Piperazine-1,4-diium pyridine-2,3-dicarboxyl­ate methanol monosolvate

Faranak Manteghi; Mohammad Ghadermazi; Nasrin Kakaei

doi:10.1107/S1600536811012384

. 2011 Apr 13;67(Pt 5):o1122. doi: 10.1107/S1600536811012384

Piperazine-1,4-diium pyridine-2,3-dicarboxylate methanol monosolvate¹

Faranak Manteghi ^a, Mohammad Ghadermazi ^b,^*, Nasrin Kakaei ^b

PMCID: PMC3089228 PMID: 21754436

Abstract

The title solvated molecular salt, C₄H₁₂N₂ ²⁺·C₇H₃NO₄ ²⁻·CH₃OH or (pipzH₂)(py-2,3-dc)·MeOH, was prepared by the reaction of pyridine-2,3-dicarboxylic acid (py-2,3-dcH₂) and piperazine (pipz) in methanol (MeOH) as solvent. One of the two carboxylate groups of the acid fragment is nearly perpendicular to the pyridine ring and the other is almost in its plane [C—C—C—O torsion angles = −85.50 (11) and 88.07 (11)° and N—C—C—O torsion angles = −176.31 (8) and 5.41 (13)°]. In the crystal, the components are linked by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, generating a three-dimensional network.

Related literature

For similar ion pairs, see: Aghabozorg, Manteghi & Ghadermazi (2008 ▶); Aghabozorg, Manteghi & Sheshmani (2008 ▶). For related metal complexes, see: Barszcz et al. (2010 ▶); Li & Li (2004 ▶).

Experimental

Crystal data

C₄H₁₂N₂ ²⁺·C₇H₃NO₄ ²⁻·CH₄O
M _r = 285.30
Monoclinic,
a = 8.2541 (6) Å
b = 11.8988 (8) Å
c = 13.8197 (9) Å
β = 90.288 (2)°
V = 1357.27 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.25 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEXII diffractometer
16044 measured reflections
3579 independent reflections
3189 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.085
S = 1.03
3579 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012384/om2416sup1.cif

e-67-o1122-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012384/om2416Isup2.hkl

e-67-o1122-Isup2.hkl^{(175.5KB, 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
N2—H2A⋯O4ⁱ	0.90	1.74	2.6257 (11)	168
N2—H2B⋯O2	0.90	1.89	2.7274 (11)	155
N3—H3A⋯O1ⁱⁱ	0.90	1.85	2.7379 (11)	169
N3—H3B⋯O3ⁱⁱⁱ	0.90	1.86	2.7393 (11)	166
O5—H5A⋯O1	0.85	1.84	2.6867 (10)	171
C3—H3⋯O5^iv	0.95	2.41	3.3163 (13)	159

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

Acknowledgments

We acknowledge financial support of this work by the Iran University of Science and Technology and the University of Kurdistan.

supplementary crystallographic information

Comment

Pyridine-2,3-dicarboxylic acid is remarkably attractive for its flexible and variable coordination modes to construct polymeric architecture. It can act as monodicarboxylate chelating anion, or tridentate coordinating anion with acid hydrogen on nitrogen and doubly deprotonated, tridentate dicarboxylate anion (py-2,3-dc) and even in Mn(II) complexes as tetradenatate and pentadentate ligands (Barszcz et al., 2010; Li & Li, 2004). Preparation of ion pairs with the acid increases the chance of its coordination to metals. Therefore, in our work to obtain proton transfer ion pairs, we have reviewed many ion pairs and their metal complexes (Aghabozorg, Manteghi & Sheshmani, 2008). Also, we have reported a similar ion pair formulated as (pipzH₂)(pydcH)₂, (Aghabozorg, Manteghi & Ghadermazi, 2008). The title structure, as shown in Fig. 1, has an asymmetric unit constructed by (pipzH₂)²⁺ and (py-2,3-dc)^2– and a neutral methanol molecule with two hydrogen bonds. There are varieties of other strong and weak hydrogen bonds in the structure, shown in Table 1. Also, a C–O···π stacking, between C6–O2 and N1/C1-C5 ring (-x, -y + 2, -z) with the distance of 3.5240 (9) Å, and a C–H···π stacking, between C12–H1A and N1/C1-C5 ring (x +1/2, -y +3/2, z -1/2), with the distance of 2.791 (1) Å, shown in Fig. 2 are observed.

Experimental

The title compound was synthesized via reaction of 1670 mg (10 mmol) pyridine-2,3-dicarboxylic acid with 860 mg (10 mmol) piperazine in a methanol solution (60 ml). The obtained white precipitate was filtered out and dissolved in water to recrystallize. Colorless crystals of the title compound were obtained after 14 days.