A hexa­gonal 2a,c superstructure of Ba₇F₁₂Cl₂

Hydro­thermal synthesis yielded crystals of hepta­barium dodeca­fluoride dichloride, Ba₇F₁₂Cl₂, displaying a new 2a,c hexa­gonal superstructure with P 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.

S1. Comment

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.

S2. Experimental

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?)].

S3. Refinement

The refined parameters varied slightly from one sample to another and differed from those of the ordered and disordered Ba₇F₁₂Cl₂ phases. A doubling of the a and b axes was found for several crystals with a normalized unit-cell volume larger than expected from our former data. Substitution with larger bivalent ions can be excluded, so a new structural arrangement had to be taken into consideration. To improve the ratio of variables to intensities, the F atoms were refined isotropically. The quality of the refinement did not improve when anisotropic displacement parameters were used. The absorption correction was carried out using the crystal shape method and the corresponding absorption coefficient. All atomic positions were standardized using STIDY (Gelato & Parthe, 1987). Constraints were applied to the (x,y) coordinates and the occupancies of the Ba3 and Ba6 sites. The maximal residual electron density of 1.954 e Å⁻³ was found in position (0.6956,0.3482, 0.0957) and the minimal residual density of −5.626 e Å⁻³ was found in position (2/3,1/3,1/2).

Computing details

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

	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

Crystal data

Ba4.6667Cl1.3333F8	Dx = 5.06 Mg m^−3
Mr = 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) Å^3	Needle, colourless
Z = 6	0.24 × 0.08 × 0.04 mm
F(000) = 2136

Data collection

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

Refinement

Refinement on Inet	1/σ^2
Least-squares matrix: full	(Δ/σ)max = 0.00041
R[F^2 > 2σ(F^2)] = 0.038	Δρmax = 1.95 e Å^−3
wR(F^2) = 0.031	Δρmin = −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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Ba1—F1	2.590 (10)	Ba5—Cl2^viii	3.385 (5)
Ba1—F3	2.659 (12)	Ba6—F9	2.089 (11)
Ba1—F3^i	2.668 (12)	Ba6—F10	2.080 (11)
Ba1—F10^ii	2.927 (7)	Ba6—F13	2.076 (12)
Ba1—F10	2.927 (7)	Ba7^ii—F3	2.669 (8)
Ba1—F12^iii	2.668 (7)	Ba7—F3	2.669 (8)
Ba1—F12^i	2.668 (7)	Ba7^ii—F5	2.670 (6)
Ba1—Cl4^ii	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—F6^i	2.614 (13)	Ba7^ii—Cl1	3.351 (5)
Ba2—F9^ii	2.918 (8)	Ba7—Cl1	3.351 (5)
Ba2—F9	2.918 (8)	Ba8^ix—F2	2.746 (8)
Ba2—F11^ii	2.628 (6)	Ba8^iv—F2	2.746 (8)
Ba2—F11	2.628 (6)	Ba8^ii—F4	2.670 (6)
Ba2—Cl2^ii	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—F9^ii	2.962 (8)	Ba8—Cl3	3.3411 (10)
Ba3—F9	2.962 (8)	Ba9^iii—F1	2.654 (6)
Ba3—F10^ii	2.955 (7)	Ba9^i—F1	2.654 (6)
Ba3—F10	2.955 (7)	Ba9^ii—F6	2.713 (8)
Ba3—F13^ii	2.953 (8)	Ba9—F6	2.713 (8)
Ba3—F13	2.953 (8)	Ba9^i—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)	Ba9^ii—Cl1	3.361 (4)
Ba4—F13^ii	2.911 (8)	Ba9—Cl1	3.361 (4)
Ba4—F13	2.911 (8)	Ba10^ii—F7	2.630 (7)
Ba4—F14^ii	2.674 (7)	Ba10—F7	2.630 (7)
Ba4—F14	2.674 (7)	Ba10^ii—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)	Ba10^ii—Cl1	3.293 (5)
Ba5—F15^ii	2.667 (6)	Ba10—Cl1	3.293 (5)
Ba5—F15	2.667 (6)	Ba11^ii—F8	2.869 (7)
Ba5—F16^ii	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—F14^ii	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—F13^ii	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—F14^ii	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—F13^ii	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—F14^ii	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—F13^ii	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)
F14^ii—Ba4—F14	103.5 (3)	F15—Ba10—F8	71.4 (3)
F14^ii—Ba4—F13^ii	65.8 (4)	F15—Ba10—F8^xiv	71.4 (3)
F14^ii—Ba4—F13	136.4 (3)	F15—Ba10—Cl1	70.5 (2)
F14^ii—Ba4—Cl2^vi	138.9 (3)	F15—Ba10—Cl1^xiv	70.5 (2)
F14^ii—Ba4—Cl2^v	76.3 (2)	F8—Ba10—F8^xiv	88.1 (3)
F14—Ba4—F13^ii	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)
F13^ii—Ba4—F13	92.3 (3)	Cl1—Ba10—Cl1^xiv	79.24 (8)
F13^ii—Ba4—Cl2^vi	140.4 (3)	F16^vii—Ba11—F16	120.0 (3)
F13^ii—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.