Bis{1-[(E)-o-tolyl­diazen­yl]-2-naphtho­l­ato}copper(II)

Wan-Ju Tai; Chi-Huan Li; Chen-Yu Li; Bao-Tsan Ko

doi:10.1107/S1600536810037888

. 2010 Sep 30;66(Pt 10):m1315. doi: 10.1107/S1600536810037888

Bis{1-[(E)-o-tolyldiazenyl]-2-naphtholato}copper(II)

Wan-Ju Tai ^a, Chi-Huan Li ^a, Chen-Yu Li ^a, Bao-Tsan Ko ^a,^*

PMCID: PMC2983183 PMID: 21587451

Abstract

In the title complex, [Cu(C₁₇H₁₃N₂O)₂], the Cu^II atom is tetracoordinated by two N atoms and two O atoms from two bidentate 1-[(E)-o-tolyldiazenyl]-2-naphtholate ligands, forming a slightly distorted square-planar environment. The two N atoms and two O atoms around the Cu^II atom are trans to each other, with an O—Cu—O bond angle of 177.00 (9)° and an N—Cu—N bond angle of 165.63 (10)°. The average distances between the Cu^II atom and the coordinated O and N atoms are 1.905 (2) and 1.995 (2)Å, respectively.

Related literature

For background to 1-phenylazo-2-naphtol derivatives, see: Shen et al. (2003 ▶); Lin et al. (2010 ▶). For related structures: see: Lin et al. (2008 ▶).

Experimental

Crystal data

[Cu(C₁₇H₁₃N₂O)₂]
M _r = 586.14
Monoclinic,
a = 12.9777 (2) Å
b = 15.2771 (3) Å
c = 15.1674 (2) Å
β = 114.514 (1)°
V = 2736.05 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 296 K
0.18 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.864, T _max = 0.921
25896 measured reflections
6767 independent reflections
3353 reflections with I > 2σ(I)
R _int = 0.067

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.117
S = 1.02
6767 reflections
372 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037888/rk2236sup1.cif

e-66-m1315-sup1.cif^{(26.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037888/rk2236Isup2.hkl

e-66-m1315-Isup2.hkl^{(331.2KB, hkl)}

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

Acknowledgments

We gratefully acknowledge financial support in part from the National Science Council, Taiwan (NSC99-2113-M-033-007-MY2) and in part from the CYCU Distinctive Research Area project in Chung Yuan Christian University, Taiwan (CYCU-98-CR-CH).

supplementary crystallographic information

Comment

Recently, the 1-phenylazo-2-naphtol (PAN-H) derivatives attract our attentions because the phenylazo-naphtolate group can provide the N,O-bidentate chelation to stabilize the transition metal or main group metal complexes. Therefore, our group is interested in the synthesis and preparation of metal complexes bearing such a ligand of this kind. For instance, our group has successfully synthesized and structural characterized the Pd(II) complex with N,O-bidentate phenylazo-naphtolate ligands (Lin et al., 2010). In addition, Shen et al., (2003) reported that Zn, Cu, and Co complexes supported by N,N,O,O-tetradentate binaphthyldiamino salen ligands have been demonstrated effectively to catalyze epoxides and CO₂ coupling reactions to achieve five-membered ring cyclic carbonates. In order to develop various metal systems originated from PAN derivatives and to investigate the catalytic behavior of these complexes, we report herein the synthesis and crystal structure of the title compound, (I), a potential catalyst for CO₂/epoxide coupling reactions (Scheme 1).

The solid structure of (I) reveals a monomeric Cu^II complex (Fig. 1) containing two six-membered rings coordinated from these two N,O-bidentate phenylazo-naphtolate ligands. The geometry around Cu atom is tetra-coordinated with a slight distorted square planar environment and two nitrogen atoms and two oxygen atoms are almost coplanar in which the sums of bond angles around Cu center are 359.81 (9)°. The two N atoms and two O atoms around Cu^II atom are trans- to each other with O1–Cu–O2 bond angle of 177.00 (9)° and N2–Cu–N4 bond angle of 165.63 (10)°. The distances between the Cu atom and O1, O2, N2 and N4 are 1.887 (2), 1.9234 (19), 2.001 (2) and 1.988 (2)Å, respectively. These average bond distances are similar to those found in the crystal structure of (5-methoxy-2-{1-[2-(dimethylamino)ethylimino]benzyl}phenolato)copper(II) acetate (Lin et al., 2008).

Experimental

The title compound (I) was synthesized by the following procedures (Fig. 2): (E)-1-(o-tolyldiazenyl)naphthalen-2-ol (0.52 g, 2.0 mmol) and Cu(OAc)₂^.H₂O (0.20 g, 1.0 mmol) was stirred at 298 K in the mixture of THF/MeOH (10/10 ml) for 24 h. Volatile materials were removed under vacuum and the residue was washed twice from hexane solution to give dark brown solids. The resulting solids were crystallized from CH₂Cl₂/Hexane (1:5) solution to yield brown crystals.