Prop-2-ynyl 3-meth­oxy-4-(prop-2-yn­yloxy)benzoate

Cresten Moodley; Alfred Muller; Yonas H Belay

doi:10.1107/S2414314624001639

. 2024 Feb 27;9(Pt 2):x240163. doi: 10.1107/S2414314624001639

Prop-2-ynyl 3-methoxy-4-(prop-2-ynyloxy)benzoate

Cresten Moodley ^a,^*, Alfred Muller ^a, Yonas H Belay ^a

Editor: W T A Harrison^b

PMCID: PMC10915548 PMID: 38455112

The title compound, C₁₄H₁₂O₄, was prepared via alkylation of 4-hydroxy-3-methoxybenzoic acid with propargyl bromide in the presence of K₂CO₃.

Keywords: crystal structure, dimer, hydrogen bonding

Abstract

The title compound, C₁₄H₁₂O₄, comprises of two crystallographically independent molecules in the asymmetric unit, linked via C—H⋯O interactions to form dimeric entities. The allylic groups are twisted out of the phenyl planes with dihedral angles varying between 7.92 (13) and 25.42 (8)°. In the crystal, the packing follows a zigzag pattern along the c-axis direction. The absolute configuration of the sample could not be determined reliably.

Structure description

Vanillic acid (4-hydroxy-3-methoxybenzoic acid) is an aromatic phenolic acid widely used as a flavouring agent in the food industry. 4-Hydroxy-3-methoxybenzoic acid is naturally observed in some forms of vanilla and many other plant extracts, but may also be chemically synthesized (Calixto-Campos et al., 2015 ▸). In addition to being a flavourant, this compound offers remarkable therapeutic (anticancer, antiobesity, antidiabetic, antibacterial, anti-inflammatory, and antioxidant) effects (Kaur et al., 2022 ▸) and versatility for use in polymeric coatings (Silva et al., 2016 ▸; El-Toni et al., 2005 ▸), as an inclusion agent for encapsulants (Rajendiran & Jude Jenita, 2015 ▸; Hong et al., 2008 ▸) and as a construct in metallomacrocyles (Xiong et al., 2000 ▸). More recently, this compound has been reported as a promising linker precursor towards novel coordination polymers (Belay et al., 2019 ▸). In this study, the title compound, C₁₄H₁₂O₄, was investigated as an intermediate toward hydroxamic acid-type linker systems and was prepared via the alkylation of 4-hydroxy-3-methoxybenzoic acid with propargyl bromide in the presence of K₂CO₃ (Buckley et al., 2014 ▸; Hoogendoorn et al., 2011 ▸).

The title compound crystallizes in the orthorhombic Pca2₁ (Z = 8) space group resulting in two independent molecules (A and B) in the asymmetric unit (Fig. 1 ▸) with all of the bond lengths and angles falling within the normal ranges. The differences between these two molecules are observed in the allyl groups attached to the carboxylate and para-hydroxy positions of 4-hydroxy-3-methoxybenzoic acid, respectively, which display dihedral angles varying between 7.91 (13) and 25.42 (8)° out of plane with each of the benzoate rings for A and B. This observation is best illustrated by superimposing the two molecules (Fig. 2 ▸).

A view of the molecular structure of the title compound as two independent molecules (A and B) in the asymmetric unit, with the atom labelling. The displacement ellipsoids are drawn at the 50% probability level.

Superimposed view of the two independent molecules in the asymmetric unit (r.m.s. deviation = 0.113 Å, max displacement = 0.258 Å).

In molecule A, the dihedral angles between the benzene ring (C4–C9) and the methoxy group (C9/O2/C10), the ester group (O4/C12–C14) and the ether group (O1/C1–C3) are 7.17 (15), 15.80 (12) and 11.48 (15)°, respectively. In molecule B, the corresponding angles between the benzene ring (C18–C22), the methoxy group (C23/O6/C24), the ester group (O8/C26–C28) and the ether group (O5/C15–C17) are 3.22 (16), 25.42 (8) and 7.92 (13)°, respectively.

Non-classical intermolecular hydrogen bonding is observed in the extended structure of the title compound. These interactions (Fig. 3 ▸) are summarized in Table 1 ▸ and a packing diagram of the title compound shows the molecules linked by infinite C—H⋯O chains along the c-axis direction (Fig. 4 ▸).

The non-classical C—H⋯O hydrogen-bonding interactions observed for the title compound, shown as dashed lines.

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O6	0.95	2.30	3.231 (5)	165
C14—H14⋯O3ⁱ	0.95	2.28	3.231 (5)	177
C15—H15⋯O2	0.95	2.28	3.213 (5)	169
C28—H28⋯O7ⁱⁱ	0.95	2.41	3.291 (5)	155

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Packing diagram showing the title compound molecules linked by infinite one-dimensional C—H⋯O chains along the c-axis direction.

Synthesis and crystallization

A solution of 4-hydroxy-3-methoxybenzoic acid (2.0 g, 11.90 mmol) was treated with K₂CO₃ (2.50 g, 17.85 mmol) in acetone. The reaction mixture was stirred under reflux for approximately 30 minutes followed by the addition of propargyl bromide (3.0 ml, 23.8 mmol of 80 wt. % in toluene). After stirring for 4 h, the reaction mixture was concentrated under vacuum. The residue was extracted using ethyl acetate, washed successively (water and brine) and dried over anhydrous sodium sulfate. The crude product was then recrystallized from the mixed solvents of dichloromethane and hexane to provide the title compound as colourless needles.

Analytical data: Melting point range: 65–68°C; ¹H NMR (CDCl₃, 400 MHZ): δ 7.69 (d, J = 8.4 Hz, 1H), 7.55 (s, 1H), 7.03 (d, J = 8.4 Hz, 1H), 4.88 (d, J = 2.4 Hz, 2H), 4.81 (d, J = 2.4 Hz, 2H), 3.91 (s, 3H), 2.52 (t, J = 2.4 Hz, 1H), 2.50 (t, J = 2.4 Hz, 1H); ¹³C NMR (CDCl₃, 400 MHZ): δ 165.2, 150.9, 149.0, 123.4, 122.8, 112.5, 77.8, 74.8, 56.4, 55.9, 52.2.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Reflection (200) was removed as discrepant. The highest electron density of 0.22 e Å⁻³ is 0.75 Å away from C5, while the deepest electron density of −0.25 e Å⁻³ is 1.27 Å away from C25.

Table 2. Experimental details.

Crystal data
Chemical formula	C₁₄H₁₂O₄
M _r	244.24
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	100
a, b, c (Å)	13.7387 (12), 20.547 (2), 8.4283 (9)
V (Å³)	2379.2 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.07 × 0.03

Data collection
Diffractometer	Bruker APEX DUO 4K CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)
T_min, T_max	0.487, 0.749
No. of measured, independent and observed [I > 2σ(I)] reflections	12893, 5028, 3236
R _int	0.072
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.111, 1.00
No. of reflections	5028
No. of parameters	326
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25
Absolute structure	Flack x determined using 833 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ▸)
Absolute structure parameter	−1.6 (10)

Open in a new tab

Computer programs: APEX2 (Bruker, 2011 ▸), SAINT and XPREP (Bruker, 2008 ▸), SIR97 (Altomare et al., 1999 ▸), SHELXL2019/2 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg & Putz, 2005 ▸) and WinGX publication routines (Farrugia, 2012 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2414314624001639/hb4463sup1.cif

x-09-x240163-sup1.cif^{(411.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2414314624001639/hb4463Isup2.hkl

x-09-x240163-Isup2.hkl^{(400.3KB, hkl)}

x-09-x240163-Isup3.cml^{(4.7KB, cml)}

Supporting information file. DOI: 10.1107/S2414314624001639/hb4463Isup3.cml

CCDC reference: 2333706

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

The University of Johannesburg, Department of Chemical Sciences, is thanked for affording the opportunity to conduct the experimental research as well as providing the instrumentation necessary to characterize the title compound.

full crystallographic data

Prop-2-ynyl 3-methoxy-4-(prop-2-ynyloxy)benzoate. Crystal data

C₁₄H₁₂O₄	D_x = 1.364 Mg m⁻³
M_r = 244.24	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pca2₁	Cell parameters from 13397 reflections
a = 13.7387 (12) Å	θ = 0.1–28.4°
b = 20.547 (2) Å	µ = 0.10 mm⁻¹
c = 8.4283 (9) Å	T = 100 K
V = 2379.2 (4) Å³	Needle, colourless
Z = 8	0.40 × 0.07 × 0.03 mm
F(000) = 1024

Open in a new tab

Prop-2-ynyl 3-methoxy-4-(prop-2-ynyloxy)benzoate. Data collection

Bruker APEX DUO 4K CCD diffractometer	5028 independent reflections
Radiation source: Sealed tube	3236 reflections with I > 2σ(I)
Detector resolution: 8.4 pixels mm^-1	R_int = 0.072
φ and ω scans	θ_max = 28.4°, θ_min = 1.0°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −18→16
T_min = 0.487, T_max = 0.749	k = −23→27
12893 measured reflections	l = −7→11

Open in a new tab

Prop-2-ynyl 3-methoxy-4-(prop-2-ynyloxy)benzoate. Refinement

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.052	w = 1/[σ²(F_o²) + (0.0426P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.111	(Δ/σ)_max = 0.003
S = 1.00	Δρ_max = 0.22 e Å⁻³
5028 reflections	Δρ_min = −0.25 e Å⁻³
326 parameters	Absolute structure: Flack x determined using 833 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −1.6 (10)

Open in a new tab

Prop-2-ynyl 3-methoxy-4-(prop-2-ynyloxy)benzoate. Special details

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. The hydrogen atoms were refined isotropically in their idealized geometrical positions while riding on their anisotropic parent atoms with U_iso = 1.2U_eq for the aromatic and methine protons, and U_iso(H) = 1.5U_eq(C) for the methyl protons, the latter groups were refined as a fixed rotor and adjusted to match the hydrogen atoms electron density from the Fourier difference map.

Open in a new tab

Prop-2-ynyl 3-methoxy-4-(prop-2-ynyloxy)benzoate. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)

	x	y	z	U_iso*/U_eq
C1	0.8623 (3)	0.4803 (2)	0.5854 (5)	0.0277 (10)
H1	0.865272	0.441594	0.523834	0.033*
C2	0.8586 (3)	0.5283 (2)	0.6621 (5)	0.0216 (9)
C3	0.8542 (3)	0.58880 (19)	0.7541 (5)	0.0218 (9)
H3A	0.792808	0.590809	0.815537	0.026*
H3B	0.909534	0.591193	0.829057	0.026*
C4	0.8578 (3)	0.70289 (19)	0.7050 (4)	0.0172 (8)
C5	0.8355 (3)	0.7179 (2)	0.8601 (5)	0.0218 (9)
H5	0.818301	0.684249	0.932124	0.026*
C6	0.8381 (3)	0.78228 (18)	0.9115 (4)	0.0201 (9)
H6	0.822973	0.792274	1.018751	0.024*
C7	0.8625 (3)	0.8317 (2)	0.8079 (4)	0.0184 (9)
C8	0.8831 (3)	0.8172 (2)	0.6488 (4)	0.0178 (9)
H8	0.898778	0.851112	0.576445	0.021*
C9	0.8806 (3)	0.7534 (2)	0.5981 (4)	0.0189 (9)
C10	0.9142 (3)	0.78343 (19)	0.3294 (5)	0.0242 (9)
H10A	0.969498	0.810891	0.359604	0.036*
H10B	0.855279	0.810159	0.322386	0.036*
H10C	0.927149	0.763268	0.226153	0.036*
C11	0.8692 (3)	0.9007 (2)	0.8589 (5)	0.0212 (9)
C12	0.8697 (3)	0.9719 (2)	1.0807 (5)	0.0299 (11)
H12A	0.931613	0.990641	1.041645	0.036*
H12B	0.815584	1.000530	1.047077	0.036*
C13	0.8716 (3)	0.9661 (2)	1.2525 (5)	0.0278 (10)
C14	0.8750 (3)	0.9624 (2)	1.3921 (5)	0.0325 (11)
H14	0.877700	0.959484	1.504519	0.039*
C15	0.9067 (3)	0.5981 (2)	0.2571 (5)	0.0260 (9)
H15	0.910724	0.635494	0.322918	0.031*
C16	0.9016 (3)	0.5515 (2)	0.1751 (5)	0.0239 (9)
C17	0.8920 (3)	0.49179 (19)	0.0811 (5)	0.0226 (9)
H17A	0.829561	0.491684	0.022371	0.027*
H17B	0.945988	0.488156	0.003873	0.027*
C18	0.8798 (3)	0.3775 (2)	0.1339 (4)	0.0177 (9)
C19	0.8565 (3)	0.3629 (2)	−0.0221 (4)	0.0203 (9)
H19	0.848605	0.396833	−0.097637	0.024*
C20	0.8446 (3)	0.29830 (19)	−0.0673 (5)	0.0197 (9)
H20	0.828592	0.288233	−0.174173	0.024*
C21	0.8561 (3)	0.24841 (19)	0.0419 (5)	0.0175 (8)
C22	0.8783 (3)	0.2632 (2)	0.2010 (5)	0.0183 (9)
H22	0.885351	0.229252	0.276632	0.022*
C23	0.8897 (3)	0.3272 (2)	0.2463 (4)	0.0186 (8)
C24	0.9196 (3)	0.2979 (2)	0.5156 (4)	0.0224 (9)
H24A	0.936300	0.317677	0.617786	0.034*
H24B	0.857032	0.275307	0.524575	0.034*
H24C	0.970282	0.266625	0.485517	0.034*
C25	0.8537 (3)	0.1789 (2)	−0.0043 (4)	0.0199 (9)
C26	0.8474 (3)	0.1063 (2)	−0.2232 (5)	0.0248 (9)
H26A	0.786129	0.081748	−0.207870	0.030*
H26B	0.900466	0.083150	−0.167331	0.030*
C27	0.8699 (3)	0.1123 (2)	−0.3932 (5)	0.0233 (10)
C28	0.8893 (3)	0.1151 (2)	−0.5294 (5)	0.0271 (10)
H28	0.904872	0.117410	−0.639094	0.032*
O1	0.8587 (2)	0.64180 (14)	0.6418 (3)	0.0215 (7)
O2	0.90058 (19)	0.73376 (13)	0.4462 (3)	0.0223 (6)
O3	0.8860 (2)	0.94679 (15)	0.7732 (3)	0.0289 (7)
O4	0.8561 (2)	0.90620 (14)	1.0171 (3)	0.0245 (7)
O5	0.89505 (19)	0.43864 (13)	0.1930 (3)	0.0218 (6)
O6	0.91275 (19)	0.34757 (13)	0.3969 (3)	0.0224 (6)
O7	0.8687 (2)	0.13363 (14)	0.0841 (3)	0.0246 (7)
O8	0.83739 (18)	0.17221 (13)	−0.1617 (3)	0.0222 (6)

Open in a new tab

Prop-2-ynyl 3-methoxy-4-(prop-2-ynyloxy)benzoate. Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.031 (2)	0.021 (2)	0.031 (2)	−0.0013 (19)	−0.003 (2)	−0.0048 (19)
C2	0.024 (2)	0.019 (2)	0.022 (2)	−0.0013 (18)	−0.0033 (17)	0.0021 (18)
C3	0.031 (2)	0.016 (2)	0.018 (2)	−0.0008 (17)	−0.0018 (17)	0.0027 (16)
C4	0.020 (2)	0.016 (2)	0.0157 (19)	0.0005 (16)	−0.0027 (15)	−0.0032 (16)
C5	0.025 (2)	0.020 (2)	0.020 (2)	−0.0004 (17)	0.0000 (16)	0.0021 (17)
C6	0.027 (2)	0.023 (2)	0.0110 (19)	0.0011 (17)	0.0023 (15)	−0.0049 (16)
C7	0.021 (2)	0.019 (2)	0.015 (2)	0.0025 (17)	0.0001 (15)	−0.0030 (16)
C8	0.025 (2)	0.017 (2)	0.0116 (17)	0.0020 (17)	−0.0006 (15)	0.0012 (16)
C9	0.024 (2)	0.020 (2)	0.0129 (19)	0.0031 (17)	−0.0022 (16)	−0.0005 (17)
C10	0.034 (2)	0.024 (2)	0.0141 (19)	0.0052 (19)	0.0022 (17)	0.0027 (17)
C11	0.029 (2)	0.022 (2)	0.0126 (19)	0.0030 (18)	0.0000 (16)	−0.0034 (17)
C12	0.051 (3)	0.018 (3)	0.021 (2)	−0.001 (2)	0.000 (2)	−0.004 (2)
C13	0.045 (3)	0.017 (3)	0.021 (2)	−0.0024 (19)	−0.0012 (19)	−0.0043 (18)
C14	0.059 (3)	0.019 (2)	0.019 (2)	−0.001 (2)	0.000 (2)	−0.002 (2)
C15	0.033 (2)	0.019 (2)	0.026 (2)	−0.0012 (19)	0.0044 (19)	0.0004 (19)
C16	0.026 (2)	0.023 (2)	0.023 (2)	0.0020 (18)	0.0028 (17)	0.0034 (18)
C17	0.034 (2)	0.017 (2)	0.0170 (19)	0.0020 (17)	0.0018 (18)	−0.0003 (16)
C18	0.023 (2)	0.014 (2)	0.0160 (19)	0.0024 (16)	0.0014 (15)	−0.0015 (17)
C19	0.026 (2)	0.021 (2)	0.0134 (18)	0.0003 (18)	−0.0002 (16)	0.0026 (16)
C20	0.024 (2)	0.022 (2)	0.0128 (19)	−0.0022 (17)	0.0021 (15)	0.0004 (17)
C21	0.0187 (19)	0.014 (2)	0.0202 (19)	0.0011 (17)	0.0005 (15)	−0.0016 (17)
C22	0.022 (2)	0.016 (2)	0.0163 (19)	−0.0011 (16)	0.0016 (15)	0.0007 (17)
C23	0.020 (2)	0.021 (2)	0.0144 (18)	0.0009 (16)	−0.0013 (15)	−0.0039 (17)
C24	0.034 (2)	0.022 (2)	0.0118 (18)	−0.0010 (19)	−0.0026 (16)	0.0028 (16)
C25	0.023 (2)	0.021 (2)	0.015 (2)	−0.0011 (18)	−0.0005 (16)	−0.0016 (17)
C26	0.041 (2)	0.017 (2)	0.0164 (18)	−0.0010 (19)	0.0006 (17)	−0.0035 (17)
C27	0.034 (2)	0.009 (2)	0.027 (2)	−0.0001 (18)	−0.0019 (18)	−0.0042 (17)
C28	0.043 (3)	0.018 (2)	0.021 (2)	0.0003 (19)	0.0010 (18)	−0.0010 (19)
O1	0.0349 (16)	0.0147 (16)	0.0150 (14)	0.0010 (12)	−0.0007 (12)	0.0013 (12)
O2	0.0337 (16)	0.0194 (16)	0.0138 (13)	0.0032 (12)	0.0009 (11)	0.0000 (11)
O3	0.053 (2)	0.0189 (18)	0.0153 (14)	−0.0030 (14)	0.0028 (13)	−0.0003 (13)
O4	0.0438 (17)	0.0150 (16)	0.0146 (14)	−0.0022 (13)	0.0017 (12)	−0.0031 (11)
O5	0.0365 (16)	0.0124 (15)	0.0165 (13)	0.0005 (13)	−0.0019 (12)	−0.0009 (11)
O6	0.0366 (16)	0.0172 (15)	0.0135 (12)	−0.0014 (12)	−0.0023 (11)	−0.0003 (11)
O7	0.0398 (18)	0.0174 (17)	0.0165 (14)	−0.0004 (13)	−0.0008 (12)	−0.0006 (12)
O8	0.0365 (17)	0.0136 (15)	0.0165 (13)	0.0000 (12)	−0.0022 (12)	−0.0006 (12)

Open in a new tab

Prop-2-ynyl 3-methoxy-4-(prop-2-ynyloxy)benzoate. Geometric parameters (Å, º)

C1—C2	1.181 (6)	C15—C16	1.182 (6)
C1—H1	0.9500	C15—H15	0.9500
C2—C3	1.466 (5)	C16—C17	1.467 (6)
C3—O1	1.444 (5)	C17—O5	1.444 (5)
C3—H3A	0.9900	C17—H17A	0.9900
C3—H3B	0.9900	C17—H17B	0.9900
C4—O1	1.364 (4)	C18—O5	1.367 (5)
C4—C5	1.378 (5)	C18—C19	1.386 (5)
C4—C9	1.410 (5)	C18—C23	1.409 (5)
C5—C6	1.392 (5)	C19—C20	1.391 (6)
C5—H5	0.9500	C19—H19	0.9500
C6—C7	1.381 (5)	C20—C21	1.387 (5)
C6—H6	0.9500	C20—H20	0.9500
C7—C8	1.403 (5)	C21—C22	1.408 (6)
C7—C11	1.484 (6)	C21—C25	1.481 (6)
C8—C9	1.379 (6)	C22—C23	1.379 (6)
C8—H8	0.9500	C22—H22	0.9500
C9—O2	1.370 (4)	C23—O6	1.373 (4)
C10—O2	1.430 (4)	C24—O6	1.433 (4)
C10—H10A	0.9800	C24—H24A	0.9800
C10—H10B	0.9800	C24—H24B	0.9800
C10—H10C	0.9800	C24—H24C	0.9800
C11—O3	1.213 (5)	C25—O7	1.209 (5)
C11—O4	1.350 (4)	C25—O8	1.353 (4)
C12—C13	1.453 (6)	C26—O8	1.456 (5)
C12—O4	1.464 (5)	C26—C27	1.471 (6)
C12—H12A	0.9900	C26—H26A	0.9900
C12—H12B	0.9900	C26—H26B	0.9900
C13—C14	1.180 (6)	C27—C28	1.180 (6)
C14—H14	0.9500	C28—H28	0.9500

C2—C1—H1	180.0	O5—C17—H17A	110.5
C1—C2—C3	178.8 (5)	C16—C17—H17A	110.5
O1—C3—C2	106.9 (3)	O5—C17—H17B	110.5
O1—C3—H3A	110.3	C16—C17—H17B	110.5
C2—C3—H3A	110.3	H17A—C17—H17B	108.7
O1—C3—H3B	110.3	O5—C18—C19	125.4 (4)
C2—C3—H3B	110.3	O5—C18—C23	114.5 (3)
H3A—C3—H3B	108.6	C19—C18—C23	120.1 (4)
O1—C4—C5	125.3 (4)	C18—C19—C20	119.6 (4)
O1—C4—C9	115.2 (3)	C18—C19—H19	120.2
C5—C4—C9	119.4 (4)	C20—C19—H19	120.2
C4—C5—C6	120.1 (4)	C21—C20—C19	120.7 (4)
C4—C5—H5	119.9	C21—C20—H20	119.6
C6—C5—H5	119.9	C19—C20—H20	119.7
C7—C6—C5	120.5 (3)	C20—C21—C22	119.8 (4)
C7—C6—H6	119.7	C20—C21—C25	122.4 (4)
C5—C6—H6	119.7	C22—C21—C25	117.6 (3)
C6—C7—C8	119.8 (4)	C23—C22—C21	119.6 (4)
C6—C7—C11	122.3 (3)	C23—C22—H22	120.2
C8—C7—C11	117.9 (4)	C21—C22—H22	120.2
C9—C8—C7	119.5 (4)	O6—C23—C22	125.0 (4)
C9—C8—H8	120.2	O6—C23—C18	114.8 (3)
C7—C8—H8	120.2	C22—C23—C18	120.2 (4)
O2—C9—C8	124.4 (3)	O6—C24—H24A	109.5
O2—C9—C4	115.1 (4)	O6—C24—H24B	109.5
C8—C9—C4	120.5 (4)	H24A—C24—H24B	109.5
O2—C10—H10A	109.5	O6—C24—H24C	109.5
O2—C10—H10B	109.5	H24A—C24—H24C	109.5
H10A—C10—H10B	109.5	H24B—C24—H24C	109.5
O2—C10—H10C	109.5	O7—C25—O8	123.7 (4)
H10A—C10—H10C	109.5	O7—C25—C21	125.1 (4)
H10B—C10—H10C	109.5	O8—C25—C21	111.1 (4)
O3—C11—O4	123.3 (4)	O8—C26—C27	106.8 (3)
O3—C11—C7	125.8 (4)	O8—C26—H26A	110.4
O4—C11—C7	111.0 (3)	C27—C26—H26A	110.4
C13—C12—O4	106.9 (4)	O8—C26—H26B	110.4
C13—C12—H12A	110.3	C27—C26—H26B	110.4
O4—C12—H12A	110.3	H26A—C26—H26B	108.6
C13—C12—H12B	110.3	C28—C27—C26	177.9 (5)
O4—C12—H12B	110.3	C27—C28—H28	180.0
H12A—C12—H12B	108.6	C4—O1—C3	116.0 (3)
C14—C13—C12	178.4 (5)	C9—O2—C10	117.3 (3)
C13—C14—H14	180.0	C11—O4—C12	114.9 (3)
C16—C15—H15	180.0	C18—O5—C17	116.9 (3)
C15—C16—C17	176.5 (5)	C23—O6—C24	116.3 (3)
O5—C17—C16	106.1 (3)	C25—O8—C26	115.3 (3)

O1—C4—C5—C6	179.3 (4)	C21—C22—C23—C18	−0.4 (5)
C9—C4—C5—C6	−1.8 (6)	O5—C18—C23—O6	0.2 (5)
C4—C5—C6—C7	0.3 (6)	C19—C18—C23—O6	−179.9 (3)
C5—C6—C7—C8	1.2 (6)	O5—C18—C23—C22	−178.6 (3)
C5—C6—C7—C11	−178.0 (4)	C19—C18—C23—C22	1.4 (5)
C6—C7—C8—C9	−1.2 (6)	C20—C21—C25—O7	175.5 (4)
C11—C7—C8—C9	178.1 (3)	C22—C21—C25—O7	0.5 (6)
C7—C8—C9—O2	−179.2 (3)	C20—C21—C25—O8	−1.2 (5)
C7—C8—C9—C4	−0.3 (6)	C22—C21—C25—O8	−176.2 (3)
O1—C4—C9—O2	−0.2 (5)	C5—C4—O1—C3	−12.5 (6)
C5—C4—C9—O2	−179.3 (3)	C9—C4—O1—C3	168.5 (3)
O1—C4—C9—C8	−179.2 (3)	C2—C3—O1—C4	−178.5 (3)
C5—C4—C9—C8	1.8 (6)	C8—C9—O2—C10	−7.4 (5)
C6—C7—C11—O3	−176.6 (4)	C4—C9—O2—C10	173.7 (3)
C8—C7—C11—O3	4.2 (6)	O3—C11—O4—C12	−3.7 (6)
C6—C7—C11—O4	4.8 (5)	C7—C11—O4—C12	175.0 (3)
C8—C7—C11—O4	−174.4 (3)	C13—C12—O4—C11	−169.1 (3)
O5—C18—C19—C20	178.8 (3)	C19—C18—O5—C17	−3.7 (5)
C23—C18—C19—C20	−1.1 (6)	C23—C18—O5—C17	176.2 (3)
C18—C19—C20—C21	−0.1 (6)	C16—C17—O5—C18	175.1 (3)
C19—C20—C21—C22	1.0 (5)	C22—C23—O6—C24	−3.7 (5)
C19—C20—C21—C25	−173.9 (4)	C18—C23—O6—C24	177.6 (3)
C20—C21—C22—C23	−0.8 (5)	O7—C25—O8—C26	−5.1 (6)
C25—C21—C22—C23	174.3 (3)	C21—C25—O8—C26	171.7 (3)
C21—C22—C23—O6	−179.0 (3)	C27—C26—O8—C25	−155.7 (3)

Open in a new tab

Prop-2-ynyl 3-methoxy-4-(prop-2-ynyloxy)benzoate. Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O6	0.95	2.30	3.231 (5)	165
C14—H14···O3ⁱ	0.95	2.28	3.231 (5)	177
C15—H15···O2	0.95	2.28	3.213 (5)	169
C28—H28···O7ⁱⁱ	0.95	2.41	3.291 (5)	155

Open in a new tab

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

Funding Statement

Funding for this research was provided by: National Research Foundation (bursary No. SFH170530234995 to Cresten Moodley).

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
Belay, Y., Coetzee, L. C., Williams, D. B. G. & Muller, A. (2019). Tetrahedron Lett.60, 501–503.
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Bruker (2008). SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2011). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Buckley, H. L., Rubin, L. K., Chromiński, M., McNicholas, B. J., Tsen, K. H., Gryko, D. T. & Arnold, J. (2014). Inorg. Chem.53, 7941–7950. [DOI] [PubMed]
Calixto-Campos, C., Carvalho, T. T., Hohmann, M. S., Pinho-Ribeiro, F. A., Fattori, V., Manchope, M. F., Zarpelon, A. C., Baracat, M. M., Georgetti, S. R., Casagrande, R. & Verri, W. A. Jr (2015). J. Nat. Prod.78, 1799–1808. [DOI] [PubMed]
El-Toni, A. M., Yin, S. & Sato, T. (2005). Mater. Chem. Phys.89, 154–158.
Farrugia, L. J. (2012). J. Appl. Cryst.45, 849–854.
Hong, M. M., Oh, J. M. & Choy, J. H. (2008). J. Nanosci. Nanotechnol.8, 5018–5021. [DOI] [PubMed]
Hoogendoorn, S., Blom, A. E., Willems, L. I., van der Marel, G. A. & Overkleeft, H. S. (2011). Org. Lett.13, 5656–5659. [DOI] [PubMed]
Kaur, J., Gulati, M., Singh, S. K., Kuppusamy, G., Kapoor, B., Mishra, V., Gupta, S., Arshad, M. F., Porwal, O., Jha, N. K., Chaitanya, M. V. N. L., Chellappan, D. K., Gupta, G., Gupta, P. K., Dua, K., Khursheed, R., Awasthi, A. & Corrie, L. (2022). Trends Food Sci. Technol.122, 187–200.
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst.48, 3–10. [DOI] [PMC free article] [PubMed]
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. [DOI] [PMC free article] [PubMed]
Rajendiran, N. & Jude Jenita, M. (2015). Spectrochim. Acta A Mol. Biomol. Spectrosc.136, 1349–1357. [DOI] [PubMed]
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.
Silva, L. D., Silva, F. A. S., Kubota, L. T., Lopes, C. B., Lima, P. R., Costa, E. O., Pinho Júnior, W. & Goulart, M. O. F. (2016). J. Solid State Electrochem.20, 2389–2393.
Xiong, R. G., Zuo, J. L., You, X. Z., Fun, H. K. & Raj (2000). Organometallics, 19, 4183–4186.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2414314624001639/hb4463sup1.cif

x-09-x240163-sup1.cif^{(411.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2414314624001639/hb4463Isup2.hkl

x-09-x240163-Isup2.hkl^{(400.3KB, hkl)}

x-09-x240163-Isup3.cml^{(4.7KB, cml)}

Supporting information file. DOI: 10.1107/S2414314624001639/hb4463Isup3.cml

CCDC reference: 2333706

Additional supporting information: crystallographic information; 3D view; checkCIF report

[bb1] Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.

[bb2] Belay, Y., Coetzee, L. C., Williams, D. B. G. & Muller, A. (2019). Tetrahedron Lett.60, 501–503.

[bb3] Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.

[bb4] Bruker (2008). SAINT and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA.

[bb5] Bruker (2011). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

[bb6] Buckley, H. L., Rubin, L. K., Chromiński, M., McNicholas, B. J., Tsen, K. H., Gryko, D. T. & Arnold, J. (2014). Inorg. Chem.53, 7941–7950. [DOI] [PubMed]

[bb7] Calixto-Campos, C., Carvalho, T. T., Hohmann, M. S., Pinho-Ribeiro, F. A., Fattori, V., Manchope, M. F., Zarpelon, A. C., Baracat, M. M., Georgetti, S. R., Casagrande, R. & Verri, W. A. Jr (2015). J. Nat. Prod.78, 1799–1808. [DOI] [PubMed]

[bb8] El-Toni, A. M., Yin, S. & Sato, T. (2005). Mater. Chem. Phys.89, 154–158.

[bb9] Farrugia, L. J. (2012). J. Appl. Cryst.45, 849–854.

[bb10] Hong, M. M., Oh, J. M. & Choy, J. H. (2008). J. Nanosci. Nanotechnol.8, 5018–5021. [DOI] [PubMed]

[bb11] Hoogendoorn, S., Blom, A. E., Willems, L. I., van der Marel, G. A. & Overkleeft, H. S. (2011). Org. Lett.13, 5656–5659. [DOI] [PubMed]

[bb12] Kaur, J., Gulati, M., Singh, S. K., Kuppusamy, G., Kapoor, B., Mishra, V., Gupta, S., Arshad, M. F., Porwal, O., Jha, N. K., Chaitanya, M. V. N. L., Chellappan, D. K., Gupta, G., Gupta, P. K., Dua, K., Khursheed, R., Awasthi, A. & Corrie, L. (2022). Trends Food Sci. Technol.122, 187–200.

[bb13] Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst.48, 3–10. [DOI] [PMC free article] [PubMed]

[bb14] Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. [DOI] [PMC free article] [PubMed]

[bb15] Rajendiran, N. & Jude Jenita, M. (2015). Spectrochim. Acta A Mol. Biomol. Spectrosc.136, 1349–1357. [DOI] [PubMed]

[bb16] Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8.

[bb17] Silva, L. D., Silva, F. A. S., Kubota, L. T., Lopes, C. B., Lima, P. R., Costa, E. O., Pinho Júnior, W. & Goulart, M. O. F. (2016). J. Solid State Electrochem.20, 2389–2393.

[bb18] Xiong, R. G., Zuo, J. L., You, X. Z., Fun, H. K. & Raj (2000). Organometallics, 19, 4183–4186.

PERMALINK

Prop-2-ynyl 3-methoxy-4-(prop-2-ynyloxy)benzoate

Cresten Moodley

Alfred Muller

Yonas H Belay

Roles

Abstract

Structure description

Figure 1.

Figure 2.