A hexa­gonal 2a,c superstructure of Ba7F12Cl2

Bernsteiner, A.; Kubel, F.

doi:10.1107/S010827010601273X

Buy article online - an online subscription or single-article purchase is required to access this article.

A hexagonal 2a,c superstructure of Ba₇F₁₂Cl₂

A. Bernsteiner and F. Kubel

Hydrothermal synthesis yielded crystals of heptabarium dodecafluoride dichloride, Ba₇F₁₂Cl₂, displaying a new 2a,c hexagonal superstructure with P $\overline{6}$ symmetry. The superstructure results from the disorder of Ba²⁺ cations over two adjacent tricapped trigonal prismatic sites located in channels parallel to the c axis.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010601273X/bc1095sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S010827010601273X/bc1095Isup2.hkl Contains datablock I

Comment top

Barium fluorochlorides and -bromides with the composition Ba₇F₁₂X₂ (X = Cl or Br) can be synthesized by high-temperature flux growth, room-temperature gel growth (Kubel et al., 1999 [Please specify which, a or b]; Kubel, 2005) and hydrothermal methods. For Ba₇F₁₂Cl₂, two distinct modifications have been characterized to date, including an ordered and a disordered modification grown from an LiF and an NaCl flux, respectively (Kubel et al., 1999 [Please specify which, a or b]). Crystals obtained from gel growth showed further disorder (Kubel et al., 1999 [Please specify which, a or b]).

In this study, selected crystals of Ba₇F₁₂Cl₂ grown by hydrothermal synthesis have been investigated. A superstructure modification, which can be described as an ordered (position) and disordered (occupancy) variant, has been discovered. The hydrothermal synthesis was carried out under the same conditions as described for Pb₇F₁₂Cl₂ (Kubel et al., 2000).

The basic crystal structure of Ba₇F₁₂Cl₂ is built up of a matrix of matlockite-like units where one type of Ba²⁺ cation has a coordination number of 9 (2Cl + 7 F). Fig. 1 shows the propeller-type arrangements, with Cl⁻ ions as the axes and F⁻ ions as the blades of the propellers. Within this framework, tricapped trigonal channels filled with the second type of Ba²⁺ ions complete the structure. Two hypothetical positions separated by a distance of c/2 can be occupied within the channels (Kubel et al., 1999 [Please specify which, a or b]). An average 50% occupancy of both sites or a full occupancy of one site defines the disordered and ordered modifications, respectively. The lattice parameters are slightly different in each case. Crystals grown by gel-growth methods show small but significant deviations from the ideal ordered structure and a small increase in unit-cell volume.

For the new hexagonal superstructure, the c parameter is close to that of the disordered variant and the normalized a axis is close to that of the ordered modification. As seen in Fig. 2, the c/a ratio is different for all types of order and disorder. A small increase of disorder as found in the gel-grown crystals shows a higher unit-cell volume but a similar c/a ratio. This tendency is strongly increased for the new superstructure, for which a, c and the unit-cell volume are significantly increased. Lattice parameters of several crystals were measured. The refinements showed only small deviations from the structure described here with, for example, slightly different populations of the Ba sites responsible for the superstructure. The superstructure was also confirmed from powder diffraction refinements showing superstructure reflections at low diffraction angle.

The formation of the 2a,c superstructure is related to the different occupancies of the Ba3 and Ba6 sites in the channels, which vary slightly with the growth conditions in the hydrothermal system. Fig. 1 can be compared with the drawing in Kubel et al. (2000). In the present superstructure, a new arrangement of three propellers connected to the fluoride channel is formed, which is not observed in the ordered or disordered modifications. The Ba—X distances are not changed significantly but consist of two sets of distances similar to each modification. The environments of Ba1, Ba3, Ba4 and Ba6 are similar to the ordered variant, whereas those of Ba2, Ba5, B7 and Ba8 are similar to the disordered modification.

Experimental top

Crystalline needles of Ba₇F₁₂Cl₂ up to 5 mm in length were formed by hydrothermal synthesis from the corresponding aqueous fluorides and chlorides placed in Teflon-lined steel containers at 523 K for 40 d. Detailed synthesis conditions have been previously described in the case of Pb₇F₁₂Cl₂ (Kubel et al., 2000). Hexagonal and optically uniaxial crystals were broken from the needles and selected under polarized light (Leitz Orthoplan Wild M3 microscope) for X-ray diffraction analysis. X-ray fluorescence analysis showed only Ba, F and Cl signals. The lattice constants and unit-cell volumes of several individual crystals were determined on a Bruker SMART diffractometer with a graphite monochromator and a SMART APEX detector. Selected powdered crystals were analyzed with powder X-ray diffraction [Philips Xpert diffractometer and TOPAS R2–1 refinement package (Reference for software?)].

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: ADDREF and SORTRF in Xtal3.2 (Hall et al., 1992); program(s) used to solve structure: Xtal3.2; program(s) used to refine structure: Xtal3.2; molecular graphics: PowderCell (version 2.4; Author?, Year?); software used to prepare material for publication: BONDLA and CIFIO in Xtal3.2.

Figures top

	Fig. 1. The superstructure of Ba₇F₁₂Cl₂, projected along the c axis, showing the propeller-type arrangement. Large, medium and small circles represent Ba, Cl and F atoms, respectively. Bold lines and filled circles correspond to z = 0 and thin lines and open circles to z = 1/2.
	Fig. 2. Lattice parameters of Ba₇F₁₂Cl₂ for different synthesis procedures (s.u.s are typically about 0.001 Å). High-temperature and gel-growth data from Kubel et al. (1999 [Please specify which, a or b]), hydrothermal data from Kubel (2005), powder diffraction data from Es-Sakhi et al. (1998) and Kubel (2005). The asterisk represents the present data.
	Fig. 3. Please provide caption.
	Fig. 4. Please provide caption.

heptabarium dodecafluoride dichloride top

Crystal data top

Ba_4.6667Cl_1.3333F₈	D_x = 5.06 Mg m⁻³
M_r = 840.14	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6	Cell parameters from 19682 reflections
Hall symbol: P-6	θ = 4.1–30.4°
a = 21.3281 (7) Å	µ = 16.81 mm⁻¹
c = 4.1993 (3) Å	T = 293 K
V = 1654.29 (16) Å³	Needle, colourless
Z = 6	0.24 × 0.08 × 0.04 mm
F(000) = 2136

Data collection top

Bruker SMART CCD area-detector diffractometer	1970 independent reflections
Radiation source: fine-focused sealed tube	1405 reflections with I_net > 3σ(I_net)
Graphite monochromator	R_int = 0.056
ω scans	θ_max = 31.0°, θ_min = 2.2°
Absorption correction: analytical (SADABS; Sheldrick, 1996)	h = −30→30
T_min = 0.217, T_max = 0.510	k = −30→29
19682 measured reflections	l = −5→6

Refinement top

Refinement on I_net	1/σ²
Least-squares matrix: full	(Δ/σ)_max = 0.00041
R[F² > 2σ(F²)] = 0.038	Δρ_max = 1.95 e Å⁻³
wR(F²) = 0.031	Δρ_min = −5.63 e Å⁻³
S = 2.38	Extinction correction: Zachariasen (1968)
1768 reflections	Extinction coefficient: 105 (5)
124 parameters	Absolute structure: Flack (1983), with how many Friedel pairs
0 restraints	Absolute structure parameter: 0.01 (7)
14 constraints

Crystal data top

Ba_4.6667Cl_1.3333F₈	Z = 6
M_r = 840.14	Mo Kα radiation
Hexagonal, P6	µ = 16.81 mm⁻¹
a = 21.3281 (7) Å	T = 293 K
c = 4.1993 (3) Å	0.24 × 0.08 × 0.04 mm
V = 1654.29 (16) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1970 independent reflections
Absorption correction: analytical (SADABS; Sheldrick, 1996)	1405 reflections with I_net > 3σ(I_net)
T_min = 0.217, T_max = 0.510	R_int = 0.056
19682 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.031	Δρ_max = 1.95 e Å⁻³
S = 2.38	Δρ_min = −5.63 e Å⁻³
1768 reflections	Absolute structure: Flack (1983), with how many Friedel pairs
124 parameters	Absolute structure parameter: 0.01 (7)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ba1	0.01701 (8)	0.12854 (7)	0.50000	0.0242 (9)
F1	0.0247 (5)	0.2537 (5)	0.50000	0.036 (2)*
Ba2	0.10906 (8)	0.48259 (8)	0.50000	0.0252 (9)
F2	0.1331 (7)	0.6139 (7)	0.50000	0.036 (3)*
F3	0.1364 (7)	0.1186 (6)	0.50000	0.031 (3)*
Ba3	0.16571 (6)	0.33356 (6)	0.50000	0.0296 (7)	0.839 (2)
F4	0.2262 (6)	0.4734 (5)	0.50000	0.037 (2)*
F5	0.2440 (5)	0.2731 (5)	0.50000	0.029 (2)*
Cl1	0.3320 (3)	0.1673 (3)	0.50000	0.02530
Ba4	0.37056 (8)	0.38957 (8)	0.50000	0.0250 (9)
F6	0.3844 (7)	0.0186 (7)	0.50000	0.032 (3)*
F7	0.4764 (6)	0.3572 (6)	0.50000	0.022 (2)*
Ba5	0.52083 (7)	0.13387 (8)	0.50000	0.0214 (8)
F8	0.5610 (6)	0.2761 (6)	0.50000	0.028 (2)*
Cl2	−0.0004 (3)	0.4999 (3)	0.00000	0.02530
F9	0.1046 (6)	0.3854 (6)	0.00000	0.043 (2)*
F10	0.1153 (6)	0.2212 (6)	0.00000	0.040 (2)*
Ba6	0.16571 (6)	0.33356 (6)	0.00000	0.0296 (7)	0.161 (2)
F11	0.1891 (6)	0.5488 (6)	0.00000	0.024 (2)*
F12	0.1938 (6)	0.0539 (6)	0.00000	0.027 (2)*
Ba7	0.22043 (7)	0.18675 (7)	0.00000	0.0213 (8)
F13	0.2780 (6)	0.3934 (6)	0.00000	0.047 (3)*
Ba8	0.31265 (7)	0.53579 (7)	0.00000	0.0207 (8)
Ba9	0.31417 (7)	0.03630 (7)	0.00000	0.0206 (8)
F14	0.3542 (7)	0.3051 (6)	0.00000	0.024 (2)*
F15	0.4503 (6)	0.1457 (6)	0.00000	0.018 (2)*
Ba10	0.45913 (7)	0.27582 (7)	0.00000	0.0198 (7)
F16	0.6073 (5)	0.1962 (5)	0.00000	0.0182 (18)*
Ba11	0.66666	0.33333	0.00000	0.0110 (5)
Cl3	0.33333	0.66666	0.50000	0.033 (5)
Cl4	0.00000	0.00000	0.00000	0.035 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ba1	0.0210 (6)	0.0306 (7)	0.0240 (6)	0.0152 (5)	0.00000	0.00000
Ba2	0.0256 (6)	0.0241 (6)	0.0245 (6)	0.0113 (5)	0.00000	0.00000
Ba3	0.0277 (5)	0.0283 (5)	0.0363 (4)	0.0165 (4)	0.00000	0.00000
Ba4	0.0293 (7)	0.0272 (6)	0.0239 (6)	0.0182 (6)	0.00000	0.00000
Ba5	0.0220 (6)	0.0190 (5)	0.0203 (5)	0.0081 (4)	0.00000	0.00000
Ba6	0.0277 (5)	0.0283 (5)	0.0363 (4)	0.0165 (4)	0.00000	0.00000
Ba7	0.0209 (6)	0.0240 (6)	0.0197 (5)	0.0119 (5)	0.00000	0.00000
Ba8	0.0205 (6)	0.0247 (6)	0.0201 (5)	0.0136 (5)	0.00000	0.00000
Ba9	0.0185 (6)	0.0223 (6)	0.0195 (5)	0.0091 (5)	0.00000	0.00000
Ba10	0.0139 (5)	0.0193 (6)	0.0228 (5)	0.0059 (4)	0.00000	0.00000
Ba11	0.0097 (3)	0.0097 (3)	0.0138 (5)	0.00483 (17)	0.00000	0.00000
Cl1	0.027 (2)	0.024 (2)	0.029 (3)	0.011 (2)	0.00000	0.00000
Cl2	0.026 (2)	0.024 (2)	0.026 (3)	0.011 (2)	0.00000	0.00000
Cl3	0.036 (3)	0.036 (3)	0.028 (5)	0.0178 (16)	0.00000	0.00000
Cl4	0.037 (3)	0.037 (3)	0.030 (5)	0.0185 (16)	0.00000	0.00000

Geometric parameters (Å, º) top

Ba1—F1	2.590 (10)	Ba5—Cl2^viii	3.385 (5)
Ba1—F3	2.659 (12)	Ba6—F9	2.089 (11)
Ba1—F3ⁱ	2.668 (12)	Ba6—F10	2.080 (11)
Ba1—F10ⁱⁱ	2.927 (7)	Ba6—F13	2.076 (12)
Ba1—F10	2.927 (7)	Ba7ⁱⁱ—F3	2.669 (8)
Ba1—F12ⁱⁱⁱ	2.668 (7)	Ba7—F3	2.669 (8)
Ba1—F12ⁱ	2.668 (7)	Ba7ⁱⁱ—F5	2.670 (6)
Ba1—Cl4ⁱⁱ	3.3258 (10)	Ba7—F5	2.670 (6)
Ba1—Cl4	3.3258 (10)	Ba7—F10	2.685 (11)
Ba2—F2	2.582 (13)	Ba7—F12	2.597 (11)
Ba2—F4	2.602 (10)	Ba7—F14	2.704 (12)
Ba2—F6ⁱ	2.614 (13)	Ba7ⁱⁱ—Cl1	3.351 (5)
Ba2—F9ⁱⁱ	2.918 (8)	Ba7—Cl1	3.351 (5)
Ba2—F9	2.918 (8)	Ba8^ix—F2	2.746 (8)
Ba2—F11ⁱⁱ	2.628 (6)	Ba8^iv—F2	2.746 (8)
Ba2—F11	2.628 (6)	Ba8ⁱⁱ—F4	2.670 (6)
Ba2—Cl2ⁱⁱ	3.294 (5)	Ba8—F4	2.670 (6)
Ba2—Cl2	3.294 (5)	Ba8^iv—F11	2.667 (11)
Ba3—F1	2.612 (10)	Ba8—F11	2.784 (10)
Ba3—F4	2.590 (10)	Ba8—F13	2.743 (12)
Ba3—F5	2.569 (10)	Ba8—Cl3	3.3411 (10)
Ba3—F9ⁱⁱ	2.962 (8)	Ba8—Cl3	3.3411 (10)
Ba3—F9	2.962 (8)	Ba9ⁱⁱⁱ—F1	2.654 (6)
Ba3—F10ⁱⁱ	2.955 (7)	Ba9ⁱ—F1	2.654 (6)
Ba3—F10	2.955 (7)	Ba9ⁱⁱ—F6	2.713 (8)
Ba3—F13ⁱⁱ	2.953 (8)	Ba9—F6	2.713 (8)
Ba3—F13	2.953 (8)	Ba9ⁱ—F9	2.719 (11)
Ba4^iv—F2	2.615 (13)	Ba9—F12	2.774 (11)
Ba4—F5	2.599 (10)	Ba9—F15	2.664 (10)
Ba4—F7	2.670 (11)	Ba9ⁱⁱ—Cl1	3.361 (4)
Ba4—F13ⁱⁱ	2.911 (8)	Ba9—Cl1	3.361 (4)
Ba4—F13	2.911 (8)	Ba10ⁱⁱ—F7	2.630 (7)
Ba4—F14ⁱⁱ	2.674 (7)	Ba10—F7	2.630 (7)
Ba4—F14	2.674 (7)	Ba10ⁱⁱ—F8	3.019 (8)
Ba4—Cl2^v	3.327 (4)	Ba10—F8	3.019 (8)
Ba4—Cl2^vi	3.327 (4)	Ba10—F14	2.606 (13)
Ba5—F6	2.713 (12)	Ba10—F15	2.687 (10)
Ba5^vii—F7	2.772 (12)	Ba10—F16	2.641 (9)
Ba5—F8	2.709 (11)	Ba10ⁱⁱ—Cl1	3.293 (5)
Ba5—F15ⁱⁱ	2.667 (6)	Ba10—Cl1	3.293 (5)
Ba5—F15	2.667 (6)	Ba11ⁱⁱ—F8	2.869 (7)
Ba5—F16ⁱⁱ	2.670 (6)	Ba11—F8	2.869 (7)
Ba5—F16	2.670 (6)	Ba11—F16	2.540 (9)
Ba5—Cl2	3.385 (5)

F1^vi—Ba1^vi—F3^vi	120.8 (4)	F6^vii—Ba5^vii—Cl2^v	67.0 (2)
F1^vi—Ba1^vi—F3^vii	113.2 (4)	F7—Ba5^vii—Cl2^vi	68.8 (3)
F1^vi—Ba1^vi—F12^x	69.7 (3)	F7—Ba5^vii—Cl2^v	68.8 (3)
F1^vi—Ba1^vi—F12^vii	69.7 (3)	Cl2^vi—Ba5^vii—Cl2^v	76.67 (12)
F1^vi—Ba1^vi—F10^v	69.5 (3)	F13^vi—Ba6^vi—F10^vi	118.8 (5)
F1^vi—Ba1^vi—F10^vi	69.5 (3)	F13^vi—Ba6^vi—F9^vi	120.6 (5)
F1^vi—Ba1^vi—Cl4^xi	140.70 (3)	F13^vi—Ba6^vi—Ba3^xiii	90.00 (6)
F1^vi—Ba1^vi—Cl4^xii	140.70 (3)	F13^vi—Ba6^vi—Ba3^vi	90.00 (6)
F3^vi—Ba1^vi—F3^vii	126.0 (4)	F10^vi—Ba6^vi—F9^vi	120.7 (6)
F3^vi—Ba1^vi—F12^x	128.0 (2)	F10^vi—Ba6^vi—Ba3^xiii	90.00 (4)
F3^vi—Ba1^vi—F12^vii	128.0 (2)	F10^vi—Ba6^vi—Ba3^vi	90.00 (4)
F3^vi—Ba1^vi—F10^v	70.3 (3)	F9^vi—Ba6^vi—Ba3^xiii	90.00 (4)
F3^vi—Ba1^vi—F10^vi	70.3 (3)	F9^vi—Ba6^vi—Ba3^vi	90.00 (4)
F3^vi—Ba1^vi—Cl4^xi	69.4 (2)	Ba3^xiii—Ba6^vi—Ba3^vi	180.00 (9)
F3^vi—Ba1^vi—Cl4^xii	69.4 (2)	F12^vi—Ba7^vi—F3^xiii	71.6 (3)
F3^vii—Ba1^vi—F12^x	70.6 (3)	F12^vi—Ba7^vi—F3^vi	71.6 (3)
F3^vii—Ba1^vi—F12^vii	70.6 (3)	F12^vi—Ba7^vi—F5^xiii	128.02 (14)
F3^vii—Ba1^vi—F10^v	133.7 (2)	F12^vi—Ba7^vi—F5^vi	128.02 (14)
F3^vii—Ba1^vi—F10^vi	133.7 (2)	F12^vi—Ba7^vi—F10^vi	122.8 (4)
F3^vii—Ba1^vi—Cl4^xi	69.34 (18)	F12^vi—Ba7^vi—F14^vi	124.9 (4)
F3^vii—Ba1^vi—Cl4^xii	69.34 (18)	F12^vi—Ba7^vi—Cl1^vi	69.3 (3)
F12^x—Ba1^vi—F12^vii	103.8 (3)	F12^vi—Ba7^vi—Cl1^xiii	69.3 (3)
F12^x—Ba1^vi—F10^v	67.8 (4)	F3^xiii—Ba7^vi—F3^vi	103.7 (4)
F12^x—Ba1^vi—F10^vi	138.6 (3)	F3^xiii—Ba7^vi—F5^xiii	66.4 (3)
F12^x—Ba1^vi—Cl4^xi	75.21 (18)	F3^xiii—Ba7^vi—F5^vi	146.9 (4)
F12^x—Ba1^vi—Cl4^xii	137.6 (3)	F3^xiii—Ba7^vi—F10^vi	74.0 (3)
F12^vii—Ba1^vi—F10^v	138.6 (3)	F3^xiii—Ba7^vi—F14^vi	128.0 (3)
F12^vii—Ba1^vi—F10^vi	67.8 (4)	F3^xiii—Ba7^vi—Cl1^vi	138.6 (2)
F12^vii—Ba1^vi—Cl4^xi	137.6 (3)	F3^xiii—Ba7^vi—Cl1^xiii	76.4 (3)
F12^vii—Ba1^vi—Cl4^xii	75.21 (18)	F3^vi—Ba7^vi—F5^xiii	146.9 (4)
F10^v—Ba1^vi—F10^vi	91.7 (3)	F3^vi—Ba7^vi—F5^vi	66.4 (3)
F10^v—Ba1^vi—Cl4^xi	81.35 (15)	F3^vi—Ba7^vi—F10^vi	74.0 (3)
F10^v—Ba1^vi—Cl4^xii	139.1 (2)	F3^vi—Ba7^vi—F14^vi	128.0 (3)
F10^vi—Ba1^vi—Cl4^xi	139.1 (2)	F3^vi—Ba7^vi—Cl1^vi	76.4 (3)
F10^vi—Ba1^vi—Cl4^xii	81.35 (15)	F3^vi—Ba7^vi—Cl1^xiii	138.6 (2)
Cl4^xi—Ba1^vi—Cl4^xii	78.29 (2)	F5^xiii—Ba7^vi—F5^vi	103.7 (2)
F2^vi—Ba2^vi—F4^vi	113.9 (5)	F5^xiii—Ba7^vi—F10^vi	72.9 (3)
F2^vi—Ba2^vi—F6^vii	125.5 (5)	F5^xiii—Ba7^vi—F14^vi	67.0 (3)
F2^vi—Ba2^vi—F11^v	72.2 (3)	F5^xiii—Ba7^vi—Cl1^vi	132.7 (3)
F2^vi—Ba2^vi—F11^vi	72.2 (3)	F5^xiii—Ba7^vi—Cl1^xiii	72.1 (2)
F2^vi—Ba2^vi—F9^v	133.51 (15)	F5^vi—Ba7^vi—F10^vi	72.9 (3)
F2^vi—Ba2^vi—F9^vi	133.51 (15)	F5^vi—Ba7^vi—F14^vi	67.0 (3)
F2^vi—Ba2^vi—Cl2^vi	69.3 (3)	F5^vi—Ba7^vi—Cl1^vi	72.1 (2)
F2^vi—Ba2^vi—Cl2^v	69.3 (3)	F5^vi—Ba7^vi—Cl1^xiii	132.7 (3)
F4^vi—Ba2^vi—F6^vii	120.6 (3)	F10^vi—Ba7^vi—F14^vi	112.4 (4)
F4^vi—Ba2^vi—F11^v	69.5 (3)	F10^vi—Ba7^vi—Cl1^vi	140.84 (8)
F4^vi—Ba2^vi—F11^vi	69.5 (3)	F10^vi—Ba7^vi—Cl1^xiii	140.84 (8)
F4^vi—Ba2^vi—F9^v	68.8 (3)	F14^vi—Ba7^vi—Cl1^vi	68.4 (2)
F4^vi—Ba2^vi—F9^vi	68.8 (3)	F14^vi—Ba7^vi—Cl1^xiii	68.4 (2)
F4^vi—Ba2^vi—Cl2^vi	140.28 (8)	Cl1^vi—Ba7^vi—Cl1^xiii	77.59 (11)
F4^vi—Ba2^vi—Cl2^v	140.28 (8)	F11^vi—Ba8—F4	128.11 (15)
F6^vii—Ba2^vi—F11^v	126.8 (2)	F11^vi—Ba8—F4^xiv	128.11 (15)
F6^vii—Ba2^vi—F11^vi	126.8 (2)	F11^vi—Ba8—F13	119.8 (4)
F6^vii—Ba2^vi—F9^v	71.0 (3)	F11^vi—Ba8—F2^xiii	69.1 (3)
F6^vii—Ba2^vi—F9^vi	71.0 (3)	F11^vi—Ba8—F2^vi	69.1 (3)
F6^vii—Ba2^vi—Cl2^vi	69.4 (2)	F11^vi—Ba8—F11	128.7 (4)
F6^vii—Ba2^vi—Cl2^v	69.4 (2)	F11^vi—Ba8—Cl3	70.9 (2)
F11^v—Ba2^vi—F11^vi	106.1 (4)	F11^vi—Ba8—Cl3^xiv	70.9 (2)
F11^v—Ba2^vi—F9^v	65.7 (3)	F4—Ba8—F4^xiv	103.7 (2)
F11^v—Ba2^vi—F9^vi	137.6 (4)	F4—Ba8—F13	73.2 (3)
F11^v—Ba2^vi—Cl2^vi	139.1 (2)	F4—Ba8—F2^xiii	146.5 (4)
F11^v—Ba2^vi—Cl2^v	74.7 (3)	F4—Ba8—F2^vi	68.3 (3)
F11^vi—Ba2^vi—F9^v	137.6 (4)	F4—Ba8—F11	66.3 (3)
F11^vi—Ba2^vi—F9^vi	65.7 (3)	F4—Ba8—Cl3	72.1 (2)
F11^vi—Ba2^vi—Cl2^vi	74.7 (3)	F4—Ba8—Cl3^xiv	132.9 (3)
F11^vi—Ba2^vi—Cl2^v	139.1 (2)	F4^xiv—Ba8—F13	73.2 (3)
F9^v—Ba2^vi—F9^vi	92.02 (19)	F4^xiv—Ba8—F2^xiii	68.3 (3)
F9^v—Ba2^vi—Cl2^vi	139.9 (3)	F4^xiv—Ba8—F2^vi	146.5 (4)
F9^v—Ba2^vi—Cl2^v	81.2 (2)	F4^xiv—Ba8—F11	66.3 (3)
F9^vi—Ba2^vi—Cl2^vi	81.2 (2)	F4^xiv—Ba8—Cl3	132.9 (3)
F9^vi—Ba2^vi—Cl2^v	139.9 (3)	F4^xiv—Ba8—Cl3^xiv	72.1 (2)
Cl2^vi—Ba2^vi—Cl2^v	79.19 (11)	F13—Ba8—F2^xiii	73.3 (3)
Ba6^v—Ba3^vi—Ba6^vi	180.00 (13)	F13—Ba8—F2^vi	73.3 (3)
Ba6^v—Ba3^vi—F5^vi	90.00 (4)	F13—Ba8—F11	111.5 (4)
Ba6^v—Ba3^vi—F4^vi	90.00 (4)	F13—Ba8—Cl3	140.79 (3)
Ba6^v—Ba3^vi—F1^vi	90.00 (6)	F13—Ba8—Cl3^xiv	140.79 (3)
Ba6^v—Ba3^vi—F13^v	44.7 (2)	F2^xiii—Ba8—F2^vi	99.7 (4)
Ba6^v—Ba3^vi—F13^vi	135.3 (2)	F2^xiii—Ba8—F11	129.9 (3)
Ba6^v—Ba3^vi—F10^v	44.73 (14)	F2^xiii—Ba8—Cl3	137.9 (2)
Ba6^v—Ba3^vi—F10^vi	135.27 (15)	F2^xiii—Ba8—Cl3^xiv	77.4 (3)
Ba6^v—Ba3^vi—F9^v	44.86 (16)	F2^vi—Ba8—F11	129.9 (3)
Ba6^v—Ba3^vi—F9^vi	135.14 (17)	F2^vi—Ba8—Cl3	77.4 (3)
Ba6^vi—Ba3^vi—F5^vi	90.00 (4)	F2^vi—Ba8—Cl3^xiv	137.9 (2)
Ba6^vi—Ba3^vi—F4^vi	90.00 (4)	F11—Ba8—Cl3	69.69 (16)
Ba6^vi—Ba3^vi—F1^vi	90.00 (6)	F11—Ba8—Cl3^xiv	69.69 (16)
Ba6^vi—Ba3^vi—F13^v	135.3 (2)	Cl3—Ba8—Cl3^xiv	77.87 (3)
Ba6^vi—Ba3^vi—F13^vi	44.7 (2)	F1^xiii—Ba9^vii—F1^vi	104.6 (3)
Ba6^vi—Ba3^vi—F10^v	135.27 (15)	F1^xiii—Ba9^vii—F15^vii	127.5 (2)
Ba6^vi—Ba3^vi—F10^vi	44.73 (14)	F1^xiii—Ba9^vii—F6^xv	67.0 (3)
Ba6^vi—Ba3^vi—F9^v	135.14 (17)	F1^xiii—Ba9^vii—F6^vii	146.6 (4)
Ba6^vi—Ba3^vi—F9^vi	44.86 (16)	F1^xiii—Ba9^vii—F9^vi	73.8 (3)
F5^vi—Ba3^vi—F4^vi	120.2 (4)	F1^xiii—Ba9^vii—F12^vii	67.2 (2)
F5^vi—Ba3^vi—F1^vi	119.8 (3)	F1^xiii—Ba9^vii—Cl1^vii	131.8 (2)
F5^vi—Ba3^vi—F13^v	68.1 (3)	F1^xiii—Ba9^vii—Cl1^xv	71.2 (3)
F5^vi—Ba3^vi—F13^vi	68.1 (3)	F1^vi—Ba9^vii—F15^vii	127.5 (2)
F5^vi—Ba3^vi—F10^v	69.9 (3)	F1^vi—Ba9^vii—F6^xv	146.6 (4)
F5^vi—Ba3^vi—F10^vi	69.9 (3)	F1^vi—Ba9^vii—F6^vii	67.0 (3)
F5^vi—Ba3^vi—F9^v	134.84 (16)	F1^vi—Ba9^vii—F9^vi	73.8 (3)
F5^vi—Ba3^vi—F9^vi	134.84 (16)	F1^vi—Ba9^vii—F12^vii	67.2 (2)
F4^vi—Ba3^vi—F1^vi	120.0 (3)	F1^vi—Ba9^vii—Cl1^vii	71.2 (3)
F4^vi—Ba3^vi—F13^v	70.9 (3)	F1^vi—Ba9^vii—Cl1^xv	131.8 (2)
F4^vi—Ba3^vi—F13^vi	70.9 (3)	F15^vii—Ba9^vii—F6^xv	71.7 (4)
F4^vi—Ba3^vi—F10^v	134.72 (14)	F15^vii—Ba9^vii—F6^vii	71.7 (4)
F4^vi—Ba3^vi—F10^vi	134.72 (14)	F15^vii—Ba9^vii—F9^vi	122.4 (3)
F4^vi—Ba3^vi—F9^v	68.2 (3)	F15^vii—Ba9^vii—F12^vii	124.0 (4)
F4^vi—Ba3^vi—F9^vi	68.2 (3)	F15^vii—Ba9^vii—Cl1^vii	69.6 (2)
F1^vi—Ba3^vi—F13^v	134.6 (2)	F15^vii—Ba9^vii—Cl1^xv	69.6 (2)
F1^vi—Ba3^vi—F13^vi	134.6 (2)	F6^xv—Ba9^vii—F6^vii	101.4 (2)
F1^vi—Ba3^vi—F10^v	68.8 (3)	F6^xv—Ba9^vii—F9^vi	72.8 (4)
F1^vi—Ba3^vi—F10^vi	68.8 (3)	F6^xv—Ba9^vii—F12^vii	129.16 (17)
F1^vi—Ba3^vi—F9^v	70.5 (3)	F6^xv—Ba9^vii—Cl1^vii	139.3 (4)
F1^vi—Ba3^vi—F9^vi	70.5 (3)	F6^xv—Ba9^vii—Cl1^xv	78.0 (3)
F13^v—Ba3^vi—F13^vi	90.6 (3)	F6^vii—Ba9^vii—F9^vi	72.8 (4)
F13^v—Ba3^vi—F10^v	74.5 (3)	F6^vii—Ba9^vii—F12^vii	129.16 (17)
F13^v—Ba3^vi—F10^vi	138.0 (3)	F6^vii—Ba9^vii—Cl1^vii	78.0 (3)
F13^v—Ba3^vi—F9^v	75.4 (3)	F6^vii—Ba9^vii—Cl1^xv	139.3 (4)
F13^v—Ba3^vi—F9^vi	139.1 (3)	F9^vi—Ba9^vii—F12^vii	113.6 (4)
F13^vi—Ba3^vi—F10^v	138.0 (3)	F9^vi—Ba9^vii—Cl1^vii	140.96 (9)
F13^vi—Ba3^vi—F10^vi	74.5 (3)	F9^vi—Ba9^vii—Cl1^xv	140.96 (9)
F13^vi—Ba3^vi—F9^v	139.1 (3)	F12^vii—Ba9^vii—Cl1^vii	67.4 (3)
F13^vi—Ba3^vi—F9^vi	75.4 (3)	F12^vii—Ba9^vii—Cl1^xv	67.4 (3)
F10^v—Ba3^vi—F10^vi	90.5 (2)	Cl1^vii—Ba9^vii—Cl1^xv	77.32 (12)
F10^v—Ba3^vi—F9^v	75.5 (2)	F14—Ba10—F7^xiv	72.3 (3)
F10^v—Ba3^vi—F9^vi	139.2 (4)	F14—Ba10—F7	72.3 (3)
F10^vi—Ba3^vi—F9^v	139.2 (4)	F14—Ba10—F16^vii	113.2 (4)
F10^vi—Ba3^vi—F9^vi	75.5 (2)	F14—Ba10—F15	128.5 (3)
F9^v—Ba3^vi—F9^vi	90.3 (2)	F14—Ba10—F8	134.6 (2)
F5—Ba4—F2^vi	122.2 (4)	F14—Ba10—F8^xiv	134.6 (2)
F5—Ba4—F7	111.2 (4)	F14—Ba10—Cl1	70.4 (2)
F5—Ba4—F14ⁱⁱ	68.5 (3)	F14—Ba10—Cl1^xiv	70.4 (2)
F5—Ba4—F14	68.5 (3)	F7^xiv—Ba10—F7	105.9 (3)
F5—Ba4—F13ⁱⁱ	68.4 (3)	F7^xiv—Ba10—F16^vii	69.1 (3)
F5—Ba4—F13	68.4 (3)	F7^xiv—Ba10—F15	126.6 (3)
F5—Ba4—Cl2^vi	140.72 (6)	F7^xiv—Ba10—F8	133.7 (3)
F5—Ba4—Cl2^v	140.72 (6)	F7^xiv—Ba10—F8^xiv	65.2 (4)
F2^vi—Ba4—F7	126.6 (4)	F7^xiv—Ba10—Cl1	140.1 (3)
F2^vi—Ba4—F14ⁱⁱ	128.1 (2)	F7^xiv—Ba10—Cl1^xiv	75.5 (2)
F2^vi—Ba4—F14	128.1 (2)	F7—Ba10—F16^vii	69.1 (3)
F2^vi—Ba4—F13ⁱⁱ	72.5 (3)	F7—Ba10—F15	126.6 (3)
F2^vi—Ba4—F13	72.5 (3)	F7—Ba10—F8	65.2 (4)
F2^vi—Ba4—Cl2^vi	68.4 (3)	F7—Ba10—F8^xiv	133.7 (3)
F2^vi—Ba4—Cl2^v	68.4 (3)	F7—Ba10—Cl1	75.5 (2)
F7—Ba4—F14ⁱⁱ	70.6 (3)	F7—Ba10—Cl1^xiv	140.1 (3)
F7—Ba4—F14	70.6 (3)	F16^vii—Ba10—F15	118.3 (4)
F7—Ba4—F13ⁱⁱ	132.8 (2)	F16^vii—Ba10—F8	65.4 (2)
F7—Ba4—F13	132.8 (2)	F16^vii—Ba10—F8^xiv	65.4 (2)
F7—Ba4—Cl2^vi	70.8 (2)	F16^vii—Ba10—Cl1	140.31 (5)
F7—Ba4—Cl2^v	70.8 (2)	F16^vii—Ba10—Cl1^xiv	140.31 (5)
F14ⁱⁱ—Ba4—F14	103.5 (3)	F15—Ba10—F8	71.4 (3)
F14ⁱⁱ—Ba4—F13ⁱⁱ	65.8 (4)	F15—Ba10—F8^xiv	71.4 (3)
F14ⁱⁱ—Ba4—F13	136.4 (3)	F15—Ba10—Cl1	70.5 (2)
F14ⁱⁱ—Ba4—Cl2^vi	138.9 (3)	F15—Ba10—Cl1^xiv	70.5 (2)
F14ⁱⁱ—Ba4—Cl2^v	76.3 (2)	F8—Ba10—F8^xiv	88.1 (3)
F14—Ba4—F13ⁱⁱ	136.4 (3)	F8—Ba10—Cl1	84.07 (17)
F14—Ba4—F13	65.8 (4)	F8—Ba10—Cl1^xiv	141.6 (3)
F14—Ba4—Cl2^vi	76.3 (2)	F8^xiv—Ba10—Cl1	141.6 (3)
F14—Ba4—Cl2^v	138.9 (3)	F8^xiv—Ba10—Cl1^xiv	84.07 (17)
F13ⁱⁱ—Ba4—F13	92.3 (3)	Cl1—Ba10—Cl1^xiv	79.24 (8)
F13ⁱⁱ—Ba4—Cl2^vi	140.4 (3)	F16^vii—Ba11—F16	120.0 (3)
F13ⁱⁱ—Ba4—Cl2^v	82.0 (2)	F16^vii—Ba11—F16^xvi	120.0 (3)
F13—Ba4—Cl2^vi	82.0 (2)	F16^vii—Ba11—F8	69.0 (3)
F13—Ba4—Cl2^v	140.4 (3)	F16^vii—Ba11—F8^xiv	69.0 (3)
Cl2^vi—Ba4—Cl2^v	78.25 (8)	F16^vii—Ba11—F8^xv	71.2 (3)
F15^x—Ba5^vii—F15^vii	103.9 (2)	F16^vii—Ba11—F8^vii	71.2 (3)
F15^x—Ba5^vii—F16^x	67.4 (2)	F16^vii—Ba11—F8^xvi	132.9 (2)
F15^x—Ba5^vii—F16^vii	148.6 (4)	F16^vii—Ba11—F8^xvii	132.9 (2)
F15^x—Ba5^vii—F8^vii	76.8 (3)	F16—Ba11—F16^xvi	120.0 (4)
F15^x—Ba5^vii—F6^vii	71.7 (3)	F16—Ba11—F8	71.2 (3)
F15^x—Ba5^vii—F7	128.04 (15)	F16—Ba11—F8^xiv	71.2 (3)
F15^x—Ba5^vii—Cl2^vi	136.5 (3)	F16—Ba11—F8^xv	132.93 (17)
F15^x—Ba5^vii—Cl2^v	75.5 (3)	F16—Ba11—F8^vii	132.93 (17)
F15^vii—Ba5^vii—F16^x	148.6 (4)	F16—Ba11—F8^xvi	69.0 (2)
F15^vii—Ba5^vii—F16^vii	67.4 (2)	F16—Ba11—F8^xvii	69.0 (2)
F15^vii—Ba5^vii—F8^vii	76.8 (3)	F16^xvi—Ba11—F8	132.93 (15)
F15^vii—Ba5^vii—F6^vii	71.7 (3)	F16^xvi—Ba11—F8^xiv	132.93 (15)
F15^vii—Ba5^vii—F7	128.04 (15)	F16^xvi—Ba11—F8^xv	69.0 (3)
F15^vii—Ba5^vii—Cl2^vi	75.5 (3)	F16^xvi—Ba11—F8^vii	69.0 (3)
F15^vii—Ba5^vii—Cl2^v	136.5 (3)	F16^xvi—Ba11—F8^xvi	71.2 (2)
F16^x—Ba5^vii—F16^vii	103.7 (3)	F16^xvi—Ba11—F8^xvii	71.2 (2)
F16^x—Ba5^vii—F8^vii	71.9 (3)	F8—Ba11—F8^xiv	94.1 (2)
F16^x—Ba5^vii—F6^vii	127.8 (2)	F8—Ba11—F8^xv	140.2 (4)
F16^x—Ba5^vii—F7	66.6 (2)	F8—Ba11—F8^vii	72.3 (2)
F16^x—Ba5^vii—Cl2^vi	132.3 (2)	F8—Ba11—F8^xvi	72.3 (3)
F16^x—Ba5^vii—Cl2^v	72.4 (3)	F8—Ba11—F8^xvii	140.2 (3)
F16^vii—Ba5^vii—F8^vii	71.9 (3)	F8^xiv—Ba11—F8^xv	72.3 (2)
F16^vii—Ba5^vii—F6^vii	127.8 (2)	F8^xiv—Ba11—F8^vii	140.2 (4)
F16^vii—Ba5^vii—F7	66.6 (2)	F8^xiv—Ba11—F8^xvi	140.2 (3)
F16^vii—Ba5^vii—Cl2^vi	72.4 (3)	F8^xiv—Ba11—F8^xvii	72.3 (3)
F16^vii—Ba5^vii—Cl2^v	132.3 (2)	F8^xv—Ba11—F8^vii	94.1 (2)
F8^vii—Ba5^vii—F6^vii	127.6 (3)	F8^xv—Ba11—F8^xvi	140.2 (3)
F8^vii—Ba5^vii—F7	109.7 (4)	F8^xv—Ba11—F8^xvii	72.3 (3)
F8^vii—Ba5^vii—Cl2^vi	141.02 (10)	F8^vii—Ba11—F8^xvi	72.3 (3)
F8^vii—Ba5^vii—Cl2^v	141.02 (10)	F8^vii—Ba11—F8^xvii	140.2 (3)
F6^vii—Ba5^vii—F7	122.7 (4)	F8^xvi—Ba11—F8^xvii	94.1 (3)
F6^vii—Ba5^vii—Cl2^vi	67.0 (2)

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

Experimental details

Crystal data
Chemical formula	Ba_4.6667Cl_1.3333F₈
M_r	840.14
Crystal system, space group	Hexagonal, P6
Temperature (K)	293
a, c (Å)	21.3281 (7), 4.1993 (3)
V (Å³)	1654.29 (16)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	16.81
Crystal size (mm)	0.24 × 0.08 × 0.04

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Analytical (SADABS; Sheldrick, 1996)
T_min, T_max	0.217, 0.510
No. of measured, independent and observed [I_net > 3σ(I_net)] reflections	19682, 1970, 1405
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.724

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.031, 2.38
No. of reflections	1768
No. of parameters	124
Δρ_max, Δρ_min (e Å⁻³)	1.95, −5.63
Absolute structure	Flack (1983), with how many Friedel pairs
Absolute structure parameter	0.01 (7)

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), ADDREF and SORTRF in Xtal3.2 (Hall et al., 1992), PowderCell (version 2.4; Author?, Year?), BONDLA and CIFIO in Xtal3.2.

Subscribe to Acta Crystallographica Section C: Structural Chemistry

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.

E-mail address*
Repeat e-mail address* (for error checking)

Format*	PDF (US $40)
	HTML (US $40)
	PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number (non-UK EC countries only)
Country*

Terms and conditions of use
Contact us

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

A hexa­gonal 2a,c superstructure of Ba7F12Cl2

Supporting information

Subscribe to Acta Crystallographica Section C: Structural Chemistry

Buy online

A hexagonal 2a,c superstructure of Ba₇F₁₂Cl₂