Bis(2,2′-bipyrid­yl)-1κ2 N,N′;3κ2 N,N′-bis­(4-bromo-2-formyl­phenolato)-1κ2 O,O′;3κ2 O,O′-bis­[μ-2-(5-bromo-2-oxidobenzylidene­amino)­ethane­sul­fon­ato]-1:2κ3 O:N,O 2;2:3κ3 N,O 2:O-tricopper(II) monohydrate

Ling Zhang

doi:10.1107/S1600536809014263

. 2009 Apr 22;65(Pt 5):m552. doi: 10.1107/S1600536809014263

Bis(2,2′-bipyridyl)-1κ² N,N′;3κ² N,N′-bis(4-bromo-2-formylphenolato)-1κ² O,O′;3κ² O,O′-bis[μ-2-(5-bromo-2-oxidobenzylideneamino)ethanesulfonato]-1:2κ³ O:N,O ²;2:3κ³ N,O ²:O-tricopper(II) monohydrate

Ling Zhang ^a,^*

PMCID: PMC2977599 PMID: 21583785

Abstract

The title complex, [Cu₃(C₉H₈BrNO₄S)₂(C₇H₄BrO₂)₂(C₁₀H₈N₂)₂]·H₂O, lies on an inversion center located on the central Cu atom, which is four-coordinated in a square-planar geometry, whereas the outer Cu atoms related by symmetry are five-coordinated in a square-pyramidal geometry. The trinuclear molecules, with an intramolecular Cu⋯Cu separation of 6.313 (3) Å, are linked to each other, forming a chain through O—H⋯O and O—H⋯Br hydrogen bonds involving the half-occupied water molecule. Futhermore, weak C—H⋯O interactions link the chains to form a supramolecular network.

Related literature

For general background on coordination polymers and open framework materials, see: Kim et al. (2003 ▶); Iglesias et al. (2003 ▶); Moulton & Zaworotko (2001 ▶). For background on 2,2′-bipyridyl and 5-bromo-2-hydroxybenzaldehyde, see: Sun & Gao (2005 ▶); Murphy et al. (2004 ▶).

Experimental

Crystal data

[Cu₃(C₉H₈BrNO₄S)₂(C₇H₄BrO₂)₂(C₁₀H₈N₂)₂]·H₂O
M _r = 1533.30
Triclinic,
a = 10.031 (2) Å
b = 11.480 (2) Å
c = 12.913 (3) Å
α = 73.13 (3)°
β = 78.58 (3)°
γ = 75.24 (3)°
V = 1363.6 (6) Å³
Z = 1
Mo Kα radiation
μ = 4.24 mm⁻¹
T = 293 K
0.23 × 0.16 × 0.10 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.442, T _max = 0.677
12051 measured reflections
4888 independent reflections
1651 reflections with I > 2σ(I)
R _int = 0.077

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.099
S = 0.76
4888 reflections
367 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014263/dn2446sup1.cif

e-65-0m552-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014263/dn2446Isup2.hkl

e-65-0m552-Isup2.hkl^{(234.5KB, 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
O1W—H1WB⋯O2	0.84	2.40	3.197 (11)	159
O1W—H1WA⋯Br2ⁱ	0.83	2.55	3.145 (9)	130
C4—H4⋯O1ⁱⁱ	0.93	2.42	3.316 (9)	163
C23—H23⋯O2ⁱⁱⁱ	0.93	2.54	3.324 (9)	142

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

Acknowledgments

The author acknowledges financial support by the Youth Foundation of Lishui University, China (No. QN05002).

supplementary crystallographic information

Comment

Molecular self-assembly of supramolecular architectures has received much attention during recent decades (Kim et al., 2003; Iglesias et al., 2003; Moulton & Zaworotko, 2001). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metals ions and bridging building blocks as well as the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions. 2,2'-bipyridyl, 5-bromo-2-hydroxybenzaldehyde are excellent candidates for the construction of supramolecula complexes, since they not only have multiple coordination modes but also can form regular hydrogen bonds by functioning as both hydrogen-bond donor and acceptor (Sun & Gao, 2005; Murphy et al., 2004). 2-(5-bromo-2-hydroxybenzylamino)ethanesulfonic has a versatile binding ability, whose structure of complexes have not been reported to date. Recently, we obtained the title novel trinuclear copper complex (I) by the reaction of copper nitryl, 2,2'-bipyridyl, 5-bromo-2-hydroxybenzaldehyde and 2-(5-bromo-2-hydroxybenzylamino)ethanesulfonic in an aqueous solution, and its crystal is reported here.

The trinuclear complex lyies on a crystallographic inversion center located on the central Cu1 atom which is four-coordinated in a square planar geometry, whereas the other Cu2 atoms related by symmetry are five-coordinated in a square pyramidal geometry (Fig. 1). The compound forms trinuclear structure via the flexible 2-(5-bromo-2-hydroxybenzylamino)ethanesulfonic ligand, with a Cu···Cu separation of 6.313 (3) Å. These trinuclear units are linked to each other to form a chain through O-H···O and O-H···Br hydrogen bonds involving the water molecule (table 1, Fig. 2). Futhermore, weak C-H···O interactions link the chain to form a supramolecular network.

Experimental

A mixture of copper chloride(1 mmol), 5-bromo-2-hydroxybenzaldehyde (1 mmol), 2,2'-bipyridyl(1 mmol), 2-(5-bromo-2-hydroxybenzylamino)ethanesulfonic (1 mmol) and H₂O (12 ml) was placed in a 23 ml Teflon reactor, which was heated to 433 K for three days and then cooled to room temperature at a rate of 10 K h^-1. The crystals obtained were washed with water and dryed in air.