Bis(diisopropyl­ammonium) naphthalene-1,5-disulfonate

Jin, Y.

doi:10.1107/S1600536811043492

organic compounds

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Volume 67| Part 11| November 2011| Page o3048

doi:10.1107/S1600536811043492

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Bis(diisopropylammonium) 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 9 September 2011; accepted 20 October 2011; online 29 October 2011)

In the title compound, 2C₆H₁₆N⁺·C₁₀H₆O₆S₂²⁻, the cations and anions are associated via N—H⋯O and C—H⋯O hydrogen-bonding interactions.

Related literature

For general background on ferroelectric metal–organic frameworks, see: Fu et al. (2009 ); Wu et al. (2011 ); Ye et al. (2006 ); Zhang et al. (2008 , 2010 ).

Experimental

Crystal data

2C₆H₁₆N⁺·C₁₀H₆O₆S₂²⁻
M_r = 490.66
Triclinic, $[P \overline 1]$
a = 7.9518 (16) Å
b = 9.1215 (18) Å
c = 9.4319 (19) Å
α = 74.33 (3)°
β = 88.60 (3)°
γ = 74.74 (3)°
V = 634.7 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.25 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
6562 measured reflections
2904 independent reflections
2621 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.129
S = 1.12
2904 reflections
150 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1ⁱ	0.90	2.03	2.887 (2)	159
N1—H1D⋯O3ⁱⁱ	0.90	2.02	2.916 (2)	174
C9—H9A⋯O3	0.96	2.58	3.480 (3)	156
C6—H6A⋯O3ⁱⁱ	0.96	2.58	3.351 (3)	138
C11—H11C⋯O1ⁱⁱ	0.96	2.61	3.439 (4)	144
C11—H11B⋯O2ⁱ	0.96	2.47	3.382 (3)	158
Symmetry codes: (i) x, y, z-1; (ii) -x+1, -y, -z+1.

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/S1600536811043492/mw2025sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043492/mw2025Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811043492/mw2025Isup3.cml

checkCIF report

Comment top

Currently, simple molecular-ionic compounds containing organic cations and anions are of considerable interest owing to the tunability of their structural features and their potential to show ferroelectric properties. There exists a series of compounds in which the components can be arranged in a disordered fashion at a relative high temperature and in an ordered fashion at a relative low temperature. (Fu et al., 2009; Zhang et al., 2010; Zhang et al., 2008;Ye et al., 2006). The transition from the disordered arrangement to the ordered one leads to sharp change in the physical properties of the compound. As part of our search for simple ferroelectric compounds we have investigated the title compound and report its room temperature structure.

The centrosymmetric anion and one cation are shown in Fig. 1 with the hydrogen bonds listed in Table 1. These interactions tie the cations and anions together in sheets approximately parallel to {100} with zig-zag rows of cations lying between rows of anions (Fig. 2). There are only van der Waals interactions between layers.

Related literature top

For general background on ferroelectric metal–organic frameworks, see: Fu et al. (2009); Wu et al. (2011); Ye et al. (2006); Zhang et al. (2008, 2010).

Experimental top

1,5-naphthalenedisulfonic acid (10 mmol, 2.88 g) was dissolved in 15 ml of distilled water and was stirred for 5 minutes after which diisopropylamine (1.5 ml) was added with stirring. The solution was filtered and left to stand undisturbed whereupon colorless block crystals suitable for X-ray diffraction were obtained in about 68% yield after two days. These were filtered off 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. Perspective view of one cation and the anion for (I).Displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Packing of (I) viewed down the a axis. The N—H···O and C—H···O interactions are shown, respectively as dashed and dotted lines.

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

Crystal data top

2C₆H₁₆N⁺·C₁₀H₆O₆S₂²⁻	Z = 1
M_r = 490.66	F(000) = 264
Triclinic, P1	D_x = 1.284 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9518 (16) Å	Cell parameters from 3450 reflections
b = 9.1215 (18) Å	θ = 3.1–27.6°
c = 9.4319 (19) Å	µ = 0.25 mm⁻¹
α = 74.33 (3)°	T = 293 K
β = 88.60 (3)°	Block, colorless
γ = 74.74 (3)°	0.3 × 0.3 × 0.2 mm
V = 634.7 (2) Å³

Data collection top

Rigaku Mercury CCD diffractometer	2904 independent reflections
Radiation source: fine-focus sealed tube	2621 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −10→10
T_min = 0.489, T_max = 1.000	k = −11→11
6562 measured reflections	l = −12→12

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)] = 0.046	H-atom parameters constrained
wR(F²) = 0.129	w = 1/[σ²(F_o²) + (0.0558P)² + 0.2055P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
2904 reflections	Δρ_max = 0.50 e Å⁻³
150 parameters	Δρ_min = −0.45 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.85 (3)

Crystal data top

2C₆H₁₆N⁺·C₁₀H₆O₆S₂²⁻	γ = 74.74 (3)°
M_r = 490.66	V = 634.7 (2) Å³
Triclinic, P1	Z = 1
a = 7.9518 (16) Å	Mo Kα radiation
b = 9.1215 (18) Å	µ = 0.25 mm⁻¹
c = 9.4319 (19) Å	T = 293 K
α = 74.33 (3)°	0.3 × 0.3 × 0.2 mm
β = 88.60 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	2904 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	2621 reflections with I > 2σ(I)
T_min = 0.489, T_max = 1.000	R_int = 0.038
6562 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.12	Δρ_max = 0.50 e Å⁻³
2904 reflections	Δρ_min = −0.45 e Å⁻³
150 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
C1	−0.0351 (2)	0.2895 (2)	0.7281 (2)	0.0369 (4)
H1B	−0.0197	0.2081	0.8148	0.044*
C2	0.1044 (2)	0.34189 (18)	0.66995 (17)	0.0283 (3)
C3	0.08495 (18)	0.46559 (17)	0.53574 (17)	0.0259 (3)
C4	0.2268 (2)	0.5223 (2)	0.47013 (19)	0.0337 (4)
H4A	0.3383	0.4773	0.5148	0.040*
C5	0.2021 (2)	0.6413 (2)	0.3430 (2)	0.0406 (4)
H5A	0.2965	0.6774	0.3026	0.049*
C6	0.1682 (3)	0.0620 (3)	0.2747 (3)	0.0628 (7)
H6A	0.2490	−0.0343	0.3287	0.094*
H6B	0.1388	0.0527	0.1800	0.094*
H6C	0.0643	0.0818	0.3284	0.094*
C7	0.2506 (2)	0.1971 (2)	0.2543 (2)	0.0429 (4)
H7A	0.2742	0.2097	0.3512	0.052*
C8	0.1320 (3)	0.3506 (3)	0.1613 (3)	0.0607 (6)
H8A	0.1903	0.4329	0.1461	0.091*
H8B	0.0266	0.3784	0.2112	0.091*
H8C	0.1040	0.3377	0.0677	0.091*
C9	0.6308 (4)	0.2023 (4)	0.3419 (3)	0.0714 (8)
H9A	0.5432	0.2048	0.4137	0.107*
H9B	0.7008	0.2709	0.3505	0.107*
H9C	0.7036	0.0964	0.3585	0.107*
C10	0.5439 (3)	0.2570 (2)	0.1895 (2)	0.0437 (5)
H10A	0.4767	0.3676	0.1709	0.052*
C11	0.6760 (3)	0.2441 (4)	0.0729 (3)	0.0661 (7)
H11A	0.7547	0.3062	0.0787	0.099*
H11B	0.6168	0.2822	−0.0227	0.099*
H11C	0.7404	0.1356	0.0886	0.099*
N1	0.42071 (17)	0.15825 (17)	0.18060 (16)	0.0335 (3)
H1C	0.3967	0.1694	0.0849	0.040*
H1D	0.4761	0.0560	0.2216	0.040*
O1	0.28340 (19)	0.14639 (18)	0.90458 (15)	0.0519 (4)
O2	0.3674 (2)	0.38559 (19)	0.79367 (18)	0.0585 (4)
O3	0.42442 (18)	0.17516 (17)	0.67405 (16)	0.0517 (4)
S1	0.31154 (5)	0.25661 (5)	0.76799 (5)	0.0357 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0390 (9)	0.0366 (9)	0.0327 (9)	−0.0133 (7)	0.0020 (7)	−0.0025 (7)
C2	0.0264 (7)	0.0285 (7)	0.0287 (8)	−0.0033 (6)	−0.0008 (6)	−0.0096 (6)
C3	0.0231 (7)	0.0279 (7)	0.0276 (7)	−0.0059 (6)	−0.0001 (6)	−0.0101 (6)
C4	0.0227 (7)	0.0399 (9)	0.0384 (9)	−0.0087 (6)	−0.0004 (6)	−0.0101 (7)
C5	0.0328 (9)	0.0468 (10)	0.0426 (10)	−0.0186 (8)	0.0049 (7)	−0.0054 (8)
C6	0.0394 (11)	0.0591 (14)	0.0805 (17)	−0.0143 (10)	0.0068 (11)	−0.0030 (12)
C7	0.0350 (9)	0.0497 (11)	0.0442 (10)	−0.0058 (8)	0.0055 (7)	−0.0187 (8)
C8	0.0441 (12)	0.0442 (11)	0.0883 (18)	0.0052 (9)	0.0023 (11)	−0.0255 (12)
C9	0.0689 (16)	0.118 (2)	0.0499 (13)	−0.0474 (16)	0.0010 (11)	−0.0383 (14)
C10	0.0414 (10)	0.0422 (10)	0.0495 (11)	−0.0152 (8)	−0.0024 (8)	−0.0114 (8)
C11	0.0519 (13)	0.105 (2)	0.0431 (12)	−0.0390 (13)	0.0018 (10)	−0.0054 (12)
N1	0.0291 (7)	0.0354 (7)	0.0345 (7)	−0.0038 (6)	−0.0022 (5)	−0.0115 (6)
O1	0.0527 (9)	0.0584 (9)	0.0318 (7)	−0.0073 (7)	−0.0081 (6)	0.0023 (6)
O2	0.0545 (9)	0.0595 (9)	0.0644 (10)	−0.0164 (7)	−0.0242 (7)	−0.0182 (8)
O3	0.0412 (8)	0.0515 (8)	0.0456 (8)	0.0119 (6)	0.0027 (6)	−0.0090 (6)
S1	0.0306 (3)	0.0390 (3)	0.0310 (3)	−0.00070 (17)	−0.00660 (16)	−0.00666 (18)

Geometric parameters (Å, º) top

C1—C2	1.366 (2)	C8—H8A	0.9600
C1—C5ⁱ	1.409 (3)	C8—H8B	0.9600
C1—H1B	0.9300	C8—H8C	0.9600
C2—C3	1.430 (2)	C9—C10	1.507 (3)
C2—S1	1.7844 (17)	C9—H9A	0.9600
C3—C4	1.422 (2)	C9—H9B	0.9600
C3—C3ⁱ	1.430 (3)	C9—H9C	0.9600
C4—C5	1.360 (3)	C10—C11	1.508 (3)
C4—H4A	0.9300	C10—N1	1.513 (2)
C5—C1ⁱ	1.409 (3)	C10—H10A	0.9800
C5—H5A	0.9300	C11—H11A	0.9600
C6—C7	1.508 (3)	C11—H11B	0.9600
C6—H6A	0.9600	C11—H11C	0.9600
C6—H6B	0.9600	N1—H1C	0.9000
C6—H6C	0.9600	N1—H1D	0.9000
C7—N1	1.508 (2)	O1—S1	1.4578 (15)
C7—C8	1.517 (3)	O2—S1	1.4401 (16)
C7—H7A	0.9800	O3—S1	1.4521 (15)

C2—C1—C5ⁱ	120.17 (16)	H8B—C8—H8C	109.5
C2—C1—H1B	119.9	C10—C9—H9A	109.5
C5ⁱ—C1—H1B	119.9	C10—C9—H9B	109.5
C1—C2—C3	121.06 (15)	H9A—C9—H9B	109.5
C1—C2—S1	118.57 (13)	C10—C9—H9C	109.5
C3—C2—S1	120.34 (12)	H9A—C9—H9C	109.5
C4—C3—C3ⁱ	118.72 (18)	H9B—C9—H9C	109.5
C4—C3—C2	123.01 (14)	C9—C10—C11	111.56 (19)
C3ⁱ—C3—C2	118.28 (17)	C9—C10—N1	109.39 (17)
C5—C4—C3	121.05 (15)	C11—C10—N1	109.33 (17)
C5—C4—H4A	119.5	C9—C10—H10A	108.8
C3—C4—H4A	119.5	C11—C10—H10A	108.8
C4—C5—C1ⁱ	120.72 (16)	N1—C10—H10A	108.8
C4—C5—H5A	119.6	C10—C11—H11A	109.5
C1ⁱ—C5—H5A	119.6	C10—C11—H11B	109.5
C7—C6—H6A	109.5	H11A—C11—H11B	109.5
C7—C6—H6B	109.5	C10—C11—H11C	109.5
H6A—C6—H6B	109.5	H11A—C11—H11C	109.5
C7—C6—H6C	109.5	H11B—C11—H11C	109.5
H6A—C6—H6C	109.5	C7—N1—C10	115.64 (14)
H6B—C6—H6C	109.5	C7—N1—H1C	108.4
N1—C7—C6	108.75 (16)	C10—N1—H1C	108.4
N1—C7—C8	109.60 (17)	C7—N1—H1D	108.4
C6—C7—C8	111.47 (19)	C10—N1—H1D	108.4
N1—C7—H7A	109.0	H1C—N1—H1D	107.4
C6—C7—H7A	109.0	O2—S1—O3	113.49 (10)
C8—C7—H7A	109.0	O2—S1—O1	112.42 (10)
C7—C8—H8A	109.5	O3—S1—O1	111.45 (9)
C7—C8—H8B	109.5	O2—S1—C2	106.31 (8)
H8A—C8—H8B	109.5	O3—S1—C2	106.05 (8)
C7—C8—H8C	109.5	O1—S1—C2	106.53 (8)
H8A—C8—H8C	109.5

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1ⁱⁱ	0.90	2.03	2.887 (2)	159
N1—H1D···O3ⁱⁱⁱ	0.90	2.02	2.916 (2)	174
C9—H9A···O3	0.96	2.58	3.480 (3)	156
C6—H6A···O3ⁱⁱⁱ	0.96	2.58	3.351 (3)	138
C11—H11C···O1ⁱⁱⁱ	0.96	2.61	3.439 (4)	144
C11—H11B···O2ⁱⁱ	0.96	2.47	3.382 (3)	158

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

Experimental details

Crystal data
Chemical formula	2C₆H₁₆N⁺·C₁₀H₆O₆S₂²⁻
M_r	490.66
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.9518 (16), 9.1215 (18), 9.4319 (19)
α, β, γ (°)	74.33 (3), 88.60 (3), 74.74 (3)
V (Å³)	634.7 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
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	6562, 2904, 2621
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.129, 1.12
No. of reflections	2904
No. of parameters	150
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.45

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—H1C···O1ⁱ	0.90	2.03	2.887 (2)	159
N1—H1D···O3ⁱⁱ	0.90	2.02	2.916 (2)	174
C9—H9A···O3	0.96	2.58	3.480 (3)	156
C6—H6A···O3ⁱⁱ	0.96	2.58	3.351 (3)	138
C11—H11C···O1ⁱⁱ	0.96	2.61	3.439 (4)	144
C11—H11B···O2ⁱ	0.96	2.47	3.382 (3)	158

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

Acknowledgements

Yu Jin thanks Ordered Matter Science Research Center, Southeast University for its excellent experimental facilities.

References

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