Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044704/zl2068sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044704/zl2068Isup2.hkl |
CCDC reference: 663793
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.034
- wR factor = 0.073
- Data-to-parameter ratio = 10.1
checkCIF/PLATON results
No syntax errors found Datablock: I
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.48 From the CIF: _reflns_number_total 1643 Count of symmetry unique reflns 1641 Completeness (_total/calc) 100.12% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2 Fraction of Friedel pairs measured 0.001 Are heavy atom types Z>Si present no
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 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 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
1,3-Di(p-fluorophenyl)acetone (prepared using a modified procedure from Resendiz & Garibay (2005)): 4-Fluorophenylacetic acid (4.14 g, 26.8 mmol), 4-(dimethylamino)pyridine (3.53 g, 28.8 mmol), N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI·HCl) (5.00 g, 26.0 mmol) and 80 ml of dichloromethane were added to a 250 ml round bottom flask. The solution was stirred for four days at room temperature, after which 100 ml of 10% HCl solution was added. The organic layer was separated, washed with 10% HCl twice, saturated NaHCO3 once, dried over MgSO4 and the solvent was removed by vacuum. The resulting solid was recrystallized from aqueous ethanol to yield 2.35 g (73.5%) of the title compound. Melting Point 335–337 K. 1H NMR (300 MHz, CDCl3), δ 3.69 (s, 4H), 6.99 (m, 4H), 7.09 (m, 4H). 13C NMR (75.4 MHz, CDCl3), δ 48.4 (s), 115.8 (d, J=21.5 Hz), 129.7 (d, J=3.2 Hz),131.2 (d, J=7.8 Hz), 162.2 (d, J=246.6 Hz), 205.3 (s). 19F NMR (282 MHz, CDCl3) δ -116 (tt, J=5.5, 8.8 Hz). HRMS (EI) (m/z): calcd. for C15H12OF2 (M+) 246.0856; found 246.0860.
Lithium enolate of 1,3-di(p-fluorophenyl)acetone ether solvate: 1,3-di(p-fluorophenyl)acetone (0.29 g, 1.19 mmol) was placed in a 15 ml conical vial, dissolved in 1 ml of diethylether and cooled to 273 K. Diisopropylamine (0.2 ml, 1.41 mmol) and 2 ml of diethyl ether were placed in to a flame dried and argon purged 5 ml round bottom flask and cooled to 195 K. nBuLi (0.53 ml, 1.32 mmol) was added and the solution was warmed to 273 K for 5 minutes. The freshly prepared lithium diisopropylamide (LDA) was added to the conical vial via cannula at 273 K and the flask was shaken to mix the reactants. The solution was allowed to warm to room temperature for 30 minutes and then cooled to 253 K. Upon sitting overnight crystals formed.
The crystal of the title compound chosen for the X-ray structural characterization was selected from the paratone oil 24 h after crystals of the lithium enolate were immersed in it. Thus, the title compound is a decomposition product of the lithium enolate under ambient conditions in paratone oil.
All H-atoms were placed in idealized locations and refined as riding with appropriate thermal displacement coefficients Uiso(H) = 1.2 or 1.5 times Ueq(bearing atom).
This paper documents an unusual fact of spontaneous crystallization of the title compound in paratone oil. Crystals of the air- and moisture-sensitive lithium enolate of 1,3-di(p-fluorophenyl)acetone ether solvate (Fig.1) were examined under ambient conditions in paratone oil to select a crystal suitable for an X-ray single-crystal diffraction experiment (Kolonko et al., 2007). During the 22-hour data acquisition on the lithium enolate the glass slide with the crystals was left under air. By the next day the crystals decomposed to yield crystals of the title compound propagating from them as thin needles (Fig. 2). Such spontaneous crystallization in paratone oil is rare, yet in this case it yielded X-ray quality crystals. The title compound, Fig. 3, can be prepared directly by a modified procedure of Resendiz & Garibay (2005). Its molecular features of are typical: the endocyclic angles at the electron-withdrawing F substituent average 123.0 (2)° while the endocyclic angles at the methylene carbon atom average 118.3 (3)°. These findings are in excellent agreement with the values of 122.3 and 118.5° computed for the theoretically (DFT) optimized geometry of (I) at the b3lyp/6–31+G* level of theory (Frisch et al., 2004).
Resendiz & Garibay (2005) report a direct synthesis of the title compound; Kolonko et al. (2007) report the synthesis and characterization of a Li salt that, upon decomposition, yields the title compound. For details of the computational calculations, see Frisch et al. (2004).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Bruker, 2007); program(s) used to refine structure: SHELXTL (Bruker, 2007); molecular graphics: SHELXTL (Bruker, 2007); software used to prepare material for publication: SHELXTL (Bruker, 2007), publCIF (Westrip, 2007), modiCIFer (Guzei, 1995).
C15H12F2O | F(000) = 512 |
Mr = 246.25 | Dx = 1.355 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 2606 reflections |
a = 4.5204 (5) Å | θ = 2.5–22.9° |
b = 11.3606 (14) Å | µ = 0.11 mm−1 |
c = 23.501 (3) Å | T = 100 K |
V = 1206.9 (2) Å3 | Needle, colourless |
Z = 4 | 0.50 × 0.10 × 0.10 mm |
Bruker CCD-1000 area-detector diffractometer | 1643 independent reflections |
Radiation source: fine-focus sealed tube | 1210 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.100 |
0.30° ω and 0.4 ° φ scans | θmax = 27.5°, θmin = 1.7° |
Absorption correction: multi-scan SADABS (Bruker, 2007) | h = −5→5 |
Tmin = 0.950, Tmax = 0.990 | k = −14→14 |
15238 measured reflections | l = −30→30 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0301P)2] where P = (Fo2 + 2Fc2)/3 |
1643 reflections | (Δ/σ)max = 0.001 |
163 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.17 e Å−3 |
C15H12F2O | V = 1206.9 (2) Å3 |
Mr = 246.25 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 4.5204 (5) Å | µ = 0.11 mm−1 |
b = 11.3606 (14) Å | T = 100 K |
c = 23.501 (3) Å | 0.50 × 0.10 × 0.10 mm |
Bruker CCD-1000 area-detector diffractometer | 1643 independent reflections |
Absorption correction: multi-scan SADABS (Bruker, 2007) | 1210 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.990 | Rint = 0.100 |
15238 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.19 e Å−3 |
1643 reflections | Δρmin = −0.17 e Å−3 |
163 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 | −0.1730 (3) | 0.96475 (11) | 0.68798 (5) | 0.0339 (4) | |
F2 | 0.0973 (4) | 0.40877 (12) | 1.10857 (5) | 0.0467 (5) | |
O1 | 0.2673 (4) | 0.71247 (12) | 0.89696 (6) | 0.0238 (4) | |
C1 | 0.3178 (5) | 0.88445 (17) | 0.80243 (8) | 0.0206 (5) | |
H1 | 0.3875 | 0.9158 | 0.8374 | 0.025* | |
C2 | 0.1182 (5) | 0.94850 (18) | 0.77045 (9) | 0.0224 (5) | |
H2 | 0.0472 | 1.0225 | 0.7834 | 0.027* | |
C3 | 0.0252 (5) | 0.90235 (19) | 0.71955 (9) | 0.0239 (5) | |
C4 | 0.1244 (5) | 0.79668 (18) | 0.69894 (9) | 0.0243 (6) | |
H4 | 0.0597 | 0.7677 | 0.6631 | 0.029* | |
C5 | 0.3225 (5) | 0.73345 (18) | 0.73208 (8) | 0.0216 (5) | |
H5 | 0.3939 | 0.6599 | 0.7186 | 0.026* | |
C6 | 0.4188 (5) | 0.77487 (18) | 0.78442 (8) | 0.0189 (5) | |
C7 | 0.6201 (5) | 0.70229 (18) | 0.82110 (8) | 0.0214 (5) | |
H7A | 0.8014 | 0.7483 | 0.8291 | 0.026* | |
H7B | 0.6796 | 0.6311 | 0.7997 | 0.026* | |
C8 | 0.4829 (5) | 0.66449 (19) | 0.87723 (9) | 0.0195 (5) | |
C9 | 0.6399 (5) | 0.56467 (18) | 0.90711 (8) | 0.0251 (6) | |
H9A | 0.6545 | 0.4973 | 0.8805 | 0.030* | |
H9B | 0.8438 | 0.5902 | 0.9163 | 0.030* | |
C10 | 0.4930 (5) | 0.52336 (18) | 0.96098 (8) | 0.0206 (5) | |
C11 | 0.3181 (5) | 0.42347 (18) | 0.96131 (9) | 0.0236 (5) | |
H11 | 0.2909 | 0.3806 | 0.9270 | 0.028* | |
C12 | 0.1816 (6) | 0.38470 (19) | 1.01073 (9) | 0.0288 (6) | |
H12 | 0.0600 | 0.3165 | 1.0108 | 0.035* | |
C13 | 0.2279 (6) | 0.4481 (2) | 1.05949 (9) | 0.0293 (6) | |
C14 | 0.3959 (6) | 0.54752 (19) | 1.06119 (9) | 0.0306 (6) | |
H14 | 0.4210 | 0.5898 | 1.0957 | 0.037* | |
C15 | 0.5291 (5) | 0.58556 (19) | 1.01147 (9) | 0.0264 (6) | |
H15 | 0.6465 | 0.6549 | 1.0118 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0310 (9) | 0.0389 (7) | 0.0318 (7) | 0.0070 (7) | −0.0021 (7) | 0.0133 (6) |
F2 | 0.0688 (12) | 0.0433 (9) | 0.0280 (8) | 0.0117 (9) | 0.0180 (8) | 0.0118 (6) |
O1 | 0.0235 (10) | 0.0256 (8) | 0.0222 (8) | 0.0052 (8) | 0.0033 (7) | 0.0004 (6) |
C1 | 0.0229 (14) | 0.0192 (10) | 0.0198 (11) | −0.0047 (10) | 0.0013 (10) | −0.0009 (9) |
C2 | 0.0229 (14) | 0.0176 (11) | 0.0266 (12) | −0.0004 (10) | 0.0067 (10) | 0.0032 (9) |
C3 | 0.0186 (13) | 0.0284 (12) | 0.0246 (12) | 0.0000 (11) | 0.0003 (10) | 0.0117 (10) |
C4 | 0.0263 (15) | 0.0282 (12) | 0.0183 (11) | −0.0044 (11) | 0.0006 (10) | 0.0025 (9) |
C5 | 0.0229 (14) | 0.0207 (11) | 0.0213 (11) | −0.0026 (11) | 0.0050 (10) | −0.0003 (9) |
C6 | 0.0168 (13) | 0.0203 (11) | 0.0196 (10) | −0.0028 (10) | 0.0044 (9) | 0.0039 (9) |
C7 | 0.0216 (14) | 0.0222 (11) | 0.0204 (11) | −0.0004 (10) | 0.0019 (10) | −0.0008 (9) |
C8 | 0.0173 (15) | 0.0203 (11) | 0.0207 (11) | −0.0027 (10) | −0.0015 (11) | −0.0021 (9) |
C9 | 0.0221 (15) | 0.0268 (12) | 0.0264 (12) | 0.0044 (11) | 0.0024 (10) | 0.0052 (10) |
C10 | 0.0194 (14) | 0.0211 (11) | 0.0214 (11) | 0.0050 (10) | 0.0006 (11) | 0.0028 (9) |
C11 | 0.0298 (15) | 0.0219 (11) | 0.0191 (10) | 0.0034 (11) | −0.0008 (10) | −0.0015 (9) |
C12 | 0.0337 (17) | 0.0211 (11) | 0.0318 (13) | −0.0033 (12) | 0.0026 (12) | 0.0037 (10) |
C13 | 0.0388 (17) | 0.0302 (13) | 0.0188 (11) | 0.0115 (12) | 0.0054 (11) | 0.0072 (10) |
C14 | 0.0421 (18) | 0.0300 (13) | 0.0197 (11) | 0.0049 (12) | −0.0059 (11) | −0.0045 (10) |
C15 | 0.0296 (16) | 0.0204 (12) | 0.0291 (12) | 0.0004 (11) | −0.0044 (11) | −0.0006 (10) |
F1—C3 | 1.362 (2) | C7—H7B | 0.9900 |
F2—C13 | 1.371 (2) | C8—C9 | 1.511 (3) |
O1—C8 | 1.209 (3) | C9—C10 | 1.505 (3) |
C1—C2 | 1.381 (3) | C9—H9A | 0.9900 |
C1—C6 | 1.392 (3) | C9—H9B | 0.9900 |
C1—H1 | 0.9500 | C10—C11 | 1.383 (3) |
C2—C3 | 1.372 (3) | C10—C15 | 1.391 (3) |
C2—H2 | 0.9500 | C11—C12 | 1.387 (3) |
C3—C4 | 1.370 (3) | C11—H11 | 0.9500 |
C4—C5 | 1.387 (3) | C12—C13 | 1.370 (3) |
C4—H4 | 0.9500 | C12—H12 | 0.9500 |
C5—C6 | 1.387 (3) | C13—C14 | 1.361 (3) |
C5—H5 | 0.9500 | C14—C15 | 1.384 (3) |
C6—C7 | 1.500 (3) | C14—H14 | 0.9500 |
C7—C8 | 1.520 (3) | C15—H15 | 0.9500 |
C7—H7A | 0.9900 | ||
C2—C1—C6 | 121.3 (2) | C9—C8—C7 | 115.1 (2) |
C2—C1—H1 | 119.3 | C10—C9—C8 | 114.70 (19) |
C6—C1—H1 | 119.3 | C10—C9—H9A | 108.6 |
C3—C2—C1 | 118.24 (19) | C8—C9—H9A | 108.6 |
C3—C2—H2 | 120.9 | C10—C9—H9B | 108.6 |
C1—C2—H2 | 120.9 | C8—C9—H9B | 108.6 |
F1—C3—C4 | 118.6 (2) | H9A—C9—H9B | 107.6 |
F1—C3—C2 | 118.52 (19) | C11—C10—C15 | 118.64 (19) |
C4—C3—C2 | 122.9 (2) | C11—C10—C9 | 120.86 (18) |
C3—C4—C5 | 117.8 (2) | C15—C10—C9 | 120.5 (2) |
C3—C4—H4 | 121.1 | C10—C11—C12 | 121.31 (19) |
C5—C4—H4 | 121.1 | C10—C11—H11 | 119.3 |
C4—C5—C6 | 121.7 (2) | C12—C11—H11 | 119.3 |
C4—C5—H5 | 119.2 | C13—C12—C11 | 117.7 (2) |
C6—C5—H5 | 119.2 | C13—C12—H12 | 121.1 |
C5—C6—C1 | 118.0 (2) | C11—C12—H12 | 121.1 |
C5—C6—C7 | 120.90 (19) | C14—C13—C12 | 123.1 (2) |
C1—C6—C7 | 121.05 (19) | C14—C13—F2 | 119.09 (19) |
C6—C7—C8 | 114.0 (2) | C12—C13—F2 | 117.8 (2) |
C6—C7—H7A | 108.8 | C13—C14—C15 | 118.5 (2) |
C8—C7—H7A | 108.8 | C13—C14—H14 | 120.8 |
C6—C7—H7B | 108.8 | C15—C14—H14 | 120.8 |
C8—C7—H7B | 108.8 | C14—C15—C10 | 120.7 (2) |
H7A—C7—H7B | 107.7 | C14—C15—H15 | 119.6 |
O1—C8—C9 | 122.59 (19) | C10—C15—H15 | 119.6 |
O1—C8—C7 | 122.3 (2) | ||
C6—C1—C2—C3 | −1.2 (3) | O1—C8—C9—C10 | 4.6 (3) |
C1—C2—C3—F1 | 179.59 (19) | C7—C8—C9—C10 | −176.77 (19) |
C1—C2—C3—C4 | −0.8 (3) | C8—C9—C10—C11 | 100.0 (2) |
F1—C3—C4—C5 | −178.96 (19) | C8—C9—C10—C15 | −79.6 (3) |
C2—C3—C4—C5 | 1.5 (3) | C15—C10—C11—C12 | −0.4 (3) |
C3—C4—C5—C6 | 0.0 (3) | C9—C10—C11—C12 | −180.0 (2) |
C4—C5—C6—C1 | −1.9 (3) | C10—C11—C12—C13 | −0.6 (4) |
C4—C5—C6—C7 | 176.6 (2) | C11—C12—C13—C14 | 1.2 (4) |
C2—C1—C6—C5 | 2.6 (3) | C11—C12—C13—F2 | −178.9 (2) |
C2—C1—C6—C7 | −176.0 (2) | C12—C13—C14—C15 | −0.8 (4) |
C5—C6—C7—C8 | −115.5 (2) | F2—C13—C14—C15 | 179.3 (2) |
C1—C6—C7—C8 | 63.1 (3) | C13—C14—C15—C10 | −0.2 (4) |
C6—C7—C8—O1 | −18.2 (3) | C11—C10—C15—C14 | 0.8 (3) |
C6—C7—C8—C9 | 163.18 (18) | C9—C10—C15—C14 | −179.6 (2) |
Experimental details
Crystal data | |
Chemical formula | C15H12F2O |
Mr | 246.25 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 4.5204 (5), 11.3606 (14), 23.501 (3) |
V (Å3) | 1206.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.50 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker CCD-1000 area-detector |
Absorption correction | Multi-scan SADABS (Bruker, 2007) |
Tmin, Tmax | 0.950, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15238, 1643, 1210 |
Rint | 0.100 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.073, 1.00 |
No. of reflections | 1643 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.17 |
Computer programs: SMART (Bruker, 2000), SAINT-Plus (Bruker, 2007), SHELXTL (Bruker, 2007), publCIF (Westrip, 2007), modiCIFer (Guzei, 1995).
This paper documents an unusual fact of spontaneous crystallization of the title compound in paratone oil. Crystals of the air- and moisture-sensitive lithium enolate of 1,3-di(p-fluorophenyl)acetone ether solvate (Fig.1) were examined under ambient conditions in paratone oil to select a crystal suitable for an X-ray single-crystal diffraction experiment (Kolonko et al., 2007). During the 22-hour data acquisition on the lithium enolate the glass slide with the crystals was left under air. By the next day the crystals decomposed to yield crystals of the title compound propagating from them as thin needles (Fig. 2). Such spontaneous crystallization in paratone oil is rare, yet in this case it yielded X-ray quality crystals. The title compound, Fig. 3, can be prepared directly by a modified procedure of Resendiz & Garibay (2005). Its molecular features of are typical: the endocyclic angles at the electron-withdrawing F substituent average 123.0 (2)° while the endocyclic angles at the methylene carbon atom average 118.3 (3)°. These findings are in excellent agreement with the values of 122.3 and 118.5° computed for the theoretically (DFT) optimized geometry of (I) at the b3lyp/6–31+G* level of theory (Frisch et al., 2004).