Crystal and Molecular Structure of Nitramino Derivatives of Tetrazole and 1,2,4-Triazole. II. 5-Nitraminotetrazole Diammonium Salt

The structure of the diammonium salt of 5-nitraminotetrazole wasestablished bysinglecrystalX-ray diffraction. The crystals are monoclinic, space group P2/c; a=7.272(1), b=8.643(1), c=10.427(1) ; =93.20(1)°; V=654.33(39) ³; Z=4;_calc=1.666 g/cm³. The dianion is nonplanar, but contains two practically planar fragments -- the tetrazole cycle and the nitramine group. The ammonium cations form an extended net of hydrogen bonds with the dianions, involving all hydrogen atoms. The negative charges of the dianion are located on the nitro oxygen atoms and the nitrogens of the tetrazole cycle. The difference between the geometrical parameters of the compound and those of other 5-nitraminotetrazole salts is examined.     

Distortion of the Cucurbituril Molecule by an Included 4‐Methylpyridinum Cation

The crystal and molecular structures of a guest–host complex of cucurbituril with 4methylpyridinium, {(4MePyH) (C₃₆H₃₆N₂₄O₁₂)}(NO₃) · 4H₂O, were determined by Xray structural analysis. The crystals are monoclinic with a = 26.276(3) , b = 25.861(2) , c = 17.375(2) , = 124.17(1)°, V_cell =9768.6(18) ³, space group Cc, and Z = 8. The structure contains two crystallographically independent supramolecular complexes. They are arranged in pillars oriented along the a axis. In each pillar, the complexes are parallel to each other. The pillars are shifted with respect to each other by onehalf of the crystallographic translation. The centers of the supermolecules are arranged according to a pseudobodycentered motif. Distortions of the cucurbituril molecule depending on the guest type have been analyzed with the use of results obtained in the present and previous studies.     

Disordered Crystal Structure of 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacozane perchlorate

Crystals of the ionic complex (salt) of 4,7,13,16,21,24hexaoxa 1,10diazabicyclo[8.8.8]hexacozane perchlorate, [H₂(Crypt2.2.2)]²⁺ · 2ClO₄ ^-, were synthesized and studied by Xray structural analysis: space group C2/c, a = 20.198(3), b = 10.119(2), c = 12.938(2), = 90.97(1)°, Z = 4, 3030 measured independent reflections, R = 0.067. In these crystals, all atoms of the 2.2.2 dication are disordered over two positions with occupancies of 0.518(4) and 0.482(4). Two conformations of the disordered 2.2.2 dication are such that two H atoms at two nodal N atoms point to its cavity.     

Synthesis and Molecular and Crystal Structure of K4.5{[Mo3(μ3-Te)(μ2-Te2)3(CN)6]I}I1.5·3H2O and Cs3{[Mo3(μ3-Te)(μ2-Te2)3(CN)6]I}·2H2O

Crystal structures of two new compounds containing trigonal tellurium-bridged cluster fragments [Mo₃(₃-Te)(₂-Te₂)₃]⁴⁺ were investigated. Crystal data for K_4.5{[Mo₃(₃-Te)(₂-Te₂)₃(CN)₆]I}I_1.5·3H₂O: space group , Z = 4, a = 13.280(1), c = 23.800(3) , V = 3635.0(6) ³, d _calc = 3.432 g/cm³, R ₁ = 0.0335, wR2 = 0.0912 for 1378 I _hkl > 2 _I from 3545 measured I _hkl ; for Cs₃{[Mo₃(₃-Te)(₂-Te₂)₃(CN)₆]I}·2H₂O: space group P2 ₁ /n, Z = 2, a= 9.650(2) , b = 22.297(5), c = 27.446(7) , = 94.10(2)°, V = 5890(2) ³, d _calc = 4.273 g/cm ³, R ₁ = 0.0384, wR ₂ = 0.0744 for 957 I _hkl > 2 _I from 3758 measured I _hkl (Enraf-Nonius CAD-4 diffractometer, MoK , graphite monochromator). In both compounds, ionic pairs {[Mo₃Te₇(CN)₆]I}^3– with Te_ax...I^– distances of 3.358-3.676 are formed. In the potassium salt, the {[Mo₃Te₇(CN)₆]I}^3– anion pairs are linked by the additional Te_eqI^– short contacts of 3.460 into two-dimensional corrugated layers perpendicular to the c axis of the unit cell. The structure of the cesium salt is ionic with interstitial H₂O molecules and double-layer closest packing of anions.     

Synthesis, Structure, and Thermal Decomposition of Chloropentamminerhodium(III) Hexabromoplatinate(IV)

The binary complex salt [Rh(NH₃)₅Cl][PtBr₆] was synthesized and studied by Xray structural analysis. The crystallographic data are as follows: a = 12.013(2) , b = 8.401(2) , c = 15.999(3) , = 91.13(3)°, V = 1614.3(6) ³, space group P2₁/m, Z = 4, d_x = 3.70 g/cm³, R = 0.086. The thermal decomposition of the salt in a hydrogen atmosphere is shown to produce a Rh_0.5Pt_0.5 solid solution with an FCC cell [a = 3.864(2) . The thermal decomposition of the salt in a helium atmosphere proceeds via the formation of metallic Pt and RhBr₃ and finally results in a mixture of several solid solutions.     

Preparation and Structure Characterization of 4-Amino-1,2,4-triazol-5-one Hydrate

4-Amino-1,2,4-triazol-5-one hydrate (ATO·H₂O) was prepared and its structure was analyzed by four-circle diffraction measurement. The obtained results show that the crystal belongs to the triclinic crystal system, space group P 1 with crystal parameters a = 6.432(1), b = 6.551(1), c = 6.740(1) ; = 68.04(1), = 82.18(1), = 81.90(1)°, V = 259.7(7) ³; Z = 2; Dc = 1.510 g/cm³; = 0.131 mm^-1; F(000) = 124. ATO·H₂O was characterized by FT-IR analysis, X-ray diffraction analysis, and single crystal diffraction analysis.     

Crystal structure of the synthetic analog of radtkeite Hg<Subscript>3</Subscript>S<Subscript>2</Subscript>Cl<Subscript>1.00</Subscript>I<Subscript>1.00</Subscript>

The results of structural studies of the synthetic analog of the radtkeite mineral Hg₃S₂Cl_1.00I_1.00 are analyzed. The crystal structure of the compound has been refined; the unit cell parameters are a _m = 16.827(4) , b _m = 9.117(1) , c _m = 13.165(5) , = 130.17(2)°, V = 1543.3(8) ³, space group C2/m, Z = 8, R = 0.0527. A possible transition a ₀ = a _m; b ₀ = a _m + 2c _m; c ₀ = –b _m to the pseudo-orthorhombic F cell previously determined for radtkeite, where one of the angles ( ₀ ) is slightly different from 90° (89.55°), has been found. Each sulfur atom in the structure is bonded to three mercury atoms, forming SHg₃ umbrellas with distances 2.240(6) –2.474(8) and angles HgSHg 94.7(2)°–102.9(2)°. The SHg₃ fragments are linked through Hg vertices to form corrugated [Hg₁₂S₈] layers. The halogen atoms lie inside and between the [Hg₁₂S₈] layers; the distances are Hg-Cl and Hg-I 2.783(7) , 2.961(7) , and 3.083(4) –3.311(3) , respectively.Original Russian Text Copyright © 2004 by N. V. Pervukhina, S. V. Borisov, S. A. Magarill, D. Yu. Naumov, V. I. Vasiliev, and B. G. NenashevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 755–758, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Crystal and Molecular Structure of Monoammonium Salt of 5‐nitroaminotetrazole

Xray structural investigation of the monoammonium salt of 5nitroaminotetrazole was performed. The crystals are orthorhombic: a = 10.077(1), b = 17.009(1), c = 6.6472(6), V = 1139.33(17)³, space group Pbca, Z =8, _calc = 1.715 g/cm³. Monodeprotonation of 5nitroaminotetrazole during formation of the salt occurs at the N(4) nitrogen atom of the heterocycle. The anion has an almost flat structure; the bond lengths suggest delocalization of electron density in the molecule. The negative charge is distributed among three nitrogen atoms and two oxygen atoms of the anion. Changes in the geometrical parameters of 5nitroaminotetrazole on monodeprotonation are considered.     

Crystal Structure of Dehydrated Wairakite

Singlecrystal Xray analysis was employed to study dehydrated wairakite Ca_0.97Na_0.06K_0.03×[Al_1.95Si_4.04O₁₂] with the following parameters: a = 18.260(4) , b = 18.284(4) , c = 13.432(3) , = 90.28(3)°, V = 4989(3) ³, Z = 16, space group B2₁/d. A comparison was carried out with the structure of the hightemperature (600°) phase, space group I4₁/acd. The coordination of the Ca cations increased from 4 to 4 + 1. Additional ligands were acquired from the fourmember ring of the framework upon its deformation and a pairwise countershift of the cations along the c axis. This resulted in a pseudotetragonal unit cell with a doubled volume and lowered symmetry.     

Crystal and Molecular Structure of 2‐nitro‐1‐ureidoguanidine

An Xray structural investigation of 2nitro1ureidoguanidine has been carried out. The crystals are monoclinic: a = 4.4690(2), b = 15.566(1), c = 9.4131(7), = 94.896(5)°, V = 652.4(3)> ³, space group P2₁/n, Z = 4, _calc = 1.650 g/cm³. The molecule consists of two planar fragments: carbamide and nitroguanidine. The geometrical characteristics of the molecule are analyzed. The system of intra and intermolecular hydrogen bonds in the crystal is considered.     

Synthesis and Crystal Structure of the (batre)[CuBr4] Complex, where Batre is bis‐1,1′‐(4‐amino‐1,2,4‐triazolio)ethane

The (batre)[CuBr₄] complex is produced by the reaction of CuBr₂ and (batre)Br₂ in concentrated HBr; its crystal structure is determined. The acentric unit cell (Pn space group) has the following parameters: a = 7.626(2), b = 8.945(2), c = 11.702(2), = 96.69(3)°, V = 792.8(3)³, and Z=1 ((batre)[CuBr₄] composition). The structure of the complex is built up of [CuBr₄]^2- tetrahedral anions and (batre)²⁺ uncoordinated cations. The Cu—Br distances are 2.362–2.385 and the BrCuBr angles are 99.73–129.79°.     

Synthesis and Crystal Structure of trans-Rb2[Pd(NO2)2Cl2]. Structure Refinement of Na2[Pd(NO2)4]

The reaction products of palladium(II) nitration with sodium nitrite in the presence of rubidium salts are described. The crystal structure of rubidium dinitrodichloropalladoate(II) — trans-Rb₂[Pd(NO₂)₂Cl₂] — has been studied (KUMA automatic diffractometer, MoK radiation, graphite monochromator, /2 scan mode for 2 < 30°, 758 experimental reflections, R = 0.030; R = 0.023 for I>2(I)). Crystal data: a = 15.123(3), b = 7.750(2), c = 7.776(2) , V = 911.4(4) ³, space group Cmca, Z = 4, d _calc = 3.209 g/cm³. The structure consists of [Pd(NO₂)₂Cl₂]^2– complex anions and Rb⁺ cations. The planar square coordination of the Pd atom is completed to distorted octahedral by the chlorine atoms of the neighboring complexes at Pd...Cl distances of 3.18 . Chains of complexes with alternating orientations are formed. The geometrical characteristics of the complex anions, the coordination polyhedra of the cations, and the heavy atom sublattice are analyzed. The crystal structure of Na₂[Pd(NO₂)₄] has been refined, and refinement data are given.     

Synthesis and structure of isomeric (μ-H)Os<Subscript>3</Subscript>(μ,η<Superscript>2</Superscript>-(O,N)-6,6-clusters of dimethyl-2-methylene-bicyclo[3.1.1]heptan-3-one oxime)(CO)<Subscript>10</Subscript>. Crystal structure of one of the isomers

(-H)₂Os₃(,²-(O,N)-6,6-dimethyl-2-methylene-bicyclo[3.1.1]heptan-3-one oxime)(CO)₁₀ isomeric clusters have been synthesized, separated chromatographically, and investigated by IR and NMR spectroscopy. The crystal structure of one of the isomers has been determined (Enraf-Nonius CAD-4 automatic diffractometer, graphite monochromator, MoK , /2 scan mode at a variable rate). The crystals are monoclinic with unit cell parameters: a = 9.125(2) , b = 13.629(3) , c = 10.098(2) , = 90.16(3)°, V = 1255.8(4) ³, space group P2₁, Z = 2, composition (-H)₂Os₃(,²-ONC₁₀H₁₄)(CO)₁₀, d _calc = 2.647 g/cm³. The structure is molecular; the planes of the Os₃ triangle and the OsONOs bridging ligand are linked according to the butterfly pattern with an angle of 102.0° between the planes. The Os-Os bonds vary within the range 2.840 –2.882 .Original Russian Text Copyright © 2004 by V. A. Maksakov, N. V. Pervukhina, S. V. Korenev, N. V. Podberezskaya, V. P. Kirin, and A. V. TkachevTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 4, pp. 698–705, July–August, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Crystal Structures of Two New Holmium Polysulfides in the Series of Rare-Earth Polychalcogenides

The crystal structures of two polysulfide phases HoS_1.885(5) (I) and HoS_1.863(8) (II) were determined; the integer stoichiometric ratio was found to be Ho₈S₁₅. The data were collected on an Enraf-Nonius CAD-4 automatic diffractometer using the standard procedure (MoK, graphite monochromator, an absorption correction applied based on -scan data). Crystal I: space group P4/nmm, a = 3.820(1), c = 7.840(3) , V = 114.40(6) ³, Z = 2 for the composition HoS_1.885(5), d _calc = 6.542 g/cm³, R = 0.0520 for 184 unique reflections with I_hkl > 2 _I; crystal II: space group P2₁/m, a = 10.961(2), b = 11.465(2), c = 10.984(2) , = 91.27(3)°, V = 1380.0(4) ³, Z = 24 for the composition HoS_1.863(8), d _calc = 6.486 g/cm³, R = 0.0596 for 5354 unique reflections with I_hkl > 2 _I. In both compounds, the Ho atoms are surrounded by 9 (8+1 for three atoms in II) S atoms forming monocapped square antiprisms. The Ho–S distances vary from 2.717 to 3.067 irrespective of the type of ion [S^2– or (S₂)^2–]; the maximal distance to the atoms completing the coordination is 3.684 . The compounds have PbFCl type structures composed of ...(S₂)^2–...Ho³⁺...S^2–...S^2–...Ho³⁺...(S₂)^2–... layer packets differently oriented in space relative to the unit cell axes. The S^2–...S^2– and S^2–...(S₂)^2– interlayer distances are mostly shorter than the sum of the ionic radii and vary within the limits of 3.331-3.558 and 3.029-3.784 for the first and second types, respectively. For I, the calculated site occupancies and densities are given depending on the composition Ho-S_2-x (x = 0.25-0); for II, the most probable formulas of rational compositions in the same range of x are presented.     

Synthesis and X‐Ray Study of Single Crystals of K5(Cd0.5Zr1.5)(MoO4)6 Triple Molybdate

Single crystals of K₅(Cd_0.5Zr_1.5)₂(MoO₄)₆ molybdate have been grown. Its composition and crystal structure have been established from Xray diffraction data CAD4 automatic diffractometer, MoK radiation, 940 F(hkl), R = 0.0234. The crystals have a trigonal unit cell a = b = 10.624(1), c = 37.694(6), V = 3684.5(8)³, and space group R3c. The 3D mixed framework of the molybdate structure is formed by two kinds of Mo tetrahedra and (Cd, Zr) octahedra joined by shared O vertices. The large cavities in the framework are occupied by K atoms of three kinds. The distribution of Cd²⁺ and Zr⁴⁺ cations over two crystallographic positions has been refined.     

Novel chromium trinuclear trifluoroacetate complexes Cr3(μ3-O)(CF3COO)6(CH3COOH)2(CF3COO) and Cr3(μ3-O)(CF3COO)6(CH3COOH)2(THF): Synthesis and crystal structure

Novel anhydrous trinuclear ₃-oxo complexes of Cr(III), Cr₃(₃-O)(CF₃COO)₆(CH₃COOH)₂(CF₃COO) (I) and of Cr(III,III,II), Cr₃(₃-O)(CF₃COO)₆(CH₃COOH)₂(THF) (II) (where THF is (CH₂)₄O) are synthesized by anodic dissolution of metallic chromium in solutions of trifluoroacetic acid in acetonitrile and in tetrahydrofuran and their structures are studied by X-ray diffraction analysis. Complex I forms orthorhombic crystals with space group Pna2₁, a = 9.778(1) , b = 16.042(2) , c = 22.851(4) , Z = 4, R ₁ = 0.0332; complex II crystallizes in monoclinic system: space group P2₁/c, a = 9.866(1) , b = 17.895(2) , c = 21.167(4) , = 100.75(2)°, Z = 4, R = 0.0422. The average Cr-(₃-O) distances in compounds I and II are almost equal (1.943(3) and 1.927(3) ). An average length of the Cr-O bond in octahedral surrounding of metal atoms is different in complexes I and II (1.985(4) and 2.003(3) , respectively), which is specified by different oxidation states of the metal atom. The CrCr distances lie in an interval of 3.366(1)–3.337(1) .__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 266–272.Original Russian Text Copyright © 2005 by Glazunova, Boltalin, Troyanov.     

Crystal Structures of [Ni(Phen)(i‐Bu2PS2)2] and [Ni(Phen)3](i‐Bu2PS2)2 Complexes and Interaction between Coordinated 1,10‐Phenanthroline Molecules

Single crystals of [Ni(Phen)(iBu₂PS₂)₂] (I) and [Ni(Phen)₃](iBu₂PS₂)₂ (III) compounds were grown, and their structures were determined by Xray diffraction analysis (CAD4 diffractometer, MoK radiation, 3336 F _hkl , R = 0.0373 for I and 2575 F _hkl for III). The crystals of complex I have a triclinic unit cell with the following parameters: a = 11.097(1) , b = 14.903(2) , c = 22.650(3); = 75.18(1)°, = 80.50(1)°, = 75.07(1)°, V = 3479.2(7)³, Z = 4, _calc = 1.255 g/cm³, and space group 1; the crystals of III have a monoclinic unit cell with the following parameters: a = 19.010(3), b = 15.481(1) , c = 17.940(3); = 97.58(1)°, V = 5233.5(12)³, Z = 4, _calc = 1.292 g/cm³, and space group C2/c. The structure of complex I is built from mononuclear molecules, and the structure of III, from [Ni(Phen)₃]²⁺ complex cations and i Bu₂PS₂ ^- outersphere anions. The NiN₂S₄ coordination polyhedra in the structure of I and NiN₆ in the structure of III are distorted octahedra. Based on structural data, the interaction between the coordinated Phen molecules of complexes I, [Ni(Phen)₂(iBu₂PS₂)](iBu₂PS₂) (II), and III is considered, as well as the packing modes of these complexes.     

Crystal and Molecular Structure of 1-( p -Tolyl)-4-[4-(N-naphthalimido)butyl]piperazine

An X-ray structure analysis of 1-(p-tolyl)-4-[4-(N-naphthalimido)butyl]piperazine (I) was carried out: a=9.551(3), b=13.775(3), á=8.917(4) , =103.96(3), =101.47(4), =92.60(3)°, V=1110.4(7) ³, Z=2,_calc=1.279 g/cm³, =0.644 mm, space group P 1, 4239 nonzero reflections, R=0.056. The molecule is linear elongated. The p-tolyl and naphthalimide fragments are almost planar, while the piperazine cycle has a chair conformation. The long well-packed molecules form parallel and antiparallel chains with van der Waals interactions between them.     

Coordination chemistry of alkali and alkaline earth cations: Synthesis and X-ray crystal structure of cesium (picrate) (benzo-15-crown-5) Cs+C6H2N3O 7 − (C14H20O5)

Crystals of the Cs⁺ Pic^– (B15C5) complex (Pic=picrate; B15C5=benzo-15-crown-5) (M _r =629.3) are yellow prisms which belong to the triclinic space groupP witha=7.377(4),b=11.372(2),c=14.806(2) , =90.31(1), =91.06(2), =108.32(2)⁰,Z=2,D _x =1.77, andD _m =1.77 g cm^–3. FinalR=0.055 for 3575 observed reflections out of a total of 4004 measured reflections. Cesium forms a 1:1 anion paired complex with B15C5 like sodium rather than a charge separated sandwich structure as found for potassium and expected for cesium in view of the ion-cavity radius concept. The Cs cation is 9-coordinate involving the five crown oxygens (Cs...O, 3.00(1) to 3.24(1) ), the phenoxide (Cs...O^–, 3.03(1) ) and anortho nitro group oxygen (Cs...O, 3.01(1) ) of the picrate counteranion and, uniquely, with two additional oxygens (Cs...O, 3.17(1) and 3.40(1) ) from apara nitro group of the picrate belonging to the adjacent molecule in the lattice. The Cs⁺ ion lies 2.07 out of the mean plane formed by the crown oxygens. This system provides the first structural evidence that the interaction stoichiometry of an alkali cation with a cyclic multidentate ligand is not a function of the ion and cavity size alone but also of its Lewis acid strength as modified by the charge neutralizing anion. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82027.     

Crystal and Molecular Structure of 5,7,12,14-Tetramethyl-1,4,8,11-tetraaza-4,6,11,13-tetraenatogold(III) Bromide [Au(C14H22N4)]Br

The crystal and molecular structure of [Au(C₁₄H₂₂N₄)]Br has been determined. Monoclinic crystals, a=12.592(2), b=6.309(1), c=19.628(2) ; =98.00(1)°, V=1544.1(4) ³, Z=4, d_calc=2.251 g/cm³, space group C2/c. The structure consists of virtually planar centrosymmetric [Au(C₁₄H₂₂N₄)]⁺ cations and Br^- anions. The coordination sphere of the gold atom involves four nitrogen atoms of the ligands, forming a planar square. The Au–N bond lengths are equal (the mean length is 1.982(7) ). The C–C and C–N bonds inside the -diiminate rings are delocalized. The parameters of the -diiminate rings of the [Au(C₁₄H₂₂N₄)]⁺ cation are compared with the parameters of the related complexes.