Synthesis and Structural Characterization of a Supramolecular Compound [(C8H9NO2)·HgI2]n Constructed from Hg…I and C-H…O Linkage

The title complex [(C8H9NO2)·HgI2]n has been synthesized from the reaction of pyridine-3-ethylformate with mercury iodide in the mixture of DMF and absolute methanol. Its structure was determined by IR, elemental analysis and X-ray single-crystal diffraction analysis. The crystal is of monoclinic system, space group P21/n with a = 4.3397(5), b = 25.051(3), c = 12.3719(13) (A)3, β = 92.2130(10)°, C8H9HgI2NO2, Mr = 605.55, V = 1344.0(3) (A)3, Z = 4, Dc = 2.993 mg·m-3, F(000) = 1064, μ = 16.024 mm-1, the final R = 0.0258 and wR = 0.0504. In the title complex, the center Hg(Ⅱ) exhibits a four-coordinated distorted tetrahedral geometry. A three-dimensional network arrangement is presented via Hg…I weak interactions among adjacent molecules.     

Synthesis and Structural Characterization of a Supramolecular Compound [(C8H9NO2)·HgI2]n Constructed from Hg…I and C-H…O Linkage

The title complex [(C8H9NO2)·HgI2]n has been synthesized from the reaction of pyridine-3-ethylformate with mercury iodide in the mixture of DMF and absolute methanol. Its structure was determined by IR, elemental analysis and X-ray single-crystal diffraction analysis. The crystal is of monoclinic system, space group P21/n with a = 4.3397(5), b = 25.051(3), c = 12.3719(13) (A)3, β = 92.2130(10)°, C8H9HgI2NO2, Mr = 605.55, V = 1344.0(3) (A)3, Z = 4, Dc = 2.993 mg·m-3, F(000) = 1064, μ = 16.024 mm-1, the final R = 0.0258 and wR = 0.0504. In the title complex, the center Hg(Ⅱ) exhibits a four-coordinated distorted tetrahedral geometry. A three-dimensional network arrangement is presented via Hg…I weak interactions among adjacent molecules.     

Synthesis,Structure, and Luminescent Property of a 3-D Strontium Complex [Sr_3(pda)_2(Hpda)_2(H2O)_2]_n·2nH_2O

The title complex [Sr3(pda)2(Hpda)2(H2O)2]n·2nH2O(H2pda = pyridine-2,6-dicar- boxylic acid) has been prepared under solvothermal conditions. It has been characterized by X-ray single-crystal diffraction, IR and elemental analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 10.3795(8), b = 9.2225(7), c = 18.5726(14) , β = 104.377(2)o, V = 1722.2(2) 3, C28H22N4O20Sr3, Mr = 997.36, Z = 2, Dc = 1.923 g/cm3, μ = 4.722 mm-1, F(000) = 984, the final R = 0.0269 and wR = 0.0538. This complex possesses a 3-D structure which is constructed from 1-D chain motifs linked by carboxylate groups. The luminescent property of the title complex has been investigated.     

Synthesis and Crystal Structure of a Novel 1D Mercury（II） Iodide Coordination Polymer Containing 40-Membered Macrocycle

A mercury coordination polymer [Hg3(TizT)2I6]n (Mr = 1921.72, TizT = 2,4,6- tri(imidazole-1-yl)-1,3,5-triazine) containing a 40-membered macrocycle which was constructed by four TizT ligands and four mercury(II) iodide molecules had been synthesized by the reaction of HgI2 with TizT. The complex was characterized by elemental analysis, FT-IR, 1H NMR spectra and X-ray crystallography. The crystal of the complex belongs to the monoclinic system and C2/c space group with a = 35.840(5), b = 8.169(5), c = 14.980(5) , β = 104.466(5)°, Z = 4, V = 4247(3) 3, Dc = 3.006 g·cm-3, μ = 15.223 mm-1, F(000) = 3384, Rint = 0.0504, wR = 0.0833 and constructs a chair-like conformation of cyclohexane one by one, which forms a 1-D polymer through the fashion of fused ring aromatic hydrocarbon. The hydrogen bonds and π-π interactions shape the 2-D network structure. The two compounds excited weak fluorescence.     

Synthesis,Crystal Structure and Photoluminescence of [Gd(C_6NO_2H_5)_3-(H_2O)_2]_(2n)·(nH_5O_2)(nHgCl_5)(2nHgCl_4)·(2nH_2O)

A heterometallic 4f-5d inorganic-organic metal-isonicotinato hybrid Gd(C6NO2H5)3-(H2O)22n·(nH5O2)(nHgCl5)(2nHgCl4)·(2nH2O) 1 has been synthesized via hydrothermal reaction and structurally characterized.Complex 1 crystallizes in the space group C2/c of monoclinic system with four formula units in a cell:a=24.234(8)=b=20.816(7)=c=15.333(3)=β=128.091(8)°=V=6088(3)3=C36H47Cl13Gd2Hg3N6O20=Mr=2260.92=Dc=2.467 g/cm3=S=0.896=μ(MoKα)=10.331 mm-1=F(000)=4216=R=0.0344 and wR=0.0629.The crystal structure analysis reveals that the title complex is characteristic of a one-dimensional chain-like structure.Photoluminescent investigation reveals that the title complex displays a broad and intense emission in the green region.     

Synthesis and Crystal Structure of Di-μ_(1,1)-azido-bis((azido)[N-ethyl-N'-(1-pyridin-2-ylmethylidene)ethane-1,2-diamino]cadmium(Ⅱ))

The dinuclear Schiff base cadmium(II) complex [Cd2(C10H15N3)2(N3)2 (μ1,1-N3)2] was prepared and characterized by elemental analysis, IR spectrum, and single-crystal X-ray dif- fraction. The crystal belongs to the monoclinic system, space group P21/n with a = 10.819(2), b = 11.058(2), c = 12.766(3) , β = 102.456(2)o, V = 1491.3(7) 3, Z = 2, Dc = 1.665 g/cm3, Mr = 747.42, λ(MoKα) = 0.71073 , μ = 1.470 mm-1, F(000) = 744, R = 0.0307 and wR = 0.0584. A total of 3420 unique reflections were collected, of which 2575 with I > 2σ(I) were observed. There is a crystallographic inversion centre at the midpoint of the two metal atoms in the complex. Each CdII atom in the complex is in a distorted octahedral coordination. The molecules in the crystal are linked through the intermolecular hydrogen bonds of N–H···N and C–H···N, forming a three- dimensional network.     

Hydrothermal Synthesis and Crystal Structure of a Manganese(II) Coordination Polymer with 1,1′-Biphenyl-2,2′,6,6′-tetracarboxyl Acid and 2,2′:6,2′′-Terpyridine Ligands

The title compound {[Mn(H2BPTC)(tpy)(H2O)]·(H2O)3}n (1, H4BPTC = 1,1′- biphenyl-2,2′,6,6′-tetracarboxylic acid, tby = 2,2′:6,2′′-terpyridine) has been synthesized by the hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of monoclinic, space group P21/c with a = 10.971(2), b = 20.776(4), c = 14.332(3) , β = 109.25(3)o, MnC31H27N3O12, Mr = 688.50, V = 3084.1(10) 3, Dc = 1.483 g/cm3, F(000) = 1420, μ = 0.498 mm-1, S = 1.066 and Z = 4. The final refinement gave R = 0.0447 and wR = 0.1103 for 5107 observed reflections with I > 2σ(I). The title complex has a {[Mn(H2BPTC)(tpy)(H2O)]}n chain structure, and the hydrogen bonding interactions make it more stable. Each chain is further connected to the adjacent ones through π···π, C-H···π and rich hydrogen bonds to form a metal-organic coordination polymer.     

Hydrothermal Synthesis and Crystal Structure of a Novel Binuclear Cd(Ⅱ) Coordination Polymer Based on 1,2-Benzenedicarboxylate and Imidazole

The hydrothermal reaction of Cd(OAc)2·H2O with 1,2-benzenedicarboxylate(1,2-BDC),imidazole and H2O resulted in the formation of a binuclear polymeric Cd(Ⅱ) complex {[Cd2(1,2-BDC)2(Im)4]·(H2O)}n which was then characterized by elemental analyses and single-crystal X-ray diffraction analysis.The crystal is of monoclinic system,space group P21/c with a = 14.6455(3),b = 9.3530(2),c = 23.7838(5) ,β = 106.6290(10)°,C112H104Cd8N32O36,Mr = 3373.47,V = 3121.64(11) 3,Dc = 1.795 g/cm3,F(000) = 1672,μ = 1.428 cm-1 and Z = 1.The final R = 0.0316 and wR = 0.0687 for 5045 reflections with I > 2σ(I).In the title complex,the two Cd(Ⅱ) ions are in different coordination environments with distorted octahedral and pengonal bipyramidal geometries,respectively.Two Cd polyhedra are linked together through one μ2-η1:η1 and one μ2-η1:η2 carboxylate groups from different 1,2-BDC ligands,giving rise to a binuclear Cd(Ⅱ) cluster,and such clusters are connected by bridged 1,2-BDC ligands to form a 2-D structure along the c axis.The inter-and intermolecular hydrogen bonds further connect the 2-D structures into a 3-D supramolecular network.     

Synthesis and Structure of a Novel Cobalt(Ⅱ)Complex with the Tertiary Carbinol Derivative of Di-4-pyridinylmethanone

The title complex [Co[(4-C5H4N)2C(OH)(NHC3H7)]2(NO3)2]∞ was obtained and characterized through elemental analysis, FT-IR and X-ray crystallography. The complex crystallizes in space group P3(2)21 with a=10.2480(11), b=10.2480(11), c=26.943(6), β=120.00°, [Co[(4-C5H4N)2C(OH)(NHC3H7)]2(NO3)2]∞, C28H34CoN8O8 , Mr=669.56, Z=3, V=2450.5(7)3 , Dc=1.361 g·cm-3 , μ=0.584 mm-1 , F(000)=1047, R=0.0498 and wR=0.1301. The Co(Ⅱ) center exhibits a N4O2-octahedral coordination geometry surrounded by a pair of nitrates at the axial positions and four pyridyl N atoms at the equatorial sites. An infinite double-bridged chain structure with μ2-bridging (4-C5H4N)2C(OH)(NHC3H7) ligands is formed, which is the in situ product of metal-promoted nucleophilic addition reaction of propan-1-amine with di-4-pyridinylmethanone ((4-C5H4N)2CO) in the presence of Co(NO3)2·6H2O. It is the first tertiary carbinol metal complex derived from di-4-pyridinylmethanone so far, and also the rare example of tertiary carbinol derivative of dipyridylmethanone family. The nucleophilic reaction at the carbonyl of dipyridylmethanone in the presence of metal salt will be discussed.     

Structural Studies and Photoluminescence of a Novel Mercury（Ⅱ） Complex Based on a Tris[4-（1-pyrazolyl）-phenyl]amine

A novel iodine-bridged mercury（Ⅱ） complex [Hg（L）（μ-I）（I）]2 was isolated by a reaction between HgI2 and the organic ligand tris[4-（1-pyrazolyl）phenyl]amine L, and the complex and ligand were both characterized by FT-IR spectroscopy, ^1H NMR and elemental analysis. The complex crystallizes in monoclinic space group P21/c with a = 9.579（5）, b = 27.331 （5）, c = 11.268（5） А, β= 105.624（5）°, Z = 2, Dc = 2.099 g·cm^-3 and μ= 7.620 mm^-1. The title complex C54H42Hg2I4N14 is a diplex bridged dinuclear complex consisting of two Hg（Ⅱ） ions, two ligands, two bridging I-anions, and two terminal I-anions. Universal hydrogen bonds in the complex with the partners of neighboring molecule have generated a supramolecular arrangement. Solid-state emission of the ligand and its complex have been investigated at room temperature.     

Synthesis and Structural Characterization of Organophosphorus Ylide-1-(3-nitrophenyl)-2-(triphenyl phosphoranylidene)ethanone

The title compound Ph3P=C(H)C(O)PhNO2(L) has been prepared by the addition of triphenylphosphine in acetone as solvent to 2-bromo-1-(3-nitrophenyl)ethanone followed by the addition of alkaline solution of sodium hydroxide. The yellow crystals of the title ylide were grown in methanol/chloroform solution by drop method without stirring at room temperature. The solid state structure of ylide has been established by X-ray crystallography analysis. In the molecule of the title compound, the geometry around the P atom is nearly tetrahedral and the O atom is in synperiplanar orientation to the P atom. The nitrophenyl ring is twisted with respect to the plane of the carbonyl group through an angle of 36.6(1)°. The crystal(C26H20NO3P, Mr = 425.40) belongs to the monoclinic system, space group P21/n with a = 10.889(3), b = 14.467(3), c = 13.872(4) , β = 103.08(3)°, V = 2128.6(10) 3, Z = 4, T = 100(2) K, R = 0.059 and w R = 0.163 for 3984 observed reflections with Ⅰ 2σ(Ⅰ).     

Synthesis, Crystal Structure and Luminescence Property of a Cd(Ⅱ) Complex Assembled by 4-Carboxymethoxy Phenylacetic Acid

A new structure with the molecular formula [CdL]n was formed by CdSO4 with 4-carboxymethoxy phenylacetic acid (H2L) through the hydrothermal method. The complex was characterized by elemental analysis and infrared spectroscopy. The structure of the complex was determined by single-crystal X-ray diffraction, which is of monoclinic system, space group P21/c with a = 10.3887(2), b = 7.10710(10), c = 14.7212(2) , β = 120.6940(10)°, V = 934.65(3) 3, Dc = 2.278 g·cm-3, Z = 4, F(000) = 624, S = 1.022, the final R = 0.0187 and wR = 0.0487 for 2000 observer reflections (Ⅰ > 2σ(Ⅰ)). The center metal ion Cd(Ⅱ) in the complex is six-coordinated in a distorted octahedral geometry, and is connected with L ligands to form a 3D fishing net structure, which is a novel (3,6) network topology. The luminescence of the complex has been investigated, and the result reveals that it displays luminescent property in the voilet region.     

Synthesis, Crystal Structure and Thermal Stability of a Saturated Dimeric Ce(III)-chelated Complex Based on Benzoate and 1,10-Phenanthroline Ligands

The title complex, [Ce(BA)3phen]2 (BA = benzoate, phen = 1,10-phenanthroline), was prepared by the reaction of Ce(NO3)3·6H2O, benzoic acid and 1,10-phenanthroline. The complex was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is of triclinic, space group P1 with a = 10.912(2), b = 11.962(3), c = 12.474(3) , α = 104.889(3), β = 93.523(3), γ = 113.332(3)o, C66H46Ce2N4O12, Mr = 1366.90, V = 1420.2(6) 3, Z = 1, Dc = 1.598 g/cm3, μ = 1.652 mm-1, S = 1.024 and F(000) = 682. The final R = 0.0391 and wR = 0.0947 for 4878 observed reflections with I > 2σ(I). The structure of the title complex consists of two Ce(C6H5COO)3(C12H8N2) units, forming a binuclear molecule. Each Ce(III) is coordinated by two O atoms of one bidentate chelating carboxylate group, five O atoms of two bidentate bridging and two tridentate chelating-bridging carboxylate groups, and two N atoms of one 1,10-phenanthroline molecule to complete a distorted monocapped square antiprism geometry. Its thermogravimetric analysis was determined by TG-DTG techniques.     

Synthesis and Crystal Structure of [Cu_2(DMF)(H_2O)(C_7H_4NO_4)_2(C_7H_3NO_4)]_2·3.5DMF

A new copper(II) complex [Cu2(DMF)(H2O)(C7H4NO4)2(C7H3NO4)]2·3.5DMF has been synthesized and its structure was determined by single-crystal X-ray diffraction.The crystal is of triclinic,space group P1 with a = 10.722(3),b = 18.170(4),c = 20.923(7),α = 105.297(9),β = 101.701(10),γ = 105.74(1)°,V = 3615(1) 3,Z = 2,C58.50H64.50Cu4N11.50O31.50,Mr = 1686.90,Dc = 1.550 g/cm3,μ = 1.255 mm-1,F(000) = 1728.00,T = 150(2) K,the final R = 0.0640 and wR = 0.173 for 11310 observed reflections with I > 2σ(I).In the crystal,each formular unit consists of two dinuclear copper(II) compounds,between which the O-H···O hydrogen bonds exist.Each CuII cation is six-coordinated in an octahedral geometry.The intermolecular hydrogen-bonding interaction leads to a 3-D framework of the title compound.     

Synthesis,Crystal Structure,and Thermal Stability of a Dibutyltin Complex {[4-Et2NC6H3（O）C=NC6H3（O）- 5-NO2]（n-Bu2Sn）}2 and Its Interaction with DNA

The Schiff base organotin(IV) complex {[4-Et2NC6H3(O)C=NC6H3(O)-5-NO2](nBu2Sn)}2 has been synthesized via the reaction between 4-(diethylamino) salicylaldehyde-2-amino-4-nitrophenol Schiff base(H2L) and dibutyltin oxide. Complex C1 has been characterized by IR, 1H NMR, 13 C NMR spectra, and elemental analysis, and its crystal structure was determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 15.6559(8), b = 9.1657(5), c = 18.8351(10) , β = 107.3440(10)°, Z = 4, V = 2579.9(2) 3, Dc = 1.442 Mg·m-3, μ(MoKα) = 1.025 mm-1, F(000) = 1152, R = 0.0250 and wR = 0.0633. The central Sn atom is coordinated in a hexadentate manner to assume a distorted octahedral configuration. Complex C1 was studied by TGA analysis in air atmosphere. The interaction between complex C1 and the herring sperm DNA was realized through the intercalation of the complex based on the studies by EB fluorescent probe.     

杂-双核配合物[CaCu(C3H2O4)2(H2O)4]n的合成、晶体结构及热稳定性

The title complex, [CaCu(C3H2O4)2(H2O)4]n, with a formula of C6H12CaCuO12 and Mr=379.78 has been sy-nthesized and characterized by single crystal X-ray diffraction structure analysis, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is Orthorhombic, space group Pbcn with a=0.669 21(5) nm, b=1.370 23(5) nm, c=1.322 39(10) nm, V=1.212 59(16) nm3, Dc=2.080 g·cm-3, μ=2.288 mm-1, F(000)=772 and Z=4. The final R=0.054 0 and wR=0.112 8 for 1 189 observed reflections with I>2σ(I). The structure of the title complex consists of CaO8 polyhedra and CuO6 elongated octahedra linked together by malonate ligands. The Ca(Ⅱ) cation, on a twofold axis, is coordinated by two water molecules and six malonate O atoms. The Cu(Ⅱ) cation, which lies in a centre of symmetry in an octahedral arrangement, is coordinated by four malonate O atoms and two water molecules. The structure comprises alternating layers along the [101] plane, with the shortest Cu…Cu distance of 0.762 46(6) nm. The whole 3D structure is maintained and stabilized by the presence of hydrogen bonds. Its thermo gravimetric analysis was determined by TG-DTG techniques. CCDC:663184.     

Synthesis,Characterization and Molecular Structure of a Diiron Complex(μ-SCH_2CH_2CH_2S-μ)Fe_2(CO)_5(Ph_2PCH_3)

The title complex,(μ-pdt)Fe_2(CO)_5(Ph_2PCH_3)(pdt = SCH_2CH_2CH_2S),was obtained by the reaction of the parent complex(μ-pdt)Fe_2(CO)_6 with Ph_2PCH_3 and Me_3NO·2H_2O in good yield(90%). The title complex was characterized by IR,~1H NMR,~(31)P{~1H} NMR and ~(13)C{~1H} NMR spectroscopy as well as by single-crystal X-ray diffraction analysis. The molecular structure shows that the title complex contains a butterfly diiron propanedithiolate cluster with five terminal carbonyls and a monophosphine ligand Ph_2PCH_3. The crystal packing diagram reveals that intermolecular C H···O hydrogen bonds between CH_2 and carbonyls,π-π stacking interactions and van der Waals' interactions stabilize the solid state to form a three-dimensional network.     

Synthesis,Crystal Structure and Photoluminescence of [Gd（C6NO2H5）3- （H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O）

A heterometallic 4f-5d inorganic-organic metaMsonicotinato hybrid [Gd（C6NO2H5）3- （H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O） 1 has been synthesized via hydrothermal reaction and structurally characterized. Complex 1 crystallizes in the space group C2/c of monoclinic system with four formula units in a cell： a = 24.234（8）, b = 20.816（7）, c = 15.333（3）A , β= 128.091（8）°, V = 6088（3）A^3, C36H47Cl13Gd2Hg3N6O20, Mr = 2260.92, Dc = 2.467 g/cm^3, S = 0.896, μ（MoKα） = 10.331 mm^-1, F（000） = 4216, R = 0.0344 and wR = 0.0629. The crystal structure analysis reveals that the title complex is characteristic of a one-dimensional chain-like structure. Photoluminescent investigation reveals that the title complex displays a broad and intense emission in the green region.     

Hydrothermal Synthesis,Crystal Structure,Spectrum Properties and Quantum Chemical Calculation of a Trinuclear Copper（Ⅱ） Complex with 3-（Pyridin-2-yl）-1,2,4-triazole

A three-dimensional framework copper(Ⅱ) coordination polymer with copper carbonate basic and 3-(pyridin-2-yl)-1,2,4-triazole (Hpt) has been hydrothemally synthesized.The complex (2,C14 H10 CuN8 ·3H2 O) crystallizes in tetragonal,space group P4 2 /n,a=2.08581(12),b=2.08581(12),c=0.72331(4) nm,M r=761.73,V=3.1468(3) nm 3,Dc=1.608 g/cm 3,Z=4,F(000)=1552,GOOF=1.07,R=0.0515 and wR=0.1689.Every asymmetric unit molecular structure of the complex is composed with one copper ion,one and half water molecules and two Hpt molecules.Each copper ion is coordinated with five nitrogen atoms from four Hpt molecules,forming a distorted square pyramidal geometry.The fluorescence spectrum analysis shows that the title complex at room temperature exhibits intense photoluminescence with maximum emission at 450 nm.The quantum chemistry calculation study on the complex has been performed.The stability,some frontier molecular orbital energies and composition characteristics of some frontier molecular orbitals of the complex have been investigated.     

Synthesis and Crystal Structure of N-(Biphenyl-2-thiocarbamoyl)-4-(1,3-dichlorophenyl) Carboxamide

The synthesis of the title molecule was achieved by the reaction of 2,4-dichlorobenzoyl chloride with potassium thiocyanate in 1:1 molar ratio in dry acetonitrile to afford the corresponding isothiocyante in situ followed by the treatment with 2-aminobiphenyl. The structure of the target compound was established by elemental analysis, FTIR, 1H, 13 C NMR and mass spectroscopy and unequivocally confirmed by the crystallographic data. The title compound crystallizes in the monoclinic space group P21/n with a = 13.356(2), b = 7.0761(11), c = 20.539(3) , β = 105.723(4)°, V = 1868.5(5) 3 and Z = 4.