Diaqua­(1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4 N 1,N 4,N 8,N 11)copper(II) dihepta­noate dihydrate

Nur Syamimi Ahmad Tajidi; Norbani Abdullah; Zainudin Arifin; Kong Wai Tan; Seik Weng Ng

doi:10.1107/S1600536810025687

. 2010 Jul 7;66(Pt 8):m887. doi: 10.1107/S1600536810025687

Diaqua(1,4,8,11-tetraazacyclotetradecane-κ⁴ N ¹,N ⁴,N ⁸,N ¹¹)copper(II) diheptanoate dihydrate

Nur Syamimi Ahmad Tajidi ^a, Norbani Abdullah ^a, Zainudin Arifin ^a, Kong Wai Tan ^a, Seik Weng Ng ^a,^*

PMCID: PMC3007509 PMID: 21588132

Abstract

The Cu^II atom in the title salt, [Cu(C₁₀H₂₄N₄)(H₂O)₂][CH₃(CH₂)₅CO₂]₂·2H₂O, is chelated by the four N atoms of the 1,4,8,11-tetraazacyclotetradecane (cyclam) ligand and is coordinated by two water molecules in a tetragonally Jahn–Teller-distorted octahedral geometry. The Cu^II atom lies on a center of inversion. The cations, anions and uncoordinated water molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds, forming a layer structure parallel to (100). The alkyl chain of the anion is disordered over two positions in a 0.82 (1):0.18 (1) ratio.

Related literature

For related diaqua(1,4,8,11-tetraazacyclotetradecane)copper carboxylates, see: Lindoy et al. (2003 ▶); Hunter et al. (2005 ▶).

Experimental

Crystal data

[Cu(C₁₀H₂₄N₄)(H₂O)₂](C₇H₁₃O₂)₂·2H₂O
M _r = 594.28
Monoclinic,
a = 11.7257 (6) Å
b = 9.9426 (5) Å
c = 13.4573 (7) Å
β = 103.1363 (7)°
V = 1527.85 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 100 K
0.35 × 0.25 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.776, T _max = 0.894
14358 measured reflections
3506 independent reflections
3140 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.079
S = 1.06
3506 reflections
212 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810025687/bt5285sup1.cif

e-66-0m887-sup1.cif^{(23.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025687/bt5285Isup2.hkl

e-66-0m887-Isup2.hkl^{(171.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Cu1—N1	2.026 (1)
Cu1—N2	2.025 (1)
Cu1—O1w	2.499 (1)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86 (1)	2.30 (1)	2.983 (2)	137 (2)
N2—H2⋯O2	0.86 (1)	2.12 (1)	2.924 (2)	156 (2)
O1w—H11⋯O2	0.83 (1)	1.93 (1)	2.730 (2)	162 (2)
O1w—H12⋯O2w	0.83 (1)	1.95 (1)	2.777 (2)	174 (2)
O2w—H21⋯O1ⁱⁱ	0.83 (1)	2.02 (1)	2.833 (2)	166 (2)
O2w—H22⋯O1ⁱ	0.84 (1)	1.91 (1)	2.743 (2)	171 (2)

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

Acknowledgments

We thank the University of Malaya (RG039/09SUS) and the Ministry of Higher Education (FP017/2009) for supporting this study.

supplementary crystallographic information

Comment

The copper(II) ion forms a number of complexes with 1,4,8,11-tetraazacyclotetradecane in which the metal atom is coordinated by the four amino donor-atoms of the cyclic ligand. Among the carboxylate derivatives, neither the acetate nor the benzoate ions bind directly with the copper atom. The copper atom is coordinated instead by water molecules so that the carboxylate group interacts indirectly with the metal atom through the coordinated water molecules (Hunter et al., 2005; Lindoy et al., 2003). The copper(II) atom in the salt, [Cu(H₂O)₂(C₁₀H₂₄N₄)]²⁺ 2[CH₃(CH₂)₅CO₂]^-.2H₂O (Scheme I), is chelated by the four nitrogen atoms of the cyclam ligand and is coordinated by two water molecules in a Jahn-Teller type of tetragonally distorted octahedral geometry. The copper atom lies on a center of inversion (Fig. 1). The cations, anions and lattice water molecules are linked by N–H···O and O–H···O hydrogen bonds to form a layer structure.

Experimental

1,4,8,11-Tetraazacyclotetradecane (0.50 g, 2.50 mmol) dissolved in ethanol (25 ml) was mixed with a suspension of copper heptanoate (0.80 g, 2.5 mmol) in ethanol (50 ml) to give a purple solution. The solution was heated for an hour and then filtered. Prismatic crystals separated from the solution when it was left to cool slowly.