[4-(4-Meth­oxy­phen­yl)-1-methyl-3-nitro­pyrrolidin-3-yl]methanol

K Prathebha; S Sathya; G Usha; N Sivakumar; M Bakthadoss

doi:10.1107/S1600536813003073

. 2013 Feb 9;69(Pt 3):o372. doi: 10.1107/S1600536813003073

[4-(4-Methoxyphenyl)-1-methyl-3-nitropyrrolidin-3-yl]methanol

K Prathebha ^a, S Sathya ^a, G Usha ^a,^*, N Sivakumar ^b, M Bakthadoss ^b

PMCID: PMC3588458 PMID: 23476560

Abstract

In the title compound, C₁₃H₁₈N₂O₄, the dihedral angle between the benzene and pyrrolidine (all atoms) rings is 70.6 (1)°. The pyrrolidine ring adopts a half-chair conformation. In the crystal, molecules form chains along the c-axis direction linked by O—H⋯N hydrogen bonds, which are then connected by C—H⋯O interactions, forming a sheet parallel to the bc plane.

Related literature

For information on the pyrrolidine ring in biologically active natural compounds, see: Gu et al. (2004 ▶). For the use of pyrrolidine-containing molecules in the treatment of diseases, see, for example: Horri et al. (1986 ▶) for diabetes and Karpas et al. (1988 ▶) for viral infections. For bond lengths in a related structure, see: Jayabharathi et al. (2009 ▶). graphic file with name e-69-0o372-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₈N₂O₄
M _r = 266.29
Monoclinic,
a = 11.6827 (10) Å
b = 11.1912 (11) Å
c = 11.1789 (11) Å
β = 109.118 (2)°
V = 1381.0 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
12464 measured reflections
3407 independent reflections
2282 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.162
S = 1.01
3407 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(18.3KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813003073/nk2193sup1.cif

e-69-0o372-sup1.cif^{(18.3KB, cif)}

Click here for additional data file.^{(163.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813003073/nk2193Isup2.hkl

e-69-0o372-Isup2.hkl^{(163.7KB, hkl)}

Click here for additional data file.^{(5.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813003073/nk2193Isup3.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—H2⋯N1ⁱ	0.82	2.01	2.8237 (16)	170
C1—H1A⋯O2ⁱⁱ	0.96	2.51	3.390 (2)	153
C3—H3⋯O3ⁱⁱⁱ	0.93	2.51	3.429 (2)	171

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

Acknowledgments

The authors thank Professor D. Velmurugan, Centre for Advanced Study in Crystallography and Biophysics, University of Madras, for providing data collection and computer facilities.

supplementary crystallographic information

Comment

The stucture of the title compound, (I), is shown below. Dimensions are available in the archived CIF.

Pyrrolidine ring is present in many biologically active natural compounds and pharmaceuticals (Gu et al., 2004), and find utility in the treatment of diseases such as diabetes (Horri et al.,1986), and viral infections (Karpas et al., 1988).

The bond lengths C8—C13 = 1.525 (2) Å; C13—N1=1.460 (2) Å; C11—N1 = 1.462 (2) Å; C11—C9= 1.520 (2) Å; C8—C9= 1.566 (2) Å are longer than the normal values but are comparable with the values of such distances in the reported structure (Jayabharathi et al., 2009). This may be due to the steric forces caused by the bulky group at C8 and C9 of pyrrolidine moiety. C1—O1 [1.416 (3) Å] is longer than C2—O1 [1.367 (2) Å]; this may be due the end atom C1.The dihedral angle between phenyl and pyrrolidine ring is 70.6 (1)°. The sum of angles around N3 [360°] and N1[329.1 (1)°] indicates sp²and sp³hybridization, respectively. The five membered ring adopts half chair conformation.The crystal structure is stabilized by intermolecular O—H···N and C—H···O type hydrogen bonds.

Experimental

Typical Procedure for the synthesis of (E)-3-(4-methoxyphenyl)-2-nitroprop-2-en-1-ol:

To a stirred soln of (E)-1-methoxy-4-(2-nitrovinyl)benzene (10 mmol) in THF (20 mL) at r.t. was added imidazole (1 equiv) followed by anthranilic acid (10 mol%). Aq formaldehyde (38%, 20 mL, excess) was then added and the mixture was stirred at r.t. for the period of 48h. On completion of the reaction (TLC analysis), the mixture was acidified with 5 M HCl (20 mL) and the aqueous layer was extracted with EtOAc (3 × 25 mL). The combined organic layers were washed with brine (50 mL), dried (anhyd Na2SO4), and concentrated in vacuo. The residue was purified by column chromatography (silica gel, EtOAc–hexanes, 0–25%, gradient elution) to afford pure (E)-3-(4-methoxyphenyl)-2-nitroprop-2-en-1-ol in 50% yield as yellow oil.

A mixture of (E)-3-(4-methoxyphenyl)-2-nitroprop-2-en-1-ol (2 mmol,0.42 g), para formaldehyde (12 mmol,0.36 g) and sacrosine (6 mmol,0.53 g) in acetonitrile(8 ml) was refluxed for 8hrs. After the completion of the reaction as indicated by TLC, the reaction mixture was concentrated and the resulting crude mass was diluted with water (20 ml) and extracted with ethyl acetate (3x10ml) and dried over anhydrous Na₂SO₄.The organic layer was concentrated and purified by column chromatography on silica gel (Acme 100–200 mesh), using ethyl acetate:hexane (3:7) to provide the title compound as a colourless solid in 73% (0.39 g) yield.