14-Hy­droxy-11-[(E)-4-meth­oxy­benzyl­idene]-8-(4-meth­oxy­phen­yl)-5-thia-3,13-diaza­hepta­cyclo­[13.7.1.19,13.02,9.02,14.03,7.019,23]tetra­cosa-1(22),15(23),16,18,20-pentaen-10-one

Raju Suresh Kumar; Hasnah Osman; A S Abdul Rahim; Madhukar Hemamalini; Hoong-Kun Fun

doi:10.1107/S160053681104061X

. 2011 Oct 8;67(Pt 11):o2881–o2882. doi: 10.1107/S160053681104061X

14-Hydroxy-11-[(E)-4-methoxybenzylidene]-8-(4-methoxyphenyl)-5-thia-3,13-diazaheptacyclo[13.7.1.1^9,13.0^2,9.0^2,14.0^3,7.0^19,23]tetracosa-1(22),15(23),16,18,20-pentaen-10-one

Raju Suresh Kumar ^a, Hasnah Osman ^a,^‡, A S Abdul Rahim ^b, Madhukar Hemamalini ^c, Hoong-Kun Fun ^c,^*,^§

PMCID: PMC3247613 PMID: 22219918

Abstract

In the title compound, C₃₆H₃₂N₂O₄S, the piperidine ring adopts a chair conformation, while the five-membered pyrrolidine (with a C atom as the flap atom) and thiazolidine (with the S atom as the flap atom) rings adopt envelope conformations. The naphthalene ring system makes dihedral angles of 18.82 (5) and 40.92 (5)° with the two methoxy-substituted benzene rings. In the crystal, centrosymmetrically-related molecules are linked into dimers via pairs of C—H⋯O and C—H⋯N hydrogen bonds. An intramolecular O—H⋯N hydrogen bond is also observed. The crystal structure is further stabilized by C—H⋯π interactions.

Related literature

For details of cycloaddition, see: Tsuge & Kanemasa (1989 ▶); Nair & Suja (2007 ▶); Aicher et al. (1998 ▶); Lalezari & Schwartz (1988 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₃₆H₃₂N₂O₄S
M _r = 588.70
Triclinic,
a = 10.6287 (1) Å
b = 11.8672 (2) Å
c = 12.6588 (2) Å
α = 84.439 (1)°
β = 75.105 (1)°
γ = 68.553 (1)°
V = 1436.19 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 100 K
0.37 × 0.25 × 0.16 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.943, T _max = 0.975
39492 measured reflections
11591 independent reflections
9231 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.142
S = 1.02
11591 reflections
394 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.38 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 datablock(s) global, I. DOI: 10.1107/S160053681104061X/hb6431sup1.cif

e-67-o2881-sup1.cif^{(30.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681104061X/hb6431Isup2.hkl

e-67-o2881-Isup2.hkl^{(555.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681104061X/hb6431Isup3.cml

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

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

Cg7 and Cg9 centroids of the C20–C25 and C31–C36 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯N2	0.86 (2)	1.96 (2)	2.6253 (14)	133.3 (19)
C24—H24A⋯N1ⁱ	0.95	2.61	3.4447 (15)	146
C26—H26C⋯O1ⁱ	0.98	2.48	3.4078 (17)	157
C19—H19B⋯Cg7ⁱⁱ	0.98	2.82	3.4652 (18)	124
C26—H26B⋯Cg7ⁱⁱⁱ	0.98	2.87	3.7720 (14)	154
C9—H9B⋯Cg9^iv	0.99	2.87	3.8211 (14)	161

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

Acknowledgments

RSK, HO and ASA thank Universiti Sains Malaysia (USM) for the University Research Grant No. 203/PKIMIA/6711179 and the Ministry of Science, Technology and Innovation Grant No. 09-05-lfn-meb-004. RSK also thanks USM for the award of a post-doctoral fellowship. HKF and MH thank the Malaysian Government and USM for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks USM for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Three-component reactions involving [3+2]-cycloaddition of azomethine ylides to olefinic dipolarophiles constitutes a facile approach for the construction of five membered heterocyclic rings of biological importance (Tsuge & Kanemasa, 1989; Nair & Suja, 2007). Among these heterocycles, pyrrolo[2,1-b]thiazole is an unusual ring system with antineoplastic (Lalezari & Schwartz, 1988) and hypoglycemic (Aicher et al., 1998) activities. In this paper we wish to report the crystal structure determination of the title compound possessing the biologically-active pyrrolothiazole ring.

The asymmetric unit of the title compound is shown in Fig. 1. The six-membered piperidine (N1/C1–C5) ring adopts a chair conformation [Q = 0.6172 (12) Å; θ = 138.18 (11)° and φ = 119.73 (17)°; Cremer & Pople, 1975] while the five-membered pyrrolidine (N2/C4/C6,C7/C10) and thiazolidine (S1/N2/C7–C9) rings adopt an envelope conformation with the C6 (displacement -0.217 (1) Å) and the S1 (displacement 0.284 (1) Å) atoms as the flap atoms and with puckering parameters, Q = 0.3565 (13) Å; φ = 89.37 (19)°; and Q = 0.5087 (11) Å; and φ = 0.44 (14)° repectively. The naphthalene (C27–C36) ring makes dihedral angles of 18.82 (5)° and 40.92 (5)° with the two methoxy-substituted (C13–C18)/(C20–C25) phenyl rings.

In the crystal structure, (Fig. 2), the centrosymmetrically-related molecules are linked into dimers via pairs of intermolecular C—H···O and C—H···N (Table 1) hydrogen bonds. An intramolecular O—H..N hydrogen bond is also observed. The crystal structure is further stabilized by weak C—H···π interactions involving the centroids Cg7 and Cg9 of the (C20–C25) and (C31–C36) rings, respectively.

Experimental

A mixture of 3,5-bis[(E)-(4-methoxyphenyl) methylidene]-tetrahydro-4(1H)-pyridinone (1 mmol), acenaphthenequinone (1 mmol), and thiazolidine-4-carboxylic acid (1 mmol) were dissolved in methanol (5 mL) and refluxed for 1 hour. After completion of the reaction as evident from TLC, the mixture was poured into water (50 mL). The precipitated solid was filtered and washed with water to obtain the product which was further purified by recrystallisation from pet.ether-ethylacetate mixture to yield colourless blocks of (I).