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.     

Syntheses and structures of dihydrocalix[4]arenes bearing O-benzonitrile and O-acetonyl substituents

Three 25,27-dihydrocalix[4]arene derivatives, bearing benzonitrile and acetone groups on the oxygens, were prepared and structurally characterized. All three structures crystallize in , with cell dimensions: bis(benzonitrile)calix[4]arene·toluene, a = 11.530(2) Å, b = 12.013(2) Å, c = 14.089(4) Å, = 103.555(18)°, = 94.341(18)°, = 104.704(16)°, and V = 1815.9(7) ų; anti-bis-acetone-calix[4]arene, a = 7.5847(8) Å, b = 12.0948(17) Å, c = 15.3375(16) Å, = 78.982(10)°, = 76.932(9)°, = 73.129(10)°, and V = 1299.6(3) ų; syn-bis-acetone-calix[4]arene, a = 9.080(3) Å, b = 10.391(3) Å, c = 14.816(3) Å, = 96.998(19)°, = 100.02(2)°, = 103.93(3)°, and V = 1299.6(3) ų.     

Crystal and molecular structure of cesium isothiocyanatotrimethylaluminate,Cs[Al(CH3)3NCS]

The crystal structure of the title compound has been determined from three-dimensional X-ray diffraction data, and refined by full-matrix least-squares techniques. The crystals belong to the monoclinic space groupP2₁/c, witha = 8.849(4),b = 13.798(5),c = 7.943(4) Å, = 102.98(3) °, andD _x = 1.85g cm^–3 forZ = 4. The finalR factor for 1283 observed reflections is 0.046. The aluminum atom is bonded to the nitrogen atom of the thiocyanate ligand, where the Al-N bond length is 1.94(1) Å. The SCN is linear, and the CN-Al angle is 175(1) °. The cesium ion exhibits four contacts less than 3.60 Å: Cs C(thiocyanate) = 3.39(1) Å, Cs C(methyl) = 3.52(1) Å, Cs C.(methyl) = 3.56(1) Å, and Cs N = 3.575(9) Å. The closest Cs S is 3.772(3) Å.     

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.     

Synthesis and crystal structure of 1-(1′,3′-dimethyl-5′-chloropyrazol-4′-carbonyl′-3-(2′-chlorophenyl)-5-amino-4-cyanopyrazole

The title compound 1-(1,3-dimethyl-5-chloropyrazol-4-carbonyl)-3-(2-chlorophenyl)-5-amino-4-cyanopyrazole (C₁₆H₁₂Cl₂N₆O) has been synthesized and characterized by X-ray diffraction: Triclinic, space group P1, with a = 8.6712(8) Å, b = 9.5091(10) Å, c = 11.2170(11) Å = 71.531(2)°, = 84.683(2)°, = 74.099(2)° Z = 2; V = 843.7(14) ų. C(10), O(1), C(11), and N(2) atoms are coplanar with the average deviation of 0.0071 Å, which form 11.03° and 43.93° dihedral angles with pyrazole planes (I) and (II), respectively.     

Hydrogen-bonded coordination network in crystal structures of [Cu(3-PM)4Cl2] and [Cu(4-PM)4Cl]Cl, (PM = pyridylmethanol)

The crystal and molecular structures of [Cu(3-PM)₄Cl₂] (1) and [Cu(4-PM)₄Cl]Cl (2) have been determinated by X-ray crystallography. Complex 1 crystallizes in the triclinic system, space group P–1, with lattice parameters a = 7.972(2) Å, b = 8.293(2) Å, c = 10.707(2) Å, = 105.73(3)°, = 90.04(3)°, = 110.38(3)°, and Z = 1 at 100 K. The coordination geometry of each Cu atom is approximately octahedral formed by four nitrogen atoms of pyridine rings of 3-pyridylmethanol molecules in the equatorial plane and two chlorine atoms occupying the axial positions. The O—HsO, C—HsCl, and O—HsCl intermolecular hydrogen bonds and s stacking link the molecules in 3-D hydrogen-bonded coordination network. Complex 2 crystallizes in the tetragonal system, space group P4/n, with lattice parameters a = 10.464(1) Å, c = 11.339(2) Å, and Z = 2 at 217 K and a = 10.352(1) Å, c = 11.201(2) Å, and Z = 2 at 293 K. The coordination geometry of Cu atom in the [Cu(4-PM)₄Cl]⁺ ion is approximately square pyramidal formed by four nitrogen atoms of pyridine rings of 4-pyridylmethanol molecules in equatorial plane and one chlorine atom in axial position. The O—HsCl and C—HsCl intermolecular hydrogen bonds link the molecules in 2-D hydrogen-bonded coordination network.     

Crystal structure of N,N-bis(2,5-dioxopyrrolidin-1-ylmethyl)glycine

The preparation and molecular and crystal structures of the title compound are reported. The compound crystallizes in the triclinic space group (No. 2) with unit cell dimensions of a = 7.2493(3) Å, b = 8.9287(4) Å, c = 10.6594(4) Å, = 90.419(3)°, = 91.287(3)°, = 103.153(3)°, V = 671.62(5) ų, and Z = 2. The molecular structure of the title compound consists of three sections, the glycine chain and the two 2,5-dioxopyrrolidin-1-ylmethyl groups. Every molecule is linked with three adjacent molecules through three hydrogen-bonding patterns which are 8-membered or 20-membered rings. The chain of rings appears periodically, which makes the molecule form a layer structure in the crystal.     

Structural studies of N(4)-substituted thiosemicarbazones prepared from 4-formylantipyrine and a thiourea derived from 4-aminoantipyrine

Reaction of 4-formylantipyrine with N(4)-dimethylthiosemicarbazide and 3-piperidylthiosemicarbazide produces the N(4)-dimethylthiosemicarbazone (1), and the 3-piperidyl-thiosemicarbazone (2), respectively. Compound 1 is triclinic, space group P-1 with a = 6.329(1) Å, b = 11.699(1) Å, c = 11.943(1) Å, = 65.83(1)°, = 80.83(1)°, = 84.90(1)°, and V = 796.1(1) ų with Z = 2, for D _calc = 1.324 g/cm³. Compound 2 is triclinic, space group P-1 with a = 6.784(1) Å, b = 10.485(2) Å, c = 13.462(3) Å, = 102.05(2)°, = 98.61(2)°, = 101.32(2)°, and V = 899.8(5) ų with Z = 2, for D _calc = 1.319 g/cm³. Reaction of 4-aminoantipyrine with phenyl isothiocyanate produced N-antipyrine-N-phenylthiourea (3). Compound 3 is monoclinic, space group P2₁/n with a = 6.863(7) Å, b = 15.361(3) Å, c = 16.332(5) Å, = 90.35(6)°, and V = 1720.7(18) ų with Z = 4, for D _calc = 1.306 g/cm³. Compounds 1 and 2 have intermolecular hydrogen bonding between the carbonyl oxygen of the antipyrine moiety and the NH hydrogen of the thiosemicarbazone moiety. In 3 the two unique molecules are held together as a dimer by interactions of the two thiourea NH's and the antipyrine moiety's\break oxygen.     

Characterization and structural analyses of trimethoxy and triethoxybenzo[b]thiophene

The crystal and molecular structures of two methoxybenzo [b] thiophenes have been determined by three-dimensional, single-crystal X-ray diffractometry. Both 3-(3,4,5-trimethoxybenzoyl)-2-(4-methoxyphenyl)-6-methoxybenzo[b]thiophene and 3-(3,4,5-triethoxybenzoyl)-2-(4-methoxyphenyl)-6-methoxybenzo[b]thiophene (hereafter referred to as I and II, respectively) crystallize in the triclinic centrosymmetric space group (No. 2, C¹) with two formula units per cell with a = 6.842(1) Å, b = 12.602(2) Å, c = 13.815(2) Å, = 94.80(1)°, = 98.27(2)°, and = 100.59(2)° and a = 10.600(1), b = 11.415(2), c = 12.137(2) Å, = 94.57(1)°, = 101.18(1)°, and = 110.45(1)°, respectively. The phase problems were solved by direct methods and the respective final full-matrix least-squares refinements converged to R = 0.039 and 0.068. The structures differ in the orientation of the trimethoxy and triethoxy groups of the benzoyl ligands. The molecules in the crystal lattice are held together by van der Waals forces. Selected bond distances, angles, and torsion angles are tabularized as well as reference to the synthesis of the title compounds and peripheral studies.     

Bis(2,6-(2′,6′-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II)

Bis(2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II) was prepared by the reaction of 2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenol with nickel chloride. The title complex crystallized in P2₁/c, with cell dimensions a = 9.962(2) Å, b = 12.087(3) Å, c = 24.445(6) Å, and = 97.032(5), giving a volume of 2921.4(13) ų. The bis(2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II) adapts an ideal parallelogram, in which the Ni atom is coordinated with two phenolic oxygen atoms [O(1), O(1A)] and two imino nitrogen atoms [N(1), N(1A)].     

Tris(triphenylphosphine)rhodium cyano and triphenylcyanoborate complexes: Structures and a DFT study

The structures of [Rh(CN)(PPh₃)₃](EtOH) (1), [Rh(NCBPh₃)(PPh₃)₃] (2), and [Rh(CNBPh₃)(PPh₃)₃] (3) are reported together with a density functional theory (DFT) study of the model compounds [Rh(NCBH₃)(PH₃)₃] and [Rh(CNBH₃)(PH₃)₃]. Compound 1 crystallizes in space group Pc with a = 10.4798(15) Å, b = 12.5410(18) Å, c = 19.974(3) Å and = 112.215(6)°; compound 2 crystallizes in space group with a = 12.929(2) Å, b = 14.362(2) Å, c = 17.575(3) Å and = 92.544(3)°, = 90.214(3)°, = 113.831(3)°; compound 3 crystallizes in space group with a = 12.915(2), b = 14.296(2), c = 17.664(3) Å and = 92.469(3)°, = 90.088(3)°, = 113.768(3)°. All three complexes show slight tetrahedral distortion from ideal square planar geometry (largest for 1). Differences in the reactivity and stability of 2 and 3 are interpreted according to the results of a density functional theory study.     

A new monoclinic crystal phase of [Bu4N][Ni(dmit)2]

The crystal structure of the title compound, tetrabutylammonium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickelate(III), [N(C₄H₉)₄][Ni(C₃S₅)₂], is the fourth known phase of this polymorphous compound. It is monoclinic space group P2₁/c, with a = 20.040(2) Å, b = 13.1151(17) Å, c = 12.1093(15) Å, = 105.456(15)°, and V = 3067.5(6) ų with Z = 4, for D _calc = 1.503 g cm^–3. The [Ni(dmit)₂] anion packing arrangement consists of arrays of side-on touching anions and these arrays are connected via head-to-tail close S S contacts.     

Crystal structure of μ-adeninatobis (methylmercury (II)) perchlorate monohydrate

The title compound belongs to the triclinic space groupP¯1,a= 8.189 Å,b = 9.863 Å,c = 10.726 Å, = 69.93 °, = 68.62 °, = 73.66 °, andZ = 2. The structure was refined on 1337 observed reflections to anR factor of 0.042. The crystals contain [adeninato(CH₃Hg)₂]⁺ complex cations in which mercury is linearly bonded to N(7) and N(9) of a deprotonated adenine ring. Centrosymmetrically related complex cations are paired via two N(6)-H(6) N(l) hydrogen bonds. Those planar units are stacked in the crystal with a distance of 3.4 Å between rings. The water molecule and the ClO₄ ^-ion are involved in hydrogen bonding and HgO contacts. This structure identifies N(7) as the best residual coordination site after H(9) has been substituted by CH₃Hg.     

4-(1,4-Dimethoxy-2-naphthyl)-4- hydroxycyclohexanone and its ethylene ketal

Intramolecular hydrogen bonding in the solid state is reported for the title compound and its ethylene ketal. The title compound crystallizes in the triclinic space group, with a = 9.590(3), b = 9.620(3), c = 9.844(2) Å, = 97.67(2), = 105.25(2), = 115.47(2), and Z=2. The ethylene ketal crystallizes in the monoclinic space group, P2₁/c, with a = 7.230(2), b = 22.639(3), c = 10.839(2) Å, = 101.47(2), and Z = 4. The intramolecular hydrogen bond length of 1.79 Å is the same for the ketone and ketal, but the O—H---O valence angle is 144° for the ketone and 165° for the ketal.     

Schiff bases and their complexes with metal ions. Part II. Structures of N-n-butyl-2-hydroxy-1-naphthaldimine and bis[N-n-pentyl-2-hydroxy-1-naphthaldiminato]nickel(II)

The Schiff base ligand (1), [C₁₅H₁₇NO] crystallizes in the monoclinic space group P2₁/c witha=10.054(3),b=10.313(3), c=13.173(4)Å, =107.42(4)°,V=1303.2(7)ų,Z=4,Dx=1.159 g cm^–3, and (MoK)=0.674 cm^–1. The C2-O[1.23(1)Å] and C3–C4 [1.33(2)Å] bond lengths are short, due to its quinoidal structure. In the Schiff base nickel complex (2), [Ni(C₁₆H₁₈NO)₂] the asymmetric unit is comprised of two half-complexes. It crystallizes in the triclinic space group witha=5.124(3),b=16.227(3),c=16.886(4)Å, =95.47(8), =96.00(1), =90.71(4)°,V=1389.6(9) ų,Z=2,Dx=1.289 g cm^–3, and (MoK) =12.1 cm^–1. The coordination of the Ni(II) ions are square planar with bond angles between 87.9(1) and 92.1(1)°. The Ni–O and Ni–N distances are 1.819(2), 1.922(2) and 1.823(2), 1.914(3)Å in these two complexes.     

Crystal structure of 6-nitrobenzo(a)pyrene

In 6-nitrobenzo(a)pyrene, an environmental pollutant, the nitro substituent lies at 69.5(1) to the mean plane of the aromatic moiety. The C–C bond distances range from 1.341(3) to 1.443(3) Å. The crystal is in the monoclinic space group, P2₁/c, with a = 8.3239(3) Å, b = 8.9530(3) Å, c = 18.0678(5) Å, = 99.264(2) and Z = 4. Molecules are assembled in sheets in the unit cell through stacking and alternating C–H O interactions.     

Structures of Z-(nitrostilbene)chromium tricarbonyl complexes: The effect of metal coordination on the nonplanarity of the stilbene system

The structures of the nitrostilbene complexes Z-(4-R–C₆H₄–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃ (R=Me₂N,1; H,2; F₃C,3), are reported. The copounds were prepared as part of a study of the synthesis of organometallic complexes with potential nonlinear optics applications. For Z-(4-Me₂N–C₆H₄–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃,1, triclinic, ,a=7.214 (3) Å,b=7.340 (3) Å,c=17.238 (9)Å, =88.23 (5)°, =88.76 (4)°, =87.66 (3) °,Z=2. For Z-(C₆H₅–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃,2, monoclinic, P2₁/C,a=12.255 (3) Å,b=9.415 (1) Å,c=13.579 (4) Å, =105.60 (2)°,Z=4. For Z-(4-F₃C–C₆H₄–CH=CH–C₆H₄-4-NO₂)Cr(CO)₃,3, triclinic, ,a=7.094 (2) Å,b=8.057 (5) Å,c=17.295 (9) Å, =87.95 (5)° =85.94 (4)°, =64.24 (5)°,Z=2. The structural data show that the Z isomers exhibit bond lengths and angles similar to those observed in the E isomers, but the stilbene fragment is considerably more nonplanar. As a consequence, these molecules are unlikely to behave as NLO materials.     

Synthesis and crystal structure of trans-bis(O, O′-diisopropylthiophosphoryl-1H-imidazole-N3) bis(O,O′-diisopropyldithiophosphato) nickel(II) complex: Ni[N3-ImSP(OiPr)2]2[S2P(OiPr)2]2 (Im = imidazole; iPr = isopropyl)

The mononuclear complex, Ni[N³-ImSP(OiPr)₂]₂[S₂P(OiPr)₂]₂ (Im = imidazole; iPr = isopropyl), was unexpectedly obtained in a reaction of bis(O,O-diisopropyl-dithiophosphato) nickel(II) complex with imidazole ligand, and its structure was determined by X-ray crystallography. It crystallizes in the triclinic system, space group P , with lattice parameters a = 12.437(3) Å, b = 13.181(3) Å, c = 8.4580(17) Å, = 93.16(3)°, = 101.93(3)°, = 65.26(3)°, and Z = 1. The Ni atom has almost perfect octahedral coordination geometry and is coordinated by two N atoms of imidazole from two O,O-diisopropylthiophosphoryl-1H-imidazole ligands in axial positions and four S atoms from two (O,O-diisopropyldithiophosphato) anions which act as bidentate ligands forming a four-membered chelate ring in the equatorial plane. The Ni—S bond distances are 2.469(1) and 2.507(1) Å, and the Ni—N bond distances are 2.097(2) Å. The IR spectra data are in agreement with the structural data.     

Crystal structures of two 1,2-bis-(1-aryl-3-methyltriazene-3-yl-)ethanes with aryl substituents of opposite polarity

The crystal and molecular structure of 1,2-bis-{1-(2-cyanophenyl)-3-methyltriazen-3-yl-}ethane (1) and 1,2-bis-{1-(2-methoxyphenyl)-3-methyltriazen-3-yl-}ethane (2) have been determined by single crystal X-ray diffraction analysis. Bis-triazene (1) exists as the staggered conformation in the solid state, with an anti-anti configuration around the N2–N3 bond of the triazene units, whereas 2 assumes a gauche conformation with the syn-syn configuration in the triazene units. Crystal data: 1 C₁₈H₁₈N₈, triclinic, space group P –1, a = 6.108(2), b = 8.118(3), c = 9.600(4)Å, = 101.37(7)°, = 96.47(7)°, = 102.71(5)°, V = 449.1(3)ų, Z = 2; 2 C₁₈H₂₄N₆O₂, monoclinic, space group P 2₁/n, a = 13.119(5), b = 7.745(2), c = 19.201(2)Å, = 96.47(7)°, V = 1910.3(9)ų, Z = 4.     

Synthesis and crystal structure of a nickel(II) complex involving imino nitroxide radicals

A new complex of formula [Ni(im2-py)₂(SCN)₂]CH₃OH (im2-py = 2-(2-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl) has been synthesized and the crystal structure determined by X-ray diffraction methods. The complex crystallizes in the monoclinic space group P2₁/n with a = 15.525(5) Å, b = 13.405(4) Å, c = 16.167(5) Å, = 113.324(5)°, V = 3089.6(16) ų, and Z = 4. The structure of this complex is mononuclear with the nickel(II) ion octahedrally coordinated and bound to the imino nitroxide radicals through the imino nitrogen atoms. The thiocyanate groups are coordinated to the metal by the nitrogen atoms.