MOLECULAR AND CRYSTAL STRUCTURES OF TETRANUCLEAR MOLYBDENUM CLUSTER[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)~6]■

The new cluster[Mo_4(μ_3-O)_2O_4Cl_2(o-CH_3C_6H_4COO)_6]has been prepared by the reaction of molybdenum pentachloride and o-methylbenzoic acid.The crystal and molecular structures were determined by the X-ray diffraction method.It crystallizes in the orthorhombic space group Pnna with cell parameters:Mr=1361.6,a=13.792(4), b=17.957(3),c=20.974(9) ,V=5194(2) ~3,Z=4,Dc=1.74/cm^3,F(OOO)=2704,μ(MoK ) =11.0/cm,R=0.074.

Synthesis and Crystal Structure of Cubane-type Molybdenum Cluster Complex Mo_4S_4(DTP)_4[μ-SOP(OEt)_2]_2

A cubane-type molybdenum cluster compound Mo4S4(DTP)4[-SOP(OEt)2]2 A (DTP = diethyl dithiophosphate) was obtained from the reaction of cation [Mo3O2S2(H2O)9]4+ B with metal tin as well as HDTP. The crystal structure has been determined by X-ray crystallography and the data for the title compound: Mo4S14P6O14C24H60, triclinic P , Mr = 1591.14, a = 12.5596(5), b = 14.3441(5), c = 18.0005(6) ? = 85.318(1), = 70.495(1), = 78.415(2)? V = 2994.2(2) ?, Z = 2, Dc = 1.765 g/cm3, (MoK? = 1.515 mm-1, F(000) = 1596, R = 0.0918 and wR = 0.1908 for 3546 reflections (I > 2(I)). X-ray analysis reveals that two weak CH贩稯 hydrogen bonds exist in the packing diagram with C贩稯 distance 3.22(5) ? The structure of A is similar to that of -Mo4S4(DTP)6 except that one sulfur of each bridging DTPs has been replaced by oxygen during the reaction, resulting in two bridging [SOP(OEt2)2] - ligands.

Synthesis and Crystal Structure of an Incomplete Cubane-like Heterobimetallic Cluster [（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）]

The reaction of[（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）]1 with Na2S in MeCN produced a trinuclear cluster [（η^5-C5Me5）2Mo2（μ3-S）（μ-S）3（CuCl）] 2. 2 crystallizes in the monoclinic system, space group P21/c with a = 15.563（3）, b = 8.9547（18）, c = 17.846（4） A, β = 101.29（3）°, V = 2438.9（9） A^3, Z = 4, Dc = 1.878 g/cm^3, T = 193（2） K, C20H30ClCuMo2S4, Mr = 689.60, F（000） = 1376, μ（MoKa） = 2.335 mm ^-1, S = 1.050, R = 0.0305 and wR = 0.0688 for 4033 observed reflections with I 〉 20-（I）. In the structure of 2, one [（η^5-C5Me5）2Mo2（μ-S）2S] moiety and one CuCI unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by one ,μ3-S atom, two μ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519（7） and 2.7689（8） A, respectively.

Synthesis and Crystal Structure of a Mo-S Cluster Compound Coordinated by Isonicotinate

A cluster compound, Mo3S4（DTP）3（IN）（Py）·EtOH I （DTP = diethyl dithiophosphate, IN = isonicotinate） has been rationally synthesized and characterized by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 13.6345（2）, b = 13.7805（2）, c = 14.5400（1）A, α = 107.078（1）, β = 113.380（1）, γ = 96.310（1）°, C25H45Mo3- N2O9P3S10, Mr = 1218.96, V = 2315.75（5） A^3, Z = 2, Dc = 1.748 g/cm^3, μ = 1.399, F（000） = 1224, R = 0.0425 and wR = 0.1144 for 6335 observed reflections （I 〉 2σ（I））. 31^P NMR spectrum has been measured with the resonance 110.050 and 108.783 （2：1）.

Synthesis and Crystal Structure of an Incomplete Cubane-type Mo_3S_4 Cluster with the N-N-O Type Tridentate Ligand: {Mo_3S_4[NH_2CH_2CH(O)CH_2NH_2]_3}(DTP)·(H_2O)_2·(DMF)

A new cluster {Mo3S4[NH2CH2CH(O)CH2NH2]3}(DTP)?(H2O)2?(DMF) (DTP = diethyldithiophosphate) has been synthesized via ligand substitution reaction of Mo3S4(DTP)4(H2O) with an alkaline ligand 1,3-diamino-2-propanol(DAPROH) in a mixed organic solvent, and its crys- tal structure was determined with the following data: Mo3S6PC16H48O8N7, Mr = 977.76, triclinic, space group P1, Z = 2, a = 10.319(2), b = 12.843(3), c = 15.335(3) ?, α = 65.26(3), β = 82.18(3), γ = 70.67(3)o, V = 1741.7(6) ?3, Dc = 1.864 g/cm3, μ = 1.517 mm-1, F(000) = 988, the final R = 0.0794 and wR = 0.2111 for 6318 observed reflections (I>2σ(I)). The structure analysis indicates that all DTP ligands of Mo3S4(DTP)4(H2O) are replaced and each DAPRO molecule acts as a tri- dentate ligand chelating to each Mo atom of the Mo3S4 core. Different from the precursor, the clus- ter symmetry is elevated to C3. In addition, the UV-spectrum of the title compound was measured.

Synthesis and Crystal Structure of a New Dimolybdenum(V) Complex Na_4[Mo_2O_4(HNTA)_2]_2·19H_2O

The new binuclear molybdenum（V） complex Na4[Mo2O4（HNTA）2]2·19H2O （NTA = nitrilotriacetate） has been prepared and characterized by single-crystal X-ray diffraction analysis and IR. The crystal has space group Pnma with a = 10.2239（2）,b = 23.8174（3）,c = 23.1845（4） A,V = 5645.58（16）A^3,Z = 4,C24H66Mo4N4Na4O51,Mr = 1702.50,Dc = 1.958 g/cm^3,μ = 1.027 mm^-1,F（000） = 3280,T = 293（2） K,the final R = 0.0609 and wR = 0.1449 for 5512 observed reflections （I 〉 2σ（I））. Each MoV atom has a distorted octahedral coordination geometry,and the two coordination octahedra share a common edge to form a dioxo-bridged Mo2O4 unit which is coordinated by NTA ligands. The dianionic binuclear units [Mo2O4（HNTA）2]^2- are interconnected by Na^＋ into a layered structure.

Synthesis and Crystal Structure of a New Mo/Au/S Cluster [Et_4N][Mo_2S_4(AuPPh_3)(edt)_2]· 0.25Et_2O·0.25MeOH(edt=Ethanedithiolate)

Reactions of the preformed cluster precursor [Et4N]2[Mo2S2（μ-S）2（edt）2] （edt = ethanedithiolate） （1） with [Au（PPh3）Cl] in MeOH/MeCN gave rise to a new heterobimetallic Mo/Au/S cluster [Et4N][Mo2S4（AuPPh3）（edt）2]·0.25Et2O·0.25MeOH （2·0.25Et2O·0.25MeOH）. It was characterized by elemental analysis, IR spectrum and X-ray analysis. 2·0.25Et2O·0.25MeOH crystallizes in the monoclinic system, space group C2/c with a = 20.117（4）, b = 9.2705（19）, c = 44.418（9） A^°, β= 93.19（3）°, V = 8271（3） A^°^3, Z = 8, Dc = 1.794 g/cm^3, T = 193 K, C31.25H43AuMo2NO0.50PS8, Mr = 1116.96, F（000） = 4380, μ（MoKa） = 4.603 mm^-1, S = 1.019, R = 0.0672 and wR = 0.1708 for 7243 observed reflections with I 〉 2σ（I）. The anion of 2 consists of a butterfly-shaped Mo2S4Au core in which one [AuPPh3]^＋ cation is coordinated by one bridging S and two terminal S atoms of the [（edt）2Mo2（S）2（μ-S）2] moiety. The Au（I） center adopts a pseudo-tetrahedral coordination geometry, and the Au-S bond lengths vary from 2.425（2） to 2.898（3）A^°.

A dinuclear molybdenum cluster containing i-mnt ligand: synthesis and crystal structure of [Mo_2S_4(i-mnt)_2] (Et_4N)_2

A dinuclear molybdenum(V) cluster compound (Et4N)2[Mo2S4(i-mnt)2] (i-mnt=l,l-dicyanoethylene-2,2-dithiol, (S2C=C(CN)2]2-) has been prepared by the ligand substitution reaction of Mo2S4(iso-pr2dtp)2 (iso-pr2dtp=S2P(OC3H7)2-) with K2(i-mnt) in the presence of Bt4NI. This cluster was characterized by inrrared spectrum, UV-Vis spectrum and single crystal structure analy-sis. The cluster anion [Mo2S4(i-mnt)2]2- possesses C, symmetry with a crystallographic mirror plane through two bridging S atoms. By the S....S supramolecular interactions between two adjacent cluster anions the [Mo2S4(i-mnt)2]2- anions are linked to form infinite chains along the b axis. Crystal data: monoclinic, space group C2/m, a=1.8748(6), b=1.5360(4), c=1.4322(5) nm, ,β=112.02(2)°, V=3.823(4) nm3, Z=4, Dc=1.50 g/cm3. The final R=0.038 and .RW=0.053 for 3015 observed unique reflections.

Synthesis and Crystal Structure of [MoOS_3Cu_3I(dmpzm)_2]·2(MeCN)_(0.5) (dmpzm=Bis(3,5-dimethylpyrazolyl)methane)

Reaction of a preformed cluster [Et4N]4[Mo2O2S6Cu6I6] with bis（3,5-dimethylpyrazolyl）methane （dmpzm） in acetonitrile afforded the title compound [MoOS3Cu3I（dmpzm）2]·2（MeCN）0.5 1. The single-crystal X-ray diffraction study shows that 1 （C24H35Cu3IMoN9OS3, Mr = 975.25） crystallizes in triclinic, space group P1^- with a = 11.442（2）, b = 11.644（2）, c = 16.211（3） A, α = 99.26（3）, β= 102.22（3）, γ = 118.51（3）°, V = 1766.5（10） A^3, Z = 2, Dc = 1.834 g/cm^3, T = 193（2） K, F（000） = 960, μ = 32.12 cm^-1, λ = 0.71073A^3, R = 0.0355 and wR = 0.0915 for 5686 observed reflections with Ⅰ 〉 2σ（Ⅰ）. In the molecular structure of 1, the [MoOS3]^2- anion acts as a tridentate ligand to bind one CuI group and two [Cu（dmpzm）]^＋ units to form a nido-like [MoOS3Cu3] core with an approximate C2v symmetry. The Mo…Cu contacts are in the range of 2.6460（12）～2.6798（11）A.

Synthesis and Crystal Structure of a 2D Honeycomb-like Polymeric Cluster （Et4N）3{[MoS4Cu2（μ-CN）]2（μ＇-CN）}·2MeCN

Reaction of a preformed cluster （Et4N）2[MoS4（CuCN）2]·H2O（1） with acetic acid in MeCN gave rise to an interesting 2D polymeric cluster （Et4N）3 {[MoS4Cu2（μ-CN）]2（μ^1-CN）}·2MeCN （2）. Compound 2 was characterized by elemental analysis, IR spectrum, and single crystal X-ray crystallography. In the structure of 2, the cluster core MoS4Cu2 of the cluster precursor 1 is retained and serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D （6,3） （honeycomb-like） network. The acetic acid induced aggregation of supramolecular compound 2 from the cluster precursor 1 suggests that this simple synthetic strategy be likely applicable to many related systems.

Synthesis and Crystal Structure of a Novel Mixed Nido-like and Half-open Cubane-like Cluster [(n-Bu)_4N]_3[MoS_4Cu_5Br_6]

Reaction of (NH 4) 2MoS 4 with [Cu(MeCN) 4](BF 4) and (n-Bu) 4NBr in CH 2Cl 2 afforded a new hexanuclear cluster [(n-Bu) 4N] 3[MoS 4Cu 5Br 6] (1). 1 crystallizes in the monoclinic system, space group P2 1/c, with lattice parameters a=1.17383(4) nm, b=2.40136(4) nm, c=2.64112(5) nm, β=94.2020(5)°, V=7.4247(5) nm 3 and Z=4. The structure of the [MoS 4Cu 5Br 6] 3- trianion of 1 is composed of one nido-like [MoS 3Cu 3] core and one half-open cubane-like [MoS 3Cu 3Br] core, which are interconnected by sharing the same MoSCuS plane. The Mo...Cu distances vary in the range of 0.2622(6)-0.2692(5) nm.

Synthesis and crystal structure of an ionic cluster {[Mo_3(μ_3-O)(μ-S)_3(dtp)_3(py)_3][CdI(dtp)_2]}

A new cluster compound {[Mo3(μ3-O)(μ-S)3(dtp)3(py)3][CdI(dtp)2]} (dtp=S2P(O-was obtained from the reaction of (Mo3OS3(dtp)4(H2O)] with a CdI2-Bu4NI mixture.The molecular structure is composed of a cluster cation [Mo3OS3(dtp)3(py)3]+ and the complex anion [CdI(dtp)2]-Crystal data:Triclinic,space group P1 with cell parameters a=1.4672(7),b=1.5356(5),c=1.6806(5) nm,α=74.59(3),β=67.89(4),7=78.86(3)°,V=3.364(2) nm3,and Z=2,least-squares refinement of 8941 reflections gives a final agreement factor of R=0.052,Rw=0.065.

Synthesis and Crystal Structure ofα-Mo_4 X S_3( μ-dtp)_3(dtp)_3( X= 0 .6S + 0 .4O)

The title compound (Mo 4XS 15 P 6O 12 C 24 H 30 ), α Mo 4XS 3( μ dtp) 3(dtp) 3 (X=0.6S+0.4O; dtp= -S 2P〔OEt〕 2), isolated as a prismatic black crystal, was prepared from ethanolic solution of Mo(CO) 6, MoCl 5 and P 2S 5. It crystallizes in triclinic system, space group P1 with a=14.031(4), b=13.372(2), c=16.270(8), α=92.15(2), β = 72.91(3), γ = 95.20(2)°, V = 2905.4(2) 3, Z = 2, D c = 1.82 g/cm 3, M r=1598.93, F(000)=1564.8, λ =0.71069 (Mo Kα ), μ =1.584 mm -1 . The final R=0.058, R w =0.057 for 5016 observed reflections with I≥3.0σ(I ). The structure analysis reveals that the title compound has a 〔Mo 4XS 3〕 core, belonging to the cubane type tetranuclear molybdenum clusters family, with one of its four μ 3 caps being statistically occupied by S and O. Three dtp ligands chelated three μ X capped Mo atoms as terminal ligands, while another three dtp bridged these three Mo atoms and the fourth one, forming an α type cluster compound.

Synthesis, Structural Characterization and Reactivity of Two New Triangular Molybdenum Cluster Compounds: Mo_3Te_7-[S_2CN(CH_2CH_2OH)_2]_3I and Mo_3Te_4Y_3[S_2P( ~iPrO)_2]_3I (Y_3=1.43Te+1.57S)

Two triangular molybdenum-tellurium clusters, Mo_3Te_7-[S_2CN(CH_2CH_2OH)_2]_3I (1) and Mo_3Te_4Y_3[S_2P(~iPrO)_2]_3I (Y_3 = 1. 43Te+ 1.57S) (2), were obtainedfrom the reaction of K·HOdtc [HOdtc = S_2CN(CH_2CH_2OH)_2] or K·~iPr_2dtp (~iPr_2dtp =S_2P[OCH(CH_3)_2]_2) with a mixed product of elements Mo, Te(S) and I_2 at high temperature. Thestructures of the two compounds were determined by X-ray crystallography study. Crystal data are,(1): monoclinic, P2_1/n, a = 1.6256(3), b = 1.3264(2), c = 1.8808(4) nm, β = 96.923°, V = 4.025.9(14) nm^3, D_(cal) = 3.050 g·cm^(-3), Z = 4, and (2): monoclinic, P2_1/n = 1.4564(2), b =2.3917(4), c = 1.5094(3) nm, β= 114.35(2)°, V = 4.0259(14) nm^3, D_(cal) = 2.449 g·cm^(-3) and Z= 4. Single crystal analyses show that 1 consists of discrete Mo_3Te_7[S_2CN(CH_2CH_2OH)_2]_3Iconnected into three-dimensional framework via hydrogen bonds, while 2 forms a linear chain viaTe(S)―I interaction.

Synthesis and structure of {Mo_3S_7[S_2P(OC_2H_5)_2]_3}{Mo_3S_4[S_2P(OC_2H_5)_2]_4(SCN)} and interaction between their cluster units

The synthesis method and crystal structure of a novel Mo 3 cluster compound are reported. The results of structural analysis and the quantum calculation for the entire cluster molecule reveal that though two Mo 3 cluster units, which belong to two different kinds of structural type respectively, show an apparent ionic characteristic, the interaction between them via the bridging S atoms is still quite certain. The relationship between cluster electron counting and stability of the Mo 3 clusters are also primarily discussed.

新型六核双网兜状簇合物[MoS_4Cu_5Br_3(Py)_7]的合成与晶体结构

以(NH4)2[Mo2S12]·2H2O与过量CuBr在吡啶溶液中反应,得到了一个新型六核Mo/Cu/S簇合物[MoS4Cu5Br3(Py)7].X-射线单晶结构分析表明它属于三斜晶系,空间群为PīC35H35Br3Cu5MoN7S4,Mr=1335.37,a=11.6274(4),b=12.0127(4),c=18.8872(5)A,α=82.46(2),β=73.25(2),γ=62.800(13)°,V=2246.8(2)A3,Z=2,F(000)=1300.0,Dc=1.974g/cm3,μ=5.482 mm－1,5718个独立可观察点(I>3?(I)),最终偏离因子R和Rw分别为0.042和0.048.标题化合物是由2个相似的网兜状MoS3Cu3簇核通过共用MoSCuS平面形成的双网兜状结构,Mo…Cu距离在2.6830(11)～2.741(2)A之间.

含柠檬酸配体的钼硫簇合物的合成与晶体结构的测定

合成了含有Mo—S簇阴离子 [Mo2 O2 ( μ S) 2 (C6H5O7) (C6H4 O7) ]5-柠檬酸簇合物 ,并通过元素分析、红外光谱、紫外 可见光谱和X射线光电子能谱对配合物进行了表征 ,用X射线衍射法测定了该化合物的晶体结构 .结果表明 ,该簇合物属于单斜晶系 ,空间群P2 1/c,a =2 3 766( 5)nm ,b =1 3 2 74 ( 3 )nm ,c =2 2 4 71 ( 5)nm ,α=γ =90°,β=1 1 8 2 1°,V =6 2 4 7( 2 )nm3 ,Z =8,一致性因子R =0 0 83 1 ,R2 ,w=0 1 536.该簇合物阴离子中每一个Mo原子都采取扭曲的八面体结构 ,柠檬酸通过羟基、α 羧基、一个 β 羧基与Mo配位 .晶体结构表明在一个结晶学上不对称的结构单元内有两个结晶学上独立的分子 .

系列含二核钼(钨)簇阴离子化合物的合成、结构特征和簇间相互作用

报道了系列共 9个以 [(M2 OnS4-n) (i mnt) 2 ] 2 -(M =Mo ,W ;i mnt=S2 CC(CN) 2 -2 ;n =0 ,1,2 )二核簇为阴离子 ,以某些有机基团如R4N (R =烷基 ) ,质子化的 4,4′ bpy或碱金属Cs ,K ,二价金属Ni,Mn配合物为阳离子的新化合物的合成 ,晶体结构 ,谱学表征和成键特征 .这些化合物通过S…S ,S…Cl,Cl…Cl超分子相互作用及离子间氢键形成双聚、链状、层状、三维网络及包合物堆积结构 .采用扩展的H櫣ｃｋｅｌ近似下的紧束缚能带方法计算了部分化合物的能带结构 ,表明正是这些簇间或离子间的相互作用提供了簇间电荷转移的可能 .

新型无机-有机杂化材料Mo_8O_(26)(H_2bpy)_2的合成、结构及性能研究(bpy=4,4′-bipyridine)

以(NH4)6[Mo7O24].4H2O、Co(NO3)2.6H2O、4,4′-联吡啶、冰乙酸和无水乙醇为原料,在150℃下反应3 d,得到粉绿色晶体Mo8O26(H2bpy)2。通过红外光谱、元素分析和单晶X-射线衍射法表征该无机-有机杂化材料的结构。结果表明:该晶体属单斜晶系,Pī空间群;晶胞参数a=10.7200(6),b=15.1819(9),c=10.7464(6),β=93.7930(10)°,V=1745.15(17)3,Z=4;用6518个独立衍射点(R(int)=0.0185)精修结构,最终残差因子R1=0.0239,wR2=0.0261。通过UV/VIS/NIR反射光谱的研究表明,此杂化材料对太阳辐射具有选择性的吸收;同时探讨了反应条件对合成产物的影响。本晶体结构数据已收录于英国剑桥晶体学数据库,编号为:CCDC286752。

具有链结构的新颖三核簇合物Mo_3S_4（μ－CH_3C_6H_4SO_3）〔S

三核钼簇Ｍｏ３Ｓ４（ｄｔｐ）４．ＨＯ２１（ｄｔｐ＝Ｓ２Ｐ（ＯＣ２Ｈ５）２）和对甲基苯磺酸反应，以Ｃ２Ｈ５ＯＨ做为介质，在ＣｄＣｌ２和ＰＰｈ３参预下获得新颖的三核簇合物Ｍｏ（μ３－Ｓ）（μ－Ｓ）３－（μ－ＣＨ３Ｃ６Ｈ４ＳＯ３）（ｄｔｐ）．（Ｃ２Ｈ５ＯＨ）２．本文报导化合物２的晶体结构、红外光谱、紫外光谱研究结果。簇合物的分子结构存在一个非络合物的对甲基苯左侧酸基和两个Ｍｏ的桥式络合，颇为罕见。