Bis[μ-3,5-bis­(2-pyrid­yl)pyrazolato]bis­(hydrogensulfato)­dicopper(II) methanol disolvate

Akio Mishima; Akira Fuyuhiro; Hitoshi Kumagai; Satoshi Kawata

doi:10.1107/S1600536811038700

. 2011 Oct 12;67(Pt 11):m1523–m1524. doi: 10.1107/S1600536811038700

Bis[μ-3,5-bis(2-pyridyl)pyrazolato]bis(hydrogensulfato)dicopper(II) methanol disolvate

Akio Mishima ^a, Akira Fuyuhiro ^b, Hitoshi Kumagai ^c, Satoshi Kawata ^a,^*

PMCID: PMC3246951 PMID: 22219771

Abstract

The title compound, [Cu₂(C₁₃H₉N₄)₂(HSO₄)₂]·2CH₃OH, consists of discrete centrosymmetric dinuclear complex molecules and methanol solvent molecules. The Cu^II atom shows a square-pyramidal coordination geometry and is bonded to four N atoms of the two bis-chelating 3,5-bis(2-pyridyl)pyrazolate ions (bpypz⁻) and one O atom of the hydrogensulfate ion. The bpypz⁻ ligands in the complex molecule are virtually coplanar [dihedral angle between the mean ligand planes = 0.000(1)°] with the Cu^II atom deviating in opposite directions from their best plane by 0.2080 (12) Å. π–π stacking interactions between the pyridyl and pyrazole rings [centroid–centroid distance = 3.391 (3) Å] and strong O—H⋯O hydrogen bonds between the hydrogensulfate ligands and the methanol molecules assemble the molecules into a one-dimensional polymeric structure extending along the a axis. The methanol molecule acts both as an accepter and a donor in the hydrogen bonding.

Related literature

For metal complexes of 3,5-bis(2-pyridyl)pyrazole, see: Munakata et al. (1995 ▶); Nakano et al. (2004 ▶); Du et al. (2005 ▶); Yoneda, Adachi, Hayami et al. (2006 ▶); Yoneda, Adachi, Nishio et al. (2006 ▶); Ishikawa et al. (2008 ▶, 2010 ▶). For an example of a coordinated hydrogensulfate ion, see: Dragancea et al. (2008 ▶).

Experimental

Crystal data

[Cu₂(C₁₃H₉N₄)₂(HO₄S)₂]·2CH₄O
M _r = 827.82
Monoclinic,
a = 6.0909 (3) Å
b = 16.0581 (6) Å
c = 15.6579 (7) Å
β = 95.2044 (14)°
V = 1525.16 (12) Å³
Z = 2
Mo Kα radiation
μ = 1.61 mm⁻¹
T = 200 K
0.35 × 0.04 × 0.03 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Rigaku, 1995 ▶) T _min = 0.926, T _max = 0.953
16136 measured reflections
2470 independent reflections
3262 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.068
S = 1.08
3470 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2002 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2010 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811038700/gk2397sup1.cif

e-67-m1523-sup1.cif^{(25.7KB, cif)}

Supplementary material file. DOI: 10.1107/S1600536811038700/gk2397Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038700/gk2397Isup2.hkl

e-67-m1523-Isup2.hkl^{(170.2KB, hkl)}

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

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

Cu1—O1	2.2696 (13)
Cu1—N1	2.0865 (13)
Cu1—N2	1.9558 (13)
Cu1—N3ⁱ	1.9507 (13)
Cu1—N4ⁱ	2.0924 (14)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by funds (No. 101501) from the Central Research Institute of Fukuoka University and Grant-in-Aids for Science Research (No. 22550067) from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

supplementary crystallographic information

Comment

3,5-Bis(2-pyridyl)pyrazole[Hbpypz] is a versatile ligand in the construction of a series of mononuclear, dinuclear and polynuclear complexes (Munakata et al., 1995; Du et al., 2005; Yoneda et al., 2006; Ishikawa et al., 2010). The dinuclear complexes show the structure where two bpypz^- ions are bridging two metal ions with the axial coordination sites. This kind of dinuclear complexes with transition metal ions were reported previously (Nakano et al., 2004; Yoneda et al., 2006; Ishikawa et al., 2008). The title compound consists of the Cu^II dinuclear complex and two methanol solvent molecules. In the dinuclear complex, four N donors from two deprotonated tetradentate bridging bpypz^- ligands form the basal plane (Table 1). The copper(II) ion is penta-coordinated and it is in a slightly deformed square-pyramidal coordination environment with the τ value of 0.001 (Fig. 1). The apical position is occupied by the hydrogensulfate ion. An uncommon feature is that a sulfate ion is actually bound as the hydrogensulfate ion as there are only a few instances of unidentately coordinated hydrogensulfate ion (Dragancea et al., 2008). The π···π stacking interactions between pyridyl and pyrazole rings [centroid-centroid distance 3.391 (3) Å ] and strong hydrogen bonds between the hydrogensulfate ligands and the methanol molecules assemble molecules into a one dimensional polymeric structure extended along the a axis (Table 2, Fig. 2). The methanol molecule acts both as an accepter and a donor in O-H···O hydrogen bond.

Experimental

A methanolic solution of CuSO₄.6H₂O (5ml, 10 mmolL^-1) was transferred to a glass tube, and then a methanolic solution of Hbpypz (5ml, 10 mmolL^-1) was poured into the glass tube without mixing the solutions. Green crystals began to form at ambient temperature within one week (yield 84%). Elemental analysis: calcd (%) for C₂₈H₂₈Cu₂N₈O₁₀S₂: C 40.62, H 3.41, N 13.54; found: C 40.45, H 3.28, N 13.60.