Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027225/hk2266sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027225/hk2266Isup2.hkl |
CCDC reference: 654911
For the preparation of the title compound, Ph3P (34.5 g, 132 mmol), NEt3 (18.2 ml, 132 mmol), CCl4 (21.1 ml, 220 mmol) and TFA (3.4 ml, 44 mmol) was added to a 200 ml three-necked round bottom flask equipped with condenser and magnetic stir bar at 273 K under nitrogen atmosphere and stirred for 10 min. Subsequently, the reaction mixture was allowed to reflux for 3 h. After cooling, the solvent was removed by rotary evaporator and the residue was washed carefully with the solution of petroleum ether and ethyl acetate (2:1) for three times, the precipitate was removed via filtration. The filtrate was combined and concentrated by rotary evaporator. The residue was then purified by column chromatography to offer the product (yield; 59%).
H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H atoms, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).
Fluorine-containing compounds have received considerable attention because of their pharmaceutical applications and unique physical properties (Goldman, 1969; Iseki, 1998). As one part of our ongoing studies on the synthesis of organofluorine compounds, we focused our attention on the synthesis of fluorinated imidoyl chloride intermediates (Ge et al., 2007). The phosphonium ylide of (3) was obtained unexpectedly, while searching of a novel flourine-containing benzimidazole.
In the molecule of the title compound, (3), (Fig. 1), the bond lengths and angles are generally within normal ranges (Allen et al., 1987), where the bonds P1—C19 [1.7509 (17) Å] and C20—O1 [1.244 (2) Å] are longer than the commonly corresponding double bonds P=C [1.66 Å] in Ph3P=CH2 and C=O [1.22 Å] in (CH3)2CO. In addition, the bonds C19—C20 [1.384 (3) Å] and C19—Cl1 [1.734 (18) Å] are shorter than the common C—C and C—Cl [1.77 Å] single bonds. Furthermore, the bond angles C20—C19—Cl1 [124.21 (14)°] and O1—C20—C19 [123.49 (17)°] are close to those of double bonds. These results strongly indicate that C19—C20 bond has significantly double bond character in the enolic structure of phosphonium ylides (3) (Berclaz et al., 1999), which could be stabilized by the strong electron-withdrawing of the trifluoro- methyl group.
Rings A (C1—C6), B (C7—C12) and C (C13—C18) are, of course, planar and the dihedral angles between them are A/B = 75.23 (2)°, A/C = 69.69 (3)° and B/C = 72.37 (3)°.
In the crystal structure, intra- and intermolecular C—H···O hydrogen bonds (Table 1, Fig. 1), linking the molecules, seem to be effective in the stabilization of the structure.
For general backgroud, see: Goldman (1969); Iseki (1998); Ge et al. (2007); Allen et al. (1987). For related literature, see: Berclaz et al. (1999).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
C21H15ClF3OP | F(000) = 832 |
Mr = 406.75 | Dx = 1.410 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5734 reflections |
a = 10.6377 (9) Å | θ = 2.3–27.4° |
b = 9.8603 (9) Å | µ = 0.32 mm−1 |
c = 18.3754 (16) Å | T = 273 K |
β = 96.059 (1)° | Block, colorless |
V = 1916.6 (3) Å3 | 0.30 × 0.30 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3014 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 25.1°, θmin = 2.2° |
φ and ω scans | h = −12→12 |
9644 measured reflections | k = −11→11 |
3391 independent reflections | l = −18→21 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0388P)2 + 0.9546P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
3391 reflections | Δρmax = 0.34 e Å−3 |
245 parameters | Δρmin = −0.33 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0079 (7) |
C21H15ClF3OP | V = 1916.6 (3) Å3 |
Mr = 406.75 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.6377 (9) Å | µ = 0.32 mm−1 |
b = 9.8603 (9) Å | T = 273 K |
c = 18.3754 (16) Å | 0.30 × 0.30 × 0.20 mm |
β = 96.059 (1)° |
Bruker SMART CCD area-detector diffractometer | 3014 reflections with I > 2σ(I) |
9644 measured reflections | Rint = 0.015 |
3391 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.34 e Å−3 |
3391 reflections | Δρmin = −0.33 e Å−3 |
245 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 | ||
Cl1 | 0.78417 (7) | 0.43490 (6) | −0.06671 (3) | 0.0659 (2) | |
P1 | 0.78933 (4) | 0.37901 (4) | 0.09492 (2) | 0.03432 (14) | |
F1 | 0.84707 (18) | −0.00956 (15) | −0.07485 (9) | 0.0985 (6) | |
F2 | 0.90527 (15) | 0.17805 (19) | −0.11684 (8) | 0.0966 (6) | |
F3 | 0.71153 (13) | 0.13165 (16) | −0.11872 (8) | 0.0822 (5) | |
O1 | 0.83346 (15) | 0.10340 (14) | 0.05088 (8) | 0.0577 (4) | |
C1 | 0.93696 (16) | 0.37741 (17) | 0.15278 (9) | 0.0378 (4) | |
C2 | 1.03455 (18) | 0.2950 (2) | 0.13624 (11) | 0.0493 (5) | |
H2 | 1.0245 | 0.2395 | 0.0951 | 0.059* | |
C3 | 1.1475 (2) | 0.2951 (3) | 0.18098 (14) | 0.0652 (6) | |
H3 | 1.2134 | 0.2395 | 0.1698 | 0.078* | |
C4 | 1.1630 (2) | 0.3765 (3) | 0.24157 (13) | 0.0670 (7) | |
H4 | 1.2394 | 0.3760 | 0.2713 | 0.080* | |
C5 | 1.0667 (2) | 0.4587 (3) | 0.25870 (12) | 0.0654 (6) | |
H5 | 1.0775 | 0.5133 | 0.3002 | 0.078* | |
C6 | 0.95318 (19) | 0.4606 (2) | 0.21433 (11) | 0.0539 (5) | |
H6 | 0.8880 | 0.5172 | 0.2256 | 0.065* | |
C7 | 0.67461 (16) | 0.27865 (18) | 0.13649 (10) | 0.0394 (4) | |
C8 | 0.69440 (19) | 0.2353 (2) | 0.20828 (11) | 0.0517 (5) | |
H8 | 0.7684 | 0.2585 | 0.2371 | 0.062* | |
C9 | 0.6036 (2) | 0.1573 (3) | 0.23702 (12) | 0.0670 (6) | |
H9 | 0.6169 | 0.1283 | 0.2854 | 0.080* | |
C10 | 0.4946 (2) | 0.1222 (3) | 0.19517 (14) | 0.0703 (7) | |
H10 | 0.4340 | 0.0699 | 0.2151 | 0.084* | |
C11 | 0.4747 (2) | 0.1643 (3) | 0.12389 (14) | 0.0703 (7) | |
H11 | 0.4007 | 0.1401 | 0.0953 | 0.084* | |
C12 | 0.56394 (19) | 0.2424 (2) | 0.09450 (12) | 0.0570 (5) | |
H12 | 0.5498 | 0.2710 | 0.0461 | 0.068* | |
C13 | 0.73744 (17) | 0.55267 (18) | 0.09040 (10) | 0.0399 (4) | |
C14 | 0.6163 (2) | 0.5899 (2) | 0.10284 (11) | 0.0531 (5) | |
H14 | 0.5590 | 0.5247 | 0.1152 | 0.064* | |
C15 | 0.5808 (2) | 0.7252 (3) | 0.09677 (13) | 0.0665 (6) | |
H15 | 0.4994 | 0.7507 | 0.1053 | 0.080* | |
C16 | 0.6647 (2) | 0.8214 (2) | 0.07825 (12) | 0.0652 (6) | |
H16 | 0.6398 | 0.9117 | 0.0739 | 0.078* | |
C17 | 0.7850 (2) | 0.7855 (2) | 0.06608 (13) | 0.0611 (6) | |
H17 | 0.8416 | 0.8512 | 0.0536 | 0.073* | |
C18 | 0.8220 (2) | 0.65176 (19) | 0.07231 (12) | 0.0521 (5) | |
H18 | 0.9040 | 0.6275 | 0.0644 | 0.063* | |
C19 | 0.80126 (16) | 0.32140 (18) | 0.00578 (9) | 0.0386 (4) | |
C20 | 0.81954 (17) | 0.18333 (19) | −0.00175 (10) | 0.0418 (4) | |
C21 | 0.82192 (19) | 0.1214 (2) | −0.07811 (12) | 0.0525 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1100 (5) | 0.0475 (3) | 0.0406 (3) | −0.0042 (3) | 0.0089 (3) | 0.0085 (2) |
P1 | 0.0371 (2) | 0.0304 (2) | 0.0353 (2) | −0.00044 (18) | 0.00313 (17) | −0.00018 (18) |
F1 | 0.1431 (15) | 0.0604 (9) | 0.0902 (11) | 0.0336 (9) | 0.0037 (10) | −0.0309 (8) |
F2 | 0.0929 (11) | 0.1209 (13) | 0.0847 (10) | −0.0327 (10) | 0.0504 (9) | −0.0435 (10) |
F3 | 0.0673 (9) | 0.1004 (12) | 0.0743 (9) | 0.0046 (8) | −0.0140 (7) | −0.0376 (8) |
O1 | 0.0781 (10) | 0.0360 (7) | 0.0584 (9) | 0.0046 (7) | 0.0049 (7) | 0.0034 (7) |
C1 | 0.0387 (9) | 0.0358 (9) | 0.0386 (9) | −0.0042 (7) | 0.0027 (7) | 0.0051 (7) |
C2 | 0.0450 (10) | 0.0484 (11) | 0.0537 (11) | 0.0025 (9) | 0.0015 (9) | 0.0007 (9) |
C3 | 0.0456 (12) | 0.0732 (16) | 0.0748 (16) | 0.0104 (11) | −0.0030 (11) | 0.0107 (13) |
C4 | 0.0498 (12) | 0.0874 (18) | 0.0596 (14) | −0.0097 (12) | −0.0140 (10) | 0.0165 (13) |
C5 | 0.0659 (14) | 0.0803 (17) | 0.0468 (12) | −0.0170 (13) | −0.0082 (10) | −0.0055 (11) |
C6 | 0.0518 (11) | 0.0598 (13) | 0.0493 (11) | −0.0040 (10) | 0.0015 (9) | −0.0097 (10) |
C7 | 0.0388 (9) | 0.0391 (10) | 0.0406 (9) | −0.0019 (7) | 0.0051 (7) | −0.0004 (8) |
C8 | 0.0484 (11) | 0.0629 (13) | 0.0435 (11) | −0.0055 (9) | 0.0036 (8) | 0.0053 (9) |
C9 | 0.0659 (14) | 0.0863 (17) | 0.0503 (12) | −0.0117 (13) | 0.0130 (10) | 0.0173 (12) |
C10 | 0.0581 (14) | 0.0840 (18) | 0.0720 (15) | −0.0201 (12) | 0.0211 (12) | 0.0103 (13) |
C11 | 0.0504 (12) | 0.0903 (18) | 0.0693 (15) | −0.0253 (12) | 0.0021 (11) | 0.0004 (14) |
C12 | 0.0508 (11) | 0.0722 (15) | 0.0469 (11) | −0.0143 (10) | −0.0006 (9) | 0.0056 (10) |
C13 | 0.0444 (10) | 0.0347 (9) | 0.0395 (9) | 0.0047 (8) | −0.0007 (7) | −0.0031 (7) |
C14 | 0.0520 (11) | 0.0536 (12) | 0.0539 (12) | 0.0112 (9) | 0.0070 (9) | 0.0029 (10) |
C15 | 0.0655 (14) | 0.0674 (16) | 0.0664 (14) | 0.0315 (12) | 0.0056 (11) | 0.0000 (12) |
C16 | 0.0926 (18) | 0.0418 (12) | 0.0572 (13) | 0.0219 (12) | −0.0114 (12) | −0.0035 (10) |
C17 | 0.0758 (15) | 0.0361 (11) | 0.0680 (14) | −0.0006 (10) | −0.0086 (11) | 0.0006 (10) |
C18 | 0.0528 (11) | 0.0352 (10) | 0.0673 (13) | −0.0002 (9) | 0.0018 (10) | −0.0013 (9) |
C19 | 0.0465 (10) | 0.0346 (9) | 0.0348 (9) | −0.0010 (7) | 0.0055 (7) | 0.0010 (7) |
C20 | 0.0418 (10) | 0.0375 (10) | 0.0460 (10) | −0.0017 (8) | 0.0043 (8) | −0.0050 (8) |
C21 | 0.0469 (11) | 0.0504 (12) | 0.0605 (13) | 0.0006 (9) | 0.0070 (9) | −0.0163 (10) |
Cl1—C19 | 1.7346 (18) | C8—C9 | 1.383 (3) |
P1—C19 | 1.7509 (17) | C8—H8 | 0.9300 |
P1—C13 | 1.7984 (18) | C9—C10 | 1.366 (3) |
P1—C1 | 1.8011 (17) | C9—H9 | 0.9300 |
P1—C7 | 1.8026 (18) | C10—C11 | 1.369 (3) |
F1—C21 | 1.319 (3) | C10—H10 | 0.9300 |
F2—C21 | 1.318 (3) | C11—C12 | 1.376 (3) |
F3—C21 | 1.327 (2) | C11—H11 | 0.9300 |
O1—C20 | 1.244 (2) | C12—H12 | 0.9300 |
C1—C2 | 1.377 (3) | C13—C14 | 1.381 (3) |
C1—C6 | 1.393 (3) | C13—C18 | 1.392 (3) |
C2—C3 | 1.382 (3) | C14—C15 | 1.388 (3) |
C2—H2 | 0.9300 | C14—H14 | 0.9300 |
C3—C4 | 1.368 (3) | C15—C16 | 1.370 (4) |
C3—H3 | 0.9300 | C15—H15 | 0.9300 |
C4—C5 | 1.369 (4) | C16—C17 | 1.368 (3) |
C4—H4 | 0.9300 | C16—H16 | 0.9300 |
C5—C6 | 1.384 (3) | C17—C18 | 1.377 (3) |
C5—H5 | 0.9300 | C17—H17 | 0.9300 |
C6—H6 | 0.9300 | C18—H18 | 0.9300 |
C7—C8 | 1.382 (3) | C19—C20 | 1.384 (3) |
C7—C12 | 1.385 (3) | C20—C21 | 1.533 (3) |
C19—P1—C13 | 108.54 (8) | C10—C11—C12 | 120.1 (2) |
C19—P1—C1 | 113.87 (8) | C10—C11—H11 | 120.0 |
C13—P1—C1 | 106.25 (8) | C12—C11—H11 | 120.0 |
C19—P1—C7 | 109.72 (8) | C11—C12—C7 | 120.5 (2) |
C13—P1—C7 | 108.90 (9) | C11—C12—H12 | 119.8 |
C1—P1—C7 | 109.40 (8) | C7—C12—H12 | 119.8 |
C2—C1—C6 | 119.66 (17) | C14—C13—C18 | 119.39 (18) |
C2—C1—P1 | 120.37 (14) | C14—C13—P1 | 122.15 (15) |
C6—C1—P1 | 119.98 (14) | C18—C13—P1 | 118.44 (14) |
C1—C2—C3 | 119.8 (2) | C13—C14—C15 | 119.5 (2) |
C1—C2—H2 | 120.1 | C13—C14—H14 | 120.2 |
C3—C2—H2 | 120.1 | C15—C14—H14 | 120.2 |
C4—C3—C2 | 120.5 (2) | C16—C15—C14 | 120.4 (2) |
C4—C3—H3 | 119.8 | C16—C15—H15 | 119.8 |
C2—C3—H3 | 119.8 | C14—C15—H15 | 119.8 |
C3—C4—C5 | 120.4 (2) | C17—C16—C15 | 120.4 (2) |
C3—C4—H4 | 119.8 | C17—C16—H16 | 119.8 |
C5—C4—H4 | 119.8 | C15—C16—H16 | 119.8 |
C4—C5—C6 | 120.0 (2) | C16—C17—C18 | 119.9 (2) |
C4—C5—H5 | 120.0 | C16—C17—H17 | 120.1 |
C6—C5—H5 | 120.0 | C18—C17—H17 | 120.1 |
C5—C6—C1 | 119.7 (2) | C17—C18—C13 | 120.3 (2) |
C5—C6—H6 | 120.1 | C17—C18—H18 | 119.8 |
C1—C6—H6 | 120.1 | C13—C18—H18 | 119.8 |
C8—C7—C12 | 119.16 (17) | C20—C19—Cl1 | 124.21 (14) |
C8—C7—P1 | 122.19 (14) | C20—C19—P1 | 115.94 (14) |
C12—C7—P1 | 118.64 (14) | Cl1—C19—P1 | 119.81 (10) |
C7—C8—C9 | 119.64 (19) | O1—C20—C19 | 123.49 (17) |
C7—C8—H8 | 120.2 | O1—C20—C21 | 116.56 (17) |
C9—C8—H8 | 120.2 | C19—C20—C21 | 119.95 (17) |
C10—C9—C8 | 120.8 (2) | F2—C21—F1 | 107.12 (18) |
C10—C9—H9 | 119.6 | F2—C21—F3 | 105.66 (19) |
C8—C9—H9 | 119.6 | F1—C21—F3 | 105.25 (18) |
C9—C10—C11 | 119.9 (2) | F2—C21—C20 | 113.74 (17) |
C9—C10—H10 | 120.1 | F1—C21—C20 | 111.79 (18) |
C11—C10—H10 | 120.1 | F3—C21—C20 | 112.67 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1 | 0.93 | 2.50 | 3.1460 | 127 |
C17—H17···O1i | 0.93 | 2.49 | 3.1937 | 133 |
Symmetry code: (i) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C21H15ClF3OP |
Mr | 406.75 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 273 |
a, b, c (Å) | 10.6377 (9), 9.8603 (9), 18.3754 (16) |
β (°) | 96.059 (1) |
V (Å3) | 1916.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.32 |
Crystal size (mm) | 0.30 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9644, 3391, 3014 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.090, 1.03 |
No. of reflections | 3391 |
No. of parameters | 245 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.33 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1 | 0.93 | 2.50 | 3.1460 | 127.0 |
C17—H17···O1i | 0.93 | 2.49 | 3.1937 | 133.0 |
Symmetry code: (i) x, y+1, z. |
Fluorine-containing compounds have received considerable attention because of their pharmaceutical applications and unique physical properties (Goldman, 1969; Iseki, 1998). As one part of our ongoing studies on the synthesis of organofluorine compounds, we focused our attention on the synthesis of fluorinated imidoyl chloride intermediates (Ge et al., 2007). The phosphonium ylide of (3) was obtained unexpectedly, while searching of a novel flourine-containing benzimidazole.
In the molecule of the title compound, (3), (Fig. 1), the bond lengths and angles are generally within normal ranges (Allen et al., 1987), where the bonds P1—C19 [1.7509 (17) Å] and C20—O1 [1.244 (2) Å] are longer than the commonly corresponding double bonds P=C [1.66 Å] in Ph3P=CH2 and C=O [1.22 Å] in (CH3)2CO. In addition, the bonds C19—C20 [1.384 (3) Å] and C19—Cl1 [1.734 (18) Å] are shorter than the common C—C and C—Cl [1.77 Å] single bonds. Furthermore, the bond angles C20—C19—Cl1 [124.21 (14)°] and O1—C20—C19 [123.49 (17)°] are close to those of double bonds. These results strongly indicate that C19—C20 bond has significantly double bond character in the enolic structure of phosphonium ylides (3) (Berclaz et al., 1999), which could be stabilized by the strong electron-withdrawing of the trifluoro- methyl group.
Rings A (C1—C6), B (C7—C12) and C (C13—C18) are, of course, planar and the dihedral angles between them are A/B = 75.23 (2)°, A/C = 69.69 (3)° and B/C = 72.37 (3)°.
In the crystal structure, intra- and intermolecular C—H···O hydrogen bonds (Table 1, Fig. 1), linking the molecules, seem to be effective in the stabilization of the structure.