Structure of bis(4-biphenylyl)sulphur diimide

Busetti, V.

doi:10.1107/s0567740882003720

Cited by 26 publications

(11 citation statements)

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“…The main difference between 5EA and 5CA is the substitution in the same relative position, containing a 4-chlorobenzoic acid and a 4-biphenylcarboxylic acid, respectively. In the last case, this group has a slight torsional angle between the rings [39.12(9)° and 36.12(9)°], being these values similar to others found in the literature for this type of group (Brown et al , 1977; Busetti, 1982). No classical hydrogen bonds were found in both structures.…”

Section: Discussionsupporting

confidence: 87%

Ab initio crystal structure determination of two chain functionalized pyrroles from synchrotron X-ray powder diffraction data

et al. 2012

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The crystal structure of two chain functionalized pyrroles, methyl 1-benzyl-5-(1-(4-chlorobenzoyloxy)-2-methoxy-2-oxoethyl)-4-(4-chlorophenyl)-1H-pyrrole-2-carboxylate and methyl 1-benzyl-4-(biphenyl-4-yl)-5-(1-(4-biphenylcarbonyloxy)-2-methoxy-2-oxoethyl)-1H-pyrrole-2-carboxylate, which are both important active candidates as antitumoral agents, have been obtained ab initio from synchrotron X-ray powder diffraction data. Both compounds crystallize in the monoclinic system (space group P21/c), with a = 20.2544(3) Å, b = 6.80442(9) Å, c = 21.1981(3) Å, β = 111.6388(9)° and a = 29.7747(6) Å, b = 6.27495(14) Å, c = 18.8525(3) Å, β = 107.053(2)°, respectively. These structures were determined using a direct space approach, by means of Monte Carlo technique, followed by Rietveld refinement.

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Section: Discussionsupporting

confidence: 87%

Ab initio crystal structure determination of two chain functionalized pyrroles from synchrotron X-ray powder diffraction data

et al. 2012

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“…The bond distances and angles for compound (7) and some related molecules are shown in Table 5. The observed structure has the expected bent NSN group with an angle at sulphur [129.5( 16)O] which is larger than that observed for syn,unti or anti,unti di-imides, but closer to the angle in syn,syn-p-CIC,H,SNSNSC,H,CI-p [ 124.0( l)"].…”

Section: Discussionmentioning

confidence: 99%

Gas-phase molecular structure of NN′-bis(trimethylsilyl)sulphur di-imide, determined by electron diffraction

Anderson¹,

Robertson²,

Rankin³

et al. 1989

J. Chem. Soc., Dalton Trans.

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The molecular geometry of Me,SiNSNSiMe, in the gas phase has been studied by electron diffraction. The molecule has C, symmetry w i t h a distorted syn,syn conformation. Principal parameters are: ra(S=N) 153.6(3), ra(Si--N) 173.8(3), and ra(Si-C) 186.9(1) pm; NSN 129.5( 16), SNSi 132.9(7), and SN twist (relative to syn,syn conformation) 42(1)".Sulphur di-imides, R,N,S, have been known since the discovery of Bu',N,S in 1956l and a number of alky12 and ary13 derivatives are known. They are isoelectronic with SO, and this had led to substantial work on their co-ordination ~h e m i s t r y , ~ including the preparation of the o-bonded complex cis-[Pt(NSNSiMe,),(PPh,),1.5 Structurally, there are three possible conformations: syn,syn; syn,anti; and anti,anti. X-Ray crystallographic studies [R = phenyl, (1),6 or biphenyl, (2) ' 1 and an electron diffraction study8 [R = Me, (3)] indicate that the syn,anti structure is often preferred. N.m.r. studies have shown that both syn,anti and anti, anti exist in solution for both alkyl and aryl di-imides.'*'' However when R = p-CIC,H,S, (4)," or PhS (5),12 the syn,syn conformation is adopted. Furthermore, we have recently determined the X-ray crystal structure of p-O,NC,H,SNSNSiMe,, (6),' which adopts the syn,anti conformation. The X-ray crystal structure l 4 of an SnCI, adduct of (Me,Si),N,S, (7), reveals the di-imide to have the anti,anti conformation in this case although the proton n.m.r. spectrum of the free di-imide consists of a singlet. Clearly, the RNSNR group has the ability to adopt a wide range of conformations. In view of the extensive use of compound (7) in synthesis we have investigated its structure in the gas phase.

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“…By contrast, the symmetrical isomer observed in solution by NMR for a variety of aryl derivatives (e.g., R = 2,4,6-Br 3 C 6 H 2 , 2,6-Me 2 C 6 H 3 , C 6 F 5 ) was recently identified as the syn , syn isomer 4-C 6 H 5 C 6 H 4 , 2,4,6-Br 3 C 6 H 2 6a ) and syn , syn conformations (R = 4-XC 6 H 4 S (X = H, Cl 10 ), 2,6-Me 2 C 6 H 4 ,6a C 6 F 5 6b ) have been identified by solid-state X-ray structural determinations. Electron diffraction studies have revealed both syn , anti (R = Me) and syn , syn (R = SiMe 3 ) conformations in the gas phase.…”

Section: Introductionmentioning

confidence: 99%

Chalcogen Diimides: Relative Stabilities of Monomeric and Dimeric Structures, [E(NMe)₂]_n (E = S, Se, Te; n = 1, 2)

1998

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Density functional theory (DFT) calculations have been used to investigate the process of dimerization for the three chalcogen diimides MeNdEdNMe (E ) S, Se, Te). DFT calculations for these monomers reveal that the energies of the syn,syn and syn, anti isomers differ by <3.5 kJ mol -1 for all three chalcogens while the anti,anti isomers are substantially higher in energy (by 25-39 kJ mol -1 ). A qualitative understanding of this difference can be derived from consideration of the electronic structures of the chalcogen diimides. In particular, the antibonding interaction between the in-plane nitrogen lone pairs and the p z orbital on sulfur destabilizes the most sterically favorable anti,anti isomer. The calculated dimerization energies for MeNdEdNMe show that the process is endothermic (∆E ) 34.9 kJ mol -1 ) for E ) S, approximately thermoneutral (∆E ) -2.8 kJ mol -1 ) for E ) Se, and strongly exothermic (∆E ) -82.9 kJ mol -1 ) for E ) Te. A qualitative analysis of the orbital interactions involved in the dimerization process reveals that the LUMOs of the diimide monomers are populated in a stabilized bonding LUMO-LUMO interaction that is lower in energy than the antibonding HOMO-HOMO interaction. The most significant contribution to the energy of dimerization is the energy required to distort the planar diimide monomer into half of the butterfly dimer.

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Structure of bis(4-biphenylyl)sulphur diimide

Cited by 26 publications

References 0 publications

Ab initio crystal structure determination of two chain functionalized pyrroles from synchrotron X-ray powder diffraction data

Ab initio crystal structure determination of two chain functionalized pyrroles from synchrotron X-ray powder diffraction data

Gas-phase molecular structure of NN′-bis(trimethylsilyl)sulphur di-imide, determined by electron diffraction

Chalcogen Diimides: Relative Stabilities of Monomeric and Dimeric Structures, [E(NMe)₂]_n (E = S, Se, Te; n = 1, 2)

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Structure of bis(4-biphenylyl)sulphur diimide

Cited by 26 publications

References 0 publications

Ab initio crystal structure determination of two chain functionalized pyrroles from synchrotron X-ray powder diffraction data

Ab initio crystal structure determination of two chain functionalized pyrroles from synchrotron X-ray powder diffraction data

Gas-phase molecular structure of NN′-bis(trimethylsilyl)sulphur di-imide, determined by electron diffraction

Chalcogen Diimides: Relative Stabilities of Monomeric and Dimeric Structures, [E(NMe)2]n (E = S, Se, Te; n = 1, 2)

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Chalcogen Diimides: Relative Stabilities of Monomeric and Dimeric Structures, [E(NMe)₂]_n (E = S, Se, Te; n = 1, 2)