Crystal structures of [(η5-C5H4COOH)W(CO)3R] (R=Me,I)

The crystal structures of [(₅-C₅H₄COOH)W(CO)₃R] (R=Me, I) have been determined. They crystallize in two different monoclinic space groups. R=Me isP2₁/c,a=10.4833(6),b=8.0144(7),c=13.0731(6) , =93.147(4)°, andD(calc)=2.374 g-cm^–3 forZ=4. R=I isP2₁/n,a=7.814(2),b=13.075(4),c=11.097(4) , =91.75(2)°, andD(calc)=2.953 g-cm^–3 forZ=4. Both possess a four-legged piano stool geometry. The methyl ligand in the R=Me complex is disordered between two positions insyn oranti relative to the substituted carbon of the cyclopentadienyl ligand. The iodo ligand in the R=I complex is, however, exclusively insyn-position.     

Crystal structure of 2-pyridiniumferrocene tetrafluoroborate Fe(η5-C5H5)[(η5-C5H4)(2-C5H4NH+)](BF 4 − )

Protonation of Fe( ⁵-C₅H₅)[( ⁵-C₅H₄)(2-C₅H₄N)]1 in 98% H₂SO₄ followed by dilution with water and addition of NaBF₄ yields Fe( ⁵-C₅H₅)[( ⁵-C₅H₄)(2-C₅H₄NH⁺)](BF ₄ ^– )2 instead of a ferrocinium derivative. Complex2 crystallizes in the monoclinic system, P2₁ /a:a=7.984(1),b=9.981(2),c=18.220(4) Å,=102.31 (1)°,V=1418.5 ų,Z=4. The pyridinium ring makes a dihedral angle of 21.0(2)° with the cyclopentadienyl ring to which it is bound. One F atom of BF ₄ ^– is involved in short van der Walls contacts with the N (2.764(5) Å) and the H (2.08(6) Å) atoms of the NH⁺ moiety.     

Substituted cyclopentadienyl complexes. 5. Crystal and molecular structure of [(η5-C5H4Me)Fe(CO)(L)I] [L = 2,6-Me2C6H3NC,P(OMe)3, and P(C6H11)3]

The crystal and molecular structures of three derivatives of [( ⁵-C₅H₄Me)Fe(CO)(L)I] [L=2,6-Me₂C₆H₃NC, P(OMe)₃, and P(C₆H₁₁)₃] have been determined. [( ⁵-C₅H₄Me)Fe(CO)(CNC₆H₃Me₂-2,6)I] (1): Space groupP¯1,Z=2,a=13.193(7),b=8.183(5),c=7.465(4) Å,=95.13(5),=94.39(5), =91.09(5)°. [( ⁵-C₅H₄Me)Fe(CO)[P(OMe)₃]I] (2): Space groupP2₁/c,Z=4,a=7.296(3),b=24.471(6),c=8.877(3) Å,=111.92(4)°. [( ⁵-C₅H₄Me)Fe(CO)[P(C₆H₁₁)₃]I] (3): Space groupP2₁/c,Z=4,a=9.809(3),b=14.147(2),c=8.276(3) Å,=103.07(2)°. The structures were refined toR values of 0.045, 0.070, and 0.061, respectively. Disorder was observed in the P(OMe)₃ ligands on2. Structural data for1 and3 reveal (i) a small movement of the Fe atom away from the ringC atom containing the methyl group, (ii) a larger movement of ring C atoms away from the ring least-squares plane for3 than for1, and (iii) a shift toward an allyl-ene bond length variation in the ring distances for3. Molecular mechanics calculations performed on2 produce a low-energy conformation similar to that found in the crystal structure determination of2 with an energy barrier to ring rotation of ±5 kcal mol^–1. A correlation of the structural and molecular mechanics data with the nmr spectra of complexes1 to3 indicates that the steric influence ofL on the ring rotation could be due to ring distortion and/or interaction with the ring methyl group.     

Assignment of relative configurations and conformational analysis of α-phenylacyliron complexes (η5-C5H5)Fe(CO)(PPh3)(COCHRPh). X-ray structural determinations of two complexes (η5-C5H5)Fe(CO) (PPh3)(COCHPhR), R=CHOHCH3 and R=COH(CH3)2

Conformational analysis of the alkylation and aldol condensation products of phenylacetyliron complex (4), based on¹H-NMR chemical shifts and¹H-¹H vicinal coupling constants, permitted the assignment of relative configurations to all products obtained. Configurations and conformations of two aldol condensation products,12A and13F, were determined by X-ray structural analysis and were compared with the structures deduced from¹H-NMR data. The crystals of12A and13F are monoclinic, space group of12A isP2₁/_n with cell dimensions:a=10.937(2),b=17.278(5),c=16.412(3)Å, andβ=107.52(2)°; space group of13F isP2₁/c, with cell dimensions:a=11.576(4),b=21.180(2),c=11.854(4)Å, andβ=99.80(3)°. Both structures were solved by direct methods, and refined by a full-matrix, least-squares procedure giving for12A R=0.0599 and for13F R=0.0459.     

Synthesis and molecular structure of the organometallic zwitterion (η5-C5H3MeBCl3)Fe(CO)3: evidence for alternative sites of nucleophilicity within the [(η5-C5R5)Fe(CO)2 − anion

The organometallic zwitterion (⁵-C₅H₃MeBCl₃)Fe(CO)₃ (2) is isolated as a minor product from the reaction between the sodium salt of the anion [(⁵-C₅H₄Me)Fe(CO)₂]^– and boron trichloride. The crystal structure of 2 [P2₁/n, a = 7.3927(5) Å, b = 13.8027(9) Å, c = 12.2759(9) Å, = = 90°, = 92.517(3)°] features discrete molecules in which the coordination sphere of the iron center comprises three carbonyls and a novel ( ⁵-C₅H₃MeBCl₃) ligand, derived from attack of BCl₃ on the ( ⁵-C₅H₄Me) moiety of the parent compound. The isolation of 2 confirms that the nucleophilic properties of organometallic anions of the type [( ⁵-C₅R₅)M(CO) _n ]^– (M = Fe, Ru, n = 2; M = Mo, W, n = 3) are not confined to the metal center, or to the carbonyl oxygens (examples of which have previously been reported) but also encompass the cyclopentadienyl ligand.     

Crystal and molecular structure of [Pd(η5-C5H5) (bis-1,2-diphenylphosphinoethane)] [CF3SO3]

The crystal structure of the complex [Pd( ⁵-C₅ H₅) (PPh₂) CH₂CH₂PPh₂]⁺ [CF₃SO₃]^– has been determined from single crystal X-ray data and refined by least-squares methods toR=0.046. The monoclinic crystals have unit cell dimensionsa=9.832(3),b=12.104(4),c=13.765(4)Å,=111.22(3)°, space group P2₁, andz=2. In the cationic complex the palladium atom is coordinated to the ⁵-cyclopentadienyl moiety and to the phoshorus atoms of the chelating diphosphine. The arrangement of the two phosphorus atoms and the centroid of the cyclopentadienyl ring is approximately trigonal.     

X-ray structural and molecular mechanics investigation of cyclopentadienyl-carbonyl-triphenylophosphine-phenylacetyliron, (η5-C5H5)Fe(CO)(PPh3)(COCH2C6H5)

The crystal and molecular structure of cyclopentadienyl-carbonyl-triphenylphosphine-phenylacetyl-iron (1) has been determined on the basis of X-ray data. The crystals are triclinic, space groupP¯1 (Z=2) with cell dimensions:a=9.546(1),b=10.233(1),c=5.012(2) Å,=93.70(1),=101.12(1), =112.58(1)°. The structure was solved by direct methods and refined anisotropically by a full-matrix, least-squares procedure against 4964 independent reflections, givingR=0.0416. The MM calculations done for a model of1 reproduced satisfactorily the X-ray structure.On leave from the Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.     

The importance of inter-molecular forces in crystal structure analysis: Solid state study of the diag-to-lat isomerization of (η5-C5H4Me)Re(CO)2Br2

Single crystal X-ray structures of diag and lat-(⁵-C₅H₄Me)Re(CO)₂Br₂ have been determined. The diag form crystallizes in the triclinic space group , a = 6.751(2), b = 8.537(1), c = 9.758(1) Å = 96.70(1), = 93.15(2), = 104.96(2)°, V = 534.8(2) ų, Z = 2. The lat form is monoclinic, P2₁/c, a = 11.820(1), b = 7.133(1), c = 12.924(1) Å = 98.278(8)°, V = 1078.2(2) ų, Z = 4. The unit cell volumes (per Z) of the two isomers differ by ca 1%. Molecular modelling reveals an energy difference between the two isomers of 1 kJ mol^–1 or less. The XRD powder diffraction patterns for the lat isomer produced by crystallization from solution or prepared by thermal isomerization are identical. The evidence thus suggests that the solid state isomerization reaction is a novel example of a reaction which yields a molecular structure determined by crystal packing forces.     

Crystal structure of the methanol solvate of (η5-cyclopentadienyl)[1,2-bis(diphenylphosphino)ethane] nitroruthunium(II) Ru(η5-C5H5)dppe)(NO2)·CH3OH

The title complex crystallizes in the centrosymmetric monoclinic space group C2/c (No. 15) withZ=8. The structure was refined toR=4.49% for those 2745 independent reflections with 2=5–50^o and |F |>6(F). Ruthenium-ligand distances are as follows: Ru-P=2.284(2) and 2.286(2) Å, Ru-NO₂=2.049(6) Å and Ru-C(Cp)=2.210(10)-2.246(9) Å. Bond lengths within the nitro ligand are N(1)-O(1)=1.226(10) Å and N(1)-O(2)=1.244(10) Å. The methanol of solvation is ordered but is subject to large thermal vibrational motions.     

X-ray structural and molecular mechanics investigations of cyclopentadienyl-carbonyl-triphenylphosphine-methoxyacetyl-iron (η5-C5H5)Fe(CO)(PPh3)(COCH2OMe)

The crystal and molecular structure of cyclopentadienyl-carbonyl-triphenylphosphine-methoxy-acetyl-iron (2) has been determined by X-ray. The crystals are monoclinic:P2₁/n,Z=4,=7.881(1),b=19.111(3),c=15.271(2) Å and=93.44(1)°. The structure was solved by direct methods, and refined anisotropically by full-matrix least-squares against 3419 independent reflections, givingR=0.0446. Molecular mechanics calculations reproduce satisfactorily the X-ray structure.On leave from the Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.     

Crystal and molecular structures of 1,1′-di-tert-butylnickelocene (η5-C5H4C4H 9 t )2Ni in the temperature range 143–243 K: Thermal motion in the crystal

The crystal structure of 1,1′-di-tert-butylnickelocene is studied by the X-ray diffraction technique in the temperature range 143–243 K. The crystals are monoclinic, space group P2₁/n, Z = 2. The molecule is centrosymmetric. The cyclic ligands are parallel and adopt a staggered conformation. At 143 K, the mean bond lengths are as follows: Ni-C, 2.194(6); C-C (in the ring), 1.421(6); and C-C (Me), 1.538(2) Å. Analysis of the thermal motion of the molecule is performed within the single-parameter model, which allows for the independent motion of the cyclopentadienyl ring with the tert-butyl group as a whole and the motion of the tert-butyl group. It is shown that the molecule is structurally nonrigid and the tert-butyl group executes librational motion. The B ₅ heights of the rotation barriers are estimated from the rms libration amplitudes: 〈?²〉 are equal to 40(5) and 34(4) kJ/mol at 143 and 243 K, respectively.     

Reinvestigation of the reaction of [Ru3(CO)12] with 2-mercaptobenzothiazole: X-ray structure of [(μ-H)2Ru3 (μ-η2-C7H4NS2)(μ3-η2-C7H4NS2)(CO)7]

Treatment of Ru₃(CO)₁₂ with 2-mercaptobenzothiazole at 68°C gave the known compound [(-H)Ru₃(₃-²-C₇H₄NS₂)(CO)₉] 1 and the new compound [(-H)₂Ru₃(-²-C ₇H₄NS₂) (₃-²-C₇H₄NS₂)(CO)₇] 2 in 15 and 10% yields respectively. Compound 2 has been characterized by elemental analysis, infrared, ¹H NMR and mass spectroscopic data together with single crystal X-ray crystallography. It crystallizes in the monoclinic space group C2/c with a = 31.662(6), b = 14.577(3), c = 11.602(2) Å, = 104.15(3)°, Z = 8, and V = 5192.4(2) ų. The compound consists of a Ru₃ triangle with three different Ru-Ru bond lengths [2.75264, 2.79084, 2.97604 Å] and the two 2-mercaptobenzothiazole ligands are differently attached to the metal atoms. Compound 2 is also obtained by the reaction of 1 with excess 2-mercaptobenzothiazole at 68°C.     

Crystal structure of bis(η5-methylcyclopentadienyl)-bis(4-methylbenzenesulfonato-O)-molybdenum(IV)

The compound bis(⁵-methylcyclopentadienyl)-bis(4-methylbenzenesulfonato-O)-molybdenum (IV) crystallizes in space-group P2₁/c, a = 8.2956(5), b = 26.896(3), c = 11.4196(11) Å, = 96.101(7)°, Z = 4. The sulfonate ligands are monodentate and the molybdenum atom has pseudotetrahedral coordination geometry, with angles O–Mo–O 72.0(1)° and Cp–Mo–Cp 134.9(1)° (Cp = ring centroid).     

Crystal structure of the Λ-[4M] enantiomer of cis-diaqua-bis(1,3-dimethylpteridine-2,4(1H,3H)-dione-N5,O4) copper(II) perchlorate monohydrate

Single-crystal X-ray diffraction studies have been performed on the complex cis-diaqua-bis(1,3-dimethylpteridine-2,4(1H,3H)-dione-O⁴,N⁵) copper(II) perchlorate monohydrate, [Cu(DLM)₂(H₂O)₂](ClO₄)₂ · H₂O. This compound crystallizes in the orthorhombic system, P2₁2₁2₁ space group, Z = 4 with a = 8.749(1) Å, b = 14.213(1) Å, c = 21.200(2) Å, and V = 2636.2(4) ų. The metal ion is surrounded in octahedral geometry by two mutually quasi-perpendicular N5,O4-coordinated lumazine chelators with the O4 atoms trans and the N5 atoms cis. The polyhedron is completed by two cis-coordinated water molecules. The absolute configuration of the complex can be described, following Bailar's nomenclature, as the enantiomer of the stereoisomer 4M. A three-dimensional hydrogen-bond network is defined by water molecules, perchlorate anions, and the O2 of the pteridine A.     

Synthesis, characterization, and single crystal X-ray diffraction studies of cis-Ph2C2H2(η5-C5H4)2Ca(THF)2

cis-[(1,2-diphenyl-1,2-dicyclopentadienyl)ethanediyl]bis(tetrahydrofuran)calcium is prepared by reductively coupling phenylfulvene with activated calcium to produce cis and trans isomers which can be separately crystallized. The cis isomer crystallizes in the monoclinic space group P2₁/c. The cell parameters are: a = 9.7006(1), b = 18.9839(1), c = 14.2018(2) Å, = 91.263(1)°, V = 2614.70(5) ų, D _calc = 1.252 mg/m³, and Z = 4. Spectroscopic and crystallographic data for the cis-isomer are presented and discussed.     

Eightfold-coordinated diethylenetriaminepentaacetates: Crystal structures of K[M(Dtpa)] ⋅3H2O (M = Zr or Hf) and NH4[Sn(Dtpa)] ⋅ H2O

The crystal structures of K[M(Dtpa)] ? 3H₂O (M = Zr or Hf) and NH₄[Sn(Dtpa)] ? H₂O are studied by X-ray diffraction. The coordination number of the metal atom in all the compounds is eight. The NH₄[Sn(Dtpa)] ? H₂O complex is isostructural to the (H₅O₂)[M(Dtpa)] ? H₂O (M = Sn or Hf) compounds studied earlier.     

Synthesis and X-ray structure of [(μ-H)Os3(CO)10(μ-η2-N=CCH=CHCH=CC2H5)]

The reaction of [Os₃(CO)₁₀(MeCN)₂] with 2-ethylpyridine at ambient temperature leads to the isolation of the cluster [(-H)Os₃(CO)₁₀(-²-N=CCH=CHCH=CC₂H₅)][3 (65% yield) which has been structurally characterized by crystallographic methods. The compound crystallizes in the triclinic space group with a = 9.334(2), b = 9.918(2), c = 11.767(1) Å, = 92.13(2), = 99.93(1), = 99.88(2)°, V = 1054.7(3) ų and Z = 2. The same edge of the osmium triangle in the cluster is bridged by both the hydrido and the heterocyclic ligands, the latter through the nitrogen and the carbon atoms of the C=N bond.