Poly[di-μ-glycinato-copper(II)]: a two-dimensional coordination polymer

Fabienne Gschwind; Martin Jansen

doi:10.1107/S1600536811031503

. 2011 Aug 11;67(Pt 9):m1218–m1219. doi: 10.1107/S1600536811031503

Poly[di-μ-glycinato-copper(II)]: a two-dimensional coordination polymer

Fabienne Gschwind ^a,^*, Martin Jansen ^a

PMCID: PMC3200596 PMID: 22058852

Abstract

The title coordination polymer, [Cu(C₂H₄NO₂)₂]_n, is two-dimensional and consists of a distorted octahedral copper coordination polyhedron with two bidentate glycine ligands chelating the metal through the O and N atoms in a trans-square-planar configuration. The two axial coordination sites are occupied by carbonyl O atoms of neighbouring glycine molecules. The Cu—O distances for the axial O atoms [2.648 (2) and 2.837 (2) Å] are considerably longer than both the Cu—O [1.9475 (17) and 1.9483 (18) Å] and Cu—N [1.988 (2) and 1.948 (2) Å] distances in the equatorial plane, which indicates a strong Jahn–Teller effect. In the crystal, the two-dimensional networks are arranged parallel to (001) and are linked via N—H⋯O hydrogen bonds, forming a three-dimensional arrangement.

Related literature

For the first work on cadmium glycinato complexes, see: Low et al. (1959 ▶). For similar mixed-metal glycinato complexes with copper(II), see: Papavinasam (1991 ▶); Davies et al. (2003 ▶); Low et al. (1959 ▶); Bi et al. (2006 ▶); Zhang et al. (2005 ▶). For further studies on cadmium–glycinato complexes, see: Barrie et al. (1993 ▶). For the properties and structure of a three-dimensional copper–glycinate polymer, see: Chen et al. (2009 ▶). For the synthesis of [NaCu₆(gly)₃(ClO₄)₃(H₂O)]_n(ClO₄)_2n, see: Aromi et al. (2008 ▶).

Experimental

Crystal data

[Cu(C₂H₄NO₂)₂]
M _r = 211.66
Monoclinic,
a = 9.4265 (19) Å
b = 5.1159 (10) Å
c = 13.912 (3) Å
β = 107.36 (3)°
V = 640.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 3.37 mm⁻¹
T = 298 K
0.21 × 0.15 × 0.09 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-SHAPE and X-RED; Stoe & Cie, 2009 ▶) T _min = 0.549, T _max = 0.692
9012 measured reflections
1876 independent reflections
1561 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.075
S = 1.03
1876 reflections
116 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2009 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811031503/su2280sup1.cif

e-67-m1218-sup1.cif^{(16.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031503/su2280Isup2.hkl

e-67-m1218-Isup2.hkl^{(90.5KB, 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
N2—H1A⋯O3ⁱ	0.94 (5)	2.12 (5)	3.029 (3)	162 (4)
N2—H1B⋯O2ⁱⁱ	0.80 (4)	2.49 (4)	3.223 (3)	154 (4)
N1—H3A⋯O1ⁱⁱⁱ	0.90 (4)	2.17 (4)	2.994 (3)	152 (3)
N1—H3A⋯O1^iv	0.90 (4)	2.44 (4)	3.003 (3)	121 (3)
N1—H3B⋯O4^v	0.86 (4)	2.41 (4)	3.152 (3)	145 (3)

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

Acknowledgments

FG thanks the Swiss National Science Foundation for financial support.

supplementary crystallographic information

Comment

Different metal glycine complexes and polymeric structures have been known since the 1960's. The first work on a cadmium glycinato complexe was done by (Low et al., 1959), and further studies were reported by (Barrie et al., 1993). Mixed metal glycinato complexes with copper(II) were investigated by (Papavinasam, 1991; Davies et al., 2003; Low et al., 1959).

The complexation of simple copper salts to amino acids is a well investigated reaction and various complexes and clusters have been reported (Low et al., 1959; Davies et al., 2003; Aromi et al., 2008; Bi et al., 2006; Zhang et al., 2005). A three-dimensional copper-glycinate coordination polymer has been reported on by (Chen et al., 2009).

While redissolving the copper cluster [NaCu₆(gly)₃(ClO₄)₃(H₂O)]_n (ClO₄)_2n (Aromi et al., 2008) in DMSO, blue crystals of the title compound were obtained and were characterized by X-ray diffraction.

The title compound is a two-dimensional coordination polymer (Fig. 1). It consists of a distorted octahedral copper coordination polyhedron with two bidentate glycine ligands chelating the metal through the oxygen and nitrogen atoms (O1, O3, N1, N2) in a trans square planar configuration. The two axial coordination sites are occupied by carbonyl oxygen atoms of the neighbouring glycine molecules (O2 and O4). The Cu—O distances are 2.648 (2) Å (Cu1—O2ⁱ) and 2.837 (2) Å (Cu1—O4ⁱⁱ) for the axial oxygen atoms [symmetry codes: (i) -x-1/2, y+1/2, -z+1/2; (ii) -x+1/2, y-1/2, -z+1/2]. In the equatorial plane the Cu-O distances are 1.9474 (15) and 1.9483 (16) Å for Cu1—O1 and Cu1—O3, respectively, while the Cu—N distances are 1.9883 (19) and 1.948 (2) Å for Cu1-N1 and Cu1—N2, respectively. These bond length differences indicate a strong Jahn-Teller effect.

In the crystal the two dimensional networks are linked via N-H···O hydrogen bonds to form a three-dimensional arrangement (Table 1 and Fig. 2).

Experimental

The title compound was prepared by dissolving 20 mg of [NaCu₆(gly)₃(ClO₄)₃(H₂O)]_n (ClO₄)_2n (Aromi et al., 2008) in 5 ml DMSO. Crystals could be grown out of the blue solution by slow diffusion of THF.