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1.
Cobalt(III) complexes with a thiolate or thioether ligand, t-[Co(mp)(tren)]+ (2), t-[Co(mtp)(tren)]2+ (1Me) and t-[Co(mta)(tren)]2+ (2Me), (mp = 3-mercaptopropionate, MA = 3-(methylthio)propionate and MTA = 2-(methylthio)acetate) have been prepared in aqueous solutions. The crystal structures of 1, 2, 1Me and 2Me were determined by X-ray diffraction methods. The crystal data are as follows, t-[Co(mp)(tren)]ClO4 (1CIO4): monoclinic, P21/n, A = 10.877(8), B = 11.570(4), c = 12.173(7) Å, β = 92.20(5)°, V = 1531(1) Å3, Z = 4 and R = 0.060; t-[Co(ma)(tren)]Cl·3H2O (2Cl·3H2O): monoclinic, P21/n, a = 7.7688(8), B = 27.128(2), C = 7.858(1) Å, β = 100.63(1)°, V = 1627.7(3) Å3, Z = 4 and R = 0.066; (+)465CD-t-[Co(mtp)(tren)](ClO4)2 ((+)465CD-1Me(ClO4)2): orthorhombic, P212121, A = 10.6610(7), B = 11.746(1), C = 15.555(1) Å, V = 1947.9(3) Å3, Z = 4 and R = 0.068; (+)465CD-t-[Co(mta)(tren)](ClO4)2 ((+)465CD-2Me(ClO4)2): orthorhombic, P212121, a = 10.564(1), B = 11.375(1), C = 15.434(2) Å, V = 1854.7(4) Å3, Z = 4 and R = 0.047. All central Co(III) atoms have approximately octahedral geometry, coordinated by four N, one O, and one S atoms. All of the complexes are only isomer, of which the sulfur atom in the didentate-O,S ligands are located at the trans position to the tertiary amine nitrogen atom of tren. 1 and 1Me contain six-membered chelate ring, and 2 and 2Me do five-membered chelate ring in the didentate ligand. The chirality of the asymmetric sulfur donor atom in (+)465CD-1Me is the S configuration and that in (+)465CD-2Me is the R one. The 1H NMR, 13C NMR and electronic absorption spectral behaviors and electrochemical properties of the present complexes are discussed in relation to their stereochemistries.  相似文献   

2.
Treatment of the A-ring aromatic steroids estrone 3-methyl ether and β-estradiol 3, 17-dimethyl ether with Mn(CO)5+BF4 in CH2Cl2 yields the corresponding [(steroid)Mn(CO)3]BF4 salts 1 and 2 as mixtures of and β isomers. The X-ray structure of [(estrone 3-methyl ether)Mn(CO)3]BF4 · CH2Cl2 (1) having the Mn(CO)3 moiety on the side of the steroid is reported: space group P21 with a=10.3958(9), b=10.9020(6), c=12.6848(9) Å, β=111.857(6)°, Z=2, V=1334.3(2) Å3, calc=.481 cm−3, R=0.0508, and wR=0.0635. The molecule has the traditional ‘piano stool’ structure with a planar arene ring and linear Mn---C---O linkages. The nucleophiles NaBH4 and LiCH2C(O)CMe3 add to [(β-estradiol 3,17-dimethyl ether)Mn(CO)3]BF4 (2) in high yield to give the corresponding - and β-cyclohexadienyl manganese tricarbonyl complexes (3). The nucleophiles add meta to the arene -OMe substituent and exo to the metal. The and β isomers of 3 were separated by fractional crystallization and the X-ray structure of the β isomer with an exo-CH2C(O)CMe3 substituent is reported (complex 4): space group P212121 with a=7.5154(8), b=15.160(2), c=25.230(3) Å, Z=4, V=2874.4(5) Å3, calc=1.244 g cm−3, R=0.0529 and wR2=0.1176. The molecule 4 has a planar set of dienyl carbon atoms with the saturated C(1) carbon being 0.592 Å out of the plane away from the metal. The results suggest that the manganese-mediated functionalization of aromatic steroids is a viable synthetic procedure with a range of nucleophiles of varying strengths.  相似文献   

3.
The syntheses of nitrosyl–dimethylsulfoxide–ruthenium(II) complexes with general formula mer-[RuCl3(L)(DMSO)(NO)] (L=DMSO or CD3CN) is reported. The mer-[RuCl3(DMSO)2(NO)] (1) complex was obtained from the reaction of [RuCl3(NO)] with the sulfoxide ligand in acetone. The mer-[RuCl3(CD3CN)(DMSO)(NO)] (2) compound was obtained from mer-[RuCl3(DMSO)2(NO)] maintained in deuterated acetonitrile. These data suggest a slow kinetic reaction due the low lability of the DMSO ligand coordinated to the {RuII–NO+} species. The crystal and molecular structures of (1) and (2) have been determined from X-ray studies. Crystal data: for (1), monoclinic, P21/c, a=8.8340(2) Å, b=12.0230(3) Å, c=13.7064(4) Å, β=114.546(2)°, Z=4, R1=0.0429; for (2), monoclinic, P21/n, a=10.0180(7) Å, b=9.5070(7) Å, c=13.3340(9) Å, β=102.264(4)°, Z=4, R1=0.0472. The spectroscopic characterization of (1), in solid state (infrared spectrum) and in solution (nuclear magnetic resonance and cyclic voltammetry) is also described.  相似文献   

4.
The first crystal and molecular structure of a transition metal complex containing 1,2-dithiocroconate (1,2-dtcr, dianion of 1,2-dimercaptocylopent-1-ene-3,4,5-trione), [Cu(bpca)(H2O)]2[Cu(1,2-dtcr)2]·2H2O (where bpca is the bis(2-pyrdidylcarbonyl)amide anion), has been determined by single crystal X-ray diffraction methods. The compound crystallizesin the monoclinic syste, space group P21/c, with a = 11.661(3), b = 20.255(6), c = 8.265(3) Å, ß = 107.26(2)° and Z = 2. The structure is formally built of [Cu(1,2-dtcr)2]2− and [Cu(bpca)(H2O)]+ ions and water of hydration. The copper atom of the anion is situated at a crystallographic inversion centre, bonded to four sulfur atoms in a planar, approximately square arrangement. In the cation the copper equatorial plane is formed by the three nitrogen atoms of the bpca ligand and a water oxygen atom. In addition there is a very weak axial bond to one of the sulfur atoms of a 1,2-dtcr ligand in the anion. Through these latter weak bonds each anion is connected to, and sandwiched between, two cations, resulting in neutral, trinuclear, centrosymmetric formula units. The triple-decker molecules are arranged in stacks along the crystallographic a-axis creating close contacts between the terminal copper atoms and bpca groups of the neighbouring molecules. This intermolecular interaction is, however, too weak to define the structure as a chain compound. The distance between adjacent copper atoms within the trinuclear unit is 4.189(1) Å, while the shortest intra-stack metal-metal separation between terminal copper atoms is 5.281(1) Å. Variable-temperature magnetic susceptibility measurements in the temperature r.2–140 K reveal that a Curie law is followed; with three non-interacting copper(II) ions in the formula unit.  相似文献   

5.
The chlorocadmate(II) systems of (H2me2pipz)[Cd2Cl6(H2O)2] (1) and (H2mepipz)2[Cd3Cl10(H2O)] (2) (L = me2pipz = N,N′-dimethylpiperazine; L′ = mepipz = N-methylpiperazine) were prepared and their structural and thermal properties investigated. Compound 1 is monoclinic, space group P21/c, A = 7.664(1), B = 7.472(4), C = 15.347(1) Å, β = 99.468(7)°, Z = 2, R = 0.024. The crystal structure consists of organic cations and infinite one-dimensional chains of [CdCl3(H2O)]n3− anions. Each Cd atom is octahedrally surrounded by bridged and terminal chlorine atoms and by a water molecule, which is in trans position with respect to the terminal chlorine atom. Inter- and intrachain hydrogen bond interactions between the terminal chlorine atoms and the water molecules contribute to the crystal packing. Compound 2 is orthorhombic, space group Cmc21, A = 15.286(3), B = 13.354(3), C = 13.154(3) Å, R = 0.023. The crystal structure consists of organic dications and infinite chains of [Cd2Cl6(CdCl4H2O]n4− units running along the [001] axis. Each unit is formed of regularly alternate six-coordinated Cd atoms, one of them linking one pentacoordinated Cd atom which completes its coordination througha water molecule. A strong hydrogen bond interaction involving the organic dication and the inorganic chain contributes to the crystal packing. Differential hydrogen bond interaction involving the organic dication and the inorganic chain contributes to the crystal packing. Differential scanning calorimetry measurements did not show the presence of any structural phase transitions. The structures are compared with those of (H2pipz)[Cd2Cl6(H2O)2] (3), (H2mepipz)[Cd2Cl6(H2O)2]·H2O (4) and (H2mepipz)[Cd2Cl6] (5) (L = pipz = piperazine, L′ = mepipz = N-ethylpiperazine).  相似文献   

6.
The methanothermal reactions of M(CO)6 (M = Mo, W) with Na2S2 gave a series of homonuclear clusters [{M(CO)4}n(MS4)]2− (M=Mo, W; N=1, 2), i.e. (Ph4P)2[(CO)4Mo(MoS4)] (I), (Ph4P)2[(CO)4W(WS4)] (II), (Ph4P)2[(CO)4Mo(MoS4)Mo(CO)4] (III) and (Ph4P)2[(CO)4W(WS4)W(CO)4] (IV). The two dimers, I and II, as well as the two trimers, III and IV, are isostructural to each other, respectively. All compounds crystallize in the triclinic space group with Z=2. The cell dimensions are: a=12.393(8), b=19.303(9), c=11.909(6) Å, =102.39(5), β=111.54(5), γ=73.61(5)°, V=2522(3) Å3 at T=23 °C for I; a=12.390(3), b=19.314(4), c=11.866(2) Å, =102.66(2), β=111.49(1), γ=73.40(2)°, V=2511(1) Å3 at T=23 °C for II; a=11.416(3), b=22.524(4), c=10.815(4) Å, =91.03(2), β=100.57(3), γ=88.96(2)°, V=2733(1) Å3 at T=−100 °C for III, a=11.498(1), b=22.600(4), c=10.864(3) Å, =90.92(2), β=100.85(1), γ=88.58(1)°, V=2771(2) Å3 at T=23 °C for IV. The dimers are each formed by the coordination of the tetrathiometalate as a bidentate chelating ligand to an M(CO)4 fragment while addition of another M(CO)4 fragment to the dimers results in the trimers. All compounds contain both tetrahedral and octahedral metal centers with the formal 6+ and 0 oxidation states, respectively.  相似文献   

7.
The preparation and structural characterization of dirhodium(II) tetrakis[N,N-dimethyl-2-pyrrolidone-5(S)-carb- oxamide], Rh2(5S-DMAP)4, a new sterically-demanding catalyst for enantioselective metal carbene transformations, is described. The pyrrolidone ligands are arrayed around the dirhodium(II) core with two oxygen and two nitrogen donor atoms, each oriented cis, bound to each octahedral rhodium. The crystal structure of this compound has been determined to be that of Rh2(5S-DMAP)4(CH3CN)2·CH3CN·6H2O: space group P212121 with cell constants a= 12.685(4), b=15.050(3), c=24.035(4) Å; V=4588.5(1.9) Å3, Z=4, R=0.0316, Rh---Rh DISTANCE =2 4538(5) Å. Decreased activity for diazodecomposition catalyzed by Rh2(5S-DMAP)4 is observed, and enantiocontrol for cyclopropanation and carbon-hydrogen insertion is lower than expected by analogy to the corresponding di- rhodium(II) tetrakis[methyl 2-pyrrolidone-5(S)-carboxylate], Rh2(5S-MEPY)4 Electronic stabilization of the in- termediate metal carbene is absent in reactions catalyzed by Rh2(5S-DMAP)4.  相似文献   

8.
Based on the new ligand bis(1-methyl-2-benzimidazolyl) propane (abbreviated as mtbz) several new copper(II) coordination compounds have been prepared and characterized structurally and spectroscopically. Two representative compounds, i.e. [Cu2(mtbz)2(CH3)2- (CF3SO3)](CF3SO3) (1) and [Cu2(mtbz)2(CH3O)2](ClO4)2 (4) were characterized structurally by X-ray diffraction. Crystal data for 1: monoclinic, space group P21/c, a=13.6585(5), B=39.981(3), C=20.919(1) Å, β=125.98(1)°, Z=8. Crystal data for 4: monoclinic, space group P21/c, a=13.115(2), B=9.523(2), C=17.908(4) Å, β=111.71(1)°, Z=2. Structures 1 and 4 each consist of a dinuclear unit with bridging methoxo groups and one ligand linked to each copper via an N atom. Structure 1 (which consists of two dinuclear, crystallographically independent, but chemically identical units) has the two copper atoms bridged by a triflate anion, providing each copper atom a square-pyramidal coordination, while the copper atoms in structure 4 have an almost a square-planar geometry. The Cu---Cu distances (Å) within the dinuclear units are: 1, 2.9775(13), 2.9751(13); 4, 2.9872(16); the Cu---O---Cu bridging angles (°) are: 1, 101.7(3), 101.7(3), 100.9(3), 102.1(3); 4, 103.2(2). The mid-IR section focused on the vibrations of the triflate anion reveals interesting results concerning the assignments of that anion related to the vas(S---O) band. Characteristic Cu---O vibrations in the far-IR section were found at 386 and 230 cm−1 for the methoxo-bridged and 454 and 332 cm−1 for the ethoxo-bridged compounds. These dinuclear species are EPR silent, and only a weak signal of monomeric impurities is observed. They also show a diamagnetic behavior below room temperature.  相似文献   

9.
The crystal structures of Li[Fe(trtda)]·3H2O and Na[Fe(eddda)]·5H2O (trtda = trimethylenediaminetetraacetate and eddda = ethylenediamine-N,N′-diacetate-N,N′-di-3-propionate) have been determined by single crystal X-ray diffraction techniques. The former crystal was monoclinic with the space group P21/n,a = 17.775(3),b = 10.261(1),c = 8.883(2)Å, β = 95.86(4)° and Z = 4. The latter was also monoclinic with the space group P21/n,a = 6.894(2),b = 20.710(6),c = 13.966(3)Å, β = 101.44(2)° and Z = 4. Both complex anions were found to adopt an octahedral six-coordinated structure with all of six ligand atoms of trdta4− or eddda4− coordinated to the Fe(III) ion, unlike the corresponding edta4− complex which is usually seven-coordinate with the seventh coordination site occupied by H2O. Of the three geometrical isomers possible for the eddda complex, the trans(O5) isomer was actually found in the latter crystal. Factors determining the structural types of metal–edta complexes are discussed in detail.  相似文献   

10.
A series of square-planar complexes [MLCl]ClO4 (M = Pd(II), Pt(II); L = bis(3-(diphenylphosphino)propyl)sulfide (psp), bis(3-(diphenylarsino)propyl)sulfide (asa)) have been prepared and characterized. The X-ray crystal structures of two of them have been determined: [Pd(psp)Cl]ClO4, P21/c, A = 12.519(2), B = 15.766(2), C = 16.501(2) Å, β = 105.22(1)°, Z = 4; and [Pt(asa)Cl]ClO4, P21/c, a = 12.583(5), B = 16.007(6), C = 16.549(6) Å, β = 104.89(3)°, Z = 4. In both structures, there is a conformational disorder between the chair and skew-boat orientation in one of the two six-membered chelate rings. The C---H…O hydrogen bond between the hybrid ligand and the perchlorate counter ion that induces the conformational disorder is discussed.  相似文献   

11.
The crystal structure of tri-O-ethylamylose has been solved by stereochemical conformation and packing analysis and by X-ray fibre diagram analysis. The unit cell is orthorhombic, space group P212121, with = 16.13 (± 0.04) Å, b = 11.66 (± 0.02) Å, and c (fibre repeat) = 15.48 (± 0.02) Å. Density measurements, together with the observation of only a fourth-order meridional reflection, indicated that portions of two four-fold helices pass through the unit cell. The actual chain conformation is that of a 43 helix with the EtO-6 group in the tg (trans to O-5, and gauche to C-4) position. The tri-O-ethylamylose structure is compared with those of other amylose derivatives.  相似文献   

12.
The molecular structure of the title complexes [Fe(H2O)4][Fe(Hedta)(H2O)]2 · 4H2O (I) and [Fe(H[2edta)(H2O)] · 2H2O (II) have been determined by single-crystal X-ray analyses. The crystal data are as follows: I: monoclinic, P21/n, A = 11.794(2), B = 15.990(2), C = 9.206(2) Å, β = 90.33(1)°, V = 1736.1(5) Å3, Z = 2 and R = 0.030; II: monoclinic, C2/c, A = 11.074(2), B = 9.856(2), C = 14.399(2) Å, β = 95.86(1)°, V = 1563.3(4) Å3, Z = 4 and R = 0.025. I is found to be isomorphous with the MnII analog reported earlier and to contain a seven-coordinate and approximately pentagonal-bipyramidal (PB) [FeII(Hedta)(H2O] unit in which Hedta acts as a hexadentate ligand. The [FeII(H2edta)(H2O)] unit in II has also a seven-coordinate PB structure with the two protonated equatorial glycine arms both remaining coordinated, and thus bears a structural resemblance to the seven-coordinate [CoII(H2edta)(H2O)] reported previously.  相似文献   

13.
(3-Trimethylsilyl-pyridine-2-thiolato-S,N)copper(I), [Cu(3-Me3Sipyt)], was obtained by electrochemical oxidation of copper metal in an acetonitrile solution of the neutral ligand. The compound is tetrameric and the four copper atoms are arranged with distorted tetrahedral geometry, each copper atom being trigonally coordinated to one nitrogen and two sulfur atoms of three different ligands. Crystal data: 141/a, a=14.608(2), C=19.366(4) Å, V=4133(2), Å, Z=4, Dcalc=1.581 g cm−3, R=0.0397 for 848 reflections.  相似文献   

14.
Chicken liver basic fatty acid-binding protein (pI = 9.0) has been purified with a high yield by a modification of a method originally applied to rat liver. The final product is highly homogeneous and can be used to grow crystals that belong to two different space groups. The crystals are either tetragonal, space group P42212 with a = b = 60.2 Å and c = 138.1 Å or orthorhombic, space group P212121 with a = 60.7 Å, b = 40.1 Å and c = 66.7 Å. The second form appears to be more suitable for X-ray diffraction studies, it diffracts to at least 2.8 Å resolution and it is believed to contain one protein molecule in the crystallographic asymmetric unit.  相似文献   

15.
The molecular structure of trans-[Pd(PhC(O)CHP(n-C4H9)3)2Cl2] has been determined via a single crystal X-ray diffraction study: triclinic,P1,a = 8.876(2),b = 10.908(3),c = 11.938(4)Å, = 97.06(2)°, β = 102.79(2)°, γ = 100.51(2)°,V= 1092.1(5)Å3,Z = 1 and R(F) = 4.61%. The phosphorus ylide molecules are bound to the palladium atom through their methine carbon atoms, the overall coordination geometry about the palladium being square planar. The protons in the ortho-positions of the two phenyl group are poised above and below the palladium atom, suggesting that the complex is a precursor of the ortho-metalated complex [Pd(μ-Cl)(C6H4C(O)CHP(n-C4H9)3)]2 synthesized earlier in our laboratory.  相似文献   

16.
Four complexes of the type [Cu4I4(CH3CN)2(L)2], L = aniline derivative: Cu4I4(CH3CN)2(2,6-dimethylaniline)2 (I), triclinic, , a = 12.449(3), B = 14.108(6), C = 10.606(4) Å, = 73.46(3), β = 95.00(2), γ = 73.42(3)°, V = 1682.3(10) Å3; Cu4I4(CH3CN)2(o-ethylaniline)2 (II), triclinic, , V = 1734.0(8) Å3; Cu4I4(CH3CN)2(6-ethyl-o-toluidine)2 (III), orthorhombic, Pnam, a = 14.976(6), b = 21.187(6), C = 12.545(2) Å, V = 3980.7(2) Å3; Cu4I4(CH3CN)2(p-anisidine)2 (IV), monoclinic, A2/a, A = 20.032(10), B = 7.863(1), C = 18.715(9) Å, β = 101.56(4)°, V = 2888.0(2) Å3; were examined by single crystal X-ray diffraction. Complexes I and II have no internal symmetry elements, III has an internal mirror and IV has a two-fold axis. Ab initio calculations based on the atomic positional parameters of complexes containing the three types of symmetry elements reveal HOMO orbitals to be dominated by the p orbitals of the iodine atoms whereas the LUMO orbitals contain major contributions from copper based p orbitals.  相似文献   

17.
A number of N,N′-bis(4-substituted phenyl)-1,7-diaza-12-crown-4 and N,N′-bis(4-substituted phenyl)-1, 10-diaza-18-crown-6 (where the substituents are OCH3, CH3, H, Cl, respectively) have been prepared by cyclization reaction of a ditosylate with the appropriately substituted diol. These new macrocyclic ligands have been characterized by means of elemental analysis, IR, 1H NMR and MS spectra. The crystal structures of N,N′-bis(4-chlorophenyl)-1,10-diaza-18-crown-6 (21) and its complex with barium thiocyanate Ba(SCN)2 (22) have been determined by single crystal X-ray diffraction. The crystallographic data are as follows: 21: C24H32Cl2N2O4, orthorhombic, P212121, A=4.852(1), B=11.989(2), C=41.231(8) Å, V=2398.7(8) Å3, Z=4; 22: C26H32Cl2N4O4S2Ba, monoclinic, P21/c, A=8.801(2), B=11.653(9), C=15.756(6) Å, ß=105.96(3)°, V=1553.7(14) Å3, Z=2. In the complex, the Ba atom is eight-coordinate (O(1), O(2), O(1)′, O(2)′, N(1), N(1)′, N(21), N(21)′) to form a distorted D6h geometry with the Ba atom at the center of crystallographic symmetry.  相似文献   

18.
Compounds of formula [Al(CH3CN)6][MCl6]3(CH3CN)3 (M=Ta (1); Nb (2); Sb (3)) have been synthesized from the reactions of MCl5 and AlCl3 in acetonitrile and characterized by X-ray crystallography. Complex 1 crystallizes in the tetragonal space group P4/mbm with a = B = 10.408(2), C = 7.670(3) Å, V = 830.9(4) Å3 and Z = 2/3. Complex 2 crystallizes in the tetragonal space group P4/mnc with a = B = 330(a), C = 15.320(3) Å3 V = 1634.8(4) Å3 and Z = 4/3. Complex 3 also crystallizes in the tetragonal space group P4/mnc with a = B = 10.313(1), C = 15.238(2) Å, V = 1621.0(1) Å3 and Z = 4/3. The non-integer Z values for complexes 1–3 result unusual problems of disorder and/or twinning in these crystal structures due to their high symmetry. The M---Cl distances range from 2.329(3) Å in the Ta complex to 2.355(1) Å in the Sb complex, while the Al---N distances are similar in all three complexes, ranging from 1.92(1) to 1.97(1) Å, respectively. Complexes 1–3 are the first structurally characterized complexes that contain a (hexaacetonitrile)aluminum(III) cation.  相似文献   

19.
New mixed metal complexes SrCu2(O2CR)3(bdmap)3 (R = CF3 (1a), CH3 (1b)) and a new dinuclear bismuth complex Bi2(O2CCH3)4(bdmap)2(H2O) (2) have been synthesized. Their crystal structures have been determined by single-crystal X-ray diffraction analyses. Thermal decomposition behaviors of these complexes have been examined by TGA and X-ray powder diffraction analyses. While compound 1a decomposes to SrF2 and CuO at about 380°C, compound 1b decomposes to the corresponding oxides above 800°C. Compound 2 decomposes cleanly to Bi2O3 at 330°C. The magnetism of 1a was examined by the measurement of susceptibility from 5–300 K. Theoretical fitting for the susceptibility data revealed that 1a is an antiferromagnetically coupled system with g = 2.012(7), −2J = 34.0(8) cm−1. Crystal data for 1a: C27H51N6O9F9Cu2Sr/THF, monoclinic space group P21/m, A = 10.708(6), B = 15.20(1), C = 15.404(7) Å, β = 107.94(4)°, V = 2386(2) Å3, Z = 2; for 1b: C27H60N6O9Cu2Sr/THF, orthorhombic space group Pbcn, A = 19.164(9), B = 26.829(8), C = 17.240(9) Å, V = 8864(5) Å3, Z = 8; for 2: C22H48O11N4Bi2, monoclinic space group P21/c, A = 17.614(9), B = 10.741(3), C = 18.910(7) Å, β = 109.99(3)°, V = 3362(2) Å3, Z = 4.  相似文献   

20.
Three new crystalline tin selenide salts have been prepared from the reactions of [PPh4]2[Sn(Se43] in supercritical solvents. The starting material pyrolyzes in supercritical acetonitrile to form [PPh4]4[Sn6Se21] (I), and it also reacts with SnSe in supercritical ammonia leading to a mixture of [PPh4]4[Sn3Se11]2 (II). and [PPh4]2[Sn(Se4)(Se6)2] (III). All three compounds have been characterized by single crystal X-ray diffraction. Crystallographic data: for I, C96H90P4Se21Sn6, space group triclinic, P-1, A = 18.763(3), B = 24.600(4), C = 13.137(1) Å, = 102.63(1), β = 93.66(1), γ = 108.72(1)°, V = 5544(1) Å3, Z = 2, R = 0.0350, RW = 0.0317: for II, C96H80P4Se22Sn6, space group monoclinic P21/c, A = 31.500(4), B = 16.572(3), C = 22.352(3) Å, β = 103.53(1)°, V = 11344(3) Å3, Z = 4, R = 0.0771, RW = 0.0664: for III, C48H40P2Se16Sn, space group monoclinic, C2/c, A = 25.381(2), B = 13.934(4), C = 19.465(3) Å, β = 121.587(8)°, V = 5867(2) Å3, Z = 4, R = 0.0807, RW = 0.0650. One of the compounds, [PPh4]2[Sn(Se4(Se62], is a molecular cluster while the other two complexes [PPh4]4[Sn3Se11]2 and [PPh4]4[Sn6Se21], are one dimensional tin selenide chains. The structures of the two chains are related and consits of tetrahedral and distorted trigonal bipyramidal tin(IV) centers bridged by Se2−, Se22− and Se32− chains.  相似文献   

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