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1.
On the Lithium Chloromolybdate Li[Mo6Cl13] Li[Mo6Cl13] was obtained as single phase product from a solid state reaction of MoCl5, Mo powder, and LiCl at 800 °C. The structure as refined by single crystal X‐ray diffraction, contains one‐dimensional [Mo6Cl Cl Cl ]– chains, formed by Cla–a bridges. Lithium ions are located in tunnels along the chain‐direction, each of them being surrounded by a distorted tetrahedral arrangement of outer chlorine ligands (Cla) belonging to four different clusters. 相似文献
2.
Electronic Structure of Structural Open Derivatives of the [Mo6X14]2?-Cluster: [Mo5Cl13]2? and [Mo4I11]2? The electronic structure of structural open derivatives of the [Mo6X14]2?-cluster [Mo5Cl13]2? and [Mo4I11]2? has been studied by the EHMO method. In [Mo5Cl13]2? 9 occupied MO's with dominant Mo4d character are responsible for the formation of the 8 metal-metal bonds. In [Mo4I11]2? the stronger covalent character of the Mo? I bonds affects the localization and the energy of molecular orbitals and also the charge distribution. The metal-metal bonds are formed by 8 MO's containing considerable participation of halogen AO's contrary to the chloride cluster. There is no bonding between the Mo atoms at the wing tips of the Mo4 butterfly and the reason for decreasing the dihedral angle between the Mo3 planes in [Mo4I11]2? compared with the octahedral angle is apparently the stabilization of the whole system (Mo? Mo and Mo? I bonds). The unpaired electron occupies in both clusters a slightly antibonding (with regard to the Mo? Mo bonds) orbital. 相似文献
3.
Synthesis and Crystal Structure of Mo2<>NCl8 and Mo3N2Cl11 The reaction of MoCl5 with Cl3VNCl at 140 °C in a sealed glass ampoule yields air sensitive black crystals of the mixed valent molybdenum(V, VI) nitride chloride, Mo2NCl8. It crystallizes in the monoclinic space group P2/c with a = 996.1(1), b = 629.4(1), c = 1780.8(3) pm, β = 101.82(2)°, and Z = 4. The crystal structure consists of dinuclear C2‐symmetrical units [Cl2(N≡)Mo(μ2‐Cl)3Mo(≡N)Cl2]— and [Cl4Mo(μ2‐Cl)MoCl4]+, connected in an alternating sequence by asymmetric nitrido bridges Mo≡N‐Mo to form chains. The reaction of Cl3VNCl with MoCl3 at 140 °C affords Mo3N2Cl11, but for the prolonged reaction period, MoNCl3 is observed in addition. Mo3N2Cl11 can also be obtained from MoNCl3 and MoCl5 (2:1) at 140 °C. It forms orthorhombic, black crystals with the space group Pca21 and a = 1256.1(1), b = 1001.9(1), c = 1330.10(5) pm, and Z = 4. The structure contains the same dinuclear units [Cl2(N≡)Mo(μ2‐Cl)3Mo(≡N)Cl2]— as in Mo2NCl8, which in this case are connected with MoCl4+ moieties by asymmetric nitrido bridges Mo≡N‐Mo forming chains. In Mo2NCl8 the Mo‐N distances in the nearly linear nitrido bridges are 167.6(2), and 214.8(2) pm, whereas in case of Mo3N2Cl11 two sets of Mo‐N distances of 166, 8(4) and 214, 0(4) pm as well as 166, 9(4) and 211, 9(4) pm are observed. 相似文献
4.
Preparation of trans-[Mo6Cl8]Cl4Br22? Starting from Crystalline [Mo6Cl8]Cl4(H2O)2 and Crystal Structure of [(C6H5)4As]2[Mo6Cl8]Cl4Br2 The synthesis of the title compound is successful if the crystallized [(Mo6Cl8)Cl4(H2O)2] containing the H2O molecules in trans-position reacts with HBr + [(C6H5)4As]Br in ethanol in a heterogeneous reaction. The X-ray structure investigation confirms the existence of discrete trans-Br-substituted cluster anions of composition [(Mo6Cl8)Cl4Br2]2? in the crystal. The reaction in homogeneous solutions proceeds to Br-enriched compounds. [(C6H5)4As]2[(Mo6Cl8)Cl4Br2] crystallizes in the triclinic space group P¯1 with a = 11.071(2), b = 11.418(2), c = 12.813(2) Å, α = 116.10(2), β = 95.27(2) and γ = 94.41(2)° (?133°C). The crystal structure at ?133°C was determined from single crystal X-ray diffraction data (R1 = 0.026). The [(Mo6Cl8)Cl4Br2]2?-anions are not completely ordered but distributed statistically among the three positions which are possible within the limits of the ordered [Mo6Cl8]-cores (ratio 11:5:4). The frameworks of the anions consist of Mo6 cluster units with (slightly distorted) octahedral arrangement of the metal atoms (d(Mo? Mo): 2.600(1) up to 2.614(1) Å), which are coordinated by the halogeno ligands in a square-pyramidal manner. The details of the structure will be discussed and compared with similar [(Mo6X8)Y4] cluster units (X, Y ? Cl, Br). 相似文献
5.
Compounds consisting of both cluster cations and cluster anions of the composition [(M6X12)(EtOH)6][(Mo6Cl8)Cl4X2] · n EtOH · m Et2O (M = Nb, Ta; X = Cl, Br) have been prepared by the reaction of (M6X12)X2 · 6 EtOH with (Mo6Cl8)Cl4. IR data are given for three compounds. The structures of [(Nb6Cl12)(EtOH)6][(Mo6Cl8)Cl6] · 3 EtOH · 3 Et2O 1 and [(Ta6Cl12)(EtOH)6][(Mo6Cl8)Cl6] · 6 EtOH 2 have been solved in the triclinic space group P1 (No. 2). Crystal data: 1 , a = 10.641(2) Å, b = 13.947(2) Å, c = 15.460(3) Å, α = 65.71(2)°, β = 73.61(2)°, γ = 85.11(2)°, V = 2005.1(8) Å3 and Z = 1; 2 , a = 11.218(2) Å, b = 12.723(3) Å, c = 14.134(3) Å, α = 108.06(2)°, β = 101.13(2)°, γ = 91.18(2)°, V = 1874.8(7) Å3 and Z = 1. Both structures are built of octahedral [(M6Cl12)(EtOH)6]2+ cluster cations and [(Mo6Cl8)Cl6]2– cluster anions, forming distorted CsCl structure types. The Nb–Nb and Ta–Ta bond lengths of 2.904 Å and 2.872 Å (mean values), respectively, are rather short, indicating weak M–O bonds. All O atoms of coordinated EtOH molecules are involved in H bridges. The Mo–Mo distances of 2.603 Å and 2.609 Å (on average) are characteristic for the [(Mo6Cl8)Cl6]2– anion, but there is a clear correlation between the number of hydrogen bridges to the terminal Cl and the corresponding Mo–Cl distances. 相似文献
6.
Thiochloro Anions of Molybdenum (IV). Crystal Structure of (NEt4)3[Mo3(μ3-S)(μ-S2)3Cl6]Cl μ CH2Cl2. Crystal Structure, Magnetic Properties, and EPR-Spectrum of (NEt4)2 [Mo2(μ-S2)(μ-Cl)2Cl6] From molybdenum pentachloride and tetraethylammonium hydrogensulfide in CH2Cl2 an insoluble product of composition (NEt4)2[Mo2S3Cl9] was obtained along with a brown solution, from which (NEt4)2[Mo2(S2)Cl8] was crystallized. The insoluble product and NEt4Cl react in CH2Cl2 to yield, among others, (NEt4)3[Mo3(S)(S2)3Cl6]Cl · CH2Cl2. The latter crystallizes in the orthorhombic space group Pnma, a = 2495.8, b = 1501.2, c = 1295.6 pm, Z = 4. According to the crystal structure determination (3070 observed reflexions, R = 0.049) the [Mo3(S)(S2)3Cl6]2? ion consists of an Mo3 triangle with Mo? Mo bonds, each side of the triangle is bridged by disulfido groups and one sulfur atom is capped over the Mo3 triangle; the single chloride ion is looseley associated to three S atoms. (NEt4)2[Mo2(S2)Cl8] also crystallizes in the space group Pnma, a = 1425.6, b = 1129.9, c = 2004.7 pm, Z = 4; structure determination with 1703 observed reflexions, R = 0.061. In the [Mo2(S2)Cl8]2? ion the Mo atoms are bridged via one disulfido group and two chlorine atoms. There is a Mo? Mo bond, but according to the magnetic properties and the EPR spectrum each Mo atom still possesses one unpaired electron. 相似文献
7.
Synthesis and Structure of Mo2NCl7 The reaction of VN with MoCl5 at 175 °C in a sealed glass ampoule yields the molybdenum(V) nitride chloride Mo2NCl7 in form of air sensitive black crystals with the triclinic space group P1¯ and a = 905.7(8); b = 975.4((6); c = 1283.4(8) pm, α = 103.13(4)°; β = 109.83(5)° und γ = 98.58(5)°. The crystal structure is built up from dinuclear units [Mo2N2Cl7]3— and [Mo2Cl7]3+, which are connected by asymmetric nitrido bridges to form endless chains. Within both dinuclear units the Mo atoms are bridged by three Cl atoms resulting in a Mo‐Mo distance of 349.2(3) pm in the unit [Mo2N2Cl7]3—. In case of [Mo2Cl7]3+, however, a shorter Mo‐Mo distance of 289.4(3) pm is observed, which can be interpreted by a single bond. Correspondingly a reduced magnetic moment of 0.95 B.M. per Mo atom is observed. 相似文献
8.
Mohyi M. El-Essawi Frank Weller Karlheinz Stahl Meinolf Kersting Kurt Dehnicke 《无机化学与普通化学杂志》1986,542(11):175-181
Mo2O3Cl4(Pyridine)4 · CH2Cl2. Synthesis, IR Spectrum, and Crystal Structure Reduction of MoO2Cl2(pyridine)2 with triphenylphosphane in toluene and recrystallisation from CH2Cl2 yields brown crystal needles of the complex Mo2O3Cl4(pyridine)4 · CH2Cl2. The compound crystallizes monoclinic in the space group P21/c with four formula units per unit cell of the dimensions a = 1 234.6 pm; b = 1 593 pm, c = 1 522.3 pm and β = 105.66° A structural investigation by X-ray methods (3 276 independent observed reflexions, R = 0.033) reveals the molecule with two molybdenum atoms in a distorted octahedral coordination linked by an almost linear Mo? O? Mo bridge with bond distances of 167 and 168 pm, respectively. The chlorine atoms are located in trans-position to the oxygen atoms which have different trans effects: The Mo? Cl bond opposite the bridge (length 242 pm) is 8 pm shorter than the bond in trans position to the terminal oxo ligands. The pyridine nitrogen atoms are in trans position to each other and complete the coordination of the molybdenum atoms. The i.r. spectrum of the compound is reported. 相似文献
9.
Reaction of [Mo6Cl8]X4 with N-Bases [Mo6Cl8]X4 (X = Cl, Br, I) in ethanol solution by titration with Ag+ showed 4 labil X atoms. The displacement of X? especially by F? accelerates the titration decisively. Conductivity measurements in ethanol or acetone showed that [Mo6Cl8]X4 at 25°C behave as weak 1:1-electrolytes. Solutions of [Mo6Cl8]X4 in DMF heated up to 60°C and than lowered to 25°C showed that the compounds in this solvent behave as (potential) strong 2:1-valent electrolytes. From the following compounds the labil halides have been determined by titration with Ag+: [Mo6Cl8]X4(Py)2 (X = Cl, Br), [Mo6Cl8]X4(bipy)2 (X = Cl, Br, I), [Mo6Cl8]X4(Phenpy)2 (X = Cl, Br, I), (PyH)2[Mo6Cl8]X6 (X = Cl, Br); (bipyH)2[Mo6Cl8]I4Cl2. Always 4 (respectively 6) labil halides have been observed; exception [Mo6Cl8]Cl4(Py)2 in acetone (2 labil Cl). Lattice constants and mole volumina for the adducts with pyridin and bipyridin have been determined. The adducts with bipyridin and phenylpyridin are isotypic. Conductivity measurements have been made in different solutions. The decomposition on the thermobalance showed that in [Mo6Cl8]Cl4(Py)2 the bond of pyridin is weak. The 2 pyridin molecules are evolved at the same time. However [Mo6Cl8]I4(Bipy)2 loses 1 bipyridin only. (PyH)2[Mo6Cl8]X6 formed during the first decomposition step the novel compounds (PyH) [Mo6Cl8]X5 (X = Cl, Br). Both compounds are isotypic. They behave in ethanol solution as strong 1:1-valent electrolytes. 相似文献
10.
An ampule reaction between Mo and PCl5 at 200 °C yielded (PCl4)2[Mo2Cl10], the first ternary compound in Mo–P–Cl system. Single crystal X-ray diffraction gave a triclinic unit cell: a = 6.870(1), b = 8.892(2), c = 9.423(2) Å, α = 100.24(2), β = 95.55(2), γ = 96.12(2)° (V = 559.3(2) Å3, Z = 1, sp. gr. P1, wR2 = 0.0575 and R1 = 0.0279. The ionic compound is built from edge sharing bioctahedra [Mo2Cl10]2– and two tetrahedra PCl4+. The averaged Mo–Clb distance, 2.503(1) Å, is longer than the Mo–Clt distance, 2.33(2) Å. The Mo … Mo distance, 3.77 Å, indicates the absence of a direct Mo–Mo interaction. Semiempirical and ab initio calculations showed the possibility for [Mo2Cl10]2– to exist with long and short Mo to Mo distances, the letter corresponding to the Mo–Mo bond. 相似文献
11.
Synthesis and Crystal Structure of (PPh4)2[Mo2(S2)2Cl8] · 2 CH3CN and its Topotactic Transformation to (PPh4)2[Mo2(S2)2Cl8] MoS2Cl3 was prepared from molybdenum and S2Cl2 at 200 °C. Its reaction with PPh4Cl in acetonitrile yielded (PPh4)2[Mo2(S2)2Cl8] · 2 CH3CN. In vacuum or upon warming, it loses the acetronitrile without degradation of the crystals. According to the X-ray crystal structure determinations both compounds, with and without acetonitrile, are triclinic. They contain the same [Cl4Mo(μ-S2)2MoCl4]2– ions, in which the Mo atoms are joined by two disulfido groups and an Mo–Mo bond. Details of the crystal packings and their topotactic transformation are given. 相似文献
12.
Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH and (C18H36N2O6Na)2[Mo6Cl8(OC6H5)6] . The reaction of Na2[Mo6Cl8(OCH3)6] and 2,2,2-crypt yields (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6 CH3OH ( 1 ), which is converted to (C18H36N2O6Na)2[Mo6Cl8(OC6H5)6] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo6Cl8i(ORa)6]2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo6Cl8(OC6H5)6]2? is investigated by means of UV/VIS spectroscopy and EHMO calculations. 相似文献
13.
The Adduct of BiCl3 and Mo6Cl12: [BiCl] Dumbbells in the Structure of [BiCl][Mo6Cl14] MoCl3 reacts under decomposition to MoCl2 and Cl2 with BiCl3 in a sealed evacuated glass ampoule at 550 °C to form light red crystals of [BiCl][Mo6Cl14]. The crystal structure determination (monoclinic, C 2/c, a = 1268.1(4) pm, b = 1304.6(3) pm, c = 2571.9(8) pm, β = 91.79(3)°, Z = 8) shows that the structure is built of [(Mo6Cl8)Cl6] units containing nearly regular octahedral Mo6 clusters. These units are arranged in the motiv of a cubic closest packing. The octahedral interstices contain [BiCl] dumbbells with a Bi–Cl bond length of 249 pm. The coordination sphere of the Bi atom is completed by six weaker Bi–Cl-contacts of 275 to 308 pm length to a distorted monocapped trigonal prism. Neglecting the secondary Bi–Cl bonds, the title compound can be formulated as [(BiCl)2+][(Mo6Cl14)2–]. 相似文献
14.
Reaction of 2,2-Dimethylpropylidynephosphine with Molybdenum Pentachloride; Crystal Structure of [Mo2Cl6(α,α′-dipyridyl)3] 2,2-Dimethylpropylidynephosphine and molybdenum pentachloride dissolved in POCl3 react with oxydation of the phosphorus and reduction of the molybdenum atom to give the alkyne complex [Mo2Cl4(μ-Cl)2(μ-H9C4? C?C? C4H9)(OPCl3)2]. Addition of α,α′-dipyridyl or of methyltriphenylphosphonium chloride in dichloromethane results in a displacement of the ligands POCl3 and H9C4? C?C? C4H9 from this complex and in the formation of [Mo2Cl6(dipy)3] or [(H5C6? )3P? CH3]3[Mo2Cl9]. Besides the latter compound small amounts of [(H5C6? )3P? CH3]2[MoCl6] can be isolated from the reaction mixture. [Mo2Cl6(dipy)3] which has already been prepared by other methods crystallizes in the monoclinic space group P21/c with {a = 1612; b = 148; c = 1296 pm; γ 109.3°; Z = 4} at 20°C. As shown by a crystal structure determination the complex is built up from [MoCl2(dipy)2]+ cations and [MoCl4(dipy)]? anions. The molybdenum atoms are both octahedrally surrounded. With average values of 238 and 243 pm the Mo? Cl bond distances in the cation, where a cis-arrangement of the chlorine atoms is observed, and in the anion differ significantly from each other. [Mo2Cl6(dipy)3] which has already been prepared by other methods crystallizes in the monoclinic space group P21/c with {a = 1612; b = 148; c = 1296 pm; γ = 109.3°; Z = 4} at 20°C. As shown by a crystal structure determination the complex is built up from [MoCl2(dipy)2]+ cations and [MoCl4(dipy)]? anions. The molybdenum atoms are both octahedrally surrounded. With average values of 238 and 243 pm the Mo? Cl bond distances in the cation, where a cis-arrangement of the chlorine atoms is observed, and in the anion differ significantly from each other. 相似文献
15.
S. Picard D. Salloum P. Gougeon M. Potel 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(6):i61-i62
The crystal structure of dicaesium pentadecamolybdenum nonadecasulfide, Cs2Mo15S19, consists of a mixture of Mo6S8S6 and Mo9S11S6 cluster units in a 1:1 ratio. Both units are interconnected via inter‐unit Mo—S bonds. The Cs+ cations occupy large voids between the different cluster units. The Cs and two inner S atoms lie on sites with 3 symmetry (Wyckoff site 12c) and the Mo and S atoms of the median plane of the Mo9S11S6 cluster unit on sites with 2 symmetry (Wyckoff site 18e). 相似文献
16.
The triangular six-electron cluster complex [Mo3S4Cl4(PEt3)
x
(thf)5] produced by the excision reaction of Mo3S7Cl4 with triethypholsphine is reduced by magnesium at – 20°C. Subsequent addition of dppe (=1,2-his(diphenylphosphino)ethane) to the reduced species affords a seven-electron triangular cluster complex [Mo3S4Cl3(dppe)2(PEt3)]. The complex crystallizes in the space groupCm witha=17.170(6),b-19.878(6),c = 13.289(5) = 121.73(2)°,V = 3858(2) A3, andZ = 2. The structure shows an almost equilateral triangle of three molybdenum atoms capped by a Sulfur atom and bridged by three sulfur atoms. The Mo Mo distances, ranging from 2.804(1) to 2.809(1) A are elongated ca. 0.04 A as compared with lose of a six-electron cluster complex with drape ligands. Two molybdenum atoms have a chlorine and a dppe ligands, and the other molybdenum atom bas a chlorine and a triethylphosphine ligands. The UV-Vis spectrum has a characteristic broad hand centered at 1410 n m, which is not observed for six-electron clusters. The ESR spectrum indicates the presence of an unpaired electron consistent with the formulation of the compound as a seven-electron cluster.Dedicated to Professor fiaxi Lu on the occasion of his 80th birthday. 相似文献
17.
Synthesis and Crystal Structure of (PPh4)2[Mo2Cl10] The title compound is obtained in the reaction of [MoCl4(Ph? C?C? Ph)]2 with tetraphenylphosphonium chloride in dichloro methane, forming brown crystals. It is characterized by the i.r. spectrum and a crystal structure analysis by the aid of X-ray diffraction data. The complex crystallizes triclinic in the space group P1 with one formula unit per unit cell. The cell dimensions are a = 1122 pm, b = 1137 pm, c = 1283 pm; α = 63.4°, β = 69.1°, γ = 86.5°. The crystal structure determination (2959 observed, independent reflexions, R = 4.5%) shows the constants of the unit cell to consist of on centrosymmetric anion, two cations and one disordered molecule of dichloro methane. The distance Mo? Mo in the anion is 380 pm, which excludes direct magnetic interaction between the molybdenum atoms. 相似文献
18.
15N and 19F NMR Spectra and Xa-Exchange Reactions of the Cluster Anions [(Mo6Cli8)(15NCS)anXa6?n]2?, Xa = F, Cl, Br, I; n = 1–6 By intermolecular ligand exchange reaction of the new compound [(Mo6Cli8)(15NCS)a6] 2? with [(Mo6Cli6)Xa6]2?, Xa = F, Cl, Br, I, in acetone, the outersphere mixed cluster ions [(Mo6Cli8)(15NCS)a6Xa6?n]2?, n = 1–6, are formed and characterized by their distinct 15N nmr chemical shifts. The ambident SCN? is exclusively N-bonded, indicated by 15N nmr and vibrational spectra. The mixed cluster ions containing Xa = F are identified in acetonitrile by 19F nmr measurement as well. The kinetic analysis reveals equilibration at room temperature within 10 hours to statistical distribution of all compounds, inclusive the ratios for the geometric isomers for each system at any time with n = 2,4 cis:trans = 4 : 1 and n = 3 fac:mer = 2 : 3, indicating the equivalence of all Xa positions with respect to exchange reactions. For [(Mo6Cli8)Xa6]2? the reaction rates increase in the series Xa = Cl < Br < I < SCN < F. The 15N nmr chemical shifts are depending on the electronegativity and the number of the Xa ligands. Furthermore an antipodal influence working on 15N trans-positioned to Xa effects an additional highfield shift for Xa = F and an additional downfield shift for Xa = Cl, Br, I. 相似文献
19.
Some Reactions with [Mo6Cl8]Cl4 The reaction of [Mo6Cl8]Cl4 with different chemical agents has been investigated: The methoxylation depends on the CH3O? concentration in CH3OH. The reaction with HF leads to a partial fluorinated [Mo6Cl8] product. With NH4F (NH4)2[Mo6Cl8]F6 in formed, the hydrolysis of which leads to [Mo6Cl8]F3(OH) · 2.5 H2O. This compound can be decomposed thermically into [Mo6Cl8]O2. [Mo6Br8]F62? on hydrolysis leads to [Mo6Br8]F3(OH) · 5 H2O. With CsF Cs2[Mo6Cl8]F6 is formed, which by hydrolysis is transformed into [Mo6Cl8]F3(OH) · 2.5 H2O and possibly to [Mo6Cl8]F4 · xH2O(?). In reaction of [Mo6Cl8]Cl4 with H2SO4 one gets [Mo6Cl8](SO4)2. Salts e. g. [(C6H5)4As]2[Mo6Cl8](OC6F5)6 and adducts e. g. [Mo6Cl8](OC6F5)4 · 2 HMPA are prepared. The compounds have been characterized by X-ray powder-diagramms and by IR-spectra. 相似文献
20.
Dithiolylium Chlorooxomolybdates(V): Synthesis and Crystal Structure of (C3Cl3S2)[MoOCl4] and (C3Cl3S2)[Mo2O2Cl7] The reaction of 3, 4, 5‐Trichlor‐1, 2‐dithiolylium chloride with MoOCl3 in dichlormethane under solvothermal conditions at 65 °C simultaneously yields the green tetrachlorooxomolybdate(V) (C3Cl3S2)[MoOCl4] and the yellow‐brown heptachlorodioxodimolybdate(V) (C3Cl3S2)[Mo2O2Cl7]. The crystal structures of both compounds contain nearly planar (C3Cl3S2)+ ions with a S—S bond length of 203 pm. The discrete [MoOCl4]— ion in the structure of (C3Cl3S2)[MoOCl4] has the shape of a square pyramid with the oxygen atom at the apex. The molybdenum atom is displaced by 58 pm from the basal plane towards the oxygen atom. The [Mo2O2Cl7]— ion in the structure of (C3Cl3S2)[Mo2O2Cl7] has the form of a face‐sharing double octahedron. It is formally composed of a [MoOCl4]— ion and a MoOCl3 molecule connected by one symmetrical and two unsymmetrical chloro bridges. The molybdenum atoms placed in the centers of such connected octahedra are 357 pm apart, indicating no Mo—Mo bond. 相似文献