organic compounds
4-(2,4,6-Trimethylphenyl)butan-2-one
aCollege of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, People's Republic of China
*Correspondence e-mail: lfy20110407@163.com
In the title compound, C13H18O, the 3-oxobutyl group is approximately planar [maximum deviation = 0.029 (4) Å] and its mean plane is twisted with respect to the benzene ring at 84.0 (2)°. In the crystal, weak C—H⋯π interactions link the molecules into supramolecular chains propagating along the a axis.
Keywords: crystal structure; π–π stacking; hydrolysis of β-diketone.
CCDC reference: 1548043
Structure description
The β-diketone motif is a versatile metal coordinating ligand that is readily derivatized and able to form complexes with a wide range of metal ions (Bray et al., 2007; Chen et al., 2010). It has also been shown to be an attractive ligand for the preparation of metallo-supramolecular structures. However, our attempts at forming lanthanide–transition metal complexes using the normal procedure of heating with a lanthanide salt in the presence of base were unsuccessful. Rather than obtaining the desired lanthanide metal complex upon cooling the reaction mixture, we isolated solids that contained no metal ion. An X-ray determination confirmed that this product was the ketone derivative of compound (II) (Fig. 2), which could be attributed to the alkaline hydrolysis of the β-diketone groups (Hauser et al., 1948; Pearson & Mayerle, 1951). Herein we report the synthesis and structure of the title compound.
In the molecule (Fig. 1), the 3′-oxo-butyl group is nearly planar, the maximum deviation being 0.029 (4) Å (C1 atom), and its mean plane is oriented at 84.0 (2)° with respect to the benzene ring.
In the crystal, weak C—H–π interactions (Table 1) link the molecules into supramolecular chains propagating along the a-axis direction.
Synthesis and crystallization
The synthesis procedures for the title compound are shown in Fig. 2. Acetylacetone (9 mmol, 900 mg) was added to 30 ml tert-butanol in the presence of t-BuOK. After 1 h, 2-(bromomethyl)-1,3,5-trimethylbenzene (9 mmol, 1917 mg) was added to the above mixture, then 0.25 g KI was added. The mixture was then refluxed under argon for 72 h. After cooling to room temperature, the solvent was evaporated. The product was extracted with dichloromethane(50 ml), and the organic phase was washed with water (50 ml). Then the organic phase was dried by magnesium sulfate and filtered. White solids were obtained after the dichloromethane solvent was evaporated [compound (II)]. Yield: 63% (based on acetylacetone). Compound (II) (6 mmol, 1392 mg) was dissolved in 20 ml ethanol, then 6 mmol NaOH (0.1 mol l−1) was added to adjust the pH of the mixture to 7. Then 2 mmol europium(III) chloride, (0.2 mol l−1 in ethanol) was added drop by drop. The mixture was refluxed for 2 h. The filtrate was dissolved in dichloromethane/ether. Colorless block-shaped crystals were obtained by slow evaporation after one week.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1548043
https://doi.org/10.1107/S2414314617006757/xu4027sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617006757/xu4027Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617006757/xu4027Isup3.cml
Data collection: CrystalStructure (Rigaku/MSC, 2006); cell
CrystalStructure (Rigaku/MSC, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2006); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).C13H18O | Dx = 1.078 Mg m−3 |
Mr = 190.27 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 11221 reflections |
a = 4.8462 (10) Å | θ = 3.3–27.5° |
b = 7.8042 (16) Å | µ = 0.07 mm−1 |
c = 30.996 (6) Å | T = 293 K |
V = 1172.3 (4) Å3 | Block, colorless |
Z = 4 | 0.28 × 0.25 × 0.23 mm |
F(000) = 416 |
Rigaku MM007-HF CCD (Saturn 724+) diffractometer | 1626 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.078 |
ω scans at fixed χ = 45° | θmax = 27.5°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→5 |
Tmin = 0.982, Tmax = 0.985 | k = −10→10 |
11150 measured reflections | l = −40→39 |
2673 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.081 | H-atom parameters constrained |
wR(F2) = 0.168 | w = 1/[σ2(Fo2) + (0.0612P)2 + 0.1143P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max < 0.001 |
2673 reflections | Δρmax = 0.12 e Å−3 |
131 parameters | Δρmin = −0.13 e Å−3 |
0 restraints | Absolute structure: Flack x determined using 411 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.5 (10) |
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 taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. H atoms were geometrically fixed and refined in riding mode with C—H = 0.93–0.97 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the others. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2549 (8) | 0.2228 (5) | 0.24165 (11) | 0.0573 (9) | |
C2 | 0.1217 (9) | 0.2873 (6) | 0.28200 (12) | 0.0719 (12) | |
H2A | 0.1694 | 0.2136 | 0.3057 | 0.108* | |
H2B | −0.0750 | 0.2883 | 0.2784 | 0.108* | |
H2C | 0.1852 | 0.4014 | 0.2879 | 0.108* | |
C3 | 0.1343 (8) | 0.2873 (5) | 0.20018 (11) | 0.0595 (10) | |
H3A | 0.1267 | 0.4114 | 0.2013 | 0.071* | |
H3B | −0.0537 | 0.2456 | 0.1978 | 0.071* | |
C4 | 0.2930 (8) | 0.2343 (5) | 0.15972 (11) | 0.0644 (11) | |
H4A | 0.4828 | 0.2724 | 0.1623 | 0.077* | |
H4B | 0.2940 | 0.1103 | 0.1576 | 0.077* | |
C5 | 0.1684 (7) | 0.3087 (5) | 0.11887 (11) | 0.0503 (9) | |
C6 | 0.2388 (7) | 0.4738 (5) | 0.10572 (11) | 0.0556 (10) | |
C7 | 0.1185 (8) | 0.5412 (5) | 0.06896 (11) | 0.0594 (10) | |
H7 | 0.1681 | 0.6510 | 0.0603 | 0.071* | |
C8 | −0.0712 (8) | 0.4524 (5) | 0.04478 (11) | 0.0591 (10) | |
C9 | −0.1382 (8) | 0.2888 (5) | 0.05782 (12) | 0.0604 (10) | |
H9 | −0.2638 | 0.2257 | 0.0416 | 0.073* | |
C10 | −0.0231 (8) | 0.2157 (5) | 0.09455 (11) | 0.0565 (10) | |
C11 | 0.4462 (9) | 0.5809 (6) | 0.13046 (14) | 0.0804 (13) | |
H11A | 0.4481 | 0.6953 | 0.1191 | 0.121* | |
H11B | 0.6264 | 0.5311 | 0.1276 | 0.121* | |
H11C | 0.3954 | 0.5841 | 0.1604 | 0.121* | |
C12 | −0.2043 (10) | 0.5318 (6) | 0.00512 (13) | 0.0871 (15) | |
H12A | −0.1128 | 0.4908 | −0.0203 | 0.131* | |
H12B | −0.1884 | 0.6542 | 0.0066 | 0.131* | |
H12C | −0.3957 | 0.5003 | 0.0041 | 0.131* | |
C13 | −0.1044 (11) | 0.0326 (6) | 0.10584 (15) | 0.0824 (14) | |
H13A | 0.0522 | −0.0414 | 0.1023 | 0.124* | |
H13B | −0.2506 | −0.0043 | 0.0871 | 0.124* | |
H13C | −0.1662 | 0.0281 | 0.1353 | 0.124* | |
O1 | 0.4465 (7) | 0.1257 (4) | 0.24275 (10) | 0.0920 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.058 (2) | 0.057 (2) | 0.057 (2) | 0.000 (2) | −0.010 (2) | 0.0008 (19) |
C2 | 0.081 (3) | 0.081 (3) | 0.053 (2) | 0.002 (3) | −0.005 (2) | 0.007 (2) |
C3 | 0.056 (2) | 0.070 (2) | 0.052 (2) | 0.018 (2) | −0.0019 (18) | 0.0011 (19) |
C4 | 0.059 (2) | 0.078 (3) | 0.056 (2) | 0.017 (2) | −0.002 (2) | 0.000 (2) |
C5 | 0.0426 (18) | 0.062 (2) | 0.0466 (18) | 0.0125 (18) | 0.0052 (17) | −0.0037 (17) |
C6 | 0.0446 (19) | 0.068 (3) | 0.054 (2) | 0.0000 (19) | 0.0102 (17) | −0.0121 (19) |
C7 | 0.062 (2) | 0.055 (2) | 0.062 (2) | 0.001 (2) | 0.013 (2) | 0.0027 (19) |
C8 | 0.062 (2) | 0.067 (3) | 0.0481 (19) | 0.007 (2) | 0.0015 (18) | 0.0006 (19) |
C9 | 0.066 (2) | 0.062 (2) | 0.053 (2) | −0.003 (2) | −0.0032 (19) | −0.0114 (19) |
C10 | 0.062 (2) | 0.054 (2) | 0.054 (2) | 0.005 (2) | 0.012 (2) | −0.0034 (18) |
C11 | 0.063 (2) | 0.095 (3) | 0.082 (3) | −0.017 (3) | 0.001 (2) | −0.014 (2) |
C12 | 0.099 (3) | 0.097 (3) | 0.066 (3) | 0.007 (3) | −0.009 (3) | 0.018 (3) |
C13 | 0.103 (3) | 0.061 (3) | 0.083 (3) | −0.004 (3) | 0.003 (3) | 0.002 (2) |
O1 | 0.089 (2) | 0.105 (2) | 0.081 (2) | 0.048 (2) | −0.0164 (18) | 0.0056 (17) |
C1—O1 | 1.199 (4) | C7—C8 | 1.374 (5) |
C1—C2 | 1.495 (5) | C7—H7 | 0.9300 |
C1—C3 | 1.499 (5) | C8—C9 | 1.378 (5) |
C2—H2A | 0.9600 | C8—C12 | 1.520 (5) |
C2—H2B | 0.9600 | C9—C10 | 1.390 (5) |
C2—H2C | 0.9600 | C9—H9 | 0.9300 |
C3—C4 | 1.528 (5) | C10—C13 | 1.523 (6) |
C3—H3A | 0.9700 | C11—H11A | 0.9600 |
C3—H3B | 0.9700 | C11—H11B | 0.9600 |
C4—C5 | 1.518 (5) | C11—H11C | 0.9600 |
C4—H4A | 0.9700 | C12—H12A | 0.9600 |
C4—H4B | 0.9700 | C12—H12B | 0.9600 |
C5—C6 | 1.394 (5) | C12—H12C | 0.9600 |
C5—C10 | 1.399 (5) | C13—H13A | 0.9600 |
C6—C7 | 1.384 (5) | C13—H13B | 0.9600 |
C6—C11 | 1.515 (5) | C13—H13C | 0.9600 |
O1—C1—C2 | 121.6 (3) | C6—C7—H7 | 118.7 |
O1—C1—C3 | 122.6 (3) | C7—C8—C9 | 117.7 (4) |
C2—C1—C3 | 115.9 (3) | C7—C8—C12 | 121.3 (4) |
C1—C2—H2A | 109.5 | C9—C8—C12 | 121.0 (4) |
C1—C2—H2B | 109.5 | C8—C9—C10 | 121.7 (4) |
H2A—C2—H2B | 109.5 | C8—C9—H9 | 119.1 |
C1—C2—H2C | 109.5 | C10—C9—H9 | 119.1 |
H2A—C2—H2C | 109.5 | C9—C10—C5 | 119.6 (3) |
H2B—C2—H2C | 109.5 | C9—C10—C13 | 118.0 (4) |
C1—C3—C4 | 114.6 (3) | C5—C10—C13 | 122.3 (4) |
C1—C3—H3A | 108.6 | C6—C11—H11A | 109.5 |
C4—C3—H3A | 108.6 | C6—C11—H11B | 109.5 |
C1—C3—H3B | 108.6 | H11A—C11—H11B | 109.5 |
C4—C3—H3B | 108.6 | C6—C11—H11C | 109.5 |
H3A—C3—H3B | 107.6 | H11A—C11—H11C | 109.5 |
C5—C4—C3 | 112.4 (3) | H11B—C11—H11C | 109.5 |
C5—C4—H4A | 109.1 | C8—C12—H12A | 109.5 |
C3—C4—H4A | 109.1 | C8—C12—H12B | 109.5 |
C5—C4—H4B | 109.1 | H12A—C12—H12B | 109.5 |
C3—C4—H4B | 109.1 | C8—C12—H12C | 109.5 |
H4A—C4—H4B | 107.9 | H12A—C12—H12C | 109.5 |
C6—C5—C10 | 119.0 (3) | H12B—C12—H12C | 109.5 |
C6—C5—C4 | 120.0 (3) | C10—C13—H13A | 109.5 |
C10—C5—C4 | 121.0 (3) | C10—C13—H13B | 109.5 |
C7—C6—C5 | 119.3 (4) | H13A—C13—H13B | 109.5 |
C7—C6—C11 | 119.1 (4) | C10—C13—H13C | 109.5 |
C5—C6—C11 | 121.6 (4) | H13A—C13—H13C | 109.5 |
C8—C7—C6 | 122.7 (4) | H13B—C13—H13C | 109.5 |
C8—C7—H7 | 118.7 | ||
O1—C1—C3—C4 | −6.0 (6) | C6—C7—C8—C9 | −1.1 (5) |
C2—C1—C3—C4 | 173.9 (4) | C6—C7—C8—C12 | 178.6 (4) |
C1—C3—C4—C5 | −177.8 (3) | C7—C8—C9—C10 | 1.1 (5) |
C3—C4—C5—C6 | 84.4 (4) | C12—C8—C9—C10 | −178.5 (4) |
C3—C4—C5—C10 | −93.8 (4) | C8—C9—C10—C5 | −0.8 (5) |
C10—C5—C6—C7 | −0.2 (5) | C8—C9—C10—C13 | −178.6 (4) |
C4—C5—C6—C7 | −178.5 (3) | C6—C5—C10—C9 | 0.3 (5) |
C10—C5—C6—C11 | −179.6 (3) | C4—C5—C10—C9 | 178.6 (3) |
C4—C5—C6—C11 | 2.1 (5) | C6—C5—C10—C13 | 178.0 (3) |
C5—C6—C7—C8 | 0.6 (5) | C4—C5—C10—C13 | −3.7 (5) |
C11—C6—C7—C8 | −180.0 (3) |
Cg1 is the centroid of the benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11B···Cg1i | 0.96 | 2.76 | 3.642 (5) | 154 |
Symmetry code: (i) x+1, y, z. |
Funding information
Funding for this research was provided by: National Natural Science Foundation of Chinahttps://doi.org/10.13039/501100001809 (award No. 21161023); Natural Science Foundation of Yunnan Province, China (award No. 2009CD048).
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