Multicomponent Crystal Forms of a Biologically Active Hydrazone with Some Dicarboxylic Acids: Salts or Cocrystals? (original) (raw)
Journal of Chemical Crystallography, 2010
The molecular and crystal structures of (E)-4-O 2 NC 6 H 4 NHN=CMeCH 2 CO 2 R 1 (4: R 1 = Me; 5: R 1 = Et) and (E)-PhNHN=CPhCH 2 CONHPh (6) are reported from data collected at 120(2) K. The major intermolecular interactions in both 4 and 5 involve the hydazonyl NH and the carbonyl oxygen, with formation of symmetric dimers. Due to 4 and 5 each having different sets of additional intermolecular interactions, different supramolecular arrays are produced: molecules of 4 are linked into a three-dimension structure, while zigzag chains of molecules of 5 are obtained. Chains of molecules of 6, prepared from PhNHNH 2 and PhCOCH 2 CONHPh, are obtained from intermolecular hydrogen bonds involving amido NH and carbonyl oxygen moieties. Further interactions, C-H-p(arene), C-H-O and p-p stacking interactions in 6 produces a three dimensional array. Compound 4 crystallizes in the triclinic space group P-1 with a = 7.7027(2) Ǻ , b = 7.8103(2) Ǻ , c = 11.1761(3) Ǻ , a = 77.054(2)°, b = 79.425(2)°, c = 81.097(2)°. Compound 5 crystallizes in the triclinic space group P-1 with a = 5.6323(2)Ǻ , b = 9.9695(3)Ǻ , c = 11.0286(4)Ǻ , a = 91.859(2)°, b = 102.034(2)°, c = 98.898(3)°. Compound 6 crystallizes in the monoclinic space group P21/c with a = 10.4255(8)Ǻ , b = 10.4255(8)Ǻ , c = 9.3368(5)Ǻ , b = 113.780(4)°.
6.10a. Inorg. Chem. 31,1233.pdf
The ruthenium complex [Ru2(CloHsN2)(CO),(PiPr3),] (1) (CloHIoN2 = 1,8-diaminonaphthalene) reacts with 1 equiv of HgX, (X = C1, Br, I, 02CCH,, 02CPh, 02CCH2C1, 02CCF3, SCN, ONC) to give the adducts [(1)HgX2], in which the Hg atoms are bonded to both Ru atoms of complex 1. Correlations between the 2J(3'P-199Hg) coupling constants of their 31P NMR spectra and the corresponding halogen electronegativities or acid pK,s have been observed. With the exception of [(1)Hg(O2CCF,),], which does not react with any other mercury(I1) salt, the compounds [(l)HgX,] react with HgX', (X' = C1, Br, I, 02CCH3, 02CPh, 02CCH2C1) to give the insertion products [(l)Hg(p-X'),HgX,] only when X' is more electron-withdrawing than X; otherwise, the addition products [(l)Hg(pX),HgX',] are formed. All reactions of [(l)HgX,] with Hg(02CCF3), give the same substitution product [(l)Hg(02CCF3)2]. The molecular structures of [(l)Hg(O,CCF,),] and [(l)Hg(p-Cl),HgCI,] have been confirmed by X-ray crystallography. [(l)Hg(O,CCF,),]: monoclinic, space group C2/c, a = 23.730 (9) A, b = 12.578 (4) A, c = 14.51 1 (7) A, fl = 94.76 (5)O, Z = 4. [(1)Hg(p-C1),HgC1,]~CH2Cl2: monoclinic, space group P 2 , / n , a = 15.840 (7) A, b = 12.694 (4) A, c = 23.366 (2) A, fl = 105.74 (2)O, Z = 4. Cabeza, J. A.; Fernindez-Colinas, J. M.; Riera, V.; Garda-Granda, S.; Van Der Maelen, J. F. Inorg. Chim. Acta 1991, 185, 187. Cabeza, J. A.; Fernindez-Colinas, J. M.; Riera, V.; Pellinghelli, M. A.; Tiripicchio, A. J. Chem. Soc., Dalton Trans. 1991, 371. Andreu, P. L.; Cabeza, J. A.; Riera, V.; Robert, F.; Jeannin, Y. J. Organomet. Chem. 1989, 372, C15. Oro, L. A.; Fernindez, M. J.; Modrego, J.; Foces-Foces, C.; Cano, F. H. Angew. Chem., Inr. Ed. Engl. 1984, 23, 913. Fernindez, M. J.; Modrego, J.; Oro, L. A.; Apreda, M. C.; Cano, F. H.; Foces-Foces, C. J. Chem. SOC., Dalton Trans. 1989, 1249. See, for example: Panizo, M.; Cano, M. J. Organomet. Chem. 1984, 266,247. Pardo, M. P.; Cano, M. J. Organomet. Chem. 1983,247,293. Faraone, F.; Lo Schiavo, S.; Bruno, G.; Bombieri, G. J. Chem. Soc., Chem. Commun. 1984, 6. (a) Ermer, S.; King, K.; Rosenberg, E.; Manotti-Lanfredi, A. M.; Tiripicchio, A.; Tiripicchio-Camellini, M. Inorg. Chem. 1983, 22, 1339. (b) Rosenberg, E.; Ryckman, D.; Hsu, I.-N.; Gellert, R. W. Inorg. Chem. 1986, 25, 194. (c) Rosenberg, E.; Hardcastle, K. I.; Day, M. W.; Gobetto, R.; Hajela, S.; Muftikian, R. Organometallics 1991, 10, 203. (d) Fadel, S.; Deutcher, J.; Ziegler, M. L. Angew. Chem., Int. Ed. Engl. 1977, 16, 704. (e) Fajardo, M.; Holden, H. D.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R. J. Chem. SOC., Chem. Commun., 1984, 24. (f) G6mez-Sa1, M. P.; Johnson, B. F. G.; Lewis, J.; Raithby, P. R.; Syed-Mustaffa, S. N. A. B.
Prediction of hydrogen bonds and hydrogen atom positions in crystalline solids
Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, 1972
In the case of a hydrogen-containin[~ inorganic crystal structure for which only the heavy atom positions are known, eight criteria can be used to predict the location of the hydrogen bonds and the positions of the hydrogen atoms: (1) the angles M-D-H will be at least 90 ° (and usually over 100°); (2) even when no hydrogen-bonding contact is made, the hydrogen atom will tend to be positioned as close as possible to potential hydrogen bond acceptor(s); (3) no hydrogen atoms will be located in the edges of coordination polyhedra around cations; (4) the requirement of linearity of hydrogen bonds is not important; (5) the hydrogen bond must be viewed in its complete environment (M),,-D-H... A-(X),,,; (6) the M-D and the AX bond lengths are influenced by the hydrogen bond; (7) the D-H. • • A distance depends on the difference in the electrostatic bond strcngths received by D and A; and (8) hydrogen atoms belonging to different donor groups should usually be at least 2.0 A, apart, because the van der Wools radius of the hydrogen atom is 1.0 :~. These criteria are based on considerations of electrostatic energy, bond strengths and bonding geometry as revealed by pertinent calculations, and an inspection of hydrogen-containing crystal structures determined by neutron diffraction. A computer program, CALHPO, which is based on the criteria, can be used to calculate hydrogen-atom positions. The program and the criteria are applied to KHs(POa)z, kinoite, Na2CO3. H20, ct-Al(OH)3, Na2S203.5H20, and yugawaralite in order to reinterpret the hydrogen-bonding in these compounds. The criteria can also be used, cum grano sails, for the calculation of hydrogen atom positions in organic crystal structures.
Journal of the American Chemical Society, 2002
This book is an update of the 1992 volume of the same title. As with the earlier volume, the editors have sought to provide comprehensive coverage of the methods of X-ray spectrometry and the applications of these methods to a wide range of analytical problems. In this, they have succeeded admirably. With this edition, the editors have provided significantly enhanced coverage; the second edition is more than one-third longer than the first. All of the chapters have been updated and, in most cases, expanded. Two chapters have been completely rewritten by new authors, and a new chapter on microbeam X-ray fluorescence has been added. As with any volume involving multiple authors, there is some variability in coverage and quality from chapter to chapter. However, unlike many such volumes, the authors and editors have been successful in merging the chapters into a coherent whole. Rather than repeating introductory information, often with different nomenclature, each chapter in this volume makes frequent reference to the appropriate sections in other parts of the book and, for the most part, uses consistent symbols and nomenclature. As a consequence, this reads like a single-author treatise. In the past decade, there has been steady, and in some cases pronounced, progress in X-ray spectrometry. Particularly important are the developments in diffractive optics (zone plates and Snigirev refractive lenses) and Kumakhov polycapillary focusing optics and the advances in synchrotron X-ray sources for X-ray fluorescence studies of ultradilute samples. All of these are discussed, and the volume as a whole is quite current. The only omissions that I noted were on flash sources (e.g., laserdriven) and fourth-generation synchrotron sources (e.g., freeelectron lasers), both of which are mentioned only in passing. However, their omission is not a concern, as neither has significant analytical application at present. The coverage is comprehensive, including measurement (wavelength-dispersive vs energy-dispersive), analysis (spectrum evaluation and quantification), excitation sources (X-ray tubes; portable, i.e., radioisotope-based, sources; synchrotron sources,; particle-induced and electron-induced excitation), sample preparation, and various special-interest topics (total reflection, polarized-beam measurements). Each of the 14 chapters starts with a summary of the physics underlying its topic and then progresses to a critical discussion of selected applications. This style makes the volume quite useful for students (and more senior scientists) looking for a single source that covers all aspects of X-ray spectrometry. Although the principal audience may be analytical chemists, this volume will be of interest to anyone who makes use of X-ray fluorescence.
Thermodynamic and Structural Aspects of Hydrated and Unhydrated Phases of 4-Hydroxybenzamide
Crystal Growth & Design, 2007
Single crystals of the anhydrate and hydrate [4-OH-BZA + H 2 O] with 1:1 stoichiometry of 4-hydroxybenzamide (4-OH-BZA) were grown, and their structures were solved by X-ray diffraction methods. Furthermore, the temperature dependence of the vapor pressure of the anhydrate phase was obtained, and the thermodynamic parameters of sublimation were calculated (∆G sub°) 58.9 kJ • mol-1 ; ∆H sub 298) 117.8 (0.6 kJ • mol-1 ; ∆S sub 298) 198 (2 J • mol-1 • K-1). The differences in crystal lattice energies between the 2:1 and 1:1 hydrates and the anhydrous phase were found to be 2.2 and 6.2 kJ • mol-1 , respectively. The absolute values of the crystal lattice energies of the outlined hydrates (∆H sub 298 (2:1)) 120 (1 kJ • mol-1 ; ∆H sub 298 (1:1)) 124 (1 kJ • mol-1) were obtained on the basis of sublimation and solution calorimetric experiments. Finally, the thermodynamic stability of the three crystalline phases of 4-hydroxybenzamide was estimated. In conclusion, the comparison of the crystal lattice energy of an unsolvated phase with the "stabilization" energy (an energy gain introduced by guest molecules) of the crystal lattice of an solvated phase enables a practical classification of host-guest molecular crystals when the sizes of the host and guest are comparable, thus making it difficult to find out an appropriate qualitative criterion to distinguish them.
European Journal of Inorganic Chemistry, 2009
Alkaline earth metal (2: Mg, 3: Ca, 4: Sr, and 5: Ba) salts with the nitrogen-rich 5,5Ј-hydrazine-1,2-diylbis(tetrazolate) anion (HBT 2-) were synthesized in high purities and yields and fully characterized by spectroscopic and analytical methods. In addition, the crystal structures of the new compounds were determined by X-ray diffraction techniques. Whereas the tetrazole rings in 2 are twisted with respect to one another, as reported for compounds with the same anion, in the heavier-metal salts 3-5 there exists "apparent coplanarity" between the same rings due to disorder, which is discussed. A detailed description of the structures is given. The compounds, obtained as the hydrated species, are insensitive to friction, shock, and electrostatic discharge (BAM testing), but react vigorously in a flame upon loss of water to give the Eur.