Carbon–hydrogen and carbon–phosphorus bond cleavage in a triruthenium cluster complex containing dppm: The crystal and molecular structures of Ru3(CO)6{μ 3-OPPh2 C2H(C6H4)PPhCH2PPh}(μ 3-OPPh2)Ph and Ru3(CO)6 {μ-OPPh2C2H(C6H4)PPhO}(μ-PPh2)(μ-PPh2O)

The crystal and molecular structures of Ru₃(CO)₆{μ ₃-OPPh₂C₂H(C₆H₄)PPhCH₂PPh}-(μ ₃-OPPh₂)Ph (1) and Ru₃(CO)₆{μ-OPPh₂C₂H(C₆H₄)PPhO}(μ-PPh₂)(μ-PPh₂O) (2) have been determined by single crystal X-ray diffraction. Both complexes contain oxygen atoms oxidatively inserted into phosphorus–ruthenium bonds, and unique σ/π multidentate ligands formed from C $---{\text{H}}$ H and C $--$ P bond cleavage in bis(diphenylphosphino)acetylene and bis(diphenylphosphino)methane. Complex 1 crystallized in the triclinic space group ${\bar 1}$ , with lattice parameters a = 11.642(4) Å, b = 15.018(5) Å, c =16.587(5) Å, α = 2.48(3)°, β = 76.47(2)°, γ = 70.35(3)°, V = 2651.1(15) ų, Z = 2. Complex 2 crystallized in the centered monoclinic space group, C2/c, with lattice parameters a = 34.467(4) Å, b = 14.274(2) Å, c = 23.258(3) Å, β = 5.29(1)°, V = 11394(3) ų, Z = 8.     

Structure of a liquid crystal of 4-cyano-4′-n-octyloxybiphenyl

The structure of a liquid crystal of 4-cyano-4′-n-octyloxybiphenyl (C₂₁H₂₅NO) is determined by X-ray diffraction analysis. The compound crystallizes in the triclinic crystal system with unit cell parameters a = 7.322(1) Å, b = 12.693(3) Å, c = 20.393(2) Å, α = 92.45(1)°, β = 99.96(1)°, γ = 99.35(2)°, and space group $P\bar 1$ . The structure is solved by the direct method and refined to R = 0.057. Two independent molecules are located in the asymmetric unit. No short intermolecular contacts are observed in the crystal packing.     

Crystal structure analysis of (Morpholino)(Phenyl)(Dicyclohexylamino) phosphiniminocyclotrithiazene

The title compound (C₆H₅)(C₄H₈NO)[N(C₆H₁₁)₂]P=N-S₃N₃ crystallizes in a triclinic crystal system with unit cell parameters a = 9.8884(4) Å, b = 10.6075(1) Å, c = 14.2276(2) Å, α = 78.14(3)°, β = 79.31(1)°, λ = 65.42(2)°, V = 1319.44(6) ų, Z = 2, and space group $P\bar 1$ . The cyclotrithiazene ring adopts a “distorted chair” conformation with a deviation of 0.682(7) Å for the tricoordinated sulfur atom. Remarkably, a short exocyclic S-N bond length 1.489(4) Å along with a large P-N-S angle 136.2(3)° are observed with the iminophosphorus moiety.     

X-ray diffraction investigation of trans-2,8-dihydroxy-2,8-diphenyl-4,4′,6,6′,10,10′, 12,12′-octamethylcyclohexasiloxane and trans-2,8-dihydroxy-2,4,4′,6,6′,8,10,10′, 12,12′-decamethyl-5-carbahexacyclosiloxane

The crystal structures of two organosilicon compounds are studied by X-ray diffraction. Crystals of trans-2,8-dihydroxy-2,8-diphenyl-4,4′,6,6′,10,10′,12,12′-octamethylcyclohexasiloxane, C₂₀H₃₆O₈Si₆, (I) are triclinic; at 110 K, a = 11.476(1) Å, b = 12.106(1) Å, c = 13.636(1) Å, α = 94.337(1)°, β = 112.669(1)°, γ = 112.216(1)°, space group $P\bar 1$ , Z = 2, and R = 0.057 for 5069 reflections with F > 4σ(F). Crystals of trans-2,8-dihydroxy-2,4,4′,6,6′,8,10,10′,12,12′-decamethyl-5-carbahexacyclosiloxane, C₁₁H₃₄O₇ Si₆, (II) are tetragonal; at 293 K, a = b = 15.487(3) Å, c = 11.364(3) Å, space group P4₂/n, Z = 4, and R = 0.055 for 955 reflections with F > 4σ (F). It is found that the structure of compound I, in which the substituents at the Si(1) atom differ in volume and inductive effect, contains two crystallographically independent molecules with different conformations of the hexasiloxane ring. In structure II, the oxygen atom and the methylene group are statistically disordered as a result of the location of the molecule at the center of symmetry. Although the SiCSi angle [122.1(1)°] differs noticeably from the tetrahedral angle, its value is characteristic of cyclohexasiloxanes and is not related to the disorder.     

Crystal structures and properties of isomers of 3,5-dinitro-(4-acetylphenyl)aminobenzoyl (p-bromophenyl)amide

The para and ortho isomers of 3,5-dinitro-(4-acetylphenyl)aminobenzoyl (p-bromophenyl)amide (I and II, respectively) are synthesized, and their physicochemical properties and structure are investigated. The para isomer I has a higher melting temperature and is less soluble in organic solvents as compared to the ortho isomer II. The electronic absorption spectra indicate that absorption for molecule I occurs at longer wavelengths than for molecule II. A correlation between the physicochemical properties and the crystal structures of compounds I and II is revealed. Crystals I · 0.5C₆H₆ are triclinic; the unit cell parameters are a = 11.760(2) Å, b = 13.958(3) Å, c = 15.012(3) Å, α = 108.01(2)°, β = 103.95(1)°, γ = 92.00(2)°, V = 2258.3(8) ų, space group $P\bar 1$ , and Z = 4. Crystals II are monoclinic; the unit cell parameters are a = 9.302(2) Å, b = 16.380(3) Å, c = 13.480(3) Å, β = 100.09(3)°, V = 2022.1(7) ų, space group P2₁/c, and Z = 4. Structures I · 0.5C₆H₆ and II are characterized by intramolecular and intermolecular hydrogen bonds.     

Synthesis and structure of (NH4)3[UO2(C3H2O4)2(NCS)] · 2H2O

Malonate-thiocyanate complex (NH₄)₃[UO₂(C₃H₂O₄)₂(NCS)] · 2H₂O is synthesized and studied by X-ray diffraction. The compound crystallizes in the monoclinic system: a = 13.9983(4) Å, b = 8.1947(2) Å, c = 16.4678(4) Å, β = 100.846(1)°, space group Cc, Z = 4, and R = 0.0158. The main structural units of the crystal are mononuclear [UO₂(C₃H₂O₄)₂(NCS)]^3? groups belonging to the AB ₂ ⁰¹ M ₁ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₂O ₄ ^2? , M ¹ = NCS^?). Discrete uranium-containing groups are connected by electrostatic interactions with ammonium ions and by hydrogen bonds. Some specific structural features of crystals containing [UO₂(L)₂(NCS)]^3? complexes, where L is the oxalate or malonate ion, are discussed.     

Refinement of the crystal structure of sanidine-like feldspar

The crystal structure of sanidine-like feldspar of the composition KAlSi₃O₈ from the Khibiny alkaline massif (the Kola Peninsula) has been refined (X-ray diffraction analysis; automated Syntex $P\bar 1$ diffractometer; 2θ: θ scanning technique; 2320 reflections; R _(hkl) = 0.0409; anisotropic refinement; AREN program package). The data obtained for KAlSi₃O₈ are: a = 8.615(9), b = 13.030(7), c = 7.200(5) Å, α = 89.99(5)°, β = 116.01(6)°, γ = 89.98(7)°, Z = 4, sp. gr. $C\bar 1$ . Microtwinning revealed in the crystal structure of the mineral explains the simultaneous existence of two structural-optical types in one sample—“high” and “low” sanidines.     

Crystal structure of 2,4′-biflavonoid

The X-ray crystal structure of 2,4′-biflavonoid has been determined. Colorless regular prism shaped crystals of C₃₀H₂₂O₄ crystallize in the space group $P\bar 1$ with cell dimensionsa=11.574(1) Å,b=12.235(1) Å,c=17.428(1) Å, α=108.46(3)^o, β=80.08(1)^o, γ=103.34(2)^o,V=2264.7(4) ų, andZ=4.     

Copper(II) bis [2-((E)-2-(pyrid-2-yl)ethylimino)methyl)-6-bromo-4-chlorophenolate]

A new complex CuL ₂ [HL = 2-((E)-(2-(pyridin-2-yl)ethylimino)methyl)-6-bromo-4-chlorophenol] was synthesized, and its structure (C₂₈H₂₂Br₂Cl₂CuN₄O₂, Mr = 740.76) was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the triclinic system, space group $P\bar 1$ , with a = 5.157(6), b = 12.090(1), c =12.310(1) Å, α = 113.962(2)°, β = 96.7910(10)°, γ = 90.0300(10)°, V = 695.4(8) ų, Z = 1, R = 0.0481. The complex molecules are linked via the weak C-H...N hydrogen bonds, leading to the formation of one dimension (1D) chains along the a axis.     

Crystal structure of (3-aminopropionato)bis(ethylenediamine)cobalt(III) catena-di(μ-chloro)dichloroplumbate(II) monohydrate

Crystals of [Co(C₂H₈N₂)₂(C₃H₆NO₂)]PbCl₄ · H₂O [a = 7.627(1) Å, b = 11.238(1) Å, c = 11.444(1) Å, α = 99.125(1)°, β = 103.80(1)°, γ = 94.739(1)°, V = 933.09(1) ų, Z = 2, and space group $P\bar 1$ ] contain the octahedral PbCl₆ groups that share edges to form infinite [Cl₂Pb(μ-Cl)₂] _n ²ⁿ chains, in which the terminal Cl atoms occupy the cis positions. The Pb-Cl bond lengths are 2.763(1)–3.180(3) Å. In the discrete cationic complexes, the Co atom is coordinated by two ethylenediamine molecules and the 3-aminopropionate anion. In the enantiomeric complex with the Δ absolute configuration, the ethylenediamine rings have the λ and δ configurations and the aminopropionate ring has the λ configuration.     

X-ray diffraction study of 2,2′,4,4′,6,8,8′,10,10′,12-decamethylbicyclo[5.5.1]hexasiloxane and 2,2′,4,4′,6,8,8′,10,10′,12-decamethylbicyclo[5.5.1]-9-carbahexasiloxane

The crystal structures of two organosilicon compounds are studied by X-ray diffraction at 200 K. Crystals of 2,2′,4,4′,6,8,8′,10,10′,12-decamethylbicyclo[5.5.1]hexasiloxane (C₁₀H₃₀O₇Si₆) are monoclinic, a = 12.260(1) Å, b = 11.716(1) Å, c = 32.169(2) Å, β = 92.802(2)°, space group C2/c, Z = 8, wR2 = 0.132, and R1 = 0.053 for 3989 reflections with F > 4σ(F). Crystals of 2,2′,4,4′,6,8,8′,10,10′, 12-decamethylbicyclo[5.5.1]-9-carbahexasiloxane (C₁₁H₃₂O₆Si₆) are triclinic, a = 10.709(1) Å, b = 11.046(1) Å, c = 12.111(1) Å, α = 117.059(1)°, β = 95.566(1)°, γ = 108.088(1)°, space group $P\bar 1$ , Z = 2, wR2 = 0.115, and R1 = 0.048 for 3948 reflections with F > 4σ(F). It is found that the substitution of the methylene group for the oxygen atom is accompanied by a minor conformational change in the bicyclic fragment and the SiCSi angle changes from the tetrahedral angle to 121.0(1)°. The high variability of the SiOSi bond angles is confirmed.     

X-Ray diffraction and IR-spectroscopic studies of UO2(n-C3H7COO)2(H2O)2 and Mg(H2O)6[UO2(n-C3H7COO)3]2

Single crystals of UO₂(n-C₃H₇COO)₂(H₂O)₂ (I) and Mg(H₂O)₆[UO₂(n-C₃H₇COO)₃]₂ (II) are synthesized. Their IR-spectroscopic and X-ray diffraction studies are performed. Crystals I are monoclinic, a = 9.8124(7) Å, b = 19.2394(14) Å, c = 12.9251(11) Å, β = 122.423(1)°, space group P2₁/c, Z = 6, and R = 0.0268. Crystals II are cubic, a = 15.6935(6) Å, space group $Pa\bar 3$ , Z = 4, and R = 0.0173. The main structural units of I and II are [UO₂(C₃H₇COO)₂(H₂O)₂] molecules and [UO₂(C₃H₇COO)₃]^? anionic complexes, respectively, which belong to AB ₂ ⁰¹ M ₂ ¹ (I) and AB ₃ ⁰¹ (II) crystal chemical groups of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₇COO^?, and M ¹ = H₂O). A crystal chemical analysis of UO₂ L ₂ · nH₂O compounds, where L is a carboxylate ion, is performed.     

Structure of tetrasodium nitrilotrimethylenetriphosphonatozincate tridecahydrate Na4[N(CH2PO3)3Zn] · 13H2O,an inhibitor of scaling and corrosion

The structure of a crystal hydrate of tetrasodium nitrilotrimethylenetriphosphonatozincate Na₄[N(CH₂PO₃)₃Zn] · 13H₂O is determined (space group $P\bar 1$ , Z = 2, a = 11.2208(2) Å, b = 11.2666(3) Å, c = 12.3286(3) Å, α = 108.455(2)°, β = 97.168(2)°, and = 117.103(2)°, Z = 2). The complex has a chelate structure; the inner coordination sphere includes three five-membered N-C-P-O-Zn cycles, which share the Zn-N bond. An oxygen atom of a neighboring complex completes a distorted trigonal bipyramidal coordination of the Zn atom.     

Synthesis and an X-ray diffraction study of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>]

The synthesis and X-ray diffraction study of compound Rb₂[(UO₂)₂(C₂O₄)₃], which crystallizes in the monoclinic crystal system, are performed. The unit cell parameters are as follows: a = 7.9996(6) Å, b = 8.8259(8) Å, c = 11.3220(7) Å, β = 105.394(2)°, and V = 770.7(1) ų; space group P2₁/n, Z = 2, and R ₁ = 0.0271. [(UO₂)₂(C₂O₄)₃]^2? layers belonging to the AK _0.5 ⁰² T ¹¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , K ⁰² = C₂O ₄ ^2? , and T ¹¹ = C₂O ₄ ^2? ) are uranium-containing structural units of the crystals. The layers are connected with outer-sphere rubidium cations by electrostatic interactions.     

Stereochemical activity of a lone electron pair in antimony(III) and bismuth(III) chelates: Crystal structures of Ca[Sb(Edta)]2 ⋅ 8H2O and Ba{[Bi(Edta)] 2H2O ⋅ H2O

The crystal structures of Ca[Sb(Edta)]₂ ? 8H₂O (I) and Ba{ [Bi(Edta)]₂H₂O} ? H₂O (II) are determined by X-ray diffraction. Crystals I are monoclinic, a = 7.132 Å, b = 21.906 Å, c = 10.896 Å, β = 91.13°, Z = 2, and space group P2₁/n. Crystals II are triclinic, a = 8.995 Å, b = 12.750 Å, c = 13.577 Å, α = 77.42°, β = 73.90°, γ = 86.53°, Z = 2, and space group $P\bar 1$ . In structure I, the coordination number of the antimony atom is 6 + LEP (lone electron pair), and the polyhedron is a ψ-pentagonal bipyramid with the lone electron pair at an equatorial position. In structure II, two crystallographically independent complexes Bi(Edta)^? and the coordination water molecule form tetranuclear associates. The environments of two independent bismuth atoms (the coordination number is eight) are similar, and their polyhedra can be described as distorted dodecahedra. The effect of the lone electron pair on the structures of polyhedra of antimony and bismuth is discussed.     

Crystal structure and IR spectroscopic study of (CN3H6)2[(UO2)2(C2O4)(CH3COO)4]

Compound (CN₃H₆)₂[(UO₂)₂(C₂O₄)(CH₃COO)₄] is synthesized and characterized by IR spectroscopy and single-crystal X-ray diffraction [a = 8.5264(2) Å, b = 13.8438(4) Å, c = 10.7284(2) Å, β = 103.543(1)°, space group P2₁/n, Z = 2, and R = 0.0258]. The main structural units of the crystals are binuclear [(UO₂)₂C₂O₄(CH₃COO)₄]^2? groups, which belong to the A ₂ K ⁰² B ₄ ⁰¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , K ⁰² = C₂O ₄ ^2? , and B ⁰¹ = CH₃COO^?). The coordination polyhedron of the uranium atom is the UO₈ hexagonal bipyramid with the oxygen atoms of the uranyl ion at the axial positions. Uranium-containing groups and guanidinium cations are connected by electrostatic interactions and by the hydrogen bond system, which involves hydrogen atoms of guanidinium cations and oxygen atoms of oxalate and acetate anions. The results of the spectroscopic study of the compound agree with the X-ray diffraction data.     

Crystal structure and properties of K<Subscript>2</Subscript>[OsO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>] · 2H<Subscript>2</Subscript>O

The synthesis and X-ray diffraction study of the compound K₂[OsO₂(C₂O₄)₂] · 2H₂O are performed. The compound crystallizes in the triclinic crystal system, space group P \(\bar 1\), a = 6.545(1) Å, b = 6.835(2) Å, c = 7.595(2) Å, α = 85.76(2)°, β = 65.33(2)°, γ = 71.14(2)°, and Z = 1. The osmium atom is located at the center of symmetry and has a distorted octahedral coordination formed by oxygen atoms: two oxygen atoms of the osmyl group occupy the apical positions [Os-O, 1.730(2) Å], and four oxygen atoms of the oxalate ions lie in the equatorial plane. The K⁺ cation is surrounded by ten oxygen atoms located at different K-O distances in the range from 2.787(2) to 3.158(2) Å. The assignment of the absorption bands in the IR spectrum of K₂[OsO₂(C₂O₄)₂] · 2H₂O is performed. The electronic absorption spectra of the compound are recorded in different solvents, and the thermal behavior in air is studied.     

Crystal structure of [N-(2-carbamoylethyl)iminodiacetato]-aqua(1,10-phenanthroline)cobalt(III) chloride 3.5 hydrate

The crystal structure of [N-(2-carbamoylethyl)iminodiacetato]-aqua(1,10-phenanthroline) cobalt(III) chloride 3.5 hydrate [Co(Ceida)(H₂O)(Phen)Cl · 3.5H₂O (I) has been determined by ¹H NMR technique and X-ray diffraction analysis. The crystals are triclinic, a = 10.352(2) Å, b = 12.534(3) Å, c = 20.665(4) Å, α = 107.02(3)°, β = 92.22(3)°, γ = 111.63(3)°, Z = 4, space group $P\bar 1$ , andR = 0.0438. The unit cell involves two crystallographically nonequivalent but virtually identical cationic complexes [Co(Ceida)(H₂O)(Phen)]⁺. The tridentate chelate ligand Ceida ^2? (N + 2O) occupies the face in the coordination octahedron of the Co atom, and the propionamide group remains free. The mean bond lengths are as follows: Co-O_Ceida, 1.876 Å; Co-N_Ceida, 1.981 Å; Co-N_Phen, 1.945 Å; and Co-O_w, 1.915 Å. In the structure, the arrangement of cationic complexes and certain water molecules exhibits a pseudosymmetry (the 2₁ axis). The cations and water molecules are located in the layers, and the anions are arranged between the layers. The structural elements are linked by hydrogen bonds and van der Waals interactions.     

Synthesis,spectroscopic characterization and crystal structure of 5-bromo-1-(2-cyano-pyridin-4-yl)-1H-indazole-3-carboxylic acid diethylamide

The title compound 5-bromo-1-(2-cyano-pyridin-4-yl)-1H-indazole-3-carboxylic acid diethylamide, C₁₈H₁₆BrN₅O, is prepared from 5-bromoindazole-3-carboxylic acid methylester. N ¹-arylation is carried out with 4-chloro-2-cyanopyridine and the resulting product is converted to diethylamide by reacting with thionyl chloride and diethylamine. The structure is identified from its FT-IR, ¹H NMR, ¹³C NMR spectroscopy, elemental analysis data and unambiguously confirmed by single crystal X-ray diffraction studies. There are two symmetry independent molecules in the asymmetric unit with no significant differences in bond lengths and angles. The title compound crystallizes in the triclinic system, space group \(P\bar 1\) , with a = 11.2330(2); b = 11.6130(2); c = 15.4710(3) Å, α = 92.515(1)°; β = 109.956(1)°; γ = 107.199(1)°; V = 1788.45(6)ų and z = 4. An intramolecular C-H…N hydrogen bond forms an S(6) ring motif in one of the unique molecules. In the crystal, two molecules are linked about a center of inversion by C-H…O hydrogen bonded dimers generating an R ₂ ² (16) ring motif. The crystal packing is stabilized by C-H…N, C-H…O hydrogen bonds and π…π stacking interactions.     

X-ray mapping in heterocyclic design: VIII. Synthesis and X-ray diffraction study of dimethyl 3-(p-chlorobenzoyl)-5-chloroindolizine-1,2-dicarboxylate and the product of its cyclization 1,2-bis(carbomethoxy)-6-chloro-3H-isoquinolino[1,2,3-d,c]indolizine-3-one

Dimethyl 3-(p-chlorobenzoyl)-5-chloroindolizine-1,2-dicarboxylate, C₁₉H₁₃Cl₂NO₅, (2) and the product of its cyclization 1,2-bis(carbomethoxy)-6-chloro-3H-isoquinolino[1,2,3-d,c]indolizine-3-one, C₁₉H₁₂ClNO₅, (3) are synthesized, and their molecular and crystal structures are determined by the single-crystal X-ray diffraction technique. Crystals 2 are monoclinic, a = 9.627(3) Å, b = 6.646(2) Å, c = 28.500(9) Å, β = 98.72(2)°, Z = 4, and space group P2₁/c. Crystals 3 are monoclinic, a = 7.048(4) Å, b = 10.582(4) Å, c = 21.760(7) Å, β = 97.23(4)°, Z = 4, and space group P2₁/c. The structures are solved by the direct method and refined in the anisotropic approximation by the full-matrix least-squares procedure to R = 0.0504 and 0.0510 for 2 and 3, respectively. In both structures, the intramolecular and intermolecular contacts involving the C, H, and O atoms are observed.