organic compounds
4-(2-Azaniumylethyl)piperazin-1-ium bis(perchlorate)
aChemistry Department, Isfahan University, 81646-73441 Isfahan, Iran, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: khaledi@siswa.um.edu.my
In the title compound, C6H17N32+·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).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell 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).
Supporting information
10.1107/S1600536811033976/xu5296sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811033976/xu5296Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811033976/xu5296Isup3.cml
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.
The C-bound H atoms were placed at calculated positions and were treated as riding on their parent C atoms with C—H = 0.99 Å. The N-bound H atoms were located in a difference Fourier map, and refined with distance restraints of N—H = 0.91 (2) Å. For all H atoms, Uiso(H) was set to 1.2Ueq(carrier atom).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008) and publCIF (Westrip, 2010).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. |
C6H17N32+·2ClO4− | F(000) = 688 |
Mr = 330.13 | Dx = 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 |
Bruker APEXII CCD diffractometer | 2969 independent reflections |
Radiation source: fine-focus sealed tube | 2671 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.863, Tmax = 0.968 | k = −14→12 |
8644 measured reflections | l = −19→18 |
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(Fo2) + (0.0388P)2 + 0.8608P] where P = (Fo2 + 2Fc2)/3 |
2969 reflections | (Δ/σ)max = 0.001 |
187 parameters | Δρmax = 0.27 e Å−3 |
5 restraints | Δρmin = −0.59 e Å−3 |
C6H17N32+·2ClO4− | V = 1298.66 (3) Å3 |
Mr = 330.13 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.5218 (1) Å | µ = 0.54 mm−1 |
b = 11.4371 (2) Å | T = 100 K |
c = 15.2239 (2) Å | 0.28 × 0.17 × 0.06 mm |
β = 97.437 (1)° |
Bruker APEXII CCD diffractometer | 2969 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2671 reflections with I > 2σ(I) |
Tmin = 0.863, Tmax = 0.968 | Rint = 0.023 |
8644 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 5 restraints |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.27 e Å−3 |
2969 reflections | Δρmin = −0.59 e Å−3 |
187 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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 |
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···O8iv | 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···O7v | 0.99 | 2.56 | 3.407 (2) | 143 |
C3—H3A···O8iii | 0.99 | 2.56 | 3.226 (2) | 124 |
C5—H5A···O5vi | 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. |
Experimental details
Crystal data | |
Chemical formula | C6H17N32+·2ClO4− |
Mr | 330.13 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 7.5218 (1), 11.4371 (2), 15.2239 (2) |
β (°) | 97.437 (1) |
V (Å3) | 1298.66 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.54 |
Crystal size (mm) | 0.28 × 0.17 × 0.06 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.863, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8644, 2969, 2671 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.080, 1.05 |
No. of reflections | 2969 |
No. of parameters | 187 |
No. of restraints | 5 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.59 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1C···O4i | 0.902 (15) | 2.158 (18) | 2.9298 (19) | 143.1 (18) |
N1—H1D···O3ii | 0.884 (15) | 2.094 (16) | 2.964 (2) | 167.8 (19) |
N3—H3C···O6i | 0.894 (15) | 2.375 (18) | 3.0741 (19) | 135.2 (16) |
N3—H3C···O4 | 0.894 (15) | 2.387 (18) | 3.0225 (19) | 128.2 (16) |
N3—H3D···O1iii | 0.894 (15) | 2.121 (16) | 2.9875 (18) | 163.0 (18) |
N3—H3E···O8iv | 0.878 (15) | 2.141 (17) | 2.9025 (19) | 144.7 (18) |
N3—H3E···O3 | 0.878 (15) | 2.517 (18) | 3.0724 (19) | 121.9 (16) |
C1—H1B···O7v | 0.99 | 2.56 | 3.407 (2) | 143.1 |
C3—H3A···O8iii | 0.99 | 2.56 | 3.226 (2) | 124.4 |
C5—H5A···O5vi | 0.99 | 2.58 | 3.436 (2) | 145.1 |
C5—H5B···O2iii | 0.99 | 2.46 | 3.452 (2) | 177.5 |
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. |
Acknowledgements
The authors thank the University of Malaya for funding this study (PPP grant No. PS359/2009C).
References
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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.