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

Manoj Kumar, K.E.; Palakshamurthy, B.S.; Suchetan, P.A.; Madan Kumar, S.; Lokanath, N.K.; Sreenivasa, S.

doi:10.1107/S1600536813028535

organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1705

doi:10.1107/S1600536813028535

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

K.E. Manoj Kumar,^a B. S. Palakshamurthy,^b P. A. Suchetan,^c S. Madan Kumar,^d N.K. Lokanath ^d and S. Sreenivasa ^a ^*

^aDepartment of Studies and Research in Chemistry, Tumkur University, Tumkur, Karnataka 572 103, India, ^bDepartment of Studies and Research in Physics, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, ^cDepartment of Studies and Research in Chemistry, U.C.S., Tumkur University, Tumkur, Karnataka 572 103, India, and ^dDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore, India
^*Correspondence e-mail: drsreenivasa@yahoo.co.in

(Received 14 October 2013; accepted 17 October 2013; online 26 October 2013)

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.

CCDC reference: 966924

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, C 2/c
a = 12.393 (4) Å
b = 13.433 (5) Å
c = 12.877 (5) Å
β = 112.49 (2)°
V = 1980.7 (13) Å³
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[F² > 2σ(F²)] = 0.074
wR(F²) = 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

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) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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.

Supporting information

CCDC reference: 966924

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813028535/hb7151sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813028535/hb7151Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813028535/hb7151Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); 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 (Sheldrick, 2008).

Figures top

	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.

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

Crystal data top

C₁₀H₅F₅O₂	Prism
M_r = 252.14	D_x = 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 top

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

Refinement top

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(F_o²) + (0.1433P)² + 2.2069P] where P = (F_o² + 2F_c²)/3
1604 reflections	(Δ/σ)_max = 0.012
154 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₁₀H₅F₅O₂	V = 1980.7 (13) Å³
M_r = 252.14	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 12.393 (4) Å	µ = 0.18 mm⁻¹
b = 13.433 (5) Å	T = 294 K
c = 12.877 (5) Å	0.24 × 0.20 × 0.16 mm
β = 112.49 (2)°

Data collection top

Bruker APEXII CCD diffractometer	1604 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1246 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.972	R_int = 0.040
5651 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	0 restraints
wR(F²) = 0.239	H-atom parameters constrained
S = 1.08	Δρ_max = 0.43 e Å⁻³
1604 reflections	Δρ_min = −0.47 e Å⁻³
154 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

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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) top

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) top

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.

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

The authors acknowledge the IOE X-ray diffractometer Facility, University of Mysore, Mysore, for the data collection. KEM and SS acknowledge Tumkur University, Tumkur, for providing laboratory facilities.

References

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