Benzene-1,3-diammonium bis­(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)cobaltate(II) penta­hydrate

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

doi:10.1107/S1600536811009858

. 2011 Mar 31;67(Pt 4):m507–m508. doi: 10.1107/S1600536811009858

Benzene-1,3-diammonium bis(pyridine-2,6-dicarboxylato-κ³ O ²,N,O ⁶)cobaltate(II) pentahydrate

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

PMCID: PMC3099797 PMID: 21754013

Abstract

In the title compound, (C₆H₁₀N₂)[Co(C₇H₃NO₄)₂]·5H₂O, the Co^II ion is six-coordinated in an N₂O₄ environment by two pyridine-2,6-dicarboxylate (pydc) ligands, having a distorted octahedral geometry. The crystal packing is stabilized by intermolecular N—H⋯O, O—H⋯O and weak C—H⋯O hydrogen bonds. There are also π–π interactions between the pyridine rings of the pydc ligands and between the pydc ligands and the benzene-1,3-diammonium cations, with centroid–centroid distances of 3.4575 (15) and 3.7521 (15) Å.

Related literature

For general background to proton-transfer compounds, see: Aghabozorg et al. (2008 ▶). For related structures, see: Beatty et al. (2002 ▶); Dobrzycki & Woźniak (2008 ▶); Imaz et al. (2007 ▶); Pasdar et al. (2010 ▶, 2011a ▶,b ▶).

Experimental

Crystal data

(C₆H₁₀N₂)[Co(C₇H₃NO₄)₂]·5H₂O
M _r = 589.38
Monoclinic,
a = 7.5236 (2) Å
b = 18.0200 (7) Å
c = 18.7122 (6) Å
β = 100.883 (2)°
V = 2491.29 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 298 K
0.50 × 0.15 × 0.10 mm

Data collection

Stoe IPDS-2 diffractometer
19874 measured reflections
6702 independent reflections
5366 reflections with I > 2σ(I)
R _int = 0.064

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.113
S = 1.21
6702 reflections
407 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.32 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 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811009858/hy2407sup1.cif

e-67-0m507-sup1.cif^{(25.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009858/hy2407Isup2.hkl

e-67-0m507-Isup2.hkl^{(328KB, 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
C10—H10⋯O3ⁱ	0.93	2.57	3.311 (3)	136
C18—H18⋯O8ⁱⁱ	0.93	2.47	3.099 (3)	125
O9—H9A⋯O3	0.86 (4)	1.97 (4)	2.789 (3)	160 (3)
O9—H9B⋯O10	0.76 (3)	2.07 (3)	2.833 (4)	176 (4)
O10—H10A⋯O6ⁱ	0.81 (6)	2.10 (6)	2.913 (4)	173 (5)
O10—H10B⋯O11	0.80 (5)	1.97 (5)	2.764 (5)	170 (5)
O11—H11A⋯O8	0.97 (5)	1.84 (5)	2.746 (4)	153 (4)
O11—H11B⋯O13ⁱⁱⁱ	0.86 (5)	2.08 (5)	2.907 (4)	161 (5)
O12—H12A⋯O10	0.93 (7)	2.03 (7)	2.946 (5)	171 (5)
O12—H12B⋯O2^iv	0.73 (5)	2.09 (5)	2.786 (4)	161 (5)
O13—H13A⋯O12	0.86 (3)	1.95 (3)	2.805 (4)	176 (5)
O13—H13B⋯O5^v	0.78 (5)	2.13 (5)	2.873 (3)	161 (5)
N3—H3A⋯O4ⁱⁱⁱ	0.87 (4)	1.93 (4)	2.791 (3)	169 (3)
N3—H3B⋯O7	0.96 (4)	1.78 (4)	2.714 (3)	163 (3)
N3—H3C⋯O13ⁱⁱⁱ	0.98 (4)	2.04 (4)	2.890 (4)	144 (3)
N3—H3C⋯O9ⁱⁱⁱ	0.98 (4)	2.29 (4)	2.899 (3)	120 (3)
N4—H4A⋯O9	0.89 (4)	1.97 (4)	2.844 (3)	168 (4)
N4—H4B⋯O2^iv	0.90 (4)	1.87 (4)	2.752 (3)	166 (3)
N4—H4C⋯O6^v	0.88 (4)	2.00 (4)	2.873 (3)	175 (3)

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

Acknowledgments

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

supplementary crystallographic information

Comment

Our group used pyridine-2,6-dicarboxylic acid (pydcH₂) in several proton-transfer systems (Aghabozorg et al., 2008; Pasdar et al., 2010, 2011a,b). Benzene-1,3-diamine (bda) has ability to act as a proton acceptor in proton-transfer compounds. The formation of mono- (Beatty et al., 2002) and diprotonated benzene-1,3-diamine (Dobrzycki & Woźniak, 2008; Imaz et al., 2007) has been observed previously.

Herein, we report the synthesis and crystal structure of the title compound (Fig. 1). The Co^II ion in the complex anion is six-coordinated by two tridentate pydc ligands in a distorted octahedral geometry. We have recently reported the synthesis and crystal structure of a nickle(II) analogue, (bdaH₂)[Ni(pydc)₂].5H₂O (Pasdar et al., 2011b). The nickle(II) and cobalt(II) complexes are isostructural. Crystal packing of the title compound is stabilized by intermolecular N—H···O, O—H···O and weak C—H···O hydrogen bonds (Fig. 2, Table 1). There are also π–π interactions between the pyridine rings of the pydc ligands and between the pyridine ring of the pydc ligand and the benzene ring of the benzene-1,3-diammonium cation, with centroid–centroid distances of 3.4575 (15) and 3.7521 (15) Å.

Experimental

A solution of pydcH₂ (162 mg, 0.9 mmol) in 17 ml water was added to a solution of bda (108 mg, 0.6 mmol) in 11 ml water with stirring for an hour, and then a solution of CoCl₂.6H₂O (118 mg, 0.6 mmol) in 5 ml water was added. The resulting solution was stirred for 2 h and dark pink crystals of the title compound suitable for X-ray analysis were obtained after one week (m.p. 260°C).