Ethyl 4-hy­droxy-1-methyl-5-oxo-2-phenyl­pyrrolidine-3-carboxyl­ate 1.25-hydrate

Nurul Shulehaf Mansor; Mohd Fazli Mohammat; Zurina Shaameri; Hamid Khaledi

doi:10.1107/S1600536813001943

. 2013 Jan 26;69(Pt 2):o293–o294. doi: 10.1107/S1600536813001943

Ethyl 4-hydroxy-1-methyl-5-oxo-2-phenylpyrrolidine-3-carboxylate 1.25-hydrate

Nurul Shulehaf Mansor ^a, Mohd Fazli Mohammat ^a, Zurina Shaameri ^a, Hamid Khaledi ^b,^*

PMCID: PMC3569816 PMID: 23424562

Abstract

The asymmetric unit of the title compound, C₁₄H₁₇NO₄·1.25H₂O, consists of four substituted pyrrolidone molecules (two pairs of enantiomers) and five water molecules. The five-membered rings each have an envelope conformation, with the C atom bonded to the ester group as the flap. The mean planes of the five-membered rings of the four pyrrolidone molecules make dihedral angles of 60.87 (5), 64.45 (5), 62.03 (5) and 65.79 (5)° with respect to the phenyl rings. In the crystal, the pyrrolidone and water molecules are connected through O—H⋯O hydrogen bonds, forming a layer parallel to the ab plane. The two-dimensional network is further stabilized by intermolecular C—H⋯O hydrogen bonds.

Related literature

For the structures of similar compounds, see: Ma & Jiang (1998 ▶); Chu et al. (2011 ▶); Gainsford & Mason (2010 ▶). For the synthesis of the precursor substituted 2,5-dihydropyrrole-2-one, see: Mohammat et al. (2009 ▶). graphic file with name e-69-0o293-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₇NO₄·1.25H₂O
M _r = 285.81
Triclinic,
a = 10.3669 (2) Å
b = 15.7466 (3) Å
c = 18.4539 (3) Å
α = 77.373 (1)°
β = 80.425 (1)°
γ = 87.058 (1)°
V = 2898.31 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.21 × 0.15 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.979, T _max = 0.991
22505 measured reflections
11260 independent reflections
9637 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.104
S = 1.02
11260 reflections
780 parameters
20 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(56.6KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813001943/is5239sup1.cif

e-69-0o293-sup1.cif^{(56.6KB, cif)}

Click here for additional data file.^{(550.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813001943/is5239Isup2.hkl

e-69-0o293-Isup2.hkl^{(550.5KB, hkl)}

Click here for additional data file.^{(5.7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813001943/is5239Isup3.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
O2A—H2A⋯O5	0.81 (2)	1.86 (2)	2.6569 (16)	166 (2)
O2B—H2B⋯O1B ⁱ	0.84 (1)	1.89 (2)	2.7111 (14)	165 (2)
O2C—H2C⋯O1C ⁱⁱ	0.85 (1)	1.89 (2)	2.7089 (14)	162 (2)
O2D—H2D⋯O8ⁱⁱⁱ	0.82 (2)	1.92 (2)	2.7134 (17)	164 (2)
O5—H5E⋯O1C ⁱⁱ	0.86 (1)	1.94 (2)	2.7857 (15)	168 (2)
O5—H5F⋯O2D ⁱⁱⁱ	0.86 (1)	1.79 (1)	2.6490 (17)	178 (2)
O6—H6F⋯O2C ^iv	0.90 (1)	1.99 (1)	2.8837 (16)	177 (2)
O6—H6E⋯O1D ⁱⁱⁱ	0.88 (1)	1.96 (2)	2.8218 (15)	167 (2)
O7—H7F⋯O1A	0.87 (1)	1.97 (2)	2.8399 (16)	176 (2)
O7—H7E⋯O2B ^v	0.89 (1)	2.01 (1)	2.8987 (16)	175 (2)
O8—H8E⋯O7	0.95 (2)	1.87 (2)	2.7637 (18)	156 (2)
O8—H8F⋯O9	0.91 (1)	1.93 (2)	2.8193 (18)	168 (2)
O9—H9F⋯O2A	0.84 (2)	1.98 (2)	2.8199 (17)	176 (2)
O9—H9E⋯O6	0.90 (1)	1.93 (2)	2.7724 (18)	155 (2)
C3B—H3B⋯O1A ^vi	1.00	2.45	3.2581 (17)	138
C3C—H3C⋯O1D	1.00	2.31	3.1537 (17)	142
C3D—H3D⋯O1D ⁱⁱⁱ	1.00	2.56	3.4252 (18)	145
C5A—H5A⋯O7^v	1.00	2.34	3.2374 (18)	148
C5B—H5B⋯O9^vi	1.00	2.40	3.2568 (19)	143
C5C—H5C⋯O8ⁱⁱⁱ	1.00	2.49	3.2395 (19)	131
C5D—H5D⋯O6	1.00	2.41	3.2010 (18)	135
C7A—H7A⋯O3B	0.95	2.38	3.2943 (17)	162
C7B—H7B⋯O3A ^vi	0.95	2.46	3.3253 (18)	151
C7C—H7C⋯O3D	0.95	2.39	3.2704 (18)	155
C11A—H11A⋯O4B ^iv	0.95	2.54	3.3027 (17)	138

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

Acknowledgments

The authors acknowledge the generous support of Universiti Teknologi MARA Malaysia (FRGS grant No. 600-RMI/ST/FRGS 5/3/Fst (11/2008) and the University of Malaya.

supplementary crystallographic information

Comment

Polyfunctionalized pyrrolidones have received significant attention in the past decades due to their role as intermediates for synthesizing more complex biologically important molecules (Ma & Jiang, 1998). The present pyrrolidone molecule was prepared through catalytic hydrogenation of the previously reported substituted 2,5-dihydropyrrole-2-one (Mohammat et al., 2009). The asymmetric unit of the crystal (Fig. 1) contains four geometrically slightly different pyrrolidone molecules: A (Fig. 2), B, C & D. The weighted r.m.s. fit for the superposition of the non-H atoms is 0.097 Å (in A & B with inversion), 0.082 Å (in A & C), 0.107 Å (in A & D with inversion), 0.141 Å (in B & C with inversion), 0.034 Å (in B & D) and 0.138 Å (in C & D with inversion). The planes of the phenyl and pyrrolidine rings in the four molecules make dihedral angles of 60.87 (5), 64.45 (5), 62.03 (5) and 65.79 (5)°. The bond lengths and angles in the four molecules are comparable to those in similar structures (Chu et al., 2011; Gainsford & Mason, 2010). There are five crystallographically independent water molecules in the crystal structure, connecting the pyrrolidone molecules into a layer parallel to the ab plane via O—H···O hydrogen bonds (Table 1). The supramolecular structure is further consolidated by intermolecular C—H···O interactions (Table 1).

Experimental

The synthetic approach to the title compound began with the preparation of ethyl 4-hydroxy-1-methyl-5-oxo-2-phenyl-2,5-dihydropyrrole-3-carboxylate as reported by (Mohammat et al., 2009). This compound was catalytically hydrogenated by addition of Pd—C (10% wt) (0.91 g, 8.60 mmol) to its stirring solution (1.69 g, 6.47 mmol) in ethanol (110 ml) under hydrogen atmosphere for 24 h. The mixture was then filtered through celite. After removal of the solvent, the crude product was purified by column chromatography using silica gel (eluent: EtOAc) to give the diastereomeric product as a white solid (1.20 g, 71%). Slow evaporation of an ethyl acetate solution of the product at room temperature gave colorless crystals of the title compound.