[2,2′-(1,1′-Binaphthyl-2,2′-diyldiimino)­diethanol-κ3 N,N′,O]dichloridocopper(II)

Wan-Yun Huang; Dong-Cheng Liu; Han-Chang Wei; Fu-Pei Liang

doi:10.1107/S1600536811049828

. 2011 Nov 25;67(Pt 12):m1844. doi: 10.1107/S1600536811049828

[2,2′-(1,1′-Binaphthyl-2,2′-diyldiimino)diethanol-κ³ N,N′,O]dichloridocopper(II)

Wan-Yun Huang ^a, Dong-Cheng Liu ^a, Han-Chang Wei ^a, Fu-Pei Liang ^a,^*

PMCID: PMC3238740 PMID: 22199617

Abstract

In the title complex, [CuCl₂(C₂₄H₂₄N₂O₂)], the Cu^II cation is N,N′,O-chelated by a 2,2′-(1,1′-binaphthyl-2,2′-diyldiimino)diethanol ligand and coordinated by two chloride anions in a distorted square-pyramidal geometry. In the diethanol ligand, the two naphthalene ring systems are twisted with respect to each other at a dihedral angle of 68.30 (9)°. The uncoordinated hydroxy group links with a coordinated chloride anion via an intramolecular O—H⋯Cl hydrogen bond. Intermolecular N—H⋯O and N—H⋯Cl hydrogen bonds occur in the crystal structure.

Related literature

For background to metal complexes containing N-substituted diethanolamine ligands, see: Saalfrank et al. (2008 ▶); Ferguson et al. (2011 ▶); Alley et al. (2008 ▶). For the synthesis of the ligand, see: Yan et al. (2008 ▶). For related structures, see: Thob et al. (2010 ▶); Telfer et al. (2004 ▶).

Experimental

Crystal data

[CuCl₂(C₂₄H₂₄N₂O₂)]
M _r = 506.89
Triclinic,
a = 7.4816 (8) Å
b = 10.4211 (11) Å
c = 15.2116 (16) Å
α = 94.130 (2)°
β = 103.633 (2)°
γ = 106.912 (2)°
V = 1090.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 185 K
0.31 × 0.17 × 0.10 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.694, T _max = 0.883
5452 measured reflections
3758 independent reflections
3363 reflections with I > 2σ(I)
R _int = 0.012

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.107
S = 1.04
3758 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 datablock(s) global, I. DOI: 10.1107/S1600536811049828/xu5393sup1.cif

e-67-m1844-sup1.cif^{(24.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811049828/xu5393Isup2.hkl

e-67-m1844-Isup2.hkl^{(184.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—N1	2.052 (2)
Cu1—N2	2.106 (2)
Cu1—O2	1.965 (2)
Cu1—Cl1	2.6190 (7)
Cu1—Cl2	2.2272 (8)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl1	0.84	2.41	3.039 (2)	132
O2—H2B⋯Cl1ⁱ	0.84	2.33	2.996 (2)	137
N2—H2A⋯O1ⁱⁱ	0.93	2.00	2.889 (3)	158

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

Acknowledgments

The authors thank the National Natural Science Foundation of China (grant No. 20971029) and the Guangxi Natural Science Foundation of China (No. 2010GXNSFD013018).

supplementary crystallographic information

Comment

N-substituted diethanolamine ligands have been proven to be fruitful in the construction of fascinating functional metal complexes (Saalfrank et al., 2008; Ferguson et al., 2011; Alley et al., 2008). But the ligand which contains two or more N-substituted diethanolamine has received much less attention. we designed and synthesized successfully a racemic ligand of N, N'-Bis-(2-hydroxy-ethyl)-(1,1'-Binaphthyl-2,2'-diamine) (BHEBA), herein we report the crystal structure of a Cu^II complex about it. The single-crystal X-ray structural analysis reveals that asymmetric unit contains one five-coordinated Cu^II ion, a new ligand N,N'-(2-hydroxy-ethyl)-(1,1'-binaphthyl-2,2'-diamine) (HEBA), namely partly decomposed of the parent ligand and two Cl^- ions as shown in Fig. 1. Due to the Jahn-Teller effect, the distance of the Cu—Cl(1) bond is elongated to 2.6188 (Å), which is consistent with the reported copper complexes (Telfer et al., 2004). Two adjacent polymeric H-bonded chains of opposite chirality (Thob et al., 2010) by the hydrogen bond N(2)—H(2 A)···O(1) and O(1)—H (1 A)···Cl(1) extend along a direction, and these chains are interconnected by the repeating weak O(2)—H(2B)···Cl(1) (symmetry code: -x + 1, -y + 1, -z + 1) hydrogen bonds (Fig. 2.), which further stabilize the structure. The corresponding lengths and angles of hydrogen bonds are listed in Table 1.

Experimental

The target ligand of racemic N,N'-Bis-(2-hydroxy-ethyl)-(1,1'-Binaphthyl-2,2'- diamine) (BHEBA) were synthesized by the reported procedure (Yan et al., 2008) in 55% yield using racemic 1,1'-binaphthyl-2,2'-diamine as materials.

CuCl₂ (25.5 mg, 0.15 mmol), NMe₄OH 18.1 mg (0.10 mmol), and BHEBA (46.1 mg, 0.10 mmol) were mixed in a CH₃OH /ⁱPrOH (10 ml, v/v 3:2) solution with vigorous stirring for 10 h. The resulting solution was filtered and left to stand at room temperature. Brown block crystals suitable for X-ray analysis were obtained in 30% yield by slow evaporation of the solvent over a period of two week. Analysis, calculated for C₂₄H₂₄N₂O₂Cl₂Cu: C 56.86, H 4.77, N 5.53%; found: C 56.45, H 4.43, N 5.62%.