Piperazine-1,4-diium naphthalene-1,5-disulfonate

Wei, B.

doi:10.1107/S1600536811038955

organic compounds

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Volume 67| Part 10| October 2011| Page o2811

https://doi.org/10.1107/S1600536811038955

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Piperazine-1,4-diium naphthalene-1,5-disulfonate

Bin Wei ^a ^*

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

(Received 9 September 2011; accepted 22 September 2011; online 30 September 2011)

The title molecular salt, C₄H₁₂N₂²⁺·C₁₀H₆O₆S₂²⁻, consists of a piperazinium cation and a 1,5-naphthalenedisulfonate anion. Crystallographic inversion centers are situated at the center of the ring of the dication as well as at the midpoint of the central carbon–carbon bond in the dianion. In the crystal, intermolecular N—H⋯O hydrogen bonds link the cations and anions.

Related literature

The title compound was obtained during attempts to obtain dielectric-ferroelectric compounds. For general background to ferroelectric metal-organic frameworks, see: Wu et al. (2011 ); Ye et al. (2006 ); Zhang et al. (2008 , 2010 ); Fu et al. (2009 ).

Experimental

Crystal data

C₄H₁₂N₂²⁺·C₁₀H₆O₆S₂²⁻
M_r = 374.42
Monoclinic, P 2₁ /c
a = 11.997 (2) Å
b = 7.2959 (15) Å
c = 9.1453 (18) Å
β = 96.00 (3)°
V = 796.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.955, T_max = 0.955
7956 measured reflections
1827 independent reflections
1629 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.088
S = 1.11
1827 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.26 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—H1A⋯O2ⁱ	0.90	1.91	2.7357 (19)	153
N1—H1B⋯O3ⁱⁱ	0.90	1.91	2.7670 (19)	159
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811038955/vm2121sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811038955/vm2121Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811038955/vm2121Isup3.cml

checkCIF report

Comment top

Dielectric-ferroelectrics are 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 (402-403K) of the compound, we have found that the title compound has no dielectric disuniformity from 80 K to 405 K. Here we descibe the crystal structure of this compound.

The asymmetric unit of the title compound consists of a half piperazinium cation and a half 1,5-naphthalenedisulfonate anion (Fig. 1). The complete complete molecular structures are generated by inversion centers at the center of the piperazinium ring and at the midpoint of the central carbon-carbon bond in the naphthalene ring. The best planes through the piperazinium ring and the naphthalene ring make a dihedral angle of 80.96 (8)°. The cations and anions are connected by intermolecular N—H···O hydrogen bonds, which contribute to the stability of the crystal structure (Fig. 2 and Table 1).

Related literature top

The title compound was obtained during attempts to produce dielectric-ferroelectric compounds. For general background to ferroelectric metal-organic frameworks, see: Wu et al. (2011); Ye et al. (2006); Zhang et al. (2008, 2010); Fu et al. (2009).

Experimental top

The title compound was obtained by the addition of 1,5-naphthalenedisulfonate acid (3.62 g, 0.01 mol) to a solution of piperazine (0.88 g, 0.01 mol) in water, in the stoichiometric ratio 1: 1. Good quality single crystals were obtained by slow evaporation after two days (yield: 48%).

Structure description top

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: SHELXS97 (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 atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes: (i) -x + 1, -y, -z + 2; (ii) -x + 2, -y, -z + 1.
	Fig. 2. A view of the packing of the title compound along the a axis. Dashed lines indicate hydrogen bonds.

Piperazine-1,4-diium naphthalene-1,5-disulfonate top

Crystal data top

C₄H₁₂N₂²⁺·C₁₀H₆O₆S₂²⁻	Z = 2
M_r = 374.42	F(000) = 392
Monoclinic, P2₁/c	D_x = 1.562 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.997 (2) Å	θ = 3.0–27.5°
b = 7.2959 (15) Å	µ = 0.37 mm⁻¹
c = 9.1453 (18) Å	T = 293 K
β = 96.00 (3)°	Block, colorless
V = 796.1 (3) Å³	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku SCXmini diffractometer	1827 independent reflections
Radiation source: fine-focus sealed tube	1629 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
CCD_Profile_fitting scans	θ_max = 27.5°, θ_min = 3.3°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −15→15
T_min = 0.955, T_max = 0.955	k = −9→9
7956 measured reflections	l = −11→11

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.038P)² + 0.4026P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
1827 reflections	Δρ_max = 0.26 e Å⁻³
109 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0

Crystal data top

C₄H₁₂N₂²⁺·C₁₀H₆O₆S₂²⁻	V = 796.1 (3) Å³
M_r = 374.42	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.997 (2) Å	µ = 0.37 mm⁻¹
b = 7.2959 (15) Å	T = 293 K
c = 9.1453 (18) Å	0.20 × 0.20 × 0.20 mm
β = 96.00 (3)°

Data collection top

Rigaku SCXmini diffractometer	1827 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1629 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.955	R_int = 0.031
7956 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.088	H-atom parameters constrained
S = 1.11	Δρ_max = 0.26 e Å⁻³
1827 reflections	Δρ_min = −0.36 e Å⁻³
109 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	0.72018 (3)	0.02705 (6)	0.55200 (4)	0.02178 (13)
C11	0.94220 (13)	−0.0264 (2)	0.49266 (17)	0.0209 (3)
C12	0.86385 (13)	0.0911 (2)	0.55496 (17)	0.0213 (3)
C7	0.89809 (14)	0.2508 (2)	0.6239 (2)	0.0291 (4)
H7	0.8460	0.3258	0.6632	0.035*
C16	0.91084 (14)	−0.1936 (2)	0.4198 (2)	0.0287 (4)
H16	0.8360	−0.2294	0.4101	0.034*
C8	1.01178 (15)	0.3021 (3)	0.6358 (2)	0.0347 (4)
H8	1.0342	0.4115	0.6822	0.042*
N1	0.39695 (11)	0.03920 (19)	0.90988 (15)	0.0230 (3)
H1A	0.3451	0.1206	0.8730	0.028*
H1B	0.3762	−0.0722	0.8746	0.028*
C5	0.40092 (15)	0.0374 (3)	1.07288 (19)	0.0292 (4)
H5A	0.3293	−0.0036	1.1011	0.035*
H5B	0.4143	0.1607	1.1104	0.035*
C1	0.50731 (14)	0.0883 (3)	0.86030 (18)	0.0270 (4)
H1C	0.5256	0.2139	0.8882	0.032*
H1D	0.5027	0.0802	0.7540	0.032*
O1	0.67590 (11)	0.0023 (2)	0.39986 (15)	0.0384 (3)
O3	0.66605 (10)	0.17560 (17)	0.62410 (15)	0.0334 (3)
O2	0.72065 (10)	−0.14134 (17)	0.63779 (14)	0.0312 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0183 (2)	0.0221 (2)	0.0249 (2)	−0.00043 (14)	0.00176 (15)	0.00085 (15)
C11	0.0206 (8)	0.0213 (8)	0.0205 (8)	−0.0020 (6)	0.0011 (6)	−0.0019 (6)
C12	0.0196 (7)	0.0220 (8)	0.0221 (8)	−0.0016 (6)	0.0015 (6)	0.0005 (6)
C7	0.0253 (8)	0.0261 (9)	0.0362 (10)	0.0007 (7)	0.0047 (7)	−0.0093 (7)
C16	0.0225 (8)	0.0279 (9)	0.0357 (10)	−0.0072 (7)	0.0024 (7)	−0.0091 (8)
C8	0.0309 (9)	0.0290 (9)	0.0440 (11)	−0.0080 (7)	0.0032 (8)	−0.0176 (8)
N1	0.0229 (7)	0.0229 (7)	0.0221 (7)	0.0017 (5)	−0.0022 (5)	0.0011 (5)
C5	0.0282 (9)	0.0363 (10)	0.0235 (8)	0.0051 (7)	0.0047 (7)	0.0003 (7)
C1	0.0275 (8)	0.0321 (9)	0.0212 (8)	−0.0028 (7)	0.0012 (6)	0.0070 (7)
O1	0.0290 (7)	0.0556 (9)	0.0284 (7)	−0.0015 (6)	−0.0070 (5)	−0.0012 (6)
O3	0.0273 (6)	0.0267 (7)	0.0478 (8)	0.0040 (5)	0.0120 (6)	−0.0017 (6)
O2	0.0324 (7)	0.0230 (6)	0.0386 (7)	−0.0042 (5)	0.0051 (5)	0.0053 (5)

Geometric parameters (Å, º) top

S1—O1	1.4477 (14)	C8—C16ⁱ	1.359 (3)
S1—O3	1.4562 (13)	C8—H8	0.9300
S1—O2	1.4574 (13)	N1—C5	1.486 (2)
S1—C12	1.7834 (16)	N1—C1	1.487 (2)
C11—C16	1.422 (2)	N1—H1A	0.9000
C11—C11ⁱ	1.432 (3)	N1—H1B	0.9000
C11—C12	1.434 (2)	C5—C1ⁱⁱ	1.512 (2)
C12—C7	1.367 (2)	C5—H5A	0.9700
C7—C8	1.408 (2)	C5—H5B	0.9700
C7—H7	0.9300	C1—C5ⁱⁱ	1.512 (2)
C16—C8ⁱ	1.359 (3)	C1—H1C	0.9700
C16—H16	0.9300	C1—H1D	0.9700

O1—S1—O3	113.07 (8)	C7—C8—H8	119.6
O1—S1—O2	113.12 (8)	C5—N1—C1	111.82 (13)
O3—S1—O2	111.13 (8)	C5—N1—H1A	109.3
O1—S1—C12	107.70 (8)	C1—N1—H1A	109.3
O3—S1—C12	105.90 (8)	C5—N1—H1B	109.3
O2—S1—C12	105.28 (8)	C1—N1—H1B	109.3
C16—C11—C11ⁱ	118.75 (18)	H1A—N1—H1B	107.9
C16—C11—C12	123.17 (15)	N1—C5—C1ⁱⁱ	110.87 (14)
C11ⁱ—C11—C12	118.07 (18)	N1—C5—H5A	109.5
C7—C12—C11	121.01 (15)	C1ⁱⁱ—C5—H5A	109.5
C7—C12—S1	118.27 (13)	N1—C5—H5B	109.5
C11—C12—S1	120.66 (12)	C1ⁱⁱ—C5—H5B	109.5
C12—C7—C8	120.27 (16)	H5A—C5—H5B	108.1
C12—C7—H7	119.9	N1—C1—C5ⁱⁱ	111.37 (14)
C8—C7—H7	119.9	N1—C1—H1C	109.4
C8ⁱ—C16—C11	121.18 (16)	C5ⁱⁱ—C1—H1C	109.4
C8ⁱ—C16—H16	119.4	N1—C1—H1D	109.4
C11—C16—H16	119.4	C5ⁱⁱ—C1—H1D	109.4
C16ⁱ—C8—C7	120.71 (16)	H1C—C1—H1D	108.0
C16ⁱ—C8—H8	119.6

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱⁱ	0.90	1.91	2.7357 (19)	153
N1—H1B···O3^iv	0.90	1.91	2.7670 (19)	159

Symmetry codes: (iii) −x+1, y+1/2, −z+3/2; (iv) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₄H₁₂N₂²⁺·C₁₀H₆O₆S₂²⁻
M_r	374.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	11.997 (2), 7.2959 (15), 9.1453 (18)
β (°)	96.00 (3)
V (Å³)	796.1 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.955, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	7956, 1827, 1629
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.088, 1.11
No. of reflections	1827
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.36

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.90	1.91	2.7357 (19)	152.5
N1—H1B···O3ⁱⁱ	0.90	1.91	2.7670 (19)	158.8

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

Acknowledgements

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

References

Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun. 12, 994–997. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, D.-H., Ge, J.-Z., Cai, H.-L., Zhang, W. & Xiong, R.-G. (2011). CrystEngComm, 13, 319–324. Web of Science CSD CrossRef CAS Google Scholar
Ye, Q., Song, Y.-M., Wang, G.-X., Chen, K. & Fu, D.-W. (2006). J. Am. Chem. Soc. 128, 6554–6555. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, W., Xiong, R.-G. & Huang, S.-P. D. (2008). J. Am. Chem. Soc. 130, 10468–10469. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, W., Ye, H.-Y., Cai, H.-L., Ge, J.-Z. & Xiong, R.-G. (2010). J. Am. Chem. Soc. 132, 7300–7302. Web of Science CSD CrossRef CAS PubMed Google Scholar