Crystal structure of NH4[La(SO4)2(H2O)]

Benslimane, M.; Redjel, Y.K.; Merazig, H.; Daran, J.-C.

doi:10.1107/S2056989015009457

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ISSN: 2056-9890

Volume 71| Part 6| June 2015| Pages 663-666

doi:10.1107/S2056989015009457

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Crystal structure of NH₄[La(SO₄)₂(H₂O)]

Meriem Benslimane,^a ^* Yasmine Kheira Redjel,^a Hocine Merazig ^a and Jean-Claude Daran ^b

^aUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, Faculté des Sciences Exactes, Département de Chimie, Université de Constantine 1, 25000 Constantine, Algeria, and ^bLaboratoire de Chimie de Coordination, UPR-CNRS 8241, 05 route de Narbonne, 31077 Toulouse Cedex 4
^*Correspondence e-mail: b_meriem80@yahoo.fr

Edited by M. Weil, Vienna University of Technology, Austria (Received 20 April 2015; accepted 18 May 2015; online 23 May 2015)

The principal building units in the crystal structure of ammonium aquabis(sulfato)lanthanate(III) are slightly distorted SO₄ tetrahedra, LaO₉ polyhedra in the form of distorted tricapped trigonal prisms, and NH₄⁺ ions. The La³⁺ cation is coordinated by eight O atoms from six different sulfate tetrahedra, two of which are bidentate coordinating and four monodentate, as well as one O atom from a water molecule; each sulfate anion bridges three La³⁺ cations. These bridging modes result in the formation of a three-dimensional anionic [La(SO₄)₂(H₂O)]⁻ framework that is stabilized by O—H⋯O hydrogen-bonding interactions. The disordered ammonium cations are situated in the cavities of this framework and are hydrogen-bonded to six surrounding O atoms.

Keywords: crystal structure; hydrous ternary sulfates; hydrothermal synthesis; hydrogen bonding.

CCDC reference: 1401662

1. Chemical context

Three-dimensional framework materials are characterized by their structural diversity. They are of continuing interest as a result of their technologically important properties and potential applications in catalysis, ion-exchange, adsorption, intercalation, and radioactive waste remediation (Szostak, 1989 ; Cheetham et al., 1999 ; Rosi et al., 2003 ; Ok et al., 2007 ). Many materials showing such functional features contain structurally versatile cations, in particular heavier metal cations with large coordination spheres. Among many other cations, lanthanide cations have been used widely, since they exhibit high coordination numbers and can show a large topological diversity in the resulting framework structures (Bataille & Louër, 2002 ; Wickleder, 2002 ; Yuan et al., 2005 ). One of the most promising synthetic methods for the preparation of compounds with framework structures is the hydrothermal (or solvothermal) reaction technique (Feng et al., 1997 ; Natarajan et al., 2000 ) in which mineralizers such as acids or bases are introduced to increase the solubility and reactivity of the reagents (Laudise, 1959 ; Laudise & Ballman, 1958 ). Moreover, organic or inorganic templates are used to direct the topologies of the framework structures and the concomitant physical and chemical properties of the products (Szostak, 1989; Breck, 1974 ; Barrer, 1982 ). Thus, we have tried to utilize the hydrothermal technique to react a lanthanide cation (La³⁺) with sulfuric acid in the presence of NH₄OH and 3-aminobenzoic acid as a template to prepare higher dimensional framework materials. However, in the present case the organic template was not incorporated in the resultant crystal structure of the title compound, NH₄[La(SO₄)₂(H₂O)], which represents a new hydrate form. Other members in the system NH₄⁺/La³⁺/SO₄²⁻/(H₂O) are two forms of anhydrous (NH₄)[La(SO₄)₂] (Sarukhanyan et al., 1984a ; Bénard-Rocherullé et al., 2001 ), (NH₄)₅[La(SO₄)₄] (Niinisto et al., 1980 ) and (NH₄)[La(SO₄)₂(H₂O)₄] (Keppert et al., 1999 ).

Sulfates with an A⁺:Ln³⁺ (A⁺ = alkaline ions, Ln³⁺ = lanthanide ions) ratio of 1:1 are one of the best investigated groups among hydrous ternary sulfates. They crystallize either as monohydrates (Blackburn & Gerkin, 1995 ; Barnes, 1995 ; Iskhakova et al., 1985a ) or tetrahydrates (Eriksson et al., 1974 ), and in few cases also as dihydrates (Kaucic et al., 1985 ; Iskhakova & Trunov, 1985 ). The tetrahydrates are mainly found for the bigger monovalent ions Cs⁺, NH₄⁺, and Rb⁺. For the smaller A⁺ ions such as Na⁺, the monohydrate becomes dominant.

2. Structural commentary

The structure of the title compound comprises LaO₉ polyhedra and SO₄ tetrahedra as the principal building units (Fig. 1), forming an anionic [La(SO₄)₂(H₂O)]⁻ framework by sharing common edges and vertices (Fig. 2). The NH₄⁺ counter-cations are situated in the cavities of this framework.

Figure 1
The principal building units, LaO₉ polyhedra and SO₄ tetrahedra, in the crystal structure of (NH₄)[La(SO₄)₂(H₂O)], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 − x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (ii) 1 − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z; (iii) 1 − x, 2 − y, −z; (iv) 2 − x, 2 − y, 1 − z; (v) x, $[{3\over 2}]$ − y, $[{1\over 2}]$ + z.]

Figure 2
The connection of LaO₉ polyhedra and SO₄ tetrahedra in the crystal structure of (NH₄)[La(SO₄)₂(H₂O)], viewed along the a axis.

The La³⁺ cation is coordinated by eight O atoms from six different sulfate tetrahedra. Two tetrahedra are in a bidentate coordination mode and four tetrahedra are in a monodentate mode. The distorted tricapped trigonal–prismatic coordination sphere is completed by one O atom from a water molecule. The La—O bond lengths, ranging from 2.472 (3) to 2.637 (3) Å with 2.496 (3) Å to the water molecule, and the O—La—O angles, ranging from 53.55 (8) to 145.43 (9)°, are similar to the analogous distances found in NaLa(SO₄)₂·H₂O (Blackburn & Gerkin, 1995). The ninefold coordination of La³⁺ in NH₄[La(SO₄)₂(H₂O)] is typical for the majority of monohydrated alkali rare earth sulfate complexes and of rare earth complexes in general. For early members of the rare earth sulfate series, the coordination number of nine is realized, e.g. for Ce, Pr, La and Nd (Blackburn & Gerkin, 1994 , 1995; Iskhakova et al., 1985b , 1988 ). For later members of the sulfate series, such as Gd (Sarukhanyan et al., 1984b ), the coordination number decreases to eight, presumably in association with the lanthanide contraction. There are two sulfur atoms (S1, S2) in the asymmetric unit of the title compound, both with very similar S—O bond lengths in the ranges 1.465 (3)–1.488 (3) and 1.468 (3)–1.490 (3) Å, respectively. The range of O—S—O bond angles, 106.04 (16)–110.89 (19)° for S1 and 104.70 (16)–111.52 (17)° for S2, reflect the distortion of the two sulfate tetrahedra. Each SO₄ anion bridges three La³⁺ cations (Fig. 2).

3. Supramolecular features

The bridging modes of the O atoms result in the formation of a three-dimensional anionic framework, stabilized by O—H⋯O hydrogen-bonding interactions between the aqua ligand and the two SO₄ tetrahedra (Table 1) whereby each sulfate tetrahedron establishes one hydrogen bond with the water molecule via the oxygen atom (O6 and O3) corresponding to the longest S—O bonds. The N atoms are situated in the cavities of this framework. Although the H atoms of the ammonium cation could not be located, the N⋯O distances between 2.865 (5) and 3.036 (5) Å strongly suggest N—H⋯O hydrogen bonds of medium strength (Table 1). It appears most likely that the number of O atoms (six) in the vicinity of the N atom is the reason for the disorder of the ammonium cation.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11⋯O3ⁱ	0.84 (5)	1.94 (5)	2.717 (5)	153 (5)
O1W—H21⋯O6ⁱⁱ	0.85 (3)	1.95 (3)	2.778 (4)	168 (5)
N1⋯O1ⁱⁱⁱ			2.942 (5)
N1⋯O6ⁱⁱ			3.036 (5)
N1⋯O3^iv			2.914 (5)
N1⋯O8^v			2.943 (5)
N1⋯O5^vi			2.865 (5)
N1⋯O4			2.866 (5)
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (iv) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) -x+1, -y+2, -z.

4. Synthesis and crystallization

The title compound was obtained during the attempted preparation of a complex resulting from the hydrothermal reaction of La₂O₃ (0.1 g, 1 mmol) with 37%wt sulfuric acid and 3-aminobenzoic acid (0.048 g, 1 mmol) in the presence of NH₄OH in 10 ml water. The mixture was kept in a 23 ml Teflon-lined steel autoclave at 433 K for 3 d. After this treatment, the autoclave was cooled slowly to room temperature. Slow evaporation of the solvent at room temperature led to the formation of prismatic colourless crystals of the title compound.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The oxygen-bound hydrogen atoms were located in a difference Fourier map and were refined with restraints of the O—H bond length [0.85 (1) Å] and H⋯H distances (1.39 Å) and with U_iso(H) = 1.5U_eq(O). The ammonium hydrogen atoms could not be located reliably by difference Fourier methods. Several disorder models considering the hydrogen-bonding environment (see Table 1) failed, eventually leading to the exclusion of the ammonium hydrogen atoms from the refinement. The maximum and minimum peaks in the final difference Fourier map are 0.93 and 0.72 Å, respectively, from atom La1.

Table 2
Experimental details

Crystal data
Chemical formula	NH₄[La(SO₄)₂(H₂O)]
M_r	367.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.4919 (16), 9.978 (2), 11.9268 (19)
β (°)	128.511 (10)
V (Å³)	790.7 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	5.96
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	For a sphere (Dwiggins, 1975 )
T_min, T_max	0.419, 0.431
No. of measured, independent and observed [I > 2σ(I)] reflections	2414, 2414, 2362
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.081, 1.26
No. of reflections	2414
No. of parameters	124
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.81, −1.48
Computer programs: COLLECT (Nonius, 1998 ), DENZO and SCALEPACK (Otwinowski & Minor, 1997 ), SIR92 (Altomare et al., 1993 ), SHELXL97 (Sheldrick, 2008 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and DIAMOND (Brandenburg & Berndt, 1999 ).

Diffraction data were collected some time ago, and merged in the corresponding crystal class. Unfortunately, the original measurement data got lost; experiments to repeat the crystal growth were unsuccessful. Therefore the crystal structure was finally solved and refined with the merged data set.

Supporting information

CCDC reference: 1401662

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015009457/wm5148sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015009457/wm5148Isup2.hkl

checkCIF report

Chemical context top

Three-dimensional framework materials are characterized by their structural diversity. They are of continuing interest as a result of their technologically important properties and potential applications in catalysis, ion-exchange, adsorption, intercalation, and radioactive waste remediation (Szostak, 1989; Cheetham et al., 1999; Rosi et al., 2003; Ok et al., 2007). Many materials showing such functional features contain structurally versatile cations, in particular heavier metal cations with large coordination spheres. Among many other cations, lanthanide cations have been used widely, since they exhibit high coordination numbers and can show a large topological diversity in the resulting framework structures (Bataille & Louër, 2002; Wickleder, 2002; Yuan et al., 2005). One of the most promising synthetic methods for the preparation of compounds with framework structures is the hydrothermal (or solvothermal) reaction technique (Feng et al., 1997; Natarajan et al., 2000) in which mineralizers such as acids or bases are introduced to increase the solubility and reactivity of the reagents (Laudise, 1959; Laudise & Ballman, 1958). Moreover, organic or inorganic templates are used to direct the topologies of the framework structures and the concomitant physical and chemical properties of the products (Szostak, 1989; Breck, 1974; Barrer, 1982). Thus, we have tried to utilize the hydrothermal technique to react a lanthanide cation (La³⁺) with sulfuric acid in the presence of NH₄OH and 3-aminobenzoic acid as a template to prepare higher dimensional framework materials. However, in the present case the organic template was not incorporated in the resultant crystal structure of the title compound, NH₄[La(SO₄)₂(H₂O)], which represents a new hydrate form. Other members in the system NH₄⁺/La³⁺/SO₄^2-/(H₂O) are two forms of anhydrous (NH₄)[La(SO₄)₂] (Sarukhanyan et al., 1984a; Bénard-Rocherullé et al., 2001), (NH₄)₅[La(SO₄)₄] (Niinisto et al., 1980) and (NH₄)[La(SO₄)₂(H₂O)₄] (Junk et al., 1999).

Sulfates with an A⁺:Ln³⁺ (A⁺ = alkaline ions, Ln³⁺ = lanthanide ions) ratio of 1:1 are one of the best investigated groups among hydrous ternary sulfates. They crystallize either as monohydrates (Blackburn & Gerkin, 1995; Barnes, 1995; Iskhakova et al., 1985a) or tetrahydrates (Eriksson et al., 1974), and in few cases also as dihydrates (Kaucic et al., 1985; Iskhakova & Trunov, 1985). The tetrahydrates are mainly found for the bigger monovalent ions Cs⁺, NH₄⁺, and Rb⁺. For the smaller A⁺ ions such as Na⁺, the monohydrate becomes dominant.

Structural commentary top

The structure of the title compound comprises LaO₉ polyhedra and SO₄ tetrahedra as the principal building units (Fig. 1), forming an anionic [La(SO₄)₂(H₂O)]^- framework by sharing common edges and vertices (Fig. 2). The NH₄⁺ counter-cations are situated in the cavities of this framework.

The La³⁺ cation is coordinated by eight O atoms from six different sulfate tetrahedra. Two tetrahedra are in a bidentate coordination mode and four tetrahedra are in a monodentate mode. The distorted tricapped trigonal–prismatic coordination sphere is completed by one O atom from a water molecule. The La—O bond lengths, ranging from 2.472 (3) to 2.637 (3) Å with 2.496 (3) Å to the water molecule, and the O—La—O angles, ranging from 53.55 (8) to 145.43 (9)°, are similar to the analogous distances found in NaLa(SO₄)₂·H₂O (Blackburn & Gerkin, 1995). The ninefold coordination of La³⁺ in NH₄[La(SO₄)₂(H₂O)] is typical for the majority of monohydrated alkali rare earth sulfate complexes and of rare earth complexes in general. For early members of the rare earth sulfate series, the coordination number of nine is realized, e.g. for Ce, Pr, La and Nd (Blackburn & Gerkin, 1994, 1995; Iskhakova et al., 1985b, 1988). For later members of the sulfate series, such as Gd (Sarukhanyan et al., 1984b), the coordination number decreases to eight, presumably in association with the lanthanide contraction. There are two sulfur atoms (S1, S2) in the asymmetric unit of the title compound, both with very similar S—O bond lengths in the ranges 1.465 (3)–1.488 (3) and 1.468 (3)–1.490 (3) Å, respectively. The range of O—S—O bond angles, 106.04 (16)–110.89 (19)° for S1 and 104.70 (16)–111.52 (17)° for S2, reflect the distortion of the two sulfate tetrahedra. Each SO₄ anion bridges three La³⁺ cations (Fig. 2).

Supramolecular features top

The bridging modes of the O atoms result in the formation of a three-dimensional anionic framework, stabilized by O—H···O hydrogen-bonding interactions between the aqua ligand and the two SO₄ tetrahedra (Table 1) whereby each sulfate tetrahedron establishes one hydrogen bond with the water molecule via the oxygen atom (O6 and O3) corresponding to the longest S—O bonds. The N atoms are situated in the cavities of this framework. Although the H atoms of the ammonium cation could not be located, the N···O distances between 2.865 (5) and 3.036 (5) Å strongly suggest N—H···O hydrogen bonds of medium strength (Table 1). It appears most likely that the number of O atoms (six) in the vicinity of the N atom is the reason for the disorder of the ammonium cation.

Synthesis and crystallization top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The oxygen-bound hydrogen atoms were located in a difference Fourier map and were refined with restraints of the O—H bond length [0.85 (1) Å] and H···H distances (1.39 Å) and with U_iso(H) = 1.5U_eq(O). The ammonium hydrogen atoms could not be located reliably by difference Fourier methods. Several disorder models considering the hydrogen-bonding environment (see Table 1) failed, eventually leading to the exclusion of the ammonium hydrogen atoms from the refinement. The maximum and minimum peaks in the final difference Fourier map are 0.93 and 0.72 Å, respectively, from atom La1.

Related literature top

For related literature, see: Barnes (1995); Barrer (1982); Bataille & Louer (2002); Bénard-Rocherullé, Tronel & Louer (2001); Blackburn & Gerkin (1994, 1995); Breck (1974); Cheetham et al. (1999); Eriksson et al. (1974); Feng et al. (1997); Iskhakova & Trunov (1985); Iskhakova et al. (1985a, 1985b, 1988); Junk et al. (1999); Kaucic et al. (1985); Laudise (1959); Laudise & Ballman (1958); Natarajan et al. (2000); Niinisto et al. (1980); Ok et al. (2007); Rosi et al. (2003); Sarukhanyan et al. (1984a, 1984b); Szostak (1989); Wickleder (2002); Yuan et al. (2005).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The principal building units, LaO₉ polyhedra and SO₄ tetrahedra, in the crystal structure of (NH₄)[La(SO₄)₂(H₂O)], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 - x, -1/2 + y, 1/2 - z; (ii) 1 - x, 1/2 + y, 1/2 - z; (iii) 1 - x, 2 - y, -z; (iv) 2 - x, 2 - y, 1 - z; (v) x, 3/2 - y, 1/2 + z.]
	Fig. 2. The connection of LaO₉ polyhedra and SO₄ tetrahedra in the crystal structure of (NH₄)[La(SO₄)₂(H₂O)], viewed along the a axis.

Ammonium aquabis(sulfato)lanthanate(III) top

Crystal data top

NH₄[La(SO₄)₂(H₂O)]	F(000) = 680
M_r = 367.07	D_x = 3.083 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2542 reflections
a = 8.4919 (16) Å	θ = 3–30.5°
b = 9.978 (2) Å	µ = 5.96 mm⁻¹
c = 11.9268 (19) Å	T = 100 K
β = 128.511 (10)°	Prism, colourless
V = 790.7 (3) Å³	0.30 × 0.20 × 0.10 × 0.10 (radius) mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2414 independent reflections
Radiation source: fine-focus sealed tube	2362 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.0000
Detector resolution: 9 pixels mm^-1	θ_max = 30.5°, θ_min = 3.0°
CCD scans	h = −12→0
Absorption correction: for a sphere (Dwiggins, 1975)	k = −14→0
T_min = 0.419, T_max = 0.431	l = −12→17
2414 measured reflections

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	w = 1/[σ²(F_o²) + (0.0427P)² + 2.7376P] where P = (F_o² + 2F_c²)/3
2414 reflections	(Δ/σ)_max = 0.001
124 parameters	Δρ_max = 1.81 e Å⁻³
3 restraints	Δρ_min = −1.48 e Å⁻³

Crystal data top

NH₄[La(SO₄)₂(H₂O)]	V = 790.7 (3) Å³
M_r = 367.07	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.4919 (16) Å	µ = 5.96 mm⁻¹
b = 9.978 (2) Å	T = 100 K
c = 11.9268 (19) Å	0.30 × 0.20 × 0.10 × 0.10 (radius) mm
β = 128.511 (10)°

Data collection top

Nonius KappaCCD diffractometer	2414 independent reflections
Absorption correction: for a sphere (Dwiggins, 1975)	2362 reflections with I > 2σ(I)
T_min = 0.419, T_max = 0.431	R_int = 0.0000
2414 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	3 restraints
wR(F²) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	Δρ_max = 1.81 e Å⁻³
2414 reflections	Δρ_min = −1.48 e Å⁻³
124 parameters

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 > σ(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

	x	y	z	U_iso*/U_eq
La1	0.71683 (3)	0.839390 (18)	0.248314 (19)	0.01052 (8)
S1	0.74128 (12)	1.09162 (8)	0.42791 (8)	0.01163 (15)
S2	0.70608 (12)	0.91270 (8)	−0.02026 (8)	0.01129 (15)
O1	0.6085 (4)	1.0290 (3)	−0.1156 (3)	0.0179 (5)
O2	0.8105 (5)	0.8337 (3)	−0.0602 (3)	0.0189 (5)
O3	0.8535 (4)	0.9585 (3)	0.1310 (3)	0.0156 (5)
O8	0.9057 (4)	1.1402 (3)	0.5727 (3)	0.0182 (5)
O4	0.5597 (4)	0.8301 (3)	−0.0221 (3)	0.0188 (5)
O7	0.5667 (4)	1.1797 (3)	0.3641 (3)	0.0229 (6)
O6	0.6873 (4)	0.9516 (3)	0.4347 (3)	0.0185 (5)
O5	0.8062 (4)	1.0870 (3)	0.3387 (3)	0.0192 (5)
O1W	0.8711 (5)	0.6537 (3)	0.2059 (3)	0.0241 (6)
H11	0.982 (5)	0.615 (6)	0.266 (4)	0.036*
H21	0.820 (8)	0.632 (6)	0.121 (2)	0.036*
N1	0.2567 (6)	0.6458 (4)	−0.2302 (4)	0.0244 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.01098 (11)	0.00981 (11)	0.01113 (11)	−0.00037 (5)	0.00706 (9)	−0.00028 (5)
S1	0.0106 (3)	0.0110 (3)	0.0114 (3)	0.0009 (3)	0.0059 (3)	−0.0005 (3)
S2	0.0118 (3)	0.0111 (3)	0.0101 (3)	0.0008 (3)	0.0064 (3)	0.0000 (2)
O1	0.0212 (12)	0.0144 (11)	0.0173 (11)	0.0055 (10)	0.0116 (10)	0.0056 (9)
O2	0.0214 (13)	0.0207 (14)	0.0180 (13)	0.0035 (10)	0.0140 (12)	−0.0013 (9)
O3	0.0158 (11)	0.0162 (11)	0.0111 (10)	−0.0037 (9)	0.0066 (9)	−0.0028 (9)
O8	0.0141 (12)	0.0206 (12)	0.0141 (12)	−0.0009 (10)	0.0059 (10)	−0.0041 (10)
O4	0.0181 (13)	0.0212 (13)	0.0174 (12)	−0.0061 (9)	0.0111 (11)	−0.0018 (9)
O7	0.0139 (12)	0.0207 (13)	0.0217 (13)	0.0068 (10)	0.0049 (11)	−0.0025 (10)
O6	0.0240 (13)	0.0145 (11)	0.0174 (12)	−0.0029 (10)	0.0130 (11)	−0.0002 (9)
O5	0.0246 (13)	0.0181 (12)	0.0211 (12)	−0.0020 (10)	0.0174 (11)	−0.0016 (10)
O1W	0.0289 (16)	0.0220 (14)	0.0177 (13)	0.0126 (11)	0.0127 (12)	0.0010 (10)
N1	0.0248 (16)	0.0252 (18)	0.0296 (18)	−0.0037 (13)	0.0201 (15)	−0.0006 (13)

Geometric parameters (Å, º) top

La1—O7ⁱ	2.472 (3)	S1—O8	1.471 (3)
La1—O1W	2.496 (3)	S1—O5	1.472 (3)
La1—O8ⁱⁱ	2.521 (3)	S1—O6	1.488 (3)
La1—O1ⁱⁱⁱ	2.533 (3)	S2—O1	1.468 (3)
La1—O2^iv	2.563 (3)	S2—O2	1.470 (3)
La1—O3	2.596 (3)	S2—O4	1.480 (3)
La1—O5	2.612 (3)	S2—O3	1.490 (3)
La1—O4	2.614 (3)	O1W—H11	0.845 (10)
La1—O6	2.637 (3)	O1W—H21	0.844 (10)
S1—O7	1.465 (3)

O7ⁱ—La1—O1W	82.44 (12)	O7ⁱ—La1—O6	99.16 (10)
O7ⁱ—La1—O8ⁱⁱ	143.78 (10)	O1W—La1—O6	145.43 (9)
O1W—La1—O8ⁱⁱ	71.36 (10)	O8ⁱⁱ—La1—O6	89.43 (9)
O7ⁱ—La1—O1ⁱⁱⁱ	71.36 (10)	O1ⁱⁱⁱ—La1—O6	70.57 (9)
O1W—La1—O1ⁱⁱⁱ	139.83 (10)	O2^iv—La1—O6	71.00 (9)
O8ⁱⁱ—La1—O1ⁱⁱⁱ	143.55 (9)	O3—La1—O6	124.69 (8)
O7ⁱ—La1—O2^iv	72.90 (10)	O5—La1—O6	53.55 (8)
O1W—La1—O2^iv	76.67 (10)	O4—La1—O6	144.28 (9)
O8ⁱⁱ—La1—O2^iv	76.96 (10)	O7—S1—O8	109.04 (17)
O1ⁱⁱⁱ—La1—O2^iv	121.24 (9)	O7—S1—O5	110.89 (19)
O7ⁱ—La1—O3	127.89 (10)	O8—S1—O5	110.49 (17)
O1W—La1—O3	76.32 (10)	O7—S1—O6	110.19 (18)
O8ⁱⁱ—La1—O3	70.11 (9)	O8—S1—O6	110.17 (16)
O1ⁱⁱⁱ—La1—O3	96.07 (9)	O5—S1—O6	106.04 (16)
O2^iv—La1—O3	142.55 (9)	O7—S1—La1	119.80 (13)
O7ⁱ—La1—O5	140.16 (10)	O8—S1—La1	131.15 (12)
O1W—La1—O5	137.02 (11)	O5—S1—La1	52.71 (11)
O8ⁱⁱ—La1—O5	71.62 (9)	O6—S1—La1	53.78 (11)
O1ⁱⁱⁱ—La1—O5	72.00 (9)	O1—S2—O2	109.67 (16)
O2^iv—La1—O5	114.84 (9)	O1—S2—O4	111.40 (17)
O3—La1—O5	71.17 (8)	O2—S2—O4	111.52 (17)
O7ⁱ—La1—O4	74.43 (10)	O1—S2—O3	109.85 (16)
O1W—La1—O4	69.69 (10)	O2—S2—O3	109.59 (17)
O8ⁱⁱ—La1—O4	116.81 (9)	O4—S2—O3	104.70 (16)
O1ⁱⁱⁱ—La1—O4	74.17 (9)	La1—O1W—H11	128 (4)
O2^iv—La1—O4	135.44 (9)	La1—O1W—H21	119 (4)
O3—La1—O4	53.65 (8)	H11—O1W—H21	112 (3)
O5—La1—O4	109.69 (9)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+2, −y+2, −z+1; (iii) −x+1, −y+2, −z; (iv) x, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O3^v	0.84 (5)	1.94 (5)	2.717 (5)	153 (5)
O1W—H21···O6^vi	0.85 (3)	1.95 (3)	2.778 (4)	168 (5)
N1···O1^vii			2.942 (5)
N1···O6^vi			3.036 (5)
N1···O3^viii			2.914 (5)
N1···O8ⁱ			2.943 (5)
N1···O5ⁱⁱⁱ			2.865 (5)
N1···O4			2.866 (5)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+2, −z; (v) −x+2, y−1/2, −z+1/2; (vi) x, −y+3/2, z−1/2; (vii) −x+1, y−1/2, −z−1/2; (viii) x−1, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O3ⁱ	0.84 (5)	1.94 (5)	2.717 (5)	153 (5)
O1W—H21···O6ⁱⁱ	0.85 (3)	1.95 (3)	2.778 (4)	168 (5)
N1···O1ⁱⁱⁱ	.	.	2.942 (5)	.
N1···O6ⁱⁱ	.	.	3.036 (5)	.
N1···O3^iv	.	.	2.914 (5)	.
N1···O8^v	.	.	2.943 (5)	.
N1···O5^vi	.	.	2.865 (5)	.
N1···O4	.	.	2.866 (5)	.

Symmetry codes: (i) −x+2, y−1/2, −z+1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z−1/2; (iv) x−1, −y+3/2, z−1/2; (v) −x+1, y−1/2, −z+1/2; (vi) −x+1, −y+2, −z.

Experimental details

Crystal data
Chemical formula	NH₄[La(SO₄)₂(H₂O)]
M_r	367.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	8.4919 (16), 9.978 (2), 11.9268 (19)
β (°)	128.511 (10)
V (Å³)	790.7 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.96
Crystal size (mm)	0.30 × 0.20 × 0.10 × 0.10 (radius)

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	For a sphere (Dwiggins, 1975)
T_min, T_max	0.419, 0.431
No. of measured, independent and observed [I > 2σ(I)] reflections	2414, 2414, 2362
R_int	0.0000
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.081, 1.26
No. of reflections	2414
No. of parameters	124
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.81, −1.48

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 1999), WinGX (Farrugia, 2012).

Acknowledgements

Technical support (X-ray measurements) from Université Henri Poincaré, Nancy 1, is gratefully acknowledged.

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Volume 71| Part 6| June 2015| Pages 663-666

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