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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2214.
Published online 2010 August 4. doi:  10.1107/S1600536810030345
PMCID: PMC3007905

Piperazine-1,4-diium bis­(perchlorate) dihydrate

Abstract

The asymmetric unit of the title compound, C4H12N2 2+·2ClO4 ·2H2O, contains half of a piperazinediium cation, one perchlorate anion and one water mol­ecule. The diprotonated piperazine ring, which is completed by crystallographic inversion symmetry, adopts a chair conformation. In the crystal structure, the cations and anions are linked by inter­molecular N—H(...)O and O—H(...)O hydrogen bonds into a three-dimensional network.

Related literature

For background to simple mol­ecular–ionic crystals containing organic cations and acid radicals (1:1 molar ratio), see: Katrusiak & Szafrański (1999 [triangle], 2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2214-scheme1.jpg

Experimental

Crystal data

  • C4H12N2 2+·2ClO4 ·2H2O
  • M r = 323.09
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2214-efi1.jpg
  • a = 7.2588 (15) Å
  • b = 6.5089 (13) Å
  • c = 14.543 (4) Å
  • β = 113.56 (3)°
  • V = 629.8 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.56 mm−1
  • T = 293 K
  • 0.28 × 0.26 × 0.20 mm

Data collection

  • Rigaku Mercury 2 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.856, T max = 0.896
  • 6362 measured reflections
  • 1458 independent reflections
  • 1130 reflections with I > 2σ(I)
  • R int = 0.060

Refinement

  • R[F 2 > 2σ(F 2)] = 0.045
  • wR(F 2) = 0.109
  • S = 1.07
  • 1458 reflections
  • 83 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810030345/pv2304sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030345/pv2304Isup2.hkl

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

Acknowledgments

This work was supported by a start-up grant from Anyang Institute of Technology.

supplementary crystallographic information

Comment

Recently, much attention has been devoted to simple molecular–ionic crystals containing organic cations and acid radicals (1:1 molar ratio) due to the tunability of their special structural features and their interesting physical properties (Katrusiak & Szafrański, 1999; Katrusiak & Szafrański, 2006). In our laboratory, the title compound has been synthesized and its crystal structure is reported herein.

The asymmetric unit of the title compound consists of a half piperazine cation, one chlorate anion and one water molecule (Fig. 1). The diprotonated piperazine ring adopts a chair conformation. In the crystal structure, cations and anions are linked by intermolecular N—H···O and O—H···O hydrogen bonds into a three-dimensional network (Tab. 1 & Fig. 2).

Experimental

Piperazine (1.7 g, 20 mmol) and 10% aqueous HClO4 (25 ml) in a molar ratio of 1:1 were mixed and dissolved in 30 ml water by heating to 353 K forming a clear solution. The reaction mixture was cooled slowly to room temperature, block crystals of the title compound were formed after fifteen days.

Refinement

The H atoms of piperzinium ion were placed in calculated positions, with C—H = 0.97 and N—H = 0.90 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C/N). The hydrogen atoms of the water molecule were located from a difference fourier map and were fixed at those positions with Uiso(H)=1.5Ueq(O).

Figures

Fig. 1.
The asymmetric unit of the title compound with atomic labels. Displacement ellipsoids were drawn at the 30% probability level.
Fig. 2.
The unit cell packing of the title compound viewed along the a-axis; hydrogen bonds are drawn as dashed lines.

Crystal data

C4H12N22+·2ClO4·2H2OF(000) = 336
Mr = 323.09Dx = 1.704 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1130 reflections
a = 7.2588 (15) Åθ = 3.1–27.5°
b = 6.5089 (13) ŵ = 0.56 mm1
c = 14.543 (4) ÅT = 293 K
β = 113.56 (3)°Block, colorless
V = 629.8 (3) Å30.28 × 0.26 × 0.20 mm
Z = 2

Data collection

Rigaku Mercury 2 diffractometer1458 independent reflections
Radiation source: fine-focus sealed tube1130 reflections with I > 2σ(I)
graphiteRint = 0.060
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)k = −8→8
Tmin = 0.856, Tmax = 0.896l = −18→18
6362 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.109w = 1/[σ2(Fo2) + (0.0357P)2 + 0.361P] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1458 reflectionsΔρmax = 0.28 e Å3
83 parametersΔρmin = −0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.044 (4)

Special details

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)

xyzUiso*/Ueq
C10.3021 (4)1.0866 (4)0.94987 (19)0.0411 (6)
H1C0.25161.01170.88700.049*
H1D0.19891.18210.94910.049*
C20.3493 (4)0.9393 (4)1.03562 (19)0.0426 (6)
H2B0.39041.01491.09810.051*
H2A0.23030.86031.02720.051*
Cl10.78737 (8)0.59992 (10)0.84112 (4)0.0390 (2)
N10.5133 (3)0.7985 (3)1.03919 (15)0.0401 (5)
H1B0.47150.72340.98250.048*
H1A0.54200.71151.09120.048*
O10.9198 (3)0.7709 (4)0.87194 (18)0.0765 (7)
O20.7472 (3)0.5298 (3)0.92385 (14)0.0561 (6)
O30.6016 (3)0.6622 (3)0.76257 (13)0.0562 (6)
O40.8781 (4)0.4421 (4)0.80648 (18)0.0853 (8)
O51.3089 (2)0.5745 (3)0.85594 (12)0.0421 (5)
H5WB1.36000.60400.82070.063*
H5WA1.18570.56530.83240.063*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0416 (14)0.0393 (14)0.0403 (14)0.0025 (11)0.0140 (11)0.0007 (11)
C20.0444 (14)0.0446 (15)0.0407 (14)−0.0009 (12)0.0189 (12)0.0031 (11)
Cl10.0336 (3)0.0498 (4)0.0351 (3)−0.0020 (3)0.0152 (2)−0.0022 (3)
N10.0538 (13)0.0292 (10)0.0348 (11)−0.0025 (9)0.0149 (9)0.0020 (9)
O10.0532 (13)0.0832 (17)0.0868 (16)−0.0303 (12)0.0214 (12)0.0037 (13)
O20.0542 (11)0.0726 (14)0.0442 (11)−0.0003 (10)0.0226 (9)0.0140 (10)
O30.0415 (10)0.0814 (15)0.0391 (10)0.0024 (10)0.0091 (9)0.0105 (10)
O40.0803 (16)0.102 (2)0.0775 (17)0.0328 (15)0.0362 (14)−0.0225 (14)
O50.0373 (9)0.0469 (11)0.0433 (10)0.0015 (8)0.0174 (8)0.0026 (8)

Geometric parameters (Å, °)

C1—N1i1.487 (3)Cl1—O11.421 (2)
C1—C21.500 (3)Cl1—O21.4218 (19)
C1—H1C0.97Cl1—O31.4339 (19)
C1—H1D0.97N1—C1i1.487 (3)
C2—N11.487 (3)N1—H1B0.90
C2—H2B0.97N1—H1A0.90
C2—H2A0.97O5—H5WB0.77
Cl1—O41.417 (2)O5—H5WA0.82
N1i—C1—C2109.6 (2)O4—Cl1—O2110.46 (15)
N1i—C1—H1C109.7O1—Cl1—O2109.05 (14)
C2—C1—H1C109.7O4—Cl1—O3110.15 (14)
N1i—C1—H1D109.7O1—Cl1—O3109.38 (14)
C2—C1—H1D109.7O2—Cl1—O3108.62 (12)
H1C—C1—H1D108.2C2—N1—C1i111.62 (19)
N1—C2—C1109.7 (2)C2—N1—H1B109.3
N1—C2—H2B109.7C1i—N1—H1B109.3
C1—C2—H2B109.7C2—N1—H1A109.3
N1—C2—H2A109.7C1i—N1—H1A109.3
C1—C2—H2A109.7H1B—N1—H1A108.0
H2B—C2—H2A108.2H5WB—O5—H5WA118.5
O4—Cl1—O1109.16 (16)

Symmetry codes: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1B···O5ii0.902.002.875 (3)165
N1—H1A···O5iii0.902.142.883 (3)140
N1—H1A···O3iv0.902.493.060 (3)122
N1—H1A···O2v0.902.563.040 (3)114
O5—H5WB···O3vi0.772.262.999 (3)161
O5—H5WA···O10.822.593.192 (3)131
O5—H5WA···O40.822.263.040 (3)159

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2304).

References

  • Katrusiak, A. & Szafrański, M. (1999). Phys. Rev. Lett.82, 576–579.
  • Katrusiak, A. & Szafrański, M. (2006). J. Am. Chem. Soc.128, 15775–15785. [PubMed]
  • Rigaku/MSC (2005). CrystalClear Rigaku/MSC, TheWoodlands, Texas, USA
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography