Bis(2-methyl-1H-imidazol-3-ium) naphthalene-1,5-disulfonate dihydrate

Wang, Y.

doi:10.1107/S1600536812019149

organic compounds

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Volume 68| Part 6| June 2012| Page o1619

doi:10.1107/S1600536812019149

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Bis(2-methyl-1H-imidazol-3-ium) naphthalene-1,5-disulfonate dihydrate

Yu-feng Wang ^a ^*

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

(Received 11 April 2012; accepted 28 April 2012; online 5 May 2012)

The asymmetric unit of the title organic salt, 2C₄H₇N₂⁺·C₁₀H₆O₆S₂²⁻·2H₂O, consists of a 2-methylimidazolium cation, a half of a naphthalene-1,5-disulfonate anion, which lies about a center of symmetry, and a water molecule. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link the cations, anions and water molecules into the layers parallel to (111).

Related literature

For general background to dielectric–ferroelectric phase transitions, see: Ye et al. (2009 ); Zhang et al. (2009 ). For the structures of naphthalene-1,5-disulfonate salts with N-heterocyclic cations, see: Janczak & Perpétuo (2008 ); Wang et al. (2008 ).

Experimental

Crystal data

2C₄H₇N₂⁺·C₁₀H₆O₆S₂²⁻·2H₂O
M_r = 488.53
Triclinic, $[P \overline 1]$
a = 7.1301 (14) Å
b = 8.1773 (16) Å
c = 9.970 (2) Å
α = 75.58 (3)°
β = 75.10 (3)°
γ = 80.34 (3)°
V = 540.7 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.23 × 0.22 × 0.18 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.933, T_max = 0.947
5695 measured reflections
2475 independent reflections
1490 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.107
S = 0.94
2475 reflections
154 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4C⋯O2ⁱ	0.82 (2)	1.95 (2)	2.754 (3)	167 (3)
O4—H4B⋯O2ⁱⁱ	0.82 (2)	1.92 (2)	2.730 (3)	166 (3)
N1—H1D⋯O1ⁱⁱⁱ	0.86	2.00	2.768 (3)	149
N2—H2B⋯O4	0.86	1.78	2.628 (3)	169
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y-1, z; (iii) -x, -y+1, -z+1.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812019149/yk2053sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019149/yk2053Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812019149/yk2053Isup3.cml

checkCIF report

Comment top

The compounds exhibiting the dielectric-ferroelectric phase transition constitute an interesting class of materials, comprising organic and metal-organic coordination compounds, organic-inorganic hybrids and organic salts (Ye et al., 2009; Zhang et al., 2009). Unfortunately, the temperature dependence of dielectric constant of the title compound indicates that the permittivity is temperature-independent below the melting point (388 - 389 K) of the compound. Herein we descibe the crystal structure of this compound.

The asymmetric unit of the title compound consists of a 2-methylimidazolium cation, a half of naphthalene-1,5-disulfonate anion and a water molecule (Fig. 1). The cations, anions and water molecules are connected by N—H···O and O—H···O hydrogen bonds, which form the layers parallel to the (1 1 1) plane (Fig. 2 and Table 1).

Related literature top

For general background to dielectric–ferroelectric structure phase transitions, see: Ye et al. (2009); Zhang et al. (2009). For the structures of naphthalene-1,5-disulfonate salts with N-heterocyclic cations, see: Janczak & Perpétuo (2008); Wang et al. (2008).

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 2-methylimidazole (1.6 g, 0.02 mol) in water. Good quality single crystals were obtained by slow evaporation after two days (the chemical yield is 45%).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms labelled with suffix A are generated by the symmetry operator (1 - x, 1 - y, -z).
	Fig. 2. A view of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds.

Bis(2-methyl-1H-imidazol-3-ium) naphthalene-1,5-disulfonate dihydrate top

Crystal data top

2C₄H₇N₂⁺·C₁₀H₆O₆S₂²⁻·2H₂O	Z = 1
M_r = 488.53	F(000) = 256
Triclinic, P1	D_x = 1.500 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1301 (14) Å	Cell parameters from 3638 reflections
b = 8.1773 (16) Å	θ = 3.0–27.5°
c = 9.970 (2) Å	µ = 0.30 mm⁻¹
α = 75.58 (3)°	T = 293 K
β = 75.10 (3)°	Block, colourless
γ = 80.34 (3)°	0.23 × 0.22 × 0.18 mm
V = 540.7 (2) Å³

Data collection top

Rigaku SCXmini diffractometer	2475 independent reflections
Radiation source: fine-focus sealed tube	1490 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.933, T_max = 0.947	l = −12→12
5695 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ²(F_o²) + (0.0396P)²] where P = (F_o² + 2F_c²)/3
2475 reflections	(Δ/σ)_max = 0.005
154 parameters	Δρ_max = 0.20 e Å⁻³
3 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

2C₄H₇N₂⁺·C₁₀H₆O₆S₂²⁻·2H₂O	γ = 80.34 (3)°
M_r = 488.53	V = 540.7 (2) Å³
Triclinic, P1	Z = 1
a = 7.1301 (14) Å	Mo Kα radiation
b = 8.1773 (16) Å	µ = 0.30 mm⁻¹
c = 9.970 (2) Å	T = 293 K
α = 75.58 (3)°	0.23 × 0.22 × 0.18 mm
β = 75.10 (3)°

Data collection top

Rigaku SCXmini diffractometer	2475 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1490 reflections with I > 2σ(I)
T_min = 0.933, T_max = 0.947	R_int = 0.059
5695 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	3 restraints
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	Δρ_max = 0.20 e Å⁻³
2475 reflections	Δρ_min = −0.33 e Å⁻³
154 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O4	0.7815 (4)	0.0540 (4)	0.1408 (3)	0.0873 (9)
C9	0.7423 (4)	0.6967 (3)	−0.0199 (3)	0.0419 (7)
H9A	0.8089	0.7809	−0.0115	0.050*
S1	0.13194 (10)	0.66733 (9)	0.23893 (7)	0.0342 (2)
O3	0.2455 (3)	0.6595 (2)	0.33926 (19)	0.0438 (5)
O2	0.1153 (3)	0.8363 (2)	0.1501 (2)	0.0481 (5)
C7	0.4534 (3)	0.5560 (3)	0.0451 (2)	0.0255 (5)
C6	0.2599 (3)	0.5340 (3)	0.1233 (2)	0.0271 (6)
O1	−0.0547 (2)	0.6045 (2)	0.3027 (2)	0.0501 (5)
N2	0.4574 (3)	0.1263 (3)	0.3230 (2)	0.0410 (6)
H2B	0.5580	0.0903	0.2647	0.049*
N1	0.2739 (3)	0.2647 (3)	0.4672 (2)	0.0438 (6)
H1D	0.2318	0.3366	0.5212	0.053*
C2	0.4508 (4)	0.2493 (3)	0.3875 (3)	0.0342 (6)
C8	0.5575 (4)	0.6821 (3)	0.0549 (3)	0.0349 (6)
H8A	0.4977	0.7567	0.1140	0.042*
C5	0.1658 (4)	0.4121 (3)	0.1091 (3)	0.0375 (7)
H5C	0.0378	0.4008	0.1597	0.045*
C3	0.2826 (4)	0.0645 (4)	0.3619 (3)	0.0571 (9)
H3A	0.2496	−0.0228	0.3308	0.069*
C1	0.6089 (4)	0.3484 (4)	0.3718 (3)	0.0500 (8)
H1A	0.6461	0.3283	0.4610	0.075*
H1B	0.5664	0.4669	0.3429	0.075*
H1C	0.7188	0.3156	0.3012	0.075*
C4	0.1682 (5)	0.1513 (4)	0.4521 (3)	0.0565 (9)
H4A	0.0386	0.1372	0.4970	0.068*
H4B	0.876 (4)	−0.014 (4)	0.158 (3)	0.083 (13)*
H4C	0.796 (4)	0.096 (4)	0.056 (2)	0.069 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0703 (17)	0.107 (2)	0.0409 (17)	0.0527 (15)	0.0101 (13)	−0.0005 (15)
C9	0.0391 (16)	0.0428 (18)	0.0478 (19)	−0.0129 (13)	0.0012 (14)	−0.0228 (14)
S1	0.0311 (4)	0.0392 (4)	0.0294 (4)	0.0027 (3)	0.0011 (3)	−0.0144 (3)
O3	0.0459 (11)	0.0558 (13)	0.0349 (11)	0.0010 (9)	−0.0114 (10)	−0.0213 (9)
O2	0.0517 (12)	0.0362 (12)	0.0419 (12)	0.0143 (9)	0.0011 (10)	−0.0067 (9)
C7	0.0236 (13)	0.0277 (14)	0.0237 (14)	0.0011 (10)	−0.0050 (11)	−0.0058 (10)
C6	0.0269 (13)	0.0310 (14)	0.0219 (14)	−0.0001 (11)	−0.0032 (11)	−0.0075 (11)
O1	0.0318 (11)	0.0682 (14)	0.0485 (13)	−0.0118 (9)	0.0141 (9)	−0.0293 (10)
N2	0.0377 (13)	0.0429 (15)	0.0381 (14)	−0.0014 (11)	0.0069 (11)	−0.0192 (11)
N1	0.0426 (14)	0.0420 (15)	0.0422 (15)	−0.0042 (11)	0.0096 (12)	−0.0209 (11)
C2	0.0340 (15)	0.0357 (16)	0.0281 (16)	−0.0021 (12)	−0.0008 (13)	−0.0059 (12)
C8	0.0340 (15)	0.0366 (16)	0.0367 (16)	−0.0023 (12)	−0.0023 (13)	−0.0194 (12)
C5	0.0231 (14)	0.0485 (18)	0.0402 (17)	−0.0082 (12)	0.0031 (13)	−0.0162 (13)
C3	0.057 (2)	0.048 (2)	0.066 (2)	−0.0220 (16)	0.0103 (18)	−0.0273 (17)
C1	0.0377 (17)	0.060 (2)	0.055 (2)	−0.0064 (15)	−0.0092 (15)	−0.0183 (16)
C4	0.0457 (18)	0.052 (2)	0.068 (2)	−0.0221 (15)	0.0142 (17)	−0.0241 (17)

Geometric parameters (Å, º) top

O4—H4B	0.824 (17)	N2—H2B	0.8600
O4—H4C	0.816 (16)	N1—C2	1.311 (3)
C9—C8	1.346 (3)	N1—C4	1.347 (3)
C9—C5ⁱ	1.382 (3)	N1—H1D	0.8600
C9—H9A	0.9300	C2—C1	1.451 (3)
S1—O3	1.4237 (18)	C8—H8A	0.9300
S1—O1	1.4392 (19)	C5—C9ⁱ	1.382 (3)
S1—O2	1.4483 (19)	C5—H5C	0.9300
S1—C6	1.761 (2)	C3—C4	1.313 (4)
C7—C8	1.402 (3)	C3—H3A	0.9300
C7—C7ⁱ	1.410 (4)	C1—H1A	0.9600
C7—C6	1.415 (3)	C1—H1B	0.9600
C6—C5	1.345 (3)	C1—H1C	0.9600
N2—C2	1.310 (3)	C4—H4A	0.9300
N2—C3	1.351 (3)

H4B—O4—H4C	112 (2)	N2—C2—N1	106.4 (2)
C8—C9—C5ⁱ	120.6 (2)	N2—C2—C1	126.3 (2)
C8—C9—H9A	119.7	N1—C2—C1	127.3 (2)
C5ⁱ—C9—H9A	119.7	C9—C8—C7	121.1 (2)
O3—S1—O1	113.33 (12)	C9—C8—H8A	119.5
O3—S1—O2	111.00 (12)	C7—C8—H8A	119.5
O1—S1—O2	112.51 (12)	C6—C5—C9ⁱ	120.6 (2)
O3—S1—C6	107.66 (11)	C6—C5—H5C	119.7
O1—S1—C6	106.15 (12)	C9ⁱ—C5—H5C	119.7
O2—S1—C6	105.65 (11)	C4—C3—N2	106.8 (3)
C8—C7—C7ⁱ	118.6 (3)	C4—C3—H3A	126.6
C8—C7—C6	123.1 (2)	N2—C3—H3A	126.6
C7ⁱ—C7—C6	118.3 (3)	C2—C1—H1A	109.5
C5—C6—C7	120.8 (2)	C2—C1—H1B	109.5
C5—C6—S1	117.62 (19)	H1A—C1—H1B	109.5
C7—C6—S1	121.57 (18)	C2—C1—H1C	109.5
C2—N2—C3	109.9 (2)	H1A—C1—H1C	109.5
C2—N2—H2B	125.1	H1B—C1—H1C	109.5
C3—N2—H2B	125.1	C3—C4—N1	107.1 (3)
C2—N1—C4	109.9 (2)	C3—C4—H4A	126.5
C2—N1—H1D	125.1	N1—C4—H4A	126.5
C4—N1—H1D	125.1

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4C···O2ⁱ	0.82 (2)	1.95 (2)	2.754 (3)	167 (3)
O4—H4B···O2ⁱⁱ	0.82 (2)	1.92 (2)	2.730 (3)	166 (3)
N1—H1D···O1ⁱⁱⁱ	0.86	2.00	2.768 (3)	149
N2—H2B···O4	0.86	1.78	2.628 (3)	169

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

Experimental details

Crystal data
Chemical formula	2C₄H₇N₂⁺·C₁₀H₆O₆S₂²⁻·2H₂O
M_r	488.53
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.1301 (14), 8.1773 (16), 9.970 (2)
α, β, γ (°)	75.58 (3), 75.10 (3), 80.34 (3)
V (Å³)	540.7 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.23 × 0.22 × 0.18

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.933, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	5695, 2475, 1490
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.107, 0.94
No. of reflections	2475
No. of parameters	154
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.33

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4C···O2ⁱ	0.816 (16)	1.952 (19)	2.754 (3)	167 (3)
O4—H4B···O2ⁱⁱ	0.824 (17)	1.92 (2)	2.730 (3)	166 (3)
N1—H1D···O1ⁱⁱⁱ	0.86	2.00	2.768 (3)	148.8
N2—H2B···O4	0.86	1.78	2.628 (3)	169.1

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

Acknowledgements

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

References

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