4-Eth­oxy-3-meth­oxy­benzaldehyde

Leka, Z.; Novaković, S.B.; Bogdanović, G.A.; Muškinja, J.; Vukićević, R.D.

doi:10.1107/S160053681302761X

organic compounds

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ISSN: 2056-9890

Volume 69| Part 12| December 2013| Page o1728

doi:10.1107/S160053681302761X

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4-Ethoxy-3-methoxybenzaldehyde

Zorica Leka,^a ^* Sladjana B. Novaković,^b Goran A. Bogdanović,^b Jovana Muškinja ^c and Rastko D. Vukićević ^c

^aFaculty of Metallurgy and Technology, University of Montenegro, Cetinjski put bb, 81000 Podgorica, Montenegro, ^bVinča Institute of Nuclear Sciences, Laboratory of Theoretical Physics and Condensed Matter Physics, PO Box 522, University of Belgrade, 11001 Belgrade, Serbia, and ^cFaculty of Sciences, Department of Chemistry, University of Kragujevac, R. Domanovića 12, 34000 Kragujevac, Serbia
^*Correspondence e-mail: zorica@ac.me

(Received 4 October 2013; accepted 9 October 2013; online 6 November 2013)

In the title compound, C₁₀H₁₂O₃, all non-H atoms are approximately coplanar, with an r.m.s. deviation of 0.046 Å. In the crystal, very weak C—H⋯O interactions link the molecules into sheets parallel to (101).

CCDC reference: 965471

Related literature

For the bioactivity of dehydrozingerone derivatives and their role in the synthesis of heterocycles, see: Tatsuzaki et al. (2006 ); Kubra et al. (2013 ); Panda & Chowdary (2008 ); Mostahar et al. (2007 ). For related crystal structures, see: Matos Beja et al. (1997 ); Velavan et al. (1995 ).

Experimental

Crystal data

C₁₀H₁₂O₃
M_r = 180.20
Monoclinic, P 2₁ /c
a = 11.5314 (16) Å
b = 8.7905 (11) Å
c = 9.3363 (13) Å
β = 97.339 (14)°
V = 938.6 (2) Å³
Z = 4
Cu Kα radiation
μ = 0.78 mm⁻¹
T = 293 K
0.39 × 0.17 × 0.14 mm

Data collection

Agilent Gemini S diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ) T_min = 0.933, T_max = 1.000
6035 measured reflections
1848 independent reflections
1299 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.148
S = 1.04
1848 reflections
120 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.93	2.67	3.547 (3)	157
C10—H10B⋯O2ⁱⁱ	0.96	2.62	3.525 (2)	156
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 2012), PLATON (Spek, 2009 ) and PARST (Nardelli, 1995 ).

Supporting information

CCDC reference: 965471

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681302761X/zq2209sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681302761X/zq2209Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681302761X/zq2209Isup3.cml

checkCIF report

Comment top

Dehydrozingerone derivatives belong to an important class of compounds, not only due to their different bioactivities (Tatsuzaki et al., 2006; Kubra et al., 2013), but also as the key substrates in synthesis of some heterocycles (Panda et al., 2008), particularly flavones (Mostahar et al., 2007). They can be synthesized by condensation of the corresponding aromatic aldehyde with acetone. Thus, starting substrate in synthesis of ethyl derivative of dehydrozingerone is 4-ethoxy-3-methoxybenzaldehyde (I), compound obtained by simple methylation of vanillin.

In the title structure, all non-hydrogen atoms are approximately coplanar with a mean deviation of 0.046 Å (Fig. 1). A somewhat higher displacement of 0.102 (2) Å has been observed for atom C9 belonging to ethoxy moiety. The dihedral angle between the best planes through the phenyl ring and the non-H atoms of ethoxy moiety is 8.1 (1)°. The aromatic C—C bond lengths are in the expected range of 1.368 (2)–1.411 (2) Å (Table 2). The five C—O bonds have various lengths. The shortest length is found for the carbonyl C1—O1 = 1.204 (2) bond in accordance with the prevaling double bond character.

The crystal structure exhibits no conventional hydrogen bonding. The molecules are held together by weak C–H···O and van der Waals interactions. The two C—H···O intermolecular contacts shorter than the sum of the van der Waals radii [C1—H1 = 0.93; H1···O1= 2.67 Å; C1—H1···O1ⁱ = 157.3° and C10—H10B = 0.96, H10B···O2 = 2.62 Å, C10—H10B···O2ⁱⁱ = 156.4° (symmetry codes: i = -x,+y - 1/2,-z + 3/2; ii = -x + 1,+y - 1/2,-z + 1/2)] connect the molecules into a sheet parallel to (101). These sheets further connect into three-dimensional structure by C—H···π interaction [C10—H10c = 0.96, H10c···Cg1 = 3.00 Å C10—H10c···Cg1ⁱⁱⁱ = 147° [(symmetry code: iii = -x + 1,-y,-z + 1)] (Fig. 2). The approximate distance between the adjacent parallel sheets is 3.5 Å. For related crystal structures, see Matos Beja et al. (1997) and Velavan et al. (1995).

Related literature top

For the bioactivity of dehydrozingerone derivatives and their role in the synthesis of heterocycles, see: Tatsuzaki et al. (2006); Kubra et al. (2013); Panda et al. (2008); Mostahar et al. (2007). For related crystal structures, see: Matos Beja et al. (1997); Velavan et al. (1995).

Experimental top

Diethyl sulfate was dropped into a water solution of sodium hydroxide and vanillin. The reaction mixture was stirred overnight at 50°C and cooled at room temperature resulting firstly an oily product, which on standing gave crude crystal 4-ethoxy-3-methoxybenzaldehyde.

One gram of crude 4-ethoxy-3-methoxybenzaldehyde was stirred vigorously in 150 ml of boiling water, the hot mixture filtered of through a cotton pad. The obtained milky-white emulsion upon overnight cooling at room temperature gave crystal needles of 4-ethoxy-3-methoxybenzaldehyde.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Three-dimensional layered structure of the title compound. All H atoms which are not involved in intermolecular interactions are omitted for clarity.

4-Ethoxy-3-methoxybenzaldehyde top

Crystal data top

C₁₀H₁₂O₃	F(000) = 384
M_r = 180.20	D_x = 1.275 Mg m⁻³
Monoclinic, P2₁/c	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ybc	Cell parameters from 1676 reflections
a = 11.5314 (16) Å	θ = 3.9–71.1°
b = 8.7905 (11) Å	µ = 0.78 mm⁻¹
c = 9.3363 (13) Å	T = 293 K
β = 97.339 (14)°	Needle, white
V = 938.6 (2) Å³	0.39 × 0.17 × 0.14 mm
Z = 4

Data collection top

Agilent Gemini S diffractometer	1848 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1299 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 16.3280 pixels mm^-1	θ_max = 73.2°, θ_min = 3.9°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −10→8
T_min = 0.933, T_max = 1.000	l = −11→9
6035 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0746P)² + 0.0716P] where P = (F_o² + 2F_c²)/3
1848 reflections	(Δ/σ)_max < 0.001
120 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₀H₁₂O₃	V = 938.6 (2) Å³
M_r = 180.20	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 11.5314 (16) Å	µ = 0.78 mm⁻¹
b = 8.7905 (11) Å	T = 293 K
c = 9.3363 (13) Å	0.39 × 0.17 × 0.14 mm
β = 97.339 (14)°

Data collection top

Agilent Gemini S diffractometer	1848 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	1299 reflections with I > 2σ(I)
T_min = 0.933, T_max = 1.000	R_int = 0.021
6035 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 1.04	Δρ_max = 0.12 e Å⁻³
1848 reflections	Δρ_min = −0.17 e Å⁻³
120 parameters

Special details top

Experimental. Absorption correction: empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm (CrysAlis PRO; Agilent, 2013)

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

	x	y	z	U_iso*/U_eq
O1	−0.01326 (13)	−0.00997 (18)	0.78722 (16)	0.0954 (5)
O2	0.27667 (11)	0.22381 (13)	0.46226 (14)	0.0818 (4)
O3	0.37383 (11)	−0.00811 (13)	0.35924 (13)	0.0780 (4)
C1	0.03443 (17)	−0.1075 (2)	0.7257 (2)	0.0824 (5)
H1	0.0130	−0.2076	0.7411	0.099*
C2	0.12260 (15)	−0.0833 (2)	0.62934 (18)	0.0683 (5)
C3	0.15663 (15)	0.0635 (2)	0.59500 (18)	0.0675 (5)
H3	0.1230	0.1470	0.6348	0.081*
C4	0.23881 (14)	0.08576 (18)	0.50352 (17)	0.0642 (4)
C5	0.29161 (15)	−0.0414 (2)	0.44602 (18)	0.0665 (5)
C6	0.25783 (15)	−0.1856 (2)	0.47925 (19)	0.0768 (5)
H6	0.2918	−0.2696	0.4406	0.092*
C7	0.17310 (17)	−0.2063 (2)	0.5703 (2)	0.0793 (6)
H7	0.1502	−0.3043	0.5917	0.095*
C8	0.22711 (16)	0.3550 (2)	0.5194 (2)	0.0889 (6)
H8A	0.1438	0.3535	0.4938	0.133*
H8B	0.2588	0.4447	0.4804	0.133*
H8C	0.2453	0.3554	0.6227	0.133*
C9	0.43966 (16)	−0.1315 (2)	0.3099 (2)	0.0812 (6)
H9A	0.3872	−0.2051	0.2583	0.097*
H9B	0.4838	−0.1823	0.3916	0.097*
C10	0.52047 (17)	−0.0694 (3)	0.2129 (2)	0.0930 (7)
H10A	0.4761	−0.0211	0.1314	0.140*
H10B	0.5659	−0.1507	0.1799	0.140*
H10C	0.5717	0.0037	0.2645	0.140*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0975 (10)	0.0929 (10)	0.1040 (11)	−0.0069 (8)	0.0448 (9)	−0.0036 (8)
O2	0.0900 (8)	0.0605 (7)	0.1034 (9)	0.0055 (6)	0.0452 (7)	0.0059 (6)
O3	0.0846 (8)	0.0715 (8)	0.0838 (8)	0.0123 (6)	0.0332 (7)	0.0019 (6)
C1	0.0844 (12)	0.0782 (12)	0.0887 (13)	−0.0103 (10)	0.0265 (10)	0.0006 (10)
C2	0.0694 (10)	0.0658 (11)	0.0714 (10)	−0.0022 (8)	0.0152 (8)	0.0024 (8)
C3	0.0679 (10)	0.0652 (10)	0.0715 (10)	0.0047 (8)	0.0170 (8)	−0.0022 (8)
C4	0.0661 (9)	0.0578 (10)	0.0706 (10)	0.0041 (7)	0.0162 (8)	0.0045 (7)
C5	0.0675 (9)	0.0694 (11)	0.0643 (9)	0.0050 (8)	0.0153 (8)	0.0017 (8)
C6	0.0872 (12)	0.0633 (11)	0.0834 (12)	0.0063 (9)	0.0239 (10)	−0.0036 (9)
C7	0.0920 (13)	0.0600 (11)	0.0887 (12)	−0.0049 (9)	0.0224 (10)	0.0028 (9)
C8	0.0965 (14)	0.0606 (11)	0.1171 (16)	0.0027 (9)	0.0431 (12)	−0.0010 (10)
C9	0.0803 (12)	0.0827 (12)	0.0839 (12)	0.0139 (10)	0.0235 (10)	−0.0118 (10)
C10	0.0837 (13)	0.1090 (17)	0.0911 (14)	0.0149 (11)	0.0294 (11)	−0.0087 (12)

Geometric parameters (Å, º) top

O1—C1	1.204 (2)	C6—C7	1.387 (2)
O2—C4	1.3618 (18)	C6—H6	0.9300
O2—C8	1.421 (2)	C7—H7	0.9300
O3—C5	1.355 (2)	C8—H8A	0.9600
O3—C9	1.433 (2)	C8—H8B	0.9600
C1—C2	1.457 (2)	C8—H8C	0.9600
C1—H1	0.9300	C9—C10	1.484 (3)
C2—C7	1.376 (2)	C9—H9A	0.9700
C2—C3	1.398 (2)	C9—H9B	0.9700
C3—C4	1.368 (2)	C10—H10A	0.9600
C3—H3	0.9300	C10—H10B	0.9600
C4—C5	1.411 (2)	C10—H10C	0.9600
C5—C6	1.374 (2)

C4—O2—C8	117.27 (13)	C2—C7—H7	119.7
C5—O3—C9	117.93 (14)	C6—C7—H7	119.7
O1—C1—C2	126.0 (2)	O2—C8—H8A	109.5
O1—C1—H1	117.0	O2—C8—H8B	109.5
C2—C1—H1	117.0	H8A—C8—H8B	109.5
C7—C2—C3	119.20 (16)	O2—C8—H8C	109.5
C7—C2—C1	119.78 (17)	H8A—C8—H8C	109.5
C3—C2—C1	121.02 (17)	H8B—C8—H8C	109.5
C4—C3—C2	120.83 (16)	O3—C9—C10	108.51 (16)
C4—C3—H3	119.6	O3—C9—H9A	110.0
C2—C3—H3	119.6	C10—C9—H9A	110.0
O2—C4—C3	125.22 (15)	O3—C9—H9B	110.0
O2—C4—C5	115.38 (14)	C10—C9—H9B	110.0
C3—C4—C5	119.40 (15)	H9A—C9—H9B	108.4
O3—C5—C6	125.06 (16)	C9—C10—H10A	109.5
O3—C5—C4	115.17 (15)	C9—C10—H10B	109.5
C6—C5—C4	119.77 (16)	H10A—C10—H10B	109.5
C5—C6—C7	120.13 (17)	C9—C10—H10C	109.5
C5—C6—H6	119.9	H10A—C10—H10C	109.5
C7—C6—H6	119.9	H10B—C10—H10C	109.5
C2—C7—C6	120.65 (17)

O1—C1—C2—C7	177.57 (19)	O2—C4—C5—O3	0.8 (2)
O1—C1—C2—C3	−2.7 (3)	C3—C4—C5—O3	−178.53 (14)
C7—C2—C3—C4	0.2 (3)	O2—C4—C5—C6	−178.87 (16)
C1—C2—C3—C4	−179.46 (15)	C3—C4—C5—C6	1.7 (3)
C8—O2—C4—C3	0.3 (3)	O3—C5—C6—C7	179.56 (16)
C8—O2—C4—C5	−179.05 (16)	C4—C5—C6—C7	−0.8 (3)
C2—C3—C4—O2	179.20 (15)	C3—C2—C7—C6	0.8 (3)
C2—C3—C4—C5	−1.5 (3)	C1—C2—C7—C6	−179.51 (17)
C9—O3—C5—C6	−6.9 (3)	C5—C6—C7—C2	−0.5 (3)
C9—O3—C5—C4	173.41 (14)	C5—O3—C9—C10	177.85 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.67	3.547 (3)	157
C10—H10B···O2ⁱⁱ	0.96	2.62	3.525 (2)	156

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x+1, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.67	3.547 (3)	157.3
C10—H10B···O2ⁱⁱ	0.96	2.62	3.525 (2)	156.4

Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) −x+1, y−1/2, −z+1/2.

Acknowledgements

This work was supported by the Ministry of Education, Science and Technological development of the Republic of Serbia (projects No. 172014, 172035 and 172034).

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