The title molecules, HL1 and HL2, differ in their conformation with the pyridine ring being inclined to the pyrazine ring by 61.34 (6) and 84.33 (12)°, respectively. The crystal packing is also slightly different, with molecules of HL1 linked by pairs of N—H⋯N hydrogen bonds, forming inversion dimers, while for HL2 molecules are linked by N—H⋯N and C—H⋯N hydrogen bonds, forming chains along [010].
Keywords: crystal structure, pyrazine, pyridine, carboxamide
Abstract
The title compounds, C11H10N4O (HL1) and C11H10N4O (HL2), are pyridine 2-ylmethyl and 4-ylmethyl derivatives, respectively, of pyrazine-2-carboxamide. HL1 was measured at 153 K and crystallized in the monoclinic space group P21/c with Z = 4. There has been a report of the same structure measured at room temperature but assumed to crystallize in the triclinic space group P-1 with Z = 4 [Sasan et al. (2008 ▸). Monatsh. Chem. 139, 773–780]. In HL1, the pyridine ring is inclined to the pyrazine ring by 61.34 (6)°, while in HL2 this dihedral angle is 84.33 (12)°. In both molecules, there is a short N—H⋯N interaction involving the pyrazine carboxamide unit. In the crystal of HL1, molecules are linked by N—H⋯N hydrogen bonds, forming inversion dimers with an R 2 2(10) ring motif. The dimers are linked via bifurcated-acceptor C—H⋯O hydrogen bonds, forming sheets lying parallel to (102). The sheets are linked via C—H⋯N hydrogen bonds, forming a three-dimensional structure. In the crystal of HL2, molecules are linked by N—H⋯N and C—H⋯N hydrogen bonds to form chains propagating along [010]. The chains are linked via C—H⋯O hydrogen bonds, forming sheets lying parallel to (100). Within the sheets there are π–π interactions involving neighbouring pyrazine rings [inter-centroid distance = 3.711 (15) Å]. Adjacent sheets are linked via parallel slipped π–π interactions involving inversion-related pyridine rings [inter-centroid distance = 3.6395 (17) Å], forming a three-dimensional structure.
Chemical context
The title compounds form part of a series of ligands synthesized in order to study their coordination chemistry with 3d transition metals (Cati, 2002 ▸).
They have been used to construct coordination polymers and multi-nuclear compounds, and to study their magnetic properties (Cati et al., 2004 ▸). Similar ligands have been synthesized by other groups who have studied, for example, the magnetic properties of some copper(II) complexes (Hausmann et al., 2003 ▸; Kingele et al., 2007 ▸).
Structural commentary
The molecular structure of ligand HL1 is illustrated in Fig. 1 ▸. HL1 was measured at 153 K and crystallized in the monoclinic space group P21/c with Z = 4. The β angle is 91.461 (11)° and the systematic absences, the Ri
nt value (0.0348) and the successful refinement {R1 [I > 2σ(I)] = 0.0319} clearly show that at 153 K the space group is monoclinic P21/c. The same structure measured at room temperature was reported to crystallize in the triclinic space group P
with Z = 4 (Sasan et al., 2008 ▸). However, the three cell angles are close 90 (2)° [α = 91.802 (6), β = 89.834 (7), γ = 91.845 (6)°] and the crystal used was a very narrow needle. The final R1 [I > 2σ(I)] factor was rather high at 0.0699, hence it is possible that the choice of crystal system and space group are incorrect. However, this could not be confirmed when analysing the coordinates using the AddSymm routine in PLATON (Spek, 2009 ▸).
Figure 1.
A view of the molecular structure of HL1, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The short intramolecular N—H⋯N interaction is shown as a dashed line (see Table 1 ▸ for details).
In the molecule of HL1 there is a short N—H⋯N hydrogen bond present in the pyrazine carboxamide unit (Table 1 ▸), and the amide group, C5(=O1)N3, is approximately coplanar with the pyrazine (N1/N2/C1–C4) ring [dihedral angle = 2.56 (14)°]. The pyrazine and pyridine (N4/C7–C10) rings are inclined to one another by 61.34 (6)°. In the triclinic structure mentioned above, the same angle in the two independent molecules is 63.31 (13) and 61.94 (13)°.
Table 1. Hydrogen-bond geometry (Å, °) for HL1 .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N3—H3N⋯N1 | 0.901 (16) | 2.332 (15) | 2.7136 (15) | 105.4 (11) |
| N3—H3N⋯N4i | 0.901 (16) | 2.206 (16) | 2.9929 (14) | 145.6 (13) |
| C3—H3⋯O1ii | 0.95 | 2.51 | 3.1544 (15) | 125 |
| C4—H4⋯O1ii | 0.95 | 2.56 | 3.1748 (15) | 123 |
| C10—H10⋯N2iii | 0.95 | 2.62 | 3.5678 (17) | 174 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
.
The molecular structure of HL2 is illustrated in Fig. 2 ▸. Here too there is a short intramolecular N—H⋯N contact involving the pyrazine carboxamide unit (Table 2 ▸), and the amide group, C5(=O1)N3, is almost coplanar with the pyrazine (N1/N2/C1–C4) ring with a dihedral angle of 3.9 (3)°. Here the pyrazine and pyridine (N4/C7–C10) rings are almost normal to one another with a dihedral angle of 84.33 (12)°.
Figure 2.
A view of the molecular structure of HL2, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The short intramolecular N—H⋯N interaction is shown as a dashed line (see Table 2 ▸ for details).
Table 2. Hydrogen-bond geometry (Å, °) for HL2 .
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| N3—H3N⋯N1 | 0.83 (3) | 2.27 (3) | 2.713 (3) | 114 (2) |
| N3—H3N⋯N2i | 0.83 (3) | 2.52 (3) | 3.214 (3) | 142 (2) |
| C2—H2⋯N1ii | 0.93 | 2.47 | 3.315 (3) | 151 |
| C8—H8⋯O1iii | 0.93 | 2.55 | 3.373 (3) | 148 |
Symmetry codes: (i) 
; (ii) 
; (iii) 
.
Supramolecular features
In the crystal of HL1, molecules are linked by N—H⋯N hydrogen bonds, forming inversion dimers with an 
(10) ring motif. The dimers are linked via bifurcated-acceptor C—H⋯O hydrogen bonds, forming sheets lying parallel to (102) (see Table 1 ▸ and Fig. 3 ▸). The sheets are linked via C—H⋯N hydrogen bonds, forming a three-dimensional structure (Table 1 ▸ and Fig. 4 ▸).
Figure 3.
A partial view along the a axis of the crystal packing of compound HL1. The N—H⋯N, C—H⋯O and C-H⋯N hydrogen bonds are shown as dashed lines (see Table 1 ▸ for details).
Figure 4.
The crystal packing of compound HL1 viewed along the b axis. The N—H⋯N, C—H⋯O and C—H⋯N hydrogen bonds are shown as dashed lines (see Table 1 ▸ for details).
In the crystal of HL2, molecules are linked by N—H⋯N and C—H⋯N hydrogen bonds to form chains propagating along [010], as shown in Table 2 ▸ and Fig. 5 ▸. The chains are linked via C—H⋯O hydrogen bonds, forming sheets lying parallel to (100). Within the sheets there are π–π interactions involving neighbouring pyrazine rings [Cg1⋯Cg1i = 3.7113 (15) Å; Cg1 is the centroid of the pyrazine ring N1/N2/C1–C4; symmetry code: (i) = x, −y + 
, z − ]. The sheets are linked via slipped parallel π–π interactions involving inversion-related pyridine rings [Cg2⋯Cg2ii = 3.6395 (11) Å, normal distance = 3.4164 (11), slippage = 1.255 Å; Cg2 is the centroid of pyridine ring N4/C7–C11; symmetry code: (ii) −x, −y, −z], forming a three-dimensional structure (Table 2 ▸ and Fig. 6 ▸).
Figure 5.
A partial view along the c axis of the crystal packing of compound HL2. The N—H⋯N, and C—H⋯N hydrogen bonds are shown as dashed lines (see Table 2 ▸ for details).
Figure 6.
The crystal packing of compound HL2 viewed along the c axis. The N—H⋯N, C—H⋯O and C—H⋯N hydrogen bonds are shown as dashed lines (see Table 2 ▸ for details).
Database survey
A search of the Cambridge Structural Database (Version 5.35, last update November 2013; Allen, 2002 ▸) indicated the presence of 282 structures containing the pyrazine-2-carboxamide unit. 81 of these concern pyrazine-2-carboxamide itself. There were 10 hits for complexes of ligand HL1. These include a cobalt(III) (Hellyer et al., 2009 ▸), a chromium(III) (Khavasi et al., 2010 ▸) and four copper(II) complexes (Mohamadou et al., 2012 ▸; Khavasi et al., 2011 ▸), all of which are mononuclear with the ligand coordinating in a tridentate manner. There are also two polymeric mercury chloride complexes (Khavasi & Sadegh, 2010 ▸), a binuclear manganese chloride complex (Khavasi et al., 2009 ▸), and a polymeric silver tetrafluoroborate complex (Hellyer et al., 2009 ▸), where the ligand coordinates in a bis-monodentate manner. Plus the report of the ligand itself as mentioned above (Sasan et al., 2008 ▸). For ligand HL2 there were no hits.
Synthesis and crystallization
The precursor pyrazine-2-carboxylic acid methyl ester (2-pze) was prepared following the procedure described by Alvarez-Ibarra et al. (1994 ▸). 6.21 g (50 mmol) of pyrazine-2-carboxylic acid were added to 50 ml of absolute methanol in a two-necked flask (100 ml). The mixture was heated to 303 K and then 0.4 ml of concentrated sulfuric acid was added slowly. The mixture was heated for 23 h, at least. It was then poured over ice and made alkaline using NaOH (2 N), then extracted with CH2Cl2. The organic extract was dried over Na2SO4. The resulting yellow product was purified by recrystallization from hexane, or by column chromatography on silica gel using CH2Cl2 as eluant, giving finally colourless crystals (yield 80%).
The ligand HL1 was prepared by refluxing 2-pze (1.80 g, 13 mmol) and an excess of 2-(aminomethyl)pyridine (1.84 g, 17 mmol) in 12 ml of methanol, for 6 h in a two-necked flask (50 ml). A yellowish oil remained when the methanol was evaporated off. The excess of 2-(aminomethyl)pyridine was eliminated by column chromatography on silica gel using CH2Cl2 as eluant (r = 2 cm, l = 8 cm). A yellow band of 2-(aminomethyl)pyridine remained on the column. After evaporation, the ligand could be recrystallized from diethyl ether, acetonitrile or ethyl acetate. HL1 is very soluble in MeOH and in CH2Cl2. Recrystallization from diethyl ether gave colourless blocks of HL1 (yield 91%; m.p. 388 K). Analysis for C11H10N4O (Mr = 214.46 g/mol) Calculated (%) C: 61.67 H: 4.71 N: 26.15; Found (%) C: 61.80 H: 4.76 N: 26.45. Spectroscopic data are available in the supporting information.
HL2 was prepared using the same procedure as for HL1. 2-pze (1.38 g, 10 mmol) with, this time, an excess of 4-(aminomethyl)pyridine (1.73 g, 16 mmol) were refluxed in 20 ml of methanol, for 20 h in a two-necked flask (50 ml). 4-(aminomethyl)pyridine (1g, 10 mmol) was then added to the red solution. After 4 h the solution was evaporated to about 8 ml. HL2 crystallized out at room temperature. About 20 ml of diethyl ether was added to filtrate the product. It was then recrystallized from a mixture of 3 ml of methanol and 40 ml of diethyl ether to give colourless blocks (yield 84%; m.p. 422 K). Anal. for C11H10N4O (Mr = 214.46 g/mol) Calculated (%) C: 61.67 H: 4.71 N: 26.15 Found (%) C: 61.57 H: 4.75 N: 26.20. Spectroscopic data are available in the supporting information.
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The NH H atoms were located in difference Fourier maps and freely refined. The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.95 Å for HL1 and = 0.93 Å for HL2, with U iso(H) = 1.2U eq(C).
Table 3. Experimental details.
| HL1 | HL2 | |
|---|---|---|
| Crystal data | ||
| Chemical formula | C11H10N4O | C11H10N4O |
| M r | 214.23 | 214.23 |
| Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
| Temperature (K) | 153 | 293 |
| a, b, c (Å) | 4.1527 (4), 20.4629 (18), 12.0106 (11) | 13.8564 (14), 11.1841 (11), 6.9122 (10) |
| β (°) | 91.461 (11) | 104.356 (14) |
| V (Å3) | 1020.28 (16) | 1037.7 (2) |
| Z | 4 | 4 |
| Radiation type | Mo Kα | Mo Kα |
| μ (mm−1) | 0.10 | 0.09 |
| Crystal size (mm) | 0.50 × 0.40 × 0.35 | 0.38 × 0.30 × 0.19 |
| Data collection | ||
| Diffractometer | Stoe IPDS 1 | Stoe AED2 four-circle |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7822, 1958, 1548 | 4132, 1937, 1198 |
| R int | 0.035 | 0.032 |
| (sin θ/λ)max (Å−1) | 0.615 | 0.605 |
| Refinement | ||
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.032, 0.088, 1.03 | 0.054, 0.127, 1.10 |
| No. of reflections | 1958 | 1937 |
| No. of parameters | 149 | 150 |
| 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 |
| Δρmax, Δρmin (e Å−3) | 0.17, −0.17 | 0.17, −0.16 |
Supplementary Material
Crystal structure: contains datablock(s) HL1, HL2, global. DOI: 10.1107/S1600536814009519/hb0007sup1.cif
Structure factors: contains datablock(s) HL1. DOI: 10.1107/S1600536814009519/hb0007HL1sup2.hkl
Supporting information file. DOI: 10.1107/S1600536814009519/hb0007HL1sup4.cml
Structure factors: contains datablock(s) HL2. DOI: 10.1107/S1600536814009519/hb0007HL2sup3.hkl
Supporting information file. DOI: 10.1107/S1600536814009519/hb0007HL2sup5.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
This work was supported by the Swiss National Science Foundation and the University of Neuchâtel.
supplementary crystallographic information
(HL1) N-(Pyridin-2-ylmethyl)pyrazine-2-carboxamide . Crystal data
| C11H10N4O | F(000) = 448 |
| Mr = 214.23 | Dx = 1.395 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 4.1527 (4) Å | Cell parameters from 6532 reflections |
| b = 20.4629 (18) Å | θ = 2.0–25.9° |
| c = 12.0106 (11) Å | µ = 0.10 mm−1 |
| β = 91.461 (11)° | T = 153 K |
| V = 1020.28 (16) Å3 | Block, colourless |
| Z = 4 | 0.50 × 0.40 × 0.35 mm |
(HL1) N-(Pyridin-2-ylmethyl)pyrazine-2-carboxamide . Data collection
| Stoe IPDS 1 diffractometer | 1548 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.035 |
| Plane graphite monochromator | θmax = 25.9°, θmin = 2.0° |
| φ rotation scans | h = −5→5 |
| 7822 measured reflections | k = −25→25 |
| 1958 independent reflections | l = −14→14 |
(HL1) N-(Pyridin-2-ylmethyl)pyrazine-2-carboxamide . Refinement
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: mixed |
| wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | w = 1/[σ2(Fo2) + (0.0539P)2 + 0.0704P] where P = (Fo2 + 2Fc2)/3 |
| 1958 reflections | (Δ/σ)max < 0.001 |
| 149 parameters | Δρmax = 0.17 e Å−3 |
| 0 restraints | Δρmin = −0.17 e Å−3 |
(HL1) N-(Pyridin-2-ylmethyl)pyrazine-2-carboxamide . Special details
| Experimental. Spectrosopic data for HL1: 1H NMR (400 MHz, DMSO-d6; code Hh/NH, Hl/C3, Hn/C1, Hm/C2, Hb/C11, Hd/C9, He/C8, Hc/C10, Hg/C6): 9.50 (t, 1H, Jhg = 6.0, Hh); 9.23 (d, 1H, Jlm = 1.5, Hl); 8.91 (d, 1H, Jnm = 2.5, Hn); 8.78 (dd, 1H, Jmn = 2.5, Jml = 1.5, Hm); 8.53 (ddd, 1H, Jbc = 4.8, Jbd = 1.8, Jbe = 0.8, Hb); 7.76 (td, 1H, Jdc = 7.7, Jdb = 1.8, Hd); 7.35 (d, 1H, Jed = 7.9, He); 7.28 (dd, 1H, Jcd = 7.7, Jcb = 4.8, Hc); 4.64 (d, 2H, Jgh = 6.0, He). 13C NMR (400 MHz, DMSO-d6): 163.9, 158.6, 149.7, 148.6, 145.5, 144.4, 144.3, 137.6, 123.1, 121.9, 45.0. IR (KBr pellet, cm-1): 3248 (m), 3066 (w), 3018 (w), 2949 (w), 1669 (versus), 1593 (m), 1570 (m), 1517 (versus), 1478 (m), 1462 (s), 1440 (s), 1423 (s), 1389 (s), 1350 (m), 1320 (m), 1287 (s), 1250 (m), 1221 (m), 1168 (s), 1148 (m), 1103 (m), 1055 (m), 1021 (s), 1000 (m), 975 (m), 870 (m), 840 (w), 776 (m), 753 (s), 707 (m), 634 (m), 611 (m), 528 (m), 444 (m). |
| 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. |
(HL1) N-(Pyridin-2-ylmethyl)pyrazine-2-carboxamide . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| N1 | 0.7345 (3) | 0.30055 (5) | 0.42625 (8) | 0.0260 (2) | |
| N2 | 0.7780 (3) | 0.16917 (5) | 0.49125 (9) | 0.0343 (3) | |
| N3 | 0.4290 (2) | 0.38859 (5) | 0.55546 (8) | 0.0224 (2) | |
| H3N | 0.514 (4) | 0.3982 (7) | 0.4892 (13) | 0.037 (4)* | |
| N4 | 0.5222 (3) | 0.53951 (5) | 0.66045 (8) | 0.0293 (3) | |
| O1 | 0.3074 (2) | 0.30857 (4) | 0.67870 (7) | 0.0344 (2) | |
| C1 | 0.6100 (3) | 0.27903 (5) | 0.52119 (9) | 0.0215 (3) | |
| C2 | 0.6318 (3) | 0.21416 (6) | 0.55317 (10) | 0.0287 (3) | |
| H2 | 0.5401 | 0.2011 | 0.6213 | 0.034* | |
| C3 | 0.9010 (3) | 0.19099 (6) | 0.39702 (10) | 0.0305 (3) | |
| H3 | 1.0071 | 0.1609 | 0.3501 | 0.037* | |
| C4 | 0.8800 (3) | 0.25567 (6) | 0.36486 (10) | 0.0290 (3) | |
| H4 | 0.9724 | 0.2686 | 0.2967 | 0.035* | |
| C5 | 0.4355 (3) | 0.32697 (6) | 0.59277 (9) | 0.0229 (3) | |
| C6 | 0.2435 (3) | 0.43932 (6) | 0.60984 (10) | 0.0263 (3) | |
| H6A | 0.0627 | 0.4186 | 0.6488 | 0.032* | |
| H6B | 0.1503 | 0.4688 | 0.5522 | 0.032* | |
| C7 | 0.4391 (3) | 0.47934 (5) | 0.69249 (9) | 0.0219 (3) | |
| C8 | 0.5266 (3) | 0.45428 (6) | 0.79615 (10) | 0.0271 (3) | |
| H8 | 0.4640 | 0.4113 | 0.8163 | 0.033* | |
| C9 | 0.7051 (3) | 0.49220 (6) | 0.86977 (10) | 0.0312 (3) | |
| H9 | 0.7682 | 0.4757 | 0.9410 | 0.037* | |
| C10 | 0.7906 (4) | 0.55455 (6) | 0.83801 (11) | 0.0350 (3) | |
| H10 | 0.9115 | 0.5822 | 0.8870 | 0.042* | |
| C11 | 0.6957 (4) | 0.57556 (6) | 0.73353 (11) | 0.0376 (3) | |
| H11 | 0.7569 | 0.6183 | 0.7117 | 0.045* |
(HL1) N-(Pyridin-2-ylmethyl)pyrazine-2-carboxamide . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0305 (6) | 0.0246 (5) | 0.0231 (5) | −0.0011 (4) | 0.0045 (4) | −0.0005 (4) |
| N2 | 0.0434 (7) | 0.0239 (5) | 0.0356 (6) | 0.0046 (5) | 0.0043 (5) | −0.0006 (4) |
| N3 | 0.0263 (5) | 0.0207 (5) | 0.0201 (5) | 0.0007 (4) | 0.0020 (4) | −0.0008 (4) |
| N4 | 0.0412 (7) | 0.0219 (5) | 0.0249 (5) | 0.0016 (4) | 0.0022 (4) | 0.0007 (4) |
| O1 | 0.0454 (6) | 0.0295 (5) | 0.0288 (5) | 0.0000 (4) | 0.0154 (4) | 0.0036 (4) |
| C1 | 0.0219 (6) | 0.0217 (6) | 0.0208 (5) | −0.0024 (5) | −0.0014 (4) | −0.0008 (4) |
| C2 | 0.0369 (8) | 0.0247 (6) | 0.0246 (6) | 0.0006 (5) | 0.0032 (5) | 0.0016 (5) |
| C3 | 0.0327 (7) | 0.0275 (6) | 0.0313 (7) | 0.0029 (5) | 0.0039 (5) | −0.0067 (5) |
| C4 | 0.0321 (7) | 0.0305 (6) | 0.0246 (6) | −0.0012 (5) | 0.0056 (5) | −0.0028 (5) |
| C5 | 0.0233 (6) | 0.0242 (6) | 0.0211 (6) | −0.0021 (5) | −0.0003 (5) | −0.0001 (4) |
| C6 | 0.0244 (7) | 0.0248 (6) | 0.0296 (6) | 0.0062 (5) | −0.0010 (5) | −0.0021 (5) |
| C7 | 0.0210 (6) | 0.0213 (6) | 0.0235 (6) | 0.0055 (5) | 0.0057 (4) | −0.0011 (4) |
| C8 | 0.0275 (7) | 0.0258 (6) | 0.0281 (6) | 0.0005 (5) | 0.0024 (5) | 0.0046 (5) |
| C9 | 0.0333 (7) | 0.0374 (7) | 0.0228 (6) | 0.0044 (6) | −0.0001 (5) | 0.0010 (5) |
| C10 | 0.0420 (8) | 0.0310 (7) | 0.0317 (7) | −0.0002 (6) | −0.0034 (6) | −0.0093 (5) |
| C11 | 0.0554 (9) | 0.0207 (6) | 0.0366 (7) | −0.0046 (6) | −0.0022 (6) | −0.0006 (5) |
(HL1) N-(Pyridin-2-ylmethyl)pyrazine-2-carboxamide . Geometric parameters (Å, º)
| N1—C4 | 1.3323 (16) | C3—H3 | 0.9500 |
| N1—C1 | 1.3386 (15) | C4—H4 | 0.9500 |
| N2—C3 | 1.3307 (17) | C6—C7 | 1.5082 (16) |
| N2—C2 | 1.3387 (16) | C6—H6A | 0.9900 |
| N3—C5 | 1.3382 (15) | C6—H6B | 0.9900 |
| N3—C6 | 1.4570 (15) | C7—C8 | 1.3865 (17) |
| N3—H3N | 0.901 (16) | C8—C9 | 1.3784 (18) |
| N4—C7 | 1.3379 (15) | C8—H8 | 0.9500 |
| N4—C11 | 1.3422 (17) | C9—C10 | 1.3806 (18) |
| O1—C5 | 1.2319 (14) | C9—H9 | 0.9500 |
| C1—C2 | 1.3842 (16) | C10—C11 | 1.3745 (19) |
| C1—C5 | 1.5028 (16) | C10—H10 | 0.9500 |
| C2—H2 | 0.9500 | C11—H11 | 0.9500 |
| C3—C4 | 1.3808 (18) | ||
| C4—N1—C1 | 115.80 (10) | N3—C6—C7 | 113.57 (9) |
| C3—N2—C2 | 115.53 (11) | N3—C6—H6A | 108.9 |
| C5—N3—C6 | 121.84 (10) | C7—C6—H6A | 108.9 |
| C5—N3—H3N | 119.7 (9) | N3—C6—H6B | 108.9 |
| C6—N3—H3N | 117.7 (9) | C7—C6—H6B | 108.9 |
| C7—N4—C11 | 117.12 (10) | H6A—C6—H6B | 107.7 |
| N1—C1—C2 | 121.86 (11) | N4—C7—C8 | 122.34 (11) |
| N1—C1—C5 | 118.36 (10) | N4—C7—C6 | 116.69 (10) |
| C2—C1—C5 | 119.76 (10) | C8—C7—C6 | 120.97 (11) |
| N2—C2—C1 | 122.19 (11) | C9—C8—C7 | 119.49 (11) |
| N2—C2—H2 | 118.9 | C9—C8—H8 | 120.3 |
| C1—C2—H2 | 118.9 | C7—C8—H8 | 120.3 |
| N2—C3—C4 | 122.47 (11) | C8—C9—C10 | 118.73 (11) |
| N2—C3—H3 | 118.8 | C8—C9—H9 | 120.6 |
| C4—C3—H3 | 118.8 | C10—C9—H9 | 120.6 |
| N1—C4—C3 | 122.14 (11) | C11—C10—C9 | 118.14 (12) |
| N1—C4—H4 | 118.9 | C11—C10—H10 | 120.9 |
| C3—C4—H4 | 118.9 | C9—C10—H10 | 120.9 |
| O1—C5—N3 | 124.27 (11) | N4—C11—C10 | 124.17 (12) |
| O1—C5—C1 | 120.30 (10) | N4—C11—H11 | 117.9 |
| N3—C5—C1 | 115.43 (10) | C10—C11—H11 | 117.9 |
| C4—N1—C1—C2 | 0.03 (17) | C2—C1—C5—N3 | 179.54 (11) |
| C4—N1—C1—C5 | −178.51 (11) | C5—N3—C6—C7 | 95.48 (13) |
| C3—N2—C2—C1 | 0.06 (19) | C11—N4—C7—C8 | −0.18 (18) |
| N1—C1—C2—N2 | −0.1 (2) | C11—N4—C7—C6 | 179.86 (11) |
| C5—C1—C2—N2 | 178.43 (11) | N3—C6—C7—N4 | 104.41 (12) |
| C2—N2—C3—C4 | 0.03 (19) | N3—C6—C7—C8 | −75.55 (14) |
| C1—N1—C4—C3 | 0.05 (18) | N4—C7—C8—C9 | 0.12 (18) |
| N2—C3—C4—N1 | −0.1 (2) | C6—C7—C8—C9 | −179.92 (11) |
| C6—N3—C5—O1 | −5.16 (19) | C7—C8—C9—C10 | 0.33 (19) |
| C6—N3—C5—C1 | 174.05 (10) | C8—C9—C10—C11 | −0.7 (2) |
| N1—C1—C5—O1 | 177.36 (11) | C7—N4—C11—C10 | −0.2 (2) |
| C2—C1—C5—O1 | −1.21 (18) | C9—C10—C11—N4 | 0.6 (2) |
| N1—C1—C5—N3 | −1.88 (16) |
(HL1) N-(Pyridin-2-ylmethyl)pyrazine-2-carboxamide . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3N···N1 | 0.901 (16) | 2.332 (15) | 2.7136 (15) | 105.4 (11) |
| N3—H3N···N4i | 0.901 (16) | 2.206 (16) | 2.9929 (14) | 145.6 (13) |
| C3—H3···O1ii | 0.95 | 2.51 | 3.1544 (15) | 125 |
| C4—H4···O1ii | 0.95 | 2.56 | 3.1748 (15) | 123 |
| C10—H10···N2iii | 0.95 | 2.62 | 3.5678 (17) | 174 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, −y+1/2, z−1/2; (iii) −x+2, y+1/2, −z+3/2.
(HL2) N-(Pyridin-4-ylmethyl)pyrazine-2-carboxamide . Crystal data
| C11H10N4O | F(000) = 448 |
| Mr = 214.23 | Dx = 1.371 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| a = 13.8564 (14) Å | Cell parameters from 20 reflections |
| b = 11.1841 (11) Å | θ = 10.4–17.6° |
| c = 6.9122 (10) Å | µ = 0.09 mm−1 |
| β = 104.356 (14)° | T = 293 K |
| V = 1037.7 (2) Å3 | Block, colourless |
| Z = 4 | 0.38 × 0.30 × 0.19 mm |
(HL2) N-(Pyridin-4-ylmethyl)pyrazine-2-carboxamide . Data collection
| Stoe AED2 four-circle diffractometer | Rint = 0.032 |
| Radiation source: fine-focus sealed tube | θmax = 25.5°, θmin = 2.4° |
| Plane graphite monochromator | h = −16→16 |
| 2θ/ω scans | k = −13→0 |
| 4132 measured reflections | l = −8→8 |
| 1937 independent reflections | 2 standard reflections every 60 min |
| 1198 reflections with I > 2σ(I) | intensity decay: 2% |
(HL2) N-(Pyridin-4-ylmethyl)pyrazine-2-carboxamide . 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)] = 0.054 | w = 1/[σ2(Fo2) + (0.0426P)2 + 0.1904P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.127 | (Δ/σ)max < 0.001 |
| S = 1.10 | Δρmax = 0.17 e Å−3 |
| 1937 reflections | Δρmin = −0.16 e Å−3 |
| 150 parameters | Extinction correction: SHELXL2013 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.014 (2) |
(HL2) N-(Pyridin-4-ylmethyl)pyrazine-2-carboxamide . Special details
| Experimental. Spectroscopic data for HL2: 1H NMR (400 MHz, DMSO-d6; code Hh/NH, Hl/C3, Hn/C1, Hm/C2, Hb/C11, Hd/C9, Ha/C11/, He/C8, Hg/C6): 9.63 (t, 1H, Jhg = 6.3, Hh); 9.21 (d, 1H, Jlm = 1.5, Hl); 8.90 (d, 1H, Jnm = 2.5, Hn); 8.77 (dd, 1H, Jmn = 2.5, Jml = 1.5, Hm); 8.49 (dd, 2H, Jba = 4.4, Jbe = 1.6, Hb = Hd); 7.31 (dd, 2H, Jab = 4.4, Jad = 1.6, Ha = He); 4.54 (d, 2H, Jgh = 6.3, Hg). 13C NMR (400 MHz, DMSO-d6): 164.2, 150.4, 149.0, 148.5, 145.4, 144.5, 144.3, 123.0, 42.4. IR (KBr pellet, cm-1): 3366 (versus), 3089 (s), 3050 (m), 3031 (s), 2967 (m), 2935 (s), 1966 (w), 1924 (w), 1834 (w), 1674 (versus), 1634 (s), 1602 (versus), 1585 (s), 1564 (s) 1526 (versus), 1467 (versus), 1429 (versus), 1415 (versus), 1399 (versus), 1359 (s), 1329 (s), 1288 (versus), 1240 (m), 1216 (versus), 1167 (s), 1155 (s), 1059 (versus), 1025 (versus), 1020 (versus), 993 (s), 981 (s), 968 (s), 887 (m), 870 (s), 842 (s), 832 (s), 804 (versus), 775 (s), 731 (m), 652 (versus), 608 (s), 517 (s), 479 (m), 445 (versus), 411 (m). |
| 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. |
(HL2) N-(Pyridin-4-ylmethyl)pyrazine-2-carboxamide . Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.32038 (14) | 0.28041 (15) | 0.2248 (3) | 0.0618 (6) | |
| N1 | 0.52051 (15) | 0.08089 (17) | 0.2297 (3) | 0.0456 (6) | |
| N2 | 0.61838 (17) | 0.29856 (19) | 0.2153 (3) | 0.0530 (6) | |
| N3 | 0.32823 (16) | 0.0787 (2) | 0.2548 (3) | 0.0495 (6) | |
| H3N | 0.367 (2) | 0.022 (2) | 0.251 (4) | 0.057 (9)* | |
| N4 | 0.04496 (18) | −0.1046 (2) | −0.2659 (4) | 0.0677 (7) | |
| C1 | 0.47371 (18) | 0.1855 (2) | 0.2255 (3) | 0.0389 (6) | |
| C2 | 0.5226 (2) | 0.2927 (2) | 0.2174 (4) | 0.0477 (7) | |
| H2 | 0.4870 | 0.3635 | 0.2132 | 0.057* | |
| C3 | 0.6641 (2) | 0.1935 (2) | 0.2189 (4) | 0.0531 (7) | |
| H3 | 0.7309 | 0.1925 | 0.2166 | 0.064* | |
| C4 | 0.61612 (19) | 0.0861 (2) | 0.2258 (4) | 0.0510 (7) | |
| H4 | 0.6515 | 0.0153 | 0.2279 | 0.061* | |
| C5 | 0.36661 (19) | 0.1863 (2) | 0.2342 (4) | 0.0442 (6) | |
| C6 | 0.22661 (19) | 0.0590 (2) | 0.2660 (4) | 0.0548 (7) | |
| H6A | 0.1972 | 0.1350 | 0.2877 | 0.066* | |
| H6B | 0.2267 | 0.0080 | 0.3795 | 0.066* | |
| C7 | 0.16399 (17) | 0.0020 (2) | 0.0798 (4) | 0.0431 (6) | |
| C8 | 0.1571 (2) | 0.0498 (2) | −0.1071 (4) | 0.0534 (7) | |
| H8 | 0.1922 | 0.1187 | −0.1216 | 0.064* | |
| C9 | 0.0979 (2) | −0.0052 (3) | −0.2711 (5) | 0.0652 (8) | |
| H9 | 0.0943 | 0.0291 | −0.3953 | 0.078* | |
| C10 | 0.0528 (2) | −0.1497 (2) | −0.0853 (5) | 0.0627 (8) | |
| H10 | 0.0171 | −0.2188 | −0.0752 | 0.075* | |
| C11 | 0.11055 (19) | −0.1010 (2) | 0.0887 (4) | 0.0517 (7) | |
| H11 | 0.1134 | −0.1374 | 0.2110 | 0.062* |
(HL2) N-(Pyridin-4-ylmethyl)pyrazine-2-carboxamide . Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0615 (13) | 0.0417 (11) | 0.0868 (15) | 0.0116 (10) | 0.0272 (11) | −0.0013 (10) |
| N1 | 0.0459 (13) | 0.0334 (12) | 0.0586 (14) | 0.0012 (10) | 0.0149 (10) | −0.0024 (10) |
| N2 | 0.0553 (15) | 0.0427 (14) | 0.0610 (15) | −0.0100 (11) | 0.0144 (11) | −0.0006 (11) |
| N3 | 0.0421 (14) | 0.0421 (14) | 0.0663 (16) | −0.0008 (11) | 0.0170 (11) | −0.0043 (11) |
| N4 | 0.0590 (16) | 0.0684 (18) | 0.0749 (19) | 0.0011 (13) | 0.0148 (14) | −0.0111 (15) |
| C1 | 0.0441 (14) | 0.0323 (13) | 0.0399 (14) | −0.0006 (11) | 0.0101 (11) | −0.0028 (11) |
| C2 | 0.0560 (18) | 0.0325 (15) | 0.0531 (17) | 0.0008 (12) | 0.0109 (13) | −0.0023 (12) |
| C3 | 0.0488 (17) | 0.0505 (16) | 0.0607 (17) | −0.0050 (14) | 0.0149 (13) | 0.0007 (14) |
| C4 | 0.0496 (16) | 0.0406 (15) | 0.0646 (18) | 0.0044 (13) | 0.0174 (13) | −0.0019 (13) |
| C5 | 0.0501 (16) | 0.0376 (14) | 0.0447 (15) | 0.0009 (13) | 0.0117 (12) | −0.0045 (12) |
| C6 | 0.0471 (16) | 0.0585 (18) | 0.0625 (19) | −0.0012 (13) | 0.0206 (14) | −0.0040 (14) |
| C7 | 0.0321 (13) | 0.0416 (14) | 0.0582 (18) | 0.0048 (11) | 0.0162 (12) | 0.0016 (12) |
| C8 | 0.0442 (15) | 0.0551 (17) | 0.0646 (19) | −0.0022 (13) | 0.0204 (14) | 0.0059 (15) |
| C9 | 0.0589 (19) | 0.084 (2) | 0.056 (2) | 0.0091 (17) | 0.0214 (16) | 0.0066 (17) |
| C10 | 0.0530 (18) | 0.0444 (16) | 0.092 (3) | −0.0008 (14) | 0.0204 (17) | −0.0063 (17) |
| C11 | 0.0457 (15) | 0.0439 (15) | 0.0674 (19) | 0.0043 (13) | 0.0179 (13) | 0.0087 (14) |
(HL2) N-(Pyridin-4-ylmethyl)pyrazine-2-carboxamide . Geometric parameters (Å, º)
| O1—C5 | 1.225 (3) | C3—H3 | 0.9300 |
| N1—C4 | 1.333 (3) | C4—H4 | 0.9300 |
| N1—C1 | 1.334 (3) | C6—C7 | 1.504 (3) |
| N2—C3 | 1.332 (3) | C6—H6A | 0.9700 |
| N2—C2 | 1.333 (3) | C6—H6B | 0.9700 |
| N3—C5 | 1.338 (3) | C7—C11 | 1.379 (3) |
| N3—C6 | 1.446 (3) | C7—C8 | 1.379 (4) |
| N3—H3N | 0.83 (3) | C8—C9 | 1.369 (4) |
| N4—C10 | 1.325 (4) | C8—H8 | 0.9300 |
| N4—C9 | 1.337 (4) | C9—H9 | 0.9300 |
| C1—C2 | 1.385 (3) | C10—C11 | 1.381 (4) |
| C1—C5 | 1.500 (3) | C10—H10 | 0.9300 |
| C2—H2 | 0.9300 | C11—H11 | 0.9300 |
| C3—C4 | 1.379 (3) | ||
| C4—N1—C1 | 116.2 (2) | N3—C6—C7 | 112.4 (2) |
| C3—N2—C2 | 115.2 (2) | N3—C6—H6A | 109.1 |
| C5—N3—C6 | 124.1 (2) | C7—C6—H6A | 109.1 |
| C5—N3—H3N | 113.8 (19) | N3—C6—H6B | 109.1 |
| C6—N3—H3N | 121.9 (19) | C7—C6—H6B | 109.1 |
| C10—N4—C9 | 115.1 (3) | H6A—C6—H6B | 107.9 |
| N1—C1—C2 | 121.3 (2) | C11—C7—C8 | 116.9 (3) |
| N1—C1—C5 | 119.0 (2) | C11—C7—C6 | 121.2 (2) |
| C2—C1—C5 | 119.6 (2) | C8—C7—C6 | 121.9 (2) |
| N2—C2—C1 | 122.8 (2) | C9—C8—C7 | 119.3 (3) |
| N2—C2—H2 | 118.6 | C9—C8—H8 | 120.3 |
| C1—C2—H2 | 118.6 | C7—C8—H8 | 120.3 |
| N2—C3—C4 | 122.5 (3) | N4—C9—C8 | 124.8 (3) |
| N2—C3—H3 | 118.7 | N4—C9—H9 | 117.6 |
| C4—C3—H3 | 118.7 | C8—C9—H9 | 117.6 |
| N1—C4—C3 | 121.9 (2) | N4—C10—C11 | 124.4 (3) |
| N1—C4—H4 | 119.0 | N4—C10—H10 | 117.8 |
| C3—C4—H4 | 119.0 | C11—C10—H10 | 117.8 |
| O1—C5—N3 | 124.2 (2) | C7—C11—C10 | 119.5 (3) |
| O1—C5—C1 | 120.9 (2) | C7—C11—H11 | 120.3 |
| N3—C5—C1 | 114.9 (2) | C10—C11—H11 | 120.3 |
| C4—N1—C1—C2 | 0.1 (3) | C2—C1—C5—N3 | −175.8 (2) |
| C4—N1—C1—C5 | −178.6 (2) | C5—N3—C6—C7 | 108.0 (3) |
| C3—N2—C2—C1 | 0.9 (4) | N3—C6—C7—C11 | 126.7 (3) |
| N1—C1—C2—N2 | −0.7 (4) | N3—C6—C7—C8 | −53.3 (3) |
| C5—C1—C2—N2 | 178.0 (2) | C11—C7—C8—C9 | 0.8 (4) |
| C2—N2—C3—C4 | −0.5 (4) | C6—C7—C8—C9 | −179.2 (2) |
| C1—N1—C4—C3 | 0.3 (4) | C10—N4—C9—C8 | 0.0 (4) |
| N2—C3—C4—N1 | −0.1 (4) | C7—C8—C9—N4 | −0.3 (4) |
| C6—N3—C5—O1 | 0.9 (4) | C9—N4—C10—C11 | −0.1 (4) |
| C6—N3—C5—C1 | −179.9 (2) | C8—C7—C11—C10 | −0.9 (4) |
| N1—C1—C5—O1 | −177.8 (2) | C6—C7—C11—C10 | 179.1 (2) |
| C2—C1—C5—O1 | 3.4 (4) | N4—C10—C11—C7 | 0.6 (4) |
| N1—C1—C5—N3 | 2.9 (3) |
(HL2) N-(Pyridin-4-ylmethyl)pyrazine-2-carboxamide . Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3N···N1 | 0.83 (3) | 2.27 (3) | 2.713 (3) | 114 (2) |
| N3—H3N···N2i | 0.83 (3) | 2.52 (3) | 3.214 (3) | 142 (2) |
| C2—H2···N1ii | 0.93 | 2.47 | 3.315 (3) | 151 |
| C8—H8···O1iii | 0.93 | 2.55 | 3.373 (3) | 148 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) x, −y+1/2, z−1/2.
Footnotes
This work forms part of the PhD thesis (Neuchâtel, 2002) of DSC.
References
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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) HL1, HL2, global. DOI: 10.1107/S1600536814009519/hb0007sup1.cif
Structure factors: contains datablock(s) HL1. DOI: 10.1107/S1600536814009519/hb0007HL1sup2.hkl
Supporting information file. DOI: 10.1107/S1600536814009519/hb0007HL1sup4.cml
Structure factors: contains datablock(s) HL2. DOI: 10.1107/S1600536814009519/hb0007HL2sup3.hkl
Supporting information file. DOI: 10.1107/S1600536814009519/hb0007HL2sup5.cml
Additional supporting information: crystallographic information; 3D view; checkCIF report