(IUCr) Crystallography Journals Online

Abstract top

Cs₂[IrF₆] possesses a framework structure constructed from Cs⁺ cations and [IrF₆]^2- complex anions. The cation is 12-coordinated by F atoms, forming a slightly distorted anticuboctahedron; the anion has the shape of an almost ideal octahedron. Cs, Ir and F atoms are located on special positions of 3m, $\overline{3}$ m and m symmetry, respectively.

Caesium hexafluoridoiridate(IV) top

Crystal data top

Cs₂[IrF₆]	Z = 1
M_r = 572.02	F₀₀₀ = 241
Trigonal, P3m1	D_x = 5.620 Mg m⁻³
Hall symbol: -P 3 2"	Mo Kα radiation λ = 0.71073 Å
a = 6.2421 (3) Å	Cell parameters from 982 reflections
b = 6.2421 (3) Å	θ = 3.8–30.0º
c = 5.0084 (5) Å	µ = 30.40 mm⁻¹
α = 90º	T = 296 (2) K
β = 90º	Needle, light-pink
γ = 120º	0.08 × 0.06 × 0.04 mm
V = 169.00 (2) Å³

Data collection top

Bruker–Nonius X8 APEX CCD area-detector diffractometer	211 independent reflections
Radiation source: fine-focus sealed tube	207 reflections with I > 2σ(I)
Monochromator: graphite	R_int = 0.019
Detector resolution: 25 pixels mm^-1	θ_max = 30.0º
T = 296(2) K	θ_min = 3.8º
φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −8→5
T_min = 0.134, T_max = 0.288	l = −7→7
1513 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0133P)² + 0.3436P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.013	(Δ/σ)_max < 0.001
wR(F²) = 0.028	Δρ_max = 1.04 e Å⁻³
S = 1.06	Δρ_min = −0.49 e Å⁻³
211 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
13 parameters	Extinction coefficient: 0.0058 (8)
Primary atom site location: structure-invariant direct methods

Crystal data top

Cs₂[IrF₆]	γ = 120º
M_r = 572.02	V = 169.00 (2) Å³
Trigonal, P3m1	Z = 1
a = 6.2421 (3) Å	Mo Kα
b = 6.2421 (3) Å	µ = 30.40 mm⁻¹
c = 5.0084 (5) Å	T = 296 (2) K
α = 90º	0.08 × 0.06 × 0.04 mm
β = 90º

Data collection top

Bruker–Nonius X8 APEX CCD area-detector diffractometer	211 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	207 reflections with I > 2σ(I)
T_min = 0.134, T_max = 0.288	R_int = 0.019
1513 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.013	13 parameters
wR(F²) = 0.028	Δρ_max = 1.04 e Å⁻³
S = 1.06	Δρ_min = −0.49 e Å⁻³
211 reflections

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 > 2sigma(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.

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 > 2sigma(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
Ir1	0.0000	0.0000	0.5000	0.01382 (13)
Cs1	0.6667	0.3333	0.19957 (9)	0.02036 (14)
F1	0.1497 (2)	0.2995 (4)	0.2862 (5)	0.0233 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ir1	0.01221 (14)	0.01221 (14)	0.0171 (2)	0.00610 (7)	0.000	0.000
Cs1	0.01903 (16)	0.01903 (16)	0.0230 (3)	0.00951 (8)	0.000	0.000
F1	0.0245 (10)	0.0171 (12)	0.0258 (13)	0.0085 (6)	0.0037 (5)	0.0075 (10)

Geometric parameters (Å, °) top

Ir1—F1ⁱ	1.941 (2)	Cs1—F1^xii	3.140 (2)
Ir1—F1ⁱⁱ	1.941 (2)	Cs1—F1^xiii	3.1564 (4)
Ir1—F1ⁱⁱⁱ	1.941 (2)	Cs1—F1^xiv	3.1564 (4)
Ir1—F1^iv	1.941 (2)	Cs1—F1^xv	3.1564 (4)
Ir1—F1	1.941 (2)	Cs1—F1	3.1564 (4)
Ir1—F1^v	1.941 (2)	Cs1—F1^v	3.1564 (4)
Ir1—Cs1^vi	3.9054 (2)	Cs1—F1^xvi	3.1564 (4)
Ir1—Cs1^vii	3.9054 (2)	Cs1—F1^xvii	3.252 (3)
Ir1—Cs1^viii	3.9054 (2)	Cs1—F1^viii	3.252 (3)
Ir1—Cs1^ix	3.9054 (2)	Cs1—F1ⁱ	3.252 (3)
Ir1—Cs1	3.9054 (2)	F1—Cs1^xii	3.140 (2)
Ir1—Cs1^iv	3.9054 (2)	F1—Cs1^vii	3.1564 (4)
Cs1—F1^x	3.140 (2)	F1—Cs1^viii	3.252 (3)
Cs1—F1^xi	3.140 (2)

F1ⁱ—Ir1—F1ⁱⁱ	180.00 (11)	F1^xii—Cs1—F1^xiii	129.02 (2)
F1ⁱ—Ir1—F1ⁱⁱⁱ	92.50 (10)	F1^x—Cs1—F1^xiv	98.23 (4)
F1ⁱⁱ—Ir1—F1ⁱⁱⁱ	87.50 (10)	F1^xi—Cs1—F1^xiv	129.02 (2)
F1ⁱ—Ir1—F1^iv	92.50 (10)	F1^xii—Cs1—F1^xiv	63.06 (8)
F1ⁱⁱ—Ir1—F1^iv	87.50 (10)	F1^xiii—Cs1—F1^xiv	118.14 (2)
F1ⁱⁱⁱ—Ir1—F1^iv	92.50 (10)	F1^x—Cs1—F1^xv	63.06 (8)
F1ⁱ—Ir1—F1	87.50 (10)	F1^xi—Cs1—F1^xv	129.02 (2)
F1ⁱⁱ—Ir1—F1	92.50 (10)	F1^xii—Cs1—F1^xv	98.23 (4)
F1ⁱⁱⁱ—Ir1—F1	87.50 (10)	F1^xiii—Cs1—F1^xv	52.74 (9)
F1^iv—Ir1—F1	180.00 (11)	F1^xiv—Cs1—F1^xv	66.00 (9)
F1ⁱ—Ir1—F1^v	87.50 (10)	F1^x—Cs1—F1	129.02 (2)
F1ⁱⁱ—Ir1—F1^v	92.50 (10)	F1^xi—Cs1—F1	63.06 (8)
F1ⁱⁱⁱ—Ir1—F1^v	180.0	F1^xii—Cs1—F1	98.23 (4)
F1^iv—Ir1—F1^v	87.50 (10)	F1^xiii—Cs1—F1	118.14 (2)
F1—Ir1—F1^v	92.50 (10)	F1^xiv—Cs1—F1	118.14 (2)
F1ⁱ—Ir1—Cs1^vi	53.317 (7)	F1^xv—Cs1—F1	162.83 (9)
F1ⁱⁱ—Ir1—Cs1^vi	126.683 (7)	F1^x—Cs1—F1^v	98.23 (4)
F1ⁱⁱⁱ—Ir1—Cs1^vi	123.86 (8)	F1^xi—Cs1—F1^v	63.06 (8)
F1^iv—Ir1—Cs1^vi	53.317 (7)	F1^xii—Cs1—F1^v	129.02 (2)
F1—Ir1—Cs1^vi	126.683 (7)	F1^xiii—Cs1—F1^v	66.00 (9)
F1^v—Ir1—Cs1^vi	56.14 (8)	F1^xiv—Cs1—F1^v	162.83 (9)
F1ⁱ—Ir1—Cs1^vii	126.683 (7)	F1^xv—Cs1—F1^v	118.14 (2)
F1ⁱⁱ—Ir1—Cs1^vii	53.317 (7)	F1—Cs1—F1^v	52.74 (9)
F1ⁱⁱⁱ—Ir1—Cs1^vii	56.14 (8)	F1^x—Cs1—F1^xvi	129.02 (2)
F1^iv—Ir1—Cs1^vii	126.683 (7)	F1^xi—Cs1—F1^xvi	98.23 (4)
F1—Ir1—Cs1^vii	53.317 (7)	F1^xii—Cs1—F1^xvi	63.06 (8)
F1^v—Ir1—Cs1^vii	123.86 (8)	F1^xiii—Cs1—F1^xvi	162.83 (9)
Cs1^vi—Ir1—Cs1^vii	180.0	F1^xiv—Cs1—F1^xvi	52.74 (9)
F1ⁱ—Ir1—Cs1^viii	53.317 (7)	F1^xv—Cs1—F1^xvi	118.14 (2)
F1ⁱⁱ—Ir1—Cs1^viii	126.683 (7)	F1—Cs1—F1^xvi	66.00 (9)
F1ⁱⁱⁱ—Ir1—Cs1^viii	53.317 (7)	F1^v—Cs1—F1^xvi	118.14 (2)
F1^iv—Ir1—Cs1^viii	123.86 (8)	F1^x—Cs1—F1^xvii	103.17 (7)
F1—Ir1—Cs1^viii	56.14 (8)	F1^xi—Cs1—F1^xvii	143.77 (3)
F1^v—Ir1—Cs1^viii	126.683 (7)	F1^xii—Cs1—F1^xvii	143.77 (3)
Cs1^vi—Ir1—Cs1^viii	106.101 (7)	F1^xiii—Cs1—F1^xvii	49.50 (7)
Cs1^vii—Ir1—Cs1^viii	73.899 (7)	F1^xiv—Cs1—F1^xvii	85.78 (5)
F1ⁱ—Ir1—Cs1^ix	126.683 (7)	F1^xv—Cs1—F1^xvii	49.50 (7)
F1ⁱⁱ—Ir1—Cs1^ix	53.317 (7)	F1—Cs1—F1^xvii	113.34 (3)
F1ⁱⁱⁱ—Ir1—Cs1^ix	126.683 (7)	F1^v—Cs1—F1^xvii	85.78 (5)
F1^iv—Ir1—Cs1^ix	56.14 (8)	F1^xvi—Cs1—F1^xvii	113.34 (3)
F1—Ir1—Cs1^ix	123.86 (8)	F1^x—Cs1—F1^viii	143.77 (3)
F1^v—Ir1—Cs1^ix	53.317 (7)	F1^xi—Cs1—F1^viii	143.77 (3)
Cs1^vi—Ir1—Cs1^ix	73.899 (7)	F1^xii—Cs1—F1^viii	103.17 (7)
Cs1^vii—Ir1—Cs1^ix	106.101 (7)	F1^xiii—Cs1—F1^viii	113.34 (3)
Cs1^viii—Ir1—Cs1^ix	180.0	F1^xiv—Cs1—F1^viii	49.50 (7)
F1ⁱ—Ir1—Cs1	56.14 (8)	F1^xv—Cs1—F1^viii	85.78 (5)
F1ⁱⁱ—Ir1—Cs1	123.86 (8)	F1—Cs1—F1^viii	85.78 (5)
F1ⁱⁱⁱ—Ir1—Cs1	126.683 (7)	F1^v—Cs1—F1^viii	113.34 (3)
F1^iv—Ir1—Cs1	126.683 (7)	F1^xvi—Cs1—F1^viii	49.50 (7)
F1—Ir1—Cs1	53.317 (7)	F1^xvii—Cs1—F1^viii	63.83 (7)
F1^v—Ir1—Cs1	53.317 (7)	F1^x—Cs1—F1ⁱ	143.77 (3)
Cs1^vi—Ir1—Cs1	73.899 (7)	F1^xi—Cs1—F1ⁱ	103.17 (7)
Cs1^vii—Ir1—Cs1	106.101 (7)	F1^xii—Cs1—F1ⁱ	143.77 (3)
Cs1^viii—Ir1—Cs1	73.899 (7)	F1^xiii—Cs1—F1ⁱ	85.78 (5)
Cs1^ix—Ir1—Cs1	106.101 (7)	F1^xiv—Cs1—F1ⁱ	113.34 (3)
F1ⁱ—Ir1—Cs1^iv	123.86 (8)	F1^xv—Cs1—F1ⁱ	113.34 (3)
F1ⁱⁱ—Ir1—Cs1^iv	56.14 (8)	F1—Cs1—F1ⁱ	49.50 (7)
F1ⁱⁱⁱ—Ir1—Cs1^iv	53.317 (7)	F1^v—Cs1—F1ⁱ	49.50 (7)
F1^iv—Ir1—Cs1^iv	53.317 (7)	F1^xvi—Cs1—F1ⁱ	85.78 (5)
F1—Ir1—Cs1^iv	126.683 (7)	F1^xvii—Cs1—F1ⁱ	63.83 (7)
F1^v—Ir1—Cs1^iv	126.683 (7)	F1^viii—Cs1—F1ⁱ	63.83 (7)
Cs1^vi—Ir1—Cs1^iv	106.101 (7)	Ir1—F1—Cs1^xii	162.69 (12)
Cs1^vii—Ir1—Cs1^iv	73.899 (7)	Ir1—F1—Cs1^vii	97.14 (4)
Cs1^viii—Ir1—Cs1^iv	106.101 (7)	Cs1^xii—F1—Cs1^vii	81.77 (4)
Cs1^ix—Ir1—Cs1^iv	73.899 (7)	Ir1—F1—Cs1	97.14 (4)
Cs1—Ir1—Cs1^iv	180.0	Cs1^xii—F1—Cs1	81.77 (4)
F1^x—Cs1—F1^xi	66.39 (7)	Cs1^vii—F1—Cs1	162.83 (9)
F1^x—Cs1—F1^xii	66.39 (7)	Ir1—F1—Cs1^viii	94.15 (9)
F1^xi—Cs1—F1^xii	66.39 (7)	Cs1^xii—F1—Cs1^viii	103.17 (7)
F1^x—Cs1—F1^xiii	63.06 (8)	Cs1^vii—F1—Cs1^viii	94.22 (5)
F1^xi—Cs1—F1^xiii	98.23 (4)	Cs1—F1—Cs1^viii	94.22 (5)

Symmetry codes: (i) y, −x+y, −z+1; (ii) −y, x−y, z; (iii) x−y, x, −z+1; (iv) −x, −y, −z+1; (v) −x+y, −x, z; (vi) −x+1, −y, −z+1; (vii) x−1, y, z; (viii) −x+1, −y+1, −z+1; (ix) x−1, y−1, z; (x) x−y+1, x, −z; (xi) y, −x+y, −z; (xii) −x+1, −y+1, −z; (xiii) −y+1, x−y, z; (xiv) −x+y+1, −x+1, z; (xv) x+1, y, z; (xvi) −y+1, x−y+1, z; (xvii) x−y+1, x, −z+1.

Selected geometric parameters (Å) top

Ir1—F1	1.941 (2)	Cs1—F1	3.1564 (4)
Cs1—F1ⁱ	3.140 (2)	Cs1—F1ⁱⁱ	3.252 (3)

Symmetry codes: (i) y, −x+y, −z; (ii) y, −x+y, −z+1.

supplementary materials

Caesium hexafluoridoiridate(IV)

A. I. Smolentsev, A. I. Gubanov, D. Y. Naumov and A. M. Danilenko

	Fig. 1. A fragment of the Cs₂[IrF₆] structure showing the complex anion surrounded by the cations. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram for Cs₂[IrF₆], viewed in perspective, with Cs-centered anticuboctahedra (orange) and Ir-centered octahedra (purple).