Crystal structures of three N-(pyridine-2-carbon­yl)pyridine-2-carboxamides as potential ligands for supra­molecular chemistry

Xu, X.; Hoogenboom, R.; Van Hecke, K.

doi:10.1107/S2056989021008562

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Volume 77| Part 9| September 2021| Pages 958-964

https://doi.org/10.1107/S2056989021008562

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Crystal structures of three N-(pyridine-2-carbonyl)pyridine-2-carboxamides as potential ligands for supramolecular chemistry

Xiaowen Xu,^a Richard Hoogenboom ^a and Kristof Van Hecke ^b ^*

^aSupramolecular Chemistry Group, Centre of Macromolecular Chemistry (CMaC), Department of Organic and Macromolecular Chemistry, Ghent University, Krijgslaan 281-S4, B-9000 Ghent, Belgium, and ^bXStruct, Department of Chemistry, Ghent University, Krijgslaan 281-S3, B-9000 Ghent, Belgium
^*Correspondence e-mail: Kristof.VanHecke@UGent.be

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 27 July 2021; accepted 17 August 2021; online 24 August 2021)

The synthesis and single-crystal X-ray structures of three N-(pyridine-2-carbonyl)pyridine-2-carboxamide imides, with or without F atoms on the 3-position of the pyridine rings are reported, namely, N-(pyridine-2-carbonyl)pyridine-2-carboxamide, C₁₂H₉N₃O₂ (1), N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide, C₁₂H₈FN₃O₂ (2), and 3-fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide, C₁₂H₇F₂N₃O₂ (3). The above-mentioned compounds were synthesized by a mild, general procedure with an excellent yield, providing straightforward access to symmetrical and/or asymmetrical heterocyclic ureas. The crystal structures of 1 and 2 are isomorphous, showing similar packing arrangements, i.e. double layers of parallel (face-to-face) molecules alternating with analogous, but perpendicularly oriented, double layers. In contrast, the crystal structure of 3, containing a fluoro- group at the 3-position of both pyridine rings, shows molecular arrangements in a longitudinal, tubular manner along the c axis, with the aromatic pyridine and carbonyl/fluorine moieties facing towards each other.

Keywords: supramolecular chemistry; N-(pyridine-2-carbonyl)pyridine-2-carboxamide; fluorine moieties; crystal structure.

CCDC references: 2103652; 2103651; 2103650

1. Chemical context

N-(Pyridine-2-carbonyl)pyridine-2-carboxamide systems and their derivatives have been shown to be very useful intermediates for the construction of molecular building blocks, able to self-assemble into a wide range of super-architectures taking advantage of acceptor–donor–donor–acceptor (ADDA) arrays of hydrogen-bonding sites (Corbin et al., 2001 ). Further interest in this family of compounds has involved the investigation of their metal coordination complexes, which possess strong luminescence characteristics (Das et al., 2018 ), as well as their electrochemical (Gasser et al., 2012 ), magnetic (Kajiwara et al., 2010 ) and catalytic properties (Chowdhury et al., 2007 ). Consequently, the synthesis of N-(pyridine-2-carbonyl)pyridine-2-carboxamide, containing different functional groups, at a large scale and in a high yield is of great importance in the field of supramolecular chemistry. Previously reported studies have shown the conversion of 2-aminopyridine to 1 in a single step (Gerchuk & Taits, 1950 ; Corbin et al., 2001). However, the utilized reaction conditions were, to some extent, harsh and the reported yield of the compound was rather low (< 32%), presumably because of the inferior nucleophilicity of the –NH₂ groups at the 2-position of the pyridine rings. Moreover, the use of this procedure is limited to the synthesis of symmetrical imides. The synthesis of high-yield asymmetrical imides, bearing different functional groups on the pyridine rings, is still challenging.

Herein, we report the single-crystal X-ray structural analysis of the imides N-(pyridine-2-carbonyl)pyridine-2-carboxamide (1) (R₁ = H, R₂ = H), N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2) (R₁ = F, R₂ = H) and 3-fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3) (R₁ = F, R₂ = F), prepared via a simple, straightforward synthesis method that does not involve high pressure nor harsh conditions and can be carried out on a large scale.

2. Structural commentary

The structure of 1, although determined at a different temperature of 200 K, has previously been deposited in the CSD (refcode COJNAT; Castaneda & Gabidullin, 2019 ). Compound 1 crystallizes in the non-centrosymmetric orthorhombic space group Pna2₁, with the asymmetric unit consisting of one N-(pyridine-2-carbonyl)pyridine-2-carboxamide molecule. The molecular structure of 1 is found almost completely planar, with a dihedral angle of 6.1 (2)° between the best planes through the two pyridine rings (Fig. 1a).

Figure 1
Molecular structures of (a) 1, (b) 2 and (c) 3, showing thermal displacement ellipsoids drawn at the 50% probability level and the atom-labelling scheme. The disorder in 2 (b) is shown in yellow. The carbon atoms in the asymmetric unit of 3 (c) are shown in green. Intramolecular hydrogen bonds are indicated.

The structure of 2 is isomorphous with 1, although the 3-fluoro-N-(pyridine-2-carbonyl)pyridine-2-carboxamide molecules are rotated 90° with respect to 1 (Fig. 2). Similarly to 1, the asymmetric unit contains one planar 3-fluoro-N-(pyridine-2-carbonyl)pyridine-2-carboxamide molecule, which shows a dihedral angle of 5.2 (2)° between the best planes through the two pyridine rings. Here, the fluoro group is found disordered over both pyridine rings, i.e. a transverse disorder by 180° rotation along the axis through the imide N—H function occurs, showing refined occupancy factors of 0.563 (8) and 0.437 (8) for the first (F1A) and second fluoro (F1B) site, respectively (Fig. 1b).

Figure 2
Unit-cell fit of the structures of 1 and 2, showing a 90° rotation of the molecules of 2 (in green). Hydrogen atoms and disorder of the fluorine atoms are omitted for clarity.

Compound 3 crystallizes in the centrosymmetric monoclinic space group I2/a, with the asymmetric unit consisting of only half of a total 3-fluoro-N-(3-fluoro-pyridine-2-carbonyl)pyridine-2-carboxamide molecule. The second half is generated by symmetry, i.e. a twofold axis runs through the N—H imide atoms. In contrast to the previous structures of 1 and 2, the molecular structure of 3 is not planar, with a dihedral angle of 29.73 (11)° between the best planes through the two pyridine rings (Fig. 1c).

3. Supramolecular features

Despite the presence of two pyridine rings in the molecular structure of 1, only weak π–π interactions are present in the crystal packing, with rather large centroid–centroid distances ranging from 4.969 (2) to 5.497 (2) Å. However, clear C=O⋯π contacts are observed in the crystal packing [C6—O1⋯Cg1(x, y, −1 + z) = 3.861 (3) Å; Cg1 is the centroid of the C1–C5/N1 ring]. Intramolecular potential hydrogen bonds are found between the imide N2—H2 hydrogen atom and both pyridine nitrogen atoms [N2—H2⋯N1 = 2.15 (6) Å; N2—H2⋯N3 = 2.15 (5) Å], while non-classical intermolecular hydrogen bonds can be observed between the first pyridine rings and carbonyl O2 atoms of symmetry-equivalent molecules [C3—H3⋯O2ⁱ = 2.48 Å; symmetry code: (i) $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, − $[{3\over 2}]$ + z], while these first pyridine rings are further connected to each other via similar hydrogen bonds with the pyridine N1 atoms [C5—H5⋯N1ⁱⁱ = 2.51 Å; symmetry code: (ii) −x, 1 − y, − $[{1\over 2}]$ + z] (Table 1). As such, in the packing, double layers of parallel (face-to-face) molecules of 1 are observed, parallel with the (100) plane, alternating with analogous double layers, oriented perpendicular to the former layers (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °) for 1

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1	0.90 (5)	2.15 (6)	2.614 (5)	111 (4)
N2—H2⋯N3	0.90 (5)	2.15 (5)	2.637 (4)	113 (5)
C3—H3⋯O2ⁱ	0.95	2.48	3.343 (5)	152
C5—H5⋯N1ⁱⁱ	0.95	2.51	3.393 (5)	154
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{3\over 2}}]$ ; (ii) $[-x, -y+1, z-{\script{1\over 2}}]$ .

Figure 3
Packing in the structure of 1, showing (a) the perpendicularly oriented molecules, viewed down the a axis and (b) the double layers of parallel-oriented (face-to-face) molecules, interchanged with analogous double layers, perpendicular to the former layers.

For the structure of 2, analogous to 1, only weak π–π interactions are present in the crystal packing between the 3-fluoro-pyridine rings, with centroid–centroid distances in the range 4.915 (3) to 5.473 (3) Å, while C=O⋯π contacts are also observed in the crystal packing [C6—O1⋯Cg1(x, y, −1 + z)= 3.865 (4) Å; Cg1 is the centroid of the C1–C5/N1 ring]. Analogous to 1, intramolecular potential hydrogen bonds between the imide N2—H2 hydrogen atom and both pyridine nitrogen atoms are observed [N2—H2⋯N1 = 2.16 (6) Å; N2—H2⋯N3 = 2.11 (6) Å], while non-classical intermolecular hydrogen bonds occur between the first pyridine rings and carbonyl O2 atoms of symmetry-equivalent molecules [C3—H3⋯O2ⁱ = 2.43 Å; symmetry code: (i) $[{1\over 2}]$ − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ + z], while these first pyridine rings are further connected to each other via similar hydrogen bonds with the pyridine N1 atoms [C5—H5⋯N1ⁱⁱ = 2.53 Å; symmetry code: (ii) 1 − x, 2 − y, $[{1\over 2}]$ + z]. Additionally, C—H⋯F hydrogen bonds are observed with the two disordered fluorine moieties [C3—H3⋯F1Bⁱ = 2.40 Å; C10—H10⋯F1Aⁱⁱⁱ = 2.45 Å; symmetry code: (iii) $[{1\over 2}]$ + x, $[{3\over 2}]$ − y, −1 + z] (Table 2). However, in the packing, analogous to 1, alternating double layers of parallel (face-to-face) molecules of 2 are observed, parallel with the (100) plane (Fig. 4). Hence, the extra C—H⋯F bonds do not alter the overall architecture.

Table 2
Hydrogen-bond geometry (Å, °) for 2

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1	0.92 (5)	2.16 (6)	2.614 (6)	109 (4)
N2—H2⋯N3	0.92 (5)	2.11 (6)	2.622 (5)	114 (5)
C3—H3⋯O2ⁱ	0.95	2.43	3.320 (6)	156
C3—H3⋯F1Bⁱ	0.95	2.40	3.049 (8)	125
C5—H5⋯N1ⁱⁱ	0.95	2.53	3.420 (6)	156
C10—H10⋯F1Aⁱⁱⁱ	0.95	2.45	3.169 (7)	132
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z+{\script{3\over 2}}]$ ; (ii) $[-x+1, -y+2, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-1]$ .

Figure 4
Packing in the structure of 2, showing (a) the perpendicularly oriented molecules, viewed down the a axis and (b) the double layers of parallel-oriented (face-to-face) molecules, interchanged with analogous double layers, perpendicular to the former layers. C10—H10⋯F1A hydrogen bonds are indicated. Hydrogen atoms and disorder of the fluorine atoms are omitted for clarity.

For 3, besides weak π–π interactions between the pyridine rings [centroid–centroid distances in the range 4.3776 (13)–5.9437 (13) Å], one strong π–π contact is observed between the pyridine ring and its symmetry-equivalent [Cg⋯Cg( $[{1\over 2}]$ − x, $[{1\over 2}]$ − y, $[{1\over 2}]$ − z) = 3.6334 (13) Å; Cg is the centroid of the C1–C5/N1 ring]. Analogous to 1 and 2, intramolecular potential hydrogen bonds are observed between the imide N2—H2 hydrogen atom and the pyridine nitrogen atom [N2—H2⋯N1 = 2.265 (15) Å], while non-classical intermolecular hydrogen bonds between the pyridine rings and carbonyl O1 atoms of symmetry-equivalent molecules are found [C4—H4⋯O1ⁱⁱ = 2.49 Å; symmetry code: (ii) −x, − $[{1\over 2}]$ + y, $[{1\over 2}]$ − z] (Table 3). Additionally, although significantly longer, other hydrogen bonds are formed between the pyridine ring and the carbonyl O1 atom [C5—H5⋯O1ⁱⁱ = 2.61 Å] and C—H⋯F hydrogen bonds are observed with the fluorine moieties [C5—H5⋯F1ⁱⁱ = 2.66 Å; C3—H3⋯F1ⁱⁱⁱ = 2.58 Å; symmetry codes: (iii) −x, 1 − y, −z]. This gives rise to a different packing assembly, i.e. the molecules are arranged in a longitudinal, tubular manner along the c-axis direction, while the aromatic pyridine and the carbonyl/fluorine moieties, face towards each other (Fig. 5).

Table 3
Hydrogen-bond geometry (Å, °) for 3

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1	0.84 (4)	2.27 (2)	2.671 (2)	110 (1)
N2—H2⋯N1ⁱ	0.84 (4)	2.27 (2)	2.671 (2)	110 (1)
C4—H4⋯O1ⁱⁱ	0.95	2.49	3.135 (3)	125
C5—H5⋯O1ⁱⁱ	0.95	2.61	3.207 (3)	122
C3—H3⋯F1ⁱⁱⁱ	0.95	2.58	3.398 (3)	145
C5—H5⋯F1ⁱⁱ	0.95	2.66	3.604 (3)	176
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y, -z+1]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) .

Figure 5
Packing in the structure of 3, showing (a) the longitudinal tubular arrangement of the molecules along the c axis and (b) the aromatic pyridine and the carbonyl/fluorine moieties facing towards each other. C5—H5⋯F1 and C3—H3⋯F1 hydrogen bonds are indicated. Hydrogen atoms are omitted for clarity.

4. Database survey

A survey of compounds related to 1, 2 and 3, deposited with the Cambridge Structural Database (CSD 2021.1, version 5.42 updates May 2021; Groom et al., 2016 ) resulted in three other compounds with refcodes COJNAT, WUXQOW and ZAVVAV.

As previously mentioned, COJNAT (Castaneda & Gabidullin, 2019) represents the same structure as 1, although determined at 200 K. When fitting the molecular structures of COJNAT and 1, an r.m.s.d. of 0.0107 Å is obtained.

The structure with refcode WUXQOW (Sahu et al., 2010 ) represents an analogous structure to 1, but featuring quinoline moieties instead of pyridine rings, i.e. N,N-bis(quinolin-2-ylcarbonyl)amine. Similarly to 1, the molecular structure is also found to be almost completely planar, with a dihedral angle of 1.34 (4)° between the best planes through the two quinoline moieties.

The structure with refcode ZAVVAV (Zebret et al., 2012 ) represents another N-(pyridine-2-carbonyl)pyridine-2-carboxamide system, in this case featuring two methoxy substituents, one on each pyridine ring, i.e. methyl 6-({[6-(methoxycarbonyl)pyridin-2-yl]carbonyl}carbamoyl)pyridine-2-carboxylate. Here, because of steric hindrance of the substituents, the planes defined by the two pyridine rings are distorted by 14.52 (11)°.

5. Synthesis and crystallization

The known compound 1 was prepared in excellent yield by the reaction between 2-pyridinecarbonyl chloride and 2-pyridinecarboxamide under mild conditions. By introducing a fluoro group at the 3-position of 2-pyridinecarbonyl chloride and/or 2-pyridinecarboxamide, the new compounds 2 and 3 could be obtained, also in excellent yield. Details for the synthesis of the precursors and the products are given below. Unless otherwise stated, all reagents were used as received.

3-Fluoropyridine-2-carboxylic acid

The preparation of 3-fluoropyridine-2-carboxylic acid was performed according to a previously reported procedure (Eller et al., 2006 ). Commercially available lithium 3-fluoropicolinate (1.47 g, 10 mmol) was recrystallized from a mixture of EtOH–H₂O (9:1), which was acidified with several drops of concentrated HCl (36.5%) to afford 3-fluoropyridine-2-carboxylic acid. Yield: 91%. ¹H NMR (300 MHz, DMSO-d₆) δ 8.49 (d, J = 4.4 Hz, 1H), 7.94–7.81 (m, 1H), 7.64–7.70 (m, 1H). ¹³C NMR (101 MHz, DMSO-d₆) δ 164.35, 159.27, 145.26, 138.65, 128.27, 125.59.

2-Pyridinecarbonyl chloride

The preparation of 2-pyridinecarbonyl chloride was performed according to a previously reported procedure (Aluri et al., 2011 ). 2-Pyridinecarboxylic acid (1.23 g, 10 mmol) and SOCl₂ (11.9 g, 100 mmol) were dissolved in 100 ml of dry toluene with 10 drops of DMF. The reaction mixture was refluxed at 383.15 K for 3 h. The reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. The resulting viscous residue was used directly in the next step without further purification.

3-Fluoropyridine-2-carbonyl chloride

The preparation of 3-fluoropyridine-2-carbonyl chloride was performed according to a previously reported procedure (Aluri et al., 2011). 3-Fluoropyridin-2-carboxylic acid (1.41 g, 10 mmol) and SOCl₂ (11.9 g, 100 mmol) were dissolved in 100 ml of dry toluene with 10 drops of DMF. The reaction mixture was refluxed at 383 K for 3 h. The reaction mixture was cooled to room temperature and the solvent was removed under reduced pressure. The resulting viscous residue was used directly in the next step without further purification.

2-Pyridinecarboxamide

The preparation of 2-pyridinecarboxamide was performed according to a previously reported procedure (Cai et al., 2014 ). 20 ml of NH₃/methanol solution (NH₃ ca 7 N in methanol solution) was slowly added to 2-pyridinecarbonyl chloride at 273 K under stirring. The resulting reaction mixture was allowed to warm to room temperature and stirred overnight. The solvent was removed under reduced pressure and the residue was purified by a silica column with an eluent of hexane/ethyl acetate (5/1) to afford the product. Yield: 88%. ¹H NMR (300 MHz, DMSO-d₆) δ 8.63 (d, J = 4.7 Hz, 1H), 8.11 (s, 1H), 8.06–7.94 (m, 2H), 7.64 (s, 1H), 7.63–7.55 (m, 1H).

3-Fluoropyridin-2-carboxamide

20 ml of NH₃/methanol (NH₃ ca 7 N in methanol solution) was added slowly to 3-fluoropyridin-2-carbonyl chloride at 273 K under stirring. The resulting reaction mixture was allowed to warm to room temperature and stirred overnight. The solvent was removed under reduced pressure and the residue was purified by silica column with an eluent of hexane/ethyl acetate (5/1) to afford the product. Yield 85%. ¹H NMR (300 MHz, CDCl₃) δ 8.34 (dt, J = 4.2, 1.4 Hz, 1H), 7.63 (s, 1H), 7.54–7.40 (m, 2H), 6.30 (s, 1H). ¹³C NMR (101 MHz, CDCl₃) δ 164.96, 164.91, 158.20, 144.12, 144.07, 137.26, 128.42, 128.37, 126.36, 126.16.

N-(Pyridine-2-carbonyl)pyridine-2-carboxamide (1)

2-Pyridinecarbonyl chloride (212.32 mg, 1.5 mmol) and 2-pyridinecarboxamide (170.98 mg, 1.4 mmol) were dissolved in toluene (20 ml). The resulting reaction mixture was refluxed at 383 K overnight. The solvent was removed under reduced pressure and the residue was purified by a silica column with an eluent of hexane/ethyl acetate (3/1) to afford the product. Yield: 91%. ¹H NMR (300 MHz, CDCl₃) δ 13.03 (s, 1H), 8.75 (ddd, J = 4.8, 1.7, 0.9 Hz, 2H), 8.35 (dt, J = 7.9, 1.1 Hz, 2H), 7.94 (td, J = 7.7, 1.7 Hz, 2H), 7.56 (ddd, J = 7.6, 4.8, 1.2 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃) δ 162.65, 149.15, 148.67, 137.73, 127.50, 123.49.

N-(3-Fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2)

3-Fluoropyridin-2-carboxamide (238.47 mg, 1.5 mmol) and 2-pyridinecarboxamide (170.98 mg, 1.4 mmol) were dissolved in toluene (20 ml). The resulting reaction mixture was refluxed at 383 K overnight. The solvent was removed under reduced pressure and the residue was purified by a silica column with an eluent of hexane/ethyl acetate (3/1) to afford the product. Yield: 89%. ¹H NMR (300 MHz, DMSO-d₆) δ 12.72 (s, 1H), 8.81 (ddd, J = 4.8, 1.6, 0.9 Hz, 1H), 8.66 (dt, J = 4.5, 1.4 Hz, 1H), 8.22 (dt, J = 7.8, 1.1 Hz, 1H), 8.13 (td, J = 7.7, 1.7 Hz, 1H), 8.02 (ddd, J = 11.3, 8.5, 1.2 Hz, 1H), 7.92–7.85 (m, 1H), 7.78 (ddd, J = 7.5, 4.8, 1.3 Hz, 1H). ¹³C NMR (101 MHz, DMSO-d₆) 161.88, 160.91, 159.53, 159.47, 158.21, 148.97, 148.16, 144.99, 144.93, 138.66, 135.97, 135.92, 130.72, 130.67, 128.35, 127.45, 127.26, 122.94.

3-Fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3)

3-Fluoropyridin-2-carboxamide (238.47 mg, 1.5 mmol) and 3-fluoropyridin-2-carbonyl chloride (196.04 mg, 1.4 mmol) were dissolved in toluene (20 ml). The resulting reaction mixture was refluxed at 383 K overnight. The solvent was removed under reduced pressure and the residue was purified by a silica column with an eluent of hexane/ethyl acetate (3/1) to afford the product. Yield: 80%. ¹H NMR (300 MHz, DMSO-d₆) δ 12.53 (s, 1H), 8.64 (dt, J = 4.5, 1.4 Hz, 2H), 8.02 (ddd, J = 11.3, 8.5, 1.2 Hz, 2H), 7.91–7.80 (m, 2H). ¹³C NMR (101 MHz, DMSO-d₆) 160.75, 159.72, 159.66, 158.05, 156.16, 144.97, 144.92, 136.12, 136.08, 130.62, 130.56, 127.36, 127.17.

Crystals of 1, 2, and 3, suitable for single-crystal X-ray diffraction analysis were prepared by slow evaporation of a 10 mg ml⁻¹ acetonitrile solution at room temperature. All crystals appeared as colourless blocks.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. For all structures, the imide N—H hydrogen atoms could be located from a difference electron-density Fourier map, and were further refined with isotropic temperature factors fixed at 1.2 times U_eq of the parent atoms.

Table 4
Experimental details

	1	2	3
Crystal data
Chemical formula	C₁₂H₉N₃O₂	C₁₂H₈FN₃O₂	C₁₂H₇F₂N₃O₂
M_r	227.22	245.21	263.21
Crystal system, space group	Orthorhombic, Pna2₁	Orthorhombic, Pna2₁	Monoclinic, I2/a
Temperature (K)	100	100	100
a, b, c (Å)	16.2689 (6), 12.8086 (7), 4.9983 (2)	16.6058 (10), 12.9096 (7), 4.9153 (3)	6.7062 (3), 14.1190 (5), 11.2074 (5)
α, β, γ (°)	90, 90, 90	90, 90, 90	90, 97.140 (4), 90
V (Å³)	1041.56 (8)	1053.71 (11)	1052.94 (8)
Z	4	4	4
Radiation type	Cu Kα	Cu Kα	Cu Kα
μ (mm⁻¹)	0.85	1.03	1.22
Crystal size (mm)	0.20 × 0.12 × 0.06	0.26 × 0.10 × 0.05	0.11 × 0.09 × 0.06

Data collection
Diffractometer	SuperNova, Dual, Cu at zero, Atlas	SuperNova, Dual, Cu at zero, Atlas	SuperNova, Dual, Cu at zero, Atlas
Absorption correction	Gaussian (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )	Gaussian (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )	Gaussian (CrysAlis PRO; Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.187, 0.563	0.983, 0.995	0.993, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	8626, 2028, 1831	5774, 1798, 1567	5200, 1083, 856
R_int	0.076	0.054	0.069
(sin θ/λ)_max (Å⁻¹)	0.627	0.629	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.170, 1.07	0.055, 0.152, 1.03	0.055, 0.161, 1.04
No. of reflections	2028	1798	1083
No. of parameters	157	176	88
No. of restraints	1	1	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.30	0.28, −0.28	0.29, −0.32
Absolute structure	Flack x determined using 673 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )	Flack x determined using 450 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)	–
Absolute structure parameter	0.0 (3)	0.2 (3)	–
Computer programs: CrysAlis PRO (Rigaku OD, 2015 $[Rigaku OD (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

For the structure of 2, the 3-fluoropyridine atom is disordered at both pyridine sites, showing final occupancy factors of 0.563 (8) and 0.437 (8), for the first and second site, respectively.

Supporting information

CCDC references: 2103652; 2103651; 2103650

Crystal structure: contains datablocks global, 1, 2, 3. DOI: https://doi.org/10.1107/S2056989021008562/vm2252sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989021008562/vm22521sup2.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989021008562/vm22522sup3.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989021008562/vm22523sup4.cml

checkCIF report

Computing details top

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

N-(Pyridine-2-carbonyl)pyridine-2-carboxamide (1) top

Crystal data top

C₁₂H₉N₃O₂	D_x = 1.449 Mg m⁻³
M_r = 227.22	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pna2₁	Cell parameters from 4719 reflections
a = 16.2689 (6) Å	θ = 4.2–74.0°
b = 12.8086 (7) Å	µ = 0.85 mm⁻¹
c = 4.9983 (2) Å	T = 100 K
V = 1041.56 (8) Å³	Block, clear colourless
Z = 4	0.20 × 0.12 × 0.06 mm
F(000) = 472

Data collection top

SuperNova, Dual, Cu at zero, Atlas diffractometer	2028 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	1831 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.076
Detector resolution: 10.4839 pixels mm^-1	θ_max = 75.3°, θ_min = 4.4°
ω scans	h = −14→20
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2015)	k = −15→15
T_min = 0.187, T_max = 0.563	l = −5→6
8626 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.060	w = 1/[σ²(F_o²) + (0.1236P)² + 0.0215P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.170	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.32 e Å⁻³
2028 reflections	Δρ_min = −0.30 e Å⁻³
157 parameters	Absolute structure: Flack x determined using 673 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.0 (3)
Primary atom site location: structure-invariant direct methods

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.29400 (14)	0.3937 (2)	0.2999 (6)	0.0362 (7)
O2	0.22855 (16)	0.2512 (2)	0.7000 (6)	0.0343 (7)
N1	0.10762 (18)	0.4562 (3)	−0.0277 (7)	0.0301 (7)
N2	0.16131 (17)	0.3339 (2)	0.3528 (7)	0.0299 (7)
N3	0.01890 (19)	0.2587 (3)	0.5153 (7)	0.0335 (8)
C1	0.1883 (2)	0.4642 (3)	0.0217 (8)	0.0288 (8)
C2	0.2393 (2)	0.5328 (3)	−0.1112 (8)	0.0322 (8)
H2A	0.296091	0.536690	−0.068626	0.039*
C3	0.2060 (2)	0.5956 (3)	−0.3071 (9)	0.0372 (9)
H3	0.239464	0.643907	−0.401515	0.045*
C4	0.1232 (2)	0.5872 (3)	−0.3640 (9)	0.0372 (9)
H4	0.098806	0.628601	−0.500275	0.045*
C5	0.0767 (2)	0.5170 (3)	−0.2176 (8)	0.0344 (8)
H5	0.019566	0.512061	−0.255151	0.041*
C6	0.2213 (2)	0.3943 (3)	0.2372 (8)	0.0279 (8)
C7	0.1662 (2)	0.2696 (3)	0.5753 (8)	0.0284 (8)
C8	0.0840 (2)	0.2245 (3)	0.6517 (8)	0.0290 (8)
C9	−0.0551 (2)	0.2220 (3)	0.5853 (10)	0.0361 (9)
H9	−0.101987	0.245492	0.489110	0.043*
C10	−0.0664 (2)	0.1513 (3)	0.7923 (9)	0.0371 (9)
H10	−0.119977	0.127904	0.838484	0.045*
C11	0.0010 (3)	0.1157 (4)	0.9290 (9)	0.0410 (10)
H11	−0.004963	0.066767	1.070577	0.049*
C12	0.0785 (2)	0.1526 (3)	0.8565 (9)	0.0368 (9)
H12	0.126414	0.128826	0.946242	0.044*
H2	0.110 (3)	0.341 (4)	0.286 (12)	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0224 (11)	0.0457 (15)	0.0404 (17)	0.0004 (11)	−0.0002 (11)	0.0017 (13)
O2	0.0291 (12)	0.0387 (14)	0.0352 (15)	0.0032 (10)	−0.0065 (10)	0.0041 (12)
N1	0.0235 (13)	0.0340 (15)	0.0328 (17)	0.0006 (11)	−0.0019 (12)	−0.0011 (13)
N2	0.0235 (13)	0.0350 (15)	0.0312 (17)	0.0004 (11)	−0.0032 (12)	0.0022 (13)
N3	0.0286 (14)	0.0353 (16)	0.0365 (19)	−0.0011 (11)	0.0011 (13)	0.0023 (15)
C1	0.0270 (15)	0.0290 (16)	0.0302 (19)	0.0025 (13)	0.0024 (14)	−0.0040 (14)
C2	0.0270 (16)	0.0333 (18)	0.036 (2)	−0.0007 (13)	0.0064 (15)	−0.0024 (16)
C3	0.0379 (19)	0.0334 (18)	0.040 (2)	0.0007 (15)	0.0100 (17)	0.0029 (17)
C4	0.0424 (19)	0.0361 (18)	0.033 (2)	0.0081 (17)	0.0016 (17)	−0.0015 (16)
C5	0.0308 (16)	0.0393 (18)	0.033 (2)	0.0036 (15)	0.0007 (16)	−0.0005 (17)
C6	0.0214 (15)	0.0318 (17)	0.0304 (19)	0.0016 (12)	−0.0011 (13)	−0.0024 (15)
C7	0.0303 (16)	0.0281 (16)	0.0269 (18)	0.0034 (13)	−0.0011 (14)	0.0002 (14)
C8	0.0283 (16)	0.0296 (17)	0.0292 (19)	0.0010 (13)	−0.0011 (13)	−0.0032 (15)
C9	0.0262 (16)	0.0390 (19)	0.043 (2)	−0.0019 (15)	0.0023 (16)	0.0022 (16)
C10	0.0350 (17)	0.0367 (18)	0.040 (2)	−0.0063 (15)	0.0072 (16)	−0.0006 (17)
C11	0.043 (2)	0.041 (2)	0.038 (3)	−0.0062 (16)	0.0010 (18)	0.0060 (18)
C12	0.0346 (17)	0.041 (2)	0.035 (2)	−0.0004 (15)	−0.0030 (15)	0.0069 (17)

Geometric parameters (Å, º) top

O1—C6	1.224 (4)	C3—C4	1.380 (6)
O2—C7	1.214 (4)	C4—H4	0.9500
N1—C1	1.339 (4)	C4—C5	1.385 (6)
N1—C5	1.327 (5)	C5—H5	0.9500
N2—C6	1.373 (5)	C7—C8	1.506 (5)
N2—C7	1.385 (5)	C8—C12	1.380 (6)
N2—H2	0.90 (5)	C9—H9	0.9500
N3—C8	1.333 (5)	C9—C10	1.387 (6)
N3—C9	1.339 (5)	C10—H10	0.9500
C1—C2	1.379 (5)	C10—C11	1.370 (6)
C1—C6	1.499 (5)	C11—H11	0.9500
C2—H2A	0.9500	C11—C12	1.394 (6)
C2—C3	1.378 (6)	C12—H12	0.9500
C3—H3	0.9500

C5—N1—C1	117.3 (3)	O1—C6—C1	122.3 (3)
C6—N2—C7	129.2 (3)	N2—C6—C1	112.6 (3)
C6—N2—H2	116 (3)	O2—C7—N2	125.1 (3)
C7—N2—H2	114 (3)	O2—C7—C8	122.5 (3)
C8—N3—C9	117.8 (4)	N2—C7—C8	112.4 (3)
N1—C1—C2	123.3 (4)	N3—C8—C7	116.7 (3)
N1—C1—C6	115.9 (3)	N3—C8—C12	123.1 (4)
C2—C1—C6	120.7 (3)	C12—C8—C7	120.1 (3)
C1—C2—H2A	120.7	N3—C9—H9	118.6
C3—C2—C1	118.6 (3)	N3—C9—C10	122.9 (4)
C3—C2—H2A	120.7	C10—C9—H9	118.6
C2—C3—H3	120.5	C9—C10—H10	120.5
C2—C3—C4	119.0 (4)	C11—C10—C9	118.9 (4)
C4—C3—H3	120.5	C11—C10—H10	120.5
C3—C4—H4	120.8	C10—C11—H11	120.6
C3—C4—C5	118.3 (4)	C10—C11—C12	118.7 (4)
C5—C4—H4	120.8	C12—C11—H11	120.6
N1—C5—C4	123.5 (4)	C8—C12—C11	118.6 (4)
N1—C5—H5	118.3	C8—C12—H12	120.7
C4—C5—H5	118.3	C11—C12—H12	120.7
O1—C6—N2	125.1 (3)

O2—C7—C8—N3	173.6 (4)	C3—C4—C5—N1	−1.0 (6)
O2—C7—C8—C12	−5.5 (5)	C5—N1—C1—C2	1.0 (6)
N1—C1—C2—C3	−0.8 (6)	C5—N1—C1—C6	−179.9 (3)
N1—C1—C6—O1	179.4 (4)	C6—N2—C7—O2	−4.7 (6)
N1—C1—C6—N2	−1.1 (5)	C6—N2—C7—C8	174.7 (3)
N2—C7—C8—N3	−5.8 (5)	C6—C1—C2—C3	−179.8 (3)
N2—C7—C8—C12	175.2 (4)	C7—N2—C6—O1	7.6 (6)
N3—C8—C12—C11	−1.6 (6)	C7—N2—C6—C1	−171.9 (3)
N3—C9—C10—C11	−1.1 (7)	C7—C8—C12—C11	177.4 (4)
C1—N1—C5—C4	−0.1 (6)	C8—N3—C9—C10	0.3 (6)
C1—C2—C3—C4	−0.3 (6)	C9—N3—C8—C7	−178.0 (3)
C2—C1—C6—O1	−1.5 (5)	C9—N3—C8—C12	1.0 (6)
C2—C1—C6—N2	178.0 (3)	C9—C10—C11—C12	0.5 (7)
C2—C3—C4—C5	1.1 (6)	C10—C11—C12—C8	0.7 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.90 (5)	2.15 (6)	2.614 (5)	111 (4)
N2—H2···N3	0.90 (5)	2.15 (5)	2.637 (4)	113 (5)
C3—H3···O2ⁱ	0.95	2.48	3.343 (5)	152
C5—H5···N1ⁱⁱ	0.95	2.51	3.393 (5)	154

Symmetry codes: (i) −x+1/2, y+1/2, z−3/2; (ii) −x, −y+1, z−1/2.

N-(3-Fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2) top

Crystal data top

C₁₂H₈FN₃O₂	D_x = 1.546 Mg m⁻³
M_r = 245.21	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pna2₁	Cell parameters from 2360 reflections
a = 16.6058 (10) Å	θ = 3.4–74.8°
b = 12.9096 (7) Å	µ = 1.03 mm⁻¹
c = 4.9153 (3) Å	T = 100 K
V = 1053.71 (11) Å³	Block, clear colourless
Z = 4	0.26 × 0.10 × 0.05 mm
F(000) = 504

Data collection top

SuperNova, Dual, Cu at zero, Atlas diffractometer	1798 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	1567 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.054
Detector resolution: 10.4839 pixels mm^-1	θ_max = 75.9°, θ_min = 5.3°
ω scans	h = −19→20
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2015)	k = −15→16
T_min = 0.983, T_max = 0.995	l = −6→5
5774 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.055	w = 1/[σ²(F_o²) + (0.0898P)² + 0.4172P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.152	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.28 e Å⁻³
1798 reflections	Δρ_min = −0.28 e Å⁻³
176 parameters	Absolute structure: Flack x determined using 450 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.2 (3)
Primary atom site location: structure-invariant direct methods

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O2	0.27904 (19)	0.7427 (2)	0.1952 (8)	0.0338 (8)
O1	0.21184 (17)	0.8809 (3)	0.5995 (8)	0.0359 (8)
N3	0.4847 (2)	0.7588 (3)	0.3876 (9)	0.0309 (9)
N2	0.3438 (2)	0.8296 (3)	0.5407 (9)	0.0271 (8)
N1	0.3932 (2)	0.9540 (3)	0.9257 (8)	0.0269 (8)
C12	0.4327 (3)	0.6517 (4)	0.0372 (11)	0.0407 (12)
H12	0.387317	0.626086	−0.059309	0.049*	0.563 (8)
C8	0.4221 (3)	0.7223 (3)	0.2426 (10)	0.0267 (9)
C9	0.5586 (3)	0.7247 (3)	0.3242 (12)	0.0358 (11)
H9	0.603043	0.749297	0.427390	0.043*
C10	0.5730 (3)	0.6555 (4)	0.1156 (11)	0.0393 (11)
H10	0.626396	0.634525	0.073279	0.047*
C11	0.5087 (3)	0.6176 (4)	−0.0299 (12)	0.0433 (13)
H11	0.516473	0.569153	−0.172922	0.052*
C7	0.3403 (2)	0.7643 (3)	0.3213 (10)	0.0270 (9)
C6	0.2827 (2)	0.8864 (3)	0.6609 (9)	0.0257 (9)
C1	0.3139 (2)	0.9587 (3)	0.8767 (10)	0.0247 (9)
C2	0.2642 (3)	1.0262 (3)	1.0150 (10)	0.0300 (10)
H2A	0.208315	1.028822	0.973723	0.036*	0.437 (8)
C3	0.2959 (3)	1.0902 (3)	1.2140 (12)	0.0351 (11)
H3	0.262391	1.137086	1.310847	0.042*
C4	0.3766 (3)	1.0842 (3)	1.2677 (11)	0.0341 (10)
H4	0.400053	1.126025	1.405499	0.041*
C5	0.4234 (3)	1.0164 (3)	1.1188 (10)	0.0302 (9)
H5	0.479609	1.013741	1.154679	0.036*
F1B	0.3801 (4)	0.6170 (5)	−0.1240 (16)	0.046 (2)	0.437 (8)
F1A	0.1855 (3)	1.0352 (3)	0.9733 (12)	0.0368 (16)	0.563 (8)
H2	0.395 (3)	0.837 (4)	0.611 (14)	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0306 (15)	0.0302 (14)	0.0407 (19)	−0.0041 (12)	−0.0077 (16)	−0.0028 (15)
O1	0.0223 (15)	0.0426 (17)	0.043 (2)	−0.0018 (12)	−0.0037 (15)	0.0012 (16)
N3	0.0279 (18)	0.0288 (17)	0.036 (2)	−0.0004 (13)	−0.0008 (17)	−0.0003 (17)
N2	0.0239 (17)	0.0283 (17)	0.029 (2)	−0.0004 (13)	−0.0022 (15)	−0.0039 (15)
N1	0.0249 (17)	0.0281 (16)	0.028 (2)	−0.0030 (13)	−0.0019 (15)	−0.0021 (15)
C12	0.055 (3)	0.034 (2)	0.033 (3)	0.006 (2)	−0.009 (3)	−0.003 (2)
C8	0.029 (2)	0.0221 (16)	0.029 (2)	−0.0005 (14)	−0.0027 (18)	0.0019 (17)
C9	0.033 (2)	0.028 (2)	0.047 (3)	0.0026 (17)	0.003 (2)	−0.001 (2)
C10	0.045 (2)	0.030 (2)	0.043 (3)	0.0102 (19)	0.012 (2)	0.005 (2)
C11	0.061 (3)	0.036 (2)	0.033 (3)	0.010 (2)	0.004 (3)	−0.004 (2)
C7	0.031 (2)	0.0227 (18)	0.027 (2)	−0.0036 (15)	−0.003 (2)	0.0033 (17)
C6	0.0198 (18)	0.0282 (18)	0.029 (3)	−0.0029 (15)	−0.0016 (17)	0.0038 (19)
C1	0.0218 (18)	0.0222 (16)	0.030 (2)	−0.0014 (14)	−0.0005 (19)	0.0011 (16)
C2	0.028 (2)	0.0232 (18)	0.039 (3)	0.0010 (15)	0.006 (2)	0.0045 (19)
C3	0.043 (3)	0.0250 (19)	0.037 (3)	−0.0003 (17)	0.009 (2)	−0.003 (2)
C4	0.044 (3)	0.0276 (19)	0.030 (2)	−0.0053 (18)	0.005 (2)	−0.002 (2)
C5	0.030 (2)	0.0301 (19)	0.031 (2)	−0.0040 (16)	−0.001 (2)	−0.002 (2)
F1B	0.036 (4)	0.053 (4)	0.050 (5)	−0.002 (3)	−0.012 (3)	−0.025 (4)
F1A	0.020 (2)	0.028 (2)	0.062 (4)	0.0007 (16)	0.002 (2)	0.001 (2)

Geometric parameters (Å, º) top

O2—C7	1.224 (5)	C9—C10	1.381 (7)
O1—C6	1.217 (5)	C10—H10	0.9500
N3—C8	1.346 (6)	C10—C11	1.376 (8)
N3—C9	1.340 (6)	C11—H11	0.9500
N2—C7	1.370 (6)	C6—C1	1.505 (6)
N2—C6	1.384 (6)	C1—C2	1.380 (6)
N2—H2	0.92 (6)	C2—H2A	0.9500
N1—C1	1.341 (5)	C2—C3	1.384 (7)
N1—C5	1.342 (6)	C2—F1A	1.327 (6)
C12—H12	0.9500	C3—H3	0.9500
C12—C8	1.372 (7)	C3—C4	1.369 (7)
C12—C11	1.376 (7)	C4—H4	0.9500
C12—F1B	1.262 (8)	C4—C5	1.381 (6)
C8—C7	1.511 (6)	C5—H5	0.9500
C9—H9	0.9500

C9—N3—C8	118.0 (4)	O2—C7—C8	122.4 (4)
C7—N2—C6	129.1 (4)	N2—C7—C8	112.6 (3)
C7—N2—H2	113 (4)	O1—C6—N2	124.9 (4)
C6—N2—H2	118 (4)	O1—C6—C1	122.9 (4)
C1—N1—C5	117.9 (4)	N2—C6—C1	112.2 (3)
C8—C12—H12	119.8	N1—C1—C6	115.9 (3)
C8—C12—C11	120.5 (5)	N1—C1—C2	121.9 (4)
C11—C12—H12	119.8	C2—C1—C6	122.2 (4)
F1B—C12—C8	127.5 (6)	C1—C2—H2A	120.1
F1B—C12—C11	111.7 (6)	C1—C2—C3	119.8 (4)
N3—C8—C12	121.5 (4)	C3—C2—H2A	120.1
N3—C8—C7	115.7 (4)	F1A—C2—C1	124.6 (5)
C12—C8—C7	122.8 (4)	F1A—C2—C3	115.6 (4)
N3—C9—H9	118.5	C2—C3—H3	120.8
N3—C9—C10	122.9 (5)	C4—C3—C2	118.4 (4)
C10—C9—H9	118.5	C4—C3—H3	120.8
C9—C10—H10	120.6	C3—C4—H4	120.5
C11—C10—C9	118.8 (5)	C3—C4—C5	119.0 (4)
C11—C10—H10	120.6	C5—C4—H4	120.5
C12—C11—H11	120.9	N1—C5—C4	123.0 (4)
C10—C11—C12	118.3 (5)	N1—C5—H5	118.5
C10—C11—H11	120.9	C4—C5—H5	118.5
O2—C7—N2	125.0 (4)

O1—C6—C1—N1	178.5 (4)	C11—C12—C8—C7	178.6 (4)
O1—C6—C1—C2	−1.9 (7)	C7—N2—C6—O1	6.0 (7)
N3—C8—C7—O2	175.2 (4)	C7—N2—C6—C1	−172.9 (4)
N3—C8—C7—N2	−3.2 (5)	C6—N2—C7—O2	−2.1 (7)
N3—C9—C10—C11	−1.7 (8)	C6—N2—C7—C8	176.3 (4)
N2—C6—C1—N1	−2.6 (5)	C6—C1—C2—C3	179.2 (4)
N2—C6—C1—C2	177.0 (4)	C6—C1—C2—F1A	−0.4 (7)
N1—C1—C2—C3	−1.2 (7)	C1—N1—C5—C4	0.2 (6)
N1—C1—C2—F1A	179.2 (4)	C1—C2—C3—C4	0.0 (7)
C12—C8—C7—O2	−4.7 (6)	C2—C3—C4—C5	1.2 (7)
C12—C8—C7—N2	176.8 (4)	C3—C4—C5—N1	−1.3 (7)
C8—N3—C9—C10	1.0 (7)	C5—N1—C1—C6	−179.3 (4)
C8—C12—C11—C10	0.6 (8)	C5—N1—C1—C2	1.1 (6)
C9—N3—C8—C12	0.6 (7)	F1B—C12—C8—N3	−175.0 (6)
C9—N3—C8—C7	−179.4 (4)	F1B—C12—C8—C7	5.0 (9)
C9—C10—C11—C12	0.9 (7)	F1B—C12—C11—C10	175.1 (6)
C11—C12—C8—N3	−1.3 (7)	F1A—C2—C3—C4	179.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.92 (5)	2.16 (6)	2.614 (6)	109 (4)
N2—H2···N3	0.92 (5)	2.11 (6)	2.622 (5)	114 (5)
C3—H3···O2ⁱ	0.95	2.43	3.320 (6)	156
C3—H3···F1Bⁱ	0.95	2.40	3.049 (8)	125
C5—H5···N1ⁱⁱ	0.95	2.53	3.420 (6)	156
C10—H10···F1Aⁱⁱⁱ	0.95	2.45	3.169 (7)	132

Symmetry codes: (i) −x+1/2, y+1/2, z+3/2; (ii) −x+1, −y+2, z+1/2; (iii) x+1/2, −y+3/2, z−1.

3-Fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3) top

Crystal data top

C₁₂H₇F₂N₃O₂	F(000) = 536
M_r = 263.21	D_x = 1.660 Mg m⁻³
Monoclinic, I2/a	Cu Kα radiation, λ = 1.54184 Å
a = 6.7062 (3) Å	Cell parameters from 1899 reflections
b = 14.1190 (5) Å	θ = 5.0–74.9°
c = 11.2074 (5) Å	µ = 1.22 mm⁻¹
β = 97.140 (4)°	T = 100 K
V = 1052.94 (8) Å³	Block, clear colourless
Z = 4	0.11 × 0.09 × 0.06 mm

Data collection top

SuperNova, Dual, Cu at zero, Atlas diffractometer	1083 independent reflections
Radiation source: micro-focus sealed X-ray tube, SuperNova (Cu) X-ray Source	856 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.069
Detector resolution: 10.4839 pixels mm^-1	θ_max = 75.4°, θ_min = 5.1°
ω scans	h = −7→8
Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2015)	k = −17→17
T_min = 0.993, T_max = 0.996	l = −14→13
5200 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.161	w = 1/[σ²(F_o²) + (0.0954P)² + 0.7955P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1083 reflections	Δρ_max = 0.29 e Å⁻³
88 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
F1	0.1012 (3)	0.49942 (9)	0.14190 (14)	0.0349 (5)
O1	0.1649 (3)	0.53996 (11)	0.37977 (16)	0.0296 (5)
N1	0.0596 (3)	0.29674 (13)	0.33292 (17)	0.0204 (5)
N2	0.250000	0.41071 (19)	0.500000	0.0218 (6)
C2	0.0612 (4)	0.41086 (16)	0.1771 (2)	0.0245 (6)
C1	0.0945 (3)	0.38567 (15)	0.2979 (2)	0.0217 (5)
C5	−0.0104 (3)	0.23375 (15)	0.2494 (2)	0.0208 (5)
H5	−0.037842	0.171355	0.274533	0.025*
C4	−0.0453 (3)	0.25475 (16)	0.1273 (2)	0.0233 (5)
H4	−0.094044	0.207588	0.070604	0.028*
C3	−0.0075 (4)	0.34557 (16)	0.0902 (2)	0.0247 (6)
H3	−0.028177	0.362470	0.007558	0.030*
C6	0.1711 (3)	0.45473 (15)	0.3944 (2)	0.0213 (5)
H2	0.250000	0.351 (3)	0.500000	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0551 (11)	0.0191 (7)	0.0292 (9)	−0.0062 (6)	−0.0002 (7)	0.0071 (6)
O1	0.0404 (10)	0.0157 (8)	0.0316 (10)	0.0016 (7)	0.0006 (8)	0.0023 (7)
N1	0.0190 (9)	0.0171 (9)	0.0254 (10)	0.0017 (7)	0.0038 (7)	0.0014 (7)
N2	0.0254 (13)	0.0141 (12)	0.0262 (15)	0.000	0.0042 (11)	0.000
C2	0.0262 (11)	0.0165 (10)	0.0309 (13)	0.0012 (9)	0.0042 (10)	0.0048 (9)
C1	0.0203 (11)	0.0167 (11)	0.0278 (12)	0.0022 (8)	0.0023 (9)	0.0021 (9)
C5	0.0188 (10)	0.0174 (10)	0.0270 (12)	0.0007 (8)	0.0058 (9)	0.0008 (8)
C4	0.0213 (11)	0.0223 (11)	0.0258 (12)	0.0025 (8)	0.0014 (9)	−0.0022 (9)
C3	0.0276 (11)	0.0239 (12)	0.0222 (12)	0.0039 (9)	0.0014 (10)	0.0028 (9)
C6	0.0222 (11)	0.0162 (10)	0.0259 (12)	0.0014 (8)	0.0051 (9)	0.0009 (9)

Geometric parameters (Å, º) top

F1—C2	1.348 (2)	C2—C3	1.378 (3)
O1—C6	1.214 (3)	C1—C6	1.498 (3)
N1—C1	1.344 (3)	C5—H5	0.9500
N1—C5	1.334 (3)	C5—C4	1.391 (3)
N2—C6ⁱ	1.383 (3)	C4—H4	0.9500
N2—C6	1.383 (3)	C4—C3	1.381 (3)
N2—H2	0.85 (4)	C3—H3	0.9500
C2—C1	1.391 (3)

C5—N1—C1	118.5 (2)	N1—C5—C4	123.4 (2)
C6ⁱ—N2—C6	126.6 (3)	C4—C5—H5	118.3
C6ⁱ—N2—H2	116.71 (13)	C5—C4—H4	120.7
C6—N2—H2	116.71 (13)	C3—C4—C5	118.6 (2)
F1—C2—C1	120.5 (2)	C3—C4—H4	120.7
F1—C2—C3	118.4 (2)	C2—C3—C4	117.8 (2)
C3—C2—C1	121.1 (2)	C2—C3—H3	121.1
N1—C1—C2	120.7 (2)	C4—C3—H3	121.1
N1—C1—C6	117.0 (2)	O1—C6—N2	124.3 (2)
C2—C1—C6	122.3 (2)	O1—C6—C1	123.0 (2)
N1—C5—H5	118.3	N2—C6—C1	112.68 (19)

F1—C2—C1—N1	−178.3 (2)	C1—C2—C3—C4	1.0 (4)
F1—C2—C1—C6	1.3 (4)	C5—N1—C1—C2	−1.0 (3)
F1—C2—C3—C4	179.1 (2)	C5—N1—C1—C6	179.41 (19)
N1—C1—C6—O1	−162.6 (2)	C5—C4—C3—C2	−0.6 (3)
N1—C1—C6—N2	17.9 (3)	C3—C2—C1—N1	−0.2 (4)
N1—C5—C4—C3	−0.6 (3)	C3—C2—C1—C6	179.3 (2)
C2—C1—C6—O1	17.8 (4)	C6ⁱ—N2—C6—O1	1.68 (18)
C2—C1—C6—N2	−161.7 (2)	C6ⁱ—N2—C6—C1	−178.8 (2)
C1—N1—C5—C4	1.4 (3)

Symmetry code: (i) −x+1/2, y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1	0.84 (4)	2.27 (2)	2.671 (2)	110 (1)
N2—H2···N1ⁱ	0.84 (4)	2.27 (2)	2.671 (2)	110 (1)
C4—H4···O1ⁱⁱ	0.95	2.49	3.135 (3)	125
C5—H5···O1ⁱⁱ	0.95	2.61	3.207 (3)	122
C3—H3···F1ⁱⁱⁱ	0.95	2.58	3.398 (3)	145
C5—H5···F1ⁱⁱ	0.95	2.66	3.604 (3)	176

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

Funding information

Funding for this research was provided by: Fonds Wetenschappelijk Onderzoek (grant No. AUGE/11/029); Bijzonder Onderzoeksfonds UGent (grant No. 01N03217); Bijzonder Onderzoeksfonds UGent (grant No. 01SC1717); China Scholarship Council (scholarship No. 201506780014).

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Volume 77| Part 9| September 2021| Pages 958-964

https://doi.org/10.1107/S2056989021008562

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of three N-(pyridine-2-carbon­yl)pyridine-2-carboxamides as potential ligands for supra­molecular chemistry

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Funding information

References

research communications

Crystal structures of three N-(pyridine-2-carbonyl)pyridine-2-carboxamides as potential ligands for supramolecular chemistry

3. Supramolecular features