Nickel hexa­yttrium deca­iodide, [NiY₆]I₁₀

Comproportionation reactions of yttrium triiodide, yttrium and nickel led to the formation of the compound [NiY₆]I₁₀, which is isostructural with the prototypical [RuY₆]I₁₀. In particular, [NiY₆]I₁₀ is composed of isolated nickel centered yttrium octa­hedra (site symmetry -1) that are further surrounded by iodide ligands to construct a three-dimensional cluster complex framework. Although this compound has been previously detected by powder X-ray diffraction techniques [Payne & Corbett (1990). Inorg. Chem. 29, 2246–2251], details of the crystal structure for triclinic [NiY₆]I₁₀ were not provided.

Related literature

For a report of the prototypical [RuY₆]I₁₀, see: Hughbanks et al. (1989). For the determination of the lattice parameters of [NiY₆]I₁₀ from PXRD data, see: Payne & Corbett (1990). For a survey of isotypic structures, see: Rustige et al. (2012). For the synthesis of the starting material YI₃, see: Corbett (1983); Meyer (1991). The symmetry of the refined structure was checked using the PLATON software package (Spek, 2009).

Experimental

Crystal data

• [NiY₆]I₁₀

• M_r = 1861.17

• Triclinic,

• a = 9.4904 (7) Å

• b = 9.4990 (7) Å

• c = 7.5702 (5) Å

• α = 97.056 (6)°

• β = 105.096 (6)°

• γ = 107.540 (5)°

• V = 613.06 (8) ų

• Z = 1

• Mo Kα radiation

• μ = 27.35 mm⁻¹

• T = 293 K

• 0.1 × 0.1 × 0.1 mm

Data collection

• Stoe IPDS 2T diffractometer

• Absorption correction: numerical [X-SHAPE (Stoe & Cie, 1999) and X-RED (Stoe & Cie, 2001)] T_min = 0.031, T_max = 0.084

• 11699 measured reflections

• 3294 independent reflections

• 2873 reflections with I > 2σ(I)

• R_int = 0.106

Refinement

• R[F² > 2σ(F²)] = 0.034

• wR(F²) = 0.091

• S = 1.05

• 3294 reflections

• 80 parameters

• Δρ_max = 1.37 e Å⁻³

• Δρ_min = −1.64 e Å⁻³

Table 1
Averaged Y—Ni, Y—Y and Y—I distances (Å) in triclinic [NiY₆]I₁₀

Inter­action	Y—Ni	Y—Y	Y—I
Distance	2.649	3.746	3.143

Data collection: X-AREA (Stoe & Cie, 2003); 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, 1999); software used to prepare material for publication: SHELXL97 and local programs.

Supporting information

S1. Comment

[NiY₆]I₁₀ crystallizes with the triclinic [RuY₆]I₁₀ type of structure (Hughbanks et al., 1989) and may be depicted as cubic closest packings of nickel and iodine atoms with yttrium atoms residing in 6/11 of all octahedral holes. Particularly, the yttrium atoms occupy those voids surrounding the nickel atoms to aggregate to octahedral [NiY₆] clusters (Fig. 1). The twelve edges of each [NiY₆] octahedron are capped by inner iodido ligands forming cuboctahedra around the endohedral nickel atoms. Additionally, the yttrium atoms bond to outer iodido ligands that reside in the inner coordination spheres of like clusters. More specifically, the iodido ligands interconnect the [NiY₆] clusters via (i)–(i)–, (i)–(a)– and (a)–(i)–functionalities (Fig. 2), which can be emphasized by the formula [NiY₆]Iⁱ_2/1I^i-i_4/2I^i-a_6/2I^a-i_6/2 (Rustige et al., 2012 and lit. cited therein). The averaged Y–Y and Y–I (see below) distances correlate well with data of recently reported yttrium cluster iodides (Rustige et al., 2012).

Related literature

For a report of the prototypical [RuY₆]I₁₀, see: Hughbanks et al. (1989). For the determination of the lattice parameters of [NiY₆]I₁₀ from PXRD data, see: Payne et al. (1990). For a survey of isotypic structures, see: Rustige et al. (2012). For the synthesis of the starting material YI₃, see: Corbett (1983); Meyer (1991). The symmetry of the refined structure was checked using the PLATON software package (Spek, 2009).

S2. Experimental

[NiY₆]I₁₀ was obtained from comproportionation reactions of yttrium triiodide, yttrium and nickel. Yttrium triiodide was synthesized from reactions of the pure elements (Corbett, 1983; Meyer, 1991), while the metals were obtained from commercial sources (Y, smart elements, 99.99%; Ni, Riedel–de Haen, 99.8%) and used without further purification. Due to the sensivity of the used chemicals and products to air and moisture, all sample preparations were performed under a nitrogen atmosphere in a glove box with strict exclusion of air and water (< 0.1 p.p.m.). The reaction mixtures were loaded as {NiY₃}I₃ in pre–cleaned, one–side He–arc welded tantalum tubes, which were closed inside a glove box, arc–welded at the other end and jacketed by evacuated, fused silica tubes. The mixtures were first heated to 1050 °C, kept at that temperature for one week, slowly–annealed to 700 °C and, then, rapidly cooled to room temperature. The product appeared as a black powder containing small crystals of polyhedral shape. Single crystals were selected from the bulk and fixed in capilleries, which were closed inside a glove box. The crystals were subsequently transferred to a Stoe IPDS 2 T diffractometer and complete sets of intensity data were collected at room temperature (293 (2) K).

S3. Refinement

The intensity data sets were corrected for Lorentz and polarization effects. The structure was solved using direct methods (SHELXS97, Sheldrick, 2008) and refined on F² (SHELXL97, Sheldrick, 2008). A numerical absorption correction and a crystal shape optimization were carried out with the programs X-RED (Stoe & Cie, 2001) and X-SHAPE (Stoe & Cie, 1999), respectively. The PLATON software package (Spek, 2009) was utilized to check the symmetry of the refined structure and no higher symmetry was identified. As the largest difference peaks (1.365 and -1.635 e.Å) are located 0.73 Å and 0.81 Å near to the I2 and I1 sites, respectively, and all thermal ellipsoids are reasonable in shape and size (Rustige et al., 2012), the presence of further atom sites was excluded. To compare the lattice parameters of the title compound to those of more recently reported yttrium cluster iodides (Rustige et al., 2012), a lattice setting unlike the standard setting was chosen for the triclinic [NiY₆]I₁₀.

Computing details

Data collection: X-AREA (Stoe & Cie, 2003); cell refinement: X-AREA (Stoe & Cie, 2003); data reduction: X-AREA (Stoe & Cie, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and local programs.

Figures

	Fig. 1. Representation of isolated [NiY6] octahedra. The edges are capped by the iodido ligands, whereas each yttrium atom bonds to one outer iodido ligand (90% probability thermal ellipsoids).
	Fig. 2. View on the (i)–(i)–, (i)–a)– and (a)–(i)–interconnections as seen in the triclinic [NiY6]I10.

Hexayttrium nickel decaiodide

Crystal data

Y6NiI10	Z = 1
Mr = 1861.17	F(000) = 792
Triclinic, P1	Dx = 5.041 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4904 (7) Å	Cell parameters from 7675 reflections
b = 9.4990 (7) Å	θ = 2.3–29.7°
c = 7.5702 (5) Å	µ = 27.35 mm^−1
α = 97.056 (6)°	T = 293 K
β = 105.096 (6)°	Polyhedral, black
γ = 107.540 (5)°	0.1 × 0.1 × 0.1 mm
V = 613.06 (8) Å^3

Data collection

Stoe IPDS 2T diffractometer	3294 independent reflections
Radiation source: fine-focus sealed tube	2873 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.106
Detector resolution: not measured pixels mm^-1	θmax = 29.2°, θmin = 2.3°
ω and ϕ scans	h = −12→12
Absorption correction: numerical [X-SHAPE (Stoe & Cie, 1999) and X-RED (Stoe & Cie, 2001)]	k = −12→12
Tmin = 0.031, Tmax = 0.084	l = −10→10
11699 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	w = 1/[σ^2(Fo^2) + (0.0426P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.091	(Δ/σ)max = 0.001
S = 1.05	Δρmax = 1.37 e Å^−3
3294 reflections	Δρmin = −1.64 e Å^−3
80 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0065 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
I1	0.46133 (4)	0.27745 (5)	0.36198 (5)	0.03196 (12)
I2	0.09092 (5)	−0.53117 (5)	−0.73275 (5)	0.03117 (12)
I3	0.62560 (4)	0.18495 (5)	−0.08746 (6)	0.03022 (12)
I4	0.18872 (4)	−0.09482 (4)	−0.45161 (4)	0.02376 (11)
I5	0.26512 (4)	0.35524 (4)	−0.21790 (6)	0.02461 (11)
Y1	0.03920 (6)	−0.24090 (6)	−0.88682 (7)	0.01994 (13)
Y2	0.28566 (6)	0.08659 (6)	−0.02824 (7)	0.02070 (13)
Y3	0.12577 (6)	0.16546 (6)	−0.65217 (7)	0.02003 (13)
Ni1	0.0000	0.0000	0.0000	0.01763 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I1	0.0218 (2)	0.0379 (3)	0.02921 (19)	0.00438 (18)	0.00735 (15)	−0.00074 (17)
I2	0.0445 (3)	0.0225 (2)	0.02586 (18)	0.01531 (18)	0.00550 (16)	0.00573 (15)
I3	0.0238 (2)	0.0314 (2)	0.0443 (2)	0.01372 (17)	0.01644 (16)	0.01687 (19)
I4	0.02514 (19)	0.0264 (2)	0.02106 (17)	0.01056 (16)	0.00748 (13)	0.00530 (14)
I5	0.02516 (19)	0.0237 (2)	0.02650 (17)	0.00764 (14)	0.01043 (13)	0.00798 (13)
Y1	0.0214 (2)	0.0197 (3)	0.0214 (2)	0.00886 (18)	0.00798 (17)	0.00681 (18)
Y2	0.0188 (2)	0.0232 (3)	0.0223 (2)	0.00806 (18)	0.00821 (17)	0.00681 (19)
Y3	0.0212 (2)	0.0205 (3)	0.0198 (2)	0.00802 (18)	0.00750 (16)	0.00500 (17)
Ni1	0.0174 (4)	0.0184 (5)	0.0191 (4)	0.0072 (3)	0.0070 (3)	0.0060 (3)

Geometric parameters (Å, º)

I1—Y3^i	3.0062 (7)	Y1—Y2^vii	3.7458 (8)
I1—Y2	3.0150 (7)	Y1—Y3	3.7913 (8)
I2—Y1^ii	3.0839 (7)	Y2—Ni1	2.6595 (5)
I2—Y3^iii	3.1124 (7)	Y2—I3^iv	3.0999 (6)
I2—Y1	3.2421 (6)	Y2—Y3^i	3.6579 (8)
I3—Y2^iv	3.0999 (6)	Y2—Y1^vi	3.7404 (8)
I3—Y1^v	3.1255 (7)	Y2—Y1^i	3.7458 (8)
I3—Y2	3.2437 (7)	Y2—Y3^vi	3.8540 (8)
I4—Y1	3.1700 (6)	Y3—Ni1^vii	2.6540 (5)
I4—Y3	3.1805 (6)	Y3—I1^vii	3.0062 (7)
I4—Y3^vi	3.1811 (7)	Y3—I2^ix	3.1124 (7)
I4—Y2	3.1999 (6)	Y3—I4^vi	3.1811 (7)
I5—Y1^vi	3.1085 (7)	Y3—Y2^vii	3.6579 (8)
I5—Y2	3.1091 (6)	Y3—Y1^viii	3.6863 (7)
I5—Y3	3.2633 (7)	Y3—Y2^vi	3.8540 (8)
Y1—Ni1^vii	2.6339 (5)	Ni1—Y1^i	2.6339 (5)
Y1—I2^ii	3.0839 (7)	Ni1—Y1^vi	2.6339 (5)
Y1—I5^vi	3.1085 (7)	Ni1—Y3^vi	2.6540 (5)
Y1—I3^v	3.1255 (7)	Ni1—Y3^i	2.6540 (5)
Y1—Y3^viii	3.6863 (7)	Ni1—Y2^x	2.6595 (5)
Y1—Y2^vi	3.7404 (8)
Y3^i—I1—Y2	74.819 (17)	I1—Y2—Y1^vi	95.963 (18)
Y1^ii—I2—Y3^iii	73.012 (17)	I3^iv—Y2—Y1^vi	142.723 (19)
Y1^ii—I2—Y1	97.915 (17)	I5—Y2—Y1^vi	53.010 (13)
Y3^iii—I2—Y1	170.822 (19)	I4—Y2—Y1^vi	95.321 (16)
Y2^iv—I3—Y1^v	73.981 (17)	I3—Y2—Y1^vi	134.546 (18)
Y2^iv—I3—Y2	97.455 (17)	Y3^i—Y2—Y1^vi	59.759 (14)
Y1^v—I3—Y2	171.270 (19)	Ni1—Y2—Y1^i	44.682 (11)
Y1—I4—Y3	73.313 (16)	I1—Y2—Y1^i	96.665 (18)
Y1—I4—Y3^vi	97.782 (17)	I3^iv—Y2—Y1^i	53.322 (14)
Y3—I4—Y3^vi	92.193 (17)	I5—Y2—Y1^i	141.452 (18)
Y1—I4—Y2	167.857 (18)	I4—Y2—Y1^i	93.299 (17)
Y3—I4—Y2	97.453 (17)	I3—Y2—Y1^i	135.838 (19)
Y3^vi—I4—Y2	74.310 (16)	Y3^i—Y2—Y1^i	61.592 (15)
Y1^vi—I5—Y2	73.966 (16)	Y1^vi—Y2—Y1^i	89.447 (15)
Y1^vi—I5—Y3	97.326 (18)	Ni1—Y2—Y3^vi	43.448 (11)
Y2—I5—Y3	97.588 (18)	I1—Y2—Y3^vi	142.34 (2)
Ni1^vii—Y1—I2^ii	99.864 (17)	I3^iv—Y2—Y3^vi	93.585 (17)
Ni1^vii—Y1—I5^vi	97.898 (17)	I5—Y2—Y3^vi	91.241 (16)
I2^ii—Y1—I5^vi	94.416 (18)	I4—Y2—Y3^vi	52.622 (13)
Ni1^vii—Y1—I3^v	97.912 (18)	I3—Y2—Y3^vi	133.462 (18)
I2^ii—Y1—I3^v	88.724 (19)	Y3^i—Y2—Y3^vi	89.881 (16)
I5^vi—Y1—I3^v	163.10 (2)	Y1^vi—Y2—Y3^vi	59.875 (14)
Ni1^vii—Y1—I4	97.867 (18)	Y1^i—Y2—Y3^vi	58.011 (13)
I2^ii—Y1—I4	162.27 (2)	Ni1^vii—Y3—I1^vii	99.248 (19)
I5^vi—Y1—I4	83.191 (17)	Ni1^vii—Y3—I2^ix	98.706 (17)
I3^v—Y1—I4	88.768 (17)	I1^vii—Y3—I2^ix	90.954 (19)
Ni1^vii—Y1—I2	178.04 (2)	Ni1^vii—Y3—I4	97.190 (17)
I2^ii—Y1—I2	82.085 (17)	I1^vii—Y3—I4	88.952 (18)
I5^vi—Y1—I2	81.656 (16)	I2^ix—Y3—I4	163.91 (2)
I3^v—Y1—I2	82.341 (16)	Ni1^vii—Y3—I4^vi	96.629 (17)
I4—Y1—I2	80.185 (15)	I1^vii—Y3—I4^vi	164.07 (2)
Ni1^vii—Y1—Y3^viii	46.028 (12)	I2^ix—Y3—I4^vi	87.890 (18)
I2^ii—Y1—Y3^viii	53.849 (14)	I4—Y3—I4^vi	87.807 (17)
I5^vi—Y1—Y3^viii	98.781 (17)	Ni1^vii—Y3—I5	176.74 (2)
I3^v—Y1—Y3^viii	96.476 (18)	I1^vii—Y3—I5	83.500 (17)
I4—Y1—Y3^viii	143.879 (19)	I2^ix—Y3—I5	82.942 (16)
I2—Y1—Y3^viii	135.914 (19)	I4—Y3—I5	81.059 (15)
Ni1^vii—Y1—Y2^vi	45.319 (11)	I4^vi—Y3—I5	80.592 (16)
I2^ii—Y1—Y2^vi	95.733 (17)	Ni1^vii—Y3—Y2^vii	46.558 (12)
I5^vi—Y1—Y2^vi	53.024 (13)	I1^vii—Y3—Y2^vii	52.700 (15)
I3^v—Y1—Y2^vi	143.204 (19)	I2^ix—Y3—Y2^vii	96.907 (18)
I4—Y1—Y2^vi	96.770 (17)	I4—Y3—Y2^vii	95.821 (17)
I2—Y1—Y2^vi	134.455 (19)	I4^vi—Y3—Y2^vii	143.186 (18)
Y3^viii—Y1—Y2^vi	59.009 (14)	I5—Y3—Y2^vii	136.194 (19)
Ni1^vii—Y1—Y2^vii	45.234 (12)	Ni1^vii—Y3—Y1^viii	45.581 (11)
I2^ii—Y1—Y2^vii	98.116 (18)	I1^vii—Y3—Y1^viii	97.251 (19)
I5^vi—Y1—Y2^vii	142.547 (19)	I2^ix—Y3—Y1^viii	53.138 (14)
I3^v—Y1—Y2^vii	52.697 (13)	I4—Y3—Y1^viii	142.755 (19)
I4—Y1—Y2^vii	94.288 (17)	I4^vi—Y3—Y1^viii	94.750 (17)
I2—Y1—Y2^vii	134.926 (19)	I5—Y3—Y1^viii	136.052 (19)
Y3^viii—Y1—Y2^vii	62.465 (15)	Y2^vii—Y3—Y1^viii	61.232 (14)
Y2^vi—Y1—Y2^vii	90.553 (16)	Ni1^vii—Y3—Y1	43.984 (11)
Ni1^vii—Y1—Y3	44.407 (11)	I1^vii—Y3—Y1	95.871 (19)
I2^ii—Y1—Y3	144.254 (18)	I2^ix—Y3—Y1	142.674 (18)
I5^vi—Y1—Y3	92.436 (17)	I4—Y3—Y1	53.216 (13)
I3^v—Y1—Y3	94.680 (17)	I4^vi—Y3—Y1	94.652 (16)
I4—Y1—Y3	53.471 (13)	I5—Y3—Y1	134.247 (18)
I2—Y1—Y3	133.650 (17)	Y2^vii—Y3—Y1	60.346 (15)
Y3^viii—Y1—Y3	90.435 (16)	Y1^viii—Y3—Y1	89.565 (16)
Y2^vi—Y1—Y3	61.551 (14)	Ni1^vii—Y3—Y2^vi	43.561 (12)
Y2^vii—Y1—Y3	58.063 (14)	I1^vii—Y3—Y2^vi	142.796 (19)
Ni1—Y2—I1	98.905 (19)	I2^ix—Y3—Y2^vi	95.413 (17)
Ni1—Y2—I3^iv	97.985 (17)	I4—Y3—Y2^vi	94.365 (16)
I1—Y2—I3^iv	90.836 (17)	I4^vi—Y3—Y2^vi	53.068 (13)
Ni1—Y2—I5	97.335 (17)	I5—Y3—Y2^vi	133.637 (19)
I1—Y2—I5	95.806 (19)	Y2^vii—Y3—Y2^vi	90.119 (16)
I3^iv—Y2—I5	162.14 (2)	Y1^viii—Y3—Y2^vi	59.523 (14)
Ni1—Y2—I4	96.070 (17)	Y1—Y3—Y2^vi	58.574 (14)
I1—Y2—I4	165.00 (2)	Y1^i—Ni1—Y1^vi	180.0
I3^iv—Y2—I4	86.140 (18)	Y1^i—Ni1—Y3^vi	88.391 (16)
I5—Y2—I4	83.167 (16)	Y1^vi—Ni1—Y3^vi	91.609 (16)
Ni1—Y2—I3	176.84 (2)	Y1^i—Ni1—Y3^i	91.609 (16)
I1—Y2—I3	84.194 (17)	Y1^vi—Ni1—Y3^i	88.391 (16)
I3^iv—Y2—I3	82.545 (17)	Y3^vi—Ni1—Y3^i	180.00 (2)
I5—Y2—I3	81.665 (16)	Y1^i—Ni1—Y2	90.083 (17)
I4—Y2—I3	80.844 (17)	Y1^vi—Ni1—Y2	89.917 (17)
Ni1—Y2—Y3^i	46.433 (12)	Y3^vi—Ni1—Y2	92.991 (17)
I1—Y2—Y3^i	52.481 (14)	Y3^i—Ni1—Y2	87.009 (17)
I3^iv—Y2—Y3^i	97.823 (18)	Y1^i—Ni1—Y2^x	89.917 (17)
I5—Y2—Y3^i	99.371 (18)	Y1^vi—Ni1—Y2^x	90.083 (17)
I4—Y2—Y3^i	142.503 (18)	Y3^vi—Ni1—Y2^x	87.009 (17)
I3—Y2—Y3^i	136.648 (19)	Y3^i—Ni1—Y2^x	92.991 (17)
Ni1—Y2—Y1^vi	44.765 (11)	Y2—Ni1—Y2^x	180.000 (7)

Symmetry codes: (i) x, y, z+1; (ii) −x, −y−1, −z−2; (iii) x, y−1, z; (iv) −x+1, −y, −z; (v) −x+1, −y, −z−1; (vi) −x, −y, −z−1; (vii) x, y, z−1; (viii) −x, −y, −z−2; (ix) x, y+1, z; (x) −x, −y, −z.