Acta Cryst. (2007). E63, m3078 [ doi:10.1107/S1600536807058643 ]
In the ionic title complex, [Nd{CO(NH2)2}4(H2O)4]I3, the neodymium is located on a twofold rotation axis and is coordinated by four urea and four water molecules in a distorted square-antiprismatic geometry.
Nonahydrate of neodymium(III) iodide NdI3.9H2O was prepared by the reaction of neodymium(III) carbonate with hydroiodic acid preliminary freed from iodine excess (Huber et al., 1985). The complex compound NdI3.4Ur.4H2O was synthesized by mixing NdI3.9H2O with CO(NH2)2 in molar ratio 1:5 without water addition. Interaction of crystalline reagents in the course of mixture grinding leads to the crystallization water liberation and formation of viscous transparent solution. Pale violet crystals are obtained after allowing the solution to stay for 2 weeks. The results of chemical analysis (titration with Na2edta solution for neodymium content determination and gravimetric analysis via AgI formation for iodide–ion content determination) are as follows: Nd (wt.%) 17.23 (calcd.), 16.15 (found); I(wt.%) 45.48 (calcd.), 42.63 (found). The reduced content of Nd and I is possibly related with the compound hygroscopicity. M.p. 371 K.
Amide H atoms were positioned geometrically and refined using a riding model with N—H = 0.86 Å, O—H = 0.85 Å and Uiso(H) = 1.2 times Ueq of the parent atom. The largest difference peak is located at 0.6172, 0.1779, 0.2360 with the distance 1.03 Å from Nd1.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./rk2058fig1thm.gif)
| Fig. 1. ORTEP–3 (Farrugia, 1997) view of the title complex, with atom labels. Displacement ellipsoids are drawn at 50% probability. H atoms are presented as a spheres of arbitrary radius. Symmetry code: (i) 1 − x, y, −z + 1/2. |
| [Nd(C1H4N2O1)4(H2O1)4]I3 | F000 = 774 |
| Mr = 837.25 | Dx = 2.349 Mg m−3 |
| Monoclinic, P2/c | Melting point: 371 K |
| Hall symbol: -P 2yc | Mo Kα radiation λ = 0.71073 Å |
| a = 7.7633 (19) Å | Cell parameters from 25 reflections |
| b = 10.597 (4) Å | θ = 14–15º |
| c = 15.140 (4) Å | µ = 6.15 mm−1 |
| β = 108.136 (19)º | T = 293 (2) K |
| V = 1183.7 (6) Å3 | Prism, violet |
| Z = 2 | 0.20 × 0.20 × 0.20 mm |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.000 |
| Radiation source: fine–focus sealed tube | θmax = 30.0º |
| Monochromator: graphite | θmin = 1.9º |
| T = 293(2) K | h = −10→10 |
| non–profiled ω–scans | k = −14→0 |
| Absorption correction: ψ scan (North et al., 1968) | l = −21→9 |
| Tmin = 0.293, Tmax = 0.304 | 1 standard reflections |
| 3446 measured reflections | every 120 min |
| 3446 independent reflections | intensity decay: 2% |
| 2589 reflections with I > 2σ(I) |
| 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)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0298P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.00 | (Δ/σ)max = 0.001 |
| 3446 reflections | Δρmax = 0.73 e Å−3 |
| 126 parameters | Δρmin = −0.55 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Nd(C1H4N2O1)4(H2O1)4]I3 | V = 1183.7 (6) Å3 |
| Mr = 837.25 | Z = 2 |
| Monoclinic, P2/c | Mo Kα |
| a = 7.7633 (19) Å | µ = 6.15 mm−1 |
| b = 10.597 (4) Å | T = 293 (2) K |
| c = 15.140 (4) Å | 0.20 × 0.20 × 0.20 mm |
| β = 108.136 (19)º |
| Enraf–Nonius CAD-4 diffractometer | 2589 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.000 |
| Tmin = 0.293, Tmax = 0.304 | 1 standard reflections |
| 3446 measured reflections | every 120 min |
| 3446 independent reflections | intensity decay: 2% |
| R[F2 > 2σ(F2)] = 0.035 | 126 parameters |
| wR(F2) = 0.070 | H-atom parameters constrained |
| S = 1.00 | Δρmax = 0.73 e Å−3 |
| 3446 reflections | Δρmin = −0.55 e Å−3 |
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 > 2σ(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 | 0.5000 | 0.15416 (3) | 0.2500 | 0.03067 (8) | |
| I1 | 0.0000 | 0.53143 (5) | 0.2500 | 0.05980 (15) | |
| I2 | 0.82533 (5) | 0.78527 (3) | 0.49371 (3) | 0.05522 (11) | |
| O1 | 0.3857 (6) | 0.3168 (4) | 0.1427 (3) | 0.0869 (14) | |
| C1 | 0.3636 (7) | 0.4170 (5) | 0.0989 (4) | 0.0535 (13) | |
| N11 | 0.2203 (6) | 0.4292 (5) | 0.0241 (4) | 0.0677 (13) | |
| H11A | 0.1446 | 0.3680 | 0.0067 | 0.081* | |
| H11B | 0.2030 | 0.4984 | −0.0072 | 0.081* | |
| N12 | 0.4807 (7) | 0.5126 (5) | 0.1217 (4) | 0.0891 (19) | |
| H12A | 0.5769 | 0.5061 | 0.1688 | 0.107* | |
| H12B | 0.4600 | 0.5807 | 0.0892 | 0.107* | |
| O2 | 0.4141 (5) | −0.0102 (3) | 0.3359 (3) | 0.0595 (10) | |
| C2 | 0.3219 (7) | −0.1020 (6) | 0.3391 (5) | 0.0649 (16) | |
| N21 | 0.2945 (10) | −0.1930 (6) | 0.2739 (5) | 0.121 (3) | |
| H21A | 0.3421 | −0.1863 | 0.2299 | 0.145* | |
| H21B | 0.2293 | −0.2578 | 0.2764 | 0.145* | |
| N22 | 0.2716 (12) | −0.1279 (7) | 0.4085 (6) | 0.165 (4) | |
| H22A | 0.3023 | −0.0796 | 0.4565 | 0.198* | |
| H22B | 0.2065 | −0.1938 | 0.4078 | 0.198* | |
| O3 | 0.2249 (5) | 0.2324 (4) | 0.2831 (3) | 0.0635 (10) | |
| H3A | 0.179 | 0.303 | 0.262 | 0.076* | |
| H3B | 0.207 | 0.225 | 0.3356 | 0.076* | |
| O4 | 0.2283 (5) | 0.0663 (4) | 0.1314 (3) | 0.0709 (12) | |
| H4A | 0.131 | 0.107 | 0.105 | 0.085* | |
| H4B | 0.209 | −0.008 | 0.109 | 0.085* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Nd1 | 0.03188 (14) | 0.02026 (13) | 0.03909 (17) | 0.000 | 0.00991 (12) | 0.000 |
| I1 | 0.0509 (3) | 0.0385 (2) | 0.0817 (4) | 0.000 | 0.0085 (2) | 0.000 |
| I2 | 0.0559 (2) | 0.03773 (17) | 0.0624 (2) | 0.00232 (14) | 0.00431 (16) | 0.00285 (15) |
| O1 | 0.083 (3) | 0.062 (3) | 0.113 (4) | 0.021 (2) | 0.027 (3) | 0.057 (3) |
| C1 | 0.052 (3) | 0.042 (3) | 0.068 (3) | 0.010 (2) | 0.020 (3) | 0.023 (3) |
| N11 | 0.059 (3) | 0.055 (3) | 0.081 (3) | −0.005 (2) | 0.009 (3) | 0.020 (3) |
| N12 | 0.064 (3) | 0.064 (3) | 0.108 (4) | −0.012 (3) | −0.018 (3) | 0.030 (3) |
| O2 | 0.0502 (19) | 0.048 (2) | 0.077 (3) | −0.0097 (16) | 0.0149 (18) | 0.0219 (19) |
| C2 | 0.056 (3) | 0.049 (3) | 0.087 (4) | −0.006 (3) | 0.020 (3) | 0.025 (3) |
| N21 | 0.152 (7) | 0.087 (5) | 0.120 (6) | −0.049 (5) | 0.039 (5) | −0.008 (4) |
| N22 | 0.234 (10) | 0.125 (7) | 0.209 (10) | −0.068 (6) | 0.175 (9) | −0.025 (6) |
| O3 | 0.063 (2) | 0.053 (2) | 0.086 (3) | 0.0198 (19) | 0.039 (2) | 0.016 (2) |
| O4 | 0.056 (2) | 0.053 (2) | 0.079 (3) | 0.0128 (18) | −0.0164 (19) | −0.027 (2) |
| Nd1—O1i | 2.345 (4) | N12—H12A | 0.8600 |
| Nd1—O1 | 2.345 (4) | N12—H12B | 0.8600 |
| Nd1—O2 | 2.389 (3) | O2—C2 | 1.218 (6) |
| Nd1—O2i | 2.389 (3) | C2—N22 | 1.259 (9) |
| Nd1—O3i | 2.484 (3) | C2—N21 | 1.348 (9) |
| Nd1—O3 | 2.484 (3) | N21—H21A | 0.8600 |
| Nd1—O4 | 2.487 (3) | N21—H21B | 0.8600 |
| Nd1—O4i | 2.487 (3) | N22—H22A | 0.8600 |
| O1—C1 | 1.235 (6) | N22—H22B | 0.8600 |
| C1—N11 | 1.324 (7) | O3—H3A | 0.8500 |
| C1—N12 | 1.333 (7) | O3—H3B | 0.8500 |
| N11—H11A | 0.8600 | O4—H4A | 0.8500 |
| N11—H11B | 0.8600 | O4—H4B | 0.8500 |
| O1i—Nd1—O1 | 85.4 (3) | N11—C1—N12 | 118.1 (5) |
| O1i—Nd1—O2 | 105.55 (16) | C1—N11—H11A | 120.0 |
| O1—Nd1—O2 | 143.45 (14) | C1—N11—H11B | 120.0 |
| O1—Nd1—O2i | 105.55 (16) | H11A—N11—H11B | 120.0 |
| O2—Nd1—O2i | 86.4 (2) | C1—N12—H12A | 120.0 |
| O1—Nd1—O3i | 77.19 (16) | C1—N12—H12B | 120.0 |
| O2—Nd1—O3i | 139.17 (13) | H12A—N12—H12B | 120.0 |
| O1—Nd1—O3 | 74.39 (15) | C2—O2—Nd1 | 150.6 (4) |
| O2—Nd1—O3 | 74.34 (13) | O2—C2—N22 | 123.1 (8) |
| O2i—Nd1—O3 | 139.17 (13) | O2—C2—N21 | 120.2 (6) |
| O3i—Nd1—O3 | 140.99 (19) | N22—C2—N21 | 115.8 (7) |
| O1i—Nd1—O4 | 145.93 (14) | C2—N21—H21A | 120.0 |
| O1—Nd1—O4 | 73.87 (16) | C2—N21—H21B | 120.0 |
| O2—Nd1—O4 | 78.60 (15) | H21A—N21—H21B | 120.0 |
| O2i—Nd1—O4 | 69.62 (12) | C2—N22—H22A | 120.0 |
| O3i—Nd1—O4 | 124.67 (16) | C2—N22—H22B | 120.0 |
| O3—Nd1—O4 | 71.41 (15) | H22A—N22—H22B | 120.0 |
| O1—Nd1—O4i | 145.93 (14) | Nd1—O3—H3A | 121 |
| O2—Nd1—O4i | 69.62 (12) | Nd1—O3—H3B | 124 |
| O3—Nd1—O4i | 124.67 (16) | H3A—O3—H3B | 105.1 |
| O4—Nd1—O4i | 136.01 (18) | Nd1—O4—H4A | 125 |
| C1—O1—Nd1 | 164.4 (4) | Nd1—O4—H4B | 130 |
| O1—C1—N11 | 118.9 (5) | H4A—O4—H4B | 105.2 |
| O1—C1—N12 | 123.0 (5) |
| Symmetry codes: (i) −x+1, y, −z+1/2. |
The authors are indebted to the Russian Foundation for Basic Research for covering the licence fee for use of the Cambridge Structural Database.
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An increased attention to investigation of different salts interaction with carbamide CO(NH2)2 (Ur) is determined by the special features of the structure and properties of this ambidentate ligand which could be coordinated by the metal cation via both nitrogen atom of amino–group and oxygen atom of the carbonyl group. It should be noted that O–coordinated carbamide has a possibility to participate in the formation of the hydrogen bonding developed system as well as layered and channel structures of the clathrate–coordination nature, these systems being related to supramolecular ones (Sulejmanov et al., 1971). The neodymium–containing complexes are of great importance for preparation of laser, fiber optic and luminescent and other materials with interesting properties.
It has been found out that interaction of the lanthanide salts with carbamide leads to a number of different complexes whose composition is to a great extent temperature dependent. For example, at 288 and 303 K lanthanide chlorides yield the anhydrous complexes of different composition such as LnCl3.4Ur, LnCl3.6Ur (Ln = La, Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er, etc.) as well as ErCl3.2Ur.6H2O and TmCl3.2Ur.4H2O (Dilebaeva & Sulajmankulov, 1973; Dilebaeva et al., 1975). At the same temperature conditions lanthanide bromides give analogous compounds LnBr3.4Ur, LnBr3.6Ur (Ln = La, Ce, Er, etc.), as well as ErBr3.Ur.6H2O (Aitimbetov et al., 1977).
Regarding lanthanide iodides, anhydrous complexes LnI3.5Ur (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) have been prepared at 273 K (Rukk et al., 1984; Alikberova et al., 1990). The compound SmI3.8Ur has been synthesized at room temperature (Savinkina et al., 2005). The single-crystal X–ray diffraction studies confirmed the IR spectra investigation results with respect to coordination of the carbamide ligands via the O–atom of the carbonyl group.
The aim of the present work is to synthesize and to investigate the new neodymium iodide complex with carbamide at room temperature.
The [Nd(Ur)4(H2O)4]3+ complex cation is located on a twofold rotation axis and its geometry represents the distorted square antiprism with eight oxygen atoms (four from water molecules and four from the carbamide ones) located in the mentioned antiprism vertices. The complex cations form double layers, the NH2 groups of coordinated carbamide molecules of neighboring layers being symmetrically disposed. Almost flat ordered layers built from the iodide–ions are located between the double layers of complex cations. The results of our investigation confirm the early proposed assumption about the layered structure of lanthanide iodide complexes with carbamide, but we were unable to investigate hydrogen bonding geometry because of poor refinement of H atoms in this structure containing such heavy atoms as Nd and I.