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The title compound, C 15 H 15 F 3 N 2 O 3 S, crystallizes in the monoclinic system, space group I 2/ a , with Z = 8. As expected, the nine-membered heterobicyclic system is virtually planar and the cyclo-hexyl group adopts a chair conformation. There is structural evidence for intra-molecular N-S⋯O chalcogen bonding between the benziso-thia-zolinone S atom and one O atom of the nitro group, approximately aligned along the extension of the covalent N-S bond [N-S⋯O = 162.7 (1)°]. In the crystal, the mol-ecules form centrosymmetric dimers through C-H⋯O weak hydrogen bonding between a C-H group of the electron-deficient benzene ring and the benzo-thia-zolinone carbonyl O atom with an R 2 2 (10) motif. In contrast to the previously described N -acyl 7-nitro-5-(tri-fluoro-meth-yl)benzo[ d ]iso-thia-zol-3(2 H )-ones, the title N -cyclo-hexyl-methyl analogue does not inhibit growth of Mycobacterium aurum and Mycobacterium smegmatis in vitro ., (© Richter et al. 2023.)

Pyridin-4-ylmethanaminium perchlorate monohydrate (synonym: 4-picolyl-ammonium perchlorate monohydrate), C 6 H 9 N 2 + ·ClO 4 - ·H 2 O, crystallizes in the monoclinic system (space group P 2 1 / n ) with the asymmetric unit comprising two formula units ( Z ' = 2). All mol-ecular entities are located on general positions. The two crystallographically distinct 4-picolyl-ammonium cations exhibit different conformations. The two unique perchlorate anions are non-disordered, showing an r.m.s. deviation of 0.011 Å from mol-ecular T d symmetry. The supra-molecular structure in the solid state features an intricate tri-periodic network of N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds., (© Seidel and Kolev 2023.)

Tuberculosis is the leading bacterial killer worldwide. 8-Nitro-4 H -benzo[ e ][1,3]thiazin-4-ones are a potent class of antitubercular agents with a new mechanism of action. BTZ043 and PBTZ169 (macozinone) have progressed to clinical studies. Herein, we give a comprehensive account of this important class of potential new drugs to treat tuberculosis. We present an overview of recent developments in the field of antitubercular benzothiazinones (BTZs) and summarize our own contributions. The review covers synthesis, structures and reactivity, mechanism of action, in vitro activity and structure activity relationships (SARs), physicochemical and pharmacokinetic properties as well as a brief summary of in vivo models and clinical studies. We address bioavailability issues and the challenge of the potentially toxic nitroaromatic moiety, including reactivity towards nucleophiles in vivo and highlight possible directions of further research into BTZs through chemical modification.

N α-2-thiophenoyl-d-phenylalanine-2-morpholinoanilide [MMV688845, Pathogen Box; Medicines for Malaria Venture; IUPAC: (2 R )- N -(1-((2-morpholinophenyl)amino)-1-oxo-3-phenylpropan-2-yl)thiophene-2-carboxamide)] is a hit compound, which shows activity against Mycobacterium abscessus (MIC 90 6.25-12.5 μM) and other mycobacteria. This work describes derivatization of MMV688845 by introducing a thiomorpholine moiety and the preparation of the corresponding sulfones and sulfoxides. The molecular structures of three analogs are confirmed by X-ray crystallography. Conservation of the essential R configuration during synthesis is proven by chiral HPLC for an exemplary compound. All analogs were characterized in a MIC assay against M. abscessus , Mycobacterium intracellulare , Mycobacterium smegmatis , and Mycobacterium tuberculosis . The sulfone derivatives exhibit lower MIC 90 values ( M. abscessus : 0.78 μM), and the sulfoxides show higher aqueous solubility than the hit compound. The most potent derivatives possess bactericidal activity (99% inactivation of M. abscessus at 12.5 μM), while they are not cytotoxic against mammalian cell lines.

The title compound, C 16 H 16 N 4 O 3 , was obtained as a side product during the synthesis of the previously reported anti-tubercular agent N -(2-fluoro-eth-yl)-1-[(6-meth-oxy-5-methyl-pyrimidin-4-yl)meth-yl]-1 H -benzo[ d ]imidazole-4-carboxamide and structurally characterized by X-ray crystallography and computational methods. In the crystal (space group P 2 1 / n , Z = 4), the title compound adopts a twisted conformation with a dihedral angle between the benzimidazole and pyrimidine mean planes of 84.11 (3)°. The carboxyl-ate group and the 5-methyl group on the pyrimidine ring exhibit partial disorder. The DFT-optimized mol-ecular structure resembles the structure of the minor component in the crystal., (© Richter et al. 2023.)

8-Nitro-1,3-benzothiazin-4-ones (BTZs) are known as potent antitubercular agents. BTZ043 as one of the most advanced compounds has reached clinical trials. The putative oxidation products of BTZ043, namely, the corresponding BTZ sulfoxide and sulfone, were reported in this journal (Tiwari et al. ACS Med. Chem Lett. 2015 , 6 , 128-133). The molecular structures were later revised to the constitutionally isomeric benzisothiazolone and its 1-oxide, respectively. Here, we report two BTZ043-derived benzisothiazolinones (BITs) with in vitro activity against mycobacteria. The constitutionally isomeric O -acyl benzisothiazol-3-ols, in contrast, show little or no antimycobacterial activity in vitro. The structures of the four compounds were investigated by X-ray crystallography and NMR spectroscopy. Molecular covalent docking of the new compounds to Mycobacerium tuberculosis decaprenylphosphoryl-β-d-ribose 2'-epimerase (DprE1) suggests that the active BITs exert antimycobacterial activity through inhibition of DprE1 like BTZs., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

8-Nitro-4H-benzo[e][1,3]thiazinones (BTZs) are potent in vitro antimycobacterial agents. New chemical transformations, viz. dearomatization and decarbonylation, of two BTZs and their influence on the compounds' antimycobacterial properties are described. Reactions of 8-nitro-2-(piperidin-1-yl)-6-(trifluoromethyl)-4H-benzo[e][1,3]thiazin-4-one and the clinical drug candidate BTZ043 with the Grignard reagent CH 3 MgBr afford the corresponding dearomatized stable 4,5-dimethyl-5H- and 4,7-dimethyl-7H-benzo[e][1,3]thiazines. These methine compounds are structurally characterized by X-ray crystallography for the first time. Reduction of the BTZ carbonyl group, leading to the corresponding markedly non-planar 4H-benzo[e][1,3]thiazine systems, is achieved using the reducing agent (CH 3 ) 2 S ⋅ BH 3 . Double methylation with dearomatization and decarbonylation renders the two BTZs studied inactive against Mycobacterium tuberculosis and Mycobacterium smegmatis, as proven by in vitro growth inhibition assays., (© 2022 The Authors. ChemMedChem published by Wiley-VCH GmbH.)

8-Nitrobenzothiazinones (BTZs) are a promising class of antimycobacterial agents currently under investigation in clinical trials. Starting from thiourea derivatives, a new synthetic pathway to BTZs was established. It allows the formation of the thiazinone ring system in one synthetic step and is applicable for preparation of a wide variety of BTZ analogues. The synthetic procedure furthermore facilitates the replacement of the sulphur atom in the thiazinone ring system by oxygen or nitrogen to afford the analogous benzoxazinone and quinazolinone systems. 36 BTZ analogues were prepared and tested in luminescence-based assays for in vitro activity against Mycobacterium tuberculosis (Mtb) using the microdilution broth method and a high-throughput macrophage infection assay., (© 2021 The Authors. ChemMedChem published by Wiley-VCH GmbH.)

Nα-2-thiophenoyl-D-phenylalanine-2-morpholinoanilide (MMV688845, IUPAC: N-(1-((2-morpholinophenyl)amino)-1-oxo-3-phenylpropan-2-yl)thiophene-2-carboxamide) from the Pathogen Box ® library (Medicines for Malaria Ventures, MMV) is a promising lead compound for antimycobacterial drug development. Two straightforward synthetic routes to the title compound starting from phenylalanine or its Boc-protected derivative are reported. Employing Boc-phenylalanine as starting material and the T3P ® and PyBOP ® amide coupling reagents enables racemization-free synthesis, avoiding the need for subsequent separation of the enantiomers. The crystal structure of the racemic counterpart gives insight into the molecular structure and hydrogen bonding interactions in the solid state. The R-enantiomer of the title compound (derived from D-phenylalanine) exhibits activity against non-pathogenic and pathogenic mycobacterial strains, whereas the S-enantiomer is inactive. Neither of the enantiomers and the racemate of the title compound shows cytotoxicity against various mammalian cells., (© 2021. The Author(s).)

8-Nitro-1,3-benzo-thia-zin-4-ones are a promising class of new anti-tubercular agents, two candidates of which, namely BTZ043 and PBTZ169 (INN: macozinone), have reached clinical trials. The crystal and mol-ecular structures of two synthetic precursors, 2-chloro-3-nitro-5-(tri-fluoro-meth-yl)benzoic acid, C 8 H 3 ClF 3 NO 4 ( 1 ), and 2-chloro-3-nitro-5-(tri-fluoro-meth-yl)benzamide, C 8 H 4 ClF 3 N 2 O 3 ( 2 ), are reported. In 1 and 2 , the respective carb-oxy, carboxamide and the nitro groups are significantly twisted out of the plane of the benzene ring. In 1 , the nitro group is oriented almost perpendicular to the benzene ring plane. In the crystal, 1 and 2 form O-H⋯O and N-H⋯O hydrogen-bonded dimers, respectively, which in 2 extend into primary amide tapes along the [101] direction. The tri-fluoro-methyl group in 2 exhibits rotational disorder with an occupancy ratio of 0.876 (3):0.124 (3)., (© Richter et al. 2021.)

8-Nitro-1,3-benzothiazin-4-ones (BTZs), with BTZ043 and PBTZ169 as the most advanced compounds, represent a new class of potent antitubercular agents, which irreversibly inhibit decaprenylphosphoryl-β-d-ribose-2'-epimerase (DprE1), an enzyme crucial for cell wall synthesis in the pathogen Mycobacterium tuberculosis . Synthesis, structural characterization and in vitro testing against Mycobacterium aurum DSM 43999 and M. tuberculosis H 37 Rv of halogenated 2-(4-ethoxycarbonylpiperazin-1-yl)-1,3-benzothiazin-4-ones lacking a nitro group are reported. X-ray crystallography reveals that the structure of the BTZ scaffold can significantly deviate from planarity. In contrast to recent reports, the results of the present study indicate that further investigation of halogenated non-nitro BTZs for antitubercular activity is less than a promising approach., Competing Interests: Conflict of interestThe authors declare no competing interests., (© The Author(s) 2021.)

The title compound, sodium ammonium sulfate dihydrate (SASD), NaNH 4 SO 4 ·2H 2 O, a synthetic analogue of the mineral lecontite, is a well known ferroelectric. The crystal structure of the paraelectric phase has been re-refined at 170 K on the basis of single-crystal X-ray data, improving the previous study [Arzt & Glazer (1994 ▸). Acta Cryst. B 50 , 425-431] in terms of accuracy regarding hydrogen-atom positions and thus details of the hydrogen bonding. O-H⋯O and N-H⋯O hydrogen bonds between the principal building units [Na(OH 2 ) 4 O 2 octa-hedra, SO 4 tetra-hedra and ammonium cations] constitute a three-dimensional network structure., (© Eckhardt et al. 2020.)

1,3-Benzothiazin-4-ones (BTZs) are a promising new class of drugs with activity against Mycobacterium tuberculosis, which have already reached clinical trials. A product obtained in low yield upon treatment of 8-nitro-2-(piperidin-1-yl)-6-(trifluoromethyl)-4H-benzothiazin-4-one with 3-chloroperbenzoic acid, in analogy to a literature report describing the formation of sulfoxide and sulfone derived from BTZ043 [Tiwari et al. (2015). ACS Med. Chem. Lett. 6, 128-133], is a ring-contracted benzisothiazolinone (BIT) 1-oxide, namely, 7-nitro-2-(piperidine-1-carbonyl)-5-(trifluoromethyl)benzo[d]isothiazol-3(2H)-one 1-oxide, C 14 H 12 F 3 N 3 O 5 S, as revealed by X-ray crystallography. Single-crystal X-ray analysis of the oxidation product originally assigned as BTZ043 sulfone provides clear evidence that the structure of the purported BTZ043 sulfone is likewise the corresponding BIT 1-oxide, namely, 2-[(S)-2-methyl-1,4-dioxa-8-azaspiro[4.5]decane-8-carbonyl]-7-nitro-5-(trifluoromethyl)benzo[d]isothiazol-3(2H)-one 1-oxide, C 17 H 16 F 3 N 3 O 7 S. A possible mechanism for the ring contraction affording the BIT 1-oxides instead of the anticipated constitutionally isomeric BTZ sulfones and antimycobacterial activities thereof are discussed., (open access.)

1,3-Benzo-thia-zin-4-ones (BTZs) are a promising new class of anti-tuberculosis drug candidates, some of which have reached clinical trials. The title compound, the benzamide derivative [2-chloro-3-nitro-5-(tri-fluoro-meth-yl)phen-yl](piper-id-in-1-yl)methanone, C 13 H 12 ClF 3 N 2 O 3 , occurs as a side product as a result of competitive reaction pathways in the nucleophilic attack during the synthesis of the BTZ 8-nitro-2-(piperidin-1-yl)-6-(tri-fluoro-meth-yl)-1,3-benzo-thia-zin-4-one, following the original synthetic route, whereby the corresponding benzoyl iso-thio-cyanate is reacted with piperidine as secondary amine. In the title compound, the nitro group and the nearly planar amide group are significantly twisted out of the plane of the benzene ring. The piperidine ring adopts a chair conformation. The tri-fluoro-methyl group exhibits slight rotational disorder with a refined ratio of occupancies of 0.972 (2):0.028 (2). There is structural evidence for inter-molecular weak C-H⋯O hydrogen bonds., (© Eckhardt et al. 2020.)

The synthesis of ethyl 2-[(4-methyl-pyridin-2-yl)amino)-4-(pyridin-2-yl)thia-zole- 5-carboxyl-ate via the Hantzsch reaction and partial in situ transesterification during recrystallization from methanol- d 4 to the d 3 -methyl ester, resulting in the title solid solution, ethyl 2-[(4-methyl-pyridin-2-yl)amino)-4-(pyridin-2-yl)thia-zole-5-carboxyl-ate- d 3 -methyl 2-[(4-methyl-pyridin-2-yl)amino)-4-(pyridin-2-yl)thia-zole-5-carboxyl-ate (0.88/0.12), 0.88C 17 H 16 N 4 O 2 S·0.12C 16 D 3 H 11 N 4 O 2 S, is reported. The refined ratio of ethyl to d 3 -methyl ester in the crystal is 0.880 (6):0.120 (6). The pyridine ring is significantly twisted out of the plane of the approximately planar picoline thia-zole ester moiety. N-H⋯N hydrogen bonds between the secondary amino group and the pyridine nitro-gen atom of an adjacent symmetry-related mol-ecule link the mol-ecules into polymeric hydrogen-bonded zigzag tapes extending by glide symmetry in the [001] direction. There is structural evidence for intra-molecular N⋯S chalcogen bonding and inter-molecular weak C-H⋯O hydrogen bonds between adjacent zigzag tapes., (© Beuchel et al. 2020.)

The title compound, [HgI 2 (C 10 H 8 N 2 O 2 S 2 )] n , a one-dimensional coordination polymer with HgI 2 units and 2,2'-di-thio-bis-(pyridine N -oxide) spacer ligands in an alternating fashion, forms helical chains running along the b axis in the crystal. Within a single coordination polymer strand, the axially chiral 2,2'-di-thio-bis-(pyridine N -oxide) ligands are homochiral, but the enanti-omeric conformation is present in adjacent strands. Within a coordination polymer strand, the iodido ligands point towards the centroids of the aromatic rings of the pyridine N -oxide moieties in the coordination sphere of Hg II . Moreover, intra-strand C-H⋯O and C-H⋯I inter-actions, and inter-strand short S⋯I and S⋯O contacts are observed.

Adiponitrile, C 6 H 8 N 2 , is a key intermediate in the synthesis of the polyamide Nylon 66 and is produced industrially on a large scale. We have determined the crystal and molecular structure of adiponitrile by single-crystal X-ray analysis at 100 K, a suitable crystal (m.p. 275 K) having been grown from the melt at low temperature. The compound crystallizes in the monoclinic space group P2 1 /c with Z = 2. In the crystal structure, the molecule adopts an exact C i -symmetric gauche-anti-gauche conformation of the C-C-C-C skeleton about an inversion centre. The molecules are densely packed, with short intermolecular contacts between the α-H and nitrile N atoms.

Porphyrin assemblies display interesting photophysical properties and a relatively high thermal stability. Moreover, meso-functionalized porphyrins with virtually fourfold symmetry can be relatively readily synthesized from pyrrole and the appropriate aldehyde. A number of metallo derivatives of 5,10,15,20-tetrakis(4-cyanophenyl)porphyrin, where the N atom of the linear cyano group can act both as a donor for coordination bonds or as an acceptor for hydrogen bonds, have been structurally characterized by single-crystal X-ray analysis. The supramolecular and structural chemistry of the corresponding 2- and 3-cyanophenyl isomers of the parent porphyrin, however, has remained largely unexplored. The crystal structure of [5,10,15,20-tetrakis(3-cyanophenyl)porphyrinato]copper(II) (CuTCNPP) nitrobenzene trisolvate, [Cu(C 48 H 24 N 8 )]·3C 6 H 5 NO 2 , has been determined at 80 K by synchrotron single-crystal X-ray diffraction. CuTCNPP exhibits a C 2h -symmetric ααββ conformation, despite an unsymmetrical crystal environment, and is situated on a crystallographic centre of symmetry. The Cu II ion adopts a genuine square-planar coordination by the four pyrrole N atoms. The 24-membered porphyrin ring system shows no marked deviation from planarity. In the crystal, the CuTCNPP molecules and two nitrobenzene molecules are face-to-face stacked in an alternating fashion, resulting in corrugated layers. The remaining nitrobenzene guest molecule per CuTCNPP resides in the region between four neighbouring columnar stacks of CuTCNPP and sandwiched nitrobenzene molecules, and is disordered over four positions about a centre of symmetry.

The analogy between ZnR fragments and the hydrogen radical represents a fruitful concept in organometallic synthesis. The organozinc(ii) and -zinc(i) sources ZnMe 2 (Me = methyl) and [Zn 2 Cp* 2 ] (Cp* = pentamethylcyclopentadienyl) provide one-electron fragments ·ZnR (R = Me, Cp*), which can be trapped by transition metal complexes [L a M], yielding [L b (ZnR) n ]. The addition of the dizinc compound [Zn 2 Cp* 2 ] to coordinatively unsaturated [L a M] by the homolytic cleavage of the Zn-Zn bond can be compared to the classic oxidative addition reaction of H 2 , forming dihydride complexes [L a M(H) 2 ]. It has also been widely shown that dihydrogen coordinates under preservation of the H-H bond in the case of certain electronic properties of the transition metal fragment. The σ-aromatic triangular clusters [Zn 3 Cp* 3 ] + and [Zn 2 CuCp* 3 ] may be regarded as the first indication of this so far unknown, side-on coordination mode of [Zn 2 Cp* 2 ]. With this background in mind the question arises if a series of complexes featuring the Zn 2 M structural motif can be prepared exhibiting a (more or less) intact Zn-Zn interaction, i.e. di-zinc complexes which are analogous to non-classical dihydrogen complexes of the Kubas type. In order to probe this idea, a series of interrelated organozinc nickel and palladium complexes and clusters were synthesized and characterized as model compounds: [Ni(ZnCp*)(ZnMe)(PMe 3 ) 3 ] ( 1 ), [Ni(ZnCp*) 2 (ZnMe) 2 (PMe 3 ) 2 ] ( 2 ), [{Ni(CN t Bu) 2 (μ 2 -ZnCp*)(μ 2 -ZnMe)} 2 ] ( 3 ), [Pd(ZnCp*) 4 (CN t Bu) 2 ] ( 4 ) and [Pd 3 Zn 6 (PCy 3 ) 2 (Cp*) 4 ] ( 5 ). The dependence of Zn···Zn interactions as a function of the ligand environments and the metal centers was studied. Experimental X-ray crystallographic structural data and DFT calculations support the analogy between dihydrogen and dizinc transition metal complexes.

The bottom-up synthesis of organometallic zinc clusters is described. The cation {[Zn10](Cp*)6 Me}(+) (1) is obtained by reacting [Zn2 Cp*2] with [FeCp2][BAr4 (F)] in the presence of ZnMe2. In the presence of suitable ligands, the high reactivity of 1 enables the controlled abstraction of single Zn units, providing access to the lower-nuclearity clusters {[Zn9 ](Cp*)6} (2) and {[Zn8 ](Cp*)5 ((t) BuNC)3}(+) (3). According to DFT calculations, 1 and 2 can be described as closed-shell species that are electron-deficient in terms of the Wade-Mingos rules because the apical ZnCp* units that constitute the cluster cage do not have three, but only one, frontier orbitals available for cluster bonding. Zinc behaves flexibly in building the skeletal metal-metal bonds, sometimes providing one major frontier orbital (like Group 11 metals) and sometimes providing three frontier orbitals (like Group 13 elements)., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The title compound, [Cu(C20H23N3O4)], crystallizes in the space group Cc with two independent mol-ecules in the asymmetric unit. The Cu(II) atoms are each coordinated by the penta-dentate Schiff base ligand in a distorted trigonal bipyramidal N3O2 geometry. The equatorial plane is formed by the two phenolic O atoms and the amine N atom, while the axial positions are occupied by the two imine N atoms. In the crystal, the two independent mol-ecules are each connected into a column along the b axis through inter-molecular O-H⋯O hydrogen bonds. The two independent columns are further linked through an N-H⋯O hydrogen bond, forming a double-column structure.

In the crystal structure of the title mononuclear Cu(II) complex, [Cu(C11H16N3O2)(NO3)]·0.25C2H5OH, the complex molecules are linked by N-H⋯O and O-H⋯O hydrogen bonds, forming a dimer with an approximate non-crystallographic twofold rotation axis of symmetry. In the monomeric unit, the Cu(2+) ion exhibits a distorted square-pyramidal configuration, whereby the anionic [HL](-) Schiff base ligand binds in a tetradentate fashion via the O and the three N atoms which all are approximately coplanar. The O atom of a nitrate anion occupies the fifth coordination site, causing the Cu(II) atom to move slightly out of the approximate basal plane toward the bound nitrate group. The structure exhibits disorder of the ethanol solvent mol-ecule.

The triangular clusters [Zn3Cp*3](+) and [Zn2CuCp*3] were obtained by addition of the in situ generated, electrophilic, and isolobal species [ZnCp*](+) and [CuCp*] to Carmona's compound, [Cp*Zn-ZnCp*], without splitting the ZnZn bond. The choice of non-coordinating fluoroaromatic solvents was crucial. The bonding situations of the all-hydrocarbon-ligand-protected clusters were investigated by quantum chemical calculations revealing a high degree of σ-aromaticity similar to the triatomic hydrogen ion [H3](+). The new species serve as molecular building units of Cu(n)Zn(m) nanobrass clusters as indicated by LIFDI mass spectrometry., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthesis and characterization of the cationic mixed metal Ga/Zn cluster [Zn2(GaCp*)6](2+) (1) is presented. The reaction of [Zn2Cp*2] with [Ga2Cp*][BAr4(F)] leads to the formation of the novel complex being the first example of a [Zn2](2+) core exclusively ligated by metalloid group-13 organyl-ligands. Compound 1 exhibits two different coordination modes: In the solid state, two of the six GaCp* ligands occupy bridging positions, whereas VT (1)H NMR indicates the coexistence of a second isomer in solution featuring six terminal GaCp* ligands. Quantum chemical calculations have been carried out to assign the gallium and zinc positions; the bonding situation in 1 is characterized and the importance of dispersion forces is discussed.

Defined molecular models for the surface chemistry of Hume-Rothery nanophases related to catalysis are very rare. The Al-Cu intermetalloid cluster [(Cp*AlCu)6H4] was selectively obtained from the clean reaction of [(Cp*Al)4] and [(Ph3PCuH)6]. The stronger affinity of Cp*Al towards Cu sweeps the phosphine ligands from the copper hydride precursor and furnishes an octahedral Al6 cage to encapsulate the Cu6 core. The resulting hydrido cluster M12H4 reacts with benzonitrile to give the stoichiometric hydrometalation product [(Cp*AlCu)6H3(N=CHPh)]., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Treatment of tetrakis(diethylamido)zirconium(IV); [Zr(NEt2)4] with a series of β-ketoimines ({[RHN]C(CH3)=C(H)C(CH3)=O} where R is a functionalized side-chain; 4-(2-methoxyethylamino)pent-3-en-2-one, Hmeap; 4-(3-methoxypropylamino)pent-3-en-2-one, Hmpap; 4-(2-(dimethylamino)ethylamino)pent-3-en-2-one, Hdeap; 4-(3-(dimethylamino)propylamino)pent-3-en-2-one, Hdpap) leads to an amine substitution reaction that yielded novel monomeric heteroleptic mixed amido-ketoiminato complexes of the type bis(4-(2-methoxyethylamino)pent-3-en-2-onato)bis(diethylamido)zirconium(IV) (1), bis(4-(3-methoxypropylamino)pent-3-en-2-onato)bis(diethylamido)zirconium(IV) (2), and bis(4-(3-(dimethylamino)propylamino)pent-3-en-2-onato)bis(diethylamido)zirconium(IV) (3), and eight-coordinated homoleptic complexes tetrakis(4-(2-methoxyethylamino)pent-3-en-2-onato)zirconium(IV) (4) and tetrakis(4-(2-(dimethylamino)ethylamino)pent-3-en-2-onato)zirconium(IV) (5), depending on the ratio of the ligand to zirconium. Adopting a similar strategy with zirconium alkoxide, namely [Zr(O(i)Pr)4·(i)PrOH], with β-ketoimine Hmeap, leads to the formation of a dimer, bis(μ2-isopropoxo)bis(4-(2-methoxyethylamino)pent-3-en-2-onato)tetrakis(isopropoxo)dizirconium(IV) (6). The newly synthesised complexes were characterized by NMR spectroscopy, mass spectrometry, single crystal X-ray diffraction, elemental analysis and thermal analysis. The low decomposition temperature facilitated by the stepwise elimination of the ketominate ligand from the complex and the stability of the complexes obtained in air as well as in solution makes them highly suitable for solution based processing of ZrO2 thin films, which is demonstrated using compound 5 on Si(100) substrates. High quality ZrO2 films were obtained and were investigated for their structure, morphology, composition and optical properties. Low temperature crystallisation of ZrO2 is achieved by a simple chemical deposition process using the new class of Zr precursors and the films exhibit an optical transmittance above 90%.

The title compound, [Zn(SiF6)(C12H8N2)2]·CH3OH, contains a neutral heteroleptic tris-chelate Zn(II) complex, viz. [Zn(SiF6)(phen)2] (phen is 1,10-phenanthroline), exhibiting approximate molecular C2 point-group symmetry. The Zn(II) cation adopts a severely distorted octahedral coordination. As far as can be ascertained, the title complex represents the first structurally characterized example of a Zn(II) complex bearing a bidentate-bound hexafluorosilicate ligand. A density functional theory study of the isolated [Zn(SiF6)(phen)2] complex was undertaken to reveal the influence of crystal packing on the molecular structure of the complex. In the crystal structure, the methanol solvent molecule forms a hydrogen bond to one F atom of the hexafluorosilicate ligand. The hydrogen-bonded assemblies so formed are tightly packed in the crystal, as indicated by a high packing coefficient (74.1%).

The synthesis, characterization, and theoretical investigation by means of quantum-chemical calculations of an oligonuclear metal-rich compound are presented. The reaction of homoleptic dinuclear palladium compound [Pd(2)(μ-GaCp*)(3)(GaCp*)(2)] with ZnMe(2) resulted in the formation of unprecedented ternary Pd/Ga/Zn compound [Pd(2)Zn(6)Ga(2)(Cp*)(5)(CH(3))(3)] (1), which was analyzed by (1)H and (13)C NMR spectroscopy, MS, elemental analysis, and single-crystal X-ray diffraction. Compound 1 consisted of two C(s)-symmetric molecular isomers, as revealed by NMR spectroscopy, at which distinct site-preferences related to the Ga and Zn positions were observed by quantum-chemical calculations. Structural characterization of compound 1 showed significantly different coordination environments for both palladium centers. Whilst one Pd atom sat in the central of a bi-capped trigonal prism, thereby resulting in a formal 18-valence electron fragment, {Pd(ZnMe)(2)(ZnCp*)(4)(GaMe)}, the other Pd atom occupied one capping unit, thereby resulting in a highly unsaturated 12-valence electron fragment, {Pd(GaCp*)}. The bonding situation, as determined by atoms-in-molecules analysis (AIM), NBO partial charges, and molecular orbital (MO) analysis, pointed out that significant Pd-Pd interactions had a large stake in the stabilization of this unusual molecule. The characterization and quantum-chemical calculations of compound 1 revealed distinct similarities to related M/Zn/Ga Hume-Rothery intermetallic solid-state compounds, such as Ga/Zn-exchange reactions, the site-preferences of the Zn/Ga positions, and direct M-M bonding, which contributes to the overall stability of the metal-rich compound., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthesis, structural characterization, and bonding situation analysis of a novel, all-zinc, hepta-coordinated palladium complex [Pd(ZnCp*)(4)(ZnMe)(2){Zn(tmeda)}] (1) is reported. The reaction of the substitution labile d(10) metal starting complex [Pd(CH(3))(2)(tmeda)] (tmeda = N,N,N',N'-tetramethyl-ethane-1,2-diamine) with stoichiometric amounts of [Zn(2)Cp*(2)] (Cp* = pentamethylcyclopentadienyl) results in the formation of [Pd(ZnCp*)(4)(ZnMe)(2){Zn(tmeda)}] (1) in 35% yield. Compound 1 has been fully characterized by single-crystal X-ray diffraction, (1)H and (13)C NMR spectroscopy, IR spectroscopy, and liquid injection field desorption ionization mass spectrometry. It consists of an unusual [PdZn(7)] metal core and exhibits a terminal {Zn(tmeda)} unit. The bonding situation of 1 with respect to the properties of the three different types of Zn ligands Zn(R,L) (R = CH(3), Cp*; L = tmeda) bonded to the Pd center was studied by density functional theory quantum chemical calculations. The results of energy decomposition and atoms in molecules analysis clearly point out significant differences according to R vs L. While Zn(CH(3)) and ZnCp* can be viewed as 1e donor Zn(I) ligands, {Zn(tmeda)} is best described as a strong 2e Zn(0) donor ligand. Thus, the 18 valence electron complex 1 nicely fits to the family of metal-rich molecules of the general formula [M(ZnR)(a)(GaR)(b)] (a + 2b = n ≥ 8; M = Mo, Ru, Rh; Ni, Pd, Pt; R = Me, Et, Cp*).

The structure of the title compound, [Zn(4)(C(40)H(24)N(8))(4)]·8C(3)H(7)NO·3H(2)O, has been redetermined at 100 K. The redetermination is of significantly higher precision and gives further insight into the disorder of pyridyl groups and solvent mol-ecules. The mol-ecules of (5,10,15,20-tetra-4-pyridyl-porphyrinato)zinc(II) (ZnTPyP) form homomolecular cyclic tetra-mers by coordination of a peripheral pyridyl group to the central Zn atom of an adjacent symmetry-related mol-ecule. The tetra-mer so formed exhibits mol-ecular S(4) symmetry and is located about a crystallographic fourfold rotoinversion axis. Severely disordered dimethyl-formamide and water mol-ecules are present in the crystal, the contributions of which were omitted from refinement. Inter-molecular C-H⋯N hydrogen bonding is observed.

The synthesis and structural characterisation of low-valent dinuclear copper(I) and copper(0) complexes supported by organogallium ligands has been accomplished for the first time by the reductive coordination reaction of [GaCp*] (Cp*=pentamethylcyclopentadienyl) and [Ga(ddp)] (ddp=HC(CMeNC(6)H(3)-2,6-iPr(2))(2) 2-diisopropylphenylamino-4-diisopropylphenylimino-2-pentene) with readily available copper(II) and copper(I) precursors. The treatment of CuBr(2) and Cu(OTf)(2) (OTf=CF(3)SO(3)) with [Ga(ddp)] under mild conditions resulted in elimination of [Ga(L)(2)(ddp)] (L=Br, OTf) and afforded the novel gallium(I)/copper(I) compounds [{(ddp)GaCu(L)}(2)] (L=Br (1), OTf (2)). The single-crystal X-ray structure determinations of 1 and 2 reveal that these molecules are composed of {(ddp)GaCu(L)} dimeric units, with planar Cu(I)-Ga(I) four-membered rings and short Cu(I)...Cu(I) distances, with 2 exhibiting the shortest Cu(I)Cu(I) contact reported to date of 2.277(3) A. The all-gallium coordinated dinuclear [Cu(2)(GaCp*)(mu-GaCp*)(3)Ga(OTf)(3)] (3) is formed when Cu(OTf)(2) is combined with [GaCp*] instead of [Ga(ddp)]. Notably, in the course of this redox reaction Lewis acidic Ga(OTf)(3) is formed, which coordinates to one of the electron-rich copper(0) centres. Compound 3 is suggested as the first case of a structurally characterised complex of copper(0). By changing the copper(II) to a copper(I) source, that is, [Cu(cod)(2)][OTf] (cod=1,5-cyclooctadiene), the salt [Cu(2)(GaCp*)(3)(mu-GaCp*)(2)][OTf](2) (4) is formed, the cationic part of which is related to previously described isoelectronic dinuclear d(10) complexes of the type [M(2)(GaCp*)(5)] (M=Pd, Pt).

The 2:1 sandwich-type complexes formed between a cyclopeptide with alternating L-proline and 6-aminopicolinic acid subunits and inorganic anions can be stabilized by covalently linking a tris-alkyne and a tris-azide derivative of this peptide through copper-catalyzed azide-alkyne cycloaddition. The resulting triply linked bis-cyclopeptide can interact with anions such as sulfate ions in aqueous solution by including them into the cavity between the two cyclopeptide rings, where they can form hydrogen bonds to amide NH groups, distributed along the inner surface. The binding kinetics of this system differ significantly from those of a bis-cyclopeptide that contains only one linker because the rate of guest exchange is considerably slower. Thermodynamically, the stability of the sulfate complex of the triply linked bis-cyclopeptide approaches a log K(a) value of 6 in H(2)O/CH(3)OH 1:1 (v/v) which is, however, only approximately one order of magnitude larger than affinity of the more flexible monolinked analogue. Titration calorimetry revealed that this behavior is mainly due to the change in the binding enthalpy from exothermic to endothermic upon increasing the number of linkers. Results from NMR spectroscopy and X-ray crystallography indicate that the mono- and triply linked bis-cyclopeptides adopt similar conformations in their complexes with sulfate ions, but the complex formation is enthalpically unfavorable for the cage. The substantial entropic contribution to sulfate complexation of this receptor more than compensates for this disadvantage, so that the overall sulfate affinity of both bis-cyclopeptides ends up in the same range. These investigations provide important insight into the structure-property relationships of such receptors, thus leading the way to further structural improvement.

The title compound, 2-(phenylethyl)ammonium hydrogensquarate hemihydrate, was synthesized and structurally and spectroscopically characterized by a single crystal X-ray diffraction and solid-state polarized IR spectroscopy of oriented colloids in a nematic host. The crystal structure consists of two crystallographically independent 2-(phenylethyl)ammonium cations, joined in a 2D hydrogen-bonded network with hydrogensquarate anions and solvent water molecules. Surprisingly, the crystallographically non-equivalent cations exhibit differing pseudo T and G trans configurations.

Heavy-metal complexes of lead and mercury stabilized by Group 13 ligands were derived from the oxidative addition of Ga(ddp) (ddp=HC(CMeNC(6)H(3)-2,6-iPr(2))(2), 2-diisopropylphenylamino-4-diisopropyl phenylimino-2-pentene) with corresponding metal precursors. The reaction of Me(3)PbCl and Ga(ddp) afforded compound [{(ddp)Ga(Cl)}PbMe(3)] (1) composed of Ga-Pb(IV) bonds. In addition, the monomeric plumbylene-type compound [{(ddp)Ga(OSO(2)CF(3))}(2)Pb(thf)] (2a) with an unsupported Ga-Pb(II)-Ga linkage was obtained by the reaction of [Pb(OSO(2)CF(3))(3)] with Ga(ddp) (2 equiv). Compound 2a falls under the rare example of a discrete plumbylene-type compound supported by a nonclassical ligand. Interesting structural changes were observed when [Pb(OSO(2)CF(3))(3)]2.H(2)O was treated with Ga(ddp) in a 1:2 ratio to yield [{(ddp)Ga(mu-OSO(2)CF(3))}(2)(OH(2))Pb] (2b) at below -10 degrees C. Compound 2b consists of a bent Ga-Pb-Ga backbone with a bridging triflate group between the Ga-Pb bond and a weakly interacting water molecule at the gallium center. Similarly, the reaction of mercury thiolate Hg(SC(6)F(5)) with Ga(ddp) (2 equiv) produced the bimetallic homoleptic compounds anti-[{(ddp)Ga(SC(6)F(5))}(2)Hg] (3a) and gauche-[{(ddp)Ga(SC(6)F(5))}(2)Hg] (3b), respectively, with a linear Ga-Hg-Ga linkage. Compounds 1-3 were structurally characterized and these are the first examples of compounds comprised of Ga-Pb(II), Ga-Pb(IV), and Ga-Hg bonds.

The crystal structure of β-cyclo-dextrin, C(42)H(70)O(35)·10.41H(2)O, consists of truncated cone-shaped β-cyclo-dextrin mol-ecules that are herringbone packed. The primary hydr-oxy groups form an intra-molecular hydrogen-bonded array. The semipolar cavity of the cyclo-dextrin host is filled with water mol-ecules, which show partial occupancy and disorder.

The title compound, {[Cu(NO(3))(C(2)H(4)N(2))(C(10)H(8)N(2)S(2))(H(2)O)]NO(3).H(2)O}(n), is composed of a one-dimensional linear coordination polymer involving cis-protected copper(II) ions and a 4,4'-dithiodipyridine bridging ligand. The polymeric chains run along the c-axis direction. N-H...O and O-H...O hydrogen bonds involving the coordinating amine groups, nitrate ions and water molecules, as well as cocrystallized noncoordinating nitrate ions and water molecules, generate a three-dimensional structure.

In the title compound, [Ni(NO(3))(2)(C(6)H(15)OP)(2)], the Ni(II) ion, lying on a crystallographic twofold axis, adopts a distorted octa-hedral coordination, consisting of O-donor atoms of two symmetry-related triethyl-phospine oxide and two bidentate nitrate ligands.

We report the synthesis, spectroscopic and structural elucidation of two prolinamide derivatives of squaric acid, i.e. prolinamide ester amide of squaric acid ethyl ester (1) and prolinamide diamide of squaric acid dihydrate (2). Both compounds crystallize in non-centrosymmetric space groups, monoclinic P2(1) (1) and orthorhombic P2(1)2(1)2(1) (2), respectively. For first time in the literature the crystal structure of homodiamide of amino acid amide of squaric acid is reported. The data for heterodiamides is also absent. Supramolecular zig-zag chains by hydrogen bonds of H(2)N-C=O ..., HNH (3.020 A) and HNH ..., OC((S(q))) (2.972 A) types with the participation of amide and squaric acid (S(q)) fragments, -CO=NH(2) and O=C((S(q))) are refined in (1). A helix supramolecular structure is formed in (2) by moderate intermolecular HNH ... O=C(NH(2)) hydrogen bond with length of 2.947A. The two crystallographical non-equivalent water molecules stabilized the helix by interactions of types HOH...OC((Sq)) (2.917A), HOH...O=C(NH(2)) (2.899A), H(2)O...NH(2)(C=O) (2.972A), respectively. Optical and magnetic properties are investigated with a view to explain the correlation structure-properties of the newly synthesized molecules.

The crystal structure of the title compound, [Cu(2)Cl(4)(C(10)H(8)N(2)O(2)S)(2)(H(2)O)(2)], comprises neutral centrosymmetric μ-chloride-bridged dinuclear units. Each Cu(II) ion is penta-coordinated by three chloride ligands, a pyridine N-oxide O atom and a water mol-ecule. Intra- and inter-molecular O-H⋯O hydrogen bonds occur between the coordinated water mol-ecules and the uncoordinated and coordinated pyridine N-oxide groups of the 2,2'-thio-bis(pyridine N-oxide) ligands, respectively.

Tyrammonium 4-nitrophthalate has been synthesized and its structural and spectroscopic properties elucidated by single-crystal X-ray diffraction, solid-state polarized IR-spectroscopy of oriented colloids in a nematic host, HPLC with tandem mass spectrometry (HPLC ESI-MSMS), and TGV and DSC methods. The compound crystallizes in the monoclinic P2(1)/c space group and its structure consists of a 3D network of molecules joined by intermolecular interactions with the participation of cations, anions and two solvent molecules. The tyrammonium cation adopts a T trans configuration with corresponding angles of phi (1) = 76.0(4) degrees, phi (2 )= 54.8(1) degrees and phi (3) = 63.4(1) degrees, respectively. In the 4-nitrophthalate anion, the COO(-) and COOH groups are turned off the plane of the benzene ring at angles of tau (1) = 88.1(5) degrees and tau (2)= 22.1(7) degrees, respectively.

A distortion of the aromatic character and stabilization of the imino-form as a result of the protonation of 4-dimethylaminopyridine was established by IR-, UV- and 1H NMR-spectral analysis of 4-diaminopyridinium hydrogensquarate. Quantum chemical calculations were carried out at MP2 and B3LYP levels of theory and a 6-311++G** basis set with a view to determining the changes in geometrical parameters and IR-spectroscopic characteristics resulting from Npy protonation. Linear-dichroic IR-spectroscopy coupled with the orientation techniques of solid samples as liquid crystal suspensions and melted solid polycrystalline films was applied for the identification of the IR-bands, characteristic for the structural fragments of the neutral and imino-form of the pyridine derivative. The spectral results were compared with the structure, obtained by a single crystal X-ray analysis. The salt contains dimmers of hydrogensquarate anions and Npy protonated cations of which the former are stabilized by strong intermolecular OH...O interactions (2.552 angstroms and 143.1(2) degrees). The 4-diaminopyridinium cation interacts with the anion through moderate NH...O bonds (2.729 angstroms and 165.0(0) degrees ). Individual cations are pi-pi stacked with their neighbors at a distance of 3.406 angstroms.

The formula unit of the title compound, 2C(6)H(7)N(2)O(+)·C(2)O(4) (2-), comprises two symmetry-equivalent 4-(hydroxy-imino-meth-yl)-pyridinium cations on general positions, linked through hydrogen bonding via an oxalate anion that resides on a crystallographic centre of symmetry. The crystal structure consists of infinite chains of cations and oxalate anions directed by O-H⋯O and multicentre N-H⋯O inter-molecular hydrogen-bonding inter-actions.