The crystal structures of three N-(pyridine-2-carbonyl)pyridine-2-carboxamide ligands, with or without F atoms on the 3-position of the pyridine ring, with potential use in supramolecular chemistry are reported.
Keywords: supramolecular chemistry, N-(pyridine-2-carbonyl)pyridine-2-carboxamide, fluorine moieties, crystal structure
Abstract
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.
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) (R 1 = H, R 2 = H), N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2) (R 1 = F, R 2 = H) and 3-fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3) (R 1 = F, R 2 = 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.
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. 1 ▸ a).
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. 1 ▸ b).
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. 1 ▸ c).
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) 
− x, + y, −
+ 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, − + 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) − x, + y, + 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, + z]. Additionally, C—H⋯F hydrogen bonds are observed with the two disordered fluorine moieties [C3—H3⋯F1B
i = 2.40 Å; C10—H10⋯F1A
iii = 2.45 Å; symmetry code: (iii) + x, − 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⋯F1B i | 0.95 | 2.40 | 3.049 (8) | 125 |
| C5—H5⋯N1ii | 0.95 | 2.53 | 3.420 (6) | 156 |
| C10—H10⋯F1A iii | 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( − x, − y, − 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, − + y, − 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) -x, -y+1, -z.
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.
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)°.
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-d 6) 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-d 6) 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-d 6) 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-d 6) 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-d 6) 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-d 6) 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-d 6) 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.
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, P n a21 | Orthorhombic, P n a21 | 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 ▸) | Gaussian (CrysAlis PRO; Rigaku OD, 2015 ▸) | Gaussian (CrysAlis PRO; Rigaku OD, 2015 ▸) |
| Tmin, Tmax | 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(F 2)], wR(F 2), 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 |
| Δρmax, Δρmin (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) | – |
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.
Supplementary Material
Crystal structure: contains datablock(s) global, 1, 2, 3. DOI: 10.1107/S2056989021008562/vm2252sup1.cif
Supporting information file. DOI: 10.1107/S2056989021008562/vm22521sup2.cml
Supporting information file. DOI: 10.1107/S2056989021008562/vm22522sup3.cml
Supporting information file. DOI: 10.1107/S2056989021008562/vm22523sup4.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
N-(Pyridine-2-carbonyl)pyridine-2-carboxamide (1) . Crystal data
| C12H9N3O2 | Dx = 1.449 Mg m−3 |
| Mr = 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 |
N-(Pyridine-2-carbonyl)pyridine-2-carboxamide (1) . Data collection
| 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 | Rint = 0.076 |
| Detector resolution: 10.4839 pixels mm-1 | θmax = 75.3°, θmin = 4.4° |
| ω scans | h = −14→20 |
| Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2015) | k = −15→15 |
| Tmin = 0.187, Tmax = 0.563 | l = −5→6 |
| 8626 measured reflections |
N-(Pyridine-2-carbonyl)pyridine-2-carboxamide (1) . Refinement
| 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(Fo2) + (0.1236P)2 + 0.0215P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.170 | (Δ/σ)max < 0.001 |
| S = 1.07 | Δρmax = 0.32 e Å−3 |
| 2028 reflections | Δρmin = −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 |
N-(Pyridine-2-carbonyl)pyridine-2-carboxamide (1) . Special details
| 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. |
N-(Pyridine-2-carbonyl)pyridine-2-carboxamide (1) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| 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* |
N-(Pyridine-2-carbonyl)pyridine-2-carboxamide (1) . Atomic displacement parameters (Å2)
| 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) |
N-(Pyridine-2-carbonyl)pyridine-2-carboxamide (1) . Geometric parameters (Å, º)
| 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) |
N-(Pyridine-2-carbonyl)pyridine-2-carboxamide (1) . Hydrogen-bond geometry (Å, º)
| 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) . Crystal data
| C12H8FN3O2 | Dx = 1.546 Mg m−3 |
| Mr = 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 |
N-(3-Fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2) . Data collection
| 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 | Rint = 0.054 |
| Detector resolution: 10.4839 pixels mm-1 | θmax = 75.9°, θmin = 5.3° |
| ω scans | h = −19→20 |
| Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2015) | k = −15→16 |
| Tmin = 0.983, Tmax = 0.995 | l = −6→5 |
| 5774 measured reflections |
N-(3-Fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2) . Refinement
| 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(Fo2) + (0.0898P)2 + 0.4172P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.152 | (Δ/σ)max < 0.001 |
| S = 1.03 | Δρmax = 0.28 e Å−3 |
| 1798 reflections | Δρmin = −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 |
N-(3-Fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2) . Special details
| 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. |
N-(3-Fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | 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* |
N-(3-Fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2) . Atomic displacement parameters (Å2)
| 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) |
N-(3-Fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2) . Geometric parameters (Å, º)
| 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) |
N-(3-Fluoropyridine-2-carbonyl)pyridine-2-carboxamide (2) . Hydrogen-bond geometry (Å, º)
| 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) . Crystal data
| C12H7F2N3O2 | F(000) = 536 |
| Mr = 263.21 | Dx = 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 |
3-Fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3) . Data collection
| 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 | Rint = 0.069 |
| Detector resolution: 10.4839 pixels mm-1 | θmax = 75.4°, θmin = 5.1° |
| ω scans | h = −7→8 |
| Absorption correction: gaussian (CrysAlisPro; Rigaku OD, 2015) | k = −17→17 |
| Tmin = 0.993, Tmax = 0.996 | l = −14→13 |
| 5200 measured reflections |
3-Fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3) . Refinement
| 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(Fo2) + (0.0954P)2 + 0.7955P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max < 0.001 |
| 1083 reflections | Δρmax = 0.29 e Å−3 |
| 88 parameters | Δρmin = −0.32 e Å−3 |
| 0 restraints |
3-Fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3) . Special details
| 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. |
3-Fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3) . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| 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* |
3-Fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3) . Atomic displacement parameters (Å2)
| 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) |
3-Fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3) . Geometric parameters (Å, º)
| 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.
3-Fluoro-N-(3-fluoropyridine-2-carbonyl)pyridine-2-carboxamide (3) . Hydrogen-bond geometry (Å, º)
| 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 Statement
This work was funded by Fonds Wetenschappelijk Onderzoek grant AUGE/11/029; Bijzonder Onderzoeksfonds UGent grant 01N03217; Bijzonder Onderzoeksfonds UGent grant 01SC1717; China Scholarship Council grant 201506780014.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) global, 1, 2, 3. DOI: 10.1107/S2056989021008562/vm2252sup1.cif
Supporting information file. DOI: 10.1107/S2056989021008562/vm22521sup2.cml
Supporting information file. DOI: 10.1107/S2056989021008562/vm22522sup3.cml
Supporting information file. DOI: 10.1107/S2056989021008562/vm22523sup4.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report