PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2218.
Published online 2010 August 4. doi:  10.1107/S1600536810030382
PMCID: PMC3007824

5-tert-Butyl-2-hy­droxy-3-(2-thien­yl)benzaldehyde

Abstract

In the crystal structure of the title compound, C15H16O2S, the thio­phene ring is essentially planar (r.m.s. deviation = 0.006 Å for all non-H atoms) and roughly coplanar with the benzene ring, the dihedral angle between the mean planes of the rings being 4.35 (8)°. An intra­molecular O—H(...)O hydrogen bond is observed between the OH group and the aldehyde O atom.

Related literature

For related salicyl­aldehyde derivative compounds, see: Qiu et al. (2009 [triangle]); Yu et al. (2007 [triangle]); Wang et al. (2009 [triangle]); Wong et al. (2004 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2218-scheme1.jpg

Experimental

Crystal data

  • C15H16O2S
  • M r = 260.34
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2218-efi1.jpg
  • a = 7.2016 (14) Å
  • b = 8.9375 (18) Å
  • c = 10.922 (2) Å
  • α = 91.50 (3)°
  • β = 107.69 (3)°
  • γ = 93.25 (3)°
  • V = 668.0 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.23 mm−1
  • T = 173 K
  • 0.10 × 0.10 × 0.10 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.977, T max = 0.977
  • 5891 measured reflections
  • 2705 independent reflections
  • 1958 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.059
  • wR(F 2) = 0.208
  • S = 1.15
  • 2705 reflections
  • 179 parameters
  • 9 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.45 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810030382/zq2050sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030382/zq2050Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This project was sponsored by the Cultivation Program of Young and Middle-aged Academic Leaders in Zhejiang Higher Education Institutions, the Natural Science Foundation of Ningbo City (Nos. 2009 A610047 and 2010 A610027) and the K. C. Wong Magna Fund of Ningbo University. We thank Professor X. Li for help with the structural analysis.

supplementary crystallographic information

Comment

Salicylaldehyde and its derivatives are widely used in the construction of metal complexes (Qiu et al., 2009; Wang et al., 2009; Yu et al., 2007). We have synthesized a series of lanthanide complexes of a Schiff base which derived from 2-pyridyl salicylaldehyde and investigated their luminescent properties (Wong et al., 2004). In the course of exploring new luminescent compounds, we synthesized the title molecule 5-tert-butyl-2-hydroxy-3-thiophen-2-ylbenzaldehyde (I) as an intermediate compound.

The molecular structure of the title compound is shown in Fig. 1. The thiophene ring is essentially planar (rms deviation = 0.006Å for all non-H atoms) and roughly coplanar with the phenyl ring, making a dihedral angle between the mean planes of the rings of 4.35 (8)°. There are no intermolecular hydrogen bonds in the crystal structure but the intramolecular interaction O2—H2D···O1 between the hydroxy OH group and the aldehyde O atom is helpful to stabilize the molecular conformation.

Experimental

3-Bromo-5-tert-butyl-2-hydroxybenzaldehyde (1.50 g, 5.86 mmol), 2-thienyl-tributyltin (2.40 g, 6.45 mmol), triphenyl phosphine (0.31 g, 0.38 mmol) and palladium dichloride (0.05 g, 0.28 mmol) were added to 20 ml THF in a round flask, and this mixture was refluxed with agitation for 24 h. Then, 20 ml toluene was added and the mixture was refluxed at 100°C for another 24 h. Finally, the reaction mixture was refluxed at 105°C after addition of 20 ml DMF for further 24 h. After evaporating the solvent, the residue was chromatographed on silica gel and a yellowish precipitate was produced. The precipitate was recrystallized from dichloromethane and yellow block-shaped crystals were obtained (0.62 g, 41%). 1H NMR (400 MHz, CDCl3): 11.73 (s, 1H), 9.93 (s, 1H), 7.91 (d, J = 2.0 Hz, 1H), 7.31 (dd, J = 1.2 Hz, J = 3.6 Hz,1H), 7.48 (d, J = 2.4 Hz, 1H), 7.37 (dd, J = 4.8 Hz, J = 0.8 Hz, 1H), 7.25 (s, 1H), 7.13 (dd, J = 3.6 Hz, J = 4.8 Hz, 1H), 1.37 (s, 9H). MS (EI, m/z): 260[M]+

Refinement

The H atoms attached to C atoms were placed in calculated positions and treated using a riding-model approximation (with C–H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, and with C–H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for the methyl H atoms). The important H atoms bonded to O2 and C6 were located in the difference Fourier map and were freely refined.

Figures

Fig. 1.
View of (I) with displacement ellipsoids drawn at the 30% probability level. The dotted line indicates the intramolecular H-bond.

Crystal data

C15H16O2SZ = 2
Mr = 260.34F(000) = 276
Triclinic, P1Dx = 1.294 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2016 (14) ÅCell parameters from 5891 reflections
b = 8.9375 (18) Åθ = 3.0–26.4°
c = 10.922 (2) ŵ = 0.23 mm1
α = 91.50 (3)°T = 173 K
β = 107.69 (3)°Block, yellow
γ = 93.25 (3)°0.10 × 0.10 × 0.10 mm
V = 668.0 (2) Å3

Data collection

Rigaku R-AXIS RAPID diffractometer2705 independent reflections
Radiation source: fine-focus sealed tube1958 reflections with I > 2σ(I)
graphiteRint = 0.020
Detector resolution: 0 pixels mm-1θmax = 26.4°, θmin = 3.0°
ω scansh = −8→8
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)k = −11→11
Tmin = 0.977, Tmax = 0.977l = −13→13
5891 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.208H atoms treated by a mixture of independent and constrained refinement
S = 1.15w = 1/[σ2(Fo2) + (0.1265P)2 + 0.0566P] where P = (Fo2 + 2Fc2)/3
2705 reflections(Δ/σ)max < 0.001
179 parametersΔρmax = 0.41 e Å3
9 restraintsΔρmin = −0.45 e Å3

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)

xyzUiso*/Ueq
S10.39900 (12)0.44272 (9)0.30990 (6)0.0798 (4)
O20.3088 (3)0.6482 (2)0.12395 (19)0.0677 (5)
C150.2702 (3)0.3967 (2)0.0406 (2)0.0482 (5)
C140.2152 (3)0.3004 (2)−0.0692 (2)0.0496 (5)
H14A0.22260.1957−0.05740.060*
C130.1403 (3)0.4992 (3)−0.2105 (2)0.0544 (6)
H13A0.09790.5352−0.29490.065*
C120.3408 (3)0.3350 (3)0.1694 (2)0.0508 (5)
C110.1504 (3)0.3476 (2)−0.1946 (2)0.0497 (5)
C100.2573 (3)0.5507 (3)0.0206 (2)0.0507 (5)
C90.1912 (3)0.6013 (3)−0.1048 (2)0.0556 (6)
C80.0927 (4)0.2304 (3)−0.3084 (2)0.0564 (6)
C70.3726 (4)0.1835 (3)0.1953 (2)0.0636 (6)
O10.2186 (4)0.8609 (2)−0.0407 (2)0.0947 (7)
C60.1769 (5)0.7611 (3)−0.1262 (3)0.0748 (8)
C50.4400 (4)0.1649 (3)0.3312 (3)0.0721 (7)
H5A0.46880.07060.36820.087*
C40.2655 (4)0.1362 (3)−0.3025 (2)0.0716 (7)
H4A0.37630.2017−0.30800.107*
H4B0.22830.0616−0.37460.107*
H4C0.30260.0851−0.22120.107*
C30.0331 (5)0.3042 (3)−0.4383 (2)0.0759 (8)
H3A0.14250.3700−0.44560.114*
H3B−0.07950.3635−0.44460.114*
H3C−0.00170.2265−0.50790.114*
C2−0.0816 (4)0.1276 (3)−0.2998 (3)0.0757 (8)
H2A−0.11910.0532−0.37210.114*
H2B−0.19220.1881−0.30320.114*
H2C−0.04430.0761−0.21870.114*
C10.4584 (4)0.2933 (4)0.4010 (3)0.0765 (8)
H70.354 (6)0.109 (3)0.140 (3)0.127 (14)*
H20.504 (4)0.303 (4)0.4875 (10)0.082 (9)*
H6A0.135 (6)0.804 (5)−0.213 (4)0.127 (14)*
H2D0.292 (4)0.726 (4)0.093 (3)0.068 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.1003 (6)0.0763 (6)0.0558 (5)0.0081 (4)0.0148 (4)−0.0179 (3)
O20.0845 (13)0.0497 (11)0.0657 (11)−0.0018 (9)0.0210 (10)−0.0186 (9)
C150.0443 (11)0.0505 (12)0.0496 (11)−0.0004 (9)0.0157 (9)−0.0095 (9)
C140.0550 (12)0.0418 (11)0.0503 (12)0.0017 (9)0.0146 (10)−0.0067 (9)
C130.0561 (13)0.0525 (13)0.0551 (12)0.0022 (10)0.0183 (10)−0.0028 (10)
C120.0469 (11)0.0555 (13)0.0485 (11)−0.0001 (9)0.0142 (9)−0.0107 (9)
C110.0525 (12)0.0471 (12)0.0487 (11)0.0010 (9)0.0155 (9)−0.0064 (9)
C100.0485 (11)0.0472 (12)0.0572 (12)−0.0019 (9)0.0197 (10)−0.0134 (9)
C90.0594 (13)0.0449 (12)0.0653 (14)−0.0011 (10)0.0245 (11)−0.0063 (10)
C80.0670 (14)0.0505 (13)0.0484 (12)0.0005 (10)0.0144 (10)−0.0097 (9)
C70.0820 (15)0.0581 (13)0.0452 (11)0.0039 (11)0.0118 (10)0.0004 (9)
O10.141 (2)0.0451 (11)0.0976 (15)−0.0011 (11)0.0388 (14)−0.0120 (10)
C60.098 (2)0.0475 (14)0.0825 (19)0.0032 (13)0.0332 (17)−0.0002 (13)
C50.0849 (15)0.0702 (14)0.0555 (11)0.0096 (12)0.0121 (11)0.0049 (10)
C40.0867 (19)0.0661 (16)0.0595 (14)0.0129 (13)0.0186 (13)−0.0165 (12)
C30.100 (2)0.0675 (17)0.0505 (13)0.0057 (15)0.0103 (13)−0.0100 (12)
C20.0847 (19)0.0693 (17)0.0667 (16)−0.0170 (14)0.0193 (14)−0.0210 (13)
C10.0772 (18)0.097 (2)0.0504 (14)0.0074 (15)0.0124 (13)−0.0067 (14)

Geometric parameters (Å, °)

S1—C11.683 (3)C8—C21.541 (4)
S1—C121.716 (2)C7—C51.432 (3)
O2—C101.352 (3)C7—H70.867 (10)
O2—H2D0.78 (3)O1—C61.230 (3)
C15—C141.399 (3)C6—H6A0.99 (4)
C15—C101.402 (3)C5—C11.339 (4)
C15—C121.476 (3)C5—H5A0.9500
C14—C111.391 (3)C4—H4A0.9800
C14—H14A0.9500C4—H4B0.9800
C13—C111.374 (3)C4—H4C0.9800
C13—C91.396 (3)C3—H3A0.9800
C13—H13A0.9500C3—H3B0.9800
C12—C71.408 (3)C3—H3C0.9800
C11—C81.544 (3)C2—H2A0.9800
C10—C91.403 (3)C2—H2B0.9800
C9—C61.457 (4)C2—H2C0.9800
C8—C41.527 (4)C1—H20.902 (10)
C8—C31.530 (4)
C1—S1—C1292.60 (13)C12—C7—H7127 (3)
C10—O2—H2D103 (2)C5—C7—H7122 (3)
C14—C15—C10116.7 (2)O1—C6—C9125.0 (3)
C14—C15—C12120.00 (19)O1—C6—H6A111 (2)
C10—C15—C12123.30 (19)C9—C6—H6A124 (3)
C11—C14—C15124.4 (2)C1—C5—C7113.4 (3)
C11—C14—H14A117.8C1—C5—H5A123.3
C15—C14—H14A117.8C7—C5—H5A123.3
C11—C13—C9121.2 (2)C8—C4—H4A109.5
C11—C13—H13A119.4C8—C4—H4B109.5
C9—C13—H13A119.4H4A—C4—H4B109.5
C7—C12—C15125.95 (19)C8—C4—H4C109.5
C7—C12—S1110.58 (17)H4A—C4—H4C109.5
C15—C12—S1123.46 (17)H4B—C4—H4C109.5
C13—C11—C14117.3 (2)C8—C3—H3A109.5
C13—C11—C8123.0 (2)C8—C3—H3B109.5
C14—C11—C8119.69 (19)H3A—C3—H3B109.5
O2—C10—C15118.8 (2)C8—C3—H3C109.5
O2—C10—C9121.1 (2)H3A—C3—H3C109.5
C15—C10—C9120.13 (19)H3B—C3—H3C109.5
C13—C9—C10120.3 (2)C8—C2—H2A109.5
C13—C9—C6119.3 (2)C8—C2—H2B109.5
C10—C9—C6120.3 (2)H2A—C2—H2B109.5
C4—C8—C3108.3 (2)C8—C2—H2C109.5
C4—C8—C2109.5 (2)H2A—C2—H2C109.5
C3—C8—C2108.3 (2)H2B—C2—H2C109.5
C4—C8—C11109.58 (19)C5—C1—S1112.9 (2)
C3—C8—C11111.9 (2)C5—C1—H2125 (2)
C2—C8—C11109.16 (19)S1—C1—H2122 (2)
C12—C7—C5110.5 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2D···O10.78 (3)1.89 (3)2.623 (3)157 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZQ2050).

References

  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Qiu, L., Lin, J. & Xu, Y. (2009). Inorg. Chem. Commun.12, 986–989.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2004). CrystalStructure Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, H., Zhang, D., Ni, Z.-H., Li, X., Tian, L. & Jiang, J. (2009). Inorg. Chem.48, 5946–5956. [PubMed]
  • Wong, W.-K., Liang, H., Guo, J., Wong, W.-Y., Lo, W.-K., Li, K.-F., Cheah, K.-W., Zhou, Z. & Wong, W.-T. (2004). Eur. J. Inorg. Chem.4, 829–836.
  • Yu, T.-Z., Su, W.-M., Li, W.-L., Hong, Z.-R., Hua, R.-N. & Li, B. (2007). Thin Solid Films, 515, 4080–4084.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography