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Acta Cryst. (2007). E63, i194    [ doi:10.1107/S1600536807056346 ]

Diholmium(III) trisulfate tetrahydrate

W. Zhou, S. Ding, X. Xu and Y. Xu

Abstract top

The single-crystal structure of the title compound {systematic name: poly[tetraaquatri-[mu]2-sulfato-diholmium(III)]}, [Ho2(SO4)3(H2O)4]n, features two-dimensional holmium(III) sulfate layers constructed by eight-coordinate holmium and sulfate groups. The coordination about Ho includes four O atoms from bridging sulfate ions. One S atom makes three S-O-Ho linkages through bridging O atoms, while a second S atom lies on a twofold axis and makes two S-O-Ho linkages. The coordination of each Ho atom is completed by four water molecules, which act as terminal ligands of Ho3+.

Comment top

Over the past decades, the synthesis of new two and three dimensional inorganic materials have received great attention, due to their functional applications. As the building elements of open-frameworks, not only silicon and germanium have been chosen to synthesize new frameworks (Li et al., 1998; Plévert et al., 2001; Xu et al., 2004a; Xu et al.,2004b), but also rare–earth elements. In the last few years, an important advance in solid inorganic materials has been achieved by study of lanthanide sulfates (Zhang et al.,2004; Yuan et al., 2004; Xu et al., 2006a; Xu et al., 2006b; Doran et al., 2002, Xu et al., 2007). In this work, we designed and synthesized the title compound, holmium(3+) sulfate octahydrate, which features a two–dimensional layered framework.

Similar to Eu2(SO4)3(H2O)8 (Xu et al.,2007) and Gd2(SO4)3(H2O)8 (Hummel et al.,1993), the layer of the title compound is constructed from HoO8 polyhedra and SO4 tetrahedra. The asymmetric unit contains 12 crystallographic independent non–hydrogen atoms, all of which belong to the inorganic framework. As show in Fig. 1, the coordination about Ho is achieved by four O atoms from bridging sulfate ions. S1 makes three S–O–Ho linkages through bridging O atoms, while S2 lies on a two fold axis and makes two S–O–Ho linkages. The coordination sphere of each Ho is completed by four water molecules, which act as terminal ligands of Ho3+. To the best of our knowledge, although many lanthanide sulfates are known, this is the first example of holmium sulfate.

The bond distances and bond angles are in agreement with those found in the reported rare-earth compounds (Xu et al., 2007). The geometry of the sulfate ions is unexceptional. Fig. 2 shows the two-dimensional arrangement in the unit cell, displaying the way the different Ho ions are connected by bridging sulfates and water molecules.

Related literature top

For related literature, see: Doran et al. (2002); Hummel et al. (1993); Li et al. (1998); Plévert et al. (2001); Xu, Fan, Chino et al. (2004); Xu, Fan, Elangovan et al. (2004); <unl>Xu, Ding, Feng et al. (2006)</unl>; Xu, Ding, Zhou & Liu (2006); Yuan et al. (2004); Zhang et al. (2004); Xu et al. (2007).

Experimental top

Colorless block crystals were synthesized hydrothermally from a mixture of Ho2O3, H2SO4, H2O and ethylenediamine. In a typical synthesis, Ho2O3(0.2584 g) was dissolved in a mixture of 5 ml water, ethylenediamine (0.3651 g) and H2SO4 (98%) (0.2148 g) with constant stirring. Finally, the mixture was kept in a 25 ml Teflon-lined steel autoclave at 453 K for 6 days. The autoclave was slowly cooled to room temperature, and then the product was filtered, washed with distilled water, and dried at room temperature. Colorless block crystals of the title compound were obtained.

Refinement top

The highest peak in the difference map is 4.55 e/Å3, and 0.94 (2) Å from Ho1, while the minimum peak is 0.83 (2) Å from Ho1. The H atom was located from a difference-Fourier map. Because the refinement for H atoms is not stable, the distances for H—O are restrained in the final refinement. All the H—O bond lengths are fixed as 0.85 (2) Å.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b.

Figures top
[Figure 1] Fig. 1. The molecular structure for title compound. Displacement ellipsoids at the 70% probability level.
[Figure 2] Fig. 2. The crystal packing in the unit cell of Ho2(SO4)3(H2O)8.
Poly[tetraaquatri-µ2-sulfato-diholmium(III)] top
Crystal data top
[Ho2(SO4)3(H2O)4]F000 = 1432
Mr = 762.17Dx = 3.155 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1579 reflections
a = 13.466 (3) Åθ = 2.8–27.0º
b = 6.6966 (15) ŵ = 10.29 mm−1
c = 18.183 (4) ÅT = 293 (2) K
β = 101.875 (3)ºBlock, colorless
V = 1604.6 (6) Å30.10 × 0.08 × 0.07 mm
Z = 4
Data collection top
Bruker APEX2 CCD
diffractometer		1725 independent reflections
Radiation source: fine-focus sealed tube1579 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.047
T = 293(2) Kθmax = 27.0º
ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −15→17
Tmin = 0.426, Tmax = 0.533k = −8→8
4131 measured reflectionsl = −21→23
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047Only H-atom coordinates refined
wR(F2) = 0.130  w = 1/[σ2(Fo2) + (0.0925P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.009
1725 reflectionsΔρmax = 4.55 e Å−3
139 parametersΔρmin = −2.86 e Å−3
13 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00497 (16)
Crystal data top
[Ho2(SO4)3(H2O)4]V = 1604.6 (6) Å3
Mr = 762.17Z = 4
Monoclinic, C2/cMo Kα
a = 13.466 (3) ŵ = 10.29 mm−1
b = 6.6966 (15) ÅT = 293 (2) K
c = 18.183 (4) Å0.10 × 0.08 × 0.07 mm
β = 101.875 (3)º
Data collection top
Bruker APEX2 CCD
diffractometer		1725 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1579 reflections with I > 2σ(I)
Tmin = 0.426, Tmax = 0.533Rint = 0.047
4131 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04713 restraints
wR(F2) = 0.130Only H-atom coordinates refined
S = 1.08Δρmax = 4.55 e Å−3
1725 reflectionsΔρmin = −2.86 e Å−3
139 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 > 2sigma(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
xyzUiso*/Ueq
Ho10.833712 (14)0.02050 (3)0.607964 (10)0.01160 (7)
S10.78096 (8)−0.02655 (15)0.41069 (6)0.0116 (3)
S21.00000.3197 (2)0.75000.0125 (3)
O10.9155 (2)0.1928 (5)0.71260 (17)0.0239 (8)
O20.8377 (2)−0.0344 (5)0.3506 (2)0.0219 (9)
O30.8517 (2)−0.0730 (5)0.48430 (16)0.0153 (7)
O41.0348 (2)0.4445 (5)0.69329 (18)0.0192 (8)
O50.6988 (2)−0.1760 (5)0.39806 (16)0.0184 (8)
O60.7382 (2)0.1712 (5)0.41740 (17)0.0211 (8)
O1W0.9839 (2)−0.1652 (5)0.6397 (2)0.0307 (10)
H1A0.989 (3)−0.2916 (17)0.641 (3)0.046*
H1B1.0392 (12)−0.101 (3)0.646 (3)0.046*
O2W0.6576 (3)−0.0171 (4)0.5448 (2)0.0199 (9)
H2A0.6163 (18)0.076 (3)0.528 (3)0.030*
H2B0.6365 (12)−0.106 (3)0.5116 (12)0.030*
O3W0.7442 (3)−0.0132 (5)0.7027 (2)0.0272 (11)
H3A0.6826 (11)−0.045 (6)0.6842 (17)0.041*
H3B0.7534 (16)0.023 (5)0.7492 (6)0.041*
O4W0.9593 (2)0.2333 (5)0.56423 (16)0.0183 (8)
H4A1.0001 (11)0.172 (4)0.5433 (12)0.028*
H4B0.992 (2)0.309 (4)0.5977 (15)0.028*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ho10.00961 (13)0.00923 (12)0.01614 (14)−0.00108 (5)0.00306 (11)−0.00041 (6)
S10.0102 (5)0.0092 (5)0.0160 (5)−0.0012 (3)0.0039 (4)0.0008 (3)
S20.0096 (5)0.0116 (7)0.0159 (6)0.0000.0015 (5)0.000
O10.0205 (14)0.0269 (19)0.0239 (16)−0.0132 (14)0.0032 (13)−0.0038 (14)
O20.0153 (18)0.0308 (18)0.0211 (17)−0.0025 (12)0.0069 (15)−0.0044 (13)
O30.0124 (12)0.0193 (15)0.0151 (13)0.0017 (13)0.0053 (11)0.0023 (13)
O40.0172 (15)0.0214 (16)0.0212 (16)−0.0008 (13)0.0092 (13)0.0067 (14)
O50.0136 (13)0.0121 (15)0.0287 (16)−0.0049 (13)0.0022 (12)0.0002 (13)
O60.0250 (14)0.0083 (14)0.0299 (17)0.0019 (13)0.0052 (13)0.0025 (13)
O1W0.0127 (13)0.0118 (16)0.063 (2)0.0014 (13)−0.0016 (16)0.0069 (17)
O2W0.0170 (17)0.0108 (15)0.0287 (19)0.0009 (11)−0.0027 (17)−0.0013 (12)
O3W0.0206 (19)0.045 (2)0.0180 (19)−0.0147 (13)0.0087 (17)−0.0067 (13)
O4W0.0152 (13)0.0208 (17)0.0199 (15)−0.0031 (13)0.0058 (12)−0.0043 (12)
Geometric parameters (Å, °) top
Ho1—O6i2.287 (3)S2—O1iii1.470 (3)
Ho1—O12.303 (3)S2—O41.477 (4)
Ho1—O3W2.308 (4)S2—O4iii1.477 (4)
Ho1—O1W2.344 (3)O5—Ho1ii2.347 (3)
Ho1—O5ii2.347 (3)O6—Ho1i2.287 (3)
Ho1—O32.394 (3)O1W—H1A0.849 (12)
Ho1—O2W2.426 (4)O1W—H1B0.847 (14)
Ho1—O4W2.466 (3)O2W—H2A0.849 (17)
S1—O21.457 (4)O2W—H2B0.855 (15)
S1—O61.459 (3)O3W—H3A0.855 (14)
S1—O51.474 (3)O3W—H3B0.866 (12)
S1—O31.507 (3)O4W—H4A0.839 (16)
S2—O11.470 (3)O4W—H4B0.845 (17)
O6i—Ho1—O179.91 (11)O2—S1—O6111.8 (2)
O6i—Ho1—O3W88.51 (12)O2—S1—O5110.55 (19)
O1—Ho1—O3W70.54 (12)O6—S1—O5109.45 (19)
O6i—Ho1—O1W146.85 (11)O2—S1—O3108.96 (19)
O1—Ho1—O1W79.67 (12)O6—S1—O3107.54 (18)
O3W—Ho1—O1W108.75 (13)O5—S1—O3108.37 (18)
O6i—Ho1—O5ii144.18 (10)O1—S2—O1iii109.4 (3)
O1—Ho1—O5ii125.75 (11)O1—S2—O4109.32 (18)
O3W—Ho1—O5ii79.48 (11)O1iii—S2—O4108.85 (18)
O1W—Ho1—O5ii68.48 (10)O1—S2—O4iii108.85 (18)
O6i—Ho1—O399.64 (11)O1iii—S2—O4iii109.32 (18)
O1—Ho1—O3141.59 (11)O4—S2—O4iii111.0 (3)
O3W—Ho1—O3147.65 (12)S2—O1—Ho1149.9 (2)
O1W—Ho1—O380.99 (12)S1—O3—Ho1127.75 (18)
O5ii—Ho1—O375.70 (11)S1—O5—Ho1ii143.27 (18)
O6i—Ho1—O2W70.48 (10)S1—O6—Ho1i163.9 (2)
O1—Ho1—O2W134.25 (12)Ho1—O1W—H1A127 (2)
O3W—Ho1—O2W74.53 (14)Ho1—O1W—H1B117.0 (16)
O1W—Ho1—O2W140.51 (11)H1A—O1W—H1B116 (3)
O5ii—Ho1—O2W73.80 (9)Ho1—O2W—H2A126.8 (19)
O3—Ho1—O2W78.83 (12)Ho1—O2W—H2B123.8 (12)
O6i—Ho1—O4W72.75 (11)H2A—O2W—H2B99 (3)
O1—Ho1—O4W74.56 (11)Ho1—O3W—H3A110 (2)
O3W—Ho1—O4W142.73 (11)Ho1—O3W—H3B135.3 (16)
O1W—Ho1—O4W76.79 (11)H3A—O3W—H3B113 (2)
O5ii—Ho1—O4W133.40 (11)Ho1—O4W—H4A114.7 (16)
O3—Ho1—O4W68.87 (10)Ho1—O4W—H4B114 (2)
O2W—Ho1—O4W125.16 (11)H4A—O4W—H4B109 (3)
Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+3/2, −y−1/2, −z+1; (iii) −x+2, y, −z+3/2.
Selected geometric parameters (Å) top
Ho1—O6i2.287 (3)Ho1—O5ii2.347 (3)
Ho1—O12.303 (3)Ho1—O32.394 (3)
Ho1—O3W2.308 (4)Ho1—O2W2.426 (4)
Ho1—O1W2.344 (3)Ho1—O4W2.466 (3)
Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+3/2, −y−1/2, −z+1.
Acknowledgements top

This work was supported by the Natural Science Foundation of Liaoning province (20062139).

references
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