Crystal structure of 1-cyclo-propane-carbon-yl-3-methyl-2,6-di-p-tolyl-piperidin-4-one.

The title compound, C24H27NO2, crystallizes with two independent mol-ecules (A and B) in the asymmetric unit. The two mol-ecules have very similar conformations and each exhibits an intra-molecular C-H⋯π inter-action. The central piperidine rings adopt boat conformations and the p-tolyl rings are inclined to the mean plane of the piperidine ring by 71.21 (11) and 89.86 (12)° in mol-ecule A and by 68.01 (12) and 89.33 (12)° in mol-ecule B. The cyclopropanecarbonyl group is oriented at an angle of 68.5 (2)° with respect to the mean plane of the piperidine ring in mol-ecule A and 66.2 (2)° in mol-ecule B. In the crystal, the A and B mol-ecules are linked by C-H⋯O hydrogen bonds, enclosing R 2 (1)(6) ring motifs, forming ribbons running along the a-axis direction.

Crystal structure of 3-[(2-acetyl-phen-oxy)carbon-yl]benzoic acid.

In the title compound, C16H12O5, synthesized from isopthaloyl chloride and 2'-hy-droxy-aceto-phenone, the dihedral angle between the planes of the aromatic rings is 71.37 (9)°. In the crystal, carb-oxy-lic acid inversion dimers generate R 2 (2)(8) loops. The dimers are linked by C-H⋯O inter-actions, generating (101) sheets.

Crystal structure of tricarbon-yl[η4-6-exo-(tri-phenyl-phosphino)cyclo-hepta-2,4-dien-1-one]iron(0) tetra-fluoro-borate.

The mol-ecular structure of tricarbon-yl[η4-6-exo-(tri-phenyl-phosphino)cyclo-hepta-2,4-dien-1-one]iron(0) tetra-fluoro-borate di-chloro-methane hemisolvate, [Fe(C28H22O4)(CO)3]BF4·0.5CH2Cl2, as determined by single-crystal X-ray diffraction is reported. The two independent tricarbon-yl[η4-6-exo-(tri-phenyl-phosphino)cyclo-hepta-2,4-dien-1-one] iron(0) cations and their corresponding anions form dimers, which constitute the asymmetric unit of the structure parallel to the (100) plane. Solid-state stability within that asymmetric unit as well as between neighboring dimeric units is afforded by C-H⋯O and C-H⋯F hydrogen bonds and C-H⋯π and Y-X⋯π (Y = B, C; X = F, O) inter-actions, which yield diperiodic sheets and a three-dimensional extended network.

trans-Carbonyl-chlorido-bis-(tri-ethyl-phosphane-κP)platinum(II) tetra-fluorido-borate.

The chemical formulation of the title compound was established as trans-[PtCl{P(C2H5)3(CO)}BF4 by single-crystal X-ray analysis, in contrast to the five-coordinate tetra-fluoro-ethyl-ene complex that had been anti-cipated. The compound had been prepared by reaction of trans-PtHCl(P(C2H5)3)2 with C2F4 in the absence of air, and the presence of the carbonyl group was not suspected. The square-planar cations and BF4 - anions are linked by C-H⋯F and C-H⋯O inter-actions into thick wavy (010) sheets. The present crystal-structure refinement is based on the original intensity data recorded in 1967.

4-[(Benzyl-amino)-carbon-yl]-1-methyl-pyridinium halogenide salts: X-ray diffraction study and Hirshfeld surface analysis.

Two salts of 4-[(benzyl-amino)-carbon-yl]-1-methyl-pyridinium (Am) with chloride (C14H15N2O+·Cl-) and bromide (C14H15N2O+·Br-) anions were studied and compared with the iodide salt. AmCl crystallizes in the centrosymmetric space group P21/n while AmBr and AmI form crystals in the Sohncke space group P212121. Crystals of AmBr are isostructural to those of AmI. The cation and anion are bound by an N-H⋯Hal hydrogen bond. Hirshfeld surface analysis was used to compare different types of inter-molecular inter-actions in the three structures under study.

4-[(Benzyl-amino)-carbon-yl]-1-methyl-pyridinium bromide hemihydrate: X-ray diffraction study and Hirshfeld surface analysis.

The hemihydrate of 4-[(benzyl-amino)-carbon-yl]-1-methyl-pyridinium bromide, C14H15N2O+·Br-·0.5H2O, was studied by single-crystal and powder X-ray diffraction methods. In the asymmetric unit, two organic cations of similar conformation, two bromide anions and one water mol-ecule are present. In the crystal, N-H⋯Br hydrogen bonds link the cations and anions. The formation of a set of inter-molecular C-H⋯Br and C-H⋯π inter-actions result in double chains extending parallel to [011]. A Hirshfeld surface analysis showed high contributions of H⋯H and C⋯H/H⋯C short contacts to the total Hirshfeld surfaces of the cations.

Dimethyl 4,5-di-chloro-phthalate.

While endeavoring to synthesize new chlorinated ligands for ruthenium-based metathesis catalysts, the title compound dimethyl 4,5-di-chloro-phthalate, C10H8Cl2O4, was prepared from commercially available 4,5-di-chloro-phthalic acid in ∼77% yield. The title mol-ecule, which also finds utility as a precursor mol-ecule for the synthesis of drugs used in the treatment of Alzheimer's disease, shows one carbonyl-containing methyl ester moiety lying nearly co-planar with the chlorine-derivatized aromatic ring while the second methyl ester shows a significant deviation of 101.05 (12)° from the least-squares plane of the aromatic ring. Within the crystal, structural integrity is maintained by the concerted effects of electrostatic inter-actions involving the electron-deficient carbonyl carbon atom and the electron-rich aromatic ring along the a-axis direction and C-H⋯O hydrogen bonds between neighboring mol-ecules parallel to b.

Crystal structure of the new palladium complexes tetra-kis-(1,3-di-methyl-imidazolium-2-yl-idene)palladium(II) hexa-deca-carbonyl-tetra-rhenium diethyl ether disolvate and octa-µ-carbonyl-di-carbonyl-tetra-kis-(tri-phenyl-phosphane)palladium-dirhenium (unknown solvate).

The investigation of the coordination chemistry of heterometallic transition-metal complexes of palladium (Pd) and rhenium (Re) led to the isolation and crystallographic characterization of tetra-kis-(1,3-di-methyl-imidazolium-2-yl-idene)palladium(II) hexa-deca-carbonyl-tetra-rhenium diethyl ether disolvate, [Pd(C5H8N2)4][Re4(CO)16]·2C4H10O or [Pd(IMe)4][Re4(CO)16]·2C4H10O, (1), and octa-µ-carbonyl-di-carbonyl-tetra-kis-(tri-phenyl-phosphane)palladium-dirhenium, [Pd4Re2(C18H15P)4(CO)10] or Pd4Re2(PPh3)4(µ-CO)8(CO)2, (2), from the reaction of Pd(PPh3)4 with 1,3-di-methyl-imidazolium-2-carboxyl-ate and Re2(CO)10 in a toluene-aceto-nitrile mixture. In complex 1 the Re-Re bond lengths [2.9767 (3)-3.0133 (2) Å] are close to double the covalent Re radii (1.51 Å). The palladium-rhenium carbonyl cluster 2 has not been structurally characterized previously; the Pd-Re bond lengths [2.7582 (2)-2.7796 (2) Å] are about 0.1 Šshorter than the sum of the covalent Pd and Re radii (1.39 + 1.51 = 2.90 Å). One carbene ligand and a diethyl ether mol-ecule are disordered over two positions with occupancy ratios of 0.5:0.5 and 0.625 (15):0.375 (15) in 1. An unidentified solvent is present in compound 2. The given chemical formula and other crystal data do not take into account the unknown solvent mol-ecule(s). The SQUEEZE routine [Spek (2015 ▸). Acta Cryst. C71, 9-18] in PLATON was used to remove the contribution of the electron density in the solvent region from the intensity data and the solvent-free model was employed for the final refinement. The cavity with a volume of ca 311 Å3 contains approximately 98 electrons.

Salts of 4-[(benzyl-amino)-carbon-yl]-1-methyl-pyridinium and iodide anions with different cation:iodine stoichiometric ratios.

The two iodide salts, 4-[(benzyl-amino)-carbon-yl]-1-methyl-pyridinium iodide-iodine (2/1), C14H15N2O+·I-·0.5I2, I, and 4-[(benzyl-amino)-carbon-yl]-1-methyl-pyridinium triiodide, C14H15N2O+·I3 -, II, with different cation:iodine atoms ratios were studied. Salt I contains one cation, one iodide anion and half of the neutral I2 mol-ecule in the asymmetric unit (cation:iodine atoms ratio is 1:2). Salt II contains two cations, one triiodide anion (I 3 -) and two half triiodide anions (cation:iodine atoms ratio is 1:3). The NH group forms N-H⋯I hydrogen bonds with the I- anion in the crystal of I or N-H⋯O hydrogen bonds in II where only triiodide anions are present.

Crystal structures of three N-(pyridine-2-carbon-yl)pyridine-2-carboxamides as potential ligands for supra-molecular chemistry.

The synthesis and single-crystal X-ray structures of three N-(pyridine-2-carbon-yl)pyridine-2-carboxamide imides, with or without F atoms on the 3-position of the pyridine rings are reported, namely, N-(pyridine-2-carbon-yl)pyridine-2-carboxamide, C12H9N3O2 (1), N-(3-fluoro-pyridine-2-carbon-yl)pyridine-2-carboxamide, C12H8FN3O2 (2), and 3-fluoro-N-(3-fluoro-pyridine-2-carbon-yl)pyridine-2-carboxamide, C12H7F2N3O2 (3). The above-mentioned compounds were synthesized by a mild, general procedure with an excellent yield, providing straightforward access to symmetrical and/or asymmetrical heterocyclic ureas. The crystal structures of 1 and 2 are isomorphous, showing similar packing arrangements, i.e. double layers of parallel (face-to-face) mol-ecules alternating with analogous, but perpendicularly oriented, double layers. In contrast, the crystal structure of 3, containing a fluoro- group at the 3-position of both pyridine rings, shows mol-ecular arrangements in a longitudinal, tubular manner along the c axis, with the aromatic pyridine and carbon-yl/fluorine moieties facing towards each other.

4-[(E)-3-(4-Methyl-phen-yl)-3-oxoprop-1-en-1-yl]benzo-nitrile.

In the title mol-ecule C17H13NO, the phenyl rings are inclined to one another by 48.04 (9)°. In the crystal, weak C-H⋯π(ring) inter-actions form a layered structure parallel to the ab plane.

1,1,2,2,2,3,3,3-Octa-carbonyl-1,1,2,3-tetra-kis-(1,3,5-tri-aza-7-phosphatri-cyclo-[3.3.1.13,7]decane-κP)-triangulo-triosmium(0).

The title compound, [Os3(C6H12N3P)4(CO)8], crystallizes in the ortho-rhom-bic space group Pbca with Z = 8. The mol-ecule consists of a triangular triosmium(0) core surrounded by eight carbonyl ligands and four 1,3,5-tri-aza-7-phosphatri-cyclo-[3.3.1.13,7]decane (or PTA) ligands. One Os atom is coordinated by two PTA ligands and two CO ligands, while the other two Os atoms are each bonded to a single PTA ligand and three CO ligands. There is a small disorder associated with the Os3 unit so that a minor orientation has an occupancy of 2.17 (4)%. The title compound represents the first structurally characterized triangular Os3 carbonyl cluster with four monodentate tertiary phosphane ligands.

Bis(µ4-adamantane-1,3-di-carboxyl-ato-1κO 1:2κO 1':3κO 3:4κO 3')octa-carbonyl-1κ2 C,2κ2 C,3κ2 C,4κ2 C-tetra-kis-[tris-(4-methyl-phen-yl)phosphane]-1κP,2κP,3κP,4κP-tetra-osmium(I)(2 Os-Os).

The title complex, [{Os2(CO)4(C21H21P)2}2(C12H14O4)2], is a centrosymmetric mol-ecular loop consisting of two Os-Os sawhorse units linked by two adamantane di-carboxyl-ato bridges. It was synthesized by the microwave-mediated reaction between Os3(CO)12 and adamantane-1,3-di-carb-oxy-lic acid. In contrast to the related complex [{Os2(CO)6}2(µ4-adamantane-1,3-di-acetate)2], the metal-metal axes within each mol-ecule are oriented parallel rather than perpendicular to one another. The crystal structure exhibits cavities that contain residual electron density peaks, but it was not possible to unambiguously identify the solvent therein. The contribution of the disordered solvent mol-ecules to the scattering was removed using the SQUEEZE (Spek (2015 ▸). Acta Cryst. C71, 9-18) routine in PLATON [Spek (2020 ▸). Acta Cryst. E76, 1-11]. These solvent mol-ecules are not considered in the given chemical formula and other crystal data.

Synthesis and crystal structures of 2-(ferrocenyl-carbon-yl)benzoic acid and 3-ferrocenylphthalide.

The title compounds, 2-(ferrocenylcarbon-yl)benzoic acid, [Fe(C5H5)(C13H9O3)], 1, and 3-ferrocenylphthalide [systematic name: 3-ferrocenyl-2-benzo-furan-1(3H)-one], [Fe(C5H5)(C13H9O2)], 2, have been synthesized and structurally characterized by single-crystal X-ray diffraction. The crystal structure of compound 1 was solved recently at room temperature [Qin, Y. (2019 ▸). CSD Communication (CCDC deposition number 1912662). CCDC, Cambridge, England]. Here we report a redetermination of its crystal structure at 90 K with improved precision by a factor of about three. The mol-ecular structures of both compounds exhibit a typical sandwich structure. In the crystal packing of compound 1, each mol-ecule engages in inter-molecular hydrogen bonding, forming a centrosymmetric dimer with graph-set notation R 2 2 (8) and an O⋯O distance of 2.6073 (15) Å. There are weak C-H⋯O and C-H⋯π inter-actions in the crystal packing of compound 2. The phthalide moiety in 2 is oriented roughly perpendicular to the ferrocene backbone, with a dihedral angle of 77.4 (2)°.

Some chalcones derived from thio-phene-3-carbaldehyde: synthesis and crystal structures.

The synthesis, spectroscopic data and crystal and mol-ecular structures of four 3-(3-phenyl-prop-1-ene-3-one-1-yl)thio-phene derivatives, namely 1-(4-hydroxy-phen-yl)-3-(thio-phen-3-yl)prop-1-en-3-one, C13H10O2S, (1), 1-(4-meth-oxy-phen-yl)-3-(thio-phen-3-yl)prop-1-en-3-one, C14H12O2S, (2), 1-(4-eth-oxy-phen-yl)-3-(thio-phen-3-yl)prop-1-en-3-one, C15H14O2S, (3), and 1-(4--bromophen-yl)-3-(thio-phen-3-yl)prop-1-en-3-one, C13H9BrOS, (4), are described. The four chalcones have been synthesized by reaction of thio-phene-3-carbaldehyde with an aceto-phenone derivative in an absolute ethanol solution containing potassium hydroxide, and differ in the substituent at the para position of the phenyl ring: -OH for 1, -OCH3 for 2, -OCH2CH3 for 3 and -Br for 4. The thio-phene ring in 4 was found to be disordered over two orientations with occupancies 0.702 (4) and 0.298 (4). The configuration about the C=C bond is E. The thio-phene and phenyl rings are inclined by 4.73 (12) for 1, 12.36 (11) for 2, 17.44 (11) for 3 and 46.1 (6) and 48.6 (6)° for 4, indicating that the -OH derivative is almost planar and the -Br derivative deviates the most from planarity. However, the substituent has no real influence on the bond distances in the α,ß-unsaturated carbonyl moiety. The mol-ecular packing of 1 features chain formation in the a-axis direction by O-H⋯O contacts. In the case of 2 and 3, the packing is characterized by dimer formation through C-H⋯O inter-actions. In addition, C-H⋯π(thio-phene) inter-actions in 2 and C-H⋯S(thio-phene) inter-actions in 3 contribute to the three-dimensional architecture. The presence of C-H⋯π(thio-phene) contacts in the crystal of 4 results in chain formation in the c-axis direction. The Hirshfeld surface analysis shows that for all four derivatives, the highest contribution to surface contacts arises from contacts in which H atoms are involved.

Undeca-carbon-yl[(4-methyl-sulfanylphen-yl)di-phenyl-phosphane]triruthenium(0): crystal structure and Hirshfeld surface analysis.

The title cluster compound, [Ru3(C19H17PS)(CO)11], comprises a triangle of Ru0 atoms, two of which are bonded to four carbonyl ligands. The third metal atom is bound to three carbonyl ligands and the phosphane-P atom of a dissymmetric phosphane ligand, PPh2(C6H4SMe-4); no Ru⋯S inter-actions are observed. The phosphane occupies an equatorial position and its proximity to an Ru-Ru edge results in the elongation of this bond with respect to the others [2.8933 (2) Šcf. 2.8575 (2) and 2.8594 (3) Å]. In the crystal, phenyl-C-H⋯O(carbon-yl) and carbonyl-O⋯O(carbon-yl) [2.817 (2) Å] inter-actions combine to form a supra-molecular chain propagating along [111]; the chains pack without directional inter-actions between them. The carbonyl-O⋯O(carbon-yl) and other weak contacts have an influence upon the Hirshfeld surfaces with O⋯H contacts making the greatest contribution, i.e. 37.4% cf. 15.8% for O⋯O and 15.6% for H⋯H contacts.

Crystal structure of [µ-1κ2C1,C4:2(1,2,3,4-η)-1,2,3,4-tetra-phenyl-buta-1,3-diene-1,4-di-yl]bis-(tri-carbonyl-osmium)(Os-Os).

In the title complex C34H20O6Os2 or (µ-η4-C4Ph4)Os2(CO)6, one Os atom is part of a metalla-cyclo-penta-diene ring, while the second Os atom is π-bonded to the organic portion of this ring. The distance of 2.7494 (2) Šbetween the two Os atoms is typical of an Os-Os single bond. Three carbonyl ligands are attached to each Os atom and these six carbonyls adopt an eclipsed conformation. There are no bridging or semibridging CO groups. Two carbonyl ligands and all four phenyl groups are disordered over two slightly different positions for which each atom in the minor components is displaced less than 1 Šfrom the corresponding atom in the major components. The refined occupancies of the major com-ponents of the carbonyl ligands are 0.568 (16) and 0.625 (13), while those for the phenyl rings are 0.50 (3), 0.510 (12), 0.519 (18), and 0.568 (12).

Crystal structures of four new iridium complexes, each containing a highly flexible carbodi-phos-phorane PCP pincer ligand.

Compound [Ir(C8H12)(C51H45P4)]Cl2 or [Ir(cod)(CH(dppm)2-κ3P,C,P)]Cl2 (1a), was obtained from [IrCl(cod)]2 and the carbodi-phospho-rane (CDP) salt [CH(dppm)2]Cl [where cod = cyclo-octa-1,5-diene and dppm = bis-(di-phenyl-phosphino)methane]. Treatment of 1a with thallium(I) tri-fluoro-methane-sulfonate [Tl(OTf)] and subsequent crystallization gave complex [Ir(C8H12)(C51H45P4)](OTf)2·CH3CO2C2H5·CH2Cl2 or [Ir(cod)(CH(dppm)2-κ3P,C,P)](OTf)2·CH3CO2C2H5·CH2Cl2 (1b) [systematic name: (cyclo-octa-1,5-diene)(1,1,3,3,5,5,7,7-octa-phenyl-1,7-diphospha-3,5-di-phospho-niaheptan-4-yl)iridium(I) bis-(tri-fluoro-methane-sulfonate)-ethyl acetate-di-chloro-methane (1/1/1)]. This five-coordinate iridium(I) complex cation adopts a trigonal-bipyramidal geometry with the CDP carbon and one cod double bond in axial sites. Compound 1b represents the first example of a non-meridional coordination of the PCP pincer ligand [CH(dppm)2]+ with a P-Ir-P angle of 98.08 (2)°. Compound 2, [IrCl2H(C51H44P4)]·(CH3)2CO or [IrCl2H(C(dppm)2-κ3P,C,P)]·(CH3)2CO [systematic name: di-chlorido-hydrido(1,1,3,3,5,5,7,7-octa-phenyl-1,5λ5,7-triphospha-3-phospho-niahept-4-en-4-yl)iridium(III) acetone monosolvate], crystallizes as an acetone monosolvate. It is a six-coordinate IrIII coordination compound. Here, the PCP pincer ligand is coordinated in a meridional manner; one chlorido ligand is positioned trans to the carbon donor, the remaining two coordination sites being occupied by the second chlorido and a hydrido ligand trans to each other. Complex 3, [IrCl2H(C51H45P4)]Cl·5H2O or [IrCl2H(CH(dppm)2-κ3P,C,P)]Cl·5H2O [systematic name: di-chlorido-hydrido(1,1,3,3,5,5,7,7-octa-phenyl-1,7-diphospha-3,5-di-phospho-niaheptan-4-yl)iridium(III) chloride penta-hydrate], represents the conjugate CH acid of 2. The ligand [CH(dppm)2]+ is coordinated in a meridional manner. In the cationic six-coordinate IrIII complex 4, [IrClH(CO)(C51H44P4)]Cl·2CH3OH·H2O or [IrClH(CO)(C(dppm)2-κ3P,C,P)]Cl·2CH3OH·H2O [systematic name: carbonyl-chlorido-hydrido(1,1,3,3,5,5,7,7-octa-phenyl-1,5λ5,7-triphospha-3-phos-pho-niahept-4-en-4-yl)iridium(III) chloride-methanol-water (1/2/1)], the chlorido ligand is found in the plane defined by the Ir center and the meridional PCP ligand; the H and CO ligands are positioned axially to this plane and trans to each other.

Crystal structure of tetra-kis-[µ-2-(meth-oxy-carbon-yl)benzoato-κ2O1:O1']bis-[(N,N-di-methyl-formamide-κO)copper(II)](Cu-Cu) di-methyl-formamide disolvate.

The title compound, [Cu2(C9H7O4)4(C3H7NO)2]·2C3H7NO, crystallizes in the monoclinic P21/c space group, with the binuclear copper unit occupying a special position on an inversion center, i.e. the asymmetric unit of the crystal consists of one CuII ion, two 2-(meth-oxy-carbon-yl)benzoate ligands, and two DMF mol-ecules (one coordinated and one solvate). The binuclear complex displays a paddle-wheel-shaped structure with the two copper atoms being in a Jahn-Teller-distorted octa-hedral coordination environment. Each 2-(meth-oxy-carbon-yl)benzoate substituent acts as a bridging ligand and links two Cu atoms with a Cu-Cu distance of 2.633 (1) Å. The carboxyl-ate groups of the 2-(meth-oxy-carbon-yl)benzoate ligands adopt bidentate syn-syn bridging modes, with dihedral angles between the carboxyl-ate planes and the aromatic rings of 18.427 (4) and 43.029 (6)°. In the crystal, adjacent DMF mol-ecules coordinated to copper atoms are arranged in a mutual 'head-to-tail' manner by offset face-to-face π-π stacking inter-actions, resulting in chains along the c-axis direction. The planes of the coordinated DMF mol-ecules are parallel to each other, the distance between them being 3.33 (1) Å. A three-dimensional structure is assembled from the chains by weak C-H⋯O and C-H⋯π inter-molecular inter-actions involving the DMF solvent mol-ecules. One of the methyl ester groups is disordered over two sites with an occupancy ratio of 0.751 (12):0.249 (12).

[µ2-Bis(di-phenyl-phosphan-yl)hexa-ne]bis-[undeca-carbonyl-triangulo-triruthenium(3 Ru-Ru)] hexane monosolvate: crystal structure and Hirshfeld surface analysis.

In the title cluster complex hexane solvate, [Ru6(C30H32P2)(CO)22]·C6H14, two Ru3(CO)11 fragments are linked by a Ph2P(CH2)6PPh2 bridge with the P atoms equatorially disposed with respect to the Ru3 triangle in each case; the hexane solvent mol-ecule is statistically disordered. The Ru⋯Ru distances span a relatively narrow range, i.e. 2.8378 (4) to 2.8644 (4) Å. The hexyl chain within the bridge has an all-trans conformation. In the mol-ecular packing, C-H⋯O inter-actions between cluster mol-ecules, and between cluster and hexane solvent mol-ecules lead to a three-dimensional architecture. In addition, there are a large number of C≡O⋯π(arene) inter-actions in the crystal. The importance of the carbonyl groups in establishing the packing is emphasized by the contribution of 53.4% to the Hirshfeld surface by O⋯H/H⋯O contacts.