A one-dimensional coordination polymer constructed from isatine-3-oximate and sodium

Bianca Barreto Martins; Leandro Bresolin; Vanessa Santana Carratu; Mariana Boneberger Behm; Adriano Bof de Oliveira

doi:10.1107/S1600536811018290

. 2011 May 25;67(Pt 6):m790–m791. doi: 10.1107/S1600536811018290

A one-dimensional coordination polymer constructed from isatine-3-oximate and sodium

Bianca Barreto Martins ^a, Leandro Bresolin ^a, Vanessa Santana Carratu ^a,^*, Mariana Boneberger Behm ^b, Adriano Bof de Oliveira ^c

PMCID: PMC3120341 PMID: 21754670

Abstract

The reaction of hydroxylamine hydrochloride with isatin in ethanol, catalysed with HCl and neutralized with Na₂CO₃, yielded the one-dimensional coordination polymer, catena-poly[[[aquasodium]-di-μ-aqua-[aquasodium]-bis(μ-2-oxoindoline-2,3-dione 3-oximato)] tetrakis(oxoindoline-2,3-dione 3-oxime)], {[Na(C₈H₅N₂O₂)(H₂O)₂]·2C₈H₆N₂O₂}_n. The Na^I atom has a six-coordinate distorted-octahedral environment. Isatine-3-oximate O atoms and water molecules bridge adjacent Na atoms, forming a one-dimensional polymeric structure parallel to [100]. Each isatine-3-oxime dimerizes through N—H⋯O interactions and in addition each oxime is linked to a coordination polymer. Thus, coordination polymers are linked by O—H⋯O and O—H⋯N interactions from isatine-3-oxime dimers, building a two-dimensional network parallel to [110].

Related literature

For the pharmacological and biological properties of oxime derivatives, see: Chafeev et al. (2008 ▶). For the preparation and characterization of some metal complexes of isatine-3-oxime, see: Hudák & Košturiak (1999 ▶).

Experimental

Crystal data

[Na(C₈H₅N₂O₂)(H₂O)₂]·2C₈H₆N₂O₂
M _r = 544.45
Triclinic,
a = 7.2987 (3) Å
b = 11.9269 (5) Å
c = 15.0756 (6) Å
α = 95.369 (2)°
β = 102.871 (2)°
γ = 102.631 (2)°
V = 1234.36 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.74 × 0.23 × 0.18 mm

Data collection

Bruker CCD X8 APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.912, T _max = 0.978
25159 measured reflections
7175 independent reflections
4225 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.135
S = 1.04
7175 reflections
388 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018290/bt5520sup1.cif

e-67-0m790-sup1.cif^{(36KB, cif)}

Supplementary material file. DOI: 10.1107/S1600536811018290/bt5520Isup2.mol

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018290/bt5520Isup3.hkl

e-67-0m790-Isup3.hkl^{(344KB, 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
N21—H21⋯O21ⁱ	0.87 (2)	1.97 (2)	2.846 (5)	175 (2)
O22—H22⋯O12	0.94 (2)	1.70 (2)	2.633 (3)	171 (2)
O22—H22⋯N12	0.94 (2)	2.45 (2)	3.226 (4)	140 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge financial support by the CNPq and FAPERGS.

supplementary crystallographic information

Comment

Oxime derivatives such as isatine-3-oxime have a wide range of properties. For example, they modulate ion flux through a voltage-dependent sodium channel in a mammal. Acting as small molecule sodium channel blockers, these compounds are used intreating diseases or conditions such as hypercholesterolemia and cancer (Chafeev et al., 2008). As part of our interest in the study of oxime derivatives, we report herein the crystal structure of [Na(C₈N₂O₂H₅)(H₂O)₂](C₈N₂O₂H₆)₂. Crystallographically independent, the structure contains two protonated isatine-3-oxime, two water molecules, one isatine-3-oximate and one sodium(I). The sodium cation has a six-coordinate distorted octahedral environment: one ON-donor bidentate oximate and two water molecules are crystallographically independent. One O-donor monodentate oximate, symmetry generatedⁱⁱ, and one symmetry generated water moleculeⁱ complete the coordination sphere. The polymeric structure is build one side with two bridging water molecules, one crystallographicaly independent and one symmetry generatedⁱ and another side with one bridging oxygen atom from a crystallographically independent oximate and one oxygen atom from a symmetry generatedⁱⁱ oximate. These O-donor bridging atoms form a 1-D zigzag chain of Na complexes in solid state. For the sodium(I) coordination sphere the metal-donor distances [Å] are: Na—O11 = 2,5721 (14), Na—O11ⁱⁱ = 2,3281 (14), Na—O2W = 2,361 (2), Na—O1W = 2,4117 (17), Na—O1Wⁱ = 2,485 (18), Na—N12 = 2,4906 (15). Selected angles (°) are: O1Wⁱ—Na—O11 = 158,74 (6), O2W—Na—O1W = 162,92 (8), O11ⁱⁱ—Na—N12 = 141,63 (6) and build a distorced octahedra. Symmetry codes: (i)-x,-y + 1,-z; (ii)-x + 1,-y + 1,-z.

Experimental

Starting materials were commercially available and were used without further purification. The synthesis was adapted from a procedure reported previously (Chafeev et al., 2008; Hudák & Košturiak, 1999). The hydrochloric acid catalyzed reaction of isatin (8,83 mmol) and hydroxylamine hydrochloride (8,83 mmol) in ethanol (50 ml) was refluxed for 6 h and neutralized with a 10% solution of sodium carbonate in water (50 ml). After cooling and filtering, crystals suitable for X-ray diffraction were obtained.