Tetraammin-Lithium-Kationen zur Stabilisierung phenylsubstituierter Zintl-Anionen: Die Verbindung [Li(NH3)4]2[Sn2Ph4]

Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH₃)₄]₂[Sn₂Ph₄] Ruby-red, brittle single crystals of [Li(NH₃)₄]₂[Sn₂Ph₄] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R₁ (F ? 4σF) = 5.13%, wR₂ (F₀² ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb₂Ph₄ isosteric centres [Sn₂Ph₄]^2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100].     

Lithiumtriamidostannat(II), Li[Sn(NH2)3] – Synthese und Kristallstruktur

Lithium Triamidostannate(II), Li[Sn(NH₂)₃] – Synthesis and Crystal Structure Rusty-red glistening, transparent crystals of Li[Sn(NH₂)₃] were obtained by reaction of metallic lithium with tetraphenyl tin in liquid ammonia at 110 °C. The structure was determined from X-ray single-crystal diffractometer data: Space group P 2₁/n, Z = 4, a = 8.0419(9) Å, b = 7.1718(8) Å, c = 8.5085(7) Å, β = 90.763(8)°, R₁ (F _o ≥ 4σ(F _o)) = 2.8%, wR₂ (F ≥ 2σ(F )) = 5.3%, N(F ≥ 2σ(F )) = 1932, N(Var.) = 65. The crystal structure contains trigonal pyramidal complex anions [Sn(NH₂)₃]^– with tin at the apex, which are connected to layers of sequence A B A B … by lithium in tetrahedra-double units [Li(NH₂)_2/2(NH₂)₂]₂.     

Synthese und Kristallstruktur von Mangan(II)‐ und Zinkamid,Mn(NH2)2 und Zn(NH2)2

Synthesis and Crystal Structure of Manganese(II) and Zinc Amides, Mn(NH₂)₂ and Zn(NH₂)₂ Metal powders of manganese resp. zinc react with supercritical ammonia in autoclaves in the presence of a mineralizer Na₂Mn(NH₂)₄ resp. Na₂Zn(NH₂)₄_.0.5NH₃ to well crystallized ruby‐red Mn(NH₂)₂ (p(NH₃) = 100 bar, T = 130°C, 10 d) resp. colourless Zn(NH₂)₂ (p(NH₃) = 3.8 kbar, T = 250°C, 60 d). The structures including all H‐positions were solved by x‐ray single crystal data: Mn(NH₂)₂: I4₁/acd, Z = 32, a = 10.185(6) Å, c = 20.349(7) Å, N(F_o) with F > 3σ (F) = 313, N(parameter) = 45, R/R_w = 0.038/0.043. Zn(NH₂)₂: I4₁/acd, Z = 32, a = 9.973(3) Å, c = 19.644(5) Å, N(F_o) with F > 3σ (F) = 489, N(parameter) = 45, R/R_w = 0.038/0.043. Both compounds crystallize isotypic with Mg(NH₂)₂ [1] resp. Be(NH₂)₂ [2]. Nitrogen of the amide ions is distorted cubic close packed. One quarter of tetrahedral voids is occupied by Mn²⁺‐ resp. Zn²⁺‐ions in such an ordered way that units M₄(NH₂)₆(NH₂)_4/2 occur. The H‐atoms of the anions have such an orientation that the distance to neighboured cations is optimum.     

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.     

Synthese und Struktur eines Caesium-tetraimidophosphat-diamids,Cs5[P(NH)4](NH2)2 = Cs3[P(NH)4] · 2 CsNH2

Synthesis and Crystal Structure of a Cesium-tetraimidophosphate-diamide, Cs₅[P(NH)₄](NH₂)₂ = Cs₃[P(NH)₄] · 2 CsNH₂ Well crystallized Cesium-tetraimidophosphate-diamide is obtained by the reaction of CsNH₂ with P₃N₅ in autoclaves at 673 K within three days. X-ray single crystal investigations led to the following data

• Ccca, Z = 4, a = 8.192(5) Å, b = 20.472(5) Å,
• c = 8.252(3) Å
• Z(F) ≥3σ(F) = 916, Z(Var.) = 32, R/R_w=1 = 0.017/0.021

The compound contains the hitherto unknown anion [P(NH)₄]^3?.     

Darstellung und Struktur eines Ammoniumdiamidodioxophosphats(V), NH4PO2(NH2)2

Synthesis and Structure of an Ammonium Diamidodioxophosphate(V), NH₄PO₂(NH₂)₂ The ammonolysis of P₃N₅ under ammonothermal conditions (T = 400°C, p(NH₃) = 6 kbar, 14 d in autoclaves) in the presence of small definite amounts of water leads to the formation of NH₄PO₂(NH₂)₂. The structure was solved by single crystal X-ray methods. NH₄PO₂(NH₂)₂: P2₁/c (Nr. 14), a = 6.886(1) Å, b = 8.366(2) Å, c = 9.151(2) Å, β = 111.78(3)°, Z = 4, R₁/wR₂ = 0.026/0.072, Z(F > 2σ(F)) = 1183, N(variables) = 87. In NH₄PO₂(NH₂)₂ the anions [PO₂(NH₂)₂]^? are linked to chains by N? H …? N and N? H …? O bridge bonds. The ammonium ions are located between these chains and are donors for N? H …? O bridge bonds which connect the chains three-dimensionally.     

Über α-Dioximin-Komplexe der übergangsmetalle. XXIII) Kobalt(III)-nyoximin-Komplexe mit aromatischen Aminen

30 new binary salts of the heretofore unknown type [Co(NioxH)₂(Amin)₂]X were obtained by air oxidation of an alcoholic aqueous solution of Co^II acetate in the presence of 1,2-cyclohexanedione dioxime (nioxime) and an aromatic amine (aniline, o-and p-ethylaniline and m-xylidine). From the brown solutions of the resulting; Co(NioxH)₂(amine)₂; acetates the desired salts were separated by means of double decomposition reactions using X ? Br^?, NO, ClO, HSO, Pikart, [Cr(NH₃)₂(NCS)₄]^?, 1/3[Cr(NCS)₆]^3? and [Co(NioxH)₂(NO₂)₂]^?; NioxH ? C₆H₉N₂O₂. From spectroscopical investigations in the UV and IR regions some structural problems are resolved and discussed.     

Synthese und Struktur von (NH4)2[(AuI4)(AuI2(μ2-I4))], einem Iodoaurat(III) mit I-Ionen als Liganden

Synthesis and Structure of (NH₄)₂[(AuI₄)(AuI₂(μ₂-I₄))], a Iodoaurate(III) with I₄^2? Anions as Ligands (NH₄)₂[(AuI₄)(AuI₂(μ₂-I₄))] is obtained in a sealed glass ampoule by slow cooling of a mixture of NH₄I, Au, and I₂ beforehand heated to 500°C. The compound forms black crystals decomposing slowly under loss of I₂. It crystallizes in the orthorhombic space group Pnma with a = 1357.7(1), b = 2169.9(2), c = 755.6(3) pm, and Z = 4. The crystal structure is built up by NH cations and square-planar [AuI₄]^? anions as well as [AuI₂(μ₂-I₄)]^? groups being linked together by the I ligands to form chains. The distances Au? I are in the range of 258.7(2) to 262.4(2) pm. The nearly linear I anions are characterized by a short central I? I distance of 270.9(3) pm and two longer outer distances of 338.7(2) pm.     

Darstellung,Kristallstrukturen und Schwingungsspektren von [OsBr(acac)(PPh3)] und [OsBr(acac)(AsPh3)]

Synthesis, Crystal Structures, and Vibrational Spectra of [OsBr(acac)(PPh₃)] and [OsBr(acac)(AsPh₃)] By reaction of tetrabromoacetylacetonatoosmate(IV) with PPh₃ or AsPh₃ in ethanol the complexes [OsBr(acac)(PPh₃)] ( 1 ) and [OsBr(acac)(AsPh₃)] ( 2 ) are formed, which are purified by chromatography on silica gel. X-ray structure determinations of single crystals of ( 1 ) (monoclinic, space group P 2₁/n, a = 13.035(2), b = 18.2640(14), c = 16.636(3) Å, β = 112.776(14)°, Z = 4) and ( 2 ) (monoclinic, space group P 2₁/c, a = 13.23(5), b = 18.35(2), c = 16.65(2) Å, β = 112.9(5)°, Z = 4) result in mean bond distances Os–P = 2.413, Os–As = 2.483, Os–Br = 2.488 and Os–O = 2.037 Å. The vibrational spectra (10 K) exhibit the inner ligand vibrations of the acac, PPh₃ and AsPh₃ groups with nearly constant frequencies and the stretching vibrations of OsP at 499–522, of OsAs at 330–339, of OsBr at 213–214 and of OsO in the range 460–694 cm^–1.     

Synthesis and Structure of a One‐Dimensional Aluminum Phosphate, [NH3(CH2)2NH2(CH2)3NH3]3+ [Al(PO4)2]3—

A one‐dimensional aluminum phosphate, [NH₃(CH₂)₂NH₂(CH₂)₃NH₃]³⁺ [Al(PO₄)₂]^3—, has been synthesized hydrothermally in the presence of N‐(2‐Aminoethyl‐)1, 3‐diaminopropane (AEDAP) and its structure determined by single crystal X‐ray diffraction. Crystal data: space group = Pbca (no. 61), a = 16.850(2), b = 8.832(1), c = 17.688(4)Å, V = 2632.4(2)ų, Z = 8, R₁ = 0.0389 [5663 observed reflections with I > 2σ(I)]. The structure consists of anionic [Al(PO₄)₂]^3— chains built up from AlO₄ and PO₄ tetrahedra, in which all the AlO₄ vertices are shared and each PO₄ tetrahedron possesses two terminal P=O linkages. The cations, which balances the negative charge of the chains, are located in between the chains and interact with the oxygen atoms through strong N—H···O hydrogen bonds. Additional characterization of the compound by powder XRD and MAS‐NMR has also been performed and described.     

Synthese und Kristallstruktur von [N(Hex)4][Cu2(CN)3]

Synthesis and Crystal Structure of [N(Hex)₄] [Cu₂(CN)₃] [N(Hex)₄][Cu₂(CN)₃] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)₆ and (CuCN)₇ rings, forming a zeolith type cyanocuprate(I) framework [Cu₂(CN)₃^—]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) ų; Z = 9.     

Darstellung,Kristallstruktur und Schwingungsspektren von (n-Bu4N)2[(Mo6I)(NCS)]

Synthesis, Crystal Structure, and Vibrational Spectra of (n-Bu₄N)₂[(Mo₆I)(NCS)] By treatment of [(Mo₆I)I]^2– with (SCN)₂ in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(Mo₆I)(NCS)]^2– is formed. The X-ray structure determination of (n-Bu₄N)₂[(Mo₆I)(NCS)] · 2 Me₂CO (monoclinic, space group P2₁/c, a = 13.168(5), b = 11.964(5), c = 24.636(5) Å, β = 104.960(5)°, Z = 2) shows, that the thiocyanate groups are coordinated exclusively via N atoms with Mo–N bond lengths of 2.141–2.150 Å, Mo–N–C angles of 166–178° and N–C–S-angles of 174–180°. The vibrational spectra exhibit characteristic innerligand vibrations at 2073–2054 (ν_CN), 846–844 (ν_CS) and 480–462 cm^–1 (δ_NCS).     

Dicyanmethanido- und Cyanamido-oxoanionen. Untersuchungen zum sauerstoffanalogen Charakter der C(CN)2- und NCN-Gruppen

The equivalence of the C(CN)₂- and the NCN-groups with oxygen in the series of homologous ions C(CN), N(CN), OCN^? and NOC(CN), NO causes us to postulate a more general value of this relation. Arguments for the formulation of a pseudochalkogen series C(CN)₂? NCN? O are discussed. Synthesis, structure and reactivity of some dicyanmethanido- and cyanamido-oxoanions RCOY^?, CO₂Y^2?, COY, NOY^?, NO₂Y^?, PO₃Y^3?, PO₂Y and SO₂Y^2? are described. (Y ? C(CN)₂, NCN.) The preparation of some triorganoleadacyles is reported.     

ESR-Untersuchungen an Kupfer(II)- und Vanadyl(IV)-bis-(1,1-dicyanoäthylen-2,2-dithiolat)-Chelaten

EPR Investigations on Copper(II) and Vanadyl(IV) Bis(1,1-dicyanoethylene-2,2-dithiolate) Chelates EPR investigations on [Cu(i-MNT)₂][NBu]₂ and on [VO(i-MNT)₂][NBu]₂ in solutions and polycristalline matrices (diamagnetically diluted) are reported. The EPR spectra can be described by an axial-symmetric spin-Hamiltonain. Using MO models of the symmetry D_4h (for[Cu(i-MNT)₂]^2?) and C_4v (for[VO(i-MNT)₂]^2?) the bonding parameters of the first coordination sphere of the chelates were calculated taking into account the influence of the ligand-spin-orbit interaction. The Cu? S σ bond has been found to be pure covalent, the inplane and out-of-plane π bonds are different with respect to the degree of covalency. Contrary to this the V? S bonds are less covalent. The results obtained are compared with those of other sulfur-containing chelates. Preparation and properties of the new compound [VO(i-MNT)₂][NBu]₂ are reported.     

Darstellung und Kristallstruktur von trans-(Ph4As)2[OsCl2(NCS)(SCN)], Schwingungsspektren und Normalkoordinatenanalyse

Preparation and Crystal Structure of trans-(Ph₄As)₂[OsCl₂(NCS) (SCN) ], Vibrational Spectra and Normal Coordinate Analysis By treatment of trans-[OsCl₂I₄]^2? with (SCN)₂ in dichloromethane a mixture of different linkage isomers is formed, from which trans-[OsCl₂(NCS)(SCN)]^2? has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determination on a single crystal of trans-(Ph₄As)₂[OsCl₂(NCS)(SCN)] (triclinic, space group P 1 , a = 12.505(5), b = 12.056(5), c = 19.833(5) Å, α = 108.047(5)°, β = 91.964(5)°, γ = 117.048(5)°, Z = 2) reveals that two cis-positioned Thiocyanate(N) groups are coordinated with Os? N? C angles of 172.1° and 173.0° and two cis-positioned Thiocyanate(S) groups are coordinated with Os? S? C angles of 106.9° and 108.7°. Using the molecular parameters of the X-Ray determination the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salt of the linkage isomer are assigned by a normal coordinate analysis based on a modified valence force field. The valence force constants are f_d(OsN) = 1.63 and f_d(OsS) = 1.30 mdyn/Å. Taking into account the trans influence a good agreement between observed and calculated frequencies is achieved.     

Darstellung und spektroskopische Charakterisierung des Clusteranions [(Mo6Cl8i)(CF3COO)6a]2−

Preparation and Spectroscopic Characterization of the Cluster Anion [(Mo₆Cl )(CF₃COO) ]^2? On heating of [(Mo₆Cl)Cl]^2? in dichloromethane with trifluoroacetic acid the new stable cluster anion [(Mo₆Cl)(CF₃COO)]^2? is formed by elimination of HCl. The (Mo₆Cl) unit remains unattacked. The ¹⁹F nmr spectrum exhibits a downfield shifted singulett as compared to free CF₃COO^? indicating the equivalence of all trifluoroacetate ligands, which unidentate coordination is deduced from characteristic i. r. frequencies of the carboxyl groups. The most intense i.r. band at 501 cm^?1 is assigned to the antisymmetric Mo? O^a vibration, the most intense Raman line at 319 cm^?1 to the breathing mode of the Cl cube.     

High- und Low-Spin-Verhalten des Ni3+ -Ions in oktaedrischer Koordination. (A) NiF-Polyeder

High and Low Spin Behaviour of Ni³⁺?Ions in Octahedral Coordination The compounds Cs₂NaNiF₆, Cs₂KNiF₆, Rb₂KNiF₆, K₃NiF₆, and Na₃NiF₆ were investigated by ligand field and EPR spectroscopy between 298 and 4,2 K. These fluorides ? with the exception of the first one – crystallise in the cubic elpasolite lattice or in distorted modifications of this structure type and contain the Ni³⁺ ions in the low spin configuration te. This configuration is stabilised versus the high spin alternative te by an appreciable Jahn-Teller splitting of the ²E_g-state of about 7000 cm^?1. The NiF₆-octahedra are tetragonally elongated, the distortion being dynamical at 298 K. In case of the cubic compound Rb₂KNiF₆ a transition to a tetragonal structure with c/a > 1 as a consequence of a ferrodistortive Jahn-Teller ordering is observed at lower temperatures. It is calculated from the anisotropic g-parameters, that the first excited quartet level ⁴A_2g(⁴T_1g ? te) has an energy which is about 1000 cm^?1 higher than that of the ²A_1g(²E_g ? te) groundstate. Spin-orbit interactions between the energetically neighboured ²A_1g(²E_g) and ⁴A_2g, ⁴E_g(⁴T_1g) states lead to third order contributions to the g-factors, which are very sensitive with respect to the doublet-quartet separation. In the hexagonal compound Cs₂NaNiF₆ finally, in which half of the Ni³⁺ ions occupy octahedral sites connected by common corners as in the other fluorides, while the other half is located in octahedral sites with common faces, high and low spin Ni³⁺ ions are found side by side. Obviously the latter half of these Ni³⁺ ions is geometrically restricted with respect to a Jahn-Teller distortion and hence the high spin configuration energetically favoured.     

19F-NMR-spektroskopischer Nachweis und statistische Untersuchung zur Bildung der gemischten Clusteranionen [(Mo6ICl)F]2−, n = 0–7, und Darstellung von (TBA)2[(Mo6I)F]

¹⁹F NMR Spectroscopic Evidence and Calculation of the Statistical Formation of Mixed Cluster Anions [(Mo₆I Cl )F ]^2?, n = 0–7, and Preparation of (TBA)₂[(Mo₆I )F ] The octa-μ₃-iodo-hexafluoro-hexamolybdate(2?)ion [(Mo₆I)F]^2? is prepared for the first time. The system of the 21 innersphere mixed clusters (Mo₆ICl)⁴⁺, n = 0–7 is formed by exchange of innersphere bound Clⁱ against outersphere bound I^a on tempering solid [(Mo₆Cl)I] at 400°C. Prolonged tempering leads to increasing average n values of the mixture, which is converted into the tetrabutylammonium salt (TBA)₂[(Mo₆ICl)F]. Using increments of chemical shifts and integral peak intensities the 54 ¹⁹F-nmr signals of the 21 species (compound n = 8 is absent) are assigned and confirmed by the 2 D-¹⁹F/¹⁹F-COSY spectrum. From the measured intensities the distribution of the different compounds is determined and proves significant deviation from statistical occupation, revealing the preference of isomers with iodine atoms occupying edges of the innersphere cube and discrimination of those sharing diagonals of the faces. Moreover all compounds with n = 3 and 4 are present overaverage in comparison to the others.     

LaCl(BO2)2 und Er2Cl2[B2O5]: Zwei Chlorid‐Oxoborate dreiwertiger Lanthanide

LaCl(BO₂)₂ and Er₂Cl₂[B₂O₅]: Two Chloride Oxoborates of Trivalent Lanthanides Er₂Cl₂[B₂O₅] is obtained as single crystals by the reaction of ErCl₃, Er₂O₃ and B₂O₃ with an excess of ErCl₃ as flux in evacuated silica tubes after two weeks at 850 °C. The compound crystallizes as long, pale pink needles and appears to be air‐ and water‐resistant. Single‐crystalline LaCl(BO₂)₂ emerges from the reaction of La₂O₃, LaCl₃, and B₂O₃ with an excess of B₂O₃ as flux in evacuated silica tubes after four weeks at 900 °C. LaCl(BO₂)₂ crystallizes as thin, colourless, air‐ and water‐resistant needles which tend to severe twinning due to their fibrous habit. The crystal structure of Er₂Cl₂[B₂O₅] (orthorhombic, Pbam; a = 1489.65(9), b = 1004.80(6), c = 524.86(3) pm; Z = 4) contains two crystallographically different erbium cations. (Er1)³⁺ resides in pentagonal‐bipyramidal coordination of seven anions while (Er2)³⁺ is surrounded by only six anions with the shape of an octahedron. The planar oxodiborate units [B₂O₅]^4— consisting of two vertex‐shared [BO₃]^3— triangles are isolated according to {([BOO]₂)^4—}. LaCl(BO₂)₂ crystallizes isostructurally with PrCl(BO₂)₂ in the triclinic space group P1¯ (a = 423.52(4), b = 662.16(7), c = 819.33(8) pm; α = 82.081(8), β = 89.238(9), γ = 72.109(7)°; Z = 2). The characteristic unit consists of endless chains built up by corner‐linked [BO₃]^3— triangles. These quasi‐planar zigzag chains of the composition {[(B1)OO(B2)OO]^2—} (≡ {[BO₂]^—} run parallel [100]. The La³⁺ cations exhibit coordination numbers of ten and are coordinated by three Cl^— and seven O^2— anions.     

Nitridsulfidchloride der Lanthanide: III. Synthese und Kristallstruktur von Pr5N3S2Cl2

Nitride Sulfide Chlorides of the Lanthanides. III. Synthesis and Crystal Structure of Pr₅N₃S₂Cl₂ By reacting praseodymium with sulfur, sodium azide and praseodymium trichloride in sealed, evacuated silica tubes (850°C, 7 d), the nitride sulfide chloride Pr₅N₃S₂Cl₂ is obtained in case of a 4:2:1:1 molar ratio of the reactants (Pr:S:NaN₃:PrCl₃). A slight excess of trichloride or the addition of NaCl as a flux supports the yield of brownish red, rod-shaped transparent crystals which prove to be stable against hydrolysis. The crystal structure (monoclinic, C2/m (no. 12), a = 1540.2(1), b = 400.92(3), c = 1656.3(1) pm, β = 101.24(1)°, Z = 4, R = 0.039, R_w = 0.028) was determined by means of X-ray single crystal data. Thus five crystallographically different cations (Pr³⁺) are present which with three distinct kinds of nitride anions (N^3?) build up two types of translationally commensurate chains from interconnected [NPr₄] tetrahedra. With an additional edge per “chain-link” in chain I, two single chains [NPr_3/3^ePr_1/1^t]³⁺ (?[NPr₂]³⁺) of cis-edge connected [NPr₄] tetrahedra (known from the Sm₄N₂S₃-type structure) are condensed into the double chain [(N1){(Pr1)_(2+2)/(2+2)^e,e(Pr2)_(2+1)/(2+1)^e,v}(N2)(Pr3)_1/1^t]³⁺ (?[N₂Pr₃]³⁺). Chain II consists of two single chains [NPr_2/2^vPr_2/1^t] ⁶⁺ (?[NPr₃]⁶⁺) of vertex-connected [NPr₄] tetrahedra (known from the Sm₃NS₃-type structure), which are condensed to the double chain [(N3)(Pr4)_2/2^e(Pr5)_2/2^v]³⁺ (?[NPr₂]³⁺) via an additional edge per “chain-link” too. Both types of chains are bundled along [010] like a closest packing of rods. Four crystallographically different but by X-ray diffraction indistinguishable anions S^2? and Cl^? hold both cationic double chains together and also adjust the charge balance in a molar ratio of 1 : 1.