Bis(2-{[(9H-fluoren-2-yl)methyl­idene]amino}­phenolato-κ2 N,O)zinc methanol disolvate

Young-Inn Kim; Sung-Jae Yun; Inn-Hye Hwang; Dae-Young Kim; Sung Kwon Kang

doi:10.1107/S160053681201272X

. 2012 Mar 31;68(Pt 4):m504–m505. doi: 10.1107/S160053681201272X

Bis(2-{[(9H-fluoren-2-yl)methylidene]amino}phenolato-κ² N,O)zinc methanol disolvate

Young-Inn Kim ^a, Sung-Jae Yun ^a, Inn-Hye Hwang ^a, Dae-Young Kim ^a, Sung Kwon Kang ^b,^*

PMCID: PMC3343889 PMID: 22589857

Abstract

In the title compound, [Zn(C₂₀H₁₄NO)₂]·2CH₃OH, the Zn^II atom lies on a crystallographic twofold rotation axis and is coordinated by two O atoms and two N atoms from two bidentate 2-{[(9H-fluoren-2-yl)methylidene]amino}phenolate ligands within a distorted tetrahedral geometry. The dihedral angle between the two chelate rings is 82.92 (5)°. In the coordinated ligand, the phenol ring is twisted at 30.22 (9)° from the mean plane of the fluorene ring. In the crystal, O—H⋯O hydrogen bonds link the complex molecules to the methanol solvent molecules.

Related literature

For general background to Schiff base complexes, see: Ji et al. (2012 ▶); Niu et al. (2012 ▶); Liu et al. (2011 ▶); Roy et al. (2009 ▶). For the structures and luminescent properties of Hg(II) complexes, see: Kim et al. (2011 ▶); Kim & Kang (2010 ▶). For the physical properties of fluorene complexes, see: Scaria et al. (2010 ▶); Loy et al. (2002 ▶); Miteva et al. (2001 ▶).

Experimental

Crystal data

[Zn(C₂₀H₁₄NO)₂]·2CH₄O
M _r = 698.1
Monoclinic,
a = 13.7294 (3) Å
b = 13.9123 (2) Å
c = 18.8383 (3) Å
β = 110.652 (1)°
V = 3367.03 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 296 K
0.10 × 0.05 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.922, T _max = 0.966
10682 measured reflections
3078 independent reflections
2134 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.096
S = 1.02
3078 reflections
227 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681201272X/tk5073sup1.cif

e-68-0m504-sup1.cif^{(23.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201272X/tk5073Isup2.hkl

e-68-0m504-Isup2.hkl^{(148.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Zn1—O1	1.9239 (17)
Zn1—N8	2.052 (2)
C7—N8	1.433 (3)
N8—C9	1.293 (3)

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O1ⁱ—Zn1—O1	115.61 (11)
O1ⁱ—Zn1—N8	125.99 (8)
O1—Zn1—N8	85.68 (8)
N8—Zn1—N8ⁱ	122.53 (11)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O24—H24⋯O1	0.98 (4)	1.82 (5)	2.794 (3)	173 (4)

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Acknowledgments

This work was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 20110003799).

supplementary crystallographic information

Comment

Schiff base ligands have attracted attention due to their facile syntheses, easily tunable steric and electronic properties resulting in a good performance in sensor technologies and electroluminescence devices (Ji et al., 2012; Niu et al., 2012; Liu et al., 2011; Roy et al., 2009). Recently, we reported group 12, Hg(II) complexes with Schiff bases with an emphasis on their luminescent properties (Kim & Kang, 2010; Kim et al., 2011). Herein, we designed new Schiff base containing a fluorene moiety since flourene has high triplet energy and good-hole transporting ability (Scaria et al., 2010; Loy et al., 2002; Miteva et al., 2001) and synthesized its Zn(II) complex. The title compound shows a red emission at 611 nm with a quantum yield of 1.2% in a DMF solution upon 300 nm excitation.

In (I), Fig. 1, the Zn^II atom lies on a twofold axis and is coordinated by two O atoms and two N atoms of two bidentate 2-((9H-fluoren-2-yl)methyleneamino)phenolato ligands in a distorted tetrahedral geometry. The angles around Zn atom are within the range of 85.68 (8)–125.99 (8) ° (Table 1). The dihedral angle between the O1/Zn1/N8 and O1ⁱ/Zn1/N1ⁱ [symmetry code: (i) -x + 1, y, -z + 3/2] is 83.48 (6) °. The fluorene moiety (C9—C22) is almost planar, with r.m.s. deviations of 0.018 Å from the corresponding least-squares plane defined by the thirteen constituent atoms. In the 2-((9H-fluoren-2-yl)methyleneamino)phenol ligand, the phenol ring (O1–C7) is twisted at 30.22 (9) ° from the mean plane of the fluorene ring. The presence of intermolecular O24—H24···O1 hydrogen bonds link the complex and solvent molecules (Table 2 and Fig. 1).

Experimental

Preparation of ligand: 9H-fluorene-2-carbaldehyde (1.94 g, 10 mmol) was slowly added to 2-aminophenol (1.09 g, 10 mmol) in methanol/methylenechloride (1:1 v/v) (40 ml) solution at 50 °C for 5 h to obtain (E)-2-((9H-fluoren-2-yl)methyleneamino)phenol (L) as a yellow powder. Yield: 1.55 g (75%).

Preparation of zinc(II) compound: the reaction of L compound (1.50 g, 10 mmol) with zinc(II) acetate (0.91 g, 5 mmol) in methanol/methylenechloride (1:1 v/v) (40 ml) at 50 °C for 5 h yielded the title compound as an orange powder. The powder was filtered off and washed with hexane. Yield: 0.95 g (30%). Orange crystals of (I) were obtained from its ethanol solution by slow evaporation of the solvent at room temperature.