Measuring outcome in child and adolescent mental health services: consumers' views of measures.

BACKGROUND: Outcome measurement in child and adolescent mental health services in New Zealand became mandatory in 2005 and little is known about how this is perceived by service users. AIMS: This study aimed to ascertain what service users think about routine outcome measurement in child and adolescent mental health services. METHOD: Nine semi-structured focus groups of child and adolescent service users (n=34) and family members (n=21) were held in different sites in New Zealand to determine their views on outcome measures. RESULTS: Consumers supported outcome assessment with some provisos that have important implications for clinical services: the method of collecting information is critical to acceptance; assessment should be done in the context of an established relationship with the clinician; care is needed over the timing and context of assessment, access to information and feedback of results; and measures should be brief and holistic and their limitations recognised. CONCLUSION: Service users support outcome measures but their implementation requires care and consultation.

Synthesis of the tricyclic core of labiatin A and australin A.

A concise synthesis of the tricyclic core of the marine diterpene natural products labiatin A and australin A has been accomplished. The key ring-forming transformation is a cascade reaction comprising generation of a copper carbenoid from a diazo ketone, intramolecular reaction of the carbenoid with a cyclic ether, and rearrangement of the resulting free oxonium ylide or its metal-bound equivalent with ring expansion of the original cyclic ether.

3-Fluoro-benzoic acid-4-acetyl-pyridine (1/1) at 100†K.

In the title compound, C(7)H(5)FO(2)·C(7)H(7)NO, a moderate-strength hydrogen bond is formed between the carboxyl group of one mol-ecule and the pyridine N atom of the other. The benzoic acid mol-ecule is observed to be disordered over two positions with the second orientation only 4% occupied. This disorder is also reflected in the presence of diffuse scattering in the diffraction pattern.

Synthesis and characterisation of a Ni4 single-molecule magnet with S4 symmetry.

[Ni4Cl4(HL)4] () {H2L=HN(CH2CH2OH)2} has S4 symmetry and crystallises in the tetragonal space group I4(1)/a. Two exchange couplings are observed between the four Ni(II) centres, with J1=7.29 cm(-1) and J2=-2.08 cm(-1), leading to an S=4 ground state. The Ni4 complex shows the onset of frequency dependent signals in the out-of-phase ac susceptibility below 3 K. In single-crystal measurements carried out using a micro-SQUID, hysteresis loops are observed below 0.5 K, confirming that shows slow relaxation of magnetisation. The loops are temperature dependent but only weakly sweep rate dependent due to the presence of small intermolecular interactions, which hinder quantum tunnelling. This exchange bias between Ni4 molecules is also seen in high-frequency high-field EPR measurements, which give the parameters D=-0.75 cm(-1), B4 degrees=-6.7x10(-5) cm(-1) and gz=2.275.

The contrasting chemistry and cancer cell cytotoxicity of bipyridine and bipyridinediol ruthenium(II) arene complexes.

The synthesis and characterization of ruthenium(II) arene complexes [(eta(6)-arene)Ru(N,N)Cl](0/+), where N,N = 2,2'-bipyridine (bipy), 2,2'-bipyridine-3,3'-diol (bipy(OH)(2)) or deprotonated 2,2'-bipyridine-3,3'-diol (bipy(OH)O) as N,N-chelating ligand, arene = benzene (bz), indan (ind), biphenyl (bip), p-terphenyl (p-terp), tetrahydronaphthalene (thn), tetrahydroanthracene (tha) or dihydroanthracene (dha), are reported, including the X-ray crystal structures of [(eta(6)-tha)Ru(bipy)Cl][PF(6)] (1), [(eta(6)-tha)Ru(bipy(OH)O)Cl] (2) and [(eta(6)-ind)Ru(bipy(OH)(2))Cl][PF(6)] (8). Complexes 1 and 2 exibit CH (arene)/pi (bipy or bipy(OH)O) interactions. In the X-ray structure of protonated complex 8, the pyridine rings are twisted (by 17.31 degrees). In aqueous solution (pH = 2-10), only deprotonated (bipy(OH)O) forms are present. Hydrolysis of the complexes was relatively fast in aqueous solution (t(1/2) = 4-15 min, 310 K). When the arene is biphenyl, initial aquation of the complexes is followed by partial arene loss. Complexes with arene = tha, thn, dha, ind and p-terp, and deprotonated bipyridinediol (bipy(OH)O) as chelating ligands, exhibited significant cytotoxicity toward A2780 human ovarian and A549 human lung cancer cells. Complexes [(eta(6)-bip)Ru(bipy(OH)O)Cl] (7) and [(eta(6)-bz)Ru(bipy(OH)O)Cl] (5) exhibited moderate cytotoxicity toward A2780 cells, but were inactive toward A549 cells. These activity data can be contrasted with those of the parent bipyridine complex [(eta(6)-tha)Ru(bipy)Cl][PF(6)] (1) which is inactive toward both A2780 ovarian and A549 lung cell lines. DFT calculations suggested that hydroxylation and methylation of the bipy ligand have little effect on the charge on Ru. The active complex [(eta(6)-tha)Ru(bipy(OH)O)Cl] (2) binds strongly to 9-ethyl-guanine (9-EtG). The X-ray crystal structure of the adduct [(eta(6)-tha)Ru(bipy(OH)O)(9-EtG-N7)][PF(6)] shows intramolecular CH (arene)/pi (bipy(OH)O) interactions and DFT calculations suggested that these are more stable than arene/9-EtG pi-pi interactions. However [(eta(6)-ind)Ru(bipy(OH)(2))Cl][PF(6)] (8) and [(eta(6)-ind)Ru(bipy)Cl][PF(6)] (16) bind only weakly to DNA. DNA may therefore not be the major target for complexes studied here.

Bis-tris propane as a new polydentate linker in the synthesis of iron(III) and manganese(II/III) complexes.

We describe the synthesis, structure, and magnetic properties of two new complexes, one decanuclear iron(III) cluster and one hexanuclear mixed-valence manganese(II/III) cluster, where the previously unexplored polydentate ligand Bis-tris propane {(CH2OH)3CNH(CH2)3NHC(CH2OH)3} is used to link small cluster fragments into high-nuclearity complexes.

Cobalt(II) citrate cubane single-molecule magnet.

An investigation of the magnetic properties of the cobalt(II) citrate cubane [C(NH 2) 3] 8{Co 4(cit) 4}.4H 2O reveals that the cluster is a new cobalt(II) single-molecule magnet, with an energy barrier to reorientation of the magnetization, Delta E/ k B = 21 K, and tau 0 = 8 x 10 (-7) s. The compound displays distinct, frequency-dependent peaks in the out-of-phase (chi'') component of the ac magnetic susceptibility and magnetization versus field hysteresis loops that are temperature and sweep rate dependent. The hysteresis loops collapse at zero field due to very fast quantum tunneling of the magnetization (QTM).

Oxidative rearrangements of isobenzofurans: studies toward the synthesis of the ajudazols.

We present a new facet of isobenzofuran chemistry which allows for its efficient manipulation to generate biologically relevant entities. This methodology has been successfully applied toward the synthesis of ajudazol A.

Linking iron(III) carboxylates into high-nuclearity complexes by using Bis-tris.

We describe the synthesis, structure and magnetic properties of two decanuclear Fe(III) complexes with novel core topologies, assembled using the tetra-deprotonated form of Bis-tris {2-[bis(2-hydroxyethyl)amino]-2-(hydroxymethyl)propane-1,3-diol, H5L}.

Using small molecule crystal structure data to obtain information about sulfonamide conformation.

Understanding the conformations adopted by the sulfonamide group is essential to the understanding of the way that sulfa drugs act upon the body. The relative energies of these conformations in the solid state are estimated from the Cambridge Structural Database (CSD) using cluster analysis, and are used to confirm earlier findings that many high-level ab initio calculations do not reproduce the observed solid-state structure. These conformational studies have been extended to the adjacent torsion angles, and it has been shown that the sulfonamide group significantly affects the form adopted. The relative energies of the observed forms in the solid state have been estimated using data available in the CSD.

A mixed-valence Co7 single-molecule magnet with C3 symmetry.

The synthesis, structure and magnetic properties of [Co(II)(4)Co(III)(3)(HL)(6)(NO(3))(3)(H(2)O)(3)](2+) [H(3)L = H(2)NC(CH(2)OH)(3)] are reported: the complex is an exchange-biased single molecule magnet.

Using cluster analysis to study transition-metal geometries: four-coordinate complexes with two salicylaldiminato or related ligands.

Cluster analysis is shown to be an effective method to analyse and classify metal coordination geometry in a very large number of four-coordinate bis-salicylaldimato (or bis-beta-iminoketonate) transition-metal complexes available in the Cambridge Structural Database. The methods described require no prior knowledge of chemistry to be input; retrieved structures are automatically clustered into groups based purely on the geometric similarity of the fragments and these groupings can then be interpreted by the structural chemist.

The application of cluster analysis to identify conformational preferences in enones and enimines from crystal structural data.

Cluster analysis can be an effective tool for analysing large quantities of data. Here it has been applied to the conformational analysis of enones and enimines in the crystalline solid state, using structural information mined from the Cambridge Structural Database. The forms that are common in the gaseous state and in solution are already known from spectroscopic studies. These forms are also found to be the most common conformations observed in the solid state; however, the clustering method highlights those structures that do not conform to the expected geometries. The study is supported by ab initio gas phase calculations on simple enone and enimine fragments.

Structure and hydrogen bonding in 2,4-dihydroxybenzoic acid at 90, 100, 110 and 150 K; a theoretical and single-crystal X-ray diffraction study.

A new polymorph of 2,4-dihydroxybenzoic acid is reported. The structure was characterized by multiple-temperature X-ray diffraction and solid-state DFT computations. The material shows a geometric pattern of hydrogen bonding consistent with cooperativity between the intermolecular carboxylic acid dimer and intramolecular hydrogen bonds. The presence of proton disorder within this hydrogen-bond system, which would support such a cooperative model, was not fully ruled out by the initial X-ray studies. However, solid-state calculations on the three possible end-point tautomers indicate that the dominant crystallographically observed configuration is substantially lower in energy than the other tautomers (by at least 9 kJ mol(-1)), indicating that no disorder should be expected. It is therefore concluded that no disorder is observed either in the intra- or intermolecular hydrogen bonds of the title compound and that the cooperativity between the hydrogen bonds is not present within the temperature range studied.

Synthesis and characterisation of a mixed-valence Mn13 complex with S6 symmetry by using 2-phenoxybenzoate.

The synthesis, structure and magnetic properties of [Mn(13)O(8)(OEt)6(O(2)CC(6)H(4)OPh)12] are reported as the first example of a high nuclearity manganese complex with 2-phenoxybenzoate: the complex possesses S6 symmetry and an S = 11/2 ground state.

Structure-activity relationships for cytotoxic ruthenium(II) arene complexes containing N,N-, N,O-, and O,O-chelating ligands.

We report structure-activity relationships for organometallic RuII complexes of the type [(eta6-arene)Ru(XY)Cl]Z, where XY is an N,N- (diamine), N,O- (e.g., amino acidate), or O,O- (e.g., beta-diketonate) chelating ligand, the arene ranges from benzene derivatives to fused polycyclic hydrocarbons, and Z is usually PF6. The X-ray structures of 13 complexes are reported. All have the characteristic "piano-stool" geometry. The complexes most active toward A2780 human ovarian cancer cells contained XY=ethylenediamine (en) and extended polycyclic arenes. Complexes with polar substituents on the arene or XY=bipyridyl derivatives exhibited reduced activity. The activity of the O,O-chelated complexes depended strongly on the substituents and on the arene. For arene=p-cymene, XY=amino acidate complexes were inactive. Complexes were not cross-resistant with cisplatin, and cross-resistance to Adriamycin was circumvented by replacing XY=en with 1,2-phenylenediamine. Some complexes were also active against colon, pancreatic, and lung cancer cells.

Synthesis and structural characterisation of polynuclear cobalt complexes with partially-deprotonated Bis-tris.

The synthesis and crystal structures of [Co4Na2(HL)2(H2L)2(MeOH)4] and [Co5(HL)2(H2L)2] are reported as the first examples of polynuclear transition metal complexes assembled using partially-deprotonated Bis-tris {2-[bis(2-hydroxyethyl)amino]-2-(hydroxymethyl)propane-1,3-diol, H5L}.

Design of base metal extractants. Part 1. Inter-ligand hydrogen bonding in the assembly of pseudo-macrocyclic bis(aminosulfonamidato)M(II) complexes.

Monosulfonyl derivatives of simple 1,2- and 1,3-diamines (R2HN-R-NHSO2R1 = L) have been shown to be easily deprotonated to give neutral 2:1 complexes, [M(L - H)(2)], with Co(II), Ni(II), Cu(II) or Zn(II). The Ni(II) and Cu(II) complexes with deprotonated N-tosyl-1,2-diaminoethane have a planar N4(2-) donor set and a 14-membered pseudo-macrocyclic structure based on head-to-tail S=O...H-N((amine)) bonding between the two bidentate ligands. In the related tetrahedral Zn(II) complex the ends of the mutually perpendicular bidentate N2- units are too far apart to form a cyclic H-bonded system. X-Ray structure determinations on five free ligands provide evidence for extensive inter-molecular H-bonding, which in the case of N-tosyl-1,3-diaminopropane and its N'-tert-butyl derivative involves formation of dimeric 16-membered pseudo-macrocycles. Despite favourable inter-ligand H-bonding in the neutral 2:1 complexes, these ligands are relatively weak extractants, showing >50% loading of Cu(II) in "pH-swing" equilibria, 2L(org)+ M2+ = [M(L - H)2](org)+ 2 H+, only when the pH of the aqueous phase is raised above 4.

Towards a system for the systematic structural study of intermolecular interactions in crystals of transition metal complexes.

Pseudo-macrocyclic complexes of copper(II), and in one instance nickel(II), incorporating the bidentate ligands methyl N-(4-oxo-5,5-diphenyl-4,5-dihydro-1H-imidazol-2-yl)imidocarbamate and N,N-dimethyl-N'-(4-oxo-5,5-diphenyl-4,5-dihydro-1H-imidazol-2-yl)guanidine are reported and their X-ray structures compared with those previously reported for related complexes of two N-(4-oxo- 5,5-diphenyl-4,5-dihydro-1H-imidazol-2-yl)alkanimidamides. A feature of these complexes is that they are capable of forming hydrogen bonded chains or chains in which adjacent complexes are linked by phenyl 'embraces'. Changes in supramolecular structure arising from small changes in ligand structure or on crystallisation from different solvents are also discussed.

New cobalt(II) and zinc(II) coordination frameworks incorporating a pyridyl-pyrazole ditopic ligand.

The metal-directed assembly of new molecular frameworks incorporating 4-(4-pyridyl)pyrazole (L), containing non-linear coordination vectors, is presented. Three metallo-arrays of types [Co(LH)2(NO3)4], [Co(LH)2(H2O)4][NO3]4.H2O and [Zn2(L-H)2Cl2].2EtOH are reported. The cobalt(II) in [Co(LH)2(NO3)4] displays distorted octahedral geometry, with the two protonated pyridyl-pyrazole ligands coordinated through their pyrazole nitrogen atoms in a trans-orientation; the remaining four coordination sites are occupied by nitrate anions. Two internal hydrogen bonds occur between each pyrazole NH and the oxygens of adjacent coordinated nitrato ligands. Short intermolecular hydrogen bonds also occur between the two pyridinium hydrogens and bound nitrate ligands on different molecules to yield a two-dimensional hydrogen-bonded array. Two of these arrays interpenetrate to form an extended two dimensional layer; such layers stack throughout the crystal structure. A second product of type [Co(LH)2(H2O)4][NO3]4.H2O exists as two crystallographically independent, but chemically similar, forms. In each form, the two protonated pyridyl-pyrazole ligands occupy trans positions about the cobalt, with the remaining four coordination sites being filled by water molecules to yield a distorted octahedral coordination geometry. Intramolecular hydrogen-bonding is observed between the two non-coordinated pyrazoyl nitrogen atoms and bound water oxygen atoms. The third complex, [Zn2(L-H)2Cl2].2EtOH, contains dimer units consisting of two zinc(II) ions bridged by two pyrazoylate groups in which the coordination geometry of each zinc approximates a tetrahedron. Each zinc is bound to two deprotonated pyridine-pyrazole ligands (L-H), one pyridyl group (from a different dimeric unit) and one chloro ligand. Each pyridyl nitrogen thus connects each of these zinc dimers to an adjacent dimer unit, forming a three-dimensional network containing small voids. The latter are occupied by ethanol molecules which form hydrogen bonds to the chloro ligands.