Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010443/cf6090sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010443/cf6090Isup2.hkl |
CCDC reference: 170890
The title compound, (I), was synthesized by treatment of phenylboronic acid (0.52 g, 4.27 mmol), dissolved in a minimum amount of methanol (ca 1 ml), with a 5.0 M solution of hydrofluoric acid (2.65 ml, 13.25 mmol), added dropwise with vigorous stirring over a period of 1 min at room temperature. The reaction mixture was then cooled to 273 K, and a 1.54 M solution of tetra-n-butylammonium hydroxide (2.76 ml, 4.27 mmol) was added dropwise over a period of 5 min. The reaction mixture was then warmed to room temperature and stirred for another hour. Dichloromethane (10 ml) was added to dilute the biphasic reaction mixture, the layers were separated, and the aqueous layer was further extracted with dichloromethane (3 × 10 ml). The combined organic layers were dried (MgSO4), filtered and concentrated in vacuo to afford the pale yellow crystalline solid (I). Subsequent recrystallization from ethyl acetate and hexanes yielded the desired crystals.
H atoms were included in calculated positions with C—H distances ranging from 0.95 to 0.99 Å.
Data collection: COLLECT (Nonius, 1997-2001); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL (Sheldrick 1999); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. View of (I) showing the atom-labelling scheme. Ellipsoids are at the 50% probability level. |
C16H36N+·C6H5BF3− | Dx = 1.087 Mg m−3 |
Mr = 387.37 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbcn | Cell parameters from 20559 reflections |
a = 13.5626 (6) Å | θ = 2.6–25.4° |
b = 17.1534 (7) Å | µ = 0.08 mm−1 |
c = 20.3567 (7) Å | T = 150 K |
V = 4735.9 (3) Å3 | Needle, colourless |
Z = 8 | 0.40 × 0.35 × 0.34 mm |
F(000) = 1696 |
Nonius KappaCCD diffractometer | 4341 independent reflections |
Radiation source: fine-focus sealed tube | 2858 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
Detector resolution: 9 pixels mm-1 | θmax = 25.4°, θmin = 2.6° |
ϕ scans, and ω scans with ϕ offsets | h = −16→16 |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | k = −20→20 |
Tmin = 0.970, Tmax = 0.974 | l = −24→24 |
20559 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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0564P)2 + 1.1252P] where P = (Fo2 + 2Fc2)/3 |
4341 reflections | (Δ/σ)max = 0.002 |
248 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C16H36N+·C6H5BF3− | V = 4735.9 (3) Å3 |
Mr = 387.37 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 13.5626 (6) Å | µ = 0.08 mm−1 |
b = 17.1534 (7) Å | T = 150 K |
c = 20.3567 (7) Å | 0.40 × 0.35 × 0.34 mm |
Nonius KappaCCD diffractometer | 4341 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2858 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.974 | Rint = 0.029 |
20559 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.19 e Å−3 |
4341 reflections | Δρmin = −0.19 e Å−3 |
248 parameters |
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 | ||
F1 | 0.59931 (8) | 0.57296 (6) | 0.92620 (5) | 0.0474 (3) | |
F2 | 0.75843 (9) | 0.59224 (6) | 0.95963 (5) | 0.0508 (3) | |
F3 | 0.65065 (8) | 0.69422 (6) | 0.95535 (5) | 0.0415 (3) | |
C1 | 0.71260 (14) | 0.64185 (10) | 0.84841 (9) | 0.0343 (5) | |
C2 | 0.64272 (17) | 0.64701 (12) | 0.79801 (10) | 0.0477 (6) | |
H2A | 0.5755 | 0.6374 | 0.8083 | 0.057* | |
C3 | 0.6668 (2) | 0.66524 (14) | 0.73437 (11) | 0.0594 (7) | |
H3A | 0.6169 | 0.6673 | 0.7017 | 0.071* | |
C4 | 0.7628 (2) | 0.68042 (13) | 0.71811 (11) | 0.0582 (7) | |
H4A | 0.7794 | 0.6948 | 0.6744 | 0.070* | |
C5 | 0.83502 (18) | 0.67485 (13) | 0.76501 (12) | 0.0558 (6) | |
H5A | 0.9019 | 0.6845 | 0.7538 | 0.067* | |
C6 | 0.80956 (16) | 0.65481 (11) | 0.82970 (10) | 0.0445 (5) | |
H6A | 0.8603 | 0.6500 | 0.8616 | 0.053* | |
B1 | 0.68074 (17) | 0.62465 (13) | 0.92269 (11) | 0.0370 (5) | |
N1 | 0.65083 (11) | 0.35374 (8) | 0.95923 (7) | 0.0317 (4) | |
C7 | 0.55031 (14) | 0.39006 (11) | 0.94591 (9) | 0.0352 (5) | |
H7A | 0.5171 | 0.3986 | 0.9886 | 0.042* | |
H7B | 0.5609 | 0.4419 | 0.9257 | 0.042* | |
C8 | 0.48082 (15) | 0.34400 (12) | 0.90189 (11) | 0.0488 (6) | |
H8A | 0.4598 | 0.2958 | 0.9247 | 0.059* | |
H8B | 0.5156 | 0.3288 | 0.8611 | 0.059* | |
C9 | 0.39061 (15) | 0.39282 (14) | 0.88469 (11) | 0.0522 (6) | |
H9A | 0.3419 | 0.3591 | 0.8623 | 0.063* | |
H9B | 0.3601 | 0.4117 | 0.9259 | 0.063* | |
C10 | 0.41242 (19) | 0.46196 (15) | 0.84130 (12) | 0.0707 (7) | |
H10A | 0.3506 | 0.4881 | 0.8297 | 0.106* | |
H10B | 0.4455 | 0.4442 | 0.8012 | 0.106* | |
H10C | 0.4553 | 0.4985 | 0.8648 | 0.106* | |
C11 | 0.64050 (15) | 0.27316 (10) | 0.98920 (9) | 0.0362 (5) | |
H11A | 0.6035 | 0.2400 | 0.9580 | 0.043* | |
H11B | 0.7072 | 0.2504 | 0.9938 | 0.043* | |
C12 | 0.58977 (14) | 0.26878 (11) | 1.05540 (9) | 0.0376 (5) | |
H12A | 0.5254 | 0.2959 | 1.0532 | 0.045* | |
H12B | 0.6307 | 0.2952 | 1.0889 | 0.045* | |
C13 | 0.57400 (17) | 0.18434 (12) | 1.07489 (11) | 0.0522 (6) | |
H13A | 0.5366 | 0.1578 | 1.0396 | 0.063* | |
H13B | 0.6390 | 0.1584 | 1.0785 | 0.063* | |
C14 | 0.51968 (19) | 0.17450 (13) | 1.13854 (11) | 0.0595 (7) | |
H14A | 0.5085 | 0.1189 | 1.1468 | 0.089* | |
H14B | 0.4562 | 0.2016 | 1.1360 | 0.089* | |
H14C | 0.5589 | 0.1966 | 1.1744 | 0.089* | |
C15 | 0.70366 (14) | 0.40930 (10) | 1.00524 (9) | 0.0330 (4) | |
H15A | 0.6640 | 0.4143 | 1.0458 | 0.040* | |
H15B | 0.7058 | 0.4613 | 0.9842 | 0.040* | |
C16 | 0.80804 (14) | 0.38684 (12) | 1.02447 (9) | 0.0387 (5) | |
H16A | 0.8502 | 0.3848 | 0.9848 | 0.046* | |
H16B | 0.8079 | 0.3345 | 1.0450 | 0.046* | |
C17 | 0.84916 (16) | 0.44636 (12) | 1.07262 (10) | 0.0473 (5) | |
H17A | 0.8059 | 0.4486 | 1.1117 | 0.057* | |
H17B | 0.8486 | 0.4985 | 1.0517 | 0.057* | |
C18 | 0.95382 (17) | 0.42737 (15) | 1.09446 (12) | 0.0637 (7) | |
H18A | 0.9754 | 0.4656 | 1.1272 | 0.095* | |
H18B | 0.9981 | 0.4292 | 1.0564 | 0.095* | |
H18C | 0.9554 | 0.3751 | 1.1138 | 0.095* | |
C19 | 0.70862 (15) | 0.34332 (10) | 0.89591 (9) | 0.0349 (5) | |
H19A | 0.7698 | 0.3144 | 0.9064 | 0.042* | |
H19B | 0.6691 | 0.3101 | 0.8661 | 0.042* | |
C20 | 0.73718 (15) | 0.41645 (11) | 0.85871 (9) | 0.0383 (5) | |
H20A | 0.7891 | 0.4449 | 0.8831 | 0.046* | |
H20B | 0.6792 | 0.4511 | 0.8543 | 0.046* | |
C21 | 0.77516 (15) | 0.39356 (11) | 0.79091 (9) | 0.0407 (5) | |
H21A | 0.8233 | 0.3505 | 0.7956 | 0.049* | |
H21B | 0.7194 | 0.3741 | 0.7642 | 0.049* | |
C22 | 0.82409 (17) | 0.46097 (12) | 0.75513 (10) | 0.0477 (6) | |
H22A | 0.8425 | 0.4444 | 0.7107 | 0.072* | |
H22B | 0.8833 | 0.4771 | 0.7792 | 0.072* | |
H22C | 0.7780 | 0.5049 | 0.7525 | 0.072* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0499 (7) | 0.0383 (6) | 0.0540 (7) | −0.0113 (6) | 0.0078 (6) | −0.0029 (5) |
F2 | 0.0560 (8) | 0.0495 (7) | 0.0470 (7) | 0.0081 (6) | −0.0111 (6) | 0.0052 (5) |
F3 | 0.0443 (7) | 0.0352 (6) | 0.0450 (6) | −0.0030 (5) | 0.0054 (5) | −0.0075 (5) |
C1 | 0.0343 (12) | 0.0256 (10) | 0.0430 (11) | 0.0018 (9) | −0.0019 (9) | −0.0051 (8) |
C2 | 0.0443 (13) | 0.0527 (13) | 0.0460 (12) | 0.0073 (11) | −0.0022 (11) | 0.0017 (10) |
C3 | 0.0674 (18) | 0.0640 (16) | 0.0468 (14) | 0.0106 (13) | −0.0039 (13) | 0.0071 (11) |
C4 | 0.082 (2) | 0.0487 (14) | 0.0439 (13) | −0.0030 (13) | 0.0106 (14) | −0.0008 (11) |
C5 | 0.0507 (15) | 0.0514 (14) | 0.0654 (16) | −0.0117 (11) | 0.0222 (13) | −0.0180 (12) |
C6 | 0.0390 (13) | 0.0423 (12) | 0.0522 (13) | −0.0021 (10) | 0.0016 (11) | −0.0150 (10) |
B1 | 0.0363 (13) | 0.0321 (12) | 0.0426 (12) | −0.0013 (11) | −0.0024 (11) | −0.0022 (10) |
N1 | 0.0345 (9) | 0.0292 (8) | 0.0313 (8) | 0.0017 (7) | 0.0005 (7) | −0.0029 (6) |
C7 | 0.0327 (11) | 0.0350 (11) | 0.0378 (10) | 0.0042 (9) | −0.0021 (9) | −0.0003 (9) |
C8 | 0.0441 (13) | 0.0467 (12) | 0.0556 (13) | −0.0024 (11) | −0.0109 (11) | −0.0066 (10) |
C9 | 0.0360 (13) | 0.0683 (15) | 0.0523 (13) | −0.0014 (11) | −0.0098 (11) | −0.0015 (12) |
C10 | 0.0569 (16) | 0.0831 (18) | 0.0722 (17) | 0.0013 (14) | −0.0238 (14) | 0.0140 (14) |
C11 | 0.0404 (12) | 0.0291 (10) | 0.0390 (11) | 0.0015 (9) | 0.0004 (9) | 0.0000 (9) |
C12 | 0.0380 (12) | 0.0371 (11) | 0.0378 (11) | 0.0023 (9) | 0.0005 (9) | 0.0028 (9) |
C13 | 0.0563 (15) | 0.0444 (13) | 0.0559 (13) | −0.0035 (11) | 0.0094 (12) | 0.0061 (10) |
C14 | 0.0649 (17) | 0.0516 (14) | 0.0619 (15) | −0.0007 (12) | 0.0111 (13) | 0.0165 (11) |
C15 | 0.0364 (11) | 0.0303 (10) | 0.0324 (10) | 0.0007 (9) | −0.0008 (9) | −0.0016 (8) |
C16 | 0.0379 (12) | 0.0408 (11) | 0.0375 (10) | 0.0043 (10) | −0.0023 (9) | −0.0031 (9) |
C17 | 0.0470 (14) | 0.0493 (13) | 0.0456 (12) | 0.0036 (11) | −0.0089 (10) | −0.0074 (10) |
C18 | 0.0480 (15) | 0.0769 (17) | 0.0661 (15) | 0.0044 (13) | −0.0167 (13) | −0.0165 (13) |
C19 | 0.0382 (11) | 0.0329 (10) | 0.0337 (10) | 0.0030 (9) | 0.0031 (9) | −0.0047 (8) |
C20 | 0.0455 (13) | 0.0355 (11) | 0.0338 (10) | 0.0020 (10) | 0.0020 (9) | −0.0018 (8) |
C21 | 0.0488 (14) | 0.0401 (11) | 0.0331 (10) | 0.0067 (10) | 0.0001 (9) | −0.0011 (9) |
C22 | 0.0531 (14) | 0.0530 (13) | 0.0370 (11) | 0.0048 (11) | 0.0067 (10) | 0.0030 (10) |
F1—B1 | 1.418 (2) | C12—C13 | 1.517 (3) |
F2—B1 | 1.409 (3) | C12—H12A | 0.990 |
F3—B1 | 1.426 (2) | C12—H12B | 0.990 |
C1—C6 | 1.387 (3) | C13—C14 | 1.500 (3) |
C1—C2 | 1.400 (3) | C13—H13A | 0.990 |
C1—B1 | 1.600 (3) | C13—H13B | 0.990 |
C2—C3 | 1.372 (3) | C14—H14A | 0.980 |
C2—H2A | 0.950 | C14—H14B | 0.980 |
C3—C4 | 1.368 (3) | C14—H14C | 0.980 |
C3—H3A | 0.950 | C15—C16 | 1.518 (3) |
C4—C5 | 1.371 (3) | C15—H15A | 0.990 |
C4—H4A | 0.950 | C15—H15B | 0.990 |
C5—C6 | 1.404 (3) | C16—C17 | 1.521 (3) |
C5—H5A | 0.950 | C16—H16A | 0.990 |
C6—H6A | 0.950 | C16—H16B | 0.990 |
N1—C15 | 1.516 (2) | C17—C18 | 1.523 (3) |
N1—C11 | 1.517 (2) | C17—H17A | 0.990 |
N1—C19 | 1.519 (2) | C17—H17B | 0.990 |
N1—C7 | 1.523 (2) | C18—H18A | 0.980 |
C7—C8 | 1.522 (3) | C18—H18B | 0.980 |
C7—H7A | 0.990 | C18—H18C | 0.980 |
C7—H7B | 0.990 | C19—C20 | 1.516 (3) |
C8—C9 | 1.523 (3) | C19—H19A | 0.990 |
C8—H8A | 0.990 | C19—H19B | 0.990 |
C8—H8B | 0.990 | C20—C21 | 1.525 (3) |
C9—C10 | 1.508 (3) | C20—H20A | 0.990 |
C9—H9A | 0.990 | C20—H20B | 0.990 |
C9—H9B | 0.990 | C21—C22 | 1.519 (3) |
C10—H10A | 0.980 | C21—H21A | 0.990 |
C10—H10B | 0.980 | C21—H21B | 0.990 |
C10—H10C | 0.980 | C22—H22A | 0.980 |
C11—C12 | 1.515 (2) | C22—H22B | 0.980 |
C11—H11A | 0.990 | C22—H22C | 0.980 |
C11—H11B | 0.990 | ||
C6—C1—C2 | 115.51 (18) | C11—C12—H12B | 109.6 |
C6—C1—B1 | 123.03 (18) | C13—C12—H12B | 109.6 |
C2—C1—B1 | 121.43 (18) | H12A—C12—H12B | 108.2 |
C3—C2—C1 | 123.0 (2) | C14—C13—C12 | 113.74 (18) |
C3—C2—H2A | 118.5 | C14—C13—H13A | 108.8 |
C1—C2—H2A | 118.5 | C12—C13—H13A | 108.8 |
C4—C3—C2 | 119.9 (2) | C14—C13—H13B | 108.8 |
C4—C3—H3A | 120.1 | C12—C13—H13B | 108.8 |
C2—C3—H3A | 120.1 | H13A—C13—H13B | 107.7 |
C3—C4—C5 | 119.9 (2) | C13—C14—H14A | 109.5 |
C3—C4—H4A | 120.1 | C13—C14—H14B | 109.5 |
C5—C4—H4A | 120.1 | H14A—C14—H14B | 109.5 |
C4—C5—C6 | 119.6 (2) | C13—C14—H14C | 109.5 |
C4—C5—H5A | 120.2 | H14A—C14—H14C | 109.5 |
C6—C5—H5A | 120.2 | H14B—C14—H14C | 109.5 |
C1—C6—C5 | 122.0 (2) | N1—C15—C16 | 116.13 (15) |
C1—C6—H6A | 119.0 | N1—C15—H15A | 108.3 |
C5—C6—H6A | 119.0 | C16—C15—H15A | 108.3 |
F2—B1—F1 | 107.99 (16) | N1—C15—H15B | 108.3 |
F2—B1—F3 | 107.19 (16) | C16—C15—H15B | 108.3 |
F1—B1—F3 | 106.08 (16) | H15A—C15—H15B | 107.4 |
F2—B1—C1 | 112.03 (17) | C15—C16—C17 | 109.73 (16) |
F1—B1—C1 | 111.91 (16) | C15—C16—H16A | 109.7 |
F3—B1—C1 | 111.33 (16) | C17—C16—H16A | 109.7 |
C15—N1—C11 | 111.58 (13) | C15—C16—H16B | 109.7 |
C15—N1—C19 | 110.75 (14) | C17—C16—H16B | 109.7 |
C11—N1—C19 | 106.36 (13) | H16A—C16—H16B | 108.2 |
C15—N1—C7 | 106.01 (13) | C16—C17—C18 | 112.73 (18) |
C11—N1—C7 | 111.19 (14) | C16—C17—H17A | 109.0 |
C19—N1—C7 | 111.03 (13) | C18—C17—H17A | 109.0 |
C8—C7—N1 | 116.54 (15) | C16—C17—H17B | 109.0 |
C8—C7—H7A | 108.2 | C18—C17—H17B | 109.0 |
N1—C7—H7A | 108.2 | H17A—C17—H17B | 107.8 |
C8—C7—H7B | 108.2 | C17—C18—H18A | 109.5 |
N1—C7—H7B | 108.2 | C17—C18—H18B | 109.5 |
H7A—C7—H7B | 107.3 | H18A—C18—H18B | 109.5 |
C7—C8—C9 | 110.32 (17) | C17—C18—H18C | 109.5 |
C7—C8—H8A | 109.6 | H18A—C18—H18C | 109.5 |
C9—C8—H8A | 109.6 | H18B—C18—H18C | 109.5 |
C7—C8—H8B | 109.6 | C20—C19—N1 | 117.28 (14) |
C9—C8—H8B | 109.6 | C20—C19—H19A | 108.0 |
H8A—C8—H8B | 108.1 | N1—C19—H19A | 108.0 |
C10—C9—C8 | 114.17 (19) | C20—C19—H19B | 108.0 |
C10—C9—H9A | 108.7 | N1—C19—H19B | 108.0 |
C8—C9—H9A | 108.7 | H19A—C19—H19B | 107.2 |
C10—C9—H9B | 108.7 | C19—C20—C21 | 109.00 (15) |
C8—C9—H9B | 108.7 | C19—C20—H20A | 109.9 |
H9A—C9—H9B | 107.6 | C21—C20—H20A | 109.9 |
C9—C10—H10A | 109.5 | C19—C20—H20B | 109.9 |
C9—C10—H10B | 109.5 | C21—C20—H20B | 109.9 |
H10A—C10—H10B | 109.5 | H20A—C20—H20B | 108.3 |
C9—C10—H10C | 109.5 | C22—C21—C20 | 112.67 (16) |
H10A—C10—H10C | 109.5 | C22—C21—H21A | 109.1 |
H10B—C10—H10C | 109.5 | C20—C21—H21A | 109.1 |
C12—C11—N1 | 116.41 (14) | C22—C21—H21B | 109.1 |
C12—C11—H11A | 108.2 | C20—C21—H21B | 109.1 |
N1—C11—H11A | 108.2 | H21A—C21—H21B | 107.8 |
C12—C11—H11B | 108.2 | C21—C22—H22A | 109.5 |
N1—C11—H11B | 108.2 | C21—C22—H22B | 109.5 |
H11A—C11—H11B | 107.3 | H22A—C22—H22B | 109.5 |
C11—C12—C13 | 110.12 (16) | C21—C22—H22C | 109.5 |
C11—C12—H12A | 109.6 | H22A—C22—H22C | 109.5 |
C13—C12—H12A | 109.6 | H22B—C22—H22C | 109.5 |
C7—C8—C9—C10 | 67.5 (2) | C15—C16—C17—C18 | 179.70 (18) |
C11—C12—C13—C14 | −177.23 (19) | C19—C20—C21—C22 | −168.75 (17) |
Experimental details
Crystal data | |
Chemical formula | C16H36N+·C6H5BF3− |
Mr | 387.37 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 150 |
a, b, c (Å) | 13.5626 (6), 17.1534 (7), 20.3567 (7) |
V (Å3) | 4735.9 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.40 × 0.35 × 0.34 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.970, 0.974 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20559, 4341, 2858 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.603 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.130, 1.02 |
No. of reflections | 4341 |
No. of parameters | 248 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.19 |
Computer programs: COLLECT (Nonius, 1997-2001), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXTL (Sheldrick 1999), SHELXTL.
C1—B1 | 1.600 (3) | ||
C7—C8—C9—C10 | 67.5 (2) | C15—C16—C17—C18 | 179.70 (18) |
C11—C12—C13—C14 | −177.23 (19) | C19—C20—C21—C22 | −168.75 (17) |
Recently, potassium organotrifluoroborate salts have gained considerable interest in organic synthesis as alternatives to boronic acids in reactions such as rhodium(I)-catalyzed 1,4-additions to α,β-unsaturated carbonyl compounds (Batey et al., 1999), Lewis acid catalyzed allylation of aldehydes (Batey et al., 2000), palladium catalyzed couplings with aryldiazonium compounds (Genet et al., 1999), and the synthesis of oxazaborolidinones (Vedejs et al., 1993). Their stability towards air and moisture also makes them ideal reagents for combinatorial synthesis. One drawback to their use, however, is their decreased solubility in non-polar organic solvents.
In an attempt to synthesize phenyldifluoroborane by treating the corresponding boronic acid with hydrofluoric acid (Kinder & Katzenellenbogen, 1985), it was discovered that the organodifluoroborane species would quickly convert to an organotrifluoroborate species (confirmed by 11B NMR). It was hypothesized that the species formed was the hydronium organotrifluoroborate salt; however, all attempts to isolate this compound were unsuccessful, and the compound was only observable spectroscopically in solution via 11B and 19F NMR. Fortunately, treatment of the intermediate with the base tetra-n-butylammonium hydroxide affected a counterion exchange to produce the isolable title compound, (I).
The tetra-n-butylammonium derivative was found to have comparable reactivity to that of its potassium counterpart in the aforementioned reactions with the added advantage of having excellent solubility in nonpolar organic solvents. Compound (I) was also found to have greater reactivity than its potassium counterpart in palladium catalyzed Suzuki cross-coupling reactions with aryl- and alkenylhalides (Batey & Quach, 2001).
Compound (I) crystallizes as discrete tetra-n-butylammonium and phenyltrifluoroborate ions (see Fig. 1). There are no close contacts between the anions and cations in the structure. The tetra-n-butylammonium ion in (I) has three butyl groups which are in the staggered conformation and one group (containing the atoms C7, C8, C9 and C10) which is in a coiled conformation (see Table 1 for torsion angles) The structure of the related potassium phenyltrifluoroborate salt (Conole et al., 1995) has also been determined.