4-(2-Azaniumyl­eth­yl)piperazin-1-ium bis(perchlorate)

doi:10.1107/S1600536811033976

Acta Crystallogr Sect E Struct Rep Online. 2011 September 1; 67(Pt 9): o2400.

Published online 2011 August 27. doi: 10.1107/S1600536811033976

PMCID: PMC3200960

4-(2-Azaniumylethyl)piperazin-1-ium bis(perchlorate)

Mohammad Reza Reisi,^a Muhammad Saleh Salga,^b Hamid Khaledi,^b^* and Hapipah Mohd Ali^b

^aChemistry Department, Isfahan University, 81646-73441 Isfahan, Iran

^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia

Correspondence e-mail: khaledi/at/siswa.um.edu.my

Received August 12, 2011; Accepted August 19, 2011.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Abstract

In the title compound, C₆H₁₇N₃ ²⁺·2ClO₄ ⁻, the piperazine ring adopts a chair conformation with the ethylammonium fragment occupying an equatorial position. In the crystal, the dications and perchlorate anions are linked through N—H (...)

O hydrogen bonding and weak C—H (...)

O hydrogen bonding into a three-dimensional supramolecular network.

Related literature

For the structures of related salts of the 4-(2-ammonioethyl)piperazin-1-ium cation, see: Guerfel et al. (1999

); Srinivasan et al. (2008

, 2009

An external file that holds a picture, illustration, etc.
Object name is e-67-o2400-scheme1.jpg Object name is e-67-o2400-scheme1.jpg

Experimental

Crystal data

C₆H₁₇N₃ ²⁺·2ClO₄ ⁻
M _r = 330.13
Monoclinic,
a = 7.5218 (1) Å
b = 11.4371 (2) Å
c = 15.2239 (2) Å
β = 97.437 (1)°
V = 1298.66 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 100 K
0.28 × 0.17 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T _min = 0.863, T _max = 0.968
8644 measured reflections
2969 independent reflections
2671 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.080
S = 1.05
2969 reflections
187 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: APEX2 (Bruker, 2007

); cell refinement: SAINT (Bruker, 2007

); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008

); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008

); molecular graphics: X-SEED (Barbour, 2001

); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010

Table 1

Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811033976/xu5296sup1.cif

Click here to view.^{(16K, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033976/xu5296Isup2.hkl

Click here to view.^{(146K, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811033976/xu5296Isup3.cml

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

Acknowledgments

The authors thank the University of Malaya for funding this study (PPP grant No. PS359/2009C).

supplementary crystallographic information

Comment

The crystals of the title compound were obtained unexpectedly during an attempt to prepare a tin(IV) complex of 1-(2-aminoethyl)piperazine in the presence of sodium perchlorate. The organic molecule is doubly protonated at its primary and secondary N atoms, while the tertiary N atom, N2, remains unprotonated. Similar to the structures of some other 1-(2-ammoniumethyl)piperazinium salts (Guerfel et al., 1999; Srinivasan et al., 2008, 2009), the piperazine ring adopts a chair conformation with the ethylammonium group occupying an equatorial position. In the crystal, the dicationic organic moieties and perchlorate anions are linked through N—H···O and C—H···O interactions (Table 1) into a three-dimensional supra-molecular network.

Experimental

A mixture of 4-(2-aminoethyl)piperazine (0.26 g, 2 mmol) and Bu₂SnCl₂ (0.6 g, 2 mmol) in methanol (50 ml) was refluxed for 2 h. NaClO₄ (0.56 g, 4 mmol) was then added and the precipitated sodium chloride was filtered off. The filtrate was evaporated and the obtained solid was recrystallized from ethanol at room temperature to give the colorless crystals of the title compound.

Figures

Fig. 1.

Molecular structure of the title compound with thermal ellipsoids at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

Crystal data

C₆H₁₇N₃²⁺·2ClO₄⁻	F(000) = 688
M_r = 330.13	D_x = 1.688 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4052 reflections
a = 7.5218 (1) Å	θ = 2.2–30.5°
b = 11.4371 (2) Å	µ = 0.54 mm⁻¹
c = 15.2239 (2) Å	T = 100 K
β = 97.437 (1)°	Blade, colourless
V = 1298.66 (3) Å³	0.28 × 0.17 × 0.06 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	2969 independent reflections
Radiation source: fine-focus sealed tube	2671 reflections with I > 2σ(I)
graphite	R_int = 0.023
and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.863, T_max = 0.968	k = −14→12
8644 measured reflections	l = −19→18

Refinement

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0388P)² + 0.8608P] where P = (F_o² + 2F_c²)/3
2969 reflections	(Δ/σ)_max = 0.001
187 parameters	Δρ_max = 0.27 e Å⁻³
5 restraints	Δρ_min = −0.59 e Å⁻³

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)

	x	y	z	U_iso*/U_eq
N1	0.3280 (2)	0.44351 (13)	0.34193 (10)	0.0188 (3)
H1C	0.390 (3)	0.5105 (15)	0.3389 (14)	0.023*
H1D	0.268 (3)	0.4345 (19)	0.2884 (11)	0.023*
N2	0.22434 (17)	0.25008 (12)	0.44167 (9)	0.0137 (3)
N3	0.26916 (19)	0.16033 (12)	0.61553 (9)	0.0138 (3)
H3C	0.308 (3)	0.2308 (14)	0.6010 (13)	0.017*
H3D	0.161 (2)	0.1729 (17)	0.6323 (13)	0.017*
H3E	0.340 (2)	0.1314 (17)	0.6606 (11)	0.017*
C1	0.4538 (2)	0.34346 (15)	0.36621 (12)	0.0212 (4)
H1A	0.5295	0.3604	0.4229	0.025*
H1B	0.5334	0.3327	0.3199	0.025*
C2	0.3466 (2)	0.23325 (15)	0.37506 (11)	0.0182 (3)
H2A	0.2769	0.2137	0.3173	0.022*
H2B	0.4289	0.1674	0.3928	0.022*
C3	0.1959 (2)	0.45727 (15)	0.40696 (12)	0.0186 (3)
H3A	0.1099	0.5205	0.3873	0.022*
H3B	0.2595	0.4787	0.4658	0.022*
C4	0.0963 (2)	0.34326 (15)	0.41350 (12)	0.0190 (3)
H4A	0.0095	0.3513	0.4568	0.023*
H4B	0.0289	0.3235	0.3552	0.023*
C5	0.1375 (2)	0.13996 (15)	0.46127 (11)	0.0165 (3)
H5A	0.1257	0.0886	0.4085	0.020*
H5B	0.0160	0.1559	0.4768	0.020*
C6	0.2498 (2)	0.08004 (14)	0.53790 (11)	0.0158 (3)
H6A	0.1911	0.0065	0.5529	0.019*
H6B	0.3694	0.0606	0.5214	0.019*
Cl1	0.72577 (5)	0.21252 (3)	0.61138 (3)	0.01391 (10)
O1	0.90644 (15)	0.24485 (11)	0.64617 (9)	0.0220 (3)
O2	0.71413 (18)	0.18723 (12)	0.51861 (8)	0.0263 (3)
O3	0.67246 (17)	0.10996 (11)	0.65736 (9)	0.0241 (3)
O4	0.60538 (16)	0.30697 (11)	0.62494 (10)	0.0246 (3)
Cl2	0.74537 (5)	0.57603 (3)	0.26377 (2)	0.01355 (10)
O5	0.59033 (15)	0.51100 (11)	0.22387 (8)	0.0188 (3)
O6	0.75093 (17)	0.57359 (11)	0.35894 (8)	0.0200 (3)
O7	0.73342 (17)	0.69479 (10)	0.23263 (8)	0.0204 (3)
O8	0.90557 (15)	0.52178 (11)	0.23899 (8)	0.0202 (3)

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0269 (8)	0.0140 (7)	0.0159 (7)	−0.0024 (6)	0.0044 (6)	0.0008 (6)
N2	0.0141 (6)	0.0131 (7)	0.0144 (7)	−0.0002 (5)	0.0034 (5)	0.0015 (5)
N3	0.0150 (6)	0.0119 (7)	0.0147 (7)	−0.0003 (5)	0.0026 (5)	0.0003 (5)
C1	0.0235 (9)	0.0174 (9)	0.0246 (9)	0.0005 (7)	0.0107 (7)	0.0029 (7)
C2	0.0227 (8)	0.0158 (8)	0.0178 (8)	−0.0002 (6)	0.0090 (6)	0.0002 (6)
C3	0.0193 (8)	0.0171 (8)	0.0195 (8)	0.0022 (6)	0.0030 (6)	0.0004 (7)
C4	0.0151 (8)	0.0187 (9)	0.0227 (9)	0.0016 (6)	0.0009 (6)	0.0016 (7)
C5	0.0175 (8)	0.0162 (8)	0.0158 (8)	−0.0044 (6)	0.0027 (6)	−0.0009 (6)
C6	0.0190 (8)	0.0125 (8)	0.0164 (8)	−0.0014 (6)	0.0046 (6)	−0.0026 (6)
Cl1	0.01169 (18)	0.01297 (19)	0.0174 (2)	−0.00018 (13)	0.00309 (13)	−0.00125 (14)
O1	0.0125 (6)	0.0229 (7)	0.0300 (7)	−0.0028 (5)	0.0010 (5)	−0.0039 (5)
O2	0.0263 (7)	0.0354 (8)	0.0176 (7)	−0.0007 (6)	0.0045 (5)	−0.0055 (6)
O3	0.0219 (6)	0.0207 (7)	0.0290 (7)	−0.0045 (5)	0.0012 (5)	0.0090 (5)
O4	0.0155 (6)	0.0157 (6)	0.0437 (8)	0.0021 (5)	0.0076 (5)	−0.0067 (6)
Cl2	0.01502 (19)	0.01298 (19)	0.01291 (19)	0.00041 (13)	0.00284 (13)	−0.00077 (13)
O5	0.0160 (6)	0.0196 (6)	0.0206 (6)	−0.0037 (5)	0.0016 (5)	−0.0013 (5)
O6	0.0283 (7)	0.0194 (6)	0.0128 (6)	0.0033 (5)	0.0045 (5)	−0.0001 (5)
O7	0.0274 (7)	0.0134 (6)	0.0207 (6)	−0.0012 (5)	0.0038 (5)	0.0031 (5)
O8	0.0164 (6)	0.0227 (7)	0.0223 (7)	0.0022 (5)	0.0056 (5)	−0.0069 (5)

Geometric parameters (Å, °)

N1—C3	1.499 (2)	C3—H3A	0.9900
N1—C1	1.500 (2)	C3—H3B	0.9900
N1—H1C	0.902 (15)	C4—H4A	0.9900
N1—H1D	0.884 (15)	C4—H4B	0.9900
N2—C4	1.463 (2)	C5—C6	1.513 (2)
N2—C5	1.467 (2)	C5—H5A	0.9900
N2—C2	1.467 (2)	C5—H5B	0.9900
N3—C6	1.489 (2)	C6—H6A	0.9900
N3—H3C	0.894 (15)	C6—H6B	0.9900
N3—H3D	0.894 (15)	Cl1—O2	1.4331 (13)
N3—H3E	0.878 (15)	Cl1—O1	1.4414 (12)
C1—C2	1.512 (2)	Cl1—O4	1.4416 (12)
C1—H1A	0.9900	Cl1—O3	1.4489 (13)
C1—H1B	0.9900	Cl2—O7	1.4376 (12)
C2—H2A	0.9900	Cl2—O6	1.4444 (12)
C2—H2B	0.9900	Cl2—O8	1.4481 (12)
C3—C4	1.513 (2)	Cl2—O5	1.4487 (12)

C3—N1—C1	111.60 (13)	H3A—C3—H3B	108.3
C3—N1—H1C	109.7 (13)	N2—C4—C3	109.53 (13)
C1—N1—H1C	110.3 (13)	N2—C4—H4A	109.8
C3—N1—H1D	108.6 (14)	C3—C4—H4A	109.8
C1—N1—H1D	111.6 (14)	N2—C4—H4B	109.8
H1C—N1—H1D	104.8 (19)	C3—C4—H4B	109.8
C4—N2—C5	113.04 (13)	H4A—C4—H4B	108.2
C4—N2—C2	109.92 (13)	N2—C5—C6	109.07 (13)
C5—N2—C2	111.30 (13)	N2—C5—H5A	109.9
C6—N3—H3C	111.2 (13)	C6—C5—H5A	109.9
C6—N3—H3D	109.1 (13)	N2—C5—H5B	109.9
H3C—N3—H3D	105.1 (18)	C6—C5—H5B	109.9
C6—N3—H3E	112.0 (13)	H5A—C5—H5B	108.3
H3C—N3—H3E	110.4 (18)	N3—C6—C5	108.67 (13)
H3D—N3—H3E	108.8 (18)	N3—C6—H6A	110.0
N1—C1—C2	109.35 (14)	C5—C6—H6A	110.0
N1—C1—H1A	109.8	N3—C6—H6B	110.0
C2—C1—H1A	109.8	C5—C6—H6B	110.0
N1—C1—H1B	109.8	H6A—C6—H6B	108.3
C2—C1—H1B	109.8	O2—Cl1—O1	110.39 (8)
H1A—C1—H1B	108.3	O2—Cl1—O4	109.44 (8)
N2—C2—C1	109.97 (14)	O1—Cl1—O4	109.57 (8)
N2—C2—H2A	109.7	O2—Cl1—O3	109.10 (8)
C1—C2—H2A	109.7	O1—Cl1—O3	109.69 (8)
N2—C2—H2B	109.7	O4—Cl1—O3	108.62 (8)
C1—C2—H2B	109.7	O7—Cl2—O6	109.97 (7)
H2A—C2—H2B	108.2	O7—Cl2—O8	109.73 (8)
N1—C3—C4	109.21 (14)	O6—Cl2—O8	109.63 (7)
N1—C3—H3A	109.8	O7—Cl2—O5	109.52 (7)
C4—C3—H3A	109.8	O6—Cl2—O5	109.14 (7)
N1—C3—H3B	109.8	O8—Cl2—O5	108.82 (7)
C4—C3—H3B	109.8

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O4ⁱ	0.90 (2)	2.16 (2)	2.9298 (19)	143.(2)
N1—H1D···O3ⁱⁱ	0.88 (2)	2.09 (2)	2.964 (2)	168.(2)
N3—H3C···O6ⁱ	0.89 (2)	2.38 (2)	3.0741 (19)	135.(2)
N3—H3C···O4	0.89 (2)	2.39 (2)	3.0225 (19)	128.(2)
N3—H3D···O1ⁱⁱⁱ	0.89 (2)	2.12 (2)	2.9875 (18)	163.(2)
N3—H3E···O8^iv	0.88 (2)	2.14 (2)	2.9025 (19)	145.(2)
N3—H3E···O3	0.88 (2)	2.52 (2)	3.0724 (19)	122.(2)
C1—H1B···O7^v	0.99	2.56	3.407 (2)	143.
C3—H3A···O8ⁱⁱⁱ	0.99	2.56	3.226 (2)	124.
C5—H5A···O5^vi	0.99	2.58	3.436 (2)	145.
C5—H5B···O2ⁱⁱⁱ	0.99	2.46	3.452 (2)	178.

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5296).

References

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
Srinivasan, B. R., Dhuri, S. N., Naik, A. R., Näther, C. & Bensch, W. (2008). Polyhedron, 27, 25–34.
Srinivasan, B. R., Naik, A. R., Dhuri, S. N., Näther, C. & Bensch, W. (2009). Polyhedron, 28, 3715–3722.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

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