Mark R. St J. Foreman

Hydrothermal synthesis of polymeric metal carboxylates from benzene-1,2,4,5-tetracarboxylic acid and benzene-1,2,4-tricarboxylic acid

Abstract Crystallisation of benzene-1,2,4,5-tetracarboxylic acid or benzene-1,2,4-tricarboxylic acid with divalent metal-ions Co, Mn or Zn and 2,2-bipyridyl gives coordination solids of composition [Co2(C10H2O8)(C10H8N2)2(H2O)] (1), [Co3(C9H3O6)2(C10H8N2)2(H2O)2] (2), [Mn3(C9H3O6)2(C10H8N2)2(H2O)2] (3) or [Zn3(C9H3O6)2(C10H8N2)2(H2O)2] (4). Each has a sheet structure with a distorted octahedral coordination environment.

Hydrothermal synthesis and characterisation of lead(II) benzene-1,3,5-tricarboxylate [Pb3BTC2]H2O: a lead(II) carboxylate polymer

Abstract The coordination polymer of formula [Pb3BTC2]·H2O (BTC=1,3,5-benzenetricarboxylate) contains 2 different BTC trianions, 3 different Pb cations and 3 different carboxylate coordination modes.

Synthesis and characterisation of polymeric metal-ion carboxylates from benzene-1,3,5-tricarboxylic acid with Mn(II), Co(II) or Zn(II) and 2,2-bipyridyl, phenanthroline or a pyridyl-2-(1-methyl-1H-pyrazol-3-yl) derivative

A total of 13 new co-ordination solids have been prepared of composition [Co(HBTC)(PHEN)(H2O)] (12), [Mn-3(BTC)(2)(PHEN)(3)] (13), [Mn(HBTC)(6)(H2O)] (14), [Mn(HBTC)(7)(H2O)] (15), [Zn-3(BTC)(2)(6)(3)(H2O)(3)]. 4H(2)O (16), [Zn-(HBTC)(6)(H2O)] (17), [Zn(H2BTC)(2)(6)] (18), [Zn(HBTC)(7)(H2O)] (19), [Zn(HBTC)(8)(H2O)] (20), [Zn-2(HBTC)(2)(9)(2)]. 2H(2)O (21), [Zn(HBTC)(10)(H2O)].H2O (22), [Co(HBTC)(10)(H2O)].H2O (23) and [Co(HBTC)(11)(H2O)] (24) 6 = pyridine-2-(1-methyl-1H-pyrazol-3-yl); 7 = pyridine-2-(1-methyl-4-bromo-1H-pyrazol-3-yl); 8 = pyridine-2-(1-methyl-4-nitro-1H-pyrazol-3-yl); 9 = pyridine-2-(1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl); 10 = pyridine-2-(1-methyl-5-tert-butyl-1H-pyrazol-3-yl); 11 = pyridine-2-(1-methyl-4-nitro-5-tert-butyl-1H-pyrazol-3-yl). Compounds 12, 14, 15 and 24 have similar structures which contain metal atoms in M2O2 rings. Compounds 17, 19 and 20 all contain single stranded coordinative chains. At low temperatures compounds 14 and 15 both have high spin S = 5 ground states.

Hydrothermal crystallisation of metal (II) orotates (M=nickel, cobalt, manganese or zinc). Effect of 2,2-bipyridyl, 2,2-dipyridyl amine, 1-methyl-3-(2-pyridyl)pyrazole, phenanthroline and 2,9-dimethyl-1,10-phenanthroline upon structure

Abstract Hydrothermal synthesis of orotic acid (H3L) with Ni(OAc)2·4H2O gives a green 1D co-ordinative network of composition [Ni(HL)(H2O)3] (3). The kinetic product [Ni(HL)·(H2O)4]H2O (4) can be prepared by conventional crystallisation. When boiled in water it is transformed into the thermodynamically favoured trihydrate 3. An unstable blue phase 5 that could not be characterised was also observed. Hydrothermal synthesis of orotic acid and M(OAc)2·4H2O (M=Ni, Co, Mn or Zn) and either 2,2-bipyridyl (bipy), 2,2-dipyridylamine (dpa), phenanthroline (phen), methyl-3-(2-pyridyl)pyrazole (pypz) or 2,9-dimethyl-1,10-phenanthroline (dmphen) gave infinite 1D co-ordinative networks of composition [M(HL)bipy(H2O)] (M=Co or Mn) (6–7) and complexes of composition [Ni(HL)bipy (H2O)2]2H2O (8); [Ni(HL)(dpa)(H2O)2]H2O (9); [Ni(HL)(phen)(H2O)2]·2H2O (10); [Ni(HL)(C9H9N3)(H2O)2]·2H2O (11); [Ni(HL)(dmphen)(H2O)] (12); [Zn(HL)bipy(H2O)] (13) and [Ni(HL)(dpa)2]·0.5H2O (14).

One-dimensional structures of manganese(II), copper(II) and cobalt(II) coordination complexes [MnII(hfac)2L] (hfac=hexafluoroacetylacetonate anion; L=4,4-bipyridyl), [CuII(hfac)2L] (L=1,3-dipyridylpropane or 4,4-bipyridyl-N,N′-dioxide) and [CoII(hfac)2L] (L=4,4-bipyridyl-N,N′-dioxide)

Abstract Treatment of bis(hexafluoroacetylacetonato)diaquamanganese(II) [Mn(hfac) 2 (H 2 O) 2 ] with 4,4-bipyridyl gives cis -[Mn II (hfac) 2 (bipy)] ( 1 ), which forms zig-zag 1-D chains. The bipyridyl ligands coordinate to the Mn cations adopting a cis geometry with an NMnN angle of 90°. Treatment of bis(hexafluoroacetylacetonato)diaquacopper(II) [Cu(hfac) 2 (H 2 O) 2 ] with 1,3-dipyridylpropane gives trans -[Cu II (hfac) 2 (1,3-dipy)] ( 2 ), which forms 1-D chains that adopt a trans NCuN angle of 180°. Treatment of [M(hfac) 2 (H 2 O) 2 ] (M=Co or Cu) with 4,4-bipyridyl- N , N ′-dioxide gives trans -[Co II (hfac) 2 (4,4-bipy- N , N ′-dioxide)] ( 3 ) and trans -[Cu II (hfac) 2 (4,4-bipy- N , N ′-dioxide)] ( 4 ), respectively, which form isostructural linear chains with an OMO angle of 180°.

Synthesis and characterisation of polymeric manganese and zinc 5-hydroxyisophthalates

The crystallisation of 5-hydroxyisophthalic acid with divalent Mn or with Mn or Zn and either 2,2-bipyridine (2,2-bipy) or pyridine-2-(1H-pyrazol-3-yl) gave solids of composition [Mn(C8H4O5)(H2O)3]·2H2 O( 1), [Mn(C8H4O5)(2,2-bipy)]·H2 O( 2), [Mn2(C8H4O5)2(C8H7N3)2]·H2 O( 3) and [Zn(C8H4O5)(2,2-bipy)] (4). Each compound has 1D co-ordinative chains that are connected by hydrogen bonds. Compounds 2–4 contain M2C2O4 rings with pseudo-chair geometries. The Mn atoms in 2 are coupled antiferromagnetically.

Synthesis of co-ordination networks from flexible bis-(4-pyridyl) ligands and cadmium salts.

Abstract Crystallisation of flexible dipyridyl ligands with Cd(NO3)2·4H2O, Cd(ClO4)2·xH2O or Cd(NO3)2·4H2O and KSCN gives co-ordination networks of composition [Cd(ClO4)2(Py2C3H6)2(H2O)2]·Py2C3H6 1 (Py2C3H6 =1,3-bis(4-pyridyl)propane); [Cd(ClO4)2(Py2C2H4)3] 2 (Py2C2H4 =1,2-bis(4-pyridyl)ethane); [Cd(NCS)2(Py2C3H6)] 3; [Cd2(NO3)4(o-C6H4(CH2CH24-Py)2)4] 4 (o-C6H4(CH2CH2Py)2 =1,2-bis[2-(4-pyridyl)ethyl] benzene and [Cd(NO3)2(PyCH2CH2CH=CHCH2CH2Py)3] 5 (PyCH2CH2CH=CHCH2CH2Py =1,6-bis(4-pyridyl)hex-3-ene). The compounds were characterised by X-ray single crystal diffraction studies which revealed the presence of different polymeric motifs. Structures 1 and 5 consist of 1-D polymeric chains, structure 4 consists of a 2-D polymeric network and structure 3 is a 3-D polymeric network. None of these exhibit lattice interpenetration. However structure 2 consists of three identical but independent interpenetrating 3-D lattice networks.

One-dimensional structures of nickel(II) and cobalt(II) coordination complexes {[ML2(H2O)2]·L·H2O·(ClO4)2} (M=Co or Ni; L=1,3-bis(4-pyridyl)propane)

Treatment of 1,3-bis(4-pyridyl)propane with Co(II)(ClO4)(2) or Ni(II)(ClO4)(2) gives isostructural one-dimensional coordination polymers. The metal ions have an octahedral geometry and are bridged by two crystallographically independent ligands along each chain. Alongside each coordination chain an array of non-coordinated ligands are hydrogen bonded at each end to the ligated water molecules.

Structures of Mn(II) thiocyanate co-ordination polymers from flexible bipyridyl ligands

Crystallisation of flexible bipyridyl ligands with MnCl 2 ·4H 2 O and KSCN gives co-ordination polymers of composition [Mn(NCS) 2 (H 2 O) 2 (Py 2 C 2 H 4 )](Py 2 C 2 H 4 ) 2 (H 2 O) 2 ( 1 ) (Py 2 C 2 H 4 =1,2-bis(4-pyridyl)ethane), [Mn 2 (NCS) 4 (Py 2 C 3 H 6 ) 4 ] n ( 2 ) (Py 2 C 3 H 6 =1,3-bis(4-pyridyl)propane) and [Mn(NCS) 2 (CH 3 CH 2 OH) 2 (Py 2 C 6 H 12 )] n ( 3 ) (Py 2 C 6 H 12 =1,6-bis(4-pyridyl)hexane). The structures were solved by single crystal structure determinations.

Synthesis and characterisation of infinite coordination networks with 1,6-bis(4-pyridyl)hexane and copper nitrate

Crystallisation of 1,6-bis(4-pyridyl)hexane (Py2C6H12) with copper nitrate gives two different phases. Phase I of composition [Cu(Py2C6H12)(3)(NO3)(2)].2[Cu(Py2C6H12)(2)(H2O)(NO3)].2(NO3). EtOH consists of two different infinite chains in a 1:2 ratio that are interlocked. Hydrogen bonds link chains I to II and chains II to II. In contrast phase 2 of composition [Cu-2(Py2C6H12)(4)(H2O)(2)]. (NO3)(4). (Py2C6H12). (EtOH).2(H2O) is based upon an infinite 3D framework. It consists of four interpenetrating 3D networks that are crystallographically equivalent.