Penta­zirconium copper tribismuth

Penta­zirconium copper tribismuth, Zr₅CuBi₃, crystallizes in the hexa­gonal Hf₅CuSn₃ structure type. The asymmetric unit contains two Zr sites (site symmetries 3.2 and m2m), one Cu site (site symmetry 3.m) and one Bi site (site symmetry m2m). The environment of the Bi atoms is a tetra­gonal anti­prism with one added atom and a coordination number (CN) of 9. The polyhedron around the Zr1 atom is a defective cubo­octa­hedron with CN = 11. The bicapped hexa­gonal anti­prism (CN = 14) is typical for Zr2 atoms. The Cu atom is enclosed in a eight-vertex polyhedron (octa­hedron with two centered faces). The metallic type of bonding was indicated by an analysis of the inter­atomic distances and electronic structure calculation data.

Related literature

For general background, see: Dolotko et al. (2003); Giza et al. (2001, 2009); Zatorska et al. (2002a,b, 2004). For isotypic structures, see: Garcia & Corbett (1990); Pöttgen (1997); Rieger & Parthé (1965); Stetskiv et al. (2011). For calculation of the electronic structure using the tight-binding linear muffin-tin orbital (TB–LMTO) method in the atomic spheres approximation, see: Andersen (1975); Andersen & Jepsen (1984); Andersen et al. (1985, 1986).

Experimental

Crystal data

• Zr₅CuBi₃

• M_r = 1146.58

• Hexagonal, P 6₃ /m c m

• a = 8.8712 (4) Å

• c = 6.0246 (3) Å

• V = 410.60 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 72.54 mm⁻¹

• T = 293 K

• 0.08 × 0.04 × 0.02 mm

Data collection

• Oxford Diffraction Xcalibur3 CCD diffractometer

• Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008) T_min = 0.231, T_max = 0.654

• 1713 measured reflections

• 193 independent reflections

• 185 reflections with I > 2σ(I)

• R_int = 0.136

Refinement

• R[F² > 2σ(F²)] = 0.023

• wR(F²) = 0.041

• S = 0.87

• 193 reflections

• 13 parameters

• Δρ_max = 1.92 e Å⁻³

• Δρ_min = −1.54 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97.

Supporting information

S1. Comment

Zirconium intermetallic compounds are extensively investigated for the last 40 years as possible hydrogen storage materials. The results that we present in this paper is a continuation of the systematic study that we carried out for zirconium alloys with transition metals (Giza et al., 2001; Dolotko et al., 2003) as well as s-and p-elements (Zatorska et al., 2002a,b; 2004; Giza et al., 2009). So far, in the literature no data on ternary intermetallic compounds of Zr—Cu—Bi system has been found. However, it is known that closely related systems such as Zr—Cu—Sn (Pöttgen, 1997), Zr—Cu—Pb (Rieger & Parthé, 1965) and Zr—Cu—Sb (Garcia & Corbett, 1990) form Zr₅CuX₃ (where X=Sn, Pb, Sb) compounds with hexagonal Hf₅CuSn₃ structure type (superstructure to Ti₅Ga₄-type) with space group P6₃/mcm. Studying alloys of the Zr—Cu—Bi system we found the existence of isostructural Zr₅CuBi₃ compound and investigated its structure by single-crystal method. The projection of the unit cell and coordination polyhedra of the atoms are shown in Fig. 1. The environment of the Bi atoms is a tetragonal antiprism with one added atom and a coordination number equal 9. The polyhedron of Zr1 atom is a defective cubooctahedron with a coordination number equal 11. The bicapped hexagonal antiprism (c.n.=14) is typical for Zr2 atom. The Cu atom is enclosed in a 8-vertex polyhedron (octahedron with two centered faces). The distribution of zirconium and copper atoms in three-dimensional-nets consisted of Bi atoms are shown in Fig. 2a and distribution of bismuth and copper atoms in three-dimensional-nets consisted of Zr atoms are shown in Fig. 2b. In the first case the Bi atoms form a 6₃ corrugated nets and the Zr atoms (second case) form a 3₂46 nets. The similar atomic nets was described for Tb₅LiSn₃ isostructural compound (Stetskiv et al., 2011).

The electronic structure of the Zr₅CuBi₃ compound was calculated using the tight-binding linear muffin-tin orbital (TB–LMTO) method in the atomic spheres approximation (TB– LMTO–ASA; Andersen, 1975; Andersen & Jepsen, 1984; Andersen et al., 1985, 1986), using the experimental crystallographic data which are presented here. The Zr and Cu atoms donate their electrons to the Bi atoms. Therefore positive charge density can be observed around the atoms of transition elements (Zr and Cu) and negative charge density is around the bismuth atoms. The electron localization function (ELF) mapping and isosurfaces (ISO) are presented in Fig. 3a and Fig. 3b, respectively. The total and partial densities of states (DOS) of Zr₅CuBi₃ compound calculated by the TB–LMTO–ASA method are shown in Fig. 4. The Fermi level (EF) lies in a continuous DOS region indicating a metallic character for the title compound. The metallic type of bonding was confirmed also by an analysis of the interatomic distances.

Related literature

For general background, see: Dolotko et al. (2003); Giza et al. (2001, 2009); Zatorska et al. (2002a,b, 2004). For isostructural/isotypic structures, see: Garcia & Corbett (1990); Pöttgen (1997); Rieger & Parthé (1965); Stetskiv et al. (2011). For calculation of the electronic structure using the tight-binding linear muffin-tin orbital (TB–LMTO) method in the atomic spheres approximation, see: Andersen (1975); Andersen & Jepsen (1984); Andersen et al. (1985, 1986).

S2. Experimental

The title compound was prepared from elemental zirconium (foil, 0.25 mm thick 99.8 at.%, Aldrich), copper (powder, pure, POCH) and bismuth (granules, 99.5 at.%, POCH). The pieces of the pure metals with a stoichiometry Zr₅₀Cu₂₀Bi₃₀ were pressed into pellet. The sample was melted in arc furnace under continuous argon flow. The losses in alloy composition during melting were checked by weight comparison of the initial mixtures and the alloys. Metallic grey prismatic crystals were found in a crushed alloy using a conventional light microscope.

S3. Refinement

The structure was solved after the analytical absorption correction. In the first stage of the refinement, the positions of the Zr, Cu and Bi atoms were obtained correctly by direct methods. After the last cycle of refinement the highest peak of 1.915 e/Å3 is at (0; 0.4552; 1/4) and 0.76 Å away from the Bi atom. The deepest hole -1.539 e/Å3 is at (0.2424; 0; 1/4) and 1.12 Å away from the same atom.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The projection of the unit cell and coordination polyhedra of the atoms.
	Fig. 2. The distribution of Zr and Cu atoms in three-dimensional-nets from Bi atoms (a) and distribution of Bi and Cu atoms in three-dimensional-nets from Zr atoms (b).
	Fig. 3. (a) The electron localization function (ELF) mapping and (b) isosurfaces of the electron localization function around the atoms for Zr5CuBi3.
	Fig. 4. Total and partial DOS (densities of states) for Zr5CuBi3.

Pentazirconium copper tribismuth

Crystal data

Zr5CuBi3	Dx = 9.274 Mg m^−3
Mr = 1146.58	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/mcm	Cell parameters from 185 reflections
Hall symbol: -P 6c 2	θ = 2.7–27.4°
a = 8.8712 (4) Å	µ = 72.54 mm^−1
c = 6.0246 (3) Å	T = 293 K
V = 410.60 (3) Å^3	Prism, metallic grey
Z = 2	0.08 × 0.04 × 0.02 mm
F(000) = 956

Data collection

Oxford Diffraction Xcalibur3 CCD diffractometer	193 independent reflections
Radiation source: fine-focus sealed tube	185 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.136
Detector resolution: 0 pixels mm^-1	θmax = 27.4°, θmin = 2.7°
ω scans	h = −11→11
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −11→11
Tmin = 0.231, Tmax = 0.654	l = 0→7
1713 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.023	Secondary atom site location: difference Fourier map
wR(F^2) = 0.041	w = 1/[σ^2(Fo^2) + (0.010P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.87	(Δ/σ)max < 0.001
193 reflections	Δρmax = 1.92 e Å^−3
13 parameters	Δρmin = −1.54 e Å^−3

Special details

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
Bi1	0.63082 (6)	0.63082 (6)	0.2500	0.00715 (19)
Zr1	0.26831 (17)	0.26831 (17)	0.2500	0.0083 (3)
Zr2	0.6667	0.3333	0.0000	0.0103 (4)
Cu1	0.0000	0.0000	0.0000	0.0102 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.0060 (2)	0.0060 (2)	0.0098 (3)	0.0033 (2)	0.000	0.000
Zr1	0.0075 (4)	0.0075 (4)	0.0102 (8)	0.0039 (5)	0.000	0.000
Zr2	0.0132 (7)	0.0132 (7)	0.0045 (11)	0.0066 (3)	0.000	0.000
Cu1	0.0106 (14)	0.0106 (14)	0.009 (3)	0.0053 (7)	0.000	0.000

Geometric parameters (Å, º)

Bi1—Zr1^i	2.9319 (6)	Zr2—Zr2^ii	3.0123 (2)
Bi1—Zr1^ii	2.9319 (6)	Zr2—Zr2^viii	3.0123 (2)
Bi1—Zr1^iii	3.1424 (5)	Zr2—Bi1^ix	3.1896 (2)
Bi1—Zr1^iv	3.1424 (5)	Zr2—Bi1^ii	3.1896 (2)
Bi1—Zr2^v	3.1896 (2)	Zr2—Bi1^vi	3.1896 (2)
Bi1—Zr2^ii	3.1896 (2)	Zr2—Bi1^x	3.1896 (2)
Bi1—Zr2	3.1896 (2)	Zr2—Bi1^iv	3.1896 (2)
Bi1—Zr2^iv	3.1896 (2)	Zr2—Zr1^ii	3.6126 (9)
Bi1—Zr1	3.2159 (17)	Zr2—Zr1^vi	3.6126 (9)
Zr1—Cu1	2.8167 (13)	Zr2—Zr1^ix	3.6126 (9)
Zr1—Cu1^v	2.8167 (13)	Zr2—Zr1^x	3.6126 (9)
Zr1—Bi1^vi	2.9319 (6)	Cu1—Zr1^xi	2.8167 (13)
Zr1—Bi1^vii	2.9319 (6)	Cu1—Zr1^ix	2.8167 (13)
Zr1—Bi1^iii	3.1424 (5)	Cu1—Zr1^xii	2.8167 (13)
Zr1—Bi1^iv	3.1424 (5)	Cu1—Zr1^xiii	2.8167 (13)
Zr1—Zr2^ii	3.6126 (9)	Cu1—Zr1^xiv	2.8167 (13)
Zr1—Zr2^v	3.6126 (9)	Cu1—Cu1^v	3.0123 (2)
Zr1—Zr2	3.6126 (9)	Cu1—Cu1^xii	3.0123 (2)
Zr1—Zr2^iv	3.6126 (9)
Zr1^i—Bi1—Zr1^ii	89.35 (6)	Zr2^viii—Zr2—Bi1^ix	61.822 (2)
Zr1^i—Bi1—Zr1^iii	78.32 (3)	Zr2^ii—Zr2—Bi1^ii	61.822 (2)
Zr1^ii—Bi1—Zr1^iii	78.32 (3)	Zr2^viii—Zr2—Bi1^ii	118.178 (2)
Zr1^i—Bi1—Zr1^iv	78.32 (3)	Bi1^ix—Zr2—Bi1^ii	88.460 (16)
Zr1^ii—Bi1—Zr1^iv	78.32 (3)	Zr2^ii—Zr2—Bi1^vi	61.822 (2)
Zr1^iii—Bi1—Zr1^iv	146.91 (6)	Zr2^viii—Zr2—Bi1^vi	118.178 (2)
Zr1^i—Bi1—Zr2^v	72.20 (3)	Bi1^ix—Zr2—Bi1^vi	73.185 (10)
Zr1^ii—Bi1—Zr2^v	145.409 (19)	Bi1^ii—Zr2—Bi1^vi	99.528 (3)
Zr1^iii—Bi1—Zr2^v	69.571 (14)	Zr2^ii—Zr2—Bi1^x	118.178 (2)
Zr1^iv—Bi1—Zr2^v	123.798 (7)	Zr2^viii—Zr2—Bi1^x	61.822 (2)
Zr1^i—Bi1—Zr2^ii	145.409 (19)	Bi1^ix—Zr2—Bi1^x	99.528 (3)
Zr1^ii—Bi1—Zr2^ii	72.20 (3)	Bi1^ii—Zr2—Bi1^x	73.185 (10)
Zr1^iii—Bi1—Zr2^ii	69.571 (14)	Bi1^vi—Zr2—Bi1^x	170.093 (17)
Zr1^iv—Bi1—Zr2^ii	123.798 (7)	Zr2^ii—Zr2—Bi1^iv	118.178 (2)
Zr2^v—Bi1—Zr2^ii	106.815 (9)	Zr2^viii—Zr2—Bi1^iv	61.822 (2)
Zr1^i—Bi1—Zr2	145.409 (19)	Bi1^ix—Zr2—Bi1^iv	99.528 (3)
Zr1^ii—Bi1—Zr2	72.20 (3)	Bi1^ii—Zr2—Bi1^iv	170.093 (17)
Zr1^iii—Bi1—Zr2	123.798 (7)	Bi1^vi—Zr2—Bi1^iv	88.460 (16)
Zr1^iv—Bi1—Zr2	69.571 (14)	Bi1^x—Zr2—Bi1^iv	99.528 (3)
Zr2^v—Bi1—Zr2	137.327 (18)	Zr2^ii—Zr2—Bi1	61.822 (2)
Zr2^ii—Bi1—Zr2	56.356 (5)	Zr2^viii—Zr2—Bi1	118.178 (2)
Zr1^i—Bi1—Zr2^iv	72.20 (3)	Bi1^ix—Zr2—Bi1	170.093 (17)
Zr1^ii—Bi1—Zr2^iv	145.409 (19)	Bi1^ii—Zr2—Bi1	99.528 (3)
Zr1^iii—Bi1—Zr2^iv	123.798 (7)	Bi1^vi—Zr2—Bi1	99.528 (3)
Zr1^iv—Bi1—Zr2^iv	69.571 (14)	Bi1^x—Zr2—Bi1	88.460 (16)
Zr2^v—Bi1—Zr2^iv	56.356 (5)	Bi1^iv—Zr2—Bi1	73.185 (9)
Zr2^ii—Bi1—Zr2^iv	137.327 (18)	Zr2^ii—Zr2—Zr1^ii	65.360 (7)
Zr2—Bi1—Zr2^iv	106.815 (10)	Zr2^viii—Zr2—Zr1^ii	114.640 (7)
Zr1^i—Bi1—Zr1	135.33 (3)	Bi1^ix—Zr2—Zr1^ii	139.216 (18)
Zr1^ii—Bi1—Zr1	135.33 (3)	Bi1^ii—Zr2—Zr1^ii	56.01 (2)
Zr1^iii—Bi1—Zr1	106.55 (3)	Bi1^vi—Zr2—Zr1^ii	127.097 (6)
Zr1^iv—Bi1—Zr1	106.55 (3)	Bi1^x—Zr2—Zr1^ii	54.600 (5)
Zr2^v—Bi1—Zr1	68.664 (9)	Bi1^iv—Zr2—Zr1^ii	114.38 (2)
Zr2^ii—Bi1—Zr1	68.664 (9)	Bi1—Zr2—Zr1^ii	50.598 (19)
Zr2—Bi1—Zr1	68.664 (9)	Zr2^ii—Zr2—Zr1^vi	65.360 (7)
Zr2^iv—Bi1—Zr1	68.664 (9)	Zr2^viii—Zr2—Zr1^vi	114.640 (7)
Cu1—Zr1—Cu1^v	64.65 (3)	Bi1^ix—Zr2—Zr1^vi	54.600 (5)
Cu1—Zr1—Bi1^vi	77.64 (3)	Bi1^ii—Zr2—Zr1^vi	50.598 (19)
Cu1^v—Zr1—Bi1^vi	77.64 (3)	Bi1^vi—Zr2—Zr1^vi	56.01 (2)
Cu1—Zr1—Bi1^vii	77.64 (3)	Bi1^x—Zr2—Zr1^vi	114.38 (2)
Cu1^v—Zr1—Bi1^vii	77.64 (3)	Bi1^iv—Zr2—Zr1^vi	139.216 (18)
Bi1^vi—Zr1—Bi1^vii	150.65 (6)	Bi1—Zr2—Zr1^vi	127.097 (6)
Cu1—Zr1—Bi1^iii	138.87 (4)	Zr1^ii—Zr2—Zr1^vi	103.844 (8)
Cu1^v—Zr1—Bi1^iii	74.221 (13)	Zr2^ii—Zr2—Zr1^ix	114.640 (7)
Bi1^vi—Zr1—Bi1^iii	94.137 (2)	Zr2^viii—Zr2—Zr1^ix	65.360 (7)
Bi1^vii—Zr1—Bi1^iii	94.137 (2)	Bi1^ix—Zr2—Zr1^ix	56.01 (2)
Cu1—Zr1—Bi1^iv	74.221 (13)	Bi1^ii—Zr2—Zr1^ix	139.216 (18)
Cu1^v—Zr1—Bi1^iv	138.87 (4)	Bi1^vi—Zr2—Zr1^ix	54.600 (5)
Bi1^vi—Zr1—Bi1^iv	94.137 (2)	Bi1^x—Zr2—Zr1^ix	127.097 (6)
Bi1^vii—Zr1—Bi1^iv	94.137 (2)	Bi1^iv—Zr2—Zr1^ix	50.598 (19)
Bi1^iii—Zr1—Bi1^iv	146.91 (6)	Bi1—Zr2—Zr1^ix	114.38 (2)
Cu1—Zr1—Bi1	147.675 (17)	Zr1^ii—Zr2—Zr1^ix	164.10 (4)
Cu1^v—Zr1—Bi1	147.675 (17)	Zr1^vi—Zr2—Zr1^ix	89.71 (3)
Bi1^vi—Zr1—Bi1	104.67 (3)	Zr2^ii—Zr2—Zr1^x	114.640 (7)
Bi1^vii—Zr1—Bi1	104.67 (3)	Zr2^viii—Zr2—Zr1^x	65.360 (7)
Bi1^iii—Zr1—Bi1	73.45 (3)	Bi1^ix—Zr2—Zr1^x	50.598 (19)
Bi1^iv—Zr1—Bi1	73.45 (3)	Bi1^ii—Zr2—Zr1^x	54.600 (5)
Cu1—Zr1—Zr2^ii	134.725 (16)	Bi1^vi—Zr2—Zr1^x	114.38 (2)
Cu1^v—Zr1—Zr2^ii	104.942 (7)	Bi1^x—Zr2—Zr1^x	56.01 (2)
Bi1^vi—Zr1—Zr2^ii	57.205 (10)	Bi1^iv—Zr2—Zr1^x	127.097 (6)
Bi1^vii—Zr1—Zr2^ii	146.09 (3)	Bi1—Zr2—Zr1^x	139.216 (18)
Bi1^iii—Zr1—Zr2^ii	55.829 (13)	Zr1^ii—Zr2—Zr1^x	89.71 (3)
Bi1^iv—Zr1—Zr2^ii	103.75 (3)	Zr1^vi—Zr2—Zr1^x	64.19 (4)
Bi1—Zr1—Zr2^ii	55.32 (2)	Zr1^ix—Zr2—Zr1^x	103.844 (8)
Cu1—Zr1—Zr2^v	134.725 (16)	Zr1—Cu1—Zr1^xi	180.00 (6)
Cu1^v—Zr1—Zr2^v	104.942 (7)	Zr1—Cu1—Zr1^ix	85.92 (2)
Bi1^vi—Zr1—Zr2^v	146.09 (3)	Zr1^xi—Cu1—Zr1^ix	94.08 (2)
Bi1^vii—Zr1—Zr2^v	57.205 (11)	Zr1—Cu1—Zr1^xii	85.92 (2)
Bi1^iii—Zr1—Zr2^v	55.829 (13)	Zr1^xi—Cu1—Zr1^xii	94.08 (2)
Bi1^iv—Zr1—Zr2^v	103.75 (3)	Zr1^ix—Cu1—Zr1^xii	94.08 (2)
Bi1—Zr1—Zr2^v	55.32 (2)	Zr1—Cu1—Zr1^xiii	94.08 (2)
Zr2^ii—Zr1—Zr2^v	90.29 (3)	Zr1^xi—Cu1—Zr1^xiii	85.92 (2)
Cu1—Zr1—Zr2	104.942 (7)	Zr1^ix—Cu1—Zr1^xiii	85.92 (2)
Cu1^v—Zr1—Zr2	134.725 (16)	Zr1^xii—Cu1—Zr1^xiii	180.00 (3)
Bi1^vi—Zr1—Zr2	57.205 (10)	Zr1—Cu1—Zr1^xiv	94.08 (2)
Bi1^vii—Zr1—Zr2	146.09 (3)	Zr1^xi—Cu1—Zr1^xiv	85.92 (2)
Bi1^iii—Zr1—Zr2	103.75 (3)	Zr1^ix—Cu1—Zr1^xiv	180.00 (3)
Bi1^iv—Zr1—Zr2	55.829 (13)	Zr1^xii—Cu1—Zr1^xiv	85.92 (2)
Bi1—Zr1—Zr2	55.32 (2)	Zr1^xiii—Cu1—Zr1^xiv	94.08 (2)
Zr2^ii—Zr1—Zr2	49.279 (13)	Zr1—Cu1—Cu1^v	57.675 (17)
Zr2^v—Zr1—Zr2	110.65 (4)	Zr1^xi—Cu1—Cu1^v	122.325 (17)
Cu1—Zr1—Zr2^iv	104.942 (7)	Zr1^ix—Cu1—Cu1^v	122.325 (17)
Cu1^v—Zr1—Zr2^iv	134.725 (16)	Zr1^xii—Cu1—Cu1^v	122.325 (17)
Bi1^vi—Zr1—Zr2^iv	146.09 (3)	Zr1^xiii—Cu1—Cu1^v	57.675 (17)
Bi1^vii—Zr1—Zr2^iv	57.205 (10)	Zr1^xiv—Cu1—Cu1^v	57.675 (17)
Bi1^iii—Zr1—Zr2^iv	103.75 (3)	Zr1—Cu1—Cu1^xii	122.325 (17)
Bi1^iv—Zr1—Zr2^iv	55.829 (13)	Zr1^xi—Cu1—Cu1^xii	57.675 (17)
Bi1—Zr1—Zr2^iv	55.32 (2)	Zr1^ix—Cu1—Cu1^xii	57.675 (17)
Zr2^ii—Zr1—Zr2^iv	110.65 (4)	Zr1^xii—Cu1—Cu1^xii	57.675 (17)
Zr2^v—Zr1—Zr2^iv	49.279 (13)	Zr1^xiii—Cu1—Cu1^xii	122.325 (17)
Zr2—Zr1—Zr2^iv	90.29 (3)	Zr1^xiv—Cu1—Cu1^xii	122.325 (17)
Zr2^ii—Zr2—Zr2^viii	180.0	Cu1^v—Cu1—Cu1^xii	180.0
Zr2^ii—Zr2—Bi1^ix	118.178 (2)

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