Crystal Structure,Magnetic Properties,and Electronic Structure of Ni(NCNH2)4Cl2 and Co(NCNH2)4Cl2

The crystal structures of Ni(NCNH₂)₄Cl₂ and Co(NCNH₂)₄Cl₂, the first complexes with cyanamide as a neutral ligand, have been determined from single crystal data (Im3m, Z = 6, a = 1259.3(2) pm, R₁ = 0.0245 for Ni(NCNH₂)₄Cl₂ and a = 1266.3(2) pm, R₁ = 0.0241 for Co(NCNH₂)₄Cl₂; both 329 intensities and 23 parameters). Ni²⁺ and Co²⁺ are octahedrally coordinated by four equatorial H₂NCN molecules and two axial chloride ions, and the 20 and 19 electron octahedral complexes are connected by a network of hydrogen bonds. The cyanamide ligands are slightly bent (166°), and the two N–C distances are 112 and 133 pm. Ni(NCNH₂)₄Cl₂/Co(NCNH₂)₄Cl₂ are Curie paramagnets with two/three unpaired electrons.     

8-羟基喹啉镍配合物[Ni2(HQ)3Q3]ClO4的晶体结构

8-羟基喹啉(HQ)是在化学分析中常用的试剂, 它与铝离子形成的配合物(AlQ3)也是目前有机电致发光领域最引人注目的明星分子. 在化学工业中, 8-羟基喹啉是有效的稀土及过渡金属的萃取剂, 它同中心离子的配合强度随条件改变亦有很大变化. 我们在钇和镍离子共同存在的条件下得到了标题化合物, 并测得其单晶结构.     

Synthesis,Crystal Structure,and Optical Properties of (CH3NH3)2CoX4 (X = Cl,Br, I,Cl0.5Br0.5, Cl0.5I0.5, Br0.5I0.5)

The reaction of methylammonium halides and cobalt halides yielded the organic‐inorganic hybrid compounds of general formula (CH₃NH₃)₂CoX₄. By varying the different halides, we were able to synthesize the whole row from Cl to I as well as some mixed halides compounds and to determinate the crystal structures. (CH₃NH₃)₂CoX₄ (X = Cl, Br, Cl_0.5Br_0.5, Br_0.5I_0.5) crystallize isotypic to (CH₃NH₃)₂HgCl₄ in space group P2₁/c with Z = 4 [X = Cl: a = 7.6483(9), b = 12.6885(18), c = 10.8752(12) Å, β = 96.639(9)°; X = Cl_0.5Br_0.5: a = 7.8271(9), b = 12.9543(9), c = 11.1007(11) Å, β = 96.320(8)°; X = Br: a = 7.9782(2), b = 13.1673(2), c = 11.2602(2) Å, β = 96.3260(10)° and X = Br_0.5I_0.5: a = 8.2435(12), b = 13.645(2), c = 11.5856(18) Å, β = 95.54(2)°]. The mixed halides show a statistic distribution in both cases. In (CH₃NH₃)₂CoCl₂I₂ an ordered variant is realized representing a new structure type [C2/m, Z = 4, a = 18.808(4), b = 7.3604(7), c = 10.4109(17) Å, β = 120.364(13)°]. (CH₃NH₃)₂CoI₄ crystallizes again isotypic to the respective mercury compound [(CH₃NH₃)₂HgCl₄] [Pbca, Z = 8, a = 10.9265(5), b = 12.1552(5), c = 20.9588(9) Å]. All structures are build up by inorganic tetrahedral [CoX₄]^2– anions and organic (CH₃NH₄)⁺ cations. Additionally the Raman spectra as well as the optical reflectance spectra are discussed.     

Isotype Strukturen einiger Hexaamminmetall(II)-halogenide von 3d-Metallen: [V(NH3)6]I2, [Cr(NH3)6]I2, [Mn(NH3)6]Cl2, [Fe(NH3)6]Cl2, [Fe(NH3)6]Br2, [Co(NH3)6]Br2 und [Ni(NH3)6]Cl2

The Structures of some Hexaammine Metal(II) Halides of 3 d Metals: [V(NH₃)₆]I₂, [Cr(NH₃)₆]I₂, [Mn(NH₃)₆]Cl₂, [Fe(NH₃)₆]Cl₂, [Fe(NH₃)₆]Br₂, [Co(NH₃)₆]Br₂ and [Ni(NH₃)₆]Cl₂ Crystals of yellow [V(NH₃)₆]I₂ and green [Cr(NH₃)₆]I₂ were obtained by the reaction of VI₂ and CrI₂ with liquid ammonia at room temperature. Colourless crystals of [Mn(NH₃)₆]Cl₂ were obtained from Mn and NH₄Cl in supercritical ammonia. Colourless transparent crystals of [Fe(NH₃)₆]Cl₂ and [Fe(NH₃)₆]Br₂ were obtained by the reaction of FeCl₂ and FeBr₂ with supercritical ammonia at 400°C. Under the same conditions orange crystals of [Co(NH₃)₆]Br₂ were obtained from [Co₂(NH₂)₃(NH₃)₆]Br₃. Purple crystals of [Ni(NH₃)₆]Cl₂ were obtained by the reaction of NiCl₂ · 6H₂O and NH₄Cl with aqueous NH₃ solution. The structures of the isotypic compounds (Fm3 m, Z = 4) were determined from single crystal diffractometer data (see “Inhaltsübersicht”). All compounds crystallize in the K₂[PtCl₆] structure type. In these compounds the metal ions have high-spin configuration. The orientation of the dynamically disordered hydrogen atoms of the ammonia ligands is discussed.     

Synthesis and Characterizaion of a New Inorganic-organic Sulfate Compound--Crystal Structure of [Ni(H2O)6][H2N(C2H4)2NH2](SO4)2

[Ni(H2O)6][H2N(C2H4)2NH2](SO4)2 is an inorganic-organic compound with a new open framework synthesized by hydrothermal method, and characterized by means of single-crystal diffraction and spectroscopic data. The compound crystallized in a monoclinic space group P21/n with a=1.29089(2) nm, b=1.06301(3) nm, c=1.33202(4) nm, β=114.0870(10)°, V=1.67127(8) nm3, Z=4, and was solved by using the direct method and the least-squares refinement converged at R=0.0214[I>2σ(I)]. The structure consists of isolated Ni(H2O)6 octahedra and SO4 tetrahedra, with both of them hydrogen-bonded to piperazine cations.     

[In2(HPO3)4]·(NH3CH2CH2NH3)的水热合成与晶体结构

用乙二胺作模板剂在水热条件下合成出一个新的三维开放骨架结构的亚磷酸铟[In2(HPO3)4]·(NH3CH2CH2NH3)(1), 并对其晶体结构进行了测定和表征.     

Tetrakis(acetonitrile)‐dibromo‐nickel(II)‐di‐acetonitrile, [Ni(CH3CN)4Br2]·2CH3CN

[Tetrakis(acetonitrile)‐dibromo‐nickel(II)]‐di‐acetonitrile was obtained from a solution of nickel(II) dibromide in acetonitrile at 258 K. The crystal structure [monoclinic, P2₁/n (no.14), a = 1005.5(5), b = 831.3(5) , c = 1131.7(5) pm, β = 106.263(5)°, V = 908.1(8)·10⁶ pm³, Z = 2, R₁ for 1580 reflections with I₀>2σ(I₀): 0.0505] contains sixfold coordinated Ni^II atoms. Two trans coordinating bromide anions and four equatorial acetonitrile molecules form an elongated octahedron around the central Ni^II atom. [Ni(CH₃CN)₄Br₂] octahedra are connected via hydrogen bonds to neighboring octahedra as well as to solvate acetonitrile molecules.     

Crystal Structure,Thermal and Electric Behaviour of [(CH3)2NH2]3[As2Cl9] and [(CH3)2NH2][AsOCl2]

Single crystals of the organic‐inorganic arsenate(III): [(CH₃)₂NH₂]₃[As₂Cl₉] and [(CH₃)₂NH₂][AsOCl₂] have been grown from aqueous hydrochloric acid solution. The crystals [(CH₃)₂NH₂]₃[As₂Cl₉] have been investigated by X‐ray diffraction (at 253 K), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dilatometric and dielectric methods. They undergo two structural phase transitions of first order at 228/235 and 298/307 K (on cooling/heating), respectively, which are classified as an "order‐disorder" type. The trigonal [(CH₃)₂NH₂]₃[As₂Cl₉] structure (at 253 K, intermediate phase (II)) refined in the space group R3c, consists of isolated [As₂Cl₉]^3‐ bioctahedral units and dimethylammonium cations hydrogen bonded to the bridging Cl atoms of the anions. The crystals of [(CH₃)₂NH₂][AsOCl₂] at 100 K are orthorhombic, space group Cmca. The structure contains one‐dimensional chains formed by strong distorted [AsO₂Cl₄] octahedra. The dimethylammonium cations reveal distinct disorder.     

Preparation and Crystal Structure of Ni16Si9Al

The new ternary phase Ni₁₆Si₉Al was synthesized from the elements. The compound is formed in a presumably peritectoid reaction at 786 °C and has a narrow homogeneity range around the nominal composition. It adopts an orthorhombic structure (space group Cmcm) related to Ni₃Si₂. It was found, that one particular position is occupied by aluminum together with silicon causing slight splitting and thus leading to a local symmetry break in the structure. Both, Ni₁₆Si₉Al and Ni₃Si₂, show related structural motifs and can be described by a combination of flat layers and puckered slabs with interatomic distances indicating covalent interactions between the atoms.     

Synthesis,Crystal Structure,and Electrochemical Behaviour of an Azido μ‐bridged Ni2+ Complex

A homo‐dinuclear Ni^II complex was prepared from 2, 6‐bis(3, 5‐dimethylpyrazolyl)pyridine (Me₄‐bpp) and azide ions in nonaqueous media. It was characterized by single crystal X‐ray structural analysis, IR spectroscopy, and elemental analysis. In addition, the electrochemical properties of the compound were determined with cyclic voltammetry in DMF. The title compound crystallizes in the P2₁/n monoclinic space group, with unit cell parameters a = 8.978(1), b = 12.459(1), c = 17.764(1) Å, ß =100.603(3)°, V = 1953.0(3) ų, Z = 2. The Ni²⁺ ion has a distorted octahedral environment involving three nitrogen atoms of the Me₄‐bpp ligand, two nitrogen atoms from the bridged azide group, and one nitrogen atom from the terminal azide group. The Ni···Ni distance is 3.273(5) Å.     

Die Einwirkung von Ammoniumfluorid auf Scandium: Synthese und Kristallstrukturen von (NH4)3[ScF6] und [Cu(NH3)4]3[ScF6]2

Action of Ammonium Fluoride on Scandium: Synthesis and Crystal Structures of (NH₄)₃[ScF₆] and [Cu(NH₃)₄]₃[ScF₆]₂ The action of (NH₄)F on scandium in copper ampoules yields either (NH₄)₃[ScF₆] or ScF₃ and a small quantity of [Cu(NH₃)₄]₃[ScF₆]₂, respectively, depending upon the molar ratio of the educts (NH₄)F : Sc (6 : 1 and 4 : 1, respectively) and temperature. (NH₄)₃[ScF₆] crystallizes with the cryolite type of structure: monoclinic, P2₁/n, Z = 2; a = 650.0(2); b = 651.4(2); c = 949.0(2) pm; β = 90.40(2)°, [Cu(NH₃)₄]₃[ScF₆]₂ is triclinic, P‐1, Z = 1; a = 821.1(2); b = 821.2(2); c = 822.7(2) pm; α = 90.04(3); β = 90.00(3); γ = 90.16(3)°. In its chemical behaviour against (NH₄)F, scandium parallels aluminium rather than gallium.     

Metallampullen als Mini‐Autoklaven: Synthese und Kristallstrukturen der Ammoniakate [Al(NH3)4Cl2][Al(NH3)2Cl4] und (NH4)2[Al(NH3)4Cl2][Al(NH3)2Cl4]Cl2

Metal Ampoules as Mini‐Autoclaves: Syntheses and Crystal Structures of [Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄] and (NH₄)₂[Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄]Cl₂ The salts [Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–≡AlCl₃ · 3 NH₃ ( 1 ) and (NH₄⁺)²[Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–(Cl^–)₂≡ AlCl₃ · 3 NH₃ · (NH₄)Cl ( 2 ) have been obtained as single crystals during the reactions of aluminum and aluminum trichloride, respectively, with ammonium chloride in sealed Monel metal containers. The crystal structure of 1 was determined again [triclinic, P‐1; a = 574.16(10); b = 655.67(12); c = 954.80(16) pm; α = 86.41(2); β = 87.16(2); γ = 84.89(2)°], that of 2 for the first time [monoclinic, I2/m; a = 657.74(12); b = 1103.01(14); c = 1358.1(3) pm; β = 103.24(2)°].     

Umsetzung von C(NMe2)4 mit Ni(CO)4 – Synthesen und Strukturen von [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12] und [C(NMe2)3]3[Ni6(CO)12][O2CNMe2]

Reaction of C(NMe₂)₄ with Ni(CO)₄ – Syntheses and Structures of [C(NMe₂)₃][(CO)₃NiC(O)NMe₂], [C(NMe₂)₃]₂[Ni₅(CO)₁₂], and [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] The reaction of C(NMe₂)₄ with Ni(CO)₄ in THF produces the carbamoyl complex [C(NMe₂)₃][(CO)₃NiC(O)NMe₂] ( 1 ); side products are the purple cluster compound [C(NMe₂)₃]₂[Ni₅(CO)₁₂] · THF ( 2 · THF) and the red cocristallization product [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] ( 3 ). All compounds were studied by X‐ray diffraction analyses. The cations of 3 are all disordered but not those of 1 and 2 . The unit cell of 1 contains two crystallographically independent anions (I and II) which differ in the dihedral angle between the plane of the carbamoyl ligand and the plane defined by the atoms C_Carbamoyl–Ni–CO amounting 0° in the anion I and 18° in the anion II.     

Reaktionen am metallischen Substrat: Einkristalle von Ni(NH3)2V2F8

Reactions at the Metallic Substrate: Single Crystals of Ni(NH₃)₂V₂F₈ Except for the main product (NH₄)₂[TaF₇] and some [Ni(NH₃)₆][TaF₆]₂, the new light green Ni(NH₃)₂V₂F₈ is obtained by the reaction of (NH₄)F with tantalum and vanadium (molar ratio of (NH₄)F : Ta : V = 36 : 6 : 1) at 400 °C in a sealed Monel ampoule (Cu32Ni68). The crystal structure (orthorhombic, Fmmm, Z = 4, a = 752.9(1), b = 762.9(1), c = 1307.6(2) pm) is related to that of (NH₄)[VF₄]. According to {Ni(NH₃)₂}_0,5[VF₄], corrugated layers of vertex-connected octahedra [VF_4/2F_2/1] are stacked in the [001] direction. Between these layers trans-{Ni(NH₃)₂} units are inserted so that Ni²⁺ enhances its coordination number to 6 by two times two F^– from the layers above and below.     

Transition Metal Halide Salts and Complexes of 2-Aminopyrimidine: Cobalt(II) and Nickel(II) compounds,Crystal Structures of Bis(2-Aminopyrimidinium)MX4 [M = Co,Ni; X = Cl,Br] and 2-Aminopyrimidinium(+2) [NiBr2(H2O)4]Br2

The reaction of MX₂ (M = Co(II), Ni(II); X = Cl, Br) with 2-aminopyrimidine in aqueous acid yields compounds [(2-apmH)₂MX₄], (2-apmH)₂[MX₄], or (2-apmH₂) [MX₂(H₂O)₄]X₂ (2-apmH = 2-aminopyrimidinium; 2-apmH₂ = 2-aminopyrimidinium(2+)). All compounds have been characterized by single crystal X-ray diffraction. The compounds [(2-apmH)₂MX₄] with M = Co, X = Cl (1); M = Ni, X = Cl (3); and M = Ni, X = Br (4) are isomorphous and crystallize as nearly square planar MX₄ units with the 2-apmH cations coordinated in the axial sites through the unprotonated ring nitrogen. (2-ApmH)₂[CoBr₄] (2) crystallizes as the salt with a nearly tetrahedral CuBr₄ ^2- anion. (2-ApmH₂)[NiBr₂(H₂O)₄]Br₂ (5) forms as a cocrystal of the neutral, six-coordinate nickel complex and (2-ampH₂)Br₂, stabilized by extensive hydrogen bonding. Crystal data (1): monoclinic, P2₁/c, a = 7.540(4), b = 12.954(4), c = 7.277(3) Å, β = 110.09(6), V = 667.4(5) ų, Z = 2, D_calc = 1.955 Mg/m³, μ = 2.079 mm^-1, R = 0.0501 for [|I|≥2(I)]. For (2): triclinic, P-1, a = 7.720(2), b = 7.916(2), c = 14.797(3) Å, α = 97.264(3), β = 104.788(3), γ = 105.171(3)°, V = 825.3(3) ų, Z = 2, D_calc = 2.296 Mg/m³, μ = 10.715 mm^-1, R = 0.0308 for [|I|≥2(I)]. For (3): monoclinic, P2₁/c, a = 7.595(3), b = 12.891(4), c = 7.204(3) Å, β = 111.07(3)°, V = 658.2 ų, Z = 2, D_calc = 1.982 Mg/m³, μ = 2.279 mm^-1, R = 0.0552 for [|I|≥2(I)]. For (4): monoclinic, P2₁/c, a = 7.840(2), b = 13.358(4), c = 7.518(2) Å, β = 110.923(3)°, V = 938.6(3) ų, Z = 2, D_calc = 2.577 Mg/m³, μ = 12.18 mm^-1, R = 0.0280 for [|I|≥2(I)]. For (5): orthorhombic, Pnma, a = 16.776(6), b = 11.943(4), c = 7.079(3) Å, V = 1418.2(9) ų, Z = 4, D_calc = 2.564 Mg/m³, μ = 12.639 mm^-1, R = 0.0381 for [|I|≥2σ(I)].     

Synthesis and Crystal Structure of [Fe(Cp)2]3(Bi2Cl9)·thf

Single crystals of [Fe(Cp)₂]₃(Bi₂Cl₉)·thf were obtained from a thf solution containing ferrocene and BiCl₃. The structure shows disorder at room temperature which disappears upon cooling, coupled with a decrease in symmetry. The title compound crystallizes in the orthorhombic space group P2₁2₁2₁ [a = 1698.64(2), b = 2318.69(3), c = 1085.66(2) pm] with three ferrocenium ions, one nonachlorodibismutate ion and one molecule of thf in the asymmetric unit.     

Single Crystal Growth and Crystal Structure of Anhydrous Mercury(I) Nitrate,Hg2(NO3)2

Polycrystalline anhydrous Hg₂(NO₃)₂ was prepared by drying Hg₂(NO₃)₂·2H₂O over concentrated sulphuric acid. Evaporation of a concentrated and slightly acidified mercury(I) nitrate solution to which the same volumetric amount of pyridine was added, led to the growth of colourless rod‐like single crystals of Hg₂(NO₃)₂. Besides the title compound, crystals of hydrous Hg₂(NO₃)₂·2H₂O and the basic (Hg₂)₂(OH)(NO₃)₃ were formed as by‐products after a crystallization period of about 2 to 4 days at room temperature. The crystal structure was determined from two single crystal diffractometer data sets collected at —100°C and at room temperature: space group P2₁, Z = 4, —100°C [room temperature]: a = 6.2051(10) [6.2038(7)]Å, b = 8.3444(14) [8.3875(10)]Å, c = 11.7028(1) [11.7620(14)]Å, ß = 93.564(3) [93.415(2)]°, 3018 [3202] structure factors, 182 [182] parameters, R[Fμ² > 2σ(Fμ²)] = 0.0266 [0.0313]. The structure is built up of two crystallographically inequivalent Hg₂²⁺ dumbbells and four NO₃^— groups which form molecular [O₂N‐O‐Hg‐Hg‐O‐NO₂] units with short Hg‐O bonds. Via long Hg‐O bonds to adjacent nitrate groups the crystal packing is achieved. The Hg‐Hg distances with an average of d(Hg‐Hg) = 2.5072Å are in the typical range for mercurous oxo compounds. The oxygen coordination around the mercury dumbbells is asymmetric with four and six oxygen atoms as ligands for the two mercury atoms of each dumbbell. The nitrate groups deviate slightly from the geometry of an equilateral triangle with an average distance of d(N‐O) = 1.255Å.     

Selenious Acid as a Ligand: Molecular and Crystal Structure of [Co(H2O)2Cl2(H2SeO3)2]

[Co(H₂O)₂Cl₂(H₂SeO₃)₂] (monoclinic, P2₁/c, Z = 2, a = 519.82(5), b = 1462.6(1), c = 643.09(7) pm, β = 92.51(1)°, R_all = 0.0583) was obtained from CoCl₂ and H₂SeO₃ as purple plate–shaped single crystals. In the compound, the Co²⁺ ions are octahedrally coordinated by two Cl^? ions, two H₂O molecules, and two monodentate H₂SeO₃ molecules, leading to neutral complexes [Co(H₂O)₂Cl₂(H₂SeO₃)₂]. They are connected by hydrogen bonds involving both chlorine and oxygen atoms as acceptor atoms.     

The Crystal Structure of Ni21Sn2P6

During an investigation of the phase equilibria in the ternary system Ni/P/Sn, the existence of a new phase Ni₂₁Sn₂P₆ with a composition close to the known Ni₁₀P₃Sn phase was found. The crystal structure of the new phase was determined using single crystal X‐ray diffraction. The structure was solved employing Patterson and Difference Fourier Analysis. Ni₂₁P₆Sn₂ (space group , a = 1112.2 pm) crystallizes in an ordered variant of the C₆Cr₂₃ structure common to many carbides, borides and phosphides. The relation between Ni₂₁Sn₂P₆ and other C₆Cr₂₃ type phases and to Ni₁₀P₃Sn was established.