A new copper(II) complex based on 1-[(1H-benzotriazol-1-yl)meth­yl]-1H-1,2,4-triazole

Huai-xia Yang; Jun Zhang; Dong Zhao

doi:10.1107/S1600536811013511

. 2011 Apr 16;67(Pt 5):m602. doi: 10.1107/S1600536811013511

A new copper(II) complex based on 1-[(1H-benzotriazol-1-yl)methyl]-1H-1,2,4-triazole

Huai-xia Yang ^a,^*, Jun Zhang ^b, Dong Zhao ^b

PMCID: PMC3089299 PMID: 21754321

Abstract

The title complex, tetraaqua{1-[(1H-benzotriazol-1-yl)methyl]-1H-1,2,4-triazole-κN ⁴}(sulfato-κO)copper(II) sesquihydrate, [Cu(SO₄)(C₉H₈N₆)(H₂O)₄]·1.5H₂O, is composed of one copper atom, one 1-[(2H-benzotriazol-1-yl)methyl]-1-H-1,2,4-triazole (bmt) ligand, one sulfate ligand, four coordinated water molecules and one and a half uncoordinated water molecules. The Cu^II atom is six-coordinated by one N atom from a bmt ligand and five O atoms from the monodentate sulfate ligand and four water molecules in a distorted octahedral geometry. In the crystal, adjacent molecules are linked through O—H⋯O and O—H⋯N hydrogen bonds involving the sulfate anion and the coordinated and uncoordinated water molecules into a three-dimensional network.

Related literature

For background to complexes based on triazole and benzotriazole derivatives, see: Aromia et al. (2011 ▶); Meng et al. (2009 ▶). For background to complexes with Cu^II atoms, see: Zhou et al. (2007 ▶); Brown et al. (2009 ▶).

Experimental

Crystal data

[Cu(SO₄)(C₉H₈N₆)(H₂O)₄]·1.5H₂O
M _r = 458.90
Monoclinic,
a = 12.496 (3) Å
b = 8.662 (2) Å
c = 31.543 (6) Å
β = 90.97 (3)°
V = 3413.7 (12) Å³
Z = 8
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 293 K
0.20 × 0.16 × 0.15 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear, Rigaku/MSC, 2006 ▶) T _min = 0.758, T _max = 0.810
13448 measured reflections
4046 independent reflections
3502 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.088
S = 1.10
4046 reflections
240 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2006 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 datablocks global, I. DOI: 10.1107/S1600536811013511/bv2183sup1.cif

e-67-0m602-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013511/bv2183Isup2.hkl

e-67-0m602-Isup2.hkl^{(198.4KB, 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
O1—H1W⋯O9	0.85	1.82	2.662 (3)	170
O2—H3W⋯O10ⁱ	0.85	1.89	2.723 (2)	165
O9—H9W⋯N6ⁱⁱ	0.85	2.00	2.836 (3)	168
O10—H11W⋯O6ⁱⁱⁱ	0.85	1.93	2.771 (2)	170
O1—H2W⋯N2ⁱⁱⁱ	0.85	2.16	2.951 (3)	155
O3—H5W⋯O8^iv	0.85	1.99	2.789 (3)	156
O4—H7W⋯O6^v	0.85	1.86	2.697 (2)	170
O9—H10W⋯O7^v	0.85	1.99	2.824 (3)	165
O3—H6W⋯O6^v	0.85	2.19	2.943 (3)	148
O2—H4W⋯O5^vi	0.85	1.92	2.766 (2)	174
O4—H8W⋯O8^vi	0.85	1.85	2.702 (2)	175

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

Acknowledgments

The study was supported by the Science and Technology Department of Henan Province (082102330003).

supplementary crystallographic information

Comment

Triazole and benzotriazole derivatives have been widely used in the construction of complexes since they can act as polydentate ligands and function as bridging ligands (Aromia et al., 2011; Meng et al., 2009). Moreover, Cu^II complexes have attracted more and more attention owing to their intrinsic esthetic appeal and potential applications in various fields (Zhou et al., 2007; Brown et al., 2009). In this work, through the reaction of 1-((benzotriazol-1-yl)methyl)-1-H-1,2,4-triazole (bmt) with copper sulfate at room temperature, we obtained the title complex [Cu(bmt) (SO₄) (H₂O)₄] (H₂O)_1.5, which is reported here. As shown in Figure 1, each Cu^II ion is located in a slightly distorted octahedral environment and is coordinated to one nitrogen atom from the bmt ligand, five oxygen atoms from four water molecules and one monodentate sulfate. Atoms O1, O2, O4, N1 and Cu1 are nearly co-planar (the mean deviation from the plane is 0.0203 Å). The apical Cu1—O3 and Cu1—O5 bond lengths (2.331 (2) and 2.465 Å) are considerably longer than the equatorial ones (1.974 (2)- 2.002 (2) Å) due to the Jahn-Teller effect. Intramolecular O—H···O hydrogen bonds stabilize the molecular configuration and O—H···O, O—H···N hydrogen bonds between adjacent molecules consolidate the crystal packing.

Experimental

The ligand 1-((benzotriazol-1-yl)methyl)-1-H-1,2,4-triazole (0.1 mmol) in methanol (4 ml) was added dropwise to an aqueous solution (2 ml) of copper sulfate (0.1 mmol). The resulting solution was allowed to stand at room temperature. After three weeks blue crystals with good quality were obtained from the filtrate and dried in air.