PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): o1359.
Published online 2009 May 23. doi:  10.1107/S1600536809018601
PMCID: PMC2969792

2-Bromo-4,4-dimethyl-1-(2,4,5-trimethoxy­phen­yl)pentan-3-one

Abstract

The three meth­oxy groups of the title compound, C16H23BrO4, are almost coplanar with the attached aromatic ring, forming dihedral angles of 7.19 (13), 2.48 (13) and 7.24 (12)°. The crystal structure shows an intra­molecular and an inter­molecular C—H(...)O inter­action.

Related literature

For background and related structures, see: Xu et al. (2007 [triangle]); Hu et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1359-scheme1.jpg

Experimental

Crystal data

  • C16H23BrO4
  • M r = 359.25
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1359-efi1.jpg
  • a = 9.0173 (5) Å
  • b = 9.2086 (5) Å
  • c = 11.4217 (6) Å
  • α = 106.752 (1)°
  • β = 106.196 (1)°
  • γ = 100.353 (1)°
  • V = 836.51 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.47 mm−1
  • T = 173 K
  • 0.47 × 0.40 × 0.21 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2004 [triangle]) T min = 0.370, T max = 0.594
  • 6537 measured reflections
  • 3237 independent reflections
  • 2940 reflections with I > 2σ(I)
  • R int = 0.017

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.073
  • S = 1.08
  • 3237 reflections
  • 196 parameters
  • H-atom parameters constrained
  • Δρmax = 0.65 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT-Plus (Bruker, 2003 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018601/bt2955sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018601/bt2955Isup2.hkl

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

Acknowledgments

This work was funded by the SIT program of Hunan University (2008).

supplementary crystallographic information

Comment

α-Bromoketone are well known for its universal applications in medical industry and play a key role in the synthesis of thiazole derivatives (Xu et al., 2007, Hu et al., 2007). It is found that α-bromoketones work as perfect intermediates and increase the efficiency. Herein we report the synthesis and structure of 2-bromo-4,4-dimethyl-1-(2,4,5-trimethyphenyl)- pentan-3-one.

Experimental

To the compound of 4,4-dimethyl-1-(2,4,5-trimethyphenyl)pentan-3-one (0.02 mol), 1-butyl-3-methylimidazolidine bromide (0.02 mol) was slowly added. The reaction mixture was stirred for 30 min, then it was extracted with ethyl acetate (30 ml×3). The organic layers were collected, washed with water (20 ml), dried with anhydrous Na2SO4 and concentrated to give the desired product. Yield: 90.5%. m.p. 366~369 K. 1H NMR (CDCl3, 600 MHz) δ: 1.01 (s, 9H, 3×CH3), 3.20~3.28 (m, 2H, CH2), 3.80 (s, 3H, OCH3), 3.85 (s, 3H, OCH3), 3.87 (s, 3H, OCH3), 4.92~4.96 (m, 1H, CHBr), 6.49 (d, J = 4.2 Hz, 1H, C6H2 3-H), 6.61 (d, J = 6.0 Hz, 1H, C6H2 6-H).

Crystals suitable for X-ray structure determination were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement

The H-atoms were positioned geometrically, with C—H = 0.95 Å for aromatic, C—H = 0.98 Å for methyl, C—H = 0.99 Å for methylene and were refined as riding with Uiso(H) = 1.2 or 1.5 Ueq(Cmethyl).

Figures

Fig. 1.
Molecular structure showing 30% probability displacement ellipsoids.
Fig. 2.
A packing diagram for the title compound. H atoms bonded to C atoms have been omitted for clarity.

Crystal data

C16H23BrO4Z = 2
Mr = 359.25F(000) = 372
Triclinic, P1Dx = 1.426 Mg m3
Hall symbol: -P 1Melting point = 366–369 K
a = 9.0173 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.2086 (5) ÅCell parameters from 4833 reflections
c = 11.4217 (6) Åθ = 2.4–27.0°
α = 106.752 (1)°µ = 2.47 mm1
β = 106.196 (1)°T = 173 K
γ = 100.353 (1)°Block, colorless
V = 836.51 (8) Å30.47 × 0.40 × 0.21 mm

Data collection

Bruker SMART 1000 CCD diffractometer3237 independent reflections
Radiation source: fine-focus sealed tube2940 reflections with I > 2σ(I)
graphiteRint = 0.017
ω scansθmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)h = −11→11
Tmin = 0.370, Tmax = 0.594k = −11→11
6537 measured reflectionsl = −14→11

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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.08w = 1/[σ2(Fo2) + (0.0411P)2 + 0.3147P] where P = (Fo2 + 2Fc2)/3
3237 reflections(Δ/σ)max = 0.002
196 parametersΔρmax = 0.65 e Å3
0 restraintsΔρmin = −0.21 e Å3

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 (Å2)

xyzUiso*/Ueq
Br11.06994 (2)0.86479 (2)0.12181 (2)0.03353 (9)
C10.8126 (2)0.6005 (2)0.07781 (19)0.0234 (4)
H1A0.74580.64590.02160.028*
H1B0.85960.53090.02430.028*
C20.9469 (2)0.7329 (2)0.19069 (19)0.0216 (4)
H20.89960.79930.24770.026*
C31.0691 (2)0.6722 (2)0.27311 (19)0.0224 (4)
C41.1235 (3)0.7470 (3)0.4214 (2)0.0310 (5)
C51.2550 (3)0.6801 (4)0.4841 (3)0.0517 (7)
H5A1.21230.56530.45710.078*
H5B1.28990.72820.57940.078*
H5C1.34680.70390.45600.078*
C61.1885 (3)0.9271 (3)0.4661 (3)0.0466 (6)
H6A1.28150.95330.43990.070*
H6B1.22130.97340.56130.070*
H6C1.10420.96960.42560.070*
C70.9764 (3)0.7038 (3)0.4612 (2)0.0399 (5)
H7A0.89450.75140.42490.060*
H7B1.00950.74390.55660.060*
H7C0.93160.58860.42740.060*
C80.7081 (2)0.5042 (2)0.12787 (18)0.0214 (4)
C90.7162 (2)0.3520 (2)0.12133 (19)0.0230 (4)
H90.79140.31070.08810.028*
C100.6174 (2)0.2603 (2)0.16207 (19)0.0223 (4)
C110.5060 (2)0.3213 (2)0.21148 (19)0.0222 (4)
C120.4989 (2)0.4740 (2)0.22142 (19)0.0222 (4)
H120.42550.51650.25650.027*
C130.5997 (2)0.5642 (2)0.17981 (19)0.0221 (4)
C140.7250 (3)0.0427 (3)0.1048 (2)0.0342 (5)
H14A0.69900.03900.01450.051*
H14B0.7131−0.06480.10580.051*
H14C0.83610.10740.15630.051*
C150.3096 (3)0.2861 (3)0.3105 (3)0.0386 (5)
H15A0.37600.37720.38970.058*
H15B0.25060.20540.33410.058*
H15C0.23300.31980.25200.058*
C160.4788 (2)0.7768 (2)0.2246 (2)0.0292 (4)
H16A0.37240.70470.16710.044*
H16B0.48660.88110.21720.044*
H16C0.49390.78620.31510.044*
O11.11572 (18)0.56644 (17)0.21908 (15)0.0306 (3)
O20.61793 (17)0.11030 (16)0.15966 (15)0.0291 (3)
O30.41020 (17)0.22188 (16)0.24643 (15)0.0283 (3)
O40.60042 (16)0.71626 (16)0.18717 (15)0.0281 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.03262 (13)0.02892 (13)0.05128 (16)0.00848 (9)0.02332 (10)0.02369 (10)
C10.0223 (9)0.0241 (9)0.0231 (10)0.0050 (7)0.0070 (8)0.0096 (8)
C20.0217 (9)0.0201 (9)0.0271 (10)0.0059 (7)0.0119 (8)0.0113 (8)
C30.0191 (9)0.0221 (9)0.0260 (10)0.0044 (7)0.0089 (8)0.0089 (8)
C40.0303 (11)0.0362 (12)0.0252 (11)0.0122 (9)0.0077 (9)0.0094 (9)
C50.0510 (15)0.081 (2)0.0325 (13)0.0360 (15)0.0117 (12)0.0258 (13)
C60.0446 (14)0.0386 (13)0.0362 (13)0.0023 (11)0.0065 (11)−0.0025 (10)
C70.0466 (14)0.0497 (14)0.0325 (12)0.0184 (11)0.0215 (11)0.0176 (11)
C80.0175 (8)0.0228 (9)0.0216 (9)0.0027 (7)0.0045 (7)0.0088 (7)
C90.0213 (9)0.0241 (9)0.0237 (10)0.0076 (7)0.0076 (8)0.0085 (8)
C100.0228 (9)0.0183 (9)0.0248 (10)0.0059 (7)0.0053 (8)0.0091 (7)
C110.0197 (9)0.0211 (9)0.0231 (9)0.0021 (7)0.0056 (8)0.0083 (7)
C120.0170 (9)0.0219 (9)0.0272 (10)0.0045 (7)0.0076 (8)0.0088 (8)
C130.0194 (9)0.0190 (9)0.0261 (10)0.0044 (7)0.0043 (8)0.0093 (7)
C140.0376 (12)0.0253 (10)0.0515 (14)0.0165 (9)0.0242 (11)0.0175 (10)
C150.0423 (13)0.0280 (11)0.0578 (15)0.0097 (9)0.0332 (12)0.0182 (11)
C160.0277 (10)0.0230 (10)0.0418 (12)0.0104 (8)0.0159 (9)0.0132 (9)
O10.0327 (8)0.0306 (8)0.0337 (8)0.0175 (6)0.0134 (6)0.0121 (6)
O20.0356 (8)0.0218 (7)0.0403 (8)0.0128 (6)0.0209 (7)0.0159 (6)
O30.0285 (7)0.0222 (7)0.0403 (8)0.0058 (6)0.0184 (7)0.0145 (6)
O40.0236 (7)0.0214 (7)0.0473 (9)0.0094 (5)0.0169 (7)0.0177 (6)

Geometric parameters (Å, °)

Br1—C21.9693 (18)C8—C91.398 (3)
C1—C81.514 (3)C9—C101.382 (3)
C1—C21.519 (3)C9—H90.9500
C1—H1A0.9900C10—O21.374 (2)
C1—H1B0.9900C10—C111.407 (3)
C2—C31.536 (3)C11—O31.365 (2)
C2—H21.0000C11—C121.392 (3)
C3—O11.205 (2)C12—C131.393 (3)
C3—C41.525 (3)C12—H120.9500
C4—C51.530 (3)C13—O41.377 (2)
C4—C61.533 (3)C14—O21.429 (2)
C4—C71.542 (3)C14—H14A0.9800
C5—H5A0.9800C14—H14B0.9800
C5—H5B0.9800C14—H14C0.9800
C5—H5C0.9800C15—O31.422 (3)
C6—H6A0.9800C15—H15A0.9800
C6—H6B0.9800C15—H15B0.9800
C6—H6C0.9800C15—H15C0.9800
C7—H7A0.9800C16—O41.428 (2)
C7—H7B0.9800C16—H16A0.9800
C7—H7C0.9800C16—H16B0.9800
C8—C131.393 (3)C16—H16C0.9800
C8—C1—C2110.66 (16)C13—C8—C9118.31 (17)
C8—C1—H1A109.5C13—C8—C1120.84 (17)
C2—C1—H1A109.5C9—C8—C1120.84 (17)
C8—C1—H1B109.5C10—C9—C8121.62 (18)
C2—C1—H1B109.5C10—C9—H9119.2
H1A—C1—H1B108.1C8—C9—H9119.2
C1—C2—C3112.96 (15)O2—C10—C9125.42 (17)
C1—C2—Br1109.43 (13)O2—C10—C11115.27 (17)
C3—C2—Br1105.97 (12)C9—C10—C11119.30 (17)
C1—C2—H2109.5O3—C11—C12124.48 (17)
C3—C2—H2109.5O3—C11—C10115.70 (16)
Br1—C2—H2109.5C12—C11—C10119.82 (17)
O1—C3—C4122.68 (18)C11—C12—C13119.80 (17)
O1—C3—C2119.30 (17)C11—C12—H12120.1
C4—C3—C2118.00 (16)C13—C12—H12120.1
C3—C4—C5109.50 (18)O4—C13—C12123.22 (17)
C3—C4—C6110.49 (19)O4—C13—C8115.67 (17)
C5—C4—C6109.6 (2)C12—C13—C8121.11 (17)
C3—C4—C7107.65 (17)O2—C14—H14A109.5
C5—C4—C7109.5 (2)O2—C14—H14B109.5
C6—C4—C7110.09 (19)H14A—C14—H14B109.5
C4—C5—H5A109.5O2—C14—H14C109.5
C4—C5—H5B109.5H14A—C14—H14C109.5
H5A—C5—H5B109.5H14B—C14—H14C109.5
C4—C5—H5C109.5O3—C15—H15A109.5
H5A—C5—H5C109.5O3—C15—H15B109.5
H5B—C5—H5C109.5H15A—C15—H15B109.5
C4—C6—H6A109.5O3—C15—H15C109.5
C4—C6—H6B109.5H15A—C15—H15C109.5
H6A—C6—H6B109.5H15B—C15—H15C109.5
C4—C6—H6C109.5O4—C16—H16A109.5
H6A—C6—H6C109.5O4—C16—H16B109.5
H6B—C6—H6C109.5H16A—C16—H16B109.5
C4—C7—H7A109.5O4—C16—H16C109.5
C4—C7—H7B109.5H16A—C16—H16C109.5
H7A—C7—H7B109.5H16B—C16—H16C109.5
C4—C7—H7C109.5C10—O2—C14116.49 (15)
H7A—C7—H7C109.5C11—O3—C15116.98 (15)
H7B—C7—H7C109.5C13—O4—C16118.02 (15)
C8—C1—C2—C366.5 (2)O2—C10—C11—O3−2.0 (2)
C8—C1—C2—Br1−175.74 (12)C9—C10—C11—O3178.37 (17)
C1—C2—C3—O143.4 (2)O2—C10—C11—C12178.26 (17)
Br1—C2—C3—O1−76.38 (19)C9—C10—C11—C12−1.4 (3)
C1—C2—C3—C4−135.17 (18)O3—C11—C12—C13−178.37 (18)
Br1—C2—C3—C4105.03 (17)C10—C11—C12—C131.4 (3)
O1—C3—C4—C56.3 (3)C11—C12—C13—O4−179.61 (17)
C2—C3—C4—C5−175.18 (19)C11—C12—C13—C80.1 (3)
O1—C3—C4—C6127.1 (2)C9—C8—C13—O4178.22 (17)
C2—C3—C4—C6−54.3 (2)C1—C8—C13—O4−2.7 (3)
O1—C3—C4—C7−112.6 (2)C9—C8—C13—C12−1.5 (3)
C2—C3—C4—C765.9 (2)C1—C8—C13—C12177.52 (18)
C2—C1—C8—C1374.0 (2)C9—C10—O2—C14−3.0 (3)
C2—C1—C8—C9−107.0 (2)C11—C10—O2—C14177.39 (18)
C13—C8—C9—C101.5 (3)C12—C11—O3—C15−7.3 (3)
C1—C8—C9—C10−177.55 (18)C10—C11—O3—C15172.93 (18)
C8—C9—C10—O2−179.66 (18)C12—C13—O4—C16−7.7 (3)
C8—C9—C10—C11−0.1 (3)C8—C13—O4—C16172.52 (17)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···O41.002.503.089 (2)117
C16—H16B···O2i0.982.573.465 (3)151

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2955).

References

  • Bruker (2001). SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2004). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hu, A.-X., Cao, G., Xu, J.-J., Xia, L. & He, D.-H. (2007). J. Hunan Univ. (Nat. Sci.), 34, 78–81.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xu, J.-J., Hu, A.-X. & Cao, G. (2007). Acta Cryst. E63, o533–o534.

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