Dimethyl­ammonium guanidinium naphthalene-1,5-disulfonate

Bin Wei

doi:10.1107/S1600536812011099

. 2012 Mar 21;68(Pt 4):o1123. doi: 10.1107/S1600536812011099

Dimethylammonium guanidinium naphthalene-1,5-disulfonate

Bin Wei ^a,^*

PMCID: PMC3344069 PMID: 22589978

Abstract

The asymmetric unit of the title salt, CH₆N₃ ⁺·C₂H₈N⁺·C₁₀H₆O₆S₂ ²⁻, consists of one dimethylammonium cation, one guanidinium cation, and two half naphthalene-1,5-disulfonate anions, which lie on inversion centers. N—H⋯O hydrogen bonds link the cations and anions into layers parallel to the ab plane. The layers have a sandwich-like structure, with the sulfonate groups and cations forming outer slices and the naphthalene ring systems inside.

Related literature

For nanoporous materials with two-dimensional hydrogen-bonded networks, see: Russell et al. (1997 ▶). For recent studies of organic and organic–inorganic salts with ferroelectric properties, see: Fu et al. (2009 ▶); Wu et al. (2011 ▶). For general background to structure phase transitions in closely related compounds, see: Ye et al. (2009 ▶); Zhang et al. (2010 ▶).

Experimental

Crystal data

CH₆N₃ ⁺·C₂H₈N⁺·C₁₀H₆O₆S₂ ²⁻
M _r = 392.45
Triclinic,
a = 8.7782 (18) Å
b = 9.0316 (18) Å
c = 11.923 (2) Å
α = 87.10 (3)°
β = 74.74 (3)°
γ = 88.77 (3)°
V = 910.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.33 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 = 0.936, T _max = 0.937
9502 measured reflections
4168 independent reflections
3097 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.121
S = 1.04
4168 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 datablock(s) I, global. DOI: 10.1107/S1600536812011099/yk2047sup1.cif

e-68-o1123-sup1.cif^{(19KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011099/yk2047Isup2.hkl

e-68-o1123-Isup2.hkl^{(204.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812011099/yk2047Isup3.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—H1D⋯O1ⁱ	0.86	2.10	2.916 (3)	159
N1—H1E⋯O5	0.86	2.02	2.825 (3)	157
N2—H2D⋯O6ⁱⁱ	0.86	2.12	2.942 (3)	160
N2—H2E⋯O2	0.86	2.08	2.921 (3)	164
N3—H3A⋯O4	0.86	2.24	3.084 (3)	167
N3—H3B⋯O3	0.86	2.11	2.940 (3)	163
N4—H4A⋯O6ⁱⁱⁱ	0.90	2.12	3.011 (3)	168
N4—H4A⋯O5ⁱⁱⁱ	0.90	2.50	3.133 (3)	128
N4—H4B⋯O1^iv	0.90	2.60	3.152 (3)	121
N4—H4B⋯O2^iv	0.90	2.04	2.914 (3)	163

Open in a new tab

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

Acknowledgments

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

supplementary crystallographic information

Comment

Recently a series of nanoporous materials has been reported, which have two-dimensional hydrogen-bond networks and adjustable porosity (Russell et al., 1997). Guanidinium ions and the sulfonate groups of arenedisulfonate ions can form rich variety of H-bonds. We prepared the title compound in attempts to find new hydrogen-bonded dielectric materials consisting of guanidinium and naphthalene-1,5-disulfonate ions. Unfortunately, the study of dielectric permeability of the title compound indicated that its dielectric constant is essentially temperature-independent below its melting point (388 — 390 K). Thus we have found that the title compound has no dielectric disuniform from 80 K to 405 K.

At room temperature (25°C), the asymmetric unit of the title compound consists of one dimethylammonium cation, one guanidinium cation, and two halves of naphthalene-1,5-disulfonate anions, which lie at inversion centers (Fig. 1). The N—H···O hydrogen bonds join cations and anions into layers parallel to the ab plane. Layers have sandwich-like structure: sulfonate groups and cations form outer slices and naphthalene bicycles are inside. (Fig. 2).

Experimental

The 1,5-naphthalenedisulfonic acid (1.824 g 8 mmol) and guanidinium tetrafluoroborate (0.588 g 4 mmol) were combined in 30 ml aqueous solution, and methanol solution of dimethylamine (0.326 g 4 mmol) was added to the mixture. The solution was stirred for 30 min to complete the reaction, and good quality blocky single crystals were obtained by slow evaporation of the filtrate after two weeks (chemical yield is 62%).