Acta Cryst. (2009). E65, i61-i62 [ doi:10.1107/S1600536809027068 ]
During our research into novel nonlinear optical materials using 1,10-phenanthroline as an appending ligand on lanthanide iodates, crystals of an infinite layered DyIII iodate compound, Dy(IO3)3(H2O)·H2O, were obtained under hydrothermal conditions. The DyIII cation has a dicapped trigonal prismatic coordination environment consisting of one water O atom and seven other O atoms from seven iodate anions. These iodate anions bridge the DyIII cations into a two-dimensional structure. Through O-H
O hydrogen bonds, all of these layers stack along [111], giving a supramolecular channel, with the solvent water molecules filling the voids.
All chemicals were obtained from commercial sources and were used as received. The title compound was handily synthesized by a hydrothermal reaction from iodic acid. To a 25 ml stainless steal Teflon-lined reaction vessel, Dy2O3 (0.2 mmol, 75 mg), HIO3 (0.8 mmol, 141 mg), 1,10-phenanthroline (0.4 mmol, 80 mg) and 13 ml H2O were added and stirred thoroughly for 1 h, then heated at 393 K for 2 d. After cooling down to room temperature, some colorless crystalline product (I) was obtained.
The structure was solved using direct methods and refined by full-matrix least-squares techniques. All non-hydrogen atoms were assigned anisotropic displacement parameters in the refinement. All H atoms were added at calculated positions and refined using a riding model.(Sheldrick, 2008). The maximum (2.79) and minumum (-3.20) in the difference electron density were found at 0.0198 0.3244 0.7024 [1.01 Å from DY1] and 0.2071 0.4512 0.7963 [0.60 Å from DY1], respectively.
The O6 has ADP max/min ratio 6.70. This result may be due to the packing of supramolecule.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009; van der Sluis & Spek, 1990); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./br2111fig1thm.gif)
| Fig. 1. Structure and labeling of the title compound, with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii. |
![[Figure 2]](./br2111fig2thm.gif)
| Fig. 2. The packing diagram viewed along the a-direction, Dy: green diagonal; I: purple inner dot; O: red; and H: small blue circles. And hydrogen bonds are denoted as dash lines. |
| Dy(IO3)3H2O·H2O | Z = 2 |
| Mr = 723.23 | F000 = 634 |
| Triclinic, P1 | Dx = 4.766 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71075 Å |
| a = 7.15990 (10) Å | Cell parameters from 1561 reflections |
| b = 7.4292 (1) Å | θ = 2.0–27.5º |
| c = 10.64430 (10) Å | µ = 16.65 mm−1 |
| α = 95.161 (12)º | T = 293 K |
| β = 104.858 (7)º | Block, colourless |
| γ = 110.081 (8)º | 0.16 × 0.12 × 0.06 mm |
| V = 504.00 (5) Å3 |
| Rigaku R-AXIS RAPID diffractometer | 2260 independent reflections |
| Radiation source: fine-focus sealed tube | 2067 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.027 |
| Detector resolution: 14.6306 pixels mm-1 | θmax = 27.5º |
| T = 293 K | θmin = 3.2º |
| CCD profile fitting scans | h = −9→9 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −7→9 |
| Tmin = 0.136, Tmax = 0.435 | l = −13→13 |
| 3819 measured reflections |
| 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)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0647P)2 + 5.3292P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.06 | (Δ/σ)max < 0.001 |
| 2260 reflections | Δρmax = 2.79 e Å−3 |
| 141 parameters | Δρmin = −3.20 e Å−3 |
| 2 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0126 (8) |
| Dy(IO3)3H2O·H2O | γ = 110.081 (8)º |
| Mr = 723.23 | V = 504.00 (5) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.15990 (10) Å | Mo Kα |
| b = 7.4292 (1) Å | µ = 16.65 mm−1 |
| c = 10.64430 (10) Å | T = 293 K |
| α = 95.161 (12)º | 0.16 × 0.12 × 0.06 mm |
| β = 104.858 (7)º |
| Rigaku R-AXIS RAPID diffractometer | 2260 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 2067 reflections with I > 2σ(I) |
| Tmin = 0.136, Tmax = 0.435 | Rint = 0.027 |
| 3819 measured reflections |
| R[F2 > 2σ(F2)] = 0.038 | 2 restraints |
| wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.06 | Δρmax = 2.79 e Å−3 |
| 2260 reflections | Δρmin = −3.20 e Å−3 |
| 141 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 | ||
| Dy1 | 0.11491 (7) | −0.58338 (7) | −0.21096 (4) | 0.01105 (18) | |
| I1 | 0.30890 (8) | −0.14149 (8) | 0.07303 (5) | 0.00659 (18) | |
| I2 | 0.28110 (8) | −0.63445 (8) | 0.16834 (5) | 0.00652 (18) | |
| I3 | 0.27848 (9) | −0.26870 (9) | −0.45631 (6) | 0.00862 (19) | |
| O1 | 0.1496 (11) | −0.2711 (12) | −0.0929 (7) | 0.0178 (15) | |
| O2 | 0.0966 (11) | −0.1450 (11) | 0.1365 (7) | 0.0144 (14) | |
| O3 | 0.3778 (11) | 0.1033 (10) | 0.0380 (7) | 0.0134 (14) | |
| O4 | 0.2940 (11) | −0.5350 (11) | 0.0209 (7) | 0.0155 (15) | |
| O5 | 0.2291 (10) | −0.4405 (11) | 0.2502 (7) | 0.0131 (14) | |
| O6 | 0.5556 (10) | −0.5510 (11) | 0.2555 (7) | 0.0121 (14) | |
| O7 | 0.0908 (11) | −0.3710 (11) | −0.3699 (7) | 0.0130 (14) | |
| O8 | 0.1065 (11) | −0.1986 (11) | −0.5813 (7) | 0.0125 (14) | |
| O9 | 0.4335 (11) | −0.0352 (12) | −0.3515 (8) | 0.0187 (16) | |
| O10 | 0.2235 (12) | −0.8611 (12) | −0.2319 (8) | 0.0185 (16) | |
| H10A | 0.198 (15) | −0.928 (9) | −0.179 (7) | 0.028* | |
| H10B | 0.346 (4) | −0.8277 (13) | −0.221 (10) | 0.028* | |
| O11 | 0.2419 (13) | −0.7837 (13) | 0.3943 (9) | 0.0257 (18) | |
| H11A | 0.225 (3) | −0.897 (15) | 0.3811 (19) | 0.039* | |
| H11B | 0.144 (13) | −0.7725 (18) | 0.412 (2) | 0.039* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Dy1 | 0.0094 (3) | 0.0136 (3) | 0.0131 (3) | 0.00658 (19) | 0.00455 (18) | 0.00444 (19) |
| I1 | 0.0048 (3) | 0.0061 (3) | 0.0105 (3) | 0.0031 (2) | 0.0028 (2) | 0.0041 (2) |
| I2 | 0.0040 (3) | 0.0067 (3) | 0.0111 (3) | 0.0040 (2) | 0.0027 (2) | 0.0039 (2) |
| I3 | 0.0076 (3) | 0.0109 (3) | 0.0101 (3) | 0.0063 (2) | 0.0032 (2) | 0.0026 (2) |
| O1 | 0.014 (3) | 0.023 (4) | 0.012 (3) | 0.010 (3) | −0.004 (3) | −0.002 (3) |
| O2 | 0.011 (3) | 0.014 (4) | 0.022 (4) | 0.006 (3) | 0.009 (3) | 0.007 (3) |
| O3 | 0.020 (3) | 0.006 (3) | 0.020 (4) | 0.007 (3) | 0.011 (3) | 0.006 (3) |
| O4 | 0.019 (4) | 0.013 (4) | 0.014 (3) | 0.006 (3) | 0.005 (3) | 0.006 (3) |
| O5 | 0.006 (3) | 0.014 (4) | 0.021 (4) | 0.005 (3) | 0.007 (3) | 0.002 (3) |
| O6 | 0.001 (3) | 0.016 (4) | 0.018 (3) | 0.002 (3) | 0.003 (3) | 0.007 (3) |
| O7 | 0.014 (3) | 0.020 (4) | 0.013 (3) | 0.012 (3) | 0.007 (3) | 0.013 (3) |
| O8 | 0.014 (3) | 0.013 (4) | 0.013 (3) | 0.005 (3) | 0.007 (3) | 0.006 (3) |
| O9 | 0.011 (3) | 0.018 (4) | 0.022 (4) | 0.005 (3) | 0.000 (3) | −0.002 (3) |
| O10 | 0.022 (4) | 0.023 (4) | 0.025 (4) | 0.019 (3) | 0.013 (3) | 0.011 (3) |
| O11 | 0.022 (4) | 0.022 (4) | 0.034 (5) | 0.007 (4) | 0.012 (4) | 0.005 (4) |
| Dy1—O4 | 2.401 (7) | I2—O6 | 1.798 (6) |
| Dy1—O2i | 2.408 (7) | I2—O4 | 1.804 (7) |
| Dy1—O8ii | 2.412 (7) | I2—O5 | 1.812 (7) |
| Dy1—O6iii | 2.415 (6) | I3—O9 | 1.783 (8) |
| Dy1—O7 | 2.429 (6) | I3—O8 | 1.812 (7) |
| Dy1—O1 | 2.438 (8) | I3—O7 | 1.813 (7) |
| Dy1—O10 | 2.453 (7) | O2—Dy1i | 2.408 (7) |
| Dy1—O5i | 2.461 (6) | O5—Dy1i | 2.461 (6) |
| I1—O1 | 1.804 (7) | O6—Dy1iii | 2.415 (6) |
| I1—O2 | 1.809 (7) | O8—Dy1ii | 2.412 (7) |
| I1—O3 | 1.814 (7) | ||
| O4—Dy1—O2i | 75.1 (2) | O7—Dy1—O10 | 126.1 (2) |
| O4—Dy1—O8ii | 149.7 (2) | O1—Dy1—O10 | 151.9 (2) |
| O2i—Dy1—O8ii | 78.5 (2) | O4—Dy1—O5i | 112.2 (2) |
| O4—Dy1—O6iii | 90.6 (2) | O2i—Dy1—O5i | 73.6 (2) |
| O2i—Dy1—O6iii | 142.8 (2) | O8ii—Dy1—O5i | 73.6 (2) |
| O8ii—Dy1—O6iii | 101.7 (2) | O6iii—Dy1—O5i | 142.8 (2) |
| O4—Dy1—O7 | 135.1 (3) | O7—Dy1—O5i | 72.9 (2) |
| O2i—Dy1—O7 | 141.9 (2) | O1—Dy1—O5i | 69.4 (2) |
| O8ii—Dy1—O7 | 75.1 (2) | O10—Dy1—O5i | 132.9 (3) |
| O6iii—Dy1—O7 | 70.3 (2) | O1—I1—O2 | 96.8 (3) |
| O4—Dy1—O1 | 69.2 (2) | O1—I1—O3 | 97.2 (3) |
| O2i—Dy1—O1 | 111.8 (3) | O2—I1—O3 | 97.7 (3) |
| O8ii—Dy1—O1 | 136.0 (2) | O6—I2—O4 | 99.6 (3) |
| O6iii—Dy1—O1 | 93.9 (3) | O6—I2—O5 | 97.8 (3) |
| O7—Dy1—O1 | 72.0 (2) | O4—I2—O5 | 95.5 (3) |
| O4—Dy1—O10 | 84.5 (3) | O9—I3—O8 | 99.4 (3) |
| O2i—Dy1—O10 | 68.8 (3) | O9—I3—O7 | 101.4 (3) |
| O8ii—Dy1—O10 | 72.1 (2) | O8—I3—O7 | 96.1 (3) |
| O6iii—Dy1—O10 | 75.9 (3) |
| Symmetry codes: (i) −x, −y−1, −z; (ii) −x, −y−1, −z−1; (iii) −x+1, −y−1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O10—H10A···O3iv | 0.80 | 2.29 | 2.873 (10) | 131 |
| O10—H10B···O9iv | 0.80 | 2.33 | 2.753 (11) | 114 |
| O11—H11A···O8v | 0.80 | 2.22 | 2.954 (11) | 153 |
| O11—H11B···O7i | 0.80 | 2.26 | 2.946 (11) | 145 |
| Symmetry codes: (iv) x, y−1, z; (v) x, y−1, z+1; (i) −x, −y−1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O10—H10A···O3i | 0.80 | 2.29 | 2.873 (10) | 131 |
| O10—H10B···O9i | 0.80 | 2.33 | 2.753 (11) | 114 |
| O11—H11A···O8ii | 0.80 | 2.22 | 2.954 (11) | 153 |
| O11—H11B···O7iii | 0.80 | 2.26 | 2.946 (11) | 145 |
| Symmetry codes: (i) x, y−1, z; (ii) x, y−1, z+1; (iii) −x, −y−1, −z. |
The authors are grateful for financial support from the National Natural Science Foundation of China (project Nos. 50702054 and 20803070) and the Analysis and Testing Foundation of Zhejiang Province (project Nos. 2008F70034 and 2008F70053).
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In the 1970s, metal iodates have been extensively studied by Bell Laboratories not only for their nonlinear optical (NLO) properties but also for ferroelectric, piezoelectric and pyroelectric properties (Rosenzweig & Morosin, 1966; Liminga et al., 1977). In attempts to prepare noncentrosymmetric structures of lanthanide iodates, about six anhydrous structure types have been reported, in addition to numerous hydrated structures ranging from hemihydrates to pentahydrates. (Assefa et al., 2006). After comparing these structure types, herein, we find that the hydrated structures favor of adopting centrosymmetric structures. Then organic ligands are come into our view because they could form noncentrosymmetric inorganic–organic framework structures with metal ion. (Sun et al., 2009). Here, we firstly report a infinite layered DyIII iodate dihydrate synthesized from the hydrothermal reaction of Dy2O3, HIO3 and 1,10-phenanthroline.
In the title compound, the DyIII cation has dicapped trigonal prismatic coordination sphere. The coordination enciroments of the rare earth DyIII cation consist of eight O atoms derived from seven iodate anions and one water molecule (see Fig. 1). And these seven iodates are classed two types, one is three 3-connected iodates (of I2) through three O atoms, and the other is four iodates 2-connected (of I1 or I3) through two O atoms. Then these iodate anions bridge Dy atoms into two dimensional structure. And between the adjacent layers, there are two types of hydrogen bonds, one is O10—H10A···O3 bond, the other is O10—H10B···O9 bond. Then through these hydrogen bonds, all of these layers stacking along [111] axis to give out of a supramolecular channel. And the solvent water molecules fill in the channels, and stick on the channel with two hydrogen bonds of O11—H11A···O8 and O11—H11B···O7. (see Fig. 2) The hydrogen bonding data of lengths and angles are in the range of ordinary examples and have been examined by the PLATON program (Spek, 2009; van der Sluis & Spek, 1990).