Variable dimensionality in 'hollow' hybrid tin iodide perovskites

We acknowledge support from the University of St Andrews and the Leverhulme trust (RPG-2018-065).Two ‘hollow’ B-site deficient perovskites, (TzH)11(H3PO2)Sn6I23 and (TzH)3Sn2I7 (TzH+ = 1,2,4-triazolium, H3PO2 = hypohosphorous acid), have been prepared. (TzH)11(H3PO2)Sn6I23 is the first example of a 2D layered structure of this type. Leaving the same reaction mixture for an extended time also affords the 3D derivative (TzH)3Sn2I7.Publisher PDFPeer reviewe

2,6-Dimethoxybenzyl bromide

The unstable title compound has been characterized for the first time. Its melting point, UV, IR, 1H and 13C NMR and high-resolution mass spectra are presented. The X-ray structure has also been determined and shows a rather long C–Br bond perpendicular to the otherwise planar molecule.Publisher PDFPeer reviewe

Correction : Assessing dimerisation degree and cooperativity in a biomimetic small-molecule model by pulsed EPR

Correction for ‘Assessing dimerisation degree and cooperativity in a biomimetic small-molecule model by pulsed EPR’ by K. Ackermann et al., Chem. Commun., 2015, 51, 5257–5260.Publisher PDFPeer reviewe

(E)-1-(2,5-Dichloro­thio­phen-3-yl)ethan­one [8-(trifluoro­meth­yl)quinolin-4-yl]hydrazone

In the title compound, C16H10Cl2F3N3S, the dihedral angle between the quinoline and thio­phene ring systems is 4.94 (10)°. The NH group of the hydrazone moiety does not form a hydrogen bond, due to a steric crowding. In the crystal, the thio­phene ring takes part in weak π–π stacking inter­actions with the pyridine ring [centroid-to-centroid separation = 3.7553 (19) Å and inter­planar angle = 5.48 (12)°] and the benzene ring [3.7927 (19) Å and 4.58 (12)°]. Together, these lead to [100] stacks of mol­ecules in an alternating head-to-tail arrangement, with two π–π stacking contacts between each adjacent pair

Template or ligand? : Different structural behaviours of aromatic amines in combination with zincophosphite networks

We thank the EPSRC National Crystallography Service (University of Southampton) for the X-ray data collection for (I)Peer reviewedPublisher PD

Access to diarylmethanols by Wittig rearrangement of ortho-, meta- and para-benzyloxy-N-butylbenzamides

Authors thank EPSRC (UK) for a DTA studentship to ADH (Grant EP/L505079/1), EPSRC (UK) and CRITICAT Centre for Doctoral Training for a studentship to RAI (Grant code: EP/L016419/1) and the EPSRC UK National Mass Spectrometry Facility at Swansea University.The N-butyl amide group, CONHBu, has been found to be an effective promoter of the [1,2]-Wittig rearrangement of aryl benzyl ethers and thus allow the two-step synthesis of isomerically-pure substituted diarylmethanols starting from simple hydroxybenzoic acid derivatives. The method is compatible with a wide range of functional groups including methyl, methoxy and fluoro, although not with nitro and, unexpectedly, is applicable to meta as well as ortho and para isomeric series.Publisher PDFPeer reviewe

Sterically restricted tin phosphines, stabilized by weak intramolecular donor-acceptor interactions

Funding: Engineering and Physical Sciences Research Council (EPSRC)Four related sterically restricted pen-substituted acenaphthenes have been prepared containing mixed tin phosphorus moieties in the proximal 5,6-positions (Acenap[SnR3][(PPr2)-Pr-i]; Acenap = acenaphthene-5,6-diyl; R-3 = Ph-3 (1), Ph2Cl (2), Me2Cl (3), Bu2Cl (4)). The degree of intramolecular P-Sn bonding within the series was investigated by X-ray crystallography, solution and solid-state NMR spectroscopy, and density functional theory (DFT/B3LYP/SBKJC/PCM) calculations. All members of the series adopt a conformation such that the phosphorus lone pair is located directly opposite the tin center, promoting an intramolecular donor acceptor P -> Sn type interaction. The extent of covalent bonding between Sn and P is found to be much greater in triorganotin chlorides 2-4 in comparison with the triphenyl derivative 1. Coordination of a highly electronegative chlorine atom naturally increases the Lewis acidity of the tin center, enhancing the Ip(P)-sigma*(Sn-Y) donor acceptor 3c-4e type interaction, as indicated by conspicuously short Sn-P peri distances and significant (1)J(P-31,Sn-119) spin spin coupling constants (SSCCs) in the range 740-754 Hz. Evidence supporting the presence of this interaction was also found in solid-state NMR spectra of some of the compounds which exhibit an indirect spin spin coupling on the same order of magnitude as observed in solution. DFT calculations confirm the increased covalent bonding between P and Sn in 2-4, with notable WBIs of ca. 0.35 obtained, in comparison to 0.1 in 1.PostprintPeer reviewe

1-[Amino­(4-chloro­phen­yl)meth­yl]-6-bromo­naphthalen-2-ol

In the title compound, C17H13BrClNO, the dihedral angle between the naphthol ring system and the chloro­benzene ring is 76.59 (11)°. This twisted conformation is supported by an intra­molecular O—H⋯N hydrogen bond. In the crystal, [100] chains arise, with adjacent mol­ecules linked by an N—H⋯O hydrogen bond, a C—H⋯π inter­action and an aromatic π–π stacking contact [centroid-to-centroid separation = 3.783 (2) Å]. Weak C—H⋯O inter­actions also occur

Main group tellurium heterocycles anchored by a P2VN2 scaffold and their sulfur/selenium analogues

The authors are grateful to the EPSRC, the EPSRC National Mass Spectrometry Service Centre (NMSSC) Swansea, the School of Chemistry St. Andrews, EaStCHEM, and NSERC Canada for financial support.A comprehensive investigation of reactions of alkali-metal derivatives of the ditelluro dianion [TePV(NtBu)(μ-NtBu)]22– (L2–, E = Te) with p-block element halides produced a series of novel heterocycles incorporating P2VN2 rings, tellurium, and group 13–16 elements. The dianion engages in Te,Te′-chelation to the metal center in Ph2Ge and R2Sn (R = tBu, nBu, Ph) derivatives; similar behavior was noted for group 14 derivatives of L2– (E = S, Se). In the case of group 13 trihalides MCl3 (M = Ga, In), neutral spirocyclic complexes (L)M[NtBu(Te)PV(μ-NtBu)2PIIIN(H)tBu)] (M = Ga, In) comprised of a Te,Te′-chelated ligand L2– and a N,Te-bonded ligand resulting from loss of Te and monoprotonation were obtained. In reactions with RPCl2 (R = tBu, Ad, iPr2N) a significant difference was observed between Se- and S-containing systems. In the former case, Se,Se′-chelated derivatives were formed in high yields, whereas the N,S-chelated isomers predominated for sulfur. All complexes were characterized by multinuclear (1H, 31P, 77Se, 119Sn, and 125Te) NMR spectroscopy; this technique was especially useful in the analysis of the mixture of (L)(Se) and (L)(SeSe) obtained from the reaction of Se2Cl2 with L2– (E = Te). Single-crystal X-ray structures were obtained for the spirocyclic In complex (9), (L)GePh2 (E = Te, 10), (L)SntBu2 (E = Te, 12a); E = Se, 12aSe, E = S, 12aS) and (L)(μ-SeSe) (E = Te, 16).PostprintPostprintPeer reviewe