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In the crystal structures of the title compounds, C11H9FN2O, (I), and C13H12FNO4, (II), the mol­ecules are joined pairwise via different hydrogen bonds and the constituent pairs are crosslinked by weak C-H...O hydrogen bonds. The basic structural motif in (I), which is partially disordered, comprises pairs of mol­ecules arranged in an anti­parallel fashion which enables C-H...N[triple bond]C inter­actions. The pairs of mol­ecules are crosslinked by two weak C-H...O hydrogen bonds. The constituent pair in (II) is formed by intra­molecular bifurcated C-H...O/O' and combined inter- and intra­molecular N-H...O hydrogen bonds. In both structures, F atoms form weak C-F...H-C inter­actions with the H atoms of the two neighbouring methyl groups, the H...F separations being 2.59/2.80 and 2.63/2.71 Å in (I) and (II), respectively. The bond orders in the mol­ecules, estimated using the natural bond orbitals (NBO) formalism, correlate with the changes in bond lengths. Deviations from the ideal mol­ecular geometry are explained by the concept of non-equivalent hybrid orbitals. The existence of possible conformers of (I) and (II) is analysed by mol­ecular calculations at the B3LYP/6-31+G** level of theory.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110023334/sk3374sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110023334/sk3374Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110023334/sk3374IIsup3.hkl
Contains datablock II

CCDC references: 790637; 790638

Comment top

The heteroarylaminoethylene type of compounds substituted with fluorine are not only excellent precursors for the synthesis of biologically active 4-quinolones, but they are also biologically active themselves as they show e.g. photobleaching activity towards cells of Nicotiana tabacum, and fungicides [fungicidal?], germicides [germicidal?] or herbicides [herbicidal?] [properties?]. The title compounds were synthesized within the framework of our continuous study (Langer et al., 2006, 2009; Smrčok et al., 2007) of the structure and properties of potential precursors of fluoroquinolones, knowledge of which has proved essential in reaction pathway considerations and planning.

Perspective drawings of the title molecules are shown in Fig.1 for (I) and in Fig.2 for (II). The structure of (I) shows a disorder of the phenyl ring (rotation by 180°) with occupancy of 0.890 (1) for the main component and the methyl group at C10 has been refined with occupancy of 50% for two orientations with 60° relative to each other. Considering the calculated dipole moments for the molecules of (I) and (II) (4.5 and 2.3 D), it can be assumed that the main packing force in both structures is electrostatic. The basic building unit in both structures comprises molecules joined pairwise via different hydrogen bonds and the constituting [resulting?] pairs are cross-linked to form three-dimensional hydrogen-bonded networks. The fundamental structural motif in the structure of (I) is pairs of molecules arranged in an antiparallel fashion which enables C—H···NC interactions (Fig. 3). Every N atom is an acceptor of two hydrogen bonds of two slightly different lengths (Table 1). The pairs of molecules are cross-linked by two weak C—H···O hydrogen bonds aiming at the O1 oxygen atom, which is also involved in the very bent intramolecular N1—H1···O1 hydrogen bond (Table 1). This arrangement can be described as a ribbon of molecules running approximately parallel to [101]. The pair of molecules in the structure of (II) is formed by the intermolecular bifurcated C2—H2···O1iv/O2iv and the combined inter- and intramolecular N1—H1···O1/O1iv hydrogen bonds (Fig. 4). These basic pairs of molecules form sheets through the C5—H5···O4v hydrogen bond. Although the arrangement of neighboring sheets is dictated mainly by electrostatic forces they also connected though C12—H12B···Ovi hydrogen bonding.

In both structures F atoms appear in such positions that they could form weak C—F···H—C interactions (Howard et al., 1996; Dunitz & Taylor, 1997) with the H atoms of the two neighbouring methyl groups, i.e. two H10A atoms in the structure of (I), and the H12C and H13C atoms in the structure of (II). The H···F separations, 2.59/2.80 Å in (I) and 2.63/2.71 Å (II), are well within the limits found for this type of non-bonded contact (Shimoni & Glusker, 1994).

NBO (natural bond orbitals) analysis (Foster & Weinhold, 1980) carried out for the isolated molecules reveals a general delocalization pattern, which can be characterized (i) by the delocalization of the lone pair of the N atom into the CC antibonding orbital resulting in the lowering of the bond order of this bond and in the increase of the bond order of the N1—C7 bond, and (ii) by shifting of the electrons from the CO double bonds towards the pπ orbital of the O atoms resulting in the relatively large partial negative charge on O1 [NBO charges are -0.621 |e| in (I) and -0.622 |e| in (II)] and also in a decrease of its bond order (Tables 2 and 3). This shift is further enhanced by formation of an intramolecular O1···H1—N1 hydrogen bond. All these changes are qualitatively described by a superposition of resonance structures, depicted in Fig. 5. The most obvious geometric consequences of such electron delocalizations are shortening of the formally single N1—C7 bond and also lengthening of the formally double C7C8 bond, reflected in the decrease of the bond order (Tables 2 and 3). Another consequence of electron redistribution is structural rigidity of the N1—C7—C8-(C9—O1)(C11—N2) moiety in (I), which is further enhanced by formation of an intramolecular N1—H1···O1 hydrogen bond.

The additional characteristic feature of the C1—N1—C7—C8 fragment is increased values of the skeletal angles, namely C1—N1—C7 [125.15 (14)° in (I), 125.6 (2)° in (II))] and N1—C7—C8 [124.79 (15)° in (I) and 127.4 (3)° in (II)] relative to the expected ideal value of 120°. The main reason is the increased s content in the hybrid orbitals on the N1 and C7 atoms as a consequence of the shortening of the N1—C7 bond. This increase in s character in turn brings about an increase in the p character in two other formally sp2 hybrids and thus lowers the angle between them (Bent, 1961; Langer et al., 2009).

The phenyl ring connected to the aminomethylene group is, in both structures, only slightly rotated from the plane of the N1—C7—C8—C9—C11 atoms, the torsion angle C7—N1—C1—C6 being -1.6 (2)° in (I) and -2.7 (4)° in (II). Full optimizations of the molecular geometry in vacuum, however, give remarkably larger torsion angles, ~13° (I) and ~11° (II), but a closer inspection of the torsion potential around the C1—N1 bond reveals that it is, in both cases, very flat. Its flatness can be documented by the fact that the strictly planar structure of (I) has a total energy of only 0.06 kJ mol-1 higher than the minimum and the calculated harmonic torsion frequency is only 14 cm-1. Such flatness of the torsion potentials is a compromise between the two competing interactions – on the one hand, the repulsion of the H1—H2 and the H6—H7 H atoms tending to rotate the ring from the planar position and, on the other hand, delocalization of a lone pair of the N atom into the phenyl ring, stabilizing the planar arrangement.

An interesting feature of this torsion potential is the low barrier for ~180° rotation of the substituted phenyl ring, leading to conformations (Ia) and (IIa). According to the molecular calculation in vacuum, these conformations are even slightly more stable than the molecules of (I) and (II), i.e. 0.6 and 0.4 kJ mol-1, respectively. In (I), this conformation (Ia) is present as a minor component with an occupancy of 0.110 (1). The rotation barriers separating these conformers are also rather small, 14.7 and 15.0 kJ mol-1, and are further reduced by a polar medium. For instance, our polarizable continuum model (PCM; Miertuš et al., 1981; Foresman et al., 1996) calculation revealed that in water the barrier further reduces to 10.2 and 11.7 kJ mol-1, respectively. The preference of the (I) and (II) over (Ia) and (IIa) in the real structures is thus apparently a result of the packing forces in the crystals.

Related literature top

For related literature, see: Bent (1961); Dunitz & Taylor (1997); Foresman et al. (1996); Foster & Weinhold (1980); Frisch et al. (1998); Glendening et al. (1993); Howard et al. (1996); Langer et al. (2006, 2009); Leya et al. (1999); Miertuš et al. (1981); Shimoni & Glusker (1994); Smrčok et al. (2007).

Experimental top

The title compounds could be easily prepared by nucleophilic vinylic substitution of equimolar amounts of 2-ethoxymethylene-3-oxobutanenitrile or 5-ethoxymethylene-4,6-dioxo-2,2-dimethyl-1,3-dioxane with 3-fluoroaniline in boiling ethanol (Leya et al., 1999).

Refinement top

For (I), a rotational disorder of the phenyl ring has been resolved on F3/F5 positions with the distance C—F restrained to a common value (refined) with an s.u. of 0.02 Å allowed. Aromatic H atoms were refined isotropically with Uĩso(H) = 1.2Ueq(C) and their positions were constrained to ideal geometry using an appropriate riding model, with N—H = 0.88 Å and C—H = 0.95 Å. For methyl groups, C—C—H angles (109.5°) were kept fixed, while the torsion angle was allowed to refine with the starting positions based on the circular Fourier synthesis averaged using the local threefold axis with Uĩso(H)= 1.5Ueq(C) and C—H = 0.98 Å. In (I), the methyl group is also disordered and has been refined with two components with 50% occupancy, rotated 60° relative to each other. Molecular calculations were done at the B3LYP/6–31+G** level of theory using GAUSSIAN98 (Frisch et al., 1998). Natural bond orbital (Foster & Weinhold, 1980) calculations were done using the NBO 3.1 version (Glendening et al., 1993) of the program included in the GAUSSIAN package.

Structure description top

The heteroarylaminoethylene type of compounds substituted with fluorine are not only excellent precursors for the synthesis of biologically active 4-quinolones, but they are also biologically active themselves as they show e.g. photobleaching activity towards cells of Nicotiana tabacum, and fungicides [fungicidal?], germicides [germicidal?] or herbicides [herbicidal?] [properties?]. The title compounds were synthesized within the framework of our continuous study (Langer et al., 2006, 2009; Smrčok et al., 2007) of the structure and properties of potential precursors of fluoroquinolones, knowledge of which has proved essential in reaction pathway considerations and planning.

Perspective drawings of the title molecules are shown in Fig.1 for (I) and in Fig.2 for (II). The structure of (I) shows a disorder of the phenyl ring (rotation by 180°) with occupancy of 0.890 (1) for the main component and the methyl group at C10 has been refined with occupancy of 50% for two orientations with 60° relative to each other. Considering the calculated dipole moments for the molecules of (I) and (II) (4.5 and 2.3 D), it can be assumed that the main packing force in both structures is electrostatic. The basic building unit in both structures comprises molecules joined pairwise via different hydrogen bonds and the constituting [resulting?] pairs are cross-linked to form three-dimensional hydrogen-bonded networks. The fundamental structural motif in the structure of (I) is pairs of molecules arranged in an antiparallel fashion which enables C—H···NC interactions (Fig. 3). Every N atom is an acceptor of two hydrogen bonds of two slightly different lengths (Table 1). The pairs of molecules are cross-linked by two weak C—H···O hydrogen bonds aiming at the O1 oxygen atom, which is also involved in the very bent intramolecular N1—H1···O1 hydrogen bond (Table 1). This arrangement can be described as a ribbon of molecules running approximately parallel to [101]. The pair of molecules in the structure of (II) is formed by the intermolecular bifurcated C2—H2···O1iv/O2iv and the combined inter- and intramolecular N1—H1···O1/O1iv hydrogen bonds (Fig. 4). These basic pairs of molecules form sheets through the C5—H5···O4v hydrogen bond. Although the arrangement of neighboring sheets is dictated mainly by electrostatic forces they also connected though C12—H12B···Ovi hydrogen bonding.

In both structures F atoms appear in such positions that they could form weak C—F···H—C interactions (Howard et al., 1996; Dunitz & Taylor, 1997) with the H atoms of the two neighbouring methyl groups, i.e. two H10A atoms in the structure of (I), and the H12C and H13C atoms in the structure of (II). The H···F separations, 2.59/2.80 Å in (I) and 2.63/2.71 Å (II), are well within the limits found for this type of non-bonded contact (Shimoni & Glusker, 1994).

NBO (natural bond orbitals) analysis (Foster & Weinhold, 1980) carried out for the isolated molecules reveals a general delocalization pattern, which can be characterized (i) by the delocalization of the lone pair of the N atom into the CC antibonding orbital resulting in the lowering of the bond order of this bond and in the increase of the bond order of the N1—C7 bond, and (ii) by shifting of the electrons from the CO double bonds towards the pπ orbital of the O atoms resulting in the relatively large partial negative charge on O1 [NBO charges are -0.621 |e| in (I) and -0.622 |e| in (II)] and also in a decrease of its bond order (Tables 2 and 3). This shift is further enhanced by formation of an intramolecular O1···H1—N1 hydrogen bond. All these changes are qualitatively described by a superposition of resonance structures, depicted in Fig. 5. The most obvious geometric consequences of such electron delocalizations are shortening of the formally single N1—C7 bond and also lengthening of the formally double C7C8 bond, reflected in the decrease of the bond order (Tables 2 and 3). Another consequence of electron redistribution is structural rigidity of the N1—C7—C8-(C9—O1)(C11—N2) moiety in (I), which is further enhanced by formation of an intramolecular N1—H1···O1 hydrogen bond.

The additional characteristic feature of the C1—N1—C7—C8 fragment is increased values of the skeletal angles, namely C1—N1—C7 [125.15 (14)° in (I), 125.6 (2)° in (II))] and N1—C7—C8 [124.79 (15)° in (I) and 127.4 (3)° in (II)] relative to the expected ideal value of 120°. The main reason is the increased s content in the hybrid orbitals on the N1 and C7 atoms as a consequence of the shortening of the N1—C7 bond. This increase in s character in turn brings about an increase in the p character in two other formally sp2 hybrids and thus lowers the angle between them (Bent, 1961; Langer et al., 2009).

The phenyl ring connected to the aminomethylene group is, in both structures, only slightly rotated from the plane of the N1—C7—C8—C9—C11 atoms, the torsion angle C7—N1—C1—C6 being -1.6 (2)° in (I) and -2.7 (4)° in (II). Full optimizations of the molecular geometry in vacuum, however, give remarkably larger torsion angles, ~13° (I) and ~11° (II), but a closer inspection of the torsion potential around the C1—N1 bond reveals that it is, in both cases, very flat. Its flatness can be documented by the fact that the strictly planar structure of (I) has a total energy of only 0.06 kJ mol-1 higher than the minimum and the calculated harmonic torsion frequency is only 14 cm-1. Such flatness of the torsion potentials is a compromise between the two competing interactions – on the one hand, the repulsion of the H1—H2 and the H6—H7 H atoms tending to rotate the ring from the planar position and, on the other hand, delocalization of a lone pair of the N atom into the phenyl ring, stabilizing the planar arrangement.

An interesting feature of this torsion potential is the low barrier for ~180° rotation of the substituted phenyl ring, leading to conformations (Ia) and (IIa). According to the molecular calculation in vacuum, these conformations are even slightly more stable than the molecules of (I) and (II), i.e. 0.6 and 0.4 kJ mol-1, respectively. In (I), this conformation (Ia) is present as a minor component with an occupancy of 0.110 (1). The rotation barriers separating these conformers are also rather small, 14.7 and 15.0 kJ mol-1, and are further reduced by a polar medium. For instance, our polarizable continuum model (PCM; Miertuš et al., 1981; Foresman et al., 1996) calculation revealed that in water the barrier further reduces to 10.2 and 11.7 kJ mol-1, respectively. The preference of the (I) and (II) over (Ia) and (IIa) in the real structures is thus apparently a result of the packing forces in the crystals.

For related literature, see: Bent (1961); Dunitz & Taylor (1997); Foresman et al. (1996); Foster & Weinhold (1980); Frisch et al. (1998); Glendening et al. (1993); Howard et al. (1996); Langer et al. (2006, 2009); Leya et al. (1999); Miertuš et al. (1981); Shimoni & Glusker (1994); Smrčok et al. (2007).

Computing details top

For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003), SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The atom-numbering scheme for (I), with atomic displacement ellipsoids drawn at the 50% probability level. Note that F3 and H5 have 0.890 (1) occupancy, while F5/H3 0.110 (1). Occupancy for H atoms attached to C10 was fixed to 50%.
[Figure 2] Fig. 2. The atom-numbering scheme for (II), with atomic displacement ellipsoids drawn at the 50% probability level.
[Figure 3] Fig. 3. Pairs of the molecules in the structure of (I) are linked by C2—H2···O1i hydrogen bonds. The C10—H10C···O1iii hydrogen bond is not shown for the sake of clarity and H atoms not involved in the hydrogen-bonding scheme have been omitted. Symmetry codes are as in Table 1. Note that just the main component present in the structure of (I) is shown.
[Figure 4] Fig. 4. Hydrogen bonds within the constitutuent pair of molecules and the hydrogen bonds linking the pairs into sheets in the structure of (II). H atoms not involved in the hydrogen-bonding scheme have been omitted. Symmetry codes are as in Table 1.
[Figure 5] Fig. 5. Possible resonance structures of the title compounds. All principal geometry feaures are compatible with a superposition of these resonance structures.
(I) 2-{[(3-Fluorophenyl)amino]methylidene}-3-oxobutanenitrile top
Crystal data top
C11H9FN2OF(000) = 424
Mr = 204.20Dx = 1.439 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2408 reflections
a = 13.907 (2) Åθ = 2.5–29.1°
b = 5.0357 (8) ŵ = 0.11 mm1
c = 14.233 (2) ÅT = 153 K
β = 108.946 (4)°Needle, colourless
V = 942.8 (3) Å30.49 × 0.12 × 0.08 mm
Z = 4
Data collection top
Siemens CCD area-detector
diffractometer
2554 independent reflections
Radiation source: fine-focus sealed tube1650 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.072
ω scansθmax = 29.3°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 1919
Tmin = 0.949, Tmax = 0.991k = 66
13411 measured reflectionsl = 1919
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0565P)2 + 0.1626P]
where P = (Fo2 + 2Fc2)/3
2554 reflections(Δ/σ)max = 0.001
148 parametersΔρmax = 0.25 e Å3
2 restraintsΔρmin = 0.20 e Å3
Crystal data top
C11H9FN2OV = 942.8 (3) Å3
Mr = 204.20Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.907 (2) ŵ = 0.11 mm1
b = 5.0357 (8) ÅT = 153 K
c = 14.233 (2) Å0.49 × 0.12 × 0.08 mm
β = 108.946 (4)°
Data collection top
Siemens CCD area-detector
diffractometer
2554 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1650 reflections with I > 2σ(I)
Tmin = 0.949, Tmax = 0.991Rint = 0.072
13411 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0472 restraints
wR(F2) = 0.128H-atom parameters constrained
S = 1.01Δρmax = 0.25 e Å3
2554 reflectionsΔρmin = 0.20 e Å3
148 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
F30.93705 (9)1.6802 (2)0.54075 (9)0.0395 (4)0.890 (3)
F50.7392 (9)1.410 (2)0.7260 (7)0.052 (4)0.110 (3)
O10.68220 (9)0.7314 (2)0.24770 (9)0.0314 (3)
N10.70183 (10)0.9774 (2)0.42203 (10)0.0244 (3)
H10.72230.97510.36960.029*
N20.46035 (11)0.2881 (3)0.38393 (11)0.0375 (4)
C10.74737 (12)1.1674 (3)0.49746 (11)0.0232 (3)
C20.82132 (12)1.3321 (3)0.48250 (12)0.0256 (3)
H20.84101.31620.42480.031*
C30.86501 (12)1.5190 (3)0.55425 (12)0.0278 (4)
H30.91561.63230.54460.033*0.110 (3)
C40.83942 (13)1.5509 (3)0.63927 (12)0.0291 (4)
H40.87121.68200.68730.035*
C50.76566 (14)1.3845 (3)0.65195 (13)0.0318 (4)
H50.74641.40210.70990.038*0.890 (3)
C60.71898 (13)1.1923 (3)0.58215 (12)0.0290 (4)
H60.66841.07950.59210.035*
C70.63120 (12)0.8040 (3)0.42450 (12)0.0252 (3)
H70.60790.80870.48020.030*
C80.58877 (11)0.6159 (3)0.35173 (11)0.0233 (3)
C90.61772 (12)0.5840 (3)0.26291 (12)0.0245 (3)
C100.56819 (14)0.3686 (3)0.19082 (12)0.0314 (4)
H10A0.56770.41880.12410.047*0.50
H10B0.49820.34330.19040.047*0.50
H10C0.60630.20280.21080.047*0.50
H10D0.54710.22450.22610.047*0.50
H10E0.61660.30000.15980.047*0.50
H10F0.50850.44050.13940.047*0.50
C110.51691 (13)0.4372 (3)0.36984 (12)0.0268 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F30.0417 (7)0.0370 (6)0.0458 (8)0.0159 (5)0.0225 (6)0.0090 (5)
F50.082 (9)0.045 (6)0.033 (6)0.003 (5)0.026 (6)0.009 (4)
O10.0384 (7)0.0270 (5)0.0320 (6)0.0064 (5)0.0159 (5)0.0015 (5)
N10.0299 (7)0.0215 (6)0.0226 (7)0.0007 (5)0.0096 (6)0.0025 (5)
N20.0389 (9)0.0370 (8)0.0410 (9)0.0077 (7)0.0191 (8)0.0064 (7)
C10.0261 (8)0.0175 (6)0.0231 (8)0.0037 (6)0.0039 (7)0.0006 (5)
C20.0267 (8)0.0248 (7)0.0257 (8)0.0037 (6)0.0090 (7)0.0001 (6)
C30.0263 (8)0.0220 (7)0.0331 (9)0.0000 (6)0.0068 (7)0.0001 (6)
C40.0337 (9)0.0235 (7)0.0274 (8)0.0011 (6)0.0063 (7)0.0045 (6)
C50.0402 (10)0.0302 (8)0.0280 (9)0.0010 (7)0.0152 (8)0.0040 (7)
C60.0320 (9)0.0252 (7)0.0315 (9)0.0032 (6)0.0126 (8)0.0006 (6)
C70.0264 (8)0.0221 (7)0.0273 (8)0.0041 (6)0.0091 (7)0.0012 (6)
C80.0221 (8)0.0208 (6)0.0254 (8)0.0008 (6)0.0054 (7)0.0002 (6)
C90.0258 (8)0.0198 (6)0.0261 (8)0.0029 (6)0.0061 (7)0.0023 (6)
C100.0388 (10)0.0286 (8)0.0276 (9)0.0045 (7)0.0120 (8)0.0053 (7)
C110.0293 (8)0.0263 (7)0.0248 (8)0.0010 (7)0.0086 (7)0.0041 (6)
Geometric parameters (Å, º) top
F3—C31.3508 (19)C5—C61.388 (2)
F5—C51.230 (10)C5—H50.9500
O1—C91.2361 (18)C6—H60.9500
N1—C71.3234 (19)C7—C81.386 (2)
N1—C11.4240 (19)C7—H70.9500
N1—H10.8800C8—C111.429 (2)
N2—C111.151 (2)C8—C91.455 (2)
C1—C21.390 (2)C9—C101.498 (2)
C1—C61.391 (2)C10—H10A0.9800
C2—C31.377 (2)C10—H10B0.9800
C2—H20.9500C10—H10C0.9800
C3—C41.377 (2)C10—H10D0.9800
C3—H30.9500C10—H10E0.9800
C4—C51.381 (2)C10—H10F0.9800
C4—H40.9500
C7—N1—C1125.15 (14)C8—C7—H7117.6
C7—N1—H1117.4C7—C8—C11116.65 (14)
C1—N1—H1117.4C7—C8—C9123.64 (14)
C2—C1—C6120.75 (14)C11—C8—C9119.62 (13)
C2—C1—N1117.09 (14)O1—C9—C8120.47 (14)
C6—C1—N1122.16 (14)O1—C9—C10120.87 (14)
C3—C2—C1117.68 (15)C8—C9—C10118.66 (14)
C3—C2—H2121.2C9—C10—H10A109.5
C1—C2—H2121.2C9—C10—H10B109.5
F3—C3—C2118.33 (15)H10A—C10—H10B109.5
F3—C3—C4118.04 (14)C9—C10—H10C109.5
C2—C3—C4123.62 (15)H10A—C10—H10C109.5
F3—C3—H30.2H10B—C10—H10C109.5
C2—C3—H3118.2C9—C10—H10D109.5
C4—C3—H3118.2H10A—C10—H10D141.1
C3—C4—C5117.33 (15)H10B—C10—H10D56.3
C3—C4—H4121.3H10C—C10—H10D56.3
C5—C4—H4121.3C9—C10—H10E109.5
F5—C5—C6119.1 (5)H10A—C10—H10E56.3
F5—C5—C4119.3 (5)H10B—C10—H10E141.1
C6—C5—C4121.60 (16)H10C—C10—H10E56.3
F5—C5—H51.2H10D—C10—H10E109.5
C6—C5—H5119.2C9—C10—H10F109.5
C4—C5—H5119.2H10A—C10—H10F56.3
C5—C6—C1119.02 (15)H10B—C10—H10F56.3
C5—C6—H6120.5H10C—C10—H10F141.1
C1—C6—H6120.5H10D—C10—H10F109.5
N1—C7—C8124.79 (15)H10E—C10—H10F109.5
N1—C7—H7117.6N2—C11—C8178.33 (16)
C7—N1—C1—C2179.33 (14)C2—C1—C6—C50.0 (2)
C7—N1—C1—C61.6 (2)N1—C1—C6—C5179.11 (14)
C6—C1—C2—C30.1 (2)C1—N1—C7—C8178.58 (14)
N1—C1—C2—C3179.17 (13)N1—C7—C8—C11177.07 (14)
C1—C2—C3—F3179.93 (13)N1—C7—C8—C90.6 (2)
C1—C2—C3—C40.0 (2)C7—C8—C9—O11.3 (2)
F3—C3—C4—C5180.00 (14)C11—C8—C9—O1177.64 (14)
C2—C3—C4—C50.1 (2)C7—C8—C9—C10178.45 (14)
C3—C4—C5—F5178.5 (6)C11—C8—C9—C102.1 (2)
C3—C4—C5—C60.1 (2)C7—C8—C11—N2129 (6)
F5—C5—C6—C1178.6 (6)C9—C8—C11—N248 (6)
C4—C5—C6—C10.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.882.052.7065 (17)131
C2—H2···O1i0.952.413.300 (2)156
C6—H6···N2ii0.952.673.618 (2)173
C7—H7···N2ii0.952.463.395 (2)167
C10—H10C···O1iii0.982.583.554 (2)172
Symmetry codes: (i) x+3/2, y+1/2, z+1/2; (ii) x+1, y+1, z+1; (iii) x, y1, z.
(II) 5-{[(3-fluorophenyl)amino]methylidene}-2,2-dimethyl-1,3-dioxane-4,6-dione top
Crystal data top
C13H12FNO4Z = 2
Mr = 265.24F(000) = 276
Triclinic, P1Dx = 1.466 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.3000 (12) ÅCell parameters from 769 reflections
b = 9.4753 (18) Åθ = 2.9–25.0°
c = 10.765 (2) ŵ = 0.12 mm1
α = 88.947 (5)°T = 153 K
β = 79.810 (4)°Needle, colourless
γ = 71.931 (4)°0.38 × 0.11 × 0.06 mm
V = 600.8 (2) Å3
Data collection top
Siemens CCD area-detector
diffractometer
2132 independent reflections
Radiation source: fine-focus sealed tube1244 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.071
ω scansθmax = 25.1°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 77
Tmin = 0.956, Tmax = 0.993k = 1111
6091 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0122P)2 + 0.015P]
where P = (Fo2 + 2Fc2)/3
2132 reflections(Δ/σ)max < 0.001
174 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C13H12FNO4γ = 71.931 (4)°
Mr = 265.24V = 600.8 (2) Å3
Triclinic, P1Z = 2
a = 6.3000 (12) ÅMo Kα radiation
b = 9.4753 (18) ŵ = 0.12 mm1
c = 10.765 (2) ÅT = 153 K
α = 88.947 (5)°0.38 × 0.11 × 0.06 mm
β = 79.810 (4)°
Data collection top
Siemens CCD area-detector
diffractometer
2132 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1244 reflections with I > 2σ(I)
Tmin = 0.956, Tmax = 0.993Rint = 0.071
6091 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.147H-atom parameters constrained
S = 1.01Δρmax = 0.26 e Å3
2132 reflectionsΔρmin = 0.25 e Å3
174 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F10.0907 (3)1.33859 (19)1.06737 (15)0.0402 (5)
O11.1625 (3)0.9092 (2)0.89957 (17)0.0272 (5)
O21.4558 (3)0.7596 (2)0.76982 (17)0.0258 (5)
O31.4308 (3)0.6984 (2)0.56241 (17)0.0269 (5)
O41.1258 (3)0.8020 (2)0.47977 (18)0.0348 (6)
N10.7576 (3)1.0267 (2)0.8114 (2)0.0231 (6)
H10.82061.02500.87630.028*
C10.5266 (4)1.1156 (3)0.8223 (3)0.0229 (7)
C20.4194 (4)1.1860 (3)0.9389 (3)0.0247 (7)
H20.49771.17681.00580.030*
C30.1953 (4)1.2696 (3)0.9530 (3)0.0269 (7)
C40.0722 (4)1.2864 (3)0.8576 (3)0.0285 (7)
H40.08041.34250.87050.034*
C50.1819 (4)1.2174 (3)0.7421 (3)0.0275 (7)
H50.10201.22830.67580.033*
C60.4086 (4)1.1323 (3)0.7223 (3)0.0254 (7)
H60.48081.08700.64360.031*
C70.8829 (4)0.9468 (3)0.7106 (3)0.0253 (7)
H70.81330.95060.64080.030*
C81.1055 (4)0.8581 (3)0.6968 (3)0.0231 (7)
C91.2332 (4)0.8455 (3)0.7968 (3)0.0226 (7)
C101.5148 (4)0.6410 (3)0.6758 (3)0.0239 (7)
C111.2106 (4)0.7871 (3)0.5742 (3)0.0267 (7)
C121.4162 (5)0.5211 (3)0.7263 (3)0.0330 (8)
H12A1.47360.48380.80130.049*
H12B1.45840.44160.66370.049*
H12C1.25380.56140.74590.049*
C131.7680 (4)0.5894 (3)0.6401 (3)0.0312 (8)
H13A1.81770.66750.59940.047*
H13B1.81530.50390.58340.047*
H13C1.83340.56370.71470.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0341 (10)0.0465 (12)0.0320 (11)0.0040 (8)0.0002 (8)0.0101 (9)
O10.0280 (10)0.0306 (12)0.0224 (12)0.0074 (9)0.0052 (9)0.0040 (10)
O20.0206 (10)0.0267 (12)0.0275 (12)0.0021 (8)0.0064 (8)0.0090 (10)
O30.0266 (10)0.0326 (12)0.0205 (11)0.0083 (9)0.0029 (8)0.0031 (10)
O40.0354 (12)0.0453 (14)0.0246 (12)0.0112 (10)0.0099 (10)0.0020 (11)
N10.0229 (12)0.0280 (14)0.0197 (13)0.0079 (10)0.0071 (10)0.0007 (11)
C10.0219 (14)0.0223 (16)0.0282 (17)0.0119 (12)0.0058 (12)0.0047 (14)
C20.0228 (15)0.0286 (18)0.0243 (16)0.0065 (13)0.0117 (12)0.0021 (14)
C30.0285 (15)0.0264 (17)0.0256 (17)0.0093 (13)0.0025 (13)0.0026 (14)
C40.0222 (15)0.0267 (17)0.0366 (19)0.0067 (13)0.0071 (14)0.0027 (15)
C50.0254 (15)0.0285 (18)0.0343 (19)0.0122 (13)0.0140 (13)0.0049 (15)
C60.0300 (16)0.0269 (17)0.0216 (16)0.0119 (13)0.0052 (13)0.0001 (14)
C70.0298 (16)0.0277 (17)0.0244 (17)0.0155 (14)0.0087 (13)0.0003 (14)
C80.0220 (15)0.0241 (16)0.0236 (16)0.0071 (13)0.0048 (12)0.0008 (14)
C90.0218 (14)0.0204 (16)0.0262 (17)0.0069 (12)0.0050 (12)0.0015 (14)
C100.0261 (15)0.0266 (17)0.0190 (15)0.0077 (13)0.0046 (12)0.0038 (14)
C110.0259 (15)0.0302 (18)0.0280 (18)0.0130 (14)0.0079 (13)0.0022 (15)
C120.0353 (17)0.0274 (18)0.0353 (19)0.0113 (14)0.0011 (14)0.0007 (15)
C130.0268 (15)0.0333 (19)0.0304 (18)0.0056 (14)0.0030 (13)0.0050 (15)
Geometric parameters (Å, º) top
F1—C31.361 (3)C4—H40.9300
O1—C91.213 (3)C5—C61.386 (3)
O2—C91.368 (3)C5—H50.9300
O2—C101.441 (3)C6—H60.9300
O3—C111.366 (3)C7—C81.377 (3)
O3—C101.446 (3)C7—H70.9300
O4—C111.216 (3)C8—C111.442 (4)
N1—C71.315 (3)C8—C91.435 (4)
N1—C11.422 (3)C10—C131.495 (3)
N1—H10.8600C10—C121.506 (4)
C1—C61.392 (4)C12—H12A0.9600
C1—C21.390 (4)C12—H12B0.9600
C2—C31.370 (3)C12—H12C0.9600
C2—H20.9300C13—H13A0.9600
C3—C41.372 (4)C13—H13B0.9600
C4—C51.377 (4)C13—H13C0.9600
C9—O2—C10117.1 (2)C11—C8—C9121.2 (2)
C11—O3—C10118.2 (2)C7—C8—C9121.6 (3)
C7—N1—C1125.6 (2)O1—C9—O2118.2 (2)
C7—N1—H1117.2O1—C9—C8125.4 (2)
C1—N1—H1117.2O2—C9—C8116.3 (2)
C6—C1—C2120.3 (2)O2—C10—O3109.8 (2)
C6—C1—N1122.7 (3)O2—C10—C13106.9 (2)
C2—C1—N1117.0 (2)O3—C10—C13105.9 (2)
C3—C2—C1118.3 (3)O2—C10—C12109.9 (2)
C3—C2—H2120.8O3—C10—C12110.3 (2)
C1—C2—H2120.8C13—C10—C12113.9 (2)
F1—C3—C4118.7 (2)O4—C11—O3116.9 (3)
F1—C3—C2118.2 (2)O4—C11—C8126.7 (3)
C4—C3—C2123.1 (3)O3—C11—C8116.3 (2)
C3—C4—C5117.8 (3)C10—C12—H12A109.5
C3—C4—H4121.1C10—C12—H12B109.5
C5—C4—H4121.1H12A—C12—H12B109.5
C6—C5—C4121.5 (3)C10—C12—H12C109.5
C6—C5—H5119.3H12A—C12—H12C109.5
C4—C5—H5119.3H12B—C12—H12C109.5
C1—C6—C5118.9 (3)C10—C13—H13A109.5
C1—C6—H6120.5C10—C13—H13B109.5
C5—C6—H6120.5H13A—C13—H13B109.5
N1—C7—C8127.4 (3)C10—C13—H13C109.5
N1—C7—H7116.3H13A—C13—H13C109.5
C8—C7—H7116.3H13B—C13—H13C109.5
C11—C8—C7117.0 (2)
C7—N1—C1—C62.7 (4)C11—C8—C9—O1174.9 (3)
C7—N1—C1—C2176.8 (2)C7—C8—C9—O10.3 (5)
C6—C1—C2—C31.1 (4)C11—C8—C9—O21.9 (4)
N1—C1—C2—C3178.5 (2)C7—C8—C9—O2177.0 (2)
C1—C2—C3—F1179.9 (2)C9—O2—C10—O351.7 (3)
C1—C2—C3—C40.2 (4)C9—O2—C10—C13166.2 (2)
F1—C3—C4—C5179.1 (2)C9—O2—C10—C1269.8 (3)
C2—C3—C4—C51.1 (4)C11—O3—C10—O248.3 (3)
C3—C4—C5—C60.7 (4)C11—O3—C10—C13163.3 (2)
C2—C1—C6—C51.4 (4)C11—O3—C10—C1273.0 (3)
N1—C1—C6—C5178.1 (2)C10—O3—C11—O4161.2 (2)
C4—C5—C6—C10.5 (4)C10—O3—C11—C821.1 (3)
C1—N1—C7—C8179.1 (3)C7—C8—C11—O43.1 (4)
N1—C7—C8—C11176.8 (3)C9—C8—C11—O4172.2 (3)
N1—C7—C8—C91.5 (5)C7—C8—C11—O3179.4 (2)
C10—O2—C9—O1155.3 (2)C9—C8—C11—O35.3 (4)
C10—O2—C9—C827.8 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.862.152.775 (3)129
N1—H1···O1i0.862.533.334 (3)156
C2—H2···O1i0.932.443.296 (3)153
C2—H2···O2i0.932.593.449 (3)154
C5—H5···O4ii0.932.463.372 (3)165
C7—H7···O40.932.452.806 (3)103
Symmetry codes: (i) x+2, y+2, z+2; (ii) x+1, y+2, z+1.

Experimental details

(I)(II)
Crystal data
Chemical formulaC11H9FN2OC13H12FNO4
Mr204.20265.24
Crystal system, space groupMonoclinic, P21/nTriclinic, P1
Temperature (K)153153
a, b, c (Å)13.907 (2), 5.0357 (8), 14.233 (2)6.3000 (12), 9.4753 (18), 10.765 (2)
α, β, γ (°)90, 108.946 (4), 9088.947 (5), 79.810 (4), 71.931 (4)
V3)942.8 (3)600.8 (2)
Z42
Radiation typeMo KαMo Kα
µ (mm1)0.110.12
Crystal size (mm)0.49 × 0.12 × 0.080.38 × 0.11 × 0.06
Data collection
DiffractometerSiemens CCD area-detectorSiemens CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.949, 0.9910.956, 0.993
No. of measured, independent and
observed [I > 2σ(I)] reflections
13411, 2554, 1650 6091, 2132, 1244
Rint0.0720.071
(sin θ/λ)max1)0.6880.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.128, 1.01 0.050, 0.147, 1.01
No. of reflections25542132
No. of parameters148174
No. of restraints20
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.25, 0.200.26, 0.25

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SADABS (Sheldrick, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2009), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, °). top
D—H···AD—HH···AD···AD—H···A
(I)
N1—H1···O10.882.052.765 (17)131
C7—H7···N2ii0.952.463.395 (2)167
C6—H6···N2ii0.952.673.618 (2)173
C2—H2···O1i0.952.413.300 (2)156
C10—H10C···O1iii0.982.583.554 (2)172
(II)
N1—H1···O10.862.152.776 (3)129
N1—H1···O1iv0.862.533.334 (3)156
C2—H2···O1iv0.932.443.296 (4)153
C2—H2···O2iv0.932.593.450 (4)154
C5—H5···O4v0.932.463.372 (4)165
Symmetry codes: (i) x, y+1/2, -z+1/2; (ii) -x+1, -y+1, -z+1; (iii) x, y-1, z; (iv) -x+2, -y+2, -z+2; (v) -x+1, -y+2, -z+1.
Selected bond distances (Å) and Wiberg bond orders (Wiberg, 1968) in (I); note that the N1—H1 and C7—H7 bond distances (in italic) are taken from the molecular calculations rather than from the structure refinement. top
Bond distanceWBO
F3—C31.3508 (19)0.893
O1—C91.2361 (18)1.654
N1—C71.3234 (19)1.307
N1—C11.4240 (19)1.041
N1—H11.0280.694
N2—C111.151 (2)2.842
C7—C81.386 (2)1.460
C7—H71.0850.904
C8—C111.429 (2)1.108
C8—C91.455 (2)1.107
C9—C101.498 (2)1.023
Selected bond distances (Å) and Wiberg bond orders (WBO) in (II); note that the N1—H1 bond distance (in italic) is taken from the molecular calculations rather than from the structure refinement. top
Bond distanceWBO
F1—C31.361 (3)0.888
O1—C91.213 (3)1.660
O4—C111.216 (3)1.696
N1—C71.315 (3)1.333
N1—C11.422 (3)1.033
N1—H11.0280.707
C7—C81.377 (3)1.433
C8—C111.442 (4)1.078
C8—C91.435 (4)1.101
 

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