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

Peng, C.

doi:10.1107/S1600536810030345

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2214

https://doi.org/10.1107/S1600536810030345

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

Cong-hu Peng ^a ^*

^aDepartment of Chemical and Environmental Engineering, Anyang Institute of Technology, Anyang 455000, People's Republic of China
^*Correspondence e-mail: ayitpch@yahoo.com.cn

(Received 7 July 2010; accepted 30 July 2010; online 4 August 2010)

The asymmetric unit of the title compound, C₄H₁₂N₂²⁺·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 , 2006 ).

Experimental

Crystal data

C₄H₁₂N₂²⁺·2ClO₄⁻·2H₂O
M_r = 323.09
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.045
wR(F²) = 0.109
S = 1.07
1458 reflections
83 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O5ⁱ	0.90	2.00	2.875 (3)	165
N1—H1A⋯O5ⁱⁱ	0.90	2.14	2.883 (3)	140
N1—H1A⋯O3ⁱⁱⁱ	0.90	2.49	3.060 (3)	122
N1—H1A⋯O2^iv	0.90	2.56	3.040 (3)	114
O5—H5WB⋯O3^v	0.77	2.26	2.999 (3)	161
O5—H5WA⋯O1	0.82	2.59	3.192 (3)	131
O5—H5WA⋯O4	0.82	2.26	3.040 (3)	159
Symmetry codes: (i) x-1, y, z; (ii) -x+2, -y+1, -z+2; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+2; (v) x+1, y, z.

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030345/pv2304Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

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

Figures top

	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.

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

Crystal data top

C₄H₁₂N₂²⁺·2ClO₄⁻·2H₂O	F(000) = 336
M_r = 323.09	D_x = 1.704 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1130 reflections
a = 7.2588 (15) Å	θ = 3.1–27.5°
b = 6.5089 (13) Å	µ = 0.56 mm⁻¹
c = 14.543 (4) Å	T = 293 K
β = 113.56 (3)°	Block, colorless
V = 629.8 (3) Å³	0.28 × 0.26 × 0.20 mm
Z = 2

Data collection top

Rigaku Mercury 2 diffractometer	1458 independent reflections
Radiation source: fine-focus sealed tube	1130 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −8→8
T_min = 0.856, T_max = 0.896	l = −18→18
6362 measured reflections

Refinement top

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.0357P)² + 0.361P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1458 reflections	Δρ_max = 0.28 e Å⁻³
83 parameters	Δρ_min = −0.25 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: 0.044 (4)

Crystal data top

C₄H₁₂N₂²⁺·2ClO₄⁻·2H₂O	V = 629.8 (3) Å³
M_r = 323.09	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.2588 (15) Å	µ = 0.56 mm⁻¹
b = 6.5089 (13) Å	T = 293 K
c = 14.543 (4) Å	0.28 × 0.26 × 0.20 mm
β = 113.56 (3)°

Data collection top

Rigaku Mercury 2 diffractometer	1458 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1130 reflections with I > 2σ(I)
T_min = 0.856, T_max = 0.896	R_int = 0.060
6362 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.07	Δρ_max = 0.28 e Å⁻³
1458 reflections	Δρ_min = −0.25 e Å⁻³
83 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.3021 (4)	1.0866 (4)	0.94987 (19)	0.0411 (6)
H1C	0.2516	1.0117	0.8870	0.049*
H1D	0.1989	1.1821	0.9491	0.049*
C2	0.3493 (4)	0.9393 (4)	1.03562 (19)	0.0426 (6)
H2B	0.3904	1.0149	1.0981	0.051*
H2A	0.2303	0.8603	1.0272	0.051*
Cl1	0.78737 (8)	0.59992 (10)	0.84112 (4)	0.0390 (2)
N1	0.5133 (3)	0.7985 (3)	1.03919 (15)	0.0401 (5)
H1B	0.4715	0.7234	0.9825	0.048*
H1A	0.5420	0.7115	1.0912	0.048*
O1	0.9198 (3)	0.7709 (4)	0.87194 (18)	0.0765 (7)
O2	0.7472 (3)	0.5298 (3)	0.92385 (14)	0.0561 (6)
O3	0.6016 (3)	0.6622 (3)	0.76257 (13)	0.0562 (6)
O4	0.8781 (4)	0.4421 (4)	0.80648 (18)	0.0853 (8)
O5	1.3089 (2)	0.5745 (3)	0.85594 (12)	0.0421 (5)
H5WB	1.3600	0.6040	0.8207	0.063*
H5WA	1.1857	0.5653	0.8324	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0416 (14)	0.0393 (14)	0.0403 (14)	0.0025 (11)	0.0140 (11)	0.0007 (11)
C2	0.0444 (14)	0.0446 (15)	0.0407 (14)	−0.0009 (12)	0.0189 (12)	0.0031 (11)
Cl1	0.0336 (3)	0.0498 (4)	0.0351 (3)	−0.0020 (3)	0.0152 (2)	−0.0022 (3)
N1	0.0538 (13)	0.0292 (10)	0.0348 (11)	−0.0025 (9)	0.0149 (9)	0.0020 (9)
O1	0.0532 (13)	0.0832 (17)	0.0868 (16)	−0.0303 (12)	0.0214 (12)	0.0037 (13)
O2	0.0542 (11)	0.0726 (14)	0.0442 (11)	−0.0003 (10)	0.0226 (9)	0.0140 (10)
O3	0.0415 (10)	0.0814 (15)	0.0391 (10)	0.0024 (10)	0.0091 (9)	0.0105 (10)
O4	0.0803 (16)	0.102 (2)	0.0775 (17)	0.0328 (15)	0.0362 (14)	−0.0225 (14)
O5	0.0373 (9)	0.0469 (11)	0.0433 (10)	0.0015 (8)	0.0174 (8)	0.0026 (8)

Geometric parameters (Å, º) top

C1—N1ⁱ	1.487 (3)	Cl1—O1	1.421 (2)
C1—C2	1.500 (3)	Cl1—O2	1.4218 (19)
C1—H1C	0.97	Cl1—O3	1.4339 (19)
C1—H1D	0.97	N1—C1ⁱ	1.487 (3)
C2—N1	1.487 (3)	N1—H1B	0.90
C2—H2B	0.97	N1—H1A	0.90
C2—H2A	0.97	O5—H5WB	0.77
Cl1—O4	1.417 (2)	O5—H5WA	0.82

N1ⁱ—C1—C2	109.6 (2)	O4—Cl1—O2	110.46 (15)
N1ⁱ—C1—H1C	109.7	O1—Cl1—O2	109.05 (14)
C2—C1—H1C	109.7	O4—Cl1—O3	110.15 (14)
N1ⁱ—C1—H1D	109.7	O1—Cl1—O3	109.38 (14)
C2—C1—H1D	109.7	O2—Cl1—O3	108.62 (12)
H1C—C1—H1D	108.2	C2—N1—C1ⁱ	111.62 (19)
N1—C2—C1	109.7 (2)	C2—N1—H1B	109.3
N1—C2—H2B	109.7	C1ⁱ—N1—H1B	109.3
C1—C2—H2B	109.7	C2—N1—H1A	109.3
N1—C2—H2A	109.7	C1ⁱ—N1—H1A	109.3
C1—C2—H2A	109.7	H1B—N1—H1A	108.0
H2B—C2—H2A	108.2	H5WB—O5—H5WA	118.5
O4—Cl1—O1	109.16 (16)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O5ⁱⁱ	0.90	2.00	2.875 (3)	165
N1—H1A···O5ⁱⁱⁱ	0.90	2.14	2.883 (3)	140
N1—H1A···O3^iv	0.90	2.49	3.060 (3)	122
N1—H1A···O2^v	0.90	2.56	3.040 (3)	114
O5—H5WB···O3^vi	0.77	2.26	2.999 (3)	161
O5—H5WA···O1	0.82	2.59	3.192 (3)	131
O5—H5WA···O4	0.82	2.26	3.040 (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.

Experimental details

Crystal data
Chemical formula	C₄H₁₂N₂²⁺·2ClO₄⁻·2H₂O
M_r	323.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.2588 (15), 6.5089 (13), 14.543 (4)
β (°)	113.56 (3)
V (Å³)	629.8 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.56
Crystal size (mm)	0.28 × 0.26 × 0.20

Data collection
Diffractometer	Rigaku Mercury 2
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.856, 0.896
No. of measured, independent and observed [I > 2σ(I)] reflections	6362, 1458, 1130
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.109, 1.07
No. of reflections	1458
No. of parameters	83
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.25

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O5ⁱ	0.90	2.00	2.875 (3)	165
N1—H1A···O5ⁱⁱ	0.90	2.14	2.883 (3)	140
N1—H1A···O3ⁱⁱⁱ	0.90	2.49	3.060 (3)	122
N1—H1A···O2^iv	0.90	2.56	3.040 (3)	114
O5—H5WB···O3^v	0.77	2.26	2.999 (3)	161
O5—H5WA···O1	0.82	2.59	3.192 (3)	131
O5—H5WA···O4	0.82	2.26	3.040 (3)	159

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

Acknowledgements

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

References

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar