4-(4-Fluoro-3-phenoxy­phen­yl)-6-(4-fluoro­phen­yl)-2-oxo-1,2-dihydro­pyridine-3-carbonitrile and the 6-(4-methyl­phen­yl)- analogue

The crystal structures of the title compounds, viz. C₂₄H₁₄F₂N₂O₂, (I), and C₂₅H₁₇FN₂O₂, (II), respectively, have been determined in order to unravel the role of an ordered F atom in generating stable supra­molecular assemblies. On changing the substitution from fluorine to a methyl group, C-H...F inter­actions are replaced by C-H...[pi] inter­actions, revealing the importance of such weak inter­actions when present alongside N-H...O and C-H...O hydrogen bonds. The dihedral angle between the planes of the 4-fluoro­phenyl ring and the pyridine ring is 26.8 (1)° in (I), while that between the planes of the 4-methyl­phenyl and pyridine rings is 29.5 (1)° in (II).

S1. Comment

Crystal engineering via manipulation of hydrogen bonding has gained a lot of interest in recent literature (Aakeröy, 1997; Guru Row, 1999; Desiraju, 2000, 2002; Hunter et al., 2001). Weak C—H···π interactions (Nishio et al., 1995; Umezawa et al., 1999; Takahashi et al., 2000), π stacking (Hunter, 1993, 1994) and C—H···O (Steiner, 2002) interactions have been found to generate different crystalline motifs. Organo-halo compounds also have been found to generate motifs via C—H···X, X···X and C—X···π interactions (Thalladi et al., 1998). It has been shown that fluorine does not readily accept hydrogen bonding and hence behaves differently than Cl and Br (Shimoni & Glusker, 1994; Howard et al., 1996; Dunitz & Taylor, 1997; Desiraju & Parthasarathi, 1989). Recently, the role of disordered fluorine with respect to a perfectly ordered F atom has played an important role in a stabilizing a crystalline lattice on cryo-cooling of fluorinated amines that are liquids (Chopra et al., 2006). We have been interested in the study of the role that organic fluorine plays in the packing of molecules that exhibit biological activity. Against this background, we report here the molecular and crystal structures of 4-(4-fluoro-3-phenoxyphenyl)-6-(4-fluorophenyl)- 2-oxo-1,2-dihydropyridine-3-carbonitrile, (I), and 4-(4-fluoro-3-phenoxyphenyl)-6-(4-methylphenyl)-2-oxo -1,2-dihydropyridine-3-carbonitrile, (II), in order to evaluate the importance of fluorine in the context of crystal engineering and also to study the influence of substituents of different sizes on the structural parameters of the molecule. Compounds (I) and (II) have important applications in the agrochemical industry and their biological activity has been studied (Mohan, 2006).

Figs. 1 and 2 are ORTEP-3 (Farrugia, 1997) views of the molecules of (I) and (II). Relevant bond lengths, bond angles and torsion angles are given in Tables 1 and 3. The compounds crystallize in the same triclinic space group P1 and are hence isostructural. The structures of (I) and (II) have the same molecular dimensions. The bond distances in the dihydropyridine ring A (C16/C17/C13/C14/C15/N1) are 1.360 (3)–1.434(5) Å in (I) and (II), suggesting possible resonance delocalization of the π electrons over the ring (Allen et al., 1987). Ring A is almost planar, with atoms C14 and C15 having deviation of 0.011 (4) and -0.011 (3) Å from the plane passing through C13, N1 and C17. The corresponding deviations in (II) are -0.009 (4) and +0.009 (4) Å, respectively. Steric interactions force the benzene rings out of the plane of ring A by 56.1 (1) and 26.8 (1)° for the fluorophenoxy (ring C) and fluorophenyl (ring D) groups in (I). Similar dihedral twists are observed for (II), the values being 55.4 (1) and 29.5 (1)°, respectively. The triple-bond character of the C18≡N2 bond [1.147 (3) and 1.144 (4) Å] and the C17—C18—N2 bond angle of ~179° defining the linearity of the cyano group are typical of this group of 3-cyano-2-pyridine compounds (Black et al., 1992; Hussain et al., 1996).

The supramolecular assembly in (I) is built up by a network of strong N—H···O hydrogen bonds (involving H1N and O2), forming molecular dimers (Fig. 3); these are further stabilized by C—H···O interactions (involving H24) to O2, leading to the formation of bifurcated hydrogen bonds (Jeffrey et al., 1985) that form motifs that can be described as R²₂(8) and R²₂(14) using the graph-set formalism (Bernstein et al., 1995). Weak intermolecular C—H···F interactions involving atom F2 link the molecular dimers, forming chains described by the graph-set descriptor C(18). Furthermore, π–π aromatic interactions, with a Cg3···Cg3 distance of 3.605 (3) Å (Cg3 is the centroid of ring C) provide additional stability.

In (II), replacement of a fluoro group by a methyl group leads to an identical supramolecular assembly (Fig. 4), except that the C—H···F interaction is now replaced by a C—H···π weak interaction involving atom H25C and the electron-rich 4-methylphenyl group (ring D, with centroid Cg4) acting as an electron donor, leading to formation of dimers. Such C—H···π dimers further link the molecules that are linked by N—H···O and C—H···O hydrogen bonds, forming alternating dimers built up by a cooperative interplay of strong hydrogen bonds, weak intermolecular interaction and isotropic van der Waals interactions. The Cg3···Cg3 stacking distance between rings C is 3.680 (3) Å, which is similar to the value observed in (I). In conclusion, ordered organic fluorine plays an important role in generating a stable packing motif in the crystalline lattice.#

S2. Experimental

The general procedure for syntheses of compounds (I) and (II) is in accordance with the literature (Dandia et al., 1996; Bhatt et al., 2001). Equimolar (0.02 mol) quantities of 4-fluoro-3-phenoxyphenyl benzaldehyde (in MeOH) were added to a mixture of 4-substituted acetophenones (X = F and methyl) in the presence of 40% NaOH (5 ml) and the mixtuer was stirred at 298 K for 24 h. The contents were poured into crushed ice and purified by recrystallization from ethanol to obtain the pure chalcone. To a mixture of this chalcone, cyanoacetamide was added in equal amount in absolute ethanol and in the presence of pyridine as a catalyst. The reaction mixture was refluxed for 4 h and then cooled, and ice-cold water was added. Pale-yellow compounds were obtained in both cases, and were purified by recrystallization from isopropyl alcohol. Crystals of (I) and (II) suitable for X-ray diffraction were grown from acetone solutions by slow evaporation at 275–277 K.

S3. Refinement

For both (I) and (II), the amine H atom was located from a difference Fourier map and refined isotropically. The other H atoms were placed in idealized positions (C—H = 0.93 and 0.96 Å) and constrained to ride on the parent atom, with U_iso(H) values of 1.2U_eq(C) for aromatic or 1.5U_eq(C) for methyl H atoms.

Computing details

For both compounds, data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

	Fig. 1. ORTEP-3 (Farrugia, 1997) view of (I), drawn with 50% probability displacement ellipsoids.
	Fig. 2. ORTEP-3 view of (II), drawn with 50% probability displacement ellipsoids.
	Fig. 3. The packing of (I), highlighting N—H···O/C—H···O dimers and C—H···F interactions (hydrogen bonds are shown as dashed lines). Other H atoms have been omitted for clarity. The symbols ' and * on atom labels indicate symmetry-related positions at (1 - x, 1 - y, 1 - z) and (x + 1, y - 1, z - 1), respectively.
	Fig. 4. The packing of (II), highlighting N—H···O/C—H···O dimers (hydrogen bonds are shown as dashed lines). Other H atoms have been omitted for clarity. The symbol ' indicates the symmetry-related position at (1 - x, 1 - y, 1 - z).

(I) 4-(4-Fluoro-3-phenoxyphenyl)-6-(4-fluorophenyl)-2-oxo-1,2-dihydropyridine- 3-carbonitrile

Crystal data

C24H14F2N2O2	Z = 2
Mr = 400.37	F(000) = 412
Triclinic, P1	Dx = 1.375 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.572 (4) Å	Cell parameters from 455 reflections
b = 9.337 (5) Å	θ = 1.4–25.4°
c = 14.027 (8) Å	µ = 0.10 mm^−1
α = 80.546 (10)°	T = 290 K
β = 86.710 (12)°	Block, colorless
γ = 81.598 (10)°	0.09 × 0.03 × 0.02 mm
V = 967.2 (9) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3843 independent reflections
Radiation source: fine-focus sealed tube	3260 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
φ and ω scans	θmax = 26.4°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.948, Tmax = 0.998	k = −11→11
10089 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0358P)^2] where P = (Fo^2 + 2Fc^2)/3
3843 reflections	(Δ/σ)max < 0.001
275 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.15 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
F1	0.0527 (2)	0.2506 (2)	−0.08774 (13)	0.0738 (6)
F2	−0.3179 (3)	1.0145 (2)	0.54226 (15)	0.1015 (8)
N1	0.3036 (3)	0.5428 (3)	0.4122 (2)	0.0523 (8)
N2	0.6198 (4)	0.2070 (3)	0.2194 (2)	0.0715 (10)
O1	0.3431 (3)	0.3911 (2)	−0.09495 (15)	0.0604 (7)
O2	0.5749 (3)	0.3997 (3)	0.41606 (16)	0.0784 (8)
C1	0.7055 (7)	0.0562 (6)	−0.1805 (5)	0.115 (2)
C2	0.5961 (7)	0.1474 (6)	−0.2458 (4)	0.1060 (17)
C3	0.4723 (5)	0.2579 (4)	−0.2164 (3)	0.0728 (12)
C4	0.4616 (4)	0.2728 (4)	−0.1202 (3)	0.0514 (9)
C5	0.5679 (5)	0.1815 (4)	−0.0543 (3)	0.0693 (11)
C6	0.6910 (5)	0.0739 (5)	−0.0849 (4)	0.1001 (15)
C7	0.2447 (4)	0.3656 (3)	−0.0089 (2)	0.0442 (8)
C8	0.2858 (4)	0.4143 (3)	0.0731 (2)	0.0466 (9)
C9	0.1757 (4)	0.4004 (3)	0.1560 (2)	0.0407 (8)
C10	0.0199 (4)	0.3384 (3)	0.1546 (2)	0.0510 (9)
C11	−0.0208 (4)	0.2870 (3)	0.0732 (2)	0.0552 (10)
C12	0.0910 (5)	0.3004 (4)	−0.0065 (2)	0.0498 (9)
C13	0.2244 (4)	0.4500 (3)	0.2452 (2)	0.0435 (8)
C14	0.1038 (4)	0.5504 (3)	0.2889 (2)	0.0505 (9)
C15	0.1435 (4)	0.5989 (3)	0.3706 (2)	0.0453 (9)
C16	0.4313 (5)	0.4423 (4)	0.3746 (2)	0.0552 (10)
C17	0.3852 (4)	0.3965 (3)	0.2880 (2)	0.0454 (9)
C18	0.5152 (4)	0.2913 (4)	0.2496 (2)	0.0523 (9)
C19	0.0249 (4)	0.7091 (3)	0.4174 (2)	0.0464 (9)
C20	−0.0958 (4)	0.8124 (4)	0.3618 (2)	0.0646 (11)
C21	−0.2121 (4)	0.9145 (4)	0.4034 (3)	0.0758 (12)
C22	−0.2052 (5)	0.9142 (4)	0.5007 (3)	0.0654 (11)
C23	−0.0877 (5)	0.8171 (4)	0.5572 (2)	0.0637 (11)
C24	0.0276 (4)	0.7149 (4)	0.5153 (2)	0.0565 (10)
H1N	0.341 (4)	0.569 (4)	0.469 (3)	0.088 (13)*
H1	0.7889	−0.0171	−0.2007	0.138*
H2	0.6049	0.1352	−0.3105	0.127*
H3	0.3984	0.3205	−0.2607	0.087*
H5	0.5573	0.1920	0.0107	0.083*
H6	0.7655	0.0123	−0.0405	0.120*
H8	0.3891	0.4572	0.0733	0.056*
H10	−0.0570	0.3318	0.2088	0.061*
H11	−0.1236	0.2435	0.0725	0.066*
H14	−0.0063	0.5849	0.2614	0.061*
H20	−0.0978	0.8123	0.2955	0.077*
H21	−0.2934	0.9820	0.3661	0.091*
H23	−0.0851	0.8197	0.6231	0.076*
H24	0.1087	0.6486	0.5534	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0795 (14)	0.0927 (16)	0.0571 (13)	−0.0088 (11)	−0.0195 (10)	−0.0317 (12)
F2	0.0902 (16)	0.1170 (19)	0.0978 (18)	0.0286 (14)	−0.0049 (13)	−0.0559 (15)
N1	0.0438 (18)	0.072 (2)	0.0430 (18)	0.0041 (15)	−0.0170 (15)	−0.0201 (17)
N2	0.056 (2)	0.080 (2)	0.075 (2)	0.0135 (17)	−0.0077 (17)	−0.0212 (18)
O1	0.0671 (15)	0.0666 (17)	0.0427 (15)	0.0068 (13)	0.0031 (12)	−0.0105 (12)
O2	0.0550 (16)	0.114 (2)	0.0683 (17)	0.0254 (14)	−0.0400 (13)	−0.0394 (15)
C1	0.106 (4)	0.082 (4)	0.164 (6)	−0.009 (3)	0.045 (4)	−0.058 (4)
C2	0.115 (4)	0.117 (5)	0.104 (4)	−0.039 (3)	0.047 (3)	−0.066 (4)
C3	0.084 (3)	0.087 (3)	0.057 (3)	−0.021 (2)	0.008 (2)	−0.035 (2)
C4	0.051 (2)	0.052 (3)	0.054 (2)	−0.0088 (19)	0.0041 (19)	−0.019 (2)
C5	0.064 (3)	0.057 (3)	0.082 (3)	0.005 (2)	0.006 (2)	−0.014 (2)
C6	0.079 (3)	0.068 (3)	0.146 (5)	0.007 (2)	0.013 (3)	−0.015 (3)
C7	0.048 (2)	0.045 (2)	0.035 (2)	0.0085 (17)	−0.0053 (17)	−0.0068 (17)
C8	0.042 (2)	0.057 (2)	0.042 (2)	−0.0009 (16)	−0.0096 (17)	−0.0116 (18)
C9	0.0370 (19)	0.047 (2)	0.037 (2)	0.0060 (16)	−0.0094 (16)	−0.0104 (17)
C10	0.036 (2)	0.070 (3)	0.047 (2)	0.0004 (18)	−0.0065 (16)	−0.0163 (19)
C11	0.043 (2)	0.072 (3)	0.056 (2)	−0.0035 (18)	−0.0134 (18)	−0.022 (2)
C12	0.057 (2)	0.057 (3)	0.037 (2)	0.0073 (19)	−0.0174 (19)	−0.0188 (19)
C13	0.0364 (19)	0.055 (2)	0.038 (2)	0.0000 (17)	−0.0052 (16)	−0.0094 (17)
C14	0.0358 (19)	0.074 (3)	0.042 (2)	0.0029 (18)	−0.0168 (16)	−0.0161 (19)
C15	0.037 (2)	0.059 (2)	0.040 (2)	−0.0018 (17)	−0.0086 (16)	−0.0089 (18)
C16	0.046 (2)	0.073 (3)	0.048 (2)	0.002 (2)	−0.0134 (18)	−0.017 (2)
C17	0.0361 (19)	0.059 (2)	0.041 (2)	0.0034 (17)	−0.0096 (15)	−0.0115 (18)
C18	0.044 (2)	0.065 (3)	0.047 (2)	−0.0014 (19)	−0.0131 (17)	−0.009 (2)
C19	0.043 (2)	0.058 (2)	0.037 (2)	0.0013 (17)	−0.0088 (16)	−0.0111 (18)
C20	0.066 (2)	0.079 (3)	0.047 (2)	0.015 (2)	−0.0161 (19)	−0.021 (2)
C21	0.074 (3)	0.082 (3)	0.068 (3)	0.022 (2)	−0.023 (2)	−0.023 (2)
C22	0.057 (3)	0.077 (3)	0.066 (3)	0.006 (2)	−0.002 (2)	−0.036 (2)
C23	0.059 (2)	0.088 (3)	0.044 (2)	−0.001 (2)	−0.003 (2)	−0.019 (2)
C24	0.049 (2)	0.074 (3)	0.045 (2)	0.0025 (19)	−0.0073 (17)	−0.015 (2)

Geometric parameters (Å, º)

F1—C12	1.361 (3)	C11—C10	1.377 (4)
O1—C7	1.387 (3)	C11—H11	0.9300
O1—C4	1.398 (3)	C24—C23	1.379 (4)
N1—C15	1.371 (3)	C24—H24	0.9300
N1—C16	1.390 (4)	C22—C23	1.361 (4)
N1—H1N	0.94 (3)	C22—C21	1.369 (4)
O2—C16	1.244 (3)	C20—C21	1.380 (4)
C13—C17	1.378 (4)	C20—H20	0.9300
C13—C14	1.401 (4)	C10—H10	0.9300
C13—C9	1.486 (4)	C8—H8	0.9300
F2—C22	1.354 (3)	C4—C5	1.362 (4)
C19—C24	1.384 (4)	C4—C3	1.376 (4)
C19—C20	1.397 (4)	C21—H21	0.9300
C19—C15	1.476 (4)	C23—H23	0.9300
C15—C14	1.364 (4)	C5—C6	1.374 (5)
C9—C10	1.390 (4)	C5—H5	0.9300
C9—C8	1.391 (4)	C3—C2	1.388 (5)
C14—H14	0.9300	C3—H3	0.9300
C7—C8	1.371 (4)	C1—C2	1.369 (6)
C7—C12	1.386 (4)	C1—C6	1.374 (6)
C16—C17	1.429 (4)	C1—H1	0.9300
C12—C11	1.363 (4)	C6—H6	0.9300
C18—N2	1.147 (3)	C2—H2	0.9300
C18—C17	1.433 (4)
C7—O1—C4	116.7 (2)	C16—C17—C18	115.9 (3)
C15—N1—C16	124.1 (3)	F2—C22—C23	118.7 (3)
C15—N1—H1N	124 (2)	F2—C22—C21	119.1 (4)
C16—N1—H1N	112 (2)	C23—C22—C21	122.2 (3)
C17—C13—C14	118.6 (3)	C21—C20—C19	121.1 (3)
C17—C13—C9	121.4 (3)	C21—C20—H20	119.4
C14—C13—C9	119.9 (3)	C19—C20—H20	119.4
C24—C19—C20	117.9 (3)	C11—C10—C9	120.1 (3)
C24—C19—C15	122.6 (3)	C11—C10—H10	119.9
C20—C19—C15	119.5 (3)	C9—C10—H10	119.9
C14—C15—N1	118.3 (3)	C7—C8—C9	121.1 (3)
C14—C15—C19	124.1 (3)	C7—C8—H8	119.4
N1—C15—C19	117.6 (3)	C9—C8—H8	119.4
C10—C9—C8	119.1 (3)	C5—C4—C3	121.6 (3)
C10—C9—C13	120.3 (3)	C5—C4—O1	122.0 (3)
C8—C9—C13	120.5 (3)	C3—C4—O1	116.4 (3)
C15—C14—C13	121.7 (3)	C22—C21—C20	118.5 (3)
C15—C14—H14	119.1	C22—C21—H21	120.7
C13—C14—H14	119.1	C20—C21—H21	120.7
C8—C7—C12	118.0 (3)	C22—C23—C24	119.0 (3)
C8—C7—O1	121.9 (3)	C22—C23—H23	120.5
C12—C7—O1	119.8 (3)	C24—C23—H23	120.5
O2—C16—N1	119.7 (3)	C4—C5—C6	119.2 (4)
O2—C16—C17	124.7 (3)	C4—C5—H5	120.4
N1—C16—C17	115.6 (3)	C6—C5—H5	120.4
F1—C12—C11	120.2 (3)	C4—C3—C2	118.4 (4)
F1—C12—C7	117.6 (3)	C4—C3—H3	120.8
C11—C12—C7	122.2 (3)	C2—C3—H3	120.8
N2—C18—C17	179.6 (4)	C2—C1—C6	119.5 (5)
C12—C11—C10	119.3 (3)	C2—C1—H1	120.3
C12—C11—H11	120.3	C6—C1—H1	120.3
C10—C11—H11	120.3	C5—C6—C1	120.7 (5)
C23—C24—C19	121.3 (3)	C5—C6—H6	119.6
C23—C24—H24	119.4	C1—C6—H6	119.6
C19—C24—H24	119.4	C1—C2—C3	120.6 (5)
C13—C17—C16	121.6 (3)	C1—C2—H2	119.7
C13—C17—C18	122.6 (3)	C3—C2—H2	119.7
C16—N1—C15—C14	2.0 (5)	O2—C16—C17—C13	−179.0 (3)
C16—N1—C15—C19	−177.7 (3)	N1—C16—C17—C13	0.2 (5)
C24—C19—C15—C14	153.2 (3)	O2—C16—C17—C18	1.6 (5)
C20—C19—C15—C14	−26.7 (5)	N1—C16—C17—C18	−179.1 (3)
C24—C19—C15—N1	−27.1 (4)	C24—C19—C20—C21	−1.7 (5)
C20—C19—C15—N1	153.0 (3)	C15—C19—C20—C21	178.2 (3)
C17—C13—C9—C10	123.0 (3)	C12—C11—C10—C9	−1.4 (5)
C14—C13—C9—C10	−55.4 (4)	C8—C9—C10—C11	2.3 (5)
C17—C13—C9—C8	−56.5 (4)	C13—C9—C10—C11	−177.2 (3)
C14—C13—C9—C8	125.1 (3)	C12—C7—C8—C9	−0.8 (4)
N1—C15—C14—C13	−2.4 (5)	O1—C7—C8—C9	173.6 (3)
C19—C15—C14—C13	177.3 (3)	C10—C9—C8—C7	−1.1 (4)
C17—C13—C14—C15	1.7 (5)	C13—C9—C8—C7	178.4 (3)
C9—C13—C14—C15	−179.9 (3)	C7—O1—C4—C5	−43.2 (4)
C4—O1—C7—C8	103.8 (3)	C7—O1—C4—C3	140.3 (3)
C4—O1—C7—C12	−81.8 (3)	F2—C22—C21—C20	179.6 (3)
C15—N1—C16—O2	178.3 (3)	C23—C22—C21—C20	0.1 (6)
C15—N1—C16—C17	−1.0 (5)	C19—C20—C21—C22	1.0 (5)
C8—C7—C12—F1	−179.1 (3)	F2—C22—C23—C24	−179.9 (3)
O1—C7—C12—F1	6.4 (4)	C21—C22—C23—C24	−0.5 (6)
C8—C7—C12—C11	1.7 (5)	C19—C24—C23—C22	−0.4 (5)
O1—C7—C12—C11	−172.8 (3)	C3—C4—C5—C6	1.2 (6)
F1—C12—C11—C10	−179.8 (3)	O1—C4—C5—C6	−175.1 (3)
C7—C12—C11—C10	−0.6 (5)	C5—C4—C3—C2	−0.5 (5)
C20—C19—C24—C23	1.4 (5)	O1—C4—C3—C2	176.1 (3)
C15—C19—C24—C23	−178.5 (3)	C4—C5—C6—C1	−1.1 (6)
C14—C13—C17—C16	−0.6 (5)	C2—C1—C6—C5	0.2 (8)
C9—C13—C17—C16	−179.0 (3)	C6—C1—C2—C3	0.5 (8)
C14—C13—C17—C18	178.7 (3)	C4—C3—C2—C1	−0.4 (7)
C9—C13—C17—C18	0.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.94 (4)	1.85 (4)	2.786 (4)	175 (3)
C24—H24···O2^i	0.93	2.42	3.191 (4)	140
C2—H2···F2^ii	0.93	2.51	3.399 (6)	159

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y−1, z−1.

(II) 4-(4-Fluoro-3-phenoxyphenyl)-6-(4-methylphenyl)-2-oxo-1,2-dihydropyridine- 3-carbonitrile

Crystal data

C25H17FN2O2	Z = 2
Mr = 396.41	F(000) = 412
Triclinic, P1	Dx = 1.310 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.828 (5) Å	Cell parameters from 535 reflections
b = 9.523 (7) Å	θ = 1.3–25.2°
c = 13.952 (10) Å	µ = 0.09 mm^−1
α = 76.460 (13)°	T = 290 K
β = 87.250 (14)°	Plate, colorless
γ = 83.705 (15)°	0.15 × 0.14 × 0.05 mm
V = 1004.9 (12) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3976 independent reflections
Radiation source: fine-focus sealed tube	1997 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
φ and ω scans	θmax = 26.4°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.946, Tmax = 0.996	k = −11→11
10474 measured reflections	l = −17→17

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.096	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0454P)^2] where P = (Fo^2 + 2Fc^2)/3
3976 reflections	(Δ/σ)max < 0.001
276 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
F1	0.0592 (3)	0.2500 (2)	−0.08137 (16)	0.0703 (7)
O1	0.3464 (3)	0.3916 (3)	−0.09466 (17)	0.0555 (8)
O2	0.5686 (3)	0.3953 (3)	0.42196 (19)	0.0669 (9)
N1	0.3120 (4)	0.5362 (3)	0.4080 (2)	0.0448 (9)
N2	0.6158 (4)	0.2192 (4)	0.2275 (2)	0.0662 (11)
C1	0.6814 (8)	0.0630 (6)	−0.1657 (5)	0.101 (2)
C2	0.5684 (8)	0.1461 (6)	−0.2331 (4)	0.0989 (19)
C3	0.4540 (6)	0.2547 (5)	−0.2087 (3)	0.0719 (14)
C4	0.4560 (5)	0.2744 (4)	−0.1147 (3)	0.0494 (11)
C5	0.5670 (5)	0.1915 (4)	−0.0459 (3)	0.0651 (12)
C6	0.6804 (6)	0.0851 (5)	−0.0722 (4)	0.0870 (16)
C7	0.2497 (5)	0.3657 (4)	−0.0076 (3)	0.0397 (9)
C8	0.2930 (4)	0.4139 (4)	0.0724 (3)	0.0403 (9)
C9	0.1851 (4)	0.4007 (4)	0.1559 (2)	0.0361 (9)
C10	0.0316 (4)	0.3409 (4)	0.1557 (3)	0.0446 (10)
C11	−0.0109 (5)	0.2882 (4)	0.0768 (3)	0.0501 (11)
C12	0.0991 (5)	0.3018 (4)	−0.0031 (3)	0.0449 (10)
C13	0.2349 (4)	0.4503 (4)	0.2427 (2)	0.0369 (9)
C14	0.1209 (5)	0.5471 (4)	0.2821 (3)	0.0409 (10)
C15	0.1591 (4)	0.5920 (4)	0.3636 (3)	0.0374 (9)
C16	0.4337 (5)	0.4392 (4)	0.3765 (3)	0.0446 (10)
C17	0.3892 (4)	0.3978 (4)	0.2892 (3)	0.0396 (9)
C18	0.5145 (5)	0.2980 (4)	0.2546 (3)	0.0442 (10)
C19	0.0460 (4)	0.6943 (4)	0.4080 (3)	0.0386 (9)
C20	−0.0640 (5)	0.8021 (4)	0.3495 (3)	0.0539 (11)
C21	−0.1692 (5)	0.9003 (4)	0.3911 (3)	0.0604 (12)
C22	−0.1687 (5)	0.8930 (4)	0.4913 (3)	0.0491 (10)
C23	−0.0596 (5)	0.7868 (4)	0.5478 (3)	0.0505 (11)
C24	0.0461 (4)	0.6881 (4)	0.5084 (3)	0.0462 (10)
C25	−0.2819 (5)	0.9994 (4)	0.5379 (3)	0.0700 (13)
H1N	0.340 (4)	0.559 (4)	0.461 (3)	0.049 (12)*
H1	0.7588	−0.0085	−0.1833	0.121*
H2	0.5684	0.1294	−0.2962	0.119*
H3	0.3784	0.3124	−0.2547	0.086*
H5	0.5658	0.2067	0.0176	0.078*
H6	0.7566	0.0280	−0.0262	0.104*
H8	0.3953	0.4557	0.0710	0.048*
H10	−0.0439	0.3361	0.2097	0.054*
H11	−0.1119	0.2446	0.0781	0.060*
H14	0.0159	0.5814	0.2519	0.049*
H20	−0.0670	0.8083	0.2820	0.065*
H21	−0.2410	0.9722	0.3510	0.073*
H23	−0.0566	0.7811	0.6152	0.061*
H24	0.1177	0.6169	0.5492	0.055*
H25A	−0.3782	0.9532	0.5713	0.105*
H25B	−0.3225	1.0821	0.4876	0.105*
H25C	−0.2168	1.0304	0.5844	0.105*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0841 (17)	0.0899 (19)	0.0496 (15)	−0.0092 (13)	−0.0182 (13)	−0.0381 (14)
O1	0.0791 (19)	0.0535 (18)	0.0331 (16)	0.0012 (14)	0.0071 (14)	−0.0136 (13)
O2	0.0550 (17)	0.092 (2)	0.0639 (19)	0.0278 (16)	−0.0343 (15)	−0.0478 (17)
N1	0.050 (2)	0.056 (2)	0.034 (2)	0.0026 (16)	−0.0127 (17)	−0.0228 (18)
N2	0.061 (2)	0.077 (3)	0.062 (3)	0.018 (2)	−0.0062 (19)	−0.028 (2)
C1	0.092 (4)	0.079 (4)	0.140 (6)	−0.005 (3)	0.044 (4)	−0.051 (4)
C2	0.115 (5)	0.111 (5)	0.091 (5)	−0.027 (4)	0.042 (4)	−0.066 (4)
C3	0.084 (3)	0.088 (4)	0.056 (3)	−0.017 (3)	0.013 (3)	−0.042 (3)
C4	0.057 (3)	0.051 (3)	0.047 (3)	−0.011 (2)	0.009 (2)	−0.023 (2)
C5	0.071 (3)	0.059 (3)	0.067 (3)	0.002 (2)	0.001 (3)	−0.023 (3)
C6	0.072 (3)	0.074 (4)	0.113 (5)	0.000 (3)	0.012 (3)	−0.024 (3)
C7	0.051 (2)	0.041 (2)	0.027 (2)	0.0041 (19)	−0.0050 (19)	−0.0118 (19)
C8	0.043 (2)	0.041 (2)	0.040 (2)	−0.0020 (17)	−0.0049 (19)	−0.0139 (19)
C9	0.036 (2)	0.039 (2)	0.035 (2)	0.0063 (17)	−0.0058 (18)	−0.0153 (18)
C10	0.036 (2)	0.063 (3)	0.037 (2)	0.0005 (19)	−0.0045 (18)	−0.017 (2)
C11	0.043 (2)	0.066 (3)	0.047 (3)	−0.006 (2)	−0.013 (2)	−0.023 (2)
C12	0.060 (3)	0.052 (3)	0.027 (2)	0.004 (2)	−0.017 (2)	−0.020 (2)
C13	0.041 (2)	0.042 (2)	0.028 (2)	−0.0019 (18)	−0.0055 (17)	−0.0100 (18)
C14	0.035 (2)	0.053 (3)	0.037 (2)	0.0025 (19)	−0.0125 (18)	−0.016 (2)
C15	0.040 (2)	0.045 (2)	0.029 (2)	0.0013 (18)	−0.0095 (17)	−0.0121 (19)
C16	0.045 (2)	0.050 (3)	0.043 (3)	0.0058 (19)	−0.012 (2)	−0.022 (2)
C17	0.039 (2)	0.050 (2)	0.035 (2)	0.0019 (18)	−0.0038 (17)	−0.0210 (19)
C18	0.044 (2)	0.054 (3)	0.037 (2)	−0.002 (2)	−0.0115 (18)	−0.014 (2)
C19	0.039 (2)	0.044 (2)	0.036 (2)	−0.0007 (18)	−0.0036 (18)	−0.0177 (19)
C20	0.060 (3)	0.061 (3)	0.041 (2)	0.013 (2)	−0.015 (2)	−0.018 (2)
C21	0.054 (3)	0.063 (3)	0.063 (3)	0.019 (2)	−0.018 (2)	−0.020 (2)
C22	0.047 (2)	0.048 (3)	0.059 (3)	−0.003 (2)	0.003 (2)	−0.026 (2)
C23	0.054 (2)	0.059 (3)	0.041 (2)	−0.002 (2)	−0.001 (2)	−0.019 (2)
C24	0.047 (2)	0.053 (3)	0.037 (2)	0.0025 (19)	−0.0040 (19)	−0.012 (2)
C25	0.060 (3)	0.077 (3)	0.080 (3)	0.005 (2)	0.009 (2)	−0.039 (3)

Geometric parameters (Å, º)

F1—C12	1.360 (4)	C11—H11	0.9300
O1—C7	1.386 (4)	C8—H8	0.9300
O1—C4	1.404 (4)	C23—C22	1.370 (5)
O2—C16	1.239 (4)	C23—C24	1.378 (5)
N1—C15	1.370 (4)	C23—H23	0.9300
N1—C16	1.383 (4)	C20—C21	1.389 (5)
N1—H1N	0.86 (3)	C20—H20	0.9300
C14—C15	1.362 (5)	C24—H24	0.9300
C14—C13	1.399 (4)	C22—C21	1.384 (5)
C14—H14	0.9300	C22—C25	1.514 (5)
C15—C19	1.469 (4)	C25—H25A	0.9600
C16—C17	1.434 (5)	C25—H25B	0.9600
C13—C17	1.386 (4)	C25—H25C	0.9600
C13—C9	1.482 (4)	C4—C5	1.369 (5)
C9—C10	1.386 (5)	C4—C3	1.369 (5)
C9—C8	1.395 (4)	C21—H21	0.9300
C7—C8	1.372 (4)	C6—C1	1.368 (7)
C7—C12	1.377 (5)	C6—C5	1.376 (5)
C19—C24	1.388 (5)	C6—H6	0.9300
C19—C20	1.394 (4)	C3—C2	1.386 (6)
C18—N2	1.144 (4)	C3—H3	0.9300
C18—C17	1.436 (5)	C5—H5	0.9300
C10—C11	1.380 (5)	C2—C1	1.368 (7)
C10—H10	0.9300	C2—H2	0.9300
C11—C12	1.367 (5)	C1—H1	0.9300
C7—O1—C4	117.0 (3)	C16—C17—C18	115.3 (3)
C15—N1—C16	125.7 (3)	C22—C23—C24	122.3 (4)
C15—N1—H1N	121 (2)	C22—C23—H23	118.8
C16—N1—H1N	113 (2)	C24—C23—H23	118.8
C15—C14—C13	121.7 (3)	C21—C20—C19	120.5 (4)
C15—C14—H14	119.3	C21—C20—H20	119.8
C13—C14—H14	119.3	C19—C20—H20	119.8
C14—C15—N1	117.8 (3)	C23—C24—C19	120.3 (4)
C14—C15—C19	124.3 (3)	C23—C24—H24	119.9
N1—C15—C19	117.9 (3)	C19—C24—H24	119.9
O2—C16—N1	120.7 (3)	C23—C22—C21	117.7 (3)
O2—C16—C17	124.9 (3)	C23—C22—C25	120.4 (4)
N1—C16—C17	114.4 (3)	C21—C22—C25	121.8 (4)
C17—C13—C14	118.7 (3)	C22—C25—H25A	109.5
C17—C13—C9	121.5 (3)	C22—C25—H25B	109.5
C14—C13—C9	119.7 (3)	H25A—C25—H25B	109.5
C10—C9—C8	118.8 (3)	C22—C25—H25C	109.5
C10—C9—C13	121.0 (3)	H25A—C25—H25C	109.5
C8—C9—C13	120.2 (3)	H25B—C25—H25C	109.5
C8—C7—C12	118.6 (3)	C5—C4—C3	122.1 (4)
C8—C7—O1	121.2 (4)	C5—C4—O1	121.6 (4)
C12—C7—O1	119.9 (3)	C3—C4—O1	116.2 (4)
C24—C19—C20	118.1 (3)	C22—C21—C20	121.1 (4)
C24—C19—C15	121.5 (3)	C22—C21—H21	119.5
C20—C19—C15	120.4 (3)	C20—C21—H21	119.5
N2—C18—C17	179.2 (4)	C1—C6—C5	120.3 (5)
C11—C10—C9	121.0 (3)	C1—C6—H6	119.9
C11—C10—H10	119.5	C5—C6—H6	119.9
C9—C10—H10	119.5	C4—C3—C2	117.9 (5)
C12—C11—C10	118.3 (4)	C4—C3—H3	121.1
C12—C11—H11	120.8	C2—C3—H3	121.1
C10—C11—H11	120.8	C4—C5—C6	119.0 (5)
F1—C12—C11	119.0 (4)	C4—C5—H5	120.5
F1—C12—C7	118.5 (3)	C6—C5—H5	120.5
C11—C12—C7	122.5 (4)	C1—C2—C3	120.9 (5)
C7—C8—C9	120.6 (4)	C1—C2—H2	119.6
C7—C8—H8	119.7	C3—C2—H2	119.6
C9—C8—H8	119.7	C2—C1—C6	119.9 (5)
C13—C17—C16	121.7 (3)	C2—C1—H1	120.0
C13—C17—C18	123.0 (3)	C6—C1—H1	120.0
C13—C14—C15—N1	−1.7 (6)	C13—C9—C8—C7	178.7 (3)
C13—C14—C15—C19	179.4 (3)	C14—C13—C17—C16	0.5 (5)
C16—N1—C15—C14	1.1 (6)	C9—C13—C17—C16	−176.4 (3)
C16—N1—C15—C19	−179.9 (3)	C14—C13—C17—C18	179.9 (3)
C15—N1—C16—O2	179.8 (4)	C9—C13—C17—C18	3.0 (5)
C15—N1—C16—C17	0.2 (5)	O2—C16—C17—C13	179.4 (4)
C15—C14—C13—C17	1.0 (5)	N1—C16—C17—C13	−1.1 (5)
C15—C14—C13—C9	178.0 (3)	O2—C16—C17—C18	−0.1 (6)
C17—C13—C9—C10	124.0 (4)	N1—C16—C17—C18	179.5 (3)
C14—C13—C9—C10	−52.9 (5)	C24—C19—C20—C21	0.3 (6)
C17—C13—C9—C8	−56.1 (5)	C15—C19—C20—C21	−179.0 (3)
C14—C13—C9—C8	127.0 (4)	C22—C23—C24—C19	0.6 (6)
C4—O1—C7—C8	104.1 (4)	C20—C19—C24—C23	−0.3 (5)
C4—O1—C7—C12	−81.7 (4)	C15—C19—C24—C23	179.0 (3)
C14—C15—C19—C24	150.1 (4)	C24—C23—C22—C21	−0.8 (6)
N1—C15—C19—C24	−28.8 (5)	C24—C23—C22—C25	−179.8 (3)
C14—C15—C19—C20	−30.6 (6)	C7—O1—C4—C5	−49.6 (5)
N1—C15—C19—C20	150.5 (4)	C7—O1—C4—C3	134.9 (4)
C8—C9—C10—C11	3.2 (5)	C23—C22—C21—C20	0.8 (6)
C13—C9—C10—C11	−176.8 (3)	C25—C22—C21—C20	179.8 (4)
C9—C10—C11—C12	−2.6 (5)	C19—C20—C21—C22	−0.6 (6)
C10—C11—C12—F1	179.8 (3)	C5—C4—C3—C2	0.4 (6)
C10—C11—C12—C7	0.1 (5)	O1—C4—C3—C2	175.9 (4)
C8—C7—C12—F1	−178.0 (3)	C3—C4—C5—C6	0.1 (6)
O1—C7—C12—F1	7.7 (5)	O1—C4—C5—C6	−175.1 (4)
C8—C7—C12—C11	1.8 (5)	C1—C6—C5—C4	−0.1 (7)
O1—C7—C12—C11	−172.6 (3)	C4—C3—C2—C1	−1.0 (8)
C12—C7—C8—C9	−1.1 (5)	C3—C2—C1—C6	1.1 (9)
O1—C7—C8—C9	173.2 (3)	C5—C6—C1—C2	−0.5 (8)
C10—C9—C8—C7	−1.3 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2^i	0.86 (4)	1.97 (4)	2.828 (5)	174 (3)
C24—H24···O2^i	0.93	2.49	3.173 (5)	130
C25—H25C···Cg4^ii	0.96	2.85	3.535 (5)	130

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+2, −z+1.