supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, i144-i145    [ doi:10.1107/S1600536807024555 ]

NH4Ce(SO4)2·4H2O

M. Boujelben, M. Toumi and T. Mhiri

Abstract top

Single crystals of ammonium cerium(III) bis(sulfate) tetrahydrate were grown by slow evaporation of an aqueous sulfate solution containing NH4+ and Ce3+. The crystal structure is isotypic with other ammonium rare earth sulfates of the type NH4RE(SO4)2·4H2O where complete single-crystal stucture analyses have already been performed for RE = La, Sm and Tb. The Ce3+ cation is coordinated by nine O atoms, six of which belong to SO4 groups and three to H2O molecules. The rare earth cation is in the centre of a distorted tricapped trigonal prism. The structure is held together by moderate hydrogen bonds between the tetrahedral SO42- and NH4+ groups and the water molecules.

Comment top

Compounds of the type MCe(SO4)2.4H2O (M = K, Na, Ag) have already been prepared and characterized by X-ray powder diffraction methods. Although space group and cell parameters were determined (Shan et al., 1998; Blackburn et al., 1995; Blackburn et al., 1994, Kepert et al., 1999), more detailed structural data were not provided. Our particular interest concerned the structure determination and hydrogen bonding of NH4CeIII(SO4)2.4H2O.

The structural arrangement of the title compound (Fig. 1) is very similar to that of the isotypic structures of NH4RE(SO4)2.4H2O with RE = Sm (Eriksson et al., 1974), La and Tb (Cameron et al., 1999). The Ce3+ cation coordinates to nine O atoms, six of which belong to SO4 groups and three to H2O molecules. The coordination polyhedron is a distorted tricapped trigonal prism, with O10, O11 and O5 as the top face, O9, O4 and O2 as bottom face and O3, O7 and O8 as capping atoms. A similar coordination of rare earth cations has been observed for TlLa(SO4)2.2H2O (Kaučič et al., 1985), and for (NH4)8Ce2(SO4)8.4H2O (Shan & Huang, 1998). In the La compound, the rare earth cation coordinates to seven O atoms belonging to sulfate groups and to O atoms of two water molecules, whereas in the Ce compound the coordination sphere of the Ce cation solely consists of sulfate O atoms. In NaCe(SO4)2.H2O (Blackburn et al., 1995), AgCe(SO4)2.H2O (Audebrand et al., 1998) and NaLa(SO4)2.H2O (Blackburn et al., 1994) only one water O atom is involved in the oxygen coordination sphere of the rare earth cations.

In the title compound the Ce—O bond lengths range from 2.420 (7) to 2.578 (6) Å [average 2.517 (4) Å; Table 1] and are comparable with those found in NaCe(SO4)2.H2O. For (NH4)8Ce2(SO4)8.4H2O, shorter Ce—O distances are observed that range from 2.325 (2) to 2.478 (2) Å [average 2.395 (6) Å], caused by the higher oxidation state of Ce4+ in this compound and thus a smaller ionic radius. The S—O bond distances in the SO4 tetrahedron are in the usual range with an average of 1.467 Å for S1 and of 1.463 Å for S2 (Table 1).

The water molecules, NH4+ cations and SO42- anions are interconnected via hydrogen bonds of medium strength, with donator acceptor distances in the range 2.705 (9) to 3.067 (11) Å (Table 2).

Related literature top

The structural arrangement of the title compound is comparable with that of the isotypic compounds NH4RE(SO4)2.4H2O with RE = Sm (Eriksson et al., 1974), La and Tb (Kepert et al., 1999). Similar coordination polyhedra around the rare earth metal cation are observed for TlLa(SO4)2.2H2O (Kaučič et al., 1985), (NH4)8Ce2(SO4)8.4H2O (Shan & Huang, 1998), NaCe(SO4)2.H2O (Blackburn & Gerkin, 1995), AgCe(SO4)2.H2O (Audebrand et al., 1998) and NaLa(SO4)2.H2O (Blackburn & Gerkin, 1994).

For related literature, see: Cameron (1999).

Experimental top

Aqueous solutions of Ce(SO4)2.4H2O, NH4CN and NH4Cl were mixed in the molar ratio 1:0.5:0.5 which resulted in a white precipitate. After filtration, the remaining solution was allowed to evaporate. Within a few days small transparent prismatic crystals of NH4Ce(SO4)2.4H2O were obtained, indicating the reduction of Ce4+ to Ce3+.

Refinement top

All H atoms were found in difference Fourier maps and were refined freely. The highest peak is located 0.52 Å from O11 and the deepest hole 0.30 Å from H10.

Computing details top

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: CRYSTALS.

Figures top
[Figure 1] Fig. 1. Projection of the structure along [100]. [Ce(H2O)3O6] polyhedra are yellow, SO4 tetrahedra are green, O, N and H atoms are displayed as red, blue and white spheres. Hydrogen bonds are indicated with dashed lines.
ammonium cerium(III) bis(sulfate) tetrahydrate top
Crystal data top
NH4Ce(SO4)2·4H2OF(000) = 820
Mr = 422.35Dx = 2.533 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6883 reflections
a = 6.673 (2) Åθ = 1.8–25.8°
b = 18.9920 (5) ŵ = 4.55 mm−1
c = 8.808 (2) ÅT = 298 K
β = 97.29 (3)°Prism, transparent
V = 1107.3 (4) Å30.10 × 0.08 × 0.06 mm
Z = 4
Data collection top
Nonius Kappa CCD area-detector
diffractometer		1489 reflections with I > 3σ(I)
graphiteRint = 0.042
φ rotation scans with 2° stepsθmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 1998)		h = −9→9
Tmin = 0.667, Tmax = 0.772k = −26→26
6836 measured reflectionsl = −12→12
3225 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068All H-atom parameters refined
S = 1.05 Method, part 1, Chebychev polynomial, (Watkin, 1994; Prince, 1982) [weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = robust weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 0.119E + 04 -0.128E + 04 956.
Prince, E. (1982). Mathematical Techniques in Crystallography and Materials Science. New York: Springer-Verlag.
Watkin, D. J. (1994). Acta Cryst. A50, 411–437.
1489 reflections(Δ/σ)max = 0.001
145 parametersΔρmax = 1.00 e Å−3
0 restraintsΔρmin = −2.62 e Å−3
Crystal data top
NH4Ce(SO4)2·4H2OV = 1107.3 (4) Å3
Mr = 422.35Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.673 (2) ŵ = 4.55 mm−1
b = 18.9920 (5) ÅT = 298 K
c = 8.808 (2) Å0.10 × 0.08 × 0.06 mm
β = 97.29 (3)°
Data collection top
Nonius Kappa CCD area-detector
diffractometer		3225 independent reflections
Absorption correction: multi-scan
(MULABS in PLATON; Spek, 1998)		1489 reflections with I > 3σ(I)
Tmin = 0.667, Tmax = 0.772Rint = 0.042
6836 measured reflectionsθmax = 30.0°
Refinement top
R[F2 > 2σ(F2)] = 0.034All H-atom parameters refined
wR(F2) = 0.068Δρmax = 1.00 e Å−3
S = 1.05Δρmin = −2.62 e Å−3
1489 reflectionsAbsolute structure: ?
145 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ce10.64763 (5)0.37838 (2)0.78484 (4)0.0152
S10.6215 (3)0.22283 (10)0.9125 (2)0.0227
S20.1859 (2)0.42436 (10)0.7628 (3)0.0268
O10.5880 (11)0.1595 (3)0.8189 (7)0.0339
O20.4532 (9)0.2738 (3)0.8726 (8)0.0299
O30.6324 (14)0.2963 (4)0.5734 (8)0.0477
O40.8046 (9)0.2604 (3)0.8841 (8)0.0317
O50.2958 (9)0.3919 (4)0.6427 (7)0.0421
O60.1221 (12)0.4953 (4)0.7296 (18)0.0859
O70.3358 (10)0.4220 (5)0.9017 (9)0.0481
O80.0153 (8)0.3808 (4)0.7888 (9)0.0384
O90.7475 (12)0.3922 (4)1.0692 (7)0.0424
O100.6715 (11)0.4456 (4)0.5367 (8)0.0374
O110.6946 (14)0.5064 (4)0.8336 (8)0.0433
N11.1550 (14)0.2781 (5)1.1103 (10)0.0465
O121.1383 (12)0.3893 (5)1.3333 (11)0.0566
H11.11040.30721.16110.0500*
H21.17570.23871.15040.0500*
H31.06990.27381.03470.0500*
H41.27870.28841.06020.0500*
H70.77800.45030.48590.0500*
H50.61880.38950.99940.0500*
H60.74830.36251.14060.0500*
H80.59800.48510.52660.0500*
H90.74580.53490.78100.0500*
H100.68840.52960.91200.0500*
H111.27190.37901.32970.0500*
H121.08540.35541.36790.0500*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ce10.01392 (14)0.01666 (15)0.01504 (14)−0.0010 (2)0.00201 (8)−0.0016 (2)
S10.0303 (8)0.0188 (8)0.0188 (7)−0.0041 (6)0.0027 (6)0.0023 (6)
S20.0159 (7)0.0214 (8)0.0439 (11)0.0001 (6)0.0071 (7)0.0021 (8)
O10.051 (4)0.028 (3)0.023 (3)−0.007 (3)0.005 (2)−0.001 (2)
O20.026 (2)0.028 (3)0.037 (3)−0.005 (2)0.010 (2)0.004 (2)
O30.096 (6)0.022 (3)0.024 (3)0.003 (4)0.004 (4)−0.008 (3)
O40.027 (3)0.024 (3)0.042 (4)−0.001 (2)0.000 (2)0.009 (2)
O50.022 (2)0.081 (6)0.023 (3)0.021 (3)0.000 (2)0.006 (3)
O60.033 (4)0.027 (4)0.199 (14)0.011 (3)0.019 (5)0.034 (5)
O70.028 (3)0.071 (5)0.047 (4)0.002 (3)0.009 (3)−0.036 (4)
O80.017 (2)0.035 (3)0.064 (4)−0.011 (3)0.008 (2)0.008 (4)
O90.054 (4)0.050 (5)0.021 (3)−0.016 (3)−0.005 (2)0.005 (3)
O100.047 (4)0.036 (3)0.030 (3)−0.008 (3)0.009 (3)0.012 (3)
O110.076 (5)0.028 (3)0.031 (3)−0.009 (3)0.023 (3)−0.010 (2)
N10.044 (4)0.053 (5)0.038 (4)0.020 (4)−0.011 (3)0.003 (4)
O120.042 (4)0.069 (6)0.055 (4)0.005 (4)−0.009 (3)0.022 (4)
Geometric parameters (Å, °) top
Ce1—O8i2.450 (5)S2—O61.432 (8)
Ce1—S13.1736 (18)S2—O71.479 (8)
Ce1—O22.545 (6)S2—O81.449 (6)
Ce1—O32.420 (7)O9—H50.992
Ce1—O42.578 (6)O9—H60.845
Ce1—O52.530 (6)O10—H70.891
Ce1—O72.573 (6)O10—H80.893
Ce1—O92.523 (6)O11—H90.815
Ce1—O102.554 (6)O11—H100.824
Ce1—O112.482 (7)N1—H10.793
Ce1—H51.935N1—H20.831
S1—O3ii1.456 (7)N1—H30.823
S1—O11.459 (6)N1—H41.003
S1—O21.491 (6)O12—H110.917
S1—O41.464 (6)O12—H120.812
S2—O51.495 (6)
O8i—Ce1—S196.44 (18)O9—Ce1—O10139.5 (2)
O8i—Ce1—O2123.9 (2)O5—Ce1—O1194.3 (3)
S1—Ce1—O227.51 (14)O7—Ce1—O1172.9 (3)
O8i—Ce1—O388.1 (3)O9—Ce1—O1173.4 (2)
S1—Ce1—O370.99 (17)O10—Ce1—O1168.8 (2)
O2—Ce1—O376.0 (2)O5—Ce1—H5105.736
O8i—Ce1—O469.4 (2)O7—Ce1—H552.304
S1—Ce1—O427.05 (13)O9—Ce1—H520.850
O2—Ce1—O454.6 (2)O10—Ce1—H5143.699
O3—Ce1—O471.1 (2)O11—Ce1—H575.529
O8i—Ce1—O5150.5 (2)Ce1—S1—O3ii125.4 (3)
S1—Ce1—O5100.40 (19)Ce1—S1—O1125.3 (3)
O2—Ce1—O575.7 (2)O3ii—S1—O1109.2 (4)
O3—Ce1—O574.9 (3)Ce1—S1—O252.1 (2)
O4—Ce1—O5124.6 (2)O3ii—S1—O2109.6 (4)
O8i—Ce1—O7148.0 (2)O1—S1—O2110.2 (4)
S1—Ce1—O794.3 (2)Ce1—S1—O453.2 (2)
O2—Ce1—O770.2 (3)O3ii—S1—O4110.4 (5)
O3—Ce1—O7123.9 (3)O1—S1—O4112.1 (4)
O4—Ce1—O7117.3 (3)O2—S1—O4105.2 (3)
O8i—Ce1—O981.1 (3)O5—S2—O6113.8 (7)
S1—Ce1—O976.39 (17)O5—S2—O7103.4 (3)
O2—Ce1—O982.0 (2)O6—S2—O7110.5 (7)
O3—Ce1—O9144.2 (2)O5—S2—O8110.0 (5)
O4—Ce1—O973.1 (2)O6—S2—O8110.5 (5)
O8i—Ce1—O1080.3 (2)O7—S2—O8108.3 (5)
S1—Ce1—O10141.35 (17)Ce1—O2—S1100.4 (3)
O2—Ce1—O10137.7 (2)Ce1—O3—S1iii154.4 (5)
O3—Ce1—O1070.4 (2)Ce1—O4—S199.8 (3)
O4—Ce1—O10131.1 (2)Ce1—O5—S2101.5 (3)
O8i—Ce1—O1182.8 (3)Ce1—O7—S2100.1 (3)
S1—Ce1—O11149.54 (17)Ce1iv—O8—S2144.5 (5)
O2—Ce1—O11140.3 (2)H5—O9—H6110.455
O3—Ce1—O11139.1 (2)Ce1—O10—H7128.308
O4—Ce1—O11139.1 (3)Ce1—O10—H8114.254
O8i—Ce1—H5101.977H7—O10—H8109.248
S1—Ce1—H574.861H9—O11—H10101.042
O2—Ce1—H570.786H1—N1—H2116.347
O3—Ce1—H5145.265H1—N1—H3104.775
O4—Ce1—H581.389H2—N1—H3108.423
O5—Ce1—O754.4 (2)H1—N1—H4119.964
O5—Ce1—O9126.3 (2)H2—N1—H4105.124
O7—Ce1—O972.2 (3)H3—N1—H4100.646
O5—Ce1—O1071.4 (2)H11—O12—H12108.302
O7—Ce1—O10108.8 (3)
Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z+1/2; (iii) x, −y+1/2, z−1/2; (iv) x−1, y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O120.793 (9)2.167 (10)2.918 (14)153.1 (7)
N1—H3···O40.823 (9)2.088 (6)2.882 (12)165.6 (7)
N1—H4···O2i1.003 (10)2.157 (6)3.067 (11)150.0 (6)
O9—H5···O70.992 (7)2.068 (7)2.998 (10)156.2 (5)
O9—H6···O1ii0.845 (7)2.052 (6)2.738 (9)138.7 (6)
O11—H9···O12v0.815 (7)1.969 (9)2.776 (11)174.6 (6)
O11—H10···O7vi0.824 (6)1.906 (7)2.705 (9)176.1 (6)
Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z+1/2; (v) −x+2, −y+1, −z+2; (vi) −x+1, −y+1, −z+2.
Table 1
Selected geometric parameters (Å) top
Ce1—O8i2.450 (5)S1—O3ii1.456 (7)
Ce1—O22.545 (6)S1—O11.459 (6)
Ce1—O32.420 (7)S1—O21.491 (6)
Ce1—O42.578 (6)S1—O41.464 (6)
Ce1—O52.530 (6)S2—O51.495 (6)
Ce1—O72.573 (6)S2—O61.432 (8)
Ce1—O92.523 (6)S2—O71.479 (8)
Ce1—O102.554 (6)S2—O81.449 (6)
Ce1—O112.482 (7)
Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O120.793 (9)2.167 (10)2.918 (14)153.1 (7)
N1—H3···O40.823 (9)2.088 (6)2.882 (12)165.6 (7)
N1—H4···O2i1.003 (10)2.157 (6)3.067 (11)150.0 (6)
O9—H5···O70.992 (7)2.068 (7)2.998 (10)156.2 (5)
O9—H6···O1ii0.845 (7)2.052 (6)2.738 (9)138.7 (6)
O11—H9···O12iii0.815 (7)1.969 (9)2.776 (11)174.6 (6)
O11—H10···O7iv0.824 (6)1.906 (7)2.705 (9)176.1 (6)
Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z+1/2; (iii) −x+2, −y+1, −z+2; (iv) −x+1, −y+1, −z+2.
Acknowledgements top

The authors thank Marc Leblanc for the data collection.

references
References top

Audebrand, N., Auffrédic, J. P. & Louër, D. (1998). Z. Kristallogr. New Cryst. Struct. 213, 453–???. [Please give final page number]

Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487–?.

Blackburn, A. C. & Gerkin, R. E. (1994). Acta Cryst. C50, 835–838.

Blackburn, A. C. & Gerkin, R. E. (1995). Acta Cryst. C51, 2215–2218.

Brandenburg, K. & Berndt, M. (1999). DIAMOND. Version 2.1b. Crystal Impact GbR, Bonn, Germany.

Cameron et al. (1999). Please give full details for missing reference.

Eriksson, B., Larson, L. O., Niinistore, L. & Skoglund, U. (1974). Inorg. Chem. 13, 290–295.

Kaučič, V., Bukovec, N. & Golič, Lj. (1985). Acta Cryst. C41, 636–638.

Kepert, C. J., Junk, P. C., Skelton, B. W. & White, A. W. (1999). Aust. J. Chem. 52, 601–615.

Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Shan, Y. & Huang, S. D. (1998). Acta Cryst. C54, 1744–1745.

Sheldrick, G. M. (1997). SHELXS97. University of Göttingen, Germany.

Spek, A. L. (1998). PLATON. University of Utrecht, The Netherlands.