N-(1-Acetyl-r-7,c-9-diphenyl-4,8-dithia-1,2-diaza­spiro­[5.4]dec-2-en-3-yl)acet­amide

D Gayathri; D Velmurugan; S Umamatheswari; S Kabilan; K Ravikumar

doi:10.1107/S1600536808001025

. 2008 Jan 23;64(Pt 2):o494–o495. doi: 10.1107/S1600536808001025

N-(1-Acetyl-r-7,c-9-diphenyl-4,8-dithia-1,2-diazaspiro[5.4]dec-2-en-3-yl)acetamide

D Gayathri ^a, D Velmurugan ^a,^*, S Umamatheswari ^b, S Kabilan ^b, K Ravikumar ^c

PMCID: PMC2960219 PMID: 21201517

Abstract

In the title compound, C₂₂H₂₃N₃O₂S₂, the five-membered ring is planar and the C₅S ring adopts a chair conformation. The crystal packing is stabilized by intermolecular N—H⋯O and C—H⋯O interactions, generating a chain and a centrosymmetric dimer, respectively.

Related literature

For related literature, see: Allen et al. (1987 ▶); Isaac et al. (2003 ▶); Pan et al. (2003 ▶); Jung et al. (2004 ▶); Foroumadi et al. (2002 ▶); Jalilian et al. (2002 ▶); Leung-Toung et al. (2003 ▶); Schmidt et al. (1970 ▶); Cremer & Pople (1975 ▶); Nardelli (1983 ▶); Singh et al. (2003 ▶).

Experimental

Crystal data

C₂₂H₂₃N₃O₂S₂
M _r = 425.55
Monoclinic,
a = 12.3310 (7) Å
b = 16.0218 (9) Å
c = 12.3852 (7) Å
β = 116.714 (1)°
V = 2185.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 (2) K
0.25 × 0.24 × 0.22 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: none
24434 measured reflections
5139 independent reflections
4587 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.116
S = 0.97
5139 reflections
264 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808001025/at2527sup1.cif

e-64-0o494-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001025/at2527Isup2.hkl

e-64-0o494-Isup2.hkl^{(246.6KB, 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
N3—H3⋯O1ⁱ	0.86	1.94	2.786 (2)	166
C5—H5⋯O2ⁱⁱ	0.98	2.49	3.446 (2)	163

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

Acknowledgments

DG thanks CSIR, India, for the award of a Senior Research Fellowship. DV thanks DST, India, for a major research project, and acknowledges the Department of Science and Technology (DST-FIST) and the University Grants Commission (UGC), Government of India, for the provision of research facilities.

supplementary crystallographic information

Comment

Tetrahydrothiopyrans play major roles in the field of medicinal chemistry (Isaac et al., 2003). 1,3,4-Thiadiazoline nucleus, a biologically active heterocyclic ring, is also associated with a wide range of pharmacological activities (Pan et al., 2003; Jung et al., 2004; Foroumadi et al., 2002; Jalilian et al., 2002; Leung-Toung et al., 2003). An essential component of the search for new leads in a drug-design programme is the synthesis of molecules, which is novel and resembles known biologically active molecules by virtue of the presence of certain pharmocophoric groups. Certain small heterocyclic molecules act as highly functionalized scaffolds and are pharmacophores of a number of biologically active and medicinally useful molecules. As the title compound (I) is of much biological importance, we have undertaken the crystal structure determination by X-ray diffraction.

The bond lengths and bond angles in (I) are comparable with those in the literature (Allen et al., 1987). The sum of the bond angles around N1 atom [360.0 (3)°] indicates the sp² hybridization. The torsion angles C19—C18—N1—N2 [-0.1 (2)°) and C19—C18—N1—C3 [-179.3 (1)°] indicate that atoms C18 and C19 lie in the plane of the five membered ring (N1/N2/C20/S2/C3). Also the torsion angles C22—C21—N3—C20 [-177.3 (2)°], O2—C21—N3—C20 [2.4 (3)°], C21—N3—C20—S2 [2.3 (2)°] and C21—N3—C20—N2 [-178.1 (2)°] indicate that the substituted moiety at C20 lie in the plane of the ring to which it is attached. The dihedral angle between the two phenyl rings in the structure is about 77.6 (1)° which clearly indicates that the two phenyl rings are nearly perpendicular to each other.

The six membered ring C1—C5/S1 adopts chair conformation with the puckering parameters (Cremer & Pople, 1975) and the smallest displacement asymmetry parameters (Nardelli, 1983) being q₂ = 0.117 (1) Å, q₃ = 0.651 (1) Å; Q_T = 0.661 (1)Å and θ = 10.2 (1)°.

The crystal packing is stabilized N—H···O and C—H···O intermolecular interaction generating a chain of C(7) and a centrosymmetric dimer of R₂²(18) ring, respectively.

Experimental

2,6-Diphenyltetrahydrothiopyran-4-one thiosemicarbazone (0.025 mol) was treated with freshly distilled acetic anhydride and the mixture was refluxed for 8 h on a water bath (363–373 K). The removal of solvent from the cooled reaction mixture in vaccuo afforded 4-acetyl-2-acetylamino-5-spiro-((r)-2,(c)6-diphenyltetrahydrothiopyran-4-yl)- 4,5-dihydro-[1,3,4]thiadiazole which was purified in neutral alumina column using n-hexane-ethyl acetate (4:1) as eluent. The pure compound was recrystallized from ethanol [m.p.: 399 K].