1-(3,5-Di­fluoro­phen­yl)-4,4,4-tri­fluoro­butane-1,3-dione

Abstract

In the title compound, C₁₀H₅F₅O₂, the C=O bonds are syn to one another. In the crystal, mol­ecules are linked into C(9) chains parallel to [101] through weak C—H⋯O inter­actions, with the O atom adjacent to the –CF₃ group acting as the acceptor.

Related literature  

For biological-activity studies of compounds with tri­fluoro­methyl substituents, see: Manoj Kumar et al. (2013 ▶).

Experimental  

Crystal data  

• C₁₀H₅F₅O₂

• M _r = 252.14

• Monoclinic,

• a = 12.393 (4) Å

• b = 13.433 (5) Å

• c = 12.877 (5) Å

• β = 112.49 (2)°

• V = 1980.7 (13) ų

• Z = 8

• Mo Kα radiation

• μ = 0.18 mm⁻¹

• T = 294 K

• 0.24 × 0.20 × 0.16 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.959, T _max = 0.972

• 5651 measured reflections

• 1604 independent reflections

• 1246 reflections with I > 2σ(I)

• R _int = 0.040

Refinement  

• R[F ² > 2σ(F ²)] = 0.074

• wR(F ²) = 0.239

• S = 1.08

• 1604 reflections

• 154 parameters

• H-atom parameters constrained

• Δρ_max = 0.43 e Å⁻³

• Δρ_min = −0.47 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT-Plus (Bruker, 2009 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2i	0.93	2.53	3.462 (5)	177

Symmetry code: (i) .

supplementary crystallographic information

1. Comment

As part of our ongoing studies of the biological activities of compounds with a trifluoromethyl substituent (Manoj Kumar et al., 2013), we now describe the structure of the title compound, (I).

The two C=O bonds are syn to one another (Fig.1), the O1—C7—C8—C9 and O2—C9—C8—C7 torsion angles being 0.4 (5) and -0.3 (6)°, respectively. In the crystal, the molecules are linked into C(9) chains parallel to [101] through a weak C3—H3···O2 interaction (Fig.2).

2. Experimental

3,5-Difluoroacetophenone (1 mmol) and sodium hydride (1.5 mmol) were taken in dry THF (20 ml), and the solution was stirred for 30 min at 0°C. To this solution trifluoroethylacetate (1.2 mmol) was added and the reaction mixture was stirred for 10 h at room temperature under nitrogen atmosphere. The reaction was monitored by TLC. The crude mass was purified by column chromatography using petroleum ether and ethyl acetate as an eluent (7:3), to obtain a yellow solid. Pale yellow prisms were obtained by recrystallisation fron dichloromethane/methanol (9:1) solution.

3. Refinement

The H atoms were positioned with idealized geometry using a riding model with C—H = 0.93–0.97 Å. All H atoms were refined with isotropic displacement parameters (set to 1.2 times of the U_eq of the parent atom).

Figures

Fig. 1.

Molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

Molecular packing foming C(9) chains parallel to [101] with hydrogen bonding shown as dashed lines.

Crystal data

C10H5F5O2	Prism
Mr = 252.14	Dx = 1.691 Mg m−3
Monoclinic, C2/c	Melting point: 393 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 12.393 (4) Å	Cell parameters from 1023 reflections
b = 13.433 (5) Å	θ = 0.0–24.6°
c = 12.877 (5) Å	µ = 0.18 mm−1
β = 112.49 (2)°	T = 294 K
V = 1980.7 (13) Å3	Prism, colourless
Z = 8	0.24 × 0.20 × 0.16 mm
F(000) = 1008

Data collection

Bruker APEXII CCD diffractometer	1604 independent reflections
Radiation source: fine-focus sealed tube	1246 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
phi and ω scans	θmax = 24.6°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
Tmin = 0.959, Tmax = 0.972	k = −15→7
5651 measured reflections	l = −14→14

Refinement

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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.239	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.1433P)2 + 2.2069P] where P = (Fo2 + 2Fc2)/3
1604 reflections	(Δ/σ)max = 0.012
154 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.47 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.0373 (3)	0.3441 (3)	0.4970 (3)	0.0558 (9)
H1	0.0691	0.4058	0.4923	0.067*
C2	−0.0308 (3)	0.3323 (3)	0.5594 (3)	0.0624 (10)
C3	−0.0787 (4)	0.2426 (3)	0.5705 (3)	0.0684 (11)
H3	−0.1238	0.2360	0.6135	0.082*
C4	−0.0565 (4)	0.1636 (3)	0.5147 (4)	0.0649 (10)
C5	0.0106 (3)	0.1700 (3)	0.4506 (3)	0.0574 (9)
H5	0.0242	0.1143	0.4144	0.069*
C6	0.0574 (3)	0.2624 (2)	0.4416 (3)	0.0474 (8)
C7	0.1298 (3)	0.2699 (2)	0.3734 (3)	0.0476 (8)
C8	0.1640 (3)	0.3603 (3)	0.3419 (3)	0.0511 (8)
H8A	0.0937	0.3983	0.3019	0.061*
H8B	0.2077	0.3967	0.4101	0.061*
C9	0.2304 (3)	0.3596 (3)	0.2760 (3)	0.0515 (9)
C10	0.2656 (3)	0.4562 (3)	0.2375 (3)	0.0624 (10)
F1	−0.0500 (3)	0.4121 (2)	0.6129 (3)	0.1000 (11)
F2	−0.1027 (3)	0.0740 (2)	0.5224 (3)	0.1010 (11)
F3	0.2245 (3)	0.4627 (2)	0.1272 (2)	0.0913 (9)
F4	0.3807 (2)	0.4629 (2)	0.2695 (3)	0.0989 (10)
F5	0.2306 (3)	0.5370 (2)	0.2748 (3)	0.1110 (13)
O1	0.1598 (2)	0.18650 (19)	0.3425 (2)	0.0671 (8)
O2	0.2645 (2)	0.2827 (2)	0.2411 (2)	0.0666 (8)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.065 (2)	0.051 (2)	0.066 (2)	0.0018 (15)	0.0410 (17)	−0.0022 (16)
C2	0.072 (2)	0.063 (2)	0.070 (2)	0.0110 (18)	0.0473 (19)	−0.0002 (17)
C3	0.070 (2)	0.083 (3)	0.073 (2)	0.007 (2)	0.050 (2)	0.012 (2)
C4	0.072 (2)	0.059 (2)	0.081 (2)	−0.0095 (18)	0.048 (2)	0.0108 (19)
C5	0.064 (2)	0.050 (2)	0.069 (2)	−0.0058 (15)	0.0380 (17)	−0.0011 (15)
C6	0.0508 (18)	0.0460 (18)	0.0561 (18)	0.0013 (13)	0.0323 (15)	0.0034 (14)
C7	0.0473 (16)	0.0457 (18)	0.0588 (19)	0.0002 (13)	0.0306 (15)	−0.0036 (14)
C8	0.0564 (18)	0.0448 (19)	0.065 (2)	0.0001 (14)	0.0373 (16)	−0.0009 (15)
C9	0.0535 (18)	0.048 (2)	0.063 (2)	−0.0011 (14)	0.0335 (16)	−0.0016 (15)
C10	0.069 (2)	0.058 (2)	0.079 (3)	−0.0047 (17)	0.049 (2)	−0.0035 (18)
F1	0.146 (3)	0.0803 (18)	0.121 (2)	0.0129 (16)	0.105 (2)	−0.0090 (15)
F2	0.125 (2)	0.0773 (18)	0.138 (3)	−0.0305 (16)	0.092 (2)	0.0011 (16)
F3	0.112 (2)	0.0859 (19)	0.0818 (18)	−0.0116 (15)	0.0440 (15)	0.0191 (13)
F4	0.0676 (15)	0.096 (2)	0.139 (3)	−0.0226 (13)	0.0460 (15)	0.0177 (17)
F5	0.169 (3)	0.0515 (16)	0.173 (3)	−0.0089 (16)	0.133 (3)	−0.0034 (16)
O1	0.0897 (19)	0.0399 (14)	0.102 (2)	0.0042 (12)	0.0704 (16)	−0.0031 (12)
O2	0.0793 (17)	0.0555 (16)	0.0924 (19)	0.0030 (12)	0.0633 (15)	−0.0029 (13)

Geometric parameters (Å, º)

C1—C2	1.379 (5)	C6—C7	1.479 (5)
C1—C6	1.383 (5)	C7—O1	1.290 (4)
C1—H1	0.9300	C7—C8	1.396 (5)
C2—F1	1.344 (5)	C8—C9	1.389 (5)
C2—C3	1.374 (6)	C8—H8A	0.9700
C3—C4	1.367 (6)	C8—H8B	0.9700
C3—H3	0.9300	C9—O2	1.262 (4)
C4—F2	1.353 (5)	C9—C10	1.512 (5)
C4—C5	1.381 (5)	C10—F3	1.316 (5)
C5—C6	1.393 (5)	C10—F5	1.327 (5)
C5—H5	0.9300	C10—F4	1.328 (4)
C2—C1—C6	118.8 (3)	O1—C7—C8	120.7 (3)
C2—C1—H1	120.6	O1—C7—C6	115.8 (3)
C6—C1—H1	120.6	C8—C7—C6	123.5 (3)
F1—C2—C3	118.5 (3)	C9—C8—C7	119.2 (3)
F1—C2—C1	118.4 (4)	C9—C8—H8A	107.5
C3—C2—C1	123.1 (4)	C7—C8—H8A	107.5
C4—C3—C2	116.4 (3)	C9—C8—H8B	107.5
C4—C3—H3	121.8	C7—C8—H8B	107.5
C2—C3—H3	121.8	H8A—C8—H8B	107.0
F2—C4—C3	118.5 (3)	O2—C9—C8	125.5 (3)
F2—C4—C5	117.9 (4)	O2—C9—C10	114.0 (3)
C3—C4—C5	123.7 (4)	C8—C9—C10	120.5 (3)
C4—C5—C6	118.0 (4)	F3—C10—F5	106.9 (4)
C4—C5—H5	121.0	F3—C10—F4	104.9 (3)
C6—C5—H5	121.0	F5—C10—F4	107.1 (3)
C1—C6—C5	120.0 (3)	F3—C10—C9	111.8 (3)
C1—C6—C7	121.5 (3)	F5—C10—C9	114.1 (3)
C5—C6—C7	118.4 (3)	F4—C10—C9	111.5 (3)
C6—C1—C2—F1	−179.9 (3)	C5—C6—C7—O1	−11.0 (5)
C6—C1—C2—C3	0.8 (6)	C1—C6—C7—C8	−12.7 (5)
F1—C2—C3—C4	−179.9 (4)	C5—C6—C7—C8	168.3 (3)
C1—C2—C3—C4	−0.6 (6)	O1—C7—C8—C9	0.4 (5)
C2—C3—C4—F2	−179.5 (4)	C6—C7—C8—C9	−178.9 (3)
C2—C3—C4—C5	0.4 (6)	C7—C8—C9—O2	−0.3 (6)
F2—C4—C5—C6	179.4 (3)	C7—C8—C9—C10	178.1 (3)
C3—C4—C5—C6	−0.5 (6)	O2—C9—C10—F3	59.0 (4)
C2—C1—C6—C5	−0.9 (5)	C8—C9—C10—F3	−119.5 (4)
C2—C1—C6—C7	−179.9 (3)	O2—C9—C10—F5	−179.5 (3)
C4—C5—C6—C1	0.7 (5)	C8—C9—C10—F5	1.9 (5)
C4—C5—C6—C7	179.8 (3)	O2—C9—C10—F4	−58.1 (4)
C1—C6—C7—O1	168.0 (3)	C8—C9—C10—F4	123.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2i	0.93	2.53	3.462 (5)	177

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.