Diaqua­(5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­azacyclo­tetra­deca­ne)nickel(II) tetra­cyanidonickelate(II)

Qian Zhang; Xiao-Ping Shen; Hu Zhou

doi:10.1107/S1600536809033820

. 2009 Aug 29;65(Pt 9):m1141. doi: 10.1107/S1600536809033820

Diaqua(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)nickel(II) tetracyanidonickelate(II)

Qian Zhang ^a, Xiao-Ping Shen ^a,^*, Hu Zhou ^a

PMCID: PMC2970059 PMID: 21577476

Abstract

In the title complex, [Ni(C₁₆H₃₆N₄)(H₂O)₂][Ni(CN)₄], the [Ni(teta)(H₂O)₂]²⁺ cations (teta = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) and [Ni(CN)₄]²⁻ anions are arranged in an alternating fashion through electrostatic and N—H⋯N and O—H⋯N hydrogen-bonding interactions, forming a two-dimensional layered structure. Adjacent layers are linked through weak van der Waals interactions, resulting in a three-dimensional supramolecular network.

Related literature

For background to cyanide-bridged complexes, see: Lescouëzec et al. (2005 ▶); Liu et al. (2008 ▶); Xu et al. (2009 ▶). For related structures, see: Jiang et al. (2005 ▶, 2007 ▶); Ni et al. (2008 ▶); Yamada & Iwasaki (1969 ▶).

Experimental

Crystal data

[Ni(C₁₆H₃₆N₄)(H₂O)₂][Ni(CN)₄]
M _r = 542.02
Monoclinic,
a = 8.065 (8) Å
b = 13.255 (12) Å
c = 13.559 (10) Å
β = 116.59 (4)°
V = 1296 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.48 mm⁻¹
T = 173 K
0.58 × 0.16 × 0.12 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.808, T _max = 0.888
9778 measured reflections
2530 independent reflections
1576 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.093
S = 1.01
2530 reflections
163 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033820/at2863sup1.cif

e-65-m1141-sup1.cif^{(17.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033820/at2863Isup2.hkl

e-65-m1141-Isup2.hkl^{(124.3KB, 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
N4—H4⋯N1ⁱ	0.81 (3)	2.46 (3)	3.250 (4)	164 (3)
N3—H3⋯N2	0.88 (3)	2.34 (3)	3.201 (4)	167 (3)
O1—H1B⋯N2	0.830 (10)	1.964 (11)	2.789 (4)	172 (3)
O1—H1A⋯N1ⁱⁱ	0.835 (10)	1.939 (11)	2.775 (4)	179 (3)

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

Acknowledgments

The authors thank the Natural Science Foundation of Jiangsu Province (BK2009196) and the Foundation of the State Key Laboratory of Coordination Chemistry (China) for financial support.

supplementary crystallographic information

Comment

In the past decades, there has been a continuous interest in the utilization of cyano-containing building blocks for constructing either ion-paired or cyano-bridged assemblies due to their potential applications and intriguing architectures (Lescouëzec et al., 2005; Liu et al., 2008; Xu et al., 2009). It has been found that cyano-bridged bimetallic assemblies, derived from tailored cyanometalate entities [ML_p(CN)_q]^n- (L = polydentate ligand) and unsaturated coordinated complex [M'(L)]^m+, possess extraordinarily excellent magnetic properties such as SMM (single molecular magnets) and SCM (single chain magnets). Recently, we had expected to obtain such low-dimensional system using [Cr(salen)(CN)₂]^- (Yamada et al., 1969; Ni et al., 2008) and [Ni(teta)]²⁺ as the building blocks. However, an unexpected tetracyanonickel(II)-based complex of [Ni(teta)(H₂O)₂][Ni(CN)₄] instead of any [Cr(salen)(CN)₂]^--based complex was obtained. So far, Jiang et al. (Jiang et al., 2005; 2007) have reported several complexes based on the direct assembly of [Ni(CN)₄]^2- and [Ni(teta)]²⁺ building blocks, and they found that all these complexes showed cyano-bridged structures. In contrast to these reported complexes, the title complex of [Ni(teta)(H₂O)₂][Ni(CN)₄] is ion-paired and its crystal structure is reported here.

The title complex consists of [Ni(teta)(H₂O)₂]²⁺ cation and [Ni(CN)₄]^2- anion (Fig. 1). In [Ni(teta)(H₂O)₂]²⁺ cation, the Ni^II ion assumes a distorted octahedral coordination geometry, in which the equatorial sites are occupied by four nitrogen atoms of the macrocyclic ligand teta with the Ni(2)—N bond distances of 2.067 (3) and 2.100 (3) Å, while the axial positions are occupied by two oxygen atoms of water molecules with Ni(2)—O distance of 2.183 (2) Å. As usual, [Ni(CN)₄]^2- anion exhibits a square planar structure, where all four cyano groups are terminal ones, with Ni(1)—C(1) and Ni(1)—C(2) distances of 1.862 (3) and 1.869 (3) Å, respectively. The Ni(1)—C—N bonds deviate slightly from linearity with the bond angles 177.2 (3) and 178.1 (3)°. [Ni(teta)(H₂O)₂]²⁺ and [Ni(CN)₄]^2- are arranged in an alternating fashion, forming a two-dimensional layered structure through electrostatic and hydrogen bonding interactions (Fig. 2). Furthermore, adjacent layers are linked through weak van der Waals interactions, resulting in a three-dimensional supramolecular network (Fig. 3).

Experimental

A solution of Ni(teta)(ClO₄)₂ (0.05 mmol) in DMF (10 ml) was added to a solution of K[Cr(salen)(CN)₂].H₂O (0.05 mmol) in MeOH/H₂O (1/1(V/V),10 ml) mixture. The resulting solution was filtrated and the filtrate was left to allow slow evaporation in dark at room temperature. Pink prism crystals of the title complex were obtained after two weeks, washed with MeOH and H₂O, respectively, and dried in air. Anal. Calc. for C₂₀H₄₀Ni₂N₈O₂: C, 44.32; H, 7.44; N, 20.68; Ni, 21.66%. Found: C, 44.28; H, 7.49; N, 20.71; Ni, 21.52%.