3,3-Dimethyl-1-[5-(1H-1,2,4-triazol-1-yl­meth­yl)-1,3,4-thia­diazol-2-ylsulfan­yl]butan-2-one

Wei, Q.-L.; He, F.-J.; Li, F.; Bi, S.

doi:10.1107/S1600536807068286

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o412

doi:10.1107/S1600536807068286

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3,3-Dimethyl-1-[5-(1H-1,2,4-triazol-1-ylmethyl)-1,3,4-thiadiazol-2-ylsulfanyl]butan-2-one

Qing-Li Wei,^a Fu-Jin He,^a Fang Li ^a and Sai Bi ^a ^*

^aCollege of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, 266042 Qingdao, Shandong, People's Republic of China
^*Correspondence e-mail: qustchemistry@126.com

(Received 7 November 2007; accepted 24 December 2007; online 9 January 2008)

In the molecule of the title compound, C₁₁H₁₅N₅OS₂, the thiadiazole and triazole rings are not coplanar, the dihedral angle formed by their mean planes being 59.9 (2)°. The exocyclic S atom, and the methylene, carbonyl, tert-butyl and one methyl carbon form an approximately planar zigzag chain, which makes a dihedral angle of 74.6 (1)° with the thiadiazole ring.

Related literature

For the structure of the related compound, 1-(2,4-dichlorophenyl)-2-[5-(1H-1,2,4-triazol-1-ylmethyl)-1,3,4-thiadiazol-2-ylsulfanyl] ethanone, see: Wei et al. (2007 ). For the synthesis of the starting material 5-(1H-1,2,4-triazol-1-yl)methyl)-1,3,4-thiadiazole-2(3H)-thione, see: Hu et al. (2006 ), Xu et al. (2005 , 2006 ).

Experimental

Crystal data

C₁₁H₁₅N₅OS₂
M_r = 297.40
Triclinic, $[P \overline 1]$
a = 8.9723 (8) Å
b = 10.1103 (8) Å
c = 10.1734 (8) Å
α = 60.728 (1)°
β = 80.340 (1)°
γ = 65.416 (1)°
V = 731.3 (1) Å³
Z = 2
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 293 (2) K
0.41 × 0.22 × 0.18 mm

Data collection

Siemens SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.865, T_max = 0.938
3810 measured reflections
2529 independent reflections
2246 reflections with I > 2σ(I)
R_int = 0.010

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.143
S = 1.05
2529 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 1997 ); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ) and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068286/ya2060sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068286/ya2060Isup2.hkl

checkCIF report

Comment top

Recently, we have reported the structure of 1-(2,4-dichlorophenyl)-2-[5-(1H-1,2,4- triazol-1-ylmethyl)-1,3,4-thiadiazol-2-ylsulfanyl] ethanone (Wei et al., 2007). As part of our ongoing investigation of biological properties of 1,2,4-triazole and 1,3,4-thiadiazole derivatives, the title compound, (I), was synthesized; its crystal structure is reported here.

The bond lengths and angles are comparable with those of the above mentioned related compound, reported by Wei et al. (2007). The whole molecule is non-planar with a dihedral angle of 59.9 (2)° between the thiadiazole (C1/C2/N1/N2/S1) and triazole (N3—N5/C4/C5) rings. The S2—C6—C7—C8—C10 atoms form approximately planar zigzag chain, which makes a dihedral angle of 74.6 (1)° with the thiadiazole ring.

Related literature top

For the structure of the related compound, 1-(2,4-dichlorophenyl)-2-[5-(1H-1,2,4- triazol-1-ylmethyl)-1,3,4-thiadiazol-2-ylsulfanyl] ethanone, see: Wei et al. (2007). For the synthesis of the starting material 5-((1H-1,2,4-triazol-1-yl)methyl)-1,3,4-thiadiazole-2(3H)-thione, see: Hu et al. (2006), Xu et al. (2005, 2006).

Experimental top

8 mmol of 5-((1H-1,2,4-triazol-1-yl)methyl)-1,3,4-thiadiazole-2(3H)-thione (Hu et al., 2006; Xu et al., 2005; Xu et al., 2006) was refluxed for 4 h with 8 mmol of 1-bromo-3,3-dimethylbutan-2-one in 50 ml of acetone in the presence of 8 mmol of triethylamine. The solid that precipitated was recrystallized from ethanol (1.21 g, yield 50.86%). Single crystals suitable for X-ray measurements were obtained by slow evaporation of ethylacetate solution at room temperature.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures top

Fig. 1. The structure of the title compound (I), showing 50% probability displacement ellipsoids and the atom numbering scheme.

3,3-Dimethyl-1-[5-(1H-1,2,4-triazol-1-ylmethyl)-1,3,4-thiadiazol-2-ψlsulfanyl]butan-2-one top

Crystal data top

C₁₁H₁₅N₅OS₂	Z = 2
M_r = 297.40	F(000) = 312
Triclinic, P1	D_x = 1.351 Mg m⁻³
a = 8.9723 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1103 (8) Å	Cell parameters from 2210 reflections
c = 10.1734 (8) Å	θ = 2.5–25.6°
α = 60.728 (1)°	µ = 0.36 mm⁻¹
β = 80.340 (1)°	T = 293 K
γ = 65.416 (1)°	Block, colourless
V = 731.3 (1) Å³	0.41 × 0.22 × 0.18 mm

Data collection top

Siemens SMART 1000 CCD area-detector diffractometer	2529 independent reflections
Radiation source: fine-focus sealed tube	2246 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.010
Detector resolution: 8.33 pixels mm^-1	θ_max = 25.0°, θ_min = 2.3°
ω scans	h = −9→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→12
T_min = 0.865, T_max = 0.938	l = −12→12
3810 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0806P)² + 0.357P] where P = (F_o² + 2F_c²)/3
2529 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₁H₁₅N₅OS₂	γ = 65.416 (1)°
M_r = 297.40	V = 731.3 (1) Å³
Triclinic, P1	Z = 2
a = 8.9723 (8) Å	Mo Kα radiation
b = 10.1103 (8) Å	µ = 0.36 mm⁻¹
c = 10.1734 (8) Å	T = 293 K
α = 60.728 (1)°	0.41 × 0.22 × 0.18 mm
β = 80.340 (1)°

Data collection top

Siemens SMART 1000 CCD area-detector diffractometer	2529 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2246 reflections with I > 2σ(I)
T_min = 0.865, T_max = 0.938	R_int = 0.010
3810 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.05	Δρ_max = 0.51 e Å⁻³
2529 reflections	Δρ_min = −0.38 e Å⁻³
172 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
N1	0.5556 (3)	0.4597 (3)	0.7067 (3)	0.0680 (7)
N2	0.6886 (3)	0.4050 (3)	0.7986 (3)	0.0670 (6)
N3	0.2627 (3)	0.8466 (3)	0.4764 (2)	0.0546 (5)
N4	0.2154 (4)	0.9710 (3)	0.5103 (3)	0.0718 (7)
N5	0.2371 (4)	1.0629 (3)	0.2618 (3)	0.0762 (7)
O1	1.0413 (3)	0.4947 (2)	0.7133 (2)	0.0746 (6)
S1	0.49906 (8)	0.68646 (9)	0.77341 (9)	0.0627 (3)
S2	0.81659 (9)	0.48127 (9)	0.96116 (8)	0.0609 (2)
C1	0.6733 (3)	0.5099 (3)	0.8425 (3)	0.0508 (6)
C2	0.4489 (3)	0.6004 (3)	0.6854 (3)	0.0548 (6)
C3	0.2921 (4)	0.6795 (4)	0.5949 (4)	0.0698 (8)
H3A	0.2954	0.6133	0.5496	0.084*
H3B	0.2013	0.6817	0.6618	0.084*
C4	0.2003 (4)	1.0979 (3)	0.3766 (3)	0.0657 (7)
H4	0.1665	1.2043	0.3630	0.079*
C5	0.2751 (4)	0.9038 (4)	0.3298 (3)	0.0695 (8)
H5	0.3066	0.8398	0.2807	0.083*
C6	0.9842 (3)	0.3090 (3)	0.9519 (3)	0.0543 (6)
H6A	1.0658	0.2611	1.0311	0.065*
H6B	0.9439	0.2261	0.9711	0.065*
C7	1.0658 (3)	0.3532 (3)	0.8017 (3)	0.0501 (6)
C8	1.1780 (4)	0.2127 (3)	0.7691 (3)	0.0629 (7)
C9	1.2994 (7)	0.0845 (7)	0.8962 (5)	0.199 (4)
H9A	1.3660	0.1311	0.9096	0.298*
H9B	1.3679	−0.0042	0.8744	0.298*
H9C	1.2430	0.0437	0.9868	0.298*
C10	1.2626 (5)	0.2749 (5)	0.6225 (4)	0.0910 (11)
H10A	1.3325	0.3208	0.6317	0.136*
H10B	1.1816	0.3581	0.5422	0.136*
H10C	1.3272	0.1853	0.6008	0.136*
C11	1.0686 (7)	0.1417 (8)	0.7445 (8)	0.154 (3)
H11A	1.1360	0.0522	0.7235	0.231*
H11B	0.9921	0.2261	0.6609	0.231*
H11C	1.0097	0.1028	0.8338	0.231*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0740 (15)	0.0541 (13)	0.0763 (16)	−0.0174 (12)	−0.0189 (12)	−0.0300 (12)
N2	0.0678 (14)	0.0555 (13)	0.0776 (16)	−0.0112 (11)	−0.0206 (12)	−0.0341 (12)
N3	0.0551 (12)	0.0475 (11)	0.0590 (13)	−0.0186 (9)	−0.0090 (10)	−0.0209 (10)
N4	0.0947 (18)	0.0605 (14)	0.0618 (14)	−0.0268 (13)	0.0001 (13)	−0.0315 (12)
N5	0.0926 (19)	0.0611 (15)	0.0560 (14)	−0.0159 (13)	−0.0140 (13)	−0.0200 (12)
O1	0.0788 (13)	0.0500 (11)	0.0763 (13)	−0.0282 (10)	0.0123 (11)	−0.0161 (10)
S1	0.0575 (4)	0.0554 (4)	0.0780 (5)	−0.0157 (3)	−0.0043 (3)	−0.0359 (4)
S2	0.0656 (4)	0.0655 (5)	0.0606 (4)	−0.0234 (3)	−0.0027 (3)	−0.0359 (4)
C1	0.0536 (13)	0.0487 (13)	0.0494 (13)	−0.0200 (11)	0.0021 (11)	−0.0222 (11)
C2	0.0572 (14)	0.0470 (14)	0.0568 (14)	−0.0238 (12)	−0.0020 (11)	−0.0175 (11)
C3	0.0673 (17)	0.0545 (15)	0.0793 (19)	−0.0301 (14)	−0.0174 (15)	−0.0138 (14)
C4	0.0773 (18)	0.0486 (15)	0.0634 (17)	−0.0160 (13)	−0.0089 (14)	−0.0239 (13)
C5	0.0795 (19)	0.0606 (17)	0.0645 (18)	−0.0124 (14)	−0.0127 (14)	−0.0336 (15)
C6	0.0585 (14)	0.0493 (13)	0.0493 (14)	−0.0200 (11)	−0.0091 (11)	−0.0161 (11)
C7	0.0472 (12)	0.0462 (13)	0.0537 (14)	−0.0198 (10)	−0.0097 (10)	−0.0162 (11)
C8	0.0658 (16)	0.0536 (15)	0.0588 (16)	−0.0192 (13)	0.0017 (13)	−0.0216 (13)
C9	0.181 (6)	0.165 (5)	0.085 (3)	0.104 (5)	−0.051 (3)	−0.063 (3)
C10	0.095 (3)	0.095 (3)	0.082 (2)	−0.037 (2)	0.021 (2)	−0.046 (2)
C11	0.170 (5)	0.186 (5)	0.237 (7)	−0.129 (5)	0.117 (5)	−0.176 (6)

Geometric parameters (Å, º) top

N1—C2	1.274 (3)	C5—H5	0.9300
N1—N2	1.387 (3)	C6—C7	1.516 (4)
N2—C1	1.290 (3)	C6—H6A	0.9700
N3—C5	1.313 (4)	C6—H6B	0.9700
N3—N4	1.347 (3)	C7—C8	1.517 (4)
N3—C3	1.456 (3)	C8—C9	1.482 (5)
N4—C4	1.314 (4)	C8—C10	1.515 (4)
N5—C5	1.310 (4)	C8—C11	1.544 (5)
N5—C4	1.332 (4)	C9—H9A	0.9600
O1—C7	1.205 (3)	C9—H9B	0.9600
S1—C1	1.715 (3)	C9—H9C	0.9600
S1—C2	1.728 (3)	C10—H10A	0.9600
S2—C1	1.751 (3)	C10—H10B	0.9600
S2—C6	1.799 (3)	C10—H10C	0.9600
C2—C3	1.498 (4)	C11—H11A	0.9600
C3—H3A	0.9700	C11—H11B	0.9600
C3—H3B	0.9700	C11—H11C	0.9600
C4—H4	0.9300

C2—N1—N2	113.0 (2)	C7—C6—H6B	108.8
C1—N2—N1	111.5 (2)	S2—C6—H6B	108.8
C5—N3—N4	109.3 (2)	H6A—C6—H6B	107.7
C5—N3—C3	130.1 (3)	O1—C7—C6	120.5 (2)
N4—N3—C3	120.6 (2)	O1—C7—C8	122.2 (2)
C4—N4—N3	102.1 (2)	C6—C7—C8	117.3 (2)
C5—N5—C4	102.3 (2)	C9—C8—C10	111.0 (4)
C1—S1—C2	86.46 (12)	C9—C8—C7	110.6 (3)
C1—S2—C6	98.80 (12)	C10—C8—C7	110.9 (2)
N2—C1—S1	114.8 (2)	C9—C8—C11	110.8 (5)
N2—C1—S2	124.2 (2)	C10—C8—C11	106.0 (3)
S1—C1—S2	121.01 (15)	C7—C8—C11	107.3 (3)
N1—C2—C3	121.9 (3)	C8—C9—H9A	109.5
N1—C2—S1	114.2 (2)	C8—C9—H9B	109.5
C3—C2—S1	123.9 (2)	H9A—C9—H9B	109.5
N3—C3—C2	112.9 (2)	C8—C9—H9C	109.5
N3—C3—H3A	109.0	H9A—C9—H9C	109.5
C2—C3—H3A	109.0	H9B—C9—H9C	109.5
N3—C3—H3B	109.0	C8—C10—H10A	109.5
C2—C3—H3B	109.0	C8—C10—H10B	109.5
H3A—C3—H3B	107.8	H10A—C10—H10B	109.5
N4—C4—N5	115.0 (3)	C8—C10—H10C	109.5
N4—C4—H4	122.5	H10A—C10—H10C	109.5
N5—C4—H4	122.5	H10B—C10—H10C	109.5
N5—C5—N3	111.1 (3)	C8—C11—H11A	109.5
N5—C5—H5	124.4	C8—C11—H11B	109.5
N3—C5—H5	124.4	H11A—C11—H11B	109.5
C7—C6—S2	113.74 (17)	C8—C11—H11C	109.5
C7—C6—H6A	108.8	H11A—C11—H11C	109.5
S2—C6—H6A	108.8	H11B—C11—H11C	109.5

C2—N1—N2—C1	0.3 (4)	S1—C2—C3—N3	53.9 (4)
C5—N3—N4—C4	0.9 (3)	N3—N4—C4—N5	−1.1 (4)
C3—N3—N4—C4	−179.3 (2)	C5—N5—C4—N4	0.9 (4)
N1—N2—C1—S1	−1.4 (3)	C4—N5—C5—N3	−0.3 (4)
N1—N2—C1—S2	179.3 (2)	N4—N3—C5—N5	−0.4 (4)
C2—S1—C1—N2	1.6 (2)	C3—N3—C5—N5	179.8 (3)
C2—S1—C1—S2	−179.13 (18)	C1—S2—C6—C7	71.9 (2)
C6—S2—C1—N2	13.2 (3)	S2—C6—C7—O1	15.0 (3)
C6—S2—C1—S1	−166.03 (16)	S2—C6—C7—C8	−165.12 (19)
N2—N1—C2—C3	−177.4 (3)	O1—C7—C8—C9	129.1 (4)
N2—N1—C2—S1	0.9 (3)	C6—C7—C8—C9	−50.8 (5)
C1—S1—C2—N1	−1.4 (2)	O1—C7—C8—C10	5.4 (4)
C1—S1—C2—C3	176.9 (2)	C6—C7—C8—C10	−174.5 (2)
C5—N3—C3—C2	105.8 (3)	O1—C7—C8—C11	−109.9 (4)
N4—N3—C3—C2	−74.1 (4)	C6—C7—C8—C11	70.2 (4)
N1—C2—C3—N3	−127.9 (3)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅N₅OS₂
M_r	297.40
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.9723 (8), 10.1103 (8), 10.1734 (8)
α, β, γ (°)	60.728 (1), 80.340 (1), 65.416 (1)
V (Å³)	731.3 (1)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.41 × 0.22 × 0.18

Data collection
Diffractometer	Siemens SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.865, 0.938
No. of measured, independent and observed [I > 2σ(I)] reflections	3810, 2529, 2246
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.143, 1.05
No. of reflections	2529
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.38

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 1997), PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Acknowledgements

This project was supported by the Natural Science Foundation of Shandong Province (grant Nos. Z2006B01 and Y2006B07).

References

Hu, Z.-Q., Yang, Y.-X., Shang, Y.-Q., Zhou, K. & Xu, L.-Z. (2006). Acta Cryst. E62, o3457–o3458. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nardelli, M. (1995). J. Appl. Cryst. 28, 659. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXTL. Version 5.10. Bruker AXS, Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments, Inc., Madison, Wisconsin, USA. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wei, Q.-L., He, F.-J., Lin, Y.-S. & Bi, S. (2007). Acta Cryst. E63, o3649. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xu, L.-Z., Li, W.-H., Si, G.-D., Zhu, C.-Y., Li, K. & Hou, B.-R. (2005). Chem. Res. Chin. Univ. 21, 444–446. CAS Google Scholar
Xu, L.-Z., Shang, Y.-Q., Yu, G.-P., Li, K. & Si, G.-D. (2006). Chin. J. Struct. Chem. 25, 673–676. CAS Google Scholar

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