Whole-molecule Disorder Research Articles

Structural characterization and comparative analysis of polymorphic forms of psilocin (4-hydroxy-N,N-dimethyltryptamine)

The title compound, C12H16N2O, is a hydroxy-substituted monoamine alkaloid, and the primary metabolite of the naturally occurring psychedelic compound psilocybin. Crystalline forms of psilocin are known, but their characterization by single-crystal structure analysis is limited. Herein, two anhydrous polymorphic forms (I and II) of psilocin are described. The crystal structure of polymorphic Form I, in space group P21/c, was first reported in 1974. Along with the redetermination to modern standards and unambiguous location of the acidic H atom and variable-temperature single-crystal unit-cell determinations for Form I, the Form II polymorph of the title compound, which crystallizes in the monoclinic space group P21/n, is described for the first time. The psilocin molecules are present in both forms in their phenol–amine tautomeric forms (not resolved in the 1974 report). The molecules in Forms I and II, however, feature different conformations of their N,N-dimethyl ethylene substituent, with the N—C—C—C link in Form I being trans and in Form II being gauche, allowing the latter to bend back to the hydroxyl group of the same molecule, leading to the formation of a strong intramolecular O—H...N hydrogen bond between the hydroxyl moiety and ethylamino-nitrogen group. In the extended structure of Form II, the molecules form one-dimensional strands through N—H...O hydrogen bonds from the indole group to the oxygen atom of the hydroxyl moiety of an adjacent molecule. Form II exhibits whole-molecule disorder due to a pseudo-mirror operation, with an occupancy ratio of 0.689 (5):0.311 (5) for the two components. In contrast, Form I does not feature intramolecular hydrogen bonds but forms a layered structure through intermolecular N—H...O and O—H...N hydrogen bonds.

Crystal structure of a heterotrimetallic 12-metallacrown-4 with 2-propylvalerate anion bridges

The synthesis and single-crystal X-ray structure for tetraaquatetrakis(μ-2-propylvalerato)tetrakis(μ4-salicylhydroximato)dysprosiumtetramanganesesodium dimethylformamide tetrasolvate, [DyMn4Na(C7H4NO3)4(C8H15O2)4(H2O)4]·4C3H7NO or DyNa(2-PV)4[12-MCMnIII Nshi-4](H2O)4·4DMF, 1, where MC is metallacrown, shi3− is salicylhydroximate, 2-PV is 2-propylvalerate, and DMF is N,N-dimethylformamide, is reported. The slightly domed metallamacrocycle contains four ring MnIII ions and four shi3− ligands that generate an [MnIII—N—O] repeat unit that recurs four times. The ring MnIII ions are five-coordinate with a square-pyramidal shape. Furthermore, the metallacrown binds both a DyIII ion and a Na+ ion in the central cavity. The central ions are located on opposite faces of the cavity with the DyIII ion located on the convex side of the MC and the Na+ ion located on the concave side. Each central ion is eight-coordinate although they possess different geometries. The DyIII ion has a square-antiprismatic shape, while the Na+ ion has an extremely distorted biaugmented trigonal–prismatic shape. The four 2-propylvalerate anions help to tether the DyIII to the MC cavity by forming bridges between the DyIII ion and each ring MnIII ion. Moreover, the interstitial DMF molecules are hydrogen bonded to the water molecules that complete the coordination environment of the Na+ ion. The metallacrown framework (excluding the DyIII and Na+ ions), the bridging 2-propylvalerate, and the interstitial DMF molecule experience whole-molecule disorder due to the rotational orientation of the metallamacrocycle. Additionally, the main moiety alkyl chain of the 2-propylvalerate is disordered over two additional orientations, and the main moiety interstitial DMF molecule is disordered over one additional orientation. The main moiety of the metallacrown framework refined to 0.9030 (14), while the minor B-moiety refined to 0.0971 (14). The main moiety alkyl chain of the 2-propylvalerate refined to 0.287 (3): 0.309 (3): 0.307 (3), and the minor B-moiety alkyl chain refined to 0.0971 (14). Lastly, the main moiety interstitial DMF refined to 0.549 (3): 0.354 (3), and the minor B-moiety DMF refined to 0.0971 (14).

4-Amidino-pyridinium hexa-chlorido-stannate(IV) dihydrate.

In the title hydrated mol-ecular salt {systematic name: 4-[amino-(iminium-yl)meth-yl]pyridin-1-ium hexa-chlorido-stannate(IV) dihydrate}, (C6H9N3)[SnCl6]·2H2O, the tin atom lies on a crystallographic inversion centre and the organic cation shows whole-mol-ecule disorder. Numerous N-H⋯O, N-H⋯Cl and O-H⋯Cl hydrogen bonds link the components in the crystal.

Crystal structure of [3,10-bis-(4-fluoro-pheneth-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-deca-ne]nickel(II) diperchlorate.

The square-planar nickel(II) title complex, [Ni(C24H36F2N6)](ClO4)2 or [NiL](ClO4)2 (L = 3,10-bis-(4-fluoro-pheneth-yl)-1,3,5,8,10,12-hexa-aza-cyclo-tetra-deca-ne) was synthesized by a one-pot reaction of template condensation and its X-ray crystal structure was determined. The nickel(II) ion lies close by a twofold axis and the complex displays whole-mol-ecule disorder. Ligand L, a hexa-aza-cyclo-tetra-decane ring having 4-fluoro-phenethyl side chains attached to uncoordinated nitro-gen atoms, adopts a trans III (R,R,S,S) configuration. The average Ni-N bond distance is 1.934 (9) Å, which is quite similar to those of other nickel(II) complexes with similar ligands. The nickel(II) ion is located 0.051 (7) Å above the least-squares plane through the four coordinated N atoms. The average C-N bond distance and C-N-C angle involving uncoordinated nitro-gen atoms are 1.425 (12) Å and 118.0 (9)°, respectively, indicating a significant contribution of sp 2 hybridization for these N atoms. The inter-molecular N-H⋯O, C-H⋯O/F hydrogen bonds of the complex form a network structure, which looks like a seamless floral lace pattern.

2H-[1,3]Thia-zolo[5,4,3-ij]quinolin-3-ium chloride monohydrate.

The structure of the title hydrated mol-ecular salt, C10H8NS+·Cl-·H2O, obtained by the reaction of sodium quinoline-8-thiolate Na(Quin-8-S) with CH2Cl2 and an aqueous solution of [Bu4N]Cl, contains π-stacked cations [plane-to-plane separation = 3.338 (4)-3.356 (4) Å] and features chains built by alternating Cl- anions and H2O mol-ecules connected by O-H⋯O hydrogen bonds. The cation shows whole-mol-ecule disorder over two flipped orientations in a 0.853 (3):0.147 (3) ratio.

Crystal structures of two heterotrimetallic dysprosium-manganese-sodium 12-metallacrown-4 complexes with the bridging ligands 3-hy-droxy-benzoate and 4-hy-droxy-benzoate.

The syntheses and crystal structures for the compounds tetra-μ-aqua--tetra-kis-{2-[aza-nid-yl-ene(oxido)meth-yl]phenolato}tetra-kis-(μ2-3-hy-droxy-benzoato)dys-pro-s-ium(III)-tetra-manganese(III)sodium(I) N,N-di-methyl-acetamide deca-solvate, [DyMn4Na(C7H5O3)4(C7H4NO2)4(H2O)4]·10C4H9NO or [DyIIINa(4-OHben)4{12-MCMn(III)N(shi)-4}(H2O)4]·10DMA, 1, and tetra-μ-aqua--tetra-kis-{2-[aza-nid-yl-ene(oxido)meth-yl]phenolato}tetra-kis-(μ2-3-hy-droxy-benzoato)dys-pros-ium(III)tetra-manganese(III)sodium(I) N,N-di-methylformamide tetra-solvate, [DyMn4Na(C7H5O3)4(C7H4NO2)4(H2O)4]·4C3H7NO or [DyIIINa(3-OHben)4{12-MCMn(III)N(shi)-4}(H2O)4]·4DMF, 2, and where MC is metallacrown, shi3- is salicyl-hydroximate, 3-OHben is 3-hy-droxy-benzoate, DMA is N,N-di-methyl-acetamide, 4-OHben is 4-hy-droxy-benzoate, and DMF is N,N-di-methyl-formamide, are reported. For both 1 and 2, the macrocyclic metallacrown consists of an [MnIII-N-O] ring repeat unit, and the domed metallacrown captures two ions in the central cavity: a DyIII ion on the convex side of the metallacrown and an Na+ ion the concave side. The MnIII ions are six-coordinate with an elongated tetra-gonally distorted octa-hedral geometry. Both the DyIII and Na+ ions are eight-coordinate. The DyIII ions possess a square-anti-prismatic geometry, while the Na+ ions have a distorted biaugmented trigonal-prismatic geometry. Four 3-hy-droxy-benzoate or 4-hy-droxy-benzoate ligands bridge each MnIII ion to the central DyIII ion. For 1, whole-mol-ecule disorder is observed for the main mol-ecule, excluding only the DyIII and Na+ ions, and the occupancy ratio refined to 0.8018 (14):0.1982 (14). Three DMA mol-ecules were refined as disordered with two in general positions by an approximate 180° rotation and the third disordered twice by general disorder as well as by an exact 180° rotation about a twofold axis that bis-ects it. The occupancy ratios refined to 0.496 (8):0.504 (8), 0.608 (9):0.392 (9), and 2×0.275 (7):2×0.225 (7), respectively. For 2, segments of the metallacrown are disordered including the DyIII ion, one of the Mn ions, two of the Mn-bound 4-hy-droxy-benzoate ligands, the Mn-bridging salicyl-hydroximate ligand, and portions of the remaining three shi3- ligands. The occupancy ratio for the metallacrown disorder refined to 0.849 (9):0.151 (9). Two DMF solvent mol-ecules are also disordered, each over two orientations. The disorder ratios refined to 0.64 (3):0.36 (3) and to 0.51 (2):0.49 (2), respectively. For 2, the crystal under investigation was refined as a non-merohedric twin by a 90° rotation around the real a axis [twin ratio 0.9182 (8):0.0818 (8)].

Whole-mol-ecule disorder of the Schiff base compound 4-chloro-N-(4-nitro-benzyl-idene)aniline: crystal structure and Hirshfeld surface analysis.

In the crystal of the title Schiff base compound, C13H9ClN2O2, [CNBA; systematic name: (E)-N-(4-chloro-phen-yl)-1-(4-nitro-phen-yl)methanimine], the CNBA mol-ecule shows whole-mol-ecule disorder (occupancy ratio 0.65:0.35), with the disorder components related by a twofold rotation about the shorter axis of the mol-ecule. The aromatic rings are inclined to each other by 39.3 (5)° in the major component and by 35.7 (9)° in the minor component. In the crystal, C-H⋯O hydrogen bonds predominate in linking the major components, while weak C-H⋯Cl inter-actions predominate in linking the minor components. The result is the formation of corrugated layers lying parallel to the ac plane. The crystal packing was analysed using Hirshfeld surface analysis and compared with related structures.

Hypervalent organoselenium compounds stabilized by intramolecular coordination: synthesis and crystal structures.

Two novel hypervalent selenium(IV) compounds stabilized by intramolecular interactions, namely 6-phenyl-6,7-dihydro-5H-2,3-dioxa-2aλ4-selenacyclopenta[hi]indene, C14H12O2Se, 14, and 5-phenyl-5,6-dihydro-4H-benzo[c][1,2]oxaselenole-7-carbaldehyde, C14H12OSe2, 15, have been synthesized by the reaction of 2-chloro-1-formyl-3-(hydroxymethylene)cyclohexene with in-situ-generated disodium diselenide (Na2Se2). The title compounds were characterized by FT-IR spectroscopy, ESI-MS, and single-crystal X-ray diffraction studies. For 14, there is whole-molecule disorder, with occupancies of 0.605 (10) and 0.395 (10), a double bond between C and Se, and the five-membered selenopentalene rings are coplanar. The packing is stabilized by π-π stacking interactions involving one of the five-membered Se/C/C/C/O rings [centroid-centroid (Cg...Cg) distance = 3.6472 (18) Å and slippage = 1.361 Å], as well as C-H...π interactions involving a C-H group and the phenyl ring. In addition, there are bifurcated C-H...Se,O interactions which link the molecules into ribbons in the c direction. For 15, the C-Se bond lengths are longer than those of 14. The two five-membered rings are coplanar. There are no π-π or C-H...π interactions; however, molecules are linked by C-H...O interactions into centrosymmetric dimers, with graph-set notation R22(16).

Whole-molecule disorder in the crystal structures of 7-chloro and 7-methyl indole

Whole-molecule disorder in the crystal structures of 7-chloro and 7-methyl indole

Green synthesis and crystal structure of 3-(benzo-thia-zol-2-yl)thio-phene.

The title compound, C11H7NS2, was prepared in high yield (87%) using a solvent-free microwave-assisted synthesis. The structure shows whole-mol-ecule disorder with occupancies for two orientations (A and B) of 0.4884 (10) and 0.5116 (10), respectively. The thio-phene and benzo-thia-zole rings are almost planar and make dihedral angles of 10.02 (18) and 12.54 (19)° for orientations A and B, respectively. Slipped π-π stacking between the aromatic rings, together with C-H⋯π, C-H⋯S and C-H⋯N inter-actions, result in a herringbone motif in the crystal packing.

Crystal structure of a 2:1 piroxicam-gentisic acid co-crystal featuring neutral and zwitterionic piroxicam mol-ecules.

A new 2:1 co-crystal of piroxicam and gentisic acid [systematic name: 4-hy-droxy-1,1-dioxo-N-(pyridin-2-yl)-2H-1λ6,2-benzo-thia-zine-3-carboxamide-2-(4-oxido-1,1-dioxo-2H-1λ6,2-benzo-thia-zine-3-amido)-pyridin-1-ium-2,5-di-hydroxy-benzoic acid, 2C15H13N3O4S·C7H6O4] has been synthesized using a microfluidic platform and initially identified using Raman spectroscopy. In the co-crystal, one piroxicam mol-ecule is in its neutral form and an intra-molecular O-H⋯O hydrogen bond is observed. The other piroxicam mol-ecule is zwitterionic (proton transfer from the OH group to the pyridine N atom) and two intra-molecular N-H⋯O hydrogen bonds occur. The gentisic acid mol-ecule shows whole-mol-ecule disorder over two sets of sites in a 0.809 (2):0.191 (2) ratio. In the crystal, extensive hydrogen bonding between the components forms layers propagating in the ab plane.

Triclinic and monoclinic polymorphs of meso-(E,E)-1,1'-[1,2-bis(4-chlorophenyl)ethane-1,2-diyl]bis(phenyldiazene): the high-yield synthesis of an unexpected product, concomitant polymorphism and configurational disorder.

Pyrazolidine-3,5-diones and their derivatives exhibit a wide range of biological activities. Seeking to explore the effect of combining a hydrocarbyl ring substituent, as present in sulfinpyrazone (used to treat gout), with a chlorinated aryl ring, as present in muzolimine (a diuretic), we explored the reaction between 1-phenylpyrazolidine-3,5-dione and 4-chlorobenzaldehyde under mildly basic conditions in the expectation of producing the simple condensation product 4-(4-chlorobenzylidene)-1-phenylpyrazolidine-3,5-dione. However, the reaction product proved to be meso-(E,E)-1,1'-[1,2-bis(4-chlorophenyl)ethane-1,2-diyl]bis(phenyldiazene), C26H20Cl2N4, and a tentative mechanism is proposed. Crystallization from ethanol produces two concomitant polymorphs, i.e. a triclinic form, (I), in the space group P-1, and a monoclinic form, (II), in the space group C2/c. In both polymorphs, the molecules lie across centres of inversion, but in (II), the molecules are subject to whole-molecule disorder equivalent to configurational disorder with occupancies of 0.6021 (19) and 0.3979 (19). There are no hydrogen bonds in the crystal structure of polymorph (I), but the molecules of polymorph (II) are linked by C-H...π(arene) hydrogen bonds into complex chains, which are further linked into sheets by C-H...N interactions.

Crystal Photodimerization Reactions of Spatially Engineered Isocoumarin Assemblies

We report the single-crystal-to-single-crystal (SCSC) photodimerization of a sulfonamide isocoumarin. When recrystallized, this material forms centrosymmetrically related supramolecular dimers that assemble via the complementary features of molecular shape and carboxyl···carboxyl contacts. This prescribed motif persists despite the presence of two-part whole-molecule disorder. Each disorder component is involved in a unique set of hydrogen-bonding interactions, N–H···O═C versus N–H···O═S, that propagate along the [111] and [110] directions of the crystal, respectively. Despite the observed disorder, the overall recognition profile of this supramolecular dimer remained intact, effectively promoting coplanar head-to-tail alignment with a separation of 3.4–4.1 A between the neighboring C═C groups. UV illumination studies using the tail-irradiation technique produced a single photodimer product in quantitative yield via a SCSC transformation.

Crystal structure of N-[(naphthalen-1-yl)carbamo-thio-yl]cyclo-hexa-necarboxamide.

The title compound, C18H20N2OS, displays whole-mol­ecule disorder over two adjacent sets of sites with an occupancy ratio of 0.630 (11):0.370 (11). In each disorder component, the cyclo­hexyl ring shows a chair conformation with the exocyclic C—C bond in an equatorial orientation. The dihedral angles between the cyclo­hexyl ring (all atoms) and the naphthyl ring system are 36.9 (6) for the major component and 20.7 (12)° for the minor component. Each component features an intra­molecular N—H⋯O hydrogen bond, which closes an S(5) ring. In the crystal, inversion dimers linked by pairs of N—H⋯S hydrogen bonds generate R 2 2(8) loops for both components. Aromatic π–π stacking inter­actions [shortest centroid–centroid separation = 3.593 (9) Å] and a C—H⋯π inter­action are also observed.

Crystal structure of 4-[(E)-(4-nitro-benzyl-idene)amino]-phenol.

The asymmetric unit of the title compound, C13H10N2O3, contains four independent mol­ecules (I, II, III and IV). Mol­ecule IV shows whole-mol­ecule disorder over two sets of adjacent sites in a 0.669 (10):0.331 (10) ratio. The dihedral angles between the aromatic rings are 32.30 (13)° in mol­ecule I, 2.24 (14)° in II, 41.61 (13)° in III, 5.0 (5)° in IV (major component) and 10.2 (3)° in IV (minor component). In the crystal, mol­ecules are linked into layers lying parallel to (024) by C—H⋯O and O—H⋯O inter­actions. The layers inter­act by C—H⋯π and weak aromatic π–π stacking inter­actions [centroid–centroid distances = 3.8476 (16), 3.725 (3) and 3.733 (5) Å].

Chlorido(2,3,7,8,12,13,17,18-octaethylporphyrinato)iron(III): a new triclinic polymorph of Fe(OEP)Cl

The previous structure determination of the title compound, [Fe(C36H44N4)Cl], was of a monoclinic polymorph [Senge (2005). Acta Cryst. E61, m399-m400]. The crystal structure of a new triclinic polymorph has been determined based on single-crystal X-ray diffraction data collected at 100 K. The asymmetric unit contains one molecule of the high-spin square-pyramidal iron(III) porphyrinate. The structure exhibits distinct nonstatistical alternative positions for most atoms and was consequently modeled as a whole-molecule disorder. The compound is characterized by an average Fe-N bond length of 2.065 (2) Å, an Fe-Cl bond length of 2.225 (4) Å, and the iron(III) cation displaced by 0.494 (4) Å from the plane of the 24-atom porphyrinate core, essentially the same as in the previously determined polymorph. Common features of the porphyrin plane-plane stacking involve two types of synthons, each of which can be further stabilized with additional H···Cl interactions to the axial chloride ligand, exhibiting concerted interactions of H atoms from the ethyl groups with the π-cloud electron density of adjacent molecules; the shortest methylene H-atom contacts are in the range 2.75-2.91 Å, resulting in plane-plane separations of 3.407 (4) and 3.416 (4) Å, and the shortest methyl H-atom contacts are 2.56-2.95 Å, resulting in plane-plane separations of 4.900 (5) and 4.909 (5) Å in the monoclinic polymorph. The plane-to-plane stacking synthons in the triclinic polymorph are similar, but at greater distances; the shortest methylene H-atom contacts are 2.86-2.94 Å, resulting in plane-plane separations of 3.45 (2) and 3.45 (3) Å, and the shortest methyl H-atom contacts are 2.89-3.20 Å, resulting in plane-plane separations of 5.081 (13) and 5.134 (13) Å, consistent with the density of the triclinic polymorph being 1.5% lower, suggesting lesser packing efficiency and lower stability in the triclinic polymorph. The major molecular differences found in the polymorphs is in three different orientations of the ethyl-group side chains on the periphery of the porphyrin core.

Structural study of six cycloalkylammonium cinnamate salt structures featuring one-dimensional columns and two-dimensional hydrogen-bonded networks

Six ammonium carboxylate salts, namely cyclopentylammonium cinnamate, C(5)H(12)N(+)·C(9)H(7)O(2)(-), (I), cyclohexylammonium cinnamate, C(6)H(14)N(+)·C(9)H(7)O(2)(-), (II), cycloheptylammonium cinnamate form I, C(7)H(16)N(+)·C(9)H(7)O(2)(-), (IIIa), and form II, (IIIb), cyclooctylammonium cinnamate, C(8)H(18)N(+)·C(9)H(7)O(2)(-), (IV), and cyclododecylammonium cinnamate, C(12)H(26)N(+)·C(9)H(7)O(2)(-), (V), are reported. Salts (II)-(V) all have a 1:1 ratio of cation to anion and feature three N(+)-H···O(-) hydrogen bonds forming one-dimensional hydrogen-bonded columns consisting of repeating R(4)(3)(10) rings, while salt (I) has a two-dimensional network made up of alternating R(4)(4)(12) and R(6)(8)(20) rings. Salt (III) consists of two polymorphic forms, viz. form I having Z' = 1 and form II with Z' = 2. The latter polymorph has disorder of the cycloheptane rings in the two cations, as well as whole-molecule disorder of one of the cinnamate anions. A similar, but ordered, Z' = 2 structure is seen in salt (IV).

Crystal structures and photoreactivity of trans- and cis-valerophenone diperoxides

AbstractThe crystal structures of valerophenone diperoxides trans-1 and cis-1 were elucidated by X-ray crystallographic analysis. The 1,2,4,5-tetraoxane rings of both compounds adopt chair conformations. Intermolecular CH···O hydrogen bond, π–π, and CH/π interactions exist in cis-1, whereas only CH/π interactions exist in trans-1. In the asymmetric unit of the crystal, a half molecule exists for trans-1, while one molecule for cis-1 which shows whole-molecule disorder. Solid-state photolysis (at 254 nm) or solution-state thermolysis (at 150 °C) of trans-1 and cis-1 produced valerophenone (2) and butyl benzoate (3). Rationalization of the solid-state photoreactivity of the diperoxides by their crystal structures was attempted.Index abstractThe crystal structure of cis-valerophenone diperoxide (cis-1) shows whole molecule disorder. Its lower photoreactivity in the solid state is explained by the locally narrow and rigid reaction cavity due to the Ph–Ph π–π overlap.[IMAGE]

Intermolecular interactions and unexpected isostructurality in the crystal structures of the dichlorobenzaldehyde isomers

The crystal structures of the six dichlorobenzaldehyde isomers, four of them newly determined, are analyzed in terms of the geometry and energies of their intermolecular interactions, quantified using the semi-classical density sums (SCDS-PIXEL) method. A consistent feature in all six structures is molecular stacks propagating along a short crystallographic axis of ca 3.8 Å. The stacks have a closely comparable geometry in each isomer, but the interaction energies between stacked molecules are variable on account of the differing relative positions of the Cl substituents. In the majority of the isomers the stacking interactions are the most stabilizing in the structure. Exceptions are the 2,4- and 3,5-isomers, where more stabilizing interactions are made between stacks. In general, the most stabilizing non-stacking intermolecular interactions in the structures are those involving C-H...O contacts. Observed motifs based on Cl...Cl interactions appear to be largely imposed by the constraints of other more stabilizing intermolecular interactions. The isomeric series displays the following noteworthy features: (i) the 2,3- and 2,6-isomers are isostructural despite having different orientations of the Cl and aldehyde functionalities; (ii) the 2,5-isomer exhibits whole-molecule disorder; (iii) the 2,5- and 3,5-isomers have more than one molecule in the crystallographic asymmetric unit (Z' > 1). These features in particular are considered on the basis of the intermolecular interaction energies.

An aza-cyclophane stacked in racemic columnar assemblies: whole-molecule disorder in a two-dimensional solid solution

The oxime derivative of [1.1.1]cyclophane cyclotriveratrylene (CTV) was ring expanded utilizing a Beckmann rearrangement to provide a ten-membered N-acetyl macrocyclic amide that crystallizes as a chloroform monosolvate in columnar assemblies manifesting an unusual disorder within the crystal. Columns made up of this structure consist of infinite columnar assemblies of alternating D and L enantiomers and therefore necessarily are made up of a racemate, yet the chiralities of individual molecules in adjacent columns are independent of one another, leading to the overall formation of a two-dimensional solid solution. The random arrangement of the columns within the structure leads to the emergence of a crystallographic mirror plane not reflected by the molecular symmetry, to a change of symmetry from Pna2(1) to Pnma and to whole-molecule disorder of the bowl-shaped molecules within the columns.