Crystal structure of 3-meth­oxy­carbonyl-2-(4-meth­oxy­phen­yl)-8-oxo-1-aza­spiro[4.5]deca-1,6,9-trien-1-ium-1-olate

Lucimara Julio Martins; Deborah de Alencar Simoni; Ricardo Aparicio; Fernando Coelho

doi:10.1107/S1600536814023277

. 2014 Oct 29;70(Pt 11):o1200–o1201. doi: 10.1107/S1600536814023277

Crystal structure of 3-methoxycarbonyl-2-(4-methoxyphenyl)-8-oxo-1-azaspiro[4.5]deca-1,6,9-trien-1-ium-1-olate

Lucimara Julio Martins ^a, Deborah de Alencar Simoni ^b, Ricardo Aparicio ^c,^*, Fernando Coelho ^a

PMCID: PMC4257292 PMID: 25484828

Abstract

The title compound, C₁₈H₁₇NO₅, was prepared by a synthetic strategy based on the Heck reaction from Morita–Baylis–Hillman adducts. The five-membered ring adopts a slightly twisted conformation on the C_a—C_m (a = aromatic and m = methylene) bond. The dihedral angle between the five-membered ring and the spiro aromatic ring is 89.35 (7)°; that between the five-membered ring and the 4-methoxybenzene ring is 4.65 (7)°. Two short intramolecular C—H⋯O contacts occur. In the crystal, molecules are linked by C—H⋯O hydrogen bonds to generate a three-dimensional network.

Keywords: single-crystal X-ray study, spirohexadienone structure, Morita–Baylis–Hillman aducts

Related literature

For compounds that contain a spirohexadienone moiety in their structures, see: Wright & König (1993 ▶); König et al. (1990 ▶); Beil et al. (1998 ▶) and for their biological activities, see: Glushkov et al. (2010 ▶); Pereira et al. (2007 ▶). For strategies for the synthesis of spiro-hexadienones from Morita–Baylis–Hillman adducts, see: Coelho et al. (2002 ▶); Ferreira et al. (2009 ▶); Pirovani et al. (2009 ▶); Martins et al. (2014 ▶). For the biological activity of compounds containing a nitrone group, see: Fangour et al. (2009 ▶); Floyd et al. (2008 ▶); Halliwell & Gutteridge (1999 ▶); Fevig et al. (1996 ▶). For a discussion about non-classical hydrogen bonds, see: Desiraju (2005 ▶).

Experimental

Crystal data

C₁₈H₁₇NO₅
M _r = 327.32
Triclinic,
a = 6.0916 (11) Å
b = 8.7713 (16) Å
c = 15.167 (3) Å
α = 80.255 (6)°
β = 81.703 (6)°
γ = 80.122 (6)°
V = 781.3 (2) Å³
Z = 2
Cu Kα radiation
μ = 0.85 mm⁻¹
T = 100 K
0.47 × 0.20 × 0.17 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2010 ▶) T _min = 0.813, T _max = 1.000
14656 measured reflections
2771 independent reflections
2727 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.105
S = 1.11
2771 reflections
220 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▶); molecular graphics: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814023277/hb7301sup1.cif

e-70-o1200-sup1.cif^{(439.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814023277/hb7301Isup2.hkl

e-70-o1200-Isup2.hkl^{(152.2KB, hkl)}

Click here for additional data file.^{(3.1KB, cdx)}

Supporting information file. DOI: 10.1107/S1600536814023277/hb7301Isup3.cdx

Click here for additional data file.^{(6.4KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814023277/hb7301Isup4.cml

Click here for additional data file.^{(1.7MB, tif)}

. DOI: 10.1107/S1600536814023277/hb7301fig1.tif

The molecular structure of the title compound with 50% probability displacement ellipsoids.

Click here for additional data file.^{(1.6MB, tif)}

. DOI: 10.1107/S1600536814023277/hb7301fig2.tif

Crystal packing of the title compound, showing hydrogen bonding interactions.

CCDC reference: 1030399

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C8H1CO1ⁱ	0.98	2.59	3.4941(18)	153
C4H3O1ⁱ	0.95	2.38	3.1345(16)	136
C3H4O1	0.95	2.22	2.8725(17)	125
C14H8O3	0.95	2.57	3.3431(18)	138
C15H9O5ⁱⁱ	0.95	2.56	3.3821(17)	146
C18H13O2ⁱⁱⁱ	0.95	2.54	3.4309(17)	155
C17H14O3^iv	0.95	2.38	3.2408(18)	151
C12H15AO5^v	0.99	2.60	3.5402(18)	159
C9H16O1^vi	1.00	2.31	3.2045(16)	148

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

Acknowledgments

The authors acknowledge Dr Cristiane Storck Schwalm for the data collection and preliminary data processing and structure refinement and thank the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP 2009/18390–4 and 2009/51602–5), the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) for financial support. RA is the recipient of a research grant from CNPq.

supplementary crystallographic information

S1. Introduction

Natural products, isolated both from terrestrial or marine sources, display great structural diversity and exhibit remarkable biological activities, many of them bearing in their structures a spiro-hexadienone moiety (Wright & König (1993); Beil et al. (1998)). Owing to the high conjugation, provided by the presence of a carbonyl group and two double bonds, this structural moiety acts as an efficient Michael acceptor and this chemical property is routinely associated with some biological activities, such as cytotoxic (Pereira et al. (2007); Glushkov et al. (2010)).

Compounds presenting a nitrone group in their structures can present biological activity related to radical trapping in chemical systems (Fangour et al. (2009); Floyd et al. (2008); Halliwell et al. (1999)). The presence of radicals is normally associated to several type of pathologies. Our interest in preparing spiro-hexadienones with great structural diversity combinated with the biological effect that can be associated to nitrone groups stimulated us to synthesize new spiro compounds containing a nitrone group into their structures and evaluate the biological profiles of these new compounds.

A strategy for the synthesis of spiro-hexadienones from Morita-Baylis-Hillman aducts had been developed. This strategy is based on the Heck reaction, followed by phenolic oxidation of functionalized b-ketoester mediated by a hypervalent iodine reagent (Coelho et al. (2002); Ferreira et al. (2009); Floyd et al. (2008); Halliwell et al. (1999)). As far as we know, we synthesized for the first time new functionalized azaspiro compounds from Morita-Baylis-Hillman.

S2. Experimental

S2.1. Synthesis and crystallization

Some β-ketoesters, prepared from Morita-Baylis-Hillman adducts, were treated with hydroxylamine hydrochloride to furnish a diastereomeric mixture of oximes, in which the E isomer cyclizes spontaneously to the corresponding isoxazoles. The Z oxime was treated with PIFA [phenyliodine(III) bis(trifluoroacetate)] to furnish the new azaspiro compounds in moderate overall yield (3-17%). The obtained 3-(Methoxycarbonyl)-2-(4-methoxyphenyl)-8-oxo-1-azaspiro[4.5]deca-1,6,9-trien-1-ium-1-olate (33 mg, 0.1 mmol) was dissolved in absolute chloroform-D1 (1 mL), followed by stirring until total dissolution was achieved. The solution was kept in the freezer. After two weeks, the resulting solution was filtered using a vacuum, washed with small portions of cold chloroform and dried in a desiccator to furnish colourless prisms.

S2.2. Refinement

A riding model was used to calculate the positions of included H atoms, with aromatic and methyl C—H bond lengths of 0.95 and 0.98 A °, respectively. The isotropic displacement parameters values (Uiso(H)) were fixed at 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for all other attached H atoms.