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

The title molecular salt, C(4)H(12)N(2) (2+)·C(10)H(6)O(6)S(2) (2-), consists of a piperazinium cation and a 1,5-naphthalene-disulfonate 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, inter-molecular 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

C4H12N2 2+·C10H6O6S2 2−

M = 374.42

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.088

S = 1.11

1827 reflections

109 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.36 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811038955/vm2121sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038955/vm2121Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811038955/vm2121Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C4H12N22+·C10H6O6S22−	Z = 2
Mr = 374.42	F(000) = 392
Monoclinic, P21/c	Dx = 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

Rigaku SCXmini diffractometer	1827 independent reflections
Radiation source: fine-focus sealed tube	1629 reflections with I > 2σ(I)
graphite	Rint = 0.031
CCD_Profile_fitting scans	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −15→15
Tmin = 0.955, Tmax = 0.955	k = −9→9
7956 measured reflections	l = −11→11

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(Fo2) + (0.038P)2 + 0.4026P] where P = (Fo2 + 2Fc2)/3
S = 1.11	(Δ/σ)max = 0.001
1827 reflections	Δρmax = 0.26 e Å−3
109 parameters	Δρmin = −0.36 e Å−3
0 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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

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···O3iv	0.90	1.91	2.7670 (19)	159.

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) ; (ii) .