organic compounds
Methyl 3-(2,5-dimethoxy-3,4,6-trimethylphenyl)propanoate
aDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
*Correspondence e-mail: jsimpson@alkali.otago.ac.nz
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)°.
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.
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 . With no heavy atoms in the molecule, the could not be determined reliably.
details are summarized in Table 2
|
Structural data
CCDC reference: 1541364
https://doi.org/10.1107/S2414314617005004/lh4018sup1.cif
contains datablocks I, global. DOI: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
Data collection: APEX2 (Bruker, 2013); cell
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).C15H22O4 | F(000) = 288 |
Mr = 266.32 | Dx = 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 |
Bruker APEXII CCD area detector diffractometer | 1781 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
φ and ω scans | θmax = 23.0°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | h = −9→9 |
Tmin = 0.660, Tmax = 0.745 | k = −9→9 |
5680 measured reflections | l = −9→10 |
1929 independent reflections |
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(Fo2) + (0.026P)2 + 0.2556P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.098 | (Δ/σ)max < 0.001 |
S = 1.09 | Δρmax = 0.14 e Å−3 |
1929 reflections | Δρmin = −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) |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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 |
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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