Synthesis and crystal structures of [Al(H2O)6](SO4)NO3·2H2O and [Al(H2O)6](SO4)Cl·H2O

Svensson, F.G.

doi:10.1107/S2056989020015741

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Volume 77| Part 1| January 2021| Pages 58-61

https://doi.org/10.1107/S2056989020015741

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Synthesis and crystal structures of [Al(H₂O)₆](SO₄)NO₃·2H₂O and [Al(H₂O)₆](SO₄)Cl·H₂O

Fredric G. Svensson ^a ^*

^aDepartment of Molecular Sciences, Swedish University of Agricultural Sciences, Box 7015, 750 07 Uppsala, Sweden
^*Correspondence e-mail: fredric.svensson@slu.se

Edited by M. Weil, Vienna University of Technology, Austria (Received 14 September 2020; accepted 1 December 2020; online 1 January 2021)

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 SO₄²⁻ 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.

Keywords: crystal structure; aluminium; double salt; hydrogen bonding.

CCDC references: 2030818; 2028868

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.

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)

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⋯O8^iv	0.85 (1)	1.91 (1)	2.745 (3)	168 (4)
O4—H8⋯O11^v	0.85 (1)	2.12 (2)	2.884 (4)	150 (4)
O4—H8⋯O13^v	0.85 (1)	2.13 (3)	2.870 (4)	147 (4)
O5—H9⋯O9^vi	0.85 (1)	1.80 (1)	2.650 (3)	179 (4)
O5—H10⋯O10^iv	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⋯O11^vii	0.85 (1)	2.35 (3)	3.044 (4)	139 (3)
O6—H12⋯O12^vii	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⋯O12^vii	0.86 (1)	2.52 (4)	3.109 (5)	127 (4)
OW1—H14⋯OW2^viii	0.86 (1)	2.55 (4)	3.073 (6)	120 (3)
OW2—H16⋯O12^viii	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).

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)

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⋯O7^iv	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⋯Cl1^v	0.85 (1)	2.18 (1)	3.0311 (18)	177 (3)
O4—H8⋯O10^vi	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⋯O8^vii	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⋯Cl1^viii	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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) ; (vi) x+1, y, z; (vii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (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⁻).

3. 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).

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 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 $[\overline{1}]$	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
θ_max (°)	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
Δρ_max, Δρ_min (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

CCDC references: 2030818; 2028868

Crystal structure: contains datablocks global, 1, 2. DOI: https://doi.org/10.1107/S2056989020015741/wm5585sup1.cif

checkCIF report

Computing details top

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
M_r = 329.18	F(000) = 344
triclinic, P1	D_x = 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	R_int = 0.026
φ and ω scans	θ_max = 23.4°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −6→6
T_min = 0.919, T_max = 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(F_o²) + (0.0404P)² + 0.6205P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
1642 reflections	Δρ_max = 0.50 e Å⁻³
213 parameters	Δρ_min = −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	U_iso*/U_eq
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···O8^iv	0.85 (1)	1.91 (1)	2.745 (3)	168 (4)
O4—H8···O11^v	0.85 (1)	2.12 (2)	2.884 (4)	150 (4)
O4—H8···O13^v	0.85 (1)	2.13 (3)	2.870 (4)	147 (4)
O5—H9···O9^vi	0.85 (1)	1.80 (1)	2.650 (3)	179 (4)
O5—H10···O10^iv	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···O11^vii	0.85 (1)	2.35 (3)	3.044 (4)	139 (3)
O6—H12···O12^vii	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···O12^vii	0.86 (1)	2.52 (4)	3.109 (5)	127 (4)
OW1—H14···OW2^viii	0.86 (1)	2.55 (4)	3.073 (6)	120 (3)
OW2—H16···O12^viii	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
M_r = 284.60	D_x = 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	R_int = 0.044
φ and ω scans	θ_max = 23.3°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2015)	h = −6→6
T_min = 0.872, T_max = 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(F_o²) + (0.0256P)² + 0.8819P] where P = (F_o² + 2F_c²)/3
1457 reflections	(Δ/σ)_max < 0.001
170 parameters	Δρ_max = 0.20 e Å⁻³
14 restraints	Δρ_min = −0.29 e Å⁻³

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

	x	y	z	U_iso*/U_eq
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···O7^iv	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···Cl1^v	0.85 (1)	2.18 (1)	3.0311 (18)	177 (3)
O4—H8···O10^vi	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···O8^vii	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···Cl1^viii	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

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