Bridging and chelating diphosphine ligands in Ru3(μ-H)(μ-N=CPh2)(CO)8(P—P). X-ray diffraction structures of Ru3(μ-H)(μ-N=CPh2)(CO)8(dmpe) and Ru3(μ-H)(μ-N=CPh2)(CO)8(bpcd)

Treatment of the azavinylidene-bridged cluster Ru₃(-H)(-N=CPh₂)(CO)₁₀ (1) with the diphosphine ligand bis(dimethylphosphino)ethane (dmpe) gives Ru₃( -H)(-N=CPh₂)(CO)₈(dmpe) (2) in moderate yield, while the ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) reacts with Ru₃( -H)(-N=CPh₂)(CO)₁₀ in the presence of Me₃NO to furnish Ru₃( -H)(-N=CPh₂)(CO)₈(bpcd) (3) in low yield. Each new cluster has been isolated and characterized in solution by IR and NMR (¹H and ³¹P) spectroscopies, and the coordination mode exhibited by the ancillary diphosphine ligand in 2 and 3 has been established by X-ray crystallography. Ru₃( -H)(-N=CPh₂)(CO)₈(dmpe) crystallizes in the monoclinic space group P2(1)/c, a = 10.791(1) Å, b = 16.377(1) Å, c = 18.148(1) Å, = 96.675(2)°, V = 3185.3(4) ų, Z = 4, D _cacl = 1.791 Mg/m³; R = 0.0360, R _w = 0.0866 for 7522 observed reflections with I > 2(I). Ru₃(-H)(-N=CPh₂)(CO)₈(bpcd) crystallizes, as the CH₂Cl₂ solvate, in the triclinic space group , a = 11.956(1) Å, b = 14.228(1) Å, c = 31.409(3) Å, = 89.377(2)°, = 79.344(2)°, = 77.235(2)°, V = 5118.4(8) ų, Z = 2, D _calc = 1.670 Mg/m³; R = 0.0557, R _w = 0.1069 for 10977 observed reflections with I > 2(I). The structural details of clusters 2 and 3 are contrasted with Ru₃(-H)(-N=CPh₂)(CO)₇(-dppm)(-dppm), which is the only known structurally characterized phosphine-substituted cluster of this genre.     

Structure of [La(NO3)3(OH2)2(OHMe)(bipy)]·15-crown-5

[La(NO₃)₃(OH₂)₂(OHMe)(bipy)·15-crown-5 is monoclinic,P2_t/n, witha=11.239(6),b=19.302(7),c=14.458(8) , =92.47(5)°, andD _calc=1.63 g cm^–3 forZ=4. In the complex, two nitrogen atoms (from bipy) and nine oxygen atoms (six from three bidentate nitrate anions, two from water molecules, and one from a methanol molecule) coordinate to the La(III) ion forming a coordination polyhedron which approximates a skewed trigonal prism with an interpenetrating pentagon. The coordinated methanol and water molecules donate hydrogen bonds to the oxygen atoms of the crown ether forming polymeric hydrogen bonded chains which propagate along theac diagonal in the unit cell.     

Cyclic dithiophosphate salts [Et3NH+[(OCH2CMe2CH2O)P(S)S]− and [Et3NH]+[CH2{6-t-Bu-4-Me-C6H4O}2P(S)S]−

X-ray structures of the cyclic dithiophosphate salts [Et₃NH]⁺[(OCH₂CMe₂CH₂O)P(S)(S)]^– (1) and [Et₃NH]⁺[CH₂{6-t-Bu-4-Me-C₆H₄O}₂P(S)S]^– (2) have been determined. Crystal data for 1: Tetragonal, P4₂/m, a = 13.416(7), b = 13.416(2), c = 9.153(2) Å, and Z = 4. Crystal data for 2 = Monoclinic, P2₁/c, a = 19.1112(17), b = 14.649(9), c = 22.7166(19) Å, = 102.883(7)°, and Z = 8. The six- and eight-membered rings in 1 and 2 have chair and boat-chair conformations respectively. Both of these compounds show weak N—H······S hydrogen bonds; interestingly, in 2 both two-center and three-center hydrogen bonds are observed in the solid state.     

Crystal and molecular structure of [(C6H5)2P(=0)(CH2CH2N(CH3)3 +][I−]

The title compound crystallizes in the centrosymmetric triclinic space group withZ=4. The crystallographic asymmetric unit contains two independent cations; interatomic distances within these include P=O=1.47(1) and 1.47(1) Å, P–C₆H₅=1.78(2)–1.81(1)Å and P–CH₂CH₂NMe₃ ⁺=1.80(1) and 1.81(1) Å. The phosphine oxide moiety is involved in intermolecular hydrogen bonding ()...H–C, with O...H2.42Å) and the iodide is involved in I...H–C contacts with I...H3.10Å.     

新的NLO化合物Ce(MoO2)(OH)(IO3)4的合成和晶体结构

新的NLO化合物Ce(MoO2)(OH)(IO3)4由水热法在170℃下制备得到.X射线单晶结构分析表明,该化合物以极性空间群P21结晶,晶体学参数为:a=0.70144(8)nm,b=1.41554(10)nm,c=0.70969(6)nm,β=115.318(7)°,V=0.6369(1)nm3,Z=2.Ce(MoO2)(OH)(IO3)4的晶体结构是由八配位的Ce3+阳离子,高度畸变的MoO66-八面体,和碘酸根阴离子基团组成的复杂三维网所构成.分析其结构表明,含有Ⅰ(3)和Ⅰ(4)的碘酸根基团的孤电子对的合成方向指向极化轴b,从而导致晶体结构具有非中心对称性.此外,红外光谱进一步证实了MoO66-,IO3-基团和Mo-OH作用的存在.     

Crystal structure of calcium trans-N-(nitrilotriacetato)(pyridine-2-carboxylato)cobaltate(III) hexahydrate, Ca[Co(Nta)(Pic)]2] · 6H2O

Crystals of Ca[Co^III (Nta)(Pic)]₂ · 6H₂O (I) (where Nta ^3? and Pic ^? are the nitrilotriacetate and picolinate ions, respectively) are prepared and characterized by the X-ray diffraction technique. Crystals I are monoclinic, a = 18.599(4) Å, b = 12.556(3) Å, c = 14.042(3) Å, β = 102.90(3)°, V = 3196(1) ų, Z = 4, space group P2₁/c, R1 = 0.0278, wR2 = 0.0716, and Goof = 1.054 for 4982 reflections with I > 2σ(I). Structure I is built of the { Ca(H₂O)₄[Co(Nta)(Pic)]₂{ _1∞ polymer ribbons and molecules of crystallization water. One of the two symmetrically independent anionic complexes (B) is included in the chain and alternates with cationic units, whereas the other anionic complex (A) forms a branch of this chain. The cationic and anionic units are interlinked via the interactions of the Ca²⁺ cations with the carbonyl atoms of the main (Nta ^3?) and additional (Pic ^?1) ligands. The octahedral environment of the Co(III) atoms consists of donor atoms of the Nta ^3? (N + 3O) and Pic ^? (N + O) ligands. The coordination polyhedron of the Ca atom (pentagonal bipyramid) includes two carbonyl O atoms of two Nta ^3? ligands, one O_Pic atom, and four O_w atoms of water molecules.     

X-ray structural and molecular mechanics investigation of cyclopentadienyl-carbonyl-triphenylophosphine-phenylacetyliron, (η5-C5H5)Fe(CO)(PPh3)(COCH2C6H5)

The crystal and molecular structure of cyclopentadienyl-carbonyl-triphenylphosphine-phenylacetyl-iron (1) has been determined on the basis of X-ray data. The crystals are triclinic, space groupP¯1 (Z=2) with cell dimensions:a=9.546(1),b=10.233(1),c=5.012(2) Å,=93.70(1),=101.12(1), =112.58(1)°. The structure was solved by direct methods and refined anisotropically by a full-matrix, least-squares procedure against 4964 independent reflections, givingR=0.0416. The MM calculations done for a model of1 reproduced satisfactorily the X-ray structure.On leave from the Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.     

Synthesis and structure of (H2O)(12-crown-4)-Co(II)(Co(II)Cl3)(μ-Cl) isolated from a liquid clathrate medium

The crystal structure of (H₂O)(12-crown-4)Co(II)(Co(II)Cl₃)(μ-Cl)1 is reported. Crystal data for1: monoclinic, space groupP2 ₁/m, a=7.958(8) Å,b=12.006(1) Å,c=69.017(9) Å, β=107.896(2)⁰, D_c=1.84 g cm^?3,Z=2,R1=0.025,wR2=0.059. The crown ether acts as a tetradentate ligand and partially completes the binding sphere of the Co(II) ion which also includes one water oxygen atom and a bridging chloride ligand, the latter of which may be regarded to originate from a [CoCl₄]^2? ion.     

Synthesis,structural, and spectroscopic study of rhenium(III) and rhenium(V) 4,6-dimethylpyrimidine-2-thiolate/triphenylphosphine mixed complexes: Crystal and molecular structure of ∥ReCl2(pymS)(PPh3)2∥·C3H6O and ∥ReOCl2(pymS)(PPh3)∥

4,6-dimethylpyrimidine-2(1H)-thione reacts with rhenium(V) precursorstrans-ReOX₃(PPh₃)₂ (X=Cl, Br) in acetone, to afford two classes of crystalline pyrimidinethiolate/triphenylphosphine mixed complexes:trans-Re^IIIX₂(C₆H₇N₂S)(PPh₃)₂·C₃H₆O and Re^vOX₂(C₆H₇N₂S)(PPh₃) (X=Cl, Br). The crystal structures oftrans-ReCl₂(C₆H₇N₂S)(PPh₃)₂·C₃H₆O (I) and ReOCl₂(C₆H₇N₂S)(PPh₃) (II) have been determined from single-crystal diffractometer data and refined toR factors of 0.0496 and 0.0365, respectively. (I) crystallizes in the triclinic space group P¯1 witha=16.875(4),b=13.969(7),c=9.510(2) Å;=81.78(2)°,=85.15(12)°, =107.97(8)° andZ=2. The coordination geometry around the rhenium center exhibit mutuallytrans phosphine groups and chloride ligands disposedtrans to the nitrogen and sulfur donors of the pyrimidinethiolate ligand which form a four-membered chelate ring with the metal. (II) crystallizes in the monoclinic space group P2₁/c witha=12.554(3),b=10.501(1),c=19.200(5) Å;=106.54(2)° andZ=4. The rhenium atom presents a very distorted octahedral configuration with a chlorine atomtrans to phosphine ligand in the axial position and the N,S-chelate ligand in the equatorial plane with the sulfur donor atomtrans the Re=O_oxo group. The compounds were characterized also by means of ir and nmr spectroscopic measurements; reaction pathways are discussed on the basis of structural data.     

Reactions of [Mn2(μ-pyS)2(CO)6] (pySH=pyridine-2-thiol) with triphenylphosphine (PPh3), diphenylphosphine (PHPh2) and bis(diphenylphosphino)methane (dppm): X-ray crystal structure of [Mn(pyS)(η1-dppm)2(CO)2]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 M equivalents of both PPh₃ and PHPh₂ to give the respective monomeric phosphine complexes [Mn(pyS)(L)(CO)₃][L = PPh₃ (2) and PHPh₂ (3)]; with 4 M equivalents of dppm, it yielded the complex [Mn(pyS)(¹-dppm)₂(CO)₂](4). An X-ray structure determination of 4 shows that it crystallizes in the monoclinic space group P2₁/n with a = 11.027(3), b = 24.984(7), c = 18.379(5) Å, = 99.870(8)°, V = 4988(2) ų, and Z = 4. The complex has an octahedral geometry with the chelating pyS ligand and two CO groups occupying the equatorial sites and the two monodentate dppm ligands lying in the trans positions.     

Reactions of [Mn2(μ-pyS)2(CO)6] with bidentate N-donor ligands: Crystal structure of [Mn(η1-pyS)(bipy)(CO)3] (bipy = 2,2′-bipyridyl, pySH = pyridine-2-thiol)

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 equivalents of 2,2-bipyridyl (bipy), 1,10-phenanthroline (phen), and ethylenediamine (en) to give the corresponding monomeric complexes [Mn(¹-pyS)(bipy)(CO)₃] (2), [Mn(¹-pyS)(phen)(CO)₃] (3), and [Mn( ¹-pyS)(en)(CO)₃] (4). The pyS ligand in these complexes acts as a monodentate, two-electron donor ligand, which coordinates to manganese through the sulfur atom. This is confirmed by an X-ray structure determination of 2, which contains two structural isomers in the asymmetric unit. Crystals of this compound are the monoclinic, space group P2 ₁/c, a = 21.593(4), b = 10.463(2), c = 16.385(3) Å, = 102.468(13)°, V = 3614.5(12) ų, and Z = 8. The three CO groups are facially distributed in both isomers, but the relative positions of the pyS and bipy ligands are different.     

Synthesis and Crystal Structure of [Mn(H2O)(tptz)(CH3COO)][N(CN)2] · 2H2O (tptz = 2,4,6-tris-(2-pyridyl)-1,3,5-triazine)

Abstract  The manganese complex [Mn(H₂O)(tptz)(CH₃COO)][N(CN)₂] · 2H₂O 1 (tptz = 2,4,6-tris-(2-pyridyl)-1,3,5-triazine) has been synthesized and structurally characterized by X-ray diffraction, element analysis and IR spectrum. It crystallizes in the monoclinic space group C2/c, a = 14.6898(1) ?, b = 13.4002(9) ?, c = 26.865(2) ?, β = 99.672(3)°, V = 5213.0(7) ?³, Z = 8. The number of coordination around Mn(II) atom is seven; it is coordinated equatorially by three nitrogen atoms from tptz, and two oxygen atoms from acetate, and axially by one nitrogen atom of dicyanamide and one coordinated water molecule. The crystal structure is stabilized through hydrogen bonds. Index Abstract  The title compound, [Mn(H₂O)(tptz)(CH₃COO)][N(CN)₂] · 2H₂O was synthesized by the treatment of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) and Mn(OAc)₂ · 4H₂O, with NaN(CN)₂ and its crystal structure determined. Single crystal X-ray diffraction analysis reveals that the number of coordination around Mn(II) atom is seven.      

Crystal structure of a new mineral lahnsteinite Zn4(SO4)(OH)6 · 3H2O

A sample of a new mineral from the oxidation zone of the hydrothermal Pb, Zn, Ag Friedrichssegen deposit (Rhineland-Palatinate, Germany) was studied by single-crystal X-ray diffraction. The parameters of the triclinic (pseudoorthorhombic) unit cell are found to be a = 8.312(1) ?, b = 14.545(1) ?, c = 18.504(2) ?, ?? = 89.71 (1)°, ?? = 90.05(1)°, ?? = 90.13(1)°, and V = 2237.3(3) ?³. The structure is solved by direct methods into the sp. gr. P1 and refined to an R factor of 10.7% using 3788 reflections with |F| > 3??(F) in the isotropic-anisotropic approximation. The crystallochemical formula of lahnsteinite (Z = 8) is [(Zn_2.6Fe_0.3Cu_0.1)^VI(OH)₃][Zn^IV(OH)₃(H₂O)][SO₄] · 2H₂O, where the compositions of the layer composed of Zn octahedra and isolated Zn and S tetrahedra are given in square brackets. The mineral under study is chemically and structurally similar to namuwite and is a natural analog of synthetic zinc hydroxide sulfate trihydrate.     

Synthesis and crystal structure of (CN3H6)2[UO2(OH)2(NCS)]NO3 and β-Cs3[UO2(NCS)5]

Compounds (CN₃H₆)₂[UO₂(OH)₂(NCS)]NO₃ (I) and β-Cs₃[UO₂(NCS)₅] (II) are synthesized and studied by IR spectroscopy and single-crystal X-ray diffraction. I and II crystallize in the orthorhombic system. For I, a = 12.2015(13) Å, b = 7.3295(8) Å, c = 16.310(2) Å, space group Pnma, Z = 4, and R = 0.0327; for II, a = 21.7891(6) Å, b = 13.5120(3) Å, c = 6.8522(2) Å, space group Pnma, Z = 4, and R = 0.0268. In structure I, complex groups form infinite chains [UO₂(OH)₂(NCS)] _n ^n? belonging to the AM ₂ ² M ¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , M ² = OH^?, and M ¹ = NCS^?). The main structural elements of crystals II are mononuclear [UO₂(NCS)₅]^3? groups belonging to the AM ₅ ¹ group of uranyl complexes (A = UO ₂ ²⁺ and M ¹ = NCS^?). In I and II, uranium-containing complexes are connected with outer-sphere cations by electrostatic interactions, and in I a system of hydrogen bonds also contributes to their binding. Specific features of the packing of complex [UO₂(NCS)₅]^3? groups in the structures of two modifications of Cs₃[UO₂(NCS)₅] are discussed.     

Ga_8(H_2O)_6(HPO_3)_(14)·(C_3N_2H_6)_3·H_3O:含有经典6* 1 SBU的新型三维开放骨架亚磷酸镓

为了丰富亚磷酸盐结构,为多孔材料的定向合成提供一定的实验数据,在溶剂热的条件下,以咪唑为结构导向剂合成了一个具有三维开放骨架结构的新型亚磷酸镓化合物Ga8(H2O)6(HPO3)14·(C3N2H6)3·H3O(化合物1),并通过粉末X-射线衍射、红外光谱、热重、ICP和CHN元素分析对化合物进行了表征。单晶X-射线衍射分析结果表明,化合物1属于三斜晶系,P-3c1空间群,晶胞参数为a=b=1.33388(8)nm,c=1.7886(2)nm,γ=120(4)°,Z=2。其结构是由Ga O6八面体和[HPO32-]假四面体单元相互连接构成。该结构沿着[100]和[010]方向具有12元环孔道。值得注意的是,在化合物1的结构中存在两种不同的次级结构单元(SBU):经典的6*1单元Ga3P4和齿轮状的Ga P6单元。     

Carbon–hydrogen and carbon–phosphorus bond cleavage in a triruthenium cluster complex containing dppm: The crystal and molecular structures of Ru3(CO)6{μ 3-OPPh2 C2H(C6H4)PPhCH2PPh}(μ 3-OPPh2)Ph and Ru3(CO)6 {μ-OPPh2C2H(C6H4)PPhO}(μ-PPh2)(μ-PPh2O)

The crystal and molecular structures of Ru₃(CO)₆{μ ₃-OPPh₂C₂H(C₆H₄)PPhCH₂PPh}-(μ ₃-OPPh₂)Ph (1) and Ru₃(CO)₆{μ-OPPh₂C₂H(C₆H₄)PPhO}(μ-PPh₂)(μ-PPh₂O) (2) have been determined by single crystal X-ray diffraction. Both complexes contain oxygen atoms oxidatively inserted into phosphorus–ruthenium bonds, and unique σ/π multidentate ligands formed from C $---{\text{H}}$ H and C $--$ P bond cleavage in bis(diphenylphosphino)acetylene and bis(diphenylphosphino)methane. Complex 1 crystallized in the triclinic space group ${\bar 1}$ , with lattice parameters a = 11.642(4) Å, b = 15.018(5) Å, c =16.587(5) Å, α = 2.48(3)°, β = 76.47(2)°, γ = 70.35(3)°, V = 2651.1(15) ų, Z = 2. Complex 2 crystallized in the centered monoclinic space group, C2/c, with lattice parameters a = 34.467(4) Å, b = 14.274(2) Å, c = 23.258(3) Å, β = 5.29(1)°, V = 11394(3) ų, Z = 8.     

Hydrothermal synthesis and X-ray structure: A reduced titanic molybdenum(V) phosphate (NH3CH2CH2NH2)5Na [Ti2Mo12O30(PO4)(HPO4)4(H2PO4)3]⋅6H2O

A novel titanic molybdenum(V) phosphate (NH₃CH₂CH₂NH₂)₅Na [Ti₂Mo₁₂O₃₀(PO₄) (HPO₄)₄(H₂PO₄)₃]6H₂O crystallizes in the triclinic space group P1 with a = 12.057(3) Å, b = 14.668(2) Å, c = 21.2680(10) Å, = 80.840(10)°, = 82.960(10)°, = 76.65(2)°, and D _c = 2.707 g cm^–3 for Z = 2, Refinement based on 12,037 observed reflections led to R = 0.0609. The result of single crystal x-ray diffraction revealed the presence of a tunnel and two crystallographically independent clusters in the solid state structure. The plane layers in its solid-state structure are interconnected in-sheet (axial) through multipoint hydrogen bonding between the ethylenediamine nitrogen atoms and the cluster oxygen atoms.     

超分子化合物(C_(12)H_(10)N_4)(C_7H_6O_3)_2的合成、晶体结构及荧光性质

合成了超分子化合物(C_(12)H_(10)N_4)(C_7H_6O_3)_2,并进行了元素分析、红外光谱、紫外光谱表征和单晶X射线衍射分析.构筑单元之间通过多重氢键和π-π堆积作用的协同效应形成超分子化合物,并研究了化合物的固体荧光性能.研究表明:该晶体属于单斜晶系P2_1/c空间群,晶胞参数为:a=0.3974(1) nm,b=2.0330(2) nm,c=1.4343(1) nm, β=94.892(2)°,V=1.15440(19) nm~3,d_c=1.400 g/cm~3,Z = 2,μ= 0.102 mm~(-1),F_((000))=508,R_1=0.0359,wR_2=0.0893 [I>2σ(I)].     

配合物[Cu2(C6H2Cl2OC=N-C3H6COO)2(H2O)2]·3H2O合成与晶体结构

本文以苏氨酸,3,5-二溴水杨醛以及醋酸铜为原料合成了新型配合物[Cu2(C6H2Cl2OC=N-C3H6COO)2(H2O)2]·3H2O,并对其晶体结构经元素分析,红外光谱及X射线单晶衍射表征.结果表明:该晶体属单斜晶体结构,晶胞参数分别为:a=0.6985(2) nm, b=1.0789(2) nm, c=1.9639(3) nm, β=92.182(3) °, Mr=797.34, V=1.4789(6) nm3 , Z=2, Dc=1.790 g/cm3, μ(MoKa) =1.867 mm-1, F(000)=808, R=0.0321, wR= 0.0566.Cu(II)与一个N原子,两个O原子以及一个水分子构成三齿链状席夫碱.不对称单元结构包含两个配合物分子及三个由氢键链接的水分子.     

Crystal structure ofmer,trans-[Ru(NO2)(trpy) (PPh3) 2 + ][PF 6 − ]: a “problem structure”

The complexmer,trans-[Ru(NO₂)(trpy)(PPh₃) ₂ ⁺ ][PF ₆ ^– ] crystallizes in the centrosymmetric monoclinic space groupP2₁/n withZ=4; the ruthenium atom lies close toy=1/4 and all data withh+l=2n+1 are systematically weak. The trpy ligand is not strictly planar, but has a dish-like geometry. The nitro ligand is rotated from the plane of the Ru(trpy) moiety, the N₃Ru/NO₂ interplanar angle being 32.5^o. Ruthenium-ligand distances are: Ru–PPh₃=2.418(4) Å and 2.429(4) Å, Ru–NO₂=2.063(12) Å, Ru–N(trpy, outer)=2.100(12) Å and 2.116(12) Å and Ru–N(trpy, central)=2.004(11) Å.