Synthesis,Crystal and Molecular Structures of [Co(MH)2(Thio)2][BF4] · H2O and [Co(DH)2(NH3)2][BF4]

Crystal structures of [Co(MH)₂(Thio)₂][BF₄] · H₂O (I) and [Co(DH)₂(NH₃)₂][BF₄] (II), where MH^– is H₃C–C(NOH)–C(NO^–)–H and DH^– is H₃C–C(NOH)–C(NO^–)–CH₃, were determined by X-ray diffraction. The crystals are monoclinic, space group C2/c, unit cell parameters (for I and II, respectively): a = 22.018(2) Å, b = 7.943(1) Å, c = 11.681(1) Å, = 92.68(1)° and a = 21.436(2) Å, b = 6.400(2) Å, c = 12.389(2) Å, = 113.13(1)°. In both cases, the Co(III) coordination polyhedron is a centrosymmetrical trans-octahedron, N₄S₂ for I and N₆ for II. In the crystals of I and II, the complex cations and the outer-sphere [BF₄]^– anions (and the crystal water molecules in I) form elaborate hydrogen bonding system.     

Structure of Complexes Formed in the CuX2–Cu–N-Allylisoquinolinium Chloride System (X = Cl,Br)

The crystals of N-allylisoquinolinium chlorides of the compositions [C₉H₇N(C₃H₅)]₂Cu^IICl₄ (I), [C₉H₇N(C₃H₅)]Cu^ICl₂ · H₂O (II), and [C₉H₇N(C₃H₅)]Cu^ICl_1.43Br_0.57 · H₂O (III) were prepared by alternating-current electrosynthesis. X-ray diffraction analysis (using diffractometer models DARCH1 for I, STOE for II, and KUMA/CCD for III, MoK radiation) showed that the crystals of I are monoclinic, space group P2₁/n, a = 14.91(1) Å, b = 10.41(1) Å, c = 16.90(1) Å, = 109.73(8)°, V = 2470(8) ų, Z = 4. The crystals of isostructural compounds II and III are triclinic, space group P, Z = 2; crystals II: a = 7.2446(6) Å, b = 7.4379(6) Å, c = 12.110(1) Å, = 80.95(1)°, = 85.55(1)°, = 86.60(1)°, V = 641.8(2) ų; crystals III: a = 7.253(2) Å, b = 7.459(4) Å, c = 12.151(5) Å, = 80.82(4)°, = 83.73(3)°, = 86.81(4)°, V = 644.6(9) ų. The structure of I is composed of Cu^IICl₄ ^2– tetrahedra and N-allylisoquinolinium cations united by C–H···Cl hydrogen bonds in corrugated layers. The crystal structures of -complexesII and III are built of [C₉H₇(C₃H₅)]₂Cu₂ ^IX₄ dimers, which form layers along the c axis due to the C–H···X hydrogen bonds. An important role in the structure formation is played by water molecules, which crosslink the organometallic layers to form a three-dimensional framework through the O–H···X contacts.     

Synthesis and Structural Features of Copper(I) Chloride and Bromide Complexes with the N,N,N′,N′-Tetraallylpiperasinium Cation (L2+) of Compositions L2+[CuCl2]– 2 and L2+[CuBr3]2–

Crystals of the -complex [C₄H₈N₂(C₃H₅)₄]²⁺[CuCl₂]^– ₂ (I) were prepared by ac electrochemical synthesis from copper and N,N,N,N-tetraallylpiperasinium chlorides in alcohol solution. Similar synthesis with the use of the metal and N,N,N,N-tetraallylpiperasinium bromides yielded the complex [C₄H₈N₂(C₃H₅)₄]²⁺[CuBr₃]^2– (II). Structures I and II were studied by X-ray diffraction (DARCh automated single-crystal diffractometer, MoK radiation). Crystals of I are triclinic, space group P1¯, a = 8.650(3) Å, b = 7.572(2) Å, c = 8.095(3) Å, = 100.45(2)°, = 83.91(2)°, = 99.89(2)°, V = 512.1(6) ų, Z = 1. Crystals of II are orthorhombic, space group Pn2₁ a, a = 17.673(3) Å, b = 14.369(6) Å, c = 8.244(2) Å, V = 2093(2) ų, Z = 4. In structure I, the potentially tetradentate N,N,N,N-tetraallylpiperasinium cation uses two centrosymmetric allyl groups for bonding with copper atoms, whose environment is completed to the trigonal-planar coordination with the chlorine atoms. The [C₄H₈N₂(C₃H₅)₄]²⁺[CuCl₂]^– ₂ groups are joined into a three-dimensional framework by weak hydrogen bonds. The inorganic fragment CuCl^– ₂ is partially disordered, which appears as splitting of the positions of the copper atom and one of the chlorine atom. In compound II, the inorganic fragment occurs as an unusual trigonal-planar CuBr^2– ₃ anion; the N,N,N,N-tetraallylpiperasinium cation is not involved in metal coordination.     

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.     

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.     

Uncommon Behavior of Copper(I) Tetrafluoroborate and Perchlorate in [Cu(DAF)(H2O)]BF4and [Cu(DAF)(ClO4)] π-Complexes (DAF—Diallyl Formamide)

Crystals of [Cu(DAF)(H₂O)]BF₄(I) and [Cu(DAF)(ClO₄)] (II) (DAF is diallyl formamide) were synthesized by an alternate-current electrochemical method, and their structures were determined (MoK radiation, 1247 and 859 independent reflections with I 2(I), R= 0.043 and 0.032 for Iand II, respectively). The complexes crystallize in space group P2₁/n, Z= 4. For I, a= 10.782(3) Å, b= 12.096(5) Å, c= 9.185(3) Å, = 103.62(3)°, and V= 1164.2(7) ų; for II, a= 10.064(3) Å, b= 10.753(6) Å, c= 10.002(3) Å, = 87.52(4)°, and V= 1081.4(8) ų. The copper atom in structures Iand IIcoordinates both C=C bonds in one DAF molecule and oxygen atom of the amide group of another DAF molecule, as well as an oxygen atom of H₂O (in I) or ClO₄(in II) in the axial position. The uncommon behavior of the anions in structures Iand IIis explained by their different values of Pierson hardness.     

Crystal and molecular structures of benzophenone phenylhydrazone derivatives with anticancer activity

The X-ray crystal structures of 4,4-dihydroxybenzophenone-2,4-dinitrophenylhydrazone (I) and 2,2-dihydroxybenzophenone-2,4-dinitrophenylhydrazone (II) have been determined in order to study the structural characteristics of these molecules that may contribute to their antiestrogenic and cytotoxic properties. These structures have been compared to other hydrazone derivatives as well as tamoxifen, an antiestrogen drug presently used clinically for the treatment of breast cancer.Crystal data: (I) C₁₉H₁₄N₄O₆ · C₄H₁₀O; MW=468.0; monoclinic,P2₁;a=8.601(2), b=15.502(8), c=16.851(4) Å,=98.58(2)°;Z=8; finalR=0.036 for 1904 observed reflections. (II C₁₉H₁₄N₄O₆ · H₂O; MW=410.0; monoclinic,P2₁/c;a=7.603(2),b=19.552(4),c=12.493(3) Å,=92.11(1)°;Z=4; finalR=0.045 for 1171 observed reflections.     

Synthesis and Crystal Structures of Copper(I) Complexes with N-Allylhexamethylenetetraminium Chloride Obtained in Different Acidic Media

The crystals of [(CH₂)₆N₄(C₃H₅)]Cu₂Cl₃ (I), [(CH₂)₆N₄(C₃H₅)]Cu₂Cl₃ (II), and [(CH₂)₆N₄(C₃H₅)]CuCl₂ (III) complexes were electrochemically synthesized (ac) from CuCl₂ · 2H₂O and N-allylhexamethylenetetraminium chloride in ethanol solutions at pH 6, 4.5, and 3. Their structures were determined using X-ray diffraction analysis (DARCh diffractometer, MoK radiation, /2 scan mode). Complex Icrystallizes in the monoclinic system: space group A2/a, a = 24.812(6) Å, b = 8.855(3) Å, c = 12.080(2) Å, = 89.21(3)°, and Z = 8. Complex II crystallizes in the triclinic system: space group P , a = 7.618(2) Å, b = 7.048(2) Å, c = 13.150(3) Å, = 97.50(2)°, = 92.70(2)°, = 100.74(2)°, and Z = 2. The crystals of complex III are orthorhombic: space group Pmn2₁, a = 7.478(2) Å, b = 8.827(2) Å, c = 9.662(3) Å, Z = 2. The organic cation in complex I acts as a tridentate ,,-ligand; that in complex II, as a bidentate ,-ligand. In complex III, the organic cation is involved in coordination with the copper(I) atom only through one nitrogen atom.     

Synthesis and Structure of Tetraphenylantimony Oximates Ph4SbON=CRR′ (CRR′ = C6H9−C6H9-2 and R = Ph,R′ = C(O)Ph)

The reaction of pentaphenylantimony and the oxime HON=CRR taken in 1 : 1 molar ratio in toluene gave tetraphenylantimony oximates Ph₄SbON=CRR (CRR = C₆H₉–C₆H₉-2 (I) and R = Ph, R = C(O)Ph (II)). According to X-ray diffraction data, the Sb atoms in I and II have a distorted trigonal-bipyramidal coordination with oximate ligands in the axial positions. The C_axSbO angles are 177.6(1)° in I and 176.58(6)° in II. The Sb–C bond lengths lie in the ranges of 2.120(4)–2.203(4) Å for I and 2.122(2)–2.181(2) Å for II. The Sb–O bond lengths are 2.120(2) Å (I) and 2.166(1) Å (II). The lengths of the intramolecular Sb···N contacts are 2.806(3) and 2.918(2) Å in I and II, respectively.     

Building three-dimensional metal phosphites from the corner-shared four-membered rings chain

Three new compounds, a one-dimensional (1D) zinc phosphite, (C₄H₈N₂H₄)[Zn(HPO₃)₂] (I), two three-dimensional (3D) metal phosphites (C₄H₈N₂H₄)[Zn₃(HPO₃)₄] (II) and (C₄H₈N₂H₄)[Zn_(3−x)Co_x(HPO₃)₄(H₂O)₂] (x≈0.83) (III) have been synthesized under hydrothermal conditions templated by piperazine and characterized by single-crystal X-ray diffraction, XRD, IR, UV-vis spectra and SQUID magnetometer. Compound I displays 1D chain-like structure, containing corner-shared (cs) four-membered rings. Interestingly, the structures of II and III show 1D chains similar to those observed in I. It is noteworthy that III represents the first cobalt-substituted zinc-phosphite. Crystal data: I, monoclinic, C2/c, a=17.748(2) Å, b=7.428(9) Å, c=8.8071(11) Å, β=105.345(3)°, V=1091.9 Å³, Z=4. II, Monoclinic P2₁/c, a=9.9435(4) Å, b=10.1438(3) Å, c=17.8164(5) Å, β=95.665(2)°, V=1788.27 Å³, Z=4, and III, Monoclinic P2₁/c, a=7.2338(2) Å, b=15.0238(5) Å, c=9.2153(3) Å, β=107.741(2)°, V=953.88(5) Å³, Z=2.     

Cupro(I)-π-complexes with 1-allyloxybenzotriazole: Synthesis and crystal structure of CuBF4 · 2C6H4N3(OC3H5) · H2O and CuCF3COO · C6H4N3(OC3H5)

The crystals of copper(I) π-complexes CuBF₄ · 2C₆H₄N₃(OC₃H₅) · H₂O (I) and CuCF₃COO · C₆H₄N₃(OC₃H₅) (II) were obtained by alternating-current electrosynthesis and studied by X-ray diffraction: I, space group P2₁/n, a = 10.226(8), b = 13.233(10), c = 16.30(1) Å, β = 98.13(1)°, V = 2249(2) ų, Z = 4, R = 0.0705, 577 reflections; I, space group P $ P\bar 1 The crystals of copper(I) π-complexes CuBF₄ · 2C₆H₄N₃(OC₃H₅) · H₂O (I) and CuCF₃COO · C₆H₄N₃(OC₃H₅) (II) were obtained by alternating-current electrosynthesis and studied by X-ray diffraction: I, space group P2₁/n, a = 10.226(8), b = 13.233(10), c = 16.30(1) ?, β = 98.13(1)°, V = 2249(2) ?³, Z = 4, R = 0.0705, 577 reflections; I, space group P , a = 8.8625(7), b = 9.0647(4), c = 9.1650(5) ?, α = 68.37(2)°, β = 85.31(3)°, γ = 69.86(2)°, V = 646(4) ?³, Z = 2, R = 0.1354, 2669 reflections. In compound I, the tetrahedrally distorted trigonal pyramidal environment of the copper atom comprises two nitrogen atoms of two organic molecules (L), the C=C bond of another L molecule, and the O atom of the water molecule. Due to the bridging function of L molecule, infinite chains [Cu · 2C₆H₄N₃(OC₃H₅) · H₂O] _n are formed in the structure along the y axis. The chains are, in turn, assembled into layers through strong O-H…F hydrogen bonds involving both hydrogen atoms of the water molecule and fluorine atoms of the BF₄⁻ anion. In compound II, two bridging oxygen atoms of two trifluoroacetate anions and two copper atoms form a centrosymmetric dimer. The nitrogen atom of the benzotriazole ring of one molecule L and the C=C double bond of the allyl group of the other molecule L complete the distorted coordination tetrahedron of the metal atom. Owing to the bridging function of the L molecule, the [CuCF₃COO · C₆H₄N₃(OC₃H₅)]₂ dimers are connected to form infinite double chains associated in a three-dimensional framework by only weak interactions. The replacement of the covalently bonded trifluoroacetate anion by an outer-sphere tetrafluoroborate ion opens up the possibility for metal atom binding to three L molecules simultaneously. Original Russian Text ? E.A. Goreshnik, M.G. Mys’kiv, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 11, pp. 826–830.     

Copper(I) π-Complexes with Alkyne Ligands: Synthesis and Crystal Structure of M[CuCl2(HOCH2C≡CCH2OH)] (M = K+, NH+ 4)

Crystals of anionic complexes of the composition M[CuCl₂(HOCH₂CCCH₂OH)], where M = NH₄ ⁺ (I), K⁺ (II), were isolated from concentrated aqueous solutions of CuCl and MCl (M = NH₄ ⁺, K⁺) in the presence of 2-butyne-1,4-diol. Their structures were studied by X-ray diffraction analysis. Isostructural crystals I and II are orthorhombic; Z = 8, space group Ibam; a = 6.735(1) and 6.666(2) Å, b = 17.206(3) and 16.874(6) Å, c = 15.172(3) and 15.032(4) Å, V = 1758(1) and 1691(1) ų, respectively. The compounds are built of individual [CuCl₂(HOCH₂CCCH₂OH)] anions; the NH₄ ⁺ (I) or K⁺ (II) cations are arranged in the voids between the anions. The -coordinated Cu(I) atoms have trigonal-planar environment of two chlorine atoms and CC bond of the 2-butyne-1,4-diol molecule. The Cu–(CC) distances in the -core are 1.892(4) and 1.887(6) Å, CC are 1.233(5) and 1.228(5) Å in I and II, respectively. In complex I, additional hydrogen bonds Cl···H–NH₃ (Cl···H 2.43(4) Å) and O···H–NH₃ (O···H 1.97(3) Å) stabilize the structure.     

Complexation with hydroxy host compounds,part 5. Structures and thermal analyses of 1,2,3,4,5-pentaphenylcyclopenta-2,4-dien-1-ol and its inclusion compounds with water and dimethylsulphoxide

The crystal and molecular structures of the title host compound (I), C₃₅H₂₆O, and its inclusion complexes with water (II), C₃₅H₂₆O·H₂O and dimethylsulphoxide (III), C₃₅H₂₆O·C₂H₆OS are reported. (I) is monoclinicC2/c,a = 9.725(1),b = 20.031(3),c = 26.545(3) Å, = 90.60(1)⁰,V = 5170 ų,Z = 8; (II) is triclinic, ,a = 10.206(1),b = 10.324(2),c = 14.425(2) Å, = 101.68(1), = 89.92(2), = 116.34(1)⁰,V = 1327 ų,Z = 2; (III) is monoclinicP2₁/n,a = 17.832(5),b = 10.109(3),c = 17.901(5) Å, = 111.93(2)⁰,V = 2993 ų,Z =4. The structures were solved by direct methods and refined to final residuals of 0.045, 0.048, and 0.071, respectively. Thermal analysis of the complexes corroborates the crystallographic results.     

Dimethyl- and Diethyltin(IV) Compounds with Perfluorobiphenyl-4-Thiolate and Perfluoronaphthalene-2-Thiolate Anions: The Crystal Structure of (CH3)2Sn(C12F9S)2

Compounds (CH₃)₂Sn(C₁₂F₉S)₂ (I), (CH₃)₂Sn(C₁₀F₇S)₂ (II), and (C₂H₅)₂Sn(C₁₀F₇S)₂ (III) were synthesized. Single crystals of Iwere grown and structurally characterized using X-ray diffraction analysis (1590 reflections, R = 0.0209). The crystals are orthorhombic, a = 40.848(8) Å, b = 6.058(1) Å, c = 11.183(2) Å, V = 2767(1) ų, (calcd.) = 2.024 g/cm³, space group Pbcn, Z = 4. The structure is built from monomeric molecules. The coordination polyhedron of the Sn atom (the SnC₂S₂ core) is a distorted tetrahedron. Compounds I–III are volatile when heated in vacuo. Thermolysis of these compounds results in SnO₂ (in air) or SnS₂ (in argon).     

Synthesis and Crystal Structure of the Heterovalent Copper(I,II) π-Complex Cu7Br6.48Cl1.52 ? 2C3N3(OC3H5)3

Single crystals of the heterovalent Cu^I,Cu^II π,σ-complex Cu₇Br_6.48Cl_1.52 ⋅ 2C₃N₃(OC₃H₅)₃ are synthesized by the ac electrochemical method from an ethanol solution containing 2,4,6-triallyloxy-1,3,5-triazine, CuCl₂ ⋅ 2H₂O, and CuBr₂. The unit cell parameters of the crystals are: space group , a = 8.271(3) Å, b = 11.391(3) Å, c = 11.821(3) Å, α = 67.43(1)°, β = 84.41(2)°, γ = 85.14(2)°, V = 1022(1) ų, and R(F) = 0.0714. The copper and halogen atoms form unique moieties Cu₆X₆ linked by bridging fragments [Cu²⁺ (C₃N₃(OC₃H₅)₃)₂]X₂ into infinite chains. Each inorganic moiety Cu₆X₆ is linked with four 2,4,6-triallyl- oxy-1,3,5-triazine molecules. The ligand molecule is coordinated to one Cu^II atom through the nitrogen atom of the triazine cycle and to two Cu^I atoms through the C=C bonds of two allyl groups. The Br content equal to 0.57 in the X(4) position linking the Cu^I and Cu^II atoms differs markedly from a value of 0.85–0.91 for the X(1), X(2), and X(3) positions linked only with the Cu(I) atoms.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 6, 2005, pp. 455–461.Original Russian Text Copyright © 2005 by Goreshnik, Schollmeyer, Mys’kiv.     

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.     

Synthesis and Structure of Complexes Formed in the CuCl2–Cu–N-allylquinolinium Chloride System

The crystals of [C₉H₇N(C₃H₅)]₂Cu^IICl₄(IV) were obtained through ac electrochemical synthesis using CuCl₂· 2H₂O, N-allylquinolinium chloride, and copper electrodes in an ethanol-benzene medium. These crystals transformed with time into crystals of the [C₉H₇N(C₃H₅)][Cu^IICl₃(C₉H₇N)] complex (V). When tin(II) chloride was added to the initial reagents, the [C₉H₇N(C₃H₅)]Cu^I ₂Cl₃complex (VI) was obtained. The X-ray diffraction analysis (DARCh-1 autodiffractometer, MoK radiation, Zr filter) indicated that complexes IVand Vcrystallize in the triclinic system: space group P ; for IV, a= 12.817(4), b= 10.435(3), c= 9.606(3) Å, = 97.94(2)°, = 107.28(2)°, = 95.99(2)°, V= 1200.6(6) ų, Z= 2; for V, a= 16.992(5), b= 8.243(2), c= 7.345(3) Å, = 91.89(3)°, = 91.19(3)°, = 88.18(3)°, V= 1027.5(6) ų, Z= 2. Crystals VIare monoclinic, space group P2₁/n, a= 13.578(5), b= 15.079(4), c= 6.953(4) Å, = 105.08(4)°, V= 1370.6(10) ų, Z= 4. Structures IV–VIconsist of N-allylquinolinium cations and different anions: isolated [CuCl₄]^2–tetrahedrons (IV), [C₉H₇NCuCl₃]^–tetrahedrons (V) containing a quinoline molecule, and a polymer chain |[Cu^I ₄Cl₆]^2–} _n (VI) in which two independent metal atoms have trigonal-pyramidal and planar-trigonal environments. The C=C bond of the allyl group is not involved in cooordination with the Cu(I) atom.     

Synthesis and properties of pyrazine-pillared Ag3Mo2O4F7 and AgReO4 layered phases

The new pyrazine-pillared solids, AgReO₄(C₄H₄N₂) (I) and Ag₃Mo₂O₄F₇(C₄H₄N₂)₃ (C₄H₄N₂=pyrazine, pyz) (II), were synthesized by hydrothermal methods at 150 °C and characterized using single crystal X-ray diffraction (I—P2₁/c, No. 14, Z=4, a=7.2238(6) Å, b=7.4940(7) Å, c=15.451(1) Å, β=92.296(4)°; II—P2/n, No. 13, Z=2, a=7.6465(9) Å, b=7.1888(5) Å, c=19.142(2) Å, β=100.284(8)°), thermogravimetric analysis, UV-Vis diffuse reflectance, and photoluminescence measurements. Individual Ag(pyz) chains in I are bonded to three perrhenate ReO₄^- tetrahedra per layer, while each layer in II contains sets of three edge-shared Ag(pyz) chains (π-π stacked) that are edge-shared to four Mo₂O₄F₇^3- dimers. A relatively small interlayer spacing results from the short length of the pyrazine pillars, and which can be removed at just slightly above their preparation temperature, at >150-175 °C, to produce crystalline AgReO₄ for I, and Ag₂MoO₄ and an unidentified product for II. Both pillared solids exhibit strong orange-yellow photoemission, at 575 nm for I and 560 nm for II, arising from electronic excitations across (charge transfer) band gaps of 2.91 and 2.76 eV in each, respectively. Their structures and properties are analyzed with respect to parent ‘organic free’ silver perrhenate and molybdate solids which manifest similar photoemissions, as well as to the calculated electronic band structures.     

Thiourea N- and S-Derivatives as Ligands: Synthesis and Crystal Structure of 4CuCl · 6All–NHCSNH2 and [(All–NH)2C–SC2H5]Cu2ClxBr3 – x (x = 0.765, All is Allyl)

Crystals of the compounds 4CuCl · 6CH₂=CH–CH₂–NHCSNH₂ (I) and [(CH₂=CH–CH₂–NH)₂C–SC₂H₅]Cu₂Cl _x Br_{3 – x} (x = 0.765) (II) were synthesized by the ac electrochemical method, and their crystal structures were determined (CuK and MoK radiation, 2575 and 1090 unique reflections with F 4(F), R = 0.050 and 0.028 for I and II, respectively). Complex I crystallizes in space group C2/c, a = 17.230(7) Å, b = 12.258(5) Å, c = 42.95(2) Å, = 97.48(4)°, V = 8994(7) ų, Z = 8. The structure of -complex II is described by space group P2₁/n, a = 10.633(5) Å, b = 9.280(5) Å, c = 16.024(4) Å, = 102.16(3)°, V = 1546(1) ų, Z = 4. Complex I is built from isolated units of the aforementioned composition; every allylthiourea molecule coordinates two metal atoms through the sulfur atom. The distorted tetrahedral surrounding of every Cu(I) atom involves three S atoms and one Cl atom. The N,N"-diallyl-S-ethylisotiouronium cation coordinates two copper atoms through the C=C bonds, 1.32(1) and 1.35(1)Å, uniting the cuprohalide chains in layers. The structure of complex II is very close to the structure of the previously studied -complex of diallylammonium [H⁺L]Cu₂Cl₃.     

A CoMFA Study of Dopamine D2 Receptor Agonists and X-Ray Crystal Structure of Quinelorane Dihydrochloride Dihydrate,R(−)-Apomorphine Hydrochloride and R(−)-<Emphasis Type="Italic">N</Emphasis>-<Emphasis Type="Italic">n</Emphasis>-Propylnorapomorphine Hydrochloride

A QSAR and CoMFA study of 33 agonists of the dopamine D2 receptor has been completed. These analogs belong to different chemical classes of compounds and include varied functional groups and stereoisomers. The CoMFA program was used to calculate the steric and electrostatic interaction energies as a probe atom or probe charge interacts with the molecules. Color contour maps show that bulky substituents with low electronegativity on the fused piperidine ring nitrogen are favored for enhanced activity. The maps also showed that small substituents with low electronegativity on the aromatic ring are favored for enhanced activity. The X-ray crystal structures of quinelorane dihydrochloride (1), R-(–)-apomorphine hydrochloride (2), and R-(–)-N-n-propylnorapomorphine hydrochloride (3) showed the three-dimensional structures and the hydrogen bonding interactions of these molecules in the crystal. Since many of the dopamine agonists are mostly rigid, conformationally restrained structures, these crystal structures are reasonable representations for the solution structures. Crystallographic data: (1) C₁₄H₂₂N₄2HCl2H₂O, orthorhombic space group P2₁2₁2₁, a = 7.223 (1) Å, b = 18.705 (2) Å, c = 13.465 (2) Å, Z = 4, final R = 0.045 for 4586 observed reflections (I > 3 (I)); (2) C₁₇H₁₇NO₂ HCl, orthorhombic space group P2₁2₁2₁, a = 11.535 (2) Å, b = 13.251 (1) Å, c = 20.348 (2) Å, Z = 8, final R = 0.08 for 1806 observed reflections (I > 3 (I)); (3) C₁₉H₂₁NO₂HCl, triclinic space group P1, a = 7.133 (1) Å, b = 11.247 (1) Å, c = 11.112 (2) Å, Z = 2, final R = 0.054 for 3779 observed reflections (I > 3(I)).