[μ-1,4-Bis(1,2,4-triazol-1-ylmeth­yl)benzene]­bis­[aqua­(pyridine-2,6-dicarboxyl­ato)copper(II)] monohydrate

Gui-Ying Dong; Cui-Hong He; Liu Tong-Fei; Xiao-Chen Deng; Xiao-Ge Shi

doi:10.1107/S1600536811022756

. 2011 Jun 18;67(Pt 7):m944. doi: 10.1107/S1600536811022756

[μ-1,4-Bis(1,2,4-triazol-1-ylmethyl)benzene]bis[aqua(pyridine-2,6-dicarboxylato)copper(II)] monohydrate

Gui-Ying Dong ^a,^*, Cui-Hong He ^a, Liu Tong-Fei ^a, Xiao-Chen Deng ^b, Xiao-Ge Shi ^b

PMCID: PMC3151849 PMID: 21836927

Abstract

The title compound, [Cu₂(C₇H₃NO₄)₂(C₁₂H₁₂N₆)(H₂O)₂]·H₂O, displays a discrete dinuclear structure, in which the central Cu^II atom is five-coordinated in a distorted square-based pyramidal coordination geometry and the flexible ligand 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene adopts a bis-monodentate bridging mode linking the Cu^II atoms. It is further assembled by O—H⋯O hydrogen-bond interactions involving both the coordinated and uncoordinated water molecules. The latter exhibits half-occupancy.

Related literature

For the versatile conformations of the flexible 1,4-bis(1,2,4- triazol-1-yl-methyl)benzene ligand and related complexes, see: Arion et al. (2003 ▶); Peng et al. (2004 ▶, 2006 ▶); Meng et al. (2004 ▶); Li et al. (2005 ▶); Lin & Dong (2007 ▶); Ding et al. (2009 ▶).

Experimental

Crystal data

[Cu₂(C₇H₃NO₄)₂(C₁₂H₁₂N₆)(H₂O)₂]·H₂O
M _r = 751.63
Monoclinic,
a = 4.9017 (4) Å
b = 10.3022 (9) Å
c = 30.178 (3) Å
β = 93.541 (1)°
V = 1521.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 298 K
0.20 × 0.15 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.881, T _max = 0.901
7340 measured reflections
2678 independent reflections
2256 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.161
S = 1.06
2678 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 1.40 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811022756/jh2295sup1.cif

e-67-0m944-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022756/jh2295Isup2.hkl

e-67-0m944-Isup2.hkl^{(131.5KB, 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
O2W—H2WA⋯O2Wⁱ	0.85	2.15	2.920 (5)	151
O2W—H2WB⋯O2Wⁱⁱ	0.85	1.96	2.807 (5)	179
O1W—H1WA⋯O4ⁱⁱⁱ	0.83	1.93	2.746 (5)	168
O1W—H1WB⋯O3^iv	0.86	1.86	2.692 (5)	164

Open in a new tab

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

Acknowledgments

The authors thank Hebei United University for supporting this work.

supplementary crystallographic information

Comment

1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (btx=1,4-bis(1,2,4-triazol-1-ylmethyl)benzene) is a ditriazole-containing bridge ligand, in which the flexible nature of spacers allows the ligands to bend and rotate when coordinating to metal centers so as to conform the coordination geometries of metal ions.(Arion, et al., 2003; Peng, et al., 2004, 2006; Meng, et al., 2004; Li et al., 2005;Lin et al. 2007; Ding, et al. 2009) To further understand the coordination behavior of this ligand, we report herein the crystal structure of the title compound,(I).

The asymmetric unit of (I) contains one copper^II,one 2,6-pyridinedicarboxylato, one half btx ligand, one coordination water molecule and one half free water molecule. The copper center is five-coordinated in distorted square-based pyramidal coordination geometry. As show in Fig.1, selected geometric parameters see table 1.Each copper^II is coordinated by one tridentate dipicolinato ligands via their carboxylate and nitrogen donors.(Cu1—N1= 1.908 (3); Cu1—O1=2.007 (3); Cu(1)—O(3)= 2.048 (3) Å) another one (Cu1—N4=1.951 (3) Å) from btx ligand together with one water molecule (Cu1—O1W = 2.217 (4) Å).Two carboxylate oxygen atoms and two nitrogen atoms define a quadrangle equatorial plane, and the water oxygen atom occupies the apical position. Each btx ligand bridges two copper atoms related by a twofold axis into dinuclear structure. The dihedral angle between the imidazole and phenyl rings is 70.0 (4)° in same btx ligang. It is noteworthy that there exist strong hydrogen-bonding interaction(table 2) involving the carboxy group oxygen atoms of dipicolinato ligands as well as coordinated and free water molecules,this may further stabilize the crytal structure.

Experimental

A mixture of Cu(NO₃)₂ 3H₂O(120.5 mg, 0.5 mmol), 2,6-Pyridinedicarboxylic acid (167 mg, 1 mmol),NaOH(80 mg, 2 mm mol), btx (60 mg, 0.5 mmol) and water (12 ml) was sealed in a 25 ml teflon-lined stainless steel reactor and heated to 413 K for 72 h. The reaction was cooled to room temperature over a period of 24 h. Blue prism crystals of 1 suitable for X-ray difraction analysis were obtained with a yield of 37%(based btx)