Bis(1H-imidazol-3-ium) naphthalene-1,5-disulfonate

Wei, B.

doi:10.1107/S1600536812016972

organic compounds

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Volume 68| Part 5| May 2012| Page o1529

doi:10.1107/S1600536812016972

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Bis(1H-imidazol-3-ium) naphthalene-1,5-disulfonate

Bin Wei ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: seuwei@126.com

(Received 29 February 2012; accepted 18 April 2012; online 25 April 2012)

The asymmetric unit of the title organic salt, 2C₃H₅N₂⁺·C₁₀H₆O₆S₂²⁻, consists of an imidazolium cation and half a naphthalene-1,5-disulfonate dianion, completed to the full dianion through an inversion center. N—H⋯S and N—H⋯O hydrogen bonds link cations and anions in the crystal, forming a chain propagating along [101].

Related literature

For general background to structure phase transitions in ferroelectrics, see: Ye et al. (2009 ); Zhang et al. (2009 ).

Experimental

Crystal data

2C₃H₅N₂⁺·C₁₀H₆O₆S₂²⁻
M_r = 424.45
Triclinic, $[P \overline 1]$
a = 6.6764 (13) Å
b = 6.7958 (14) Å
c = 10.251 (2) Å
α = 93.66 (3)°
β = 103.30 (3)°
γ = 96.77 (3)°
V = 447.48 (16) Å³
Z = 1
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.55 × 0.44 × 0.36 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.837, T_max = 0.885
4578 measured reflections
2043 independent reflections
1901 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.095
S = 1.13
2043 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S1ⁱ	0.86	2.84	3.588 (2)	147
N2—H2A⋯O3ⁱ	0.86	1.90	2.745 (2)	168
N1—H1A⋯O2ⁱⁱ	0.86	2.09	2.847 (2)	147
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x, y+1, z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812016972/bh2419sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016972/bh2419Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812016972/bh2419Isup3.cml

checkCIF report

Comment top

Dielectric-ferroelectric constitute an interesting class of materials, comprising organic ligands, metal-organic coordination compounds, organic-inorganic hybrids and organic salts (Ye et al., 2009; Zhang et al., 2009). 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 of the compound. We have found that title compound has no dielectric anomaly from 80 K to 405 K. Herein we describe the crystal structure of this compound.

The asymmetric unit of the title compound consists of an imidazolium cation in general position, and a half naphthalene-1,5-disulfonate anion, close to a inversion center (Fig. 1). The imidazolium ring and the naphthalene ring make a dihedral angle of 69.3°. The cations and anions are connected in the crystal by N—H···S and N—H···O hydrogen bonds, which improve the stability of the crystal structure. These hydrogen bonds link the cations and anions into a chain oriented in the [101] direction (Fig. 2 and Table 1).

Related literature top

For general background to structure phase transitions in ferroelectrics, see: Ye et al. (2009); Zhang et al. (2009).

Experimental top

The title compound was obtained by the addition of naphthalene-1,5-disulfonic acid (2.88 g, 0.01 mol) to a solution of imidazole (1.36 g, 0.02 mol) in water, in the stoichiometric ratio 1:2. Good quality single crystals were obtained by slow evaporation, after two days (yield: 38%).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, along the b axis. Dashed lines indicate hydrogen bonds.

Bis(1H-imidazol-3-ium) naphthalene-1,5-disulfonate top

Crystal data top

2C₃H₅N₂⁺·C₁₀H₆O₆S₂²⁻	V = 447.48 (16) Å³
M_r = 424.45	Z = 1
Triclinic, P1	F(000) = 220
Hall symbol: -P 1	D_x = 1.575 Mg m⁻³
a = 6.6764 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.7958 (14) Å	µ = 0.34 mm⁻¹
c = 10.251 (2) Å	T = 293 K
α = 93.66 (3)°	Block, colorless
β = 103.30 (3)°	0.55 × 0.44 × 0.36 mm
γ = 96.77 (3)°

Data collection top

Rigaku SCXmini diffractometer	2043 independent reflections
Radiation source: fine-focus sealed tube	1901 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
CCD_Profile_fitting scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −8→8
T_min = 0.837, T_max = 0.885	k = −8→8
4578 measured reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0312P)² + 0.2736P] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max = 0.001
2043 reflections	Δρ_max = 0.34 e Å⁻³
128 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.473 (17)
Primary atom site location: structure-invariant direct methods

Crystal data top

2C₃H₅N₂⁺·C₁₀H₆O₆S₂²⁻	γ = 96.77 (3)°
M_r = 424.45	V = 447.48 (16) Å³
Triclinic, P1	Z = 1
a = 6.6764 (13) Å	Mo Kα radiation
b = 6.7958 (14) Å	µ = 0.34 mm⁻¹
c = 10.251 (2) Å	T = 293 K
α = 93.66 (3)°	0.55 × 0.44 × 0.36 mm
β = 103.30 (3)°

Data collection top

Rigaku SCXmini diffractometer	2043 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1901 reflections with I > 2σ(I)
T_min = 0.837, T_max = 0.885	R_int = 0.025
4578 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.13	Δρ_max = 0.34 e Å⁻³
2043 reflections	Δρ_min = −0.36 e Å⁻³
128 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.1864 (3)	0.8251 (3)	0.5703 (2)	0.0502 (5)
H1A	0.3103	0.8750	0.5689	0.060*
C1	0.0353 (3)	0.7669 (3)	0.4648 (2)	0.0414 (5)
H1C	0.0430	0.7727	0.3757	0.050*
N2	−0.1299 (2)	0.6987 (2)	0.50561 (17)	0.0339 (4)
H2A	−0.2490	0.6512	0.4542	0.041*
C2	−0.0821 (4)	0.7151 (3)	0.6423 (2)	0.0429 (5)
H2C	−0.1709	0.6782	0.6970	0.051*
C3	0.1172 (4)	0.7945 (4)	0.6829 (3)	0.0561 (7)
H3B	0.1939	0.8233	0.7715	0.067*
S1	0.59698 (6)	0.27214 (7)	0.74446 (4)	0.02816 (18)
O1	0.8155 (2)	0.3366 (2)	0.80260 (13)	0.0360 (3)
O2	0.5600 (2)	0.0983 (2)	0.64608 (13)	0.0381 (4)
O3	0.4864 (2)	0.4326 (2)	0.68915 (14)	0.0399 (4)
C4	0.2276 (3)	0.2277 (3)	1.0055 (2)	0.0349 (4)
H4A	0.1216	0.2937	1.0241	0.042*
C5	0.3273 (3)	0.2901 (3)	0.90549 (19)	0.0317 (4)
H5A	0.2866	0.3968	0.8582	0.038*
C6	0.4841 (3)	0.1945 (3)	0.87756 (16)	0.0253 (4)
C7	0.5517 (2)	0.0313 (2)	0.94962 (16)	0.0239 (3)
C8	0.7149 (3)	−0.0712 (3)	0.92461 (18)	0.0304 (4)
H8A	0.7835	−0.0309	0.8595	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0278 (8)	0.0370 (10)	0.0858 (15)	−0.0023 (7)	0.0143 (9)	0.0151 (10)
C1	0.0479 (12)	0.0383 (11)	0.0473 (12)	0.0133 (9)	0.0237 (10)	0.0131 (9)
N2	0.0272 (8)	0.0314 (8)	0.0409 (9)	0.0021 (6)	0.0048 (7)	0.0024 (7)
C2	0.0543 (13)	0.0361 (10)	0.0402 (11)	−0.0044 (9)	0.0206 (10)	0.0036 (8)
C3	0.0621 (15)	0.0423 (12)	0.0477 (13)	−0.0113 (11)	−0.0098 (11)	0.0023 (10)
S1	0.0252 (2)	0.0347 (3)	0.0221 (2)	−0.00415 (16)	0.00433 (16)	0.00418 (16)
O1	0.0263 (7)	0.0450 (8)	0.0331 (7)	−0.0064 (5)	0.0048 (5)	0.0061 (6)
O2	0.0400 (8)	0.0454 (8)	0.0260 (7)	−0.0091 (6)	0.0119 (6)	−0.0049 (6)
O3	0.0363 (7)	0.0451 (8)	0.0360 (7)	0.0012 (6)	0.0029 (6)	0.0155 (6)
C4	0.0326 (9)	0.0414 (10)	0.0351 (10)	0.0129 (8)	0.0130 (8)	0.0027 (8)
C5	0.0319 (9)	0.0323 (9)	0.0311 (9)	0.0069 (7)	0.0063 (7)	0.0044 (7)
C6	0.0246 (8)	0.0295 (8)	0.0202 (7)	−0.0008 (6)	0.0047 (6)	0.0000 (6)
C7	0.0210 (7)	0.0287 (8)	0.0200 (7)	0.0000 (6)	0.0038 (6)	−0.0019 (6)
C8	0.0276 (9)	0.0395 (10)	0.0266 (8)	0.0054 (7)	0.0111 (7)	0.0033 (7)

Geometric parameters (Å, º) top

N1—C1	1.301 (3)	O3—S1	1.4601 (15)
N1—C3	1.358 (4)	S1—C6	1.7828 (18)
N1—H1A	0.8600	C4—H4A	0.9300
C1—H1C	0.9300	C4—C8ⁱ	1.363 (3)
N2—C1	1.312 (3)	C5—H5A	0.9300
N2—C2	1.358 (3)	C5—C4	1.406 (3)
N2—H2A	0.8600	C6—C5	1.369 (3)
C2—C3	1.334 (3)	C6—C7	1.431 (2)
C2—H2C	0.9300	C7—C8	1.422 (2)
C3—H3B	0.9300	C7—C7ⁱ	1.428 (3)
O1—S1	1.4464 (14)	C8—C4ⁱ	1.363 (3)
O2—S1	1.4621 (15)	C8—H8A	0.9300

C1—N1—C3	109.10 (18)	O1—S1—C6	107.15 (8)
C1—N1—H1A	125.4	O3—S1—C6	106.12 (9)
C3—N1—H1A	125.4	O2—S1—C6	105.93 (8)
N1—C1—N2	108.4 (2)	C8ⁱ—C4—C5	120.55 (17)
N1—C1—H1C	125.8	C8ⁱ—C4—H4A	119.7
N2—C1—H1C	125.8	C5—C4—H4A	119.7
C1—N2—C2	108.91 (18)	C6—C5—C4	120.21 (17)
C1—N2—H2A	125.5	C6—C5—H5A	119.9
C2—N2—H2A	125.5	C4—C5—H5A	119.9
C3—C2—N2	106.7 (2)	C5—C6—C7	121.20 (16)
C3—C2—H2C	126.7	C5—C6—S1	118.37 (14)
N2—C2—H2C	126.7	C7—C6—S1	120.39 (13)
C2—C3—N1	106.9 (2)	C8—C7—C7ⁱ	118.9 (2)
C2—C3—H3B	126.5	C8—C7—C6	123.07 (16)
N1—C3—H3B	126.5	C7ⁱ—C7—C6	118.00 (19)
O1—S1—O3	112.88 (9)	C4ⁱ—C8—C7	121.10 (17)
O1—S1—O2	112.73 (9)	C4ⁱ—C8—H8A	119.5
O3—S1—O2	111.46 (9)	C7—C8—H8A	119.5

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱⁱ	0.86	2.84	3.588 (2)	147
N2—H2A···O3ⁱⁱ	0.86	1.90	2.745 (2)	168
N1—H1A···O2ⁱⁱⁱ	0.86	2.09	2.847 (2)	147
N1—H1A···O2^iv	0.86	2.56	3.118 (3)	124

Symmetry codes: (ii) −x, −y+1, −z+1; (iii) x, y+1, z; (iv) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	2C₃H₅N₂⁺·C₁₀H₆O₆S₂²⁻
M_r	424.45
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.6764 (13), 6.7958 (14), 10.251 (2)
α, β, γ (°)	93.66 (3), 103.30 (3), 96.77 (3)
V (Å³)	447.48 (16)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.55 × 0.44 × 0.36

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.837, 0.885
No. of measured, independent and observed [I > 2σ(I)] reflections	4578, 2043, 1901
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.095, 1.13
No. of reflections	2043
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.36

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.86	2.84	3.588 (2)	146.5
N2—H2A···O3ⁱ	0.86	1.90	2.745 (2)	167.7
N1—H1A···O2ⁱⁱ	0.86	2.09	2.847 (2)	147.1

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y+1, z.

Acknowledgements

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

References

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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