Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056346/br2059sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056346/br2059Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (S-O) = 0.003 Å
- R factor = 0.047
- wR factor = 0.130
- Data-to-parameter ratio = 12.4
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.91
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.913 Tmax scaled 0.487 Tmin scaled 0.389 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Ho1 (3) 3.28 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 13
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
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).
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.
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.
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.
Fig. 1. The molecular structure for title compound. Displacement ellipsoids at the 70% probability level. | |
Fig. 2. The crystal packing in the unit cell of Ho2(SO4)3(H2O)8. |
[Ho2(SO4)3(H2O)4] | F(000) = 1432 |
Mr = 762.17 | Dx = 3.155 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1579 reflections |
a = 13.466 (3) Å | θ = 2.8–27.0° |
b = 6.6966 (15) Å | µ = 10.29 mm−1 |
c = 18.183 (4) Å | T = 293 K |
β = 101.875 (3)° | Block, colorless |
V = 1604.6 (6) Å3 | 0.10 × 0.08 × 0.07 mm |
Z = 4 |
Bruker APEX2 CCD diffractometer | 1725 independent reflections |
Radiation source: fine-focus sealed tube | 1579 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω scans | θmax = 27.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −15→17 |
Tmin = 0.426, Tmax = 0.533 | k = −8→8 |
4131 measured reflections | l = −21→23 |
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)] = 0.047 | Only 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 reflections | Δρmax = 4.55 e Å−3 |
139 parameters | Δρmin = −2.86 e Å−3 |
13 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00497 (16) |
[Ho2(SO4)3(H2O)4] | V = 1604.6 (6) Å3 |
Mr = 762.17 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.466 (3) Å | µ = 10.29 mm−1 |
b = 6.6966 (15) Å | T = 293 K |
c = 18.183 (4) Å | 0.10 × 0.08 × 0.07 mm |
β = 101.875 (3)° |
Bruker APEX2 CCD diffractometer | 1725 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 1579 reflections with I > 2σ(I) |
Tmin = 0.426, Tmax = 0.533 | Rint = 0.047 |
4131 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 13 restraints |
wR(F2) = 0.130 | Only H-atom coordinates refined |
S = 1.08 | Δρmax = 4.55 e Å−3 |
1725 reflections | Δρmin = −2.86 e Å−3 |
139 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Ho1 | 0.833712 (14) | 0.02050 (3) | 0.607964 (10) | 0.01160 (7) | |
S1 | 0.78096 (8) | −0.02655 (15) | 0.41069 (6) | 0.0116 (3) | |
S2 | 1.0000 | 0.3197 (2) | 0.7500 | 0.0125 (3) | |
O1 | 0.9155 (2) | 0.1928 (5) | 0.71260 (17) | 0.0239 (8) | |
O2 | 0.8377 (2) | −0.0344 (5) | 0.3506 (2) | 0.0219 (9) | |
O3 | 0.8517 (2) | −0.0730 (5) | 0.48430 (16) | 0.0153 (7) | |
O4 | 1.0348 (2) | 0.4445 (5) | 0.69329 (18) | 0.0192 (8) | |
O5 | 0.6988 (2) | −0.1760 (5) | 0.39806 (16) | 0.0184 (8) | |
O6 | 0.7382 (2) | 0.1712 (5) | 0.41740 (17) | 0.0211 (8) | |
O1W | 0.9839 (2) | −0.1652 (5) | 0.6397 (2) | 0.0307 (10) | |
H1A | 0.989 (3) | −0.2916 (17) | 0.641 (3) | 0.046* | |
H1B | 1.0392 (12) | −0.101 (3) | 0.646 (3) | 0.046* | |
O2W | 0.6576 (3) | −0.0171 (4) | 0.5448 (2) | 0.0199 (9) | |
H2A | 0.6163 (18) | 0.076 (3) | 0.528 (3) | 0.030* | |
H2B | 0.6365 (12) | −0.106 (3) | 0.5116 (12) | 0.030* | |
O3W | 0.7442 (3) | −0.0132 (5) | 0.7027 (2) | 0.0272 (11) | |
H3A | 0.6826 (11) | −0.045 (6) | 0.6842 (17) | 0.041* | |
H3B | 0.7534 (16) | 0.023 (5) | 0.7492 (6) | 0.041* | |
O4W | 0.9593 (2) | 0.2333 (5) | 0.56423 (16) | 0.0183 (8) | |
H4A | 1.0001 (11) | 0.172 (4) | 0.5433 (12) | 0.028* | |
H4B | 0.992 (2) | 0.309 (4) | 0.5977 (15) | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ho1 | 0.00961 (13) | 0.00923 (12) | 0.01614 (14) | −0.00108 (5) | 0.00306 (11) | −0.00041 (6) |
S1 | 0.0102 (5) | 0.0092 (5) | 0.0160 (5) | −0.0012 (3) | 0.0039 (4) | 0.0008 (3) |
S2 | 0.0096 (5) | 0.0116 (7) | 0.0159 (6) | 0.000 | 0.0015 (5) | 0.000 |
O1 | 0.0205 (14) | 0.0269 (19) | 0.0239 (16) | −0.0132 (14) | 0.0032 (13) | −0.0038 (14) |
O2 | 0.0153 (18) | 0.0308 (18) | 0.0211 (17) | −0.0025 (12) | 0.0069 (15) | −0.0044 (13) |
O3 | 0.0124 (12) | 0.0193 (15) | 0.0151 (13) | 0.0017 (13) | 0.0053 (11) | 0.0023 (13) |
O4 | 0.0172 (15) | 0.0214 (16) | 0.0212 (16) | −0.0008 (13) | 0.0092 (13) | 0.0067 (14) |
O5 | 0.0136 (13) | 0.0121 (15) | 0.0287 (16) | −0.0049 (13) | 0.0022 (12) | 0.0002 (13) |
O6 | 0.0250 (14) | 0.0083 (14) | 0.0299 (17) | 0.0019 (13) | 0.0052 (13) | 0.0025 (13) |
O1W | 0.0127 (13) | 0.0118 (16) | 0.063 (2) | 0.0014 (13) | −0.0016 (16) | 0.0069 (17) |
O2W | 0.0170 (17) | 0.0108 (15) | 0.0287 (19) | 0.0009 (11) | −0.0027 (17) | −0.0013 (12) |
O3W | 0.0206 (19) | 0.045 (2) | 0.0180 (19) | −0.0147 (13) | 0.0087 (17) | −0.0067 (13) |
O4W | 0.0152 (13) | 0.0208 (17) | 0.0199 (15) | −0.0031 (13) | 0.0058 (12) | −0.0043 (12) |
Ho1—O6i | 2.287 (3) | S2—O1iii | 1.470 (3) |
Ho1—O1 | 2.303 (3) | S2—O4 | 1.477 (4) |
Ho1—O3W | 2.308 (4) | S2—O4iii | 1.477 (4) |
Ho1—O1W | 2.344 (3) | O5—Ho1ii | 2.347 (3) |
Ho1—O5ii | 2.347 (3) | O6—Ho1i | 2.287 (3) |
Ho1—O3 | 2.394 (3) | O1W—H1A | 0.849 (12) |
Ho1—O2W | 2.426 (4) | O1W—H1B | 0.847 (14) |
Ho1—O4W | 2.466 (3) | O2W—H2A | 0.849 (17) |
S1—O2 | 1.457 (4) | O2W—H2B | 0.855 (15) |
S1—O6 | 1.459 (3) | O3W—H3A | 0.855 (14) |
S1—O5 | 1.474 (3) | O3W—H3B | 0.866 (12) |
S1—O3 | 1.507 (3) | O4W—H4A | 0.839 (16) |
S2—O1 | 1.470 (3) | O4W—H4B | 0.845 (17) |
O6i—Ho1—O1 | 79.91 (11) | O2—S1—O6 | 111.8 (2) |
O6i—Ho1—O3W | 88.51 (12) | O2—S1—O5 | 110.55 (19) |
O1—Ho1—O3W | 70.54 (12) | O6—S1—O5 | 109.45 (19) |
O6i—Ho1—O1W | 146.85 (11) | O2—S1—O3 | 108.96 (19) |
O1—Ho1—O1W | 79.67 (12) | O6—S1—O3 | 107.54 (18) |
O3W—Ho1—O1W | 108.75 (13) | O5—S1—O3 | 108.37 (18) |
O6i—Ho1—O5ii | 144.18 (10) | O1—S2—O1iii | 109.4 (3) |
O1—Ho1—O5ii | 125.75 (11) | O1—S2—O4 | 109.32 (18) |
O3W—Ho1—O5ii | 79.48 (11) | O1iii—S2—O4 | 108.85 (18) |
O1W—Ho1—O5ii | 68.48 (10) | O1—S2—O4iii | 108.85 (18) |
O6i—Ho1—O3 | 99.64 (11) | O1iii—S2—O4iii | 109.32 (18) |
O1—Ho1—O3 | 141.59 (11) | O4—S2—O4iii | 111.0 (3) |
O3W—Ho1—O3 | 147.65 (12) | S2—O1—Ho1 | 149.9 (2) |
O1W—Ho1—O3 | 80.99 (12) | S1—O3—Ho1 | 127.75 (18) |
O5ii—Ho1—O3 | 75.70 (11) | S1—O5—Ho1ii | 143.27 (18) |
O6i—Ho1—O2W | 70.48 (10) | S1—O6—Ho1i | 163.9 (2) |
O1—Ho1—O2W | 134.25 (12) | Ho1—O1W—H1A | 127 (2) |
O3W—Ho1—O2W | 74.53 (14) | Ho1—O1W—H1B | 117.0 (16) |
O1W—Ho1—O2W | 140.51 (11) | H1A—O1W—H1B | 116 (3) |
O5ii—Ho1—O2W | 73.80 (9) | Ho1—O2W—H2A | 126.8 (19) |
O3—Ho1—O2W | 78.83 (12) | Ho1—O2W—H2B | 123.8 (12) |
O6i—Ho1—O4W | 72.75 (11) | H2A—O2W—H2B | 99 (3) |
O1—Ho1—O4W | 74.56 (11) | Ho1—O3W—H3A | 110 (2) |
O3W—Ho1—O4W | 142.73 (11) | Ho1—O3W—H3B | 135.3 (16) |
O1W—Ho1—O4W | 76.79 (11) | H3A—O3W—H3B | 113 (2) |
O5ii—Ho1—O4W | 133.40 (11) | Ho1—O4W—H4A | 114.7 (16) |
O3—Ho1—O4W | 68.87 (10) | Ho1—O4W—H4B | 114 (2) |
O2W—Ho1—O4W | 125.16 (11) | H4A—O4W—H4B | 109 (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. |
Experimental details
Crystal data | |
Chemical formula | [Ho2(SO4)3(H2O)4] |
Mr | 762.17 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.466 (3), 6.6966 (15), 18.183 (4) |
β (°) | 101.875 (3) |
V (Å3) | 1604.6 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 10.29 |
Crystal size (mm) | 0.10 × 0.08 × 0.07 |
Data collection | |
Diffractometer | Bruker APEX2 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.426, 0.533 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4131, 1725, 1579 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.130, 1.08 |
No. of reflections | 1725 |
No. of parameters | 139 |
No. of restraints | 13 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 4.55, −2.86 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL (Sheldrick, 1997b.
Ho1—O6i | 2.287 (3) | Ho1—O5ii | 2.347 (3) |
Ho1—O1 | 2.303 (3) | Ho1—O3 | 2.394 (3) |
Ho1—O3W | 2.308 (4) | Ho1—O2W | 2.426 (4) |
Ho1—O1W | 2.344 (3) | Ho1—O4W | 2.466 (3) |
Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+3/2, −y−1/2, −z+1. |
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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.