1-[3-Meth­oxy-4-(prop-2-yn-1-yl­oxy)phen­yl]ethanone

Zhang, C.-H.; Zhao, J.-M.; Chen, B.-G.

doi:10.1107/S1600536810052074

organic compounds

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Volume 67| Part 1| January 2011| Page o150

https://doi.org/10.1107/S1600536810052074

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1-[3-Methoxy-4-(prop-2-yn-1-yloxy)phenyl]ethanone

Chun-Hua Zhang,^a ^* Jing-Min Zhao ^b and Bao-Guo Chen ^a

^aCollege of Chemistry and Chemical Engineering, Inner Mongolia University for the Nationalities, Inner Mongolia Autonomous Region Tongliao, 22 Huolinhe street, 028000, People's Republic of China, and ^bInstitute of Higher Vocational Education, Tongliao Vocational College, Inner Mongolia Autonomous Region Tongliao, 152 Huolinhe street, 028000, People's Republic of China
^*Correspondence e-mail: zhangchtl@hotmail.com

(Received 3 December 2010; accepted 12 December 2010; online 18 December 2010)

In the title compound, C₁₂H₁₂O₃, the methoxy and prop-2-ynyloxy groups are nearly coplanar with the attached benzene ring [C—O—C—C torsion angles = 1.2 (3) and 2.2 (3)°, respectively]. In the crystal, inversion dimers linked by pairs of C—H⋯O interactions occur.

Related literature

For the β-O-4 substructure in lignin, see: Cathala et al. (2003 ). For attempts to prepare well defined linear polymers with the β-O-4 structure and to develop new methods of utilizing lignins, see: Kishimoto et al. (2005 ). For a related structure, see: Yang et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₂O₃
M_r = 204.22
Monoclinic, P 2₁ /c
a = 12.152 (2) Å
b = 8.9870 (18) Å
c = 10.179 (2) Å
β = 103.86 (3)°
V = 1079.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.974, T_max = 0.991
2908 measured reflections
1988 independent reflections
1400 reflections with I > 2σ(I)
R_int = 0.052
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.169
S = 1.00
1988 reflections
141 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12A⋯O2ⁱ	0.90 (4)	2.40 (4)	3.270 (3)	164 (3)
Symmetry code: (i) -x+1, -y, -z+2.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810052074/nc2210sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810052074/nc2210Isup2.hkl

checkCIF report

Comment top

Lignin is natural polymer occurring in plant cell walls and considered to be the second most abundant biopolymer after cellulose and the β-O-4 structure is the most abundant substructure in lignin (Cathala B. et al., 2003). Lignin is an amorphous polyphenolic material arising from an enzyme-mediated dehydrogenate polymerization of three major phenylpropanoid monomers, i. e., coniferyl, sinapyl and p-coumaril alcohol. Therefore, lignin can be oxidized to produce syringaldehyde, vanillin, p-hydroxybenzaldehyde and acetovanillone etc. Acetovanillone and vanillin are usually used to synthesize lignin mimics (Kishimoto T. et al., 2005). In order to prepare well defined linear lignin mimics composed of the β-O-4 structure by "Click Chemistry" using acetovanillone, an intermediate product C₁₂H₁₂O₃, the title compound was synthesized and identified by crystal structure analysis. In the molecular structure of the title compound, the acetophenone unit is almost a planar with a torsion angle C5—C6—C7—O1, -3.5 (3)° (Fig. 1). In addition, the methoxy group and the prop-2-ynyloxy group are nearly coplanar with the attached benzene ring [C9—O2—C4—C5 = 1.2 (3)° and C10—O3—C3—C2, 2.2 (3)°]. In the crystal structure weak intermolecular C_{terminal alkynes}—H···O_methoxy interactions aref found.

Related literature top

For the β-O-4 substructure in lignin, see: Cathala et al. (2003). For attempts to prepare well defined linear polymers with the β-O-4 structure and to develop new methods of utilizing lignins, see: Kishimoto et al. (2005). For a related structure, see: Yang et al. (2009).

Experimental top

A mixture of 4'-hydroxy-3'-methoxyacetophenon (5 mmol), propargyl bromide (5 mmol) and triethylamine (5 mmol) was stirred in acetone (20 ml) at 353 K. After completion of the reaction (TLC monitoring), the reaction mixture was diluted with ether (100 ml) and washed with water 3 times. The organic phase was dried over with anhydrous Na₂SO₄ and concentrated to dryness in vacuo. The obtained crude crystalline was purified by column chromatography to obtain a pure white solid. Colourless single crystals suitable for X-ray crystallographic analysis were grown by slow evaporation of an ethyl actate solution of the title compound.

Structure description top

For the β-O-4 substructure in lignin, see: Cathala et al. (2003). For attempts to prepare well defined linear polymers with the β-O-4 structure and to develop new methods of utilizing lignins, see: Kishimoto et al. (2005). For a related structure, see: Yang et al. (2009).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

1-[3-Methoxy-4-(prop-2-yn-1-yloxy)phenyl]ethanone top

Crystal data top

C₁₂H₁₂O₃	F(000) = 432
M_r = 204.22	D_x = 1.257 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.152 (2) Å	θ = 9–13°
b = 8.9870 (18) Å	µ = 0.09 mm⁻¹
c = 10.179 (2) Å	T = 293 K
β = 103.86 (3)°	Block, colourless
V = 1079.3 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	1400 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.052
Graphite monochromator	θ_max = 25.4°, θ_min = 1.7°
ω/2θ scans	h = −14→0
Absorption correction: ψ scan (North et al., 1968)	k = −3→10
T_min = 0.974, T_max = 0.991	l = −11→12
2908 measured reflections	3 standard reflections every 200 reflections
1988 independent reflections	intensity decay: 1%

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)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.169	w = 1/[σ²(F_o²) + (0.1P)² + 0.1P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
1988 reflections	Δρ_max = 0.21 e Å⁻³
141 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.066 (9)

Crystal data top

C₁₂H₁₂O₃	V = 1079.3 (4) Å³
M_r = 204.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.152 (2) Å	µ = 0.09 mm⁻¹
b = 8.9870 (18) Å	T = 293 K
c = 10.179 (2) Å	0.30 × 0.20 × 0.10 mm
β = 103.86 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1400 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.052
T_min = 0.974, T_max = 0.991	3 standard reflections every 200 reflections
2908 measured reflections	intensity decay: 1%
1988 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.169	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.21 e Å⁻³
1988 reflections	Δρ_min = −0.20 e Å⁻³
141 parameters

Special details top

Experimental. Absorption correction: semi-empirical absorption based on psi-scan (North et al., 1968)

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. 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
O1	0.02729 (15)	−0.0061 (2)	0.20836 (17)	0.0658 (6)
C1	0.29554 (18)	0.1655 (3)	0.3643 (2)	0.0511 (6)
H1A	0.3039	0.2296	0.2956	0.061*
O2	0.26138 (12)	−0.10284 (18)	0.68203 (14)	0.0529 (5)
C2	0.37931 (19)	0.1593 (3)	0.4840 (2)	0.0506 (6)
H2A	0.4444	0.2170	0.4943	0.061*
O3	0.44025 (13)	0.05304 (19)	0.71063 (15)	0.0527 (5)
C3	0.36568 (17)	0.0674 (2)	0.5876 (2)	0.0428 (5)
C4	0.26800 (18)	−0.0201 (2)	0.5718 (2)	0.0409 (5)
C5	0.18711 (18)	−0.0157 (2)	0.4518 (2)	0.0426 (6)
H5A	0.1230	−0.0754	0.4405	0.051*
C6	0.19980 (18)	0.0773 (2)	0.3462 (2)	0.0433 (6)
C7	0.1073 (2)	0.0778 (3)	0.2195 (2)	0.0493 (6)
C8	0.1143 (2)	0.1817 (4)	0.1077 (3)	0.0835 (10)
H8A	0.0491	0.1684	0.0338	0.125*
H8B	0.1818	0.1612	0.0775	0.125*
H8C	0.1164	0.2824	0.1397	0.125*
C9	0.1630 (2)	−0.1939 (3)	0.6694 (3)	0.0616 (7)
H9A	0.1675	−0.2465	0.7526	0.092*
H9B	0.1590	−0.2640	0.5973	0.092*
H9C	0.0965	−0.1323	0.6498	0.092*
C10	0.54011 (18)	0.1439 (3)	0.7385 (2)	0.0510 (6)
H10A	0.5201	0.2485	0.7291	0.061*
H10B	0.5873	0.1203	0.6768	0.061*
C11	0.59931 (19)	0.1100 (3)	0.8775 (3)	0.0547 (6)
C12	0.6418 (3)	0.0809 (4)	0.9899 (3)	0.0737 (9)
H12A	0.669 (3)	0.067 (4)	1.079 (4)	0.094 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0531 (10)	0.0781 (13)	0.0590 (11)	−0.0090 (10)	−0.0009 (8)	0.0004 (9)
C1	0.0513 (13)	0.0543 (14)	0.0470 (12)	−0.0053 (12)	0.0105 (10)	0.0068 (11)
O2	0.0519 (9)	0.0597 (10)	0.0453 (9)	−0.0136 (8)	0.0080 (7)	0.0078 (7)
C2	0.0457 (12)	0.0544 (14)	0.0507 (13)	−0.0109 (11)	0.0097 (10)	0.0047 (11)
O3	0.0472 (9)	0.0611 (10)	0.0448 (9)	−0.0132 (8)	0.0011 (7)	0.0045 (7)
C3	0.0422 (11)	0.0469 (13)	0.0377 (11)	−0.0025 (10)	0.0065 (9)	−0.0021 (10)
C4	0.0446 (11)	0.0379 (11)	0.0411 (11)	−0.0014 (9)	0.0120 (9)	−0.0010 (9)
C5	0.0397 (11)	0.0439 (12)	0.0443 (12)	−0.0027 (10)	0.0105 (9)	−0.0046 (10)
C6	0.0456 (12)	0.0429 (12)	0.0411 (11)	0.0044 (10)	0.0096 (9)	−0.0007 (9)
C7	0.0467 (12)	0.0523 (14)	0.0464 (13)	0.0077 (12)	0.0065 (10)	−0.0001 (11)
C8	0.0727 (18)	0.102 (2)	0.0613 (16)	−0.0064 (18)	−0.0130 (14)	0.0324 (17)
C9	0.0553 (14)	0.0652 (16)	0.0652 (15)	−0.0146 (13)	0.0160 (12)	0.0131 (13)
C10	0.0437 (12)	0.0570 (14)	0.0495 (13)	−0.0083 (11)	0.0056 (10)	−0.0030 (11)
C11	0.0470 (12)	0.0611 (16)	0.0533 (14)	−0.0080 (12)	0.0071 (11)	−0.0022 (12)
C12	0.0720 (18)	0.086 (2)	0.0551 (17)	−0.0111 (16)	−0.0008 (14)	0.0035 (16)

Geometric parameters (Å, º) top

O1—C7	1.214 (3)	C6—C7	1.494 (3)
C1—C6	1.383 (3)	C7—C8	1.490 (4)
C1—C2	1.389 (3)	C8—H8A	0.9600
C1—H1A	0.9300	C8—H8B	0.9600
O2—C4	1.365 (3)	C8—H8C	0.9600
O2—C9	1.429 (3)	C9—H9A	0.9600
C2—C3	1.381 (3)	C9—H9B	0.9600
C2—H2A	0.9300	C9—H9C	0.9600
O3—C3	1.365 (3)	C10—C11	1.457 (3)
O3—C10	1.433 (3)	C10—H10A	0.9700
C3—C4	1.400 (3)	C10—H10B	0.9700
C4—C5	1.373 (3)	C11—C12	1.167 (4)
C5—C6	1.399 (3)	C12—H12A	0.90 (3)
C5—H5A	0.9300

C6—C1—C2	120.7 (2)	C8—C7—C6	119.5 (2)
C6—C1—H1A	119.7	C7—C8—H8A	109.5
C2—C1—H1A	119.7	C7—C8—H8B	109.5
C4—O2—C9	116.81 (17)	H8A—C8—H8B	109.5
C3—C2—C1	119.8 (2)	C7—C8—H8C	109.5
C3—C2—H2A	120.1	H8A—C8—H8C	109.5
C1—C2—H2A	120.1	H8B—C8—H8C	109.5
C3—O3—C10	118.19 (17)	O2—C9—H9A	109.5
O3—C3—C2	125.65 (19)	O2—C9—H9B	109.5
O3—C3—C4	114.25 (18)	H9A—C9—H9B	109.5
C2—C3—C4	120.1 (2)	O2—C9—H9C	109.5
O2—C4—C5	125.21 (19)	H9A—C9—H9C	109.5
O2—C4—C3	115.26 (19)	H9B—C9—H9C	109.5
C5—C4—C3	119.53 (19)	O3—C10—C11	105.73 (19)
C4—C5—C6	120.9 (2)	O3—C10—H10A	110.6
C4—C5—H5A	119.6	C11—C10—H10A	110.6
C6—C5—H5A	119.6	O3—C10—H10B	110.6
C1—C6—C5	119.0 (2)	C11—C10—H10B	110.6
C1—C6—C7	123.2 (2)	H10A—C10—H10B	108.7
C5—C6—C7	117.8 (2)	C12—C11—C10	176.8 (3)
O1—C7—C8	120.6 (2)	C11—C12—H12A	173 (2)
O1—C7—C6	119.9 (2)

C6—C1—C2—C3	−1.8 (4)	C3—C4—C5—C6	−1.4 (3)
C10—O3—C3—C2	2.2 (3)	C2—C1—C6—C5	1.6 (3)
C10—O3—C3—C4	−176.96 (19)	C2—C1—C6—C7	−179.4 (2)
C1—C2—C3—O3	−178.8 (2)	C4—C5—C6—C1	0.0 (3)
C1—C2—C3—C4	0.4 (3)	C4—C5—C6—C7	−179.01 (19)
C9—O2—C4—C5	1.2 (3)	C1—C6—C7—O1	177.5 (2)
C9—O2—C4—C3	−179.78 (19)	C5—C6—C7—O1	−3.5 (3)
O3—C3—C4—O2	1.4 (3)	C1—C6—C7—C8	−2.5 (4)
C2—C3—C4—O2	−177.8 (2)	C5—C6—C7—C8	176.5 (2)
O3—C3—C4—C5	−179.54 (19)	C3—O3—C10—C11	177.2 (2)
C2—C3—C4—C5	1.2 (3)	O3—C10—C11—C12	−25 (6)
O2—C4—C5—C6	177.52 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O2ⁱ	0.90 (4)	2.40 (4)	3.270 (3)	164 (3)

Symmetry code: (i) −x+1, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂O₃
M_r	204.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.152 (2), 8.9870 (18), 10.179 (2)
β (°)	103.86 (3)
V (Å³)	1079.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.974, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2908, 1988, 1400
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.169, 1.00
No. of reflections	1988
No. of parameters	141
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.20

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12A···O2ⁱ	0.90 (4)	2.40 (4)	3.270 (3)	164 (3)

Symmetry code: (i) −x+1, −y, −z+2.

References

Cathala, B., Saake, B., Faix, O. & Monties, B. (2003). J. Chromatogr. A, 1020, 229–239. Web of Science CrossRef PubMed CAS Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1996). XCAD4. University of Marburg, Germany. Google Scholar
Kishimoto, T., Uraki, Y. & Ubukata, M. (2005). Org. Biomol. Chem. 3, 1067–1073. Web of Science CrossRef PubMed CAS Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, X.-H., Zhou, Y.-H. & Song, X. (2009). Acta Cryst. E65, o1489. Web of Science CSD CrossRef IUCr Journals Google Scholar

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