F. Iwasaki

Structures of 6a-thia/selena-1,3,4,6-tetraazapentalene derivatives : hypervalent S/SE-N bonds

C 18 H 16 N 4 O 2 S (I) cristallise dans Iba2 avec a=20,490, b=21,420, c=7,575 A, Z=8; affinement jusqua R=0,051. C 10 H 16 N 4 O 2 S (II) cristallise dans P2 1 /n avec a=23,888, b=4,8422, c=22,518 A, β=102,62°, Z=8; affinement jusqua R=0,073. C 10 H 16 N 4 S 2 Se (III) cristallise dans P2 1 avec a=13,025, b=10,233, c=5,2535 A, β=98,36°, Z=2; affinement jusqua R=0,043. Les caracteristiques structurales montrent lhypervalence π du systeme 1.2 π

Crystal and molecular structures of bismuth compounds of a spiro-σ-sulfurane type

The crystal and molecular structures of [2-(2-methoxy-2-propyl)phenyl-C ~](2-phenyl-2-propanolatoC,O)bismuth (I), [2-(2-hydroxy-2-propylphenyl-CI)](2-phenyl-2-propanolato-C~,O)bismuth (II) and tetraethylammonium bis(2-phenyl-2-hexafluoropropanolato-C~,O)bismuthate monohydrate (III) were determined by the X-ray method. Crystal data: (I), [Bi(CI9H2302)], Mr = 492.37, monoclinic, P21/n, a = 11.635 (3), b = 8.837 (2), c= 18.149 (4) A,, /3 = 103.17(3) ° , V= 1817.0(7)A 3, Z=4, Dx = 1.800 Mg m -3, a(Mo Ka) = 0.71069 A,, # = 9.680 mm-~, F(000) = 944, T = 298 K, R = 0.046, wR=0.061 for 3033 observed reflections. (II), [Bi(CtsH2102)], Mr = 478.34, monoclinic, C2/c, a = 19.902 (4), b = 18.353 (2), c = 17.303 (2) A,, /3 = 109.69(2) °, V=5951(1) A, 3, Z=12, Dx=1.602, Dm= 1.663 Mg m -3, ,~(Mo Ka) = 0.71069 A,, /z = 8.865 mm-i, F(000) = 2736, T= 298 K, R = 0.070, wR=0.096 for 3609 observed reflections. (III), [N(C2Hs)4][Bi(C,sH8F,202)].H20, Mr = 841.49, monoclinic, P21/n, a = 15.547 (2), b = 15.900 (2), c = 11.996.(2) A,, /3 = 90.19 (2) °, V = 2965.4 (8) A 3, Z = 4, Dx = 1.885, Dm = 1.896Mgm --3, A(MoKa)=

Synthesis, structure, and reactions of 10-Bi-4 organobismuth ate complexes

Abstract The anionic 10-Bi-4 species ( 2a , 2b ) were synthesized by the reaction of BiCl 3 with 2 equiv of lithium 2-(2-lithiophenyl)-2-propoxide derivatives ( 1a , 1b ). The X-ray crystallographic analysis showed 2a- Et 4 N + to be distorted pseudotrigonal bipyramid in geometry. Reaction of dimethyl-substituted 2b- Li + with methyl iodide took place exclusively not at the bismuth but at the oxygen to give an ether 4 .

Syntheses, second-order NLO properties, and crystal structures of tetra-substituted ethylene, tri-substituted schiff-base, and diphenoxymethane derivatives

Abstract In order to obtain frequency doubler of the infrared semiconductor lasers, a series of push-pull ethylenes were synthesized. Among them, ethyl 2,2-bis(methylthio)-1-cyanoacrylate, ethyl 2-dimethylamino-2-methylthio-1-cyanoacrylate, and 2-dimethylamino-2-methylthio-1-cyanoacrylonitrile gave SHG with intensities of 5.5, 0.8, and 0.5 times, respectively, that of urea by a powder technique using an Nd: YAG laser as a fundamental wave. Their absorption edges located below 370 nm. The crystal structure analysis showed the distorted ethylene structure mainly due to the contribution of an intramolecular charge-transfer in their ground states. Their β values were calculated in an MNDO level. Diphenoxymethanes are expected to be Λ-shaped molecules and to favor columnar and non-centrosymmetric structures when packed in a crystal. Bis[ p -(2,2-dicyanovinyl)phenoxy]methane, bis[ p -(2-cyano-2-ethoxycarbonylvinyl)phenoxy]methane, and bis( p -bromophenylthio)methane gave SHG intensities 0.4, 1.4, and 0.1 times, respectively, that of urea.

Synthesis and characterization of 10-Se-3 type selenatetraazapentalene derivatives with a hypervalent selenium

Abstract Symmetrical 12π-selenatetraazapentalene derivatives 3–5 were synthesized by a convenient one-pot reaction using the lithium selenoureide/phenacyl chloride/alkyl (or allyl) isothiocyanate system. The structure was determined by a single crystal X-ray diffraction of 4. The reactions of 3 and 5 with alkyl iodides and ω-bromoalkyl isothiocyanates gave the novel selenatetraazapentalene derivatives.