Two Fe3(µ3-S)2(CO)8 clusters with terminal N-heterocyclic carbenes.

The title compounds with terminal N-heterocyclic carbenes, namely octacarbonyl(imidazolidinylidene-κC(2))di-µ3-sulfido-triiron(II)(2 Fe-Fe), [Fe3(C3H6N2)(µ3-S)2(CO)8], (I), and octacarbonyl(1-methylimidazo[1,5-a]pyridin-3-ylidene-κC(3))di-µ3-sulfido-triiron(II)(2 Fe-Fe), [Fe3(C8H8N2)(µ3-S)2(CO)8], (II), have been synthesized. Each compound contains two Fe-Fe bonds and two S atoms above and below a triiron triangle. One of the eight carbonyl ligands deviates significantly from linearity. In (I), dimers generated by an N-H···S hydrogen bond are linked into [001] double chains by a second N-H···S hydrogen bond. These chains are packed by a C-H···O hydrogen bond to yield [101] sheets. In (II), dimers generated by an N-H···S hydrogen bond are linked by C-H···O hydrogen bonds to form [111] double chains.

Two seven-membered heterocycles with 1,2-diaza ring N atoms: 3,5,7-triphenyl-1,2-diazacyclohepta-1(7),2-diene and 3,7-bis(2-hydroxyphenyl)-5-phenyl-1,2-diazacyclohepta-1(7),2-diene.

The title compounds, 3,5,7-triphenyl-1,2-diazacyclohepta-1(7),2-diene, C23H20N2, (I), and 3,7-bis(2-hydroxyphenyl)-5-phenyl-1,2-diazacyclohepta-1(7),2-diene, C23H20N2O2, (II), constitute the first structurally characterized examples of seven-membered heterocycles with 1,2-diaza ring N atoms. Compound (I) crystallizes in the space group P1, with two independent molecules in the asymmetric unit that differ in the conformation of one of the phenyl rings, while (II) crystallizes in the space group C2/c. The C5N2 ring in each of (I) and (II) adopts a twist-boat conformation. Compound (I) exhibits neither C-H···π interactions nor π-π stacking interactions, whereas (II) shows both intramolecular O-H···N hydrogen bonds and a C-H···π interaction that joins the molecules into an infinite chain in the [010] direction.

A novel hexairon cluster with one disulfide and two Ph2PCS(3-) ligands.

The title compound, hexadecacarbonylbis{µ3-[(diphenylphosphanyl)methanediidyl]sulfanido}-µ4-disulfido(2-)-hexairon(4 Fe-Fe), [Fe6(C13H10PS)2(S2)(CO)16], contains two inversion-related [Fe3(Ph2PCS)(CO)8] subclusters linked by an equatorial disulfide bond [S-S = 2.1490 (9) Å]. Each Ph2PCS(3-) ligand is coordinated to a triiron core in a µ3-κP:κ(2)C:κ(2)S fashion.

Syntheses and crystal structures of neutral tetrairon complexes with the unique SCPPh2S ligand.

The novel reactions of cluster salts [(µ-RS)Fe(2)(CO)(6)(µ(4)-CS(2))Fe(2)(CO)(6)][Et(3)NH] with Ph(2)PCl, via the insertion of the PPh(2) group into an activated C-S bond, afford the unprecedented tetrairon complexes with the unique SCPPh(2)S ligand which is coordinated to (µ-RS)Fe(2)(CO)(6) and Fe(2)(CO)(6) units in a µ(4)-k(2)C:k(4)S,S' mode (R = Ph, CH(3)O(2)CCH(2)).

Monoclinic form of (Z)-1-ferrocenyl-3-(3-hy-droxy-anilino)but-2-en-1-one.

The title compound, [Fe(C(5)H(5))(C(15)H(14)NO(2))], is a monoclinic polymorph of the previously reported triclinic form [Shi et al. (2006 ▶). Acta Cryst. C62, m407-m410]. The polymorphs feature the same strong intra-molecular N-H⋯O=C hydrogen bonds, but show different packing modes. The mol-ecules in the monoclinic form associate into double chains via O-H⋯O=C and (Cp)C-H⋯O-H inter-actions.

Ethyl (Z)-4-ferrocenyl-2-(4-hy-droxy-anilino)-4-oxobutenoate.

In the title compound, [Fe(C(5)H(5))(C(17)H(16)NO(4))], the O=C-C=C-N mean plane is twisted with respect to the mean planes of the benzene and substituted cyclo-penta-dienyl rings by 44.2 (2) and 13.8 (3)°, respectively. Furthermore, the O=C-C=C-N mean plane and the O=C-O(ester) plane make a dihedral angle of 55.5 (6)°. Consistent with this large dihedral angle, the linking C-C bond [1.507 (6) Å] does not show any (delocalized) double-bond character.

Undeca-carbonyl-µ(2)-methane-thiol-ato-µ(2)-[(pyridin-2-yl)methane-thiol-ato]-µ(4)-sulfido-tetra-iron(II)(2 Fe-Fe).

The title compound, [Fe(4)(C(6)H(6)NS)(CH(3)S)S(CO)(11)], com-prises two butterfly-shaped sub-cluster cores, Fe(2)S(2)N and Fe(2)S(2), joined together by a spiro-type µ(4)-S atom. The (pyridin-2-yl)methane-thiol-ate ligand is attached to the Fe(2)(CO)(5) unit in a µ-κN:κ(2)S mode, and the methane-thiol-ate ligand is coordinated to the Fe(2)(CO)(6) unit in a µ-κ(2)S fashion.

1,1'-Bis(1-acetyl-5-methyl-1H-pyrazol-3-yl)ferrocene.

The title compound, [Fe(C(11)H(11)N(2)O)(2)], crystallizes with two independent mol-ecules in the asymmetric unit which have have different conformations. In one mol-ecule, the two ferrocene cyclo-penta-dienyl rings are fully eclipsed and the two pyrazole rings are syn to each other; in the other, the two cyclo-penta-dienyl rings are synclinal and the pyrazole rings are anti. In both mol-ecules, the acetyl group attached to the pyrazole ring is oriented away from the iron-cyclo-penta-dienyl group of ferrocene.

µ(4)-Orthothio-carbonato-tetra-kis-[tri-carbonyl-iron(I)](2 Fe-Fe).

The fused bis-butterfly-shaped title compound, [Fe(4)(CS(4))(CO)(12)], possesses an orthothio-carbonate (CS(4) (4-)) ligand that acts as a bridge between two Fe(2)(CO)(6) units. A short intra-molecular S⋯S contact [2.6984 (8) and 2.6977 (8) Å] occurs in each S(2)Fe(2)(CO)(6) fragment.

(Z)-1-Phenyl-3-(3-pyridyl-meth-ylamino)-but-2-en-1-one.

The reaction of 3-C(5)H(4)NCH(2)NH(2) and C(6)H(5)COCH(2)COCH(3) affords the title compound, C(16)H(16)N(2)O. The O=C-C=C-N portion is essentially planar [maximum deviation = 0.046 (2) Å] and is aligned at dihedral angles of 22.6 (1) and 78.9 (1)° to the phenyl and pyridyl rings, respectively. The N-H and O=C groups are linked by an intra-molecular hydrogen bond. In the crystal, C-H⋯O hydrogen bonds and C-H⋯π inter-actions occur.

(E)-1-Ferrocenyl-3-(3-nitro-phen-yl)prop-2-en-1-one.

In the title compound, [Fe(C(5)H(5))(C(14)H(10)NO(3))], one cyclo-penta-diene ring is substituted and one is unsubstituted. The two rings are almost parallel and are eclipsed and ordered. The conjugated substituent is slightly twisted with respect to the cyclo-penta-diene ring. The crystal structure contains four inter-molecular C-H⋯O hydrogen-bonds in the range 3.324 (3)-3.539 (3) Šand one π(aryl ring)-π (Cp ring) stacking inter-action with a ring-centroid distance of 3.894 (2) Å.

1-Acetyl-3-ferrocenyl-5-methyl-1H-pyrazole and 1-acetyl-5-ferrocenyl-3-(2-pyridyl)-1H-pyrazole.

Molecules of 1-acetyl-3-ferrocenyl-5-methyl-1H-pyrazole, [Fe(C5H5)(C11H11N2O)], form a centrosymmetric dimer generated by a combination of one C-H...pi(pyrazole) and one C-H...pi(cyclopentadienyl) interaction. The dimers are linked by C-H...pi interactions, involving the pyrazole rings as acceptors, into layers parallel to (10-1). Molecules of 1-acetyl-5-ferrocenyl-3-(2-pyridyl)-1H-pyrazole, [Fe(C5H5)(C15H12N3O)], are linked by C-H...O interactions into a chain running in the [010] direction. Two chains of this type passing through each unit cell are connected by O...pi(pyridyl) interactions into an [010] double chain.

N,N'-Bis(2-pyridylmethyl)ferrocene-1,1'-diyldicarboxamide and N,N'-bis(3-pyridylmethyl)ferrocene-1,1'-diyldicarboxamide.

The molecules of N,N'-bis(2-pyridylmethyl)ferrocene-1,1'-diyldicarboxamide, [Fe(C12H11N2O)2], contain intramolecular N-H...N hydrogen bonds and are linked into sheets by three independent C-H...O hydrogen bonds. The molecules of the isomeric compound N,N'-bis(3-pyridylmethyl)ferrocene-1,1'-diyldicarboxamide lie across inversion centres, and the molecules are linked into sheets by a combination of N-H...N hydrogen bonds and pi-pi stacking interactions between pyridyl groups.

(Z)-1-Ferrocenyl-3-(3-hydroxyanilino)but-2-en-1-one and (Z)-1-ferrocenyl-3-(4-hydroxyanilino)but-2-en-1-one.

The title compounds, both [Fe(C5H5)(C15H14NO2)], crystallize with Z'=2 in the centrosymmetric space group P-1. In each compound, there is an intramolecular N-H...O=C hydrogen bond, and pairs of intermolecular O-H...O=C hydrogen bonds link the molecules into chains, parallel to [110] in the 3-hydroxy compound and parallel to [101] in the 4-hydroxy compound.