4-({[4-Amino-6-(p-bromo­benz­yl)-5-oxo-4,5-dihydro-1,2,4-triazin-3-yl]sulfan­yl}acet­yl)-3-phenyl­sydnone

Hoong-Kun Fun; Ching Kheng Quah; Nithinchandra; Balakrishna Kalluraya

doi:10.1107/S1600536811010798

. 2011 Mar 31;67(Pt 4):o1004. doi: 10.1107/S1600536811010798

4-({[4-Amino-6-(p-bromobenzyl)-5-oxo-4,5-dihydro-1,2,4-triazin-3-yl]sulfanyl}acetyl)-3-phenylsydnone

Hoong-Kun Fun ^a,^*,^‡, Ching Kheng Quah ^a,^§, Nithinchandra ^b, Balakrishna Kalluraya ^b

PMCID: PMC3099816 PMID: 21754025

Abstract

In the title compound, C₂₀H₁₅BrN₆O₄S [symstematic name: 4-({[4-amino-6-(p-bromobenzyl)-5-oxo-4,5-dihydro-1,2,4-triazin-3-yl]sulfanyl}acetyl)-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate], the 4,5-dihydro-1,2,4-triazine ring is essentially planar [maximum deviation = 0.020 (1) Å] and is inclined at dihedral angles of 89.06 (9), 82.21 (8) and 83.98 (8)° with respect to the oxadiazol-3-ium, phenyl and benzene rings. The oxadiazol-3-ium ring forms dihedral angles of 52.71 (9) and 8.77 (9)°, respectively, with the phenyl and benzene rings. In the crystal, the molecules are linked via pairs of intermolecular N—H⋯O hydrogen bonds, generating R ₂ ²(10) ring motifs and are further linked via intermolecular N—H⋯N and weak C—H⋯O hydrogen bonds into infinite columns along [100].

Related literature

For general background to and the biological activity of sydnone derivatives, see: Rai et al. (2008) ▶; Jyothi et al. (2008 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₀H₁₅BrN₆O₄S
M _r = 515.35
Triclinic,
a = 6.3842 (3) Å
b = 10.0832 (5) Å
c = 17.1563 (8) Å
α = 104.873 (1)°
β = 93.507 (1)°
γ = 98.189 (1)°
V = 1050.99 (9) Å³
Z = 2
Mo Kα radiation
μ = 2.10 mm⁻¹
T = 100 K
0.32 × 0.26 × 0.06 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.553, T _max = 0.892
21938 measured reflections
6161 independent reflections
5241 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.089
S = 1.03
6161 reflections
297 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.95 e Å⁻³
Δρ_min = −0.50 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/S1600536811010798/lh5224sup1.cif

e-67-o1004-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010798/lh5224Isup2.hkl

e-67-o1004-Isup2.hkl^{(301.6KB, 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
N6—H1N6⋯N3ⁱ	0.81 (3)	2.47 (3)	2.9835 (19)	123 (2)
N6—H1N6⋯N4ⁱ	0.81 (3)	2.40 (3)	3.050 (2)	138 (3)
N6—H2N6⋯O4ⁱⁱ	0.86 (3)	2.15 (3)	2.989 (2)	164 (2)
C14—H14B⋯O3ⁱⁱⁱ	0.97	2.50	3.416 (2)	157

Open in a new tab

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

Acknowledgments

HKF and CKQ thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160).

supplementary crystallographic information

Comment

Sydnones are mesoionic heterocyclic aromatic chemical compounds. The study of sydnones remains as a field of interest because of their electronic structures and varied types of biological activities (Rai et al., 2008). Recently sydnone derivatives were found to exhibit promising antimicrobial properties (Jyothi et al., 2008). Since their discovery, sydnones have shown diverse biological activities and it is thought that the mesoionic nature of the sydnone ring promotes significant interactions with biological systems. Photochemical bromination of 3-aryl-4-acetylsydnone affords 3-aryl-4 bromoacetylsydnones. Condensation of 4-amino-6-(4-bromobenzyl)-3- sulfanyl-1,2,4-triazin-5(4H)-one with 3-aryl-4-bromoacetylsydnones yields S-substituted triazinone derivatives (Jyothi et al., 2008).

The molecular structure is shown in Fig. 1. The 4,5-dihydro-1,2,4-triazine ring (N3-N5/C11-C13) is essentially planar [maximum deviation = 0.020 (1) Å at atom N5] and is inclined at angles of 89.06 (9), 82.21 (8) and 83.98 (8) ° with respect to the oxadiazol-3-ium (O1/N1/N2/C7/C8) phenyl (C1-C6) and benzene (C15-C20) rings. The dihedral angles between oxadiazol-3-ium ring (O1/N1/N2/C7/C8) and the phenyl and benzene rings (C1-C6 and C15-C20) are 52.71 (9) and 8.77 (9)°, respectively. The bond lengths (Allen et al., 1987) and angles are within normal ranges.

In the crystal (Fig. 2), the molecules are linked via pairs of intermolecular N6–H2N6···O4ⁱⁱ hydrogen bonds (Table 1), generating R₂²(10) ring motifs (Bernstein et al., 1995) and are further linked via intermolecular N6–H1N6···N3ⁱ, N6–H1N6···N4ⁱ and weak C14–H14B···O3ⁱⁱⁱ hydrogen bonds (Table 1) into infinite one-dimensional columns along [100].

Experimental

To a solution of 4-bromoacetyl-3-phenylsydnone (0.01 mol) and 4-amino-6-(4-bromobenzyl)-3-sulfanyl-1,2,4-triazin-5(4H)-one (0.01 mol) in ethanol, catalytic amount of anhydrous sodium acetate was added. The solution was stirred at room temperature for 2 to 3 h. The solid product that separated out was filtered and dried. It was then recrystallized from ethanol. Crystals suitable for X-ray analysis were obtained from 1:2 mixtures of DMF and ethanol by slow evaporation.