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3 tert Butyl 2 hydr­­oxy 5 methyl­benzaldehyde: a redetermination

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organic papers

o282

Odabas¸og˘lu and Bu¨yu¨kgu¨ngo¨r C

12H16O2 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

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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]
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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) =

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[image:4.610.124.486.70.366.2]

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]
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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 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)

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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)

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supporting information

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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

Figure

Figure 2
Figure 2

References

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