Octa(p-hydroxy)octakis(propyloxy)calix[8]arene: The First Crystal Structure of a p-Hydroxy Calixarene

Octa(p-ydroxy)octakis(propyloxy)calix[8]arene.9(pyridine).2(H₂O) crystallises in the triclinic space group P-1, a = 14.083(2), b = 14.478(2), c = 15.652(2) Å, = 70.109(4), = 74.146(3), = 75.572(4)°, V = 2843(1) ų, Z = 1. Refinement led to a final R₁ value of 0.0757 for 4693 reflections. The calixarene sits around a crystallographic centre of inversion and is in the `chair-like' conformation. All p-hydroxyl groups form hydrogen bonds with either pyridine or water molecules leading the extended structure to be composed of infinite ribbons parallel to the [1,0,-1] direction.     

Palladium Clusters Pd4(SEt)4(OAc)4and Pd6(SEt)12: Structure and Properties

Palladium clusters Pd₄(SEt)₄(OAc)₄(I) and Pd₆(SEt)₁₂(II) were synthesized and studied. Their structure was determined by X-ray diffraction analysis. For I, a= 9.774(2) Å, b= 10.821(2) Å, c= 13.061(3) Å, = 92.88(3)°, V= 1379.6(5) ų, (calcd.) = 2.182 g/cm³, space group P2₁/n, Z= 4, N _ref= 1558, and R= 0.031; for II, a= 10.581(1) Å, b= 10.584(2) Å, c= 11.478(2) Å, = 101.62(1)°, = 104.95(1)°, = 106.74(1)°, V= 1135.2(4) ų, (calcd) = 2.007 g/cm³, space group P1, Z= 1, N _ref= 2828, and R= 0.022. In cluster I, four Pd atoms form a planar cycle. The neighboring palladium atoms are bound by two acetate or by two mercaptide bridges, the Pd···Pd distances being 3.036–3.195 Å. In cluster II, Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.083–3.127 Å. The neighboring palladium atoms are bound by two mercaptide bridges. The formation of analogous clusters in solution was confirmed by IR spectroscopy.     

A doubly deprotonated form of calix[6]arene: Crystal and molecular structure of (calix[6]arene-2H)2−·(HNEt 3 + )2

The doubly deprotonated form of calix[6]arene, with two protonated triethylamines as counter-ions, crystallizes in the monoclinic system: space groupP2₁/n,a=8.465(4),b=17.822(8),c=15.182(6) Å,=90.18(4)°,V=2291(2) ų,Z=2. Refinement led to a final conventionalR value of 0.063 for 1046 reflections. The macrocycle conformation is not apinched cone, usual for freeR-calix[6]arene, but a distorted 1,2,3-alternate cone, since the molecule lies on a symmetry center. Furthermore, one of the torsion angles defined by the methylene bridges is near to zero, which is unusual in calixarene structures. Supplementary Data relating to this article (atomic coordinates for hydrogen atoms, anisotropic displacement parameters for oxygen and nitrogen atoms, and observed and calculated structure factors) are deposited with the British Library as Supplementary Publication No. SUP 82182 (7 pages).     

Reaction of early transition metal complexes with macrocycles. II. Synthesis and structure of TiCl3(H2O) · 18-crown-6, a compound with a unique bidentate bonding mode for the 18-crown-6 molecule

18-crown-6 reacts with TiCl₃ in CH₂Cl₂ to form a complex in which the crown ether functions as a tridentate ligand. Addition of moist hexane affords a molecular complex in which the crown ether functions as a bidentate ligand. A water molecule is bonded directly to the titanium atom and is further hydrogen bonded to three of the oxygen atoms of the crown. The deep blue crystals of the CH₂Cl₂ adduct belong to the monoclinic space groupP2₁/n witha=13.481(8),b=8.021(5),c=21.425(9) Å, =97.32(5)°, and _calc = 1.51 g cm^–3 forZ=4. Refinement led to a conventionalR value of 0.040 based on 873 observed reflections. The Ti–O bond distances for the crown oxygen atoms are 2.123(8) and 2.154(9) Å, while the oxygen atom of the water molecule is bonded at 2.072(8) Å. The octahedral coordination sphere of the titanium atom is completed by the three chlorine atoms at distances of 2.340(5), 2.352(4), and 2.373(4) Å. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82034 (10 pages).     

Crystalline complexes of N,N'-ditritylurea (DTU) and N-tritylurea (NTU) hosts with molecular guests

This paper reports crystalline complexes of the new hosts N,N'-ditritylurea (DTU) and N-tritylurea (NTU) with various uncharged molecular guests. The crystal structures of the following complexes were elucidated by single crystal X-ray diffraction analysis at 115^oK: (I) 1:1 DTU-propanamide — space group C2/c, a=15.839Å, b=9.088Å, c=24.584Å, =111.05^o, Z=4; (II) 1:1 DTU-ethyl N-acetylglycinate — space group P1, a=9.010Å, b=10.800Å, c=19.810 Å, =105.29^o =94.33^o, =93.03^o, Z=2; (III) 2:1 NTU-N, N-dimethylformamide — space group Cc, a=29.614Å, b=8.906Å, c=16.127Å, =121.04^o, Z=4. The three crystal structures are stabilized mainly by a cooperative effect of hydrogen bonding between amide fragments displaced along the shortest axis of each crystal. This interaction occurs between host and guest in complexes I and II, and between host and host in complex III. The latter also represents a cage-type clathrate in which the guest molecules are accommodated in voids between the hydrophobic fragments of four neighboring NTU hosts. On the other hand, complexes of DTU are characterized by a more specific interaction between the two components, each guest molecule being inserted between two adjacent hosts (related by translation) and strongly bound to them via hydrogen bridges. These results illustrate a useful concept in the design of molecular species which can be potential hosts upon crystallization with neutral molecular guests. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82022 (7 pages).     

Copper(II) Complexes with N-(3-Hydroximino-2-methylbutan-2-yl)methylamine (HL): Synthesis and Properties. Crystal and Molecular Structures of [Cu(HL)Cl2] and [Cu(HL)(H2O)2SO4]n

Paramagnetic copper(II) complexes with N-(3-hydroximino-2-methylbutan-2-yl)methylamine (HL), namely, Cu(HL)Cl₂(I), Cu(HL)(SO₄) · 2H₂O (II), and Cu(HL)(NO₃)₂(III), were obtained. The crystal structures of I and II were determined. The blue crystals of these compounds are monoclinic. For I(C₆H₁₄Cl₂CuN₂O): a = 8.820(1) Å, b = 6.511(1) Å, c = 18.255(2) Å, = 92.86(1)° V = 1047.0(2) ų, space group P2₁/c, _calcd = 1.679 g/cm³, Z = 4 for R ₁ = 0.0250; for II(C₆H₁₈CuN₂O₇S): a = 9.999(2) Å, b = 9.927(2) Å, c = 12.963(3) Å, = 106.37(3)°, V = 1234.5(4) ų, space group P2₁/c, _calcd = 1.753 g/cm³, Z = 4 for R ₁ = 0.0324. Crystals of I have a molecular structure. The Cu coordination polyhedron is a square bipyramid (2N + 2Cl + Cl + Cl) due to additional contacts with two Cl atoms from the neighboring molecules. Structure II is built from polymeric chains. The environment of the Cu atom is a distorted cis-octahedron (2N + 2O(H₂O) + 2O(SO₄)). Complexes I–IIIare characterized by IR and EPR spectroscopy.     

Molecular structure of the cobalt(ii) chloride complex with triphenyl-N-(2-pyrimidyl)phosphineimine

An X-ray structural study of the cobalt(ii) chloride complex with triphenyl-N-(2-pyrimidyl)phosphineimine has been performed (automatic diffractometer, Mo-–K , 2916 observed reflections, the heavy-atom method, the least squares method in anisotropicisotropic approximation toR=0.043). The crystals are monoclinic,a=15.979(6) Å,b=17.391(6) Å,c=14.976(6) Å, =104.21(2)°,V=4034(5) ų,d _calc=1.384 g cm^–3,Z=4, space groupP2₁/c. The Co atom has a distorted tetrahedral coordination by two Cl atoms (2.268(2) Å and 2.278(3) Å) and two N atoms (2.030(4) Å and 2.025(5) Å) of the two pyrimidine heterocycles. The Cl-Co-Cl and N-Co-N bond angles are equal to 107.7(1)° and 123.4(2)°, respectively. Additional weak coordination of the Co atom by two N atoms of the imine groups [Co...N 2.982(4) Å and 3.045(4) Å] is also observed in the molecule of the complex, and this coordination changes the nearest environment of the Co atom to distorted octahedral coordination. The lengths of the phosphorus-imine P=N bonds are 1.596(6) Å and 1.585(6) Å. The results obtained are compared with previous structural investigations of similar complexes of transition metals with iminophosphoranes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1203–1206, July, 1993.     

Preparation and structure of (calix[8]arene methyl ether) · 2CDCl3

The methyl ether of calix[8]arene crystallizes from CDCl₃ with two molecules of the solvent per molecule of host. An X-ray structural investigation has shown that the CDCl₃ guests exist within the calixarene framework. The complex resides on a crystallographic center of inversion, and the cavity is roughly circular in projection as measured by the distance between centroids of aromatic rings related by the center: 14.5, 13.9, 10.1, and 11.2 Å. Six of the oxygen atoms are found on the inside and two on the outside. Crystals belong to the triclinic space group witha=11.741(9),b=11.810(9),c=12.484(8) Å, =94.74(8), =104.41(8), =111.30(9)°, andD _c =1.31 g cm^–3 forZ=1. Refinement led to a finalR value of 0.086 for 949 observed reflections. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82038 (10 pages).     

An inclusion complex between acetonitrile andp-tert-butylcalix[6]arene

p-tert-Butylcalix[6]arene forms a complex with 1.5 acetonitrile molecules, that are included in the macrocycle cavity. This complex crystallizes in the monoclinic system: space groupP2₁/m,a=14.043(4),b=16.916(11),c=14.199(11) Å,=98.27(6)°,V=3338(4) ų,Z=2 (formula units). Refinement led to a final conventionalR value of 0.113 for 1654 reflections. Thepinched cone conformation of the calixarene is the same as that of the neutral and freeR-calix[6]arene already described. The two acetonitrile molecules interact with some phenyl ring -clouds, a methylene bridge and sometert-butyl groups of the calixarene. Supplementary Data relating to this article (atomic coordinates for hydrogen atoms, anisotropic displacement parameters, selected geometrical parameters and observed and calculated structure factors) are deposited with the British Library as Supplementary Publication No. SUP 82188 (16 pages).     

Interaction of Np(V) with N,N-Dimethylacetamide

A new Np(V) complex [(NpO₂)(NO₃)(DMAA)₂(H₂O)] was synthesized and its crystal structure was determined. Its absorption spectra were recorded in IR and near-IR regions. The unit cell parameters are a = 9.389(3) Å, b = 8.075(3) Å, c = 20.956(7) Å, = 92.53(3)°, space group P2₁/c, Z = 4, V = 1585.8(9) ų, R = 0.054, wR(F ²) = 0.170. The coordination polyhedron of the Np atom is a pentagonal bipyramid with the O atoms of two DMAA molecules, bidentate nitrate ion, and the water molecule in its equatorial plane.     

The crystal structure of the syn-proximal-5,11,17,23-tetra-tert-butyl-25,26-bis[(2-pyridylmethyl)oxy]-27,28-dihydroxy-calix[4]arene ethanol 1 : 1 Inclusion Complex

The crystal structure of the title compound (1 · C₂H₅OH) has been determined by single-crystal X-ray analysis and refined to anR-value of 0.074 for 2732 observed reflections [I > 2.0(I)]. Crystals are triclinic, space group P , witha = 13.6150(18),b = 13.7195(11),c = 16.5497(16) Å, = 73.132(7), = 66.165(9), = 65.580(8)° andZ = 2. Calix[4]arene (1) adopts a relatively open distorted cone conformation in the solid state, with two pendantsyn-proximal O-CH₂-Py groups. The major conformation determining features in (1 · C₂H₅OH) are the presence of (a) an intramolecular O-H...O hydrogen bond between adjacent proximal phenolic oxygens, O...O 2.719(7) Å and (b) an intramolecular O-H...N hydrogen bond between a phenolic oxygen and a proximal pyridinyl nitrogen, O...N 2.810(8) Å. The intramolecular hydrogen bonding and the interplanar angles of 65.1(3) and 50.7(3)° between opposite aromatic rings facilitate the inclusion of an ethanol molecule within the calixarene cup.Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82141 (26 pages).     

The designed synthesis and crystallographic characterization of three novel heterotrimetallic linear complexes of [Et4N][(Ph3P)2{M′S2 MS2Fe}Cl2] (M=Mo,M′=Ag;M=W,M′=Cu,Ag)

The complexes [Et₄N][(Ph₃P)₂{MS₂ MS₂Fe}Cl₂] (M=Mo,M=Ag;M=W,M=Cu, Ag) have been obtained by reaction of [Et₄N]₂[S₂ MS₂FeCl₂] (M=Mo, W) with Cu(PPh₃)₃Cl or Ag(PPh₃)₃NO₃ in MeCN/CH₂Cl₂, respectively. Crystal data for [Et₄N][(PPh₃)₂ {AgS₂MoS₂Fe}Cl₂] (I): triclinic, P (No. 2),Z=2,a=13.41(1)Å,b=15.54(1)Å,c=12.30(1)Å, =105.24(6)°, =94.63(7)°, =101.38(6)°, andV=2399(4)ų. The bond lengths of Mo-Fe bond and the Mo-Ag distance are 2.756(2)Å and 3.033(2)Å, respectively. Crystal data for [Et₄N][(PPh₃)₂ {AgS₂WS₂Fe}Cl₂] (II): triclinic, P (No. 2),Z=2,a=13.457(5))Å,b=15.601(6)Å,c=12.338(4)Å, =105.20(3)°, =94.61(4)°, =101.43(4)°, andV=2426(2)ų. The bond length of W-Fe bond and the W-Ag distance are 2.786(2)Å and 3.076(1)Å, respectively. Crystal data for [Et₄N][(PPh₃)₂ {CuS₂WS₂Fe}Cl₂] (III): triclinic, P (No. 2),Z=2,a=13.498(5)Å,b=15.372(4)Å,c=12.340(4)Å, =105.54(2)°, =93.32(3)°, =101.40(3)°, andV=2401(1)ų. The bond lengths of W-Fe bond and the W-Cu bond are 2.800(1)Å and 2.851(1)Å, respectively.     

Preparation and x-ray structure determination of penta-and tetracyano-oxomolybdenum(IV) anions. The influence of water on their reactivity

Summary Several penta-and tetracyanooxomolybdenum(IV) anions have been synthesized containing different numbers of H₂O molecules, either coordinated or present as crystallisation molecules. The influence of these molecules on the reactivity of the complex, especially towards O₂, is discussed. Three compounds were characterized by x-ray structure determination. [Mo(O)(CN)₅(H₂O)₂(MeCN)₂][PPh₄]₄Cl belongs to triclinic space group P-1 witha=13.146(3) Å,b=16.944(5) Å,c=21.761(6) Å, =84.72(2)°, =87.15(2)° and =85.25(2)°. The volume of the unit cell is 4678(6)ų withz=2. The structure was refined to R=6.5%. [Mo(O)(CN)₄(H₂O)·6H₂O][PPh₄]₂ belongs to monoclinic space group P2₁/n witha=15.313(2)Å,b=19.983(3)Å,c=17.006(2)Å, =100.51(2)°. The volume of the unit cell is 5117(3)ų withz=4. The structure was refined to R=8.7%. [Mo(O)(CN)₄(MeCN)](PH₃)₂N]₂ belongs to triclinic space group P-1 witha=13.770(4)Å,b=16.292(5)Å,c=16.889(5)Å, =73.23(2)°, =72.02(2)° and =71.57(2)°. The volume of the unit cell is 3342(3)ų withz=2. The structure was refined to R=7.2%.     

Synthesis and crystal structure of ammonium (picrate) (dibenzo-18-crown-6)

NH₄(Pic)(DB18C6) (Pic=picrate and DB18C6=dibenzo-18-crown-6), (C₂₆H₃₀N₄O₁₃) FW 606.56, arthorhombic,Pmn2₁,a=26.045(5),b=12.055(3),c=8.982(3) Å,V=2820(1) ų,Z=4,D _c =1.429 g/cm³, CuK, =1.54184 Å, (CuK)=9.5 cm^–1,F(000)=1272,T=298 K. The structure has been refined toR=0.0475 for 2617 unique observed reflections. In the lattice the 1:1 complex exists as a 2:2 dimer in which the crown are coupled through the Pic anions and NH₄ ⁺ cations. The asymmetric unit consists of two independent half crown ethers of which two opposite O atoms are on the mirror plane, two half ammonium cations of which the N and two H atoms are also on the mirror plane while the Pic anion is in a general position. Relative to each other, the corwn ethers are shifted by about 7.3 Å alongb and 1 Å alongc. The 1:1 sandwich of NH₄ with DB18C6 and Pic on dimerisation becomes a club pseudo-sandwich with three phenyl rings on either side of the mirror plane, thus forming a nearly parallel stack with a 3.6 Å inter-ring distance. The NH₄ ions hold the structure; two H atoms on the mirror plane are hydrogen-bonded to the opposite oxygens of the crown located on the purely aliphatic part of the ring (2.10(1), 2.06(3) and 2.26(3), 2.05(1) Å) for the two independent crowns, respectively, while the other two H atoms form mirror-related bifurcated hydrogen bonds with the phenoxide oxygen (1.99(1) and 2.01(1) Å) and theo-nitrogen oxygen (2.44(2) and 2.34(1) Å) of the picrates. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82037 (29 pages)     

Solid state synthesis of copper(I) thiotungstate cluster compounds at low heating temperatures. Crystal structures of [(n-Bu)4N]3-[WS4Cu3Cl3Br] and [Et4N]4[WS4Cu4I6]

Summary Reaction of [NH₄]₂[WS₄] with CuX (X = Cl or I) and R₄NX (R = Et or n-Bu) in the solid state gave two new bimetallic compounds with W:Cu compositions from 1:3 to 1:4. Compound (1), [(n-Bu)₄N]₃[WS₄Cu₃Cl₃Br], crystallizes in the hexagonal space group R3c with a = 17.051(5), c = 38.372(5) Å, V = 9661.8 ų, Z = 6. The cluster anion of (1) comprises a cubane-like cluster core [WS₃Cu₃Br] of C₃ symmetry with a Cl atom attached to each of the three Cu atoms and one terminal sulphido ligand attached to the W atom. Compound (2), [Et₄N]₄[WS₄Cu₄I₆], crystallizes in the monoclinic space group C2/m with a = 29.702(6), b = 12.7887(5), c = 15.327(3)Å, = 99.69(2), V = 5738.1 ų, Z = 4. In the cluster anion of (2), four edges of the WS₄ core are coordinated by four Cu atoms, giving a WS₄Cu₄ aggregate of approximate C_2V symmetry.     

Two clathrates of bis(isothiocyanato)tetrakis(4-methylpyridine)magnesium(II) as a host with 4-methylpyridine as a guest

Two clathrate modifications of the title host with 4-methylpyridine (4-CH₃C₅H₄N) as a guest have been determined at –50°C. [Mg(4-CH₃C₅H₄N)₄(NCS)₂] · 2/3(4-CH₃C₅H₄N) · 1/3H₂O is trigonal, space group , witha=27.630(7),c=11.219(3) ÅV=7417(4) ų,Z=9,D _calc=1.171 g cm^–3,(CuK )=18.506 cm^–1, finalR=0.064. [Mg(4-CH₃C₅H₄N)₄(NCS)₂] · (4-CH₃C₅H₄N) is tetragonal, space group I4_l/a, witha=16.944(7),c=23.552(9)Å,V=6762(5) Å,Z=8,D _calc=1.191 g cm^–3, (CuK )=18.200 cm^–1, finalR=0.071.The structures consist of molecular packings of the same host complex units and the guest species. The Mg(II) cation is octahedrally coordinated to theN-atoms of four 4-methylpyridine and twotrans-coordinated isothiocyanato ligands in the host molecule. The conformations of the molecule are considerably different both in symmetry and in geometry in these two structures. The guest 4-methylpyridine molecules are disordered into channels which have different topology in these two clathrates resulting in different thermal stability.     

Coordination chemistry of alkali and alkaline earth cations: Synthesis and crystal structure of potassium(benzo-15-crown-5)2 [3,5-dinitrobenzoate(3,5-dinitrobenzoic acid)2]

The interaction of K(35-Dnb) (35-Dnb=3,5-dinitrobenzoate) with benzo-15-crown-5 (B15C5) in ethanol yields a charge-separated sandwich structured complex [K(B15C5)₂]⁺[35-Dnb(35-DnbH)₂]^– even when equimolar amounts of reactants were used and no external 35-DnbH was added to the reaction mixture. The complex (KC₄₉H₅₁O₂₈N₆, FW=1211.1), is monoclinic,P2₁/c,a=11.063(2),b=10.680(1),c=46.548(8) Å, =91.629(2)⁰,Z=4,D ₀=1.485 g/cm³,D _c=1.468 g/cm³, CuK =1.5418 Å, =17.01 cm^–1, 2<130⁰,F(000)=2520,T=298 K. FinalR for the 6618 observed reflections was 0.071. In the sandwich moiety, the K⁺ is 10-coordinated through all the oxygens of the crown molecules (K⁺–O, 2.76–3.11 Å). The 35-Dnb anion lies 5.3 Å below the lower crown mean plane and is charge separated with respect to K⁺ (K⁺–O^–>7 Å) but undergoes strong hydrogen bonding (2.59 and 2.49 Å) through each carboxylate oxygen with the carboxylic protons of two separate 35-DnbH molecules. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82014 (52 pages).     

On the crystal chemistry of three copper(II)-arsenates: Cu3(AsO4)2-III,Na4Cu(AsO4)2, and KCu4(AsO4)3

The three copper(II)-arsenates were synthesized under hydrothermal conditions; their crystal structures were determined by single-crystal X-ray diffraction methods:Cu₃(AsO₄)₂-III:a=5.046(2) Å,b=5.417(2) Å,c=6.354(2) Å, =70.61(2)°, =86.52(2)°, =68.43(2)°,Z=1, space group ,R=0.035 for 1674 reflections with sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a=4.882(2) Å,b=5.870(2) Å,c=6.958(3) Å, =98.51(2)°, =90.76(2)°, =105.97(2)°,Z=1, space group ,R=0.028 for 2157 reflections with sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a=12.234(5) Å,b=12.438(5) Å,c=7.307(3) Å, =118.17(2)°,Z=4, space group C2/c,R=0.029 for 1896 reflections with sin / 0.80 Å^–1.Within these three compounds the Cu atoms are square planar [4], tetragonal pyramidal [4+1], and tetragonal bipyramidal [4+2] coordinated by O atoms; an exception is the Cu(2)^[4+1] atom in Cu₃(AsO₄)₂-III: the coordination polyhedron is a representative for the transition from a tetragonal pyramid towards a trigonal bipyramid. In KCu₄(AsO₄)₃ the Cu(1)^[4]O₄ square and the As(1)O₄ tetrahedron share a common O—O edge of 2.428(5) Å, resulting in distortions of both the CuO₄ square and the AsO₄ tetrahedron. The two Na atoms in Na₄Cu(AsO₄)₂ are [6] coordinated, the K atom in KCu₄(AsO₄)₃ is [8] coordinated by O atoms.Die drei Kupfer(II)-Arsenate wurden unter Hydrothermalbedingungen gezüchtet und ihre Kristallstrukturen mittels Einkristall-Röntgenbeugungsmethoden ermittelt:Cu₃(AsO₄)₂-III:a = 5.046(2) Å,b = 5.417(2) Å,c = 6.354(2) Å, = 70.61 (2)°, = 86.52(2)°, = 68.43(2)°,Z = 1, Raumgruppe ,R = 0.035 für 1674 Reflexe mit sin / 0.90 Å^–1.Na₄Cu(AsO₄)₂:a = 4.882(2) Å,b = 5.870(2) Å,c = 6.958(3) Å, = 98.51(2)°, = 90.76(2)°, = 105.97(2)°,Z = 1, Raumgruppe ,R = 0.028 für 2157 Reflexe mit sin / 0.90 Å^–1.KCu₄(AsO₄)₃:a = 12.234(5) Å,b = 12.438(5) Å,c = 7.307(3) Å, = 118.17(2)°,Z = 4, Raumgruppe C2/c,R = 0.029 für 1896 Reflexe mit sin / 0.80 Å^–1.Die Cu-Atome in diesen drei Verbindungen sind durch O-Atome quadratisch planar [4], tetragonal pyramidal [4 + 1] und tetragonal dipyramidal [4 + 2]-koordiniert; eine Ausnahme ist das Cu(2)^{[4 + 1]}-Atom in Cu₃(AsO₄)₂-III: Das Koordinationspolyeder stellt einen Vertreter des Übergangs von einer tetragonalen Pyramide zu einer trigonalen Dipyramide dar. In KCu₄(AsO₄)₃ haben das Cu(1)^[4]O₄-Quadrat und das As(1)O₄-Tetraeder eine gemeinsame O—O-Kante von 2.428(5) Å, was eine Verzerrung der beiden Koordinationsfiguren CuO₄-Quadrat und AsO₄-Tetraeder bedingt. Die zwei Na-Atome in Na₄Cu(AsO₄)₃ sind durch O-Atome [6]-koordiniert, das K-Atom in KCu₄(AsO₄)₃ ist [8]-koordiniert.

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Zur Kristallchemie dreier Kupfer (II)-Arsenate: Cu₃(AsO₄)₂-III, Na₄Cu(AsO₄)₂ und KCu₄(AsO₄)₃

     

The Crystal Structures of Rubidium and 4-Amino-1,2,4-Triazolium Tetrafluoroantimonates(III)

The crystal structures of complex antimony(III) fluorides RbSbF₄ (I) and (C₂N₄H₅)SbF₄ (II) were determined. The crystals of I and II are monoclinic; for I: a = 4.628(1) Å, b = 6.167(1) Å, c = 7.922(1) Å, = 100.582(3)°, V = 222.24(7) ų, Z = 2, (calcd.) = 4.23 g/cm³, (exp.) = 4.25 g/cm³, F(000) = 248, space group P2₁/m, R = 0.0395; for II: a = 4.678(1) Å, b = 7.339(4) Å, c = 10.185(1) Å, = 90.88(2)°, V = 349.6(2) ų, Z = 2, (calcd.) = 2.69 g/cm³, (exp.) = 2.70 g/cm³, F(000) = 264, space group P2₁. The structure of I is formed by Rb⁺ cations and [SbF₄] ^n– _n anionic chains composed of SbF₅E octahedra with two bridging fluorine atoms. The structure of IIis formed by (C₂N₄H₅)⁺ cations and isolated [SbF₄]^– anions in which the antimony polyhedra are SbF₄E trigonal bipyramids. The relationship between the crystal structures and electrophysical and biological properties of single-charged cation tetrafluoroantimonates(III) was studied.     

Coordination chemistry of alkali and alkaline earth cations: Crystal structure of rubidium (benzo-15-crown-5)2NO3·H2O

The complex Rb(B15C5)₂NO₃·H₂O is monoclinic,P2_1/c,a=12.695(3),b=19.471(3),c=12.991(2)Å, =99.60(2)^o,V=3166 ų,D _c =1.473 g/cm³ (163 K),D _c =1.434 g/cm³ (298 K),D _o =1.44 g/cm³ (298 K),T=163K,Z=4, MoK=0.71069 Å, 2(4^o–53^o), =16.43 cm^–1,F(000)=1424. FinalR for the 4588 observed reflections (F>3) is 0.062. All ten oxygens of the two benzo-crowns are shown to coordinate to the rubidium ion (Rb...O,2.92 to 3.07 Å) forming a charge-separated sandwich. The nearest nitrate oxygen is displaced 6.51 Å from the rubidium ion and is hydrogen bonded to a water molecule. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82028 (28 pages)