Redetermination of the structure of 2-amino-8-thia-1,5-diazaspiro[4,5]dec-1-en-5-ium chloride monohydrate

The reaction of β-(thiomorpholin-1-yl)propioamidoxime with tosyl chloride in CHCl3 in the presence of DIPEA when heated at 343 K for 8 h afforded the title hydrated salt, C7H14N3S+·Cl−·H2O, in 84% yield. This course of the tosylation reaction differs from the result of tosylation obtained for this substrate at room temperature, when only 2-amino-8-thia-1,5-diazaspiro[4.5]dec-1-ene-5-ammonium tosylate was isolated in 56% yield. The structure of the reaction product was established by physicochemical methods, spectroscopy, and X-ray diffraction. The single-crystal data demonstrated that the previously reported crystal structure of this compound [Kayukova et al. (2021). Chem. J. Kaz, 74, 21–31] had been refined in a wrong space group. In the extended structure, the chloride anions, water molecules and amine groups of the cations form two-periodic hydrogen-bonded networks with the fes topology.

Synthesis, crystal structure, DFT studies, and Hirshfeld surface analysis of N,N'-bis(3-quinolyl-methylene)diphenylethanedione dihydrazone

The synthesis, characterization, and theoretical studies of a novel hydrazine, N,N’-bis-(3-quinolylmethylene)diphenylethanedione dihydrazone (1) has been reported. The molecular structure has been characterized by room-temperature single-crystal X-ray diffraction which reveals that two quinoline moieties are disposed nearly perpendicularly around the central C-C bond giving a ‘L’ shape of the molecule. This particular geometry gives rise to the hydrogen-bonded supramolecular rectangle of two self-complementary molecules. These supramolecular units are further assembled by π-π interaction. The Hirshfeld surface analysis of compound 1 shows that C···C, C···H, H···H, and N···H interactions of 13.1, 9.9, 52.3, and 7.4%, respectively, which exposed that the main intermolecular interactions were H···H intermolecular interactions. Crystal data for C34H24N6: Triclinic, space group P-1 (no. 2), a = 10.885(3) Å, b = 11.134(3) Å, c = 12.870(3) Å, α = 90.122(6)°, β = 114.141(6)°, γ = 110.277(5)°, V = 1316.1(6) Å3, Z = 2, T = 100(2) K, μ(MoKα) = 0.080 mm-1, Dcalc = 1.304 g/cm3, 7309 reflections measured (3.518° ≤ 2Θ ≤ 39.276°), 2318 unique (Rint = 0.0527, Rsigma = 0.0565) which were used in all calculations. The final R1 was 0.0416 (I > 2σ(I)) and wR2 was 0.1074 (all data).

Five Dinuclear Lanthanide Complexes Based on 2,4-dimethylbenzoic Acid and 5,5′-dimethy-2,2′-bipyridine: Crystal Structures, Thermal Behaviour and Luminescent Property

A series of new complexes, [Ln (2,4-DMBA)3(5,5′-DM-2,2′-bipy)]2 (Ln = Sm(1), Eu (2)), [Pr (2,4-DMBA)3 (5,5′-DM-2,2′-bipy)]2·0.5(C2H5OH) (3), [Ln (2,4-DMBA)3 (5,5′-DM-2,2′-bipy)]2·0.5(2,4-DMBAH)·0.25(5,5′-DM-2,2′-bipy) (Ln = Tb (4), Dy (5)) (2,4-DMBA = 2,4-dimethylbenzoate, 5,5′-DM-2,2′-bipy = 5,5′-dimethy-2,2′-bipyridine) were synthesized via hydrothermal reaction conditions. The complexes were characterized through elemental analysis, Infrared spectra (IR), Raman (R) spectra, UV-Vis spectra, single X-ray diffraction. Single crystal data show that complexes 1–5 are binuclear complexes, but they can be divided into three different crystal structures. The thermal decomposition mechanism of complexes 1–5 were investigated by the technology of simultaneous TG/DSC-FTIR. What’s more, the luminescent properties of complexes 1–2 and 4 were discussed, and the luminescence lifetime (τ) of complexes 2 and 4 were calculated.

Synthesis, crystal structure elucidation, Hirshfeld surface analysis, 3D energy frameworks and DFT studies of 2-(4-fluorophenoxy) acetic acid

The compound 2-(4-fluorophenoxy) acetic acid was synthesized by refluxing, 4-fluoro-phenol as a starting material with ethyl chloroacetate in acetone as solvent. The compound crystallizes in the monoclinic crystal system with the space group P21/c. Crystal data for C8H7FO3, a = 13.3087(17) Å, b = 4.9912(6) Å, c = 11.6018(15) Å, β = 104.171(4)°, V = 747.21(16) Å3, Z = 4, T = 293(2) K, μ(CuKα) = 1.142 mm-1, Dcalc = 1.512 g/cm3, 8759 reflections measured (13.72° ≤ 2Θ ≤ 130.62°), 1246 unique (Rint = 0.0528) which were used in all calculations. The final R1 was 0.0458 (>2sigma(I)) and wR2 was 0.1313 (all data). The structure was stabilized by C-H···O and C-H···Cg interactions. The intermolecular interactions in the crystal were studied using Hirshfeld surface analysis. 3D energy frameworks were computed to visualize the packing modes. DFT calculations were performed. The FMOs were studied to estimate the kinetic stability and reactivity of the molecule. The MEP surface was generated to investigate the charge distribution and chemical reactive sites in the molecule.

Crystal structure of bis[cis-diaquabis(phenanthroline)cobalt(II)] bis(citrato)germanate(IV) dinitrate

The asymmetric unit of the title compound, [Co(C12H8N2)2(H2O)2]2[Ge(C6H5O7)2](NO3)2, features two complex [(C12H8N2)2(H2O)2Co]2+ cations, two NO3 − anions as well as one centrosymmetric [(C6H5O7)2Ge]2− anion. Two HCit ligands (Cit = citrate, C6H4O7) each coordinate via three different oxygen atoms (hydroxylate, α-carboxylate, β-carboxylate) to the Ge atom, forming a slightly distorted octahedron. The coordination polyhedron of the Co atom is also octahedral, formed by coordination of four nitrogen atoms from two phenanthroline molecules and two water oxygen atoms. In the crystal, the cations and anions are linked by hydrogen bonds and form layers parallel to the bc plane. The structure exhibits disorder of the NO3 − anion [disorder ratio 0.688 (9) to 0.312 (9)]. There are also highly disordered solvent molecules (presumably water and/or ethanol) in the crystal structure; explicit refinement of these molecules was not possible, and the content of the voids was instead taken into account using reverse Fourier transform methods [SQUEEZE procedure in PLATON; Spek (2015). Acta Cryst. C71, 9–18]. The given chemical formula and other crystal data do not take into account the unknown solvent molecule(s).

Synthesis and characterization of Ti(IV), Zr(IV) and Al(III) salen-based complexes

New Ti(IV), Zr(IV) and Al(III) salen-based complexes of formulae [(L)TiCl2], 2, [(L)ZrCl2], 3, and [(L){Al(CH2CH(CH3)2)2}2], 4, where L = meso-(R,S)-diphenylethylene-salen, were synthesized in high yields. [(L){Al(CH2CH(CH3)2)2}2] is a bimetallic complex that results from the reaction of H2L with either 1 or 2 equivalent of Al(CH2CH(CH3)2)3. The solid-state molecular structures of compounds 2 and 4·(C7H8) were obtained by single-crystal X-ray diffraction. Crystal data for C44H54Cl2N2O2Ti, (2a): monoclinic, space group C2/c (no. 15), a = 27.384(1) Å, b = 12.1436(8) Å, c = 28.773(2) Å, β = 112.644(2)°, V = 8830.6(9) Å3, Z = 8, μ(MoKα) = 0.350 mm-1, Dcalc = 1.146 g/cm3, 26647 reflections measured (5.204° ≤ 2Θ ≤ 50.7°), 8072 unique (Rint = 0.0967, Rsigma = 0.1241) which were used in all calculations. The final R1 was 0.0640 (I > 2σ(I)) and wR2 was 0.1907 (all data). Crystal data for C62H72Cl2N2O2Ti (2b): monoclinic, space group P21/c (no. 14), a = 19.606(1) Å, b = 12.793(1) Å, c = 23.189(2) Å, β = 105.710(4)°, V = 5599.0(7) Å3, Z = 4, μ(MoKα) = 0.291 mm-1, Dcalc = 1.182 g/cm3, 37593 reflections measured (3.65° ≤ 2Θ ≤ 50.928°), 10304 unique (Rint = 0.0866, Rsigma = 0.1032) which were used in all calculations. The final R1 was 0.0593 (I > 2σ(I)) and wR2 was 0.1501 (all data). Crystal data for C67H97Al2N2O2 (4·(C7H8)): triclinic, space group P-1 (no. 2), a = 10.0619(9) Å, b = 16.612(2) Å, c = 21.308(2) Å, α = 67.193(5)°, β = 78.157(6)°, γ = 77.576(5)°, V = 3176.8(6) Å3, Z = 2, μ(MoKα) = 0.088 mm-1, Dcalc = 1.063 g/cm3, 42107 reflections measured (5.382° ≤ 2Θ ≤ 51.624°), 12111 unique (Rint = 0.0624, Rsigma = 0.0706) which were used in all calculations. The final R1 was 0.0568 (I > 2σ(I)) and wR2 was 0.1611 (all data). The solid-state molecular structure of [(L){Al(CH2CH(CH3)2)2}2] reveals that both metal centres display a slightly distorted tetrahedral geometry bridged by the salen ligand. Both [(L)TiCl2] and [(L)ZrCl2] complexes display octahedral geometry with trans-chlorido ligands.

Refinement of K[HgI3]·H2O using non-spherical atomic form factors

The crystal structure model for potassium triiodidomercurate(II) monohydrate, K[HgI3]·H2O, based on single-crystal data, was reported 50 years ago [Nyqvist & Johansson (1971). Acta Chem. Scand. 25, 1615–1629]. We have now redetermined this structure with X-ray diffraction data at 0.70 Å resolution collected at 153 K using Ag Kα radiation. Combined quantum mechanical methods (ORCA) and computation of non-spherical scattering form factors (NoSpherA2) allowed the refinement of the shape of the water molecule with anisotropic H atoms, despite the presence of heavy elements in the crystal. The refined shape of the water molecule via this Hirshfeld refinement is close to that determined for liquid water by neutron diffraction experiments. Moreover, the Laplacian of the electron density clearly shows how electron density accumulates along the O—H σ-valence bonds in the water molecule.

13-Benzyl-4,11-dihydroxy-1,8-diphenyl-2,9-dithia-13-azadispiro[4.1.4.3]tetradecan-6-one

In the title compound, C30H31NO3S2, the piperidine ring adopts a distorted chair conformation. The thiophene rings have twisted conformations about the C—C bonds. The mean plane of the piperidine ring makes a near orthogonal conformation with the toluene ring. Two of the phenyl rings in the structure are positionally disordered over two sets of sites with occupancies of 0.56 (2)/0.44 (2) and 0.672 (16)/0.328 (16). A region of disordered electron density was corrected for using the SQUEEZE [Spek (2015). Acta Cryst. C71, 9–18] routine in PLATON. The given chemical formula and other crystal data do not take into account the unknown solvent molecule. In the crystal, O—H...O hydrogen bonds are observed along with intramolecular S...H, O...H, C...H and H...H contacts.

Redetermination of K2Mg3(OH)2(SO4)3(H2O)2 from single-crystal X-ray data revealing the correct hydrogen-atom positions

In comparison with the previous structure determination of K2Mg3(OH)2(SO4)3(H2O)2, dipotassium trimagnesium dihydroxide tris(sulfate) dihydrate, from laboratory powder X-ray diffraction data [Kubel & Cabaret-Lampin (2013). Z. Anorg. Allg. Chem. 639, 1782–1786], the present redetermination against CCD single-crystal data has allowed for the modelling of all non-H atoms with anisotropic displacement parameters. As well as higher accuracy and precision in terms of bond lengths and angles, the clear localization of the H-atom positions leads also to a reasonable hydrogen-bonding scheme for this hydroxy hydrate. The structure consists of (100) sheets composed of corner- and edge-sharing [MgO6] octahedra and sulfate tetrahedra. Adjacent sheets are linked by the potassium cations and a hydrogen bond of medium strength involving the water molecule. The title compound is isotypic with its CoII and MnII analogues: the three K2 M 3(OH)2(SO4)3(H2O)2 (M = Mg, Co, Mn) structures are quantitatively compared.

Regiospecific substitution of the β-vinylic sp2 carbon of cyclohexenones bearing the α-chloro- and β-tosylate-groups: Single crystal XRD/Hirshfeld surface/in-silico studies of three representative compounds

2-Chloro-3-tosyl-5,5-dimethyl-2-cyclohexenone was subjected to a series of regiospecific Suzuki-Miyaura cross-coupling reactions in suspensions of nine different substituted boronic acids, Pd(OAc)2, P(Ph3)3, K3PO4 and 1,4-dioxane solvent, under sealed tube conditions. The regiospecific substitution of the tosyl-group by the aryl group in preference over the chloride- group was observed. A comparison between the bromo- and tosylate group’s reactivities is highlighted. Using the methodology, the products: 2-chloro-3-aryl-5,5-dimethyl-2-cyclohexenones were isolated in greater than 85% yields. Good quality crystals of three representative compounds were obtained by slow evaporation technique and subjected to single crystal XRD studies, Hirshfeld surface analysis, 3-D energy framework, and molecular docking studies. Crystal data for compound 3; C15H17ClO4S: monoclinic, space group P21/c (no. 14), a = 8.8687(3) Å, b = 10.5537(4) Å, c = 16.6862(7) Å, β = 89.807(3)°, V = 1561.78(10) Å3, Z = 4, T = 290 K, μ(MoKα) = 0.390 mm-1, Dcalc = 1.398 g/cm3, 13623 reflections measured (6.716° ≤ 2Θ ≤ 54.962°), 3570 unique (Rint = 0.0467, Rsigma = 0.0512) which were used in all calculations. The final R1 was 0.0452 (I > 2σ(I)) and wR2 was 0.1019 (all data). Crystal data for compound 5e; C20H18O2FCl: monoclinic, space group P21/c (no. 14), a = 6.4900(5) Å, b = 18.6070(13) Å, c = 14.2146(11) Å, β = 102.324(2)°, V = 1677.0(2) Å3, Z = 4, T = 296(2) K, μ(MoKα) = 0.239 mm-1, Dcalc = 1.309 g/cm3, 25575 reflections measured (6.262° ≤ 2Θ ≤ 52.224°), 3283 unique (Rint = 0.0494, Rsigma = 0.0307) which were used in all calculations. The final R1 was 0.0875 (I > 2σ(I)) and wR2 was 0.2056 (all data). Crystal data for compound 5h; C12H13OSCl: triclinic, space group P-1 (no. 2), a = 6.7517(6) Å, b = 8.8376(9) Å, c = 12.6049(12) Å, α = 109.538(3)°, β = 98.597(3)°, γ = 90.417(3)°, V = 699.52(12) Å3, Z = 2, T = 290 K, μ(MoKα) = 0.410 mm-1, Dcalc = 1.376 g/cm3, 28754 reflections measured (6.114° ≤ 2Θ ≤ 59.288°), 3898 unique (Rint = 0.0544, Rsigma = 0.0349) which were used in all calculations. The final R1 was 0.1101 (I > 2σ(I)) and wR2 was 0.2481 (all data).