2-Hy­droxy-3-meth­oxy­benzaldehyde (o-vanillin) revisited

Shin, D.; Müller, P.

doi:10.1107/S1600536812029571

Volume 68
Part 8
Pages o2336-o2337
August 2012

Received 12 June 2012
Accepted 28 June 2012
Online 4 July 2012

Key indicators
Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R = 0.034
wR = 0.095
Data-to-parameter ratio = 11.6
Details

2-Hydroxy-3-methoxybenzaldehyde (o-vanillin) revisited

David Shin ^a and Peter Müller ^b ^*

^aPhillips Academy, 180 Main St, Andover, MA 01810, USA, and ^bX-Ray Diffraction Facility, MIT Department of Chemistry, 77 Massachusetts Avenue, Building 2, Room 325, Cambridge, MA 02139-4307, USA
Correspondence e-mail: pmueller@mit.edu

The structure of ortho-vanillin, C₈H₈O₃, has been revisited with modern methods and at low temperature (100 K). The previous structure [Iwasaki et al. (1976). Acta Cryst. B32, 1264-1266] is confirmed, but geometric precision is improved by an order of magnitude. The C atom of the methoxy group lies close to the benzene ring plane, which is the most common geometry for -OMe groups lying ortho to -OH groups on an aromatic ring. The crystal structure displays one intramolecular O-HO and three weak intermolecular C-HO hydrogen bonds.

Related literature

For the original structure of o-vanillin, see: Iwasaki et al. (1976). For C-Hacceptor interactions, see: Steiner (1996). For a summary of general refinement techniques applied, see: Müller (2009). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental

Crystal data

C₈H₈O₃
M_r = 152.14
Orthorhombic, F d d 2
a = 24.367 (5) Å
b = 24.407 (3) Å
c = 4.7786 (5) Å
V = 2842.0 (7) Å³
Z = 16
Mo K radiation
= 0.11 mm^-1
T = 100 K
0.45 × 0.20 × 0.06 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2009) T_min = 0.709, T_max = 1.000
21987 measured reflections
1203 independent reflections
1153 reflections with I > 2(I)
R_int = 0.053

Refinement

R[F² > 2(F²)] = 0.034
wR(F²) = 0.095
S = 1.11
1203 reflections
104 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 0.32 e Å^-3
_min = -0.21 e Å^-3

Table 1
Selected torsion angles (°)

C8-O3-C3-C4	7.5 (2)
C8-O3-C3-C2	-172.98 (13)

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
O2-H2O1	0.85 (2)	1.84 (2)	2.6017 (17)	148 (2)
C8-H8BO1ⁱ	0.98	2.56	3.064 (2)	112
C6-H6O3ⁱⁱ	0.95	2.53	3.374 (2)	149
C7-H7O3ⁱⁱ	0.95	2.59	3.414 (2)	146
Symmetry codes: (i) $[-x+{\script{3\over 4}}, y+{\script{1\over 4}}, z-{\script{5\over 4}}]$ ; (ii) $[x+{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

Table 3
Comparison (Å) between the room and low temperature structures of o-vanillin

parameter	room tempreature	low temperature (this study)
R1[I>2(I)]	0.077	0.034
C1-C7	1.427	1.452 (2)
O1-C7	1.229	1.233 (2)
O2-C2	1.354	1.3535 (17)
O3-C3	1.364	1.3689 (16)
O3-C8	1.430	1.434 (2)

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTLand PLATON (Spek, 2009).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB6851 ).

Acknowledgements

The diffractometer was purchased with the help of funding from the National Science Foundation (NSF) under grant No. CHE-0946721. DS and PM would like to thank Jeff Simpson for kindly providing the o-vanillin crystals.

References

Allen, F. H. (2002). Acta Cryst. B58, 380-388.
Bruker (2011). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Iwasaki, F., Tanaka, I. & Aihara, A. (1976). Acta Cryst. B32, 1264-1266.
Müller, P. (2009). Crystallogr. Rev. 15, 57-83.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Sheldrick, G. M. (2009). SADABS. University of Göttingen, Germany.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.
Steiner, Th. (1996). Crystallogr. Rev. 6, 1-57.

organic compounds