Chloridobis(1,2,3,4-tetra-hydro-1,4,6,11-tetra-aza-naphthacene-κN)copper(I).

In the title complex, [CuCl(C(14)H(12)N(4))(2)], the Cu(I) atom, lying on a twofold rotation axis, is coordinated by two N atoms of two 1,2,3,4-tetra-hydro-1,4,6,11-tetra-aza-naphthacene ligands and one Cl atom, also lying on the twofold rotation axis, in a distorted trigonal-planar geometry. The complex mol-ecules are connected into a one-dimensional structure along [001] via N-H⋯N hydrogen bonds and further into a three-dimensional structure via N-H⋯Cl hydrogen bonds. π-π inter-actions between the pyrazine and benzene rings and between the benzene rings [centroid-centroid distances = 3.5635 (15) and 3.9128 (16) Å] are present.

Bis[1,3-bis-(diphenyl-phosphan-yl)propane]-copper(I) tetra-chlorido-gallate(III).

In the title compound, [Cu(C27H26P2)2][GaCl4], the Cu(I) atom in the complex cation is P,P'-chelated by two 1,3-bis-(diphenyl-phosphan-yl)propane ligands in a distorted tetra-hedral geometry, while the Ga(III) cation is coordinated by four chloride anions in a distorted tetra-hedral geometry. In the crystal, weak C-H⋯π inter-actions occur between adjacent complex cations.

Bis[3,3'-(piperazine-1,4-di-yl)-dipropan-aminium] di-µ(2)-sulfido-bis-[disulfido-german-ate(IV)].

In the title compound, (C(10)H(26)N(4))(2)[Ge(2)S(6)], the dimeric [Ge(2)S(6)](4-) anion formed by two edge-sharing GeS(4) tetra-hedral units lies around an inversion centre. The average terminal and bridging Ge-S bond lengths are 2.162 (7) and 2.267 (15) Å, respectively. The inorganic anions and organic cations are organized into a three-dimensional network by numerous N-H⋯S hydrogen bonds.

Bis{2,2'-[(2-amino-eth-yl)aza-nedi-yl]diethanaminium} di-µ-sulfido-bis-(disulfido-germanate).

In the title compound, (C(6)H(20)N(4))(2)[Ge(2)S(6)], the dimeric [Ge(2)S(6)](4-) anion is formed by two edge-sharing GeS(4) tetra-hedral units. The average terminal and bridging Ge-S bond lengths are 2.158 (14) and 2.276 (6) Å, respectively. The anions and the diprotonated ammonium cations are organized into a three-dimensional network by N-H⋯S and N-H⋯N hydrogen bonds.

Bis[4-(2-aza-niumyleth-yl)piperazin-1-ium] di-µ-sulfido-bis-[disulfido-germanate(II)].

In the title compound, (C(6)H(17)N(3))(2)[Ge(2)S(6)], the dimeric [Ge(2)S(6)](4-) anion is formed by two edge-sharing GeS(4) tetra-hedral units. The average terminal and bridging Ge-S bond lengths are 2.164 (2) and 2.272 (8) Å, respectively. The dimeric inorganic anions and the organic piperazinium cations are organized into a three-dimensional network by N-H⋯S hydrogen bonds.

Bis[(diphenyl-phosphanylmeth-yl)diphenyl-phosphane sulfide-κ(2)P,S]copper(I) hexa-fluoridophosphate.

In the title compound, [Cu(C(25)H(22)P(2)S)(2)]PF(6), the Cu(I) atom, lying on a twofold rotation axis, adopts a distorted tetra-hedral geometry. The (diphenyl-phosphanylmeth-yl)diphenyl-phos-phane sulfide ligand coordinates to the Cu(I) atom through one S and one P atom, forming a stable five-membered chelate ring. The P atom of the PF(6) (-) anion also lies on a twofold rotation axis.

Ferrocenyl-phospho-nic acid.

In the title compound, [Fe(C(5)H(5))(C(5)H(6)O(3)P)], the phosphate group is bonded to the ferrocene unit with a P-C bond length of 1.749 (3) Å. In the crystal, six ferrocenyl-phospho-nic acid mol-ecules are connected by 12 strong inter-molecular O-H⋯O hydrogen bonds, leading to the formation of a highly distorted octa-hedral cage. The volume of the octa-hedral cage is about 270 Å(3).

4,4'-Bipyridine-pyridine-3,5-dicarb-oxy-lic acid (3/4).

In the title compound, 3C(10)H(8)N(2)·4C(7)H(5)NO(4), the asymmetric unit contains two mol-ecules of pyridine-3,5-dicarb-oxy-lic acid and one mol-ecule of 4,4'-bipyridine in general positions together with one mol-ecule of 4,4'-bipyridine lying across a centre of inversion, thus giving a 4:3 molar ratio of pyridine-3,5-dicarb-oxy-lic acid to 4,4'-bipyridine. The dihedral angle between the bipyridine rings on general positions is 21.2 (2)°. These mol-ecular units are linked by O-H⋯N hydrogen bonds forming an extended two-dimensional framework in the crystal.

Ga(8)Br(8).6NEt(3): formation and structure of donor-stabilized GaBr. A nanoscaled step on the way to beta-gallium?

Because of their thermodynamic instability, their sophisticated formation, and their high reactivity, only three textbook examples of Al(I)/Ga(I) subhalides have been crystallized so far: Al(4)Br(4), Al(4)I(4), and Ga(8)I(8). Here, we present the formation and structural characterization of molecular Ga(8)Br(8) species. The different structures of Ga(8)I(8) and Ga(8)Br(8) are discussed with regard to their different formation conditions and their different thermodynamic stability based on results from DFT calculations. Structural as well as thermodynamic properties of Ga(8)I(8) and Ga(8)Br(8) are strongly related to the low-temperature modifications beta-Ga and gamma-Ga. Therefore, our fruitful hypothesis about the fundamental relation between structure and energy of a number of metalloid clusters and the corresponding element modifications is now supported by two binary Ga(I)-halide compounds.

Heterometallic aggregates of copper(I) with metalloligand Sn(edt)2 (edt = ethane-1,2-dithiolate): syntheses and structures of [Sn(edt)2Cl(mu-I)(mu3-I)(CuPPh3)3], [Sn(edt)2(mu-Br)2(mu3-Br)2(CuPPh3)4], and [{Sn(edt)2}3(mu-OH)3Cu5(PPh3)8][PF6]2.

The treatment of a slurry of an equimolar mixture of [Sn(edt)(2)] (edt = ethane-1,2- dithiolate) and [Et(4)N]Cl.xH(2)O with CuI in the presence of PPh(3) gave a tetranuclear compound, [Sn(edt)(2)Cl(mu-I)(mu(3)-I)(CuPPh(3))(3)] (1), which consists of a rectangular-pyramidal [Sn(edt)(2)Cl](-) moiety ligated by three [Cu(PPh(3))](+) fragments via the sulfur atoms of the edt(2-) ligands. The treatment of a slurry of [Sn(edt)(2)] and excess [Et(4)N]Br with [Cu(MeCN)(4)][PF(6)] in the presence of PPh(3) afforded a pentanuclear compound, [Sn(edt)(2)(mu-Br)(2)(mu(3)-Br)(2)(CuPPh(3))(4)] (2), which comprises two [(CuPPh(3))(2)(mu-Br)](+) fragments symmetrically ligating an octahedral trans-[Sn(edt)(2)Br(2)](2-) moiety via the sulfur and bromide atoms. Reaction of [Sn(edt)(2)] with [Cu(MeCN)(4)][PF(6)] and PPh(3) in a mixed MeCN/CH(2)Cl(2) solution yielded a novel octanuclear compound, [{Sn(edt)(2)}(3)(mu-OH)(3)Cu(5)(PPh(3))(8)][PF(6)](2) (3), which may be described as a triangular [{Sn(edt)(2)}(3)(mu-OH)(3)](3-) core chelated by three [Cu(PPh(3))(2)](+) species and capped by two [Cu(PPh(3))](+) species. The luminescent properties of compounds 1, 2, and 3 were investigated in a CH(2)Cl(2) solution at room temperature. Upon excitation at lambda > 360 nm, these compounds are luminescent in CH(2)Cl(2) solution with emissions having maxima at 422, 515, and 494 nm, respectively.

Tetra-ethyl-ammonium trichlorido(η-p-cymene)ruthenate(II).

In the title salt, [(C(2)H(5))(4)N][RuCl(3)(C(10)H(14))], the Ru(II) atom shows an octa-hedral coordination in which the aromatic ring of the p-cymene mol-ecule occupies three coordination positions.

Bis(η-ethyl-ene)[aza-nidediylbis(diiso-propyl-phosphine selenide)-κSe,Se']iridium(III).

In the title compound, [Ir(η(2)-C(2)H(4))(2)(C(12)H(28)NP(2)Se(2))], the central Ir atom is chelated by the [N((i)Pr(2)PSe)(2)](-) ligand via two Se atoms and is coordinated by two η(2)-ethyl-ene mol-ecules via four C atoms in an octa-hedral coordination geometry.

trans-Bis(4,6-dimethyl-pyrimidine-2-thiol-ato-κN,S)bis-(thio-urea-κS)nickel(II).

In the title complex, [Ni(C(6)H(7)N(2)S)(2)(CH(4)N(2)S)(2)], the central Ni atom (located on a centre of inversion) is six-coordinated by two monoanionic N,S-chelating 4,6-dimethyl-pyrimidine-2-thiol-ate ligands and two trans S-coordinating thio-urea groups. The trans-N(2)S(4) donor set defines a distorted octa-hedral geometry.