N-(2-Hydroxy­ethyl)-2-[2-(hydroxy­imino)propanamido]ethanaminium 2-(hydroxy­imino)propanoate

Turganbay S Iskenderov; Valentina A Kalibabchuk; Irina A Golenya; Nikolay M Dudarenko; Natalia I Usenko

doi:10.1107/S1600536809029778

. 2009 Aug 8;65(Pt 9):o2077–o2078. doi: 10.1107/S1600536809029778

N-(2-Hydroxyethyl)-2-[2-(hydroxyimino)propanamido]ethanaminium 2-(hydroxyimino)propanoate

Turganbay S Iskenderov ^a,^*, Valentina A Kalibabchuk ^b, Irina A Golenya ^c, Nikolay M Dudarenko ^c, Natalia I Usenko ^c

PMCID: PMC2970128 PMID: 21577497

Abstract

The cation of the title salt, C₇H₁₆N₃O₃ ⁺·C₃H₄NO₃ ⁻, the oxime group is trans with respect to the amide–carbonyl group. The components of the structure are united into a three-dimensional network by an extensive system of O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For background to oximes in coordination chemistry, see: Kukushkin et al. (1996 ▶); Chaudhuri (2003 ▶). For polynuclear species arising from bridging and/or functionalized oximes, see: Cervera et al. (1997 ▶); Costes et al. (1998 ▶); Moroz et al. (2008 ▶); Onindo et al. (1995 ▶); Sliva et al. (1997a ▶,b ▶); Gumienna-Kontecka et al. (2000 ▶). For oximes stabilizing high oxidation states, see: Kanderal et al. (2005 ▶); Fritsky et al. (2006 ▶). For related structures, see: Duda et al. (1997 ▶); Fritsky et al. (1999 ▶); Fritsky (1999 ▶); Mokhir et al. (2002 ▶). For the synthesis, see: Lau & Gutsche (1978 ▶).

Experimental

Crystal data

C₇H₁₆N₃O₃ ⁺·C₃H₄NO₃ ⁻
M _r = 292.30
Monoclinic,
a = 9.355 (2) Å
b = 6.996 (1) Å
c = 20.606 (4) Å
β = 96.99 (3)°
V = 1338.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 120 K
0.30 × 0.24 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (North et al., 1968 ▶) T _min = 0.957, T _max = 0.979
8410 measured reflections
3090 independent reflections
1887 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.088
S = 0.92
3090 reflections
201 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: COLLECT (Bruker, 2004 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029778/tk2512sup1.cif

e-65-o2077-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029778/tk2512Isup2.hkl

e-65-o2077-Isup2.hkl^{(151.6KB, 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
O3—H3O⋯O5ⁱ	0.90 (2)	1.78 (2)	2.677 (2)	173 (2)
O4—H4O⋯O2ⁱⁱ	0.95 (2)	1.63 (2)	2.5733 (18)	172.3 (19)
O6—H6O⋯O2	0.87 (2)	2.25 (2)	3.101 (2)	163.4 (18)
N3—H3N⋯O6ⁱⁱ	0.86 (2)	2.11 (2)	2.940 (2)	162.6 (18)
N4—H4N⋯O1ⁱⁱⁱ	0.970 (19)	1.93 (2)	2.838 (2)	155.1 (15)
N4—H5N⋯O1^iv	0.895 (18)	1.921 (19)	2.796 (2)	165.1 (17)

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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. F28/241–2009).

supplementary crystallographic information

Comment

Oximes are classical type of chelating ligands traditionally widely used in coordination and analytical chemistry (Kukushkin et al., 1996; Chaudhuri, 2003). They are also important bridging ligands extensively used in molecular magnetism for obtaining of polynuclear complexes (Cervera et al., 1997; Costes et al., 1998; Moroz et al., 2008). The presence of an additional donor function in the vicinity to the oxime group may result in important increase of chelating efficiency and ability to form polynuclear species. For example, amide derivatives of 2-hydroxyiminopropanoic acid were shown to act as highly efficient chelators with respect to Cu(II), Ni(II) and Al(III) (Onindo et al., 1995; Sliva et al., 1997a; Sliva, et al., 1997b; Gumienna-Kontecka et al., 2000). Recently, owing to their strong σ-donor capacity, open-chain tetradentate oxime and amide ligands were shown to efficiently stabilize unusual oxidation states of metal ions, such as Cu³⁺ and Ni³⁺ (Kanderal et al., 2005; Fritsky et al., 2006). The present investigation is dedicated to the study of the molecular structure of the title compound (I), which is a new polynucleative ligand containing several donor functions: oxime, amine, amide and alcohol.

The structure of (I) is ionic and and comprises cations of N-[2-(2-hydroxy-ethylammonium)ethyl]-2-hydroxyiminopropanamide and 2-(hydroxyimino)propanoate anions (Fig. 1). The cation has a Γ-shaped conformation and consists of two nearly planar CH₃C(=NOH)C(O)NHCH₂and CH₂CH₂NH₂CH₂ fragments. The dihedral plane between their mean planes, defined by the non-hydrogen atoms, is 75.8 (1)°. The hydroxyl group is situated nearly perpendicular to the CH₂CH₂NH₂CH₂ moiety: the torsion angle N4/C9/C10/O6 is 60.2 (2)°. The observed conformation of the CH₃C(=NOH)C(O)NHCH₂moiety is the same as that observed in the structure of N,N'-bis(2-hydroxyiminopropionylpropane)-1,2-diamine and its homologues (Duda et al., 1997; Fritsky, Karaczyn et al., 1999). The oxime group is trans to the amide-carbonyl. It is noted that the CH₃C(=NOH)C(O)NHCH₂moiety deviates somewhat from planarity because of a twisting of the oxime and amide groups along the C5—C6 bond. The dihedral angle between the corresponding least square planes is 9.5 (1)°. The C=N, C=O, N—O, C—N bond lengths are typical for 2-hydroxyiminopropanoic acid and its amide derivatives (Duda et al., 1997; Fritsky, 1999; Mokhir et al., 2002).

The elements of the structure are united into a 3-D network by extensive system of the O—H···O and N—H···O hydrogen bonds (Table 1).

Experimental

Ethyl 2-(hydroxyimino)propanoate (1.31 g, 0.01 mol) was dissolved in methanol (50 ml) to which 2-((2-aminoethyl)amino)ethanol (1.04 g, 0.01 mol) was added. The mixture was set aside for 24 h at room temperature, then the solvent was removed on a rotary evaporator. Recrystallization of the crude product from water afforded the pure (I) in the form of single crystals. Ethyl 2-(hydroxyimino)propanoate was prepared according to the reported method (Lau & Gutsche, 1978).