Three hexa­fluorido­iridates(IV), Ca[IrF₆]·2H₂O, Sr[IrF₆]·2H₂O and Ba[IrF₆]

The structures of the hexa­fluorido­iridates(IV) of calcium, Ca[IrF₆]·2H₂O [calcium hexa­fluorido­iridate(IV) dihydrate], strontium, Sr[IrF₆]·2H₂O [strontium hexa­fluorido­iridate(IV) dihydrate], and barium, Ba[IrF₆] [barium hexa­fluorido­iridate(IV)], have been determined by single-crystal X-ray analysis. The first two compounds are isomorphous. Their metal cations are eight-coordinated in a distorted square-anti­prismatic coordination environment, and their anions are represented by an almost ideal octa­hedron. These two structures can be described as frameworks in which all atoms occupy general positions. Sr[RhF₆] and Ba[RhF₆] have a different space group (, from powder diffraction data) but similar cell dimensions. The structures are very close to that of Ba[IrF₆]. The cation is in a cubocta­hedral coordination. The metal atoms are located on special positions of symmetry, while the F atoms are in general positions.

S1. Comment

Fluorine-containing complexes of noble metals attract attention in various areas of chemistry, such as chemical analysis, electrochemistry and applied chemistry (Mitkin, 2001). In particular, this concerns hexafluorometallates. However, structure determination using single-crystal X-ray analysis for many of these compounds has not been carried out yet. Among the complexes of Ir^IV, several have been characterized by X-ray powder diffraction (Babel, 1967) but only one structure solved by the single-crystal method (K₂[IrF₆]; Fitz et al., 2002) is currently available. A new contribution to the crystal chemistry of these compounds seemed useful. We focused our attention on the investigation of alkali and alkaline earth metal hexafluoroiridates. In this paper, the syntheses and structures of three complexes, namely Ca[IrF₆]·2H₂O, (I), Sr[IrF₆]·2H₂O, (II), and Ba[IrF₆], (III), are reported.

The first two title compounds, (I) and (II), are isostructural. The coordination environment of the alkaline earth metal cations includes five F atoms and three H₂O molecules, forming a distorted square-antiprism (Fig. 1). The complex anion, [IrF₆]²⁻, has the shape of an almost ideal octahedron, with average Ir—F distances of 1.934 (7) and 1.913 (10) Å for the Ca and Sr compounds, respectively. In each anion, five F atoms coordinate to the metal cation and one is involved in hydrogen bonding. There are two types of H₂O molecules, each with a different function. The molecules of one type bridge two cations, while the others coordinate only to single cations. Both types also form strong hydrogen bonds with each other and with the F atoms. In addition, there are longer O—H···F contacts, with distances of about 3.4 Å.

The barium compound, (III), is isostructural with the Sr[RhF₆] and Ba[RhF₆] complexes (Wilhelm & Hoppe, 1974). They all belong to the Ba[GeF₆] structural type. The coordination environment of the Ba²⁺ cation includes 12 equidistant F atoms, forming a slightly distorted cuboctahedron. Each F atom is shared between two cuboctahedra and forms one vertex of the [IrF₆]²⁻ octahedron. Thus, the anion interconnects eight Ba²⁺ cations. The Ba and Ir atoms form two rhombohedral sublattices separated by c/2 (Fig. 2).

S2. Experimental

The title compounds were synthesized by the following method. Firstly, K₂[IrCl₆] was obtained by reaction between IrCl₄·4H₂O dissolved in concentrated HCl and KCl solution in the ratio K:Ir = 2:1. In the second stage, K₂[IrF₆] was obtained by the interaction of K₂[IrCl₆] with gaseous F₂ at atmospheric pressure and 573 K in a flow reactor. An aqueous solution of K₂[IrF₆] was then treated with ion-exchange resin in the H form for one day. The mixture was filtered and a solution of H₂[IrF₆] acid was collected. Concentration by evaporation at room temperature yielded a solution of 0.11 M. Ca[IrF₆]·2H₂O, Sr[IrF₆]·2H₂O and Ba[IrF₆] were prepared by the reaction between 0.11 M H₂[IrF₆] (5 ml) and the corresponding reagent, CaO (56 mg), SrCO₃ (74 mg) or BaCO₃ (99 mg). Crystals suitable for X-ray analysis were obtained by slow evaporation at room temperature.

S3. Refinement

The H atoms were located in difference electron-density maps and refined with O—H distances restrained to 0.82 (5) Å and H···H distances restrained to 1.30 (5) Å (to obtain H—O—H angles of about 105°).

Computing details

For all compounds, data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Bruker, 2004); program(s) used to refine structure: SHELXTL (Bruker, 2004); molecular graphics: BS (Ozawa & Kang, 2004); software used to prepare material for publication: SHELXTL (Bruker, 2004).

Figures

	Fig. 1. A packing diagram for the Ca[IrF6]·2H2O and Sr[IrF6]·2H2O structures, viewed along [100]. Hydrogen bonds have been omitted for clarity.
	Fig. 2. A packing diagram for the Ba[IrF6] structure, viewed along [110].

(I) calcium hexafluoroiridate(IV) dihydrate

Crystal data

Ca[IrF6]·2H2O	F(000) = 684
Mr = 382.31	Dx = 4.148 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3691 reflections
a = 5.9055 (2) Å	θ = 3.7–30.0°
b = 9.5369 (3) Å	µ = 22.72 mm^−1
c = 11.0140 (3) Å	T = 296 K
β = 99.262 (1)°	Needle, light pink
V = 612.22 (3) Å^3	0.10 × 0.06 × 0.04 mm
Z = 4

Data collection

Bruker Nonius X8 APEX CCD area-detector diffractometer	1790 independent reflections
Radiation source: fine-focus sealed tube	1688 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 25 pixels mm^-1	θmax = 30.0°, θmin = 2.8°
ϕ scans	h = −7→8
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −11→13
Tmin = 0.210, Tmax = 0.464	l = −11→15
5426 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)] = 0.021	Hydrogen site location: difference Fourier map
wR(F^2) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.25	w = 1/[σ^2(Fo^2) + (0.0253P)^2] where P = (Fo^2 + 2Fc^2)/3
1790 reflections	(Δ/σ)max = 0.001
107 parameters	Δρmax = 0.94 e Å^−3
6 restraints	Δρmin = −2.84 e Å^−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
Ir1	0.40499 (2)	0.539327 (15)	0.265398 (13)	0.00857 (7)
Ca1	0.66063 (14)	0.18588 (9)	0.45306 (8)	0.01119 (16)
F2	0.6581 (4)	0.6440 (3)	0.2159 (2)	0.0184 (5)
F1	0.6254 (4)	0.4059 (3)	0.3455 (2)	0.0199 (5)
F4	0.1480 (5)	0.4431 (3)	0.3160 (3)	0.0211 (6)
F3	0.1815 (4)	0.6693 (3)	0.1806 (2)	0.0198 (5)
F6	0.3794 (5)	0.4293 (3)	0.1160 (2)	0.0208 (6)
F5	0.4356 (5)	0.6502 (3)	0.4133 (2)	0.0210 (6)
O1	1.0353 (6)	0.3009 (4)	0.5137 (4)	0.0247 (7)
O2	0.3779 (6)	0.0763 (4)	0.5856 (3)	0.0167 (6)
H1A	1.065 (11)	0.362 (6)	0.563 (5)	0.04 (2)*
H1B	1.095 (13)	0.328 (8)	0.457 (5)	0.07 (3)*
H2A	0.280 (8)	0.136 (5)	0.561 (4)	0.015 (14)*
H2B	0.423 (10)	0.092 (7)	0.655 (4)	0.033 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.01050 (9)	0.00778 (10)	0.00746 (10)	−0.00010 (5)	0.00158 (6)	−0.00031 (4)
Ca1	0.0131 (4)	0.0109 (4)	0.0095 (4)	0.0003 (3)	0.0015 (3)	0.0000 (3)
F2	0.0194 (12)	0.0188 (14)	0.0191 (13)	−0.0046 (10)	0.0097 (11)	0.0033 (10)
F1	0.0208 (12)	0.0166 (13)	0.0208 (14)	0.0043 (11)	−0.0010 (10)	0.0061 (11)
F4	0.0193 (13)	0.0226 (15)	0.0225 (15)	−0.0081 (11)	0.0063 (11)	0.0044 (11)
F3	0.0184 (12)	0.0140 (12)	0.0248 (14)	0.0045 (10)	−0.0037 (11)	0.0032 (10)
F6	0.0231 (13)	0.0231 (14)	0.0151 (14)	−0.0004 (11)	−0.0004 (11)	−0.0100 (11)
F5	0.0288 (14)	0.0217 (14)	0.0139 (13)	−0.0008 (11)	0.0078 (11)	−0.0099 (10)
O1	0.0251 (17)	0.0260 (19)	0.0227 (19)	−0.0078 (15)	0.0031 (15)	0.0036 (16)
O2	0.0175 (15)	0.0173 (16)	0.0142 (16)	0.0036 (13)	−0.0009 (12)	−0.0008 (13)

Geometric parameters (Å, º)

Ir1—F5	1.926 (2)	Ca1—O2	2.607 (3)
Ir1—F1	1.929 (3)	Ca1—Ca1^v	4.2273 (17)
Ir1—F4	1.931 (3)	Ca1—H2A	2.75 (5)
Ir1—F6	1.937 (3)	F2—Ca1^vi	2.326 (3)
Ir1—F3	1.937 (2)	F3—Ca1^vii	2.306 (3)
Ir1—F2	1.947 (2)	F6—Ca1^viii	2.313 (3)
Ca1—F5^i	2.281 (3)	F5—Ca1^i	2.281 (3)
Ca1—F3^ii	2.306 (3)	O1—H1A	0.79 (4)
Ca1—F6^iii	2.313 (3)	O1—H1B	0.81 (4)
Ca1—F2^iv	2.326 (3)	O2—Ca1^v	2.540 (4)
Ca1—F1	2.402 (3)	O2—H2A	0.83 (4)
Ca1—O1	2.464 (4)	O2—H2B	0.78 (4)
Ca1—O2^v	2.540 (4)
F5—Ir1—F1	90.62 (12)	F3^ii—Ca1—O2	75.88 (10)
F5—Ir1—F4	89.31 (12)	F6^iii—Ca1—O2	72.72 (10)
F1—Ir1—F4	93.33 (12)	F2^iv—Ca1—O2	142.93 (11)
F5—Ir1—F6	178.94 (11)	F1—Ca1—O2	127.87 (10)
F1—Ir1—F6	89.19 (12)	O1—Ca1—O2	130.91 (12)
F4—Ir1—F6	91.74 (13)	O2^v—Ca1—O2	69.58 (12)
F5—Ir1—F3	91.15 (11)	F5^i—Ca1—Ca1^v	104.40 (8)
F1—Ir1—F3	178.21 (12)	F3^ii—Ca1—Ca1^v	73.57 (7)
F4—Ir1—F3	86.39 (12)	F6^iii—Ca1—Ca1^v	68.19 (7)
F6—Ir1—F3	89.05 (12)	F2^iv—Ca1—Ca1^v	109.52 (7)
F5—Ir1—F2	89.05 (11)	F1—Ca1—Ca1^v	147.84 (7)
F1—Ir1—F2	88.54 (11)	O1—Ca1—Ca1^v	136.56 (10)
F4—Ir1—F2	177.53 (11)	O2^v—Ca1—Ca1^v	35.31 (7)
F6—Ir1—F2	89.90 (12)	O2—Ca1—Ca1^v	34.28 (8)
F3—Ir1—F2	91.79 (11)	F5^i—Ca1—H2A	62.2 (11)
F5^i—Ca1—F3^ii	100.10 (10)	F3^ii—Ca1—H2A	64.6 (9)
F5^i—Ca1—F6^iii	89.47 (11)	F6^iii—Ca1—H2A	88.6 (8)
F3^ii—Ca1—F6^iii	141.76 (11)	F2^iv—Ca1—H2A	146.1 (11)
F5^i—Ca1—F2^iv	145.96 (10)	F1—Ca1—H2A	110.7 (8)
F3^ii—Ca1—F2^iv	86.90 (10)	O1—Ca1—H2A	136.2 (10)
F6^iii—Ca1—F2^iv	105.53 (10)	O2^v—Ca1—H2A	81.1 (10)
F5^i—Ca1—F1	73.07 (10)	O2—Ca1—H2A	17.5 (8)
F3^ii—Ca1—F1	75.37 (10)	Ca1^v—Ca1—H2A	47.0 (10)
F6^iii—Ca1—F1	142.25 (11)	Ir1—F2—Ca1^vi	141.72 (14)
F2^iv—Ca1—F1	76.70 (9)	Ir1—F1—Ca1	143.17 (14)
F5^i—Ca1—O1	79.99 (12)	Ir1—F3—Ca1^vii	144.14 (14)
F3^ii—Ca1—O1	149.31 (12)	Ir1—F6—Ca1^viii	150.91 (15)
F6^iii—Ca1—O1	68.66 (11)	Ir1—F5—Ca1^i	157.35 (15)
F2^iv—Ca1—O1	77.55 (12)	Ca1—O1—H1A	127 (5)
F1—Ca1—O1	75.37 (11)	Ca1—O1—H1B	114 (5)
F5^i—Ca1—O2^v	139.27 (11)	H1A—O1—H1B	103 (6)
F3^ii—Ca1—O2^v	77.27 (11)	Ca1^v—O2—Ca1	110.42 (12)
F6^iii—Ca1—O2^v	71.74 (11)	Ca1^v—O2—H2A	126 (4)
F2^iv—Ca1—O2^v	74.76 (10)	Ca1—O2—H2A	91 (4)
F1—Ca1—O2^v	141.14 (11)	Ca1^v—O2—H2B	111 (5)
O1—Ca1—O2^v	122.42 (12)	Ca1—O2—H2B	109 (5)
F5^i—Ca1—O2	70.41 (10)	H2A—O2—H2B	107 (5)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x+1/2, −y+1/2, z+1/2; (iv) −x+3/2, y−1/2, −z+1/2; (v) −x+1, −y, −z+1; (vi) −x+3/2, y+1/2, −z+1/2; (vii) −x+1/2, y+1/2, −z+1/2; (viii) x−1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···F4^ix	0.81 (4)	1.96 (5)	2.736 (4)	159 (8)
O2—H2B···F4^iii	0.78 (4)	2.07 (4)	2.777 (5)	152 (6)
O2—H2A···O1^x	0.83 (4)	2.14 (4)	2.966 (5)	175 (5)

Symmetry codes: (iii) x+1/2, −y+1/2, z+1/2; (ix) x+1, y, z; (x) x−1, y, z.

(II) strontium hexafluoroiridate(IV) dihydrate

Crystal data

Sr[IrF6]·2H2O	F(000) = 756
Mr = 429.85	Dx = 4.354 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3998 reflections
a = 6.0328 (2) Å	θ = 2.8–30.0°
b = 9.8264 (4) Å	µ = 28.47 mm^−1
c = 11.2123 (5) Å	T = 296 K
β = 99.363 (1)°	Needle, light pink
V = 655.82 (5) Å^3	0.18 × 0.08 × 0.04 mm
Z = 4

Data collection

Bruker Nonius X8 APEX CCD area-detector diffractometer	1895 independent reflections
Radiation source: fine-focus sealed tube	1753 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
Detector resolution: 25 pixels mm^-1	θmax = 30.0°, θmin = 2.8°
ϕ scans	h = −4→8
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −13→13
Tmin = 0.080, Tmax = 0.336	l = −15→15
5732 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)] = 0.019	Hydrogen site location: difference Fourier map
wR(F^2) = 0.053	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0251P)^2 + 3.0724P] where P = (Fo^2 + 2Fc^2)/3
1895 reflections	(Δ/σ)max = 0.003
107 parameters	Δρmax = 2.33 e Å^−3
6 restraints	Δρmin = −1.25 e Å^−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
Ir1	0.40999 (3)	0.536839 (17)	0.267134 (15)	0.01472 (6)
Sr1	0.66440 (7)	0.18841 (4)	0.45219 (4)	0.01520 (9)
F2	0.6486 (5)	0.6473 (3)	0.2231 (3)	0.0263 (7)
F1	0.6320 (6)	0.4104 (3)	0.3390 (3)	0.0269 (7)
F4	0.1699 (6)	0.4326 (3)	0.3126 (3)	0.0291 (7)
F3	0.1867 (6)	0.6603 (3)	0.1904 (3)	0.0319 (7)
F6	0.3908 (6)	0.4395 (4)	0.1175 (3)	0.0287 (7)
F5	0.4344 (6)	0.6358 (3)	0.4146 (3)	0.0290 (7)
O1	1.0533 (8)	0.3064 (5)	0.5159 (4)	0.0328 (9)
O2	0.3823 (6)	0.0811 (4)	0.5915 (4)	0.0205 (7)
H1B	1.095 (11)	0.344 (6)	0.459 (4)	0.022 (16)*
H2A	0.263 (7)	0.118 (6)	0.580 (5)	0.016 (15)*
H2B	0.426 (9)	0.089 (6)	0.656 (4)	0.011 (14)*
H1A	1.016 (16)	0.364 (7)	0.557 (7)	0.06 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.01644 (10)	0.01326 (9)	0.01493 (9)	−0.00037 (6)	0.00393 (6)	−0.00003 (6)
Sr1	0.01645 (19)	0.01469 (19)	0.01464 (18)	−0.00055 (14)	0.00308 (14)	0.00093 (14)
F2	0.0276 (15)	0.0283 (16)	0.0258 (16)	−0.0048 (13)	0.0123 (13)	0.0043 (12)
F1	0.0275 (16)	0.0221 (15)	0.0294 (16)	0.0040 (12)	−0.0003 (13)	0.0072 (13)
F4	0.0280 (16)	0.0305 (16)	0.0305 (17)	−0.0123 (13)	0.0097 (13)	0.0018 (13)
F3	0.0254 (16)	0.0227 (15)	0.044 (2)	0.0043 (13)	−0.0048 (14)	0.0040 (14)
F6	0.0291 (17)	0.0340 (17)	0.0216 (15)	−0.0007 (14)	0.0000 (13)	−0.0124 (13)
F5	0.0351 (18)	0.0279 (16)	0.0264 (16)	−0.0042 (14)	0.0121 (13)	−0.0124 (13)
O1	0.027 (2)	0.040 (2)	0.030 (2)	−0.0099 (18)	0.0001 (17)	0.0052 (19)
O2	0.0157 (16)	0.0228 (17)	0.0230 (18)	0.0007 (13)	0.0032 (14)	0.0015 (14)

Geometric parameters (Å, º)

Ir1—F5	1.903 (3)	Sr1—O2^v	2.700 (4)
Ir1—F1	1.907 (3)	Sr1—O2	2.704 (4)
Ir1—F4	1.909 (3)	Sr1—Sr1^v	4.4143 (8)
Ir1—F3	1.910 (3)	F2—Sr1^vi	2.454 (3)
Ir1—F6	1.919 (3)	F3—Sr1^vii	2.453 (3)
Ir1—F2	1.930 (3)	F6—Sr1^viii	2.461 (3)
Sr1—F5^i	2.421 (3)	F5—Sr1^i	2.421 (3)
Sr1—F2^ii	2.454 (3)	O1—H1B	0.81 (4)
Sr1—F3^iii	2.453 (3)	O1—H1A	0.79 (4)
Sr1—F6^iv	2.461 (3)	O2—Sr1^v	2.700 (4)
Sr1—F1	2.515 (3)	O2—H2A	0.80 (4)
Sr1—O1	2.610 (4)	O2—H2B	0.73 (4)
F5—Ir1—F1	90.91 (15)	F6^iv—Sr1—O2^v	70.39 (12)
F5—Ir1—F4	89.84 (15)	F1—Sr1—O2^v	139.65 (12)
F1—Ir1—F4	92.79 (15)	O1—Sr1—O2^v	123.23 (14)
F5—Ir1—F3	90.93 (15)	F5^i—Sr1—O2	71.37 (11)
F1—Ir1—F3	178.15 (15)	F2^ii—Sr1—O2	144.39 (11)
F4—Ir1—F3	87.20 (15)	F3^iii—Sr1—O2	76.96 (12)
F5—Ir1—F6	178.70 (15)	F6^iv—Sr1—O2	71.96 (11)
F1—Ir1—F6	89.03 (15)	F1—Sr1—O2	128.68 (11)
F4—Ir1—F6	91.45 (15)	O1—Sr1—O2	129.60 (13)
F3—Ir1—F6	89.13 (16)	O2^v—Sr1—O2	70.45 (13)
F5—Ir1—F2	88.80 (14)	F5^i—Sr1—Sr1^v	106.45 (8)
F1—Ir1—F2	88.44 (14)	F2^ii—Sr1—Sr1^v	109.86 (8)
F4—Ir1—F2	178.18 (15)	F3^iii—Sr1—Sr1^v	71.89 (8)
F3—Ir1—F2	91.62 (14)	F6^iv—Sr1—Sr1^v	66.74 (8)
F6—Ir1—F2	89.90 (15)	F1—Sr1—Sr1^v	148.09 (8)
F5^i—Sr1—F2^ii	143.44 (11)	O1—Sr1—Sr1^v	136.52 (10)
F5^i—Sr1—F3^iii	102.07 (12)	O2^v—Sr1—Sr1^v	35.26 (8)
F2^ii—Sr1—F3^iii	85.43 (12)	O2—Sr1—Sr1^v	35.19 (8)
F5^i—Sr1—F6^iv	93.55 (12)	Ir1—F2—Sr1^vi	139.16 (16)
F2^ii—Sr1—F6^iv	104.37 (11)	Ir1—F1—Sr1	140.36 (17)
F3^iii—Sr1—F6^iv	138.41 (12)	Ir1—F3—Sr1^vii	146.71 (18)
F5^i—Sr1—F1	71.68 (12)	Ir1—F6—Sr1^viii	149.37 (18)
F2^ii—Sr1—F1	75.33 (11)	Ir1—F5—Sr1^i	155.32 (19)
F3^iii—Sr1—F1	77.34 (11)	Sr1—O1—H1B	112 (5)
F6^iv—Sr1—F1	144.19 (12)	Sr1—O1—H1A	99 (7)
F5^i—Sr1—O1	79.32 (14)	H1B—O1—H1A	106 (6)
F2^ii—Sr1—O1	77.44 (14)	Sr1^v—O2—Sr1	109.56 (13)
F3^iii—Sr1—O1	150.55 (13)	Sr1^v—O2—H2A	111 (4)
F6^iv—Sr1—O1	69.93 (13)	Sr1—O2—H2A	111 (4)
F1—Sr1—O1	75.25 (12)	Sr1^v—O2—H2B	107 (5)
F5^i—Sr1—O2^v	141.54 (11)	Sr1—O2—H2B	112 (5)
F2^ii—Sr1—O2^v	75.00 (11)	H2A—O2—H2B	106 (5)
F3^iii—Sr1—O2^v	73.61 (12)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) x+1/2, −y+1/2, z+1/2; (v) −x+1, −y, −z+1; (vi) −x+3/2, y+1/2, −z+1/2; (vii) −x+1/2, y+1/2, −z+1/2; (viii) x−1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···F4^ix	0.81 (4)	1.97 (4)	2.784 (6)	175 (7)
O2—H2B···F4^iv	0.73 (4)	2.11 (4)	2.788 (5)	154 (6)
O2—H2A···O1^x	0.80 (4)	2.29 (5)	3.002 (6)	149 (6)

Symmetry codes: (iv) x+1/2, −y+1/2, z+1/2; (ix) x+1, y, z; (x) x−1, y, z.

(III) barium hexafluoroiridate(IV)

Crystal data

Ba[IrF6]	Dx = 6.404 Mg m^−3
Mr = 443.54	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 967 reflections
Hall symbol: -R 3	θ = 4.2–30.0°
a = 7.3965 (5) Å	µ = 37.44 mm^−1
c = 7.2826 (7) Å	T = 293 K
V = 345.04 (5) Å^3	Needle, light pink
Z = 3	0.12 × 0.04 × 0.04 mm
F(000) = 561

Data collection

Bruker Nonius X8 APEX CCD area-detector diffractometer	182 independent reflections
Radiation source: fine-focus sealed tube	182 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 25 pixels mm^-1	θmax = 27.4°, θmin = 4.2°
ϕ scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −7→9
Tmin = 0.178, Tmax = 0.216	l = −9→9
889 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)] = 0.024	w = 1/[σ^2(Fo^2) + (0.0408P)^2 + 6.1383P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.066	(Δ/σ)max < 0.001
S = 1.22	Δρmax = 1.91 e Å^−3
182 reflections	Δρmin = −2.46 e Å^−3
15 parameters	Extinction correction: SHELXTL (Bruker, 2004), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0108 (11)

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
Ir1	0.0000	0.0000	0.0000	0.0074 (4)
F1	0.0729 (6)	0.2325 (6)	0.1640 (5)	0.0154 (10)
Ba1	0.3333	0.6667	0.1667	0.0099 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ir1	0.0064 (4)	0.0064 (4)	0.0093 (5)	0.0032 (2)	0.000	0.000
F1	0.017 (2)	0.0127 (19)	0.015 (2)	0.0068 (16)	−0.0006 (14)	−0.0042 (15)
Ba1	0.0092 (5)	0.0092 (5)	0.0112 (6)	0.0046 (2)	0.000	0.000

Geometric parameters (Å, º)

Ir1—F1^i	1.935 (4)	Ba1—F1^ix	2.800 (4)
Ir1—F1	1.935 (4)	Ba1—F1^x	2.800 (4)
Ir1—F1^ii	1.935 (4)	Ba1—F1^xi	2.800 (4)
Ir1—F1^iii	1.935 (4)	Ba1—F1^xii	2.800 (4)
Ir1—F1^iv	1.935 (4)	Ba1—F1^xiii	2.883 (4)
Ir1—F1^v	1.935 (4)	Ba1—F1^xiv	2.883 (4)
Ir1—Ba1^vi	3.6413 (4)	Ba1—F1^xv	2.883 (4)
Ir1—Ba1^vii	3.6413 (4)	Ba1—F1^xvi	2.883 (4)
Ba1—F1	2.800 (4)	Ba1—F1^xvii	2.883 (4)
F1—Ba1^vii	2.883 (4)	Ba1—F1^xviii	2.883 (4)
Ba1—F1^viii	2.800 (4)
F1^i—Ir1—F1	180.0 (3)	F1^xi—Ba1—F1^xiii	119.63 (13)
F1^i—Ir1—F1^ii	85.93 (18)	F1—Ba1—F1^xiii	96.28 (14)
F1—Ir1—F1^ii	94.07 (18)	F1^xii—Ba1—F1^xiii	113.77 (12)
F1^i—Ir1—F1^iii	94.07 (18)	F1^viii—Ba1—F1^xiv	96.28 (14)
F1—Ir1—F1^iii	85.93 (18)	F1^ix—Ba1—F1^xiv	119.63 (13)
F1^ii—Ir1—F1^iii	180.0 (3)	F1^x—Ba1—F1^xiv	66.23 (12)
F1^i—Ir1—F1^iv	94.07 (18)	F1^xi—Ba1—F1^xiv	83.72 (14)
F1—Ir1—F1^iv	85.93 (18)	F1—Ba1—F1^xiv	113.77 (12)
F1^ii—Ir1—F1^iv	94.07 (18)	F1^xii—Ba1—F1^xiv	60.37 (13)
F1^iii—Ir1—F1^iv	85.93 (18)	F1^xiii—Ba1—F1^xiv	54.47 (12)
F1^i—Ir1—F1^v	85.93 (18)	F1^viii—Ba1—F1^xv	113.77 (12)
F1—Ir1—F1^v	94.07 (18)	F1^ix—Ba1—F1^xv	83.72 (14)
F1^ii—Ir1—F1^v	85.93 (18)	F1^x—Ba1—F1^xv	119.63 (13)
F1^iii—Ir1—F1^v	94.07 (18)	F1^xi—Ba1—F1^xv	66.23 (12)
F1^iv—Ir1—F1^v	180.0 (5)	F1—Ba1—F1^xv	60.37 (13)
F1^i—Ir1—Ba1^vi	51.91 (12)	F1^xii—Ba1—F1^xv	96.28 (14)
F1—Ir1—Ba1^vi	128.09 (12)	F1^xiii—Ba1—F1^xv	54.47 (12)
F1^ii—Ir1—Ba1^vi	51.91 (12)	F1^xiv—Ba1—F1^xv	54.47 (12)
F1^iii—Ir1—Ba1^vi	128.09 (12)	F1^viii—Ba1—F1^xvi	66.23 (12)
F1^iv—Ir1—Ba1^vi	128.09 (12)	F1^ix—Ba1—F1^xvi	96.28 (14)
F1^v—Ir1—Ba1^vi	51.91 (12)	F1^x—Ba1—F1^xvi	60.37 (13)
F1^i—Ir1—Ba1^vii	128.09 (12)	F1^xi—Ba1—F1^xvi	113.77 (12)
F1—Ir1—Ba1^vii	51.91 (12)	F1—Ba1—F1^xvi	119.63 (13)
F1^ii—Ir1—Ba1^vii	128.09 (12)	F1^xii—Ba1—F1^xvi	83.72 (14)
F1^iii—Ir1—Ba1^vii	51.91 (12)	F1^xiii—Ba1—F1^xvi	125.53 (12)
F1^iv—Ir1—Ba1^vii	51.91 (12)	F1^xiv—Ba1—F1^xvi	125.53 (13)
F1^v—Ir1—Ba1^vii	128.09 (12)	F1^xv—Ba1—F1^xvi	180.0
Ba1^vi—Ir1—Ba1^vii	180.0	F1^viii—Ba1—F1^xvii	83.72 (14)
Ir1—F1—Ba1	138.56 (19)	F1^ix—Ba1—F1^xvii	60.37 (13)
Ir1—F1—Ba1^vii	96.20 (15)	F1^x—Ba1—F1^xvii	113.77 (12)
Ba1—F1—Ba1^vii	119.63 (13)	F1^xi—Ba1—F1^xvii	96.28 (14)
F1^viii—Ba1—F1^ix	60.004 (3)	F1—Ba1—F1^xvii	66.23 (12)
F1^viii—Ba1—F1^x	60.004 (3)	F1^xii—Ba1—F1^xvii	119.63 (13)
F1^ix—Ba1—F1^x	119.994 (2)	F1^xiii—Ba1—F1^xvii	125.53 (12)
F1^viii—Ba1—F1^xi	180.0	F1^xiv—Ba1—F1^xvii	180.0
F1^ix—Ba1—F1^xi	119.996 (3)	F1^xv—Ba1—F1^xvii	125.53 (13)
F1^x—Ba1—F1^xi	119.996 (3)	F1^xvi—Ba1—F1^xvii	54.47 (12)
F1^viii—Ba1—F1	119.995 (3)	F1^viii—Ba1—F1^xviii	119.63 (13)
F1^ix—Ba1—F1	60.005 (3)	F1^ix—Ba1—F1^xviii	113.77 (12)
F1^x—Ba1—F1	180.0	F1^x—Ba1—F1^xviii	96.28 (14)
F1^xi—Ba1—F1	60.005 (2)	F1^xi—Ba1—F1^xviii	60.37 (13)
F1^viii—Ba1—F1^xii	119.995 (3)	F1—Ba1—F1^xviii	83.72 (14)
F1^ix—Ba1—F1^xii	180.0	F1^xii—Ba1—F1^xviii	66.23 (12)
F1^x—Ba1—F1^xii	60.006 (2)	F1^xiii—Ba1—F1^xviii	180.0
F1^xi—Ba1—F1^xii	60.005 (3)	F1^xiv—Ba1—F1^xviii	125.53 (12)
F1—Ba1—F1^xii	119.995 (2)	F1^xv—Ba1—F1^xviii	125.53 (12)
F1^viii—Ba1—F1^xiii	60.37 (13)	F1^xvi—Ba1—F1^xviii	54.47 (12)
F1^ix—Ba1—F1^xiii	66.23 (12)	F1^xvii—Ba1—F1^xviii	54.47 (12)
F1^x—Ba1—F1^xiii	83.72 (14)

Symmetry codes: (i) −x, −y, −z; (ii) x−y, x, −z; (iii) −x+y, −x, z; (iv) −y, x−y, z; (v) y, −x+y, −z; (vi) x−1/3, y−2/3, z−2/3; (vii) x−1/3, y−2/3, z+1/3; (viii) −x+y, −x+1, z; (ix) y−1/3, −x+y+1/3, −z+1/3; (x) −x+2/3, −y+4/3, −z+1/3; (xi) x−y+2/3, x+1/3, −z+1/3; (xii) −y+1, x−y+1, z; (xiii) x−y+1/3, x+2/3, −z+2/3; (xiv) y+1/3, −x+y+2/3, −z+2/3; (xv) −x+1/3, −y+2/3, −z+2/3; (xvi) x+1/3, y+2/3, z−1/3; (xvii) −y+1/3, x−y+2/3, z−1/3; (xviii) −x+y+1/3, −x+2/3, z−1/3.