catena-Poly[dieth­yl(2-hydroxy­ethyl)­ammonium [[tetra-μ-acetato-κ8 O:O′-dicuprate(II)(Cu—Cu)]-μ-acetato-κ2 O:O′] dichloro­methane solvate]

Muhammad Shahid; Muhammad Mazhar; Paul O’Brien; Mohammad Afzaal; James Raftery

doi:10.1107/S1600536808044048

. 2009 Jan 8;65(Pt 2):m163–m164. doi: 10.1107/S1600536808044048

catena-Poly[diethyl(2-hydroxyethyl)ammonium [[tetra-μ-acetato-κ⁸ O:O′-dicuprate(II)(Cu—Cu)]-μ-acetato-κ² O:O′] dichloromethane solvate]

Muhammad Shahid ^a, Muhammad Mazhar ^a,^*, Paul O’Brien ^b, Mohammad Afzaal ^b, James Raftery ^b

PMCID: PMC2968312 PMID: 21581773

Abstract

The title compound, {(C₆H₁₆NO)[Cu₂(CH₃COO)₅]·CH₂Cl₂}_n, consists of acetate-bridged Cu₂(CH₃COO)₄ units that are connected via another acetate anion at each terminus to form infinite anionic [{Cu₂(CH₃COO)₄}(CH₃COO)]_n chains along [100]. The connecting acetate is hydrogen bonded to the diethyl(2-hydroxyethyl)ammonium cation, and the dichloromethane solvent molecule fills the remaining voids in the structure. The O—Cu—Cu angles along the polymeric chain are nearly linear [175.49 (5)°], but individual O—Cu—Cu—O units along the chain are bent and rotated against each other at the bridging acetate ion. Translation of each Cu₂(CH₃COO)₄ unit along the chain, represented by the least-squares plane of the two copper ions along with four of the acetate O atoms, rotated these units by 35.16 (3)°.

Related literature

Shahid, Mazhar, Helliwell et al. (2008 ▶) describe the study of dinuclear Cu complexes; Van Niekerk & Schoening (1953 ▶) provide X-ray evidence for Cu—Cu bonds in cupric acetate; Brown & Chidambaram (1973 ▶) report the redetermination of the structure of cupric acetate by neutron-diffraction; Shahid, Mazhar, Malik et al. (2008 ▶); Hamid et al. (2007 ▶) and Zhang et al. (2004 ▶) describe geometric parameters of organo–copper complexes.

Experimental

Crystal data

(C₆H₁₆NO)[Cu₂(C₂H₃O₂)₅]·CH₂Cl₂
M _r = 625.42
Orthorhombic,
a = 17.6366 (11) Å
b = 12.1078 (8) Å
c = 11.9148 (7) Å
V = 2544.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.94 mm⁻¹
T = 100 (2) K
0.40 × 0.40 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.657, T _max = 0.830
21202 measured reflections
5939 independent reflections
5693 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.080
S = 1.08
5939 reflections
306 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.40 e Å⁻³
Absolute structure: Flack (1983 ▶), 2726 Friedel pairs
Flack parameter: 0.017 (11)

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); 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/S1600536808044048/zl2161sup1.cif

e-65-0m163-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808044048/zl2161Isup2.hkl

e-65-0m163-Isup2.hkl^{(290.8KB, 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
N1—H1⋯O10ⁱ	0.93	1.97	2.832 (4)	153
N1—H1⋯O9ⁱ	0.93	2.45	3.056 (3)	123
O11—H11⋯O9ⁱ	0.84	2.04	2.840 (3)	159

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Symmetry code: (i) Inline graphic .

Acknowledgments

MS is grateful to the Higher Education Commission of Pakistan and the Pakistan Science Foundation for financial support via their PhD program.

supplementary crystallographic information

Comment

The background of this study has been set out in our previous work on the structural chemistry of metal-organic compounds (Shahid, Mazhar, Helliwell et al., 2008). Herein, as a continuation of these studies, the structure of the title compound is described which consists of acetate bridged Cu₂(CH₃COO)₄ units that are connected via another acetate anion at each terminus to form infinite anionic [{Cu₂(CH₃COO)₄}(CH₃COO)]_n chains along the [100] direction of the crystal. Crystallographically speaking the chain is generated from a glide related copies of the monomer. The connecting acetate is hydrogen bonded to the (diethylammonium)ethanol cation (Fig. 2). The dichloromethane solvate molecule occupies voids in the structure. The O—Cu—Cu angles along the polymeric chain are nearly linear (175.49 (5)°), but individual O—Cu—Cu—O units along the chain are rotated relative to each other. Representing the orientation of Cu₂(CH₃COO)₄ unit by the least squares plane Cu1 Cu2 O1 O2 O5 O6, translation along the chain rotates the orientation by 35.16 (3)°.

In the title compound (Fig.1), the two metal centers are similar; each has a coordination number of six having a coordination geometry close to octahedral, with a CuO₅Cu core similar to that of Cu centers in Cu₂(OAc)₄(H₂O)₂. The basal planes of Cu(1) and Cu(2) are each composed of an oxygen from each of the four acetate groups (O(1), O(3), O(5), O(8) and O(2), O(4), O(6), O(7) respectively), which link the two copper atoms in the monomer. Coordination by the fifth acetate's O atoms, O(9) and O(10) (from a symmetry generated copy), form one apical bond for Cu(2) and Cu(1) respectively. The octahedral coordination of the copper atoms is completed by the apical Cu(1)—Cu(2) bond of 2.6259 (4) Å. This is significantly shorter than the 2.64 Å as reported for dinuclear copper (II) acetate monohydrate in 1953 (Van Niekerk & Schoening, 1953), but close to the more accurate value obtained in a redetermination by neutron diffraction analysis (2.6143 (17) Å, Brown & Chidambaram, 1973). The Cu—O bond lengths in the basal planes for both the Cu atoms range from 1.949 (2) to 1.985 (2) Å and the average distance is in good agreement with 1.97 Å, as reported for copper acetate (Van Niekerk & Schoening, 1953). The most striking structural difference between the title compound and the dinuclear units in cupric acetate appears to be the weaker apixal bonds Cu—O which are 2.148 (18) and 2.124 (18) Å for Cu(1) and Cu(2), respectively in the title compound and 2.20 Å in the cupric acetate. The distortion is further evident from the slight deviation of trans angles in the basal plane and axial angle from ideal value of 180°. This is in good agreement with the literature (Shahid, Mazhar, Malik et al., 2008); Hamid et al., 2007; Zhang et al., 2004). In the structure, the (diethylamonium)ethanol cations are linked through hydrogen bonds [O(11)—H(11)···O(9)], [N(1)—H(1)···O(9)] and [N(1)—H(1)···O(10)] to the connecting acetate group occupying cis positions at the main polymeric chain (Table 1, Fig. 3).

Experimental

N,N-Diethylaminoethanol (deaeH) (0.27 g, 2.34 mmol) and acetic acid (0.14 g, 2.34 mmol) were added to a stirred suspension of Cu(CH₃COO)₂.H₂O (0.85 g, 4.67 mmol) in 25 ml dichloromethane. After two hours stirring, the mixture was vacuum evaporated to dryness and the solid was redissolved in minimum amount of dichloromethane to give blue block-shaped crystals at room temperature after two weeks.