Dichlorido[2-(3,5-dimethyl-1H-pyrazol-1-yl-κN 2)quinoline-κN]zinc

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

doi:10.1107/S1600536812014390

. 2012 Apr 13;68(Pt 5):m571–m572. doi: 10.1107/S1600536812014390

Dichlorido[2-(3,5-dimethyl-1H-pyrazol-1-yl-κN ²)quinoline-κN]zinc

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

PMCID: PMC3344321 PMID: 22590087

Abstract

The Zn^II atom in the title compound, [ZnCl₂(C₁₄H₁₃N₃)], is coordinated by a Cl₂N₂ donor set defined by quinoline and pyrazole N atoms of the chelating ligand and two Cl atoms. Distortions from the ideal tetrahedral geometry relate to the restricted bite angle of the chelating ligand [N—Zn—N = 78.54 (12)°]. In the crystal, molecules are connected into a three-dimensional structure by C—H⋯Cl interactions, involving both Cl atoms, and π–π interactions that occur between the pyrazole ring and each of the pyridine and benzene rings of the quinoline residue [intercentroid distances = 3.655 (2) and 3.676 (2) Å].

Related literature

For background to luminescent coordination complexes, see: Bai et al. (2012 ▶); Chou et al., (2011 ▶); Hu et al. (2011 ▶); Wang (2001 ▶). For the synthesis, see: Savel’eva et al. (2009 ▶); Scott et al. (1952 ▶).

Experimental

Crystal data

[ZnCl₂(C₁₄H₁₃N₃)]
M _r = 359.54
Monoclinic,
a = 14.3353 (10) Å
b = 8.7683 (5) Å
c = 11.9839 (8) Å
β = 102.181 (7)°
V = 1472.42 (17) Å³
Z = 4
Mo Kα radiation
μ = 2.02 mm⁻¹
T = 100 K
0.25 × 0.20 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.597, T _max = 1.000
6070 measured reflections
3370 independent reflections
2438 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.124
S = 1.02
3370 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 1.04 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); 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/S1600536812014390/hg5206sup1.cif

e-68-0m571-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014390/hg5206Isup2.hkl

e-68-0m571-Isup2.hkl^{(165.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Zn—N1	2.021 (3)
Zn—N3	2.072 (3)
Zn—Cl1	2.2099 (11)
Zn—Cl2	2.2076 (11)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cl1ⁱ	0.98	2.81	3.680 (4)	148
C12—H12A⋯Cl2ⁱⁱ	0.95	2.82	3.579 (4)	138

Open in a new tab

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

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

Luminescent coordination complexes are used as emitting materials in light-emitting devices (Chou et al., 2011) and it is known that many Zn^II nitrogen donor complexes are brightly luminescent in the blue region of the spectrum (Wang, 2001). The title compound (I) was prepared as part of our on-going quest for luminescent organometallic and coordination complexes with improved quantum efficiencies and colour purity (Bai et al., 2012; Hu et al., 2011;).

The Zn^II atom in (I), Fig. 1, is chelated by quinolinyl- and pyrazolyl-N atoms and two chloride atoms, Table 1. The resulting Cl₂N₂ donor set defines a tetrahedron with a significant distortion apparent owing to the restricted bite angle of the chelating ligand, i.e. N1—Zn—N3 78.54 (12)°; the remaining angles lie in the range 111.52 (9)°, for N1—Zn—Cl1, to 115.73 (9)°, for N1—Zn—Cl2. The five-membered chelate ring is essentially planar with a r.m.s. deviation = 0.035 Å with maximum deviations of 0.034 (3) and -0.029 (3) Å for the N2 and N1 atoms, respectively. A small twist is apparent in the bidentate ligand with the dihedral angle between the quinolinyl and pyrazolyl rings being 6.84 (17)°. The overall coordination geometry found for (I) matches that seen in the species carrying an additional methyl group in the 4-position of the quinolinyl residue (Savel'eva et al., 2009).

In the crystal packing, Fig. 2, molecules are connected into a three-dimensional architecture by C—H···Cl interactions, Table 1, involving both chloride atoms, and π—π interactions between the pyrazoyl ring and each of the pyridyl and benzene rings of the quinolinyl residue [inter-centroid distances = 3.655 (2) and 3.676 (2) Å, respectively; angles of inclination = 3.2 (2) and 3.5 (2)°, respectively; for symmetry operation: x, 1/2 - y, -1/2 + z].

Experimental

The title compound was prepared by modification of literature procedures (Savel'eva et al., 2009; Scott et al. 1952). 3,5-Dimethyl-1-(2'-quinolyl)pyrazole (0.080 g) in a mixture of EtOH (4 ml) and CH₂Cl₂ (2 ml) was added to a solution of ZnCl₂ (0.061 g) in EtOH (8 ml). A white precipitate formed and was collected by filtration after 1 h, washed with EtOH and air-dried. The crude product was recrystallized from its CH₂Cl₂/hexane solution. Yield 0.054 g (42%). M. pt: 607–608 K. IR ν/cm^-1: 1619, 1596, 1579, 1559, 1511, 1479, 1439, 1386, 1380, 1346, 1319, 1142, 1090, 994, 983, 825, 783, 760.