1,5-Bis(2-hy-droxy-3-meth-oxy-benzyl-idene)carbonohydrazide methanol 0.47-solvate.

In the title compound, C17H18N4O5·0.47CH3OH, the virtually planar (r.m.s. deviation = 0.128 Å) carbonohydrazide mol-ecule is located on a twofold axis and conformation of its C=N bonds is E. There are short intra-molecular O-H⋯N hydrogen bonds between the hy-droxy groups and hydrazide N atoms. In the crystal, bifurcated N-H⋯(O,O) hydrogen bonds assemble the carbonohydrazide mol-ecules into a three-dimensional network. There are C 2 symmetric voids in this network, 47% of which are occupied by disordered methanol mol-ecules.

Crystal structure of 1-(1,3-benzo-thia-zol-2-yl)-3-(4-bromo-benzo-yl)thio-urea.

The chemical reaction of 4-bromo-benzoyl-chloride and 2-amino-thia-zole in the presence of potassium thio-cyanate yielded a white solid formulated as C15H10BrN3OS2, which consists of 4-bromo-benzamido and 2-benzo-thia-zolyl moieties connected by a thio-urea group. The 4-bromo-benzamido and 2-benzo-thia-zolyl moieties are in a trans conformtion (sometimes also called s-trans due to the single bond) with respect to the N-C bond. The dihedral angle between the mean planes of the 4-bromo-phenyl and the 2-benzo-thia-zolyl units is 10.45 (11)°. The thio-urea moiety, -C-NH-C(=S) -NH- fragment forms a dihedral angle of 8.64 (12)° with the 4-bromo-phenyl ring and is almost coplanar with the 2-benzo-thia-zolyl moiety, with a dihedral angle of 1.94 (11)°. The mol-ecular structure is stabilized by intra-molecular N-H⋯O hydrogen bonds, resulting in the formation of an S(6) ring. In the crystal, pairs of adjacent mol-ecules inter-act via inter-molecular hydrogen bonds of type C-H⋯N, C-H⋯S and N-H⋯S, resulting in mol-ecular layers parallel to the ac plane.

Crystal structure of poly[hexa-µ-bro-mido-bis{2-[1-(py-ri-din-2-yl)ethyl-idene-amino]ethanol-ato}tetracopper(II)].

The reaction of the Schiff base 2-[1-(pyridin-2-yl)ethyl-idene-amino]-ethanol (HL), which is formed by reaction of 2-amino-ethanol and 2-acetyl-pyridine with CuBr2 in ethanol results in the isolation of the new polymeric complex poly[hexa-µ-bromido-bis-{2-[1-(pyridin-2-yl)ethyl-idene-amino]-ethano-lato}tetra-copper(II)], [Cu4Br6(C9H11N2O)2]n or [Cu4Br6 L 2]n. The asymmetric unit of the crystal structure of the polymeric [Cu4Br6 L 2]n complex is composed by four copper (II) cations, two monodeprotonated mol-ecules of the ligand, and six bromide anions, which act as bridges. The ligand mol-ecules act in a tridentate fashion through their azomethine nitro-gen atoms, their pyridine nitro-gen atoms, and their alcoholate O atoms. The crystal structure shows two types of geometries in the coordination polyhedrons around Cu2+ ions. Two copper cations are situated in a square-based pyramidal environment, while the two other copper cations adopt a tetra-hedral geometry. Bromides anions acting as bridges between two metal ions connect the units, resulting in a tetra-nuclear polymer compound.

Dichlorido{N'-[phen-yl(pyridin-2-yl-κN)methyl-idene]isonicotinohydrazide-κ(2)N',O}zinc.

The title compound, [ZnCl(2)(C(18)H(14)N(4)O)], crystallizes with two mol-ecules in the asymmetric unit, which differ in the tautomeric (neutral and zwitterionic) forms of the coordin-ating organic ligand. In both mol-ecules, the Zn(II) atom adopts a distorted square-pyramidal geometry by two N and one O atoms of the Schiff base ligand and two Cl atoms acting as monodentate chloride anions. The crystal packing is stabilized by N-H⋯N and N-H⋯Cl hydrogen bonds, forming a two-dimensional network parallel to the ac plane.

Aqua-{2-(pyridin-2-yl)-N-[(pyridin-2-yl)methyl-idene]ethanamine-κ(3) N,N',N''}(sulfato-κ(2) O,O')copper(II) tetra-hydrate.

The title complex, [Cu(SO4)(C13H13N3)(H2O)]·4H2O, was obtained by mixing copper sulfate penta-hydrate and 2-(pyridin-2-yl)-N-(pyridin-2-yl-methyl-idene)ethanamine in eth-anol under reflux conditions. The Cu(II) ion shows a Jahn-Teller-distorted octa-hedral geometry, with equatorial positions occupied by three N atoms from the tridentate ligand (average Cu-N = 2.004 Å) and one O atom from a bidentate sulfate anion [Cu-O = 1.963 (2) Å]. The axial positions are occupied by one O atom from a coordinating water mol-ecule [Cu-O = 2.230 (3) Å] and one weakly bonded O atom [Cu-O = 2.750 (2) Å] from the bidentate sulfate ion. The complex mol-ecules are connected through O-H⋯O hydrogen bonds between the coordinating water mol-ecules and sulfate ions from neighboring complexes, forming a double chain parallel to the c axis. The chains are stabilized through additional hydrogen bonds by one of the non-coordinating water mol-ecules bridging between neighboring strands of the double chains. The remaining three water mol-ecules fill the inter-stitial space between the double chains and are involved in an intricate hydrogen-bonding network that consolidates the structure.

Synthesis and crystal structures of two related Co and Mn complexes: a celebration of collaboration between the universities of Dakar and Southampton.

We report the synthesis and structures of two transition-metal complexes involving 2-(2-hy-droxy-phen-yl)benzimidazole (2hpbi - a ligand of inter-est for its photoluminescent applications), with cobalt, namely, bis-[µ-2-(1H-1,3-benzo-diazol-2-yl)phenolato]bis-[ethanol(thio-cyanato)-cobalt(II)], [Co2(C13H9N2O)2(NCS)2(C2H6O)2], (1), and manganese, namely, bis-[µ-2-(1H-1,3-benzo-diazol-2-yl)phenolato]bis-{[2-(1H-1,3-benzo-diazol-2-yl)phenolato](thio-cyanato)-mang-an-ese(III)} dihydrate, [Mn2(C13H9N2O)4(NCS)2]·2H2O, (2). These structures are two recent examples of a fruitful collaboration between researchers at the Laboratoire de Chimie de Coordination Organique/Organic Coordination Chemistry Laboratory (LCCO), University of Dakar, Senegal and the National Crystallography Service (NCS), School of Chemistry, University Southampton, UK. This productive partnership was forged through meeting at Pan-African Conferences on Crystallography and quickly grew as the plans for the AfCA (African Crystallographic Association) developed. This article therefore also showcases this productive partnership, in celebration of the IUCr's 75 year anniversary and the recent inclusion of AfCA as a Regional Associate of the IUCr.

Syntheses and crystal structure of 4-[(pyridin-3-yl)diazen-yl]morpholine and 1-[(pyridin-3-yl)diazen-yl]-1,2,3,4-tetra-hydro-quinoline.

Two new heterocyclic 1,2,3-triazenes were synthesized by diazo-tation of 3-amino-pyridine following respectively by coupling with morpholine or 1,2,3,4-tetra-hydro-quinoline. 4-[(Pyridin-3-yl)diazen-yl]morpholine (I), C9H12N4O, has monoclinic P21/c symmetry at 100 K, while 1-[(pyridin-3-yl)diazen-yl]-1,2,3,4-tetra-hydro-quinoline (II), C14H14N4, has monoclinic P21/n symmetry at 100 K. These 1,2,3-triazene derivatives were synthesized by the organic medium method by coupling reactions of 3-amino-pyridine with morpholine and 1,2,3,4-tetra-hydro-quinoline, respectively, and characterized by 1H NMR, 13C NMR, IR, mass spectrometry, and single-crystal X-ray diffraction. The mol-ecule of compound I consists of pyridine and morpholine rings connected by an azo moiety (-N=N-). In the mol-ecule of II, the pyridine ring and the 1,2,3,4-tetra-hydro-quinoline unit are also connected by an azo moiety. The double- and single-bond distances in the triazene chain are comparable for the two compounds. In both crystal structures, the mol-ecules are connected by C-H⋯N inter-actions, forming infinite chains for I and layers parallel to the bc plane for II.

Dichlorido[2-(pyridin-2-yl)-N-(pyridin-2-yl-methyl-idene)ethanamine-κ(3)N,N',N'']manganese(II) monohydrate.

In the title complex, [MnCl(2)(C(13)H(13)N(3))]·H(2)O, the Mn(II) atom is in a distorted square-pyramidal environment, with an Addison τ parameter of 0.037. The coordination geometry is defined by three N-atom donors from the tridentate 2-(pyridin-2-yl)-N-(pyridin-2-yl-methyl-idene)ethanamine ligand and two terminal Cl atoms. Although the H atoms of the lattice water molecule were not located, O⋯O distances of 3.103 (7) Šand O⋯Cl distances of 3.240 (3) and 3.482 (4) Šsuggest that hydrogen bonding is responsible for the stabilization of the crystal packing.

(S,E)-3-[(2-Hy-droxy-benzyl-idene)amino]-2-(2-hy-droxy-phen-yl)-2,3-dihydro-quinazolin-4(1H)-one.

In the title compound, C(21)H(17)N(3)O(3), the dihydro-quinazoline ring adopts a screw-boat conformation and its stereogenic C atom has an S configuration. The dihedral angle between the mean planes of the two hy-droxy-phenyl rings is 86.61 (12)°. The amino H atom forms an intra-molecular hydrogen bond with a phenol O atom, while the hydrazine N atom acts as an acceptor for the H atom of the other phenol group. In the crystal, O-H⋯N and O-H⋯O hydrogen bonds and weak C-H⋯centroid(π-ring) inter-molecular inter-actions are observed, forming chains along [1-10] and [110].

Bis(2-{[2-(2-hy-droxy-benzyl-amino)-eth-yl]amino-meth-yl}phenolato-κN,N',O)cobalt(III) nitrate monohydrate.

In the title compound, [Co(C(16)H(19)N(2)O(2))(2)]NO(3)·H(2)O, the Co(III) ion is located on an inversion center and is six-coordinated by two phenolate O atoms and four amino N atoms from two diamine ligands, forming an octa-hedral geometry. The water mol-ecule and the nitrate anion are located close to an inversion center, and are thus equally disordered by symmetry. The crystal packing is stabilized by inter-molecular O-H⋯O hydrogen bonds involving the uncoordinated water mol-ecule and the free phenol hydroxyl group with the nitrate anion. N-H⋯O hydrogen bonds involving the amino groups and the nitrate anions connect the complex mol-ecules along the c axis.

Bis{2-amino-2-oxo-N-[(1E)-1-(pyridin-2-yl-κN)ethyl-idene]acetohydrazidato-κ(2)N',O(1)}nickel(II).

In the title compound, [Ni(C(9)H(9)N(4)O(2))(2)], the Ni(II) ion is situated on a twofold rotation axis and is coordinated by two O and four N atoms from two tridentate {2-amino-2-oxo-N-[(1E)-1-(pyridin-2-yl-κN)ethyl-idene]acetohydrazidate ligands in a distorted octa-hedral geometry. In the crystal, N-H⋯O and N-H⋯N hydrogen bonds link the mol-ecules into columns in [001]. The porous crystal packing is further stabilized via π-π inter-actions between the pyridine rings of neighbouring mol-ecules [centroid-centroid distance = 3.746 (3) Å] with voids of 270 Å(3).

Synthesis, crystal structure and Hirshfeld surface analysis of tert-butyl N-acetyl-carbamate.

This article reports a practical synthesis of tert-butyl acetyl-carbamate, C7H13NO3, from N-Boc-thio-acetamide and the study of its crystal structure. The reaction proceeds in the presence of natural phosphate as a catalyst, with excellent yield, simple workup and benign environment. The crystal structure was refined using a transferred multipolar atom model. In the crystal, symmetrical pairs of strong N-H⋯O hydrogen bonds connect the mol-ecules into dimers with an R 2 2(8) ring motif. The inter-actions between neighbouring dimers are mostly van der Waals, between hydro-phobic methyl groups. Hirshfeld surface analysis shows the major contributions to the crystal packing are from H⋯H (42.6%) and O⋯H (26.7%) contacts.

Tetra-nuclear copper(II) complex of 2-hydroxy-N,N'-bis-[1-(2-hy-droxy-phen-yl)ethyl-idene]-propane-1,3-di-amine.

The title mol-ecular structure, namely, (µ3-acetato)(µ2-acetato)-bis-(µ3-1,3-bis-{[1-(2-oxidophen-yl)ethyl-idene]amino}-propan-2-olato)tetra-copper(II) monohydrate, [Cu4(C19H19N2O3)2(CH3CO2)2]·H2O, corresponds to a non-symmetric tetra-nuclear copper complex. The complex exhibits one ligand mol-ecule that connects two copper CuII metal centres via its ethano-lato oxygen anion acting in a µ2-mode and one ligand mol-ecule that connects three copper CuII metal centres via its ethano-lato oxygen anion acting in a µ3-mode. One bridging acetate group acting in an η1:η1-µ2-mode connects two copper(II) ions while another bridging acetate group connects three copper(II) ions in an η1:-η2-µ3-mode. A chair-like Cu3O3 structure is generated in which the two CuO4N units are connected by one µ2-O ethano-late oxygen atom. These two units are connected respectively to the CuO3N unit via one µ3-O ethano-late oxygen atom and one µ2-O atom from an acetate group. The µ3-O atom also connects one of the CuO4N units and the CuO3N unit to another CuO3N unit, which is out of the chair-like structure. Each of the two penta-coordinated CuII cations has a distorted NO4 square-pyramidal environment. The geometry of each of the two CuNO3 units is best described as a slightly square-planar environment. A series of intra-molecular O-H⋯O hydrogen bonds is observed. In the crystal, the units are connected by inter-molecular C-H⋯O and O-H⋯O hydrogen bonds, thus forming sheets parallel to the ac plane.

Poly[di-µ-aqua-diaqua-di-µ(6)-malonato-cobalt(II)dipotassium(I)].

In the title complex, [CoK(2)(C(3)H(2)O(4))(2)(H(2)O)(4)](n), the Co atom is located on a position with site symmetry 2/m, the K atom and one water mol-ecule are located on a mirror plane, and the malonate and one water mol-ecule are located on a twofold rotation axis. The K(I) atom is seven-coordinated by four carboxyl-ate O atoms from four malonate ligands and by three water O atoms, forming a distorted polyhedron. The Co(II) atom is in an almost octa-hedral environment formed by four carboxyl-ate O atoms from two malonate ligands and two water O atoms. The structure consists of layers parallel to (20[Formula: see text]) built up from edge-sharing KO(7) and CoO(6) polyhedra, which are connected by O-H⋯O hydrogen bonding including water mol-ecules into a three-dimensional network.

1-(Thio-phen-2-yl)ethanone thio-semi-carbazone.

The title compound, C(7)H(9)N(3)S(2), crystallizes with two unique mol-ecules in the unit cell, both present as thio-semicarbazide tautomers. The mol-ecules differ principally in the dihedral angles between the thio-phene ring planes and the planes through the non-H atoms of the hydrazinecarbothio-amide units, viz. 9.80 (8)° for one mol-ecule and 19.37 (7)° for the other. The hydrazinecarbothio-amide units are reasonably planar, with r.m.s. deviations of 0.001Å for each of the mol-ecules. In the crystal, N-H⋯S hydrogen bonds link like mol-ecules into R(2) (2)(8) inversion dimers. A three-dimensional network structure is generated by additional N-H⋯S hydrogen bonds and weak C-H⋯S contacts between the unique mol-ecules.

Bis(N,N'-dimethyl-ethylenediammonium) tris-(oxalato-κO,O)cobaltate(II) dihydrate: an ion-pair complex.

The Co(II) ion in the title complex, (C(4)H(14)N(2))(2)[Co(C(2)O(4))(3)]·2H(2)O, is coordinated by three oxalate ions, resulting in a distorted octa-hedral geometry. Two uncoordinated water mol-ecules are present in asymmetric unit. Inter-molecular N-H⋯O and O-H⋯O hydrogen bonds between the different entities stabilize the crystal structure.

N,N'-Dimethyl-ethylenediammonium dioxalatocuprate(II).

The asymmetric unit of the title salt, (C(4)H(14)N(2))[Cu(C(2)O(4))(2)], consists of one complex anion and two cationic half-mol-ecules, the other halves being generated by inversion symmetry. The Cu(II) atom in the anion is coordinated by two bidentate oxalate ligands in a distorted square-planar geometry. Inter-molecular hydrogen bonds, involving the NH groups as donors and O atoms as acceptors, are observed, which lead to the formation of a three-dimensional network structure.

(2-{[2-(2-Amino-ethyl-amino)-ethyl-imino]-meth-yl}phenolato-κO,N',N'',N''')copper(II) perchlorate.

The asymmetric unit of the title complex, [Cu(C(11)H(16)N(3)O)]ClO(4), consists of two Cu(II) ions coordinated by Schiff base ligands and two perchlorate anions. The Schiff base mol-ecules are linked to the Cu(II) atoms via three N atoms and one O atom, resulting in a square-planar geometry. Inter-molecular hydrogen bonds involving the NH groups as donors and O atoms of the perchlorate anions as acceptors are observed.

Hexanuclear copper(II) complex of 2-hy-droxy-N,N'-bis-[1-(2-hy-droxy-phen-yl)ethyl-idene]propane-1,3-di-amine incorporating an open-cubane core.

The title mol-ecular structure, namely, di-aqua-tris-(µ3-1,3-bis-{[1-(2-oxidophen-yl)ethyl-idene]amino}-propan-2-olato)-µ3-hydroxido-dinitrato-hexa-copper(II) ethanol tris-olvate, [Cu6(C19H19N2O3)3(NO3)2(OH)(H2O)2]·3C2H5OH, corres-ponds to a non-symmetric hexa-nuclear copper complex. The complex exhibits one core in which three CuII metal centres are mutually inter-connected, two by two, via three phenolato oxygen anions acting in a µ2-mode. These three copper cations are inter-connected in a µ3-mode by one hydroxyl group. An open-cube structure is generated in which each of the CuII cations of the three CuO4N units is connected by two µ2-O anions from phenolate groups and one µ3-O atom from a hy-droxy anion. Each of the three penta-coordinated CuII cations situated in the open-cube unit has a distorted NO4 square-pyramidal environment. Each of these three CuII centres is inter-connected with another CuII cation via one enolate O atom in µ2-mode, yielding one CuNO4 unit and two CuNO3 units. The penta-coordinated CuII atom has a distorted square-pyramidal environment while the two tetra-coordinated copper(II) cations are situated in a square-planar environment. A series of intra-molecular O-H⋯O hydrogen bonds are observed. In the crystal, the units are connected two by two by inter-molecular C-H⋯O and O-H⋯O hydrogen bonds, thus forming sheets parallel to the ac plane.

{2-[(2-Acetyl-hydrazin-1-yl-idene)methyl-κN,O]-6-methoxy-phenolato-κO}(nitrato-κO)copper(II) monohydrate.

In the title complex, [Cu(C(10)H(11)N(2)O(3))(NO(3))]·H(2)O, prepared from the Schiff base N'-(3-meth-oxy-2-oxidobenzyl-idene)-acetohydrazide, the Cu(II) atom is coordinated by two O atoms and one N atom from the ligand and one O atom from a nitrate group in a distorted square-planar geometry. The Cu(II) atom has a weak inter-action with another O atom of the nitrate group. The two O atoms of the tridentate Schiff base ligand are in a trans arrangement. O-H⋯O and N-H⋯O hydrogen bonds involving the uncoordinated water mol-ecule are observed.