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Acta Cryst. (2009). E65, o2112    [ doi:10.1107/S1600536809030645 ]

2-(3,5-Di-tert-butyl-4-hydroxybenzylsulfanyl)-N'-(3-methoxybenzylidene)acetohydrazide

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

Abstract top

The title compound, C25H34N2O3S, is a derivative of N'-benzylideneacetohydrazide having substituents on the acetyl and benzylidenyl parts, and displays a planar Ccarbonyl-NH-NCanisyl fragment [torsion angle = 174.9 (3)°]. The -NH- unit forms an N-H...O hydrogen bond with the carbonyl O atom of an inversion-related molecule.

Related literature top

For N-(benzylidene)acetohydrazide, see: Litvinov et al. (1991).

Experimental top

2-(3,5-Di-tert-butyl-4-hydroxybenzylthio)acetohydrazine (0.5 g, 1.54 mmol) and 3-methoxybenzaldehyde (0.21 g, 1.54 mmol) were heated in toluene (10 ml) for 4 h in the presence of p-toluene sulphonic acid as catalyst. The cool mixture was poured onto ice; the resulting solid was collected, dried and recrystallized from toluene in 70% yield.

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 to 1.5U(C). The imino H-atom was similarly treated (N–H 0.88 Å).; the hydroxy H-atom was placed in a position such that all H···H contacts exceeded 2.0 Å (O–H 0.84 Å).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 C25H34N2O3S at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
2-(3,5-Di-tert-butyl-4-hydroxybenzylsulfanyl)-N'-(3- methoxybenzylidene)acetohydrazide top
Crystal data top
C25H34N2O3SZ = 2
Mr = 442.60F(000) = 476
Triclinic, P1Dx = 1.190 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.9952 (2) ÅCell parameters from 1620 reflections
b = 10.3199 (3) Åθ = 2.6–21.7°
c = 20.6141 (7) ŵ = 0.16 mm−1
α = 97.279 (2)°T = 223 K
β = 95.916 (2)°Prism, colorless
γ = 99.981 (2)°0.35 × 0.10 × 0.10 mm
V = 1235.72 (7) Å3
Data collection top
Bruker SMART APEX
diffractometer		4294 independent reflections
Radiation source: fine-focus sealed tube2577 reflections with I > 2σ(I)
graphiteRint = 0.035
ω scansθmax = 25.0°, θmin = 1.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −7→7
Tmin = 0.947, Tmax = 0.984k = −12→12
8285 measured reflectionsl = −24→23
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)] = 0.075Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.219H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.1218P)2]
where P = (Fo2 + 2Fc2)/3
4294 reflections(Δ/σ)max = 0.001
287 parametersΔρmax = 0.61 e Å−3
0 restraintsΔρmin = −0.27 e Å−3
Crystal data top
C25H34N2O3Sγ = 99.981 (2)°
Mr = 442.60V = 1235.72 (7) Å3
Triclinic, P1Z = 2
a = 5.9952 (2) ÅMo Kα radiation
b = 10.3199 (3) ŵ = 0.16 mm−1
c = 20.6141 (7) ÅT = 223 K
α = 97.279 (2)°0.35 × 0.10 × 0.10 mm
β = 95.916 (2)°
Data collection top
Bruker SMART APEX
diffractometer		4294 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2577 reflections with I > 2σ(I)
Tmin = 0.947, Tmax = 0.984Rint = 0.035
8285 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.075H-atom parameters constrained
wR(F2) = 0.219Δρmax = 0.61 e Å−3
S = 1.06Δρmin = −0.27 e Å−3
4294 reflectionsAbsolute structure: ?
287 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
S10.75715 (19)0.78337 (10)0.36105 (5)0.0691 (4)
O10.1621 (4)0.5619 (2)0.06464 (11)0.0613 (8)
H1O0.25380.50930.06050.092*
O20.4442 (5)0.5039 (2)0.40994 (12)0.0635 (8)
O31.6583 (5)0.8943 (3)0.72616 (13)0.0731 (9)
N10.7590 (5)0.5928 (3)0.48032 (14)0.0545 (8)
H10.69260.56600.51370.065*
N20.9784 (5)0.6642 (3)0.49141 (14)0.0531 (8)
C10.2353 (5)0.6087 (3)0.13041 (16)0.0433 (8)
C20.1613 (5)0.5357 (3)0.17936 (15)0.0400 (8)
C30.2413 (6)0.5907 (3)0.24438 (16)0.0435 (8)
H30.19650.54250.27810.052*
C40.3841 (6)0.7132 (3)0.26141 (15)0.0424 (8)
C50.4527 (6)0.7824 (3)0.21091 (16)0.0454 (9)
H50.55170.86540.22210.054*
C60.3814 (5)0.7343 (3)0.14524 (16)0.0432 (9)
C7−0.0028 (6)0.3992 (3)0.16267 (18)0.0495 (9)
C8−0.0615 (7)0.3430 (4)0.22584 (19)0.0628 (11)
H8A0.07780.33300.25160.094*
H8B−0.16230.25700.21410.094*
H8C−0.13670.40360.25170.094*
C90.1096 (7)0.2961 (4)0.1244 (2)0.0632 (11)
H9A0.15370.32750.08430.095*
H9B0.00230.21240.11320.095*
H9C0.24400.28340.15150.095*
C10−0.2303 (7)0.4132 (4)0.1249 (2)0.0725 (13)
H10A−0.20180.44750.08420.109*
H10B−0.30190.47410.15180.109*
H10C−0.33070.32680.11470.109*
C110.4605 (6)0.8127 (4)0.09063 (17)0.0538 (10)
C120.2542 (7)0.8470 (4)0.04992 (19)0.0673 (12)
H12A0.15210.76560.02910.101*
H12B0.30700.89820.01630.101*
H12C0.17350.89890.07870.101*
C130.6181 (8)0.9471 (4)0.1203 (2)0.0835 (15)
H13A0.75360.93060.14540.125*
H13B0.53720.99880.14900.125*
H13C0.66210.99590.08490.125*
C140.5967 (7)0.7360 (5)0.0464 (2)0.0770 (14)
H14A0.73160.72100.07240.115*
H14B0.64240.78700.01190.115*
H14C0.50300.65110.02660.115*
C150.4592 (7)0.7738 (3)0.33293 (17)0.0567 (10)
H15A0.36800.72110.36070.068*
H15B0.42530.86370.33920.068*
C160.7607 (7)0.6107 (4)0.36385 (18)0.0634 (11)
H16A0.68440.55810.32200.076*
H16B0.91910.59760.36930.076*
C170.6438 (7)0.5632 (3)0.41904 (18)0.0519 (9)
C181.0622 (6)0.6942 (3)0.55202 (18)0.0484 (9)
H180.97390.66580.58450.058*
C191.2932 (6)0.7721 (3)0.57209 (17)0.0456 (9)
C201.4309 (7)0.8176 (4)0.52624 (19)0.0574 (10)
H201.37570.80050.48100.069*
C211.6485 (8)0.8877 (4)0.5475 (2)0.0653 (11)
H211.74180.91770.51640.078*
C221.7322 (7)0.9150 (3)0.6137 (2)0.0547 (10)
H221.88150.96260.62760.066*
C231.5954 (7)0.8718 (3)0.65910 (18)0.0519 (9)
C241.3768 (6)0.8000 (3)0.63807 (17)0.0475 (9)
H241.28430.76980.66930.057*
C251.8769 (8)0.9736 (5)0.7502 (2)0.0793 (14)
H25A1.90130.98190.79790.119*
H25B1.88431.06120.73720.119*
H25C1.99400.93190.73180.119*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0859 (8)0.0701 (7)0.0346 (6)−0.0270 (6)−0.0044 (5)0.0117 (4)
O10.0721 (17)0.0705 (17)0.0310 (14)−0.0100 (14)−0.0009 (12)0.0066 (11)
O20.085 (2)0.0483 (15)0.0520 (17)0.0036 (14)−0.0108 (14)0.0139 (12)
O30.082 (2)0.0767 (19)0.0480 (17)−0.0086 (16)−0.0075 (14)0.0083 (13)
N10.070 (2)0.0470 (17)0.0455 (19)0.0155 (16)−0.0058 (16)0.0090 (13)
N20.063 (2)0.0553 (18)0.0430 (19)0.0242 (16)−0.0048 (15)0.0065 (14)
C10.0435 (19)0.054 (2)0.0297 (18)0.0018 (16)0.0059 (14)0.0076 (15)
C20.0431 (18)0.0427 (19)0.0349 (19)0.0042 (15)0.0099 (15)0.0092 (14)
C30.055 (2)0.0402 (19)0.038 (2)0.0082 (16)0.0128 (16)0.0129 (15)
C40.059 (2)0.0423 (19)0.0268 (18)0.0117 (16)0.0039 (15)0.0062 (14)
C50.055 (2)0.0417 (18)0.0359 (19)−0.0017 (16)−0.0001 (15)0.0112 (14)
C60.0425 (19)0.050 (2)0.0348 (19)−0.0036 (16)0.0046 (15)0.0146 (15)
C70.050 (2)0.048 (2)0.048 (2)−0.0032 (17)0.0141 (17)0.0076 (16)
C80.080 (3)0.049 (2)0.060 (3)−0.002 (2)0.026 (2)0.0144 (18)
C90.070 (3)0.051 (2)0.064 (3)−0.003 (2)0.019 (2)−0.0008 (19)
C100.052 (2)0.072 (3)0.087 (3)−0.010 (2)0.005 (2)0.019 (2)
C110.058 (2)0.063 (2)0.034 (2)−0.0093 (19)−0.0006 (17)0.0154 (17)
C120.072 (3)0.078 (3)0.049 (2)−0.004 (2)0.000 (2)0.033 (2)
C130.097 (3)0.080 (3)0.056 (3)−0.039 (3)−0.006 (2)0.031 (2)
C140.064 (3)0.111 (4)0.054 (3)−0.007 (3)0.019 (2)0.027 (2)
C150.091 (3)0.0354 (19)0.043 (2)0.0132 (19)0.004 (2)0.0085 (15)
C160.064 (2)0.086 (3)0.039 (2)0.027 (2)0.0017 (18)−0.0077 (19)
C170.070 (3)0.042 (2)0.043 (2)0.0183 (19)−0.0060 (19)0.0027 (16)
C180.061 (2)0.0413 (19)0.046 (2)0.0183 (17)0.0036 (18)0.0109 (16)
C190.059 (2)0.0429 (19)0.040 (2)0.0186 (17)0.0070 (17)0.0114 (15)
C200.073 (3)0.063 (2)0.043 (2)0.025 (2)0.0118 (19)0.0108 (18)
C210.081 (3)0.068 (3)0.059 (3)0.028 (2)0.030 (2)0.023 (2)
C220.055 (2)0.045 (2)0.068 (3)0.0146 (18)0.015 (2)0.0109 (18)
C230.063 (2)0.041 (2)0.051 (2)0.0108 (18)0.0031 (19)0.0114 (17)
C240.060 (2)0.0440 (19)0.040 (2)0.0101 (17)0.0085 (17)0.0112 (15)
C250.073 (3)0.080 (3)0.073 (3)0.002 (2)−0.019 (2)0.005 (2)
Geometric parameters (Å, °) top
S1—C161.794 (4)C10—H10C0.9700
S1—C151.802 (4)C11—C141.524 (6)
O1—C11.379 (4)C11—C121.540 (5)
O1—H1O0.8400C11—C131.549 (5)
O2—C171.230 (4)C12—H12A0.9700
O3—C231.374 (4)C12—H12B0.9700
O3—C251.423 (5)C12—H12C0.9700
N1—C171.347 (4)C13—H13A0.9700
N1—N21.373 (4)C13—H13B0.9700
N1—H10.8800C13—H13C0.9700
N2—C181.276 (4)C14—H14A0.9700
C1—C21.397 (4)C14—H14B0.9700
C1—C61.411 (4)C14—H14C0.9700
C2—C31.389 (4)C15—H15A0.9800
C2—C71.548 (4)C15—H15B0.9800
C3—C41.380 (4)C16—C171.487 (5)
C3—H30.9400C16—H16A0.9800
C4—C51.392 (4)C16—H16B0.9800
C4—C151.516 (5)C18—C191.465 (5)
C5—C61.378 (5)C18—H180.9400
C5—H50.9400C19—C241.376 (5)
C6—C111.534 (4)C19—C201.391 (5)
C7—C101.538 (5)C20—C211.375 (6)
C7—C91.534 (5)C20—H200.9400
C7—C81.540 (5)C21—C221.382 (5)
C8—H8A0.9700C21—H210.9400
C8—H8B0.9700C22—C231.373 (5)
C8—H8C0.9700C22—H220.9400
C9—H9A0.9700C23—C241.385 (5)
C9—H9B0.9700C24—H240.9400
C9—H9C0.9700C25—H25A0.9700
C10—H10A0.9700C25—H25B0.9700
C10—H10B0.9700C25—H25C0.9700
C16—S1—C15100.04 (17)C11—C12—H12C109.5
C1—O1—H1O95.8H12A—C12—H12C109.5
C23—O3—C25117.4 (3)H12B—C12—H12C109.5
C17—N1—N2120.9 (3)C11—C13—H13A109.5
C17—N1—H1119.6C11—C13—H13B109.5
N2—N1—H1119.6H13A—C13—H13B109.5
C18—N2—N1114.8 (3)C11—C13—H13C109.5
O1—C1—C2120.9 (3)H13A—C13—H13C109.5
O1—C1—C6116.7 (3)H13B—C13—H13C109.5
C2—C1—C6122.4 (3)C11—C14—H14A109.5
C3—C2—C1117.1 (3)C11—C14—H14B109.5
C3—C2—C7120.8 (3)H14A—C14—H14B109.5
C1—C2—C7122.0 (3)C11—C14—H14C109.5
C4—C3—C2122.6 (3)H14A—C14—H14C109.5
C4—C3—H3118.7H14B—C14—H14C109.5
C2—C3—H3118.7C4—C15—S1115.0 (3)
C3—C4—C5118.1 (3)C4—C15—H15A108.5
C3—C4—C15121.4 (3)S1—C15—H15A108.5
C5—C4—C15120.4 (3)C4—C15—H15B108.5
C6—C5—C4122.7 (3)S1—C15—H15B108.5
C6—C5—H5118.7H15A—C15—H15B107.5
C4—C5—H5118.7C17—C16—S1111.4 (3)
C5—C6—C1117.0 (3)C17—C16—H16A109.4
C5—C6—C11121.5 (3)S1—C16—H16A109.4
C1—C6—C11121.5 (3)C17—C16—H16B109.4
C10—C7—C9111.7 (3)S1—C16—H16B109.4
C10—C7—C8106.5 (3)H16A—C16—H16B108.0
C9—C7—C8105.8 (3)O2—C17—N1120.4 (4)
C10—C7—C2110.6 (3)O2—C17—C16121.4 (3)
C9—C7—C2110.9 (3)N1—C17—C16118.1 (4)
C8—C7—C2111.1 (3)N2—C18—C19121.4 (3)
C7—C8—H8A109.5N2—C18—H18119.3
C7—C8—H8B109.5C19—C18—H18119.3
H8A—C8—H8B109.5C24—C19—C20119.1 (3)
C7—C8—H8C109.5C24—C19—C18119.1 (3)
H8A—C8—H8C109.5C20—C19—C18121.8 (3)
H8B—C8—H8C109.5C21—C20—C19119.6 (4)
C7—C9—H9A109.5C21—C20—H20120.2
C7—C9—H9B109.5C19—C20—H20120.2
H9A—C9—H9B109.5C20—C21—C22121.1 (4)
C7—C9—H9C109.5C20—C21—H21119.4
H9A—C9—H9C109.5C22—C21—H21119.4
H9B—C9—H9C109.5C23—C22—C21119.4 (4)
C7—C10—H10A109.5C23—C22—H22120.3
C7—C10—H10B109.5C21—C22—H22120.3
H10A—C10—H10B109.5C22—C23—O3124.7 (3)
C7—C10—H10C109.5C22—C23—C24119.8 (4)
H10A—C10—H10C109.5O3—C23—C24115.5 (3)
H10B—C10—H10C109.5C19—C24—C23121.0 (3)
C14—C11—C6111.2 (3)C19—C24—H24119.5
C14—C11—C12110.8 (3)C23—C24—H24119.5
C6—C11—C12110.4 (3)O3—C25—H25A109.5
C14—C11—C13107.0 (3)O3—C25—H25B109.5
C6—C11—C13111.0 (3)H25A—C25—H25B109.5
C12—C11—C13106.3 (3)O3—C25—H25C109.5
C11—C12—H12A109.5H25A—C25—H25C109.5
C11—C12—H12B109.5H25B—C25—H25C109.5
H12A—C12—H12B109.5
C17—N1—N2—C18174.9 (3)C1—C6—C11—C1262.1 (5)
O1—C1—C2—C3−179.3 (3)C5—C6—C11—C13−1.3 (5)
C6—C1—C2—C3−1.2 (5)C1—C6—C11—C13179.7 (4)
O1—C1—C2—C70.7 (5)C3—C4—C15—S1111.0 (3)
C6—C1—C2—C7178.8 (3)C5—C4—C15—S1−71.0 (4)
C1—C2—C3—C41.3 (5)C16—S1—C15—C4−71.7 (3)
C7—C2—C3—C4−178.7 (3)C15—S1—C16—C17−71.2 (3)
C2—C3—C4—C5−1.2 (5)N2—N1—C17—O2−177.0 (3)
C2—C3—C4—C15176.9 (3)N2—N1—C17—C16−0.3 (5)
C3—C4—C5—C60.9 (5)S1—C16—C17—O297.8 (4)
C15—C4—C5—C6−177.2 (3)S1—C16—C17—N1−78.9 (4)
C4—C5—C6—C1−0.8 (5)N1—N2—C18—C19−179.0 (3)
C4—C5—C6—C11−179.8 (3)N2—C18—C19—C24−179.0 (3)
O1—C1—C6—C5179.1 (3)N2—C18—C19—C200.5 (5)
C2—C1—C6—C51.0 (5)C24—C19—C20—C210.9 (5)
O1—C1—C6—C11−1.8 (5)C18—C19—C20—C21−178.5 (3)
C2—C1—C6—C11−180.0 (3)C19—C20—C21—C22−0.6 (6)
C3—C2—C7—C10119.7 (4)C20—C21—C22—C23−0.3 (6)
C1—C2—C7—C10−60.3 (5)C21—C22—C23—O3−179.1 (3)
C3—C2—C7—C9−115.8 (4)C21—C22—C23—C241.0 (5)
C1—C2—C7—C964.3 (4)C25—O3—C23—C223.3 (5)
C3—C2—C7—C81.6 (5)C25—O3—C23—C24−176.8 (4)
C1—C2—C7—C8−178.4 (3)C20—C19—C24—C23−0.3 (5)
C5—C6—C11—C14117.7 (4)C18—C19—C24—C23179.2 (3)
C1—C6—C11—C14−61.3 (4)C22—C23—C24—C19−0.7 (5)
C5—C6—C11—C12−118.9 (4)O3—C23—C24—C19179.4 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O2i0.882.002.884 (4)176
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···O2i0.882.002.884 (4)176
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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