Hydrate Stabilization in the Three-Dimensional Hydrogen-Bonded Structure of the Brucinium Compound,Bis(2,3-dimethoxy-10-oxostrychnidinium) Biphenyl-4,4′-disulfonate Hexahydrate

Abstract  

The crystal structure of the 2:1 proton-transfer compound of brucine with biphenyl-4,4 ′ -disulfonate, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4 ′ -disulfonate hexahydrate (1) has been determined at 173 K. Crystals are monoclinic, space group P2₁ with Z = 2 in a cell with a = 8.0314(2), b = 29.3062(9), c = 12.2625(3) ?, β = 101.331(2)°. The crystallographic asymmetric unit comprises two brucinium cations, a biphenyl-4,4 ′ -disulfonate dianion and six water molecules of solvation. The brucinium cations form a variant of the common undulating and overlapping head-to-tail sheet sub-structure. The sulfonate dianions are also linked head-to-tail by hydrogen bonds into parallel zig-zag chains through clusters of six water molecules of which five are inter-associated, featuring conjoint cyclic eight-membered hydrogen-bonded rings [graph sets R ₃³(8) and R ₄³(8)], comprising four of the water molecules and closed by sulfonate O acceptors. These chain structures occupy the cavities between the brucinium cation sheets and are linked to them peripherally through both brucine N⁺–H···O_sulfonate and O_carbonyl···H–O_water to sulfonate O bridging hydrogen bonds, forming an overall three-dimensional framework structure. This structure determination confirms the importance of water in the stabilization of certain brucine compounds which have inherent crystal instability.     

Structural study of the molecular complex in crystals of brucine with pantolactone

We have determined an X-ray crystal structure, a = 12.482(1), b = 14.349(1), c = 14.342(1) Å, orthorhombic, P2₁2₁2₁ for a molecular complex of brucine with pantolactone. The crystal structure is composed of corrugated sheets of brucine molecules containing the guest pantolactone molecules. The conformational twist of the pyrrolidine ring in brucine may probably be important in projecting the amine N2 to provide a strong and specific binding site for a chiral complexation. The pseudo-equatorial orientation of the hydroxyl group of the pantolactone anchors itself for binding via hydrogen bonding. In the crystal packing, the pantolactone molecules form helices and the brucine molecules are attached to these helices by O=H···N hydrogen bonds.     

X-Ray crystal structure determination of a series of 1-aryl- 2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1, 3-diazepan-1-yl]-1-diazenes obtained from the reaction of diazonium salts with mixtures of formaldehyde and 1,4-diaminobutane

A new series of bis-triazenes, the 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes has been synthesized from the reaction of diazonium salts with a mixture of 1,4-diaminobutane and formaldehyde. The structures of 1-(p-bromophenyl)-2-[3-{3-[2-(p-bromophenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene(1), 1-(p-cyanophenyl)-2-[3-{3-[2-(p-cyanophenyl)-1-diazenyl]-1,3-di azepan-1-ylmethyl}-1,3-diazepan-1-yl]-1-diazene(2), and 1-(p-methoxyphenyl)-2-[3-{3-[2-(p-methoxy-phenyl)-1-diazenyl]-1,3-diazepan-1-ylmethyl}-1,3-diazepan-1-yl]-1 diazene(3) have been unequivocally determined by X-ray crystallography. The new bis-triazenes are important since the structure contains the novel saturated heterocycle, 1,3-diazepane. The general conclusion of this study is that alkanediamines with 3 or 4 carbon atoms in the spacer link between the nitrogen atoms give rise to the linear bicyclic molecules of type 5, in contrast to the case of ethylenediamine (spacer link 2 carbon atoms), which affords molecules of type 6, which exemplify the general cage structure of type 4. The crystal structures of 1, 2 and 3 are compared with the previously reported structure of the hexahydropyrimidine analogue 8a(X=CN); compounds 2 and 8a(X=CN) are homologous with respect to the alkane spacer moiety. The structures of 2 and 8a(X=CN) are very different in one respect; in 2 the aryldiazenyl-1,3-diazepanyl groups are in the s-trans orientation around the central methylene group whereas in 8a(X=CN) the arrangement of the aryldiazenyl-hexahydropyrimidinyl groups is the s-cis orientation.Crystal data: 1 C₂₃H₃₀N₈Br₂, triclinic, space group P-1, a=8.3979(2), b=10.7828(3), c=14.4692(5) ?, α=83.670(1), β=78.662(1), γ=78.758(1)°, V=1256.48(6) ?³, for Z=2. 2 C₂₅H₃₀N₁₀, monoclinic, space group P2 ₁ /n, a=13.4046(6), b=9.4482(4), c=10.6913(4)?, β=103.239(2)°, V=2490.5(2) ?³, for Z=4. 3 C₂₅H₃₆N₈O₂, triclinic, space group P-1, a=8.5223(3), b=10.6913(4), c=14.4034(7)?, α=85.657(2), β=78.731(2), γ=80.153(1)°, V=1266.88(9) ?³, for Z=2.     

Crystal structure of usnic acid sodium salt 2 1/2 hydrate

Usnic acid, 1,3(2H,9bH)-dibenzofurandione-2,6-diacetyl-7,9-dihydroxy-8,9b-dimethyl, (1) was isolated from the lichenUsnea barbata by supercritical CO₂ extraction. The corresponding sodium salt 2 1/2 hydrate was obtained by reacting the acid with sodium carbonate. (C₁₈H₁₅O₇Na·2.5 H₂O) × 2,M _r =822.68, triclinic,P1,a=14.179(8),b=7.369(4),c=9.109(6)Å,=88.47(2),=105.35(2),=92.27(2)°,V=917(2)ų,Z=1,D _x =1.490 g cm^–3, (MoK)=0.71073 Å,=1.32 cm^–1,F(000)=430,T=293(2)K. The structure was solved by direct methods and refined toR=0.038 for 3229 observed reflections. Both Na ions are pentacoordinated. Their coordination polyhedra are distorted square pyramids bound together by a common water molecule (OW1). The molecules are also joined together by a common water oxygen (OW2) in an infinite chain which lies parallel to theb-axis. The chains are held together by hydrogen bonds. The conformation of usnic acid in the complex differs from that found previously by a rotation of the acetyl group bound to the cyclohexadienone ring.     

Crystal Structure of the Dihydrogen Phosphate Salt of Ozagrel (ozagrel=(E)-3-[4-(1H-Imidiazol-1-ylmethyl)phenyl]-2-Propenic Acid)

Abstract  Ozagrel, (E)-3-[4-(1H-Imidiazol-1-ylmethyl)phenyl]-2-propenic acid, crystallizes with phosphoric acid from aqueous solution to give the dihydrogen phosphate salt of ozagrel which crystallizes in the orthorhombic space group P2₁2₁2₁ with a = 4.6901(14), b = 8.929(4), c = 34.558(13) ?, V = 1447.2(9) ?³, Z = 4, C₁₃H₁₅N₂O₆P, M _r  = 326.24, D _c  = 1.497 g/cm³. In the crystal structure, phosphate anions interact with ozagrel through two kinds of hydrogen bonds forming a 1D hydrogen-bonded chain. Phosphate anions are hydrogen-bonded to each other through supramolecular synthon R₃³(12) forming a 1D double-chain structure which links ozagrel molecules into a 3D structure. Index Abstract  In crystal structure of the title compound, phosphate anions interact with ozagrel through two kinds of hydrogen bonds forming a 1D hydrogen-bonded chain. Phosphate anions are hydrogen-bonded to each other through supramolecular synthon R₃³(12) forming a 1D double-chain structure which links ozagrel molecules into a 3D structure.      

Synthesis and crystal structures of two novel 3,4,5- trimethoxyphenyl derivatives from (Z)-1-[(2′,3′-dinitro-4′-methoxy)-phenyl]-2-[(3″,4″,5″-trimethoxy)-phenyl] ethene

The title compounds, (Z)-1-[(2′,4′-dimethoxy-3′-nitro)-phenyl]-2-[(3″,4″,5″-trimethoxy)-phenyl]ethene, C₁₉H₂₁O₇N (I), and 2-amino-4-methyl-6-(3,4,5-trimethoxy-phenyl)-pyrimidine, C₁₄H₁₇O₃N₃ (II), were obtained unexpectedly from a reaction involving (Z)-1-[(2′,3′-dinitro-4′-methoxy)-phenyl]-2-[(3″,4″,5″-trimethoxy)-phenyl]ethene (IV). The molecular structures of these compounds were obtained by single-crystal X-ray diffraction. Crystallization of I occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a=7.7311(5), b=19.9239(13), c=11.5725(8); and β=92.193(3) and Z=4. Crystallization of II occurs in the centrosymmetric monoclinic space group C2/c (No. 15) with a=21.296(2), b=6.8963(7), c=20.001(2); and β=114.121(6) and Z=8. Details of the synthesis and the structural characterization of the title compounds are presented and discussed.     

Crystal and molecular structure of 1-amino-1-methylethylphosphonic acid monohydrate

The crystal and molecular structure of 1-amino-1-methylethylphosphonic acid monohydrate (C₃H₁₀NO₃P·H₂O) has been determined by single-crystal X-ray diffraction methods. The crystals are orthorhombic:Pna2₁,a=11.665(2),b=9.415(1),c=6.386(1) Å,Z=4. The structure was solved by the heavy-atom method and refined to a finalR=0.028. The molecule exists as a zwitterion, H ₃ ⁺ N-C-(CH₃)₂-PO₃₄H^–. There are six independent hydrogen bonds in the structure, three of the type N-HO with lengths 2.904(5), 2.745(6), and 2.765(5) Å and three of the type O-HO with lengths 2.754(4), 2.833 (7), and 2.548(5) Å.     

Hydrogen-Bonding in the Structures of the Hydrated Proton-Transfer Compounds of Isonipecotamide with the Isomeric Indole-2- and Indole-3-Carboxylic Acids

Abstract  

The structures of two hydrated proton-transfer compounds of 4-piperidinecarboxamide (isonipecotamide) with the isomeric heteroaromatic carboxylic acids indole-2-carboxylic acid and indole-3-carboxylic acid, namely 4-carbamoylpiperidinium indole-2-carboxylate dihydrate (1) and 4-carbamoylpiperidinium indole-3-carboxylate hemihydrate (2) have been determined at 200 K. Crystals of both 1 and 2 are monoclinic, space groups P2₁/c and P2/c, respectively with Z = 4 in cells having dimensions a = 10.6811(4), b = 12.2017(4), c = 12.5456(5) ?, β = 96.000(4)° (1) and a = 15.5140(4), b = 10.2908(3), c = 9.7047(3) ?, β = 97.060(3)° (2). Hydrogen-bonding in 1 involves a primary cyclic interaction involving complementary cation amide N–H···O(carboxyl) anion and anion hetero N–H···O(amide) cation hydrogen bonds [graph set R₂²(9)]. Secondary associations involving also the water molecules of solvation give a two-dimensional network structure which includes weak water O–H···π interactions. In the three-dimensional hydrogen-bonded structure of 2, there are classic centrosymmetric cyclic head-to-head hydrogen-bonded amide–amide interactions [graph set R₂²(8)] as well as lateral cyclic amide-O linked amide–amide extensions [graph set R₄²(8)]. The anions and the water molecule, which lies on a twofold rotation axis, are involved in secondary extensions.     

Crystal and molecular structure oftrans-1-isopropyl-1-methyl-4-acetyl-4-phenylpiperidinium iodide

The crystal structure oftrans-1-isopropyl-1-methyl-4-acetyl-4-phenylpiperidinium iodide has been determined from single-crystal X-ray data and refined by least-squares methods toR=0.052. The orthorhombic crystals have unit-cell dimensions ofa=10.792(6),b=11.594(8),c=13.746(9) Å, space groupP2₁2₁2₁, andZ=4. The piperidine ring is in the chair form with the bulky substituents, the isopropyl and the phenyl groups, respectively in equatorial and axial positions.     

Isolation and crystal structures of triethylenediamine-hydroquinone (1/1) and triethylenediamine-phenol (1/2)

Two crystalline adducts of triethylenediamine with hydroquinone [N(CH₂CH₂)₃N·C₆H₄(OH)₂,I] and phenol [N(CH₂CH₂)₃N·2C₆H₅OH,II] have been isolated and characterized by X-ray analysis. ComplexI crystallizes in the monoclinic space groupC2/c, witha=11.944(2),b=9.491(2),c=11.986(2) Å,=121.70(1)°, andZ=4. Both molecular components occupy sites of symmetry 2, and are linked alternately by N H-O hydrogen bonds to form infinite zigzag chains. Crystals ofII are also monoclinic, with space groupP2₁/c,a=12.987(2),b=6.376(1),c=21.350(3) Å,=106.94(1)°, andZ=4. The structure is composed of discrete hydrogen-bonded molecular aggregates corresponding to the stoichiometric formula. The triethylenediamine moieties in both adducts closely approximate to the idealizedD ₃ h conformation. The structures have been refined toR values of 0.097 (I) and 0.092 (II) using, respectively, 479 and 1580 observed MoK data.     

Palladium(II) and platinum(II) tetrakisthiourea dichloride bis(7-hydroxy-5-methyl[1,2,4]triazolo[1,5a]pyrimidine) dihydrate solvates

The title compounds palladium(II) and platinum(II) tetrakisthiourea dichloride bis(7-hydroxy-5-methyl[1,2,4]triazolo[1,5a]pyrimidine (Hmtpo)) dihydrate solvates, have been synthesized by reacting thecis-[MCl₂(Hmtpo)₂] (where M=Pt(II), Pd(II)) complexes with an excess of thiourea (tu) and the structure of the palladium compound was solved by X-ray diffraction. Crystals of [Pd(tu)₄]Cl₂·2Hmtpo·2H₂O are triclinic with space groupP and unit cell dimensionsa=7.972(1),b=9.049(1),c=11.808(2)Å, =88.20(1), =75.15(1), =76.54(1)^o. The cation [Pd(tu)₄]²⁺ is centrosymmetric involving four sulfur thiourea atoms in a near square planar environment. The triazolopyrimidine molecules, chloride anions and water molecules do not take part in the metal center coordination but interact by hydrogen bonding between them and the thiourea moieties. A comparison between powder diffraction data of palladium(II) and platinum(II) compounds clearly indicates that both compounds are isomorphous.     

Crystal structure of the 1:1 complex formed by 4-nitropyridine N-oxide and 4-nitrophenol

The title complex (C₆H₅NO₃·C₅H₄N₂O₃,M _r =279.21) crystallizes in the orthorhombic space groupPna2₁ witha=18.862(2),b=5.876(1),c=10.803(2) Å,V=1197.3(6) ų,D _c =1.549 g cm^–3 forZ=4,F(000)=576, (MoK)=0.71073 Å,=0.84 mm^–1,T=297 K. The structure was solved by direct methods and refined by block matrix least-squares. FinalR=0.032, wR=0.037 for 904 observed reflections. The complex is held together by an intermediate hydrogen bond between the hydroxyl and the N-oxide group with an OO distance equal to 2.618(3) Å. The stacking of thea glide related complex molecules by translation in theb direction results in a herringbone structure with an overlap of the nitrophenol and 4-nitropyridine N-oxide rings and a mean interplanar distance of 3.4(1) Å between those rings.On leave from Universidad del Valle, Departamento de Quimica, Cali, Colombia.     

Crystal and molecular structure of a naphthalene-tolan photoadduct: 1,8-Diphenyl-1a,2,7,7a-tetrahydro-1,2,7-metheno-1H-cyclopropa[b]naphthalene

The title compound, C₂₄H₁₈, crystallizes in the monoclinic space groupP2₁/c with cell parametersa=16.382(10),b=6.360(3),c=18.051(11) Å, =116.6(1) °,Z=4,V=1695.6 ų. The structure was solved by direct methods and refined using least-squares procedures to a finalR of 0.097 for 811 observed (I>2₁) structure magnitudes. The variables refined were the fractional coordinates of all atoms and the individual isotropic temperature factors of the nonhydrogen atoms. The highly strained molecule has single carbon-carbon bond distances of 1.47–1.59 Å, and bond angles between 59 and 136 °.     

Hydrothermal Synthesis, Structural Characterization and Luminescent Property of a New 1-D Chain-like [Er(NC6H4O2)3(H2O)2]n

Abstract  

Erbium (III) coordination compound with the formula [Er(IN)₃(H₂O)₂]_n 1 (HIN = isonicotinic acid) was synthesized by mixing Er₂O₃ with isonicotinic acid under hydrothermal condition. The structure of the title compound was determined by single crystal X-ray diffraction analysis, which reveals that the 1-D chain-like structure is formed by the erbium polyhedra through the carboxyl groups of IN. It crystallizes in the monoclinic system, possesses space group C2/c, with lattice parameters: a = 20.229(10) ?, b = 11.594(6) ?, c = 9.871(5) ?, α = γ=90°, β = 115.509(6)°, V = 2089.3(18) ?³, and D _calc = 1.811 mg/cm³ for Z = 4, F(000) = 1108, GOF = 1.109, R1 = 0.0675. Compound 1 has been characterized by IR absorption spectroscopy, ultraviolet excitation and emission spectrum.     

Crystal structure of a 1:1 molecular adduct of hexamethylenetetramine with phenylacetic acid

A 11 crystalline adduct of hexamethylenetetramine with phenylacetic acid, (CH₂)₆N₄·C₆H₅CH₂COOH, has been isolated and characterized by X-ray analysis. The compound crystallizes in space groupI¯4 (No. 82), witha=20.576(3),c=6.907(1) Å, andZ=8. The crystal structure is composed of a packing of discrete molecular aggregates corresponding to the stoichiometric formula, each being consolidated by a NH-O hydrogen bond of length 2.643(8) Å, which has no significant effect on the regular geometry of the (CH₂)₆N₄ cage system. The C-CO₂ and phenyl groups in the C₆H₅CH₂COOH moiety make a dihedral angle of 74(1)°. The structure has been refined toR=0.071 for 1350 observed (F _o >2F _o ) MoK data.     

Synthesis and X-ray analysis of 1-((1S)-phenylethyl)-azetidine-(2R)-piperidinamide

The crystal and molecular structure of a new azetidine-2-carboxylic amide derivative is described. The structure was solved by direct methods and refined by least squares methods toR1=0.0393 for 4264 reflections (withI>2(I)) The structure consists of two independent molecules which are chemically the same with slight differences in geometry. Crystal data: C₁₇H₂₄N₂O, monoclinic, space groupP2₁,a=8.3782(4),b=20.0342(13),c=9.7769(8) Å, =109.687(6)°,V=1545.1(2)ų,Z=4.     

Solid-state formation of an inclusion compound of cholic acid withp-toluidine

Cholic acid undergoes solid-solid reactions with some aromatic molecules to form inclusion compounds. Simple shaking of a mixture of powdered cholic acid andp-toluidine results in formation of the 11 (host:guest) inclusion compound which has the same structure as that formed by conventional crystallization methods: monoclinic space groupP2₁ witha=13.577(4),b=8.078(2),c=14.182(6) Å, =114.42(3)°,Z=2 andR ₁=0.061 for 2680 unique reflections.     

Crystal and molecular structure of 2-isopropylidene-5-methyl-1,3-dithiolane-1-oxide,C7H12OS2

The acid catalyzed cyclization of 2-propyl(allylthio)sulfine to methyl substituted 2-isopropylidene-1,3-dithiolane-1-oxide occursvia enethiolization of the sulfine followed by an intramolecular addition of thus formed sulfenic acid to the olefinic bond. Crystal data: C₇H₁₂OS₂,M _r=176.3, orthorhombic, space group Pbca,a=9.5551(13),b=17.3407(18),c=10.6417(9)Å,V=1763.2(3)ų,Z=8. The structure was solved by a combination of Patterson and direct methodswR ₂=0.115 for 1554 observations and 106 parameters. The stereochemical relationship between the methyl and sulfoxide oxygen iscis.     

Hydrogen bonding in proton-transfer compounds of 5-sulfosalicylic acid with ortho-substituted monocyclic heteroaromatic Lewis bases

The crystal structures of the 1:1 proton-transfer compounds of 5-sulfosalicylic acid with the ortho-substituted monocyclic heteroaromatic Lewis bases, 2-aminopyridine, 2-hydroxypyridine and 2-aminopyrimidine, viz. 2-aminopyridinium 5-sulfosalicylate (1), 2-hydroxypyridinium 5-sulfosalicylate monohydrate (2) and 2-aminopyrimidinium 5-sulfosalicylate monohydrate (3) have been determined and their hydrogen-bonding patterns described. All compounds are monoclinic, space group P2₁/c, with Z=4 in cells with dimensions a=7.898(5), b=11.159(11), c=14.912(7) ?, β=96.849(11)° (1);=7.260(2), b=15.292(3), c=12.615(2) ?, β=102.45(5)° (2) and a=7.0430(7), b=12.1871(16), c=16.2825(12) ?, β=101.364(7)° (3). All three compounds show some molecular disorder, in 1 within the cation species and with both 2 and 3, a similar rotational disorder in the anion sulfonate group. Hydrogen bonding in all three compounds together with significant cation-anion or cation-cation inter-ring π–π interactions generate three-dimensional layered polymer structures.     

Crystal structures of (?)-(SS, 1R, 2S, 5R)-menthyl p-tolyl sulfinate and (+)-(SS)-[(p-tolyl)sulfinyl]ferrocene

The absolute configuration at the chiral sulfurs centers of (−)-(S _S , 1R, 2S, 5R)-menthyl-p-tolylsulfinate (1) and (S _S )-[(p-tolyl)sulfinyl]ferrocene (2) were determined by single crystal X-ray diffraction with anomalous dispersion effects and the corresponding calculation of Flack’s absolute structure parameters. Both compounds crystallize in the monoclinic crystal system in space group P2₁ (no. 4); chiral sulfinate ester 1: a = 8.2868(6), b = 6.1399(3), c = 16.366(2) ?, β = 91.816(6)°, V = 832.3(2) ?³, Z = 2 and absolute structure parameter −0.03(7); chiral ferrocenyl sulfoxide 2: a = 5.8371(3), b = 15.390(2), c = 16.143(2) ?, β = 97.748(6)°, V = 1436.9(3) ?³, Z = 4 and absolute structure parameter +0.01(1). The trigonal pyramidal geometry at the chiral sulfur atom of 2 is close to expected values while the one of 1 is slightly distorted. With direct determination of the absolute configuration at the chiral sulfur centers an important gap concerning the widely used precursors 1 and 2 for the syntheses of chiral sulfoxides and 1,2-disubstituted planar chiral ferrocenyl ligands is now closed. The latter substance class is playing a key role in enantioselective catalysis.