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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o730.
Published online 2009 March 11. doi:  10.1107/S1600536809007843
PMCID: PMC2968854

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

Abstract

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

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

An external file that holds a picture, illustration, etc.
Object name is e-65-0o730-scheme1.jpg

Experimental

Crystal data

  • C20H32N2O2S
  • M r = 364.54
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o730-efi1.jpg
  • a = 30.8643 (10) Å
  • b = 10.0128 (3) Å
  • c = 13.9596 (5) Å
  • β = 96.227 (2)°
  • V = 4288.6 (2) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.17 mm−1
  • T = 100 K
  • 0.25 × 0.15 × 0.10 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.960, T max = 0.984
  • 14652 measured reflections
  • 4886 independent reflections
  • 3240 reflections with I > 2σ(I)
  • R int = 0.052

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.135
  • S = 1.05
  • 4886 reflections
  • 237 parameters
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.28 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: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007843/tk2379sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007843/tk2379Isup2.hkl

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

Acknowledgments

We thank the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

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

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.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C20H32N2O2S at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii.

Crystal data

C20H32N2O2SF(000) = 1584
Mr = 364.54Dx = 1.129 Mg m3
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 mm1
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

Bruker SMART APEX diffractometer4886 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

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 = 1.05w = 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 Å3
0 restraintsΔρmin = −0.28 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2379).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Khusainova, N. G., Mostovaya, O. M., Azancheev, N. M., Litvinov, I. A., Krivolapov, B. D. & Cherkasov, R. A. (2004). Mendeleev Commun.14, 212–214.
  • MacLeay, R. E. & Meyers, T. D. (1989). Eur. Patent EP 303986 A2 19890222.
  • Myers, T. D. & MacLeay, R. E. (1989). Eur. Patent EP 306729 A1 19890315.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.

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