Crystal structure of Cs2GdNb6Cl15O3 in the structural evolution of niobium oxychlorides with octa­hedral Nb6-cluster units

Silaban, S.; Haryani, M.E.; Gulo, F.; Perrin, C.

doi:10.1107/S205698902300871X

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ISSN: 2056-9890

Volume 79| Part 11| November 2023| Pages 1008-1011

https://doi.org/10.1107/S205698902300871X

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Crystal structure of Cs₂GdNb₆Cl₁₅O₃ in the structural evolution of niobium oxychlorides with octahedral Nb₆-cluster units

Saronom Silaban,^a Maefa Eka Haryani,^b Fakhili Gulo ^c ^* and Christiane Perrin ^d

^aDepartment of Chemistry, Medan State University, Medan 20221, Indonesia, ^bDepartment of Chemistry Education, Sriwijaya University, Inderalaya, Ogan Ilir 30662, South Sumatra, Indonesia, ^cStudy Program of Environmental Science, Postgraduate Program, Sriwijaya University, Palembang 30139, South Sumatra, Indonesia, and ^dInstitut de Chimie de Rennes, Laboratoire de Chimie du Solide et Inorganique Moleculaire, UMR 6511, CNRS-Université de Rennes 1, Avenue du Général Leclerc, 35042 Rennes Cedex, France
^*Correspondence e-mail: fgulo@unsri.ac.id

Edited by M. Weil, Vienna University of Technology, Austria (Received 21 August 2023; accepted 4 October 2023; online 10 October 2023)

Cs₂GdNb₆Cl₁₅O₃, dicaesium gadolinium hexaniobium pentadecachloride trioxide, was synthesized by solid-state reactions starting from a stoichiometric mixture of CsCl, Gd₂O₃, Nb, NbCl₅, and Nb₂O₅. The crystal structure is based on octahedral Nb₆ cluster units (point group symmetry 3.2) with composition [(Nb₆Clⁱ₉Oⁱ₃)Cl^a₆]^5– where i and a denote inner and outer ligands. Cs₂GdNb₆Cl₁₅O₃ exhibits 14 valence electrons per cluster unit. The cluster units are linked to each other by Cs^I and Gd^III atoms, whereby Cs^I (site symmetry 3..) is 12-coordinated by six Clⁱ and six Cl^a ligands belonging to six neighboring cluster units and Gd^III (site symmetry 3.2) is 9-coordinated by three Oⁱ and six Clⁱ ligands belonging to three adjacent cluster units. The arrangement of cluster units corresponds to a stacking of …AA′A… layers along [001]. Cs₂GdNb₆Cl₁₅O₃ is isotypic with Cs₂UNb₆Cl₁₅O₃.

Keywords: cluster compound; crystal structure; valence electron count.

CCDC reference: 2299097

1. Chemical context

Transition-metal clusters have high potentials and synergetic effects in the fields of biotechnology, catalysis, or sensor applications (Nguyen et al., 2022 ). The use of these clusters as supramolecular building units is advantageous because of their unique structural, chemical and physical properties (Zhou & Lachgar, 2007 ). For example, charge-transfer (CT) solids with an anti-perovskite crystal structure have been derived from molybdenum cluster units by electro-crystallization (Hiramatsu et al., 2015 ), or octahedral cluster units of niobium have been widely used as raw materials for the preparation of novel compounds with interesting structures and magnetic properties (Naumov et al., 2003 ; Zhang et al., 2011 ).

A large number of binary, ternary and quaternary niobium compounds with octahedral clusters based on the [Nb₆Lⁱ₁₂L^a₆] unit (L = halogen or oxygen ligands) have been reported previously (Perrin et al., 2001 ). In this cluster unit, the edge of the Nb₆ octahedron is bridged by twelve inner ligands (Lⁱ) while the other six outer ligands (L^a) are located at apical positions (Schäfer & von Schnering, 1964 ). The number of electrons involved in the formation of metal–metal bonds in the cluster is called the valence electron count (VEC). The ideal VEC value per cluster is 16 for chloride compounds and 14 for oxide compounds. In chlorides, the cluster units are interlinked by involving outer ligands (Perrin, 1997 ), whereas in oxides, the connectivity between the units is achieved through the inner ligands (Köhler et al., 1991 ).

Mixing of halogen and oxygen as ligands for Nb₆ cluster compounds is a very interesting topic for in-depth studies to enrich our knowledge about new materials and their physical and chemical properties. It has been reported that the structural, magnetic and electronic properties of octahedral clusters of niobium oxychlorides are influenced by oxygen ligands (Fontaine et al., 2011 ). In this respect, preparation and characterization of new oxychloride compounds with octahedral Nb₆ clusters were reported by Perrin et al. with one Oⁱ (Cordier et al., 1996 ), two Oⁱ (Gulo & Perrin, 2000 ), three Oⁱ (Cordier et al., 1994 , 1997 ; Gulo & Perrin, 2002 ), and six Oⁱ (Gulo et al., 2001 ) ligands per cluster unit. Other oxychloride compounds containing four Oⁱ (Anokhina et al., 1998 , 2000 ) and six Oⁱ (Anokhina et al., 2001 ) ligands per cluster unit are also known.

The niobium oxychloride compound Cs₂UNb₆Cl₁₅O₃ was synthesized and structurally characterized many years ago (Cordier et al., 1997). We have now prepared a related compound with composition Cs₂GdNb₆Cl₁₅O₃ and have determined its crystal structure where gadolinium occupies the same position as uranium in the previous compound. In the current communication, the crystal structure, interatomic distances, and the role of monovalent and trivalent cations in Cs₂GdNb₆Cl₁₅O₃ are compared with other niobium oxychlorides containing octahedral Nb₆ clusters.

2. Structural commentary

The structure of Cs₂GdNb₆Cl₁₅O₃ is isotypic with Cs₂UNb₆Cl₁₅O₃ and displays the Nb₆ octahedron as the basic cluster motif. The asymmetric unit comprises seven sites: one Cs (site symmetry 3.., multiplicity 4, Wyckoff letter e), one Gd (3.2, 2 c), one Nb (1, 12 i), one O (..2, 6 h) and three Cl (Cl1: 6 h; Cl2 12 i; Cl3: 12 i). Six symmetry-equivalent niobium atoms build up the octahedral cluster (centered at a position with site symmetry 3.2, 2 a). Each niobium atom is surrounded by one oxygen (O) inner-ligand, three chlorine (Cl1 and Cl2) inner-ligands, and one chlorine (Cl3) outer-ligand. Every edge of the Nb₆ octahedron is bridged by a chlorine or oxygen ligand as inner-ligands, and six other chlorine ligands are attached in apical positions as outer ligands, as shown in Fig. 1. This cluster motif can be written as a developed unit, [(Nb₆Clⁱ₉Oⁱ₃)Cl^a₆]^5–.

Figure 1
The [(Nb₆Clⁱ₉Oⁱ₃)Cl^a₆]^5– unit in the crystal structure of Cs₂GdNb₆Cl₁₅O₃. Displacement ellipsoids are shown at the 60% probability level.

The length of the intracluster Nb—Nb bonds range from 2.7686 (5) to 3.0317 (5) Å corresponding to the edge bridged by the Oⁱ and Clⁱ ligands, respectively; the average bond length is 2.954 Å. Thus, the Nb₆ octahedron undergoes distortions as observed in other niobium oxychloride compounds. The Nb—Nb distances in this compound are significantly shorter than those observed in other compounds containing two or fewer Oⁱ ligands but are significantly longer than those observed in compounds containing four or more Oⁱ ligands (Gulo & Perrin, 2012 ). In the various oxychloride compounds that have been isolated so far, it seems that an increase in the number of Oⁱ ligands per formula leads to a decrease in the length of intracluster Nb—Nb bonds. This difference is due to a stronger steric effect as observed, for example, in PbLu₃Nb₆Cl₁₅O₆ (Gulo et al., 2001) with six Oⁱ ligands. Cs₂GdNb₆Cl₁₅O₃ has three Oⁱ ligands per cluster. They are localized at trans-inner positions relative to the Nb₆ cluster, similar to the arrangement of three Oⁱ ligands in Na_0.21Nb₆Cl_10.5O₃ where the cluster exhibits point group symmetry 3 (Gulo & Perrin, 2002). In contrast, the three Oⁱ ligands in ScNb₆Cl₁₃O₃ occupy a cis-inner position relative to the Nb₆ octahedron to produce a cluster motif with 2 symmetry (Cordier et al., 1994). In the title compound, the Nb₆ clusters are arranged in (001) layers with an …AA′A… stacking along [001] (Fig. 2).

Figure 2
The …AA′A… stacking of the Nb₆ clusters in the crystal structure of Cs₂GdNb₆Cl₁₅O₃. Cl and O atoms are omitted for clarity

The Nb—Clⁱ distances vary from 2.4543 (7) Å to 2.4802 (7) Å (average 2.468 Å) while the Nb—Cl^a bond is longer, 2.5728 (7) Å. In general, the Nb—L (L = O, Cl) bond lengths in Cs₂GdNb₆Cl₁₅O₃ are not significantly different from that of other niobium oxychloride compounds (Naumov et al., 2003).

In the crystal structure of Cs₂GdNb₆Cl₁₅O₃, the [(Nb₆Clⁱ₉Oⁱ₃)Cl^a₆]^5– units are interconnected through the Cs^I and Gd^III atoms that are located in between the layers of Nb₆ clusters (Fig. 2). The existence of such discrete cluster units or the absence of intercluster connectivity has also been observed in PbLu₃Nb₆Cl₁₅O₆ (Gulo et al., 2001) and Cs₂Ti₄Nb₆Cl₁₈O₆ (Anokhina et al., 2001) where Nb₆-clusters likewise are formed by six symmetry-equivalent Nb atoms in contrast to CsNb₆Cl₁₂O₂ (Gulo & Perrin, 2000) where the Nb₆-octahedron is formed by three different Nb atoms. In the crystal structure of the latter, the the cluster units are linked together via bridging O and Cl ligands.

The Gd^III atom in Cs₂GdNb₆Cl₁₅O₃ has a coordination number of 9, defined by three Oⁱ and six Cl^a ligands provided by three nearby cluster units (Fig. 3), with bond lengths of Gd—O = 2.322 (3) Å and Gd—Cl = 3.0994 (8) Å. In comparison, in the crystal structure of PbLu₃Nb₆Cl₁₅O₆, the Lu^III atom is surrounded by only six ligands, viz. two O and four Cl atoms, defining Lu₂Cl₂ entities (Gulo et al., 2001). The Nb₆-clusters in PbLu₃Nb₆Cl₁₅O₆ connect to each other via these Lu₂Cl₂ entities whereby each cluster is surrounded by six Lu₂Cl₂ entities, and each of them bridging four adjacent clusters via O and Cl ligands. A related motif is found in Ti₂Nb₆Cl₁₄O₄ where Ti^III atoms form zigzag chains of edge-sharing [TiCl₄O₂] octahedra (Anokhina et al., 2000). In other cases, the trivalent ions, such as Sc^III in ScNb₆Cl₁₃O₃ (Cordier et al., 1994) or Ti^III in Cs₂Ti₃Nb₁₂Cl₂₇O₈ (Anokhina et al., 2000), have a coordination number of five, defined by three O and two Cl ligands. In another case, the Gd^III atom in RbGdNb₆Cl₁₈ is octahedrally surrounded by six Cl ligands from six neighboring cluster units (Gulo et al., 2023 ). In general, in the series of niobium oxychloride compounds containing octahedral Nb₆ clusters, the crystallographic sites associated with trivalent cations are always fully occupied and are surrounded by Cl and O ligands (Gulo & Perrin, 2012). Only in Cs₂GdNb₆Cl₁₅O₃ and the isotypic uranium analogue, the trivalent cation occupy the center of a triangle formed by three adjacent cluster units and are bonded to nine ligands.

Figure 3
The environment of the Gd^III atom in Cs₂GdNb₆Cl₁₅O₃.

In Cs₂GdNb₆Cl₁₅O₃, the monovalent Cs^I atom is surrounded by six Nb₆ clusters and coordinated by twelve Cl ligands (Fig. 4). The lengths of Cs—Cl bonds range from 3.5074 (8) to 3.9770 (6) Å. A similar environment around Cs is found in CsNb₆Cl₁₂O₂ with Cs—Cl distances between 3.330 (5) and 3.862 (4) Å (Gulo & Perrin, 2000). In contrast, the Cs^I atom in Cs₂LuNb₆Cl₁₇O is surrounded by four Nb₆-clusters and is bonded to twelve chlorine ligands with Cs—Cl distances in the range 3.567 (1) to 3.619 (1) Å (Cordier et al., 1996). In RbGdNb₆Cl₁₈ with its smaller monovalent cation Rb^I, the coordination number is likewise 12. Here, the cation is surrounded also by four Nb₆ clusters, and the Rb—Cl bond lengths range from 3.471 (1) Å to 3.557 (2) Å with an average of 3.512 Å (Gulo et al., 2023). The sites of monovalent cations encountered in the crystal structures of oxychlorides with Nb₆ clusters are always surrounded by Cl ligands with the exception of Cs₂LuNb₆Cl₁₇O where an O atom statistically occupies a site among the twelve inner ligands defining the coordination environment of Cs. On the other hand, the sites associated with the (large) monovalent cation often show partial occupancy. For example, in Na_0.21Nb₆Cl_10.5O₃, the corresponding Na site has an occupancy of only 42.6% (Gulo & Perrin, 2002) and the three Cs sites in Cs₂Ti₄Nb₆Cl₁₈O₆ have occupancies of 38.1%, 57.0% and 6.9% (Anokhina et al., 2001).

Figure 4
The environment of the Cs^I atom in Cs₂GdNb₆Cl₁₅O₃.

The VEC in Cs₂GdNb₆Cl₁₅O₃ is 14 per cluster unit, as observed in most oxide (Köhler et al., 1991) and oxychloride compounds (Gulo & Perrin, 2012). The number of Oⁱ ligands per cluster can affect the VEC value. Compounds containing one Oⁱ ligand (Cordier et al., 1996) or two Oⁱ ligands (Gulo & Perrin, 2000) exhibit VEC values of 16 and 15. However, niobium oxychloride compounds containing three or more Oⁱ ligands per cluster unit have always a VEC of 14 per cluster unit.

3. Synthesis and crystallization

Cs₂GdNb₆Cl₁₅O₃ was prepared by solid-state reactions, starting from a stoichiometric mixture of CsCl (Prolabo, purity 99.5%), Gd₂O₃ (Rhône Poulenc), Nb₂O₅ (Merck, Optipur), NbCl₅ (Ventron, purity 99.998%) and niobium powder (Ventron, purity 99.8%). A total of 300 mg of the mixture was mashed and then loaded in a silica tube under argon atmosphere in a glove box. The silica tube sample was then sealed under vacuum condition. The sample was heated in a vertical heating furnace at 973 K for two days, followed by slow cooling to room temperature. Brown single crystals with a block-like form suitable for structural determination were obtained this way.

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The remaining maximum and minimum electron density peaks are located 0.19 Å from Nb and 0.54 Å from Cs, respectively.

Table 1
Experimental details

Crystal data
Chemical formula	Cs₂GdNb₆Cl₁₅O₃
M_r	1560.28
Crystal system, space group	Trigonal, P $[\overline{3}]$ 1c
Temperature (K)	293
a, c (Å)	9.1318 (1), 17.1558 (2)
V (Å³)	1238.95 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	9.83
Crystal size (mm)	0.08 × 0.07 × 0.05

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.004, 0.017
No. of measured, independent and observed [I > 2σ(I)] reflections	7607, 2020, 1790
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.833

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.068, 1.15
No. of reflections	2020
No. of parameters	44
Δρ_max, Δρ_min (e Å⁻³)	1.38, −1.35
Computer programs: COLLECT (Nonius, 1999 ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg, 2014 ), and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2299097

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698902300871X/wm5695sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698902300871X/wm5695Isup2.hkl

checkCIF report

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: COLLECT (Nonius, 1999); data reduction: COLLECT (Nonius, 1999); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

(I) top

Crystal data top

Cs₂GdNb₆Cl₁₅O₃	D_x = 4.182 Mg m⁻³
M_r = 1560.28	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31c	Cell parameters from 25 reflections
a = 9.1318 (1) Å	θ = 12–18°
c = 17.1558 (2) Å	µ = 9.83 mm⁻¹
V = 1238.95 (3) Å³	T = 293 K
Z = 2	Block, brown
F(000) = 1398	0.08 × 0.07 × 0.05 mm

Data collection top

Nonius KappaCCD diffractometer	1790 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
ω scans	θ_max = 36.3°, θ_min = 2.4°
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997)	h = −15→15
T_min = 0.004, T_max = 0.017	k = −12→12
7607 measured reflections	l = −27→28
2020 independent reflections

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)] = 0.029	w = 1/[σ²(F_o²) + (0.0258P)² + 3.5848P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.068	(Δ/σ)_max = 0.001
S = 1.15	Δρ_max = 1.38 e Å⁻³
2020 reflections	Δρ_min = −1.35 e Å⁻³
44 parameters	Extinction correction: SHELXL2018/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00259 (19)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cs	0.333333	0.666667	0.54654 (2)	0.02645 (9)
Gd	0.666667	0.333333	0.750000	0.01649 (8)
Nb	0.19768 (3)	0.01608 (3)	0.68239 (2)	0.01105 (7)
Cl1	0.21283 (6)	−0.21283 (6)	0.750000	0.01643 (17)
Cl2	0.01675 (8)	−0.20367 (8)	0.58643 (4)	0.01569 (12)
Cl3	0.47649 (9)	0.07637 (10)	0.61760 (5)	0.02252 (15)
O	0.3730 (3)	0.18650 (17)	0.750000	0.0142 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cs	0.02466 (12)	0.02466 (12)	0.03002 (19)	0.01233 (6)	0.000	0.000
Gd	0.00919 (9)	0.00919 (9)	0.03108 (19)	0.00460 (5)	0.000	0.000
Nb	0.00836 (10)	0.00944 (10)	0.01540 (12)	0.00448 (7)	0.00090 (7)	0.00034 (7)
Cl1	0.0149 (3)	0.0149 (3)	0.0233 (4)	0.0103 (3)	0.0031 (3)	0.0031 (3)
Cl2	0.0144 (3)	0.0143 (3)	0.0180 (3)	0.0068 (2)	0.0007 (2)	−0.0028 (2)
Cl3	0.0177 (3)	0.0231 (3)	0.0298 (4)	0.0125 (3)	0.0090 (3)	0.0033 (3)
O	0.0092 (10)	0.0139 (9)	0.0179 (13)	0.0046 (5)	0.000	−0.0004 (8)

Geometric parameters (Å, º) top

Cs—Cl3ⁱ	3.5074 (8)	Gd—Cl3	3.0994 (8)
Cs—Cl3ⁱⁱ	3.5074 (8)	Gd—Cl3^viii	3.0994 (8)
Cs—Cl3ⁱⁱⁱ	3.5074 (8)	Gd—Cl3^vii	3.0994 (8)
Cs—Cl3^iv	3.5180 (8)	Gd—Cl3^ix	3.0994 (8)
Cs—Cl3^v	3.5180 (8)	Gd—Cl3^x	3.0994 (8)
Cs—Cl3^vi	3.5180 (8)	Gd—Cl3ⁱⁱⁱ	3.0994 (8)
Cs—Cl2ⁱ	3.6948 (7)	Nb—O	1.9593 (19)
Cs—Cl2ⁱⁱⁱ	3.6948 (7)	Nb—Cl1	2.4543 (7)
Cs—Cl2ⁱⁱ	3.6948 (7)	Nb—Cl2ⁱⁱ	2.4684 (7)
Cs—Cl1ⁱⁱⁱ	3.9770 (6)	Nb—Cl2	2.4802 (7)
Cs—Cl1ⁱⁱ	3.9770 (6)	Nb—Cl3	2.5728 (7)
Cs—Cl1ⁱ	3.9770 (5)	Nb—Nb^x	2.7686 (5)
Gd—O	2.322 (3)	Nb—Nb^xi	3.0075 (4)
Gd—O^vii	2.322 (3)	Nb—Nbⁱⁱ	3.0075 (4)
Gd—Oⁱⁱⁱ	2.322 (3)	Nb—Nb^xii	3.0317 (5)

Cl3ⁱ—Cs—Cl3ⁱⁱ	108.589 (15)	Oⁱⁱⁱ—Gd—Cl3^vii	80.189 (14)
Cl3ⁱ—Cs—Cl3ⁱⁱⁱ	108.589 (15)	Cl3—Gd—Cl3^vii	72.21 (2)
Cl3ⁱⁱ—Cs—Cl3ⁱⁱⁱ	108.589 (15)	Cl3^viii—Gd—Cl3^vii	98.06 (3)
Cl3ⁱ—Cs—Cl3^iv	108.89 (2)	O—Gd—Cl3^ix	80.189 (13)
Cl3ⁱⁱ—Cs—Cl3^iv	76.72 (2)	O^vii—Gd—Cl3^ix	60.971 (13)
Cl3ⁱⁱⁱ—Cs—Cl3^iv	137.786 (19)	Oⁱⁱⁱ—Gd—Cl3^ix	130.969 (15)
Cl3ⁱ—Cs—Cl3^v	76.72 (2)	Cl3—Gd—Cl3^ix	98.06 (3)
Cl3ⁱⁱ—Cs—Cl3^v	137.786 (19)	Cl3^viii—Gd—Cl3^ix	72.21 (2)
Cl3ⁱⁱⁱ—Cs—Cl3^v	108.89 (2)	Cl3^vii—Gd—Cl3^ix	121.94 (2)
Cl3^iv—Cs—Cl3^v	62.55 (2)	O—Gd—Cl3^x	60.971 (13)
Cl3ⁱ—Cs—Cl3^vi	137.786 (19)	O^vii—Gd—Cl3^x	130.969 (14)
Cl3ⁱⁱ—Cs—Cl3^vi	108.89 (2)	Oⁱⁱⁱ—Gd—Cl3^x	80.189 (14)
Cl3ⁱⁱⁱ—Cs—Cl3^vi	76.72 (2)	Cl3—Gd—Cl3^x	121.94 (3)
Cl3^iv—Cs—Cl3^vi	62.55 (2)	Cl3^viii—Gd—Cl3^x	72.21 (2)
Cl3^v—Cs—Cl3^vi	62.55 (2)	Cl3^vii—Gd—Cl3^x	160.38 (3)
Cl3ⁱ—Cs—Cl2ⁱ	61.822 (15)	Cl3^ix—Gd—Cl3^x	72.21 (2)
Cl3ⁱⁱ—Cs—Cl2ⁱ	54.828 (15)	O—Gd—Cl3ⁱⁱⁱ	80.189 (14)
Cl3ⁱⁱⁱ—Cs—Cl2ⁱ	148.77 (2)	O^vii—Gd—Cl3ⁱⁱⁱ	130.969 (14)
Cl3^iv—Cs—Cl2ⁱ	69.076 (17)	Oⁱⁱⁱ—Gd—Cl3ⁱⁱⁱ	60.971 (13)
Cl3^v—Cs—Cl2ⁱ	97.986 (17)	Cl3—Gd—Cl3ⁱⁱⁱ	72.20 (2)
Cl3^vi—Cs—Cl2ⁱ	131.531 (19)	Cl3^viii—Gd—Cl3ⁱⁱⁱ	121.94 (3)
Cl3ⁱ—Cs—Cl2ⁱⁱⁱ	54.828 (15)	Cl3^vii—Gd—Cl3ⁱⁱⁱ	72.21 (2)
Cl3ⁱⁱ—Cs—Cl2ⁱⁱⁱ	148.77 (2)	Cl3^ix—Gd—Cl3ⁱⁱⁱ	160.38 (3)
Cl3ⁱⁱⁱ—Cs—Cl2ⁱⁱⁱ	61.822 (15)	Cl3^x—Gd—Cl3ⁱⁱⁱ	98.06 (3)
Cl3^iv—Cs—Cl2ⁱⁱⁱ	131.531 (19)	O—Nb—Cl1	91.438 (10)
Cl3^v—Cs—Cl2ⁱⁱⁱ	69.076 (18)	O—Nb—Cl2ⁱⁱ	95.39 (2)
Cl3^vi—Cs—Cl2ⁱⁱⁱ	97.986 (17)	Cl1—Nb—Cl2ⁱⁱ	165.85 (2)
Cl2ⁱ—Cs—Cl2ⁱⁱⁱ	116.649 (8)	O—Nb—Cl2	169.99 (6)
Cl3ⁱ—Cs—Cl2ⁱⁱ	148.77 (2)	Cl1—Nb—Cl2	85.583 (18)
Cl3ⁱⁱ—Cs—Cl2ⁱⁱ	61.822 (15)	Cl2ⁱⁱ—Nb—Cl2	85.58 (3)
Cl3ⁱⁱⁱ—Cs—Cl2ⁱⁱ	54.828 (15)	O—Nb—Cl3	75.97 (6)
Cl3^iv—Cs—Cl2ⁱⁱ	97.986 (17)	Cl1—Nb—Cl3	85.14 (2)
Cl3^v—Cs—Cl2ⁱⁱ	131.531 (19)	Cl2ⁱⁱ—Nb—Cl3	84.52 (2)
Cl3^vi—Cs—Cl2ⁱⁱ	69.076 (17)	Cl2—Nb—Cl3	94.24 (3)
Cl2ⁱ—Cs—Cl2ⁱⁱ	116.649 (8)	O—Nb—Nb^x	45.05 (6)
Cl2ⁱⁱⁱ—Cs—Cl2ⁱⁱ	116.649 (8)	Cl1—Nb—Nb^x	94.843 (15)
Cl3ⁱ—Cs—Cl1ⁱⁱⁱ	62.628 (14)	Cl2ⁱⁱ—Nb—Nb^x	98.75 (2)
Cl3ⁱⁱ—Cs—Cl1ⁱⁱⁱ	97.912 (19)	Cl2—Nb—Nb^x	144.687 (16)
Cl3ⁱⁱⁱ—Cs—Cl1ⁱⁱⁱ	53.624 (14)	Cl3—Nb—Nb^x	121.017 (19)
Cl3^iv—Cs—Cl1ⁱⁱⁱ	168.335 (15)	O—Nb—Nb^xi	137.22 (6)
Cl3^v—Cs—Cl1ⁱⁱⁱ	119.844 (17)	Cl1—Nb—Nb^xi	89.097 (14)
Cl3^vi—Cs—Cl1ⁱⁱⁱ	129.093 (15)	Cl2ⁱⁱ—Nb—Nb^xi	94.227 (16)
Cl2ⁱ—Cs—Cl1ⁱⁱⁱ	99.332 (16)	Cl2—Nb—Nb^xi	52.396 (17)
Cl2ⁱⁱⁱ—Cs—Cl1ⁱⁱⁱ	51.659 (16)	Cl3—Nb—Nb^xi	146.53 (2)
Cl2ⁱⁱ—Cs—Cl1ⁱⁱⁱ	88.306 (13)	Nb^x—Nb—Nb^xi	92.291 (4)
Cl3ⁱ—Cs—Cl1ⁱⁱ	97.912 (19)	O—Nb—Nbⁱⁱ	94.52 (4)
Cl3ⁱⁱ—Cs—Cl1ⁱⁱ	53.623 (14)	Cl1—Nb—Nbⁱⁱ	139.044 (15)
Cl3ⁱⁱⁱ—Cs—Cl1ⁱⁱ	62.629 (14)	Cl2ⁱⁱ—Nb—Nbⁱⁱ	52.752 (17)
Cl3^iv—Cs—Cl1ⁱⁱ	129.092 (15)	Cl2—Nb—Nbⁱⁱ	93.982 (16)
Cl3^v—Cs—Cl1ⁱⁱ	168.336 (16)	Cl3—Nb—Nbⁱⁱ	135.56 (2)
Cl3^vi—Cs—Cl1ⁱⁱ	119.844 (17)	Nb^x—Nb—Nbⁱⁱ	63.159 (10)
Cl2ⁱ—Cs—Cl1ⁱⁱ	88.305 (13)	Nb^xi—Nb—Nbⁱⁱ	60.0
Cl2ⁱⁱⁱ—Cs—Cl1ⁱⁱ	99.332 (16)	O—Nb—Nb^xii	93.78 (4)
Cl2ⁱⁱ—Cs—Cl1ⁱⁱ	51.660 (16)	Cl1—Nb—Nb^xii	51.856 (14)
Cl1ⁱⁱⁱ—Cs—Cl1ⁱⁱ	49.043 (19)	Cl2ⁱⁱ—Nb—Nb^xii	139.534 (16)
Cl3ⁱ—Cs—Cl1ⁱ	53.623 (14)	Cl2—Nb—Nb^xii	91.888 (19)
Cl3ⁱⁱ—Cs—Cl1ⁱ	62.629 (15)	Cl3—Nb—Nb^xii	135.895 (19)
Cl3ⁱⁱⁱ—Cs—Cl1ⁱ	97.912 (19)	Nb^x—Nb—Nb^xii	62.269 (11)
Cl3^iv—Cs—Cl1ⁱ	119.843 (17)	Nb^xi—Nb—Nb^xii	54.570 (9)
Cl3^v—Cs—Cl1ⁱ	129.092 (15)	Nbⁱⁱ—Nb—Nb^xii	87.296 (5)
Cl3^vi—Cs—Cl1ⁱ	168.336 (16)	Nb^xii—Cl1—Nb	76.29 (3)
Cl2ⁱ—Cs—Cl1ⁱ	51.659 (16)	Nb^xii—Cl1—Cs^xiii	142.343 (15)
Cl2ⁱⁱⁱ—Cs—Cl1ⁱ	88.305 (13)	Nb—Cl1—Cs^xiii	87.830 (6)
Cl2ⁱⁱ—Cs—Cl1ⁱ	99.333 (16)	Nb^xii—Cl1—Cs^xiv	87.831 (6)
Cl1ⁱⁱⁱ—Cs—Cl1ⁱ	49.043 (19)	Nb—Cl1—Cs^xiv	142.343 (15)
Cl1ⁱⁱ—Cs—Cl1ⁱ	49.043 (19)	Cs^xiii—Cl1—Cs^xiv	122.73 (2)
O—Gd—O^vii	120.0	Nb^xi—Cl2—Nb	74.85 (2)
O—Gd—Oⁱⁱⁱ	120.0	Nb^xi—Cl2—Cs^xiii	146.20 (3)
O^vii—Gd—Oⁱⁱⁱ	120.000 (1)	Nb—Cl2—Cs^xiii	94.06 (2)
O—Gd—Cl3	60.971 (13)	Nb—Cl3—Gd	88.01 (2)
O^vii—Gd—Cl3	80.190 (14)	Nb—Cl3—Cs^xiii	96.94 (2)
Oⁱⁱⁱ—Gd—Cl3	130.969 (14)	Gd—Cl3—Cs^xiii	146.22 (3)
O—Gd—Cl3^viii	130.969 (14)	Nb—Cl3—Cs^v	126.46 (3)
O^vii—Gd—Cl3^viii	80.189 (14)	Gd—Cl3—Cs^v	100.30 (2)
Oⁱⁱⁱ—Gd—Cl3^viii	60.971 (13)	Cs^xiii—Cl3—Cs^v	103.28 (2)
Cl3—Gd—Cl3^viii	160.38 (3)	Nb^x—O—Nb	89.91 (11)
O—Gd—Cl3^vii	130.969 (15)	Nb^x—O—Gd	135.05 (6)
O^vii—Gd—Cl3^vii	60.971 (13)	Nb—O—Gd	135.05 (6)

Symmetry codes: (i) x, y+1, z; (ii) −y, x−y, z; (iii) −x+y+1, −x+1, z; (iv) y, −x+y+1, −z+1; (v) −x+1, −y+1, −z+1; (vi) x−y, x, −z+1; (vii) −y+1, x−y, z; (viii) −y+1, −x+1, −z+3/2; (ix) −x+y+1, y, −z+3/2; (x) x, x−y, −z+3/2; (xi) −x+y, −x, z; (xii) −y, −x, −z+3/2; (xiii) x, y−1, z; (xiv) −y+1, −x, −z+3/2.

Acknowledgements

The authors thank T. Roisnel, Centre de Diffractométrie de l'Université de Rennes 1, France, for the data collection on the Enraf–Nonius KappaCCD X-ray diffractometer.

Funding information

The authors wish to thank the Research Institute of Sriwijaya University for research funding.

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