Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024555/wm2108sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024555/wm2108Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (S-O) = 0.007 Å
- R factor = 0.034
- wR factor = 0.068
- Data-to-parameter ratio = 10.3
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT416_ALERT_2_B Short Intra D-H..H-D H5 .. H6 .. 1.51 Ang. PLAT417_ALERT_2_B Short Inter D-H..H-D H8 .. H8 .. 1.45 Ang. PLAT417_ALERT_2_B Short Inter D-H..H-D H9 .. H11 .. 1.90 Ang. PLAT417_ALERT_2_B Short Inter D-H..H-D H1 .. H12 .. 2.06 Ang. PLAT420_ALERT_2_B D-H Without Acceptor O12 - H12 ... ? PLAT707_ALERT_1_B D...A Calc 2.729(11), Rep 2.705(9), Dev.. 2.18 Sigma O11 -O7 1.555 2.667
Alert level C CRYSC01_ALERT_1_C The word below has not been recognised as a standard identifier. transparent CRYSC01_ALERT_1_C No recognised colour has been given for crystal colour. PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT213_ALERT_2_C Atom O6 has ADP max/min Ratio ............. 3.50 prola PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.89 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O5 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O7 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Ce1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for S2 PLAT707_ALERT_1_C D...A Calc 2.896(13), Rep 2.918(14), Dev.. 1.69 Sigma N1 -O12 1.555 1.555 PLAT755_ALERT_4_C D-H Calc 0.79000, Rep 0.793(9) ...... Senseless su N1 -H1 1.555 1.555 PLAT755_ALERT_4_C D-H Calc 0.82000, Rep 0.823(9) ...... Senseless su N1 -H3 1.555 1.555 PLAT755_ALERT_4_C D-H Calc 1.00000, Rep 1.003(10) ...... Senseless su N1 -H4 1.555 1.555 PLAT755_ALERT_4_C D-H Calc 0.99000, Rep 0.992(7) ...... Senseless su O9 -H5 1.555 1.555 PLAT755_ALERT_4_C D-H Calc 0.84000, Rep 0.845(7) ...... Senseless su O9 -H6 1.555 1.555 PLAT755_ALERT_4_C D-H Calc 0.82000, Rep 0.815(7) ...... Senseless su O11 -H9 1.555 1.555 PLAT755_ALERT_4_C D-H Calc 0.82000, Rep 0.824(6) ...... Senseless su O11 -H10 1.555 1.555 PLAT756_ALERT_4_C H...A Calc 2.17000, Rep 2.167(10) ...... Senseless su H1 -O12 1.555 1.555 PLAT756_ALERT_4_C H...A Calc 2.09000, Rep 2.088(6) ...... Senseless su H3 -O4 1.555 1.555 PLAT756_ALERT_4_C H...A Calc 2.16000, Rep 2.157(6) ...... Senseless su H4 -O2 1.555 1.655 PLAT756_ALERT_4_C H...A Calc 2.07000, Rep 2.068(7) ...... Senseless su H5 -O7 1.555 1.555 PLAT756_ALERT_4_C H...A Calc 2.05000, Rep 2.052(6) ...... Senseless su H6 -O1 1.555 4.555 PLAT756_ALERT_4_C H...A Calc 1.97000, Rep 1.969(9) ...... Senseless su H9 -O12 1.555 2.767 PLAT756_ALERT_4_C H...A Calc 1.91000, Rep 1.906(7) ...... Senseless su H10 -O7 1.555 2.667 PLAT758_ALERT_4_C D-H..A Calc 153.00, Rep 153.1(7) ...... Senseless su N1 -H1 -O12 1.555 1.555 1.555 PLAT758_ALERT_4_C D-H..A Calc 166.00, Rep 165.6(7) ...... Senseless su N1 -H3 -O4 1.555 1.555 1.555 PLAT758_ALERT_4_C D-H..A Calc 156.00, Rep 156.2(5) ...... Senseless su O9 -H5 -O7 1.555 1.555 1.555
0 ALERT level A = In general: serious problem 6 ALERT level B = Potentially serious problem 27 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 11 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 17 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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+.
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.
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).
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).
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.
NH4Ce(SO4)2·4H2O | F(000) = 820 |
Mr = 422.35 | Dx = 2.533 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6883 reflections |
a = 6.673 (2) Å | θ = 1.8–25.8° |
b = 18.9920 (5) Å | µ = 4.55 mm−1 |
c = 8.808 (2) Å | T = 298 K |
β = 97.29 (3)° | Prism, transparent |
V = 1107.3 (4) Å3 | 0.10 × 0.08 × 0.06 mm |
Z = 4 |
Nonius Kappa CCD area-detector diffractometer | 1489 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.042 |
φ rotation scans with 2° steps | θmax = 30.0°, θmin = 2.2° |
Absorption correction: multi-scan (MULABS in PLATON; Spek, 1998) | h = −9→9 |
Tmin = 0.667, Tmax = 0.772 | k = −26→26 |
6836 measured reflections | l = −12→12 |
3225 independent reflections |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | All 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 parameters | Δρmax = 1.00 e Å−3 |
0 restraints | Δρmin = −2.62 e Å−3 |
NH4Ce(SO4)2·4H2O | V = 1107.3 (4) Å3 |
Mr = 422.35 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.673 (2) Å | µ = 4.55 mm−1 |
b = 18.9920 (5) Å | T = 298 K |
c = 8.808 (2) Å | 0.10 × 0.08 × 0.06 mm |
β = 97.29 (3)° |
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 = 0.772 | Rint = 0.042 |
6836 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.068 | All H-atom parameters refined |
S = 1.05 | Δρmax = 1.00 e Å−3 |
1489 reflections | Δρmin = −2.62 e Å−3 |
145 parameters |
x | y | z | Uiso*/Ueq | ||
Ce1 | 0.64763 (5) | 0.37838 (2) | 0.78484 (4) | 0.0152 | |
S1 | 0.6215 (3) | 0.22283 (10) | 0.9125 (2) | 0.0227 | |
S2 | 0.1859 (2) | 0.42436 (10) | 0.7628 (3) | 0.0268 | |
O1 | 0.5880 (11) | 0.1595 (3) | 0.8189 (7) | 0.0339 | |
O2 | 0.4532 (9) | 0.2738 (3) | 0.8726 (8) | 0.0299 | |
O3 | 0.6324 (14) | 0.2963 (4) | 0.5734 (8) | 0.0477 | |
O4 | 0.8046 (9) | 0.2604 (3) | 0.8841 (8) | 0.0317 | |
O5 | 0.2958 (9) | 0.3919 (4) | 0.6427 (7) | 0.0421 | |
O6 | 0.1221 (12) | 0.4953 (4) | 0.7296 (18) | 0.0859 | |
O7 | 0.3358 (10) | 0.4220 (5) | 0.9017 (9) | 0.0481 | |
O8 | 0.0153 (8) | 0.3808 (4) | 0.7888 (9) | 0.0384 | |
O9 | 0.7475 (12) | 0.3922 (4) | 1.0692 (7) | 0.0424 | |
O10 | 0.6715 (11) | 0.4456 (4) | 0.5367 (8) | 0.0374 | |
O11 | 0.6946 (14) | 0.5064 (4) | 0.8336 (8) | 0.0433 | |
N1 | 1.1550 (14) | 0.2781 (5) | 1.1103 (10) | 0.0465 | |
O12 | 1.1383 (12) | 0.3893 (5) | 1.3333 (11) | 0.0566 | |
H1 | 1.1104 | 0.3072 | 1.1611 | 0.0500* | |
H2 | 1.1757 | 0.2387 | 1.1504 | 0.0500* | |
H3 | 1.0699 | 0.2738 | 1.0347 | 0.0500* | |
H4 | 1.2787 | 0.2884 | 1.0602 | 0.0500* | |
H7 | 0.7780 | 0.4503 | 0.4859 | 0.0500* | |
H5 | 0.6188 | 0.3895 | 0.9994 | 0.0500* | |
H6 | 0.7483 | 0.3625 | 1.1406 | 0.0500* | |
H8 | 0.5980 | 0.4851 | 0.5266 | 0.0500* | |
H9 | 0.7458 | 0.5349 | 0.7810 | 0.0500* | |
H10 | 0.6884 | 0.5296 | 0.9120 | 0.0500* | |
H11 | 1.2719 | 0.3790 | 1.3297 | 0.0500* | |
H12 | 1.0854 | 0.3554 | 1.3679 | 0.0500* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ce1 | 0.01392 (14) | 0.01666 (15) | 0.01504 (14) | −0.0010 (2) | 0.00201 (8) | −0.0016 (2) |
S1 | 0.0303 (8) | 0.0188 (8) | 0.0188 (7) | −0.0041 (6) | 0.0027 (6) | 0.0023 (6) |
S2 | 0.0159 (7) | 0.0214 (8) | 0.0439 (11) | 0.0001 (6) | 0.0071 (7) | 0.0021 (8) |
O1 | 0.051 (4) | 0.028 (3) | 0.023 (3) | −0.007 (3) | 0.005 (2) | −0.001 (2) |
O2 | 0.026 (2) | 0.028 (3) | 0.037 (3) | −0.005 (2) | 0.010 (2) | 0.004 (2) |
O3 | 0.096 (6) | 0.022 (3) | 0.024 (3) | 0.003 (4) | 0.004 (4) | −0.008 (3) |
O4 | 0.027 (3) | 0.024 (3) | 0.042 (4) | −0.001 (2) | 0.000 (2) | 0.009 (2) |
O5 | 0.022 (2) | 0.081 (6) | 0.023 (3) | 0.021 (3) | 0.000 (2) | 0.006 (3) |
O6 | 0.033 (4) | 0.027 (4) | 0.199 (14) | 0.011 (3) | 0.019 (5) | 0.034 (5) |
O7 | 0.028 (3) | 0.071 (5) | 0.047 (4) | 0.002 (3) | 0.009 (3) | −0.036 (4) |
O8 | 0.017 (2) | 0.035 (3) | 0.064 (4) | −0.011 (3) | 0.008 (2) | 0.008 (4) |
O9 | 0.054 (4) | 0.050 (5) | 0.021 (3) | −0.016 (3) | −0.005 (2) | 0.005 (3) |
O10 | 0.047 (4) | 0.036 (3) | 0.030 (3) | −0.008 (3) | 0.009 (3) | 0.012 (3) |
O11 | 0.076 (5) | 0.028 (3) | 0.031 (3) | −0.009 (3) | 0.023 (3) | −0.010 (2) |
N1 | 0.044 (4) | 0.053 (5) | 0.038 (4) | 0.020 (4) | −0.011 (3) | 0.003 (4) |
O12 | 0.042 (4) | 0.069 (6) | 0.055 (4) | 0.005 (4) | −0.009 (3) | 0.022 (4) |
Ce1—O8i | 2.450 (5) | S2—O6 | 1.432 (8) |
Ce1—S1 | 3.1736 (18) | S2—O7 | 1.479 (8) |
Ce1—O2 | 2.545 (6) | S2—O8 | 1.449 (6) |
Ce1—O3 | 2.420 (7) | O9—H5 | 0.992 |
Ce1—O4 | 2.578 (6) | O9—H6 | 0.845 |
Ce1—O5 | 2.530 (6) | O10—H7 | 0.891 |
Ce1—O7 | 2.573 (6) | O10—H8 | 0.893 |
Ce1—O9 | 2.523 (6) | O11—H9 | 0.815 |
Ce1—O10 | 2.554 (6) | O11—H10 | 0.824 |
Ce1—O11 | 2.482 (7) | N1—H1 | 0.793 |
Ce1—H5 | 1.935 | N1—H2 | 0.831 |
S1—O3ii | 1.456 (7) | N1—H3 | 0.823 |
S1—O1 | 1.459 (6) | N1—H4 | 1.003 |
S1—O2 | 1.491 (6) | O12—H11 | 0.917 |
S1—O4 | 1.464 (6) | O12—H12 | 0.812 |
S2—O5 | 1.495 (6) | ||
O8i—Ce1—S1 | 96.44 (18) | O9—Ce1—O10 | 139.5 (2) |
O8i—Ce1—O2 | 123.9 (2) | O5—Ce1—O11 | 94.3 (3) |
S1—Ce1—O2 | 27.51 (14) | O7—Ce1—O11 | 72.9 (3) |
O8i—Ce1—O3 | 88.1 (3) | O9—Ce1—O11 | 73.4 (2) |
S1—Ce1—O3 | 70.99 (17) | O10—Ce1—O11 | 68.8 (2) |
O2—Ce1—O3 | 76.0 (2) | O5—Ce1—H5 | 105.736 |
O8i—Ce1—O4 | 69.4 (2) | O7—Ce1—H5 | 52.304 |
S1—Ce1—O4 | 27.05 (13) | O9—Ce1—H5 | 20.850 |
O2—Ce1—O4 | 54.6 (2) | O10—Ce1—H5 | 143.699 |
O3—Ce1—O4 | 71.1 (2) | O11—Ce1—H5 | 75.529 |
O8i—Ce1—O5 | 150.5 (2) | Ce1—S1—O3ii | 125.4 (3) |
S1—Ce1—O5 | 100.40 (19) | Ce1—S1—O1 | 125.3 (3) |
O2—Ce1—O5 | 75.7 (2) | O3ii—S1—O1 | 109.2 (4) |
O3—Ce1—O5 | 74.9 (3) | Ce1—S1—O2 | 52.1 (2) |
O4—Ce1—O5 | 124.6 (2) | O3ii—S1—O2 | 109.6 (4) |
O8i—Ce1—O7 | 148.0 (2) | O1—S1—O2 | 110.2 (4) |
S1—Ce1—O7 | 94.3 (2) | Ce1—S1—O4 | 53.2 (2) |
O2—Ce1—O7 | 70.2 (3) | O3ii—S1—O4 | 110.4 (5) |
O3—Ce1—O7 | 123.9 (3) | O1—S1—O4 | 112.1 (4) |
O4—Ce1—O7 | 117.3 (3) | O2—S1—O4 | 105.2 (3) |
O8i—Ce1—O9 | 81.1 (3) | O5—S2—O6 | 113.8 (7) |
S1—Ce1—O9 | 76.39 (17) | O5—S2—O7 | 103.4 (3) |
O2—Ce1—O9 | 82.0 (2) | O6—S2—O7 | 110.5 (7) |
O3—Ce1—O9 | 144.2 (2) | O5—S2—O8 | 110.0 (5) |
O4—Ce1—O9 | 73.1 (2) | O6—S2—O8 | 110.5 (5) |
O8i—Ce1—O10 | 80.3 (2) | O7—S2—O8 | 108.3 (5) |
S1—Ce1—O10 | 141.35 (17) | Ce1—O2—S1 | 100.4 (3) |
O2—Ce1—O10 | 137.7 (2) | Ce1—O3—S1iii | 154.4 (5) |
O3—Ce1—O10 | 70.4 (2) | Ce1—O4—S1 | 99.8 (3) |
O4—Ce1—O10 | 131.1 (2) | Ce1—O5—S2 | 101.5 (3) |
O8i—Ce1—O11 | 82.8 (3) | Ce1—O7—S2 | 100.1 (3) |
S1—Ce1—O11 | 149.54 (17) | Ce1iv—O8—S2 | 144.5 (5) |
O2—Ce1—O11 | 140.3 (2) | H5—O9—H6 | 110.455 |
O3—Ce1—O11 | 139.1 (2) | Ce1—O10—H7 | 128.308 |
O4—Ce1—O11 | 139.1 (3) | Ce1—O10—H8 | 114.254 |
O8i—Ce1—H5 | 101.977 | H7—O10—H8 | 109.248 |
S1—Ce1—H5 | 74.861 | H9—O11—H10 | 101.042 |
O2—Ce1—H5 | 70.786 | H1—N1—H2 | 116.347 |
O3—Ce1—H5 | 145.265 | H1—N1—H3 | 104.775 |
O4—Ce1—H5 | 81.389 | H2—N1—H3 | 108.423 |
O5—Ce1—O7 | 54.4 (2) | H1—N1—H4 | 119.964 |
O5—Ce1—O9 | 126.3 (2) | H2—N1—H4 | 105.124 |
O7—Ce1—O9 | 72.2 (3) | H3—N1—H4 | 100.646 |
O5—Ce1—O10 | 71.4 (2) | H11—O12—H12 | 108.302 |
O7—Ce1—O10 | 108.8 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O12 | 0.793 (9) | 2.167 (10) | 2.918 (14) | 153.1 (7) |
N1—H3···O4 | 0.823 (9) | 2.088 (6) | 2.882 (12) | 165.6 (7) |
N1—H4···O2i | 1.003 (10) | 2.157 (6) | 3.067 (11) | 150.0 (6) |
O9—H5···O7 | 0.992 (7) | 2.068 (7) | 2.998 (10) | 156.2 (5) |
O9—H6···O1ii | 0.845 (7) | 2.052 (6) | 2.738 (9) | 138.7 (6) |
O11—H9···O12v | 0.815 (7) | 1.969 (9) | 2.776 (11) | 174.6 (6) |
O11—H10···O7vi | 0.824 (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. |
Experimental details
Crystal data | |
Chemical formula | NH4Ce(SO4)2·4H2O |
Mr | 422.35 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 6.673 (2), 18.9920 (5), 8.808 (2) |
β (°) | 97.29 (3) |
V (Å3) | 1107.3 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.55 |
Crystal size (mm) | 0.10 × 0.08 × 0.06 |
Data collection | |
Diffractometer | Nonius Kappa CCD area-detector |
Absorption correction | Multi-scan (MULABS in PLATON; Spek, 1998) |
Tmin, Tmax | 0.667, 0.772 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 6836, 3225, 1489 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.068, 1.05 |
No. of reflections | 1489 |
No. of parameters | 145 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 1.00, −2.62 |
Computer programs: COLLECT (Nonius, 2001), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS97 (Sheldrick, 1997), CRYSTALS (Betteridge et al., 2003), DIAMOND (Brandenburg & Berndt, 1999), CRYSTALS.
Ce1—O8i | 2.450 (5) | S1—O3ii | 1.456 (7) |
Ce1—O2 | 2.545 (6) | S1—O1 | 1.459 (6) |
Ce1—O3 | 2.420 (7) | S1—O2 | 1.491 (6) |
Ce1—O4 | 2.578 (6) | S1—O4 | 1.464 (6) |
Ce1—O5 | 2.530 (6) | S2—O5 | 1.495 (6) |
Ce1—O7 | 2.573 (6) | S2—O6 | 1.432 (8) |
Ce1—O9 | 2.523 (6) | S2—O7 | 1.479 (8) |
Ce1—O10 | 2.554 (6) | S2—O8 | 1.449 (6) |
Ce1—O11 | 2.482 (7) |
Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O12 | 0.793 (9) | 2.167 (10) | 2.918 (14) | 153.1 (7) |
N1—H3···O4 | 0.823 (9) | 2.088 (6) | 2.882 (12) | 165.6 (7) |
N1—H4···O2i | 1.003 (10) | 2.157 (6) | 3.067 (11) | 150.0 (6) |
O9—H5···O7 | 0.992 (7) | 2.068 (7) | 2.998 (10) | 156.2 (5) |
O9—H6···O1ii | 0.845 (7) | 2.052 (6) | 2.738 (9) | 138.7 (6) |
O11—H9···O12iii | 0.815 (7) | 1.969 (9) | 2.776 (11) | 174.6 (6) |
O11—H10···O7iv | 0.824 (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. |
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).