PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1606.
Published online 2010 June 9. doi:  10.1107/S1600536810020234
PMCID: PMC3006816

2-Oxo-4-trifluoro­meth­yl-2H-chromen-7-yl 2-bromo-2-methyl­propano­ate

Abstract

In the title compound, C14H10BrF3O4, the coumarin ring system is almost plannar (r.m.s. deviation = 0.025 Å) and a short C—H(...)F contact occurs. The propano­ate fragment is orientated almost perpendicular to the ring [dihedral angle = 71.80 (12)°]. In the crystal, mol­ecules are linked by C—H(...)O hydrogen bonds, generating [100] chains.

Related literature

For the applications of the title compound in polymer chemistry, see: Sinkel et al. (2008 [triangle]); Matyjaszewski et al. (2008 [triangle]); Stenzel-Rosenbaum et al. (2001 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1606-scheme1.jpg

Experimental

Crystal data

  • C14H10BrF3O4
  • M r = 379.13
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1606-efi1.jpg
  • a = 6.1842 (4) Å
  • b = 11.0297 (6) Å
  • c = 11.0619 (7) Å
  • α = 99.982 (2)°
  • β = 91.797 (2)°
  • γ = 104.387 (2)°
  • V = 717.61 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.91 mm−1
  • T = 298 K
  • 0.40 × 0.26 × 0.24 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2004 [triangle]) T min = 0.389, T max = 0.542
  • 9951 measured reflections
  • 3796 independent reflections
  • 2390 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.109
  • S = 1.01
  • 3796 reflections
  • 201 parameters
  • H-atom parameters constrained
  • Δρmax = 0.78 e Å−3
  • Δρmin = −0.85 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: SAINT-Plus (Bruker, 2004 [triangle]); data reduction: SAINT-Plus and XPREP (Bruker, 2004 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020234/hb5450sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810020234/hb5450Isup2.hkl

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

Acknowledgments

The authors acknowledge the Department of Chemistry, IIT Madras, for the X-ray data collection.

supplementary crystallographic information

Comment

The title compound C14H10BrF3O4, is a monofunctional coumarin derivative, which is used as an initiator (Sinkelet al. 2008) in Atom Transfer Radical Polymerization (ATRP). Being a monofunctional unit it can form end-functionalized linear polymers (Matyjaszewski et al. 2008; Stenzel-Rosenbaum et al.2001) when used as an initiator. Since most of the synthesized functionalized initiators are characterized by other techniques, their single crystal XRD reports are few.

The title compound is one such successful ATRP initiator which was crystallised from chloroform. It contains coumarin derivative with bromo methyl propanoate. The coumarin moiety is an important oxygen containing heterocyclic compound with diverse bioactivities such as non peptidic HIV protease inhibition and tyrosine kinase inhibition. Owing to such interesting properties, the synthesis of coumarin based initiators and their crystal structures are worth while to study.

In the title compound C14 H10 Br F3 O4, the coumarin ring system is plannar with the 2-bromo-2-methyl propanoate moiety almost perpendicular. The C—F bond lengths of 1.333 (2) Å,1.324 (3)Å and 1.331 (3)Å are normal in this structure. One F atom (F1) lie in plane with the coumarin ring system and the other two F atoms are above and below the plane. The torsion angle of C6—C7—O3—C11 and C8—C7—O3—C11 are -114.21 (3)° and 71.42 (2)° respectively. The crystal is stabilized by intermolecular C—H···O hydrogen bond.

Experimental

7-Hydroxy-4-trifluoromethylcoumarin 5 g (0.02 mole), triethylamine 4.83 g (0.04 mole) and THF (400 ml) were placed in a 3-neck round bottomed flask. Bromoisobutyrl bromide 10.9 g (0.04 mole) was added slowly, using a syringe, with stirring, upon which an white precipitate of triethylammonium bromide was formed. The mixture was left to react for 6 hours, with stirring. Subsequently, triethylammonium bromide, the precipitate was removed by filtration and the THF was removed by rotary evaporation. The resulting crude product was dissolved in ethyl acetate, washed with bicarbonate solution and then with water thrice followed by brine solution and dried over anhydrous sodium sulphate. The resulting solvent was removed by rotary evaporation. The product was purified by column chromatography technique using 15% ethyl acetate in hexane as the eluent to obtain pure initiator as a bright white solid. Recrystallization of the compound from chloroform gave colourless blocks of (I).

Refinement

All hydrogen atoms were fixed geometrically and allowed to ride on the parent carbon atoms, with aromatic C—H = 0.93 Å and methyl C—H = 0.96 Å. The displacement parameters were set for phenyl H atoms at Uiso(H) = 1.2Ueq(C) and methyl H atoms at Uiso(H) = 1.5Ueq(C).

Figures

Fig. 1.
View of (I) with atoms represented as 30% probability ellipsoids.
Fig. 2.
The packing diagram showing the C—H···O interaction.

Crystal data

C14H10BrF3O4Z = 2
Mr = 379.13F(000) = 376
Triclinic, P1Dx = 1.755 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.1842 (4) ÅCell parameters from 3404 reflections
b = 11.0297 (6) Åθ = 2.4–25.3°
c = 11.0619 (7) ŵ = 2.91 mm1
α = 99.982 (2)°T = 298 K
β = 91.797 (2)°Rectangular, colourless
γ = 104.387 (2)°0.40 × 0.26 × 0.24 mm
V = 717.61 (8) Å3

Data collection

Bruker APEXII CCD diffractometer3796 independent reflections
Radiation source: fine-focus sealed tube2390 reflections with I > 2σ(I)
graphiteRint = 0.022
phi and ω scansθmax = 30.8°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)h = −7→8
Tmin = 0.389, Tmax = 0.542k = −15→14
9951 measured reflectionsl = −13→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0464P)2 + 0.448P] where P = (Fo2 + 2Fc2)/3
3796 reflections(Δ/σ)max < 0.001
201 parametersΔρmax = 0.78 e Å3
0 restraintsΔρmin = −0.85 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)are estimated using the full covariance matrix. The cell esds are takeninto account individually in the estimation of esds in distances, anglesand torsion angles; correlations between esds in cell parameters are onlyused when they are defined by crystal symmetry. An approximate (isotropic)treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
Br10.06908 (6)−0.04175 (3)0.29516 (4)0.06662 (16)
C10.2614 (5)0.5339 (3)−0.2219 (3)0.0450 (7)
C20.4147 (5)0.4806 (3)−0.2966 (3)0.0450 (7)
H20.45740.5118−0.36750.054*
C30.4972 (4)0.3873 (3)−0.2666 (2)0.0363 (6)
C40.4377 (4)0.3379 (2)−0.1559 (2)0.0322 (5)
C50.5183 (4)0.2437 (3)−0.1127 (2)0.0375 (6)
H50.62320.2098−0.15570.045*
C60.4449 (5)0.2007 (3)−0.0080 (3)0.0408 (6)
H60.49950.13850.02020.049*
C70.2881 (4)0.2518 (3)0.0548 (2)0.0359 (6)
C80.2074 (4)0.3459 (3)0.0179 (2)0.0386 (6)
H80.10410.38010.06220.046*
C90.2849 (4)0.3880 (2)−0.0872 (2)0.0333 (6)
C100.6453 (5)0.3300 (3)−0.3523 (3)0.0464 (7)
C110.0108 (4)0.1442 (3)0.1690 (3)0.0361 (6)
C12−0.0307 (4)0.1167 (3)0.2974 (3)0.0389 (6)
C130.1076 (6)0.2198 (3)0.4010 (3)0.0541 (8)
H13A0.26390.23170.38870.081*
H13B0.07840.19400.47870.081*
H13C0.06720.29830.40050.081*
C14−0.2790 (5)0.0855 (3)0.3145 (3)0.0516 (8)
H14A−0.33310.15960.31290.077*
H14B−0.30450.05910.39230.077*
H14C−0.35690.01790.24930.077*
F10.6893 (4)0.3893 (2)−0.44723 (18)0.0775 (6)
F20.8423 (3)0.3353 (2)−0.29621 (18)0.0652 (5)
F30.5518 (3)0.20819 (19)−0.39741 (17)0.0645 (5)
O10.2025 (3)0.48421 (18)−0.11926 (17)0.0429 (5)
O20.1777 (4)0.6161 (2)−0.2441 (2)0.0648 (6)
O30.2269 (3)0.2130 (2)0.16562 (17)0.0452 (5)
O4−0.1216 (3)0.1118 (2)0.08271 (19)0.0498 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0781 (3)0.0645 (3)0.0835 (3)0.04411 (19)0.0312 (2)0.0426 (2)
C10.0603 (18)0.0383 (16)0.0422 (16)0.0201 (13)0.0037 (14)0.0123 (13)
C20.0613 (18)0.0436 (17)0.0361 (15)0.0170 (13)0.0083 (13)0.0174 (13)
C30.0408 (14)0.0373 (15)0.0311 (13)0.0087 (11)0.0039 (11)0.0083 (11)
C40.0354 (13)0.0320 (13)0.0301 (13)0.0100 (10)0.0012 (11)0.0066 (11)
C50.0398 (14)0.0386 (15)0.0398 (15)0.0179 (11)0.0082 (12)0.0103 (12)
C60.0420 (15)0.0426 (16)0.0436 (16)0.0157 (12)0.0015 (13)0.0166 (13)
C70.0355 (13)0.0419 (15)0.0314 (13)0.0071 (11)0.0006 (11)0.0141 (12)
C80.0399 (14)0.0448 (16)0.0359 (14)0.0165 (12)0.0090 (12)0.0114 (12)
C90.0371 (13)0.0322 (13)0.0343 (14)0.0136 (11)−0.0003 (11)0.0097 (11)
C100.0507 (17)0.055 (2)0.0388 (16)0.0182 (14)0.0111 (13)0.0158 (14)
C110.0355 (13)0.0387 (15)0.0409 (15)0.0163 (11)0.0076 (12)0.0150 (12)
C120.0410 (14)0.0400 (15)0.0434 (16)0.0164 (12)0.0110 (12)0.0184 (13)
C130.063 (2)0.062 (2)0.0375 (16)0.0097 (16)0.0049 (14)0.0203 (15)
C140.0483 (17)0.0514 (18)0.060 (2)0.0164 (14)0.0240 (15)0.0162 (16)
F10.1027 (17)0.1013 (16)0.0556 (12)0.0515 (13)0.0434 (12)0.0444 (12)
F20.0437 (10)0.0907 (15)0.0663 (12)0.0224 (10)0.0112 (9)0.0201 (11)
F30.0773 (13)0.0584 (12)0.0548 (11)0.0235 (10)0.0128 (10)−0.0077 (9)
O10.0573 (12)0.0422 (11)0.0403 (11)0.0277 (9)0.0093 (9)0.0146 (9)
O20.0941 (18)0.0559 (14)0.0647 (15)0.0455 (13)0.0132 (13)0.0270 (12)
O30.0371 (10)0.0647 (13)0.0372 (10)0.0071 (9)0.0029 (8)0.0271 (9)
O40.0422 (11)0.0607 (13)0.0453 (12)0.0078 (9)−0.0033 (10)0.0161 (10)

Geometric parameters (Å, °)

Br1—C121.990 (3)C8—H80.9300
C1—O21.205 (3)C9—O11.378 (3)
C1—O11.366 (3)C10—F31.324 (4)
C1—C21.444 (4)C10—F11.332 (3)
C2—C31.340 (4)C10—F21.333 (4)
C2—H20.9300C11—O41.181 (3)
C3—C41.447 (4)C11—O31.368 (3)
C3—C101.507 (4)C11—C121.520 (4)
C4—C91.391 (4)C12—C141.513 (4)
C4—C51.404 (4)C12—C131.529 (4)
C5—C61.375 (4)C13—H13A0.9600
C5—H50.9300C13—H13B0.9600
C6—C71.385 (4)C13—H13C0.9600
C6—H60.9300C14—H14A0.9600
C7—C81.373 (4)C14—H14B0.9600
C7—O31.400 (3)C14—H14C0.9600
C8—C91.382 (4)
O2—C1—O1117.5 (3)F3—C10—F2106.4 (3)
O2—C1—C2125.6 (3)F1—C10—F2106.6 (2)
O1—C1—C2116.9 (2)F3—C10—C3111.5 (2)
C3—C2—C1121.9 (3)F1—C10—C3112.1 (3)
C3—C2—H2119.1F2—C10—C3112.4 (2)
C1—C2—H2119.1O4—C11—O3123.6 (2)
C2—C3—C4120.6 (3)O4—C11—C12126.0 (2)
C2—C3—C10119.4 (3)O3—C11—C12110.4 (2)
C4—C3—C10119.9 (2)C14—C12—C11110.2 (2)
C9—C4—C5117.5 (2)C14—C12—C13112.9 (3)
C9—C4—C3116.5 (2)C11—C12—C13114.2 (2)
C5—C4—C3126.0 (2)C14—C12—Br1107.64 (19)
C6—C5—C4121.1 (2)C11—C12—Br1102.84 (17)
C6—C5—H5119.4C13—C12—Br1108.4 (2)
C4—C5—H5119.4C12—C13—H13A109.5
C5—C6—C7118.8 (2)C12—C13—H13B109.5
C5—C6—H6120.6H13A—C13—H13B109.5
C7—C6—H6120.6C12—C13—H13C109.5
C8—C7—C6122.4 (2)H13A—C13—H13C109.5
C8—C7—O3119.5 (2)H13B—C13—H13C109.5
C6—C7—O3117.8 (2)C12—C14—H14A109.5
C7—C8—C9117.7 (2)C12—C14—H14B109.5
C7—C8—H8121.2H14A—C14—H14B109.5
C9—C8—H8121.2C12—C14—H14C109.5
O1—C9—C8115.6 (2)H14A—C14—H14C109.5
O1—C9—C4121.9 (2)H14B—C14—H14C109.5
C8—C9—C4122.5 (2)C1—O1—C9122.1 (2)
F3—C10—F1107.5 (2)C11—O3—C7117.3 (2)
O2—C1—C2—C3−178.7 (3)C2—C3—C10—F3−115.9 (3)
O1—C1—C2—C3−0.5 (4)C4—C3—C10—F361.5 (3)
C1—C2—C3—C4−1.1 (4)C2—C3—C10—F14.7 (4)
C1—C2—C3—C10176.3 (3)C4—C3—C10—F1−177.9 (2)
C2—C3—C4—C92.8 (4)C2—C3—C10—F2124.8 (3)
C10—C3—C4—C9−174.5 (2)C4—C3—C10—F2−57.8 (3)
C2—C3—C4—C5−177.8 (3)O4—C11—C12—C14−20.7 (4)
C10—C3—C4—C54.8 (4)O3—C11—C12—C14159.3 (2)
C9—C4—C5—C61.5 (4)O4—C11—C12—C13−149.0 (3)
C3—C4—C5—C6−177.9 (3)O3—C11—C12—C1331.0 (3)
C4—C5—C6—C70.2 (4)O4—C11—C12—Br193.8 (3)
C5—C6—C7—C8−1.6 (4)O3—C11—C12—Br1−86.2 (2)
C5—C6—C7—O3−175.8 (2)O2—C1—O1—C9178.6 (3)
C6—C7—C8—C91.2 (4)C2—C1—O1—C90.3 (4)
O3—C7—C8—C9175.3 (2)C8—C9—O1—C1−178.9 (2)
C7—C8—C9—O1−178.8 (2)C4—C9—O1—C11.6 (4)
C7—C8—C9—C40.6 (4)O4—C11—O3—C73.3 (4)
C5—C4—C9—O1177.5 (2)C12—C11—O3—C7−176.7 (2)
C3—C4—C9—O1−3.1 (4)C8—C7—O3—C1171.5 (3)
C5—C4—C9—C8−1.9 (4)C6—C7—O3—C11−114.2 (3)
C3—C4—C9—C8177.5 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C5—H5···F20.932.473.019 (3)118
C6—H6···O4i0.932.523.261 (4)136

Symmetry codes: (i) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5450).

References

  • Bruker (2004). APEX2, SAINT-Plus and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Matyjaszewski, K. & Mueller, L. (2008). Macromolecules, 41, 1067–1069.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sinkel, C., Greiner, A. & Agarwal, S. (2008). Macromolecules, 41, 1067–1069.
  • Stenzel-Rosenbaum, M., Davis, T. P., Chen, V. & Fane, A. G. (2001). J. Polym. Sci. A Polym. Chem 39, 2777–2783.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography