2,7-Dichloro-6-O-methylnorlichexanthone

We report the hydro-thermal syntheses and crystal structures of aqua-bis-(2,2'-bi-pyridine-κ2 N,N')copper(II) hexa-fluorido-silicate tetra-hydrate, [Cu(bpy)2(H2O)][SiF6]·4H2O (bpy is 2,2'-bi-pyridine, C10H8N2), (I), bis-(2,2'-bi-pyridine-3κ2 N,N')-di-μ-fluorido-1:3κ2 F:F;2:3κ2 F:F-deca-fluorido-1κ5 F,2κ5 F-ditantalum(V)copper(II), [Cu(bpy)2(TaF6)2], (II), tris-(2,2'-bi-pyridine-κ2 N,N')copper(II) bis[hexa-fluorido-tantalate(V)], [Cu(bpy)3][TaF6]2, (III), and catena-poly[[di-aqua-(2,2'-bi-pyridine-κ2 N,N')copper(II)]-μ-fluorido-tetra-fluorido-tin-μ-fluorido], [Cu(bpy)(H2O)2SnF6] n , (IV). Compounds (I), (II) and (III) contain locally chiral copper coordination complexes with C 2, D 2, and D 3 symmetry, respectively. The extended structures of (I) and (IV) are consolidated by O-H⋯F and O-H⋯O hydrogen bonds. The structure of (III) was found to be a merohedral (racemic) twin.

In the title compound, C19H17Cl2N3O2, there are three mol-ecules (A, B and C) in the asymmetric unit and each differs in the conformation adopted. As a result of steric repulsion, the amide group is rotated with respect to both the dichloro-phenyl and 2,3-dihydro-1H-pyrazol-4-yl rings, making dihedral angles of 44.5 (2) and 56.2 (2)°, respectively in A, 51.1 (2) and 54.1 (2)° in B, and 53.8 (2) and 54.6 (2)° in C. The dihedral angles between the dichloro-phenyl and 2,3-dihydro-1H-pyrazol-4-yl rings are 54.8 (2), 76.2 (2) and 77.5 (2)° in mol-ecules A, B and C, respectively, while the 2,3-dihydro-1H-pyrazol-4-yl and phenyl rings make dihedral angles of 45.3 (2), 51.2 (2) and 42.8 (2)°, respectively. In the crystal, two of the mol-ecules are linked through N-H⋯O hydrogen bonding to an adjoining mol-ecule, forming dimers of the R2(2)(10) type, while the third mol-ecule forms such dimers with itself. C-H⋯O inter-actions link the dimers.

The zwitterionic complex formed by NiII and 2,2':6',2″-terpyridine-4'-carboxylate, Ni(tpyc)2, has been used as a coligand with a diverse group of polycarboxylates in uranyl ion complexes synthesized under solvo-hydrothermal conditions, thus giving a series of 14 mixed ligand, heterometallic compounds. Both [(UO2)2(c-1,2-chdc)Ni(tpyc)2(NO3)2]2·4CH3CN (1) and [(UO2)2(tdc)Ni(tpyc)2(NO3)2]2 (2), where c-1,2-chdc2- is cis-1,2-cyclohexanedicarboxylate and tdc2- is 2,5-thiophenedicarboxylate, display discrete U4Ni2 dinickelatetrauranacycles, a motif which is also found as part of a daisychain coordination polymer in [(UO2)4(bdc)3Ni2(tpyc)4(NO3)2]·2CH3CN·2H2O (3), where bdc2- is 1,4-benzenedicarboxylate. Similar U4Ni2 rings associate to form a nanotubular polymer in [(UO2)2(tca)Ni(tpyc)2(NO3)]·2CH3CN·2H2O (4), where tca3- is tricarballylate. [(UO2)2(1,2-pda) (1,2-pdaH)Ni(tpyc)2(NO3)]·CH3CN (5), where 1,2-pda2- is 1,2-phenylenediacetate, crystallizes as a meander-like chain in which each bent section can be seen as an open, semi-U4Ni2 ring. Oxalate (ox2-) gives [(UO2)2(ox)2Ni(tpyc)2] (6), a monoperiodic polymer containing smaller U4Ni rings, while 1,2,3-benzenetricarboxylate (1,2,3-btc3-) and citrate (citH3-) give [Ni(tpycH)(H2O)3][UO2(1,2,3-btc)]2·2H2O (7) and [UO2Ni2(tpyc)4][UO2(citH)]2 (8), two complexes with charge separation, the latter displaying one-periodic + two-periodic semi-interpenetration. [(UO2)2(btcH)Ni(tpyc)2(NO3)] (9) and [(UO2)2(cbtcH)Ni(tpyc)2(NO3)] (10), where btc4- and cbtc4- are 1,2,3,4-butanetetracarboxylate and cis,trans,cis-1,2,3,4-cyclobutanetetracarboxylate, respectively, are diperiodic networks with hcb topology, and [(UO2)2(ndc)Ni(tpyc)2(OH)(NO3)] (11), where ndc2- is 2,6-naphthalenedicarboxylate, is a sql network containing dinuclear nodes and involving 100-membered U10Ni4 metallacyclic units. U4Ni2 rings are found in the diperiodic polymer formed in [(UO2)4(t-R-1,2-chdc)4Ni2(tpyc)4] (12), where t-R-1,2-chdc2- is trans-R,R-1,2-cyclohexanedicarboxylate, the heavily puckered sheets being interlocked. 1,3-Phenylenediacetate (1,3-pda2-) gives a very thick diperiodic polymer with KIa topology, [(UO2)4(1,3-pda)4Ni2(tpyc)4]·CH3CN·2H2O (13). A triperiodic framework is formed with nitrilotriacetate (nta3-) in [(UO2)2(nta)2Ni2(tpyc)2] (14), where NiII is found in Ni(tpyc)2 units as well as in Ni(nta)24- moieties which both act as 4-coordinated nodes.