Über Polygermane. VI. 1,4-Diiodoctaphenyltetragerman l-(Ph2Ge-)4l,Kristallstruktur und Schwingungsspektren

On Polygermanes. VI. 1,4-Diiodooctaphenyltetragermane I-(Ph₂Ge-)₄I, Crystal Structure and Vibrational Spectra The crystal structure of the title compound has been determined and refined to a R of 0.060. The arrangement of the heavy atoms in the six membered chain I-Ge₄-I is all trans with a fully staggered conformation of the substituents. The torsion of the phenyl rings results in a molecular propeller with eight wings (symmetry C_i). Distances: Ge—Ge 245.1 (1) and 245.9 (2), Ge—I 255.9 (1) pm. The packing of the I-(Ph₂Ge-)₄I molecules resembles a tetragonal body centred sphere packing with coordination number (10+4). Domains for the 12 normal vibrations of the chain I-Ge₄-I are given.     

Über polygermane: XIV. Polygermane als nebenprodukte der Grignard-reaktion von PhMgBr mit GeCl4

The synthesis of GePh₄ and Ge₂Ph₆ by Grignard reaction in THF or ether/toluene leads to the by-products Ge₃Ph₈ (up to 11%) and Ge₄Ph₁₀ (up to 18%) which is dependant on using an excess of Mg. A quantitative analysis of the resulting products by HPLC and a semipreparative separation by column, flash, and HPL chromatography is described. The crystal structures of Ge₃Ph₈ (R = 0.075) and Ge₄Ph₁₀ · 2C₆H₆ (R = 0.054) have been determined. Ge₄Ph₁₀ has C_i symmetry and both chain conformations are well staggered (49–70° for Ge₃Ph₈, 53–66° for Ge₄Ph₁₀). The GeGe distances and GeGeGe angles are 244 pm and 121° (Ge₃Ph₈), and 246 pm and 118° (Ge₄Ph₁₀).     

Über polygermane: XV. Darstellung von phenylierten trigermanen in HMPT

The optimum conditions for the synthesis of the trigermanes Ge₃Ph₈ and Ge₃Me₂Ph₆ according to R₂GeCl₂ + 2 Ph₃GeAk (Ak = Li, K) in HMPT have been determined. The main difficulty is to repress a nucleophilic attack of Ph₃Ge⁻ at newly formed GeGe bonds. The mass spectrum of Ge₃Me₂Ph₆ shows rearrangements of the GePh₃ and Ph/Me groups. The ¹³C NMR phenyl signals of di-, tri- and tetra-germanes are nearly identical. Ge₃Ph₈ and Ge₄Ph₁₀ transform to the plastically-crystalline state before melting (ΔH 45.3 and 54.9 kJ mol⁻¹). The crystal structure of Ge₃Me₂Ph₆ has been determined. The molecule has C₂ symmetry (GeGe 242.9(1) pm, GeGeGe 120.3(1)°).     

Über Polygermane. X. Schwingungsspektren der Homocyclen (Ph2Ge)4, (Ph2Ge)5 und (Ph2Ge)6

On Polygermanes. X. Vibrational Spectra of the Homorings (Ph₂Ge)₄, (Ph₂Ge)₅, and (Ph₂Ge)₆ IR and Raman transitions of the crystalline title compounds are given from 3100 to 100 cm^?1. The spectra are nearly identical above 350 cm^?1. The Ge_n ring vibrations range from 330 to 140 cm^?1 and are unspecifically coupled with mass sensitive phenyl modes. The distribution of the individual values is discussed by means of the intracyclic bond angles determined by X-ray structure analysis.     

Über Polygermane. VII [1]. Kristallstruktur von Dodecaphenylcyclohexagerman · Ditoluol

On Polygermanes. VII. Crystal Structure of Dodecaphenylcyclohexagermane Ditoluene The crystal structure of the title compound ( 1 d ) has been determined, refined to a R of 0.071, and compared with the structure of Ge₆Ph₁₂ · 7 benzene ( 1 c ). The molecular structure of Ge₆Ph₁₂ ( 1 ) is a Ge₆-chair with 6 axial and equatorial phenyl substituents respectively. The two toluene molecules in 1 d sandwich 1 above and below the plane of the six-membered ring resulting in steeper axial phenyl groups, stronger rippling of the Ge₆-chair and stretched Ge–Ge distances (246.3 pm) compared to 1 c . 1 has C_i-symmetry in both structures with nearly identical torsion of the phenyl groups. The Ge₆(Ph_eq)₆-part of the molecule approximates C_2h-symmetry. The arrangement of any two phenyl groups realizes largely either a parallel or a perpendicular setting of their respective planes. The joint conformation found is a normal conformation for molecules of the type X₆Ph₁₂.     

Über polygermane: XVI. Synthese α,ω-dichlorierter polygermane Cl(Ph2Ge)nCl (n = 2,3,4) durch germylen-einschub

The germylene Ph₂Ge of Ph₂GeHCl and Net₃ inserts in excess Ph₂GeHCl and forms polygermanes Cl(Ph₂Ge)_nH. This one-pot reaction and subsequent chlorination to Cl(Ph₂Ge)_nCl has been optimized. Increasing amounts of NEt₃ step up the yields of higher polygermanes. The ¹³C NMR phenyl signals for C(ipso) shift to low field with increasing chain length. The crystal structures of Cl(Ph₂Ge)_3,4Cl (R = 0.072 and 0.087) have been determined. The position of Cl(Ph₂Ge)₄Cl is split off by disorder (main molecule 82%, side molecule 18%). Two crystallographically different molecules of the trigermane are present; the ClGe₃Cl chain contains anti-gauche and gauche-gauche conformation respectively (distances GeGe 241.3–243.7 pm, angles GeGeGe 110.4 and 116.7°). The ClGe₄Cl chain is centrosymmetric and has all-anti conformation (distances GeGe 245.0 and 244.2 and 244.2 pm, angle GeGeGe 116.2°).     

Beiträge zur Strukturchemie phosphorhaltiger Ketten und Ringe. 7. Die Kristall- und Molekülstruktur des Diphosphagermetans (t-BuP)2(GePh2)2

Structural Chemistry of Phosphorus Containing Chains and Rings. 7. Molecular and Crystal Structure of the Diphosphagermetane (t-BuP)₂(GePh₂)₂ The compound 1,2-di-tert-butyl-3,3,4,4-tetraphenyl-diphospha-3,4-digerma-cyclobutan, (t-BuP)₂(GePh₂)₂, crystallizes monoclinically in the space group P2₁/c with a = 996.8 pm, b = 1337.3 pm, c = 2403.4 pm, β = 92.66° and Z = 4 formula units. The main structural feature is a non-planar four-membered ring. The (average) bond lengths are d(Ge? Ge) = 242.1 pm, d(Ge? P) = 234.0 pm, d(P? P) = 221.6 pm, d(Ge? C) = 194.9 pm, d(P? C) = 188.tyl4 pm, d(C? C)_Ph = 136.l5 pm, d(C? C)_t-Bu = 151.8 pm, d(C? H)_Ph = 91 pm, d(C? H)_t-Bu ? 95 pm. The geometry of the substituents phenyl and tert-butyl is quite normal.     

Hypervalent organoselenium compounds stabilized by intramolecular coordination: synthesis and crystal structures

Two novel hypervalent selenium(IV) compounds stabilized by intramolecular interactions, namely 6‐phenyl‐6,7‐dihydro‐5H‐2,3‐dioxa‐2aλ⁴‐selenacyclopenta[hi]indene, C₁₄H₁₂O₂Se, 14 , and 5‐phenyl‐5,6‐dihydro‐4H‐benzo[c][1,2]oxaselenole‐7‐carbaldehyde, C₁₄H₁₂OSe₂, 15 , have been synthesized by the reaction of 2‐chloro‐1‐formyl‐3‐(hydroxymethylene)cyclohexene with in‐situ‐generated disodium diselenide (Na₂Se₂). The title compounds were characterized by FT–IR spectroscopy, ESI–MS, and single‐crystal X‐ray diffraction studies. For 14 , there is whole‐molecule disorder, with occupancies of 0.605 (10) and 0.395 (10), a double bond between C and Se, and the five‐membered selenopentalene rings are coplanar. The packing is stabilized by π–π stacking interactions involving one of the five‐membered Se/C/C/C/O rings [centroid–centroid (Cg…Cg) distance = 3.6472 (18) Å and slippage = 1.361 Å], as well as C—H…π interactions involving a C—H group and the phenyl ring. In addition, there are bifurcated C—H…Se,O interactions which link the molecules into ribbons in the c direction. For 15 , the C—Se bond lengths are longer than those of 14 . The two five‐membered rings are coplanar. There are no π–π or C—H…π interactions; however, molecules are linked by C—H…O interactions into centrosymmetric dimers, with graph‐set notation R₂²(16).     

Über polygermane: XI. Funktionalisierung von hexaphenyldigerman

The optimum conditions for selectively cleaving off two phenyl groups in Ge₂Ph₆ by trichloroacetic acid have been determined. Neither trihaloacetic acids nor HCl/AlCl₃ nor reactive tetrahalides MCl₄ are suitable reagents for cleaving one phenyl group alone. The ¹³C NMR chemical shifts of functional phenyl-mono- and -digermanes are given. The crystal structure of 1,2-bis(trichloroacetate)tetraphenyldigermane has been determined and refined to R = 0.048. The digermane bond is bridged by both acetates (distances GeGe 239.3(2), GeO 207.3(3) and 231.4(3) pm). The Ge atoms have trigonal bipyramidal coordination.     

Über Polygermane. II [1]. Die Modifikationen des Dodecaphenylcyclohexagermans [2]

On Polygermanes. II. Modifications of Dodecaphenylcyclohexagermane Dodecaphenylcyclohexagermane (1) can be obtained from solutions pure (1a) , with 2 und 7 moles of crystal benzene (1b, 1c) and with 2 moles of crystal toluene (1d). Mass spectrum, ¹³C-nmr spectrum, assigned vibrational spectra (v_{s, Ge? Ge? Ge} = 220–235 cm^?1, v_{as, Ge? Ge? Ge} = 245–260 cm^?1) and crystal data are given. The crystal structure of 1c has been determined and refined to a R of 0.059. 1 forms a flattened Ge₆-chair (Ge-Ge distance 245.7(1) pm) with 6 axial and equatorial substituents respectively. The molecules of 1 approach spheres with a packing midway between a simple cubic and a cubic closest-packed arrangement.     

Über Glasbildung und Eigenschaften von Chalkogenidsystemen. XXXIII. [1] Kondensierte Thio- und Selenohypodigermanate und -silicate Na8M4X10 (MSi,Ge) und Na4Ge4X8 (XS,Se)

About Glass Formation and Properties of Chalcogenide Systems. XXXIII. Condensed Thio- and Selenohypodigermanates and -silicates Na₈M₄X₁₀ (M?Si, Ge) and Na₄Ge₄X₈ (X?S, Se) The formation of the compounds Na₈Si₄X₁₀ and Na₈Ge₄X₁₀ (X?S, Se) is reported prepared by reaction of Ge₂S₃ or Ge₂Se₃ with Na₂S or Na₂Se, respectively, in CH₃OH utilizing a mole ratio of 1 to 2 or in the case of the Si compounds by synthesis from the elements. Applying the mole ratio Ge₂X₃:Na₂X = 1 the compounds Na₄Ge₄X₈ (X?S, Se) are obtained. The anion constitution is discussed in relation with cryoscopic mole weight measurements in Glauber-salt melts.     

Die Kristallstruktur von Ag2Ge2O5: Eine neuartige Gerüststruktur von Ge2O52−

Crystal Structure of Ag₂Ge₂O₅: A New Ge₂O₅^2? Network Structure Ag₂Ge₂O₅ was prepared from the binary oxides at high O₂ pressures. Single crystal X-ray diffraction work indicated monoclinic symmetry (P2₁/c; a = 1101.3(2); b = 1006.3(1); c = 1221.9(3) pm; ß = 94.6(1)°). The structure was determined by direct methods (3372 independent structure factors) and refined to a conventional R value of 0.084. A new Ge₂O₅^2? network structure was found with germanium coordinated octahedrally (­d(Ge—O) = 188,7 pm) and tetrahedrally (­d(Ge—O) = 175,9 pm), in equal proportions, by oxygen. The polyhedra share vertices and edges, thus forming a three dimensional channel system, which is occupied by Ag⁺ ions. The shortest Ag—Ag distance of 284 pm, like the pale yellow colour of the compound, indicates Ag⁺—Ag⁺ interaction.     

Über Glasbildung und Eigenschaften von Chalkogenidsystemen. XXVIII. Zur Bindungsenergie der Si?Si- und Ge?Ge-Bindung in den Verbindungen Na6Si2X6 und Na6Ge2X6 (X = S,Se)

About Glas Formation and Properties of Chalcogenide Systems. XXVIII. On Bonding Energies of Si? Si and Ge? Ge Bonds in Na₆Si₂X₆ and Na₆Ge₂X₆ (X = S, Se) Potentiometric titration of 0.01 molar solutions of Na₆Si₂S₆, Na₆Si₂Se₆, Na₆Ge₂S₆, and Na₆Ge₂Se₆ in methanol with bromine yields the thermodynamic data of the reactions which take place under scission of the Si—Si or Ge—Ge bonds, respectively. The bonding energies of these homonuclear bonds are estimated and compared with data from the literature.     

Isolation of an Imino‐N‐heterocyclic Carbene/Germanium(0) Adduct: A Mesoionic Germylene Equivalent

An autoionization of germanium dichloride/dioxane complex with an imino‐N‐heterocyclic carbene ligand ( L ) afforded a novel germyliumylidene ion, [( L )GeCl]⁺[GeCl₃]^?, which was fully characterized. Reduction of the germyliumylidene ion with potassium graphite produced a cyclic species [( L )Ge], which can be viewed as both a Ge⁰ species and a mesoionic germylene. X‐ray diffraction analysis and computational studies revealed one of the lone pairs on the Ge atom is involved in the π system on the GeC₂N₂ five‐membered ring. It was also confirmed that the nucleophilic behavior of [( L )Ge] as a two lone‐pair donor.     

Quaternary Germanides RE3TRh4Ge4 (RE = Ce,Pr, Nd; T = Nb,Ta) – A New Coloring Variant of the Aristotype AlB2

The quaternary germanides RE₃TRh₄Ge₄ (RE = Ce, Pr, Nd; T = Nb, Ta) were synthesized from the elements by arc‐melting and subsequent annealing in a muffle furnace. The structure of Ce₃TaRh₄Ge₄ was refined from single‐crystal X‐ray diffractometer data: new type, Pbam, a = 719.9(2), b = 1495.0(3), c = 431.61(8), wR₂ = 0.0678, 1004 F² values, and 40 variables. Isotypy of the remaining phases was evident from X‐ray powder patterns. Ce₃TaRh₄Ge₄ is a new superstructure variant of the aristotype AlB₂ with an ordering of cerium and tantalum on the aluminum site, whereas the honey‐comb network is built up by a 1:1 ordering of rhodium and germanium. This crystal‐chemical relationship is discussed based on a group‐subgroup scheme. The distinctly different size of tantalum and cerium leads to a pronounced puckering of the [Rh₄Ge₄] network, which shows the shortest interatomic distances (253–271 pm Rh–Ge) within the Ce₃TaRh₄Ge₄ structure. Another remarkable structural feature concerns the tantalum coordination with six shorter Ta–Rh bonds (265–266 pm) and six longer Ta–Ge bonds (294–295 pm). The [Rh₄Ge₄] network fully separates the tantalum and cerium atoms (Ce–Ce > 387 pm, Ta–Ta > 431 pm, and Ce–Ta > 359 pm). The electronic density of states DOS from DFT calculations show metallic behavior with large contributions of localized Ce 4f as well as itinerant ones from all constituents at the Fermi level but no significant magnetic polarization on Ce could be identified. The bonding characteristics described based on overlap populations illustrate further the crystal chemistry observations of the different coordination of Ce1 and Ce2 in Ce₃TaRh₄Ge₄. The Rh–Ge interactions within the network are highlighted as dominant. The bonding magnitudes follow the interatomic distances and identify differences of Ta bonding vs. Ce1/Ce2 bonding with the Rh and Ge substructures.     

The Crystal Structures of Eu5Ge3 and EuIrGe2

Eu₅Ge₃ and EuIrGe₂ were prepared from the elements in tantalum tubes, and their crystal structures were determined from single crystal X-ray data. Eu₅Ge₃ adopts the structure of Cr₅B₃: I4/mcm, a = 799.0(1)pm, c = 1 536.7(1)pm, Z = 4, wR2 = 0.0421 for 669 F² values and 16 variables. The structure of Eu₅Ge₃ contains isolated germanium atoms and germanium atom pairs with a Ge? Ge distance of 256.0 pm. Eu₅Ge₃ may be described as a Zintl phase with the formulation [5 Eu²⁺]¹⁰⁺[Ge]^4?[Ge₂]^6?. Magnetic investigations of Eu₅Ge₃ show Curie-Weiss behaviour above 50 K with a magnetic moment of μ_exp = 7.6(1) μ_B which is close to the free ion value of μ_eff = 7.94 μ_B for Eu²⁺. EuIrGe₂ is isotypic with CeNiSi₂: Cmcm, a = 445.5(2) pm, b = 1 737.4(4) pm, c = 426.6(1) pm, Z = 4, wR2 = 0.0507 for 295 F² values and 18 variables. The structure of EuIrGe₂ is an intergrowth of ThCr₂Si₂-like slabs with composition EuIr₂Ge₂ and AlB₂-like slabs with composition EuGe₂ in an AB stacking sequence. Both slabs are distorted when compared to the symmetry of the prototypes. The Ge? Ge distance of 256.6 pm in the AlB₂-like fragment is comparable to that in Eu₅Ge₃.     

Beiträge zur Chemie der Schwefelhalogenide. 12. Triphenylmethyl-chlorsulfan, -bromsulfan und -iodsulfan

Contribution to the Chemistry of Sulfur Halides. 12. Triphenylmethane-chlorosulfane, -bromosulfane, and -iodosulfane Vibrational frequencies of the triphenylmethanehalogenosulfanes Ph₃CSX (X = Cl, Br, I) are assigned under special consideration of the S—I frequency at 370 cm^?1. Ph₃CSBr crystallizes in the triclinic space group P1 with a = 877.1(4) pm, b = 939.7(9) pm, c = 1035.5(9) pm, α = 113.29(9)°, β = 98.88(9)°, γ = 97.34(9)°, Z = 2 and d(S–Br) = 216.9(2) pm according to a X-ray structure analysis at 163 K.     

Synthetic and structural studies on some 1,3-diselena- and 1,3-dithia-[3]ferrocenophanes of germanium and tin. crystal and molecular structure of 1,3-diselena-2,2- dichlorogermyl-[3]ferrocenophane

A series of [3]ferrocenophanes of general formula Fe(C₅H₄X)₂YCl₂ and the spiro compounds [Fe(C₅H₄X)₂]₂Ge (X = S, Se; Y = Ge, Sn) have been prepared by the reaction of ferrocene 1,1′-dithiol and ferrocene 1,1′-diselenol with tetrahalides of germanium and tin. Spectroscopic properties of the compounds are reported. In solution, the compounds are fluxional by a bridge reversal process. The crystal structure of 1,3-diselena-2,2-dichlorogermyl-[3]ferrocenophane at 163 K. has been determined by X-ray diffraction methods. At that temperature, crystals have space group P2₁/n with a 6.222(3), b 16.156(13), c 12.968(4) Å, β 97.53(1)° and Z = 4. Least-squares refinement gave R = 0.033 for 2834 unique significant reflections whose intensities were measured by counter diffractometry. The two SeGe bond lengths are 2.323 and 2.325(1) Å, with GeCl 2.148 and 2.161(1) Å. The SeGeSe bond angle is 118.2(1)°, ClGeCl 104.7(1)°, and SeGeCl angles range from 106.2 to 109.8(1)°. The SeC bond lengths are 1.901 and 1.904(5) Å, with CSeGe angles of 95.8 and 96.5(2)°. The cyclopentadienyl rings are in an eclipsed conformation with a mean twist angle of 2.7°, and are inclined to one another at 6.1°. The Se atoms are displaced from the ring planes by 0.17 and 0.20 Å yielding a non-bonded intramolecular Se…Se contact of 3.99 Å.     

Neue Sr‐Verbindungen mit planaren Al‐Si/Ge‐Anionen und eine Korrektur zu SrSi‐II und SrGe0.76

New Sr Compounds with Planar Al‐Si/Ge Anions and a Correction of SrSi‐II and SrGe_0.76 Planar anions with considerable p_π‐p_π interactions between heavier group 13 and 14 elements are observed in several alkaline earth trielides and tetrelides. In the intermetallics of the series SrAlxGe_2?x (border phases: x = 1: , a = 429.4(3), c = 474.4(3) pm, Z = 1, R1 = 0.0305, SrPtSb type and x = 1.6: P6/mmm, a = 440.4(2), c = 478.2(2) pm, Z = 1, R1 = 0.0125, AlB₂ type) graphite analogue planar Al/Ge nets with short Al‐Ge bonds are stacked in identical orientation, showing inter‐layer distances of approx. 475 pm. Starting from the related planar ribbons of condensed six‐membered rings in the known intermetallics (M^IV = Si, Ge) a series of new metal‐rich oxides with chain pieces consisting of three, two and finally only one six‐membered ring have been prepared and characterized on the basis of single crystal X‐ray data. The formal fragmentation of the ribbons is achieved by the incorporation of [OSr₆] octahedra, chains of which (connected via common corners) exactly fit the distance between the planar anions. The structures of the two compounds (M^IV = Si, Ge; formerly erroneously reported as SrSi and SrGe_0.76, space group Immm, a = 482.48(5)/484.55(8), b = 1306.5(2)/1342.2(2), c = 1814.0(2)/1857.4(3) pm, Z = 2, R1 = 0.0369/0.0316) contain isolated planar anions [M₂Al₂M₂Al₂M₂]^18? with only one six‐membered ring. In the monoclinic structures of the silicide Sr₁₃[Al₆Si₈][O] (C2/m, a = 2245.1(4), b = 482.76(5), c = 1720.6(5) pm, β=125.21(2)°, Z = 2, R1 = 0.0579) and the germanide Sr₁₆[Al₈Ge₁₀][O] (C2/m, a = 2287.23(14), b = 484.94(3), c = 2065.70(13) pm, β=120.150(4)°, Z = 2, R1 = 0.0730) anions [Si₂Al₂Si₂Al₂Si₂Al₂Si₂] and [Ge₂M₂Ge₂M₂Ge₂M₂Ge₂M₂Ge₂] with two and three six‐membered rings are left as fragments of the ribbons in Sr₃Al₂M₂. The puzzling bonding situation in these type of polar intermetallics at the Zintl border is calculated (using the DFT FP‐LAPW approach) for the structures with manageably small unit cells and discussed for the series SrAlM – Sr₃Al₂M₂ – Sr₁₆[Al₈M₁₀][O] – Sr₁₃[Al₆M₈][O] – Sr₁₀[Al₄M₆][O].     

Germanates of 1D Chains, 2D Layers,and 3D Frameworks Built from Ge–O Clusters by Using Metal‐Complex Templates: Host–Guest Symmetry and Chirality Transfer

The self‐assembly of Ge–O polyhedra by metal‐complex templates leads to initial examples of open germanate structures under mild solvothermal conditions. These materials are constructed from Ge–O cluster building bocks (Ge₇X₁₉ (X=O, OH, or F) or Ni@Ge₁₄O₂₄(OH)₃) and span the full range of dimensionalities from 1D chains of Ge₇O₁₃(OH)₂F₃?Cl?2[Ni(dien)₂] (FJ‐ 6 ) to 2D layers of Ge₇O₁₄F₃?0.5[In(dien)₂]?0.5H₃dien? 2H₂O ( 1 ) and 3D frameworks of Ni@ Ge₁₄O₂₄(OH)₃?2[Ni(L)₃] (FJ‐ 1 a /FJ‐ 1 b ) (dien=diethylenetriamine, L=ethylenediamine (en) or 1,2‐diaminopropane (enMe)). The Ge₇X₁₉ cluster in FJ‐ 6 and 1 is formed by condensation of four GeX₄ tetrahedra, two GeX₅ trigonal bipyramids, and one GeX₆ octahedron with a μ₃‐O atom at the center of the cluster, whereas the Ni@ Ge₁₄O₂₄(OH)₃ cluster in FJ‐ 1 a /FJ‐ 1 b is formed by condensation of nine peripheral GeO₄ tetrahedra and five interior GeO₃Ni units with one μ₅‐Ni atom at the center of the cluster. FJ‐ 6 is characterized by a pair of racemic Ge₇O₁₄(OH)₂F₃ cluster chains and represents only one example of 1D germanates; 1 exhibits unique germanate layers with uniform 10‐membered‐ring apertures encapsulating an unknown indium complex, and the framework structure of FJ‐ 1 a /FJ‐ 1 b with large 24‐membered‐ring channels is the first example of porous materials that contain metal–metal bonds (Ge²⁺? Ni⁺). These initial examples of germanates from metal‐complex templates provide a useful model system for understanding the mechanisms of host–guest interactions, which may further facilitate the design and development of new porous materials “on demand”. It is shown that the symmetry and configuration of the guest metal complex can be imprinted onto the host inorganic framework through hydrogen bonding between host and guest.