11-[(E)-Benzyl­idene]-14-hy­droxy-8-phenyl-6-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; Abdulrahman I Almansour; Suhana Arshad; Ibrahim Abdul Razak

doi:10.1107/S1600536812024270

. 2012 Jun 13;68(Pt 7):o2013–o2014. doi: 10.1107/S1600536812024270

11-[(E)-Benzylidene]-14-hydroxy-8-phenyl-6-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,^‡, Abdulrahman I Almansour ^b, Suhana Arshad ^c, Ibrahim Abdul Razak ^c,^*,^§

PMCID: PMC3393284 PMID: 22807841

Abstract

In the title compound, C₃₄H₂₈N₂O₂S, the piperidine ring adopts a chair conformation. One of the pyrrolidine rings adopts an envelope conformation with the methylene C atom at the flap whereas the other pyrrolidine ring and the thiazolidine ring adopt half-chair conformations. The mean plane of the dihydroacenaphthylene ring system [maximum deviation = 0.067 (1) Å] makes dihedral angles of 28.31 (5) and 31.32 (6)° with the two terminal benzene rings. An intramolecular O—H⋯N hydrogen bond forms an S(5) ring motif. In the crystal, molecules are linked by C—H⋯O and C—H⋯S hydrogen bonds into layers lying parallel to the ac plane.

Related literature

For general background to heterocycles, see: Corey et al. (2007 ▶); Padwa (1984 ▶); Lee et al. (2001 ▶); Lalezari & Schwartz (1988 ▶); Aicher et al. (1998 ▶). For related structures, see: Kumar et al. (2010a ▶,b ▶, 2011 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₃₄H₂₈N₂O₂S
M _r = 528.64
Monoclinic,
a = 11.2911 (1) Å
b = 15.4317 (2) Å
c = 15.1920 (2) Å
β = 92.790 (1)°
V = 2643.93 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 100 K
0.45 × 0.41 × 0.31 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.932, T _max = 0.953
37231 measured reflections
9686 independent reflections
8170 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.129
S = 1.04
9686 reflections
344 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.18 e Å⁻³
Δρ_min = −1.12 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/S1600536812024270/hb6800sup1.cif

e-68-o2013-sup1.cif^{(37.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024270/hb6800Isup2.hkl

e-68-o2013-Isup2.hkl^{(473.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812024270/hb6800Isup3.cml

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
O2—H1O2⋯N2	0.86 (2)	1.95 (2)	2.6277 (12)	134.4 (18)
C8—H8A⋯O1ⁱ	0.99	2.55	3.1981 (14)	123
C15—H15A⋯S1ⁱⁱ	0.95	2.72	3.4970 (13)	139
C18—H18A⋯O1ⁱⁱⁱ	0.95	2.60	3.2550 (15)	127
C24—H24A⋯O2^iv	0.95	2.59	3.4077 (18)	145

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the Research University grants Nos. 203/PKIMIA/6711179 and 1001/PFIZIK/811151. RSK and AIM thank the Research Center, Deanship of Scientific Research, College of Science, King Saud University. SA thanks the Malaysian Government and USM for an Academic Staff Training Scheme (ASTS) Fellowship.

supplementary crystallographic information

Comment

The synthesis and chemistry of heterocyclic compounds has been an interesting field in view of their structural diversity and remarkable ability to serve as biomimetics and active pharmacophores. Many of the most famous natural alkaloids or unnatural drugs consist of at least one heterocyclic ring (Corey et al., 2007). 1,3-Dipolar cycloaddition of azomethine ylides to olefinic dipolarophiles affords five membered heterocyclic rings of biological importance (Padwa, 1984). Heterocycles with piperidine sub-structures are being used as synthons in the construction of alkaloid natural products (Lee et al., 2001). Pyrrolothiazole ring possesses antineoplastic (Lalezari & Schwartz, 1988) and hypoglycemic (Aicher et al., 1998) activity. The importance of aforesaid heterocycles, incited us to investigate the X-ray diffraction study of the title compound and report the results in this paper.

In the molecular structure (Fig. 1), the piperidine ring (N1/C1–C5) adopts a chair conformation with puckering parameters (Cremer & Pople, 1975), Q= 0.6090 (10) Å, Θ= 37.98 (10)° and Φ= 303.45 (16)°.

For the two pyrrolidine rings, N1/C4/C5/C10/C11 is in envelope conformation with atom C5 deviating by 0.298 (1) Å from the mean plane through the remaining atoms [puckering parameters Q= 0.4579 (10) Å and φ=29.43 (13)°] whereas N2/C4/C6/C7/C10 is twisted about C6–C4 bond, [puckering parameters, Q= 0.3869 (10) Å and φ= 261.97 (15)°] adopting a half-chair conformation. The thiazolidine ring, S1/N2/C7–C9 is twisted about C8–S1 bond [puckering parameters, Q= 0.4519 (10) Å and φ= 333.87 (14)°] thereby, also adopting a half-chair conformations.

The mean plane of the dihydroacenaphthylene ring system [C10/C11/C25–C33, maximum deviation = 0.067 (1) Å at atom C10] makes dihedral angles of 28.31 (5) and 31.32 (6)°, respectively, with the two terminal benzene rings (C13–C18 & C19–C24).

An intramolecular O2—H1O2···N2 hydrogen bond (Table 1) forms an S(5) ring motif (Bernstein et al., 1995). The bond lengths and angles are within normal ranges and comparable to the related structure (Kumar et al., 2010a,b; Kumar et al., 2011).

The crystal packing is shown in Fig. 2. The intermolecular C8—H8A···O1, C15—H15A···S1, C18—H18A···O1 and C24—H24A···O2 (Table 1) hydrogen bonds link the molecules into two-dimensional network parallel to ac-plane.

Experimental

A mixture of 3,5-bis[(E)-phenylmethylidene] tetrahydro-4(1H)-pyridinone (1 mmol), acenaphthenequinone (1 mmol), and thiazolidine-2-carboxylic acid (1 mmol) were dissolved in methanol (5 ml) and refluxed for 1 h. 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 recrystallization from pet.ether-ethyl acetate mixture to obtain colourless blocks.