3,6-Dihydr­oxy-2′-[(2-hydr­oxy-1-naphth­yl)methyl­eneamino]xanthene-9-spiro-1′-isoindolin-3′-one acetonitrile solvate

Pei-San Wang; Gen-Hua Wu

doi:10.1107/S1600536808000974

. 2008 Jan 16;64(Pt 2):o442. doi: 10.1107/S1600536808000974

3,6-Dihydroxy-2′-[(2-hydroxy-1-naphthyl)methyleneamino]xanthene-9-spiro-1′-isoindolin-3′-one acetonitrile solvate

Pei-San Wang ^a,^b, Gen-Hua Wu ^a,^*

PMCID: PMC2960338 PMID: 21201469

Abstract

The title compound, C₃₁H₂₀N₂O₅·C₂H₃N, was synthesized by the reaction of fluorescein hydrazide and excess 2-hydroxy-1-naphthaldehyde in acetonitrile. The spirolactam ring is planar and is nearly at right angles to the two benzene rings of the xanthene system. The dihedral angle between the two benzene rings of the xanthene system is 9.92 (4)°. In the crystal structure, the molecules are linked into extended two-dimensional networks by intermolecular hydrogen bonding. Acetonitrile molecules are located in the voids between the two-dimensional networks.

Related literature

For general background, see: Chen et al., (2006 ▶). For related literature, see: Wu et al., (2007 ▶).

Experimental

Crystal data

C₃₁H₂₀N₂O₅·C₂H₃N
M _r = 541.54
Monoclinic,
a = 18.729 (5) Å
b = 15.572 (4) Å
c = 9.021 (2) Å
β = 98.495 (4)°
V = 2601.9 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 (2) K
0.26 × 0.22 × 0.16 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.976, T _max = 0.985
12963 measured reflections
4627 independent reflections
3272 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.098
S = 1.03
4627 reflections
375 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT-Plus (Bruker, 1997 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Bruker, 2000 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808000974/at2535sup1.cif

e-64-0o442-sup1.cif^{(26KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808000974/at2535Isup2.hkl

e-64-0o442-Isup2.hkl^{(226.7KB, 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
O4—H4⋯N1	0.82	1.83	2.5600 (16)	147
O3—H6⋯N3ⁱ	0.82	2.08	2.882 (2)	165
O1—H1⋯O4ⁱⁱ	0.82	1.94	2.7484 (16)	170

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Project No. 20775003) and the Natural Science Foundation of the Education Committee of Anhui Province, China (Project No. 2002 K J201).

supplementary crystallographic information

Comment

Fluorescein dyes have been used extensively for conjugation with biomolecules, owing to their excellent fluorescence properties. A few Fluorescein have also been used as fluorescent chemosensors for metal ions. It was reported that rhodamine B hydrazide could be used as a fluorescent probe for Cu²⁺(Chen et al., 2006). In addition, Fluorescein-based fluorescent chemosensors have received increasing interest in recent years by virtue of their long-wavelength emission and availability. In our previous research using 2-pyridinecarbaldehyde and rhodamine 6 G hydrazide synthesized probe (Wu et al., 2007). The structures are similar with rhodamine 6 G hydrazone probe and fluorescein hydrazone probe. As an extension of our work on this series of complexes, we herein report the crystal structure of the title comound.

The asymmetric unit contains one organic molecule and one acetonitriler molecule. The benzene ring of phenol deviates only slightly from planarity with a dihedral angle of 9.12 (3)°. The water O atom acts as a hydrogen bond acceptor and donor from the hydroxy group in a neighouring organic molecule, thereby forming extended 2-D networks (Table1, Fig. 2). Acetonitrile molecules are located in the voids between the two-dimensional networks.

Experimental

Briefly, to a suspended solution of fluorescein (300 mg, 0.9 mmol) in CH₃OH (15 ml), an excess of hydrazine hydrate (1.2 ml, 36 mmol) was added, and the reaction mixture was refluxed for 5 h with stirring. The resulting clear orange solution was evaporated in vacuo to give a brown oil, which was then recrystallized from ethanol–water, affording 1 as a light orange crystal (230 mg, yield 70%). Fluorescein hydrazide (0.46 g, 1 mmol) was dissolved in 20 ml absolute acetonitrile. An excessive 2-hydroxy-1-naphthaldehyde (4 mmol) was added then the mixture was refluxed in an air bath for 6 h. After that, the solution was cooled and allowed to stand at room temperature overnight. The yellow single-crystal which appeared after ten days was growed.