6-(3-Chloro­phen­yl)imidazo[2,1-b][1,3,4]thia­diazole

Praveen, A.S.; Jasinski, J.P.; Krauss, S.T.; Yathirajan, H.S.; Narayana, B.

doi:10.1107/S1600536812049793

organic compounds

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Volume 69| Part 1| January 2013| Page o66

https://doi.org/10.1107/S1600536812049793

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6-(3-Chlorophenyl)imidazo[2,1-b][1,3,4]thiadiazole

A.S. Praveen,^a Jerry P. Jasinski,^b ^* Shannon T. Krauss,^b H. S. Yathirajan ^a and B. Narayana ^c

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and ^cDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 25 November 2012; accepted 4 December 2012; online 12 December 2012)

In the title compound, C₁₀H₈ClN₃S, the dihedral angle between the mean planes of the benzene and imidazo[2,1-b][1,3,4]thiadiazole rings is 6.0 (9)°. In the crystal, molecules are assembled by the formation of centrosymmetric dimers by π-stacking of the thiadiazole and benzene rings of neighboring molecules [centroid–centroid distance = 3.6938 (11) Å] along [010].

Related literature

For related imidazothiadiazole derivatives and their pharmacological potential, see: Palagiano et al. (1995 ). For related structures, see: Banu et al. (2011a ,b ); Fun et al. (2011a ,b ). For standard bond lengths, see Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₆ClN₃S
M_r = 235.70
Monoclinic, P 2₁ /n
a = 5.43804 (19) Å
b = 12.4222 (4) Å
c = 14.1684 (4) Å
β = 100.269 (3)°
V = 941.77 (5) Å³
Z = 4
Cu Kα radiation
μ = 5.37 mm⁻¹
T = 173 K
0.26 × 0.12 × 0.06 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ) T_min = 0.691, T_max = 1.000
5495 measured reflections
1846 independent reflections
1650 reflections with I > 2σ(I))
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.100
S = 1.06
1846 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812049793/im2414sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049793/im2414Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812049793/im2414Isup3.cml

checkCIF report

Comment top

Many imidazothiadiazole derivatives have been reported to possess diverse medicinal properties such as anthelmintic, antimicrobial, anti-inflammatory, antipyretic, analgesic properties and many other activities of therapeutic significance (Palagiano et al., 1995). The crystal structures of some imidazothiadiazole molecules, viz., 6-(4-bromophenyl)-2-(4-fluorobenzyl)imidazo[2,1-b][1,3,4] thiadiazole, 3-{[6-(4-Chlorophenyl)imidazo[2,1-b][1,3,4]thiadiazol-2-yl] methyl}-1,2-benzoxazole (Banu et al., 2011a,b), 2-isobutyl-6-(4-methoxyphenyl)imidazo[2,1-b][1,3,4]thiadiazole and 6-(4-chlorophenyl)-2-isobutylimidazo[2,1-b][1,3,4]thiadiazole (Fun et al., 2011a,b) have been reported.

In the title compound, C₁₀H₈N₃SCl, the dihedral angle between the mean planes of the benzene and imidazo[2,1b][1,3,4]thiadiazole rings is 6.0 (9)° (Fig. 1). Bond lengths are in normal ranges (Allen et al., 1987). In the crystal, molecules are assembled by the formation of centrosymmetric dimers by π-stacking of thiadiazole and benzene rings of neighboring molecules (centroid–centroid distance = 3.6938 (11) Å) along [010] (Fig. 2). Additional weak π-stacking interactions involving nearby benzene rings (centroid-centroid distance = 3.7739 (11) Å) are also observed.

Related literature top

For related imidazothiadiazole derivatives and their pharmacological potential, see: Palagiano et al. (1995). For related structures, see: Banu et al. (2011a,b); Fun et al. (2011a,b). For standard bond lengths, see Allen et al. (1987).

Experimental top

A solution of 1,3,4-thiadiazol-2-amine (500 mg, 4.9 mmol) and 2-bromo-1-(3-chlorophenyl)ethanone (1.1 g, 4.9 mmol) in DMF (10 mL) was placed in a microwave pyrex tube which was introduced into a Biotage Initiator-microwave reactor fitted with a rotational system. Microwave irradiation was performed for 10 minutes at 373 K, then the mixture was cooled to ambient temperature. The reaction mass was poured into ice, the precipitated solid was filtered and dried. The single crystal was grown from a solution in ethyl acetate by slow evaporation of the solvent (yield: 97%; (m.p.: 437–440 K).

Structure description top

For related imidazothiadiazole derivatives and their pharmacological potential, see: Palagiano et al. (1995). For related structures, see: Banu et al. (2011a,b); Fun et al. (2011a,b). For standard bond lengths, see Allen et al. (1987).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed along the a axis. Dashed lines indicate π-stacking of thiadiazole and benzene rings of neighboring molecules (centroid–centroid distance = 3.6938 (11)Å) into centrosymmetric dimers along [010]. Hydrogen atoms have been removed for clarity.

6-(3-Chlorophenyl)imidazo[2,1-b][1,3,4]thiadiazole top

Crystal data top

C₁₀H₆ClN₃S	F(000) = 480
M_r = 235.70	D_x = 1.676 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 2788 reflections
a = 5.43804 (19) Å	θ = 3.2–72.4°
b = 12.4222 (4) Å	µ = 5.37 mm⁻¹
c = 14.1684 (4) Å	T = 173 K
β = 100.269 (3)°	Chunk, colorless
V = 941.77 (5) Å³	0.26 × 0.12 × 0.06 mm
Z = 4

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	1846 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1650 reflections with I > 2σ(I))
Graphite monochromator	R_int = 0.046
Detector resolution: 16.0416 pixels mm^-1	θ_max = 72.5°, θ_min = 4.8°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	k = −12→15
T_min = 0.691, T_max = 1.000	l = −17→13
5495 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.100	w = 1/[σ²(F_o²) + (0.0559P)² + 0.2711P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
1846 reflections	Δρ_max = 0.36 e Å⁻³
137 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0028 (5)

Crystal data top

C₁₀H₆ClN₃S	V = 941.77 (5) Å³
M_r = 235.70	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 5.43804 (19) Å	µ = 5.37 mm⁻¹
b = 12.4222 (4) Å	T = 173 K
c = 14.1684 (4) Å	0.26 × 0.12 × 0.06 mm
β = 100.269 (3)°

Data collection top

Agilent Xcalibur (Eos, Gemini) diffractometer	1846 independent reflections
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)	1650 reflections with I > 2σ(I))
T_min = 0.691, T_max = 1.000	R_int = 0.046
5495 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.06	Δρ_max = 0.36 e Å⁻³
1846 reflections	Δρ_min = −0.23 e Å⁻³
137 parameters

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.

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
Cl1	0.35900 (10)	0.10200 (4)	0.67741 (4)	0.02949 (18)
S1	0.39725 (10)	0.62878 (4)	0.24567 (3)	0.02652 (18)
N1	0.0469 (3)	0.61595 (14)	0.34925 (13)	0.0253 (4)
N2	0.2006 (3)	0.52794 (13)	0.36757 (12)	0.0199 (4)
N3	0.5314 (3)	0.43233 (13)	0.34504 (12)	0.0222 (4)
C1	0.1320 (4)	0.67447 (17)	0.28675 (15)	0.0261 (4)
H1	0.0545	0.7386	0.2645	0.031*
C2	0.3979 (4)	0.51895 (15)	0.32099 (13)	0.0208 (4)
C3	0.2043 (4)	0.44025 (16)	0.42652 (14)	0.0217 (4)
H3	0.0929	0.4235	0.4671	0.026*
C4	0.4101 (4)	0.38271 (15)	0.41207 (13)	0.0190 (4)
C5	0.5067 (3)	0.28278 (15)	0.46084 (13)	0.0192 (4)
C6	0.3963 (3)	0.24196 (15)	0.53512 (14)	0.0205 (4)
H6	0.2605	0.2769	0.5531	0.025*
C7	0.4911 (4)	0.14891 (16)	0.58176 (13)	0.0213 (4)
C8	0.6921 (4)	0.09440 (16)	0.55644 (16)	0.0258 (4)
H8	0.7526	0.0317	0.5881	0.031*
C9	0.8008 (4)	0.13562 (16)	0.48276 (15)	0.0254 (4)
H9	0.9360	0.1001	0.4650	0.030*
C10	0.7107 (4)	0.22930 (15)	0.43499 (14)	0.0219 (4)
H10	0.7861	0.2563	0.3860	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0325 (3)	0.0305 (3)	0.0269 (3)	0.00059 (19)	0.0091 (2)	0.00925 (19)
S1	0.0346 (3)	0.0247 (3)	0.0222 (3)	0.00174 (19)	0.0104 (2)	0.00440 (18)
N1	0.0239 (9)	0.0224 (8)	0.0297 (9)	0.0063 (6)	0.0050 (7)	0.0021 (7)
N2	0.0198 (8)	0.0193 (8)	0.0212 (8)	0.0029 (6)	0.0052 (6)	−0.0002 (6)
N3	0.0228 (8)	0.0234 (8)	0.0221 (8)	0.0031 (7)	0.0087 (7)	0.0004 (6)
C1	0.0292 (11)	0.0235 (10)	0.0246 (10)	0.0033 (8)	0.0019 (8)	0.0003 (8)
C2	0.0243 (10)	0.0224 (9)	0.0167 (9)	−0.0007 (7)	0.0069 (7)	−0.0006 (7)
C3	0.0237 (10)	0.0215 (9)	0.0220 (9)	0.0030 (7)	0.0096 (8)	0.0032 (7)
C4	0.0195 (10)	0.0208 (9)	0.0166 (9)	0.0000 (7)	0.0027 (7)	−0.0023 (7)
C5	0.0190 (9)	0.0200 (9)	0.0181 (9)	−0.0005 (7)	0.0021 (7)	−0.0034 (7)
C6	0.0194 (9)	0.0220 (9)	0.0203 (9)	0.0013 (7)	0.0045 (7)	−0.0021 (7)
C7	0.0212 (10)	0.0228 (9)	0.0197 (9)	−0.0031 (8)	0.0035 (8)	0.0002 (7)
C8	0.0256 (10)	0.0220 (10)	0.0289 (11)	0.0044 (8)	0.0023 (9)	0.0022 (8)
C9	0.0220 (10)	0.0258 (10)	0.0292 (10)	0.0043 (8)	0.0069 (8)	−0.0028 (8)
C10	0.0229 (10)	0.0221 (9)	0.0214 (9)	−0.0003 (8)	0.0063 (8)	−0.0023 (7)

Geometric parameters (Å, º) top

Cl1—C7	1.7432 (19)	C4—C5	1.471 (3)
S1—C2	1.7318 (19)	C5—C6	1.397 (3)
S1—C1	1.744 (2)	C5—C10	1.397 (3)
N1—C1	1.293 (3)	C6—C7	1.385 (3)
N1—N2	1.373 (2)	C6—H6	0.9300
N2—C2	1.361 (3)	C7—C8	1.386 (3)
N2—C3	1.371 (2)	C8—C9	1.386 (3)
N3—C2	1.309 (2)	C8—H8	0.9300
N3—C4	1.393 (2)	C9—C10	1.391 (3)
C1—H1	0.9300	C9—H9	0.9300
C3—C4	1.373 (3)	C10—H10	0.9300
C3—H3	0.9300

C2—S1—C1	87.81 (9)	C6—C5—C10	119.54 (18)
C1—N1—N2	107.27 (17)	C6—C5—C4	119.66 (17)
C2—N2—C3	107.63 (16)	C10—C5—C4	120.79 (18)
C2—N2—N1	118.68 (16)	C7—C6—C5	119.29 (17)
C3—N2—N1	133.69 (17)	C7—C6—H6	120.4
C2—N3—C4	103.49 (15)	C5—C6—H6	120.4
N1—C1—S1	117.63 (16)	C6—C7—C8	121.87 (18)
N1—C1—H1	121.2	C6—C7—Cl1	118.69 (15)
S1—C1—H1	121.2	C8—C7—Cl1	119.41 (16)
N3—C2—N2	112.95 (17)	C9—C8—C7	118.44 (19)
N3—C2—S1	138.46 (15)	C9—C8—H8	120.8
N2—C2—S1	108.59 (14)	C7—C8—H8	120.8
N2—C3—C4	104.29 (16)	C8—C9—C10	121.00 (19)
N2—C3—H3	127.9	C8—C9—H9	119.5
C4—C3—H3	127.9	C10—C9—H9	119.5
C3—C4—N3	111.64 (16)	C9—C10—C5	119.86 (18)
C3—C4—C5	126.96 (18)	C9—C10—H10	120.1
N3—C4—C5	121.37 (17)	C5—C10—H10	120.1

C1—N1—N2—C2	0.2 (2)	C2—N3—C4—C3	0.4 (2)
C1—N1—N2—C3	179.7 (2)	C2—N3—C4—C5	−177.68 (17)
N2—N1—C1—S1	0.3 (2)	C3—C4—C5—C6	−4.9 (3)
C2—S1—C1—N1	−0.45 (17)	N3—C4—C5—C6	172.90 (17)
C4—N3—C2—N2	−0.1 (2)	C3—C4—C5—C10	176.33 (19)
C4—N3—C2—S1	179.75 (18)	N3—C4—C5—C10	−5.9 (3)
C3—N2—C2—N3	−0.2 (2)	C10—C5—C6—C7	−0.1 (3)
N1—N2—C2—N3	179.44 (17)	C4—C5—C6—C7	−178.88 (17)
C3—N2—C2—S1	179.87 (13)	C5—C6—C7—C8	−0.4 (3)
N1—N2—C2—S1	−0.5 (2)	C5—C6—C7—Cl1	177.50 (14)
C1—S1—C2—N3	−179.4 (2)	C6—C7—C8—C9	0.5 (3)
C1—S1—C2—N2	0.47 (14)	Cl1—C7—C8—C9	−177.37 (15)
C2—N2—C3—C4	0.5 (2)	C7—C8—C9—C10	−0.1 (3)
N1—N2—C3—C4	−179.12 (19)	C8—C9—C10—C5	−0.4 (3)
N2—C3—C4—N3	−0.6 (2)	C6—C5—C10—C9	0.5 (3)
N2—C3—C4—C5	177.43 (17)	C4—C5—C10—C9	179.27 (18)

Experimental details

Crystal data
Chemical formula	C₁₀H₆ClN₃S
M_r	235.70
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	5.43804 (19), 12.4222 (4), 14.1684 (4)
β (°)	100.269 (3)
V (Å³)	941.77 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	5.37
Crystal size (mm)	0.26 × 0.12 × 0.06

Data collection
Diffractometer	Agilent Xcalibur (Eos, Gemini)
Absorption correction	Multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012)
T_min, T_max	0.691, 1.000
No. of measured, independent and observed [I > 2σ(I))] reflections	5495, 1846, 1650
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.100, 1.06
No. of reflections	1846
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.23

Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008).

Acknowledgements

ASP thanks the UOM for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

References

Agilent (2012). CrysAlis PRO and CrysAlis RED Agilent Technologies, Yarnton, England. Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Banu, A., Begum, N. S., Lamani, R. S. & Khazi, I. M. (2011a). Acta Cryst. E67, o779. Web of Science CSD CrossRef IUCr Journals Google Scholar
Banu, A., Ziaulla, M., Begum, N. S., Lamani, R. S. & Khazi, I. M. (2011b). Acta Cryst. E67, o617–o618. Web of Science CrossRef IUCr Journals Google Scholar
Fun, H.-K., Hemamalini, M., Prasad, D. J., Nagaraja, G. K. & Anitha, V. V. (2011b). Acta Cryst. E67, o207. Web of Science CrossRef IUCr Journals Google Scholar
Fun, H.-K., Yeap, C. S., Prasad, D. J., Castelino, P. A. & Anitha, V. V. (2011a). Acta Cryst. E67, o255. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Palagiano, F., Arenare, L., Laraschi, E., de Caprariis, P., Abignente, E., Amico, M. D., Filippelli, W. & Rossi, F. (1995). Eur. J. Med. Chem. 30, 901–910. CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar