(2Z)-2-Anilino-2-[oxido(phen­yl)iminio]-N-(2-pyrid­yl)acetamide methanol 0.425-solvate

Maciej Hodorowicz; Katarzyna Stadnicka; Bartosz Trzewik; Barbara Zaleska

doi:10.1107/S1600536808003346

. 2008 Feb 15;64(Pt 3):o599–o600. doi: 10.1107/S1600536808003346

(2Z)-2-Anilino-2-[oxido(phenyl)iminio]-N-(2-pyridyl)acetamide methanol 0.425-solvate

Maciej Hodorowicz ^a,^*, Katarzyna Stadnicka ^a, Bartosz Trzewik ^a, Barbara Zaleska ^a

PMCID: PMC2960779 PMID: 21201937

Abstract

The title compound, C₁₉H₁₆N₄O₂·0.425CH₄O, crystallizes with two formula units per asymmetric unit. Researching its crystal structure constitutes part of a study of the nature of interactions between the N⁺—O⁻ group and the vicinal NH group. The nitrone group and methanol solvent molecules are linked via four N—H⋯O and one O—H⋯O hydrogen bonds, with donor–acceptor distances of 2.603 (3)–2.730 (3) and 2.770 (3) Å, respectively. The crystal structure also involves two intermolecular N—H⋯N hydrogen bonds.

Related literature

For literature related to the synthesis of the title compound, see: Branco et al. (1992 ▶); Aurich (1968 ▶); Guimanini et al. (1999 ▶); Szantay et al. (1965 ▶); Southan et al. (1998 ▶); Warshaw et al. (1989 ▶). For literature on nitrones as an active equivalent of the C=O group, see: Boruah et al. (2003 ▶); Freisleben et al. (2002 ▶); Saito et al. (2001 ▶); Gravestock et al. (2000 ▶); Torssell (1988 ▶). For examples of nitrones with a vicinal NH group, see: Janzen et al. (1997 ▶); Clement et al. (1987 ▶); Baranowska et al. (1977 ▶); Aurich et al. (1976 ▶); Rosenberg et al. (1972 ▶). For literature on the medical use of these compounds, see: Floyd (2006 ▶). For related literature, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₉H₁₆N₄O₂·0.425CH₄O
M _r = 345.98
Monoclinic,
a = 18.7604 (3) Å
b = 9.4701 (2) Å
c = 21.2839 (5) Å
β = 104.375 (1)°
V = 3662.97 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.11 × 0.09 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.991, T _max = 0.998
12501 measured reflections
6668 independent reflections
3520 reflections with I > 2σ(I)
R _int = 0.065

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.156
S = 1.03
6668 reflections
474 parameters
548 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808003346/er2043sup1.cif

e-64-0o599-sup1.cif^{(31.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808003346/er2043Isup2.hkl

e-64-0o599-Isup2.hkl^{(319.8KB, 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
N7A—H7A⋯O13B	0.86	1.94	2.730 (3)	152
N11A—H11A⋯N1Bⁱ	0.86	2.30	3.095 (3)	153
N11A—H11A⋯O13A	0.86	2.25	2.603 (3)	105
N7B—H7B⋯O13Aⁱⁱ	0.86	1.90	2.724 (3)	160
N11B—H11B⋯N1A	0.86	2.32	3.056 (3)	144
N11B—H11B⋯O13B	0.86	2.28	2.604 (3)	102
O51—H51⋯O13B	0.82	1.95	2.770 (3)	179

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

Acknowledgments

The authors thank the Joint X-ray Laboratory, Faculty of Chemistry, and SLAFiBS, Jagiellonian University, for making available the Nonius KappaCCD diffractometer.

supplementary crystallographic information

Comment

Nitrones have attracted attention of organic chemists as nitrone N⁺–O^- moiety can be treated as an active equivalent of C=O group (Boruah et al. 2003, Freisleben et al. 2002, Saito et al. 2001, Gravestock et al. 2000, Torssell 1988, Floyd 2006). However, only several examples of nitrones bearing a vicinal NH group have been reported so far (Janzen et al. 1997, Clement et al. 1987, Baranowska et al. 1977, Aurich et al. 1976, Rosenberg et al. 1972). As reported, the compounds could be derived from nitriles (Branco et al. 1992), imidoformic acid esters or α-chloroimines (Aurich 1968), hydroxylamines and methylene amines (Aurich 1968, Guimanini et al. 1999), secondary amines (Szantay et al. 1965), and nitroso compounds, from hydroxyguanidines (Southan et al. 1998) or from other nitrones (Warshaw et al.1989). We have succeeded in developing a straightforward way of obtaining nitrones with a vicinal NH group in excellent yields, starting from easily available pyridilides of 3-oxobutanoic acid and nitrosobenzene. The crystal structure analysis of (2Z)-2-anilino-2-[oxido(phenyl)imino]-N-pyridin-2-ylacetamide was performed in order to determine the nature of the interactions between the N⁺–O^- moiety of the title nitrone with the vicinal NH group; this should help us to understand the compound's versatile reactivity towards various diamines. The symmetrically independent part of the unit cell is composed of two 2-anilino-2-[oxido(phenyl)imino]-N-pyridin-2-ylacetamide molecules and a 0.85 methanol molecule disordered between two positions with partial occupancy parameters of 0.586 (7) and 0.264 (7) for O51A—C51A and O51B—C51B, respectively. The conformation of the two symetrically independent nitrone molecules is shown in Figs. 1a and 1 b. No appreciable differences can be observed between the bond lengths and angles of the independent nitrone molecules and they are comparable with the values reported in the literature (Allen et al. 1987). The planarity of the C–C=N⁺→(O^-) part with Z configuration, in respect of N12–C10 double bond, observed for both symmetrically independent molecules is the most interesting feature of the investigated molecules, from the geometrical point of view. The O13—N12—C10—N11 and O13—N12—C10—C8 torsion angles are 2.6° and -174.3°, respectively for molecule A and -4.1° and 174.4°, respectively for molecule B. Significant torsion angles observed for nitrone molecules A and B are compared in Table 1. A l l aryl rings are twisted against each other: 〈 (C14···C19/N1···C6) = 68.0 (1)° for A and 53.8 (1)° for B; 〈 (C20···C25/N1···C6) = 75.5 (1)° for A and 66.4 (1)° for B. The crystal packing (Fig. 2) is controlled by N—H···O, N—H···N and O—H···O hydrogen bonds and weak van der Waals interactions (Table 2). The two N atoms (N7 and N11) in each molecule of the title compound are involved in the hydrogen bonds as donors forming two intra- and one intermolecular hydrogen bonds (Table 2). The intermolecular N11—H11···N1 interactions are relatively weak, with donor–acceptor distances of 3.095 (3) Å and 3.056 (3) Å due to simultaneous donor participation in intramolecular N11—H11···O13 interactions.

Experimental

Slow recrystallization from methanol at room temperature afforded crystals suitable for X-ray measurements. The ratio (2Z)-2-anilino-2-[oxido(phenyl)imino]-N-pyridin-2-ylacetamide to metanol molecule equals 2: 0.85 was confirmed by elemental analysis.