Abstract
C12H9BrN2, monoclinic, P21/c (no. 14), a = 19.2197(12) Å, b = 4.8579(3) Å, c = 11.4679(9) Å, β = 106.880(4)°, V = 1024.60(12) Å3, Z = 4, Rgt(F) = 0.0449, wRref(F2) = 0.1257, T = 100(2) K.
The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Colourless block |
| Size: | 0.29 × 0.21 × 0.14 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 3.98 mm−1 |
| Diffractometer, scan mode: | Bruker SMART APEX-II, φ and ω |
| θmax, completeness: | 28.5°, 98% |
| N(hkl)measured, N(hkl)unique, Rint: | 25389, 2527, 0.066 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 2166 |
| N(param)refined: | 136 |
| Programs: | Bruker [1], SHELX [2], [3], Mercury [4] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | Uiso*/Ueq |
|---|---|---|---|---|
| Br1 | 0.04566(2) | 1.42267(7) | 0.35506(3) | 0.01610(14) |
| N1 | 0.38153(17) | 0.0788(7) | 0.6529(3) | 0.0209(7) |
| N2 | 0.25245(17) | 0.5885(6) | 0.6725(3) | 0.0184(6) |
| C1 | 0.3501(2) | 0.2097(8) | 0.8336(3) | 0.0227(7) |
| H1 | 0.322357 | 0.323049 | 0.870810 | 0.027* |
| C2 | 0.3990(2) | 0.0194(10) | 0.9019(3) | 0.0263(8) |
| H2 | 0.405417 | 0.000766 | 0.986784 | 0.032* |
| C3 | 0.4387(2) | −0.1440(9) | 0.8442(3) | 0.0240(8) |
| H3 | 0.471805 | −0.279112 | 0.888065 | 0.029* |
| C4 | 0.4281(2) | −0.1026(8) | 0.7204(3) | 0.0223(8) |
| H4 | 0.455978 | −0.210746 | 0.681273 | 0.027* |
| C5 | 0.34250(18) | 0.2314(8) | 0.7095(3) | 0.0179(7) |
| C6 | 0.29112(19) | 0.4255(7) | 0.6300(3) | 0.0173(7) |
| H6 | 0.286731 | 0.429397 | 0.545340 | 0.021* |
| C7 | 0.20549(18) | 0.7756(7) | 0.5917(3) | 0.0163(6) |
| C8 | 0.1497(2) | 0.8906(8) | 0.6324(3) | 0.0176(7) |
| H8 | 0.145246 | 0.839072 | 0.709781 | 0.021* |
| C9 | 0.10111(19) | 1.0775(7) | 0.5619(3) | 0.0166(7) |
| H9 | 0.062235 | 1.147986 | 0.588680 | 0.020* |
| C10 | 0.11014(18) | 1.1601(8) | 0.4516(3) | 0.0161(6) |
| C11 | 0.1658(2) | 1.0554(7) | 0.4098(3) | 0.0163(7) |
| H11 | 0.171249 | 1.113686 | 0.333830 | 0.020* |
| C12 | 0.21327(19) | 0.8651(8) | 0.4805(3) | 0.0183(7) |
| H12 | 0.251765 | 0.794142 | 0.452846 | 0.022* |
Source of material
An ethanolic solution of 2-pyridinecarboxaldehyde (1.07 g, 10 mmol) was added to a solution of 4-bromoaniline (1.72 g, 10 mmol) in ethanol and the solution was refluxed for 6 hours. The reaction mixture was then cooled to room temperature and MgSO4 was added to remove excess water. The MgSO4 was filtered off and the filtrate was dried overnight under reduced pressure. This gave an off-white powder (1.92 g, 73%). Mp: 69–69.4 °C. Crystals were grown through a slow evaporation of an ethanol solution at 25 °C.
Experimental details
The structure was solved by the direct method using the SHELXS [2] program and refined. The visual crystal structure information was performed using Mercury [4] system software. All hydrogen atoms were placed in idealized positions and refined in riding models with Uiso assigned the values of 1.2 times those of their parent atoms and the distances of C—H were constrained to 0.95 Å for all the aromatic H atoms.
Comment
Schiff bases were described by Hugo Schiff in 1864 as a condensation reaction of imines and aldehydes. Their ease of synthesis, ability to coordinate to various metals with different oxidation states and influence the way a metal reacts in various catalytic transformations has led to remarkable use of these N,N′- bidentate ligands. Ligand design has enabled chemists to explore the steric and electronic properties of these ligands on various catalytic platforms [5], [6], [7]. Metal complexes of these pyridyl imine ligands have been found to perform various catalytic transformations such as alcohol oxidation [8] and transfer hydrogenation of ketones [9].
The asymmetric unit has one molecular unit of the title compound (cf. the figure). The compound exhibits an E conformation around the N2=C6 bond which is comparable to related compounds in literature [10], [11], [12], [13], [14]. The analogous compound with a methyl group instead of the bromo substituent forms an isotypic structure [15]. The dihedral angle between the phenyl and pyridyl moieties was measured to be 19.2°, whilst all bond parameters appear normal. The crystal packing contains intermolecular C10—Br1⋯Cgphenyli interactions crystal packing with Br1⋯Cgphenyli distance of 3.601(2) Å and C10—Br1⋯Cgphenyli angle of 89.97(1)° (symmetry code: (i) = x, 1 + y, z). Short Br1⋯Br1ii,iii contacts (symmetry codes: (ii) = −x, −1/2 + y, 1/2 − z; (iii) = −x, 1/2 + y, 1/2 − z) with distances of 3.5115(6) Å were also observed. The two types of intermolecular interactions observed in the crystal packing link together neighboring molecules to form a one dimensional supramolecular structure which propagates along the crystallographic b axis.
Acknowledgements
We would like to thank the DST- National Research Foundation Centre of Excellence in Catalysis C* change for financial support.
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©2019 Nyameka Diko et al., published by De Gruyter, Berlin/Boston
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