The solid solution Ba5.78Pb1.22F12Cl2

Weil, M.

doi:10.1107/S241431461502427X

inorganic compounds

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ISSN: 2414-3146

Volume 1| Part 1| January 2016| x152427

doi:10.1107/S241431461502427X

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The solid solution Ba_5.78Pb_1.22F₁₂Cl₂

Matthias Weil ^a ^*

^aInstitute for Chemical Technologies and Analytics, Division of Structural Chemistry, TU Wien, Getreidemarkt 9/164-SC, A-1060 Vienna, Austria
^*Correspondence e-mail: Matthias.Weil@tuwien.ac.at

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 30 October 2015; accepted 17 December 2015; online 12 January 2016)

The title compound, hexabarium lead(II) dodecafluoride dichloride, is a solid solution in the system Pb₇F₁₂Cl₂–Ba₇F₁₂Cl₂ and crystallizes isotypically with the ordered modification of the parent compounds in the space group P-6. The coordination polyhedra of the three different metal sites are distorted tricapped trigonal prisms with F₇Cl₂ coordination sets for two of these sites (Wyckoff positions 3k and 3j, each with site symmetry m..), and the remaining site being exclusively coordinated by fluoride ions (1a, -6..). By sharing faces, a three-dimensional structure is accomplished. The three metal sites have remarkably different occupancies by the two types of metal ions. Whereas the site on the 3k position shows only a minor incorporation of Pb²⁺ [occupancy ratio Ba:Pb = 0.93 (4):0.07 (4)], the 3j site shows the highest amount of incorporated Pb²⁺ [Ba:Pb = 0.71 (5):29 (5)]. The occupancy ratio with respect to the 1a site is Ba:Pb = 0.86 (5):0.14 (5).

Keywords: crystal structure; solid solution; Ba₇F₁₂Cl₂ structure type; tricapped trigonal–prismatic coordination.

CCDC reference: 1443101

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Structure description

The current study provides indications as to which of the three metal sites of the Ba₇F₁₂Cl₂ structure is preferentially substituted in solid solutions of the type Ba_7-_xM_xF₁₂Cl₂ (M = divalent metal with ionic radius comparable to Ba²⁺) and hence could help to better understand spectroscopic data of europium-doped Ba₇F₁₂Cl₂ phosphors (Hagemann et al., 2015 ). The isotypic ordered parent phases Pb₇F₁₂Cl₂ and Ba₇F₁₂Cl₂ were first reported by Aurivillius (1976 ) and Es-Sakhi et al. (1998 ), respectively. For a review of crystal–chemical peculiarities in the system BaF₂/BaCl₂, including the ordered (space group P $[\overline{6}]$ ) and disordered modifications (space group P6₃) of Ba₇F₁₂Cl₂, see: Hagemann et al. (2012 ). The crystal structure of the title compound is shown in Fig. 1. Selected bond lengths are given in Table 1.

Table 1
Selected bond lengths (Å)

(Ba,Pb)1—F3	2.618 (8)	(Ba,Pb)2—F3ⁱⁱ	2.560 (13)
(Ba,Pb)1—F2	2.659 (16)	(Ba,Pb)2—F4	2.746 (14)
(Ba,Pb)1—F4	2.683 (8)	(Ba,Pb)2—F2	3.001 (11)
(Ba,Pb)1—F1	2.760 (14)	(Ba,Pb)2—Cl2	3.2922 (9)
(Ba,Pb)1—Cl1	3.3375 (10)	(Ba,Pb)3—F3	2.549 (15)
(Ba,Pb)2—F4ⁱ	2.531 (15)	(Ba,Pb)3—F2	2.870 (11)
(Ba,Pb)2—F1ⁱⁱ	2.559 (7)
Symmetry codes: (i) -y+1, x-y, z; (ii) -x+y, -x, z.

Figure 1
The crystal structure of the title compound in a projection along [00 $[\overline{1}]$ ]. Displacement ellipsoids are drawn at the 97% probability level.

Synthesis and crystallization

BaF₂, BaCl₂, PbF₂ and PbCl₂ were mixed in stoichiometric amounts according to a nominal composition of Ba₆PbF₁₂Cl₂. The mixture was placed in a teflon container (capacity 10 ml) which was two-thirds filled with water. The container was closed with a teflon lid and placed in a steel autoclave at 493 K for one week. Colourless crystals with a needle-like form were obtained from the mother liquor by filtration. Unit-cell determination of several selected crystals with subsequent least-squares refinements of the lattice parameters revealed nearly identical unit cells, indicating that the composition of the grown crystals was consistent and very similar to that of the title compound.

Refinement

The three M²⁺ sites are occupied by both Ba and Pb. For the final model, the three metal sites were constrained to be fully occupied. Each of the sites was refined with common coordinates and displacement parameters for the two types of metals. The highest and lowest remaining electron density peaks are found 2.08 and 0.16 Å, respectively, from the M1 site. The crystal measured was twinned by inversion with an approximate ratio of the twin domains of 1:1 [Flack parameter 0.55 (5)]. Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	Ba_5.78Pb_1.22F₁₂Cl₂
M_r	1345.45
Crystal system, space group	Hexagonal, P $[\overline{6}]$
Temperature (K)	293
a, c (Å)	10.5878 (15), 4.1528 (8)
V (Å³)	403.17 (16)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	27.00
Crystal size (mm)	0.50 × 0.02 × 0.02

Data collection
Diffractometer	Philips PW100 diffractometer
Absorption correction	Numerical (HABITUS; Herrendorf, 1997 )
T_min, T_max	0.204, 0.888
No. of measured, independent and observed [I > 2σ(I)] reflections	2616, 877, 766
R_int	0.145
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.127, 1.05
No. of reflections	877
No. of parameters	48
Δρ_max, Δρ_min (e Å⁻³)	4.03, −4.13
Absolute structure	Flack (1983 ), 466 Friedel pairs
Absolute structure parameter	0.55 (5)
Computer programs: PW1100 Operation Software (Philips, 1980 ), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008), ATOMS (Dowty, 2006 ), publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1443101

Crystal structure: contains datablocks global, I. DOI: 10.1107/S241431461502427X/hb4002sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S241431461502427X/hb4002Isup2.hkl

checkCIF report

Synthesis and crystallization top

BaF₂, BaCl₂, PbF₂ and PbCl₂ were mixed in stoichiometric amounts according to a nominal composition of Ba₆PbF₁₂Cl₂. The mixture was placed in a teflon container (capacity 10 ml) which was two-thirds filled with water. The container was closed with a teflon lid and placed in a steel autoclave at 493 K for one week. Colourless crystals with a needle-like form were obtained from the mother liquor by filtration. Unit cell determination of several selected crystals with subsequent least-squares refinements of the lattice parameters revealed nearly identical unit cells, indicating that the composition of the grown crystals was consistent and very similar to that of the title compound.

Refinement top

The three M²⁺ sites are occupied by both Ba and Pb. For the final model, the three metal sites were constrained to be fully occupied. Each of the sites was refined with common coordinates and displacement parameters for the two types of metals. The highest and lowest remaining electron density peaks are found 2.08 Å and 0.16 Å, respectively, from the M1 site. The crystal measured was twinned by inversion with an approximate ratio of the twin domains of 1:1 [Flack parameter 0.55 (5)].

Related literature top

The current study provides indications as to which of the three metal sites of the Ba₇F₁₂Cl₂ structure is preferentially substituted in solid solutions of the type Ba_7-_xM_xF₁₂Cl₂ (M = divalent metal with ionic radius comparable to Ba²⁺) and hence could help to better understand spectroscopic data of europium-doped Ba₇F₁₂Cl₂ phosphors (Hagemann et al., 2015). The isotypic ordered parent phases Pb₇F₁₂Cl₂ and Ba₇F₁₂Cl₂ were first reported by Aurivillius (1976) and Es-Sakhi et al. (1998), respectively. For a review of crystal-chemical peculiarities in the system BaF₂/BaCl₂, including the ordered (space group P6) and disordered modifications (space group P6₃) of Ba₇F₁₂Cl₂, see: Hagemann et al. (2012).

Experimental top

Structure description top

The current study provides indications as to which of the three metal sites of the Ba₇F₁₂Cl₂ structure is preferentially substituted in solid solutions of the type Ba_7-_xM_xF₁₂Cl₂ (M = divalent metal with ionic radius comparable to Ba²⁺) and hence could help to better understand spectroscopic data of europium-doped Ba₇F₁₂Cl₂ phosphors (Hagemann et al., 2015). The isotypic ordered parent phases Pb₇F₁₂Cl₂ and Ba₇F₁₂Cl₂ were first reported by Aurivillius (1976) and Es-Sakhi et al. (1998), respectively. For a review of crystal–chemical peculiarities in the system BaF₂/BaCl₂, including the ordered (space group P6) and disordered modifications (space group P6₃) of Ba₇F₁₂Cl₂, see: Hagemann et al. (2012). Selected bond lengths are given in Table 1.

Computing details top

Data collection: PW1100 Operation Software (Philips, 1980); cell refinement: PW1100 Operation Software (Philips, 1980); data reduction: PW1100 Operation Software (Philips, 1980); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS (Dowty, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The crystal structure of the title compound in a projection along [001]. Displacement ellipsoids are drawn at the 97% probability level.

Hexabarium lead(II) dodecafluoride dichloride top

Crystal data top

Ba_5.78Pb_1.22F₁₂Cl₂	D_x = 5.542 Mg m⁻³
M_r = 1345.45	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6	Cell parameters from 25 reflections
Hall symbol: P -6	θ = 5.4–10.9°
a = 10.5878 (15) Å	µ = 27.00 mm⁻¹
c = 4.1528 (8) Å	T = 293 K
V = 403.17 (16) Å³	Needle, colourless
Z = 1	0.50 × 0.02 × 0.02 mm
F(000) = 566

Data collection top

Philips PW100 diffractometer	766 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.145
Graphite monochromator	θ_max = 30.0°, θ_min = 3.9°
θ/2θ scans	h = −14→14
Absorption correction: numerical (HABITUS; Herrendorf, 1997)	k = −14→14
T_min = 0.204, T_max = 0.888	l = 0→5
2616 measured reflections	3 standard reflections every 120 min
877 independent reflections	intensity decay: 0.3%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0538P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.057	(Δ/σ)_max < 0.001
wR(F²) = 0.127	Δρ_max = 4.03 e Å⁻³
S = 1.05	Δρ_min = −4.13 e Å⁻³
877 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
48 parameters	Extinction coefficient: 0.0019 (6)
0 restraints	Absolute structure: Flack (1983), 466 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.55 (5)

Crystal data top

Ba_5.78Pb_1.22F₁₂Cl₂	Z = 1
M_r = 1345.45	Mo Kα radiation
Hexagonal, P6	µ = 27.00 mm⁻¹
a = 10.5878 (15) Å	T = 293 K
c = 4.1528 (8) Å	0.50 × 0.02 × 0.02 mm
V = 403.17 (16) Å³

Data collection top

Philips PW100 diffractometer	766 reflections with I > 2σ(I)
Absorption correction: numerical (HABITUS; Herrendorf, 1997)	R_int = 0.145
T_min = 0.204, T_max = 0.888	3 standard reflections every 120 min
2616 measured reflections	intensity decay: 0.3%
877 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.127	Δρ_max = 4.03 e Å⁻³
S = 1.05	Δρ_min = −4.13 e Å⁻³
877 reflections	Absolute structure: Flack (1983), 466 Friedel pairs
48 parameters	Absolute structure parameter: 0.55 (5)

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	Occ. (<1)
Ba1	0.28701 (11)	0.40001 (12)	0.5000	0.0144 (4)	0.93 (4)
Pb1	0.28701 (11)	0.40001 (12)	0.5000	0.0144 (4)	0.07 (4)
Ba2	0.41287 (11)	0.10688 (12)	0.0000	0.0192 (4)	0.71 (5)
Pb2	0.41287 (11)	0.10688 (12)	0.0000	0.0192 (4)	0.29 (5)
Ba3	0.0000	0.0000	0.0000	0.0269 (8)	0.86 (5)
Pb3	0.0000	0.0000	0.0000	0.0269 (8)	0.14 (5)
Cl1	0.3333	0.6667	0.0000	0.019 (2)
Cl2	0.6667	0.3333	0.5000	0.022 (2)
F1	0.0449 (14)	0.4338 (13)	0.5000	0.024 (4)
F2	0.2156 (17)	0.1209 (18)	0.5000	0.038 (5)
F3	0.1191 (14)	0.2771 (16)	0.0000	0.024 (3)
F4	0.4344 (16)	0.3763 (16)	0.0000	0.020 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.0111 (6)	0.0125 (6)	0.0194 (7)	0.0058 (5)	0.000	0.000
Pb1	0.0111 (6)	0.0125 (6)	0.0194 (7)	0.0058 (5)	0.000	0.000
Ba2	0.0131 (6)	0.0148 (6)	0.0254 (7)	0.0037 (4)	0.000	0.000
Pb2	0.0131 (6)	0.0148 (6)	0.0254 (7)	0.0037 (4)	0.000	0.000
Ba3	0.0137 (8)	0.0137 (8)	0.0533 (16)	0.0068 (4)	0.000	0.000
Pb3	0.0137 (8)	0.0137 (8)	0.0533 (16)	0.0068 (4)	0.000	0.000
Cl1	0.019 (3)	0.019 (3)	0.020 (5)	0.0094 (14)	0.000	0.000
Cl2	0.016 (2)	0.016 (2)	0.033 (7)	0.0078 (12)	0.000	0.000
F1	0.020 (6)	0.010 (6)	0.047 (10)	0.010 (5)	0.000	0.000
F2	0.036 (9)	0.016 (7)	0.055 (12)	0.009 (7)	0.000	0.000
F3	0.012 (6)	0.026 (7)	0.032 (8)	0.009 (5)	0.000	0.000
F4	0.022 (7)	0.028 (7)	0.019 (8)	0.018 (6)	0.000	0.000

Geometric parameters (Å, º) top

Ba1—F3	2.618 (8)	Ba3—F2ⁱⁱⁱ	2.870 (11)
Ba1—F3ⁱ	2.618 (8)	Ba3—F2^vi	2.870 (11)
Ba1—F2	2.659 (16)	Ba3—Pb2^vi	3.9297 (12)
Ba1—F1ⁱⁱ	2.670 (12)	Ba3—Ba2^vi	3.9297 (12)
Ba1—F4ⁱ	2.683 (8)	Cl1—Ba1^ix	3.3374 (10)
Ba1—F4	2.683 (8)	Cl1—Ba1^x	3.3374 (10)
Ba1—F1	2.760 (14)	Cl1—Ba1ⁱⁱ	3.3375 (10)
Ba1—Cl1ⁱ	3.3375 (10)	Cl1—Ba1^xi	3.3375 (10)
Ba1—Cl1	3.3375 (10)	Cl1—Ba1ⁱⁱⁱ	3.3375 (10)
Ba1—Ba1ⁱ	4.1528 (8)	Cl2—Ba2^xii	3.2921 (9)
Ba1—Ba1ⁱⁱⁱ	4.1528 (8)	Cl2—Ba2^iv	3.2921 (9)
Ba1—Pb1ⁱ	4.1528 (8)	Cl2—Ba2ⁱ	3.2922 (9)
Ba2—F4^iv	2.531 (15)	Cl2—Ba2^xiii	3.2922 (9)
Ba2—F1^v	2.559 (7)	Cl2—Ba2^xiv	3.2922 (9)
Ba2—F1^vi	2.559 (7)	F1—Pb2^vii	2.559 (7)
Ba2—F3^vi	2.560 (13)	F1—Ba2^vii	2.559 (7)
Ba2—F4	2.746 (14)	F1—Pb2^xv	2.559 (7)
Ba2—F2ⁱⁱⁱ	3.001 (11)	F1—Ba2^xv	2.559 (7)
Ba2—F2	3.001 (11)	F1—Pb1^x	2.670 (12)
Ba2—Cl2	3.2922 (9)	F1—Ba1^x	2.670 (12)
Ba2—Cl2ⁱⁱⁱ	3.2922 (9)	F2—Ba3ⁱ	2.870 (11)
Ba2—Ba3	3.9297 (12)	F2—Ba2ⁱ	3.001 (11)
Ba2—Pb2ⁱ	4.1528 (8)	F3—Pb2^vii	2.560 (13)
Ba3—F3^vii	2.549 (15)	F3—Ba2^vii	2.560 (13)
Ba3—F3	2.549 (15)	F3—Ba1ⁱⁱⁱ	2.618 (8)
Ba3—F3^vi	2.549 (15)	F3—Pb1ⁱⁱⁱ	2.618 (8)
Ba3—F2	2.870 (11)	F4—Pb2^xiv	2.531 (15)
Ba3—F2^v	2.870 (11)	F4—Ba2^xiv	2.531 (15)
Ba3—F2^viii	2.870 (11)	F4—Pb1ⁱⁱⁱ	2.683 (8)
Ba3—F2^vii	2.870 (11)	F4—Ba1ⁱⁱⁱ	2.683 (8)

F3—Ba1—F3ⁱ	105.0 (5)	F3^vii—Ba3—F2^vi	69.4 (4)
F3—Ba1—F2	72.7 (4)	F3—Ba3—F2^vi	133.7 (2)
F3ⁱ—Ba1—F2	72.7 (4)	F3^vi—Ba3—F2^vi	70.2 (4)
F3—Ba1—F1ⁱⁱ	127.5 (2)	F2—Ba3—F2^vi	73.4 (4)
F3ⁱ—Ba1—F1ⁱⁱ	127.5 (2)	F2^v—Ba3—F2^vi	92.7 (5)
F2—Ba1—F1ⁱⁱ	120.7 (4)	F2^viii—Ba3—F2^vi	139.61 (17)
F3—Ba1—F4ⁱ	148.1 (4)	F2^vii—Ba3—F2^vi	73.4 (4)
F3ⁱ—Ba1—F4ⁱ	67.8 (4)	F2ⁱⁱⁱ—Ba3—F2^vi	139.61 (17)
F2—Ba1—F4ⁱ	75.6 (3)	Ba1^ix—Cl1—Ba1^x	76.95 (3)
F1ⁱⁱ—Ba1—F4ⁱ	68.0 (3)	Ba1^ix—Cl1—Ba1ⁱⁱ	133.912 (9)
F3—Ba1—F4	67.8 (4)	Ba1^x—Cl1—Ba1ⁱⁱ	85.38 (2)
F3ⁱ—Ba1—F4	148.1 (4)	Ba1^ix—Cl1—Ba1^xi	85.38 (2)
F2—Ba1—F4	75.6 (3)	Ba1^x—Cl1—Ba1^xi	133.912 (9)
F1ⁱⁱ—Ba1—F4	68.0 (3)	Ba1ⁱⁱ—Cl1—Ba1^xi	76.95 (3)
F4ⁱ—Ba1—F4	101.4 (4)	Ba1^ix—Cl1—Ba1ⁱⁱⁱ	85.38 (2)
F3—Ba1—F1	67.7 (3)	Ba1^x—Cl1—Ba1ⁱⁱⁱ	133.911 (9)
F3ⁱ—Ba1—F1	67.7 (3)	Ba1ⁱⁱ—Cl1—Ba1ⁱⁱⁱ	133.909 (9)
F2—Ba1—F1	112.2 (4)	Ba1^xi—Cl1—Ba1ⁱⁱⁱ	85.38 (2)
F1ⁱⁱ—Ba1—F1	127.1 (4)	Ba1^ix—Cl1—Ba1	133.911 (10)
F4ⁱ—Ba1—F1	129.3 (2)	Ba1^x—Cl1—Ba1	85.38 (2)
F4—Ba1—F1	129.3 (2)	Ba1ⁱⁱ—Cl1—Ba1	85.38 (2)
F3—Ba1—Cl1ⁱ	133.6 (3)	Ba1^xi—Cl1—Ba1	133.909 (9)
F3ⁱ—Ba1—Cl1ⁱ	72.7 (3)	Ba1ⁱⁱⁱ—Cl1—Ba1	76.95 (3)
F2—Ba1—Cl1ⁱ	141.26 (4)	Ba2^xii—Cl2—Ba2^iv	78.21 (3)
F1ⁱⁱ—Ba1—Cl1ⁱ	70.1 (2)	Ba2^xii—Cl2—Ba2	134.340 (9)
F4ⁱ—Ba1—Cl1ⁱ	75.6 (3)	Ba2^iv—Cl2—Ba2	84.45 (2)
F4—Ba1—Cl1ⁱ	135.6 (3)	Ba2^xii—Cl2—Ba2ⁱ	84.45 (2)
F1—Ba1—Cl1ⁱ	69.12 (19)	Ba2^iv—Cl2—Ba2ⁱ	134.340 (9)
F3—Ba1—Cl1	72.7 (3)	Ba2—Cl2—Ba2ⁱ	78.21 (3)
F3ⁱ—Ba1—Cl1	133.6 (3)	Ba2^xii—Cl2—Ba2^xiii	84.45 (2)
F2—Ba1—Cl1	141.26 (4)	Ba2^iv—Cl2—Ba2^xiii	134.339 (9)
F1ⁱⁱ—Ba1—Cl1	70.1 (2)	Ba2—Cl2—Ba2^xiii	134.337 (9)
F4ⁱ—Ba1—Cl1	135.6 (3)	Ba2ⁱ—Cl2—Ba2^xiii	84.45 (2)
F4—Ba1—Cl1	75.6 (3)	Ba2^xii—Cl2—Ba2^xiv	134.339 (9)
F1—Ba1—Cl1	69.12 (19)	Ba2^iv—Cl2—Ba2^xiv	84.45 (2)
Cl1ⁱ—Ba1—Cl1	76.95 (3)	Ba2—Cl2—Ba2^xiv	84.450 (19)
F4^iv—Ba2—F1^v	72.1 (3)	Ba2ⁱ—Cl2—Ba2^xiv	134.337 (9)
F4^iv—Ba2—F1^vi	72.1 (3)	Ba2^xiii—Cl2—Ba2^xiv	78.20 (3)
F1^v—Ba2—F1^vi	108.5 (5)	Pb2^vii—F1—Ba2^vii	0.00 (10)
F4^iv—Ba2—F3^vi	115.8 (4)	Pb2^vii—F1—Pb2^xv	108.5 (5)
F1^v—Ba2—F3^vi	71.7 (3)	Ba2^vii—F1—Pb2^xv	108.5 (5)
F1^vi—Ba2—F3^vi	71.7 (3)	Pb2^vii—F1—Ba2^xv	108.5 (5)
F4^iv—Ba2—F4	126.1 (5)	Ba2^vii—F1—Ba2^xv	108.5 (5)
F1^v—Ba2—F4	125.7 (2)	Pb2^xv—F1—Ba2^xv	0.00 (10)
F1^vi—Ba2—F4	125.7 (2)	Pb2^vii—F1—Pb1^x	109.6 (3)
F3^vi—Ba2—F4	118.2 (4)	Ba2^vii—F1—Pb1^x	109.6 (3)
F4^iv—Ba2—F2ⁱⁱⁱ	135.8 (2)	Pb2^xv—F1—Pb1^x	109.6 (3)
F1^v—Ba2—F2ⁱⁱⁱ	67.5 (3)	Ba2^xv—F1—Pb1^x	109.6 (3)
F1^vi—Ba2—F2ⁱⁱⁱ	137.7 (4)	Pb2^vii—F1—Ba1^x	109.6 (3)
F3^vi—Ba2—F2ⁱⁱⁱ	67.1 (4)	Ba2^vii—F1—Ba1^x	109.6 (3)
F4—Ba2—F2ⁱⁱⁱ	69.3 (4)	Pb2^xv—F1—Ba1^x	109.6 (3)
F4^iv—Ba2—F2	135.8 (2)	Ba2^xv—F1—Ba1^x	109.6 (3)
F1^v—Ba2—F2	137.7 (4)	Pb1^x—F1—Ba1^x	0.00 (5)
F1^vi—Ba2—F2	67.5 (3)	Pb2^vii—F1—Ba1	108.1 (3)
F3^vi—Ba2—F2	67.1 (4)	Ba2^vii—F1—Ba1	108.1 (3)
F4—Ba2—F2	69.3 (4)	Pb2^xv—F1—Ba1	108.1 (3)
F2ⁱⁱⁱ—Ba2—F2	87.6 (4)	Ba2^xv—F1—Ba1	108.1 (3)
F4^iv—Ba2—Cl2	70.5 (2)	Pb1^x—F1—Ba1	112.9 (4)
F1^v—Ba2—Cl2	139.3 (3)	Ba1^x—F1—Ba1	112.9 (4)
F1^vi—Ba2—Cl2	74.6 (3)	Ba1—F2—Ba3	102.5 (4)
F3^vi—Ba2—Cl2	140.896 (13)	Ba1—F2—Ba3ⁱ	102.5 (4)
F4—Ba2—Cl2	68.3 (2)	Ba3—F2—Ba3ⁱ	92.7 (5)
F2ⁱⁱⁱ—Ba2—Cl2	137.3 (3)	Ba1—F2—Ba2ⁱ	103.7 (4)
F2—Ba2—Cl2	82.1 (3)	Ba3—F2—Ba2ⁱ	153.7 (6)
F4^iv—Ba2—Cl2ⁱⁱⁱ	70.5 (2)	Ba3ⁱ—F2—Ba2ⁱ	83.99 (13)
F1^v—Ba2—Cl2ⁱⁱⁱ	74.6 (3)	Ba1—F2—Ba2	103.7 (4)
F1^vi—Ba2—Cl2ⁱⁱⁱ	139.3 (3)	Ba3—F2—Ba2	83.99 (13)
F3^vi—Ba2—Cl2ⁱⁱⁱ	140.896 (13)	Ba3ⁱ—F2—Ba2	153.7 (6)
F4—Ba2—Cl2ⁱⁱⁱ	68.3 (2)	Ba2ⁱ—F2—Ba2	87.6 (4)
F2ⁱⁱⁱ—Ba2—Cl2ⁱⁱⁱ	82.1 (3)	Ba3—F3—Pb2^vii	100.6 (5)
F2—Ba2—Cl2ⁱⁱⁱ	137.3 (3)	Ba3—F3—Ba2^vii	100.6 (5)
Cl2—Ba2—Cl2ⁱⁱⁱ	78.21 (3)	Pb2^vii—F3—Ba2^vii	0.000 (6)
F3^vii—Ba3—F3	120.0	Ba3—F3—Ba1	113.2 (4)
F3^vii—Ba3—F3^vi	120.0	Pb2^vii—F3—Ba1	112.6 (4)
F3—Ba3—F3^vi	120.0	Ba2^vii—F3—Ba1	112.6 (4)
F3^vii—Ba3—F2	133.7 (2)	Ba3—F3—Ba1ⁱⁱⁱ	113.2 (4)
F3—Ba3—F2	70.2 (4)	Pb2^vii—F3—Ba1ⁱⁱⁱ	112.6 (4)
F3^vi—Ba3—F2	69.4 (4)	Ba2^vii—F3—Ba1ⁱⁱⁱ	112.6 (4)
F3^vii—Ba3—F2^v	69.4 (4)	Ba1—F3—Ba1ⁱⁱⁱ	105.0 (5)
F3—Ba3—F2^v	133.7 (2)	Ba3—F3—Pb1ⁱⁱⁱ	113.2 (4)
F3^vi—Ba3—F2^v	70.2 (4)	Pb2^vii—F3—Pb1ⁱⁱⁱ	112.6 (4)
F2—Ba3—F2^v	139.61 (17)	Ba2^vii—F3—Pb1ⁱⁱⁱ	112.6 (4)
F3^vii—Ba3—F2^viii	70.2 (4)	Ba1—F3—Pb1ⁱⁱⁱ	105.0 (5)
F3—Ba3—F2^viii	69.4 (4)	Ba1ⁱⁱⁱ—F3—Pb1ⁱⁱⁱ	0.00 (6)
F3^vi—Ba3—F2^viii	133.7 (2)	Pb2^xiv—F4—Ba2^xiv	0.00 (5)
F2—Ba3—F2^viii	139.61 (17)	Pb2^xiv—F4—Pb1ⁱⁱⁱ	110.1 (4)
F2^v—Ba3—F2^viii	73.4 (4)	Ba2^xiv—F4—Pb1ⁱⁱⁱ	110.1 (4)
F3^vii—Ba3—F2^vii	70.2 (4)	Pb2^xiv—F4—Ba1ⁱⁱⁱ	110.1 (4)
F3—Ba3—F2^vii	69.4 (4)	Ba2^xiv—F4—Ba1ⁱⁱⁱ	110.1 (4)
F3^vi—Ba3—F2^vii	133.7 (2)	Pb1ⁱⁱⁱ—F4—Ba1ⁱⁱⁱ	0.00 (5)
F2—Ba3—F2^vii	73.4 (4)	Pb2^xiv—F4—Ba1	110.1 (4)
F2^v—Ba3—F2^vii	139.61 (17)	Ba2^xiv—F4—Ba1	110.1 (4)
F2^viii—Ba3—F2^vii	92.7 (5)	Pb1ⁱⁱⁱ—F4—Ba1	101.4 (4)
F3^vii—Ba3—F2ⁱⁱⁱ	133.7 (2)	Ba1ⁱⁱⁱ—F4—Ba1	101.4 (4)
F3—Ba3—F2ⁱⁱⁱ	70.2 (4)	Pb2^xiv—F4—Ba2	113.9 (5)
F3^vi—Ba3—F2ⁱⁱⁱ	69.4 (4)	Ba2^xiv—F4—Ba2	113.9 (5)
F2—Ba3—F2ⁱⁱⁱ	92.7 (5)	Pb1ⁱⁱⁱ—F4—Ba2	110.3 (4)
F2^v—Ba3—F2ⁱⁱⁱ	73.4 (4)	Ba1ⁱⁱⁱ—F4—Ba2	110.3 (4)
F2^viii—Ba3—F2ⁱⁱⁱ	73.4 (4)	Ba1—F4—Ba2	110.3 (4)
F2^vii—Ba3—F2ⁱⁱⁱ	139.61 (17)

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

Selected bond lengths (Å) top

Ba1—F3	2.618 (8)	Ba2—F3ⁱⁱ	2.560 (13)
Ba1—F2	2.659 (16)	Ba2—F4	2.746 (14)
Ba1—F4	2.683 (8)	Ba2—F2	3.001 (11)
Ba1—F1	2.760 (14)	Ba2—Cl2	3.2922 (9)
Ba1—Cl1	3.3375 (10)	Ba3—F3	2.549 (15)
Ba2—F4ⁱ	2.531 (15)	Ba3—F2	2.870 (11)
Ba2—F1ⁱⁱ	2.559 (7)

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

Experimental details

Crystal data
Chemical formula	Ba_5.78Pb_1.22F₁₂Cl₂
M_r	1345.45
Crystal system, space group	Hexagonal, P6
Temperature (K)	293
a, c (Å)	10.5878 (15), 4.1528 (8)
V (Å³)	403.17 (16)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	27.00
Crystal size (mm)	0.50 × 0.02 × 0.02

Data collection
Diffractometer	Philips PW100
Absorption correction	Numerical (HABITUS; Herrendorf, 1997)
T_min, T_max	0.204, 0.888
No. of measured, independent and observed [I > 2σ(I)] reflections	2616, 877, 766
R_int	0.145
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.127, 1.05
No. of reflections	877
No. of parameters	48
Δρ_max, Δρ_min (e Å⁻³)	4.03, −4.13
Absolute structure	Flack (1983), 466 Friedel pairs
Absolute structure parameter	0.55 (5)

Computer programs: PW1100 Operation Software (Philips, 1980), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ATOMS (Dowty, 2006), publCIF (Westrip, 2010).

Acknowledgements

The author thanks Professor H. Völlenkle for measurement time and introduction to the PW1100 four-circle diffractometer.

References

Aurivillius, B. (1976). Chem. Scr. 10, 206–209. CAS Google Scholar
Dowty, E. (2006). ATOMS. Shape Software, Kingsport, Tennessee, USA. Google Scholar
Es-Sakhi, B., Gravereau, P. & Fouassier, C. (1998). Powder Diffr. 13, 152–156. CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hagemann, H., Bill, H., Rey, J. M., Kubel, F., Calame, L. & Lovy, D. (2015). J. Phys. Chem. C, 119, 141–147. Web of Science CrossRef CAS Google Scholar
Hagemann, H., D'Anna, V., Lawson Daku, M. & Kubel, F. (2012). Cryst. Growth Des. 12, 1124–1131. Web of Science CrossRef CAS Google Scholar
Herrendorf, W. (1997). HABITUS. University of Giessen, Germany. Google Scholar
Philips (1980). PW1100 Operation Software. Philips, Eindhoven, The Netherlands. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 1| Part 1| January 2016| x152427

doi:10.1107/S241431461502427X

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