(2E)-N-(3,5-Dibromo-4-methoxy­phen­yl)-2-(hydroxy­imino)acetamide

Simon J Garden; Angelo C Pinto; Fernanda R da Cunha; Silvia P Fontes; A S Lima; Edward R T Tiekink

doi:10.1107/S1600536810018623

. 2010 May 22;66(Pt 6):o1436–o1437. doi: 10.1107/S1600536810018623

(2E)-N-(3,5-Dibromo-4-methoxyphenyl)-2-(hydroxyimino)acetamide

Simon J Garden ^a,^‡, Angelo C Pinto ^a, Fernanda R da Cunha ^a, Silvia P Fontes ^a, A S Lima ^a, Edward R T Tiekink ^b,^*

PMCID: PMC2979508 PMID: 21579511

Abstract

The title compound, C₉H₈Br₂N₂O₃, is planar (r.m.s. deviation = 0.030 Å) with the exception of the terminal methyl group which lies out of the plane [1.219 (3) Å]. The conformation about the C=N double bond [1.268 (3) Å] is E. An intramolecular N—H⋯N hydrogen bond occurs. Linear supramolecular chains along the b axis mediated by O—H⋯O hydrogen-bonding interactions feature in the crystal structure. These chains are also stabilized by weak C—H⋯N contacts.

Related literature

For the preparation of isonitrosoacetanilides from aniline derivatives, see: Garden et al. (1997 ▶). For the use of isonitrosoacetanilides as precursors of pharmacologically important heterocyclic compounds, see: da Silva et al. (2001 ▶); Garden et al. (2002 ▶); Matheus et al. (2007 ▶); Maronas et al. (2008 ▶). For related structures, see: Briansó et al. (1974 ▶); Plana et al. (1976 ▶).

Experimental

Crystal data

C₉H₈Br₂N₂O₃
M _r = 351.98
Monoclinic,
a = 10.3841 (2) Å
b = 8.8535 (1) Å
c = 13.0164 (3) Å
β = 106.356 (1)°
V = 1148.24 (4) Å³
Z = 4
Mo Kα radiation
μ = 7.05 mm⁻¹
T = 120 K
0.20 × 0.10 × 0.01 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.715, T _max = 1.000
14309 measured reflections
2643 independent reflections
2306 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.090
S = 1.16
2643 reflections
149 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.77 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); 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: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018623/hg2689sup1.cif

e-66-o1436-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018623/hg2689Isup2.hkl

e-66-o1436-Isup2.hkl^{(127.2KB, 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
N1—H1n⋯N2	0.88	2.30	2.702 (3)	108
O2—H2o⋯O1ⁱ	0.84	1.83	2.672 (3)	175
C2—H2⋯N2ⁱⁱ	0.95	2.51	3.345 (3)	146

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

Acknowledgments

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. SJG thanks CNPq and FAPERJ for financial support.

supplementary crystallographic information

Comment

Isonitrosoacetanilides, readily available from aniline derivatives (Garden et al., 1997), have found use as precursors of pharmacologically important heterocyclic compounds (da Silva et al., 2001; Garden et al., 2002; Matheus et al., 2007; Maronas et al., 2008).

The molecular structure of (I), Fig. 1, is essentially planar with the exception of the terminal methyl group. Thus, the r.m.s. deviation of all non-hydrogen atoms, excluding the methyl-C9 atom, is 0.030 Å; the C9 atom lies 1.219 (3) Å out of the plane. The conformation about the C2═N2 double bond [1.268 (3) Å] is E. The observed planarity is partially stabilised by an intramolecular N–H···N hydrogen bond (Table 1). There two other methoxy substituted 2-(hydroxyimino)-N-arylacetamide structures available for comparison,i.e. o-OMe (Plana et al., 1976) and p-OMe (Briansó et al., 1974) derivatives. The geometric parameters in these match closely those in (I). The major difference in the three structures relate to the non-planarity of (I) compared to the planarity in the literature structures. The proximity of the OMe group to two bromido substituents in (I) is the likely explanation for the deviation from planarity in (I). The crystal packing is dominated by O–H···O hydrogen bonding interactions that lead to the formation of a supramolecular linear chain along the b axis, Fig. 2 and Table 1. These chains are also stabilised by weak C–H···N contacts, Table 1.

Experimental

The compound was prepared as previously reported from 3,5-dibromo-4-methoxyaniline, hydroxylamine.hydrogen sulfate in aqueous ethanol, containing sodium sulfate and CCl₃CH(OH)₂ (Garden et al., 1997). The sample for the crystallographic study was recrystallised from EtOH, m.p. 463 K.