Structures of triphenylbismuth dicarboxylates

Tripheylbismuth bis(trichloroacetate) (I), triphenylbismuth bis(chloroacetate) (II), and triphenylbismuth bis(bromoacetate) (III) were synthesized by the reaction of triphenylbismuth with carboxylic acid. The Bi atoms of the synthesized compounds have a distorted trigonal-bipyramidal coordination with phenyl ligands in equatorial positions. The Bi-C bond lengths lie within intervals 2.194(2)–2.201(2), 2.193(8)–2.223(7), 2.191(4)–2.220(3) Å, the distances Bi-O and Bi···O(=C) are equal 2.308(2), 2.315(2), and 2.896(2), 2.931(2); 2.289(6), 2.302(6), and 2.891(6), 2.910(6); 2.295(3), 2.312(3), and 2.893(3), 2.920(3) Å in I, II, and III, respectively. Molecules of triphenylbismuth dicarboxylates show linear dependence between the maximum equatorial angle CBiC (on the side of a contact) and intramolecular distance Bi···O(=C).     

Synthesis and Characterization of Cobalt(II), Nickel(II), and Zinc(II) Complexes with N,N ′-bis( Trans- Cinnamaldehyde)-1,2-Diiminoethane Ligand, (ca 2 en): Crystal and Molecular Structures of Co(ca 2 en)Cl 2 , Co(ca 2 en)Br 2 and Ni(ca 2 en)Br 2

A series of new complexes of the Schiff base obtained from trans- cinnamaldehyde and 1,2-diaminoethane (en) with the general formula of M(ca 2 en)X 2 (M = Co(II), Ni(II), Zn(II); X = Cl, Br, I, NCS, N 3 ; (ca 2 en) = N,N '-bis( trans- cinnamaldehyde)-1,2-diiminoethane) have been synthesized and characterized. The crystal structures of three pseudo -tetrahedral complexes, Co(ca 2 en)Cl 2 ( 1 ), Co(ca 2 en)Br 2 ( 2 ), and Ni(ca 2 en)Br 2 ( 5 ), were determined by X-ray diffraction. Crystal data for 1 , Co(ca 2 en)Cl 2 : monoclinic; space group P 2 1 / c ; a = 7.1925(14) Å, b = 20.327(4) Å, c = 14.029(3) Å; g =95.06(3)°; V = 2043.1(7) Å 3 ; Z = 4; and final R 1 = 0.0381 ( wR 2 = 0.0718) for 4653 independent reflections with I > 2 σ ( I ) and 226 parameters; 2 , Co(ca 2 en)Br 2 ; monoclinic, space group P 2 1 / c ; a = 7.3780(6) Å, b = 20.4372(17) Å, c = 14.1649(12) Å; g = 94.902(2)°; V = 2128.1(3) Å 3 ; Z = 4; and final R 1 = 0.0491 ( wR 2 = 0.1052) for 5858 independent reflections with I > 2 σ ( I ) and 227 parameters; 5 , Ni(ca 2 en)Br 2 : monoclinic, space group P 2 1 / c ; a = 7.2388(6) Å, b = 20.4651(16) Å, c = 14.2782(12) Å; g = 94.160(2)°; V = 2109.6(3) Å 3 ; Z = 4; R 1 = 0.0481 ( wR 2 = 0.0907) for 5914 independent reflections with I > 2 σ ( I ) and 227 parameters. The structures consist of discrete molecules in which the coordination polyhedra about the central metal ion are highly distorted tetrahedra with Cl(1)-Co-Cl(2), 115.51(3)°; N(1)-Co-N(2), 83.71(7)°; Br(1)-Co-Br(2), 114.58(4)°; N(1)-Co-N(2), 84.92(19)°; and Br(1)-Ni-Br(2), 125.23(3)°; N(1)-Ni-N(2), 85.11(15)° in 1 , 2 , and 5 , respectively. The stiryl groups are cis -endo with respect to the metal atom and the chelate ring is puckered. Utilization is made of electronic and vibrational spectra in structural diagnosis of other complexes.     

Coordination Networks Self-assembled by Transition Metal Salts With 4,4′-oxydianiline (4,4′-oda). Syntheses and Structures of ∞ 1 [Ni(NCS) 2 (4,4′-oda) 2 ], ∞ 2 [Co(NCS) 2 (4,4′-oda) 2 ] and ∞ 2 [M(N 3 )(4,4′-oda) 2 ]NO 3 (M=Cd II or Co II )

Four infinite complexes X 1 [Ni(NCS) 2 (4,4'-oda) 2 ], X 2 [Co(NCS) 2 (4,4'-oda) 2 ] and X 2 [M(N 3 )(4,4'-oda) 2 ]NO 3 [M=Cd II ( 3 ) or Co II ( 4 )] were obtained by reactions 4,4'-oxydianiline (4,4'-oda) with Ni(SCN) 2 , Co(SCN) 2 , Cd(N 3 ) 2 and Co(N 3 ) 2 , respectively which have been structurally established by single-crystal X-ray diffraction. Complex 1 contains one-dimensional double-stranded chains comprising 24-membered Ni 2 (4,4'-oda) 2 macrocycles, each formed by two 4,4'-oda ligands and two octahedral Ni II centers. Complex 2 exhibits two-dimensional non-interpenetrating networks consisting of large 48-membered macrocycles each formed by four 4,4'-oda ligands and four octahedral Co II centers. The crystal structures of 3 and 4 are isomorphous and both contain one-dimensional double-stranded chains comprising 24-membered M 2 (4,4'-oda) 2 macrocycles, which are interlinked by w -1,3-azide groups to generate cationic two-dimensional sheets. These sheets are further connected by hydrogen bonds between the amine groups and nitrate ions to furnish three-dimensional networks. Crystal data: complex 1 crystallizes in the monoclinic space group P 2 1 / c with a =11.990(4) Å, b =9.413(4) Å, c =12.827(4) Å, g =116.32(2), V =1297.6(8) Å 3 and Z =2; complex 2 crystallizes in the orthorhombic space group Pbca with a =9.583(2) Å, b =12.738(3) Å, c =21.039(4) Å, V =2568.2(9) Å 3 and Z =4; complex 3 crystallizes in the monoclinic space group C 2/ c with a =23.036(5) Å, b =5.920(1) Å, c =17.800(4) Å, g = 92.67(3), V =2424.8(9) Å 3 and Z =4; complex 4 crystallizes in the monoclinic space group C 2/ c with a = 22.861(5) Å, b =5.812(1) Å, c =17.720(4) Å, g =93.00(3), V =2351.2(8) Å 3 and Z =4.     

Molecular and crystal structure of 1-amino-3,5-diphenyl-2,4,4,6,6-Pentacyano-cyclohex-1-ene and 1-amino-3,5-diphenyl-2,4,4,6-tetracyanocyclohex-1-ene

Molecular and crystal structures of 1-amino-3,5-diphenyl-2,4,4,6,6-pentacyano-cyclohex-1-ene (I) and 1-amino-3,5-diphenyl-2,4,4,6-tetracyanocyclohex-1-ene (II) are studied to examine intermolecular interactions. Crystal data for (I): space group P2₁, a=11.172(3), b=6.561(2), c=16.390(4) Å, β=100.25(2)⁰, V=1182.1 ų, Z=2, R=0.046; for (II): space group P1, a=10.756(3), b=10.890(3), c=12.999(3) Å, α=62.20(2), β=70.73(2), γ=65.42(2)⁰, V=1207.2 ų, Z=2, R=0.074. Intermolecular bonds via the aminonitrile fragment in (I) lead to formation of chains along they axis: N1…N6′ (1?x, ?1/2+y, 1?z) of 3.465(8) Å, N6…N1″ (1?x, 1/2+y, 1?z), and the contact with the solvent (acetone) O1…N1 of 2.984(7) Å. In compound (II), the intermolecular contacts N1…N5′ (?x+1, ?y, ?z+1) of 3.064(7) Å link the molecules into dimeric associates.     

Formation of stable polymeric vesicles by tocopherol-containing amphiphiles

Polymeric vesicles were obtained by a free radical polymerization of aqueous dispersions of the tocopherol-containing nonionic single-chain amphiphile 3 synthesized by the reaction of O-tocopheryloligo(oxyethylene) chloroacetate ( 2 ) and 2-(N,N-dimethylamino)ethyl methacrylate. Weight-average molar masses (M̄_w) of the polymeric vesicles estimated by gel permeation chromatography are in the range of 75000–115000. The phase transition temperature (T_c) of the polymeric vesicles is 77°C, which is higher than that of the monomeric vesicles, 51°C. Transmission electron microscopy photographs show that the polymerization of monomeric vesicles of 3 leads to the formation of mostly polymeric, elliptic vesicles of distinct morphology having short axes of ca. 300–1200 Å and long axes of ca. 600–2400 Å. The polymeric vesicles exhibit an enhanced stability compared with their monomeric counterparts.     

Ring geometry and secondary interactions in a salt of S3N2Cl+; the crystal structure of 1-chloro- 1,2,4-trithia-3,5-diazolium tetrachloroferrate(III)

The structure of the title compound has been determined using single crystal X-ray methods. The tetrachloroferrate(III) ion is approximately tetrahedral, with three FeCl bonds at 2.178(2), 2.182(2) and 2.183(2) Å, and one, FeCl(2), at 2.215(2) Å, which is weakened by interactions between Cl(2) and two sulphurs of the cation. The four sulphur-nitrogen distances[l.546(6)1.604(6) Å, mean 1.578 Å] are typical of a delocalised SN system; the two-coordinate atoms (only) are coplanar within experimental error. The S(2)S(3) bond [2.181(2) Å] and exocyclic S(2)Cl(1) bond [2.086(2) Å] are respectively 0.045 Å longer and 0.08 Å shorter than in S₃N₂Cl⁺Cl^?; this is interpreted as being due to weaker cation-anion interaction in the tetrachloroferrate (III) salt. Ring angles at S(1) [105.8(3)°], N(2) [121.5(4)°], S(3) [95.6(2)°] S(2) [95.9(2)°] and N(1) [119.6(4)°] are under compression due to constraint within the small ring.     

Bonding trends in pyrites and a reinvestigation of the structures of PdAs2, PdSb2, PtSb2 and PtBi2

PdAs₂, PdSb₂, PtSb₂ and PtBi₂ have been formed from reactions of 1-gram samples of the elements in quartz tubes at 923 K, and their crystal structures have been reinvestigated. These materials crystallize with the pyrite structure. The lattice constant, a, and the positional parameter, x, of the nonmetal atoms are the following: PdAs₂ 5.9790(3) Å, 0.38317(3); PdSb₂ 6.464(1) Å, 0.3733(1); PtSb₂ 6.4423(9) Å, 0.3753(2); PtBi₂ 6.7014(8) Å, 0.3710(1). The metal-nonmetal and the closest nonmetal-nonmetal bond lengths are the following: PdAs₂, 2.4949(2), 2.4198(3) Å; PdSb₂, 2.6765(9), 2.838(2) Å; PtSb₂, 2.671(1), 2.782(2) Å; PtBi₂, 2.7706(8), 2.995(2) Å. The platinum-group dipnictides show a strengthening of the nonmetal-nonmetal bond with heavier nonmetal atoms, as evidenced by a bond-valence analysis. These dumbbell bonds are compared to other observed dumbbells in crystals. Comparisons are made to the transition-metal pyrite disulfides, where electronic effects are correlated with the nonmetal-nonmetal bond strength. The valence-matching principle is shown to correlate well with the observed structures of the alkali metal superoxides and alkaline earth metal peroxides. Bond valence analysis for a hypothetical ?cubic”? MnO₂ is given along a fluorite to pyrite pathway.     

Reaction of copper(II) cysteinate with thiosemicarbazide: Crystal structure of a complex of copper(II) thiocyanate with thiosemicarbazide

The reaction of copper(II) cysteinate with thiosemicarbazide (TSC) in water was found to yield complex of copper(II) thiocyanate of the [Cu(TSC)₂(SCN)₂] composition, whose crystal structure was determined by X-ray crystallography. Crystals of the complex are triclinic with a = 6.040 Å, b = 7.112 Å, c = 8.276 Å, α = 91.34°, β = 101.72°, Γ = 114.83°, Z = 2, space group \(P\bar 1\). Structural units of the complex are [Cu(TSC)₂]²⁺ centrosymmetric cations and (SCN)^? anions linked by hydrogen bonds (HB), as well as by electrostatic and π-π stacking interactions. The coordination polyhedron of Cu atoms is a square completed to bipyramid; the bonds Cu(1)-N(3), Cu(1)-S(1), and Cu(1)-S(2) are 2.002 Å, 2.303 Å, and 3.015 Å, respectively.     

Einkristall-RöntgenStrukturanalysen von Verbindungen mit einer kovalenten Metall-Metall-Bindung. VII. Die Kristall- und Molekülstruktur von dimeren Halogenobis- (pentacarbonylrhenium)indium(III), [(Re(CO)5)2In(μ-X)]2 (X = Cl,Br, I)

Single-Crystal X-Ray Analysis of Compounds with a Covalent Metal-Metal Bond. VII. Crystal and Molecular Structure of the Halogeno-Bridged Dimers of Halogenobis(pentacarbonylrhenium)indium(III), [(Re(CO)₅)₂In(μ-X)]₂ (X = Cl, Br, I) [(Re(CO)₅)₂In(μ-X)]₂ crystallizes if X = Cl and X = Br in the monoclinic system, space group P2₁/c (No. 14), with the lattice constants X = Cl: a = 10.540(6), b = 12.961(7), c = 26.071(12) Å, β = 106.3(1) Å, Z = 4, X = Br: a = 10.548(9), b = 13.108(7), c = 26.192(15) Å, β = 106.0(2)°, Z = 4 and if X = I in the triclinic system, space group P1 (No. 2), with the lattice constants a = 10.739(2), b = 7.160(1), c = 13.647(1) Å, α = 68.65(9), β = 71.89(9), γ = 65.52(9)°, Z = 1. The central molecular fragment consists of a plane In₂X₂ ring with the mean In—X distances: X = Cl: 2.624(6) Å, X = Br: 2.764(3) Å and X = I: 2.986(2) Å and the angles In—X—In/X—In—X, X = Cl: 97.2(2)°/ 82.8(2)°, X = Br: 94.8(1)°/85.2(1)° and X = I: 96.47(5)°/83.53(5)°. Two Re(CO)₅ groups are bonded to each of these In atoms to form a distorted tetrahedral coordination. The mean In—Re bond-distances are: X = Cl: 2.797(2), X = Br: 2.796(2) and X = I:2.811 (2) Å. There is a octahedral coordination around the Re atoms.     

Molecular and crystal structure of pyrylium squarylium dyes

The crystal structures of new dyes: 4-[[3-[[2,6-bis-(tert-butyl)-4H-pyran-4-ylidene]methyl]-2-oxido-4-oxo2-cyclobuten-]-ylidene]methyl]2,6-bis(tert-butyl)pyrylium (I) and its thio analog (II) were determined. Crystal data: space group P1 (I), P2₁/n (II); a = 5.960(9) Å (I), 10.400(4) Å (II); b = 9.366(3) Å (I), 12.242(4) Å (II); c = 13.948(3) Å (I), 14.482(6) Å (II); α = 70.43(2)° (I), 90.0° (II); ß = 84.82(9)° (I), 94.65(3)° (II); γ = 79.10(9)° (I), 90.0° (II); V = 720.0 ų (I), 1837.7 ų (II); Z = I (I), 2 (II); d_calc = 1.131 g/cm³ (I), 086 g/cm³ (II); R1(F) 0.049 (I), 0.045 (II). The substituents are trans-oriented relative to the planar 4-membered ring. Bond length distribution points to a considerable electron density delocalization over the whole molecule except the Bu^t groups. The pyrane rings are oriented differently relative to the central group; in II the rings lie in the same plane which is rotated through 7.7° with respect to the central fragment, whereas in I they lie in parallel planes which are 1.38 Å apart and deviate from the central fragment to opposite sides, forming with it dihedral angles of 12.8°. These conformational differences are possibly the result of the action of crystal field forces. In I molecules are arranged as overlapping stacks, whereas in II the pairwise parallel dye molecules are oriented in such a way that their long molecular axes are perpendicular to the long axes of the neighboring pair, resulting in a herringbone packing.     

Struktur von S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantan und 9,10-Diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantan

Structure of S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane and 9,10-Diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane S-9,10-Dimethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane ( 1 ) and 9,10-diethyl-1,3,5,7-tetraarsa-2,4,6,8-tetraoxaadamantane ( 2 ) have been prepared by the reaction of propionic acid, propionic anhydride and butyric acid, butyric anhydride, respectively, with arsenic(III)-oxide. The crystals of 1 are rhombic, a = 6.902(4), b = 11.121(5), c = 13.988(8), space group P2₁2₁2₁. The crystals of 2 are monoclinic, a = 11.757(10), b = 11.255(10), c = 18.631 (18), β = 91.78(7), space group P2₁/n. The mean bond lengths and angles in 1 are AsO = 1.790 Å, AsC = 1.959 Å, OAsO = 100.60°, CAsO = 99.65°, AsOAs = 128.77°, AsCAs = 118.73°, and in 2 they are AsO = 1.780 Å, AsC = 1.978 Å, OAsO = 101.45°, CAsO = 99.55°, AsOAs = 129.64°, AsCAs = 117.72°.     

Mesityl‐phenolato‐vanadium(III)‐Komplexe: Synthese,Struktur und Verhalten

Mesityl‐vanadium(III)‐phenolate Complexes: Synthesis, Structure, and Reactivity Protolysis reactions of [VMes₃(THF)] with ortho‐substituted phenols (2‐iso‐propyl‐(H–IPP), 2‐tert‐butyl(H–TBP), 2,4,6‐trimethylphenol (HOMes) and 2,2′biphenol (H₂–Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)₂(THF)₂] (OAr = IPP ( 1 ), TBP ( 2 )), [VMes₂(OMes)(THF)] ( 4 ), [V(OAr)₃(THF)₂] (OAr = TBP ( 3 ), OMes ( 5 )), and [V₂(Biphen)₃(THF)₄] ( 6 ). Treatment of 6 with Li₂Biphen(Et₂O)₄ results in formation of [{Li(OEt₂)}₃V(Biphen)₃] ( 7 ) and with MesLi complexes [{Li(THF)₂}₂VMes(Biphen)₂] · THF ( 8 ) and [{Li(DME)}VMes₂(Biphen)] ( 9 ) are formed. Reacting [VCl₃(THF)₃] with LiOMes in 1 : 1 to 1 : 4 ratios yields the componds [VCl_3–n(OMes)_n(THF)₂] (n = 1 ( 5 b ), 2 ( 5 a ), 3 ( 5 )) and [{Li(DME)₂}V(OMes)₄] ( 5 c ), the latter showing thermochromism due to a complexation/decomplexation equilibrium of the solvated cation. The mixed ligand mesityl phenolate complexes [{Li(DME)_n}{VMes₂(OAr)₂}] (OAr = IPP ( 10 ), TBP ( 11 ), OMes ( 12 ) (n = 2 or 3) and [{Li(DME)₂}{VMes(OMes)₃}] ( 15 ) are obtained by reaction of 1 , 2 , 5 a and 5 with MesLi. With [{Li(DME)₂(THF)}{VMes₃(IPP)}] ( 13 ) a ligand exchange product of 10 was isolated. Addition of LiOMes to [VMes₃(THF)] forming [Li(THF)₄][VMes₃(OMes)] ( 14 ) completes the series of [Li(solv.)_x][VMes_4–n(OMes)_n] (n = 1 to 4) complexes which have been oxidised to their corresponding neutral [VMes_4–n(OMes)_n] derivatives 16 to 19 by reaction with p‐chloranile. They were investigated by epr spectroscopy. The molecular structures of 1 , 3 , 5 , 5 a , 5 a – Br , 7 , 10 and 13 have been determined by X‐ray analysis. In 1 (monoclinic, C2/c, a = 29.566(3) Å, b = 14.562(2) Å, c = 15.313(1) Å, β = 100.21(1)°, Z = 8), 3 (orthorhombic, Pbcn, a = 28.119(5) Å, b = 14.549(3) Å, c = 17.784(4) Å, β = 90.00°, Z = 8), ( 5 ) (triclinic, P1, a = 8.868(1) Å, b = 14.520(3) Å, c = 14.664(3) Å, α = 111.44(1)°, β = 96.33(1)°, γ = 102.86(1)°, Z = 2), 5 a (monoclinic, P2₁/c, a = 20.451(2) Å, b = 8.198(1) Å, c = 15.790(2) Å, β = 103.38(1)°, Z = 4) and 5 a – Br (monoclinic, P2₁/c, a = 21.264(3) Å, b = 8.242(4) Å, c = 15.950(2) Å, β = 109.14(1)°, Z = 4) the vanadium atoms are coordinated trigonal bipyramidal with the THF molecules in the axial positions. The central atom in 7 (trigonal, P3c1, a = 20.500(3) Å, b = 20.500(3) Å, c = 18.658(4) Å, Z = 6) has an octahedral environment. The three Li(OEt₂)⁺ fragments are bound bridging the biphenolate ligands. The structures of 10 (monoclinic, P2₁/c, a = 16.894(3) Å, b = 12.181(2) Å, c = 25.180(3) Å, β = 91.52(1)°, Z = 4) and 13 (orthorhombic, Pna2₁, a = 16.152(4) Å, b = 17.293(6) Å, c = 16.530(7) Å, Z = 4) are characterised by separated ions with tetrahedrally coordinated vanadate(III) anions and the lithium cations being the centres of octahedral and trigonal bipyramidal solvent environments, respectively.     

Synthesis,Crystal Structure,and Magnetic Properties of (2,2′‐dipyridylamine)(X−) Copper(II) Complexes (X−: Cyanate,Dicyanamide, Acetate,Thiocyanato)

The synthesis, structure, and magnetic properties of four 2,2′‐dipyridylamine ligand (abbreviated as Hdpa) containing copper(II) complexes. There is one binuclear compound, which is [Cu₂(μ_1,1‐NCO)₂(NCO)₂(Hdpa)₂] ( 1 ), and three mononuclear compounds, which are [Cu{N(CN)₂}₂(Hdpa)₂] ( 2 ), [Cu(CH₃CO₂)(Hdpa)₂·N(CN)₂] ( 3 ), and [Cu(NCS)(Acac)] ( 4 ). Compounds 1 and 4 crystallize in the monoclinic system, space group P2(1)/c and Z = 4, with a = 8.2465(6) Å, b = 9.3059(7) Å, c = 16.0817(12) Å, β = 91.090(1)°, and V = 1233.90(16) ų for 1 and a = 7.6766(6) Å, b = 21.888(3) Å, c = 10.4678(12) Å, β = 90.301(2)°, and V= 1758.8(4) ų for 4 . Compounds 2 and 3 crystallize in the triclinic system, space group P‐1 and Z = 1, with a = 8.1140(3) Å, b = 8.2470(3) Å, c = 9.3120(4) Å, β = 102.2370(10)°, and V = 592.63(4) ų for 2 and a = 7.4780(2) Å, b = 12.5700(3) Å, c = 13.0450(3) Å, β = 96.351(2)°, and V = 1211.17(5) ų for 3 . Complex ( 1 ), the magnetic data was fitted by the Bleaney‐Bowers equation (1). A very good fit was derived with J = 23.96, Θ = ?1.5 (g = 1.97). Complex ( 1 ) shows the ferromagnetism. Complexes ( 2 ), ( 3 ) and ( 4 ) of have the it is the typical paramagnetic behavior of unpaired electrons. Under a low temperature around 25 K, complexes ( 2 ) and ( 3 ) show weak ferromagnetic behavior. They are the cause of hydrogen bonds.     

Synthesis,crystal structure,and luminescent properties of a new modification of the zinc(II) dichloride complex with phthalazine

The coordination compound [ZnCl₂(Phtz)₂] has been synthesized by the reaction of ZnCl₂ with phthalazine (Phtz, L, C₈H₆N₂) in an ethanol solution. Its crystal structure has been determined: crystals are triclinic, space group P 0000000, a = 7.346(1) Å, b = 8.095(1) Å, c = 14.275(1) Å, α = 85.63(1)°, β = 75.75(1)°, γ = 88.43(1)°, V = 820.4(2) ų, ρ_calc = 1.605 g/cm³, Z = 2. The zinc atom is tetrahedrally coordinated to two crystallographically nonequivalent chlorine atoms and two nitrogen atoms of the ligands L (Zn(1)–N(1), 2.036(4) Å; Zn(1)–N(3), 2.043(4) Å; Zn(1)–Cl(1), 2.225(2) Å; Zn(1)–Cl(2), 2.220(2) Å; angles NZnN, 106.1(2)°; ClZnCl, 116.47(7)°). The complexes are combined into a 1D supramolecular structure by nonclassical hydrogen bonds C–H···Cl and π–π-stacking interaction between centrosymmetric pairs of aromatic rings of one of the independent ligands. The compounds [CdI₂(Phtz)] and [HgBr₂(Phtz)] have also been synthesized, and their luminescent properties have been studied.     

A New Type of Divalent Europium Compound MEuPO4 (M = K,Rb, Cs), its Synthesis,Crystal Structure,and Properties

Phosphates MEuPO₄ with M = K, Rb, and Cs were synthesized by the reduction of EuPO₄ with alkali metal vapour under 1 Pa of argon pressure at 260–530°C in sealed tantalum or niobium lined glass tubes. All the compounds belong to the β-K₂SO₄ orthorhombic structure with a = 7.359(3), b = 9.630(4), c = 5.569(2) Å, V = 394.7(2) ų for KEuPO₄, a = 7.462(3), b = 9.797(3), c = 5.649(2) Å, V = 413.0(2) ų for RbEuPO₄ and a = 7.889(2), b = 10.099(2), c = 5.820(4) Å, V = 463.6(2) ų for CsEuPO₄. Samples are stable and not hygroscopic in air at room temperature but hydrolyse to Eu₅(PO₄)₃OH, hexagonal, a = 9.764(2), c = 7.262(2) Å, on heating in water and decompose to Eu₃(PO₄)₂, hexagonal, a = 5.393(1), c = 19.838(3) Å, under argon at ca. 600°C. All the five compounds are paramagnetic.     

Darstellung und Kristallstrukturen von Ln2Al3Si2 und Ln2AlSi2 (Ln: Y,Tb–Lu)

Synthesis and Crystal Structures of Ln ₂Al₃Si₂ and Ln ₂AlSi₂ ( Ln : Y, Tb–Lu) Eight new ternary aluminium silicides were prepared by heating mixtures of the elements and investigated by means of single‐crystal X‐ray methods. Tb₂Al₃Si₂ (a = 10.197(2), b = 4.045(1), c = 6.614(2) Å, β = 101.11(2)°) and Dy₂Al₃Si₂ (a = 10.144(6), b = 4.028(3), c = 6.580(6) Å, β = 101.04(6)°) crystallize in the Y₂Al₃Si₂ type structure, which contains wavy layers of Al and Si atoms linked together by additional Al atoms and linear Si–Al–Si bonds. Through this there are channels along [010], which are filled by Tb and Dy atoms respectively. The silicides Ln₂AlSi₂ with Ln = Y (a = 8.663(2), b = 5.748(1), c = 4.050(1) Å), Ho (a = 8.578(2), b = 5.732(1), c = 4.022(1) Å), Er (a = 8.529(2), b = 5.719(2), c = 4.011(1) Å), Tm (a = 8.454(5), b = 5.737(2), c = 3.984(2) Å) and Lu (a = 8.416(2), b = 5.662(2), c = 4.001(1) Å) crystallize in the W₂CoB₂ type structure (Immm; Z = 2), whereas the structure of Yb₂AlSi₂ (a = 6.765(2), c = 4.226(1) Å; P4/mbm; Z = 2) corresponds to a ternary variant of the U₃Si₂ type structure. In all compounds the Si atoms are coordinated by trigonal prisms of metal atoms, which are connected by common faces so that Si₂ pairs (d_Si–Si: 2.37–2.42 Å) are formed.     

Synthesis and crystal structure of the silver nitrate complex with 4,4′-trimethylenedipiperidine [Ag(C<Subscript>13</Subscript>H<Subscript>26</Subscript>N<Subscript>2</Subscript>)]NO<Subscript>3</Subscript>

A new coordination compound [AgNO₃(C₁₃H₂₆N₂)] was synthesized and structurally characterized. The crystals are triclinic: space group P \(\bar 1\), a = 6.157(1) Å, b = 10.074(1) Å, c = 14.153(1) Å, α = 102.36(1)°, β = 92.16(1)°, γ = 107.33(1)°, V = 813.7(2) ų, ρ_calcd = 1.552 g/cm³, Z = 2. The structure contains centrosymmetric rings formed by two Ag⁺ ions and two bridging trimethylenedipiperidine ligands. The coordination of Ag⁺ ions is close to linear (Ag(1)-N(1), 2.192(5) Å; Ag(1)-N(2), 2.212(5) Å; angle N(1)Ag(1)N(2), 162.7(2)°). Anions NO ₃ ^? form weak bonds with silver ions (Ag(1)…O(1), 2.783(5) Å; Ag(1)-O(3), 2.893(5) Å) and combine rings into supramolecular bands running in the diagonal direction of the unit cell.     

Untersuchungen über S?H …︁ S-Wasserstoffbrücken Die Kristallstruktur der Diphenyldithiophosphinsäure bei 140 und 293 K

Die Kristallstruktur der Diphenyldithiophosphinsäure (C₆H₅)₂P(S)SH wurde röntgenographisch bei tiefer Temperatur und Normaltemperatur aus Einkristalldiffraktometerdaten bestimmt und bis zu R-Werten von 0,037 (140 K, (sin Θ)/λ < 0,81 Å^?1) und 0,035 (293 K, (sin Θ)/λ < 0,64 Å^?1) verfeinert. Die Verbindung kristallisiert in der monoklinen Raumgruppe P2₁/c mit den bei 140 K (in Klammern: 293 K) gemessenen Gitterkonstanten a = 9,824(3) (9,887), b = 10,061(3) (10,175), c = 14,342(4) (14,433) Å, β = 122,08(3) (121,73)° und V = 1201,1 (1234,9) ų, Z - 4. Im Kristall sind individuelle Moleküle über fast lineare S? H…?S-Wasserstoffbrückenbindungen zu schraubenförmig gewundenen Ketten verknüpft. Bei 140 K beträgt der S…?S-Abstand innerhalb der Brücke 3,790(1) Å; die weiteren geometrischen Daten der Wasserstoffbrücke sind: d(S? H): 1,25(2), d(S…?H): 2,56(2), d(P? S): 2,077(1), d(P?S): 1,954(1) Å, ? (S? H…?S): 169,5(14), ? (P? S…?S): 98,87(2), ? (P?S…?S): 96,65(2)°. Investigations on Compounds Containing S? H…?S Hydrogen Bonds. Crystal Structure of Diphenyldithiophosphinic Acid at 140 and 293 K The crystal structure of diphenyldithiophosphinic acid (C₆H₅)₂P(S)SH was determined from X-ray diffraction data collected at 140 and 293 K and was refined to R factors of 0.037 (140 K, (sin Θ)/λ < 0.81 Å^?1) and 0.035 (293 K, (sin Θ)/λ < 0.64 Å^?1) respectively. The compound crystallizes in the monoclinic space group P2₁/c with unit cell parameters at 140 K (in parentheses: at 293 K): a = 9.824(3) (9.887), b = 10.061(3) (10.175), c = 14.342(4) (14.433) Å, β = 122.08(3) (121.73)° and V = 1201.1 (1234.9) ų, Z = 4. In the crystalline state individual molecules are linked together by nearly linear S? H…?S hydrogen bonds so that endless helical chains are formed. At 140 K the S…?S distance within the hydrogen bond is 3.790(1) Å; the other distances and angles associated with the bridge are: d(S? H): 1,25(2), d(S…?H): 2,56(2), d(P? S): 2,077(1), d(P?S): 1.954(1) Å, ? (S? H…?S): 169.5(14), ? (P? S…?S): 98.87(2), ? (P? S…?S): 96.65(2)°.     

The crystal structure of bisphenoxatelluronium dinitrate,C24H16O9N2Te2

Bisphenoxatelluronium dinitrate is monoelinie, P2₁/c: a = 11.638(4), b = 28.266(8), c = 8.546(3) å, β = 119.73(2)°, z = 4 at t = 22°. All atoms including hydrogen were located. The two ring systems, I and II, are folded along their Te-O axes, 147° and 163°, respectively. The average ring bond distances are: Te-C = 2.091, C-C = 1.377, C-O = 1.370 Å. Each Te is bonded to one NO₃ group, Te1-ON1 = 2.485(5), Te2-ON4 = 2.393(4) Å, and an oxygen bridge connects the ring systems, Te1-OB = 1.966(4), Te2-OB = 2.001(4) Å, Te1-OB-Te2 = 125.0(2)°. The bond distances and angles of the structure are compared to those of related compounds.     

The crystal structure of [Mg(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>][VO(edta)] · 3.5H<Subscript>2</Subscript>O

The crystal structure of complex [Mg(H₂O)₆][VO(edta)] · 3.5H₂O (I) was determined by X-ray diffraction study. The crystals are monoclinic, a = 6.779 Å, b = 13.373(6) Å, c = 25.054 Å, β = 96.55°, Z = 4, space group P2₁. The unit cell contains two independent [VO(edta)]^2? anions, two independent [Mg(H₂O)₆]²⁺ cations, and seven crystal-water molecules. The coordination polyhedron of each vanadium atom is formed by five donor atoms of the edta ligand (2N + 3O) (V(1)-N(1), 2.278 Å; V(1)-N(2), 2.149 Å; V(2)-N(3), 2.301 Å; V(2)-N(4), 2.165 Å; V-O(acet), 2.00 ± 0.02 Å) and the oxygen atom of the oxo group (V-O, 1.60 ± 0.01 Å). The edta ligands and the vanadium atom form three glycinate rings: two R-type rings and one G-type ring (one acetate branch remains free), as well as an E-type ring with an asymmetric gauche configuration. The [Mg(H₂O)₆] cations are slightly distorted octahedra (Mg-O, 2.013–2.132 Å, the OMgO angles are 86.6°–94.2°). The H₂O molecules form a bifurcate system of H-bonds. The crystals of compound I belong to OD-type structures with an incomplete ordering of layers.