With the goal of eventually synthesizing radialene (3), the still missing member of the parent radialene hydrocarbons, we have prepared the pentaacetates 21 and 31, the pentabromide 29 and the hexabromide 32. In principle these should be convertible by elimination reactions to the desired target molecule.
bromination; cyclopentanes; esterification; permethylcyclopentadiene; polyfunctional compounds; radialenes
The molecule of the title compound, C9H9N5O, is essentially planar (r.m.s. deviation of all atoms = 0.02 Å) except for the NH2 H atoms. An intramolecular hydrazinylidene–carbonyl N—H⋯O=C hydrogen bond is present. In the crystal, molecules are connected via N—H⋯N/O hydrogen bonds, forming thick layers parallel to (100).
The title compound, C9H12N2O2, is approximately planar (r.m.s. deviation = 0.13 Å for all non-H atoms). The carbonyl O atom is involved as acceptor in three different hydrogen-bond interactions. One N—H⋯O and the C—H⋯O(carbonyl) contact together with a weak C—H⋯O(ethoxy) interaction link the molecules into sheets parallel to (102). These are further linked into a three-dimensional network via the remaining C—H⋯O(carbonyl) hydrogen bond and a C(methylene)—H⋯π interaction
The title compound, C24H23N3O3S2, crystallizes with two independent molecules in the asymmetric unit. They differ essentially in the orientation of the tolyl rings, between which there is π–π stacking (centroid–centroid distance = 3.01 Å). The absolute configuration was confirmed by the determination of the Flack parameter [x = 0.008 (9)]. In the crystal, molecules are connected by two classical N—H⋯N hydrogen bonds and two weak but very short C—H⋯Osulfonyl interactions, forming layers lying parallel to the bc plane.
The title compound, C18H18ClN3O3S2, adopts by folding the form of a distorted disc. Interplanar angles are 29.51 (7) and 63.43 (7)° from the five-membered ring to the aromatic systems and 34.80 (6)° between these two latter rings. The absolute configuration was confirmed by determination of the Flack parameter. In the crystal, the molecules are linked by four hydrogen bonds, one classical (N—H⋯N) and three ‘weak’ (C—H⋯O), forming layers parallel to the ac plane; these are in turn linked in the third dimension by Cl⋯N [3.1689 (16) Å] and Cl⋯O [3.3148 (13) Å] contacts to the heterocyclic ring.
In the title compound, [Zr(C16H13P)Cl2], the geometry at the metal atom is distorted tetrahedral; the Cl—Zr—Cl angle is 101.490 (16)° and the cyclopentadienyl (Cp) centroids subtend an angle of 122.63 (3)° at the Zr atom. The P atom lies 0.474 (3) and 0.496 (3) Å out of the planes of the Cp rings. The C—P—C angle of 91.42 (7)° reflects the pincer effect of the two Cp rings. Three C—H⋯Cl, one C—H⋯P, one C—H⋯π and one Cl⋯P interaction link the molecules to form thick layers parallel to the bc plane.
In the title compound, [Ir(C13H9N4)(C15H10N)2]·2CDCl3, the coordination at iridium is octahedral, but with narrow ligand bite angles ranging from 74.85 (8) to 83.99 (8)°. The bond lengths at iridium show the expected trans influence, with Ir—N trans to C being appreciably longer than trans to N. The chelate rings are mutually perpendicular to a reasonable approximation [interplanar angles ranging from 77.79 (6) to 83.93 (7)°]. All ligands are approximately planar; the maximum interplanar angles within ligands are ca 12°. One CDCl3 solvent molecule is severly disordered and was excluded from the refinement.
In the title compound, [Ir(C13H9N4)(C13H8NS)2]·3.5CDCl3, the coordination at iridium is octahedral, but with narrow ligand bite angles. The bond lengths at iridium show the expected trans influence, with the Ir—N bonds trans to C being appreciably longer than those trans to N. The chelate rings are mutually perpendicular, the interplanar angles between them all lying within 6° of 90°. All ligands are approximately planar; the maximum interplanar angles within ligands are ca 10°. The three ordered deuterochloroform molecules are all involved in C⋯D—A contacts that can be interpreted as hydrogen bonds of various types. The fourth deuterochloroform is disordered over an inversion centre.
The title compound, C14H12Br4, crystallizes with imposed inversion symmetry. In the crystal, the molecules pack in layers parallel to (10). The layers involve two Br⋯Br and one H⋯Br contact. Between the layers, one contact each of types Br⋯Br, H⋯Br and Br⋯π is observed.
In the title compound, C18H19FN2O, the hydrazide side chain is approximately perpendicular to the central ring [dihedral angle = 76.80 (5)°]. The F atom is disordered over two positions with occupancies of 0.818 (2) and 0.182 (2). The packing consists of chains of molecules parallel to the a axis, connected by a bifurcated N—H⋯(O,N) hydrogen bond and a weak Cphenyl—H⋯O hydrogen bond. The packing is extended to a layer structure parallel to the ab plane by a weak Cphenyl—H⋯F hydrogen bond.
In the title compound, [Ir(C11H6F2N)2(C22H17N4O)]·CH3OH, the coordination at iridium is essentially octahedral, but with distortions associated with the bite angles of the ligands [76.25 (9)–80.71 (12)°] and the differing trans influences of C and N ligands [Ir—N = 2.04 Å (average) trans to N but 2.14 Å trans to C]. All three bidentate ligands have coordinating ring systems that are almost coplanar [interplanar angles = 1.7 (1)–3.8 (2)°]. The vinylbenzyl group is disordered over two positions with occupations of 0.653 (4) and 0.347 (4). The methanol solvent molecule is involved in a classical O—H⋯N hydrogen bond to a triazole N atom.
In the title compound, C16H12BrNO, the ring systems subtend an interplanar dihedral angle of 75.95 (3)°. In the crystal packing, molecules are linked to form centrosymmetric pairs by pairs of classical N—H⋯O hydrogen bonds.
The title compound, C17H19N3O3S, crystallizes with two closely similar independent molecules related by a pseudotranslation of c/2. Each molecule consists of three approximately planar moieties centred on the N2CS group and the two ring systems. The packing involves classical H bonds of the form Namide—H⋯S and Nhydrazine—H⋯OC, together with various weak hydrogen bonds and Nhydrazine—H⋯π interactions. The overall packing is three-dimensional, but layer substructures parallel to the xz plane can be readily identified. Each molecule forms a topologically equivalent set of hydrogen-bond interactions.
The title compound, C12H9BrN2OS2, consists of two planar parts, viz. the thiophene ring including all substituents (r.m.s. deviation 0.007 Å) and the benzene ring including the respective substituents as well as the thione group (r.m.s. deviation 0.05 Å). The interplanar angle is 18.84 (6)°. An intramolecular Cphenyl—N—H⋯OC hydrogen bond is observed. The three-dimensional packing involves three types of interactions, viz. N—H⋯S, C—H⋯S (× 2) and Br⋯S [3.6924 (6) Å].
In the title compound, C16H11BrO2, the isocoumarin ring system is planar (r.m.s. deviation = 0.015 Å) and subtends a dihedral angle of 88.90 (2)° with the bromobenzene ring. In the crystal, molecules are linked, forming a three-dimensional packing pattern involving C—H⋯O interactions, Br⋯O contacts [3.4734 (10) Å] and π–π stacking interactions with centroid–centroid distances ranging from 3.667 (2) to 3.765 (2) Å.
The title compound, C27H22N2O2, consists of two chemically equivalent halves. However, it displays no crystallographic symmetry, only an approximate local twofold symmetry (r.m.s. deviation = 0.15 Å between the two halves of the molecule) is observed. In the crystal, molecules are connected by two antiparallel classical N—H⋯O hydrogen bonds, forming broad chains parallel to (10). A series of weak C—H⋯N/O hydrogen bonds is also present.
The molecule of the title compound, C15H10N4O3S2, is almost planar (r.m.s. deviation = 0.1Å for all non-H atoms). An intramolecular N—H⋯O=C hydrogen bond is observed. In the crystal, molecules are connected into layers parallel to (10) by a classical intermolecular hydrogen bond from the second NH group to a nitro O atom and by three weak hydrogen bonds of the C—H⋯X type (X = O or Sthione).
In the enantiomerically pure title compound, C11H19N3O3S, the chain C—N—C(O)—O—C—C (from the asymmetric carbon to a methyl of the tert-butyl group) displays an extended conformation. In the crystal, molecules are linked into chains parallel to the c axis by classical N—H⋯Odiazocarbonyl hydrogen bonding and an unusual intermolecular three-centre interaction involving the amino acid (aa) carbonyl Oaa and the diazocarbonyl grouping C(O)—CH—N N, with H⋯Oaa = 2.51 Å and N⋯Oaa = 2.8141 (14) Å.
The title compound, C14H10BrN3O3S, crystallizes as two concomitant polymorphs that differ in colour (one yellow and one colourless). Only the structure of the colourless form could be determined. The molecule exists in the thioamide form with an intramolecular N—H⋯O=C hydrogen bond across the thiourea system. Molecules are linked into layers parallel to (120) by Br⋯Onitro contacts [3.103 (1) Å], classical hydrogen bonds from the other NH function to the S atom and Nnitro⋯O=C contacts. The layers are linked by weak C—H⋯Onitro hydrogen bonds to produce the observed three-dimensional network.
In the enantiomerically pure title compound, C15H15NO6, the five-membered ring displays a twist conformation with the local axis through the N atom. The acetyl groups are perpendicular to the ring [dihedral angles 80.3 (1) and 89.3 (1)°] and project to opposite sides. The packing is governed by two weak C—H⋯O interactions, forming layers of molecules parallel to the ab plane.
In the title compound, C14H12Br2, the Br atoms lie on opposite sides of their ring plane. The biphenyl interplanar angle is 53.52 (8)°. The packing is characterized by several H⋯Br contacts to each Br atom, but at long distances of 3.07–3.43 Å.
The enantiomerically pure title compound, C12H16ClNO4S2, contains a pyramidal N atom with an S—N bond length of 1.6306 (15) Å. Molecules are linked to form chains parallel to the a axis by classical N—H⋯O hydrogen bonding involving a sulfonyl O atom, supported by three weak C—H⋯X interactions. (X = S, O).
The enantiomerically pure title compound, C11H15NO4S, contains a pyramidal N atom with an S—N bond length of 1.6262 (8) Å. In the crystal, molecules are linked to form chains parallel to the a axis by the hydrogen bond from NH to the carbonyl oxygen. C—H⋯O interactions are also present.
In the title compound, C13H18O5S, the five-membered ring has an envelope conformation. The packing involves four C—H⋯O interactions, three of which combine to form layers of molecules parallel to the bc plane.
In the title compound, C10H16O6, the five-membered ring has an envelope conformation. The packing involves hydrogen-bonded carboxylic acid inversion dimers and three C—H⋯O interactions.