Dichloromethane Solvate Research Articles

Metal Complexes oftrans-2,2,4,4-Tetrafluoro-1,3-di-tert-butyl-1,3-diphosphetane

The title ligand, L, forms metal complexes LW(CO)5 {pentacarbonyl(trans-1,3-di-tert-butyl-2,2,4,4-tetrafluoro-1,3-diphosphetane-P)tungsten, [W(C10H18F4P2)(CO)5], (1)} and L(AuCl)2.2CH2Cl2 {μ-(trans-1,3-di-tert-butyl-2,2,4,4-tetrafluoro-1,3-diphosphetane-P:P′)-bis(chlorogold) dichloromethane solvate, [Au2Cl2(C10H18F4P2)].2CH2Cl2, (2)}. Complex (1) crystallizes with two independent but closely similar molecules; the P—W bond is short [2.482, 2.488 (2) Å] and the P—CBu bonds are lengthened by ca 0.03 Å compared with those in the ligand disulfide, LS2 [Fild, Jones, Ruhnau & Thöne (1994), Z. Naturforsch. Teil B, 49, 1361–1367; the structure of L is not available for comparison]. The diphosphetane ring is folded by angle of 21.4 (3)/22.0 (1)° about the C⋯C axis, in contrast with its exact planarity in both LS2 and complex (2), which crystallizes with imposed 2/m symmetry (m for the solvent); the Au—P bond is slightly shorter than the normal range at 2.212 (2) Å. Short contacts of 3.604 (2) Å are observed between the Au and solvent Cl atoms.

Solvate-Dependent Polymorphism: Crystallization of [{Mn(CO)3}2{μ-(η5-C6H6-η5-C6H6)}] from CH2Cl2 as a Mono-Solvate in the Rare Tetragonal Space Group P42/mbc

Recrystallization from methylene chloride gives a tetragonal pseudo-polymorph of(μ-η 5 :η 5 -bicyclohexadienyl)bis(tricarbonylmanganese), [Mn 2 (C 12 H 12 )(CO) 6 ].-CH 2 Cl 2 , in the rare space group P4 2 /mbc. Molecules in these crystals and in the monoclinic unsolvated form are virtually superimposable, and it is the inclusion of the methylene chloride solvate molecule which allows for crystallization in P4 2 /mbc. The Mn dimers are packed in layers with fourfold symmetry, with disordered methylene chloride molecules filling interstices between the layers.

Bond length–bond order relations and calculated geometries for some benzenoid aromatics, including phenanthridine. Structures of 5,6-dimethylphenanthridinium triflate, [N-(6-phenanthridinylmethyl)-aza-18-crown-6-κ5 O,O',O'',O''',O''''](picrate-κ2-O,O')potassium, and [N,N'-bis(6-phenanthridinyl-κN-methyl)-7,16-diaza-18-crown-6-κ4 O,O',O'',O''']sodium iodide dichloromethane solvate

The crystal structures of the title compounds are studied in order to investigate the role of novel fluoroionophores in complexation of sodium and potassium. In the potassium complex seven coordination, including the picrate ligand, is encountered. An additional coordination site is via the phenanthridine nitrogen at 3.252 (2) Å (second coordination). The complex is of C 1 symmetry and the aza-18-crown-6 macrocylic ring exhibits a crown-type conformation. The 7,16-diaza-18-crown-6 macrocycle accommodates a six-coordinate sodium with two additional ligands, via nitrogen from phenanthridine units. The complex cation shows a crystallographic twofold symmetry. The macrocycle is not of the crown-type conformation. In both complexes the alkali metals are shifted out of the cavity centres towards a picrate ligand in [N-(6-phenanthridinylmethyl)-aza-18-crown-6-κ5 O,O′,O′′,O′′′,O′′′′](picrate-κ2 O,O′)potassium and the phenanthridine units in [N,N′-bis-(6-phenanthridinyl-κN-methyl)-7,16-diaza-18-crown-6-κ4 O,O′,O′′,O′′′]sodium iodide dichloromethane solvate. Semi-empirical and molecular mechanics calculations based on various force fields were used for the optimization of phenanthridine geometry. The values obtained are compared with experimental data. Valence bond calculations of bond lengths in some benzenoid aromatic systems (C—C bonds in benzenoid hydrocarbons, azabenzenoid hydrocarbons and picrate-like systems; C—N bonds in the azabenzenoids; C—O bonds in the picrate-like systems), as well as some analogous Hückel molecular orbital calculations (C—C bonds in the benzenoid hydrocarbons and the azabenzenoids), were found to agree with the observed values (average differences up to 0.015 Å). These approaches can be used by means of bond length-bond order relations for prediction of bond lengths in the phenanthridine units as well as in the picrate.

Crystal structure ofcis-[Ru(bpy)2(PPh3)Cl+][ClO 4 − ]·(toluene)·∼0.5(CH2Cl2), a species with two different disordered solvent molecules of crystallization

The complexcis-[Ru(bpy)2(PPh3)Cl+][ClO4−] (where bpy=2,2′-bipyridyl) crystallizes from a solution in toluene/dichloromethane as the toluene-hemi(dichloromethane) solvate in the centrosymmetric space group\(P\bar 1\) witha=10.343(2)A,b=11.823(3)A,c=18.469(4)A, α=98.90(2)o, β=93.32(2)o, γ=101.46(2)o,V=2177.8(8)A3 andZ=2. The structure was refined toR(F)=4.6% for those 4248 reflections above 6σ(Fo). The octahedral Ru(II) cation is associated with the bond lengths Ru−Cl=2.424(2)A, Ru−PPh3=2.328(1) A and Ru−N=2.045(5)–2.109(4)A. Both the cation and the perchlorate anion are ordered. However, the unit cell also contains two disordered toluene molecules (centered about inversion centers at 1, 1/2, 0 and 1/2, 0, 1/2), and a disordered dichloromethane molecule of a partial occupancy (centered about 1/2, 0, 1).

A Bis(6-methyl-2-pyridylmethyl) Thioether (DMPT) Copper(II) Complex, [Cu(OSO2CF3)2(C14H16N2S)].CH2Cl2

The X-ray crystal structure determination of the title copper derivative, [bis(6-methyl-2-pyridylmethyl)sulfide-N,N',S]bis(trifluoromethylsulfonato-O)copper(II) dichloromethane solvate, shows that this compound contains monomeric [Cu(DMPT)(OSO 2 CF 3 ) 2 ] molecules in which the Cu II ion is surrounded by a tridentate DMPT ligand [Cu-N1 2.001(4), Cu-N2 1.977 (4) and Cu-S3 2.319 (1) A] and by a pair of trifluoromethylsulfonato ligands [Cu-O1 2.205 (4) and Cu-O4 2.043 (3) A] in a distorted tetragonal-pyramidal environment.

Imidotitanium Tris(pyrazolyl)hydroborates: Synthesis, Solution Dynamics, and Solid-State Structure.

Reaction of [Ti(NBu(t))Cl(2)(py-Bu(t))(2)] (1; py-Bu(t) = 4-tert-butyl pyridine) with 1 equivalent of K[Tp(Me2)], K[Tp(Pri)] or K[Tp(Pri,Br)] affords the corresponding complexes [Tp(Me2)Ti(NBu(t))Cl(py-Bu(t))] (2), [Tp(Pri)Ti(NBu(t))Cl(py-Bu(t))] (3), and [Tp(Pri,Br)Ti(NBu(t))Cl(py-Bu(t))] (4), respectively, which are the first examples of imido Group 4 tris(pyrazolyl)hydroborates [Tp(Me2) = tris(3,5-dimethylpyrazolyl)hydroborate; Tp(Pri) = tris(3-isopropylpyrazolyl)hydroborate; Tp(Pri,Br) = tris(3-isopropyl-4-bromopyrazolyl)hydroborate]. Complexes 2-4 are fluxional on the (1)H and (13)C NMR time scales, the spectra indicating restricted rotation about the Ti-py-Bu(t) bond. Activation parameters for this dynamic process have been determined both by (13)C NMR lineshape analysis and by coalescence measurements. The solution-state structure for 2 has been unambiguously assigned from a low temperature, phase-sensitive (1)H NOESY DQF spectrum and the solid-state X-ray crystal structure of the dichloromethane solvate of 3 has been determined (space group P2(1)/n; a = 12.539(3), b = 14.686(3), c = 21.747(4) Å; beta = 91.28(3) degrees; R(1) = 0.0694 and wR(2) = 0.154 for 1578 observed reflections). (13)C NMR Deltadelta values (Deltadelta = delta(C(alpha)) - delta(C(beta))) for the tert-butyl imido ligand in 2-4 suggest that the donor ability of the tris(pyrazolyl)hydroborate ligands increases in the order Tp(Pri,Br) < Tp(Pri) < Tp(Me2). None of these ligands, however, is as effective a donor to the metal center as either eta-C(5)H(5) or eta-C(5)Me(5).

Difunctionalised arene Ru6C cluster compounds with electron-withdrawing groups

Thermolysis of [Ru6C(CO)17]1 with dimethyl cyclohexa-1,3-diene-1,4-dicarboxylate [C6H6(CO2Me)2-1,4] in dibutyl ether gave two isomeric cluster compounds [Ru6C(CO)14(η6-C6H4(CO2Me)2-1,4]2 and [Ru6C(CO)14(µ3-η2:η2:η2-{C6H4(CO2Me)2-1,4)]3. The solid-state molecular structures of 2 and 3 have been established by low-temperature single-crystal X-ray diffraction analysis. These constitute the first example of co-ordination isomerism for the Ru6C(CO)14 unit with respect to a specific arene. In 2 the arene is η6 bonded to a single ruthenium atom whereas in 3 the arene is bonded in the µ3 mode to a triangular Ru3 face of the octahedral cluster unit. The solid-state structure of 3 is comprised of two rotamers along with two molecules of dichloromethane solvate. The solid-state architectures of 2 and 3 were also examined. The bifunctionalised arene ligand in 2 and 3 has the potential for further organic chemistry at these sites including possible copolymerisation with primary/secondary diamines.

Stereochemistry of aquo(5,10,15,20-tetraphenylporphinato)zinc(II) as its 18-crown-6, methylene chloride solvate

The structure of [Zn(TOO) (H 2O)]· 1 2 (18-C-^)· 1 2 (CH 2Cl 2) (C 50.5H 38ClN 4O 4Zn) has been determined with ligand resolution (to 0.5 Å) X-ray diffraction data collected with an rea detector at 128 K. No crystallographically required symmetry is found for the molecule. The four ZnN p bond distances have an average value of 2.066(3) Å and the acial ZnO bond length is 2.1109(aa) Å. The zinc(II) displacement from the mean plane of the 24-atom porphinato core is determined to be 0.36 Å, significantly larger than the previously found for [Zn(TPP)(H 2O)] and [Zn(TMP) (H 2O)]· 1 2 H 2 O , but comparable to that of other five-coordinate zinc porphyrins with an oxygen donor axial ligand. A comparison of core structure with all other five-coordinate zinc(II) porphyrins is given. Strucutal data are based of F 2 refinement using all aunique data i ncluding negative intensities. Crystal data: a = 16.775(1), b = 18.372(1), c = 27.843(2) A ̊ , β = 100.80(1) °, monoclinic, space group C2 c , V = 8428.9(9) A ̊ 3, Z = 8, R 1 = 0.0585 for 14 489 ‘observed’ data with F 0 ⩾ 4.0 α ( F 0), and wR 2 = 0.1681 for 26313 total unique data.

Molecular and crystal structure of dichloro(5,10,15,20-tetraphenylporphinato)phosphorus(V) chloride dichloromethane solvate

The crystal structure of dichloro(5,10,15,20-tetraphenylporphinato)phosphorus(V) chloride dichloromethane solvate has been determined by X-ray diffraction at ambient temperature. A saddle shape of the meso-tetraphenylporphinate disc is attributed to marked S 4 deviation from planarity. The mode of the torsion of four phenyl rings around the CC bonds connecting these rings to the respective meso carbon atoms are also of S 4 character. The phosphorus atom lies just in the mean plane of the porphinate nitrogen atoms. The PN bond distances range from 1.804(3) to 1.821(3) Å, which are shorter than those observed in [P(OH) 2(tpp)] + (1.870–1.916 Å), while the axial PCl bond distances [2.149(1) and 2.153(1) Å] are significantly longer than the distance expected for the normal covalent PCl bond (2.10 Å). This phosphorus porphyrin reveals characteristic features peculiar to the structure of metalloporphyrins with the smallest-sized central cations.

Five-coordinate copper(II) complexes of GEM-N 3P 3Ph 2(dmpz) 4

2,2-Diphenyl-4,4,6,6-tetrakis(3,5-dimethyl-1-pyrazolyl)cyclotriphosphazene, N 3P 3Ph 2(dmpz) 4 ( 2), forms mononuclear five-coordinate complexes N 3P 3Ph 2(dmpz) 4·CuX 2 [X  Cl ( 3) and Br ( 4)] with copper(II) halides. The structure of dichloromethane solvate of the chloro derivative, N 3P 3Ph 2(dmpz) 4·CuCl 2, has been determined by single crystal X-ray diffraction. The metal exists in a distorted trigonal bipyramidal geometry and the ligand 2 acts as an N 3 capping tridentate ligand with two non-geminal pyrazolyl pyridine and one cyclotriphosphazene ring nitrogen and two chloride ions complete the trigonal bipyramidal environment. The spectroscopic (IR, UV-vis and EPR) characterization of the complexes is also reported.

A Solvate of the Diacetate Salt of the Octaethyltetraphenylporphyrin Dication, H4OETPP2+.2CH3COO−.3CH3COOH.CH2Cl2

The structure of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin(2+) diacetate acetic acid dichloromethane solvate, C 60 H 64 N 4 2+ .2C 2 H 3 O 2 - .3C 2 H 4 O 2 .CH 2 Cl 2 , has been determined at 200K. The molecule is severely non-planar and adopts an S 4 saddle shape. It is the most distorted member of the OETPP series reported to date, with displacements of the β-pyrrole C atoms from the plane of the four N atoms as great as 1.42 A and acute tilts of the phenyl rings relative to the porphyrin plane. The two acetate counterions act as bidentate ligands which bond to the H atoms on opposite pairs of N atoms. The crystal lattice also contains three acetic acid molecules of solvation per porphyrin molecule, all of which are involved in hydrogen bonds to the acetate molecules. An «innocent» molecule of CH 2 Cl 2 is also present

Bis(dimethylglyoximato)(phenylacetylido)(triphenylphosphine)rhodium(III) Dichloromethane, [Rh(C4H7N2O2)2(C8H5)(C18H15P)].CH2Cl2

The title structure {alternative name: bis[2,3-butanedial dioximato(1 −)-N,N'](phenylethynyl)(triphenylphosphine-P)rhodium(III) dichloromethane solvate} consists of discrete complexes [Rh(dmgH) 2 (PPh 3 )R] (R = C≡CPh and dmgH = dimethylglyoximato, C 4 H 7 N 2 O 2 − ) in which the Rh atom displays distorted octahedral coordination with the two dimethylglyoximato ligands in the equatorial plane and the phenylacetylide and triphenylphosphine groups in axial positions. The Rh atom is displaced by 0.073 (1) A from the mean plane through the four oxime N-atom donors. The average Rh−N distance is 1.971 (2) A, while the axial Rh−P and Rh−C distances are 2.409 (1) and 1.991 (3) A, respectively. Comparison of the results with those obtained previously for the ethyl and vinyl analogues (R = Et, CH=CH 2 ) indicates a lower trans influence of the phenylacetylide ligand in the P−Rh−C fragment, in accordance with its sp-hybridized C atom

Ferrocenylpyridines: a new synthesis of 4′-ferrocenylterpyridine and the single crystal structure of a C 3-ferrocenophane, [( η-C 5H 4CHCH 2C(O)2-C 5H 4N) 2CHC(O)2-C 5H 4N]Fe

The synthesis and characterization of the new ligand 4′-ferrocenylterpyridine is reported together with the synthesis and characterization of a new C 3-ferrocenophane containing three acylpyridine units. The terpyridine ligand was prepared in a two-step synthesis from ferrocenecarbaldehyde by aldol condensation and subsequent cyclization. Attempts to prepare the analogous 1,1′-bis-terpyridylferrocene derivative resulted in the formation of a new ferrocenophane : a consequence of inter-annular attack of an anion generated on the side chain of one cyclopentadienyl ring on a carbonyl centre on the side chain of the other cyclopentadienyl ring. The single crystal X-ray structure of this ferrocenophane, [( η-C 5H 4CHCH 2C(O)2-C 5H 4N) 2CHC(O)2-C 5H 4N]Fe, as its dichloromethane solvate, [Fe(C 33H 27N 3O 3)] · CH 2Cl 2, has been determined.

1-(3-Benzoylphenyl)ethanone (I) and 3-benzoyl-α-methylbenzeneacetamide methylene chloride solvate (2/1) (II)

While the acetyl group in (1) (m-benzoylacetophenone, C 15 H 12 O 2 ) is nearly coplanar with the phenyl ring [O2-C14-C1-C2 6.8 (5) o ] and positioned opposite the C7=O1 group, the 2-propanamido group in (II) [2-(3-benzoylphenyl)propanamide, C 16 H 15 NO 2 .0.5CH 2 Cl 2 ] is almost perpendicular to the corresponding phenyl ring [C16-C14-C1-C2 134.0 (4), C15-C14-C1-C2 -102.4(5) o ] and occupies the same side as the C7=O1 group

C–H.I− interactions in ferrocene derivatives: structures of (Ferrocenylmethyl)triphenylphosphonium iodide and 1,1'-ferrocenediylbis(methyltriphenylphosphonium iodide) dichloromethane solvate (1/1)

The cations in (ferrocenylmethyl)triphenylphosphonium iodide, [{(C5H5)Fe(C5Ha)}CH2P(C6Hs)3]+.I -, (1), and in 1, l'-ferrocenediylbis(methyltriphenylphosphonium iodide) dichloromethane solvate, [Fe{(C5H4)CH2- P(C6H5)3}212+.2I-.CH2C12, (2), are involved in three dimensional networks of C--H. • .I- interactions between phenyl C--H groups and I- anions. In (1), the cation resides in a general position while one I- anion is on a twofold axis and a second I- anion is at an inversion centre. The shortest C...I- distances are 3.886 (2) and 3.989 (2)A to the I- ion which resides on an inversion centre. The cation in (2) has approximate mirror symmetry and lies in a general position in the unit cell along with its two I- anions. The shortest C--.I- interactions are 3.810 (4) and 3.886 (5) A,.

Crystal structure of 1,4-bis[β(9-anthryl)ethyloxycarbonyl]piperazine dichloromethane solvate, (C38H34N2O4)(CH2Cl2 )

Article Crystal structure of 1,4-bis[β(9-anthryl)ethyloxycarbonyl]piperazine dichloromethane solvate, (C38H34N2O4)(CH2Cl2 ) was published on November 1, 1993 in the journal Zeitschrift für Kristallographie - Crystalline Materials (volume 207, issue 1-2).

Crystal structure of tetracarbonylchromium-µ-(Ν- bis(2-diphenylphosphino)ethyl-N′-dimethyl-diaminopropane)- dichloro-N,N′-zinc dichloro-methane solvate, (CO)4Cr(P(C6H5)2)2(CH)(C6N2H15)ZnCl2

Article Crystal structure of tetracarbonylchromium-µ-(Ν- bis(2-diphenylphosphino)ethyl-N′-dimethyl-diaminopropane)- dichloro-N,N′-zinc dichloro-methane solvate, (CO)4Cr(P(C6H5)2)2(CH)(C6N2H15)ZnCl2 was published on October 1, 1993 in the journal Zeitschrift für Kristallographie - Crystalline Materials (volume 206, issue 1-2).

Copper(II) tetrakis(pentafluorophenyl)-β-octachloroporphyrin

The title compound, {4,5,9,10,14,15,19,20-octachloro-2,7,12, 17-tetrakis(pentafluorophenyl)-20,22,23,24- tetraazapentacyclo[l6.2.l.1^(3·6).l^(8·11).l^(13·16)]tetracosa-1,3(21),4,6,8(22),9,11, 13(23), 14, 16, 18(24), 19-dodecaene}copper(II)(CuTFPPC1_8)dichloromethane solvate, shows a large tetrahedral distortion or ruffling, with pairs of Cl atoms alternately averaging + 1.20 and -1.18 A out of the plane of the four N atoms; the Cu atom is 0.01 A out of the plane and the N atoms show a slight (±0.12 A) tetrahedral distortion. A Cl atom of the solvent, at 3.515 (6) A in an approximately axial position, is the closest non-bonded neighbor of the Cu atom.

Structure of dicarbonylbis-(μ-3,5-dimethylpyrazolyl)-bis(4-tolyl diphenylphosphinite)diiridium(I)–dichloromethane (1/1)

In bis(μ-3,5-dimethylpyrazolyl-N:N')-bis[carbonyl( 4-tolyl diphenylphosphinite-P)iridium(I)] dichloromethane solvate, two Ir^I atoms are joined by two 3,5-dimethylpyrazolyl bridges with one carbonyl and one 4-tolyl diphenylphosphinite ligand completing the square-planar geometry about each Ir atom. The Ir· · ·Ir distance of 3.307 (1) A is greater than the distance of 3.22 A found in a similar pyrazolyl-bridged iridium(I) dimer [Fox (1989). PhD dissertation, California Institute of Technology, USA].

Synthesis of orthometallated rhodium(III) compounds. Crystal structures of [RhCl 2{η 2(C 6H 4)PPh 2}(η 2-dppm)] and [RhCl{η 2(C 6H 4)PPh 2}(η 1-PCCl)(phen)] (SbF 6)·CH 2Cl 2 (dppm=bis(diphenylphosphino)methane; PCCl=P( o-ClC 6H 4)Ph 2; phen=1,10 phenanthroline)

Neutral and cationic rhodium(III) metallated compounds containing a four-membered ring are prepared by different synthetic methods: (i) from rhodium(I) compounds that contain the ligand P( o-ClC 6H 4)PPh 2, by 2c-2e intramolecular oxidative addition; (ii) from metallated dirhodium(II) compounds; (iii) by ligand substitution in [RhCl 2{η 2-(C 6H 4)PPh 2}{η 2-P( o-ClC 6H 4)Ph 2}]. The crystal structures of [RhCl 2{η 2-(C 6H 4)PPh 2}(η 2-dppm)] ( 2) and of the dichloromethane solvate of [RhCl{η 2-(C 6H 4)PPh 2}{η 1-P( o-ClC 6H 4)Ph 2}(phen)](SbF 6) ( 11) have been determined by X-ray diffraction methods. In both complexes the Rh atom is in the distorted octahedral arrangement and the metallated phosphine forms, through P and C atoms, a four-membered ring with the metal. A dppm molecule in 2 and a phen molecule in 11 act also as chelating ligands. In 11 the P( o-ClC 6H 4)PPh 2 phosphine behaves as a monodentate ligand.