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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.


A view of the zigzag supra­molecular chain in (II) mediated by hydrazide-N—H⋯N(pyrid­yl) hydrogen bonds shown as blue dashed lines. The Br⋯O halogen bonds are indicated by purple dashed lines.
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fig8: A view of the zigzag supra­molecular chain in (II) mediated by hydrazide-N—H⋯N(pyrid­yl) hydrogen bonds shown as blue dashed lines. The Br⋯O halogen bonds are indicated by purple dashed lines.

Mentions: The most closely related structure to (I) in the crystallographic literature (Groom et al., 2016 ▸) is one that lacks the imine-methyl substituent and is anhydrous, hereafter referred to as (II); a similar numbering scheme is adopted here. This structure has been reported twice (Yang, 2006 ▸; Sedaghat et al., 2014 ▸) and data from the first determination are employed herein. Selected geometric parameters are collected in Table 4 ▸, from which it can be seen that there are no experimentally significant differences between the structures. However, there are conformational differences between the mol­ecules as highlighted in the overlay diagram shown in Fig. 7 ▸. While there is a close coincidence between the benzene rings and the first few atoms of the chain linking the rings, a twist occurs about the C1—C10 bond in (II), as seen in the N1—C1—C10–C14 torsion angle of 24.2 (5)°. The major consequence of this is seen in the dihedral angle between the rings of 11.23 (11)° cf. the near to orthogonal relationship in (I). This conformational difference likely relates to the distinct supra­molecular association in the crystals of (I) and (II). In (II), with no water mol­ecule to form hydrogen bonds, direct links between the organic mol­ecules are of the type hydrazide-N—H⋯N(pyrid­yl) and lead to zigzag supra­molecular chains, as illustrated in Fig. 8 ▸. Also evident from Fig. 8 ▸, is the close proximity of the bromide and oxygen atoms, which form type I Br⋯O halogen bonds, the separation between the atoms being 3.117 (3)°.


N ′ -[1-(5-Bromo-2-hy ­ droxy ­ phen ­ yl)ethyl ­ idene]isonicotinohydrazide monohydrate: crystal structure and Hirshfeld surface analysis
A view of the zigzag supra­molecular chain in (II) mediated by hydrazide-N—H⋯N(pyrid­yl) hydrogen bonds shown as blue dashed lines. The Br⋯O halogen bonds are indicated by purple dashed lines.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig8: A view of the zigzag supra­molecular chain in (II) mediated by hydrazide-N—H⋯N(pyrid­yl) hydrogen bonds shown as blue dashed lines. The Br⋯O halogen bonds are indicated by purple dashed lines.
Mentions: The most closely related structure to (I) in the crystallographic literature (Groom et al., 2016 ▸) is one that lacks the imine-methyl substituent and is anhydrous, hereafter referred to as (II); a similar numbering scheme is adopted here. This structure has been reported twice (Yang, 2006 ▸; Sedaghat et al., 2014 ▸) and data from the first determination are employed herein. Selected geometric parameters are collected in Table 4 ▸, from which it can be seen that there are no experimentally significant differences between the structures. However, there are conformational differences between the mol­ecules as highlighted in the overlay diagram shown in Fig. 7 ▸. While there is a close coincidence between the benzene rings and the first few atoms of the chain linking the rings, a twist occurs about the C1—C10 bond in (II), as seen in the N1—C1—C10–C14 torsion angle of 24.2 (5)°. The major consequence of this is seen in the dihedral angle between the rings of 11.23 (11)° cf. the near to orthogonal relationship in (I). This conformational difference likely relates to the distinct supra­molecular association in the crystals of (I) and (II). In (II), with no water mol­ecule to form hydrogen bonds, direct links between the organic mol­ecules are of the type hydrazide-N—H⋯N(pyrid­yl) and lead to zigzag supra­molecular chains, as illustrated in Fig. 8 ▸. Also evident from Fig. 8 ▸, is the close proximity of the bromide and oxygen atoms, which form type I Br⋯O halogen bonds, the separation between the atoms being 3.117 (3)°.

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.