Bis(piperazinediium) benzene-1,2,4,5-tetra­carboxyl­ate hexa­hydrate

Hossein Aghabozorg; Faranak Manteghi; Mohammad Ghadermazi

doi:10.1107/S1600536808007332

. 2008 Mar 29;64(Pt 4):o740. doi: 10.1107/S1600536808007332

Bis(piperazinediium) benzene-1,2,4,5-tetracarboxylate hexahydrate

Hossein Aghabozorg ^a,^*, Faranak Manteghi ^a, Mohammad Ghadermazi ^b

PMCID: PMC2960987 PMID: 21202130

Abstract

The title compound, 2C₄H₁₂N₂ ²⁺·C₁₀H₂O₈ ⁴⁻·6H₂O or (pipzH₂)₂(btc)·6H₂O, was formed from the reaction between benzene-1,2,4,5-tetracarboxylic acid (btcH₄) as a proton donor and piperazine (pipz) as a proton acceptor. A variety of O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, as well as C—H⋯π interactions, are present in the crystal structure. Two water O atoms are each disordered over two positions; for both the site occupany factors are ca 0.66 and 0.34.

Related literature

For related literature, see: Aghabozorg et al. (2006 ▶, 2007 ▶); Arora & Pedireddi (2003 ▶); Biradha & Zaworotko (1998 ▶).

Experimental

Crystal data

2C₄H₁₂N₂ ²⁺·C₁₀H₂O₈ ⁴⁻·6H₂O
M _r = 534.52
Triclinic,
a = 6.7420 (4) Å
b = 12.4636 (7) Å
c = 16.0100 (9) Å
α = 99.0920 (10)°
β = 90.3470 (10)°
γ = 105.5280 (10)°
V = 1278.27 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 (2) K
0.23 × 0.21 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.970, T _max = 0.982
13995 measured reflections
5839 independent reflections
4805 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.159
S = 1.02
5839 reflections
323 parameters
H-atom parameters constrained
Δρ_max = 2.20 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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/S1600536808007332/bt2674sup1.cif

e-64-0o740-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007332/bt2674Isup2.hkl

e-64-0o740-Isup2.hkl^{(285.8KB, 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
N1—H1C⋯O5ⁱ	0.92	1.74	2.642 (2)	166
N1—H1D⋯O7ⁱⁱ	0.92	1.84	2.763 (2)	178
N2—H2C⋯O1ⁱⁱⁱ	0.92	1.82	2.723 (2)	165
N2—H2D⋯O4	0.92	1.72	2.635 (2)	179
N3—H3C⋯O2ⁱⁱⁱ	0.92	1.90	2.787 (2)	163
N3—H3D⋯O6	0.92	1.92	2.690 (2)	141
N4—H4C⋯O8^iv	0.92	1.85	2.753 (2)	168
N4—H4D⋯O3	0.92	2.00	2.748 (2)	138
O1S—H1SA⋯O5SA	0.82	2.02	2.837 (2)	172
O1S—H1SA⋯O5SA	0.82	2.02	2.837 (2)	172
O1S—H1SB⋯O2^v	0.82	1.95	2.763 (2)	172
O2S—H2SA⋯O4Sⁱⁱⁱ	0.82	2.04	2.839 (2)	165
O2S—H2SB⋯O8^vi	0.82	2.05	2.835 (2)	160
O3S—H3SA⋯O2S	0.82	1.90	2.722 (2)	176
O3S—H3SB⋯O5ⁱⁱ	0.82	2.00	2.817 (2)	171
O4S—H4SA⋯O1	0.82	1.95	2.772 (2)	175
O4S—H4SB⋯O3S	0.82	1.95	2.764 (2)	170
C5—H5A⋯O6SA	0.99	2.50	3.288 (4)	136
C5—H5B⋯O7^iv	0.99	2.35	3.272 (3)	154
C7—H7A⋯O1ⁱⁱⁱ	0.99	2.48	3.414 (3)	156
C8—H8B⋯O4Sⁱⁱⁱ	0.99	2.51	3.299 (3)	137
C4—H4B⋯Cg1ⁱⁱ	0.99	2.64	3.518 (2)	148
C4—H4B⋯Cg1^vi	0.99	2.64	3.518 (2)	148

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . Cg1 is the centroid of the C14,C15,C16,C14′,C15′,C16′ benzene ring.

Acknowledgments

The authors acknowledge Tarbiat Moallem University for supporting this work.

supplementary crystallographic information

Comment

Continuing the path to synthesize proton transfer compounds, our team works have recently been focused on forming ion pairs between benzene-1,2,4,5-tetracarboxylic acid and various organic bases such as propane-1,3-diamine (Aghabozorg et al., 2007) and 1,10-phenanthroline (Aghabozorg et al., 2006). Due to its flat and symmetric structure and four proton donor sites, benzene-1,2,4,5-tetracarboxylic acid has a potential of constructing a supramolecular network. Supramolecular assemblies of 1,2,4,5-benzenetetracarboxylic acid, with aza donor molecules such as 1,10-phenanthroline, 1,7-phenanthroline, phenazine, 4-(N,N-dimethylamino)pyridine, 1,2-bis(4-pyridyl)ethene, and 1,2-bis(4- pyridyl)ethane have been synthesized and characterized by single-crystal X-ray diffraction methods (Arora et al., 2003). Among the known structures, cyclic network mediated supramolecular assemblies of benzene-1,2,4,5-tetracarboxylic acid with pyridine and some of its derivatives is quite significant (Biradha et al., 1998). The title compound has a structure constituted of one fully deprotonated benzene-1,2,4,5-tetracarboxylic acid unit, two doubly protonated piperazine units and six water molecules, two of which are disordered.

Various hydrogen bonds are formed between the named fragments, the water molecules are hydrogen bonded to each other and to carboxylate groups by O—H···O bonds, piperazinium ions are linked to carboxylate groups by N—H···O bonds, also the carbon atoms of piperaziniedium ion have C—H···O hydrogen bonds to oxygen atoms of water molecules and carboxyl groups. It is notable that the shortest hydrogen bond N2—H2D···O4 has the least deviation i.e. 1° from linearity. As shown in Fig. 2, in the cell packing there are six water molecules surrounded by cationic and anionic fragments. So if the structure expanded and the layers appeared, it can be seen a channel in which water molecules are trapped. This is previously observed for ion pairs of the tetraacid (Arora et al., 2003), in which the three-dimensional arrangement of the layers are stacked such that the cavities align to yield channels. It appears that the size and direction of water molecules plays an important role in constructing of channel structures in the supramolecular assemblies of acid.

As shown in Fig. 3, there are C—H···π interactions between C4—H4B bond of piperazinium ion and two benzene rings containing C14, C15 and C16 atoms with different symmetry codes [(x, y - 1, z), (-x, -y + 1, 1 - z)] for which the C—H···π distance and angle are 3.518 (2) Å and 148°, respectively.

Finally in Fig. 4, it can be seen how ribbons of constituents of the compound are arranged.

Experimental

For synthesizing the title compoud, a solution of 2540 mg (10 mmol) benzene-1,2,4,5-tetracarboxylic acid in 10 ml tetrahydrofuran and another solution of 860 mg (10 mmol) of piperazine in 10 ml of the same solvent were prepared and mixed. By heating, a white precipitate was obtained. The colorless prisms of the compound were obtained by recrystallization from water solution.