The title compound, Y
2(SO
4)
3·8H
2O, consists of infinite layers parallel to (10
), with [Y(H
2O)
4(SO
4)
3/2] as the unique repeat unit. The layers are linked only by hydrogen bonds of medium strength. The trivalent yttrium cation is coordinated by eight O atoms from four sulfate groups and four water molecules, in the form of a distorted square antiprism [YO
8]. The title compound is isostructural with the well known members of the rare-earth sulfate octahydrate structure type.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (S-O) = 0.003 Å
- R factor = 0.040
- wR factor = 0.095
- Data-to-parameter ratio = 16.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
The crystallization of Y2(SO4)3·8H2O from an aqueous solution of sulfuric acid, yttrium sulfate and ethylenediamine in the molar ratio 1:1:1 was not expected (in our search for double sulfates of ethylenediammonium and trivalent cations). Heating, to 330 K, of the solution involved in the neutralization reaction of sulfuric acid and ethylenediamine is the key to the synthesis of the title compound. It crystallized by slow evaporation of the solvent at room temperature, in the form of colourless flat crystals with dimensions up to 5 mm.
We used geometrical restraints in the refinement calculation of several H atoms. Distances restaints were placed on O1—H12, O2—H21, O2—H22, O3—H31, O3—H32 with a target value of 0.98 (6) Å.
Data collection: MACH3 (Enraf-Nonius, 1993); cell refinement: MACH3; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ATOMS (Dowty, 2002) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
yttrium(III) sulfate octahydrate
top
Crystal data top
H16O20S3Y2 | F(000) = 1208 |
Mr = 610.11 | Dx = 2.524 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 13.4802 (9) Å | θ = 12.5–17.4° |
b = 6.6846 (4) Å | µ = 7.69 mm−1 |
c = 18.216 (1) Å | T = 293 K |
β = 101.977 (7)° | Parallelepiped, colourless |
V = 1605.71 (17) Å3 | 0.25 × 0.23 × 0.19 mm |
Z = 4 | |
Data collection top
Nonius MACH3 diffractometer | 1614 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed X-ray tube | Rint = 0.034 |
Graphite monochromator | θmax = 30.4°, θmin = 3.1° |
ω/2θ scans | h = −18→19 |
Absorption correction: ψ scan MolEN (Fair, 1990) | k = −9→0 |
Tmin = 0.168, Tmax = 0.232 | l = −25→0 |
2498 measured reflections | 3 standard reflections every 60 min |
2424 independent reflections | intensity decay: 2.7% |
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)] = 0.040 | All H-atom parameters refined |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.039P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
2424 reflections | Δρmax = 0.94 e Å−3 |
147 parameters | Δρmin = −0.87 e Å−3 |
5 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Sheldrick (1997b) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0029 (2) |
Crystal data top
H16O20S3Y2 | V = 1605.71 (17) Å3 |
Mr = 610.11 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.4802 (9) Å | µ = 7.69 mm−1 |
b = 6.6846 (4) Å | T = 293 K |
c = 18.216 (1) Å | 0.25 × 0.23 × 0.19 mm |
β = 101.977 (7)° | |
Data collection top
Nonius MACH3 diffractometer | 1614 reflections with I > 2σ(I) |
Absorption correction: ψ scan MolEN (Fair, 1990) | Rint = 0.034 |
Tmin = 0.168, Tmax = 0.232 | 3 standard reflections every 60 min |
2498 measured reflections | intensity decay: 2.7% |
2424 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 5 restraints |
wR(F2) = 0.095 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.94 e Å−3 |
2424 reflections | Δρmin = −0.87 e Å−3 |
147 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 | Uiso*/Ueq | |
Y1 | 0.33379 (3) | 0.02041 (6) | 0.10809 (2) | 0.01068 (13) | |
S1 | 0.21929 (7) | 0.52632 (16) | 0.08912 (6) | 0.0104 (2) | |
S2 | 0.5000 | 0.3198 (2) | 0.2500 | 0.0119 (3) | |
O11 | 0.1622 (2) | 0.5340 (5) | 0.14883 (17) | 0.0200 (7) | |
O12 | 0.2623 (3) | 0.3277 (5) | 0.0828 (2) | 0.0220 (8) | |
O13 | 0.3012 (2) | 0.6751 (5) | 0.10203 (18) | 0.0166 (7) | |
O14 | 0.1489 (2) | 0.5714 (5) | 0.01598 (17) | 0.0160 (7) | |
O21 | 0.4162 (2) | 0.1941 (5) | 0.21213 (18) | 0.0221 (8) | |
O22 | 0.5346 (2) | 0.4450 (5) | 0.19352 (18) | 0.0184 (7) | |
O1 | 0.4840 (3) | −0.1622 (6) | 0.1395 (2) | 0.0302 (10) | |
O2 | 0.4599 (3) | 0.2311 (5) | 0.0638 (2) | 0.0174 (7) | |
O3 | 0.2444 (3) | −0.0158 (6) | 0.20215 (19) | 0.0254 (8) | |
O4 | 0.1582 (3) | −0.0159 (6) | 0.0455 (2) | 0.0172 (7) | |
H11 | 0.495 (4) | −0.263 (8) | 0.157 (3) | 0.06 (1)* | |
H12 | 0.554 (4) | −0.109 (11) | 0.146 (4) | 0.07 (2)* | |
H21 | 0.484 (5) | 0.331 (9) | 0.101 (4) | 0.06 (2)* | |
H22 | 0.498 (4) | 0.180 (10) | 0.039 (4) | 0.06 (2)* | |
H31 | 0.265 (4) | 0.047 (8) | 0.240 (3) | 0.028 (17)* | |
H32 | 0.179 (4) | −0.044 (11) | 0.192 (4) | 0.07 (3)* | |
H41 | 0.136 (5) | 0.064 (9) | 0.021 (3) | 0.03 (2)* | |
H42 | 0.151 (6) | −0.113 (12) | 0.020 (4) | 0.07 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Y1 | 0.01156 (19) | 0.0081 (2) | 0.0123 (2) | −0.00079 (18) | 0.00237 (13) | −0.00024 (18) |
S1 | 0.0118 (5) | 0.0072 (5) | 0.0125 (5) | −0.0011 (4) | 0.0029 (4) | −0.0001 (4) |
S2 | 0.0129 (7) | 0.0093 (7) | 0.0129 (7) | 0.000 | 0.0010 (6) | 0.000 |
O11 | 0.0180 (15) | 0.027 (2) | 0.0161 (16) | −0.0037 (15) | 0.0071 (13) | −0.0003 (15) |
O12 | 0.0263 (19) | 0.0095 (16) | 0.030 (2) | 0.0032 (14) | 0.0049 (16) | −0.0005 (14) |
O13 | 0.0141 (15) | 0.0094 (15) | 0.0258 (19) | −0.0056 (12) | 0.0032 (14) | −0.0013 (13) |
O14 | 0.0169 (16) | 0.0175 (17) | 0.0121 (16) | −0.0007 (13) | −0.0005 (13) | −0.0006 (13) |
O21 | 0.0229 (18) | 0.0265 (19) | 0.0166 (17) | −0.0159 (15) | 0.0036 (14) | −0.0041 (15) |
O22 | 0.0212 (16) | 0.0166 (17) | 0.0192 (17) | −0.0055 (14) | 0.0083 (13) | 0.0031 (14) |
O1 | 0.0146 (19) | 0.0160 (19) | 0.056 (3) | −0.0009 (15) | −0.0007 (18) | 0.0101 (19) |
O2 | 0.0170 (17) | 0.0166 (17) | 0.0198 (18) | −0.0063 (14) | 0.0064 (14) | −0.0043 (14) |
O3 | 0.0218 (17) | 0.042 (2) | 0.0149 (16) | −0.0159 (19) | 0.0089 (14) | −0.0058 (18) |
O4 | 0.0168 (15) | 0.0131 (17) | 0.0208 (17) | 0.0001 (15) | 0.0015 (13) | 0.0015 (16) |
Geometric parameters (Å, º) top
Y1—O12 | 2.275 (3) | S1—O11 | 1.458 (3) |
Y1—O3 | 2.303 (3) | S1—O12 | 1.463 (3) |
Y1—O21 | 2.302 (3) | S1—O13 | 1.468 (3) |
Y1—O1 | 2.332 (4) | S1—O14 | 1.497 (3) |
Y1—O13i | 2.348 (3) | S2—O21iii | 1.461 (3) |
Y1—O14ii | 2.400 (3) | S2—O21 | 1.461 (3) |
Y1—O4 | 2.416 (3) | S2—O22iii | 1.475 (3) |
Y1—O2 | 2.468 (3) | S2—O22 | 1.475 (3) |
| | | |
O12—Y1—O3 | 88.89 (14) | O14ii—Y1—O4 | 78.91 (11) |
O12—Y1—O21 | 79.79 (13) | O12—Y1—O2 | 73.13 (12) |
O3—Y1—O21 | 71.21 (12) | O3—Y1—O2 | 143.62 (13) |
O12—Y1—O1 | 146.31 (13) | O21—Y1—O2 | 74.56 (12) |
O3—Y1—O1 | 108.91 (15) | O1—Y1—O2 | 75.95 (13) |
O21—Y1—O1 | 79.40 (14) | O13i—Y1—O2 | 132.89 (12) |
O12—Y1—O13i | 144.19 (12) | O14ii—Y1—O2 | 68.28 (11) |
O3—Y1—O13i | 79.05 (13) | O4—Y1—O2 | 125.22 (12) |
O21—Y1—O13i | 126.03 (12) | O11—S1—O12 | 111.7 (2) |
O1—Y1—O13i | 68.99 (12) | O11—S1—O13 | 110.64 (19) |
O12—Y1—O14ii | 99.21 (12) | O12—S1—O13 | 109.27 (19) |
O3—Y1—O14ii | 147.38 (12) | O11—S1—O14 | 108.75 (19) |
O21—Y1—O14ii | 141.23 (11) | O12—S1—O14 | 107.54 (19) |
O1—Y1—O14ii | 81.25 (13) | O13—S1—O14 | 108.85 (18) |
O13i—Y1—O14ii | 76.01 (11) | O21iii—S2—O21 | 109.8 (3) |
O12—Y1—O4 | 70.32 (13) | O21iii—S2—O22iii | 108.81 (18) |
O3—Y1—O4 | 74.21 (12) | O21—S2—O22iii | 109.25 (18) |
O21—Y1—O4 | 134.17 (13) | O21iii—S2—O22 | 109.25 (18) |
O1—Y1—O4 | 141.15 (14) | O21—S2—O22 | 108.81 (18) |
O13i—Y1—O4 | 73.95 (12) | O22iii—S2—O22 | 110.9 (3) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, −y+1/2, −z; (iii) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O22i | 0.74 (5) | 2.10 (5) | 2.837 (5) | 172 (5) |
O1—H12···O11iv | 0.99 (5) | 1.74 (5) | 2.711 (5) | 167 (7) |
O2—H21···O22 | 0.96 (5) | 1.84 (5) | 2.766 (5) | 160 (7) |
O2—H22···O14iv | 0.82 (5) | 2.28 (5) | 3.052 (5) | 156 (6) |
O3—H31···O11v | 0.80 (4) | 2.07 (5) | 2.765 (5) | 146 (6) |
O3—H32···O22vi | 0.89 (5) | 1.95 (5) | 2.812 (5) | 163 (7) |
O4—H41···O2ii | 0.72 (6) | 2.26 (6) | 2.968 (5) | 168 (6) |
O4—H42···O14i | 0.79 (8) | 2.11 (8) | 2.809 (5) | 147 (7) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, −y+1/2, −z; (iv) x+1/2, y−1/2, z; (v) −x+1/2, y−1/2, −z+1/2; (vi) x−1/2, y−1/2, z. |
Experimental details
Crystal data |
Chemical formula | H16O20S3Y2 |
Mr | 610.11 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.4802 (9), 6.6846 (4), 18.216 (1) |
β (°) | 101.977 (7) |
V (Å3) | 1605.71 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 7.69 |
Crystal size (mm) | 0.25 × 0.23 × 0.19 |
|
Data collection |
Diffractometer | Nonius MACH3 diffractometer |
Absorption correction | ψ scan MolEN (Fair, 1990) |
Tmin, Tmax | 0.168, 0.232 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2498, 2424, 1614 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.712 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.095, 1.06 |
No. of reflections | 2424 |
No. of parameters | 147 |
No. of restraints | 5 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.94, −0.87 |
Selected bond lengths (Å) topY1—O12 | 2.275 (3) | Y1—O2 | 2.468 (3) |
Y1—O3 | 2.303 (3) | S1—O11 | 1.458 (3) |
Y1—O21 | 2.302 (3) | S1—O12 | 1.463 (3) |
Y1—O1 | 2.332 (4) | S1—O13 | 1.468 (3) |
Y1—O13i | 2.348 (3) | S1—O14 | 1.497 (3) |
Y1—O14ii | 2.400 (3) | S2—O21 | 1.461 (3) |
Y1—O4 | 2.416 (3) | S2—O22 | 1.475 (3) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, −y+1/2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O22i | 0.74 (5) | 2.10 (5) | 2.837 (5) | 172 (5) |
O1—H12···O11iii | 0.99 (5) | 1.74 (5) | 2.711 (5) | 167 (7) |
O2—H21···O22 | 0.96 (5) | 1.84 (5) | 2.766 (5) | 160 (7) |
O2—H22···O14iii | 0.82 (5) | 2.28 (5) | 3.052 (5) | 156 (6) |
O3—H31···O11iv | 0.80 (4) | 2.07 (5) | 2.765 (5) | 146 (6) |
O3—H32···O22v | 0.89 (5) | 1.95 (5) | 2.812 (5) | 163 (7) |
O4—H41···O2ii | 0.72 (6) | 2.26 (6) | 2.968 (5) | 168 (6) |
O4—H42···O14i | 0.79 (8) | 2.11 (8) | 2.809 (5) | 147 (7) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, −y+1/2, −z; (iii) x+1/2, y−1/2, z; (iv) −x+1/2, y−1/2, −z+1/2; (v) x−1/2, y−1/2, z. |
Most of the octahydrates of the rare-earth sulfates (RE2(SO4)3·8H2O) were structurally characterized in the last two decades. The temporary interest in the compounds was based on an erroneous structure determination of Pr2(SO4)3·8H2O in the non-centrosymmetric space group Cc, accompanied by the supposed existence of pyroelectricity of the crystals (Sherry, 1976). About the same time, structure analyses of Sm2(SO4)3·8H2O (Podberezskaya & Borisov, 1976), Yb2(SO4)3·8H2O (Hiltunen & Niinistö, 1976) and Nd2(SO4)3·8H2O (Bartl & Rodek, 1983) showed that the octahydrates belong to one structure type, which crystallizes in the centrosymmetric space group C2/c. In 1981, Ahmed Farag et al. redetermined the structure of Pr2(SO4)3·8H2O and validated the isostructurality of this compound to the members of the octahydrate series. Recently, structure determinations of the Ce, Dy and Lu (Junk et al., 1999) and Er (Wickleder, 1999) compounds expanded the structurally known octahydrate series. Wickleder (2002) gave a summary of all known hydrated rare-earth sulfates. In this paper we present one missing member of this structure type: Y2(SO4)3·8H2O, (I).
Although the calculated bond-valence sum points to a sevenfold coordination (2.969 v.u. up to O4, see Table 1), trivalent yttrium is surrounded by eight O atoms in the range 2.275 (3) to 2.468 (3) Å [dmean = 2.36 (7) Å, 3.267 v.u.] in the form of a distorted square antiprism [YO8]. Four O atoms belong to monodentate sulfate groups, the remaining O atoms are water molecules (Fig.1). Both symmetrically non-equivalent sulfate groups differ in their bridging function. In sulfate group (S1O4)2−, the oxygen atoms O12, O13 and O14 are linked to three Y3+ cations, while (S2O4)2− connects only two Y3+ cations (2 × O21) (Fig. 2). The yttrium coordination can be written as Y(H2O)4(S1O4)3(S2O4). The remaining O atoms (O11 and O22) of both sulfate groups serve as acceptor atoms of hydrogen bonds. The tetrahedral configuration of the sulfate atoms is almost ideal with one exception. As O14 of S1O4 takes part not only in yttrium coordination, but also in hydrogen-bond formation, the bonds O14 forms are weaker than those formed by other O atoms. As a result, the S—O bond distance is elongated. Notwithstanding, all calculated distances and angles fit well into the ranges found for many other structures.
Sulfate groups of first type alternating with [YO8] antiprisms build chains parallel to the b axis sharing common O atoms. Two chains form a strand with opposite stave ends of different kind, [SO4] and [YO8] respectively. In the strand, the yttrium cations are separated by a distance of 5.1322 (9) Å. With sulfur atoms S2 lying on the special Wykoff site 4 e, the S2O4 sulfate groups link the double chains into infinite layers parallel (101) (Fig. 3). Hence the repeated identical unit of the layer has to be written as [Y(H2O)4/1(S1O4)3/3(S2O4)1/2]∞. Hydrogen bonds of medium-to-weak strength in the range 2.711 (5)–3.052 (5) Å interconnect the layers into a three-dimensional framework. The reliability of the hydrogen-bonding data is restricted, because five out of eight hydrogen positions were restrained in bond length during the refinement calculation, though we found an analogous hydrogen-bonding system in known octahydrate rare-earth sulfate structures [RE = Ce and Lu (Junk et al. 1999), Nd (Bartl & Rodek, 1983) and Er (Wickleder, 1999)] in which the hydrogen positions had been determined experimentally.