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

Madan Kumar, S.; Madhu Kumar, D.J.; Harish, K.S.; Jagadeesha, P.D.; Byrappa, K.; Abdoh, M.M.M.

doi:10.1107/S2414314616011391

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161139

https://doi.org/10.1107/S2414314616011391

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

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

^aPURSE Lab, Mangalagangotri, Mangalore University, Mangaluru 574 199, India, ^bDepartment of Post-Graduate and Research In Chemistry, Mangalagangori, Mangalore University, India, ^cDepartment of Physics, Sheshadripuram PU college, Mysore 570 017, 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 P. C. Healy, Griffith University, Australia (Received 4 July 2016; accepted 13 July 2016; online 15 July 2016)

In the title compound, C₁₀H₉ClN₄OS₂, the dihedral angle between the planes of the chlorophenyl and thiadiazole groups is 32.93 (16)°. The molecules are connected through intermolecular N—H⋯N and N—H⋯O hydrogen bonds. An N—H⋯N hydrogen bond forms R₂²(8) ring motifs.

Keywords: crystal structure; 1,3,4-thiadiazole; intermolecular hydrogen bonds.

CCDC reference: 1428528

Structure description

As part of our research on synthesis and crystal structure determination of imidazo[2,1-b][1,3,4]thiadiazole derivatives, we report here the crystal and molecular structure of 2-[(5-amino-1,3,4-thiadiazol-2-yl)sulfanyl]-N-(4-chlorophenyl)acetamide (Fig. 1).

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

The dihedral angle between the chlorophenyl (C5–C10) and thiadiazol (C1/C2/N1/N2/S1) rings is 32.93 (16)°. In the crystal (Fig. 2), the molecules are connected through N—H⋯N and N—H⋯O hydrogen bonds (Table 1), the N3—H3A⋯N2 hydrogen bonds forming R₂²(8) ring motifs. Overall, these interactions generate a two-dimensional network parallel to (100).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2ⁱ	0.86	2.12	2.978 (3)	172
N3—H3B⋯N1ⁱⁱ	0.86	2.17	2.973 (3)	156
N3—H3B⋯N2ⁱⁱ	0.86	2.58	3.319 (3)	144
N11—H11⋯O1ⁱⁱⁱ	0.86	2.09	2.926 (3)	164
Symmetry codes: (i) -x, -y+2, -z+1; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x, y-1, z.

Figure 2
A view along the b axis of the crystal packing of the title compound. Hydrogen bonds are drawn as dashed lines.

Synthesis and crystallization

An equimolar ratio of 2-[(5-amino-1,3,4- thiadiazol-2-yl)thio]-N-(4-chlorophenyl)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	C₁₀H₉ClN₄OS₂
M_r	300.78
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	26.379 (5), 4.7704 (8), 10.1866 (18)
β (°)	96.996 (7)
V (Å³)	1272.3 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.62
Crystal size (mm)	0.32 × 0.23 × 0.12

Data collection
Diffractometer	Rigaku Saturn724+
Absorption correction	Multi-scan (NUMABS; Rigaku 1999 )
T_min, T_max	0.843, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	10559, 2881, 2019
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.127, 1.06
No. of reflections	2881
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.34
Computer programs: CrystalClear SM Expert (Rigaku, 2011 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ), OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1428528

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616011391/hg4010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616011391/hg4010Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616011391/hg4010Isup3.cml

checkCIF report

Computing details top

Data collection: CrystalClear SM Expert (Rigaku, 2011); cell refinement: CrystalClear SM Expert (Rigaku, 2011); data reduction: CrystalClear SM Expert (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-(4-chlorophenyl)acetamide top

Crystal data top

C₁₀H₉ClN₄OS₂	F(000) = 616
M_r = 300.78	D_x = 1.570 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 2881 reflections
a = 26.379 (5) Å	θ = 3.1–27.5°
b = 4.7704 (8) Å	µ = 0.62 mm⁻¹
c = 10.1866 (18) Å	T = 293 K
β = 96.996 (7)°	Block, brown
V = 1272.3 (4) Å³	0.32 × 0.23 × 0.12 mm
Z = 4

Data collection top

Rigaku Saturn724+ diffractometer	2019 reflections with I > 2σ(I)
profile data from ω–scans	R_int = 0.066
Absorption correction: multi-scan (NUMABS; Rigaku 1999)	θ_max = 27.5°, θ_min = 3.1°
T_min = 0.843, T_max = 0.928	h = −34→34
10559 measured reflections	k = −6→5
2881 independent reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.127	w = 1/[Σ²(F_o²) + (0.049P)² + 0.4848P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2881 reflections	Δρ_max = 0.34 e Å⁻³
163 parameters	Δρ_min = −0.34 e Å⁻³

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	U_iso*/U_eq
Cl1	0.45400 (4)	0.6782 (3)	0.30886 (13)	0.1062 (6)
S1	0.10780 (3)	0.59735 (16)	0.36162 (7)	0.0389 (2)
S2	0.15876 (3)	0.17391 (16)	0.55874 (7)	0.0409 (2)
O1	0.24709 (8)	0.7463 (4)	0.6213 (2)	0.0543 (8)
N1	0.08143 (8)	0.5253 (5)	0.5913 (2)	0.0386 (8)
N2	0.04937 (8)	0.7301 (5)	0.5344 (2)	0.0372 (7)
N3	0.03064 (8)	0.9734 (6)	0.3363 (2)	0.0422 (8)
N11	0.27991 (9)	0.3229 (5)	0.5821 (3)	0.0476 (9)
C1	0.05795 (10)	0.7883 (6)	0.4124 (2)	0.0331 (8)
C2	0.11406 (10)	0.4409 (6)	0.5160 (2)	0.0348 (9)
C3	0.20296 (10)	0.3442 (6)	0.6846 (3)	0.0394 (9)
C4	0.24508 (10)	0.4915 (6)	0.6270 (3)	0.0382 (9)
C5	0.32186 (11)	0.4125 (6)	0.5165 (3)	0.0435 (10)
C6	0.31545 (12)	0.6126 (7)	0.4193 (3)	0.0554 (11)
C7	0.35637 (14)	0.6942 (9)	0.3561 (4)	0.0704 (14)
C8	0.40275 (13)	0.5755 (9)	0.3893 (4)	0.0638 (14)
C9	0.40974 (13)	0.3734 (9)	0.4832 (4)	0.0719 (15)
C10	0.36869 (13)	0.2904 (8)	0.5480 (4)	0.0654 (16)
H3A	0.00600	1.06190	0.36610	0.0510*
H3B	0.03760	1.00480	0.25730	0.0510*
H3C	0.18440	0.47870	0.73200	0.0470*
H3D	0.21750	0.20480	0.74750	0.0470*
H6	0.28350	0.69330	0.39610	0.0670*
H7	0.35210	0.83100	0.29060	0.0840*
H9	0.44160	0.29080	0.50410	0.0860*
H10	0.37310	0.15200	0.61270	0.0790*
H11	0.27660	0.14560	0.59390	0.0570*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0674 (7)	0.1549 (13)	0.1040 (9)	−0.0259 (7)	0.0419 (6)	0.0066 (8)
S1	0.0432 (4)	0.0475 (5)	0.0289 (3)	0.0042 (3)	0.0162 (3)	−0.0013 (3)
S2	0.0409 (4)	0.0356 (4)	0.0466 (4)	−0.0003 (3)	0.0076 (3)	−0.0044 (3)
O1	0.0574 (13)	0.0294 (12)	0.0784 (17)	0.0021 (10)	0.0176 (12)	−0.0010 (11)
N1	0.0427 (13)	0.0462 (15)	0.0290 (11)	0.0023 (11)	0.0127 (10)	0.0006 (11)
N2	0.0389 (12)	0.0488 (15)	0.0259 (11)	0.0054 (10)	0.0127 (9)	0.0016 (10)
N3	0.0479 (14)	0.0551 (17)	0.0260 (11)	0.0120 (12)	0.0140 (10)	0.0046 (11)
N11	0.0482 (15)	0.0326 (14)	0.0654 (17)	−0.0006 (11)	0.0206 (12)	0.0012 (13)
C1	0.0339 (13)	0.0420 (17)	0.0251 (12)	−0.0035 (12)	0.0105 (10)	−0.0049 (12)
C2	0.0353 (13)	0.0394 (17)	0.0315 (14)	−0.0064 (12)	0.0109 (11)	−0.0019 (12)
C3	0.0434 (15)	0.0429 (18)	0.0328 (14)	0.0029 (13)	0.0086 (12)	0.0016 (13)
C4	0.0378 (14)	0.0358 (17)	0.0399 (15)	0.0025 (12)	0.0000 (12)	−0.0009 (13)
C5	0.0424 (16)	0.0399 (18)	0.0497 (18)	−0.0041 (13)	0.0116 (13)	−0.0058 (15)
C6	0.0480 (18)	0.065 (2)	0.054 (2)	−0.0009 (16)	0.0099 (15)	0.0080 (18)
C7	0.066 (2)	0.087 (3)	0.060 (2)	−0.006 (2)	0.0153 (18)	0.020 (2)
C8	0.051 (2)	0.082 (3)	0.061 (2)	−0.0152 (19)	0.0178 (17)	−0.006 (2)
C9	0.0408 (18)	0.091 (3)	0.086 (3)	0.0049 (19)	0.0159 (18)	−0.003 (2)
C10	0.050 (2)	0.072 (3)	0.077 (3)	0.0151 (18)	0.0187 (18)	0.019 (2)

Geometric parameters (Å, º) top

Cl1—C8	1.735 (4)	N3—H3A	0.8600
S1—C1	1.730 (3)	C5—C10	1.368 (5)
S1—C2	1.730 (2)	C5—C6	1.371 (4)
S2—C2	1.754 (3)	C6—C7	1.379 (5)
S2—C3	1.816 (3)	C7—C8	1.353 (5)
O1—C4	1.218 (3)	C8—C9	1.355 (6)
N1—N2	1.373 (3)	C9—C10	1.393 (5)
N1—C2	1.285 (3)	N11—H11	0.8600
N2—C1	1.320 (3)	C3—H3C	0.9700
N3—C1	1.328 (4)	C3—H3D	0.9700
N11—C4	1.343 (4)	C6—H6	0.9300
N11—C5	1.426 (4)	C7—H7	0.9300
C3—C4	1.494 (4)	C9—H9	0.9300
N3—H3B	0.8600	C10—H10	0.9300

C1—S1—C2	86.98 (12)	C6—C7—C8	120.0 (4)
C2—S2—C3	101.82 (13)	Cl1—C8—C9	119.2 (3)
N2—N1—C2	113.2 (2)	Cl1—C8—C7	119.8 (3)
N1—N2—C1	112.3 (2)	C7—C8—C9	121.0 (4)
C4—N11—C5	125.6 (2)	C8—C9—C10	119.4 (3)
S1—C1—N2	113.3 (2)	C5—C10—C9	120.0 (3)
S1—C1—N3	123.62 (17)	C4—N11—H11	117.00
N2—C1—N3	123.1 (2)	C5—N11—H11	117.00
S1—C2—S2	121.71 (14)	S2—C3—H3C	109.00
S1—C2—N1	114.2 (2)	S2—C3—H3D	109.00
S2—C2—N1	123.92 (18)	C4—C3—H3C	109.00
S2—C3—C4	112.2 (2)	C4—C3—H3D	109.00
H3A—N3—H3B	120.00	H3C—C3—H3D	108.00
C1—N3—H3B	120.00	C5—C6—H6	120.00
C1—N3—H3A	120.00	C7—C6—H6	120.00
N11—C4—C3	115.1 (2)	C6—C7—H7	120.00
O1—C4—C3	121.8 (3)	C8—C7—H7	120.00
O1—C4—N11	123.1 (3)	C8—C9—H9	120.00
N11—C5—C6	120.8 (3)	C10—C9—H9	120.00
N11—C5—C10	119.5 (3)	C5—C10—H10	120.00
C6—C5—C10	119.6 (3)	C9—C10—H10	120.00
C5—C6—C7	120.0 (3)

C2—S1—C1—N2	0.4 (2)	C4—N11—C5—C6	−44.4 (5)
C2—S1—C1—N3	−179.1 (3)	C4—N11—C5—C10	137.8 (3)
C1—S1—C2—S2	176.98 (19)	S2—C3—C4—O1	107.9 (3)
C1—S1—C2—N1	1.0 (2)	S2—C3—C4—N11	−71.8 (3)
C3—S2—C2—S1	112.82 (18)	N11—C5—C6—C7	−179.3 (3)
C3—S2—C2—N1	−71.6 (3)	C10—C5—C6—C7	−1.5 (5)
C2—S2—C3—C4	−89.6 (2)	N11—C5—C10—C9	179.1 (3)
C2—N1—N2—C1	2.3 (3)	C6—C5—C10—C9	1.2 (5)
N2—N1—C2—S1	−2.1 (3)	C5—C6—C7—C8	0.5 (6)
N2—N1—C2—S2	−177.95 (19)	C6—C7—C8—Cl1	179.7 (3)
N1—N2—C1—S1	−1.5 (3)	C6—C7—C8—C9	0.9 (6)
N1—N2—C1—N3	177.9 (2)	Cl1—C8—C9—C10	180.0 (3)
C5—N11—C4—O1	−3.4 (5)	C7—C8—C9—C10	−1.1 (6)
C5—N11—C4—C3	176.3 (3)	C8—C9—C10—C5	0.1 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱ	0.86	2.12	2.978 (3)	172
N3—H3B···N1ⁱⁱ	0.86	2.17	2.973 (3)	156
N3—H3B···N2ⁱⁱ	0.86	2.58	3.319 (3)	144
N11—H11···O1ⁱⁱⁱ	0.86	2.09	2.926 (3)	164

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

Acknowledgements

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

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2011). CrystalClear SM Expert. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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