4-(2,4,6-Tri­methyl­phen­yl)butan-2-one

Zhang, L.-J.; Kou, J.-F.; Liu, F.-Y.

doi:10.1107/S2414314617006757

organic compounds

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ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170675

https://doi.org/10.1107/S2414314617006757

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4-(2,4,6-Trimethylphenyl)butan-2-one

Lang-Jing Zhang,^a Jun-Feng Kou ^a and Feng-Yi Liu ^a ^*

^aCollege of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, People's Republic of China
^*Correspondence e-mail: lfy20110407@163.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 24 April 2017; accepted 5 May 2017; online 9 May 2017)

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 crystal structure 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.

Figure 2
Steps in the synthesis 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.

Figure 1
The molecular structure of the title compound, shown with atom labels and 30% probability displacement ellipsoids.

In the crystal, weak C—H–π interactions (Table 1) link the molecules into supramolecular chains propagating along the a-axis direction.

Table 1
Hydrogen-bond geometry (Å, °)

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.

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₈O
M_r	190.27
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	4.8462 (10), 7.8042 (16), 30.996 (6)
V (Å³)	1172.3 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.07
Crystal size (mm)	0.28 × 0.25 × 0.23

Data collection
Diffractometer	Rigaku MM007-HF CCD (Saturn 724+)
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.982, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	11150, 2673, 1626
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.081, 0.168, 1.09
No. of reflections	2673
No. of parameters	131
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.13
Absolute structure	Flack x determined using 411 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.5 (10)
Computer programs: CrystalStructure (Rigaku/MSC, 2006 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1548043

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2414314617006757/xu4027sup1.cif

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

checkCIF report

Computing details top

Data collection: CrystalStructure (Rigaku/MSC, 2006); cell refinement: 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).

4-(2,4,6-Trimethylphenyl)butan-2-one top

Crystal data top

C₁₃H₁₈O	D_x = 1.078 Mg m⁻³
M_r = 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

Data collection top

Rigaku MM007-HF CCD (Saturn 724+) diffractometer	1626 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.078
ω scans at fixed χ = 45°	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→5
T_min = 0.982, T_max = 0.985	k = −10→10
11150 measured reflections	l = −40→39
2673 independent reflections

Refinement top

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(F_o²) + (0.0612P)² + 0.1143P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2673 reflections	Δρ_max = 0.12 e Å⁻³
131 parameters	Δρ_min = −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)

Special details top

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 U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the others.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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 China (award No. 21161023); Natural Science Foundation of Yunnan Province, China (award No. 2009CD048).

References

Bray, D. J., Jolliffe, K. A., Lindoy, L. F. & McMurtrie, J. C. (2007). Tetrahedron, 63, 1953–1958. Web of Science CSD CrossRef CAS Google Scholar
Chen, X.-Y., Yang, X.-P. & Holliday, B. J. (2010). Inorg. Chem. 49, 2583–2585. Web of Science CSD CrossRef CAS PubMed Google Scholar
Hauser, C. R., Swamer, F. W. & Ringler, B. I. (1948). J. Am. Chem. Soc. 70, 4023–4026. CrossRef PubMed CAS Web of Science Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Pearson, R. G. & Mayerle, E. A. (1951). J. Am. Chem. Soc. 73, 926–930. CrossRef CAS Web of Science Google Scholar
Rigaku/MSC (2006). CrystalStructure. Rigaku Americas, The Woodlands. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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ISSN: 2414-3146

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-(2,4,6-Tri­methyl­phen­yl)butan-2-one

Structure description

Synthesis and crystallization

Refinement

Structural data

Funding information

References

organic compounds

4-(2,4,6-Trimethylphenyl)butan-2-one