S. P. Kpranenko1, E. A. Bykova1, K. V. Yusenko1,2, A. P. Tyutyunnik3, S. A. Gromilov1,4 1A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk 2Solid-chem GmbH, Bochum, Germany 3Institute of Solid State Chemistry, Ural Division, Russian Academy of Sciences, Ekaterinburg 4Novosibirsk State University
Keywords: ruthenium, molybdenum, rhenium, iridium, complex salt, crystal chemistry, X-ray crystallographic analysis
X-ray crystallographic analysis is used to determine the crystal structures of [Ru(NH3)6](MoO4)Cl×3H2O and [М(NH3)6](ReO4)3×2H2O (M = Ru, Ir) complex salts. The features of the fragment packing are studied.
A. V. Belyaev, A. I. Smolentsev, I. A. Baidina, S. V. Tkachev
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk
Keywords: rhodium, trans-diamminetetranitrites, salts, crystal structure, 14,15N NMR
Complex rhodium(III) salts with the composition trans-М[Rh(NH3)2(NO2)4], where М = K+, Cs+, Ag+, and N(CH3)4+, are prepared and characterized. The molecular and crystal structures are determined by X-ray crystallography.
E. E. Netreba
V. I. Vernadsky Taurida National University, Simferopol, Ukraine
Keywords: copper(II), trigonal bipyramid, spirocarbone, coordination polymer, structure, single-crystal XRD
A coordination polymer {[Cu(C11H20N4O2)2(H2O)]2+×2(NO3–)}n (I) is synthesized and analyzed using single-crystal XRD. The crystals are monoclinic: space group P2/c, a = 12.5237(6) Å, b = 7.3310(3) Å, c = 16.8926(8) Å, β = 92.569(4)°, V = 1549.38(13) Å3, rcalc = 1.47 g/cm3, and Z = 2. The copper atom is in a special position in the second-order axis. The coordination polyhedron of the metal is a trigonal bipyramid. In the axial direction, it is coordinated by two oxygen atoms O(1) of the organic ligand molecules connected by the symmetry operation [–x, y, 0.5–z]; the angle O(1)Cu(1)O(1)i is 175.16(15)°. In the equatorial direction, the copper atom is coordinated by oxygen atoms O(2) of two ligand molecules connected with the reference molecule by the symmetry operations [–x, y, 0.5–z] and [x, 1–y, –0.5+z] and the water molecule О(6) in a special position on the twofold axis. The OCuO angles between the equatorial oxygen atoms are 96.80(16)-131.60(8)°, and those between the axial and equatorial atoms are 87.58(8)-91.60(10)°. It is noteworthy that the length of the Cu–O(1) bond (1.955(2) Å) with the axial carbonyl oxygen atom is somewhat shorter than the bond (2.060(3) Å) with the equatorial atom. Nitrate anions are outside the coordination sphere of the metal. The Cu…Cu distance in the polymer is 8.33 Å. To confirm the purity of the sample of I, the powder X-ray pattern is refined by the Rietveld method; the lattice parameters at room temperature are: a = 12.535(4) Å, b = 7.3161(13) Å, c = 16.841(5) Å, β = 92.11(2)°, and V = 1543.4(7) Å3.
S. I. Levchenkov1, L. D. Popov2, I. N. Shcherbakov2, G. G. Aleksandrov3, A. A. Zubenko4, V. A. Kogan2 1Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don 2Chemistry Department, Southern Federal University, Rostov-on-Don 3N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 4North-Caucasian Zonal Research Veterinary Institute, Novocherkassk, Russia
Keywords: hydrazones, tautomerism, X-ray crystallography, hydrogen bond, density functional theory
Subsection: STRUCTURE OF BIOLOGICALLY ACTIVE SYSTEMS
1'-Phthalazinylhydrazones of salicylaldehyde, its substituted derivatives, and 2-diphenylphosphinebenzaldehyde are synthesized and studied. A description is given of the structures salicylaldehyde 1'-phthalazinylhydrazone (1а) and 2-diphenylphosphinebenzaldehyde 1'-phthalazinylhydrazone (2), which exist in the crystal in the hydrazonophthalazone tautomeric form. Molecules of hydrazone 1а form in the crystal infinite stacks of hydrogen bonded dimers with intermolecular π-stacking interactions. A quantum chemical calculation is made of the geometry and total energy of the possible tautomers in vacuum and in aqueous and chloroform solutions. The hydrazonophthalazone tautomers are shown to be the most stable in all cases. The X-ray crystallography results are compared with the calculated data.
S. G. Semenov1, Yu. F. Sigolaev2, A. V. Belyakov2 1Saint-Petersburg State University, Saint-Petersburg 2Saint-Petersburg State Institute of Technology, Saint-Petersburg
Keywords: nanostructures, polycyclic compounds, cavitands, icosahedral symmetry, M06-2X/6-31G(d,p), M06-2X/6-311G(d)
By quantum chemical DFT M06-2X/6-31G(d,p) method, the equilibrium parameters of rigid and stable hydrocarbon clusters of icosahedral symmetry with a dodecahedron structure whose sites are occupied by 20 adamant-1,3,5-triyl moieties linked with each other either directly or through bridges containing two or four carbon atoms are determined. The radius of the smallest studied quasispherical molecules is 1.05 nm and that of the largest one is 1.76 nm. The radius of the inner cavity in them varies from 0.37 nm (C200H260) to 1.06 nm (C320H260). Perfluorination increases the outer and decreases the inner radius of super dodecahedrane.
N. N. Golovnev1, M. S. Molokeev2 1Siberian Federal University, Krasnoyarsk 2L. V. Kirensky Institute of Physics, Siberian Division, Russian Academy of Sciences, Krasnoyarsk
Keywords: catena-di(μ2-2-thiobarbiturato-O,S)aqualead(II), crystal structure, hydrogen bonds, π–π interaction
The crystal structure of catena-di(μ2-2-thiobarbiturato-O,S)aqualead(II) C8H8N4O5S2Pb (C4H4N2O2S is 2-thiobarbituric acid, H2TBA) is determined. Crystallographic data for catena-[Pb(H2O)(μ2-HTBA-O,S)2] are as follows: a = 6.5972(1) Å, b = 9.8917(2) Å, c = 10.0893(2) Å, α = 106.702(1)°, β = 93.395(2)°, γ = 107.48(1)°, V = 593.82(2) Å3, space group P1, Z = 2. The Pb2+ ion is linked with six monodentate HTBA − ligands through two O atoms and four S atoms and also connected with a water molecule. Additionally, there is a shortened Pb–S contact (3.622 Å), given which the complex polyhedron represents a distorted square antiprism. Hydrogen bonds N–H⋯O and O–H⋯O form a branched three-dimensional network. The structure is also stabilized by the π–π-interaction of heterocyclic HTBA− ions.
E.-J. Gao, T.-L. Liu, W. Jiao, L.-L. Jiang, D. Zhang, Y.-J. Zhang, J. Xu, G.-L. Wu
Shenyang University of Chemical Technology, Shenyang 110142, P. R. China
Keywords: Zn(II) complex, 2-mercaptonicotinic acid, crystal structure, coordination
A novel Zn(II) coordination polymer [Zn2(phen)2]L4×3H2O(1) is synthesized by the reaction of Zn(NO3)2, Phen(1,10-phenanthroline), and L(2-mercaptonicotinic acid) at room temperature and structurally characterized by X-ray single crystal diffraction along with IR spectra and elemental analysis. Title complex 1 belongs to the triclinic system with the space group ( P-1), a = 10.9373(11) Å, b = 11.6201(12) Å, c = 13.1371(14) Å; α = 116.100(1)°, β = 97.717(2)°, γ = 108.652(2)°, V = 1344.4(2) Å3; Z = 2, ρcalcd = 1.596 g×cm–3, F(000) = 664, R1 = 0.0708 and wR2 = 0.1823 independent reflections for 18523 observed ones (I > 2σ(I)), and the zinc atom is rendered five-coordinated in a distorted tetragonal pyramid coordination geometry by two nitrogen atoms from the phen molecule, two oxygen atoms from two L molecules, and an oxygen atom from the H2O molecule. Complex 1 forms a 1D chain by O—H⋯O hydrogen bonds from free-water, while the 2D layer structure is formed by C—H⋯O hydrogen bonds through the L ligand of adjacent chains. These compounds further result in a 3D network structure by the intermolecular π⋯π stacking interaction of the neighbouring layers.
E.-J. Gao, L.-L. Jiang, D. Zhang, W. Jiao, T.-L. Liu, Y.-J. Zhang, G.-L. Wu, J. Xu
Shenyang University of Chemical Technology, Shenyang 110142, P. R. China
Keywords: 2,2'-bipyridine-3,3'-dicarboxylic acid (3,3'-bpbc), cobalt(II) complex, crystal structure, coordination
A novel coordination polymer constructed with [Co(3,3'-bpbc)(H2O)3]×H2O(I) (3,3'-bpbc = 2,2'-bipyridine-3,3'-dicarboxylic acid) is successfully synthesized at room temperature and characterized by elemental analysis and IR spectra. The crystal structure of the complex is determined by single crystal X-ray diffraction. The unit cell parameters for complex I are: a = 9.9606(11) Å, b = 9.2552(10) Å, c = 16.0258(17) Å, β = 96.731(0)°, V = 1467.2(3) Å3, Z = 4, space group P2(1)/n. In the crystal, the cobalt(II) ion adopts a hexa-coordinate environment, and the structure units aggregate together to give birth to infinite 1D chains. The 2D and 3D framework is constructed via intermolecular hydrogen bonds.
A new compound of 6-ferrocenyl-3-phenyl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole is synthesized and its single crystal structure is determined by X-ray diffraction method. The compound belongs to the monoclinic P21/c space group with cell parameters: a = 10.5523(12) Å, b = 13.8414(16) Å, c = 11.4303(13) Å, V = 1603.5(3) Å3.
Yu. M. Chumakov1, T. B. Capatina2, P. Petrenko1, V. I. Tsapkov2, A. P. Gulea2 1Institute of Applied Physics, Academy of Sciences of Moldova, Moldova, Chisinau 2Moldova State University, Moldova, Chisinau
Keywords: 3d metal complexes, single crystal X‑ray diffraction study, carbamide derivatives
The crystal structure of tetra(m-acetato)-bis{[1-ethyl-3-(pyridine-2-yl)carbamide]copper} Cu2(L)2(CH3COO)4 (I), where L is 1-ethyl-3-(pyridine-2-yl)carbamide, is determined. The asymmetric unit cell of the crystal structure of I contains a copper complex with two acetate ions and a monodentate molecule of 1-ethyl-3-(pyridine-2-yl)carbamide, which is coordinated via the pyridine nitrogen atom. Due to the symmetry center, binuclear complexes form in the crystal, in which the acetate ions act as bridges between the metal atoms. In them, the coordination polyhedron of the central copper atoms represents an almost ideal tetragonal pyramid. Its base is formed from the oxygen atoms of acetate ions. In the crystal of the binuclear complex, hydrogen bonds form between the acetate ions and the L ligand along with an intramolecular hydrogen bond, which stabilize the conformation of the organic L molecule. Between the neighboring complexes in the crystal, the van der Waals interaction occurs.
