[μ-N,N′-Bis(2-amino­eth­yl)ethane-1,2-diamine-κ4 N 1,N 1′:N 2,N 2′]bis­{[N,N′-bis­(2-amino­eth­yl)ethane-1,2-diamine-κ4 N,N′,N′′,N′′′]cadmium} tetra­kis­(perchlorate)

Hamid Goudarziafshar; Yunes Abbasityula; Václav Eigner; Michal Dušek

doi:10.1107/S1600536812033880

. 2012 Aug 4;68(Pt 9):m1153–m1154. doi: 10.1107/S1600536812033880

[μ-N,N′-Bis(2-aminoethyl)ethane-1,2-diamine-κ⁴ N ¹,N ^1′:N ²,N ^2′]bis{[N,N′-bis(2-aminoethyl)ethane-1,2-diamine-κ⁴ N,N′,N′′,N′′′]cadmium} tetrakis(perchlorate)

Hamid Goudarziafshar ^a,^*, Yunes Abbasityula ^a, Václav Eigner ^b,^c, Michal Dušek ^c

PMCID: PMC3435582 PMID: 22969455

Abstract

The centrosymmetric dinuclear cadmium title complex, [Cd₂(C₆H₁₈N₄)₃](ClO₄)₄, was obtained by the reaction of N,N′-bis(2-aminoethyl)ethane-1,2-diamine (trien) with Cd(NO₃)₂·4H₂O and sodium perchlorate in methanol. The Cd^II cation is coordinated by four N atoms of a non-bridging trien ligand and by two N atoms of a bridging trien ligand in a slightly distorted octahedral coordination geometry. The bridging ligand shares another two N atoms with a neighboring symmetry-equivalent Cd^II cation. The structure displays C—H⋯O and N—H⋯O hydrogen bonding. The perchlorate anion is disordered over two sets of sites in a 0.854 (7): 0.146 (7) ratio.

Related literature

Polyamines are an important class of N-donor ligands, particularly for transition metals, see: Patel et al. (2007 ▶); Blackman (2005 ▶). For polynuclear complexes, see: Gustafsson et al. (2010 ▶); Ambrosi et al. (2009 ▶); You et al. (2011 ▶). For polynuclear complexes of cadmium, see: Evans & Lin (2002 ▶); For background to the use of the trien ligand in complexation, see: Cai et al. (2001a ▶,b ▶); Buckingham et al. (1974 ▶, 1975 ▶); Chowdhury et al. (2007 ▶). Buckingham & Jones (1965 ▶); Shinohara et al. (1991 ▶); He (2009 ▶); Patel et al. (2008 ▶); Anderson et al. (1977 ▶); Shoukry et al. (1998 ▶); Hu et al. (2000 ▶). For dinuclear Cd complexes, see: Das et al. (2010 ▶); Nie et al. (2010 ▶); Wang et al. (2011 ▶); Sun et al. (2010 ▶). For details of the preparation, see: Harrowfield et al. (1996 ▶).

Experimental

Crystal data

[Cd₂(C₆H₁₈N₄)₃](ClO₄)₄
M _r = 1061.3
Monoclinic,
a = 8.8056 (2) Å
b = 15.0259 (3) Å
c = 14.7516 (3) Å
β = 95.4420 (17)°
V = 1943.02 (7) Å³
Z = 2
Mo Kα radiation
μ = 1.45 mm⁻¹
T = 120 K
0.70 × 0.51 × 0.33 mm

Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer
Absorption correction: analytical (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.509, T _max = 0.738
31295 measured reflections
4952 independent reflections
4373 reflections with I > 3σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.106
S = 2.02
4952 reflections
269 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.13 e Å⁻³
Δρ_min = −0.92 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812033880/ru2040sup1.cif

e-68-m1153-sup1.cif^{(21.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033880/ru2040Isup2.hkl

e-68-m1153-Isup2.hkl^{(218.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cd1—N1	2.362 (2)
Cd1—N4	2.390 (3)
Cd1—N7	2.377 (3)
Cd1—N10	2.380 (3)
Cd1—N11	2.374 (3)
Cd1—N14	2.375 (2)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H1c5⋯O4c ⁱ	0.96	2.49	3.449 (3)	172
N1—H2n1⋯O3c ⁱⁱ	0.80 (4)	2.46 (4)	3.149 (4)	145 (3)
N11—H1n11⋯O2c ⁱⁱⁱ	0.82 (4)	2.40 (4)	3.140 (4)	149 (3)
N11—H2n11⋯O4a ⁱⁱ	0.92 (4)	2.44 (4)	3.210 (5)	141 (3)
N4—H1n4⋯O4a ⁱⁱ	0.98 (3)	2.36 (3)	3.271 (4)	154 (2)
N4—H1n4⋯O5a ⁱⁱ	0.98 (3)	2.38 (3)	3.236 (4)	145 (2)
N4—H1n4⋯O5b ⁱⁱ	0.98 (3)	2.22 (3)	3.113 (13)	151 (3)

Open in a new tab

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

Acknowledgments

This work was supported by the University of Ilam, the Institutional research plan No. AVOZ10100521 of the Institute of Physics and the Praemium Academiae project of the Academy of Sciences (ASCR).

supplementary crystallographic information

Comment

Polyamines are an important class of N donor ligands, particularly for the transition metals (Patel et al., 2007, 2008; Blackman, 2005). Considerable attention has been focused on the polynuclear complexes containing bridging ligands because of their interesting molecular topologies, as well as the fact that they may be designed with specific functionalities (Gustafsson et al. 2010;. Ambrosi et al. 2009; You et al. 2011). The investigation of polynuclear complexes of cadmium(II) is an important objective in view of their electronic and optoelectronic properties (Evans et al. 2002; Chowdhury et al. 2007).

The molecular structure of the title complex is shown in Fig. 1. The cadmium(II) centers are six-coordinate by four nitrogen atoms of the non-bridging tetradentate (trien) ligand and two nitrogen atoms of the bridging trien ligand, with a substantial departure from an ideal octahedral geometry [cisoid angles: 73.97 (8)–114.67 (9)°; transoid angles: 141.95 (1)–159.20 (6)°] (Table 1). The distance between the two cadmium(II) centers of the dinuclear complex is 7.735 Å, which is longer than the corresponding distance in dinickel(II) complex (7.497 Å) of the same ligand (Cai et al. 2001b) due to larger radius of cadmium. Cadmium atoms in the dinuclear complex are related by a 2 fold symmetry operation. Bond distance of Cd—N(trien) are in the range of 2.62 (3)- 2.90 (3) Å (Table 1). The structure exhibits disorder of one of the perchlorate anions in two positions with refined occupancy 0.854 (7) and 0.146 (7) for the major and minor componet,respectively. The disorder was described using the rigid body approach. In the title complex the C—H···O and N—H···O hydrogen bonds have been found between the amine nitrogen/carbon donors and perchlorate acceptors (Fig.2),(Table 2).

Experimental

N,N'-bis(2-aminoethyl)ethane-1,2-diamine (0.45 g, 3 mmol) was placed in one arm of a branched tube (Harrowfield et al., 1996) and a mixture of Cd(NO₃)₂.4H₂O (0.616 g, 2 mmol) and sodium perchlorate (0.488 g, 4 mmol) in the other. Methanol was then carefully added to fill both arms, the tube sealed and the ligand-containing arm immersed in a bath at 333 K, while the other was left at ambient temperature. After one week, colorless crystals were collected in the cooler arm. Then they were filtered off, washed with acetone and diethylether, and air dried. Yield: (53%).