An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The crystal structures of three compounds have been determined at room temperature, namely [Gd(hfa)(3)Cu(salen)] (1), [Y(hfa)(3)Cu(salen)] (2), and [Gd(hfa)(3)Cu(salen)(Meim)] (3), and the crystal structure of a fourth compound, [La(hfa)(3)(H2O)Cu(salen)] (4), has been determined at -100 degrees C; hfa = hexafluoroacetylacetonato, salen N,N'-ethylenebis(salicylideneaminato), and Meim = 1-methylimidazole. [La(hfa)(3)Ni(salen)] (5), isomorphous with 1, has also been synthesized. 1 crystallizes in the monoclinic system, space group P2(1)/n, with a 17.292(5) Angstrom, b = 22.370(5) Angstrom, c 19.658(6) Angstrom, beta = 90.07(2)degrees, and Z = 8. 2 crystallizes in the triclinic system, space group Pi, with a = 12.207(3) Angstrom, b = 13.019() Angstrom, c = 13.011(6) Angstrom, alpha 82.87(4)degrees, beta = 83.55(3)degrees, gamma = 70.91(3)degrees, Z = 2. 3 crystallizes in the monoclinic system, Space group P2(1)/n, with a 16.521(9) A, b = 20.381(5) Angstrom, c 12.758(6) Angstrom, beta = 93.22(6)degrees, and Z = 4. 4 crystallizes in the monoclinic system, space group P2(1)/1, with a 12.826(2) Angstrom, b = 23.067(8) Angstrom, c = 13.081(3) Angstrom, beta 91.37(2)degrees, and Z = 4. The structures of 1, 2, and 4 consist of dimers of binuclear units in which the metal ions are bridged by the oxygen atoms of the salen ligand, with rather short Cu-Cu intermolecular separations (3.630(3) Angstrom for 1, 4.251(2) Angstrom for 2, and 3.620(2) Angstrom for 4). The Gd-III ion in 1 and the Y-III ion in 2 have a square antiprismatic environment, while the La-III ion in 4 is nine-coordinate with a water molecule in the La-III coordination polyhedron. In compounds 1, 2, and 4 the CUII ion has a square planar environment. The Gd-Cu distances are 3.198(2) and 3.231(2) Angstrom for 1, the Y-Cu distance is 3.257(1) Angstrom for 2, and the La-Cu distance is 3.381(2) Angstrom for 4. The structure of 3 consists of perfectly isolated binuclear species, the Meim ligand occupying a peripheral apical position in the copper coordination sphere. The magnetic properties of 1 and 3 have been investigated. They have revealed Gd-III-Cu-II ferromagnetic interactions. The ground state of 3 is an S = 4 state, stabilized by 5.68 cm(-1) with respect to the S = 3 excited state. The situation is more complicated for 1, due to the presence of Cu-Cu intermolecular interactions.

Reaction of either (n-Bu4N)2[Mo5O13(OMe)4(NO){Na(MeOH)}]·xMeOH or (n-Bu4N)3[Mo6O18(NO)] with various reducing agents, including N2H4·2HCl, in methanol or in a mixture of methanol and acetonitrile, yields reduced nitrosyl decamolybdates, among which (n-Bu4N)[Mo10O25(OMe)6(NO)] ((n-Bu4N)II) and two forms of (n-Bu4N)2[Mo10O24(OMe)7(NO)] ((n-Bu4N)2IVa and (n-Bu4N)2IVb) have been crystallographically characterized. IVa,b are diastereoisomers that differ in the location of methoxo groups. The molecular structures of II and IV are closely related to that of [W10O32]4-, the so-called decatungstate Y, and consist of two halves of five edge-sharing octahedra connected through four quasi-linear Mo−O−Mo bridges. Besides the four electrons essentially residing at the Mo(II) center bearing the nitrosyl ligand, II and IV further accommodate two and four delocalized "blue" electrons, respectively. II and IV thus contain molybdenum atoms in three different oxidation states, Mo(II), Mo(V), and Mo(VI). On the basis of their optical spectra, they are best described as class II mixed-valence complexes according to the classification of Robin and Day. Their intimate electronic structure has been further investigated by means of extended Hückel calculations on the model compound [Mo10O26(OH)6]. The composition of the HOMO clearly demonstrates that the "blue" electrons are circulating among the eight equatorial molybdenum sites, the delocalization being strongly favored by the quasi-linear M−O−Mo bridges.

Reaction of either (n-Bu4N)(2)[Mo5O13(OMe)(4)(NO){Na(MeOH)}]. xMeOH or (n-Bi4N)(3)[Mo6O18(NO)] with various reducing agents, including N2H4 .2HCl, in methanol or in a mixture of methanol and acetonitrile, yields reduced nitrosyl decamolybdates, among which (n-Bu4N)[Mo10O25(OMe)(6)(NO)] ((n-Bu4N)II) and two forms of (n-Bu4N)(2)[Mo10O24(OMe)(7)(NO)] ((n-Bu4N)(2)IVa and (n-Bu4N)(2)IVb) have been crystallographically characterized. IVa,b are diastereoisomers that differ in the location of methoxo groups. The molecular structures of II and N are closely related to that of [W10O32](4-), the so-called decatungstate Y, and consist of two halves of five edge-sharing octahedra connected through four quasi-linear Mo-O-Mo bridges. Besides the four electrons essentially residing at the Mo(ll) center bearing the nitrosyl ligand, II and IV further accommodate two and four delocalized ''blue'' electrons, respectively. II and IV thus contain molybdenum atoms in three different oxidation states, Mo(II), Mo(V), and Mo(VI). On the basis of their optical spectra, they are best described as class II mixed-valence complexes according to the classification of Robin and Day. Their intimate electronic structure has been further investigated by means of extended Huckel calculations on the model compound [Mo10O26(OH)(6)]. The composition of the HOMO clearly demonstrates that the ''blue'' electrons are circulating among the eight equatorial molybdenum sites, the delocalization being strongly favored by the quasi-linear M-o-Mo bridges.

A new Cu-Zn bimetallic precursor Cu0.06Zn0.94C4O4H2 . 2H(2)O useful as a model catalyst for methanolation of syngas was prepared and identified. It crystallises in the monoclinic space group Cc with cell parameters a = 5.725(1), b = 16.251(2), c = 6.825(1) Angstrom, beta = 90.72(1)degrees, Z = 4. The structure analysis shows a two-dimensional polymeric structure with layers containing metal atoms interconnected by tridentate maleate anions. The smallest ring in the layer contains 18 atoms among which are three metal atoms. These metal atoms are connected by two maleate ligands through the opposite carboxylic groups and the ring is completed by one syn-anti carboxylate bridge Zn-O-C-O-Zn. The metal atom is five-co-ordinated in the MO2O3 form through three oxygen atoms from three different maleate anions and two terminal water ligands. The packing of the structure is stabilised by intra-and inter-layer hydrogen bonds. Thermal decomposition begins with dehydration (75-170 degrees C) followed by decomposition of the maleate anions (190-635 degrees C). As final phases, zincite ZnO (major) and tenorite CuO (minor) were identified.

Dreifach ungesättigt sind α‐A‐[PW9O34]9− ‐lonen, die mit tBuSiCl3, zum Anion 1 reagieren. Dieses läßt sich mit Trichlorsilanen zu α‐A‐[PW9O34(tBuSiO)3(RSi)]3− ‐Ionen umsetzen (R = H, Me, Et, CHCH2, CH2CH2CH2Cl). Auch über ähnliche Arsenverbindungen berichten die Autoren.magnified image

The compounds [Rh-2(mu-OAc)(4)(terpy)(2)] (1) and [Rh2Cl2(mu-OAc)(terpy)(2)](H3O)Cl-2 .-9H(2)O (2) have been synthesized in reactions of [Rh-2(mu-OAc)(4)(H2O)(2)] with 2,2':6',2 ''-terpyridine (terpy) (compound 1) and with terpy and NaCl (compound 2) in ethanol using stoichiometric quantities of reactants. Both compounds were structurally and spectroscopically characterized. In 1 terpyridine acts as a monodentate ligand. The compound 2 is the first Rh(II) complex containing only one carboxylato bridging ligand to be analyzed crystallographically. The Rh-Rh distance in 1 is considerably shorter than in 2, The complex 2 in basic solutions in alcohols is an efficient catalyst for reduction of ketones.

The reactions of 2-thienylamidoxime and 2-thienylmethylamidoxime with [MoO2(acae)2] or x-(NBu4 [Mo8O26]. in alcohols or acetonitrile, yield a number of compounds with different nuclearities and various molybdenum cores, such as the compact {Mo4O10(OMe)2}2+ the cyclic {Mo4O12}, and the open {Mo11On211-1}2+ (n= 2 or 4) cores. Addition of NH2OH to the reaction mixtures results in the formation of nitrosyl complexes containing either the Mo(NO)3 or the Mo(NO) 2 2 units. The amidoxime component may be present either as RC(NH2)NHO. RC(NHi2), RC(NH)NHO or RC(NH)NO2: ligands, or as hydrogen-bonded RC(NH2)NOH molecules. The crystal structures of [MoO(acac)RIC'(NH2)NO] {RJC(NH)NO}](1), [Mo(NO)(acae)2 {RIC(NH2)NO}] (4), (NBu4)2[Mo4O10(OMe)2{RIC(NH) NO}2] (12a),(NBu4)2(H3O)[Mo5O13(OMe)4(NO)].2R1C(NH2)NOH(13b) and [R1C(NH2)2)]3[Mo5O13(OEt)4(NO)] (14) (R1=2-thienyl) are reported. The cryslallographic data for these compounds are as follows:1, mono-clinic. P21 a.a=24.547(4)A. b=8.188(4)A. c=9.607(3)A, ß=96.18(3)c, R=0.046. R10=0.050: 4. monoclinic, P21c.a=8.265(2)A, b=9.381(2)A,c=24.770(4)A, c = 24.7701(4) A, ß=93.99(2). R=0.039. R=0.042;12a, monoclinic, C2/c, a= 19.570(5)A. b=16.883(4)A, c = 19.82(l)A. ß= 114.36(5)°, R=0.064,R.=0.074;13b monoclinic;. P21 c.a=18.197(5)A, b=15.857(14) A, c = 23.075(17) A, β=93.20(3). R=O.050. Rw=0.057;14, trictinic PI, a = 9.871(3),b= 14.138(3).c= 14.781(8)A. α=92.67(2)c β=99.36(1)° γ=90.52(2)°. R = 0.044. Rw = 0.049. Particular attention is focused on the various coordination modes that the different ligand forms adopt: µ- κO, κ2N,O, κ2N',O, µ-κN: κ2O. and μ3- κN:κN:κ2O.

In acetonitrile, bis(acetylacetonato)dioxomolybdenum(VI), [MoO2(acac)2], reacts with disubstituted hydrazine hydrohalides (RR'NNH3+X-: R = R' = Ph; R = Ph, R' = Me; X = Cl, Br, I) to yield a new series of complexes, which have been characterized by elemental analysis, electrochemistry and spectroscopy (IR, UV-visible, and H-1 NMR) and formulated as [Mo(NHNPh2)(NNPh2)(acac)X2] (X = Cl (1), Br (2), I (3)) and [Mo(NHNMePh)-(NNMePh)2 (NNMePh)(acaC)X2] (X = Cl (4), Br (5), I (6)). The X-ray crystal structures of 1 and 4 are reported. Crystals of 1 are monoclinic, space group P2(1)/a, with a = 9.352(1) angstrom, b = 31.320(2) angstrom, c = 9.612(1) angstrom, beta = 95.35(1)degrees, and Z = 4. The structure was solved using 3833 unique reflections, and refinement gave final R and R(w) values of 0.037 and 0.052, respectively. Crystals of 4 are triclinic, space group P1BAR, with a = 7.765(1) angstrom, b = 7.715(2) angstrom, c = 17.910(2) angstrom, alpha = 89.18(1)degrees, beta = 91.35(1)degrees, gamma = 92.64(1)degrees, and Z = 2. The structure was solved using 4515 unique reflections, and refinement gave final R and R(w) values of 0.032 and 0.033, respectively. Both complexes display similar distorted octahedral geometries. The coordination sphere consists of two mutually cis organohydrazido ligands, two mutually trans chloro ligands and one chelated acetylacetonato ligand. The organohydrazido(2-) and organohydrazido(1-) ligands adopt the linear and bent 'end-on' conformations, respectively.

The reaction of NH4VO3 with S2-2in ammonia in the presence of 2,2'-bipyridine (bipy) and [N(Bu)4]Br gives the mononuclear compound [N(Bu)4][V(O)(S2)2bipy] (1) isolated at room temperature in crystalline form. The X-ray crystal structure determination shows that the vanadium(V) centre is ligated by four sulphur atoms and a nitrogen atom of the bipy ligand forming the equatorial plane of pentagonal bipyramid, an oxygen and the remaining nitrogen atom of the bipy occupying the two apices of the bipyramid.

The reaction of NH4VO3 with S 2 -2 in ammonia in the presence of 2,2′-bipyridine (bipy) and [N(Bu)4]Br gives the mononuclear compound [N(Bu)4][V(O)(S2)2bipy] (1) isolated at room temperature in crystalline form. The X-ray crystal structure determination shows that the vanadium(V) centre is ligated by four sulphur atoms and a nitrogen atom of the bipy ligand forming the equatorial plane of pentagonal bipyramid, an oxygen and the remaining nitrogen atom of the bipy occupying the two apices of the bipyramid.

The reactions of salicylaldoxime and salicylamidie oxime with [VO(acac)(2)] yield several unusual compounds, including [V3O3(OR)(5)(OC6H4CH=No)(2)] (R = Me,Et), [VO2{OC(6)H(4)CX=NOC(Me)=NH}] (X = H,NH2) and [VO(OR){OC6H4CH=NCHC6H4OC(O)(Me)CHCOMe}] where the tetradentate ligand results from the coupling of acetylacetone with salicylaldimine and salicylaldehyde.

The complexes [Mo(NNPh(2))(2)Cl-2(PPh(3))] (3), [M(NNMePh)(2)Cl-2(PPh(3))(2)] (4), [Mo(NNRPh)(2)Cl-2(PMePh(2))(2)](R Ph, 5; R = Me, 6), [Mo(NNRPh)(2)Cl-2(PMe(2)Ph)(2)] (R = Ph, 7; R = Me, 8), and [Mo(NNRPh)(2)Cl-2(dppe)] (R = Ph, 9; R = Me, 10) have been obtained in good yields by reaction of [Mo(NHNRPh)(NNRPh)(acac)Cl-2] (R = Me, 1; R = Ph, 2) with PMe(3-n)Ph(n) (n = 1-3) or Ph(2)PCH(2)CH(2)PPh(2) in acetonitrile. In refluxing toluene, 4 undergoes dissociation of a PPh(3) ligand to give [Mo(NNMePh)(2)Cl-2(PPh(3))] (11). Complexes 3, 4, and 11 react with an excess of acetylacetone in refluxing acetonitrile to give back 1 or 2. Complexes 3-11 have been studied by H-1, P-31 NMR, IR, and UV-visible spectroscopy and by electrochemistry. In addition, compounds 3 and 4.0.5CH(2)Cl(2) have been characterized by X-ray crystal analyses. Complex 3 is monoclinic, space group P2(1)/c, with a = 21.787(5) Angstrom, b = 17.638(1) Angstrom, c = 20.066(14) Angstrom, beta = 95.32(1)degrees, and Z = 8. The structure was solved using 3965 unique observed reflections; the refinements of 735 variables gave final R and R(w). values of 0.049 and 0.053, respectively. Compound 4.0.5CH(2)Cl(2) is triclinic, space group P (1) over bar, with a 14.384(12) Angstrom, b = 16.599(6) Angstrom, c = 23.919(11) Angstrom, a = 77.44(4)degrees; beta = 77.51(1)degrees, gamma = 64.39(2)degrees, and Z = 4. The structure was solved using 5456 unique observed reflections; the refinements of 901 variables converged to R and R(w) values of 0.070 and 0.083, respectively. Complex 3 displays a distorted trigonal bipyramidal geometry with the cis-hydrazido ligands in the equatorial plane, while 4 disp,lays a distorted octahedral geometry with cis-hydrazido and trans-phosphine ligands.

The reaction of Cp2MMe2 (M = Zr, Hf) with Ph2Si(OH)2 yields the eight-membered ring [Cp2M(mu-OSiPh2O)]2 (M = Zr (1), Hf (2)). 1 crystallizes in the space group P1BAR with a = 10.410(9) angstrom, b = 12.140(6) angstrom, c = 16.318(5) angstrom, alpha = 94.26(3)degrees, beta = 103.42(5)degrees, gamma = 93.16(6)degrees, and Z = 2. The crystal structure reveals that the ring is not planar. The Cp2Zr units are bent 20-degrees out of the Si2O4 Plane to give a ''chaise longue conformation; however, in solution the molecule is fluxional on the NMR timescale. The zirconium-oxygen distances of 1.974(2) and 1.983(2) angstrom are significantly longer than those reported in other Zr-O-Si compounds. EHMO calculations suggest that the Zr-O bond order may be rationalized in terms of an in-plane pi-system.

[MoO2(acac)2] reacts with two equivalents of arylhydrazines in MeOH or MeCN to give mononuclear bis(aryldiazenido) molybdenum complexes of the type [Mo-(NNC6H4R-p)2(acac)2], where R = H (1); Me (2); MeO (3); F (4) or NO2 (5). These complexes have been characterized by i.r., 1H-n.m.r. and u.v.-vis. spectroscopy. The crystal structures of (2) and (3) have been determined. Both lattices are made of discrete mononuclear species containing the cis-[Mo(NNAr)2]2+ unit with singly bent aryldiazenido ligands.

Several salts of the general formula O3[PMo4O24] were obtained from the reaction of molybdic oxide, MoO3, or Na2H[PMo12O40].aq with hydrogen peroxide, orthophosphoric acid and the appropriate onium salt, QX, (Q+=[(n-C6H13)4N]+; [n-C4H9)4N]+; {[(C6H5)3P]2N}+; [o-NH2-C5H5N]+; Arquad 2HT(R)). The structure of [(n-C6H13)4N]3 [PMo4O24] (monoclinic C2,a=20.485(3) angstrom; b=15.996(2) angstrom;c= 14.822(3) angstrom;beta=91.42(1)-degrees;Z=2) was refined with R=0.0465 and R(w)=0.0520. The polyanion has one bridging and one non-bridging peroxo group on each Mo centre with relatively short O-O bonds (1.46-1.48 angstrom). The structural features compare well with those of the previously described complex, [(n-C6H13)4N]3[PW4O24], and with a recently isolated hydrogen-bis(oxodiperoxotungsto)phosphate(2-), [(n-C4H9)4N]2[HPW2O14], but the tungsten complexes have longer O-O bonds than the molybdenum complex. The vibrational (IR and Raman) and P-31 NMR spectra suggest that the structure is conserved in a biphasic medium (CHCl3/H2O2-H2O). 1-Octene and (R)-(+)-limonene are stoichiometrically, or catalytically, in the presence of hydrogen peroxide, epoxidized by Q3[PM4O24] (M = Mo or W) and Q2[HPW2O14]. The two anionic tungsten (VI) species are about 30 times more active than the Mo(VI) complex. These differences correlate with the O-O bond distances in the peroxo groups and with the observed nu(O-O) frequencies (IR and Raman, both solid state and solution spectra).

The synthesis, crystal structure, and magnetic properties of [CP2Ti(mu-OCH3)]2 (1) (CP = eta-5-C5H5) and [Cp2Ti(mu-OC2H5)]2 (2) are described. The two compounds are obtained from [CP2Ti(CH3)2] and trimethoxy- and triethoxysilane, respectively, in hexane. Both crystallize in the tetragonal system, space group P4n2BAR. Data for 1: a = 8.003 (1) angstrom, b = 8.003 (1) angstrom, c = 16.078 (4) angstrom, and Z = 2; Ti-O = 2.065 (2) angstrom, Ti-O-Ti = 108.8 (1)-degrees; R(w) = 0.039. Data for 2: a = 8.238 (1) angstrom, b = 8.238 (1) angstrom, c = 15.717 (2) angstrom; Ti-O = 2.076 (3) angstrom, Ti-O-Ti = 108.0 (2)-degrees; R(w) = 0.029. The Ti-Ti distances of 3.35 angstrom for both compounds are remarkably short. 1 and 2 are paramagnetic dimers exhibiting antiferromagnetic behavior with J = -268 +/- 4 cm-1 for 1. Their frozen-solution EPR spectra are typical of triplet states with a rhombic zero field splitting (ZFS) tensor (D = -0.0446 and -0.0463 cm-1 and E = -0.0069 and -0.0066 cm-1 for 1 and 2, respectively). Analysis of this ZFS tensor is presented in terms of dipolar and pseudodipolar magnetic interactions, the latter in connection with exchange interactions between the ground state of one metal center with excited states of the other center. EPR spectra of the [CP2TiCl]2 (3) dimer are also presented, and the parameters are compared with those of 1 and 2.