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Acta Cryst. (2009). E65, o730    [ doi:10.1107/S1600536809007843 ]

2-[(3,5-Di-tert-butyl-4-hydroxybenzyl)sulfanyl]-N'-isopropylideneacetohydrazide

W. A. Yehye, A. Ariffin and S. W. Ng

Abstract top

The title compound, C20H32N2O2S, the condensation product of a thioacetohydrazine and acetone, has a two-coordinate S atom and the angle at this atom is 100.7 (1)°. The (CH3)C=N-NH-C(O)- substituent engages in N-H...O hydrogen-bonding interactions with the substituent of an adjacent molecule across a center of inversion, generating a dimeric structure.

Related literature top

There are several structural studies of (CH3)C=N–NH–C(O)–X compounds; for N-acetyl-N'-isopropylidenehydrazine, see: Khusainova et al. (2004). For the synthesis of the thioacetohydrazine reactant, see: MacLeay & Meyers (1989); Myers & MacLeay (1989).

Experimental top

2-(3,5-Di-tert-butyl-4-hydroxybenzylthio)acetohydrazine (0.5 g, 1.54 mmol) and acetone (10 ml) were heated for 6 h; several drops of acetic acid were added to the reaction. The solvent was removed and the product recrystallized from hexane.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C–H 0.95–0.99 Å) and were included in the refinement in the riding model approximation with U(H) set to 1.2–1.5U(C). The oxygen- and nitrogen-bound H-atoms were similarly treated (O–H 0.84 and N–H 0.88 Å).

The hydroxy H-atom does not form a hydrogen bond; it is probably disordered over several positions. In one position, it is less than 2 Å from a hydrogen atom of the C14 methyl group. The two tert-butyl groups are probably also disordered, but the disorder could not be resolved into multiple positions.

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, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C20H32N2O2S at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.
2-[(3,5-Di-tert-butyl-4-hydroxybenzyl)sulfanyl]-N'- isopropylideneacetohydrazide top
Crystal data top
C20H32N2O2SF(000) = 1584
Mr = 364.54Dx = 1.129 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1963 reflections
a = 30.8643 (10) Åθ = 2.6–26.3°
b = 10.0128 (3) ŵ = 0.17 mm−1
c = 13.9596 (5) ÅT = 100 K
β = 96.227 (2)°Block, colorless
V = 4288.6 (2) Å30.25 × 0.15 × 0.10 mm
Z = 8
Data collection top
Bruker SMART APEX
diffractometer		4886 independent reflections
Radiation source: fine-focus sealed tube3240 reflections with I > 2σ(I)
graphiteRint = 0.052
ω scansθmax = 27.5°, θmin = 1.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −39→40
Tmin = 0.960, Tmax = 0.984k = −13→13
14652 measured reflectionsl = −18→14
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0627P)2 + 0.8959P]
where P = (Fo2 + 2Fc2)/3
4886 reflections(Δ/σ)max = 0.001
237 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.28 e Å−3
Crystal data top
C20H32N2O2SV = 4288.6 (2) Å3
Mr = 364.54Z = 8
Monoclinic, C2/cMo Kα radiation
a = 30.8643 (10) ŵ = 0.17 mm−1
b = 10.0128 (3) ÅT = 100 K
c = 13.9596 (5) Å0.25 × 0.15 × 0.10 mm
β = 96.227 (2)°
Data collection top
Bruker SMART APEX
diffractometer		4886 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3240 reflections with I > 2σ(I)
Tmin = 0.960, Tmax = 0.984Rint = 0.052
14652 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.135Δρmax = 0.31 e Å−3
S = 1.05Δρmin = −0.28 e Å−3
4886 reflectionsAbsolute structure: ?
237 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.394869 (18)0.18708 (5)0.52819 (4)0.02810 (16)
O10.32415 (5)0.04431 (14)0.08151 (10)0.0287 (4)
H1O0.34790.03040.05910.066 (10)*
O20.45752 (5)0.41852 (14)0.43360 (10)0.0284 (4)
N10.49822 (5)0.32105 (16)0.55791 (12)0.0228 (4)
H10.51090.39700.57620.033 (6)*
N20.51037 (5)0.20268 (16)0.60634 (12)0.0233 (4)
C10.34695 (6)0.22530 (19)0.35011 (14)0.0212 (4)
C20.31851 (6)0.11801 (18)0.33503 (15)0.0208 (4)
H20.30450.08510.38760.025*
C30.30992 (6)0.05737 (18)0.24556 (15)0.0205 (4)
C40.33196 (6)0.10754 (18)0.17019 (14)0.0207 (4)
C50.35919 (6)0.21967 (19)0.18074 (14)0.0206 (4)
C60.36638 (6)0.27540 (19)0.27299 (14)0.0213 (4)
H60.38530.35020.28300.026*
C70.27708 (7)−0.0579 (2)0.22932 (15)0.0257 (5)
C80.25474 (7)−0.0877 (2)0.31963 (16)0.0326 (5)
H8A0.2394−0.00770.33830.049*
H8B0.2767−0.11380.37230.049*
H8C0.2338−0.16060.30610.049*
C90.30019 (9)−0.1865 (2)0.2033 (2)0.0425 (6)
H9A0.2790−0.25940.19460.064*
H9B0.3229−0.20930.25540.064*
H9C0.3135−0.17290.14350.064*
C100.24093 (7)−0.0210 (2)0.14912 (17)0.0360 (6)
H10A0.22600.06000.16740.054*
H10B0.2199−0.09450.13980.054*
H10C0.2538−0.00490.08900.054*
C110.38057 (7)0.2813 (2)0.09618 (16)0.0284 (5)
C120.40558 (9)0.4089 (2)0.12623 (17)0.0404 (6)
H12A0.42930.38790.17640.061*
H12B0.38580.47340.15130.061*
H12C0.41770.44720.07030.061*
C130.34528 (10)0.3206 (3)0.01478 (18)0.0480 (7)
H13A0.32550.38610.03900.072*
H13B0.32870.2410−0.00780.072*
H13C0.35910.3596−0.03870.072*
C140.41348 (10)0.1852 (2)0.0594 (2)0.0544 (8)
H14A0.43420.15580.11350.082*
H14B0.42920.23070.01160.082*
H14C0.39810.10750.02970.082*
C150.35698 (7)0.2863 (2)0.44856 (14)0.0242 (5)
H15A0.32950.29680.47830.029*
H15B0.36950.37640.44170.029*
C160.44235 (7)0.18946 (19)0.46239 (16)0.0258 (5)
H16A0.46150.11280.48230.031*
H16B0.43320.18160.39240.031*
C170.46677 (6)0.3174 (2)0.48258 (14)0.0221 (4)
C180.54119 (7)0.2084 (2)0.67522 (15)0.0252 (5)
C190.55491 (8)0.0790 (2)0.72261 (16)0.0328 (5)
H19A0.53610.00700.69460.049*
H19B0.55240.08520.79190.049*
H19C0.58520.06000.71240.049*
C200.56467 (8)0.3315 (2)0.71190 (17)0.0376 (6)
H20A0.54350.40230.72030.056*
H20B0.58440.36070.66550.056*
H20C0.58160.31240.77390.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0292 (3)0.0299 (3)0.0231 (3)−0.0090 (2)−0.0063 (2)0.0075 (2)
O10.0321 (9)0.0280 (8)0.0264 (9)−0.0086 (7)0.0057 (7)−0.0100 (6)
O20.0270 (8)0.0279 (8)0.0286 (9)−0.0029 (6)−0.0044 (7)0.0037 (6)
N10.0219 (9)0.0237 (8)0.0219 (9)−0.0034 (7)−0.0018 (7)−0.0016 (7)
N20.0237 (9)0.0257 (9)0.0203 (9)0.0017 (7)0.0019 (7)0.0006 (7)
C10.0188 (10)0.0232 (9)0.0207 (11)0.0016 (8)−0.0024 (8)0.0014 (8)
C20.0174 (10)0.0224 (9)0.0223 (11)0.0006 (8)0.0009 (8)0.0044 (8)
C30.0170 (10)0.0193 (9)0.0243 (11)0.0003 (8)−0.0015 (8)0.0014 (8)
C40.0200 (10)0.0199 (9)0.0214 (11)−0.0004 (8)−0.0012 (8)−0.0024 (8)
C50.0208 (10)0.0201 (9)0.0208 (11)0.0006 (8)0.0015 (8)0.0007 (8)
C60.0190 (10)0.0193 (9)0.0244 (11)−0.0026 (8)−0.0031 (8)0.0013 (8)
C70.0237 (11)0.0250 (10)0.0282 (12)−0.0071 (9)0.0023 (9)−0.0018 (9)
C80.0303 (12)0.0305 (11)0.0373 (14)−0.0113 (10)0.0048 (10)0.0031 (10)
C90.0496 (16)0.0223 (11)0.0580 (18)−0.0087 (11)0.0172 (13)−0.0045 (11)
C100.0269 (12)0.0433 (13)0.0359 (14)−0.0155 (11)−0.0046 (10)−0.0016 (11)
C110.0367 (13)0.0260 (11)0.0232 (12)−0.0095 (9)0.0066 (10)0.0000 (9)
C120.0553 (16)0.0360 (13)0.0310 (14)−0.0208 (12)0.0096 (12)0.0026 (10)
C130.0673 (19)0.0478 (15)0.0261 (14)−0.0202 (14)−0.0072 (13)0.0108 (11)
C140.0605 (18)0.0398 (14)0.071 (2)−0.0102 (13)0.0424 (16)−0.0037 (14)
C150.0231 (11)0.0274 (10)0.0214 (11)−0.0001 (9)−0.0013 (9)0.0000 (8)
C160.0252 (11)0.0233 (10)0.0270 (12)0.0028 (9)−0.0065 (9)−0.0036 (9)
C170.0181 (10)0.0275 (10)0.0207 (11)−0.0004 (8)0.0024 (8)−0.0024 (9)
C180.0276 (11)0.0279 (11)0.0199 (11)0.0001 (9)0.0018 (9)−0.0020 (8)
C190.0395 (13)0.0323 (12)0.0253 (13)0.0048 (10)−0.0031 (10)−0.0029 (9)
C200.0441 (14)0.0353 (12)0.0294 (13)−0.0072 (11)−0.0145 (11)0.0031 (10)
Geometric parameters (Å, °) top
S1—C161.812 (2)C10—H10A0.9800
S1—C151.819 (2)C10—H10B0.9800
O1—C41.388 (2)C10—H10C0.9800
O1—H1O0.8400C11—C141.528 (3)
O2—C171.237 (2)C11—C121.527 (3)
N1—C171.352 (2)C11—C131.537 (3)
N1—N21.396 (2)C12—H12A0.9800
N1—H10.8800C12—H12B0.9800
N2—C181.278 (3)C12—H12C0.9800
C1—C61.382 (3)C13—H13A0.9800
C1—C21.389 (3)C13—H13B0.9800
C1—C151.505 (3)C13—H13C0.9800
C2—C31.388 (3)C14—H14A0.9800
C2—H20.9500C14—H14B0.9800
C3—C41.406 (3)C14—H14C0.9800
C3—C71.536 (3)C15—H15A0.9900
C4—C51.401 (3)C15—H15B0.9900
C5—C61.399 (3)C16—C171.498 (3)
C5—C111.542 (3)C16—H16A0.9900
C6—H60.9500C16—H16B0.9900
C7—C81.531 (3)C18—C201.493 (3)
C7—C91.535 (3)C18—C191.495 (3)
C7—C101.537 (3)C19—H19A0.9800
C8—H8A0.9800C19—H19B0.9800
C8—H8B0.9800C19—H19C0.9800
C8—H8C0.9800C20—H20A0.9800
C9—H9A0.9800C20—H20B0.9800
C9—H9B0.9800C20—H20C0.9800
C9—H9C0.9800
C16—S1—C15100.65 (10)C14—C11—C5111.09 (18)
C4—O1—H1O109.5C12—C11—C5111.70 (17)
C17—N1—N2119.11 (16)C13—C11—C5109.91 (19)
C17—N1—H1120.4C11—C12—H12A109.5
N2—N1—H1120.4C11—C12—H12B109.5
C18—N2—N1117.74 (17)H12A—C12—H12B109.5
C6—C1—C2118.89 (18)C11—C12—H12C109.5
C6—C1—C15120.02 (18)H12A—C12—H12C109.5
C2—C1—C15121.09 (18)H12B—C12—H12C109.5
C3—C2—C1122.04 (19)C11—C13—H13A109.5
C3—C2—H2119.0C11—C13—H13B109.5
C1—C2—H2119.0H13A—C13—H13B109.5
C2—C3—C4117.15 (17)C11—C13—H13C109.5
C2—C3—C7121.32 (18)H13A—C13—H13C109.5
C4—C3—C7121.52 (17)H13B—C13—H13C109.5
O1—C4—C5120.24 (17)C11—C14—H14A109.5
O1—C4—C3116.94 (17)C11—C14—H14B109.5
C5—C4—C3122.76 (18)H14A—C14—H14B109.5
C6—C5—C4116.74 (18)C11—C14—H14C109.5
C6—C5—C11120.44 (17)H14A—C14—H14C109.5
C4—C5—C11122.82 (17)H14B—C14—H14C109.5
C1—C6—C5122.24 (18)C1—C15—S1113.01 (14)
C1—C6—H6118.9C1—C15—H15A109.0
C5—C6—H6118.9S1—C15—H15A109.0
C8—C7—C9107.06 (18)C1—C15—H15B109.0
C8—C7—C3111.95 (17)S1—C15—H15B109.0
C9—C7—C3110.44 (17)H15A—C15—H15B107.8
C8—C7—C10106.88 (18)C17—C16—S1109.51 (14)
C9—C7—C10110.41 (19)C17—C16—H16A109.8
C3—C7—C10110.01 (17)S1—C16—H16A109.8
C7—C8—H8A109.5C17—C16—H16B109.8
C7—C8—H8B109.5S1—C16—H16B109.8
H8A—C8—H8B109.5H16A—C16—H16B108.2
C7—C8—H8C109.5O2—C17—N1120.74 (18)
H8A—C8—H8C109.5O2—C17—C16120.97 (18)
H8B—C8—H8C109.5N1—C17—C16118.26 (18)
C7—C9—H9A109.5N2—C18—C20126.07 (19)
C7—C9—H9B109.5N2—C18—C19116.51 (19)
H9A—C9—H9B109.5C20—C18—C19117.41 (19)
C7—C9—H9C109.5C18—C19—H19A109.5
H9A—C9—H9C109.5C18—C19—H19B109.5
H9B—C9—H9C109.5H19A—C19—H19B109.5
C7—C10—H10A109.5C18—C19—H19C109.5
C7—C10—H10B109.5H19A—C19—H19C109.5
H10A—C10—H10B109.5H19B—C19—H19C109.5
C7—C10—H10C109.5C18—C20—H20A109.5
H10A—C10—H10C109.5C18—C20—H20B109.5
H10B—C10—H10C109.5H20A—C20—H20B109.5
C14—C11—C12106.5 (2)C18—C20—H20C109.5
C14—C11—C13110.9 (2)H20A—C20—H20C109.5
C12—C11—C13106.61 (18)H20B—C20—H20C109.5
C17—N1—N2—C18177.73 (18)C4—C3—C7—C965.2 (3)
C6—C1—C2—C31.8 (3)C2—C3—C7—C10122.0 (2)
C15—C1—C2—C3−177.81 (18)C4—C3—C7—C10−56.9 (2)
C1—C2—C3—C41.2 (3)C6—C5—C11—C14114.5 (2)
C1—C2—C3—C7−177.73 (18)C4—C5—C11—C14−65.8 (3)
C2—C3—C4—O1178.34 (17)C6—C5—C11—C12−4.3 (3)
C7—C3—C4—O1−2.8 (3)C4—C5—C11—C12175.47 (19)
C2—C3—C4—C5−4.5 (3)C6—C5—C11—C13−122.4 (2)
C7—C3—C4—C5174.38 (18)C4—C5—C11—C1357.3 (3)
O1—C4—C5—C6−178.28 (17)C6—C1—C15—S1−102.63 (19)
C3—C4—C5—C64.7 (3)C2—C1—C15—S177.0 (2)
O1—C4—C5—C111.9 (3)C16—S1—C15—C161.45 (16)
C3—C4—C5—C11−175.14 (19)C15—S1—C16—C1781.49 (15)
C2—C1—C6—C5−1.6 (3)N2—N1—C17—O2−174.54 (18)
C15—C1—C6—C5178.00 (18)N2—N1—C17—C167.7 (3)
C4—C5—C6—C1−1.5 (3)S1—C16—C17—O2−87.7 (2)
C11—C5—C6—C1178.29 (18)S1—C16—C17—N189.99 (19)
C2—C3—C7—C83.3 (3)N1—N2—C18—C202.5 (3)
C4—C3—C7—C8−175.55 (18)N1—N2—C18—C19−177.17 (17)
C2—C3—C7—C9−115.9 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.882.102.940 (2)159
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.882.102.940 (2)159
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

We thank the University of Malaya for supporting this study.

references
References top

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Westrip, S. P. (2009). publCIF. In preparation.