The crystal structures of [6-nitro-12,14-dimethyl-3,9-bis(propylsulphonyl)-1,2,4,8,10,11-hexaazacyclotetra-deca-2,4,6,9,12, 14-hexaenato(2-)-N1, N4, N8, N11]nickel(II) and [12,14-dimethyl-3,9-bis(ethylsulphonyl)-1,2,4,8,10,11-hexaazacyclotetra-deca-2,4,6,9,12,14- hexaenato(2-)-N1, N4, N8, N11]nic... (original) (raw)
Related papers
Journal of Chemical Crystallography, 2008
A new isomer of [Ni(tet-a)] 2+ (assigned as c-isomer) (tet-a = C-meso-5,5,7,12,12,14-hexamethyl-1,4,8,11tetraazacyclotetradecane), which is found in the complex of trans-c-[Ni(tet-a)(NCS) 2 ], has been isolated from the reaction of b-[Ni(tet-a)](ClO 4) 2 with NaSCN in a mixture of MeOH-H 2 O (1:1, v/v) solution and characterized by X-ray crystallography. The complex crystallizes in orthorhombic Pca2(1) space group with the crystal cell parameters of a = 12.5787(10) Å , b = 11.6834(10) Å , c = 15.4019(12) Å , V = 2263.5(3) Å 3 , and Z = 4. The crystal structure shows that the complex is noncentrosymmetric. The conformations of the six-asymmetric centers are assigned as 1R,4R,8S,11S, 7R,14S or 1S,4S,8R,11R,7S,14R (Trans-III). The coordination polyhedron around the nickel atom is axially elongated octahedron with an N 6 chromophore. The association of the complex units through N(3)-HÁÁÁS(1) (2.665 Å) hydrogen bonding interactions leads one-dimensional hydrogen bonded network along c-axis.
Polyhedron, 2011
Nickel(II) compounds of a tri-amine mono-imine macrocycle: Preparations and structures of (5,a b s t r a c t Reduction of one imine function of (5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11diene)nickel(II) with 1 molar proportion of NaBH 4 produces as the major product the tri-amine-monoimine macrocyclic cation (5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradec-4-ene)nickel(II), Ni(tm)] 2+ . Pairs of isomeric singlet ground state perchlorate and tetrachlorozincate salts of [Ni(tm)] 2+ were prepared and the structures determined for the 1RS,8SR,11SR,12RS (labeled as b) and 1RS,8RS,11RS,12SR (labeled as a) tetrachlorozincate salts. Triplet ground state trans-b-[Ni(tm)(NCS) 2 ] and catena-trans-{b-Ni(tm)-NC-Ni(CN) 2 -CN-} n Á2nH 2 O have the macrocycle in planar coordination and a-[{Ni(tm)} 2 (C 2 O 4 )](ClO 4 ) 2 has the macrocycle folded. With pentane-2,4-dione the compounds [b- -meso-5,5,7,12,12,14hexamethyl-1,4,8,11-tetraazacyclotetradecane) with both square-planar and octahedral Ni(II) cations were prepared and the latter was structurally characterized. Isomerisation in solution of metastable a-[Ni(tm)] 2+ to stable b-[Ni(tm)] 2+ is extremely slow, even in base.
Polyhedron, 2002
Dithiophosphate and dithiophosphonate complexes of pentacoordinate nickel(II) containing the [Ni([12]aneN 3)] 2' fragment ([12]aneN 3 0/2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene ([12]aneN 3-mc1) and its 9-methyl derivative ([12]aneN 3-mc2)) were prepared by using a 'one-pot' synthesis. This consists of the reaction between the corresponding O ,O ?-dialkyldithiophosphoric acid HS(S)P(OR) 2 or (4-methoxyphenyl)-O-alkyldithiophosphonic acid and the hydroxo precursor [Ni([12]aneN 3)(m-OH)] 2 (PF 6) 2 in the appropriate alcohol ROH (R0/Me, Et, i Pr) as solvent to give [Ni([12]aneN 3)(S 2 P(OR) 2 ](PF 6) 2 or [Ni([12]aneN 3){S 2 P(p-CH 3 OPh)(OR)}](PF 6). Among them, [Ni([12]aneN 3-mc1)(S 2 P(OEt) 2 ](PF 6) (2) and [Ni([12]aneN 3-mc1){S 2 P(p-CH 3 O-Ph)(O i Pr)}](PF 6) (9) were characterised by means of X-ray diffraction measurements on a single crystal. These studies show that the dithiophosphate or dithiophosphonate are bonded to the nickel atom as chelating S ,S-ligands and the nickel atoms are in a distorted square pyramidal geometry. Complex 9 is the first structurally characterised example of an O-alkyldithiophosphonate Ni(II) derivative in a distorted square pyramidal geometry. Analytical (C, H, N, S), spectroscopic (IR, UV Á/Vis and 1 H NMR) and mass spectrometry (FAB) data have been used for structural assignments.
Polyhedron, 2002
Dithiophosphate and dithiophosphonate complexes of pentacoordinate nickel(II) containing the [Ni([12]aneN3)]2+ fragment ([12]aneN3=2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene ([12]aneN3-mc1) and its 9-methyl derivative ([12]aneN3-mc2)) were prepared by using a ‘one-pot’ synthesis. This consists of the reaction between the corresponding O,O′-dialkyldithiophosphoric acid HS(S)P(OR)2 or (4-methoxyphenyl)-O-alkyldithiophosphonic acid and the hydroxo precursor [Ni([12]aneN3)(μ-OH)]2(PF6)2 in the appropriate alcohol ROH (R=Me, Et, iPr) as solvent to give [Ni([12]aneN3)(S2P(OR)2](PF6)2 or [Ni([12]aneN3){S2P(p-CH3OPh)(OR)}](PF6). Among them, [Ni([12]aneN3-mc1)(S2P(OEt)2](PF6) (2) and [Ni([12]aneN3-mc1){S2P(p-CH3OPh)(OiPr)}](PF6) (9) were characterised by means of X-ray diffraction measurements on a single crystal. These studies show that the dithiophosphate or dithiophosphonate are bonded to the nickel atom as chelating S,S-ligands and the nickel atoms are in a distorted square pyramidal geometry. Complex 9 is the first structurally characterised example of an O-alkyldithiophosphonate Ni(II) derivative in a distorted square pyramidal geometry. Analytical (C, H, N, S), spectroscopic (IR, UV–Vis and 1H NMR) and mass spectrometry (FAB) data have been used for structural assignments.Dithiophosphate and dithiophosphonate complexes of pentacoordinate nickel(II) with the macrocycles 2,4,4-trimethyl-1,5,9-triazacyclododec-1-ene and its 9-methyl derivative have been prepared by reaction between [Ni([12]aneN3)(μ-OH)]2(PF6)2 and O,O′-dialkyldithiophosphoric acid or O-alkyldithiophosphonic acid, respectively, in the appropriate alcohol ROH.
Acta Crystallographica Section E Structure Reports Online, 2014
In the molecular structure of the title compound, [NaNi(C 18 H 18 N 2 O 4 )(NO 3 )(-CH 3 OH)], the Ni 2+ ion has a slightly distorted square-planar coordination environment defined by two N and two O atoms which belong to a Schiff base ligand, viz. 6,6 0 -dimethoxy-2,2 0 -[ethane-1,2-diylbis(nitrilomethanylylidene)]diphenolate. Seven O atoms form the coordination environment of the Na + ion: four from the Schiff base ligand, two from a bidentate chelating nitrate anion and one O atom from a coordinating methanol molecule. In the crystal, the bimetallic complexes are assembled into chains along the b-axis direction via weak C-HÁ Á ÁO hydrogen-bond interactions. Neighbouring chains are in turn connected through bifurcated O-HÁ Á ÁO hydrogen bonds that involve the coordinating methanol molecules and the nitrate anions, and throughstacking interactions between phenyl rings of neighbouring molecules.
Polyhedron, 1997
The hydroxo complexes [{Ni(N3-macrocycle)(p-OH)}2](CIO4)2 (N3-macrocycle = 2,4,4-trimethyl-1,5,9-triazacyclododec-l-ene (N3-mc) and 2,4,4,9-tetramethyl-l,5,9-triazacyclododec-l-ene (9-Me-N3-mc)) react with the appropriate ~-ketoimine to give five-coordinate nickel(II) complexes of the type [Ni(N3-macrocycle) (C6HsCOCHC(NR)CH3)](CIO4). The complexes have been studied by spectroscopic (IR, UV-vis, 1H NMR and NOE) and thermal methods. An X-ray diffraction study carried out with the complex [Ni(9-Me-N3-mc){C6HsCOCHC(NC6Hs)CH3}](ColO4) has established that the Ni atom presents a square pyramidal coordination and is displaced 0.325(1) A out of the basal plane towards the apical N1 atom.
Zeitschrift für Kristallographie - New Crystal Structures, 2021
C20H48Cl2N4NiO10S2, monoclinic, P21/n (no. 14), a = 8.657(2) Å, b = 15.233(4) Å, c = 11.956(3) Å, β = 102.737(2)°, V = 1537.9(7) Å3, Z = 2, R gt (F) = 0.0237, wR ref (F 2) = 0.0655, T = 93(2) K.
Acta Crystallographica Section E Structure Reports Online, 2009
2 ], the asymmetric unit contains a Ni II atom, two molecules of 2-(benzylamino)pyridine, a molecule of deprotonated o-vanillin (3-methoxysalicylaldehydate) and a bidentate nitrate anion. The Ni II center is six-coordinated by two pyridine N atoms from 2-(benzylamino)pyridine, two O atoms from o-vanillin and two O atoms from the nitrate anion. The crystal packing shows two hydrogen bonds from the amine N-H group to the deprotonated phenol O atom of the o-vanillin moieties, as well as weak C-HÁ Á ÁO secondary interactions. These interactions link the molecules into ribbons in the c direction. The steric requirement of the bidentate nitrate and its small bite angle [61.01 (3) ] cause some orientation of the two 2-(benzylamino)pyridine groups. As a result, this coordination environment of the Ni II center is distorted octahedral, as the trans angles range from 158.65 to 175.76 (3) and the cis angles range from 61.01 (3) (for the bidentate nitrate O atoms) to 102.30 (4) .
Inorganic Chemistry, 1994
The nickel(II) complexes of hexaaza macrocyclic ligands 1-4, which incorporate functional groups such as-OH and-CN into the pendant arms attached at the uncoordinated bridgehead nitrogen atoms, are synthesized by the simple template condensation of ethylenediamine, formaldehyde, and primary amines with the appropriate functional groups. The hydroxyl pendant groups in the nickel(I1) complex of 1 react with acetic anhydride to produce the Ni(I1) complex of 5. The Ni(I1) complexes of 1-5 are in a square-planar geometry in solution. Their UVIvis spectra and electrochemical data are slightly affected by the type of functional group and the length of the pendant chain. The pendant hydroxyl groups in [Ni(1)I2+ and [Ni(2)12+ do not coordinate Ni(II) ion in water at pH 5 13.0 and an ionic strength 1.0 M (NaC104) or at pH 5 10.0 and an ionic strength 0.1 M (NaC104). The nickel(I1) complex with macrocycle 3 forms a coordination polymer on crystallization. [Ni(2)](C104)2 (NiC14H34N6C12010) crystallizes in the monoclinic space group P211c with a = 8.724(2) A, b = 14.581(2) A, c = 9.255(2) A, p = 103.84(1)", and Z = 2. The structure was solved by the direct method and refined to R values of R = 0.0335 and wR(F) = 0.0785 for 175 1 observed reflections (F > 4a(F)) measured with Mo Ka radiation on an Enraf-Nonius CAD-4 diffractometer. The Ni(I1) ion forms a square-planar geometq, coordinated by four secondary nitrogen donors of the macrocycle with the average Ni-N bond distance of 1.929(2) A. The oxygen atoms of the pendant hydroxyl groups form hydrogen bondings with the secondary NH's of the neighboring macrocyclic ligands. Coordination polymer [Ni(3)],(BF&,, (NiC1&8N&Fg) crystallizes in the monoclinic space group P21/n with a = 8.269(1) A, b = 8.559(1) A, c = 15.814(2) A, , 8 = 101.27(1)", and Z = 2. The structure was solved by the direct method and refined to R values of R = 0.0485 and wR(F) = 0.1395 for 1509 observed reflections (F > 6a(F)) measured with Mo Ka radiation on an Enraf-Nonius CAD-4 diffractometer. In the Ni(II) coordination polymer, each Ni(II) ion in the macrocyclic unit is coordinated by two nitrile groups of the neighboring macrocycles. The Ni(I1) atom is virtually in an octahedral geometry with the average Ni-N(macrocyc1e) bond distance of 2.056(3) 8, and the Ni(I1)-N(nitri1e) bond distance of 2.162(4) A.