A new rhombohedral modification of EuNi₅In

A rhombohedral modification of europium penta­nickel indide, r-EuNi₅In, crystallizes in the Rm space group and adopts the UCu₅In structure type. The structure is closely related to the hexa­gonal, h-EuNi₅In, form (CeNi₅Sn type). Both EuNi₅In modifications are composed of CaCu₅ (EuNi₅)-, MgCu₂ (InNi₂)- and NiAs (EuNi)-type slabs in a 1:2:1 ratio. The atoms in the structure have high coordination numbers, viz. 20 and 18 for europium, 14 for indium, and 12 and 10 for nickel. The structure features a two-dimensional network of ²_∞[Ni₈] tetra­hedral clusters arranged in the ab plane.

S1. Comment

Extensive investigations focused on the interaction of rare earths (RE) with transition metals and indium have clearly demonstrated that the formation of numerous intermetallic compounds is typical for RE–Ni–In systems (Kalychak et al., 2004; Kalychak, 1997). More than 25 structure types have been reported for these intermetallics (Kalychak et al., 2004). Besides the large structural variety, the R_xNi_yIn_z compounds have attracted considerable interest owing to their distinctive magnetic and electrical properties as well as their hydrogen-storage behavior. In this context the representatives with cerium, europium and ytterbium are the most interesting. Several of these compounds show valence instabilities or unusual magnetic ordering phenomena. Rare earth intermetallics containing europium exhibit a wide range of interesting and unusual physical properties, which are mostly related to their mixed-valence nature (II/III) (Zaremba et al., 2006; Pöttgen et al., 1996). Unfortunately, these systems remain much less well known, which, along with other reasons, may be explained by the experimental difficulties of alloy synthesis. To date, the existence of seven compounds in the Eu–Ni–In system has been confirmed: EuNi_{7+ x}In_{6 -x} (LaNi₇In₆ structure type) (Zaremba et al., 2006), EuNi₉In₂ (YNi₉In₂ structure type) (Kalychak et al., 1984), EuNi₃In₆ (LaNi₃In₆ structure type) (Kalychak et al., 1997), EuNi₅In (CeNi₅Sn structure type) (Baranyak et al., 1992), EuNiIn₄ (YNiAl₄ structure type) (Kalychak et al., 1988; Pöttgen et al., 1996), EuNiIn₂ (MgCuAl₂ structure type) (Kalychak et al., 1997) and EuNi_0.5In_1.5 (AlB₂ structure type) (Baranyak, Dmytrakh et al., 1988).

During the study of the ternary Eu–Ni–In phase diagram, the novel modification of EuNi₅In was found and its crystal structure determined by single-crystal X-ray diffraction. The compound adopts the UCu₅In (Stępień-Damm et al., 1999; Hlukhyy, 2003) structure type. An orthorhombic projection of the unit cell and the coordination polyhedra of atoms are shown in Fig. 1. Two types of polyhedra were observed for Eu1 and Eu2 atoms on Wyckoff sites 3a and 3b, namely eight-capped hexagonal [Eu1Ni₁₈In₂] prisms and six-equatorially and two-base capped pentagonal [Eu2Ni₁₂In₆] antiprisms. Distorted [Ni1Ni₉Eu₃] and [Ni3Ni₇In₂Eu₃] icosahedra are filled by Ni1 and Ni3 atoms, respectively, Ni2 has ten-vertex [Ni2Ni₃In₄Eu₃] polyhedra. Indium atoms are located in the centers of [InNi₁₀Eu₄] polyhedra.

EuNi₅In is a nickel-rich compound. Three crystallographically different nickel sites with Ni—Ni distances ranging from 2.4330 (16) to 2.4785 (17) Å can be found within the rhomobhedral EuNi₅In (r-EuNi₅In) structure. Compared to the Ni—Ni distance of 2.49 Å in the face-centered cubic (f.c.c.) nickel (Donohue, 1974), we can assume a significant degree of Ni—Ni bonding. Here the central building unit is a distorted tetrahedron formed by three Ni3 in the 18h position and one Ni1 or Ni2, both occupying the 6c sites. The tetrahedra now alternately share vertices and faces along the c axis, thereby forming a [Ni₈] unit (Fig. 2a). Each fragment is connected through Ni3 atoms with three other fragments turned by 180°. Six [Ni₈] units are linked together by vertices in the ab plane, building up ring units of 18 tetrahedra (Fig. 2b). The resulting substructure of Ni atoms features a two-dimensional network in the ab plane (Fig. 2c). Eu1 atoms fill holes in the hexagonal rings [thus] formed; Eu2 and In1 atoms separate different sheets of nickel networks. The vertices of the tetrahedra in the next layer are located under the centers of the hexagonal rings. The orientation of the layers in the structure can be described as an ABC sequence (Fig. 2d). The different nickel clusters have been found for several compounds with a high content of transition element in R–Ni–In systems: a three-dimensional network of ³∞[Ni₄] corner-sharing tetrahedra is a characteristic of CeNi₄In (Koterlin et al., 1998), two-dimensional ²∞[Ni₂] fragments occur in LaNi₂In (Kalychak & Zaremba, 1994) and one-dimensional ¹∞[Ni₅] and ¹∞[Ni₇] cluster chains are present in Ce₄Ni₇In₈ (Baranyak, Kalychak et al., 1988) and EuNi₇In₆ (Zaremba et al., 2006), respectively.

Previously, the hexagonal EuNi₅In (h-EuNi₅In) (Baranyak et al., 1992) intermetallic of the CeNi₅Sn type was observed at 670 K. The synthesis of our compound was carried out at 870 K. Therefore we believe that the new compound with the UCu₅In type is probably a high-temperature polymorphic modification of h-EuNi₅In with the CeNi₅Sn type. Structures of both intermetallics can be considered as an intergrowth of the CaCu₅ (Bruzzone, 1971), MgCu₂ (Ohba et al., 1984) and NiAs (Brand & Briest, 1965) related slabs (Fig. 3) with the compositions EuNi₅, InNi₂ and EuNi in the ratio of 1:2:1: 2EuNi₅In = EuNi₅ + 2InNi₂ + EuNi. Hence, the unit cell of each compound in the orthorhombic projection is deduced as follows: for the UCu₅In structure type: 3Eu₂Ni₁₀ (6CaCu₅) + 6In₂Ni₄ (12MgCu₂) + 3Eu₂Ni₂ (6NiAs) = Eu₁₂Ni₆₀In₁₂ = 12 r-EuNi₅In and for the CeNi₅Sn structure type: 2Eu₂Ni₁₀ (4CaCu₅) + 4In₂Ni₄ (8MgCu₂) + 2Eu₂Ni₂ (4NiAs) = Eu₈Ni₄₀In₈ = 8 h-EuNi₅In. In both structures the fragments alternate along the c axis. Consequently, the unit-cell dimension c is proportional to the number of the layers: the hexagonal phase has two sets of fragments and c ≈ 20 Å, the rhombohedral phase has three sets of fragments and c ≈ 30 Å. It should be noticed that the original prototype UCu₅In of the novel compound (Stępień-Damm et al., 1999; Hlukhyy, 2003) has three polymorphic modifications, two of which have the same structure as reported herein.

Related literature

For related literature, see: Baranyak et al. (1992); Baranyak, Dmytrakh et al. (1988); Baranyak, Kalychak et al. (1988); Brand & Briest (1965); Bruzzone (1971); Donohue (1974); Hlukhyy (2003); Kalychak (1997); Kalychak & Zaremba (1994); Kalychak et al. (1984, 1988, 2004); Kalychak, Galadzhun & Stepien-Damm (1997); Koterlin et al. (1998); Ohba et al. (1984); Pöttgen et al. (1996); Stępień-Damm, Zaremba & Hlukhyy (1999); Zaremba et al. (2006).

S2. Experimental

The sample with the composition EuNi₄In and weight of ~2 g was prepared by arc-melting of the pure components (the purity of the ingredients was higher than 99.9 wt%) under a high-purity argon atmosphere. The ingot was remelted twice to ensure homogeneity. The sample was wrapped in a tantalum foil and sealed in an evacuated quartz tube. The ampoule was heated to 1070 K, followed by cooling to 870 K for 24 h. The annealing was carried out at this temperature for 75 h. After the thermal treatment the ampoule with samples was quenched in water. The sample obtained showed a small weight loss which could be explained by evaporation of Eu. The sample is air and moisture sensitive and decomposes outside of the inert atmosphere within a few days. The X-ray diffraction powder pattern was collected using monochromatic Cu Kα radiation on a DRON-3 diffractometer. X-ray phase analysis revealed the presence of two phases: EuNi₅In and a small amount of In, which could be explained by a partial decomposition of the sample. Single crystals of EuNi₅In of an irregular form were extracted from the crushed sample. In contrast to the powder these remain stable in air for a long time.

S3. Refinement

Analyses of the systematic absences for the single-crystal data led to the possible space groups R3 (No. 148), R3 (No. 146), R3m (No. 160), R32 (No. 155), R3m (No. 166). The space group with the highest symmetry, R3m, was found to be correct during the structure refinement. The starting atomic parameters were deduced from an automatic interpretation of direct methods and the structure was successfully refined using full-matrix least squares on F² with anisotropic atomic displacement parameters for all atoms. All crystallographic positions are fully occupied. Final difference Fourier synthesis revealed a slightly elevated, but not significant, residual peak of 2.55 e. However, it was too close to a nickel (0.90 Å) position to be indicative of an additional atomic site. It is probably due to the irregular shape of the crystal and consequently an incomplete absorption correction.

Computing details

Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT (Bruker,1996); 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. A projection of the EuNi5In unit cell in an orthorhombic aspect and a view of the coordination polyhedra of the atoms.
	Fig. 2. (a) The [Ni8] tetrahedral unit; (b) the hexagonal ring of six [Ni8] units; (c) the ^2∞[Ni8] two-dimensional layer; (d) the ABC sequence of ^2∞[Ni8] layers in the EuNi5In structure. (Bond lengths are given in Å.)
	Fig. 3. The packing of CaCu5, MgCu2 and NiAs related slabs in the (a) UCu5In and (b) CeNi5Sn forms of EuNi5In. The atoms designs in (c) CaCu5, (e) MgCu2 and (d) NiAs structures are given as the designs of Eu, Ni and In atoms, respectively. [please clarify]

europium pentanickel indide

Crystal data

EuNi5In	Dx = 9.041 Mg m^−3
Mr = 560.33	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3m	Cell parameters from 1820 reflections
a = 4.8956 (7) Å	θ = 2.1–28.3°
c = 29.751 (6) Å	µ = 42.64 mm^−1
V = 617.51 (18) Å^3	T = 293 K
Z = 6	Xenomorphic fragment, metallic-grey
F(000) = 1512	0.15 × 0.10 × 0.05 mm

Data collection

Bruker CCD diffractometer	229 independent reflections
Radiation source: fine-focus sealed tube	209 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements) (Blessing, 1995)	h = −6→6
Tmin = 0.003, Tmax = 0.100	k = −6→6
1820 measured reflections	l = −39→39

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)] = 0.022	Secondary atom site location: difference Fourier map
wR(F^2) = 0.051	w = 1/[σ^2(Fo^2) + (0.0246P)^2 + 10.2303P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
229 reflections	Δρmax = 2.55 e Å^−3
20 parameters	Δρmin = −1.31 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
Eu1	0.0000	0.0000	0.0000	0.0098 (2)
Eu2	0.0000	0.0000	0.5000	0.0095 (2)
In1	0.0000	0.0000	0.11026 (3)	0.0091 (2)
Ni1	0.0000	0.0000	0.33355 (5)	0.0099 (4)
Ni2	0.0000	0.0000	0.19824 (5)	0.0130 (4)
Ni3	0.49899 (10)	0.50101 (10)	0.06802 (3)	0.0089 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Eu1	0.0094 (3)	0.0094 (3)	0.0107 (4)	0.00472 (14)	0.000	0.000
Eu2	0.0087 (3)	0.0087 (3)	0.0111 (4)	0.00433 (14)	0.000	0.000
In1	0.0092 (3)	0.0092 (3)	0.0091 (4)	0.00458 (14)	0.000	0.000
Ni1	0.0107 (5)	0.0107 (5)	0.0085 (7)	0.0053 (3)	0.000	0.000
Ni2	0.0146 (6)	0.0146 (6)	0.0098 (8)	0.0073 (3)	0.000	0.000
Ni3	0.0086 (3)	0.0086 (3)	0.0111 (5)	0.0055 (4)	0.00014 (18)	−0.00014 (18)

Geometric parameters (Å, º)

Eu1—Ni1^i	2.8265 (4)	In1—Ni2^v	2.9214 (6)
Eu1—Ni1^ii	2.8265 (4)	In1—Eu2^iii	3.2870 (6)
Eu1—Ni1^iii	2.8265 (4)	Ni1—Ni3^xv	2.4581 (15)
Eu1—Ni1^iv	2.8265 (4)	Ni1—Ni3^xxi	2.4581 (15)
Eu1—Ni1^v	2.8265 (4)	Ni1—Ni3^xix	2.4581 (15)
Eu1—Ni1^vi	2.8265 (4)	Ni1—Ni3^i	2.4784 (16)
Eu1—Ni3	3.1760 (7)	Ni1—Ni3^xxv	2.4784 (16)
Eu1—Ni3^vii	3.1760 (7)	Ni1—Ni3^xxvi	2.4784 (16)
Eu1—Ni3^viii	3.1760 (7)	Ni1—Eu1^xiii	2.8265 (4)
Eu1—Ni3^ix	3.1760 (7)	Ni1—Eu1^xv	2.8265 (4)
Eu1—Ni3^x	3.1760 (7)	Ni1—Ni1^xii	2.8265 (4)
Eu1—Ni3^xi	3.1760 (7)	Ni1—Ni1^xiv	2.8265 (4)
Eu2—Ni2^xii	2.9785 (6)	Ni1—Eu1^xvii	2.8265 (4)
Eu2—Ni2^xiii	2.9785 (6)	Ni1—Ni1^xvi	2.8265 (4)
Eu2—Ni2^xiv	2.9785 (6)	Ni2—Ni3^i	2.4502 (16)
Eu2—Ni2^xv	2.9785 (6)	Ni2—Ni3^xxvi	2.4503 (16)
Eu2—Ni2^xvi	2.9785 (6)	Ni2—Ni3^xxv	2.4503 (16)
Eu2—Ni2^xvii	2.9785 (6)	Ni2—In1^i	2.9214 (6)
Eu2—Ni3^xiv	3.2536 (10)	Ni2—In1^ii	2.9214 (6)
Eu2—Ni3^xv	3.2536 (10)	Ni2—In1^v	2.9214 (6)
Eu2—Ni3^xviii	3.2537 (10)	Ni2—Eu2^iv	2.9785 (6)
Eu2—Ni3^xix	3.2537 (10)	Ni2—Eu2^iii	2.9785 (6)
Eu2—Ni3^xx	3.2537 (10)	Ni2—Eu2^vi	2.9785 (6)
Eu2—Ni3^xxi	3.2537 (10)	Ni3—Ni3^ix	2.4330 (15)
In1—Ni2	2.6175 (19)	Ni3—Ni3^xxvii	2.4330 (15)
In1—Ni3^xxii	2.7516 (7)	Ni3—Ni2^i	2.4502 (16)
In1—Ni3^xxiii	2.7516 (7)	Ni3—Ni1^iii	2.4581 (15)
In1—Ni3^xxiv	2.7516 (7)	Ni3—Ni3^xxviii	2.4626 (15)
In1—Ni3	2.7516 (7)	Ni3—Ni3^x	2.4626 (15)
In1—Ni3^x	2.7516 (7)	Ni3—Ni1^i	2.4784 (16)
In1—Ni3^ix	2.7516 (7)	Ni3—In1^xxix	2.7516 (7)
In1—Ni2^i	2.9214 (6)	Ni3—Eu1^xxix	3.1760 (7)
In1—Ni2^ii	2.9214 (6)	Ni3—Eu2^iii	3.2536 (10)
Ni1^i—Eu1—Ni1^ii	120.0	Ni3^xxii—In1—Eu2^iii	153.418 (18)
Ni1^i—Eu1—Ni1^iii	60.0	Ni3^xxiii—In1—Eu2^iii	103.642 (18)
Ni1^ii—Eu1—Ni1^iii	180.0	Ni3^xxiv—In1—Eu2^iii	153.417 (18)
Ni1^i—Eu1—Ni1^iv	180.0	Ni3—In1—Eu2^iii	64.49 (2)
Ni1^ii—Eu1—Ni1^iv	60.0	Ni3^x—In1—Eu2^iii	103.641 (18)
Ni1^iii—Eu1—Ni1^iv	120.0	Ni3^ix—In1—Eu2^iii	64.49 (2)
Ni1^i—Eu1—Ni1^v	120.0	Ni2^i—In1—Eu2^iii	56.971 (15)
Ni1^ii—Eu1—Ni1^v	120.0	Ni2^ii—In1—Eu2^iii	134.66 (4)
Ni1^iii—Eu1—Ni1^v	60.0	Ni2^v—In1—Eu2^iii	56.972 (15)
Ni1^iv—Eu1—Ni1^v	60.0	Eu1—In1—Eu2^iii	120.696 (14)
Ni1^i—Eu1—Ni1^vi	60.0	Ni3^xv—Ni1—Ni3^xxi	59.32 (5)
Ni1^ii—Eu1—Ni1^vi	60.0	Ni3^xv—Ni1—Ni3^xix	59.32 (5)
Ni1^iii—Eu1—Ni1^vi	120.0	Ni3^xxi—Ni1—Ni3^xix	59.32 (5)
Ni1^iv—Eu1—Ni1^vi	120.0	Ni3^xv—Ni1—Ni3^i	110.14 (3)
Ni1^v—Eu1—Ni1^vi	180.0	Ni3^xxi—Ni1—Ni3^i	146.730 (12)
Ni1^i—Eu1—Ni3	48.34 (3)	Ni3^xix—Ni1—Ni3^i	146.730 (11)
Ni1^ii—Eu1—Ni3	132.09 (3)	Ni3^xv—Ni1—Ni3^xxv	146.730 (11)
Ni1^iii—Eu1—Ni3	47.91 (3)	Ni3^xxi—Ni1—Ni3^xxv	146.728 (11)
Ni1^iv—Eu1—Ni3	131.66 (3)	Ni3^xix—Ni1—Ni3^xxv	110.14 (3)
Ni1^v—Eu1—Ni3	89.93 (2)	Ni3^i—Ni1—Ni3^xxv	59.58 (5)
Ni1^vi—Eu1—Ni3	90.07 (2)	Ni3^xv—Ni1—Ni3^xxvi	146.730 (12)
Ni1^i—Eu1—Ni3^vii	131.66 (3)	Ni3^xxi—Ni1—Ni3^xxvi	110.14 (3)
Ni1^ii—Eu1—Ni3^vii	47.91 (3)	Ni3^xix—Ni1—Ni3^xxvi	146.728 (11)
Ni1^iii—Eu1—Ni3^vii	132.09 (3)	Ni3^i—Ni1—Ni3^xxvi	59.58 (5)
Ni1^iv—Eu1—Ni3^vii	48.34 (3)	Ni3^xxv—Ni1—Ni3^xxvi	59.58 (5)
Ni1^v—Eu1—Ni3^vii	90.07 (2)	Ni3^xv—Ni1—Eu1^xiii	73.51 (2)
Ni1^vi—Eu1—Ni3^vii	89.93 (2)	Ni3^xxi—Ni1—Eu1^xiii	73.51 (2)
Ni3—Eu1—Ni3^vii	180.00 (3)	Ni3^xix—Ni1—Eu1^xiii	124.98 (5)
Ni1^i—Eu1—Ni3^viii	90.07 (2)	Ni3^i—Ni1—Eu1^xiii	73.221 (19)
Ni1^ii—Eu1—Ni3^viii	47.91 (3)	Ni3^xxv—Ni1—Eu1^xiii	124.88 (6)
Ni1^iii—Eu1—Ni3^viii	132.09 (3)	Ni3^xxvi—Ni1—Eu1^xiii	73.221 (19)
Ni1^iv—Eu1—Ni3^viii	89.93 (2)	Ni3^xv—Ni1—Eu1^xv	73.51 (2)
Ni1^v—Eu1—Ni3^viii	131.66 (3)	Ni3^xxi—Ni1—Eu1^xv	124.98 (5)
Ni1^vi—Eu1—Ni3^viii	48.34 (3)	Ni3^xix—Ni1—Eu1^xv	73.51 (2)
Ni3—Eu1—Ni3^viii	134.96 (3)	Ni3^i—Ni1—Eu1^xv	73.221 (19)
Ni3^vii—Eu1—Ni3^viii	45.04 (3)	Ni3^xxv—Ni1—Eu1^xv	73.221 (19)
Ni1^i—Eu1—Ni3^ix	89.93 (2)	Ni3^xxvi—Ni1—Eu1^xv	124.88 (6)
Ni1^ii—Eu1—Ni3^ix	132.09 (3)	Eu1^xiii—Ni1—Eu1^xv	120.0
Ni1^iii—Eu1—Ni3^ix	47.91 (3)	Ni3^xv—Ni1—Ni1^xii	106.83 (6)
Ni1^iv—Eu1—Ni3^ix	90.07 (2)	Ni3^xxi—Ni1—Ni1^xii	106.83 (6)
Ni1^v—Eu1—Ni3^ix	48.34 (3)	Ni3^xix—Ni1—Ni1^xii	55.41 (5)
Ni1^vi—Eu1—Ni3^ix	131.66 (3)	Ni3^i—Ni1—Ni1^xii	106.44 (6)
Ni3—Eu1—Ni3^ix	45.04 (3)	Ni3^xxv—Ni1—Ni1^xii	54.73 (5)
Ni3^vii—Eu1—Ni3^ix	134.96 (3)	Ni3^xxvi—Ni1—Ni1^xii	106.44 (6)
Ni3^viii—Eu1—Ni3^ix	180.00 (5)	Eu1^xiii—Ni1—Ni1^xii	179.61 (9)
Ni1^i—Eu1—Ni3^x	48.34 (3)	Eu1^xv—Ni1—Ni1^xii	60.0
Ni1^ii—Eu1—Ni3^x	89.93 (2)	Ni3^xv—Ni1—Ni1^xiv	106.83 (6)
Ni1^iii—Eu1—Ni3^x	90.07 (2)	Ni3^xxi—Ni1—Ni1^xiv	55.41 (5)
Ni1^iv—Eu1—Ni3^x	131.66 (3)	Ni3^xix—Ni1—Ni1^xiv	106.83 (6)
Ni1^v—Eu1—Ni3^x	132.09 (3)	Ni3^i—Ni1—Ni1^xiv	106.44 (6)
Ni1^vi—Eu1—Ni3^x	47.91 (3)	Ni3^xxv—Ni1—Ni1^xiv	106.44 (6)
Ni3—Eu1—Ni3^x	45.62 (3)	Ni3^xxvi—Ni1—Ni1^xiv	54.73 (5)
Ni3^vii—Eu1—Ni3^x	134.38 (3)	Eu1^xiii—Ni1—Ni1^xiv	60.0
Ni3^viii—Eu1—Ni3^x	96.26 (2)	Eu1^xv—Ni1—Ni1^xiv	179.61 (9)
Ni3^ix—Eu1—Ni3^x	83.74 (2)	Ni1^xii—Ni1—Ni1^xiv	119.999 (1)
Ni1^i—Eu1—Ni3^xi	131.66 (3)	Ni3^xv—Ni1—Eu1^xvii	124.98 (5)
Ni1^ii—Eu1—Ni3^xi	90.07 (2)	Ni3^xxi—Ni1—Eu1^xvii	73.51 (2)
Ni1^iii—Eu1—Ni3^xi	89.93 (2)	Ni3^xix—Ni1—Eu1^xvii	73.51 (2)
Ni1^iv—Eu1—Ni3^xi	48.34 (3)	Ni3^i—Ni1—Eu1^xvii	124.88 (6)
Ni1^v—Eu1—Ni3^xi	47.91 (3)	Ni3^xxv—Ni1—Eu1^xvii	73.220 (19)
Ni1^vi—Eu1—Ni3^xi	132.09 (3)	Ni3^xxvi—Ni1—Eu1^xvii	73.220 (19)
Ni3—Eu1—Ni3^xi	134.38 (3)	Eu1^xiii—Ni1—Eu1^xvii	120.0
Ni3^vii—Eu1—Ni3^xi	45.62 (3)	Eu1^xv—Ni1—Eu1^xvii	120.0
Ni3^viii—Eu1—Ni3^xi	83.74 (2)	Ni1^xii—Ni1—Eu1^xvii	60.0
Ni3^ix—Eu1—Ni3^xi	96.26 (2)	Ni1^xiv—Ni1—Eu1^xvii	60.0
Ni3^x—Eu1—Ni3^xi	180.00 (2)	Ni3^xv—Ni1—Ni1^xvi	55.41 (5)
Ni2^xii—Eu2—Ni2^xiii	180.00 (6)	Ni3^xxi—Ni1—Ni1^xvi	106.83 (6)
Ni2^xii—Eu2—Ni2^xiv	110.53 (3)	Ni3^xix—Ni1—Ni1^xvi	106.83 (6)
Ni2^xiii—Eu2—Ni2^xiv	69.47 (3)	Ni3^i—Ni1—Ni1^xvi	54.73 (5)
Ni2^xii—Eu2—Ni2^xv	69.47 (3)	Ni3^xxv—Ni1—Ni1^xvi	106.44 (6)
Ni2^xiii—Eu2—Ni2^xv	110.53 (3)	Ni3^xxvi—Ni1—Ni1^xvi	106.44 (6)
Ni2^xiv—Eu2—Ni2^xv	180.0	Eu1^xiii—Ni1—Ni1^xvi	60.0
Ni2^xii—Eu2—Ni2^xvi	110.53 (3)	Eu1^xv—Ni1—Ni1^xvi	60.0
Ni2^xiii—Eu2—Ni2^xvi	69.47 (3)	Ni1^xii—Ni1—Ni1^xvi	119.998 (1)
Ni2^xiv—Eu2—Ni2^xvi	110.53 (3)	Ni1^xiv—Ni1—Ni1^xvi	119.998 (1)
Ni2^xv—Eu2—Ni2^xvi	69.47 (3)	Eu1^xvii—Ni1—Ni1^xvi	179.61 (9)
Ni2^xii—Eu2—Ni2^xvii	69.47 (3)	Ni3^i—Ni2—Ni3^xxvi	60.33 (5)
Ni2^xiii—Eu2—Ni2^xvii	110.53 (3)	Ni3^i—Ni2—Ni3^xxv	60.33 (5)
Ni2^xiv—Eu2—Ni2^xvii	69.47 (3)	Ni3^xxvi—Ni2—Ni3^xxv	60.33 (5)
Ni2^xv—Eu2—Ni2^xvii	110.53 (3)	Ni3^i—Ni2—In1	144.53 (3)
Ni2^xvi—Eu2—Ni2^xvii	180.00 (6)	Ni3^xxvi—Ni2—In1	144.53 (3)
Ni2^xii—Eu2—Ni3^xiv	94.57 (3)	Ni3^xxv—Ni2—In1	144.53 (3)
Ni2^xiii—Eu2—Ni3^xiv	85.43 (3)	Ni3^i—Ni2—In1^i	60.88 (2)
Ni2^xiv—Eu2—Ni3^xiv	94.57 (3)	Ni3^xxvi—Ni2—In1^i	60.88 (2)
Ni2^xv—Eu2—Ni3^xiv	85.43 (3)	Ni3^xxv—Ni2—In1^i	110.82 (6)
Ni2^xvi—Eu2—Ni3^xiv	133.96 (3)	In1—Ni2—In1^i	104.65 (3)
Ni2^xvii—Eu2—Ni3^xiv	46.04 (3)	Ni3^i—Ni2—In1^ii	60.88 (2)
Ni2^xii—Eu2—Ni3^xv	85.43 (3)	Ni3^xxvi—Ni2—In1^ii	110.82 (6)
Ni2^xiii—Eu2—Ni3^xv	94.57 (3)	Ni3^xxv—Ni2—In1^ii	60.88 (2)
Ni2^xiv—Eu2—Ni3^xv	85.43 (3)	In1—Ni2—In1^ii	104.65 (3)
Ni2^xv—Eu2—Ni3^xv	94.57 (3)	In1^i—Ni2—In1^ii	113.83 (3)
Ni2^xvi—Eu2—Ni3^xv	46.04 (3)	Ni3^i—Ni2—In1^v	110.82 (6)
Ni2^xvii—Eu2—Ni3^xv	133.96 (3)	Ni3^xxvi—Ni2—In1^v	60.88 (2)
Ni3^xiv—Eu2—Ni3^xv	180.000 (13)	Ni3^xxv—Ni2—In1^v	60.88 (2)
Ni2^xii—Eu2—Ni3^xviii	133.96 (3)	In1—Ni2—In1^v	104.65 (3)
Ni2^xiii—Eu2—Ni3^xviii	46.04 (3)	In1^i—Ni2—In1^v	113.83 (3)
Ni2^xiv—Eu2—Ni3^xviii	94.57 (3)	In1^ii—Ni2—In1^v	113.83 (3)
Ni2^xv—Eu2—Ni3^xviii	85.43 (3)	Ni3^i—Ni2—Eu2^iv	122.15 (3)
Ni2^xvi—Eu2—Ni3^xviii	94.57 (3)	Ni3^xxvi—Ni2—Eu2^iv	122.15 (3)
Ni2^xvii—Eu2—Ni3^xviii	85.43 (3)	Ni3^xxv—Ni2—Eu2^iv	72.92 (2)
Ni3^xiv—Eu2—Ni3^xviii	43.91 (3)	In1—Ni2—Eu2^iv	71.61 (3)
Ni3^xv—Eu2—Ni3^xviii	136.09 (3)	In1^i—Ni2—Eu2^iv	176.26 (6)
Ni2^xii—Eu2—Ni3^xix	46.04 (3)	In1^ii—Ni2—Eu2^iv	67.709 (8)
Ni2^xiii—Eu2—Ni3^xix	133.96 (3)	In1^v—Ni2—Eu2^iv	67.710 (8)
Ni2^xiv—Eu2—Ni3^xix	85.43 (3)	Ni3^i—Ni2—Eu2^iii	122.15 (3)
Ni2^xv—Eu2—Ni3^xix	94.57 (3)	Ni3^xxvi—Ni2—Eu2^iii	72.92 (2)
Ni2^xvi—Eu2—Ni3^xix	85.43 (3)	Ni3^xxv—Ni2—Eu2^iii	122.15 (3)
Ni2^xvii—Eu2—Ni3^xix	94.57 (3)	In1—Ni2—Eu2^iii	71.61 (3)
Ni3^xiv—Eu2—Ni3^xix	136.09 (3)	In1^i—Ni2—Eu2^iii	67.709 (8)
Ni3^xv—Eu2—Ni3^xix	43.91 (3)	In1^ii—Ni2—Eu2^iii	176.26 (6)
Ni3^xviii—Eu2—Ni3^xix	180.0	In1^v—Ni2—Eu2^iii	67.710 (8)
Ni2^xii—Eu2—Ni3^xx	94.57 (3)	Eu2^iv—Ni2—Eu2^iii	110.53 (3)
Ni2^xiii—Eu2—Ni3^xx	85.43 (3)	Ni3^i—Ni2—Eu2^vi	72.92 (2)
Ni2^xiv—Eu2—Ni3^xx	133.96 (3)	Ni3^xxvi—Ni2—Eu2^vi	122.16 (3)
Ni2^xv—Eu2—Ni3^xx	46.04 (3)	Ni3^xxv—Ni2—Eu2^vi	122.16 (3)
Ni2^xvi—Eu2—Ni3^xx	94.57 (3)	In1—Ni2—Eu2^vi	71.61 (3)
Ni2^xvii—Eu2—Ni3^xx	85.43 (3)	In1^i—Ni2—Eu2^vi	67.710 (8)
Ni3^xiv—Eu2—Ni3^xx	43.91 (3)	In1^ii—Ni2—Eu2^vi	67.710 (8)
Ni3^xv—Eu2—Ni3^xx	136.09 (3)	In1^v—Ni2—Eu2^vi	176.26 (6)
Ni3^xviii—Eu2—Ni3^xx	43.91 (3)	Eu2^iv—Ni2—Eu2^vi	110.53 (3)
Ni3^xix—Eu2—Ni3^xx	136.09 (3)	Eu2^iii—Ni2—Eu2^vi	110.53 (3)
Ni2^xii—Eu2—Ni3^xxi	85.43 (3)	Ni3^ix—Ni3—Ni3^xxvii	60.0
Ni2^xiii—Eu2—Ni3^xxi	94.57 (3)	Ni3^ix—Ni3—Ni2^i	120.17 (2)
Ni2^xiv—Eu2—Ni3^xxi	46.04 (3)	Ni3^xxvii—Ni3—Ni2^i	120.17 (2)
Ni2^xv—Eu2—Ni3^xxi	133.96 (3)	Ni3^ix—Ni3—Ni1^iii	60.34 (2)
Ni2^xvi—Eu2—Ni3^xxi	85.43 (3)	Ni3^xxvii—Ni3—Ni1^iii	60.34 (2)
Ni2^xvii—Eu2—Ni3^xxi	94.57 (3)	Ni2^i—Ni3—Ni1^iii	179.38 (5)
Ni3^xiv—Eu2—Ni3^xxi	136.09 (3)	Ni3^ix—Ni3—Ni3^xxviii	180.00 (9)
Ni3^xv—Eu2—Ni3^xxi	43.91 (3)	Ni3^xxvii—Ni3—Ni3^xxviii	120.0
Ni3^xviii—Eu2—Ni3^xxi	136.09 (3)	Ni2^i—Ni3—Ni3^xxviii	59.83 (2)
Ni3^xix—Eu2—Ni3^xxi	43.91 (3)	Ni1^iii—Ni3—Ni3^xxviii	119.66 (2)
Ni3^xx—Eu2—Ni3^xxi	180.0	Ni3^ix—Ni3—Ni3^x	120.0
Ni2—In1—Ni3^xxii	117.18 (2)	Ni3^xxvii—Ni3—Ni3^x	180.00 (8)
Ni2—In1—Ni3^xxiii	117.18 (2)	Ni2^i—Ni3—Ni3^x	59.83 (2)
Ni3^xxii—In1—Ni3^xxiii	52.48 (4)	Ni1^iii—Ni3—Ni3^x	119.66 (2)
Ni2—In1—Ni3^xxiv	117.18 (2)	Ni3^xxviii—Ni3—Ni3^x	60.0
Ni3^xxii—In1—Ni3^xxiv	53.17 (4)	Ni3^ix—Ni3—Ni1^i	119.79 (2)
Ni3^xxiii—In1—Ni3^xxiv	100.78 (3)	Ni3^xxvii—Ni3—Ni1^i	119.79 (2)
Ni2—In1—Ni3	117.18 (2)	Ni2^i—Ni3—Ni1^i	109.52 (5)
Ni3^xxii—In1—Ni3	125.64 (5)	Ni1^iii—Ni3—Ni1^i	69.86 (3)
Ni3^xxiii—In1—Ni3	100.78 (3)	Ni3^xxviii—Ni3—Ni1^i	60.21 (2)
Ni3^xxiv—In1—Ni3	100.78 (3)	Ni3^x—Ni3—Ni1^i	60.21 (2)
Ni2—In1—Ni3^x	117.18 (2)	Ni3^ix—Ni3—In1^xxix	116.583 (18)
Ni3^xxii—In1—Ni3^x	100.78 (3)	Ni3^xxvii—Ni3—In1^xxix	63.762 (18)
Ni3^xxiii—In1—Ni3^x	125.64 (5)	Ni2^i—Ni3—In1^xxix	68.05 (2)
Ni3^xxiv—In1—Ni3^x	52.48 (4)	Ni1^iii—Ni3—In1^xxix	112.12 (2)
Ni3—In1—Ni3^x	53.17 (4)	Ni3^xxviii—Ni3—In1^xxix	63.417 (18)
Ni2—In1—Ni3^ix	117.18 (2)	Ni3^x—Ni3—In1^xxix	116.238 (18)
Ni3^xxii—In1—Ni3^ix	100.78 (3)	Ni1^i—Ni3—In1^xxix	111.86 (2)
Ni3^xxiii—In1—Ni3^ix	53.17 (4)	Ni3^ix—Ni3—In1	63.762 (18)
Ni3^xxiv—In1—Ni3^ix	125.64 (5)	Ni3^xxvii—Ni3—In1	116.583 (18)
Ni3—In1—Ni3^ix	52.48 (4)	Ni2^i—Ni3—In1	68.05 (2)
Ni3^x—In1—Ni3^ix	100.78 (3)	Ni1^iii—Ni3—In1	112.12 (2)
Ni2—In1—Ni2^i	75.35 (3)	Ni3^xxviii—Ni3—In1	116.238 (18)
Ni3^xxii—In1—Ni2^i	149.58 (3)	Ni3^x—Ni3—In1	63.417 (18)
Ni3^xxiii—In1—Ni2^i	149.58 (3)	Ni1^i—Ni3—In1	111.86 (2)
Ni3^xxiv—In1—Ni2^i	96.46 (2)	In1^xxix—Ni3—In1	125.64 (5)
Ni3—In1—Ni2^i	51.07 (3)	Ni3^ix—Ni3—Eu1	67.479 (15)
Ni3^x—In1—Ni2^i	51.07 (3)	Ni3^xxvii—Ni3—Eu1	112.811 (15)
Ni3^ix—In1—Ni2^i	96.46 (2)	Ni2^i—Ni3—Eu1	121.16 (2)
Ni2—In1—Ni2^ii	75.35 (3)	Ni1^iii—Ni3—Eu1	58.577 (18)
Ni3^xxii—In1—Ni2^ii	51.07 (3)	Ni3^xxviii—Ni3—Eu1	112.521 (15)
Ni3^xxiii—In1—Ni2^ii	96.46 (2)	Ni3^x—Ni3—Eu1	67.189 (15)
Ni3^xxiv—In1—Ni2^ii	51.07 (3)	Ni1^i—Ni3—Eu1	58.437 (19)
Ni3—In1—Ni2^ii	149.58 (3)	In1^xxix—Ni3—Eu1	167.59 (3)
Ni3^x—In1—Ni2^ii	96.46 (2)	In1—Ni3—Eu1	66.76 (2)
Ni3^ix—In1—Ni2^ii	149.58 (3)	Ni3^ix—Ni3—Eu1^xxix	112.811 (15)
Ni2^i—In1—Ni2^ii	113.83 (3)	Ni3^xxvii—Ni3—Eu1^xxix	67.479 (15)
Ni2—In1—Ni2^v	75.35 (3)	Ni2^i—Ni3—Eu1^xxix	121.16 (2)
Ni3^xxii—In1—Ni2^v	96.46 (2)	Ni1^iii—Ni3—Eu1^xxix	58.577 (18)
Ni3^xxiii—In1—Ni2^v	51.07 (3)	Ni3^xxviii—Ni3—Eu1^xxix	67.189 (15)
Ni3^xxiv—In1—Ni2^v	149.58 (3)	Ni3^x—Ni3—Eu1^xxix	112.521 (15)
Ni3—In1—Ni2^v	96.46 (2)	Ni1^i—Ni3—Eu1^xxix	58.437 (19)
Ni3^x—In1—Ni2^v	149.58 (3)	In1^xxix—Ni3—Eu1^xxix	66.76 (2)
Ni3^ix—In1—Ni2^v	51.07 (3)	In1—Ni3—Eu1^xxix	167.59 (3)
Ni2^i—In1—Ni2^v	113.83 (3)	Eu1—Ni3—Eu1^xxix	100.84 (3)
Ni2^ii—In1—Ni2^v	113.83 (3)	Ni3^ix—Ni3—Eu2^iii	68.045 (13)
Ni2—In1—Eu1	180.0	Ni3^xxvii—Ni3—Eu2^iii	68.045 (13)
Ni3^xxii—In1—Eu1	62.82 (2)	Ni2^i—Ni3—Eu2^iii	61.05 (3)
Ni3^xxiii—In1—Eu1	62.82 (2)	Ni1^iii—Ni3—Eu2^iii	119.57 (4)
Ni3^xxiv—In1—Eu1	62.82 (2)	Ni3^xxviii—Ni3—Eu2^iii	111.955 (13)
Ni3—In1—Eu1	62.82 (2)	Ni3^x—Ni3—Eu2^iii	111.955 (13)
Ni3^x—In1—Eu1	62.82 (2)	Ni1^i—Ni3—Eu2^iii	170.57 (4)
Ni3^ix—In1—Eu1	62.82 (2)	In1^xxix—Ni3—Eu2^iii	65.75 (2)
Ni2^i—In1—Eu1	104.65 (3)	In1—Ni3—Eu2^iii	65.75 (2)
Ni2^ii—In1—Eu1	104.65 (3)	Eu1—Ni3—Eu2^iii	125.162 (17)
Ni2^v—In1—Eu1	104.65 (3)	Eu1^xxix—Ni3—Eu2^iii	125.162 (17)
Ni2—In1—Eu2^iii	59.304 (14)

Symmetry codes: (i) −x+2/3, −y+1/3, −z+1/3; (ii) −x−1/3, −y−2/3, −z+1/3; (iii) x+1/3, y+2/3, z−1/3; (iv) x−2/3, y−1/3, z−1/3; (v) −x−1/3, −y+1/3, −z+1/3; (vi) x+1/3, y−1/3, z−1/3; (vii) −x, −y, −z; (viii) x−y, x−1, −z; (ix) −x+y, −x+1, z; (x) −y+1, x−y, z; (xi) y−1, −x+y, −z; (xii) −x−2/3, −y−1/3, −z+2/3; (xiii) x+2/3, y+1/3, z+1/3; (xiv) −x+1/3, −y+2/3, −z+2/3; (xv) x−1/3, y−2/3, z+1/3; (xvi) −x+1/3, −y−1/3, −z+2/3; (xvii) x−1/3, y+1/3, z+1/3; (xviii) x−y+1/3, x−1/3, −z+2/3; (xix) −x+y−1/3, −x+1/3, z+1/3; (xx) y−2/3, −x+y−1/3, −z+2/3; (xxi) −y+2/3, x−y+1/3, z+1/3; (xxii) x−1, y−1, z; (xxiii) −y, x−y, z; (xxiv) −x+y, −x, z; (xxv) x−y−1/3, x−2/3, −z+1/3; (xxvi) y−1/3, −x+y+1/3, −z+1/3; (xxvii) −y+1, x−y+1, z; (xxviii) −x+y+1, −x+1, z; (xxix) x+1, y+1, z.