7-(4-Chloro­benzyl­idene)-3-[(4-chloro­phen­oxy)meth­yl]-6-(4-nitro­thio­phen-2-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thia­diazine

Hoong-Kun Fun; Safra Izuani Jama Asik; Ibrahim Abdul Razak; Nithinchandra; Balakrishna Kalluraya

doi:10.1107/S1600536811015637

. 2011 Apr 29;67(Pt 5):o1266–o1267. doi: 10.1107/S1600536811015637

7-(4-Chlorobenzylidene)-3-[(4-chlorophenoxy)methyl]-6-(4-nitrothiophen-2-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine

Hoong-Kun Fun ^a,^*,^‡, Safra Izuani Jama Asik ^a, Ibrahim Abdul Razak ^a, Nithinchandra ^b, Balakrishna Kalluraya ^b

PMCID: PMC3089255 PMID: 21754553

Abstract

In the title compound, C₂₂H₁₃Cl₂N₅O₃S₂, the thiadiazine ring adopts a half-chair conformation. The benzene rings of the chlorophenoxy and chlorobenzyl groups and the thiophene ring form dihedral angles of 35.6 (1), 80.7 (1) and 14.2 (1)°, respectively, with the triazole ring. In the crystal, molecules are connected into sheets parallel to ( Inline graphic 11) by intermolecular C—H⋯N and C—H⋯Cl hydrogen bonds. In addition, π–π stacking interactions are observed between thiophene and triazole rings, and between inversion-related triazole rings [centroid–centroid distances = 3.5975 (11) and 3.4324 (11) Å].

Related literature

For general background to and applications of 1,2,4-triazole derivatives, see: Shujuan et al. (2004 ▶); Clemons et al. (2004 ▶); Johnston (2002 ▶); Wei et al. (2007 ▶). For ring conformations and ring puckering analysis, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶); Jin et al. (2004 ▶). For related structures, see: Goh et al. (2010a ▶,b ▶,c ▶,d ▶).

Experimental

Crystal data

C₂₂H₁₃Cl₂N₅O₃S₂
M _r = 530.39
Triclinic,
a = 8.5021 (2) Å
b = 10.0379 (2) Å
c = 14.3623 (3) Å
α = 94.434 (1)°
β = 97.981 (1)°
γ = 109.242 (1)°
V = 1136.07 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 296 K
0.39 × 0.32 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.827, T _max = 0.946
19590 measured reflections
6548 independent reflections
5142 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.133
S = 1.04
6548 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015637/ci5185sup1.cif

e-67-o1266-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015637/ci5185Isup2.hkl

e-67-o1266-Isup2.hkl^{(320.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15A⋯N2ⁱ	0.93	2.60	3.495 (3)	162
C21—H21A⋯Cl1ⁱⁱ	0.93	2.81	3.691 (2)	159

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

HKF, SIJA and IAR thank Universiti Sains Malaysia for the Research University Grants (Nos.1001/PFIZIK/811160 and 1001/PFIZIK/811151).

supplementary crystallographic information

Comment

The 1,2,4-triazole nucleus has been incorporated into a wide variety of therapeutically interesting compounds. Several compounds containing 1,2,4-triazole rings are well known as drugs. For example, fluconazole is used as an antimicrobial drug (Shujuan et al., 2004), while vorozole, letrozole and anastrozole are non-steroidal drugs used for the treatment of cancer (Clemons et al., 2004) and loreclezole is used as an anticonvulsant (Johnston et al., 2002). Similarly substituted derivatives of triazole possess comprehensive bioactivities such as antimicrobial, anti-inflammatory, analgesic, antihypertensive, anticonvulsant and antiviral activities (Wei et al., 2007). In continuation of our search on the synthesis of biologically active compounds, we synthesized triazolothiadiazine from triazole.

In the title compound, the 1,2,4-triazole (C8/N1–N3/C9) and thiophene (C12–C15/S2) rings are essentially planar, with maximum deviations of 0.006 (2) and 0.003 (2) Å for atom C9 and C14, respectively. The 1,3,4-thiadiazine (C9–C11/N3/N4/S1) ring is slightly distorted and may be regarded as having a half-chair conformation with puckering parameters, Q = 0.474 (2) Å, θ = 113.9 (2)°, φ = 149.1 (2)° (Cremer & Pople, 1975).

The two benzene rings (C1–C6 and C17–C22) and the thiophene (C12–C15/S2) ring form dihedral angles of 35.6 (1), 80.7 (1) and 14.2 (1)°, respectively, with the 1,2,4-triazole ring (C8/N1–N3/C9). The geometric parameters are consistent with those observed in closely related structures (Goh et al., 2010a,b,c,d). The bond lengths show normal values (Allen et al. 1987).

In the crystal packing (Fig. 2), the molecules are connected by intermolecular C15—H15A···N2 and C21—H21A···Cl1 interactions that link the molecules into two–dimensional arrays parallel to the (1 1 1). In addition, the molecular packing is also stabilized by π–π stacking interactions between thiophene (C12–C15/S2; centroid Cg1) and 1,2,4-triazole (C8/N1–N3/C9; centroid Cg2) rings, with a Cg1···Cg2^# separation of 3.5975 (11) Å (symmetry code #: 1-x, 1-y, -z), and that between 1,2,4-triazole (C8/N1–N3/C9) rings at (x, y, z) and (-x, 1-y, -z), with their centroids separated by 3.4324 (11) Å.

Experimental

To a soultion of 4-Amino-5-[(p-chlorophenoxy)methyl]-4H-1,2,4-triazole-3-thiol (0.01 mol) and 2-bromo-3-(p-chlorophenyl)-1-(5-nitrothiophen-2-yl) prop-2-en-1-one (0.01 mol) in ethanol, a catalytic amount of anhydrous sodium acetate was added. The solution was refluxed on a water bath for 9 h. The solid product that separated out was filtered and dried. It was then recrystallized from ethanol. Single crystals suitable for X-ray analysis were obtained from a 1:2 mixture of DMF and ethanol by slow evaporation.