11-[(E)-2-Fluoro­benzyl­idene]-8-(2-fluoro­phen­yl)-14-hy­droxy-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/S1600536812025512

. 2012 Jun 13;68(Pt 7):o2094–o2095. doi: 10.1107/S1600536812025512

11-[(E)-2-Fluorobenzylidene]-8-(2-fluorophenyl)-14-hydroxy-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: PMC3393908 PMID: 22798773

Abstract

In the title compound, C₃₄H₂₆F₂N₂O₂S, an intramolecular O—H⋯N hydrogen bond forms an S(5) ring motif. The piperidine ring adopts a chair conformation. The thiazolidine ring and one of the pyrrolidine rings adopt envolope conformations with methylene C atoms at the flap, whereas the other pyrrolidine ring adopts a half-chair conformation. The fluoro-substituted benzene rings form dihedral angles of 32.25 (10) and 38.27 (10)°, respectively, with the mean plane of the dihydroacenaphthylene ring system [maximum deviation = 0.043 (2) Å]. The dihedral angle between the fluoro-substituted benzene rings is 64.13 (14)°. In the crystal, molecules are linked by weak C—H⋯O, C—H⋯F and C—H⋯S hydrogen bonds into a three-dimensional network.

Related literature

For general background to the applications of nitrogen heterocycles, see: Orru & de Greef (2003 ▶); Kirsch et al. (2004 ▶); Padwa (1984 ▶); For related structures, see: Kumar et al. (2010a ▶,b ▶, 2011a ▶,b ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₃₄H₂₆F₂N₂O₂S
M _r = 564.63
Monoclinic,
a = 11.1783 (10) Å
b = 16.1033 (14) Å
c = 15.2165 (13) Å
β = 92.838 (2)°
V = 2735.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 296 K
0.40 × 0.26 × 0.15 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.936, T _max = 0.976
30643 measured reflections
7981 independent reflections
4714 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.173
S = 1.03
7981 reflections
374 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.37 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/S1600536812025512/lh5479sup1.cif

e-68-o2094-sup1.cif^{(38.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025512/lh5479Isup2.hkl

e-68-o2094-Isup2.hkl^{(390.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812025512/lh5479Isup3.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
O1—H1O1⋯N1	0.89 (3)	1.96 (3)	2.636 (2)	132 (3)
C14—H14A⋯O2ⁱ	0.97	2.54	3.156 (3)	121
C22—H22A⋯F1ⁱⁱ	0.93	2.44	3.351 (3)	166
C25—H25A⋯S1ⁱⁱⁱ	0.93	2.78	3.545 (3)	140

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

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 the Academic Staff Training Scheme (ASTS) Fellowship.

supplementary crystallographic information

Comment

The development of new efficient methods to synthesize nitrogen heterocycles with structural diversity is one of the major objectives of modern synthetic organic chemists as these heterocycles are widely prevalent in nature and play a pivotal role in the pharmaceutical and drug industry (Orru & de Greef, 2003; Kirsch et al., 2004). 1,3-Dipolar cycloaddition of azomethine ylides is a versatile protocol for the construction of highly functionalized N-heterocycles (Padwa, 1984). As a continuation of our research program (Kumar et al., 2010a,b; Kumar et al., 2011a,b), we report the X-ray crystal structure determination of the title compound.

The molecular structure is shown in Fig. 1. The bond lengths and angles are within normal ranges and comparable to related structures (Kumar et al., 2010a,b; Kumar et al., 2011a,b). An intramolecular O1—H1O1···N1 hydrogen bond (Table 1) forms an S(5) ring motif (Bernstein et al., 1995). The piperidine ring (N2/C17–C21) adopts a chair conformation with puckering parameters (Cremer & Pople, 1975), Q= 0.6115 (19) Å, Θ= 142.58 (18)° and Φ= 236.7 (3)°. For the thiazolidine ring, S1/N1/C13–C15 adopts an envelope conformation with atom C14 on the flap with puckering parameters Q= 0.4212 (19) Å and φ= 209.8 (3)°. The two pyrrolidine rings adopt different conformations, N1/C12/C15–C17 is twisted about C16–C17 bond [puckering parameters, Q= 0.3857 (19) Å and φ= 273.7 (3)°], hence adopting a half-chair conformation. Meanwhile, the N2/C11/C12/C17/C18 ring is in envelope conformation with atom C18 at the flap [puckering parameters Q= 0.4598 (19) Å and φ= 148.3 (2)°]. The fluoro-substituted benzene rings (C23–C28 & C29–C34) form dihedral angles of 32.25 (10) and 38.27 (10)°, respectively, with the mean plane of the dihydroacenaphthylene ring system [C2–C12, maximum deviation of 0.043 (2) Å at atom C11]. The dihedral angle between the fluoro substituted benzene rings is 64.13 (14)°.

In the crystal packing (Fig. 2), the molecules are linked into three dimensional network via intermolecular C14—H14A···O2ⁱ, C22—H22A···F1ⁱⁱ and C25—H25A···S1ⁱⁱⁱ (Table 1) hydrogen bonds.

Experimental

A mixture of 3,5-bis[(E)-(2-fluorophenyl) methylidene]-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 (200 mL) and recrystallized from ethyl acetate to give the title compound as colourless crystals.