A 1:1:2 complex between 1,4,8,11-tetraazacyclotetradecane (cyclam), anthraflavic acid, and water

A 1:1:2 complex of 1,4,8,11-tetraazacyclotetradecane (cyclam), anthraflavic acid, and water has been obtained and characterized by X-ray diffraction. C₂₄H₃₆N₄O₆, monoclinic, P2₁/c, a = 11.966(1) Å, b = 11.570(1) Å, c = 9.604(1) Å, = 107.16(1)°,V = 1270.5(2) ų, Z = 2. Two of the four N atoms of the macrocyclic ring are protonated, and the corresponding anthraflavic acid exists as a dianion. The following types of H-bonding have been found in this complex: (1) between protonated NH groups of the macrocycle and O atoms of the ionized anthraflavic hydroxyls; (2) between protonated and nonprotonated NH groups of the macrocycle; (3) between the water molecules and O atoms of the ionized anthraflavic hydroxyls. The above interactions give rise to the formation of a 2D-supramolecular network in the cyclam complex; however, the major difference from the azamacrocyclic anthraflavates studied previously is that there is no direct interaction between the anthraflavic anions.Deceased     

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.     

Structure of tetrahydro-2-naphthyl-4H-1,3,6,2-dioxazaboracine

Intramolecular B-N coordination occurs in tetrahydro-2-naphthyl-4H-1,3,6,2-dioxazaboracine, 2: (R = 2-naphthyl; R = H) both in the solid state and in CDCl₃ solution. Compound 2: (R = 2-naphthyl; R = H) crystallizes in the orthorhombic space group P2₁2₁2₁ (Z = 4), with a = 9.266(6), b = 11.034(8), c = 12.0635(10) Å. Molecules are linked, in the solid state, into spiral chains. As only one of the two oxygen atoms present in each molecule is involved in H-bonding, the boron and nitrogen centres are chiral. The intramolecular B-N bond length is 1.671(4) Å; other geometric parameters are B-O bond lengths of 1.448(4) and 1.464(4) Å, a B-C bond length of 1.598(4) Å, and bond angles at B between 100.6(3) and 115.4(3)°. The ¹¹B value for 2 (R = 2-naphthyl, R = H) at 25°C in CDCl₃ solution is 10.7 ppm.     

Synthesis,spectroscopic studies,and crystal structure of theophyllinium tetrabromopalladate(II)

The theophyllinium tetrabromopalladate(II), [Thph]₂PdBr₄, has been synthesized and its molecular structure has been determined by single crystal X-ray diffraction. The salt crystallizes in the monoclinic space group C2 with two formula units in a cell of dimensionsa=11.074(1),b=8.545(2),c=11.804(2) Å;=95.22(1)°,V=1112.3(4) ų,D _c=2.353 mg m^–3,D _exp=2.352 mg m^–3,M _w=788.4, (MoK)=84.5 cm^–1,F(000)=752. The structure has been refined by full-matrix least-squares techniques to a final value of theR factor of 0.058 based on 907 independent intensities. The compound consists of theophyllinium cations protonated at N(9). The [PdBr₄]^2– anion is planar, with distances Pd-Br(1)=2.441(12) and Pd-Br(2)=2.412(6) Å, and Br(1)-Pd-Br(2) and Br(1)-Pd-Br(3) angles of 90.34(14)° and 89.66(14)°, respectively. The¹H-NMR spectrum of [Thph]₂PdBr₄ in DMSO-d₆ (300 MHz) is consistent with the observed solid-state structure, and its thermal behavior shows two steps: (i) a dehalogenation process about 327°C and (ii) a rapid pyrolitic decomposition in the 340–575°C temperature range giving PdO as final product.     

A 1:2:2 complex between 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (4,13-diaza-18-crown-6), 2,6-dihydroxyanthraquinone and water

A 1:2:2 complex of diaza crown ether 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, anthraflavic acid (2,6-dihydroxyanthraquinone) and water has been synthesized. The crystal is triclinic, P1, with a = 7.705(2), b = 10.871(2), c = 11.540(2) Å, = 100.40(2), = 91.38(2), = 98.01(2)°, Z = 1, and D_calc = 1.375 mg m^–3. The main feature of the crystal structure is the formation of a supramolecular sheet by hydrogen bonding of the anthraflavic monoanions, not only head-to-tail through the hydroxyl oxygens, but sideways through the quinone oxygens. This complex represents an intermediate case between total transfer of protons of a hydroxy-guest to crown N-atoms, and no transfer.     

Study of the sulfur atom as hydrogen bond acceptor in N(2)-pyridylmethyl-N′-arylthioureas

The hydrogen acceptor capability of the sulfur atom in the biologically relevant N-2-pyridylmethyl-N-arilthioureas was explored. N-2-Pyridylmethyl thioreas were selected to avoid the formation of intramolecular six-membered hydrogen-bonded ring. The compounds studied were N-2-pyridylmethyl-N-phenylthiourea (1), N-2-pyridylmethyl-N-2-methoxythiourea (2), N-2-pyridylmethyl-N-4-methoxyphenylthiourea (3), and N-2-pyridylmethyl-N-4-bromophenylthiourea (4). 1 crystallizes in the monoclinic space group P2₁/c, with a = 7.419(1) Å, b = 18.437(2) Å, c = 9.656(1) Å, = 106.277(6)°, V = 1267.8(3) ų, Z = 4. 2 crystallizes in the monoclinic space group P2₁/c, with a = 8.064(2) Å, b = 18.382(7) Å, c = 9.865(5) Å, = 97.81(3)°, V = 1448.8(11) ų, Z = 4. 3 crystallizes in the monoclinic space group P2₁/c, with a = 11.472(1) Å, b = 13.520(1) Å, c = 10.088(1) Å, = 112.60(1)°, V = 1444.5(2) ų, Z = 4. 4 crystallizes in the triclinic space group P-1, with a = 4.583(3) Å, b = 10.263(3) Å, c = 14.396(3) Å, = 77.92(2)°, = 88.55(4)°, = 80.02(4)°, V = 652.1(5) ų, Z = 2. Both thiourea N–H groups form intermolecular hydrogen bonds, one with the thione sulfur atom and the other with the pyridine nitrogen atom but the H-bonding schemes are not the same maybe due to the flexibility of the molecules.     

Crystal structure of the nonlinear optical compound L-arginine fluoride

L-arginine fluoride is a promising compound that exhibits nonlinear optical properties. It efficiently converts two single photons of the same polarization and frequency to one photon of frequency 2 (type I phase matching). C₆H₁₅N₄O₂ ⁺F^– is monoclinic, space group P2₁, a = 5.4475(4) Å, b = 8.5133(6) Å, c = 10.2195(7) Å, = 93.475(6)°. The cation has a zwitterionic form, protonated at both the guanidyl and amino groups. The arginine C atom is in a trans position to the carboxyl group. A complex three-dimensional hydrogen bond network links the anions and cations together.     

Synthesis and structure determination of a 2D open-framework zincophosphate templated by cyclohexylamine molecules

The synthesis and crystal structure of a new bidimensional zincophosphate (ZnPO) are reported. Zn₂(HPO₄)₂Cl₂·2NC₆H₁₄ crystallizes in the monoclinic space group P2₁/a (n°14) with a = 8.830(3) Å, b = 9.278(3) Å, c = 26.950(9) Å, = 90.74(3)°, V = 2207.7(1) ų and Z = 4. This new material consists of a 2D open-framework of corner sharing ZnO₃Cl and PO₃OH tetrahedra alternating with planes of protonated cyclohexylamine molecules (NC₆H₁₄)⁺. The organic molecules are interconnected to the framework through hydrogen bonds.     

Structures and nonlinear optical properties of polar 2-amino-1,2,3-triazolequinone derivatives

A series of phenyldialkylamine, dimethoxyphenyl, and nitrothiophene derivatives of 2-amino-1,2,3-triazolequinones was characterized by NMR, IR, mass spectroscopy, cyclic voltammetry, and chemical analyses. The solvatochromic procedure was used to evaluate the potential of nine compounds for nonlinear optical applications, and the possible failure of this model is discussed. The crystal structures of seven compounds were determined: (4) P2₁/c, a = 15.430(3) Å, b = 7.633(2) Å, c = 15.940(3) Å, = 105.19(3)° (5) P2₁/c, a = 20.201(2) Å, b = 9.6579(9) Å , c = 18.517(2) Å, = 95.907(2)° (6) P-1, a = 7.769(2) Å, b = 8.515(3) Å, c = 17.312(5) Å, = 89.347(7)°, = 83.219(6)°, = 86.001(7)° (7) P-1, a = 8.1365(7) Å, b = 8.9605(8) Å, c = 11.630(1) Å, = 79.553(2)°, = 75.048(2)°, = 82.080(2)° (8) P-1, a = 8.298(3) Å, b = 9.720(3) Å, c = 10.033(3) Å, = 84.803(6)°, = 83.735(6)°, = 77.659(5)° (10) P2₁/n, a = 8.4300(7) Å, b = 13.980(1) Å, c = 13.975(1) Å, = 106.590(2)° (12) P2₁/n, a = 7.715(2) Å, b = 14.206(3) Å, c = 12.758(3) Å, = 91.016(5)°.     

Thiophene substituted dihydropyridines

The crystal structures of 4-(2-thiophenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-bis(methoxy-carbonyl) (I)[a = 10.273(5) Å, b = 10.428(5) Å, c = 14.799(9) Å, = 98.13(4)°, P2₁/c], 4-(3-thiophenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-bis(methoxycarbonyl) (II)[a = 10.636(9) Å, b = 10.372(8) Å, c = 15.043(15) Å, = 98.13(6)°, P2₁/c], and 4-(2-thiophenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-bis(ethoxycarbonyl) (III) [a = 26.793(16) Å, b = 7.610(6) Å, c = 17.612(10) Å, = 97.61(2)°, C2/c] reveal patterns of hydrogen bonding pertinent to behavior of these members of the 1,4-dihydropyridine family in receptor site docking. Carbonyl groups substituted at C3 and C5 are seen in ap conformation when hydrogen bonded. Sulphur atoms of the hetero rings do not participate in hydrogen bonding. In these structures the position of the herero atom is seen to be disordered over two equivalent sites. Thus, there is no demonstrated preference for conformation of the hetero ring.     

Isolation and structures of eudesmanolides from Tanacetum cadmeum ssp. cadmeum

Eight sesquiterpene lactones, two coumarins, and two flavonoid derivatives were isolated from Tanacetum cadmeum (Boiss.) Heywood ssp. cadmeum. All compounds have been found previously in other plant species. The crystal structures of artesin and taurin are reported. Crystals of artesin (C₁₅H₂₂O₃) belong to the monoclinic space group P2₁: a = 8.300(1), b = 6.304(1), c = 13.118(2) Å, = 101.836(3)°, V = 671.8(2), Z = 2, R ₁ = 0.0291. Crystals of taurin belong to the monoclinic space group P2₁: a = 5.722(1), b = 8.279(2), c = 14.503(3) Å, = 90.025(1)° , V = 687.0(3), Z = 2, R ₁ = 0.0493. An investigation of the space group indicated a monoclinic system rather than orthorhombic.     

Cage-annulated thiacrown ethers and thiacryptands

A series of cage-annulated sulfur-containing crown ethers and cryptands have been synthesized as possible specific metal host systems. The synthesis and structures of seven compounds are described, including a thiacryptand complex with Hg(II). The trishomocubane cage is essentially spherical except for a methylene group, which imparts no steric restrictions, and two disordered superimposed orientations occur in most structures. This superposition of four- and five-membered rings usually cannot be resolved into separate entities, resulting in distorted distances, angles, and thermal parameters for the cage. (3) I4₁ cd, a = 13.207(3) Å, b = 13.207(3) Å, c = 35.876(12) Å; (10) C2, a = 14.551(2) Å, b = 10.028(1) Å, c = 10.491(1) Å, = 107.108(2)°; (14) P2₁/n, a = 10.6277(8) Å, b = 9.8488(7) Å, c = 21.822(2) Å, = 97.945(2)°; (19) P2₁/c, a = 15.381(3) Å, b = 6.667(1) Å, c = 18.158(3) Å, = 94.838(4)°; (25) C2/c, a = 34.386(4) Å, b = 11.318(1) Å, c = 13.409(2) Å, = 110.044(2)°; (28) , a = 10.4487(8) Å, b = 11.5677(9) Å, c = 13.354(1) Å, = 71.042(1)°, = 87.344(1)°, = 65.839(1)°; (29) P2₁/c, a = 10.8138(5) Å, b = 16.4949(8) Å, c = 22.054(1) Å, = 96.087(1)°.     

A novel class of naturally occurring halogenated pyrroles, 1,1′-dimethyl-3,3′,4,4′,5,5′-hexabromo-2,2′-bipyrrole, 5,5′-dichloro-1,1′-dimethyl-3,3′,4,4′-tetrabromo-2,2′-bipyrrole, and 1,1′-dimethyl-3,3′,4,4′,5,5′-hexachloro-2,2′-bipyrrole

Crystal structure determinations of the three title hexahalogenated bipyrroles, (I) C₁₀H₆Br₆N₂, (II) C₁₀H₆Br₄Cl₂N₂, and (III) C₁₀H₆Cl₆N₂, reveal essentially planar pyrrole rings having dihedral angles of 64.7, 65.1, and 64.2° between the least-squares planes, favoring in each case a closer methyl–halogen conformation. All three complexes crystallize in the orthorhombic space group Pbcn with the following cell dimensions: (I) a = 12.654(3) Å, b = 8.853(2) Å, c = 13.753(3) Å, = = = 90°, Z = 4; (II) a = 12.438(6) Å, b = 8.753(6) Å, c = 13.696(3) Å, = = = 90°, Z = 4; (III) a = 12.088(6) Å, b = 8.566(4) Å, c = 13.486(8) Å, = = = 90°, Z = 4.     

A new class of flexible energetic salts. Part 7: The structures of the guanidinium and hydroxyguanidinium salts of dinitramide

The crystal structures of two amine base salts of dinitramide, the guanidinium 1, and the hydroxyguanidinium 2, have been determined. 1 crystallizes in the triclinic space group with cell dimensions a = 8.325(2) Å, b = 9.301 (2) Å, c = 9.868(2) Å, = 84.73(3)°, = 69.25(3)°, = 67.55(3)°, while 2 crystallizes in the noncentric monoclinic space group Pc with cell dimensions a = 7.098 (2) Å, b = 3.5160 (10) Å, c = 14.358(3) Å, = 98.940(10)°. The structures of 1 and 2 contain protonated amine cations and dinitramide anions linked by hydrogen bonding. In both structures the conformations adopted by the dinitramine anions can be related to the types of hydrogen bonds it forms with the surrounding amine cations.     

Terbium and holmium trans-2,3-dimethylacrylic acid complexes with 1,10-phenanthroline

Novel dinuclear complexes, [REL₃(phen)]₂ (where RE = Tb, Ho; HL = trans-2,3-dimethylacrylic acid; phen = 1,10-phenantheoline), were synthesized and determined by elemental analysis, infrared absorption spectra (IR), thermogravimetric analysis (TGA), and X-ray diffraction. The Tb complex crystallizes in space group P2_1/n with the cell dimensions a = 12.939(2) Å, b = 13.018(2) Å, c = 15.400(3) Å and = 94.72(1)°. The Ho complex crystallizes in P ⁽⁹⁾ with a = 12.406(3) Å, b = 13.280(3) Å, c = 9.823(2) Å, = 110.80(2)°, = 103.42(2)°, = 63.67(1)°. The Tb atom is nine coordinate and the separation of Tb...Tb* is 3.97 Å. The Ho atom is eight coordinate and the separation of Ho...Ho* is 4.01 Å.     

Structures of dinitroazetidine and three of its carbonyl derivatives

The structures of DNAZ (3,3-dinitroazetidine), DNAZ-COH, DNAZ-CO-DNAZ, and (DNAZ-CO)₂ have been determined. DNAZ crystallizes in the space group P2₁/c with cell parameters a = 5.928(7) Å, b = 15.8380(2) Å, c = 12.6837(15) and = 93.23°. DNAZ-COH crystallizes in the space group P2₁/c with cell parameters a = 10.3270(10) Å, b = 6.0615(12) Å, c = 11.2514(12), and = 100.17°. DNAZ-CO-DNAZ crystallizes in the space group P2₁/n with cell parameters a = 10.3630(6) Å, b = 6.0901(5) Å, c = 19.9421(11) and = 102.74°. (DNAZ-CO)₂ crystallizes in the orthorhombic space group Fdd2 with cell parameters a = 13.1956(10) Å, b = 19.524(3) Å, c = 10.3259(11). This last compound is unique in that the trans carbonyls are planar and the adjoining azetidine rings are also planar to within 0.1° in all torsion angles. DNAZ crystals have a dimeric asymmetric unit where two nonequal molecules are bonded to each other with a single hydrogen bond. Like other four-membered rings with gem-dinitro groups, most of these dinitroazetidines display mutually perpendicular nitro groups.     

Crystallographic characterization of N,N′-diarylformamidines bearing an alkoxy substituent at either the meta- or ortho-position

Crystal structures of four diphenylformamidines bearing phenyl substituents ortho-CH₃O (1), ortho-C₂H₅O (2), meta-CH₃O (3), and meta- ⁿ BuO (4) are reported. In each of the structures, formamidine exists as an unsymmetrical cyclic hydrogen bond dimer, and the geometry of the amidine unit is consistent with the localized C–N and C=N bonds. Interesting conformations due to the orientation of aryl groups were also observed. Crystal Data: 1, orthorhombic, Pbca, a = 11.297(1) Å, b = 15.092(1) Å, c = 16.380(2) Å, V = 2792.6(4) ų, Z = 8; 2, triclinic, P , a = 9.651(1) Å, b = 11.974(1) Å, c = 14.583(2) Å, = 101.789(2)°, = 99.320(2)°, = 99.048(2)°, V = 1595.9(3) ų, Z = 4; 3, orthorhombic, Pbca, a = 15.562(2) Å, b = 8.626(1) Å, c = 20.110(2) Å, V = 2699.4(5) ų, Z = 8; 4, monoclinic, P2₁/c, a = 14.525(2) Å, b = 15.534(2) Å, c = 8.818(1) Å, = 93.113(2)°, V = 1986.6(4) ų, Z = 4.     

Crystal structure and thermal analysis of 1,5-diammonium-2-methyl pentane sulfate monohydrate

Chemical preparation, x-ray single crystal, and thermal analysis of C₆H₁₈N₂SO₄·H₂O (denoted DMPS) are described. The compound crystallizes in the triclinic system with P space group. Its unit cell dimensions are a = 5.826(1) Å, b = 10.014(1) Å, c = 11.221(1) Å, = 66.716(1)°, = 84.395(1)°, = 83.759(1)°, V = 596.7(1) ų, and Z = 2. The DMPS structure is built up from inorganic chains parallel to the a axis and linked via O(W)-H···O hydrogen bonds. These chains are interconnected by organic groups. Thermal analysis reveals the presence of one water molecule in the structure and shows a reversible weak phase transition.     

Synthesis and crystal structure of 3,5-di(2-propenyl)-6-phenyl-1,3,5-triazine-2,4-dione and 2-dimethylamino-4-ethoxycarbonylmethoxy-6-phenyl-1,3,5-triazine

The title compound 3,5-di(2-propenyl)-6-phenyl-1,3,5-triazine-2,4-dione has been synthesized by the reaction of 6-phenyl-1,3,5-triazine-2,4-dione with allyl bromide. Its structure was determined by X-ray single crystal diffraction. The crystal belongs to orthorhombic, space group Pbca with the following crystallographic parameters: a = 16.282(4) Å, b = 8.888(2) Å, c = 19.281(5) Å, = 90°, = 90°, = 90°, = 0.088 mm^–1, V = 2790.1(13) ų, z = 8, Dx = 1.282 mg/m³, F(000) = 1136, T = 293(2) K, 2.11° 25.02°, the final R factor: R ₁ = 0.0430, wR₂ = 0.0981. The X-ray results demonstrate that the reaction of 6-phenyl-1,3,5-triazine-2,4-dione with allyl bromide in the presence of N,N-dimethylformamide and potassium carbonate yields the N-alkylated product. The title compound 2-dimethylamino-4-ethoxycarbonylmethoxy-6-phenyl-1,3,5-triazine has been synthesized by a new reaction, in which the solvent N,N-dimethylformamide involves. Its structure was determined by X-ray single crystal diffraction. The crystal belongs to triclinic, space group P-1 with the following crystallographic parameters: a = 7.977(2) Å, b = 10.394(3) Å, c = 10.837(3) Å, = 111.774(5)°, = 104.050(5)°, = 99.446(5)°, = 0.093 mm^–1, V = 776.6(4) ų, z = 2, Dx = 1.293 mg/m³, F(000) = 320, T = 293(2) K, 2.14° 25.03°, the final R factor: R ₁ = 0.0582, wR ₂ = 0.1399. The distance of N(4) C(2) (1.339 Å) is much shorter than the length of normal C N (1.47 Å) and very close to that of C-N (1.33 Å), which is indicative of the significant double bond character.     

Crystal structure of bis[dihydrobis(3,5-dimethy-1-pyrazolyl)borato]cadmium(II)

The structure of [H₂B(3,5-Me₂pz)₂]₂Cd shows the four nitrogen donor atoms form a pseudotetrahedral arrangement about the cadmium(II). The intraligand N—Cd—N angles are restricted to an average of 91.4° by the chelate rings forcing the interligand N—Cd—N bond angles to average 119.4°. The Cd—N bond distances average 2.21 Å with a range of 0.04 Å. The crystal is in the triclinic space group, P with a = 7.6793(2) Å, b = 8.5992(2) Å, c = 25.0874(4) Å, = 91.0791(2)°, = 97.9769(4)°, = 110.2344(6)°, and Z = 2.