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N ′ -[1-(5-Bromo-2-hy ­ droxy ­ phen ­ yl)ethyl ­ idene]isonicotinohydrazide monohydrate: crystal structure and Hirshfeld surface analysis

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ABSTRACT

In the title isonicotinohydrazide hydrate, C14H12BrN3O2·H2O {systematic name: N′-[(1E)-1-(5-bromo-2-hy­droxy­phen­yl)ethyl­idene]pyridine-4-carbohydrazide monohydrate}, the central CN2O region of the organic mol­ecule is planar and the conformation about the imine-C=N bond is E. While an intra­molecular hy­droxy-O—H⋯N(imine) hydrogen bond is evident, the dihedral angle between the central residue and the benzene rings is 48.99 (9)°. Overall, the mol­ecule is twisted, as seen in the dihedral angle of 71.79 (6)° between the outer rings. In the crystal, hydrogen-bonding inter­actions, i.e. hydrazide-N—H⋯O(water), water-O—H⋯O(carbon­yl) and water-O—H⋯N(pyrid­yl), lead to supra­molecular ribbons along the a-axis direction. Connections between these, leading to a three-dimensional architecture, are mediated by Br⋯Br halogen bonding [3.5366 (3) Å], pyridyl-C—H⋯O(carbon­yl) as well as weak π–π inter­actions [inter-centroid separation between benzene rings = 3.9315 (12) Å]. The Hirshfeld surface analysis reveals the importance of hydrogen atoms in the supra­molecular connectivity as well as the influence of the Br⋯Br halogen bonding.

No MeSH data available.


Views of the Hirshfeld surface for (I) mapped over dnorm over the range −0.150 to 1.528 au.
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fig4: Views of the Hirshfeld surface for (I) mapped over dnorm over the range −0.150 to 1.528 au.

Mentions: The analysis of the Hirshfeld surface for (I) was performed as per a recent publication (Wardell et al., 2016 ▸). Views of the Hirshfeld surface mapped over the calculated electrostatic potential are given in Fig. 3 ▸. It is important to note that despite its small size relative to the organic species, the presence of water in the crystal lattice exerts a great influence on the packing of (I) owing to the involvement of all of its atoms in conventional hydrogen bonds as well as short inter­atomic contacts (Table 2 ▸). This is also seen through the appearance in Fig. 3 ▸a of a light-red spot (negative potential) within the surface near the water-O1W atoms as well as the blue regions (positive potential) about the water-H1W and H2W atoms, which correspond to the acceptor and donors of the hydrogen bonds, respectively. Similarly, the other donor and acceptor atoms participating in the more significant inter­molecular inter­actions are viewed as the blue and red regions, respectively, in Fig. 3 ▸. The donors and acceptors of water-O—H⋯O(carbon­yl) and water-O—H⋯N(pyrid­yl) hydrogen bonds on the Hirshfeld surfaces mapped over dnorm in Fig. 4 ▸ appear as bright-red spots near the respective atoms. The presence of red spots near the Br1 and pyridine-C12 atoms in Fig. 4 ▸b also highlight the significant contribution of Br⋯Br and C⋯C contacts to the mol­ecular packing. The presence of faint-red spots near the pyridyl-N3, C13 and H13 atoms and the carbonyl-O1 atom indicate their contributions to short inter­atomic C⋯N/N⋯C contacts (Table 2 ▸) and comparatively weak inter­molecular C—H⋯O inter­actions, respectively. The immediate environments about a reference pair of mol­ecules comprising (I) within the dnorm- (Fig. 5 ▸a and b) and shape-index- (Fig. 5 ▸c) mapped Hirshfeld surfaces highlighting the various short inter­atomic contacts influential on the mol­ecular packing are illustrated in Fig. 5 ▸. The C⋯H/H⋯C and O⋯H/H⋯O contacts, Fig. 5 ▸a, C⋯C and C⋯N/N⋯C contacts, Fig. 5 ▸b, and Br⋯Br and Br⋯H/H⋯Br contacts, Fig. 5 ▸c, identify their roles in consolidating the packing in the crystal.


N ′ -[1-(5-Bromo-2-hy ­ droxy ­ phen ­ yl)ethyl ­ idene]isonicotinohydrazide monohydrate: crystal structure and Hirshfeld surface analysis
Views of the Hirshfeld surface for (I) mapped over dnorm over the range −0.150 to 1.528 au.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC5382638&req=5

fig4: Views of the Hirshfeld surface for (I) mapped over dnorm over the range −0.150 to 1.528 au.
Mentions: The analysis of the Hirshfeld surface for (I) was performed as per a recent publication (Wardell et al., 2016 ▸). Views of the Hirshfeld surface mapped over the calculated electrostatic potential are given in Fig. 3 ▸. It is important to note that despite its small size relative to the organic species, the presence of water in the crystal lattice exerts a great influence on the packing of (I) owing to the involvement of all of its atoms in conventional hydrogen bonds as well as short inter­atomic contacts (Table 2 ▸). This is also seen through the appearance in Fig. 3 ▸a of a light-red spot (negative potential) within the surface near the water-O1W atoms as well as the blue regions (positive potential) about the water-H1W and H2W atoms, which correspond to the acceptor and donors of the hydrogen bonds, respectively. Similarly, the other donor and acceptor atoms participating in the more significant inter­molecular inter­actions are viewed as the blue and red regions, respectively, in Fig. 3 ▸. The donors and acceptors of water-O—H⋯O(carbon­yl) and water-O—H⋯N(pyrid­yl) hydrogen bonds on the Hirshfeld surfaces mapped over dnorm in Fig. 4 ▸ appear as bright-red spots near the respective atoms. The presence of red spots near the Br1 and pyridine-C12 atoms in Fig. 4 ▸b also highlight the significant contribution of Br⋯Br and C⋯C contacts to the mol­ecular packing. The presence of faint-red spots near the pyridyl-N3, C13 and H13 atoms and the carbonyl-O1 atom indicate their contributions to short inter­atomic C⋯N/N⋯C contacts (Table 2 ▸) and comparatively weak inter­molecular C—H⋯O inter­actions, respectively. The immediate environments about a reference pair of mol­ecules comprising (I) within the dnorm- (Fig. 5 ▸a and b) and shape-index- (Fig. 5 ▸c) mapped Hirshfeld surfaces highlighting the various short inter­atomic contacts influential on the mol­ecular packing are illustrated in Fig. 5 ▸. The C⋯H/H⋯C and O⋯H/H⋯O contacts, Fig. 5 ▸a, C⋯C and C⋯N/N⋯C contacts, Fig. 5 ▸b, and Br⋯Br and Br⋯H/H⋯Br contacts, Fig. 5 ▸c, identify their roles in consolidating the packing in the crystal.

View Article: PubMed Central - HTML - PubMed

ABSTRACT

In the title isonicotinohydrazide hydrate, C14H12BrN3O2·H2O {systematic name: N′-[(1E)-1-(5-bromo-2-hy­droxy­phen­yl)ethyl­idene]pyridine-4-carbohydrazide monohydrate}, the central CN2O region of the organic mol­ecule is planar and the conformation about the imine-C=N bond is E. While an intra­molecular hy­droxy-O—H⋯N(imine) hydrogen bond is evident, the dihedral angle between the central residue and the benzene rings is 48.99 (9)°. Overall, the mol­ecule is twisted, as seen in the dihedral angle of 71.79 (6)° between the outer rings. In the crystal, hydrogen-bonding inter­actions, i.e. hydrazide-N—H⋯O(water), water-O—H⋯O(carbon­yl) and water-O—H⋯N(pyrid­yl), lead to supra­molecular ribbons along the a-axis direction. Connections between these, leading to a three-dimensional architecture, are mediated by Br⋯Br halogen bonding [3.5366 (3) Å], pyridyl-C—H⋯O(carbon­yl) as well as weak π–π inter­actions [inter-centroid separation between benzene rings = 3.9315 (12) Å]. The Hirshfeld surface analysis reveals the importance of hydrogen atoms in the supra­molecular connectivity as well as the influence of the Br⋯Br halogen bonding.

No MeSH data available.