Bis(trimethyl­ammonium) naphthalene-1,5-disulfonate

Jin, Y.

doi:10.1107/S1600536811052718

organic compounds

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Volume 68| Part 1| January 2012| Page o90

doi:10.1107/S1600536811052718

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Bis(trimethylammonium) naphthalene-1,5-disulfonate

Yu Jin ^a ^*

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

(Received 2 December 2011; accepted 7 December 2011; online 10 December 2011)

The asymmetric unit of the title compound, 2C₃H₁₀N⁺·C₁₀H₆S₂O₆²⁻, contains a half-anion, which is completed by inversion symmetry, and one cation. The cations and anions are associated via strong N—H⋯O(sulfonate) hydrogen-bonding interactions, forming cation–anion–cation groups. Secondary interactions such as C—H(ammonium)⋯O(sulfonate) and van der Waals interactions link the cations and anions together in a three-dimensional crystal structure, with zigzag rows of cations lying between layers of anions.

Related literature

The title compound was investigated as part of our search for simple ferroelectric compounds. For general background to ferroelectric metal-organic frameworks, see: Ye et al. (2006 ); Zhang et al. (2008 , 2009 , 2010 ); Fu et al. (2009 ). For a related structure, see: Wang & Yang (2011 ).

Experimental

Crystal data

2C₃H₁₀N⁺·C₁₀H₆O₆S₂²⁻
M_r = 406.51
Monoclinic, P 2₁ /c
a = 8.3428 (17) Å
b = 10.502 (2) Å
c = 11.742 (2) Å
β = 105.81 (3)°
V = 989.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.3 × 0.3 × 0.2 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.489, T_max = 1.000
10031 measured reflections
2265 independent reflections
2016 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.109
S = 1.10
2265 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.28 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
N1—H1E⋯O2ⁱ	0.91	1.81	2.718 (2)	173
C1—H1C⋯O1	0.96	2.43	3.372 (3)	166
C2—H2B⋯O3ⁱⁱ	0.96	2.31	3.232 (4)	162
Symmetry codes: (i) x+1, y, z; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811052718/bh2404sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811052718/bh2404Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811052718/bh2404Isup3.cml

checkCIF report

Comment top

Ferroelectric compounds have displayed a variety of technical applications, such as ferroelectric random access memories, infrared detectors, piezoelectric sensors, nonlinear optical devices, as a result of their excellent ferroelectric, piezoelectric, pyroelectric, and optical properties. Most of the new ferroelectric metal-organic compounds consistent with the necessary requirements for ferroelectric properties have been explored. However, the conditions required in these systems, such as a phase transition, a good electric hysteresis loop and electric domain, and a dielectric anomaly, often disappear (Zhang et al., 2009). Hence, pure organic compounds can be of great potential and can probably make up for the drawbacks found in ferroelectric metal-organic compounds. Reversible structural phase transition remains one of the prominent properties for ferroelectrics. For a small part of these compounds, the components can be arranged in a disordered fashion at a relative high temperature and in an ordered fashion at a relative low temperature. The transition from the disordered arrangement to the ordered one gives rise to sharp change in the physical properties of the compound (Fu et al., 2009; Zhang et al., 2008, 2010; Ye et al., 2006). As part of our search for simple ferroelectric compounds, we have investigated the title compound and report now its room temperature crystal structure.

The centrosymmetric anion and one cation are shown in Fig. 1 with the hydrogen bonds listed in Table 1. The existence of numerous hydrogen-bonding interactions helps to make the substance more stable, and thus forms a three-dimensional layered structure. The interactions tie the cations and anions together in sheets with zigzag rows of cations lying between layers of anions (Fig. 2). There are only van der Waals interactions between layers. The reported structure is similar to that of a related naphthalene-1,5-disulfonate salt (Wang & Yang, 2011).

Related literature top

For general background to ferroelectric metal-organic frameworks, see: Ye et al. (2006); Zhang et al. (2008, 2009, 2010); Fu et al. (2009). For a related structure, see: Wang & Yang (2011).

Experimental top

(C₃H₁₀N⁺)₂(C₁₀H₆S₂O₆^2-) was formed from a mixture of N(CH₃)₃ (8 mL), C₁₀H₈O₆S₂ (288.28 mg, 1.00 mmol), and distilled water (10 ml), which was stirred for few minutes at room temperature, giving a clear transparent solution. After evaporation over few days, block-shaped colorless crystals suitable for X-ray diffraction were obtained in about 82% yield, filtered and washed with distilled water.

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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The crystal structure of the title compound viewed along the c axis. Intermolecular interactions are shown as dashed lines.

Bis(trimethylammonium) naphthalene-1,5-disulfonate top

Crystal data top

2C₃H₁₀N⁺·C₁₀H₆O₆S₂²⁻	F(000) = 432
M_r = 406.51	D_x = 1.364 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3450 reflections
a = 8.3428 (17) Å	θ = 6.2–55.3°
b = 10.502 (2) Å	µ = 0.30 mm⁻¹
c = 11.742 (2) Å	T = 293 K
β = 105.81 (3)°	Block, colourless
V = 989.8 (3) Å³	0.3 × 0.3 × 0.2 mm
Z = 2

Data collection top

Rigaku Mercury CCD diffractometer	2265 independent reflections
Radiation source: fine-focus sealed tube	2016 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −10→10
T_min = 0.489, T_max = 1.000	k = −13→13
10031 measured reflections	l = −15→15

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)] = 0.041	H-atom parameters constrained
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.0505P)² + 0.3652P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
2265 reflections	Δρ_max = 0.28 e Å⁻³
119 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: 0.055 (4)
Primary atom site location: structure-invariant direct methods

Crystal data top

2C₃H₁₀N⁺·C₁₀H₆O₆S₂²⁻	V = 989.8 (3) Å³
M_r = 406.51	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3428 (17) Å	µ = 0.30 mm⁻¹
b = 10.502 (2) Å	T = 293 K
c = 11.742 (2) Å	0.3 × 0.3 × 0.2 mm
β = 105.81 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	2265 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2016 reflections with I > 2σ(I)
T_min = 0.489, T_max = 1.000	R_int = 0.036
10031 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.10	Δρ_max = 0.28 e Å⁻³
2265 reflections	Δρ_min = −0.36 e Å⁻³
119 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.7732 (3)	0.1761 (3)	0.4624 (2)	0.0783 (8)
H1B	0.7949	0.2389	0.4090	0.117*
H1C	0.6593	0.1826	0.4647	0.117*
H1D	0.7929	0.0927	0.4357	0.117*
C2	0.8549 (4)	0.1033 (3)	0.6651 (3)	0.0926 (10)
H2B	0.9280	0.1194	0.7423	0.139*
H2C	0.8760	0.0197	0.6395	0.139*
H2D	0.7413	0.1087	0.6683	0.139*
C3	0.8748 (4)	0.3266 (3)	0.6265 (3)	0.0824 (9)
H3B	0.9491	0.3339	0.7046	0.124*
H3C	0.7629	0.3436	0.6293	0.124*
H3D	0.9061	0.3868	0.5749	0.124*
C4	0.4055 (2)	0.39604 (16)	0.66437 (14)	0.0336 (4)
H4A	0.3567	0.3452	0.7105	0.040*
C5	0.37869 (18)	0.37009 (14)	0.54673 (13)	0.0279 (3)
C6	0.44909 (18)	0.44781 (14)	0.47321 (13)	0.0258 (3)
C7	0.4218 (2)	0.42584 (15)	0.35041 (14)	0.0315 (4)
H7A	0.3535	0.3589	0.3146	0.038*
C8	0.4940 (2)	0.50113 (16)	0.28418 (14)	0.0353 (4)
H8A	0.4764	0.4842	0.2040	0.042*
N1	0.88425 (18)	0.19790 (16)	0.58184 (15)	0.0444 (4)
H1E	0.9904	0.1864	0.5772	0.053*
O1	0.3624 (2)	0.15499 (14)	0.43979 (16)	0.0635 (5)
O2	0.21016 (15)	0.17580 (12)	0.58538 (12)	0.0406 (3)
O3	0.11286 (19)	0.28226 (17)	0.39993 (14)	0.0646 (5)
S1	0.25686 (5)	0.23499 (4)	0.48711 (4)	0.03500 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0441 (12)	0.127 (3)	0.0569 (15)	−0.0063 (14)	0.0017 (11)	−0.0125 (16)
C2	0.112 (2)	0.086 (2)	0.0729 (18)	−0.0519 (19)	0.0134 (17)	0.0023 (15)
C3	0.0762 (18)	0.0563 (15)	0.104 (2)	0.0190 (13)	0.0066 (16)	−0.0161 (14)
C4	0.0363 (8)	0.0363 (8)	0.0301 (8)	−0.0014 (7)	0.0123 (7)	0.0050 (6)
C5	0.0247 (7)	0.0274 (7)	0.0310 (8)	0.0002 (6)	0.0068 (6)	0.0011 (6)
C6	0.0256 (7)	0.0249 (7)	0.0265 (7)	0.0029 (6)	0.0064 (6)	0.0005 (6)
C7	0.0347 (8)	0.0298 (8)	0.0285 (8)	−0.0014 (6)	0.0061 (6)	−0.0041 (6)
C8	0.0423 (9)	0.0385 (9)	0.0254 (7)	−0.0014 (7)	0.0100 (7)	−0.0011 (6)
N1	0.0267 (7)	0.0521 (10)	0.0534 (10)	−0.0035 (6)	0.0092 (7)	−0.0075 (8)
O1	0.0751 (11)	0.0409 (8)	0.0925 (12)	−0.0193 (7)	0.0537 (10)	−0.0242 (8)
O2	0.0332 (6)	0.0420 (7)	0.0471 (7)	−0.0069 (5)	0.0118 (5)	0.0085 (5)
O3	0.0455 (8)	0.0811 (11)	0.0533 (9)	−0.0226 (8)	−0.0101 (7)	0.0189 (8)
S1	0.0322 (2)	0.0350 (3)	0.0379 (3)	−0.00957 (16)	0.00984 (17)	−0.00121 (16)

Geometric parameters (Å, º) top

C1—N1	1.473 (3)	C4—H4A	0.9300
C1—H1B	0.9600	C5—C6	1.426 (2)
C1—H1C	0.9600	C5—S1	1.7744 (16)
C1—H1D	0.9600	C6—C7	1.416 (2)
C2—N1	1.460 (3)	C6—C6ⁱ	1.424 (3)
C2—H2B	0.9600	C7—C8	1.359 (2)
C2—H2C	0.9600	C7—H7A	0.9300
C2—H2D	0.9600	C8—C4ⁱ	1.400 (2)
C3—N1	1.459 (3)	C8—H8A	0.9300
C3—H3B	0.9600	N1—H1E	0.9100
C3—H3C	0.9600	O1—S1	1.4338 (15)
C3—H3D	0.9600	O2—S1	1.4541 (13)
C4—C5	1.365 (2)	O3—S1	1.4379 (16)
C4—C8ⁱ	1.400 (2)

N1—C1—H1B	109.5	C6—C5—S1	120.33 (11)
N1—C1—H1C	109.5	C7—C6—C6ⁱ	119.11 (17)
H1B—C1—H1C	109.5	C7—C6—C5	123.01 (14)
N1—C1—H1D	109.5	C6ⁱ—C6—C5	117.88 (16)
H1B—C1—H1D	109.5	C8—C7—C6	120.95 (15)
H1C—C1—H1D	109.5	C8—C7—H7A	119.5
N1—C2—H2B	109.5	C6—C7—H7A	119.5
N1—C2—H2C	109.5	C7—C8—C4ⁱ	120.58 (15)
H2B—C2—H2C	109.5	C7—C8—H8A	119.7
N1—C2—H2D	109.5	C4ⁱ—C8—H8A	119.7
H2B—C2—H2D	109.5	C3—N1—C2	110.7 (2)
H2C—C2—H2D	109.5	C3—N1—C1	113.8 (2)
N1—C3—H3B	109.5	C2—N1—C1	110.8 (2)
N1—C3—H3C	109.5	C3—N1—H1E	107.0
H3B—C3—H3C	109.5	C2—N1—H1E	107.0
N1—C3—H3D	109.5	C1—N1—H1E	107.0
H3B—C3—H3D	109.5	O1—S1—O3	114.11 (11)
H3C—C3—H3D	109.5	O1—S1—O2	112.49 (9)
C5—C4—C8ⁱ	120.29 (15)	O3—S1—O2	111.10 (8)
C5—C4—H4A	119.9	O1—S1—C5	105.98 (8)
C8ⁱ—C4—H4A	119.9	O3—S1—C5	106.41 (9)
C4—C5—C6	121.16 (14)	O2—S1—C5	106.10 (8)
C4—C5—S1	118.50 (12)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1E···O2ⁱⁱ	0.91	1.81	2.718 (2)	173
C1—H1C···O1	0.96	2.43	3.372 (3)	166
C2—H2B···O3ⁱⁱⁱ	0.96	2.31	3.232 (4)	162
N1—H1E···S1ⁱⁱ	0.91	2.76	3.5967 (18)	154

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

Experimental details

Crystal data
Chemical formula	2C₃H₁₀N⁺·C₁₀H₆O₆S₂²⁻
M_r	406.51
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.3428 (17), 10.502 (2), 11.742 (2)
β (°)	105.81 (3)
V (Å³)	989.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.3 × 0.3 × 0.2

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.489, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10031, 2265, 2016
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.109, 1.10
No. of reflections	2265
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −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
N1—H1E···O2ⁱ	0.91	1.81	2.718 (2)	172.6
C1—H1C···O1	0.96	2.43	3.372 (3)	166
C2—H2B···O3ⁱⁱ	0.96	2.31	3.232 (4)	162

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

Acknowledgements

The author thanks the Ordered Matter Science Research Center, Southeast University, for its excellent experimental conditions and its generous financial support.

References

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