trans-Diaqua­bis(ethyl­enediamine-κ2 N,N′)copper(II) bis[3-(3-pyrid­yl)propionate] dihydrate

Jan Moncol; Peter Segľa; Dušan Mikloš; Andreas Fischer; Koman Marian

doi:10.1107/S1600536808005400

. 2008 Mar 5;64(Pt 4):m509–m510. doi: 10.1107/S1600536808005400

trans-Diaquabis(ethylenediamine-κ² N,N′)copper(II) bis[3-(3-pyridyl)propionate] dihydrate

Jan Moncol ^a,^*, Peter Segľa ^a, Dušan Mikloš ^a, Andreas Fischer ^b, Koman Marian ^a

PMCID: PMC2960896 PMID: 21201981

Abstract

The asymmetric unit of the title complex, [Cu(C₂H₈N₂)₂(H₂O)₂](C₈H₈NO₂)₂·2H₂O, contains one anion, one half-cation and one water molecule. The Cu^II atom in the [Cu(en)₂(H₂O)₂]²⁺ cation (en is ethylenediamine) lies on an inversion centre. The four N atoms of the en ligands in the equatorial plane around the Cu^II atom form a slightly distorted square-planar arrangement, while the slightly distorted Jahn–Teller octahedral coordination is completed by two water O atoms in axial positions. In the crystal structure, intra- and intermolecular N—H⋯O and O—H⋯O hydrogen bonds form a three-dimensional network.

Related literature

For general background, see: Hathaway & Hodgson (1973 ▶); Bernstein et al. (1995 ▶); Janiak (2000 ▶); Jeffrey (1997 ▶). For similar structures, see: Jašková et al. (2007 ▶); Miminoshvili et al. (2005 ▶); Carballo et al. (2005 ▶); Segla et al. (2000 ▶); Liu et al. (2004 ▶); Sharma et al. (2005 ▶); Anacona et al. (2002 ▶); Emsley et al. (1988 ▶, 1990 ▶); Li et al. (2005 ▶); Gonzalez-Alvarez et al. (2003 ▶); Lee et al. (2005 ▶); Mahadevan et al. (1986 ▶); Kovbasyuk et al. (1997 ▶); Harrison et al. (2007 ▶).

Experimental

Crystal data

[Cu(C₂H₈N₂)₂(H₂O)₂](C₈H₈NO₂)₂·2H₂O
M _r = 556.13
Triclinic,
a = 6.2620 (1) Å
b = 8.5660 (2) Å
c = 13.3550 (4) Å
α = 75.271 (1)°
β = 83.809 (1)°
γ = 70.863 (1)°
V = 654.30 (3) Å³
Z = 1
Ag Kα radiation
μ = 0.47 mm⁻¹
T = 153 (2) K
0.45 × 0.25 × 0.20 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: numerical (HABITUS; Herrendorf & Bärnighausen, 1997 ▶) T _min = 0.808, T _max = 0.915
15039 measured reflections
2989 independent reflections
2644 reflections with I > 2σ(I)
R _int = 0.079

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.086
S = 1.07
2989 reflections
160 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: KappaCCD Software (Nonius, 1997 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808005400/hk2427sup1.cif

e-64-0m509-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005400/hk2427Isup2.hkl

e-64-0m509-Isup2.hkl^{(143.7KB, 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—H1A⋯O2ⁱ	0.92	2.32	3.130 (3)	147
N1—H1A⋯O1ⁱ	0.92	2.41	3.247 (2)	152
N1—H1B⋯O2W	0.92	2.11	2.944 (3)	151
N2—H2A⋯O1ⁱⁱ	0.92	2.29	3.150 (3)	155
N2—H2B⋯O1	0.92	2.12	3.019 (2)	164
O1W—H1W⋯O2ⁱ	0.84	2.06	2.873 (3)	164
O1W—H2W⋯O1	0.84	2.00	2.814 (2)	164
O2W—H3W⋯N3ⁱⁱⁱ	0.84	2.08	2.899 (3)	163
O2W—H4W⋯O2^iv	0.84	2.03	2.859 (3)	169

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

Acknowledgments

We thank the Scientific Grant Agency of the Ministry of Education of the Slovak Republic and the Slovak Academy of Sciences (grant Nos. 1/4454/07 and 1/0353/08).

supplementary crystallographic information

Comment

It is well known that copper(II) complexes having ethylenediamine (en) ligands show flexible coordination environment and adopt semi-coordation with tetragonal distortion. As part of our efforts to investigate metal(II) complexes based on pyridyl-carboxylic acids, we report herein the crystal structure of the title compound, (I).

The asymmetric unit of (I), (Fig. 1), contains one anion, one half-cation and one water molecule. The Cu^II atom in the centrosymmetric [Cu(en)₂(H₂O)₂]²⁺ cation lies on the inversion centre. The four N atoms of the ethylenediamine ligands in the equatorial plane around the Cu^II atom form a slightly distorted square-planar arrangement, while the slightly distorted Jahn-Teller octahedral coordination is completed by the two O atoms of water molecules in the axial positions (Table 1 and Fig. 1).

The Cu—N1 [2.015 (2) Å] and Cu—N2 [2.022 (2) Å] bond lengths and N1—Cu—N2 [84.91 (7)°] bond angle agree with those found in other [Cu(en)₂(H₂O)₂]²⁺ complexes (Table 1). The Cu—O1W [2.503 (2) Å] bond is much longer than Cu—N bonds, as a result of the Jahn-Teller distortion. The Cu—OW bonds in other [Cu(en)₂(H₂O)₂]²⁺ complexes are in the range of 2.416 (3)–2.693 (9) Å (Table 1). The value of the T parameter (Hathaway & Hodgson, 1973), which indicates the degree of tetragonal distortion about the Cu^II atom, is 0.81 and it agrees with the reported values, in the range of 0.76–0.84, for other [Cu(en)₂(H₂O)₂]²⁺ complexes (Table 1).

In the crystal structure, the [Cu(en)₂(H₂O)₂]²⁺ coordination cations and 3-(3-pyridyl)propionate anions are linked by O—H···O and N—H···O hydrogen-bonds (Table 2, Fig. 2) in parallel to the a axis. The amine H atom is linked to both carboxylate O atoms of 3-(3-pyridyl)propionate by three-centered/bifurcated N—H···O hydrogen-bonds (Jeffrey, 1997) and both of them form the R₁²(4) ring motif (Bernstein et al., 1995). The similar R₁²(4) ring motifs with sulfonate or carboxylate groups are reported in[Cu(en)₂(H₂O)₂](4-amino- naphthalene-1-sulfonate)₂.2 H₂O (Li et al., 2005)and [Cu(en)₂(H₂O)₂]- (N-carboxyglycinate).H₂O (Kovbasyuk et al., 1997).

The O—H···O hydrogen bonds between the coordinated water molecules and the carboxylate O atoms of 3-(3-pyridyl)propionate anions and N—H···O hydrogen bonds of amine H atoms form the R₂¹(6) and R₂²(8) ring motifs (Bernstein et al., 1995). These ring motifs are also reported for other [Cu(en)₂(H₂O)₂]X₂ complexes, while only the R₂²(8) ring motifs are present in [Cu(en)₂(H₂O)₂]X₂ complexes, [where X = 4-chlorobenzoate (Lee et al., 2005); X = 4-fluorobenzoate (Liu et al., 2004), X = isonicotinate (Segla et al., 2000) and X = 4-nitrobenzoate (Harrison et al., 2007)]. On the other hand, the R₂¹(6) ring motifs are reported for [Cu(en)₂(H₂O)₂]X₂ complexes, [where X = naphthalene-2-sulfonate (Sharma et al., 2005) and X = 2,6-dimethoxynicotinate (Jašková et al., 2007)]. To the best of our knowledge, only [Cu(en)₂(H₂O)₂](2-aminobenzoate)₂ complex (Miminoshvili et al., 2005), exhibits both R₂¹(6) and R₂²(8) ring motifs, in the crystal structure.

The additional N—H···O hydrogen bonds form further R₂¹(6) ring motifs. Finally, two [Cu(en)₂(H₂O)₂]²⁺ cations and two 3-(3-pyridyl)propionate anions are joined through R₄²(8) ring motifs to form a layer parallel to the a axis. The layers of [Cu(en)₂(H₂O)₂]²⁺ cations and 3-(3-pyridyl)- propionate anions are linked to form a three-dimensional network through uncoordinated water molecules by O—H···O and O—H···N hydrogen-bonds (Fig. 3).

The additional interactions between the 3-(3-pyridyl)propionate anions of (I) are the π-π stacking interactions (Janiak, 2000) between the two adjacent pyridine rings, (N3/C6—C10), with the centroid to centroid distances of C_g···C_g^v = 3.66 Å [symmetry code: (v) -x,-y + 2,-z + 2]. The distance between parallel planes of the stacked pyridine rings is 3.33 Å.

Experimental

The violet [Cu(en)₂(H₂O)₂](3-pypr)₂.2H₂O was formed in a methanolic solution of [Cu(3-pypr)₂(H₂O)₂] (1.25 mmol) by adding ethylenediamine in the molar ratio of 1:2. The resulting solution was left to slowly evaporate at room temperature. In isolating the complex, it was necessary to add acetone to the concentrated solution. Well shaped violet crystals, suitable for X-ray structure analysis were collected after a few hours by filtration and finally dried in vacuo (yield; 90%). Anal. Calc. for C₂₀H₄₀N₆O₈; C, 43.20; H, 7.25; N, 15.11; Cu, 11.43. Found: C, 43.45; H, 7.47; N, 15.30; Cu, 11.21%. Selected IR data (cm^-1): 1592 versus,br (ν_a(COO^-) + ν(C?N)); 1392 versus (ν_s(COO^-)); 605 s (δ(py), pyridine ring in-plane bending); 405 m (γ(py), pyridine ring out-of-plane bending). Electronic data (cm^-1): 18 400 br.