catena-Poly[[diaqua­copper(II)]-μ-hy­drox­ido-κ2 O:O-μ-[4-(4H-1,2,4-triazol-4-yl)benzoato]-κ2 N 1:N 2]

Haochen Shi; Feng Gao; Jingang Qi

doi:10.1107/S1600536811032624

. 2011 Aug 17;67(Pt 9):m1255–m1256. doi: 10.1107/S1600536811032624

catena-Poly[[diaquacopper(II)]-μ-hydroxido-κ² O:O-μ-[4-(4H-1,2,4-triazol-4-yl)benzoato]-κ² N ¹:N ²]

Haochen Shi ^a,^b,^*, Feng Gao ^b, Jingang Qi ^b

PMCID: PMC3200671 PMID: 22058866

Abstract

The title compound, [Cu(C₉H₆N₃O₂)(OH)(H₂O)₂]_n, adopts a chain motif along [010] in which the Cu^II atoms are bridged by hydroxy groups and 4-(1,2,4-triazol-4-yl)benzoate (tab) ligands. The Cu^II atom lies on an inversion center and is six-coordinated by two N atoms from two tab ligands, two hydroxy groups and two water molecules, giving a distorted octahedral geometry. The hydroxy group and the tab ligand are located on a mirror plane. One of the water H atoms is disordered over two positions with equal occupancy factors. Intermolecular O—H⋯O hydrogen bonds extend the chains into a layer parallel to (100) and C—H⋯O hydrogen bonds connect the layers into a three-dimensional network.

Related literature

For general background to the applications of coordination polymers, see: Aghabozorg et al. (2008 ▶); Liu et al. (2010 ▶); Wang et al. (2009 ▶); Zhang et al. (2004 ▶). For a related structure, see: Lin et al. (2011 ▶).

Experimental

Crystal data

[Cu(C₉H₆N₃O₂)(OH)(H₂O)₂]
M _r = 304.75
Monoclinic,
a = 6.787 (5) Å
b = 6.758 (5) Å
c = 12.036 (5) Å
β = 102.919 (5)°
V = 538.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 2.05 mm⁻¹
T = 293 K
0.21 × 0.19 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.64, T _max = 0.75
3021 measured reflections
1165 independent reflections
1010 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.083
S = 1.12
1165 reflections
111 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.37 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811032624/hy2457sup1.cif

e-67-m1255-sup1.cif^{(14.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032624/hy2457Isup2.hkl

e-67-m1255-Isup2.hkl^{(56.4KB, 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
O3—H9⋯O2ⁱ	0.84 (3)	2.07 (3)	2.907 (4)	172 (3)
O4—H10A⋯O2ⁱⁱ	0.83 (3)	1.94 (3)	2.746 (3)	164 (3)
O4—H10⋯O4ⁱⁱⁱ	0.85 (6)	1.94 (6)	2.762 (4)	165 (6)
O4—H10′⋯O4^iv	0.85 (2)	1.93 (2)	2.759 (4)	165 (7)
C6—H6⋯O1^v	0.93	2.44	3.172 (5)	135
C8—H8⋯O1^vi	0.93	2.23	3.052 (4)	147

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

Acknowledgments

The authors thank Jilin University for supporting this work.

supplementary crystallographic information

Comment

Coordination polymers are currently of great interest due to structural versatility, unique properties and potential applications in catalysis, gas storage and in molecular-based magnetic materials (Liu et al., 2010; Zhang et al., 2004). Heterocyclic carboxylates have often been used as mono-, bi- or multidentate ligands to bind transition metal centers, leading to the formation of moderately robust metal–organic coordination frameworks (Aghabozorg et al., 2008; Wang et al., 2009). In this contribution, we selected 4-(1,2,4-triazol-4-yl)benzoic acid (Htab) as an organic carboxylate ligand, generating a coordination polymer, [Cu(C₉H₆N₃O₂)(H₂O)₂(OH)], which is reported here.

The title compound adopts a chain motif, in which the hydroxy groups and tab ligands as bridges to connect adjacent octahedrally coordinated Cu^II atoms (Fig. 1). The Cu^II atom lies on an inversion center and is six-coordinated by two N atoms from two tab ligands, two O atoms from hydroxy groups and two water molecules, giving a distorted octahedral geometry. The Cu—O and Cu—N bond lengths and the O—Cu—O, O—Cu—N and N—Cu—N bond angles are in the normal range (Lin et al., 2011). The hydroxy group and the tab ligand are located on a mirro plane. One of the water H atoms is disordered over two positions with equal occupancy factors. Intermolecular O—H···O hydrogen bonds extend the chains into a layer parallel to (1 0 0). C—H···O hydrogen bonds connect the layers into a three-dimensional network (Fig. 2).

Experimental

The synthesis was performed under hydrothermal conditions. A mixture of CuCl₂.2H₂O (0.2 mmol, 0.034 g), 4-(1,2,4-triazol-4-yl)benzoic acid (0.2 mmol, 0.038 g), NaOH (0.2 mmol, 0.008 g) and H₂O (15 ml) in a 25 ml stainless steel reactor with a Teflon liner was heated from 293 to 433 K and a constant temperature was maintained at 433 K for 96 h. After the mixture was cooled to 293 K, blue crystals of the title compound were obtained from the reaction.