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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2244–o2245.
Published online 2010 August 11. doi:  10.1107/S1600536810030813
PMCID: PMC3008102

4-Phenyl­piperazin-1-ium dihydrogen phosphate

Abstract

The title compound, C10H15N2 +·H2PO4 , is built up from 4-phenyl­piperazin-1-ium cations and dihydrogen phosphate anions. The inter­connection between two adjacent anions is assured by two strong O—H(...)O hydrogen bonds, which lead to the formation of infinite wave-like chains which spread along the a axis. The organic cations connect these chains via N—H(...)O hydrogen bonds. The crystal cohesion and stability are ensured by electrostatic and van der Waals inter­actions which, together with N—H(...)O and O—H(...)O hydrogen bonds, build up a two-dimensional network.

Related literature

For the pharmacological properties of phenyl­piperazines and their derivatives, see: Cohen et al. (1982 [triangle]); Conrado et al. (2008 [triangle]); Neves et al. (2003 [triangle]); Hanano et al. (2000 [triangle]). For related structures, see: Zouari et al. (1995 [triangle]); Ben Gharbia et al. (2005 [triangle]). For a discussion of hydrogen bonding, see: Brown (1976 [triangle]); Blessing (1986 [triangle]). For tetra­hedral distortions, see: Baur (1974 [triangle]). For structural discussion, see: Ferraris & Ivaldi (1984 [triangle]); Janiak (2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2244-scheme1.jpg

Experimental

Crystal data

  • C10H15N2 +·H2PO4
  • M r = 260.23
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2244-efi1.jpg
  • a = 6.175 (3) Å
  • b = 8.276 (3) Å
  • c = 24.408 (9) Å
  • V = 1247.3 (9) Å3
  • Z = 4
  • Ag Kα radiation
  • λ = 0.56083 Å
  • μ = 0.12 mm−1
  • T = 293 K
  • 0.50 × 0.40 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • 4505 measured reflections
  • 4296 independent reflections
  • 2134 reflections with I > 2σ(I)
  • R int = 0.029
  • 2 standard reflections every 120 min intensity decay: 6%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.056
  • wR(F 2) = 0.127
  • S = 0.94
  • 4296 reflections
  • 154 parameters
  • H-atom parameters constrained
  • Δρmax = 0.44 e Å−3
  • Δρmin = −0.27 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 812 Friedel pairs
  • Flack parameter: −0.1 (2)

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg & Putz, 2005 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810030813/dn2592sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030813/dn2592Isup2.hkl

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

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

Research relate to a novel group of phenylpiperazines and its derivatives having interesting pharmacological, cardiovascular and autonomic properties such as a high affinity for the dopamine D.sub.2 receptor and/or the serotonin reuptake site, and the ability to treat conditions related to disturbances in the dopaminergic and/or the serotonergic systems such as anxiety disorders, depression, Parkinson's disease, and schizophrenia (Conrado et al., 2008); (Cohen et al., 1982); (Neves et al., 2003). In addition, novel phenylpiperazine derivatives were synthesized as dual cytokine regulators with TNF-alpha suppressing and IL-10 augmenting activity (Hanano et al., 2000).

In this work, we report the preparation and the structural investigation of the noncentrosymmetric, (C10H15N2)H2PO4, (I). This compound is built up from the H2PO4- anion and the organic 4-phenylpiperazin-1-ium cation (Fig. 1). The atomic arrangement can be described as a stacking of H2PO4- anions according to the a axis, forming chains located in the planes z = 0 and z = 1/2. These chains are themselves interconnected by means of the N—H···O hydrogen bonds. Between which are located the organic cations. Examination of the H2PO4- geometry shows two types of P—O distances. The largest ones, 1.567 (2) Å and 1.568 (5) Å, can be attributed to the P—OH distances, while the shortest ones, 1.511 (6) Å and 1.495 (9) Å, correspond to the phosphoric atom doubly bonded to the oxygen atom (P=O). The average values of the P—O distances and O—P—O angles are 1.533 Å and 109.4 °, respectively. These geometrical features have also been noticed in other crystal structures (Ferraris, et al., 1984). Nevertheless, the calculated average values of the distortion indices (Baur, 1974). corresponding to the different angles and distances in the PO4 tetrahedron [DI(PO) = 0.019, DI(OPO) = 0.027, and DI(OO) = 0.014] show a slight distortion of the OPO angles if compared to O—O and PO distances. So, the PO4 group can be considered as a rigid regular arrangement of oxygen atoms, with the phosphorus atom slightly displaced from the gravity centre.

The interconnection between two adjacent anions H2PO4- is assured by two strong H-bond [d (O···O) < 2.73 Å] (Brown, 1976); (Blessing, 1986) to form infinite waved chains which spread along the a axis.

The protonation of the phenylpiperazine can be due to the higher basicity and less constraint on this hydrogen. The piperazinium ring has a chair conformation, the most stable chemical conformation, with bond angles of around 109 °. The distances of the N atoms from the main plane through the carbon atoms of 0.64 and 0.63 Å. The interatomic bond lengths and angles of the organic groups spread respectively within the ranges [1.366 (6)–1.498 (5) Å] and [110.3 (2)–122.6 (3)°]. The aromatic rings are planar with an average deviation of 0.000343 Å show no significant deviation from those obtained in other 4-phenylpiperazin-1-ium salts such as [C10H15N2]HgCl3 (Zouari, et al., 1995) and [C10H16N2]2ZnCl4 (Ben Gharbia, et al., 2005). The phenylpiperazinium cations are organized in opposite direction along the b axis between the inorganic layers. Furthermore, the inorganic anion chains screen the interaction between the organic cations and probably lead to a non-centrosymmetric atomic arrangement. Therefore, the title compound could be an interesting material in the non-linear optics.

The interplanar distance between nearby phenyl rings is in the vicinity of 4.870 Å, which is significantly longer than 3.80 Å for the π-π interaction (Janiak, 2000). The organic cations are linked onto the anionic chains, by forming H-bonds with the oxygen atoms with N—H···O distances in the range 2.675 (3) - 2.731 (3) Å. 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 phosphoric acid (2 mmol), 1-phenylpiperazine (2 mmol), ethanol (10 ml) and water (10 ml). The resulting solution was stirred during 1 h then evaporated slowly at room temperature for several days until the formation of good quality of prismatic single crystals.

Refinement

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.97 Å (methylene) and N—H = 0.90 Å with Uiso(H) = 1.2Ueq(C or N).

Owing to the low number of Friedel pairs, the standard deviation on the Flack parameter is large, -0.1 (2). However inverting the structure lead to a value of 1.1 (2) and then it was assumed that the correct absolute structure corresponds to the refined model.

Figures

Fig. 1.
An ORTEP view of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
Fig. 2.
Projection of (I) along the b axis. H atoms non committed in H-bonds are omitted.

Crystal data

C10H15N2+·H2PO4F(000) = 552
Mr = 260.23Dx = 1.386 Mg m3
Orthorhombic, P212121Ag Kα radiation, λ = 0.56083 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 6.175 (3) Åθ = 9–11°
b = 8.276 (3) ŵ = 0.12 mm1
c = 24.408 (9) ÅT = 293 K
V = 1247.3 (9) Å3Prism, colourless
Z = 40.50 × 0.40 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.029
Radiation source: Enraf Nonius FR590θmax = 28.0°, θmin = 2.6°
graphiteh = 0→10
non–profiled ω scansk = 0→13
4505 measured reflectionsl = −10→40
4296 independent reflections2 standard reflections every 120 min
2134 reflections with I > 2σ(I) intensity decay: 6%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056H-atom parameters constrained
wR(F2) = 0.127w = 1/[σ2(Fo2) + (0.0539P)2] where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max < 0.001
4296 reflectionsΔρmax = 0.44 e Å3
154 parametersΔρmin = −0.27 e Å3
0 restraintsAbsolute structure: Flack (1983), 812 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.1 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
C10.9900 (5)0.0405 (3)0.07656 (13)0.0538 (8)
H1C1.0834−0.04970.08580.065*
H1D0.91180.01280.04340.065*
C20.8320 (5)0.0668 (4)0.12197 (12)0.0540 (8)
H2A0.72620.14680.11070.065*
H2B0.7557−0.03330.12930.065*
C31.0653 (6)0.2676 (3)0.16155 (12)0.0529 (7)
H3A1.13870.29960.19500.063*
H3B0.96970.35490.15070.063*
C41.2291 (5)0.2386 (4)0.11736 (13)0.0525 (8)
H4A1.30890.33750.11050.063*
H4B1.33130.15700.12940.063*
C50.8136 (4)0.1192 (3)0.21995 (12)0.0413 (6)
C60.6143 (5)0.0404 (4)0.22358 (14)0.0516 (8)
H60.5592−0.01170.19290.062*
C70.4984 (6)0.0382 (4)0.27123 (16)0.0647 (10)
H70.3657−0.01490.27210.078*
C80.5724 (7)0.1121 (4)0.31782 (16)0.0705 (10)
H80.49070.11160.34980.085*
C90.7710 (8)0.1870 (5)0.31582 (15)0.0769 (12)
H90.82610.23520.34730.092*
C100.8895 (6)0.1921 (4)0.26826 (13)0.0588 (8)
H101.02250.24480.26800.071*
N11.1243 (4)0.1849 (3)0.06624 (10)0.0396 (5)
H1A1.22620.16150.04110.047*
H1B1.04090.26490.05290.047*
N20.9374 (4)0.1210 (2)0.17176 (9)0.0406 (5)
P10.95373 (11)0.58755 (7)0.02154 (3)0.03303 (15)
O11.1831 (3)0.5806 (2)0.04795 (8)0.0458 (5)
H11.24220.66880.04480.069*
O20.8135 (3)0.6752 (3)0.06613 (8)0.0484 (5)
H20.69120.69060.05420.073*
O30.8824 (3)0.4159 (2)0.01488 (9)0.0521 (5)
O40.9544 (3)0.6870 (2)−0.03041 (7)0.0418 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.069 (2)0.0385 (12)0.0542 (18)−0.0065 (13)0.0118 (16)−0.0106 (12)
C20.0533 (16)0.0602 (18)0.0485 (16)−0.0178 (16)0.0073 (14)−0.0121 (15)
C30.0628 (17)0.0529 (15)0.0428 (15)−0.0225 (17)0.0014 (16)−0.0069 (13)
C40.0454 (15)0.0566 (17)0.0555 (18)−0.0096 (14)−0.0052 (15)0.0093 (15)
C50.0455 (14)0.0342 (13)0.0441 (15)0.0061 (10)0.0024 (13)0.0034 (11)
C60.0549 (17)0.0519 (17)0.0480 (17)−0.0019 (13)0.0034 (15)0.0042 (14)
C70.061 (2)0.066 (2)0.067 (2)0.0014 (15)0.0155 (19)0.0143 (18)
C80.091 (3)0.0611 (19)0.059 (2)0.017 (2)0.028 (2)0.0121 (18)
C90.123 (4)0.062 (2)0.0452 (19)−0.005 (3)0.008 (2)−0.0109 (17)
C100.075 (2)0.0543 (16)0.0471 (17)−0.0141 (16)0.0025 (17)−0.0121 (15)
N10.0432 (11)0.0319 (9)0.0436 (12)0.0102 (9)0.0062 (11)0.0050 (10)
N20.0445 (11)0.0364 (10)0.0410 (12)−0.0047 (10)0.0008 (11)−0.0046 (9)
P10.0347 (3)0.0253 (2)0.0391 (3)−0.0019 (3)−0.0063 (3)0.0030 (3)
O10.0424 (9)0.0369 (9)0.0582 (12)−0.0069 (9)−0.0132 (9)0.0143 (9)
O20.0507 (11)0.0541 (11)0.0403 (10)0.0097 (10)0.0004 (9)0.0037 (9)
O30.0599 (10)0.0271 (7)0.0693 (13)−0.0028 (8)−0.0286 (11)0.0008 (10)
O40.0392 (8)0.0443 (8)0.0418 (10)0.0089 (9)0.0007 (9)0.0084 (8)

Geometric parameters (Å, °)

C1—N11.476 (4)C6—C71.366 (5)
C1—C21.492 (4)C6—H60.9300
C1—H1C0.9700C7—C81.370 (6)
C1—H1D0.9700C7—H70.9300
C2—N21.450 (4)C8—C91.375 (6)
C2—H2A0.9700C8—H80.9300
C2—H2B0.9700C9—C101.373 (5)
C3—N21.469 (3)C9—H90.9300
C3—C41.498 (5)C10—H100.9300
C3—H3A0.9700N1—H1A0.9000
C3—H3B0.9700N1—H1B0.8998
C4—N11.474 (4)P1—O31.496 (2)
C4—H4A0.9700P1—O41.5114 (19)
C4—H4B0.9700P1—O11.5572 (19)
C5—C61.395 (4)P1—O21.569 (2)
C5—N21.403 (4)O1—H10.8197
C5—C101.405 (4)O2—H20.8194
N1—C1—C2112.1 (2)C6—C7—C8121.7 (3)
N1—C1—H1C109.2C6—C7—H7119.1
C2—C1—H1C109.2C8—C7—H7119.1
N1—C1—H1D109.2C7—C8—C9118.0 (3)
C2—C1—H1D109.2C7—C8—H8121.0
H1C—C1—H1D107.9C9—C8—H8121.0
N2—C2—C1112.0 (2)C10—C9—C8121.3 (4)
N2—C2—H2A109.2C10—C9—H9119.4
C1—C2—H2A109.2C8—C9—H9119.4
N2—C2—H2B109.2C9—C10—C5121.2 (3)
C1—C2—H2B109.2C9—C10—H10119.4
H2A—C2—H2B107.9C5—C10—H10119.4
N2—C3—C4110.7 (2)C4—N1—C1110.3 (2)
N2—C3—H3A109.5C4—N1—H1A109.6
C4—C3—H3A109.5C1—N1—H1A109.6
N2—C3—H3B109.5C4—N1—H1B109.6
C4—C3—H3B109.5C1—N1—H1B109.6
H3A—C3—H3B108.1H1A—N1—H1B108.2
N1—C4—C3111.2 (2)C5—N2—C2117.0 (2)
N1—C4—H4A109.4C5—N2—C3116.4 (2)
C3—C4—H4A109.4C2—N2—C3110.8 (2)
N1—C4—H4B109.4O3—P1—O4115.26 (11)
C3—C4—H4B109.4O3—P1—O1106.11 (11)
H4A—C4—H4B108.0O4—P1—O1111.40 (11)
C6—C5—N2122.6 (3)O3—P1—O2110.60 (12)
C6—C5—C10116.2 (3)O4—P1—O2109.38 (11)
N2—C5—C10121.1 (3)O1—P1—O2103.41 (12)
C7—C6—C5121.5 (3)P1—O1—H1109.5
C7—C6—H6119.2P1—O2—H2109.5
C5—C6—H6119.2

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O4i0.821.812.587 (3)158
O2—H2···O4ii0.821.872.642 (3)156
N1—H1B···O30.901.842.731 (3)171
N1—H1A···O3iii0.901.792.675 (3)167

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2592).

References

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