supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

tk2295 scheme

Acta Cryst. (2008). E64, o1778    [ doi:10.1107/S1600536808026056 ]

2-(3,5-Di-tert-butyl-4-hydroxybenzylsulfanyl)nicotinic acid

S. Mansor, W. A. Yehye, A. Ariffin, N. A. Rahman and S. W. Ng

Abstract top

Two molecules of the title compound, C21H27NO3S, are disposed about a center of inversion, generating an O-H...O hydrogen-bonded dimer.

Comment top

The compound (I, Fig. 1) is the precursor for the synthesis of hindered phenol-based antioxidants. Phenol-based antioxidants and their derivative have applications in industries such as pharmaceutical, textiles, plastics, polymers, oils, pesticides,dyestuffs, explosives, fluorescent-brightening industries (Kim & Lee, 2003; Um & Lee, 2005). Molecules are connected into centrosymmetric dimers via the eight- membered {OCOH}2 synthon (Table 1). The hydroxyl-H projects between the two sterically hindered aromatic rings and is therefore precluded from forming a hydrogen bonding interaction.

Related literature top

For the applications of hindered phenol-based antioxidants, see: Kim & Lee (2003); Um & Lee (2005).

Experimental top

2-Mercaptonicotinic acid (1.50 g, 1 mmol), 2,6-di-t-butylphenol (2.00 g, 1 mmol) and paraformaldehyde (0.291 g,1 mmol) were intimately ground into a powder and to this was added di-n-butylamine (0.09 ml). The slurry was heated to 373–383 K and after an hour, this solidified. The solid was purified by column chromatography, with chloroform as solvent, to give two products, one of which was the expected acid, (I), and the other, the di-n-butylammonium salt of the acid.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U(C). The acid H-atom was located in a difference Fourier map, and was refined with a distance restraint of O–H 0.84±0.01 Å; its temperature factor were freely refined. The hydroxy H-atom was placed in a chemically sensible position, with a distance of more than 2 Å from the neighboring methyl H-atoms. The C–O–H fragment is then perpendicular to the aromatic ring.

Computing details top

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

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the hydrogen-bonded dimeric structure of (I) drawn at the 70% probability level. Dashed lines denote the hydrogen bonds. Hydrogen atoms are drawn as spheres of arbitrary radius.
2-(3,5-Di-tert-butyl-4-hydroxybenzylsulfanyl)nicotinic acid top
Crystal data top
C21H27NO3SZ = 2
Mr = 373.50F000 = 400
Triclinic, P1Dx = 1.253 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 5.6305 (1) ÅCell parameters from 3920 reflections
b = 9.3489 (2) Åθ = 2.2–28.4º
c = 18.8749 (3) ŵ = 0.18 mm−1
α = 85.505 (1)ºT = 100 (2) K
β = 89.453 (1)ºPrism, colorless
γ = 87.834 (1)º0.25 × 0.15 × 0.05 mm
V = 989.77 (3) Å3
Data collection top
Bruker SMART APEX
diffractometer		4507 independent reflections
Radiation source: fine-focus sealed tube3746 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
T = 100(2) Kθmax = 27.5º
ω scansθmin = 1.1º
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		h = −7→7
Tmin = 0.956, Tmax = 0.991k = −9→12
12688 measured reflectionsl = −24→24
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.127  w = 1/[σ2(Fo2) + (0.0642P)2 + 0.2102P]
where P = (Fo2 + 2Fc2)/3
S = 1.18(Δ/σ)max = 0.001
4507 reflectionsΔρmax = 0.75 e Å−3
239 parametersΔρmin = −0.71 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C21H27NO3Sγ = 87.834 (1)º
Mr = 373.50V = 989.77 (3) Å3
Triclinic, P1Z = 2
a = 5.6305 (1) ÅMo Kα
b = 9.3489 (2) ŵ = 0.18 mm−1
c = 18.8749 (3) ÅT = 100 (2) K
α = 85.505 (1)º0.25 × 0.15 × 0.05 mm
β = 89.453 (1)º
Data collection top
Bruker SMART APEX
diffractometer		4507 independent reflections
Absorption correction: Multi-scan
(SADABS; Sheldrick, 1996)		3746 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.991Rint = 0.028
12688 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0421 restraint
wR(F2) = 0.127H atoms treated by a mixture of
independent and constrained refinement
S = 1.18Δρmax = 0.75 e Å−3
4507 reflectionsΔρmin = −0.71 e Å−3
239 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.58009 (7)0.68988 (5)0.60316 (2)0.01722 (13)
O10.0857 (2)0.63037 (14)0.42620 (6)0.0211 (3)
H1O−0.014 (4)0.566 (2)0.4379 (14)0.053 (8)*
O20.2215 (2)0.56848 (14)0.53598 (6)0.0222 (3)
O30.8816 (2)0.54828 (13)0.92906 (6)0.0161 (3)
H3O0.78480.49340.95030.024*
N10.7549 (3)0.87163 (16)0.50351 (7)0.0177 (3)
C10.2358 (3)0.64038 (19)0.47879 (9)0.0184 (4)
C20.4212 (3)0.74553 (19)0.46400 (8)0.0176 (4)
C30.4393 (3)0.8192 (2)0.39715 (9)0.0203 (4)
H30.33160.80150.36070.024*
C40.6135 (3)0.9179 (2)0.38393 (9)0.0214 (4)
H40.62840.96890.33860.026*
C50.7661 (3)0.9404 (2)0.43878 (9)0.0203 (4)
H50.88561.00870.42990.024*
C60.5857 (3)0.77544 (19)0.51655 (8)0.0165 (3)
C70.8320 (3)0.7718 (2)0.64204 (8)0.0171 (3)
H7A0.98000.74890.61590.021*
H7B0.80700.87750.63970.021*
C80.8498 (3)0.71171 (19)0.71821 (8)0.0149 (3)
C90.9743 (3)0.58333 (19)0.73576 (8)0.0152 (3)
H91.05140.53500.69900.018*
C100.9903 (3)0.52279 (18)0.80543 (8)0.0131 (3)
C110.8749 (3)0.59945 (18)0.85839 (8)0.0126 (3)
C120.7483 (3)0.73030 (18)0.84288 (8)0.0126 (3)
C130.7379 (3)0.78302 (18)0.77173 (8)0.0148 (3)
H130.65140.87060.75950.018*
C141.1234 (3)0.37706 (18)0.82171 (8)0.0151 (3)
C151.3288 (3)0.38746 (19)0.87432 (9)0.0184 (4)
H15A1.40890.29300.88320.028*
H15B1.26530.41960.91920.028*
H15C1.44260.45640.85410.028*
C160.9495 (3)0.2627 (2)0.85004 (10)0.0213 (4)
H16A0.82230.25630.81550.032*
H16B0.88070.28960.89520.032*
H16C1.03470.16950.85750.032*
C171.2390 (3)0.3219 (2)0.75437 (9)0.0233 (4)
H17A1.11580.30970.71930.035*
H17B1.32240.22950.76650.035*
H17C1.35250.39140.73450.035*
C180.6287 (3)0.81640 (18)0.90074 (8)0.0141 (3)
C190.8187 (3)0.8637 (2)0.95129 (9)0.0188 (4)
H19A0.90640.77890.97270.028*
H19B0.74150.91590.98880.028*
H19C0.92910.92650.92450.028*
C200.4410 (3)0.72805 (19)0.94254 (8)0.0164 (3)
H20A0.32260.69790.90960.025*
H20B0.36250.78690.97730.025*
H20C0.51840.64310.96740.025*
C210.4985 (3)0.95322 (19)0.86854 (9)0.0197 (4)
H21A0.37530.92720.83610.029*
H21B0.61231.01450.84230.029*
H21C0.42501.00530.90670.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0224 (2)0.0166 (2)0.0123 (2)−0.00013 (16)−0.00189 (15)0.00089 (15)
O10.0269 (7)0.0187 (7)0.0178 (6)−0.0001 (5)−0.0059 (5)−0.0022 (5)
O20.0291 (7)0.0214 (7)0.0161 (6)−0.0030 (5)−0.0045 (5)−0.0001 (5)
O30.0184 (6)0.0173 (6)0.0118 (5)0.0002 (5)0.0019 (4)0.0032 (5)
N10.0214 (7)0.0164 (8)0.0147 (6)0.0038 (6)0.0009 (5)0.0005 (6)
C10.0240 (8)0.0151 (9)0.0164 (8)0.0056 (7)−0.0031 (6)−0.0053 (7)
C20.0233 (8)0.0145 (9)0.0149 (8)0.0050 (7)−0.0009 (6)−0.0034 (6)
C30.0278 (9)0.0192 (10)0.0135 (8)0.0066 (7)−0.0025 (6)−0.0030 (7)
C40.0301 (9)0.0202 (10)0.0131 (7)0.0047 (7)0.0015 (7)0.0012 (7)
C50.0236 (9)0.0190 (9)0.0176 (8)0.0021 (7)0.0029 (7)0.0012 (7)
C60.0217 (8)0.0140 (9)0.0134 (7)0.0051 (7)0.0010 (6)−0.0015 (6)
C70.0193 (8)0.0175 (9)0.0143 (7)0.0010 (7)−0.0013 (6)0.0004 (6)
C80.0156 (7)0.0154 (9)0.0135 (7)−0.0001 (6)−0.0003 (6)−0.0001 (6)
C90.0154 (7)0.0163 (9)0.0143 (7)0.0008 (6)0.0003 (6)−0.0035 (6)
C100.0129 (7)0.0115 (8)0.0153 (7)−0.0007 (6)−0.0012 (6)−0.0017 (6)
C110.0123 (7)0.0132 (8)0.0122 (7)−0.0018 (6)−0.0013 (5)0.0000 (6)
C120.0121 (7)0.0125 (8)0.0135 (7)−0.0013 (6)−0.0003 (5)−0.0020 (6)
C130.0152 (7)0.0126 (8)0.0162 (8)0.0014 (6)−0.0009 (6)0.0004 (6)
C140.0154 (7)0.0125 (8)0.0172 (8)0.0013 (6)−0.0008 (6)−0.0016 (6)
C150.0145 (8)0.0162 (9)0.0242 (9)0.0035 (7)−0.0031 (6)−0.0011 (7)
C160.0190 (8)0.0137 (9)0.0312 (9)−0.0008 (7)−0.0021 (7)0.0000 (7)
C170.0285 (9)0.0186 (10)0.0224 (9)0.0108 (8)−0.0003 (7)−0.0045 (7)
C180.0155 (7)0.0120 (8)0.0147 (7)0.0009 (6)0.0011 (6)−0.0014 (6)
C190.0186 (8)0.0194 (9)0.0191 (8)−0.0016 (7)0.0014 (6)−0.0061 (7)
C200.0141 (7)0.0173 (9)0.0180 (8)−0.0001 (6)0.0020 (6)−0.0027 (7)
C210.0238 (9)0.0144 (9)0.0202 (8)0.0068 (7)0.0032 (7)−0.0017 (7)
Geometric parameters (Å, °) top
S1—C61.7634 (16)C12—C131.395 (2)
S1—C71.8239 (17)C12—C181.542 (2)
O1—C11.321 (2)C13—H130.9500
O1—H1O0.850 (10)C14—C171.538 (2)
O2—C11.230 (2)C14—C161.538 (2)
O3—C111.3817 (18)C14—C151.542 (2)
O3—H3O0.8400C15—H15A0.9800
N1—C51.337 (2)C15—H15B0.9800
N1—C61.342 (2)C15—H15C0.9800
C1—C21.471 (3)C16—H16A0.9800
C2—C31.394 (2)C16—H16B0.9800
C2—C61.415 (2)C16—H16C0.9800
C3—C41.380 (3)C17—H17A0.9800
C3—H30.9500C17—H17B0.9800
C4—C51.385 (2)C17—H17C0.9800
C4—H40.9500C18—C211.536 (2)
C5—H50.9500C18—C191.540 (2)
C7—C81.505 (2)C18—C201.539 (2)
C7—H7A0.9900C19—H19A0.9800
C7—H7B0.9900C19—H19B0.9800
C8—C91.386 (2)C19—H19C0.9800
C8—C131.387 (2)C20—H20A0.9800
C9—C101.393 (2)C20—H20B0.9800
C9—H90.9500C20—H20C0.9800
C10—C111.414 (2)C21—H21A0.9800
C10—C141.541 (2)C21—H21B0.9800
C11—C121.405 (2)C21—H21C0.9800
C6—S1—C7100.24 (8)C17—C14—C10111.47 (13)
C1—O1—H1O109.8 (18)C16—C14—C10110.37 (13)
C11—O3—H3O126.6C17—C14—C15105.58 (13)
C5—N1—C6118.43 (15)C16—C14—C15110.68 (14)
O2—C1—O1122.91 (17)C10—C14—C15111.98 (14)
O2—C1—C2122.32 (15)C14—C15—H15A109.5
O1—C1—C2114.77 (15)C14—C15—H15B109.5
C3—C2—C6117.92 (17)H15A—C15—H15B109.5
C3—C2—C1120.55 (15)C14—C15—H15C109.5
C6—C2—C1121.54 (15)H15A—C15—H15C109.5
C4—C3—C2120.04 (16)H15B—C15—H15C109.5
C4—C3—H3120.0C14—C16—H16A109.5
C2—C3—H3120.0C14—C16—H16B109.5
C3—C4—C5117.91 (16)H16A—C16—H16B109.5
C3—C4—H4121.0C14—C16—H16C109.5
C5—C4—H4121.0H16A—C16—H16C109.5
N1—C5—C4123.84 (17)H16B—C16—H16C109.5
N1—C5—H5118.1C14—C17—H17A109.5
C4—C5—H5118.1C14—C17—H17B109.5
N1—C6—C2121.87 (15)H17A—C17—H17B109.5
N1—C6—S1115.97 (12)C14—C17—H17C109.5
C2—C6—S1122.16 (14)H17A—C17—H17C109.5
C8—C7—S1107.24 (11)H17B—C17—H17C109.5
C8—C7—H7A110.3C21—C18—C19107.13 (14)
S1—C7—H7A110.3C21—C18—C20106.49 (13)
C8—C7—H7B110.3C19—C18—C20110.50 (13)
S1—C7—H7B110.3C21—C18—C12111.61 (13)
H7A—C7—H7B108.5C19—C18—C12109.74 (13)
C9—C8—C13119.07 (14)C20—C18—C12111.26 (14)
C9—C8—C7120.60 (15)C18—C19—H19A109.5
C13—C8—C7120.31 (15)C18—C19—H19B109.5
C8—C9—C10122.24 (15)H19A—C19—H19B109.5
C8—C9—H9118.9C18—C19—H19C109.5
C10—C9—H9118.9H19A—C19—H19C109.5
C9—C10—C11116.84 (15)H19B—C19—H19C109.5
C9—C10—C14120.15 (14)C18—C20—H20A109.5
C11—C10—C14122.99 (14)C18—C20—H20B109.5
O3—C11—C12116.25 (13)H20A—C20—H20B109.5
O3—C11—C10121.08 (14)C18—C20—H20C109.5
C12—C11—C10122.67 (14)H20A—C20—H20C109.5
C13—C12—C11117.06 (14)H20B—C20—H20C109.5
C13—C12—C18120.13 (14)C18—C21—H21A109.5
C11—C12—C18122.80 (14)C18—C21—H21B109.5
C8—C13—C12122.10 (15)H21A—C21—H21B109.5
C8—C13—H13118.9C18—C21—H21C109.5
C12—C13—H13118.9H21A—C21—H21C109.5
C17—C14—C16106.52 (15)H21B—C21—H21C109.5
O2—C1—C2—C3176.46 (16)C9—C10—C11—O3−179.75 (14)
O1—C1—C2—C3−4.1 (2)C14—C10—C11—O31.8 (2)
O2—C1—C2—C6−3.6 (3)C9—C10—C11—C120.3 (2)
O1—C1—C2—C6175.85 (15)C14—C10—C11—C12−178.16 (15)
C6—C2—C3—C4−0.1 (2)O3—C11—C12—C13−179.46 (13)
C1—C2—C3—C4179.83 (16)C10—C11—C12—C130.5 (2)
C2—C3—C4—C5−0.1 (3)O3—C11—C12—C181.9 (2)
C6—N1—C5—C4−0.3 (3)C10—C11—C12—C18−178.11 (14)
C3—C4—C5—N10.3 (3)C9—C8—C13—C120.6 (2)
C5—N1—C6—C20.0 (2)C7—C8—C13—C12179.43 (15)
C5—N1—C6—S1−179.54 (12)C11—C12—C13—C8−1.0 (2)
C3—C2—C6—N10.2 (3)C18—C12—C13—C8177.73 (15)
C1—C2—C6—N1−179.77 (15)C9—C10—C14—C173.8 (2)
C3—C2—C6—S1179.70 (12)C11—C10—C14—C17−177.85 (15)
C1—C2—C6—S1−0.2 (2)C9—C10—C14—C16−114.38 (17)
C7—S1—C6—N1−1.21 (15)C11—C10—C14—C1664.0 (2)
C7—S1—C6—C2179.23 (14)C9—C10—C14—C15121.83 (16)
C6—S1—C7—C8178.80 (11)C11—C10—C14—C15−59.8 (2)
S1—C7—C8—C985.94 (17)C13—C12—C18—C212.6 (2)
S1—C7—C8—C13−92.91 (16)C11—C12—C18—C21−178.80 (15)
C13—C8—C9—C100.3 (2)C13—C12—C18—C19−116.01 (16)
C7—C8—C9—C10−178.57 (15)C11—C12—C18—C1962.6 (2)
C8—C9—C10—C11−0.7 (2)C13—C12—C18—C20121.40 (16)
C8—C9—C10—C14177.77 (15)C11—C12—C18—C20−60.00 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···O2i0.85 (1)1.79 (1)2.640 (2)179 (3)
Symmetry codes: (i) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1o···O2i0.85 (1)1.79 (1)2.640 (2)179 (3)
Symmetry codes: (i) −x, −y+1, −z+1.
Acknowledgements top

We thank the University of Malaya (grant No. FS338/2008 A) for supporing this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Kim, T. H. & Lee, N. (2003). Bull. Kor. Chem. Soc., 24, 1809–1813.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Um, S.-I. & Lee, J.-Y. (2005). Dyes Pigm. 64, 93–99.

Westrip, S. P. (2008). publCIF. In preparation.