Benzene-1,3-diammonium bis­(pyridine-2,6-dicarboxyl­ato)nickelate(II) penta­hydrate

Hoda Pasdar; Saghi Sadat Kashani; Hossein Aghabozorg; Behrouz Notash

doi:10.1107/S1600536810054371

. 2011 Jan 15;67(Pt 2):m193–m194. doi: 10.1107/S1600536810054371

Benzene-1,3-diammonium bis(pyridine-2,6-dicarboxylato)nickelate(II) pentahydrate

Hoda Pasdar ^a, Saghi Sadat Kashani ^a,^*, Hossein Aghabozorg ^a, Behrouz Notash ^b

PMCID: PMC3051631 PMID: 21522862

Abstract

In the title compound, (C₆H₁₀N₂)[Ni(C₇H₃NO₄)₂]·5H₂O, the Ni^II ion is six-coordinated by two N and four O atoms from two pyridine-2,6-dicarboxylate ligands in a distorted octahedral fashion. The crystal packing is stabilized by intermolecular O—H⋯O and N—H⋯O and weak C—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distances = 3.4669 (19) and 3.764 (2) Å].

Related literature

For background to proton-transfer compounds, see: Aghabozorg et al. (2008 ▶). For related structures, see: Aghabozorg et al. (2009 ▶); Beatty et al. (2002 ▶); Dobrzycki & Woźniak (2008 ▶); Attar Gharamaleki et al. (2009 ▶); Imaz et al. (2007 ▶); MacDonald et al. (2000 ▶, 2004 ▶); Sharif et al. (2007 ▶).

Experimental

Crystal data

(C₆H₁₀N₂)[Ni(C₇H₃NO₄)₂]·5H₂O
M _r = 589.14
Monoclinic,
a = 7.5331 (15) Å
b = 18.085 (4) Å
c = 18.578 (4) Å
β = 100.90 (3)°
V = 2485.3 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.86 mm⁻¹
T = 298 K
0.20 × 0.15 × 0.10 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 2005 ▶) T _min = 0.855, T _max = 0.920
18439 measured reflections
6687 independent reflections
3608 reflections with I > 2σ(I)
R _int = 0.090

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.086
S = 0.92
6687 reflections
407 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; 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, global. DOI: 10.1107/S1600536810054371/bt5430sup1.cif

e-67-0m193-sup1.cif^{(26.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810054371/bt5430Isup2.hkl

e-67-0m193-Isup2.hkl^{(327.3KB, 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
C18—H18⋯O2ⁱ	0.93	2.48	3.118 (4)	126
C3—H3⋯O7ⁱⁱ	0.93	2.56	3.284 (4)	135
O13—H13B⋯O9ⁱⁱⁱ	0.82 (5)	2.14 (5)	2.945 (6)	166 (5)
O13—H13A⋯O6^iv	0.76 (4)	2.05 (4)	2.776 (5)	158 (6)
O12—H12B⋯O13^v	0.79 (4)	2.02 (4)	2.808 (5)	176 (8)
O12—H12A⋯O3^vi	0.89 (6)	1.95 (6)	2.838 (4)	174 (5)
O11—H11B⋯O9	0.75 (3)	2.08 (3)	2.829 (4)	173 (5)
O11—H11A⋯O7	0.79 (4)	2.03 (4)	2.798 (4)	163 (4)
O10—H10B⋯O2	0.97 (5)	1.80 (5)	2.750 (4)	168 (5)
O10—H10A⋯O12^vii	0.79 (3)	2.20 (5)	2.880 (5)	146 (6)
O9—H9B⋯O4ⁱⁱ	0.85 (5)	2.07 (5)	2.918 (4)	172 (5)
O9—H9A⋯O10	0.86 (5)	1.91 (5)	2.772 (5)	176 (4)
N4—H4C⋯O6^viii	0.97 (4)	1.78 (4)	2.730 (4)	167 (3)
N4—H4B⋯O4^vi	0.82 (3)	2.05 (4)	2.854 (4)	168 (3)
N4—H4A⋯O11	0.91 (4)	1.94 (4)	2.842 (4)	173 (3)
N3—H3C⋯O1	0.91 (5)	1.82 (5)	2.702 (4)	164 (4)
N3—H3B⋯O8^vii	0.93 (5)	1.85 (5)	2.773 (4)	173 (4)
N3—H3A⋯O12^vii	0.91 (4)	2.07 (4)	2.899 (5)	152 (4)

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

Acknowledgments

The authors are grateful to the Islamic Azad University, North Branch, for financial support of this work.

supplementary crystallographic information

Comment

Pyridine-2,6-dicarboxylic acid (pydcH₂) was commonly used as an acid in proton transfer systems (Aghabozorg et al. 2008). It has been reported that several proton transfer systems containing the anionic [Ni(pydc)₂]^2- moiety and different cationic parts (Aghabozorg et al. 2009; Attar Gharamaleki et al. 2009; MacDonald et al. 2000; MacDonald et al. 2004; Sharif et al. 2007). In addition, the formation of mono (Beatty et al. 2002) and diprotonated benzene-1,3-diamine (Dobrzycki & Woźniak 2008; Imaz et al. 2007) have been observed previously.

In the title compound, (bdaH₂)[Ni(pydc)₂].5H₂O, the anionic part is comprised of a Ni^II ion which is six-coordinated by two pyridyl nitrogen and four oxygen atoms from pydc ligands. The Ni(II) ion has a distorted octahedral geometry. (Fig. 1). Bond lengths for Ni—O and Ni—N and angles (Table 1) are in normal ranges (Aghabozorg et al. 2009; Attar Gharamaleki et al. 2009; Sharif et al. 2007). Crystal packing is stabilized by intermolecular O—H···O, N—H···O and weak C—H···O intermolecular hydrogen bonds which formed between [Ni(pydc)₂]^2-, (bdaH₂)²⁺ and water molecules (Fig. 2 & Table 2). There are also π-π interactions between pyridine rings of pydc and between benzene ring of (bdaH₂)²⁺ and pyridine ring of pydc molecule by distances Cg5···Cg5^ix and Cg6···Cg7 of 3.4669 (19) and 3.764 (2) Å, respectively. [Cg5, Cg6 and Cg7 are centroids of N1/C1—C6, N2/C8—C12 and C15—C20 rings, respectively. Symmetry code: (ix) 1 - x,2 - y,2 - z]. Intermolecular π-π interactions are shown in Fig. 3.

Experimental

A solution of pyridine-2,6-dicarboxylic acid (pydcH₂) (162 mg, 0.9 mmol) in 15 ml water was added to a solution of benzene-1,3-diamine (bda) (108 mg, 0.6 mmol) in 12 ml water and stirred for half an hour. Then a solution of NiCl₂.6H₂O (7 mg, 0.7 mmol) in 5 ml water was added to the solution of pydcH₂ and bda. The resulted solution was stirred for 2 hrs and green crystals of the title compound were obtained after one week which were suitable for X-ray analysis (m.p 200°C).