Fluoro-substituted Benzene Rings Research Articles

Crystal structure of (2Z)-2-{(5Z)-5-[3-fluoro-2-(4-phenyl-piperidin-1-yl)benzyl-idene]-4-oxo-3-(p-tol-yl)-1,3-thia-zolidin-2-yl-idene}-N-(p-tol-yl)ethane-thio-amide dimethyl sulfoxide monosolvate.

The title compound, C37H34FN3OS2·C2H6OS, was obtained by the Knoevenagel condensation. The thia­zolidine ring is essentially planar (r.m.s. deviation = 0.025 Å) and forms dihedral angles of 4.2 (3), 68.60 (14) and 39.57 (15)° with the attached thio­amide group, p-tolyl group benzene ring and fluoro-substituted benzene ring, respectively. The exocyclic double bonds are in a Z configuration. In the crystal, the dimethyl sulfoxide solvent mol­ecule is connected to the main mol­ecule via an N—H⋯O hydrogen bond. Weak C—H⋯O hydrogen bonds link the components of the structure into a two-dimensional network parallel to (10-1). Weak intra­molecular C—H⋯S hydrogen bonds are also observed. The crystal is an inversion twin with a ratio of twin components 0.78 (2):0.22 (6).

Flunarizinium isonicotinate.

In the cation of the title salt {systematic name: 4-[bis­(4-fluoro­phen­yl)meth­yl]-1-[(2E)-3-phenyl­prop-2-en-1-yl]piperazin-1-ium pyridine-4-carboxyl­ate}, C26H27F2N2 +·C6H4NO2 −, the piperazine ring is in a slightly distorted chair conformation. The dihedral angle between the mean planes of the fluoro-substituted benzene rings is 81.9 (1)° and these benzene rings form dihedral angles of 6.5 (1) and 87.8 (1)° with the phenyl ring. In the crystal, a single N—H⋯O hydrogen bond links the cation and the anion. In addition, weak C—H⋯O hydrogen bonds and π–π stacking inter­actions involving one of the fluoro-substituted benzene rings and the phenyl ring, with a centroid–centroid distance of 3.700 (7) Å, link mol­ecules along [100].

4′-(4-Fluorophenyl)-1′-methyldispiro[indane-2,2′-pyrrolidine-3′,2′′-indane]-1,3,1′′-trione methanol hemisolvate

The asymmetric unit of the title compound, C29H24FNO5·0.5CH3OH, contains two independent mol­ecules and a one methanol solvent mol­ecule. The methanol mol­ecule is O—H⋯O hydrogen bonded to one of the independent mol­ecules. The pyrrolidine rings in both mol­ecules adopt half-chair conformations, while the cyclo­pentane rings within the indane groups are in flattened envelope conformations, with the spiro C atoms forming the flaps. The benzene rings of the indane ring systems form a dihedral angle of 35.06 (7)° in one independent mol­ecule and 31.16 (8)° in the other. The fluoro-substituted benzene ring forms dihedral angles of 65.35 (6) and 85.87 (7)° with the indane group benzene rings in one mol­ecule, and 72.78 (8) and 77.27 (8)° in the other. In each mol­ecule, a weak intra­molecular C—H⋯O hydrogen bond forms an S(6) ring motif. In the crystal, weak C—H⋯O, C—H⋯N and C—H⋯F hydrogen bonds link the mol­ecules into a three-dimensional network.

5-(4-Bromophenyl)-3-(4-fluorophenyl)-1-phenyl-4,5-dihydro-1H-pyrazole

In the title compound, C21H16BrFN2, the fluoro-substituted benzene ring is disordered over two orientations about the C—F bond and the C—C bond between the benzene and pyrazole groups with a site-occupancy ratio of 0.516 (8):0.484 (8). The central pyrazole ring [maximum deviation = 0.035 (3) Å] makes dihedral angles of 22.4 (2), 11.0 (2), 77.19 (16) and 7.44 (17)° with the two disorder components of the benzene ring, the bromo-substituted benzene ring and the phenyl ring, respectively. In the crystal, mol­ecules are linked into a layer parallel to the bc plane through C—H⋯π inter­actions.

(2E)-3-(2-Fluorophenyl)-1-(4-fluorophenyl)prop-2-en-1-one

In the title compouund, C15H10F2O, the mol­ecule exists in an E conformation with respect to the C=C bond [1.3382 (16) Å]. The dihedral angle between the fluoro-substituted benzene rings is 6.80 (6)° and the whole mol­ecule is roughly planar (r.m.s. deviation for the non-H atoms = 0.069 Å). In the crystal, mol­ecules are linked by C—H⋯F and C—H⋯O inter­actions into sheets lying parallel to the bc plane.

1-[3-(4-Fluorophenyl)-5-phenyl-4,5-dihydro-1H-pyrazol-1-yl]ethanone

In the title compound, C17H15FN2O, the pyrazoline ring adopts a flattened envelope conformation. The dihedral angle between the fluoro-substituted benzene ring and the phenyl ring is 69.20 (5)°. In the crystal, a pair of C—H⋯O hydrogen bonds link neighbouring mol­ecules, forming an inversion dimer. The crystal structure is further consolidated by C—H⋯π inter­actions and by a π–π inter­action with a centroid–centroid distance of 3.7379 (6) Å.

N-(1,3-Dioxo-2,3-dihydro-1H-isoindol-2-yl)-4,4′′-difluoro-5′-hydroxy-1,1′:3′,1′′-terphenyl-4′-carboxamide

The asymmetric unit of the title compound, C27H16F2N2O4, consists of two crystallographically independent mol­ecules (A and B). In mol­ecule B, the isoindoline-1,3-dione ring system is disordered over two set of sites with a site-occupancy ratio of 0.658 (12):0.342 (12). In mol­ecule A, the fluoro-substituted benzene rings make dihedral angles of 18.36 (8) and 46.37 (8)° with the central benzene ring, whereas the corresponding angles are 40.90 (8) and 52.89 (9)° in mol­ecule B. The isoindoline ring system in mol­ecule A and the major and minor components of the disordered isoindoline ring system in mol­ecule B make dihedral angles of 58.50 (4), 54.13 (16) and 70.01 (28) °, respectively, with their attached benzene rings, linked through the amide group. An intra­molecular O—H⋯O hydrogen bond generates an S(6) ring in each mol­ecule. In the crystal, mol­ecules are linked by N—H⋯O, C—H⋯F and C—H⋯O hydrogen bonds into sheets lying parallel to the bc plane. The crystal studied was a non-merohedral twin with a refined twin component ratio of 0.9316 (8):0.0684 (8).

(2E)-1-(4,4′′-Difluoro-5′-methoxy-1,1′:3′,1′′-terphenyl-4′-yl)-3-[4-(methylsulfanyl)phenyl]prop-2-en-1-one

In the title compound, C29H22F2O2S, the central benzene ring makes dihedral angles of 45.83 (7), 38.90 (7) and 55.50 (7)° with the two fluoro-substituted benzene rings and the methyl­sulfanyl-substituted benzene ring, respectively. In the crystal, C—H⋯O contacts connect the mol­ecules into layers lying perpendicular to the c axis. In addition, π–π stacking inter­actions between one of the fluoro­phenyl groups [centroid–centroid distances = 3.681 (1) and 3.818 (1) Å] are observed.

(1Z)-1-[(2E)-3-(4-Bromophenyl)-1-(4-fluorophenyl)prop-2-en-1-ylidene]-2-(2,4-dinitrophenyl)hydrazine

In the title mol­ecule, C21H14BrFN4O4, the mean planes of the two nitro groups form dihedral angles of 3.1 (2) and 7.1 (5)° with the benzene ring to which they are attached. The dinitro-substituted ring forms dihedral angles of 8.6 (2) and 71.9 (2)° with the bromo- and fluoro-substituted benzene rings, respectively. The dihedral angle between the bromo- and fluoro-substituted benzene rings is 80.6 (2)°. There is an intra­molecular N—H⋯O hydrogen bond. In the crystal, pairs of weak C—H⋯O hydrogen bonds form inversion dimers. In addition, π–π stacking inter­actions between the bromo- and dinitro-substituted rings [centroid–centroid separation = 3.768 (2) Å] are observed.

11-[(E)-2-Fluorobenzylidene]-8-(2-fluorophenyl)-14-hydroxy-6-thia-3,13-diazaheptacyclo[13.7.1.19,13.02,9.02,14.03,7.019,23]tetracosa-1(22),15(23),16,18,20-pentaen-10-one

In the title compound, C34H26F2N2O2S, an intra­molecular O—H⋯N hydrogen bond forms an S(5) ring motif. The piperidine ring adopts a chair conformation. The thia­zolidine ring and one of the pyrrolidine rings adopt envolope conformations with methyl­ene C atoms at the flap, whereas the other pyrrolidine ring adopts a half-chair conformation. The fluoro-substituted benzene rings form dihedral angles of 32.25 (10) and 38.27 (10)°, respectively, with the mean plane of the dihydro­acenaphthyl­ene ring system [maximum deviation = 0.043 (2) Å]. The dihedral angle between the fluoro-substituted benzene rings is 64.13 (14)°. In the crystal, mol­ecules are linked by weak C—H⋯O, C—H⋯F and C—H⋯S hydrogen bonds into a three-dimensional network.

2-Amino-4-(4-fluorophenyl)-6-methoxy-4H-benzo[h]chromene-3-carbonitrile

In the title mol­ecule, C21H15FN2O2, the dihedral angle between the fluoro-substituted benzene ring and the mean plane of the 4H-benzo[h]chromene ring system [maximum deviation = 0.109 (2) Å] is 83.35 (7)°. The pyran ring adopts a slight sofa conformation with the tertiary C(H) atom forming the flap. The meth­oxy group is slightly twisted from the attached benzene ring of the 4H-benzo[h]chromene moiety [C—O—C—C = −4.3 (3)°]. In the crystal, mol­ecules are linked by inter­molecular N—H⋯N hydrogen bonds into infinite wave-like chains along the b axis. The crystal packing is further stabilized by π–π inter­actions [centroid–centroid distance = 3.7713 (9) Å].

Ethyl 2-amino-4-(4-fluorophenyl)-6-methoxy-4H-benzo[h]chromene-3-carboxylate

In the title compound, C23H20FNO4, the fluoro-substituted benzene ring is approximately perpendicular to the mean plane of the 4H-benzo[h]chromene ring system [maximum deviation = 0.264 (1) Å], with a dihedral angle of 83.79 (6)°. The pyran ring adopts a flattened boat conformation. The meth­oxy group is slightly twisted from the attached benzene ring of the 4H-benzo[h]chromene moiety [C—O—C—C = −2.1 (2)°]. An intra­molecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, mol­ecules are linked by N—H⋯O and N—H⋯F hydrogen bonds into a layer parallel to the bc plane. The crystal packing also features C—H⋯π inter­actions.

(Z)-1-[4-Fluoro-2-(pyrrolidin-1-yl)phenyl]-3-phenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-one

In the title mol­ecule, C21H19FN4O, the triazole ring forms dihedral angles of 67.0 (1) and 59.6 (1)° with the phenyl and fluoro-substituted benzene rings, respectively. The dihedral angle between the phenyl ring and the fluoro-substituted benzene ring is 79.1 (1)°. The pyrrolidine ring is in a half-chair conformation. In the crystal, weak C—H⋯O and C—H⋯N hydrogen bonds connect mol­ecules into layers parallel to (001).

2-[3,5-Bis(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]-4,6-bis(4-fluorophenyl)pyrimidine

In the title compound, C31H20F4N4, the pyrazole ring adopts an envelope conformation and forms a dihedral angle of 9.91 (6)° with the adjacent pyrimidine ring. The pyrimidine ring forms dihedral angles of 9.23 (6) and 2.16 (5)° with its adjacent fluoro-substituted benzene rings, whereas these angles are 88.22 (6) and 9.66 (6)° for the pyrazole ring and its adjacent benzene rings. In the crystal, mol­ecules are linked by C—H⋯F hydrogen bonds into ribbons along [01-1]. The crystal packing is further stabilized by C—H⋯π and by π–π inter­actions, with centroid–centroid distances of 3.7428 (7) and 3.7630 (6) Å.

(E)-3-(4-Chlorophenyl)-1-(4-fluorophenyl)prop-2-en-1-one

In the title compound, C15H10ClFO, the fluoro-substituted benzene ring forms a dihedral angle of 44.41 (6)° with the chloro-substituted benzene ring. The only significant directional bonds in the crystal are weak C—H⋯π inter­actions.

(E)-1-(4,4''-Difluoro-5'-meth-oxy-1,1':3',1''-terphenyl-4'-yl)-3-(6-meth-oxy-naphthalen-2-yl)prop-2-en-1-one.

In the title compound, C33H24F2O3, the central benzene ring makes dihedral angles of 44.71 (10), 47.80 (10) and 63.68 (9)° with the two fluoro-substituted benzene rings and the naphthalene ring system, respectively. In the crystal, mol­ecules are connected via inter­molecular C—H⋯F and C—H⋯O hydrogen bonds. Furthermore, the crystal structure is stabilized by weak C—H⋯π and π–π inter­actions [centroid–centroid distance = 3.6816 (13) Å].

5-[(E)-4-Fluorobenzylidene]-8-(4-fluorophenyl)-2-hydroxy-9-phenyl-3,10-diazahexacyclo[10.7.1.13,7.02,11.07,11.016,20]henicosa-1(20),12,14,16,18-pentaen-6-one

In the title compound, C38H28F2N2O2, the piperidine ring adopts a chair conformation and the pyrrolidine ring adopts an envelope conformation with the spiro C atom as the flap atom. The naphthalene ring system makes dihedral angles of 39.89 (8), 35.33 (8) and 46.45 (8)° with the two fluoro-substituted benzene rings and the phenyl ring, respectively, while the dihedral angle between the two fluoro-substituted benzene rings is 75.21 (10)°. An intra­molecular O—H⋯N hydrogen bond generates an S(5) ring. In the crystal, mol­ecules are connected by C—H⋯O hydrogen bonds, forming supra­molecular chains propagating along the c-axis direction. Weak C—H⋯π inter­actions further consolidate the structure.

Methyl (2Z)-2-(2-fluoro-4-methoxybenzylidene)-5-(4-methoxyphenyl)-7-methyl-3-oxo-2,3-dihydro-5H-[1,3]thiazolo[3,2-a]pyrimidine-6-carboxylate

The asymmetric unit of the title compound, C24H21FN2O5S, consists of two crystallographically independent mol­ecules. In each mol­ecule, the central dihydro­pyrimidine ring is significantly puckered and adopts a conformation which is best described as an inter­mediate between a boat and a screw boat. The least-squares planes of the dihydro­pyrimidine rings are almost coplanar with the fluoro-substituted benzene rings, making dihedral angles of 9.04 (7) and 6.68 (7)°, and almost perpendicular to the meth­oxy-substituted benzene rings with dihedral angles of 89.23 (7) and 88.30 (7)°. In the mol­ecular structure, S(6) ring motifs are formed by C—H⋯O and C—H⋯S hydrogen bonds. In the crystal, mol­ecules are linked into a three-dimensional network by inter­molecular C—H⋯O and C—H⋯F hydrogen bonds. The crystal structure is further stabilized by a C—H⋯π inter­action.

N-(3-Chloro-4-fluoro-phen-yl)-2-(naphthalen-1-yl)acetamide.

In the title compound, C18H13ClFNO, the dihedral angle between the mean planes of the chloro- and fluoro-substituted benzene ring and the naphthalene ring system is 60.5 (8)°. In the crystal, mol­ecules are linked by N—H⋯O hydrogen bonds, forming a zigzag chain along [101].

Bis{2-[(E)-(4-fluorobenzyl)iminomethyl]-6-methoxyphenolato}palladium(II)

In the title compound, [Pd(C15H13FNO2)2], the PdII atom is tetra­coordinated by two N atoms and two O atoms from the two 2-[(4-fluoro­benz­yl)imino­meth­yl]-6-meth­oxy­phen­oxy ligands, forming a square-planar geometry. The two N atoms and the two O atoms around the PdII atom are trans to each other. The dihedral angle between the two fluoro-substituted benzene rings is 39.03 (6)°. The mol­ecular structure is stabilized by an intra­molecular C—H⋯O hydrogen bond. In the crystal, weak inter­molecular C—H⋯π inter­actions occur.