3-Meth­oxy-4-(prop-2-yn-1-yl­oxy)benzaldehyde

Ezhilarasu, T.; Balasubramanian, S.

doi:10.1107/S2414314616019192

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 12| December 2016| x161919

https://doi.org/10.1107/S2414314616019192

Open

access

3-Methoxy-4-(prop-2-yn-1-yloxy)benzaldehyde

Tamilarasu Ezhilarasu ^a and Sengottuvelan Balasubramanian ^a ^*

^aDepartment of Inorganic Chemistry, Guindy Campus, University of Madras, Chennai 600 025, India
^*Correspondence e-mail: bala2010@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 9 November 2016; accepted 2 December 2016; online 9 December 2016)

In the title compound, C₁₁H₁₀O₃, the prop-2-yn-1-yl group is inclined to the benzene ring by 69 (7)°. In the crystal, molecules are linked by a pair of C—H⋯O hydrogen bonds, forming inversion dimers with an R₂²(12) ring motif. The dimers are linked by a second C—H⋯O hydrogen bond, forming sheets parallel to the (102) plane. The sheets stack along the c-axis direction with a separation of ca 3.4 Å.

Keywords: crystal structure; vanillin; propynyloxy; C—H⋯O hydrogen bonds; inversion dimer.

CCDC reference: 1014207

Structure description

Vanillin and vanillin derivatives are used in food and non-food applications, in fragrances and as flavouring agents for pharmaceutical products (Hocking, 1997 ; Walton et al., 2003 ). Synthetic vanillin is used as an intermediate in chemical and pharmaceutical industries for the production of herbicides, antifoaming agents and drugs, such as papaverine, L-dopa and L-methyldopa, as well as antimicrobial agents such as trimethoprim (Fitzgerald et al., 2005 ). In the past few years, 1,2,3-triazole molecules have been synthesized which can be employed as chemotherapeutic agents for various diseases (Wang et al., 2008 ). In particular, vanillin when treated with propargyl bromide forms propargyloxybenzaldehyde which is linked via a 1,2,3-triazole ring with an alkane side arm (Ahmed Kamal et al., 2011 ). We report herein on the synthesis and crystal structure of a new vanillin derivative.

The molecular structure of the title compound is illustrated in Fig. 1. The prop-2-yn-1-yl group (C1≡C2—C3) is inclined to the benzene ring by 69 (7)°.

Figure 1
The molecular structure of the title compound, showing the atom labelling and 50% probability displacement ellipsoids.

In the crystal, molecules are linked by a pair of C—H⋯O hydrogen bonds, forming inversion dimers with an $[R_{2}^{2}]$ (12) ring motif (Table 1 and Fig. 2). The dimers are linked by a second C—H⋯O hydrogen bond, involving the propynyl group (H1), forming sheets parallel to plane (102); see Table 1 and Fig. 2. The sheets stack along the c-axis direction, with a separation of ca 3.4 Å, but with no significant intermolecular interactions being present.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O2ⁱ	0.97	2.42	3.374 (2)	166
C1—H1⋯O3ⁱⁱ	0.93	2.39	3.274 (2)	158
Symmetry codes: (i) -x, -y+1, -z; (ii) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Figure 2
The crystal packing of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines (see Table 1

) and, for clarity, only H atoms H1 and H3A (grey balls) have been included.

Synthesis and crystallization

4-Hydroxy-3-methoxybenzaldehyde (0.378 g, 2.48 mmol) and anhydrous K₂CO₃ (0.414 g, 3.0 mmol) were dissolved in 15 ml of dry DMF and propargyl bromide (1 g, 2.48 mmol) was added. The reaction mixture was stirred at room temperature for 24 h, and then poured into 100 ml of water and extracted with CHCl₃. The organic phases were combined and washed with water, brine solution, dried over anhydrous sodium sulfate and the solvent evaporated under vacuum. The crude product was purified by column chromatography using silica gel (hexane/ethyl acetate = 4:1 v/v) and the title compound was obtained as a yellow solid (yield 0.915 g, 78%; m.p. 458 K). The compound was dissolved in acetone and slowly evaporated to give brown block-like crystals.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₁H₁₀O₃
M_r	190.19
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.8560 (6), 11.8836 (6), 6.8348 (4)
β (°)	92.044 (1)
V (Å³)	962.36 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.961, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	10764, 1896, 1528
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.093, 1.07
No. of reflections	1896
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.13
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SIR92 (Altomare et al., 1993 ), SHELXL97 (Sheldrick, 2008 ) and Mercury (Macrae et al., 2008 ).

Structural data

CCDC reference: 1014207

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2414314616019192/su4097sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616019192/su4097Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616019192/su4097Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

3-Methoxy-4-(prop-2-yn-1-yloxy)benzaldehyde top

Crystal data top

C₁₁H₁₀O₃	F(000) = 400
M_r = 190.19	D_x = 1.313 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4115 reflections
a = 11.8560 (6) Å	θ = 2.4–28.4°
b = 11.8836 (6) Å	µ = 0.10 mm⁻¹
c = 6.8348 (4) Å	T = 296 K
β = 92.044 (1)°	Block, brown
V = 962.36 (9) Å³	0.35 × 0.30 × 0.25 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	1896 independent reflections
Radiation source: fine-focus sealed tube	1528 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω and φ scan	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→14
T_min = 0.961, T_max = 0.980	k = −14→14
10764 measured reflections	l = −8→8

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)] = 0.035	H-atom parameters constrained
wR(F²) = 0.093	w = 1/[σ²(F_o²) + (0.0353P)² + 0.2349P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1896 reflections	Δρ_max = 0.15 e Å⁻³
129 parameters	Δρ_min = −0.13 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: 0.0104 (19)

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.

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 > 2sigma(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
C1	0.25864 (14)	0.36251 (15)	−0.2945 (3)	0.0699 (5)
H1	0.2947	0.3419	−0.4077	0.084*
C2	0.21334 (12)	0.38838 (13)	−0.1523 (3)	0.0539 (4)
C3	0.15648 (13)	0.41756 (12)	0.0269 (2)	0.0547 (4)
H3A	0.0865	0.3755	0.0317	0.066*
H3B	0.2039	0.3955	0.1390	0.066*
C4	0.22014 (11)	0.60814 (11)	0.06716 (18)	0.0383 (3)
C5	0.33237 (11)	0.57799 (12)	0.09667 (19)	0.0433 (3)
H5	0.3527	0.5024	0.0997	0.052*
C6	0.41399 (11)	0.65991 (12)	0.12150 (19)	0.0445 (3)
H6	0.4893	0.6394	0.1408	0.053*
C7	0.38435 (11)	0.77230 (11)	0.11782 (18)	0.0416 (3)
C8	0.27149 (11)	0.80274 (11)	0.09066 (18)	0.0403 (3)
H8	0.2516	0.8784	0.0902	0.048*
C9	0.18929 (11)	0.72245 (11)	0.06453 (18)	0.0379 (3)
C10	0.04141 (14)	0.85726 (13)	0.0341 (3)	0.0610 (4)
H10A	0.0620	0.8914	0.1576	0.091*
H10B	−0.0390	0.8607	0.0131	0.091*
H10C	0.0773	0.8969	−0.0691	0.091*
C11	0.46886 (14)	0.86149 (14)	0.1404 (2)	0.0579 (4)
H11	0.4424	0.9352	0.1418	0.069*
O1	0.13206 (8)	0.53520 (8)	0.03999 (15)	0.0511 (3)
O2	0.07696 (8)	0.74270 (8)	0.03513 (15)	0.0518 (3)
O3	0.56883 (10)	0.84848 (12)	0.1572 (2)	0.0815 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0562 (10)	0.0683 (12)	0.0853 (13)	−0.0013 (8)	0.0054 (9)	−0.0240 (10)
C2	0.0445 (8)	0.0405 (8)	0.0762 (11)	−0.0023 (6)	−0.0035 (7)	−0.0097 (7)
C3	0.0559 (9)	0.0348 (8)	0.0739 (10)	−0.0050 (6)	0.0070 (8)	−0.0006 (7)
C4	0.0421 (7)	0.0379 (7)	0.0349 (6)	−0.0026 (6)	0.0015 (5)	−0.0017 (5)
C5	0.0475 (8)	0.0389 (7)	0.0431 (7)	0.0049 (6)	−0.0024 (6)	−0.0015 (6)
C6	0.0402 (7)	0.0542 (9)	0.0390 (7)	0.0019 (6)	−0.0016 (5)	−0.0036 (6)
C7	0.0464 (8)	0.0466 (8)	0.0321 (6)	−0.0061 (6)	0.0052 (5)	−0.0040 (6)
C8	0.0513 (8)	0.0358 (7)	0.0341 (6)	−0.0002 (6)	0.0054 (5)	−0.0016 (5)
C9	0.0410 (7)	0.0407 (7)	0.0320 (6)	0.0030 (6)	0.0020 (5)	−0.0019 (5)
C10	0.0585 (9)	0.0513 (9)	0.0729 (11)	0.0178 (8)	−0.0019 (8)	−0.0047 (8)
C11	0.0568 (10)	0.0608 (10)	0.0568 (10)	−0.0121 (8)	0.0107 (7)	−0.0090 (7)
O1	0.0439 (6)	0.0375 (5)	0.0720 (7)	−0.0023 (4)	0.0033 (5)	−0.0072 (5)
O2	0.0434 (6)	0.0431 (6)	0.0684 (7)	0.0068 (4)	−0.0034 (5)	−0.0062 (5)
O3	0.0540 (8)	0.0867 (10)	0.1042 (10)	−0.0200 (7)	0.0096 (7)	−0.0199 (8)

Geometric parameters (Å, º) top

C1—C2	1.168 (2)	C6—H6	0.9300
C1—H1	0.9300	C7—C8	1.3921 (19)
C2—C3	1.460 (2)	C7—C11	1.463 (2)
C3—O1	1.4311 (17)	C8—C9	1.3711 (18)
C3—H3A	0.9700	C8—H8	0.9300
C3—H3B	0.9700	C9—O2	1.3612 (16)
C4—O1	1.3647 (16)	C10—O2	1.4251 (17)
C4—C5	1.3858 (18)	C10—H10A	0.9600
C4—C9	1.4068 (18)	C10—H10B	0.9600
C5—C6	1.3789 (19)	C10—H10C	0.9600
C5—H5	0.9300	C11—O3	1.1968 (19)
C6—C7	1.3812 (19)	C11—H11	0.9300

C2—C1—H1	180.0	C8—C7—C11	118.51 (13)
C1—C2—C3	178.47 (18)	C9—C8—C7	120.80 (12)
O1—C3—C2	112.64 (13)	C9—C8—H8	119.6
O1—C3—H3A	109.1	C7—C8—H8	119.6
C2—C3—H3A	109.1	O2—C9—C8	125.69 (12)
O1—C3—H3B	109.1	O2—C9—C4	115.16 (11)
C2—C3—H3B	109.1	C8—C9—C4	119.15 (12)
H3A—C3—H3B	107.8	O2—C10—H10A	109.5
O1—C4—C5	125.57 (12)	O2—C10—H10B	109.5
O1—C4—C9	114.47 (11)	H10A—C10—H10B	109.5
C5—C4—C9	119.96 (12)	O2—C10—H10C	109.5
C6—C5—C4	120.10 (13)	H10A—C10—H10C	109.5
C6—C5—H5	120.0	H10B—C10—H10C	109.5
C4—C5—H5	120.0	O3—C11—C7	126.07 (16)
C5—C6—C7	120.23 (13)	O3—C11—H11	117.0
C5—C6—H6	119.9	C7—C11—H11	117.0
C7—C6—H6	119.9	C4—O1—C3	118.26 (11)
C6—C7—C8	119.76 (12)	C9—O2—C10	117.21 (11)
C6—C7—C11	121.73 (13)

C1—C2—C3—O1	−174 (100)	C5—C4—C9—O2	−179.79 (11)
O1—C4—C5—C6	179.69 (12)	O1—C4—C9—C8	179.94 (11)
C9—C4—C5—C6	−0.66 (19)	C5—C4—C9—C8	0.26 (18)
C4—C5—C6—C7	0.2 (2)	C6—C7—C11—O3	2.6 (2)
C5—C6—C7—C8	0.6 (2)	C8—C7—C11—O3	−176.98 (15)
C5—C6—C7—C11	−178.98 (12)	C5—C4—O1—C3	−4.62 (19)
C6—C7—C8—C9	−0.97 (19)	C9—C4—O1—C3	175.72 (12)
C11—C7—C8—C9	178.59 (12)	C2—C3—O1—C4	−69.00 (17)
C7—C8—C9—O2	−179.39 (11)	C8—C9—O2—C10	−0.92 (19)
C7—C8—C9—C4	0.55 (18)	C4—C9—O2—C10	179.13 (12)
O1—C4—C9—O2	−0.11 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O2ⁱ	0.97	2.42	3.374 (2)	166
C1—H1···O3ⁱⁱ	0.93	2.39	3.274 (2)	158

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

Acknowledgements

TE is grateful to the University of Madras, Chennai, for financial support (URF). The authors thank the SAIF, IIM, Chennai, India, for recording the single-crystal X-ray data, and V. Maheshwaran, Department of Crystallography and Biophysics, University of Madras, for solving the crystal structure.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Bruker. (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fitzgerald, D. J., Stratford, M., Gasson, M. J. & Narbod, A. (2005). J. Agric. Food Chem. 53, 1769–1775. CrossRef CAS Google Scholar
Hocking, M. B. (1997). J. Chem. Educ. 74, 1055–1059. CrossRef CAS Google Scholar
Kamal, A., Prabhakar, S., Janaki Ramaiah, M., Venkat Reddy, P., Ratna Reddy, Ch., Mallareddy, A., Shankaraiah, N., Lakshmi Narayan Reddy, T., Pushpavalli, S. N. & Pal-Bhadra, M. (2011). Eur. J. Med. Chem. 46, 3820–3831. CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Walton, N. J., Mayer, M. J. & Narbad, A. (2003). Phytochemistry, 63, 505–515. Web of Science CrossRef PubMed CAS Google Scholar
Wang, S., Wang, Q., Wang, Y., Liu, L., Weng, X., Zhang, G. L. X. & Zhou, X. (2008). Bioorg. Med. Chem. Lett. 18, 6505–6510. CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.