1,4-Bis(2-ammonio­ethyl)­piperazin-1,4-ium tetraperchlorate tetrahydrate

Ye, M.-D.; Hu, M.-L.; Zain, S.M.; Ng, S.W.

doi:10.1107/S1600536802014782

1,4-Bis(2-ammonioethyl)piperazin-1,4-ium tetraperchlorate tetrahydrate

M.-D. Ye, M.-L. Hu, S. M. Zain and S. W. Ng

The tetracation of bis(2-ammonioethyl)piperazin-1,4-ium tetraperchlorate tetrahydrate, C₈H₂₄N₄⁴⁺·4ClO₄^-·4H₂O, lies over a center of symmetry and the piperazinyl ring adopts a chair conformation. Four ammonium N atoms, perchlorate anions and lattice water molecules are linked by hydrogen bonds into an infinite three-dimensional framework.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802014782/ya6122sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802014782/ya6122Isup2.hkl Contains datablock I

CCDC reference: 197475

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.003 Å
R factor = 0.050
wR factor = 0.146
Data-to-parameter ratio = 14.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_735  Alert C D-H     Calc     0.84(3), Rep   0.840(10) ....       3.00 s.u-Ratio
                     O1W  -H1W2    1.555   1.555

PLAT_736  Alert C H...A   Calc     2.19(3), Rep   2.190(10) ....       3.00 s.u-Ratio
                     H1W2 -O5      1.555   1.555


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

Comment top

The red title tetraammonium perchorate, (I), was a suprize product from the reaction between triethylenetetramine and perchloric acid; the reaction is probably catalyzed by ferrous ions. A search through the Cambridge Structural Database (Allen et al., 1983) for the neutral bis(2-ethylamino)-1,4-piperazine residue found only one example where this ligand forms a complex with silver nitrate in which the amino group and one of the tertiary nitrogen atoms of the piperazinyl ring chelate to the metal atom (Zhang et al., 2001; Cai & Ng, 2002).

The piperazinium portion of the cation adopts a chair conformation, and both ammonioethyl groups occupy equatorial positions (Fig. 1). A pair of ammonio and piperazinium groups form two hydrogen bonds to a water molecule [N_ammonio···O = 2.695 (2) Å and N_piperazinium···O = 2.905 (3) Å]; this water molecule then uses one of its H atoms to interact with a perchlorate anion and the other with a second lattice water molecule. The second water molecule interacts with two other perchlorate O atoms to furnish a three-dimensional network structure.

The cationic portion of the structure that has been optimized at the PM3 level (Table 2) also adopts a chair conformation, but the calculated bond distances are somewhat longer than the experimental distances. On the other hand, the experimental distances are closer to the values calculated for the neutral ligand itself.

Experimental top

Iron(II) chloride (0.13 g, 1 mmol) was dissolved in water (10 ml) and the solution was mixed with an aqueous solution (10 ml) of triethylenetetramine (0.15 g, 1 mmol) to give a green precipitate. Perchloric acid (0.40 g, 4 mmol) was then added to dissolve the precipitate to give a red solution. Red crystals separated from solution after several weeks.

For the geometry-optimization calculations, the initial structures of the tetracation and the neutral bis(2-aminoethyl)piperazine were taken from the X-ray structure. They were optimized at their lowest energy state (singlet spin state) by using the semi-empirical quantum chemical PM3 Hamiltonian in HYPERCHEM (Hypercube, Inc., 2001). The unrestricted Hartree Fock method was employed in the optimization.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. ORTEPII (Johnson, 1976) plot of the fragment of the structure of (I) at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.

1,4-Bis(2-ammonioethyl)piperazin-1,4-ium tetraperchlorate tetrahydrate top

Crystal data top

C₈H₂₄N₄⁴⁺·4ClO₄⁻·4H₂O	F(000) = 672
M_r = 646.18	D_x = 1.742 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.862 (1) Å	Cell parameters from 3500 reflections
b = 19.644 (3) Å	θ = 2.8–28.0°
c = 8.204 (1) Å	µ = 0.58 mm⁻¹
β = 103.53 (1)°	T = 298 K
V = 1231.9 (3) Å³	Block, red
Z = 2	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker CCD area-detector diffractometer	2449 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 28.0°, θ_min = 2.8°
ω scans	h = −9→10
7255 measured reflections	k = −18→25
2885 independent reflections	l = −10→10

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0965P)² + 0.3123P] where P = (F_o² + 2F_c²)/3
2885 reflections	(Δ/σ)_max < 0.001
195 parameters	Δρ_max = 0.75 e Å⁻³
13 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₈H₂₄N₄⁴⁺·4ClO₄⁻·4H₂O	V = 1231.9 (3) Å³
M_r = 646.18	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.862 (1) Å	µ = 0.58 mm⁻¹
b = 19.644 (3) Å	T = 298 K
c = 8.204 (1) Å	0.30 × 0.20 × 0.20 mm
β = 103.53 (1)°

Data collection top

Bruker CCD area-detector diffractometer	2449 reflections with I > 2σ(I)
7255 measured reflections	R_int = 0.029
2885 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	13 restraints
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.75 e Å⁻³
2885 reflections	Δρ_min = −0.27 e Å⁻³
195 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.46188 (7)	0.17189 (3)	0.85643 (7)	0.0384 (2)
Cl2	−0.20735 (7)	0.11224 (3)	0.42162 (7)	0.0395 (2)
O1	0.3558 (3)	0.1991 (1)	0.7030 (2)	0.0658 (6)
O2	0.6130 (3)	0.2126 (1)	0.9091 (3)	0.0726 (6)
O3	0.3603 (3)	0.1736 (1)	0.9797 (2)	0.0625 (6)
O4	0.5084 (4)	0.1034 (1)	0.8342 (4)	0.0862 (8)
O5	−0.2798 (3)	0.1471 (2)	0.5396 (3)	0.0893 (9)
O6	−0.2883 (4)	0.1376 (2)	0.2598 (3)	0.0849 (8)
O7	−0.0241 (3)	0.1221 (2)	0.4601 (4)	0.0888 (8)
O8	−0.2487 (3)	0.0420 (1)	0.4248 (3)	0.0788 (7)
O1w	−0.0069 (3)	0.2256 (1)	0.7820 (2)	0.0541 (5)
O2w	−0.0018 (2)	0.1633 (1)	1.0763 (2)	0.0497 (4)
N1	0.3052 (3)	0.1593 (1)	0.3538 (3)	0.0444 (5)
N2	0.1421 (2)	0.0380 (1)	0.1092 (2)	0.0297 (4)
C1	0.3244 (3)	0.0846 (1)	0.3809 (2)	0.0337 (4)
C2	0.3222 (2)	0.0455 (1)	0.2215 (3)	0.0353 (4)
C3	0.1514 (3)	0.0145 (1)	−0.0628 (3)	0.0391 (5)
C4	−0.0295 (3)	0.0105 (1)	−0.1768 (3)	0.0369 (5)
H1a	0.2300	0.0683	0.4285	0.040*
H1b	0.4337	0.0755	0.4614	0.040*
H2a	0.3965	0.0687	0.1601	0.042*
H2b	0.3711	0.0006	0.2507	0.042*
H3a	0.2064	−0.0300	−0.0552	0.047*
H3b	0.2225	0.0460	−0.1095	0.047*
H4a	−0.0827	0.0554	−0.1875	0.044*
H4b	−0.0209	−0.0043	−0.2874	0.044*
H1n1	0.308 (3)	0.175 (2)	0.452 (2)	0.09 (1)*
H1n2	0.209 (2)	0.171 (1)	0.289 (2)	0.06 (1)*
H1n3	0.390 (2)	0.176 (1)	0.320 (3)	0.04 (1)*
H2n	0.091 (3)	0.076 (1)	0.100 (3)	0.03 (1)*
H1w1	0.097 (2)	0.224 (2)	0.771 (4)	0.11 (2)*
H1w2	−0.076 (3)	0.210 (2)	0.696 (3)	0.07 (1)*
H2w1	−0.002 (3)	0.175 (2)	0.978 (2)	0.05 (1)*
H2w2	−0.098 (2)	0.172 (2)	1.100 (3)	0.07 (1)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0445 (3)	0.0302 (3)	0.0403 (3)	−0.0010 (2)	0.0094 (2)	−0.0019 (2)
Cl2	0.0383 (3)	0.0377 (3)	0.0438 (3)	−0.0001 (2)	0.0123 (2)	0.0029 (2)
O1	0.071 (1)	0.081 (2)	0.040 (1)	−0.000 (1)	0.002 (1)	0.004 (1)
O2	0.060 (1)	0.063 (1)	0.086 (2)	−0.025 (1)	−0.001 (1)	0.009 (1)
O3	0.065 (1)	0.077 (2)	0.050 (1)	0.010 (1)	0.021 (1)	0.003 (1)
O4	0.109 (2)	0.036 (1)	0.128 (2)	0.013 (1)	0.058 (2)	−0.008 (1)
O5	0.061 (1)	0.118 (2)	0.097 (2)	−0.015 (1)	0.033 (1)	−0.055 (2)
O6	0.097 (2)	0.089 (2)	0.062 (1)	0.007 (1)	0.005 (1)	0.028 (1)
O7	0.040 (1)	0.103 (2)	0.125 (2)	−0.007 (1)	0.022 (1)	−0.011 (2)
O8	0.091 (2)	0.041 (1)	0.103 (2)	−0.005 (1)	0.017 (1)	0.017 (1)
O1w	0.051 (1)	0.061 (1)	0.048 (1)	0.004 (1)	0.008 (1)	−0.003 (1)
O2w	0.057 (1)	0.038 (1)	0.056 (1)	0.015 (1)	0.018 (1)	0.007 (1)
N1	0.060 (1)	0.029 (1)	0.043 (1)	−0.008 (1)	0.010 (1)	−0.008 (1)
N2	0.033 (1)	0.023 (1)	0.032 (1)	−0.002 (1)	0.005 (1)	−0.004 (1)
C1	0.035 (1)	0.030 (1)	0.033 (1)	−0.003 (1)	0.003 (1)	−0.003 (1)
C2	0.031 (1)	0.033 (1)	0.041 (1)	0.001 (1)	0.004 (1)	−0.006 (1)
C3	0.042 (1)	0.041 (1)	0.036 (1)	−0.009 (1)	0.013 (1)	−0.008 (1)
C4	0.046 (1)	0.033 (1)	0.033 (1)	−0.009 (1)	0.009 (1)	−0.002 (1)

Geometric parameters (Å, º) top

Cl1—O2	1.413 (2)	O1w—H1w2	0.84 (1)
Cl1—O4	1.416 (2)	O2W—H2W1	0.84 (1)
Cl1—O3	1.428 (2)	O2W—H2W2	0.84 (1)
Cl1—O1	1.440 (2)	N1—H1n1	0.86 (1)
Cl2—O5	1.410 (2)	N1—H1n2	0.85 (1)
Cl2—O7	1.414 (2)	N1—H1n3	0.85 (1)
Cl2—O8	1.420 (2)	N2—H2n	0.85 (1)
Cl2—O6	1.421 (2)	C1—H1a	0.9700
N1—C1	1.486 (3)	C1—H1b	0.9700
N2—C4ⁱ	1.493 (3)	C2—H2a	0.9700
N2—C3	1.503 (3)	C2—H2b	0.9700
N2—C2	1.505 (2)	C3—H3a	0.9700
C1—C2	1.513 (3)	C3—H3b	0.9700
C3—C4	1.510 (3)	C4—H4a	0.9700
C4—N2ⁱ	1.493 (3)	C4—H4b	0.9700
O1w—H1w1	0.84 (1)

O2—Cl1—O4	110.7 (2)	H1n1—N1—H1n3	109 (2)
O2—Cl1—O3	109.8 (2)	H1n2—N1—H1n3	111 (2)
O4—Cl1—O3	108.5 (2)	C4ⁱ—N2—H2n	107 (2)
O2—Cl1—O1	109.3 (1)	C3—N2—H2n	109 (2)
O4—Cl1—O1	110.7 (2)	C2—N2—H2n	109 (2)
O3—Cl1—O1	107.8 (1)	N1—C1—H1a	109.0
O5—Cl2—O7	109.5 (2)	C2—C1—H1a	109.0
O5—Cl2—O8	109.2 (2)	N1—C1—H1b	109.0
O7—Cl2—O8	110.8 (2)	C2—C1—H1b	109.0
O5—Cl2—O6	107.9 (2)	H1a—C1—H1b	107.8
O7—Cl2—O6	111.7 (2)	N2—C2—H2a	108.9
O8—Cl2—O6	107.7 (2)	C1—C2—H2a	108.9
C4ⁱ—N2—C3	108.4 (2)	N2—C2—H2b	108.9
C4ⁱ—N2—C2	113.0 (2)	C1—C2—H2b	108.9
C3—N2—C2	111.1 (2)	H2a—C2—H2b	107.7
N1—C1—C2	113.0 (2)	N2—C3—H3a	109.5
N2—C2—C1	113.5 (2)	C4—C3—H3a	109.5
N2—C3—C4	110.6 (2)	N2—C3—H3b	109.5
N2ⁱ—C4—C3	110.9 (2)	C4—C3—H3b	109.5
H1w1—O1w—H1w2	110 (2)	H3a—C3—H3b	108.1
H2W1—O2W—H2W2	112 (2)	N2ⁱ—C4—H4a	109.5
C1—N1—H1n1	103 (2)	C3—C4—H4a	109.5
C1—N1—H1n2	114 (2)	N2ⁱ—C4—H4b	109.5
H1n1—N1—H1n2	108 (2)	C3—C4—H4b	109.5
C1—N1—H1n3	111 (2)	H4a—C4—H4b	108.0

C4ⁱ—N2—C2—C1	−71.7 (2)	C4ⁱ—N2—C3—C4	58.2 (2)
C3—N2—C2—C1	166.2 (2)	C2—N2—C3—C4	−177.1 (2)
N1—C1—C2—N2	−76.4 (2)	N2—C3—C4—N2ⁱ	−59.7 (2)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O1	0.84 (1)	2.29 (1)	3.113 (3)	167 (3)
O1w—H1w2···O5	0.84 (1)	2.19 (1)	2.990 (3)	160 (3)
O2w—H2w1···O1w	0.84 (1)	1.89 (1)	2.700 (3)	164 (3)
O2w—H2w2···O6ⁱⁱ	0.84 (1)	2.31 (2)	3.030 (3)	144 (3)
N1—H1n1···O1	0.86 (1)	2.06 (1)	2.906 (3)	168 (3)
N1—H1n2···O2wⁱⁱⁱ	0.85 (1)	2.11 (1)	2.905 (3)	155 (2)
N1—H1n3···O1w^iv	0.85 (1)	2.15 (2)	2.838 (3)	138 (2)
N2—H2n···O2wⁱⁱⁱ	0.85 (1)	1.85 (1)	2.695 (2)	175 (2)

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

Experimental details

Crystal data
Chemical formula	C₈H₂₄N₄⁴⁺·4ClO₄⁻·4H₂O
M_r	646.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.862 (1), 19.644 (3), 8.204 (1)
β (°)	103.53 (1)
V (Å³)	1231.9 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7255, 2885, 2449
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.146, 1.05
No. of reflections	2885
No. of parameters	195
No. of restraints	13
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.27

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O1	0.84 (1)	2.29 (1)	3.113 (3)	167 (3)
O1w—H1w2···O5	0.84 (1)	2.19 (1)	2.990 (3)	160 (3)
O2w—H2w1···O1w	0.84 (1)	1.89 (1)	2.700 (3)	164 (3)
O2w—H2w2···O6ⁱ	0.84 (1)	2.31 (2)	3.030 (3)	144 (3)
N1—H1n1···O1	0.86 (1)	2.06 (1)	2.906 (3)	168 (3)
N1—H1n2···O2wⁱⁱ	0.85 (1)	2.11 (1)	2.905 (3)	155 (2)
N1—H1n3···O1wⁱⁱⁱ	0.85 (1)	2.15 (2)	2.838 (3)	138 (2)
N2—H2n···O2wⁱⁱ	0.85 (1)	1.85 (1)	2.695 (2)	175 (2)

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

Comparison of the bond dimensions (Å, °) of the 1,4-bis(2-ammonioethyl)piperazin-1,4-ium cation in the solid-state structure with the PM3-optimized tetracationic structure, and with the PM3-optimized 1,4-bis(2-aminoethyl)piperazine molecule top

Bond	X-ray	PM3-optimized	PM3-optimized
dimension	structure	cation	molecule
N1—C1	1.486 (3)	1.529	1.472
N2—C2	1.505 (2)	1.544	1.492
N2—C3	1.503 (3)	1.537	1.492
N2—C4ⁱ	1.493 (3)	1.533	1.492
C1—C2	1.513 (3)	1.542	1.533
C3—C4	1.510 (3)	1.532	1.526

C4ⁱ—N2—C3	108.4 (2)	107.0	111.4
C4ⁱ—N2—C2	113.0 (2)	112.6	111.8
C3—N2—C2	111.1 (2)	111.0	112.3
N1—C1—C2	113.0 (2)	113.6	111.4
N2—C2—C1	113.5 (2)	113.6	115.6
N2—C3—C4	110.6 (2)	113.0	110.2
N2ⁱ—C4—C3	110.9 (2)	113.0	110.7

Symmetry code for the X-ray structure: (i) −x, −y, −z.

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1,4-Bis(2-ammonio­ethyl)­piperazin-1,4-ium tetraperchlorate tetrahydrate

Supporting information

Key indicators

checkCIF results

1,4-Bis(2-ammonioethyl)piperazin-1,4-ium tetraperchlorate tetrahydrate