1-(3,4-Di­meth­oxy­phen­yl)ethanone

Mills-Robles, H.A.; Desikan, V.; Golen, J.A.; Manke, D.R.

doi:10.1107/S2414314616017946

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161794

https://doi.org/10.1107/S2414314616017946

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1-(3,4-Dimethoxyphenyl)ethanone

Heather A. Mills-Robles,^a Vasumathi Desikan,^a James A. Golen ^b and David R. Manke ^b ^*

^aDepartment of Science & Math, Massasoit Community College, 1 Massasoit Boulevard, Brockton, MA 02302, USA, and ^bDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 8 November 2016; accepted 8 November 2016; online 10 November 2016)

The title compound, C₁₀H₁₂O₃, has a single near planar molecule in the asymmetric unit, with the non-H atoms possessing a mean deviation from planarity of 0.132 Å. The molecules dimerize in the solid state through C—H⋯O interactions. These dimers are further linked through parallel slipped π–π interactions of the aryl rings [intercentroid distance = 3.5444 (11) Å, interplanar distance = 3.3998 (12) Å, slippage = 1.002 (2) Å].

Keywords: crystal structure; π–π interactions; ketones.

CCDC reference: 1515734

Structure description

Herein, we report the crystal structure of 3,4-dimethoxyacetophenone (Fig. 1). The structure has a single near planar molecule in the asymmetric unit, with the non-hydrogen atoms possessing a mean deviation from planarity of 0.132 Å. A closer look reveals a planar dimethoxy aryl unit with a mean deviation from planarity of only 0.033 Å, and an acetyl group that is rotated 16.83 (7)^o from this plane. The structure exhibits bond distances and angles consistent with the structure of other 3,4-dimethoxy-substituted aryl compounds (de Ronde et al., 2016 ; Mills-Robles et al., 2015 ; Yang et al., 2011 ).

Figure 1
The molecular structure of the title compound, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

In the crystal, the molecule dimerizes through C9—H9A⋯O3 interactions (Table 1). This interaction is also observed in the propionyl derivative of this compound (Fun et al., 1997 ). These dimers are further linked through parallel slipped π–π interactions [intercentroid distance = 3.5444 (11) Å, interplanar distance = 3.3998 (12) Å, and slippage = 1.002 (2) Å]. These intermolecular interactions do not yield any infinite chains, sheets or networks in the structure. The packing of the title compound is shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯O3ⁱ	0.98	2.60	3.5418 (17)	162
Symmetry code: (i) -x+1, -y+1, -z.

Figure 2
The molecular packing of the title compound, viewed along the a axis.

Synthesis and crystallization

A commercial sample (TCI) of 3,4-dimethoxyacetophenone was used for crystallization. A sample suitable for single-crystal X-ray analysis was grown from the slow evaporation of its methylene chloride solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₂O₃
M_r	180.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	7.9543 (7), 13.3271 (11), 8.8107 (7)
β (°)	92.761 (3)
V (Å³)	932.92 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.18 × 0.1 × 0.05

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.308, 0.331
No. of measured, independent and observed [I > 2σ(I)] reflections	22589, 1717, 1348
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.603

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.096, 1.04
No. of reflections	1717
No. of parameters	122
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1515734

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017946/vm4018sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017946/vm4018Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616017946/vm4018Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 and publCIF (Westrip, 2010).

1-(3,4-Dimethoxyphenyl)ethanone top

Crystal data top

C₁₀H₁₂O₃	F(000) = 384
M_r = 180.20	D_x = 1.283 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6345 reflections
a = 7.9543 (7) Å	θ = 3.0–25.0°
b = 13.3271 (11) Å	µ = 0.09 mm⁻¹
c = 8.8107 (7) Å	T = 200 K
β = 92.761 (3)°	PLATE, colourless
V = 932.92 (13) Å³	0.18 × 0.1 × 0.05 mm
Z = 4

Data collection top

Bruker D8 Venture CMOS diffractometer	1717 independent reflections
Radiation source: Mo	1348 reflections with I > 2σ(I)
TRIUMPH monochromator	R_int = 0.049
φ and ω scans	θ_max = 25.4°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −9→9
T_min = 0.308, T_max = 0.331	k = −16→16
22589 measured reflections	l = −10→10

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0459P)² + 0.2372P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.096	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.17 e Å⁻³
1717 reflections	Δρ_min = −0.15 e Å⁻³
122 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.027 (5)

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.

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

	x	y	z	U_iso*/U_eq
O1	0.96346 (14)	0.59482 (10)	0.63260 (13)	0.0553 (4)
O2	0.55355 (12)	0.52425 (8)	0.17851 (10)	0.0358 (3)
O3	0.28281 (12)	0.61821 (8)	0.23518 (11)	0.0390 (3)
C1	0.7983 (2)	0.65151 (14)	0.83175 (17)	0.0471 (4)
H1A	0.7053	0.6122	0.8703	0.071*
H1B	0.7707	0.7231	0.8360	0.071*
H1C	0.9011	0.6385	0.8944	0.071*
C2	0.82541 (19)	0.62201 (11)	0.67004 (16)	0.0346 (4)
C3	0.67942 (17)	0.62562 (10)	0.55786 (15)	0.0287 (3)
C4	0.69107 (17)	0.57335 (10)	0.41998 (14)	0.0277 (3)
H4	0.7914	0.5382	0.3995	0.033*
C5	0.55772 (17)	0.57306 (10)	0.31485 (14)	0.0275 (3)
C6	0.40893 (17)	0.62552 (10)	0.34497 (15)	0.0297 (3)
C7	0.39924 (18)	0.67871 (11)	0.47885 (16)	0.0342 (4)
H7	0.3006	0.7158	0.4982	0.041*
C8	0.53410 (18)	0.67777 (11)	0.58520 (16)	0.0339 (4)
H8	0.5261	0.7135	0.6779	0.041*
C9	0.69905 (19)	0.46789 (12)	0.14399 (16)	0.0393 (4)
H9A	0.6803	0.4353	0.0449	0.059*
H9B	0.7207	0.4167	0.2224	0.059*
H9C	0.7963	0.5129	0.1410	0.059*
C10	0.12522 (19)	0.66319 (14)	0.26553 (19)	0.0480 (4)
H10A	0.0433	0.6485	0.1818	0.072*
H10B	0.1395	0.7360	0.2752	0.072*
H10C	0.0846	0.6360	0.3604	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0393 (7)	0.0773 (9)	0.0483 (7)	0.0084 (6)	−0.0082 (5)	−0.0194 (6)
O2	0.0348 (6)	0.0445 (6)	0.0277 (5)	0.0075 (5)	−0.0018 (4)	−0.0078 (4)
O3	0.0308 (6)	0.0485 (6)	0.0374 (6)	0.0064 (5)	−0.0026 (4)	−0.0009 (5)
C1	0.0522 (10)	0.0559 (10)	0.0324 (8)	−0.0068 (8)	−0.0050 (7)	−0.0059 (8)
C2	0.0391 (9)	0.0297 (7)	0.0348 (8)	−0.0045 (6)	−0.0005 (6)	−0.0038 (6)
C3	0.0352 (8)	0.0234 (7)	0.0277 (7)	−0.0037 (6)	0.0029 (6)	−0.0003 (5)
C4	0.0292 (7)	0.0259 (7)	0.0284 (7)	0.0007 (5)	0.0035 (6)	0.0004 (5)
C5	0.0328 (7)	0.0257 (7)	0.0243 (7)	−0.0013 (6)	0.0040 (5)	0.0000 (5)
C6	0.0301 (7)	0.0280 (7)	0.0310 (7)	−0.0007 (6)	0.0005 (6)	0.0052 (6)
C7	0.0355 (8)	0.0302 (8)	0.0373 (8)	0.0067 (6)	0.0072 (6)	−0.0004 (6)
C8	0.0425 (9)	0.0296 (8)	0.0301 (7)	−0.0001 (6)	0.0062 (6)	−0.0052 (6)
C9	0.0392 (9)	0.0481 (9)	0.0306 (7)	0.0085 (7)	0.0017 (6)	−0.0097 (7)
C10	0.0315 (9)	0.0570 (10)	0.0553 (10)	0.0088 (7)	−0.0002 (7)	0.0018 (8)

Geometric parameters (Å, º) top

O1—C2	1.2169 (18)	C4—C5	1.3742 (19)
O2—C5	1.3651 (16)	C5—C6	1.4107 (19)
O2—C9	1.4249 (17)	C6—C7	1.382 (2)
O3—C6	1.3631 (16)	C7—H7	0.9500
O3—C10	1.4263 (18)	C7—C8	1.390 (2)
C1—H1A	0.9800	C8—H8	0.9500
C1—H1B	0.9800	C9—H9A	0.9800
C1—H1C	0.9800	C9—H9B	0.9800
C1—C2	1.504 (2)	C9—H9C	0.9800
C2—C3	1.489 (2)	C10—H10A	0.9800
C3—C4	1.4073 (19)	C10—H10B	0.9800
C3—C8	1.380 (2)	C10—H10C	0.9800
C4—H4	0.9500

C5—O2—C9	116.97 (10)	O3—C6—C7	124.97 (12)
C6—O3—C10	117.41 (11)	C7—C6—C5	119.78 (13)
H1A—C1—H1B	109.5	C6—C7—H7	120.1
H1A—C1—H1C	109.5	C6—C7—C8	119.86 (13)
H1B—C1—H1C	109.5	C8—C7—H7	120.1
C2—C1—H1A	109.5	C3—C8—C7	120.84 (13)
C2—C1—H1B	109.5	C3—C8—H8	119.6
C2—C1—H1C	109.5	C7—C8—H8	119.6
O1—C2—C1	120.49 (13)	O2—C9—H9A	109.5
O1—C2—C3	120.98 (13)	O2—C9—H9B	109.5
C3—C2—C1	118.53 (13)	O2—C9—H9C	109.5
C4—C3—C2	118.38 (12)	H9A—C9—H9B	109.5
C8—C3—C2	122.24 (12)	H9A—C9—H9C	109.5
C8—C3—C4	119.38 (13)	H9B—C9—H9C	109.5
C3—C4—H4	119.9	O3—C10—H10A	109.5
C5—C4—C3	120.16 (13)	O3—C10—H10B	109.5
C5—C4—H4	119.9	O3—C10—H10C	109.5
O2—C5—C4	125.43 (12)	H10A—C10—H10B	109.5
O2—C5—C6	114.62 (12)	H10A—C10—H10C	109.5
C4—C5—C6	119.94 (12)	H10B—C10—H10C	109.5
O3—C6—C5	115.25 (12)

O1—C2—C3—C4	16.3 (2)	C4—C3—C8—C7	0.4 (2)
O1—C2—C3—C8	−164.02 (15)	C4—C5—C6—O3	−178.32 (12)
O2—C5—C6—O3	1.10 (17)	C4—C5—C6—C7	1.3 (2)
O2—C5—C6—C7	−179.26 (12)	C5—C6—C7—C8	−2.0 (2)
O3—C6—C7—C8	177.64 (13)	C6—C7—C8—C3	1.1 (2)
C1—C2—C3—C4	−162.91 (13)	C8—C3—C4—C5	−1.1 (2)
C1—C2—C3—C8	16.7 (2)	C9—O2—C5—C4	1.0 (2)
C2—C3—C4—C5	178.62 (12)	C9—O2—C5—C6	−178.43 (12)
C2—C3—C8—C7	−179.25 (13)	C10—O3—C6—C5	175.11 (13)
C3—C4—C5—O2	−179.16 (12)	C10—O3—C6—C7	−4.5 (2)
C3—C4—C5—C6	0.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···O3ⁱ	0.98	2.60	3.5418 (17)	162

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

We greatly acknowledge support from the Massachusetts Clean Energy Center and the National Science Foundation (CHE-1429086).

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