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1.
The reaction of thiols with the heterocyclic compound 2,3-dichloropyrrolo[1,2-a] benzimidazol-1-one (1) has been investigated as a route to new redox-active, bidentate sulfur ligands. Treatment of 1 with either methylthiol or benzylthiol in the presence of pyridine affords monosulfide compounds 2-chloro-3-methylthiopyrrolo[1,2-a] benzimidazol-1-one (2) and 2-chloro-3-benzylthiopyrrolo[1,2-a]benzimidazol-1-one (3) and the disulfide derivatives 2,3-di(methylthio)pyrrolo[1,2-a]benzimidazol-1-one (4) and 2,3-di(benzylthio)pyrrolo[1,2-a]benzimidazol-1-one (5). The substitution of the first chlorine group in 2,3-dichloropyrrolo[1,2-a]benzimidazol-1-one (1) occurs regioselectively at C-3 to produce 2-chloro-3-methylthiopyrrolo[1,2-a]benzimidazol-1-one (2) and 2-chloro-3-benzylthiopyrrolo[1,2-a]benzimidazol-1-one (3), followed by replacement of the remaining chlorine group to furnish the disulfide compounds 4 and 5. The new thiols have been isolated by column chromatography and characterized in solution by spectroscopic methods. The molecular structures of 2-chloro-3-methylthiopyrrolo[1,2-a]benzimidazol-1-one and 2,3-di(benzylthio)pyrrolo[1,2-a]benzimidazol-1-one have been determined by X-ray crystallography. Compound 2 crystallizes as two independent molecules in the monoclinic space group P21/c, a = 13.221(2) Å, b = 18.478(2) Å, c = 8.948(1) Å, = 100.088(3)°, V = 2152.3(5) Å3, Z = 8, and dcalc = 1.547 Mg/m3; R = 0.0354, Rw = 0.0739 for 2820 reflections with I > 2(I). Compound 5 crystallizes in the triclinic space group P-1, a = 5.180(1) Å, b = 11.494(2) Å, c = 17.243(3) Å, = 86.024(3)°, = 88.606(4)°, = 81.235(3)°, V = 1012.1(4) Å3, Z = 2, and dcalc = 1.360 Mg/m3; R = 0.0354, Rw = 0.0692 for 2655 reflections with I > 2(I). The redox properties of the disulfide compounds 4 and 5 have been explored by cyclic voltammetry, where a one-electron reduction at ca. –1.10 V has been observed for each compound. The site of electron accession in has been established by carrying out molecular orbital calculations at the extended Hüuckel level on the model compound 2,3-di(thio)pyrrolo[1,2-a]benzimidazol-1-one.  相似文献   

2.
A series of organosulfur compounds was characterized by NMR, IR, mass spectroscopy, cyclic voltammetry, and chemical analyses. The crystal structures of six compounds were determined: 1,3-dithioleno[4,5-e]naphtho[2,3-b]1,4-dithiin-2,5, 10-trione (1b), P , a = 7.665(4), b = 7.997(4), c = 11.443(5) Å, = 91.311(8), = 92.516(8), = 117.53(7)° 6,7-dimethylbenzo[1,2-b]1,3-dithioleno[4,5-e]1,4-dithiin-2,5,8-trione (2b), P21/m, a = 3.933(1), b = 12.864(2), c = 11.943(3) Å, = 99.161(4)° 6-phenyl-2-thioxo-6-hydrocyclopenta[2,1-b]1,3-dithioleno[4,5-e]1,4-dithiin-5,7-dione (3a), C2/c, a = 32.408(6), b = 3.8743(8), c = 27.123(5) Å, = 125.171(7)° 6-phenyl-1,3-dithioleno[4,5-e]3-pyrrolino[3,4-b]1,4-dithiin-5,7-trione (3b), P21/n, a = 7.9712(9), b = 6.1976(7), c = 55.978(6) Å, = 91.096(1)° 2,3,7,8-tetramethylthianthrene-1,4,6,9-tetraone (4), P21/c, a = 4.195(1), b = 17.924(5), c = 9.682(3) Å, = 98.509(5)° 3H,6H-1,4-oxathiino[6,5-2,1]naphtho[3,4-e]1,4-oxathiin-2,7-dione (5), P21/n, a = 9.3522(7), b = 7.8782(6), c = 17.118(1) Å, = 93.171(1)°. Several structures exhibited significant S—S intermolecular interactions, suggesting that the molecules might be precursors for preparing nonmetallic conductors.  相似文献   

3.
A new salt (EV)2[Cu(mnt)2] [EV = tris(p-(diethylamino)phenyl)methylium; mnt = bis(1,2-dicyanovinylene-1,2-dithiolato)] was prepared by the reaction of [NBu4]2[Cu(mnt)2] with ethyl violet dye (EV)Cl. The crystallographic data are: triclinic P–1, a = 11.1102(11) Å, b= 12.2768(12) Å, c = 14.0265(14) Å, = 98.987(2)°, = 97.972(2)°, = 110.402(2)°, V = 1732.2(3) Å3, Z = 1. The [Cu(mnt)2] dianion exhibits a quasi-square planar structure and the EV cation has a trigonal planar geometry with an A symmetric propeller-like conformation. A pseudo-dimmer of the EV cation and weak hydrogen bonds between the cation and the anion were observed in the crystal.  相似文献   

4.
A benzo-phenanthro-fused planar cyclooctatetraene derivative, namely, 5,6,15,16-tetradehydrobenzo[a]phenanthro[9, 10-e]cyclooctene (5) was synthesized in two steps from the known benzo[a]phenanthro[9, 10-e]cyclooctene (6). Compound5 crystallizes in space groupPbam witha=9.828(2),b=19.466(4),c=15.901(3) Å, and Z=8. X-Ray analysis (MoK radiation,R=0.060 for 1233 observed data) has shown that both independent molecules have the same planarC 2v configuration with averaged bond lengths of 1.381(7) and 1.208(7) Å for the phenanthrene C6a–C14b bond and the acetylenic CC bond, respectively.1H and13C NMR spectral results of 5 and 5,6,15,16-tetrabromo-5,6,15,16-tetrahydrobenzo[a]phenanthro[9, 10-e]cyclooctene (7) are also presented.  相似文献   

5.
The coordination chemistry of the caged phosphites 4-2,6,7-trioxa-1-phosphabicyclo [2.2.2]octane (MeCage) and 4-nitro-t2,6,7-trioxa-1t-phosphabicyclo[2.2.2]octane (NO2Caget) with copper(I) halides is reported. Reactions of CuX = CuCl, CuBr, and CuI with the phosphite ligands afford complexes of the type [CuX(MeCage)]4, [CuX(NO2Cage)]4, [CuX(MeCage)2]2, [CuX(NO2Cage)2]2, and [CuX(MeCage)3]. Recrystallization of [CuBr(NO2Cage)2]2 in MeCN produced [CuBr(NO2Cage)(NCMe)]2. Three X-ray crystal structures are reported: [CuCl(MeCage)]4 (I – 4, a = 13.4292(5) Å, b = 13.4292(5) Å, c = 9.4641(5) Å, V = 1706.79(13) Å3, Z = 2), [CuBr(MeCage)2]2 (I41/a, a = 19.5751(17) Å, b = 19.5751(17) Å, c = 16.4513(15) Å, V = 6303.9(10) Å3, Z = 8), and [CuBr(NO2Cage)(NCMe)]2 (P21/c, a = 9.0506(4) Å, b = 15.2428(7) Å, c = 8.8673(4) Å, = 109.7640(10), V = 1151.24(9) Å3, Z = 2).  相似文献   

6.
Both the cis and trans isomers of 3,11,18,26-tetrathiatricyclo[26.2.2.15,9.213,16.120,24] hexatriaconta-5,7,9,20,22,24-hexene have been prepared and structurally characterized. Each of these centrosymmetric tetrathia dimers includes two cyclohexane rings in chair conformations with either 1,4-cis or 1,4-trans bonding and two meta-substituted benzene rings. The cis isomer packs into the monoclinic space group P21/a with a = 10.485(3)Å, b = 10.3956(18)Å, c = 14.1343(10)Å, = 105.200(13)°, Z = 2 and refined to an R factor of 0.046. The trans isomer crystallizes in the monoclinic space group P21/c with a = 10.7217(12)Å, b = 5.6797(7)Å, c = 25.415(5)Å, = 96.001(12)°, Z = 2 and refined to an R factor of 0.043. In the cis structure each benzene ring faces a cyclohexane ring while in the trans structure the cyclohexane rings face one another.  相似文献   

7.
2-bromobenzo[b]indeno[1,2-e]pyran crystallizes in the monoclinic system: space groupP21/c,a = 7·508,b = 5·959,c= 26·172 Å, = 92·55 °. The structure has been determined by the heavy-atom method and refined by full-matrix least squares toR = 0·072 for 1027 observed reflections.The molecule is non-planar; the maximum deviations from the best plane occur at both ends of the length of the molecule, which results in distortion of the central portion from the expected geometry. The closest approach of two molecules, those related by a 21 axis, is 3·5 Å.  相似文献   

8.
The structures of anionic pyridine-2,6-dicarboxylato (pdc2–) complexes of cobalt, nickel, and copper have been studied. The stoichiometries and structures are very much dependent on whether KOH, Et4NOH, or NaOH is used in the synthesis to deprotonate the H2pdc ligand. Crystallographic results are: (1) K2[Co(pdc)2] · 7H2O, orthorhombic, Pnna, Z = 4, a = 20.637(2)Å, b = 13.480(1)Å, c = 8.200(1)Å (2) K2[Ni(pdc)2] · 7H2O, orthorhombic, Pnna, Z = 4, a = 20.648(1)Å, b = 13.375(1)Å, c = 8.2393(8)Å (3) [Co2(H2O)5(pdc)2] · 2H2O, monoclinic, P21/c, Z = 4, a = 8.3880(6)Å, b = 27.384(2)Å, c = 9.6110(8)Å, = 98.271(6)° (4) [Ni(Hpdc)2] · 3H2O, monoclinic, P21/c, Z = 4, a = 13.679(1)Å, b = 10.0450(9)Å, c = 13.767(2)Å, = 115.184(7)° (5) Na6[Co(H2O)6][Co(pdc)2]4 · 28H2O, monoclinic, P21/n, Z = 2, a = 13.363(1)Å, b = 8.437(1)Å, c = 40.689(3)Å, = 91.288(5)° (6) Na[Ni(Hpdc)(pdc)] · 11.5H2O, monoclinic, C2/m, Z = 4, a = 15.200(2)Å, b = 22.299(2)Å, c = 8.3596(7)Å, = 118.894(7)° (7) Na[Cu(Hpdc)(pdc)] · 3H2O, monoclinic, P21/n, Z = 4, a = 9.516(4)Å, b = 14.917(6)Å, c = 12.247(5)Å, = 92.00(5)°. The potassium and sodium complexes have extensive K+—H2O and Na+—H2O networks. The fact the Et4N+ ion does not appear in any of the complexes is likely due to the fact that it is incapable of forming the intricate cation—water and hydrogen-bonding networks observed in all of the other structures.  相似文献   

9.
Crystal structures of four dibromomethylene-functionalized hexa- and heptacyclotetradecane cages are reported. 7-(Dibromomethylene)heptacyclo[6.6.0.02,6.03,13.04,11.05,9.010,14]tetradecane (3): orthorhombic, Pnma, a = 14.744(1), b = 11.237(1), c = 7.4625(7) Å Z = 4; R = 0.0531 for 504 observed reflections. 7,12-Bis(dibromomethylene)heptacyclo[6.6.0.02,6.03,13-04,11 .05,9.010,14]tetradecane (4): monoclinic, I2/a, a = 11.257(1), b = 9.5844(8), c = 13.884(2) Å, = 92.254(8)° Z = 4; R = 0.0413 for 663 observed reflections. 10,14-bis(dibromomethylene)hexacyclo[6.6.0.02,6.03,13.04,11.05,9]tetradecane (6): monoclinic, P21/n, a = 8.118(1), b = 15.273(4), c = 12.826(3) Å, = 104.20(1)° Z = 4; R = 0.0384 for 1392 observed reflections. 14-(dibromomethylene)hexacyclo[6.6.0.02,6.03,13.04,11.05,9]tetradecan-10-one (7): monoclinic, P21/n, a = 8.2879(7), b = 15.273(1), c = 10.0565(9) Å, = 92.271(8)° Z = 4; R = 0.0320 for 1402 observed reflections. The functional groups lead to slight shortening of bond lengths.  相似文献   

10.
The crystal and molecular structure of copper(II) complexes of benzil bis(3-piperidylthiosemicarbazone), [Cu(Bnzpip)] and 1-phenylpropane-1,2-dione bis(3-piperidylthiosemicarbazone), [Cu(Pmpip)] have been determined. [Cu(Bnzpip)] is monoclinic, space group P21/n with a = 13.9375(10) Å, b = 11.6621(4) Å, c = 16.4710(10) Å, = 100.667(2)°, and V = 2630.9(3) Å3 with Z = 4, for d calc = 1.399 g/cm3. [Cu(Pmpip)] is also monoclinic, space group P21/n with a = 11.292(6) Å, b = 10.219(5) Å, c = 20.292(6) Å, = 101.50(3)°, and V = 2295(2) Å3 with Z = 4, for d calc = 1.525 g/cm3. Both complexes involve N2S2 coordination, are relatively planar except for the phenyl rings and have similar bond distances and angles to copper(II) complexes of other 3-piperidylthiosemicarbazones.  相似文献   

11.
4-Methyl-2-phenylbenzo[de]cyclobut[i]isoquinoline-3,5(2H)-dione, C21H15NO2, resulted from the photochemical reaction of N-methyl-1,8-naphthalenedicarboximide with phenylacetylene, has been characterized by 1H NMR, IR, and MS spectra and established by single-crystal X-ray crystallography. The crystal structure belongs to the monoclinic space group P21/n with cell parameters a = 12.530(2) Å, b = 9.324(2) Å, c = 13.296(2) Å, = 96.85(1), V = 1542.3(4) Å3, and Z = 4.  相似文献   

12.
The structure of complex [PyH][Ni(mnt)2], as determined by X-ray single crystal analysis, consists of pyridinium cations and [Ni(mnt)2] anions. Crystallographic data for the complex: monoclinic P21/c, a = 16.5430(18) Å, b = 6.3847(9) Å, c = 17.430(2) Å, = 118.040(7)°, V = 1625.4(3) Å3, Z = 4. The [Ni(mnt)2] anion is not a planar and the CN groups bend away from the S4 plane. The interactions between anions and cations via the formation of bifurcated N–H···NC hydrogen bonds give rise to an 1D zigzag chain of alternating cations and anions.  相似文献   

13.
The molecular structure of (tBu)3Al[O=C(OPh)2] has been determined. The increase in the C=O bond distance [1.258(4) Å] when compared to free O=C(OPh)2 [1.191(3) Å], is presented in respect to the activating ability of aluminum Lewis acids. Crystal data: monoclinic, P21/n, a = 10.653(2), b = 18.486(4), c = 14.551(3) Å, = 108.07(3)°, and V = 2724.3(9) Å3 for Z = 4.  相似文献   

14.
The new macrocyclic compound bearing hydroxyethyl pendant arms containing p-xylyl spacers, 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)-tricyclo[22,2,2,211,14] triaconta-1,11,13,24,27,29-hexaene, crystallizes in the monoclinic space group P21/c with a = 8.700(2) Å, b = 18.301(4) Å, c = 11.766(2) Å, = 108.57(2)°. The two hydroxyethyl pendants are at the opposite sides of the macrocyclic plane. Benzene rings in macrocycle are parallel and exist the - weak interaction with distance of 4.28 Å. The crystal packing of the macrocycle is stabilized by the hydrogen bonds.  相似文献   

15.
A single crystal X-ray diffraction study of two annulated bicyclo[2.2.2]octenones has been carried out to establish their precise stereostructures. The compounds, with their crystal data, are:1, 9-hydroxy-9-chloromethyl-endo-tricyclo[5.2.2.02,6]undeca-4,10-diene-3-spiro(1-cyclopropane)-8-one, C14H15O2Cl, space group P21/c,a=10.540(2),b=9.668(1),c=11.841(4)Å, =95.67(2)°,Z=4, and2, 12-hydroxy-12-chloromethyl-endo-tricyclo[8.2.2.02,9]tetradeca-13-en-11-one, C15H21O2Cl, space group C2/c,a=20.747(8),b=6.498(1),c=20.525(3)Å, =93.04(3)°,Z=8. The molecule of1 has endo stereochemistry at the ring junction and the spirocyclopropane ring is proximal to the hydroxyl group. In2, the eight membered ring deviates from a chair conformation and one ring atom is disordered. Crystals of1 and2 contain centrosymmetric dimers formed by C=O...O–H hydrogen bonds.  相似文献   

16.
A three-dimensional coordination polymer [Ni(en)2Ag3(CN)5]n (en = 1,2-diaminoethane) was synthesized and characterized by X-ray crystallography. It crystallizes in the triclinic space group ,a = 7.520(2) Å, b = 8.194(2) Å, c = 8.426(2) Å, = 65.35(3)°, = 69.57(3)°, = 68.91(3)°, V = 428.0(2), Å3 Z = 1. The 2D hexagonal grids are constructed using cyanides as bridges, and the Ag···Ag interactions between layers lead to a three-dimensional network.  相似文献   

17.
Crystals of (Z)-2-(1-methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2]octan-3-one (I) were obtained from a condensation reaction of 1-methyl-1H-indole-3-carboxaldehyde with 1-aza-bicyclo[2.2.2]octan-3-one and subsequent crystallization of the product from methanol. The isomeric (E)-2-(1-methyl-1H-indol-3-ylmethylene)-1-aza-bicyclo[2.2.2] octan-3-one hydrochloride (II) was obtained by treating a methanolic solution of I with a 1M solution of hydrogen chloride diethyl ether, followed by crystallization of resultant product from methanol. Crystal data: I, is monoclinic, P21, a = 5.7440(10), b = 11.102(2), c = 10.708(2) Å, = 91.751(10)°, and V = 682.5(2) Å3 with Z = 2, for D cal= 1.296 mg/m3 and II, is monoclinic, P21/c, a = 8.8510(2), b = 17.4990(5), c = 20.4300(5) Å, = 101.3620(12)°, V = 3102.26(14) with Z = 8, for D cal= 1.316 mg/m3.  相似文献   

18.
[BrFPy]2[Ni(dto)2] (1) and [BrPy]2[Ni(dto)2] (2) complexes have been prepared by reaction of Na2[Ni(S2C2O2)2] and the corresponding 1-(Rbenzyl)pyridinium bromide salt (R1 = 4-bromo-2-fluoro, R2 = 4-bromo). The crystallographic data for 1: monoclinic P21/c, a = 14.2192(1) Å, b = 14.2533(4) Å, c = 15.6535(3) Å, = 96.463(1)°, V = 3152.34(11) Å3, Z = 4. Two cations, [Br1F1Py]+ and [Br2F2Py]+, both adopt a conformation where both the aromatic rings are twisted to the corresponding N(1)–C(10)–C(11) or N(2)–C(22)–C(23) reference plane. Data for 2: triclinic , a = 9.4042(3) Å, b = 9.6814(4) Å, c = 10.3357(4) Å, = 80.155(1)°, = 65.245(1)°, = 64.259(1)°, V = 769.68(5) Å3, Z = 1. The [Ni(dto)2]2– anion exhibits a quasi-planar structure in both complexes. An extensive hydrogen bond network of C–H O is clearly observed in 1 and 2, and two complexes show similar crystal packing.  相似文献   

19.
The crystal and molecular structure of 3-phenyl-7-bromoisoxazolo[4,5-d]-pyridazin-4(5H-one, C11H6BrN3O2, has been determined from two- and three-dimensional X-ray data and refined by Fourier and least-squares methods toR = 0·101 for 1187 observed reflexions. Crystals of 3-phenyl-7-bromoisoxazolo-[4, 5-d]pyridazin-4(5H)-one are monoclinic:a = 7·67,b = 6·84,c = 20·52 Å, = 91·5 °,Z = 4, space groupP21/c. The benzene ring makes an angle of 4·5 ° with the plane of the isoxazole ring, and the other part of the molecule is slightly non-planar. The bond distances and angles compare well with those of other similar molecules. Two N-H...O hydrogen bonds join the two molecules related by a centre of symmetry. Close molecular packing is found in layers parallel to (100).  相似文献   

20.
A single crystal of phase 1 of 1,2-difluoroethane was grown from the melt directly on an X-ray diffractometer close to the melting point of 169 K. It crystallizes in the monoclinic space group C2/c with lattice parameters a = 7.775(4), b = 4.4973(7), c = 9.024(3) Å, = 101.73(1)°, V = 308.9(2) Å3, d calc = 1.420 g cm–3 for Z = 4. A second phase of 1,2-difluoroethane was obtained under similar conditions which crystallizes in the orthorhombic space group P212121 with the unit cell parameters a = 8.0467(16), b = 4.5086(9), c = 8.279(2) Å,V = 300.36(11) Å3, d calc = 1.461 g cm–3 for Z = 4. In both phases the 1,2-difluoroethane molecules adopt the gauche conformation with F–C–C–F torsion angles close to 68°. Crystals of 1,2-diiodoethane C2H4I2 were grown from pentane at –30°C. A platelet single crystal of the size 0.35 × 0.25 × 0.03 mm was measured with Mo K-radiation at 153 K. 1,2-Diiodoethane crystallizes in the monoclinic space group P21/n with a unit cell of a = 4.6051(7), b = 12.939(2), c = 4.7318(7) Å, = 104.636(3)°, V = 272.79(7) Å3, Z = 2, d calc = 3.431 g cm–3, (MoK) = 11.353 mm–1. In the molecule the two neighboring iodine atoms are positioned anti. The shortest intermolecular contacts occur via iodine–iodine interactions resulting in layers of molecules in the crystal.  相似文献   

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