pH-Dependent Assembly of Hybrid Materials Based on Molybdates and Copper/imidazole Complexes

Three novel inorganic-organic hybrid materials, [Cu（imi）2（H2O）（MoO4）]n 1, [Cuz（imi）3（MoO4）E]n.nH2O 2 and [Cu3（imi）2（OH）2（MoO4）2]n 3 （imi = imidazole）, were synthesized and characterized by X-ray single-crystal structure determination. 1 crystallizes in orthorhombic, space group Pca21 with a = 13.382（4）, b = 8.527（2）, c = 9.622（3）A, V = 1098.0（5） A^3 Z = 4, C6H10CuMoN4O5, Mr = 377.66, Dc = 2.285 g/cm^3, F（000） = 740,μ（MoKa） = 3.095 mm^-1, the final R = 0.0256 and wR = 0.0722 for 1896 observed reflections with I 〉 2σ（I）. 2 crystallizes in monoclinic, space group P2t/c with a= 11.170（2）, b = 7.8244（15）, c = 22.631（4）A, β = 115.790（7）°, V = 1780.9（6）A^3 Z = 4, C9H14Cu2Mo2N6O9, Mr = 669.24, Dc= 2.496 g/cm^3, F（000）=1295,μ（MoKa） = 3.792 mm^-1, the final R = 0.0225 and wR = 0.0615 for 3838 observed reflections with I 〉 2σ（I）. 3 crystallizes in monoclinic, space group P21/c with a = 5.5599（19）, b = 23.771（8）, c = 7.3044（18）A , β = 129.356（16）°, V = 746.5（4）A^3, Z = 2, C6H10Cu3Mo2N4O10, Mr = 680.71, Dc = 3.029 g/cm^3, F（000） = 650,μ（MoKa） = 5.900 mm^-1, the final R = 0.0215 and wR = 0.0524 for 1620 observed reflections with I 〉 2σ（I）.     

Synthesis and Crystal Structure of （E）-ethyl 6-benzyl-2-[（cyclopropylmethylamino）（4-fluorophenylamino）-methyleneamino]-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate ethanol monosolvate

The crystal structure of the new title compound (E)-ethyl 6-benzyl-2-[(cyclopropylmethylamino)(4-fluorophenylamino)methyleneamino]-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate ethanol monosolvate (C28H31FN 4O2S·C2H6O, Mr=552.70) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P21/c with a=13.806(10), b=10.850(7), c=19.938(14), β=98.842(9)° , V=2951(4)3 , Z=4, Dc=1.244g/cm 3 , F(000)=1176, μ=0.153 mm-1 , MoKα radiation (λ=0.71073), R=0.0758 and wR=0.2234 for 4262 observed reflections with I > 2σ(I). Intramolecular N-H…S and C-H…N interactions as well as intermolecular N-H…O and O-H…N hydrogen bonds help to stabilize the crystal structure. X-ray diffraction analysis reveals that the asymmetric unit contains one title molecule and one ethanol molecule.     

Syntheses and Crystal Structures of Two New Macrocyclic Compounds

Two new macrocyclic compounds, [Cu2(L)2](ClO4)4·2CH3OH (1) and [Cu(L)](ClO4)2·2H2O (2) (L = 1,3,10,12,15,18-hexaazatetracyclodocosane) were synthesized by condensation reactions involving amines and formaldehyde in the presence of copper anion. Compound 1 crystallizes in triclinic, space group Pí with a = 10.442(2), b = 14.197(3), c = 17.388(4), α = 91.218(4), β = 90.69(3), γ = 93.756(4)o, V = 2520.4(9)3, Z = 2, F(000) = 1260, Dc = 1.589 Mg/m3, Mr = 1205.92, μ = 1.137 mm-1, λ = 0.71073, the final R = 0.0668 and wR = 0.1573 for 9703 observed reflections with I > 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 16.911(2), b = 11.4172(15), c = 27.059(4), β = 107.787(2)o, V = 4974.7(12)3, Z = 8, F(000) = 2504, Dc = 1.610 Mg/m3, Mr = 602.92, μ = 1.155 mm-1, λ = 0.71073 , the final R = 0.0419 and wR = 0.1131 for 4374 observed reflections with I > 2σ(I).     

Syntheses and Crystal Structures of(H_3O)(C_3H_5N_2)[Mn(OH)_6Mo_6O_(18)]·3.5H_2O and (H_3O)_3[Co(OH)_6Mo_6O_(18)]·7H_2O

1 INTRODUCTION Polyoxometalates, a rich and remarkable classof inorganic cluster system[1], exhibit diverse appli-cation possibilities due to their topological and elec-tronic properties, ranging from their well-known roleas reagents in analytical, b…     

Syntheses and Crystal Structures of Two Cadmium(Ⅱ) Compounds Linked by N,N-Bis(3-pyridylmethyl)amine

Two cadmium(Ⅱ) compounds linked by a flexible dipyridyl ligand {[Cd2(Hbpma) Cl5(H2O)]·2H2O}n 1 and [Cd(Hbpma)Cl(H2O)2]2·2SO4·3H2O 2 (bpma = N,N-bis(3-pyridylmethyl)amine) have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P with a = 9.5612(6), b = 11.3401(7), c = 11.5069(12), α = 112.8540(10), β = 106.5330(10), γ = 101.6680(10)°, V = 1030.77(14)3, C12H20Cd2Cl5N3O3, Mr = 656.36, Z = 2, Dc = 2.115 g/cm3, μ(MoKα) = 2.727 mm-1, F(000) = 636, S = 1.059, the final R = 0.0319 and wR = 0.0822 for 3443 observed reflections (I > 2σ(I)). For complex 2, it belongs to triclinic, space group P with a = 10.9487(4), b = 11.4197(4), c = 15.4288(5), α = 94.7470(10), β = 104.1000(10), γ = 104.42°, V = 1790.76(11)3, C24H42Cd2Cl2N6O15S2, Mr = 1014.46, Z = 2, Dc = 1.881 g/cm3, μ(MoKα) = 1.529 mm-1, F(000) = 1020, S = 1.050, the final R = 0.0178 and wR = 0.0451 for 6026 observed reflections (I > 2σ(I)). Complex 1 is found to have tetranuclear Cd(Ⅱ) clusters which are bridged by the protonated bpma ligands leading to one-dimensional coordination polymers, whereas complex 2 consists of binuclear Cd(Ⅱ) structures linked by the protonated bpma ligands. Both complexes are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions.     

Template Syntheses and Crystal Structures of Hexaaza Macrocyclic Complexes with C-Methyl Substituents

1 INTRODUCTION Polyaza-macrocyclic compounds with functional substituents have been extensively investigated recen- tly because of their potential applications in radioac- tive therapy, recovery of metal ions, biomimetic che- mistry, and catalysis[1, 2]. With various structures and distinctive properties, they have become significant building blocks for further chemical studies[3～6]. As far as the preparation method is concerned, metal template condensation reactions are shown to be effec…     

From Chain to Layer Structure: ZnⅡ Coordination Polymers Derived from Diphenic Acid

Three ZnⅡ coordination polymers, [Zn(py)(H2O)(dpa)]n 1, [Zn2(4,4'-bipy)2(dpa)2]n 2 and [Zn(bpe)(H2O)2(Hdpa)2]n 3 (py = pyridine, H2dpa = diphenic acid, 4,4'-bipy = 4,4'-bipyridine,bpe = 1,2-bis(4-pyridyl)ethane), were synthesized and characterized by X-ray single-crystal structure determination. 1 crystallizes in monoclinic, space group C2/c with a = 23.014(3), b = 8.7184(13), c = 18.091(3) (A), β = 95.964(3)°, V = 3610.2(9) (A)3, Z = 8, C19H15NO5Zn, Mr = 402.69,Dc= 1.482 g/cm3, F(000) = 1648, μ(MoKα) = 1.389 mm-1, the final R = 0.0431 and wR = 0.1120 for 4239 observed reflections with I ＞ 2σ(Ⅰ). 2 crystallizes in orthorhombic, space group Fddd with a = 23.1613(5), b = 24.0324(6), c = 29.4785(1) (A), V= 16408.4(5) (A)3, Z = 32, C24H16N2O4Zn, Mr = 461.76, Dc= 1.495 g/cm3, F(000) = 7552, μ(MoKα) = 1.232 mm-1, the final R = 0.0542 and wR = 0.1724 for 3632 observed reflections with I ＞ 2σ(Ⅰ). 3 crystallizes in orthorhombic, space group C2/c with a = 19.142(4), b = 13.862(3), c = 15.625(3) (A), β = 122.404(3)°, V = 3500.3(11) (A)3, Z = 8,C20H17NO5Zn0.50, Mr = 384.03, Dc= 1.457 g/cm3, F(000) = 1592,μ(MoKα) = 0.766 mm-1, the final R = 0.0400 and wR = 0.1210 for 4024 observed reflections with I ＞ 2σ(Ⅰ).     

From Chain to Layer Structure: Zn~(II) Coordination Polymers Derived from Diphenic Acid

1 INTRODUCTION The rational design and synthesis of metal-organic coordination polymers have generated considerable interest in supramolecular chemistry and material science owing to their intriguing structural diver- sities and potential applications as functional mate- rials[1～3]. Up to now, some structural motifs with specific topologies and functions have been con- structed through rational combination of organic li- gands containing appropriate coordination sites and metal ions beari…     

Synthesis and Crystal Structure of a New Nickel（II） Complex with 2,4-Pyridinedicarboxylic Acid and 1,4-Bis（imidazol-1-ylmethyl）-benzene） Ligands

A metal-organic coordination polymer [Ni(PDC)(bix)(H2O)]n (H2PDC = 2,4-pyri- dinedicarboxylic acid, bix = 1,4-bis(imidazol-1-ylmethyl)-benzene) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. Blue crystals crystallize in the monoclinic system, space group C2/c with a = 25.1475(18), b = 13.1621(9), c = 14.2739(10), β = 118.4150(10)o, V = 4155.4(5) 3, C21H19N5NiO5, Mr = 480.12, Dc = 1.535 g/cm3, F(000) = 1984, Z = 8, μ(MoKα) = 0.979 mm-1, the final R = 0.0478 and wR = 0.1004 for 3727 observed reflections (I > 2σ(I)). The structure of 1 exhibits a one-dimensional chain-like structure.     

Syntheses and Structure Determination of Two Copper Compounds with 4,4--Sulfonyldibenzoilate Ligands

The two title compounds [Cu(sdba)(py)2(H2O)]n·2n(py) 1 and [Cu(sdba)(phen)(H2O)]n 2(H2sdba = 4,4'-sulfonyldibenzoic acid,py = pyridine,phen = 1,10-phenanthroline) have been synthesized and characterized by single-crystal structure determination,IR and TG analyses.Compound 1 crystallizes in orthorhombic,space group Pbcm with a = 5.9833(12),b = 22.333(5),c = 24.571(5),V = 3283.3(12) 3,Z = 4,C34H30N4O7SCu,Mr = 702.22,Dc = 1.388 g/cm3,F(000) = 1396,μ(MoKα) = 0.780 mm-1,the final R = 0.0599 and wR = 0.1767 for 3416 observed reflections with I > 2σ(I).Compound 2 crystallizes in monoclinic,space group C2/c with a = 22.9549(4),b = 12.2443(3),c = 17.8687(4) ,β = 110.873(1)°,V = 4692.69(18) 3,Z = 8,C26H18N2O7SCu,Mr = 566.02,Dc = 1.602 g/cm3,F(000) = 2312,μ(MoKα) = 1.078 mm-1,the final R = 0.0697 and wR = 0.1330 for 3452 observed reflections with I > 2σ(I).In both structures,the CuII metal centers adopt five-coordination in slightly distorted tetragonal pyramidal geometries,while the second N-donor ligands bond or chelate to CuII ions as the terminal moiety.The weak interactions extend the two structures into high-dimensional supramolecular coordination-polymers.     

Crystal Structure and Photochromism in Paint of 1,3,3-Trimethyl-6'-dihydro-indolinyl- spiro[2,3'-[3H]-naphtho[2,1-b][1,4]]oxazine

The title compound 2 (C30H27N3O, Mr = 445.55) has been synthesized and its structure was determined by X-ray crystallography method. The crystal is of monoclinic, space group P21/c with a = 17.520(15), b = 8.640(7), c = 15.439(13) , β = 98.642(14)°, V = 2310(3) 3, Dc = 1.281 g/cm3, μ = 0.780 mm-1, F(000) = 944, Z = 4, the final R = 0.0671 and wR = 0.1790 for 1952 observed reflections with I > 2σ(I). X-ray analysis revealed that the interatomic distance of C(20)O(1) is 1.464(4) , longer than that of the normal CO bond (1.41～1.43 ) in the six-membered heterocycle, but this kind of change coincides with other spiro compounds. The six-membered heterocycle containing spiro Csp3O is nonplanar. The UV-vis spectra of the title compound in polymer films showed that it exhibits excellent photochromic property.     

Syntheses and Crystal Structures of (H3O)(C3H5N2)[Mn(OH)6 Mo6O18]·3.5H2O and (H3O)3[Co(OH)6Mo6O18]·7H2O

The crystals of the title compounds (H3O)(C3H5N2)[Mn(OH)6Mo6O18]·3.5H2O 1 and (H3O)3[Co(OH)6Mo6O18]·7H2O 2 have been prepared and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 21.5018(9), b = 10.9331(5), c = 11.8667(5)A,β = 95.3570(10)o, V = 2777.5(2)A3, Z = 4, Dc = 2.802 g/cm3, Mr = 1171.80,μ(MoKα) = 3.173 mm-1, F(000) = 223, the final R = 0.0458 and wR = 0.1041 for 2093 observed reflections (I>2σ(I)); Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.4042(12), b = 10.9481(11), c = 11.6722(12)A, β= 99.948(2)o, V = 1435.4(3)A3, Z = 2, Dc = 2.794 g/cm3, Mr = 1207.80,μ(MoKα) = 3.223 mm-1, F(000) = 1160, the final R = 0.0544 and wR = 0.1066 for 1906 observed reflections (I > 2σ(I)). Both compounds 1 and 2 adopt the Anderson structure, in which the anion is of centrosymmetry and formed by six octahedral edge-sharing MoO6 units surrounding the central MO6 (M = Mn or Co) octahedron.     

Hydrothermal Synthesis, Crystal Structure and Photoluminescent Property of a Zinc（II） Complex with 2,2′-Diphenic Acid and 2,2′-Bipyridine Ligands

A new dinuclear complex [Zn(dpa)(bipy)(H2O)]2 (dpa = 2,2'-diphenic acid, bipy = 2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 10.960(2), b = 9.4841(18), c = 20.599(4), β = 104.452(3)o, V = 2073.4(7)3, C48H36N4O10Zn2, Mr = 959.55, Dc = 1.537 g/cm3, μ(MoKα) = 1.225 mm-1, F(000) = 984, Z = 2, the final R = 0.0364 and wR = 0.0843 for 2788 observed reflections (I > 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas, one coordinated water molecule and two nitrogen atoms from bipy ligands, showing a slightly distorted triangular bipyramidal geometry. Furthermore, it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.     

Hydrothermal Synthesis and Crystal Structure of a Novel Isophthalate-bridged Copper(Ⅱ) Polymer with Two-dimensional Network Structure: [Cu2(phen)(ipt)2]2n·nH2O (ipt = isophthalate, phen = 1,10-phenanthroline)

A novel metal-organic coordination polymer [Cu2(phen)(ipt)2]2n·nH2O 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 12.338(3), b = 12.167(3), c = 18.167(4)(A), β = 111.686(14)o, V = 2534.1(10) A)3, C28H18Cu2N2O9, Mr = 653.52, Dc = 1.713 g/cm3, μ(MoKα) = 1.740 mm-1, F(000) = 1320, Z = 4, the final R = 0.0443 and wR = 0.0853 for 3543 observed reflections (I > 2σ(I)). It exhibits a novel two-dimensional network with tetra- Cu-ipt- as building units.     

Synthesis and Crystal Structure of a New Complex [Cd（C20H14N4）2Cl2]

The title compound [Cd(C20H14N4)2Cl2] 1 was synthesized via the hydrothermal reaction of CdCl2·7H2O and NaOH with 1,3-bis(benzimidazol-2-yl)benzene (BMB), and characterized by elemental analysis and infrared spectra. The crystal of 1 crystallizes in monoclinic, space group C2/c with a = 21.021(6), b = 9.489(3), c = 18.302(6), β = 108.686(6)o, V = 3458.2(19)3, Z = 4, C40H28CdN8Cl2, Mr = 804.01, Dc = 1.544 g/cm3, F(000) = 1624 and μ(MoKα) = 0.829 mm-1. The final R = 0.0306 and wR = 0.0779 for 3334 observed reflections with I > 2σ(I) and R = 0.0796 and wR = 0.0360 for all data. The cadmium atom is four-coordinated by the BMB ligands and Cl atom with a tetrahedral geometry. The extensive N-H···N hydrogen bonding interactions are observed in the structure, which further extend the [Cd(C20H14N4)2Cl2] units into a 1D structure. The thermogravimetric analysis measurement showed that compound 1 has thermal stability as no strictly clean weight loss step occurred below 425 ℃.     

Hydrothermal Synthesis, Structure and Thermal Properties of a Novel Three-dimensional La(Ⅲ)-Sebacate Framework

A novel lanthanide-organic framework compound [La(seb)(Hseb)(H2O)]n (H2seb = sebacic acid) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectra, TG and single-crystal X-ray diffraction. Complex 1 crystallizes in the triclinic system, space group P with a = 8.5849(7), b = 9.0641(8), c = 15.4049(13), α = 98.1830(10), β = 100.6870(10), γ= 97.5650(10)°, Z = 2, V = 1150.44(17) 3, Dc = 1.612 g/cm3, Mr = 558.39, λ(MoKα) = 0.71073 , μ = 1.903 mm-1, F(000) = 568, R = 0.0219 and wR = 0.0507 for 3797 observed reflections with I > 2σ(I). The structure contains edge-shared chains of [LaO8(H2O)] tricapped trigonal prisms that propagate along the b axis. In aliphatic ligand participation, complex 1 exhibits a three-dimensional supramolecular framework. Moreover, the thermal stability of complex 1 has been investigated.     

Syntheses and Characterizations of （CH3CH2CH2CH2NH3）6（BiI6）（I）2I3 and （NH3CH2CH2NH3）2Bi2I10

The title compounds have been respectively synthesized by solution process and solvothermal reaction, and their crystal structures were determined by X-ray diffraction method. For （CH3CH2CH2CH2NH3）6（BiI6）（I）2I3 1, it crystallizes in tficlinic, space group P1^- with Mr = 2049.76, a = 8.5719（1）, b = 11.7461（3）, c = 15.700（1）A, V = 1451.4（1）A^3, Z = 1, Dc = 2.345 g/cm^3, F（000） = 924, μ（MoKα） = 8.907 mm^-1, T = 293（2） K, the final R = 0.0655 and wR = 0.0804 for 2399 observed reflections with I 〉 2σ（I）. For （NH3CH2CH2NH3）2Bi2I10 2, it crystallizes in monoclinic, space group P21/n with Mr= 1811.20, a = 8.434（4）, b = 13.862（6）, c = 13.362（6）A, V = 1499.9（12）A^3, Z = 2, Dc = 4.010 g/cm^3, F（000） = 1536,μ（MoKα） = 22.007 mm^-1, T = 293（2） K, the final R = 0.0584 and wR = 0.1451 for 1798 observed reflections with I 〉 2σ（I）. The structures of 1 and 2 contain halobismuthate monomer and dimers, respectively. It is noteworthy that the dimers and their organic counters in 2 connect each other by N…I hydrogen bonds to form a layered structure, and the electrostatic interactions and crystal packing forces between layers give rise to the packing of the crystal. The optical absorption spectra of 1 and 2 reveal the appearance of sharp optical gaps of 2.13 and 2.01 eV, respectively.     

Synthesis, Crystal Structure and Biological Activity of a New 1,2,4-Triazole Derivative

A new 1,2,4-triazole containing cyclopropane moiety was synthesized and characte- rized by 1H NMR, MS and elemental analyses. The crystal structure of the title compound (C13H14FN3S, Mr = 263.33) has been determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 12.614(3), b = 7.0202(14), c = 15.556(3), β = 110.92(3)°, V = 1286.7(4)3 , Z = 4, F(000) = 552, Dc = 1.359 g/cm 3 , μ = 0.25 mm-1 , the final R = 0.0336 and wR = 0.0898 for 2568 observed reflections with Ⅰ > 2σ(Ⅰ). A total of 10093 reflections were collected, of which 3045 were independent (Rint = 0.0268). The herbicidal activity of the title compound was determined, and this compound displays excellent herbicidal activity against Brassica campestris.     

Hydrothermal Synthesis and Crystal Structure of a Cadmium(II) Polymer with One-dimensional Chain Structure: [Cd(bpy)(BDC)]_n·nbpy

A metal-organic coordination polymer [Cd(bpy)(BDC)]n·nbpy (bpy = 2,2-bipyri- dine, H2BDC = terephthalic acid) has been hydrothermally synthesized and structurally characteri- zed by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group C2/c with a = 15.723(5), b = 21.695(5), c = 7.576(5) , β = 116.171(7)o, V = 2319.3(18) 3, C28H20CdN4O4, Mr = 588.88, Dc = 1.686 g/cm3, μ(MoKα) = 0.987 mm-1, F(000) = 1184, Z = 4, the final R = 0.0464 and wR = 0.0831 for 1882 observed reflections (I > 2σ(I)). It exhibits a three-dimensional network with channels constructed from one-dimensional coordination chains via C–H···O hydrogen bonds and significant aromatic π-π stacking interactions.     

Synthesis, Crystal Structure and Luminescent Property of a One-dimensional Zinc（Ⅱ） Complex

A metal-organic coordination polymer [Zn2(cbba)4(bix)2]n·nH2O (Hcbba = 2-(4′- chlorine-benzoyl)-benzoic acid, bix = 1,4-bis(imidazol-1-ylmethyl)-benzene) 1 has been hydrothermally synthesized and characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Pale yellow crystals crystallize in the triclinic system, space group Pī, a = 10.2796(13), b = 17.636(2), c = 23.237(3), α = 105.046(2), β = 102.534(2), γ = 100.758(2)o, V = 3837.0(9)3, C84H59Cl4N8O13Zn2, Mr = 1660.93, Dc = 1.438 g/cm3, F(000) = 1702, Z = 2, μ(MoKα) = 0.835 mm-1, the final R = 0.0525 and wR = 0.1211 for 9129 observed reflections (I > 2σ(I)). The structure of 1 exhibits a one-dimensional chain-like structure and shows yellow luminescent property at room temperature.