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The title compound, C21H15ClF3OP, was obtained by a convenient and efficient one-pot synthesis. The length of the C=C bond indicates a large enolic contribution to the structure. Intra- and inter­molecular C—H...O hydrogen bonds are present in the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027225/hk2266sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027225/hk2266Isup2.hkl
Contains datablock I

CCDC reference: 654911

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.035
  • wR factor = 0.090
  • Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C21 PLAT747_ALERT_1_C D...A Calc 3.146(2), Rep 3.14600 ...... Missing su C2 -O1 1.555 1.555 PLAT747_ALERT_1_C D...A Calc 3.194(2), Rep 3.19370 ...... Missing su C17 -O1 1.555 1.565
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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.

Related literature top

For general backgroud, see: Goldman (1969); Iseki (1998); Ge et al. (2007); Allen et al. (1987). For related literature, see: Berclaz et al. (1999).

Experimental top

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%).

Refinement top

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).

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A packing diagram for (3). Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. The reaction scheme for the formation of (3).
3-Chloro-1,1,1-trifluoro-3-(triphenylphosphoranylidene)propan-2-one top
Crystal data top
C21H15ClF3OPF(000) = 832
Mr = 406.75Dx = 1.410 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5734 reflections
a = 10.6377 (9) Åθ = 2.3–27.4°
b = 9.8603 (9) ŵ = 0.32 mm1
c = 18.3754 (16) ÅT = 273 K
β = 96.059 (1)°Block, colorless
V = 1916.6 (3) Å30.30 × 0.30 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
3014 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.015
Graphite monochromatorθmax = 25.1°, θmin = 2.2°
φ and ω scansh = 1212
9644 measured reflectionsk = 1111
3391 independent reflectionsl = 1821
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-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 reflectionsΔρmax = 0.34 e Å3
245 parametersΔρmin = 0.33 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0079 (7)
Crystal data top
C21H15ClF3OPV = 1916.6 (3) Å3
Mr = 406.75Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.6377 (9) ŵ = 0.32 mm1
b = 9.8603 (9) ÅT = 273 K
c = 18.3754 (16) Å0.30 × 0.30 × 0.20 mm
β = 96.059 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3014 reflections with I > 2σ(I)
9644 measured reflectionsRint = 0.015
3391 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.03Δρmax = 0.34 e Å3
3391 reflectionsΔρmin = 0.33 e Å3
245 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.78417 (7)0.43490 (6)0.06671 (3)0.0659 (2)
P10.78933 (4)0.37901 (4)0.09492 (2)0.03432 (14)
F10.84707 (18)0.00956 (15)0.07485 (9)0.0985 (6)
F20.90527 (15)0.17805 (19)0.11684 (8)0.0966 (6)
F30.71153 (13)0.13165 (16)0.11872 (8)0.0822 (5)
O10.83346 (15)0.10340 (14)0.05088 (8)0.0577 (4)
C10.93696 (16)0.37741 (17)0.15278 (9)0.0378 (4)
C21.03455 (18)0.2950 (2)0.13624 (11)0.0493 (5)
H21.02450.23950.09510.059*
C31.1475 (2)0.2951 (3)0.18098 (14)0.0652 (6)
H31.21340.23950.16980.078*
C41.1630 (2)0.3765 (3)0.24157 (13)0.0670 (7)
H41.23940.37600.27130.080*
C51.0667 (2)0.4587 (3)0.25870 (12)0.0654 (6)
H51.07750.51330.30020.078*
C60.95318 (19)0.4606 (2)0.21433 (11)0.0539 (5)
H60.88800.51720.22560.065*
C70.67461 (16)0.27865 (18)0.13649 (10)0.0394 (4)
C80.69440 (19)0.2353 (2)0.20828 (11)0.0517 (5)
H80.76840.25850.23710.062*
C90.6036 (2)0.1573 (3)0.23702 (12)0.0670 (6)
H90.61690.12830.28540.080*
C100.4946 (2)0.1222 (3)0.19517 (14)0.0703 (7)
H100.43400.06990.21510.084*
C110.4747 (2)0.1643 (3)0.12389 (14)0.0703 (7)
H110.40070.14010.09530.084*
C120.56394 (19)0.2424 (2)0.09450 (12)0.0570 (5)
H120.54980.27100.04610.068*
C130.73744 (17)0.55267 (18)0.09040 (10)0.0399 (4)
C140.6163 (2)0.5899 (2)0.10284 (11)0.0531 (5)
H140.55900.52470.11520.064*
C150.5808 (2)0.7252 (3)0.09677 (13)0.0665 (6)
H150.49940.75070.10530.080*
C160.6647 (2)0.8214 (2)0.07825 (12)0.0652 (6)
H160.63980.91170.07390.078*
C170.7850 (2)0.7855 (2)0.06608 (13)0.0611 (6)
H170.84160.85120.05360.073*
C180.8220 (2)0.65176 (19)0.07231 (12)0.0521 (5)
H180.90400.62750.06440.063*
C190.80126 (16)0.32140 (18)0.00578 (9)0.0386 (4)
C200.81954 (17)0.18333 (19)0.00175 (10)0.0418 (4)
C210.82192 (19)0.1214 (2)0.07811 (12)0.0525 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.1100 (5)0.0475 (3)0.0406 (3)0.0042 (3)0.0089 (3)0.0085 (2)
P10.0371 (2)0.0304 (2)0.0353 (2)0.00044 (18)0.00313 (17)0.00018 (18)
F10.1431 (15)0.0604 (9)0.0902 (11)0.0336 (9)0.0037 (10)0.0309 (8)
F20.0929 (11)0.1209 (13)0.0847 (10)0.0327 (10)0.0504 (9)0.0435 (10)
F30.0673 (9)0.1004 (12)0.0743 (9)0.0046 (8)0.0140 (7)0.0376 (8)
O10.0781 (10)0.0360 (7)0.0584 (9)0.0046 (7)0.0049 (7)0.0034 (7)
C10.0387 (9)0.0358 (9)0.0386 (9)0.0042 (7)0.0027 (7)0.0051 (7)
C20.0450 (10)0.0484 (11)0.0537 (11)0.0025 (9)0.0015 (9)0.0007 (9)
C30.0456 (12)0.0732 (16)0.0748 (16)0.0104 (11)0.0030 (11)0.0107 (13)
C40.0498 (12)0.0874 (18)0.0596 (14)0.0097 (12)0.0140 (10)0.0165 (13)
C50.0659 (14)0.0803 (17)0.0468 (12)0.0170 (13)0.0082 (10)0.0055 (11)
C60.0518 (11)0.0598 (13)0.0493 (11)0.0040 (10)0.0015 (9)0.0097 (10)
C70.0388 (9)0.0391 (10)0.0406 (9)0.0019 (7)0.0051 (7)0.0004 (8)
C80.0484 (11)0.0629 (13)0.0435 (11)0.0055 (9)0.0036 (8)0.0053 (9)
C90.0659 (14)0.0863 (17)0.0503 (12)0.0117 (13)0.0130 (10)0.0173 (12)
C100.0581 (14)0.0840 (18)0.0720 (15)0.0201 (12)0.0211 (12)0.0103 (13)
C110.0504 (12)0.0903 (18)0.0693 (15)0.0253 (12)0.0021 (11)0.0004 (14)
C120.0508 (11)0.0722 (15)0.0469 (11)0.0143 (10)0.0006 (9)0.0056 (10)
C130.0444 (10)0.0347 (9)0.0395 (9)0.0047 (8)0.0007 (7)0.0031 (7)
C140.0520 (11)0.0536 (12)0.0539 (12)0.0112 (9)0.0070 (9)0.0029 (10)
C150.0655 (14)0.0674 (16)0.0664 (14)0.0315 (12)0.0056 (11)0.0000 (12)
C160.0926 (18)0.0418 (12)0.0572 (13)0.0219 (12)0.0114 (12)0.0035 (10)
C170.0758 (15)0.0361 (11)0.0680 (14)0.0006 (10)0.0086 (11)0.0006 (10)
C180.0528 (11)0.0352 (10)0.0673 (13)0.0002 (9)0.0018 (10)0.0013 (9)
C190.0465 (10)0.0346 (9)0.0348 (9)0.0010 (7)0.0055 (7)0.0010 (7)
C200.0418 (10)0.0375 (10)0.0460 (10)0.0017 (8)0.0043 (8)0.0050 (8)
C210.0469 (11)0.0504 (12)0.0605 (13)0.0006 (9)0.0070 (9)0.0163 (10)
Geometric parameters (Å, º) top
Cl1—C191.7346 (18)C8—C91.383 (3)
P1—C191.7509 (17)C8—H80.9300
P1—C131.7984 (18)C9—C101.366 (3)
P1—C11.8011 (17)C9—H90.9300
P1—C71.8026 (18)C10—C111.369 (3)
F1—C211.319 (3)C10—H100.9300
F2—C211.318 (3)C11—C121.376 (3)
F3—C211.327 (2)C11—H110.9300
O1—C201.244 (2)C12—H120.9300
C1—C21.377 (3)C13—C141.381 (3)
C1—C61.393 (3)C13—C181.392 (3)
C2—C31.382 (3)C14—C151.388 (3)
C2—H20.9300C14—H140.9300
C3—C41.368 (3)C15—C161.370 (4)
C3—H30.9300C15—H150.9300
C4—C51.369 (4)C16—C171.368 (3)
C4—H40.9300C16—H160.9300
C5—C61.384 (3)C17—C181.377 (3)
C5—H50.9300C17—H170.9300
C6—H60.9300C18—H180.9300
C7—C81.382 (3)C19—C201.384 (3)
C7—C121.385 (3)C20—C211.533 (3)
C19—P1—C13108.54 (8)C10—C11—C12120.1 (2)
C19—P1—C1113.87 (8)C10—C11—H11120.0
C13—P1—C1106.25 (8)C12—C11—H11120.0
C19—P1—C7109.72 (8)C11—C12—C7120.5 (2)
C13—P1—C7108.90 (9)C11—C12—H12119.8
C1—P1—C7109.40 (8)C7—C12—H12119.8
C2—C1—C6119.66 (17)C14—C13—C18119.39 (18)
C2—C1—P1120.37 (14)C14—C13—P1122.15 (15)
C6—C1—P1119.98 (14)C18—C13—P1118.44 (14)
C1—C2—C3119.8 (2)C13—C14—C15119.5 (2)
C1—C2—H2120.1C13—C14—H14120.2
C3—C2—H2120.1C15—C14—H14120.2
C4—C3—C2120.5 (2)C16—C15—C14120.4 (2)
C4—C3—H3119.8C16—C15—H15119.8
C2—C3—H3119.8C14—C15—H15119.8
C3—C4—C5120.4 (2)C17—C16—C15120.4 (2)
C3—C4—H4119.8C17—C16—H16119.8
C5—C4—H4119.8C15—C16—H16119.8
C4—C5—C6120.0 (2)C16—C17—C18119.9 (2)
C4—C5—H5120.0C16—C17—H17120.1
C6—C5—H5120.0C18—C17—H17120.1
C5—C6—C1119.7 (2)C17—C18—C13120.3 (2)
C5—C6—H6120.1C17—C18—H18119.8
C1—C6—H6120.1C13—C18—H18119.8
C8—C7—C12119.16 (17)C20—C19—Cl1124.21 (14)
C8—C7—P1122.19 (14)C20—C19—P1115.94 (14)
C12—C7—P1118.64 (14)Cl1—C19—P1119.81 (10)
C7—C8—C9119.64 (19)O1—C20—C19123.49 (17)
C7—C8—H8120.2O1—C20—C21116.56 (17)
C9—C8—H8120.2C19—C20—C21119.95 (17)
C10—C9—C8120.8 (2)F2—C21—F1107.12 (18)
C10—C9—H9119.6F2—C21—F3105.66 (19)
C8—C9—H9119.6F1—C21—F3105.25 (18)
C9—C10—C11119.9 (2)F2—C21—C20113.74 (17)
C9—C10—H10120.1F1—C21—C20111.79 (18)
C11—C10—H10120.1F3—C21—C20112.67 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O10.932.503.1460127
C17—H17···O1i0.932.493.1937133
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC21H15ClF3OP
Mr406.75
Crystal system, space groupMonoclinic, P21/c
Temperature (K)273
a, b, c (Å)10.6377 (9), 9.8603 (9), 18.3754 (16)
β (°) 96.059 (1)
V3)1916.6 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.32
Crystal size (mm)0.30 × 0.30 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
9644, 3391, 3014
Rint0.015
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.090, 1.03
No. of reflections3391
No. of parameters245
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.34, 0.33

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.

Selected bond lengths (Å) top
C19—C201.384 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O10.932.503.1460127.0
C17—H17···O1i0.932.493.1937133.0
Symmetry code: (i) x, y+1, z.
 

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