Ca5Zr3F22

Oudahmane, A.; El-Ghozzi, M.; Avignant, D.

doi:10.1107/S1600536812008495

inorganic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page i23

doi:10.1107/S1600536812008495

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Ca₅Zr₃F₂₂

Abdelghani Oudahmane,^a Malika El-Ghozzi ^a and Daniel Avignant ^a ^*

^aClermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, 63000 Clermont-Ferrand, France and CNRS, UMR 6296, ICCF, BP 80026, 63171 Aubière, France
^*Correspondence e-mail: daniel.avignant@univ-bpclermont.fr

(Received 17 February 2012; accepted 25 February 2012; online 3 March 2012)

Single crystals of Ca₅Zr₃F₂₂, pentacalcium trizirconium docosafluoride, were obtained unexpectedly by solid-state reaction between CaF₂ and ZrF₄ in the presence of AgF. The structure of the title compound is isotypic with that of Sr₅Zr₃F₂₂ and can be described as being composed of layers with composition [Zr₃F₂₀]⁸⁻ made up from two different [ZrF₈]⁴⁻ square antiprisms (one with site symmetry 2) by corner-sharing. The layers extending parallel to the (001) plane are further linked by Ca²⁺ cations, forming a three-dimensional network. Amongst the four crystallographically different Ca²⁺ ions, three are located on twofold rotation axes. The Ca²⁺ ions exhibit coordination numbers ranging from 8 to 12, depending on the cut off, with very distorted fluorine environments. Two of the Ca²⁺ ions occupy interstices between the layers whereas the other two are located in void spaces of the [Zr₃F₂₀]⁸⁻ layer and alternate with the two Zr atoms along [010]. The crystal under investigation was an inversion twin.

Related literature

For the isotypic Sr analogue, see: Le Bail (1996 ). The crystal chemistry of fluorides has been reviewed by Babel & Tressaud (1985 ). For phase relationships in the CaF₂–ZrF₄ system, see: L'Helgoualch et al. (1971 ); Kotsar et al. (1973 ); Ratnikov et al. (1977 ); Laval et al. (1987 ). For bond-valence analysis, see: Brese & O'Keeffe (1991 ).

Experimental

Crystal data

Ca₅Zr₃F₂₂
M_r = 892.06
Orthorhombic, P 2₁ 2₁ 2
a = 9.9844 (3) Å
b = 7.4059 (2) Å
c = 9.9046 (3) Å
V = 732.38 (4) Å³
Z = 2
Mo Kα radiation
μ = 4.09 mm⁻¹
T = 296 K
0.19 × 0.06 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.587, T_max = 0.747
7993 measured reflections
3466 independent reflections
2909 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.058
S = 0.99
3466 reflections
139 parameters
Δρ_max = 0.88 e Å⁻³
Δρ_min = −0.77 e Å⁻³
Absolute structure: Flack (1983 ), 1462 Friedel pairs
Flack parameter: 0.0 (4)

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CaRine (Boudias & Monceau, 1998 ) and ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812008495/wm2595sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008495/wm2595Isup2.hkl

checkCIF report

Comment top

Despite several reports related to investigations of the pseudo-binary system CaF₂–ZrF₄ (L'Helgoualch et al. 1971; Kotsar et al. 1973; Ratnikov et al. 1977; Babel & Tressaud, 1985; Laval et al. 1987) the title compound has never been mentioned previously. Therefore the determination of its crystal structure was of prime importance to complete a thorough examination of the phase diagram of this system.

The orthorhombic structure of the title compound is isotypic with that of Sr₅Zr₃F₂₂ reported by Le Bail (1996). As with this latter, the structure of Ca₅Zr₃F₂₂ has also been determined from an inversion twinned crystal although the crystals were grown in very different ways. Figure 1 displays the polyhedral string in Ca₅Zr₃F₂₂. Both Zr1 and Zr2 cations are 8-coordinated by the fluoride ions, in distorted square antiprismatic environments. The square antiprism surrounding Zr2 (site symmetry 2) with Zr—F distances ranging from 2.0771 (19) Å to 2.148 (2) Å is less distorted than that surrounding Zr1 (site symmetry 1) where Zr—F distances range from 2.062 (2) to 2.2154 (19) Å. Each Zr2 square antiprism is connected by sharing corners to four Zr1 square antiprisms as shown in Fig. 2. The crystal structure is built up from layers of corner-sharing [ZrF₈]^4- square antiprisms. The layers extending parallel to (001) are further held together by Ca²⁺ cations to form the three-dimensional network (Fig. 3). The calcium ions are divided into four crystallographically different atoms exhibiting coordination numbers from 8 to 12, depending on the cut off, with very distorted fluorine environments. The bond-valence analysis of the title structure carried out using Brese & O'Keeffe's R_ij parameters for solids (Brese & O'Keeffe, 1991) is displayed in Figure 4. Large deviations from the ideal value 2 have been obtained for both Ca1 and Ca2. For this latter the value of 1.730 valence units (v.u.) is obtained with Ca—F distances up to 2.661 Å considered as relevant for the first coordination sphere whereas the value of 1.843 v.u. is reached with four additional interactions involving distances up to 3.109 Å. Despite these four additional contributions the formal charge for Ca2 still shows a deficit. For comparison, bond-valence calculations have also been performed for the homologuous Sr₅Zr₃F₂₂ from bond lengths reported by Le Bail (1996). Significant deviations (see Fig. 4) are also observed for the alkaline earth cations but the formal charges are in excess in this case. This may be most likely related to the size difference of the ionic radii of Ca²⁺ and Sr²⁺. Ca2 and Ca4 occupy interstices between the layers whereas Ca3 and Ca1 are located in void spaces of the [Zr₃F₂₀]^8- layer and alternate with Zr2 and Zr1, respectively, along [010]. Thus Ca3 and Ca4 also appear as being located in channels parallel to [001].

Related literature top

For the isotypic Sr analogue, see: Le Bail (1996). The crystal chemistry of fluorides has been reviewed by Babel & Tressaud (1985). For phase relationships in the CaF₂–ZrF₄ system, see: L'Helgoualch et al. (1971); Kotsar et al. (1973); Ratnikov et al. (1977); Laval et al. (1987). For bond-valence analysis, see: Brese & O'Keeffe (1991).

Experimental top

Single crystals of Ca₅Zr₃F₂₂ were unexpectedly obtained from an equimolar mixture of AgF, CaF₂ and ZrF₄ heated at 873 K in a sealed platinum tube during the study of the phase diagram of the ternary system AgF–CaF₂–ZrF₄. After heating at this temperature for 24 h, the sample was cooled to room temperature at the rate of 5 K^.h^-1 for the first 24 h and then by switching the power off. Small platelet like crystals of Ca₅Zr₃F₂₂ could have been extracted from the batch.

Both AgF and CaF₂ were commercial products whereas ZrF₄ was prepared by direct fluorination of ZrO₂ under pure fluorine gas flow at 873 K with intermediate grindings. CaF₂ was also heated at 873 K overnight under fluorine gas flow prior to use.

Structure description top

For the isotypic Sr analogue, see: Le Bail (1996). The crystal chemistry of fluorides has been reviewed by Babel & Tressaud (1985). For phase relationships in the CaF₂–ZrF₄ system, see: L'Helgoualch et al. (1971); Kotsar et al. (1973); Ratnikov et al. (1977); Laval et al. (1987). For bond-valence analysis, see: Brese & O'Keeffe (1991).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CaRine (Boudias & Monceau, 1998) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the polyhedral linkage in Ca₅Zr₃F₂₂. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: (i) 3/2 - x, -1/2 + y, 2 - z; (ii) x, -1 + y, z; (iii) 2 - x, -y, z; (iv) 2 - x, 1 - y, z; (v) x, 1 + y, z; (vi) 3/2 - x, 1/2 + y, 2 - z; (vii) 3/2 - x, -1/2 + y, 1 - z; (viii) 1/2 + x, -1/2 - y, 1 - z; (ix) -1/2 + x, -1/2 - y, 2 - z; (x) 1/2 + x, 1/2 - y, 1 - z; (xi) 2 - x, -1 - y, z; (xii) 3/2 - x, 1/2 + y, 1 - z; (xiii) -1/2 + x, 1/2 - y, 2 - z; (xiv) 1 - x, -y, z; (xv) 1 - x, 1 - y, z; (xvi) -1/2 + x, -1/2 - y, 1 - z;
	Fig. 2. Details of the connection between Zr2 and Zr1 square antiprisms in Ca₅Zr₃F₂₂.
	Fig. 3. Projection of the structure of Ca₅Zr₃F₂₂ along [010] showing the [Zr₃F₂₀]^8- layers held together by Ca²⁺ ions.
	Fig. 4. Bond-valence analysis of the structures of Ca₅Zr₃F₂₂ (top) and Sr₅Zr₃F₂₂ (bottom) using parameters for solids (R_Zr—F = 1.854, R_Ca—F = 1.842, R_Sr—F = 2.019) from Brese & O'Keeffe (1991). It should be noted that the atom labelling in the two isotypic structures is different.

pentacalcium trizirconium docosafluoride top

Crystal data top

Ca₅Zr₃F₂₂	F(000) = 836
M_r = 892.06	D_x = 4.045 Mg m⁻³
Orthorhombic, P2₁2₁2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 1507 reflections
a = 9.9844 (3) Å	θ = 4.0–35.8°
b = 7.4059 (2) Å	µ = 4.09 mm⁻¹
c = 9.9046 (3) Å	T = 296 K
V = 732.38 (4) Å³	Platelet, colourless
Z = 2	0.19 × 0.06 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	3466 independent reflections
Radiation source: fine-focus sealed tube	2909 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 8.3333 pixels mm^-1	θ_max = 36.0°, θ_min = 3.4°
ω and φ–scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −12→6
T_min = 0.587, T_max = 0.747	l = −16→12
7993 measured reflections

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)] = 0.036	w = 1/[σ²(F_o²) + (0.0112P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.058	(Δ/σ)_max = 0.001
S = 0.99	Δρ_max = 0.88 e Å⁻³
3466 reflections	Δρ_min = −0.77 e Å⁻³
139 parameters	Absolute structure: Flack (1983), 1462 Friedel pairs
0 restraints	Absolute structure parameter: 0.0 (4)

Crystal data top

Ca₅Zr₃F₂₂	V = 732.38 (4) Å³
M_r = 892.06	Z = 2
Orthorhombic, P2₁2₁2	Mo Kα radiation
a = 9.9844 (3) Å	µ = 4.09 mm⁻¹
b = 7.4059 (2) Å	T = 296 K
c = 9.9046 (3) Å	0.19 × 0.06 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	3466 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2909 reflections with I > 2σ(I)
T_min = 0.587, T_max = 0.747	R_int = 0.037
7993 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.058	Δρ_max = 0.88 e Å⁻³
S = 0.99	Δρ_min = −0.77 e Å⁻³
3466 reflections	Absolute structure: Flack (1983), 1462 Friedel pairs
139 parameters	Absolute structure parameter: 0.0 (4)

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
Zr1	0.71210 (3)	0.25190 (5)	0.77653 (3)	0.00516 (5)
Zr2	0.5000	0.0000	0.46134 (5)	0.00610 (9)
Ca1	0.71132 (6)	−0.23978 (10)	0.75189 (6)	0.00980 (11)
Ca2	1.0000	0.5000	0.94489 (11)	0.01098 (18)
Ca3	1.0000	0.0000	0.53761 (10)	0.00549 (16)
Ca4	1.0000	0.0000	0.97774 (11)	0.01109 (19)
F1	0.88717 (17)	−0.2405 (3)	0.89417 (19)	0.0127 (4)
F2	0.85135 (16)	0.2410 (3)	0.93117 (18)	0.0108 (3)
F3	0.8514 (2)	0.0603 (2)	0.7085 (3)	0.0170 (5)
F4	0.88835 (19)	0.4117 (2)	0.7118 (3)	0.0126 (4)
F5	1.10993 (18)	0.2790 (3)	0.6049 (2)	0.0128 (4)
F6	0.65761 (18)	0.0167 (3)	0.8771 (2)	0.0113 (4)
F7	0.69569 (18)	0.4936 (3)	0.87846 (19)	0.0114 (4)
F8	0.6504 (2)	0.4338 (3)	0.6301 (2)	0.0156 (5)
F9	1.10631 (18)	−0.2758 (3)	0.4672 (2)	0.0131 (4)
F10	0.51040 (18)	0.2795 (2)	0.83055 (19)	0.0139 (4)
F11	0.6171 (2)	0.0833 (3)	0.6283 (3)	0.0177 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.00491 (11)	0.00437 (10)	0.00621 (12)	0.00005 (14)	−0.00025 (10)	0.00010 (14)
Zr2	0.0070 (2)	0.00559 (19)	0.0057 (2)	−0.0005 (2)	0.000	0.000
Ca1	0.0079 (2)	0.0118 (3)	0.0097 (3)	−0.0004 (3)	0.0000 (2)	0.0002 (3)
Ca2	0.0104 (4)	0.0085 (4)	0.0139 (5)	0.0006 (4)	0.000	0.000
Ca3	0.0047 (4)	0.0059 (4)	0.0059 (4)	0.0005 (5)	0.000	0.000
Ca4	0.0097 (4)	0.0065 (4)	0.0170 (5)	−0.0010 (4)	0.000	0.000
F1	0.0108 (8)	0.0113 (8)	0.0161 (9)	−0.0008 (9)	−0.0033 (7)	−0.0009 (10)
F2	0.0100 (8)	0.0125 (8)	0.0098 (8)	−0.0027 (10)	−0.0044 (6)	0.0024 (10)
F3	0.0194 (11)	0.0113 (9)	0.0203 (13)	0.0026 (8)	0.0086 (10)	−0.0019 (9)
F4	0.0118 (10)	0.0128 (9)	0.0133 (11)	−0.0041 (7)	0.0021 (9)	0.0004 (8)
F5	0.0103 (8)	0.0159 (11)	0.0122 (10)	0.0038 (7)	−0.0044 (7)	−0.0006 (8)
F6	0.0129 (9)	0.0090 (9)	0.0120 (10)	−0.0019 (8)	0.0002 (7)	−0.0007 (8)
F7	0.0129 (9)	0.0084 (8)	0.0130 (10)	−0.0016 (9)	−0.0016 (8)	−0.0023 (9)
F8	0.0202 (12)	0.0145 (10)	0.0120 (12)	0.0008 (8)	−0.0061 (9)	0.0047 (8)
F9	0.0135 (9)	0.0108 (10)	0.0151 (10)	−0.0034 (8)	0.0041 (7)	0.0002 (8)
F10	0.0077 (8)	0.0177 (10)	0.0161 (10)	0.0009 (8)	0.0012 (8)	−0.0044 (7)
F11	0.0233 (12)	0.0146 (10)	0.0151 (13)	−0.0028 (9)	−0.0065 (10)	−0.0028 (9)

Geometric parameters (Å, º) top

Zr1—F7	2.062 (2)	Ca2—F6^x	2.366 (2)
Zr1—F2	2.0701 (16)	Ca2—F2^xi	2.429 (2)
Zr1—F8	2.073 (2)	Ca2—F2	2.429 (2)
Zr1—F6	2.079 (2)	Ca2—F4	2.645 (3)
Zr1—F10	2.0937 (18)	Ca2—F4^xi	2.645 (3)
Zr1—F3	2.098 (2)	Ca2—F10^x	3.040 (2)
Zr1—F11	2.148 (2)	Ca2—F10^ix	3.040 (2)
Zr1—F4	2.2154 (19)	Ca2—F7	3.1091 (18)
Zr2—F5ⁱ	2.0771 (19)	Ca2—F7^xi	3.1091 (18)
Zr2—F5ⁱⁱ	2.0771 (19)	Ca3—F8ⁱ	2.292 (2)
Zr2—F9ⁱⁱⁱ	2.0939 (18)	Ca3—F8^xii	2.292 (2)
Zr2—F9^iv	2.0939 (18)	Ca3—F3^vi	2.295 (2)
Zr2—F11	2.117 (2)	Ca3—F3	2.295 (2)
Zr2—F11^v	2.117 (2)	Ca3—F9	2.4055 (19)
Zr2—F4ⁱⁱ	2.148 (2)	Ca3—F9^vi	2.4055 (19)
Zr2—F4ⁱ	2.148 (2)	Ca3—F5	2.4327 (19)
Ca1—F1	2.2514 (18)	Ca3—F5^vi	2.4327 (19)
Ca1—F5^vi	2.3214 (19)	Ca4—F1	2.264 (2)
Ca1—F6	2.331 (2)	Ca4—F1^vi	2.264 (2)
Ca1—F7^vii	2.344 (2)	Ca4—F2^vi	2.367 (2)
Ca1—F10^v	2.3651 (19)	Ca4—F2	2.367 (2)
Ca1—F9^iv	2.412 (2)	Ca4—F7^ix	2.418 (2)
Ca1—F3	2.661 (2)	Ca4—F7^xiii	2.418 (2)
Ca1—F8^vii	2.769 (2)	Ca4—F10^ix	2.5067 (19)
Ca1—F11	2.848 (2)	Ca4—F10^xiii	2.5067 (19)
Ca2—F1^viii	2.283 (2)	Ca4—F3	3.085 (3)
Ca2—F1^vi	2.283 (2)	Ca4—F3^vi	3.085 (3)
Ca2—F6^ix	2.366 (2)

F7—Zr1—F2	74.04 (8)	F1^viii—Ca2—F7	58.94 (6)
F7—Zr1—F8	75.80 (8)	F1^vi—Ca2—F7	115.01 (6)
F2—Zr1—F8	137.96 (9)	F6^ix—Ca2—F7	143.78 (7)
F7—Zr1—F6	118.16 (7)	F6^x—Ca2—F7	60.56 (6)
F2—Zr1—F6	77.79 (8)	F2^xi—Ca2—F7	126.67 (6)
F8—Zr1—F6	143.31 (8)	F2—Ca2—F7	51.62 (6)
F7—Zr1—F10	73.37 (7)	F4—Ca2—F7	53.12 (6)
F2—Zr1—F10	117.44 (7)	F4^xi—Ca2—F7	103.35 (6)
F8—Zr1—F10	80.18 (8)	F10^x—Ca2—F7	97.57 (5)
F6—Zr1—F10	73.00 (7)	F10^ix—Ca2—F7	100.25 (5)
F7—Zr1—F3	142.87 (8)	F1^viii—Ca2—F7^xi	115.01 (6)
F2—Zr1—F3	76.47 (9)	F1^vi—Ca2—F7^xi	58.94 (6)
F8—Zr1—F3	114.32 (10)	F6^ix—Ca2—F7^xi	60.56 (6)
F6—Zr1—F3	76.16 (8)	F6^x—Ca2—F7^xi	143.78 (7)
F10—Zr1—F3	141.78 (8)	F2^xi—Ca2—F7^xi	51.62 (6)
F7—Zr1—F11	143.54 (8)	F2—Ca2—F7^xi	126.67 (6)
F2—Zr1—F11	141.23 (9)	F4—Ca2—F7^xi	103.35 (6)
F8—Zr1—F11	76.60 (8)	F4^xi—Ca2—F7^xi	53.12 (6)
F6—Zr1—F11	74.05 (8)	F10^x—Ca2—F7^xi	100.25 (5)
F10—Zr1—F11	78.86 (8)	F10^ix—Ca2—F7^xi	97.57 (5)
F3—Zr1—F11	71.33 (9)	F7—Ca2—F7^xi	155.57 (8)
F7—Zr1—F4	74.98 (8)	F8ⁱ—Ca3—F8^xii	87.10 (12)
F2—Zr1—F4	72.62 (8)	F8ⁱ—Ca3—F3^vi	156.41 (7)
F8—Zr1—F4	71.74 (8)	F8^xii—Ca3—F3^vi	98.78 (8)
F6—Zr1—F4	142.56 (8)	F8ⁱ—Ca3—F3	98.78 (8)
F10—Zr1—F4	141.80 (7)	F8^xii—Ca3—F3	156.41 (7)
F3—Zr1—F4	75.04 (7)	F3^vi—Ca3—F3	84.96 (13)
F11—Zr1—F4	117.61 (9)	F8ⁱ—Ca3—F9	84.10 (7)
F5ⁱ—Zr2—F5ⁱⁱ	143.17 (11)	F8^xii—Ca3—F9	71.48 (7)
F5ⁱ—Zr2—F9ⁱⁱⁱ	117.63 (7)	F3^vi—Ca3—F9	76.31 (7)
F5ⁱⁱ—Zr2—F9ⁱⁱⁱ	75.52 (7)	F3—Ca3—F9	131.65 (7)
F5ⁱ—Zr2—F9^iv	75.52 (7)	F8ⁱ—Ca3—F9^vi	71.48 (7)
F5ⁱⁱ—Zr2—F9^iv	117.63 (7)	F8^xii—Ca3—F9^vi	84.10 (7)
F9ⁱⁱⁱ—Zr2—F9^iv	140.46 (11)	F3^vi—Ca3—F9^vi	131.65 (7)
F5ⁱ—Zr2—F11	140.20 (8)	F3—Ca3—F9^vi	76.31 (7)
F5ⁱⁱ—Zr2—F11	74.04 (8)	F9—Ca3—F9^vi	146.27 (10)
F9ⁱⁱⁱ—Zr2—F11	77.57 (8)	F8ⁱ—Ca3—F5	132.51 (7)
F9^iv—Zr2—F11	71.76 (8)	F8^xii—Ca3—F5	73.82 (7)
F5ⁱ—Zr2—F11^v	74.04 (8)	F3^vi—Ca3—F5	70.82 (6)
F5ⁱⁱ—Zr2—F11^v	140.20 (8)	F3—Ca3—F5	85.66 (7)
F9ⁱⁱⁱ—Zr2—F11^v	71.76 (8)	F9—Ca3—F5	126.99 (6)
F9^iv—Zr2—F11^v	77.57 (8)	F9^vi—Ca3—F5	63.72 (6)
F11—Zr2—F11^v	77.30 (13)	F8ⁱ—Ca3—F5^vi	73.82 (7)
F5ⁱ—Zr2—F4ⁱⁱ	73.35 (7)	F8^xii—Ca3—F5^vi	132.51 (7)
F5ⁱⁱ—Zr2—F4ⁱⁱ	77.41 (8)	F3^vi—Ca3—F5^vi	85.66 (7)
F9ⁱⁱⁱ—Zr2—F4ⁱⁱ	76.44 (8)	F3—Ca3—F5^vi	70.82 (6)
F9^iv—Zr2—F4ⁱⁱ	140.78 (7)	F9—Ca3—F5^vi	63.72 (6)
F11—Zr2—F4ⁱⁱ	145.25 (7)	F9^vi—Ca3—F5^vi	126.99 (6)
F11^v—Zr2—F4ⁱⁱ	115.20 (9)	F5—Ca3—F5^vi	148.20 (10)
F5ⁱ—Zr2—F4ⁱ	77.41 (8)	F1—Ca4—F1^vi	137.12 (11)
F5ⁱⁱ—Zr2—F4ⁱ	73.35 (7)	F1—Ca4—F2^vi	69.36 (7)
F9ⁱⁱⁱ—Zr2—F4ⁱ	140.78 (7)	F1^vi—Ca4—F2^vi	102.12 (7)
F9^iv—Zr2—F4ⁱ	76.44 (8)	F1—Ca4—F2	102.12 (7)
F11—Zr2—F4ⁱ	115.20 (9)	F1^vi—Ca4—F2	69.36 (7)
F11^v—Zr2—F4ⁱ	145.25 (7)	F2^vi—Ca4—F2	157.52 (10)
F4ⁱⁱ—Zr2—F4ⁱ	73.99 (11)	F1—Ca4—F7^ix	129.24 (8)
F1—Ca1—F5^vi	78.04 (7)	F1^vi—Ca4—F7^ix	78.34 (7)
F1—Ca1—F6	81.27 (8)	F2^vi—Ca4—F7^ix	67.84 (6)
F5^vi—Ca1—F6	127.77 (7)	F2—Ca4—F7^ix	127.36 (7)
F1—Ca1—F7^vii	73.44 (8)	F1—Ca4—F7^xiii	78.34 (7)
F5^vi—Ca1—F7^vii	106.33 (7)	F1^vi—Ca4—F7^xiii	129.24 (8)
F6—Ca1—F7^vii	112.73 (7)	F2^vi—Ca4—F7^xiii	127.36 (7)
F1—Ca1—F10^v	121.56 (7)	F2—Ca4—F7^xiii	67.84 (6)
F5^vi—Ca1—F10^v	155.59 (7)	F7^ix—Ca4—F7^xiii	107.84 (10)
F6—Ca1—F10^v	73.18 (7)	F1—Ca4—F10^ix	144.10 (7)
F7^vii—Ca1—F10^v	69.93 (7)	F1^vi—Ca4—F10^ix	75.15 (7)
F1—Ca1—F9^iv	154.42 (7)	F2^vi—Ca4—F10^ix	127.81 (7)
F5^vi—Ca1—F9^iv	77.06 (7)	F2—Ca4—F10^ix	71.47 (6)
F6—Ca1—F9^iv	109.85 (7)	F7^ix—Ca4—F10^ix	60.51 (6)
F7^vii—Ca1—F9^iv	119.50 (7)	F7^xiii—Ca4—F10^ix	66.43 (7)
F10^v—Ca1—F9^iv	84.00 (7)	F1—Ca4—F10^xiii	75.15 (7)
F1—Ca1—F3	72.14 (9)	F1^vi—Ca4—F10^xiii	144.10 (7)
F5^vi—Ca1—F3	66.37 (7)	F2^vi—Ca4—F10^xiii	71.47 (6)
F6—Ca1—F3	61.73 (7)	F2—Ca4—F10^xiii	127.81 (7)
F7^vii—Ca1—F3	145.59 (7)	F7^ix—Ca4—F10^xiii	66.43 (7)
F10^v—Ca1—F3	130.46 (7)	F7^xiii—Ca4—F10^xiii	60.51 (6)
F9^iv—Ca1—F3	92.47 (8)	F10^ix—Ca4—F10^xiii	81.52 (9)
F1—Ca1—F8^vii	116.23 (8)	F1—Ca4—F3	63.80 (7)
F5^vi—Ca1—F8^vii	77.68 (7)	F1^vi—Ca4—F3	79.01 (6)
F6—Ca1—F8^vii	153.18 (7)	F2^vi—Ca4—F3	104.03 (7)
F7^vii—Ca1—F8^vii	58.87 (7)	F2—Ca4—F3	54.59 (6)
F10^v—Ca1—F8^vii	80.17 (7)	F7^ix—Ca4—F3	153.52 (7)
F9^iv—Ca1—F8^vii	63.55 (6)	F7^xiii—Ca4—F3	97.08 (6)
F3—Ca1—F8^vii	140.74 (8)	F10^ix—Ca4—F3	125.49 (6)
F1—Ca1—F11	121.92 (8)	F10^xiii—Ca4—F3	136.83 (6)
F5^vi—Ca1—F11	95.13 (7)	F1—Ca4—F3^vi	79.01 (6)
F6—Ca1—F11	57.87 (7)	F1^vi—Ca4—F3^vi	63.80 (7)
F7^vii—Ca1—F11	156.31 (7)	F2^vi—Ca4—F3^vi	54.59 (6)
F10^v—Ca1—F11	86.38 (7)	F2—Ca4—F3^vi	104.03 (7)
F9^iv—Ca1—F11	55.22 (6)	F7^ix—Ca4—F3^vi	97.08 (6)
F3—Ca1—F11	53.29 (7)	F7^xiii—Ca4—F3^vi	153.52 (7)
F8^vii—Ca1—F11	118.27 (6)	F10^ix—Ca4—F3^vi	136.83 (6)
F1^viii—Ca2—F1^vi	154.59 (11)	F10^xiii—Ca4—F3^vi	125.49 (6)
F1^viii—Ca2—F6^ix	122.41 (8)	F3—Ca4—F3^vi	60.32 (8)
F1^vi—Ca2—F6^ix	77.99 (7)	Ca1—F1—Ca4	127.94 (11)
F1^viii—Ca2—F6^x	77.99 (7)	Ca1—F1—Ca2^vii	121.63 (10)
F1^vi—Ca2—F6^x	122.41 (8)	Ca4—F1—Ca2^vii	109.64 (7)
F6^ix—Ca2—F6^x	83.69 (10)	Zr1—F2—Ca4	126.50 (10)
F1^viii—Ca2—F2^xi	67.95 (7)	Zr1—F2—Ca2	114.89 (9)
F1^vi—Ca2—F2^xi	110.54 (6)	Ca4—F2—Ca2	101.62 (6)
F6^ix—Ca2—F2^xi	71.13 (7)	Zr1—F3—Ca3	142.87 (12)
F6^x—Ca2—F2^xi	114.00 (7)	Zr1—F3—Ca1	99.48 (8)
F1^viii—Ca2—F2	110.54 (6)	Ca3—F3—Ca1	107.24 (8)
F1^vi—Ca2—F2	67.95 (7)	Zr1—F3—Ca4	97.99 (9)
F6^ix—Ca2—F2	114.00 (7)	Ca3—F3—Ca4	107.36 (8)
F6^x—Ca2—F2	71.13 (7)	Ca1—F3—Ca4	89.55 (7)
F2^xi—Ca2—F2	173.59 (9)	Zr2ⁱⁱⁱ—F4—Zr1	143.70 (12)
F1^viii—Ca2—F4	78.94 (7)	Zr2ⁱⁱⁱ—F4—Ca2	113.76 (8)
F1^vi—Ca2—F4	78.93 (7)	Zr1—F4—Ca2	102.38 (9)
F6^ix—Ca2—F4	156.54 (6)	Zr2ⁱⁱⁱ—F5—Ca1^vi	134.66 (9)
F6^x—Ca2—F4	112.50 (7)	Zr2ⁱⁱⁱ—F5—Ca3	110.14 (8)
F2^xi—Ca2—F4	113.82 (7)	Ca1^vi—F5—Ca3	114.36 (8)
F2—Ca2—F4	59.90 (6)	Zr1—F6—Ca1	111.56 (9)
F1^viii—Ca2—F4^xi	78.93 (7)	Zr1—F6—Ca2^xiii	125.08 (9)
F1^vi—Ca2—F4^xi	78.94 (7)	Ca1—F6—Ca2^xiii	120.46 (8)
F6^ix—Ca2—F4^xi	112.50 (6)	Zr1—F7—Ca1^viii	117.66 (9)
F6^x—Ca2—F4^xi	156.54 (6)	Zr1—F7—Ca4^x	111.69 (8)
F2^xi—Ca2—F4^xi	59.90 (6)	Ca1^viii—F7—Ca4^x	110.63 (8)
F2—Ca2—F4^xi	113.82 (7)	Zr1—F7—Ca2	92.24 (7)
F4—Ca2—F4^xi	58.49 (9)	Ca1^viii—F7—Ca2	92.03 (6)
F1^viii—Ca2—F10^x	64.60 (6)	Ca4^x—F7—Ca2	131.65 (8)
F1^vi—Ca2—F10^x	138.65 (7)	Zr1—F8—Ca3ⁱⁱⁱ	147.21 (10)
F6^ix—Ca2—F10^x	60.87 (6)	Zr1—F8—Ca1^viii	101.38 (9)
F6^x—Ca2—F10^x	52.89 (6)	Ca3ⁱⁱⁱ—F8—Ca1^viii	105.84 (7)
F2^xi—Ca2—F10^x	61.59 (5)	Zr2ⁱ—F9—Ca3	110.58 (8)
F2—Ca2—F10^x	123.90 (6)	Zr2ⁱ—F9—Ca1^xiv	124.23 (9)
F4—Ca2—F10^x	142.40 (5)	Ca3—F9—Ca1^xiv	114.33 (8)
F4^xi—Ca2—F10^x	118.98 (5)	Zr1—F10—Ca1^v	143.51 (9)
F1^viii—Ca2—F10^ix	138.65 (7)	Zr1—F10—Ca4^x	107.27 (8)
F1^vi—Ca2—F10^ix	64.60 (6)	Ca1^v—F10—Ca4^x	106.96 (7)
F6^ix—Ca2—F10^ix	52.89 (6)	Zr1—F10—Ca2^xiii	98.83 (7)
F6^x—Ca2—F10^ix	60.87 (6)	Ca1^v—F10—Ca2^xiii	97.15 (6)
F2^xi—Ca2—F10^ix	123.90 (6)	Ca4^x—F10—Ca2^xiii	83.57 (6)
F2—Ca2—F10^ix	61.59 (5)	Zr2—F11—Zr1	161.30 (11)
F4—Ca2—F10^ix	118.98 (5)	Zr2—F11—Ca1	105.85 (7)
F4^xi—Ca2—F10^ix	142.40 (5)	Zr1—F11—Ca1	92.79 (8)
F10^x—Ca2—F10^ix	85.95 (7)

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

Experimental details

Crystal data
Chemical formula	Ca₅Zr₃F₂₂
M_r	892.06
Crystal system, space group	Orthorhombic, P2₁2₁2
Temperature (K)	296
a, b, c (Å)	9.9844 (3), 7.4059 (2), 9.9046 (3)
V (Å³)	732.38 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.09
Crystal size (mm)	0.19 × 0.06 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.587, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	7993, 3466, 2909
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.827

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.058, 0.99
No. of reflections	3466
No. of parameters	139
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.77
Absolute structure	Flack (1983), 1462 Friedel pairs
Absolute structure parameter	0.0 (4)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CaRine (Boudias & Monceau, 1998) and ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

References

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