Penta­lanthanum zinc diplumbide, La₅Zn_1−xPb_2+x (x ≃ 0.6)

The title non-stoichiometric penta­lanthanum zinc diplumbide, La₅Zn_1−xPb_2+x (x ≃ 0.6), was prepared from the elements in an evacuated silica ampoule. It adopts the Nb₅Sn₂Si-type structure (space group I4/mcm, Pearson symbol tI32), a ternary ordered superstructure of the W₅Si₃ type. Among the four independent crystallographic positions, three are fully occupied by La (Wyckoff 16k), La (4b), and Pb (8h) and one is occupied by a statistical mixture [occupancy ratio 0.394 (12):0.606 (12)] of Zn and Pb (4a). The structure is constructed by face-sharing 10-vertex polyhedra around the unmixed Pb sites. These fragments enclose channels of trans-face-sharing tetra­gonal anti­prisms occupied by the disordered Zn and Pb sites.

Related literature

For general background to electronic structure calculations, see: Andersen et al. (1986); Becke & Edgecombe (1990); Dronskowski & Blöchl (1993); Lange (1999); Nowak et al. (1991). For related structures, see: Aronsson (1955); Oshchapovsky et al. (2011a,b, 2012a,b); Stetskiv et al. (2012). For isotypic structures, see: Horyn & Lukaszewich (1970).

Experimental

Crystal data

• La₅Zn_0.394Pb_2.606

• M_r = 1259.40

• Tetragonal, I 4/m c m

• a = 12.7630 (18) Å

• c = 6.3680 (13) Å

• V = 1037.3 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 63.04 mm⁻¹

• T = 153 K

• 0.04 × 0.02 × 0.01 mm

Data collection

• Bruker P4 CCD diffractometer

• Absorption correction: multi-scan (XSCANS; Bruker, 1999) T_min = 0.332, T_max = 0.525

• 3933 measured reflections

• 365 independent reflections

• 352 reflections with I > 2σ(I)

• R_int = 0.122

Refinement

• R[F² > 2σ(F²)] = 0.024

• wR(F²) = 0.058

• S = 1.25

• 352 reflections

• 18 parameters

• Δρ_max = 2.55 e Å⁻³

• Δρ_min = −1.27 e Å⁻³

Table 1
Bond lengths, negative iCOHP^a values and distance contractions in the La₅Zn_1−xPb_2+x compound

Bond	Length (δ in Å)	-iCOHP^a (eV)	Contraction^b (%) 100%
La1—La1	3.611	0.59	3.4
La1—La1	3.825	0.45	−2.3
La1—La1	3.997	0.40	−6.9
La1—La2	4.088	0.40	−9.3
La1—La1	4.193	0.32	−12.1
La2I—La2	3.184	1.26	14.9
La1—Zn4	3.365	0.26	−5.2
La2—Pb3	3.319	1.10	7.0
La1—Pb3	3.339	1.09	6.5
La1—Pb3	3.484	0.93	2.4
La1—Pb3	3.681	0.72	−3.1
Zn4—Zn4	3.184	−0.49	−19.7
Notes: (a) integrated Crystal Orbital Hamiltonian Population (see Dronskowski & Blöchl, 1993); calculated negative iCOHP values enable qualitative estimation of energies of two-center bonds; (b) based on metallic radii of elements R(La) = 1.86 Å R(Zn) = 1.33 Å and R(Pb) = 1.70 Å.

Data collection: XSCANS (Bruker, 1999); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006) and VESTA (Momma & Izumi, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Supporting information

S1. Comment

The title compound, (I), adopts a Nb₅Sn₂Si (Horyn & Lukaszewich, 1970) type structure (space group I4/mcm, Pearson symbol tI32), a ternary ordered superstructure of the W₅Si₃ type (Aronsson, 1955). A relevant detail of the structure of (I) is presented in Fig. 1.

The coordination polyhedron of the La1 atoms is a 15-vertices polyhedron (CN=15). The nearest neighbours of La2 atoms form 14-vertices polyhedra with CN=14 (see Fig. 1a). The 10-vertices polyhedra around Pb3 can be seen as the major building block of the structure. The face-sharing 10-vertices polyhedra form a three-dimensional framework encasing channels of face-sharing tetragonal antiprisms which in turn accommodate Zn4 and Pb4 with C·N. 10 in a statistical way (see Fig. 1 b, 1c).

This work continues the investigation of {La,Tb}-Zn-{Sn,Pb} ternary systems. In previous articles the bonding interactions in the compounds LaZn₄ (Oshchapovsky et al., 2012a), LaZn₅ (Oshchapovsky et al., 2012b), LaZn_12.37 (Oshchapovsky et al., 2011b) and TbLi_{1 - x}Zn_xSn₂ (Stetskiv et al., 2012) were estimated on the basis of electronic structure calculations using the TB-LMTO-ASA program package (Andersen et al., 1986; Nowak et al., 1991) with the additional implementation of two algorithms, the electron localization function (ELF) (Becke & Edgecombe, 1990) and – for quantifying nearest-neighbour bonding interactions – crystal orbital Hamilton population (COHP) (Dronskowski & Blöchl, 1993) analyses. Results arising from these analyses were put in relation to selected crystallographic data of La₅Zn₂Sn (Oshchapovsky et al., 2011a), namely a differential electronic density map obtained from diffraction data.

In all above mentioned compounds bonding interactions evolve similarly. Atoms of the rare-earth elements usually form metallic bonds with a certain ionic component as they donate part of their electrons to other atoms. The atoms of d- and p-metals, namely zinc and tin, accept these electrons used for covalent bonds among each other. This outcome can be easily explained by the higher electronegativity of zinc and tin compared with rare-earth and alkaline metals (Lange, 1999). Judged on the basis of integrated COHP, (iCOHP) values, R-{Zn,Sn} bonds are significantly weaker than {Zn,Sn}-{Zn,Sn} bonds. Latter mostly show significant bond length contraction compared to the next contacts in the elemental metals. The differential electronic density map of the structure of La₅Zn₂Sn, obtained from experimental diffraction data, indicate donation of electrons to zinc and tin atoms in the similar way as in other compounds, for which electronic structure calculations were performed.

The results of electronic structure calculations for (I) are given in Fig. 2 and 3. As an algorithm for calculating electronic structures for substances with mixed-occupied sites is not implemented in TB-LMTO-ASA package, a fictitious, crystallographically ordered phase was introduced by assuming the statistically occupied Zn/Pb site solely occupied by Zn without change of other crystallographic data.

Similar to R—Zn binary and R—Zn—Sn ternary compounds, large values of the electron localization function (ELF) around Pb3 and Zn4 (originally mixed-occupied) are found. In accordance with similar results for previously cited, structurally related compounds, these findings are interpreted as resulting from donation of electrons from lanthanum atoms to zinc and lead atoms (see Fig. 2a,b).

The values of ELF around Pb3 atoms are significantly larger than around Zn4 atoms, which indicate that bonds between Pb3 and their neighbours should be significantly stronger than bonds between Zn4 atoms and their neighbours. The calculated iCOHP values enable qualitative estimation of energies of two-center bonds and confirm previous assumption. Negative values of iCOHP together with bond lengths and bond contractions are given in Table.

The DOS plot indicates metallic conductivity for the ordered model compound (see Fig. 3a) with small dip at -1 eV relative to Fermi level. Based on a rigid band approximation it can be suggested that these features don't change qualitatively for the title compound. A small dip in the DOS plot near Fermi level could be indirect proof of donation of electrons from lanthanum atoms towards zinc and lead atoms.

The graph negative iCOHP values versus. distance contraction shown in Fig. 3 b substantiates the assumption that the polyhedra around Pb3 are indeed the building blocks of the structure if seen as condensed into the given three-dimensional framework by sharing faces. Apparently, this interpretation is not only useful from a crystallographic point of view but also supported by the hierarchy of bonding interactions in the solid: La—Pb bonds are stronger and show larger distance contractions than most La—La bonds. An exception is the particularly strong La2^IX—La2^X bond enhancing the stability of the framework by connecting adjacent building blocks.

Related literature

For general background, see: Andersen et al. (1986); Becke & Edgecombe (1990); Dronskowski & Blöchl (1993); Lange (1999); Nowak et al. (1991). For related structures, see: Aronsson (1955); Oshchapovsky et al. (2011a,b, 2012a,b); Stetskiv et al. (2012). For isostructural/isotypic structures, see: Horyn & Lukaszewich (1970).

S2. Experimental

A small irregular grey single-crystal of the title compound of suitable quality was isolated from an alloy with composition La₇ZnPb₂ prepared in the course of a systematic investigation of the ternary La—Zn—Pb system. The preparation process was according to that described for La₅Zn₂Sn (Oshchapovsky et al., 2011a).

The sample was prepared by melting pieces of pure metals (99.9% La, 99.999% Zn, 99.99% Pb) in an evacuated silica ampoule in a resistance furnace with subsequent annealing at 600°C for 30 days. Final phase analysis revealed the presence of the title compound in samples with composition La₇ZnPb₂ together with other lanthanum-rich ternary alloys. The latter samples, however, had not reached completely the liquid state, since the use of silica ampoules constraints the maximum temperature to 900°C. This limitation may hamper complete equilibration of the sample.

S3. Refinement

The fractional site occupancies of Pb4 and Zn4 were constrained to sum to unity.

Computing details

Data collection: XSCANS (Bruker, 1999); cell refinement: XSCANS (Bruker, 1999); data reduction: XSCANS (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006) and VESTA (Momma & Izumi, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. Details of the crystal structure of La5Zn1 - xPb2 + x: Projection of the unit cell and coordination polyhedra (a); building blocks (b); channels in the structure (c).
	Fig. 2. Results of ELF calculations for the La5Zn1 - xPb2 + xcompound: Isosurfaces drawn at 0.45 level (a); section [001] drawn at z=1/2 (b).
	Fig. 3. Density of states plot (a); Comparison of bond contractions and -iCOHP values in the title compound (b).

Pentalanthanum zinc diplumbide

Crystal data

La5Pb2.606Zn0.394	Dx = 8.068 Mg m^−3
Mr = 1259.40	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4/mcm	Cell parameters from 3933 reflections
Hall symbol: -I 4 2c	θ = 4.5–27.9°
a = 12.7630 (18) Å	µ = 63.04 mm^−1
c = 6.3680 (13) Å	T = 153 K
V = 1037.3 (3) Å^3	Irregularly shaped, metallic grey
Z = 4	0.04 × 0.02 × 0.01 mm
F(000) = 2041.6

Data collection

Bruker P4 CCD diffractometer	365 independent reflections
Radiation source: fine-focus sealed tube	352 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.122
ω scans	θmax = 27.9°, θmin = 4.5°
Absorption correction: multi-scan (XSCANS; Bruker, 1999)	h = −16→16
Tmin = 0.332, Tmax = 0.525	k = −15→16
3933 measured reflections	l = −8→8

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)] = 0.024	w = 1/[σ^2(Fo^2) + 23.7905P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.058	(Δ/σ)max = 0.012
S = 1.25	Δρmax = 2.55 e Å^−3
352 reflections	Δρmin = −1.27 e Å^−3
18 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 3948 (389)

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	Occ. (<1)
La1	0.08312 (9)	0.21698 (9)	0.0000	0.0229 (4)
La2	0.0000	0.5000	0.2500	0.0188 (6)
Pb3	0.16124 (5)	0.66124 (5)	0.0000	0.0187 (4)
Pb4	0.0000	0.0000	0.2500	0.0231 (9)	0.606 (12)
Zn4	0.0000	0.0000	0.2500	0.0231 (9)	0.394 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
La1	0.0150 (6)	0.0150 (6)	0.0386 (9)	0.0005 (4)	0.000	0.000
La2	0.0171 (6)	0.0171 (6)	0.0222 (12)	0.000	0.000	0.000
Pb3	0.0137 (4)	0.0137 (4)	0.0287 (7)	−0.0013 (3)	0.000	0.000
Pb4	0.0142 (8)	0.0142 (8)	0.0410 (16)	0.000	0.000	0.000
Zn4	0.0142 (8)	0.0142 (8)	0.0410 (16)	0.000	0.000	0.000

Geometric parameters (Å, º)

La1—Pb3^i	3.3394 (14)	La2—La1^iii	4.0875 (12)
La1—Zn4^ii	3.3658 (11)	Pb3—La2^iii	3.3173 (9)
La1—Pb4^ii	3.3658 (11)	Pb3—La1^xiv	3.3394 (14)
La1—Pb4	3.3658 (11)	Pb3—La1^xv	3.3394 (14)
La1—Pb3^iii	3.4846 (12)	Pb3—La1^iii	3.4846 (12)
La1—La1^iv	3.608 (2)	Pb3—La1^iv	3.4846 (12)
La1—Pb3^v	3.6807 (8)	Pb3—La1^xii	3.6807 (8)
La1—Pb3^vi	3.6807 (8)	Pb3—La1^xvi	3.6807 (8)
La1—La1^vii	3.8261 (13)	Pb3—La1^xi	3.6807 (8)
La1—La1^viii	3.8261 (13)	Pb3—La1^xvii	3.6807 (8)
La1—La1^ix	3.9969 (14)	Pb4—Zn4^xviii	3.1840 (7)
La2—La2^x	3.1840 (7)	Pb4—Zn4^ii	3.1840 (6)
La2—La2^iii	3.1840 (6)	Pb4—Pb4^xviii	3.1840 (7)
La2—Pb3^iii	3.3173 (9)	Pb4—Pb4^ii	3.1840 (6)
La2—Pb3	3.3173 (9)	Pb4—La1^xix	3.3658 (11)
La2—Pb3^v	3.3173 (9)	Pb4—La1^ii	3.3658 (11)
La2—Pb3^xi	3.3173 (9)	Pb4—La1^viii	3.3658 (11)
La2—La1^xii	4.0875 (12)	Pb4—La1^xx	3.3658 (11)
La2—La1^xi	4.0875 (12)	Pb4—La1^xxi	3.3658 (11)
La2—La1^xiii	4.0875 (12)	Pb4—La1^xxii	3.3658 (11)
La2—La1^v	4.0875 (12)	Pb4—La1^xxiii	3.3658 (11)
Pb3^i—La1—Zn4^ii	97.62 (3)	La1^xii—La2—La1	149.92 (3)
Pb3^i—La1—Pb4^ii	97.62 (3)	La1^xi—La2—La1	98.725 (6)
Zn4^ii—La1—Pb4^ii	0.0	La1^xiii—La2—La1	107.88 (3)
Pb3^i—La1—Pb4	97.62 (3)	La1^v—La2—La1	98.725 (6)
Zn4^ii—La1—Pb4	56.46 (2)	La1^iii—La2—La1	134.156 (16)
Pb4^ii—La1—Pb4	56.46 (2)	La2^iii—Pb3—La2	57.36 (2)
Pb3^i—La1—Pb3^iii	165.81 (4)	La2^iii—Pb3—La1^xiv	137.584 (15)
Zn4^ii—La1—Pb3^iii	94.87 (3)	La2—Pb3—La1^xiv	137.584 (15)
Pb4^ii—La1—Pb3^iii	94.87 (3)	La2^iii—Pb3—La1^xv	137.584 (15)
Pb4—La1—Pb3^iii	94.87 (3)	La2—Pb3—La1^xv	137.584 (15)
Pb3^i—La1—La1^iv	57.30 (2)	La1^xiv—Pb3—La1^xv	65.40 (4)
Zn4^ii—La1—La1^iv	143.576 (15)	La2^iii—Pb3—La1^iii	73.83 (2)
Pb4^ii—La1—La1^iv	143.576 (15)	La2—Pb3—La1^iii	73.83 (2)
Pb4—La1—La1^iv	143.576 (15)	La1^xiv—Pb3—La1^iii	75.81 (4)
Pb3^iii—La1—La1^iv	108.51 (2)	La1^xv—Pb3—La1^iii	141.21 (2)
Pb3^i—La1—Pb3^v	79.94 (3)	La2^iii—Pb3—La1^iv	73.83 (2)
Zn4^ii—La1—Pb3^v	147.35 (3)	La2—Pb3—La1^iv	73.83 (2)
Pb4^ii—La1—Pb3^v	147.35 (3)	La1^xiv—Pb3—La1^iv	141.21 (2)
Pb4—La1—Pb3^v	91.356 (15)	La1^xv—Pb3—La1^iv	75.81 (4)
Pb3^iii—La1—Pb3^v	93.10 (3)	La1^iii—Pb3—La1^iv	142.98 (5)
La1^iv—La1—Pb3^v	60.650 (17)	La2^iii—Pb3—La1^xii	120.60 (3)
Pb3^i—La1—Pb3^vi	79.94 (3)	La2—Pb3—La1^xii	71.26 (2)
Zn4^ii—La1—Pb3^vi	91.356 (15)	La1^xiv—Pb3—La1^xii	69.21 (3)
Pb4^ii—La1—Pb3^vi	91.356 (15)	La1^xv—Pb3—La1^xii	100.06 (3)
Pb4—La1—Pb3^vi	147.35 (3)	La1^iii—Pb3—La1^xii	64.48 (2)
Pb3^iii—La1—Pb3^vi	93.10 (3)	La1^iv—Pb3—La1^xii	119.919 (19)
La1^iv—La1—Pb3^vi	60.650 (17)	La2^iii—Pb3—La1^xvi	71.26 (2)
Pb3^v—La1—Pb3^vi	119.78 (3)	La2—Pb3—La1^xvi	120.60 (3)
Pb3^i—La1—La1^vii	122.81 (3)	La1^xiv—Pb3—La1^xvi	69.21 (3)
Zn4^ii—La1—La1^vii	55.363 (14)	La1^xv—Pb3—La1^xvi	100.06 (3)
Pb4^ii—La1—La1^vii	55.363 (14)	La1^iii—Pb3—La1^xvi	64.48 (2)
Pb4—La1—La1^vii	102.64 (3)	La1^iv—Pb3—La1^xvi	119.919 (19)
Pb3^iii—La1—La1^vii	60.24 (3)	La1^xii—Pb3—La1^xvi	119.78 (3)
La1^iv—La1—La1^vii	113.086 (18)	La2^iii—Pb3—La1^xi	120.60 (3)
Pb3^v—La1—La1^vii	150.47 (3)	La2—Pb3—La1^xi	71.26 (2)
Pb3^vi—La1—La1^vii	55.274 (16)	La1^xiv—Pb3—La1^xi	100.06 (3)
Pb3^i—La1—La1^viii	122.81 (3)	La1^xv—Pb3—La1^xi	69.21 (3)
Zn4^ii—La1—La1^viii	102.64 (3)	La1^iii—Pb3—La1^xi	119.919 (19)
Pb4^ii—La1—La1^viii	102.64 (3)	La1^iv—Pb3—La1^xi	64.48 (2)
Pb4—La1—La1^viii	55.363 (14)	La1^xii—Pb3—La1^xi	58.70 (3)
Pb3^iii—La1—La1^viii	60.24 (3)	La1^xvi—Pb3—La1^xi	167.71 (4)
La1^iv—La1—La1^viii	113.086 (18)	La2^iii—Pb3—La1^xvii	71.26 (2)
Pb3^v—La1—La1^viii	55.274 (16)	La2—Pb3—La1^xvii	120.60 (3)
Pb3^vi—La1—La1^viii	150.47 (3)	La1^xiv—Pb3—La1^xvii	100.06 (3)
La1^vii—La1—La1^viii	112.64 (6)	La1^xv—Pb3—La1^xvii	69.21 (3)
Pb3^i—La1—La1^ix	59.42 (3)	La1^iii—Pb3—La1^xvii	119.919 (19)
Zn4^ii—La1—La1^ix	53.576 (15)	La1^iv—Pb3—La1^xvii	64.48 (2)
Pb4^ii—La1—La1^ix	53.576 (15)	La1^xii—Pb3—La1^xvii	167.71 (4)
Pb4—La1—La1^ix	99.20 (3)	La1^xvi—Pb3—La1^xvii	58.70 (3)
Pb3^iii—La1—La1^ix	124.98 (2)	La1^xi—Pb3—La1^xvii	119.78 (3)
La1^iv—La1—La1^ix	90.0	Zn4^xviii—Pb4—Zn4^ii	180.0
Pb3^v—La1—La1^ix	138.92 (3)	Zn4^xviii—Pb4—Pb4^xviii	0.0
Pb3^vi—La1—La1^ix	51.362 (18)	Zn4^ii—Pb4—Pb4^xviii	180.0
La1^vii—La1—La1^ix	64.79 (2)	Zn4^xviii—Pb4—Pb4^ii	180.0
La1^viii—La1—La1^ix	154.150 (9)	Zn4^ii—Pb4—Pb4^ii	0.0
La2^x—La2—La2^iii	180.0	Pb4^xviii—Pb4—Pb4^ii	180.0
La2^x—La2—Pb3^iii	118.679 (10)	Zn4^xviii—Pb4—La1^xix	61.771 (11)
La2^iii—La2—Pb3^iii	61.321 (10)	Zn4^ii—Pb4—La1^xix	118.229 (11)
La2^x—La2—Pb3	118.679 (10)	Pb4^xviii—Pb4—La1^xix	61.771 (11)
La2^iii—La2—Pb3	61.321 (10)	Pb4^ii—Pb4—La1^xix	118.229 (11)
Pb3^iii—La2—Pb3	122.64 (2)	Zn4^xviii—Pb4—La1^ii	118.229 (11)
La2^x—La2—Pb3^v	61.321 (10)	Zn4^ii—Pb4—La1^ii	61.771 (11)
La2^iii—La2—Pb3^v	118.679 (10)	Pb4^xviii—Pb4—La1^ii	118.229 (11)
Pb3^iii—La2—Pb3^v	103.315 (9)	Pb4^ii—Pb4—La1^ii	61.771 (11)
Pb3—La2—Pb3^v	103.315 (9)	La1^xix—Pb4—La1^ii	137.93 (4)
La2^x—La2—Pb3^xi	61.321 (10)	Zn4^xviii—Pb4—La1^viii	61.771 (11)
La2^iii—La2—Pb3^xi	118.679 (10)	Zn4^ii—Pb4—La1^viii	118.229 (11)
Pb3^iii—La2—Pb3^xi	103.315 (9)	Pb4^xviii—Pb4—La1^viii	61.771 (11)
Pb3—La2—Pb3^xi	103.315 (9)	Pb4^ii—Pb4—La1^viii	118.229 (11)
Pb3^v—La2—Pb3^xi	122.64 (2)	La1^xix—Pb4—La1^viii	77.072 (9)
La2^x—La2—La1^xii	67.078 (8)	La1^ii—Pb4—La1^viii	143.26 (4)
La2^iii—La2—La1^xii	112.922 (8)	Zn4^xviii—Pb4—La1	118.229 (11)
Pb3^iii—La2—La1^xii	153.655 (15)	Zn4^ii—Pb4—La1	61.771 (11)
Pb3—La2—La1^xii	58.513 (15)	Pb4^xviii—Pb4—La1	118.229 (11)
Pb3^v—La2—La1^xii	101.555 (15)	Pb4^ii—Pb4—La1	61.771 (11)
Pb3^xi—La2—La1^xii	54.961 (15)	La1^xix—Pb4—La1	72.85 (3)
La2^x—La2—La1^xi	67.078 (8)	La1^ii—Pb4—La1	123.54 (2)
La2^iii—La2—La1^xi	112.922 (8)	La1^viii—Pb4—La1	69.27 (3)
Pb3^iii—La2—La1^xi	153.655 (15)	Zn4^xviii—Pb4—La1^xx	118.229 (11)
Pb3—La2—La1^xi	58.513 (15)	Zn4^ii—Pb4—La1^xx	61.771 (11)
Pb3^v—La2—La1^xi	54.961 (15)	Pb4^xviii—Pb4—La1^xx	118.229 (11)
Pb3^xi—La2—La1^xi	101.555 (15)	Pb4^ii—Pb4—La1^xx	61.771 (11)
La1^xii—La2—La1^xi	52.38 (3)	La1^xix—Pb4—La1^xx	69.27 (3)
La2^x—La2—La1^xiii	112.922 (8)	La1^ii—Pb4—La1^xx	77.072 (9)
La2^iii—La2—La1^xiii	67.078 (8)	La1^viii—Pb4—La1^xx	137.93 (4)
Pb3^iii—La2—La1^xiii	54.961 (15)	La1—Pb4—La1^xx	77.072 (9)
Pb3—La2—La1^xiii	101.555 (15)	Zn4^xviii—Pb4—La1^xxi	118.229 (11)
Pb3^v—La2—La1^xiii	153.655 (15)	Zn4^ii—Pb4—La1^xxi	61.771 (11)
Pb3^xi—La2—La1^xiii	58.513 (15)	Pb4^xviii—Pb4—La1^xxi	118.229 (11)
La1^xii—La2—La1^xiii	98.725 (6)	Pb4^ii—Pb4—La1^xxi	61.771 (11)
La1^xi—La2—La1^xiii	149.92 (3)	La1^xix—Pb4—La1^xxi	143.26 (4)
La2^x—La2—La1^v	67.078 (8)	La1^ii—Pb4—La1^xxi	77.072 (9)
La2^iii—La2—La1^v	112.922 (8)	La1^viii—Pb4—La1^xxi	72.85 (3)
Pb3^iii—La2—La1^v	58.513 (15)	La1—Pb4—La1^xxi	77.072 (10)
Pb3—La2—La1^v	153.655 (15)	La1^xx—Pb4—La1^xxi	123.54 (2)
Pb3^v—La2—La1^v	101.555 (15)	Zn4^xviii—Pb4—La1^xxii	61.771 (11)
Pb3^xi—La2—La1^v	54.961 (15)	Zn4^ii—Pb4—La1^xxii	118.229 (11)
La1^xii—La2—La1^v	107.88 (3)	Pb4^xviii—Pb4—La1^xxii	61.771 (11)
La1^xi—La2—La1^v	134.156 (16)	Pb4^ii—Pb4—La1^xxii	118.229 (11)
La1^xiii—La2—La1^v	55.81 (2)	La1^xix—Pb4—La1^xxii	123.54 (2)
La2^x—La2—La1^iii	112.922 (8)	La1^ii—Pb4—La1^xxii	72.85 (3)
La2^iii—La2—La1^iii	67.078 (8)	La1^viii—Pb4—La1^xxii	77.072 (9)
Pb3^iii—La2—La1^iii	101.555 (15)	La1—Pb4—La1^xxii	137.93 (4)
Pb3—La2—La1^iii	54.961 (15)	La1^xx—Pb4—La1^xxii	143.26 (4)
Pb3^v—La2—La1^iii	153.655 (15)	La1^xxi—Pb4—La1^xxii	69.27 (3)
Pb3^xi—La2—La1^iii	58.513 (15)	Zn4^xviii—Pb4—La1^xxiii	61.771 (11)
La1^xii—La2—La1^iii	55.81 (2)	Zn4^ii—Pb4—La1^xxiii	118.229 (11)
La1^xi—La2—La1^iii	98.725 (6)	Pb4^xviii—Pb4—La1^xxiii	61.771 (11)
La1^xiii—La2—La1^iii	52.38 (3)	Pb4^ii—Pb4—La1^xxiii	118.229 (11)
La1^v—La2—La1^iii	98.725 (6)	La1^xix—Pb4—La1^xxiii	77.072 (9)
La2^x—La2—La1	112.922 (8)	La1^ii—Pb4—La1^xxiii	69.27 (3)
La2^iii—La2—La1	67.078 (8)	La1^viii—Pb4—La1^xxiii	123.54 (2)
Pb3^iii—La2—La1	54.961 (15)	La1—Pb4—La1^xxiii	143.26 (4)
Pb3—La2—La1	101.555 (15)	La1^xx—Pb4—La1^xxiii	72.85 (3)
Pb3^v—La2—La1	58.513 (15)	La1^xxi—Pb4—La1^xxiii	137.93 (4)
Pb3^xi—La2—La1	153.655 (15)	La1^xxii—Pb4—La1^xxiii	77.072 (9)

Symmetry codes: (i) −y+1, x, z; (ii) −x, −y, −z; (iii) −x, −y+1, −z; (iv) −y+1/2, −x+1/2, z; (v) y−1/2, −x+1/2, −z+1/2; (vi) y−1/2, −x+1/2, −z−1/2; (vii) −x, y, −z−1/2; (viii) −x, y, −z+1/2; (ix) y, x, −z−1/2; (x) −x, −y+1, −z+1; (xi) −y+1/2, x+1/2, z+1/2; (xii) x, −y+1, z+1/2; (xiii) y−1/2, x+1/2, −z; (xiv) y, −x+1, −z; (xv) −x+1/2, y+1/2, −z; (xvi) x, −y+1, z−1/2; (xvii) −y+1/2, x+1/2, z−1/2; (xviii) −x, −y, −z+1; (xix) y, x, −z+1/2; (xx) y, −x, −z; (xxi) −y, x, z; (xxii) −y, −x, z+1/2; (xxiii) x, −y, z+1/2.

 

Footnotes

‡Also at Institute of Chemistry and Environmental Protection, Jan Dlugosz University, Armii Krajowej 13/15 Ave., 42-200 Czestochowa, Poland