Crystal Structures of the [2.2.2]Cryptates [Cd(cryptand 222)][CdCl4] and [Hg(cryptand 222)][Hg2Cl6] with 8-Coordinated Metal Ions

Reactions of [2.2.2]cryptand, 4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo-[8.8.8]hexacosane, (“cryptand 222”) with cadmium chloride and mercuric chloride yielded crystals of [Cd(cryptand 222)][CdCl4] (1) and [Hg(cryptand 222)][Hg2Cl6] (2). 1 crystallizes tetragonally, space group P42/n, Z = 4, a = 1239.8(2), c = 1801.2(8) pm; 2 is monoclinic, space group P2/n, Z = 2, a = 1060.3(3), b = 955.2(2), c = 1607.0(3) pm. and β = 108.85(2)°. In the cations of both complexes the metal ions are enclosed in the bicyclic ligand and show 8-coordination to its six oxygen and two nitrogen atoms, the coordination polyhedron is a distorted cube for 1 and a bicapped trigonal antiprism for 2. The anion of 2 is dimeric, the two mercury atoms are connected via chlorine bridges with Hg-Cl distances of 258 and 278 pm, the Hg-Cl bond lengths to the two terminal chloro ligands being shorter at 236 and 238 pm

Supramolecular Chloride Bridged Metal(II) Dichloride Diazine Complexes: Crystal Structures of [Cd(pyrazine)Cl2], [Zn(pyrazine)Cl2], and [Zn(pyrimidine)Cl2]

Single crystals of [Cd(pyrazine)Cl2],[Zn(pyrazine)Cl2] and [Zn(pyrimidine)Cl2] were obtained by a diffusion technique from aqueous solutions of the metal dichlorides and solutions of the respective diazine. The structures consist of “supramolecular” networks of-M-Cl-M - and -M-diazine-M-chains

Crystal Structures of Two Copper(II) Cyclam Complexes: [{CuCl(C10N4H24 )}2][CdCl4] and [Cu(C10N4H24)][CdCl3 (H2O)2]Cl

Crystals of both complexes were obtained by evaporation of the ethanol solvent. The crystals of [{CuCl(C10N4H24)}2][CdCl4] are tetragonal, space group I4̄2d, Z = 4, a = b = 1784.1(11), c = 1101.1(8) pm. Each copper atom is bonded to one cyclam ligand and two chlorine atoms which are acting as bridging ligands and connect the copper atoms to chains of distorted octahedra. Distorted tetrahedra of CdCl4 are situated in cavities between these chains. The crystals of [Cu(C10N4H24)][CdCl3(H2O)2]Cl are monoclinic (b), space group C2/c, Z = 4, a = 1581.9(8), b = 1323.3(7), c = 924.0(5) pm, β = 94.31(5)°. Cadmium is coordinated to four chlorine atoms and two water molecules, while all of the chlorine atoms act as bridging ligands connecting every cadmium atom to two adjacent cadmium atoms and to two copper atoms which lie in plane with the N atoms

Crystal Structure of the Cyano Linked Polymeric Zinc Cyanide Pyridine Complex [Zn(py)2][Zn(CN)4]

The reaction of aqueous solutions of potassium tetracyanozincate, zinc chloride, and pyridine yields crystals of [Zn(py)2][Zn(CN)4], The crystals are orthorhombic, space group Cccm, a = 926.7(4), b = 1340.8(4), c = 1343.3(4) pm. The structure is polymeric and consists of alternate arrays of tetrahedrally and octahedrally coordinated zinc atoms, bridged by CN ligands. Two pyridine molecules ligate at the axial positions of the octahedrally coordinated zinc atoms

The Crystal Structure of Hexa-μ-chloro-μ4- oxo-tetrakis [hexamethylenetetraminecopper- (II)], [Cu4Cl6O(C6H12N4)4], a Copper(II) Complex with a Structure Related to that of Beryllium Oxoacetate

By reaction of solutions of CuCl2·2H2O and hexamethylenetetramine, C6H12N4, in acetone, a complex [Cu4Cl6O(C6H12N4)] could be obtained as single crystals. An X-ray analysis shows that the complex has a structure related to that of basic beryllium acetate. An oxygen atom is tetrahedrally surrounded by four cop-per atoms which, together with six chlorine atoms, form an adamantane-like core. Each copper atom is bonded via a nitrogen atom to a hexamethylenetetramine molecule

Molecular and Crystal Structure of l,r-Dimethylsilylene Titanocene Dichloride, (CH3)2Si(C5H4)2TiCl2

The molecular structure of the bridged [1]-titanocenophane 1,1'-dimethylsilylene titanocene dichloride, (CH3)2Si(C5H4)2TiCl2, has been investigated by an X-ray structure determination. Crystal data: monoclinic, space group C2/c, Z = 4, a = 1332.9(3), 6 = 988.7(3), c = 1068.9(3) pm, β = 113.43(2)°. The results are compared with the structural dimensions of similar compounds: 1,1'-methylene titanocene dichloride, CH2(C5H4)TiCl2, with the unbridged titanocene dichloride, (C5H5)2TiCl2 and the ethylene-bridged compound (CH2)2(C5H4)2TiCl2

Metal Complexes with Hexamethylenetetramine as a Ligand, V II [1] Crystal Structures of the Zinc Chloride Adduct ZnCl2 • C6H12N4, and the Zinc Bromide Adduct ZnBr2 • C6H12N4

By reaction of zinc chloride and zinc bromide with hexamethylenetetramine in water/methanol crystals of the adducts ZnCl2 • C6H12N4 and ZnBr2 • C6H12N4, resp. were obtained. The compounds are isotypic, they crystallize in the orthorhombic space group P21am (non-standard setting of space group Pmc21, No. 26), Z = 2. The lattice parameters of the zinc chloride adduct are a = 1168.0(4), b = 685.7(4), and c = 601.1(4) pm, of the zinc bromide adduct a - 1188.9(6), b = 721.5(5), and c = 602.3(4) pm. The adducts are polymeric, they form parallel chains in the crystal. The zinc atoms are bonded to two halogen atoms and, via nitrogen atoms, to two hexamethylenetetramine molecules, which act as bidentate ligands. The coordination of the zinc atoms is approximately tetrahedral

Crystal Structure of the “Supramolecular” Silver(I)thiocyanate Cyclam Complex [Ag(SCN)·(C10H24N4)1/2]

Colourless crystals of the 1,4,8,11-tetraazacyclotetradecane (cyclam) silver(I) thiocyanate complex [Ag(SCN) · (C10H24N4)1/2] were obtained by diffusion of a solution of cyclam in ethanol into an aqueous solution of K[Ag(SCN)2], The crystals are tetragonal, space group P42/n, Z = 8, a = b - 1256.0(4), c = 1185.5(9) pm. The SCN groups act as μ3 ligands, the S atoms of two SCN groups bridge two neighbouring Ag ions, which are only 297.5 pm apart, forming butterfly-like Ag2S2 moieties, the N atoms of the SCN groups form bonds to Ag atoms of adjacent Ag2S2 moieties. Two Ag2S2 units are again connected by cyclam molecules which act as two-dentate bridging ligands. Thus a complicated three-dimensional “supramolecular” structure results

Metal Complexes with Hexamethylenetetramine as a Ligand, VI [1J Crystal Structure of Bis-hexamethylenetetramine-bisisocyanatocopper(II), [Cu(NCO)2(C6Hl2N4)2]

Crystals of the complex [Cu(NCO)2(C6Hi2N4)2] could be obtained by reaction of copper- (II)nitrate, hexamethylenetetramine, and KNCO in CHCI3 as a solvent. The crystals are triclinic, space group Cl, Z = 4, a = 1373.1(9), b = 2083.1(9), c = 642.6(3) pm, a = 91.05(4), β = 90.54(6), y = 107.39(6)°. The copper atom is bonded to two terminal cyanato groups via the nitrogen atoms, and to two liexamethylentetramine molecules. In the solid state the coordination of the copper atom is, however, tetragonal pyramidal, because there is an additional, rather long bond to one of the hexamethylenetetramine molecules of the neighbouring complex unit, resulting in the formation of chains

The Crystal Structure of Calciumhexacyanoferrate(II)- Hexamethylenetetramine-Water(1/1/6) Ca2[Fe(CN)6] · C 6H12N4 · 6H2O

Ca2[Fe(CN)6]•Ct,H12N4-6H20 crystallizes in the monoclinic space group B2lb with a = 1130,2(4), b = 1373,5(4), c = 1353,0(4) pm and y = 97,17°. The X-ray single crystal structure determination converged at R - 0.055 (2057 reflections). Each of the four Fe(CN)6 octahedra (Z = 4) in the unit cell is coordinated by six Ca atoms with mean NCYAN —Ca distances of 253.5(3) pm. The Ca atoms are bridged by hexamethylenetetramine and water molecule