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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o2114.
Published online 2010 July 24. doi:  10.1107/S160053681002862X
PMCID: PMC3007435

(±)-2-Methyl­piperazin-1-ium perchlorate

Abstract

In the title compound, C5H13N2 +·ClO4 , the monoprotonated piperazine ring adopts a chair conformation. In the crystal structure, cations and anions are linked by inter­molecular N—H(...)O and N—H(...)N hydrogen bonds into layers parallel to (An external file that holds a picture, illustration, etc.
Object name is e-66-o2114-efi1.jpg01).

Related literature

For the properties of simple mol­ecular–ionic crystals, see: Czupiński et al. (2002 [triangle]); Katrusiak & Szafrański (1999 [triangle], 2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2114-scheme1.jpg

Experimental

Crystal data

  • C5H13N2 +·ClO4
  • M r = 200.62
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2114-efi2.jpg
  • a = 6.8977 (5) Å
  • b = 8.1292 (6) Å
  • c = 16.2201 (11) Å
  • β = 98.614 (3)°
  • V = 899.25 (11) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.41 mm−1
  • T = 293 K
  • 0.30 × 0.25 × 0.20 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.80, T max = 0.90
  • 8953 measured reflections
  • 2055 independent reflections
  • 1541 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.075
  • wR(F 2) = 0.224
  • S = 1.05
  • 2055 reflections
  • 109 parameters
  • H-atom parameters constrained
  • Δρmax = 0.86 e Å−3
  • Δρmin = −0.56 e Å−3

Data collection: CrystalClear (Rigaku, 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/S160053681002862X/rz2472sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002862X/rz2472Isup2.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 in 1:1 molar ratio due to the tunability of their special structural features and their interesting physical properties (Czupiński et al., 2002; Katrusiak & Szafrański, 1999; Katrusiak & Szafrański, 2006). As a contribution in this field, the crystal structure of title salt is reported here.

The asymmetric unit of the title compound (Fig.1) consists of a monoprotonated 2-methylpiperazinium cation and a ClO4-anions. The piperazine ring adopts a chair conformation. In the crystal structure, cations and anions are linked by intermolecular N—H···O and N—H···N hydrogen bonds (Table 1) into layers parallel to the (1 0 1) plane (Fig.2).

Experimental

(±)-2-Methylpiperazine (20 mmol) and 10% aqueous HClO4 solution in a molar ratio of 1:1 were mixed and dissolved in 25 ml water. The mixture was heated to 343 K to form a clear solution. On slow cooling of the reaction mixture to room temperature, block crystals of the title compound were formed.

Refinement

All H atoms were placed in calculated positions, with C—H = 0.96–0.98Å and N—H = 0.90 Å, and refined using a riding model, with Uiso(H) = 1.2Ueq(C, N) or 1.5 Ueq(C) for methyl H atoms.

Figures

Fig. 1.
The asymmetric unit of the title compound with atom labels. Displacement ellipsoids were drawn at the 30% probability level
Fig. 2.
Packing viewed along the a axis. Hydrogen bonds are drawn as dashed lines

Crystal data

C5H13N2+·ClO4F(000) = 424
Mr = 200.62Dx = 1.482 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ynCell parameters from 1541 reflections
a = 6.8977 (5) Åθ = 3.1–27.5°
b = 8.1292 (6) ŵ = 0.41 mm1
c = 16.2201 (11) ÅT = 293 K
β = 98.614 (3)°Block, colourless
V = 899.25 (11) Å30.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Rigaku SCXmini diffractometer2055 independent reflections
Radiation source: fine-focus sealed tube1541 reflections with I > 2σ(I)
graphiteRint = 0.040
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −10→10
Tmin = 0.80, Tmax = 0.90l = −21→20
8953 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.075Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.224H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.1123P)2 + 1.4914P] where P = (Fo2 + 2Fc2)/3
2055 reflections(Δ/σ)max < 0.001
109 parametersΔρmax = 0.86 e Å3
0 restraintsΔρmin = −0.56 e Å3

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
C10.4992 (5)0.6921 (5)0.6807 (2)0.0414 (8)
H1B0.59750.77300.70190.050*
H1A0.55250.62330.64070.050*
C20.4487 (5)0.5875 (5)0.7518 (2)0.0406 (8)
H2A0.56440.52670.77590.049*
H2B0.41180.65910.79470.049*
C30.1170 (5)0.5531 (5)0.6809 (2)0.0389 (8)
H3A0.05990.62270.71940.047*
H3B0.02050.47030.66030.047*
C40.1591 (5)0.6579 (5)0.6075 (2)0.0384 (8)
H4A0.20620.58560.56640.046*
C5−0.0190 (7)0.7490 (7)0.5654 (3)0.0646 (13)
H5A0.01520.81170.51960.097*
H5B−0.06560.82180.60480.097*
H5C−0.12010.67160.54520.097*
Cl10.56264 (14)0.19954 (12)0.59443 (6)0.0442 (4)
N10.2890 (5)0.4712 (4)0.7261 (2)0.0392 (7)
H1C0.33050.39410.69290.047*
N20.3194 (4)0.7764 (3)0.63945 (18)0.0352 (7)
H2D0.34940.83690.59660.042*
H2C0.27610.84530.67610.042*
O10.3667 (7)0.1613 (7)0.6079 (3)0.1041 (16)
O20.5363 (11)0.2923 (9)0.5226 (3)0.154 (3)
O30.6614 (5)0.2921 (5)0.6628 (2)0.0759 (11)
O40.6557 (9)0.0550 (9)0.5835 (6)0.215 (5)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0355 (18)0.044 (2)0.046 (2)−0.0020 (15)0.0098 (15)0.0026 (16)
C20.0404 (19)0.0397 (19)0.0410 (19)0.0043 (15)0.0037 (15)0.0042 (15)
C30.0395 (19)0.0380 (18)0.0401 (18)−0.0068 (15)0.0095 (15)−0.0047 (15)
C40.043 (2)0.0402 (19)0.0315 (17)−0.0016 (15)0.0028 (14)−0.0028 (14)
C50.054 (3)0.079 (3)0.056 (3)0.010 (2)−0.007 (2)0.004 (2)
Cl10.0500 (6)0.0457 (6)0.0378 (5)0.0080 (4)0.0094 (4)−0.0044 (4)
N10.0481 (18)0.0298 (14)0.0415 (16)0.0004 (13)0.0130 (13)0.0016 (12)
N20.0422 (16)0.0319 (15)0.0329 (15)−0.0012 (12)0.0103 (12)0.0013 (12)
O10.089 (3)0.149 (4)0.080 (3)−0.040 (3)0.034 (2)−0.028 (3)
O20.196 (7)0.199 (7)0.067 (3)−0.086 (5)0.017 (3)0.048 (4)
O30.072 (2)0.076 (2)0.074 (2)0.0078 (18)−0.0083 (19)−0.0251 (19)
O40.132 (5)0.151 (5)0.318 (11)0.089 (4)−0.105 (6)−0.155 (7)

Geometric parameters (Å, °)

C1—N21.485 (5)C4—C51.507 (6)
C1—C21.514 (5)C4—H4A0.9800
C1—H1B0.9700C5—H5A0.9600
C1—H1A0.9700C5—H5B0.9600
C2—N11.465 (5)C5—H5C0.9600
C2—H2A0.9700Cl1—O41.363 (5)
C2—H2B0.9700Cl1—O21.377 (5)
C3—N11.459 (5)Cl1—O31.426 (4)
C3—C41.526 (5)Cl1—O11.436 (4)
C3—H3A0.9700N1—H1C0.8998
C3—H3B0.9700N2—H2D0.9000
C4—N21.500 (5)N2—H2C0.9000
N2—C1—C2109.3 (3)C3—C4—H4A108.5
N2—C1—H1B109.8C4—C5—H5A109.5
C2—C1—H1B109.8C4—C5—H5B109.5
N2—C1—H1A109.8H5A—C5—H5B109.5
C2—C1—H1A109.8C4—C5—H5C109.5
H1B—C1—H1A108.3H5A—C5—H5C109.5
N1—C2—C1113.3 (3)H5B—C5—H5C109.5
N1—C2—H2A108.9O4—Cl1—O2111.5 (6)
C1—C2—H2A108.9O4—Cl1—O3112.1 (3)
N1—C2—H2B108.9O2—Cl1—O3110.9 (3)
C1—C2—H2B108.9O4—Cl1—O1107.8 (5)
H2A—C2—H2B107.7O2—Cl1—O1103.9 (4)
N1—C3—C4114.3 (3)O3—Cl1—O1110.3 (2)
N1—C3—H3A108.7C3—N1—C2111.6 (3)
C4—C3—H3A108.7C3—N1—H1C109.0
N1—C3—H3B108.7C2—N1—H1C109.1
C4—C3—H3B108.7C1—N2—C4112.5 (3)
H3A—C3—H3B107.6C1—N2—H2D109.1
N2—C4—C5110.5 (3)C4—N2—H2D109.1
N2—C4—C3107.8 (3)C1—N2—H2C109.1
C5—C4—C3113.0 (4)C4—N2—H2C109.1
N2—C4—H4A108.5H2D—N2—H2C107.8
C5—C4—H4A108.5
N2—C1—C2—N154.6 (4)C1—C2—N1—C3−52.3 (4)
N1—C3—C4—N2−54.1 (4)C2—C1—N2—C4−57.7 (4)
N1—C3—C4—C5−176.4 (3)C5—C4—N2—C1−179.4 (3)
C4—C3—N1—C252.7 (4)C3—C4—N2—C156.8 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···O10.902.383.258 (6)166
N1—H1C···O30.902.543.250 (5)136
N2—H2D···O2i0.902.432.998 (7)121
N2—H2C···N1ii0.901.992.883 (4)169

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2472).

References

  • Czupiński, O., Bator, G., Ciunik, Z., Jakubas, R., Medycki, W. & Świergiel, J. (2002). J. Phys. Condens. Matter, 14, 8497–8512.
  • 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 (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • 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