Piperazine-1,4-diium bis­(pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)cobaltate(II) tetra­hydrate

Akbar Raissi Shabari; Nazanin Ghoddoosi; Mehrdad Pourayoubi; Shahram Moradi

doi:10.1107/S1600536811023518

. 2011 Jun 25;67(Pt 7):m985–m986. doi: 10.1107/S1600536811023518

Piperazine-1,4-diium bis(pyridine-2,6-dicarboxylato-κ³ O ²,N,O ⁶)cobaltate(II) tetrahydrate

Akbar Raissi Shabari ^a,^*, Nazanin Ghoddoosi ^a, Mehrdad Pourayoubi ^b, Shahram Moradi ^a

PMCID: PMC3151836 PMID: 21836959

Abstract

The asymmetric unit of the title complex, (C₄H₁₂N₂)[Co(C₇H₃NO₄)₂]·4H₂O, consists of one piperazinediium dication, one [Co(py-2,6-dc)₂]²⁻ dianion (where py-2,6-dc is pyridine-2,6-dicarboxylate) and four water molecules. The piperazinediium cation adopts a chair conformation and the Co^II ion is six-coordinated in an N₂O₄ environment, having a distorted octahedral geometry. In the crystal, intermolecular O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds link the components, forming a three-dimensional network.

Related literature

The structure determination of title compound was performed as a part of our project on the synthesis of new proton-transfer compounds, see: Raissi Shabari et al. (2010 ▶). For bond lengths in a related cobaltate(II) complex, see: Pasdar et al. (2011 ▶). For bond lengths and angles in the piperazinediium dication, see: Sutherland & Harrison (2009 ▶); Allen et al. (1995 ▶). For positive-charge-assisted hydrogen bonds, see: Gilli et al. (1994 ▶).

Experimental

Crystal data

(C₄H₁₂N₂)[Co(C₇H₃NO₄)₂]·4H₂O
M _r = 549.36
Monoclinic,
a = 7.9537 (16) Å
b = 13.420 (3) Å
c = 21.004 (4) Å
β = 90.55 (3)°
V = 2241.8 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 150 K
0.5 × 0.40 × 0.15 mm

Data collection

Stoe IPDS 2T diffractometer
Absorption correction: numerical [shape of crystal determined optically (X-RED and X-SHAPE; Stoe & Cie, 2005 ▶)] T _min = 0.670, T _max = 0.878
15339 measured reflections
6018 independent reflections
5226 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.077
S = 1.07
6018 reflections
364 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.33 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 ▶) and enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811023518/lh5266sup1.cif

e-67-0m985-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023518/lh5266Isup2.hkl

e-67-0m985-Isup2.hkl^{(294.6KB, 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
O12—H12B⋯O3ⁱ	0.79 (3)	2.06 (3)	2.8428 (18)	174 (3)
O11—H11B⋯O5	0.83 (3)	2.00 (3)	2.8290 (18)	177 (3)
O11—H11A⋯O1ⁱⁱ	0.81 (3)	2.02 (3)	2.8173 (19)	170 (3)
O10—H10B⋯O7	0.79 (3)	2.15 (3)	2.9213 (19)	165 (3)
O10—H10A⋯O11ⁱⁱⁱ	0.87 (3)	1.99 (3)	2.854 (2)	172 (3)
O9—H9B⋯O8	0.79 (3)	1.96 (3)	2.7521 (18)	175 (2)
O9—H9A⋯O12^iv	0.83 (3)	2.01 (3)	2.840 (2)	173 (3)
N4—H4B⋯O3^v	0.89 (2)	1.92 (2)	2.7973 (18)	165 (2)
N4—H4A⋯O6ⁱⁱⁱ	0.91 (2)	1.89 (2)	2.7592 (17)	161 (2)
N3—H3B⋯O9^vi	0.91 (2)	1.86 (2)	2.6958 (18)	152 (2)
N3—H3A⋯O2	0.91 (2)	2.50 (2)	3.1126 (19)	124.5 (18)
N3—H3A⋯O1	0.91 (2)	1.88 (2)	2.7957 (18)	176 (2)
C18—H18B⋯O10^vii	0.97	2.58	3.457 (2)	151
C17—H17B⋯O7^vii	0.97	2.36	3.127 (2)	135
C16—H16B⋯O12^iv	0.97	2.52	3.293 (2)	137
C15—H15B⋯O10^vi	0.97	2.60	3.261 (2)	126
C15—H15A⋯O2	0.97	2.54	3.140 (2)	120

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

Acknowledgments

Support of this investigation by the North Tehran Branch, Islamic Azad University, is gratefully acknowledged.

supplementary crystallographic information

Comment

The structure determination of title compound was performed as a part of a project on the synthesis of new proton-transfer compounds (Raissi Shabari et al., 2010).

The Co atom in title compound adopts a distorted octahedral coordination arising from four oxygen and two nitrogen atoms of two pyridine-2,6-dicarboxylato ligands, Fig. 1. The Co—O and Co—N bond lengths are similar to those in a recently published bis(pyridine-2,6-dicarboxylato)cobaltate(II) complex, (C₆H₁₀N₂)[Co(C₇H₃NO₄)₂].5H₂O (Pasdar et al., 2011). The organic dication adopts a typical chair geometry with normal bond lengths and angles (Sutherland & Harrison, 2009; Allen et al., 1995).

The protonated piperazine nitrogen atoms are involved in positive charge assisted (Gilli et al., 1994) N—H···O hydrogen bonds, atom N3 is involved with the O atoms of an adjacent carbonyl of one pyridine-2,6-dicarboxylato ligand and a neighbouring H₂O molecule and atom N4 with two pyridine-2,6-dicarboxylato ligands in two neighbouring complexes.

Cations, anions and four crystallographically independent H₂O molecules are hydrogen bonded in a three-dimensional network through N—H···O, O—H···O and weak C—H···O hydrogen bonds (Table 1).

Experimental

A solution of Co(NO₃)₂.6H₂O (2 mmol) in H₂O was added to a solution of pyridine-2,6-dicarboxylic acid (4 mmol) in H₂O and stirred (45 minutes) at room temperature. To the resulting solution, a solution of piperazine (4 mmol) in H₂O was added and stirred (4 h) at 323 K. Suitable single crystals for X-ray analysis were obtained after slow evaporation at room temperature. IR (KBr, ν, cm^-1): 3425, 3240, 3013, 3001, 2725, 2467, 1608, 1568, 1425, 1371, 1279, 1182, 1074, 1036, 914, 824, 760, 733, 692, 677, 592, 534.