Synthese und Struktur des tetrameren Tris(trimethylsilyl)silylindium(I) und neuer silylsubstituierter Indiumverbindungen

Synthesis and Structure of Tetrameric Tris(trimethylsilyl)indium(I) and of New Silyl substituted Indium Compounds The reaction of InCp* with [LiSi(SiMe₃)₃·3thf] yielded in the first silylsubstituted tetrahedrane of indium [In₄{Si(SiMe₃)₃}₄] ( 1 ). It crystallizes together with [In{Si(SiMe₃)₃}₃] ( 2 ) in dark green crystals. Colourless crystals of [Li(OH)(OSiMe₃)In{Si(SiMe₃)₃}₂]₂ ( 3 ) were isolated as a byproduct from this reaction. It's structural core are three connected four membered rings made up of In‐, Li‐ and O‐atoms. From the reaction of [InOSO₂CF₃] with [LiSi(SiMe₃)₃·3thf] colourless crystals of [In{Si(SiMe₃)₃}₂OSO₂CF₃·thf] ( 4 ) were isolated. InCp* reacted with [LiSiMe(SiMe₃)₂·3thf] to form the orange‐coloured monoindane [In{SiMe(SiMe₃)₂}₃] ( 5 ). 1 – 4 were characterized by X‐ray crystal structure analyses.     

Synthese und Kristallstrukturen der Bismutchalkogenolate Bi(SC6H5)3, Bi(SeC6H5)3 und Bi(S‐4‐CH3C6H4)3

Synthesis and Crystal Structures of Bismuth Chalcogenolato Compounds Bi(SC₆H₅)₃, Bi(SeC₆H₅)₃, and Bi(S‐4‐CH₃C₆H₄)₃ Bismuth(III) acetate reacts with thiophenol in ethyl alcohol at 80 °C to yield Bi(SC₆H₅)₃ ( 1 ). Slow cool down of the deep yellow mixture lead to the formation of orange crystals of 1 . The homotype phenylselenolato compound of bismuth Bi(SeC₆H₅)₃ ( 2 ) has been prepared by the reaction of BiX₃ (X = Cl, Br) with Se(C₆H₅)SiMe₃ in diethyl ether. In the same way as Bi(SC₆H₅)₃ ( 1 ) the reaction between bismuth(III) acetate and 4‐tolulenethiole results in red crystals of Bi(S‐4‐CH₃C₆H₄)₃ ( 3 ). In consideration of three longer Bi–E distances (intermolecular interactions, E = S; Se) the Bi(EPh)₃ molecules form via face‐linked octahedra 1‐dimensional chains in the crystal lattice, while for 3 the 1‐dimensional chain is formed by face‐linked trigonal prisma. We reported herein the synthesis and structures of Bi(SC₆H₅)₃ ( 1 ), Bi(SeC₆H₅)₃ ( 2 ), and Bi(S‐4‐CH₃C₆H₄)₃ ( 3 ).     

Synthese,Struktur und Eigenschaften von [nacnac]MX3‐Verbindungen (M = Ge,Sn; X = Cl,Br, I)

Synthesis, Structure, and Properties of [nacnac]MX₃ Compounds (M = Ge, Sn; X = Cl, Br, I) Reactions of [nacnac]Li [(2,6‐ⁱPr₂C₆H₃)NC(Me)C(H)C(Me)N(2,6‐ⁱPr₂C₆H₃)]Li ( 1 ) with SnX₄ (X = Cl, Br, I) and GeCl₄ in Et₂O resulted in metallacyclic compounds with different structural moieties. In the [nacnac]SnX₃ compounds (X = Cl 2 , Br 3 , I 4 ) the tin atom is five coordinated and part of a six‐membered ring. The Sn–N‐bond length of 3 is 2.163(4) Å and 2.176(5) Å of 4 . The five coordinated germanium of the [nacnac]GeCl₃ compound 5 shows in addition to the three chlorine atoms further bonds to a carbon and to a nitrogen atom. In contrast to the known compounds with the [nacnac] ligand the afore mentioned reaction creates a carbon–metal‐bond (1.971(3) Å) forming a four‐membered ring. The Ge–N bond length (2.419(2) Å) indicates the formation of a weakly coordinating bond.     

[Me3SnVO3] und [(Me2Sn)4V2O9], zwei Organozinnvanadate mit neuen 3D‐Netzwerkstrukturen

[Me₃SnVO₃] and [(Me₂Sn)₄V₂O₉], two Organotin Vanadates with Novel 3D Network Structures Two new organotin vanadates [Me₃SnVO₃] ( 1 ) and [(Me₂Sn)₄V₂O₉] ( 2 ) have been prepared by the reaction of NH₄VO₃ with Me₃SnBr and Me₂SnBr₂ resp. in agar gel. The structures of 1 and 2 have been determined by x‐ray crystallography at 220 K. 1 crystallizes monoclinic in the space group P2₁/c with a = 1335.6(2), b = 1144.4(2), c = 1118.8(2) pm, β = 113.54(2)°. 2 crystallizes orthorhombic in the space group Pnnm with a = 1257.6(2), b = 1345.4(2), c = 1323.1(1) pm. 1 consists of infinite metavanadate chains which are linked by Me₃Sn⁺ cations. 2 exhibits a complex 3D‐ network structure with VO₄ tetrahedra, Me₂SnO₃ trigonal bipyramides and Me₂SnO₄ octahedra linked by common oxygen atoms.     

Ag3Bi14Br21: ein Subbromid mit Bi24+‐Hanteln und Bi95+‐Polyedern – Synthese,Kristallstruktur und Chemische Bindung

Ag₃Bi₁₄Br₂₁: a Subbromide with Bi₂⁴⁺ Dumbbells and Bi₉⁵⁺ Polyhedra – Synthesis, Crystal Structure and Chemical Bonding Black crystals of Ag₃Bi₁₄Br₂₁ = (Bi₉⁵⁺)[Ag₃Bi₃Br₁₅^3?](Bi₂Br₆^2?), the first argentiferous bismuth subhalide, were obtained from a stoichiometric melt of Ag, Bi, and BiBr₃. The compound crystallizes in the monoclinic space group P2₁/m with lattice parameters a = 1277.78(5) pm, b = 1466.87(6) pm, c = 1342.62(5) pm, and β = 108.47(1)° at 110(5) K. In contrast to all other bismuth subhalides that contain an electron‐rich transition metal, the silver atoms are not bonded to bismuth atoms. Instead they are integrated into the anionic bromometallate network, which consists of [MBr₆]‐octahedra (M = Ag, Bi) that share edges and vertices. These corrugated sheets alternate with tessellated layers formed by Bi₉⁵⁺ polycations and hitherto unknown (Bi^II₂Br₆)^2? groups. The latter anions contain Bi₂⁴⁺ dumbbells (299 pm) and can be represented by the structured formula [Br₂Bi^II(μ–Br)₂Bi^IIBr₂]^2?. The multi‐center bonding within the Bi₉⁵⁺ cluster and the bent single‐bond in the Bi₂ dumbbell can be visualized using the electron localization indicator (ELI‐D).     

Darstellung,Eigenschaften und Kristallstruktur von RuSn6[(Al1/3–xSi3x/4)O4]2 (0 ≤ x ≤ 1/3) – einem Oxid mit isolierten RuSn6‐Oktaedern

Preparation, Properties, and Crystal Structure of RuSn₆[(Al_1/3–xSi_3x/4)O₄]₂ (0 ≤ x ≤ 1/3) – an Oxide with isolated RuSn₆ Octahedra RuSn₆[(Al_1/3–xSi_3x/4)O₄]₂ is obtained by the solid state reaction of RuO₂, SnO₂, Sn, and Si in an Al₂O₃‐crucible at 1273 to 1373 K. The compound is cubic with the space group Fm 3 m (a = 9.941(1) Å, Z = 4, R₁ = 0.0277, wR₂ = 0.0619), a semiconductor and stable in air. Results of Mößbauer measurements as well as bond length‐bond strength calculations justify the ionic formulation Ru²⁺Sn₆²⁺[(Al_1/3–x³⁺Si_3x/4⁴⁺)O₄^2–]₂. The central motif of the crystal structure are separated RuSn₆‐octahedrea. These are interconnected by oxygen atoms, arranged tetrahedrely above the surfaces of the RuSn₆‐octahedrea and partialy filled with Al and Si, respectively. Because of these features the compound can be considered as a variant of the crystal structure type of pentlandite.     

[(Ph3Sn)3VO4]·CH3CN und [(Ph3Sn)3VO4]·2 DMF,Triphenylzinnvanadate mit neuartigen Kettenstrukturen

[(Ph₃Sn)₃VO₄]·CH₃CN and [(Ph₃Sn)₃VO₄]·2 DMF, Triphenyltin Vanadates with Novel Chain Structures The reaction of Na₃VO₄ with Ph₃SnCl in a water/CH₂Cl₂ mixture leads to the formation of [(Ph₃Sn)₃VO₄] ( 1 ). Recrystallization of 1 from toluene/CH₃CN gives pale yellow crystals of [(Ph₃Sn)₃VO₄]·CH₃CN ( 2 ). 2 crystallizes as coordination polymer which consists of infinite chains composed of corner‐sharing VO₄ tetrahedra and Ph₃SnO₂ trigonal bipyramides. Additionally the VO₄ groups are connected to two terminal SnPh₃‐Groups containing tin atoms in a tetrahedral environment. [(Ph₃Sn)₃VO₄]·2 DMF ( 3 ) which is obtained from Na₃VO₄ and Ph₃SnCl in a water/DMF mixture contains a polymeric chain structure similar to 2 and additionally one of the terminal SnPh₃ groups is coordinated to a DMF solvent molecule.     

Iodostannate mit polymeren Anionen: (Me3PhN)4 [Sn3I10], [Me2HN–(CH2)2–NMe2H]2 [Sn3I10] und [Me2HN–(CH2)2–NMe2H][Sn3I8]

Iodostannates with Polymeric Anions: (Me₃PhN)₄ [Sn₃I₁₀], [Me₂HN–(CH₂)₂–NMe₂H]₂ [Sn₃I₁₀], and [Me₂HN–(CH₂)₂–NMe₂H] [Sn₃I₈] The polymeric iodostannate anions in (Me₃PhN)₄ [Sn₃I₁₀] ( 1 ) and [Me₂HN–(CH₂)₂–NMe₂H]₂ [Sn₃I₁₀] ( 2 ) consist of Sn₃I₁₂‐trioctahedra, which share four common iodine atoms with adjacent units to form infinite layers in 1 and polymeric chains in 2 . In the anion of [Me₂HN–(CH₂)₂–NMe₂H] [Sn₃I₈] ( 3 ) distorted SnI₆ octahedra sharing common edges and vertices form a two‐dimensional network. (Me₃PhN)₄ [Sn₃I₁₀] ( 1 ): Space group C2/c (No. 15), a = 2406.9(2), b = 968.26(7), c = 2651.7(2) pm, β = 111.775(9), V = 5738.9(8) · 10⁶ pm³; [Me₂HN–(CH₂)₂–NMe₂H]₂ [Sn₃I₁₀] ( 2 ): Space group P2₁/n (No. 14), a = 1187.2(1), b = 1554.4(1), c = 1188.9(1) pm, β = 116.620(8), V = 1961.4(3) · 10⁶ pm³; [Me₂HN–(CH₂)₂–NMe₂H] [Sn₃I₈] ( 3 ): Space group P2₁/c (No. 14), a = 1098.9(2), b = 803.93(7), c = 1571.5(2) pm, β = 102.96(1), V = 1352.9(2) · 10⁶ pm³.     

Synthese,Struktur und Eigenschaften von [(C4H9)2NH2]4[Sn2Se6], [(C4H9)2NH2]4[Sn4Se10] · 2 H2O und [(C3H7)3NH]2[Sn3Se7]

About Selenidostannates. I Synthesis, Structure, and Properties of [Sn₂Se₆]^4–, [Sn₄Se₁₀]^4–, and [Sn₃Se₇]^2– The selenidostannates [(C₄H₉)₂NH₂]₄Sn₂Se₆ · H₂O ( I ), [(C₄H₉)₂NH₂]₄Sn₄Se₁₀ · 2 H₂O ( II ) und [(C₃H₇)₃NH]₂Sn₃Se₇ ( III ) were prepared by hydrothermal syntheses from the elements and the amines. I crystallizes in the monoclinic spacegroup P2₁/n (a = 1262.9(3) pm, b = 1851.3(4) pm, c = 2305.2(4) pm, β = 104.13(3)° and Z = 4). The [Sn₂Se₆]^4– anion consists of two edge‐sharing tetrahedra. II crystallizes in the orthorhombic spacegroup Pna2₁ (a = 2080.3(4) pm, b = 1308.2(3) pm, c = 2263.5(5) pm and Z = 4). The anion is formed from four SnSe₄ tetrahedra which are joined by common corners to the adamantane cage [Sn₄Se₁₀]^4–. III crystallizes in the orthorhombic spacegroup Pbcn (a = 1371.1(3) pm, b = 2285.4(5) pm, c = 2194.7(4) pm and Z = 8). The anion is a chain, built from edge‐sharing [Sn₃Se₅Se_4/2]^2– units, in which two corner sharing tetrahedra are connected to a trigonal bipyramid by an edge of one and a corner of the other tetrahedron. The results of the TG/DSC measurements and of temperature dependent X‐ray diffractograms reveal that I and II decompose at first by release of minor quantities of triethylammonium to compounds with layer structure and larger cell dimensions. At still higher temperature the rest of triethylammonium and H₂Se is evolved, leaving SnSe₂ and Se in the bulk. The former decomposes partially at the highest temperature to SnSe. In the measurements of III the complex intermediate compound was not observed. III decomposes directly to SnSe₂.     

Synthese und Kristallstruktur von [(Me3Si)2BiCu(PMe3)3], dem ersten Komplex mit einer Bismut—Kupfer‐Bindung

Synthesis and Crystal Structure of [(Me₃Si)₂BiCu(PMe₃)₃] — the First Complex with a Bismuth—Copper Bond The reaction of CuO^t Bu with PMe₃ and Bi(SiMe₃)₃ in hexane yields the phosphine‐stabilized complex [(Me₃Si)₂Bi‐Cu( PMe₃)₃]. This synthesis gave rise to the first binuclear Bi—Cu compound to be structurally characterized by X‐ray crystallography.     

Die Cluster‐Salze Bi14Si2MI12 (M = Rh,Ir): [Bi8Si2]‐ und [MBi6I12]‐Baugruppen in CsCl‐analoger Anordnung

The Cluster Salts Bi₁₄Si₂MI₁₂ (M = Rh, Ir): [Bi₈Si₂] and [MBi₆I₁₂] Building Groups in CsCl‐like Structure The reaction of bismuth and iridium with iodine in evacuated quartz ampoules at 1320 K yields black, air insensitive crystals of Bi₁₄Si₂IrI₁₂. The silicon therein is abstracted from the ampoule material whereby the oxygen is gettered in BiOI. The synthesis of Bi₁₄Si₂RhI₁₂ requires the addition of niobium, which gives NbOI₂ with the oxygen originating from the SiO₂. X‐ray diffraction on single crystals showed that the two isotypic compounds crystallize in the space groups P 4/m c c with a = 1018.3(1), c = 2020.1(4) pm for M = Ir, and a = 1019.0(1), c = 2018.7(4) pm for M = Rh. The crystal structures consist of two types of isolated clusters, which form a CsCl‐like packing. In the [MBi₆I₁₂] cuboctahedron the central transition metal atom is octahedrally surrounded by bismuth atoms, and the iodine atoms bridge the edges of the octahedron. The [Bi₈Si₂] polyhedron is a tetragonal antiprism of bismuth atoms of which square faces are capped by silicon atoms. Based on crystal chemistry and band structure calculations the compounds may be formulated as cluster salts [Bi₈Si₂]³⁺[MBi₆I₁₂]^3–. Measurements of the electrical conductivity showed that Bi₁₄Si₂IrI₁₂ is a semiconductor with a band gap of about 0.1 eV. A single unpaired electron out of 1903 electrons per formula causes paramagnetic behaviour that is superposed by strong diamagnetic contributions.     

Synthese,Spektren und Strukturen einfacher Derivate des Tris(bis(trimethylsilyl)methyl)indiums,In(CH(Si(CH3)3)2)3

Syntheses, Spectra, and Structures of Simple Derivatives of Tris(bis(trimethylsilyl)methyl Indium, In(CH(Si(CH₃)₃)₂)₃ Like trimethyl- or triethylindium tris(disyl)indium, In(CH(SiMe₃)₂)₃ (≙ InR₃) also reacts with equimolar amounts of water, D₂O, MeOH, HCl and HCOOH, respectively, in ether solution at room temperature to form the corresponding alkane, here (Me₃Si)₂CH₂, and the simple monosubstitution products R₂InX. With the dibasic oxalic and sulfuric acid the multinuclear derivatives (R₂In)₂C₂O₄ and [RIn(R₂In)₂(SO₄)₂]₂ are formed, respectively. The halogenides R₂InCl, RInCl₂, and RInBr₂ have been prepared by metathesis from InHal₃ and InR₃ (molar ratios 1 : 2 and 2 : 1). The ¹H, ¹³C, and ²⁹Si NMR- as well as the vibrational spectra (IR, Raman) are discussed. According to the X-ray structure elucidations the monosubstitution products R₂InX (with X = OH, OMe, Cl) are dimeric in the solid state and consist of planar, centrosymmetric fourmembered In₂X₂ skeletons. The dibromide RInBr₂ forms a polymeric chain structure with five-fold co-ordinated metal centres and vertex linked, alternately appearing planar as well as slightly folded In₂Br₂-moities. The “sesquisulfate” [R₅In₃(SO₄)₂]₂ has an uncommon, cage-like structure with four as well as five-fold co-ordinated In atoms. The structural data could not be optimally refined due to the highly disordered disyl groups.     

Synthese,Strukturen und Reaktivität von [(2,4,6-Ph3C6H2)Te(μ2-O)X]2 (X  Br und I)

Synthesis, Structures, and Reactivity of [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)X]₂ (X ? Br, I) [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with iodine affording the aryltellurenic halide (2,4,6-Ph₃C₆H₂)TeI, which is oxidized by oxygen to yield [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂. It crystallizes with two molecules of dichloromethane in the monoclinic space group P2₁/c with a unit cell of the dimensions a = 911.3(4); b = 1153.3(2); c = 2244.1(9) pm; β = 93.53(2)°, Z = 2). The analogues bromo compound [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)Br]₂ is obtained by the reaction of [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂ with NH₄Br. It crystallizes with two molecules of xylene in the monoclinic space group P2₁/n (a = 1067.5(5); b = 1018.4(4); c = 2486.5(8) pm; β = 101.71(2)°; Z = 2). Both compounds are built up by two (2,4,6-Ph₃C₆H₂)TeX units (X ? Br, I) which are linked by two oxgen bridges to form centrosymmetric molecules. The Te? O? Te angles are 102°. Distinct Te? O bond lengths have been found (191.4(2) and 208.6(2) pm in [(2,4,6-Ph₃C₆H₂)Te(μ₂-O)I]₂ and 189.8(4)/208.4(5 pm in the bromo compound).     

Neue mehrkernige Organozinn(IV)–Stickstoff‐Verbindungen. Synthese und Kristallstrukturen von [(PhSn)4(NPh)5Cl2] und [(MeSn)4(NHPh)4(NPh)4]

New Polynuclear Organotin(IV)–Nitrogen Compounds. Synthesis and Crystal Structures of [(PhSn)₄(NPh)₅Cl₂] and [(MeSn)₄(NHPh)₄(NPh)₄] The reaction of the organotin halides PhSnCl₃ and MeSnCl₃ with LiNHPh leads to the formation of two new nitrogen bridged organotin compounds, [(PhSn)₄(NPh)₅Cl₂] ( 1 ) and [(MeSn)₄(NHPh)₄(NPh)₄] ( 2 ). The crystal structures of 1 and 2 have been determined by low temperature X‐ray diffraction. 1 contains a bicyclic Sn₄N₅ framework, which consists of two six‐membered Sn₃N₃‐rings. All tin atoms are coordinated nearly tetrahedrally. Two tin atoms are bonded to a phenyl group and three nitrogen atoms, the other two tin atoms are coordinated by a phenyl group, two nitrogen atoms and a terminal chlorine atom. In 2 the tin atoms define the corners of a distorted square. Each edge of the square is bridged by a μ²‐NHPh and a μ²‐NPh group. The bridging NHPh and NPh groups are arranged at opposite sides of the Sn₄ plane. The tin atoms are coordinated square pyramidally by 4 nitrogen atoms and a methyl group.     

Hexasupersilyl-triprismo-hexastannane (tBu3Si)6Sn6—The First Molecular Tin Compound Containing a Sn6 Prism

Dark violet hexastannane ( t Bu ₃ Si) ₆ Sn ₆ displays a new framework motif for molecular tin compounds, in which six Sn atoms are located at the corners of a trigonal prism. The compound can be synthesized according to Equation (a). R*=SitBu₃.     

Easy Access to Soluble Polyanions—Stabilization of the One‐Dimensional Chain 1∞[K4Sn9] by [18]Crown‐6 in [K4Sn9([18]crown‐6)3]⋅ethylenediamine

Well‐characterized Group 14 Zintl anions were accessible by solution methods only in low yields up to now. An easy and inexpensive reaction route to polyanions, which starts from the elements, is admissible through the usage of [18]crown‐6 as reaction medium at 40°C. The [K([18]crown‐6)] unit proves to be an advantageous connecting device between intermetallic and organic networks. The title compound can be regarded as a supramolecular aggregate of a one‐dimensional substructure of the composition K₄Sn₉ (see picture) and an organic component.     

Synthese und Kristallstruktur des gemischt‐valenten Komplexes [Sn2I3(NPPh3)3]

Synthesis and Crystal Structure of the Mixed Valent Complex [Sn₂I₃(NPPh₃)₃] The mixed valent phosphoraneiminato complex [Sn₂I₃(NPPh₃)₃] ( 1 ) was prepared by the reaction of the tin(II) complex [SnI(NPPh₃)]₂ with sodium in tetrahydrofuran. 1 crystallizes with two formula units of THF to form yellow, moisture sensitive single crystals, which were characterized by a crystal structure determination. 1 · 2 THF: Space group P2₁/c, Z = 4, lattice dimensions at –80 °C: a = 1964.5(2), b = 1766.0(2), c = 2058.6(2) pm; β = 118.33(1)°, R = 0.052. 1 forms dimeric molecules in which the tin atoms are linked by two nitrogen atoms of two (NPPh₃^–) groups to form a planar Sn₂N₂ four‐membered ring. The Sn^IV atom is additionally coordinated by a terminal iodine atom and by a terminal (NPPh₃^–) group, whereas the Sn^II atom is additionally coordinated by two iodine atoms forming a ψ trigonal‐bipyramidal surrounding.     

Sn3N4, ein Zinn(IV)-nitrid – Synthese und erste Strukturbestimmung einer binären Zinn–Stickstoff-Verbindung

Sn₃N₄, a Tin(IV) Nitride – Syntheses and the First Crystal Structure Determination of a Binary Tin-Nitrogen Compound By reaction of SnI₄ with KNH₂ in liquid ammonia at 243 K a white product mixture was obtained. After evaporation of ammonia the solid residue was annealed in vacuum for 2–5 d at 573 K. Subsequently collected x-ray powder diffraction patterns exhibited reflections of KI and a new compound Sn₃N₄. Analogous reactions of SnBr₂ and KNH₂ led to KBr and dark brown microcrystalline Sn₃N₄ but also to metallic tin. The structure of tin(IV)-nitride was determined from X-ray and neutron powder diffraction data: Space group Fd 3 m, Z = 8, a = 9.037(3) Å. Sn₃N₄ crystallizes in a spinel type structure. Both metal atom positions are occupied by tin atoms of oxidation state plus four.     

Dimeric Structure of [(η2‐NO3)2(tpy)Bi(μ‐OH)2Bi(tpy)(η2‐NO3)2]

The synthesis and single crystal X‐ray structure determination are reported for the 2,2′ : 6′,2″‐terpyridine (= tpy) adduct of bismuth(III) nitrate. The hydroxide‐bridged dimer [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy)(η²‐NO₃)₂] with nine‐coordinate geometry about Bi was the only isolable product from all crystallization attempts in varying ratios of Bi(NO₃) : terpy.; [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy) · (η²‐NO₃)₂] is triclinic, P 1, a = 7.941(8), b = 10.732(9), c = 11.235(9) Å; α = 63.05(1), β = 85.01(1), γ = 79.26(1)°, Z = 1, dimer, R = 0.058 for N₀ = 2319.