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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): i15.
Published online 2008 January 23. doi:  10.1107/S1600536808001992
PMCID: PMC2960266

Terbium(III) hydrogendiphosphate(V) tetra­hydrate

Abstract

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.

Related literature

Isostructural compounds of the type REHP2O7·4H2O were reported for RE = Sm by Chehimi-Moumen et al. (2002 [triangle]), for RE = Gd by Hraiech et al. (2005 [triangle]) and for RE = Eu by Anna-Rabah et al. (2006 [triangle]).

Experimental

Crystal data

  • TbHP2O7·4H2O
  • M r = 405.9
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00i15-efi1.jpg
  • a = 6.6006 (6) Å
  • b = 11.4744 (9) Å
  • c = 11.7252 (13) Å
  • β = 92.150 (8)°
  • V = 887.42 (15) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 8.38 mm−1
  • T = 295 K
  • 0.14 × 0.06 × 0.03 mm

Data collection

  • Oxford Diffraction Xcalibur 2 diffractometer with Sapphire 2 CCD area-detector
  • Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2005 [triangle]), using a multifaceted crystal model based on expressions derived by Clark & Reid (1995 [triangle])] T min = 0.329, T max = 0.635
  • 8671 measured reflections
  • 1850 independent reflections
  • 1628 reflections with I > 3σ(I)
  • R int = 0.019

Refinement

  • R[F 2 > 2σ(F 2)] = 0.011
  • wR(F 2) = 0.034
  • S = 1.21
  • 1850 reflections
  • 155 parameters
  • 10 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.29 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2005 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SIR2002 (Burla et al., 2003 [triangle]); program(s) used to refine structure: JANA2000 (Petříček et al., 2007 [triangle]); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 [triangle]); software used to prepare material for publication: JANA2000.

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808001992/wm2172sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808001992/wm2172Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the Grant Agency of the Czech Republic (grant No. 202/05/0421).

supplementary crystallographic information

Comment

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)°.

Experimental

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.

Refinement

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)°.

Figures

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]
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 ...

Crystal data

TbHP2O7·4H2OF000 = 768
Mr = 405.9Dx = 3.037 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 972 reflections
a = 6.6006 (6) Åθ = 2.5–26.5º
b = 11.4744 (9) ŵ = 8.38 mm1
c = 11.7252 (13) ÅT = 295 K
β = 92.150 (8)ºPrism, colorless
V = 887.42 (15) Å30.14 × 0.06 × 0.03 mm
Z = 4

Data collection

Oxford Diffraction CCD diffractometer1850 independent reflections
Radiation source: X-ray tube1628 reflections with I > 3σ(I)
Monochromator: graphiteRint = 0.019
Detector resolution: 8.3438 pixels mm-1θmax = 26.6º
T = 295 Kθmin = 2.5º
ω scansh = −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 = 0.635l = −14→14
8671 measured reflections

Refinement

Refinement on F2H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.011Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0004I2]
wR(F2) = 0.034(Δ/σ)max = 0.009
S = 1.21Δρmax = 0.29 e Å3
1850 reflectionsΔρmin = −0.21 e Å3
155 parametersExtinction correction: B-C type 1 Lorentzian isotropic [Becker, P. J. & Coppens, P. (1974). Acta Cryst. A30, 129–147]
10 restraintsExtinction coefficient: 2.9 (8)
9 constraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Tb10.755557 (17)0.417027 (10)0.836213 (10)0.00831 (5)
P10.25551 (9)0.54805 (6)0.85787 (5)0.00834 (18)
P20.47954 (9)0.63300 (5)0.66266 (5)0.00860 (18)
O10.4213 (3)0.45787 (15)0.87403 (15)0.0122 (5)
O20.0629 (3)0.50007 (16)0.80317 (16)0.0157 (5)
O30.2158 (3)0.61576 (15)0.96588 (15)0.0149 (5)
O40.3423 (3)0.57670 (15)0.56618 (17)0.0169 (6)
O50.6553 (3)0.55618 (15)0.69557 (16)0.0137 (5)
O60.5259 (2)0.75465 (15)0.62791 (15)0.0135 (5)
O70.3378 (3)0.64547 (14)0.77094 (14)0.0112 (5)
O80.7671 (3)0.62083 (18)0.93419 (17)0.0177 (6)
O90.8201 (4)0.34050 (17)0.64753 (17)0.0252 (7)
O100.5535 (3)0.24098 (19)0.8262 (2)0.0333 (7)
O110.2577 (4)0.36300 (19)0.5980 (2)0.0394 (9)
H810.697 (4)0.614 (3)0.9904 (18)0.0212*
H1110.294 (4)0.3021 (18)0.572 (3)0.0472*
H820.881 (2)0.643 (3)0.955 (2)0.0212*
H1120.141 (2)0.375 (3)0.577 (3)0.0472*
H1010.593 (5)0.1757 (15)0.810 (3)0.04*
H910.776 (5)0.380 (3)0.593 (2)0.0303*
H920.777 (4)0.2742 (13)0.633 (3)0.0303*
H410.323 (4)0.5072 (10)0.574 (3)0.0203*
H1020.434 (2)0.243 (3)0.807 (3)0.04*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Tb10.00694 (8)0.00827 (8)0.00975 (8)0.00064 (4)0.00087 (5)0.00041 (4)
P10.0067 (3)0.0093 (3)0.0092 (3)0.0008 (2)0.0021 (2)0.0011 (2)
P20.0082 (3)0.0085 (3)0.0092 (3)−0.0007 (2)0.0009 (2)0.0011 (2)
O10.0097 (9)0.0127 (8)0.0146 (9)0.0029 (7)0.0037 (7)0.0037 (7)
O20.0095 (9)0.0182 (9)0.0192 (10)−0.0040 (7)−0.0004 (8)0.0001 (7)
O30.0201 (10)0.0137 (8)0.0110 (10)0.0048 (8)0.0034 (7)−0.0010 (7)
O40.0225 (11)0.0120 (9)0.0157 (10)−0.0038 (8)−0.0041 (8)−0.0012 (7)
O50.0113 (9)0.0156 (9)0.0143 (10)0.0031 (7)0.0031 (8)0.0039 (7)
O60.0141 (9)0.0107 (8)0.0159 (9)−0.0034 (7)0.0016 (7)0.0022 (7)
O70.0115 (9)0.0091 (8)0.0133 (9)0.0003 (7)0.0055 (7)0.0018 (7)
O80.0163 (11)0.0208 (10)0.0160 (11)−0.0033 (9)0.0013 (8)0.0035 (8)
O90.0432 (13)0.0160 (10)0.0159 (11)0.0057 (10)−0.0061 (9)−0.0017 (8)
O100.0138 (10)0.0163 (10)0.0697 (17)−0.0019 (9)−0.0005 (11)−0.0122 (11)
O110.0541 (17)0.0120 (11)0.0542 (16)−0.0102 (10)0.0317 (14)−0.0094 (10)

Geometric parameters (Å, °)

Tb1—O12.3145 (17)P1—O11.5129 (18)
Tb1—O2i2.2877 (17)P1—O21.5063 (18)
Tb1—O3ii2.3514 (18)P1—O31.5169 (19)
Tb1—O52.3718 (18)P1—O71.6201 (18)
Tb1—O6iii2.3842 (17)P2—O41.562 (2)
Tb1—O82.605 (2)P2—O51.4957 (19)
Tb1—O92.433 (2)P2—O61.4891 (18)
Tb1—O102.421 (2)P2—O71.6116 (18)
O1—Tb1—O2i143.70 (6)O6iii—Tb1—O8128.03 (6)
O1—Tb1—O3ii83.41 (6)O6iii—Tb1—O975.70 (7)
O1—Tb1—O575.74 (6)O6iii—Tb1—O1071.65 (6)
O1—Tb1—O6iii134.37 (6)O8—Tb1—O9136.20 (6)
O1—Tb1—O875.29 (6)O8—Tb1—O10141.01 (7)
O1—Tb1—O9116.61 (7)O9—Tb1—O1076.69 (8)
O1—Tb1—O1069.56 (7)O1—P1—O2113.46 (10)
O2i—Tb1—O3ii101.23 (6)O1—P1—O3113.12 (10)
O2i—Tb1—O580.10 (6)O1—P1—O7107.03 (10)
O2i—Tb1—O6iii79.67 (6)O2—P1—O3111.92 (11)
O2i—Tb1—O871.90 (6)O2—P1—O7106.35 (10)
O2i—Tb1—O979.03 (7)O3—P1—O7104.14 (10)
O2i—Tb1—O10146.08 (7)O4—P2—O5111.48 (10)
O3ii—Tb1—O5143.50 (6)O4—P2—O6107.99 (10)
O3ii—Tb1—O6iii71.04 (6)O4—P2—O7105.60 (10)
O3ii—Tb1—O873.05 (6)O5—P2—O6117.25 (10)
O3ii—Tb1—O9146.04 (7)O5—P2—O7108.46 (10)
O3ii—Tb1—O1086.44 (8)O6—P2—O7105.28 (10)
O5—Tb1—O6iii143.13 (6)H81—O8—H82109 (3)
O5—Tb1—O872.85 (6)H91—O9—H92104 (3)
O5—Tb1—O970.39 (6)H101—O10—H102106 (3)
O5—Tb1—O10112.90 (7)H111—O11—H112109 (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.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O4—H41···O110.813 (13)1.736 (14)2.546 (3)174 (3)
O8—H81···O1ii0.82 (2)1.98 (3)2.762 (3)159 (3)
O8—H82···O3i0.822 (18)2.231 (14)2.972 (3)150 (3)
O9—H91···O4iv0.83 (3)2.06 (3)2.851 (3)161 (3)
O9—H92···O8iii0.828 (18)1.95 (2)2.750 (3)164 (3)
O10—H101···O5iii0.82 (2)2.16 (3)2.880 (3)147 (3)
O10—H102···O7v0.812 (16)2.28 (2)2.991 (3)147 (3)
O11—H111···O3v0.80 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2172).

References

  • Anna-Rabah, Z., Chehimi-Moumen, F., Ben Hassen-Chehimi, D. & Trabelsi-Ayadi, M. (2006). Solid State Sci.8, 932–939.
  • Brandenburg, K. & Putz, H. (2005). DIAMOND. Version 3. Crystal Impact GbR, Postfach 1251, D-53002 Bonn, Germany.
  • Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst.36, 1103.
  • Chehimi-Moumen, F., Ferid, M., Ben-Hassen-Chehimi, D. & Trabelsi-Ayadi, M. (2002). Solid State Sci.4, 979–983.
  • Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.
  • Hraiech, S., Chehimi-Moumen, F., Ferid, M., Ben Hassen-Chehimi, D. & Trabelsi-Ayadi, D. (2005). Mater. Res. Bull.40, 2170–2179.
  • Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
  • Petříček, V., Dušek, M. & Palatinus, L. (2007). JANA2000 Institute of Physics, Prague, Czech Republic.

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