1-Phenyl­piperazine-1,4-diium bis­(hydrogen sulfate)

Houda Marouani; Mohamed Rzaigui; Salem S Al-Deyab

doi:10.1107/S1600536810037001

. 2010 Sep 25;66(Pt 10):o2613. doi: 10.1107/S1600536810037001

1-Phenylpiperazine-1,4-diium bis(hydrogen sulfate)

Houda Marouani ^a,^*, Mohamed Rzaigui ^a, Salem S Al-Deyab ^b

PMCID: PMC2983403 PMID: 21587588

Abstract

In the title compound, C₁₀H₁₆N₂ ²⁺·2HSO₄ ⁻, the S atoms adopt slightly distorted tetrahedral geometry and the diprotonated piperazine ring adopts a chair conformation. In the crystal, the 1-phenylpiperazine-1,4-diium cations are anchored between chains formed by the sulfate entities via intermolecular bifurcated N—H⋯(O,O) and weak C—H⋯O hydrogen bonds. These hydrogen bonds contribute to the cohesion and stability of the network of the crystal structure.

Related literature

For pharmacological properties of phenylpiperazine, see: Cohen et al. (1982 ▶); Conrado et al. (2008 ▶); Neves et al. (2003 ▶). For related structures, see: Ben Gharbia et al. (2005 ▶). For a discussion on hydrogen bonding, see: Brown (1976 ▶); Blessing (1986 ▶). For structural discussion, see: Arbuckle et al. (2009 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₀H₁₆N₂ ²⁺·2HSO₄ ⁻
M _r = 358.38
Monoclinic,
a = 17.535 (6) Å
b = 10.996 (2) Å
c = 7.631 (2) Å
β = 99.86 (2)°
V = 1449.7 (7) Å³
Z = 4
Ag Kα radiation
λ = 0.56083 Å
μ = 0.22 mm⁻¹
T = 293 K
0.5 × 0.4 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
8212 measured reflections
7100 independent reflections
4535 reflections with I > 2σ(I)
R _int = 0.022
2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.127
S = 1.03
7100 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-32 for Windows (Farrugia, 1998 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037001/pv2328sup1.cif

e-66-o2613-sup1.cif^{(17.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037001/pv2328Isup2.hkl

e-66-o2613-Isup2.hkl^{(340.4KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.82	1.80	2.6140 (17)	172
O5—H5⋯O7ⁱⁱ	0.82	1.80	2.6066 (18)	169
N1—H1A⋯O2ⁱⁱⁱ	0.90	2.23	2.8636 (19)	128
N1—H1A⋯O3^iv	0.90	2.30	3.0279 (19)	138
N1—H1B⋯O3	0.90	2.14	2.9251 (18)	145
N1—H1B⋯O2ⁱ	0.90	2.35	2.9892 (18)	128
N2—H2⋯O7	0.91	2.02	2.8216 (16)	146
N2—H2⋯O6ⁱⁱ	0.91	2.32	2.9037 (17)	122

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

Acknowledgments

We would like to acknowledge the support provided by the Secretary of State for Scientific Research and Technology of Tunisia.

supplementary crystallographic information

Comment

The phenylpiperazine and its derivatives have been intensively investigated recently owing to their interesting pharmacological, cardiovascular and autonomic properties (Conrado et al., 2008; Cohen et al., 1982; Neves et al., 2003). We report here the preparation and the crystal structure of the title compound, (I).

The asymmetric unit of the title compound (Fig.1) consists of two HSO₄^- anions and a 1-phenylpiperazine-1,4-diium cation. The interatomic bond lengths and angles of the cation show no significant deviation from those reported in other 1-phenylpiperazinium salts such as [C₁₀H₁₆N₂]₂ZnCl₄ (Ben Gharbia, et al., 2005). In the title compound, the distances S—O are significantly longer than the S═O distances as reported in the hydrogen sulfate ion previously (Arbuckle, et al., 2009). The aromatic ring is essentially planar while the diprotonated piperazine ring adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975): Q = 0.5913 (14) Å, θ = 178.61 (15)° and φ = 76 (5)°.

The atomic arrangement is characterized by infinite chains built by HSO₄^- anions. The inorganic chains, extending along the c direction, are located around planes perpendicular to the a axis at x = 0 (for HS1O₄^-) and x = 1/4, x = 3/4 (for HS2O₄^-). The hydrogen sulfate groups of the same type are interconnected via strong O—H···O hydrogen bonds (Table 1)[d (O···O) < 2.73 Å] (Brown, 1976; Blessing, 1986). Chains formed by HS1O₄ are linked by N1 nitrogen atom of the cation to form layers parallel to the bc plane at x = 0. Two chains of different type are bound between them by the cations through their two nitrogen atoms by means of the N—H···O hydrogen bonds (Fig. 2).

The cations are linked onto the anionic chains, by forming H-bonds with the oxygen atoms with N—H···O distances in the range 2.8216 (16)–3.0279 (19) Å and C—H···O distances in the range 2.949 (2)–3.520 (2) Å. It should be noticed that all the amino hydrogen atoms are involved in bifurcated N—H···(O, O) hydrogen bonding. These hydrogen bonds contribute to the cohesion and stability of the network of the studied crystal structure.

Experimental

Single crystals of the title compound were prepared at room temperature from a mixture of an aqueous solution of sulfuric acid (2 mmol), 1-phenylpiperazine (1 mmol), ethanol (10 ml) and water (10 ml). The solution was stirred for 1 h then evaporated slowly at room temperature for several days until the formation of good quality of prismatic single crystals.