8) |
C105—P11—C111—C113 | 167.3 (13) | C220—C221—C224—F18 | −145.3 (4) |
C108—P11—C111—C113 | 59.3 (13) | C222—C221—C224—F18 | 36.2 (5) |
Rh1—P11—C111—C113 | −64.2 (13) | C220—C221—C224—F16 | −30.5 (5) |
C20—P2—C14—C15 | 137.9 (3) | C222—C221—C224—F16 | 150.9 (5) |
C17—P2—C14—C15 | 29.3 (3) | C220—C221—C224—F116 | 122.6 (6) |
Rh1—P2—C14—C15 | −98.3 (3) | C222—C221—C224—F116 | −55.9 (7) |
C20—P2—C14—C16 | −96.8 (3) | C217—B200—C225—C226 | −80.6 (3) |
C17—P2—C14—C16 | 154.6 (3) | C209—B200—C225—C226 | 156.6 (2) |
Rh1—P2—C14—C16 | 27.1 (3) | C201—B200—C225—C226 | 39.7 (4) |
C20—P2—C17—C19 | 89.2 (3) | C217—B200—C225—C230 | 93.5 (3) |
C14—P2—C17—C19 | −166.0 (3) | C209—B200—C225—C230 | −29.3 (3) |
Rh1—P2—C17—C19 | −36.2 (3) | C201—B200—C225—C230 | −146.2 (3) |
C20—P2—C17—C18 | −38.7 (3) | C230—C225—C226—C227 | 1.9 (4) |
C14—P2—C17—C18 | 66.1 (3) | B200—C225—C226—C227 | 176.3 (3) |
Rh1—P2—C17—C18 | −164.1 (3) | C225—C226—C227—C228 | 0.4 (4) |
C17—P2—C20—C22 | −65.6 (3) | C225—C226—C227—C231 | −176.5 (3) |
C14—P2—C20—C22 | −173.4 (3) | C226—C227—C228—C229 | −2.2 (5) |
Rh1—P2—C20—C22 | 60.0 (3) | C231—C227—C228—C229 | 174.8 (3) |
C17—P2—C20—C21 | 168.2 (3) | C227—C228—C229—C230 | 1.6 (5) |
C14—P2—C20—C21 | 60.5 (3) | C227—C228—C229—C232 | −170.6 (3) |
Rh1—P2—C20—C21 | −66.2 (3) | C227—C228—C229—C332 | 170.4 (4) |
C217—B200—C201—C206 | 144.5 (3) | C228—C229—C230—C225 | 0.8 (5) |
C209—B200—C201—C206 | −90.9 (3) | C232—C229—C230—C225 | 173.2 (3) |
C225—B200—C201—C206 | 28.1 (4) | C332—C229—C230—C225 | −167.9 (4) |
C217—B200—C201—C202 | −40.0 (4) | C226—C225—C230—C229 | −2.5 (4) |
C209—B200—C201—C202 | 84.6 (3) | B200—C225—C230—C229 | −177.0 (3) |
C225—B200—C201—C202 | −156.4 (3) | C228—C227—C231—F21 | 167.5 (3) |
C206—C201—C202—C203 | −2.7 (4) | C226—C227—C231—F21 | −15.4 (4) |
B200—C201—C202—C203 | −178.6 (3) | C228—C227—C231—F20 | 45.0 (4) |
C201—C202—C203—C204 | 2.9 (5) | C226—C227—C231—F20 | −137.9 (3) |
C201—C202—C203—C207 | −175.9 (3) | C228—C227—C231—F19 | −72.6 (4) |
C202—C203—C204—C205 | −0.8 (5) | C226—C227—C231—F19 | 104.5 (3) |
C207—C203—C204—C205 | 178.0 (3) | C230—C229—C232—F23 | −69.8 (5) |
C203—C204—C205—C206 | −1.2 (5) | C228—C229—C232—F23 | 102.6 (5) |
C203—C204—C205—C208 | −179.8 (3) | C332—C229—C232—F23 | −169.3 (15) |
C202—C201—C206—C205 | 0.7 (4) | C230—C229—C232—F22 | 167.4 (5) |
B200—C201—C206—C205 | 176.4 (3) | C228—C229—C232—F22 | −20.2 (6) |
C204—C205—C206—C201 | 1.3 (5) | C332—C229—C232—F22 | 68.0 (13) |
C208—C205—C206—C201 | 179.9 (3) | C230—C229—C232—F24 | 49.1 (5) |
C204—C203—C207—F102 | −35.8 (9) | C228—C229—C232—F24 | −138.5 (5) |
C202—C203—C207—F102 | 143.0 (8) | C332—C229—C232—F24 | −50.4 (12) |
C204—C203—C207—F2 | 108.8 (5) | C230—C229—C332—F123 | 73.4 (6) |
C202—C203—C207—F2 | −72.3 (5) | C228—C229—C332—F123 | −95.5 (6) |
C204—C203—C207—F101 | −161.4 (10) | C232—C229—C332—F123 | 163.2 (15) |
C202—C203—C207—F101 | 17.4 (10) | C230—C229—C332—F122 | −46.3 (6) |
C204—C203—C207—F1 | −13.8 (6) | C228—C229—C332—F122 | 144.8 (6) |
C202—C203—C207—F1 | 165.0 (5) | C232—C229—C332—F122 | 43.5 (11) |
C204—C203—C207—F3 | −130.3 (4) | C230—C229—C332—F124 | −163.9 (6) |
C202—C203—C207—F3 | 48.5 (4) | C228—C229—C332—F124 | 27.2 (8) |
C204—C203—C207—F103 | 83.7 (8) | C232—C229—C332—F124 | −74.1 (13) |
Experimental details
Crystal data | |
Chemical formula | [RhH2(C9H21P)2(C4H18B2N2)](C32H12BF24) |
Mr | 1404.43 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 12.8309 (2), 14.0813 (2), 19.1638 (3) |
α, β, γ (°) | 73.0175 (6), 76.4127 (5), 86.6877 (6) |
V (Å3) | 3218.56 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.42 |
Crystal size (mm) | 0.22 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.92, 1.0 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24556, 14566, 11987 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.129, 1.02 |
No. of reflections | 14566 |
No. of parameters | 1069 |
No. of restraints | 1142 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.80, −0.69 |
Computer programs: COLLECT (Nonius, 1998), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), publCIF (Westrip, 2010).
Rh1—P1 | 2.3078 (12) | B1—N1 | 1.591 (4) |
Rh1—B1 | 2.316 (4) | B1—H1A | 1.22 (4) |
Rh1—P2 | 2.3259 (7) | B1—H1B | 1.18 (4) |
Rh1—P11 | 2.397 (5) | B1—H1C | 1.12 (4) |
Rh1—H0A | 1.44 (3) | N1—B2 | 1.577 (7) |
Rh1—H0B | 1.44 (3) | N1—B12 | 1.585 (7) |
Rh1—H1A | 1.88 (4) | B2—N2 | 1.611 (7) |
Rh1—H1B | 1.91 (4) | B12—N12 | 1.607 (7) |
P1—Rh1—P2 | 160.86 (4) | H0A—Rh1—H0B | 72.8 (19) |
P2—Rh1—P11 | 153.57 (14) | H1A—Rh1—H1B | 61.1 (16) |
B1—N1—B2—N2 | −49.2 (9) | B1—N1—B12—N12 | −45.1 (10) |
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The transition metal-mediated dehydrogenation and dehydrocoupling of amine-boranes (prototypically H3B.NH3) is an area of significant contemporary interest, having relevance to hydrogen storage and the synthesis of new main group polymeric materials (Staubitz et al., 2010; Alcaraz & Sabo-Etienne, 2010). Despite this interest, details of the intimate mechanisms of these reactions remain scarce. Such details are particularly significant due to the potential to control the kinetics of hydrogen release and the product distributions of the resulting group 13/15 materials (e.g. linear oligomeric, cyclic or polymeric materials).
During the course of our work in the dehydrocoupling of amine-boranes using rhodium and iridium bis-phosphane compounds, we have been engaged in the characterization (solution and solid-state) and reactivity of σ-complexes of BN species implicated in the catalytic cycle of this process, or closely related models [(I)–(XIV) in the scheme; Johnson et al., 2011; Stevens et al., 2011; Alcaraz, Chaplin et al., 2010; Chaplin & Weller, 2010; Douglas et al., 2009, 2008]. The formation of related amine- and amino-borane σ-complexes has also been reported using a range of other metal fragments: {M(CO)5} (M = Cr, Mo, W; Shimoi et al., 1999), {M(H)2(carbene)2}+ (Tang et al., 2010a,b) and {Ru(H)2(PCy3)2} (Alcaraz, Vendier et al., 2010).
As part of our investigation into the use of [Rh(PiPr3)2(C6H5F)][BArF4] (ArF = C6H3(CF3)2) as a catalyst precursor for the dehydrogcoupling of H3B.NMe2H, ultimately affording the dimeric amino-borane [H2BNMe2]2, we have demonstrated the kinetic importance of H3B.NMe2BH2.NMe2H as an intermediate species (Chaplin & Weller, 2010), as have others (Friedrich et al., 2009; Jaska et al., 2003). Due to the high reactivity and dynamic composition of the organometallic species implicated during catalysis, we were only able to characterize a rhodium(I) adduct of H3B.NMe2BH2.NMe2H using the {Rh(PiBu3)2}+ fragment in the solid state [(X); Douglas et al., 2009]. The structure of a corresponding dihydride rhodium(III) adduct remained elusive, although evidence for such a species had been inferred from solution data (Douglas et al., 2009). We report now the structure of such an adduct, [Rh(H)2(η2–H3B.NMe2BH2.NMe2H)(PiPr3)2][BArF4], (XV), which crystallized in parallel with [Rh(H)2(η2–H3B.NMe2H)(PiPr3)2][BArF4] during attempted cystallization of the latter, formed from reaction of [Rh(PiPr3)2(C6H5F)][BArF4] with two equivalents of H3B.NMe2H. The structure of (XV) is important because it represents a rare example of a highly reactive transition metal B–H σ-complex and, crucially, completes the series of well characterized organometallic intermediates in the dehydrocoupling of amine-boranes (see scheme), which together add significantly to our understanding of this complex process.
Complex (XV) crystallizes in the triclinic space group P1; the molecular structure is depicted in Figs. 1 and 2 (cationic portion only), with the atomic numbering schemes. It is best described as having a distorted octahedral RhIII centre, with trans-phosphane and cis-hydride ligands, a formulation that is fully consistent with the solution NMR characterization. In particular, low-frequency resonances at -0.70 (3H) and -19.6 (2H) p.p.m. in the 1H NMR spectrum confirm the presence of borane and hydride ligands, respectively, in the structure. One of the phosphane ligands is disordered and was consequently modelled over two sites, with the minor component (P11, 0.23) containing one isopropyl substituent with an inverted conformation to that seen in the major component (P1, 0.77) (see Fig. 2).
The phosphane ligands are distorted from ideal trans-geometry, with the P1/P11—Rh1—P2 angles contracted significantly from 180° [160.86 (4) and 153.57 (14)°, respectively] in a similar manner to those observed in the related σ-complexes (V) [151.10 (14)°], (VI) [163.65 (7)°] and (VII) [157.05 (3)°]. The hydride ligands were located in a Fourier difference map and refined to give Rh1—H0A and Rh1—H0B distances of 1.44 (3) and 1.44 (3) Å, respectively, typical of hydride ligands and close to those reported in (V), (VI) and (VII) [1.41 (6)–1.50 (3) Å]. Overall, these metrics are consistent with the H3B.NMe2BH2.NMe2H ligand exerting significant steric pressure in the coordination sphere.
The diborazine ligand is partially disordered and was modelled almost equally over two sites from N1 along the B—N—B—N backbone (B2,N2 0.51 and B12,N12 0.49). The components are related to each other by a small torsional twist (Fig. 2). This ligand is bound to the rhodium centre through two Rh—H—B σ-bonds, with Rh1—H1A and Rh1—H1B contacts that are, within error, equivalent [1.88 (4) and 1.91 (4) Å, respectively]. The resulting Rh1···B1 distance is 2.316 (4) Å, markedly longer than those in the reported rhodium(I) analogue (X) [Z' = 2; 2.166 (8) and 2.202 (9) Å]. Such a difference is expected based on the high trans influence of the hydride ligands compared with phosphane ligands and has been noted previously for the rhodium(I)–rhodium(III) pairs (II)/(VII) and (IV)/(V). The Rh1···B1 distance is the smallest in the rhodium(III) bis(isopropylphosphane) σ-complexes (V) [2.386 (15) Å] and (VII) [2.325 (4) Å]. Comparison with (XV), the diborazine (albeit the less substituted H3B.NMeHBH2.NMeH2) in the iridium(III) complex (XIV) is more tightly bound with a shorter Ir···B distance of 2.228 (5) Å.
A notable feature in the structure of (XV) is the conformation of the diborazine ligand, which adopts a gauche conformation with respect to the B—N—B—N backbone [ABS(B—N—B—N) = 49.2 (9) and 45.2 (10)° for the major and minor components, respectively]. In the rhodium(I) complex (X) [Z' = 2; 47.1 (11) and 44.9 (9)°] and in the free state [45.4 (2)°] (Nöth & Thomas, 1999), the diborazine also adopts this conformation. In the case of uncoordinated H3B.NMe2BH2.NMe2H, strong intermolecular hydrogen bonds between the hydridic B—H and protic N—H H atoms (ca 2.3 Å) were cited as important factors in determining its conformation. However, in both (X) and (XV) no such interactions are observed, presumably because strong packing interactions between the cations and anions predominate. Inspection of the packing diagram for (XV) reveals a number of moderately close intermolecular interactions (2.8–3.5 Å, Fig. 3), which could suggest that crystal packing effects could play some role in the adoption of the gauche conformation of the diborazine in this structure. It is interesting to note that, while the less substituted diborazine H3B.NMeHBH2.NMeH2 adopts a gauche conformation in (XIV) [60.0 (4)°], in the free state an anti conformation is found [175.90 (11)°] (Johnson et al., 2011).