2-[(5-Amino-1,3,4-thia­diazol-2-yl)sulfan­yl]-N-(2,4,5-tri­chloro­phen­yl)acetamide

Madan Kumar, S.; Madhu Kumar, D.J.; Shivakumar, H.P.; Jagadeesha Prasad, D.; Byrappa, K.; Abdoh, M.M.M.

doi:10.1107/S2414314616011238

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161123

https://doi.org/10.1107/S2414314616011238

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2-[(5-Amino-1,3,4-thiadiazol-2-yl)sulfanyl]-N-(2,4,5-trichlorophenyl)acetamide

S. Madan Kumar,^a D. J. Madhu Kumar,^b H. P. Shivakumar,^c D. Jagadeesha Prasad,^b K. Byrappa ^d and M. M. M. Abdoh ^e ^*

^aPURSE Lab, Mangalagangotri, Mangalore University, Mangaluru 574 199, India, ^bDepartment of Post-Graduate Research In Chemistry, Mangalagangori, Mangalore University, India, ^cDepartment of Physics, Government College, Mandya 571 401, India, ^dDepartment of Material Science, Mangalore University, Mangaluru 574 199, India, and ^eDepartment of Physics, Faculty of Science, An Najah National University, Nablus, West Bank, Palestinian Territories
^*Correspondence e-mail: muneer@najah.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 1 July 2016; accepted 11 July 2016; online 19 July 2016)

In the title compound, C₁₀H₇Cl₃N₄OS₂, the dihedral angle between the trichlorobenzene and thiadiazole rings is 29.26 (17)°. In the crystal, molecules are connected by N—H⋯O and C—H⋯O hydrogen bonds, forming chains propagating along [001]. The chains are linked via N—H⋯N hydrogen bonds to form slabs parallel to (100).

Keywords: crystal structure; imidazothiadiazole; hydrogen bonding.

CCDC reference: 1491987

Structure description

As part of our research on the syntheses and crystal structure analyses of thiadiazole derivatives, we report herein on the synthesis and crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between the trichlorobenzene ring (C5–C10) and the thiadiazol moiety (C1/C2/N1/N2/S1) is 29.26 (17)°.

Figure 1
A view of the molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, molecules are connected by N—H⋯O and C—H⋯O hydrogen bonds, forming chains propagating along the c-axis direction (Table 1 and Fig. 2). The chains are linked via N—H⋯N hydrogen bonds to form slabs parallel to the bc plane (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O8ⁱ	0.86	2.09	2.927 (3)	163
C3—H3D⋯O8ⁱ	0.97	2.43	3.166 (3)	133
N3—H3A⋯N1ⁱⁱ	0.86	2.51	3.304 (4)	154
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
A viewed along the b axis of the crystal packing of the title compound. Hydrogen bonds are drawn as dashed lines (see Table 1

Synthesis and crystallization

An equimolar ratio of compound 2-((5-amino-1,3,4-thiadiazol-2-yl)thio)-N-(trichlorophenyl)acetamide (0.005 mol) and ethyl chloroacetate (0.005 mol) in glacial acetic acid (20 ml) was heated under reflux for 17 h. The reaction mixture was poured into ice-cold water. The precipitated solid was filtered, dried and recrystallized from ethanol.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₇Cl₃N₄OS₂
M_r	369.67
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	12.4679 (12), 11.9467 (11), 9.5278 (8)
β (°)	95.701 (7)
V (Å³)	1412.1 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.94
Crystal size (mm)	0.32 × 0.23 × 0.1

Data collection
Diffractometer	Rigaku Saturn724+
Absorption correction	Multi-scan (NUMABS; Rigaku, 1999 )
T_min, T_max	0.771, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	9999, 3200, 2292
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.128, 1.09
No. of reflections	3200
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.41
Computer programs: CrystalClear (Rigaku, 2011 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1491987

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616011238/su4061sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616011238/su4061Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616011238/su4061Isup3.cml

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku, 2011); cell refinement: CrystalClear (Rigaku, 2011); data reduction: CrystalClear (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

2-[(5-Amino-1,3,4-thiadiazol-2-yl)sulfanyl]-N-(2,4,5-trichlorophenyl)acetamide top

Crystal data top

C₁₀H₇Cl₃N₄OS₂	F(000) = 744
M_r = 369.67	D_x = 1.739 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 12.4679 (12) Å	Cell parameters from 3200 reflections
b = 11.9467 (11) Å	θ = 3.1–27.5°
c = 9.5278 (8) Å	µ = 0.94 mm⁻¹
β = 95.701 (7)°	T = 273 K
V = 1412.1 (2) Å³	Block, colourless
Z = 4	0.32 × 0.23 × 0.1 mm

Data collection top

Rigaku Saturn724+ diffractometer	R_int = 0.052
profile data from ω–scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (NUMABS; Rigaku, 1999)	h = −16→16
T_min = 0.771, T_max = 0.910	k = −15→15
9999 measured reflections	l = −9→12
3200 independent reflections	3200 standard reflections
2292 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.0554P)² + 0.4363P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
3200 reflections	Δρ_max = 0.46 e Å⁻³
182 parameters	Δρ_min = −0.41 e Å⁻³
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Cl1	0.27431 (8)	0.33324 (7)	0.75005 (10)	0.0522 (3)
Cl2	0.10023 (8)	0.19165 (6)	0.56097 (9)	0.0479 (3)
Cl3	0.01952 (7)	0.54537 (6)	0.22229 (8)	0.0393 (2)
S1	0.38818 (8)	1.08239 (7)	0.62462 (9)	0.0427 (3)
S2	0.35323 (7)	0.87823 (7)	0.43499 (8)	0.0381 (2)
O8	0.1844 (2)	0.73427 (18)	0.6362 (2)	0.0415 (6)
N1	0.4321 (3)	0.8833 (2)	0.7082 (3)	0.0447 (7)
N2	0.4623 (3)	0.9512 (2)	0.8237 (3)	0.0505 (8)
N3	0.4728 (3)	1.1403 (3)	0.8894 (3)	0.0576 (9)
H3A	0.4773	1.2027	0.8453	0.069*
H3B	0.4237	1.1454	0.9466	0.069*
N4	0.1841 (2)	0.6632 (2)	0.4152 (3)	0.0332 (6)
H4	0.1894	0.6797	0.3283	0.040*
C1	0.4452 (3)	1.0570 (3)	0.7939 (3)	0.0390 (8)
C2	0.3929 (3)	0.9389 (3)	0.5991 (3)	0.0333 (7)
C3	0.2102 (3)	0.8607 (2)	0.4479 (3)	0.0331 (7)
H3C	0.1845	0.9190	0.5071	0.040*
H3D	0.1710	0.8665	0.3550	0.040*
C4	0.1910 (2)	0.7478 (2)	0.5102 (3)	0.0291 (7)
C5	0.1687 (2)	0.5499 (2)	0.4494 (3)	0.0285 (7)
C6	0.2261 (3)	0.4997 (2)	0.5656 (3)	0.0336 (7)
H6	0.2784	0.5405	0.6202	0.040*
C7	0.2061 (3)	0.3899 (3)	0.6005 (3)	0.0336 (7)
C8	0.1297 (3)	0.3284 (2)	0.5181 (3)	0.0316 (7)
C9	0.0733 (3)	0.3762 (2)	0.4015 (3)	0.0315 (7)
H9	0.0224	0.3346	0.3457	0.038*
C10	0.0930 (2)	0.4854 (2)	0.3683 (3)	0.0295 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0694 (7)	0.0412 (5)	0.0413 (5)	0.0011 (4)	−0.0173 (4)	0.0066 (4)
Cl2	0.0716 (7)	0.0291 (4)	0.0417 (5)	−0.0121 (4)	−0.0004 (4)	0.0057 (3)
Cl3	0.0487 (5)	0.0355 (4)	0.0316 (4)	−0.0010 (4)	−0.0065 (4)	0.0017 (3)
S1	0.0567 (6)	0.0308 (4)	0.0373 (5)	0.0017 (4)	−0.0116 (4)	−0.0020 (4)
S2	0.0461 (5)	0.0388 (4)	0.0295 (5)	−0.0096 (4)	0.0043 (4)	−0.0046 (4)
O8	0.0680 (17)	0.0346 (12)	0.0224 (12)	−0.0034 (11)	0.0067 (11)	−0.0042 (9)
N1	0.065 (2)	0.0304 (14)	0.0357 (16)	−0.0071 (14)	−0.0080 (14)	0.0003 (12)
N2	0.078 (2)	0.0364 (16)	0.0329 (16)	−0.0065 (15)	−0.0137 (15)	−0.0010 (13)
N3	0.086 (3)	0.0422 (17)	0.0415 (19)	−0.0042 (17)	−0.0088 (17)	−0.0072 (15)
N4	0.0512 (18)	0.0266 (12)	0.0218 (13)	−0.0073 (12)	0.0028 (12)	−0.0026 (10)
C1	0.046 (2)	0.0341 (16)	0.0348 (18)	−0.0052 (15)	−0.0067 (15)	−0.0024 (14)
C2	0.0362 (18)	0.0303 (15)	0.0324 (17)	−0.0055 (13)	−0.0007 (14)	0.0014 (13)
C3	0.0391 (19)	0.0272 (15)	0.0310 (17)	0.0001 (14)	−0.0073 (14)	−0.0026 (13)
C4	0.0306 (17)	0.0295 (15)	0.0266 (17)	−0.0016 (13)	−0.0012 (13)	−0.0043 (13)
C5	0.0368 (18)	0.0255 (14)	0.0236 (15)	−0.0027 (13)	0.0054 (12)	−0.0039 (12)
C6	0.0387 (19)	0.0317 (16)	0.0298 (17)	−0.0047 (14)	0.0003 (14)	−0.0033 (13)
C7	0.0398 (19)	0.0328 (16)	0.0279 (16)	0.0030 (14)	0.0011 (14)	0.0016 (13)
C8	0.045 (2)	0.0233 (14)	0.0271 (16)	−0.0053 (13)	0.0061 (14)	−0.0008 (12)
C9	0.0396 (18)	0.0297 (15)	0.0254 (16)	−0.0053 (14)	0.0032 (13)	−0.0040 (13)
C10	0.0347 (18)	0.0319 (15)	0.0216 (15)	0.0006 (13)	0.0011 (13)	−0.0039 (12)

Geometric parameters (Å, º) top

Cl1—C7	1.724 (3)	N4—H4	0.8600
Cl2—C8	1.733 (3)	N4—C4	1.354 (4)
Cl3—C10	1.742 (3)	N4—C5	1.410 (4)
S1—C1	1.723 (3)	C3—H3C	0.9700
S1—C2	1.733 (3)	C3—H3D	0.9700
S2—C2	1.750 (3)	C3—C4	1.503 (4)
S2—C3	1.812 (3)	C5—C6	1.393 (4)
O8—C4	1.222 (4)	C5—C10	1.392 (4)
N1—N2	1.388 (4)	C6—H6	0.9300
N1—C2	1.287 (4)	C6—C7	1.383 (4)
N2—C1	1.308 (4)	C7—C8	1.383 (4)
N3—H3A	0.8607	C8—C9	1.378 (4)
N3—H3B	0.8611	C9—H9	0.9300
N3—C1	1.369 (4)	C9—C10	1.371 (4)

C1—S1—C2	86.57 (15)	O8—C4—N4	123.5 (3)
C2—S2—C3	100.39 (15)	O8—C4—C3	122.4 (3)
C2—N1—N2	113.0 (3)	N4—C4—C3	114.1 (3)
C1—N2—N1	111.5 (3)	C6—C5—N4	121.7 (3)
H3A—N3—H3B	109.4	C10—C5—N4	120.2 (3)
C1—N3—H3A	109.3	C10—C5—C6	118.0 (3)
C1—N3—H3B	109.0	C5—C6—H6	119.7
C4—N4—H4	117.9	C7—C6—C5	120.6 (3)
C4—N4—C5	124.3 (3)	C7—C6—H6	119.7
C5—N4—H4	117.9	C6—C7—Cl1	119.0 (2)
N2—C1—S1	114.6 (2)	C6—C7—C8	119.9 (3)
N2—C1—N3	122.2 (3)	C8—C7—Cl1	121.1 (2)
N3—C1—S1	123.2 (3)	C7—C8—Cl2	121.1 (2)
S1—C2—S2	121.61 (18)	C9—C8—Cl2	118.5 (2)
N1—C2—S1	114.4 (2)	C9—C8—C7	120.4 (3)
N1—C2—S2	124.0 (3)	C8—C9—H9	120.3
S2—C3—H3C	109.9	C10—C9—C8	119.4 (3)
S2—C3—H3D	109.9	C10—C9—H9	120.3
H3C—C3—H3D	108.3	C5—C10—Cl3	119.3 (2)
C4—C3—S2	109.1 (2)	C9—C10—Cl3	118.9 (2)
C4—C3—H3C	109.9	C9—C10—C5	121.8 (3)
C4—C3—H3D	109.9

Cl1—C7—C8—Cl2	−0.5 (4)	C2—N1—N2—C1	−1.0 (5)
Cl1—C7—C8—C9	177.8 (2)	C3—S2—C2—S1	−87.5 (2)
Cl2—C8—C9—C10	177.9 (2)	C3—S2—C2—N1	95.8 (3)
S2—C3—C4—O8	95.0 (3)	C4—N4—C5—C6	−44.6 (5)
S2—C3—C4—N4	−83.7 (3)	C4—N4—C5—C10	134.0 (3)
N1—N2—C1—S1	1.5 (4)	C5—N4—C4—O8	−0.2 (5)
N1—N2—C1—N3	−177.3 (3)	C5—N4—C4—C3	178.6 (3)
N2—N1—C2—S1	0.0 (4)	C5—C6—C7—Cl1	−176.9 (2)
N2—N1—C2—S2	177.0 (3)	C5—C6—C7—C8	1.1 (5)
N4—C5—C6—C7	177.1 (3)	C6—C5—C10—Cl3	179.9 (2)
N4—C5—C10—Cl3	1.3 (4)	C6—C5—C10—C9	0.9 (5)
N4—C5—C10—C9	−177.7 (3)	C6—C7—C8—Cl2	−178.4 (2)
C1—S1—C2—S2	−176.4 (2)	C6—C7—C8—C9	−0.2 (5)
C1—S1—C2—N1	0.6 (3)	C7—C8—C9—C10	−0.4 (5)
C2—S1—C1—N2	−1.2 (3)	C8—C9—C10—Cl3	−179.0 (2)
C2—S1—C1—N3	177.5 (3)	C8—C9—C10—C5	0.0 (5)
C2—S2—C3—C4	−90.1 (2)	C10—C5—C6—C7	−1.5 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O8ⁱ	0.86	2.09	2.927 (3)	163
C3—H3D···O8ⁱ	0.97	2.43	3.166 (3)	133
N3—H3A···N1ⁱⁱ	0.86	2.51	3.304 (4)	154

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+3/2.

Acknowledgements

The authors thank DST–PURSE, Mangalore University, Mangaluru, for providing the single-crystal X-ray diffraction facility.

References

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