Acta Cryst. (2008). E64, i15 [ doi:10.1107/S1600536808001992 ]
The Tb atom of the title compound, TbHP2O7·4H2O, is coordinated by the O atoms of three symmetrically independent water molecules and by five O atoms belonging to HP2O7- groups. The TbO8 polyhedra are interconnected by the diphospate anions, forming a three-dimensional network which is additionally stabilized by O-H
O hydrogen bonding between water molecules and O atoms of the HP2O7- anions. Uncoordinated water molecules are situated in channels and are connected via hydrogen bonds with the framework.
An aqueous solution of TbCl3.6H2O (0.1M) was added dropwise to anhydrous Na4P2O7 dissolved in destilled water (0.1M). The pH of the mixture was controlled with diluted hydrochloric acid to be slightly acidic, and the solution was stirred for two h at room temperature. Prismatic-shaped colourless crystals with a maximal size of 0.3 mm formed after a few days on slow evaporation.
The H atoms were localized from a difference Fourier map. Their coordinates were refined independently with O—H distances restrained to 0.82 (1) Å. The isotropic temperature parameters of the H atoms were refined with 1.2Ueq of the parent atom. The H111—O11—H112 angle of the free water molecule was restrained to 109.47 (10)°.
Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 2005); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2000 (Petříček et al., 2007); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2000 (Petříček et al., 2007).
![[Figure 1]](./wm2172fig1thm.gif)
| Fig. 1. Part of the structure of HTbP2O7.4H2O drawn with displacement ellipsoids at the 50% probability level. [Symmetry codes: (i) 1 + x, y, z; (ii) 1.5 - x, -1/2 + y, 1.5 - z; (iii) 1 - x, 1 - y, 2 - z] |
![[Figure 2]](./wm2172fig2thm.gif)
| Fig. 2. The packing of TbHP2O7.4H2O viewed along a. Hydrogen bonds are represented by dashed lines. Colour code: Pink (P2O7 polyhedra), red spheres (O), grey spheres (Tb), dark grey spheres (H). All atoms are displayed with arbitrary radii. For clarity, O atoms belonging to PO4 tetrahedra have a smaller size than O atoms of water molecules. O atoms that would obscure H atoms important for understanding the hydrogen bonding scheme are plotted semitransparently. |
| TbHP2O7·4H2O | F000 = 768 |
| Mr = 405.9 | Dx = 3.037 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71069 Å |
| Hall symbol: -P 2yn | Cell parameters from 972 reflections |
| a = 6.6006 (6) Å | θ = 2.5–26.5º |
| b = 11.4744 (9) Å | µ = 8.38 mm−1 |
| c = 11.7252 (13) Å | T = 295 K |
| β = 92.150 (8)º | Prism, colorless |
| V = 887.42 (15) Å3 | 0.14 × 0.06 × 0.03 mm |
| Z = 4 |
| Oxford Diffraction CCD diffractometer | 1850 independent reflections |
| Radiation source: X-ray tube | 1628 reflections with I > 3σ(I) |
| Monochromator: graphite | Rint = 0.019 |
| Detector resolution: 8.3438 pixels mm-1 | θmax = 26.6º |
| T = 295 K | θmin = 2.5º |
| ω scans | h = −8→7 |
| Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2005), using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | k = −14→14 |
| Tmin = 0.329, Tmax = 0.635 | l = −14→14 |
| 8671 measured reflections |
| Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.011 | Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0004I2] |
| wR(F2) = 0.034 | (Δ/σ)max = 0.009 |
| S = 1.21 | Δρmax = 0.29 e Å−3 |
| 1850 reflections | Δρmin = −0.21 e Å−3 |
| 155 parameters | Extinction correction: B-C type 1 Lorentzian isotropic [Becker, P. J. & Coppens, P. (1974). Acta Cryst. A30, 129–147] |
| 10 restraints | Extinction coefficient: 2.9 (8) |
| 9 constraints |
| TbHP2O7·4H2O | V = 887.42 (15) Å3 |
| Mr = 405.9 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 6.6006 (6) Å | µ = 8.38 mm−1 |
| b = 11.4744 (9) Å | T = 295 K |
| c = 11.7252 (13) Å | 0.14 × 0.06 × 0.03 mm |
| β = 92.150 (8)º |
| Oxford Diffraction CCD diffractometer | 1850 independent reflections |
| Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2005), using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)] | 1628 reflections with I > 3σ(I) |
| Tmin = 0.329, Tmax = 0.635 | Rint = 0.019 |
| 8671 measured reflections |
| R[F2 > 2σ(F2)] = 0.011 | 10 restraints |
| wR(F2) = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.21 | Δρmax = 0.29 e Å−3 |
| 1850 reflections | Δρmin = −0.21 e Å−3 |
| 155 parameters |
Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F2 for refinement carried out on F and F2, respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement. The program used for refinement, Jana2000, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S may be larger then the ones from the SHELX program. |
| x | y | z | Uiso*/Ueq | ||
| Tb1 | 0.755557 (17) | 0.417027 (10) | 0.836213 (10) | 0.00831 (5) | |
| P1 | 0.25551 (9) | 0.54805 (6) | 0.85787 (5) | 0.00834 (18) | |
| P2 | 0.47954 (9) | 0.63300 (5) | 0.66266 (5) | 0.00860 (18) | |
| O1 | 0.4213 (3) | 0.45787 (15) | 0.87403 (15) | 0.0122 (5) | |
| O2 | 0.0629 (3) | 0.50007 (16) | 0.80317 (16) | 0.0157 (5) | |
| O3 | 0.2158 (3) | 0.61576 (15) | 0.96588 (15) | 0.0149 (5) | |
| O4 | 0.3423 (3) | 0.57670 (15) | 0.56618 (17) | 0.0169 (6) | |
| O5 | 0.6553 (3) | 0.55618 (15) | 0.69557 (16) | 0.0137 (5) | |
| O6 | 0.5259 (2) | 0.75465 (15) | 0.62791 (15) | 0.0135 (5) | |
| O7 | 0.3378 (3) | 0.64547 (14) | 0.77094 (14) | 0.0112 (5) | |
| O8 | 0.7671 (3) | 0.62083 (18) | 0.93419 (17) | 0.0177 (6) | |
| O9 | 0.8201 (4) | 0.34050 (17) | 0.64753 (17) | 0.0252 (7) | |
| O10 | 0.5535 (3) | 0.24098 (19) | 0.8262 (2) | 0.0333 (7) | |
| O11 | 0.2577 (4) | 0.36300 (19) | 0.5980 (2) | 0.0394 (9) | |
| H81 | 0.697 (4) | 0.614 (3) | 0.9904 (18) | 0.0212* | |
| H111 | 0.294 (4) | 0.3021 (18) | 0.572 (3) | 0.0472* | |
| H82 | 0.881 (2) | 0.643 (3) | 0.955 (2) | 0.0212* | |
| H112 | 0.141 (2) | 0.375 (3) | 0.577 (3) | 0.0472* | |
| H101 | 0.593 (5) | 0.1757 (15) | 0.810 (3) | 0.04* | |
| H91 | 0.776 (5) | 0.380 (3) | 0.593 (2) | 0.0303* | |
| H92 | 0.777 (4) | 0.2742 (13) | 0.633 (3) | 0.0303* | |
| H41 | 0.323 (4) | 0.5072 (10) | 0.574 (3) | 0.0203* | |
| H102 | 0.434 (2) | 0.243 (3) | 0.807 (3) | 0.04* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Tb1 | 0.00694 (8) | 0.00827 (8) | 0.00975 (8) | 0.00064 (4) | 0.00087 (5) | 0.00041 (4) |
| P1 | 0.0067 (3) | 0.0093 (3) | 0.0092 (3) | 0.0008 (2) | 0.0021 (2) | 0.0011 (2) |
| P2 | 0.0082 (3) | 0.0085 (3) | 0.0092 (3) | −0.0007 (2) | 0.0009 (2) | 0.0011 (2) |
| O1 | 0.0097 (9) | 0.0127 (8) | 0.0146 (9) | 0.0029 (7) | 0.0037 (7) | 0.0037 (7) |
| O2 | 0.0095 (9) | 0.0182 (9) | 0.0192 (10) | −0.0040 (7) | −0.0004 (8) | 0.0001 (7) |
| O3 | 0.0201 (10) | 0.0137 (8) | 0.0110 (10) | 0.0048 (8) | 0.0034 (7) | −0.0010 (7) |
| O4 | 0.0225 (11) | 0.0120 (9) | 0.0157 (10) | −0.0038 (8) | −0.0041 (8) | −0.0012 (7) |
| O5 | 0.0113 (9) | 0.0156 (9) | 0.0143 (10) | 0.0031 (7) | 0.0031 (8) | 0.0039 (7) |
| O6 | 0.0141 (9) | 0.0107 (8) | 0.0159 (9) | −0.0034 (7) | 0.0016 (7) | 0.0022 (7) |
| O7 | 0.0115 (9) | 0.0091 (8) | 0.0133 (9) | 0.0003 (7) | 0.0055 (7) | 0.0018 (7) |
| O8 | 0.0163 (11) | 0.0208 (10) | 0.0160 (11) | −0.0033 (9) | 0.0013 (8) | 0.0035 (8) |
| O9 | 0.0432 (13) | 0.0160 (10) | 0.0159 (11) | 0.0057 (10) | −0.0061 (9) | −0.0017 (8) |
| O10 | 0.0138 (10) | 0.0163 (10) | 0.0697 (17) | −0.0019 (9) | −0.0005 (11) | −0.0122 (11) |
| O11 | 0.0541 (17) | 0.0120 (11) | 0.0542 (16) | −0.0102 (10) | 0.0317 (14) | −0.0094 (10) |
| Tb1—O1 | 2.3145 (17) | P1—O1 | 1.5129 (18) |
| Tb1—O2i | 2.2877 (17) | P1—O2 | 1.5063 (18) |
| Tb1—O3ii | 2.3514 (18) | P1—O3 | 1.5169 (19) |
| Tb1—O5 | 2.3718 (18) | P1—O7 | 1.6201 (18) |
| Tb1—O6iii | 2.3842 (17) | P2—O4 | 1.562 (2) |
| Tb1—O8 | 2.605 (2) | P2—O5 | 1.4957 (19) |
| Tb1—O9 | 2.433 (2) | P2—O6 | 1.4891 (18) |
| Tb1—O10 | 2.421 (2) | P2—O7 | 1.6116 (18) |
| O1—Tb1—O2i | 143.70 (6) | O6iii—Tb1—O8 | 128.03 (6) |
| O1—Tb1—O3ii | 83.41 (6) | O6iii—Tb1—O9 | 75.70 (7) |
| O1—Tb1—O5 | 75.74 (6) | O6iii—Tb1—O10 | 71.65 (6) |
| O1—Tb1—O6iii | 134.37 (6) | O8—Tb1—O9 | 136.20 (6) |
| O1—Tb1—O8 | 75.29 (6) | O8—Tb1—O10 | 141.01 (7) |
| O1—Tb1—O9 | 116.61 (7) | O9—Tb1—O10 | 76.69 (8) |
| O1—Tb1—O10 | 69.56 (7) | O1—P1—O2 | 113.46 (10) |
| O2i—Tb1—O3ii | 101.23 (6) | O1—P1—O3 | 113.12 (10) |
| O2i—Tb1—O5 | 80.10 (6) | O1—P1—O7 | 107.03 (10) |
| O2i—Tb1—O6iii | 79.67 (6) | O2—P1—O3 | 111.92 (11) |
| O2i—Tb1—O8 | 71.90 (6) | O2—P1—O7 | 106.35 (10) |
| O2i—Tb1—O9 | 79.03 (7) | O3—P1—O7 | 104.14 (10) |
| O2i—Tb1—O10 | 146.08 (7) | O4—P2—O5 | 111.48 (10) |
| O3ii—Tb1—O5 | 143.50 (6) | O4—P2—O6 | 107.99 (10) |
| O3ii—Tb1—O6iii | 71.04 (6) | O4—P2—O7 | 105.60 (10) |
| O3ii—Tb1—O8 | 73.05 (6) | O5—P2—O6 | 117.25 (10) |
| O3ii—Tb1—O9 | 146.04 (7) | O5—P2—O7 | 108.46 (10) |
| O3ii—Tb1—O10 | 86.44 (8) | O6—P2—O7 | 105.28 (10) |
| O5—Tb1—O6iii | 143.13 (6) | H81—O8—H82 | 109 (3) |
| O5—Tb1—O8 | 72.85 (6) | H91—O9—H92 | 104 (3) |
| O5—Tb1—O9 | 70.39 (6) | H101—O10—H102 | 106 (3) |
| O5—Tb1—O10 | 112.90 (7) | H111—O11—H112 | 109 (3) |
| Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+2; (iii) −x+3/2, y−1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H41···O11 | 0.813 (13) | 1.736 (14) | 2.546 (3) | 174 (3) |
| O8—H81···O1ii | 0.82 (2) | 1.98 (3) | 2.762 (3) | 159 (3) |
| O8—H82···O3i | 0.822 (18) | 2.231 (14) | 2.972 (3) | 150 (3) |
| O9—H91···O4iv | 0.83 (3) | 2.06 (3) | 2.851 (3) | 161 (3) |
| O9—H92···O8iii | 0.828 (18) | 1.95 (2) | 2.750 (3) | 164 (3) |
| O10—H101···O5iii | 0.82 (2) | 2.16 (3) | 2.880 (3) | 147 (3) |
| O10—H102···O7v | 0.812 (16) | 2.28 (2) | 2.991 (3) | 147 (3) |
| O11—H111···O3v | 0.80 (2) | 2.18 (2) | 2.941 (3) | 157 (3) |
| Symmetry codes: (ii) −x+1, −y+1, −z+2; (i) x+1, y, z; (iv) −x+1, −y+1, −z+1; (iii) −x+3/2, y−1/2, −z+3/2; (v) −x+1/2, y−1/2, −z+3/2. |
| Tb1—O1 | 2.3145 (17) | P1—O1 | 1.5129 (18) |
| Tb1—O2i | 2.2877 (17) | P1—O2 | 1.5063 (18) |
| Tb1—O3ii | 2.3514 (18) | P1—O3 | 1.5169 (19) |
| Tb1—O5 | 2.3718 (18) | P1—O7 | 1.6201 (18) |
| Tb1—O6iii | 2.3842 (17) | P2—O4 | 1.562 (2) |
| Tb1—O8 | 2.605 (2) | P2—O5 | 1.4957 (19) |
| Tb1—O9 | 2.433 (2) | P2—O6 | 1.4891 (18) |
| Tb1—O10 | 2.421 (2) | P2—O7 | 1.6116 (18) |
| Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+2; (iii) −x+3/2, y−1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O4—H41···O11 | 0.813 (13) | 1.736 (14) | 2.546 (3) | 174 (3) |
| O8—H81···O1ii | 0.82 (2) | 1.98 (3) | 2.762 (3) | 159 (3) |
| O8—H82···O3i | 0.822 (18) | 2.231 (14) | 2.972 (3) | 150 (3) |
| O9—H91···O4iv | 0.83 (3) | 2.06 (3) | 2.851 (3) | 161 (3) |
| O9—H92···O8iii | 0.828 (18) | 1.95 (2) | 2.750 (3) | 164 (3) |
| O10—H101···O5iii | 0.82 (2) | 2.16 (3) | 2.880 (3) | 147 (3) |
| O10—H102···O7v | 0.812 (16) | 2.28 (2) | 2.991 (3) | 147 (3) |
| O11—H111···O3v | 0.80 (2) | 2.18 (2) | 2.941 (3) | 157 (3) |
| Symmetry codes: (ii) −x+1, −y+1, −z+2; (i) x+1, y, z; (iv) −x+1, −y+1, −z+1; (iii) −x+3/2, y−1/2, −z+3/2; (v) −x+1/2, y−1/2, −z+3/2. |
This work was supported by the Grant Agency of the Czech Republic, grant No. 202/05/0421.
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Acidic rare earth diphosphates of general formula REHP2O7.nH2O exhibit interesting luminescent and optical properties (Hraiech et al., 2005 and references herein). The title compound is isostructural with other compounds of formula type REHP2O7.4H2O, RE = Sm (Chehimi-Moumen et al., 2002), Gd (Hraiech et al., 2005), and Eu (Anna-Rabah et al., 2006).
The structure of TbHP2O7.4H2O is made up of TbO8 polyhedra and HP2O7 groups that form a three-dimensional framework. In channels running along a (Fig. 2) free water molecules are located which are connected via hydrogen bonds with the framework (see hydrogen-bonding Table).
The P2O7 group is protonated, with the H atom located at O4 (Fig. 1), as also indicated by elongation of the corresponding P—O distance. The bridging angle P1—O7—P2 between the two PO4 tetrahedra is 130.73 (11)°.