5-Ethyl-5-methyl-4-phenyl-5H-1,2,4-triazol-3(4H)-thione

Tan, K.W.; Maah, M.J.; Ng, S.W.

doi:10.1107/S1600536810030503

organic compounds

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Volume 66| Part 9| September 2010| Page o2224

https://doi.org/10.1107/S1600536810030503

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5-Ethyl-5-methyl-4-phenyl-5H-1,2,4-triazol-3(4H)-thione

Kong Wai Tan,^a M. Jamil Maah ^a ^* and Seik Weng Ng ^a

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: mjamil@um.edu.my

(Received 30 July 2010; accepted 30 July 2010; online 11 August 2010)

The five-membered ring of the title compound Δ¹-1,2,4-triazoline-5-thione, C₁₁H₁₃N₃S, is almost planar (r.m.s. deviation = 0.009 Å); the phenyl ring is aligned at 84.6 (2)° with respect to the five-membered ring. The crystal studied was a racemic twin with an approximate 20% minor twin component. Weak intermolecular C—H⋯N hydrogen bonding is present in the crystal structure.

Related literature

For the synthesis of this and other Δ¹-[1,2,4]-triazoline-5-thiones, see: Kabashima et al. (1991 ); Landquist (1970 ); Tripathi & Dhar (1986 ). For the crystal structure of the related compound 5,5-dimethyl-4-phenyl-1,2,4-triazol-3-thione, see: Katritzky et al. (1984 ).

Experimental

Crystal data

C₁₁H₁₃N₃S
M_r = 219.30
Tetragonal, $[P \overline 42_1 c ]$
a = 17.962 (4) Å
c = 6.9992 (14) Å
V = 2258.2 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 100 K
0.30 × 0.05 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.927, T_max = 0.987
10418 measured reflections
1987 independent reflections
1546 reflections with I > 2σ(I)
R_int = 0.087

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.186
S = 1.07
1987 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.31 e Å⁻³
Absolute structure: Flack (1983 ), 837 Friedel pairs
Flack parameter: −0.2 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9A⋯N2ⁱ	0.98	2.56	3.519 (9)	165
Symmetry code: (i) -y+1, x, -z+2.

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810030503/xu5008sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030503/xu5008Isup2.hkl

checkCIF report

Comment top

3-Phenyl-Δ¹-[1,2,4]-triazoline-5-thiones are synthesized by the heterocyclization of the Schiff base condensation product of the reaction between phenylthiosemicarbazide and a ketone in the presence of chlorocarbonylsulfenyl chloride (Kabashima et al., 1991), chlorosulfonyl isocyanate (Tripathi & Dhar, 1986) and manganese dioxide (Landquist, 1970). In the present study, the oxidizing agent is 1,10-phenanthroline-5,6-dione, commonly known as phendione. 4-Phenyl thiosemicarbazide condensed with methyl ethyl ketone to form the initial Schiff base, which was then oxidized to the title compound by phendione (Scheme I, Fig. 1). Intermolecular weak C—H···N hydrogen bonding is present in the crystal structure (Table 1).

Related literature top

For the synthesis of this and other Δ¹-[1,2,4]-triazoline-5-thiones, see: Kabashima et al. (1991); Landquist (1970); Tripathi & Dhar (1986). For the crystal structure of the related compound 5,5-dimethyl-4-phenyl-1,2,4-triazol-3-thione, see: Katritzky et al. (1984).

Experimental top

4-Phenyl thiosemicarbazide (2 mmol, 0.33 g) and 1,10-phenanthroline-5,6-dione (1 mmol, 0.21 g) were heated in a mixture of methyl ethyl ketone (5 ml) and ethanol (10 ml). The yellow precipitate that formed was removed by filtration. Slow evaporation of the orange filtrate afforded the title compound.

Structure description top

For the synthesis of this and other Δ¹-[1,2,4]-triazoline-5-thiones, see: Kabashima et al. (1991); Landquist (1970); Tripathi & Dhar (1986). For the crystal structure of the related compound 5,5-dimethyl-4-phenyl-1,2,4-triazol-3-thione, see: Katritzky et al. (1984).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₁H₁₃N₃S at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

5-Ethyl-5-methyl-4-phenyl-5H-1,2,4-triazol-3(4H)-thione top

Crystal data top

C₁₁H₁₃N₃S	D_x = 1.290 Mg m⁻³
M_r = 219.30	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42₁c	Cell parameters from 926 reflections
Hall symbol: P -4 2n	θ = 2.5–18.5°
a = 17.962 (4) Å	µ = 0.26 mm⁻¹
c = 6.9992 (14) Å	T = 100 K
V = 2258.2 (6) Å³	Prism, orange
Z = 8	0.30 × 0.05 × 0.05 mm
F(000) = 928

Data collection top

Bruker SMART APEX diffractometer	1987 independent reflections
Radiation source: fine-focus sealed tube	1546 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→20
T_min = 0.927, T_max = 0.987	k = −21→21
10418 measured reflections	l = −8→5

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.065	H-atom parameters constrained
wR(F²) = 0.186	w = 1/[σ²(F_o²) + (0.0992P)² + 1.8759P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1987 reflections	Δρ_max = 0.69 e Å⁻³
136 parameters	Δρ_min = −0.31 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 837 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.2 (2)

Crystal data top

C₁₁H₁₃N₃S	Z = 8
M_r = 219.30	Mo Kα radiation
Tetragonal, P42₁c	µ = 0.26 mm⁻¹
a = 17.962 (4) Å	T = 100 K
c = 6.9992 (14) Å	0.30 × 0.05 × 0.05 mm
V = 2258.2 (6) Å³

Data collection top

Bruker SMART APEX diffractometer	1987 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1546 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.987	R_int = 0.087
10418 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	H-atom parameters constrained
wR(F²) = 0.186	Δρ_max = 0.69 e Å⁻³
S = 1.07	Δρ_min = −0.31 e Å⁻³
1987 reflections	Absolute structure: Flack (1983), 837 Friedel pairs
136 parameters	Absolute structure parameter: −0.2 (2)
0 restraints

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

	x	y	z	U_iso*/U_eq
S1	0.47452 (8)	0.23341 (7)	1.2411 (2)	0.0351 (4)
N1	0.4463 (3)	0.2810 (3)	0.8841 (6)	0.0351 (11)
N2	0.4094 (3)	0.3589 (3)	1.1143 (7)	0.0531 (15)
N3	0.3934 (3)	0.3924 (3)	0.9623 (8)	0.0511 (14)
C1	0.4778 (3)	0.2198 (2)	0.7806 (6)	0.0237 (10)
C2	0.5518 (3)	0.2275 (3)	0.7230 (8)	0.0353 (13)
H2	0.5801	0.2706	0.7530	0.042*
C3	0.5823 (3)	0.1677 (3)	0.6175 (9)	0.0441 (15)
H3	0.6323	0.1704	0.5738	0.053*
C4	0.5409 (4)	0.1065 (3)	0.5785 (8)	0.0480 (17)
H4	0.5623	0.0671	0.5066	0.058*
C5	0.4687 (4)	0.1003 (3)	0.6404 (8)	0.0435 (15)
H5	0.4406	0.0568	0.6136	0.052*
C6	0.4381 (3)	0.1576 (3)	0.7413 (9)	0.0351 (12)
H6	0.3881	0.1537	0.7846	0.042*
C7	0.4431 (3)	0.2869 (3)	1.0741 (7)	0.0371 (14)
C8	0.4127 (3)	0.3477 (3)	0.7940 (8)	0.0398 (14)
C9	0.4652 (4)	0.3911 (3)	0.6695 (9)	0.0525 (17)
H9A	0.5098	0.4041	0.7429	0.079*
H9B	0.4407	0.4367	0.6254	0.079*
H9C	0.4794	0.3607	0.5590	0.079*
C10	0.3418 (3)	0.3257 (4)	0.6851 (9)	0.0528 (18)
H10A	0.3210	0.3707	0.6231	0.063*
H10B	0.3554	0.2902	0.5828	0.063*
C11	0.2824 (4)	0.2911 (5)	0.8070 (11)	0.073 (2)
H11A	0.2391	0.2789	0.7276	0.109*
H11B	0.2675	0.3262	0.9072	0.109*
H11C	0.3017	0.2455	0.8659	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0531 (8)	0.0347 (6)	0.0174 (6)	−0.0009 (6)	−0.0038 (7)	0.0016 (7)
N1	0.051 (3)	0.033 (2)	0.021 (2)	0.014 (2)	−0.004 (2)	−0.001 (2)
N2	0.069 (4)	0.058 (3)	0.033 (3)	0.025 (3)	−0.008 (3)	−0.007 (3)
N3	0.058 (3)	0.048 (3)	0.047 (3)	0.010 (3)	−0.015 (3)	−0.009 (3)
C1	0.035 (2)	0.024 (2)	0.012 (2)	0.0085 (19)	−0.006 (2)	0.000 (2)
C2	0.042 (3)	0.031 (3)	0.032 (3)	−0.009 (2)	−0.009 (3)	0.000 (3)
C3	0.036 (3)	0.055 (4)	0.041 (4)	0.012 (3)	0.015 (3)	0.008 (3)
C4	0.088 (5)	0.034 (3)	0.022 (3)	0.023 (3)	0.001 (3)	0.002 (3)
C5	0.072 (4)	0.029 (3)	0.029 (3)	−0.006 (3)	−0.010 (3)	−0.003 (2)
C6	0.038 (3)	0.038 (3)	0.030 (3)	−0.001 (2)	0.006 (3)	0.001 (3)
C7	0.053 (4)	0.042 (3)	0.016 (3)	0.019 (2)	−0.002 (2)	−0.008 (2)
C8	0.044 (3)	0.039 (3)	0.037 (4)	0.006 (2)	−0.001 (3)	−0.001 (3)
C9	0.059 (4)	0.048 (3)	0.051 (4)	−0.006 (3)	−0.019 (3)	0.021 (3)
C10	0.047 (4)	0.066 (4)	0.046 (4)	0.004 (3)	−0.003 (3)	−0.009 (3)
C11	0.045 (4)	0.101 (6)	0.072 (6)	−0.004 (4)	−0.009 (4)	−0.012 (5)

Geometric parameters (Å, º) top

S1—C7	1.614 (5)	C5—C6	1.364 (8)
N1—C7	1.335 (7)	C5—H5	0.9500
N1—C1	1.433 (6)	C6—H6	0.9500
N1—C8	1.483 (7)	C8—C9	1.502 (8)
N2—N3	1.255 (7)	C8—C10	1.535 (8)
N2—C7	1.456 (7)	C9—H9A	0.9800
N3—C8	1.466 (8)	C9—H9B	0.9800
C1—C6	1.355 (7)	C9—H9C	0.9800
C1—C2	1.396 (7)	C10—C11	1.502 (10)
C2—C3	1.415 (8)	C10—H10A	0.9900
C2—H2	0.9500	C10—H10B	0.9900
C3—C4	1.355 (9)	C11—H11A	0.9800
C3—H3	0.9500	C11—H11B	0.9800
C4—C5	1.372 (9)	C11—H11C	0.9800
C4—H4	0.9500

C7—N1—C1	125.5 (5)	N2—C7—S1	122.3 (4)
C7—N1—C8	110.0 (5)	N3—C8—N1	101.3 (4)
C1—N1—C8	124.5 (4)	N3—C8—C9	109.3 (5)
N3—N2—C7	110.9 (5)	N1—C8—C9	114.2 (5)
N2—N3—C8	111.4 (4)	N3—C8—C10	110.1 (5)
C6—C1—C2	121.7 (4)	N1—C8—C10	109.9 (5)
C6—C1—N1	121.8 (5)	C9—C8—C10	111.5 (5)
C2—C1—N1	116.5 (4)	C8—C9—H9A	109.5
C1—C2—C3	116.4 (5)	C8—C9—H9B	109.5
C1—C2—H2	121.8	H9A—C9—H9B	109.5
C3—C2—H2	121.8	C8—C9—H9C	109.5
C4—C3—C2	120.6 (5)	H9A—C9—H9C	109.5
C4—C3—H3	119.7	H9B—C9—H9C	109.5
C2—C3—H3	119.7	C11—C10—C8	114.4 (6)
C3—C4—C5	121.4 (5)	C11—C10—H10A	108.7
C3—C4—H4	119.3	C8—C10—H10A	108.7
C5—C4—H4	119.3	C11—C10—H10B	108.7
C6—C5—C4	119.0 (5)	C8—C10—H10B	108.7
C6—C5—H5	120.5	H10A—C10—H10B	107.6
C4—C5—H5	120.5	C10—C11—H11A	109.5
C1—C6—C5	121.0 (5)	C10—C11—H11B	109.5
C1—C6—H6	119.5	H11A—C11—H11B	109.5
C5—C6—H6	119.5	C10—C11—H11C	109.5
N1—C7—N2	106.3 (5)	H11A—C11—H11C	109.5
N1—C7—S1	131.2 (5)	H11B—C11—H11C	109.5

C7—N2—N3—C8	0.9 (7)	C8—N1—C7—S1	−176.6 (5)
C7—N1—C1—C6	85.0 (7)	N3—N2—C7—N1	0.5 (7)
C8—N1—C1—C6	−95.6 (6)	N3—N2—C7—S1	175.9 (5)
C7—N1—C1—C2	−94.8 (7)	N2—N3—C8—N1	−1.9 (6)
C8—N1—C1—C2	84.7 (6)	N2—N3—C8—C9	−122.7 (6)
C6—C1—C2—C3	1.5 (7)	N2—N3—C8—C10	114.5 (6)
N1—C1—C2—C3	−178.8 (4)	C7—N1—C8—N3	2.2 (6)
C1—C2—C3—C4	−0.7 (8)	C1—N1—C8—N3	−177.3 (5)
C2—C3—C4—C5	−0.5 (9)	C7—N1—C8—C9	119.6 (6)
C3—C4—C5—C6	0.9 (9)	C1—N1—C8—C9	−60.0 (7)
C2—C1—C6—C5	−1.1 (8)	C7—N1—C8—C10	−114.3 (5)
N1—C1—C6—C5	179.1 (5)	C1—N1—C8—C10	66.2 (7)
C4—C5—C6—C1	−0.1 (9)	N3—C8—C10—C11	−50.8 (8)
C1—N1—C7—N2	177.8 (5)	N1—C8—C10—C11	60.0 (7)
C8—N1—C7—N2	−1.8 (7)	C9—C8—C10—C11	−172.4 (6)
C1—N1—C7—S1	2.9 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···N2ⁱ	0.98	2.56	3.519 (9)	165

Symmetry code: (i) −y+1, x, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃N₃S
M_r	219.30
Crystal system, space group	Tetragonal, P42₁c
Temperature (K)	100
a, c (Å)	17.962 (4), 6.9992 (14)
V (Å³)	2258.2 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.30 × 0.05 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.927, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	10418, 1987, 1546
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.186, 1.07
No. of reflections	1987
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.31
Absolute structure	Flack (1983), 837 Friedel pairs
Absolute structure parameter	−0.2 (2)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9A···N2ⁱ	0.98	2.56	3.519 (9)	165

Symmetry code: (i) −y+1, x, −z+2.

Acknowledgements

We thank the University of Malaya (UMRG RG090 10AFR) for supporting this study.

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