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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 is P21/m.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041887/dn6289sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041887/dn6289Isup2.hkl
Contains datablock I

CCDC reference: 296560

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.039
  • wR factor = 0.109
  • Data-to-parameter ratio = 12.0

checkCIF/PLATON results

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Alert level C PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.77 mm PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety C11 PLAT391_ALERT_3_C Deviating Methyl C11 H-C-H Bond Angle ...... 101.90 Deg.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

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 CO double bond in carbonyl compounds (Loudon, 2002).

Experimental top

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).

Refinement top

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) = 1.5Ueq(methyl C) and Uiso(H) = 1.2Ueq(O).

Computing details top

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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 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] Fig. 2. A packing diagram of (I), showing the hydrogen-bonding scheme (dashed lines).
3-tert-butyl-2-hydroxy-5-methylbenzaldehyde top
Crystal data top
C12H16O2F(000) = 208
Mr = 192.25Dx = 1.194 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybCell parameters from 5006 reflections
a = 8.3633 (8) Åθ = 3.0–28.8°
b = 6.6200 (6) ŵ = 0.08 mm1
c = 9.7328 (11) ÅT = 100 K
β = 97.170 (9)°Prism, yellow
V = 534.64 (9) Å30.77 × 0.50 × 0.20 mm
Z = 2
Data collection top
Stoe
diffractometer
1037 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.029
Graphite monochromatorθmax = 26.0°, θmin = 3.4°
Detector resolution: 6.67 pixels mm-1h = 1010
ϕ scan rotation methodk = 88
5006 measured reflectionsl = 1212
1136 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0624P)2 + 0.1473P]
where P = (Fo2 + 2Fc2)/3
1136 reflections(Δ/σ)max < 0.001
95 parametersΔρmax = 0.30 e Å3
5 restraintsΔρmin = 0.21 e Å3
Crystal data top
C12H16O2V = 534.64 (9) Å3
Mr = 192.25Z = 2
Monoclinic, P21/mMo Kα radiation
a = 8.3633 (8) ŵ = 0.08 mm1
b = 6.6200 (6) ÅT = 100 K
c = 9.7328 (11) Å0.77 × 0.50 × 0.20 mm
β = 97.170 (9)°
Data collection top
Stoe
diffractometer
1037 reflections with I > 2σ(I)
5006 measured reflectionsRint = 0.029
1136 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0395 restraints
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.30 e Å3
1136 reflectionsΔρmin = 0.21 e Å3
95 parameters
Special details top

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) top
xyzUiso*/Ueq
C10.55851 (17)0.25000.48411 (16)0.0178 (3)
C20.49028 (17)0.25000.34480 (15)0.0167 (3)
C30.32167 (17)0.25000.31042 (15)0.0162 (3)
C40.23035 (17)0.25000.41980 (15)0.0168 (3)
H40.11880.25000.39900.020*
C50.29523 (18)0.25000.55985 (15)0.0176 (3)
C60.46025 (18)0.25000.58976 (15)0.0176 (3)
H60.50700.25000.68160.021*
C70.73224 (18)0.25000.51989 (17)0.0218 (4)
H70.77220.25000.61340.026*
C80.24411 (18)0.25000.15894 (15)0.0191 (4)
C90.29509 (14)0.44005 (19)0.08592 (11)0.0279 (3)
H9A0.24690.43910.00890.042*
H9B0.41030.44250.08950.042*
H9C0.26000.55770.13150.042*
C100.0601 (2)0.25000.14759 (17)0.0276 (4)
H10A0.017 (3)0.25000.0513 (11)0.041*
H10B0.0202 (18)0.1301 (18)0.1902 (15)0.041*
C110.1852 (2)0.25000.67075 (17)0.0250 (4)
H11A0.243 (2)0.25000.7616 (13)0.037*
H11B0.1125 (15)0.1377 (18)0.6625 (15)0.037*
O10.83007 (13)0.25000.43643 (13)0.0277 (3)
O20.58647 (13)0.25000.24303 (12)0.0245 (3)
H20.6816 (14)0.25000.2856 (19)0.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0160 (7)0.0120 (6)0.0249 (8)0.0000.0010 (6)0.000
C20.0170 (7)0.0141 (7)0.0199 (7)0.0000.0064 (6)0.000
C30.0174 (7)0.0132 (7)0.0178 (7)0.0000.0019 (5)0.000
C40.0134 (7)0.0160 (7)0.0210 (7)0.0000.0025 (5)0.000
C50.0200 (7)0.0145 (7)0.0190 (7)0.0000.0054 (6)0.000
C60.0216 (8)0.0141 (7)0.0163 (7)0.0000.0007 (6)0.000
C70.0182 (8)0.0169 (7)0.0293 (8)0.0000.0011 (6)0.000
C80.0206 (7)0.0199 (7)0.0164 (7)0.0000.0012 (5)0.000
C90.0354 (6)0.0271 (7)0.0204 (5)0.0036 (5)0.0005 (4)0.0055 (4)
C100.0217 (8)0.0379 (10)0.0215 (8)0.0000.0041 (6)0.000
C110.0260 (8)0.0300 (9)0.0203 (8)0.0000.0085 (6)0.000
O10.0145 (5)0.0274 (6)0.0414 (7)0.0000.0045 (5)0.000
O20.0163 (5)0.0344 (7)0.0241 (6)0.0000.0079 (4)0.000
Geometric parameters (Å, º) top
C1—C61.394 (2)C7—H70.9300
C1—C21.404 (2)C8—C101.529 (2)
C1—C71.451 (2)C8—C91.5315 (14)
C2—O21.3517 (17)C8—C9i1.5315 (14)
C2—C31.408 (2)C9—H9A0.9600
C3—C41.385 (2)C9—H9B0.9600
C3—C81.5348 (19)C9—H9C0.9600
C4—C51.403 (2)C10—H10A0.961 (10)
C4—H40.9300C10—H10B0.974 (9)
C5—C61.375 (2)C11—H11A0.953 (10)
C5—C111.503 (2)C11—H11B0.957 (9)
C6—H60.9300O2—H20.850 (10)
C7—O11.223 (2)
C6—C1—C2120.43 (13)C1—C7—H7117.5
C6—C1—C7119.19 (14)C10—C8—C9107.60 (9)
C2—C1—C7120.39 (14)C10—C8—C9i107.60 (9)
O2—C2—C1120.02 (13)C9—C8—C9i110.48 (13)
O2—C2—C3119.72 (13)C10—C8—C3111.73 (12)
C1—C2—C3120.25 (13)C9—C8—C3109.70 (8)
C4—C3—C2116.69 (13)C9i—C8—C3109.70 (8)
C4—C3—C8122.06 (13)C8—C9—H9A109.5
C2—C3—C8121.26 (13)C8—C9—H9B109.5
C3—C4—C5124.28 (13)H9A—C9—H9B109.5
C3—C4—H4117.9C8—C9—H9C109.5
C5—C4—H4117.9H9A—C9—H9C109.5
C6—C5—C4117.52 (13)H9B—C9—H9C109.5
C6—C5—C11122.45 (14)C8—C10—H10A109.0 (13)
C4—C5—C11120.03 (13)C8—C10—H10B111.4 (9)
C5—C6—C1120.83 (13)H10A—C10—H10B107.9 (12)
C5—C6—H6119.6C5—C11—H11A112.4 (13)
C1—C6—H6119.6C5—C11—H11B112.2 (9)
O1—C7—C1124.99 (15)H11A—C11—H11B108.7 (11)
O1—C7—H7117.5C2—O2—H2104.4 (14)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.85 (1)1.80 (1)2.5954 (16)155 (2)
C4—H4···O1ii0.932.493.3717 (18)159
Symmetry code: (ii) x1, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC12H16O2
Mr192.25
Crystal system, space groupMonoclinic, P21/m
Temperature (K)100
a, b, c (Å)8.3633 (8), 6.6200 (6), 9.7328 (11)
β (°) 97.170 (9)
V3)534.64 (9)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.77 × 0.50 × 0.20
Data collection
DiffractometerStoe
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5006, 1136, 1037
Rint0.029
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.109, 1.07
No. of reflections1136
No. of parameters95
No. of restraints5
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.30, 0.21

Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.850 (10)1.800 (12)2.5954 (16)155 (2)
C4—H4···O1i0.932.493.3717 (18)159
Symmetry code: (i) x1, y+1/2, z.
 

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