3,4-Di­meth­oxy­benzaldehyde

Ronde, E. de; Brugman, S.J.T.; Koning, N.; Tinnemans, P.; Vlieg, E.

doi:10.1107/S2414314616010087

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161008

https://doi.org/10.1107/S2414314616010087

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3,4-Dimethoxybenzaldehyde

Erik de Ronde,^a Sander J.T. Brugman,^a Niels Koning,^a Paul Tinnemans ^a ^* and Elias Vlieg ^a

^aRadboud University, Institute for Molecules and Materials, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands
^*Correspondence e-mail: p.tinnemans@science.ru.nl

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 15 June 2016; accepted 21 June 2016; online 2 July 2016)

In the title compound, C₉H₁₀O₃, one of the methoxy C atoms deviates from the plane of the aromatic ring by 0.337 (2) Å. Crystallization was hindered by oiling out in various solvents. The crystal contains neither hydrogen bonds nor aromatic π–π stacking.

Keywords: crystal structure; vanillin derivative; oiling out.

CCDC reference: 1486850

Structure description

The title compound, shown in Fig. 1, has a strong vanilla fragrance. It crystallizes in the orthorhombic space group Pna2₁. Differential scanning calorimetry measurements were performed to screen for polymorphic transitions, but none were observed between 150 K and the melting point of the title compound, 319 K (not shown).

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.

The compound oils out in water and several organic solvents. Similar behaviour has been observed for the closely related molecule vanillin (Svärd et al., 2007 ). For the crystal structure of vanillin-I, see: Velavan et al. (1995 ).

In the crystal, no hydrogen bonds are present.

Synthesis and crystallization

Commercial 3,4-dimethoxybenzaldehyde (99% pure, Aldrich) was used for the crystallization. A few crystals of the commercial powder were added to an aqueous saturated solution of 3,4-dimethoxybenzaldehyde at room temperature. Subsequently, the temperature was cycled between 298 and 303 K. After 2 weeks colourless needles were grown, suitable for single-crystal X-ray diffraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₉H₁₀O₃
M_r	166.17
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	150
a, b, c (Å)	11.374 (2), 14.363 (3), 5.050 (2)
V (Å³)	825.0 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Colour	Colourless
Crystal size (mm)	0.35 × 0.15 × 0.13

Data collection
Diffractometer	Bruker D8 Quest APEX3
Absorption correction	Multi-scan (SADABS; Bruker, 2001 )
T_min, T_max	0.90, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	34976, 2608, 2237
R_int	0.050

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.097, 1.03
No. of reflections	2608
No. of parameters	111
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.19
Absolute structure	Flack x determined using 930 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.2 (3)
Computer programs: APEX3 and SAINT (Bruker, 2012 ), PEAKREF (Schreurs, 2013 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and ShelXLe (Sheldrick, 2015a).

Structural data

CCDC reference: 1486850

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616010087/hb4058sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616010087/hb4058Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616010087/hb4058Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S2414314616010087/hb4058Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2012); cell refinement: PEAKREF (Schreurs, 2013); data reduction: SAINT (Bruker, 2012) and SADABS (Bruker, 2001); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009) and ShelXLe (Sheldrick, 2015a).

3,4-Dimethoxybenzaldehyde top

Crystal data top

C₉H₁₀O₃	D_x = 1.338 Mg m⁻³
M_r = 166.17	Melting point: 319 K
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
a = 11.374 (2) Å	Cell parameters from 2237 reflections
b = 14.363 (3) Å	θ = 2.2–30°
c = 5.050 (2) Å	µ = 0.10 mm⁻¹
V = 825.0 (4) Å³	T = 150 K
Z = 4	Needle, colourless
F(000) = 352	0.35 × 0.15 × 0.13 mm

Data collection top

Bruker D8 Quest APEX3 diffractometer	2608 independent reflections
Radiation source: sealed tube	2237 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 10.4 pixels mm^-1	θ_max = 31.0°, θ_min = 2.3°
φ and ω scans	h = −16→15
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −20→20
T_min = 0.90, T_max = 0.99	l = −7→7
34976 measured reflections

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) = 0.097	w = 1/[σ²(F_o²) + (0.0572P)² + 0.1158P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2608 reflections	Δρ_max = 0.34 e Å⁻³
111 parameters	Δρ_min = −0.19 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 930 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.2 (3)

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
O01	0.62471 (10)	0.74604 (8)	0.1630 (3)	0.0242 (3)
O02	0.51301 (9)	0.63612 (8)	0.4799 (3)	0.0244 (3)
O03	0.84277 (11)	0.46485 (8)	1.0130 (3)	0.0286 (3)
C04	0.63269 (12)	0.63367 (10)	0.5011 (4)	0.0177 (3)
C05	0.69492 (12)	0.57807 (10)	0.6762 (4)	0.0182 (3)
H05	0.6543	0.5369	0.7914	0.022*
C06	0.69401 (13)	0.69467 (10)	0.3273 (4)	0.0179 (3)
C07	0.81632 (13)	0.69977 (10)	0.3360 (4)	0.0200 (3)
H07	0.8574	0.7408	0.2212	0.024*
C08	0.88522 (14)	0.52368 (11)	0.8669 (4)	0.0219 (3)
H08	0.9681	0.5319	0.8726	0.026*
C09	0.87817 (13)	0.64383 (10)	0.5155 (4)	0.0198 (3)
H09	0.9615	0.6475	0.5233	0.024*
C10	0.81847 (12)	0.58287 (11)	0.6827 (4)	0.0181 (3)
C11	0.44789 (14)	0.59171 (13)	0.6874 (4)	0.0263 (3)
H11A	0.4698	0.6191	0.8582	0.040*
H11B	0.4658	0.5250	0.6888	0.040*
H11C	0.3635	0.6007	0.6572	0.040*
C12	0.68316 (17)	0.80898 (11)	−0.0137 (4)	0.0281 (4)
H12A	0.6248	0.8402	−0.1256	0.042*
H12B	0.7382	0.7742	−0.1254	0.042*
H12C	0.7264	0.8556	0.0893	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O01	0.0249 (6)	0.0236 (5)	0.0242 (6)	0.0029 (4)	−0.0010 (5)	0.0068 (5)
O02	0.0146 (5)	0.0269 (5)	0.0318 (6)	0.0019 (4)	−0.0009 (5)	0.0074 (5)
O03	0.0247 (6)	0.0284 (6)	0.0328 (7)	0.0016 (5)	−0.0036 (6)	0.0090 (6)
C04	0.0151 (6)	0.0163 (6)	0.0217 (7)	0.0005 (5)	−0.0003 (7)	−0.0014 (6)
C05	0.0170 (6)	0.0161 (6)	0.0215 (7)	−0.0003 (5)	0.0000 (7)	0.0020 (6)
C06	0.0214 (7)	0.0157 (6)	0.0166 (6)	0.0012 (5)	−0.0013 (6)	−0.0006 (6)
C07	0.0215 (7)	0.0192 (7)	0.0193 (7)	−0.0016 (6)	0.0031 (7)	0.0001 (6)
C08	0.0165 (7)	0.0239 (7)	0.0254 (8)	0.0014 (6)	−0.0036 (6)	0.0006 (7)
C09	0.0155 (6)	0.0219 (7)	0.0222 (8)	−0.0014 (5)	0.0001 (6)	−0.0016 (6)
C10	0.0166 (6)	0.0182 (6)	0.0194 (7)	0.0016 (5)	−0.0013 (7)	−0.0022 (6)
C11	0.0153 (6)	0.0316 (8)	0.0321 (8)	−0.0009 (6)	0.0032 (7)	0.0016 (7)
C12	0.0385 (9)	0.0213 (7)	0.0244 (8)	0.0026 (6)	0.0012 (8)	0.0075 (7)

Geometric parameters (Å, º) top

O01—C06	1.361 (2)	C07—H07	0.9500
O01—C12	1.434 (2)	C08—C10	1.471 (2)
O02—C04	1.3659 (17)	C08—H08	0.9500
O02—C11	1.433 (2)	C09—C10	1.393 (2)
O03—C08	1.221 (2)	C09—H09	0.9500
C04—C05	1.386 (2)	C11—H11A	0.9800
C04—C06	1.423 (2)	C11—H11B	0.9800
C05—C10	1.4073 (19)	C11—H11C	0.9800
C05—H05	0.9500	C12—H12A	0.9800
C06—C07	1.394 (2)	C12—H12B	0.9800
C07—C09	1.401 (3)	C12—H12C	0.9800

C06—O01—C12	116.90 (14)	C10—C09—H09	119.7
C04—O02—C11	116.51 (14)	C07—C09—H09	119.7
O02—C04—C05	125.02 (15)	C09—C10—C05	120.23 (15)
O02—C04—C06	115.10 (14)	C09—C10—C08	119.66 (13)
C05—C04—C06	119.88 (12)	C05—C10—C08	120.11 (15)
C04—C05—C10	119.78 (14)	O02—C11—H11A	109.5
C04—C05—H05	120.1	O02—C11—H11B	109.5
C10—C05—H05	120.1	H11A—C11—H11B	109.5
O01—C06—C07	124.66 (14)	O02—C11—H11C	109.5
O01—C06—C04	115.20 (13)	H11A—C11—H11C	109.5
C07—C06—C04	120.12 (14)	H11B—C11—H11C	109.5
C06—C07—C09	119.45 (15)	O01—C12—H12A	109.5
C06—C07—H07	120.3	O01—C12—H12B	109.5
C09—C07—H07	120.3	H12A—C12—H12B	109.5
O03—C08—C10	125.30 (15)	O01—C12—H12C	109.5
O03—C08—H08	117.4	H12A—C12—H12C	109.5
C10—C08—H08	117.4	H12B—C12—H12C	109.5
C10—C09—C07	120.53 (14)

C11—O02—C04—C05	12.6 (2)	O01—C06—C07—C09	179.45 (17)
C11—O02—C04—C06	−166.89 (15)	C04—C06—C07—C09	0.6 (2)
O02—C04—C05—C10	−178.91 (16)	C06—C07—C09—C10	0.6 (2)
C06—C04—C05—C10	0.6 (2)	C07—C09—C10—C05	−1.1 (2)
C12—O01—C06—C07	0.5 (2)	C07—C09—C10—C08	179.07 (15)
C12—O01—C06—C04	179.47 (14)	C04—C05—C10—C09	0.6 (2)
O02—C04—C06—O01	−0.6 (2)	C04—C05—C10—C08	−179.65 (16)
C05—C04—C06—O01	179.87 (14)	O03—C08—C10—C09	−176.38 (16)
O02—C04—C06—C07	178.39 (14)	O03—C08—C10—C05	3.8 (3)
C05—C04—C06—C07	−1.1 (2)

References

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