Dichlorido[(4E,11E)-5,7,12,14-tetra­benzyl-7,14-dimethyl-1,4,8,11-tetra­aza­cyclo­tetra­deca-4,11-diene]cobalt(III) perchlorate

Tapashi G Roy; Saroj K S Hazari; Kanak K Barua; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811046484

. 2011 Nov 9;67(Pt 12):m1722–m1723. doi: 10.1107/S1600536811046484

Dichlorido[(4E,11E)-5,7,12,14-tetrabenzyl-7,14-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene]cobalt(III) perchlorate

Tapashi G Roy ^a,^‡, Saroj K S Hazari ^a, Kanak K Barua ^a, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3238638 PMID: 22199529

Abstract

The Co^III atom in the title complex, [CoCl₂(C₄₀H₄₈N₄)]ClO₄, is octahedrally coordinated within a trans-Cl₂N₄ donor set provided by the tetradentate macrocylic ligand and two chloride ions. The N—H atoms, which are orientated to one side of the N₄ plane, form hydrogen bonds with chloride ions and perchlorate-O atoms. These along with C—H⋯O interactions consolidate the three-dimensional crystal structure. One of the benzene rings was disordered. This was resolved over two positions with the major component of the disorder having a site-occupancy factor of 0.672 (4).

Related literature

For background to the synthesis, characterization, kinetic studies and biological activity of 14-membered methyl-substituted tetraazamacrocyclic ligands, their N-substituted derivatives and metal complexes, see: Bembi et al. (1990 ▶); Roy et al. (2007 ▶, 2011a ▶); Hazari et al. (2008 ▶). For a related structure, see: Roy et al. (2011b ▶).

Experimental

Crystal data

[CoCl₂(C₄₀H₄₈N₄)]ClO₄
M _r = 814.10
Triclinic,
a = 10.8111 (7) Å
b = 13.835 (2) Å
c = 14.868 (3) Å
α = 73.66 (3)°
β = 70.06 (3)°
γ = 68.65 (2)°
V = 1915.6 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 153 K
0.30 × 0.20 × 0.10 mm

Data collection

Rigaku AFC12/SATURN724 diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.627, T _max = 1.000
20336 measured reflections
7470 independent reflections
6940 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.142
S = 1.05
7470 reflections
476 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) & DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811046484/pv2479sup1.cif

e-67-m1722-sup1.cif^{(37.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046484/pv2479Isup2.hkl

e-67-m1722-Isup2.hkl^{(358.1KB, 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
N2—H2n⋯O1	0.88 (3)	2.24 (3)	3.063 (4)	155 (2)
N4—H4n⋯Cl2ⁱ	0.88 (3)	2.64 (2)	3.432 (2)	150 (3)
C10—H10a⋯O3ⁱⁱ	0.99	2.50	3.437 (4)	159
C19—H19b⋯O1ⁱⁱⁱ	0.99	2.54	3.409 (4)	147
C38a—H38a⋯O4^iv	0.95	2.57	3.480 (3)	160

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

Acknowledgments

The authors are grateful to the University Grant Commission (UGC), Bangladesh, for the award of a research grant to TGR.

supplementary crystallographic information

Comment

In continuation of on-going studies of the synthesis, characterization and biological activities of substituted tetraazamacrocyclic ligands and their metal complexes (Bembi et al., 1990; Roy et al., 2007; Hazari et al., 2008; Roy et al., 2011a; Roy et al. 2011b), the synthesis and crystal structure of the title complex, (I), was investigated.

In (I), Fig. 1, the Co^III atom exists within a trans-Cl₂N₄ donor set defined by the four nitrogen atoms of the macrocyclic ligand and two chlorido atoms. The coordination geometry is based on an octahedron, with the greatest angular distortion manifested in the N2—Co—N3 angle of 83.81 (9)°. With respect to the central N₄ plane, the rings adopt three distinct orientations. Two rings adopt similar orientations lying approximately perpendicular and parallel to the N₄ plane: the dihedral angle between the N₄ and the C12–C17 and C20–C25 planes are 86.928 (8) and 78.645 (10) °, respectively. The C27–C32 ring is also orientated in a perpendicular fashion (dihedral angle = 88.921 (10)°) but lies to one side of the N₄ plane, with the C6—C26—C27—C28 torsion angle = 117.15 (4)°. The final ring is disordered over two positions. The major component is approximately planar with the N₄ donor set, forming a dihedral angle of 20.644 (10)°, whereas the minor component forms a dihedral angle of 13.400 (9) °, i.e. even more co-planar. Within the N₄ donor set, the two amine-H atoms are orientated to one side of the plane. The N2—H atom forms a contact with the perchlorate-O1 atom, and the N4—H forms an intramolecular N—H···Cl hydrogen bond, Table 2. These interactions along with several C—H···O contacts lead to the formation of supramolecular arrays in the ab plane. The layers stack along the c axis with the closest connection being of the type C—H···O, involving the perchlorate-O4 atom (Fig. 2 and Table 1).

Experimental

The macrocyclic ligand, (4E,11E)-5,7,12,14-tetrabenzyl-7,14-dimethyl- 1,4,8,11-tetraazacyclotetradeca-4,11-diene (0.783 g, 1.0 mmol) was suspended in methanol (30 ml). Separately, cobaltous acetate (0.248 g, 1.0 mmol) was dissolved in methanol (30 ml). The combined solutions were heated on a water bath until the solution turned red. Concentrated HCl was added drop-wise so that the solution turned green. Then, about 1 ml HClO₄ was added whereupon a green product started to appear. The mixture was heated in order to reduce the volume to 15 ml. The resulting solution was kept at room temperature for about 1 h. The solid product, (I), was separated by filtration, washed with dry ethanol, followed by diethylether and dried in a vacuum desiccator over silica-gel. The yield was about 50%. The same complex was also prepared by using the acetonitrile as the solvent instead of methanol. However, the yield was about 42%. Green crystals of (I) were isolated from the slow evaporation of its methanol solution.