Piperazine-1,4-diium naphthalene-1,5-disulfonate

Bin Wei

doi:10.1107/S1600536811038955

. 2011 Sep 30;67(Pt 10):o2811. doi: 10.1107/S1600536811038955

Piperazine-1,4-diium naphthalene-1,5-disulfonate

Bin Wei ^a,^*

PMCID: PMC3201365 PMID: 22065696

Abstract

The title molecular salt, C₄H₁₂N₂ ²⁺·C₁₀H₆O₆S₂ ²⁻, consists of a piperazinium cation and a 1,5-naphthalenedisulfonate anion. Crystallographic inversion centers are situated at the center of the ring of the dication as well as at the midpoint of the central carbon–carbon bond in the dianion. In the crystal, intermolecular N—H⋯O hydrogen bonds link the cations and anions.

Related literature

The title compound was obtained during attempts to obtain dielectric-ferroelectric compounds. For general background to ferroelectric metal-organic frameworks, see: Wu et al. (2011 ▶); Ye et al. (2006 ▶); Zhang et al. (2008 ▶, 2010 ▶); Fu et al. (2009 ▶).

Experimental

Crystal data

C₄H₁₂N₂ ²⁺·C₁₀H₆O₆S₂ ²⁻
M _r = 374.42
Monoclinic,
a = 11.997 (2) Å
b = 7.2959 (15) Å
c = 9.1453 (18) Å
β = 96.00 (3)°
V = 796.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.955, T _max = 0.955
7956 measured reflections
1827 independent reflections
1629 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.088
S = 1.11
1827 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811038955/vm2121sup1.cif

e-67-o2811-sup1.cif^{(13.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038955/vm2121Isup2.hkl

e-67-o2811-Isup2.hkl^{(90KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811038955/vm2121Isup3.cml

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—H1A⋯O2ⁱ	0.90	1.91	2.7357 (19)	153
N1—H1B⋯O3ⁱⁱ	0.90	1.91	2.7670 (19)	159

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

Acknowledgments

The author is grateful to the starter fund of Southeast University for the purchase of the diffractometer.

supplementary crystallographic information

Comment

Dielectric-ferroelectrics are an interesting class of materials, comprising organic ligands,metal-organic coordination compounds and organic-inorganic hybrids (Fu et al., 2009; Zhang et al., 2010; Zhang et al., 2008; Ye et al., 2006). Unfortunately, the dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent. Below the melting point (402-403K) of the compound, we have found that the title compound has no dielectric disuniformity from 80 K to 405 K. Here we descibe the crystal structure of this compound.

The asymmetric unit of the title compound consists of a half piperazinium cation and a half 1,5-naphthalenedisulfonate anion (Fig. 1). The complete complete molecular structures are generated by inversion centers at the center of the piperazinium ring and at the midpoint of the central carbon-carbon bond in the naphthalene ring. The best planes through the piperazinium ring and the naphthalene ring make a dihedral angle of 80.96 (8)°. The cations and anions are connected by intermolecular N—H···O hydrogen bonds, which contribute to the stability of the crystal structure (Fig. 2 and Table 1).

Experimental

The title compound was obtained by the addition of 1,5-naphthalenedisulfonate acid (3.62 g, 0.01 mol) to a solution of piperazine (0.88 g, 0.01 mol) in water, in the stoichiometric ratio 1: 1. Good quality single crystals were obtained by slow evaporation after two days (yield: 48%).