Qiong-Hua Jin

Syntheses, crystal structures and nonlinear optical properties of MS4Pd(dppp) (M=Mo, W)

Abstract The title compounds [MS4Pd(dppp)] [M=Mo (1), W (2); dppp=Ph2PCH2CH2CH2PPh2] were synthesized for nonlinear optical studies by the reaction of (Et4N)2MS4 (M=Mo, W) and (dppp)PdCl2 in the CH2Cl2CH3CN. Single-crystal X-ray analyses revealed that the two compounds consisted of a distorted tetrahedral MS4 (M=Mo, W) unit with a Pd atom and two S atom bridges. The Pd atom has a cis-quasisquare coordination geometry with two P donors of dppp and two S donors of MS4. The nonlinear optical properties of 1 and 2 were investigated by a Z-scan technique with 7 ns laser pulses at 532 nm. It was observed that the nonlinear absorption for 1 is very small, but it has considerable large nonlinear refractive index; no nonlinear optical behavior was observed for 2, although it shows a similar structure to that of compound 1.

Iodo(1,10-phenanthroline-N,N')(triphenylphosphine)copper(I)

In the title complex, [CuI(C12H8N2)(C18H15P)], phenanthroline acts as a bidentate ligand coordinating via two N atoms to copper. The coordination polyhedron around Cu is a distorted tetrahedron, with a Cu—P distance of 2.1977 (9) A, Cu—N distances of 2.111 (3) and 2.071 (3) A, and a Cu—I distance of 2.6157 (6) A.

catena-Poly[silver(I)-bis­[μ-bis­(diphenyl­phosphino)methane-κ2P:P′]-μ-thio­cyanato-κ2S:S-silver(I)-μ-thio­cyanato-κ2S:N]

The title compound, [Ag(NCS)(C25H22P2)]n, contains two Ag+ ions, two thiocyanate ions and two bis(diphenylphosphino)methane (dppm) ligands in the asymmetric unit. One of the thiocyanate ions bridges the two Ag+ ions in a μ2-mode from its S atom and the two dppm ligands bridge the silver ions in a μ1,μ1 mode. The remaining SCN− ion bridges the binuclear units via its N and S atoms, generating a one-dimensional polymer propagating in [01]: the resulting AgP2SN and AgP2S2 coordination geometries could be described as distorted tetrahedral.

(Methanol-κO)(perchlorato-κO)bis-(triphenyl-phosphine-κP)silver(I).

In the title complex, [Ag(ClO4)(CH3OH)(C18H15P)2], the angles around the central Ag+ ion indicate that it is in a distorted tetrahedral coordination. The coordination sphere of silver is formed by two P atoms of two triphenylphosphine ligands, one O atom of a perchlorate anion and one O atom of a methanol molecule. The crystal structure is stablized by a bifurcated intermolecular O—H⋯O hydrogen bond, involving the O—H donor from methanol and two acceptor O atoms from the perchlorate anion, so forming a zigzag chain propagating in [010].

(Perchlorato-κO)tris­(triphenyl­phosphine-κP)silver(I)

In the title complex, [Ag(C18H15P)3(ClO4)], the silver coordination environment is dominated by the distorted P3AgO tetrahedron in which Ag—O = 2.608 (12) Å and the Ag—P bond lengths are 2.5663 (17), 2.5076(16) and 2.5450 (17) Å. The perchlorate O-atoms are disordered over two positions in a 0.584 (14):0.416 (14) ratio.

6-Nitro-1,3-benzothia-zole-2(3H)-thione.

In the title molecule, C7H4N2O2S2, the nitro group is twisted by 5.5 (1)° from the plane of the attached benzene ring. In the crystal, N—H⋯S hydrogen bonds link pairs of molecules into inversion dimers, which are linked by weak C—H⋯O interactions into sheets parallel to (101). The crystal packing exhibits short intermolecular S⋯O contacts of 3.054 (4) Å and π–π interactions of 3.588 (5) Å between the centroids of the five- and six-membered rings of neighbouring molecules.

[Bis[μ-bis-(diphenyl-phosphino)methane-1:2κ(2)P:P']-bis-(nitrito-κ(2)O,O')]disilver(I) acetonitrile disolvate.

The title complex, [Ag2(NO2)2(C25H22P2)2]·2CH3CN, is a centrosymmetric dimer in which two bis(diphenylphosphino)methane ligands bridge two Ag+ ions, forming an eight-membered ring with a short Ag⋯Ag separation of 3.1809 (5) Å. The distorted P2O2 coordination of the cation is completed by two O-donors from a symmetric bidentate chelate NO2 − anion [Ag—O = 2.550 (3) and 2.567 (3) Å].

[μ-1,2-Bis(diphenyl-phosphino)ethane-κP:P']bis-{[1,2-bis-(diphenyl-phosphino)ethane-κP,P']cyanidocopper(I)} methanol disolvate.

The title centrosymmetric complex, [Cu2(CN)2(C26H24P2)3]·2CH3OH, consists of two five-membered [Cu(dppe)CN] rings [dppe is 1,2-bis(diphenylphosphino)ethane] bridged by one μ2-dppe ligand, and two methanol solvent molecules. The angles around the central metal atom indicate that each CuI atom is located in the center of a distorted tetrahedron. The coordination sphere of each CuI atom is formed by three P atoms from two dppe ligands, and one C atom from the cyanide ligand. The crystal structure is stabilized by O—H⋯N hydrogen bonds, which are formed by the O—H donor group from methanol and the N-atom acceptor from a cyanide ligand.

Bis(2,2′-bi-1H-imidazole-κ2 N 3,N 3′)bis­(dimethyl sulfoxide-κO)copper(II) bis­(tetra­fluoridoborate)

In the title copper(II) salt, [Cu(C6H6N4)2(C2H6OS)2](BF4)2, the Jahn–Teller distorted octahedral coordination sphere of copper is formed from four 2,2′-bi-1H-imidazole N atoms and two dimethyl sulfoxide O atoms. The Cu atom lies on a center of inversion. N—H⋯O and N—H⋯F hydrogen bonds give rise to a one-dimensional structure. The BF4 − anion is disordered over two sites in a 0.671 (10):0.329 (10) ratio.

Bis[μ-bis­(diphenyl­phosphan­yl)methane-κ2P:P′]bis­[(isoquinoline-κN)silver(I)] bis­(trifluoro­methane­sulfonate)–isoquinoline (1/1)

The title complex, [Ag2(C25H22P2)2(C9H7N)2](CF3SO3)2·C9H7N, was prepared by the reaction of silver(I) trifluoromethanesulfonate with isoquinoline and bis(diphenylphosphanyl)methane (dppm). The dinuclear molecule is located about a center of inversion and the AgI atom is coordinated by two dppm P atoms and one isoquinoline N atom, forming an eight-membered metalla ring. In addition, in the asymmetric unit, there is a half-molecule of isoquinoline located about a center of inversion. Since this molecule does not possess this symmetry, for one position in the ring there is superposition of both a C atom of a C—H group and the isoquinoline N atom. In the structure, the Ag—P distances [2.4296 (9) and 2.4368 (9) Å] agree with the corresponding distances in related structures, while the Ag—N bond length [2.489 (3) Å] is slightly longer than that in related structures. On the other hand, the P—Ag—P angle [156.44 (3)°] is much larger than the corresponding angles in related structures. The trifluoromethanesulfonate anions do not coordinate to AgI atoms. As is usually found for these anions, the –CF3 group is disordered over two orientations [occupancies = 0.57 (12) and 0.43 (12)].