Bis(2,2′-bipyridine-κ2 N,N′)(nitrato-κO)copper(II) perchlorate

Yu Zhu; Yun-Long Wu; Chun-Xia Huang; Ji-Min Xie

doi:10.1107/S1600536811002571

. 2011 Feb 5;67(Pt 3):m306. doi: 10.1107/S1600536811002571

Bis(2,2′-bipyridine-κ² N,N′)(nitrato-κO)copper(II) perchlorate

Yu Zhu ^a, Yun-Long Wu ^a, Chun-Xia Huang ^a, Ji-Min Xie ^a,^*

PMCID: PMC3051949 PMID: 21522243

Abstract

In the title compound, [Cu(NO₃)(C₁₀H₈N₂)₂]ClO₄, the five-coordinated Cu^II atom has a distorted square-pyramidal CuN₄O environment; the O atom is in the axial position whereas the N atoms from two bipyridine (bipy) ligands are in the equatorial plane. In the crystal, molecules are assembled by C—H⋯O hydrogen bonding and π–π interactions between bipy groups [centroid–centroid distances = 3.7686 (16) and 3.7002 (16) Å] into a three-dimensional network. The nitrite anion is equally disordered over two sets of sites.

Related literature

For the applications of complexes with bipyridine and its derivatives in catalysis and visible-light-driven water oxidation, see: Morrow & Trogler (1989 ▶) and Duan et al. (2010 ▶), respectively.

Experimental

Crystal data

[Cu(NO₃)(C₁₀H₈N₂)₂]ClO₄
M _r = 537.38
Triclinic,
a = 7.5882 (15) Å
b = 10.473 (2) Å
c = 14.041 (3) Å
α = 76.15 (3)°
β = 81.46 (4)°
γ = 78.86 (3)°
V = 1056.9 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.22 mm⁻¹
T = 295 K
0.24 × 0.20 × 0.18 mm

Data collection

Rigaku Saturn 724 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ▶) T _min = 0.747, T _max = 0.803
10121 measured reflections
4037 independent reflections
3579 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.088
S = 1.05
4037 reflections
351 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002571/kp2303sup1.cif

e-67-0m306-sup1.cif^{(27.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002571/kp2303Isup2.hkl

e-67-0m306-Isup2.hkl^{(197.8KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—N1	1.986 (2)
Cu1—N4	1.9890 (19)
Cu1—N2	2.0426 (19)
Cu1—N3	2.0534 (18)
Cu1—O3	2.38 (4)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O5ⁱ	0.93	2.58	3.276 (3)	132
C7—H7⋯O4ⁱⁱ	0.93	2.53	3.322 (4)	144
C13—H13⋯O7ⁱⁱⁱ	0.93	2.43	3.249 (3)	147

Open in a new tab

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

Acknowledgments

We thank the Social Development Foundation of Jiangsu Province of China (BS2006038) and the Industry High Technology Foundation of Jiangsu (BG2007025).

supplementary crystallographic information

Comment

Complexes with bipyridine and its derivatives have been extensively studied because of their potential applications in catalysis (Morrow & Trogler, 1989) and visible light driven water oxidation (Duan et al., 2010). Herein we report the synthesis and structure of the title copper complex with 2, 2'-bipyridine.

The structure of the title complex (Fig. 1)consists of a discrete cation [Cu(bipy)₂(NO₃)]⁺ and an uncoordinated ClO₄^- anion which is in disorder. The Cu(II) atom is five coordinated by four nitrogen atoms from two bipy ligands and one oxygen atom from one nitrate anion, exhibiting a distorted square pyramidal coordination with the oxygen atom in the axial position (Fig. 1 and Table 1). The uncoordinated perchlorate anion displays the expected tetrahedral geometry. There are weak intermolecular C—H···O hydrogen bonds in the crystal structure(C3—H3···O5ⁱ, C7—H7···O4ⁱⁱ and C13—H13···O7ⁱⁱⁱ; Table 2). Crystal packing is stabilised by the C—H···O hydrogen bonds and π-π interactions between two parallel bipy rings [centroid (N1, C1—C5)···centroid (N1, C1—C5)^iv = 3.77 Å; centroid (N2, C6—C10) ···centroid (N2, C6—C10)^v= 3.70 Å; centroid (N3, C16—C20)···centroid (N4, C11—C15)^vi = 3.75 Å; symmetry codes: (iv)-x, 1 - y, -z; (v) 1 - x, -y, -z; (vi) -x, -y, 1 - z)](Fig. 2).

Experimental

2, 2'-bipyridine (31.3 mg, 0.2 mmol), Cu(NO₃)₂.3H₂O(42 mg, 0.2 mmol), NaClO₄ (28 mg, 0.2 mmol), acetone (10 mL) and methanol (6 mL) were stirred for 8 h at 313 K. The solution was then filtered, evaporated in the air and prismatic blue crystals were formed after 2 days (yieled 78%).