Methyl 3-(2,5-dimeth­oxy-3,4,6-tri­methyl­phen­yl)propano­ate

Goswami, S.K.; Hanton, L.R.; McAdam, C.J.; Moratti, S.C.; Simpson, J.

doi:10.1107/S2414314617005004

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 4| April 2017| x170500

https://doi.org/10.1107/S2414314617005004

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Methyl 3-(2,5-dimethoxy-3,4,6-trimethylphenyl)propanoate

Shailesh K. Goswami,^a Lyall R. Hanton,^a C. John McAdam,^a Stephen C. Moratti ^a and Jim Simpson ^a ^*

^aDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
^*Correspondence e-mail: jsimpson@alkali.otago.ac.nz

Edited by A. J. Lough, University of Toronto, Canada (Received 28 March 2017; accepted 30 March 2017; online 4 April 2017)

In the title compound, C₁₅H₂₂O₄, the fully substituted benzene ring carries a methyl propanoate, two methoxy and three methyl substituents. Both methoxy substituents are almost orthogonal to the benzene ring plane. The methyl propanoate group is almost planar, r.m.s. deviation 0.0138 Å, and is inclined to the benzene ring plane by 80.26 (14)°. In the crystal, C—H⋯O hydrogen bonds form head-to-tail chains of molecules along the b-axis direction that are supported by very weak C—H⋯π(ring) contacts.

Keywords: crystal structure; hydrogen bonds; dimethoxybenzene synthon.

CCDC reference: 1541364

Structure description

The title compound, Fig. 1, is an intermediate in the synthesis of dimethoxybenzene-appended acrylate and methacrylate monomers (Goswami et al., 2017 ). The fully substituted benzene ring carries a methyl propanoate, two methoxy and three methyl substituents. The methoxy substituents are para to each other and lie almost at right angles to the benzene ring in a cis conformation; the C2/O2/C21 and C5/O5/C51 planes are inclined to the benzene ring plane by 83.7 (3) and 84.8 (3)°, respectively, and overall present a C21–O2⋯O5–C51 torsion angle of approximately 11.57°. The C1/C7/C8/C9/O9/O91/C91 methyl propanoate group is almost planar, r.m.s. deviation 0.0138 Å; the dihedral angle between this plane and that of the benzene ring is 80.26 (14)°.

Figure 1
The structure of the title compound showing the atom numbering, with displacement ellipsoids drawn at the 50% probability level.

In the crystal, C41—H41B⋯O91 and C41—H41C⋯O9 hydrogen bonds, supported by very weak C8—H8A⋯Cg contacts form chains of molecules arranged in a head-to-tail fashion along the b axis, Fig. 2 and Table 1. No significant additional contacts are found between adjacent chains that stack the molecules along the b-axis direction, Fig. 3.

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C41—H41B⋯O91ⁱ	0.98	2.59	3.205 (6)	121
C41—H41C⋯O9ⁱⁱ	0.98	2.41	3.392 (5)	175
C8—H8A⋯Cgⁱⁱ	0.99	3.15	3.763 (6)	121
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+2]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+2]$ .

Figure 2
Chains of molecules along the b axis with hydrogen bonds drawn as dashed lines. Ring centroids are shown as red spheres and C—H⋯π(ring) contacts are drawn as green dotted lines.

Figure 3
Overall packing of the title compound viewed along the b-axis direction.

Structures of compounds with 2,5-dimethoxy-3,4,6-trimethyl-substituted benzene rings are rare with only two entries (Wickramasinhage et al., 2016 ; Wiedenfeld et al., 2003 ) found in the CSD (Version 5.37, November 2015 with three updates; Groom et al. 2016 ). In addition, we have recently reported the structure of a third related compound, 3-(2,5-dimethoxy-3,4,6-trimethylphenyl)propyl methacrylate (Goswami et al., 2017).

Synthesis and crystallization

Synthesis is by methylation of 6-hydroxy-5,7,8-trimethylchroman-2-one (Goswami et al., 2011 ) as reported previously (Goswami et al., 2017). Crystals for this study were obtained by slow crystallization of the pure liquid at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. With no heavy atoms in the molecule, the absolute structure could not be determined reliably.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₅H₂₂O₄
M_r	266.32
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	92
a, b, c (Å)	8.7453 (13), 8.6888 (10), 9.2511 (11)
β (°)	95.936 (8)
V (Å³)	699.19 (16)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.42 × 0.08 × 0.07

Data collection
Diffractometer	Bruker APEXII CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )
T_min, T_max	0.660, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	5680, 1929, 1781
R_int	0.042
θ_max (°)	23.0
(sin θ/λ)_max (Å⁻¹)	0.549

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.098, 1.09
No. of reflections	1929
No. of parameters	178
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.20
Absolute structure	Flack x determined using 713 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] Parsons et al. (2013 )
Absolute structure parameter	0.4 (10)
Computer programs: APEX2 and (Bruker, 2013), SHELXS2013 (Sheldrick, 2008 ), SHELXL2014/7 (Sheldrick, 2015 ), TITAN (Hunter & Simpson, 1999 ), Mercury (Macrae et al., 2008 ), enCIFer (Allen et al., 2004 ), PLATON (Spek, 2009 ) and publCIF (Westrip 2010 ).

Structural data

CCDC reference: 1541364

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617005004/lh4018sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617005004/lh4018Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617005004/lh4018Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: APEX2 and SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008) and TITAN (Hunter & Simpson, 1999); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015) and TITAN (Hunter & Simpson, 1999); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015), enCIFer (Allen et al., 2004), PLATON (Spek, 2009), publCIF (Westrip 2010).

Methyl 3-(2,5-dimethoxy-3,4,6-trimethylphenyl)propanoate top

Crystal data top

C₁₅H₂₂O₄	F(000) = 288
M_r = 266.32	D_x = 1.265 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 8.7453 (13) Å	Cell parameters from 1870 reflections
b = 8.6888 (10) Å	θ = 2.3–22.9°
c = 9.2511 (11) Å	µ = 0.09 mm⁻¹
β = 95.936 (8)°	T = 92 K
V = 699.19 (16) Å³	Needle, colourless
Z = 2	0.42 × 0.08 × 0.07 mm

Data collection top

Bruker APEXII CCD area detector diffractometer	1781 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
φ and ω scans	θ_max = 23.0°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −9→9
T_min = 0.660, T_max = 0.745	k = −9→9
5680 measured reflections	l = −9→10
1929 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.026P)² + 0.2556P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.098	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 0.14 e Å⁻³
1929 reflections	Δρ_min = −0.20 e Å⁻³
178 parameters	Absolute structure: Flack x determined using 713 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] Parsons et al. (2013)
1 restraint	Absolute structure parameter: 0.4 (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.

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

	x	y	z	U_iso*/U_eq
C1	0.5363 (5)	0.2874 (4)	1.0124 (4)	0.0200 (10)
C2	0.3827 (5)	0.3202 (5)	0.9690 (4)	0.0182 (9)
O2	0.3348 (3)	0.3264 (3)	0.8198 (3)	0.0230 (7)
C21	0.2666 (6)	0.1845 (5)	0.7645 (5)	0.0293 (12)
H21A	0.3403	0.1003	0.7840	0.044*
H21B	0.2389	0.1936	0.6595	0.044*
H21C	0.1741	0.1631	0.8125	0.044*
C3	0.2758 (5)	0.3498 (4)	1.0677 (4)	0.0187 (10)
C31	0.1112 (5)	0.3877 (6)	1.0153 (5)	0.0264 (10)
H31A	0.1033	0.4137	0.9117	0.040*
H31B	0.0773	0.4755	1.0702	0.040*
H31C	0.0459	0.2985	1.0298	0.040*
C4	0.3252 (5)	0.3437 (4)	1.2163 (4)	0.0197 (10)
C41	0.2135 (5)	0.3755 (5)	1.3269 (4)	0.0236 (10)
H41A	0.2616	0.3490	1.4242	0.035*
H41B	0.1207	0.3132	1.3043	0.035*
H41C	0.1859	0.4848	1.3241	0.035*
C5	0.4781 (5)	0.3086 (5)	1.2598 (4)	0.0187 (10)
O5	0.5276 (4)	0.3041 (3)	1.4082 (3)	0.0249 (8)
C51	0.5258 (6)	0.1493 (5)	1.4649 (5)	0.0298 (12)
H51A	0.4198	0.1112	1.4571	0.045*
H51B	0.5684	0.1493	1.5672	0.045*
H51C	0.5880	0.0824	1.4090	0.045*
C6	0.5844 (5)	0.2821 (4)	1.1611 (4)	0.0199 (10)
C61	0.7503 (5)	0.2498 (6)	1.2148 (5)	0.0268 (11)
H6A	0.7664	0.2667	1.3200	0.040*
H61B	0.8171	0.3190	1.1661	0.040*
H61C	0.7749	0.1428	1.1930	0.040*
C7	0.6461 (5)	0.2592 (5)	0.8990 (5)	0.0213 (10)
H7A	0.5929	0.1994	0.8178	0.026*
H7B	0.7341	0.1972	0.9425	0.026*
C8	0.7060 (5)	0.4088 (5)	0.8402 (5)	0.0222 (10)
H8A	0.6181	0.4699	0.7951	0.027*
H8B	0.7573	0.4695	0.9219	0.027*
C9	0.8177 (5)	0.3819 (5)	0.7297 (4)	0.0209 (10)
O9	0.8613 (4)	0.2584 (3)	0.6916 (3)	0.0284 (8)
O91	0.8665 (4)	0.5155 (3)	0.6762 (3)	0.0253 (8)
C91	0.9723 (6)	0.4994 (5)	0.5678 (5)	0.0262 (11)
H91A	1.0648	0.4454	0.6099	0.039*
H91B	1.0007	0.6016	0.5345	0.039*
H91C	0.9235	0.4403	0.4854	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.023 (3)	0.015 (2)	0.023 (2)	−0.0006 (19)	0.007 (2)	0.0047 (19)
C2	0.020 (2)	0.0145 (19)	0.020 (2)	−0.002 (2)	0.0022 (18)	0.0028 (19)
O2	0.0250 (18)	0.0244 (16)	0.0191 (16)	−0.0028 (14)	0.0005 (13)	0.0022 (13)
C21	0.031 (3)	0.029 (3)	0.028 (3)	−0.002 (2)	0.001 (2)	−0.001 (2)
C3	0.017 (2)	0.014 (2)	0.025 (2)	−0.0024 (18)	0.0051 (19)	0.0043 (17)
C31	0.022 (3)	0.027 (2)	0.030 (3)	0.002 (2)	0.005 (2)	0.002 (2)
C4	0.020 (2)	0.014 (2)	0.026 (2)	0.0007 (18)	0.009 (2)	0.0005 (18)
C41	0.023 (3)	0.021 (2)	0.029 (2)	0.004 (2)	0.010 (2)	−0.002 (2)
C5	0.024 (3)	0.014 (2)	0.018 (2)	−0.002 (2)	0.0034 (19)	0.0021 (19)
O5	0.032 (2)	0.0235 (16)	0.0185 (16)	0.0000 (15)	0.0019 (14)	−0.0024 (14)
C51	0.037 (3)	0.030 (3)	0.022 (3)	−0.001 (2)	0.000 (2)	0.002 (2)
C6	0.019 (3)	0.017 (2)	0.023 (2)	−0.0027 (19)	−0.002 (2)	−0.0019 (18)
C61	0.026 (3)	0.030 (2)	0.024 (2)	−0.001 (2)	0.001 (2)	0.000 (2)
C7	0.021 (3)	0.020 (2)	0.024 (2)	−0.0018 (19)	0.006 (2)	0.0014 (18)
C8	0.026 (3)	0.018 (2)	0.024 (2)	0.000 (2)	0.008 (2)	0.0035 (19)
C9	0.018 (2)	0.022 (2)	0.022 (2)	−0.003 (2)	0.0018 (19)	0.001 (2)
O9	0.033 (2)	0.0203 (19)	0.0343 (19)	−0.0004 (15)	0.0155 (16)	−0.0031 (14)
O91	0.030 (2)	0.0189 (17)	0.0286 (18)	0.0002 (14)	0.0135 (15)	0.0040 (14)
C91	0.030 (3)	0.027 (2)	0.024 (2)	0.002 (2)	0.011 (2)	0.002 (2)

Geometric parameters (Å, º) top

C1—C2	1.391 (6)	O5—C51	1.444 (5)
C1—C6	1.397 (6)	C51—H51A	0.9800
C1—C7	1.513 (6)	C51—H51B	0.9800
C2—C3	1.397 (6)	C51—H51C	0.9800
C2—O2	1.402 (5)	C6—C61	1.511 (6)
O2—C21	1.440 (5)	C61—H6A	0.9800
C21—H21A	0.9800	C61—H61B	0.9800
C21—H21B	0.9800	C61—H61C	0.9800
C21—H21C	0.9800	C7—C8	1.522 (6)
C3—C4	1.399 (6)	C7—H7A	0.9900
C3—C31	1.507 (6)	C7—H7B	0.9900
C31—H31A	0.9800	C8—C9	1.503 (6)
C31—H31B	0.9800	C8—H8A	0.9900
C31—H31C	0.9800	C8—H8B	0.9900
C4—C5	1.390 (6)	C9—O9	1.203 (5)
C4—C41	1.511 (6)	C9—O91	1.348 (5)
C41—H41A	0.9800	O91—C91	1.440 (5)
C41—H41B	0.9800	C91—H91A	0.9800
C41—H41C	0.9800	C91—H91B	0.9800
C5—C6	1.388 (6)	C91—H91C	0.9800
C5—O5	1.397 (5)

C2—C1—C6	118.3 (4)	O5—C51—H51B	109.5
C2—C1—C7	119.8 (4)	H51A—C51—H51B	109.5
C6—C1—C7	121.9 (4)	O5—C51—H51C	109.5
C1—C2—C3	122.7 (4)	H51A—C51—H51C	109.5
C1—C2—O2	118.2 (4)	H51B—C51—H51C	109.5
C3—C2—O2	119.0 (4)	C5—C6—C1	119.3 (4)
C2—O2—C21	112.8 (3)	C5—C6—C61	120.0 (4)
O2—C21—H21A	109.5	C1—C6—C61	120.7 (4)
O2—C21—H21B	109.5	C6—C61—H6A	109.5
H21A—C21—H21B	109.5	C6—C61—H61B	109.5
O2—C21—H21C	109.5	H6A—C61—H61B	109.5
H21A—C21—H21C	109.5	C6—C61—H61C	109.5
H21B—C21—H21C	109.5	H6A—C61—H61C	109.5
C2—C3—C4	118.4 (4)	H61B—C61—H61C	109.5
C2—C3—C31	120.8 (4)	C1—C7—C8	112.1 (3)
C4—C3—C31	120.8 (4)	C1—C7—H7A	109.2
C3—C31—H31A	109.5	C8—C7—H7A	109.2
C3—C31—H31B	109.5	C1—C7—H7B	109.2
H31A—C31—H31B	109.5	C8—C7—H7B	109.2
C3—C31—H31C	109.5	H7A—C7—H7B	107.9
H31A—C31—H31C	109.5	C9—C8—C7	112.5 (4)
H31B—C31—H31C	109.5	C9—C8—H8A	109.1
C5—C4—C3	118.9 (4)	C7—C8—H8A	109.1
C5—C4—C41	120.9 (4)	C9—C8—H8B	109.1
C3—C4—C41	120.2 (4)	C7—C8—H8B	109.1
C4—C41—H41A	109.5	H8A—C8—H8B	107.8
C4—C41—H41B	109.5	O9—C9—O91	122.6 (4)
H41A—C41—H41B	109.5	O9—C9—C8	125.8 (4)
C4—C41—H41C	109.5	O91—C9—C8	111.6 (4)
H41A—C41—H41C	109.5	C9—O91—C91	115.0 (3)
H41B—C41—H41C	109.5	O91—C91—H91A	109.5
C6—C5—C4	122.3 (4)	O91—C91—H91B	109.5
C6—C5—O5	118.8 (4)	H91A—C91—H91B	109.5
C4—C5—O5	118.8 (4)	O91—C91—H91C	109.5
C5—O5—C51	111.6 (3)	H91A—C91—H91C	109.5
O5—C51—H51A	109.5	H91B—C91—H91C	109.5

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 benzene ring.

D—H···A	D—H	H···A	D···A	D—H···A
C41—H41B···O91ⁱ	0.98	2.59	3.205 (6)	121
C41—H41C···O9ⁱⁱ	0.98	2.41	3.392 (5)	175
C8—H8A···Cgⁱⁱ	0.99	3.15	3.763 (6)	121

Symmetry codes: (i) −x+1, y−1/2, −z+2; (ii) −x+1, y+1/2, −z+2.

Acknowledgements

We thank the NZ Ministry of Business, Innovation and Employment Science Investment Fund (grant No. UOOX1206) for support of this work and the University of Otago for the purchase of the diffractometer. JS thanks the Chemistry Department, University of Otago, for the support of his work.

Funding information

Funding for this research was provided by: NZ Ministry of Business, Innovation and Employment Science Investment Fund (award No. UOOX1206).

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