1′-Methyl-3′-(4-methyl­benzo­yl)-4′-[5-(2-thien­yl)-2-thien­yl]spiro­[acenaphthyl­ene-1,2′-pyrrolidin]-2(1H)-one

S Thenmozhi; E Govindan; D Gavaskar; R Raghunathan; A SubbiahPandi

doi:10.1107/S1600536810053869

. 2011 Jan 8;67(Pt 2):o267. doi: 10.1107/S1600536810053869

1′-Methyl-3′-(4-methylbenzoyl)-4′-[5-(2-thienyl)-2-thienyl]spiro[acenaphthylene-1,2′-pyrrolidin]-2(1H)-one

S Thenmozhi ^a, E Govindan ^a, D Gavaskar ^b, R Raghunathan ^b, A SubbiahPandi ^a,^*

PMCID: PMC3051628 PMID: 21522959

Abstract

In the title compound, C₃₂H₂₅NO₂S₂, the mean plane through the five-membered pyrrolidine ring, which exhibits an envelope conformation, makes dihedral angles of 82.3 (1) and 83.9 (9)° with the benzene ring and the acenaphthylene ring system, respectively. The dihedral angle between the thiophene rings is 19.0(3)°. The crystal structure shows C—H⋯π and π–π interactions [centroid–centroid distance = 3.869 (2) Å].

Related literature

For puckering parameters, see: Cremer & Pople (1975 ▶). For asymmetry parameters, see: Nardelli (1983 ▶).

Experimental

Crystal data

C₃₂H₂₅NO₂S₂
M _r = 519.65
Monoclinic,
a = 10.2188 (5) Å
b = 10.0191 (5) Å
c = 24.8192 (11) Å
β = 96.115 (2)°
V = 2526.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.931, T _max = 0.953
24301 measured reflections
4373 independent reflections
3294 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.127
S = 1.06
4373 reflections
357 parameters
5 restraints
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810053869/bt5402sup1.cif

e-67-0o267-sup1.cif^{(28.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053869/bt5402Isup2.hkl

e-67-0o267-Isup2.hkl^{(209.9KB, hkl)}

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

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

Cg8 is the centroid of the C18–C23 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C32—H32⋯Cg8ⁱ	0.93	2.86	3.661 (3)	145

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Symmetry code: (i) Inline graphic .

Acknowledgments

ST and ASP thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

Comment

Fig. 1 shows a displacement ellipsoid diagram of the molecule with the atomic numbering scheme. The geometry of the acenaphthylene moiety compares well with that reported in other compounds. The N—C and C—C bond lengths in the pyrrolidine moiety are slightly longer than the normal values reported for similar structures. This may be due to steric forces caused by the bulky substituents on the pyrrolidine moiety. The pyrrolidine ring makes dihedral angles of 82.3 (1) and 83.9 (9)° with the phenyl ring and the acenaphthylene ring system respectively. Ketone atom O1 deviates by 0.272 (2)Å from the (C1/C2/C11/C10/C12) plane. The sum of the angles at N1 of the pyrrolidine ring (340.1°) is in accordance with sp³ hybridization.

The pyrrolidine ring adopt an twist conformation, with the puckering parameters q₂ and φ (Cremer & Pople, 1975) and the smallest displacement asymmetric parameters, Δ, (Nardelli et al., 1983) as follows: q₂= 0.379 (2) Å, φ=160.3 (3)°, Δ_s(C12)= 16.28 (19)°. The ring (C1/C2/C11/C10/C12) adopt an twist conformation, with the puckering parameters q₂ and φ (Cremer & Pople, 1975) and the smallest displacement asymmetric parameters, Δ, (Nardelli et al., 1983) as follows: q₂= 0.122 (2) Å, φ=162.5 (10)°, Δ_s(C11)= 4.1 (2)°.

The molecular structure is influenced by C–H···O intramolecular interactions. In addition to van der Waals interaction, the crystal packing is stabilized by C–H···π (Table. 1) hydrogen bonds as well as by π–π electron interactions. The π–π electron interactions between the rings Cg7 - Cg8 at x, y, z with the centroid-centroid distance equal to 3.8655 (12) Å, is observed in the crystal structure [Cg7 and Cg8 are the centeroid of the rings C6—C11 and C18—C23].

Experimental

A solution of the (4-chloro-phenyl-3-Bithiophenyl-prop-2-ene-1-one derived from Bithiophene (1- mmol), Acenapthoquinone (1 mmol), sarcosine (1 mmol) in toluene (30 ml) was refluxed for 8 hrs. The progress of the reacion was evidenced by the TLC analysis. The solvent was removed under reduced pressure and the crude product was subjected to column chromatogarphy using petroleum ether/ethyl acetate (4:1) as solvent. X-ray diffraction were obtained by slow evaporation of a solution of the title compound in hexene at room temperature.