Synthese und Struktur der Nitridoborat‐Nitride Ln4(B2N4)N (Ln = La,Ce) des Formeltyps Ln3+x(B2N4)Nx (x = 0, 1, 2)

Synthesis and Structure of Nitridoborate Nitrides Ln₄(B₂N₄)N (Ln = La, Ce) of the Formula Type Ln_3+x(B₂N₄)N_x (x = 0, 1, 2) The missing member of the formula type Ln_3+x(B₂N₄)N_x with x = 1 was synthesized and characterized for Ln = La and Ce. According to the single‐crystal X‐ray structure solution Ce₄(B₂N₄)N crystallizes in the space group C2/m (Z = 2) with the lattice parameters a = 1238.2(1) pm, b = 357.32(3) pm, c = 905.21(7) pm and β = 129.700(1)°. The anisotropic structure refinement converged at R1 = 0.039 and wR2 = 0.099 for all independent reflections. A powder pattern of La₄(B₂N₄)N was indexed isotypically with a = 1260.4(1) pm, b = 366.15(3) pm, c = 919.8(1) pm and β = 129.727(6)°. A structure rational for nitridoborates and nitridoborate nitrides containing B₂N₄ ions with the general formula Ln_3+x(B₂N₄)N_x with x = 0, 1, 2 is presented.     

Über das metallreiche Lanthannitridoboratnitrid La5(B2N4)N2

On the Metal‐rich Lanthanum Nitridoborate Nitride La₅(B₂N₄)N₂ La₅(B₂N₄)N₂ was synthesized by solid state reactions in fused tantalum containers from Li₃(BN₂), LaCl₃, Li₃N and La at 950 °C. The crystal structure refinement on a needle‐shaped single‐crystal yielded the monoclinic space group C2/m, the lattice parameters a = 1259.5(2), b = 368.53(4), c = 909.4(2) pm, β = 106.03(2)°, and R values of R1 = 0.041, wR2 = 0.066 for all independent reflections. The new compound La₅(B₂N₄)N₂ introduces the member with x = 2 to the formula type RE_3+x(B₂N₄)N_x (RE = rare earth, x = 0, 1). The structure contains the nitridoborate ion B₂N₄^8– that is isoelectronic with the oxalate ion and N^3–. Corresponding with (La³⁺)₅(B₂N₄)^8–(N^3–)₂(e^–) one additional electron is present.     

Anionische Fragmente aus h‐BN in der Struktur La6B4N10

Anionic Fragments of h‐BN in the Structure La₆B₄N₁₀ The compound La₆B₄N₁₀ was synthesized by solid state reactions at high temperatures. Crystals obtained for La₆B₄N₁₀ were systematically twinned and showed orthorhombic symmetry. An X‐ray crystal structure refinement on a needle shaped pseudo‐merohedral twin yielded the monoclinic space group P2₁/c, Z = 2, lattice parameters a = 971.89(6) pm, b = 1479.41(9) pm, c = 762.32(4) pm, β = 90.005(9)° and converged at R1 = 0.0352, wR2 = 0.0555 for all independent reflections. The structure of La₆(B₃N₆)(BN₃)N contains cyclic B₃N₆ ions with three exocyclic N atoms, carbonate ion like BN₃ units and nitride ions that can be considered as fragments or products of a nitration reaction of hexagonal boron nitride.     

Neue Vertreter des Er6[Si11N20]O‐Strukturtyps Hochtemperatur‐Synthesen und Kristallstrukturen von Ln(6+x/3)[Si(11–y)AlyN(20+x–y)]O(1–x+y) mit Ln = Nd,Er, Yb,Dy und 0 ≤ x ≤ 3, 0 ≤ y ≤ 3

New Representatives of the Er₆[Si₁₁N₂₀]O Structure Type. High‐Temperature Synthesis and Single‐Crystal Structure Refinement of Ln_(6+x/3)[Si_(11–y)Al_yN_(20+x–y)]O_(1–x+y) with Ln = Nd, Er, Yb, Dy and 0 ≤ x ≤ 3, 0 ≤ y ≤ 3 According to the general formula Ln_(6+x/3)[Si_(11–y)Al_yN_(20+x–y)]O_(1–x+y) (0 ≤ x ≤ 3, 0 ≤ y ≤ 3) four nitridosilicates, namely Er₆[Si₁₁N₂₀]O, Yb_6.081[Si₁₁N_20.234]O_0.757, Dy_0.33Sm₆[Si₁₁N₂₀]N, and Nd₇[Si₈Al₃N₂₀]O were synthesized in a radiofrequency furnace at temperatures between 1300 and 1650 °C. The homeotypic crystal structures of all four compounds were determined by single‐crystal X‐ray diffraction. The nitridosilicates are trigonal with the following lattice constants: Er₆[Si₁₁N₂₀]O: a = 978.8(4) pm, c = 1058.8(3) pm; Yb_6.081[Si₁₁N_20.243]O_0.757: a = 974.9(1) pm, c = 1055.7(2) pm; Dy_0.33Sm₆[Si₁₁N₂₀]N: a = 989.8(1) pm, c = 1078.7(1) pm; Nd₇[Si₈Al₃N₂₀]O: a = 1004.25(9) pm, c = 1095.03(12) pm. The crystal structures were solved and refined in the space group P31c with Z = 2. The compounds contain three‐dimensional networks built up by corner sharing SiN₄ and AlN₄ tetrahedra, respectively. The Ln³⁺ and the “isolated” O^2– ions are situated in the voids of the structures. According to Ln_(6+x/3)[Si_(11–y)Al_yN_(20+x–y)]O_(1–x+y) an extension of the Er₆[Si₁₁N₂₀]O structure type has been found.     

La6(BN3)O6, ein Nitridoborat‐Oxid des Lanthans

La₆(BN₃)O₆, a Nitridoborate Oxide of Lanthanum Single‐crystals of La₆(BN₃)O₆ were formed in reactions of Li₃BN₂, Li₃N, and LaOCl at 950 °C. The structure was solved by single‐crystal X‐ray diffraction. La₆(BN₃)O₆crystallizes with the space group Cmcm (no. 63) containing Z = 4 formula units in the unit cell, with lattice parameters of a = 366.88(3) pm, b = 2509.2(3) pm, and c = 1101.1(1) pm (R1 = 0.054, wR2 = 0.065 for all collected symmetry independant reflections). The crystal structure reflects typical patterns obtained in structures of nitridoborates. Tri‐nitridoborate ions are coordinated by La³⁺ ions in a tricapped trigonal prismatic arrangement, being stacked via shared trigonal faces to form columns. The arrangement of the columns in the structure provides space for O^2— ions with CN = 4, 5, and 6.     

Über das Tri(phosphorano)borazinium-Monokation [H3B3(NPEt3)3Cl2]+. Kristallstrukturen von Me3SiNPR3 · BH3 (R = Et,Ph), [H3B3(NPEt3)3Cl1,85Br0,15]Br · CCl4 und des Hydrolyseproduktes NH4[B5O6(OH)4] · 2 H2O

On the Tri(phosphorano)borazinium Monocation [H₃B₃(NPEt₃)₃Cl₂]⁺. Crystal Structures of Me₃SiNPR₃ · BH₃ (R = Et, Ph), [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄, and of the Product of Hydrolysis NH₄[B₅O₆(OH)₄] · 2 H₂O The crystal structures of the donor-acceptor complexes of the silylated phosphanimines with borane which are suitable as educts for the synthesis of tri(phosphorano)borazinium ions, Me₃SiNPR₃ · BH₃ (R = Et, Ph), are described. After addition of CCl₄ the reaction of Me₃SiNPEt₃ with HBBr₂ · SMe₂ in CH₂Cl₂ leads to the tri(phosphorano)borazinium monocation [H₃B₃(NPEt₃)₃Cl₂]⁺, which is characterized crystallographically as [H₃B₃ · (NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄. It complements the series of the tri(phosphorano) cations [H₃B₃(NPEt₃)₃]³⁺ and [H₄B₃(NPEt₃)₃]²⁺ by the monocation. NH₄[B₅O₆(OH)₄] · 2 H₂O can be isolated as product of hydrolysis of the tri(phosphorano)borazinium ions; its crystal structure is redetermined, because in the literature it is based on a wrong space group. Me₃SiNPEt₃ · BH₃ ( 1 ): Space group P1, Z = 4, lattice dimensions at 213 K: a = 710.9(4), b = 1465.9(3), c = 1536.0(3) pm, α = 107.05°, β = 99.40(3)°, γ = 97.41(3)°; R = 0.0740. Me₃SiNPPh₃ · BH₃ ( 2 ): Space group P2₁/c, Z = 4, lattice dimensions at 203 K: a = 934.6(1), b = 1398.6(1), c = 1626.1(1) pm, β = 103.52(1)°; R = 0.0556. [H₃B₃(NPEt₃)₃Cl_1.85Br_0.15]Br · CCl₄ ( 3 ): Space group P2₁/n, Z = 4, lattice dimensions at 223 K: a = 1237.9(3), b = 1214.1(3), c = 2402.4(4) pm, β = 93.52(1)°. 3 holds a B₃N₃ six-membered ring in a distorted boat conformation. NH₄[B₅O₆(OH)₄] · 2 H₂O ( 4 ): Space group Aba2, Z = 4, lattice dimensions at 273 K: a = 1131.3(1), b = 1103.0(1), c = 923.0(1) pm; R = 0.0564.     

X‐Ray Single Crystal Refinement and Superconductivity of La3Ni2B2N3

Crystalline samples of La₃Ni₂B₂N₃ were synthesized using solid state metathesis reactions from combinations of La, LaCl₃, NiCl₂ together with Li₃BN₂. The structure was determined by single crystal X‐ray diffraction (I4/mmm (No. 139), a = 372.95(2) pm, c = 2056.3(2) pm, R₁ = 0.027, wR₂ = 0.062) and confirmed earlier results from neutron powder diffraction. La₃Ni₂B₂N₃ contains BN units capping square planar Ni layers. Isolated nitrogen atoms reside in La₆ octahedra. Magnetic measurements on several bulk samples exhibit superconductivity at temperatures below 14.6 K.     

Zur Kenntnis von Tripraseodym‐hexanitridotriborat Pr3B3N6: Neue Synthese und Verfeinerung der Kristallstruktur

On Tripraseodymium Hexanitridotriborate Pr₃B₃N₆: New Synthesis and Crystal Structure Refinement Single‐crystalline Pr₃B₃N₆ was obtained by the reaction of praseodymium and BN_x(NH)_y(NH₂)_z in a NaCl melt under N₂ atmosphere in a high‐frequency furnace at 1250 °C. Contrary to literature data, Pr₃B₃N₆ crystallizes in the centrosymmetric space group R 3 c as revealed by single‐crystal X‐ray diffraction (a = 1211.95(9), c = 701.53(7) pm, Z = 6, R1 = 0.0258, wR2 = 0.0658). In the solid, Pr₃B₃N₆ contains Pr³⁺ and planar cyclotrinitridoborate units B₃N₆^9–. The anions represent motifs from the structure of hexagonal boron nitride (h‐BN) and they are stacked analogously along [001]. Both the bond lengths B–N (average value 147.8 pm) and the interionic distances between the anions (350.8 pm) are comparable with the values in h‐BN.     

Darstellung,Kristallstrukturen und Schwingungsspektren neuer ternärer Verbindungen mit dem Anion [N–B–N]3–

Ternary Nitridoborates. 2. Synthesis, Crystal Structure, and Vibrational Spectra of New Ternary Compounds with the [N–B–N]^3– Anion The isotypic compounds LiM₄[BN₂]₃ (M = Ca, Sr, Ba, Eu) and NaM₄[BN₂]₃ (M = Sr, Ba) are formed as colorless to pale yellow prismatic crystals (black with Eu) by reaction of the binary components Li₃N, M₃N₂, EuN and Na, NaN₃, Ba₃N₂ and BN in sealed niobium ampoules at 1375 and 1275 K, respectively. The linear anions [N–B–N]^3– have bond lengths d(B–N) between 132.6 and 136.6 pm. Vibrational frequencies and force constants f(B–N) = 7.25–7.89 Ncm^–1 reveal significant drifts related to bond length and effective anionic charge. The cubic crystal structures (Im3m (No. 229), Z = 2; LiM₄[BN₂]₃: a(Ca) = 711.5 pm; a(Sr) = 745.6 pm; a(Eu) = 742.5 pm, a(Ba) = 788.0 pm and NaM₄[BN₂] ${}_{\text{3}\text{: a(Sr) = 756.8 pm; a(Ba) = 791.7 pm)) are stuffed derivatives of the β‐PtHg4}}$ structure type, and the range of existence of this cubic structure is derived from the molar volume and the ionic radii. The cations form a partial structure of centered cubes E1(E2)₈ which are condensed to a [E1(E2)_8/2] network (E1 = Li, Na; E2 = Ca, Sr, Ba, Eu). The remaining open cubes are filled by the [BN₂]^3– anions yielding two interpenetrating [E1(BN₂)_6/2] networks. Periodic Nodal Surfaces (PNS) of Im3m symmetry show the regions of different interactions.     

Nitrido-Azido-Komplexe des Molybdän(VI): Synthese und Kristallstruktur von [MoN(N3)2(terpy)]+ [MoN(N3)4]−·MoN(N3)3 (terpy)

Nitrido-Azido-Complexes of Molybdenum(VI). Synthesis and Crystal Structure of [MoN(N₃)₂(terpy)]⁺[MoN(N₃)₄] ^? · MoN(N₃)₃(terpy) (CH₃)₃SiN₃ reacts with Mo(CO)₃(terpy) in CH₃CN yielding red crystals of [MoN(N₃)₂(terpy)]⁺[MoN(N₃)₄] ^?· MoN(N₃)₃(terpy) (space group P1 , a = 1039.3 pm, b = 1384.6 pm, c = 1685.4 pm, α = 112.4°, β = 108.1°, γ = 88.3°, Z = 2, R = 0.035 for 4376 independent reflections). The structure consists of three different mononuclear complexes. In the neutral complex MoN(N₃)₃(terpy) Mo exhibits the coordination number 7 in form of a distorted pentagonal bipyramid, with the terpyridine ligand and two azido groups in the equatorial plane. The axial positions are occupied by the nitrido ligand and another azido group. The triply bonded nitrido nitrogen atom (Mo1? N1 = 165.6 pm) causes a strong trans effect resulting in a long distance of 245.7 pm to N_α of the trans bonded azido group. The cationic complex [MoN(N₃)₂(terpy)]⁺ derives from MoN(N₃)₃-(terpy) by abstraction of the trans bonded azido group. For the molybdenum atom remains the coordination number 6 in form of the rarely found pentagonal pyramid. In the anion [MoN(N₃)₄]^? the molybdenum atom exhibits the coordination number 5 in form of a tetragonal pyramid with the nitrido ligand in the apex. The square basic plane is formed by the N_α atoms of the azido groups.     

Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.     

Synthese und Kristallstrukturen der mehrkernigen Rhenium–Nitrido‐Komplexe [Re2N2Cl4(PMe2Ph)4(MeCN)] und [Re4N3Cl9(PMe2Ph)6]

Synthesis and Structures of the Multinuclear Rhenium Nitrido Complexes [Re₂N₂Cl₄(PMe₂Ph)₄(MeCN)] and [Re₄N₃Cl₉(PMe₂Ph)₆] The binuclear rhenium complex [Re₂N₂Cl₄(PMe₂Ph)₄(MeCN)] ( 1 ) is obtained as a byproduct of the synthesis of [(Me₂PhP)₃(MeCN)ClReNZrCl₅] from [ReNCl₂(PMe₂Ph)₃] and [ZrCl₄(MeCN)₂] in toluene. It crystallizes as 1 · 2 toluene in the monoclinic space group P2₁/n with a = 1517.0(3); b = 1847.7(2); c = 1952.4(6) pm; β = 106.44(1)° and Z = 4. The two Re atoms are connected by an asymmetric nitrido bridge Re≡N–Re with distances Re–N of 169.9(5) and 208.7(5) pm. In course of the reaction of [ReNCl₂(PMe₂Ph)₃] with [ZrCl₄(THF)₂] in CH₂Cl₂ hydrochloric acid is formed by acting of the Lewis acid on the solvent. HCl protonates and eliminates phosphine ligands of the educt [ReNCl₂(PMe₂Ph)₃] to form the phosphonium salt [PMe₂PhH]₂[ZrCl₆] ( 2 ). It crystallizes in the monoclinic space group C2/c with a = 1536.9(3); b = 1148.8(1); c = 1402.2(3) pm, β = 100.70(2)° and Z = 4. The remaining fragments of the rhenium complex combine to yield the tetranuclear mixed valent complex [Re₄N₃Cl₉(PMe₂Ph)₆] ( 3 ), crystallizing as 3 · CH₂Cl₂ in the triclinic space group P 1 with a = 1312.9(19); b = 1661.4(2); 1897.1(2) pm; α = 78.62(1)°; β = 86.77(1)°; γ = 68.28(1)° and Z = 2. The four Re atoms occupy the corners of a tetrahedron. Its edges are formed by three nitrido and three chloro bridges. The asymmetric nitrido bridges Re≡N–Re are characterized by short distances in the range of 172(2) to 176(3) pm and long distances of 194(3) to 204(2) pm. The angles Re–N–Re are between 154(1) and 160(1)°.     

Sterisch abgeschirmte Nitridokomplexe von Molybdän und Wolfram Die Kristallstrukturen von [MoN(NPh2)3] und [W4N4(NPh2)6(OnC4H9)2]

Stericly Shielded Nitrido Complexes of Molybdenum and Tungsten. The Crystal Structures of [MoN(NPh₂)₃] and [W₄N₄(NPh₂)₆(OⁿC₄H₉)₂] The reactions of MoNCl₃ and WNCl₃, respectively, with lithium diphenylamide in tetrahydrofurane produce the monomeric nitrido complexes MN(NPh₂)₃ with CN = 4 at the metal atoms. In the presence of lithium-n-butyl LiNPh₂ and WNCl₃ also form the tetrameric nitrido complex [W₄N₄(NPh₂)₆(OⁿC₄H₉)₂] which contains W^V and W^VI. The compounds are characterized by their i.r. spectra, by X-ray structural analysis, and, partially, by ¹H and ¹³C n.m.r. spectroscopy. MoN(NPh₂)₃: Space group P1 , Z = 2, 4060 observed independent reflexions, R = 0.031. Lattice dimensions at 20°C: a = 956.2(4) pm, b = 1 015.9(2) pm, c = 1 598.1(3) pm; α = 79.06(2)°, β = 85.67(3)°, γ = 82.57(3)°. The compound forms monomeric molecules with Mo?N bond lengths of 163.4 pm and mean Mo? NPh₂ distances of 199.2 pm. [W₄N₄(NPh₂)₆(OⁿC₄H₉)₂]: Space group P2₁/n, Z = 2, 1903 observed independent reflexions, R=0.039. Lattice parameters at 19°C: a = 1582.2(3) pm, b = 1182.4(2) pm, c = 2053.3(4) pm; β = 103.77(2)°. The compound forms centrosymmetric molecules, in which the central W–W dumb-bell (bond length 253.5 pm) is linked by the nitrido ligands of two WN₂(NPh₂)₂=units in a T shaped order of the N-atoms.     

Zn5Ir7B3, Zn5Rh7B3 und Zn7+xRh9–xB3 (x ≈ 0,4) – neue ternäre Zink‐Platinmetallboride

Zn₅Ir₇B₃, Zn₅Rh₇B₃, and Zn_7+xRh_9–xB₃ (x ≈ 0.4) – New Ternary Zinc Platinum Metal Borides The new ternary zinc borides Zn₅Ir₇B₃, Zn₅Rh₇B₃, and Zn_7+xRh_9–xB₃ (x ≈ 0.4) were prepared by reaction of the elemental components at temperatures in the range 1200 to 1230 ?C. They crystallize orthorhombically in the space group Pmma with Z = 2. Zn₅Ir₇B₃ (a = 1116.1(2) pm, b = 284.96(4) pm, c = 1178.1(2) pm; R = 0.042, 1414 reflections, 47 parameters) and Zn₅Rh₇B₃ (a = 1101.6(2) pm, b = 283.94(3) pm, c = 1166.6(4) pm, R = 0.033, 787 reflections, 47 parameters) are isotypic. Along the short axis planar nets of platinum metal atoms at y = 0 alternate with layers containing the boron and zinc atoms at z = ¹/₂. By the stacking of the platinum metal nets columns of trigonal prisms centered by boron atoms, columns of pentagonal prisms containing zinc atoms and channels with horse shoe shaped cross sections, all running along the b‐axis are formed. The latter are filled by an aggregation of zinc atoms consisting of four parallel rows. In the structure of Zn_7+xRh_9–xB₃ (a = 1117.1(3) pm, b = 285.38(8) pm, c = 1484.8(5) pm; R = 0.026, 975 reflections, 59 parameters) one of the sitesets is occupied by Rh and Zn atoms approximately in the ratio 6 : 4. The structure contains the same building elements as those found in Zn₅Rh₇B₃ and in addition Rh prisms with elongated hexagon cross sections accommodating pairs of zinc atoms. These prisms are connected by common faces to form layers perpendicular to the c axis.     

Isotype Borophosphate MII(C2H10N2)[B2P3O12(OH)] (MII = Mg,Mn, Fe,Ni, Cu,Zn): Verbindungen mit Tetraeder‐Schichtverbänden

Isotypic Borophosphates M^II(C₂H₁₀N₂)[B₂P₃O₁₂(OH)] (M^II = Mg, Mn, Fe, Ni, Cu, Zn): Compounds containing Tetrahedral Layers The isotypic compounds M^II(C₂H₁₀N₂) · [B₂P₃O₁₂(OH)] (M^II = Mg, Mn, Fe, Ni, Cu, Zn) were prepared under hydrothermal conditions (T = 170 °C) from mixtures of the metal chloride (chloride hydrate, resp.), Ethylenediamine, H₃BO₃ and H₃PO₄. The orthorhombic crystal structures (Pbca, No. 61, Z = 8) were determined by X‐ray single crystal methods (Mg(C₂H₁₀N₂)[B₂P₃O₁₂(OH)]: a = 936.81(2) pm, b = 1221.86(3) pm, c = 2089.28(5) pm) and Rietveld‐methods (M^II = Mn: a = 931.91(4) pm, b = 1234.26(4) pm, c = 2129.75(7) pm, Fe: a = 935.1(3) pm, b = 1224.8(3) pm, c = 2088.0(6) pm, Ni: a = 939.99(3) pm, b = 1221.29(3) pm, c = 2074.05(7) pm, Cu: a = 941.38(3) pm, b = 1198.02(3) pm, c = 2110.01(6) pm, Zn: a = 935.06(2) pm, b = 1221.33(2) pm, c = 2094.39(4) pm), respectively. The anionic part of the structure contains tetrahedral layers, consisting of three‐ and nine‐membered rings. The M^II‐ions are in a distorted octahedral or tetragonal‐bipyramidal [4 + 2] (copper) coordination formed by oxygen functions of the tetrahedral layers. The resulting three‐dimensional structure contains channels running along [010]. Protonated Ethylenediamine ions are fixed within the channels by hydrogen bonds.     

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2NbCl4 und [Re3N3Cl5(PMe2Ph)6][NbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂NbCl₄ and [Re₃N₃Cl₅(PMe₂Ph)₆][NbCl₆] The reaction of ReNCl₂(PMe₂Ph)₃ with NbCl₅ in toluene yields the trinuclear complexes [(Me₂PhP)₃Cl₂ReN]₂‐ NbCl₄ (1) and [Re₃N₃Cl₅(PMe₂Ph)₆][NbCl₆] ( 2 ). 1 forms triclinic crystals with the composition 1 · 2 C₇H₈ (P 1, a = 1074.5(1), b = 1289.1(2), c = 1299.3(2) pm, α = 85.25(2)°, β = 81.04(2)°, γ = 86.02(1)°, Z = 1). In the centrosymmetric compound 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit NbCl₄ to form an almost linear arrangement Re≡N–Nb–N≡Re. The length of the Re–N triple bonds is 172,2 pm, and the Nb–N distances of 216.0 pm correspond to coordinative single bonds. 2 forms orthorhombic crystals with the space group P2₁2₁2₁ and a = 1286.0(1), b = 2109.2(4), c = 2436.2(3) pm, Z = 4. The three Re atoms are located at the corners of a triangle. They are connected by two asymmetric nitrido bridges and two asymmetric chloro bridges. The weakly bent nitrido bridges (Re–N–Re = 152° and 157°) are characterized by Re–N distances of 169 und 207 pm as well as 171 and 207 pm. Re1, in addition, binds a terminal nitrido ligand with Re1–N1 = 166 pm.     

Darstellung und Kristallstruktur des TetramethylammoniumthiocyanatSchwefeldioxid‐Adduktes, (CH3)4N+SCN– · SO2

Preparation and Crystal Structure of the Tetramethylammonium Thiocyanate Sulfur Dioxide Adduct, (CH₃)₄N⁺SCN^– · SO₂ Tetramethylammonium thiocyanate reacts with sulfur dioxide under formation of tetramethylammonium thiocyanate sulfur dioxide adduct. The resulting salt is characterised by NMR and vibrational spectroscopy and its crystal structure. (CH₃)₄N⁺SCN^– · SO₂ crystallizes in the monoclinic space group P2₁/c with a = 578.4(1) pm, b = 1634.3(1) pm, c = 1054.6(1) pm, β = 105.17(1)°, and four formula units in the unit cell. The crystal structure possesses a strong S–S interaction between the NCS^– anion and the SO₂ molecule. The NCS–SO₂ distance of 301.02(9) pm is longer than a covalent single bond, thus the compound is rather described as an adduct. The structure is compared with ab initio calculated data.     

Synthese,Kristallstruktur und Eigenschaften der käfigartigen,sechsbasigen Säure P12S12N8(NH)6 · 14 H2O sowie ihrer Salze Li6[P12S12N14] · 26 H2O, (NH4)6[P12S12N14] · 10 H2O und K6[P12S12N14] · 8 H2O

Syntheses, Crystal Structure, and Properties of the Cage‐like, Hexaacidic P₁₂S₁₂N₈(NH)₆ · 14 H₂O and its Salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O, (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O, and K₆[P₁₂S₁₂N₁₄] · 8 H₂O The cage‐like acid P₁₂S₁₂N₈(NH)₆ · 14 H₂O was obtained by the reaction of KSCN with P₄S₁₀ via the formation of K₆[P₁₂S₁₂N₁₄] · 8 H₂O and subsequent ion exchange reactions in aqueous solution. Starting from the acid the salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O and (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O were synthesized. According to X‐ray single‐crystal structure analyses the compounds are built up by isosteric P–N cages [P₁₂S₁₂N^[3]₈N^[2]₆]^6–. Each of them is made up of twelve P₃N₃ rings, which exclusively exhibit the boat conformation. The cages have the idealized symmetry 2/m3; P₁₂S₁₂N₈(NH)₆ · 14 H₂O: P1, a = 1119.11(7), b = 1123.61(7), c = 1125.80(6) pm, α = 80.186(4), β = 60.391(4), γ = 60.605(4)°, Z = 1; Li₆[P₁₂S₁₂N₁₄] · 26 H₂O: Fm3, a = 1797.4(1) pm, Z = 4; (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O: P6₃, a = 1153.2(1), c = 2035.6(2) pm, Z = 2; K₆[P₁₂S₁₂N₁₄] · 8 H₂O: R3c, a = 1142.37(5), c = 6009.6(3) pm, Z = 6. In the crystal the cages of the acid are crosslinked via hydrate molecules by hydrogen bonds. The cations in the salts show a high‐mobility and are located between the cages.     

Synthese,Struktur und Eigenschaften der Komplexe [(Me2PhP)3Cl2Re≡N‐IrCl2(C5Me5)], [(Me2PhP)3Cl2Re≡N‐IrCl(COD)], [PPh4][O3Os≡N‐IrCl2(C5Me5)] und [PPh4][O3Os≡N‐IrCl(COD)] mit Nitridobrücken Re≡N‐Ir und Os≡N‐Ir

Synthesis and Crystal Structures of the Complexes [(Me₂PhP)₃Cl₂Re≡N‐IrCl₂(C₅Me₅)], [(Me₂PhP)₃Cl₂Re≡N‐IrCl(COD)], [PPh₄][O₃Os≡N‐IrCl₂(C₅Me₅)], and [PPh₄][O₃Os≡N‐IrCl(COD)] with Nitrido bridges Re≡N‐Ir and Os≡N‐Ir The heteronuclear complexes [(Me₂PhP)₃Cl₂Re≡N‐IrCl₂(C₅Me₅)] ( 1 ), [(Me₂PhP)₃Cl₂Re≡N‐IrCl(COD)] ( 2 ), [PPh₄][O₃Os≡N‐IrCl₂(C₅Me₅)] ( 3 ) and [PPh₄][O₃Os≡N‐IrCl(COD)] ( 4 ) were obtained by the reaction of the nitrido complexes [ReNCl₂(PMe₂Ph)₃] and [OsO₃N]^— with the iridium compounds [IrCl₂(C₅Me₅)]₂ and [IrCl(COD)]₂ in benzonitrile. 1 forms red crystals with the composition 1 ·C₆H₅CN in the monoclinic space group P2₁/c and a = 1264.7(2); b = 1945.3(2); c = 1835.4(1) pm, β = 90.35(1)°, Z = 4. The complex fragment [IrCl₂(C₅Me₅)] in the dinuclear complex is connected by an asymmetric nitrido bridge Re≡N‐Ir to the nitrido complex [ReNCl₂(PMe₂Ph)₃]. The nitrido bridge is characterized by a Re‐N‐Ir bond angle of 179.4(2)° and distances Re‐N = 170.9(4) pm and Ir‐N = 203.3(4) pm. 2 forms brownish red, triclinic crystals with the space group P1¯ and a = 1076.6(2), b = 1373.2(2), c = 1452.4(1) pm, α = 107.513(8), β = 101.843(9), γ = 110.04(1)°, Z = 2. The nitrido bridge to the complex fragment [IrCl(COD)] has a Re‐N‐Ir bond angle of 173, 8(4)° and distances Re‐N = 170, 4(8) pm and Ir‐N = 196, 2(8) pm. 3 crystallizes as monoclinic red crystals in the space group P2₁/n and a = 1449.9(2), b = 906.74(4), c = 2628.9(5) pm, β = 103.50(1)°, Z = 4. The nitrido bridge Os≡N‐Ir is slightly bent (Os‐N‐Ir = 165.0(3)°). The distances are Os‐N = 168.3(5) pm and Ir‐N = 201.9(5) pm. 4 forms dark brown, orthorhombic crystals with the space group P2₁2₁2₁ and a = 704.35(2), b = 1228.17(6), c = 3442.0(4) pm, Z = 4. The distances in the slightly bent nitrido bridge (Os‐N‐Ir = 161.8(4)°) are Os‐N = 169.3(7) pm und Ir‐N = 197.8(7) pm.     

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2ReCl4, [(Me2PhP)3Cl2ReN]2ReCl4 · 2 SbCl3 und [Re(NH)Cl2(PMe2Ph)3][SbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂ReCl₄, [(Me₂PhP)₃Cl₂ReN]₂ReCl₄ · 2 SbCl₃ and [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] The reaction of ReNCl₂(PMePh)₃ with SbCl₅ in toluene yields the trinuclear complex [(Me₂PhP)₃Cl₂Re≡N]₂ReCl₄ · 2 SbCl₃ ( 1 · 2 SbCl₃). It forms triclinic crystals with the composition 1 · 2 SbCl₃, as well as monoclinic crystals 1 · 2 SbCl₃ · 4 C₇H₈. The monoclinic crystals with the space group P2₁/c, and a = 1212.3(2), b = 2098.5(4), c = 1827.7(3) pm, β = 95.51(1)°, Z = 2, have been used for a crystal structure determination. In the centrosymmetric complex 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit ReCl₄. The SbCl₃ molecules are coordinated by chlorine bridges to Cl atoms of 1 , and, in addition, connect the complexes 1 with each other. The SbCl₃ free compound 1 is obtained in good yield by the reaction of ReNCl₂(PMePh)₃ with ReCl₄(NCEt)₂. It crystallizes in the triclinic space group P1 with a = 1037.7(3), b = 1153.0(2), c = 1393.8(3) pm, α = 72.31(2)°, β = 74.06(2)°, γ = 67.94(2)°, and Z = 1. The bond lengths of the Re–N triple bonds are 172 pm in 1 and 170 pm in 1 · 2 SbCl₃. By the reaction of ReNCl₂(PMePh)₃ with SbCl₅ in CH₂Cl₂ the solvent is decomposed forming HCl which protonates the nitrido ligand to afford the imido complex [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] ( 2 ) crystallizing in the monoclinic space group P2₁/n with a = 1221.4(2), b = 1358.6(2), c = 2177.3(1) pm, β = 92,72(1)° and Z = 4. The Re–N distance in the almost linear unit Re≡N–H is 169,1 pm.