2-(2-Pyrid­yl)pyridinium bis­(pyridine-2,6-dicarboxyl­ato-κ3 O,N,O′)aluminate(III) trihydrate

Janet Soleimannejad; Hossein Aghabozorg; Yaghoub Mohammadzadeh; Shabnam Hooshmand

doi:10.1107/S1600536808015973

. 2008 Jun 7;64(Pt 7):m870–m871. doi: 10.1107/S1600536808015973

2-(2-Pyridyl)pyridinium bis(pyridine-2,6-dicarboxylato-κ³ O,N,O′)aluminate(III) trihydrate

Janet Soleimannejad ^a,^*, Hossein Aghabozorg ^b, Yaghoub Mohammadzadeh ^a, Shabnam Hooshmand ^a

PMCID: PMC2961889 PMID: 21202744

Abstract

The title compound, (C₁₀H₉N₂)[Al(C₇H₃NO₄)₂]·3H₂O or (2,2′-bipyH)[Al(pydc)₂]·3H₂O (where 2,2′-bipy is 2,2′-bipyridine and pydcH₂ is pyridine-2,6-dicarboxylic acid), was synthesized by the reaction of aluminium(III) nitrate nonahydrate with pyridine-2,6-dicarboxylic acid and 2,2′-bipyridine in a 1:2:4 molar ratio in aqueous solution. This compound is composed of an anionic complex, [Al(pydc)₂]⁻, a protonated 2,2′-bipyridine molecule as a counter-ion, (2,2′-bipyH)⁺, and three uncoordinated water molecules. The anion is a six-coordinate complex, with the Al^III atom in a distorted octahedral geometry coordinated by two tridentate pyridine-2,6-dicarboxylate groups. In the crystal structure, intermolecular O—H⋯O, N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds, π–π stacking between two aromatic rings [centroid–centroid distance = 3.827 (10) Å], and C=O⋯π stacking [with distances of 3.2311 (13), 3.4924 (14) and 3.5731 (13) Å], connect the various components to form a supramolecular structure.

Related literature

For related literature, see: Aghabozorg et al. (2007 ▶, 2008 ▶); Aghabozorg, Ghadermazi & Attar Gharamaleki (2006 ▶); Aghabozorg, Ghadermazi & Ramezanipour (2006 ▶).

Experimental

Crystal data

(C₁₀H₉N₂)[Al(C₇H₃NO₄)₂]·3H₂O
M _r = 568.43
Triclinic,
a = 9.3744 (13) Å
b = 10.9039 (16) Å
c = 13.005 (2) Å
α = 106.335 (7)°
β = 98.889 (7)°
γ = 97.521 (7)°
V = 1238.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 150 (2) K
0.32 × 0.32 × 0.15 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.952, T _max = 0.977
25116 measured reflections
4350 independent reflections
3975 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.082
S = 1.07
4350 reflections
361 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015973/su2057sup1.cif

e-64-0m870-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015973/su2057Isup2.hkl

e-64-0m870-Isup2.hkl^{(844KB, 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
O1S—H1B⋯O2	0.85	1.98	2.8166 (14)	166
O1S—H1A⋯O3Sⁱ	0.85	1.92	2.7472 (18)	165
O2S—H2A⋯O1Sⁱⁱ	0.85	1.92	2.7650 (17)	175
O2S—H2B⋯O6	0.85	1.92	2.7703 (16)	174
O3S—H3B⋯O7	0.85	2.02	2.8647 (16)	170
O3S—H3A⋯O2Sⁱⁱⁱ	0.85	1.94	2.7886 (18)	172
N3—H3C⋯O4^iv	0.85	2.04	2.7312 (15)	138
N3—H3C⋯N4	0.85	2.31	2.6497 (19)	104
C12—H12⋯O1Sⁱ	0.95	2.46	3.372 (2)	160
C15—H15⋯O4^iv	0.95	2.52	2.965 (2)	109
C16—H16⋯O2Sⁱⁱⁱ	0.95	2.33	3.248 (2)	162
C17—H17⋯O1^v	0.95	2.25	3.136 (2)	155
C18—H18⋯O8^vi	0.95	2.50	3.331 (2)	146
C1—O1⋯Cg1^vii	1.22 (1)	3.49 (1)	3.9906 (17)	105 (1)
C7—O4⋯Cg2^vi	1.22 (1)	3.23 (1)	3.4319 (17)	89 (1)
C1—O1⋯Cg3^vii	1.22 (1)	3.57 (1)	3.8161 (18)	92 (1)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . Cg1, Cg2 and Cg3 are the centroids of the N1/C2–C6, N3/C15–C19 and N4/C20–C24 rings, respectively.

supplementary crystallographic information

Comment

Our research interests are centered on the preparation of water soluble proton transfer compounds as novel self assembled systems that can function as suitable ligands in the synthesis of metal complexes. In this regard, we have reported cases in which proton transfer from pyridine-2,6-dicarboxylic acid, pydcH₂, and benzene-1,2,4,5-tetracarboxylicacid, btcH₄, to propane-1,3-diamine (pn) and 1,10-phenanthroline, (phen), has occured. This work has resulted in the formation of some novel proton transfer compounds such as (pnH₂)(pydc).(pydcH₂).2.5H₂O (Aghabozorg, Ghadermazi, Ramezanipour, 2006), (pnH₂)₂(btc).2H₂O (Aghabozorg, et al., 2007) and (phenH)₄(btcH₃)₂(btcH₂) (Aghabozorg, Ghadermazi, Attar Gharamaleki, 2006). For more details and related literature see our recent review article (Aghabozorg, et al., 2008).

The molecular structure and the crystal packing diagram of the title compound, (2,2'-bipyH)[Al(pydc)₂].3H₂O, are shown in Figs. 1 and 2, respectively. The title compound is composed of an anionic complex, [Al(pydc)₂]^-, protonated 2,2'-bipyridine as a counter ion, (2,2'-bipyH)⁺, and three uncoordinated water molecules. The Al^III atom is six-coordinated by two pyridine-2,6-dicarboxylate, (pydc)^2-, groups which act as a tridentate ligand through two O and one N atoms. The O5—Al1—O3 and O8—Al1—O2 angles (90.72 (5)° and 91.91 (5)°, repectively) and O5—Al1—O2—C1 and O5—Al1—O3—C7 torsion angles (-98.48 (10)° and 97.57 (10)°, respectively) show that these two (pydc)^2- anions are almost perpendicular to one another. So the anionic complex has a distorted octahedral geometry around the Al^III atom. For balancing the anionic complex, a protonated 2,2'-bipyridinium cation, (2,2'-bipyH)⁺, is present. The O2—Al1—O3 [159.56 (5)^°] and O5—Al1—O8 [159.66 (5)^°] bond angles indicate that the four carboxylate groups of the two dianions are oriented in a flattened tetrahedral arrangement around the Al^III atom.

In the crystal structure of the title compound, the spaces between two layers of [Al(pydc)₂]^- anions are filled with (2,2'-bipyH)⁺ cations and water molecules (Fig. 3). An important feature of the title compound is the presence of π-π and C═O···π staking interactions. The π-π stacking between the aromatic rings of Cg1 (Cg1: N1/C2—C6) and Cg1 [-x, 1 - y, 1 - z], with distances of 3.8271 (10) Å , are observed in Fig. 4. The C═O···π stacking interactions between C1═ O1 and Cg1, C7═O4 and Cg2 [Cg2 centroid of ring N3/C15—C19] and C1═O1 and Cg3 [Cg3 centroid of ring N4/C20—C24] with O···π distances of 3.4924 (14) Å (1 - x, 1 - y, 1 - z), 3.2311 (13) Å (1 - x, 2 - y, 1 - z) and 3.5731 (15) Å (1 - x, 1 - y, 1 - z), respectively, are shown in Fig. 5. Intermolecular O—H···O, N—H···O, N—H···N and C—H···O hydrogen bonds, D···A ranging from 2.6497 (19) Å to 3.372 (2) Å (Table 1), appear to be effective in the stabilization of the crystal structure, resulting in the formation of an interesting supramolecular structure.

Experimental

A solution of Al(NO₃)₃.9H₂O (187 mg, 0.5 mmol) in water (5 ml) was added to an aqueous solution of pyridine-2,6-dicarboxylic acid (167 mg, 1 mmol) and 2,2'-bipyridine (312 mg, 2 mmol) in water (10 ml) in a 1:2:4 molar ratio and refluxed for an hour. Colourless crystals of the title compound were obtained after allowing the mixture to stand for two months at room temperature