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

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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%).

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The mol­ecular packing in (I): (a) immediate environment about the [H2NNH3] cation, (b) supra­molecular chain comprising anions and water mol­ecules only, orientated along the b axis and sustained by water-O—H⋯O(carboxyl­ate) hydrogen bonding, (c) decoration of the chain of (b) with cations and additional water mol­ecules to highlight the formation of various supra­molecular synthons (see text) and (d) a view of the unit-cell contents in projection down the b axis. The O—H⋯O, N—H⋯O, N—H⋯N and intra­molecular N—H⋯O hydrogen bonds are shown as orange, blue, brown and pink dashed lines, respectively. In (b) and (c), all but the CO2 groups of the two central benzoate residues have been removed for clarity.
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fig2: The mol­ecular packing in (I): (a) immediate environment about the [H2NNH3] cation, (b) supra­molecular chain comprising anions and water mol­ecules only, orientated along the b axis and sustained by water-O—H⋯O(carboxyl­ate) hydrogen bonding, (c) decoration of the chain of (b) with cations and additional water mol­ecules to highlight the formation of various supra­molecular synthons (see text) and (d) a view of the unit-cell contents in projection down the b axis. The O—H⋯O, N—H⋯O, N—H⋯N and intra­molecular N—H⋯O hydrogen bonds are shown as orange, blue, brown and pink dashed lines, respectively. In (b) and (c), all but the CO2 groups of the two central benzoate residues have been removed for clarity.

Mentions: As expected from the chemical composition of (I), there are a number of conventional hydrogen-bonding inter­actions in the crystal, involving all possible hydrogen-bond donors and acceptors, Table 1 ▸. These sustain a three-dimensional architecture. A view of the inter­actions involving the hydrazinium cation is shown in Fig. 2 ▸a. Each of the ammonium-N3—H atoms forms a charge-assisted hydrogen bond to a water mol­ecule, with the HN4 atom also forming a hydrogen bond to a nitro-O4 atom indicating that the HN4 atom is bifurcated [i.e.: N—H⋯(O,O)]. The amine-N4—H atoms form a hydrogen bond to a carboxyl­ate-O1 atom and to a water mol­ecule and at the same time accept a hydrogen bond from an amino-H atom, this being the only N—H⋯N hydrogen bond in the structure; the second amino-H atom forms an intra­molecular hydrogen bond with the carboxyl­ate-O1 atom, as mentioned above. Each of the water-H atoms forms a charge-assisted hydrogen bond with a carboxyl­ate-O atom, leading to a zigzag supra­molecular chain aligned along the b axis, as shown in Fig. 2 ▸b. The chain comprises alternating twelve-membered {⋯OCO⋯HOH}2 and eight-membered {⋯O⋯HOH}2 synthons. As shown in Fig. 2 ▸c, two of the ammonium-N3—H atoms bridge water mol­ecules in the chain shown in Fig. 2 ▸b to form a non-symmetric, eight-membered {⋯HNH⋯OH⋯O⋯HO} synthon while the amine-H atoms provide a second bridge between water- and carboxyl­ate-O atoms to form a ten-membered {⋯HNH⋯OH⋯O⋯HOH⋯O} synthon. Further hydrogen bonds to water mol­ecules leads to the formation of additional synthons, i.e. ten-membered {⋯HNNH⋯O}2 and eight-membered {⋯HNH⋯O}2. A view of the unit-cell contents is shown in Fig. 2 ▸d. In addition to the above, π(phen­yl)–π(phen­yl) inter­actions are noted between inversion-related rings with the inter-centroid separation being 3.6190 (8) Å [symmetry operation 1 − x, −y, 1 − z].


Hydrazinium 2-amino-4-nitro ­ benzoate dihydrate: crystal structure and Hirshfeld surface analysis
The mol­ecular packing in (I): (a) immediate environment about the [H2NNH3] cation, (b) supra­molecular chain comprising anions and water mol­ecules only, orientated along the b axis and sustained by water-O—H⋯O(carboxyl­ate) hydrogen bonding, (c) decoration of the chain of (b) with cations and additional water mol­ecules to highlight the formation of various supra­molecular synthons (see text) and (d) a view of the unit-cell contents in projection down the b axis. The O—H⋯O, N—H⋯O, N—H⋯N and intra­molecular N—H⋯O hydrogen bonds are shown as orange, blue, brown and pink dashed lines, respectively. In (b) and (c), all but the CO2 groups of the two central benzoate residues have been removed for clarity.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

fig2: The mol­ecular packing in (I): (a) immediate environment about the [H2NNH3] cation, (b) supra­molecular chain comprising anions and water mol­ecules only, orientated along the b axis and sustained by water-O—H⋯O(carboxyl­ate) hydrogen bonding, (c) decoration of the chain of (b) with cations and additional water mol­ecules to highlight the formation of various supra­molecular synthons (see text) and (d) a view of the unit-cell contents in projection down the b axis. The O—H⋯O, N—H⋯O, N—H⋯N and intra­molecular N—H⋯O hydrogen bonds are shown as orange, blue, brown and pink dashed lines, respectively. In (b) and (c), all but the CO2 groups of the two central benzoate residues have been removed for clarity.
Mentions: As expected from the chemical composition of (I), there are a number of conventional hydrogen-bonding inter­actions in the crystal, involving all possible hydrogen-bond donors and acceptors, Table 1 ▸. These sustain a three-dimensional architecture. A view of the inter­actions involving the hydrazinium cation is shown in Fig. 2 ▸a. Each of the ammonium-N3—H atoms forms a charge-assisted hydrogen bond to a water mol­ecule, with the HN4 atom also forming a hydrogen bond to a nitro-O4 atom indicating that the HN4 atom is bifurcated [i.e.: N—H⋯(O,O)]. The amine-N4—H atoms form a hydrogen bond to a carboxyl­ate-O1 atom and to a water mol­ecule and at the same time accept a hydrogen bond from an amino-H atom, this being the only N—H⋯N hydrogen bond in the structure; the second amino-H atom forms an intra­molecular hydrogen bond with the carboxyl­ate-O1 atom, as mentioned above. Each of the water-H atoms forms a charge-assisted hydrogen bond with a carboxyl­ate-O atom, leading to a zigzag supra­molecular chain aligned along the b axis, as shown in Fig. 2 ▸b. The chain comprises alternating twelve-membered {⋯OCO⋯HOH}2 and eight-membered {⋯O⋯HOH}2 synthons. As shown in Fig. 2 ▸c, two of the ammonium-N3—H atoms bridge water mol­ecules in the chain shown in Fig. 2 ▸b to form a non-symmetric, eight-membered {⋯HNH⋯OH⋯O⋯HO} synthon while the amine-H atoms provide a second bridge between water- and carboxyl­ate-O atoms to form a ten-membered {⋯HNH⋯OH⋯O⋯HOH⋯O} synthon. Further hydrogen bonds to water mol­ecules leads to the formation of additional synthons, i.e. ten-membered {⋯HNNH⋯O}2 and eight-membered {⋯HNH⋯O}2. A view of the unit-cell contents is shown in Fig. 2 ▸d. In addition to the above, π(phen­yl)–π(phen­yl) inter­actions are noted between inversion-related rings with the inter-centroid separation being 3.6190 (8) Å [symmetry operation 1 − x, −y, 1 − z].

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.


Related in: MedlinePlus