Synthesis, crystal structures and chemical bonding of RE_5−xLi_xGe₄ (RE = Nd, Sm and Gd; x ≃ 1) with the ortho­rhom­bic Gd₅Si₄ type

The syntheses and single-crystal and electronic structures of three new ternary lithium rare earth germanides, RE_5−xLi_xGe₄ (RE = Nd, Sm and Gd; x ≃ 1), namely tetra­samarium lithium tetra­germanide (Sm_3.97Li_1.03Ge₄), tetra­neodymium lithium tetra­germanide (Nd_3.97Li_1.03Ge₄) and tetra­gadolinium lithium tetra­germanide (Gd_3.96Li_1.03Ge₄), are reported. All three compounds crystallize in the ortho­rhom­bic space group Pnma and adopt the Gd₅Si₄ structure type (Pearson code oP36). There are six atoms in the asymmetric unit: Li1 in Wyckoff site 4c, RE1 in 8d, RE2 in 8d, Ge1 in 8d, Ge2 in 4c and Ge3 in 4c. One of the RE sites, i.e. RE2, is statistically occupied by RE and Li atoms, accounting for the small deviation from ideal RE₄LiGe₄ stoichiometry.

S1. Comment

Following the discovery of giant magnetocaloric effects in Gd₅Si₂Ge₂ in 1997 (Pecharsky & Gschneidner, 1997a), great effort has been devoted to the synthesis and study of the structures and physical properties of rare earth silicides and germanides with the Gd₅Si₄ or Sm₅Ge₄ structure types, and also of their intermediates (Kyunghan et al., 1997; Misra & Miller, 2008)

Many articles have already discussed the structural similarities and differences between the Gd₅Si₄ and Sm₅Ge₄ structures, which are isopointal but not isostructural (Pecharsky & Gschneidner, 1997b) (Fig. 1). Summarizing these findings briefly, we must point out that there are two pairs of Si—Si bonds in Gd₅Si₄ but only one type of Ge—Ge bond in Sm₅Ge₄ (Pecharsky & Gschneidner, 1997b). Furthermore, there are many factors, such as temperature, pressure and chemical make-up, which can cause one of the interslab bonds to form or cleave reversibly (Levin et al., 2002; Magen et al., 2003).

Our previous work on Mg substitutions in RE₅Ge₄ has already demonstrated that the structure is amenable to variations. For brevity, RE will denote a rare earth metal throughout this article. Note that RE³⁺ ions are replaced with Mg²⁺, which allows for structural changes that are also coupled with the magnetic properties of the resultant RE_5–xMg_xGe₄ materials (Tobash et al., 2009). Importantly, our study has also shown that Mg first replaces the rare earth metal at the 4c site. Mg also replaces some of the RE2 at site 8d, leading to the final formula RE_5-xMg_xGe₄ (x ≈ 2).

The `phase width' can be easily understood from the point of view of the Zintl–Klemm concept (Kauzlarich, 1996). In RE₅Ge₄ (Sm₅Ge₄ type), two of the Ge atoms are dimerized and two remain as isolated Ge atoms. The Ge dimer needs six electrons (three on each Ge) to satisfy the octet rule and the isolated Ge atom needs four electrons. Accordingly, the overall electron count for the RE₅Ge₄ structure will be (RE³⁺)₅(Ge^3-)₂(Ge^4-)₂(e^-). For RE₃Mg₂Ge₄, the total number of valence electrons contributed by the cations decreases, leading to a structural distortion that brings the isolated Ge atoms together to form an additional dimer. The electronic structure change here can be rationalized as (RE³⁺)₃(Mg²⁺)₂(Ge^3-)₄(e^-). The ideal electron count will be realised for the formula RE₂Mg₃Ge₄, but our studies have not shown evidence for extending the stoichiometry much beyond RE_5-xMg_xGe₄ (x ≈ 2) (Tobash et al., 2009). This suggests that metal–metal bonding and efficient packing are also critical for the stabilization of the phase, and the Zintl–Klemm concept is just a good starting point for consideration. Nonetheless, the ideas above can help to explain the fewer substitutions of RE³⁺ by Li⁺ cations, as discussed next.

Since Li⁺ is very similar to Mg²⁺ in terms of ionic size (Shannon, 1976), it is not surprising that the crystal chemistry observed when replacing the rare earth metal with lithium mirrors the results obtained with Mg. The RE_5-xLi_xGe₄ structure (Gd₅Si₄ type) is the same as that of RE_5-xMg_xGe₄ and has been considered in detail elsewhere (Pavlyuk et al. 1990; Xie et al. 2008; Peter et al. 2012; Fornasini et al. 2012). It can be broken down into two simpler building units (Fig. 2). One is the framework made by the rare earth metals, which is a combination of trigonal prisms and parallelepipeds, with Ge atoms located at the centres of the trigonal prisms. The second building unit is the pentagonal ring (Fig. 2c) made by Li and Ge atoms (paired in the ac plane). The interatomic distances within the Ge1—Ge1 [Symmetry code?] and Ge2—Ge3 dumbbells fall in the range 2.633 (2)–2.528 (3) Å. There does not appear to be any correlation between the refined Ge—Ge contacts and the decreasing unit-cell volumes due to the lanthanide contraction. We also note that the Ge—Ge distances are slightly longer than the sum of the corresponding Pauling radii (Pauling, 1960), which suggests the Ge—Ge interactions to be best regarded as covalent two-centre–two-electron bonds. Therefore, the electron count for the RE₄LiGe₄ structure can be represented as (RE³⁺)₄(Li⁺)(Ge^3-)₄(e^-). Such an electronic structure also accounts for the different homogeneity range of RE_5-xLi_xGe₄ compared with RE_5-xMg_xGe₄. For instance, if we apply the same electron count for RE₃Li₂Ge₄, we now have only 11 electrons from the cations, which are not sufficient to supply the electrons needed to form two pairs of Ge—Ge dimers (12 negative charges).

Li substitutions in RE₅Ge₄ were known before our work commenced, the first report being the example of Tm₄LiGe₄, which was characterized by Pavlyuk et al. (1990) on the basis of single-crystal X-ray diffraction data. The same paper also identifies the isotypic RE₄LiGe₄ (RE = Y, Gd, Er Lu) from powder X-ray diffraction data without discussing the possible homogeneity range. Very recently, Fornasini et al. (2012) reported the Nd₄LiGe₄ structure, also refined from single-crystal X-ray diffraction data, but they also did not comment on the small RE/Li disorder we have identified in our sample. The compound Yb₂Li_0.5Ge₂ (Yb₄LiGe₄) has been studied twice in the last four years, first by Xie et al. (2008) and then by Peter et al. (2012). Yb₄LiGe₄ was suggested to be a mixed-valent Yb²⁺/Yb³⁺ system, similar to Yb_5-xMg_xGe₄ (Tobash & Bobev, 2006), but again with no mention of the homogeneity range.

It should also be noted that we have chosen to discuss the present structures not as line [Linear?] compounds RE₄LiGe₄, as done previously, but rather as RE_5-xLi_xGe₄. The deviation from the idealized formula RE₄LiGe₄ is very small indeed, making it not very conspicuous, but the signs of the narrow phase width cannot be ignored.

Powder patterns of the products of reactions with different amounts of lithium metal as a starting material revealed peak shifts, which indicate that the unit-cell volumes change as a function of the nominal composition. Unfortunately, these were not phase-pure materials and further structural analysis was severely hindered. Fornasini et al. (2012) also commented on the heterogeneity of the samples. Some of the common RE–Li–Ge phases identified in this process include RELiGe₂ (RE = La–Nd, Sm and Eu; Pavlyuk et al., 1986; Bobev et al., 2012), RE₂Li₂Ge₃ and RE₃Li₄Ge₄ (Pavlyuk et al., 1989; Guo, You & Bobev, 2012), and RE₇Li₈Ge₁₀ and RE₁₁Li₁₂Ge₁₆ (RE = La–Nd, Sm; Guo, You, Jung & Bobev, 2012). The fact that Pavlyuk et al. (1990) reported a smaller unit cell for their Gd₄LiGe₄ sample than ours is yet another indicator that the amount of Li in RE_5-xLi_xGe₄ can be varied within a certain range. The major difficulty in establishing the solubility limits arises from the fact that Li and the rare earth metals have very different melting points, so obtaining equilibrium conditions is nearly impossible. Since the studied crystals were chosen from reactions with an excess of Li, we may speculate that RE_5-xLi_xGe₄ (x ≈ 1) most likely represents the Li-richest compositions that can be synthesized under the given conditions.

When the occupancy factors of the Wyckoff sites 8d were freed to vary durning trial refinements, for RE1 in all three cases the freed variable was always close to 100%, while the RE2 site consistently refined with 97% occupancy. A very similar observation was made with regard to the RE_5–xMg_xGe₄ (x ≈ 2) structure (Tobash et al., 2009), so we have assumed that Li can also partially substitute the RE2 atoms just like Mg does. Single-crystal X-ray data for the latter metal show that the substitution effect is well pronounced and easy to identify, while the very light Li makes it hard to detect or characterize. However, the refinement of a mixed occupied RE2/Li2 site was found to be statistically significant according to the Hamilton test (Hamilton, 1965). Specifically, at a significance level of 0.005, for model A (RE_5-xLi_xGe₄) and for model B (RE₄LiGe₄), respectively, the hypothesis that the former is better than the latter can be verified based on R = 1.004 < R_B/R_A = 1.013, where R is the interpolated value at the given significance level.

All of the above confirms that the title compounds are better described as solid solutions RE_5-xLi_xGe₄ (x ≈ 1) with narrow homogeneity ranges, rather than line [Linear?] compounds RE₄LiGe₄.

Related literature

For related literature, see: Bobev et al. (2012); Bruker (2002); Fornasini et al. (2012); Gelato & Parthé (1987); Guo, You & Bobev (2012); Guo, You, Jung & Bobev (2012); Hamilton (1965); Kauzlarich (1996); Kyunghan et al. (1997); Levin et al. (2002); Magen et al. (2003); Misra & Miller (2008); Pauling (1960); Pavlyuk et al. (1986, 1989, 1990); Pecharsky & Gschneidner (1997a, 1997b); Peter et al. (2012); Shannon (1976); Sheldrick (2008b); Tobash & Bobev (2006); Tobash et al. (2009); Xie et al. (2008).

S2. Experimental

All starting materials were purchased from common chemical vendors [pure elements from Alfa or Aldrich (>99.9 wt%)] and stored and handled inside an argon-filled glove box to prevent their deterioration from moisture and oxygen. All reactions were carried out by loading stoichiometric amounts of the respective elements inside Nb containers, which were then sealed with an arc welder. Subsequently, the Nb containers were flame sealed in evacuated (ca 10 ^-5 Torr; 1 Torr = 133.322 Pa) fused silica jackets. The synthesis followed the conventional solid-state route through direct fusion, but the process was somewhat complicated due to the very high melting points of the rare earth metals. The general synthetic route was that the reactions were heated in a tube furnace to 1358 K (200 K h^-1), kept for 5 h and then cooled slowly to 573 K (10 K h^-1). The title compounds were first identified as side products of reactions aimed at synthesizing NdLiGe₂ and SmLiGe₂. As mentioned in our previous work [Reference?], due to the high melting points of Nd (1300 K) and Sm (1315 K) it is necessary to increase the synthetic temperature. However, this also increases the possibility of Li leaking out of the Nb container, which would destroy the stoichiometric ratio and could lead to other phases. If Li were to leak outside the Nb tube and condense in the silica tube, it could be dangerous and the furnace should be stopped immediately.

S3. Refinement

Crystals were selected under an optical microscope and cut under oil to the desired small dimensions. They were then mounted on glass fibres and quickly placed under a cold nitrogen stream (ca 200 K) on a Bruker SMART CCD-based diffractometer.

The crystals diffracted strongly and an exposure time of 8–12 s per frame was sufficient. Data acquisition and integration were performed with the programs SMART (Bruker, 2002) and SAINT (Bruker, 2002), respectively. Structures were solved readily using direct methods and refined on F² using the SHELXL package (Sheldrick, 2008b). Refined parameters included the scale factor, extinction coefficients and atomic positions, with the corresponding anisotropic displacement parameters. Li had to be refined with an isotropic displacement parameter in the case of the Nd and Gd compounds, likely because of the inferior crystal quality compared with the Sm analogue. This is not without a precedent for elements with such a low Z number in structures dominated by very heavy elements. The atomic positions were standardized using STRUCTURE TIDY (Gelato & Parthé, 1987) prior to the final refinement step.

Structure refinements using the coordinates from the parent Sm₅Ge₄ type did not converge and it was obvious that the RE3 site (site 4c) was occupied by a much lighter atom. Therefore, in the next least-squares refinement cycles, RE3 was assigned as Li1, and its occupancy factor was allowed to vary. This time the refinements converged, and the site-occupancy factor for Li1 was very close to the full value. In the next round of least-squares refinement, all atoms (Li excluded in the case of the Nd and Gd compounds) were refined with anisotropic displacement parameters (ADP) and with fixed occupancies. Refinements converged at much lower R values. Subsequent refinement with free RE and Ge site-occupancy factors (done for an individual site, while the remaining site-occupancy factors were kept fixed) proved that the RE2 sites in all three structures are slightly underoccupied (within 6–8σ). All remaining crystallographic sites proved to be fully occupied, with the corresponding deviations from full occupancy less than 2σ.

Since Li is too light when refined together with RE atoms at the RE2 sites, its occupancy factor was very small. The actual solubility limits were not probed, as obtaining phase-pure samples was hindered by the very different melting points of Li and the rare earth metals. However, we note that such a stoichiometry breadth (and substitution pattern) is not unusual for germanide compounds with this structure type, as evidenced by studies of RE_5-xMg_xGe₄ (Tobash et al., 2009).

The highest residual density for the Sm compound is located 1.86 Å from Ge1 and the deepest hole is 1.84 Å from Ge2. For the Nd and Gd analogues, the peaks are close to Nd2 (1.9 Å) and Gd1 (0.85 Å), while the holes are located near Nd1 (0.84 Å) and Ge2 (0.72 Å), respectively.

Computing details

For all compounds, data collection: SMART (Bruker, 2002); cell refinement: SMART (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures

Fig. 1. Side-by-side comparison of the Sm₅Ge₄ and Gd₅Si₄ structures. The rare earth metals are shown as large spheres (green in the electronic version of the paper), Ge/Si atoms as light spheres (orange in the electronic version) and Li atoms as dark spheres (blue). The `interslab' dimers and broken dimers are outlined.

Fig. 2. (a) A representation of the RE_5–xLi_xGe₄ structure, viewed approximately down the [100] direction. The rare earth metals are shown as green spheres, Ge atoms as orange spheres and Li atoms as blue spheres. [Green and orange are not distinguishable in black and white - can alternatives be used, or different sizes?] (b) A representation of the first building unit, comprised of a trigonal prism (shaded, orange in the electronic version) and a parallelepiped (hollow framework of rare earth metals) (c) A view of the chain of vertex/edge-shared pentagonal rings built by Li atoms and Ge—Ge dimers.

(I) Tetrasamarium lithium tetragermanide

Crystal data

Sm3.97Li1.03Ge4	F(000) = 1508
Mr = 893.68	Dx = 6.940 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ac 2n	Cell parameters from 958 reflections
a = 7.2846 (16) Å	θ = 4.1–23.5°
b = 14.938 (3) Å	µ = 40.51 mm^−1
c = 7.8594 (17) Å	T = 200 K
V = 855.3 (3) Å^3	Irregular, grey
Z = 4	0.04 × 0.03 × 0.03 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1188 independent reflections
Radiation source: fine-focus sealed tube	968 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
ϕ and ω scans	θmax = 29.1°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
Tmin = 0.316, Tmax = 0.408	k = −20→20
11551 measured reflections	l = −10→10

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)] = 0.028	w = 1/[σ^2(Fo^2) + (0.015P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.051	(Δ/σ)max = 0.001
S = 1.02	Δρmax = 1.93 e Å^−3
1188 reflections	Δρmin = −2.07 e Å^−3
48 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00082 (5)

Special details

Experimental. Data collection is performed with two batch runs at ϕ = 0.00 ° (456 frames), and at ϕ = 90.00 ° (456 frames). Frame width = 0.40 ° in ω. Data is merged, corrected for decay, 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 > 2sigma(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)
Sm1	0.01938 (6)	0.59890 (3)	0.18707 (5)	0.00832 (12)
Sm2	0.32672 (6)	0.12815 (3)	0.17864 (5)	0.00764 (14)	0.983 (2)
Li2	0.32672 (6)	0.12815 (3)	0.17864 (5)	0.00764 (14)	0.017 (2)
Ge1	0.16093 (12)	0.03620 (6)	0.46727 (11)	0.0091 (2)
Ge2	0.01671 (16)	0.2500	0.08118 (16)	0.0091 (3)
Ge3	0.27599 (16)	0.2500	0.86645 (15)	0.0083 (3)
Li1	0.158 (3)	0.2500	0.528 (3)	0.015 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sm1	0.0078 (2)	0.0092 (2)	0.0080 (2)	0.00064 (16)	−0.00022 (16)	0.00073 (16)
Sm2	0.0077 (2)	0.0076 (2)	0.0076 (2)	0.00000 (15)	−0.00011 (17)	0.00003 (16)
Li2	0.0077 (2)	0.0076 (2)	0.0076 (2)	0.00000 (15)	−0.00011 (17)	0.00003 (16)
Ge1	0.0089 (4)	0.0099 (4)	0.0085 (4)	−0.0015 (3)	−0.0003 (3)	0.0017 (3)
Ge2	0.0078 (6)	0.0094 (6)	0.0102 (6)	0.000	0.0014 (5)	0.000
Ge3	0.0079 (6)	0.0078 (6)	0.0092 (6)	0.000	0.0009 (5)	0.000
Li1	0.011 (11)	0.022 (11)	0.013 (10)	0.000	0.003 (9)	0.000

Geometric parameters (Å, º)

Sm1—Ge1^i	3.0472 (11)	Ge1—Sm1^xvi	3.5161 (11)
Sm1—Ge3^ii	3.0504 (10)	Ge2—Ge3^xi	2.5329 (17)
Sm1—Ge2^iii	3.0999 (11)	Ge2—Li1^viii	2.75 (2)
Sm1—Ge3^iv	3.1467 (10)	Ge2—Li2^viii	2.9652 (11)
Sm1—Ge1^v	3.1595 (11)	Ge2—Sm2^viii	2.9652 (11)
Sm1—Ge1^vi	3.1600 (10)	Ge2—Li2^vii	2.9652 (11)
Sm1—Li1^iv	3.432 (15)	Ge2—Sm2^vii	2.9652 (11)
Sm1—Li1^ii	3.490 (16)	Ge2—Li2^vi	2.9999 (11)
Sm1—Ge1^vii	3.5160 (11)	Ge2—Sm2^vi	2.9999 (11)
Sm1—Sm1^viii	3.7742 (8)	Ge2—Sm1^xvii	3.0999 (11)
Sm1—Sm1^ix	3.7743 (8)	Ge2—Sm1^iii	3.0999 (11)
Sm1—Sm2^vii	3.8194 (9)	Ge3—Ge2^xviii	2.5329 (17)
Sm2—Ge1	2.9139 (10)	Ge3—Li1	2.80 (2)
Sm2—Ge2^ix	2.9651 (11)	Ge3—Li1^xix	2.90 (2)
Sm2—Ge1^x	2.9658 (10)	Ge3—Sm1^xiv	3.0504 (10)
Sm2—Ge2	3.0000 (11)	Ge3—Sm1^xx	3.0504 (10)
Sm2—Ge1^ix	3.0214 (11)	Ge3—Li2^xviii	3.0773 (11)
Sm2—Ge3^xi	3.0773 (11)	Ge3—Sm2^xviii	3.0773 (11)
Sm2—Li1^ix	3.432 (17)	Ge3—Li2^xxi	3.0773 (11)
Sm2—Li1	3.516 (17)	Ge3—Sm2^xxi	3.0773 (11)
Sm2—Li2^vi	3.6405 (11)	Ge3—Sm1^xv	3.1467 (10)
Sm2—Sm2^vi	3.6405 (11)	Ge3—Sm1^iv	3.1467 (10)
Sm2—Sm2^viii	3.8111 (8)	Li1—Ge2^ix	2.75 (2)
Sm2—Li2^viii	3.8111 (8)	Li1—Ge3^xxii	2.90 (2)
Ge1—Ge1^xii	2.6328 (18)	Li1—Ge1^vi	3.229 (3)
Ge1—Li2^xiii	2.9657 (10)	Li1—Li2^viii	3.432 (17)
Ge1—Sm2^xiii	2.9657 (10)	Li1—Sm2^viii	3.432 (17)
Ge1—Li2^viii	3.0214 (11)	Li1—Li2^vii	3.432 (17)
Ge1—Sm2^viii	3.0214 (11)	Li1—Sm2^vii	3.432 (17)
Ge1—Sm1^xiv	3.0472 (11)	Li1—Sm1^xv	3.432 (15)
Ge1—Sm1^xv	3.1595 (11)	Li1—Sm1^iv	3.432 (15)
Ge1—Sm1^vi	3.1600 (10)	Li1—Sm1^xiv	3.490 (16)
Ge1—Li1	3.229 (3)
Ge1^i—Sm1—Ge3^ii	96.66 (3)	Sm2^viii—Ge1—Sm1^xvi	136.75 (3)
Ge1^i—Sm1—Ge2^iii	84.43 (3)	Sm1^xiv—Ge1—Sm1^xvi	78.72 (3)
Ge3^ii—Sm1—Ge2^iii	79.45 (3)	Sm1^xv—Ge1—Sm1^xvi	140.85 (3)
Ge1^i—Sm1—Ge3^iv	131.86 (3)	Sm1^vi—Ge1—Sm1^xvi	68.61 (2)
Ge3^ii—Sm1—Ge3^iv	82.25 (2)	Li1—Ge1—Sm1^xvi	128.6 (4)
Ge2^iii—Sm1—Ge3^iv	47.84 (3)	Ge3^xi—Ge2—Li1^viii	120.0 (4)
Ge1^i—Sm1—Ge1^v	135.57 (3)	Ge3^xi—Ge2—Li2^viii	140.56 (2)
Ge3^ii—Sm1—Ge1^v	91.44 (3)	Li1^viii—Ge2—Li2^viii	75.8 (3)
Ge2^iii—Sm1—Ge1^v	139.94 (3)	Ge3^xi—Ge2—Sm2^viii	140.56 (2)
Ge3^iv—Sm1—Ge1^v	92.49 (3)	Li1^viii—Ge2—Sm2^viii	75.8 (3)
Ge1^i—Sm1—Ge1^vi	87.099 (19)	Li2^viii—Ge2—Sm2^viii	0.000 (19)
Ge3^ii—Sm1—Ge1^vi	89.49 (3)	Ge3^xi—Ge2—Li2^vii	140.55 (2)
Ge2^iii—Sm1—Ge1^vi	165.17 (3)	Li1^viii—Ge2—Li2^vii	75.8 (3)
Ge3^iv—Sm1—Ge1^vi	140.75 (3)	Li2^viii—Ge2—Li2^vii	75.74 (4)
Ge1^v—Sm1—Ge1^vi	49.24 (3)	Sm2^viii—Ge2—Li2^vii	75.74 (4)
Ge1^i—Sm1—Li1^iv	149.3 (3)	Ge3^xi—Ge2—Sm2^vii	140.55 (2)
Ge3^ii—Sm1—Li1^iv	52.8 (3)	Li1^viii—Ge2—Sm2^vii	75.8 (3)
Ge2^iii—Sm1—Li1^iv	86.2 (2)	Li2^viii—Ge2—Sm2^vii	75.74 (4)
Ge3^iv—Sm1—Li1^iv	50.1 (3)	Sm2^viii—Ge2—Sm2^vii	75.74 (4)
Ge1^v—Sm1—Li1^iv	58.5 (2)	Li2^vii—Ge2—Sm2^vii	0.000 (14)
Ge1^vi—Sm1—Li1^iv	95.1 (3)	Ge3^xi—Ge2—Li2^vi	66.97 (4)
Ge1^i—Sm1—Li1^ii	58.7 (2)	Li1^viii—Ge2—Li2^vi	142.641 (19)
Ge3^ii—Sm1—Li1^ii	50.1 (3)	Li2^viii—Ge2—Li2^vi	124.15 (4)
Ge2^iii—Sm1—Li1^ii	48.9 (3)	Sm2^viii—Ge2—Li2^vi	124.15 (4)
Ge3^iv—Sm1—Li1^ii	87.0 (2)	Li2^vii—Ge2—Li2^vi	79.42 (2)
Ge1^v—Sm1—Li1^ii	141.2 (3)	Sm2^vii—Ge2—Li2^vi	79.42 (2)
Ge1^vi—Sm1—Li1^ii	116.3 (3)	Ge3^xi—Ge2—Sm2^vi	66.97 (4)
Li1^iv—Sm1—Li1^ii	93.6 (3)	Li1^viii—Ge2—Sm2^vi	142.641 (19)
Ge1^i—Sm1—Ge1^vii	101.28 (3)	Li2^viii—Ge2—Sm2^vi	124.15 (4)
Ge3^ii—Sm1—Ge1^vii	161.28 (3)	Sm2^viii—Ge2—Sm2^vi	124.15 (4)
Ge2^iii—Sm1—Ge1^vii	96.91 (3)	Li2^vii—Ge2—Sm2^vi	79.42 (2)
Ge3^iv—Sm1—Ge1^vii	81.83 (3)	Sm2^vii—Ge2—Sm2^vi	79.42 (2)
Ge1^v—Sm1—Ge1^vii	79.500 (18)	Li2^vi—Ge2—Sm2^vi	0.00 (2)
Ge1^vi—Sm1—Ge1^vii	96.67 (3)	Ge3^xi—Ge2—Sm2	66.97 (4)
Li1^iv—Sm1—Ge1^vii	108.8 (3)	Li1^viii—Ge2—Sm2	142.641 (19)
Li1^ii—Sm1—Ge1^vii	138.4 (3)	Li2^viii—Ge2—Sm2	79.42 (2)
Ge1^i—Sm1—Sm1^viii	152.39 (2)	Sm2^viii—Ge2—Sm2	79.42 (2)
Ge3^ii—Sm1—Sm1^viii	110.52 (3)	Li2^vii—Ge2—Sm2	124.15 (4)
Ge2^iii—Sm1—Sm1^viii	95.53 (2)	Sm2^vii—Ge2—Sm2	124.15 (4)
Ge3^iv—Sm1—Sm1^viii	51.33 (2)	Li2^vi—Ge2—Sm2	74.71 (4)
Ge1^v—Sm1—Sm1^viii	51.207 (19)	Sm2^vi—Ge2—Sm2	74.71 (4)
Ge1^vi—Sm1—Sm1^viii	97.60 (2)	Ge3^xi—Ge2—Sm1^xvii	67.05 (3)
Li1^iv—Sm1—Sm1^viii	57.7 (3)	Li1^viii—Ge2—Sm1^xvii	73.0 (3)
Li1^ii—Sm1—Sm1^viii	138.0 (2)	Li2^viii—Ge2—Sm1^xvii	86.93 (2)
Ge1^vii—Sm1—Sm1^viii	51.225 (18)	Sm2^viii—Ge2—Sm1^xvii	86.93 (2)
Ge1^i—Sm1—Sm1^ix	53.92 (2)	Li2^vii—Ge2—Sm1^xvii	147.18 (4)
Ge3^ii—Sm1—Sm1^ix	53.65 (2)	Sm2^vii—Ge2—Sm1^xvii	147.18 (4)
Ge2^iii—Sm1—Sm1^ix	105.07 (2)	Li2^vi—Ge2—Sm1^xvii	132.79 (4)
Ge3^iv—Sm1—Sm1^ix	134.02 (2)	Sm2^vi—Ge2—Sm1^xvii	132.79 (4)
Ge1^v—Sm1—Sm1^ix	100.13 (3)	Sm2—Ge2—Sm1^xvii	78.21 (2)
Ge1^vi—Sm1—Sm1^ix	60.16 (2)	Ge3^xi—Ge2—Sm1^iii	67.05 (3)
Li1^iv—Sm1—Sm1^ix	101.1 (3)	Li1^viii—Ge2—Sm1^iii	73.0 (3)
Li1^ii—Sm1—Sm1^ix	56.2 (3)	Li2^viii—Ge2—Sm1^iii	147.18 (4)
Ge1^vii—Sm1—Sm1^ix	143.813 (17)	Sm2^viii—Ge2—Sm1^iii	147.18 (4)
Sm1^viii—Sm1—Sm1^ix	149.61 (3)	Li2^vii—Ge2—Sm1^iii	86.93 (2)
Ge1^i—Sm1—Sm2^vii	99.47 (2)	Sm2^vii—Ge2—Sm1^iii	86.93 (2)
Ge3^ii—Sm1—Sm2^vii	135.15 (3)	Li2^vi—Ge2—Sm1^iii	78.21 (2)
Ge2^iii—Sm1—Sm2^vii	143.46 (2)	Sm2^vi—Ge2—Sm1^iii	78.21 (2)
Ge3^iv—Sm1—Sm2^vii	115.01 (3)	Sm2—Ge2—Sm1^iii	132.79 (4)
Ge1^v—Sm1—Sm2^vii	49.186 (17)	Sm1^xvii—Ge2—Sm1^iii	93.47 (4)
Ge1^vi—Sm1—Sm2^vii	50.22 (2)	Ge2^xviii—Ge3—Li1	113.9 (4)
Li1^iv—Sm1—Sm2^vii	105.4 (2)	Ge2^xviii—Ge3—Li1^xix	121.6 (4)
Li1^ii—Sm1—Sm2^vii	157.0 (2)	Li1—Ge3—Li1^xix	124.5 (6)
Ge1^vii—Sm1—Sm2^vii	46.585 (17)	Ge2^xviii—Ge3—Sm1^xiv	132.25 (2)
Sm1^viii—Sm1—Sm2^vii	64.721 (11)	Li1—Ge3—Sm1^xiv	73.2 (3)
Sm1^ix—Sm1—Sm2^vii	106.391 (13)	Li1^xix—Ge3—Sm1^xiv	70.3 (3)
Ge1—Sm2—Ge2^ix	89.27 (3)	Ge2^xviii—Ge3—Sm1^xx	132.25 (2)
Ge1—Sm2—Ge1^x	93.35 (2)	Li1—Ge3—Sm1^xx	73.2 (3)
Ge2^ix—Sm2—Ge1^x	148.28 (3)	Li1^xix—Ge3—Sm1^xx	70.3 (3)
Ge1—Sm2—Ge2	99.95 (3)	Sm1^xiv—Ge3—Sm1^xx	95.46 (4)
Ge2^ix—Sm2—Ge2	98.13 (3)	Ge2^xviii—Ge3—Li2^xviii	63.79 (3)
Ge1^x—Sm2—Ge2	112.47 (3)	Li1—Ge3—Li2^xviii	142.72 (9)
Ge1—Sm2—Ge1^ix	114.53 (3)	Li1^xix—Ge3—Li2^xviii	70.0 (3)
Ge2^ix—Sm2—Ge1^ix	98.31 (3)	Sm1^xiv—Ge3—Li2^xviii	82.65 (2)
Ge1^x—Sm2—Ge1^ix	52.16 (3)	Sm1^xx—Ge3—Li2^xviii	138.38 (4)
Ge2—Sm2—Ge1^ix	141.77 (3)	Ge2^xviii—Ge3—Sm2^xviii	63.79 (3)
Ge1—Sm2—Ge3^xi	148.18 (3)	Li1—Ge3—Sm2^xviii	142.72 (9)
Ge2^ix—Sm2—Ge3^xi	101.57 (3)	Li1^xix—Ge3—Sm2^xviii	70.0 (3)
Ge1^x—Sm2—Ge3^xi	92.68 (3)	Sm1^xiv—Ge3—Sm2^xviii	82.65 (2)
Ge2—Sm2—Ge3^xi	49.24 (3)	Sm1^xx—Ge3—Sm2^xviii	138.38 (4)
Ge1^ix—Sm2—Ge3^xi	93.61 (3)	Li2^xviii—Ge3—Sm2^xviii	0.00 (2)
Ge1—Sm2—Li1^ix	155.5 (3)	Ge2^xviii—Ge3—Li2^xxi	63.79 (3)
Ge2^ix—Sm2—Li1^ix	69.3 (3)	Li1—Ge3—Li2^xxi	142.72 (9)
Ge1^x—Sm2—Li1^ix	98.8 (2)	Li1^xix—Ge3—Li2^xxi	70.0 (3)
Ge2—Sm2—Li1^ix	95.0 (3)	Sm1^xiv—Ge3—Li2^xxi	138.38 (4)
Ge1^ix—Sm2—Li1^ix	59.65 (19)	Sm1^xx—Ge3—Li2^xxi	82.65 (2)
Ge3^xi—Sm2—Li1^ix	52.7 (3)	Li2^xviii—Ge3—Li2^xxi	72.53 (3)
Ge1—Sm2—Li1	59.42 (17)	Sm2^xviii—Ge3—Li2^xxi	72.53 (3)
Ge2^ix—Sm2—Li1	49.3 (3)	Ge2^xviii—Ge3—Sm2^xxi	63.79 (3)
Ge1^x—Sm2—Li1	151.2 (2)	Li1—Ge3—Sm2^xxi	142.72 (9)
Ge2—Sm2—Li1	67.8 (3)	Li1^xix—Ge3—Sm2^xxi	70.0 (3)
Ge1^ix—Sm2—Li1	144.4 (3)	Sm1^xiv—Ge3—Sm2^xxi	138.38 (4)
Ge3^xi—Sm2—Li1	105.9 (2)	Sm1^xx—Ge3—Sm2^xxi	82.65 (2)
Li1^ix—Sm2—Li1	109.9 (3)	Li2^xviii—Ge3—Sm2^xxi	72.53 (3)
Ge1—Sm2—Li2^vi	118.125 (19)	Sm2^xviii—Ge3—Sm2^xxi	72.53 (3)
Ge2^ix—Sm2—Li2^vi	52.129 (18)	Li2^xxi—Ge3—Sm2^xxi	0.000 (16)
Ge1^x—Sm2—Li2^vi	145.88 (2)	Ge2^xviii—Ge3—Sm1^xv	65.11 (3)
Ge2—Sm2—Li2^vi	52.644 (18)	Li1—Ge3—Sm1^xv	70.3 (3)
Ge1^ix—Sm2—Li2^vi	117.039 (19)	Li1^xix—Ge3—Sm1^xv	133.91 (4)
Ge3^xi—Sm2—Li2^vi	53.735 (17)	Sm1^xiv—Ge3—Sm1^xv	75.02 (2)
Li1^ix—Sm2—Li2^vi	57.97 (18)	Sm1^xx—Ge3—Sm1^xv	143.43 (4)
Li1—Sm2—Li2^vi	58.82 (17)	Li2^xviii—Ge3—Sm1^xv	76.37 (2)
Ge1—Sm2—Sm2^vi	118.125 (19)	Sm2^xviii—Ge3—Sm1^xv	76.37 (2)
Ge2^ix—Sm2—Sm2^vi	52.129 (18)	Li2^xxi—Ge3—Sm1^xv	127.81 (4)
Ge1^x—Sm2—Sm2^vi	145.88 (2)	Sm2^xxi—Ge3—Sm1^xv	127.81 (4)
Ge2—Sm2—Sm2^vi	52.644 (18)	Ge2^xviii—Ge3—Sm1^iv	65.11 (3)
Ge1^ix—Sm2—Sm2^vi	117.039 (19)	Li1—Ge3—Sm1^iv	70.3 (3)
Ge3^xi—Sm2—Sm2^vi	53.735 (17)	Li1^xix—Ge3—Sm1^iv	133.91 (4)
Li1^ix—Sm2—Sm2^vi	57.97 (18)	Sm1^xiv—Ge3—Sm1^iv	143.43 (4)
Li1—Sm2—Sm2^vi	58.82 (17)	Sm1^xx—Ge3—Sm1^iv	75.02 (2)
Li2^vi—Sm2—Sm2^vi	0.000 (19)	Li2^xviii—Ge3—Sm1^iv	127.81 (4)
Ge1—Sm2—Sm2^viii	51.30 (2)	Sm2^xviii—Ge3—Sm1^iv	127.81 (4)
Ge2^ix—Sm2—Sm2^viii	104.99 (3)	Li2^xxi—Ge3—Sm1^iv	76.37 (2)
Ge1^x—Sm2—Sm2^viii	101.18 (2)	Sm2^xxi—Ge3—Sm1^iv	76.37 (2)
Ge2—Sm2—Sm2^viii	49.89 (2)	Sm1^xv—Ge3—Sm1^iv	91.67 (4)
Ge1^ix—Sm2—Sm2^viii	151.860 (19)	Ge2^ix—Li1—Ge3	90.3 (6)
Ge3^xi—Sm2—Sm2^viii	96.89 (3)	Ge2^ix—Li1—Ge3^xxii	178.4 (8)
Li1^ix—Sm2—Sm2^viii	144.2 (2)	Ge3—Li1—Ge3^xxii	91.3 (6)
Li1—Sm2—Sm2^viii	55.7 (3)	Ge2^ix—Li1—Ge1	87.0 (4)
Li2^vi—Sm2—Sm2^viii	90.0	Ge3—Li1—Ge1	98.0 (4)
Sm2^vi—Sm2—Sm2^viii	90.0	Ge3^xxii—Li1—Ge1	92.8 (4)
Ge1—Sm2—Li2^viii	51.30 (2)	Ge2^ix—Li1—Ge1^vi	87.0 (4)
Ge2^ix—Sm2—Li2^viii	104.99 (3)	Ge3—Li1—Ge1^vi	98.0 (4)
Ge1^x—Sm2—Li2^viii	101.18 (2)	Ge3^xxii—Li1—Ge1^vi	92.8 (4)
Ge2—Sm2—Li2^viii	49.89 (2)	Ge1—Li1—Ge1^vi	163.0 (7)
Ge1^ix—Sm2—Li2^viii	151.860 (19)	Ge2^ix—Li1—Li2^viii	121.4 (5)
Ge3^xi—Sm2—Li2^viii	96.89 (3)	Ge3—Li1—Li2^viii	131.8 (5)
Li1^ix—Sm2—Li2^viii	144.2 (2)	Ge3^xxii—Li1—Li2^viii	57.4 (3)
Li1—Sm2—Li2^viii	55.7 (3)	Ge1—Li1—Li2^viii	53.84 (18)
Li2^vi—Sm2—Li2^viii	90.0	Ge1^vi—Li1—Li2^viii	117.3 (5)
Sm2^vi—Sm2—Li2^viii	90.0	Ge2^ix—Li1—Sm2^viii	121.4 (5)
Sm2^viii—Sm2—Li2^viii	0.000 (17)	Ge3—Li1—Sm2^viii	131.8 (5)
Ge1^xii—Ge1—Sm2	135.63 (5)	Ge3^xxii—Li1—Sm2^viii	57.4 (3)
Ge1^xii—Ge1—Li2^xiii	65.01 (3)	Ge1—Li1—Sm2^viii	53.84 (18)
Sm2—Ge1—Li2^xiii	144.46 (3)	Ge1^vi—Li1—Sm2^viii	117.3 (5)
Ge1^xii—Ge1—Sm2^xiii	65.01 (3)	Li2^viii—Li1—Sm2^viii	0.000 (15)
Sm2—Ge1—Sm2^xiii	144.46 (3)	Ge2^ix—Li1—Li2^vii	121.4 (6)
Li2^xiii—Ge1—Sm2^xiii	0.00 (2)	Ge3—Li1—Li2^vii	131.8 (5)
Ge1^xii—Ge1—Li2^viii	62.83 (4)	Ge3^xxii—Li1—Li2^vii	57.4 (3)
Sm2—Ge1—Li2^viii	79.88 (3)	Ge1—Li1—Li2^vii	117.3 (5)
Li2^xiii—Ge1—Li2^viii	127.84 (3)	Ge1^vi—Li1—Li2^vii	53.84 (18)
Sm2^xiii—Ge1—Li2^viii	127.84 (3)	Li2^viii—Li1—Li2^vii	64.1 (4)
Ge1^xii—Ge1—Sm2^viii	62.83 (4)	Sm2^viii—Li1—Li2^vii	64.1 (4)
Sm2—Ge1—Sm2^viii	79.88 (3)	Ge2^ix—Li1—Sm2^vii	121.4 (6)
Li2^xiii—Ge1—Sm2^viii	127.84 (3)	Ge3—Li1—Sm2^vii	131.8 (5)
Sm2^xiii—Ge1—Sm2^viii	127.84 (3)	Ge3^xxii—Li1—Sm2^vii	57.4 (3)
Li2^viii—Ge1—Sm2^viii	0.000 (9)	Ge1—Li1—Sm2^vii	117.3 (5)
Ge1^xii—Ge1—Sm1^xiv	134.11 (5)	Ge1^vi—Li1—Sm2^vii	53.84 (18)
Sm2—Ge1—Sm1^xiv	88.84 (3)	Li2^viii—Li1—Sm2^vii	64.1 (4)
Li2^xiii—Ge1—Sm1^xiv	85.05 (3)	Sm2^viii—Li1—Sm2^vii	64.1 (4)
Sm2^xiii—Ge1—Sm1^xiv	85.05 (3)	Li2^vii—Li1—Sm2^vii	0.000 (10)
Li2^viii—Ge1—Sm1^xiv	133.73 (3)	Ge2^ix—Li1—Sm1^xv	124.2 (5)
Sm2^viii—Ge1—Sm1^xiv	133.73 (3)	Ge3—Li1—Sm1^xv	59.7 (3)
Ge1^xii—Ge1—Sm1^xv	65.39 (4)	Ge3^xxii—Li1—Sm1^xv	56.8 (3)
Sm2—Ge1—Sm1^xv	134.58 (3)	Ge1—Li1—Sm1^xv	56.53 (13)
Li2^xiii—Ge1—Sm1^xv	77.08 (3)	Ge1^vi—Li1—Sm1^xv	138.5 (6)
Sm2^xiii—Ge1—Sm1^xv	77.08 (3)	Li2^viii—Li1—Sm1^xv	72.2 (3)
Li2^viii—Ge1—Sm1^xv	81.75 (3)	Sm2^viii—Li1—Sm1^xv	72.2 (3)
Sm2^viii—Ge1—Sm1^xv	81.75 (3)	Li2^vii—Li1—Sm1^xv	113.1 (6)
Sm1^xiv—Ge1—Sm1^xv	74.88 (2)	Sm2^vii—Li1—Sm1^xv	113.1 (6)
Ge1^xii—Ge1—Sm1^vi	65.37 (4)	Ge2^ix—Li1—Sm1^iv	124.2 (5)
Sm2—Ge1—Sm1^vi	83.90 (3)	Ge3—Li1—Sm1^iv	59.7 (3)
Li2^xiii—Ge1—Sm1^vi	82.62 (3)	Ge3^xxii—Li1—Sm1^iv	56.8 (3)
Sm2^xiii—Ge1—Sm1^vi	82.62 (3)	Ge1—Li1—Sm1^iv	138.5 (6)
Li2^viii—Ge1—Sm1^vi	76.29 (3)	Ge1^vi—Li1—Sm1^iv	56.53 (13)
Sm2^viii—Ge1—Sm1^vi	76.29 (3)	Li2^viii—Li1—Sm1^iv	113.1 (6)
Sm1^xiv—Ge1—Sm1^vi	147.22 (3)	Sm2^viii—Li1—Sm1^iv	113.1 (6)
Sm1^xv—Ge1—Sm1^vi	130.76 (3)	Li2^vii—Li1—Sm1^iv	72.2 (3)
Ge1^xii—Ge1—Li1	111.8 (4)	Sm2^vii—Li1—Sm1^iv	72.2 (3)
Sm2—Ge1—Li1	69.6 (4)	Sm1^xv—Li1—Sm1^iv	82.2 (4)
Li2^xiii—Ge1—Li1	137.4 (4)	Ge2^ix—Li1—Sm1^xiv	58.1 (3)
Sm2^xiii—Ge1—Li1	137.4 (4)	Ge3—Li1—Sm1^xiv	56.8 (3)
Li2^viii—Ge1—Li1	66.5 (4)	Ge3^xxii—Li1—Sm1^xiv	122.9 (5)
Sm2^viii—Ge1—Li1	66.5 (4)	Ge1—Li1—Sm1^xiv	53.77 (15)
Sm1^xiv—Ge1—Li1	67.5 (4)	Ge1^vi—Li1—Sm1^xiv	133.5 (6)
Sm1^xv—Ge1—Li1	65.0 (4)	Li2^viii—Li1—Sm1^xiv	107.46 (6)
Sm1^vi—Ge1—Li1	137.1 (4)	Sm2^viii—Li1—Sm1^xiv	107.46 (6)
Ge1^xii—Ge1—Sm1^xvi	119.54 (5)	Li2^vii—Li1—Sm1^xiv	170.5 (5)
Sm2—Ge1—Sm1^xvi	72.19 (2)	Sm2^vii—Li1—Sm1^xiv	170.5 (5)
Li2^xiii—Ge1—Sm1^xvi	72.27 (2)	Sm1^xv—Li1—Sm1^xiv	66.1 (2)
Sm2^xiii—Ge1—Sm1^xvi	72.27 (2)	Sm1^iv—Li1—Sm1^xiv	116.4 (6)
Li2^viii—Ge1—Sm1^xvi	136.75 (3)

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

(II) Tetraneodymium lithium tetragermanide

Crystal data

Nd3.97Li1.03Ge4	F(000) = 1477
Mr = 870.14	Dx = 6.548 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ac 2n	Cell parameters from 387 reflections
a = 7.3649 (12) Å	θ = 5.1–18.0°
b = 15.092 (2) Å	µ = 36.23 mm^−1
c = 7.9406 (13) Å	T = 200 K
V = 882.6 (2) Å^3	Irregular, black
Z = 4	0.03 × 0.03 × 0.02 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1094 independent reflections
Radiation source: fine-focus sealed tube	823 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.124
ϕ and ω scans	θmax = 27.9°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
Tmin = 0.410, Tmax = 0.531	k = −19→19
10856 measured reflections	l = −10→10

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)] = 0.036	w = 1/[σ^2(Fo^2) + (0.0075P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.060	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 2.69 e Å^−3
1094 reflections	Δρmin = −2.16 e Å^−3
45 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00024 (4)

Special details

Experimental. Data collection is performed with two batch runs at ϕ = 0.00 ° (456 frames), and at ϕ = 90.00 ° (456 frames). Frame width = 0.40 ° in ω. Data is merged, corrected for decay, 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 > 2sigma(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)
Nd1	0.02129 (8)	0.59950 (4)	0.18745 (8)	0.01011 (19)
Nd2	0.32566 (9)	0.12811 (4)	0.17943 (8)	0.0092 (2)	0.985 (3)
Li2	0.32566 (9)	0.12811 (4)	0.17943 (8)	0.0092 (2)	0.015 (3)
Ge1	0.15859 (17)	0.03601 (8)	0.46828 (15)	0.0106 (3)
Ge2	0.0155 (2)	0.2500	0.0794 (2)	0.0109 (4)
Ge3	0.2731 (2)	0.2500	0.8672 (2)	0.0104 (4)
Li1	0.163 (4)	0.2500	0.528 (3)	0.008 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nd1	0.0101 (3)	0.0114 (3)	0.0089 (3)	0.0004 (3)	0.0006 (3)	0.0002 (3)
Nd2	0.0095 (3)	0.0096 (3)	0.0085 (3)	0.0002 (2)	0.0002 (3)	−0.0001 (3)
Li2	0.0095 (3)	0.0096 (3)	0.0085 (3)	0.0002 (2)	0.0002 (3)	−0.0001 (3)
Ge1	0.0107 (6)	0.0123 (7)	0.0088 (6)	−0.0011 (5)	−0.0002 (5)	0.0013 (5)
Ge2	0.0116 (9)	0.0116 (10)	0.0095 (9)	0.000	−0.0003 (7)	0.000
Ge3	0.0124 (10)	0.0105 (10)	0.0082 (9)	0.000	0.0002 (7)	0.000

Geometric parameters (Å, º)

Nd1—Ge3^i	3.0806 (14)	Ge2—Ge3^xii	2.537 (2)
Nd1—Ge1^ii	3.0831 (14)	Ge2—Li1^vii	2.73 (3)
Nd1—Ge2^iii	3.1179 (14)	Ge2—Li2^vii	3.0013 (15)
Nd1—Ge3^iv	3.1699 (14)	Ge2—Nd2^vii	3.0013 (15)
Nd1—Ge1^v	3.1853 (14)	Ge2—Li2^ix	3.0013 (15)
Nd1—Ge1^vi	3.1903 (14)	Ge2—Nd2^ix	3.0013 (15)
Nd1—Li1^iv	3.48 (2)	Ge2—Nd2^vi	3.0387 (16)
Nd1—Li1^i	3.49 (2)	Ge2—Li2^vi	3.0387 (16)
Nd1—Nd1^vii	3.8141 (7)	Ge2—Nd1^xvii	3.1179 (14)
Nd1—Nd1^viii	3.8141 (7)	Ge2—Nd1^iii	3.1179 (14)
Nd1—Nd2^ix	3.8721 (10)	Ge3—Ge2^xviii	2.537 (2)
Nd1—Nd2^x	3.8990 (10)	Ge3—Li1	2.82 (3)
Nd2—Ge1	2.9507 (14)	Ge3—Li1^xix	2.99 (3)
Nd2—Ge1^xi	2.9932 (14)	Ge3—Nd1^xv	3.0805 (14)
Nd2—Ge2^viii	3.0013 (16)	Ge3—Nd1^xx	3.0805 (14)
Nd2—Ge2	3.0386 (16)	Ge3—Li2^xviii	3.1115 (15)
Nd2—Ge1^viii	3.0529 (14)	Ge3—Nd2^xviii	3.1115 (15)
Nd2—Ge3^xii	3.1115 (15)	Ge3—Li2^xxi	3.1115 (15)
Nd2—Li1^viii	3.50 (2)	Ge3—Nd2^xxi	3.1115 (15)
Nd2—Li1	3.53 (2)	Ge3—Nd1^xvi	3.1698 (14)
Nd2—Li2^vi	3.6793 (14)	Ge3—Nd1^iv	3.1698 (14)
Nd2—Nd2^vi	3.6793 (14)	Li1—Ge2^viii	2.73 (3)
Nd2—Nd2^vii	3.8492 (7)	Li1—Ge3^xxii	2.99 (3)
Nd2—Nd2^viii	3.8493 (7)	Li1—Nd1^xvi	3.48 (2)
Ge1—Ge1^xiii	2.625 (3)	Li1—Nd1^iv	3.48 (2)
Ge1—Li2^xiv	2.9933 (14)	Li1—Nd1^xv	3.49 (2)
Ge1—Nd2^xiv	2.9933 (14)	Li1—Nd1^xx	3.49 (2)
Ge1—Li2^vii	3.0528 (14)	Li1—Li2^vii	3.50 (2)
Ge1—Nd2^vii	3.0528 (14)	Li1—Nd2^vii	3.50 (2)
Ge1—Nd1^xv	3.0831 (14)	Li1—Li2^ix	3.50 (2)
Ge1—Nd1^xvi	3.1854 (14)	Li1—Nd2^ix	3.50 (2)
Ge1—Nd1^vi	3.1903 (14)
Ge3^i—Nd1—Ge1^ii	96.59 (4)	Nd1^xvi—Ge1—Nd1^vi	131.37 (4)
Ge3^i—Nd1—Ge2^iii	79.65 (4)	Ge3^xii—Ge2—Li1^vii	120.3 (5)
Ge1^ii—Nd1—Ge2^iii	84.80 (4)	Ge3^xii—Ge2—Li2^vii	140.54 (3)
Ge3^i—Nd1—Ge3^iv	82.61 (3)	Li1^vii—Ge2—Li2^vii	75.9 (4)
Ge1^ii—Nd1—Ge3^iv	131.95 (4)	Ge3^xii—Ge2—Nd2^vii	140.54 (3)
Ge2^iii—Nd1—Ge3^iv	47.59 (4)	Li1^vii—Ge2—Nd2^vii	75.9 (4)
Ge3^i—Nd1—Ge1^v	91.64 (4)	Li2^vii—Ge2—Nd2^vii	0.00 (3)
Ge1^ii—Nd1—Ge1^v	135.15 (5)	Ge3^xii—Ge2—Li2^ix	140.54 (3)
Ge2^iii—Nd1—Ge1^v	140.01 (4)	Li1^vii—Ge2—Li2^ix	75.9 (4)
Ge3^iv—Nd1—Ge1^v	92.78 (4)	Li2^vii—Ge2—Li2^ix	75.61 (5)
Ge3^i—Nd1—Ge1^vi	89.60 (4)	Nd2^vii—Ge2—Li2^ix	75.61 (5)
Ge1^ii—Nd1—Ge1^vi	87.30 (2)	Ge3^xii—Ge2—Nd2^ix	140.54 (3)
Ge2^iii—Nd1—Ge1^vi	165.82 (4)	Li1^vii—Ge2—Nd2^ix	75.9 (4)
Ge3^iv—Nd1—Ge1^vi	140.52 (4)	Li2^vii—Ge2—Nd2^ix	75.61 (5)
Ge1^v—Nd1—Ge1^vi	48.63 (4)	Nd2^vii—Ge2—Nd2^ix	75.61 (5)
Ge3^i—Nd1—Li1^iv	53.8 (4)	Li2^ix—Ge2—Nd2^ix	0.00 (3)
Ge1^ii—Nd1—Li1^iv	150.2 (4)	Ge3^xii—Ge2—Nd2	67.14 (5)
Ge2^iii—Nd1—Li1^iv	86.1 (3)	Li1^vii—Ge2—Nd2	142.73 (3)
Ge3^iv—Nd1—Li1^iv	49.8 (4)	Li2^vii—Ge2—Nd2	79.18 (3)
Ge1^v—Nd1—Li1^iv	58.4 (3)	Nd2^vii—Ge2—Nd2	79.18 (3)
Ge1^vi—Nd1—Li1^iv	95.0 (3)	Li2^ix—Ge2—Nd2	123.67 (6)
Ge3^i—Nd1—Li1^i	50.3 (4)	Nd2^ix—Ge2—Nd2	123.67 (6)
Ge1^ii—Nd1—Li1^i	59.2 (3)	Ge3^xii—Ge2—Nd2^vi	67.14 (5)
Ge2^iii—Nd1—Li1^i	48.4 (4)	Li1^vii—Ge2—Nd2^vi	142.73 (3)
Ge3^iv—Nd1—Li1^i	86.5 (3)	Li2^vii—Ge2—Nd2^vi	123.67 (6)
Ge1^v—Nd1—Li1^i	141.7 (4)	Nd2^vii—Ge2—Nd2^vi	123.67 (6)
Ge1^vi—Nd1—Li1^i	117.4 (4)	Li2^ix—Ge2—Nd2^vi	79.18 (3)
Li1^iv—Nd1—Li1^i	94.1 (4)	Nd2^ix—Ge2—Nd2^vi	79.18 (3)
Ge3^i—Nd1—Nd1^vii	110.73 (4)	Nd2—Ge2—Nd2^vi	74.52 (5)
Ge1^ii—Nd1—Nd1^vii	152.30 (3)	Ge3^xii—Ge2—Li2^vi	67.14 (5)
Ge2^iii—Nd1—Nd1^vii	95.34 (4)	Li1^vii—Ge2—Li2^vi	142.73 (3)
Ge3^iv—Nd1—Nd1^vii	51.34 (3)	Li2^vii—Ge2—Li2^vi	123.67 (6)
Ge1^v—Nd1—Nd1^vii	51.31 (3)	Nd2^vii—Ge2—Li2^vi	123.67 (6)
Ge1^vi—Nd1—Nd1^vii	97.12 (3)	Li2^ix—Ge2—Li2^vi	79.18 (3)
Li1^iv—Nd1—Nd1^vii	56.9 (4)	Nd2^ix—Ge2—Li2^vi	79.18 (3)
Li1^i—Nd1—Nd1^vii	137.6 (3)	Nd2—Ge2—Li2^vi	74.52 (5)
Ge3^i—Nd1—Nd1^viii	53.46 (3)	Nd2^vi—Ge2—Li2^vi	0.000 (19)
Ge1^ii—Nd1—Nd1^viii	53.75 (3)	Ge3^xii—Ge2—Nd1^xvii	67.28 (4)
Ge2^iii—Nd1—Nd1^viii	105.12 (4)	Li1^vii—Ge2—Nd1^xvii	72.9 (4)
Ge3^iv—Nd1—Nd1^viii	134.11 (3)	Li2^vii—Ge2—Nd1^xvii	86.94 (3)
Ge1^v—Nd1—Nd1^viii	100.25 (4)	Nd2^vii—Ge2—Nd1^xvii	86.94 (3)
Ge1^vi—Nd1—Nd1^viii	60.79 (3)	Li2^ix—Ge2—Nd1^xvii	147.11 (6)
Li1^iv—Nd1—Nd1^viii	102.0 (4)	Nd2^ix—Ge2—Nd1^xvii	147.11 (6)
Li1^i—Nd1—Nd1^viii	56.7 (4)	Nd2—Ge2—Nd1^xvii	78.58 (3)
Nd1^vii—Nd1—Nd1^viii	149.80 (4)	Nd2^vi—Ge2—Nd1^xvii	133.16 (6)
Ge3^i—Nd1—Nd2^ix	135.28 (4)	Li2^vi—Ge2—Nd1^xvii	133.16 (6)
Ge1^ii—Nd1—Nd2^ix	99.38 (3)	Ge3^xii—Ge2—Nd1^iii	67.28 (4)
Ge2^iii—Nd1—Nd2^ix	143.08 (4)	Li1^vii—Ge2—Nd1^iii	72.9 (4)
Ge3^iv—Nd1—Nd2^ix	114.74 (3)	Li2^vii—Ge2—Nd1^iii	147.11 (6)
Ge1^v—Nd1—Nd2^ix	49.01 (2)	Nd2^vii—Ge2—Nd1^iii	147.11 (6)
Ge1^vi—Nd1—Nd2^ix	50.09 (3)	Li2^ix—Ge2—Nd1^iii	86.94 (3)
Li1^iv—Nd1—Nd2^ix	104.8 (3)	Nd2^ix—Ge2—Nd1^iii	86.94 (3)
Li1^i—Nd1—Nd2^ix	157.6 (3)	Nd2—Ge2—Nd1^iii	133.16 (6)
Nd1^vii—Nd1—Nd2^ix	64.511 (14)	Nd2^vi—Ge2—Nd1^iii	78.58 (3)
Nd1^viii—Nd1—Nd2^ix	106.748 (17)	Li2^vi—Ge2—Nd1^iii	78.58 (3)
Ge3^i—Nd1—Nd2^x	125.92 (3)	Nd1^xvii—Ge2—Nd1^iii	93.52 (5)
Ge1^ii—Nd1—Nd2^x	96.54 (3)	Ge2^xviii—Ge3—Li1	114.9 (5)
Ge2^iii—Nd1—Nd2^x	49.81 (3)	Ge2^xviii—Ge3—Li1^xix	122.2 (5)
Ge3^iv—Nd1—Nd2^x	50.96 (3)	Li1—Ge3—Li1^xix	123.0 (7)
Ge1^v—Nd1—Nd2^x	113.70 (3)	Ge2^xviii—Ge3—Nd1^xv	132.47 (3)
Ge1^vi—Nd1—Nd2^x	143.22 (3)	Li1—Ge3—Nd1^xv	72.4 (3)
Li1^iv—Nd1—Nd2^x	99.1 (4)	Li1^xix—Ge3—Nd1^xv	70.0 (3)
Li1^i—Nd1—Nd2^x	95.3 (4)	Ge2^xviii—Ge3—Nd1^xx	132.47 (3)
Nd1^vii—Nd1—Nd2^x	64.02 (2)	Li1—Ge3—Nd1^xx	72.4 (3)
Nd1^viii—Nd1—Nd2^x	145.83 (3)	Li1^xix—Ge3—Nd1^xx	70.0 (3)
Nd2^ix—Nd1—Nd2^x	93.346 (18)	Nd1^xv—Ge3—Nd1^xx	95.01 (5)
Ge1—Nd2—Ge1^xi	93.54 (3)	Ge2^xviii—Ge3—Li2^xviii	64.15 (5)
Ge1—Nd2—Ge2^viii	89.25 (4)	Li1—Ge3—Li2^xviii	143.03 (10)
Ge1^xi—Nd2—Ge2^viii	147.84 (4)	Li1^xix—Ge3—Li2^xviii	70.0 (4)
Ge1—Nd2—Ge2	100.08 (4)	Nd1^xv—Ge3—Li2^xviii	82.65 (3)
Ge1^xi—Nd2—Ge2	112.56 (4)	Nd1^xx—Ge3—Li2^xviii	138.07 (6)
Ge2^viii—Nd2—Ge2	98.39 (3)	Ge2^xviii—Ge3—Nd2^xviii	64.15 (5)
Ge1—Nd2—Ge1^viii	114.78 (5)	Li1—Ge3—Nd2^xviii	143.03 (10)
Ge1^xi—Nd2—Ge1^viii	51.46 (4)	Li1^xix—Ge3—Nd2^xviii	70.0 (4)
Ge2^viii—Nd2—Ge1^viii	98.63 (4)	Nd1^xv—Ge3—Nd2^xviii	82.65 (3)
Ge2—Nd2—Ge1^viii	141.16 (5)	Nd1^xx—Ge3—Nd2^xviii	138.07 (6)
Ge1—Nd2—Ge3^xii	147.78 (5)	Li2^xviii—Ge3—Nd2^xviii	0.00 (3)
Ge1^xi—Nd2—Ge3^xii	92.74 (4)	Ge2^xviii—Ge3—Li2^xxi	64.14 (5)
Ge2^viii—Nd2—Ge3^xii	101.77 (4)	Li1—Ge3—Li2^xxi	143.03 (10)
Ge2—Nd2—Ge3^xii	48.71 (5)	Li1^xix—Ge3—Li2^xxi	70.0 (4)
Ge1^viii—Nd2—Ge3^xii	93.61 (4)	Nd1^xv—Ge3—Li2^xxi	138.07 (6)
Ge1—Nd2—Li1^viii	155.3 (4)	Nd1^xx—Ge3—Li2^xxi	82.65 (3)
Ge1^xi—Nd2—Li1^viii	98.3 (3)	Li2^xviii—Ge3—Li2^xxi	72.49 (5)
Ge2^viii—Nd2—Li1^viii	69.3 (4)	Nd2^xviii—Ge3—Li2^xxi	72.49 (5)
Ge2—Nd2—Li1^viii	95.3 (3)	Ge2^xviii—Ge3—Nd2^xxi	64.14 (5)
Ge1^viii—Nd2—Li1^viii	59.3 (2)	Li1—Ge3—Nd2^xxi	143.03 (10)
Ge3^xii—Nd2—Li1^viii	53.4 (4)	Li1^xix—Ge3—Nd2^xxi	70.0 (4)
Ge1—Nd2—Li1	59.7 (2)	Nd1^xv—Ge3—Nd2^xxi	138.07 (6)
Ge1^xi—Nd2—Li1	152.0 (3)	Nd1^xx—Ge3—Nd2^xxi	82.65 (3)
Ge2^viii—Nd2—Li1	48.6 (4)	Li2^xviii—Ge3—Nd2^xxi	72.49 (5)
Ge2—Nd2—Li1	68.5 (4)	Nd2^xviii—Ge3—Nd2^xxi	72.49 (5)
Ge1^viii—Nd2—Li1	144.2 (4)	Li2^xxi—Ge3—Nd2^xxi	0.00 (3)
Ge3^xii—Nd2—Li1	105.9 (3)	Ge2^xviii—Ge3—Nd1^xvi	65.13 (4)
Li1^viii—Nd2—Li1	109.5 (4)	Li1—Ge3—Nd1^xvi	70.9 (4)
Ge1—Nd2—Li2^vi	118.10 (3)	Li1^xix—Ge3—Nd1^xvi	134.03 (5)
Ge1^xi—Nd2—Li2^vi	145.84 (3)	Nd1^xv—Ge3—Nd1^xvi	75.20 (2)
Ge2^viii—Nd2—Li2^vi	52.20 (2)	Nd1^xx—Ge3—Nd1^xvi	143.24 (6)
Ge2—Nd2—Li2^vi	52.74 (2)	Li2^xviii—Ge3—Nd1^xvi	76.73 (3)
Ge1^viii—Nd2—Li2^vi	117.08 (3)	Nd2^xviii—Ge3—Nd1^xvi	76.73 (3)
Ge3^xii—Nd2—Li2^vi	53.75 (2)	Li2^xxi—Ge3—Nd1^xvi	128.16 (6)
Li1^viii—Nd2—Li2^vi	58.3 (2)	Nd2^xxi—Ge3—Nd1^xvi	128.16 (6)
Li1—Nd2—Li2^vi	58.6 (2)	Ge2^xviii—Ge3—Nd1^iv	65.13 (4)
Ge1—Nd2—Nd2^vi	118.10 (3)	Li1—Ge3—Nd1^iv	70.9 (4)
Ge1^xi—Nd2—Nd2^vi	145.84 (3)	Li1^xix—Ge3—Nd1^iv	134.02 (5)
Ge2^viii—Nd2—Nd2^vi	52.20 (2)	Nd1^xv—Ge3—Nd1^iv	143.24 (6)
Ge2—Nd2—Nd2^vi	52.74 (2)	Nd1^xx—Ge3—Nd1^iv	75.20 (2)
Ge1^viii—Nd2—Nd2^vi	117.08 (3)	Li2^xviii—Ge3—Nd1^iv	128.16 (6)
Ge3^xii—Nd2—Nd2^vi	53.75 (2)	Nd2^xviii—Ge3—Nd1^iv	128.16 (6)
Li1^viii—Nd2—Nd2^vi	58.3 (2)	Li2^xxi—Ge3—Nd1^iv	76.73 (3)
Li1—Nd2—Nd2^vi	58.6 (2)	Nd2^xxi—Ge3—Nd1^iv	76.73 (3)
Li2^vi—Nd2—Nd2^vi	0.00 (3)	Nd1^xvi—Ge3—Nd1^iv	91.54 (5)
Ge1—Nd2—Nd2^vii	51.30 (3)	Ge2^viii—Li1—Ge3	91.4 (8)
Ge1^xi—Nd2—Nd2^vii	101.55 (3)	Ge2^viii—Li1—Ge3^xxii	178.1 (10)
Ge2^viii—Nd2—Nd2^vii	105.06 (4)	Ge3—Li1—Ge3^xxii	90.5 (7)
Ge2—Nd2—Nd2^vii	49.98 (3)	Ge2^viii—Li1—Nd1^xvi	124.9 (6)
Ge1^viii—Nd2—Nd2^vii	151.67 (3)	Ge3—Li1—Nd1^xvi	59.3 (4)
Ge3^xii—Nd2—Nd2^vii	96.49 (4)	Ge3^xxii—Li1—Nd1^xvi	56.2 (4)
Li1^viii—Nd2—Nd2^vii	144.6 (3)	Ge2^viii—Li1—Nd1^iv	124.9 (6)
Li1—Nd2—Nd2^vii	56.5 (4)	Ge3—Li1—Nd1^iv	59.3 (4)
Li2^vi—Nd2—Nd2^vii	90.0	Ge3^xxii—Li1—Nd1^iv	56.2 (4)
Nd2^vi—Nd2—Nd2^vii	90.0	Nd1^xvi—Li1—Nd1^iv	81.4 (6)
Ge1—Nd2—Nd2^viii	99.94 (3)	Ge2^viii—Li1—Nd1^xv	58.7 (4)
Ge1^xi—Nd2—Nd2^viii	97.24 (3)	Ge3—Li1—Nd1^xv	57.3 (4)
Ge2^viii—Nd2—Nd2^viii	50.84 (3)	Ge3^xxii—Li1—Nd1^xv	122.6 (6)
Ge2—Nd2—Nd2^viii	142.68 (2)	Nd1^xvi—Li1—Nd1^xv	66.3 (3)
Ge1^viii—Nd2—Nd2^viii	48.97 (3)	Nd1^iv—Li1—Nd1^xv	116.6 (7)
Ge3^xii—Nd2—Nd2^viii	110.55 (4)	Ge2^viii—Li1—Nd1^xx	58.7 (4)
Li1^viii—Nd2—Nd2^viii	57.2 (4)	Ge3—Li1—Nd1^xx	57.3 (4)
Li1—Nd2—Nd2^viii	95.5 (4)	Ge3^xxii—Li1—Nd1^xx	122.6 (6)
Li2^vi—Nd2—Nd2^viii	90.0	Nd1^xvi—Li1—Nd1^xx	116.6 (7)
Nd2^vi—Nd2—Nd2^viii	90.0	Nd1^iv—Li1—Nd1^xx	66.3 (3)
Nd2^vii—Nd2—Nd2^viii	146.14 (4)	Nd1^xv—Li1—Nd1^xx	81.2 (6)
Ge1^xiii—Ge1—Nd2	135.66 (7)	Ge2^viii—Li1—Li2^vii	121.9 (7)
Ge1^xiii—Ge1—Li2^xiv	65.44 (5)	Ge3—Li1—Li2^vii	130.8 (7)
Nd2—Ge1—Li2^xiv	144.00 (5)	Ge3^xxii—Li1—Li2^vii	56.6 (4)
Ge1^xiii—Ge1—Nd2^xiv	65.44 (5)	Nd1^xvi—Li1—Li2^vii	71.7 (4)
Nd2—Ge1—Nd2^xiv	144.00 (5)	Nd1^iv—Li1—Li2^vii	111.8 (7)
Li2^xiv—Ge1—Nd2^xiv	0.00 (3)	Nd1^xv—Li1—Li2^vii	107.55 (7)
Ge1^xiii—Ge1—Li2^vii	63.10 (5)	Nd1^xx—Li1—Li2^vii	170.3 (6)
Nd2—Ge1—Li2^vii	79.74 (3)	Ge2^viii—Li1—Nd2^vii	121.9 (7)
Li2^xiv—Ge1—Li2^vii	128.54 (4)	Ge3—Li1—Nd2^vii	130.8 (7)
Nd2^xiv—Ge1—Li2^vii	128.54 (4)	Ge3^xxii—Li1—Nd2^vii	56.6 (4)
Ge1^xiii—Ge1—Nd2^vii	63.10 (5)	Nd1^xvi—Li1—Nd2^vii	71.7 (4)
Nd2—Ge1—Nd2^vii	79.74 (3)	Nd1^iv—Li1—Nd2^vii	111.8 (7)
Li2^xiv—Ge1—Nd2^vii	128.54 (4)	Nd1^xv—Li1—Nd2^vii	107.55 (7)
Nd2^xiv—Ge1—Nd2^vii	128.54 (4)	Nd1^xx—Li1—Nd2^vii	170.3 (6)
Li2^vii—Ge1—Nd2^vii	0.00 (3)	Li2^vii—Li1—Nd2^vii	0.00 (3)
Ge1^xiii—Ge1—Nd1^xv	134.49 (7)	Ge2^viii—Li1—Li2^ix	121.9 (7)
Nd2—Ge1—Nd1^xv	88.48 (4)	Ge3—Li1—Li2^ix	130.8 (7)
Li2^xiv—Ge1—Nd1^xv	84.91 (4)	Ge3^xxii—Li1—Li2^ix	56.6 (4)
Nd2^xiv—Ge1—Nd1^xv	84.91 (4)	Nd1^xvi—Li1—Li2^ix	111.8 (7)
Li2^vii—Ge1—Nd1^xv	133.60 (5)	Nd1^iv—Li1—Li2^ix	71.7 (4)
Nd2^vii—Ge1—Nd1^xv	133.60 (5)	Nd1^xv—Li1—Li2^ix	170.3 (6)
Ge1^xiii—Ge1—Nd1^xvi	65.78 (5)	Nd1^xx—Li1—Li2^ix	107.55 (7)
Nd2—Ge1—Nd1^xvi	134.33 (5)	Li2^vii—Li1—Li2^ix	63.4 (4)
Li2^xiv—Ge1—Nd1^xvi	77.55 (3)	Nd2^vii—Li1—Li2^ix	63.4 (4)
Nd2^xiv—Ge1—Nd1^xvi	77.55 (3)	Ge2^viii—Li1—Nd2^ix	121.9 (7)
Li2^vii—Ge1—Nd1^xvi	81.88 (4)	Ge3—Li1—Nd2^ix	130.8 (7)
Nd2^vii—Ge1—Nd1^xvi	81.88 (4)	Ge3^xxii—Li1—Nd2^ix	56.6 (4)
Nd1^xv—Ge1—Nd1^xvi	74.94 (3)	Nd1^xvi—Li1—Nd2^ix	111.8 (7)
Ge1^xiii—Ge1—Nd1^vi	65.59 (5)	Nd1^iv—Li1—Nd2^ix	71.7 (4)
Nd2—Ge1—Nd1^vi	83.73 (4)	Nd1^xv—Li1—Nd2^ix	170.3 (6)
Li2^xiv—Ge1—Nd1^vi	82.72 (4)	Nd1^xx—Li1—Nd2^ix	107.55 (7)
Nd2^xiv—Ge1—Nd1^vi	82.72 (4)	Li2^vii—Li1—Nd2^ix	63.4 (4)
Li2^vii—Ge1—Nd1^vi	76.63 (3)	Nd2^vii—Li1—Nd2^ix	63.4 (4)
Nd2^vii—Ge1—Nd1^vi	76.63 (3)	Li2^ix—Li1—Nd2^ix	0.00 (2)
Nd1^xv—Ge1—Nd1^vi	146.74 (4)

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

(III) Tetragadolinium lithium tetragermanide

Crystal data

Gd3.96Li1.03Ge4	F(000) = 1539
Mr = 920.66	Dx = 7.393 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ac 2n	Cell parameters from 999 reflections
a = 7.188 (2) Å	θ = 2.8–28.1°
b = 14.816 (5) Å	µ = 45.51 mm^−1
c = 7.767 (3) Å	T = 200 K
V = 827.2 (5) Å^3	Irregular, grey
Z = 4	0.06 × 0.05 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1044 independent reflections
Radiation source: fine-focus sealed tube	800 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.141
ϕ and ω scans	θmax = 28.1°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
Tmin = 0.181, Tmax = 0.277	k = −19→19
10177 measured reflections	l = −10→10

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)] = 0.040	w = 1/[σ^2(Fo^2) + (0.030P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.087	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 2.35 e Å^−3
1044 reflections	Δρmin = −2.66 e Å^−3
45 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00110 (10)

Special details

Experimental. Data collection is performed with two batch runs at ϕ = 0.00 ° (456 frames), and at ϕ = 90.00 ° (456 frames). Frame width = 0.40 ° in ω. Data is merged, corrected for decay, 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 > 2sigma(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)
Gd1	0.01762 (9)	0.59847 (5)	0.18663 (9)	0.0099 (2)
Gd2	0.32797 (10)	0.12807 (5)	0.17807 (9)	0.0091 (3)	0.977 (4)
Li2	0.32797 (10)	0.12807 (5)	0.17807 (9)	0.0091 (3)	0.023 (4)
Ge1	0.1626 (2)	0.03613 (10)	0.46676 (19)	0.0108 (4)
Ge2	0.0170 (3)	0.2500	0.0827 (3)	0.0105 (5)
Ge3	0.2792 (3)	0.2500	0.8658 (3)	0.0103 (5)
Li1	0.154 (6)	0.2500	0.531 (6)	0.035 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Gd1	0.0106 (4)	0.0096 (4)	0.0094 (4)	0.0003 (3)	−0.0001 (3)	0.0006 (3)
Gd2	0.0106 (4)	0.0079 (4)	0.0088 (4)	0.0000 (3)	0.0005 (3)	0.0000 (3)
Li2	0.0106 (4)	0.0079 (4)	0.0088 (4)	0.0000 (3)	0.0005 (3)	0.0000 (3)
Ge1	0.0126 (8)	0.0111 (8)	0.0087 (7)	−0.0009 (6)	−0.0003 (6)	0.0007 (6)
Ge2	0.0106 (11)	0.0112 (12)	0.0098 (10)	0.000	0.0013 (8)	0.000
Ge3	0.0129 (11)	0.0085 (11)	0.0095 (10)	0.000	0.0002 (8)	0.000

Geometric parameters (Å, º)

Gd1—Ge1^i	3.0088 (18)	Ge1—Gd1^xvi	3.4509 (18)
Gd1—Ge3^ii	3.0182 (17)	Ge2—Ge3^xi	2.528 (3)
Gd1—Ge2^iii	3.0785 (18)	Ge2—Li1^viii	2.75 (4)
Gd1—Ge3^iv	3.1240 (17)	Ge2—Li2^viii	2.9264 (19)
Gd1—Ge1^v	3.1271 (18)	Ge2—Gd2^viii	2.9264 (19)
Gd1—Ge1^vi	3.1301 (18)	Ge2—Li2^vii	2.9264 (19)
Gd1—Li1^iv	3.37 (3)	Ge2—Gd2^vii	2.9264 (19)
Gd1—Ge1^vii	3.4508 (18)	Ge2—Gd2^vi	2.9681 (19)
Gd1—Li1^ii	3.48 (3)	Ge2—Li2^vi	2.9681 (19)
Gd1—Gd1^viii	3.7265 (12)	Ge2—Gd1^xvii	3.0784 (18)
Gd1—Gd1^ix	3.7265 (12)	Ge2—Gd1^iii	3.0785 (18)
Gd1—Gd2^vii	3.7720 (14)	Ge3—Ge2^xviii	2.528 (3)
Gd2—Ge1	2.8803 (17)	Ge3—Li1	2.75 (4)
Gd2—Ge2^ix	2.9264 (19)	Ge3—Li1^xix	2.81 (4)
Gd2—Ge1^x	2.9354 (18)	Ge3—Gd1^xiv	3.0181 (16)
Gd2—Ge2	2.9681 (19)	Ge3—Gd1^xx	3.0181 (16)
Gd2—Ge1^ix	2.9845 (18)	Ge3—Li2^xviii	3.0447 (19)
Gd2—Ge3^xi	3.0447 (19)	Ge3—Gd2^xviii	3.0447 (19)
Gd2—Li1^ix	3.37 (4)	Ge3—Li2^xxi	3.0448 (19)
Gd2—Li1	3.51 (4)	Ge3—Gd2^xxi	3.0448 (19)
Gd2—Li2^vi	3.6131 (18)	Ge3—Gd1^xv	3.1240 (17)
Gd2—Gd2^vi	3.6131 (18)	Ge3—Gd1^iv	3.1240 (17)
Gd2—Gd2^viii	3.7637 (12)	Li1—Ge2^ix	2.75 (4)
Gd2—Li2^viii	3.7637 (12)	Li1—Ge3^xxii	2.81 (4)
Ge1—Ge1^xii	2.623 (3)	Li1—Ge1^vi	3.208 (7)
Ge1—Li2^xiii	2.9355 (18)	Li1—Gd1^xv	3.37 (3)
Ge1—Gd2^xiii	2.9355 (18)	Li1—Li2^viii	3.37 (4)
Ge1—Li2^viii	2.9845 (18)	Li1—Gd2^viii	3.37 (4)
Ge1—Gd2^viii	2.9845 (18)	Li1—Li2^vii	3.37 (4)
Ge1—Gd1^xiv	3.0088 (18)	Li1—Gd2^vii	3.37 (4)
Ge1—Gd1^xv	3.1272 (18)	Li1—Gd1^iv	3.37 (3)
Ge1—Gd1^vi	3.1301 (18)	Li1—Gd1^xiv	3.48 (3)
Ge1—Li1	3.208 (7)
Ge1^i—Gd1—Ge3^ii	96.91 (6)	Gd2^viii—Ge1—Gd1^xvi	136.86 (5)
Ge1^i—Gd1—Ge2^iii	84.26 (5)	Gd1^xiv—Ge1—Gd1^xvi	78.96 (5)
Ge3^ii—Gd1—Ge2^iii	79.04 (5)	Gd1^xv—Ge1—Gd1^xvi	140.74 (5)
Ge1^i—Gd1—Ge3^iv	131.95 (5)	Gd1^vi—Ge1—Gd1^xvi	68.78 (4)
Ge3^ii—Gd1—Ge3^iv	81.72 (4)	Li1—Ge1—Gd1^xvi	129.7 (8)
Ge2^iii—Gd1—Ge3^iv	48.10 (5)	Ge3^xi—Ge2—Li1^viii	119.6 (9)
Ge1^i—Gd1—Ge1^v	135.60 (6)	Ge3^xi—Ge2—Li2^viii	140.30 (4)
Ge3^ii—Gd1—Ge1^v	91.33 (5)	Li1^viii—Ge2—Li2^viii	76.3 (7)
Ge2^iii—Gd1—Ge1^v	140.07 (5)	Ge3^xi—Ge2—Gd2^viii	140.30 (4)
Ge3^iv—Gd1—Ge1^v	92.38 (5)	Li1^viii—Ge2—Gd2^viii	76.3 (7)
Ge1^i—Gd1—Ge1^vi	86.82 (3)	Li2^viii—Ge2—Gd2^viii	0.00 (4)
Ge3^ii—Gd1—Ge1^vi	89.56 (5)	Ge3^xi—Ge2—Li2^vii	140.30 (4)
Ge2^iii—Gd1—Ge1^vi	164.54 (5)	Li1^viii—Ge2—Li2^vii	76.3 (7)
Ge3^iv—Gd1—Ge1^vi	140.88 (5)	Li2^viii—Ge2—Li2^vii	76.24 (6)
Ge1^v—Gd1—Ge1^vi	49.56 (5)	Gd2^viii—Ge2—Li2^vii	76.24 (6)
Ge1^i—Gd1—Li1^iv	148.5 (7)	Ge3^xi—Ge2—Gd2^vii	140.30 (4)
Ge3^ii—Gd1—Li1^iv	51.8 (7)	Li1^viii—Ge2—Gd2^vii	76.3 (7)
Ge2^iii—Gd1—Li1^iv	85.8 (5)	Li2^viii—Ge2—Gd2^vii	76.24 (6)
Ge3^iv—Gd1—Li1^iv	50.0 (7)	Gd2^viii—Ge2—Gd2^vii	76.24 (6)
Ge1^v—Gd1—Li1^iv	59.0 (5)	Li2^vii—Ge2—Gd2^vii	0.00 (3)
Ge1^vi—Gd1—Li1^iv	95.3 (6)	Ge3^xi—Ge2—Gd2	66.72 (6)
Ge1^i—Gd1—Ge1^vii	101.04 (4)	Li1^viii—Ge2—Gd2	142.51 (3)
Ge3^ii—Gd1—Ge1^vii	161.24 (5)	Li2^viii—Ge2—Gd2	79.36 (4)
Ge2^iii—Gd1—Ge1^vii	97.30 (5)	Gd2^viii—Ge2—Gd2	79.36 (4)
Ge3^iv—Gd1—Ge1^vii	82.26 (5)	Li2^vii—Ge2—Gd2	124.53 (8)
Ge1^v—Gd1—Ge1^vii	79.64 (3)	Gd2^vii—Ge2—Gd2	124.53 (8)
Ge1^vi—Gd1—Ge1^vii	96.78 (5)	Ge3^xi—Ge2—Gd2^vi	66.72 (6)
Li1^iv—Gd1—Ge1^vii	109.8 (7)	Li1^viii—Ge2—Gd2^vi	142.51 (3)
Ge1^i—Gd1—Li1^ii	58.8 (5)	Li2^viii—Ge2—Gd2^vi	124.53 (8)
Ge3^ii—Gd1—Li1^ii	49.6 (7)	Gd2^viii—Ge2—Gd2^vi	124.53 (8)
Ge2^iii—Gd1—Li1^ii	49.2 (7)	Li2^vii—Ge2—Gd2^vi	79.36 (4)
Ge3^iv—Gd1—Li1^ii	87.4 (5)	Gd2^vii—Ge2—Gd2^vi	79.36 (4)
Ge1^v—Gd1—Li1^ii	140.6 (7)	Gd2—Ge2—Gd2^vi	74.99 (6)
Ge1^vi—Gd1—Li1^ii	115.3 (7)	Ge3^xi—Ge2—Li2^vi	66.72 (6)
Li1^iv—Gd1—Li1^ii	92.6 (8)	Li1^viii—Ge2—Li2^vi	142.51 (3)
Ge1^vii—Gd1—Li1^ii	139.0 (7)	Li2^viii—Ge2—Li2^vi	124.53 (8)
Ge1^i—Gd1—Gd1^viii	152.47 (4)	Gd2^viii—Ge2—Li2^vi	124.53 (8)
Ge3^ii—Gd1—Gd1^viii	110.17 (5)	Li2^vii—Ge2—Li2^vi	79.36 (4)
Ge2^iii—Gd1—Gd1^viii	95.83 (4)	Gd2^vii—Ge2—Li2^vi	79.36 (4)
Ge3^iv—Gd1—Gd1^viii	51.36 (4)	Gd2—Ge2—Li2^vi	74.99 (6)
Ge1^v—Gd1—Gd1^viii	51.17 (3)	Gd2^vi—Ge2—Li2^vi	0.00 (3)
Ge1^vi—Gd1—Gd1^viii	97.90 (4)	Ge3^xi—Ge2—Gd1^xvii	66.89 (5)
Li1^iv—Gd1—Gd1^viii	58.4 (7)	Li1^viii—Ge2—Gd1^xvii	72.9 (6)
Ge1^vii—Gd1—Gd1^viii	51.54 (3)	Li2^viii—Ge2—Gd1^xvii	86.77 (4)
Li1^ii—Gd1—Gd1^viii	138.3 (5)	Gd2^viii—Ge2—Gd1^xvii	86.77 (4)
Ge1^i—Gd1—Gd1^ix	54.06 (4)	Li2^vii—Ge2—Gd1^xvii	147.58 (8)
Ge3^ii—Gd1—Gd1^ix	53.95 (4)	Gd2^vii—Ge2—Gd1^xvii	147.58 (8)
Ge2^iii—Gd1—Gd1^ix	104.92 (4)	Gd2—Ge2—Gd1^xvii	77.68 (3)
Ge3^iv—Gd1—Gd1^ix	133.88 (3)	Gd2^vi—Ge2—Gd1^xvii	132.41 (7)
Ge1^v—Gd1—Gd1^ix	99.91 (4)	Li2^vi—Ge2—Gd1^xvii	132.41 (7)
Ge1^vi—Gd1—Gd1^ix	59.68 (3)	Ge3^xi—Ge2—Gd1^iii	66.89 (5)
Li1^iv—Gd1—Gd1^ix	100.4 (7)	Li1^viii—Ge2—Gd1^iii	72.9 (6)
Ge1^vii—Gd1—Gd1^ix	143.56 (3)	Li2^viii—Ge2—Gd1^iii	147.58 (8)
Li1^ii—Gd1—Gd1^ix	55.8 (7)	Gd2^viii—Ge2—Gd1^iii	147.58 (8)
Gd1^viii—Gd1—Gd1^ix	149.36 (4)	Li2^vii—Ge2—Gd1^iii	86.77 (4)
Ge1^i—Gd1—Gd2^vii	99.27 (4)	Gd2^vii—Ge2—Gd1^iii	86.77 (4)
Ge3^ii—Gd1—Gd2^vii	135.10 (4)	Gd2—Ge2—Gd1^iii	132.41 (7)
Ge2^iii—Gd1—Gd2^vii	144.00 (4)	Gd2^vi—Ge2—Gd1^iii	77.68 (3)
Ge3^iv—Gd1—Gd2^vii	115.40 (4)	Li2^vi—Ge2—Gd1^iii	77.68 (3)
Ge1^v—Gd1—Gd2^vii	49.28 (3)	Gd1^xvii—Ge2—Gd1^iii	93.65 (7)
Ge1^vi—Gd1—Gd2^vii	50.19 (3)	Ge2^xviii—Ge3—Li1	112.7 (9)
Li1^iv—Gd1—Gd2^vii	106.2 (5)	Ge2^xviii—Ge3—Li1^xix	121.6 (9)
Ge1^vii—Gd1—Gd2^vii	46.74 (3)	Li1—Ge3—Li1^xix	125.7 (13)
Li1^ii—Gd1—Gd2^vii	156.5 (5)	Ge2^xviii—Ge3—Gd1^xiv	131.91 (3)
Gd1^viii—Gd1—Gd2^vii	65.030 (18)	Li1—Ge3—Gd1^xiv	73.9 (6)
Gd1^ix—Gd1—Gd2^vii	105.96 (2)	Li1^xix—Ge3—Gd1^xiv	70.6 (6)
Ge1—Gd2—Ge2^ix	89.38 (6)	Ge2^xviii—Ge3—Gd1^xx	131.91 (3)
Ge1—Gd2—Ge1^x	93.03 (3)	Li1—Ge3—Gd1^xx	73.9 (6)
Ge2^ix—Gd2—Ge1^x	148.87 (5)	Li1^xix—Ge3—Gd1^xx	70.6 (6)
Ge1—Gd2—Ge2	99.87 (6)	Gd1^xiv—Ge3—Gd1^xx	96.13 (7)
Ge2^ix—Gd2—Ge2	97.62 (5)	Ge2^xviii—Ge3—Li2^xviii	63.57 (6)
Ge1^x—Gd2—Ge2	112.47 (5)	Li1—Ge3—Li2^xviii	142.2 (2)
Ge1—Gd2—Ge1^ix	114.22 (6)	Li1^xix—Ge3—Li2^xviii	70.2 (7)
Ge2^ix—Gd2—Ge1^ix	98.45 (6)	Gd1^xiv—Ge3—Li2^xviii	82.54 (4)
Ge1^x—Gd2—Ge1^ix	52.58 (5)	Gd1^xx—Ge3—Li2^xviii	138.85 (8)
Ge2—Gd2—Ge1^ix	142.25 (6)	Ge2^xviii—Ge3—Gd2^xviii	63.57 (6)
Ge1—Gd2—Ge3^xi	148.58 (6)	Li1—Ge3—Gd2^xviii	142.2 (2)
Ge2^ix—Gd2—Ge3^xi	101.13 (5)	Li1^xix—Ge3—Gd2^xviii	70.2 (7)
Ge1^x—Gd2—Ge3^xi	92.81 (5)	Gd1^xiv—Ge3—Gd2^xviii	82.54 (4)
Ge2—Gd2—Ge3^xi	49.70 (6)	Gd1^xx—Ge3—Gd2^xviii	138.85 (8)
Ge1^ix—Gd2—Ge3^xi	93.63 (5)	Li2^xviii—Ge3—Gd2^xviii	0.00 (3)
Ge1—Gd2—Li1^ix	156.0 (8)	Ge2^xviii—Ge3—Li2^xxi	63.57 (6)
Ge2^ix—Gd2—Li1^ix	69.6 (7)	Li1—Ge3—Li2^xxi	142.2 (2)
Ge1^x—Gd2—Li1^ix	99.2 (5)	Li1^xix—Ge3—Li2^xxi	70.2 (7)
Ge2—Gd2—Li1^ix	94.4 (6)	Gd1^xiv—Ge3—Li2^xxi	138.85 (8)
Ge1^ix—Gd2—Li1^ix	60.2 (4)	Gd1^xx—Ge3—Li2^xxi	82.54 (4)
Ge3^xi—Gd2—Li1^ix	51.7 (7)	Li2^xviii—Ge3—Li2^xxi	72.79 (6)
Ge1—Gd2—Li1	59.3 (4)	Gd2^xviii—Ge3—Li2^xxi	72.79 (6)
Ge2^ix—Gd2—Li1	49.6 (7)	Ge2^xviii—Ge3—Gd2^xxi	63.57 (6)
Ge1^x—Gd2—Li1	150.6 (5)	Li1—Ge3—Gd2^xxi	142.2 (2)
Ge2—Gd2—Li1	67.2 (6)	Li1^xix—Ge3—Gd2^xxi	70.2 (7)
Ge1^ix—Gd2—Li1	144.7 (7)	Gd1^xiv—Ge3—Gd2^xxi	138.85 (8)
Ge3^xi—Gd2—Li1	106.0 (5)	Gd1^xx—Ge3—Gd2^xxi	82.54 (4)
Li1^ix—Gd2—Li1	110.3 (7)	Li2^xviii—Ge3—Gd2^xxi	72.79 (6)
Ge1—Gd2—Li2^vi	118.22 (3)	Gd2^xviii—Ge3—Gd2^xxi	72.79 (6)
Ge2^ix—Gd2—Li2^vi	51.88 (3)	Li2^xxi—Ge3—Gd2^xxi	0.00 (3)
Ge1^x—Gd2—Li2^vi	145.97 (3)	Ge2^xviii—Ge3—Gd1^xv	65.01 (5)
Ge2—Gd2—Li2^vi	52.51 (3)	Li1—Ge3—Gd1^xv	69.7 (6)
Ge1^ix—Gd2—Li2^vi	117.16 (3)	Li1^xix—Ge3—Gd1^xv	133.77 (10)
Ge3^xi—Gd2—Li2^vi	53.61 (3)	Gd1^xiv—Ge3—Gd1^xv	74.68 (3)
Li1^ix—Gd2—Li2^vi	57.6 (4)	Gd1^xx—Ge3—Gd1^xv	143.61 (7)
Li1—Gd2—Li2^vi	59.0 (4)	Li2^xviii—Ge3—Gd1^xv	75.88 (4)
Ge1—Gd2—Gd2^vi	118.22 (3)	Gd2^xviii—Ge3—Gd1^xv	75.88 (4)
Ge2^ix—Gd2—Gd2^vi	51.88 (3)	Li2^xxi—Ge3—Gd1^xv	127.50 (7)
Ge1^x—Gd2—Gd2^vi	145.97 (3)	Gd2^xxi—Ge3—Gd1^xv	127.50 (7)
Ge2—Gd2—Gd2^vi	52.51 (3)	Ge2^xviii—Ge3—Gd1^iv	65.01 (5)
Ge1^ix—Gd2—Gd2^vi	117.16 (3)	Li1—Ge3—Gd1^iv	69.7 (6)
Ge3^xi—Gd2—Gd2^vi	53.61 (3)	Li1^xix—Ge3—Gd1^iv	133.77 (10)
Li1^ix—Gd2—Gd2^vi	57.6 (4)	Gd1^xiv—Ge3—Gd1^iv	143.61 (7)
Li1—Gd2—Gd2^vi	59.0 (4)	Gd1^xx—Ge3—Gd1^iv	74.68 (3)
Li2^vi—Gd2—Gd2^vi	0.00 (3)	Li2^xviii—Ge3—Gd1^iv	127.50 (7)
Ge1—Gd2—Gd2^viii	51.31 (4)	Gd2^xviii—Ge3—Gd1^iv	127.50 (7)
Ge2^ix—Gd2—Gd2^viii	104.77 (5)	Li2^xxi—Ge3—Gd1^iv	75.88 (4)
Ge1^x—Gd2—Gd2^viii	100.84 (3)	Gd2^xxi—Ge3—Gd1^iv	75.88 (4)
Ge2—Gd2—Gd2^viii	49.83 (4)	Gd1^xv—Ge3—Gd1^iv	91.89 (7)
Ge1^ix—Gd2—Gd2^viii	151.83 (3)	Ge3—Li1—Ge2^ix	89.6 (13)
Ge3^xi—Gd2—Gd2^viii	97.27 (4)	Ge3—Li1—Ge3^xxii	92.4 (13)
Li1^ix—Gd2—Gd2^viii	143.7 (5)	Ge2^ix—Li1—Ge3^xxii	178.0 (18)
Li1—Gd2—Gd2^viii	55.1 (7)	Ge3—Li1—Ge1	98.0 (8)
Li2^vi—Gd2—Gd2^viii	90.0	Ge2^ix—Li1—Ge1	86.1 (8)
Gd2^vi—Gd2—Gd2^viii	90.0	Ge3^xxii—Li1—Ge1	93.6 (8)
Ge1—Gd2—Li2^viii	51.31 (4)	Ge3—Li1—Ge1^vi	98.0 (8)
Ge2^ix—Gd2—Li2^viii	104.77 (5)	Ge2^ix—Li1—Ge1^vi	86.1 (8)
Ge1^x—Gd2—Li2^viii	100.84 (3)	Ge3^xxii—Li1—Ge1^vi	93.6 (8)
Ge2—Gd2—Li2^viii	49.83 (4)	Ge1—Li1—Ge1^vi	162.1 (16)
Ge1^ix—Gd2—Li2^viii	151.83 (3)	Ge3—Li1—Gd1^xv	60.3 (7)
Ge3^xi—Gd2—Li2^viii	97.27 (4)	Ge2^ix—Li1—Gd1^xv	123.7 (10)
Li1^ix—Gd2—Li2^viii	143.7 (5)	Ge3^xxii—Li1—Gd1^xv	57.5 (7)
Li1—Gd2—Li2^viii	55.1 (7)	Ge1—Li1—Gd1^xv	56.7 (3)
Li2^vi—Gd2—Li2^viii	90.0	Ge1^vi—Li1—Gd1^xv	139.9 (13)
Gd2^vi—Gd2—Li2^viii	90.0	Ge3—Li1—Li2^viii	132.9 (11)
Gd2^viii—Gd2—Li2^viii	0.00 (3)	Ge2^ix—Li1—Li2^viii	120.3 (12)
Ge1^xii—Ge1—Gd2	135.58 (9)	Ge3^xxii—Li1—Li2^viii	58.1 (7)
Ge1^xii—Ge1—Li2^xiii	64.67 (6)	Ge1—Li1—Li2^viii	53.9 (4)
Gd2—Ge1—Li2^xiii	144.86 (6)	Ge1^vi—Li1—Li2^viii	117.9 (12)
Ge1^xii—Ge1—Gd2^xiii	64.67 (6)	Gd1^xv—Li1—Li2^viii	72.7 (6)
Gd2—Ge1—Gd2^xiii	144.86 (6)	Ge3—Li1—Gd2^viii	132.9 (11)
Li2^xiii—Ge1—Gd2^xiii	0.00 (4)	Ge2^ix—Li1—Gd2^viii	120.3 (12)
Ge1^xii—Ge1—Li2^viii	62.75 (6)	Ge3^xxii—Li1—Gd2^viii	58.1 (7)
Gd2—Ge1—Li2^viii	79.82 (4)	Ge1—Li1—Gd2^viii	53.9 (4)
Li2^xiii—Ge1—Li2^viii	127.42 (5)	Ge1^vi—Li1—Gd2^viii	117.9 (12)
Gd2^xiii—Ge1—Li2^viii	127.42 (5)	Gd1^xv—Li1—Gd2^viii	72.7 (6)
Ge1^xii—Ge1—Gd2^viii	62.75 (6)	Li2^viii—Li1—Gd2^viii	0.00 (3)
Gd2—Ge1—Gd2^viii	79.82 (4)	Ge3—Li1—Li2^vii	132.9 (11)
Li2^xiii—Ge1—Gd2^viii	127.42 (5)	Ge2^ix—Li1—Li2^vii	120.3 (12)
Gd2^xiii—Ge1—Gd2^viii	127.42 (5)	Ge3^xxii—Li1—Li2^vii	58.1 (7)
Li2^viii—Ge1—Gd2^viii	0.000 (16)	Ge1—Li1—Li2^vii	117.9 (12)
Ge1^xii—Ge1—Gd1^xiv	133.99 (9)	Ge1^vi—Li1—Li2^vii	53.9 (4)
Gd2—Ge1—Gd1^xiv	88.93 (5)	Gd1^xv—Li1—Li2^vii	114.5 (12)
Li2^xiii—Ge1—Gd1^xiv	85.38 (5)	Li2^viii—Li1—Li2^vii	64.8 (8)
Gd2^xiii—Ge1—Gd1^xiv	85.38 (5)	Gd2^viii—Li1—Li2^vii	64.8 (8)
Li2^viii—Ge1—Gd1^xiv	133.59 (6)	Ge3—Li1—Gd2^vii	132.9 (11)
Gd2^viii—Ge1—Gd1^xiv	133.59 (6)	Ge2^ix—Li1—Gd2^vii	120.3 (12)
Ge1^xii—Ge1—Gd1^xv	65.28 (6)	Ge3^xxii—Li1—Gd2^vii	58.1 (7)
Gd2—Ge1—Gd1^xv	134.54 (6)	Ge1—Li1—Gd2^vii	117.9 (12)
Li2^xiii—Ge1—Gd1^xv	76.88 (4)	Ge1^vi—Li1—Gd2^vii	53.9 (4)
Gd2^xiii—Ge1—Gd1^xv	76.88 (4)	Gd1^xv—Li1—Gd2^vii	114.5 (12)
Li2^viii—Ge1—Gd1^xv	81.71 (5)	Li2^viii—Li1—Gd2^vii	64.8 (8)
Gd2^viii—Ge1—Gd1^xv	81.71 (5)	Gd2^viii—Li1—Gd2^vii	64.8 (8)
Gd1^xiv—Ge1—Gd1^xv	74.76 (4)	Li2^vii—Li1—Gd2^vii	0.000 (17)
Ge1^xii—Ge1—Gd1^vi	65.16 (6)	Ge3—Li1—Gd1^iv	60.3 (7)
Gd2—Ge1—Gd1^vi	84.12 (5)	Ge2^ix—Li1—Gd1^iv	123.7 (10)
Li2^xiii—Ge1—Gd1^vi	82.43 (5)	Ge3^xxii—Li1—Gd1^iv	57.5 (7)
Gd2^xiii—Ge1—Gd1^vi	82.43 (5)	Ge1—Li1—Gd1^iv	139.9 (13)
Li2^viii—Ge1—Gd1^vi	76.14 (4)	Ge1^vi—Li1—Gd1^iv	56.7 (3)
Gd2^viii—Ge1—Gd1^vi	76.14 (4)	Gd1^xv—Li1—Gd1^iv	83.4 (10)
Gd1^xiv—Ge1—Gd1^vi	147.62 (6)	Li2^viii—Li1—Gd1^iv	114.5 (12)
Gd1^xv—Ge1—Gd1^vi	130.44 (5)	Gd2^viii—Li1—Gd1^iv	114.5 (12)
Ge1^xii—Ge1—Li1	110.8 (8)	Li2^vii—Li1—Gd1^iv	72.7 (6)
Gd2—Ge1—Li1	70.2 (8)	Gd2^vii—Li1—Gd1^iv	72.7 (6)
Li2^xiii—Ge1—Li1	137.1 (8)	Ge3—Li1—Gd1^xiv	56.5 (7)
Gd2^xiii—Ge1—Li1	137.1 (8)	Ge2^ix—Li1—Gd1^xiv	57.9 (7)
Li2^viii—Ge1—Li1	65.9 (8)	Ge3^xxii—Li1—Gd1^xiv	123.4 (10)
Gd2^viii—Ge1—Li1	65.9 (8)	Ge1—Li1—Gd1^xiv	53.3 (3)
Gd1^xiv—Ge1—Li1	67.9 (8)	Ge1^vi—Li1—Gd1^xiv	132.8 (13)
Gd1^xv—Ge1—Li1	64.4 (8)	Gd1^xv—Li1—Gd1^xiv	65.9 (5)
Gd1^vi—Ge1—Li1	136.9 (8)	Li2^viii—Li1—Gd1^xiv	107.06 (13)
Ge1^xii—Ge1—Gd1^xvi	119.42 (9)	Gd2^viii—Li1—Gd1^xiv	107.06 (13)
Gd2—Ge1—Gd1^xvi	72.51 (4)	Li2^vii—Li1—Gd1^xiv	170.1 (11)
Li2^xiii—Ge1—Gd1^xvi	72.37 (4)	Gd2^vii—Li1—Gd1^xiv	170.1 (11)
Gd2^xiii—Ge1—Gd1^xvi	72.37 (4)	Gd1^iv—Li1—Gd1^xiv	116.8 (13)
Li2^viii—Ge1—Gd1^xvi	136.86 (5)

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