Crystal structures of a series of 3,8-di[-2-aryl-1-azenyl]-1,3,6,8-tetraazabicyclo[4.4.1]undecanes

The crystal and molecular structure of a series of 3,8-di[-2-aryl-1-azenyl]-1,3,6,8-tetraazabicyclo[4.4.1]undecanes (1–5) have been determined by single crystal X-ray diffraction analysis. In all five compounds, the tetraazabicycloundecane portion of the molecule assumes a cage-like, folded structure with the aryltriazene moieties aligned approximately parallel; the structure is held in the folded configuration by either intramolecular or intermolecular – stacking forces. Crystal data: 1 C₁₉H₂₂N₁₀O₄, monoclinic space group P2₁/c, a = 10.1846(7), b = 9.9556(7), c = 20.819(2) Å, = 98.725(1)°, V = 2086.5 (3) ų, Z = 4; 2 C₂₃H₂₈N₈O₄, triclinic, space group P, a = 6.7064(7), b = 12.9662(14), c = 14.054(2) Å, = 94.796(2), = 91.621(2), = 104.836(2)°, V = 1175.7(2) ų, Z = 2; 3 C₁₉H₂₂N₁₀O₄, monoclinic, space group P2₁/c, a = 14.237(2), b = 13.520(2), c = 11.5805(12) Å, = 113.514(2)°, V = 2044.0(4) ų, Z = 4; 4 C₂₁H₂₂N₁₀, monoclinic, space group C2/c, a = 54.247(3), b = 11.5531(7), c = 12.9670(7) Å, = 95.710(1)°, V = 8086.4(8) ų, Z = 16; 5 C₂₅H₃₂N₈ 0₄, monoclinic, space group P2₁/c, a = 10.2908(7), b = 16.5687(12), c = 15.1662(10) Å, = 94,188(1)°, V = 2579.0(3) ų, Z = 4.     

Synthesis, characterization, and X-ray crystal structure of di-(2,4-imidazolidinedione-5-ethyl)disulfide, C10H14N4O4S2

Di-(2,4-imidazolidinedione-5-ethyl)disulfide or homocystine hydantoin, C₁₀H₁₄N₄O₄S₂ (I), crystallizes in the non-centrosymmetric space group P2₁ (No. 4) with two molecules in the unit cell with a = 7.132(1), b = 9.282(2), c = 10.770(2) Å and = 105.68(1)°. The two imidazolidinedione rings are planar with a dihedral angle of 46.9°. The rings are joined by a diethyl disulfide bridge at chiral centers on the rings. The C-S-S-C torsion angle is –80°(–sc). The absolute stereochemistry of the chiral centers was determined to be (5S, 5S), = + 0.92 (11). Important bond distances include: S-S = 2.022(4); S-C (mean) = 1.809(8); and C=O (mean) = 1.224(7) Å. The compound is stabilized by a network of intermolecular carbonyl-to-amine hydrogen bonding and van der Waals cohesive forces.     

Crystal structure, thermal analysis, and IR spectrometric investigation of bis(tert-butylammonium) sulfate

Chemical preparation, X-ray single crystal, thermal analysis, and IR spectrometric investigation of (C₄H₁₂N)₂SO₄, denoted tBAS, are described. The compound crystallizes in the monoclinic system with C2/c space group. Its unit cell dimensions are a = 11.1585(5) Å, b = 6.2148(4) Å, c = 20.070(1) Å, = 102.004(4)°, V = 1361.4(1) ų, and Z = 4. The crystal structure of tBAS can be described as a typical thick layered organization built by all the components of the structure and centered by planes z = 1/4 and 3/4. Connection in these layers are established by N—H···O hydrogen bonds. Thermal analysis shows a reversible weak phase transition.     

Crystallographic studies of dihalogeno-tetramethylethylenediamine complexes of zinc,cadmium and mercury. I: crystal and molecular structure of dichloro-(N,N,N′,N′-tetramethylethylenediamine)zinc(II)

The crystal structure of dichloro-(N,N,N,N-tetramethylethylenediamine)zinc(II), C₆H₁₆Cl₂N₂Zn, has been determined from 1684 reflexions measured on a Siemens four-circle diffractometer (A.E.D.) using the /2-scan technique and CuK radiation. The crystals are monoclinic, space groupP2₁/c,a = 7·716(3),b = 13·335(9),c =11·545(5) Å, = 105·59(6) ° andZ = 4. The structure was solved by Fourier methods, and refined by full-matrix least squares to a finalR (conventional) of 6·7 %. Anisotropic thermal parameters were evaluated for the non-hydrogen atoms, but the hydrogen atoms were assigned the equivalent isotropic thermal parameters of the carbon atoms to which they were bonded. The geometry around the zinc atom is distorted tetrahedral, with the Zn-Cl and Zn-N average bond lengths of 2·207(4) and 2·08(1) Å respectively.     

Six-coordinated zinc complexes: [Zn(H2O)4(phen)] (NO3)2·H2O and [ZnNO3(H2O)(bipy)(Him)]NO3 (phen = 1,10-phenanthroline, bipy = 2,2′-bipyridine, and Him = imidazole)

Two novel six-coordinated zinc complexes, tetra-aqua(1,10-phenanthroline)zinc dinitrate monohydrate, [Zn(H₂O)₄(phen)](NO₃)₂·H₂O (1) and aqua(2,2-bipyridine)(imidazole)-nitratozinc nitrate, [ZnNO₃(H₂O)(bipy)(Him)]NO₃ (2) were prepared. Compound 1 crystallizes in the monoclinic space group P2₁/c with a = 8.780(4), b = 13.609(4), c = 15.368(5) Å, = 93.86(2)°C, V = 1832.1(12) ų. In 1, a phenanthroline molecule chelates the zinc atom and four water molecules complete the octahedral geometry around the metal. Compound 2 crystallizes in the monoclinic space group P2₁/n with a = 7.250(1), b = 24.554(4), c = 10.258(2) Å, = 107.880(10)°, V = 1737.9(5) ų. In 2, a bipyridine molecule and a nitrate anion chelate the zinc atom. An imidazole molecule and a water molecule then complete the six-coordinated geometry around zinc. The intermolecular packing is controlled by hydrogen bonding, especially in 1 and by stacking. The thermal stability of the compounds and the loss of water molecules and ligands was monitored by a thermogravimetric study.     

Complexes of 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (4,13-diaza-18-crown-6) with 2,5-pyridinedicarboxylic and 2,2′-dithiosalicylic acids

A 1:2:2 complex of 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane with 2,5-pyridinedicarboxylic acid and water (1) and its 1:1:1.75 complex with 2,2-dithiosalicylic acid and water (2) have been obtained and characterized by x-ray diffraction. C₂₆H₄₀N₄O₁₄ (1), triclinic, , a = 9.574(1) Å, b = 9.632(1) Å, c = 9.723(1) Å, = 112.70(1)°, = 91.07(1)°, = 115.45(1)°, V = 728.35(13) ų, Z = 1. C₂₆H_39.5N₂O_9.75S₂ (2), M = 600.22, triclinic, , a = 10.492(1) Å, b = 10.945(1) Å, c = 14.535(2) Å, = 102.74(1)°, = 109.08(1)°, = 90.68(1)°, V = 1532.2(3) ų, Z = 2. In complex 1, both N-atoms of the macrocyclic ring are protonated. The following types of H-bonding have been found: (1) between protonated aza groups of the macrocycle and ionized carboxylic groups; (2) between the protonated aza groups and N-atoms of the pyridine nuclei (D–A distance slightly exceeds 3 Å); (3) between water molecules and C=O groups of the non-ionized carboxylic groups; and (4) between the nonionized and ionized groups of the carboxylic acid. The above interactions give rise to the formation of a developed supramolecular network in the crystals of 1. In complex 2, despite the presence of several types of hydrogen bonds involving the aza crown, 2,2-dithiosalicylic acid and water, the aromatic anions are H-bound only to the two other components, and not to each other. The H-bonds found in complex 2 are between (1) one of the protonated aza groups and water, (2) protonated aza groups and O-atoms of the ionized carboxylic groups, (3) water molecule and carboxylic O-atom, (4) water molecule and sulfur atom, and (5) water molecule and O-atom of diaza-18-crown-6.     

Molecular structure of P-(2,4,6-tri-tert-buthylphenyl)-phenylmethylene(phenylsulfonylimino)-σ3λ5-phosphorane

The crystal and molecular structure of P-(2,4,6-tri-tert-buthylphenyl)-phenylmethylene (phenylsulfonylimino)-³⁵-phosphorane, 2,4,6-Bu^t ₃-C₆H₂-P(=CHPh)(=N--SO₂Ph), has been determined. Crystal data: triclinic, , a = 9.472(5), b = 11.427(5), c = 13.684(5) Å, = 90.61(3), = 101.21(4), = 97.02(4)°, V = 1441.1 ų, Z = 2, D _c = 1.20 g cm^–3. The observed in 1 noticeable elongation of the P=N bond 1.563(3) Å and shortening of the P=C bond 1.617(3)Å have been discussed in terms of the electron withdrawing ability of substituents on the basis of ab initio (HF/6–31+G**) calculations of the model systems.     

Structure of tetra(β-propiophenone-1,2,4,triazole-N4) dichloro metal hexahydrate complex: [MCl2(C2H2N3CH2CH2COPh)4]⋅6H2O (M = Ni, Co)

The crystal and molecular structures of the complexes of [NiCl₂(N⁴-trzCH₂CH₂ COPh)₄]6H₂O and [CoCl₂(N⁴-trzCH₂CH₂COPh)₄] 6H₂O (trz = 1,2,4-triazole) have been determined by X-ray crystallography. They are isomorphous. The crystal structures are very similar. They both crystallize in the monoclinic system, space group P2 ₁/c, Z = 4; the former with lattice parameters a = 8.0391(2), b = 10.8215(2), c = 29.0133(2) Å, = 94.792(1)°; the latter with a = 8.039(2), b = 10.822(2), c = 29.013(6) Å, = 94.79(3)°. They all display almost perfect octahedral coordination geometry around the central metal atom. Each metal atom is coordinated by four N atoms of triazole from four -propiophenone-1,2,4-triazole ligands and two chloride anions in a trans arrangement. In addition to the coordinating metal complex, there are six uncoordinated water molecules, which complete the crystal structure. In the solid state, the title two compounds form three dimensional network structures through hydrogen bonds. The intermolecular hydrogen bonds connect the [MCl₂(C₂H₂N₃CH₂CH₂COPh)₄] and H₂O moieties.     

Synthesis and crystal structures of 2-amino-3-cyano-4-(2-chlorophenyl)-1,4-dihydro-2H-pyrano[3, 2-h]quinoline and 2-amino-3-cyano-4-(2-chlorophenyl)-8-(2-chlorobenzylidene)-1,4,5,6,7,8-hexahydrobenzo[b]pyran

The title compounds 2-amino-3-cyano-4-(2-chlorophenyl)-1,4-dihydro-2H-pyrano[3, 2-h]quinoline 1 (C₁₉H₁₂ClN₃O, M _r = 333.77) and 2-amino-3-cyano-4-(2-chlorophenyl)-8-(2-chlorobenzylidene)-1,4,5,6,7,8-hexahydrobenzo[b]pyran 2 were synthesized and crystallized. The crystals of compound 1 are triclinic, space group P-1, a = 7.488(2), b = 9.127(3), c = 12.252(3) Å, = 73.58(2), = 78.38(2)°, = 75.39(2), Z = 2, V = 769.5(4) ų; The compound 2 crystallizes in space group P2₁/n, with cell parameters a = 13.582(2), b = 8.974(1), c = 16.960(2) Å, = 103.34(1)° and D _calc = 1.352 g/cm^–3 for Z = 4. X-ray analysis reveals that atoms C(1)—C(5) and O form a pyran ring in compound 1, which adopts half-chair conformation. In compound 2 the atoms C(12)—C(16) and O form a pyran ring which adopts boat conformation, another six-membered ring (C(8)—C(13)) adopts a half-chair conformation. In addition, there are intermolecular hydrogen bonds in the crystal structures 1 and 2.     

Synthesis, characterization, and crystal structures of two strained cyclic diacetylenes and their precursors

The synthesis, characterization, and crystal structures of two novel strained cyclic diacetylenes are reported. A discussion is presented about the relative bond distances of the diacetylenes compared to a previously reported strained cyclic diacetylene to further determine the degree of aromaticity of that compound. 1,2:5,6:9,10:13,14-Tetrabenzo-3,7,11,15,17-pentadehydro[18] annulene (5) is triclinic, P ^–1, with = 9.489(5), b = 10.550(5), c = 12.155(6) Å, = 100.50(4), = 106.50(4), = 100.85(4)°. 1,2:5,6:9,10:13,14:17,18-Pentabenzo-3,7,11,15,19,23,25-heptadehydro[26]annulene (7) is triclinic, P ^–1, with a = 9.611(2), b = 10.388(3), c = 15.963(3) Å, = 88.67(2), = 76.25(1), = 68.69(2). In addition, two precursors of 5, 3 and 4 which have a helical twist, are reported. [1,2-ethynediyl-bis(2,1-phenylene-2,1-ethynediyl-2,1-phenylene-2,1-ethynediyl]bis[trimethyl-silane] (3) is monoclinic, P2₁/c, with a = 13.682(4), b = 9.787(2), c = 13.448(4) Å, = 112.37(2)°. 1,1-(1,2-ethynyldiyl)bis[2-[(2-ethynylphenyl)ethynyl]-benzene (4) is monoclinic, P2₁/n, with a = 15.951(3), b = 3.999(1), c = 18.168(4) Å, = 99.05(3)°.     

Structural characterization of Elisabatin B and Elisabatin C

X-ray structures of Elisabatin B (1) and Elisabatin C (2) have been determined. Crystal data for 1: Triclinic, P (No. 2), a = 7.528(2) Å, b = 9.404(2) Å, c = 11.414(2) Å, = 75.363(3)°, = 86.668(4)°, = 89.683(4)°, and Z = 2. Crystal data for 2: Monoclinic, P2₁/c (No. 14), a = 8.242(2) Å, b = 14.870(2) Å, c = 13.060(2) Å, = 101.458(3)°, and Z = 4. Both compounds are highly unsaturated leading to extended aromatic conjugation. They show different intermolecular O–HO hydrogen bonds, via which 1 forms dimers, and 2 zig-zag polymeric chains.     

Short H· · ·H distances in norbornene derivatives

A short H···H intramolecular interaction was reported previously for an anhydride of syn-sesquinorbornene. The synthesis and structure of a such an anhydride with an additional five-membered dithiole ring has been investigated. While hydrogen atom positions are not accurately located, the 1.62 Å separation indicates this molecule is a candidate for the shortest H···H interaction. Two cycloadducts of norbornadiene, which literature suggests might exhibit additional short interactions, are reported also; however, the isomers with minimal intramolecular interactions are the isolated products. C₂₂H₂₀O₃S₂, 3, crystallizes in P with a = 10.881(4), b = 13.712(8), C = 6.548(8) Å, = 101.32(6), = 107.49(5), = 90.49(4)°, D _calc = 1.445 g cm^–3, and Z = 2, C₂₁H₂₀O₄Cl₈, 5, in P2₁/n with a = 8.168(2), b = 13.488(4), c = 23.500(6) Å, = 94.72(2)°, D _calc = 1.597 g cm^–3, and Z = 4, C₂₁H₂₈O₄, 6, in P> with a = 12.667(2), b = 12.792(2), c = 12.540(2) Å, = 113.51(1), = 98.18(1), = 74.39(1)°, D _calc = 1.276 g cm^–3, and Z = 4.     

X-ray structures of new substituted 2-(pyrazol-1-yl)-2′-nitroacetanilides with pharmacological activity

The X-ray structures of four pharmacologically active lidocaine analogs, containing substituted pyrazole moieties as the basic residue and an o-nitrophenyl moiety as the hydrophobic residue, have been determined. They are 2-(pyrazol-1-yl)-2-nitroacetanilide (1), 2-(3,5-dimethyl-pyrazol-1-yl)-2-nitroacetanilide (2), 2-(3,5-dimethyl-4-iodo-pyrazol-1-yl)-2-nitroacetanilide (3), and 2-(3,5-dimethyl-4-nitro-pyrazol-1-yl)-2-nitroacetanilide (4). Crystal data are 1: space group Pn with a = 4.6944(1), b = 22.3890(3), c = 15.7481(2) Å, = 96.810(1)°, Z = 6; 2: P with a = 4.7277(2), b = 11.6878(5), c = 12.0355(6) Å, = 87.689(2), = 85.048(2), = 85.975(2)°, Z = 2; 3: I2/a with a = 24.108(5), b = 4.7321(9), c = 25.337(5) Å, = 96.09(3)°, Z = 8; 4: P2₁ with a = 5.7788(2), b = 8.9844(3), c = 14.0304(5) Å, = 101.611(1)°, Z = 2. Molecules of compound 1 adopt a unique, folded conformation stabilized by intramolecular hydrogen bonds and the crystal structure lacks significant intermolecular interactions. In contrast, molecules of 2–4 adopt common, extended conformations and their crystal structures are based on linear arrays of hydrogen bonded (N—H...O=C) molecules. Compound 3 displayed the highest local anesthetic activity while 2 was the most active in tests for anti-arrhythmic effects.     

Crystal structure of chloro(dicarbonyl) bis(acetonitrile) (π-2-methallyl) molybdenum(II)

The title compound crystallizes in the monoclinic spacegroup P2₁/m with a = 6.796(9), b = 12.145(14), c = 7.749(8)Å, = 101.86(1)°, and Z = 2. The crystal structure consists of molecules of [MoCl(CO)₂(NCMe)₂(³-C₃H₄Me-2)] with crystallographically imposed C_s symmetry and has a pseudo-octahedral geometry, with the -allyl group trans- to the chloro group and the two cis-carbonyl and acetonitrile groups occupying the equatorial plane.     

Crystal structures of two substituted biphenyl derivatives: 5,5′-di t-butyl-2-2′-biphenyldiol and 5,5′-dimethyl-2,2′-biphenyldiol

5,5-Di t-butyl-2,2-biphenyldiol (I), C₂₀H₂₆O₂, crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 18.243(2), b = 9.947(2), c = 9.685(3) Å, and Z = 4; 5,5-dimethyl-2,2-biphenyldiol (II), C₁₄H₁₄O₂, crystallizes in the monoclinic space group P2₁/c with a = 9.959(2), b = 7.932(3), c = 15.392(2) Å, = 105.43(2)°, and Z = 4. The aromatic rings are tilted by 52.7(1) and 43.8(1)° to each other in compounds (I) and (II), respectively. Strong intra- and inter-molecular H-bonds connect the molecules in the crystals.     

Synthesis and characterization of the dodecanuclear heterobimetallic Mo—Cu—S cage cluster: (Ph4P)2[{Mo2Cu2O2S2(S2)2}3(μ6-S)]

The complex (Ph₄P)₂[Mo₂S₂O₂(S₂)(S₄)] reacts with CuBr to give the dodecanuclear heterobimetallic Mo—Cu—S cage cluster: (Ph₄P)₂[{Mo₂Cu₂O₂S₂(S₂)₂}₃(₆-S)] (1), which crystallizes in the triclinic space group P1¯, a = 14.445(5), b = 15.396(5), c = 18.858(5) Å, = 103.12(3), = 101.93(2), = 113.92(3)°, and V = 3517(2) ų for Z = 2. The anion 1 can be described as a cage with S^2– at the center binding to six Cu atoms; the cage has two big windows each composed of a puckered Cu₃S₆ 9-membered ring.     

Molecular structure of a novel heterocycle: 1,1,4,4,tetramethyl-1H,4H-thieno[3,4-c]thiophene

The X-ray crystal structure of the title compound, C₁₀H₁₄S₁, is reported. Crystals are monoclinic, space groupP2₁/c with Z = 2 in a unit cell of dimensionsa = 8.517(2),b = 6.109(1),c = 10.730(1) Å, and = 107.01(2)°. The structure was solved by direct methods and refined by full-matrix least squares toR = 0.032 for 1059 diffractometer data. The bicyclic molecular framework contains eight -electrons and is planar and rigid, all relevant interatomic distances corresponding to either ideally single or ideally double bonds. The first UV absorption observed at 3.61 eV, and tentatively described as due to a (b_g) *(a _u*) electron transition, is significantly higher than that found in a related aromatic tetraphenylthienothiophene system.     

Structure of hexakis(imidazole)nickel(II) disalicylate, [Ni(Im)6](Sal)2

The crystal and molecular structures of [Ni(Im)₆](Sal)₂ (Im = imidazole, Sal = salicylate) have been determined by X-ray crystallography. It crystallizes in the triclinic system, space group P1¯, with lattice parameters a = 8.3125(2), b = 8.7168(1), c = 12.3262(3) Å, = 90.341(1), = 96.33(1), = 101.544(1)°, and Z = 1. The crystal structure of the title compound is built up of discrete monomeric molecules of [Ni(Im)₆](Sal)₂. The nickel(II) ions have an octahedral geometry with the NiN₆ chromophore. In the solid state, the title compound forms a network through N—H···O hydrogen bonds, the intermolecular hydrogen bonds connect the Ni(Im)²⁺ ₆ moieties and salicylate molecules.     

Crystal structure and vibrational spectra of two complexes of manganese(II) with glicyne

Two polymeric complexes of glicyne with manganese(II) have been prepared and characterized by means of spectroscopic and x-ray analyses. The first complex of the formula [Mn(Gly)Cl₂(H₂O)₂] crystallizes in the monoclinic space group P2₁/n with a = 6.519(2), b = 15.981(3), c = 7.893(2) Å, and = 97.18(3)°. The Mn atoms are in distorted octahedral environments with all ligands in cis positions. The adjacent manganese(II) ions are linked in polymeric chains via carboxylate groups. The second complex [Mn(Gly)₂Cl₂] crystallizes in the triclinic space group P with a = 4.968(2), b = 6.582(2), c = 7.925(3) Å, = 106.17(3), = 92.86(3), and = 107.21(3)°. The octahedral-coordinated manganese(II) ion is situated on a crystallographic center of symmetry and is bound to four carboxylate oxygen atoms from different glicyne molecules and two chloride ions.     

Molecular structure of N-(2-phenylethyl)amide of α-(1,1-ethylenedioxy)-ethyl γ-hydroxybutyric acid (I) and1H NMR spectra of (I) and N-(p-methoxybenzyl)derivative (III)

The spectroscopic and X-ray investigation of the N-(2-phenylethyl) amide of -(1,1-ethylenedioxy)-ethyl--hydroxybutyric acid are reported. The¹H NMR spectra for the title structure and for the N-(p-methoxybenzyl) amide of -(1,1-ethylenedioxy)-ethyl--hydroxybutyric acid are given. The N-(2-phenylethyl)amide of -(1,1-ethylenedioxy)-ethyl--hydroxybutyric acid, C₁₆H₂₃O₄N, crustallizes in the monoclinic space groupP2 ₁/c witha=21.547(5),b=6.333(2),c=11.822(3) Å and =101.01(2)°. The dioxolane ring has a half-chair conformation with C₂(O3)=2.4° and ||_av=18.2°. The inconsiderable deviations from planarity of the six atoms of the amide group are caused mainly by twist around the C4–N1 bond and out-of-plane bending at the N1 atom ((C4–N1)=4°, X_N =7°, X_c =0.4° ). The amide group plane is nearly coplanar with the phenyl ring. The molecules are connected by two intermolecular hydrogen bonds.