High-pressure synthesis of ν-DyBO₃

ν-Dysprosium borate (ν-DyBO₃) was synthesized under conditions of high temperature and pressure in a Walker-type multi-anvil apparatus at 3 GPa and 1323 K. The compound is isotypic with the already known ν-samarium and ν-europium orthoborates.

S1. Comment

The rare earth orthoborates REBO₃ exhibit a complex polymorphism. According to Meyer (1969, 1972; Meyer & Skokan, 1971), the first polymorphs were designated with the greek letters β, λ, µ, π and ν. Additionally, monoclinic phases H-REBO₃ (RE is La or Ce) were described by Böhlhoff et al. (1971) and Lemanceau et al. (1999). Depending on the cation size, rare earth orthoborates are related to the three crystalline forms of CaCO₃, i.e. aragonite (λ-phase), vaterite (π- and µ-phases) and calcite (β-phase). Recently, the vaterite-type rare-earth orthoborates have been well investigated by Ren et al. (1999) and Lin et al. (2004), who finally solved the long-debated structures of the π- and µ-phases by means of neutron diffraction. Additionally, Huppertz et al. (2002) were able to synthesize the high-pressure orthoborate phases χ-REBO₃ with RE = Dy and Er. These phases contain the new non-cyclic [B₃O₉]⁹⁻ anion and represent intermediates between the low- (π) and high-temperature (µ) polymorphs. In 1972, Meyer reported the syntheses and lattice parameters of the triclinic rare earth orthoborates REBO₃ (RE = Pr—Dy), which were designated as ν-phases. For RE = Pr—Eu, the syntheses were performed at ambient pressure, whereas for RE = Gd—Dy, high-pressure conditions (1–4.5 GPa) were applied. However, the structure solution and refinement of triclinic ν-SmBO₃ were first performed by Palkina et al. (1976) in the space group P1, but corrected afterwards to P1. Corbel et al. (1999) confirmed the new space group in their characterization of ν-EuBO₃ and also briefly reported on the isotypic gadolinium compound. All three compounds were synthesized from the binary oxides with additional Na₂B₄O₇ as a flux.

In this work, we have been able to synthesize single crystals of the isotypic dysprosium compound, ν-DyBO₃, starting from the pure binary oxides using conditions of high temperature and pressure (3 GPa and 1323 K). The structure solution confirmed the P1 model (Fig. 1) found by Palkina et al. (1976). The lattice parameters of ν-DyBO₃ agree well with the results published by Meyer (1972) [a = 6.147 (1), b = 6.386 (1) and c = 6.391 (1) Å, and α = 92.53 (1), β = 107.64 (1) and γ = 108.28 (1)°]. As expected, the lattice parameters decrease regularly from Pr to Dy, along with the size of the cations.

In the structure of ν-DyBO₃, the rare earth atoms occupy the centres of distorted DyO₈ triangulated dodecahedra (Fig. 2). Each dodecahedron shares edges with four others to build infinite double chains along the [110] direction (Fig. 3). The isolated threefold coordination of B is regular, with B—O distances corresponding to the known average value of 1.370 Å for ortho-borates (Table 1).

A calculation of the bond-valence sums (Brese & O'Keeffe, 1991) around atoms Dy1 and Dy2 led to values of 3.22 and 3.00, respectively. This corresponds to values found for the six crystallographically different Dy atoms in χ-DyBO₃ (2.94–3.13).

In-situ X-ray diffractometry showed that ν-DyBO₃ is stable up to a temperature of 1073 K, followed by a structural re-transformation into the high-temperature polymorph µ-DyBO₃. Subsequent cooling leads to a complete transformation into the room-temperature modification π-DyBO₃.

S2. Experimental

The starting material for the synthesis of triclinic ν-DyBO₃ in this work was a 1:1 molar mixture of B₂O₃ [from H₃BO₃ (99.8%, Merck, Darmstadt) fired at 873 K] with the rare earth oxide Dy₂O₃ (99.9%). The compounds were compressed and heated via a multi-anvil assembly. Details of the assembly can be found elsewhere (Huppertz, 2001, 2004; Walker et al., 1990; Walker, 1991; Rubie, 1999). For the synthesis of ν-DyBO₃, the 18/11 assembly was compressed within 1 h to 3 GPa and heated to 1323 K in the following 10 min. After holding this temperature for 10 min, the sample was cooled down to room temperature over another 10 min period. After decompression, the octahedral sample assembly was broken apart and the sample was carefully separated from the surrounding boron nitride. ν-DyBO₃ was obtained as a single-phase crystalline product (yield 75 mg per run). The compound is air and water resistant and crystallizes as long thin colourless needles.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: enCIFer (Allen et al., 2004) and SHELXL97.

Figures

	Fig. 1. A schematic drawing of the unit cell of ν-DyBO3. Shaded and unshaded polyhedra contain atoms Dy1 and Dy2, respectively. [Symmetry codes: (i) 1 + x, y, z; (ii) 2 − x, 1 − y, 1 − z; (iii) 2 − x, 2 − y, 1 − z; (iv) x, y, 1 + z; (v) 1 − x, 1 − y, 1 − z; (vi) 1 − x, 2 − y, 1 − z; (vii) x, y, z − 1; (viii) x − 1, y, z.]
	Fig. 2. The coordination environments of Dy^3+ (grey spheres) in the crystal structure of ν-DyBO3. Symmetry codes are as given in Fig. 1.
	Fig. 3. The crystal structure of ν-DyBO3. Shaded and unshaded polyhedra contain atoms Dy1 and Dy2, respectively.

Dysprosium borate

Crystal data

DyBO3	Z = 4
Mr = 221.31	F(000) = 380
Triclinic, P1	Dx = 6.557 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1463 (12) Å	Cell parameters from 3498 reflections
b = 6.3856 (13) Å	θ = 3.1–37.8°
c = 6.3894 (13) Å	µ = 33.01 mm^−1
α = 92.52 (3)°	T = 293 K
β = 107.65 (3)°	Rod, colourless
γ = 108.29 (3)°	0.03 × 0.02 × 0.01 mm
V = 224.20 (10) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	1623 independent reflections
Radiation source: fine-focus sealed tube	1446 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 9 pixels mm^-1	θmax = 32.5°, θmin = 3.4°
95 mm CCD camera on κ–Goniostat scans	h = −9→9
Absorption correction: ψ scan (XPREP; Siemens, 1996)	k = −9→9
Tmin = 0.432, Tmax = 0.760	l = −9→9
6397 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	w = 1/[σ^2(Fo^2) + (0.0081P)^2 + 0.5392P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.051	(Δ/σ)max = 0.001
S = 1.15	Δρmax = 2.53 e Å^−3
1623 reflections	Δρmin = −2.72 e Å^−3
92 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0101 (5)

Special details

Experimental. Crystal embedded in oil and mounted with wax

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Dy1	0.94025 (4)	0.71995 (4)	0.81700 (3)	0.00547 (8)
Dy2	0.55505 (4)	0.84498 (4)	0.27142 (3)	0.00615 (8)
O1	0.5894 (6)	0.8664 (6)	0.6455 (6)	0.0079 (7)
O2	0.5327 (6)	0.5246 (6)	0.7716 (6)	0.0099 (7)
O4	1.1206 (6)	0.6610 (6)	0.2034 (6)	0.0073 (6)
O3	0.3484 (6)	0.7820 (6)	0.8760 (6)	0.0085 (7)
O5	0.8722 (6)	0.8830 (6)	0.1289 (5)	0.0068 (6)
O6	0.9555 (8)	0.7643 (7)	0.4773 (6)	0.0155 (8)
B1	0.4778 (10)	0.7132 (9)	0.7601 (9)	0.0065 (9)
B2	0.9897 (10)	0.7686 (9)	0.2815 (9)	0.0062 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Dy1	0.00589 (11)	0.00596 (12)	0.00546 (11)	0.00244 (9)	0.00266 (8)	0.00142 (8)
Dy2	0.00758 (12)	0.00668 (13)	0.00577 (11)	0.00329 (9)	0.00347 (8)	0.00131 (8)
O1	0.0104 (16)	0.0068 (17)	0.0075 (15)	0.0030 (13)	0.0041 (13)	0.0020 (13)
O2	0.0090 (16)	0.0069 (17)	0.0145 (17)	0.0033 (14)	0.0045 (13)	0.0010 (13)
O4	0.0071 (15)	0.0068 (16)	0.0097 (15)	0.0035 (13)	0.0037 (12)	0.0017 (13)
O3	0.0067 (15)	0.0117 (18)	0.0086 (15)	0.0034 (14)	0.0045 (12)	0.0009 (13)
O5	0.0059 (14)	0.0105 (17)	0.0049 (14)	0.0047 (13)	0.0012 (12)	0.0027 (12)
O6	0.026 (2)	0.019 (2)	0.0103 (16)	0.0133 (18)	0.0112 (15)	0.0074 (15)
B1	0.007 (2)	0.004 (2)	0.006 (2)	0.0014 (19)	−0.0005 (17)	−0.0011 (18)
B2	0.010 (2)	0.003 (2)	0.007 (2)	0.0019 (19)	0.0047 (18)	0.0000 (17)

Geometric parameters (Å, º)

Dy1—O6	2.227 (4)	Dy2—B1^vi	2.903 (6)
Dy1—O3^i	2.320 (3)	Dy2—Dy1^iii	3.6678 (13)
Dy1—O4^ii	2.334 (4)	Dy2—Dy2^vi	3.8000 (11)
Dy1—O2	2.341 (4)	B1—O1	1.382 (7)
Dy1—O5^iii	2.393 (4)	B1—O2	1.347 (6)
Dy1—O5^iv	2.414 (3)	B1—O3	1.386 (6)
Dy1—O4^iv	2.480 (4)	B2—O4	1.388 (6)
Dy1—O1	2.578 (4)	B2—O5	1.405 (6)
Dy1—B1	2.740 (5)	B2—O6	1.330 (6)
Dy1—B2^iv	2.882 (5)	B1—Dy2^vi	2.903 (6)
Dy1—Dy2^iii	3.6678 (13)	B2—Dy1^vii	2.882 (5)
Dy1—Dy2^v	3.8061 (16)	O1—Dy2^vi	2.386 (3)
Dy2—O2^v	2.234 (4)	O2—Dy2^v	2.234 (4)
Dy2—O1	2.329 (3)	O4—Dy1^ii	2.334 (4)
Dy2—O5	2.342 (3)	O4—Dy2^i	2.446 (4)
Dy2—O1^vi	2.386 (3)	O4—Dy1^vii	2.480 (4)
Dy2—O3^vii	2.409 (4)	O3—Dy1^viii	2.320 (3)
Dy2—O4^viii	2.446 (4)	O3—Dy2^iv	2.409 (3)
Dy2—O3^vi	2.562 (4)	O3—Dy2^vi	2.562 (4)
Dy2—O6	2.635 (4)	O5—Dy1^iii	2.393 (4)
Dy2—B2	2.845 (5)	O5—Dy1^vii	2.414 (3)
O6—Dy1—O3^i	79.20 (14)	O3^vii—Dy2—O6	126.53 (11)
O6—Dy1—O4^ii	98.96 (14)	O4^viii—Dy2—O6	135.73 (13)
O3^i—Dy1—O4^ii	87.93 (12)	O3^vi—Dy2—O6	111.21 (13)
O6—Dy1—O2	106.20 (15)	O2^v—Dy2—B2	73.33 (14)
O3^i—Dy1—O2	158.74 (13)	O1—Dy2—B2	101.50 (14)
O4^ii—Dy1—O2	70.99 (12)	O5—Dy2—B2	29.43 (14)
O6—Dy1—O5^iii	80.44 (14)	O1^vi—Dy2—B2	141.65 (14)
O3^i—Dy1—O5^iii	74.91 (12)	O3^vii—Dy2—B2	100.06 (13)
O4^ii—Dy1—O5^iii	162.68 (12)	O4^viii—Dy2—B2	143.79 (13)
O2—Dy1—O5^iii	125.98 (12)	O3^vi—Dy2—B2	96.45 (14)
O6—Dy1—O5^iv	143.47 (13)	O6—Dy2—B2	27.76 (13)
O3^i—Dy1—O5^iv	112.85 (12)	O2^v—Dy2—B1^vi	163.07 (14)
O4^ii—Dy1—O5^iv	115.28 (12)	O1—Dy2—B1^vi	93.84 (14)
O2—Dy1—O5^iv	75.38 (13)	O5—Dy2—B1^vi	98.94 (14)
O5^iii—Dy1—O5^iv	70.66 (14)	O1^vi—Dy2—B1^vi	28.20 (13)
O6—Dy1—O4^iv	151.56 (13)	O3^vii—Dy2—B1^vi	83.37 (14)
O3^i—Dy1—O4^iv	73.03 (12)	O4^viii—Dy2—B1^vi	94.39 (13)
O4^ii—Dy1—O4^iv	74.30 (13)	O3^vi—Dy2—B1^vi	28.52 (12)
O2—Dy1—O4^iv	97.74 (13)	O6—Dy2—B1^vi	124.78 (14)
O5^iii—Dy1—O4^iv	97.91 (12)	B2—Dy2—B1^vi	120.33 (16)
O5^iv—Dy1—O4^iv	57.50 (11)	O2^v—Dy2—Dy1^iii	129.08 (9)
O6—Dy1—O1	76.70 (13)	O1—Dy2—Dy1^iii	111.51 (10)
O3^i—Dy1—O1	143.95 (13)	O5—Dy2—Dy1^iii	39.73 (9)
O4^ii—Dy1—O1	121.94 (12)	O1^vi—Dy2—Dy1^iii	87.54 (9)
O2—Dy1—O1	56.02 (13)	O3^vii—Dy2—Dy1^iii	87.89 (9)
O5^iii—Dy1—O1	74.96 (12)	O4^viii—Dy2—Dy1^iii	151.12 (9)
O5^iv—Dy1—O1	74.60 (11)	O3^vi—Dy2—Dy1^iii	38.86 (7)
O4^iv—Dy1—O1	130.64 (11)	O6—Dy2—Dy1^iii	72.99 (10)
O6—Dy1—B1	100.34 (15)	B2—Dy2—Dy1^iii	58.72 (12)
O3^i—Dy1—B1	171.62 (15)	B1^vi—Dy2—Dy1^iii	61.96 (11)
O4^ii—Dy1—B1	100.38 (15)	O2^v—Dy2—Dy2^vi	122.24 (10)
O2—Dy1—B1	29.44 (14)	O1—Dy2—Dy2^vi	36.81 (9)
O5^iii—Dy1—B1	96.74 (14)	O5—Dy2—Dy2^vi	137.13 (9)
O5^iv—Dy1—B1	62.69 (13)	O1^vi—Dy2—Dy2^vi	35.78 (8)
O4^iv—Dy1—B1	108.03 (14)	O3^vii—Dy2—Dy2^vi	128.80 (8)
O1—Dy1—B1	29.94 (14)	O4^viii—Dy2—Dy2^vi	77.03 (8)
O6—Dy1—B2^iv	166.88 (16)	O3^vi—Dy2—Dy2^vi	85.53 (7)
O3^i—Dy1—B2^iv	95.39 (14)	O6—Dy2—Dy2^vi	104.10 (8)
O4^ii—Dy1—B2^iv	92.73 (14)	B2—Dy2—Dy2^vi	127.92 (11)
O2—Dy1—B2^iv	83.18 (15)	B1^vi—Dy2—Dy2^vi	59.18 (11)
O5^iii—Dy1—B2^iv	86.63 (14)	Dy1^iii—Dy2—Dy2^vi	101.41 (3)
O5^iv—Dy1—B2^iv	29.07 (13)	B1—O1—Dy2	131.1 (3)
O4^iv—Dy1—B2^iv	28.78 (13)	B1—O1—Dy2^vi	97.2 (3)
O1—Dy1—B2^iv	102.13 (13)	Dy2—O1—Dy2^vi	107.41 (14)
B1—Dy1—B2^iv	83.26 (15)	B1—O1—Dy1	81.5 (3)
O6—Dy1—Dy2^iii	58.44 (12)	Dy2—O1—Dy1	103.23 (12)
O3^i—Dy1—Dy2^iii	43.85 (10)	Dy2^vi—O1—Dy1	139.57 (15)
O4^ii—Dy1—Dy2^iii	126.88 (9)	B1—O2—Dy2^v	154.6 (3)
O2—Dy1—Dy2^iii	155.69 (10)	B1—O2—Dy1	91.9 (3)
O5^iii—Dy1—Dy2^iii	38.73 (8)	Dy2^v—O2—Dy1	112.55 (14)
O5^iv—Dy1—Dy2^iii	105.35 (9)	B2—O4—Dy1^ii	125.6 (3)
O4^iv—Dy1—Dy2^iii	102.99 (9)	B2—O4—Dy2^i	120.8 (3)
O1—Dy1—Dy2^iii	100.25 (9)	Dy1^ii—O4—Dy2^i	105.53 (13)
B1—Dy1—Dy2^iii	128.92 (12)	B2—O4—Dy1^vii	91.9 (3)
B2^iv—Dy1—Dy2^iii	109.52 (12)	Dy1^ii—O4—Dy1^vii	105.70 (13)
O6—Dy1—Dy2^v	103.85 (12)	Dy2^i—O4—Dy1^vii	101.72 (13)
O3^i—Dy1—Dy2^v	126.19 (9)	B1—O3—Dy1^viii	135.2 (3)
O4^ii—Dy1—Dy2^v	38.25 (8)	B1—O3—Dy2^iv	111.5 (3)
O2—Dy1—Dy2^v	32.83 (9)	Dy1^viii—O3—Dy2^iv	107.77 (13)
O5^iii—Dy1—Dy2^v	158.81 (8)	B1—O3—Dy2^vi	89.5 (3)
O5^iv—Dy1—Dy2^v	96.11 (9)	Dy1^viii—O3—Dy2^vi	97.29 (13)
O4^iv—Dy1—Dy2^v	87.97 (9)	Dy2^iv—O3—Dy2^vi	109.22 (14)
O1—Dy1—Dy2^v	85.73 (9)	B2—O5—Dy2	95.5 (3)
B1—Dy1—Dy2^v	62.13 (12)	B2—O5—Dy1^iii	116.6 (3)
B2^iv—Dy1—Dy2^v	89.02 (12)	Dy2—O5—Dy1^iii	101.54 (12)
Dy2^iii—Dy1—Dy2^v	158.539 (13)	B2—O5—Dy1^vii	94.3 (2)
O2^v—Dy2—O1	92.83 (13)	Dy2—O5—Dy1^vii	138.82 (16)
O2^v—Dy2—O5	89.63 (13)	Dy1^iii—O5—Dy1^vii	109.34 (14)
O1—Dy2—O5	126.00 (12)	B2—O6—Dy1	169.8 (3)
O2^v—Dy2—O1^vi	143.27 (13)	B2—O6—Dy2	84.9 (3)
O1—Dy2—O1^vi	72.59 (14)	Dy1—O6—Dy2	104.38 (14)
O5—Dy2—O1^vi	126.41 (13)	O2—B1—O1	116.4 (4)
O2^v—Dy2—O3^vii	84.30 (14)	O2—B1—O3	126.4 (5)
O1—Dy2—O3^vii	156.42 (12)	O1—B1—O3	116.5 (4)
O5—Dy2—O3^vii	77.47 (11)	O2—B1—Dy1	58.7 (2)
O1^vi—Dy2—O3^vii	95.94 (12)	O1—B1—Dy1	68.6 (2)
O2^v—Dy2—O4^viii	70.74 (12)	O3—B1—Dy1	140.1 (3)
O1—Dy2—O4^viii	84.78 (12)	O2—B1—Dy2^vi	169.8 (4)
O5—Dy2—O4^viii	145.04 (11)	O1—B1—Dy2^vi	54.6 (2)
O1^vi—Dy2—O4^viii	74.41 (12)	O3—B1—Dy2^vi	62.0 (3)
O3^vii—Dy2—O4^viii	72.16 (12)	Dy1—B1—Dy2^vi	111.29 (19)
O2^v—Dy2—O3^vi	151.17 (12)	O6—B2—O4	127.0 (5)
O1—Dy2—O3^vi	115.80 (12)	O6—B2—O5	117.9 (4)
O5—Dy2—O3^vi	71.37 (12)	O4—B2—O5	114.9 (4)
O1^vi—Dy2—O3^vi	56.71 (11)	O6—B2—Dy2	67.3 (3)
O3^vii—Dy2—O3^vi	70.78 (14)	O4—B2—Dy2	153.4 (3)
O4^viii—Dy2—O3^vi	112.98 (11)	O5—B2—Dy2	55.0 (2)
O2^v—Dy2—O6	72.06 (14)	O6—B2—Dy1^vii	166.2 (4)
O1—Dy2—O6	73.92 (12)	O4—B2—Dy1^vii	59.3 (2)
O5—Dy2—O6	55.81 (12)	O5—B2—Dy1^vii	56.6 (2)
O1^vi—Dy2—O6	131.17 (12)	Dy2—B2—Dy1^vii	102.04 (17)
O2^v—Dy2—O1—B1	−29.1 (4)	O2^v—Dy2—O6—Dy1	−87.59 (18)
O5—Dy2—O1—B1	−120.7 (4)	O1—Dy2—O6—Dy1	10.89 (14)
O1^vi—Dy2—O1—B1	116.5 (4)	O5—Dy2—O6—Dy1	170.2 (2)
O3^vii—Dy2—O1—B1	53.1 (5)	O1^vi—Dy2—O6—Dy1	59.1 (2)
O4^viii—Dy2—O1—B1	41.2 (4)	O3^vii—Dy2—O6—Dy1	−155.88 (13)
O3^vi—Dy2—O1—B1	154.3 (4)	O4^viii—Dy2—O6—Dy1	−53.5 (2)
O6—Dy2—O1—B1	−99.6 (4)	O3^vi—Dy2—O6—Dy1	122.86 (15)
B2—Dy2—O1—B1	−102.7 (4)	B2—Dy2—O6—Dy1	−175.7 (4)
B1^vi—Dy2—O1—B1	135.3 (3)	B1^vi—Dy2—O6—Dy1	94.3 (2)
Dy1^iii—Dy2—O1—B1	−163.4 (4)	Dy1^iii—Dy2—O6—Dy1	130.05 (16)
Dy2^vi—Dy2—O1—B1	116.5 (4)	Dy2^vi—Dy2—O6—Dy1	32.21 (16)
O2^v—Dy2—O1—Dy2^vi	−145.64 (14)	Dy2^v—O2—B1—O1	−125.6 (7)
O5—Dy2—O1—Dy2^vi	122.75 (15)	Dy1—O2—B1—O1	38.8 (4)
O1^vi—Dy2—O1—Dy2^vi	0.0	Dy2^v—O2—B1—O3	63.8 (10)
O3^vii—Dy2—O1—Dy2^vi	−63.4 (4)	Dy1—O2—B1—O3	−131.8 (5)
O4^viii—Dy2—O1—Dy2^vi	−75.28 (14)	Dy2^v—O2—B1—Dy1	−164.4 (8)
O3^vi—Dy2—O1—Dy2^vi	37.76 (17)	Dy2^v—O2—B1—Dy2^vi	−153.0 (14)
O6—Dy2—O1—Dy2^vi	143.94 (17)	Dy1—O2—B1—Dy2^vi	11 (2)
B2—Dy2—O1—Dy2^vi	140.80 (15)	Dy2—O1—B1—O2	65.1 (6)
B1^vi—Dy2—O1—Dy2^vi	18.79 (16)	Dy2^vi—O1—B1—O2	−174.3 (4)
Dy1^iii—Dy2—O1—Dy2^vi	80.10 (13)	Dy1—O1—B1—O2	−35.1 (4)
O2^v—Dy2—O1—Dy1	61.07 (14)	Dy2—O1—B1—O3	−123.4 (4)
O5—Dy2—O1—Dy1	−30.5 (2)	Dy2^vi—O1—B1—O3	−2.7 (4)
O1^vi—Dy2—O1—Dy1	−153.3 (2)	Dy1—O1—B1—O3	136.5 (4)
O3^vii—Dy2—O1—Dy1	143.3 (3)	Dy2—O1—B1—Dy1	100.2 (3)
O4^viii—Dy2—O1—Dy1	131.43 (14)	Dy2^vi—O1—B1—Dy1	−139.20 (15)
O3^vi—Dy2—O1—Dy1	−115.53 (13)	Dy2—O1—B1—Dy2^vi	−120.6 (4)
O6—Dy2—O1—Dy1	−9.35 (12)	Dy1—O1—B1—Dy2^vi	139.20 (15)
B2—Dy2—O1—Dy1	−12.49 (17)	Dy1^viii—O3—B1—O2	−87.0 (6)
B1^vi—Dy2—O1—Dy1	−134.50 (15)	Dy2^iv—O3—B1—O2	62.6 (6)
Dy1^iii—Dy2—O1—Dy1	−73.19 (12)	Dy2^vi—O3—B1—O2	173.1 (5)
Dy2^vi—Dy2—O1—Dy1	−153.3 (2)	Dy1^viii—O3—B1—O1	102.4 (5)
O6—Dy1—O1—B1	141.3 (3)	Dy2^iv—O3—B1—O1	−108.0 (4)
O3^i—Dy1—O1—B1	−169.4 (3)	Dy2^vi—O3—B1—O1	2.5 (4)
O4^ii—Dy1—O1—B1	48.9 (3)	Dy1^viii—O3—B1—Dy1	−169.9 (3)
O2—Dy1—O1—B1	20.9 (2)	Dy2^iv—O3—B1—Dy1	−20.3 (7)
O5^iii—Dy1—O1—B1	−135.2 (3)	Dy2^vi—O3—B1—Dy1	90.2 (5)
O5^iv—Dy1—O1—B1	−61.6 (3)	Dy1^viii—O3—B1—Dy2^vi	99.9 (4)
O4^iv—Dy1—O1—B1	−47.7 (3)	Dy2^iv—O3—B1—Dy2^vi	−110.5 (2)
B2^iv—Dy1—O1—B1	−52.1 (3)	O6—Dy1—B1—O2	104.7 (3)
Dy2^iii—Dy1—O1—B1	−164.9 (2)	O4^ii—Dy1—B1—O2	3.5 (3)
Dy2^v—Dy1—O1—B1	35.9 (2)	O5^iii—Dy1—B1—O2	−173.8 (3)
O6—Dy1—O1—Dy2	10.94 (15)	O5^iv—Dy1—B1—O2	−109.7 (3)
O3^i—Dy1—O1—Dy2	60.3 (2)	O4^iv—Dy1—B1—O2	−73.2 (3)
O4^ii—Dy1—O1—Dy2	−81.43 (17)	O1—Dy1—B1—O2	143.0 (4)
O2—Dy1—O1—Dy2	−109.40 (17)	B2^iv—Dy1—B1—O2	−88.1 (3)
O5^iii—Dy1—O1—Dy2	94.43 (15)	Dy2^iii—Dy1—B1—O2	162.3 (2)
O5^iv—Dy1—O1—Dy2	168.07 (16)	Dy2^v—Dy1—B1—O2	4.4 (2)
O4^iv—Dy1—O1—Dy2	−178.02 (12)	O6—Dy1—B1—O1	−38.2 (3)
B1—Dy1—O1—Dy2	−130.3 (3)	O4^ii—Dy1—B1—O1	−139.5 (2)
B2^iv—Dy1—O1—Dy2	177.54 (14)	O2—Dy1—B1—O1	−143.0 (4)
Dy2^iii—Dy1—O1—Dy2	64.82 (12)	O5^iii—Dy1—B1—O1	43.2 (3)
Dy2^v—Dy1—O1—Dy2	−94.39 (12)	O5^iv—Dy1—B1—O1	107.3 (3)
O6—Dy1—O1—Dy2^vi	−127.7 (3)	O4^iv—Dy1—B1—O1	143.8 (2)
O3^i—Dy1—O1—Dy2^vi	−78.3 (3)	B2^iv—Dy1—B1—O1	129.0 (3)
O4^ii—Dy1—O1—Dy2^vi	140.0 (2)	Dy2^iii—Dy1—B1—O1	19.3 (3)
O2—Dy1—O1—Dy2^vi	112.0 (3)	Dy2^v—Dy1—B1—O1	−138.5 (3)
O5^iii—Dy1—O1—Dy2^vi	−44.2 (2)	O6—Dy1—B1—O3	−144.4 (6)
O5^iv—Dy1—O1—Dy2^vi	29.5 (2)	O4^ii—Dy1—B1—O3	114.4 (6)
O4^iv—Dy1—O1—Dy2^vi	43.4 (3)	O2—Dy1—B1—O3	110.9 (7)
B1—Dy1—O1—Dy2^vi	91.1 (3)	O5^iii—Dy1—B1—O3	−63.0 (6)
B2^iv—Dy1—O1—Dy2^vi	38.9 (3)	O5^iv—Dy1—B1—O3	1.2 (5)
Dy2^iii—Dy1—O1—Dy2^vi	−73.8 (2)	O4^iv—Dy1—B1—O3	37.6 (6)
Dy2^v—Dy1—O1—Dy2^vi	127.0 (2)	O1—Dy1—B1—O3	−106.2 (7)
O6—Dy1—O2—B1	−82.3 (3)	B2^iv—Dy1—B1—O3	22.8 (6)
O3^i—Dy1—O2—B1	175.7 (3)	Dy2^iii—Dy1—B1—O3	−86.9 (6)
O4^ii—Dy1—O2—B1	−176.4 (3)	Dy2^v—Dy1—B1—O3	115.3 (6)
O5^iii—Dy1—O2—B1	7.6 (3)	O6—Dy1—B1—Dy2^vi	−73.14 (19)
O5^iv—Dy1—O2—B1	59.8 (3)	O4^ii—Dy1—B1—Dy2^vi	−174.34 (15)
O4^iv—Dy1—O2—B1	113.3 (3)	O2—Dy1—B1—Dy2^vi	−177.8 (4)
O1—Dy1—O2—B1	−21.3 (3)	O5^iii—Dy1—B1—Dy2^vi	8.33 (18)
B2^iv—Dy1—O2—B1	88.4 (3)	O5^iv—Dy1—B1—Dy2^vi	72.46 (17)
Dy2^iii—Dy1—O2—B1	−35.2 (4)	O4^iv—Dy1—B1—Dy2^vi	108.94 (18)
Dy2^v—Dy1—O2—B1	−172.8 (4)	O1—Dy1—B1—Dy2^vi	−34.89 (19)
O6—Dy1—O2—Dy2^v	90.54 (19)	B2^iv—Dy1—B1—Dy2^vi	94.11 (18)
O3^i—Dy1—O2—Dy2^v	−11.5 (4)	Dy2^iii—Dy1—B1—Dy2^vi	−15.6 (2)
O4^ii—Dy1—O2—Dy2^v	−3.56 (13)	Dy2^v—Dy1—B1—Dy2^vi	−173.4 (2)
O5^iii—Dy1—O2—Dy2^v	−179.62 (12)	Dy1—O6—B2—O4	2 (3)
O5^iv—Dy1—O2—Dy2^v	−127.38 (19)	Dy2—O6—B2—O4	−153.9 (5)
O4^iv—Dy1—O2—Dy2^v	−73.95 (17)	Dy1—O6—B2—O5	178.3 (19)
O1—Dy1—O2—Dy2^v	151.5 (2)	Dy2—O6—B2—O5	22.3 (4)
B1—Dy1—O2—Dy2^v	172.8 (4)	Dy1—O6—B2—Dy2	156 (2)
B2^iv—Dy1—O2—Dy2^v	−98.83 (18)	Dy1—O6—B2—Dy1^vii	115 (2)
Dy2^iii—Dy1—O2—Dy2^v	137.63 (13)	Dy2—O6—B2—Dy1^vii	−40.7 (16)
O2^v—Dy2—O5—B2	−55.1 (3)	Dy1^ii—O4—B2—O6	54.4 (7)
O1—Dy2—O5—B2	38.2 (3)	Dy2^i—O4—B2—O6	−89.9 (6)
O1^vi—Dy2—O5—B2	132.5 (3)	Dy1^vii—O4—B2—O6	165.3 (5)
O3^vii—Dy2—O5—B2	−139.3 (3)	Dy1^ii—O4—B2—O5	−122.0 (4)
O4^viii—Dy2—O5—B2	−109.3 (3)	Dy2^i—O4—B2—O5	93.8 (4)
O3^vi—Dy2—O5—B2	147.0 (3)	Dy1^vii—O4—B2—O5	−11.1 (4)
O6—Dy2—O5—B2	13.3 (3)	Dy1^ii—O4—B2—Dy2	−60.9 (9)
B1^vi—Dy2—O5—B2	139.6 (3)	Dy2^i—O4—B2—Dy2	154.9 (6)
Dy1^iii—Dy2—O5—B2	118.7 (3)	Dy1^vii—O4—B2—Dy2	50.0 (8)
Dy2^vi—Dy2—O5—B2	85.9 (3)	Dy1^ii—O4—B2—Dy1^vii	−110.9 (3)
O2^v—Dy2—O5—Dy1^iii	−173.73 (13)	Dy2^i—O4—B2—Dy1^vii	104.9 (3)
O1—Dy2—O5—Dy1^iii	−80.50 (17)	Dy2—O5—B2—O6	−25.3 (5)
O1^vi—Dy2—O5—Dy1^iii	13.88 (18)	Dy1^iii—O5—B2—O6	80.6 (5)
O3^vii—Dy2—O5—Dy1^iii	102.03 (14)	Dy1^vii—O5—B2—O6	−165.3 (4)
O4^viii—Dy2—O5—Dy1^iii	132.05 (18)	Dy2—O5—B2—O4	151.4 (4)
O3^vi—Dy2—O5—Dy1^iii	28.34 (11)	Dy1^iii—O5—B2—O4	−102.7 (4)
O6—Dy2—O5—Dy1^iii	−105.32 (17)	Dy1^vii—O5—B2—O4	11.4 (4)
B2—Dy2—O5—Dy1^iii	−118.7 (3)	Dy1^iii—O5—B2—Dy2	105.9 (2)
B1^vi—Dy2—O5—Dy1^iii	20.92 (15)	Dy1^vii—O5—B2—Dy2	−139.97 (19)
Dy2^vi—Dy2—O5—Dy1^iii	−32.72 (18)	Dy2—O5—B2—Dy1^vii	139.97 (19)
O2^v—Dy2—O5—Dy1^vii	48.0 (2)	Dy1^iii—O5—B2—Dy1^vii	−114.2 (2)
O1—Dy2—O5—Dy1^vii	141.2 (2)	O2^v—Dy2—B2—O6	−83.0 (3)
O1^vi—Dy2—O5—Dy1^vii	−124.4 (2)	O1—Dy2—B2—O6	6.5 (3)
O3^vii—Dy2—O5—Dy1^vii	−36.3 (2)	O5—Dy2—B2—O6	155.8 (5)
O4^viii—Dy2—O5—Dy1^vii	−6.3 (4)	O1^vi—Dy2—B2—O6	82.9 (4)
O3^vi—Dy2—O5—Dy1^vii	−110.0 (2)	O3^vii—Dy2—B2—O6	−163.9 (3)
O6—Dy2—O5—Dy1^vii	116.4 (3)	O4^viii—Dy2—B2—O6	−90.4 (3)
B2—Dy2—O5—Dy1^vii	103.0 (4)	O3^vi—Dy2—B2—O6	124.5 (3)
B1^vi—Dy2—O5—Dy1^vii	−117.4 (2)	B1^vi—Dy2—B2—O6	107.9 (3)
Dy1^iii—Dy2—O5—Dy1^vii	−138.3 (3)	Dy1^iii—Dy2—B2—O6	114.8 (3)
Dy2^vi—Dy2—O5—Dy1^vii	−171.03 (13)	Dy2^vi—Dy2—B2—O6	35.2 (4)
O3^i—Dy1—O6—B2	42 (2)	O2^v—Dy2—B2—O4	45.5 (8)
O4^ii—Dy1—O6—B2	−44 (2)	O1—Dy2—B2—O4	135.0 (8)
O2—Dy1—O6—B2	−117 (2)	O5—Dy2—B2—O4	−75.7 (8)
O5^iii—Dy1—O6—B2	118 (2)	O1^vi—Dy2—B2—O4	−148.6 (8)
O5^iv—Dy1—O6—B2	156 (2)	O3^vii—Dy2—B2—O4	−35.4 (9)
O4^iv—Dy1—O6—B2	29 (2)	O4^viii—Dy2—B2—O4	38.1 (9)
O1—Dy1—O6—B2	−165 (2)	O3^vi—Dy2—B2—O4	−107.0 (8)
B1—Dy1—O6—B2	−146 (2)	O6—Dy2—B2—O4	128.5 (10)
B2^iv—Dy1—O6—B2	109 (2)	B1^vi—Dy2—B2—O4	−123.6 (8)
Dy2^iii—Dy1—O6—B2	84 (2)	Dy1^iii—Dy2—B2—O4	−116.7 (9)
Dy2^v—Dy1—O6—B2	−83 (2)	Dy2^vi—Dy2—B2—O4	163.7 (8)
O3^i—Dy1—O6—Dy2	−162.68 (17)	O2^v—Dy2—B2—O5	121.1 (3)
O4^ii—Dy1—O6—Dy2	111.17 (15)	O1—Dy2—B2—O5	−149.3 (2)
O2—Dy1—O6—Dy2	38.48 (18)	O1^vi—Dy2—B2—O5	−72.9 (3)
O5^iii—Dy1—O6—Dy2	−86.37 (15)	O3^vii—Dy2—B2—O5	40.3 (3)
O5^iv—Dy1—O6—Dy2	−48.7 (3)	O4^viii—Dy2—B2—O5	113.7 (3)
O4^iv—Dy1—O6—Dy2	−175.33 (19)	O3^vi—Dy2—B2—O5	−31.3 (3)
O1—Dy1—O6—Dy2	−9.70 (13)	O6—Dy2—B2—O5	−155.8 (5)
B1—Dy1—O6—Dy2	8.81 (18)	B1^vi—Dy2—B2—O5	−47.9 (3)
B2^iv—Dy1—O6—Dy2	−96.1 (6)	Dy1^iii—Dy2—B2—O5	−41.0 (2)
Dy2^iii—Dy1—O6—Dy2	−120.79 (16)	Dy2^vi—Dy2—B2—O5	−120.6 (2)
Dy2^v—Dy1—O6—Dy2	72.43 (13)	O2^v—Dy2—B2—Dy1^vii	87.83 (17)
O2^v—Dy2—O6—B2	88.1 (3)	O1—Dy2—B2—Dy1^vii	177.36 (14)
O1—Dy2—O6—B2	−173.4 (3)	O5—Dy2—B2—Dy1^vii	−33.3 (2)
O5—Dy2—O6—B2	−14.1 (3)	O1^vi—Dy2—B2—Dy1^vii	−106.2 (2)
O1^vi—Dy2—O6—B2	−125.1 (3)	O3^vii—Dy2—B2—Dy1^vii	6.95 (18)
O3^vii—Dy2—O6—B2	19.8 (4)	O4^viii—Dy2—B2—Dy1^vii	80.4 (3)
O4^viii—Dy2—O6—B2	122.2 (3)	O3^vi—Dy2—B2—Dy1^vii	−64.61 (16)
O3^vi—Dy2—O6—B2	−61.4 (3)	O6—Dy2—B2—Dy1^vii	170.9 (4)
B1^vi—Dy2—O6—B2	−90.0 (3)	B1^vi—Dy2—B2—Dy1^vii	−81.22 (19)
Dy1^iii—Dy2—O6—B2	−54.2 (3)	Dy1^iii—Dy2—B2—Dy1^vii	−74.32 (15)
Dy2^vi—Dy2—O6—B2	−152.1 (3)	Dy2^vi—Dy2—B2—Dy1^vii	−153.96 (7)

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