The crystal structure of 3′-methoxy-5-phenyl-5,10-dihydrophenarsazine,C19H16AsNO

The crystal structure of 3′-methoxy-5-phenyl-5,10-dihydrophenarsazine, C₁₉H₁₆AsNO has been determined by the single crystal x-ray diffraction method. The crystals are monoclinic with a = 15.305(6), b = 5.809(2), c = 17.595(6)Å, β = 92.92(2)°, V = 1562.3(1.0ų, space group P2,/n, Z = 4 and d_calc = 1.485g cm⁻³. An automatic diffractometer with graphite monochromatized MoKα radiation was used to obtain 1480 observed reflection with I > 3σ(I) at 2θ < 50°. Final R = 0.040 and wR = 0.032. The tricyclic ring is folded with the central ring in a flattened boat conformation. The folding angle between the least-squares planes of the two benzo rings is 164.6(2)°. The 3′-methoxyphenyl group is in a boat-axial conformation with respect to the central ring.     

Die ersten Hydrogencarbonate mit einer trimeren [H2(CO3)3]4−-Baugruppe: Zur Darstellung und Kristallstruktur von Rb4H2(CO3)3 · H2O und K4H2(CO3)3 · 1,5 H2O

The First Hydrogencarbonates with a Trimeric [H₂(CO₃)₃]^4? Group: Preparation and Crystal Structure of Rb₄H₂(CO₃)₃ · H₂O and K₄H₂(CO₃)₃ · 1.5 H₂O Rb₄H₂(CO₃)₃ · H₂O and K₄H₂(CO₃)₃ · 1,5 H₂O were prepared by means of the reaction of (CH₃)₂CO₃ with RbOH resp. KOH in aqueous methanole. Trimer [H₂(CO₃)₃]^4?-anions were found in the crystal structure of Rb₄H₂(CO₃)₃ · H₂O (orthorhombic, Pnma (no. 62), a = 1 218.0(1) pm, b = 1 572.3(6) pm, c = 615.9(1) pm, V_EZ = 1 179.5(5) · 10⁶ pm³, Z = 4, R1(I ≥ 2σ(I)) = 0.027, wR2(I ≥ 2σ(I)) = 0.055). K₄H₂(CO₃)₃ · 1,5 H₂O crystallizes in an OD-structure. The determined superposition structure (orthorhombic, Pbam (no. 55), a = 1 161.8(1) pm, b = 597.0(1) pm, c = 383.85(3) pm, V_EZ = 266.3(1) · 10⁶ pm³, Z = 1, R1(I ≥ 2σ(I)) = 0.035, wR2(I ≥ 2σ(I)) = 0.074) can be derived from the structure of the rubidium compound. The thermal decomposition of the substances is discussed.     

Die Kristallstruktur von Kaliummonomethylcarbonat

Crystal Structure of Potassium Monomethylcarbonate Potassium monomethylcarbonate KCH₃CO₃ was obtained from reaction of dimethylcarbonate with potassium hydroxide in methanole. The crystal structure was determined (triclinic, P1 (no. 2), Z = 2, a = 380.9(2) pm, b = 558.9(3) pm, c = 985.3(3) pm, α = 100.71(2)°, β = 90.06(3)°, γ = 92.48(3)°, V = 205.9(2) · 10⁶ pm³, wR(F²) = 0.054, wR_obs(F) = 0.022). Structural relations between potassium monomethylcarbonate and potassium hydrogencarbonate are discussed.     

Complexation of Alkali Triflates by Crown Ethers: Synthesis and Crystal Structure of [Na(12‐crown‐4)2][SO3CF3], [Na(15‐crown‐5)][SO3CF3], [Rb(18‐crown‐6)][SO3CF3], and [Cs(18‐crown‐6)][SO3CF3]

Complexes of trifluoromethanesulfonates (triflates) with alkali metals Na, Rb, Cs have been prepared in the presence of various macrocyclic polyether crowns [(12‐crown‐4), (15‐crown‐5) and (18‐crown‐6)]. Depending on the combination of alkali ion with crown, the complexes include separated ion pairs [Na(12‐crown‐4)₂] [SO₃CF₃] ( 1 ) and contact ion pairs [Na(15‐crown‐5)] [SO₃CF₃] ( 2 ), [Rb(18‐crown‐6)] [SO₃CF₃] ( 3 ), and [Cs(18‐crown‐6)] [SO₃CF₃] ( 4 ), in which the triflate acts as a bidentate ligand. It is shown that the choice of crown ether is of paramount importance in determining the solid‐state structural outcome. The complex resulting from the pairing of crown ether ( 1 ) develops, when the crown ether is too small in relation to the alkali ion radius. When the cavity size of the crown ether is matched with the alkali ion radius, simple monomeric structures are identified in 2 , 3 and 4 . The title compounds crystallize in the monoclinic crystal system: 1 : space group P2/c with a = 9.942(3), b = 11.014(2), c = 10.801(3) Å, β = 97.30(2)°, V = 1173.1(4) ų, Z = 2, R1 = 0.0812, wR2 = 0.1133: 2 : space group P2₁/m with a = 7.949(2), b = 12.063(3), c = 9.094(2) Å, β = 105.98(2)°, V = 838.3(4) ų, Z = 2, R1 = 0.0869, wR2 = 0.1035: 3 : space group P2₁/c with a = 12.847(5), b = 8.448(2), c = 22.272(6) Å, β = 122.90(3)°, V = 2029.5(1) ų, Z = 4, R1 = 0.0684, wR2 = 0.1044: 4 : space group P2₁/n with a = 12.871(3), b = 8.359(1), c = 19.019(4) Å, β = 92.61(2)°, V = 2044.2(6) ų, Z = 4, R1 = 0.0621, wR2 = 0.0979.     

Die Tieftemperaturmodifikationen von Ag6Si2O7 und Ag6Ge2O7 – Darstellung,Kristallstruktur und Vergleich der Ag?Ag-Abstände

On the Low Temperature Modifications of Ag₆Si₂O₇ and Ag₆Ge₂O₇ – Synthesis, Crystal Structure, and Comparison of Ag? Ag Distances For the first time, single crystals of Ag₆Si₂O₇ and Ag₆Ge₂O₇ have been obtained by solid state reactions of the binary oxides at temperatures of 350°C while applying oxygen pressures of 700 bar. According to the results of X-ray crystal structure determinations both compounds crystallize isostructural in P2₁ (Ag₆Si₂O₇: a = 5.3043(5) Å, b = 9.7533(7) Å, c = 15.9283(13) Å, β = 91.165(8)°, 3881 independent reflections, R1 = 3.3%, wR2 = 7.2%; Ag₆Ge₂O₇: a = 5.3713(4) Å, b = 9.9835(8) Å, c = 16.2249(14) Å, β = 90.904(8)°, 2111 independent reflections, R1 = 4.3%, wR2 = 6.0%, Z = 4). The crystal structures contain two independent M₂O₇^6? anions, one in a staggered, and the other in an ecliptic conformation. The cationic partial structure may be described as a distorted bcc arrangement of Ag⁺ and M⁴⁺. Comparison of the structures with respect to the Ag? Ag separations reveals the latter to be probably due to intrinsic d¹⁰–d¹⁰ bonding interactions as far as the range of 2.89 Å to 3.25 Å is considered.     

Substituierte Halogenocarbonylmetallate des Chroms,Molybdäns und Wolframs. IV. Die Kristallstruktur von Tetramethylammonium-Chloropentacarbonylwolframat

Substituted Halocarbonyl Metallates of Chromium, Molybdenum, and Tungsten. IV. Crystal Structure of Tetramethylammonium Chloropentacarbonyltungstate The structure of tetramethylammonium chloropentacarbonyltungstate has been determined from single crystal X-ray data. The compound crystallizes with four formula units in the monoclinic unit cell (space group P2₁/c) of the dimensions a = 1111.3(4) pm, b = 1110.3(4) pm c = 1204.1(3) pm, β = 99.63(3)°, V = 1464.8 × 10⁶ pm³ (R = 0.028). The anion possesses approximately C_4v symmetry with the principal interatomic distances d(W–C(cis)) = 203 pm, d(W–C(trans)) = 197 pm d(W–Cl) = 256.6 pm. No unusual contacts between cation and anion have been found.     

The Structure of 2‐[(1S)‐(+)‐10‐camphorsulfonamino]‐6‐aminopyridine in the Solid State and in Solution; Unprecedented Cocrystallization of Four Stereoisomers

The solid and solution structures of a new optically active aminopyridine compound, 2‐[(1S)‐(+)‐10‐camphorsulfonamino]‐6‐aminopyridine [(S)‐csaap], 1 , are reported. Crystal data: space group P2₁, a = 8.9729 (5), b = 10.9447 (6), c = 36.693 (2) Å, β = 96.435 (1)°, V = 3580.8 (3) ų, Z = 8, R₁ = 0.0673 and wR₂ = 0.1600 with I > 2σ(I). This chiral compound shows an unprecedented cocrystallization of four stereoisomers, which are characterized by X‐ray crystallography and NMR spectroscopy.     

Novel Hydrogen‐bond Three Dimensional Networks Generated from the Reaction of Metal Nitrate Hydrate (M = Co,Ni) with Ammonium Thiocynate and Bidentate Ligand Piperazine

The reaction of Co(NO₃)₂·6H₂O with two equivalents of PPz (PPz = piperazine hexahydrate) and two equivalents of NH₄SCN in CH₃OH afforded the complex [Co(NCS)₂(PPz)₂(CH₃OH)₂]. The reaction of Ni(NO₃)₂·6H₂O with two equivalents of PPz and four equivalents of NH₄SCN in CH₃OH afforded the complex [Ni(NCS)₄(PPz)₂]. Their IR spectra have been recorded and the structures have been determined. Crystal data for 1 : space group P&1bar;, a = 6.7208(6) Å, b = 8.4310(8) Å, c = 8.5923(8) Å, a = 77.881(2)°, β = 76.342(2)°, γ = 83.936(2)°, V = 461.75(1) ų, Z = 1 with final residuals R1 = 0.0650 and wR2 = 0.1725. Crystal data for 2 : space group P2(1)/n, a = 7.4209(6) Å, b = 11.0231(9) Å, c = 12.317(1) Å, β = 96.642(9)°, V = 1000.9(2) ų, Z = 2 with final residuals R1 = 0.0378 and wR2 = 0.0809. Important NCS—H‐N and O‐H—N(PPz) hydrogen‐bonding interactions in compound 1 and NCS···H‐N hydrogen‐bonding interactions and NCS—SCN interactions in compound 2 play a significant role in aligning the polymer strands in crystalline solids.     

Spezielle Alkylammoniumhexachlorometallate. I. Kristallisationsverhalten und Kristallstruktur von Diethylentriammoniumhexachlororhodat, [H3N(CH2)2NH2(CH2)2NH3][RhCl6]

Alkylammonium Hexachlorometallates. I. Crystallization Properties and Crystal Structure of Diethylenetriammonium Hexachlororhodate, [H₃N(CH₂)₂NH₂(CH₂)₂NH₃][RhCl₆] The reaction of RhCl₃ · 3H₂O with diethylenetriamine in 12 m hydrochloric acid yielded diethylenetriammonium hexachlororhodate [H₃N(CH₂)₂NH₂(CH₂)₂NH₃][RhCl₆] ( 1 ). Dark red single crystals of the compound were grown under hydrothermal conditions at a temperature interval of 180°C to 125°C in closed glass ampoules over several weeks (space group C2/c, a = 30.956(4) Å, b = 7.371(2) Å, c = 12.9736(15) Å, β = 113.787(11)°, Z = 8, 2385 reflections with I > 0, wR²(obs.) = 0.0279, R¹(I > 2σ(I)) = 0.0271). The crystal structure is determined by a complex framework of hydrogen bonds between the hexachlororhodate anions and the diethylenetriammonium cations.     

Synthesis,Characterization of a Novel 1,2,4‐Thiotriazine Derivative (CAMTTO), and Copper(I) and Silver(I) Complexes thereof (CAMTTO = {(4‐[(4‐Chlorobenzylidene)‐amino]‐6‐methyl‐3‐thioxo‐[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one)}

The reaction of 4‐amino‐6‐methyl‐1,2,4‐triazin‐thione‐5‐one (H₂AMTTO, 1 ) with 4‐chlorobenzaldhyde led to the corresponding iminic compound {(4‐[(4‐chloro‐benzylidene)‐amino]‐6‐methyl‐3‐thioxo[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one), CAMTTO ( 2 ). Treatment of 2 with copper(I) chloride in chloroform gave the dimeric complex [{(CAMTTO)₂CuCl}₂]·2CHCl₃ ( 3 ). Treatment of 2 with copper(I) chloride and silver(I) nitrate in the presence of the co‐ligand triphenylphophane gave the complexes [(CAMTTO)CuCl(PPh₃)₂] ( 4 ) and [(CAMTTO)Ag(PPh₃)₂]NO₃·2CHCl₃ ( 5 ). All compounds have been characterized by elemental analyses, ¹H NMR spectroscopy, IR spectroscopy, and partly by mass spectrometry and X‐ray diffraction studies. In addition 4 and 5 have been characterized by ³¹P{¹H} NMR spectroscopy. Crystal data for 2 at ?80 °C: monoclinic, space group P2₁/c, a = 1370.3(1), b = 767.8(1), c = 1268.7(1) pm, β = 107.12(1)°, Z = 4, R₁ = 0.0379; for 3 at ?80 °C: monoclinic, space group P2₁/c, a = 1442.6(2), b = 878.8(1), c = 2558.7(3) pm, β = 95.31(1)°, Z = 2, R₁ = 0.0746; for 4 at ?80 °C: triclinic, space group , a = 1287.9(1), b = 1291.7(1), c = 1359.5(1) pm, α = 90.44(1)°, β = 94.81(1)°, γ = 107.54(1)°, Z = 2, R₁ = 0.0359 and for 5 at ?80 °C: triclinic, space group , a = 1060.5(1), b = 1578.2(2), c = 1689.6(2) pm, α = 87.70(1)°, β = 86.66(1)°, γ = 76.84(1)°, Z = 2, R₁ = 0.0487.     

Synthesis and Structures of Infinite Coordination Polymers from 1,3‐Bis(4‐pyridyl)propane Ligand and Zinc Salts

The reaction of Zn(NO₃)₂‐6H₂O, NH₄SCN and bpp (bpp = 1,3‐bis(4‐pyridyl)propane) in CH₃OH afforded the complex [Zn(NCS)₂(bpp)]_n, 1 , while the reaction of Zn(ClO₄)₂‐6H₂O and bpp in CH₃OH afforded the complex [Zn(ClO₄)₂(bpp)₂]_n, 2 . Both complexes have been characterized by spectroscopic methods and their structures have been determined by X‐ray crystallography. Crystal data for 1 : Orthorhombic, space group P2₁2₁2, a= 12.857(6), b = 14.822(7), c = 4.820(2) Å, β = 90°, V = 918.5(8) ų, Z = 2 with final residuals R1 = 0.0747 and wR2 = 0.1657. Crystal data for 2 : Tetragonal, space group I4/mcm, a = 11.612(1), b = 11.612(1), c = 23.247(9) Å, β = 90°, V = 3135(1) ų, Z = 4 with final residuals R1 = 0.0523 and wR2 = 0.1064. The coordination polymers display a variety of structural architectures, ranging from zigzag chains ( 1 ) and one‐dimensional channel‐type architectures ( 2 ). The effects of the orientation of the nitrogen atom in the pyridine rings on the resultant structures are discussed.     

Preparation and Structure Determination of SrMn2(PO4)2 and Redetermination of b ′‐Mn3(PO4)2

Pale rose single crystals of SrMn₂(PO₄)₂ were obtained from a mixture of SrCl₂ · 6 H₂O, Mn(CH₃COO)₂, and (NH₄)₂HPO₄ after thermal decomposition and finally melting at 1100 °C. The new crystal structure of strontium manganese orthophosphate [P‐1, Z = 4, a = 8.860(6) Å, b = 9.054(6) Å, c = 10.260(7) Å, α = 124.27(5)°, β = 90.23(5)°, γ = 90.26(6)°, 4220 independent reflections, R1 = 0.034, wR2 = 0.046] might be described as hexagonal close‐packing of phosphate groups. The octahedral, tetrahedral and trigonal‐bipyramidal voids within this [PO₄] packing provide different positions for 8‐ and 10‐fold [SrO_x] and distorted octahedral [MnO₆] coordination according to a formulation Mn Mn Mn Sr (PO₄)₄. Single crystals of β′‐Mn₃(PO₄)₂ (pale rose) were grown by chemical vapour transport (850 °C → 800 °C, P/I mixtures as transport agent). The unit cell of β′‐Mn₃(PO₄)₂ [P2₁/c, Z = 12, a = 8.948(2) Å, b = 10.050(2) Å, c = 24.084(2) Å, β = 120.50°, 2953 independent reflections, R1 = 0.0314, wR2 = 0.095] contains 9 independent Mn²⁺. The reinvestigation of the crystal structure led to distinctly better agreement factors and significantly reduced standard deviations for the interatomic distances.     

Intermetallic Phases in the Ca‐Cu‐Sn System

Twelve ternary alloys in the Ca‐Cu‐Sn system were synthesized as a test on the existing phases. They were prepared from the elements sealed under argon in Ta crucibles, melted in an induction furnace and annealed at 700 °C or 600 °C. Four ordered compounds were found: CaCuSn (YbAuSn type), Imm2, a = 4.597(1) Å, b = 22.027(2) Å, c = 7.939(1) Å, Z = 12, wR2 = 0.080, 1683 F² values; Ca₃Cu₈Sn₄ (Nd₃Co₈Sn₄ type), P6₃mc, a = 9.125(1) Å, c = 7.728(1) Å, Z = 2, wR2 = 0.087, 704 F² values; CaCu₂Sn₂ (new structure type), C2/m, a = 10.943(3) Å, b = 4.222(1) Å, c = 4.834(1) Å, β = 107.94(1)°, Z = 2, wR2 = 0.051, 343 F² values; CaCu₉Sn₄ (LaFe₉Si₄ type), I4/mcm, a = 8.630(1) Å, c = 12.402(1) Å, Z = 4, wR2 = 0.047, 566 F² values. In all phases the shortest Cu‐Sn distances are in the range 2.59‐2.66Å, while the shortest Cu‐Cu distances are practically the same, 2.53‐2.54Å, except CaCuSn where no Cu‐Cu contacts occur.     

Darstellung und Struktur der ersten gemischten Alkalimetallhydrogencarbonate NaA2[H(CO3)2] · 2H2O mit A = K,Rb

Preparation and Crystal Structure of the First Mixed Alkalimetal Hydrogencarbonates NaA₂[H(CO₃)₂] · 2H₂O with A = K, Rb The new hydrogencarbonates NaK₂[H(CO₃)₂] · 2H₂O (Pnma, a = 934.07(13) pm, b = 789.31(10) pm, c = 1142.1(5) pm, V_EZ = 842.0(4) · 10⁶ pm³, Z = 4, R1 (I ? 2σ(I)) = 0.023, wR2 = 0.066 for 989 reflections) and NaRb₂[H(CO₃)₂] · 2H₂O (Pnma, a = 948.24(11) pm, b = 811.37(9) pm, c = 1189.0(2) pm, V_EZ = 914.8(2) · 10⁶ pm³, Z = 4, R1 (I ≤ 2σ(I)) = 0.031, wR2 = 0.077 for 1063 reflections) were prepared from aqueous solutions. The crystal structures were determined. The isostructural compounds contain dimeric, non centrosymmetric [H(CO₃)₂]^3? anions. In NaK₂[H(CO₃)₂] · 2H₂O a short hydrogen bond (d(O … O) = 246.1(2) pm) with an asymmetric potential was detected. In NaRb₂[H(CO₃)₂] · 2H₂O a hydrogen bond with symmetric potential (d(O … O) = 247.8(5) pm) can be assumed. The IR-spectra of NaK₂[H(CO₃)₂] · 2H₂O and Na₃[H(CO₃)₂] · 2H₂O are compared.     

Synthese und Kristallstrukturen der Polytelluridokomplexe (PPh4)4[M2Te12] von Kupfer(I) und Silber(I)

Syntheses and Crystal Structures of the Polytellurido Complexes (PPh₄)₄[M₂Te₁₂] of Copper(I) and Silver(I) The title compounds have been prepared as black crystal needles by reactions of Na₂Te₃ with CuCl and AgNO₃, respectively, in dimethylformamide in the presence of PPh₄Br. With regard to the large cell dimensions the crystal structure determinations were done by an imaging plate instrument. (PPh₄)₄[Cu₂Te₁₂]: Space group P2₁/n, Z = 6, 51 338 detected reflections, structure determination with 14 177 unique reflections with I > 4σ(I), R = 0.081. Lattice dimensions at ? 50°C: a = 1 704.5, b = 1 694.5, c = 5 044 pm, β = 94.20°. (PPh₄)₄[Ag₂Te₁₂]: Space group P2₁/n, Z = 6, 80 811 detected reflections, structure determination with 16 092 unique reflections with I > 3σ(I), R = 0.052. Lattice dimensions at ? 50°C: a = 1 703.8, b = 1 722.9, c = 5 123 pm, β = 94.65°. The structures of the isotypic compounds consist of six symmetry independent PPh₄⁺ ions and two symmetry independent anions [M₂Te₁₂]^4?, in which the metal atoms of two (MTe₄)^?-fivering fragments are linked by a Te₄^2? chain.     

Effects on Coordination of Thioether Sites. 4. Structural Analysis of η3-Tripodal Ligand Manganese(I) Complexes

Crystal structures of a series of manganese(I) complexes containing tripodal ligands were determined. For [η³-{CH₃C(CH₂PPh₂)₂(CH₂SPh)-P,P′,S}Mn(CO)₃]PF₆ ( 1 ): a = 10.856(3) Å, b = 19.698(3) Å, c = 17.596(5) Å, β = 96.17(2)°, monoclinic, Z = 4, P2₁/c, R(F_o) = 0.068, R_w(F_o) = 0.055 for 3617 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)(CH₂SPh)₂-P,P′,S}Mn(CO)₃]PF₆ ( 2 ): a = 9.890(2) Å, b = 20.403(4) Å, c = 10.269(3) Å, β = 117.44(2)°, monoclinic, Z = 2, P2_l, R(F_o) = 0.050, R_w(F_o) = 0.037 for 1760 reflections with I_o > 2σ(I_o). For [η³-{CH₃C(CH₂PPh₂)₂(CH₂S)-P,P′,S}Mn(CO)₃] ( 4 ): a = 8.191(7) Å, b = 10.495(3) Å, c = 19.858(6) Å, α = 99.61(2)°, β = 96.17(2)°, γ = 92.70(4)°, triclinic, Z = 2, P-I, R(F_o) = 0.048, R_w(F_o) = 0.039 for 2973 reflections with I_o > 2σ(I_o). There is no significant difference in the bond lengths of Mn-S bonds among three species in their crystal structures [2.325(2) Å in 1; 2.358(4) in 2; 2.380(2) in 4], but the better donating ability of thiolate in complex 4 appears on the lower frequencies of its carbonyl stretching absorptions.     

Crystal structure of 4-n-nonylbenzoic acid

The title compound, 4-n-nonylbenzoic acid, CH₃(CH₂)₈C₆H₄COOH (NBA), has been characterized thus: triclinic, P1, a = 13.514(4)Å, b = 23.4672(5)Å, c = 7.658(3)Å, alpha = 90.914(3)°, beta = 100.403(3)°, gamma = 77.781(2)°, V = 2334(2)ų, Z = 2, and F.W = 745.06, D_m = 1.161 g cm^-3, D_c = 1.061 g cm^-3, F₀₀₀ = 816.00, lambda = 0.71069Å, mu = 0.6 cm^-1, goodness-of-fit is 1.029, final R1 = 0.063 and wR2 = 0.16.     

Weak Interactions in Silver Complexes of 15-Crown-5

Abstract

The X-ray crystal structures of two closely related Ag(I) complexes of 15-crown-5 and benzo-15-crown-5 are reported. In the case of [Ag(15-crown-5)₂][SbF₆] 1, pointing one of its oxygen atoms away from the Ag⁺ cation enables one of the crown ligands to take part in an intermolecular C?H…O hydrogen bond. The analogous benzo-15-crown-5 species, [Ag(benzo-15-crown-5)₂][SbF₆] 2, is too rigid to attain the necessary conformation. Crystal data for 1: P2_1/c, a = 8.4481(3), b = 25.5813(9), c = 13.2773(4) Å, β = 101.354(2)°. Z = 4, unique data: 5187 R ₁ [F ² > 2σ(F ²)] 0.0259. Compound 2: P1, a = 8.6511 (15) Å, b =10.2322(18) Å, c = 19.291(3) Å, α = 103.704 (2)°, β = 101.274(2)°, γ = 95.952(2)°, Z = 2, unique data: 5803 R ₁ [F ²>2σ(F ²)] 0.0931.     

Phosphanimin- und Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BF3(Me3SiNPEt3)], [BCl2(NPPh3)]2, [BCl2(NPEt3)]2, [B2Cl3(NPEt3)2]+BCl4− und [B2Cl2(NPiPr3)3]+BCl4−

Phosphaneimine and Phosphoraneiminato Complexes of Boron. Synthesis and Crystal Structures of [BF₃(Me₃SiNPEt₃)], [BCl₂(NPPh₃)]₂, [BCl₂(NPEt₃)]₂, [B₂Cl₃(NPEt₃)₂]⁺BCl₄^?, and [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? The title compounds have been prepared from the corresponding silylated phosphaneimines and boron trifluoride etherate and boron trichloride, respectively. The compounds form white moisture sensitive crystals, which were characterized by ¹¹B-nmr-spectroscopy, IR-spectroscopy and by crystal structure determinations. [BF₃(Me₃SiNPEt₃)] : Space group P2₁/c, Z = 4, R = 0.032 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1361.0, b = 819.56, c = 1422.5 pm, β = 109.86°. The donor acceptor complex forms monomeric molecules with a B? N bond length of 157.8 pm. [BCl₂(NPPh₃)]₂ · 2 CH₂Cl₂ : Space group P2₁/c, Z = 2, R = 0.049 for reflections with I > 2σ(I). Lattice dimensions at ?50°C: a = 1184.6, b = 2086.4, c = 843.0 pm, β = 96.86°. The compound forms centrosymmetric dimeric molecules in which the boron atoms are linked to B₂N₂ four-membered rings with B? N distances of 152.7 pm via μ₂-N bridges of the NPPh₃ groups. [BCl₂(NPEt₃)]₂ : Space group Pbca, Z = 4, R = 0.029 for reflections with I > 2σ(I). Lattice dimensions at ?90°C: a = 1269.5, b = 1138.7, c = 1470.3 pm. The compound has a molecular structure corresponding to the phenyl compound with B? N ring distances of 151.0 pm. [B₂Cl₃(NPEt₃)₂]⁺BCl₄^? : Space group Pbca, Z = 8, R = 0.034 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1309.3, b = 1619.8, c = 2410.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 155.1 and 143.1 pm via the μ₂-N atoms of the NPEt₃ groups. [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? · CH₂Cl₂: Space group Pna2, Z = 4, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1976.5, b = 860.2, c = 2612.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 153.7 and 150.5 pm via the μ₂-N atoms of two of the NPⁱPr₃ groups. The third NPⁱPr₃ group is terminally connected to the sp²-hybridized boron atom with a B? N distance of 133.5 pm and with a B? N? P bond angle of 165.3°.     

Ternary Indides RE4Pd10In21 (RE = La,Ce, Pr,Nd, Sm) — Synthesis,Structure, and Physical Properties

The ternary indium compounds RE₄Pd₁₀In₂₁ (RE = La, Ce, Pr, Nd, Sm) were synthesized from the elements in glassy carbon crucibles in a high‐frequency furnace. Single crystals of Sm₄Pd₁₀In₂₁ were obtained from an indium flux. An arc‐melted precursor alloy of the starting composition ～SmPd₃In₆ was annealed with a slight excess of indium at 1200 K followed by slow cooling (5 K/h) to 870 K. All compounds were investigated by X‐ray powder diffraction and the structures were refined from single crystal diffractometer data. The RE₄Pd₁₀In₂₁ indides are isotypic with Ho₄Ni₁₀Ga₂₁, space group C2/m: a = 2314.3(2), b = 454.70(7), c = 1940.7(2) pm, β = 133.43(2)°, wR2 = 0.0681, 1678 F² values for La₄Pd₁₀In₂₁, a = 2308.2(1), b = 452.52(4), c = 1944.80(9) pm, β = 133.40(1)°, wR2 = 0.0659, 1684 F² values for Ce₄Pd₁₀In₂₁, a = 2303.8(2), b = 450.78(4), c = 1940.6(1) pm, β = 133.39(1)°, wR2 = 0.0513, 1648 F² values for Pr₄Pd₁₀In₂₁, a = 2300.2(2), b = 449.75(6), c = 1937.8(2) pm, β = 133.32(1)°, wR2 = 0.1086, 1506 F² values for Nd₄Pd₁₀In₂₁, and a = 2295.6(2), b = 447.07(4), c = 1935.7(1) pm, β = 133.16(1)°, wR2 = 0.2291, 2350 F² values for Sm₄Pd₁₀In₂₁, with 108 variables per refinement. All palladium atoms have a trigonal prismatic coordination. The strongest bonding interactions occur for the Pd—In and In—In contacts. The structures are composed of covalently bonded three‐dimensional [Pd₁₀In₂₁] networks in which the rare earth metal atoms fill distorted pentagonal channels. The crystal chemistry and chemical bonding in these indides is briefly discussed. Magnetic susceptibility measurements show diamagnetism for La₄Pd₁₀In₂₁ and Curie‐Weiss paramagnetism for Ce₄Pd₁₀In₂₁, Pr₄Pd₁₀In₂₁, and Nd₄Pd₁₀In₂₁. The neodymium compound orders antiferromagnetically at T_N = 4.5(2) K and undergoes a metamagnetic transition at a critical field of 1.5(2) T. All the RE₄Pd₁₀In₂₁ indides studied are metallic conductors.