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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1787.
Published online 2010 June 26. doi:  10.1107/S1600536810023731
PMCID: PMC3006858

2-[(3,5-Di-tert-butyl-4-hy­droxy­benz­yl)sulfan­yl]benzoic acid

Abstract

In the title compound, C22H28O3S, the dihedral angle between the two aromatic rings is 80.56 (6)°. The hy­droxy group is shielded by the two sterically hindered tert-butyl groups and therefore is not involved in any hydrogen bonding. The C—O—H fragment is coplanar with the aromatic ring, the dihedral angle between them being 7(5)°. In the crystal structure, pairs of mol­ecules are hydrogen bonded across crystallographic centers of symmetry.

Related literature

For a similar structure based on nicotinic acid, see: Mansor et al. (2008 [triangle]).

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Object name is e-66-o1787-scheme1.jpg

Experimental

Crystal data

  • C22H28O3S
  • M r = 372.50
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1787-efi1.jpg
  • a = 18.1496 (4) Å
  • b = 5.6863 (1) Å
  • c = 20.2159 (4) Å
  • β = 101.172 (1)°
  • V = 2046.83 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.18 mm−1
  • T = 296 K
  • 0.35 × 0.28 × 0.18 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.941, T max = 0.969
  • 15313 measured reflections
  • 3610 independent reflections
  • 2477 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.123
  • S = 1.02
  • 3610 reflections
  • 247 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810023731/pk2249sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810023731/pk2249Isup2.hkl

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

Acknowledgments

The authors thank the University of Malaya for funding this study (FRGS grant FP009/2008 C).

supplementary crystallographic information

Comment

Interest in the title compound stems from its use as an antioxidant. The hydroxyl group resides in a sterically encumbered pocket provided by the 3,5-di tert-butyl groups. Consequently, it is capable of forming a stable phenoxy radical. The position of the hydroxyl hydrogen atom is interesting since it has little space. The final difference map shows the hydrogen atom as the largest peak, and it is nearly in the plane of the phenyl ring. The hydrogen (H3) was refined in this position with U(H3) = 1.5Ueq(O3); however, there are unavoidable short contacts, the shortest being 1.83 Å to one of the methyl H atoms (H18A). In the structure of the similar compound (Mansor et al., 2008), the hydrogen atom was placed in a "chemically sensible" position, perpendicular to the phenyl group, that yielded a more distant contact (the shortest is 2.05 Å to one of the methyl H atoms). However, we have examined the difference map for this structure and found that the peak of maximum electron density is not perpendicular to the phenyl ring and clearly lies in the plane of the phenyl ring, as it does in the title compound. Upon free refinement, the shortest contact from the hydroxyl hydrogen to the nearest methyl hydrogen is 1.80 Å. Therefore, we would like to suggest that these structures do, indeed, display short H···H contacts that bear further investigation, preferably at very low (i.e. He cryostat) temperatures.

Experimental

Thiosalicylic acid (0.154 g, 1 mmol), 2,6-di-t-butylphenol (2.00 g, 1 mmol) and paraformaldehyde (0.291 g,1 mmol) were ground into a homogenous powder and to this was added di-n-butylamine (0.09 ml). The slurry was heated to 353 K for 2.5 h, then cooled to 323 K, ethanol (20 ml) was added and stirred for 1 h. The mixture was then acidified to pH= 5–5.5 by using 1.5% hydrochloric acid solution. The slurry was filtered and the filtrate was kept in the dark for 5 days whereupon the colorless crystals of the title compound were obtained.

Refinement

The C-bound hydrogen atoms were placed at calculated positions (C—H 0.93–0.97 Å) and were treated as riding on their parent atoms with U(H) set to 1.2–1.5 Ueq(C). The carboxylic acid H-atom was located in a difference Fourier map and was refined with a distance restraint of O—H 0.82 (2) Å. The hydroxyl H-atom was located in a difference Fourier map and was refined with U(H) set to 1.5Ueq(O3).

Figures

Fig. 1.
A perspective drawing of two molecules of the title compound showing dimerization through intermolecular H-bonds. Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C22H28O3SF(000) = 800
Mr = 372.50Dx = 1.209 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2170 reflections
a = 18.1496 (4) Åθ = 2.2–21.4°
b = 5.6863 (1) ŵ = 0.18 mm1
c = 20.2159 (4) ÅT = 296 K
β = 101.172 (1)°Block, colourless
V = 2046.83 (7) Å30.35 × 0.28 × 0.18 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer3610 independent reflections
Radiation source: fine-focus sealed tube2477 reflections with I > 2σ(I)
graphiteRint = 0.041
[var phi] and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −21→21
Tmin = 0.941, Tmax = 0.969k = −6→6
15313 measured reflectionsl = −24→24

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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 1.01w = 1/[σ2(Fo2) + (0.0518P)2 + 0.6688P] where P = (Fo2 + 2Fc2)/3
3610 reflections(Δ/σ)max < 0.001
247 parametersΔρmax = 0.32 e Å3
1 restraintΔρmin = −0.17 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
S10.08318 (3)0.07380 (12)0.38838 (3)0.0556 (2)
O1−0.08616 (10)−0.4044 (4)0.44667 (10)0.0713 (6)
H1−0.0691 (18)−0.500 (5)0.4773 (14)0.107*
O20.03143 (10)−0.2849 (3)0.45796 (9)0.0722 (6)
H30.437 (2)0.532 (6)0.4727 (18)0.108*
O30.42604 (9)0.4524 (3)0.44311 (8)0.0570 (5)
C1−0.03435 (13)−0.2647 (5)0.43156 (12)0.0511 (6)
C2−0.06278 (12)−0.0867 (4)0.37992 (11)0.0455 (5)
C3−0.13987 (13)−0.0776 (5)0.35422 (12)0.0560 (6)
H3A−0.1715−0.18270.37040.067*
C4−0.17013 (14)0.0820 (5)0.30591 (13)0.0602 (7)
H4−0.22170.08690.28980.072*
C5−0.12312 (14)0.2351 (5)0.28141 (13)0.0617 (7)
H5−0.14310.34190.24780.074*
C6−0.04738 (14)0.2318 (5)0.30594 (12)0.0555 (6)
H6−0.01680.33740.28870.067*
C7−0.01457 (12)0.0736 (4)0.35630 (11)0.0453 (5)
C80.11580 (13)0.3226 (4)0.34536 (13)0.0551 (6)
H8A0.10710.29360.29720.066*
H8B0.08870.46370.35320.066*
C90.19819 (13)0.3541 (4)0.37237 (12)0.0476 (6)
C100.25124 (13)0.2638 (4)0.33862 (11)0.0482 (6)
H100.23480.17820.29930.058*
C110.32779 (12)0.2952 (4)0.36066 (11)0.0438 (5)
C120.34993 (12)0.4227 (4)0.42063 (11)0.0424 (5)
C130.29827 (13)0.5169 (4)0.45709 (11)0.0448 (5)
C140.22284 (13)0.4794 (4)0.43102 (12)0.0506 (6)
H140.18740.54100.45390.061*
C150.32235 (14)0.6534 (4)0.52338 (12)0.0545 (6)
C160.25557 (18)0.7412 (8)0.55221 (18)0.1132 (14)
H16A0.22530.84360.52020.170*
H16B0.27350.82570.59330.170*
H16C0.22590.60960.56130.170*
C170.3697 (2)0.4965 (6)0.57768 (14)0.0901 (10)
H17A0.33930.36950.58860.135*
H17B0.38760.58830.61740.135*
H17C0.41170.43420.56090.135*
C180.36869 (19)0.8726 (5)0.51428 (16)0.0828 (9)
H18A0.41400.82600.50000.124*
H18B0.38120.95550.55630.124*
H18C0.33990.97340.48080.124*
C190.38448 (14)0.1959 (4)0.31979 (11)0.0518 (6)
C200.34466 (17)0.0547 (6)0.25871 (14)0.0856 (10)
H20A0.31110.15590.22900.128*
H20B0.3166−0.07120.27360.128*
H20C0.3813−0.00920.23520.128*
C210.42732 (18)0.3964 (5)0.29384 (16)0.0828 (10)
H21A0.45380.48570.33130.124*
H21B0.39250.49700.26510.124*
H21C0.46250.33260.26880.124*
C220.43946 (16)0.0255 (5)0.36205 (14)0.0700 (8)
H22A0.4747−0.03020.33580.105*
H22B0.4123−0.10540.37540.105*
H22C0.46600.10500.40150.105*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0401 (4)0.0669 (4)0.0595 (4)−0.0046 (3)0.0088 (3)0.0124 (3)
O10.0490 (11)0.0898 (15)0.0741 (13)−0.0145 (10)0.0098 (9)0.0283 (11)
O20.0433 (11)0.0890 (14)0.0831 (13)−0.0060 (9)0.0095 (9)0.0368 (11)
O30.0446 (10)0.0721 (12)0.0559 (11)−0.0047 (8)0.0137 (8)−0.0186 (9)
C10.0431 (15)0.0646 (16)0.0484 (14)−0.0046 (12)0.0156 (11)0.0040 (12)
C20.0401 (13)0.0562 (14)0.0413 (12)0.0000 (11)0.0108 (10)−0.0043 (11)
C30.0454 (15)0.0684 (17)0.0564 (15)−0.0010 (12)0.0152 (12)−0.0016 (14)
C40.0394 (14)0.0803 (19)0.0595 (16)0.0066 (13)0.0060 (12)−0.0020 (15)
C50.0558 (17)0.0677 (18)0.0595 (16)0.0139 (14)0.0058 (13)0.0074 (14)
C60.0488 (15)0.0601 (16)0.0574 (15)0.0003 (12)0.0102 (12)0.0096 (13)
C70.0415 (13)0.0538 (14)0.0420 (12)0.0015 (11)0.0112 (10)−0.0032 (11)
C80.0468 (15)0.0589 (16)0.0610 (16)−0.0042 (12)0.0136 (12)0.0061 (12)
C90.0458 (14)0.0485 (14)0.0505 (14)−0.0057 (11)0.0142 (11)0.0037 (11)
C100.0532 (15)0.0498 (14)0.0424 (13)−0.0057 (11)0.0112 (11)−0.0051 (11)
C110.0470 (14)0.0464 (13)0.0405 (12)−0.0016 (10)0.0151 (10)−0.0006 (10)
C120.0410 (13)0.0451 (13)0.0435 (12)−0.0036 (10)0.0139 (10)−0.0015 (10)
C130.0505 (14)0.0458 (13)0.0421 (12)−0.0036 (10)0.0190 (11)−0.0026 (10)
C140.0503 (15)0.0532 (15)0.0543 (15)−0.0017 (11)0.0254 (12)−0.0018 (12)
C150.0667 (17)0.0565 (15)0.0455 (14)−0.0068 (12)0.0235 (12)−0.0099 (12)
C160.088 (2)0.158 (4)0.105 (3)−0.013 (2)0.047 (2)−0.074 (3)
C170.128 (3)0.094 (2)0.0485 (17)−0.005 (2)0.0170 (18)−0.0055 (16)
C180.106 (3)0.071 (2)0.076 (2)−0.0196 (17)0.0289 (18)−0.0233 (16)
C190.0579 (15)0.0574 (15)0.0440 (14)0.0023 (12)0.0197 (11)−0.0077 (12)
C200.084 (2)0.114 (3)0.0609 (18)0.0135 (18)0.0185 (16)−0.0377 (18)
C210.101 (2)0.080 (2)0.086 (2)0.0036 (17)0.0625 (19)0.0039 (17)
C220.0738 (19)0.0719 (19)0.0671 (18)0.0182 (15)0.0205 (15)−0.0081 (14)

Geometric parameters (Å, °)

S1—C71.767 (2)C13—C141.385 (3)
S1—C81.819 (2)C13—C151.537 (3)
O1—C11.311 (3)C14—H140.9300
O1—H10.837 (18)C15—C161.527 (4)
O2—C11.215 (3)C15—C181.535 (4)
O3—C121.378 (3)C15—C171.541 (4)
O3—H30.75 (3)C16—H16A0.9600
C1—C21.474 (3)C16—H16B0.9600
C2—C31.396 (3)C16—H16C0.9600
C2—C71.409 (3)C17—H17A0.9600
C3—C41.368 (3)C17—H17B0.9600
C3—H3A0.9300C17—H17C0.9600
C4—C51.377 (4)C18—H18A0.9600
C4—H40.9300C18—H18B0.9600
C5—C61.368 (3)C18—H18C0.9600
C5—H50.9300C19—C221.528 (3)
C6—C71.402 (3)C19—C211.529 (4)
C6—H60.9300C19—C201.532 (4)
C8—C91.500 (3)C20—H20A0.9600
C8—H8A0.9700C20—H20B0.9600
C8—H8B0.9700C20—H20C0.9600
C9—C141.381 (3)C21—H21A0.9600
C9—C101.382 (3)C21—H21B0.9600
C10—C111.386 (3)C21—H21C0.9600
C10—H100.9300C22—H22A0.9600
C11—C121.403 (3)C22—H22B0.9600
C11—C191.546 (3)C22—H22C0.9600
C12—C131.406 (3)
C7—S1—C8102.81 (11)C16—C15—C18105.9 (3)
C1—O1—H1113 (2)C16—C15—C13112.7 (2)
C12—O3—H3115 (3)C18—C15—C13112.0 (2)
O2—C1—O1121.9 (2)C16—C15—C17107.0 (3)
O2—C1—C2123.7 (2)C18—C15—C17108.2 (2)
O1—C1—C2114.4 (2)C13—C15—C17110.7 (2)
C3—C2—C7119.6 (2)C15—C16—H16A109.5
C3—C2—C1118.5 (2)C15—C16—H16B109.5
C7—C2—C1121.9 (2)H16A—C16—H16B109.5
C4—C3—C2121.7 (2)C15—C16—H16C109.5
C4—C3—H3A119.2H16A—C16—H16C109.5
C2—C3—H3A119.2H16B—C16—H16C109.5
C3—C4—C5119.0 (2)C15—C17—H17A109.5
C3—C4—H4120.5C15—C17—H17B109.5
C5—C4—H4120.5H17A—C17—H17B109.5
C6—C5—C4120.7 (2)C15—C17—H17C109.5
C6—C5—H5119.7H17A—C17—H17C109.5
C4—C5—H5119.7H17B—C17—H17C109.5
C5—C6—C7121.9 (2)C15—C18—H18A109.5
C5—C6—H6119.1C15—C18—H18B109.5
C7—C6—H6119.1H18A—C18—H18B109.5
C6—C7—C2117.2 (2)C15—C18—H18C109.5
C6—C7—S1121.41 (18)H18A—C18—H18C109.5
C2—C7—S1121.41 (18)H18B—C18—H18C109.5
C9—C8—S1108.23 (17)C22—C19—C21110.1 (2)
C9—C8—H8A110.1C22—C19—C20105.9 (2)
S1—C8—H8A110.1C21—C19—C20107.8 (2)
C9—C8—H8B110.1C22—C19—C11111.29 (19)
S1—C8—H8B110.1C21—C19—C11110.3 (2)
H8A—C8—H8B108.4C20—C19—C11111.3 (2)
C14—C9—C10118.3 (2)C19—C20—H20A109.5
C14—C9—C8120.6 (2)C19—C20—H20B109.5
C10—C9—C8121.1 (2)H20A—C20—H20B109.5
C9—C10—C11123.0 (2)C19—C20—H20C109.5
C9—C10—H10118.5H20A—C20—H20C109.5
C11—C10—H10118.5H20B—C20—H20C109.5
C10—C11—C12116.5 (2)C19—C21—H21A109.5
C10—C11—C19120.7 (2)C19—C21—H21B109.5
C12—C11—C19122.8 (2)H21A—C21—H21B109.5
O3—C12—C11116.68 (19)C19—C21—H21C109.5
O3—C12—C13120.53 (19)H21A—C21—H21C109.5
C11—C12—C13122.8 (2)H21B—C21—H21C109.5
C14—C13—C12116.9 (2)C19—C22—H22A109.5
C14—C13—C15120.2 (2)C19—C22—H22B109.5
C12—C13—C15122.9 (2)H22A—C22—H22B109.5
C9—C14—C13122.5 (2)C19—C22—H22C109.5
C9—C14—H14118.7H22A—C22—H22C109.5
C13—C14—H14118.7H22B—C22—H22C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.84 (2)1.83 (2)2.661 (2)178 (4)

Symmetry codes: (i) −x, −y−1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2249).

References

  • Barbour, L. J. (2001). J. Supramol. Chem 1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Mansor, S., Yehye, W. A., Ariffin, A., Rahman, N. A. & Ng, S. W. (2008). Acta Cryst. E64, o1778. [PMC free article] [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43 Submitted.

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