catena-Poly[[[(2,2′-bipyrid­yl)copper(II)]-μ-l-alaninato] perchlorate monohydrate]

Mircea Braban; Ionel Haiduc; Peter Lönnecke

doi:10.1107/S1600536808040725

. 2008 Dec 13;65(Pt 1):m51. doi: 10.1107/S1600536808040725

catena-Poly[[[(2,2′-bipyridyl)copper(II)]-μ-l-alaninato] perchlorate monohydrate]

Mircea Braban ^a,^*, Ionel Haiduc ^a, Peter Lönnecke ^b

PMCID: PMC2967894 PMID: 21581521

Abstract

In the structure of the polymeric title complex, {[Cu(C₃H₆NO₂)(C₁₀H₈N₂)]ClO₄·H₂O}_n, the carboxylate group of the chelating amino acid is further linked to a neighbouring Cu centre, generating a supramolecular single-stranded chain parallel to [010]. The structure displays intermolecular N—H⋯O and O—H⋯O hydrogen bonding, which consolidates the crystal packing.

Related literature

For related structures, see: Antolini et al. (1983 ▶); Masuda et al. (1991 ▶); Sgarabotto et al. (1999 ▶); Solans et al. (1992 ▶).

Experimental

Crystal data

[Cu(C₃H₆NO₂)(C₁₀H₈N₂)]ClO₄·H₂O
M _r = 425.28
Monoclinic,
a = 13.1807 (10) Å
b = 8.2656 (6) Å
c = 16.1195 (13) Å
β = 110.606 (2)°
V = 1643.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.53 mm⁻¹
T = 220 (2) K
0.60 × 0.30 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.460, T _max = 0.656
13671 measured reflections
3939 independent reflections
3611 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.078
S = 1.11
3939 reflections
290 parameters
All H-atom parameters refined
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040725/tk2300sup1.cif

e-65-00m51-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040725/tk2300Isup2.hkl

e-65-00m51-Isup2.hkl^{(176.4KB, 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
N3—H2N3⋯O7ⁱ	0.74 (4)	2.60 (4)	3.293 (4)	159 (5)
N3—H1N3⋯O1ⁱⁱ	0.83 (4)	2.48 (4)	3.225 (3)	149 (3)
N3—H1N3⋯O2ⁱⁱ	0.83 (4)	2.91 (4)	3.225 (3)	105 (3)
N3—H1N3⋯O7ⁱⁱ	0.83 (4)	2.70 (5)	3.059 (3)	108 (3)
N3—H2N3⋯O7ⁱⁱ	0.74 (4)	2.69 (5)	3.059 (3)	114 (4)
O7—H1O7⋯O2ⁱⁱ	0.79 (4)	2.08 (4)	2.857 (3)	166 (3)

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

Acknowledgments

The authors thank Professor Evamarie Hey-Hawkins for cooperation.

supplementary crystallographic information

Comment

The structure of the title complex, (I) and Fig. 1, is of interest with respect to the stereochemistry of the complexed aminoacid, the coordination geometry of the metal centre and the single-stranded supramolecular assembly created primarly by further coordination of the carboxylate group of the aminoacid, Fig. 2. The secondary association is by crosslinks realised through H-bonds between the created chains, Fig. 3. The supramolecular structure described for (I) is found in other (aminoacidato)(2,2'-bipyridyl)copper(II) complexes, such as in the tryptophanato (Masuda et al., 1991) and aspartato complexes (Antolini et al., 1983). The assembly has also been identified in the proline complex but not described as a supramolecular association (Sgarabotto et al., 1999). For the alaninate complex, see also Solans et al. (1992).

Experimental

The synthesis of (I) was realized by using an intermediate complex, i.e. tris(2,2'-bipyridyl)copper(II), as shown in Fig. 4. The cation in (I) was prepared according to the following procedure: Two ethanolic solutions, one containing 2,2'-bipyridyl (0.31 g, 2 mmol/5 mL) and another containing Cu(ClO₄)₂.2H₂O (0.6 g, 2 mmol/5 mL) were mixed with stirring. To the resulting suspension of a blue powder, an alkaline solution of L-alanine (0.18 g alanine + 0.08 g NaOH 2 mmol/10 mL water) was added dropwise (see also Scheme 2). The suspension cleared and changed colour to dark-blue. The mixture was heated to 50°C and Na₂ClO₄ (1 mmol) was added. After 10 mins, the solution was cooled and filtered. The filtrate was allowed to stand at room temperature for several days when dark-blue crystals, suitable for X-ray analysis, separated, collected and washed with a methanolic solution.