[{C8H12Rh}3(μ3‐OH)2]SbF6: Ein neuer metallorganischer Rhodiumkomplex mit Rh3O2‐Kern

[{C₈H₁₂Rh}₃(μ₃‐OH)₂]SbF₆: A New Organometallic Rhodium Complex with Rh₃O₂ Core Crystals of C₂₄H₃₈F₇O₂Rh₃Sb ( 3 ) obtained from the crystallisation of 2 from wet solvents consist of [{C₈H₁₂Rh}₃(μ₃‐OH)₂]⁺ cations connected with the SbF₆^– anions via hydrogen bonds. In the cations, the Rh₃ faces are bicapped by OH^– ligands.     

Synthesis and Structure of a New Vanadium(IV)‐Cadmium(II) Compound with the Nitrilotriacetate Ligand: {(NH4)2[(VIVO)2(μ2‐O)(nta)2Cd(H2O)2]·H2O}n

A polymeric V^IV‐Cd compound, {(NH₄)₂[(V^IVO)₂(μ₂‐O)(nta)₂Cd(H₂O)₂]·H₂O}_n (H₃nta = nitrilotriacetic acid), has been prepared and characterized by single‐crystal X‐ray diffraction. The compound crystallizes in the monoclinic space group C2/c with a = 17.3760(2) Å, b = 8.0488(1) Å, c = 17.3380(2) Å, β = 107.9690(10)°, V = 2306.55(5) ų, Z = 4, and R₁ = 0.0303 for 1958 observed reflections. The structure exhibits a heterometallic three‐dimensional network formed by polymeric [(V^IVO)₂(μ₂‐O)(nta)₂Cd(H₂O)₂]^2? anions.     

Synthesis,Crystal Structure and Magnetic Behaviour of {[Co(dimb)2(H2O)2]·(NO3)2·(H2O)2}n

The title complex {[Co(dimb)₂(H₂O)₂]·(NO₃)₂·(H₂O)₂}_n ( 1 ) (dimb = 1,3‐di(imidazol‐1‐ylmethyl)‐5‐methylbenzene) has been hydrothermally synthesized by the reaction of dimb with Co(NO₃)₂·6H₂O in aqueous solution. The cobalt(II) atoms are linked by bridging dimb ligands to form 2D corrugated and wavy networks containing Co₄(dimb)₄ macrocyclic motifs. Two neighboring independent layers interlinked each other in a parallel fashion to construct three‐dimensional structure by O–H···O, N–H···O and C–H···O hydrogen bonds. Magnetic measurement shows the weak antiferromagnetic interaction with a one‐dimensional chain model in the range of 5–300 K, with J of –0.68 cm⁻¹.     

Structure and Magnetic Properties of a Novel Two‐Dimensional Complex from 1, 3, 5‐Benzenetricarboxylate and Neodymium(III) — {[Nd(1, 3, 5‐benzenetricarboxylate)(H2O)4] · H2O}n

A unique neodymium(III) complex, {[Nd(BTC)(H₂O)₄] · H₂O}_n (BTC = 1, 3, 5‐benzenetricarboxylate), was obtained from the reaction between Nd(ClO₄)₃ · xH₂O and Na₃BTC. Coordination bonds, hydrogen bonds, and π‐π stacking form a supramolecular structure with a novel, two‐dimensional framework. The temperature‐dependent magnetic susceptibilities were analyzed by the Curie‐Weiss law; the following values were found C = 1.32, θ = —18.3 K, respectively.     

The 3D Supramolecular Compound {[Cu2(L‐val)2(4,4′‐bipy)(H2O)2](NO3)2}n (L‐val = L‐valine anion, 4,4′‐bipy = 4,4′‐bipyridine)

{[Cu₂(L‐val)₂(4,4′‐bipy)(H₂O)₂](NO₃)₂}_n was synthesized and its crystal structure was determined by X‐ray diffraction. In the presence of 4,4′‐bipyridine, deprotoned L‐valine chelates Cu^II ions into coordination layers which were linked into a framework by hydrogen‐bonded chains resulting from nitrate anions and water molecules.     

Crystal Structures of [Cu2(bpy)2(H2O)(OH)2(SO4)]·4H2O and [Cu(bpy)(H2O)2]SO4 with bpy = 2, 2′‐Bipyridine

Two sulfato Cu^II complexes [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)]· 4H₂O ( 1 ) and [Cu(bpy)(H₂O)₂]SO₄ ( 2 ) were synthesized and structurally characterized by single crystal X—ray diffraction. Complex 1 consists of the asymmetric dinuclear [Cu₂(bpy)₂(H₂O)(OH)₂(SO₄)] complex molecules and hydrogen bonded H₂O molecules. Within the dinuclear molecules, the Cu atoms are in square pyramidal geometries, where the equatorial sites are occupied by two N atoms of one bpy ligand and two O atoms of different μ₂—OH groups and the apical position by one aqua ligand or one sulfato group. Through intermolecular O—H···O and C—H···O hydrogen bonds and intermolecular π—π stacking interactions, the dinuclear complex molecules are assembled into layers, between which the hydrogen bonded H₂O molecules are located. The Cu atoms in 2 are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two H₂O molecules and two sulfato groups with the sulfato O atoms at the trans positions and are bridged by sulfato groups into ¹[Cu(bpy)(H₂O)₂(SO₄)_2/2] chains. Through the interchain π—π stacking interactions and interchain C—H···O hydrogen bonds, the resulting chains are assembled into bi—chains, which are further interlinked into layers by O—H···O hydrogen bonds between adjacent bichains.     

The topotactic dehydration of monoclinic {[Co(pht)(bpy)(H2O)2]·2H2O}n into orthorhombic [Co(pht)(bpy)(H2O)2]n (pht is phthalate and bpy is 4,4′‐bipyridine)

Controlled heating of single crystals of the previously reported [Köferstein & Robl (2007). Z. Anorg. Allg. Chem. 633 , 1127–1130] dihydrate {[Co(pht)(bpy)(H₂O)₂]·2H₂O}_n, (II) [where pht is phthalate (C₈H₄O₄) and bpy is 4,4′‐bipyridine (C₁₀H₈N₂)], produced a topotactic transformation into an unreported diaqua anhydrate, namely poly[diaqua(μ₂‐benzene‐1,2‐dicarboxylato‐κ²O¹:O²)(μ₂‐4,4′‐bipyridine‐κ²N:N′)cobalt(II)], [Co(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)₂]_n, (IIa). The structural change consists of the loss of the two solvent water molecules linking the original two‐dimensional covalent substructures which are the `main frame' of the monoclinic P2/n hydrate (strictly preserved during the transformation), with further reaccommodation of the latter. The anhydrate organizes itself in the orthorhombic system (space group Pmn2<sub>1</sub>) in a disordered fashion, where the space‐group‐symmetry restrictions are achieved only in a statistical sense, with mirror‐related two‐dimensional planar substructures, mirrored in a plane perpendicular to [100]. Thus, the asymmetric unit in the refined model is composed of two superimposed mirror‐related `ghosts' of half‐occupancy each. Similarities and differences with the parent dihydrate and some other related structures in the literature are discussed.     

Synthesis and crystal structure of heteronuclear La( III )‐Cu(II ) complex { [LaCu2(NTA)2(4,4′‐bpy)(H2O)3]NO3·5H2O}n

A novel La( III )‐Cu( II ) heterometallic coordination polymer {[LaCu₂(NTA)₂(4,4′‐bpy)(H₂O)₃]NO₃·5H₂O]_n, where H₃NTA denotes nitrilotriacetic acid and 4,4′‐bpy denotes 4, 4‐bipyridine, was synthesized and characterized by IR spectrum, elemental analysis and X‐ray diffraction. The complex crystallizes in the triclinic space group Pi with cell parameters a = 1.33710(10) nm, b = 1,44530(10) nm, c =1.0949(2) nm, α = 71.905(7)°, β = 74.327(7)°, γ = 64.427(9)°, V = 1.7912(4) nm³and Z = 2. It consists of heterometallic units, in which each La( II ) ion is coordinated in a distorted monocapped square antiprism by three oxygen atoms from water molecules and six carboxyl oxygen atoms from five NTA^3? ions, and each Cu( I ) ion is coordinated by one nitrogen atom from 4,4′‐bpy and one nitrogen atom, three oxygen atoms from NTA^3?. In the title complex, La( I ) ions and Cu( II ) ions are connected by the heterometallic bridging of NTA^3?, constructing a two‐dimensional network structure along the [110]. And it is extended into an infinite three‐dimensional network structure by the formation of homometallic bridging of Cu‐4, 4′‐bpy‐Cu, exhibiting a certain inclusion ability.     

A Novel Adipate Bridged Supramolecular Layer: Crystal Structure of the Cobalt(II) Complex [(μ‐C6H8O4)4/2Co(μ‐H2O)2Co(H2O)4] · 4 H2O

The pale‐rose compound [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] · 4 H₂O was prepared from adipic acid and CoCO₃ in aqueous solution. The crystal structure (monoclinic, P2₁/n (no. 14), a = 8.061(1), b = 15.160(2), c = 9.708(2) Å, β = 90.939(7)°, Z = 2, R = 0.0405, wR² = 0.0971) consists of adipate bridged supramolecular [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] layers and hydrogen bonded H₂O molecules. The cobalt atoms Co1 and Co2 are distorted octahedrally coordinated by the O atoms of two bridging trans‐H₂O molecules and four bidentate adipate anions (Co1) and by the O atoms of two bridging trans‐H₂O molecules and four monodentate H₂O molecules (Co2), respectively. Equatorial bonds: d(Co1–O) = 2.048 Å (2 × ), 2.060 Å (2 × ); d(Co2–O) = 2.057 Å (2 × ), 2.072 Å (2 × ). Axial bonds: d(Co1–O) = 2.235 Å (2 × ); d(Co2–O) = 2.156 Å (2 × ).     

Heterodinukleare Komplexe: Synthese und Kristallstrukturen von [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)]

Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)], [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], and [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] [Ru₃Rh(CO)₇(μ₃‐H)(μ‐P^tBu₂)₂(^tBu₂PH)(μ‐Cl)₂] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) ų. The reaction of 4 with dppm (Ph₂PCH₂PPh₂) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 ų. Moreover single crystals of [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P2₁/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) ų.     

Koordinationspolymere 1, 2‐Dithiooxalato‐ und 1, 2‐Dithioquadratato‐Komplexe. Synthese und Strukturen von [BaCr2(bipy)2(1, 2‐dtox)4(H2O)2], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)2(H2O)2]·2H2O und [H3O][H5O2][Cu(cyclam)]3[Cu2(1, 2‐dtsq)3]2

Coordination Polymeric 1, 2‐Dithiooxalato and 1, 2‐Dithiosquarato Complexes. Syntheses and Structures of [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H2₂, and [H₃O][H₅O₂][Cu(cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ 1, 2‐Dithioxalate and 1, 2‐dithiosquarate ions have a pair of soft and hard donor centers and thus are suited for the formation of coordination polymeric complexes containing soft and hard metal ions. The structures of four compounds with building blocks containing these ligands are reported: In [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂] Barium ions and pairs of Cr(bipy)(1, 2‐dtox)₂ complexes form linear chains by the bisbidentate coordination of the dithiooxalate ligands towards Ba²⁺ and Cr³⁺. In [Ni(cyclam)(1, 2‐dtsq)]·2DMF short NÖH···O hydrogen bonds link the NiS₂N₄‐octahedra with C_2v‐symmetry to an infinite chain. In [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H₂O the 1, 2‐dithiosquarato ligand shows a rare example of S‐coordination towards manganese(II). The sulfur atoms of cis‐MnO₂S₄‐polyedra are weakly coordinated towards the axial sites of square‐planar NiN₄‐centers, thus forming a zig‐zag‐chain of Mn···Ni···Mn···Ni polyhedra. [H₃O][H₅O₂][Cu (cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ contains square planar [Cu^II(cyclam)]²⁺ ions and dinuclear [Cu^I₂(1, 2‐dtsq)₃]^4— ions. Here each copper atom is trigonally planar coordinated by S‐donor atoms of the ligands. The Cu…Cu distance is 2.861(4)Å.     

Synthesis and Crystal Structure of [La(phen)2(H2O)2(NO3)2]NO3 · 2(phen)(H2O) with phen = 1,10‐phenanthroline

The title compound [La(phen)₂(H₂O)₂(NO₃)₂](NO₃) · 2(phen)(H₂O) with phen = 1,10‐phenanthroline was prepared by the stoichiometric reaction of La(NO₃)₃ · 6 H₂O and 1,10‐phenanthroline monohydrate in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 11.052(2), b = 13.420(2), c = 16.300(2) Å, α = 78.12(1)°, β = 88.77(1)°, γ = 83.03(1)°, Z = 2, R = 0.0488, wR² = 0.1028) consists of [La(phen)₂(H₂O)₂(NO₃)₂]²⁺ complex cations, NO₃^– anions, phen and H₂O molecules. The La atom is 10‐fold coordinated by four N atoms of two bidentate chelating phen ligands and six O atoms of two H₂O molecules and two bidentate chelating NO₃^2– ligands with d(La–O) = 2.522–2.640 Å and d(La–N) = 2.689–2.738 Å. The intermolecular π‐π stacking interactions play an essential role in the formation of two different 2 D layers parallel to (001), which are formed by complex cations and uncoordinating phen molecules, respectively. The uncoordinated NO₃^– anions and H₂O molecules are sandwiched between the cationic and phen layers.     

[Co7(μ4‐O)2(O2C–CH3)8(NCO)2(HNPEt3)4] · 2 OEt2, ein siebenkerniger Komplex mit vier‐, fünf‐ und sechsfach koordinierten Cobalt‐Atomen

[Co₇(μ₄‐O)₂(O₂C–CH₃)₈(NCO)₂(HNPEt₃)₄] · 2 OEt₂, a Seven Nuclearity Complex with Four, Five, and Sixfold Coordinated Cobalt Atoms The title compound was prepared from cobalt(II) acetate with Me₃SiNPEt₃ at 180 °C and subsequent crystallization from diethylether to give blue, moisture sensitive single crystals, which were characterized by a crystal structure determination. Space group P2₁/n, Z = 2, lattice dimensions at –80 °C: a = 1544.0(1), b = 1522.1(2), c = 1702.0(1) pm, β = 103.911(10)°, R = 0.0490. [Co₇(μ₄‐O)₂(O₂C–CH₃)₈(NCO)₂ · (HNPEt₃)₄] has a centrosymmetric cluster‐like structure in which the octahedrally coordinated central cobalt atom is connected with the remaining six cobalt atoms via two μ₄‐oxygen atoms as well as via four bridging acetato groups to form a Co(Co)₆ octahedral skeleton. Four of the peripheric cobalt atoms have a distorted trigonal‐bipyramidal coordination sphere, the other two cobalt atoms are tetrahedrally coordinated. The latter are connected with the nitrogen atoms of the cyanato groups.     

Darstellung und Struktur der Komplexverbindungen trans‐[CoIII(py)4F2][H2F3] und [Pd(py)4]F2 · 1,5 HF · 2 H2O

Synthesis and Crystal Structures of the Complexes trans ‐[Co^III(py)₄F₂][H₂F₃] and [Pd(py)₄]F₂ · 1.5 HF · 2 H₂O The cobalt complex trans‐[Co(III)(py)₄F₂][H₂F₃] ( 1 ) has been prepared by electrochemical oxidation of CoF₂ in a pyridine/HF mixture and the palladium complex [Pd(py)₄]F₂ · 1.5 HF · 2 H₂O ( 2 ) has been obtained via halogen exchange between Pd(py)₂Cl₂ and AgF₂ in pyridine. 1 and 2 crystallize in the space group C2/c with a = 27.928(14), b = 9.019(3), c = 18.335(8) Å, β = 113.41(3)° for 1 and a = 28.183(9), b = 9.399(3), c = 17.397(6) Å, β = 104.66(3)° for 2 , respectively. Concerning the shape and location of the M(py)₄ fragments 1 and 2 are isostructural. The metal atoms occupy special positions in their unit cells with the result that four complex atoms have C₂ symmetry and four complex cations have C_i symmetry giving a total of Z = 8. In 1 two F^– ions complete an octahedral coordination around the Co atoms (Co–F 1.820(2) to 1.834(3) Å). In 2 the shortest Pd–F distance is 3.031(2) Å. This precludes the existence of Pd–F bonds. In 1 one can identify H₂F₃^– groups. In 2 there are larger aggregates, consisting of F^–, HF, and H₂O subunits, connected by H‐bridges. In spite of these differences, both complexes belong to the same type of structure, which may be of a common type M^x+(py)₄F_x · y HF · z H₂O.     

Identification of the Structural Boundary between [Ln(18‐crown‐6)(NO3)3] and [Ln(NO3)3(H2O)3] · 18‐crown‐6 Motifs in the Lanthanide Series

Recrystallization of Ln(NO₃)₃ (Ln = Sm, Eu, Yb) in the presence of 18‐crown‐6 under aqueous conditions yielded [Ln(NO₃)₃(H₂O)₃] · 18‐crown‐6. X‐ray crystallography revealed isomorphous structures for each of the lanthanide complexes where [Ln(NO₃)₃(H₂O)₃] is involved in hydrogen bonding interactions with 18‐crown‐6. The transition point where the structural motif changes from [Ln(18‐crown‐6)(NO₃)₃] (with the metal residing in the crown cavity) to [Ln(NO₃)₃(H₂O)₃] · 18‐crown‐6 has been identified as at the Nd/Sm interface. A similar investigation involving [Ln(tos)₃(H₂O)₆] (tos = p‐toluenesulfonate) and 18‐crown‐6 were resistant to crown incorporation. X‐ray studies show extensive intra‐ and intermolecular hydrogen bonding is present.     

The structure of {[Co(pht)(bpy)(H2O)]·3H2O}n (pht is phthalate and bpy is 4,4′‐bipyridine) and the role of solvent water clusters in structure stability

The Co^II cation in poly[[aqua(μ‐benzene‐1,2‐dicarboxylato‐κ³O¹,O²:O¹)(μ‐4,4′‐bipyridine‐κ²N:N′)cobalt(II)] trihydrate], {[Co(C₈H₄O₄)(C₁₀H₈N₂)(H₂O)]·3H₂O}_n, is octahedrally coordinated by two N atoms of two 4,4′‐bipyridine ligands, three O atoms from phthalate anions and a fourth O atom from a coordinated water molecule. The packing consists of planes of coordination polymers linked by hydrogen bonds mediated by three solvent water molecules; the linkage is achieved by the water molecules forming intricate oligomeric clusters which also involve the O atoms of the phthalate ligands.     

[{Cp″Co}3(μ3-P)(μ3-PSe)], ein Dreikerncluster mit einem PSe-Liganden

[{Cp″Co}₃(μ₃-P)(μ₃-PSe)], a Trinuclear Cluster with a PSe Ligand The cothermolysis of [Cp″Co(CO)₂] ( 1 ), Cp″ = C₅H₃Bu-1.3, and P₄ gives besides [{Cp″Co}₃(μ₃-P)₂] ( 2 ) the cobalt P_n complexes [{Cp″Co}₄(μ₃-P)₄] ( 3 ) and [{Cp″Co}₂(μ, η^2:2-P₂)₂] ( 4 ). 2 can be oxidized with grey selenium forming [{Cp″Co}₃(μ₃-P)(μ₃-PSe)] ( 5 ) and [{Cp″Co}₃(μ₃-PSe)₂] ( 6 ), complexes with the hitherto unknown PSe ligand. The crystal structure of 5 reveals a trigonal-bipyramidal Co₃P₂ skeleton with one μ₃-PSe ligand.     

[{Er(NC5H4COOH)(H2O)2}2(H5O2)(HgCl5)(HgCl4)2(H2O)2]n – Synthesis,Crystal Structure and Properties

The first heterometallic 4f‐5d inorganic‐organic metal‐isonicotinic acid hybrid [{Er(NC₅H₄COOH)(H₂O)₂}₂(H₅O₂)(HgCl₅)(HgCl₄)₂(H₂O)₂]_n ( 1 ) has been synthesized via hydrothermal reaction and structurally characterized. Complex 1 crystallizes in the space group C2/c of the monoclinic system with four formula units per unit cell: a = 24.194(3), b = 20.792(3), c = 15.289(4) Å, β = 128.39(2)°, V = 6028(2) ų, C₃₆H₄₇Cl₁₃Er₂Hg₃N₆O₂₀, M_r = 2280.94, D_c = 2.513 g/cm³, S = 0.929, μ(MoKα) = 11.017 mm^?1, F(000) = 4248, R = 0.0425 and wR = 0.0739. The crystal structure analysis reveals that the title complex is characteristic of a one‐dimensional chain‐like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions. Optical absorption spectra of 1 reveal the presence of an optical gap of 3.45 eV. The magnetic properties show that complex 1 exhibits antiferromagnetic interactions.     

A Nitrilotriacetate Bridged Heteronuclear Co(II)-Na(I) Polymer: {[CoNa(NTA)(H_2O)_3]·2H_2O}_n

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Cobalt(II) and Cobalt(III) Tri‐tert‐butoxysilanethiolates. Synthesis,Properties, Crystal and Molecular Structures of [Co{μ‐SSi(OBut)3}{SSi(OBut)3}(NH3)]2 and [Co{SSi(OBut)3}2(NH3)4][SSi(OBut)3] Complexes

The heteroleptic neutral tri‐tert‐butoxysilanethiolate of cobalt(II) incorporating ammonia as additional ligand ( 1 ) has been prepared by the reaction of a cobalt(II) ammine complex with tri‐tert‐butoxysilanethiol in water. Complex 1 , dissolved in hexane, undergoes oxidation in an ammonia saturated atmosphere to the ionic cobalt(III) compound 2 . Molecular and crystal structures of 1 and 2 have been determined by single crystal X‐ray structural analysis. 1 forms a dimeric molecule [Co{μ‐SSi(OBu^t)₃}{SSi(OBu^t)₃}(NH₃)]₂ with a folded central Co₂S₂ ring and distorted tetrahedral ligand arrangement at both Co^II atoms (CoNS₃ core). The product 2 is composed of the octahedral Co^III complex cation [Co{SSi(OBu^t)₃}₂(NH₃)₄]⁺ and the tri‐tert‐butoxysilanethiolate anion. Within the crystal two pairs of ions interact by hydrogen bonds forming well separated entities. 1 and 2 are the first structurally characterized cobalt thiolates where metal is also bonded to ammonia and 2 is the first cobalt(III) silanethiolate.