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Acta Cryst. (2007). E63, m1919    [ doi:10.1107/S1600536807028152 ]

Hemi(piperazinediium) hexaaquaaluminium(III) bis(sulfate) tetrahydrate: a redetermination at 100 K

M. Ghadermazi, H. Aghabozorg and S. Sheshmani

Abstract top

The reaction of aluminium(III) sulfate with piperazinediium pyridine-2,6-dicarboxylate, (pipzH2)(pydc), where pipz is piperazine and pydcH2 is pyridine-2,6-dicarboxylic acid, in aqueous solution leads to the formation of the title complex, (C4H12N2)1/2[Al(H2O)6](SO4)2·4H2O. The crystal structure of this compound has been published previously [Bataille (2003), Acta Cryst. C59, m459-m461], and our report is a redetermination of the structure at 100 K. As previously observed, intermolecular O-H...O and N-H...O hydrogen bonds result in the formation of a three-dimensional network and a supramolecular structure.

Comment top

In this work, our goal was the generation of the self-assembling coordination compound using a self-assembling ligand. The structure of the Al(III) complex was reported recently (Bataille, 2003), but the goal and method of synthesis were completely different from ours. The data collection temperature in our work was 100 K, whereas, the previous work was conducted at room temperature. For our complex, the final R value was 0.0237, whereas in the reported structure it was 0.0384. In the present study the measured reflections was 4639, while in the earlier work it was 2991.

As previously observed (Bataille, 2003), the structure of (I) consists of Al3+ ions octahedrally coordinated to six water molecules, together with sulfate tetrahedra, piperazinium cations (lying about inversion centres) and non-bonded water molecules, linked by hydrogen bonds only (Fig. 1, Table 1). All the O—H···O and N—H···O hydrogen bonds build up a three dimensionnal network as previously reported (Table 1).

Related literature top

For the crystal structure of the title compound at 293 K, see: Bataille (2003). For related literature, see: Aghabozorg et al. (2006).

Experimental top

A solution of Al2(SO4)3.18H2O (333 mg, 0.5 mmol) in water (10 ml) was added to an aqueous solution of the proton-transfer compound (pipzH2)(pydc) (Aghabozorg et al., 2006) (506 mg, 2 mmol) in water (20 ml). Colorless crystals of (I) were obtained after allowing the mixture to stand for seven weeks at room temperature.

Refinement top

All H atoms were located in difference Fourier maps but they were treated in the refinement as riding on their parent atoms with Uiso(H) = 1.2Ueq(C or N). H or Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. / The asymmetric unit of (I), showing the atom-labelling scheme. Ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. H atoms are represented as small spheres of arbitrary radii.
Hemi(piperazinediium) hexaaquaaluminium(III) bis(sulfate) tetrahydrate top
Crystal data top
(C4H12N2)0.5[Al(H2O)6](SO4)2·4H2OF000 = 936
Mr = 443.34Dx = 1.746 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9176 reflections
a = 6.5438 (3) Åθ = 3.1–33.5º
b = 11.9938 (5) ŵ = 0.46 mm−1
c = 21.4916 (9) ÅT = 100 (2) K
β = 90.164 (1)ºNeedle, colourless
V = 1686.76 (13) Å30.55 × 0.50 × 0.45 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4639 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
Monochromator: graphiteθmax = 30.0º
T = 100(2) Kθmin = 1.9º
ω scansh = −9→9
Absorption correction: nonek = −16→16
21192 measured reflectionsl = −30→30
4847 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.065  w = 1/[σ2(Fo2) + (0.0314P)2 + 0.8179P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max = 0.002
4847 reflectionsΔρmax = 0.45 e Å−3
217 parametersΔρmin = −0.43 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C4H12N2)0.5[Al(H2O)6](SO4)2·4H2OV = 1686.76 (13) Å3
Mr = 443.34Z = 4
Monoclinic, P21/nMo Kα
a = 6.5438 (3) ŵ = 0.46 mm−1
b = 11.9938 (5) ÅT = 100 (2) K
c = 21.4916 (9) Å0.55 × 0.50 × 0.45 mm
β = 90.164 (1)º
Data collection top
Bruker APEXII CCD area-detector
diffractometer		4847 independent reflections
Absorption correction: none4639 reflections with I > 2σ(I)
21192 measured reflectionsRint = 0.017
Refinement top
R[F2 > 2σ(F2)] = 0.024217 parameters
wR(F2) = 0.065H-atom parameters constrained
S = 1.12Δρmax = 0.45 e Å−3
4847 reflectionsΔρmin = −0.43 e Å−3
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 > 2sigma(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
xyzUiso*/Ueq
Al10.46318 (4)0.06332 (2)0.367174 (13)0.00638 (6)
S1−0.04729 (3)−0.026950 (19)0.191802 (10)0.00698 (6)
S2−0.03384 (3)0.191544 (19)0.543172 (10)0.00664 (6)
O110.15644 (11)0.00561 (7)0.21597 (3)0.01263 (14)
O12−0.16492 (11)−0.08210 (6)0.24163 (3)0.01111 (13)
O13−0.15781 (11)0.07318 (6)0.16977 (3)0.01059 (13)
O14−0.02011 (11)−0.10239 (6)0.13764 (3)0.01058 (13)
O210.03790 (11)0.10582 (6)0.58850 (3)0.01070 (13)
O22−0.23346 (11)0.15446 (6)0.51731 (3)0.01083 (13)
O23−0.06166 (12)0.29846 (6)0.57654 (3)0.01124 (14)
O240.11598 (12)0.20524 (6)0.49313 (4)0.01263 (14)
O910.70177 (11)0.13100 (6)0.39764 (3)0.00987 (13)
H110.73810.13660.43960.015*
H120.79110.17360.37190.015*
O920.58088 (11)−0.07843 (6)0.37551 (3)0.00921 (13)
H210.5367−0.13580.34900.014*
H220.7117−0.08980.39040.014*
O930.34321 (11)0.20329 (6)0.35718 (3)0.00985 (13)
H310.41070.27130.35790.015*
H320.20670.21220.34750.015*
O940.22216 (11)−0.00281 (6)0.33634 (3)0.00985 (13)
H410.1923−0.00350.29480.015*
H420.1263−0.03950.36180.015*
O950.56726 (11)0.07184 (6)0.28547 (3)0.00972 (13)
H510.54020.12440.25380.015*
H520.66320.01990.26930.015*
O960.36145 (11)0.05062 (6)0.44869 (3)0.00899 (13)
H610.26610.10140.46370.013*
H620.3291−0.02080.46040.013*
C10.21352 (15)−0.03328 (9)−0.00316 (5)0.01139 (17)
H1A0.3297−0.07640.01400.014*
H1B0.26220.0082−0.04010.014*
N20.13773 (13)0.04702 (7)0.04474 (4)0.01019 (15)
H21N0.24690.09660.05710.012*
H22N0.09290.00360.08080.012*
C30.04290 (15)−0.11226 (8)−0.02208 (5)0.01135 (17)
H3A0.0914−0.1625−0.05550.014*
H3B0.0028−0.15860.01400.014*
O970.46083 (11)0.23332 (6)0.20641 (3)0.01154 (14)
H710.54730.29170.22010.017*
H720.46630.22470.16300.017*
O980.46950 (11)−0.03204 (6)0.13234 (3)0.01213 (14)
H810.3761−0.01780.16450.018*
H820.58710.00820.13940.018*
O99−0.03940 (11)0.25482 (6)0.33251 (3)0.01119 (13)
H91−0.03420.32540.35000.017*
H92−0.04420.26570.28830.017*
O9100.02956 (12)0.26417 (6)0.20367 (4)0.01238 (14)
H1010.17340.25440.20300.019*
H102−0.02460.19500.19150.019*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Al10.00647 (12)0.00660 (13)0.00607 (12)−0.00009 (9)0.00003 (9)0.00003 (9)
S10.00685 (10)0.00767 (10)0.00641 (10)0.00039 (7)0.00017 (7)0.00016 (7)
S20.00686 (10)0.00652 (10)0.00655 (10)0.00020 (7)0.00028 (7)0.00008 (7)
O110.0081 (3)0.0195 (4)0.0103 (3)−0.0020 (3)−0.0016 (2)−0.0005 (3)
O120.0118 (3)0.0117 (3)0.0099 (3)0.0006 (3)0.0035 (2)0.0028 (2)
O130.0119 (3)0.0073 (3)0.0126 (3)0.0018 (2)−0.0009 (2)0.0012 (2)
O140.0139 (3)0.0095 (3)0.0083 (3)0.0017 (3)0.0005 (2)−0.0017 (2)
O210.0089 (3)0.0105 (3)0.0127 (3)0.0008 (2)−0.0013 (2)0.0045 (2)
O220.0099 (3)0.0129 (3)0.0097 (3)−0.0026 (3)−0.0030 (2)0.0013 (3)
O230.0142 (3)0.0085 (3)0.0110 (3)0.0025 (3)−0.0014 (3)−0.0031 (2)
O240.0135 (3)0.0111 (3)0.0133 (3)−0.0001 (3)0.0069 (3)0.0009 (3)
O910.0095 (3)0.0125 (3)0.0076 (3)−0.0034 (2)−0.0011 (2)0.0007 (2)
O920.0087 (3)0.0080 (3)0.0109 (3)0.0013 (2)−0.0018 (2)−0.0008 (2)
O930.0083 (3)0.0070 (3)0.0142 (3)0.0001 (2)−0.0004 (2)0.0008 (2)
O940.0089 (3)0.0126 (3)0.0081 (3)−0.0030 (2)−0.0014 (2)0.0008 (2)
O950.0110 (3)0.0110 (3)0.0071 (3)0.0025 (2)0.0016 (2)0.0014 (2)
O960.0107 (3)0.0081 (3)0.0082 (3)0.0000 (2)0.0017 (2)0.0005 (2)
C10.0094 (4)0.0137 (4)0.0110 (4)0.0004 (3)0.0003 (3)−0.0022 (3)
N20.0103 (4)0.0112 (4)0.0091 (4)−0.0012 (3)−0.0011 (3)−0.0004 (3)
C30.0122 (4)0.0102 (4)0.0117 (4)0.0008 (3)−0.0021 (3)−0.0008 (3)
O970.0146 (3)0.0111 (3)0.0089 (3)−0.0003 (3)−0.0001 (2)0.0011 (2)
O980.0106 (3)0.0126 (3)0.0131 (3)−0.0005 (3)0.0006 (3)0.0000 (3)
O990.0110 (3)0.0104 (3)0.0122 (3)0.0001 (3)0.0002 (2)0.0014 (3)
O9100.0129 (3)0.0086 (3)0.0156 (3)−0.0001 (3)−0.0009 (3)0.0006 (3)
Geometric parameters (Å, °) top
Al1—O931.8654 (8)O95—H510.9440
Al1—O921.8748 (8)O95—H520.9504
Al1—O911.8760 (8)O96—H610.9304
Al1—O961.8820 (8)O96—H620.9177
Al1—O941.8841 (8)C1—N21.4954 (13)
Al1—O951.8880 (8)C1—C31.5187 (14)
S1—O121.4770 (7)C1—H1A0.9900
S1—O131.4791 (7)C1—H1B0.9900
S1—O111.4818 (7)N2—C3i1.4977 (13)
S1—O141.4854 (7)N2—H21N0.9666
S2—O241.4666 (7)N2—H22N0.9802
S2—O231.4808 (7)C3—N2i1.4977 (13)
S2—O221.4862 (7)C3—H3A0.9900
S2—O211.4913 (7)C3—H3B0.9900
O91—H110.9343O97—H710.9466
O91—H120.9543O97—H720.9395
O92—H210.9386O98—H810.9403
O92—H220.9229O98—H820.9208
O93—H310.9273O99—H910.9268
O93—H320.9227O99—H920.9595
O94—H410.9126O910—H1010.9484
O94—H420.9433O910—H1020.9390
O93—Al1—O92178.68 (4)Al1—O93—H32122.5
O93—Al1—O9190.02 (3)H31—O93—H32111.3
O92—Al1—O9191.02 (3)Al1—O94—H41121.6
O93—Al1—O9691.73 (3)Al1—O94—H42123.3
O92—Al1—O9689.08 (3)H41—O94—H42115.0
O91—Al1—O9690.36 (3)Al1—O95—H51129.7
O93—Al1—O9489.24 (3)Al1—O95—H52123.0
O92—Al1—O9489.72 (3)H51—O95—H52107.3
O91—Al1—O94179.26 (4)Al1—O96—H61120.6
O96—Al1—O9489.73 (3)Al1—O96—H62114.4
O93—Al1—O9589.83 (3)H61—O96—H62111.1
O92—Al1—O9589.36 (3)N2—C1—C3109.93 (8)
O91—Al1—O9589.95 (3)N2—C1—H1A109.7
O96—Al1—O95178.41 (4)C3—C1—H1A109.7
O94—Al1—O9589.97 (3)N2—C1—H1B109.7
O12—S1—O13109.90 (4)C3—C1—H1B109.7
O12—S1—O11109.52 (4)H1A—C1—H1B108.2
O13—S1—O11109.68 (5)C1—N2—C3i112.06 (7)
O12—S1—O14111.05 (4)C1—N2—H21N109.9
O13—S1—O14107.65 (4)C3i—N2—H21N110.5
O11—S1—O14109.00 (4)C1—N2—H22N107.7
O24—S2—O23109.97 (5)C3i—N2—H22N107.3
O24—S2—O22110.36 (4)H21N—N2—H22N109.3
O23—S2—O22109.34 (4)N2i—C3—C1109.88 (8)
O24—S2—O21110.27 (4)N2i—C3—H3A109.7
O23—S2—O21108.64 (4)C1—C3—H3A109.7
O22—S2—O21108.22 (4)N2i—C3—H3B109.7
Al1—O91—H11125.3C1—C3—H3B109.7
Al1—O91—H12122.7H3A—C3—H3B108.2
H11—O91—H12111.5H71—O97—H72111.4
Al1—O92—H21118.7H81—O98—H82109.1
Al1—O92—H22123.2H91—O99—H92106.2
H21—O92—H22112.7H101—O910—H102105.1
Al1—O93—H31126.1
Symmetry codes: (i) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O91—H11···O22ii0.931.692.6205 (10)171
O91—H12···O99ii0.951.702.6546 (10)174
O92—H21···O910iii0.941.702.6411 (10)175
O92—H22···O21iv0.921.712.6302 (10)175
O93—H31···O14v0.931.682.6046 (10)176
O93—H32···O990.921.722.6313 (10)169
O94—H41···O110.911.712.6232 (10)174
O94—H42···O21vi0.941.712.6547 (10)177
O95—H51···O970.941.742.6677 (10)169
O95—H52···O12ii0.951.772.7161 (10)177
O96—H61···O240.931.712.6345 (10)173
O96—H62···O22vi0.921.792.6997 (10)173
N2—H21N···O23vii0.971.822.7864 (11)174
N2—H22N···O140.981.912.8769 (11)167
O97—H71···O12v0.951.892.8149 (10)166
O97—H72···O23vii0.941.892.8203 (10)172
O98—H81···O110.941.842.7663 (10)169
O98—H82···O13ii0.921.952.8594 (11)168
O99—H91···O98v0.931.802.7042 (11)164
O99—H92···O9100.961.882.8091 (11)161
O910—H101···O970.951.902.8468 (11)177
O910—H102···O130.941.762.6974 (10)173
Symmetry codes: (ii) x+1, y, z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1, −y, −z+1; (v) −x+1/2, y+1/2, −z+1/2; (vi) −x, −y, −z+1; (vii) x+1/2, −y+1/2, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O91—H11···O22i0.931.692.6205 (10)171
O91—H12···O99i0.951.702.6546 (10)174
O92—H21···O910ii0.941.702.6411 (10)175
O92—H22···O21iii0.921.712.6302 (10)175
O93—H31···O14iv0.931.682.6046 (10)176
O93—H32···O990.921.722.6313 (10)169
O94—H41···O110.911.712.6232 (10)174
O94—H42···O21v0.941.712.6547 (10)177
O95—H51···O970.941.742.6677 (10)169
O95—H52···O12i0.951.772.7161 (10)177
O96—H61···O240.931.712.6345 (10)173
O96—H62···O22v0.921.792.6997 (10)173
N2—H21N···O23vi0.971.822.7864 (11)174
N2—H22N···O140.981.912.8769 (11)167
O97—H71···O12iv0.951.892.8149 (10)166
O97—H72···O23vi0.941.892.8203 (10)172
O98—H81···O110.941.842.7663 (10)169
O98—H82···O13i0.921.952.8594 (11)168
O99—H91···O98iv0.931.802.7042 (11)164
O99—H92···O9100.961.882.8091 (11)161
O910—H101···O970.951.902.8468 (11)177
O910—H102···O130.941.762.6974 (10)173
Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1, −y, −z+1; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x, −y, −z+1; (vi) x+1/2, −y+1/2, z−1/2.
Acknowledgements top

The authors are grateful to Islamic Azad University, Shahr-e Rey Branch, for financial support of this work. The Teacher Training University is also gratefully acknowledged.

references
References top

Aghabozorg, H., Ghadermazi, M., Manteghi, F. & Nakhjavan, B. (2006). Z. Anorg. Allg. Chem. 632, 2058–2064.

Bataille, T. (2003). Acta Cryst. C59, m459–m461.

Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Sheldrick, G. M. (1998). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.