Synthesis,crystal and molecular structure ofN-(p-chlorobenzylamide) ofα-(1,1-ethylenedioxy)-ethyl-γ-hydroxybutyric acid

N-(p-chlorobenzylamide) derivative of-(1, 1-ethylenedioxy)-ethyl--hydroxybutyric acid has been synthesized and the its crystal structure was solved. The dioxolane ring adopts a half-chair conformation, with asymmetry parameter C₂(13)=5.4°. Deformation of the amide group is caused mainly by twist around the C4-N bond.     

X-ray and NMR structural investigations of (±) (u) N-(1-phenylethyl)-1-t-butylsulfinyl-1-propenyl-2-amine,C15H23NOS

The structure of the title compound has been investigated in the solid state and in solution by X-ray and NMR-NOE methods, respectively. The crystals are monoclinic:P2₁/c,a=9.828(1),b=12.326(2),c=13.976(2) Å,=107.36(1)°. The structure was solved by direct methods, and refined against 2495 unique reflections by a full-matrix, least-squares procedure givingR=0.046. In the solid state the compound exists as theE isomer with unlike relative configurations on asymmetric atoms. In solution the compound is found as a mixture of a single enamine and two imine forms. The MM calculations suggest that of the two possible geometrical isomers of both diastereoisomersu andl of the enamine, theZ forms should be of lower energy. The total recognition of the homonuclear¹H NMR-NOE data interpreted in terms of their distance dependence in the two geometrical forms also favors theZ isomer in both diastereomers.     

Synthesis and crystal structure of a polymeric erbium(III)–sodium(I) coordination complex of picolinic acid N-oxide

A new Er(III)–Na(I) coordination polymer of stoichiometry [NaEr₂L₅(H₂O)₆(NO₃)](NO₃)·3.5H₂O (HL = picolinic acid N-oxide) has been synthesized and characterized by single-crystal X-ray analysis. Crystals are triclinic, P with a = 9.823(2), b = 12.453(2), c = 20.643(4) Å; = 98.49(3), ( = 101.40(3), = 108.69(3)°; V = 2284(1) ų; Z = 2. Of the two independent eight-coordinate erbium(III) ions in this complex, one is surrounded by four bidentate chelating L ligands, and the other by one bidentate chelating L ligand, four aqua ligands and two anti-carboxylate oxygen atoms from two neighboring [ErL₄] units. The sodium(I) ion is in a distorted octahedral environment, being coordinated by a unidentate nitrate anion, three aqua ligands and two anti-carboxylate oxygen atoms from two adjacent [ErL₄] units. The complex is built from zigzag chains of syn-anti carboxylate-bridged erbium(III) moieties directed in the a direction, which are cross-linked pairwise by aqua-bridgeddimericsodium(I) units. The resulting composite polymeric chains are further connected by hydrogen bonds to form a three-dimensional network.     

An unusual function of the anion of 1-hydroxyethane-1,1-diphosphonic acid (H4 L): Crystal structure of [Ni(Phen)3](H7 L 2)0.5(H5 L 2)0.5 ⋅ 2H2O

Crystals of [Ni(Phen)₃](H₃ L)₂ ? 2H₂O (H₄ L is 1-hydroxyethane-1,1-diphosphonic acid) have been synthesized, and their structure has been determined by X-ray diffraction analysis. The cationic complexes [Ni(Phen)₃]²⁺, the centrosymmetric dimeric anions H₇ L ₂ ^? and H₅ L ₂ ^3? , and the molecules of crystallization water are the structural units of the crystal. The outer-sphere function of the H4 L anions in transition metal compounds and also the presence of differently charged dimeric anions are revealed for the first time. The structural units are joined together by an extended system of hydrogen bonds, including symmetric (or pseudosymmetric) hydrogen bonds in dimeric anions (O?O, 2.436 and 2.466 Å). The Ni-N(Phen) bond lengths fall in the range 2.074–2.107 Å. The compound has the structural formula [Ni(Phen)₃](H₇ L ₂)_0.5(H₅ L ₂)_0.5 ? 2H₂O.     

Crystal and molecular structure of the inclusion compound between 1,1′-binaphthyl-2,2′-dicarboxylic acid and acetylacetone (1∶1)

The lattice type crystalline inclusion compound of 1,1-binaphthyl-2,2-dicarboxylic acid (BNDA) with acetylacetone (AcAc) 11 has been investigated by single crystal X-ray diffraction. AcAc is present as the enolic tautomer, stabilized by a notably short intramolecular hydrogen bond. This H-bond closes a six-membered ring with delocalization of the system of conjugated double bonds. In the crystal the AcAc molecules are incorporated into channels, delimited by bulky binaphyl moieties, in a hydrogen-bonded framework of BNDA, and they do not show any disorder. The strictly stoichiometric host:guest ratio seems to be enforced by packing forces only.     

Crystal and molecular structure of dipotassium-aquapentachlororhodate (III): (K2)++ [RhCl5(H2O)]2−

The structure of K₂[RhCl₅(H₂O)] has been established by X-ray crystallography. It crystallizes in the orthorhombic space groupPcmn, with cell dimensionsa=7.065(1),b=9.453(1),c=13.567(1) Å,V=906.1(3) ų,Z=4,M _r =376.4,D _x =2.76 g cm^–3,F(000)=712,T=293 K. The final wasR=0.046. The rhodium atom has a distorted octahedral coordination involving five chlorine atoms and an oxygen of the water molecule with Rh, O, and three chlorine atoms on the mirror plane. Rh-Cl distances range from 2.284(7) Å to 2.345(7) Å. The Cl(4)O intermolecular distance, 3.140(12) Å indicates strong hydrogen bonding between oxygen and chlorine atoms of the neighboring octahedra.N. C. L. Communication No. 5353.     

Synthesis and structure analysis of 2-(2′-propanonylthio)-3-(o-methyl phenyl) quinazol-4(3H)-one

The three-dimensional molecular and crystal structure of 2-(2'-propanonylthio)3-(o-methyl phenyl)quinazol-4(3H)-one has been determined by X-ray crystallographic methods. This compound crystallizes in the orthorhombic space group P_bca with unit cell parameters: a=9.649(5), b=30.102(10), c=11.403(9)Å. It has been solved by direct methods and refined to a residual index of 0.054. The magnitude of torsion along C16— C11— N3— C4 bond is 93.5(4)°. The dihedral angle between the plane comprising all the ring atoms of quinazoline moiety and the atoms of the methyl substituted phenyl ring is 94.12(1)°. The crystal structure is stabilized by one intramolecular C— HsO interaction and three intermolecular C— HsN contacts.     

Synthesis and crystal structure of manganese(III) hydroxyl-containing Schiff base complexes: [Mn(III)(Hvanpa)2]N3 (H2vanpa = 1−(3-hydroxysalicylaldeneamino)-3-hydroxypropane)

The manganese complex, [Mn(III)(Hvanpa)₂]N₃ has been prepared and the crystal structure determined using x-ray crystallography. The mononuclear complex has a six-coordinate octahedral geometry. The complex crystallizes in the monoclinic space group P2₁/c with a = 9.867(1), b = 13.316(2), c = 9.0110(1) Å, = 107.870(1)°, V = 1126.8(2) ų, and Z = 2. The Mn-O and Mn-N distances in the equatorial plane are in good agreement with those found for other manganese(III) Schiff base complexes. In the axial direction, the Mn-O distances of 2.274(2) Å is about 0.3 Å longer than those in the equatorial plane due to a Jahn-Teller distortion at the d⁴ manganese(III) center. In the crystal, each azido ion is linked through hydrogen bonding with two hydrogen atoms from the coordinate hydroxyl groups at the apical site.     

Crystal and molecular structure of 4-(3-indolyl)butyric acid-picric acid 2/2 π complex

The title compound, IBA-PIC, is 2C₁₂H₁₃NO₂·2C₆H₃N₃O₇, triclinic,P¯1,a=7.137(1),b=15.355(4),c=18.282(5) Å,=79.72(2),=79.85(2), =76.87(2)°. The structure was solved by direct methods and refined by least-squares techniques to anR factor of 0.068 for 3395 observed reflections. The IBA-PIC complex occurs as two independent molecules with different conformations. The crystallographic evidence for a prominent overlapping between the phenyl and indole rings corroborates earlier conclusions from UV spectroscopy. Molecules of both IBA and picric acid lie approximately parallel to (100) in layers and -bonding interactions across the 3.55 Å spacing. The angles between the indole ring and carboxyl-group planes are 82.9 and 86.9° for the A and B molecules, respectively.     

Structural studies of N-2-(3-picolyl)- and N-2-(4-picolyl)-N′-tolylthioureas

Reactions of 2-aminopicolines with 2- and 4-tolyl isothiocyanates yielded N-2-(4-picolyl)-N-4-tolylthiourea, 1, N-2-(3-picolyl)-N-4-tolylthiourea, 2, and N-2-(4-picolyl)-N-2-tolylthiourea, 3. Compound 1 is monoclinic, of space group P2₁/c with a = 7.456(1) Å, b = 13.135(3) Å, c = 13.959(3) Å, = 104.99(3)°, and V = 1320.5(5) ų with Z = 4, for d _calc = 1.294 g/cm³. Compound 2 is triclinic, of space group with a = 6.877(3) Å, b = 7.590(5) Å, c = 13.213(9) Å, = 78.38(2)°, = 77.96(4)°, = 86.36(4)°, and V = 660.5(7) ų with Z = 2, for d _calc = 1.294 g/cm³. Compound 3 is monoclinic, of space group P2₁/c with a = 12.604(2) Å, b = 15.592(3) Å, c = 6.875(2) Å, = 91.05(2)°, and V = 1350.9(2) ų with Z = 4, for d _calc = 1.265 g/cm³. The three thioureas are found in both solid state and solution in a conformation resulting from intramolecular hydrogen bonding. Compounds 1 and 3 present an intermolecular hydrogen bond involving the thione sulfur and the NH hydrogen, which is not present in 2 owing to the steric hindrance of the methyl group in the phenyl ring. The geometry of the molecule is affected by the position of the methyl groups on the pyridine and aryl rings.     

Molecular structure of 3α-ethoxy-8α-acetoxy-13-hydroxy-lactar-6(7)en-5-oic acid γ-lactone

The structure of the title compound has been investigated in the solid state by X-ray diffraction. The crystals are tetragonal, space groupP4₁2₁,2 (No. 92), with cell dimensions:a=10.463(1),c=34.603(8)Å. The structure was solved by direct methods and refined with 3634 unique reflections by a full-matrix, least-squares procedure givingR=0.0460,R _w=0.0472 (w=1/ _F ² . The stereochemical analysis of the molecule confirmed the expectations based on earlier NMR investigations of the title compound and its precursors.     

Crystal and molecular structure of (±)-1-phenyl-2-amino-1-propanol,C9H13NO

The crystal structure of (±)-phenylpropanolamine has been determined by single-crystal X-ray diffraction methods. The structure was solved by direct methods and refined by least-squares toR=0.055 andR _w=0.045 for 2000 reflections (I2 (I)). The molecule was found to adoptgauche geometry. Inter- and intramolecular N-HO and O-HN hydrogen bonds were observed in the crystal structure.     

Molecular structure of [trans-FeCl2(imidazole)4]Cl·THF·H2O

The structure of [trans-FeCl₂(imidazole)₄]Cl has been determined as the THF/H₂O solvate. The Fe-Cl and Fe-N distances in the cation are shorter than analogous trans-FeCl₂(L)₄ compounds, concomitant with the decreased ionic radius of Fe³⁺ versus Fe²⁺. Crystal data: orthorhombic, Pnma, a = 8.456(2), b = 20.991(4), c = 13.288(3) Å, V = 2358.6(8), andZ = 4.     

Molecular structure of 1-phenyl-1-dimethylamino-4,4-bis(trimethylsilyl)-2-aza-3λ3-phosphabutadiene-1,3

The crystal and molecular structure of 1-phenyl-1-dimethylamino-4,4-bis(trimethylsilyl)-2-aza-3³-phosphabutadiene-1,3, Me₂N(Ph)C=N—P=C(SiMe₃)₂ (1), has been determined. Crystal data: triclinic, P1¯, a = 8.975(4), b = 10.001(5), c = 12.440(6) Å, = 79.04(4), = 77.98(4), = 73.07(4)°, V = 1034.7 ų, Z = 2, and D _c = 1.08 g cm^–3. The main geometrical parameters of 1 as well as ab initio (HF/6-31+G**) calculations of the model systems show no clear evidence of high efficiency of the (C=N)— (P=C) conjugation.     

Synthesis and crystal structure of catena-μ-chloro-bis(acetonitrile)copper(I) [(H3CCN)2CuCl]∞

The new crystalline compound of catena--chloro-bis(acetonitrile)copper(I) [(H₃CCN)₂ CuCl] has been synthesized and structurally characterized by X-ray crystallography. The compound is an infinite polymeric chain in which chlorides bridge the coppers. Copper exhibits tetrahedral coordination geometry with two acetonitrile molecules acting as coordinating ligands. The compound crystallizes in the orthorhombic Pbcm space group with a = 12.585(3) Å, b = 7.496(2) Å, and c = 7.275(2) Å.     

Synthesis and structure of (H2O·HBF4)2(18-crown-6)

The title compound has been prepared by the addition of fluoroboric acid to 18-crown-6 in toluene. The compound crystallizes in the triclinic space group P¯1 witha=7.341(2),b=8.364(2),c=10.631(3)Å,=71.48(2),=67.91(2), =67.94(2)°, andD _c =1.44 g cm^–3 forZ=1. The final conventionalR value was 0.079 based on 1575 observed reflections. The molecule resides on a center of inversion. The (H₂O·HBF₄) moieties are best viewed as fluoroboric acid monohydrate molecules hydrogen bonded to the crown ether, one above and one below the plane of the crown. The FO(water) hydrogen bond separation is 2.474(5)Å, and the O(crown)O(water) separations are 2.834(5) and 2.841(6) Å. The oxygen atoms of the crown ether are planar to 0.23 Å.     

Crystal and molecular structure of the (−)-N-hydroxyimide of (10-pinene-2-yl) succinimic acid

Two independent molecules in the unit cell are the same enantiomer of the title compound but possess slightly different conformations. Both conformers are joined by H-bonds to one water molecule. The configuration at C11 was established asR.Crystal data: C₁₄H₁₉O₃N×1/2H₂O; trigonal,P3₂;a=17.486(2),b=17.486(2),c=8.024(1)Å;V=2124.72(6)ų;Z=6; (CuK)=1.54178 Å;F(000)=834; finalR=0.0495 for 2376 reflections (of 2747 unique data).     

X-ray crystal structure of 2-hydroxy-2′-(1,4-bisoxo-6-hexanol)-1,1′-biphenyl

The X-ray crystal structure of 2-hydroxy-2-(1,4-bisoxo-6-hexanol)-1,1-biphenyl, 3, is presented. This molecule crystallizes in the monoclinic space group P2₁/n (a = 9.440(2), b = 12.679(3), c = 11.679(3) Å = 94.60(2)° V = 1382.5(5) ų; Z = 4). One of the unique features of the X-ray structure of 3 is the intramolecular hydrogen bonding. The hydrogens of the phenolic and hydroxy groups occupies bridging positions via hydrogen bonding to an ether oxygen (O₁) and a phenolic oxygen (O₄), respectively. This hydrogen bonding does not affect the interplanar angle between phenyl rings (49.34°), which is in the range expected for ortho-disubstituted biphenyl compounds. The hydrogen bonding of this type explains why it is difficult to alkylate both phenoxy groups of 2,2-biphenol with tetrahydropyranyl protected 2-(2-chloroethoxy)ethanol.     

Crystal structure of chloro[1-hydroxyethane-1,1-diphosphonato(3−)]ditin(II) monohydrate Sn2(HL)Cl · H2O

The synthesis and X-ray structure analysis of Sn₂(HL)Cl · H₂O, where HL ^3? is the anion of 1-hydroxyethane-1,1-diphosphonic acid, are reported. The coordination polyhedra of two independent tin(II) atoms are the Sn(1)O₂Cl and Sn(2)O₃ trigonal pyramids, in which one of the vertices is occupied by a lone electron pair (Sn-O, 2.144–2.218 Å and Sn-Cl, 2.573 Å). The pyramids are complemented by weaker Sn?O and Sn?Cl contacts to form severely distorted (3 + 3) octahedra. The SnO₂Cl and SnO₃ pyramids are linked by the HL ^3? bridging ligands into the [Sn₂(HL)Cl]₆ cyclic molecules, which, in turn, are joined by additional Sn?O, Sn?Cl, O(H₂O)?O(L), and O(H₂O)?Cl contacts with each other and with crystallization water molecules into a three-dimensional framework.     

Keto–enol tautomerism, conformations, and structure of 1-[N-(4-chlorophenyl)]aminomethylidene-2(1H)naphthalenone

1-[N-(4-chlorophenyl)]aminomethylidene-2(1H)naphthalenone (C₁₇H₁₂NOCl) (1) was synthesized and the crystal structure was determined. Compound 1 crystallizes in the monoclinic space group P2₁/n with a = 4.761(3) Å, b = 20.347(1) Å, c = 13.773(2) Å, = 92.89(3)°, V = 1332.4(3) ų, Z = 4, D _c = 1.404 g cm^–3, (Mo K) = 0.28 mm^–1, and R = 0.036 for 2680 reflections [I > 2(I)]. Molecule 1 is not planar, and the dihedral angle between the naphthaldeyde plane A [C1–C11, 01] and the 4-chloroaniline plane B [C12–C17, C11, N1] is 20.1(3)°. An intramolecular hydrogen bond occurs between the hydroxyl oxygen and imine nitrogen atoms [2.528(3) Å]. IR, ¹H NMR, and UV measurements and AM1 semiempirical quantum mechanical calculations support the keto form found in the X-ray structure.