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The molecular structure of free aniline has been investigated by gas-phase electron diffraction and ab initio MO calculations at the HF and MP2 levels of theory, using the 6-31G*(6D) basis set.Least-squares refinement of a model with Cs symmetry, with constraints from MP2 calculations, has led to an accurate determination of the C--C--C angle at the ipso position of the benzene ring, ce = 119.0 + 0.2* (where the uncertainty represents total error). This parameter provides information on the extent of the interaction between the nitrogen lone pair and the 7r system of the benzene ring, and could not be determined accurately by microwave spectroscopy. The angles at the ortho, meta, and para positions of the ring are 120.3 + 0.1 ~ 120.7 + 0.1 ~ and 119.0 + 0.3 ~ respectively. Important bond distances are (rg(C--C)) --1.398 5:0.003 A. and rg(C--N) = 1.407 + 0.003 .~. The effective dihedral angle between the H--N--H plane and the ring plane, averaged over the large-amplitude inversion motion of the amino group, is (Irl) = 44:1: 4 ~ The equilibrium dihedral angle is calculated to be 41.8 ~ at the HF level and 43.6 ~ at the MP2 level, in agreement with far-infrared spectroscopic information. The MO calculations predict that the difference r(Cortho--Cmeta ) --r(Cipso--Cortho) is 0.008-0.009 .~. They also indicate that the nitrogen atom is displaced from the ring plane, on the side opposite to the amino hydrogens. The displacement is 0.049 .A, at the HF level and 0.072 ~, at the MP2 level. The two calculations, however, yield very different patterns for the minute deviations from planarity of the ring carbons.

The crystal and molecular structure of the layered weak-ferromagnet Fe[CH(3)PO(3)] x H(2)O has been solved by X-ray single-crystal diffraction techniques. Crystal data for Fe[CH(3)PO(3)] x H(2)O are the following: orthorhombic space group Pna2(1); a =17.538(2), b = 4.814(1), c = 5.719(1) A. The structure is lamellar, and it consists of alternating organic and inorganic layers along the a direction of the unit cell. The inorganic layers are made of Fe(II) ions octahedrally coordinated by five phosphonate oxygen atoms and one from oxygen of the water molecule. Each phosphonate group coordinates four metal ions, through chelation and bridging, making in this way a cross-linked Fe-O network. The resultant layers are then separated by bilayers of the methyl groups, with van der Waals contacts between them. The compound is air stable, and it dehydrates under inert atmosphere at temperatures above 120 degrees C. The oxidation state of the metal ion is +2, and the electronic configuration is d(6)( )()high spin (S = 2), as determined from dc magnetic susceptibility measurements from 150 K to ambient temperature. Below 100 K, the magnetic moment of Fe[CH(3)PO(3)] x H(2)O rises rapidly to a maximum at T(max) approximately equal to 24 K, and then it decreases again. The onset of peak at T = 25 K is associated with the 3D antiferromagnetic long-range ordering, T(N). The observed critical temperature, T(N), is like all the other previously reported Fe(II) phosphonates, and it appears to be nearly independent of the interlayer spacing in this family of hybrid organic-inorganic layered compounds. Below T(N), the compound behaves as a "weak ferromagnet", and represents the third kind of magnetic materials with a spontaneous magnetization below a finite critical temperature, ferromagnets and ferrimagnets being the other two types.

Four organic salts, namely benzamidinidium orotate (2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylate) hemihydrate, C(7)H(9)N(2)(+).C(5)H(3)N(2)O(4)(-).0.5H(2)O (BenzamH(+).Or(-)), (I), benzamidinium isoorotate (2,4-dioxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate) trihydrate, C(7)H(9)N(2)(+).C(5)H(3)N(2)O(4)(-).3H(2)O (BenzamH(+).Isor(-)), (II), benzamidinium diliturate (5-nitro-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-olate) dihydrate, C(7)H(9)N(2)(+).C(4)H(2)N(3)O(5)(-).2H(2)O (BenzamH(+).Dil(-)), (III), and benzamidinium 5-nitrouracilate (5-nitro-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-1-ide), C(7)H(9)N(2)(+).C(4)H(2)N(3)O(4)(-) (BenzamH(+).Nit(-)), (IV), have been synthesized by a reaction between benzamidine (benzenecarboximidamide or Benzam) and the appropriate carboxylic acid. Proton transfer occurs to the benzamidine imino N atom. In all four acid-base adducts, the asymmetric unit consists of one tautomeric aminooxo anion (Or(-), Isor(-), Dil(-) and Nit(-)) and one monoprotonated benzamidinium cation (BenzamH(+)), plus one-half (which lies across a twofold axis), three and two solvent water molecules in (I), (II) and (III), respectively. Due to the presence of protonated benzamidine, these acid-base complexes form supramolecular synthons characterized by N(+)-H...O(-) and N(+)-H...N(-) (+/-)-charge-assisted hydrogen bonds (CAHB).

Abstract A new X-ray diffraction study of p-nitroaniline shows that through-conjugation has highly significant effects on the geometry of the molecule, as compared to aniline and p-nitrobenzoic acid. The effects include a moderate decrease of the internal angles of the ring at substituted carbons, with respect to values derived by superimposing independent angular distortions from each substituent.