Acta Cryst. (2009). E65, i9 [ doi:10.1107/S1600536809001640 ]
Single crystals of {FeHo6}I12Ho were obtained during the reaction of HoI3 with metallic holmium and iron in a sealed tantalum container. The crystal structure consists of isolated holmium clusters encapsulating a single Fe atom, {FeHo6} (
symmetry). The rare earth metal atoms are surrounded by 12 edge-capping and six terminal iodide ligands that either connect the clusters to each other directly or via HoI6 octahedra ( symmetry).
Black, almost cubic crystals of {FeHo6}I12Ho were obtained by the reaction of HoI3 (200 mg) with holmium powder (84 mg, Chempur, 99.9%) and iron powder (10 mg, Merck, p.a.) in a tantalum container at 1273 K for 200 h. HoI3 had been synthesized from stoichiometric amounts of holmium and iodine, followed by sublimation in high vacuum for purification (Meyer, 1991). Due to air and moisture sensitivity of both reagents and products, all handlings were carried out in an argon-filled glove box (M. Braun, Garching, Germany).
The displacement parameter for the Fe atom was refined isotropically. The highest peak (2.36 e Å-3) in the final difference Fourier map is 1.20 Å from atom Ho1 and the deepest hole (-2.44 e Å-3) is 2.40 Å from the same atom.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./wm2215fig1thm.gif)
| Fig. 1. : {FeHo6} clusters connected via HoI6 units, drawn with displacement ellipsoids at the 90% probability level [Symmetry codes: (i) 1 + y, 1 - x + y, 1 - z; (ii) 1 - y, -1 + x-y, z; (iii) -x + 8/3, -y + 1/3, -z + 4/3; (iv) x-y, -1 + x, 1 - z; v) 2 - x, -y, 1 - z; vi) 2 - x + y, 1 - x, z.] |
| FeHo7I12 | Dx = 6.323 Mg m−3 |
| Mr = 2733.16 | Mo Kα radiation, λ = 0.71073 Å |
| Trigonal, R3 | Cell parameters from 1775 reflections |
| Hall symbol: -R 3 | θ = 1.9–28.2° |
| a = 15.2973 (17) Å | µ = 32.43 mm−1 |
| c = 10.6252 (16) Å | T = 293 K |
| V = 2153.3 (5) Å3 | Cubic, black |
| Z = 3 | 0.2 × 0.2 × 0.2 mm |
| F(000) = 3393 |
| Stoe IPDS-II diffractometer | 1166 independent reflections |
| Radiation source: fine-focus sealed tube | 861 reflections with I > 2σ(I) |
| graphite | Rint = 0.115 |
| ω scans | θmax = 28.1°, θmin = 2.5° |
| Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)] | h = −20→19 |
| Tmin = 0.027, Tmax = 0.071 | k = −19→20 |
| 6920 measured reflections | l = −14→14 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.047P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.096 | (Δ/σ)max = 0.001 |
| S = 0.97 | Δρmax = 2.36 e Å−3 |
| 1166 reflections | Δρmin = −2.44 e Å−3 |
| 32 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.00035 (3) |
| FeHo7I12 | Z = 3 |
| Mr = 2733.16 | Mo Kα radiation |
| Trigonal, R3 | µ = 32.43 mm−1 |
| a = 15.2973 (17) Å | T = 293 K |
| c = 10.6252 (16) Å | 0.2 × 0.2 × 0.2 mm |
| V = 2153.3 (5) Å3 |
| Stoe IPDS-II diffractometer | 1166 independent reflections |
| Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)] | 861 reflections with I > 2σ(I) |
| Tmin = 0.027, Tmax = 0.071 | Rint = 0.115 |
| 6920 measured reflections | θmax = 28.1° |
| R[F2 > 2σ(F2)] = 0.039 | Δρmax = 2.36 e Å−3 |
| wR(F2) = 0.096 | Δρmin = −2.44 e Å−3 |
| S = 0.97 | Absolute structure: ? |
| 1166 reflections | Flack parameter: ? |
| 32 parameters | Rogers parameter: ? |
| 0 restraints |
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 | ||
| Ho1 | 1.15739 (5) | 0.04355 (5) | 0.63807 (6) | 0.0153 (2) | |
| Ho2 | 1.0000 | 0.0000 | 1.0000 | 0.0213 (4) | |
| I1 | 1.05135 (6) | −0.13025 (7) | 0.83941 (7) | 0.0190 (2) | |
| I2 | 1.31674 (7) | 0.23705 (7) | 0.50663 (8) | 0.0242 (3) | |
| Fe1 | 1.0000 | 0.0000 | 0.5000 | 0.0132 (9)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Ho1 | 0.0155 (3) | 0.0161 (3) | 0.0147 (3) | 0.0083 (3) | −0.0004 (2) | −0.0002 (2) |
| Ho2 | 0.0223 (5) | 0.0223 (5) | 0.0194 (7) | 0.0111 (3) | 0.000 | 0.000 |
| I1 | 0.0202 (5) | 0.0195 (5) | 0.0183 (4) | 0.0106 (4) | −0.0006 (3) | 0.0010 (3) |
| I2 | 0.0167 (5) | 0.0233 (5) | 0.0260 (5) | 0.0050 (4) | −0.0030 (3) | 0.0060 (3) |
| Ho1—Fe1 | 2.6056 (7) | Ho2—I1vii | 3.0106 (9) |
| Ho1—I2 | 3.0722 (11) | Ho2—I1 | 3.0106 (9) |
| Ho1—I2i | 3.1144 (11) | Ho2—I1ii | 3.0106 (9) |
| Ho1—I1 | 3.1565 (11) | Ho2—I1viii | 3.0106 (9) |
| Ho1—I1ii | 3.1758 (11) | I1—Ho1v | 3.1758 (11) |
| Ho1—I2iii | 3.3116 (11) | I2—Ho1iv | 3.1144 (11) |
| Ho1—Ho1i | 3.6394 (11) | I2—Ho1iii | 3.3116 (11) |
| Ho1—Ho1iv | 3.6394 (11) | Fe1—Ho1ix | 2.6056 (7) |
| Ho1—Ho1v | 3.7297 (12) | Fe1—Ho1iv | 2.6056 (7) |
| Ho1—Ho1ii | 3.7297 (12) | Fe1—Ho1ii | 2.6056 (7) |
| Ho2—I1v | 3.0106 (9) | Fe1—Ho1i | 2.6056 (7) |
| Ho2—I1vi | 3.0106 (9) | Fe1—Ho1v | 2.6056 (7) |
| Fe1—Ho1—I2 | 100.19 (3) | I2iii—Ho1—Ho1ii | 133.68 (2) |
| Fe1—Ho1—I2i | 99.12 (3) | Ho1i—Ho1—Ho1ii | 90.0 |
| I2—Ho1—I2i | 89.813 (17) | Ho1iv—Ho1—Ho1ii | 59.176 (12) |
| Fe1—Ho1—I1 | 98.41 (3) | Ho1v—Ho1—Ho1ii | 60.0 |
| I2—Ho1—I1 | 161.02 (3) | I1v—Ho2—I1vi | 180.0 |
| I2i—Ho1—I1 | 90.95 (3) | I1v—Ho2—I1vii | 88.96 (2) |
| Fe1—Ho1—I1ii | 97.93 (3) | I1vi—Ho2—I1vii | 91.04 (2) |
| I2—Ho1—I1ii | 88.28 (3) | I1v—Ho2—I1 | 91.04 (2) |
| I2i—Ho1—I1ii | 162.91 (3) | I1vi—Ho2—I1 | 88.96 (2) |
| I1—Ho1—I1ii | 85.44 (4) | I1vii—Ho2—I1 | 180.0 |
| Fe1—Ho1—I2iii | 177.02 (3) | I1v—Ho2—I1ii | 91.04 (2) |
| I2—Ho1—I2iii | 81.94 (3) | I1vi—Ho2—I1ii | 88.96 (2) |
| I2i—Ho1—I2iii | 82.92 (3) | I1vii—Ho2—I1ii | 88.96 (2) |
| I1—Ho1—I2iii | 79.33 (3) | I1—Ho2—I1ii | 91.04 (2) |
| I1ii—Ho1—I2iii | 80.00 (3) | I1v—Ho2—I1viii | 88.96 (2) |
| Fe1—Ho1—Ho1i | 45.702 (10) | I1vi—Ho2—I1viii | 91.04 (2) |
| I2—Ho1—Ho1i | 99.07 (3) | I1vii—Ho2—I1viii | 91.04 (2) |
| I2i—Ho1—Ho1i | 53.43 (2) | I1—Ho2—I1viii | 88.96 (2) |
| I1—Ho1—Ho1i | 96.59 (2) | I1ii—Ho2—I1viii | 180.00 (3) |
| I1ii—Ho1—Ho1i | 143.57 (2) | Ho2—I1—Ho1 | 91.20 (3) |
| I2iii—Ho1—Ho1i | 136.24 (3) | Ho2—I1—Ho1v | 90.83 (3) |
| Fe1—Ho1—Ho1iv | 45.702 (10) | Ho1—I1—Ho1v | 72.17 (3) |
| I2—Ho1—Ho1iv | 54.50 (2) | Ho1—I2—Ho1iv | 72.07 (3) |
| I2i—Ho1—Ho1iv | 96.45 (3) | Ho1—I2—Ho1iii | 98.06 (3) |
| I1—Ho1—Ho1iv | 144.05 (2) | Ho1iv—I2—Ho1iii | 170.08 (3) |
| I1ii—Ho1—Ho1iv | 96.25 (2) | Ho1ix—Fe1—Ho1 | 180.00 (2) |
| I2iii—Ho1—Ho1iv | 136.44 (2) | Ho1ix—Fe1—Ho1iv | 91.403 (19) |
| Ho1i—Ho1—Ho1iv | 61.65 (2) | Ho1—Fe1—Ho1iv | 88.597 (19) |
| Fe1—Ho1—Ho1v | 44.298 (10) | Ho1ix—Fe1—Ho1ii | 88.597 (19) |
| I2—Ho1—Ho1v | 144.47 (2) | Ho1—Fe1—Ho1ii | 91.403 (19) |
| I2i—Ho1—Ho1v | 96.42 (3) | Ho1iv—Fe1—Ho1ii | 88.597 (19) |
| I1—Ho1—Ho1v | 54.16 (2) | Ho1ix—Fe1—Ho1i | 91.403 (19) |
| I1ii—Ho1—Ho1v | 94.97 (2) | Ho1—Fe1—Ho1i | 88.597 (19) |
| I2iii—Ho1—Ho1v | 133.49 (2) | Ho1iv—Fe1—Ho1i | 91.403 (19) |
| Ho1i—Ho1—Ho1v | 59.176 (12) | Ho1ii—Fe1—Ho1i | 180.0 |
| Ho1iv—Ho1—Ho1v | 90.0 | Ho1ix—Fe1—Ho1v | 88.597 (19) |
| Fe1—Ho1—Ho1ii | 44.298 (10) | Ho1—Fe1—Ho1v | 91.403 (19) |
| I2—Ho1—Ho1ii | 95.36 (3) | Ho1iv—Fe1—Ho1v | 180.00 (3) |
| I2i—Ho1—Ho1ii | 143.40 (2) | Ho1ii—Fe1—Ho1v | 91.404 (19) |
| I1—Ho1—Ho1ii | 95.30 (2) | Ho1i—Fe1—Ho1v | 88.597 (19) |
| I1ii—Ho1—Ho1ii | 53.68 (2) |
| Symmetry codes: (i) y+1, −x+y+1, −z+1; (ii) −y+1, x−y−1, z; (iii) −x+8/3, −y+1/3, −z+4/3; (iv) x−y, x−1, −z+1; (v) −x+y+2, −x+1, z; (vi) x−y, x−1, −z+2; (vii) −x+2, −y, −z+2; (viii) y+1, −x+y+1, −z+2; (ix) −x+2, −y, −z+1. |
This work was supported by the Deutsche Forschungsgemeinschaft (DFG), SFB 608 (Complex transition metal compounds with spin and charge degrees of freedom and disorder) and the Fonds der Chemischen Industrie.
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Rare earth cluster compounds of the general formula {Z(RE)6}I12RE, where Z is an interstitial transition metal or main group element and RE is a rare earth element, have been well explored by Hughbanks and Corbett (1988) for RE = Sc, Y, Pr and Gd. Additionally, compounds of the formula {Z(RE)6}I12+yAx, where A is an alkali metal (Rb or Cs) with x = 1–4 and y = 0–1 and Z = C, C2, are known for the rare earth elements Pr and Er that were compiled and studied by Meyer & Wickleder (2000) and Wiglusz et al. (2007). With {FeHo6}I12Ho we were able to extend the knowledge of this structure type to the element holmium, where only {CHo6}I12Ho had been synthesized previously by Hohnstedt (1993). Other reviews of reduced rare earth metal halides without and with metal clusters were given, for example, by Corbett (1973, 1996, 2000, 2006), Meyer (1988, 2007), Meyer & Wickleder (2000), Simon (1981) and Simon et al. (1991).
The structure of {FeHo6}I12Ho is isotypic with {FePr6}I12Pr (Palasyuk et al., 2006) and consists of isolated {FeHo6} clusters, i.e. the metal atoms are not shared with other clusters. The {FeHo6} cluster core is surrounded by twelve edge-capping and six terminal iodide ligands that either connect the clusters to each other directly or via HoI6 octahedra (Fig. 1). In {FeHo6}I12Ho, the {FeHo6} octahedra have 3 symmetry, only slightly deviating from ideal octahedral symmetry. The Ho—Ho distances range from 3.6394 (11) to 3.7297 (12) Å. The Ho—I distances vary between 3.0106 (9) and 3.3116 (12) Å.