Undeca­europium hexa­zinc dodeca­arsenide

Saparov, B.; Bobev, S.

doi:10.1107/S1600536810006938

inorganic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page i24

doi:10.1107/S1600536810006938

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Undecaeuropium hexazinc dodecaarsenide

Bayrammurad Saparov ^a and Svilen Bobev ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716, USA
^*Correspondence e-mail: sbobev@mail.chem.udel.edu

(Received 9 February 2010; accepted 23 February 2010; online 27 February 2010)

The title compound, Eu₁₁Zn₆As₁₂, crystallizes with the Sr₁₁Cd₆Sb₁₂ structure type (Pearson's symbol mC58). The complex monoclinic structure of the first arsenide to form with this type features chains made of corner-sharing ZnAs₄ tetrahedra, separated by Eu atoms. There are a total of 15 unique positions in the asymmetric unit. Except for one Eu atom with site symmetry 2/m, all atoms are located on mirror planes. An usual aspect of the structure are some Zn—As distances, which are much longer than the sum of the covalent radii, indicating weaker interactions.

Related literature

The growing interest in ternary pnictides of alkaline- and rare-earth metals with group 12 metals has feen fueled by the recent discovery of superconductivity (Rotter et al., 2008 ). Such compounds have also been investigated because of their promising behaviour as materials with high thermoelectric conversion efficiency (Snyder & Toberer, 2008 ). Our own exploratory studies revealed a wealth of new compounds with diverse crystal structures, including Ca₂CdSb₂ and Yb₂CdSb₂ (Xia & Bobev, 2007a ), A₉Cd₄₊_xPn₉ and A₉Zn₄₊_xPn₉ (A = Ca, Sr, Eu, Yb; Pn = Sb, Bi) (Xia & Bobev, 2007b ), A₁₁Cd₆Sb₁₂ (A = Sr, Ba, Eu) and Eu₁₁Zn₆Sb₁₂ (Park & Kim, 2004 ; Xia & Bobev, 2008b ; Saparov et al., 2008a ), A₂₁Cd₄Pn₁₈ (A = Sr, Ba, Eu; Pn = Sb, Bi) (Xia & Bobev, 2008a ), Ba₃Cd₂Sb₄ (Saparov et al., 2008b ), Ba₂Cd₂Pn₃ (Pn = As, Sb) (Saparov et al., 2010 ). The title compound is the As-analog of Eu₁₁Zn₆Sb₁₂ (Saparov et al., 2008a). For covalent radii, see: Pauling (1960 ).

Experimental

Crystal data

Eu₁₁Zn₆As₁₂
M_r = 2962.82
Monoclinic, C 2/m
a = 30.310 (8) Å
b = 4.3318 (11) Å
c = 11.774 (3) Å
β = 109.746 (4)°
V = 1455.0 (7) Å³
Z = 2
Mo Kα radiation
μ = 41.68 mm⁻¹
T = 200 K
0.07 × 0.05 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.161, T_max = 0.256
7178 measured reflections
1796 independent reflections
1498 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.062
S = 1.01
1796 reflections
90 parameters
Δρ_max = 1.70 e Å⁻³
Δρ_min = −1.74 e Å⁻³

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810006938/wm2307sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810006938/wm2307Isup2.hkl

checkCIF report

Comment top

The structure of Eu₁₁Zn₆As₁₂ projected along b-axis is shown in Figure 1. The asymmetric unit is composed of 6 Eu, 3 Zn and 6 As atoms, all in special positions (Wyckoff position for Eu6 is 2a, for all others 4i).

The anionic substructure is made of Zn-centered ZnAs₄ tetrahedra that share common corners to form chains. The terminal As atoms of two chains are close together, so that they form a covalent bond. This can be inferred from the resulting As5—As5 distance at 2.457 (3) Å, which is on par with the As—As separation in elemental As (2.517 Å). All other interatomic distances fall within the expected range, excluding the Zn3—As5 distance at 3.288 Å. The latter is too long - more than 30% longer than the sum of the Pauling's covalent radii (Pauling, 1960) - to be considered a simple 2-center-2-electron bond. Analogously longer than normal Cd3—Sb5 and Zn3—Sb5 distances have been reported in Eu₁₁Cd₆Sb₁₂ and Eu₁₁Zn₆Sb₁₂ (Saparov et al., 2008a). We refer to the theoretical studies on Sr₁₁Cd₆Sb₁₂ and Ba₁₁Cd₆Sb₁₂ (Xia & Bobev, 2008b) for a more detailed discussion of the bonding interactions in this structure type.

d-metal centered tetrahedra of the pnicogen elements are recurring motifs in the structural chemistry of such solid-state compounds, as evidenced by a number of reports (Rotter et al., 2008; Snyder & Toberer, 2008; Xia & Bobev, 2008a; Saparov et al., 2008b; Saparov et al., 2010). Sr₁₁Cd₆Sb₁₂, the first structurally characterized phase with this monoclinic structure, was synthesized from a high temperature reaction of elements using Sn as metal flux (Park & Kim, 2004). In this report, the crystal structure was described as being composed of "double pentagonal tubes". A slightly different description of the structure was given in the light of the very long Cd3—Sb5 bond in Ba₁₁Cd₆Sb₁₂ (Xia & Bobev, 2008b). Therein, the authors performed comprehensive electronic structure calculations aimed at full understanding of the bonding in Sr₁₁Cd₆Sb₁₂ and Ba₁₁Cd₆Sb₁₂. From these computational results, and from earlier results pertaining to related materials such as Yb₂CdSb₂ (Xia & Bobev, 2007a), A₉Cd₄₊_xPn₉ and A₉Zn₄₊_xPn₉ (A=Ca, Sr, Eu, Yb; Pn= Sb, Bi) (Xia & Bobev, 2007b), it can be expected that the Eu cations in Eu₁₁Zn₆As₁₂ will be divalent, and the spins of the Eu's 7 unpaired electrons may couple magnetically at low temperatures. We were unable to experimentally confirm this conjecture because the title compound was not isolated as a pure phase, but magnetic property measurements on the isotypic europium antimonides Eu₁₁Cd₆Sb₁₂ and Eu₁₁Zn₆Sb₁₂ (Saparov et al., 2008a) confirmed Eu²⁺ cations (4f⁷ state). These measurements also suggested antiferromagnetic ordering in Eu₁₁Cd₆Sb₁₂ below T_N=7.5 K. The temperature dependent electrical resistivity measurements carried out on a single crystal of Eu₁₁Cd₆Sb₁₂ suggested poorly metallic behavior, as expected from band structure calculations performed for Sr₁₁Cd₆Sb₁₂ and Ba₁₁Cd₆Sb₁₂ (Xia & Bobev, 2008b).

Related literature top

The growing interest in ternary pnictides of alkaline- and rare-earth metals with group 12 metals has feen fueled by the recent discovery of superconductivity (Rotter et al., 2008). Such compounds have also been investigated because of their promising behaviour as materials with high thermoelectric conversion efficiency (Snyder & Toberer, 2008). Our own exploratory studies revealed a wealth of new compounds with diverse crystal structures, including Ca₂CdSb₂ and Yb₂CdSb₂ (Xia & Bobev, 2007a), A₉Cd₄₊_xPn₉ and A₉Zn₄₊_xPn₉ (A = Ca, Sr, Eu, Yb; Pn = Sb, Bi) (Xia & Bobev, 2007b), A₁₁Cd₆Sb₁₂ (A = Sr, Ba, Eu) and Eu₁₁Zn₆Sb₁₂ (Park & Kim, 2004; Xia & Bobev, 2008b; Saparov et al., 2008a), A₂₁Cd₄Pn₁₈ (A = Sr, Ba, Eu; Pn = Sb, Bi) (Xia & Bobev, 2008a), Ba₃Cd₂Sb₄ (Saparov et al., 2008b), Ba₂Cd₂Pn₃ (Pn = As, Sb) (Saparov et al., 2010). The title compound is the As-analog of Eu₁₁Zn₆Sb₁₂ (Saparov et al., 2008a). For covalent radii, see: Pauling (1960).

Experimental top

The starting materials, Eu, Zn, As, and Pb, with stated purity greater than 99.9%, were purchased from Alfa or Aldrich, and used as received. Elements were loaded into an alumina crucible in a Eu:Zn:As:Pb=2:1:2:10 molar ratio inside an argon-filled glove-box. The alumina crucible was then sealed under vacuum in a silica tube. The reaction mixture was heated to 1223 K, kept at this temperature for 20 hours, and then slowly cooled to 723 K at a rate of 3 K/hour. Finally, the Pb-flux was removed by centrifugation at this temperature. Together with irregular-shaped crystals with hitherto unknown structure, black needle shaped crystals of Eu₁₁Zn₆As₁₂ were also obtained.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A plot of the Eu₁₁Zn₆As₁₂ structure viewed down the b-axis. Displacement ellipsoids are drawn at the 95% probability level. Color key: Eu - red, Zn - green, All As atoms, excluding As5 - blue. As5, which form dimers are shown in yellow. The long As5—Zn3 bonds are depicted as thiner solid lines. The unit cell is outlined.

Undecaeuropium hexazinc dodecaarsenide, Eu₁₁Zn₆As₁₂ top

Crystal data top

Eu₁₁Zn₆As₁₂	F(000) = 2538
M_r = 2962.82	D_x = 6.763 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 1796 reflections
a = 30.310 (8) Å	θ = 1.4–27.1°
b = 4.3318 (11) Å	µ = 41.68 mm⁻¹
c = 11.774 (3) Å	T = 200 K
β = 109.746 (4)°	Needle, black
V = 1455.0 (7) Å³	0.07 × 0.05 × 0.05 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	1796 independent reflections
Radiation source: fine-focus sealed tube	1498 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
ω scans	θ_max = 27.1°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −38→38
T_min = 0.161, T_max = 0.256	k = −5→5
7178 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0242P)² + 16.9522P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.062	(Δ/σ)_max < 0.001
S = 1.01	Δρ_max = 1.70 e Å⁻³
1796 reflections	Δρ_min = −1.74 e Å⁻³
90 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.000263 (17)

Crystal data top

Eu₁₁Zn₆As₁₂	V = 1455.0 (7) Å³
M_r = 2962.82	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 30.310 (8) Å	µ = 41.68 mm⁻¹
b = 4.3318 (11) Å	T = 200 K
c = 11.774 (3) Å	0.07 × 0.05 × 0.05 mm
β = 109.746 (4)°

Data collection top

Bruker SMART APEX diffractometer	1796 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1498 reflections with I > 2σ(I)
T_min = 0.161, T_max = 0.256	R_int = 0.042
7178 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.062	w = 1/[σ²(F_o²) + (0.0242P)² + 16.9522P] where P = (F_o² + 2F_c²)/3
S = 1.01	Δρ_max = 1.70 e Å⁻³
1796 reflections	Δρ_min = −1.74 e Å⁻³
90 parameters

Special details top

Experimental. Selected in the glove box, crystals were put in a Paratone N oil and cut to the desired dimensions. The chosen crystal was mounted on a tip of a glass fiber and quickly transferred onto the goniometer. The crystal was kept under a cold nitrogen stream to protect from the ambient air and moisture.

Data collection is performed with four batch runs at ϕ = 0.00 ° (600 frames), at ϕ = 90.00 ° (600 frames), at ϕ = 180.00 ° (600 frames), and at ϕ = 270.00 (600 frames). Frame width = 0.30 \& in ω. Data are merged and treated with multi-scan absorption corrections.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 (Å²) top

	x	y	z	U_iso*/U_eq
Eu1	0.01672 (2)	0.0000	0.67859 (6)	0.01461 (16)
Eu2	0.11288 (2)	0.0000	0.51100 (6)	0.01520 (16)
Eu3	0.12610 (2)	0.0000	0.02177 (6)	0.01671 (17)
Eu4	0.19815 (2)	0.0000	0.34699 (6)	0.01708 (16)
Eu5	0.28179 (2)	0.0000	0.13448 (6)	0.01841 (17)
Eu6	0.0000	0.0000	0.0000	0.0151 (2)
As1	0.08620 (4)	0.0000	0.23794 (11)	0.0139 (3)
As2	0.14491 (4)	0.0000	0.78289 (12)	0.0141 (3)
As3	0.30702 (5)	0.0000	0.45283 (12)	0.0147 (3)
As4	0.45498 (4)	0.0000	0.12128 (12)	0.0137 (3)
As5	0.45839 (4)	0.0000	0.49049 (12)	0.0139 (3)
As6	0.70775 (4)	0.0000	0.14605 (12)	0.0150 (3)
Zn1	0.21901 (6)	0.0000	0.66996 (14)	0.0204 (3)
Zn2	0.40088 (5)	0.0000	0.24844 (14)	0.0175 (3)
Zn3	0.54783 (6)	0.0000	0.23600 (16)	0.0226 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Eu1	0.0163 (3)	0.0135 (3)	0.0139 (3)	0.000	0.0050 (3)	0.000
Eu2	0.0129 (3)	0.0186 (3)	0.0146 (3)	0.000	0.0053 (3)	0.000
Eu3	0.0155 (3)	0.0209 (3)	0.0146 (4)	0.000	0.0063 (3)	0.000
Eu4	0.0142 (3)	0.0209 (3)	0.0164 (4)	0.000	0.0056 (3)	0.000
Eu5	0.0159 (3)	0.0153 (3)	0.0249 (4)	0.000	0.0080 (3)	0.000
Eu6	0.0138 (5)	0.0176 (4)	0.0142 (5)	0.000	0.0050 (4)	0.000
As1	0.0137 (6)	0.0153 (6)	0.0129 (7)	0.000	0.0048 (5)	0.000
As2	0.0145 (6)	0.0131 (6)	0.0149 (7)	0.000	0.0055 (5)	0.000
As3	0.0153 (7)	0.0135 (6)	0.0149 (7)	0.000	0.0047 (5)	0.000
As4	0.0136 (6)	0.0146 (6)	0.0135 (7)	0.000	0.0052 (5)	0.000
As5	0.0116 (6)	0.0140 (6)	0.0163 (7)	0.000	0.0050 (5)	0.000
As6	0.0129 (6)	0.0148 (6)	0.0164 (7)	0.000	0.0040 (5)	0.000
Zn1	0.0208 (8)	0.0175 (7)	0.0177 (8)	0.000	−0.0005 (7)	0.000
Zn2	0.0146 (7)	0.0165 (7)	0.0218 (8)	0.000	0.0066 (6)	0.000
Zn3	0.0197 (8)	0.0145 (7)	0.0330 (10)	0.000	0.0080 (7)	0.000

Geometric parameters (Å, º) top

Eu1—As4ⁱ	3.1006 (12)	Eu6—Zn3^viii	3.4339 (15)
Eu1—As4ⁱⁱ	3.1006 (12)	Eu6—Zn3ⁱⁱⁱ	3.4339 (15)
Eu1—As5ⁱⁱⁱ	3.1742 (12)	Eu6—Eu3^xi	3.7434 (12)
Eu1—As5^iv	3.1742 (12)	As1—Zn3ⁱⁱⁱ	2.4548 (11)
Eu1—Zn2ⁱ	3.1965 (13)	As1—Zn3^iv	2.4548 (11)
Eu1—Zn2ⁱⁱ	3.1965 (13)	As1—Eu1^v	3.5733 (16)
Eu1—As5ⁱⁱ	3.1997 (12)	As2—Zn2ⁱⁱ	2.5313 (12)
Eu1—As5ⁱ	3.1997 (12)	As2—Zn2ⁱ	2.5313 (12)
Eu1—Zn3ⁱⁱ	3.2954 (14)	As2—Zn1	2.971 (2)
Eu1—Zn3ⁱ	3.2954 (14)	As2—Eu5ⁱ	3.0187 (11)
Eu1—As1^v	3.5732 (16)	As2—Eu5ⁱⁱ	3.0187 (11)
Eu1—As2	3.6580 (17)	As2—Eu3^xii	3.0526 (16)
Eu2—As2	3.0150 (17)	As3—Zn1ⁱⁱ	2.5754 (12)
Eu2—As1	3.0386 (16)	As3—Zn1ⁱ	2.5754 (12)
Eu2—As5ⁱⁱ	3.0548 (11)	As3—Eu2ⁱ	3.1731 (12)
Eu2—As5ⁱ	3.0548 (11)	As3—Eu2ⁱⁱ	3.1731 (12)
Eu2—Zn1	3.1276 (18)	As3—Eu4ⁱ	3.2434 (12)
Eu2—As3ⁱ	3.1730 (12)	As3—Eu4ⁱⁱ	3.2434 (12)
Eu2—As3ⁱⁱ	3.1730 (12)	As4—Zn2	2.567 (2)
Eu2—Zn2ⁱ	3.6993 (15)	As4—Zn3	2.679 (2)
Eu2—Zn2ⁱⁱ	3.6993 (15)	As4—Eu1ⁱ	3.1006 (12)
Eu2—Eu4	3.7123 (11)	As4—Eu1ⁱⁱ	3.1006 (12)
Eu2—Eu1^v	3.8063 (13)	As4—Eu6^xiii	3.1477 (10)
Eu3—As2^vi	3.0526 (16)	As4—Eu6^xiv	3.1477 (10)
Eu3—As1	3.1656 (15)	As4—Eu3^vii	3.2820 (12)
Eu3—As6^iv	3.2419 (12)	As4—Eu3^viii	3.2820 (12)
Eu3—As6ⁱⁱⁱ	3.2419 (12)	As5—As5^xv	2.456 (3)
Eu3—As4^vii	3.2819 (12)	As5—Zn2	2.794 (2)
Eu3—As4^viii	3.2819 (12)	As5—Eu2ⁱⁱ	3.0548 (11)
Eu3—Zn2^vii	3.7045 (16)	As5—Eu2ⁱ	3.0548 (11)
Eu3—Zn2^viii	3.7045 (16)	As5—Eu1^xiv	3.1743 (12)
Eu3—Eu4	3.7122 (13)	As5—Eu1^xiii	3.1743 (12)
Eu3—Eu6	3.7434 (12)	As5—Eu1ⁱⁱ	3.1996 (12)
Eu3—Eu1^vi	4.2739 (13)	As5—Eu1ⁱ	3.1996 (12)
Eu3—Eu3^ix	4.3318 (11)	As6—Zn1^xv	2.524 (2)
Eu4—As3	3.1086 (16)	As6—Eu5^xiv	3.1547 (12)
Eu4—As1	3.1966 (16)	As6—Eu5^xiii	3.1547 (12)
Eu4—As3ⁱ	3.2435 (12)	As6—Eu3^xiii	3.2418 (12)
Eu4—As3ⁱⁱ	3.2435 (12)	As6—Eu3^xiv	3.2418 (12)
Eu4—As6ⁱⁱⁱ	3.2922 (13)	As6—Eu4^xiv	3.2922 (13)
Eu4—As6^iv	3.2922 (13)	As6—Eu4^xiii	3.2922 (13)
Eu4—Zn1ⁱ	3.3727 (15)	As6—Eu5^x	3.4229 (17)
Eu4—Zn1ⁱⁱ	3.3727 (15)	Zn1—As6^xv	2.524 (2)
Eu4—Zn1	3.638 (2)	Zn1—As3ⁱⁱ	2.5754 (12)
Eu4—Eu5	4.1199 (12)	Zn1—As3ⁱ	2.5754 (12)
Eu5—As2ⁱ	3.0188 (11)	Zn1—Eu5ⁱ	3.1671 (14)
Eu5—As2ⁱⁱ	3.0188 (11)	Zn1—Eu5ⁱⁱ	3.1671 (14)
Eu5—As6ⁱⁱⁱ	3.1546 (12)	Zn1—Eu4ⁱ	3.3727 (15)
Eu5—As6^iv	3.1546 (12)	Zn1—Eu4ⁱⁱ	3.3727 (15)
Eu5—Zn1ⁱ	3.1672 (14)	Zn2—As2ⁱⁱ	2.5313 (12)
Eu5—Zn1ⁱⁱ	3.1672 (14)	Zn2—As2ⁱ	2.5313 (12)
Eu5—Zn2	3.3995 (19)	Zn2—Eu1ⁱ	3.1964 (13)
Eu5—As6^x	3.4230 (17)	Zn2—Eu1ⁱⁱ	3.1964 (13)
Eu5—As3	3.5633 (18)	Zn2—Eu2ⁱ	3.6993 (15)
Eu5—Eu5^vii	3.7827 (13)	Zn2—Eu2ⁱⁱ	3.6993 (15)
Eu5—Eu5^viii	3.7827 (13)	Zn2—Eu3^vii	3.7045 (16)
Eu6—As1^xi	3.1191 (14)	Zn2—Eu3^viii	3.7045 (16)
Eu6—As1	3.1191 (14)	Zn3—As1^xiv	2.4548 (11)
Eu6—As4^vii	3.1478 (10)	Zn3—As1^xiii	2.4548 (11)
Eu6—As4^iv	3.1478 (10)	Zn3—Eu1ⁱⁱ	3.2954 (14)
Eu6—As4^viii	3.1478 (10)	Zn3—Eu1ⁱ	3.2954 (14)
Eu6—As4ⁱⁱⁱ	3.1478 (10)	Zn3—Eu6^xiii	3.4339 (15)
Eu6—Zn3^vii	3.4339 (15)	Zn3—Eu6^xiv	3.4339 (15)
Eu6—Zn3^iv	3.4339 (15)

As4ⁱ—Eu1—As4ⁱⁱ	88.62 (4)	As4^iv—Eu6—As4^viii	93.04 (4)
As4ⁱ—Eu1—As5ⁱⁱⁱ	162.32 (4)	As1^xi—Eu6—As4ⁱⁱⁱ	92.72 (3)
As4ⁱⁱ—Eu1—As5ⁱⁱⁱ	89.97 (3)	As1—Eu6—As4ⁱⁱⁱ	87.28 (3)
As4ⁱ—Eu1—As5^iv	89.97 (3)	As4^vii—Eu6—As4ⁱⁱⁱ	93.04 (4)
As4ⁱⁱ—Eu1—As5^iv	162.32 (4)	As4^iv—Eu6—As4ⁱⁱⁱ	86.96 (4)
As5ⁱⁱⁱ—Eu1—As5^iv	86.05 (4)	As4^viii—Eu6—As4ⁱⁱⁱ	180.00 (5)
As4ⁱ—Eu1—Zn2ⁱ	48.09 (4)	As1^xi—Eu6—Zn3^vii	43.67 (2)
As4ⁱⁱ—Eu1—Zn2ⁱ	106.18 (4)	As1—Eu6—Zn3^vii	136.33 (2)
As5ⁱⁱⁱ—Eu1—Zn2ⁱ	148.25 (4)	As4^vii—Eu6—Zn3^vii	47.79 (4)
As5^iv—Eu1—Zn2ⁱ	85.74 (3)	As4^iv—Eu6—Zn3^vii	132.21 (4)
As4ⁱ—Eu1—Zn2ⁱⁱ	106.18 (4)	As4^viii—Eu6—Zn3^vii	101.31 (4)
As4ⁱⁱ—Eu1—Zn2ⁱⁱ	48.09 (4)	As4ⁱⁱⁱ—Eu6—Zn3^vii	78.69 (4)
As5ⁱⁱⁱ—Eu1—Zn2ⁱⁱ	85.74 (3)	As1^xi—Eu6—Zn3^iv	136.33 (2)
As5^iv—Eu1—Zn2ⁱⁱ	148.25 (4)	As1—Eu6—Zn3^iv	43.67 (2)
Zn2ⁱ—Eu1—Zn2ⁱⁱ	85.31 (4)	As4^vii—Eu6—Zn3^iv	132.21 (4)
As4ⁱ—Eu1—As5ⁱⁱ	151.99 (4)	As4^iv—Eu6—Zn3^iv	47.79 (4)
As4ⁱⁱ—Eu1—As5ⁱⁱ	86.40 (3)	As4^viii—Eu6—Zn3^iv	78.69 (4)
As5ⁱⁱⁱ—Eu1—As5ⁱⁱ	45.32 (4)	As4ⁱⁱⁱ—Eu6—Zn3^iv	101.31 (4)
As5^iv—Eu1—As5ⁱⁱ	102.75 (3)	Zn3^vii—Eu6—Zn3^iv	180.00 (5)
Zn2ⁱ—Eu1—As5ⁱⁱ	107.39 (4)	As1^xi—Eu6—Zn3^viii	43.67 (2)
Zn2ⁱⁱ—Eu1—As5ⁱⁱ	51.79 (4)	As1—Eu6—Zn3^viii	136.33 (2)
As4ⁱ—Eu1—As5ⁱ	86.40 (3)	As4^vii—Eu6—Zn3^viii	101.31 (4)
As4ⁱⁱ—Eu1—As5ⁱ	151.99 (4)	As4^iv—Eu6—Zn3^viii	78.69 (4)
As5ⁱⁱⁱ—Eu1—As5ⁱ	102.75 (3)	As4^viii—Eu6—Zn3^viii	47.79 (4)
As5^iv—Eu1—As5ⁱ	45.32 (4)	As4ⁱⁱⁱ—Eu6—Zn3^viii	132.21 (4)
Zn2ⁱ—Eu1—As5ⁱ	51.79 (4)	Zn3^vii—Eu6—Zn3^viii	78.21 (4)
Zn2ⁱⁱ—Eu1—As5ⁱ	107.39 (4)	Zn3^iv—Eu6—Zn3^viii	101.79 (4)
As5ⁱⁱ—Eu1—As5ⁱ	85.20 (4)	As1^xi—Eu6—Zn3ⁱⁱⁱ	136.33 (2)
As4ⁱ—Eu1—Zn3ⁱⁱ	105.52 (4)	As1—Eu6—Zn3ⁱⁱⁱ	43.67 (2)
As4ⁱⁱ—Eu1—Zn3ⁱⁱ	49.41 (4)	As4^vii—Eu6—Zn3ⁱⁱⁱ	78.69 (4)
As5ⁱⁱⁱ—Eu1—Zn3ⁱⁱ	61.07 (4)	As4^iv—Eu6—Zn3ⁱⁱⁱ	101.31 (4)
As5^iv—Eu1—Zn3ⁱⁱ	114.41 (4)	As4^viii—Eu6—Zn3ⁱⁱⁱ	132.21 (4)
Zn2ⁱ—Eu1—Zn3ⁱⁱ	148.64 (5)	As4ⁱⁱⁱ—Eu6—Zn3ⁱⁱⁱ	47.79 (4)
Zn2ⁱⁱ—Eu1—Zn3ⁱⁱ	87.89 (4)	Zn3^vii—Eu6—Zn3ⁱⁱⁱ	101.79 (4)
As5ⁱⁱ—Eu1—Zn3ⁱⁱ	91.95 (3)	Zn3^iv—Eu6—Zn3ⁱⁱⁱ	78.21 (4)
As5ⁱ—Eu1—Zn3ⁱⁱ	157.49 (4)	Zn3^viii—Eu6—Zn3ⁱⁱⁱ	180.00 (8)
As4ⁱ—Eu1—Zn3ⁱ	49.41 (4)	As1^xi—Eu6—Eu3	125.98 (3)
As4ⁱⁱ—Eu1—Zn3ⁱ	105.52 (4)	As1—Eu6—Eu3	54.02 (3)
As5ⁱⁱⁱ—Eu1—Zn3ⁱ	114.41 (4)	As4^vii—Eu6—Eu3	56.08 (2)
As5^iv—Eu1—Zn3ⁱ	61.07 (4)	As4^iv—Eu6—Eu3	123.92 (2)
Zn2ⁱ—Eu1—Zn3ⁱ	87.89 (4)	As4^viii—Eu6—Eu3	56.08 (2)
Zn2ⁱⁱ—Eu1—Zn3ⁱ	148.64 (5)	As4ⁱⁱⁱ—Eu6—Eu3	123.92 (2)
As5ⁱⁱ—Eu1—Zn3ⁱ	157.49 (4)	Zn3^vii—Eu6—Eu3	101.40 (3)
As5ⁱ—Eu1—Zn3ⁱ	91.95 (3)	Zn3^iv—Eu6—Eu3	78.60 (3)
Zn3ⁱⁱ—Eu1—Zn3ⁱ	82.18 (4)	Zn3^viii—Eu6—Eu3	101.40 (3)
As4ⁱ—Eu1—As1^v	80.45 (3)	Zn3ⁱⁱⁱ—Eu6—Eu3	78.60 (3)
As4ⁱⁱ—Eu1—As1^v	80.45 (3)	As1^xi—Eu6—Eu3^xi	54.02 (3)
As5ⁱⁱⁱ—Eu1—As1^v	81.93 (3)	As1—Eu6—Eu3^xi	125.98 (3)
As5^iv—Eu1—As1^v	81.93 (3)	As4^vii—Eu6—Eu3^xi	123.92 (2)
Zn2ⁱ—Eu1—As1^v	126.98 (3)	As4^iv—Eu6—Eu3^xi	56.08 (2)
Zn2ⁱⁱ—Eu1—As1^v	126.98 (3)	As4^viii—Eu6—Eu3^xi	123.92 (2)
As5ⁱⁱ—Eu1—As1^v	125.62 (3)	As4ⁱⁱⁱ—Eu6—Eu3^xi	56.08 (2)
As5ⁱ—Eu1—As1^v	125.62 (3)	Zn3^vii—Eu6—Eu3^xi	78.60 (3)
Zn3ⁱⁱ—Eu1—As1^v	41.63 (2)	Zn3^iv—Eu6—Eu3^xi	101.40 (3)
Zn3ⁱ—Eu1—As1^v	41.63 (2)	Zn3^viii—Eu6—Eu3^xi	78.60 (3)
As4ⁱ—Eu1—As2	75.82 (3)	Zn3ⁱⁱⁱ—Eu6—Eu3^xi	101.40 (3)
As4ⁱⁱ—Eu1—As2	75.82 (3)	Eu3—Eu6—Eu3^xi	180.0
As5ⁱⁱⁱ—Eu1—As2	120.82 (3)	Zn3ⁱⁱⁱ—As1—Zn3^iv	123.85 (9)
As5^iv—Eu1—As2	120.82 (3)	Zn3ⁱⁱⁱ—As1—Eu2	88.04 (5)
Zn2ⁱ—Eu1—As2	42.68 (2)	Zn3^iv—As1—Eu2	88.04 (5)
Zn2ⁱⁱ—Eu1—As2	42.68 (2)	Zn3ⁱⁱⁱ—As1—Eu6	75.00 (5)
As5ⁱⁱ—Eu1—As2	76.23 (3)	Zn3^iv—As1—Eu6	75.00 (5)
As5ⁱ—Eu1—As2	76.23 (3)	Eu2—As1—Eu6	142.47 (5)
Zn3ⁱⁱ—Eu1—As2	124.78 (3)	Zn3ⁱⁱⁱ—As1—Eu3	107.52 (5)
Zn3ⁱ—Eu1—As2	124.78 (3)	Zn3^iv—As1—Eu3	107.52 (5)
As1^v—Eu1—As2	146.58 (4)	Eu2—As1—Eu3	144.42 (5)
As2—Eu2—As1	176.86 (4)	Eu6—As1—Eu3	73.11 (4)
As2—Eu2—As5ⁱⁱ	88.83 (3)	Zn3ⁱⁱⁱ—As1—Eu4	116.04 (4)
As1—Eu2—As5ⁱⁱ	93.38 (3)	Zn3^iv—As1—Eu4	116.04 (4)
As2—Eu2—As5ⁱ	88.83 (3)	Eu2—As1—Eu4	73.03 (3)
As1—Eu2—As5ⁱ	93.38 (3)	Eu6—As1—Eu4	144.50 (5)
As5ⁱⁱ—Eu2—As5ⁱ	90.31 (4)	Eu3—As1—Eu4	71.39 (3)
As2—Eu2—Zn1	57.82 (4)	Zn3ⁱⁱⁱ—As1—Eu1^v	63.11 (4)
As1—Eu2—Zn1	119.04 (4)	Zn3^iv—As1—Eu1^v	63.11 (4)
As5ⁱⁱ—Eu2—Zn1	125.86 (3)	Eu2—As1—Eu1^v	69.76 (3)
As5ⁱ—Eu2—Zn1	125.86 (3)	Eu6—As1—Eu1^v	72.71 (3)
As2—Eu2—As3ⁱ	84.27 (3)	Eu3—As1—Eu1^v	145.82 (4)
As1—Eu2—As3ⁱ	93.44 (3)	Eu4—As1—Eu1^v	142.79 (5)
As5ⁱⁱ—Eu2—As3ⁱ	172.86 (4)	Zn2ⁱⁱ—As2—Zn2ⁱ	117.67 (8)
As5ⁱ—Eu2—As3ⁱ	91.39 (3)	Zn2ⁱⁱ—As2—Zn1	113.26 (5)
Zn1—Eu2—As3ⁱ	48.25 (3)	Zn2ⁱ—As2—Zn1	113.26 (5)
As2—Eu2—As3ⁱⁱ	84.27 (3)	Zn2ⁱⁱ—As2—Eu2	83.18 (5)
As1—Eu2—As3ⁱⁱ	93.44 (3)	Zn2ⁱ—As2—Eu2	83.18 (5)
As5ⁱⁱ—Eu2—As3ⁱⁱ	91.39 (3)	Zn1—As2—Eu2	62.99 (4)
As5ⁱ—Eu2—As3ⁱⁱ	172.86 (4)	Zn2ⁱⁱ—As2—Eu5ⁱ	165.57 (6)
Zn1—Eu2—As3ⁱⁱ	48.25 (3)	Zn2ⁱ—As2—Eu5ⁱ	74.97 (4)
As3ⁱ—Eu2—As3ⁱⁱ	86.09 (4)	Zn1—As2—Eu5ⁱ	63.83 (3)
As2—Eu2—Zn2ⁱ	42.80 (3)	Eu2—As2—Eu5ⁱ	106.27 (4)
As1—Eu2—Zn2ⁱ	138.72 (3)	Zn2ⁱⁱ—As2—Eu5ⁱⁱ	74.97 (4)
As5ⁱⁱ—Eu2—Zn2ⁱ	99.04 (4)	Zn2ⁱ—As2—Eu5ⁱⁱ	165.57 (6)
As5ⁱ—Eu2—Zn2ⁱ	47.69 (3)	Zn1—As2—Eu5ⁱⁱ	63.83 (3)
Zn1—Eu2—Zn2ⁱ	84.32 (4)	Eu2—As2—Eu5ⁱⁱ	106.27 (4)
As3ⁱ—Eu2—Zn2ⁱ	77.09 (3)	Eu5ⁱ—As2—Eu5ⁱⁱ	91.70 (4)
As3ⁱⁱ—Eu2—Zn2ⁱ	125.16 (4)	Zn2ⁱⁱ—As2—Eu3^xii	82.55 (5)
As2—Eu2—Zn2ⁱⁱ	42.80 (3)	Zn2ⁱ—As2—Eu3^xii	82.55 (5)
As1—Eu2—Zn2ⁱⁱ	138.72 (3)	Zn1—As2—Eu3^xii	144.78 (6)
As5ⁱⁱ—Eu2—Zn2ⁱⁱ	47.69 (3)	Eu2—As2—Eu3^xii	152.23 (5)
As5ⁱ—Eu2—Zn2ⁱⁱ	99.04 (4)	Eu5ⁱ—As2—Eu3^xii	92.82 (4)
Zn1—Eu2—Zn2ⁱⁱ	84.32 (4)	Eu5ⁱⁱ—As2—Eu3^xii	92.82 (4)
As3ⁱ—Eu2—Zn2ⁱⁱ	125.16 (4)	Zn2ⁱⁱ—As2—Eu1	58.88 (4)
As3ⁱⁱ—Eu2—Zn2ⁱⁱ	77.09 (3)	Zn2ⁱ—As2—Eu1	58.88 (4)
Zn2ⁱ—Eu2—Zn2ⁱⁱ	71.68 (4)	Zn1—As2—Eu1	136.67 (6)
As2—Eu2—Eu4	121.41 (4)	Eu2—As2—Eu1	73.68 (3)
As1—Eu2—Eu4	55.45 (3)	Eu5ⁱ—As2—Eu1	133.69 (2)
As5ⁱⁱ—Eu2—Eu4	127.75 (3)	Eu5ⁱⁱ—As2—Eu1	133.69 (2)
As5ⁱ—Eu2—Eu4	127.75 (3)	Eu3^xii—As2—Eu1	78.55 (3)
Zn1—Eu2—Eu4	63.59 (4)	Zn1ⁱⁱ—As3—Zn1ⁱ	114.49 (8)
As3ⁱ—Eu2—Eu4	55.54 (3)	Zn1ⁱⁱ—As3—Eu4	72.10 (5)
As3ⁱⁱ—Eu2—Eu4	55.54 (3)	Zn1ⁱ—As3—Eu4	72.10 (5)
Zn2ⁱ—Eu2—Eu4	132.58 (3)	Zn1ⁱⁱ—As3—Eu2ⁱ	136.45 (6)
Zn2ⁱⁱ—Eu2—Eu4	132.58 (3)	Zn1ⁱ—As3—Eu2ⁱ	64.95 (4)
As2—Eu2—Eu1^v	121.40 (3)	Eu4—As3—Eu2ⁱ	135.58 (2)
As1—Eu2—Eu1^v	61.74 (3)	Zn1ⁱⁱ—As3—Eu2ⁱⁱ	64.95 (4)
As5ⁱⁱ—Eu2—Eu1^v	53.77 (3)	Zn1ⁱ—As3—Eu2ⁱⁱ	136.45 (6)
As5ⁱ—Eu2—Eu1^v	53.77 (3)	Eu4—As3—Eu2ⁱⁱ	135.58 (2)
Zn1—Eu2—Eu1^v	179.22 (4)	Eu2ⁱ—As3—Eu2ⁱⁱ	86.09 (4)
As3ⁱ—Eu2—Eu1^v	132.06 (2)	Zn1ⁱⁱ—As3—Eu4ⁱ	152.71 (6)
As3ⁱⁱ—Eu2—Eu1^v	132.06 (2)	Zn1ⁱ—As3—Eu4ⁱ	76.44 (4)
Zn2ⁱ—Eu2—Eu1^v	95.05 (3)	Eu4—As3—Eu4ⁱ	89.20 (3)
Zn2ⁱⁱ—Eu2—Eu1^v	95.05 (3)	Eu2ⁱ—As3—Eu4ⁱ	70.69 (2)
Eu4—Eu2—Eu1^v	117.19 (3)	Eu2ⁱⁱ—As3—Eu4ⁱ	125.51 (5)
As2—Eu2—Eu1	60.49 (3)	Zn1ⁱⁱ—As3—Eu4ⁱⁱ	76.44 (4)
As1—Eu2—Eu1	122.65 (3)	Zn1ⁱ—As3—Eu4ⁱⁱ	152.71 (6)
As5ⁱⁱ—Eu2—Eu1	51.43 (2)	Eu4—As3—Eu4ⁱⁱ	89.20 (3)
As5ⁱ—Eu2—Eu1	51.43 (2)	Eu2ⁱ—As3—Eu4ⁱⁱ	125.51 (5)
Zn1—Eu2—Eu1	118.31 (4)	Eu2ⁱⁱ—As3—Eu4ⁱⁱ	70.69 (2)
As3ⁱ—Eu2—Eu1	125.51 (3)	Eu4ⁱ—As3—Eu4ⁱⁱ	83.79 (4)
As3ⁱⁱ—Eu2—Eu1	125.51 (3)	Zn1ⁱⁱ—As3—Eu5	59.56 (4)
Zn2ⁱ—Eu2—Eu1	48.59 (2)	Zn1ⁱ—As3—Eu5	59.56 (4)
Zn2ⁱⁱ—Eu2—Eu1	48.59 (2)	Eu4—As3—Eu5	75.93 (3)
Eu4—Eu2—Eu1	178.10 (2)	Eu2ⁱ—As3—Eu5	91.36 (3)
Eu1^v—Eu2—Eu1	60.91 (3)	Eu2ⁱⁱ—As3—Eu5	91.36 (3)
As2^vi—Eu3—As1	169.05 (4)	Eu4ⁱ—As3—Eu5	135.93 (2)
As2^vi—Eu3—As6^iv	93.68 (3)	Eu4ⁱⁱ—As3—Eu5	135.93 (2)
As1—Eu3—As6^iv	94.47 (4)	Zn2—As4—Zn3	118.37 (7)
As2^vi—Eu3—As6ⁱⁱⁱ	93.68 (3)	Zn2—As4—Eu1ⁱ	67.91 (4)
As1—Eu3—As6ⁱⁱⁱ	94.47 (4)	Zn3—As4—Eu1ⁱ	69.09 (4)
As6^iv—Eu3—As6ⁱⁱⁱ	83.84 (4)	Zn2—As4—Eu1ⁱⁱ	67.91 (4)
As2^vi—Eu3—As4^vii	82.40 (3)	Zn3—As4—Eu1ⁱⁱ	69.09 (4)
As1—Eu3—As4^vii	89.39 (4)	Eu1ⁱ—As4—Eu1ⁱⁱ	88.62 (4)
As6^iv—Eu3—As4^vii	176.07 (4)	Zn2—As4—Eu6^xiii	136.452 (19)
As6ⁱⁱⁱ—Eu3—As4^vii	96.65 (3)	Zn3—As4—Eu6^xiii	71.71 (4)
As2^vi—Eu3—As4^viii	82.40 (3)	Eu1ⁱ—As4—Eu6^xiii	140.75 (5)
As1—Eu3—As4^viii	89.39 (4)	Eu1ⁱⁱ—As4—Eu6^xiii	79.23 (2)
As6^iv—Eu3—As4^viii	96.65 (3)	Zn2—As4—Eu6^xiv	136.452 (19)
As6ⁱⁱⁱ—Eu3—As4^viii	176.07 (4)	Zn3—As4—Eu6^xiv	71.71 (4)
As4^vii—Eu3—As4^viii	82.59 (4)	Eu1ⁱ—As4—Eu6^xiv	79.23 (2)
As2^vi—Eu3—Zn2^vii	42.65 (3)	Eu1ⁱⁱ—As4—Eu6^xiv	140.75 (5)
As1—Eu3—Zn2^vii	131.07 (3)	Eu6^xiii—As4—Eu6^xiv	86.96 (4)
As6^iv—Eu3—Zn2^vii	133.76 (4)	Zn2—As4—Eu3^vii	77.53 (4)
As6ⁱⁱⁱ—Eu3—Zn2^vii	84.86 (3)	Zn3—As4—Eu3^vii	137.37 (2)
As4^vii—Eu3—Zn2^vii	42.58 (3)	Eu1ⁱ—As4—Eu3^vii	144.88 (5)
As4^viii—Eu3—Zn2^vii	92.03 (3)	Eu1ⁱⁱ—As4—Eu3^vii	84.03 (2)
As2^vi—Eu3—Zn2^viii	42.65 (3)	Eu6^xiii—As4—Eu3^vii	71.18 (3)
As1—Eu3—Zn2^viii	131.07 (3)	Eu6^xiv—As4—Eu3^vii	125.84 (5)
As6^iv—Eu3—Zn2^viii	84.86 (3)	Zn2—As4—Eu3^viii	77.53 (4)
As6ⁱⁱⁱ—Eu3—Zn2^viii	133.76 (4)	Zn3—As4—Eu3^viii	137.37 (2)
As4^vii—Eu3—Zn2^viii	92.03 (3)	Eu1ⁱ—As4—Eu3^viii	84.03 (2)
As4^viii—Eu3—Zn2^viii	42.58 (3)	Eu1ⁱⁱ—As4—Eu3^viii	144.88 (5)
Zn2^vii—Eu3—Zn2^viii	71.56 (4)	Eu6^xiii—As4—Eu3^viii	125.84 (5)
As2^vi—Eu3—Eu4	136.26 (4)	Eu6^xiv—As4—Eu3^viii	71.18 (3)
As1—Eu3—Eu4	54.69 (3)	Eu3^vii—As4—Eu3^viii	82.59 (4)
As6^iv—Eu3—Eu4	56.02 (2)	As5^xv—As5—Zn2	111.14 (8)
As6ⁱⁱⁱ—Eu3—Eu4	56.02 (2)	As5^xv—As5—Eu2ⁱⁱ	134.67 (2)
As4^vii—Eu3—Eu4	127.36 (3)	Zn2—As5—Eu2ⁱⁱ	78.34 (4)
As4^viii—Eu3—Eu4	127.36 (3)	As5^xv—As5—Eu2ⁱ	134.67 (2)
Zn2^vii—Eu3—Eu4	140.18 (2)	Zn2—As5—Eu2ⁱ	78.34 (4)
Zn2^viii—Eu3—Eu4	140.18 (2)	Eu2ⁱⁱ—As5—Eu2ⁱ	90.31 (4)
As2^vi—Eu3—Eu6	116.17 (3)	As5^xv—As5—Eu1^xiv	67.89 (4)
As1—Eu3—Eu6	52.87 (3)	Zn2—As5—Eu1^xiv	136.08 (2)
As6^iv—Eu3—Eu6	129.57 (2)	Eu2ⁱⁱ—As5—Eu1^xiv	135.55 (5)
As6ⁱⁱⁱ—Eu3—Eu6	129.57 (3)	Eu2ⁱ—As5—Eu1^xiv	75.31 (3)
As4^vii—Eu3—Eu6	52.74 (2)	As5^xv—As5—Eu1^xiii	67.89 (4)
As4^viii—Eu3—Eu6	52.74 (2)	Zn2—As5—Eu1^xiii	136.08 (2)
Zn2^vii—Eu3—Eu6	90.98 (3)	Eu2ⁱⁱ—As5—Eu1^xiii	75.31 (3)
Zn2^viii—Eu3—Eu6	90.98 (3)	Eu2ⁱ—As5—Eu1^xiii	135.55 (5)
Eu4—Eu3—Eu6	107.57 (2)	Eu1^xiv—As5—Eu1^xiii	86.05 (4)
As2^vi—Eu3—Eu1^vi	57.02 (3)	As5^xv—As5—Eu1ⁱⁱ	66.79 (4)
As1—Eu3—Eu1^vi	112.03 (4)	Zn2—As5—Eu1ⁱⁱ	64.04 (4)
As6^iv—Eu3—Eu1^vi	131.05 (2)	Eu2ⁱⁱ—As5—Eu1ⁱⁱ	80.29 (2)
As6ⁱⁱⁱ—Eu3—Eu1^vi	131.05 (2)	Eu2ⁱ—As5—Eu1ⁱⁱ	142.30 (5)
As4^vii—Eu3—Eu1^vi	46.18 (2)	Eu1^xiv—As5—Eu1ⁱⁱ	134.68 (4)
As4^viii—Eu3—Eu1^vi	46.18 (2)	Eu1^xiii—As5—Eu1ⁱⁱ	77.25 (3)
Zn2^vii—Eu3—Eu1^vi	46.56 (2)	As5^xv—As5—Eu1ⁱ	66.79 (4)
Zn2^viii—Eu3—Eu1^vi	46.56 (2)	Zn2—As5—Eu1ⁱ	64.04 (4)
Eu4—Eu3—Eu1^vi	166.72 (2)	Eu2ⁱⁱ—As5—Eu1ⁱ	142.30 (5)
Eu6—Eu3—Eu1^vi	59.155 (18)	Eu2ⁱ—As5—Eu1ⁱ	80.29 (2)
As2^vi—Eu3—Eu3^ix	90.0	Eu1^xiv—As5—Eu1ⁱ	77.25 (3)
As1—Eu3—Eu3^ix	90.0	Eu1^xiii—As5—Eu1ⁱ	134.68 (4)
As6^iv—Eu3—Eu3^ix	48.08 (2)	Eu1ⁱⁱ—As5—Eu1ⁱ	85.21 (4)
As6ⁱⁱⁱ—Eu3—Eu3^ix	131.919 (19)	Zn1^xv—As6—Eu5^xiv	66.73 (4)
As4^vii—Eu3—Eu3^ix	131.297 (19)	Zn1^xv—As6—Eu5^xiii	66.73 (4)
As4^viii—Eu3—Eu3^ix	48.705 (19)	Eu5^xiv—As6—Eu5^xiii	86.72 (4)
Zn2^vii—Eu3—Eu3^ix	125.780 (18)	Zn1^xv—As6—Eu3^xiii	134.69 (3)
Zn2^viii—Eu3—Eu3^ix	54.221 (18)	Eu5^xiv—As6—Eu3^xiii	152.24 (5)
Eu4—Eu3—Eu3^ix	90.0	Eu5^xiii—As6—Eu3^xiii	88.14 (3)
Eu6—Eu3—Eu3^ix	90.001 (1)	Zn1^xv—As6—Eu3^xiv	134.69 (3)
Eu1^vi—Eu3—Eu3^ix	90.0	Eu5^xiv—As6—Eu3^xiv	88.14 (3)
As3—Eu4—As1	179.95 (4)	Eu5^xiii—As6—Eu3^xiv	152.24 (5)
As3—Eu4—As3ⁱ	90.81 (3)	Eu3^xiii—As6—Eu3^xiv	83.84 (4)
As1—Eu4—As3ⁱ	89.23 (3)	Zn1^xv—As6—Eu4^xiv	69.45 (4)
As3—Eu4—As3ⁱⁱ	90.81 (3)	Eu5^xiv—As6—Eu4^xiv	79.41 (2)
As1—Eu4—As3ⁱⁱ	89.23 (3)	Eu5^xiii—As6—Eu4^xiv	136.02 (5)
As3ⁱ—Eu4—As3ⁱⁱ	83.79 (4)	Eu3^xiii—As6—Eu4^xiv	121.64 (4)
As3—Eu4—As6ⁱⁱⁱ	87.04 (3)	Eu3^xiv—As6—Eu4^xiv	69.23 (3)
As1—Eu4—As6ⁱⁱⁱ	92.92 (3)	Zn1^xv—As6—Eu4^xiii	69.45 (4)
As3ⁱ—Eu4—As6ⁱⁱⁱ	177.74 (4)	Eu5^xiv—As6—Eu4^xiii	136.02 (5)
As3ⁱⁱ—Eu4—As6ⁱⁱⁱ	96.93 (3)	Eu5^xiii—As6—Eu4^xiii	79.41 (2)
As3—Eu4—As6^iv	87.04 (3)	Eu3^xiii—As6—Eu4^xiii	69.23 (3)
As1—Eu4—As6^iv	92.92 (3)	Eu3^xiv—As6—Eu4^xiii	121.64 (4)
As3ⁱ—Eu4—As6^iv	96.93 (3)	Eu4^xiv—As6—Eu4^xiii	82.28 (4)
As3ⁱⁱ—Eu4—As6^iv	177.74 (4)	Zn1^xv—As6—Eu5^x	119.13 (6)
As6ⁱⁱⁱ—Eu4—As6^iv	82.28 (4)	Eu5^xiv—As6—Eu5^x	70.08 (3)
As3—Eu4—Zn1ⁱ	46.61 (3)	Eu5^xiii—As6—Eu5^x	70.08 (3)
As1—Eu4—Zn1ⁱ	133.37 (3)	Eu3^xiii—As6—Eu5^x	82.52 (3)
As3ⁱ—Eu4—Zn1ⁱ	80.44 (3)	Eu3^xiv—As6—Eu5^x	82.52 (3)
As3ⁱⁱ—Eu4—Zn1ⁱ	133.75 (4)	Eu4^xiv—As6—Eu5^x	138.84 (2)
As6ⁱⁱⁱ—Eu4—Zn1ⁱ	97.56 (4)	Eu4^xiii—As6—Eu5^x	138.844 (19)
As6^iv—Eu4—Zn1ⁱ	44.49 (3)	As6^xv—Zn1—As3ⁱⁱ	119.71 (4)
As3—Eu4—Zn1ⁱⁱ	46.61 (3)	As6^xv—Zn1—As3ⁱ	119.71 (4)
As1—Eu4—Zn1ⁱⁱ	133.37 (3)	As3ⁱⁱ—Zn1—As3ⁱ	114.49 (8)
As3ⁱ—Eu4—Zn1ⁱⁱ	133.75 (4)	As6^xv—Zn1—As2	101.21 (7)
As3ⁱⁱ—Eu4—Zn1ⁱⁱ	80.44 (3)	As3ⁱⁱ—Zn1—As2	96.70 (5)
As6ⁱⁱⁱ—Eu4—Zn1ⁱⁱ	44.49 (3)	As3ⁱ—Zn1—As2	96.70 (5)
As6^iv—Eu4—Zn1ⁱⁱ	97.56 (4)	As6^xv—Zn1—Eu2	160.40 (7)
Zn1ⁱ—Eu4—Zn1ⁱⁱ	79.91 (4)	As3ⁱⁱ—Zn1—Eu2	66.80 (4)
As3—Eu4—Zn1	78.17 (4)	As3ⁱ—Zn1—Eu2	66.80 (4)
As1—Eu4—Zn1	101.88 (4)	As2—Zn1—Eu2	59.19 (5)
As3ⁱ—Eu4—Zn1	43.49 (2)	As6^xv—Zn1—Eu5ⁱ	66.21 (4)
As3ⁱⁱ—Eu4—Zn1	43.49 (2)	As3ⁱⁱ—Zn1—Eu5ⁱ	155.11 (7)
As6ⁱⁱⁱ—Eu4—Zn1	136.45 (2)	As3ⁱ—Zn1—Eu5ⁱ	75.93 (4)
As6^iv—Eu4—Zn1	136.45 (2)	As2—Zn1—Eu5ⁱ	58.81 (3)
Zn1ⁱ—Eu4—Zn1	101.07 (4)	Eu2—Zn1—Eu5ⁱ	100.14 (4)
Zn1ⁱⁱ—Eu4—Zn1	101.07 (4)	As6^xv—Zn1—Eu5ⁱⁱ	66.21 (4)
As3—Eu4—Eu3	126.04 (3)	As3ⁱⁱ—Zn1—Eu5ⁱⁱ	75.93 (4)
As1—Eu4—Eu3	53.92 (3)	As3ⁱ—Zn1—Eu5ⁱⁱ	155.11 (7)
As3ⁱ—Eu4—Eu3	126.41 (3)	As2—Zn1—Eu5ⁱⁱ	58.81 (3)
As3ⁱⁱ—Eu4—Eu3	126.41 (3)	Eu2—Zn1—Eu5ⁱⁱ	100.14 (4)
As6ⁱⁱⁱ—Eu4—Eu3	54.74 (3)	Eu5ⁱ—Zn1—Eu5ⁱⁱ	86.29 (5)
As6^iv—Eu4—Eu3	54.74 (3)	As6^xv—Zn1—Eu4ⁱ	66.06 (4)
Zn1ⁱ—Eu4—Eu3	97.42 (3)	As3ⁱⁱ—Zn1—Eu4ⁱ	126.86 (7)
Zn1ⁱⁱ—Eu4—Eu3	97.42 (3)	As3ⁱ—Zn1—Eu4ⁱ	61.30 (4)
Zn1—Eu4—Eu3	155.80 (3)	As2—Zn1—Eu4ⁱ	135.80 (3)
As3—Eu4—Eu2	128.52 (4)	Eu2—Zn1—Eu4ⁱ	126.90 (4)
As1—Eu4—Eu2	51.53 (3)	Eu5ⁱ—Zn1—Eu4ⁱ	78.03 (3)
As3ⁱ—Eu4—Eu2	53.77 (2)	Eu5ⁱⁱ—Zn1—Eu4ⁱ	132.14 (5)
As3ⁱⁱ—Eu4—Eu2	53.77 (2)	As6^xv—Zn1—Eu4ⁱⁱ	66.06 (4)
As6ⁱⁱⁱ—Eu4—Eu2	128.31 (3)	As3ⁱⁱ—Zn1—Eu4ⁱⁱ	61.30 (4)
As6^iv—Eu4—Eu2	128.31 (3)	As3ⁱ—Zn1—Eu4ⁱⁱ	126.86 (7)
Zn1ⁱ—Eu4—Eu2	133.94 (3)	As2—Zn1—Eu4ⁱⁱ	135.80 (3)
Zn1ⁱⁱ—Eu4—Eu2	133.94 (3)	Eu2—Zn1—Eu4ⁱⁱ	126.90 (4)
Zn1—Eu4—Eu2	50.35 (3)	Eu5ⁱ—Zn1—Eu4ⁱⁱ	132.14 (5)
Eu3—Eu4—Eu2	105.44 (3)	Eu5ⁱⁱ—Zn1—Eu4ⁱⁱ	78.03 (3)
As3—Eu4—Eu5	57.03 (3)	Eu4ⁱ—Zn1—Eu4ⁱⁱ	79.91 (4)
As1—Eu4—Eu5	122.92 (3)	As6^xv—Zn1—Eu4	133.54 (7)
As3ⁱ—Eu4—Eu5	129.20 (3)	As3ⁱⁱ—Zn1—Eu4	60.08 (4)
As3ⁱⁱ—Eu4—Eu5	129.20 (3)	As3ⁱ—Zn1—Eu4	60.08 (4)
As6ⁱⁱⁱ—Eu4—Eu5	48.82 (2)	As2—Zn1—Eu4	125.24 (6)
As6^iv—Eu4—Eu5	48.82 (2)	Eu2—Zn1—Eu4	66.06 (3)
Zn1ⁱ—Eu4—Eu5	48.77 (3)	Eu5ⁱ—Zn1—Eu4	135.94 (3)
Zn1ⁱⁱ—Eu4—Eu5	48.77 (3)	Eu5ⁱⁱ—Zn1—Eu4	135.94 (3)
Zn1—Eu4—Eu5	135.20 (3)	Eu4ⁱ—Zn1—Eu4	78.93 (4)
Eu3—Eu4—Eu5	69.01 (3)	Eu4ⁱⁱ—Zn1—Eu4	78.93 (4)
Eu2—Eu4—Eu5	174.45 (2)	As2ⁱⁱ—Zn2—As2ⁱ	117.66 (8)
As2ⁱ—Eu5—As2ⁱⁱ	91.69 (4)	As2ⁱⁱ—Zn2—As4	109.99 (5)
As2ⁱ—Eu5—As6ⁱⁱⁱ	159.31 (4)	As2ⁱ—Zn2—As4	109.99 (5)
As2ⁱⁱ—Eu5—As6ⁱⁱⁱ	87.15 (3)	As2ⁱⁱ—Zn2—As5	105.73 (5)
As2ⁱ—Eu5—As6^iv	87.15 (3)	As2ⁱ—Zn2—As5	105.73 (5)
As2ⁱⁱ—Eu5—As6^iv	159.31 (4)	As4—Zn2—As5	107.07 (7)
As6ⁱⁱⁱ—Eu5—As6^iv	86.72 (4)	As2ⁱⁱ—Zn2—Eu1ⁱ	163.56 (6)
As2ⁱ—Eu5—Zn1ⁱ	57.36 (4)	As2ⁱ—Zn2—Eu1ⁱ	78.43 (3)
As2ⁱⁱ—Eu5—Zn1ⁱ	116.22 (4)	As4—Zn2—Eu1ⁱ	64.00 (4)
As6ⁱⁱⁱ—Eu5—Zn1ⁱ	104.95 (4)	As5—Zn2—Eu1ⁱ	64.16 (4)
As6^iv—Eu5—Zn1ⁱ	47.06 (4)	As2ⁱⁱ—Zn2—Eu1ⁱⁱ	78.43 (3)
As2ⁱ—Eu5—Zn1ⁱⁱ	116.22 (4)	As2ⁱ—Zn2—Eu1ⁱⁱ	163.56 (6)
As2ⁱⁱ—Eu5—Zn1ⁱⁱ	57.36 (4)	As4—Zn2—Eu1ⁱⁱ	64.00 (4)
As6ⁱⁱⁱ—Eu5—Zn1ⁱⁱ	47.06 (4)	As5—Zn2—Eu1ⁱⁱ	64.16 (4)
As6^iv—Eu5—Zn1ⁱⁱ	104.95 (4)	Eu1ⁱ—Zn2—Eu1ⁱⁱ	85.31 (4)
Zn1ⁱ—Eu5—Zn1ⁱⁱ	86.29 (5)	As2ⁱⁱ—Zn2—Eu5	59.05 (4)
As2ⁱ—Eu5—Zn2	45.98 (2)	As2ⁱ—Zn2—Eu5	59.05 (4)
As2ⁱⁱ—Eu5—Zn2	45.98 (2)	As4—Zn2—Eu5	124.90 (7)
As6ⁱⁱⁱ—Eu5—Zn2	131.21 (3)	As5—Zn2—Eu5	128.03 (6)
As6^iv—Eu5—Zn2	131.21 (3)	Eu1ⁱ—Zn2—Eu5	137.32 (2)
Zn1ⁱ—Eu5—Zn2	88.91 (4)	Eu1ⁱⁱ—Zn2—Eu5	137.32 (2)
Zn1ⁱⁱ—Eu5—Zn2	88.91 (4)	As2ⁱⁱ—Zn2—Eu2ⁱ	114.49 (6)
As2ⁱ—Eu5—As6^x	90.74 (3)	As2ⁱ—Zn2—Eu2ⁱ	54.02 (4)
As2ⁱⁱ—Eu5—As6^x	90.74 (3)	As4—Zn2—Eu2ⁱ	134.91 (4)
As6ⁱⁱⁱ—Eu5—As6^x	109.93 (3)	As5—Zn2—Eu2ⁱ	53.97 (3)
As6^iv—Eu5—As6^x	109.93 (3)	Eu1ⁱ—Zn2—Eu2ⁱ	71.18 (3)
Zn1ⁱ—Eu5—As6^x	136.67 (2)	Eu1ⁱⁱ—Zn2—Eu2ⁱ	118.09 (5)
Zn1ⁱⁱ—Eu5—As6^x	136.67 (2)	Eu5—Zn2—Eu2ⁱ	85.58 (3)
Zn2—Eu5—As6^x	87.06 (4)	As2ⁱⁱ—Zn2—Eu2ⁱⁱ	54.02 (4)
As2ⁱ—Eu5—As3	77.76 (3)	As2ⁱ—Zn2—Eu2ⁱⁱ	114.49 (6)
As2ⁱⁱ—Eu5—As3	77.76 (3)	As4—Zn2—Eu2ⁱⁱ	134.91 (4)
As6ⁱⁱⁱ—Eu5—As3	81.81 (3)	As5—Zn2—Eu2ⁱⁱ	53.97 (3)
As6^iv—Eu5—As3	81.81 (3)	Eu1ⁱ—Zn2—Eu2ⁱⁱ	118.09 (5)
Zn1ⁱ—Eu5—As3	44.51 (2)	Eu1ⁱⁱ—Zn2—Eu2ⁱⁱ	71.18 (3)
Zn1ⁱⁱ—Eu5—As3	44.51 (2)	Eu5—Zn2—Eu2ⁱⁱ	85.58 (3)
Zn2—Eu5—As3	76.28 (4)	Eu2ⁱ—Zn2—Eu2ⁱⁱ	71.68 (4)
As6^x—Eu5—As3	163.35 (4)	As2ⁱⁱ—Zn2—Eu3^vii	54.79 (4)
As2ⁱ—Eu5—Eu5^vii	142.36 (4)	As2ⁱ—Zn2—Eu3^vii	115.09 (6)
As2ⁱⁱ—Eu5—Eu5^vii	88.30 (3)	As4—Zn2—Eu3^vii	59.89 (4)
As6ⁱⁱⁱ—Eu5—Eu5^vii	58.29 (3)	As5—Zn2—Eu3^vii	139.18 (3)
As6^iv—Eu5—Eu5^vii	105.11 (4)	Eu1ⁱ—Zn2—Eu3^vii	123.56 (5)
Zn1ⁱ—Eu5—Eu5^vii	150.85 (4)	Eu1ⁱⁱ—Zn2—Eu3^vii	76.14 (3)
Zn1ⁱⁱ—Eu5—Eu5^vii	95.17 (3)	Eu5—Zn2—Eu3^vii	76.36 (3)
Zn2—Eu5—Eu5^vii	120.20 (3)	Eu2ⁱ—Zn2—Eu3^vii	161.91 (5)
As6^x—Eu5—Eu5^vii	51.63 (3)	Eu2ⁱⁱ—Zn2—Eu3^vii	105.42 (2)
As3—Eu5—Eu5^vii	138.43 (2)	As2ⁱⁱ—Zn2—Eu3^viii	115.09 (6)
As2ⁱ—Eu5—Eu5^viii	88.30 (3)	As2ⁱ—Zn2—Eu3^viii	54.79 (4)
As2ⁱⁱ—Eu5—Eu5^viii	142.36 (4)	As4—Zn2—Eu3^viii	59.89 (4)
As6ⁱⁱⁱ—Eu5—Eu5^viii	105.11 (4)	As5—Zn2—Eu3^viii	139.18 (3)
As6^iv—Eu5—Eu5^viii	58.29 (3)	Eu1ⁱ—Zn2—Eu3^viii	76.14 (3)
Zn1ⁱ—Eu5—Eu5^viii	95.17 (3)	Eu1ⁱⁱ—Zn2—Eu3^viii	123.56 (5)
Zn1ⁱⁱ—Eu5—Eu5^viii	150.85 (4)	Eu5—Zn2—Eu3^viii	76.36 (3)
Zn2—Eu5—Eu5^viii	120.20 (3)	Eu2ⁱ—Zn2—Eu3^viii	105.42 (2)
As6^x—Eu5—Eu5^viii	51.63 (3)	Eu2ⁱⁱ—Zn2—Eu3^viii	161.91 (5)
As3—Eu5—Eu5^viii	138.43 (2)	Eu3^vii—Zn2—Eu3^viii	71.56 (4)
Eu5^vii—Eu5—Eu5^viii	69.86 (3)	As1^xiv—Zn3—As1^xiii	123.84 (9)
As2ⁱ—Eu5—Eu4	109.95 (3)	As1^xiv—Zn3—As4	114.73 (5)
As2ⁱⁱ—Eu5—Eu4	109.95 (3)	As1^xiii—Zn3—As4	114.73 (5)
As6ⁱⁱⁱ—Eu5—Eu4	51.77 (2)	As1^xiv—Zn3—Eu1ⁱⁱ	154.86 (7)
As6^iv—Eu5—Eu4	51.77 (2)	As1^xiii—Zn3—Eu1ⁱⁱ	75.26 (4)
Zn1ⁱ—Eu5—Eu4	53.21 (3)	As4—Zn3—Eu1ⁱⁱ	61.51 (4)
Zn1ⁱⁱ—Eu5—Eu4	53.21 (3)	As1^xiv—Zn3—Eu1ⁱ	75.26 (4)
Zn2—Eu5—Eu4	123.33 (4)	As1^xiii—Zn3—Eu1ⁱ	154.86 (7)
As6^x—Eu5—Eu4	149.61 (3)	As4—Zn3—Eu1ⁱ	61.51 (4)
As3—Eu5—Eu4	47.04 (3)	Eu1ⁱⁱ—Zn3—Eu1ⁱ	82.18 (4)
Eu5^vii—Eu5—Eu4	105.33 (3)	As1^xiv—Zn3—Eu6^xiii	129.29 (7)
Eu5^viii—Eu5—Eu4	105.33 (3)	As1^xiii—Zn3—Eu6^xiii	61.33 (4)
As1^xi—Eu6—As1	180.0	As4—Zn3—Eu6^xiii	60.50 (3)
As1^xi—Eu6—As4^vii	87.28 (3)	Eu1ⁱⁱ—Zn3—Eu6^xiii	72.57 (3)
As1—Eu6—As4^vii	92.72 (3)	Eu1ⁱ—Zn3—Eu6^xiii	121.98 (5)
As1^xi—Eu6—As4^iv	92.72 (3)	As1^xiv—Zn3—Eu6^xiv	61.33 (4)
As1—Eu6—As4^iv	87.28 (3)	As1^xiii—Zn3—Eu6^xiv	129.29 (7)
As4^vii—Eu6—As4^iv	180.00 (5)	As4—Zn3—Eu6^xiv	60.50 (3)
As1^xi—Eu6—As4^viii	87.28 (3)	Eu1ⁱⁱ—Zn3—Eu6^xiv	121.98 (5)
As1—Eu6—As4^viii	92.72 (3)	Eu1ⁱ—Zn3—Eu6^xiv	72.57 (3)
As4^vii—Eu6—As4^viii	86.96 (4)	Eu6^xiii—Zn3—Eu6^xiv	78.21 (4)

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

Experimental details

Crystal data
Chemical formula	Eu₁₁Zn₆As₁₂
M_r	2962.82
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	200
a, b, c (Å)	30.310 (8), 4.3318 (11), 11.774 (3)
β (°)	109.746 (4)
V (Å³)	1455.0 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	41.68
Crystal size (mm)	0.07 × 0.05 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.161, 0.256
No. of measured, independent and observed [I > 2σ(I)] reflections	7178, 1796, 1498
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.062, 1.01
No. of reflections	1796
No. of parameters	90
	w = 1/[σ²(F_o²) + (0.0242P)² + 16.9522P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.70, −1.74

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), XP in SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was funded by the University of Delaware and the Petroleum Research Fund (ACS-PRF).

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