A structural systematic study of three isomers of difluoro-N-(4-pyrid­yl)benzamide

The isomers 2,3-, (I), 2,4-, (II), and 2,5-di­fluoro-N-(4-pyrid­yl)benzamide, (III), all with formula C₁₂H₈F₂N₂O, all exhibit intra­molecular C—H...O=C and N—H...F contacts [both with S(6) motifs]. In (I), inter­molecular N—H...O=C inter­actions form one-dimensional chains along [010] [N...O = 3.0181 (16) Å], with weaker C—H...N inter­actions linking the chains into sheets parallel to the [001] plane, further linked into pairs via C—H...F contacts about inversion centres; a three-dimensional herring-bone network forms via C—H...π(py) (py is pyrid­yl) inter­actions. In (II), weak aromatic C—H...N(py) inter­actions form one-dimensional zigzag chains along [001]; no other inter­actions with H...N/O/F < 2.50 Å are present, apart from long N/C—H...O=C and C—H...F contacts. In (III), N—H...N(py) inter­actions form one-dimensional zigzag chains [as C(6) chains] along [010] augmented by a myriad of weak C—H...π(arene) and O=C...O=C inter­actions and C—H...O/N/F contacts. Compound (III) is isomorphous with the parent N-(4-pyrid­yl)benzamide [Noveron, Lah, Del Sesto, Arif, Miller & Stang (2002). J. Am. Chem. Soc. 124, 6613–6625] and the three 2/3/4-fluoro-N-(4-pyrid­yl)benzamides [Donnelly, Gallagher & Lough (2008). Acta Cryst. C64, o335–o340]. The study expands our series of fluoro­(pyrid­yl)benzamides and augments our understanding of the competition between strong hydrogen-bond formation and weaker influences on crystal packing.

S1. Comment

Our group has initiated a structural systematic study of fluoro-N'-(pyridyl)benzamide isomers (Donnelly et al., 2008) and are augmenting this research with the closely related difluoro-N-(pyridyl)benzamide series (see scheme) of which a total of 18 isomers are possible through condensation of the 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-difluorobenzoyl chlorides with the 4-/3-/2-aminopyridines. In contrast to the abundance of monosubstituted fluorobenzene FC₆H₄—X and pentafluorobenzene F₅C₆—Y derivatives in structural chemistry, there is a paucity of structural information on all six possible difluorobenzene derivatives F₂C₆H₃—Z (X,Y,Z = remainder of molecule) from analysis of structural data in the Cambridge Structural Database (CSD, Version 5.29; Allen, 2002) (Fig. 1). In contrast to the 3531 (8) structures containing the pentafluorobenzene C₆F₅—Y group, the cumulative reported total of the six C₆F₂H₃Z difluorobenzene moieties in compounds (at 438) is only < 13% of the C₆F₅ reported systems (see scheme).

Disorder in the orientation of the aromatic ring can arise and can influence the choice of a particular difluorobenzene fragment in crystal structures in order to minimize solid-state disorder effects. The potential for twofold rotational disorder is at a minimum in the more symmetrical 2,6-F₂ and 3,5-F₂ (no change on twofold rotation about the C_ipso—C_para axis) and at a maximum in the 2,3-F₂, 2,5-F₂ systems (two F atoms have to occupy different H-atom sites): the potential for disorder also exists for 2,4-F₂ and 3,4-F₂ substitution (where only one F atom has to swop sites with an H atom after twofold rotation). No disorder is present in either of the 2,3-, (I), 2,4-, (II) or 2,5-difluoro(4-pyridyl)benzamide systems (III).

Many structural studies have been reported to date on a variety of organic molecular classes and often with a particular emphasis on polymorphism, pseudopolymorphism and isomers (Gelbrich et al., 2007; Wardell et al., 2007; 2008; Chopra & Row, 2008). Augmenting our initial communication (Donnelly et al., 2008) we report here the molecular and crystal structures of the 2,3-difluoro-N-(4-pyridyl)benzamide, (I), 2,4-difluoro-N-(4-pyridyl)benzamide, (II), and 2,5-difluoro-N-(4-pyridyl)benzamide, (III), isomers.

The three isomers (I)–(III) are depicted in Figs. 2–4 and in the packing diagrams (Figs. 5–8). The geometric data (bond lengths and angles) are normal and are not discussed except for comparisons with related systems and their hydrogen bonding/packing (interactions in Tables 1–3 and torsion angles in Table 4). The defining feature of the molecular conformation is the benzene–pyridine dihedral angle, which is mutally oriented at 10.02 (8)° in (I), 7.02 (13)° in (II) and 42.39 (6)° in (III). In all three systems the ortho-F atom is positioned cisoid to the carbonyl O atom and as such there are two intramolecular contacts present involving C22···O1 and N1···F12 [both with S(6) motifs]. The C22···O1 distances vary from 2.868 (2) to 2.8807 (18) Å [C—H···O = 114–120°]; however, N1···F1 varies from 2.720 (3) (II) to 2.7803 (14) Å (I) and with angles 109.7 (15)° (III) to 131 (3)° (I) (as C1—N1—C21—C26 increases in angle, Table 4). The intramolecular contact data for (III) are similar to data for 2-fluoro-N'-(4-pyridyl)benzamide (Fop) (Donnelly et al., 2008). Moreover, (III) is isomorphous with all three 4-/3-/2-fluoro-N'-(4-pyridyl)benzamide isomers (Fpp/Fmp/Fop) and differs in composition with an extra F atom replacing a H atom on the benzene ring (see scheme) (Donnelly et al., 2008). For comparison, the unit-cell similarity indices Π of (III) with Fmp and Fop are 0.003 and 0.002, respectively, (Kálmán et al., 1993).

In (I), standard amide N—H···O═C hydrogen bonds (Table 1) form chains along [010], further linked by C—H14···N interactions to form sheets of R⁴₄(28) rings parallel to (001) (Fig. 5). Pairs of inversion-related sheets form short C—H···F contacts and these pairs of sheets form a three-dimensional network via C—H···π(pyridyl) interactions (Table 1).

In (II), a C—H···N hydrogen bond (Table 2) forms a zigzag C(10) chain along [001] (Fig. 6): there are no other interactions with an H···O/N/F distance < 2.5 Å. Conventional amide N—H···O═C interactions [as C(4) chains or R²₂(8) rings] are absent and the closest amide···amide contact for N1···O1ⁱ = 3.460 (3) Å: this is 0.45 Å longer than for (I) [symmetry code: (i) = x,y + 1,z]. The three closest intermolecular contacts with the carbonyl O1 atom range from 2.69 to 2.76 Å and with corresponding C—H···O1 angles of 126–141°. There are also two weak C_15/23—H_15/23···F14 contacts with C···F distances of 3.322 (3), 3.339 (3) Å. Though the interaction distances differ between (I) and (II), there is a broad similarity in overall packing.

In (III), the primary interaction is an N—H···N hydrogen bond (Table 3) which forms a zigzag C(96) chain along the [010] direction (Fig. 7). This interaction is augmented by longer C—H···π(arene) hydrogen bonds (Table 3), dipolar C=O···O═C interactions (Fig. 8) and weaker C—H···N/O/F contacts forming a three-dimensional network. The C=O···(O═C)ⁱ interactions link molecules about inversion centres in an antiparallel arrangement, with C1···O1ⁱ distances of 3.150 (2) Å [symmetry code: (i) = -x + 2,-y,-z + 1] (Fig. 8). The internal angles within the [C=O···(O═C)ⁱ] motif are 85.00 (10)° (for C1=O1···C1ⁱ) and 95.00 (10)° (for O1=C1···O1ⁱ) and close to the idealized antiparallel arrangement [90° angles – motif (II)] (Allen et al., 1998).

Data for (III) are similar to Fop (Donnelly et al., 2008) where the C1···O1ⁱ distance is 3.1919 (16) Å. The closest intermolecular amide···amide N1···O1ⁱⁱ distance is 4.005 (2) Å [with H1···O1ⁱⁱ 3.37 (2) Å] along the [100] axis, highlighting the lack of conventional intermolecular amide···amide hydrogen bonding in (III). This N1···O1ⁱⁱ distance [symmetry code: (ii) = x - 1,y,z] is longer than the corresponding N···O distances in the three isomers (Fpp), (Fmp) and (Fop) [3.438 (2)–3.7854 (16) Å] (Table 5) (these isomers have N—H···N_py as their primary interaction) (Donnelly et al., 2008). The trend of increasing _amideN···O_carbonyl distance correlates well with the increasing unit-cell 'a' dimension (amide···amide distance along [100]) and decreasing C₆/C₅N dihedral angle (preventing closer intermolecular N···O approach).

The primary interactions in (I)–(III) differ, although (I) and (II) are more closely matched in comparison to the hydrogen bonding in (III) (where N—H···N_py hydrogen bonding dominates) and they also differ in intermolecular N—H···O distance. The influence of π···π stacking interactions is small for (I)–(III) and with no substantial aromatic ring overlap: there are no parallel and overlapping aromatic planes within 3.5 Å of each other.

It is of interest that (III) crystallizes in the same space group, P2₁/c (No. 14), and with a similar unit cell as the (Fpp/Fmp/Fop) series (Donnelly et al., 2008) and also the parent N-(4-pyridyl)benzamide (IV) (Noveron et al., 2002) (Table 5). This isomorphous series of five compounds facilitates comparisons (where H is replaced by F) on progressing from the parent C₁₂H₁₀N₂O (MOHQOP) (IV) to the isomorphous (Fpp/Fmp/Fop) C₁₂H₉FN₂O series to C₁₂H₈F₂N₂O (III). The molecular conformations of (III) and the (Fpp/Fmp/Fop) series are similar as the spatial orientation of the 2,5-F₂ atoms on the C₆ benzene ring in (III) compares favourably with the ortho (2-substituted) F atom in (Fop) and the meta (3-substituted) F atom in (Fmp) (Table 5). The dominance and influence of the _amideN—H···N_py hydrogen bonding in the packing for all five compounds is notable as it competes with potential N—H···O═C interactions and other weaker types of hydrogen bonding: there is a negligible influence of the isosteric replacement of H atoms by F atoms on packing. The molecular similarity in combination with the dominance of N—H···N hydrogen bonding influences the observed isomorphism in the five structures (IV), (Fpp/Fmp/Fop) and (III).

In expanding our structural systematic study of fluoro(pyridyl)benzamides, incorporating isomers, polymorphs and pseudopolymorphs, we will strive to group together examples with similar properties and behaviour as well as making comparisons with related published work so as 'not to impose a discontinuity on Nature's continuum' (Threlfall & Gelbrich, 2007). Work is in progress to expand these fluoro(pyridyl)benzamide series.

Related literature

For related literature, see: Allen (2002); Chopra & Row (2008); Donnelly et al. (2008); Gelbrich et al. (2007); Kálmán et al. (1993); Noveron et al. (2002); Sheldrick (2008); Threlfall & Gelbrich (2007); Wardell et al. (2007, 2008).

S2. Experimental

For the preparation of (I)–(III) (Fink & Kurys, 1996), typically, the 2,3-, 2,4- and 2,5-difluorobenzoyl chlorides in dry CH₂Cl₂ (20–30 ml) were added dropwise (over a period of 2–3 min) to a cold (273 K) 20–30 ml solution of 4-aminopyridine containing Et₃N (1.5 ml), and the reaction was stirred overnight at room temperature. Typical organic workup and washings furnished the products in reasonable yields of 40–90%. Crystals suitable for diffraction were grown from CHCl₃ as colourless blocks over a period of 1–2 weeks. The three compounds gave clean ¹H and ¹³C NMR spectra in δ₆-DMSO and the infrared spectra (in CHCl₃ solution, KBr disks) are as expected.

For (I), m.p. 385–387 K (uncorrected). IR (ν_C=O cm^-1): 1684s, 1674m (CHCl₃); 1667s (KBr). ¹H NMR (400 MHz, DMSO): δ 10.98 (s, 1H, N—H), 8.51 (d, 2H, 4-pyr), 7.70 (d, 2H, 4-pyr), 7.67 (m [2 td], 1H, 2,3-Fbenz), 7.53 (m [tt], 1H, 2,3-Fbenz), 7.38 (m [2 t d], 1H, 2,3-Fbenz).

For (II), m.p. 391–393 K (uncorrected). IR (ν_C=O cm^-1): 1662s (CHCl₃); 1685s, 1674s (KBr). ¹H NMR (400 MHz, DMSO): δ 10.85 (s, 1H, N—H), 8.50 (d, 2H, 4-pyr), 7.69 (d, 2H, 4-pyr), 7.80 (m, 1H, 2,4-Fbenz), 7.47 (m [td], 1H, 2,4-Fbenz), 7.26 (m [td], 1H, 2,4-Fbenz).

For (III), m.p. 433–435 K (uncorrected). IR (ν_C=O cm^-1): 1684s (CHCl₃); 1685s (KBr). ¹H NMR (400 MHz, DMSO): δ 10.93 (s, 1H, N—H), 8.51 (d, 2H, 4-pyr), 7.70 (d, 2H, 4-pyr), 7.61 (m, 1H, 2,5-Fbenz), 7.48 (m, 2H, 2,5-Fbenz).

S3. Refinement

H atoms attached to C atoms were treated as riding using SHELXL97 (Sheldrick, 2008) defaults at 150 (1) K with [C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C); N-bound H atoms were refined freely with isotropic displacement parameters to bond lengths of 0.88 (2) Å in (I), 0.92 (4) Å in (II) and 0.89 (2) Å in (III).

Computing details

For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and SORTX (McArdle, 1995); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PREP8 (Ferguson, 1998).

Figures

	Fig. 1. Relative abundance of difluorobenzene fragments in the CSD (version 5.29, January updates 2008)]. X = any element, Z = any element but H.
	Fig. 2. A view of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. A view of (II), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. A view of (III), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 5. The primary N—H···O═C interactions in (I) forming C(4) chains along [010] and linked by C—H···N interactions to form sheets: H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) x,y + 1,z; (ii) x + 1,y,z].
	Fig. 6. A view of the C—H···N interaction propagating in the [001] direction and forming a chain in (II): H atoms attached to C not involved in hydrogen bonding have been omitted for clarity. [Symmetry code: (i) x,y - 1/2,z + 1/2].
	Fig. 7. A view of the N—H···N intermolecular interaction in (III) forming zigzag chains along [010] and similar to the isomorphous series, (Donnelly et al., 2008). [Symmetry codes: (i) -x + 1,y + 1/2,-z + 1/2; (ii) -x + 1,y - 1/2,-z + 1/2].
	Fig. 8. A view of the C—H···π(arene) (linking chains into sheets) and antiparallel C=O···O═C interactions in (III) (linking sheets into a three-dimensional network): H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) -x + 2,-y,-z + 1; (ii) x,-y + 1/2,z + 1/2].

(I) 2,3-difluoro-N-(4-pyridyl)benzamide

Crystal data

C12H8F2N2O	F(000) = 480
Mr = 234.20	Dx = 1.536 Mg m^−3
Monoclinic, P21/n	Melting point: 385 K
Hall symbol: -p 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 12.5700 (6) Å	Cell parameters from 12328 reflections
b = 5.1257 (2) Å	θ = 2.6–27.5°
c = 16.5178 (8) Å	µ = 0.13 mm^−1
β = 107.847 (2)°	T = 150 K
V = 1013.03 (8) Å^3	Block, colourless
Z = 4	0.38 × 0.36 × 0.30 mm

Data collection

Nonius KappaCCD diffractometer	2292 independent reflections
Radiation source: fine-focus sealed X-ray tube	1872 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ϕ, ω scans with κ offsets	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −16→16
Tmin = 0.889, Tmax = 0.965	k = −6→6
5827 measured reflections	l = −21→21

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0452P)^2 + 0.3718P] where P = (Fo^2 + 2Fc^2)/3
2292 reflections	(Δ/σ)max < 0.001
158 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
F12	0.20330 (7)	0.77680 (17)	0.02099 (5)	0.0309 (2)
F13	0.40168 (7)	0.87823 (19)	0.00503 (6)	0.0377 (3)
O1	0.14765 (9)	0.1291 (2)	0.14635 (8)	0.0360 (3)
C1	0.16668 (11)	0.3556 (3)	0.13137 (9)	0.0251 (3)
N1	0.09370 (10)	0.5544 (2)	0.12683 (8)	0.0254 (3)
C11	0.27630 (11)	0.4290 (3)	0.11850 (8)	0.0239 (3)
C12	0.29056 (11)	0.6304 (3)	0.06672 (9)	0.0245 (3)
C13	0.39432 (12)	0.6836 (3)	0.05801 (9)	0.0279 (3)
C14	0.48711 (12)	0.5420 (3)	0.10112 (9)	0.0308 (3)
C15	0.47431 (12)	0.3376 (3)	0.15251 (9)	0.0320 (3)
C16	0.37000 (12)	0.2807 (3)	0.16037 (9)	0.0288 (3)
C21	−0.01346 (11)	0.5355 (3)	0.13734 (9)	0.0240 (3)
C22	−0.04349 (12)	0.3409 (3)	0.18500 (9)	0.0270 (3)
C23	−0.15038 (12)	0.3501 (3)	0.19325 (10)	0.0300 (3)
N24	−0.22677 (10)	0.5331 (3)	0.15855 (9)	0.0327 (3)
C25	−0.19528 (12)	0.7184 (3)	0.11343 (10)	0.0326 (4)
C26	−0.09093 (12)	0.7281 (3)	0.10129 (10)	0.0285 (3)
H1	0.1150 (15)	0.710 (4)	0.1162 (12)	0.038 (5)*
H14	0.5584	0.5830	0.0959	0.037*
H15	0.5373	0.2361	0.1825	0.038*
H16	0.3623	0.1382	0.1949	0.035*
H22	0.0074	0.2061	0.2110	0.032*
H23	−0.1706	0.2171	0.2258	0.036*
H25	−0.2476	0.8513	0.0882	0.039*
H26	−0.0729	0.8644	0.0688	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F12	0.0274 (4)	0.0300 (5)	0.0369 (5)	0.0041 (4)	0.0121 (4)	0.0083 (4)
F13	0.0361 (5)	0.0365 (5)	0.0462 (5)	−0.0037 (4)	0.0212 (4)	0.0076 (4)
O1	0.0373 (6)	0.0210 (5)	0.0572 (7)	0.0001 (4)	0.0254 (5)	0.0019 (5)
C1	0.0259 (7)	0.0229 (7)	0.0275 (7)	−0.0010 (6)	0.0098 (5)	−0.0012 (6)
N1	0.0238 (6)	0.0205 (6)	0.0340 (6)	−0.0008 (5)	0.0121 (5)	0.0023 (5)
C11	0.0242 (7)	0.0232 (7)	0.0252 (7)	−0.0005 (6)	0.0086 (5)	−0.0029 (5)
C12	0.0231 (7)	0.0242 (7)	0.0257 (7)	0.0024 (6)	0.0068 (5)	−0.0009 (5)
C13	0.0302 (7)	0.0275 (7)	0.0289 (7)	−0.0040 (6)	0.0133 (6)	−0.0013 (6)
C14	0.0234 (7)	0.0377 (9)	0.0330 (8)	−0.0034 (6)	0.0110 (6)	−0.0081 (7)
C15	0.0259 (7)	0.0374 (9)	0.0312 (7)	0.0070 (6)	0.0067 (6)	−0.0017 (7)
C16	0.0299 (7)	0.0294 (8)	0.0277 (7)	0.0034 (6)	0.0097 (6)	0.0010 (6)
C21	0.0225 (6)	0.0237 (7)	0.0264 (7)	−0.0030 (6)	0.0084 (5)	−0.0045 (6)
C22	0.0261 (7)	0.0248 (7)	0.0307 (7)	−0.0010 (6)	0.0097 (6)	0.0003 (6)
C23	0.0292 (7)	0.0283 (8)	0.0356 (8)	−0.0048 (6)	0.0145 (6)	−0.0024 (6)
N24	0.0256 (6)	0.0322 (7)	0.0414 (7)	−0.0017 (5)	0.0118 (5)	−0.0053 (6)
C25	0.0254 (7)	0.0289 (8)	0.0420 (9)	0.0032 (6)	0.0082 (6)	−0.0013 (7)
C26	0.0279 (7)	0.0242 (7)	0.0333 (7)	−0.0006 (6)	0.0095 (6)	0.0011 (6)

Geometric parameters (Å, º)

F12—C12	1.3523 (16)	C21—C22	1.393 (2)
F13—C13	1.3487 (17)	C22—C23	1.392 (2)
O1—C1	1.2259 (17)	C23—N24	1.339 (2)
C1—N1	1.3574 (18)	N24—C25	1.340 (2)
C1—C11	1.5048 (19)	C25—C26	1.387 (2)
N1—C21	1.4133 (17)	N1—H1	0.88 (2)
C11—C12	1.3872 (19)	C14—H14	0.9500
C11—C16	1.394 (2)	C15—H15	0.9500
C12—C13	1.3824 (19)	C16—H16	0.9500
C13—C14	1.373 (2)	C22—H22	0.9500
C14—C15	1.389 (2)	C23—H23	0.9500
C15—C16	1.388 (2)	C25—H25	0.9500
C21—C26	1.386 (2)	C26—H26	0.9500
O1—C1—N1	123.47 (13)	N24—C23—C22	124.67 (14)
O1—C1—C11	120.58 (12)	C23—N24—C25	116.06 (12)
N1—C1—C11	115.93 (12)	N24—C25—C26	124.02 (14)
C1—N1—C21	126.54 (12)	C21—C26—C25	118.90 (14)
C1—C11—C12	124.75 (12)	C1—N1—H1	116.9 (12)
C1—C11—C16	117.70 (13)	C21—N1—H1	116.5 (12)
C12—C11—C16	117.54 (13)	C13—C14—H14	120.8
F12—C12—C11	121.43 (12)	C15—C14—H14	120.8
F12—C12—C13	117.53 (13)	C16—C15—H15	119.8
C11—C12—C13	121.02 (13)	C14—C15—H15	119.8
F13—C13—C12	117.90 (13)	C15—C16—H16	119.4
F13—C13—C14	120.74 (13)	C11—C16—H16	119.4
C12—C13—C14	121.36 (14)	C23—C22—H22	121.1
C13—C14—C15	118.48 (13)	C21—C22—H22	121.1
C14—C15—C16	120.36 (13)	N24—C23—H23	117.7
C15—C16—C11	121.21 (14)	C22—C23—H23	117.7
C26—C21—C22	118.45 (13)	N24—C25—H25	118.0
C22—C21—N1	123.50 (13)	C26—C25—H25	118.0
C26—C21—N1	117.98 (13)	C21—C26—H26	120.6
C21—C22—C23	117.89 (13)	C25—C26—H26	120.6
O1—C1—N1—C21	−0.6 (2)	F13—C13—C14—C15	−177.70 (13)
O1—C1—C11—C12	149.52 (15)	C12—C13—C14—C15	1.7 (2)
C11—C1—N1—C21	−179.45 (12)	C13—C14—C15—C16	−0.6 (2)
C1—N1—C21—C26	−156.89 (14)	C14—C15—C16—C11	−1.2 (2)
N1—C1—C11—C12	−31.6 (2)	C12—C11—C16—C15	1.9 (2)
O1—C1—C11—C16	−29.2 (2)	C1—C11—C16—C15	−179.31 (13)
N1—C1—C11—C16	149.63 (13)	C1—N1—C21—C22	26.1 (2)
C16—C11—C12—F12	177.19 (12)	C26—C21—C22—C23	0.4 (2)
C1—C11—C12—F12	−1.5 (2)	N1—C21—C22—C23	177.44 (13)
C16—C11—C12—C13	−0.8 (2)	C21—C22—C23—N24	0.0 (2)
C1—C11—C12—C13	−179.54 (13)	C22—C23—N24—C25	−0.3 (2)
F12—C12—C13—F13	0.4 (2)	C23—N24—C25—C26	0.2 (2)
C11—C12—C13—F13	178.43 (12)	C22—C21—C26—C25	−0.5 (2)
F12—C12—C13—C14	−179.05 (13)	N1—C21—C26—C25	−177.72 (13)
C11—C12—C13—C14	−1.0 (2)	N24—C25—C26—C21	0.2 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.88 (2)	2.21 (2)	3.0181 (16)	152.3 (16)
N1—H1···F12	0.88 (2)	2.212 (18)	2.7803 (14)	122.2 (15)
C22—H22···O1	0.95	2.36	2.8807 (18)	114
C14—H14···N24^ii	0.95	2.59	3.4273 (19)	147
C15—H15···Cg1^iii	0.95	2.86	3.5941 (16)	135
C25—H25···F13^iv	0.95	2.49	3.4240 (18)	166

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

(II) 2,4-Difluoro-N-(4-pyridyl)benzamide

Crystal data

C12H8F2N2O	F(000) = 480
Mr = 234.20	Dx = 1.559 Mg m^−3
Monoclinic, P21/c	Melting point: 391 K
Hall symbol: -p 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.3187 (6) Å	Cell parameters from 12237 reflections
b = 5.5868 (6) Å	θ = 2.6–27.5°
c = 21.715 (2) Å	µ = 0.13 mm^−1
β = 98.517 (6)°	T = 150 K
V = 998.07 (16) Å^3	Block, colourless
Z = 4	0.24 × 0.16 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer	2248 independent reflections
Radiation source: fine-focus sealed X-ray tube	1197 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.083
ϕ, ω scans with κ offsets	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −10→10
Tmin = 0.969, Tmax = 0.996	k = −6→7
6812 measured reflections	l = −27→28

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0684P)^2] where P = (Fo^2 + 2Fc^2)/3
2248 reflections	(Δ/σ)max < 0.001
158 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.27 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
F12	0.33130 (18)	0.2730 (2)	0.08087 (6)	0.0475 (4)
F14	0.06367 (18)	−0.0413 (3)	0.23708 (6)	0.0528 (5)
O1	0.2144 (2)	−0.3342 (3)	−0.02686 (8)	0.0520 (5)
C1	0.2306 (3)	−0.1351 (5)	−0.00339 (11)	0.0371 (6)
N1	0.2865 (2)	0.0569 (4)	−0.03263 (9)	0.0390 (5)
C11	0.1865 (3)	−0.0936 (4)	0.06019 (11)	0.0362 (6)
C12	0.2364 (3)	0.0969 (4)	0.10006 (11)	0.0383 (6)
C13	0.1983 (3)	0.1188 (4)	0.15936 (11)	0.0420 (6)
C14	0.1035 (3)	−0.0589 (5)	0.17904 (11)	0.0403 (6)
C15	0.0484 (3)	−0.2528 (5)	0.14245 (12)	0.0417 (6)
C16	0.0914 (3)	−0.2671 (4)	0.08382 (11)	0.0398 (6)
C21	0.3302 (3)	0.0663 (4)	−0.09274 (11)	0.0353 (6)
C22	0.2967 (3)	−0.1138 (5)	−0.13730 (11)	0.0391 (6)
C23	0.3446 (3)	−0.0780 (5)	−0.19485 (12)	0.0430 (7)
N24	0.4182 (2)	0.1182 (4)	−0.21226 (9)	0.0427 (6)
C25	0.4485 (3)	0.2890 (5)	−0.16867 (11)	0.0419 (7)
C26	0.4088 (3)	0.2708 (4)	−0.10933 (11)	0.0404 (6)
H1	0.296 (4)	0.200 (7)	−0.0118 (14)	0.083 (11)*
H13	0.2358	0.2501	0.1854	0.050*
H15	−0.0171	−0.3727	0.1573	0.050*
H16	0.0550	−0.4004	0.0584	0.048*
H22	0.2427	−0.2567	−0.1283	0.047*
H23	0.3235	−0.2033	−0.2245	0.052*
H25	0.5005	0.4314	−0.1793	0.050*
H26	0.4349	0.3966	−0.0801	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F12	0.0610 (10)	0.0400 (9)	0.0426 (9)	−0.0101 (7)	0.0115 (7)	−0.0039 (7)
F14	0.0730 (11)	0.0510 (10)	0.0385 (9)	0.0092 (8)	0.0218 (7)	0.0011 (7)
O1	0.0809 (14)	0.0355 (11)	0.0441 (11)	−0.0072 (9)	0.0238 (9)	−0.0036 (9)
C1	0.0426 (14)	0.0324 (15)	0.0365 (14)	−0.0010 (11)	0.0067 (11)	0.0007 (11)
N1	0.0489 (13)	0.0343 (13)	0.0354 (12)	−0.0026 (10)	0.0114 (9)	−0.0005 (10)
C11	0.0408 (14)	0.0333 (14)	0.0351 (14)	0.0031 (11)	0.0079 (11)	−0.0016 (11)
C12	0.0422 (14)	0.0338 (15)	0.0396 (15)	−0.0020 (11)	0.0081 (11)	0.0045 (11)
C13	0.0521 (16)	0.0353 (15)	0.0383 (15)	0.0044 (12)	0.0055 (12)	−0.0038 (12)
C14	0.0485 (15)	0.0425 (16)	0.0315 (14)	0.0098 (12)	0.0113 (11)	0.0040 (12)
C15	0.0471 (15)	0.0388 (15)	0.0412 (15)	0.0004 (12)	0.0130 (11)	0.0049 (12)
C16	0.0461 (15)	0.0343 (15)	0.0393 (15)	−0.0004 (11)	0.0078 (12)	−0.0003 (11)
C21	0.0388 (14)	0.0301 (14)	0.0378 (14)	0.0024 (10)	0.0081 (10)	0.0029 (11)
C22	0.0444 (14)	0.0339 (15)	0.0398 (15)	−0.0014 (11)	0.0085 (11)	0.0004 (11)
C23	0.0538 (16)	0.0335 (15)	0.0414 (15)	0.0005 (12)	0.0064 (12)	−0.0035 (12)
N24	0.0546 (13)	0.0361 (13)	0.0394 (13)	0.0027 (10)	0.0132 (10)	0.0014 (10)
C25	0.0514 (16)	0.0332 (15)	0.0431 (16)	0.0014 (11)	0.0141 (12)	0.0020 (11)
C26	0.0496 (15)	0.0323 (15)	0.0401 (15)	−0.0002 (11)	0.0095 (11)	−0.0019 (11)

Geometric parameters (Å, º)

F12—C12	1.365 (3)	C21—C22	1.395 (3)
F14—C14	1.353 (3)	C22—C23	1.381 (3)
O1—C1	1.222 (3)	C23—N24	1.337 (3)
C1—N1	1.363 (3)	N24—C25	1.341 (3)
C1—C11	1.498 (3)	C25—C26	1.381 (3)
N1—C21	1.407 (3)	N1—H1	0.92 (4)
C11—C12	1.396 (3)	C13—H13	0.9500
C11—C16	1.396 (3)	C15—H15	0.9500
C12—C13	1.376 (3)	C16—H16	0.9500
C13—C14	1.375 (4)	C22—H22	0.9500
C14—C15	1.381 (4)	C23—H23	0.9500
C15—C16	1.375 (3)	C25—H25	0.9500
C21—C26	1.390 (3)	C26—H26	0.9500
O1—C1—N1	123.1 (2)	N24—C23—C22	125.5 (2)
O1—C1—C11	119.9 (2)	C23—N24—C25	115.4 (2)
N1—C1—C11	117.0 (2)	N24—C25—C26	124.1 (2)
C1—N1—C21	127.9 (2)	C25—C26—C21	119.3 (2)
C12—C11—C16	115.7 (2)	C1—N1—H1	118 (2)
C12—C11—C1	126.8 (2)	C21—N1—H1	114 (2)
C16—C11—C1	117.4 (2)	C14—C13—H13	121.7
F12—C12—C13	116.4 (2)	C12—C13—H13	121.7
F12—C12—C11	119.5 (2)	C16—C15—H15	121.0
C13—C12—C11	124.0 (2)	C14—C15—H15	121.0
C14—C13—C12	116.7 (2)	C15—C16—H16	118.7
F14—C14—C13	117.9 (2)	C11—C16—H16	118.7
F14—C14—C15	119.1 (2)	C23—C22—H22	121.0
C13—C14—C15	123.0 (2)	C21—C22—H22	121.0
C16—C15—C14	117.9 (2)	C22—C23—H23	117.3
C15—C16—C11	122.7 (2)	N24—C23—H23	117.3
C26—C21—C22	117.8 (2)	N24—C25—H25	118.0
C26—C21—N1	117.9 (2)	C26—C25—H25	118.0
C22—C21—N1	124.4 (2)	C25—C26—H26	120.4
C23—C22—C21	117.9 (2)	C21—C26—H26	120.4
O1—C1—N1—C21	1.7 (4)	F14—C14—C15—C16	−179.6 (2)
O1—C1—C11—C12	161.5 (2)	C13—C14—C15—C16	0.1 (4)
C11—C1—N1—C21	−177.7 (2)	C14—C15—C16—C11	−0.5 (4)
C1—N1—C21—C26	−169.8 (2)	C12—C11—C16—C15	0.2 (4)
N1—C1—C11—C12	−19.1 (4)	C1—C11—C16—C15	177.6 (2)
O1—C1—C11—C16	−15.6 (3)	C1—N1—C21—C22	11.7 (4)
N1—C1—C11—C16	163.8 (2)	C26—C21—C22—C23	0.4 (3)
C16—C11—C12—F12	179.25 (19)	N1—C21—C22—C23	178.9 (2)
C1—C11—C12—F12	2.2 (4)	C21—C22—C23—N24	−1.4 (4)
C16—C11—C12—C13	0.5 (4)	C22—C23—N24—C25	1.2 (4)
C1—C11—C12—C13	−176.6 (2)	C23—N24—C25—C26	0.1 (4)
F12—C12—C13—C14	−179.6 (2)	N24—C25—C26—C21	−1.1 (4)
C11—C12—C13—C14	−0.9 (4)	C22—C21—C26—C25	0.8 (3)
C12—C13—C14—F14	−179.7 (2)	N1—C21—C26—C25	−177.9 (2)
C12—C13—C14—C15	0.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F12	0.92 (4)	2.03 (3)	2.720 (3)	131 (3)
C22—H22···O1	0.95	2.29	2.868 (3)	118
C13—H13···N24^i	0.95	2.60	3.430 (3)	146

Symmetry code: (i) x, −y+1/2, z+1/2.

(III) 2,5-difluoro(4-pyridyl)benzamide

Crystal data

C12H8F2N2O	F(000) = 480
Mr = 234.20	Dx = 1.537 Mg m^−3
Monoclinic, P21/c	Melting point: 433 K
Hall symbol: -p 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 6.2088 (4) Å	Cell parameters from 3173 reflections
b = 11.0182 (5) Å	θ = 2.6–27.5°
c = 14.8139 (9) Å	µ = 0.13 mm^−1
β = 93.018 (3)°	T = 150 K
V = 1012.01 (10) Å^3	Block, colourless
Z = 4	0.22 × 0.16 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer	2295 independent reflections
Radiation source: fine-focus sealed X-ray tube	1555 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ϕ, ω scans with κ offsets	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −8→8
Tmin = 0.932, Tmax = 0.988	k = −13→14
6136 measured reflections	l = −19→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.0625P)^2 + 0.0245P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2295 reflections	Δρmax = 0.21 e Å^−3
159 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (4)

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
F12	0.52432 (15)	0.14293 (9)	0.52228 (6)	0.0348 (3)
F15	1.22204 (17)	0.43599 (9)	0.56952 (8)	0.0430 (3)
O1	1.06883 (18)	0.04700 (10)	0.40055 (8)	0.0290 (3)
C1	0.8934 (3)	0.09249 (14)	0.41366 (11)	0.0231 (4)
N1	0.7049 (2)	0.05987 (12)	0.36865 (9)	0.0251 (3)
C11	0.8758 (2)	0.19442 (14)	0.48050 (10)	0.0223 (4)
C12	0.6988 (3)	0.21626 (15)	0.53140 (11)	0.0265 (4)
C13	0.6938 (3)	0.30864 (16)	0.59425 (12)	0.0328 (4)
C14	0.8705 (3)	0.38450 (16)	0.60598 (12)	0.0345 (5)
C15	1.0471 (3)	0.36289 (15)	0.55668 (12)	0.0306 (4)
C16	1.0556 (3)	0.26969 (14)	0.49455 (11)	0.0255 (4)
C21	0.6718 (3)	−0.03641 (14)	0.30797 (10)	0.0230 (4)
C22	0.8243 (3)	−0.12549 (14)	0.29181 (11)	0.0246 (4)
C23	0.7666 (3)	−0.21728 (15)	0.23112 (11)	0.0272 (4)
N24	0.5755 (2)	−0.22661 (12)	0.18534 (9)	0.0286 (4)
C25	0.4321 (3)	−0.13938 (15)	0.20199 (12)	0.0301 (4)
C26	0.4708 (3)	−0.04471 (14)	0.26199 (11)	0.0274 (4)
H1	0.592 (3)	0.1084 (19)	0.3720 (13)	0.042 (6)*
H13	0.5708	0.3199	0.6289	0.039*
H14	0.8695	0.4503	0.6474	0.041*
H16	1.1814	0.2570	0.4620	0.031*
H22	0.9637	−0.1234	0.3215	0.030*
H23	0.8709	−0.2783	0.2213	0.033*
H25	0.2950	−0.1429	0.1705	0.036*
H26	0.3620	0.0138	0.2717	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F12	0.0312 (6)	0.0413 (6)	0.0324 (6)	−0.0037 (5)	0.0076 (5)	−0.0018 (4)
F15	0.0454 (7)	0.0335 (6)	0.0492 (8)	−0.0087 (5)	−0.0077 (5)	−0.0103 (5)
O1	0.0279 (7)	0.0273 (7)	0.0320 (7)	0.0012 (5)	0.0041 (5)	−0.0041 (5)
C1	0.0271 (9)	0.0204 (8)	0.0218 (9)	−0.0001 (7)	0.0020 (7)	0.0039 (6)
N1	0.0265 (8)	0.0217 (7)	0.0271 (8)	0.0043 (6)	−0.0003 (6)	−0.0037 (6)
C11	0.0273 (9)	0.0205 (8)	0.0189 (8)	0.0035 (7)	−0.0009 (7)	0.0019 (6)
C12	0.0266 (9)	0.0274 (9)	0.0255 (9)	0.0007 (7)	0.0000 (7)	0.0022 (7)
C13	0.0352 (10)	0.0365 (10)	0.0269 (10)	0.0104 (9)	0.0049 (8)	−0.0023 (8)
C14	0.0468 (12)	0.0284 (9)	0.0277 (10)	0.0087 (9)	−0.0032 (8)	−0.0064 (7)
C15	0.0359 (10)	0.0238 (9)	0.0313 (10)	−0.0007 (8)	−0.0067 (8)	−0.0007 (7)
C16	0.0303 (9)	0.0238 (8)	0.0223 (9)	0.0038 (7)	−0.0003 (7)	0.0012 (6)
C21	0.0297 (9)	0.0198 (8)	0.0196 (9)	−0.0006 (7)	0.0037 (7)	0.0016 (6)
C22	0.0265 (9)	0.0242 (8)	0.0231 (9)	0.0014 (7)	0.0013 (7)	0.0020 (7)
C23	0.0331 (9)	0.0229 (9)	0.0258 (9)	0.0029 (7)	0.0040 (7)	−0.0014 (7)
N24	0.0345 (8)	0.0247 (7)	0.0266 (8)	0.0005 (6)	0.0008 (6)	−0.0022 (6)
C25	0.0300 (10)	0.0287 (9)	0.0312 (10)	−0.0016 (8)	−0.0021 (7)	−0.0004 (7)
C26	0.0295 (9)	0.0228 (8)	0.0297 (10)	0.0031 (7)	0.0009 (7)	0.0000 (7)

Geometric parameters (Å, º)

F12—C12	1.3527 (18)	C21—C26	1.393 (2)
F15—C15	1.357 (2)	C22—C23	1.388 (2)
O1—C1	1.2239 (19)	C23—N24	1.339 (2)
C1—N1	1.364 (2)	N24—C25	1.342 (2)
C1—C11	1.505 (2)	C25—C26	1.383 (2)
N1—C21	1.399 (2)	N1—H1	0.89 (2)
C11—C12	1.386 (2)	C13—H13	0.9500
C11—C16	1.397 (2)	C14—H14	0.9500
C12—C13	1.381 (2)	C16—H16	0.9500
C13—C14	1.383 (3)	C22—H22	0.9500
C14—C15	1.370 (3)	C23—H23	0.9500
C15—C16	1.382 (2)	C25—H25	0.9500
C21—C22	1.393 (2)	C26—H26	0.9500
O1—C1—N1	124.22 (15)	N24—C23—C22	125.13 (16)
O1—C1—C11	120.40 (15)	C23—N24—C25	115.51 (14)
N1—C1—C11	115.35 (14)	N24—C25—C26	124.33 (16)
C1—N1—C21	127.41 (14)	C25—C26—C21	118.99 (16)
C1—C11—C12	125.07 (15)	C1—N1—H1	118.4 (13)
C1—C11—C16	117.11 (14)	C21—N1—H1	113.8 (13)
C12—C11—C16	117.76 (15)	C12—C13—H13	120.5
F12—C12—C11	119.72 (14)	C14—C13—H13	120.5
F12—C12—C13	117.45 (15)	C15—C14—H14	120.7
C11—C12—C13	122.80 (16)	C13—C14—H14	120.7
C12—C13—C14	118.95 (16)	C15—C16—H16	120.6
C13—C14—C15	118.69 (16)	C11—C16—H16	120.6
F15—C15—C14	118.63 (15)	C23—C22—H22	121.0
F15—C15—C16	118.44 (16)	C21—C22—H22	121.0
C14—C15—C16	122.94 (17)	N24—C23—H23	117.4
C11—C16—C15	118.83 (16)	C22—C23—H23	117.4
C22—C21—C26	117.98 (15)	N24—C25—H25	117.8
C26—C21—N1	117.51 (15)	C26—C25—H25	117.8
C22—C21—N1	124.50 (14)	C25—C26—H26	120.5
C21—C22—C23	118.06 (15)	C21—C26—H26	120.5
O1—C1—N1—C21	7.0 (3)	C13—C14—C15—C16	1.1 (3)
O1—C1—C11—C12	−148.88 (16)	F15—C15—C16—C11	−179.62 (14)
C11—C1—N1—C21	−175.26 (14)	C14—C15—C16—C11	0.6 (3)
C1—N1—C21—C26	−172.89 (16)	C12—C11—C16—C15	−1.2 (2)
N1—C1—C11—C12	33.3 (2)	C1—C11—C16—C15	−178.79 (14)
O1—C1—C11—C16	28.5 (2)	C1—N1—C21—C22	8.4 (3)
N1—C1—C11—C16	−149.35 (14)	C26—C21—C22—C23	−0.2 (2)
C16—C11—C12—F12	−177.66 (13)	N1—C21—C22—C23	178.52 (15)
C1—C11—C12—F12	−0.3 (2)	C21—C22—C23—N24	1.0 (3)
C16—C11—C12—C13	0.3 (2)	C22—C23—N24—C25	−0.7 (2)
C1—C11—C12—C13	177.64 (15)	C23—N24—C25—C26	−0.3 (2)
F12—C12—C13—C14	179.32 (14)	N24—C25—C26—C21	1.0 (3)
C11—C12—C13—C14	1.3 (3)	C22—C21—C26—C25	−0.7 (2)
C12—C13—C14—C15	−2.0 (3)	N1—C21—C26—C25	−179.51 (15)
C13—C14—C15—F15	−178.76 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N24^i	0.89 (2)	2.24 (2)	3.010 (2)	145.3 (17)
N1—H1···F12	0.89 (2)	2.32 (2)	2.7465 (17)	109.7 (15)
C22—H22···O1	0.95	2.29	2.873 (2)	119
C22—H22···Cg1^ii	0.95	2.86	3.4966 (18)	126
C14—H14···Cg2^iii	0.95	2.95	3.8012 (19)	149

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