Di-aqua-{µ2-N,N'-bis-[(cyclo-hexa-nyl-idene)amino]-oxamide}-bis-(tri-phenyl-phosphane)silver(I) dinitrate.

The dinuclear title compound, [Ag2(C14H22N4O2)(C18H15P)2(H2O)2](NO3)2, lies across an inversion center and consists of two [Ag(H2O)(PPh3)] units bridged by a bis-(cyclo-hexa-none)oxalydihydrazone ligand. The charge-balance is supplied by two nitrate anions. The symmetry-unique Ag(I) ion is in a distorted tetra-hedral geometry coordinated by a P atom from a tri-phenyl-phosphane ligand, an O atom from a water mol-ecule and a bis-(cyclo-hexa-none)oxalydihydrazone ligand bidentate chelating through the O atom and one of N atoms. In the crystal, O-H⋯O and N-H⋯O hydrogen bonds link the components, forming chains along the b-axis direction. These chains are connected through weak C-H⋯O hydrogen bonds, leading to the formation of a two-dimensional supra-molecular network parallel to (001).

[1H-1,2,4-Triazole-5(4H)-thione-κS]bis-(tri-phenyl-phosphane-κP)(nitrato-κO)silver(I) methanol monosolvate.

In the title complex, [Ag(NO3)(C2H3N3S)(C18H15P)2]·CH3OH, the Ag(I) ion exhibits a distorted tetra-hedral coordination geometry formed by two P atoms from two tri-phenyl-phosphine ligands, one S atom from a 1H-1,2,4-triazole-5(4H)-thione ligand and one O atom from a nitrate ion. In the crystal, complex and solvent mol-ecules are linked by O-H⋯O and N-H⋯O hydrogen bonds forming a chain along the b-axis direction. The chains are linked by weak C-H⋯O hydrogen bonds forming a two-dimensional supra-molecular architecture parallel to (001). In addition, an intra-molecular N-H⋯O hydrogen bond is observed.

Controllable formation of heterotrimetallic coordination compounds: systematically incorporating lanthanide and alkali metal ions into the manganese 12-metallacrown-4 framework.

The inclusion of Ln(III) ions into the 12-MC-4 framework generates the first heterotrimetallic complexes of this molecular class. The controllable and deliberate preparations of these compounds are demonstrated through 12 crystal structures of the Ln(III)M(I)(OAc)4[12-MCMn(III)(N)shi-4](H2O)4·6DMF complex, where OAc(-) is acetate, shi(3-) is salicylhydroximate, and DMF is N,N-dimethylformamide. Compounds 1-12 have M(I) as Na(I), and Ln(III) can be Pr(III) (1), Nd(III) (2), Sm(III) (3), Eu(III) (4), Gd(III) (5), Tb(III) (6), Dy(III) (7), Ho(III) (8), Er(III) (9), Tm(III) (10), Yb(III) (11), and Y(III) (12). An example with M(I) = K(I) and Ln(III) = Dy(III) is also reported (Dy(III)K(OAc)4[12-MCMn(III)(N)shi-4](DMF)4·DMF (14)). When La(III), Ce(III), or Lu(III) is used as the Ln(III) ions to prepare the Ln(III)Na(I)(OAc)4[12-MCMn(III)(N)shi-4] complex, the compound Na2(OAc)2[12-MCMn(III)(N)shi-4](DMF)6·2DMF·1.60H2O (13) results. For compounds 1-12, the identity of the Ln(III) ion affects the 12-MCMn(III)(N)shi-4 framework as the largest Ln(III), Pr(III), causes an expansion of the 12-MCMn(III)(N)shi-4 framework as demonstrated by the largest metallacrown cavity radius (0.58 Å for 1 to 0.54 Å for 11), and the Pr(III) causes the 12-MCMn(III)(N)shi-4 framework to be the most domed structure as evident in the largest average angle about the axial coordination of the ring Mn(III) ions (103.95° for 1 to 101.69° for 11). For 14, the substitution of K(I) for Na(I) does not significantly affect the 12-MCMn(III)(N)shi-4 framework as many of the structural parameters such as the metallacrown cavity radius (0.56 Å) fall within the range of compounds 1-12. However, the use of the larger K(I) ion does cause the 12-MCMn(III)(N)shi-4 framework to become more planar as evident in a smaller average angle about the axial coordination of the ring Mn(III) ions (101.35°) compared to the analogous Dy(III)/Na(I) (7) complex (102.40°). In addition to broadening the range of structures available through the metallacrown analogy, these complexes allow for the mixing and matching of a diverse range of metals that might permit the fine-tuning of molecular properties where one day they may be exploited as magnetic materials or luminescent agents.

Bis(2,4,6-tri-amino-pyrimidin-1-ium) sulfate penta-hydrate.

The asymmetric unit of the title salt, 2C4H8N5 (+)·SO4 (2-)·5H2O, contains four 2,4,6-tri-amino-pyrimidinium (TAPH(+)) cations, two sulfate anions and ten lattice water mol-ecules. Each two of the four TAPH(+) cations form dimers via N-H⋯N hydrogen bonds between the amino groups and the unprotonated pyrimidine N atoms [graph-set motif R 2 (2)(8)]. The (TAPH(+))2 dimers, in turn, form slightly offset infinite π-π stacks parallel to [010], with centroid-centroid distances between pyrimidine rings of 3.5128 (15) and 3.6288 (16) Å. Other amino H atoms, as well as the pyrimidinium N-H groups, are hydrogen-bonded to sulfate and lattice water O atoms. The SO4 (2-) anions and water mol-ecules are inter-connected with each other via O-H⋯O hydrogen bonds. The combination of hydrogen-bonding inter-actions and π-π stacking leads to the formation of a three-dimensional network with alternating columns of TAPH(+) cations and channels filled with sulfate anions and water mol-ecules. One of the sulfate anions shows a minor disorder by a ca 37° rotation around one of the S-O bonds [occupancy ratio of the two sets of sites 0.927 (3):0.073 (3)]. One water mol-ecule is disordered over two mutually exclusive positions with an occupancy ratio of 0.64 (7):0.36 (7).

(anti-Chlorido-thio-semicabazide-κS)bis-(tri-phenyl-phosphane-κP)copper(I) 0.48-hydrate.

In the mononuclear title complex, [CuCl(CH5N3S)(C18H15P)2]·0.48H2O, the Cu(I) ion is in a slightly distorted tetra-hedral coordination geometry formed by two P atoms from two tri-phenyl-phosphane ligands, one S atom from a thio-semicarbazide ligand and one chloride anion. An intra-molecular N-H⋯N hydrogen bond [graph-set motif S(5)] stabilizes the thio-semicarbazide ligand in its anti conformation, and an intra-molecular N-H⋯Cl hydrogen bond between the hydrazine N-H group and the chloride anion influences the arrangement and orientation of the ligands around the metal center. A weak intra-molecular C-H⋯Cl hydrogen bond is also present. In the crystal, complex mol-ecules are connected through N-H⋯Cl hydrogen bonds originating from the amide -NH2 group, and through O-H⋯S and O-H⋯Cl hydrogen bonds involving the solvent water mol-ecule. Both the direct N-H⋯Cl hydrogen bonds as well as the bridging hydrogen bonds mediated by the water mol-ecule connect the complex mol-ecules into zigzag chains that propagate along [010]. The solvent water mol-ecule is partially occupied, with a refined occupancy of 0.479 (7).

Bis[µ-bis-(diphenyl-phosphan-yl)methane-κ(2) P:P'](µ-1-ethyl-thio-urea-κ(2) S:S)bis-[iodidocopper(I)] acetonitrile sesquisolvate.

In the dinuclear title compound, [Cu2I2(C3H8N2S)(C25H22P2)2]·1.5CH3CN, each Cu(I) atom exhibits a distorted tetra-hedral coordination with two P atoms from two bis-(diphenyl-phosphan-yl)methane (dppm) ligands, one metal-bridging S atom from the 1-ethyl-thio-urea (ettu) ligand and one iodide ion. The dppm ligand and the bridging S atom of the ettu ligand force the two copper atoms into close proximity, leading to the formation of a close intra-molecular Cu⋯Cu contact [3.3747 (17) Å]. The conformation of the dimeric complex is such that the two dppm ligands are located on one side of the dinuclear metal complex, while the two iodine atoms are pointed towards the other side of the complex, a conformation that is stabilized by two intra-molecular N-H⋯I hydrogen bonds between the ettu NH2 and NHEt moieties and the I atoms. Another pair of symmetry-equivalent N-H⋯I hydrogen bonds is established between neighboring mol-ecules across an inversion center, linking mol-ecules into dimers. The dimers are connected with each other and with the inter-stitial acetonitrile solvent mol-ecules via a range of weaker C-H⋯I and C-H⋯S inter-actions and through weak C-H⋯π inter-actions, leading to the formation of a three-dimensional network. One of the acetonitrile solvent mol-ecules is disordered in a 1:1 ratio across a crystallographic inversion center.

Di-µ-thio-semicarbazide-κ(4)S:S-bis-[chlori-dobis(triphenyl-phosphane-κP)silver(I)].

The dinuclear title complex, [Ag(2)Cl(2)(CH(5)N(3)S)(2)(C(18)H(15)P)(2)], lies across an inversion center. The Ag(I) ion exhibits a slightly distorted tetra-hedral coordination geometry formed by a P atom from a triphenyl-phosphane ligand, two metal-bridging S atoms from thio-semicabazide ligands and one chloride ion. The S atoms bridge two symmetry-related Ag(I) ions, forming a strictly planar Ag(2)S(2) core with an Ag⋯Ag separation of 2.7802 (7) Å. There is an intra-molecular N-H⋯Cl hydrogen bond. In the crystal, N-H⋯Cl and N-H⋯S hydrogen bonds link complex mol-ecules, forming layers parallel to (001). These layers are connected through π-π stacking inter-actions [centroid-centroid distance = 3.665 (2) Å], leading to the formation of a three-dimensional network.

[4,6-Dimethyl-pyrimidine-2(1H)-thione-κS]iodidobis(triphenyl-phosphane-κP)copper(I).

In the mononuclear title complex, [CuI(C(6)H(8)N(2)S)(C(18)H(15)P)(2)], the Cu(I) ion is in a slightly distorted tetra-hedral coordination geometry formed by two P atoms from two triphenyl-phosphane ligands, one S atom from a 4,6-dimethyl-pyrimidine-2(1H)-thione ligand and one iodide ion. There is an intra-molecular N-H⋯I hydrogen bond. In the crystal, π-π stacking inter-actions [centroid-centroid distance = 3.594 (1) Å] are observed.

Di-µ-bromido-bis-({2-[(4,6-dimethyl-pyrimidin-2-yl)disulfan-yl]-4,6-dimethyl-pyrimidine-κ(2)N(1),S(2)}copper(I)).

The title dinuclear complex, [Cu(2)Br(2)(C(12)H(14)N(4)S(2))(2)], is located about an inversion center. The Cu(I) ion is coordinated in a distorted tetra-hedral geometry by two bridging Br atoms in addition to an N and an S atom from the 2-[(4,6-dimethyl-pyrimidin-2-yl)disulfan-yl]-4,6-dimethyl-pyrimidine ligand. In the crystal, π-π stacking inter-actions are observed with a centroid-centroid distance of 3.590 (2) Å.

(1-Acetyl-thio-urea-κS)bromido-bis(triphenyl-phosphane-κP)silver(I).

In the title complex, [AgBr(C3H6N2OS)(C18H15P)2], the Ag(I) ion is in a distorted tetra-hedral geometry coordinated by two P atoms from two triphenyl-phosphane ligands, one S atom of an acetyl-thio-urea ligand and one bromide ligand. There are intra-molecular N-H⋯Br and N-H⋯O hydrogen bonds present. In the crystal, pairs of N-H⋯S hydrogen bonds involving thio-urea groups form inversion dimers. In addition, moleclues pack to give sixfold phenyl embraces with an inter-molecular P⋯P distance of 6.4586 (17) Å.

Bis(µ-4,6-dimethyl-pyrimidine-2-thiol-ato)-κ(3) N,S:S;κ(3) S:N,S-bis-[(triphenyl-phosphane-κP)silver(I)].

The dinuclear title complex, [Ag2(C6H7N2S)2(C18H15P)2], comprises two inversion-related [Ag(C6H7N2S)(C18H15P)] units. The pyrimidine-thiol-ate anion acts both as a bridging and a chelating ligand. The Ag(I) ions are linked via two µ2-S donor atoms, which generate a strictly planar Ag2S2 core with an Ag⋯Ag separation of 2.9569 (4) Å. The Ag(I) ion presents a distorted tetra-hedral coordination geometry. In the crystal, weak C-H⋯N and C-H⋯S hydrogen bonds link the complex mol-ecules into a two-dimensional network parallel to (010).

Iodido[1-(propan-2-yl-idene)thio-semi-carbazide-κS]bis-(triphenyl-phosphane-κP)copper(I).

In the mononuclear title complex, [CuI(C(4)H(9)N(3)S)(C(18)H(15)P)(2)], the Cu(I) ion displays a distorted tetra-hedral coordination geometry involving two P atoms of two triphenyl-phosphane mol-ecules, one S atom of a 1-(propan-2-yl-idene)thio-semicarbazide mol-ecule and one iodide ion. In the crystal, C-H⋯π inter-actions [C-H⋯centroid distances = 3.443 (3) and 3.788 (3) Å] and N-H⋯S hydrogen bonds form layers parallel to (100). An intra-molecular N-H⋯I hydrogen bond is also observed.

Iodido(N-phenyl-thio-urea)bis-(triphenyl-phosphine)copper(I).

The coordination geometry of the Cu atom in the title compound, [CuI(C(7)H(8)N(2)S)(C(18)H(15)P)(2)], is distorted tetra-hedral; it is coordinated by two triphenyl-phosphine P atoms, one S atom from N-phenyl-thio-urea (ptu) and one I atom. The crystal structure is stabilized by intra- and inter-molecular N-H⋯I and N-H⋯S inter-actions.