Crystallographic report: Diisopropylammonium [3‐(2‐thienyl)‐2‐sulfanylpropenoato]triphenylstannate

The title compound comprises trigonal bipyramidal SnPh₃(tspa) anions and ⁱPr₂NH₂ cations linked into centrosymmetric dimers by N? H·O hydrogen bonds. Copyright © 2004 John Wiley & Sons, Ltd.     

Hypervalent selenium compounds containing N → Se intramolecular interactions: synthesis,characterization and X‐ray structures of [2‐(Me2NCH2)C6H4]SeS(S)PR2 (R = Ph,OiPr)

[2‐(Me₂NCH₂)C₆H₄]Se? S(S)PR₂ [R = Ph (1), OⁱPr (2)] were prepared by reacting [2‐(Me₂NCH₂)C₆H₄]₂Se₂ with the appropriate disulfanes, [R₂P(S)S]₂. The compounds were characterized by multinuclear magnetic resonance (¹H, ¹³C, ³¹P). The molecular structures of 1 and 2 were determined by single‐crystal X‐ray diffraction. Both compounds are monomeric and the nitrogen atom of the pendent CH₂NMe₂ arm is strongly coordinated to the selenium atom. The organophosphorus ligands are monodentate, thus resulting in a T‐shaped coordination geometry around selenium. Copyright © 2002 John Wiley & Sons, Ltd.     

From a Si3‐Cyclopropene to a Si3S‐Bicyclo[1.1.0]butane to a Si3S‐Cyclopropene to a Si3S2‐Bicyclo[1.1.0]butane: Back‐and‐Forth,and In‐Between

Compact and highly reactive bicyclo[1.1.0]butanes constitute one of the most fascinating classes of organic compounds. Furthermore, interplay of bicyclo[1.1.0]butanes with their valence isomers, such as buta‐1,3‐dienes and cyclobutenes, is among the fundamental pericyclic transformations in organic chemistry. Herein we report the back‐and‐forth interconversion between the cyclotrisilenes and thiatrisilabicyclo[1.1.0]butanes, allowing for the synthesis of novel representatives of such classes of highly reactive organometallics. The peculiar structural and bonding features of the newly synthesized compounds, as well as the mechanism of their isomerization, were verified both experimentally and computationally.     

New Phases in the Lithiumnitridovanadate System — The Solid Solution Li7‐2xMgx[VN4] with 0 ≤ x ≤ 1

Solid solution phases Li_7‐2xMg_x[VN₄] (0 < x ≤ 1) with varying Mg‐content are obtained as yellow microcrystalline powders from heat treatment of mixtures of VN, Li₃N and Mg₃N₂ or from mixtures of Li₇[VN₄] and Mg₃N₂ at 1370 K in N₂ atmosphere at ambient pressure. At substitution parameter values of x > 0.5 a subsequent distortion from the ideal cubic unit cell to an orthorhombic unit cell is observed. The crystal structure of Li_7‐2xMg_x[VN₄] with x ≈ 1 was refined from neutron and X‐ray powder diffraction data (space group Pbca, No. 61, a = 963.03(3) pm, b = 958.44(3) pm, c = 951.93(2) pm, neutron pattern 14° — 156° 2θ, step non‐linear ≈ 0.0782° 2θ, No. of measured points 1816, R_p = 0.089, R_wp = 0.115, R_Bragg = 0.155, R_F = 0.114; X‐ray pattern 10° — 98° 2θ, step 0.005° 2θ, No. of measured points 17600, R_p = 0.028, R_wp = 0.045, R_Bragg = 0.113, R_F = 0.133, structure variables: 45). The crystal structure resembles a Li₂O type superstructure with the atomic arrangement of β‐Li₇[VN₄] and with two crystallographic Li‐sites each substituted by Mg with statistical occupation factors of 0.5. Chemical analyses prove the composition and XAS spectroscopy at the V K‐edge support the +5 oxidation state assignment for vanadium. XAS data also support the tetrahedral coordination of vanadium by N as indicated by the structure refinements.     

Hypervalent Organoselenium(II) Compounds with Organophosphorus Ligands. Crystal and Molecular Structure of [2‐(iPr2NCH2)C6H4]Se[S2PR′2] (R′ = Ph,OiPr)

Redistribution reactions between diorganodiselenides of type [2‐(R₂NCH₂)C₆H₄]₂Se₂ [R = Et, iPr] and bis(diorganophosphinothioyl disulfanes of type [R′₂P(S)S]₂ (R = Ph, OiPr) resulted in the hypervalent [2‐(R₂NCH₂)C₆H₄]SeSP(S)R′₂ [R = Et, R′ = Ph ( 1 ), OiPr ( 2 ); R = iPr, R′ = Ph ( 3 ), OiPr ( 4 )] species. All new compounds were characterized by solution multinuclear NMR spectroscopy (¹H, ¹³C, ³¹P, ⁷⁷Se) and the solid compounds 1 , 3 , and 4 also by FT‐IR spectroscopy. The crystal and molecular structures of 3 and 4 were determined by single‐crystal X‐ray diffraction. In both compounds the N(1) atom is intramolecularly coordinated to the selenium atom, resulting in T‐shaped coordination arrangements of type (C,N)SeS. The dithio organophosphorus ligands act monodentate in both complexes, which can be described as essentially monomeric species. Weak intermolecular S ··· H contacts could be considered in the crystal of 3 , thus resulting in polymeric zig‐zag chains of R and S isomers, respectively.     

Bis{2‐[(phenylimino)ethyl]‐1H‐pyrrol‐1‐ido‐κ2N,N′}nickel(II): a supramolecular structure formed by C—H...π hydrogen bonds

In the title compound, [Ni(C₁₂H₁₁N₂)₂], the Ni^II cation lies on an inversion centre and has a square‐planar coordination geometry. This transition metal complex is composed of two deprotonated N,N′‐bidentate 2‐[(phenylimino)ethyl]‐1H‐pyrrol‐1‐ide ligands around a central Ni^II cation, with the pyrrolide rings and imine groups lying trans to each other. The Ni—N bond lengths range from 1.894 (3) to 1.939 (2) Å and the bite angle is 83.13 (11)°. The Ni—N(pyrrolide) bond is substantially shorter than the Ni—N(imino) bond. The planes of the phenyl rings make a dihedral angle of 78.79 (9)° with respect to the central NiN₄ plane. The molecules are linked into simple chains by an intermolecular C—H...π interaction involving a phenyl β‐C atom as donor. Intramolecular C—H...π interactions are also present.     

Heterocyclic tautomerism: reassignment of two crystal structures of 2‐amino‐1,3‐thiazolidin‐4‐one derivatives

The structures of 5‐(2‐hydroxyethyl)‐2‐[(pyridin‐2‐yl)amino]‐1,3‐thiazolidin‐4‐one, C₁₀H₁₁N₃O₂S, (I), and ethyl 4‐[(4‐oxo‐1,3‐thiazolidin‐2‐yl)amino]benzoate, C₁₂H₁₂N₂O₃S, (II), which are identical to the entries with refcodes GACXOZ [Váňa et al. (2009). J. Heterocycl. Chem. 46 , 635–639] and HEGLUC [Behbehani & Ibrahim (2012). Molecules, 17 , 6362–6385], respectively, in the Cambridge Structural Database [Allen (2002). Acta Cryst. B 58 , 380–388], have been redetermined at 130 K. This structural study shows that both investigated compounds exist in their crystal structures as the tautomer with the carbonyl–imine group in the five‐membered heterocyclic ring and an exocyclic amine N atom, rather than the previously reported tautomer with a secondary amide group and an exocyclic imine N atom. The physicochemical and spectroscopic data of the two investigated compounds are the same as those of GACXOZ and HEGLUC, respectively. In the thiazolidin‐4‐one system of (I), the S and chiral C atoms, along with the hydroxyethyl group, are disordered. The thiazolidin‐4‐one fragment takes up two alternative locations in the crystal structure, which allows the molecule to adopt R and S configurations. The occupancy factors of the disordered atoms are 0.883 (2) (for the R configuration) and 0.117 (2) (for the S configuration). In (I), the main factor that determines the crystal packing is a system of hydrogen bonds, involving both strong N—H...N and O—H...O and weak C—H...O hydrogen bonds, linking the molecules into a three‐dimensional hydrogen‐bond network. On the other hand, in (II), the molecules are linked via N—H...O hydrogen bonds into chains.     

Preparation of 1‐X‐2, 2‐Difluoroethenylxenon(II) Tetrafluoroborates [CF2=CXXe][BF4]

The new type of alkenylxenon(II) salts [CF₂=CXXe] [BF₄] (X = H, Cl, CF₃) was prepared by reacting the corresponding alkenyldifluoroboranes CF₂=CXBF₂ with XeF₂ in 1, 1, 1, 3, 3‐pentafluoropropane (PFP) at —60 °C. The alkenylxenon(II) salts were characterised by multinuclear NMR spectroscopy. The influence of the substituent X at C‐1 on the stability of alkenylxenon(II) salts is discussed. Additionally the preparation of the potassium alkenyltrifluoroborate salts K [CF₂=CXBF₃] and their transformation into the boranes CF₂=CXBF₂ by fluoride abstraction in PFP is reported.     

Alloyed transition‐metal complexes of tricyanomethide (tcm), [Mn1−xCox(tcm)2]

Alloying in the coordination polymer [Mn_1?xCo_x(tcm)₂], (tcm = [C(CN)₃]^?) has been attempted and the physical properties have been investigated. All compounds are isostructural, but the lattice parameters and the distance between manganese and the adjacent nitrogen atom decrease with increasing cobalt content x. Magnetic susceptibility measurements show a Curie–Weiss behavior, with decreasing Weiss temperature with increasing cobalt content. Copyright © 2004 John Wiley & Sons, Ltd.     

Aurophilicity in Tetraphenylphosphonium 7,8‐Bis(diphenylphosphino)‐7,8‐dicarba‐nido‐undecaborato‐dibromo‐digold(I) [PPh4][{(PPh2)2‐C2B9H10}(AuBr)2]

Reactions of tetraphenylphosphonium dibromoaurate(I) with 1,2‐bis(diphenylphosphino)‐1,2‐dicarba‐closo‐dodecaborane in 2:1 ratio in acetone solution yields brown crystals shown to be the title compound. A single crystal X‐ray study shows coordination of AuBr moieties by the phosphorus atoms of the ligand (Au‐P 2.253(1), 2.246(1); Ag‐Br 2.4041(7), 2.4067(7) Å), permitting a close Au···Au contact (2.9536(3) Å) with concomitant bending of the P‐Au‐Br arrays (173.99(4), 166.14(4)°) and a Br‐Au···Au‐Br torsion of 47.80(2)°.     

配合物[Cu2(bpe)X2] n (bpe =1, 2–trans–(4–pyridyl)ethene, X=Cl, Br, I )的合成、晶体结构及热稳定性研究

以1,2-反式-二（4-吡啶基）乙烯桥连卤化铜分别得到配合物[Cu₂(bpe)Cl ₂] _n (1), [Cu₂(bpe)Br₂] _n (2) 和 [Cu₂(bpe)I₂] _n (3)。通过X-射线单晶衍射法对配合物1的结构进行了研究,晶体学数据：单斜晶系, P 2(1)/c空间群, a = 0.3788(8) nm, b = 1.5059(3) nm, c = 1.0875(2)nm, β = 96.262(4) °, V = 616.5(2)ų, Z = 2, S = 1.002,最终残差因子( I >2 σ ( I )) R ₁ = 0.0288, wR ₂ = 0.0579,对于全部数据 R ₁ = 0.0509, wR ₂ = 0.0615。元素分析及红外光谱分析表明,该类配合物为同晶化合物。另外,通过热重分析对配合物的热稳定性进行了研究。     

Preparation and structures of [2‐(dimethylamino)phenyl]diorganotin(IV) acetates substituted with organophosphorus groups in the α‐position of the acetate ligand

Organotin(IV) carboxylates R₂L^NCSnOC(O)CH₂P(E)Ph₂, where L^NC is an N‐chelating 2‐(dimethylamino)phenyl group, and R/E = Ph/void (1a), Ph/O (1b), Ph/S (1c), Me/void (2a), Me/O (2b) and Me/S (2c), were synthesized, characterized by ¹H, ¹³C, ³¹P and ¹¹⁹Sn NMR, IR and MS spectra, and the solid‐state structures of 1b, 1c, 2b and 2c were determined by single‐crystal X‐ray diffraction. Spectral and structural data showed that the compounds are monomeric in CDCl₃ solution and the solid state, with the organophosphorus groups in the α‐position of the monodentate carboxylate ligands not interacting with the tin atom. Copyright © 2005 John Wiley & Sons, Ltd.     

Novel Copper(I) Clusters with 2‐(Diphenylphosphanyl)anilide Ligands. Synthesis and Crystal Structures of [Cu6X2(NHR)4] (X = Cl,Br, I; R = C6H4‐2‐PPh2)

Treatment of copper(I) halides CuX (X = Cl, Br, I) with lithium 2‐(diphenylphosphanyl)anilide [Li(HL)] in THF led to the formation of hexanuclear copper(I) complexes [Cu₆X₂(HL)₄] [X = Cl ( 1 ), Br ( 2 ), I ( 3 )]. In compounds 1 – 3 , the copper atoms are in a distorted octahedral arrangement and the amide ligands adopt a μ₃‐κP,κ²N bridging mode. Additionally there are two μ₂‐bridging halide ligands. Each of the [Cu₆X₂(HL)₄] clusters comprises two copper atoms, which are surrounded by two amide nitrogen atoms in an almost linear coordination [Cu–N: 186.2(3)–188.0(3) pm] and four copper atoms, which are connected to an amide N atom, a P atom, and a halogen atom in a distorted trigonal planar fashion [Cu–N: 199.6(3)–202.3(3) pm)].     

Synthesis and Characterization of Tetrahedral Zinc(II) Complexes with 3, 6,7‐Triamino‐7H‐[1, 2,4]triazolo[4, 3‐b][1, 2,4]triazole as Nitrogen‐Rich Ligand

Triaminotriazolotriazole (TATOT) was used as a nitrogen‐rich ligand for the formation of the energetic Zn^II complexes [ZnCl₂(TATOT)₂] · H₂O ( 2 ), [Zn(H₂O)(TATOT)₃](NO₃)₂ · 2H₂O ( 3 ), and [Zn(TATOT)₄](ClO₄)₂ · 2H₂O ( 4 ). The zinc species were prepared in a straightforward and inexpensive synthesis. The complexes 2 – 4 were structurally characterized using X‐ray diffraction. Additionally, the compounds were characterized using elemental analysis and infrared (IR) spectroscopy. Finally, the sensitivities toward thermal and mechanical stimuli were determined by differential thermal analysis (DTA) and BAM (Bundesanstalt für Materialforschung und ‐prüfung) methods.     

A New Germanium Complex Containing Chelating Pyridinecarboxylate Ligands: cis‐Dihydroxybis(pyridine‐2‐carboxylato‐κN1,κO2)germanium Hydrate (1 : 2) (cis‐[Ge(pyca)2(OH)2]⋅2 H2O)

A new germanium complex, cis‐[Ge(pyca)₂(OH)₂]?2 H₂O ( 1 ; pyca=pyridine‐2‐carboxylato), was synthesized by the reaction of [Ge(acac)₂Cl₂] (acac=acetylacetonato=pentane‐2,4‐dionato) with potassium pyridine‐2‐carboxylate (Kpyca) in H₂O/THF. According to the single‐crystal X‐ray diffraction analysis, each Ge‐atom of 1 is coordinated by two pyca ligands and two OH^? groups (Fig. 1). These molecules are bonded to each other via a system of H‐bonds resulting in a sheet‐like structure (Fig. 2). The complex is decomposed during heating with stepwise mass loss and formation of GeO₂ as final product (Fig. 3).     

Synthese und Eigenschaften von Triphenylzinnmolybdaten mit kettenförmigen Anionen des Typs 1∞[(Ph3Sn)MoO4]–. Die Kristallstrukturen von (nPr4N)[(Ph3Sn)MoO4]·CH3CN, (nBu4N)[(Ph3Sn)MoO4], [Zn(en)2(Ph3Sn)2(MoO4)2]·2DMF·EtOH und [Cu(en)2(Ph3Sn)2(MoO4)2]·2DMF·EtOH

The reaction of Ph₃SnCl, (R₄N)₂[Mo₆O₁₉] and (R₄N)OH in a molar ratio of 6:1:10 leads to the formation of (R₄N)[(Ph₃Sn)MoO₄] (R = ⁿPr ( 1 ), ⁿBu ( 2 )). Compounds 1· CH₃CN and 2 have been charactarized by IR spectroscopy and single crystal X‐ray diffraction. 1· CH₃CN forms orthorhombic crystals, space group P2₁2₁2₁ with a = 1339.9(2), b = 1508.9(2), c = 1733.2(3) pm. 2 crystallizes in the monoclinic space group P2₁ with a = 1342.6(2), b = 2280.3(4), c = 1344.0(2) pm, β = 118.34(1). Both compounds 1 and 2 consist of isolated R₄N⁺ cations and polymeric $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains with an alternating arrangement of Ph₃Sn⁺ and MoO₄^2– groups. Treatment of (Ph₃Sn)₂MoO₄ with bis(ethylenediamine)copper(II) succinate yields [Cu(en)₂(Ph₃Sn)₂(MoO₄)₂] ( 3 ). The zinc derivative [Zn(en)₂(Ph₃Sn)₂(MoO₄)₂] ( 4 ) is obtained similarly by reaction of (Ph₃Sn)₂MoO₄ with bis(ethylenediamine)zinc(II) formiate. Compounds 3· 2DMF · EtOH and 4· 2DMF · EtOH crystallize in the monoclinic space group P2₁/n with a = 1998.0(2), b = 1313.3(1), c = 2181.6(2) pm, β = 90.97(1)° for 3 and a = 2015.4(1), b = 1316.7(1), c = 2157.0(1) pm, β = 90.40(1)° for 4 . Like in the cases of 1 and 2, polymeric $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains are observed. The [M(en)₂]²⁺ units (M = Cu, Zn) act as linkers between the $\rm^{1}_{\infty}$ [(Ph₃Sn)MoO₄]^– chains to give 2D layer structures with (6, 3) net topology.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

Synthesis,characterization and biological activity of a novel binuclear organotin complex,Ph3Sn(HL)·Ph2SnL [L = 3,5‐Br2‐2‐OC6H2CHNCH(i‐Pr)COO]

A 1:1 reaction of triphenyltin chloride with potassium N‐[(3,5‐dibromo‐2‐hydroxyphenyl)methylene] valinate in benzene under reflux leads to the formation of a novel mixed organotin binuclear complex, Ph₃Sn(HL)·Ph₂SnL [L = 3,5‐Br₂‐2‐OC₆H₂CH?NCH(i‐Pr)COO], by means of a facile phenyl–tin bond cleavage process. The X‐ray structure reveals that there are two distinct types of carboxylate coordination mode and trans‐O₂SnC₂N and trans‐O₂SnC₃ in distorted trigonal bipyramidal geometries. The complex displays good in vitro cytotoxicity and antibacterial activities. Copyright © 2005 John Wiley & Sons, Ltd.