organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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[Wei, Q.-L., He, F.-J., Lin, Y.-S. & Bi, S. (2007). Acta Cryst. E63, o3649.]). 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[Hu, Z.-Q., Yang, Y.-X., Shang, Y.-Q., Zhou, K. & Xu, L.-Z. (2006). Acta Cryst. E62, o3457-o3458.]), Xu et al. (2005[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.], 2006[Xu, L.-Z., Shang, Y.-Q., Yu, G.-P., Li, K. & Si, G.-D. (2006). Chin. J. Struct. Chem. 25, 673-676.]).

[Scheme 1]

Experimental

Crystal data
  • C11H15N5OS2

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.865, Tmax = 0.938

  • 3810 measured reflections

  • 2529 independent reflections

  • 2246 reflections with I > 2σ(I)

  • Rint = 0.010

Refinement
  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.143

  • S = 1.05

  • 2529 reflections

  • 172 parameters

  • H-atom parameters constrained

  • Δρmax = 0.51 e Å−3

  • Δρmin = −0.38 e Å−3

Data collection: SMART (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments, Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments, Inc., Madison, Wisconsin, USA.]); data reduction: SAINT (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments, Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXTL. Version 5.10. Bruker AXS, Inc., Madison, Wisconsin, USA.]); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995[Nardelli, M. (1995). J. Appl. Cryst. 28, 659.]) and PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]).

Supporting information


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.

Refinement top

After the H atoms were located in the difference map, they were fixed geometrically in the idealized positions and allowed to ride on the parent C atoms, with C—H distances of 0.96 Å (methyl), 0.97 Å (CH2) or 0.93 Å (CH), and with Uiso(H) values of 1.2Ueq(C) and 1.5 Ueq(C) (for methyl H atoms).

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
[Figure 1] 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
C11H15N5OS2Z = 2
Mr = 297.40F(000) = 312
Triclinic, P1Dx = 1.351 Mg m3
a = 8.9723 (8) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.1103 (8) ÅCell parameters from 2210 reflections
c = 10.1734 (8) Åθ = 2.5–25.6°
α = 60.728 (1)°µ = 0.36 mm1
β = 80.340 (1)°T = 293 K
γ = 65.416 (1)°Block, colourless
V = 731.3 (1) Å30.41 × 0.22 × 0.18 mm
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer
2529 independent reflections
Radiation source: fine-focus sealed tube2246 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.010
Detector resolution: 8.33 pixels mm-1θmax = 25.0°, θmin = 2.3°
ω scansh = 910
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 912
Tmin = 0.865, Tmax = 0.938l = 1212
3810 measured reflections
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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0806P)2 + 0.357P]
where P = (Fo2 + 2Fc2)/3
2529 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
C11H15N5OS2γ = 65.416 (1)°
Mr = 297.40V = 731.3 (1) Å3
Triclinic, P1Z = 2
a = 8.9723 (8) ÅMo Kα radiation
b = 10.1103 (8) ŵ = 0.36 mm1
c = 10.1734 (8) ÅT = 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)
Tmin = 0.865, Tmax = 0.938Rint = 0.010
3810 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 1.05Δρmax = 0.51 e Å3
2529 reflectionsΔρmin = 0.38 e Å3
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
xyzUiso*/Ueq
N10.5556 (3)0.4597 (3)0.7067 (3)0.0680 (7)
N20.6886 (3)0.4050 (3)0.7986 (3)0.0670 (6)
N30.2627 (3)0.8466 (3)0.4764 (2)0.0546 (5)
N40.2154 (4)0.9710 (3)0.5103 (3)0.0718 (7)
N50.2371 (4)1.0629 (3)0.2618 (3)0.0762 (7)
O11.0413 (3)0.4947 (2)0.7133 (2)0.0746 (6)
S10.49906 (8)0.68646 (9)0.77341 (9)0.0627 (3)
S20.81659 (9)0.48127 (9)0.96116 (8)0.0609 (2)
C10.6733 (3)0.5099 (3)0.8425 (3)0.0508 (6)
C20.4489 (3)0.6004 (3)0.6854 (3)0.0548 (6)
C30.2921 (4)0.6795 (4)0.5949 (4)0.0698 (8)
H3A0.29540.61330.54960.084*
H3B0.20130.68170.66180.084*
C40.2003 (4)1.0979 (3)0.3766 (3)0.0657 (7)
H40.16651.20430.36300.079*
C50.2751 (4)0.9038 (4)0.3298 (3)0.0695 (8)
H50.30660.83980.28070.083*
C60.9842 (3)0.3090 (3)0.9519 (3)0.0543 (6)
H6A1.06580.26111.03110.065*
H6B0.94390.22610.97110.065*
C71.0658 (3)0.3532 (3)0.8017 (3)0.0501 (6)
C81.1780 (4)0.2127 (3)0.7691 (3)0.0629 (7)
C91.2994 (7)0.0845 (7)0.8962 (5)0.199 (4)
H9A1.36600.13110.90960.298*
H9B1.36790.00420.87440.298*
H9C1.24300.04370.98680.298*
C101.2626 (5)0.2749 (5)0.6225 (4)0.0910 (11)
H10A1.33250.32080.63170.136*
H10B1.18160.35810.54220.136*
H10C1.32720.18530.60080.136*
C111.0686 (7)0.1417 (8)0.7445 (8)0.154 (3)
H11A1.13600.05220.72350.231*
H11B0.99210.22610.66090.231*
H11C1.00970.10280.83380.231*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0740 (15)0.0541 (13)0.0763 (16)0.0174 (12)0.0189 (12)0.0300 (12)
N20.0678 (14)0.0555 (13)0.0776 (16)0.0112 (11)0.0206 (12)0.0341 (12)
N30.0551 (12)0.0475 (11)0.0590 (13)0.0186 (9)0.0090 (10)0.0209 (10)
N40.0947 (18)0.0605 (14)0.0618 (14)0.0268 (13)0.0001 (13)0.0315 (12)
N50.0926 (19)0.0611 (15)0.0560 (14)0.0159 (13)0.0140 (13)0.0200 (12)
O10.0788 (13)0.0500 (11)0.0763 (13)0.0282 (10)0.0123 (11)0.0161 (10)
S10.0575 (4)0.0554 (4)0.0780 (5)0.0157 (3)0.0043 (3)0.0359 (4)
S20.0656 (4)0.0655 (5)0.0606 (4)0.0234 (3)0.0027 (3)0.0359 (4)
C10.0536 (13)0.0487 (13)0.0494 (13)0.0200 (11)0.0021 (11)0.0222 (11)
C20.0572 (14)0.0470 (14)0.0568 (14)0.0238 (12)0.0020 (11)0.0175 (11)
C30.0673 (17)0.0545 (15)0.0793 (19)0.0301 (14)0.0174 (15)0.0138 (14)
C40.0773 (18)0.0486 (15)0.0634 (17)0.0160 (13)0.0089 (14)0.0239 (13)
C50.0795 (19)0.0606 (17)0.0645 (18)0.0124 (14)0.0127 (14)0.0336 (15)
C60.0585 (14)0.0493 (13)0.0493 (14)0.0200 (11)0.0091 (11)0.0161 (11)
C70.0472 (12)0.0462 (13)0.0537 (14)0.0198 (10)0.0097 (10)0.0162 (11)
C80.0658 (16)0.0536 (15)0.0588 (16)0.0192 (13)0.0017 (13)0.0216 (13)
C90.181 (6)0.165 (5)0.085 (3)0.104 (5)0.051 (3)0.063 (3)
C100.095 (3)0.095 (3)0.082 (2)0.037 (2)0.021 (2)0.046 (2)
C110.170 (5)0.186 (5)0.237 (7)0.129 (5)0.117 (5)0.176 (6)
Geometric parameters (Å, º) top
N1—C21.274 (3)C5—H50.9300
N1—N21.387 (3)C6—C71.516 (4)
N2—C11.290 (3)C6—H6A0.9700
N3—C51.313 (4)C6—H6B0.9700
N3—N41.347 (3)C7—C81.517 (4)
N3—C31.456 (3)C8—C91.482 (5)
N4—C41.314 (4)C8—C101.515 (4)
N5—C51.310 (4)C8—C111.544 (5)
N5—C41.332 (4)C9—H9A0.9600
O1—C71.205 (3)C9—H9B0.9600
S1—C11.715 (3)C9—H9C0.9600
S1—C21.728 (3)C10—H10A0.9600
S2—C11.751 (3)C10—H10B0.9600
S2—C61.799 (3)C10—H10C0.9600
C2—C31.498 (4)C11—H11A0.9600
C3—H3A0.9700C11—H11B0.9600
C3—H3B0.9700C11—H11C0.9600
C4—H40.9300
C2—N1—N2113.0 (2)C7—C6—H6B108.8
C1—N2—N1111.5 (2)S2—C6—H6B108.8
C5—N3—N4109.3 (2)H6A—C6—H6B107.7
C5—N3—C3130.1 (3)O1—C7—C6120.5 (2)
N4—N3—C3120.6 (2)O1—C7—C8122.2 (2)
C4—N4—N3102.1 (2)C6—C7—C8117.3 (2)
C5—N5—C4102.3 (2)C9—C8—C10111.0 (4)
C1—S1—C286.46 (12)C9—C8—C7110.6 (3)
C1—S2—C698.80 (12)C10—C8—C7110.9 (2)
N2—C1—S1114.8 (2)C9—C8—C11110.8 (5)
N2—C1—S2124.2 (2)C10—C8—C11106.0 (3)
S1—C1—S2121.01 (15)C7—C8—C11107.3 (3)
N1—C2—C3121.9 (3)C8—C9—H9A109.5
N1—C2—S1114.2 (2)C8—C9—H9B109.5
C3—C2—S1123.9 (2)H9A—C9—H9B109.5
N3—C3—C2112.9 (2)C8—C9—H9C109.5
N3—C3—H3A109.0H9A—C9—H9C109.5
C2—C3—H3A109.0H9B—C9—H9C109.5
N3—C3—H3B109.0C8—C10—H10A109.5
C2—C3—H3B109.0C8—C10—H10B109.5
H3A—C3—H3B107.8H10A—C10—H10B109.5
N4—C4—N5115.0 (3)C8—C10—H10C109.5
N4—C4—H4122.5H10A—C10—H10C109.5
N5—C4—H4122.5H10B—C10—H10C109.5
N5—C5—N3111.1 (3)C8—C11—H11A109.5
N5—C5—H5124.4C8—C11—H11B109.5
N3—C5—H5124.4H11A—C11—H11B109.5
C7—C6—S2113.74 (17)C8—C11—H11C109.5
C7—C6—H6A108.8H11A—C11—H11C109.5
S2—C6—H6A108.8H11B—C11—H11C109.5
C2—N1—N2—C10.3 (4)S1—C2—C3—N353.9 (4)
C5—N3—N4—C40.9 (3)N3—N4—C4—N51.1 (4)
C3—N3—N4—C4179.3 (2)C5—N5—C4—N40.9 (4)
N1—N2—C1—S11.4 (3)C4—N5—C5—N30.3 (4)
N1—N2—C1—S2179.3 (2)N4—N3—C5—N50.4 (4)
C2—S1—C1—N21.6 (2)C3—N3—C5—N5179.8 (3)
C2—S1—C1—S2179.13 (18)C1—S2—C6—C771.9 (2)
C6—S2—C1—N213.2 (3)S2—C6—C7—O115.0 (3)
C6—S2—C1—S1166.03 (16)S2—C6—C7—C8165.12 (19)
N2—N1—C2—C3177.4 (3)O1—C7—C8—C9129.1 (4)
N2—N1—C2—S10.9 (3)C6—C7—C8—C950.8 (5)
C1—S1—C2—N11.4 (2)O1—C7—C8—C105.4 (4)
C1—S1—C2—C3176.9 (2)C6—C7—C8—C10174.5 (2)
C5—N3—C3—C2105.8 (3)O1—C7—C8—C11109.9 (4)
N4—N3—C3—C274.1 (4)C6—C7—C8—C1170.2 (4)
N1—C2—C3—N3127.9 (3)

Experimental details

Crystal data
Chemical formulaC11H15N5OS2
Mr297.40
Crystal system, space groupTriclinic, 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)
V3)731.3 (1)
Z2
Radiation typeMo Kα
µ (mm1)0.36
Crystal size (mm)0.41 × 0.22 × 0.18
Data collection
DiffractometerSiemens SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.865, 0.938
No. of measured, independent and
observed [I > 2σ(I)] reflections
3810, 2529, 2246
Rint0.010
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.143, 1.05
No. of reflections2529
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

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First citationNardelli, M. (1995). J. Appl. Cryst. 28, 659.  CrossRef IUCr Journals Google Scholar
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First citationSheldrick, G. M. (1997). SHELXTL. Version 5.10. Bruker AXS, Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
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First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWei, Q.-L., He, F.-J., Lin, Y.-S. & Bi, S. (2007). Acta Cryst. E63, o3649.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationXu, 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
First citationXu, 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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