organic papers
o282
Odabas¸og˘lu and Bu¨yu¨kgu¨ngo¨r C12H16O2 doi:10.1107/S1600536805041887 Acta Cryst.(2006). E62, o282–o283 Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
3-
tert
-Butyl-2-hydroxy-5-methylbenzaldehyde:
a redetermination
Mustafa Odabas¸og˘lua* and Orhan Bu¨yu¨kgu¨ngo¨rb
a
Department of Chemistry, Faculty of Arts & Science, Ondokuz Mayıs University, TR-55139 Kurupelit Samsun, Turkey, andbDepartment of
Physics, Ondokuz Mayıs University, TR-55139 Kurupelit Samsun, Turkey
Correspondence e-mail: muodabas@omu.edu.tr
Key indicators
Single-crystal X-ray study T= 100 K
Mean(C–C) = 0.002 A˚ Rfactor = 0.039 wRfactor = 0.109
Data-to-parameter ratio = 12.0
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2006 International Union of Crystallography Printed in Great Britain – all rights reserved
In the molecule of the title compound, C12H16O2, all atoms
except one methyl group and two H atoms are located on a crystallographic mirror plane; thus the molecule is essentially
planar. An intramolecular O—H O hydrogen bond and
weak C—H O intermolecular hydrogen bonds stabilize the
packing. The structure has been previously reported in the non-centrosymmetric space group P21; our study shows that
the correct space group isP21/m.
Comment
Hydroxy-substituted benzaldehyde reagents used for
condensation with primary amines, hydrazines, hydroxylamine and other primary amine derivatives afford imine derivatives which can function as ligands towards a number of metal cations (Loudon, 2002; Khandar & Nejati, 2000; Khandar & Rezvani, 1999).
The structure of (I) has been previously reported
[Cambridge Structural Database (Version 5.26; Allen, 2002)
refcode ZOJRAR (Matilainen et al., 1996)]; however, the
choice of the space group P21 appears to be wrong and the
correct space group isP21/m. All atoms except for one methyl
group and two H atoms are located on a crystallographic mirror plane; thus the molecule except for one methyl group is essentially planar (Fig. 1). A significant intramolecular inter-action is noted, involving phenol atom H1 and carbonyl atom O2, such that a six-membered ring is formed (Table 1 and Fig. 1). The aromatic ring C—C bond distances in (I) agree with those observed in
bis(3-formyl-4-hydroxy-5-methoxyphen-yl)methane (Odabas¸og˘lu et al., 2006). The C7—O1 bond
distance in (I) is also consistent with the value of the C O double bond in carbonyl compounds (Loudon, 2002).
Experimental
A mixture of 2-tert-butyl-4-methylphenol (0.1 mol) and CHCl3
(0.4 mol) and NaOH (0.8 mol) in ethyl alcohol was stirred at reflux temperature for 2 h. 20% H2SO4solution (50 ml) was added to this
reaction mixture and the crude product was purified with a neutral alumina column. Well shaped crystals of (I) were obtained by slow evaporation of an ethyl alcohol solution (yield 0.96 g, 5%, m.p. 345 K).
Crystal data
C12H16O2 Mr= 192.25 Monoclinic,P21=m a= 8.3633 (8) A˚
b= 6.6200 (6) A˚
c= 9.7328 (11) A˚ = 97.170 (9)
V= 534.64 (9) A˚3 Z= 2
Dx= 1.194 Mg m3
MoKradiation Cell parameters from 5006
reflections = 3.0–28.8 = 0.08 mm1 T= 100 K Prism, yellow 0.770.500.20 mm
Data collection
Stoe IPDS-II diffractometer ’scans
5006 measured reflections 1136 independent reflections 1037 reflections withI> 2(I)
Rint= 0.029
max= 26.0
h=10!10
k=8!8
l=12!12
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.039 wR(F2) = 0.109 S= 1.07 1136 reflections 95 parameters
H atoms treated by a mixture of independent and constrained refinement
w= 1/[2(F
o2) + (0.0624P)2
+ 0.1473P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.30 e A˚
3 min=0.21 e A˚
3
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
O2—H2 O1 0.85 (1) 1.80 (1) 2.5954 (16) 155 (2)
C4—H4 O1i
0.93 2.49 3.3717 (18) 159
Symmetry code: (i)x1;yþ1 2;z.
All H atoms were located in a Fourier difference map, but the H atoms of the aromatic ring and the C9 methyl group were then placed in calculated positions and refined as riding, with C—H distances in the range 0.93 (2)–0.96 (2) A˚ andUiso(H) = 1.5Ueq(C) for methyl and
Uiso(H) = 1.2Ueq(C) for aromatic H atoms. The positions of the H
atoms on O2 (which takes part in a hydrogen bond) and on C10 and C11 were refined using C—H and O—H restraints of 0.96 (2) and 0.85 (2) A˚ , respectively, and withUiso(H) = 1.5Ueq(methyl C) and
Uiso(H) = 1.2Ueq(O).
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement:
X-AREA; data reduction:X-RED32(Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:ORTEP3 for Windows(Farrugia, 1997); software used to prepare material for publication:WinGX(Farrugia, 1999).
References
Allen, F. H. (2002).Acta Cryst.B58, 380–388. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837–838.
Khandar, A. A. & Nejati, K. (2000).Polyhedron,19, 607–613. Khandar, A. A. & Rezvani, Z. (1999).Polyhedron,18, 129–133.
Loudon, M. G. (2002).Organic Chemistry, , 4th ed., pp. 837, 874–880. Oxford University Press.
Matilainen, L., Klinga, M. & Leskela, M. (1996).J. Chem. Soc. Dalton Trans.
pp. 219–225.
Odabas¸og˘lu, M., Albayrak, C, & Bu¨yu¨kgu¨ngo¨r, O. (2006).Acta Cryst.E62, o239–o240.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.
[image:2.610.311.566.70.279.2]Stoe & Cie (2002).X-AREA(Version 1.18) andX-RED32(Version 1.04). Stoe & Cie, Darmstadt, Germany.
Figure 1
A view of (I), showing the atomic numbering scheme and the intramolecular hydrogen bond as a dashed line. Displacement ellipsoids are drawn at the 50% probability level.
Figure 2
[image:2.610.315.566.338.461.2]supporting information
sup-1
Acta Cryst. (2006). E62, o282–o283
supporting information
Acta Cryst. (2006). E62, o282–o283 [doi:10.1107/S1600536805041887]
3-
tert
-Butyl-2-hydroxy-5-methylbenzaldehyde: a redetermination
Mustafa Odaba
ş
o
ğ
lu and Orhan B
ü
y
ü
kg
ü
ng
ö
r
S1. Comment
Hydroxy-substituted benzaldehyde reagents used for condensation with primary amines, hydrazines, hydroxylamine and
other primary amine derivatives afford imine derivatives which can function as ligands towards a number of metal cations
(Loudon, 2002; Khandar & Nejati, 2000; Khandar & Rezvani, 1999).
The structure of (I) has been previously reported [Matilainen or Matlainen et al., 1996; Cambridge Structural Database
(Allen, 2002) refcode ZOJRAR]; however, the choice of the space group P21 appears to be wrong and the correct space
group is P21/m. All atoms except for one methyl and two H atoms are located in a crystallographic mirror plane thus the
molecule except for one methyl is perfectly planar (Fig. 1). A significant intramolecular interaction is noted, involving
phenol atom H1 and carbonyl atom O2, such that a six-membered ring is formed (Table 1 and Fig. 1). The aromatic ring
C—C bond distances in (I) agree with those observed in bis(3-formyl-4-hydroxy-5-methoxyphenyl)methane (Odabaşoğlu
et al., 2006). The C7—O1 bond distance in (I) is also consistent with the value of the C═O double bond in carbonyl
compounds (Loudon, 2002).
S2. Experimental
A mixture of 2-tert-butyl-4-methylphenol (0.1 mol) and CHCl3 (0.4 mol) and NaOH (0.8 mol) in ethyl alcohol was stirred
at reflux temperature for 2 h. The 50 ml 20% H2SO4 solution was added to this reaction mixture and crude product was
purified with neutral alumina column. Well shaped crystals of (I) were obtained by slow evaporation from ethyl alcohol
solution (yield 0.96 g, 5%, m.p. 345 K).
S3. Refinement
All H atoms were located at first in a Fourier difference map without any problem. However, because of the need to
reduce the number of free parameters, the H atoms of the aromatic ring and the C9 methyl group were place in calculated
positions and refined as riding, with C—H distances in the range 0.96 (2)–0.93 (2) Å and Uiso(H) = 1.5Ueq of the parent
atom for methyl and Uiso(H) = 1.2Ueq of the parent atom for aromatic H atoms. The H atoms on O2 (which takes part in a
hydrogen bond) and on C10 and C11 belonging to the mirror plane were located in a Fourier difference map and their
coordinates were refined using C—H and O—H restraints of 0.96 and 0.85 Å, respectively, and with Uiso(H) =
Figure 1
A view of (I), showing the atomic numbering scheme and the intramolecular hydrogen bond as a dashed line.
Displacement ellipsoids are drawn at the 50% probability level.
Figure 2
A packing diagram of (I), showing the hydrogen-bonding scheme (dashed lines).
3-tert-butyl-2-hydroxy-5-methylbenzaldehyde
Crystal data
C12H16O2
Mr = 192.25
Monoclinic, P21/m
Hall symbol: -P 2yb
a = 8.3633 (8) Å
[image:4.610.127.482.419.592.2]supporting information
sup-3
Acta Cryst. (2006). E62, o282–o283
c = 9.7328 (11) Å
β = 97.170 (9)°
V = 534.64 (9) Å3
Z = 2
F(000) = 208
Dx = 1.194 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 5006 reflections
θ = 3.0–28.8°
µ = 0.08 mm−1
T = 100 K
Prism, yellow
0.77 × 0.50 × 0.20 mm
Data collection
Stoe
diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
Detector resolution: 6.67 pixels mm-1
φ scan rotation method
5006 measured reflections
1136 independent reflections 1037 reflections with I > 2σ(I)
Rint = 0.029
θmax = 26.0°, θmin = 3.4°
h = −10→10
k = −8→8
l = −12→12
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.039
wR(F2) = 0.109
S = 1.07
1136 reflections 95 parameters 5 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.0624P)2 + 0.1473P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.30 e Å−3
Δρmin = −0.21 e Å−3
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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)
x y z Uiso*/Ueq
C1 0.55851 (17) 0.2500 0.48411 (16) 0.0178 (3)
C2 0.49028 (17) 0.2500 0.34480 (15) 0.0167 (3)
C3 0.32167 (17) 0.2500 0.31042 (15) 0.0162 (3)
C4 0.23035 (17) 0.2500 0.41980 (15) 0.0168 (3)
H4 0.1188 0.2500 0.3990 0.020*
C5 0.29523 (18) 0.2500 0.55985 (15) 0.0176 (3)
C6 0.46025 (18) 0.2500 0.58976 (15) 0.0176 (3)
H6 0.5070 0.2500 0.6816 0.021*
C7 0.73224 (18) 0.2500 0.51989 (17) 0.0218 (4)
C8 0.24411 (18) 0.2500 0.15894 (15) 0.0191 (4)
C9 0.29509 (14) 0.44005 (19) 0.08592 (11) 0.0279 (3)
H9A 0.2469 0.4391 −0.0089 0.042*
H9B 0.4103 0.4425 0.0895 0.042*
H9C 0.2600 0.5577 0.1315 0.042*
C10 0.0601 (2) 0.2500 0.14759 (17) 0.0276 (4)
H10A 0.017 (3) 0.2500 0.0513 (11) 0.041*
H10B 0.0202 (18) 0.1301 (18) 0.1902 (15) 0.041*
C11 0.1852 (2) 0.2500 0.67075 (17) 0.0250 (4)
H11A 0.243 (2) 0.2500 0.7616 (13) 0.037*
H11B 0.1125 (15) 0.1377 (18) 0.6625 (15) 0.037*
O1 0.83007 (13) 0.2500 0.43643 (13) 0.0277 (3)
O2 0.58647 (13) 0.2500 0.24303 (12) 0.0245 (3)
H2 0.6816 (14) 0.2500 0.2856 (19) 0.029*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.0160 (7) 0.0120 (6) 0.0249 (8) 0.000 0.0010 (6) 0.000
C2 0.0170 (7) 0.0141 (7) 0.0199 (7) 0.000 0.0064 (6) 0.000
C3 0.0174 (7) 0.0132 (7) 0.0178 (7) 0.000 0.0019 (5) 0.000
C4 0.0134 (7) 0.0160 (7) 0.0210 (7) 0.000 0.0025 (5) 0.000
C5 0.0200 (7) 0.0145 (7) 0.0190 (7) 0.000 0.0054 (6) 0.000
C6 0.0216 (8) 0.0141 (7) 0.0163 (7) 0.000 −0.0007 (6) 0.000
C7 0.0182 (8) 0.0169 (7) 0.0293 (8) 0.000 −0.0011 (6) 0.000
C8 0.0206 (7) 0.0199 (7) 0.0164 (7) 0.000 0.0012 (5) 0.000
C9 0.0354 (6) 0.0271 (7) 0.0204 (5) −0.0036 (5) −0.0005 (4) 0.0055 (4)
C10 0.0217 (8) 0.0379 (10) 0.0215 (8) 0.000 −0.0041 (6) 0.000
C11 0.0260 (8) 0.0300 (9) 0.0203 (8) 0.000 0.0085 (6) 0.000
O1 0.0145 (5) 0.0274 (6) 0.0414 (7) 0.000 0.0045 (5) 0.000
O2 0.0163 (5) 0.0344 (7) 0.0241 (6) 0.000 0.0079 (4) 0.000
Geometric parameters (Å, º)
C1—C6 1.394 (2) C7—H7 0.9300
C1—C2 1.404 (2) C8—C10 1.529 (2)
C1—C7 1.451 (2) C8—C9 1.5315 (14)
C2—O2 1.3517 (17) C8—C9i 1.5315 (14)
C2—C3 1.408 (2) C9—H9A 0.9600
C3—C4 1.385 (2) C9—H9B 0.9600
C3—C8 1.5348 (19) C9—H9C 0.9600
C4—C5 1.403 (2) C10—H10A 0.961 (10)
C4—H4 0.9300 C10—H10B 0.974 (9)
C5—C6 1.375 (2) C11—H11A 0.953 (10)
C5—C11 1.503 (2) C11—H11B 0.957 (9)
C6—H6 0.9300 O2—H2 0.850 (10)
supporting information
sup-5
Acta Cryst. (2006). E62, o282–o283
C6—C1—C2 120.43 (13) C1—C7—H7 117.5
C6—C1—C7 119.19 (14) C10—C8—C9 107.60 (9)
C2—C1—C7 120.39 (14) C10—C8—C9i 107.60 (9)
O2—C2—C1 120.02 (13) C9—C8—C9i 110.48 (13)
O2—C2—C3 119.72 (13) C10—C8—C3 111.73 (12)
C1—C2—C3 120.25 (13) C9—C8—C3 109.70 (8)
C4—C3—C2 116.69 (13) C9i—C8—C3 109.70 (8)
C4—C3—C8 122.06 (13) C8—C9—H9A 109.5
C2—C3—C8 121.26 (13) C8—C9—H9B 109.5
C3—C4—C5 124.28 (13) H9A—C9—H9B 109.5
C3—C4—H4 117.9 C8—C9—H9C 109.5
C5—C4—H4 117.9 H9A—C9—H9C 109.5
C6—C5—C4 117.52 (13) H9B—C9—H9C 109.5
C6—C5—C11 122.45 (14) C8—C10—H10A 109.0 (13)
C4—C5—C11 120.03 (13) C8—C10—H10B 111.4 (9)
C5—C6—C1 120.83 (13) H10A—C10—H10B 107.9 (12)
C5—C6—H6 119.6 C5—C11—H11A 112.4 (13)
C1—C6—H6 119.6 C5—C11—H11B 112.2 (9)
O1—C7—C1 124.99 (15) H11A—C11—H11B 108.7 (11)
O1—C7—H7 117.5 C2—O2—H2 104.4 (14)
Symmetry code: (i) x, −y+1/2, z.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O2—H2···O1 0.85 (1) 1.80 (1) 2.5954 (16) 155 (2)
C4—H4···O1ii 0.93 2.49 3.3717 (18) 159