Three New Thioantimonates(V): Solvothermal Syntheses and Crystal Structures of [M(chxn)3]3(SbS4)2·4H2O (M = Ni,Co) and [Co(dien)2][Co(tren)SbS4]2·4H2O

The three new thioantimonates(V) [Ni(chxn)₃]₃(SbS₄)₂·4H₂O ( I ), [Co(chxn)₃]₃(SbS₄)₂·4H₂O ( II ) (chxn is trans‐1,2‐diaminocyclohexane) and [Co(dien)₂][Co(tren)SbS₄]₂·4H₂O ( III ) (dien is diethylenetriamine and tren is tris(2‐aminoethyl)amine) were synthesized under solvothermal conditions. Compounds I and II are isostructural crystallizing in space group C2/c. The structures are composed of isolated [M(chxn)₃]²⁺ complexes (M = Ni, Co), [SbS₄]^3? anions and crystal water molecules. Short S···N/S···O/O···O separations indicate hydrogen bonding interactions between the different constituents. Compound III crystallizes in space group and is composed of [Co(dien)₂]²⁺ and [Co(tren)SbS₄]^? anions and crystal water molecules. In the cationic complex the Co²⁺ ion is in an octahedral environment of two dien ligands whereas in [Co(tren)SbS₄]^? the Co²⁺ ion is in a trigonal bipyramidal coordination of four N atoms of tren and one S atom of the [SbS₄]^3? anion, i.e., two different coordination polyhedra around Co²⁺ coexist in this compound. Like in the former compounds an extended hydrogen bonding network connects the complexes and the water molecules into a three‐dimensional network.     

A Missing Structural Link in the Werner Series of Cobalt(III) Complexes: The Crystal Structure of Δ‐(–)589‐Tris(ethylenediamine)cobalt(III) Iodide Monohydrate

Alfred Werner's historic resolution of Δ/Λ‐[Co(en)₃]³⁺ (where en = ethylenediamine) provided conclusive evidence for octahedral geometry coordination compounds and the first example of chirality in an inorganic molecule. Herein, we report the historically significant structure and absolute configuration of Δ‐(–)₅₈₉‐tris(ethylenediamine) cobalt(III) iodide monohydrate, Δ‐[Co(en)₃]I₃ ( 1 ), the missing crystallographic piece in the series of [Co(en)₃]³⁺ complexes. Complex 1 crystallizes in an orthorhombic space group P2₁2₁2₁ with unit cell dimensions of a = 8.4016(10), b = 11.2573(13), c = 18.825(2) Å, V = 1780.4(4) ų, and Z = 4. The absolute configuration of the complex cation [Co(en)₃]³⁺ is Δ and the en ligands adopt a λλδ configuration.     

Darstellung und Kristallstruktur von Tris(äthylendiamin)kobalt(III)-trichlorostannat(II)-dichlorid, [Co(en)3][SnCl3]Cl2

Preparation and Crystal Structure of Tris(ethylenediamine) cobalt(III)-trichlorostannate(II)-dichloride, [Co(en)₃] [SnCl₃]Cl₂ The title compound has been prepared from [Co(en)₃]Cl₃ and SnCl₂ · 2H₂O in aqueous HCl solution. It crystallizes in the orthorhombic space group Pbca, with a = 21.906(7), b = 10.607(3), c = 15.356(7) Å. The crystal structure has been determined from 1606 independent reflections by Patterson snd Fourier syntheses, and has been refined by least squares methods to R = 0.074. The [Co(en)₃]³⁺ ion is found to have the conformation of Λ(δδλ) resp. Δ(λλδ). The structure of the [SnCl₃]^? ion corresponds to a distorted tetrahedron, in which one site is occupied by the stereochemically active 5s electron pair. The following Sn? Cl distances have been found 2.493(7), 2.492(5), 2.479(7) Å, the distances of the two anionic Cl atoms from Sn are >4 Å.     

Polymorphism of the dinuclear CoIII–Schiff base complex [Co2(o‐van‐en)3]·4CH3CN (o‐van‐en is a salen‐type ligand)

Reactions of Co(OH)₂ with the Schiff base bis(2‐hydroxy‐3‐methoxybenzylidene)ethylenediamine, denoted H₂(o‐van‐en), under different conditions yielded the previously reported complex aqua[bis(3‐methoxy‐2‐oxidobenzylidene)ethylenediamine]cobalt(II), [Co(C₁₈H₁₈N₂O₄)(H₂O)], 1 , under anaerobic conditions and two polymorphs of [μ‐bis(3‐methoxy‐2‐oxidobenzylidene)ethylenediamine]bis{[bis(3‐methoxy‐2‐oxidobenzylidene)ethylenediamine]cobalt(III)} acetonitrile tetrasolvate, [Co₂(C₁₈H₁₈N₂O₄)₃]·4CH₃CN, i.e. monoclinic 2 and triclinic 3 , in the presence of air. Both novel polymorphs were chemically and spectroscopically characterized. Their crystal structures are built up of centrosymmetric dinuclear [Co₂(o‐van‐en)₃] complex molecules, in which each Co^III atom is coordinated by one tetradentate dianionic o‐van‐en ligand in an uncommon bent fashion. The pseudo‐octahedral coordination of the Co^III atom is completed by one phenolate O and one amidic N atom of the same arm of the bridging o‐van‐en ligand. In addition, the asymmetric units of both polymorphs contain two acetonitrile solvent molecules. The polymorphs differ in the packing orders of the dinuclear [Co₂(o‐van‐en)₃] complex molecules, i.e. alternating ABABAB in 2 and AAA in 3 . In addition, differences in the conformations, the positions of the acetonitrile solvent molecules and the pattern of intermolecular interactions were observed. Hirshfeld surface analysis permits a qualitative inspection of the differences in the intermolecular space in the two polymorphs. A knowledge‐based study employing Full Interaction Maps was used to elucidate possible reasons for the polymorphism.     

Synthesis,Crystal Structure,and Hydrogen Bonding of μ‐Hydroxo‐μ‐peroxo‐bis[bis(ethylenediamine)cobalt(III)] Squarate

Black‐brown needle‐shaped single crystals of [Co₂(en)₄(O₂)(OH)][C₄O₄]_1.5 · 4H₂O (en = ethylenediamine) were prepared in aqueous solution at room temperature [space group P$\bar{1}$ (no.2) with a = 800.20(8), b = 1225.48(7), c = 1403.84(9) pm, α = 100.282(5), β = 94.515(7), and γ = 95.596(6)°]. The Co³⁺ cations [Co(1), Co(2)] are coordinated in an octahedral manner by four nitrogen atoms stemming from the ethylenediamine molecules and two oxygen atoms each from a hydroxo group and a peroxo group, respectively. Both Co³⁺ coordination polyhedra are connected by a common corner and by the peroxo group leading to the dinuclear [(en)₂Co(O₂)(OH)Co(en)₂]³⁺ cation. The squarate dianions, not bonded to Co³⁺, and the [(en)₂Co(O₂)(OH)Co(en)₂]³⁺ cations are linked by hydrogen bonds forming a three‐dimensional supramolecular network containing water molecules. Magnetic measurements revealed a diamagnetic behavior indicating a low‐spin electron configuration of Co³⁺. The UV/Vis spectra show two LMCT bands [π*(O₂^2–) → d_σ*(Co³⁺)] at 274 and 368 nm and the d–d transition (¹A_1g → ¹T_1g) at 542 nm. Thermoanalytical investigations in air show that the compound is stable up to 120 °C. Subsequent decomposition processes to cobalt oxide are finished at 460 °C.     

[M(en)3] (ndt)•H2O的水热合成、晶体结构和光学性能 ( M=NiⅡ, CoⅡ, MnⅡ and ndt=1,5-naphthalenedithiolate )

水热条件下，合成了三个新的配合物[Ni(en)₃] (ndt) ·H₂O 1, [Co(en)₃] (ndt) ·H₂O 2 和[Mn(en)₃] (ndt) ·H₂O 3。晶体结构通过X-射线单晶衍射进行了表征。三个配合物均属于单斜晶系，Cc空间群。[M(en)₃]²⁺阳离子、ndt阴离子和结晶水分子通过氢键自组装出相同结构的三维网。通过紫外-可见-近红外漫反射光谱对这三个配合物的光吸收性能和能带进行了测定。     

Solvothermal Synthesis of two 2‐D Thioantimonates(III) with Metal Complexes as Template Ions, [M(dap)3]Sb4S7 (M = Ni2+ and Co2+)

Two new thioantimonates [M(dap)₃]Sb₄S₇ (M = Ni²⁺ ( 1 ) and Co²⁺ ( 2 )) were synthesized under solvothermal conditions by the reaction of NiS (or Co metal), Sb and S in an aqueous solution of 1,2‐diaminopropane (dap). Compounds 1 and 2 are isostructural. The polymeric [Sb₄S₇^2?]_n anion is composed of two SbS₃ trigonal pyramids and two SbS₄ units. The SbS₃ and SbS₄ units are interconnected by corners and edges to build a 2‐D puckered layer with Sb₄S₄ and Sb₁₆S₁₆ heterorings. The apertures of the large Sb₁₆S₁₆ hetero‐rings are filled by two [M(dap)₃]²⁺ complex cations which serve as template ions. The band gaps of 2.44 eV for 1 and 2.43 eV for 2 have been estimated from optical absorption spectra.     

Crystal structure of tris(ethylenediamine)cobalt(III) (aqua)hexachloromercurate(II) chloride [Co(En)3]2[Hg2(H2O)Cl6]Cl4

The compound [Co(En)₃]₂[Hg₂(H₂O)Cl₆]Cl₄ (I, En is ethylenediamine) has been synthesized and studied by X-ray diffraction. The crystals of I (a = 21.8745(14) Å, b = 10.6008(6) Å, c=15.4465(12) Å, space group Pna2₁) consist of tris(ethylenediamine)cobalt(III) complexes (the unit cell contains two [Co(En)₃]³⁺ cations of opposite chirality). [Hg₂(H₂O)Cl₆]^2? anions, and isolated chloride ions. The complex anion consists of the tetrahedral [HgCl₄]^2? group (Hg-Cl, 2.44–2.56 Å) and the hydrated molecule [Hg(H₂O)Cl₂] (Hg-Cl, 2.301 and 2.308 Å; Hg-O, 2.788 Å) combined by weak Hg-Cl interactions (2.915 and 3.220 Å).     

Low‐Temperature Synthesis of Diamminesodium(1+) Triamminesodium(1+) Trithioantimonate(3−) Ammoniate (1 : 2 : 1 : 2) ([Na(NH3)3]2[Na(NH3)2]SbS3⋅2 NH3), A Solvated Neutral Sodium Trithioantimonate(3−) (3 : 1) Na3SbS3) Ion Complex

A solution of sodium in liquid ammonia reacts with Sb₂S₃ to form large colorless crystals of the composition Na₃SbS₃⋅10 NH₃. The trigonal‐pyramidal SbS₃³⁻ anion is ion‐paired with three Na⁺ counter ions, the coordination spheres of which are completed by eight ammine ligands. The resulting neutral [Na(NH₃)₃]₂[Na(NH₃)₂]SbS₃ molecules crystallize together with two ammonia molecules of solvation in the space group P2₁/c (a=9.828(2), b=6.0702(4), c=33.4377(6) Å, β=91.362(7)°, V=1994.2(5) ų, Z=4).     

Activity and Osmotic Coefficients from the Emf of Liquid Membrane Cells. X. Tris(Ethylenediamine) Cobalt(III) Nitrate, Perchlorate, and Chloride

Activity coefficients of [Co(en)₃](NO₃)₃ and [Co(en)₃](ClO₄)₃, to be compared with [Co(en)₃]Cl₃ and the corresponding lanthanum salts previously studied, are determined. [Co(en)₃]Cl₃ data are revised. Ion interaction strengths vary in the same order found for La³⁺, i.e., as if nitrate and perchlorate ions were of smaller and larger size, respectively, than chloride ions; however, the differences are much smaller than in lanthanum salts. Tris(ethylenediamine)cobalt III and lanthanum nitrate, chloride, and perchlorate—like the corresponding hexacyanoferrate(III) and hexacyanocobaltate(III) salts, but contrary to sulfate salts—behave as if [Co(en)₃]³⁺ were smaller in size than La³⁺. In the dilute regions, [Co(en)₃](NO₃)₃ displays negative deviations from the limiting slope, a kind of behavior typical for 2:2, 2:3, 3:2, and 3:3 electrolytes, but unnoticed earlier for 3:1 or 1:3 electrolytes. Pitzer's equation parameters able to provide accurate activity and osmotic coefficients for [Co(en)₃](NO₃)₃, [Co(en)₃](ClO₄)₃, and, revised, [Co(en)₃]Cl₃ are reported.     

Über Reaktionen oxygenierter Kobalt(II)-Chelate. VI. Präparative Darstellung von diastereoisomeren Tetrakis(äthylendiamin)-μ-peroxo-μ-hydroxodikobalt(III)-perchloraten

On Reactions of oxygenated Cobalt(II) Chelates. VI. Preparation of diastereoisomeric tetrakis(ethylenediamine)-μ-peroxo-μl-hydroxo-dicobalt(III) Perchlorates Oxygenation of Co(en)₂²⁺ leads to a mixture of two isomeric forms of [(en)₂Co(O₂, OH)-Co(en)₂] (ClO₄)₃ · H₂O from which the less soluble meso form can be readily crystallized. Further crystallization from the mother liquor yields the racemate ΔΔ/ΔΔ. The pure racemate may be obtained by either of the following methods: (a) By ligand exchange starting from mono bridged [(NH₃)₅CoO₂Co(NH₃)₅] (NO₃)₄ or from doubly bridged [(SCN) (NH₃)₃Co(O₂, OH)Co(NH₃)₃(SCN)] SCN · 2H₂O. (b) By reaction of cis-[Co(en)₂(OH₂)₂]³⁺ with H₂O₂. Reaction (b) proceeds via an intermediate cis-[Co(en)₂(OOH) (OH₂)] (ClO₄)₂ · H₂O which at higher pH reacts with [Co(en)₂(OH) (OH₂)]²⁺ to yield the desired doubly bridged ΔΔ/ΔΔ tetrakis(ethylenediamine)-μ-peroxo-μ-hydroxodikobalt(III)-perchlorate.     

Kobalt-Komplexe mit O2-Brücken: Die Struktur der Kationen μ-Hydroxo-μ-peroxo-bis[bis(äthylendiamin) kobalt(III)]3+ und μ-Hydroxo-μ-superoxo-bis[bis (äthylendiamin)kobalt(III)]4+

Cobalt Complexes with O₂ Bridges: The Structure of the Cations μ-Hydroxo-μ-peroxo-bis[bis(ethylenediamine) cobalt (III)]³⁺and μ-Hydroxo-μ-superoxo-bis [bis (ethylenediamine) cobalt (III)]⁴⁺ X-ray structure determinations of one salt of each of the two chemically and structurally closely related dinuclear cobalt cations [(en)₂Co · μ(OH, O₂) · Co(en)₂]³⁺ 1a and [(en)₂Co · μ(OH, O₂) · Co(en)₂]⁴⁺ 1b have been performed. In both cases the cations exist as racemic mixtures of ΔΔ and ΔΔ isomers. The O–O distance in the μ-peroxo cation 1a is 1.465 Å and the Co–O–O–Co torsion angle is 60.7°. The corresponding values for the μ-superoxo cation 1b are 1.339 Å and 22.0°.     

Double-salt formation in crystal structures containing [Co(en)3]Cl3

The structures of three racemic double salts of [Co(en)₃]Cl₃ (en is ethane-1,2-diamine, C₂H₈N₂), namely, bis[tris(ethane-1,2-diamine-κ²N,N′)cobalt(III)] hexaaquasodium(I) heptachloride, [Co(en)₃]₂[Na(H₂O)₆]Cl₇, bis[tris(ethane-1,2-diamine-κ²N,N′)cobalt(III)] hexaaquapotassium(I) heptachloride, [Co(en)₃]₂[K(H₂O)₆]Cl₇, and ammonium bis[tris(ethane-1,2-diamine-κ²N,N′)cobalt(III)] heptachloride hexahydrate, (NH₄)[Co(en)₃]₂Cl₇·6H₂O, have been determined, and the structural similarities with the parent compound, tris(ethane-1,2-diamine-κ²N,N′)cobalt(III) trichloride tetrahydrate, [Co(en)₃]Cl₃·4H₂O, are highlighted. All four compounds crystallize in the trigonal space group Pc1. When compared with the parent compound, the double salts show a modest increase in the unit-cell volume. The structure of the chiral derivative [Λ-Co(en)₃]₂[Na(H₂O)₆]Cl₇ has also been redetermined at cryogenic temperatures (120 K) and the disorder noted in a previous report has been accounted for.     

Solvothermal synthesis and crystal structure of Sb(III) and Sb(V) thioantimonates: [Mn(en)3]2Sb2S5 and [Ni(en)3(Hen)]SbS4

Thioantimonate compounds of [Mn(en)₃]₂Sb₂S₅ (1) and [Ni(en)₃(Hen)]SbS₄ (2) (en=ethylenediamine) were prepared by reaction of transition metal chloride with Sb and S₈ powders under solvothermal conditions. Compound 1 consists of discrete [Sb₂S₅]⁴⁻ anion, which is formed by corner-sharing SbS₃ trigonal pyramids. Compound 2 is composed of discrete tetrahedral [SbS₄]³⁻ anion. The compounds 1 and 2 are charge compensated by [M(en)₃]²⁺ cations, whereas in the crystal of 2 there is another counter ion of [Hen]⁺. The results of the synthesis suggest that the temperature, the concentration and the existing states of the starting materials and so on are important for the structure and composition of the final products. In addition, the oxidation-state of antimony might be related to the molar ratio of the reactants. Excess amount of elemental S is beneficial to the higher oxidation-state of thioantimonate (V). Compound 1 decomposes from 150°C to 350°C, while compound 2 decomposes from 200°C to 350°C remaining Sb₂S₃ and NiSbS as residues.     

Dinuclear complexes with a μ-cyano ligand. Part XI(1). Synthesis and characterization of several derivatives ofcis-[Co(NH3)(en)2(H2O)]3+

Summary The new complex double saltscw-[Co(NH₃)(en)₂(H₂O)]₂ [M(CN)₄]₃ (en = ethylenediamine; M = Ni, Pd or Pt),cis-[Co(NH₃(en)₂(H₂O)]₂[FeNO(CN)₅]₃ andcis-[Co(NH₃)(en)₂(H₂O)][Co(CN)₆] have been synthesized and by anation in the solid state the corresponding new dinuclear complexes with a cyano bridgecis- ortrans-[(NH₃)(en)₂Co-NC-M(CN)₃]₂ [M(CN)₄] (M = Ni, Pd or Pt);cis-, trans-[(NH₃)(en)₂Co-NC-FeNO(CN)₄]₂[FeNO(CN)₅] andcis-[(NH₃)(en)₂Co-NC-Co(CN)₅ have been prepared. The complexes have been characterized by chemical analysis, t.g. measurements, and by i.r. and electronic spectroscopy. With [Ni(CN)₄][^2– and [Co(CN)in]₆ ^3– only thecis-isomer is produced; with [Pd(CN)₄]^2–, [Pt(CN)₄]^2– and [FeNO(CN)₅]^2– thetrans- isomer is the dominant species. The dinuclear complex derived from [Pt(CN)₄]^2– shows strong Pt-Pt interactions both in the solid state and in solution.     

Novel Copper(I)‐Thioantimonates(III): Solvothermal Synthesis,Crystal Structures,Thermal Stability and Magnetic Properties of (C2N2H10)0.5Cu2SbS3, (C3N2H12)0.5Cu2SbS3, and (C4N2H14)0.5Cu2SbS3

The novel copper(I)‐thioantimonates(III) (enH₂²⁺)_0.5Cu₂SbS₃ ( I ) (en = ethylendiamine), (1, 3‐DAPH₂²⁺)_0.5Cu₂SbS₃ ( II ) (1, 3‐DAP = 1, 3 diaminopropane) and (1, 4‐DABH₂²⁺)_0.5Cu₂SbS₃ ( III ) (1, 4‐DAB = 1, 4‐diaminobutane) were synthesized under solvothermal conditions reacting Sb₂S₃, CuCl₂·2H₂O, S with the amines. The compounds crystallize in the monoclinic space group P2₁/n. The primary building units are a SbS₃ trigonal pyramid and two distorted CuS₃ units. In the structures the SbS₃ pyramid is connected to six CuS₃ moieties and every S atom has bonds to one Sb atom and to two Cu atoms. Further interconnection leads to the formation of ten‐membered (10 MR) Cu₃Sb₂S₅ and six‐membered (6 MR) Cu₂SbS₃ rings. Every 10 MR is condensed to four 10 MR and four 6 MR to form a single layer within the (010) plane. Two such single layers are connected to a double layer thus forming the final [Cu₂SbS₃]^— layered anion. The [CuSbS₃]^— protonated amines are located between the layers and the interlayer spacing depends on the size and orientation of these amines. Between the Sb atom and one Cu atom a remarkable short distance of about 2.7Å is observed. At elevated temperatures the compounds decompose into CuSbS₂ and Cu₃SbS₄ suggesting a complex redox reaction. Diamagnetic susceptibilities indicate the copper(I) in the metal sulfide frameworks. All three compounds are semiconductors with intermediate band gaps of about 2 eV.     

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds with the [SbS4]3— Anion Acting as a Monodentate Ligand: [Mn(C6H18N4)(C6H19N4)]SbS4 and [Mn(C6H14N2)3]2[Mn(C6H14N2)2(SbS4)2]·6H2O

The two novel thioantimonate(V) compounds [Mn(C₆H₁₈N₄)(C₆H₁₉N₄)]SbS₄ ( I ) and [Mn(C₆H₁₄N₂)₃][Mn(C₆H₁₄N₂)₂(SbS₄)₂]·6H₂O ( II ) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in the stoichiometric ratio in 5 ml tris(2‐aminoethyl)amine (tren) at 140 °C or chxn (trans‐1, 2‐diaminocyclohexane, aqueous solution 50 %) at 130 °C. Compound I crystallises in the triclinic space group P1¯, a = 9.578(2), b = 11.541(2), c = 12.297(2)Å, α = 62.55(1), β = 85.75(1), γ = 89.44(1)°, V = 1202.6(4)ų, Z = 2, and II in the monoclinic space group C2/c, a = 32.611(2), b = 13.680(1), c = 19.997(1)Å, β = 117.237(5)°, V = 7931.7(8)ų, Z = 4. In I the Mn²⁺ cation is surrounded by one tetradentate tren molecule, one protonated tren acting as a monodentate ligand and a monodentate [SbS₄]^3— anion yielding a distorted octahedral environment. In II one unique Mn²⁺ ion is in an octahedral environment of three bidentate chxn molecules and the second independent Mn²⁺ ion is coordinated by two chxn ligands and two monodentate [SbS₄]^3— units leading to a distorted octahedral surrounding. The compounds were investigated and characterized with thermal and spectroscopic methods.     

Über Reaktionen oxygenierter Kobalt(II)-Komplexe. IX. Oxydative Eigenschaften von Tetrakis(äthylendiamin)-μ-peroxo-μ-hydroxo-dikobalt(III)

Reactions of oxygenated cobalt(II) complexes. IX. Oxidative properties of tetrakis(ethylenediamine)-μ-peroxo-μ-hydroxo-dicobalt(III)

1 VIII s. [1].

[(en)₂Co(O₂, OH)Co(en)₂]³⁺ ( a ) reacts with I^? in acidic aqueous solution according to: Co^III(O₂, OH)Co^III + 21^? + 5H⁺ ? 2Co^III + 3H₂O + I₂. Using I^? in excess first order rate constants are obtained which, to a first approximation, are independent of [I^?]. Comparison with kinetic data of deoxygenation of [(en)₂Co(O₂, OH)Co(en)₂]³⁺ under analogous conditions suggests that both reactions have the same rate determining step. The singly bridged species [(en)₂(H₂O)CoO₂Co(H₂O) (en)₂]⁴⁺ is shown to be the reactive intermediate in the iodide oxidation (Schema 2).     

Three-layered close packing in the crystal structure of tris(ethylenediamine)cobalt(III) hexanitrorhodate(III) hydrate, [Co(en)3][Rh(NO2)6]·3H2O,en=C2H8N2

In the structure of cubic tris(ethylenediamine)cobalt(III) hexanitrorhodate(III) hydrate, [Co(en)₃][Rh(NO₂)₆]·3H₂O, en=C₂H₈N₂, with a=16.540(5) Å, space group Pa3 (nonstandard, reduced to orthorhombic Pcab), the complex cations, anions, and water molecules are arranged by the law of three-layered (fcc) close packing of “quasispherical” species according to two structural types, NaCl and CaF₂. The packing is formed of [Rh(NO₂)₆]^3? anions, which also fill the octahedral voids. The tetrahedral voids are occupied by the central atoms of the [Co(en)₃]³⁺ cations, and the H₂O molecules lie between the cations, performing the packing function: the Ow...N_en contacts of 3.04 Å and the Ow..O_{NO 2} contacts of 3.01 Å characterize weak van der Waals interactions. The values of the interatomic distances Co?N, Rh?N, N?O, N?C, and C?C are in good agreement with the known data.     

Bis­[tris(1,2‐ethanedi­amine‐N,N′)nickel(II)] tetra­thio­antimonate(V) nitrate

The title double salt, [Ni(C₂H₈N₂)₃]₂(SbS₄)(NO₃), was crystallized under solvothermal conditions. Hydro­gen bonds between the SbS₄^3? anions (at four sites) and the [Ni(en)₃]²⁺ (en = ethyl­enedi­amine) cations (at two sites) form a three‐dimensional network. The NO₃^? anion is disordered over four sites. The cation lies on a twofold rotation axis and the SbS₄^3? anion on a axis.