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

Peng, C.-H.

doi:10.1107/S160053681002862X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2114

https://doi.org/10.1107/S160053681002862X

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

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 30 June 2010; accepted 17 July 2010; online 24 July 2010)

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 ( $[\overline{1}]$ 01).

Related literature

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

Experimental

Crystal data

C₅H₁₃N₂⁺·ClO₄⁻
M_r = 200.62
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.075
wR(F²) = 0.224
S = 1.05
2055 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1	0.90	2.38	3.258 (6)	166
N1—H1C⋯O3	0.90	2.54	3.250 (5)	136
N2—H2D⋯O2ⁱ	0.90	2.43	2.998 (7)	121
N2—H2C⋯N1ⁱⁱ	0.90	1.99	2.883 (4)	169
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681002862X/rz2472Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

(±)-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.

Structure description top

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

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 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 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

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

Crystal data top

C₅H₁₃N₂⁺·ClO₄⁻	F(000) = 424
M_r = 200.62	D_x = 1.482 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2yn	Cell parameters from 1541 reflections
a = 6.8977 (5) Å	θ = 3.1–27.5°
b = 8.1292 (6) Å	µ = 0.41 mm⁻¹
c = 16.2201 (11) Å	T = 293 K
β = 98.614 (3)°	Block, colourless
V = 899.25 (11) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2055 independent reflections
Radiation source: fine-focus sealed tube	1541 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −10→10
T_min = 0.80, T_max = 0.90	l = −21→20
8953 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.224	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1123P)² + 1.4914P] where P = (F_o² + 2F_c²)/3
2055 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.86 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₅H₁₃N₂⁺·ClO₄⁻	V = 899.25 (11) Å³
M_r = 200.62	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.8977 (5) Å	µ = 0.41 mm⁻¹
b = 8.1292 (6) Å	T = 293 K
c = 16.2201 (11) Å	0.30 × 0.25 × 0.20 mm
β = 98.614 (3)°

Data collection top

Rigaku SCXmini diffractometer	2055 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1541 reflections with I > 2σ(I)
T_min = 0.80, T_max = 0.90	R_int = 0.040
8953 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	0 restraints
wR(F²) = 0.224	H-atom parameters constrained
S = 1.05	Δρ_max = 0.86 e Å⁻³
2055 reflections	Δρ_min = −0.56 e Å⁻³
109 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	0.4992 (5)	0.6921 (5)	0.6807 (2)	0.0414 (8)
H1B	0.5975	0.7730	0.7019	0.050*
H1A	0.5525	0.6233	0.6407	0.050*
C2	0.4487 (5)	0.5875 (5)	0.7518 (2)	0.0406 (8)
H2A	0.5644	0.5267	0.7759	0.049*
H2B	0.4118	0.6591	0.7947	0.049*
C3	0.1170 (5)	0.5531 (5)	0.6809 (2)	0.0389 (8)
H3A	0.0599	0.6227	0.7194	0.047*
H3B	0.0205	0.4703	0.6603	0.047*
C4	0.1591 (5)	0.6579 (5)	0.6075 (2)	0.0384 (8)
H4A	0.2062	0.5856	0.5664	0.046*
C5	−0.0190 (7)	0.7490 (7)	0.5654 (3)	0.0646 (13)
H5A	0.0152	0.8117	0.5196	0.097*
H5B	−0.0656	0.8218	0.6048	0.097*
H5C	−0.1201	0.6716	0.5452	0.097*
Cl1	0.56264 (14)	0.19954 (12)	0.59443 (6)	0.0442 (4)
N1	0.2890 (5)	0.4712 (4)	0.7261 (2)	0.0392 (7)
H1C	0.3305	0.3941	0.6929	0.047*
N2	0.3194 (4)	0.7764 (3)	0.63945 (18)	0.0352 (7)
H2D	0.3494	0.8369	0.5966	0.042*
H2C	0.2761	0.8453	0.6761	0.042*
O1	0.3667 (7)	0.1613 (7)	0.6079 (3)	0.1041 (16)
O2	0.5363 (11)	0.2923 (9)	0.5226 (3)	0.154 (3)
O3	0.6614 (5)	0.2921 (5)	0.6628 (2)	0.0759 (11)
O4	0.6557 (9)	0.0550 (9)	0.5835 (6)	0.215 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0355 (18)	0.044 (2)	0.046 (2)	−0.0020 (15)	0.0098 (15)	0.0026 (16)
C2	0.0404 (19)	0.0397 (19)	0.0410 (19)	0.0043 (15)	0.0037 (15)	0.0042 (15)
C3	0.0395 (19)	0.0380 (18)	0.0401 (18)	−0.0068 (15)	0.0095 (15)	−0.0047 (15)
C4	0.043 (2)	0.0402 (19)	0.0315 (17)	−0.0016 (15)	0.0028 (14)	−0.0028 (14)
C5	0.054 (3)	0.079 (3)	0.056 (3)	0.010 (2)	−0.007 (2)	0.004 (2)
Cl1	0.0500 (6)	0.0457 (6)	0.0378 (5)	0.0080 (4)	0.0094 (4)	−0.0044 (4)
N1	0.0481 (18)	0.0298 (14)	0.0415 (16)	0.0004 (13)	0.0130 (13)	0.0016 (12)
N2	0.0422 (16)	0.0319 (15)	0.0329 (15)	−0.0012 (12)	0.0103 (12)	0.0013 (12)
O1	0.089 (3)	0.149 (4)	0.080 (3)	−0.040 (3)	0.034 (2)	−0.028 (3)
O2	0.196 (7)	0.199 (7)	0.067 (3)	−0.086 (5)	0.017 (3)	0.048 (4)
O3	0.072 (2)	0.076 (2)	0.074 (2)	0.0078 (18)	−0.0083 (19)	−0.0251 (19)
O4	0.132 (5)	0.151 (5)	0.318 (11)	0.089 (4)	−0.105 (6)	−0.155 (7)

Geometric parameters (Å, º) top

C1—N2	1.485 (5)	C4—C5	1.507 (6)
C1—C2	1.514 (5)	C4—H4A	0.9800
C1—H1B	0.9700	C5—H5A	0.9600
C1—H1A	0.9700	C5—H5B	0.9600
C2—N1	1.465 (5)	C5—H5C	0.9600
C2—H2A	0.9700	Cl1—O4	1.363 (5)
C2—H2B	0.9700	Cl1—O2	1.377 (5)
C3—N1	1.459 (5)	Cl1—O3	1.426 (4)
C3—C4	1.526 (5)	Cl1—O1	1.436 (4)
C3—H3A	0.9700	N1—H1C	0.8998
C3—H3B	0.9700	N2—H2D	0.9000
C4—N2	1.500 (5)	N2—H2C	0.9000

N2—C1—C2	109.3 (3)	C3—C4—H4A	108.5
N2—C1—H1B	109.8	C4—C5—H5A	109.5
C2—C1—H1B	109.8	C4—C5—H5B	109.5
N2—C1—H1A	109.8	H5A—C5—H5B	109.5
C2—C1—H1A	109.8	C4—C5—H5C	109.5
H1B—C1—H1A	108.3	H5A—C5—H5C	109.5
N1—C2—C1	113.3 (3)	H5B—C5—H5C	109.5
N1—C2—H2A	108.9	O4—Cl1—O2	111.5 (6)
C1—C2—H2A	108.9	O4—Cl1—O3	112.1 (3)
N1—C2—H2B	108.9	O2—Cl1—O3	110.9 (3)
C1—C2—H2B	108.9	O4—Cl1—O1	107.8 (5)
H2A—C2—H2B	107.7	O2—Cl1—O1	103.9 (4)
N1—C3—C4	114.3 (3)	O3—Cl1—O1	110.3 (2)
N1—C3—H3A	108.7	C3—N1—C2	111.6 (3)
C4—C3—H3A	108.7	C3—N1—H1C	109.0
N1—C3—H3B	108.7	C2—N1—H1C	109.1
C4—C3—H3B	108.7	C1—N2—C4	112.5 (3)
H3A—C3—H3B	107.6	C1—N2—H2D	109.1
N2—C4—C5	110.5 (3)	C4—N2—H2D	109.1
N2—C4—C3	107.8 (3)	C1—N2—H2C	109.1
C5—C4—C3	113.0 (4)	C4—N2—H2C	109.1
N2—C4—H4A	108.5	H2D—N2—H2C	107.8
C5—C4—H4A	108.5

N2—C1—C2—N1	54.6 (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—C2	52.7 (4)	C3—C4—N2—C1	56.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1	0.90	2.38	3.258 (6)	166
N1—H1C···O3	0.90	2.54	3.250 (5)	136
N2—H2D···O2ⁱ	0.90	2.43	2.998 (7)	121
N2—H2C···N1ⁱⁱ	0.90	1.99	2.883 (4)	169

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

Experimental details

Crystal data
Chemical formula	C₅H₁₃N₂⁺·ClO₄⁻
M_r	200.62
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.8977 (5), 8.1292 (6), 16.2201 (11)
β (°)	98.614 (3)
V (Å³)	899.25 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku SCXmini
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.80, 0.90
No. of measured, independent and observed [I > 2σ(I)] reflections	8953, 2055, 1541
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.224, 1.05
No. of reflections	2055
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.56

Computer programs: CrystalClear (Rigaku, 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—H1C···O1	0.90	2.38	3.258 (6)	166.3
N1—H1C···O3	0.90	2.54	3.250 (5)	135.8
N2—H2D···O2ⁱ	0.90	2.43	2.998 (7)	121.1
N2—H2C···N1ⁱⁱ	0.90	1.99	2.883 (4)	168.9

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

Acknowledgements

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

References

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