Bis(2-methyl­piperidinium) naphthalene-1,5-disulfonate

Xu, Q.

doi:10.1107/S1600536812020041

organic compounds

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Volume 68| Part 6| June 2012| Page o1733

doi:10.1107/S1600536812020041

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Bis(2-methylpiperidinium) naphthalene-1,5-disulfonate

Qian Xu ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: xqchem@yahoo.com.cn

(Received 24 April 2012; accepted 4 May 2012; online 16 May 2012)

In the structure of the title molecular salt, 2C₆H₁₄N⁺·C₁₀H₆O₆S₂²⁻, the asymmetric unit consists of one 2-methylpiperidinium cation and one-half of a naphthalene-1,5-disulfonate anion; the anion lies across a centre of symmetry. In the crystal, the cations and anions are linked through N—H⋯O hydrogen bonds, forming a two-dimensional network.

Related literature

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

Experimental

Crystal data

2C₆H₁₄N⁺·C₁₀H₆O₆S₂²⁻
M_r = 486.63
Monoclinic, P 2₁ /c
a = 12.040 (2) Å
b = 8.8133 (18) Å
c = 12.715 (3) Å
β = 112.62 (3)°
V = 1245.4 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.32 × 0.27 × 0.22 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.924, T_max = 0.947
12383 measured reflections
2814 independent reflections
1942 reflections with I > 2σ(I)
R_int = 0.069
Standard reflections: ?

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.134
S = 1.04
2814 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2	0.90	1.91	2.795 (3)	169
N1—H1A⋯O1ⁱ	0.90	1.93	2.820 (3)	169
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812020041/go2054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020041/go2054Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020041/go2054Isup3.cml

checkCIF report

Comment top

The title compound, (I), was synthesized to assess its ferroelectric properties by dielectric measurements as a function of temperature (Fu et al., 2009; Ye et al., 2006; Zhang et al., 2008; Zhang et al., 2010). In the range from 190K to near its melting point (m.p. >370K), no dielectric anomaly was observed.

A view of (I) is shown in Fig.1. Two intermolecular N–H···O hydrogen bonds form a two-dimensional network, Table, 1, Fig. 2.

Related literature top

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

Experimental top

A mixture of 2-methy piperidine (0.98 g, 10 mmol), naphthalene-1,5-disulfonic acid (2.5 g, 10 mmol) in water was stirred for several days at ambient temperature, colourless crystals were obtained.

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: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with the displacement ellipsoids drawn at the 30% probability level. Symmetry code for A: 1 - x, 1 - y, 1 - z.
	Fig. 2. Packing diagram of the title compound, hydrogen bonds are shown as dashed lines.

Bis(2-methylpiperidinium) naphthalene-1,5-disulfonate top

Crystal data top

2C₆H₁₄N⁺·C₁₀H₆O₆S₂²⁻	F(000) = 520
M_r = 486.63	D_x = 1.298 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2814 reflections
a = 12.040 (2) Å	θ = 3.1–27.5°
b = 8.8133 (18) Å	µ = 0.25 mm⁻¹
c = 12.715 (3) Å	T = 293 K
β = 112.62 (3)°	Block, colourless
V = 1245.4 (4) Å³	0.32 × 0.27 × 0.22 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	2814 independent reflections
Radiation source: fine-focus sealed tube	1942 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.069
CCD_Profile_fitting scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −15→15
T_min = 0.924, T_max = 0.947	k = −11→11
12383 measured reflections	l = −16→16

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0546P)² + 0.481P] where P = (F_o² + 2F_c²)/3
2814 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

2C₆H₁₄N⁺·C₁₀H₆O₆S₂²⁻	V = 1245.4 (4) Å³
M_r = 486.63	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.040 (2) Å	µ = 0.25 mm⁻¹
b = 8.8133 (18) Å	T = 293 K
c = 12.715 (3) Å	0.32 × 0.27 × 0.22 mm
β = 112.62 (3)°

Data collection top

Rigaku SCXmini diffractometer	2814 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1942 reflections with I > 2σ(I)
T_min = 0.924, T_max = 0.947	R_int = 0.069
12383 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.04	Δρ_max = 0.22 e Å⁻³
2814 reflections	Δρ_min = −0.28 e Å⁻³
146 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
S1	0.78457 (5)	0.59654 (7)	0.69286 (5)	0.0339 (2)
O1	0.88140 (15)	0.6629 (2)	0.66486 (16)	0.0499 (5)
O2	0.81475 (16)	0.4419 (2)	0.73778 (15)	0.0452 (5)
O3	0.74714 (16)	0.6921 (2)	0.76559 (16)	0.0508 (5)
C7	0.6587 (2)	0.5777 (3)	0.5596 (2)	0.0306 (5)
C8	0.6710 (2)	0.6257 (3)	0.4618 (2)	0.0376 (6)
H8	0.7426	0.6706	0.4663	0.045*
C9	0.5757 (2)	0.6074 (3)	0.3545 (2)	0.0439 (7)
H9	0.5848	0.6414	0.2890	0.053*
C10	0.5479 (2)	0.5101 (3)	0.55522 (19)	0.0286 (5)
C11	0.5297 (2)	0.4597 (3)	0.6538 (2)	0.0388 (6)
H11	0.5907	0.4727	0.7253	0.047*
N1	0.88441 (18)	0.1722 (2)	0.66473 (18)	0.0395 (5)
H1A	0.9617	0.1614	0.7127	0.047*
H1B	0.8586	0.2628	0.6790	0.047*
C1	0.8782 (2)	0.1714 (3)	0.5439 (2)	0.0475 (7)
H1	0.9076	0.0732	0.5292	0.057*
C2	0.7463 (3)	0.1887 (3)	0.4635 (2)	0.0509 (8)
H2A	0.7176	0.2877	0.4750	0.061*
H2B	0.7404	0.1834	0.3854	0.061*
C3	0.6666 (3)	0.0666 (4)	0.4827 (3)	0.0713 (10)
H3A	0.6888	−0.0317	0.4624	0.086*
H3B	0.5833	0.0860	0.4341	0.086*
C4	0.6799 (3)	0.0642 (4)	0.6077 (3)	0.0668 (10)
H4A	0.6468	0.1569	0.6248	0.080*
H4B	0.6345	−0.0204	0.6196	0.080*
C5	0.8109 (3)	0.0494 (3)	0.6881 (3)	0.0552 (8)
H5A	0.8172	0.0568	0.7663	0.066*
H5B	0.8415	−0.0490	0.6780	0.066*
C6	0.9591 (3)	0.2953 (4)	0.5302 (3)	0.0726 (10)
H6A	0.9276	0.3927	0.5383	0.109*
H6B	0.9623	0.2879	0.4561	0.109*
H6C	1.0387	0.2838	0.5875	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0244 (3)	0.0376 (4)	0.0378 (4)	−0.0008 (3)	0.0099 (2)	−0.0067 (3)
O1	0.0283 (9)	0.0686 (14)	0.0508 (12)	−0.0130 (9)	0.0130 (8)	−0.0050 (10)
O2	0.0429 (11)	0.0441 (11)	0.0426 (11)	0.0092 (8)	0.0099 (8)	0.0024 (8)
O3	0.0425 (11)	0.0563 (13)	0.0549 (12)	−0.0018 (9)	0.0201 (9)	−0.0229 (10)
C7	0.0239 (12)	0.0284 (12)	0.0400 (14)	−0.0010 (10)	0.0128 (10)	0.0001 (10)
C8	0.0287 (13)	0.0395 (15)	0.0466 (16)	−0.0077 (11)	0.0166 (12)	0.0011 (12)
C9	0.0392 (14)	0.0593 (18)	0.0380 (15)	−0.0038 (13)	0.0200 (12)	0.0103 (13)
C10	0.0260 (12)	0.0274 (12)	0.0318 (13)	0.0005 (10)	0.0103 (9)	0.0013 (10)
C11	0.0304 (13)	0.0516 (16)	0.0307 (14)	−0.0030 (12)	0.0077 (11)	0.0052 (11)
N1	0.0324 (11)	0.0387 (13)	0.0425 (13)	0.0040 (9)	0.0088 (10)	0.0010 (10)
C1	0.0460 (16)	0.0509 (18)	0.0490 (17)	0.0072 (13)	0.0221 (14)	−0.0056 (13)
C2	0.0547 (18)	0.0561 (19)	0.0350 (16)	−0.0007 (15)	0.0097 (13)	−0.0042 (13)
C3	0.061 (2)	0.074 (2)	0.061 (2)	−0.0227 (18)	0.0029 (17)	−0.0099 (18)
C4	0.0486 (19)	0.075 (2)	0.070 (2)	−0.0180 (17)	0.0150 (17)	0.0046 (17)
C5	0.0578 (19)	0.0477 (18)	0.0576 (19)	−0.0046 (14)	0.0196 (16)	0.0110 (14)
C6	0.055 (2)	0.102 (3)	0.064 (2)	−0.0095 (19)	0.0280 (17)	0.017 (2)

Geometric parameters (Å, º) top

S1—O3	1.4452 (18)	C1—C6	1.518 (4)
S1—O1	1.4652 (18)	C1—C2	1.530 (4)
S1—O2	1.4687 (19)	C1—H1	0.9800
S1—C7	1.794 (3)	C2—C3	1.523 (4)
C7—C8	1.374 (3)	C2—H2A	0.9700
C7—C10	1.442 (3)	C2—H2B	0.9700
C8—C9	1.414 (4)	C3—C4	1.535 (5)
C8—H8	0.9300	C3—H3A	0.9700
C9—C11ⁱ	1.367 (3)	C3—H3B	0.9700
C9—H9	0.9300	C4—C5	1.519 (4)
C10—C11	1.424 (3)	C4—H4A	0.9700
C10—C10ⁱ	1.445 (4)	C4—H4B	0.9700
C11—C9ⁱ	1.367 (3)	C5—H5A	0.9700
C11—H11	0.9300	C5—H5B	0.9700
N1—C5	1.498 (3)	C6—H6A	0.9600
N1—C1	1.509 (3)	C6—H6B	0.9600
N1—H1A	0.90	C6—H6C	0.9600
N1—H1B	0.90

O3—S1—O1	113.33 (12)	C2—C1—H1	108.6
O3—S1—O2	112.56 (12)	C3—C2—C1	112.2 (2)
O1—S1—O2	111.33 (12)	C3—C2—H2A	109.2
O3—S1—C7	107.48 (11)	C1—C2—H2A	109.2
O1—S1—C7	105.63 (11)	C3—C2—H2B	109.2
O2—S1—C7	105.90 (11)	C1—C2—H2B	109.2
C8—C7—C10	120.8 (2)	H2A—C2—H2B	107.9
C8—C7—S1	118.69 (18)	C2—C3—C4	110.8 (2)
C10—C7—S1	120.49 (18)	C2—C3—H3A	109.5
C7—C8—C9	120.6 (2)	C4—C3—H3A	109.5
C7—C8—H8	119.7	C2—C3—H3B	109.5
C9—C8—H8	119.7	C4—C3—H3B	109.5
C11ⁱ—C9—C8	120.6 (2)	H3A—C3—H3B	108.1
C11ⁱ—C9—H9	119.7	C5—C4—C3	111.5 (3)
C8—C9—H9	119.7	C5—C4—H4A	109.3
C11—C10—C7	123.2 (2)	C3—C4—H4A	109.3
C11—C10—C10ⁱ	118.8 (3)	C5—C4—H4B	109.3
C7—C10—C10ⁱ	118.0 (3)	C3—C4—H4B	109.3
C9ⁱ—C11—C10	121.3 (2)	H4A—C4—H4B	108.0
C9ⁱ—C11—H11	119.3	N1—C5—C4	110.1 (2)
C10—C11—H11	119.3	N1—C5—H5A	109.6
C5—N1—C1	113.4 (2)	C4—C5—H5A	109.6
C5—N1—H1A	109.0	N1—C5—H5B	109.6
C1—N1—H1A	108.8	C4—C5—H5B	109.6
C5—N1—H1B	108.9	H5A—C5—H5B	108.1
C1—N1—H1B	108.9	C1—C6—H6A	109.5
H1A—N1—H1B	107.7	C1—C6—H6B	109.5
N1—C1—C6	109.3 (2)	H6A—C6—H6B	109.5
N1—C1—C2	108.2 (2)	C1—C6—H6C	109.5
C6—C1—C2	113.5 (3)	H6A—C6—H6C	109.5
N1—C1—H1	108.6	H6B—C6—H6C	109.5
C6—C1—H1	108.6

O3—S1—C7—C8	120.4 (2)	S1—C7—C10—C10ⁱ	−176.5 (2)
O1—S1—C7—C8	−0.8 (2)	C7—C10—C11—C9ⁱ	−178.3 (2)
O2—S1—C7—C8	−119.0 (2)	C10ⁱ—C10—C11—C9ⁱ	0.4 (4)
O3—S1—C7—C10	−61.0 (2)	C5—N1—C1—C6	−177.8 (2)
O1—S1—C7—C10	177.70 (18)	C5—N1—C1—C2	58.2 (3)
O2—S1—C7—C10	59.5 (2)	N1—C1—C2—C3	−56.1 (3)
C10—C7—C8—C9	−1.1 (4)	C6—C1—C2—C3	−177.6 (3)
S1—C7—C8—C9	177.49 (19)	C1—C2—C3—C4	55.1 (4)
C7—C8—C9—C11ⁱ	−0.7 (4)	C2—C3—C4—C5	−53.6 (4)
C8—C7—C10—C11	−179.3 (2)	C1—N1—C5—C4	−58.2 (3)
S1—C7—C10—C11	2.1 (3)	C3—C4—C5—N1	54.5 (4)
C8—C7—C10—C10ⁱ	2.0 (4)

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—H1B···O2	0.90	1.91	2.795 (3)	169
N1—H1A···O1ⁱⁱ	0.90	1.93	2.820 (3)	169

Symmetry code: (ii) −x+2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	2C₆H₁₄N⁺·C₁₀H₆O₆S₂²⁻
M_r	486.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.040 (2), 8.8133 (18), 12.715 (3)
β (°)	112.62 (3)
V (Å³)	1245.4 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.32 × 0.27 × 0.22

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.924, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	12383, 2814, 1942
R_int	0.069
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.134, 1.04
No. of reflections	2814
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.28

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2	0.90	1.91	2.795 (3)	169
N1—H1A···O1ⁱ	0.90	1.93	2.820 (3)	169

Symmetry code: (i) −x+2, y−1/2, −z+3/2.

Acknowledgements

This work was supported by Southeast University.

References

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