Bis(3-methyl­piperidinium) naphthalene-1,5-disulfonate

Xu, Q.

doi:10.1107/S160053681202003X

organic compounds

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Volume 68| Part 6| June 2012| Page o1687

doi:10.1107/S160053681202003X

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Bis(3-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 12 May 2012)

The asymmetric unit of the title compound, 2C₆H₁₄N⁺·C₁₀H₆O₆S₂²⁻, contains one 3-methylpiperidinium cation and one-half of the centrosymmetric naphthalene-1,5-disulfonate anion. In the crystal, anions and cations are linked through N—H⋯O hydrogen bonds into layers parallel to (101).

Related literature

The crystal structure of the related bis(2-methylpiperidinium) pentachloridoantimonate(III) has been reported by Xu (2012 ).

Experimental

Crystal data

2C₆H₁₄N⁺·C₁₀H₆O₆S₂²⁻
M_r = 486.63
Monoclinic, C 2/c
a = 18.100 (4) Å
b = 9.1763 (18) Å
c = 15.151 (3) Å
β = 102.06 (3)°
V = 2460.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.34 × 0.27 × 0.22 mm

Data collection

Rigaku Mercury70 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.965, T_max = 0.993
12253 measured reflections
2816 independent reflections
1835 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.151
S = 1.03
2816 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.65 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—H1C⋯O2	0.90	2.01	2.855 (3)	156
N1—H1D⋯O1ⁱ	0.90	1.91	2.804 (3)	175
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SCXmini (Rigaku, 2006 ); cell refinement: SCXmini; data reduction: SCXmini; 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/S160053681202003X/cv5290sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681202003X/cv5290Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681202003X/cv5290Isup3.cml

checkCIF report

Comment top

In a continuation of a structural study of new potent ferroelectric materials containing methylpiperidinium cations (Xu, 2012), we present here the title compound, (I).

The asymmetric unit of (I) contains one 3-methylpiperidinium cation and one-half of the centrosymmetric naphthalene-1,5-disulfonate anion (Fig. 1). Intermolecular N—H···O hydrogen bonds (Table 1, Fig. 2) link anions and cations into layers parallel to (101).

Related literature top

The crystal structure of the related bis(2-methylpiperidinium) pentachloridoantimonate(III) has been reported by Xu (2012).

Experimental top

A mixture of 3-methylpiperdine (0.98 g, 10 mmol), 1,5-naphthalenedisulfonic acid (2.5 g, 10 mmol) in a water was stirred for several days at ambient temperature to obtain colourless crystals.

Computing details top

Data collection: SCXmini (Rigaku, 2006); cell refinement: SCXmini (Rigaku, 2006); data reduction: SCXmini (Rigaku, 2006); 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 (I) showing the atomic numbering and displacement ellipsoids drawn at the 30% probability level [symmetry code: (A) -x, 1 - y, -z]. Dashed line denotes hydrogen bond.
	Fig. 2. A portion of the crystal packing viewed down the c axis. Hydrogen bonds are shown as dashed lines.

Bis(3-methylpiperidinium) naphthalene-1,5-disulfonate top

Crystal data top

2C₆H₁₄N⁺·C₁₀H₆O₆S₂²⁻	F(000) = 1040
M_r = 486.63	D_x = 1.313 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2816 reflections
a = 18.100 (4) Å	θ = 3.1–27.5°
b = 9.1763 (18) Å	µ = 0.26 mm⁻¹
c = 15.151 (3) Å	T = 293 K
β = 102.06 (3)°	Prism, colourless
V = 2460.9 (8) Å³	0.34 × 0.27 × 0.22 mm
Z = 4

Data collection top

Rigaku Mercury70 CCD diffractometer	2816 independent reflections
Radiation source: fine-focus sealed tube	1835 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −22→23
T_min = 0.965, T_max = 0.993	k = −11→11
12253 measured reflections	l = −19→19

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.151	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0675P)² + 2.1939P] where P = (F_o² + 2F_c²)/3
2816 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

2C₆H₁₄N⁺·C₁₀H₆O₆S₂²⁻	V = 2460.9 (8) Å³
M_r = 486.63	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.100 (4) Å	µ = 0.26 mm⁻¹
b = 9.1763 (18) Å	T = 293 K
c = 15.151 (3) Å	0.34 × 0.27 × 0.22 mm
β = 102.06 (3)°

Data collection top

Rigaku Mercury70 CCD diffractometer	2816 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1835 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.993	R_int = 0.051
12253 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.151	H-atom parameters constrained
S = 1.03	Δρ_max = 0.65 e Å⁻³
2816 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
C1	0.29821 (16)	0.5641 (4)	0.3876 (2)	0.0640 (8)
H1A	0.2607	0.4947	0.3987	0.077*
H1B	0.2754	0.6602	0.3829	0.077*
C2	0.36527 (17)	0.5617 (4)	0.4661 (2)	0.0627 (8)
H2	0.3851	0.4620	0.4727	0.075*
C3	0.42612 (18)	0.6595 (4)	0.4453 (3)	0.0757 (10)
H3A	0.4710	0.6497	0.4927	0.091*
H3B	0.4094	0.7600	0.4449	0.091*
C4	0.44594 (19)	0.6248 (5)	0.3555 (3)	0.0841 (11)
H4A	0.4828	0.6947	0.3434	0.101*
H4B	0.4685	0.5285	0.3581	0.101*
C5	0.3770 (2)	0.6296 (4)	0.2807 (3)	0.0745 (10)
H5A	0.3566	0.7277	0.2745	0.089*
H5B	0.3902	0.6023	0.2241	0.089*
C6	0.3419 (3)	0.6035 (6)	0.5532 (3)	0.1106 (15)
H6A	0.3198	0.6990	0.5471	0.166*
H6B	0.3854	0.6033	0.6018	0.166*
H6C	0.3055	0.5345	0.5657	0.166*
C7	0.02115 (13)	0.5265 (3)	0.04203 (16)	0.0363 (6)
C8	0.09422 (13)	0.5875 (3)	0.04328 (17)	0.0401 (6)
C9	0.12180 (15)	0.5968 (3)	−0.03345 (19)	0.0491 (7)
H9	0.1687	0.6394	−0.0316	0.059*
C10	−0.01080 (15)	0.5181 (3)	0.11938 (18)	0.0463 (7)
H10	0.0160	0.5547	0.1740	0.056*
C11	0.08005 (16)	0.5426 (3)	−0.11543 (19)	0.0538 (7)
H11	0.0998	0.5482	−0.1673	0.065*
N1	0.32008 (12)	0.5276 (3)	0.30185 (17)	0.0556 (7)
H1C	0.2788	0.5298	0.2569	0.067*
H1D	0.3388	0.4365	0.3052	0.067*
O1	0.11209 (11)	0.7517 (2)	0.18646 (14)	0.0616 (6)
O2	0.16835 (11)	0.5125 (2)	0.20070 (14)	0.0660 (6)
O3	0.22131 (11)	0.7037 (2)	0.12446 (15)	0.0667 (6)
S1	0.15360 (4)	0.64375 (7)	0.14678 (5)	0.0470 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0435 (16)	0.075 (2)	0.071 (2)	−0.0021 (15)	0.0072 (15)	−0.0047 (18)
C2	0.0613 (19)	0.0546 (18)	0.066 (2)	−0.0005 (15)	−0.0021 (16)	−0.0012 (16)
C3	0.063 (2)	0.060 (2)	0.091 (3)	−0.0163 (16)	−0.0146 (18)	−0.0074 (18)
C4	0.057 (2)	0.083 (3)	0.112 (3)	−0.0254 (19)	0.016 (2)	−0.007 (2)
C5	0.086 (2)	0.066 (2)	0.072 (2)	−0.0020 (19)	0.0185 (19)	0.0072 (18)
C6	0.129 (4)	0.130 (4)	0.072 (3)	0.000 (3)	0.019 (3)	−0.005 (3)
C7	0.0346 (12)	0.0353 (13)	0.0356 (13)	0.0082 (10)	−0.0003 (10)	0.0027 (10)
C8	0.0342 (12)	0.0392 (13)	0.0436 (15)	0.0049 (10)	0.0003 (11)	0.0013 (11)
C9	0.0373 (14)	0.0532 (17)	0.0561 (17)	0.0006 (12)	0.0083 (12)	0.0004 (13)
C10	0.0438 (14)	0.0526 (16)	0.0386 (14)	0.0018 (12)	−0.0001 (11)	0.0003 (12)
C11	0.0509 (16)	0.069 (2)	0.0421 (15)	0.0000 (14)	0.0120 (13)	0.0001 (14)
N1	0.0452 (13)	0.0484 (13)	0.0630 (15)	0.0077 (11)	−0.0122 (12)	−0.0001 (12)
O1	0.0608 (12)	0.0539 (12)	0.0676 (13)	−0.0040 (10)	0.0075 (11)	−0.0187 (10)
O2	0.0629 (13)	0.0571 (13)	0.0623 (13)	0.0007 (10)	−0.0233 (10)	0.0095 (10)
O3	0.0442 (11)	0.0723 (14)	0.0791 (15)	−0.0137 (10)	0.0026 (10)	−0.0100 (12)
S1	0.0399 (4)	0.0442 (4)	0.0493 (4)	−0.0003 (3)	−0.0077 (3)	−0.0029 (3)

Geometric parameters (Å, º) top

C1—N1	1.474 (4)	C6—H6C	0.9600
C1—C2	1.512 (4)	C7—C10	1.413 (4)
C1—H1A	0.9700	C7—C7ⁱ	1.427 (5)
C1—H1B	0.9700	C7—C8	1.433 (3)
C2—C3	1.504 (4)	C8—C9	1.360 (4)
C2—C6	1.517 (5)	C8—S1	1.782 (3)
C2—H2	0.9800	C9—C11	1.403 (4)
C3—C4	1.512 (5)	C9—H9	0.9300
C3—H3A	0.9700	C10—C11ⁱ	1.361 (4)
C3—H3B	0.9700	C10—H10	0.9300
C4—C5	1.501 (5)	C11—C10ⁱ	1.361 (4)
C4—H4A	0.9700	C11—H11	0.9300
C4—H4B	0.9700	N1—H1C	0.9000
C5—N1	1.476 (4)	N1—H1D	0.9000
C5—H5A	0.9700	O1—S1	1.447 (2)
C5—H5B	0.9700	O2—S1	1.449 (2)
C6—H6A	0.9600	O3—S1	1.447 (2)
C6—H6B	0.9600

N1—C1—C2	111.8 (2)	H6A—C6—H6B	109.5
N1—C1—H1A	109.3	C2—C6—H6C	109.5
C2—C1—H1A	109.3	H6A—C6—H6C	109.5
N1—C1—H1B	109.3	H6B—C6—H6C	109.5
C2—C1—H1B	109.3	C10—C7—C7ⁱ	119.0 (3)
H1A—C1—H1B	107.9	C10—C7—C8	123.1 (2)
C3—C2—C6	112.4 (3)	C7ⁱ—C7—C8	117.8 (3)
C3—C2—C1	109.3 (3)	C9—C8—C7	121.0 (2)
C6—C2—C1	110.9 (3)	C9—C8—S1	118.2 (2)
C3—C2—H2	108.1	C7—C8—S1	120.68 (19)
C6—C2—H2	108.1	C8—C9—C11	120.6 (2)
C1—C2—H2	108.1	C8—C9—H9	119.7
C2—C3—C4	112.6 (3)	C11—C9—H9	119.7
C2—C3—H3A	109.1	C11ⁱ—C10—C7	121.2 (2)
C4—C3—H3A	109.1	C11ⁱ—C10—H10	119.4
C2—C3—H3B	109.1	C7—C10—H10	119.4
C4—C3—H3B	109.1	C10ⁱ—C11—C9	120.3 (3)
H3A—C3—H3B	107.8	C10ⁱ—C11—H11	119.8
C5—C4—C3	110.9 (3)	C9—C11—H11	119.8
C5—C4—H4A	109.5	C1—N1—C5	112.1 (3)
C3—C4—H4A	109.5	C1—N1—H1C	109.2
C5—C4—H4B	109.5	C5—N1—H1C	109.2
C3—C4—H4B	109.5	C1—N1—H1D	109.2
H4A—C4—H4B	108.0	C5—N1—H1D	109.2
N1—C5—C4	109.0 (3)	H1C—N1—H1D	107.9
N1—C5—H5A	109.9	O3—S1—O1	112.05 (13)
C4—C5—H5A	109.9	O3—S1—O2	112.52 (13)
N1—C5—H5B	109.9	O1—S1—O2	112.66 (14)
C4—C5—H5B	109.9	O3—S1—C8	106.81 (13)
H5A—C5—H5B	108.3	O1—S1—C8	107.07 (12)
C2—C6—H6A	109.5	O2—S1—C8	105.17 (12)
C2—C6—H6B	109.5

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2	0.90	2.01	2.855 (3)	156
N1—H1D···O1ⁱⁱ	0.90	1.91	2.804 (3)	175

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

Experimental details

Crystal data
Chemical formula	2C₆H₁₄N⁺·C₁₀H₆O₆S₂²⁻
M_r	486.63
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.100 (4), 9.1763 (18), 15.151 (3)
β (°)	102.06 (3)
V (Å³)	2460.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.34 × 0.27 × 0.22

Data collection
Diffractometer	Rigaku Mercury70 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.965, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	12253, 2816, 1835
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.151, 1.03
No. of reflections	2816
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.28

Computer programs: SCXmini (Rigaku, 2006), 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—H1C···O2	0.90	2.01	2.855 (3)	156.1
N1—H1D···O1ⁱ	0.90	1.91	2.804 (3)	174.5

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 20701007) and Jiangsu Province (grant No. BK2008286).

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2006). SCXmini Benchtop Crystallography System Software. Rigaku Americas Corporation, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, Q. (2012). Acta Cryst. E68, m671. CSD CrossRef IUCr Journals Google Scholar