Aqua­(4-methyl­quinoline-κN)[N-(2-oxidobenzyl­idene)glycinato-κ3 O,N,O′]copper(II) hemihydrate

Zdeněk Trávníček; Jaromír Marek; Ján Vančo; Oľga Švajlenová

doi:10.1107/S1600536807067852

. 2008 Jan 4;64(Pt 2):m282–m283. doi: 10.1107/S1600536807067852

Aqua(4-methylquinoline-κN)[N-(2-oxidobenzylidene)glycinato-κ³ O,N,O′]copper(II) hemihydrate

Zdeněk Trávníček ^a,^*, Jaromír Marek ^a,^b, Ján Vančo ^a,^c, Oľga Švajlenová ^d

PMCID: PMC2960168 PMID: 21201263

Abstract

The title complex, [Cu(C₉H₇NO₃)(C₁₀H₉N)(H₂O)]·0.5H₂O, crystallizes with two independent formula units in the asymmetric unit; the solvent molecule is located on a twofold axis of symmetry. The Cu^II atom is coordinated by one tridentate N-salicylideneglycinate Schiff base ligand, one 4-methylquinoline ligand and one water molecule, leading to a slightly distorted square-pyramidal N₂O₃ geometry. In the crystal structure, the molecules are linked by O—H⋯O hydrogen bonds into linear chains in the [100] direction. The structure is further stabilized by intermolecular C—H⋯O interactions and C⋯C contacts with C⋯C = 3.3058 (2), 3.3636 (2) and 3.3946 (2) Å.

Related literature

For synthesis, see: Kishita et al. (1964 ▶). For related literature, see: Katsuki (2003 ▶); Vančo et al. (2004 ▶, 2008 ▶); Bauerová et al. (2005 ▶). For related structures, see: Valent et al. (2002 ▶); Warda (1998a ▶,b ▶,c ▶,d ▶).

Experimental

Crystal data

[Cu(C₉H₇NO₃)(C₁₀H₉N)(H₂O)]·0.5H₂O
M _r = 410.9
Monoclinic,
a = 10.0966 (7) Å
b = 12.3483 (6) Å
c = 28.8133 (17) Å
β = 97.730 (6)°
V = 3559.7 (4) Å³
Z = 8
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 120 (2) K
0.30 × 0.25 × 0.25 mm

Data collection

Kuma KM-4-CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.690, T _max = 0.729
19645 measured reflections
6242 independent reflections
4225 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.113
S = 1.09
6242 reflections
499 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067852/tk2236sup1.cif

e-64-0m282-sup1.cif^{(33KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067852/tk2236Isup2.hkl

e-64-0m282-Isup2.hkl^{(305.5KB, 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
O4—H4V⋯O102ⁱ	0.879 (19)	1.88 (2)	2.756 (4)	174 (4)
O4—H4W⋯O2ⁱⁱ	0.87 (4)	2.01 (3)	2.825 (4)	155 (4)
O5—H5V⋯O101ⁱⁱⁱ	0.890 (19)	1.99 (2)	2.865 (4)	169 (4)
O6—H6V⋯O1	0.876 (19)	2.01 (2)	2.867 (4)	165 (4)
O104—H4Y⋯O2	0.879 (19)	1.90 (2)	2.751 (4)	162 (4)
O104—H4Z⋯O102ⁱⁱⁱ	0.87 (4)	1.98 (2)	2.823 (4)	162 (4)

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

Acknowledgments

Financial support of this work by the Ministry of Education, Youth and Sports of the Czech Republic (grant Nos. MSM6198959218, MSM0021622415 and MSM6215712403) and the Scientific Grant Agency of the Ministry of Education of the Slovak Republic (grant No. VEGA 1/3416/06) is gratefully acknowledged.

supplementary crystallographic information

Comment

Schiff bases, as condensation products of carbonyls and amines, and their coordination compounds find their utilization in different branches of chemical technology (Katsuki, 2003) and participate in some biochemical pathways, e.g. transamination processes, catalyzed by metalloenzymes.

In connection with our recent studies on copper and zinc salicylidene-derived Schiff base complexes, we report now the structure of (I). The Schiff base (Salgly) ligand represents a condensation product of salicylaldehyde and glycine. The title complex, in the form of an anhydrous compound, showed significant microbistatic and fungistatic effects (Valent et al., 2002). Moreover, similar compounds derived from different N-salicylideneamino acids have been intensively studied and showed some remarkable biological features, from which the antioxidant (Vančo et al., 2008), antiflogistic, antirheumatic (Bauerová et al., 2005), or antidiabetic activities (Vančo et al., 2004) could be considered as the most interesting.

To date, only four X-ray structures of monomeric copper(II) complexes involving the aqua-(N-salicylideneglycinato-κO,N,O')copper(II) moiety in combination with another N-donor ligand, i.e. an alkylated pyridine derivative, have been reported (Warda, 1998a-d). While the present structure is the first one with two-ring one-N-donor aromatic ligand, i.e. 4-methylquinoline (Mqui), there are similarities in the interatomic parameters defining the coordination of the central atom in these complexes.

Two independent formula units of Cu(Salgly)(Mqui)(H₂O).1/2(H₂O) comprise the asymmetric unit of (I), see Fig. 1; each of the solvent water molecules lies on a 2-fold axis. Each Cu^II atom is chelated by two N atoms and a O atom, derived from the Salgly ligand, one N atom from the Mqui ligand. The resultant penta-coordinated geometry is completed by a water molecule. The O atom of the latter ligand occupies an apical position in a slightly distorted square-pyramidal coordination geometry [τ = 0.102 (for Cu1) and 0.091 (for Cu2)]. The bond distances of Cu—N_azomethine [1.927 (3) and 1.926 (3) Å], Cu—N_imine [1.993 (3) and 1.982 (3) Å], Cu—O_carboxy [1.986 (3) and 1.982 (3) Å], Cu—O_phenoxy [1.910 (3) and 1.909 (3) Å] and Cu—O_water [2.371 (3) and 2.367 (3) Å] as well as O_carboxy—Cu—O_phenoxy [166.61 (12) and 166.81 (12) °] and N_azomethine—Cu—N_imine [172.74 (14) and 172.24 (14) °] bond angles are quite similar in the independent complex molecules.

The primary intermolecular contacts in the crystal structure are of the type O—H···O (Fig. 2 & Table 1) and involve both coordinated and free water molecules, and both O atoms of carboxy groups, joining them into linear chains in the [100] direction. Moreover, the secondary structure is stabilized by intermolecular C—H···O interactions and C···C contacts (Fig. 3).

Experimental

The title complex, (I), was prepared by the reaction of an ethanol/water solution (2:1, v/v) of aqua-(N-salicylideneglycinato)copper(II) hemihydrate (Kishita et al., 1964) with an ethanolic solution of 4-methylquinoline in the molar ratio of 1:4. The reaction mixture was stirred at 60 °C for 30 minutes. After cooling overnight, well developed single crystals of (I) suitable for X-ray analysis were isolated.