(Acetato-κO)(acetato-κ2 O,O′)[2-(3,5-di­methyl-1H-pyrazol-1-yl-κN 2)quinoline-κN]zinc(II)

Muhd Hidayat bin Najib; Ai Ling Tan; David J Young; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536812025664

. 2012 Jun 13;68(Pt 7):m897–m898. doi: 10.1107/S1600536812025664

(Acetato-κO)(acetato-κ² O,O′)[2-(3,5-dimethyl-1H-pyrazol-1-yl-κN ²)quinoline-κN]zinc(II)

Muhd Hidayat bin Najib ^a, Ai Ling Tan ^a, David J Young ^a,^‡, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3393171 PMID: 22807739

Abstract

The Zn^II atom in the title compound, [Zn(C₂H₃O₂)₂(C₁₄H₁₃N₃)], is coordinated by an N₂O₃ donor set defined by the quinolinyl- and pyrazolyl-N atoms of the chelating heterocyclic ligand, and three carboxylate-O atoms derived from the monodentate and bidentate carboxylate ligands. Distortions from the ideal square-pyramidal coordination geometry relate to the restricted bite angle of the chelating ligands, i.e. O—Zn—O = 59.65 (5) and N—Zn—N = 76.50 (6)°, and the close approach of the non-coordinating carbonyl atom [Zn⋯O = 2.858 (2) Å]. In the crystal, molecules are consolidated into a three-dimensional architecture by C—H⋯O interactions

Related literature

For background to luminescent coordination complexes, see: Bai et al. (2011 ▶, 2012 ▶); Chou et al. (2011 ▶); Wang (2001 ▶). For the synthesis, see: Savel’eva et al. (2009 ▶); Scott et al. (1952 ▶). For the structure of the dichlorido analogue, see: Najib et al. (2012 ▶). For additional geometric analysis, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Zn(C₂H₃O₂)₂(C₁₄H₁₃N₃)]
M _r = 406.73
Triclinic,
a = 7.6586 (4) Å
b = 10.7334 (6) Å
c = 11.5772 (4) Å
α = 69.437 (4)°
β = 81.546 (3)°
γ = 72.736 (4)°
V = 849.93 (7) Å³
Z = 2
Cu Kα radiation
μ = 2.27 mm⁻¹
T = 100 K
0.25 × 0.15 × 0.05 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.617, T _max = 1.000
6205 measured reflections
3498 independent reflections
3322 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.081
S = 1.03
3498 reflections
239 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 datablock(s) global, I. DOI: 10.1107/S1600536812025664/hb6839sup1.cif

e-68-0m897-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812025664/hb6839Isup2.hkl

e-68-0m897-Isup2.hkl^{(171.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Zn—O1	2.0388 (14)
Zn—O2	2.3240 (15)
Zn—O3	1.9397 (13)
Zn—N1	2.0570 (15)
Zn—N3	2.1460 (14)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯O3ⁱ	0.98	2.57	3.544 (2)	176
C5—H5A⋯O2ⁱⁱ	0.98	2.60	3.417 (3)	141
C7—H7⋯O2ⁱⁱ	0.95	2.56	3.235 (2)	128
C9—H9C⋯O4ⁱⁱⁱ	0.98	2.36	3.274 (2)	156
C12—H12⋯O1^iv	0.95	2.51	3.310 (2)	142

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

Acknowledgments

We gratefully acknowledge funding from the Brunei Research Council, and thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/3).

supplementary crystallographic information

Comment

Many Zn^II complexes of nitrogen-containing ligands exhibit intense emission at room temperature (Wang, 2001; Chou et al., 2011; Bai et al., 2011; Bai et al., 2012). The title compound was prepared as part of a series of potentially luminescent coordination complexes for use in organic light emitting diode (OLED) materials. We have previously reported the solid-state structure of dichlorido[2-(3,5-dimethyl-1H-pyrazol-1-yl-2)quinoline]zinc(II) (Najib et al., 2012), i.e. the dichlorido analogue of the title compound, (I).

The Zn^II atom in (I), Fig. 1, is chelated by quinolinyl- and pyrazolyl-N atoms of the heterocyclic ligand, and three carboxylate-O atoms derived from the monodentate and bidentate carboxylates, Table 1. The resulting N₂O₃ donor set defines an approximate square pyramid with the Zn atom lying 0.8591 (8) Å out of the plane defined by the O1, O2, N1 and N3 atoms [r.m.s. deviation = 0.1122 Å] in the direction of the O3 atom. The assignment of coordination geometry is quantified by the value of τ = 0.06 which compares to the τ values of 0.0 and 1.0 for ideal square pyramidal and trigonal bipyramidal geometries, respectively (Addison et al., 1984). Significant distortions in the coordination geometry are apparent owing the restricted bite angles of the chelating ligands, i.e. O1—Zn—O2 = 59.65 (5)° and N1—Zn—N3 = 76.50 (6)°. Further distortions are related to the relatively close approach of the O4 atom to Zn, the Zn···O4 separation is 2.858 (2) Å. The five-membered chelate ring is approximately planar with a r.m.s. deviation = 0.088 Å and with maximum deviations of 0.074 (2) and -0.057 (1) Å for the N1 and Zn atoms, respectively. The bidentate ligand is planar with the dihedral angle between the quinolinyl and pyrazolyl rings being 2.14 (6)°.

Molecules are consolidated into a three-dimensional architecture by C—H···O interactions, Fig. 2 and Table 2.

Experimental

The title compound was prepared by modification of a literature procedure (Savel'eva et al., 2009) and as previously described for the corresponding dichloride (Najib et al., 2012). 3,5-Dimethyl-1-(2'-quinolyl)pyrazole (0.0908 g), prepared as in the literature (Scott et al., 1952), in a mixture of EtOH (4 ml) and CH₂Cl₂ (2 ml) was added to a suspension of Zn(OAc)₂ (0.0764 g) in EtOH (8 ml). The solution was heated to dissolve the Zn(OAc)₂. Light-brown prisms formed over a period of 16 h and were collected by filtration, washed with EtOH and recrystallized from CH₂Cl₂/hexane. Yield 0.0733 g (44%). M.pt: 474 K. IR v/cm^-1: 2925, 2864, 2365, 2323, 1604, 1507, 1424, 1388.