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C14H20Cl6N8O5Pt, monoclinic, P21/n(no. 14), a= 13.4907(2) Å, b= 13.32240(10) Å, c= 13.8035(2) Å, β= 102.241(1)∘, Z= 4, V= 2424.48(5) Å3, Rgt(F) = 0.0256, wRref(F2) = 0.0740, T= 290 K.

C19H14FN5O, monoclinic, P21/c(no. 14), a= 7.2944(3) Å, b= 12.2032(5) Å, c= 18.1070(7) Å, β= 95.807(4)°, V= 1603.52(11) Å3, Z= 4, Rgt(F) = 0.0451, wRref= 0.1217, T = 100(2) K.

C18H21FN2O, triclinic, P1‾$P\overline{1}$(no. 2), a= 10.6377(5) Å, b= 14.4869(7) Å, c= 21.0557(13) Å, α= 98.583(5)°, β= 91.979(4)°, γ= 90.101(4)°, V= 3206.5(3) Å3, Z= 8, Rgt(F) = 0.0815, wRref(F2) = 0.1930, T= 172 K.

C5H6BrN3, orthorhombic, P212121(no. 19), a= 3.82640(10) Å, b= 8.7336(2) Å, c= 18.6007(3) Å, V= 621.60(2) Å3, Z= 4, Rgt(F) = 0.0184, wRref= 0.0473, T= 100(2) K.

C21H23N5O6, monoclinic, P21/c(no. 14), a= 8.4861(4) Å, b= 16.3198(8) Å, c= 15.8521(8) Å, β= 97.605(5)°, V= 2176.1(2) Å3, Z= 4, Rgt(F) = 0.0463, wRref= 0.1201, T= 293(2) K.

By the reaction of (dimethylphosphoryl)methanamine (dpma) with one equivalent of zinc(II) chloride in a concentrated hydrochloric acid solution and subsequent slow evaporation of the solvent, the title compound (dpmaH)ZnCl3was obtained in quantitative yield. The primary reaction product mainly consists of larger brick-shaped colorless and smaller cuboide colorless crystals. Long-time storage over several months of these crystals in the mother liquor yielded a third polymorph (P21/n; a= 9.6639(1); b= 10.0271(1); c= 11.2446(1) Å; β= 98.964(1)°) of this compound. Similar to the two other modifications, its crystal structure consists of a zwitterionic dpmaHZnCl3complex containing the cationic dpmaH+ligand, which coordinates the zinc atom through its oxygen atom. Hydrogen bonds connect neighboring zwitterionic complexes to a layered structure. The motif of a hydrogen bonded dimer, similar to that found in the chain structure of polymorph I, is also present, but in the title structure these dimers form hydrogen bonds in two dimensions.

C7H11I3N4O3, triclinic, P1‾$P\overline{1}$ (no. 2), a= 9.28478(14) Å, b= 12.2214(2) Å, c= 13.4088(2) Å, α= 76.2062(14)°, β= 88.2421(13)°, γ= 89.4102(13)°, Z= 4, V= 1476.95(4) Å3, Rgt(F) = 0.0198, wRref= 0.0494, T= 100 K.

C10H16N2SnCl6, monoclinic, I2 (no. 5), a= 14.0477(4) Å, b= 8.9140(2) Å, c= 27.6199(6) Å, β= 93.060(2)°, Z= 8, V= 3453.67(15) Å3, Rgt(F) = 0.0395, wRref= 0.0858, T= 290 K.

C10H10N2SnCl6, monoclinic, I2/a(no. 15), a= 7.4941(3) Å, b= 12.8731(4) Å, c= 15.8688(5) Å, β= 93.042(3)°, Z= 4, V= 1528.73(9) Å3, Rgt(F) = 0.0264, wRref= 0.0485, T= 100 K.

C21H33Cl9Fe2N12O9, trigonal, R3‾$R\overline{3}$ (no. 148), a= 13.1897(3) Å, c= 39.5222(9) Å, Z= 6, V= 5954.4(3) Å3, Rgt(F) = 0.0255, wRref(F2) = 0.0743, T = 120 K.

C14H18N8O8SnCl6, monoclinic, P21/n(no. 14), a= 8.1810(2) Å, b= 12.6195(3) Å, c= 11.3811(2) Å, β= 90.258(2)°, Z= 2, V= 1174.97(5) Å3, Rgt(F) = 0.0266, wRref= 0.0620, T= 290 K.

Dibrominated bis[1]benzothieno[3,2-b;2′,3′-e][1,4]thiazines (BBTT) are efficiently synthesized and applied in Suzuki and Buchwald–Hartwig cross-coupling reactions to give access to 3,9-disubstituted BBTT derivatives with extended π-conjugation and enhanced electronic properties. For instance, 3,9-di(hetero)aryl substituted BBTT derivatives surpass their parent congeners phenothiazines with lower oxidation potentials and pronounced yellow to orange-red fluorescence (Φf≈ 30–45%). In addition, 3,9-bis(di(hetero)arylamino substituted BBTT possess very high lying HOMO energy (EHOMO= −4.46 to −4.83 eV), a favorable property of hole transport molecules. A representative X-ray structure analysis reveals that the central BBTT core in these extended π-systems is essentially planarized. Upon protonation of a 3,9-bis(di(hetero)arylamino) substituted BBTT, the absorption color shifts from yellow to deep blue with a concomitant loss of the emission. The optical properties of these novel BBTT derivatives can be plausibly rationalized by time-dependent density functional theory (TD(DFT)) calculations and correlation between experimentally determined oxidation potentials and σpparameters as well as between photophysical data and the specific substituent parameter σp–by establishing electronic structure–property relationships.

C18H20Cl4N2OZr, monoclinic, Pnma(no. 62), a= 12.457(3) Å, b= 22.806(8) Å, c= 7.398(2) Å, V= 2101.7(11) Å3, Z= 4, Rgt(F) = 0.0291, wRref(F2) = 0.0685, T= 110 K.

C10H16I4ZnN2, monoclinic, P21(no. 4), a= 7.3340(1) Å, b= 14.4781(3) Å, c= 8.6768(2) Å, β= 94.919(2)°, V= 917.93(3) Å3, Z= 2, Rgt(F) = 0.0165, wRref(F2) = 0.0397, T= 110 K.

C10H18Cl4ZnN2O, orthorhombic, P212121(no. 19), a= 7.0752(1) Å, b= 7.5085(1) Å, c= 29.3383(5) Å, V= 1558.57(4) Å3, Z= 4, Rgt(F) = 0.0330, wRref(F2) = 0.0672, T= 290(2) K.

C6H7I4N, monoclinic, P21/m(no. 11), a= 9.2818(2) Å, b= 6.55289(16) Å, c= 11.0561(3) Å, β= 114.051(3)°, V= 614.08(3) Å3, Z= 2, Rgt(F) = 0.0180, wRref(F2) = 0.0367, T= 109(2) K.

C8H16Cl3NO2, monoclinic, P21(no. 4), a= 9.1804(5), Å, b= 19.4133(10) Å, c= 13.9191(7) Å, β= 90.593(3)°, V= 2480.6(2) Å3, Z= 8, Rgt(F) = 0.0605, wRref(F2) = 0.1387, T= 296(2) K.

Two regioisomers of bis[1]benzothieno[1,4]thiazine are unexpectedly obtained by tuning the catalytic conditions of the intermolecular–intramolecular Buchwald–Hartwig amination. Mechanistic insights and evidence of intermediates support a conclusive mechanistic rationale. Furthermore, a computationally based study on the influence of conformational aspects on the HOMO energy level of anellated 1,4-thiazine paves the way to enhance the electronic properties, thus successfully achieving higher luminescent and easier oxidizable syn–synbis[1]benzothieno[1,4]thiazines.

C13H17Cl2NO2, triclinic, P1 (no. 1), a= 7.1486(3) Å, b= 7.8265(3) Å, c= 13.6579(5) Å, α= 81.085(3)°, β= 77.487(4)°, γ= 73.335(4)°, Z= 2, V= 711.13(5) Å3, Rgt(F) = 0.0536, wRref= 0.0878, T= 290 K.

C8H14Br2N2, monoclinic, I2/a(no. 15), a= 9.0331(9) Å, b= 13.4475(14) Å, c= 27.586(3) Å, β= 94.879(9)°, Z= 12, V= 3338.8(6) Å3, Rgt(F) = 0.0582, wRref= 0.0885, T= 290 K.

1,3,5-Trisubstituted adamantane carboxamide and amine hydrochloride, Ad(CONH2)3·2.5H2O and [Ad(NH3)3]Cl3·H2O (Ad = adamant-n-yl) respectively, crystallized from aqueous solutions, possess crystal structures with predictable H-bonded assembly, consistent with the C3vsymmetry of the building blocks. The triamide structure consists of interpenetrated hexagonal networks, sustained by the well-known cyclic H-bonded bis-amide synthon, R22(8), which ensures linear connectivity. The structure of the triamine hydrochloride, assembled through the tetrahedral {RN+H3···(Cl–)3} synthon, features a remarkably symmetric assembly with narrow trigonal pore channels, hosting water molecules. The structures of the tetrahedral 1,3,5,7-tetrasubstituted Ad(CONH2)4and [Ad(NH3)4]Cl4, obtained similarly, demonstrate a formal prediction failure of synthon-based approach. Instead of the anticipated bis-amide synthon-based diamond network (1.485 g cm–3) analogous to the 5-fold interpenetrated paradigmatic structure of Ad(COOH)4, a non-interpenetrated assembly, sustained by a dense network of H-bonds, is realized (1.433 g cm−3). Lessened geometric regularity was also found in the tetrahydrochloride salt assembled via 5-connected nodes, {RN+H3···(Cl–)4}, which involve a bifurcated H-bond. The failures of the supramolecular synthons in these simple cases could be interpreted in terms of either symmetry and/or limitations associated with the “synthon density”. A potential machine-learning approach oriented on heuristic retro-supramolecular synthesis relies on such selected high-weight conceptual cases.

C10H16Cl4MnN2, monoclinic, P21(no. 4), a= 7.28276(7) Å, b= 13.22972(12) Å, c= 8.01007(7) Å, β= 97.5018(9)°, V= 765.155(12) Å3, Z= 2, Rgt(F) = 0.0165, wRref(F2) = 0.0392, T= 123(2) K.

C16H21I3N8O4, monoclinic, P21/n(no. 14), a= 14.7257(7) Å, b= 10.5712(5) Å, c= 16.7501(8) Å, β= 114.408(2)°, V= 2374.4(2) Å3, Z= 4, Rgt(F) = 0.0254, wRref(F2) = 0.0760, T = 290(2) K.

Methyl α-cyano β-(hetero)aryl acrylates are excellent substrates for CAL-B catalyzed aminolyses. However, upon concatenation of the substrate Knoevenagel condensation (of (hetero)aryl carbaldehydes and methyl cyano acetate) and the CAL-B catalyzed aminolysis, an interesting bifurcating domino Knoevenagel-CAL-B catalyzed aryl methylaminolysis/hydrolysis reaction furnishing either amides or salts in the sense of a three-component process was found. The enzyme mediated acylative bifurcation of water vs benzyl amines depends on the substitution pattern of the aldehydes and on the presence or absence of a water scavenger. In the former case, amidation is favored while in the latter case hydrolysis/salt formation prevails.

The reaction of dpma(dpma=(dimethylphosphoryl)methanamine) with hydroiodic acid in the presence of an excess of elemental iodine gives red coloured crystals of (dpmaH)3(H3O)I4·1/2I2(1) as the main product and a small amount of a by-product (dpmaH)2[I3]2·dpma(2). Single crystal structure determinations on both compounds were carried out. In the crystal structure of 1(space group P3̅, a=12.2166(3) Å, c=10.8788(4) Å, Rgt(F)= 0.0224, wRref(F2)=0.0377), six symmetry related dpmaH+cations and iodide anions, both located in general positions, form a cage through NH···I hydrogen bonds. These cages are connected to neighbouring ones by H3O+cations by means of strong OH···O hydrogen bonds, thereby constructing a 2-dimensional network perpendicular to the cdirection. In the center of each cage a three-fold disordered I2molecule is present. This disorder is a consequence of space group symmetry. Each iodine molecule forms two halogen bonds to two adjacent iodide anions (Δ(I···I)=3.2449(7) Å) formally resulting in an almost linear I42−anion. The second iodide counter anion is located alternatively beneath and below the H3O+cation and is not involved in any stronger hydrogen bonding interaction. The dominant feature of the crystal structure of 2(space group C2/c, a=28.885(5) Å, b=10.6854(15) Å, c=20.659(4) Å, β=110.64(2)°, Rgt(F)=0.0776, wRref(F2)=0.1410) is a ladder substructure formed by dpmaH cations and neutral dpmamolecules viaNH···O and NH···N hydrogen bonds. Triiodide counter anions occupy gaps in the ladder. A characteristic Raman signal representing the iodine molecule in the Raman spectrum of 1is shifted to lower wavenumbers (173 cm−1). It corresponds to an iodine molecule trapped in the cage of a hydrogen bonded network forming medium strong halogen bonds. The Raman spectrum of 2shows the typical bands of a weakly connected I3−anion.

C7H9I5N4O2, monoclinic, P21/c(no. 14), a= 9.46793(10) Å, b= 11.58276(12) Å, c= 16.41497(18) Å, β= 100.844(1)°, Z= 4, V= 1768.00(3) Å3, Rgt(F) = 0.0306, wRref(F2) = 0.0728, T= 130(2) K.

The reaction of S-nicotine with hydroiodic acid in the presence of iodine gave the new polyiodide-containing salt nicotine-1,1′-diium bis(triiodide)-diiodine (1/1) (C10H16N2) [I3]2·I2(1). The title compound has been characterised by spectroscopic methods (Raman and IR) and single-crystal X-ray diffraction. The asymmetric unit of the title structure consists of one dication, two triiodide anions, and one iodine molecule, all located in general positions in the non-centrosymmetric space group P1. One of the two crystallographically independent triiodide anions and the doubly protonated nicotinium dication form hydrogen-bonded chains along b, which are arranged parallel to each other in the ½bcplane. The second crystallographically independent triiodide anion and the iodine molecule form an I5–moiety, which is end-on connected to two symmetry-related anions resulting in polyiode zig–zag chains along the [0 1 1̅] direction. These polyiodide chains are stacked parallel to each other in the 0bcplane. The Raman spectrum of the title compound shows characteristic lines in the 50–200 cm–1range, which are in excellent agreement with the findings derived from the crystal structure.

In a comparative structural study, the solid state structures within the homologous series of alkane-α,ω-diphosphonic acids, H2O3P–(CH2)n–PO3H2with n= 6–12, have been characterised by powder and single crystal X-ray diffraction. The crystal structures of the odd-numbered diphosphonic acids were found to be homotypic. For the even-numbered diphosphonic acids – including the two already known polymorphs of butane-1,4-diphosphonic acid – two different types are found. Basically, all alkane-α,ω-diphosphonic acids exhibit pillared-layered structures with their terminal groups forming two-dimensional hydrogen bonded networks which are covalently bridged by alkylene chains. Structural differences occur within the hydrogen bonding systems as well as in the arrangement of the alkylene chains. Based on the existence of different structure types of the alkane-α,ω-diphosphonic acids, the progression of their melting points can be explained.

Irradiation of tricarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)manganese (1) in tetrahydrofuran (THF) at 208 K affords the carmine solvent complex dicarbonyl(η5-2,4-dimethyl-2,4-pentadien-1-yl)(THF)manganese (2). Complex 2thermally reacts with acetylene (3) to give tricarbonyl(η3:2-1,3-dimethyl-bicyclo[3.3.1]-3,6-nonadien-2-yl)manganese (4) and dicarbonyl(5-7,10-13-η-6,8-dimethyl-1,3,5,8,10,12-tridecahexaen-5-yl)manganese (5). The crystal structure of complex 4was determined at room temperature [triclinic space group P1¯,$P\bar 1,$a=7.6891(9), b=8.3860(8), c=10.5252(13) Å, α=93.000(9)°, β=93.390(10)°, γ=108.032(8)°, V=642.43(13) Å3]. The manganese atom is trigonal-bipyramidally coordinated by three carbonyl ligands, one ethenylic and one allylic fragment. Consequently, the bicyclic olefin ligand 1,3-dimethyl-bicyclo[3.3.1]-3,6-nonadiene coordinates the manganese atom in a η3:2mode. The constitution of complex 5was deduced from IR data, elemental analysis, and 1H NMR spectra. For the formation of complexes 4and 5, a reaction mechanism is proposed.

The reaction of 2,2-dimethylpropane-1,3-diamine with hydroiodic acid in the presence of iodine gave a new polyiodide best described as bis(2,2-dimethylpropane-1,3-diazanium) tetraiodidediiodine (1 : 1), (C5H16N2)2I4·I2(1). The title compound can be transformed into the known 2,2-dimethylpropane-1,3-diazanium diiodide, (C5H16N2)I2(2), upon iodine release at 433 K and 2 × 10−3mbar. Both compounds have been characterised by spectroscopic methods (Raman and IR) and powder diffraction. For 1the single-crystal structure determination has been successful. The asymmetric unit of 1consists of one half 2,2-dimethylpropane-1,3-diazanium cation and two half iodide anions, all lying in a mirror plane. In addition, there is one quarter of an iodine molecule located near to a centre of inversion (2/m site) which is disordered over two positions with occupancy factors of 0.22 and 0.78. The structure of the title compound contains cube-shaped structural units in which the -NH3+groups of four 2,2-dimethylpropane-1,3-diazanium cations occupy the corners. The iodide anions lie near the midpoints of eight of the twelve edges, and the disordered iodine molecule fills the void in the centre. Weak I...I interactions between the disordered iodine molecules and adjacent iodide anions may also allow a description as conceivable I42−dianions. The cube-type building units are further connected to adjacent ones by weak to medium strong N-H...I hydrogen bonds resulting in a two-dimensional layered structure parallel to the ab plane.

The reaction of 1,4-diaminobutane with hydroiodic acid in the presence of iodine yields the title compound 1,4-diazaniumbutane tetraiodide, C4H14N2I4(1). The title compound has been structurally characterized by crystallographic and spectroscopic methods (Raman and IR). 1is built up by centrosymmetric 1,4-diazaniumbutane cations in all-trans conformation and linear I42-anions. Both, cations and anions are located on centers of inversion (2/m) in the monoclinic space group C2/m. The hydrogen bonds between the azanium groups and the terminal iodine atoms of the I42-anions lead to a three-dimensional framework. The structural parameters of the tetraiodide anion, derived from X-ray crystallographic data are in excellent agreement with the results from Raman spectroscopy. The Raman and IR data for the analogous a,w-diazaniumalkane tetraiodide salts (H3N-(CH2)6-NH3)I4(2) and (H3N-(CH2)7-NH3)I4(3) are reported, and the structures of 1, 2and 3are compared.

The reaction of bipyridine with hydroiodic acid in the presence of iodine gave two new polyiodide-containing salts best described as 4,4´-bipyridinium bis(triiodide), C10H10N2[I3]2, 1, and bis(4,4´-bipyridinium) diiodide bis(triiodide) tris(diiodine) solvate dihydrate, (C10H10N2)2I2[I3]2· 3 I2·2H2O, 2. Both compounds have been structurally characterized by crystallographic and spectroscopic methods (Raman and IR). Compound 1 is composed of I3 − anions forming one-dimensional polymers connected by interionic halogen bonds. These chains run along [101] with one crystallographically independent triiodide anion aligned and the other triiodide anion perpendicular to the chain direction. There are no classical hydrogen bonds present in 1. The structure of 2 consists of a complex I144−anion, 4,4´-bipyridinium dications and hydrogen-bonded water molecules in the ratio of 1 : 2 : 2. The I144−polyiodide anion is best described as an adduct of two iodide and two triiodide anions and three diiodine molecules. Two 4,4´-bipyridinium cations and two water molecules form a cyclic dimer through N-H· · ·O hydrogen bonds. Only weak hydrogen bonding is found between these cyclic dimers and the polyiodide anions.

CO‐releasing molecules (CORMs) were coordinated to polymeric carrier systems for passive transport to tumour tissue or sites of inflammation, as described by the enhanced permeability and retention (EPR) effect. The developed conjugates consist of an organometallic fac‐Mn(CO)3fragment, which is bound to a methacrylate or methacrylamide polymer backbone by bis(pyridylmethyl)amine‐type ligands. The resulting Mn(CO)3–polymer conjugates were investigated as photoinducible CO‐releasing molecules (photoCORMs). Furthermore, three model complexes [LMn(CO)3]O2SCF3containing N,N,N‐ligands L = bis(pyridylmethyl)amine (bpma), bis(pyridylmethyl)ethanolamine (bpmea) and bis(pyridylmethyl)‐p‐vinylbenzylamine (bpmvba) were also investigated. The solid‐state structure of the bromide complex [(bpmea)Mn(CO)3]Br.(CH3)2CHOH (4·(CH3)2CHOH) was determined by X‐ray analysis. The complexes and the polymer conjugates show photoCORM activity with polymer molecular weights and size distributions suitable for passive drug delivery.

C10H18Cl4CoN2O, orthorhombic, P212121(no. 19), a= 7.0057(3) Å, b= 7.4317(3) Å, c= 29.2510(13) Å, V= 1522.93(11) Å3, Z= 4, Rgt(F)= 0.0356, wRref(F2)= 0.0737, T= 110 K.

[Me(HO)2P-(CH2)10-P(O)OHMe]2[I3]2·MeHO(O)P-(CH2)10-P(O)OHMe (1) was synthesized and characterized by IR, Raman and NMR spectroscopy. Its structure was determined by singlecrystal X-ray diffraction (T = 100 K; space group P1¯). The structure consists of decane-1,10-diyl-bis- (methylphosphinic acid) molecules and the analogous mono-protonated cations in a ratio 1:2 connected with each other by strong O-H···O hydrogen bonds to form a two-dimensional network. Between these hydrogen-bonded layers, there are elongated cavities each containing two triiodide anions. The intermolecular I· · · I distance of the two enclosed triiodide anions is 3.6317(4) Å and should be considered as an interhalogen bonding interaction.

Square planar arenidotriphenylphosphanenickelII complexes 3 containing a N,Ochelate ligand are catalysts for the carbon monoxideethene copolymerisation reaction. Pathways for catalyst deactivation have been elucidated by investigating the reactions of such complexes with aliphatic unsaturated compounds like olefins and alkynes. We have shown that the double or triple bond, respectively, inserts into the nickel–carbon bond followed by βhydride elimination resulting in arylsubstituted olefins and allenes, which have been identified by means of GCMS. The remaining nickel forms a bisN,Ochelate ligandnickel complex, the crystal structure of which has been determined. The nickel atom is coordinated in a squareplanar manner by two ligands. Additional coordination of two neighbouring complexes via their nitrile groups completes the coordination of the nickel to a distorted octahedron and forms a twodimensional metalorganic framework MOF.

Diisopropylammonium trifluoroacetate ({[iPr2NH2][CF3COO]}; dip tfa; 1) and diisopropylammonium pentafluoropropionate ({[iPr2NH2][C2F5COO]}; dip pfp; 2) have been synthesized and structurally characterized by X-ray diffraction and spectroscopic methods. Both compounds form hydrogen-bonded cyclic dimers (Etter symbol: R44(12)) in the solid state. The asymmetric unit of 1 contains one trifluoroacetate anion and one dip cation in the centrosymmetric space group Pi. The asymmetric unit of 2 consists of two crystallographically independent pentafluoropropionate anions and two independent dip cations forming dimers in the form of rings, both lying around centers of symmetry in the space group Pi. In dip tfa and dip pfp the cations act as double hydrogen bond donors, and each of the two oxygen atoms of the carboxyl group are single hydrogen bond acceptors. The donor acceptor distances of the N-H...O hydrogen bonds are within the expected range for medium strong hydrogen bonds. The quasi-molecular cyclic dimers are connected with neighboring units only by van der Waals interactions.

Reactions of [3-NC-B11F10]2–with aqueous bases resulted in a cluster degradation. From the reaction mixtures, salts of the [B3O3F2(OH)2]–anion (1) with [Ph4P]+or [Ph3MeP]+as countercations were isolated. Both salts were investitgated by single-crystal X-ray diffraction. In the solid state the triborate anions form infinite hydrogen-bonded chains. In the [Ph4P]+salt the anions and the chains are coplanar, whereas in the [Ph3MeP]+salt the planes of the anions are twisted against each other. The bonding parameters of the anion are compared to values of the related [B3O3(OH)4]–anion (2) and to values derived from density functional calculations. In addition, the triborate anion 1was characterized by 11B and 19F NMR spectroscopy as well as by MALDI mass spectrometry. The experimental chemical shifts are compared to calculated values (DFT-GIAO).(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Synthesis and Characterization of the Compounds AIrP (A: La – Nd; Sr)

The reaction of 1,9-diaminononane with hydroiodic acid in the presence of iodine gave a compound best described as 1,9-diammoniononane bis-triiodide iodine, (H3N-(CH2)9-NH3)[I3]2· I2. The structure is built from two crystallographically independent I3-anions, which are connected via secondary I···I interactions to the iodine molecules, and the 1,9-diammonioalkane cations are connected via weak hydrogen bonds to neighbouring iodine atoms. By a cooperative phenomenon, the shape and the functionality of the cation lead to a solid state structure that includes a polyiodide substructure with the formula 28[I8]2-or 28[I3· I2· I3]2-, is best described as a brick-shaped layered array. Its rectangular pores fit excellently with the hydrogen bonding functionality as well as with the conformational needs of the 1,9-diammoniononane template. The Raman spectrum shows typical bands of coordinated triiodide anions and iodine molecules. The thermal analysis (DSC/TG) of the title compound indicates decomposition at temperatures above 210°C.

Tris[2-isopropylimidazol-4(5)-yl]phosphane (4-TIP^iPr), a novel model ligand for the tris(histidine) motif of many zinc enzymes, has been prepared. 4-TIP^iPr is hydrolytically stable and soluble in protic solvents. It readily forms chloro- and nitratocobalt, -nickel and -zinc complexes in aqueous methanol. The crystal structures of the solvates [(4-TIP^iPr)Co(MeOH)(NO3)]NO3·2Et2O (3·2Et2O), [(4-TIP^iPr)Ni(MeOH)(NO3)]NO3·Et2O·MeOH (4·Et2O·MeOH), [(4-TIP^iPr)CoCl]Cl·MeOH·2.5H2O (5·MeOH·2.5H2O), and [(4-TIP^iPr)ZnCl]Cl·MeOH·2.5H2O (6·MeOH·2.5H2O) have been determined. The complex 3 shows striking structural similarities to the hydrogencarbonate complex of cobalt-substituted human carbonic anhydrase II (HCA II). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

The thallium(I) salts of tris(pyrazolyl)methanesulfonate (Tpms) and tris(3-tert-butylpyrazolyl)methanesulfonate (Tpms^tBu) have been used to prepare the following complexes: [(Tpms^tBu)ZnX] [X = Cl (1a), Br (1b), I (1c), Et (3), OAc (5a)], [(Tpms^tBu)NiX] [X = Cl (2a), Br (2b)], [(Tpms^tBu)CoCl(Hpz^tBu)] (3), [(Tpms^tBu)Zn(μ-OAc)(μ-OH)Zn(Tpms^tBu)] (5b), [(Tpms^tBu)Cu(CO)] (6a), and [(Tpms)Cu(CO)] (6b). The solid-state structures of 1b, 2a, 3, and 5b have been determined by X-ray analysis. The optical spectra of 2a and 3 were investigated by means of the angular overlap model to elucidate their electronic structures in view of the underlying molecular geometries. Variable-temperature NMR and IR spectroscopic studies show that Tpms and Tpms^tBu can act as N,N,N and N,N,O ligands. Both coordination modes are present in solution for the zinc complexes 1a,b and the copper carbonyl complexes 6a,b. The N,N,O bonding mode is entropically favoured in solution. For the nickel complexes 2a,b, the Tpms^tBu ligand acts as a tripodal nitrogen ligand in the solid state and in solution. For the dinuclear zinc complex 5b, one of the Tpms^tBu ligands acts as an N,N,O ligand and one as an N,O ligand. Complex 5b is one of the very few structural models of the dinuclear zinc enzymes phospholipase C and phosphotriesterase. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

cis-3,4-Diaminopyrrolidine (cis-dap), trans-3,4-diaminopyrrolidine (trans-dap), cis-1,2-cyclopentanediamine (cis-cptn), and trans-1,2-cyclopentanediamine (trans-cptn) have been prepared in multigram quantities. The complexation of these ligands and of 3-aminopyrrolidine (ampy) with Ni^II, Cu^II, Zn^II, and Cd^II has been studied in solution by means of potentiometric and spectrophotometric titrations. The complexes of the triamines cis-dap and trans-dap show a pronounced tendency to form protonated species such as [M^II(HL)]³⁺, [M^II(HL)2]⁴⁺, and [M^II(HL)L]³⁺, indicative of a bidentate coordination mode of the ligand L. The UV/Vis spectra of the corresponding Cu^II complexes further confirmed bidentate coordination with trans-CuN4 geometry. The overall stabilities of the bis complexes [ML2]²⁺ decrease in the order cis-cptn > cis-dap > trans-cptn > ampy > trans-dap. The considerably lower stabilities of the ampy complexes as compared to the corresponding cis-dap complexes indicate metal binding to the two primary amino groups of the latter ligand. This was supported by molecular mechanics calculations (Cu^II and Co^III complexes) and confirmed by single-crystal X-ray diffraction studies of [Pt(Hcis-dap)Cl4]Cl·H2O, [Pd(Hcis-dap)2](ClO4)4·2H2O, and [Cu(Hcis-dap)2(OH2)2](SO4)2·3.5H2O − 2x H⁺ + x Cu²⁺ with 0.01  x  0.11. For the diamine ligands, coordination through the two exocyclic amino groups or through one exocyclic and one endocyclic amino group was established from the X-ray structure analyses of [Ni(cis-cptn)2](ClO4)2 and [Cu(3R-ampy)(3S-ampy)](ClO4)2, respectively. The crystal structure determination of [Co(cis-dap)(tach)][ZnCl4]Cl·C2H5OH (tach = cis-1,3,5-cyclohexanetriamine) revealed tridentate, facial coordination of cis-dap in this particular complex. However, the structural parameters of the [Co(cis-dap)(tach)]³⁺ moiety indicate significant strain for this coordination mode. The coordinating properties of the ligand cis-dap are compared with those of other aliphatic and alicyclic triamines.