Crystal structure of {2-[({2-[(2-amino­eth­yl)amino]­eth­yl}imino)­meth­yl]pheno­lato}aqua­copper(II) bromide

Nataliya I Plyuta; Julia A Rusanova; Svitlana R Petrusenko; Irina V Omelchenko

doi:10.1107/S1600536814017590

. 2014 Aug 16;70(Pt 9):m330–m331. doi: 10.1107/S1600536814017590

Crystal structure of {2-[({2-[(2-aminoethyl)amino]ethyl}imino)methyl]phenolato}aquacopper(II) bromide

Nataliya I Plyuta ^a, Julia A Rusanova ^a, Svitlana R Petrusenko ^a,^*, Irina V Omelchenko ^b

PMCID: PMC4186199 PMID: 25309185

Abstract

In the mononuclear copper(II) title complex, [Cu(C₁₁H₁₆N₃O)(H₂O)]Br, the Cu^II atom is coordinated by one O and three N atoms of the Schiff base ligand that forms together with one water molecule a slightly distorted [CuN₃O₂] square-pyramidal polyhedron. The deviation of the Cu^II atom from the mean equatorial plane is 0.182 (2) Å. The equatorial plane is nearly coplanar to the aromatic ring of the ligand [angle between planes = 10.4 (1)°], and the water molecule is situated in the apical site. All coordinating atoms (except the imine nitrogen) and the bromide ion contribute to the formation of the N—H⋯Br, O—H⋯Br and O—H⋯O hydrogen bonds, which link molecules into chains along [01-1].

Keywords: crystal structure, copper(II) complex, Schiff base ligand, bromide, hydrogen bonding

Related literature

For structures isotypic with that of the title compound, see: Zhu et al. (2002 ▶, 2004 ▶); He (2003 ▶). For the direct synthesis of copper-containing coordination compounds using the salt route, see: Kovbasyuk et al. (1997 ▶); Pryma et al. (2003 ▶); Buvaylo et al. (2005 ▶); Nikitina et al. (2008 ▶); Vassilyeva et al. (1997 ▶); Makhankova et al. (2002 ▶). For the direct synthesis of polynuclear copper-containing complexes, see: Nesterova (Pryma) et al. (2004 ▶); Nesterova et al. (2005 ▶).

Experimental

Crystal data

[Cu(C₁₁H₁₆N₃O)(H₂O)]Br
M _r = 367.73
Monoclinic,
a = 9.2226 (11) Å
b = 14.0333 (13) Å
c = 10.9206 (11) Å
β = 102.355 (11)°
V = 1380.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.47 mm⁻¹
T = 293 K
0.40 × 0.40 × 0.40 mm

Data collection

Agilent Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.268, T _max = 0.268
7804 measured reflections
4004 independent reflections
2334 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.097
S = 0.95
4004 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2011 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: OLEX2 (Dolomanov et al., 2009 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814017590/rn2126sup1.cif

e-70-0m330-sup1.cif^{(21.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017590/rn2126Isup2.hkl

e-70-0m330-Isup2.hkl^{(204.2KB, hkl)}

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S1600536814017590/rn2126fig1.tif

Structure of the title compound, with displacement ellipsoids drawn at the 50% probability level for non-H atoms with hydrogen bonds shown as dashed lines.

Click here for additional data file.^{(2.1MB, tif)}

. DOI: 10.1107/S1600536814017590/rn2126fig2.tif

Crystal packing of the title compound with hydrogen bonds shown as dashed lines.

CCDC reference: 1017209

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2OB⋯Br1	0.82	2.51	3.323 (3)	173
N2—H2N⋯Br1	0.85	2.58	3.429 (3)	177
O2—H2OA⋯O1ⁱ	0.82	1.90	2.712 (4)	171
N3—H3NA⋯Br1ⁱⁱ	0.85	2.68	3.499 (3)	164

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

Acknowledgments

This work was partly supported by the State Fund for Fundamental Researches of Ukraine (project 54.3/005).

supplementary crystallographic information

S1. Comment

It has been shown that the direct synthesis is an efficient method to obtain novel homo and heterometallic mono/polynuclear coordination compounds (Kovbasyuk et al., 1997; Vassilyeva et al., 1997; Makhankova et al., 2002; Pryma et al., 2003; Nesterova (Pryma) et al., 2004; Nesterova et al., 2005; Buvaylo et al., 2005; Nikitina et al., 2008). The title compound, [Cu(C₁₁H₁₈N₃O₂)(H₂O)]Br, was obtained unintentionally as the product of an attempted synthesis of a Cu/ Mn heterometallic complex using zerovalent copper and manganese powders, ammonium bromide, salicylic aldehyde and diethylenetriamine in dimethylformamide on air.

As shown in Fig. 1, the Cu^II atom has a slightly distorted square-pyramidal geometry formed by one oxygen and three nitrogen atoms of the Schiff base ligand as well one oxygen atom of the coordinated water molecule. The deviation of the copper atom from the mean equatorial plane is 0.182 (2) Å. The range of Cu–N and Cu–O bond distances in the equatorial plane is 1.918 (3) - 2.018 (3) Å, while the Cu–O axial distance is 2.333 (2) Å. These data are in a good agreement with literature values (Zhu et al.,2002, 2004; He et al., 2003). The equatorial plane is nearly coplanar to the aromatic ring of the ligand [angle between planes is 10.4 (1)°].

In the crystal, OH···O hydrogen bonds form molecular dimers. OH···Br and NH···Br hydrogen bonds link the dimers into chains along the [011] crystallographic direction (See Table containing Hydrogen-bond geometry and Fig.2).

S2. Experimental

The title compound was synthesized by addition of manganese powder 0.055 g (1 mmol), copper powder 0.06 g (1 mmol) and NH₄Br 0.392 g (4 mmol) to the previously prepared Schiff base ligand solution [mixture of salicylic aldehyde 0.21 ml (2 mmol) and diethylenetriamine 0.108 ml (1 mmol) in dimethylformamide (10 ml) which was stirred about 15 min at 323–333 K until the mixture turned yellow]. The total reaction mixture was stirred magnetically for 4 h until the complete dissolution of manganese and copper powders was observed. Dark green crystals that precipitated after 1 day were collected by filtration and dried in air.