4,4-Dimethyl-2-[3-nitro-2-phenyl-1-(phenyl­sulfan­yl)prop­yl]-4,5-dihydro-1,3-oxazole

Ignez Caracelli; Julio Zukerman-Schpector; José A F P Villar; Alfredo R M Oliveira; Edward R T Tiekink

doi:10.1107/S1600536812012512

. 2012 Mar 31;68(Pt 4):o1225–o1226. doi: 10.1107/S1600536812012512

4,4-Dimethyl-2-[3-nitro-2-phenyl-1-(phenylsulfanyl)propyl]-4,5-dihydro-1,3-oxazole

Ignez Caracelli ^a,^*, Julio Zukerman-Schpector ^b, José A F P Villar ^c, Alfredo R M Oliveira ^d, Edward R T Tiekink ^e

PMCID: PMC3344158 PMID: 22606161

Abstract

In the title compound, C₂₀H₂₂N₂O₃S, the oxazoline ring is planar (r.m.s. deviation = 0.045 Å) and forms dihedral angles of 47.24 (8) and 10.11 (8)° with the S- and C-bound phenyl rings, respectively. The nitro group lies to the same side of the molecule as the oxazoline ring but is orientated so as not to interact with the ring. Linear supramolecular chains along [010] are formed via C—H⋯O and C—H⋯S contacts. Chains are consolidated into a three-dimensional architecture by C—H⋯π and van der Waals interactions.

Related literature

For background on the biological activities of Rolipram, see: de Visser et al. (2008 ▶). For the synthesis of the title compound, see Villar (2008 ▶); Oliveira et al. (2007 ▶).

Experimental

Crystal data

C₂₀H₂₂N₂O₃S
M _r = 370.47
Monoclinic,
a = 15.339 (3) Å
b = 5.7040 (8) Å
c = 22.786 (4) Å
β = 107.166 (2)°
V = 1904.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 98 K
0.25 × 0.15 × 0.15 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.809, T _max = 1.000
15389 measured reflections
4362 independent reflections
4146 reflections with I > 2σ(I)
R _int = 0.035
Standard reflections: 0

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.114
S = 1.11
4362 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR92 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶), DIAMOND (Brandenburg, 2006 ▶) and MarvinSketch (ChemAxon, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812012512/qk2035sup1.cif

e-68-o1225-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812012512/qk2035Isup2.hkl

e-68-o1225-Isup2.hkl^{(209.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812012512/qk2035Isup3.cml

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

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

Cg2 and Cg3 are the centroids of the C7–C12 and C15–C20 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯O3ⁱ	0.99	2.52	3.376 (2)	145
C20—H20⋯S1ⁱⁱ	0.95	2.79	3.7194 (19)	166
C8—H8⋯Cg2ⁱⁱⁱ	0.95	2.71	3.4345 (18)	134
C17—H17⋯Cg3^iv	0.95	2.99	3.712 (2)	134

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

Acknowledgments

The authors thank FAPESP, CNPq (grant No. 306532/2009-3 to JZS; grant No. 308116/2010-0 to IC) and CAPES (grant No. 808/2009 to JZS and IC) for financial support. The authors also gratefully thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (grant No. UM.C/HIR/MOHE/SC/12).

supplementary crystallographic information

Comment

While developing a new route aiming at the synthesis of 4-[3-(cyclopentyloxy)-4-methoxyphenyl]pyrrolidin-2-one (Rolipram), a phosphodiesterase-4 inhibitor which has been shown to have anti-inflammatory properties (de Visser et al., 2008), the title compound, (I), was obtained during a systematic study of the addition reaction of oxazolines to nitroestyrene (Villar, 2008; Oliveira et al. 2007). The crystals were crystallographically characterized and the results are now reported herein.

In (I), Fig. 1, the oxazoline ring is planar (r.m.s. deviation = 0.045 Å) with the maximum deviations being 0.036 (2) Å for the C3 atom and -0.038 (2) Å for the C4 atom. The five-membered ring and the S-bound phenyl ring (C7–C12) are proximate and make a dihedral angle of 47.24 (8)°. The dihedral angles formed by these rings and the C-bound phenyl ring (C15–C20) are 10.11 (8) and 57.13 (8)°, respectively. The nitro group lies to the same side of the molecule as the oxazoline ring but is orientated away from the ring.

In the crystal packing, inversion related molecules are linked via C14—H14B···O3 contacts with the resultant dimeric aggregates connected into a linear supramolecular chain along [010] via C20—H20···S1 contacts, Fig. 2 and Table 1. Chains are consolidated in the three-dimensional packing by C—H···π and van der Waals interactions, Fig. 3 and Table 1.

Experimental

The detailed synthesis of the title compound is described in a Ph.D. thesis (Villar, 2008). Crystals were grown by slow evaporation from an ethylacetate/ hexane solution held at 293 K. ¹H-NMR (CDCl₃, 400 MHz): δ (p.p.m.) 1.07 (s, 3H); 1.18 (s, 3H); 3.87(d, 1H, J = 8.15 Hz); 3.93 (d, 1H, J = 8.15 Hz); 3.98 (ddd, 1H, J = 8.43, 9.15, 5.27 Hz); 4.17 (d, 1H, J = 8.43 Hz); 4.97 (dd, 1H, J = 13.25, 5.27 Hz); 5.01 (dd, 1H, J = 13.25, 9.15 Hz); 7.18–7.34 (m, 8H); 7.38–7.42 (m, 2H); ¹³C (CDCl₃, 100 MHz) δ (p.p.m.) 162.01; 136.34; 133.75; 132.43; 129.08; 128.91; 128.55; 128.39; 127.93; 79.44; 77.22; 67.44; 49.93; 45.85; 28.04. Analysis found: C 64.83, H 5.97, N 7.61, S 8.85%. C₂₀H₂₂N₂O₃S requires: C 64.84, H 5.99, N 7.56, S 8.65%.