Bis(1H-pyrazole-κN 2)bis­(2,4,6-tri­isopropyl­benzoato-κO)cobalt(II)

The title compound, [Co(C16H23O2)2(C3H4N2)2] or (C3H4N2)2Co(O2CC6H2 iPr3-2,4,6), is a rare example of a tetra­coordinate cobalt(II) carboxyl­ate stabilized by ancillary N-heterocyclic ligands. The Co(II) ion resides on a crystallographic twofold axis so that the asymmetric unit comprises one half-mol­ecule. Due to the steric bulk of the 2,4,6-triisopropyl­phenyl substituents, the carboxyl­ate ligands are both coordinated in a monodentate fashion despite the low coordination number. The coordination geometry around the central Co(II) ion is distorted tetra­hedral with angles at Co ranging from 92.27 (18)° to 121.08 (14)°

Bis({tris[2-(3,5-di-tert-butyl-2-oxido­benzylideneamino)ethyl]amine}cerium(III)) diethyl ether solvate

The title compound, 2[Ce(C51H75N4O3)]·C4H10O, was obtained in high yield (92%) by reduction of (TRENDSAL)CeIVCl [TRENDSAL is N,N′,N′′-tris­(3,5-di-tert-butyl­salicyl­ide­natoamino)­triethyl­amine] with potassium in THF. The bulky tripodal TRENDSAL ligand effectively encapsulates the central CeIII cation with a Ce—N(imine) distance of 2.860 (2) Å and an average C—N(amine) distance of 2.619 Å within a distorted monocapped octahedral coordination

Tris(N,N′-diisopropyl­benzamidinato)cerium(III)

The title compound, [Ce(C13H19N2)3], was obtained in moderate yield (67%) by treatment of anhydrous cerium trichloride with three equivalents of Li[PhC(NiPr)2] in tetra­hydro­furan. It is the first homoleptic lanthanide complex of this amidinate ligand. The central CeIII ion is coordinated by three chelating benzamidinate anions in a distorted octa­hedral fashion, with Ce—N distances in the narrow range 2.482 (2)–2.492 (2) Å. The dihedral angles between the phenyl rings and the chelating N—C—N units are in the range 73.3–87.9°, thus preventing conjugation between the two π-systems. The mol­ecule is located on a twofold rotation axis, and one of the phenyl rings is equally disordered over two alternative symmetry-equivalent positions around this axis

Bis(η7-cyclo­hepta­trien­yl)tri-μ-hydrido-dimolybdenum(0,I)

In the title compound, [Mo2(η7-C7H7)2(μ-H)3], which displays crystallographic mirror symmetry, two (η7-C7H7)Mo units are linked along the Mo—Mo axis by three bridging hydride ligands. The Mo—Mo distance is 2.5732 (4) Å. The perpendicular distances of the Mo atoms from the C7 planes are 1.5827 (8) and 1.5814 (8) Å, with individual Mo—C bond lengths in the range 2.261 (2)–2.2789 (14) Å. Mo—H distances range from 1.77 (3) to 1.85 (4) Å, with Mo—H—Mo angles of 89 (2) and 92 (1)°

5-Bromo-4-(3,5-dibromo-2-hydroxyphenyl)-2-(piperidin-1-yl)-1,3-dithiol-2-ylium bromide

In the title salt, C14H13Br3NOS2+·Br−, synthesized by bromination of mesoionic 2-[2-(piperidin-1-yl)-1,3-dithiol-2-ylium-4-yl]phenolate in glacial acetic acid, the dihedral angle between the 1,3-dithiolium ring and the phenolic substituent ring is 45.9 (3)° due to the steric influence of the ortho-Br group on the 1,3-dithiolium ring. The piperidine ring adopts a chair conformation. In the crystal, the cation and anion are linked by an O—H...Br hydrogen bond

4-Bromo-2-[5-methyl-2-(morpholin-4-yl)-1,3-thiazol-4-yl]phenol

In the title compound, C14H15BrN2O2S, synthesized by the reaction of the corresponding phenacyl thiocyanate with morpholine, the dihedral angle between the 1,3-thiazole ring and the phenolic substituent ring is 23.46 (10)° as a result of the steric influence of the ortho-methyl group on the thiazole ring. A strong intramolecular phenolic O—H...N hydrogen bond is present in the molecule. In the crystal, a weak C—H...Ophenol hydrogen bond gives rise to chains lying parallel to [20-1]. A short intermolecular Br...Omorpholine interaction is also present [3.1338 (19) Å]

New Lanthanide Alkynylamidinates and Diiminophosphinates

This contribution reports the synthesis and structural characterization of several new lithium and lanthanide alkynylamidinate complexes. Treatment of PhC≡CLi with N,N′-diorganocarbodiimides, R–N=C=N–R (R = iPr, Cy (cyclohexyl)), in THF or diethyl ether solution afforded the lithium-propiolamidinates Li[Ph–C≡C–C(NCy)2] S (1: R = iPr, S = THF; 2: R = Cy, S = THF; 3: R = Cy, S = Et2O). Single-crystal X-ray diffraction studies of 1 and 2 showed the presence of typical ladder-type dimeric structures in the solid state. Reactions of anhydrous LnCl3 (Ln = Ce, Nd, Sm or Ho) with 2 in a 1:3 molar ratio in THF afforded a series of new homoleptic lanthanide tris(propiolamidinate) complexes, [Ph–C≡C–C(NCy)2]3Ln (4: Ln = Ce; 5: Ln = Nd; 6: Ln = Sm; 7: Ln = Ho). The products were isolated in moderate to high yields (61%–89%) as brightly colored, crystalline solids. The chloro-functional neodymium(III) bis(cyclopropylethynylamidinate) complex [{c-C3H5–C≡C–C(NiPr)2}2Ln(µ-Cl)(THF)]2 (8) was prepared from NdCl3 and two equiv. of Li[c-C3H5–C≡C–C(NiPr)2] in THF and structurally characterized. A new monomeric Ce(III)-diiminophosphinate complex, [Ph2P(NSiMe3)2]2Ce(µ-Cl)2Li(THF)2 (9), has also been synthesized in a similar manner from CeCl3 and two equiv. of Li[Ph2P(NSiMe3)2]. Structurally, this complex resembles the well-known “ate” complexes (C5Me5)2Ln(µ-Cl)2Li(THF)2. Attempts to oxidize compound 9 using trityl chloride or phenyliodine(III) dichloride did not lead to an isolable cerium(IV) species

Synthesis and structure of a heterotrimetallic (Li/Er/In), heptacyclic metallasiloxane cage compound ☆

The unusual heterotrimetallic (Li/Er/In), heptacyclic metallasiloxane cage compound [{(Ph 2 SiO) 2 O} 3 {Li(THF) 2 } {InMe}]Er (2) has been prepared in 98% yield by reaction of the erbium bis(disiloxanediolate) derivative [{(Ph 2 SiO) 2 O} 2 {Li(THF) 2 } 2 ]ErCl (1) with trimethylindium, InMe 3 . The product was structurally characterized by single-crystal X-ray diffraction. © 2014 Elsevier B.V. All rights reserved. Well-defined molecular metal siloxides (=metallasiloxanes) comprising M-O-Si functionalities attract significant interest due to their diverse potential applications [1]. Not only are metal siloxides excellent molecular models for silica-supported heterogeneous metal catalysts [2], but they can also serve as precursors for new materials [3], nanoparticles [4], well-defined surface species [5], and homogeneous catalysts [6]. A particularly useful and versatile precursor for a large variety of metal siloxides is the simple and readily accessible 1,1,3,3-tetraphenyl-disiloxane-1,3-diol, (HO)SiPh 2 OSiPh 2 (OH), which forms stable complexes with virtually all metallic elements across the Periodic Table ranging from lithium to uranium [1,7]. Among these, lanthanide disiloxanediolates form a well-investigated class of compounds [1]. Most prominent are heterometallic lanthanide bis(disiloxanediolates) of the type [{(Ph 2 SiO) 2 O}{Li(S) n }] 2 LnCl(S) (Ln = rare-earth metal; S = Et 2 O, THF, DME; n = 1, 2 Initial reactivity studies revealed that unusual heterometallic products could be isolated from reactions of these lanthanide bis(disiloxanediolates) with Group 13 metal trialkyls. Scheme 2 illustrates the outcome of reactions of type A complexes (Ln = Sc, Y) with AlMe 3 and InMe 3 , resp. Treatment of the Sc complex with Yet another, completely different product was obtained when a praseodymium complex of type C was treated with trimethylindium (Scheme 3). This reaction resulted in double insertion of InMe 2 units into the 12-membered Si 4 O 6 Li 2 inorganic ring system attached to praseodymium and formation of the novel ionic product [Li(THF) In the present study, we found that a reaction of the type B erbium bis(disiloxanediolate) complex [{(Ph 2 SiO) 2 O} 2 {Li(THF) 2 } 2 ]ErCl (1) with trimethylindium yet again took an entirely different course (Scheme 4). The reaction of [{(Ph 2 SiO) 2 O} 2 {Li(THF) 2 } 2 ]ErCl (1) with trimethylindium was carried out in toluene solution using a molar ratio of 1:3 [8]. The reaction mixture was first stirred at r.t. and then refluxed for 1 h. After removal of a small amount of insoluble material (presumably Li[InMe 4 ]) by filtration, the product 2 crystallized directly from the concentrated filtrate in the form of colorless prisms. Meaningful NMR spectra of 2 could not be obtained due to the strongly paramagnetic nature of the Er 3+ ion. After all, as is characteristic for the chemistry of metal disiloxanediolates, the usual combination of spectroscopi

Molecular and Crystal Structure of a New High Energy Density Material: Aminoguanidinium-styphnate, [H2NNHC(NH2)2]2[C6HO2(NO2)3]

The title compound [H2NNHC(NH2)2]2[C6HO2(NO2)3] (2) was prepared in 85% yield by treatment of sodium styphnate with 2 equivalents of aminoguanidinium nitrate, followed by crystallization from aqueous solution. Compound 2 crystallizes in the triclinic space group Pī with unit cell dimensions a = 6.7224(3) Å, b = 10.7473(4) Å, c = 11.9604(5) Å, α = 113.212(4)°, β = 90.579(3)°, γ = 99.815(3)°, V = 779.68(6) Å3, Z = 2. In the solid state structure of 2, no water of crystallization is present. Bond angles within the aromatic ring of the styphnate anion indicate a significant distortion with larger angles (122.04(18)–125.96(18) Å) at the carbons bearing the nitro groups, and smaller ones (113.30(17) and 114.07(17) Å) at the C-O− carbon atoms. The crystal structure of 2 consists of layers formed by an extensive network of N-H...O hydrogen bonds between NH2 groups of the aminoguanidinium cation and the negatively charged oxygens of the styphnate anion. The layers are again interconnected by N-H...N hydrogen bonds between neighboring aminoguanidinium cations