4-[(3-Benzamido­methyl-6-phenyl-6,7-dihydro-5H-1,2,4-triazolo[3,4-b][1,3,4]thia­diazin-7-yl)carbon­yl]-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate 0.06-hydrate

Hoong-Kun Fun; Madhukar Hemamalini; Nithinchandra; Balakrishna Kalluraya

doi:10.1107/S1600536810049998

. 2010 Dec 15;67(Pt 1):o128–o129. doi: 10.1107/S1600536810049998

4-[(3-Benzamidomethyl-6-phenyl-6,7-dihydro-5H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazin-7-yl)carbonyl]-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate 0.06-hydrate

Hoong-Kun Fun ^a,^*,^‡, Madhukar Hemamalini ^a, Nithinchandra ^b, Balakrishna Kalluraya ^b

PMCID: PMC3050302 PMID: 21522639

Abstract

The asymmetric unit of the title compound, C₂₇H₂₁N₇O₄S·0.06H₂O, contains four syndone molecules and a water molecule with a site occupancy of 0.25. In two of the syndone molecules, three atoms in a terminal phenyl ring are disordered over two sets of sites, with occupancy ratios of 0.500 (18):0.500 (18) and 0.512 (17):0.488 (17). The dihedral angles between terminal phenyl rings for the syndone molecules are 23.3 (4), 45.57 (16), 68.46 (16) and 56.5 (3)°. In the crystal, molecules are connected via N—H⋯N, N—H⋯O, O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For biological applications of sydnones, see: Newton & Ramsden (1982 ▶); Wagner & Hill (1974 ▶); Kalluraya & Rahiman (1997 ▶); Kalluraya et al. (2002 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₇H₂₁N₇O₄S·0.06H₂O
M _r = 540.69
Triclinic,
a = 15.6242 (19) Å
b = 18.7430 (19) Å
c = 18.9689 (19) Å
α = 111.235 (2)°
β = 93.970 (2)°
γ = 101.636 (2)°
V = 5009.4 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 100 K
0.64 × 0.08 × 0.07 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009) ▶ T _min = 0.893, T _max = 0.988
54193 measured reflections
17604 independent reflections
12624 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.141
S = 1.04
17604 reflections
1498 parameters
54 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.41 e Å⁻³
Δρ_min = −0.30 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/S1600536810049998/hb5742sup1.cif

e-67-0o128-sup1.cif^{(76.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810049998/hb5742Isup2.hkl

e-67-0o128-Isup2.hkl^{(843KB, 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
O1W—H2W1⋯O2C	0.85	1.92	2.772 (4)	175
O1W—H1W1⋯N6B	0.85	2.10	2.944 (4)	174
N7A—H1NA⋯N5Bⁱ	0.94 (5)	2.15 (5)	3.017 (4)	153 (4)
N7A—H1NA⋯N6Bⁱ	0.94 (5)	2.19 (6)	3.016 (4)	146 (3)
N2A—H2NA⋯O3A	0.78 (3)	2.35 (3)	2.912 (3)	130 (3)
N7B—H1NB⋯N6Aⁱⁱ	0.86 (4)	2.16 (4)	2.964 (4)	155 (3)
N3B—H2NB⋯O3B	0.88 (3)	2.25 (3)	2.865 (3)	127 (3)
N7C—H1NC⋯N6Dⁱⁱⁱ	0.80 (3)	2.21 (3)	2.990 (4)	165 (3)
N3C—H2NC⋯O3C	0.91 (3)	2.21 (3)	2.895 (3)	132 (3)
N7D—H1ND⋯N6Cⁱⁱⁱ	0.89 (3)	2.25 (3)	3.082 (4)	157 (3)
N3D—H2ND⋯O3D	0.94 (3)	2.07 (3)	2.841 (3)	138 (3)
C1A—H1XA⋯O2Bⁱ	1.16	2.43	3.471 (10)	148
C5A—H5AA⋯O4A^iv	0.93	2.45	3.294 (4)	151
C1B—H1BA⋯O4B^v	0.93	2.40	3.278 (4)	158
C11A—H11A⋯O4A^iv	0.98	2.60	3.291 (4)	128
C5B—H5BA⋯O2Aⁱⁱ	0.93	2.51	3.405 (4)	162
C19D—H19D⋯O2B^vi	0.93	2.41	3.289 (11)	157
C5D—H5DA⋯O4Dⁱⁱⁱ	0.93	2.47	3.328 (4)	154
C23A—H23A⋯O3A^iv	0.93	2.59	3.318 (4)	136
C23B—H23B⋯O3B^v	0.93	2.41	3.240 (4)	149
C27C—H27C⋯O3C^vii	0.93	2.52	3.359 (4)	150
C27D—H27D⋯O3Dⁱⁱⁱ	0.93	2.42	3.258 (4)	149

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160. MH thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Sydnones are class of mesoionic compounds containing a 1,2,3-oxadiazole ring system. A number of sydnone derivatives have shown diverse biological activities such as anti-inflammatory, analgesic and anti-arthritic (Newton & Ramsden, 1982; Wagner & Hill, 1974) properties. Sydnones possessing heterocyclic moieties at the 4-position are also known for a wide range of biological properties (Kalluraya & Rahiman, 1997). Encouraged by these reports and in continuation of our research for biologically active nitrogen containing heterocycles, a triazolothiadiazole moiety at the 4-position of the phenylsydnone was introduced. A series of triazolothiadiazoles were synthesized by the reaction of 2,3-dibromo-1-(3'-arylsydnon-4'-yl)-3-aryl- propan-1-one with 3-substituted-4-amino-5-mercapto-1,2,4-triazoles (Kalluraya et al., 2002).

The asymmetric unit of the title compound consists of two crystallographically independent syndone molecules (B & C) (Fig. 1a), two crystallographically independent disordered syndone molecules (A & D) (Fig. 1b) and a water molecule with a refined site occupancy of 0.25. In the disordered syndone molecules, three atoms C1A, C2A, C3A (molecule A) and C19D, C20D, C21D (molecule D) in the terminal phenyl rings are disordered over two positions, with occupancy ratios of 0.500 (18):0.500 (18) (molecule A) and 0.512 (17): 0.488 (17) (molecule D). The dihedral angles between terminal phenyl rings (C1A–C6A)/(C16A–C21A), (C1B–C6B)/(C16B–C21B), (C1C–C6C)/(C16C–C21C) and (C1D–C6D)/ (C16D–C21D) for all the syndone molecules are 23.3 (4)°, 45.57 (16)°, 68.46 (16)° and 56.5 (3)° respectively.

In the crystal structure (Fig. 2), all molecules are connected via intra and inter molecular N—H···N, N—H···O and C—H···O (Table 1) hydrogen bonds to form a three-dimensional network.

Experimental

N-[(4-amino-5-mercapto-4H-1,2,4-triazol-3-yl)methyl]benzamide (0.01 mol) and 2,3-dibromo-1-(3'-phenylsydnon-4'-yl)-3-phenyl-propan-1-one (0.01 mol) in ethanol was treated with aqueous solution of sodium acetate (0.01 mol). The reaction mixture was refluxed on a water bath for 1–2 hours. The excess of ethanol was removed by distillation and the reaction mixture was kept overnight. The solid product separated was filtered. It was then recrystallized from ethanol. Colourless needles were obtained from 1:2 mixtures of DMF and ethanol by slow evaporation.