Crystal structure of bis­(μ2-tetra­bromo­phthalato-κ2 O 1:O 2)bis[aqua(N,N,N′,N′-tetra­methyl­ethane-1,2-di­amine-κ2 N,N′)copper(II)]

Luis Manuel Tobón-Trujillo; Luis Felipe Villanueva-Sánchez; Diego Martínez-Otero; Alejandro Dorazco-González

doi:10.1107/S2056989015015194

. 2015 Aug 22;71(Pt 9):m171–m172. doi: 10.1107/S2056989015015194

Crystal structure of bis(μ₂-tetrabromophthalato-κ² O ¹:O ²)bis[aqua(N,N,N′,N′-tetramethylethane-1,2-diamine-κ² N,N′)copper(II)]

Luis Manuel Tobón-Trujillo ^a, Luis Felipe Villanueva-Sánchez ^a, Diego Martínez-Otero ^a, Alejandro Dorazco-González ^a,^*

PMCID: PMC4555376 PMID: 26396871

Abstract

In the title complex, [Cu₂(C₈Br₄O₄)₂(C₆H₁₆N₂)₂(H₂O)₂], the Cu^II cation is chelated by a tetramethylethane-1,2-diamine ligand and coordinated by a water molecule as well as bridged by two tetrabromophthalate anions in a distorted O₃N₂ trigonal–bipyramidal geometry. The two symmetry-related tetrabromophthalate anions bridge the two Cu^II cations, forming a centrosymmetric dinuclear complex in which the Cu⋯Cu separation is 5.054 (2) Å. Intramolecular classic O—H⋯O hydrogen bonds and weak C—H⋯O hydrogen bonds occur in the dinuclear molecule. In the crystal, the molecules are linked by weak C—H⋯Br and C—H⋯O interactions into supramolecular chains propagating along the b-axis direction.

Keywords: crystal structure; copper(II) complex; tetramethylethane-1,2-diamine; tetrabromophthalate anion; hydrogen bonding

Related literature

For the crystal structures of related copper(II) complexes with tetramethylethylen-1,2-diamine and carboxylate ligands; see: Ene et al. (2009 ▸); Dorazco-González et al. (2013 ▸); Liang et al. (2004 ▸). For the synthesis of coordination compounds with one-dimensional polymeric structures, see: Hong & You (2004 ▸); Colacio et al. (2009 ▸); Rodpun et al. (2015 ▸); Yang et al. (2002 ▸). For their magnetic properties, see: Ene et al. (2009 ▸); Kozlevčar et al. (2004 ▸). For supramolecular polymorphism, see: Dorazco-González et al. (2013 ▸); Stibrany et al. (2009 ▸); Aakeröy et al. (2003 ▸); Valdés-Martínez et al. (1993 ▸); Julve et al. (1984 ▸). For molecular recognition and sensing; see: Dorazco-González & Yatsimirsky (2010 ▸); Mendy et al. (2010 ▸).

Experimental

Crystal data

[Cu₂(C₈Br₄O₄)₂(C₆H₁₆N₂)₂(H₂O)₂]
M _r = 1354.97
Monoclinic,
a = 9.0961 (2) Å
b = 9.2281 (2) Å
c = 24.4026 (7) Å
β = 95.4910 (6)°
V = 2038.95 (9) Å³
Z = 2
Mo Kα radiation
μ = 8.94 mm⁻¹
T = 100 K
0.25 × 0.15 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ▸) T _min = 0.442, T _max = 0.745
17394 measured reflections
3739 independent reflections
3547 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.016
wR(F ²) = 0.039
S = 1.07
3739 reflections
245 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2012 ▸); cell refinement: SAINT (Bruker, 2012 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015015194/xu5866sup1.cif

e-71-0m171-sup1.cif^{(539.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015015194/xu5866Isup2.hkl

e-71-0m171-Isup2.hkl^{(298.3KB, hkl)}

Click here for additional data file.^{(1.6MB, tif)}

. DOI: 10.1107/S2056989015015194/xu5866fig1.tif

The structure with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015015194/xu5866fig2.tif

View of interactions in the crystal.

CCDC reference: 1418832

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O5H5AO2	0.81(2)	1.87(2)	2.649(2)	161(2)
O5H5BO4ⁱ	0.82(2)	1.83(2)	2.630(2)	167(3)
C10H10ABr4ⁱⁱ	0.99	2.84	3.729(3)	150
C11H11CO4	0.98	2.40	3.376(3)	179
C13H13AO4ⁱⁱⁱ	0.98	2.58	3.506(3)	158

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

Acknowledgments

We thank MSc Lizbeth Triana Cruz for technical assistence. The financial support of this research by CONACyT (CB239648) is gratefully acknowledged.

supplementary crystallographic information

S1. Introduction

The self-assembly of metal complexes with benzene-multicarboxylate ligands remains an active area in coordination chemistry especially with copper due to the very wide structural diversity and interesting properties in magnetism, host-guest systems, porous material (Ene et al., 2009; Dorazco-González et al., 2013; Liang et al., 2004). Dinuclear copper(II) compounds have been used in magnetism, as biomimetic active sites in bioinorganic chemistry and in the design and synthesis of metallic networks (Lu et al., 2004). Herein we present a dinuclear copper complex synthesised by self-assembly between copper perchlorate, a aliphatic diamine (tmen) and a bulky benzendicarboxylate (tetrabromophthalate). The tittle compound represents the first example of copper complex with tetrabromophthalate.

S2. Experimental

Compound. Cu(ClO₄)₂.6H₂O (0.1 mmol, 0.037 g) was added directly to a solution of tmen (0.1 mmol) in metanol-water solution 1:1 (8 mL). Then the dianion of tetrabromophthalic acid (0.1 mmol, 0.055 g) in methanol-water solution 1:1 again (12 mL) was slowly added with stirring at room temperature, and a slight warming at 50 °C for 3 minutes.

S2.1. Synthesis and crystallization

Blue deep suitable crystals for diffraction X-ray were grown directly from solution by slow evaporation during 5 days. IR(KBr pellet), 3012 (w), 2971 (w), 2947 (w), 1741 (s), 1606 (m), 1396 (m), 1504 (w), 1459 (w), 1371 (s), 1315 (m), 1213 (m), 1096 (w), 1018 (w), 951 (w), 867 (w), 805 (w), 765 (w), 733 (w), 558 (w), 525 (w).

S2.2. Refinement

Water H atoms were placed in a difference Fourier map and positional parameters were refined, U_iso(H) = 1.2U_eq(O). Other H atoms were placed in calculated positions with C—H = 0.98–0.99 Å and refined in riding mode, U_iso(H) = 1.2U_eq(C) for methylene H atoms and 1.5U_eq(C) for methyl H atoms.

S3. Results and discussion

The reaction between the aqua-complex [Cu(tmen)(H₂O)_x](ClO₄)₂ and potassium salt of tetrabromophthalate in mixture ethanol gives the title compound in good yield (>94 %) as blue suitable crystals for X ray diffraction. The single-crystal X-ray analysis reveals that the compound is a neutral dinuclear centro-symmetric copper (II) complex which crystallizes in monoclinic crystal system, space group P21/n (Figure 1). The asymmetric unit contains a five-coordinate copper atom [Cu(N₂O₃)] with two sites occupied by diamine and three sites by oxygen atoms from two carboxylate groups and one molecule of water. The Addison tau-parameter has been used to describe the distortion around coordination geometry, τ = (difference between two largest angles/60 for five-coordinated metal centers allows the distinction between trigonal-bipyramidal (ideally τ = 1) and square-pyramidal (ideally τ = 0). In this context, the coordination geometry of complex is distorted trigonal-bypiramide, τ = 0.68. The distance Cu ··· Cu is 5.054 (2) Å and a macrocycle is formed by 14 atoms containing two TBr-phthalate-bridge ligands. The combination of copper(II) with multi-carboxylic acids has formed one of the largest subgroups in metal-organic compounds and despite this there are few examples of coordination complex with 1,2,3,4,-tetrahalogenated benzenes among these only with tetrachlorophthalate have been reported (Hong & You, 2004; Yang et al., 2002). The present compound represents the first example with tetrabromophthalate.