Common features in the crystal structures of [Al(H2O)6](SO4)NO3·2H2O and [Al(H2O)6](SO4)Cl·H2O are [Al(H2O)6]3+ octahedra and sulfate tetrahedra. These components, the remaining anion (NO3 − and Cl−, respectively) and lattice water molecules are separated from each other. Interactions are mediated via medium–strong hydrogen bonding.
Keywords: crystal structure, aluminium, double salt, hydrogen bonding
Abstract
Two novel aluminium double salts, [Al(H2O)6](SO4)NO3·2H2O, hexaquaaluminium sulfate nitrate dihydrate, (1), and [Al(H2O)6](SO4)Cl·H2O, hexaquaaluminium sulfate chloride hydrate, (2), were obtained in the form of single crystals. Their crystal structures are each based on an octahedral [Al(H2O)6]3+ unit and both structures have in common one charge-balancing SO4 2− anion. The final positive charge from the aluminium(III) cation is balanced by an NO3 − or a Cl− anion for (1) and (2), respectively. Compound (1) further contains two unligated water molecules while compound (2) only contains one unligated water molecule. In the crystal structures, all components are spatially separated and interactions are mediated via medium–strong hydrogen bonding, compared to many other reported aluminium sulfates where corner-sharing of the building units is common. The two compounds represent rare cases where one aluminium(III) cation is charge-balanced by two different anions.
Chemical context
Aluminium is one of the most common elements in Earth’s crust and is predominantly found in oxides and silicates. The far most common oxidation state for inorganic compounds is +III. Aluminium is found in many double salts with numerous other cations and sulfate, such as the industrially important alums MAl(SO4)2·12H2O (M = monovalent cation; Greenwood & Earnshaw, 1997 ▸). At low pH, aluminium mainly exists in solution as the [Al(H2O)6]3+ cation (Hay & Myneni, 2008 ▸).
One of the title compounds, [Al(H2O)6](SO4)NO3·2H2O, (1), was obtained as an unintentional side product when attempting to synthesize an aluminium-modified bismuth-titanium oxo-complex. Efforts to obtain (1) by other routes resulted in the formation of [Al(H2O)6]SO4Cl·H2O (2).
Structural commentary
The crystal structure of (1) comprises an [Al(H2O)6]3+ cation charge-balanced by one sulfate and one nitrate anion as well as two unligated water molecules; all building units are separated from each other (Fig. 1 ▸). Bond lengths in the components are summarized in Table 1 ▸. The aqua ligands (O1–O6) of the complex cations serve as hydrogen-bonding donor groups. They connect through O—H⋯O hydrogen bonds to the two types of anions and to the two unbound water molecules, forming a three-dimensional network (Fig. 2 ▸, Table 2 ▸). Hydrogen bonds involving H8 and H12 are bifurcated. The water molecules OW1 and OW2 likewise serve as donor groups, whereby OW1 hydrogen-bonds to the nitrate anion (O12, O13) and to the second water molecule OW2. The latter hydrogen bond involving H14 is also bifurcated. Interestingly, OW2 shows only one hydrogen bond to a nitrate anion (H16⋯O12); the second H atom (H15) is not engaged in hydrogen-bonding. The H⋯O distances involving the [Al(H2O)6]3+ group are between 1.76 (3) and 2.35 (3) Å and thus can be considered as medium–strong whereas the H⋯O distances [2.05 (2) to 2.55 (3) Å] involving the unbound water molecules as donor groups indicate much weaker hydrogen bonds.
Figure 1.
The asymmetric unit of (1), representing the building units. Displacement ellipsoids are drawn at the 50% probability level.
Table 1. Selected bond lengths (Å) for (1).
| Al1—O6 | 1.869 (2) | S1—O10 | 1.466 (2) |
| Al1—O5 | 1.872 (2) | S1—O7 | 1.470 (2) |
| Al1—O2 | 1.876 (2) | S1—O9 | 1.479 (2) |
| Al1—O3 | 1.880 (2) | N1—O12 | 1.209 (4) |
| Al1—O1 | 1.880 (2) | N1—O11 | 1.225 (4) |
| Al1—O4 | 1.887 (2) | N1—O13 | 1.232 (4) |
| S1—O8 | 1.464 (2) |
Figure 2.
Packing in the crystal structure of compound (1). Hydrogen bonding is indicated by dotted lines.
Table 2. Hydrogen-bond geometry (Å, °) for (1).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O1—H1⋯O10 | 0.85 (1) | 1.78 (1) | 2.627 (3) | 173 (4) |
| O1—H2⋯O7i | 0.85 (1) | 1.85 (1) | 2.689 (3) | 171 (4) |
| O2—H3⋯O8ii | 0.85 (1) | 1.84 (1) | 2.684 (3) | 176 (4) |
| O2—H4⋯OW1 | 0.85 (1) | 1.76 (1) | 2.600 (3) | 171 (4) |
| O3—H5⋯O7iii | 0.85 (1) | 1.83 (1) | 2.675 (3) | 178 (4) |
| O3—H6⋯O9i | 0.85 (1) | 1.83 (1) | 2.670 (3) | 169 (4) |
| O4—H7⋯O8iv | 0.85 (1) | 1.91 (1) | 2.745 (3) | 168 (4) |
| O4—H8⋯O11v | 0.85 (1) | 2.12 (2) | 2.884 (4) | 150 (4) |
| O4—H8⋯O13v | 0.85 (1) | 2.13 (3) | 2.870 (4) | 147 (4) |
| O5—H9⋯O9vi | 0.85 (1) | 1.80 (1) | 2.650 (3) | 179 (4) |
| O5—H10⋯O10iv | 0.85 (1) | 1.79 (1) | 2.640 (3) | 175 (4) |
| O6—H11⋯OW2 | 0.85 (1) | 1.79 (2) | 2.596 (4) | 160 (4) |
| O6—H12⋯O11vii | 0.85 (1) | 2.35 (3) | 3.044 (4) | 139 (3) |
| O6—H12⋯O12vii | 0.85 (1) | 2.06 (2) | 2.876 (4) | 162 (4) |
| OW1—H13⋯O13 | 0.86 (1) | 2.05 (2) | 2.850 (5) | 155 (3) |
| OW1—H14⋯O12vii | 0.86 (1) | 2.52 (4) | 3.109 (5) | 127 (4) |
| OW1—H14⋯OW2viii | 0.86 (1) | 2.55 (4) | 3.073 (6) | 120 (3) |
| OW2—H16⋯O12viii | 0.86 (1) | 2.20 (3) | 2.908 (5) | 139 (3) |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
; (vi) 
; (vii) 
; (viii) 
.
In the crystal structure of compound (2), the charge-balancing nitrate anion of (1) is exchanged for a chloride anion, and the formula unit only contains one additional water molecule (Fig. 3 ▸). Table 3 ▸ collates bond lengths of the individual building units. The [Al(H2O)6]3+ cation donates hydrogen bonds through the aqua ligands (O1– O6) to the sulfate group, the unligated water molecule and to the chloride anion, resulting in a three-dimensional network (Fig. 4 ▸, Table 4 ▸). Each sulfate group is hydrogen-bonded to four different [Al(H2O)6]3+ cations, and the unbound water molecule exclusively hydrogen-bonds to the chloride anions, partly with a bifurcated bond. The O⋯H distances vary between 1.726 (11) and 1.917 (11) Å and thus are slightly stronger than in (1).
Figure 3.
The asymmetric unit of (2), representing the building units. Displacement ellipsoids are drawn at the 50% probability level.
Table 3. Selected bond lengths (Å) for (2).
| Al1—O3 | 1.8624 (17) | Al1—O2 | 1.8940 (17) |
| Al1—O5 | 1.8718 (18) | S1—O10 | 1.4670 (16) |
| Al1—O6 | 1.8752 (17) | S1—O9 | 1.4672 (16) |
| Al1—O1 | 1.8798 (17) | S1—O8 | 1.4753 (16) |
| Al1—O4 | 1.8855 (17) | S1—O7 | 1.4767 (16) |
Figure 4.
Packing in the crystal structure of compound (2). Hydrogen bonding is indicated by dotted lines.
Table 4. Hydrogen-bond geometry (Å, °) for (2).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O1—H1⋯O9i | 0.85 (1) | 1.88 (1) | 2.714 (2) | 165 (3) |
| O1—H2⋯O8ii | 0.85 (1) | 1.85 (1) | 2.690 (2) | 170 (3) |
| O2—H3⋯OW1iii | 0.85 (1) | 1.85 (1) | 2.692 (2) | 178 (3) |
| O2—H4⋯O10 | 0.85 (1) | 1.92 (1) | 2.767 (2) | 177 (3) |
| O3—H5⋯O7iv | 0.85 (1) | 1.78 (1) | 2.629 (2) | 174 (3) |
| O3—H6⋯O7 | 0.85 (1) | 1.73 (1) | 2.578 (2) | 176 (3) |
| O4—H7⋯Cl1v | 0.85 (1) | 2.18 (1) | 3.0311 (18) | 177 (3) |
| O4—H8⋯O10vi | 0.85 (1) | 1.83 (1) | 2.669 (2) | 176 (3) |
| O5—H9⋯OW1 | 0.85 (1) | 1.82 (1) | 2.650 (2) | 166 (3) |
| O5—H10⋯Cl1 | 0.85 (1) | 2.17 (1) | 3.0120 (18) | 171 (3) |
| O6—H11⋯O8vii | 0.85 (1) | 1.83 (1) | 2.672 (2) | 172 (3) |
| O6—H12⋯O9ii | 0.85 (1) | 1.83 (1) | 2.671 (2) | 171 (3) |
| OW1—H13⋯Cl1viii | 0.85 (1) | 2.33 (2) | 3.083 (2) | 149 (3) |
| OW1—H14⋯Cl1i | 0.84 (1) | 2.68 (2) | 3.390 (2) | 143 (3) |
| OW1—H14⋯Cl1iii | 0.84 (1) | 2.74 (3) | 3.280 (2) | 123 (3) |
Symmetry codes: (i) 
; (ii) 
; (iii) 
; (iv) 
; (v) 
; (vi) 
; (vii) 
; (viii) 
.
According to the Pearson concept, sulfate, nitrate, and chloride are all considered intermediate hard bases while Al3+ is a hard acid. The higher charge (2+) of the sulfate group compared to the nitrate group and chloride is a likely reason that the sulfate group is present in both structures while the two latter ones can be interchanged, possibly related to their relative abundance. The chloride ions in the reaction mixture of (1) might also have been bonded to the titanium(IV) and bismuth(III) cations, preventing the formation of (2). In particular Bi3+ tends to form insoluble BiOCl. Furthermore, (1) contains two extra water molecules while (2) only contains one of them. The average Al—O bond lengths are 1.880 and 1.884 Å for (1) and (2), respectively, which is slightly shorter than the literature average distance of 1.90 Å (Hay & Myneni, 2008 ▸; Veillard, 1977 ▸).
Structures of aluminium sulfate, Al2(SO4)3, and derivatives thereof have been reported with different amounts of additional structural water and varying connectivities. Sabelli & Ferroni (1978 ▸) reported an aluminium sulfate structure (Al2(OH)4SO4·7H2O) where six hydrated aluminum(III) ions are connected via edge- and face sharing. These aluminum ‘hexamers’ are linked via hydrogen bonding with unligated water and sulfate ions. In the crystal structure of Al2(SO4)3·8H2O, hydrated aluminum(III) ions are connected via corner sharing with sulfate groups and a rather extensive hydrogen-bond network between sulfate, aqua ligands, and unligated, structural water molecules (Fischer et al., 1996 ▸). In the Al(SO4)OH structure reported by Anderson et al. (2015 ▸), each sulfate group connects three different aluminium(III) ions via corner sharing. The structures of the two reported compounds herein are more open and the principal building units are only connected via hydrogen bonding, which may be due to the presence of another anion (NO3 −/Cl−).
Database survey
According to a database survey using the Inorganic Crystal Structure Database (ICSD), aluminium compounds with an additional cation charge-balanced by sulfate anions appear to be common [e.g. KAl(SO4)2, FeAl(SO4)3 (Demartin et al., 2010 ▸), or CsAl(SO4)2 (Beattie et al., 1981 ▸)]. However, compounds with aluminium as the single cation but with two different anions were found to be much less common although examples include Al(H2PO4)2F (Parnham & Morris, 2006 ▸) or Al(SO4)OH (Anderson et al., 2015 ▸).
Synthesis and crystallization
Compound (1) was obtained by mixing equimolar solutions of TiOSO4 (Aldrich) and Bi(NO3)3·5H2O (Aldrich), both dissolved in 1 M nitric acid (Sigma–Aldrich), and two equivalents of AlCl3·6H2O (Mallinckrodt Chemical Works) dissolved in 1 M hydrochloric acid (Sigma–Aldrich). Colorless needle-shaped crystals formed on a glass substrate after about a week of slow evaporation of the solvent at room temperature. Elemental analysis by energy-dispersive X-ray spectroscopy using a Hitachi TM-1000 scanning electron microscope with an Oxford Instruments EDS system revealed a molar Al:S ratio of 1.37 (expected 1:1). In an attempt to synthesize compound (1) by a direct route, aluminium(III) chloride was changed to aluminium(III) lactate to avoid chloride ions. This resulted in formation of crystals with very poor quality that were not suitable for X-ray diffraction.
Compound (2) was obtained by dissolving 1 M AlCl3·6H2O in 1 ml of 1 M hydrochloric acid and adding one equivalent of 1 M sulfuric acid (Sigma–Aldrich), or making a 1 M AlCl3·6H2O solution in 0.5 ml of 1 M H2SO2 plus 0.5 ml of 1 M HNO3. The solution was poured into a Petri dish and left for slow evaporation. After a few days of evaporation of the solvent, colorless block-shaped crystals suitable for single X-ray crystal diffraction were obtained. The crystals were somewhat fragile. EDS analysis of (2) revealed an S:Al:Cl molar composition of 0.9:0.9:1.17 (expected 1:1:1).
For the data collection, both types of crystals were mounted on a glass needle and protected by a layer of paraffin oil.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 5 ▸. In each of the two structures, all hydrogen atoms were discernible in difference-Fourier maps. They were refined with O—H distance restraints of 0.85 (1) Å and a common U iso(H) parameter. Reasonable geometries for the unligated water water molecules were ensured by using restrained H⋯H distances of 1.55 (1) Å.
Table 5. Experimental details.
| (1) | (2) | |
|---|---|---|
| Crystal data | ||
| Chemical formula | [Al(H2O)6](NO3)(SO4)·2H2O | [Al(H2O)6]Cl(SO4)·H2O |
| M r | 329.18 | 284.60 |
| Crystal system, space group | Triclinic, P
|
Monoclinic, P21/c |
| Temperature (K) | 296 | 296 |
| a, b, c (Å) | 6.088 (4), 7.377 (5), 13.721 (9) | 6.1640 (14), 22.933 (5), 7.2876 (14) |
| α, β, γ (°) | 77.340 (6), 89.561 (7), 82.712 (7) | 90, 97.328 (2), 90 |
| V (Å3) | 596.3 (7) | 1021.8 (4) |
| Z | 2 | 4 |
| Radiation type | Mo Kα | Mo Kα |
| μ (mm−1) | 0.43 | 0.71 |
| Crystal size (mm) | 0.20 × 0.02 × 0.02 | 0.20 × 0.10 × 0.10 |
| Data collection | ||
| Diffractometer | Bruker APEXII CCD | Bruker APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Bruker, 2015 ▸) | Multi-scan (SADABS; Bruker, 2015 ▸) |
| T min, T max | 0.919, 0.992 | 0.872, 0.933 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 4506, 1642, 1519 | 8454, 1457, 1304 |
| R int | 0.026 | 0.044 |
| θmax (°) | 23.4 | 23.3 |
| (sin θ/λ)max (Å−1) | 0.559 | 0.556 |
| Refinement | ||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.034, 0.090, 1.10 | 0.024, 0.064, 1.03 |
| No. of reflections | 1642 | 1457 |
| No. of parameters | 213 | 170 |
| No. of restraints | 97 | 14 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.50, −0.38 | 0.20, −0.29 |
Supplementary Material
Crystal structure: contains datablock(s) global, 1, 2. DOI: 10.1107/S2056989020015741/wm5585sup1.cif
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
Professor Vadim Kessler is acknowledged for valuable discussions.
supplementary crystallographic information
Hexaquaaluminium sulfate nitrate dihydrate (1). Crystal data
| [Al(H2O)6](NO3)(SO4)·2H2O | Z = 2 |
| Mr = 329.18 | F(000) = 344 |
| triclinic, P1 | Dx = 1.833 Mg m−3 |
| a = 6.088 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 7.377 (5) Å | Cell parameters from 3914 reflections |
| c = 13.721 (9) Å | θ = 2.9–23.4° |
| α = 77.340 (6)° | µ = 0.43 mm−1 |
| β = 89.561 (7)° | T = 296 K |
| γ = 82.712 (7)° | Needle, colorless |
| V = 596.3 (7) Å3 | 0.20 × 0.02 × 0.02 mm |
Hexaquaaluminium sulfate nitrate dihydrate (1). Data collection
| Bruker APEXII CCD diffractometer | 1642 independent reflections |
| Radiation source: fine-focus sealed tube | 1519 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.026 |
| φ and ω scans | θmax = 23.4°, θmin = 2.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −6→6 |
| Tmin = 0.919, Tmax = 0.992 | k = −8→8 |
| 4506 measured reflections | l = −15→15 |
Hexaquaaluminium sulfate nitrate dihydrate (1). Refinement
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0404P)2 + 0.6205P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max < 0.001 |
| 1642 reflections | Δρmax = 0.50 e Å−3 |
| 213 parameters | Δρmin = −0.38 e Å−3 |
| 97 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.021 (4) |
Hexaquaaluminium sulfate nitrate dihydrate (1). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Al1 | 0.49771 (11) | −0.14486 (9) | 0.30419 (5) | 0.0196 (2) | |
| S1 | 1.01766 (9) | −0.31760 (8) | 0.62701 (4) | 0.0206 (2) | |
| O1 | 0.7790 (3) | −0.2120 (2) | 0.36672 (13) | 0.0244 (4) | |
| O2 | 0.5436 (3) | 0.1080 (2) | 0.27387 (14) | 0.0283 (4) | |
| O3 | 0.4467 (3) | −0.3969 (2) | 0.33515 (14) | 0.0290 (5) | |
| O4 | 0.2144 (3) | −0.0792 (3) | 0.24229 (14) | 0.0286 (4) | |
| O5 | 0.3748 (3) | −0.1058 (2) | 0.42456 (13) | 0.0270 (4) | |
| O6 | 0.6292 (3) | −0.1776 (3) | 0.18465 (14) | 0.0316 (5) | |
| O7 | 0.9553 (3) | −0.4996 (2) | 0.67900 (14) | 0.0288 (4) | |
| O8 | 1.0542 (3) | −0.2042 (3) | 0.69915 (14) | 0.0315 (5) | |
| O9 | 1.2243 (3) | −0.3510 (2) | 0.57270 (14) | 0.0322 (5) | |
| O10 | 0.8384 (3) | −0.2193 (3) | 0.55706 (14) | 0.0353 (5) | |
| N1 | 0.2189 (5) | 0.8543 (4) | 0.0100 (2) | 0.0446 (7) | |
| O11 | 0.2452 (5) | 1.0059 (4) | 0.0276 (2) | 0.0725 (8) | |
| O12 | 0.2331 (6) | 0.8332 (5) | −0.0748 (2) | 0.0901 (10) | |
| O13 | 0.1767 (6) | 0.7326 (4) | 0.0821 (2) | 0.0823 (9) | |
| OW1 | 0.3034 (5) | 0.3374 (4) | 0.1321 (2) | 0.0754 (8) | |
| OW2 | 0.7579 (7) | −0.4488 (6) | 0.0962 (4) | 0.1134 (14) | |
| H1 | 0.809 (7) | −0.220 (6) | 0.4280 (11) | 0.069 (3)* | |
| H2 | 0.867 (6) | −0.294 (4) | 0.347 (3) | 0.069 (3)* | |
| H3 | 0.672 (3) | 0.139 (6) | 0.279 (3) | 0.069 (3)* | |
| H4 | 0.478 (6) | 0.187 (4) | 0.225 (2) | 0.069 (3)* | |
| H5 | 0.320 (3) | −0.432 (6) | 0.332 (3) | 0.069 (3)* | |
| H6 | 0.540 (5) | −0.487 (4) | 0.364 (3) | 0.069 (3)* | |
| H7 | 0.117 (5) | 0.004 (4) | 0.256 (3) | 0.069 (3)* | |
| H8 | 0.193 (7) | −0.087 (6) | 0.1826 (13) | 0.069 (3)* | |
| H9 | 0.327 (7) | −0.183 (5) | 0.473 (2) | 0.069 (3)* | |
| H10 | 0.313 (6) | 0.001 (3) | 0.431 (3) | 0.069 (3)* | |
| H11 | 0.648 (7) | −0.279 (3) | 0.164 (3) | 0.069 (3)* | |
| H12 | 0.657 (7) | −0.083 (4) | 0.141 (2) | 0.069 (3)* | |
| H13 | 0.265 (7) | 0.451 (2) | 0.137 (3) | 0.069 (3)* | |
| H14 | 0.367 (7) | 0.298 (4) | 0.083 (2) | 0.069 (3)* | |
| H15 | 0.616 (2) | −0.421 (5) | 0.091 (3) | 0.069 (3)* | |
| H16 | 0.831 (5) | −0.555 (3) | 0.092 (3) | 0.069 (3)* |
Hexaquaaluminium sulfate nitrate dihydrate (1). Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Al1 | 0.0169 (4) | 0.0196 (4) | 0.0222 (4) | −0.0027 (3) | −0.0003 (3) | −0.0041 (3) |
| S1 | 0.0178 (4) | 0.0187 (4) | 0.0248 (4) | −0.0008 (2) | −0.0005 (2) | −0.0046 (2) |
| O1 | 0.0199 (9) | 0.0249 (9) | 0.0279 (10) | 0.0008 (7) | −0.0036 (7) | −0.0068 (8) |
| O2 | 0.0250 (10) | 0.0236 (10) | 0.0349 (11) | −0.0063 (8) | −0.0027 (8) | −0.0011 (8) |
| O3 | 0.0202 (9) | 0.0205 (10) | 0.0453 (12) | −0.0043 (7) | −0.0014 (8) | −0.0040 (8) |
| O4 | 0.0209 (9) | 0.0333 (11) | 0.0323 (10) | 0.0002 (8) | −0.0040 (8) | −0.0106 (8) |
| O5 | 0.0313 (10) | 0.0220 (10) | 0.0255 (10) | 0.0014 (8) | 0.0054 (8) | −0.0032 (7) |
| O6 | 0.0321 (10) | 0.0358 (11) | 0.0268 (10) | −0.0035 (9) | 0.0052 (8) | −0.0075 (8) |
| O7 | 0.0229 (9) | 0.0220 (9) | 0.0406 (11) | −0.0050 (7) | 0.0033 (8) | −0.0039 (8) |
| O8 | 0.0263 (9) | 0.0310 (10) | 0.0411 (11) | −0.0042 (8) | −0.0033 (8) | −0.0158 (8) |
| O9 | 0.0282 (10) | 0.0257 (10) | 0.0373 (11) | 0.0021 (8) | 0.0103 (8) | 0.0012 (8) |
| O10 | 0.0368 (11) | 0.0348 (11) | 0.0313 (10) | 0.0134 (8) | −0.0101 (8) | −0.0107 (8) |
| N1 | 0.0476 (15) | 0.0430 (16) | 0.0396 (16) | 0.0011 (12) | 0.0073 (12) | −0.0053 (12) |
| O11 | 0.0610 (16) | 0.0542 (16) | 0.103 (2) | −0.0068 (13) | −0.0250 (15) | −0.0186 (15) |
| O12 | 0.126 (3) | 0.100 (2) | 0.0455 (16) | 0.008 (2) | 0.0206 (16) | −0.0325 (16) |
| O13 | 0.098 (2) | 0.0772 (19) | 0.0586 (17) | −0.0316 (17) | −0.0027 (15) | 0.0257 (15) |
| OW1 | 0.085 (2) | 0.0536 (16) | 0.0713 (19) | 0.0160 (15) | −0.0088 (16) | 0.0071 (14) |
| OW2 | 0.092 (3) | 0.107 (3) | 0.171 (4) | −0.005 (2) | 0.016 (3) | −0.101 (3) |
Hexaquaaluminium sulfate nitrate dihydrate (1). Geometric parameters (Å, º)
| Al1—O6 | 1.869 (2) | S1—O10 | 1.466 (2) |
| Al1—O5 | 1.872 (2) | S1—O7 | 1.470 (2) |
| Al1—O2 | 1.876 (2) | S1—O9 | 1.479 (2) |
| Al1—O3 | 1.880 (2) | N1—O12 | 1.209 (4) |
| Al1—O1 | 1.880 (2) | N1—O11 | 1.225 (4) |
| Al1—O4 | 1.887 (2) | N1—O13 | 1.232 (4) |
| S1—O8 | 1.464 (2) | ||
| O6—Al1—O5 | 177.66 (9) | O2—Al1—O4 | 90.05 (8) |
| O6—Al1—O2 | 90.30 (9) | O3—Al1—O4 | 89.21 (8) |
| O5—Al1—O2 | 87.90 (8) | O1—Al1—O4 | 179.48 (9) |
| O6—Al1—O3 | 90.38 (9) | O8—S1—O10 | 109.31 (11) |
| O5—Al1—O3 | 91.45 (9) | O8—S1—O7 | 110.17 (12) |
| O2—Al1—O3 | 179.02 (8) | O10—S1—O7 | 108.97 (12) |
| O6—Al1—O1 | 88.42 (9) | O8—S1—O9 | 109.41 (12) |
| O5—Al1—O1 | 90.10 (9) | O10—S1—O9 | 110.42 (12) |
| O2—Al1—O1 | 90.37 (8) | O7—S1—O9 | 108.55 (11) |
| O3—Al1—O1 | 90.36 (8) | O12—N1—O11 | 119.5 (3) |
| O6—Al1—O4 | 91.88 (9) | O12—N1—O13 | 124.4 (3) |
| O5—Al1—O4 | 89.61 (9) | O11—N1—O13 | 116.2 (3) |
Hexaquaaluminium sulfate nitrate dihydrate (1). Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O10 | 0.85 (1) | 1.78 (1) | 2.627 (3) | 173 (4) |
| O1—H2···O7i | 0.85 (1) | 1.85 (1) | 2.689 (3) | 171 (4) |
| O2—H3···O8ii | 0.85 (1) | 1.84 (1) | 2.684 (3) | 176 (4) |
| O2—H4···OW1 | 0.85 (1) | 1.76 (1) | 2.600 (3) | 171 (4) |
| O3—H5···O7iii | 0.85 (1) | 1.83 (1) | 2.675 (3) | 178 (4) |
| O3—H6···O9i | 0.85 (1) | 1.83 (1) | 2.670 (3) | 169 (4) |
| O4—H7···O8iv | 0.85 (1) | 1.91 (1) | 2.745 (3) | 168 (4) |
| O4—H8···O11v | 0.85 (1) | 2.12 (2) | 2.884 (4) | 150 (4) |
| O4—H8···O13v | 0.85 (1) | 2.13 (3) | 2.870 (4) | 147 (4) |
| O5—H9···O9vi | 0.85 (1) | 1.80 (1) | 2.650 (3) | 179 (4) |
| O5—H10···O10iv | 0.85 (1) | 1.79 (1) | 2.640 (3) | 175 (4) |
| O6—H11···OW2 | 0.85 (1) | 1.79 (2) | 2.596 (4) | 160 (4) |
| O6—H12···O11vii | 0.85 (1) | 2.35 (3) | 3.044 (4) | 139 (3) |
| O6—H12···O12vii | 0.85 (1) | 2.06 (2) | 2.876 (4) | 162 (4) |
| OW1—H13···O13 | 0.86 (1) | 2.05 (2) | 2.850 (5) | 155 (3) |
| OW1—H14···O12vii | 0.86 (1) | 2.52 (4) | 3.109 (5) | 127 (4) |
| OW1—H14···OW2viii | 0.86 (1) | 2.55 (4) | 3.073 (6) | 120 (3) |
| OW2—H16···O12viii | 0.86 (1) | 2.20 (3) | 2.908 (5) | 139 (3) |
Symmetry codes: (i) −x+2, −y−1, −z+1; (ii) −x+2, −y, −z+1; (iii) −x+1, −y−1, −z+1; (iv) −x+1, −y, −z+1; (v) x, y−1, z; (vi) x−1, y, z; (vii) −x+1, −y+1, −z; (viii) −x+1, −y, −z.
Hexaquaaluminium sulfate chloride monohydrate (2). Crystal data
| [Al(H2O)6]Cl(SO4)·H2O | F(000) = 592 |
| Mr = 284.60 | Dx = 1.850 Mg m−3 |
| monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.1640 (14) Å | Cell parameters from 3645 reflections |
| b = 22.933 (5) Å | θ = 3.0–23.3° |
| c = 7.2876 (14) Å | µ = 0.71 mm−1 |
| β = 97.328 (2)° | T = 296 K |
| V = 1021.8 (4) Å3 | Block, coloress |
| Z = 4 | 0.20 × 0.10 × 0.10 mm |
Hexaquaaluminium sulfate chloride monohydrate (2). Data collection
| Bruker APEXII CCD diffractometer | 1457 independent reflections |
| Radiation source: fine-focus sealed tube | 1304 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.044 |
| φ and ω scans | θmax = 23.3°, θmin = 3.0° |
| Absorption correction: multi-scan (SADABS; Bruker, 2015) | h = −6→6 |
| Tmin = 0.872, Tmax = 0.933 | k = −25→25 |
| 8454 measured reflections | l = −8→8 |
Hexaquaaluminium sulfate chloride monohydrate (2). 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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0256P)2 + 0.8819P] where P = (Fo2 + 2Fc2)/3 |
| 1457 reflections | (Δ/σ)max < 0.001 |
| 170 parameters | Δρmax = 0.20 e Å−3 |
| 14 restraints | Δρmin = −0.29 e Å−3 |
Hexaquaaluminium sulfate chloride monohydrate (2). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Al1 | 0.94442 (10) | 0.36368 (3) | 0.83030 (9) | 0.01735 (19) | |
| S1 | 0.41721 (9) | 0.32296 (2) | 0.34162 (7) | 0.01806 (17) | |
| O1 | 0.8883 (3) | 0.34621 (7) | 1.0718 (2) | 0.0242 (4) | |
| O2 | 0.6779 (3) | 0.40544 (7) | 0.7845 (2) | 0.0236 (4) | |
| O3 | 0.7994 (3) | 0.29620 (7) | 0.7410 (2) | 0.0236 (4) | |
| O4 | 1.0001 (3) | 0.38033 (7) | 0.5873 (2) | 0.0243 (4) | |
| O5 | 1.0925 (3) | 0.43174 (7) | 0.9146 (2) | 0.0262 (4) | |
| O6 | 1.2075 (3) | 0.32177 (7) | 0.8685 (2) | 0.0218 (4) | |
| O7 | 0.5853 (3) | 0.28049 (7) | 0.4172 (2) | 0.0288 (4) | |
| O8 | 0.2061 (2) | 0.29253 (7) | 0.2976 (2) | 0.0251 (4) | |
| O9 | 0.4791 (3) | 0.34900 (7) | 0.1719 (2) | 0.0257 (4) | |
| O10 | 0.3963 (2) | 0.36795 (7) | 0.4814 (2) | 0.0237 (4) | |
| Cl1 | 1.22318 (11) | 0.52579 (3) | 0.66184 (10) | 0.0399 (2) | |
| OW1 | 1.2769 (3) | 0.47795 (8) | 1.2298 (3) | 0.0329 (4) | |
| H1 | 0.768 (3) | 0.3524 (14) | 1.115 (4) | 0.054 (3)* | |
| H2 | 0.977 (4) | 0.3286 (12) | 1.152 (3) | 0.054 (3)* | |
| H3 | 0.691 (5) | 0.4422 (5) | 0.783 (5) | 0.054 (3)* | |
| H4 | 0.588 (4) | 0.3942 (14) | 0.693 (3) | 0.054 (3)* | |
| H5 | 0.734 (5) | 0.2727 (11) | 0.805 (4) | 0.054 (3)* | |
| H6 | 0.734 (5) | 0.2915 (14) | 0.632 (2) | 0.054 (3)* | |
| H7 | 0.933 (4) | 0.4067 (10) | 0.520 (4) | 0.054 (3)* | |
| H8 | 1.126 (3) | 0.3750 (14) | 0.557 (4) | 0.054 (3)* | |
| H9 | 1.143 (5) | 0.4415 (13) | 1.025 (2) | 0.054 (3)* | |
| H10 | 1.130 (5) | 0.4554 (11) | 0.834 (3) | 0.054 (3)* | |
| H11 | 1.215 (5) | 0.2853 (5) | 0.855 (4) | 0.054 (3)* | |
| H12 | 1.304 (4) | 0.3305 (14) | 0.957 (3) | 0.054 (3)* | |
| H13 | 1.400 (3) | 0.4634 (13) | 1.270 (4) | 0.054 (3)* | |
| H14 | 1.220 (5) | 0.4762 (14) | 1.329 (3) | 0.054 (3)* |
Hexaquaaluminium sulfate chloride monohydrate (2). Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Al1 | 0.0135 (4) | 0.0205 (4) | 0.0175 (4) | −0.0001 (3) | 0.0002 (3) | 0.0011 (3) |
| S1 | 0.0136 (3) | 0.0220 (3) | 0.0178 (3) | 0.0011 (2) | −0.0007 (2) | −0.0008 (2) |
| O1 | 0.0173 (9) | 0.0370 (10) | 0.0184 (9) | 0.0042 (8) | 0.0026 (7) | 0.0054 (7) |
| O2 | 0.0171 (9) | 0.0264 (9) | 0.0260 (9) | 0.0017 (7) | −0.0017 (7) | 0.0001 (8) |
| O3 | 0.0230 (9) | 0.0267 (10) | 0.0194 (9) | −0.0064 (7) | −0.0034 (7) | 0.0031 (7) |
| O4 | 0.0193 (9) | 0.0306 (10) | 0.0236 (9) | 0.0051 (7) | 0.0052 (7) | 0.0074 (7) |
| O5 | 0.0265 (9) | 0.0250 (10) | 0.0256 (10) | −0.0063 (7) | −0.0028 (8) | 0.0010 (8) |
| O6 | 0.0176 (9) | 0.0234 (9) | 0.0233 (9) | 0.0033 (7) | −0.0022 (7) | −0.0020 (8) |
| O7 | 0.0267 (9) | 0.0316 (10) | 0.0253 (9) | 0.0133 (8) | −0.0071 (7) | −0.0062 (8) |
| O8 | 0.0188 (9) | 0.0258 (9) | 0.0286 (9) | −0.0053 (7) | −0.0042 (7) | 0.0044 (7) |
| O9 | 0.0210 (9) | 0.0364 (10) | 0.0197 (9) | −0.0048 (7) | 0.0030 (7) | 0.0009 (7) |
| O10 | 0.0202 (9) | 0.0260 (9) | 0.0249 (9) | 0.0015 (7) | 0.0027 (7) | −0.0049 (7) |
| Cl1 | 0.0288 (4) | 0.0426 (4) | 0.0458 (4) | −0.0069 (3) | −0.0045 (3) | 0.0166 (3) |
| OW1 | 0.0298 (10) | 0.0329 (11) | 0.0349 (11) | 0.0066 (8) | 0.0000 (8) | 0.0006 (9) |
Hexaquaaluminium sulfate chloride monohydrate (2). Geometric parameters (Å, º)
| Al1—O3 | 1.8624 (17) | Al1—O2 | 1.8940 (17) |
| Al1—O5 | 1.8718 (18) | S1—O10 | 1.4670 (16) |
| Al1—O6 | 1.8752 (17) | S1—O9 | 1.4672 (16) |
| Al1—O1 | 1.8798 (17) | S1—O8 | 1.4753 (16) |
| Al1—O4 | 1.8855 (17) | S1—O7 | 1.4767 (16) |
| O3—Al1—O5 | 178.65 (8) | O5—Al1—O2 | 90.67 (8) |
| O3—Al1—O6 | 89.63 (8) | O6—Al1—O2 | 178.38 (8) |
| O5—Al1—O6 | 90.14 (8) | O1—Al1—O2 | 90.78 (8) |
| O3—Al1—O1 | 90.72 (8) | O4—Al1—O2 | 89.41 (7) |
| O5—Al1—O1 | 90.61 (8) | O10—S1—O9 | 110.75 (10) |
| O6—Al1—O1 | 90.61 (7) | O10—S1—O8 | 109.30 (10) |
| O3—Al1—O4 | 88.68 (8) | O9—S1—O8 | 109.04 (9) |
| O5—Al1—O4 | 89.99 (8) | O10—S1—O7 | 108.95 (9) |
| O6—Al1—O4 | 89.19 (7) | O9—S1—O7 | 109.71 (10) |
| O1—Al1—O4 | 179.37 (8) | O8—S1—O7 | 109.07 (10) |
| O3—Al1—O2 | 89.53 (8) |
Hexaquaaluminium sulfate chloride monohydrate (2). Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O9i | 0.85 (1) | 1.88 (1) | 2.714 (2) | 165 (3) |
| O1—H2···O8ii | 0.85 (1) | 1.85 (1) | 2.690 (2) | 170 (3) |
| O2—H3···OW1iii | 0.85 (1) | 1.85 (1) | 2.692 (2) | 178 (3) |
| O2—H4···O10 | 0.85 (1) | 1.92 (1) | 2.767 (2) | 177 (3) |
| O3—H5···O7iv | 0.85 (1) | 1.78 (1) | 2.629 (2) | 174 (3) |
| O3—H6···O7 | 0.85 (1) | 1.73 (1) | 2.578 (2) | 176 (3) |
| O4—H7···Cl1v | 0.85 (1) | 2.18 (1) | 3.0311 (18) | 177 (3) |
| O4—H8···O10vi | 0.85 (1) | 1.83 (1) | 2.669 (2) | 176 (3) |
| O5—H9···OW1 | 0.85 (1) | 1.82 (1) | 2.650 (2) | 166 (3) |
| O5—H10···Cl1 | 0.85 (1) | 2.17 (1) | 3.0120 (18) | 171 (3) |
| O6—H11···O8vii | 0.85 (1) | 1.83 (1) | 2.672 (2) | 172 (3) |
| O6—H12···O9ii | 0.85 (1) | 1.83 (1) | 2.671 (2) | 171 (3) |
| OW1—H13···Cl1viii | 0.85 (1) | 2.33 (2) | 3.083 (2) | 149 (3) |
| OW1—H14···Cl1i | 0.84 (1) | 2.68 (2) | 3.390 (2) | 143 (3) |
| OW1—H14···Cl1iii | 0.84 (1) | 2.74 (3) | 3.280 (2) | 123 (3) |
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+1; (iii) −x+2, −y+1, −z+2; (iv) x, −y+1/2, z+1/2; (v) −x+2, −y+1, −z+1; (vi) x+1, y, z; (vii) x+1, −y+1/2, z+1/2; (viii) −x+3, −y+1, −z+2.
Funding Statement
This work was funded by Vetenskapsrådet grant 2014-3938.
References
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, 1, 2. DOI: 10.1107/S2056989020015741/wm5585sup1.cif
Additional supporting information: crystallographic information; 3D view; checkCIF report