Acetonitrile­{3-[bis­(2-pyridyl­methyl-κN)amino-κN]propanol-κO}(perchlorato-κO)copper(II) perchlorate

Jong Won Shin; Sankara Rao Rowthu; Hyun Jung Cho; Kil Sik Min

doi:10.1107/S1600536810053985

. 2011 Jan 8;67(Pt 2):m143–m144. doi: 10.1107/S1600536810053985

Acetonitrile{3-[bis(2-pyridylmethyl-κN)amino-κN]propanol-κO}(perchlorato-κO)copper(II) perchlorate

Jong Won Shin ^a, Sankara Rao Rowthu ^a, Hyun Jung Cho ^b, Kil Sik Min ^b,^*

PMCID: PMC3051508 PMID: 21522828

Abstract

In the title compound, [Cu(ClO₄)(C₂H₃N)(C₁₅H₁₉N₃O)]ClO₄, the Cu^II ion is coordinated by three N atoms and a hydroxyl-O atom of the tetradentate ligand, an O atom of a perchlorate ion and an N atom of an acetonitrile ligand giving a tetragonally distorted octahedral environment around the copper(II) atom. There is an offset inter-complex face-to-face π–π interaction [centroid–centroid distance = 3.718 (2) Å] involving one of the pyridine rings of the ligand as well as an intra-complex O—H⋯O hydrogen-bonding interaction between the coordinated hydroxyl group of the ligand and the perchlorate counter-ion.

Related literature

The preparation and characterization of polyamine complexes have allowed the elucidatation of the mechanisms of metalloenzyme reactions, see: Tshuva & Lippard (2004 ▶). For studies of complexes with bis(2-pyridylmethyl)amine moieties, see: Bebout et al. (1998 ▶); Shin et al. (2010 ▶). For potential biological applications of the tridentate unit, see: van Staveren et al. (2002 ▶). Examples include the use of Pd^II and Pt^II complexes with bis(2-pyridylmethyl)amine or its derivatives as anticancer agents, e.g. cis-platin (Rauterkus et al., 2003 ▶). For intercomplex π–π stacking interactions, see: Shetty et al. (1996 ▶). For the preparation of N,N-bis(2-pyridylmethyl)-3-aminopropanol, see: Young et al. (1995 ▶).

Experimental

Crystal data

[Cu(ClO₄)(C₂H₃N)(C₁₅H₁₉N₃O)]ClO₄
M _r = 560.83
Monoclinic,
a = 18.8394 (16) Å
b = 10.6049 (9) Å
c = 23.171 (2) Å
β = 102.998 (2)°
V = 4510.7 (7) Å³
Z = 8
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 200 K
0.20 × 0.17 × 0.08 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.777, T _max = 0.904
16472 measured reflections
5616 independent reflections
3249 reflections with I > 2σ(I)
R _int = 0.066

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.188
S = 1.11
5616 reflections
303 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.66 e Å⁻³
Δρ_min = −1.16 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810053985/zs2085sup1.cif

e-67-0m143-sup1.cif^{(22.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053985/zs2085Isup2.hkl

e-67-0m143-Isup2.hkl^{(269.5KB, 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
O1—H1A⋯O9	0.74 (5)	2.46 (5)	3.090 (12)	145 (5)

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Acknowledgments

This work was supported by a Korea Research Foundation (KRF) grant funded by the Korea government (MEST) (No. 2009–0073897). The authors acknowledge the Korea Basic Science Institute for the X-ray data collection.

supplementary crystallographic information

Comment

The preparation and characterization of polyamine complexes have allowed the elucidatation of the mechanisms of metalloenzyme reactions (Tshuva & Lippard, 2004). The complexes with bis(2-pyridylmethyl)amine moieties have been widely studied (Bebout et al.,1998; Shin et al., 2010) because the tridentate unit has potential in biological applications (van Staveren et al., 2002), examples being the Pd^II and Pt^II complexes with bis(2-pyridylmethyl)amine or its derivatives, as anticancer agents, e.g. cis-platin (Rauterkus et al., 2003). Here, we report the synthesis and crystal structure of a six-coordidine Cu^II complex with N,N-bis(2-pyridylmethyl)-3-aminopropanol (bpapOH), the title compound [Cu(bpapOH)(CH₃CN)(ClO₄)] ClO₄ (I).

In the title compound (Fig. 1) the copper(II) ion is bonded to three N atoms of the tetradentate ligand and one N atom from an acetonitrile solvent molecule in an equatorial plane and two O atoms in axial sites, one from the hydroxyl group of the ligand, the other from a perchlorate ion, resulting in a tetragonally distorted octahedral stereochemistry. The bond lengths around Cu^II in the equatorial plane are in the range of 1.986 (4)–2.021 (4) Å while the axial Cu–O distances are 2.232 (4) Å (hydroxy) and 2.868 (4) Å (perchlorate), due to Jahn-Teller distortion. The bond angles about the copper atom lie in the range 84.12 (17)–178.30 (19)°. One of the pyridyl groups of the coordinated bpapOH ligand (N1–C5) is involved in a an offset face-to-face π–π inter-complex stacking interaction (Shetty et al., 1996) (ring centroid separation Cg1···Cgⁱ, 3.718 (2) Å], giving dimers (Fig. 2) [symmetry code: (i) -x + 1/2, -y + 1/2, -z + 1]. The inter-planar separation of these pyridine rings is 3.491 (2) Å and the dihedral angle between the pyridine ring planes is 0.0°. Additionally, an intra-complex O—H···O hydrogen-bonding interaction is found between the hydroxyl group of the ligand and the free perchlorate anion (Table 1) (Fig. 3).

Experimental

A MeOH solution (5 ml) of Cu(ClO₄)₂ . 6H₂O (72 mg, 0.194 mmol) was added to a MeOH solution (5 ml) of N,N-bis(2-pyridylmethyl)-3-aminopropanol (bpapOH) (50 mg, 0.194 mmol) (Young et al., 1995). The mixture was stirred for 10 min at room temperature, resulting in a color change to blue-green. Diffusion of diethylether into the mixture gave blue crystals of the title compound after a few days and these were washed with diethyl ether and dried in air (yield: 43 mg, 40%). FTIR (KBr, cm^-1): ν(OH), 3393; ν(ClO₄^-), 1087, 627; ν(C—H), 3070, 2862; ν(C—N), 1607.