[2,9-Bis(3,5-dimethyl-1H-pyrazol-1-yl-κN 2)-1,10-phenanthroline-κ2 N,N′]bis­(thio­cyanato-κN)cadmium(II)

Lu Yi Zheng; Yan Hui Chi

doi:10.1107/S1600536810051275

. 2010 Dec 11;67(Pt 1):m68. doi: 10.1107/S1600536810051275

[2,9-Bis(3,5-dimethyl-1H-pyrazol-1-yl-κN ²)-1,10-phenanthroline-κ² N,N′]bis(thiocyanato-κN)cadmium(II)

Lu Yi Zheng ^a,^*, Yan Hui Chi ^b

PMCID: PMC3050342 PMID: 21522586

Abstract

In the title complex, [Cd(NCS)₂(C₂₂H₂₀N₆)], the Cd^II ion is in a CdN₆ coordination geometry which is intermediate between octahedral and trigonal–prismatic. The dihedral angles formed between the mean planes of the pyrazole rings and the phenanthroline system are 15.74 (15) and 16.30 (13)°. In the crystal, there is a π–π stacking interaction involving two symmetry-related pyrazole rings, with a centroid–centroid distance of 3.664 (3) Å. In addition, there is a relatively short intermolecular contact between C atoms [C⋯C = 3.399 (6) Å] involving symmetry-related pyridine rings along the a axis.

Related literature

For a related structure, see: Wang et al. (2009 ▶).

Experimental

Crystal data

[Cd(NCS)₂(C₂₂H₂₀N₆)]
M _r = 597.00
Monoclinic,
a = 8.1350 (15) Å
b = 20.601 (4) Å
c = 14.633 (3) Å
β = 99.323 (3)°
V = 2420.0 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.11 mm⁻¹
T = 298 K
0.35 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.698, T _max = 0.917
14038 measured reflections
5272 independent reflections
4099 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.101
S = 1.05
5272 reflections
320 parameters
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.56 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810051275/lh5181sup1.cif

e-67-00m68-sup1.cif^{(25.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051275/lh5181Isup2.hkl

e-67-00m68-Isup2.hkl^{(258.2KB, hkl)}

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

Acknowledgments

The authors thank the Science Foundation of University of Jinan of China.

supplementary crystallographic information

Comment

Derivatives of 1,10-phenanthroline play an important role in modern coordination chemistry and many complexes have been reported with these types of compounds as ligands [see e.g. Wang et al. (2009) for a closely related Cd complex]. To the best of our knowledge, no crystal structures of complexes with 2,9-bis(3,5-Dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline as a ligand have been reported so far. Herein we report the crystal structure of the title compound (I).

Fig. 1 shows the title complex. The Cd^II ion is in a CdN₆ coordination geometry which is approximately intermediate between octahedral and triginal-prismatic and this may be attributed to the chelation mode of the 2,9-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline ligand. The dihedral angles between the planes that consist of the non-hydrogen atoms of the 1,10-phenanthroline ring system and the pyrazole rings are 15.74 (15)° (involving the pyrazole ring containing atoms N1 and N2) and 16.30 (13)° (involving the pyrazole ring containing atoms N5 and N6), respectively. In the crystal structure, there is a π–π stacking interaction involving symmetry related pyrazole rings, with the relevant distance being Cg1···Cg2ⁱ 3.664 (3) Å and Cg1···Cg2ⁱ_perp = 3.610 Å (symmetry code: (i) 1+x, y, z; Cg1 and Cg2 are the centroids of C2-C4/N1N2 pyrazole ring and C19-C21/N5N6 pyrazole ring, respectively; Cg1···Cg2ⁱ_perp is the perpendicular distance from Cg1 ring to Cg2ⁱ ring). In addition, there is a relatively short intermolecular contact between atom C16 and C7ⁱⁱ (symmetry code: (ii) -1+x, y, z with a C···C separation of 3.399 (6) Å involving pyridine rings along the a axis (Fig. 2).

Experimental

A 10 ml methanol solution of Cd(ClO₄).6H₂O (0.0744 g, 0.177 mmol) was added into 10 ml dichloromethane solution of 2,9-bis(3,5-Dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline (0.0299 g, 0.081 mmol) in drops, and 5 ml of methanol solution containing NaNCS (0.0149 g, 0.184 mmol) was added into the mixed soluton. This solution was stirred for a few minutes. Colorless single crystals were obtained after the filtrate had been allowed to stand at room temperature for about a week.