Diaqua­bis(1,3-propane­diamine)nickel(II) squarate tetrahydrate

Ersin Temel; Hakan Erer; Okan Zafer Yeşilel; Orhan Büyükgüngör

doi:10.1107/S160053680902087X

. 2009 Jun 6;65(Pt 7):m735–m736. doi: 10.1107/S160053680902087X

Diaquabis(1,3-propanediamine)nickel(II) squarate tetrahydrate

Ersin Temel ^a, Hakan Erer ^b, Okan Zafer Yeşilel ^b, Orhan Büyükgüngör ^a,^*

PMCID: PMC2969320 PMID: 21582677

Abstract

The asymmetric unit of the title compound, [Ni(C₃H₁₀N₂)₂(H₂O)₂](C₄O₄)·4H₂O, contains one-half of the diaquabis(1,3-propanediamine)nickel(II) cation, one-half of the centrosymmetric squarate anion and two uncoordinated water molecules. In the cation, the Ni^II atom is located on a crystallographic inversion centre and has a slightly distorted octahedral coordination geometry. The six-membered chelate ring adopts a chair conformation. O—H⋯O hydrogen bonds link the cation and anion through the water molecule, while N—H⋯O hydrogen bonds link the cation and anion and cation and water molecules. In the crystal structure, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into a three-dimensional network structure.

Related literature

For general background, see: Bertolasi et al. (2001 ▶); Gollogly & Hawkins (1972 ▶); Lam & Mak (2000 ▶); Liebeskind et al. (1993 ▶); Mathew et al. (2002 ▶); Reetz et al. (1994 ▶); Seitz & Imming (1992 ▶); Zaman et al. (2001 ▶). For related structures, see: Ghosh et al. (1997 ▶); Mukherjee et al. (1990 ▶); Pariya et al. (1995 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Ni(C₃H₁₀N₂)₂(H₂O)₂](C₄O₄)·4H₂O
M _r = 427.09
Monoclinic,
a = 8.0429 (4) Å
b = 9.1752 (5) Å
c = 14.6510 (8) Å
β = 117.570 (4)°
V = 958.40 (9) Å³
Z = 2
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 296 K
0.75 × 0.45 × 0.05 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.638, T _max = 0.949
7288 measured reflections
2204 independent reflections
2003 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.054
S = 1.06
2204 reflections
139 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I. DOI: 10.1107/S160053680902087X/hk2703sup1.cif

e-65-0m735-sup1.cif^{(16.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902087X/hk2703Isup2.hkl

e-65-0m735-Isup2.hkl^{(106.1KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

O1—Ni1	2.1429 (9)
N1—Ni1	2.1090 (10)
N2—Ni1	2.0997 (10)

Open in a new tab

N1—Ni1—O1	88.86 (4)
N2—Ni1—O1	91.46 (4)
N2—Ni1—N1	91.94 (4)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O5ⁱ	0.90	2.35	3.1715 (16)	152
N2—H2A⋯O2ⁱⁱ	0.90	2.33	3.2174 (14)	170
O1—H1F⋯O2ⁱⁱⁱ	0.77 (2)	2.08 (2)	2.8345 (15)	165 (2)
O4—H4A⋯O2ⁱⁱⁱ	0.80 (2)	2.10 (2)	2.8765 (16)	165 (2)
O4—H4B⋯O2^iv	0.82 (3)	2.07 (3)	2.8965 (16)	178 (2)
O5—H5B⋯O4^v	0.77 (2)	2.10 (3)	2.8730 (19)	177 (2)
N1—H1A⋯O4	0.90	2.38	3.2442 (17)	160
N2—H2B⋯O3	0.90	2.04	2.9333 (14)	174
O1—H1E⋯O5	0.80 (2)	1.93 (2)	2.7311 (16)	175.8 (19)
O5—H5A⋯O3	0.80 (2)	1.94 (2)	2.7296 (16)	166 (2)

Open in a new tab

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

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences of Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant No. F279 of the University Research Grant of Ondokuz Mayıs University).

supplementary crystallographic information

Comment

The conformation of six-membered rings arranged by the bidentate coordination of pen (1,3-propanediamine) to transition metals has long been of theoretical interest (Gollogly & Hawkins, 1972). Despite this interest, only a limited number of such complexes have been structurally described. Because of their ability to undergo solid-state phase transitions, some nickel(II) complexes of bis(N-substituted-pen) have been studied in recent times (Mukherjee et al., 1990; Pariya et al., 1995; Ghosh et al., 1997).

Squaric acid (H₂C₄O₄) has been of much interest because of its cyclic structure and possible aromaticity. Recently, considerable progress has been made in the crystal engineering of multidimensional arrays and networks containing metal ions as nodes. Squaric acid is a useful tool for constructing crystalline architectures, due to its rigid, planar four membered ring skeleton, and its proton donating and accepting capabilities for hydrogen bonding (Bertolasi et al., 2001; Reetz et al., 1994; Lam & Mak, 2000; Zaman et al., 2001; Mathew et al., 2002). In addition, squaric acid has been studied for potetial application in xerographic photoreceptors, organic solar cells and optical recording (Liebeskind et al., 1993; Seitz & Imming, 1992).

The asymmetric unit of the title compound contains one centrosymmetric cation, where Ni^II is located on a crystallographic inversion centre, one centrosymmetric anion and two uncoordinated water molecules (Fig.1 ), in which the bond lengths (Allen et al., 1987) and angles are within normal ranges. In cation, the Ni^II is hexacoordinated by two O atoms of two water molecules in a trans order and by four N atoms of two pen ligands at the equatorial positions (Table 1). It is suggested that the trans geometry is preferred, when the amine ligand is more bulky. Thus, the coordination environment of Ni^II is a slightly distorted octahedral. Intramolecular O-H···O hydrogen bonds (Table 2) link the cation and anion through the water molecule, while intramolecular N-H···O hydrogen bonds (Table 2) link the cation and anion and cation and water molecule. The six-membered chelate ring (Ni1/N1/N2/C1-C3) is not planar, having total puckering amplitude, Q_T, of 0.765 (3) Å and chair conformation [φ = 166.25 (3) and θ = 40.42 (3) °] (Cremer & Pople, 1975).

In the crystal structure, intermolecular O-H···O and N-H···O hydrogen bonds (Table 2) link the molecules into chains (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, a solution of squaric acid (0.57 g, 5 mmol) in water (25 ml) was neutralized with sodium hydroxide (0.40 g, 10 mmol) and added dropwise with stirring to a solution of Ni(CH₃COO)₂.4(H₂O) (1.24 g, 5 mmol) in water (25 ml) at 323 K. The solution immediately became suspension and was stirred for 2 h. Then, 1,3-propandiamine (0.74 g, 10 mmol) in methanol (10 ml) was added dropwise to the obtained suspension. The clear solution was stirred for 2 h, and then cooled to room temperature. The crystals formed were filtered and washed with water (10 ml) and methanol (1:1), then dried in air. Anal. Calcd. : C 28.12, H 7.55, N 13.12%; Found C 28.06, H 7.61, N 13.18%.