cis‐Dinitrito(1,4,8,11‐tetra­aza­cyclo­tetra­decane‐κ4N)­chromium(III) nitrite

In the title compound, [Cr(ONO)₂(cyclam)]NO₂ (cyclam is 1,4,8,11‐tetra­aza­cyclo­tetra­decane, C₁₀H₂₄N₂), the complex cation is located on a twofold symmetry axis. The central Cr atom has a distorted octahedral coordination, involving two Cr—O bonds, with the monodentate nitrite O atoms adopting a cis configuration, and four Cr—N bonds. The mean Cr—N and Cr—O distances are 2.0895 (14) and 1.9698 (14) Å.     

Tetrakis­[1‐(3‐chloro­propyl)‐1,2,4‐tri­azole‐κN4]­bis­(tetrafluoroborato‐κF)copper(II)

In the title complex, [Cu(BF₄)₂(1tpc)₄] [1tpc is 1‐(3‐chloro­propyl)‐1,2,4‐triazole, C₅H₈ClN₃], the copper(II) centres reside in a tetragonally distorted octahedral coordination environment. Four 1tpc ligands are coordinated to the metal atom via the N4 atom of the triazole rings in a square‐planar arrangement, with Cu—N bond lengths in the range 2.002 (2)–2.019 (2) Å. Two tetra­fluoro­borate anions, in the axial positions above and below the square plane, are weakly coordinated to the copper(II) centre, with Cu—F distances of 2.4009 (18) and 2.5096 (18) Å.     

Bis­[bis­(pyrimidin‐2‐yl‐κN)­amine](dicyan­amido‐κN1)(tri­fluoro­methanesulfonato‐κO)copper(II) ethanol hemisolvate forms a hydrogen‐bonded chain

In the crystal structure of [Cu(CF₃SO₃)(C₂N₃)(C₈H₇N₅)₂]·0.5C₂H₆O, the Cu^II atom adopts a distorted octahedral geometry, with the basal plane formed by two N atoms of one dipyrimidinyl­amine ligand, one N atom of the second pyrimidine ligand and a nitrile N atom of the dicyan­amide anion [Cu—N = 1.972 (2)–2.021 (2) Å]. The apical positions are occupied by an N atom of the second ligand [Cu—N = 2.208 (2) Å], and an O atom of the tri­fluoro­methane­sulfonate anion [Cu—O = 2.747 (2) Å] at a semi‐coordination distance. Pairs of inversion‐related N—H⋯N hydrogen bonds of the so‐called Watson–Crick type, augmented by two C—H⋯N contacts, link adjacent complexes into an infinite one‐dimensional chain running in the [101] direction.     

catena‐Poly­[[bis­(quinoxaline‐κN)cobalt(II)]‐di‐μ‐dicyan­amido‐κ2N1:N5] and catena‐poly­[[bis(quinoxaline‐κN)copper(II)]‐di‐μ‐dicyan­amido‐κ2N1:N5]

Two new complexes, [Co(C₂N₃)₂(C₈H₆N₂)₂], (I), and [Cu(C₂N₃)₂(C₈H₆N₂)₂], (II), are reported. They are essentially isomorphous. Complex (I) displays distorted octahedral geometry, with the Co atom coordinated by four dicyan­amide nitrile N atoms [Co—N = 2.098 (3) and 2.104 (3) Å] in the basal plane, along with two monodentate quinoxaline N atoms [Co—N = 2.257 (2) Å] in the apical positions. In complex (II), the Cu atom is surrounded by four dicyan­amide nitrile N atoms [Cu—N = 2.003 (3) and 2.005 (3) Å] in the equatorial plane and two monodentate quinoxaline N atoms [Cu—N = 2.479 (3) Å] in the axial sites, to form a distorted tetragonal–bipyramidal geometry. The metal atoms reside on twofold axes of rotation. Neighbouring metal atoms are connected via double dicyan­amide bridges to form one‐dimensional infinite chains. Adjacent chains are then linked by π–π stacking interactions of the quinoxaline mol­ecules, resulting in the formation of a three‐dimensional structure.     

Tetra­kis(1‐eth­yl‐1H‐1,2,4‐triazole‐κN4)bis­(nitrato‐κO)copper(II) and bis­(nitrato‐κO)tetra­kis­(1‐prop­yl‐1H‐1,2,4‐triazole‐κN4)copper(II)

The copper(II) environments for tetra­kis­(1‐eth­yl‐1,2,4‐triaz­ole)­dinitratocopper(II), [Cu(NO₃)₂(C₄H₇N₃)₄], and tetrakis­(1‐prop­yl‐1,2,4‐triazole)dinitratocopper(II), [Cu(NO₃)₂(C₅H₉N₃)₄], are distorted square bipyramidal. Both structures are centrosymmetric, with the copper(II) ions located at inversion centers coordinated by four N atoms of four triazole mol­ecules and by two O atoms of two nitrate ions in an elongated octa­hedral geometry. This elongation is a result of the Jahn–Teller effect. The largest distortion is that of the N—Cu—O angles, which differ from 90° by 5.68 (10)° in the eth­yl and 5.59 (8)° in the prop­yl derivative.     

trans‐Aquachloro[(1R,4R,8S,11S)‐6,13‐diammonio‐6,13‐dimethyl‐1,4,8,11‐tetra­azacyclo­tetra­decane‐κ4N1,4,8,11]nickel(II) trichloride trihydrate

The title compound, [NiCl(C₁₂H₃₂N₆)(H₂O)]Cl₃·3H₂O, has the bis­(diamine)‐substituted cyclic tetra­amine in a planar coordination to triplet ground‐state Ni^II [average Ni—N = 2.068 (3) Å], with a chloride ion [Ni—Cl = 2.4520 (5) Å] and a water mol­ecule [Ni—O = 2.177 (2) Å] coordinated in the axial sites. The amine substituents are protonated and equatorially oriented. The amine groups, ammonium groups, water molecules and chloride ions are linked by an extensive hydrogen‐bonding network.     

mer‐Di­aqua­bis(1H‐imidazole‐κN3)(orotato‐κ2N3,O4)­nickel(II)

The title mononuclear complex, [Ni(C₅H₂N₂O₄)(C₃H₄N₂)₂(H₂O)₂] or [Ni(HOr)(im)₂(H₂O)₂] (im is imidazole and H₃Or is orotic acid, or 2,6‐dioxo‐1,2,3,6‐tetra­hydro­pyrimidine‐4‐carboxylic acid), has been synthesized and the crystal structure determination is reported. The Ni^II ion in the complex has a distorted octahedral coordination geometry comprised of one deprotonated pyrimidine N atom and the adjacent carboxyl­ate O atom of the orotate ligand, two tertiary imidazole N atoms and two aqua ligands. An extensive three‐dimensional network of OW—H⋯O and N—H⋯O hydrogen bonds, and π–π and π–ring interactions are responsible for crystal stabilization.     

Chloro­(3,6,13,16‐tetraethyl‐2,7,12,17‐tetra­methyl­porphycenato‐κ4N)iron(III) chloro­form solvate

The X‐ray crystallographic analysis of the title complex, chloro­[3,10,13,20‐tetraethyl‐4,9,14,19‐tetra­methyl­penta­cyclo[16.2.1.1^2,5.1^8,11.1^12,15]­tetracosa‐2,4,6,8(23),9,12,14,16,18(21),19‐decaene]­iron(III) chloro­form solvate, [Fe(C₃₃H₃₇N₄)Cl]·CHCl₃, reveals a twisted macrocyclic framework with a slightly distorted rectangular pyramidal core, where the deviation of the central Fe^III atom from the least‐squares plane of the C₂₀N₄ core is 0.594 (1) Å. Some important bond distances are as follows: Fe—N 2.019 (3), 2.026 (3), 2.028 (3) and 2.034 (3) Å; Fe—Cl 2.232 (1) Å.     

Bis­[1,3‐bis(2‐methyl­tetrazol‐5‐yl‐κN4)­triazenido‐κN2]­nickel(II)

The title compound, [Ni(BMTT)₂], where BMTT is 1,3‐bis(2‐methyl­tetrazol‐5‐yl)­triazenide (C₄H₆N₁₁), presents a molecular complex with tridentate ligands. The tridentate mode of the ligand is realised through the central N atom of the triazene group and two N atoms of the two tetrazole rings. The [Ni(BMTT)₂] mol­ecule is the meridional isomer, with crystallographic symmetry in space group P4₂/n. The nickel centre has a distorted octahedral environment, with two axial Ni—N bonds of 2.041 (2) Å and four equatorial Ni—N bonds of 2.0739 (14) Å. The mol­ecules are linked together by van der Waals interactions only.     

catena‐Poly­[[[1,8‐bis(2‐hydroxy­ethyl)‐1,3,6,8,10,13‐hexa­aza­cyclo­tetra­decane]copper(II)]‐μ‐cyano‐[tri­cyano­nitro­soiron(III)]‐μ‐cyano]

The bimetallic title complex, [CuFe(CN)₅(C₁₂H₃₀N₆O₂)(NO)] or [Cu(L)Fe(CN)₅(NO)] [where L is 1,8‐bis(2‐hydroxy­ethyl)‐1,3,6,8,10,13‐hexa­aza­cyclo­tetra­decane], has a one‐dimensional zigzag polymeric –Cu(L)–NC–Fe(NO)(CN)₃–CN–Cu(L)– chain, in which the Cu^II and Fe^II centres are linked by two CN groups. In the complex, the Cu^II ion is coordinated by four N atoms from the L ligand [Cu—N(L) = 1.999 (2)–2.016 (2) Å] and two cyanide N atoms [Cu—N = 2.383 (2) and 2.902 (3) Å], and has an elongated octahedral geometry. The Fe^II centre is in a distorted octahedral environment, with Fe—N(nitroso) = 1.656 (2) Å and Fe—C(CN) = 1.938 (3)–1.948 (3) Å. The one‐dimensional zigzag chains are linked to form a three‐dimensional network via N—H⋯N and O—H⋯N hydrogen bonds.     

Bis­(dicyan­amido)(diethyl­enetri­amine‐κ3N)copper(II) and (dicyan­amido)(tri­ethyl­enetetr­amine‐κ4N)copper(II) dicyan­amide

Two new complexes, [Cu(C₂N₃)₂(dien)] (dien is diethyl­ene­tri­amine, C₄H₁₃N₃), (I), and [Cu(C₂N₃)(trien)](C₂N₃) (trien is triethyl­ene­tetr­amine, C₆H₁₈N₄), (II), have been characterized by single‐crystal X‐ray diffraction. Both complexes display a distorted tetragonal–pyramidal geometry. In (I), the Cu atom is coordinated in the basal plane by three diethyl­ene­tri­amine N atoms [Cu—N = 2.000 (2), 2.004 (2) and 2.025 (2) Å] and one terminal N atom [Cu—N = 1.974 (2) Å] from one monodentate dicyan­amide group, and in the apical position by one terminal N atom [Cu—N = 2.280 (2) Å] from the other monodentate dicyan­amide group. In (II), the Cu atom is surrounded by four triethyl­ene­tetr­amine N atoms [Cu—N = 2.012 (2), 2.014 (2), 2.019 (2) and 2.031 (2) Å in the basal plane] and a terminal N atom [Cu—N = 2.130 (2) Å in the apical site] from one monodentate dicyan­amide group. The other dicyan­amide anion is not directly coordinated to the metal atom. In both (I) and (II), hydro­gen‐bond interactions between the uncoordinated terminal N atoms of two dicyan­amide ions and the amine H atoms lead to the formation of three‐dimensional networks.     

Tris­[(R)‐lact­amide‐κ2O,O′]­zinc(II) tetra­bromo­zincate

The title compound, tris­[(R)‐2‐hydroxy­propan­amide‐κ²O,O′]­zinc(II) tetra­bromo­zincate, [Zn(C₃H₇NO₂)₃][ZnBr₄], contains one monomeric six‐coordinate zinc complex cation and one tetrahedral [ZnBr₄]²⁻ anion. Both Zn^II atoms lie on threefold axes. Coordination in the cation occurs via the amide and hydroxy O atoms [Zn—O = 2.074 (5) and 2.073 (6) Å] and has a distorted octahedral geometry, with cis‐O—Zn—O angles in the range 76.2 (2)–109.2 (2)°. In the crystal structure, the cations and anions are linked by N—H⋯Br and O—H⋯O hydrogen bonds, generating a three‐dimensional network.     

[2,2′‐(1,3,5,8,10,12‐Hexaazacyclotetradecane‐3,10‐diyl)diethanol‐κ4N1,N5,N8,N12]bis(thiocyanato‐κS)copper(II)

In the crystal structure of the title compound, [Cu(NCS)₂(C₁₂H₃₀N₆O₂)], the Cu atom lies on an inversion centre and has an elongated octahedral coordination, with Cu—N distances of 2.004 (2) and 2.015 (2) Å, and a Cu—S distance of 2.9696 (10) Å. The 2,2′‐ethanol chains are axially oriented. The mol­ecules are linked to form a three‐dimensional network via O—H?N, N—H?O and N—H?S hydrogen bonds.     

Low‐dimensional compounds containing cyano groups. X. (Dicyan­amido‐κN1)­bis(1,10‐phenanthroline‐κ2N,N′)copper(II) perchlorate

The title compound, [Cu(C₂N₃)(C₁₂H₈N₂)₂]ClO₄, represents a relatively rare class of compounds with dicyan­amide coordinated in a monodentate manner. The structure is formed by the [Cu{N(CN)₂}(phen)₂]⁺ complex cation (phen is 1,10‐phenanthroline) and an uncoordinated ClO₄⁻ anion. The Cu atom is five‐coordinate, with a slightly distorted trigonal–bipyramidal environment. The dicyan­amide ligand is coordinated through one nitrile N atom in the equatorial plane, at a distance of 2.033 (6) Å from the metal. The two axial Cu—N distances are similar [mean 1.999 (4) Å] and are substantially shorter than the remaining two equatorial Cu—N bonds [mean 2.087 (1) Å].     

[μ‐N,N′‐Bis(2‐amino­ethyl)­oxamidato(2–)]­bis­[(4,5‐di­aza­fluoren‐9‐one)­perchloratocopper(II)] 4,5‐di­aza­fluoren‐9‐one disolvate

The title compound, [Cu₂(C₆H₁₂N₄O₂)(ClO₄)₂(C₁₁H₆N₂O)₂]·2C₁₁H₆N₂O, contains a dinuclear copper(II) complex which lies about a twofold axis at the mid‐point of the C—C bond of the ox­amide ligand that bridges the two Cu^II atoms. The Cu·Cu distance is 5.215 (2) Å and the Cu atoms have distorted octahedral coordination geometry. Intramolecular N—H·O and N—H·N hydrogen bonds and intermolecular C—H·O hydrogen bonds, together with π–π stacking interactions, dominate throughout the crystal structure.     

Tetrakis­(tetra­hydro­furan‐κO)­lithium mer‐tris­(carbazolyl‐κN)‐trans‐di­chloro(tetra­hydro­furan‐κO)­zirconate

In the title compound, [Li(C₄H₈O)₄][ZrCl₂(C₁₂H₈N)₃(C₄H₈O)], the environment of the Zr atom is pseudo‐octahedral, with the three carbazolyl ligands in a mer configuration. The counter‐ion of the zirconium complex is composed of an Li atom surrounded by four tetra­hydro­furan (THF) mol­ecules. The THF mol­ecule attached to the Zr atom is disordered over two sites, as are two of the THF mol­ecules in the lithium moiety. All bond distances and angles are consistent with those in complexes with similar structural entities. The Zr—N bond distances are 2.2185 (18) and 2.167 (3) Å.     

Tetra­aqua(5‐fluoro­uracil‐1‐acetato‐O)copper(II) tetra­hydrate

In the title complex, [Cu(C₆H₄FN₂O₄)₂(H₂O)₄]·4H₂O, the Cu atom is located in the centre of a distorted octahedral geometry. The coordination atoms are six O atoms provided by two carboxyl­ate groups [coordinated in a monodentate mode, with Cu—O = 1.9551 (10) Å] and four water mol­ecules [Cu—O = 1.9241 (13) and 2.5771 (14) Å]. In addition, one intramolecular hydrogen bond and ten intermolecular hydrogen bonds make up a three‐dimensional network.     

Tetra­kis(μ2‐1,8‐naphthyridine)‐1:2κ4N:N′;3:4κ4N:N′‐bis­(μ2‐salicylato)‐1:4κ2O:O′;2:3κ2O:O′‐tetrakis­(salicylic acid)‐1κO,2κO,3κO,4κO‐tetra­silver(I)(4 Ag—Ag)

The title complex, [Ag₄(C₇H₅O₃)₂(C₈H₆N₂)₄(C₇H₆O₃)₄], lies about an inversion centre and has a unique tetra­nuclear structure consisting of four Ag^I atoms bridged by four N atoms from two 1,8‐naphthyridine (napy) ligands to form an N:N′‐bridge and four O atoms from two salicylate (SA) ligands to form an O:O′‐bridge. The Ag atoms have distorted octa­hedral coordination geometry. The centrosymmetric Ag₄ ring has Ag—Ag separations of 2.772 (2) and 3.127 (2) Å, and Ag—Ag—Ag angles of 107.70 (4) and 72.30 (4)°. All SA hydroxy groups take part in intra­molecular O—H⋯O hydrogen bonding. In the crystal packing, the napy rings are oriented parallel and overlap one another. These π–π inter­actions, together with weak inter­molecular C—H⋯O contacts, stabilize the crystal structure.     

Diacetatobis(2‐amino­benzothia­zole‐κN)cobalt(II)

The title complex, [Co(C₂H₃O₂)₂(C₇H₆N₂S)₂], contains a Co centre with a slightly distorted tetra­hedral coordination geometry, involving two acetate ligands and two N atoms from the thia­zole moiety [Co—O = 2.0025 (14) and 1.9953 (16) Å, and Co—N = 2.0524 (18) and 2.0568 (18) Å]. The inter­planar angle between the two benzothia­zole moieties is 77.86 (3)°. The amine groups, acting as donors, participate in intra‐ and inter­molecular N—H⋯O hydrogen bonds, with N⋯O distances in the range 2.806 (2)–2.857 (2) Å.     

cis‐Bis­(dicyan­amido)bis(1,10‐phen­an­throline)­manganese(II) and cis‐bis(dicyan­amido)­bis(1,10‐phen­an­thro­line)­zinc(II)

The title compounds are isomorphous, comprised of neutral monomeric [M(phen)₂(dca)₂] [(I): M = Mn, (II): M = Zn; phen is 1,10‐phenanthroline, C₁₂H₈N₂; dca is dicyan­amide, C₂N₃] mol­ecules. In the mol­ecule, the divalent metal ion is in a distorted octahedral coordination environment formed by six N atoms from the phen and dca ligands. The Mn—N [2.144 (2)–2.319 (2) Å] and Zn—N [2.075 (2)–2.245 (2) Å] distances are in agreement with the difference in size of the two divalent ions.