Holmium dodeca­iodidoiron-octa­hedro-hexa­holmium, {FeHo6}I12Ho

Daub, K.; Meyer, G.

doi:10.1107/S1600536809001640

inorganic compounds

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Volume 65| Part 2| February 2009| Page i9

doi:10.1107/S1600536809001640

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Holmium dodecaiodidoiron-octahedro-hexaholmium, {FeHo₆}I₁₂Ho

Kathrin Daub ^a and Gerd Meyer ^a ^*

^aInstitut für Anorganische Chemie, Universität zu Köln, Greinstrasse 6, D-50939 Köln, Germany
^*Correspondence e-mail: gerd.meyer@uni-koeln.de

(Received 6 January 2009; accepted 13 January 2009; online 23 January 2009)

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} ( $[\overline{3}]$ 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 ( $[\overline{3}]$ symmetry).

Related literature

Reduced rare earth metal halides without and with metal clusters have been reviewed several times, see, for example: Corbett (1973 , 1996 , 2000 , 2006 ); Hughbanks & Corbett (1988 ); Meyer (1988 , 2007 ); Meyer & Wickleder (2000 ); Simon (1981 ); Simon et al. (1991 ); Wiglusz et al. (2007 ). For the synthesis of the starting material HoI₃, see: Meyer (1991 ). Isotypic structures have been reported by Hohnstedt (1993 ), {CHo₆}I₁₂Ho, and Palasyuk et al. (2006 ), {FePr₆}I₁₂Pr.

Experimental

Crystal data

FeHo₇I₁₂
M_r = 2733.16
Trigonal, $[R \overline 3]$
a = 15.2973 (17) Å
c = 10.6252 (16) Å
V = 2153.3 (5) Å³
Z = 3
Mo Kα radiation
μ = 32.43 mm⁻¹
T = 293 (2) K
0.2 × 0.2 × 0.2 mm

Data collection

Stoe IPDS-II diffractometer
Absorption correction: numerical [X-RED (Stoe & Cie, 2001 ) and X-SHAPE (Stoe & Cie, 1999 )] T_min = 0.027, T_max = 0.071
6920 measured reflections
1166 independent reflections
861 reflections with I > 2σ(I)
R_int = 0.115

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.096
S = 0.97
1166 reflections
32 parameters
Δρ_max = 2.36 e Å⁻³
Δρ_min = −2.44 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809001640/wm2215sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001640/wm2215Isup2.hkl

checkCIF report

Comment top

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₊_yA_x, 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.

Related literature top

Reduced rare earth metal halides without and with metal clusters have been reviewed several times, see, for example: Corbett (1973, 1996, 2000, 2006); Hughbanks & Corbett (1988); Meyer (1988, 2007); Meyer & Wickleder (2000); Simon (1981); Simon et al. (1991); Wiglusz et al. (2007). For the synthesis of the starting material HoI₃, see: Meyer (1991). Isotypic structures have been reported by Hohnstedt (1993), {CHo₆}I₁₂Ho, and Palasyuk et al. (2006), {FePr₆}I₁₂Pr).

Experimental top

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).

Computing details top

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).

Figures top

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.]

Iron heptadysprosium dodecaiodide top

Crystal data top

FeHo₇I₁₂	D_x = 6.323 Mg m⁻³
M_r = 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

Data collection top

Stoe IPDS-II diffractometer	1166 independent reflections
Radiation source: fine-focus sealed tube	861 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.115
ω scans	θ_max = 28.1°, θ_min = 2.5°
Absorption correction: numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]	h = −20→19
T_min = 0.027, T_max = 0.071	k = −19→20
6920 measured reflections	l = −14→14

Refinement top

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(F_o²) + (0.047P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.096	(Δ/σ)_max = 0.001
S = 0.97	Δρ_max = 2.36 e Å⁻³
1166 reflections	Δρ_min = −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)

Crystal data top

FeHo₇I₁₂	Z = 3
M_r = 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

Data collection top

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)
T_min = 0.027, T_max = 0.071	R_int = 0.115
6920 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	32 parameters
wR(F²) = 0.096	0 restraints
S = 0.97	Δρ_max = 2.36 e Å⁻³
1166 reflections	Δρ_min = −2.44 e Å⁻³

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

Ho1—Fe1	2.6056 (7)	Ho2—I1^vii	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—I1^viii	3.0106 (9)
Ho1—I1ⁱⁱ	3.1758 (11)	I1—Ho1^v	3.1758 (11)
Ho1—I2ⁱⁱⁱ	3.3116 (11)	I2—Ho1^iv	3.1144 (11)
Ho1—Ho1ⁱ	3.6394 (11)	I2—Ho1ⁱⁱⁱ	3.3116 (11)
Ho1—Ho1^iv	3.6394 (11)	Fe1—Ho1^ix	2.6056 (7)
Ho1—Ho1^v	3.7297 (12)	Fe1—Ho1^iv	2.6056 (7)
Ho1—Ho1ⁱⁱ	3.7297 (12)	Fe1—Ho1ⁱⁱ	2.6056 (7)
Ho2—I1^v	3.0106 (9)	Fe1—Ho1ⁱ	2.6056 (7)
Ho2—I1^vi	3.0106 (9)	Fe1—Ho1^v	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)	Ho1^iv—Ho1—Ho1ⁱⁱ	59.176 (12)
Fe1—Ho1—I1	98.41 (3)	Ho1^v—Ho1—Ho1ⁱⁱ	60.0
I2—Ho1—I1	161.02 (3)	I1^v—Ho2—I1^vi	180.0
I2ⁱ—Ho1—I1	90.95 (3)	I1^v—Ho2—I1^vii	88.96 (2)
Fe1—Ho1—I1ⁱⁱ	97.93 (3)	I1^vi—Ho2—I1^vii	91.04 (2)
I2—Ho1—I1ⁱⁱ	88.28 (3)	I1^v—Ho2—I1	91.04 (2)
I2ⁱ—Ho1—I1ⁱⁱ	162.91 (3)	I1^vi—Ho2—I1	88.96 (2)
I1—Ho1—I1ⁱⁱ	85.44 (4)	I1^vii—Ho2—I1	180.0
Fe1—Ho1—I2ⁱⁱⁱ	177.02 (3)	I1^v—Ho2—I1ⁱⁱ	91.04 (2)
I2—Ho1—I2ⁱⁱⁱ	81.94 (3)	I1^vi—Ho2—I1ⁱⁱ	88.96 (2)
I2ⁱ—Ho1—I2ⁱⁱⁱ	82.92 (3)	I1^vii—Ho2—I1ⁱⁱ	88.96 (2)
I1—Ho1—I2ⁱⁱⁱ	79.33 (3)	I1—Ho2—I1ⁱⁱ	91.04 (2)
I1ⁱⁱ—Ho1—I2ⁱⁱⁱ	80.00 (3)	I1^v—Ho2—I1^viii	88.96 (2)
Fe1—Ho1—Ho1ⁱ	45.702 (10)	I1^vi—Ho2—I1^viii	91.04 (2)
I2—Ho1—Ho1ⁱ	99.07 (3)	I1^vii—Ho2—I1^viii	91.04 (2)
I2ⁱ—Ho1—Ho1ⁱ	53.43 (2)	I1—Ho2—I1^viii	88.96 (2)
I1—Ho1—Ho1ⁱ	96.59 (2)	I1ⁱⁱ—Ho2—I1^viii	180.00 (3)
I1ⁱⁱ—Ho1—Ho1ⁱ	143.57 (2)	Ho2—I1—Ho1	91.20 (3)
I2ⁱⁱⁱ—Ho1—Ho1ⁱ	136.24 (3)	Ho2—I1—Ho1^v	90.83 (3)
Fe1—Ho1—Ho1^iv	45.702 (10)	Ho1—I1—Ho1^v	72.17 (3)
I2—Ho1—Ho1^iv	54.50 (2)	Ho1—I2—Ho1^iv	72.07 (3)
I2ⁱ—Ho1—Ho1^iv	96.45 (3)	Ho1—I2—Ho1ⁱⁱⁱ	98.06 (3)
I1—Ho1—Ho1^iv	144.05 (2)	Ho1^iv—I2—Ho1ⁱⁱⁱ	170.08 (3)
I1ⁱⁱ—Ho1—Ho1^iv	96.25 (2)	Ho1^ix—Fe1—Ho1	180.00 (2)
I2ⁱⁱⁱ—Ho1—Ho1^iv	136.44 (2)	Ho1^ix—Fe1—Ho1^iv	91.403 (19)
Ho1ⁱ—Ho1—Ho1^iv	61.65 (2)	Ho1—Fe1—Ho1^iv	88.597 (19)
Fe1—Ho1—Ho1^v	44.298 (10)	Ho1^ix—Fe1—Ho1ⁱⁱ	88.597 (19)
I2—Ho1—Ho1^v	144.47 (2)	Ho1—Fe1—Ho1ⁱⁱ	91.403 (19)
I2ⁱ—Ho1—Ho1^v	96.42 (3)	Ho1^iv—Fe1—Ho1ⁱⁱ	88.597 (19)
I1—Ho1—Ho1^v	54.16 (2)	Ho1^ix—Fe1—Ho1ⁱ	91.403 (19)
I1ⁱⁱ—Ho1—Ho1^v	94.97 (2)	Ho1—Fe1—Ho1ⁱ	88.597 (19)
I2ⁱⁱⁱ—Ho1—Ho1^v	133.49 (2)	Ho1^iv—Fe1—Ho1ⁱ	91.403 (19)
Ho1ⁱ—Ho1—Ho1^v	59.176 (12)	Ho1ⁱⁱ—Fe1—Ho1ⁱ	180.0
Ho1^iv—Ho1—Ho1^v	90.0	Ho1^ix—Fe1—Ho1^v	88.597 (19)
Fe1—Ho1—Ho1ⁱⁱ	44.298 (10)	Ho1—Fe1—Ho1^v	91.403 (19)
I2—Ho1—Ho1ⁱⁱ	95.36 (3)	Ho1^iv—Fe1—Ho1^v	180.00 (3)
I2ⁱ—Ho1—Ho1ⁱⁱ	143.40 (2)	Ho1ⁱⁱ—Fe1—Ho1^v	91.404 (19)
I1—Ho1—Ho1ⁱⁱ	95.30 (2)	Ho1ⁱ—Fe1—Ho1^v	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.

Experimental details

Crystal data
Chemical formula	FeHo₇I₁₂
M_r	2733.16
Crystal system, space group	Trigonal, R3
Temperature (K)	293
a, c (Å)	15.2973 (17), 10.6252 (16)
V (Å³)	2153.3 (5)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	32.43
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Stoe IPDS-II diffractometer
Absorption correction	Numerical [X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999)]
T_min, T_max	0.027, 0.071
No. of measured, independent and observed [I > 2σ(I)] reflections	6920, 1166, 861
R_int	0.115
(sin θ/λ)_max (Å⁻¹)	0.663

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.096, 0.97
No. of reflections	1166
No. of parameters	32
Δρ_max, Δρ_min (e Å⁻³)	2.36, −2.44

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2005).

Acknowledgements

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.

References

Brandenburg, K. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Corbett, J. D. (1973). Rev. Chim. Miner. 10, 239–257. CAS Google Scholar
Corbett, J. D. (1996). J. Chem. Soc. Dalton Trans. pp. 575–587. CrossRef Web of Science Google Scholar
Corbett, J. D. (2000). Inorg. Chem. 39, 5178–5191. Web of Science CrossRef PubMed CAS Google Scholar
Corbett, J. D. (2006). J. Alloys Compds, 418, 1–20. Web of Science CrossRef CAS Google Scholar
Hohnstedt, C. (1993). Dissertation, Universität Hannover, Germany. Google Scholar
Hughbanks, T. & Corbett, J. D. (1988). Inorg. Chem. 27, 2022–2026. CrossRef CAS Web of Science Google Scholar
Meyer, G. (1988). Chem. Rev. 88, 93–107. CrossRef CAS Web of Science Google Scholar
Meyer, G. (1991). Synthesis of Lanthanide and Actinide Compounds, edited by G. Meyer & L. R. Morss, pp. 135–144. Kluwer: Dordrecht. Google Scholar
Meyer, G. (2007). Z. Anorg. Allg. Chem. 633, 2537–2552. Web of Science CrossRef CAS Google Scholar
Meyer, G. & Wickleder, M. S. (2000). Handbook on the Physics and Chemistry of Rare Earths, Vol. 28, edited by K. A. Gscheidner Jr. & L. Eyring, pp. 53–129. Elsevier: Amsterdam. Google Scholar
Palasyuk, A., Pantenburg, I. & Meyer, G. (2006). Acta Cryst. E62, i61–i63. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Simon, A. (1981). Angew. Chem. Int. Ed. Engl. 20, 1–22. CrossRef Web of Science Google Scholar
Simon, A., Mattausch, Hj., Miller, G. J., Bauhofer, W. & Kremer, R. (1991). Handbook on the Physics and Chemistry of Rare Earths, Vol. 15, edited by K. A. Gschneidner Jr. & L. Eyring, pp. 191–285. Elsevier: Amsterdam. Google Scholar
Stoe & Cie (1999). X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Stoe & Cie (2001). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany. Google Scholar
Wiglusz, R., Pantenburg, I. & Meyer, G. (2007). Z. Anorg. Allg. Chem. 633, 1317–1319. Web of Science CrossRef CAS Google Scholar