X-ray diffraction study of the clathrate [MnPy4(NO3)2)]·2Py and complex [MnPy3(NO3)2] formed in the pyridine (Py)-manganese nitrate system

A clathrate compound [MnPy₄(NO₃)₂]·2Py was synthesized and studied by single-crystal X-ray diffraction analysis (KM-4 diffractometer, CuK_α,ω/2? scan mode,? _max=78°). The unit cell is base-centered orthorhombic, space group Ccca, a=12.097(4), b=15.197(4), c=17.213(4) Å, V=3164(2) ų, Z=4, R=0.072, for 632 reflections and 107 parameters in the least-squares analysis. The host molecule has 222 symmetry. Two monodentate nitrato groups and four pyridine ligands are coordinated to Mn(II) along the symmetry axes (the former via O). The pyridine guest molecules lie in the cavities of the crystal framework. For [MnPy₃(NO₃)₂)], only unit cell parameters were determined: a=12.467(5), b=9.514(2), c=16.383(5) Å,β=108.93(4), V=1838(1) ų space group C2/c or Cc (according to extinctions). The pyridine-manganese nitrate system is shown to be analogous to the previously investigated Co, Ni, Cu, Zn, and Cd systems.     

Die Molekül- und Kristallstruktur von [Co3(CN)2 {(OH)4} (NH3)8][Co2(NO2)6 {(OH)2, NO2}] · H2O

The structure of [Co₃(CN)₂ {(OH)₄} (NH₃)₈] [Co₂(NO₂)₆ {(OH)₂, NO₂}] · H₂O has been determined by X-ray methods. The compound crystallizes in the monoclinic space group C_2h⁵–P2₁/n with a = 7.21, b = 12.38, c = 33.13 Å, β = 94°, Z = 4. The crystals contain trinuclear cations in which three Co(III) atoms are bound to two pairs of oxygen atoms. At the central Co atom there are two CN^– ligands in the cis position. The cation is of symmetry C₂. The anion is found to be a binuclear Co(III) complex. The two Co atoms are bound to two OH^– and one NO₂^– groups.     

Crystal structure of the monoclinic polymorph [Co(NH3)5NO2]I2

X-ray diffraction study of [Co(NH₃)₅NO₂]I₂ needle crystals was carried out at 293 and 150 K: an automatic diffractometer, MoK_α radiation, λ=0.71073 Å, space group C2/m, Z=8. The unit cell parameters are a=24.047(5), b=7.648(2), c=17.599(4) Å, β=132.48(3)°, V_cell=2387.0910) ų, d_calc=2.479 g/cm³ at 293 K and a=23.763(5), b=7.577(2), c=17.551(4), Å, β=132.12(3)°, V_cell=2343.9(1) ų, d_calc=2.516 g/cm³ at 150 K, respectively. The R_F values are 11.93% (at 293 K) and 12.30% (at 150 K) for 2032 and 2948 observed reflections, respectively. The structure is of the ionic-island type. [Co(NH₃)₅NO₂]²⁺ complex cations are clustered in [Co(NH₃)₅NO₂]₄ “supercations,” which are linked by N_{(NH 3})...O_{(NO 2}) hydrogen bonds and have 2/m symmetry. A shortening of the distances between certain I ions is indicative of their noticeable interaction. Short contacts also exist between the iodine anions and the ammonia molecules of the complex cations, suggesting the possible formation of NH₃...I hydrogen bonds. The structure investigated is compared with the structures of the orthorhombic and tetragonal modifications of [Co(NH₃)₅NO₂]I₂ along with the structures of α-AgI and transition-metal hexaammoniate polyiodides.     

Synthesis and Crystal Structure of Cesium Nitratometalates(II), Cs2[M(NO3)4] (M = Mn,Co, Ni,Zn)

Crystalline cesium nitratometalates(II), Cs₂[M(NO₃)₄] (M = Mn ( I ), Co ( II ), Ni ( III ), and Zn ( IV )) were synthesized from M(NO₃)₂ · n H₂O and CsNO₃ by heating at 80–120 °C over 10–12 h. According to X-ray crystal structure analysis, the compounds are built from Cs⁺ cations and [M(NO₃)₄]^2– anions. The latter differ by the type of metal coordination: a dodecahedron for Mn in I (CN = 8, r_Mn–O 2.24–2.37 Å), a seven coordination for Co in II (CN = 4 + 3, r_Co–O 2.03–2.16 Å and 2.21–2.35 Å) and a tetrahedral distorted dodecahedron for Zn in IV (CN = 4 + 4, r_Zn–O 1.98–2.15 Å and 2.38–2.72 Å). Ni atom in III has a distorted octahedral NiO₆ environment provided by two unidentate and two bidentate NO₃ groups with Ni–O distances of 2.01–2.14 Å. The differences in metal coordination are discussed in terms of valence electron configurations, ionic radii, and the packing effects.     

Crystal structure of [Co(NH3)5NO2]C2O4. Analysis of specific contacts and structural effects hindering inner-spheric nitro-nitrito isomerization

The structure of [Co(NH₃)₅NO₂]C₂O₄ is solved and refined (space group Immm, a=7.428(2), b=9.790(3), c=6.568(1) Å, V=477.6(2) ų, Z=2; R₁=0.0177, wR₂=0.0279 for F²>4σ(F²); R₁=0.1177, wR₂=0.0643 for all data; residual electron density from 0.125 to ?0.140 e/ų). Specific contacts in the structure are analyzed. Crystal chemical interpretation is suggested to explain the occurrence of photodecomposition rather than photochemical bond isomerization under the action of light in cobalt(III) nitropentammoniate oxalate crystals, in contrast to all previously investigated cobalt(III) nitropentammoniates.     

Synthesis and crystal structure of New Amminecopper(II) Nitrates: [Cu(NH3)2](NO3)2 and [Cu(NH3)](NO3)2

[Cu(NH₃)₂](NO₃)₂ ( I ) and [Cu(NH₃](NO₃)₂ ( II ) were synthesized by interaction of molten NH₄NO₃ with [Cu(NH₃)₄](NO₃)₂ and Cu(NO₃)₂ · 3 H₂O, respectively, at 180 to 195°C for 24 hr. According to X-Ray single crystal analysis, I is orthorhombic (sp. gr. Pbca) with a = 5.678(1), b = 9.765(2), c = 11.596(2) Å, Z = 4, R = 0.060; II is monoclinic (sp. gr. P2₁/c) with a = 6.670(1), b = 8.658(2), c = 9.661(2) Å, β = 101.78(2)°, Z = 4, R = 0.027. In both structures, the nearest coordination environment of Cu is a slightly distorted square formed by N (from NH₃) and O atoms (from NO₃ groups). The structure of I consists of centrosymmetrical [Cu(NH₃)₂](NO₃)₂ molecules linked by hydrogen bonds. The Cu? N and Cu? O distances are 1.98 and 2.01 Å, respectively. In II , the Cu? N distance is 1.95 Å, the Cu? O distances are 1.96, 2.02, and 2.03 Å. The [CuO₃NH₃] squares are connected by NO₃ bridges into zigzag chains, which are linked into layers by longer Cu? O interactions (2.31 Å). Obviously, the layers are additionally strengthened and held together by hydrogen bonds.     

STEREOCHEMISTRY OF (R)-2-METHYLAZIRIDINE COMPLEXES OF COBALT(III) AND DIMERIZATION OF THE LIGAND

Abstract

A cobalt(III) complex containing (R)-2-methylaziridine (R-meaz), [Co(R-meaz)(NH₃)₅]³⁺, was prepared and the two diastereomers arising from the presence of the chiral nitrogen atom (N(R) and N(S)) were separated by column chromatography. Molecular mechanics calculations estimated the N(R)-isomer to be more stable. This result was supported by the x-ray structure determination of the more abundant (ca. 94%) isomer, N(R)-[Co(R-meaz)(NH₃)₅]Br₃H₂O. Crystal data: monoclinic, P2₁, a = 7.357(1), b = 9.780(1), c = 10.426(1) Å, μ = 93.58(1)°, V= 748.7(3) ų, Z= 2. Kinetic studies of isomerization (epimerization) between the two isomers revealed that inversion at the nitrogen center was very slow (5 × 10^?2 M^?1 S^?1at 25 °C). The small rate constant seems to be related to the strained three-membered structure of the meaz ligand. The reaction of Na₃[Co(N0₂)6] and R-meaz yielded a complex containing two dimerized R-meaz chelates, trans-[Co(NO₂)2(di-R-meaz)₂] (di-R-meaz =RR)-α,2-dimethyl-l-aziridineethanamine). The crystal strucrure of trans-[Co(NO₂)₂ (di-R-meaz)₂]C1O₄H₂O was established by x-ray crystallography. Crystal data: orthorhombic, P2₁2₁2₁, a = 11.784(6), b = 21.023(9), c = 8.608(7) Å, V = 2133(2) ų, Z = 4.     

Synthesis and Crystal Structure of Alkali Metal and Ammonium Nitratocuprates(II): M3[Cu(NO3)4](NO3) (M = K,NH4, Rb) and Cs2[Cu(NO3)4]

Blue crystals of metal nitratocuprates(II), M₃[Cu(NO₃)₄](NO₃) (M = K ( I ), NH₄ ( II ), Rb ( III )) and Cs₂[Cu(NO₃)₄] ( IV ) were synthesized from Cu(NO₃)₂ · 3 H₂O and MNO₃ by heating at 100–140 °C during 3–12 h. X-ray single crystal structures for isotypic I and II reveal the presence of the [Cu(NO₃)₄]^2– and NO₃^– anions and M⁺ cations. Structure IV contains [Cu(NO₃)₄]^2– and Cs⁺. In structures I , II , and IV , Cu atoms have a square-planar coordination [CuO₄] with short Cu–O distances of 1.92–2.00 Å, the oxygen atoms belonging to four different NO₃ groups. Each coordinated NO₃ group is a nonsymmetrical bidentate ligand with the second, longer Cu–O distance from 2.38 to 2.74 Å. Rubidium derivative III was shown to be isotypic to I on the basis of unit cell dimensions and symmetry. Eight-coordinate metal(II) environment in tetranitrates is compared for transition metals with different electronic configurations.     

Low‐Dimensional Structural Units in Amine‐Templated Uranyl Oxoselenates(VI): Synthesis and Crystal Structures of [C3H12N2][(UO2)(SeO4)2(H2O)2](H2O), [C5H16N2]2[(UO2)(SeO4)2(H2O)](NO3)2, [C4H12N][(UO2)(SeO4)(NO3)], and [C4H14N2][(UO2)(SeO4)2(H2O)]

The crystals of four amine‐templated uranyl oxoselenates(VI), [C₃H₁₂N₂][(UO₂)(SeO₄)₂(H₂O)₂](H₂O) ( 1 ), [C₅H₁₆N₂]₂[(UO₂)(SeO₄)₂(H₂O)](NO₃)₂ ( 2 ), [C₄H₁₂N][(UO₂)(SeO₄)(NO₃)] ( 3 ), and [C₄H₁₄N₂][(UO₂)(SeO₄)₂(H₂O)] ( 4 ) were prepared by evaporation from aqueous solution of uranyl nitrate, selenic acid and the respective amine. The crystal structures of all four compounds have been solved by direct methods from X‐ray diffraction data. The structure of 1 (triclinic, , a = 7.5611(16), b = 7.7650(17), c = 12.925(3) Å, α = 94.605(18), β = 94.405(17), γ = 96.470(17)°, V = 748.8(3) ų, R₁ = 0.029 for 2769 unique observed reflections) is based upon 0D‐units of the composition [(UO₂)₂(SeO₄)₄(H₂O)₄]^4?. These discrete units are composed from two pentagonal [UO₇]^8? bipyramids linked via [SeO₄]^2? tetrahedra and are unknown in structural chemistry of uranium so far. The structure of 2 (monoclinic, C2/c, a = 28.916(5), b = 8.0836(10), c = 11.9856(16) Å, β = 110.909(11)°, V = 2617.1(6) ų, R₁ = 0.035 for 2578 unique observed reflections) contains [(UO₂)(SeO₄)₂(H₂O)]^2? chains of corner‐sharing pentagonal [UO₇]^8? bipyramids and [SeO₄]^2? tetrahedra. The chains run parallel to the c axis and are arranged into layers parallel to (100). In the structure of 3 (monoclinic, C2/m, a = 21.244(5), b = 7.1092(11), c = 8.6581(18) Å, β = 97.693(17)°, V = 1295.8(4) ų, R₁ = 0.027 for 1386 unique observed reflections), pentagonal [UO₇]^8? bipyramids share corners with three [SeO₄]^2? tetrahedra each and an edge with a [NO₃]^? anion to form [(UO₂)(SeO₄)(NO₃)]^? chains parallel to the b axis. In the structure of 4 (triclinic, , a = 6.853(2), b = 10.537(3), c = 10.574(3) Å, α = 99.62(3), β = 94.45(3), γ = 100.52(3)°, V = 735.6(4) ų, R₁ = 0.045 for 2713 unique observed reflections), one symmetrically independent pentagonal [UO₇]^8? bipyramid shares corners with four [SeO₄]^2? tetrahedra to form the [(UO₂)(SeO₄)₂(H₂O)]^2? chains parallel to the a axis. A comparison to related uranyl compounds is given.     

Synthese und Struktur der ternären Ammoniumnitrate (NH4)2[M(NO3)5] (M = Tb?Lu,Y

Synthesis and Structure of the Ternary Ammonium Nitrates (NH₄)₂[M(NO₃)₅] (M = Tb? Lu, Y) Single crystals of the ternary ammonium nitrates (NH₄)₂[M(NO₃)₅] (M = Tb? Lu, Y) are obtained from the solution of the sesquioxides in a melt of NH₄NO₃ and sublimation of the excess NH₄NO₃. In the crystal structure of (NH₄)₂[Tm(NO₃)₅] (trigonal, P3₁, Z = 3; a = 1 123.76(8), c = 930.1(1) pm; R = 0.062; R_w = 0.034) Tm³⁺ is surrounded by five bidentate nitrate ligands. The isolated [Tm(NO₃)₅]^2? groups are held together by ammonium ions.     

Hexachloroplatinates of the Lanthanides: Syntheses and Thermal Decomposition of [M(NO3)2(H2O)6]2[PtCl6]·2H2O (M = La,Pr) and [M(NO3)(H2O)7][PtCl6]·4H2O (M = Gd,Dy)

The reaction of the nitrates M(NO₃)₃·6H₂O (M = La, Pr) and (H₃O)₂PtCl₆ led to yellow single crystals of [M(NO₃)₂(H₂O)₆]₂[PtCl₆]·2H₂O (M = La, Pr) (monoclinic, P2₁/c, Z = 2, La/Pr: a = 697.4(3)/695.5(1), b = 1654.5(1)/1652.5(2), c = 1317.7(6)/1318.5(3) pm, β = 93.97°(7)/93.93°(2), R_all = 0.0169/0.0659) while the reaction of M(NO₃)₃·5H₂O (M = Gd, Dy) and (H₃O)₂PtCl₆ yielded yellow single crystals of [M(NO₃)(H₂O)₇][PtCl₆]·4H₂O (monoclinic, P2₁/n, Z = 4, Gd/Dy: a = 838.72(3)/838.40(2), b = 2131.98(6)/2139.50(7), c = 1142.63(3)/1143.10(3) pm, β = 95.670(4)/95.698(3), R_all = 0.0475/0.0337). The crystal structures consist of octahedral [PtCl₆]^2? anions and complex [M(NO₃)₂(H₂O)₆]₂⁺ and [M(NO₃)(H₂O)₇]²⁺ cations, respectively. The thermal decomposition of both types of compounds leads via various steps to elemental platinum and the oxide chlorides MOCl (M = La, Pr, Gd, Dy).     

Die Reaktionen von M[BF4] (M = Li,K) und (C2H5)2O·BF3 mit (CH3)3SiCN. Bildung von M[BFx>(CN)4—x] (M = Li,K; x = 1, 2) und (CH3)3SiNCBFx(CN)3—x, (x = 0, 1)

The Reactions of M[BF₄] (M = Li, K) and (C₂H₅)₂O·BF₃ with (CH₃)₃SiCN. Formation of M[BF_x(CN)_4—x] (M = Li, K; x = 1, 2) and (CH₃)₃SiNCBF_x(CN)_3—x, (x = 0, 1) The reaction of M[BF₄] (M = Li, K) with (CH₃)₃SiCN leads selectively, depending on the reaction time and temperature, to the mixed cyanofluoroborates M[BF_x(CN)_4—x] (x = 1, 2; M = Li, K). By using (C₂H₅)₂O·BF₃ the synthesis yields the compounds (CH₃)₃SiNCBF_x(CN)_3—x x = 0, 1. The products are characterized by vibrational and NMR‐spectroscopy, as well as by X‐ray diffraction of single‐crystals: Li[BF₂(CN)₂]·2Me₃SiCN Cmc2₁, a = 24.0851(5), b = 12.8829(3), c = 18.9139(5) Å V = 5868.7(2) ų, Z = 12, R₁ = 4.7%; K[BF₂(CN)₂] P4₁2₁2, a = 13.1596(3), c = 38.4183(8) Å, V = 6653.1(3) ų, Z = 48, R₁ = 2.5%; K[BF(CN)₃] P1¯, a = 6.519(1), b = 7.319(1), c = 7.633(2) Å, α = 68.02(3), β = 74.70(3), γ = 89.09(3)°, V = 324.3(1) ų, Z = 2, R₁ = 3.6%; Me₃SiNCBF(CN)₂ Pbca, a = 9.1838(6), b = 13.3094(8), c = 16.840(1) Å, V = 2058.4(2) ų, Z = 8, R₁ = 4.4%     

New Volatile Nitronium Nitratometalates: NO2[Fe(NO3)4] and NO2[Zr(NO3)5] — Synthesis and Crystal Structure

Crystalline NO₂[Fe(NO₃)₄] was obtained by dehydration of a solution of Fe(NO₃)₃ in 100 % HNO₃ and subsequent sublimation. NO₂[Zr(NO₃)₅] was synthesized by reaction of ZrCl₄ with N₂O₅ followed by sublimation in vacuum. X‐ray single crystal structure determination showed both compounds to consist of nitronium cations, NO₂⁺, and nitratometalate anions. N‐O distances in the linear NO₂⁺ cations are in the range of 1.08—1.13Å. In both [Fe(NO₃)₄]⁻ and [Zr(NO₃)₅]⁻ anions, all nitrate groups are coordinated bidentately with average M‐O distances 2.134 and 2.293Å, respectively. Taking into account the position of N atoms around the M atoms, the arrangement of nitrate groups can be described as tetrahedral for the Fe complex and trigonal‐bipyramidal for the Zr complex. There are four shortest N(nitronium)····O(nitrate group) contacts with average distances of 2.705 and 2.726Å in NO₂[Fe(NO₃)₄] and 2.749Å in NO₂[Zr(NO₃)₅]. Nitronium pentanitratohafnate is isotypic to the zirconium complex.     

Hydrothermal Synthesis,Structures and Thermal Stability of Two Novel Lanthanide Complexes: [Er4(tp)6(H2O)6], [Lu(tp)1.5(H2O)3]

Two novel lanthanide complexes with the formula [Er₄(tp)₆(H₂O)₆] ( 1 ) and [Lu(tp)_1.5(H₂O)₃] ( 2 ) (tp = terephthalate) were synthesized by treating Er(NO₃)₃, Lu(NO₃)₃ with terephthalic acid under hydrothermal conditions, respectively. The structures were determined by X‐ray crystallography. The crystal 1 is of orthorhombic, space group Pbca(61) with a = 9.6656(2) Å, b = 26.2338(5) Å, c = 37.9022(7) Å, C₄₈H₃₆Er₄O₃₀, M = 1761.81, Z = 8, V = 9610.69(32) ų, F(000) = 6688, R₁ = 0.0326 and ωR = 0.0650. The crystal of 2 is of triclinic, space group with a = 7.8204(1) Å, b = 9.5355(1) Å, c = 10.6348(1) Å, α = 68.869(1)°, β = 71.081(1)°, γ = 75.151(1)°, C₂₄H₂₄Lu₂O₁₈, M = 475.19, Z = 2, V = 690.98(1) ų, F(000) = 454, R₁ = 0.0215 and ωR = 0.0474. Both of the two coordination polymers exhibit sandwich‐like packing structures.     

Die Struktur der Hydrate von Co3[Co(CN)6]2 und Cd3[Co(CN)6]2

The crystal structures of Co₃[Co(CN)₆]₂, 12 H₂O (a, = 10.210 ± 0.005 Å) and Cd₃[Co(CN)₆]₂, 12 H₂O (a = 10.590 ± 0.005 Å) have been determined by X-ray powder methods. According to the measured density the unit cell contains 1 1/3 formula units with 4 Co²⁺ (Cd²⁺) in 4a, 2 2/3 Co³⁺ in 4b, 16 C and 16 N in 24e, 8 H₂O_I near 24e, (96k) and 8 H₂O_II near 8 _c (192 l). Structure factor calculations based on the space group O_h⁵ - F m 3 m lead to the following final values of the reliability index R: 0.038 (Co₃[Co(CN)₆]₂, 12 H₂O) and 0.037 (Cd₃[Co(CN)₆]₂, 12 H₂O). The interatomic distances for the cobaltous compound (in parentheses for the cadmium compound) are: Co³⁺-C: 1.88 Å (1.89); C-N: 1.15 Å (1.17); Co²⁺-N: 2.08 Å (2.24); Co²⁺-O_I: 2.10 Å (2.27); shortest O_I-H-O_II-bonds: 2.89 Å (2.82). Co³⁺ is octahedrally coordinated by six carbon atoms, the divalent metal ion by four nitrogen atoms and two water molecules. The two different metal ions are connected by M²⁺-N-C-Co³-bonds to a threedimensional network. The infrared and electronic spectra are shown to be in agreement with the results of the structure analyses of these compounds. The observed positions of the OH-stretching vibrations lead to a hydrogenbond-length of 2.8–2.95 Å.     

Transition Metal Halide Salts and Complexes of 2-Aminopyrimidine: Cobalt(II) and Nickel(II) compounds,Crystal Structures of Bis(2-Aminopyrimidinium)MX4 [M = Co,Ni; X = Cl,Br] and 2-Aminopyrimidinium(+2) [NiBr2(H2O)4]Br2

The reaction of MX₂ (M = Co(II), Ni(II); X = Cl, Br) with 2-aminopyrimidine in aqueous acid yields compounds [(2-apmH)₂MX₄], (2-apmH)₂[MX₄], or (2-apmH₂) [MX₂(H₂O)₄]X₂ (2-apmH = 2-aminopyrimidinium; 2-apmH₂ = 2-aminopyrimidinium(2+)). All compounds have been characterized by single crystal X-ray diffraction. The compounds [(2-apmH)₂MX₄] with M = Co, X = Cl (1); M = Ni, X = Cl (3); and M = Ni, X = Br (4) are isomorphous and crystallize as nearly square planar MX₄ units with the 2-apmH cations coordinated in the axial sites through the unprotonated ring nitrogen. (2-ApmH)₂[CoBr₄] (2) crystallizes as the salt with a nearly tetrahedral CuBr₄ ^2- anion. (2-ApmH₂)[NiBr₂(H₂O)₄]Br₂ (5) forms as a cocrystal of the neutral, six-coordinate nickel complex and (2-ampH₂)Br₂, stabilized by extensive hydrogen bonding. Crystal data (1): monoclinic, P2₁/c, a = 7.540(4), b = 12.954(4), c = 7.277(3) Å, β = 110.09(6), V = 667.4(5) ų, Z = 2, D_calc = 1.955 Mg/m³, μ = 2.079 mm^-1, R = 0.0501 for [|I|≥2(I)]. For (2): triclinic, P-1, a = 7.720(2), b = 7.916(2), c = 14.797(3) Å, α = 97.264(3), β = 104.788(3), γ = 105.171(3)°, V = 825.3(3) ų, Z = 2, D_calc = 2.296 Mg/m³, μ = 10.715 mm^-1, R = 0.0308 for [|I|≥2(I)]. For (3): monoclinic, P2₁/c, a = 7.595(3), b = 12.891(4), c = 7.204(3) Å, β = 111.07(3)°, V = 658.2 ų, Z = 2, D_calc = 1.982 Mg/m³, μ = 2.279 mm^-1, R = 0.0552 for [|I|≥2(I)]. For (4): monoclinic, P2₁/c, a = 7.840(2), b = 13.358(4), c = 7.518(2) Å, β = 110.923(3)°, V = 938.6(3) ų, Z = 2, D_calc = 2.577 Mg/m³, μ = 12.18 mm^-1, R = 0.0280 for [|I|≥2(I)]. For (5): orthorhombic, Pnma, a = 16.776(6), b = 11.943(4), c = 7.079(3) Å, V = 1418.2(9) ų, Z = 4, D_calc = 2.564 Mg/m³, μ = 12.639 mm^-1, R = 0.0381 for [|I|≥2σ(I)].     

Darstellung,Kristallstruktur, Schwingungsspektren und Normalkoordinatenanalyse von [Co(NH3)6][Os(SCN)6]

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of [Co(NH₃)₆][Os(SCN)₆] From the mixture of the linkage isomers [Os(NCS)_n(SCN)_6–n]^3–, n = 0–2, pure [Os(SCN)₆]^3– has been isolated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐ray structure determination on a single crystal of [Co(NH₃)₆][Os(SCN)₆] (trigonal, space group R 3, a = 12.368(2), c = 11.830(2) Å, Z = 3) reveals that the thiocyanate ligands are exclusively S‐coordinated with the Os–S distance of 2.388 Å and the Os–S–C angle of 108.8°. The IR and Raman spectra of (n‐Bu₄N)₃[Os(SCN)₆] are assigned by normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constant f_d(OsS) is 1.42 mdyn/Å.     

The New Homoleptic Tetracyanamidoaluminate LiBa2[Al(CN2)4]

The new tetracyanamidoaluminate LiBa₂[Al(CN₂)₄] was prepared by solid state metathesis reaction in a fused copper ampoule from a mixture of BaF₂, AlF₃, and Li₂(CN₂) at 550 °C. The crystal structure was solved and refined based on single‐crystal X‐ray diffraction data [P2₁2₁2₁, Z = 4, a = 6.843(1) Å, b = 11.828(2) Å, c = 11.857(2) Å]. The compound belongs to the known formula type LiM₂[Al(CN₂)₄] (M = Sr, Eu) containing the homoleptic [Al(CN₂)₄]^5– ion. However, LiBa₂[Al(CN₂)₄] forms a distinct crystal structure, containing a two‐dimensional [(NCN)_2/2Li(NCN)₂Al(NCN)_2/2] network with four‐coordinate Li⁺ and Al³⁺ ions. Two crystallographically independent Ba²⁺ ions are situated in eightfold environment of terminal nitrogen atoms of cyanamide ions.     

Synthesis and Crystal Structure of [La(phen)2(H2O)2(NO3)2]NO3 · 2(phen)(H2O) with phen = 1,10‐phenanthroline

The title compound [La(phen)₂(H₂O)₂(NO₃)₂](NO₃) · 2(phen)(H₂O) with phen = 1,10‐phenanthroline was prepared by the stoichiometric reaction of La(NO₃)₃ · 6 H₂O and 1,10‐phenanthroline monohydrate in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 11.052(2), b = 13.420(2), c = 16.300(2) Å, α = 78.12(1)°, β = 88.77(1)°, γ = 83.03(1)°, Z = 2, R = 0.0488, wR² = 0.1028) consists of [La(phen)₂(H₂O)₂(NO₃)₂]²⁺ complex cations, NO₃^– anions, phen and H₂O molecules. The La atom is 10‐fold coordinated by four N atoms of two bidentate chelating phen ligands and six O atoms of two H₂O molecules and two bidentate chelating NO₃^2– ligands with d(La–O) = 2.522–2.640 Å and d(La–N) = 2.689–2.738 Å. The intermolecular π‐π stacking interactions play an essential role in the formation of two different 2 D layers parallel to (001), which are formed by complex cations and uncoordinating phen molecules, respectively. The uncoordinated NO₃^– anions and H₂O molecules are sandwiched between the cationic and phen layers.     

Tetranitratogoldsäure, (H5O2)[Au(NO3)4]·H2O: Synthese,Kristallstruktur und thermisches Verhalten des ersten sauren Nitrates des Goldes

Tetranitratogold(III) Acid, (H₅O₂)[Au(NO₃)₄]·H₂O: Synthesis, Crystal Structure, and Thermal Behaviour of the First Acidic Nitrate of Gold Yellow single crystals of (H₅O₂)[Au(NO₃)₄]·H₂O grow upon cooling of a solution of Au(OH)₃ in conc. nitric acid. The crystal structure contains (monoclinic, C2/c, Z = 4, a = 1214.5(2), b = 854.4(1), c = 1225.7(2) pm, β = 117.75(1)°, R_all = 0.0331) the Au³⁺ ion in coordination of four monodentate NO₃^— ligands. The [Au(NO₃)₄]^— units are linked by H₅O₂⁺‐ions. Significant hydrogen bonding is observed in the crystal structure between the H₅O₂⁺ ions and the H₂O molecules. The thermal analysis reveals a five step decomposition leading to elemental gold.