Crystal structures of cesium and rubidium 2-thiobarbiturates

The crystal structures of cesium 2-thiobarbiturate C₄H₃CsN₂O₂S (I) and rubidium 2-thiobarbiturate C₄H₃N₂O₂RbS (II) (C₄H₄N₂O₂S is 2-thiobarbituric acid, H₂TBA) have been determined. Isostructural crystals are monoclinic; a = 7.9609(3) Å,b = 11.8474(3) Å, c = 7.7317(2) Å, β = 101.285(3)°, V = 715.13(4) ų, space group C2/m, Z = 4 for I and a = 7.6369(2) Å, b = 11.7690(3) Å, c = 7.5568(2) Å, β = 100.212(1)°, V = 668.44(3) ų, space group C2/m, Z = 4 for II. Each metal ion in complexes I and II is bonded to four oxygen atoms and two sulfur atoms at the vertices of a six-vertex polyhedron. N-H…O hydrogen bonds link HTBA-ions into chains. The structure is also stabilized by the “head-to-tail” π-π interaction of HTBA-ions.     

Crystal structure of catena-DI(2-thiobarbiturato-O,S)aqualead(II)

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) ų, space group $P\bar 1$ , 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.     

Nickel(II) complex with 4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dione and dimethyl sulfoxide: Crystal and molecular structures

A nickel(II) complex with 4,4,4-trifluoro-1-(2-thienyl)butane-1,3-dione and dimethyl sulfoxide, [Ni(C₈H₄F₃O₂S)₂(C₂H₆OS)₂], was obtained and examined by X-ray diffraction. The crystals are monoclinic: a = 7.557(2) Å, b = 17.854(3) Å, c = 10.470(2) Å, β = 106.412(3)°, V = 1355.1(4) ų, ρ_calcd = 1.611 g/cm³, Z = 2, space group P2₁, R = 0.032. The coordination polyhedron of the nickel atom is a distorted octahedron consisting of four equatorial O atoms of two β-diketonate ligands and two axial O atoms of DMSO. The average Ni-O_ax and Ni-O_eq distances are 2.083(2) and 2.019(2)Å, respectively. The crystal structure is built from the discrete mononuclear complexes [Ni(C₈H₄F₃O₂S)₂(C₂H₆OS)₂] linked only by van der Waals contacts.     

Crystal structure of catena-(2-thiobarbiturato) dithallium(I)

By powder X-ray diffraction the crystal structure of catena-(2-thiobarbiturato)dithallium(I) C₄H₂N₂O₂STl₂ (C₄H₄N₂O₂S is 2-thiobarbituric acid, H₂TBA), Tl₂TBA, is determined. Crystallographic data for Tl₂TBA are as follows: a = 15.1039(3) Å, b = 12.0818(2) Å, c = 3.86455(6) Å, β = 97.203(1)°, V = 741.34(2) ų, space group P2₁/n, Z = 4. There are two non-equivalent thallium atoms in the structure. The Tl1 polyhedron is a distorted trigonal prism due to the shortened Tl-S contact (3.634 Å), and the Tl2 polyhedron is a distorted square antiprism.     

Crystallochemical study of ruthenium(III) tris-dipivaloylmethanate

The structure of ruthenium(III) dipivaloylmethanate is determined by single crystal X-ray diffraction at temperature of 150 K. The crystallographic data for C₃₃H₅₇O₆Ru are as follows: a = 9.6119(11) Å, b = 17.4603(19) Å, c = 21.519(2) Å, β = 95.187(2)°, C2/c space group, V = 3596.7(7) ų, Z = 4, d_calc = = 1.202 g/cm³, R = 0.0642. The structure is molecular, the metal atom coordinates six oxygen atoms of three ligands of β-diketone. The Ru–O distances are in the range of 1.99 Å to2.03 Å. The complexes have a distorted single layer hexagonal packing with the Ru…Ru distances being 9.84 Å within the layer, and 10.93 Å between the layers.     

Double helix of the coordination polymer of silver with 1,3-bis(4-pyridyl)propane: Synthesis and crystal structure of [Ag(C<Subscript>13</Subscript>H<Subscript>14</Subscript>N<Subscript>2</Subscript>)](CF<Subscript>3</Subscript>CO<Subscript>2</Subscript>)

The [Ag(Bpp)](CF₃CO₂) complex (Bpp is 1,3-bis(4-pyridyl)propane, C₁₃H₁₄N₂) is synthesized, and its structure is determined. The crystals are monoclinic, space group C2/c, a = 26.169(5), b = 10.521(2), c = 12.906(3) Å, β = 117.99(3)°, V = 3137.7(11) ų, ρ_calcd = 1.775 g/cm³, Z = 8. The structure contains double helices of-Ag-Bpp-Ag-Bpp-cationic chains with a helix period of 21.042 Å. The Ag…Ag distance between a pair of silver atoms from different chains in the helix is 3.201 Å, and the distance between the adjacent helices is 3.279 Å. The silver atom is linked with two bridging nitrogen atoms of two Bpp ligands in an almost linear coordination: Ag-N_avg 2.142 Å; NagN, 171.3(4)°. The CF₃C ₂ ^? anion has a weak contact with the silver ion (Ag…O 2.62(2) Å).     

Coordination polymer of uranyl nitrate with 4,4,10,10-Tetramethyl-1,3,7,9-Tetraazaspiro[5.5]undecane-2,8-dione (Spirocarbone, Sk): Synthesis and study of molecular and crystal structures

The coordination polymer {[UO₂(NO₃)₂(C₁₁H₂₀N₄O₂)] · 2H₂O} _n (I) was obtained and examined by X-ray diffraction. The crystals are monoclinic, space group C2/c; a = 23.1386(13), b = 5.41575(15), c = 19.7769(11) Å, β = 125.285(8)°, V = 2023.01(17) ų, ρ_calcd = 2.20 g/cm³, Z = 4. The U atom occupies a special position in the center of inversion. Its coordination polyhedron is a distorted hexagonal bipyramid with axial oxo ligands. In the equatorial plane, the U(1) atom is coordinated by four O atoms of two bidentate nitrate anions and two O atoms of two carbonyl groups of organic spirocarbone (Sk) molecules, which are related by the symmetry operation (0.5 ? x, 0.5 ? y, ?z). In the crystal, polymer chains are parallel to the direction (101). Water molecules are hydrogen-bonded to the N(1) atom of ligand Sk; in addition, they are linked together by the intermolecular hydrogen bonds O(6)-H(6d)…O(6)ⁱ(ⁱ1/2 ? x, ?1/2 + y, 1/2 ? z); H…O 2.11 Å angle O-H…O 160°) and to the nitrate anions by the hydrogen bonds O(6)-H(6e)…O(3)ⁱ; H…O 2.29 Å; the angle O-H…O 149°). In the crystal, hydrogen-bonded water molecules form chains along the axis y that are perpendicular to the coordination polymers. To verify the purity of complex I, the Rietveld refinement of its X-ray powder diffraction pattern was performed. At room temperature, the unit cell parameters are a = 23.2965(6), b = 5.51225(15), c = 19.8588(6) Å, β = 125.6063(17)°, V = 2073.40(10) ų.     

Unique Isle Anion [Cu6Cl10]4- in π-Complex of Cu(I) Chloride with 1-(2-Pyridyl)-4-allyl-piperazinium. Synthesis and crystal structure of [(C5H4NH)NC4H8NH(C3H5]2+[Cu3Cl5]2-

Single crystals of [(C₅H₄NH)NC₄H₈NH(C₃H₅)]²⁺[Cu₃Cl₅]^2? are obtained by ac synthesis in ethanol from 1-(2-pyridyl)-4-allyl-piperazinium and Cu(II) dichlorides and their structure is studied by X-ray diffraction analysis (space group P-1, a = 7.246(7) Å, b = 8.54(1) Å, c = 16.41(1) Å, α = 70.76(8)°, β = 77.24(8)°, λ = 80.42(9)°, V = 30(4) ų, Z = 2, R(F) = 0.0686. In the structure of this π-complex, the Cu and Cl atoms form unusual centrosymmetrical Cu₆Cl₁₀ fragments, each fragment being bonded to two 1-(2-pyridyl)-4-allyl-piper-azinium cations via π-interaction Cu-(C=C). A three-dimensional structure is formed by means of N-H…Cl hydrogen bonds. The trigonal-pyramidal surrounding of the Cu(1) atom includes three Cl atoms and the C=C bond, while the tetrahedral surrounding of Cu(2) and the trigonal surrounding of Cu(3) involve the Cl atoms only.     

Crystal structure of thallium(I) 2-thiobarbiturate

The crystal and molecular structures of thallium(I) thiobarbiturate C₄H₃N₂O₂STl (C₄H₄N₂O₂S is 2-thiobarbituric acid, Н₂ТВА) have been determined. Crystallographic data for Tl(НТВА) are a = 11.2414(7) Å, b = 3.8444(3) Å, с = 14.8381(9) Å, β = 99.452(2)°, V = 649.00(7) ų, space group P2/с, Z = 4. Each of the two independent thallium ions is bonded to four oxygen and two sulfur atoms to form a distorted tetrahedron. N?H…O and C?H…S hydrogen bonds form a branched three-dimensional network. The structure is also stabilized by π?π interaction between heterocyclic НТВА^- ions. The IR spectra of Tl(НТВА) agree with X-ray powder diffraction data. The compound is also stable below 280°C, and Tl₂SO₄ is one of the thermolysis products in an oxidative medium in the region of 500?650°C.     

Crystal structure of lithium(i) 1,1,1,-trifluoro-5,5-dimethyl-2,4-hexanedionate

Lithium pivalyltrifluoroacetonate has been studied by X-ray crystallography. The compound has a structure of a coordination polymer [Li(pta)]_∞ with Li…Li distances of 2.74 Å. Crystal data for C₁₆H₂₀F₆Li₂O₄: a = 19.151(4) Å, b = 10.723(2) Å, c = 19.801(4) Å, space group Pbca, Z = 8, d _calc = 1.321 g/cm³.     

Crystal structure of a Mn(II) complex with isatin-hydrazone-S-benzyldithiocarbazate

The reaction of Mn(OAc)₂·4H₂O with isatin-hydrazone-S-benzyldithiocarbazate (HIsa-SBn) results in the formation of a bis-ligand complex [Mn(Isa-SBn)₂]·2DMF. Its single crystal is obtained and the structure is determined by X-ray diffraction. It belongs to a monoclinic space group C2/c with the cell parameters: a = 23.290(4) Å, b = 11.4980(18) Å, c = 18.483(5) Å, V = 4087.6(14) ų. The Mn(II) atom is six-coordinated with two amide O atoms, two azomethine N atoms, and two thiolate S atoms, resulting in a distorted octahedral geometry.     

Crystal structures of two 4-phenylbenzophenones

Two 4-phenylbenzophenones (I) and (II) are synthesized via Friedel-Crafts reactions. There are four crystallographically independent molecules with different conformations in the crystal structure of [1,1′-biphenyl]-4-yl(2-chlorophenyl)methanone (I). Crystals are orthorhombic, Pca2₁, C₁₉H₁₃ClO, a = 13.699(3) Å, b = 8.9385(17) Å, c = 46.836(9) Å; V = 5735(2) ų, Z = 16, d _x = 1.356 g/cm³. Torsion angles between the biphenyl rings are between 28.5° and 30.8°. Several C-H…O and C-H…Cl hydrogen bonds and weak π-π stacking contacts consolidate the crystal. Crystals of [1,1′-biphenyl]-4-yl(3-methoxyphenyl)methanone (II) are orthorhombic, Pbca, C₂₀H₁₆O₂, a = 7.8179(15) Å, b = 16.003(3) Å, c = 23.345(5) Å; V = 2920.7(10) ų, Z = 8, d _x = 1.311 g/cm³. The torsion angle between the biphenyl rings is 28.1° and C-H…O hydrogen bonds are observed in compound (II).     

Crystal structure of catena-Bis(2-thiobarbiturato-O,S)diaquacadmium

The crystal structure of catena-bis(2-thiobarbiturato-O,S)diaquacadmium (C₈H₁₀CdN₄O₆S₂) _n (I), [Cd(H₂O)₂(HTBA)₂] _n (C₄H₄N₂O₂S is 2-thiobarbituric acid, H₂TBA) has been determined. The crystals of compound I are triclinic, a = 6.9433(3) Å, b = 7.2257(3) Å, c = 7.4047(3) Å, α = 88.559(2)°, β = 75.346(2)°, γ = 111.687(1)°, V = 331.05(3) ų, space group $P\bar 1$ , Z = 1. The Cd²⁺ ion is coordinated to the two oxygen atoms of water molecules and the two oxygen and two sulfur atoms of four HTBA^? ions at the vertices of an octahedron. Octahedra are linked by bridging μ₂-HTBA^?-O,S ions into infinite chains. Intermolecular hydrogen bonds form infinite chains. The structure is also stabilized by the π-π interaction of HTBA^? ions.     

Crystal structure of L-leucinium tetrafluoroantimonate(III)

The crystal structure of L-leucinium tetrafluoroantimonate(III) of the composition (C₆H₁₄NO₂)SbF₄ (orthorhombic symmetry: a = 6.1459(6) Å, b = 14.994(1) Å, c = 24.789(2) Å, Z = 8, P 2₁2₁2₁ space group) synthesized for the first time is determined. The (C₆H₁₄NO₂)SbF₄ structure represents a new structure type of tetrafluoroantimonate(III). It is formed by (C₆H₁₄NO₂)+ cations and chain complex [Sb₂F₈]_n ²ⁿ anions composed of Sb₂F₈ dimers linked into chains by bridging F atoms. The Sb₂F₈ dimers consist of SbF₃ and SbF₅ groups bound by bridging fluoride atoms of the SbF₅ group. Chains in the structure are linked by N-H…F, N-H…O, and O-H…F hydrogen bonds into a three-dimensional framework.     

<Emphasis Type="Italic">N,N</Emphasis>-diethylanilinium complex with borodicitric acid: Synthesis and crystal structure

N,N-Diethylanilinium dicitratoborate [C₆H₅NH(C₂H₅)₂][(C₆H₆O₇)₂B] (I) has been synthesized for the first time. Single crystals has been synthesized in an aqueous solution to study the crystal structure of complex I by single-crystal X-ray diffraction. Crystals are triclinic, space group Р1 a = 9.6183(2) Å, b = 10.3153(3) Å, c = 13.7364(4) Å, α = 69.0304(12)°, β = 77.0394(13)°, γ = 89.5518(10)°, V = 1236.25(6) ų, Z = 2, ρ_calcd = 1.454 g/cm³. Structural units in a crystal of complex I are large complex dicitratoborate anions with a spirane structure and N,N-diethylanilinium cations. The crystal packing is a three-dimensional framework implemented via a system of hydrogen bonds like О–Н…О, О–Н…О, ОI, and N–Н…О.     

Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

Synthesis and crystal structure of two derivatives of benzodiazepines

Two benzodiazepine derivatives, C₂₃H₂₂N₂O (I), 2-methyl-8-methoxy-2,4-diphenyl-2,3-dihydro-1H-1,5-benzodiazepine, and C₂₂H₁₇N₃O₂Br₂ (II), 2-methyl-7-nitro-2,4-bis(4′-bromophenyl)-2,3-dihydro-1H-1,5-benzodiazepine, were studied by single crystal X-ray diffraction method. Compound (I) crystallizes in the monoclinic system, space group P2₁/c, a = 13.1703(17) Å, b = 11.1990(14) Å, c = 12.9093(16) Å, β = 107.831(2)°, V = 1812.6(3) ų, Z = 4. Compound (II) crystallizes in the monoclinic system, space group P2₁/n, a = 11.7345(12) Å, b = 12.7477(13) Å, c = 13.5965(14) Å, β = 95.221(2)°, V = 2025.4(4) ų, Z = 4. The molecules of (I) and (II) have T-shape form with the diazepine ring at the junction point. The seven membered central benzodiazepine ring in both structures adopt a twist-boat conformation. The crystal packing is stabilized by C-H…π (in I) and C-H…O (in II) interactions.     

Complexes of acetic acid α-(N-benzoxazolin-2-one) with Zn(II), Cu(II), and Co(II): Syntheses and crystal structures

The results of syntheses and X-ray diffraction analyses of mononuclear complexes [ML₂(H₂O)₄] (M = Co²⁺(I), Cu²⁺(II), and Zn²⁺(III)) containing water molecules and anions of acetic acid α-(N-benzoxazolin-2-one) (L = C₉H₆O₄) are presented. The crystals of complexes I–III are isostructural (space group P2₁/n, Z = 2) and are built of discrete neutral complex molecules. The crystallographic data are as follows: for complex I, a = 6.1470(5), b = 5.3310(3), c = 30.5894(17) Å, β = 95.056(6)°, V = 998.50(11) ų; for complex II, a = 5.9661(6) Å, b = 5.1414(4) Å, c = 32.672(2) Å, β = 92.395(6)°, V = 1001.33(14) ų; and for complex III, a = 6.1404(3) Å, b = 5.3476(2) Å, c = 30.5865(12) Å, β = 94.708(4)°, V = 1000.96(7) ų. The metal atoms (M) of the complexing agents are localized in the crystallographic symmetry centers and have a distorted octahedral environment due to two oxygen atoms of the carboxy groups of two monodentate ligands (L) and four water molecules. The M-O(1w)(H₂O) and M-O(2w)(H₂O) bond lengths for the indicated complexes are 2.088(3) and 2.118(3), 2.446(3) and 1.971(3), and 2.113(4) and 2.093(3) Å for M = Co²⁺, Cu²⁺, and Zn²⁺, respectively. The crystal structures are formed due to packing of chains built of inter-molecular hydrogen bonds O-H…O.     

Crystal structure refinement for trans-[Pd(NO3)2(H2O)2]

Single crystals of trans-[Pd(NO₃)₂(H₂O)₂] were obtained, and the crystal structure of this complex, previously obtained for polycrystals, was refined. Crystal data (BRUKER X8APEX diffractometer): a = 4.9973(7) Å, b = 10.5982(14) Å, c = 11.7008(17) Å, V = 619.70(15) ų, space group Pbca, Z = 4, d _calc = 2.856 g/cm³. The structure is composed of neutral complexes with a trans configuration. The square plane environment of the Pd atom is formed by four oxygen atoms (Pd-O(NO₃) 1.999(5) Å, Pd-O(H₂O) 2.030(5) Å) and completed to a distorted bipyramid by two intramolecular contacts (Pd…O(NO₃) 2.926 Å). The shortest hydrogen bonds are O…H 2.72 Å.     

Crystal structure of olanzapinium benzoate (1:1)

Olanzapinium benzoate, 1-methyl-4-(2-methyl-10H-thieno[2,3-b][1,5]benzodiazepin-4-yl)-piperazin-1-ium benzoate, (C₁₇H₂₁N₄S)⁺(C₇H₅O₂)^? (I), crystallizes in triclinic space group P-1 with unit cell dimensions a = 9.2957(6) Å, b = 11.2416(7) Å, c = 12.0003(8) Å; α = 64.585(1)°, β = 87.568(1)°, γ = 83.248(1)°; V = 1124.8(1) ų. The asymmetric part of the structure comprises a singly charged olanzapinium cation and a singly charged benzoate anion. The central 1,5-diazepine ring adopts the expected boat conformation, while the piperazine ring favors the chair conformation. The olanzapinium and benzoate ions are linked by intermolecular N-H...O hydrogen bonds forming infinite chains running along the c-axis of the crystal.