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

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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.051
• wR factor = 0.144
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT242_ALERT_2_A Check Low       Ueq as Compared to Neighbors for         C8

Author Response: That is because the methyl groups bonded to C8 have higher Ueq values. These methyl groups may be partly disordered, but it is difficult to model them.

Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.98 Ratio
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.59 Ratio

Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)         80 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT213_ALERT_2_C Atom C9      has ADP max/min Ratio .............       3.10 prola
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3

Author Response: That is because the methyl groups bonded to C8 have higher Ueq values. These methyl groups may be partly disordered, but it is difficult to model them.

PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   1 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) values of 1.2U_eq(C) and 1.5 U_eq(C) (for methyl H atoms).

Computing details

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

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

Crystal data

C11H15N5OS2	Z = 2
Mr = 297.40	F(000) = 312
Triclinic, P1	Dx = 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) Å^3	0.41 × 0.22 × 0.18 mm

Data collection

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

Refinement

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)