Limits...
Hydrazinium 2-amino-4-nitro ­ benzoate dihydrate: crystal structure and Hirshfeld surface analysis

View Article: PubMed Central - HTML - PubMed

ABSTRACT

In the anion of the title salt hydrate, H5N2+·C7H5N2O4−·2H2O, the carboxyl­ate and nitro groups lie out of the plane of the benzene ring to which they are bound [dihedral angles = 18.80 (10) and 8.04 (9)°, respectively], and as these groups are conrotatory, the dihedral angle between them is 26.73 (15)°. An intra­molecular amino-N—H⋯O(carboxyl­ate) hydrogen bond is noted. The main feature of the crystal packing is the formation of a supra­molecular chain along the b axis, with a zigzag topology, sustained by charge-assisted water-O—H⋯O(carboxyl­ate) hydrogen bonds and comprising alternating twelve-membered {⋯OCO⋯HOH}2 and eight-membered {⋯O⋯HOH}2 synthons. Each ammonium-N—H atom forms a charge-assisted hydrogen bond to a water mol­ecule and, in addition, one of these forms a hydrogen bond with a nitro-O atom. The amine-N—H atoms form hydrogen bonds to carboxyl­ate-O and water-O atoms, and the amine N atom accepts a hydrogen bond from an amino-H atom. The hydrogen bonds lead to a three-dimensional architecture. An analysis of the Hirshfeld surface highlights the major contribution of O⋯H/H⋯O hydrogen bonding to the overall surface, i.e. 46.8%, compared with H⋯H contacts (32.4%).

No MeSH data available.


(a)The full two-dimensional fingerprint plot for (I) and fingerprint plots delineated into (b) O⋯H/H⋯O, (c) H⋯H, (d) C⋯C, (e) C⋯H/H⋯C, (f) C⋯O/O⋯C and (g) N⋯O/O⋯N contacts.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
getmorefigures.php?uid=PMC5382626&req=5

fig6: (a)The full two-dimensional fingerprint plot for (I) and fingerprint plots delineated into (b) O⋯H/H⋯O, (c) H⋯H, (d) C⋯C, (e) C⋯H/H⋯C, (f) C⋯O/O⋯C and (g) N⋯O/O⋯N contacts.

Mentions: The overall two-dimensional fingerprint plot for (I) and those delineated (McKinnon et al., 2007 ▸) into O⋯H/H⋯O, H⋯H, C⋯C, C⋯H/H⋯C, C⋯O/O⋯C and N⋯O/O⋯N contacts are illustrated in Fig. 6 ▸a–g, respectively; their relative contributions to the Hirshfeld surfaces are summarized in Table 3 ▸. It is important to note that the most significant contribution to the Hirshfeld surface in (I) comes from O⋯H/H⋯O contacts, i.e. 46.8%, due to the involvement of all the acidic hydrogen atoms in hydrogen bonds, mainly to oxygen, many of which are charge-assisted. Reflecting this dominance, sharp spikes are evident in the fingerprint plot delineated into O⋯H/H⋯O contacts shown in Fig. 6 ▸b. The pair of green spikes have their tips at de + di ∼1.9 Å and extend linearly up to de + di ∼2.3 Å. The points merged within the plot up to de + di ∼2.7 Å indicate the presence of short inter­atomic O⋯H/H⋯O contacts, Table 2 ▸. The extensive hydrogen bonding is the cause of the relatively small percentage contribution to the Hirshfeld surface from H⋯H contacts, i.e. 32.4%, Fig. 6 ▸c, as relatively few hydrogen atoms are available to form inter­atomic contacts. The pair of tips at de + di ∼2.3 Å in the mirror-reflected saw-tooth distribution are due to short inter­atomic H⋯H contacts involving water- and hydrazinium-hydrogen atoms, Table 2 ▸. The distributions of points in the fingerprint plot delineated into C⋯C contacts, shown in Fig. 6 ▸d, represents two π–π stacking inter­actions. In the first of these, the symmetry-related phenyl rings have a face-to-face overlap to give the arrow-like distribution in lower (de, di) region at around de = di = 1.6 Å. This inter­action is also seen as the flat region appearing about the phenyl ring on the Hirshfeld surface mapped over curvedness, shown in Fig. 7 ▸. The other π–π stacking inter­action involves edge-to-edge overlap through short inter­atomic C⋯C contacts involving the C2–C4 atoms, Fig. 4 ▸b and Table 2 ▸, and is viewed as the arrow-like distribution of points around de = di = 1.8 Å, i.e. adjacent to first arrow-like distribution. Even though C⋯H/H⋯C contacts have a significant contribution to the Hirshfeld surface, i.e. 5.9%, as seen from the fingerprint plot in Fig. 6 ▸e, the inter­atomic separations are much greater than sum of their van der Waals radii and hence do not appear to have influence on the mol­ecular packing. The presence of short inter­atomic C⋯O/O⋯C and N⋯O/O⋯N contacts in the crystal, Table 2 ▸, is also evident from the small but significant contributions of 3.3 and 1.3%, respectively, to the Hirshfeld surfaces and appear as pairs of forceps-like tips, Fig. 6 ▸f, and conical tips, Fig. 6 ▸g, at de + di ∼3.1 Å in their respective fingerprint plots. The small contributions from the other inter­atomic O⋯O, C⋯N/N⋯C, N⋯N and N⋯H/H⋯N contacts listed in Table 2 ▸ have a negligible effect on the packing in the crystal.


Hydrazinium 2-amino-4-nitro ­ benzoate dihydrate: crystal structure and Hirshfeld surface analysis
(a)The full two-dimensional fingerprint plot for (I) and fingerprint plots delineated into (b) O⋯H/H⋯O, (c) H⋯H, (d) C⋯C, (e) C⋯H/H⋯C, (f) C⋯O/O⋯C and (g) N⋯O/O⋯N contacts.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC5382626&req=5

fig6: (a)The full two-dimensional fingerprint plot for (I) and fingerprint plots delineated into (b) O⋯H/H⋯O, (c) H⋯H, (d) C⋯C, (e) C⋯H/H⋯C, (f) C⋯O/O⋯C and (g) N⋯O/O⋯N contacts.
Mentions: The overall two-dimensional fingerprint plot for (I) and those delineated (McKinnon et al., 2007 ▸) into O⋯H/H⋯O, H⋯H, C⋯C, C⋯H/H⋯C, C⋯O/O⋯C and N⋯O/O⋯N contacts are illustrated in Fig. 6 ▸a–g, respectively; their relative contributions to the Hirshfeld surfaces are summarized in Table 3 ▸. It is important to note that the most significant contribution to the Hirshfeld surface in (I) comes from O⋯H/H⋯O contacts, i.e. 46.8%, due to the involvement of all the acidic hydrogen atoms in hydrogen bonds, mainly to oxygen, many of which are charge-assisted. Reflecting this dominance, sharp spikes are evident in the fingerprint plot delineated into O⋯H/H⋯O contacts shown in Fig. 6 ▸b. The pair of green spikes have their tips at de + di ∼1.9 Å and extend linearly up to de + di ∼2.3 Å. The points merged within the plot up to de + di ∼2.7 Å indicate the presence of short inter­atomic O⋯H/H⋯O contacts, Table 2 ▸. The extensive hydrogen bonding is the cause of the relatively small percentage contribution to the Hirshfeld surface from H⋯H contacts, i.e. 32.4%, Fig. 6 ▸c, as relatively few hydrogen atoms are available to form inter­atomic contacts. The pair of tips at de + di ∼2.3 Å in the mirror-reflected saw-tooth distribution are due to short inter­atomic H⋯H contacts involving water- and hydrazinium-hydrogen atoms, Table 2 ▸. The distributions of points in the fingerprint plot delineated into C⋯C contacts, shown in Fig. 6 ▸d, represents two π–π stacking inter­actions. In the first of these, the symmetry-related phenyl rings have a face-to-face overlap to give the arrow-like distribution in lower (de, di) region at around de = di = 1.6 Å. This inter­action is also seen as the flat region appearing about the phenyl ring on the Hirshfeld surface mapped over curvedness, shown in Fig. 7 ▸. The other π–π stacking inter­action involves edge-to-edge overlap through short inter­atomic C⋯C contacts involving the C2–C4 atoms, Fig. 4 ▸b and Table 2 ▸, and is viewed as the arrow-like distribution of points around de = di = 1.8 Å, i.e. adjacent to first arrow-like distribution. Even though C⋯H/H⋯C contacts have a significant contribution to the Hirshfeld surface, i.e. 5.9%, as seen from the fingerprint plot in Fig. 6 ▸e, the inter­atomic separations are much greater than sum of their van der Waals radii and hence do not appear to have influence on the mol­ecular packing. The presence of short inter­atomic C⋯O/O⋯C and N⋯O/O⋯N contacts in the crystal, Table 2 ▸, is also evident from the small but significant contributions of 3.3 and 1.3%, respectively, to the Hirshfeld surfaces and appear as pairs of forceps-like tips, Fig. 6 ▸f, and conical tips, Fig. 6 ▸g, at de + di ∼3.1 Å in their respective fingerprint plots. The small contributions from the other inter­atomic O⋯O, C⋯N/N⋯C, N⋯N and N⋯H/H⋯N contacts listed in Table 2 ▸ have a negligible effect on the packing in the crystal.

View Article: PubMed Central - HTML - PubMed

ABSTRACT

In the anion of the title salt hydrate, H5N2+·C7H5N2O4−·2H2O, the carboxyl­ate and nitro groups lie out of the plane of the benzene ring to which they are bound [dihedral angles = 18.80 (10) and 8.04 (9)°, respectively], and as these groups are conrotatory, the dihedral angle between them is 26.73 (15)°. An intra­molecular amino-N—H⋯O(carboxyl­ate) hydrogen bond is noted. The main feature of the crystal packing is the formation of a supra­molecular chain along the b axis, with a zigzag topology, sustained by charge-assisted water-O—H⋯O(carboxyl­ate) hydrogen bonds and comprising alternating twelve-membered {⋯OCO⋯HOH}2 and eight-membered {⋯O⋯HOH}2 synthons. Each ammonium-N—H atom forms a charge-assisted hydrogen bond to a water mol­ecule and, in addition, one of these forms a hydrogen bond with a nitro-O atom. The amine-N—H atoms form hydrogen bonds to carboxyl­ate-O and water-O atoms, and the amine N atom accepts a hydrogen bond from an amino-H atom. The hydrogen bonds lead to a three-dimensional architecture. An analysis of the Hirshfeld surface highlights the major contribution of O⋯H/H⋯O hydrogen bonding to the overall surface, i.e. 46.8%, compared with H⋯H contacts (32.4%).

No MeSH data available.