Bis(pyridinium) naphthalene-1,5-di­sulfonate dihydrate

Wei, B.

doi:10.1107/S1600536812016960

organic compounds

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Volume 68| Part 5| May 2012| Page o1489

doi:10.1107/S1600536812016960

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Bis(pyridinium) naphthalene-1,5-disulfonate dihydrate

Bin Wei ^a ^*

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

(Received 21 March 2012; accepted 18 April 2012; online 21 April 2012)

The asymmetric unit of the title organic salt, 2C₅H₆N⁺·C₁₀H₆O₆S₂²⁻·2H₂O, consists of a pyridinium cation, half a naphthalene-1,5-disulfonate dianion and a water molecule. The dianion has a crystallographically imposed centre of symmetry. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link cations, anions and water molecules into a three-dimensional network.

Related literature

For general background to ferroelectric metal-organic frameworks, see: Ye et al. (2006 ); Zhang et al. (2008 , 2010 ); Fu et al. (2009 ).

Experimental

Crystal data

2C₅H₆N⁺·C₁₀H₆O₆S₂²⁻·2H₂O
M_r = 482.52
Monoclinic, P 2₁ /n
a = 9.5876 (19) Å
b = 12.065 (2) Å
c = 9.843 (2) Å
β = 103.51 (3)°
V = 1107.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.29 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 = 0.860, T_max = 0.902
11131 measured reflections
2533 independent reflections
2150 reflections with I > 2σ(I)
R_int = 0.072

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.150
S = 1.10
2533 reflections
148 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4B⋯O1	0.82	2.07	2.801 (3)	148
O4—H4A⋯O2ⁱ	0.82	1.91	2.731 (3)	174
N1—H10⋯O4ⁱⁱ	0.86	1.82	2.667 (3)	170
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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/S1600536812016960/rz2728sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016960/rz2728Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812016960/rz2728Isup3.cml

checkCIF report

Comment top

Dielectric-ferroelectric constitute 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 (411k-412k) of the compound, we have found that title compound has no dielectric disuniform from 80 K to 405 K. Herein we descibe the crystal structure of this compound.

The asymmetric unit of the title compound (Fig. 1) consists of a pyridinium cation, a half of a naphthalene-1,5-disulfonate anion and a free water molecule, the anion having crystallographically imposed centre of symmetry. The pyridinium and naphthalene rings are oriented to form a dihedral angle of 13.89 (6)°. In the crystal, cations, anions and water molecules are connected by N—H···O and O—H···O intermolecular hydrogen bonds into a three-dimensional structure (Fig. 2; Table 1)

Related literature top

For general background to ferroelectric metal-organic frameworks, see: Ye et al. (2006); Zhang et al. (2008, 2010); Fu et al. (2009).

Experimental top

The title compound was obtained by the addition of naphthalene-1,5-disulfonate acid (3.62 g, 0.01 mol) to a solution of pyridine (1.6 g, 0.02 mol) in methanol, in the stoichiometric ratio 1: 2. Good quality single crystals were obtained by slow evaporation of the solvent after six days (yield 52%).

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 molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. Atoms labelled with suffix A are generated by the symmetry operator (2-x, -y, 1-z).
	Fig. 2. Crystal packing of the title compound viewed along the a axis. Dashed lines indicate hydrogen bonds.

Bis(pyridinium) naphthalene-1,5-disulfonate dihydrate top

Crystal data top

2C₅H₆N⁺·C₁₀H₆O₆S₂²⁻·2H₂O	F(000) = 504
M_r = 482.52	D_x = 1.448 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3638 reflections
a = 9.5876 (19) Å	θ = 3.0–27.5°
b = 12.065 (2) Å	µ = 0.29 mm⁻¹
c = 9.843 (2) Å	T = 293 K
β = 103.51 (3)°	Block, colourless
V = 1107.0 (4) Å³	0.55 × 0.44 × 0.36 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	2150 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.072
Graphite monochromator	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −12→12
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −15→15
T_min = 0.860, T_max = 0.902	l = −12→12
11131 measured reflections	2 standard reflections every 150 reflections
2533 independent 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.150	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0555P)² + 0.5924P] where P = (F_o² + 2F_c²)/3
2533 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.52 e Å⁻³
2 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

2C₅H₆N⁺·C₁₀H₆O₆S₂²⁻·2H₂O	V = 1107.0 (4) Å³
M_r = 482.52	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.5876 (19) Å	µ = 0.29 mm⁻¹
b = 12.065 (2) Å	T = 293 K
c = 9.843 (2) Å	0.55 × 0.44 × 0.36 mm
β = 103.51 (3)°

Data collection top

Rigaku SCXmini diffractometer	2533 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2150 reflections with I > 2σ(I)
T_min = 0.860, T_max = 0.902	R_int = 0.072
11131 measured reflections	2 standard reflections every 150 reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	2 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.10	Δρ_max = 0.52 e Å⁻³
2533 reflections	Δρ_min = −0.48 e Å⁻³
148 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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	0.4852 (3)	0.2836 (3)	0.5829 (3)	0.1102 (12)
H4A	0.4806	0.2959	0.4999	0.19 (3)*
H4B	0.5648	0.2599	0.6216	0.15 (2)*
S1	0.83962 (6)	0.15020 (5)	0.71768 (6)	0.0461 (2)
C1	0.9846 (2)	0.04729 (16)	0.53702 (19)	0.0316 (4)
C2	1.0533 (2)	0.14879 (17)	0.5220 (2)	0.0411 (5)
H2	1.0350	0.2108	0.5712	0.049*
C4	0.8853 (2)	0.03502 (17)	0.6239 (2)	0.0348 (4)
C3	1.1457 (3)	0.15711 (19)	0.4368 (3)	0.0483 (6)
H3	1.1884	0.2249	0.4269	0.058*
O3	0.7426 (2)	0.10851 (18)	0.7975 (2)	0.0700 (6)
C5	0.8229 (3)	−0.0643 (2)	0.6363 (2)	0.0450 (5)
H5	0.7588	−0.0708	0.6937	0.054*
O2	0.9728 (2)	0.19099 (18)	0.8046 (2)	0.0659 (6)
O1	0.7752 (2)	0.23031 (17)	0.6128 (2)	0.0712 (6)
N1	0.7941 (3)	0.0855 (3)	0.1614 (3)	0.0736 (8)
H10	0.8605	0.1283	0.1461	0.088*
C9	0.7696 (4)	−0.0066 (4)	0.0948 (4)	0.0811 (11)
H9	0.8240	−0.0255	0.0314	0.097*
C6	0.6178 (5)	0.0513 (4)	0.2786 (4)	0.0933 (13)
H6	0.5660	0.0718	0.3435	0.112*
C8	0.6691 (6)	−0.0745 (3)	0.1146 (4)	0.0943 (12)
H8	0.6521	−0.1410	0.0656	0.113*
C11	0.7207 (4)	0.1164 (3)	0.2526 (4)	0.0804 (10)
H11	0.7408	0.1838	0.2989	0.097*
C7	0.5903 (4)	−0.0464 (4)	0.2074 (6)	0.1002 (15)
H7	0.5183	−0.0932	0.2223	0.120*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O4	0.0640 (15)	0.206 (4)	0.0579 (14)	0.0563 (18)	0.0094 (11)	−0.0121 (17)
S1	0.0446 (3)	0.0501 (4)	0.0488 (4)	0.0077 (2)	0.0215 (3)	−0.0075 (2)
C1	0.0306 (9)	0.0345 (10)	0.0306 (9)	0.0028 (7)	0.0090 (7)	0.0042 (8)
C2	0.0482 (12)	0.0334 (10)	0.0450 (12)	−0.0010 (9)	0.0177 (10)	−0.0007 (8)
C4	0.0337 (10)	0.0403 (11)	0.0329 (10)	0.0044 (8)	0.0125 (8)	0.0016 (8)
C3	0.0544 (14)	0.0389 (11)	0.0579 (14)	−0.0099 (10)	0.0263 (12)	0.0035 (10)
O3	0.0734 (12)	0.0738 (13)	0.0809 (14)	−0.0020 (11)	0.0546 (11)	−0.0165 (11)
C5	0.0456 (12)	0.0509 (13)	0.0453 (12)	−0.0030 (10)	0.0244 (10)	0.0037 (10)
O2	0.0611 (11)	0.0809 (13)	0.0583 (11)	−0.0078 (10)	0.0192 (9)	−0.0258 (10)
O1	0.0746 (14)	0.0612 (12)	0.0818 (14)	0.0320 (10)	0.0263 (11)	0.0060 (10)
N1	0.0460 (13)	0.094 (2)	0.0767 (18)	−0.0075 (13)	0.0056 (12)	0.0324 (16)
C9	0.087 (2)	0.102 (3)	0.0581 (18)	0.036 (2)	0.0238 (17)	0.0150 (18)
C6	0.080 (2)	0.125 (4)	0.087 (2)	0.039 (2)	0.046 (2)	0.026 (2)
C8	0.116 (3)	0.061 (2)	0.091 (3)	0.006 (2)	−0.005 (3)	−0.0072 (19)
C11	0.090 (3)	0.0665 (19)	0.074 (2)	0.0054 (18)	−0.0035 (19)	−0.0072 (17)
C7	0.063 (2)	0.091 (3)	0.141 (4)	−0.017 (2)	0.012 (2)	0.050 (3)

Geometric parameters (Å, º) top

O4—H4A	0.8207	C5—C3ⁱ	1.401 (3)
O4—H4B	0.8202	C5—H5	0.9300
S1—O3	1.4413 (19)	N1—C9	1.283 (5)
S1—O1	1.443 (2)	N1—C11	1.317 (5)
S1—O2	1.447 (2)	N1—H10	0.8600
S1—C4	1.779 (2)	C9—C8	1.314 (6)
C1—C2	1.415 (3)	C9—H9	0.9300
C1—C1ⁱ	1.422 (4)	C6—C11	1.332 (6)
C1—C4	1.428 (3)	C6—C7	1.365 (6)
C2—C3	1.358 (3)	C6—H6	0.9300
C2—H2	0.9300	C8—C7	1.357 (6)
C4—C5	1.358 (3)	C8—H8	0.9300
C3—C5ⁱ	1.401 (3)	C11—H11	0.9300
C3—H3	0.9300	C7—H7	0.9300

H4A—O4—H4B	110.7	C4—C5—H5	119.8
O3—S1—O1	113.62 (13)	C3ⁱ—C5—H5	119.8
O3—S1—O2	112.87 (13)	C9—N1—C11	122.1 (3)
O1—S1—O2	111.49 (14)	C9—N1—H10	119.0
O3—S1—C4	106.19 (11)	C11—N1—H10	119.0
O1—S1—C4	105.55 (11)	N1—C9—C8	121.1 (4)
O2—S1—C4	106.42 (11)	N1—C9—H9	119.4
C2—C1—C1ⁱ	118.9 (2)	C8—C9—H9	119.4
C2—C1—C4	122.98 (18)	C11—C6—C7	118.3 (4)
C1ⁱ—C1—C4	118.1 (2)	C11—C6—H6	120.9
C3—C2—C1	121.0 (2)	C7—C6—H6	120.9
C3—C2—H2	119.5	C9—C8—C7	119.1 (4)
C1—C2—H2	119.5	C9—C8—H8	120.4
C5—C4—C1	120.97 (19)	C7—C8—H8	120.4
C5—C4—S1	118.43 (16)	N1—C11—C6	120.1 (4)
C1—C4—S1	120.60 (16)	N1—C11—H11	120.0
C2—C3—C5ⁱ	120.5 (2)	C6—C11—H11	120.0
C2—C3—H3	119.8	C8—C7—C6	119.4 (4)
C5ⁱ—C3—H3	119.8	C8—C7—H7	120.3
C4—C5—C3ⁱ	120.48 (19)	C6—C7—H7	120.3

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4B···O1	0.82	2.07	2.801 (3)	148
O4—H4A···O2ⁱⁱ	0.82	1.91	2.731 (3)	174
N1—H10···O4ⁱⁱⁱ	0.86	1.82	2.667 (3)	170

Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	2C₅H₆N⁺·C₁₀H₆O₆S₂²⁻·2H₂O
M_r	482.52
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.5876 (19), 12.065 (2), 9.843 (2)
β (°)	103.51 (3)
V (Å³)	1107.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
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	0.860, 0.902
No. of measured, independent and observed [I > 2σ(I)] reflections	11131, 2533, 2150
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.150, 1.10
No. of reflections	2533
No. of parameters	148
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.48

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—H4B···O1	0.82	2.07	2.801 (3)	148.2
O4—H4A···O2ⁱ	0.82	1.91	2.731 (3)	174.3
N1—H10···O4ⁱⁱ	0.86	1.82	2.667 (3)	170.3

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z−1/2.

Acknowledgements

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

References

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