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.     

Crystal structure of radical cation salt (BEDT-TTF)4(GaCl4)2 · C6H5CH3

A new radical cation salt based on bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with the tetrahedral anion GaCl ₄ ^? , namely, (BEDT-TTF)₄(GaCl₄)₂ · C₆H₅CH₃, has been synthesized. The crystal structure of this salt is determined by X-ray diffraction analysis [a = 31.757(2) Å, b = 6.8063(3) Å, c = 34.879(2) Å, β = 90.453(4)°, V = 7538.8(7) ų, space group I2/c, and Z = 4]. In the structure, the radical cation layers alternate with the anion layers along the c-axis. The anion layers consist of the GaCl ₄ ^? tetrahedra and solvent molecules. The packing of BEDT-TTF molecules in the radical cation layer differs from that in the structure of the known salt (BEDT-TTF)₂GaCl₄, even though both compounds exhibit semiconductor properties.     

Crystal structure of hexakis(tetrahydrofuran)sodium hexacarbonylvanadate(−I), [Na(THF)6 +][V(CO)6 −]

The title compound crystallizes in the space group with unit cell parameters (hexagonal setting)a=14.922(5)Å,c=14.379(9)Å,V=2773(3)ų andZ=3. The cation and the anion each lie on a site of (S₆) symmetry. Interatomic distances include Na–O(THF)=2.40(1) Å and V–C(CO)=1.91(2) Å.     

Crystal structure of NH3(CH2)2NH3BiCl5·2H2O

The ethylenediammonium pentachlorobismuthate(III) dihydrate salt is monoclinic with the following unit cell dimensions: a = 10.902(8)Å, b = 7.926(6)Å, c = 15.199(6)Å, = 96.40(1)°, space group P2₁/n with Z = 4. The structure shows a layer arrangement parallel to the axis: planes of the [Bi₂Cl₁₀]^4– bioctahedra alternate with planes of [NH₃(CH₂)₂NH₃]²⁺ dications. The [Bi₂Cl₁₀]^4– bioctahedra are connected through O(W)–H··· Cl hydrogen bonds, so that infinite unidimensional chains of composition [Bi₂Cl₁₀(H₂O)₂] _n ^4n– are formed in the structure parallel to the axis. These chains are themselves interconnected by means of the N–H···Cl bonds originating from the [NH₃(CH₂)₂NH₃]²⁺ entities, forming a three-dimensional network.     

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.     

Crystal and molecular structure of complex compound [Fe3O(CH3COO)6(H2O)3]2[ZnCl4] ⋅ 2H2O

The X-ray crystal structure of trinuclear iron acetate [Fe₃O(CH₃COO)₆(H₂O)₃]₂ [ZnCl₄] ? 2H₂O was determined. The crystal has a ionic structure. It is monoclinic, a = 25.363(7), b = 14.533(4), c = 15.692(4) Å, β = 103.11(2)°, space group _C2/c, and R = 0.0685. The structure of the cationic complex [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ is typical of trinuclear iron(III) compounds containing a μ₃-O bridge: the iron atoms are situated at the vertices of an almost equilateral triangle with the O atom at the center. Each Fe atom is coordinated by four O atoms of bridging carboxy groups, the μ₃-bridging O atom, and the water molecule in the trans position to the latter O atom. Mössbauer spectroscopy evidence indicates the high-spin state (_S = 5/2) of the iron(III) ions.     

Crystal structure of N-benzylmethylammonium dihydrogen-monophosphate monohydrate, [C6H5CH2NH2CH3]H2PO4·H2O

The salt N-benzylmethylammonium dihydrogenmonophosphate monohydrate is monoclinic with the following unit cell dimensions: a = 6.356(1)Å, b = 8.385(7)Å, c = 11.472(5)Å, = 104.32(1)°, space group P2₁ with Z = 2. The structure consists of infinite parallel two-dimensional [110] planes built of mutually connected ions and water molecules by strong O–H···O and N–H···O hydrogen bonding. There are no contacts other than normal van der Waals interactions between the layers.     

Crystal Packing of Potentially Mesomorphic Azobenezene Derivatives R1–C6H4–N=N–C6H4–R2 (R1, R2 = CH3COO,C2H5O; CH2=C(CH3)COO,C2H5; C6H13COO,C2H5O)

Crystallography Reports - The structure and thermal properties of azobenzene derivatives R1–C6H4–N=N–C6H4–R2, where R1/R2 = CH3COO/C2H5O (I), CH2=C(CH3)COO/C2H5 (II), or...     

Complexation between molybdenum(VI) and citrate: Crystal and molecular structure of [Mo4O11(citrate)2](Me3N(CH2)6NMe3)2·12H2O

The X-ray structure of the tetrameric complex [Mo₄O₁₁(C₆H₅O₇)₂]-(Me₃N(CH₂)₆NMe₃)₂·12H₂O has been determined. Crystals are monoclinic,C2/c, witha=19.886(8),b=11.773(6),c=26.97(1) Å,=90.69(4)°,V=6313 ų,Z=4. FinalR=0.050,R _w =0.053,w=(² F)^–1 for 4451 reflections withI _rel>2I _rel. The configuration of the Mo(VI) complex is similar to that previously reported for a Mo(VI)-malate anion [Mo₄O₁₁(mal)₂]^4– but differs from that proposed previously for a Mo(VI)-citrate complex.     

Phase Transition and Phase Diagram of Anion Radical Salts of [(C6H5)3PCH3]+ [(C6H5)3AsCH3]+ ×(TCNO)− 2 (0 ≤×≤ 1)

Abstract

Much attention has been paid to the solid anion radical salts of 7,7,8,8-tetracyanoquinodimethane (TCNQ), because of their prominent electronic properties.^1–4 In particular, the salts containing mixed cations represented by [(C₆H₅)₃PCH₃]⁺ _1–x [(C₆H₅)₃AsCH₃]⁺ _× (TCNQ)^? ₂, (0 ≤×≤ 1), are known to undergo phase transitions at 1 atm pressure in the solid state.^1–4 The phase transition of pure methyltriphenylphosphonium salt, (x = 0.00), takes place at 315.7 K. Heat-capacity measurements of this phase transition have been made by Kosaki et al. ³ The transition has thus been found to be of the first order. The enthalpy and the total entropy change associated with the phase transition were experimentally determined to be 485.18 cal/mol and 1.7206 cal/deg.mol, respectively. For the solid solutions, it was found that the transition temperature (T_c ) is increased, while the magnitude of the heat of transition (δH) is decreased, progressively with an increase in the composition parameter (x) and that pure methyltriphenylarsonium salt, (x = 1.00), has no such phase transition up to the decomposition temperature of about 480 K at 1 atm pressure.^1–3 Figure 1 shows the experimental relation between T _c and x, together with the relation between δH and x.⁴ In the present paper, we attempted to explain thermodynamically the phase diagram of Figure 1 for the solid solutions of those TCNQ anion radical salts.     

Crystal structure of Al(tBu)3(NH2CH2CH2Ph): A molecular “slinky”

The molecular structure of Al(^tBu)₃(NH₂CH₂CH₂Ph) is determined by the crystal packing of the phenyl rings and the pseudo spherical Al(^tBu)₃ units, and may be viewed as a layered structure consisting of double sheets of the phenyl rings and the Al(^tBu)₃ units. The Al–N–C–C linkage shows severe disorder as a result of its flexibility. The structure of Al(^tBu)₃ (NH₂CH₂CH₂Ph) can be likened to a molecular slinky, in which the rigid ends are fixed in space by molecular packing forces, leaving the interior link to adopt multiple orientations. Crystal data: orthorhombic, Cmca,a=13.282(9),b=25.01(1),c=13.210(9), Å,V=4388(10) ų,Z=4,R=0.0957,R _w=0.0957.     

Structural studies on molecular complexes,I: Crystal and molecular structure of 9-aminoacridine-sulfamethoxypyridazine (1∶1), C13H10N2·C11H12N4O3S

The crystal structure of the molecular complex of the antiseptic 9-aminoacridme and the sulfa drug sulfamethoxypyridazine (11), C₁₃H₁₀N₂·C₁₁H₁₂N₄O₃S, has been determined by X-ray diffraction methods. The crystals are orthorhombic: Pbca (No. 61),a=16.321(1),b=16.951(1),c=16.331(1) Å,Z=8,F(000)=1984, andV _c =4518.1(5) ų. The structural parameters have been refined to a finalR value of 0.046 for 3134 observed reflections. The results of X-ray analysis show that the structure contains an acridinium-sulfanilamidate ion pair. A hydrogen atom is transferred from the sulfonamide nitrogen atom to the nitrogen atom of the acridine ring, and an N(acridinium)-HN(sulfonamide) hydrogen bond is formed. A slight folding of the acridine moiety is observed.     

Crystal and molecular structure of 2-(2′-chloro-5′-nitrostyryl)benzoselenazole

The title compound C₁₅H₉ClN₂O₂Se (nsbse) is orthorhombic, witha=6.823(2),b=7.860(2),c=26.349(5) Å,Z=4,D _x =1.709,(MoK)=28.3 cm^–1,F(000)=720,T=298K in space groupP2₁2₁2₁. The structure was solved by heavy atom and Fourier methods and refined toR=0.045 for 1095 unique observed reflections. The molecule is almost planar, with a dihedral angle of 4.8(2)° between the benzoselenazole and phenyl rings. The C-Se-C angle in the selenazole ring is very small, 84.6(4)°, while the C-N-C angle in that ring is 113.7(7)°.     

Synthesis and crystal structure of a dinuclear organometallic phosphonium ylid complex, [(η5-C5H5(CO)C2(ε-CO)(ε-CHP(C6H5)3)+][PF – 6 ]

The title compound crystallizes in the centrosymmetric monoclinic space group P2₁/n withZ=4. The cation consists of two (⁵-C⁵h⁵)Fe(CO) units which are linked via a metal-metal bond (Fe(1)–Fe(2)=2.530(1) Å), a bridging carbonyl ligand (Fe(1)–C(4)=1.912(8) Å. Fe(2)–C(4)=1.940(9) Å) and a bridging phosphonium ylid ligand (Fe(1)–C(1)=1.991(6) Å, Fe(2)–C(1)=1.985(6) Å and C(1)–P(1)=1.781(6) Å).     

Crystal and molecular structure of 7-hydroxyflavone monohydrate, C14H10O3·H2O

The X-ray crystal structure of 7-hydroxyflavone monohydrate, C₁₄H₁₀O₃ · H₂O, is determined. The compound crystallizes in the monoclinic space group, P2₁/n with a = 3.801(3), b = 19.665(4), c = 16. 039(6), = 93.69(3)°, and = 0.68 mm^–1 for Z = 4. The phenyl ring of the flavone moiety is rotated 18.6(1)° out of the penzopyran plane, which is a typical value for flavones. In the crystal lattice, there are wide channels which are lined mainly by C–H groups. The water molecules enclosed in these channels are severely disordered.     

Synthesis and X-ray crystal structure of an organometallic phosphonate [η6-1,2-C6H4(OCH3)(P(O)(OCH2CH3)2)]Cr(CO)3

The chiral, racemic, arene phosphonate complex, [t⁶-1,2-C₆H₄(OCH₃t)(P(O)(OCH²CH₃t)²)t] Cr(CO)₃ (1), was prepared via the reaction of 1,2-C₆H₄(OCH₃)(P(O)(OCH²CH₃)²) with Cr(CO)₆ in refluxing dioxane/THF. The title complex crystallized in P1 with the cell dimensions: a = 8.4893(4) Å, b = 11.0638(9) Å, c = 11.2135(8) Å, and = 62.151(8), = 105.154(5), = 112.426(6), giving a volume of 856.34(10) ų. The conformation of 1 is described as eclipsed (E) in which the methoxy substituent eclipses a carbonyl ligand of the tripod, and the phosphonate substituent is staggered.     

The Crystal Structure of a RAS (N–CH3-2-NH2-5-Cl–Py)(TCNQ)(CH3CN) Solvate

Crystallography Reports - The structure of the radical anion salt (RAS) of 7,7,8,8-tetracyanedimethane (TCNQ) with a cation based on 2-amin-5-chloro-pyridine (2-NH2-5-Cl–Py, Am), that is,...