Studies in Nonlinear Optical Materials: Structure of 3-Menthyl 2-[Bis(dimethylarnino)methylene]-3-oxobutyrate Hemihydrate

C 19Ha4N203.~xH 2 O, Mr= 347.5, monoclinic, C2, a = 15.473 (3), b = 6.963 (2), c = 20.708 (4) ]1, //=108.2(2) ° , V=2119(2)A 3, Z=4, Ox= 1.089 Mg m -3, ,~(Cu Ktx) = 1.5418 ]1, p = 0.523 mm -~, F(000) = 760.0, T= 293 K, R = 0.068 for 1967 unique reflections. The C=C bond length is 1-447 (6)]1, significantly longer than in ethylene, 1.336 (2)]1. The crystal structure is stabilized by O-H...O hydrogen bonding. Explanation for the observed low second-harmonic-generation efficiency (0.5 times that of urea) is provided.

Dynamics of plant populations in Heteropogon contortus(black speargrass) pastures on a granite landscape in southern Queensland. 2. Seed production and soil seed banks of H. contortus

Seed production and soil seed hanks of H. contortus were studied in a subset of treatments within an extensive grazing study conducted in H. contortus pasture in southern Queensland between 1990 and 1996. Seed production of H. contortus in autumn ranged from 260 to 1800 seeds/m2 with much of this variation due to differences in rainfall between years. Seed production was generally higher in the silver-leaved ironbark than in the narrow-leaved ironbark land class and was also influenced by a consistent stocking rate x pasture type interaction. Inflorescence density was the main factor contributing to the variable seed production and was related to the rainfall received during February. The number of seeds per inflorescence was unaffected by seasonal rainfall, landscape position, stocking rate or legume oversowing. Seed viability was related to the rainfall received during March. Soil seed banks in spring varied from 130 to 520 seeds/m2 between 1990 and 1995 with generally more seed present in the silver-leaved ironbark than in the narrow-leaved ironbark land class. There were poor relationships between viable seed production and the size of the soil seed bank, and between the size of the soil seed bank and seedling recruitment. This study indicates that H. contortus has the potential to produce relatively large amounts of seed and showed that the seasonal pattern of rainfall plays a major role in achieving this potential

Push-pull ethylenes: the structures of 3-(2-imidazolidinylidene)-2,4-pentanedione (I), C8H12N2O2, and 3-(1,3-dimethyl-2-imidazolidinylidene)-2,4-pentanedione trihydrate (II), C10H16N2O2.3H2O

(I): Mr= 168, triclinic, P1, Z=2, a= 5.596 (2), b = 6.938 (3), c = 10.852 (4) A, ~t= 75.64 (3), fl= 93.44 (3), ),= 95.47 (3) °, V= 406.0A 3, Din= 1.35 (by flotation using carbon tetrachloride and n-hexane), D x= 1.374 Mg m -3, g(Mo Kct, 2 = 0.7107 A) = 1.08 cm -l, _F(000) = 180, T= 293 K. (II): Mr= 250, triclinic, P1, Z= 2, a = 7.731(2), b=8.580(2), c=11.033(3)A, a= 97-66 (2), fl= 98.86 (2), y= 101.78 (2) °, V= 697.5 A 3, D m = 1.18 (by flotation using KI solution), Dx= 1.190Mgm -3, g(MoKa, 2=0.7107A)= 1.02 cm -1, F(000) = 272, T= 293 K. Both structures were solved by direct methods and refined to R = 4.4% for 901 reflexions for (I) and 5.7% for 2001 reflexions for (II). The C=C bond distances are 1.451 (3) A in (I) and 1.468 (3)A in (II), quite significantly longer than the C=C bond in ethylene [1.336 (2).~; Bartell, Roth, Hollowell, Kuchitsu & Young (1965). J. Chem. Phys. 42, 2683-2686]. The twist angle about the C=C bond in (II) is 72.9 (5) ° but molecule (I) is essentially planar, the twist angle being only 4.9 (5) ° .

Synthesis and Reactions of Binuclear Diolefin Rhodium(I) Compounds bridged by Nitrogen Heterocycles, Crystal Structure of Dichloro-Di-1,5-Cyclooctadiene(Mu-Pyrazine)-Dirhodium(I) [[Rh(1,5-C8h12)Cl]2(Mu-C4h4n2)]

Binuclear complexes of rhodium(I) of the type [(dien)(X)Rh(μ-N-N)Rh(X)(dien)] (dien = 1,5-cyclooctadiene or norbornadiene; N-N = pyrazine, 4,4′-bipyridine or Phenazine and X = Cl or Br) with bridging heterocycles have been isolated and their reactions with carbon monoxide, 2,2′-bipyridine and 1,10-phenanthroline investigated. The crystal structure of [(COD)(Cl)Rh(μ-pyrazine)Rh(Cl)(COD)] has been determined.

Studies in Nonlinear Optical Materials: Structure of Methyl 2-(4-Ethyl-5-methyl- 2-thioxo-2,3-dihydro-l,3-thiazol- 3-yl) propionate

CIoH15NO282, Mr=245"0, orthorhombic, P21212 ~, a = 6.639 (2), b = 8.205 (2), c = 22.528(6)A, V= I227.2(6)A 3, z=4, Dm= 1.315, Dx= 1.326gem -3, MoKa, 2=0.7107A, 12= 3.63 cm -1, F(000) = 520, T= 293 K, R = 0.037 for 1115 significant reflections. The second-harmonicgeneration (SHG) efficiency of this compound is only 1/10th of the urea standard. The observed low second-order nonlinear response may be attributed to the unfavourable packing of the molecules in the crystal lattice.

Synthesis and structure of mixed ligand isonitroso-β-ketoiminenickel(II) complexes. Crystal structure of (1-ethoxycarbonyl-2-npropylimino-1-propanoneoximato) (1-methoxycarbonyl-2-imino-1-propanoneoximato)nickel(II)

Mixed ligand complexes of the type Ni(R-AB)(AC') and Ni(R-AC)(AB') where AB/AC denote N-bonded isonitroso- [3-ketoimino ligands, AB'/AC' denote the corresponding Obonded ligands and R = Me, Et, n-Pr are synthesised and characterised. The complexes are neutral with square planar geometry around nickel(II). The bonding isomerism of the isonitroso group is discussed on the basis of i.r. and 1H n.m.r. studies. The crystal structure of the title complex, Ni(n-Pr-IEAI)(IMAI') has been determined from diffractometer data by Patterson and Fourier methods and refined by least squares to R = 0.088 for 2209 observed reflections. Unit cell constants are: a = 11.945(2), b = 22.436(7), c = 13.248(5) ~, [3 = 95.13(2) ~ The space group is P2Jc with Z = 8. Niekel(II) has a square planar coordination of two imine nitrogens, an isonitroso-nitrogen (from n-Pr-IEAI) and another isonitrosooxygen (from IMAI').

A high yield synthesis of (±)-5,8-dimethoxy-2-α-hydroxyethyl-3,4-dihydronaphthalene, a key intermediate in anthracyclinone synthesis

The dimethoxytetralol gives on Vilsmeier reaction the dihydronaphthaldehyde (yield,92%), which on Grignard reaction with MeMgI affords the title compound (yield,�100%), the reactions constituting a high yield synthesis of this important anthracyclinone intermediate.

Structure of 7-methyl-1(2)a,1(6)a,3(4)a-trihomocubane-1(6)a,3(4)a-dione,star-c12h12o2- a case of enantiomeric and rotational disorder

M r = 188.22, monoclinic, P21/n, a = 6.219 (2), b= 10.508 (2), c=7.339 (1)A, t= 107.64 (2) °, V= 457 ,/k 3, Z = 2, D m - - 1.360 (3), D x = 1.366 (2)Mgm -3, ~,(MoKa) = 0.7107/~, #= 0.053 mm -I, F(000) = 200, T= 293 K. Final R = 5.8% for 614 significant reflections. The molecule, which does not possess a centre of symmetry, occupies a crystallographic centre of symmetry because of the statistical enantiomeric and rotational disorder. Latticeenergy calculations, based on van der Waals attractive and repulsive potentials, clearly show minima at the observed disordered positions.

Assessment of internal quality attributes of mandarin fruit. 2. NIR calibration model robustness

The robustness of multivariate calibration models, based on near infrared spectroscopy, for the assessment of total soluble solids (TSS) and dry matter (DM) of intact mandarin fruit (Citrus reticulata cv. Imperial) was assessed. TSS calibration model performance was validated in terms of prediction of populations of fruit not in the original population (different harvest days from a single tree, different harvest localities, different harvest seasons). Of these, calibration performance was most affected by validation across seasons (signal to noise statistic on root mean squared error of prediction of 3.8, compared with 20 and 13 for locality and harvest day, respectively). Procedures for sample selection from the validation population for addition to the calibration population (‘model updating’) were considered for both TSS and DM models. Random selection from the validation group worked as well as more sophisticated selection procedures, with approximately 20 samples required. Models that were developed using samples at a range of temperatures were robust in validation for TSS and DM.

Stabilization of the Alleged 'Bishomoaromatic' Bicyclo[3.2.l]octa-2,6-dienyl Anion by Counterion Interactions and by Hyperconjugation

Hyperconjugation and inductive effects, rather than homoaromaticity, are responsible for the stabilization of the title anion in the gas phase; interaction of the double bond with the Li+ gegenion in the endo geometry contributes additionally in solution.

Synthesis, characterization and X-ray structure of hexahydrazinium diuranyl pentaoxalate dihydrate, (N2H5)6(UO2)2(C2O4)5·2H2O

A new hydrazinium uranyl oxalate complex (N2H5)6[(UO2)2(C2O4)5]·2H2O has been prepared and characterized by chemical analysis, infrared, visible spectra and TG-DTA. The single crystal X-ray structure of the complex shows the presence of discrete N2H5+ cations, water molecules and [(UO2)2(C2O4)5]6− anions. In the anion, the linear uranyl groups are coordinated by two chelating bidentate oxalates and one bridging oxalate which lies on the center of symmetry between the two uranyl groups. The coordination polyhedron around each uranium atom is approximately a pentagonal bipyramid.

Structure of 5-Bromo-2',3'-O-isopropylideneuridine, C12H15BrN206

Mr= 363.17, orthorhombic, P21212 ~, a= 5.251(4), b=14.962(5), c=19.112(5)A, U= 1501.41/k 3, Z=4, Dx=1.61Mgm -3, /t(CuKa)= 3.02 mm -1, 2(Cu Ka)= 1.5418/~, final R = 7.0% for 1091 reflections with Fo> 2e(Fo). The glycosidic torsion angle ZCN is 13"1 (12) °. The ribose has a C (3')-exo,C (4)-endo twist geometry. The dioxolane ring assumes an envelope conformation with 0(3') displaced by 0.453 (10)/k from the plane of the other four atoms. The conformation about the C(4')-C(5') bond is gauche-gauche. The structure is stabilized by two hydrogen bonds between screw-axis-related molecules. The crystal packing and the conformation of the molecule are very similar to those found in the structure of 2',3'-O-isopropylideneuridine which lacks the Br atom at the 5-position.

Structure of 2',3'-O-Isopropylidene-5'-O-tosyluridine, C19H22N 2Oas

M r = 438.45, trigonal, P32, a = b = 13.385 (4), c = 9.900 (5) A,, V = 1536.0 A 3, Z = 3, D x = 1.42, D m = 1.42 Mg m -3, 2(Cu Ka) = 1.5418 A,,g(CuKa) = .800mm -], T=290K, F(000)=690, R=6.0% for 1222 unique reflections with F o>_2o(Fo). This is the first 2',3'-O-isopropylidene pyrimidine nucleoside with the base in a syn orientation with respect to the ribose [Xcy= 116.0(7)°]. The ribose has a C(3')-endo conformation with the phase angle of pseudorotation P = 16.36 (2) °. The dioxolane ring assumes an envelope conformation with 0(2') displaced from the best four-atom plane by 0.50 (1) k. The crystal structure is possibly stabilized by a bifurcated hydrogen bond between N(3) and the 0(2) and 0(4) atoms of screw-related molecules.

Temperature dependence of 35Cl NQR in 2,6-dichloropyridine

Chlorine NQR in 2,6-dichloropyridine has been investigated in the temperature range 77 K to room temperature and a single resonance line has been observed throughout. Using this data, torsional frequencies of the molecule have been evaluated on the basis of both the Bayer theory and the modified Bayer theory incorporating Tatsuzaki correction.