Hemipiperazinediium bis­(pyridine-2,6-dicarboxyl­ato-κ3 O,N,O′)gallate(III) pyridine-2,6-dicarboxylic acid dihydrate

Masoud Rafizadeh; Andya Nemati; Zohreh Derikvand

doi:10.1107/S1600536808029140

. 2008 Sep 20;64(Pt 10):m1298–m1299. doi: 10.1107/S1600536808029140

Hemipiperazinediium bis(pyridine-2,6-dicarboxylato-κ³ O,N,O′)gallate(III) pyridine-2,6-dicarboxylic acid dihydrate

Masoud Rafizadeh ^a,^*, Andya Nemati ^a, Zohreh Derikvand ^a

PMCID: PMC2959419 PMID: 21201039

Abstract

The asymmetric unit of the title compound, (C₄H₁₂N₂)_0.5[Ga(pydc)₂]·pydcH₂·2H₂O, where pydcH₂ is pyridine-2,6-dicarboxylic acid, C₇H₅NO₄, contains one half of a centrosymmetric piperazinediium dication, one anion, one uncoordinated pydcH₂ molecule and two uncoordinated water molecules, one of which is disordered over two sites in a 1:1 ratio. In the anion, the Ga^III ion is coordinated by four O atoms [Ga—O = 1.9706 (16)–2.0494 (15) Å] and two N atoms [Ga—N = 1.9660 (18) and 1.9709 (17) Å] from two pydc ligands in a distorted octahedral geometry. The crystal structure exhibits intermolecular O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonds and π–π interactions [centroid–centroid distances of 3.5359 (13) and 3.6550 (14) Å].

Related literature

For self-assembling systems involving pydcH₂, see: Aghabozorg et al. (2006a ▶,b ▶). For related complexes of the pyridine-2,6-dicarboxylate ligand with transition metals, see: Rafizadeh et al. (2005 ▶, 2006 ▶); Rafizadeh & Amani (2006 ▶); Aghabozorg et al. (2007 ▶, 2008 ▶). For details of the synthesis, see: Sheshmani et al. (2006 ▶).

Experimental

Crystal data

(C₄H₁₂N₂)_0.5[Ga(C₇H₃NO₄)₂·C₇H₅NO₄·2H₂O
M _r = 647.16
Triclinic,
a = 8.6434 (4) Å
b = 11.8582 (5) Å
c = 13.7907 (6) Å
α = 65.7151 (10)°
β = 80.0391 (10)°
γ = 86.9150 (11)°
V = 1268.74 (10) Å³
Z = 2
Mo Kα radiation
μ = 1.17 mm⁻¹
T = 120 (2) K
0.25 × 0.20 × 0.18 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1998 ▶) T _min = 0.749, T _max = 0.807
13018 measured reflections
6067 independent reflections
5263 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.099
S = 1.00
6067 reflections
382 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; 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/S1600536808029140/cv2438sup1.cif

e-64-m1298-sup1.cif^{(27.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808029140/cv2438Isup2.hkl

e-64-m1298-Isup2.hkl^{(879.5KB, 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
N4—H4B⋯O13ⁱ	0.92	1.84	2.754 (3)	169
N4—H4C⋯O14	0.92	1.94	2.818 (4)	160
N4—H4C⋯O14′	0.92	1.85	2.681 (4)	150
O9—H9O⋯O8ⁱⁱ	0.89	1.90	2.710 (2)	150
O11—H11O⋯O8ⁱⁱ	0.87	1.91	2.725 (2)	155
O13—H13A⋯O4	0.97	1.88	2.823 (3)	163
O13—H13B⋯O2ⁱⁱⁱ	0.92	1.84	2.765 (3)	175
O14—H14A⋯O10	0.91	1.95	2.798 (5)	153
O14—H14B⋯O1^iv	0.96	2.15	2.974 (5)	143
N4—H4C⋯O12ⁱⁱ	0.92	2.50	2.863 (3)	104
O9—H9O⋯N3	0.89	2.20	2.678 (3)	113
O11—H11O⋯N3	0.87	2.22	2.690 (2)	114

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

supplementary crystallographic information

Comment

In continuation of our study of self-assembling systems (pipzH₂)₃²⁺[In(pydc)₃]₂^3-.12H₂O, (pipzH₂)²⁺[Tl₂(pydc)₂Cl₄(H₂O)₂]^2-.4H₂O and some others (Aghabozorg et al., 2006a,b), we present here the crystal structure of the title compound, (I).

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in the related complexes of pyridine-2,6-dicarboxylate ligand with transition metals (Rafizadeh et al., 2005; Rafizadeh, Mehrabi & Amani, 2006; Rafizadeh & Amani, 2006; Aghabozorg et al., 2007, 2008). In the anion, the angles O1—Ga—O3 [158.69 (6)°], O5—Ga—O7 [158.65 (6)°] and N1—Ga—N2 [171.11 (7)°] indicate that the coordination environment around Ga^III ion is a distorted octahedron.

In the crystal, the π–π interactions (Table 1) and extensive three-dimensional network of intermolecular O—H···O, O—H···N and N—H···O hydrogen bonds (Table 2) contribute to the crystal packing stability.

Experimental

The proton transfer compound (pipzH₂)(pydcH)₂.3H₂O, was prepared by the reaction of pyridine-2,6-dicarboxylic acid, pydcH₂, with piperazine, pipz, (Sheshmani et al., 2006). The reaction between Ga(NO₃)₃.8H₂O (200.0 mg, 0.5 mmol) in water (25 ml) and the proton transfer compound (pipzH₂)(pydcH)₂.3H₂O (253.0 mg, 1.0 mmol) in water (25 ml), in a 1:2 molar ratio was carried by slow evaporation of the solvent at room temperature.