(2RS)-3-Hydr­oxy-2-methyl-2-(2-pyrid­yl)imidazolidine-4-one

Turganbay S Iskenderov; Irina A Golenya; Elźbieta Gumienna-Kontecka; Igor O Fritsky; Elena V Prisyazhnaya

doi:10.1107/S1600536809030840

. 2009 Aug 8;65(Pt 9):o2123–o2124. doi: 10.1107/S1600536809030840

(2RS)-3-Hydroxy-2-methyl-2-(2-pyridyl)imidazolidine-4-one

Turganbay S Iskenderov ^a, Irina A Golenya ^b, Elźbieta Gumienna-Kontecka ^c, Igor O Fritsky ^b, Elena V Prisyazhnaya ^d,^*

PMCID: PMC2970069 PMID: 21577537

Abstract

The title structure, C₉H₁₁N₃O₂, is a racemate. The chiral centre is situated at the N—C—N C atom of the imidazolidine ring. The interplanar angle between the mean planes of the pyridine and imidazolidine rings is 89.41 (5)°. The methyl group is in a trans position with respect to the pyridine N atom. In the crystal, the molecules are arranged in zigzag layers parallel to the b axis. The molecules within the layers are interconnected by strong O—H⋯N and weak N—H⋯O hydrogen bonds; the former take place between OH groups and amine N atoms and the latter between the amine N atom and the carbonyl O atom. In addition, C—H⋯O interactions are also present.

Related literature

For background to hydroxamic acids in biological and coordination chemistry, see: Miller (1989 ▶); Lipczynska-Kochany (1991 ▶); Kurzak et al. (1992 ▶); Whittaker et al. (1999 ▶). For reactions of α-amino hydroxamic acids with aldehydes and ketones resulting in 3-hydroxyimidazolidin-4-one derivatives, see: Vystorop et al. (2002 ▶, 2003 ▶); Marson & Pucci (2004 ▶). For related structures, see: Krämer & Fritsky (2000 ▶); Świątek-Kozłowska et al. (2000 ▶); Krämer et al. (2002 ▶); Kovbasyuk et al. (2004 ▶). For the synthesis, see: Cunningham et al. (1949 ▶). For hydrogen bonds, see: Desiraju & Steiner (1999 ▶).

Experimental

Crystal data

C₉H₁₁N₃O₂
M _r = 193.21
Monoclinic,
a = 8.207 (2) Å
b = 10.604 (2) Å
c = 10.642 (2) Å
β = 106.43 (3)°
V = 888.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.25 × 0.17 × 0.12 mm

Data collection

Kuma KM-4-CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED, Oxford Diffraction, 2006 ▶) T _min = 0.976, T _max = 0.986
6025 measured reflections
2048 independent reflections
1772 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.092
S = 1.12
2048 reflections
137 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809030840/fb2163sup1.cif

e-65-o2123-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030840/fb2163Isup2.hkl

e-65-o2123-Isup2.hkl^{(100.8KB, hkl)}

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—H1O⋯N1ⁱ	0.95 (2)	1.78 (2)	2.7287 (16)	175.5 (18)
N1—H1N⋯O2ⁱⁱ	0.874 (17)	2.135 (18)	3.0058 (15)	173.7 (15)
C6—H6⋯O1ⁱⁱⁱ	0.93	2.47	3.2867 (17)	147
C7—H7⋯O2ⁱⁱⁱ	0.93	2.81	3.3559 (17)	119
C8—H8⋯O2^iv	0.93	2.80	3.4177 (17)	125

Open in a new tab

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

Acknowledgments

The authors thank the Ministry of Education and Science of Ukraine for financial support (grant No. M/42–2008).

supplementary crystallographic information

Comment

Hydroxamic acids are important bioligands possessing a wide spectrum of biological activities (Lipczynska-Kochany, 1991). Notably, they have a high affinity to the transition metal ions (Kurzak et al., 1992). For example, naturally occurring hydroxamate siderophores are strong Fe(III) chelators (Miller, 1989). Hydroxamic acids are also efficient metalloenzyme inhibitors, e.g. urease and matrix metalloproteinase inhibitors (Whittaker et al., 1999).

These properties have provoked current interest in the development of novel synthetic routes for preparation of new selective hydroxamate chelating agents and siderophore mimics. Recently it was found that the reactions of α-amino hydroxamic acids with aldehydes and ketons do not result in the open-chain Schiff base hydroxamic acids but afford five-membered cyclic products containing residues of 3-hydroxyimidazolidine-4-one (Marson & Pucci, 2004; Vystorop et al., 2002; Vystorop et al., 2003). Here we describe a crystal structure of the title structure, 2-methyl-2-(pyridine-2-yl)-3-hydroxyimidazolidine-4-one, obtained as a result of the condensation of glycine hydroxamic acid and 2-acetylpyridine.

The molecules of the title structure are interconnected by the H-bonds. The molecules contain a chiral centre at the C2 atom (Fig. 1) and the structure is a racemate. The molecule is not planar: the interplanar angle between the mean planes of the pyridine and imidazolidine rings equals to 89.41 (5)°. The imidazolidine ring exhibits the envelope conformation: the C2 atom is displaced by 0.320 (2) Å out of the mean plane defined by four other atoms of the ring. The methyl group is in the trans-position with respect to the pyridine nitrogen.

The bond lengths C—O, N—O and C—N in the hydroxamic function suggest the presence of the hydroxamic function in the hydroxamic form rather than in the oximic one (Świątek-Kozłowska et al., 2000). The C—N and C—C bond lengths within the pyridine ring are normal for 2-substituted pyridine derivatives (Krämer & Fritsky, 2000; Krämer et al., 2002; Kovbasyuk et al., 2004).

In the crystal packing, the molecules are arranged into zig-zagged layers by the O1—H···N2 and N2—H···O2 hydrogen bonds. These layers are parallel to the axis b. The former one takes place between NOH group and it is considered as a strong hydrogen bond (Desiraju & Steiner, 1999) while the latter one between the amine nitrogen and the carbonyl oxygen atom (Fig. 2) is considered as weak one (Desiraju & Steiner, 1999). Moreover, the mentioned layers are interconnected by C—H···O H-bonds (Tab. 1).

Experimental

A suspension of glycine hydroxamic acid (0.9 g, 10 mmol) and 2-acetylpyridine (12 mmol) in 30 ml of 96% aqueous ethanol was refluxed for at 78°C for 1-2 h. The hot reaction mixture was filtered, the filtrate produced a white precipitate on cooling. The precipitate was filtered, air-dried and recrystallized from absolute ethanol to yield the title structure as colourless prismatic crystals of average size 0.25 × 0.15 × 0.15 mm. The reagent, glycine hydroxamic acid, was prepared according to the procedure described by Cunningham et al. (1949).