Cs4[La(NO3)6](NO3). HNO3: Das erste Salpetersäureaddukt eines ternären Alkali-Lanthanidnitrats

Cs₄[La(NO₃)₆](NO₃) · HNO₃: The First Nitric Acid Adduct of a Ternary Alkali Lanthanide Nitrate In the crystal structure of Cs₄[La(NO₃)₆](NO₃). HNO₃ (monoclinic, P2₁/c, Z = 2, a = 787.3(2); b = 1353.0(3); c = 1141.8(7) pm; β = 94,37(3)°) La³⁺ has a coordination number of twelve (six bidentate nitrate ligands). The structure may be viewed at as a layer structure: Layers of the composition [Cs(1)₄La₂(NO₃)₁₂]^2?, and [Cs(2)₄(NO₃)₂(HNO₃)₂]²⁺ are stacked alternatively in the [100] direction.     

Ternäre Lithium-Selten-Erd-Nitrate mit einsamen Nitrationen: Li3[M(NO3)5](NO3) (M = Gd?Lu,Y). Die Kristallstruktur von Li3Er(NO3)6

Ternary Lithium Rare Earth Nitrates with Lonesome Nitrate Ions: Li₃[M(NO₃)₅](NO₃) (M = Gd? Lu, Y). The Crystal Structure of Li₃Er(NO₃)₆ Single crystals of the ternary nitrate Li₃Er(NO₃)₆ are obtained from a solution of “Er(NO₃)₃” in the melt of LiNO₃. In Li₃Er(NO₃)₆ (monoclinic, P2₁/n, Z = 4; a = 776.0(1); b = 748.86(8); c = 2 396(1) pm; β = 90.76(3)°; R1 = 0.0490; wR2 = 0.0792), Er³⁺ is surrounded by five bidentate nitrate ligands yielding the anionic units [Er(NO₃)₅]^2?. These are arranged in the direction of the 2₁ screw axis. Two lonesome NO₃^? ions are in the middle of such a “helix” and are connected by Li⁺ with the anions [Er(NO₃)₅]^2?. The helices are moved against each other by about half of the lattice constant a and are connected by further Li⁺ ions.     

Rubidiumhexaamidolanthanat und -neodymat,Rb3[La(NH2)6] und Rb3[Nd(NH2)6]; Strukturverwandtschaft zu K3[Cr(OH6)] und K4CdCl6

Rubidium Hexaamidolanthanate and -neodymate, Rb₃[La(NH₂)₆] and Rb₃[Nd(NH₂)₆]; Compounds. Structurally Related to K₃[Cr(OH)₆] and K₄CdCl₆ Colourless Rb₃[La(NH₂)₆] (a = 12.298(4) Å, c = 13.759(2) Å, N = 6, R3 c) and pale blue Rb₃[Nd(NH₂)₆] (a = 12.199(6) Å, c = 13.626(4) Å, N = 6, R32) have been prepared by the reaction of the corresponding metals (Rb: La resp. Nd = 3:1) with NH₃(P(NH₃) = 4–4.5 kbar) at 300°C. Single crystal x-ray methods gave their structures. It is shown by space group relations that these compounds are structurally related to one another and to further ternary amides as well as to K₃[Cr(OH)₆] and K₄CdCl₆.     

Synthese und Struktur der ternären Ammoniumnitrate (NH4)2[M(NO3)5] (M = Tb?Lu,Y

Synthesis and Structure of the Ternary Ammonium Nitrates (NH₄)₂[M(NO₃)₅] (M = Tb? Lu, Y) Single crystals of the ternary ammonium nitrates (NH₄)₂[M(NO₃)₅] (M = Tb? Lu, Y) are obtained from the solution of the sesquioxides in a melt of NH₄NO₃ and sublimation of the excess NH₄NO₃. In the crystal structure of (NH₄)₂[Tm(NO₃)₅] (trigonal, P3₁, Z = 3; a = 1 123.76(8), c = 930.1(1) pm; R = 0.062; R_w = 0.034) Tm³⁺ is surrounded by five bidentate nitrate ligands. The isolated [Tm(NO₃)₅]^2? groups are held together by ammonium ions.     

Bildung von NH4[Hg3(NH)2](NO3)3 und Umwandlung in [Hg2N](NO3)

Formation of NH₄[Hg₃(NH)₂](NO₃)₃ and Transformation to [Hg₂N](NO₃) NH₄[Hg₃(NH)₂](NO₃)₃ ( 1 ) and [Hg₂N](NO₃) ( 2 ) are obtained from conc. aqueous ammonia solutions of Hg(NO₃)₂ at ambient temperature and under hydrothermal conditions at 180 °C, respectively, as colourless and dark yellow to light brown single crystals. The crystal structures {NH₄[Hg₃(NH)₂](NO₃)₃: cubic, P4₁32, a = 1030.4(2) pm, Z = 4, R_all = 0.028; [Hg₂N](NO₃): tetra gonal, P4₃2₁2, a = 1540.4(1), c = 909.8(1) pm, Z = 4, R_all = 0.054} have been determined from single crystal data. Both exhibit network type structures in which [HNHg₃] and [NHg₄] tetrahedra of the partial structures of 1 and 2 are connected via three and four vertices, respectively. 1 transforms at about 270 °C in a straightforward reaction to 2 whereby the decomposition products of NH₄NO₃ are set free. 2 decomposes at about 380 °C forming yellow HgO. Most certainly, 1 is identical with a mineral previously analyzed as “Hg(NH₂)(NO₃)” with the same Hg:N:O ratio.     

Synthese,Struktur und Thermolyse der ternären Ammoniumnitrate (NH4)3[M2(NO3)(9] (M  La?Gd)

Synthesis, Structure, and Thermolysis of the (NH₄)₃[M₂(NO₃)₉] (M ? La? Gd) The ternary ammonium nitrates (NH₄)₃[M₂(NO₃)₉] (M ? La-Gd) are obtained as single crystals from a solution of the respective sesquioxides in a melt of NH₄NO₃ and sublimation of the excess NH₄NO₃. In the crystal structure of (NH₄)₃[Pr₂(NO₃)₉] (cubic, P4₃32, Z = 4, a = 1 377.0(1) pm, R = 0.038, R_w = 0.023) Pr³⁺ is surrounded by six bidentate nitrate ligands of which three are bridging to neighbouring Pr³⁺ ions. This results in a branched folded chain, held together by the NH₄⁺ ions which occupy cavities in the structure. (NH₄)₃[Pr₂(NO₃)₉] is the first intermediate product of the thermal decomposition of (NH₄)₂[Pr(NO₃)₅(H₂O)₂] · 2H₂O.     

Synthesis and crystal structure of New Amminecopper(II) Nitrates: [Cu(NH3)2](NO3)2 and [Cu(NH3)](NO3)2

[Cu(NH₃)₂](NO₃)₂ ( I ) and [Cu(NH₃](NO₃)₂ ( II ) were synthesized by interaction of molten NH₄NO₃ with [Cu(NH₃)₄](NO₃)₂ and Cu(NO₃)₂ · 3 H₂O, respectively, at 180 to 195°C for 24 hr. According to X-Ray single crystal analysis, I is orthorhombic (sp. gr. Pbca) with a = 5.678(1), b = 9.765(2), c = 11.596(2) Å, Z = 4, R = 0.060; II is monoclinic (sp. gr. P2₁/c) with a = 6.670(1), b = 8.658(2), c = 9.661(2) Å, β = 101.78(2)°, Z = 4, R = 0.027. In both structures, the nearest coordination environment of Cu is a slightly distorted square formed by N (from NH₃) and O atoms (from NO₃ groups). The structure of I consists of centrosymmetrical [Cu(NH₃)₂](NO₃)₂ molecules linked by hydrogen bonds. The Cu? N and Cu? O distances are 1.98 and 2.01 Å, respectively. In II , the Cu? N distance is 1.95 Å, the Cu? O distances are 1.96, 2.02, and 2.03 Å. The [CuO₃NH₃] squares are connected by NO₃ bridges into zigzag chains, which are linked into layers by longer Cu? O interactions (2.31 Å). Obviously, the layers are additionally strengthened and held together by hydrogen bonds.     

Synthesis and crystal structures of zirconium(IV) nitrate complexes (NO2)[Zr(NO3)3(H2O)3]2(NO3) 3, Cs[Zr(NO3)5], and (NH4)[Zr(NO3)5](HNO3)

The zirconium nitrate complexes (NO₂)[Zr(NO₃)₃(H₂O)₃]₂(NO₃)₃ (1), Cs[Zr(NO₃)₅] ((2), (NH₄)[Zr(NO₃)₅](HNO₃) (3), and (NO₂)_0.23(NO)_0.77[Zr(NO₃)₅] ((4) were prepared by crystallization from nitric acid solutions in the presence of H₂SO₄ or P₂O₅. The complexes were characterized by X-ray diffraction. The crystal structure of 1 consists of nitrate anions, nitronium cations, and [Zr(NO₃)₃(H₂O)₃]⁺ complex cations in which the Zr^IV atom is coordinated by three water molecules and three bidentate nitrate groups. The coordination polyhedron of the Zr^IV atom is a tricapped trigonal prism formed by nine oxygen atoms. The island structures of 2 and 3 contain [Zr(NO₃)₅]^? anions and Cs⁺ or NH₄ ⁺ cations, respectively. In addition, complex 3 contains HNO₃ molecules. Complex 4 differs from (NO₂)[Zr(NO₃)₅] in that three-fourth of the nitronium cations in 4 are replaced by nitrosonium cations NO⁺, resulting in a decrease in the unit cell parameters. In the [Zr(NO₃)₅]^? anion involved in complexes 2–4, the Zr^IV atom is coordinated by five bidentate nitrate groups and has an unusually high coordination number of 10. The coordination polyhedron is a bicapped square antiprism.     

Kristallstruktur von (NH4)3SnF7: Ein Doppelsalz gemäß (NH4)3[SnF6]F und kein (NH4)4SnF8

Crystal Structure of (NH₄)₃SnF₇: A Double Salt According to (NH₄)₃[SnF₆]F and not (NH₄)₄SnF₈ (NH₄)₃SnF₇ is obtained as colourless single crystals from the reaction of NH₄HF₂ with tin powder at 300°C. The crystal structure (cubic, Pm3m, Z = 1, a = 602.5(1) pm at 293 K; a = 598.0(1) pm at 100 K) contains [SnF₆]^2? octahedra and lonesome F^? ions surrounded by NH₄⁺ cations only; it may be considered as a derivative of the Cu₃Au-type of structure according to Cu₃[Au]□ ?(NH₄)₃[SnF₆]F. The F^? ions of the [SnF₆]^2? octahedra with their Sn⁴⁺ centre in the origin of the unit cell at m3m are disordered in different ways at 293 and 100 K, respectively.     

Synthese und Kristallstruktur von Na10[P4(NH)6N4](NH2)6(NH3)0,5 mit dem adamantanartig aufgebauten Anion [P4(NH)6N4]4−

Synthesis and Crystal Structure of Na₁₀[P₄(NH)₆N₄](NH₂)₆(NH₃)_0.5 with an Adamantane-like Anion [P₄(NH)₆N₄]^4? Crystals of Na₁₀[P₄(NH)₆N₄](NH₂)₆(NH₃)_0.5 were obtained by the reaction of P₃N₅ with NaNH₂ (molar ratio 1:20) within 5 d at 600°C in autoclaves. The following data characterize X-ray investigations: Fm3 m, Z = 8, a = 15.423(2) Å, Z(F) = 261 with F ≥ 3 σ(F) Z(Variables) = 27, R/R_w = 0.086/0.089 The compound contains the hitherto unknown anion [P₄(NH)₆N₄]^4?, which resembles adamantane. The total structure can be described as follows: The centers of gravity of units of [Na₈(NH₂)₆(NH₃)]²⁺ – 8Na⁺ on the corners of a cube, 6NH₂^? on the ones of an inscribed octahedron with NH₃ in the center – follow the motif of a cubic-closest packed arrangement. Units of [Na₁₂(NH₂)₆]⁶⁺ – 12Na⁺ on the corners of a cuboctahedron and 6NH₂^? on the ones of an inscribed octahedron – occupy all octahedral and those of [P₄(NH)₆N₄]^4? all tetrahedral sites.     

Synthesis and Crystal Structure of Alkali Metal and Ammonium Nitratocuprates(II): M3[Cu(NO3)4](NO3) (M = K,NH4, Rb) and Cs2[Cu(NO3)4]

Blue crystals of metal nitratocuprates(II), M₃[Cu(NO₃)₄](NO₃) (M = K ( I ), NH₄ ( II ), Rb ( III )) and Cs₂[Cu(NO₃)₄] ( IV ) were synthesized from Cu(NO₃)₂ · 3 H₂O and MNO₃ by heating at 100–140 °C during 3–12 h. X-ray single crystal structures for isotypic I and II reveal the presence of the [Cu(NO₃)₄]^2– and NO₃^– anions and M⁺ cations. Structure IV contains [Cu(NO₃)₄]^2– and Cs⁺. In structures I , II , and IV , Cu atoms have a square-planar coordination [CuO₄] with short Cu–O distances of 1.92–2.00 Å, the oxygen atoms belonging to four different NO₃ groups. Each coordinated NO₃ group is a nonsymmetrical bidentate ligand with the second, longer Cu–O distance from 2.38 to 2.74 Å. Rubidium derivative III was shown to be isotypic to I on the basis of unit cell dimensions and symmetry. Eight-coordinate metal(II) environment in tetranitrates is compared for transition metals with different electronic configurations.     

Die Einwirkung von Ammoniumfluorid auf Scandium: Synthese und Kristallstrukturen von (NH4)3[ScF6] und [Cu(NH3)4]3[ScF6]2

Action of Ammonium Fluoride on Scandium: Synthesis and Crystal Structures of (NH₄)₃[ScF₆] and [Cu(NH₃)₄]₃[ScF₆]₂ The action of (NH₄)F on scandium in copper ampoules yields either (NH₄)₃[ScF₆] or ScF₃ and a small quantity of [Cu(NH₃)₄]₃[ScF₆]₂, respectively, depending upon the molar ratio of the educts (NH₄)F : Sc (6 : 1 and 4 : 1, respectively) and temperature. (NH₄)₃[ScF₆] crystallizes with the cryolite type of structure: monoclinic, P2₁/n, Z = 2; a = 650.0(2); b = 651.4(2); c = 949.0(2) pm; β = 90.40(2)°, [Cu(NH₃)₄]₃[ScF₆]₂ is triclinic, P‐1, Z = 1; a = 821.1(2); b = 821.2(2); c = 822.7(2) pm; α = 90.04(3); β = 90.00(3); γ = 90.16(3)°. In its chemical behaviour against (NH₄)F, scandium parallels aluminium rather than gallium.     

Kaliumhexahydroxochromat(III), K3[Cr(OH)6]: Beispiel eines neuen Syntheseweges für Metallhydroxide und Hydroxometallate

Potassium Hexaydroxochromate(III), K₃[Cr(OH)₆]: An Example for a New Synthetic Way to Metal Hydroxides and Hydroxometallates The comproportionation of nitrate with amide ions in supercritical ammonia leads to the formation of hydroxide ions and elementary nitrogen: [Cr(NH₃)₆](NO₃)₃ reacts with KNH₂ at 250°C and 6 kbar NH₃-pressure to K₃[Cr(OH)₆], K(H₂O)OH and an unknown yellow microcrystalline phase. The bluegreen hydroxochromate is well crystallized. The x-ray structure determination on K₃[Cr(OH)₆] gave the atomic arrangement inclusive the hydrogen position. The unit cell with a = 10.672(4) Å and c = 11.083(3) Å contains six formular units; the space group is R3 c. The chemical bonding in this compound is discussed.     

Metallampullen als Mini‐Autoklaven: Synthese und Kristallstrukturen der Ammoniakate [Al(NH3)4Cl2][Al(NH3)2Cl4] und (NH4)2[Al(NH3)4Cl2][Al(NH3)2Cl4]Cl2

Metal Ampoules as Mini‐Autoclaves: Syntheses and Crystal Structures of [Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄] and (NH₄)₂[Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄]Cl₂ The salts [Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–≡AlCl₃ · 3 NH₃ ( 1 ) and (NH₄⁺)²[Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–(Cl^–)₂≡ AlCl₃ · 3 NH₃ · (NH₄)Cl ( 2 ) have been obtained as single crystals during the reactions of aluminum and aluminum trichloride, respectively, with ammonium chloride in sealed Monel metal containers. The crystal structure of 1 was determined again [triclinic, P‐1; a = 574.16(10); b = 655.67(12); c = 954.80(16) pm; α = 86.41(2); β = 87.16(2); γ = 84.89(2)°], that of 2 for the first time [monoclinic, I2/m; a = 657.74(12); b = 1103.01(14); c = 1358.1(3) pm; β = 103.24(2)°].     

Thermal decomposition of polycrystalline [Ni(NH3)6](NO3)2

The thermal decompositions of polycrystalline samples of [Ni(NH₃)₆](NO₃)₂ were studied by thermogravimetric analysis with simultaneous gaseous products of the decomposition identified by a quadruple mass spectrometer. Two measurements were made for samples placed in alumina crucibles, heated from 303 K up to 773 K in the flow (80 cm³ min^?1) of Ar 6.0 and He 5.0, at a constant heating rate of 10 K min^?1. Thermal decomposition process undergoes two main stages. First, the deamination of [Ni(NH₃)₆](NO₃)₂ to [Ni(NH₃)₂](NO₃)₂ occurs in four steps, and 4NH₃ molecules per formula unit are liberated. Then, decomposition of survivor [Ni(NH₃)₂](NO₃)₂ undergoes directly to the final decomposition products: NiO_1+x, N₂, O₂, nitrogen oxides and H₂O, without the formation of a stable Ni(NO₃)₂, because of the autocatalytic effect of the formed NiO_1+x. Obtained results were compared both with those published by us earlier, by Farhadi and Roostaei-Zaniyani later and also with the results published by Rejitha et al. quite recently. In contradiction to these last ones, in the first and second cases agreement between the results was obtained.     

Synthese und Kristallstrukturen von NH4[Si(NH3)F5] und [Si(NH3)2F4]

Synthesis and Crystal Structures of NH₄[Si(NH₃)F₅] and [Si(NH₃)₂F₄] Single crystals of NH₄[Si(NH₃)F₅] and [Si(NH₃)₂F₄] are obtained by reaction of silicon powder with NH₄HF₂ in sealed Monel ampoules at 400°C. NH₄[Si(NH₃)F₅] crystallizes with the tetragonal space group P4/n (no. 85) with a = 614.91(7) pm, c = 721.01(8) pm, Z = 2. Characteristic for the structure is the anionic octahedron [Si(NH₃)F₅]^?. Si(NH₃)₂F₄ crystallizes with the monoclinic space group P2₁/c (no. 14) with a = 506.9(1) pm, b = 728.0(1) pm, c = 675.9(1), β = 93,21(2)°, Z = 2. Trans-[Si(NH₃)₂F₄] molecules are characteristic for this structure.     

A New Octadecanuclear Copper(II)‐Lanthanide(III) Cluster Complex: Synthesis and Structural Characterization of [Cu12Nd6(OH)24(betaine)16(NO3)3(H2O)10](NO3)[PF6]14·5H2O

The new octadecanuclear Cu‐Ln complex, [Cu₁₂Nd₆(OH)₂₄(betaine)₁₆(NO₃)₃(H₂O)₁₀](NO₃)[PF₆]₁₄·5H₂O, was synthesized, which crystallizes in triclinic P1¯ space group, a = 18.649(6)Å, b = 20.363(7)Å, c = 19.865(7)Å, α = 116.61(2)°, β = 91.99(2)°, γ = 117.93(2)°, V = 5666(3)ų. Its crystal structure features a [Cu₁₂Nd₆(OH)₂₄(betaine)₁₆(NO₃)₃(H₂O)₁₀]¹⁵⁺ core of pseudocubic O_h symmetry, with the six Nd ions positioned at the vertices of a regular octahedron and the twelve Cu ions located at the midpoints of the twelve octahedral edges. The Cu‐Nd metal framework may be viewed as a cuboctahedron, which is interconnected by twenty‐four μ₃‐OH bridges that are each linked to one Nd ion and two Cu ions. In the centre of metal polyhedron, there is an encapsulated NO₃^— anion that exhibits a multi‐ coordinating mode.     

Die Ammonolyse von (NH4)2GeF6. Darstellung und Struktur von NH4[Ge(NH3)F5]

Ammonolysis Reaction of (NH₄)₂GeF₆. Synthesis and Structure of NH₄[Ge(NH₃)F₅] (NH₄)₂GeF₆ reacts with ammonia to yield NH₄[Ge(NH₃)F₅] at 280°C. The reaction path was elucidated by in situ time and temperature resolved X-ray powder diffraction. NH₄[Ge(NH₃)F₅] crystallizes isostructurally to NH₄[Si(NH₃)F₅] in the tetragonal space group P4/n (No. 85) with lattice constants a = 619.41(1) pm and c = 724.70(1) pm. The germanium atom is coordinated by five fluorine atoms and the nitrogen atom of the ammonia molecule. The ammonium cation is located on the Wyckoff position (2 a) in P4/n. The crystal structure is stabilized by extensive hydrogen bonding.     

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

Crystalline NO₂[Fe(NO₃)₄] was obtained by dehydration of a solution of Fe(NO₃)₃ in 100 % HNO₃ and subsequent sublimation. NO₂[Zr(NO₃)₅] was synthesized by reaction of ZrCl₄ with N₂O₅ followed by sublimation in vacuum. X‐ray single crystal structure determination showed both compounds to consist of nitronium cations, NO₂⁺, and nitratometalate anions. N‐O distances in the linear NO₂⁺ cations are in the range of 1.08—1.13Å. In both [Fe(NO₃)₄]⁻ and [Zr(NO₃)₅]⁻ anions, all nitrate groups are coordinated bidentately with average M‐O distances 2.134 and 2.293Å, respectively. Taking into account the position of N atoms around the M atoms, the arrangement of nitrate groups can be described as tetrahedral for the Fe complex and trigonal‐bipyramidal for the Zr complex. There are four shortest N(nitronium)····O(nitrate group) contacts with average distances of 2.705 and 2.726Å in NO₂[Fe(NO₃)₄] and 2.749Å in NO₂[Zr(NO₃)₅]. Nitronium pentanitratohafnate is isotypic to the zirconium complex.     

Nd3NCl6 und Nd4NS3Cl3: Zwei Neodymnitrid‐Derivate mit diskreten Einheiten kantenverknüpfter ([N2Nd6]12+) bzw. isolierter [NNd4]9+‐Tetraeder

Nd₃NCl₆ and Nd₄NS₃Cl₃: Two Derivatives of Neodymium Nitride with Discrete Units of Edge‐Shared ([N₂Nd₆]¹²⁺) and Isolated [NNd₄]⁹⁺ Tetrahedra, respectively For the preparation of Nd₃NCl₆ (orthorhombic, Pbca; a = 1049.71(8), b = 1106.83(8), c = 1621.1(1) pm; Z = 8) and Nd₄NS₃Cl₃ (hexagonal, P6₃mc; a = 922.78(6), c = 683.06(4) pm; Z = 2) elemental neodymium is reacted with sodium azide (NaN₃), neodymium trichloride (NdCl₃) and in the case of Nd₄NS₃Cl₃ additionally with sulfur in evacuated silica tubes at 750 °C (Nd₃NCl₆) and 850 °C (Nd₄NS₃Cl₃), respectively. Thereby the hydrolysis‐sensitive nitride chloride forms coarse, brick‐shaped single crystals, while those of the insensitive nitride sulfide chloride emerge hexagonally and pillar‐shaped. The pale violet compounds each exhibit [NNd₄] tetrahedra as characteristic structural features, which are connected via a common edge to form discrete pairs of tetrahedra ([N₂Nd₆]¹²⁺) in Nd₃NCl₆ and are present in Nd₄NS₃Cl₃ even as isolated [NNd₄]⁹⁺ units. Their three‐dimensional cross‐linkage as well as the charge‐balance regulation proceed solely through Cl^– anions in the nitride chloride, but through equimolar amounts of S^2– and Cl^– anions in the nitride sulfide chloride. The crystal structure of Nd₃NCl₆ shows three crystallographically independent Nd³⁺ cations, each of which is eightfold coordinated by anions (Nd1: 2 N^3– + 6 Cl^–; Nd2 and Nd3: 1 N^3– + 7 Cl^–). Only two different kinds of Nd³⁺ underlie the structure of Nd₄NS₃Cl₃: Nd1 is surrounded by one N^3–, six S^2– and three Cl^– with CN = 10, whereas one N^3–, four S^2– and three Cl^– only are coordinating Nd2 with CN = 8.