Crystal structure of 1′-(2-methyl­prop­yl)-2,3-di­hydro­spiro­[1-benzo­thio­pyran-4,4′-imidazolidine]-2′,5′-dione

Cynthia E Theodore; S Naveen; S B Benaka Prasad; M Madaiah; C S Ananda Kumar; N K Lokanath

doi:10.1107/S1600536814018030

. 2014 Aug 23;70(Pt 9):o1043–o1044. doi: 10.1107/S1600536814018030

Crystal structure of 1′-(2-methylpropyl)-2,3-dihydrospiro[1-benzothiopyran-4,4′-imidazolidine]-2′,5′-dione

Cynthia E Theodore ^a, S Naveen ^b, S B Benaka Prasad ^a, M Madaiah ^c, C S Ananda Kumar ^d, N K Lokanath ^e,^*

PMCID: PMC4186156 PMID: 25309216

Abstract

In the title compound, C₁₅H₁₈N₂O₂S, the 2,3-dihydro-1-benzothiopyran ring adopts a sofa conformation and the hydantoin ring is twisted with respect to the benzene ring at 78.73 (17)°. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into inversion dimers.

Keywords: crystal structure; hydantoin compounds; hydrogen bonding; spiro[1-benzothiopyran-4,4′-imidazolidine]

Related literature

For background and applications of hydantoin compounds, see: Nefzi et al. (2002 ▶); Park & Kurth (2000 ▶); Manjunath et al. (2012 ▶); Hussein et al. (2014 ▶). For related structures, see: Manjunath et al. (2011 ▶); Hussein et al. (2014 ▶).

Experimental

Crystal data

C₁₅H₁₈N₂O₂S
M _r = 290.38
Monoclinic,
a = 13.279 (3) Å
b = 9.939 (3) Å
c = 13.264 (3) Å
β = 118.56 (1)°
V = 1537.6 (7) Å³
Z = 4
Cu Kα radiation
μ = 1.90 mm⁻¹
T = 296 K
0.20 × 0.15 × 0.15 mm

Data collection

Bruker X8 Proteum diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶) T _min = 0.747, T _max = 0.753
5024 measured reflections
2397 independent reflections
1959 reflections with I > 2σ(I)
R _int = 0.067

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.195
S = 1.06
2397 reflections
184 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); 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, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814018030/xu5809sup1.cif

e-70-o1043-sup1.cif^{(25.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018030/xu5809Isup2.hkl

e-70-o1043-Isup2.hkl^{(117.8KB, hkl)}

Click here for additional data file.^{(5.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814018030/xu5809Isup3.cml

Click here for additional data file.^{(3.3MB, tif)}

. DOI: 10.1107/S1600536814018030/xu5809fig1.tif

A view of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1.8MB, tif)}

. DOI: 10.1107/S1600536814018030/xu5809fig2.tif

A view of the crystal packing of the title compound showing inverted dimers.

CCDC reference: 1018087

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11⋯O16ⁱ	0.86	2.03	2.850 (3)	160

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are thankful to the IOE, Vijnana Bhavana, University of Mysore, Mysore, for providing the single-crystal X-ray diffraction facility.

supplementary crystallographic information

S1. Comment

The combinatorial generation of organic compound libraries has emerged as a powerful tool for drug discovery. Small substituted heterocyclic compounds play an important role in the development of biologically active substances by offering a high structural diversity. Among such heterocycles, particularly the hydantoin scaffold opens the possibility of different kinds and degrees of substitution. They have been the focus of attention as a ubiquitous moiety incorporated into compounds with numerous biological activities and therapeutic applications (Nefzi et al., 2002). A variety of combinatorial approaches have been described by which pharmacophoric groups were attached to such a relatively rigid scaffold (Park & Kurth, 2000). Therefore, the chemistry of multiple substituted hydantoins has newly attracted much interest, and traditional approaches have been combined with recently developed strategies. Hence as a part of our ongoing research on hydantoins (Manjunath et al., 2012; Hussein et al., 2014), the synthesis, characterization and the structural work of the title compound was undertaken and herein we report its crystal structure.

The hydantoin ring in the structure is planar within the experimental limits with a maximum deviation of 0.012 (2) Å for N1 atom from the least-squares plane of the hydantoin ring. The N—C bong length values of N11—C12 = 1.349 (3) Å, N13—C12 = 1.400 (4) Å and N13—C14 = 1.359 (2) Å are comparable with the values reported earlier (Manjunath et al., 2011; Hussein et al., 2014). The shortened bond length values can be attributed to the π conjugation in the hydantoin ring. The isobutyl group is twisted out of the plane of the hydantoin ring as indicated by the torsion angle values of -175.6 (3)° and 61.5 (3)° for the atoms N13—C17—C18—C20 and N13—C17—C18—C19 indicating that they are in antiperiplanar and synclinal conformations respectively.

The study of torsion angles, asymmetric parameters and least-squares plane reveals that the 2,3-dihydro-1-benzothiopyran ring in the structure adopts envelope conformation with S1 atom deviating by 0.0851 (14) Å from the least-squares plane. This is confirmed by the puckering amplitude Q = 0.519 (3) Å. The hydantoin ring is in a equatorial position with the 2,3-dihydro-1-benzothiopyran ring which is evident by the dihedral angle of 81.15 (15)°. This value is slightly lesser than the value reported earlier (Hussein et al., 2014) for 1-ethyl-2',3'-dihydrospiro[imidazoline-4,1-indene]-2,5-dione. The molecules are interlinked by N—H···O hydrogen bonds to form inverted dimers.

S2. Experimental

A solution of spiro[1-benzothiopyran-4,4'-imidazolidine]-2',5'-dione (1.0 eq) in N,N-dimethylformamide was taken, anhydrous K₂CO₃ (3.0 eq) was added to the solution and stirred for 10 min. 1-Bromo–2 methyl propane (1–1.1 eq) was then added. The reaction mixture was stirred at room temperature for 8 h and the progress of the reaction was monitored by TLC. Upon completion, the solvent was removed under reduced pressure and the residue was taken in water and extracted with ethyl acetate. Finally water wash was given to the organic layer and dried over anhydrous sodium sulfate. The solvent was evaporated. The crude product was purified by column chromatography using chloroform:methanol (9:1) as an eluent. Single crystals were obtained from slow evaporation of its solvent.