Bis(triethano­lamine)nickel(II) sulfate

Hong-Xu Guo; Zi-Xian Du; Xi-Zhong Li

doi:10.1107/S1600536809023046

. 2009 Jun 20;65(Pt 7):m810–m811. doi: 10.1107/S1600536809023046

Bis(triethanolamine)nickel(II) sulfate

Hong-Xu Guo ^a,^*, Zi-Xian Du ^b, Xi-Zhong Li ^a

PMCID: PMC2969259 PMID: 21582734

Abstract

The title compound, [Ni(C₆H₁₅NO₃)₂]SO₄, contains two triethanolamine (TEA) ligands bound to an Ni²⁺ metal centre, which lies on a crystallographic inversion centre, and one sulfate anion located on a twofold rotation axis such that the asymmetric unit contains one-half molecule of the cation and of the anion. The triethanolamine ligands coordinate via each axial N atom and two of the three O atoms, while the third arm of the ligand has the hydroxyl group pointing away from the metal centre. The sulfate anions are hydrogen bonded to the coordinated hydroxyl groups and also to the free arm, forming a two-dimensional supramolecular hydrogen-bonded network expanding parallel to (010).

Related literature

For background to metal-ion-containing supramolecular compounds, see: Venkataraman et al. (1995 ▶); Kepert & Rosseinsky (1999 ▶); Fujita et al. (1994 ▶). For magnetic materials, see: Kahn (1993 ▶). For other TEA compounds, see: Krabbes et al. (2000 ▶); Topcu et al. (2001 ▶); Ucar et al. (2004 ▶); Haukka et al. (2005 ▶). For similar structures, see: İçbudak et al. (1995 ▶); Yeşilel et al. (2004 ▶).

Experimental

Crystal data

[Ni(C₆H₁₅NO₃)₂]SO₄
M _r = 453.15
Monoclinic,
a = 10.316 (2) Å
b = 11.234 (2) Å
c = 15.498 (3) Å
β = 90.04 (3)°
V = 1796.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.25 mm⁻¹
T = 293 K
0.41 × 0.21 × 0.11 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.741, T _max = 0.879
8633 measured reflections
2042 independent reflections
1905 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.085
S = 1.02
2042 reflections
120 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: SMART (Siemens, 1994 ▶); cell refinement: SAINT (Siemens, 1994 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023046/pk2167sup1.cif

e-65-0m810-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023046/pk2167Isup2.hkl

e-65-0m810-Isup2.hkl^{(100.5KB, 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
O1—H1C⋯O5ⁱ	0.82	2.19	2.663 (2)	117
O2—H2C⋯O4ⁱⁱ	0.82	2.28	2.6227 (19)	106
O3—H3C⋯O5	0.82	2.00	2.818 (2)	174
C3—H3B⋯O3	0.97	2.26	3.055 (3)	139

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

Acknowledgments

This work was supported by the Natural Science Foundation of Fujian Province (2008 J0172)

supplementary crystallographic information

Comment

Many workers from a variety of scientific disciplines are interested in the crystal design and engineering of multidimensional arrays and networks containing metal ions as nodes. Metal-ion containing supramolecular structures can be used as zeolite-like materials (Venkataraman et al., 1995; Kepert & Rosseinsky, 1999), catalysts (Fujita et al., 1994) or magnetic materials (Kahn, 1993). Triethanolamine (TEA) is a good potential ligand to the incorporation of metals into metal-ion containing supramolecular framework, and many compounds constructed from TEA have been reported in the last decade (Krabbes et al., 2000; Topcu et al., 2001; Ucar et al., 2004; Haukka et al., 2005). In this work we employed TEA and NiSO₄ to produce a novel complex, [Ni(C₆H₁₅NO₃)₂]SO₄(I).

A view of the title compound and its numbering scheme are shown in Fig. 1. The crystal structure consists of a complex cation and one sulfate anion. In the cation, the Ni^II ion lies on a centre of symmetry, sandwiched by two bulky TEA ligands. Each TEA acts as a tridentate ligand through two of the three hydroxyl O atoms and the amine N atom, resulting in a six-coordinate Ni^II ion similar to those observed for the Ni complex of TEA with chloride (İçbudak et al., 1995), saccharine (Topcu et al., 2001), acetate (Krabbes et al., 2000) and squarate (Yeşilel et al., 2004).

The coordination geometry around the Ni^II ion is that of a distorted octahedron. The hydroxyl O atoms of two TEA ligands form the equatorial plane of the octahedral geometry, while atoms N1 and N1ⁱ are placed in axial positions (symmetry code as in Fig. 1). In the complex, Ni—O distances are in the range 2.0762 (13)–2.0768 (12)Å and the Ni—N distance is 2.1072 (16) Å, while the bond angles at Ni range from 82.30 (5)° to 97.70 (6)°.

In the crystal structure, classical intermolecular O—H···O hydrogen bonds are observed (Table 1), which link the cations and one sulfate anion into a two-dimensional hydrogen-bonded network and stabilize the crystal packing (Fig. 2). Each cation is bonded to four SO₄^2- anions, which in turn link four cations through O—H···O hydrogen bonding interactions to form a 2-D hydrogen bonding network. In addition, there is extensive hydrogen bonding between the –CH₂ and the uncoordinated hydroxyl O atoms, with C···O interatomic distances of 3.055 (3) Å.

Experimental

NiSO₄.7H₂O (0.5257 g, 2 mmol) was dissolved in 10 ml water and the pH was adjusted to 7 with triethanolamine. Blue crystals of separated from the filtered solution at room temperature over several days.