Crystal Structures of the Amide and Iminol Tautomers O-(3,5-dinitrobenzoyloxy)benzohydroxamate. A Case of a Disappearing Solvate?

2016 ◽  
Vol 69 (10) ◽  
pp. 1193 ◽  
Author(s):  
Abigail L. Albright ◽  
Lucy Collins ◽  
John Li ◽  
Benjamin Harris ◽  
Jonathan M. White
Keyword(s):  
Dimethyl Sulfoxide ◽  
Crystal Structures ◽  
Infrared Spectra ◽  
Tautomeric Form ◽  
Spectral Characteristics ◽  
Benzohydroxamic Acid ◽  
Hydrogen Bonded

The O-(3,5-dinitrobenzoyl) derivative of benzohydroxamic acid 1 crystallizes in its iminol tautomeric form, hydrogen bonded to a molecule of dimethyl sulfoxide (DMSO) when crystallized from methanol in the presence of DMSO. In contrast, in the absence of DMSO, 1 crystallizes in its amide tautomeric form. Computations suggest that in the absence of DMSO, the amide tautomer of 1 is significantly more stable than the iminol form. Conversely, in the presence of DMSO, the two forms have comparable stabilities. Solution infrared spectra of 1 run in dichloromethane are consistent with the amide tautomeric form predominating; however, titration of aliquots of DMSO results in the formation of a second species with spectral characteristics consistent with the iminol tautomer.

2-Ammonio-5-chloro-4-methylbenzenesulfonate, its 1-methyl-2-pyrrolidone and dimethyl sulfoxide monosolvates and a corrected structure of 2,2′-(1,4-phenylene)di(4,5-dihydroimidazolium) bis(4-aminobenzenesulfonate) dihydrate

2012 ◽  
Vol 68 (2) ◽  
pp. o45-o50 ◽  
Author(s):  
Sándor L. Bekö ◽  
Jan W. Bats ◽  
Martin U. Schmidt
Keyword(s):  
Dimethyl Sulfoxide ◽  
Tautomeric Form ◽  
Solvent Molecule ◽  
Mirror Plane ◽  
Acta Cryst ◽  
Ladder Graph ◽  
Diffraction Determination ◽  
Graph Set ◽  
Polymorph Screening ◽  
Hydrogen Bonded

2-Ammonio-5-chloro-4-methylbenzenesulfonate, C7H8ClNO3S, (Ia), is an intermediate in the synthesis of lake red azo pigments. The present structure determination from single-crystal data confirms the results of a previous powder diffraction determination [Bekö, Thoms, Brüning, Alig, van de Streek, Lakatos, Glaubitz & Schmidt (2010).Z. Kristallogr.225, 382–387]. The zwitterionic tautomeric form is confirmed. During a polymorph screening, two additional pseudopolymorphs were obtained,viz.2-ammonio-5-chloro-4-methylbenzenesulfonate 1-methyl-2-pyrrolidone monosolvate, C7H8ClNO3S·C5H9NO, (Ib), and 2-ammonio-5-chloro-4-methylbenzenesulfonate dimethyl sulfoxide monosolvate, C7H8ClNO3S·C2H6OS, (Ic). The molecules of (Ib) have crystallographicmsymmetry. The 1-methyl-2-pyrrolidone solvent molecule has an envelope conformation and is disordered around the mirror plane. The structure shows hydrogen-bonded ladders of molecules [graph-set notationC22(6)R22(12)] in the [010] direction. The benzene groups of adjacent ladders are also stacked in this direction. A different type of hydrogen-bonded ladder [graph-set notationC(6)R22(4)R44(12)] occurs in (Ic). In (Ia), (Ib) and (Ic), the molecules correspond to the zwitterionic tautomer. The structure of the cocrystal of 4-aminobenzenesulfonic acid with 1,4-bis(4,5-dihydroimidazol-2-yl)benzene [Shang, Ren, Wang, Lu & Yang (2009).Acta Cryst.E65, o2221–o2222] is corrected; it actually contains 4-aminobenzenesulfonate anions and 2,2′-(1,4-phenylene)di(dihydroimidazolium) dications,i.e.2,2′-(1,4-phenylene)di(4,5-dihydroimidazolium) bis(4-aminobenzenesulfonate) dihydrate, C12H16N42+·2C6H6NO3S−·2H2O. Hence, all known structures of aminobenzenesulfonic acid complexes contain ionic or zwitterionic molecules; there is no known structure with a neutral aminobenzenesulfonic acid molecule.

Effect of Pressure on the Infrared Spectra of Some Hydrogen‐Bonded Solids

1964 ◽  
Vol 41 (1) ◽  
pp. 47-50 ◽  
Author(s):  
Joseph Reynolds ◽  
Sanford S. Sternstein
Keyword(s):  
Infrared Spectra ◽  
Effect Of Pressure ◽  
Hydrogen Bonded

Structural and spectroscopic studies of transition metal nitrite complexes. VIII. Crystal structures and spectra of three pentanuclear species with stoichiometry [Ni5(N-substituted ethane-1,2-diamine)4(OH)2(NO2)8]

1981 ◽  
Vol 34 (10) ◽  
pp. 2139 ◽  
Author(s):  
AJ Finney ◽  
MA Hitchman ◽  
CL Raston ◽  
GL Rowbottom ◽  
AH White
Keyword(s):  
Transition Metal ◽  
Crystal Structures ◽  
General Formula ◽  
Infrared Spectra ◽  
Spectroscopic Studies ◽  
Molecular Structures ◽  
Structural Variations ◽  
Crystal And Molecular Structures

The preparation of a series of novel compounds of general formula [Ni5L4(NO2)8(OH)2] formed by ethane-1,2-diamine or one of five N-substituted ethane-1,2-diamines (L) is described. The crystal and molecular structures of the ethane-1,2-diamine, N,N'-diethylethane-1,2-diamine and N,N-dimethylethane-1,2-diamine complexes are reported. Each compound contains a planar, pentameric arrangement of nickel(II) ions, linked by bridging hydroxide and nitrite ligands. The details of the nitrite bridges differ among the complexes, causing differences in their electronic and infrared spectra. The structural variations are probably caused by the differing steric requirements of the amine substituents.

Crystal Structures and Magnetic Properties of Hydrogen-Bonded Nitronyl Nitroxide Radicals and Their Metal Complexes

2002 ◽  
Vol 379 (1) ◽  
pp. 153-158 ◽  
Author(s):  
Mikio Ueda ◽  
Tomoyuki Mochida ◽  
Sachie Furukawa ◽  
Hideaki Suzuki ◽  
Hirosi Moriyama ◽  
...  
Keyword(s):  
Magnetic Properties ◽  
Metal Complexes ◽  
Crystal Structures ◽  
Nitronyl Nitroxide ◽  
Nitroxide Radicals ◽  
Hydrogen Bonded

Synthesis and X-ray crystal structures of dinuclear hydrogen-bonded cadmium and lead 2-aminoethanethiolates

Polyhedron ◽  
2005 ◽  
Vol 24 (8) ◽  
pp. 865-871 ◽  
Author(s):  
Mohan S. Bharara ◽  
Chong H. Kim ◽  
Sean Parkin ◽  
David A. Atwood
Keyword(s):  
Crystal Structures ◽  
X Ray ◽  
Cadmium And Lead ◽  
Hydrogen Bonded

Ribbons of hydrogen-bonded rings in the 1:2 complex of pyromellitic acid and dimethyl sulfoxide

2003 ◽  
Vol 59 (4) ◽  
pp. o205-o206 ◽  
Author(s):  
Zhi Min Jin ◽  
Yuan Jian Pan ◽  
Liang Shen ◽  
Mei Chao Li ◽  
Mao Lin Hu
Keyword(s):  
Dimethyl Sulfoxide ◽  
Pyromellitic Acid ◽  
Hydrogen Bonded

Metal Phenoxyalkanoic Acid Interactions. XXV. The Crystal Structures of (2-Formyl-6-Methoxyphenoxy)Acetic Acid and Its Zinc(II) Complex and the Lithium, Zinc(II) and Cadmium(II) Complexes of (2-Chlorophenoxy)Acetic Acid

1987 ◽  
Vol 40 (7) ◽  
pp. 1147 ◽  
Author(s):  
EJ Oreilly ◽  
G Smith ◽  
CHL Kennard ◽  
TCW Mak
Keyword(s):  
Acetic Acid ◽  
Crystal Structures ◽  
Free Acid ◽  
Rotational Symmetry ◽  
Carboxyl Groups ◽  
X Ray Diffraction ◽  
X Ray ◽  
The Third ◽  
Planar Complex ◽  
Hydrogen Bonded

The crystal structures of (2-formyl-6-methoxyphenoxy)acetic acid (1), diaquabis [(2-formyl-6-methoxyphenoxy) acetato ]zinc(11) (2), tetraaquabis [(2-chlorophenoxy) acetato ]zinc(11) (3), triaquabis [(2-chlorophenoxy) acetato ]cadmium(11) dihydrate (4) and lithium (2-chloro- phenoxy )acetate 1.5 hydrate (5) have been determined by X-ray diffraction. The acid (1) forms centrosymmetric hydrogen-bonded cyclic dimers [O…0, 2.677(6) �] which are non-planar. Complex (2) is six-coordinate with two waters [Zn- Ow , 1.997(2) �] and four oxygens from two asymmetric bidentate carboxyl groups [Zn-O, 2.073, 2.381(2) �] completing a skew trapezoidal bipyramidal stereochemistry. Complex (5) is also six-coordinate but is octahedral, with two trans-related unidentate carboxyl oxygens [mean Zn-O, 2.134(9) �] and four waters [mean Zn-O, 2.081(9) �]. The seven-coordinate complex (4) has crystallographic twofold rotational symmetry relating two :symmetric bidentate acid ligands [ Cd -O, 2.26, 2 48(:) �] and two waters [ Cd -O, 2.34(2) �] while the third water lies on this axis [ Cd -O, 2.27(2) �]. In contrast to the monomers (2)-(4), complex (5) is polymeric with tetrahedral lithium coordinated to one water and three carboxylate oxygens [mean Li-0, 1.95(1) �]. The essential conformation of the free acid is retained in complexes (2), (3) and (4) but in (5), it is considerably changed.

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