Acta Cryst. (2008). E64, i49 [ doi:10.1107/S1600536808021818 ]
![[mu]](/logos/entities/mu_rmgif.gif)
2-hydroxido-4-sulfato-neodymium(III)]The title compound, [Nd(OH)(SO4)]n, was obtained hydrothermally from an aqueous solution of neodymium nitrate, 1,2-propanediamine and sulfuric acid. The structure features nonacoordinated neodymium with sulfate and hydroxide anions acting as bridging ligands. The OH group forms a weak O-H
O hydrogen bond with an OO distance of 3.224 (5) Å.
Pink block crystals were synthesized hydrothermally from a mixture of Nd(NO3)3.6H2O, 1,2-propane diamine, H2SO4 and water. In a typical synthesis, Nd(NO3)3.6H2O (0.6066 g) was dissolved in a mixture of 1,2-propane diamine (0.2205 g) and water (3.2 ml) followed by the addition of H2SO4 (98%) (0.3093 g) with constant stirring. Finally, the mixture was kept in a 25 ml Teflon-lined steel autoclave at 180 °C for 7 days. After the autoclave was slowly cooled to room temperature, Pink block crystals of the title compound were obtained.
The H atom of water was located from difference map, while the distance of O—H was restrained 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, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./br2079fig1thm.gif)
| Fig. 1. The molecular structure for title compound. Displacement ellipsoids at the 50% probability level. |
![[Figure 2]](./br2079fig2thm.gif)
| Fig. 2. The crystal packing in the unit cell of Nd(SO4)(OH). |
| [Nd(OH)(SO4)] | F000 = 468 |
| Mr = 257.31 | Dx = 4.676 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 150 reflections |
| a = 4.4678 (9) Å | θ = 2.3–22.5º |
| b = 12.432 (2) Å | µ = 14.66 mm−1 |
| c = 6.8575 (13) Å | T = 293 (2) K |
| β = 106.324 (3)º | Block, pink |
| V = 365.53 (12) Å3 | 0.10 × 0.08 × 0.06 mm |
| Z = 4 |
| Bruker APEXII CCD diffractometer | 675 independent reflections |
| Radiation source: fine-focus sealed tube | 669 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.013 |
| T = 293(2) K | θmax = 25.5º |
| ω scans | θmin = 3.3º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −3→5 |
| Tmin = 0.322, Tmax = 0.473 | k = −14→15 |
| 1837 measured reflections | l = −7→8 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.022 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.035P)2 + 0.7631P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.24 | (Δ/σ)max = 0.001 |
| 675 reflections | Δρmax = 0.56 e Å−3 |
| 67 parameters | Δρmin = −2.27 e Å−3 |
| 1 restraint | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| [Nd(OH)(SO4)] | V = 365.53 (12) Å3 |
| Mr = 257.31 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 4.4678 (9) Å | µ = 14.66 mm−1 |
| b = 12.432 (2) Å | T = 293 (2) K |
| c = 6.8575 (13) Å | 0.10 × 0.08 × 0.06 mm |
| β = 106.324 (3)º |
| Bruker APEXII CCD diffractometer | 675 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 669 reflections with I > 2σ(I) |
| Tmin = 0.322, Tmax = 0.473 | Rint = 0.013 |
| 1837 measured reflections |
| R[F2 > 2σ(F2)] = 0.022 | 1 restraint |
| wR(F2) = 0.056 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.24 | Δρmax = 0.56 e Å−3 |
| 675 reflections | Δρmin = −2.27 e Å−3 |
| 67 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 | ||
| Nd1 | 0.14116 (6) | 0.93569 (2) | 0.80136 (4) | 0.00655 (15) | |
| S1 | 0.4852 (3) | 0.85400 (10) | 0.38900 (18) | 0.0059 (3) | |
| O1 | 0.3672 (9) | 0.8343 (3) | 0.5628 (6) | 0.0136 (8) | |
| O2 | 0.2485 (9) | 0.9040 (3) | 0.2196 (6) | 0.0127 (8) | |
| O3 | 0.7563 (9) | 0.9295 (3) | 0.4498 (6) | 0.0105 (8) | |
| O4 | 0.5923 (9) | 0.7539 (3) | 0.3200 (6) | 0.0129 (8) | |
| O5 | 0.3028 (9) | 1.0847 (3) | 1.0385 (6) | 0.0081 (7) | |
| H1 | 0.295 (14) | 1.148 (2) | 0.997 (9) | 0.010* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Nd1 | 0.0075 (2) | 0.0051 (2) | 0.0073 (2) | 0.00001 (8) | 0.00245 (14) | −0.00073 (8) |
| S1 | 0.0073 (6) | 0.0040 (6) | 0.0068 (6) | 0.0003 (4) | 0.0026 (5) | −0.0001 (4) |
| O1 | 0.0172 (19) | 0.0129 (19) | 0.0136 (19) | 0.0013 (16) | 0.0093 (16) | 0.0003 (15) |
| O2 | 0.0096 (18) | 0.0133 (18) | 0.0131 (18) | 0.0026 (16) | −0.0002 (15) | 0.0032 (15) |
| O3 | 0.0088 (19) | 0.008 (2) | 0.015 (2) | −0.0023 (13) | 0.0036 (16) | −0.0004 (13) |
| O4 | 0.0196 (19) | 0.0066 (19) | 0.015 (2) | 0.0037 (15) | 0.0092 (17) | −0.0002 (14) |
| O5 | 0.0080 (18) | 0.0034 (16) | 0.0122 (18) | 0.0005 (14) | 0.0016 (14) | 0.0027 (14) |
| Nd1—O4i | 2.374 (4) | S1—O1 | 1.453 (4) |
| Nd1—O5ii | 2.431 (4) | S1—O4 | 1.459 (4) |
| Nd1—O5 | 2.437 (4) | S1—O2 | 1.470 (4) |
| Nd1—O1 | 2.492 (4) | S1—O3 | 1.496 (4) |
| Nd1—O3iii | 2.535 (4) | O2—Nd1vi | 2.624 (4) |
| Nd1—O5iv | 2.536 (4) | O2—Nd1viii | 2.800 (4) |
| Nd1—O3v | 2.538 (4) | O3—Nd1iii | 2.535 (4) |
| Nd1—O2vi | 2.624 (4) | O3—Nd1ix | 2.538 (4) |
| Nd1—O2vii | 2.800 (4) | O4—Nd1x | 2.374 (4) |
| Nd1—Nd1iv | 3.6744 (7) | O5—Nd1ii | 2.431 (4) |
| Nd1—Nd1ii | 3.9178 (7) | O5—Nd1iv | 2.536 (4) |
| O4i—Nd1—O5ii | 88.26 (13) | O4i—Nd1—Nd1iv | 109.65 (10) |
| O4i—Nd1—O5 | 137.19 (13) | O5ii—Nd1—Nd1iv | 103.34 (9) |
| O5ii—Nd1—O5 | 72.81 (14) | O5—Nd1—Nd1iv | 43.41 (9) |
| O4i—Nd1—O1 | 66.02 (13) | O1—Nd1—Nd1iv | 173.45 (9) |
| O5ii—Nd1—O1 | 72.10 (13) | O3iii—Nd1—Nd1iv | 112.42 (8) |
| O5—Nd1—O1 | 136.35 (13) | O5iv—Nd1—Nd1iv | 41.33 (8) |
| O4i—Nd1—O3iii | 136.85 (12) | O3v—Nd1—Nd1iv | 115.79 (9) |
| O5ii—Nd1—O3iii | 91.10 (13) | O2vi—Nd1—Nd1iv | 49.41 (8) |
| O5—Nd1—O3iii | 82.80 (13) | O2vii—Nd1—Nd1iv | 45.37 (8) |
| O1—Nd1—O3iii | 72.80 (12) | O4i—Nd1—Nd1ii | 115.94 (9) |
| O4i—Nd1—O5iv | 77.43 (13) | O5ii—Nd1—Nd1ii | 36.45 (9) |
| O5ii—Nd1—O5iv | 128.19 (16) | O5—Nd1—Nd1ii | 36.35 (9) |
| O5—Nd1—O5iv | 84.74 (13) | O1—Nd1—Nd1ii | 105.03 (9) |
| O1—Nd1—O5iv | 138.09 (13) | O3iii—Nd1—Nd1ii | 86.21 (9) |
| O3iii—Nd1—O5iv | 132.32 (12) | O5iv—Nd1—Nd1ii | 109.06 (9) |
| O4i—Nd1—O3v | 88.46 (12) | O3v—Nd1—Nd1ii | 151.19 (8) |
| O5ii—Nd1—O3v | 139.42 (13) | O2vi—Nd1—Nd1ii | 97.41 (9) |
| O5—Nd1—O3v | 130.63 (11) | O2vii—Nd1—Nd1ii | 58.27 (8) |
| O1—Nd1—O3v | 69.68 (13) | Nd1iv—Nd1—Nd1ii | 72.017 (16) |
| O3iii—Nd1—O3v | 65.06 (14) | O1—S1—O4 | 110.5 (2) |
| O5iv—Nd1—O3v | 90.27 (13) | O1—S1—O2 | 111.9 (2) |
| O4i—Nd1—O2vi | 133.45 (13) | O4—S1—O2 | 109.4 (2) |
| O5ii—Nd1—O2vi | 133.02 (12) | O1—S1—O3 | 109.2 (2) |
| O5—Nd1—O2vi | 61.74 (12) | O4—S1—O3 | 108.2 (2) |
| O1—Nd1—O2vi | 137.14 (12) | O2—S1—O3 | 107.5 (2) |
| O3iii—Nd1—O2vi | 72.81 (13) | S1—O1—Nd1 | 139.5 (2) |
| O5iv—Nd1—O2vi | 60.80 (12) | S1—O2—Nd1vi | 133.1 (2) |
| O3v—Nd1—O2vi | 73.07 (12) | S1—O2—Nd1viii | 138.3 (2) |
| O4i—Nd1—O2vii | 78.28 (12) | Nd1vi—O2—Nd1viii | 85.22 (11) |
| O5ii—Nd1—O2vii | 70.32 (12) | S1—O3—Nd1iii | 120.8 (2) |
| O5—Nd1—O2vii | 59.36 (12) | S1—O3—Nd1ix | 124.3 (2) |
| O1—Nd1—O2vii | 128.08 (12) | Nd1iii—O3—Nd1ix | 114.94 (14) |
| O3iii—Nd1—O2vii | 141.03 (12) | S1—O4—Nd1x | 155.2 (3) |
| O5iv—Nd1—O2vii | 58.11 (12) | Nd1ii—O5—Nd1 | 107.19 (14) |
| O3v—Nd1—O2vii | 147.55 (12) | Nd1ii—O5—Nd1iv | 128.19 (16) |
| O2vi—Nd1—O2vii | 94.78 (11) | Nd1—O5—Nd1iv | 95.26 (12) |
| Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+1, −y+2, −z+2; (iii) −x+1, −y+2, −z+1; (iv) −x, −y+2, −z+2; (v) x−1, y, z; (vi) −x, −y+2, −z+1; (vii) x, y, z+1; (viii) x, y, z−1; (ix) x+1, y, z; (x) x+1/2, −y+3/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O5—H1···O1xi | 0.83 (3) | 2.43 (3) | 3.224 (5) | 160 (6) |
| Symmetry codes: (xi) −x+1/2, y+1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O5—H1···O1i | 0.83 (3) | 2.43 (3) | 3.224 (5) | 160 (6) |
| Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2. |
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In the last few years, the synthesis of new three dimensional lanthanide sulfates have received great attention, due to their functional applications in catalysis, ion-exchange, and optical device (Zhang et al.,2004; Yuan et al., 2004; Xu, Ding, Feng et al., 2006; Xu, Ding, Zhou & Liu, 2006; Doran et al., 2002, Xu et al., 2007). In this work, we designed and synthesized the title compound, neodymium(3+) sulfate hydroxide, which features a three–dimensional framework constructed from NdO9 polyhedra and SO4 tetrahedra.
Nd(SO4)(OH) is isostructural with La(SO4)(OH) (Zhang et al.,2004) and Eu(SO4)(OH)(Ding et al.,2006), the framework of title compound constructed from NdO9 polyhedra and SO4 tetrahedra. As show in Fig. 1, the asymmetric unit contains one Nd3+, one SO42– group and one hydroxide group. The Nd3+ is coordinated by six bridging sulfate ions, each S atom makes four S–O–Nd linkages by sharing the bridging O atoms. The coordination sphere of Nd is completed by three OH- groups, which act as briding ligands between three Nd^3+^.
The O-H group is involved hydrogen bonding interactions with O1, O2 and O4, the distances of O—H···O are vary from 2.60 (2) to 2.90 (2) Å.
The Nd —O distances are between of 2.374 (4)– 2.800 (4)Å (Table 1)while the O—Nd—O angles are between 66.02 (13) and 141.55 (12)°. These bond distances and bond angles are in agreement with those found in the reported rare-earth compounds (Zhang et al.,2004; Ding et al.,2006). The bond distances of S—O and angles of O—S—O are unexceptional. Fig. 2 shows the three-dimensional arrangement in the unit cell, displaying the way the different Nd3+ are connected by bridging hydroxide and sulfates groups.