Bis(glycinato‐κ2N,O)dinitrosylmolybdenum(0) and bis(2‐aminoethanethiolato‐κ2N,S)dinitrosylmolybdenum(0) acetonitrile monosolvate

The title compounds, [Mo(C₂H₄NO₂)₂(NO)₂], (I), and [Mo(C₂H₆NS)₂(NO)₂]·CH₃CN, (II), contain distorted octahedral complexes in which the monoanionic N,S‐ and N,O‐bidentate ligands coordinate the molybdenum centres in different modes. The anionic O atoms of the glycinate ligands in (I) are coordinated trans to the nitrosyl ligands and the amine N atoms are located trans to each other, whereas in (II) the anionic S atoms are coordinated trans to each other and the amine N atoms are located trans to the nitrosyl ligands. Each compound has a single complete complex in the asymmetric unit on a general position. Six N—H...O contacts with N...O distances of less than 3.2 Å are observed in (I) between the amine groups and the nitrosyl and carboxylate O atoms. In the 1:1 solvate (II), the acetonitrile molecule forms short N—H...N contacts (N...N < 3.2 Å) between the solvent N atoms and one of the amine H atoms. In addition, three weak intermolecular N—H...S interactions (N...S > 3.3 Å) contribute to the stabilization of the structure of (II).     

Tetrakis(μ‐guanidino­acetic acid‐κ2O:O′)­bis­[(nitrato‐κO)copper(II)]

The title compound, [Cu₂(NO₃)₂(C₃H₇N₃O₂)₄], forms a centrosymmetric dimer, with the two Cu²⁺ ions separated by 2.6525 (6) Å. The asymmetric unit contains a Cu atom coordinated to two guanidino­acetic acid ligands (via one carboxyl­ate O atom from each ligand) and to a nitrate group. The inversion centre in P generates the entire mol­ecule, in which each Cu atom is coordinated to four carboxyl­ate and to one nitrate O atom; ignoring the Cu—Cu separation, the geometry about each Cu atom is square pyramidal. The amino acid ligand is in the zwitterionic form. Strong N—H?O hydrogen bonds lead to a three‐dimensional supramolecular structure, in which the N?O distances are in the range 2.931 (4)–3.278 (3) Å, with N—H?O angles ranging from 128 to 170°.     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.     

Bis(4,4′‐bi­pyridine‐κN)­bis­(hydrogen phthalato)‐κ2O,O′;κO‐zinc(II)

The title compound, [Zn(C₈H₅O₄)₂(C₁₀H₈N₂)₂], was obtained by the hydro­thermal reaction of ZnSO₄·7H₂O with phthalic acid (H₂pht) and 4,4′‐bi­pyridine (4,4′‐bipy). Crystallographic analysis shows that it has a one‐dimensional double‐chain structure via hydrogen‐bonding interactions. Each Zn^II atom, adopting a distorted tetrahedral geometry, is coordinated by two N atoms from two 4,4′‐bipy ligands, with Zn—N distances of 2.054 (4) and 2.104 (4) Å, and by two O atoms from symmetry‐related Hpht⁻ ligands, with Zn—O distances of 1.921 (4) and 2.019 (4) Å.     

Hexa­aqua­bis­(di­methyl sulfoxide)­yttrium(III) trichloride

The title compound, [Y(C₂H₆OS)₂(H₂O)₆]Cl₃, contains the cation [Y(H₂O)₆{(CH₃)₂SO}₂]³⁺ with a distorted square antiprismatic geometry of the eight coordinated O atoms. The six water mol­ecules are coordinated with an average Y—O distance of 2.38 (2) Å, ranging from 2.360 (3) to 2.404 (3) Å. Each water mol­ecule forms two hydrogen bonds to the chloride anions with O—Cl distances ranging from 3.068 (4) to 3.422 (4) Å. The two di­methyl­ sulfoxide ligands, situated in the cis position with the O—Y—O angle equal to 83.22 (11)°, have Y—O distances of 2.269 (3) and 2.278 (3) Å.     

Bis(4‐hydroxy­benzoato‐O)(1,4,8,11‐tetra­aza­cyclo­tetra­decane‐κ4N)nickel(II): a three‐dimensional framework built from O—H⋯O and N—H⋯O hydrogen bonds

The title compound, [Ni(C₇H₅O₃)₂(C₁₀H₂₄N₄)], contains octahedral Ni^II in a centrosymmetric trans configuration with Ni—N distances of 2.0637 (17) and 2.0699 (16) Å and an Ni—O distance of 2.1100 (14) Å. The mol­ecules are linked by a single type of O—H?O hydrogen bond [O?O 2.618 (2) Å and O—H?O 161°] into two‐dimensional sheets; a singletype of N—H?O hydrogen bond [N?O 2.991 (2) Å and N—H?O 139°] links these sheets into a three‐dimensional framework.     

Chloro{2,2′‐[(1S,2S)‐1,2‐di­phenyl‐1,2‐ethanediyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ4O,N,N′,O′}(ethanol‐κO)­manganese(III)

The crystal structure of the title compound, [MnCl(C₂₈H₂₂N₂O₂)(C₂H₆O)], has been determined at 173 (2) K in the non‐centrosymmetric space group P2₁2₁2₁. The asymmetric unit contains two molecular units. An intermolecular O—H⋯Cl hydrogen bond is formed between the OH group of an ethanol mol­ecule coordinated to the Mn atom and the coordinated Cl⁻ anion, and so polymeric chains of Mn‐containing fragments are formed [O—H⋯Cl = 3.1281 (16) and 3.1282 (15) Å]. The Mn atoms have a pseudo‐octahedral coordination sphere, with the four donor atoms of the Schiff base forming an equatorial plane [Mn—O distances are 1.8740 (13), 1.8717 (13), 1.8749 (13) and 1.8823 (13) Å, and Mn—N distances are 1.9868 (15), 1.9910 (14), 1.9828 (15) and 1.9979 (14) Å]. The axial positions are occupied by an ethanol mol­ecule [Mn—O distances of 2.3069 (15) and 2.3130 (15) Å] and a Cl⁻ ligand [Mn—Cl distances of 2.5732 (6) and 2.5509 (6) Å].     

Tetrapotassium dicarbonato­dioxo­peroxo­uranium(VI) 2.5‐hydrate,K4[U(CO3)2O2(O2)]·2.5H2O

The title compound was obtained by reacting UO₂ powder in 2 M K₂CO₃ with hydrogen peroxide. The compound contains individual [U(CO₃)₂O₂(O₂)]⁴⁻ ions, which are linked via an extended network of K atoms and hydrogen bonding. The U atom is coordinated to two trans‐axial O atoms and six O atoms in the equatorial plane, forming distorted hexagonal bipyramids. The carbonate ligands are bound to the U center in a bidentate manner, with U—O bond distances ranging from 2.438 (5) to 2.488 (5) Å. The peroxo group forms a three‐membered ring with the U atom, with U—O bond distances of 2.256 (6) and 2.240 (6) Å. The U=O bond distances of 1.806 (5) and 1.817 (5) Å, and an O—U—O angle of 175.3 (3)° are characteristic of the linear uranyl(VI) unit.     

Chains of fused rings in the hydrogen‐bonded structure of meso‐­6,13‐di­amino‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane–2,2′‐biphenol (1/2)

The title compound is a salt, [C₁₂H₃₂N₆]²⁺·2[HOC₆H₄C₆H₄O]^?. The centrosymmetric cation contains two intramolecular N—H?N hydrogen bonds with an N?N distance of 2.8290 (13) Å, and the pendent amino groups are in axial sites; the anion contains an intramolecular O—H?O hydrogen bond with an O?O distance of 2.4656 (11) Å. The ions are linked into continuous chains by means of four types of N—H?O hydrogen bonds with N?O distances ranging from 2.7238 (12) Å to 3.3091 (13) Å, associated with N—H?O angles in the range 148–160°.     

Bis(tetraphenylphosphonium) tris(oxalato‐O,O′)germanate(IV)

The synthesis and structure of the title compound, (C₂₄H₂₀P)₂[Ge(C₂O₄)₃], are reported. The PPh₄⁺ cations in the structure form infinite zigzag chains in which the P?P distances alternate between 6.229 (1) and 7.118 (1) Å, and the P?P?P angle is 131.4 (1) Å. The shorter P?P distance is associated with a sixfold phenyl embrace. However, the longer P?P distance is associated with both phenyl–phenyl interactions and interactions between the cations and a twofold symmetric [Ge(C₂O₄)₃]^2? anion. In the cation–anion interactions, the P?O distance is 4.444 (2) Å, the O?P—C_distal angle is 175.0 (1)° and the shortest H?O distances are 2.74 and 3.09 Å.     

The cyclic vanadylacetate (C24H20P)[V4O8(C2H3O2)4(NO3)]

In the title complex, tetraphenylphosphonium μ₄‐nitrato‐κ⁴O‐cyclo‐tetrakis(μ‐acetato‐O:O′)tetra‐μ‐oxo‐tetrakis[oxovana‐dium(V)], the anion lies about a twofold axis and consists of the cyclic [V₄O₈] unit coordinated by four acetato ligands with interatomic V?V distances of 3.269 (1) and 3.273 (1) Å. The double‐bonded O atom [N=O 1.102 (6) and N—O 1.268 (4) Å] of the nitrato ligand links the four V atoms with V—O bond distances of 2.613 (2) and 2.813 (2) Å. The negative charge of the complex is balanced by tetraphenyl­phosphonium cations occupying the Na positions in the NaCl‐type ionic packing of the structure.     

Contributions on thermal behaviour and crystal chemistry of anhydrous phosphates. XIX. Tri-chromium(II)-bis-phosphate Cr3(PO4)2 (≙ Cr6(PO4)4) – A transition metal(II)-orthophosphate with new structure type

Deep blue-violet single crystals of hitherto unknown chromous orthophosphate have been obtained reducing CrPO₄ by elemental Cr at temperatures above 1050°C in evacuated silica ampoules (NH₄I or I₂ as mineraliser). The complex structure of Cr₃(PO₄)₂ (P2₁2₁2₁, Z = 8, a = 8.4849(10) Å, b = 10.3317(10) Å, c = 14.206(2) Å) contains six crystallographically independent Cr²⁺ per unit cell. Five of them are coordinated by four oxygen atoms which form a distorted (roof shaped) square plane as first coordination sphere at interatomic distances 1.96 Å ? d(Cr? O) ? 2.15 Å. Their coordination is completed by additional oxygen atoms (2 or 3) at distances 2.32 Å ? d(Cr? O) ? 3.21 Å. The sixth Cr²⁺ shows six-fold octahedral coordination with strong radial distortion (d(Cr? O): 1.97, 2.04, 2.15, 2.28, 2.29, 2.53 Å). The four different [PO₄] groups exhibit only minor deviations from ideal tetrahedral geometry (1.51 Å ? d(P? O) ? 1.57 Å, 104.3° ? ∠(O? P? O) ? 114.4°). An unusually low magnetic moment μ_exp = 4.28(2) μ_B (θ_P = ?54.8(5) K) has been observed for Cr²⁺.     

trans‐Bis(dimethyl sulfoxide‐κO)bis(3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylato‐κ2N1,O2)copper(II)

The title compound, [Cu(C₉H₅N₂O₃)₂(C₂H₆OS)₂], consists of octahedrally coordinated Cu^II ions, with the 3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylate ligands acting in a bidentate manner [Cu—O = 1.9116 (14) Å and Cu—N = 2.1191 (16) Å] and a dimethyl sulfoxide (DMSO) molecule coordinated axially via the O atom [Cu—O = 2.336 (5) and 2.418 (7) Å for the major and minor disorder components, respectively]. The whole DMSO molecule exhibits positional disorder [0.62 (1):0.38 (1)]. The octahedron around the Cu^II atom, which lies on an inversion centre, is elongated in the axial direction, exhibiting a Jahn–Teller effect. The ligand exhibits tautomerization by H‐atom transfer from the hydroxyl group at position 3 to the N atom at position 4 of the quinoxaline ring of the ligand. The complex molecules are linked through an intermolecular N—H...O hydrogen bond [N...O = 2.838 (2) Å] formed between the quinoxaline NH group and a carboxylate O atom, and by a weak intermolecular C—H...O hydrogen bond [3.392 (11) Å] formed between a carboxylate O atom and a methyl C atom of the DMSO ligand. There is a weak intramolecular C—H...O hydrogen bond [3.065 (3) Å] formed between a benzene CH group and a carboxylate O atom.     

Preparative and structural studies of halodimolybdates(II). IV. Synthesis and crystal structure of (pyH)3Mo2Br7(H2O)2

(pyH)₃Mo₂Br₇(H₂O)₂ (pyH = Pyridinium cation) was prepared from the solution of (NH₄)₅Mo₂Cl₉ · H₂O in 1:1 HBr by the addition of pyHBr. The compound has monoclinic unit cell: P 2₁/n with a = 10.250(4), b = 11.891(4), c = 11.971(3) Å and β = 112.86(2)°. Z = 2, D calcd. = 2.54, D obsd. = 2.52(2) g cm^?3. The structure has been refined to the unweighted and weighted residuals of 7.8 and 8.7%. The structure contains Mo₂Br₆(H₂O)₂^2?, C₅H₆N⁺ and Br^? ions. Short Mo? Mo distance 2.130(4) Å reflects the strong bond. H₂O is coordinated to molybdenum at 2.19(3) Å. Distribution of H₂O molecules and Br^? ions around Mo₂ is different from (picH)₂Mo₂X₆(H₂O)₂ (X = Br, I) and determined by the two-fold axes perpendicular to the Mo? Mo direction and the plane defined by two H₂O molecules and 2 Br atoms. Three independent Mo? Br distances are 2.574(4), 2.606(5) and 2.569(5) Å. Specific structure of the Mo₂Br₆(H₂O)₂^2? ion has no synthetic consequences and reaction with neutral aromatic nitrogen bases leads to the known Mo₂Br₄L₄ compounds.     

μ‐Terephthalato‐bis­[bis(1,10‐phenanthroline)copper(I)] diperchlorate

The title compound, [Cu₂(C₈H₄O₄)(C₁₂H₈N₂)₄](ClO₄)₂, was prepared from the hydro­thermal reaction of CuCl₂, 1,4‐di­cyano­benzene, 1,10‐phenanthroline and water at 443 K. The compound is a dimer in which the cation lies about an inversion center. The terephthalate moiety acts as a bridging ligand and the phenanthrolines as terminal ligands. The unique Cu atom is coordinated by two O and four N atoms in a distorted octahedral geometry, with Cu—O distances of 1.955 (2) and 2.815 (2) Å, and Cu—N distances of 2.008 (2) to 2.216 (2) Å.     

catena‐Poly­[[bis­(nitrato)(pyrimidine)­copper(II)]‐μ‐pyrimidine‐N:N′]

The title compound, [Cu(NO₃)₂(C₄H₄N₂)₂]_n, crystallizes as a linear polymeric compound with one pyrimidine ligand bridging between two Cu^II atoms and a second pyrimidine ligand coordinated in a monodentate manner. The distorted octahedral geometry around the Cu^II atom consists of two pyrimidine N atoms at distances of 2.033 (4) and 2.025 (4) Å, and two nitrate O atoms at distances at 1.987 (3) and 1.973 (3) Å. The apical positions are occupied by an N atom of a bridging pyrimidine ligand [2.291 (4) Å] and a nitrate O atom at a long distance of 2.781 (3) Å. The basal plane is almost planar, with trans angles of 176.23 (14) and 165.34 (15)°.     

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

The title compound, [Cu{N(CN)₂}(C₁₂H₈N₂)₂]BF₄, was prepared as part of our study of the shape of coordination polyhedra in five‐coordinated copper(II) complexes. Single‐crystal X‐ray analysis reveals that the structure consists of [Cu{N(CN)₂}(phen)₂]⁺ cations (phen is 1,10‐phenanthroline) and BF₄⁻ anions. The Cu centre is five‐coordinated in a distorted trigonal bipyramidal manner by four N atoms of two phen ligands and one N atom of a dicyanamide anion, which is coordinated in the equatorial plane at a distance of 1.996 (2) Å. The two axial Cu—N_phen distances have similar values [average 1.994 (6) Å] and are shorter than the two equatorial Cu—N_phen bonds [average 2.09 (6) Å]. This work demonstrates the effect of ligand rigidity on the shape of coordination polyhedra in five‐coordinated copper(II) complexes.     

trans‐Diaquabis(1H‐imidazole‐4,5‐di­carboxyl­ate‐κ2N3,O4)­manganese(II)

In the title compound, [Mn(C₅H₃N₂O₄)₂(H₂O)₂], the Mn^II atom lies on an inversion centre, is trans‐coordinated by two N,O‐bidentate 1H‐imidazole‐4,5‐di­carboxyl­ate monoanionic ligands [Mn—O = 2.202 (3) Å and Mn—N = 2.201 (4) Å] and two water mol­ecules [Mn—O = 2.197 (4) Å], and exhibits a distorted octahedral geometry, with adjacent cis angles of 76.45 (13), 86.09 (13) and 89.20 (13)°. The complete solid‐state structure can be described as a three‐dimensional supramol­ecular framework, stabilized by extensive hydrogen‐bonding interactions involving the coordinated water mol­ecules, the carboxy O atoms and the protonated imidazole N atoms of the imidazole‐4,5‐di­carboxyl­ate ligands.     

Bis­(tetra­methyl­ammonium) nona­decaoxohexamolybdenum(VI) mono­hydrate

The six Mo atoms in the title compound, (C₄H₁₂N)₂[Mo₆O₁₉].H₂O, form a standard octahedral cage through bridging O atoms. The [Mo₆O₁₉]^2? anion as a whole has O_h symmetry with three crystallographic fourfold axes aligned along Mo—O—Mo. There exist weak O?O hydrogen bonds (O100?O3 2.951 Å) between the terminal O3 atoms of the anions and O100 atoms of the solvate hydrates in the unit cell.     

Bis(methanol‐κO)dioxido[3,3′‐(1H‐1,2,4‐triazole‐3,5‐diyl)diphenolato‐κ3O,N4,O′]uranium(VI) methanol monosolvate

The structure of the title compound, [U(C₁₄H₉N₃O₂)O₂(CH₃OH)₂]·CH₃OH, is the first to be reported for an actinide complex including triazole ligands. The U^VI atom exhibits a pentagonal–bipyramidal NO₆ coordination environment, involving two axial oxide ligands [U=O = 1.766 (3) and 1.789 (3) Å], four equatorial O atoms [U—O = 2.269 (3)–2.448 (3) Å] from the ligand and the two coordinated methanol molecules, and one equatorial N atom [U—N = 2.513 (4) Å] from the ligand. In the crystal structure, the complex molecules are linked via intermolecular N—H...O and O—H...O hydrogen bonds to form a two‐dimensional structure.