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1.
A novel two‐dimensional cobalt complex, [Co(btrm)2(dca)]ClO4 ( 1 , btrm = 1,2‐bis(1,2,4‐triazole‐1‐yl)methane, dca = dicyanamide), was synthesized and characterized. X‐ray diffraction analyses reveal that the title complex crystallizes in the monoclinic space group C2/m with a = 29.507(13)Å, b = 17.804(8) Å, c = 14.709(7) Å, β = 119.916(7)°, Z = 12, and R1 = 0.0784, wR2 = 0.2041. The cobalt atom involves a six‐coordinated CoN6 environment, with a distorted octahedral coordination. Two btrm ligands connect the CoII atoms with the exodentate nitrogen atoms on the 4‐position of triazole rings to form a sixteen‐membered rhombic grid. The unprecedented double btrm bridges and μ1,5‐dca bridge connect the cobalt atoms to form a two‐dimensional grid‐like layered structure. The spectroscopic and magnetic properties have also been investigated.  相似文献   

2.
One binuclear complex [Co(bpm*)2(dca)]2(ClO4)2 ( 1 ) and two 1D chain CoII complexes, {[Co(bpm)2(dca)](ClO4)}n ( 2 ) and [Co(dmf)2(dca)2]n ( 3 ), (bpm*: bis[(3, 5‐dimethyl)pyrazolyl]methane; bpm: bis(pyrazolyl)methane; dca: dicyanamide; dmf: N, N‐dimethyl formamide) have been prepared and structurally characterized. The cobalt atoms are hexa‐coordinated forming a slightly distorted octahedral coordination. Compound 1 crystallizes in the monoclinic system, space group P21/c, a = 9.849(3)Å, b = 21.944(7)Å, c = 13.814(5)Å, β = 94.824(6), Z = 4, R1 = 0.0672, wR2 = 0.1395. 1 is a binuclear complex linked by two dca ligands, and each CoII ion is coordinated by two terminal bpm* ligands. Compound 2 crystallizes in the orthorhombic system, space group Cmcm, a = 10.377(4)Å, b = 13.594(5)Å, c = 15.999(6)Å, Z = 4, R1 = 0.0609, wR2 = 0.1328. The structure of 2 can be described as a one‐dimensional zigzag chain of CoII ions bridged by one dca ligand. Each CoII ion in the chain is coordinated by two bpm ligands. Compound 3 crystallizes in the monoclinic system, space group C2, a = 13.559(15)Å, b = 7.393(8)Å, c = 8.110(9)Å, β = 112.228(15), Z = 2, R1 = 0.0260, wR2 = 0.0760. 3 has a one‐dimensional linear chain of CoII ions bridged by two dca ligands, in which each CoII ion is coordinated with two dmf molecules.  相似文献   

3.
A new energetic material, 4,5‐diacetoxyl‐2‐(dinitromethylene)‐imidazolidine (DADNI), was synthesized by the reaction of 4,5‐dihydroxyl‐2‐(dinitromethylene)‐imidazolidine (DDNI) and acetic anhydride, and characterized by single crystal X‐ray diffraction. Crystal data for DADNI are monoclinic, space group C2/c, a=15.9167(3) Å, b=8.6816(4) Å, c=8.5209(3) Å, β=103.294(9)°, V=1145.9(3) Å3, Z=4, µ=0.150 mm−1, F(000)=600, Dc=1.682 g·cm−3, R1=0.0565 and wR2=0.1649. Thermal decomposition behavior of DADNI was studied and an intensely exothermic process was observed. The kinetic equation of the decomposition reaction is: dα/dT=(1016.64/β)×4α3/4exp(−1.582×105/RT). The critical temperature of thermal explosion is 163.76°C. The specific heat capacity of DADNI was studied with micro‐DSC method and theoretical calculation method. The molar heat capacity is 343.30 J·mol−1·K−1 at 298.15 K. The adiabatic time‐to‐explosion of DADNI was calculated to be 87.7 s.  相似文献   

4.
Two novel dicyanamide complexes [Co(dmf)2(NCNCN)2] ( 1 ) and [Cu(bipy)(NCNCN)]ClO4 ( 2 ) have been synthesized and structurally characterized. 1 crystallizes in the monoclinic space group C2 with a = 13.568(6)Å, b = 7.403(3)Å, c = 8.118(3)Å and Z = 2, whereas 2 crystallizes in the monoclinic system, Cc group, a = 14.270(7)Å, b = 9.143(5)Å, c = 12.371(1) Å, β = 118.612(7)°, and Z = 4. According to X‐ray crystallographic studies, in complex 1 each CoII ion is six‐coordinated with four nitrogen atoms from four μ1, 5‐dca (dca = dicyanamide) ligands and two oxygen atoms from two dmf ligands to form distorted octahedra. 1 forms a 1‐D network bridged via μ1, 5‐dca. 2 consists of a uniform Cu(NCNCN)Cu chain, each CuII ion is octahedrally coordinated with four nitrogen atoms from two μ1, 5‐dca ligands and one bipy ligand and two oxygen atoms from two ClO4 ions. The octahedral CuII ion shows a significant Jahn‐Teller distortion, with two axial oxygen atoms considerably farther from the copper than the four equatorial nitrogens.  相似文献   

5.
Two new trans‐disubstituted cyclam ligands; 1,8‐di(6‐hydroxymethylpyridin‐2‐ylmethyl)‐1,4,8,11‐tetra‐azacyclotetradecane ( 5 ) and 1,8‐dimethyl‐4, 11‐di(6‐hydroxymethylpyridin‐2‐ylmethyl)‐1,4,8,11 ‐tetraaza‐cyclotetradecane ( 6 ); have been synthesized and characterized. The crystal structures of ligand 6 and its Ni(II) and Co(II) complexes have been determined. Crystal data are given for 6 , space group, P21/c, a = 11.095 (6) Å, b = 9.467 (5) Å, c = 13.283 (8) Å; β = 106.95 (5)°, Z = 2, R = 0.0715; for [Ni 6 ](C104)2, space group P21/c, a = 9.4848 (14) Å, b = 33.941(6) Å, c = 9.793(2) A, β = 95.264(14)°, Z = 4, R = 0.0567; for [Co 6 ](C104)2, space group, P21/c, a = 9.440 (6) Å, b = 33.848 (13) Å, c = 9.820 (3) Å, β = 95.16(3)°, Z = 4, R = 0.0718. In both complexes, the metal atoms are six‐coordinate with only one of the pendants interacting with the central metal atom and the other pendant remaining uncoordinated.  相似文献   

6.
The η2‐thio‐indium complexes [In(η2‐thio)3] (thio = S2CNC5H10, 2 ; SNC4H4, (pyridine‐2‐thionate, pyS, 3 ) and [In(η2‐pyS)22‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η2‐acac)indium complex [In(η2‐acac)3], 1 with HS2CNC5H10, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) Å3, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P21 with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) Å3, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.  相似文献   

7.
The title hydrated ionic complex, [Ni(CH3COO)(C12H12N2)2]ClO4·H2O or [Ni(ac)(5,5′‐dmbpy)2]ClO4·H2O (where 5,5′‐dmbpy is 5,5′‐dimethyl‐2,2′‐bipyridine and ac is acetate), (1), was isolated as violet crystals from the aqueous ethanolic nickel acetate–5,5′‐dmbpy–KClO4 system. Within the complex cation, the NiII atom is hexacoordinated by two chelating 5,5′‐dmbpy ligands and one chelating ac ligand. The mean Ni—N and Ni—O bond lengths are 2.0628 (17) and 2.1341 (15) Å, respectively. The water solvent molecule is disordered over two partially occupied positions and links two complex cations and two perchlorate anions into hydrogen‐bonded centrosymmetric dimers, which are further connected by π–π interactions. The magnetic properties of (1) at low temperatures are governed by the action of single‐ion anisotropy, D, which arises from the reduced local symmetry of the cis‐NiO2N4 chromophore. The fitting of the variable‐temperature magnetic data (2–300 K) gives giso = 2.134 and D/hc = 3.13 cm−1.  相似文献   

8.
The title compound, [Th(C12H15O4)4]n, is the first homoleptic thorium–carboxylate coordination polymer. It has a one‐dimensional structure supported by the bidentate bridging coordination of the singly charged 3‐carboxyadamantane‐1‐carboxylate (HADC) anions. The metal ion is situated on a fourfold axis (site symmetry 4) and possesses a square‐antiprismatic ThO8 coordination, including four bonds to anionic carboxylate groups [Th—O = 2.359 (2) Å] and four to neutral carboxyl groups [Th—O = 2.426 (2) Å], while a strong hydrogen bond between these two kinds of O‐atom donor [O...O = 2.494 (3) Å] affords planar pseudo‐chelated Th{CO2...HO2C} cycles. This combination of coordination and hydrogen bonding is responsible for the generation of quadruple helical strands of HADC ligands, which are wrapped around a linear chain of ThIV ions [Th...Th = 7.5240 (4) Å] defining the helical axis.  相似文献   

9.
The self‐assembly of NiCl2·6H2O with a diaminodiamide ligand 4,8‐diazaundecanediamide (L‐2,3,2) gave a [Ni(C9H20N4O2)(Cl)(H2O)] Cl·2H2O ( 1 ). The structure of 1 was characterized by single‐crystal X‐ray diffraction analysis. Structural data for 1 indicate that the Ni(II) is coordinated to two tertiary N atoms, two O atoms, one water and one chloride in a distorted octahedral geometry. Crystal data for 1: orthorhombic, space group P 21nb, a = 9.5796(3) Å, b = 12.3463(4) Å, c = 14.6305(5) Å, Z = 4. Through NH···Cl–Ni (H···Cl 2.42 Å, N···Cl 3.24 Å, NH···Cl 158°) and OH···Cl–Ni contacts (H···Cl 2.36 Å, O···Cl 3.08 Å, OH···Cl 143°), each cationic moiety [Ni(C9H20N4O2) (Cl)(H2O)]+ in 1 is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chainlike structure. Thermogrametric analysis of compound 1 is consistent with the crystallographic observations. The electronic absorption spectrum of Ni(L‐2,3,2)2+ in aqueous solution shows four absorption bands, which are assigned to the 3A2g3T2g, 3T2g1Eg, 3T2g3T1g, and 3A2g3T1g transitions of triplet‐ground state, distorted octahedral nickel(II) complex. The cyclic volammetric measurement shows that Ni2+ is more easily reduced than Ni(L‐2,3,2)2+ in aqueous solution.  相似文献   

10.
Reaction between an aqueous ethanol solution of tin(II) chloride and that of 4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐one in the presence of O2 gave the compound cis‐dichlorobis(4‐propanoyl‐2,4‐dihydro‐5‐methyl‐2‐phenyl‐3 H‐pyrazol‐3‐onato) tin(IV) [(C26H26N4O4)SnCl2]. The compound has a six‐coordinated SnIV centre in a distorted octahedral configuration with two chloro ligands in cis position. The tin atom is also at a pseudo two‐fold axis of inversion for both the ligand anions and the two cis‐chloro ligands. The orange compound crystallizes in the triclinic space group P 1 with unit cell dimensions, a = 8.741(3) Å, b = 12.325(7) Å, c = 13.922(7) Å; α = 71.59(4), β = 79.39(3), γ = 75.18(4); Z = 2 and Dx = 1.575 g cm–3. The important bond distances in the chelate ring are Sn–O [2.041 to 2.103 Å], Sn–Cl [2.347 to 2.351 Å], C–O [1.261 to 1.289 Å] and C–C [1.401 Å] the bond angles are O–Sn–O 82.6 to 87.7° and Cl–Sn–Cl 97.59°. The UV, IR, 1H NMR and 119Sn Mössbauer spectral data of the compound are reported and discussed.  相似文献   

11.
By alternating‐current electrochemical technique crystals of copper(I) π‐complex with 1‐allylpyridinium chloride of [C5H5N(C3H5)][Cu2Cl3] ( 1 ) composition have been obtained and structurally investigated. Compound 1 crystallizes in monoclinic system, space group C2/c a = 24.035(1) Å, b = 11.4870(9) Å, c = 7.8170(5) Å, β = 95.010(5)°, V = 2150.0(2) Å3 (at 100 K), Z = 8, R = 0.028, for 4836 independent reflections. In the structure 1 trigonal‐pyramidal environment of π‐coordinated copper(I) atom is formed by a lengthened to 1.376(2) Å C=C bond of allyl group and by three chlorine atoms. Other two copper atoms are tetrahedrally surrounded by chlorine atoms only. The coordination polyhedra are combined into an original infinite (Cu4Cl62—)n fragment. Structural comparison of 1 and the recently studied copper(I) chloride π‐complexes with 3‐amino‐, 2‐amino‐, 4‐amino‐1‐allylpyridinium chlorides of respective [LCu2Cl3] ( 2 ), [L2Cu2Cl4] ( 3 ), and [LCuCl2] ( 4 ) compositions allowed us to reveal the trend of the inorganic fragment complication which depends on pKa (base) value of the corresponding initial heterocycle.  相似文献   

12.
Complex formation of 2, 6‐bis(2′‐hydroxyphenyl)pyridine (H2Li) with Fe3+ and Cu2+ was investigated in a H2O/DMSO medium (mole fraction xDMSO = 0.2) by potentiometric and spectrophotometric methods. The pKa values of [H3Li]+ are 2.25, 10.51 and 14.0 (25 °C, 0.1 M KCl). The formation constants of [FeIII(Li)]+ and [CuII(Li)] (25 °C, 0.1 M KCl) are log β1 = 21.5 for Fe3+ and log β1 = 18.5 for Cu2+. The crystal structures of [Al(Li)2Na(EtOH)3], [Fe(Li)2Na(EtOH)3], and [Cu(Li)(py)]2 were investigated by single‐crystal X‐ray diffraction analyses. The FeIII and the AlIII compound are isotypic and crystallize in the monoclinic space group P21/n. Al‐compound (215 K): a = 12.599(3) Å, b = 16.653(3) Å, c = 17.525(4) Å, β = 100.27(3)°, Z = 4 for C40H40AlN2NaO7; Fe‐compound (293 K): a = 12.753(3) Å, b = 16.715(3) Å, c = 17.493(3) Å, β = 99.68(3)°, Z = 4 for C40H40FeN2NaO7. Both compounds contain a homoleptic, anionic bis‐complex [M(Li)2] of approximate D2 symmetry. The Cu compound crystallized as an uncharged, dinuclear and centrosymmetric [Cu(Li)(py)]2 complex in the monoclinic space group P21/n with (293 K) a = 13.386(3) Å, b = 9.368(2) Å, c = 14.656(3) Å, β = 100.65(3)°, Z = 2 for C44H32Cu2N4O4. The structural properties and in particular the possible influence of the ligand geometry on the stability of the metal complexes is discussed.  相似文献   

13.
The title compound 4 , i.e. 9‐chloro‐4,5‐dihydro‐2‐ethyl‐1‐(2,4,6‐trichlorophenyl)‐1H‐1,2,4‐triazolo[3,2‐d]‐[1,5]benzoxazepinium hexachloroantimonate, is a novel 6‐7‐5 tricyclic heterocycle. C18H14Cl4N3O·SbCJ6, M = 764.61, P21/c(#14), a = 13.457(4), b = 11.583(2), c = 18.992(3) Å α = 90, β = 110.11(1)°, Z = 4, V = 2780(1) Å3, Dc = 1.827 g/cc, μ (MoKα) = 19.69 cm?1, F(000) = 1488.00, T = 293 K, Rint = 0.055 for 3094 independent reflections with I>3.00σ(I). The five‐membered heterocyclic ring is nearly planar, with the trichlorophenyl ring at N(2) almost perpendicular to it. However, the seven‐membered ring is not planar, but adopts a twist‐boat conformation.  相似文献   

14.
15.
The crystal structure of the title compound, [CoCl‐(C16H26N6)]ClO4, consists of discrete [CoCl­(C16­H26N6)]+ cations and perchlorate anions. The five‐coordinate CoII atom has four nitro­gen donors from the new mesocyclic ligand 1,5‐bis(1‐methyl‐1H‐­imidazol‐2‐ylmethyl)‐1,5‐di­aza­cyclo­octane [Co—N 2.046 (3)–2.214 (4) Å], and a chloride anion at the apical site [Co—Cl 2.3184 (13) Å]. The coordination geometry of the complex is essentially square pyramidal. The mesocyclic ligand takes a boat–chair configuration and the two imidazole pendants are not coplanar. The dihedral angle between the two imidazole planes is 15.97°. An H atom from the 1,5‐diaza­cyclo­octane group effectively blocks the axial coordination site opposite the Cl ligand.  相似文献   

16.
The title compound, [Cu(C2H3N)2(C10H24N4)](C32H12BF24)2·0.31H2O, crystallizes as an ionic species with no interactions between the ions. The [CuII(cyclam)(MeCN)2]2+ dication (cyclam is 1,4,8,11‐tetra­aza­tetra­decane), located on a 2/m symmetry site, forms as a distorted octahedral species with four Cu—Ncyclam bonds of 2.013 (2) Å and two C—NMeCN bonds of 2.499 (4) Å. The [B{C6H3(CF3)‐3,5}4] anion, located on a twofold axis, is a distorted octahedral species. A small amount of water is present, occupying sites between columns of ions.  相似文献   

17.
The unusual 12‐membered ring compound, octahydro‐5H,12H‐4,11‐methano‐1H,7H‐bis[1,2,5]oxadiazolo[3,4‐d:3′,4′‐j][1,7,3,9]dioxadiazacyclododecine is obtained from the acid catalyzed reaction of 3‐amino‐4‐hydroxymethylfurazan with formaldehyde instead of the expected methylene‐bridged compound, 4,4′‐methylenebis[4,5‐dihydro‐7H‐[1,2,5]oxadiazolo[3,4‐d][1,3]oxazine]. The compound crystallizes in Tetragonal, P43212, a = 6.4141(4) Å, b = 6.4141(4) Å, c = 26.525(3) Å, α = 90°, β = 90°, γ = 90°, V = 1091.27(16) Å3, Z = 4, dcalc = 1.614 Mg/m3.  相似文献   

18.
In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ4N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ2N,S]­zinc(II) ethanol sol­vate, [Zn(C8H22N4)2(C3HN3S3)]·C2H6O, the ZnII atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH2−) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.  相似文献   

19.
The title compound, [Cu(C2N3)(C3H10N2)2]ClO4, is made up of [Cu(tn)2{N(CN)2}]+ complex cations (tn is 1,3‐diamino­propane) and ClO4 anions. The CuII atom is coordinated by four N atoms of two equatorial tn ligands, with an average distance of 2.041 (7) Å, and one nitrile N atom of the dicyanamide anion in an axial position, at a distance of 2.236 (3) Å, in a manner approaching square‐planar coordination geometry. The complex has Cs symmetry, with the mirror plane lying through the central C atoms of both tn ligands and the dca ligand. The ClO4 anion might be considered as very weakly coordinated in the opposite axial position [Cu—O = 2.705 (3) Å], thus completing the CuII coordination to asymmetric elongated octa­hedral (4+1+1*). The Cu atom and the perchlorate anion both lie on mirror planes.  相似文献   

20.
Crystals of the zwitterionic copper(I) π‐complex [(HC≡CCH2NH3)Cu2Br3] have been synthesized by interaction of CuBr with [HC≡CCH2NH3]Br in aqueous solution (pH < 1) and X‐ray studied. The crystals are monoclinic: space group P21/n, a = 6.722(4), b = 12.818(8), c = 9.907(3) Å, β = 100.25(4)°, V = 840.0(8) Å3, Z = 4, R = 0.0592 for 3015 reflections. The crystal structure of the π‐complex contains isolated [(HC≡CCH2NH3)+(Cu2Br3)?]2 units which are incorporated into a framework by strong hydrogen N–H···Br and C≡C–H···Br bonds. The length of π‐coordinated propargylammonium C≡C bond is equal 1.216(8) Å and Cu(I)–(C≡C) distance equals 1.958(5) Å.  相似文献   

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