1. 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).
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.
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) | | | | |
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) . | |
| Figure 1 The asymmetric unit of (1), representing the building units. Displacement ellipsoids are drawn at the 50% probability level. |
| Figure 2 Packing in the crystal structure of compound (1). Hydrogen bonding is indicated by dotted lines. |
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).
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) | | |
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) ; (iv) ; (v) ; (vi) x+1, y, z; (vii) ; (viii) . | |
| Figure 3 The asymmetric unit of (2), representing the building units. Displacement ellipsoids are drawn at the 50% probability level. |
| Figure 4 Packing in the crystal structure of compound (2). Hydrogen bonding is indicated by dotted lines. |
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−).
4. 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.
5. 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 Uiso(H) parameter. Reasonable geometries for the unligated water water molecules were ensured by using restrained H⋯H distances of 1.55 (1) Å.
| (1) | (2) | Crystal data | Chemical formula | [Al(H2O)6](NO3)(SO4)·2H2O | [Al(H2O)6]Cl(SO4)·H2O | Mr | 329.18 | 284.60 | Crystal system, space group | Triclinic, P![[\overline{1}]](teximages/wm5585fi17.gif) | 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 ) | Tmin, Tmax | 0.919, 0.992 | 0.872, 0.933 | No. of measured, independent and observed [I > 2σ(I)] reflections | 4506, 1642, 1519 | 8454, 1457, 1304 | Rint | 0.026 | 0.044 | θmax (°) | 23.4 | 23.3 | (sin θ/λ)max (Å−1) | 0.559 | 0.556 | | Refinement | R[F2 > 2σ(F2)], wR(F2), 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 | Computer programs: APEX2 and SAINT (Bruker, 2015 ), SHELXS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ). | |
Supporting information
For both structures, data collection: APEX2 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: publCIF (Westrip, 2010).
Hexaquaaluminium sulfate nitrate dihydrate (1)
top Crystal data top [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 |
Data collection top 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 |
Refinement top 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) |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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)* | |
Atomic displacement parameters (Å2) top | 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) |
Geometric parameters (Å, º) top 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) |
Hydrogen-bond geometry (Å, º) top 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)
top Crystal data top [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 |
Data collection top 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 |
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)] = 0.024 | 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 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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)* | |
Atomic displacement parameters (Å2) top | 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) |
Geometric parameters (Å, º) top 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) | | |
Hydrogen-bond geometry (Å, º) top 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. |
Acknowledgements
Professor Vadim Kessler is acknowledged for valuable discussions.
Funding information
The support from the Swedish Research Council (Vetenskapsrådet) (grant 2014–3938) is gratefully acknowledged.
References
Anderson, A. J., Yang, H. X. & Downs, R. T. (2015). Am. Mineral. 100, 330–333. CrossRef ICSD Google Scholar
Beattie, J. K., Best, S. P., Skelton, B. W. & White, A. H. (1981). J. Chem. Soc. Dalton Trans. pp. 2105–2111. CrossRef ICSD Web of Science Google Scholar
Bruker (2015). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Demartin, F., Castellano, C., Gramaccioli, C. M. & Campostrini, I. (2010). Can. Mineral. 48, 323–333. Web of Science CrossRef ICSD CAS Google Scholar
Fischer, T., Eisenmann, B. & Kniep, R. Z. (1996). Z. Kristallogr. 211, 473–474. CAS Google Scholar
Greenwood, N. N. & Earnshaw, A. (1997). Chemistry of the Elements. London: Butterworth–Heinemann. Google Scholar
Hay, M. B. & Myneni, S. C. B. (2008). J. Phys. Chem. A, 112, 10595–10603. CrossRef PubMed CAS Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Parnham, E. R. & Morris, R. E. (2006). J. Mater. Chem. 16, 3682–3684. CrossRef ICSD CAS Google Scholar
Sabelli, C. & Ferroni, R. T. (1978). Acta Cryst. B34, 2407–2412. CrossRef ICSD CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Veillard, M. (1977). J. Am. Chem. Soc. 99, 7194–7199. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
 | CRYSTALLOGRAPHIC COMMUNICATIONS |
ISSN: 2056-9890
Open

access