Crystal structure of the anticancer drug carmustine determined by X-ray powder diffraction

The structure of the anticancer drug carmustine (1,3-bis(2-chloroethyl)-1-nitrosourea, C5H9Cl2N3O2) was successfully determined from laboratory X-ray powder diffraction data recorded at 278 K and at 153 K. Carmustine crystallizes in the orthorhombic space group P212121 with Z = 4. The lattice parameters are a = 19.6935(2) Å, b = 9.8338(14) Å, c = 4.63542(6) Å, V = 897.71(2) ų at 153 K, and a = 19.8522(2) Å, b = 9.8843(15) Å, c = 4.69793(6) Å, V = 921.85(2) ų at 278 K. The Rietveld fits are very good, with low R-values and smooth difference curves of calculated and experimental powder data. The molecules form a one-dimensional hydrogen bond pattern. At room temperature, the investigated commercial sample of carmustine was amorphous.

Conformational analysis of two new organotin(IV) structures completed with a CSD survey

The conformational flexibilities are studied in two new organotin(IV) complexes, namely, trans-dichloridodimethylbis[N,N′,N′′-tris(2-chlorobenzyl)phosphoric triamide]tin(IV), [Sn(CH3)2(C21H21Cl3N3OP)2Cl2] or Sn(CH3)2Cl2{OP[NHCH2C6H4(2-Cl)]3}2, (I), and bis(dipropylammonium) tetrachloridodimethylstannate(IV), [(CH3CH2CH2)2NH2]2[Sn(CH3)2Cl4], (II), and their analogous structures from the Cambridge Structural Database (CSD). The conformations are considered based on the N—P=O—Sn torsion angles for (I) and the C—C—C—N, C—C—N—C, C—N—C—C and N—C—C—C torsion angles for the two symmetry-independent [CH3CH2CH2NH2CH2CH2CH3]+ cations in (II), and the ±ac±sp±ac (ac = anticlinal and sp = synperiplanar) and ±ap±ap±ap±ap (ap = antiperiplanar) conformations are observed, respectively. In both structures, the four atoms in the corners of the square-planar segment of the octahedral shape around the Sn atom participate in normal hydrogen-bonding interactions as acceptors, which include two O and two Cl atoms for (I), and four Cl atoms for (II). However, the phosphoric triamide ligands block the environment around the Sn atom and limit the hydrogen-bond pattern to form a supramolecular ribbon assembly, while in the presence of small organic cations in (II), a two-dimensional hydrogen-bonded architecture is achieved. The weak interactions π–π, C—H...π and C—Cl...π in (I), and C—H...Cl in (II) do not change the dimensionality of the hydrogen-bond pattern. The 62 CSD structures analogous to (I), i.e. with an SnOPN3 segment (including 83 entries) fall into four categories of conformations based on the N—P=O—Sn torsion angles. The 132 [(CH3CH2CH2)2NH2]+ cations from 85 CSD structures are classified into seven groups based on the torsion angles noted for (II). Most of the CSD structures adopt the same associated conformations noted for (I) and (II). 15 [Sn(CH3)2Cl4]2− anions extracted from the CSD are compared with the structure of (II).

Synthesis, Characterization, and Electrochemistry of Diferrocenyl β-Diketones, -Diketonates, and Pyrazoles

The synthesis of FcC(O)CH(R)C(O)Fc (Fc = Fe(η5-C5H4)(η5-C5H5); R = H, 5; nBu, 7; CH2CH2(OCH2CH2)2OMe, 9), [M(κ2O,O′-FcC(O)CHC(O)Fc)n] (M = Ti, n = 3, 10; M = Fe, n = 3, 11; M = BF2, n = 1, 12), and 1-R′-3,5-Fc2-cC3HN2 (R′ = H, 13; Me, 14; Ph, 15) is discussed. The solid-state structures of 5, 7, 9, 12, 13, 15, and 16 ([TiCl2(κ2O,O′-PhC(O)CHC(O)Ph)2]) show that 7 and 9 exist in their β-diketo form. Compound 13 crystallizes as a tetramer based on a hydrogen bond pattern, including one central water molecule. The electrochemical behavior of 5–7 and 9–16 was studied by cyclic and square-wave voltammetry, showing that the ferrocenyls can separately be oxidized reversibly between −50 and 750 mV (5–7, 9, 12–15: two Fc-related events; 10, 11: six events, being partially superimposed). For complex 10, Ti-centered reversible redox processes appear at −985 (TiII/TiIII) and −520 mV (TiIII/TiIV). Spectro-electrochemical UV-Vis/NIR measurements were carried out on 5, 6, and 12, whereby only 12 showed an IVCT (intervalence charge-transfer) band of considerable strength (νmax = 6250 cm−1, Δν½ = 4725 cm−1, εmax = 240 L·mol−1·cm−1), due to the rigid C3O2B cycle, enlarging the coupling strength between the Fc groups.

Bifurcated Hydrogen Bonds and the Fold Switching of Lymphotactin

Lymphotactin (Ltn) exists under physiological conditions in an equilibrium between two interconverting structures with distinct biological functions. Using Replica-Exchange-with-Tunneling we study the conversion between the two folds. Unlike previously proposed, we find that the fold switching does not require unfolding of Lymphotactin, but proceeds through a series of intermediates that remain partially structured. This process relies on two bifurcated hydrogen bonds that connect the β2 and β3 strands and eases the transition between the hydrogen bond pattern by which the central three-stranded β-sheet in the two forms differ.

Interplay between packing, dimer interaction energy and morphology in a series of tricyclic imide crystals

Crystal morphology is a very important feature in many industrial applications. Tricyclic imides, derivatives of 10-oxa-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione with differing small hydrophobic groups (Me, Et), were studied and grouped based on Etter's rule. Using experimental X-ray studies, dimer energy calculations, framework analysis and periodic DFT-D calculations, it is shown that knowledge of the hydrogen-bond pattern can be used to determine the final crystal shape. Molecules forming a ring hydrogen-bond motif crystallize as plate crystals with the {100} facet as the slowest growing, whereas those molecules forming an infinite hydrogen-bond motif in the crystal structure crystallize as needles with the {101} facet having the largest surface area.

Hydrogen-bond pattern to characterize water network

Hydrogen-bond (HB) patterns correspond to topologically distinct isomers of water clusters, and can be expressed by digraphs. The HB pattern is used to divide the configuration space of water cluster at a finite temperature. The populations of the HB patterns are transformed into the relative Helmholtz energies. The method is based on the combination of molecular simulation with graph theory. At a finite temperature it can be observed that other isomers than local minimum structures on the potential energy surface are highly populated. The dipole moment of a constituent molecule in a water cluster is enhanced depending on the local HB network around the water molecule. Rooted digraph is used to represent topologically distinct isomers of protonated water (PW) clusters. O–H bonds of PW clusters are classified into 10 topological types based on the combination of the local HB types of the contributing water molecules to the O–H bond. If the topological type is the same, vibrational frequencies of those O–H bonds of PW clusters are similar even in different isomers; i.e. vibrational frequency of O–H bond is transferable, and can be used as a vibrational spectral signature of PW clusters.

Crystal structure of 3-hydroxy-2-(4-hydroxy-3-methoxyphenylmethyl)-5,5-dimethylcyclohex-2-enone

In the title compound, C16H20O4, a new starting compound for the synthesis of various heterocycles, the partially saturated six-membered ring adopts a sofa conformation. An intramolecular O—H...O hydrogen bond is observed in the guaiacol residue. In the crystal, molecules are assembled into a sheet structure parallel to the ab plane via O—H...O hydrogen bonds. The hydrogen-bond pattern is described by an R 4 4(28) graph-set motif. The sheets are further linked by C—H...O hydrogen bonds into a three-dimensional network.

Migrating hydrogen in 2,4,6-triaminopyrimidinium(1+) x hydrogen trioxofluorophosphate(−) x monohydrate/2,4,6-triaminopyrimidinium(2+)1–x trioxofluorophosphate(2–)1–x monohydrate (0.0 < x < 0.73) with changing temperature

The data of the title structure of 2,4,6-triaminopyrimidinium(1+) x hydrogen trioxofluorophosphate(1−) x monohydrate/2,4,6-triaminopyrimidinium(2+)1−x trioxofluorophosphate(2−)1−x monohydrate (0.0 < x < 0.73), with the sum formula C4H11FN5O4P, were collected in 10 K intervals between 290 and 150 K, as well as at 100 K. The most interesting feature is the presence of a moderate though still strong O—H...N/O...H—N hydrogen bond. Its bridging H atom was found to be disordered over two positions in the temperature interval 290–220 K, with the larger occupation towards the O atom. The occupation in the latter position decreased with decreasing temperature, though not monotonously. At 210 K and below, the difference electron-density maps showed just one maximum which was closer to the N atom. Though difference scanning calorimetry (DSC) revealed no anomaly in the interval 303–93 K, the dependence of the length of the unit-cell axes b and c on temperature showed a kink in the slope at about 190 K. The N...O distance of the mentioned hydrogen bond or the occupational parameter of the electron density of the disordered H atom indicate less pronounced anomalies for the temperatures 270 and 230 K. The cation and the anion, as well as the water molecules, form layers which are parallel to (10\overline{1}) and which are interconnected by O—H...N (in the interval 290–220 K), N—H...O and O—H...O hydrogen bonds of moderate strength. The layers are arranged into centrosymmetric double layers in which the F atoms are directed outwards. The layers are interconnected by water–acid O—H...O hydrogen bonds, weak N—H...F interactions and π-electron ring...π-electron ring interactions. The dependence of P—F bond lengths on bonding properties of the trioxofluorophosphate or hydrogen trioxofluorophosphate anions is discussed. It has been recognized that a carbon-bonded F atom avoids participation in a hydrogen-bond pattern; however, this property seems to be also common to fluorine bonded to P, As and S, especially if an oxygen ligand is also present in a molecule. The deposited material contains an overview of the determined structures with trioxofluorophosphate or hydrogen trioxofluorophosphate anions.

4-Aminobenzoic acid 4-methylpyridine/4-methylpyridinium 4-aminobenzoate 0.58/0.42: a redetermination from the original data

The title structure, 4-aminobenzoic acid 4-methylpyridine/4-methylpyridinium 4-aminobenzoate 0.58/0.42, 0.58(C6H7N·C7H7NO2)·0.42(C6H8N+·C7H6NO2−), has been redetermined from the data published by Kumaret al.(2015).Acta Cryst.E71, o125-o126. The improvement of the present redetermination consists in the introduction of disorder of the methyl group over two positions as well as in the correction of the positional parameters of the hydrogen atoms that are involved in the O—H...N or N—H...O hydrogen bonds. After the correction, the hydroxyl hydrogen atom turned out to be disordered over two positions about the centre of the O...N bond, which is relatively long [2.642 (2) Å], while the H atoms of the primary amine group account more realistically for the hydrogen-bond pattern after the removal of the positional constraints. All the O—H...N or N—H...O hydrogen bonds which are present in the title structure are of moderate strength.

A novel tubular hydrogen-bond pattern in a new diazaphosphole oxide: a combination of X-ray crystallography and theoretical study of hydrogen bonds

In the structure of 2-(4-chloroanilino)-1,3,2λ4-diazaphosphol-2-one, C12H11ClN3OP, each molecule is connected with four neighbouring molecules through (N—H)2...O hydrogen bonds. These hydrogen bonds form a tubular arrangement along the [001] direction built from R 3 3(12) and R 4 3(14) hydrogen-bond ring motifs, combined with a C(4) chain motif. The hole constructed in the tubular architecture includes a 12-atom arrangement (three P, three N, three O and three H atoms) belonging to three adjacent molecules hydrogen bonded to each other. One of the N—H groups of the diazaphosphole ring, not co-operating in classical hydrogen bonding, takes part in an N—H...π interaction. This interaction occurs within the tubular array and does not change the dimension of the hydrogen-bond pattern. The energies of the N—H...O and N—H...π hydrogen bonds were studied by NBO (natural bond orbital) analysis, using the experimental hydrogen-bonded cluster of molecules as the input file for the chemical calculations. In the 1H NMR experiment, the nitrogen-bound proton of the diazaphosphole ring has a high value of 17.2 Hz for the 2 J H–P coupling constant.