共查询到20条相似文献,搜索用时 828 毫秒
1.
The reaction of N-benzoylphosphoramidic dichloride with amines afforded some new N-benzoylphos-phoric triamides with formula C6H5C(O)NHP(O)(X)2, X=NH–CH(CH3)2 (1), NH–CH2–CH(CH3)2 (2), NH–CH2–CH(OCH3)2 (3), N(CH3)[CH2CH(OCH3)2] (4) and N(CH3)(C6H11) (5) that were characterized by 1H,13C,31P NMR, IR spectroscopy and elemental analysis. The structures have been determined for compounds 4 and 5 by X-ray crystallography. These compounds contain one amidic hydrogen atom and form centrosymmetric dimmers via intermolecular
–P–O⋯H–N–hydrogen bonds besides weak C–H⋯O hydrogen bonds that lead to three-dimensional polymeric clusters in the crystalline
lattice. 相似文献
2.
M. M. Monchak A. V. Pavlyuk V. V. Kinzhibalo M. G. Mys’kiv 《Russian Journal of Coordination Chemistry》2009,35(6):405-410
The alkylation of ethylenediamine with allyl bromide in the presence of a fourfold (with respect to ethylenediamine) molar
amount of NaHCO3 in acetone with an ethanol admixture (15: 1) affords LBr2 · 2H2O (I), where L2+ is the N,N,N,N′,N′,N′-hexaallylethylenediaminium cation. Single crystals of complexes L[CuII(Br0.45Cl3.55)] (II), L[Cu4I(Br4.55Cl1.45)] (III), and L[Cu4IBr6] (IV) are prepared by ac electrochemical synthesis from an ethanolic solution of LBr2 · 2H2O, CuCl2 · 2H2O (or CuBr2) at copper wire electrodes. The crystal structures of compounds I–IV are determined by X-ray diffraction analysis. The crystals of complex I are monoclinic: space group P21/n, a = 8.544(3), b = 10.404(3), c = 13.350(4) ?, β = 97.29(3)°, V = 1177.2(6) ?3, Z = 2. The bromine anions in compound I are bonded to the L2+ cations and water molecules through hydrogen contacts (E)H…Br (E = O, C) of 2.57(3)–2.86(3) ?. The crystals of compounds
II–IV are triclinic: space group P
. For II: a = 8.762(4), b = 9.163(4), c = 16.500(6) ?, α = 95.62(4)°, β = 96.39(4)°, γ = 111.46(4)°, V = 1211.4(9) ?3, Z = 2; for III: a = 9.074(4), b = 9.435(4), c = 9.829(5) ?, α = 116.12(4)°, β = 104.14(4)°, γ = 100.22(4)°, V = 692.3(6) ?3, Z = 1; for IV isostructural III: a = 9.084(4), b = 9.404(4), c = 9.869(4) ?, α = 116.31(3)°, β = 104.00(3)°, γ = 100.37(3)°, V = 692.1(5) ?3, Z = 1. Unlike the isolated tetrahedral CuX42− anion in structure II, an original chain anion (Cu4X62−)
n
is observed in the structures of π complexes III and IV.
Original Russian Text ? M.M. Monchak, A.V. Pavlyuk, V.V. Kinzhibalo, M.G. Mys’kiv, 2009, published in Koordinatsionnaya Khimiya,
2009, Vol. 35, No. 6, pp. 414–419. 相似文献
3.
The ortho-metalated complex [Pd(x){κ
2
(C,N)-[C6H4CH2NRR′ (Y)}] (2a–4a and 2b–3b) was prepared by refluxing in benzene equimolecular amounts of Pd(OAc)2 and secondary benzylamine [a, EtNHCH2Ph; b, t-BuNHCH2Ph followed by addition of excess NaCl. The reaction of the complexes [Pd(x){κ
2
(C,N)-[C6H4CH2NRR′ (Y)}] (2a–4a and 2b–3b) with a stoichiometric amount of Ph3P=C(H)COC6H4-4-Z (Z = Br, Ph) (ZBPPY) (1:1 molar ratio), in THF at low temperature, gives the cationic derivatives [Pd(OC(Z-4-C6H4C=CHPPh3){κ
2
(C,N)-[C6H4CH2NRR′(Y)}] (5a–9a, 4b–6b, and 4b′–6b′), in which the ylide ligand is O-coordinated to the Pd(II) center and trans to the ortho-metalated C(6)H(4) group, in an “end-on
carbonyl”. Ortho-metallation, ylide O-coordination, and C-coordination in complexes (5a–9a, 4b–6b, and 4b′–6b′) were characterized by elemental analysis as well as various spectroscopic techniques. 相似文献
4.
Two new 3,5-diaryl-1H-pyrazoles: 3(5)-(4-tert-butylphenyl)-5(3)-(naphthalene-2-yl)-1H-pyrazole (1) and 5-(4-(benzyloxy)phenyl)-3-(furan-2-yl)-1H-pyrazole (2) were synthesized and characterized. Two strong ions peaks [2M]+ and [2M + Na]+ observed in the ESI–MS spectra are attributed to the dimerization process in solution formed by intermolecular N–H···N hydrogen
bonds. The crystal structures have been determined by X-ray crystal structure analysis. Compound 1 exists as a pair of tautomers 1a and 1b, and its dimer [R
22(6) motif] is formed by the tautomers 1a and 1b. Compound 2 only exists as a 2a tautomer, and interesting intermolecular N–H···O and O–H···N hydrogen bonds link two pyrazoles and two methanol molecules,
leading to the formation of an R
44(10) dimer motif. 相似文献
5.
Sumitava Khan Subhasis Roy Kishalay Bhar Partha Mitra Alexandra M. Z. Slawin Barindra Kumar Ghosh 《Transition Metal Chemistry》2011,36(1):99-106
Two hexacoordinated mononuclear Co(III) compounds of the type cis-[Co(L)(N3)2] X [1, X = ClO4; 2, X = PF6; L = N,N′-(bis(pyridine-2-yl)benzylidine)-1,4-butanediamine] have been synthesized and characterized by physicochemical and spectroscopic
methods. The crystal structures of complexes 1 and 2 both have distorted octahedral geometry with two terminal azides in mutual cis orientations. In the crystalline state, two
mononuclear units of 1 are associated by weak C–H…π interactions to produce a dimeric unit, which packs through C–H…O hydrogen bonds and π…π interactions
leading to a 2-D continuum. The mononuclear units in 2 are engaged in weak cooperative intermolecular C–H…π interactions and multiple C–H…F hydrogen bonds giving rise to a 3-D
network structure. These diamagnetic compounds are redox active and show luminescence in DMF solutions. 相似文献
6.
The paper reports the synthesis and characterization of vanadium complexes of N,N′-(±)-trans-bis(2,4-dihydroxyacetophenone)-1,2-cyclohexanediamine (H2L1) and N,N′-(±)-trans-bis(2,4-dihyroxy-5-nitroacetophenone)-1,2-chyclohexanediamine (H2L2). All the complexes were characterized by elemental analysis, magnetic susceptibility measurements, infrared and electronic
spectra, and thermogravimetric analysis. The X-ray patterns of the [VO(L1)] · H2O (I) and [VO(L2)] · H2O (II) complexes show the monoclinic system with the unit cell parameters a = 26.1352, b = 11.7149, c = 6.0401 β = 115.38° and a = 29.3787, b = 12.9398, c = 5.9175 β = 96.84°, respectively. The complexes I and II catalyze the oxidation of styrene in the presence of hydrogen peroxide. 相似文献
7.
X. F. Wang J. Gao J. Wang Zh. H. Zhang Y. F. Wang L. J. Chen W. Sun X. D. Zhang 《Journal of Structural Chemistry》2008,49(4):724-731
The title compounds, (NH4)2[MnII(edta)(H2O)]·3H2O (H4edta = ethylenediamine-N,N,N′,N′-tetraacetic acid), (NH4)2[MnII(cydta)(H2O)]·4H2O (H4cydta = trans-1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid) and K2[MnII(Hdtpa)]·3.5H2O (H5dtpa = diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid), were prepared; their compositions and structures were determined
by elemental analysis and single-crystal X-ray diffraction technique. In these three complexes, the Mn2+ ions are all seven-coordinated and have a pseudomonocapped trigonal prismatic configuration. All the three complexes crystallize
in triclinic system in P-1 space group. Crystal data: (NH4)2[MnII(edta)(H2O)]·3H2O complex, a = 8.774(3) ?, b = 9.007(3) ?, c = 13.483(4) ?, α = 80.095(4)°, β = 80.708(4)°, γ = 68.770(4)°, V = 972.6(5) ?3, Z = 2, D
c = 1.541 g/cm3, μ = 0.745 mm−1, R = 0.033 and wR = 0.099 for 3406 observed reflections with I ≥ 2σ(I); (NH4)2[MnII(cydta)(H2O)]·4H2O complex, a = 8.9720(18) ?, b = 9.4380(19) ?, c = 14.931(3) ?, α = 76.99(3)°, β = 83.27(3)°, γ = 75.62(3)°, V = 1190.8(4)?3, Z = 2, D
c = 1.426 g/cm3, μ = 0.625 mm−1, R = 0.061 and wR = 0.197 for 3240 observed reflections with I ≥ 2σ(I); K2[MnII(Hdtpa)]·3.5H2O complex, a = 8.672(3) ?, b = 9.059(3) ?, c = 15.074(6) ?, α = 95.813(6)°, β = 96.665(6)°, γ = 99.212(6)°, V = 1152.4(7) ?3, Z = 2, D
c = 1.687 g/cm3, μ = 1.006 mm−1, R = 0.037 and wR = 0.090 for 4654 observed reflections with I ≥ 2σ(I).
Original Russian Text Copyright ? 2008 by X. F. Wang, J. Gao, J. Wang, Zh. H. Zhang, Y. F. Wang, L. J. Chen, W. Sun, and X.
D. Zhang
The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 753–759, July–August, 2008. 相似文献
8.
J. Q. Gao T. Wu J. Wang X. D. Jin D. Li B. X. Wang K. Li Y. Li 《Russian Journal of Coordination Chemistry》2011,37(11):817-824
In this work, the title complexes, (EnH2)1.5[ErIII(Ttha)] · 3H2O (I) and (EnH2)[ErIII(Egta)(H2O)]2 · 6H2O (II), where En = ethylenediamine, H6Ttha = triethylenetetramine-N,N,N′,N″,N″’,N″′-hexaacetic acid, H4Egta = ethyleneglycol-bis-(2-aminoethylether)-N,N,N′,N′-tetraacetic acid, have been successfully synthesized. Their structures have been characterized by IR spectroscopy and single-crystal
X-ray diffraction techniques. The X-ray diffraction reveals that I is nine-coordinated and crystallizes in the monoclinic crystal space group P2/n with cell dimensions a = 17.6058(16), b = 9.6249(9), c = 20.560(2) ?, β = 109.7440(10)°, and V = 3279.1(5) ?3. Compound II is also nine-coordinated and crystallizes in the monoclinic crystal space group P21/n with the cell dimensions a = 12.938(6), b = 12.651(5), c = 14.943(6) ?, β = 105.441(5)°, and V = 2357.5(17) ?3. In I, each EnH22+ cation connects three adjacent [ErIII(Egta)(H2O)]− complex anions through hydrogen bonds, while in I, there are two types of EnH2
2+ anions. One is highly symmetrical, forming hydrogen bonds with two neighboring [ErIII(Ttha)]3− complex anions. The other anion connects three adjacent [ErIII(Ttha)]3− complex anions through hydrogen bonds. These hydrogen bonds lead to the formation of 2D ladder-like layer structure. 相似文献
9.
N. N. Pesyan 《Journal of Structural Chemistry》2010,51(5):991-995
A new tetracyclic compound, 1,9-dimethyl-4,5-dihydro-6H-pyrido[3’,2’:4,5]thieno[2,3-f]pyrrolo[l,2-a][1,4]diazepin-6-one (2) was isolated and studied by X-ray crystallography. Compound 2 crystallizes in the orthorhombic system,
space group Pna21, a = 11.1098(8) ?, b = 8.4815(6) ?, c = 28.367(2) ?, V= 2673.0(3) ?3, Z=8. The crystal structure comprises two crystallographically independent molecules of the compound. They relate as stereoisomers;
in each the diazepine ring exhibits a boat conformation. The crystal packing reveals zigzag H-bonded chains with two distinct
hydrogen bonds. The H…O distances and N-H…O angles for N3-H3…O1’ are 2.012? and 174°, and for N3’-H3’…O1 are 1.974? and 154°,
respectively. 相似文献
10.
Zuzana Vasková Zdenka Padělková Milan Mazur Dušan Valigura Jan Moncol 《Transition Metal Chemistry》2011,36(8):883-889
The synthesis, spectral characterization and crystal structures of two nitrobenzoatocopper(II) complexes, namely [Cu(2-O2Nbz)2(pca)2(H2O)2] (1) and [Cu(3,5-(O2N)2bz)2(pca)2(H2O)2] (2) (where 2-O2Nbz = 2-nitrobenzoate, 3,5-(O2N)2bz = 3,5-dinitrobenzoate, pca = pyrazinecarboxamide), are reported. Complexes 1 and 2 consist of centrosymmetric molecules with the Cu(II) atom monodentately coordinated by a pair of anionic 2-nitrobenzoato
(1) or 3,5-dinitrobenzoato (2) ligands and a pair of pyrazinecarboxamide ligands, forming a nearly tetragonal basal plane, and by a pair of water ligands
that complete the tetragonal–bipyramidal coordination polyhedron. The molecules of both complexes are linked by N–H⋯O and
O–H⋯O hydrogen bonds and lie in planes, which have different orientations depending on the space group. Similar experiments
with 3-nitrobenzoic acid resulted in the isolation of the hydrolysis product [Cu(pyzCOO)2]
n
(3) (pyzCOO = pyrazinecarboxylate). The known crystal structure of complex 3 has been re-determined at low temperature with significantly higher precision. The crystal packing and C–H⋯O/C–H⋯N hydrogen
bonds are discussed. 相似文献
11.
Reaction of [Au2(dppm)Cl2] with AgOTf in CH2Cl2 medium followed ligand addition and leads to [Au2(dppm)(RaaiR′)](OTf) [RaaiR′ = p-R–C6H4–N = N–C3H2–NN–1–R′, (1–3), abbreviated as N,N′-chelator, where N(imidazole) and N(azo) represent N and N′, respectively; R = H (a), Me (b), Cl (c) and R′ = Me (1), CH2CH3
(2), CH2Ph (3), OSO2CF3 is the triflate anion, and dppm is the diphenylphosphinomethane-ring]. The 1H-n.m.r. spectral measurements suggest methylene, –CH2–, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets with coupling constant of avg. 6 Hz. Considering all the moities there are a lot of different
carbon atoms in the molecule which gives a lot of different peaks in the 13C-n.m.r spectrum. In the 1H–1H-COSY spectrum of the present complexes and contour peaks in the 1H–13C-HMQC spectrum in the present complexes, assign the solution structure and stereoretentive transformation in each step. 相似文献
12.
Ming-Li Liu Jian-Min Dou Da-Cheng Li Da-Qi Wang Jian-Zhong Cui 《Transition Metal Chemistry》2012,37(1):117-124
The thiosemicarbazide and hydrazide Cu(II) complexes, [Cu3L21(py)4Cl2] (1), [Cu(HL2)py] (2) and [Cu(HL3)py] (3), (H2L1 = 1-picolinoylthiosemicarbazide, H3L2 = N′-(2-hydroxybenzylidene)-3-hydroxy-2-naphthohydrazide, H3L3 = 2-hydroxy-N′-((2-hydroxy-naphthalen-1-yl)methylene)benzohydrazide) have been prepared and characterized through physicochemical and spectroscopic
methods as well as X-ray crystallography. Complex 1 has a centrosymmetric structure with –N–N– bridged Cu3 skeleton. Neighboring molecules are linked into a 3D supermolecular framework by π–π stacking interactions, N–H···Cl and
C–H···Cl hydrogen bonds. Complexes 2 and 3 have similar planar structures but different dimers formed by concomitant Cu···N and Cu···O interactions, respectively. Solvent
accessible voids with a volume of 391 ?3 are included in the structure of complex 2, indicating that this complex is a potential host candidate. Thermogravimetric analysis shows that the three complexes are
stable up to 100 °C. 相似文献
13.
Franz A. Mautner Febee R. Louka August A. Gallo Jörg H. Albering Mohamed R. Saber Nagua B. Burham Salah S. Massoud 《Transition Metal Chemistry》2010,35(5):613-619
Two thiocyanato-Cu(II) complexes including mononuclear dithiocyanato Cu(Me3dpt)(NCS)2 (1) and the polymeric 1D [Cu(d,l-Ala)(μN,S–NCS)(H2O)]
n
(2) were synthesized and structurally characterized (Me3dpt = bis(N-methyl-3-propyl)methylamine, Ala = alaninate anion). The IR spectrum of complex 1 confirmed the N-bonding coordination mode of the thiocyanate groups, and its visible spectrum revealed the square pyramidal
geometry around the central Cu2+ ion. Single X-ray crystallography of 1 showed that the Cu(II) center displays square pyramidal geometry with severe distortion toward trigonal bipyramidal environment. Complex 2 forms a 1-D polymeric chain with the NCS− acting as a μN,S-ligand. A distorted SP geometry around the Cu2+ centers was achieved by the O and N atoms of alaninato anion, the aqua ligand and by the N and S atoms of the bridging thiocyanate
groups. Hydrogen bonds of the type N–H···O, N–H···S and O–H···O are formed in this complex leading to the extension of the
1D chain to a supramolecular network. 相似文献
14.
Conformational analysis of N-isopropylbenzohydroxamic acids: crystal structure, DFT, and NMR studies
X-ray crystal structure determinations together with density functional theory (DFT) calculations in vacuo and NMR studies
in solution have been carried out for 4-MeOC6H4CONPriOH 2a and 3,5-(NO2)2C6H3CONPriOH 2b. The results were compared with that for the respective N-methyl benzohydroxamic acids. For crystal structures as well as for DFT-optimized geometries of 2 (both isomers) in vacuo, the effect of substituents in aromatic ring manifested by changing of charges is inconspicuous.
Studies of potential energy surfaces showed that libration barrier around ω
1 = 0° is low enough to make electron conjugation feasible, and that for 2b rotation barrier around C(O)N bond is higher by 6 kcal/mol and additionally, that rotation around N–C bond is hindered. A
careful analysis of low-temperature 1H NMR spectra confirmed the greater stability of Z-2a, the greater rigidity of E-2b and the influence of solvent on both isomers population. Despite solvent-dependent conformational alteration, both 2a and 2b crystallize exclusively as E isomers from ethyl acetate solution. Correlations of absolute 1H, 13C, and 15N shielding calculations with experimental data were also analyzed.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
15.
R. Xu D. Li J. Wang Y. X. Kong B. X. Wang Y. M. Kong T. T. Fan B. Liu 《Russian Journal of Coordination Chemistry》2010,36(11):810-819
Two novel ethylenediaminium salt of europium complexes with aminopolycarboxylic acid ligands, (EnH2)3[EuIII(Ttha)]2 · 11H2O (I) (En is ethylenediamine, H6Ttha is triethylenetetramine-N,N,N′,N″,N‴,N‴-hexaacetic acid) and (EnH2)[EuIII(Egta)(H2O)]2 · 6H2O (II) (H4Egta is ethyleneglycol-bis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid) complexes were synthesized, and their crystal structures
were determined by single-crystal X-ray diffraction techniques. Both of the two complexes adopt nine-coordinate structures
with the pseudo-monocapped square antiprism and crystallize in the monoclinic crystal system with the P21/n space group. The crystal data for complex I are as follows: a = 17.8262(8), b = 19.3137(5), c = 20.6233(8) ?, β = 111.301(2)°, V = 6615.3(4) ?3, Z = 8, ρ
c
= 1.677 mg/m3, μ = 1.981 mm−1, F(000) = 3432, R = 0.0308, and wR = 0.0737 for 43622 observed reflections with I ≥ 2σ(I). The crystal data for complex II are as follows: a = 12.952(3), b = 12.618(2), c = 14.809(3) ?, β = 105.695(2)°, V = 2330.0(8) ?3, Z = 4, ρ
c
= 1.800 mg/m3, μ = 2.765 mm−1, F(000) = 1276, R = 0.0297, and wR = 0.0638 for 18416 observed reflections with I ≥ 2σ(I). One remarkable feature of the two complexes is that the protonated [EnH22+] cations conjugating to [EuIII(Ttha)]26− and [EuIII(Egta)(H2O)]22− complex anions are reviewed, respectively, which open the path for the EuIII complexes conjugating with other various biomolecules. 相似文献
16.
Nathan C. Tice Chad A. Snyder Andrew Z. Preston Marika B. Wieliczko Jason O. E. Young Daniel F. Hinson 《Transition Metal Chemistry》2012,37(2):141-147
A series of 1,2-diacyl cyclopentadienyl tricarbonyl manganese and rhenium complexes, [M(CO)3{η5-1,2-C5H3(CO-(R)2}] (3a–c and 4a–b), were isolated utilizing a straightforward, 3-step route. The synthetic pathway began with a 1,2-diacyl cyclopentadiene
(fulvene), followed by the formation of its corresponding thallium salt and transmetallation with the appropriate pentacarbonyl
metal bromide. X-ray crystallographic analysis and high-accuracy mass spectrometry confirmed the structures of the both the
4-methoxyphenyl and 4-chlorophenyl diacyl rhenium complexes, [Re(CO)3{η5-1,2-C5H3(CO-(4-OCH3)C6H4)2}] (4a) and [Re(CO)3{η5-1,2-C5H3(CO-(4-Cl)C6H4)2}] (4b). Diacyl complexes 3a–c and 4a–b were then ring-closed with hydrazine hydrate to form their corresponding pyridazine complexes, [M(CO)3{η5-1,2-C5H3(1,4-(R)2N2C2}] (5a–c and 6a–b), in good yields (60–83%). The pyridazyl ligands were found to be relatively labile, and recrystallization of the target
complexes 5a–c and 6a–b afforded only the free pyridazine ligands. 相似文献
17.
Diacetylplatinum(II) complexes [Pt(COMe)2(N^N)] (N^N = bpy, 3a; 4,4′-t-Bu2-bpy, 3b) were found to undergo oxidative addition reactions with organyl halides. The reaction of 3a with methyl iodide and propargyl bromide led to the formation of the cis addition products (OC-6-34)-[Pt(COMe)2(R)X(bpy)] (R = Me, X = I, 4a; CH2C≡CH, X = Br, 4k). Analogous reactions of 3a with ethyl iodide, benzyl bromide, and substituted benzyl bromides, 3-(bromomethyl)pyridine, 2-(bromomethyl)thiophene, allyl
bromide, and cyclohex-2-enyl bromide led to exclusive formation of the trans addition products (OC-6-43)-[Pt(COMe)2(R)X(bpy)] (X = I, R = Et, 4b; X = Br, R = CH2C6H5, 4c; CH2C6H4(o-Br), 4d; CH2C6H4(p-COOH), 4e; CH2-3-py (3-pyridylmethyl), 4f; CH2-2-tp (2-thiophenylmethyl), 4g; CH2CH=CH2, 4h; c-hex-2-enyl (cyclohex-2-enyl), 4i). All complexes 4 were characterized by microanalysis, 1H and 13C NMR and IR spectroscopy. Additionally, complexes 4a, 4f, and 4g were characterized by single-crystal X-ray diffraction analyses. Reactions of 3a and 3b with o-, m- and p-bis(bromomethyl)benzene, respectively, led to the formation of dinuclear platinum(IV) complexes [{Pt(COMe)2Br(N^N)}2-{μ-(CH2)2C6H4}] (5). These complexes were characterized by microanalysis, IR spectroscopy, and depending on their solubility by 1H and 13C NMR spectroscopy, too. A single-crystal X-ray diffraction analysis of complex [{Pt(COMe)2Br(bpy)}2{μ-m-(CH2)2C6H4}] (5b) confirmed its dinuclear composition. The solid-state structures of 4a, 4f, 4g, and 5b are discussed in terms of C–H···O and O–H···O hydrogen bonds as well as π–π stacking between aromatic rings. 相似文献
18.
Atekeh Tarahhomi Mehrdad Pourayoubi Arnold L. Rheingold James A. Golen 《Structural chemistry》2011,22(1):201-210
Different orientations of P(O) versus C(O) in P(O)NHC(O) skeleton have been discussed in two new phosphorus(V)-nitrogen compounds
with formula XP(O)Y and XP(O)Z2 where X = NHC(O)C6H4(4-F) and Y = NHCH2C(CH3)2CH2NH (1), Z = NHC6H4(4-CH3) (2). Compound 1 is the first example of an aliphatic diazaphosphorinane with a gauche orientation which has been studied by X-ray crystallography; the P=O bond is in the equatorial position of the ring. Both
compounds show
n
J(F,C) and
m
J(F,H) coupling constants (n = 1, 2, 3 and 4; m = 3 and 4) and 3
J(P,C) > 2
J(P,C). Quantum chemical calculations were performed with HF and Density Functional Theory (DFT) methods using 6−31+G(d,p)
basis set. A tentative assignment of the observed vibrational bands for these molecules is discussed. Compound 1 shows a deshielded C atom of the carbonyl moiety (in 13C NMR spectrum) relative to that of 2, which is supported by IR spectroscopy in which the considerably lower C=O frequency is observed for 1. Comparing the X-ray crystallography and IR spectra of 1 and 2 shows that the acyclic compound 2, containing P=O and C=O bonds in an anti position, are involving in a stronger N–H···O=P hydrogen bond in crystal network. This leads to a weaker P=O and NC(O)NHP(O)–H bonds and stronger N···O interaction. The Namide–H is involved in an intramolecular N–H···O hydrogen bond. 相似文献
19.
J. Wang P. Hu G. Han L. Zhang D. Li R. Xu X. Chen X. D. Zhang 《Journal of Structural Chemistry》2011,52(3):575-581
The (NH4)3[YbIII(ttha)]·5H2O (I) (H6ttha = triethylenetetramine-N,N,N′,N″,N‴,N‴-hexaacetic acid) and (NH4)[YbIII(pdta)(H2O)2]·5H2O (II) (H4pdta = propylenediamine-N,N,N′,N′-tetraacetic acid) complexes are synthesized by heat-refluxing and acidity-adjusting methods,
and their structures are determined by single crystal X-ray diffraction techniques. These two complexes are all mononuclear
structures. The complex I crystallizes in ttha monoclinic crystal system with the P21/c space group. The central YbIII ion is nine-coordinated only by one the ligand, and one non-coordinate carboxyl group is left. The crystal data are as follows:
a = 10.321(4) ?, b = 12.744(5) ?, c = 23.203(9) ?, β = 91.082(6)°, V = 3051(2) ?3, Z = 4, D
c = 1.754 g/cm3, μ = 3.150 mm−1, F(000) = 1636, R = 0.0357, and wR = 0.0672 for 6203 observed reflections with I ≥ 2σ(I). The YbN4O5 part in the [YbIII(ttha)]3− complex anion forms a pseudo-monocapped square antiprismatic polyhedron. The complex II is coordinated with one pdta ligand and two water molecules, which form an eight-coordinate structure, and crystallizes in
the triclinic crystal system with the P[`1]P\bar 1 space group. The YbN2O6 part in the [YbIII(pdta)(H2O)2]− complex anion makes a pseudo-square antiprismatic polyhedron. The crystal data are as follows: a = 9.8923(9)?, b = 10.9627(10) ?, c = 12.2618(11) ?, α = 67.284(5)°, β = 70.956(6)°, γ = 68.741(5)°, V = 1115.97(18) ?3, Z = 2, D
c = 1.843 g/cm3, μ = 4.264 mm−1, F(000) = 618, R = 0.0177, and wR = 0.0409 for 4036 observed reflections with I ≥ 2σ(I). 相似文献
20.
1-Allyl-4-aminopyridinium chloride reacts with Cu(NO3)2 · 3H2O in an ethanolic solution under the conditions of ac electrochemical synthesis at copper electrodes to form crystals of compound
[(NH2C5H4N(C3H5))2Cu3Cl3(NO3)2] (I). The crystals of compound I are monoclinic: space group P21/c, Z = 4, a = 25.770(7), b = 7.230(4), c = 12.505(5) ?, β = 92.58(3)°, V = 2328(2) ?3. The direct interaction of 1-allylquinolinium nitrate with Cu(NO3)2 · 3H2O in a methanolic solution in the presence of metallic copper yields crystals of compound [C9H7N(C3H5)Cu(NO3)2] (II). The crystals of compound II are triclinic: space group P
, a = 6.756(3), b = 8.391(4), c = 12.489(5) ?, α = 77.18(3)°, β = 89.48(4)°, γ = 73.32(3)°, V = 662.0(5) ?3. The structure of compound I is built of infinite linear anions: polymeric fragments {(NH2C5H4N(C3H5))2Cu3Cl3(NO3)2}
n
. Each of two copper atoms (Cu(1) and Cu(2)) π-coordinates the C=C bonds of the allyl groups of the 1-allyl-4-aminopyridinium
cations, the oxygen atom of the nitrate ions, and two chlorine atoms. The third copper atom Cu(3) is linearly linked with
two chlorine atoms. Particular polymeric fragments are additionally joined by the N-H…O, C-H…O, C-H…Cl hydrogen bonds. The
crystal structure of compound II is built-up of the isolated L2Cu2(NO3)4 fragments (L is the 1-allylquinolinium cation). The metal atom is localized in the trigonal pyramidal coordination environment
of three oxygen atoms of the nitrate ions and of the C=C bond of the allyl group of the cation. The particular L2Cu2(NO3)4 fragments are additionally joined by the C-H…O hydrogen bonds.
Original Russian Text ? A.V. Pavlyuk, T. Lis, M.G. Mys’kiv, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No.
6, pp. 458–462. 相似文献