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.
Supporting information
CCDC reference: 197475
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
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.
The nitrogen-bound and water H atoms were located and refined, subject to N—H = 0.85±0.01 Å and O—H = 0.84±0.01 Å, respectively. The H atoms attached the C atoms were generated geometrically and were allowed to ride on their parent C atoms, with Uiso(H) = 1.2Ueq(C). Water H atoms were refined
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.
1,4-Bis(2-ammonioethyl)piperazin-1,4-ium tetraperchlorate tetrahydrate
top
Crystal data top
C8H24N44+·4ClO4−·4H2O | F(000) = 672 |
Mr = 646.18 | Dx = 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 | Rint = 0.029 |
Graphite monochromator | θmax = 28.0°, θmin = 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(Fo2) + (0.0965P)2 + 0.3123P] where P = (Fo2 + 2Fc2)/3 |
2885 reflections | (Δ/σ)max < 0.001 |
195 parameters | Δρmax = 0.75 e Å−3 |
13 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
C8H24N44+·4ClO4−·4H2O | V = 1231.9 (3) Å3 |
Mr = 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 | Rint = 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 | Δρmax = 0.75 e Å−3 |
2885 reflections | Δρmin = −0.27 e Å−3 |
195 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
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···O1wiv | 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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.75, −0.27 |
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 topBond | 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. |
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 [Nammonio···O = 2.695 (2) Å and Npiperazinium···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.