Holmium dodeca-iodidoiron-octa-hedro-hexa-holmium, {FeHo(6)}I(12)Ho.

Single crystals of {FeHo(6)}I(12)Ho were obtained during the reaction of HoI(3) with metallic holmium and iron in a sealed tantalum container. The crystal structure consists of isolated holmium clusters encapsulating a single Fe atom, {FeHo(6)} ( 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 HoI(6) octa-hedra ( 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 = 2733.16

Trigonal,

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[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.096

S = 0.97

1166 reflections

32 parameters

Δρmax = 2.36 e Å−3

Δρmin = −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.

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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)

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)