Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106013527/rb3006sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013527/rb3006IIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013527/rb3006IIIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013527/rb3006IVsup4.hkl |
CCDC references: 612454; 612455; 612456
For the preparation of each of compounds (II)–(IV), boronic acid (2.7 mmol) was added to a solution of the diolamine [Which diolamine for which compound?] (2.8 mmol) in dry [Diethyl?] ether (10 ml). CaH2 (6 mmol) was added and the reaction was refluxed for 12 h. The CaH2 was filtered off and the ether was removed under reduced pressure, affording the dioxazaborocanes as white foams. Single crystals of compounds (II) and (IV) for X-ray analysis were obtained by dissolving the compounds in a minimal amount of warm diethyl ether and allowing the flask to stand at room temperature overnight. Single crystals of compound (III) for X-ray analysis were obtained similarly, but CDCl3–diethyl ether (1:1) was used as the recrystallization solvent.
For (II) and (III), H atoms were treated as riding, with fixed C—H distances in the range 0.95–1.00 Å, and with Uiso(H) = 1.2Ueq(C). For (IV), H atoms were freely refined with the use of isotropic displacement parameters, yielding a range of C—H distances of 0.93 (3)–1.03 (3) Å. Friedel pairs were merged for the final refinement in all three structures. The absolute configurations of all three compounds were assumed from the synthesis.
Data collection: APEX2 (Bruker, 2004) for (II), (III); SMART (Bruker, 2003) for (IV). Cell refinement: SAINT (Bruker, 2004) for (II), (III); SAINT (Bruker, 2003) for (IV). Data reduction: SAINT (Bruker, 2004) for (II), (III); SAINT (Bruker, 2003) for (IV). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.
C27H30BNO2 | F(000) = 880 |
Mr = 411.33 | Dx = 1.175 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 9196 reflections |
a = 12.0141 (4) Å | θ = 2.4–30.2° |
b = 12.3388 (5) Å | µ = 0.07 mm−1 |
c = 15.6913 (6) Å | T = 90 K |
V = 2326.07 (15) Å3 | Needle, colourless |
Z = 4 | 0.40 × 0.04 × 0.03 mm |
Bruker SMART APEXII diffractometer | 3885 independent reflections |
Radiation source: fine-focus sealed tube | 3493 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 8.3 pixels mm-1 | θmax = 30.3°, θmin = 2.1° |
ω scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | k = −17→17 |
Tmin = 0.990, Tmax = 0.998 | l = −22→22 |
32109 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0633P)2 + 0.2206P] where P = (Fo2 + 2Fc2)/3 |
3885 reflections | (Δ/σ)max < 0.001 |
282 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C27H30BNO2 | V = 2326.07 (15) Å3 |
Mr = 411.33 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 12.0141 (4) Å | µ = 0.07 mm−1 |
b = 12.3388 (5) Å | T = 90 K |
c = 15.6913 (6) Å | 0.40 × 0.04 × 0.03 mm |
Bruker SMART APEXII diffractometer | 3885 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 3493 reflections with I > 2σ(I) |
Tmin = 0.990, Tmax = 0.998 | Rint = 0.030 |
32109 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.26 e Å−3 |
3885 reflections | Δρmin = −0.16 e Å−3 |
282 parameters |
Experimental. Compound II: 97% yield. [α]D25 = 35.0° (c = 4.3, CHCl3); 1H NMR (500 MHz, CCDl3): δ 1.80 (d, J= 7 Hz, 3H), 1.93 (s, 3H), 2.53 (t, J = 11.5 Hz, 1H), 2.72 (t, J = 10.75 Hz, 1H), 2.94 (dd, J = 11, 3.5 Hz, 1H), 3.60 (dd, J = 12.5, 4.5 Hz, 1H), 3.88 (d, J = 14 Hz, 1H), 4.07 (d, J = 14.5 Hz, 1H), 5.23 (dd, J = 10.5, 4 Hz, 2H), 6.34 (q, J = 7, Hz, 1H), 7.29–7.39 (m, 10H), 7.53 (t, J = 7.75 Hz, 4H); 13C NMR (125 MHz, CDCl3): δ 14.43, 15.78, 59.80, 60.25, 66.24, 73.39, 73.75, 125.80, 126.14, 127.79, 127.82, 128.58, 129.17, 129.28, 131.10, 131.55, 133.06, 141.09, 141.58; 11B NMR (80.25 MHz, CDCl3): δ 15.29. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.56682 (9) | 0.52069 (9) | 0.41157 (7) | 0.0277 (2) | |
O2 | 0.65189 (8) | 0.45888 (8) | 0.27993 (7) | 0.0260 (2) | |
N1 | 0.76852 (9) | 0.47946 (9) | 0.40810 (7) | 0.0226 (2) | |
C1 | 0.59091 (11) | 0.43605 (12) | 0.46886 (9) | 0.0245 (3) | |
H1 | 0.5794 | 0.3642 | 0.4406 | 0.029* | |
C2 | 0.71433 (11) | 0.45195 (13) | 0.49076 (9) | 0.0246 (3) | |
H2A | 0.7239 | 0.5115 | 0.5324 | 0.029* | |
H2B | 0.7464 | 0.3848 | 0.5150 | 0.029* | |
C3 | 0.79537 (12) | 0.38110 (12) | 0.35666 (9) | 0.0236 (3) | |
H3A | 0.7550 | 0.3169 | 0.3786 | 0.028* | |
H3B | 0.8763 | 0.3660 | 0.3576 | 0.028* | |
C4 | 0.75664 (12) | 0.40982 (12) | 0.26662 (9) | 0.0236 (3) | |
H4 | 0.8091 | 0.4634 | 0.2406 | 0.028* | |
C5 | 0.52088 (12) | 0.44382 (13) | 0.54868 (10) | 0.0289 (3) | |
C6 | 0.45133 (13) | 0.53172 (17) | 0.56272 (11) | 0.0380 (4) | |
H6 | 0.4446 | 0.5870 | 0.5209 | 0.046* | |
C7 | 0.39109 (14) | 0.5386 (2) | 0.63887 (12) | 0.0491 (5) | |
H7 | 0.3429 | 0.5984 | 0.6482 | 0.059* | |
C8 | 0.40092 (15) | 0.4594 (2) | 0.70042 (11) | 0.0492 (5) | |
H8 | 0.3595 | 0.4648 | 0.7518 | 0.059* | |
C9 | 0.47155 (18) | 0.37193 (18) | 0.68713 (12) | 0.0475 (5) | |
H9 | 0.4790 | 0.3176 | 0.7296 | 0.057* | |
C10 | 0.53137 (18) | 0.36414 (15) | 0.61132 (11) | 0.0413 (4) | |
H10 | 0.5796 | 0.3042 | 0.6022 | 0.050* | |
C11 | 0.86861 (11) | 0.55095 (12) | 0.42022 (9) | 0.0255 (3) | |
H11A | 0.8438 | 0.6214 | 0.4438 | 0.031* | |
H11B | 0.9027 | 0.5651 | 0.3639 | 0.031* | |
C12 | 0.95611 (12) | 0.50354 (11) | 0.47866 (9) | 0.0242 (3) | |
C13 | 0.94934 (13) | 0.51939 (13) | 0.56683 (9) | 0.0291 (3) | |
H13 | 0.8903 | 0.5615 | 0.5897 | 0.035* | |
C14 | 1.02784 (13) | 0.47436 (14) | 0.62123 (10) | 0.0327 (3) | |
H14 | 1.0211 | 0.4844 | 0.6810 | 0.039* | |
C15 | 1.11570 (14) | 0.41504 (13) | 0.58899 (10) | 0.0309 (3) | |
H15 | 1.1694 | 0.3844 | 0.6263 | 0.037* | |
C16 | 1.12496 (13) | 0.40044 (13) | 0.50137 (11) | 0.0300 (3) | |
H16 | 1.1858 | 0.3606 | 0.4787 | 0.036* | |
C17 | 1.04537 (12) | 0.44393 (13) | 0.44684 (9) | 0.0274 (3) | |
H17 | 1.0520 | 0.4328 | 0.3871 | 0.033* | |
C18 | 0.74702 (12) | 0.31199 (12) | 0.20997 (9) | 0.0240 (3) | |
C19 | 0.83359 (14) | 0.28520 (14) | 0.15487 (10) | 0.0309 (3) | |
H19 | 0.8971 | 0.3308 | 0.1509 | 0.037* | |
C20 | 0.82705 (17) | 0.19167 (16) | 0.10555 (10) | 0.0396 (4) | |
H20 | 0.8869 | 0.1727 | 0.0689 | 0.047* | |
C21 | 0.73421 (17) | 0.12659 (15) | 0.10963 (11) | 0.0417 (4) | |
H21 | 0.7300 | 0.0630 | 0.0756 | 0.050* | |
C22 | 0.64688 (15) | 0.15353 (15) | 0.16325 (12) | 0.0377 (4) | |
H22 | 0.5825 | 0.1089 | 0.1655 | 0.045* | |
C23 | 0.65341 (13) | 0.24593 (13) | 0.21375 (10) | 0.0290 (3) | |
H23 | 0.5938 | 0.2639 | 0.2509 | 0.035* | |
C24 | 0.66847 (12) | 0.66011 (12) | 0.32330 (9) | 0.0248 (3) | |
C25 | 0.68680 (14) | 0.68679 (13) | 0.24179 (10) | 0.0310 (3) | |
H25 | 0.6980 | 0.6281 | 0.2035 | 0.037* | |
C26 | 0.69180 (19) | 0.79861 (16) | 0.20332 (13) | 0.0450 (4) | |
H26A | 0.6442 | 0.8013 | 0.1526 | 0.067* | |
H26B | 0.7687 | 0.8153 | 0.1872 | 0.067* | |
H26C | 0.6657 | 0.8519 | 0.2451 | 0.067* | |
C27 | 0.64758 (15) | 0.74444 (13) | 0.39113 (10) | 0.0334 (3) | |
H27A | 0.6599 | 0.8168 | 0.3672 | 0.050* | |
H27B | 0.6987 | 0.7327 | 0.4389 | 0.050* | |
H27C | 0.5706 | 0.7386 | 0.4113 | 0.050* | |
B1 | 0.65489 (13) | 0.53563 (13) | 0.34979 (10) | 0.0235 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0248 (5) | 0.0296 (5) | 0.0287 (5) | 0.0027 (4) | 0.0050 (4) | 0.0070 (4) |
O2 | 0.0241 (4) | 0.0253 (5) | 0.0287 (5) | 0.0039 (4) | −0.0036 (4) | −0.0025 (4) |
N1 | 0.0232 (5) | 0.0229 (5) | 0.0216 (5) | −0.0017 (4) | 0.0025 (4) | 0.0002 (4) |
C1 | 0.0250 (6) | 0.0261 (7) | 0.0224 (6) | −0.0040 (5) | 0.0016 (5) | 0.0026 (5) |
C2 | 0.0262 (6) | 0.0268 (7) | 0.0207 (6) | −0.0046 (5) | 0.0016 (5) | 0.0008 (5) |
C3 | 0.0242 (6) | 0.0224 (6) | 0.0243 (6) | 0.0025 (5) | −0.0009 (5) | 0.0000 (5) |
C4 | 0.0225 (6) | 0.0248 (6) | 0.0235 (6) | 0.0007 (5) | −0.0001 (5) | 0.0016 (5) |
C5 | 0.0256 (6) | 0.0358 (7) | 0.0253 (6) | −0.0118 (6) | 0.0031 (5) | −0.0015 (6) |
C6 | 0.0252 (7) | 0.0602 (11) | 0.0286 (7) | 0.0025 (7) | 0.0008 (6) | 0.0001 (8) |
C7 | 0.0273 (7) | 0.0857 (15) | 0.0341 (8) | 0.0074 (9) | 0.0044 (7) | −0.0069 (10) |
C8 | 0.0306 (8) | 0.0911 (16) | 0.0259 (7) | −0.0222 (10) | 0.0067 (6) | −0.0051 (9) |
C9 | 0.0578 (11) | 0.0555 (11) | 0.0293 (8) | −0.0257 (10) | 0.0073 (8) | 0.0021 (8) |
C10 | 0.0549 (10) | 0.0369 (9) | 0.0320 (8) | −0.0147 (8) | 0.0096 (8) | 0.0020 (7) |
C11 | 0.0247 (6) | 0.0232 (6) | 0.0287 (7) | −0.0045 (5) | 0.0006 (5) | 0.0022 (5) |
C12 | 0.0235 (6) | 0.0241 (6) | 0.0251 (6) | −0.0060 (5) | 0.0012 (5) | −0.0007 (5) |
C13 | 0.0268 (6) | 0.0326 (7) | 0.0278 (7) | −0.0067 (6) | 0.0033 (5) | −0.0095 (6) |
C14 | 0.0334 (7) | 0.0423 (9) | 0.0223 (6) | −0.0125 (7) | −0.0003 (6) | −0.0036 (6) |
C15 | 0.0310 (7) | 0.0317 (7) | 0.0301 (7) | −0.0069 (6) | −0.0068 (6) | 0.0023 (6) |
C16 | 0.0267 (7) | 0.0302 (7) | 0.0330 (7) | −0.0006 (6) | −0.0002 (6) | −0.0025 (6) |
C17 | 0.0267 (6) | 0.0320 (7) | 0.0234 (6) | −0.0030 (6) | 0.0020 (5) | −0.0010 (6) |
C18 | 0.0254 (6) | 0.0274 (6) | 0.0192 (6) | 0.0054 (5) | −0.0023 (5) | 0.0023 (5) |
C19 | 0.0314 (7) | 0.0373 (8) | 0.0241 (7) | 0.0088 (6) | 0.0033 (6) | 0.0072 (6) |
C20 | 0.0504 (10) | 0.0476 (9) | 0.0207 (7) | 0.0224 (8) | 0.0027 (7) | 0.0012 (7) |
C21 | 0.0557 (11) | 0.0404 (9) | 0.0291 (8) | 0.0170 (8) | −0.0170 (8) | −0.0123 (7) |
C22 | 0.0371 (8) | 0.0356 (8) | 0.0403 (9) | 0.0039 (7) | −0.0157 (7) | −0.0086 (7) |
C23 | 0.0268 (6) | 0.0313 (7) | 0.0288 (7) | 0.0025 (6) | −0.0033 (6) | −0.0031 (6) |
C24 | 0.0258 (6) | 0.0231 (6) | 0.0254 (6) | 0.0005 (5) | 0.0014 (5) | −0.0004 (5) |
C25 | 0.0353 (8) | 0.0291 (7) | 0.0286 (7) | −0.0009 (6) | 0.0025 (6) | 0.0040 (6) |
C26 | 0.0588 (11) | 0.0384 (9) | 0.0376 (9) | −0.0052 (9) | 0.0026 (8) | 0.0132 (8) |
C27 | 0.0421 (8) | 0.0273 (7) | 0.0307 (8) | 0.0019 (7) | 0.0031 (7) | −0.0025 (6) |
B1 | 0.0230 (6) | 0.0247 (7) | 0.0227 (7) | 0.0014 (6) | 0.0010 (5) | 0.0022 (6) |
O1—C1 | 1.4080 (17) | C12—C13 | 1.400 (2) |
O1—B1 | 1.4469 (18) | C13—C14 | 1.388 (2) |
O2—C4 | 1.4121 (17) | C13—H13 | 0.9500 |
O2—B1 | 1.4490 (19) | C14—C15 | 1.381 (2) |
N1—C2 | 1.4906 (17) | C14—H14 | 0.9500 |
N1—C3 | 1.4928 (18) | C15—C16 | 1.391 (2) |
N1—C11 | 1.5034 (18) | C15—H15 | 0.9500 |
N1—B1 | 1.7836 (19) | C16—C17 | 1.391 (2) |
C1—C5 | 1.512 (2) | C16—H16 | 0.9500 |
C1—C2 | 1.5346 (19) | C17—H17 | 0.9500 |
C1—H1 | 1.0000 | C18—C23 | 1.390 (2) |
C2—H2A | 0.9900 | C18—C19 | 1.392 (2) |
C2—H2B | 0.9900 | C19—C20 | 1.392 (2) |
C3—C4 | 1.5292 (19) | C19—H19 | 0.9500 |
C3—H3A | 0.9900 | C20—C21 | 1.376 (3) |
C3—H3B | 0.9900 | C20—H20 | 0.9500 |
C4—C18 | 1.503 (2) | C21—C22 | 1.385 (3) |
C4—H4 | 1.0000 | C21—H21 | 0.9500 |
C5—C6 | 1.387 (3) | C22—C23 | 1.391 (2) |
C5—C10 | 1.396 (2) | C22—H22 | 0.9500 |
C6—C7 | 1.400 (2) | C23—H23 | 0.9500 |
C6—H6 | 0.9500 | C24—C25 | 1.339 (2) |
C7—C8 | 1.378 (3) | C24—C27 | 1.510 (2) |
C7—H7 | 0.9500 | C24—B1 | 1.600 (2) |
C8—C9 | 1.389 (3) | C25—C26 | 1.507 (2) |
C8—H8 | 0.9500 | C25—H25 | 0.9500 |
C9—C10 | 1.393 (2) | C26—H26A | 0.9800 |
C9—H9 | 0.9500 | C26—H26B | 0.9800 |
C10—H10 | 0.9500 | C26—H26C | 0.9800 |
C11—C12 | 1.513 (2) | C27—H27A | 0.9800 |
C11—H11A | 0.9900 | C27—H27B | 0.9800 |
C11—H11B | 0.9900 | C27—H27C | 0.9800 |
C12—C17 | 1.393 (2) | ||
C1—O1—B1 | 111.84 (11) | C13—C12—C11 | 120.32 (14) |
C4—O2—B1 | 111.71 (10) | C14—C13—C12 | 120.83 (15) |
C2—N1—C3 | 112.32 (11) | C14—C13—H13 | 119.6 |
C2—N1—C11 | 111.90 (11) | C12—C13—H13 | 119.6 |
C3—N1—C11 | 111.88 (11) | C15—C14—C13 | 120.42 (14) |
C2—N1—B1 | 101.57 (10) | C15—C14—H14 | 119.8 |
C3—N1—B1 | 101.77 (10) | C13—C14—H14 | 119.8 |
C11—N1—B1 | 116.69 (10) | C14—C15—C16 | 119.47 (15) |
O1—C1—C5 | 111.56 (12) | C14—C15—H15 | 120.3 |
O1—C1—C2 | 104.29 (11) | C16—C15—H15 | 120.3 |
C5—C1—C2 | 110.12 (12) | C17—C16—C15 | 120.21 (15) |
O1—C1—H1 | 110.2 | C17—C16—H16 | 119.9 |
C5—C1—H1 | 110.2 | C15—C16—H16 | 119.9 |
C2—C1—H1 | 110.2 | C16—C17—C12 | 120.83 (14) |
N1—C2—C1 | 104.85 (11) | C16—C17—H17 | 119.6 |
N1—C2—H2A | 110.8 | C12—C17—H17 | 119.6 |
C1—C2—H2A | 110.8 | C23—C18—C19 | 119.44 (14) |
N1—C2—H2B | 110.8 | C23—C18—C4 | 120.51 (13) |
C1—C2—H2B | 110.8 | C19—C18—C4 | 120.02 (14) |
H2A—C2—H2B | 108.9 | C20—C19—C18 | 120.00 (16) |
N1—C3—C4 | 104.21 (11) | C20—C19—H19 | 120.0 |
N1—C3—H3A | 110.9 | C18—C19—H19 | 120.0 |
C4—C3—H3A | 110.9 | C21—C20—C19 | 120.26 (16) |
N1—C3—H3B | 110.9 | C21—C20—H20 | 119.9 |
C4—C3—H3B | 110.9 | C19—C20—H20 | 119.9 |
H3A—C3—H3B | 108.9 | C20—C21—C22 | 120.14 (16) |
O2—C4—C18 | 111.30 (11) | C20—C21—H21 | 119.9 |
O2—C4—C3 | 103.52 (11) | C22—C21—H21 | 119.9 |
C18—C4—C3 | 112.56 (11) | C21—C22—C23 | 120.00 (17) |
O2—C4—H4 | 109.8 | C21—C22—H22 | 120.0 |
C18—C4—H4 | 109.8 | C23—C22—H22 | 120.0 |
C3—C4—H4 | 109.8 | C22—C23—C18 | 120.13 (15) |
C6—C5—C10 | 119.57 (15) | C22—C23—H23 | 119.9 |
C6—C5—C1 | 121.09 (14) | C18—C23—H23 | 119.9 |
C10—C5—C1 | 119.24 (15) | C25—C24—C27 | 122.10 (14) |
C5—C6—C7 | 119.63 (19) | C25—C24—B1 | 120.07 (14) |
C5—C6—H6 | 120.2 | C27—C24—B1 | 117.50 (12) |
C7—C6—H6 | 120.2 | C24—C25—C26 | 127.89 (16) |
C8—C7—C6 | 120.7 (2) | C24—C25—H25 | 116.1 |
C8—C7—H7 | 119.6 | C26—C25—H25 | 116.1 |
C6—C7—H7 | 119.6 | C25—C26—H26A | 109.5 |
C7—C8—C9 | 119.85 (16) | C25—C26—H26B | 109.5 |
C7—C8—H8 | 120.1 | H26A—C26—H26B | 109.5 |
C9—C8—H8 | 120.1 | C25—C26—H26C | 109.5 |
C8—C9—C10 | 119.80 (19) | H26A—C26—H26C | 109.5 |
C8—C9—H9 | 120.1 | H26B—C26—H26C | 109.5 |
C10—C9—H9 | 120.1 | C24—C27—H27A | 109.5 |
C9—C10—C5 | 120.40 (19) | C24—C27—H27B | 109.5 |
C9—C10—H10 | 119.8 | H27A—C27—H27B | 109.5 |
C5—C10—H10 | 119.8 | C24—C27—H27C | 109.5 |
N1—C11—C12 | 113.93 (11) | H27A—C27—H27C | 109.5 |
N1—C11—H11A | 108.8 | H27B—C27—H27C | 109.5 |
C12—C11—H11A | 108.8 | O1—B1—O2 | 113.92 (12) |
N1—C11—H11B | 108.8 | O1—B1—C24 | 111.78 (12) |
C12—C11—H11B | 108.8 | O2—B1—C24 | 115.69 (12) |
H11A—C11—H11B | 107.7 | O1—B1—N1 | 99.58 (10) |
C17—C12—C13 | 118.22 (14) | O2—B1—N1 | 98.81 (10) |
C17—C12—C11 | 121.46 (13) | C24—B1—N1 | 115.36 (11) |
B1—O1—C1—C5 | 161.21 (12) | C13—C12—C17—C16 | 0.6 (2) |
B1—O1—C1—C2 | 42.37 (15) | C11—C12—C17—C16 | −179.73 (13) |
C3—N1—C2—C1 | −82.70 (14) | O2—C4—C18—C23 | −34.66 (18) |
C11—N1—C2—C1 | 150.49 (12) | C3—C4—C18—C23 | 81.04 (16) |
B1—N1—C2—C1 | 25.30 (13) | O2—C4—C18—C19 | 147.15 (13) |
O1—C1—C2—N1 | −41.83 (14) | C3—C4—C18—C19 | −97.15 (16) |
C5—C1—C2—N1 | −161.64 (12) | C23—C18—C19—C20 | −1.4 (2) |
C2—N1—C3—C4 | 134.69 (11) | C4—C18—C19—C20 | 176.79 (13) |
C11—N1—C3—C4 | −98.49 (13) | C18—C19—C20—C21 | 1.4 (2) |
B1—N1—C3—C4 | 26.82 (12) | C19—C20—C21—C22 | −0.3 (3) |
B1—O2—C4—C18 | 165.89 (12) | C20—C21—C22—C23 | −0.7 (3) |
B1—O2—C4—C3 | 44.74 (14) | C21—C22—C23—C18 | 0.6 (2) |
N1—C3—C4—O2 | −43.96 (13) | C19—C18—C23—C22 | 0.4 (2) |
N1—C3—C4—C18 | −164.25 (11) | C4—C18—C23—C22 | −177.78 (14) |
O1—C1—C5—C6 | −5.75 (19) | C27—C24—C25—C26 | 0.9 (3) |
C2—C1—C5—C6 | 109.54 (16) | B1—C24—C25—C26 | 174.18 (17) |
O1—C1—C5—C10 | 177.91 (13) | C1—O1—B1—O2 | 79.99 (14) |
C2—C1—C5—C10 | −66.80 (18) | C1—O1—B1—C24 | −146.54 (12) |
C10—C5—C6—C7 | −1.1 (2) | C1—O1—B1—N1 | −24.18 (14) |
C1—C5—C6—C7 | −177.39 (16) | C4—O2—B1—O1 | −130.03 (12) |
C5—C6—C7—C8 | 0.6 (3) | C4—O2—B1—C24 | 98.38 (14) |
C6—C7—C8—C9 | 0.2 (3) | C4—O2—B1—N1 | −25.37 (13) |
C7—C8—C9—C10 | −0.5 (3) | C25—C24—B1—O1 | −138.92 (15) |
C8—C9—C10—C5 | 0.1 (3) | C27—C24—B1—O1 | 34.66 (18) |
C6—C5—C10—C9 | 0.7 (3) | C25—C24—B1—O2 | −6.3 (2) |
C1—C5—C10—C9 | 177.11 (16) | C27—C24—B1—O2 | 167.24 (13) |
C2—N1—C11—C12 | 56.88 (16) | C25—C24—B1—N1 | 108.26 (16) |
C3—N1—C11—C12 | −70.16 (15) | C27—C24—B1—N1 | −78.16 (16) |
B1—N1—C11—C12 | 173.24 (11) | C2—N1—B1—O1 | −2.65 (13) |
N1—C11—C12—C17 | 93.60 (16) | C3—N1—B1—O1 | 113.36 (11) |
N1—C11—C12—C13 | −86.79 (17) | C11—N1—B1—O1 | −124.59 (12) |
C17—C12—C13—C14 | −1.7 (2) | C2—N1—B1—O2 | −118.90 (11) |
C11—C12—C13—C14 | 178.63 (14) | C3—N1—B1—O2 | −2.89 (12) |
C12—C13—C14—C15 | 1.5 (2) | C11—N1—B1—O2 | 119.16 (12) |
C13—C14—C15—C16 | −0.1 (2) | C2—N1—B1—C24 | 117.11 (13) |
C14—C15—C16—C17 | −0.9 (2) | C3—N1—B1—C24 | −126.87 (12) |
C15—C16—C17—C12 | 0.7 (2) | C11—N1—B1—C24 | −4.82 (16) |
C24H32BNO2 | F(000) = 816 |
Mr = 377.32 | Dx = 1.173 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 988 reflections |
a = 10.5916 (14) Å | θ = 2.6–32.0° |
b = 11.3683 (15) Å | µ = 0.07 mm−1 |
c = 17.747 (2) Å | T = 90 K |
V = 2136.8 (5) Å3 | Block, colourless |
Z = 4 | 0.32 × 0.16 × 0.13 mm |
Bruker SMART APEXII diffractometer | 2773 independent reflections |
Radiation source: fine-focus sealed tube | 2576 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 8.3 pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | k = −14→14 |
Tmin = 0.988, Tmax = 0.993 | l = −23→23 |
23473 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)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0415P)2 + 0.4322P] where P = (Fo2 + 2Fc2)/3 |
2773 reflections | (Δ/σ)max < 0.001 |
256 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C24H32BNO2 | V = 2136.8 (5) Å3 |
Mr = 377.32 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.5916 (14) Å | µ = 0.07 mm−1 |
b = 11.3683 (15) Å | T = 90 K |
c = 17.747 (2) Å | 0.32 × 0.16 × 0.13 mm |
Bruker SMART APEXII diffractometer | 2773 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2576 reflections with I > 2σ(I) |
Tmin = 0.988, Tmax = 0.993 | Rint = 0.028 |
23473 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.081 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.27 e Å−3 |
2773 reflections | Δρmin = −0.16 e Å−3 |
256 parameters |
Experimental. Compound III: 72% yield. [α]D25 = 22.5° (c= 4.6, CHCl3); 1H NMR (500 MHz, CCDl3): δ 1.79 (d, J = 7 Hz, 3H), 1.89 (s, 3H), 2.68 (apparent t, J = 11.5 Hz, 1H), 3.23 (dd, J = 11.5 Hz, 1H), 4.01 (d, J = 14 Hz, 1H), 4.08 (d, J = 14.5 Hz, 1H), 4.29 (dd, J = 10.5, 7 Hz, 1H), 4.35 (ap t, J = 7 Hz, 1H), 4.56 (dd, J = 10.5, 8 Hz, 1H), 5.23 (dd, J = 11, 4.5 Hz, 1H), 6.35 (m, J = 6.5 Hz, 1H), 7.16–7.40 (m, 15H);13C NMR (125 MHz, CDCl3): δ 14.54, 15.62, 61.40, 64.98, 67.61, 67.68, 76.39, 125.45, 127.58, 128.46,128.50, 128.89, 129.06, 129.22, 130.35, 130.87, 132.33, 133.67, 134.52, 142.14; 11B NMR (80.25 MHz, CDCl3): δ 15.37. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.40574 (10) | 0.58073 (10) | 0.47798 (6) | 0.0165 (2) | |
O2 | 0.49577 (10) | 0.77688 (10) | 0.47349 (6) | 0.0169 (2) | |
N1 | 0.62204 (12) | 0.60979 (12) | 0.42669 (7) | 0.0144 (3) | |
C1 | 0.40705 (15) | 0.55745 (14) | 0.39932 (8) | 0.0161 (3) | |
H1 | 0.3855 | 0.6305 | 0.3707 | 0.019* | |
C2 | 0.54477 (14) | 0.52282 (14) | 0.38419 (9) | 0.0161 (3) | |
H2A | 0.5617 | 0.4420 | 0.4023 | 0.019* | |
H2B | 0.5638 | 0.5268 | 0.3296 | 0.019* | |
C3 | 0.64364 (15) | 0.72127 (14) | 0.38358 (9) | 0.0170 (3) | |
H3A | 0.5906 | 0.7234 | 0.3377 | 0.020* | |
H3B | 0.7334 | 0.7286 | 0.3687 | 0.020* | |
C4 | 0.60636 (15) | 0.81979 (13) | 0.43787 (9) | 0.0158 (3) | |
H4 | 0.6744 | 0.8304 | 0.4763 | 0.019* | |
C5 | 0.31901 (14) | 0.45915 (14) | 0.37709 (9) | 0.0165 (3) | |
C6 | 0.29435 (15) | 0.36581 (15) | 0.42562 (9) | 0.0185 (3) | |
H6 | 0.3296 | 0.3656 | 0.4748 | 0.022* | |
C7 | 0.21843 (16) | 0.27298 (15) | 0.40248 (10) | 0.0209 (3) | |
H7 | 0.2012 | 0.2100 | 0.4362 | 0.025* | |
C8 | 0.16748 (15) | 0.27166 (15) | 0.33027 (10) | 0.0205 (3) | |
H8 | 0.1154 | 0.2082 | 0.3146 | 0.025* | |
C9 | 0.19321 (15) | 0.36348 (16) | 0.28131 (10) | 0.0212 (3) | |
H9 | 0.1593 | 0.3626 | 0.2318 | 0.025* | |
C10 | 0.26844 (16) | 0.45683 (15) | 0.30443 (9) | 0.0199 (3) | |
H10 | 0.2856 | 0.5195 | 0.2706 | 0.024* | |
C11 | 0.74222 (14) | 0.55748 (15) | 0.45645 (8) | 0.0164 (3) | |
H11A | 0.7211 | 0.5083 | 0.5007 | 0.020* | |
H11B | 0.7967 | 0.6225 | 0.4744 | 0.020* | |
C12 | 0.81928 (15) | 0.48222 (15) | 0.40129 (9) | 0.0183 (3) | |
H12 | 0.7637 | 0.4176 | 0.3823 | 0.022* | |
C13 | 0.92803 (17) | 0.42651 (19) | 0.44524 (10) | 0.0292 (4) | |
H13A | 0.9717 | 0.3694 | 0.4131 | 0.044* | |
H13B | 0.8947 | 0.3865 | 0.4899 | 0.044* | |
H13C | 0.9875 | 0.4879 | 0.4608 | 0.044* | |
C14 | 0.87123 (16) | 0.54906 (16) | 0.33339 (10) | 0.0229 (4) | |
H14A | 0.9329 | 0.4998 | 0.3070 | 0.034* | |
H14B | 0.9123 | 0.6215 | 0.3505 | 0.034* | |
H14C | 0.8018 | 0.5688 | 0.2991 | 0.034* | |
C15 | 0.58197 (15) | 0.93533 (14) | 0.39873 (9) | 0.0171 (3) | |
C16 | 0.67459 (17) | 1.02211 (15) | 0.39844 (9) | 0.0208 (3) | |
H16 | 0.7541 | 1.0072 | 0.4212 | 0.025* | |
C17 | 0.6512 (2) | 1.13097 (16) | 0.36483 (10) | 0.0270 (4) | |
H17 | 0.7149 | 1.1898 | 0.3648 | 0.032* | |
C18 | 0.5353 (2) | 1.15341 (15) | 0.33154 (10) | 0.0284 (4) | |
H18 | 0.5191 | 1.2278 | 0.3092 | 0.034* | |
C19 | 0.44299 (18) | 1.06682 (16) | 0.33100 (10) | 0.0258 (4) | |
H19 | 0.3638 | 1.0818 | 0.3078 | 0.031* | |
C20 | 0.46591 (16) | 0.95779 (16) | 0.36438 (9) | 0.0216 (3) | |
H20 | 0.4024 | 0.8988 | 0.3637 | 0.026* | |
C21 | 0.56116 (14) | 0.63548 (14) | 0.58135 (8) | 0.0162 (3) | |
C22 | 0.60831 (16) | 0.72490 (15) | 0.62136 (9) | 0.0201 (3) | |
H22 | 0.6128 | 0.7989 | 0.5967 | 0.024* | |
C23 | 0.65519 (18) | 0.72065 (17) | 0.70173 (9) | 0.0256 (4) | |
H23A | 0.6081 | 0.7771 | 0.7322 | 0.038* | |
H23B | 0.7453 | 0.7398 | 0.7030 | 0.038* | |
H23C | 0.6426 | 0.6410 | 0.7220 | 0.038* | |
C24 | 0.55077 (16) | 0.51355 (15) | 0.61543 (9) | 0.0208 (3) | |
H24A | 0.6320 | 0.4913 | 0.6378 | 0.031* | |
H24B | 0.5282 | 0.4569 | 0.5760 | 0.031* | |
H24C | 0.4854 | 0.5136 | 0.6545 | 0.031* | |
B1 | 0.51150 (16) | 0.65556 (16) | 0.49695 (10) | 0.0155 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0135 (5) | 0.0199 (5) | 0.0161 (5) | −0.0006 (5) | 0.0021 (4) | −0.0021 (4) |
O2 | 0.0154 (5) | 0.0170 (5) | 0.0183 (5) | 0.0007 (4) | 0.0021 (4) | 0.0007 (4) |
N1 | 0.0128 (6) | 0.0155 (6) | 0.0150 (6) | −0.0003 (5) | 0.0010 (5) | −0.0002 (5) |
C1 | 0.0156 (7) | 0.0174 (7) | 0.0154 (7) | −0.0002 (6) | 0.0015 (6) | −0.0001 (6) |
C2 | 0.0165 (7) | 0.0165 (7) | 0.0154 (7) | −0.0009 (6) | 0.0007 (6) | −0.0025 (6) |
C3 | 0.0180 (7) | 0.0159 (7) | 0.0170 (7) | −0.0006 (6) | 0.0023 (6) | 0.0024 (6) |
C4 | 0.0155 (7) | 0.0164 (7) | 0.0155 (7) | 0.0009 (6) | −0.0001 (6) | 0.0012 (6) |
C5 | 0.0126 (6) | 0.0174 (7) | 0.0195 (7) | 0.0021 (6) | 0.0015 (6) | −0.0019 (6) |
C6 | 0.0169 (7) | 0.0208 (8) | 0.0178 (7) | 0.0008 (7) | −0.0001 (6) | −0.0010 (6) |
C7 | 0.0203 (7) | 0.0184 (7) | 0.0241 (8) | 0.0002 (7) | 0.0027 (7) | 0.0000 (7) |
C8 | 0.0151 (7) | 0.0186 (7) | 0.0278 (8) | 0.0004 (6) | 0.0005 (7) | −0.0067 (7) |
C9 | 0.0185 (7) | 0.0251 (8) | 0.0201 (8) | 0.0036 (7) | −0.0032 (6) | −0.0029 (7) |
C10 | 0.0198 (7) | 0.0214 (8) | 0.0184 (7) | 0.0007 (7) | 0.0003 (6) | 0.0011 (6) |
C11 | 0.0133 (7) | 0.0196 (8) | 0.0163 (7) | 0.0029 (6) | 0.0005 (6) | −0.0008 (6) |
C12 | 0.0141 (7) | 0.0217 (8) | 0.0192 (8) | 0.0012 (6) | 0.0009 (6) | −0.0036 (7) |
C13 | 0.0236 (8) | 0.0395 (10) | 0.0245 (8) | 0.0153 (8) | 0.0024 (7) | −0.0012 (8) |
C14 | 0.0212 (8) | 0.0281 (9) | 0.0195 (7) | 0.0002 (7) | 0.0050 (7) | −0.0038 (7) |
C15 | 0.0212 (8) | 0.0157 (7) | 0.0145 (7) | 0.0023 (6) | 0.0005 (6) | −0.0022 (6) |
C16 | 0.0246 (8) | 0.0201 (8) | 0.0177 (8) | −0.0007 (7) | −0.0010 (6) | −0.0007 (6) |
C17 | 0.0390 (10) | 0.0197 (8) | 0.0222 (8) | −0.0035 (8) | 0.0026 (8) | −0.0017 (7) |
C18 | 0.0486 (11) | 0.0177 (8) | 0.0188 (8) | 0.0100 (8) | 0.0031 (8) | 0.0028 (7) |
C19 | 0.0307 (9) | 0.0288 (9) | 0.0179 (7) | 0.0124 (8) | −0.0009 (7) | 0.0009 (7) |
C20 | 0.0224 (8) | 0.0243 (9) | 0.0180 (7) | 0.0036 (7) | −0.0018 (6) | −0.0006 (7) |
C21 | 0.0148 (7) | 0.0183 (7) | 0.0156 (7) | 0.0031 (6) | 0.0032 (6) | 0.0006 (6) |
C22 | 0.0220 (7) | 0.0212 (8) | 0.0171 (7) | 0.0003 (7) | 0.0022 (6) | 0.0011 (6) |
C23 | 0.0280 (9) | 0.0290 (9) | 0.0198 (8) | −0.0051 (8) | 0.0004 (7) | −0.0025 (7) |
C24 | 0.0237 (8) | 0.0208 (8) | 0.0178 (7) | 0.0012 (7) | 0.0010 (7) | 0.0012 (6) |
B1 | 0.0131 (7) | 0.0174 (8) | 0.0159 (8) | 0.0023 (7) | 0.0027 (6) | −0.0020 (6) |
O1—C1 | 1.4208 (18) | C12—C13 | 1.528 (2) |
O1—B1 | 1.446 (2) | C12—C14 | 1.527 (2) |
O2—C4 | 1.4176 (19) | C12—H12 | 1.0000 |
O2—B1 | 1.450 (2) | C13—H13A | 0.9800 |
N1—C2 | 1.4885 (19) | C13—H13B | 0.9800 |
N1—C3 | 1.498 (2) | C13—H13C | 0.9800 |
N1—C11 | 1.5010 (19) | C14—H14A | 0.9800 |
N1—B1 | 1.788 (2) | C14—H14B | 0.9800 |
C1—C5 | 1.508 (2) | C14—H14C | 0.9800 |
C1—C2 | 1.535 (2) | C15—C16 | 1.391 (2) |
C1—H1 | 1.0000 | C15—C20 | 1.396 (2) |
C2—H2A | 0.9900 | C16—C17 | 1.396 (2) |
C2—H2B | 0.9900 | C16—H16 | 0.9500 |
C3—C4 | 1.529 (2) | C17—C18 | 1.386 (3) |
C3—H3A | 0.9900 | C17—H17 | 0.9500 |
C3—H3B | 0.9900 | C18—C19 | 1.387 (3) |
C4—C15 | 1.508 (2) | C18—H18 | 0.9500 |
C4—H4 | 1.0000 | C19—C20 | 1.395 (2) |
C5—C6 | 1.391 (2) | C19—H19 | 0.9500 |
C5—C10 | 1.397 (2) | C20—H20 | 0.9500 |
C6—C7 | 1.389 (2) | C21—C22 | 1.337 (2) |
C6—H6 | 0.9500 | C21—C24 | 1.516 (2) |
C7—C8 | 1.391 (2) | C21—B1 | 1.604 (2) |
C7—H7 | 0.9500 | C22—C23 | 1.511 (2) |
C8—C9 | 1.385 (2) | C22—H22 | 0.9500 |
C8—H8 | 0.9500 | C23—H23A | 0.9765 |
C9—C10 | 1.389 (2) | C23—H23B | 0.9793 |
C9—H9 | 0.9500 | C23—H23C | 0.9838 |
C10—H10 | 0.9500 | C24—H24A | 0.9800 |
C11—C12 | 1.535 (2) | C24—H24B | 0.9800 |
C11—H11A | 0.9900 | C24—H24C | 0.9800 |
C11—H11B | 0.9900 | ||
C1—O1—B1 | 109.31 (12) | C14—C12—C11 | 114.67 (14) |
C4—O2—B1 | 111.13 (12) | C13—C12—H12 | 108.1 |
C2—N1—C3 | 112.78 (12) | C14—C12—H12 | 108.1 |
C2—N1—C11 | 112.42 (12) | C11—C12—H12 | 108.1 |
C3—N1—C11 | 112.67 (12) | C12—C13—H13A | 109.5 |
C2—N1—B1 | 100.76 (11) | C12—C13—H13B | 109.5 |
C3—N1—B1 | 102.12 (11) | H13A—C13—H13B | 109.5 |
C11—N1—B1 | 115.16 (11) | C12—C13—H13C | 109.5 |
O1—C1—C5 | 112.89 (13) | H13A—C13—H13C | 109.5 |
O1—C1—C2 | 103.24 (12) | H13B—C13—H13C | 109.5 |
C5—C1—C2 | 110.61 (13) | C12—C14—H14A | 109.5 |
O1—C1—H1 | 110.0 | C12—C14—H14B | 109.5 |
C5—C1—H1 | 110.0 | H14A—C14—H14B | 109.5 |
C2—C1—H1 | 110.0 | C12—C14—H14C | 109.5 |
N1—C2—C1 | 105.28 (12) | H14A—C14—H14C | 109.5 |
N1—C2—H2A | 110.7 | H14B—C14—H14C | 109.5 |
C1—C2—H2A | 110.7 | C16—C15—C20 | 119.31 (15) |
N1—C2—H2B | 110.7 | C16—C15—C4 | 119.91 (15) |
C1—C2—H2B | 110.7 | C20—C15—C4 | 120.76 (15) |
H2A—C2—H2B | 108.8 | C15—C16—C17 | 120.35 (17) |
N1—C3—C4 | 104.98 (12) | C15—C16—H16 | 119.8 |
N1—C3—H3A | 110.8 | C17—C16—H16 | 119.8 |
C4—C3—H3A | 110.8 | C18—C17—C16 | 120.15 (17) |
N1—C3—H3B | 110.8 | C18—C17—H17 | 119.9 |
C4—C3—H3B | 110.8 | C16—C17—H17 | 119.9 |
H3A—C3—H3B | 108.8 | C17—C18—C19 | 119.77 (16) |
O2—C4—C15 | 111.32 (13) | C17—C18—H18 | 120.1 |
O2—C4—C3 | 104.02 (12) | C19—C18—H18 | 120.1 |
C15—C4—C3 | 113.08 (12) | C18—C19—C20 | 120.32 (17) |
O2—C4—H4 | 109.4 | C18—C19—H19 | 119.8 |
C15—C4—H4 | 109.4 | C20—C19—H19 | 119.8 |
C3—C4—H4 | 109.4 | C19—C20—C15 | 120.09 (17) |
C6—C5—C10 | 119.02 (15) | C19—C20—H20 | 120.0 |
C6—C5—C1 | 121.29 (14) | C15—C20—H20 | 120.0 |
C10—C5—C1 | 119.52 (15) | C22—C21—C24 | 120.69 (14) |
C7—C6—C5 | 120.35 (15) | C22—C21—B1 | 120.69 (15) |
C7—C6—H6 | 119.8 | C24—C21—B1 | 118.60 (14) |
C5—C6—H6 | 119.8 | C21—C22—C23 | 126.86 (16) |
C6—C7—C8 | 120.35 (16) | C21—C22—H22 | 116.6 |
C6—C7—H7 | 119.8 | C23—C22—H22 | 116.6 |
C8—C7—H7 | 119.8 | C22—C23—H23A | 109.5 |
C9—C8—C7 | 119.58 (16) | C22—C23—H23B | 109.5 |
C9—C8—H8 | 120.2 | H23A—C23—H23B | 109.8 |
C7—C8—H8 | 120.2 | C22—C23—H23C | 109.3 |
C8—C9—C10 | 120.21 (15) | H23A—C23—H23C | 109.4 |
C8—C9—H9 | 119.9 | H23B—C23—H23C | 109.2 |
C10—C9—H9 | 119.9 | C21—C24—H24A | 109.5 |
C9—C10—C5 | 120.48 (16) | C21—C24—H24B | 109.5 |
C9—C10—H10 | 119.8 | H24A—C24—H24B | 109.5 |
C5—C10—H10 | 119.8 | C21—C24—H24C | 109.5 |
N1—C11—C12 | 116.57 (12) | H24A—C24—H24C | 109.5 |
N1—C11—H11A | 108.1 | H24B—C24—H24C | 109.5 |
C12—C11—H11A | 108.1 | O1—B1—O2 | 113.80 (13) |
N1—C11—H11B | 108.1 | O1—B1—C21 | 112.82 (13) |
C12—C11—H11B | 108.1 | O2—B1—C21 | 116.18 (13) |
H11A—C11—H11B | 107.3 | O1—B1—N1 | 100.00 (11) |
C13—C12—C14 | 109.71 (14) | O2—B1—N1 | 98.73 (11) |
C13—C12—C11 | 107.83 (13) | C21—B1—N1 | 113.28 (12) |
B1—O1—C1—C5 | 166.99 (12) | O2—C4—C15—C20 | −34.98 (19) |
B1—O1—C1—C2 | 47.53 (15) | C3—C4—C15—C20 | 81.70 (18) |
C3—N1—C2—C1 | −84.55 (15) | C20—C15—C16—C17 | 0.7 (2) |
C11—N1—C2—C1 | 146.74 (12) | C4—C15—C16—C17 | −177.59 (15) |
B1—N1—C2—C1 | 23.61 (14) | C15—C16—C17—C18 | 0.1 (3) |
O1—C1—C2—N1 | −43.92 (15) | C16—C17—C18—C19 | −0.7 (3) |
C5—C1—C2—N1 | −164.94 (12) | C17—C18—C19—C20 | 0.6 (3) |
C2—N1—C3—C4 | 129.25 (13) | C18—C19—C20—C15 | 0.2 (3) |
C11—N1—C3—C4 | −102.16 (14) | C16—C15—C20—C19 | −0.8 (2) |
B1—N1—C3—C4 | 21.96 (14) | C4—C15—C20—C19 | 177.45 (15) |
B1—O2—C4—C15 | 167.73 (12) | C24—C21—C22—C23 | −0.4 (3) |
B1—O2—C4—C3 | 45.65 (15) | B1—C21—C22—C23 | 178.18 (15) |
N1—C3—C4—O2 | −40.96 (14) | C1—O1—B1—O2 | 74.05 (16) |
N1—C3—C4—C15 | −161.87 (13) | C1—O1—B1—C21 | −150.83 (12) |
O1—C1—C5—C6 | −31.7 (2) | C1—O1—B1—N1 | −30.20 (14) |
C2—C1—C5—C6 | 83.42 (18) | C4—O2—B1—O1 | −134.02 (13) |
O1—C1—C5—C10 | 153.15 (14) | C4—O2—B1—C21 | 92.43 (15) |
C2—C1—C5—C10 | −91.74 (17) | C4—O2—B1—N1 | −28.97 (14) |
C10—C5—C6—C7 | −1.3 (2) | C22—C21—B1—O1 | −146.68 (15) |
C1—C5—C6—C7 | −176.47 (14) | C24—C21—B1—O1 | 31.95 (19) |
C5—C6—C7—C8 | 0.8 (2) | C22—C21—B1—O2 | −12.7 (2) |
C6—C7—C8—C9 | 0.2 (2) | C24—C21—B1—O2 | 165.95 (14) |
C7—C8—C9—C10 | −0.6 (2) | C22—C21—B1—N1 | 100.61 (17) |
C8—C9—C10—C5 | 0.1 (2) | C24—C21—B1—N1 | −80.76 (17) |
C6—C5—C10—C9 | 0.9 (2) | C2—N1—B1—O1 | 2.22 (14) |
C1—C5—C10—C9 | 176.14 (15) | C3—N1—B1—O1 | 118.58 (12) |
C2—N1—C11—C12 | 46.27 (18) | C11—N1—B1—O1 | −118.98 (13) |
C3—N1—C11—C12 | −82.50 (17) | C2—N1—B1—O2 | −113.98 (12) |
B1—N1—C11—C12 | 160.91 (13) | C3—N1—B1—O2 | 2.37 (14) |
N1—C11—C12—C13 | −173.45 (14) | C11—N1—B1—O2 | 124.81 (13) |
N1—C11—C12—C14 | 64.03 (19) | C2—N1—B1—C21 | 122.52 (14) |
O2—C4—C15—C16 | 143.24 (15) | C3—N1—B1—C21 | −121.12 (14) |
C3—C4—C15—C16 | −100.08 (17) | C11—N1—B1—C21 | 1.32 (18) |
C27H30BNO2 | F(000) = 880 |
Mr = 411.33 | Dx = 1.224 Mg m−3 Dm = 0 Mg m−3 Dm measured by not measured |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 7925 reflections |
a = 9.8152 (4) Å | θ = 2.2–30.0° |
b = 22.6374 (9) Å | µ = 0.08 mm−1 |
c = 10.0469 (4) Å | T = 90 K |
β = 90.449 (2)° | Block, colourless |
V = 2232.26 (16) Å3 | 0.34 × 0.27 × 0.17 mm |
Z = 4 |
Make? Model? CCD area-detector diffractometer | 6663 independent reflections |
Radiation source: fine-focus sealed tube | 6078 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ϕ and ω scans | θmax = 30.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −13→13 |
Tmin = 0.982, Tmax = 0.990 | k = −31→31 |
25742 measured reflections | l = −14→14 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | All H-atom parameters refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0652P)2 + 0.2168P] where P = (Fo2 + 2Fc2)/3 |
6663 reflections | (Δ/σ)max = 0.002 |
799 parameters | Δρmax = 0.34 e Å−3 |
1 restraint | Δρmin = −0.20 e Å−3 |
C27H30BNO2 | V = 2232.26 (16) Å3 |
Mr = 411.33 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.8152 (4) Å | µ = 0.08 mm−1 |
b = 22.6374 (9) Å | T = 90 K |
c = 10.0469 (4) Å | 0.34 × 0.27 × 0.17 mm |
β = 90.449 (2)° |
Make? Model? CCD area-detector diffractometer | 6663 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 6078 reflections with I > 2σ(I) |
Tmin = 0.982, Tmax = 0.990 | Rint = 0.029 |
25742 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 1 restraint |
wR(F2) = 0.095 | All H-atom parameters refined |
S = 1.03 | Δρmax = 0.34 e Å−3 |
6663 reflections | Δρmin = −0.20 e Å−3 |
799 parameters |
Experimental. Compound IV: 79% yield. [α]D25 = 67.7° (c = 4.6, CHCl3); 1H NMR (500 MHz, CCDl3): δ 1.98 (ap t, J = 1.5 Hz, 3H), 2.07 (dd, J = 6.5, 1 Hz, 3H), 2.53 (apparent t, J = 11.5 Hz, 1H), 2.75–2.80 (m, 1H), 2.92 (dd, J = 10.5, 3.5 Hz, 1H), 3.65 (dd, J = 12.5, 4.5 Hz, 1H), 4.01 (d, J = 2 Hz, 2H), 5.19 (dd, J = 10.5, 4.5 Hz, 1H), 5.28 (dd, J = 10.5, 3 Hz, 1H), 6.14 (q, J = 7, Hz, 1H), 7.26–7.41 (m, 15H), 7.51 (dd, J = 13.5, 7.5 Hz, 2H; 13C NMR (125 MHz, δ CDCl3): 17.24, 25.77, 59.60, 60.73, 66.46, 72.52, 73.86, 125.75, 126.03, 127.62, 127.72, 127.82, 128.52, 128.61, 129.14, 129.22, 130.99, 133.23, 134.55, 140.68; 11B NMR (80.25 MHz, CDCl3): δ 14.29. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(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. |
x | y | z | Uiso*/Ueq | ||
B1 | 0.84702 (18) | 0.84654 (8) | 0.91169 (17) | 0.0152 (3) | |
C1 | 0.91701 (16) | 0.85668 (7) | 1.13465 (15) | 0.0157 (3) | |
H1 | 0.910 (3) | 0.8133 (11) | 1.162 (2) | 0.024 (6)* | |
N1 | 1.02736 (13) | 0.84304 (6) | 0.92400 (13) | 0.0152 (2) | |
O1 | 0.81385 (11) | 0.87044 (5) | 1.04033 (11) | 0.0170 (2) | |
C2 | 1.05124 (16) | 0.86684 (7) | 1.06084 (16) | 0.0160 (3) | |
H2A | 1.127 (2) | 0.8489 (10) | 1.102 (2) | 0.015 (5)* | |
H2B | 1.066 (2) | 0.9099 (11) | 1.056 (2) | 0.018 (5)* | |
O2 | 0.81905 (12) | 0.78340 (5) | 0.89948 (12) | 0.0180 (2) | |
C3 | 1.05352 (17) | 0.77796 (7) | 0.91582 (17) | 0.0170 (3) | |
H3A | 1.142 (2) | 0.7690 (10) | 0.878 (2) | 0.016 (5)* | |
H3B | 1.056 (2) | 0.7600 (10) | 1.004 (2) | 0.018 (5)* | |
C4 | 0.93052 (16) | 0.75459 (7) | 0.83803 (16) | 0.0166 (3) | |
H4 | 0.936 (2) | 0.7668 (11) | 0.739 (2) | 0.020 (5)* | |
C5 | 0.90884 (17) | 0.89632 (7) | 1.25559 (16) | 0.0176 (3) | |
C6 | 0.79965 (18) | 0.93485 (8) | 1.27311 (17) | 0.0212 (3) | |
H6 | 0.728 (3) | 0.9364 (12) | 1.211 (3) | 0.028 (6)* | |
C7 | 0.7978 (2) | 0.97343 (9) | 1.38152 (19) | 0.0266 (4) | |
H7 | 0.715 (3) | 1.0000 (13) | 1.384 (3) | 0.036 (7)* | |
C8 | 0.9058 (2) | 0.97442 (9) | 1.47134 (18) | 0.0273 (4) | |
H8 | 0.910 (3) | 1.0018 (14) | 1.548 (3) | 0.036 (7)* | |
C9 | 1.0141 (2) | 0.93558 (9) | 1.45604 (18) | 0.0256 (4) | |
H9 | 1.086 (3) | 0.9359 (13) | 1.517 (3) | 0.036 (7)* | |
C10 | 1.01591 (18) | 0.89623 (8) | 1.34859 (17) | 0.0210 (3) | |
H10 | 1.092 (3) | 0.8688 (12) | 1.340 (3) | 0.027 (6)* | |
C11 | 1.10364 (16) | 0.87672 (7) | 0.81873 (16) | 0.0170 (3) | |
H11A | 1.107 (2) | 0.8503 (11) | 0.745 (2) | 0.019 (5)* | |
H11B | 1.047 (2) | 0.9107 (11) | 0.801 (2) | 0.020 (5)* | |
C12 | 1.24407 (16) | 0.89668 (8) | 0.86214 (16) | 0.0180 (3) | |
C13 | 1.26605 (19) | 0.95672 (8) | 0.88707 (18) | 0.0235 (3) | |
H13 | 1.191 (3) | 0.9838 (12) | 0.870 (2) | 0.027 (6)* | |
C14 | 1.3920 (2) | 0.97685 (10) | 0.9331 (2) | 0.0293 (4) | |
H14 | 1.405 (3) | 1.0178 (13) | 0.954 (3) | 0.034 (7)* | |
C15 | 1.4974 (2) | 0.93710 (11) | 0.95455 (19) | 0.0316 (4) | |
H15 | 1.583 (3) | 0.9536 (14) | 0.987 (3) | 0.041 (7)* | |
C16 | 1.47766 (18) | 0.87751 (10) | 0.92829 (19) | 0.0270 (4) | |
H16 | 1.552 (3) | 0.8490 (14) | 0.941 (3) | 0.040 (7)* | |
C17 | 1.35201 (17) | 0.85733 (8) | 0.88164 (17) | 0.0213 (3) | |
H17 | 1.338 (2) | 0.8167 (11) | 0.861 (2) | 0.018 (5)* | |
C18 | 0.91950 (17) | 0.68829 (7) | 0.84175 (17) | 0.0183 (3) | |
C19 | 0.94230 (19) | 0.65537 (8) | 0.72670 (19) | 0.0236 (3) | |
H19 | 0.961 (3) | 0.6763 (12) | 0.647 (3) | 0.032 (7)* | |
C20 | 0.9418 (2) | 0.59371 (8) | 0.7319 (2) | 0.0306 (4) | |
H20 | 0.958 (3) | 0.5701 (13) | 0.652 (3) | 0.033 (7)* | |
C21 | 0.9175 (2) | 0.56509 (9) | 0.8512 (3) | 0.0348 (5) | |
H21 | 0.921 (4) | 0.5212 (17) | 0.850 (4) | 0.064 (10)* | |
C22 | 0.8918 (2) | 0.59782 (9) | 0.9655 (2) | 0.0328 (4) | |
H22 | 0.871 (3) | 0.5799 (14) | 1.049 (3) | 0.047 (8)* | |
C23 | 0.8928 (2) | 0.65925 (8) | 0.96138 (19) | 0.0257 (4) | |
H23 | 0.877 (3) | 0.6835 (12) | 1.041 (3) | 0.032 (7)* | |
C24 | 0.79070 (16) | 0.88559 (7) | 0.78918 (16) | 0.0173 (3) | |
C25 | 0.78499 (17) | 0.94480 (8) | 0.78419 (17) | 0.0192 (3) | |
H25 | 0.744 (2) | 0.9632 (10) | 0.704 (2) | 0.015 (5)* | |
C26 | 0.84002 (19) | 0.98873 (8) | 0.88305 (19) | 0.0227 (3) | |
H26A | 0.879 (3) | 0.9714 (13) | 0.963 (3) | 0.036 (7)* | |
H26B | 0.915 (3) | 1.0120 (15) | 0.847 (3) | 0.048 (8)* | |
H26C | 0.765 (3) | 1.0164 (12) | 0.902 (3) | 0.031 (7)* | |
C27 | 0.7291 (2) | 0.85226 (8) | 0.67250 (18) | 0.0251 (4) | |
H27A | 0.689 (3) | 0.8786 (12) | 0.602 (3) | 0.028 (6)* | |
H27B | 0.797 (3) | 0.8295 (13) | 0.628 (3) | 0.031 (6)* | |
H27C | 0.659 (3) | 0.8238 (12) | 0.708 (3) | 0.032 (7)* | |
B31 | 0.35330 (17) | 0.74185 (8) | 0.35139 (18) | 0.0154 (3) | |
C31 | 0.41925 (16) | 0.73309 (7) | 0.12748 (15) | 0.0157 (3) | |
H31 | 0.410 (2) | 0.7751 (11) | 0.099 (2) | 0.023 (6)* | |
N31 | 0.53157 (13) | 0.74932 (6) | 0.33795 (13) | 0.0148 (2) | |
O31 | 0.31930 (11) | 0.71749 (5) | 0.22239 (11) | 0.0170 (2) | |
C32 | 0.55525 (16) | 0.72547 (7) | 0.20195 (15) | 0.0162 (3) | |
H32A | 0.633 (2) | 0.7435 (10) | 0.159 (2) | 0.016 (5)* | |
H32B | 0.574 (2) | 0.6831 (10) | 0.209 (2) | 0.016 (5)* | |
O32 | 0.31744 (12) | 0.80432 (5) | 0.36315 (12) | 0.0176 (2) | |
C33 | 0.55105 (16) | 0.81486 (7) | 0.34473 (16) | 0.0164 (3) | |
H33A | 0.636 (2) | 0.8252 (10) | 0.389 (2) | 0.018 (5)* | |
H33B | 0.548 (2) | 0.8320 (11) | 0.254 (2) | 0.022 (6)* | |
C34 | 0.42733 (16) | 0.83575 (7) | 0.42324 (16) | 0.0161 (3) | |
H34 | 0.441 (2) | 0.8241 (9) | 0.516 (2) | 0.012 (5)* | |
C35 | 0.41414 (17) | 0.69280 (7) | 0.00726 (16) | 0.0179 (3) | |
C36 | 0.30865 (18) | 0.65227 (8) | −0.01066 (17) | 0.0220 (3) | |
H36 | 0.235 (3) | 0.6523 (12) | 0.050 (3) | 0.030 (6)* | |
C37 | 0.3119 (2) | 0.61239 (9) | −0.11601 (19) | 0.0257 (4) | |
H37 | 0.238 (3) | 0.5846 (11) | −0.127 (2) | 0.025 (6)* | |
C38 | 0.4210 (2) | 0.61215 (9) | −0.20315 (19) | 0.0277 (4) | |
H38 | 0.426 (3) | 0.5852 (11) | −0.274 (3) | 0.027 (6)* | |
C39 | 0.52525 (19) | 0.65323 (10) | −0.18715 (19) | 0.0273 (4) | |
H39 | 0.602 (3) | 0.6521 (12) | −0.248 (3) | 0.031 (6)* | |
C40 | 0.52172 (19) | 0.69395 (9) | −0.08330 (17) | 0.0230 (3) | |
H40 | 0.594 (2) | 0.7209 (11) | −0.073 (2) | 0.020 (5)* | |
C41 | 0.61279 (16) | 0.71731 (7) | 0.44386 (16) | 0.0168 (3) | |
H41A | 0.565 (2) | 0.6819 (11) | 0.466 (2) | 0.019 (5)* | |
H41B | 0.612 (2) | 0.7431 (11) | 0.522 (2) | 0.020 (5)* | |
C42 | 0.75474 (16) | 0.70077 (7) | 0.40167 (16) | 0.0165 (3) | |
C43 | 0.78148 (17) | 0.64198 (7) | 0.36862 (17) | 0.0194 (3) | |
H43 | 0.711 (3) | 0.6138 (11) | 0.377 (2) | 0.024 (6)* | |
C44 | 0.90913 (18) | 0.62481 (9) | 0.32343 (19) | 0.0238 (3) | |
H44 | 0.930 (3) | 0.5832 (13) | 0.302 (3) | 0.033 (7)* | |
C45 | 1.01187 (18) | 0.66639 (9) | 0.30942 (18) | 0.0242 (3) | |
H45 | 1.100 (3) | 0.6564 (14) | 0.273 (3) | 0.041 (7)* | |
C46 | 0.98779 (17) | 0.72500 (9) | 0.34468 (18) | 0.0226 (3) | |
H46 | 1.059 (3) | 0.7546 (12) | 0.343 (3) | 0.030 (6)* | |
C47 | 0.86032 (16) | 0.74196 (8) | 0.39141 (17) | 0.0188 (3) | |
H47 | 0.848 (2) | 0.7834 (12) | 0.416 (2) | 0.021 (5)* | |
C48 | 0.40344 (16) | 0.90129 (7) | 0.41945 (16) | 0.0168 (3) | |
C49 | 0.40198 (17) | 0.93347 (7) | 0.53761 (17) | 0.0191 (3) | |
H49 | 0.422 (2) | 0.9135 (11) | 0.624 (2) | 0.022 (5)* | |
C50 | 0.3770 (2) | 0.99432 (8) | 0.53569 (18) | 0.0223 (3) | |
H50 | 0.378 (2) | 1.0172 (11) | 0.619 (2) | 0.021 (5)* | |
C51 | 0.3546 (2) | 1.02277 (8) | 0.41508 (19) | 0.0239 (3) | |
H51 | 0.332 (3) | 1.0646 (13) | 0.414 (3) | 0.034 (7)* | |
C52 | 0.3573 (2) | 0.99099 (8) | 0.29654 (18) | 0.0237 (3) | |
H52 | 0.336 (2) | 1.0110 (10) | 0.213 (2) | 0.018 (5)* | |
C53 | 0.38071 (18) | 0.93047 (8) | 0.29832 (17) | 0.0205 (3) | |
H53 | 0.381 (3) | 0.9075 (12) | 0.218 (3) | 0.027 (6)* | |
C54 | 0.30553 (16) | 0.70206 (8) | 0.47593 (16) | 0.0178 (3) | |
C55 | 0.29691 (17) | 0.64300 (8) | 0.47741 (17) | 0.0203 (3) | |
H55 | 0.261 (3) | 0.6223 (12) | 0.558 (3) | 0.029 (6)* | |
C56 | 0.3382 (2) | 0.60003 (8) | 0.3718 (2) | 0.0246 (3) | |
H56A | 0.383 (3) | 0.6171 (12) | 0.303 (3) | 0.030 (6)* | |
H56B | 0.399 (3) | 0.5684 (13) | 0.410 (3) | 0.033 (7)* | |
H56C | 0.261 (3) | 0.5766 (15) | 0.338 (3) | 0.051 (9)* | |
C57 | 0.2594 (2) | 0.73447 (9) | 0.60012 (19) | 0.0261 (4) | |
H57A | 0.218 (3) | 0.7096 (14) | 0.665 (3) | 0.042 (8)* | |
H57B | 0.338 (3) | 0.7541 (12) | 0.641 (3) | 0.035 (7)* | |
H57C | 0.201 (3) | 0.7654 (12) | 0.576 (3) | 0.029 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
B1 | 0.0132 (7) | 0.0147 (7) | 0.0178 (7) | −0.0006 (6) | −0.0009 (6) | −0.0005 (6) |
C1 | 0.0150 (6) | 0.0165 (7) | 0.0157 (6) | −0.0004 (5) | 0.0008 (5) | 0.0015 (5) |
N1 | 0.0152 (6) | 0.0142 (6) | 0.0162 (6) | −0.0006 (5) | 0.0017 (5) | −0.0011 (5) |
O1 | 0.0145 (5) | 0.0206 (6) | 0.0161 (5) | 0.0011 (4) | −0.0004 (4) | 0.0000 (4) |
C2 | 0.0141 (6) | 0.0182 (7) | 0.0157 (6) | −0.0020 (5) | 0.0005 (5) | −0.0007 (5) |
O2 | 0.0154 (5) | 0.0153 (5) | 0.0234 (5) | −0.0005 (4) | 0.0015 (4) | −0.0013 (4) |
C3 | 0.0173 (7) | 0.0118 (6) | 0.0219 (7) | 0.0007 (5) | −0.0002 (6) | −0.0008 (6) |
C4 | 0.0163 (7) | 0.0144 (7) | 0.0192 (7) | −0.0001 (5) | 0.0001 (5) | −0.0013 (5) |
C5 | 0.0190 (7) | 0.0184 (7) | 0.0153 (7) | −0.0036 (6) | 0.0025 (5) | 0.0015 (6) |
C6 | 0.0222 (8) | 0.0235 (8) | 0.0180 (7) | 0.0014 (6) | 0.0024 (6) | −0.0003 (6) |
C7 | 0.0315 (9) | 0.0250 (9) | 0.0234 (8) | 0.0016 (7) | 0.0061 (7) | −0.0030 (7) |
C8 | 0.0363 (10) | 0.0263 (9) | 0.0196 (8) | −0.0083 (8) | 0.0062 (7) | −0.0053 (7) |
C9 | 0.0284 (8) | 0.0308 (9) | 0.0176 (7) | −0.0088 (7) | −0.0003 (6) | −0.0003 (7) |
C10 | 0.0206 (7) | 0.0238 (8) | 0.0186 (7) | −0.0029 (6) | −0.0001 (6) | 0.0010 (6) |
C11 | 0.0155 (6) | 0.0179 (7) | 0.0175 (7) | −0.0008 (6) | 0.0012 (5) | 0.0018 (6) |
C12 | 0.0161 (7) | 0.0221 (7) | 0.0160 (7) | −0.0022 (6) | 0.0035 (5) | −0.0001 (6) |
C13 | 0.0216 (8) | 0.0233 (8) | 0.0257 (8) | −0.0049 (7) | 0.0067 (6) | −0.0029 (7) |
C14 | 0.0280 (9) | 0.0330 (10) | 0.0269 (9) | −0.0129 (8) | 0.0073 (7) | −0.0078 (7) |
C15 | 0.0208 (8) | 0.0515 (13) | 0.0225 (8) | −0.0132 (8) | 0.0030 (7) | 0.0006 (8) |
C16 | 0.0161 (7) | 0.0403 (11) | 0.0246 (8) | −0.0020 (7) | 0.0018 (6) | 0.0071 (8) |
C17 | 0.0175 (7) | 0.0256 (8) | 0.0210 (7) | −0.0010 (6) | 0.0040 (6) | 0.0042 (6) |
C18 | 0.0180 (7) | 0.0138 (7) | 0.0229 (8) | −0.0011 (5) | −0.0028 (6) | −0.0010 (6) |
C19 | 0.0238 (8) | 0.0193 (8) | 0.0278 (9) | 0.0011 (6) | −0.0018 (6) | −0.0046 (7) |
C20 | 0.0311 (10) | 0.0181 (8) | 0.0426 (11) | 0.0033 (7) | −0.0066 (8) | −0.0111 (8) |
C21 | 0.0376 (11) | 0.0154 (8) | 0.0510 (13) | −0.0004 (7) | −0.0146 (9) | −0.0001 (8) |
C22 | 0.0410 (11) | 0.0210 (9) | 0.0361 (10) | −0.0067 (8) | −0.0109 (9) | 0.0077 (8) |
C23 | 0.0326 (9) | 0.0183 (8) | 0.0262 (8) | −0.0036 (7) | −0.0042 (7) | 0.0020 (7) |
C24 | 0.0161 (6) | 0.0193 (7) | 0.0164 (7) | 0.0010 (6) | 0.0000 (5) | −0.0017 (5) |
C25 | 0.0177 (7) | 0.0209 (8) | 0.0189 (7) | 0.0015 (6) | 0.0008 (6) | 0.0011 (6) |
C26 | 0.0249 (8) | 0.0165 (7) | 0.0268 (8) | −0.0019 (6) | 0.0003 (7) | 0.0003 (6) |
C27 | 0.0315 (9) | 0.0224 (8) | 0.0212 (8) | 0.0041 (7) | −0.0082 (7) | −0.0055 (7) |
B31 | 0.0123 (7) | 0.0156 (7) | 0.0182 (7) | −0.0006 (6) | 0.0011 (6) | 0.0000 (6) |
C31 | 0.0150 (6) | 0.0164 (7) | 0.0158 (7) | 0.0000 (5) | −0.0002 (5) | −0.0007 (5) |
N31 | 0.0145 (6) | 0.0137 (6) | 0.0162 (6) | 0.0001 (5) | −0.0004 (4) | −0.0007 (5) |
O31 | 0.0149 (5) | 0.0192 (5) | 0.0170 (5) | −0.0020 (4) | 0.0013 (4) | −0.0021 (4) |
C32 | 0.0146 (6) | 0.0186 (7) | 0.0153 (6) | 0.0007 (6) | 0.0004 (5) | −0.0012 (5) |
O32 | 0.0140 (5) | 0.0156 (5) | 0.0231 (6) | −0.0002 (4) | −0.0003 (4) | −0.0025 (4) |
C33 | 0.0158 (7) | 0.0129 (6) | 0.0205 (7) | −0.0005 (5) | 0.0000 (5) | 0.0000 (5) |
C34 | 0.0156 (7) | 0.0135 (7) | 0.0193 (7) | −0.0001 (5) | 0.0004 (5) | −0.0010 (5) |
C35 | 0.0191 (7) | 0.0191 (7) | 0.0153 (7) | 0.0020 (6) | −0.0028 (5) | −0.0009 (6) |
C36 | 0.0222 (8) | 0.0239 (8) | 0.0198 (7) | −0.0021 (6) | −0.0021 (6) | −0.0007 (6) |
C37 | 0.0287 (9) | 0.0251 (9) | 0.0231 (8) | −0.0048 (7) | −0.0059 (7) | −0.0034 (7) |
C38 | 0.0312 (9) | 0.0312 (10) | 0.0207 (8) | 0.0044 (8) | −0.0045 (7) | −0.0082 (7) |
C39 | 0.0244 (8) | 0.0365 (10) | 0.0210 (8) | 0.0018 (7) | 0.0022 (7) | −0.0057 (7) |
C40 | 0.0224 (8) | 0.0270 (8) | 0.0196 (8) | −0.0014 (7) | 0.0007 (6) | −0.0026 (6) |
C41 | 0.0148 (6) | 0.0181 (7) | 0.0174 (7) | −0.0003 (6) | 0.0004 (5) | 0.0019 (6) |
C42 | 0.0146 (6) | 0.0186 (7) | 0.0163 (7) | 0.0007 (6) | −0.0012 (5) | 0.0020 (5) |
C43 | 0.0189 (7) | 0.0162 (7) | 0.0231 (8) | −0.0012 (6) | −0.0010 (6) | 0.0010 (6) |
C44 | 0.0219 (8) | 0.0237 (8) | 0.0257 (8) | 0.0069 (7) | −0.0021 (6) | −0.0029 (7) |
C45 | 0.0162 (7) | 0.0332 (9) | 0.0232 (8) | 0.0067 (7) | −0.0010 (6) | 0.0008 (7) |
C46 | 0.0148 (7) | 0.0284 (9) | 0.0246 (8) | −0.0001 (6) | −0.0008 (6) | 0.0052 (7) |
C47 | 0.0146 (7) | 0.0200 (8) | 0.0217 (7) | 0.0000 (6) | −0.0020 (5) | 0.0017 (6) |
C48 | 0.0163 (7) | 0.0140 (7) | 0.0202 (7) | 0.0006 (5) | 0.0006 (5) | −0.0005 (5) |
C49 | 0.0214 (7) | 0.0160 (7) | 0.0199 (7) | 0.0000 (6) | 0.0015 (6) | −0.0006 (6) |
C50 | 0.0300 (9) | 0.0159 (7) | 0.0210 (8) | 0.0002 (6) | 0.0026 (6) | −0.0027 (6) |
C51 | 0.0313 (9) | 0.0151 (7) | 0.0254 (8) | 0.0027 (7) | 0.0030 (7) | 0.0004 (6) |
C52 | 0.0298 (9) | 0.0200 (8) | 0.0214 (8) | 0.0031 (7) | 0.0004 (6) | 0.0027 (6) |
C53 | 0.0236 (8) | 0.0193 (8) | 0.0186 (7) | 0.0017 (6) | −0.0004 (6) | −0.0020 (6) |
C54 | 0.0154 (6) | 0.0218 (7) | 0.0163 (7) | −0.0024 (6) | 0.0016 (5) | −0.0017 (6) |
C55 | 0.0184 (7) | 0.0219 (8) | 0.0206 (7) | −0.0011 (6) | −0.0008 (6) | 0.0016 (6) |
C56 | 0.0277 (9) | 0.0181 (8) | 0.0281 (9) | 0.0017 (7) | 0.0004 (7) | 0.0008 (7) |
C57 | 0.0321 (9) | 0.0257 (9) | 0.0207 (8) | −0.0041 (8) | 0.0080 (7) | −0.0035 (7) |
B1—O1 | 1.441 (2) | B31—O31 | 1.445 (2) |
B1—O2 | 1.460 (2) | B31—O32 | 1.462 (2) |
B1—C24 | 1.610 (2) | B31—C54 | 1.614 (2) |
B1—N1 | 1.775 (2) | B31—N31 | 1.764 (2) |
C1—O1 | 1.4161 (19) | C31—O31 | 1.4181 (19) |
C1—C5 | 1.513 (2) | C31—C35 | 1.514 (2) |
C1—C2 | 1.534 (2) | C31—C32 | 1.535 (2) |
C1—H1 | 1.02 (2) | C31—H31 | 0.99 (3) |
N1—C2 | 1.493 (2) | N31—C32 | 1.489 (2) |
N1—C3 | 1.498 (2) | N31—C33 | 1.498 (2) |
N1—C11 | 1.508 (2) | N31—C41 | 1.510 (2) |
C2—H2A | 0.94 (2) | C32—H32A | 0.97 (2) |
C2—H2B | 0.99 (2) | C32—H32B | 0.98 (2) |
O2—C4 | 1.4193 (19) | O32—C34 | 1.4226 (19) |
C3—C4 | 1.528 (2) | C33—C34 | 1.528 (2) |
C3—H3A | 0.97 (2) | C33—H33A | 0.97 (2) |
C3—H3B | 0.97 (2) | C33—H33B | 0.99 (2) |
C4—C18 | 1.505 (2) | C34—C48 | 1.503 (2) |
C4—H4 | 1.03 (2) | C34—H34 | 0.98 (2) |
C5—C6 | 1.394 (2) | C35—C36 | 1.394 (2) |
C5—C10 | 1.401 (2) | C35—C40 | 1.399 (2) |
C6—C7 | 1.396 (3) | C36—C37 | 1.392 (2) |
C6—H6 | 0.94 (3) | C36—H36 | 0.95 (3) |
C7—C8 | 1.387 (3) | C37—C38 | 1.388 (3) |
C7—H7 | 1.01 (3) | C37—H37 | 0.97 (3) |
C8—C9 | 1.389 (3) | C38—C39 | 1.391 (3) |
C8—H8 | 0.99 (3) | C38—H38 | 0.94 (3) |
C9—C10 | 1.400 (3) | C39—C40 | 1.393 (3) |
C9—H9 | 0.93 (3) | C39—H39 | 0.97 (3) |
C10—H10 | 0.97 (3) | C40—H40 | 0.94 (3) |
C11—C12 | 1.512 (2) | C41—C42 | 1.507 (2) |
C11—H11A | 0.95 (2) | C41—H41A | 0.96 (2) |
C11—H11B | 0.96 (2) | C41—H41B | 0.98 (2) |
C12—C17 | 1.397 (2) | C42—C43 | 1.397 (2) |
C12—C13 | 1.399 (2) | C42—C47 | 1.398 (2) |
C13—C14 | 1.393 (3) | C43—C44 | 1.391 (2) |
C13—H13 | 0.97 (3) | C43—H43 | 0.94 (3) |
C14—C15 | 1.387 (3) | C44—C45 | 1.387 (3) |
C14—H14 | 0.96 (3) | C44—H44 | 0.99 (3) |
C15—C16 | 1.388 (3) | C45—C46 | 1.394 (3) |
C15—H15 | 0.97 (3) | C45—H45 | 0.97 (3) |
C16—C17 | 1.393 (3) | C46—C47 | 1.394 (2) |
C16—H16 | 0.98 (3) | C46—H46 | 0.97 (3) |
C17—H17 | 0.95 (2) | C47—H47 | 0.98 (3) |
C18—C19 | 1.395 (2) | C48—C49 | 1.393 (2) |
C18—C23 | 1.397 (3) | C48—C53 | 1.401 (2) |
C19—C20 | 1.397 (3) | C49—C50 | 1.399 (2) |
C19—H19 | 0.95 (3) | C49—H49 | 0.99 (2) |
C20—C21 | 1.385 (3) | C50—C51 | 1.388 (3) |
C20—H20 | 0.98 (3) | C50—H50 | 0.99 (2) |
C21—C22 | 1.391 (3) | C51—C52 | 1.392 (3) |
C21—H21 | 0.99 (4) | C51—H51 | 0.97 (3) |
C22—C23 | 1.391 (3) | C52—C53 | 1.389 (2) |
C22—H22 | 0.95 (3) | C52—H52 | 0.97 (2) |
C23—H23 | 0.98 (3) | C53—H53 | 0.96 (3) |
C24—C25 | 1.343 (2) | C54—C55 | 1.340 (2) |
C24—C27 | 1.516 (2) | C54—C57 | 1.519 (2) |
C25—C26 | 1.503 (2) | C55—C56 | 1.498 (3) |
C25—H25 | 0.99 (2) | C55—H55 | 1.00 (3) |
C26—H26A | 0.97 (3) | C56—H56A | 0.91 (3) |
C26—H26B | 0.97 (3) | C56—H56B | 1.00 (3) |
C26—H26C | 0.99 (3) | C56—H56C | 0.98 (3) |
C27—H27A | 1.01 (3) | C57—H57A | 0.95 (3) |
C27—H27B | 0.96 (3) | C57—H57B | 0.98 (3) |
C27—H27C | 1.01 (3) | C57—H57C | 0.94 (3) |
O1—B1—O2 | 113.52 (13) | O31—B31—O32 | 112.79 (14) |
O1—B1—C24 | 113.64 (13) | O31—B31—C54 | 114.57 (13) |
O2—B1—C24 | 114.21 (13) | O32—B31—C54 | 113.92 (13) |
O1—B1—N1 | 100.74 (11) | O31—B31—N31 | 100.96 (11) |
O2—B1—N1 | 98.56 (11) | O32—B31—N31 | 98.80 (11) |
C24—B1—N1 | 114.46 (12) | C54—B31—N31 | 114.02 (12) |
O1—C1—C5 | 111.40 (13) | O31—C31—C35 | 111.58 (13) |
O1—C1—C2 | 104.82 (12) | O31—C31—C32 | 104.35 (12) |
C5—C1—C2 | 110.51 (13) | C35—C31—C32 | 110.15 (13) |
O1—C1—H1 | 109.9 (14) | O31—C31—H31 | 111.7 (14) |
C5—C1—H1 | 110.7 (14) | C35—C31—H31 | 110.3 (14) |
C2—C1—H1 | 109.3 (14) | C32—C31—H31 | 108.6 (14) |
C2—N1—C3 | 112.31 (12) | C32—N31—C33 | 112.34 (12) |
C2—N1—C11 | 112.84 (12) | C32—N31—C41 | 112.79 (12) |
C3—N1—C11 | 111.87 (12) | C33—N31—C41 | 112.14 (12) |
C2—N1—B1 | 101.38 (11) | C32—N31—B31 | 101.39 (11) |
C3—N1—B1 | 102.20 (11) | C33—N31—B31 | 102.58 (11) |
C11—N1—B1 | 115.40 (12) | C41—N31—B31 | 114.75 (11) |
C1—O1—B1 | 110.63 (12) | C31—O31—B31 | 110.61 (12) |
N1—C2—C1 | 105.17 (12) | N31—C32—C31 | 105.37 (12) |
N1—C2—H2A | 111.6 (13) | N31—C32—H32A | 112.5 (13) |
C1—C2—H2A | 113.7 (13) | C31—C32—H32A | 115.0 (13) |
N1—C2—H2B | 109.7 (14) | N31—C32—H32B | 108.8 (13) |
C1—C2—H2B | 107.1 (14) | C31—C32—H32B | 107.9 (13) |
H2A—C2—H2B | 109.5 (19) | H32A—C32—H32B | 107.1 (19) |
C4—O2—B1 | 109.95 (12) | C34—O32—B31 | 109.62 (12) |
N1—C3—C4 | 103.51 (13) | N31—C33—C34 | 103.20 (12) |
N1—C3—H3A | 112.4 (14) | N31—C33—H33A | 111.6 (14) |
C4—C3—H3A | 115.7 (13) | C34—C33—H33A | 112.0 (14) |
N1—C3—H3B | 111.4 (14) | N31—C33—H33B | 110.0 (14) |
C4—C3—H3B | 109.7 (13) | C34—C33—H33B | 109.6 (14) |
H3A—C3—H3B | 104.3 (19) | H33A—C33—H33B | 110 (2) |
O2—C4—C18 | 113.06 (13) | O32—C34—C48 | 111.43 (13) |
O2—C4—C3 | 103.13 (13) | O32—C34—C33 | 103.24 (12) |
C18—C4—C3 | 112.91 (13) | C48—C34—C33 | 114.64 (13) |
O2—C4—H4 | 109.9 (14) | O32—C34—H34 | 111.7 (12) |
C18—C4—H4 | 107.1 (14) | C48—C34—H34 | 108.1 (12) |
C3—C4—H4 | 110.8 (14) | C33—C34—H34 | 107.7 (12) |
C6—C5—C10 | 119.36 (16) | C36—C35—C40 | 119.45 (16) |
C6—C5—C1 | 121.20 (15) | C36—C35—C31 | 121.29 (15) |
C10—C5—C1 | 119.37 (15) | C40—C35—C31 | 119.15 (15) |
C5—C6—C7 | 120.28 (17) | C37—C36—C35 | 120.23 (17) |
C5—C6—H6 | 121.1 (16) | C37—C36—H36 | 120.7 (16) |
C7—C6—H6 | 118.6 (16) | C35—C36—H36 | 119.1 (16) |
C8—C7—C6 | 120.22 (18) | C38—C37—C36 | 120.32 (17) |
C8—C7—H7 | 125.6 (17) | C38—C37—H37 | 120.5 (15) |
C6—C7—H7 | 114.2 (17) | C36—C37—H37 | 119.2 (15) |
C7—C8—C9 | 119.97 (17) | C37—C38—C39 | 119.65 (17) |
C7—C8—H8 | 122.8 (17) | C37—C38—H38 | 121.6 (16) |
C9—C8—H8 | 117.2 (17) | C39—C38—H38 | 118.8 (16) |
C8—C9—C10 | 120.14 (17) | C38—C39—C40 | 120.42 (17) |
C8—C9—H9 | 120.1 (18) | C38—C39—H39 | 118.8 (16) |
C10—C9—H9 | 119.7 (18) | C40—C39—H39 | 120.8 (16) |
C9—C10—C5 | 119.98 (17) | C39—C40—C35 | 119.88 (17) |
C9—C10—H10 | 119.3 (16) | C39—C40—H40 | 119.2 (14) |
C5—C10—H10 | 120.7 (15) | C35—C40—H40 | 120.8 (14) |
N1—C11—C12 | 113.92 (13) | C42—C41—N31 | 113.91 (13) |
N1—C11—H11A | 104.6 (14) | C42—C41—H41A | 108.4 (14) |
C12—C11—H11A | 111.9 (14) | N31—C41—H41A | 107.9 (14) |
N1—C11—H11B | 104.2 (14) | C42—C41—H41B | 112.9 (14) |
C12—C11—H11B | 109.5 (14) | N31—C41—H41B | 105.8 (14) |
H11A—C11—H11B | 112 (2) | H41A—C41—H41B | 107.6 (19) |
C17—C12—C13 | 118.62 (16) | C43—C42—C47 | 118.49 (15) |
C17—C12—C11 | 122.59 (16) | C43—C42—C41 | 118.65 (14) |
C13—C12—C11 | 118.77 (15) | C47—C42—C41 | 122.85 (15) |
C14—C13—C12 | 120.84 (18) | C44—C43—C42 | 121.00 (16) |
C14—C13—H13 | 121.4 (15) | C44—C43—H43 | 120.2 (15) |
C12—C13—H13 | 117.8 (16) | C42—C43—H43 | 118.8 (15) |
C15—C14—C13 | 119.87 (19) | C45—C44—C43 | 120.05 (17) |
C15—C14—H14 | 119.8 (17) | C45—C44—H44 | 118.4 (16) |
C13—C14—H14 | 120.3 (17) | C43—C44—H44 | 121.6 (16) |
C14—C15—C16 | 119.92 (18) | C44—C45—C46 | 119.68 (16) |
C14—C15—H15 | 116.3 (18) | C44—C45—H45 | 122.1 (18) |
C16—C15—H15 | 123.8 (18) | C46—C45—H45 | 118.2 (18) |
C15—C16—C17 | 120.30 (19) | C47—C46—C45 | 120.16 (16) |
C15—C16—H16 | 120.8 (18) | C47—C46—H46 | 117.7 (16) |
C17—C16—H16 | 118.9 (18) | C45—C46—H46 | 122.0 (16) |
C16—C17—C12 | 120.43 (18) | C46—C47—C42 | 120.58 (16) |
C16—C17—H17 | 120.9 (14) | C46—C47—H47 | 117.8 (14) |
C12—C17—H17 | 118.7 (14) | C42—C47—H47 | 121.6 (14) |
C19—C18—C23 | 119.60 (16) | C49—C48—C53 | 119.42 (15) |
C19—C18—C4 | 120.01 (16) | C49—C48—C34 | 119.82 (15) |
C23—C18—C4 | 120.32 (15) | C53—C48—C34 | 120.75 (14) |
C18—C19—C20 | 120.15 (19) | C48—C49—C50 | 120.39 (16) |
C18—C19—H19 | 117.8 (16) | C48—C49—H49 | 120.0 (14) |
C20—C19—H19 | 122.0 (16) | C50—C49—H49 | 119.6 (14) |
C21—C20—C19 | 120.03 (19) | C51—C50—C49 | 119.70 (16) |
C21—C20—H20 | 119.1 (17) | C51—C50—H50 | 120.0 (14) |
C19—C20—H20 | 120.9 (17) | C49—C50—H50 | 120.3 (14) |
C20—C21—C22 | 119.92 (18) | C50—C51—C52 | 120.20 (16) |
C20—C21—H21 | 117 (2) | C50—C51—H51 | 120.0 (16) |
C22—C21—H21 | 123 (2) | C52—C51—H51 | 119.7 (16) |
C23—C22—C21 | 120.4 (2) | C53—C52—C51 | 120.20 (17) |
C23—C22—H22 | 117 (2) | C53—C52—H52 | 120.3 (14) |
C21—C22—H22 | 123 (2) | C51—C52—H52 | 119.4 (14) |
C22—C23—C18 | 119.85 (19) | C52—C53—C48 | 120.09 (16) |
C22—C23—H23 | 122.4 (16) | C52—C53—H53 | 121.6 (15) |
C18—C23—H23 | 117.8 (16) | C48—C53—H53 | 118.3 (15) |
C25—C24—C27 | 116.86 (15) | C55—C54—C57 | 116.97 (15) |
C25—C24—B1 | 126.22 (15) | C55—C54—B31 | 125.74 (15) |
C27—C24—B1 | 116.77 (14) | C57—C54—B31 | 117.21 (15) |
C24—C25—C26 | 128.40 (16) | C54—C55—C56 | 128.53 (16) |
C24—C25—H25 | 117.9 (13) | C54—C55—H55 | 119.9 (15) |
C26—C25—H25 | 113.7 (13) | C56—C55—H55 | 111.6 (15) |
C25—C26—H26A | 114.8 (17) | C55—C56—H56A | 113.3 (17) |
C25—C26—H26B | 112.4 (19) | C55—C56—H56B | 110.9 (16) |
H26A—C26—H26B | 103 (3) | H56A—C56—H56B | 108 (2) |
C25—C26—H26C | 106.5 (16) | C55—C56—H56C | 112 (2) |
H26A—C26—H26C | 112 (2) | H56A—C56—H56C | 110 (3) |
H26B—C26—H26C | 107 (3) | H56B—C56—H56C | 102 (3) |
C24—C27—H27A | 113.8 (15) | C54—C57—H57A | 113.9 (19) |
C24—C27—H27B | 110.8 (16) | C54—C57—H57B | 109.2 (17) |
H27A—C27—H27B | 105 (2) | H57A—C57—H57B | 108 (3) |
C24—C27—H27C | 108.3 (16) | C54—C57—H57C | 109.3 (16) |
H27A—C27—H27C | 111 (2) | H57A—C57—H57C | 111 (3) |
H27B—C27—H27C | 107 (2) | H57B—C57—H57C | 104 (2) |
O1—B1—N1—C2 | −0.20 (14) | O31—B31—N31—C32 | −1.19 (14) |
O2—B1—N1—C2 | −116.27 (12) | O32—B31—N31—C32 | −116.61 (13) |
C24—B1—N1—C2 | 122.13 (14) | C54—B31—N31—C32 | 122.19 (14) |
O1—B1—N1—C3 | 115.88 (13) | O31—B31—N31—C33 | 115.06 (13) |
O2—B1—N1—C3 | −0.18 (14) | O32—B31—N31—C33 | −0.36 (14) |
C24—B1—N1—C3 | −121.79 (14) | C54—B31—N31—C33 | −121.56 (14) |
O1—B1—N1—C11 | −122.47 (13) | O31—B31—N31—C41 | −123.06 (13) |
O2—B1—N1—C11 | 121.46 (13) | O32—B31—N31—C41 | 121.52 (13) |
C24—B1—N1—C11 | −0.15 (18) | C54—B31—N31—C41 | 0.31 (18) |
C5—C1—O1—B1 | 161.91 (13) | C35—C31—O31—B31 | 160.77 (13) |
C2—C1—O1—B1 | 42.37 (16) | C32—C31—O31—B31 | 41.86 (16) |
O2—B1—O1—C1 | 78.80 (16) | O32—B31—O31—C31 | 79.68 (16) |
C24—B1—O1—C1 | −148.45 (13) | C54—B31—O31—C31 | −147.81 (13) |
N1—B1—O1—C1 | −25.55 (15) | N31—B31—O31—C31 | −24.82 (15) |
C3—N1—C2—C1 | −85.37 (15) | C33—N31—C32—C31 | −84.88 (15) |
C11—N1—C2—C1 | 147.05 (13) | C41—N31—C32—C31 | 147.20 (13) |
B1—N1—C2—C1 | 23.03 (14) | B31—N31—C32—C31 | 23.98 (14) |
O1—C1—C2—N1 | −40.46 (15) | O31—C31—C32—N31 | −40.88 (15) |
C5—C1—C2—N1 | −160.59 (13) | C35—C31—C32—N31 | −160.76 (13) |
O1—B1—O2—C4 | −134.78 (14) | O31—B31—O32—C34 | −134.66 (13) |
C24—B1—O2—C4 | 92.75 (15) | C54—B31—O32—C34 | 92.51 (15) |
N1—B1—O2—C4 | −29.04 (14) | N31—B31—O32—C34 | −28.77 (14) |
C2—N1—C3—C4 | 134.01 (13) | C32—N31—C33—C34 | 134.35 (13) |
C11—N1—C3—C4 | −97.90 (14) | C41—N31—C33—C34 | −97.39 (14) |
B1—N1—C3—C4 | 26.14 (14) | B31—N31—C33—C34 | 26.25 (14) |
B1—O2—C4—C18 | 170.74 (13) | B31—O32—C34—C48 | 171.79 (13) |
B1—O2—C4—C3 | 48.49 (16) | B31—O32—C34—C33 | 48.25 (15) |
N1—C3—C4—O2 | −45.64 (15) | N31—C33—C34—O32 | −45.59 (15) |
N1—C3—C4—C18 | −168.00 (13) | N31—C33—C34—C48 | −166.98 (13) |
O1—C1—C5—C6 | 8.0 (2) | O31—C31—C35—C36 | 8.9 (2) |
C2—C1—C5—C6 | 124.15 (16) | C32—C31—C35—C36 | 124.33 (17) |
O1—C1—C5—C10 | −169.05 (14) | O31—C31—C35—C40 | −167.25 (15) |
C2—C1—C5—C10 | −52.95 (19) | C32—C31—C35—C40 | −51.8 (2) |
C10—C5—C6—C7 | 0.7 (3) | C40—C35—C36—C37 | 1.5 (3) |
C1—C5—C6—C7 | −176.36 (16) | C31—C35—C36—C37 | −174.69 (16) |
C5—C6—C7—C8 | 1.1 (3) | C35—C36—C37—C38 | 0.8 (3) |
C6—C7—C8—C9 | −2.1 (3) | C36—C37—C38—C39 | −2.0 (3) |
C7—C8—C9—C10 | 1.3 (3) | C37—C38—C39—C40 | 0.9 (3) |
C8—C9—C10—C5 | 0.5 (3) | C38—C39—C40—C35 | 1.3 (3) |
C6—C5—C10—C9 | −1.6 (2) | C36—C35—C40—C39 | −2.5 (3) |
C1—C5—C10—C9 | 175.60 (15) | C31—C35—C40—C39 | 173.73 (17) |
C2—N1—C11—C12 | 37.64 (18) | C32—N31—C41—C42 | 38.83 (18) |
C3—N1—C11—C12 | −90.17 (16) | C33—N31—C41—C42 | −89.20 (16) |
B1—N1—C11—C12 | 153.55 (13) | B31—N31—C41—C42 | 154.27 (13) |
N1—C11—C12—C17 | 70.3 (2) | N31—C41—C42—C43 | −104.02 (17) |
N1—C11—C12—C13 | −107.99 (17) | N31—C41—C42—C47 | 74.6 (2) |
C17—C12—C13—C14 | −1.4 (3) | C47—C42—C43—C44 | −1.5 (2) |
C11—C12—C13—C14 | 177.05 (16) | C41—C42—C43—C44 | 177.14 (16) |
C12—C13—C14—C15 | 0.1 (3) | C42—C43—C44—C45 | −0.6 (3) |
C13—C14—C15—C16 | 0.9 (3) | C43—C44—C45—C46 | 2.0 (3) |
C14—C15—C16—C17 | −0.6 (3) | C44—C45—C46—C47 | −1.2 (3) |
C15—C16—C17—C12 | −0.7 (3) | C45—C46—C47—C42 | −0.9 (3) |
C13—C12—C17—C16 | 1.7 (2) | C43—C42—C47—C46 | 2.3 (2) |
C11—C12—C17—C16 | −176.68 (15) | C41—C42—C47—C46 | −176.33 (15) |
O2—C4—C18—C19 | 132.61 (16) | O32—C34—C48—C49 | 122.06 (16) |
C3—C4—C18—C19 | −110.79 (18) | C33—C34—C48—C49 | −121.15 (17) |
O2—C4—C18—C23 | −50.4 (2) | O32—C34—C48—C53 | −57.1 (2) |
C3—C4—C18—C23 | 66.2 (2) | C33—C34—C48—C53 | 59.7 (2) |
C23—C18—C19—C20 | −1.6 (3) | C53—C48—C49—C50 | 0.5 (2) |
C4—C18—C19—C20 | 175.39 (17) | C34—C48—C49—C50 | −178.64 (16) |
C18—C19—C20—C21 | 0.6 (3) | C48—C49—C50—C51 | −0.5 (3) |
C19—C20—C21—C22 | 0.8 (3) | C49—C50—C51—C52 | −0.2 (3) |
C20—C21—C22—C23 | −1.2 (3) | C50—C51—C52—C53 | 0.8 (3) |
C21—C22—C23—C18 | 0.2 (3) | C51—C52—C53—C48 | −0.8 (3) |
C19—C18—C23—C22 | 1.2 (3) | C49—C48—C53—C52 | 0.2 (3) |
C4—C18—C23—C22 | −175.77 (18) | C34—C48—C53—C52 | 179.31 (16) |
O1—B1—C24—C25 | 37.3 (2) | O31—B31—C54—C55 | 31.7 (2) |
O2—B1—C24—C25 | 169.71 (16) | O32—B31—C54—C55 | 163.70 (16) |
N1—B1—C24—C25 | −77.7 (2) | N31—B31—C54—C55 | −83.9 (2) |
O1—B1—C24—C27 | −138.07 (16) | O31—B31—C54—C57 | −144.98 (15) |
O2—B1—C24—C27 | −5.7 (2) | O32—B31—C54—C57 | −13.0 (2) |
N1—B1—C24—C27 | 106.92 (16) | N31—B31—C54—C57 | 99.38 (17) |
C27—C24—C25—C26 | −178.45 (17) | C57—C54—C55—C56 | −178.15 (17) |
B1—C24—C25—C26 | 6.2 (3) | B31—C54—C55—C56 | 5.1 (3) |
Experimental details
(II) | (III) | (IV) | |
Crystal data | |||
Chemical formula | C27H30BNO2 | C24H32BNO2 | C27H30BNO2 |
Mr | 411.33 | 377.32 | 411.33 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 | Monoclinic, P21 |
Temperature (K) | 90 | 90 | 90 |
a, b, c (Å) | 12.0141 (4), 12.3388 (5), 15.6913 (6) | 10.5916 (14), 11.3683 (15), 17.747 (2) | 9.8152 (4), 22.6374 (9), 10.0469 (4) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 90.449 (2), 90 |
V (Å3) | 2326.07 (15) | 2136.8 (5) | 2232.26 (16) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.07 | 0.08 |
Crystal size (mm) | 0.40 × 0.04 × 0.03 | 0.32 × 0.16 × 0.13 | 0.34 × 0.27 × 0.17 |
Data collection | |||
Diffractometer | Bruker SMART APEXII diffractometer | Bruker SMART APEXII diffractometer | Make? Model? CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) | Multi-scan (SADABS; Sheldrick, 2004) | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.990, 0.998 | 0.988, 0.993 | 0.982, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32109, 3885, 3493 | 23473, 2773, 2576 | 25742, 6663, 6078 |
Rint | 0.030 | 0.028 | 0.029 |
(sin θ/λ)max (Å−1) | 0.710 | 0.649 | 0.703 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.099, 1.03 | 0.030, 0.081, 1.13 | 0.035, 0.095, 1.03 |
No. of reflections | 3885 | 2773 | 6663 |
No. of parameters | 282 | 256 | 799 |
No. of restraints | 0 | 0 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.26, −0.16 | 0.27, −0.16 | 0.34, −0.20 |
Computer programs: APEX2 (Bruker, 2004), SMART (Bruker, 2003), SAINT (Bruker, 2004), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1994), SHELXL97.
O1—B1 | 1.4469 (18) | N1—C11 | 1.5034 (18) |
O2—B1 | 1.4490 (19) | N1—B1 | 1.7836 (19) |
N1—C2 | 1.4906 (17) | C24—B1 | 1.600 (2) |
N1—C3 | 1.4928 (18) |
O1—B1 | 1.446 (2) | N1—C11 | 1.5010 (19) |
O2—B1 | 1.450 (2) | N1—B1 | 1.788 (2) |
N1—C2 | 1.4885 (19) | C21—B1 | 1.604 (2) |
N1—C3 | 1.498 (2) |
B1—O1 | 1.441 (2) | B31—O31 | 1.445 (2) |
B1—O2 | 1.460 (2) | B31—O32 | 1.462 (2) |
B1—C24 | 1.610 (2) | B31—C54 | 1.614 (2) |
B1—N1 | 1.775 (2) | B31—N31 | 1.764 (2) |
N1—C2 | 1.493 (2) | N31—C32 | 1.489 (2) |
N1—C3 | 1.498 (2) | N31—C33 | 1.498 (2) |
N1—C11 | 1.508 (2) | N31—C41 | 1.510 (2) |
Enantiomerically pure organoboron compounds are versatile synthetic intermediates that can be transformed into numerous functionalities without loss of optical purity (Brown & Singaram, 1987, 1988). Different methods for their synthesis therefore continue to be developed. Vinyl boronates containing a chiral auxiliary via attachment to the boron group are potentially useful starting materials for the production of these compounds. Such vinyl boronates have been used to control the absolute stereochemistry of cyclopropanations (Imai et al., 1990; Pietruszka & Widenmayer, 1997), Diels–Alder reactions (Bonk & Avery, 1997) and dipolar cycloadditions (Marsden et al., 1998, 2000). We recently reported a novel method for the synthesis of chiral organoboron compounds via asymmetric hydrogenation of vinyl oxazaborolidines under ambient conditions (Gamsey et al., 2005). However, although relatively easy to prepare, these chiral vinyl oxazaborolidines have a few drawbacks in terms of their utility in asymmetric reactions. For example, apart from being hydrolytically unstable, the prochiral olefin is somewhat distal from the chiral ligand, due to the planarity of the boronate group. We anticipated that both these problems could be ameliorated through the use of vinyl dioxazaborocanes. Since dioxazaborocanes are stable to air and water, their preparation, isolation, storage and handling are straightforward. Most importantly, the tetrahedral geometry of the B atom should exert more sterochemical influence in asymmetric reactions (Seebach et al., 1996). Marsden et al. (2000) have synthesized vinyl dioxazaborocanes from trans-disubstituted alkenylboronic acids. We report here the synthesis and X-ray structures of three new vinyl dioxazaborocanes, (II)–(IV), derived from α-substituted alkenylboronic acids. Diolamines (Ia) and (Ib) were synthesized from either benzylamine or isobutylamine and two equivalents of (R)-(+)-styrene oxide, according to previously published procedures (Trost et al., 1992; Sundararajan & Manickam, 1997).
The compounds in this report were synthesized as shown in the scheme. The structural results confirm that they are chiral. Compounds (II), (III) and (IV) all crystallize with no molecules of solvation and no unusual intermolecular contacts. Their structures are depicted in Figs. 1, 2 and 3, respectively. Compound (IV) has two molecules in the asymmetric unit which differ slightly in the dihedral angles of the phenyl rings. In addition, the two N—B distances differ by five s.u.s for no apparent reason.
In all three compounds, each of the dioxazaborocane rings is in a chair-like conformation. The most surprising structural feature is the length of the N—B donor–acceptor bonds, which are significantly longer than those in the previously reported structures with the same dioxazaborocane ring size and similar derivatization (Rettig & Trotter, 1975; Caron & Hawkins, 1998; Doidge-Harrison et al., 1998; Thadani et al., 2001a,b, 2002; Sopková-de Oliveira Santos et al., 2004). In this set of eight related molecules, the average N—B bond length is 1.667[11] Å, whereas it is 1.778[8] Å in the four independent molecules in this study (the average deviations from the mean are given in square brackets).
The individual bond distances involving N and B are presented in Tables 1–3 for compounds (II), (III) and (IV), respectively. In seven of the previous structures, the N atom is bonded to H, and in the eighth it is bonded to methyl. It has already been noted (Sopková-de Oliveira Santos et al., 2004) that the N—B bond is lengthened [1.696 (7) Å] in the methyl derivative. However, the lengthening is far greater in (II), (III) and (IV), in which the N atom is bonded to either benzyl or iBu groups. Thus, the bulkier substituent appears to have an impact on the basicity of the N atom. In fact, an examination of the degree of pyramidalization of both the N and B atoms in this study shows that they are flattened relative to the other eight similar molecules. Using the program POAV1 (Haddon, 1999), the pyramidalization angles at N and B in this study have averages of 16.4 and 13.6°, respectively (the angle for sp2 is 0° and for sp3 is 19.5°). Average values for the other eight structures are 17.4 and 15.6° for N and B, respectively. These results suggest a loss of p character in the lone-pair orbital used by N and a weaker dative bond, in agreement with the increased bond length.