{3,14-Dimethyl-2,6,13,17-tetra­aza­tricyclo­[16.4.0.07,12]docosane-κ4 N,N′,N′′,N′′′)bis­(nitrato-κO)copper(II)

Jong-Ha Choi; Md Abdus Subhan; Seik Weng Ng

doi:10.1107/S1600536812001845

. 2012 Jan 21;68(Pt 2):m190. doi: 10.1107/S1600536812001845

{3,14-Dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.0^7,12]docosane-κ⁴ N,N′,N′′,N′′′)bis(nitrato-κO)copper(II)

Jong-Ha Choi ^a, Md Abdus Subhan ^a, Seik Weng Ng ^b,^c,^*

PMCID: PMC3274913 PMID: 22346860

Abstract

The Cu^II atom in the title compound, [Cu(NO₃)₂(C₂₀H₄₀N₄)], is N,N′,N′′,N′′′-chelated by the macrocyclic ligand: the four N atoms form a square, above and below which are located the O atoms of the nitrate ions. The metal atom exists in a tetragonally distorted octahedron, on a special position of Inline graphic site symmetry. One of the amino groups is hydrogen bonded to an O atom of the nitrate ion. The other amino group is hydrogen bonded to O atom of an adjacent molecule, generating a supramolecular dimeric hydrogen-bonded dinuclear aggregate.

Related literature

For the synthesis of the cyclam, see: Choi et al. (2012 ▶). For similar copper nitrate–cyclam adducts, see: Amadei et al. (1999 ▶); Choi et al. (2001 ▶, 2006 ▶); Dong et al. (1999 ▶); Liu & Chu (2010 ▶).

Experimental

Crystal data

[Cu(NO₃)₂(C₂₀H₄₀N₄)]
M _r = 524.12
Triclinic,
a = 8.2552 (10) Å
b = 8.8074 (11) Å
c = 9.1399 (10) Å
α = 67.879 (12)°
β = 68.780 (11)°
γ = 75.096 (11)°
V = 568.23 (12) Å³
Z = 1
Mo Kα radiation
μ = 1.01 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) ▶ T _min = 0.751, T _max = 0.906
4122 measured reflections
2332 independent reflections
1963 reflections with I > 2σ(I)
R _int = 0.064

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.132
S = 1.02
2332 reflections
159 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.96 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 datablock(s) global, I. DOI: 10.1107/S1600536812001845/xu5440sup1.cif

e-68-0m190-sup1.cif^{(18KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812001845/xu5440Isup2.hkl

e-68-0m190-Isup2.hkl^{(114.6KB, 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
N1—H1⋯O2ⁱ	0.88 (1)	2.15 (2)	2.992 (3)	160 (3)
N2—H2⋯O3ⁱⁱ	0.88 (1)	2.23 (2)	2.961 (3)	140 (3)

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

Acknowledgments

We thank Andong National University and the Ministry of Higher Education of Malaysia (grant No. UM·C/HIR/MOHE/SC/12) for supporting this study.

supplementary crystallographic information

Comment

The macrocycle, cyclam (1,4,8,11-tetraazacyclotetradecane), forms a large number of complexes with copper(II) salts in which the macrocle chelates in a tetradentate matter. In same cases, the counterion bonded to the metal atoms and in other cases, the metal atom exists in square-pyramidal geometry as the counterion is far away. The crystal structure of copper nitrate–cyclam has not been reported; the crystal structures of other substituted cyclams have the metal atom in a tetragonally elongated octahedral geometry (Amadei et al., 1999; Choi et al., 2006; Choi et al., 2001; Dong et al., 1999; Liu & Chu, 2010). The Cu^II atom in the title compound (Scheme I) is similarly chelated by the macrocyclic ligand in a tetragonally distorted octahedron (Fig.1). The atom lies on a special position of –1 site symmetry. One of the amino groups is hydrogen-bonded to an O atom of the nitrate ion. The other amino group is hydrogen-bonded to O atom of an adjacent molecule to generate a hydrogen-bonded dinuclear molecule (Table 1).

Experimental

The macrocycle co-crystal, 3,14-dimethyl-2,6,13,17-tetraazatricyclo(16.4.0.0^7,12)docosane (naphthalen-1-yl)methanol prepared as described (Choi et al., 2012). Copper nitrate trihydrate (0.242 g, 1 mmol) dissolved in methanol (10 ml) was mixed with a suspension of the macrocycle co-crystal (0.163 g, 2.5 mmol) dissolved in methanol (10 ml). The mixture was heated for 30 minutes and then set aside for the growth of purple crystals.