Crystal structure of piperazine-1,4-diium bis-(4-amino-benzene-sulfonate).

The asymmetric unit of the title salt, C4H12N2 (2+)·2C6H6NO3S(-), consists of half a piperazindiium dication, located about an inversion centre, and a 4-amino-benzene-sulfonate anion. The piperazine ring adopts a chair conformation. In the crystal, the cations and anions are linked via N-H⋯O and C-H⋯O hydrogen bonds, forming a three-dimensional framework. Within the framework there are C-H⋯π inter-actions and the N-H⋯O hydrogen bonds result in the formation of R 4 (4)(22) and R 3 (4)(13) ring motifs.

Related literature

For examples of the the numerous biological activities of piperazines and their various salts, see: Kaur et al. (2010 ▸); Eswaran et al. (2010 ▸); Chou et al. (2010 ▸); Chen et al. (2004 ▸); Shingalapur et al. (2009 ▸); Shchekotikhin et al. (2005 ▸); Faist et al. (2012 ▸); Kulig et al. (2007 ▸). For a related structure, see: Wei (2011 ▸).

Experimental

Crystal data

C4H12N2 2+·2C6H6NO3S−

M = 432.52

Orthorhombic,

a = 10.1709 (4) Å

b = 8.4461 (3) Å

c = 21.5569 (9) Å

V = 1851.83 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.33 mm−1

T = 293 K

0.25 × 0.22 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T min = 0.920, T max = 0.939

31521 measured reflections

2731 independent reflections

2130 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.107

S = 1.03

2731 reflections

160 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.73 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015024457/su5262sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015024457/su5262Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015024457/su5262Isup3.cml

Click here for additional data file.

x y z . DOI: 10.1107/S2056989015024457/su5262fig1.tif

The mol­ecular structure of the title salt, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The unlabelled atoms of the cation are related to the labelled atoms by inversion symmetry (- x + 2, − y, − z + 1).

Click here for additional data file.

a a c . DOI: 10.1107/S2056989015024457/su5262fig2.tif

A partial view of the crystal packing of the title salt, viewed along the a axis. Hydrogen-bonded chains (dashed lines) run along the a and c axes (see Table 1).

Click here for additional data file.

b b . DOI: 10.1107/S2056989015024457/su5262fig3.tif

Crystal packing of the title salt, viewed along the b axis, illustrating the formation of the hydrogen-bonded (dashed lines) mol­ecular ribbons running along the b axis direction (see Table 1). For the sake of clarity, H atoms not involved in hydrogen bonds have been omitted.

Click here for additional data file.

a . DOI: 10.1107/S2056989015024457/su5262fig4.tif

A view along the a axis of the crystal packing of the title salt. The hydrogen bonds are shown as dashed lines (Table 1), and H atoms not involved in these inter­actions have been omitted for clarity.

CCDC reference: 1443504

Additional supporting information: crystallographic information; 3D view; checkCIF report

C4H12N22+·2C6H6NO3S−	F(000) = 912
Mr = 432.52	Dx = 1.551 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2731 reflections
a = 10.1709 (4) Å	θ = 2.8–30.8°
b = 8.4461 (3) Å	µ = 0.33 mm−1
c = 21.5569 (9) Å	T = 293 K
V = 1851.83 (12) Å3	Block, white crystalline
Z = 4	0.25 × 0.22 × 0.19 mm

Bruker APEXII CCD area-detector diffractometer	2731 independent reflections
Radiation source: fine-focus sealed tube	2130 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω and φ scans	θmax = 30.8°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
Tmin = 0.920, Tmax = 0.939	k = −12→10
31521 measured reflections	l = −29→30

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107	w = 1/[σ2(Fo2) + (0.0431P)2 + 1.5618P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
2731 reflections	Δρmax = 0.73 e Å−3
160 parameters	Δρmin = −0.42 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: 0.0332 (17)

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
C1	0.65542 (16)	0.21272 (19)	0.21371 (7)	0.0266 (3)
C2	0.72879 (17)	0.09868 (19)	0.24541 (8)	0.0302 (3)
H2	0.7986	0.0490	0.2255	0.036*
C3	0.69927 (16)	0.05863 (19)	0.30585 (8)	0.0290 (3)
H3	0.7489	−0.0179	0.3262	0.035*
C4	0.59536 (15)	0.13233 (18)	0.33669 (7)	0.0245 (3)
C5	0.52268 (16)	0.24672 (19)	0.30563 (8)	0.0280 (3)
H5	0.4540	0.2976	0.3260	0.034*
C6	0.55133 (16)	0.2859 (2)	0.24479 (8)	0.0292 (3)
H6	0.5009	0.3615	0.2244	0.035*
C7	0.97012 (19)	0.0404 (2)	0.43662 (8)	0.0317 (4)
C8	0.8928 (2)	0.0027 (2)	0.54312 (9)	0.0358 (4)
N1	0.68534 (18)	0.2535 (2)	0.15357 (7)	0.0380 (4)
N2	0.89658 (17)	0.11265 (18)	0.48903 (7)	0.0331 (3)
O1	0.5723 (2)	−0.09171 (16)	0.41653 (7)	0.0586 (5)
O2	0.41824 (14)	0.1269 (2)	0.42189 (6)	0.0514 (4)
O3	0.63822 (14)	0.16386 (17)	0.45474 (6)	0.0413 (3)
S1	0.55342 (4)	0.07560 (5)	0.412784 (18)	0.02600 (14)
H2B	0.934 (2)	0.207 (3)	0.5007 (11)	0.046 (6)*
H1A	0.744 (2)	0.202 (3)	0.1367 (11)	0.042 (6)*
H7A	0.971 (2)	0.119 (3)	0.4049 (11)	0.042 (6)*
H1B	0.635 (2)	0.318 (3)	0.1336 (11)	0.047 (6)*
H8B	0.853 (2)	0.057 (3)	0.5758 (11)	0.046 (6)*
H2A	0.819 (3)	0.132 (3)	0.4765 (11)	0.046 (6)*
H7B	0.924 (2)	−0.044 (3)	0.4239 (10)	0.033 (5)*
H8A	0.842 (2)	−0.089 (3)	0.5299 (10)	0.045 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0248 (7)	0.0274 (7)	0.0278 (7)	−0.0045 (6)	−0.0003 (6)	−0.0017 (6)
C2	0.0275 (8)	0.0283 (7)	0.0349 (8)	0.0040 (6)	0.0058 (6)	−0.0030 (6)
C3	0.0274 (8)	0.0261 (7)	0.0336 (8)	0.0045 (6)	−0.0003 (6)	0.0024 (6)
C4	0.0249 (7)	0.0222 (7)	0.0266 (7)	−0.0019 (6)	0.0005 (6)	−0.0004 (6)
C5	0.0258 (7)	0.0261 (7)	0.0319 (8)	0.0030 (6)	0.0040 (6)	0.0009 (6)
C6	0.0258 (8)	0.0300 (8)	0.0318 (8)	0.0030 (6)	−0.0009 (6)	0.0064 (7)
C7	0.0423 (10)	0.0247 (7)	0.0282 (8)	−0.0012 (7)	−0.0005 (7)	−0.0003 (6)
C8	0.0379 (10)	0.0366 (9)	0.0328 (9)	0.0006 (8)	0.0060 (7)	−0.0005 (7)
N1	0.0366 (8)	0.0500 (10)	0.0275 (7)	0.0068 (8)	0.0036 (6)	0.0022 (7)
N2	0.0366 (8)	0.0265 (7)	0.0362 (8)	0.0072 (6)	−0.0033 (7)	−0.0028 (6)
O1	0.1135 (16)	0.0226 (7)	0.0395 (8)	0.0040 (8)	0.0162 (8)	0.0038 (5)
O2	0.0303 (7)	0.0879 (12)	0.0361 (7)	0.0069 (7)	0.0056 (6)	0.0168 (8)
O3	0.0462 (8)	0.0451 (8)	0.0327 (7)	−0.0063 (6)	−0.0078 (6)	−0.0035 (6)
S1	0.0292 (2)	0.0235 (2)	0.0252 (2)	0.00047 (14)	0.00009 (14)	0.00065 (14)

C1—N1	1.376 (2)	C7—H7A	0.95 (2)
C1—C6	1.397 (2)	C7—H7B	0.90 (2)
C1—C2	1.397 (2)	C8—N2	1.491 (2)
C2—C3	1.379 (2)	C8—C7i	1.506 (3)
C2—H2	0.9300	C8—H8B	0.93 (2)
C3—C4	1.395 (2)	C8—H8A	0.98 (2)
C3—H3	0.9300	N1—H1A	0.82 (3)
C4—C5	1.389 (2)	N1—H1B	0.86 (3)
C4—S1	1.7614 (16)	N2—H2B	0.92 (3)
C5—C6	1.384 (2)	N2—H2A	0.85 (3)
C5—H5	0.9300	O1—S1	1.4285 (14)
C6—H6	0.9300	O2—S1	1.4548 (15)
C7—N2	1.486 (2)	O3—S1	1.4553 (13)
C7—C8i	1.506 (3)	S1—O3	1.4553 (13)
N1—C1—C6	120.59 (16)	N2—C8—C7i	110.69 (15)
N1—C1—C2	121.04 (16)	N2—C8—H8B	107.1 (15)
C6—C1—C2	118.37 (15)	C7i—C8—H8B	107.5 (15)
C3—C2—C1	121.00 (15)	N2—C8—H8A	106.3 (13)
C3—C2—H2	119.5	C7i—C8—H8A	112.6 (14)
C1—C2—H2	119.5	H8B—C8—H8A	113 (2)
C2—C3—C4	120.37 (15)	C1—N1—H1A	116.5 (16)
C2—C3—H3	119.8	C1—N1—H1B	119.8 (16)
C4—C3—H3	119.8	H1A—N1—H1B	123 (2)
C5—C4—C3	118.95 (15)	C7—N2—C8	110.61 (14)
C5—C4—S1	120.62 (12)	C7—N2—H2B	111.1 (15)
C3—C4—S1	120.39 (12)	C8—N2—H2B	109.7 (15)
C6—C5—C4	120.74 (15)	C7—N2—H2A	107.8 (16)
C6—C5—H5	119.6	C8—N2—H2A	110.2 (16)
C4—C5—H5	119.6	H2B—N2—H2A	107 (2)
C5—C6—C1	120.56 (15)	O1—S1—O2	114.48 (12)
C5—C6—H6	119.7	O1—S1—O3	113.06 (10)
C1—C6—H6	119.7	O2—S1—O3	108.89 (10)
N2—C7—C8i	110.17 (15)	O1—S1—O3	113.06 (10)
N2—C7—H7A	105.4 (14)	O2—S1—O3	108.89 (10)
C8i—C7—H7A	111.3 (14)	O1—S1—C4	106.80 (8)
N2—C7—H7B	107.0 (14)	O2—S1—C4	105.87 (8)
C8i—C7—H7B	112.6 (14)	O3—S1—C4	107.21 (8)
H7A—C7—H7B	110.0 (19)	O3—S1—C4	107.21 (8)
N1—C1—C2—C3	179.55 (16)	O3—O3—S1—O1	0.00 (18)
C6—C1—C2—C3	0.2 (2)	O3—O3—S1—O2	0.00 (18)
C1—C2—C3—C4	−0.3 (3)	O3—O3—S1—C4	0.0 (2)
C2—C3—C4—C5	−0.2 (2)	C5—C4—S1—O1	140.98 (15)
C2—C3—C4—S1	177.43 (13)	C3—C4—S1—O1	−36.62 (17)
C3—C4—C5—C6	0.9 (2)	C5—C4—S1—O2	18.58 (16)
S1—C4—C5—C6	−176.76 (13)	C3—C4—S1—O2	−159.02 (14)
C4—C5—C6—C1	−1.0 (3)	C5—C4—S1—O3	−97.55 (15)
N1—C1—C6—C5	−178.90 (16)	C3—C4—S1—O3	84.85 (15)
C2—C1—C6—C5	0.5 (2)	C5—C4—S1—O3	−97.55 (15)
C8i—C7—N2—C8	−57.3 (2)	C3—C4—S1—O3	84.85 (15)
C7i—C8—N2—C7	57.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ii	0.82 (3)	2.27 (3)	3.066 (2)	164 (2)
N1—H1B···O1iii	0.86 (3)	2.49 (3)	3.296 (3)	156 (2)
N2—H2A···O3	0.85 (3)	1.92 (3)	2.764 (2)	175 (2)
N2—H2B···O2iv	0.92 (3)	2.19 (2)	2.928 (2)	137 (2)
N2—H2B···O3iv	0.92 (3)	2.54 (2)	3.328 (2)	145 (2)
C7—H7A···O1v	0.95 (2)	2.50 (2)	3.167 (2)	128 (2)
C6—H6···Cg1iii	0.93	2.92	3.753 (2)	149

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2i	0.82 (3)	2.27 (3)	3.066 (2)	164 (2)
N1—H1B⋯O1ii	0.86 (3)	2.49 (3)	3.296 (3)	156 (2)
N2—H2A⋯O3	0.85 (3)	1.92 (3)	2.764 (2)	175 (2)
N2—H2B⋯O2iii	0.92 (3)	2.19 (2)	2.928 (2)	137 (2)
N2—H2B⋯O3iii	0.92 (3)	2.54 (2)	3.328 (2)	145 (2)
C7—H7A⋯O1iv	0.95 (2)	2.50 (2)	3.167 (2)	128 (2)
C6—H6⋯Cg1ii	0.93	2.92	3.753 (2)	149

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .