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In the title compound [systematic name: (1Z,3Z)-1,3-di­hydra­zin­yl­idene-1H-inden-2(3H)-one], C9H8N4O, isolated mol­e­cules possess approximate noncrystallographic C2v symmetry and their cis conformation and planarity are assisted by a pair of short intra­molecular N-H...O hydrogen bonds. Each mol­ecule is asymmetrically involved in an extensive three-dimensional network of N-H...O and N-H...N hydrogen bonds, and the structure also exhibits weaker [pi]-[pi] and C=O...C inter­actions. The structure features an R44(12) motif consisting solely of N and H atoms and possessing crystallographic \overline{4} symmetry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112034749/uk3049sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112034749/uk3049Isup2.hkl
Contains datablock I

cdx

Chemdraw file https://doi.org/10.1107/S0108270112034749/uk3049Isup3.cdx
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112034749/uk3049Isup4.cml
Supplementary material

CCDC reference: 908139

Comment top

Ninhydrin is a widely used reagent for qualitative and quantitative analysis of all amino acids possessing a primary amine function (Holme & Peck, 1998); together they form a purple-coloured compound, popularly known as Ruhemann's Purple. Several methods which utilize ninhydrin have been developed for enhancing fingerprints (Everse & Menzel, 1986; Menzel & Mitchell, 1990; Fregeau et al., 2000). It also exhibits strong antibacterial and antiviral properties. Derivatives of ninhydrin are of importance as multidentate ligands in metal complexation. Reactions between ninhydrin and α-amino acids in the presence of transition metal ions have been documented to form a variety of coloured compounds, which are different from Ruhemann's Purple (Koteswara Rao & Ram Reddy, 1990; Mehabaw, 2001; Derebe et al., 2002, 2003; Negash, 2003).

Derivatives of ninhydrin with simple amines carrying suitable substituents, such as hydrazine, hydroxylamine, semicarbazide and thiosemicarbazide, with the potential for metal binding have not been systematically investigated for their structural and metal-complexation characteristics. Literature surveys reveal that no significant attempts have been made to investigate the structural characteristics of ninhydrin dihydrazone. Being a tricarbonyl system, ninhydrin can exhibit variable reactivity towards amine functions. In the case of α-amino acids, only one of the three carbonyl functions is known to be involved in the condensation process, with several subsequent steps leading to Ruhemann's Purple. However, with other amines, a variable number of carbonyls may be involved in the condensation reaction, depending upon steric and electronic factors. It is therefore worthwhile to undertake studies of the reactivity of ninhydrin towards amine systems other than α-amino acids as they are likely to result in interesting network systems. Consequently, these systems could have further applications in fingerprinting, metal targeting and biochemical processes.

Isolated molecules of the title compound, (I), exhibit a good approximation to C2v symmetry, with the atoms lying close to the molecular plane and the NH2 groups both cis to the carbonyl group (Fig. 1). Although the atoms of the two rings are coplanar to within 0.04 Å, they can also be visualized as two separate rings which exhibit greater degrees of planarity, with C1–C5 and C4–C9 showing r.m.s. deviations of only 0.011 and 0.004 Å, respectively: the dihedral angle between these rings is 1.43 (6)°. The inclusion of the NH2 groups in this planar arrangement is assisted by the presence of short intramolecular N11—H11A···O2 and N13—H13A···O2 hydrogen bonds (Fig. 1 and Table 2); these favour the mutually cis arrangement of NH2 groups over a trans arrangement which might be more favourable to the formation of intermolecular hydrogen bonding. The only significant deviation from this local symmetry appears for the N—N distances, where N10—N11 is 0.022 (3) Å longer than N12—N13 (Table 1); we attribute this to the differing contributions made by the NH2 groups of N11 and N13 to the formation of the intermolecular hydrogen-bonding network (see below).

Fig. 2 shows the central molecule in the same orientation as in Fig. 1 to illustrate the local hydrogen-bonding network, which is extensive despite the presence of the short intramolecular hydrogen bonds. A significant feature of the structure is the very different patterns of interaction with neighbouring molecules: whereas the N10/N11 side of the molecule forms pairwise N—H···N hydrogen bonds with a single molecule [graph-set notation R22(6); Etter et al., 1990], the N12/N13 side participates in three hydrogen bonds to three different molecules, with atom N12 acting as a hydrogen-bond acceptor and both H atoms on N13 acting as hydrogen-bond donors. The molecules form undulating chains via N13—H13B···N12i and pairwise N11—H11B···N10ii interactions [symmetry codes: (i) -y + 1/2, x, -z - 1/2; (ii) -x, -y + 1, -z + 1], with the mean planes through alternate pairs of molecules disposed approximately orthogonal to each other. The molecules of each pair are related by inversion [symmetry code (-x, -y + 1, -z + 1)] but are not coplanar, occupying parallel molecular planes 0.547 Å apart.

The undulating chains are crosslinked by N12···H13Biv—N13Biv hydrogen bonds [symmetry code: (iv) y, -x + 1/2, -z - 1/2], resulting in the formation of a three-dimensional network (Fig. 3) which includes an R44(12) motif comprising only N and H atoms and exhibiting crystallographically imposed 4 symmetry. Only about 40 examples of this motif are known, and they are dominated by pyrazoles and similar species containing cyclic NNH units (Cambridge Structural Database, Version 5.33, May 2012; Allen, 2002). However, two hydrazone examples have been reported, namely anthracene-9-carbaldehyde hydrazone (Urban et al., 2003) and 2-nitrobenzaldehyde hydrazone (Glidewell et al., 2004).

An intermolecular O2···C3iii contact of 2.944 (2) Å [symmetry code: (iii) y + 1/2, x, -z + 1/2] is observed between two molecules which lie approximately perpendicular to each other, as indicated by the dihedral angle of 85.82 (4)° between the molecular planes (Fig. 2). The related C2O2···C3iii and O2···C3iii—C2iii angles have values of 173.84 (11) and 81.71 (11)°, respectively. Stacking interactions occur between the five-membered ring and the symmetry-related six-membered ring at (-x, -y + 1, -z), with a centroid-to-centroid distance of 3.473 (2) Å and a perpendicular distance of 3.3980 (7) Å.

In summary, the most interesting features of the title molecule are its approximate C2v symmetry and the cis orientation of its NH2 groups, which are assisted by intramolecular N—H···O hydrogen bonding; its asymmetric involvement in a three-dimensional intermolecular hydrogen-bonded network; the presence of an R44(12) motif with 4 symmetry containing only N and H atoms; and the presence of weaker ππ and C O···C interactions.

Related literature top

For related literature, see: Allen (2002); Derebe et al. (2002, 2003); Etter et al. (1990); Everse & Menzel (1986); Fregeau et al. (2000); Glidewell et al. (2004); Holme & Peck (1998); Koteswara & Ram Reddy (1990); Mehabaw (2001); Menzel & Mitchell (1990); Negash (2003); Urban et al. (2003); Vogel (1989).

Experimental top

All reagents used were of analytical grade and solvents were dried and distilled prior to use (Vogel, 1989). Ninhydrin (2.00 g, 11.23 mmol) was dissolved in hot ethanol (100 ml). The solution was cooled to room temperature and hydrazine monohydrate (20 ml, 41.2 mmol) was added. The reaction mixture was stirred continuously for 1 h. Water (100 ml) was then added and the mixture left to stand overnight. The yellow precipitate which formed was filtered off and washed with aqueous ethanol. The product, (I), was recrystallized from ethanol (yield 1.40 g, 60%; m.p. 517–518 K).

Refinement top

The H atoms of the NH2 groups were located in ΔF syntheses and refined freely, with restraints of 0.88 (1) Å on the N—H distances and with Uiso(H) = 1.5Ueq(N). The remaining H atoms were placed geometrically and treated as riding, with C—H = 0.96 Å and Uiso(H) = 1.2Ueq(C). Six reflections flagged as outliers were omitted from the refinement.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002) and SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. A view of (I), showing the atom-numbering scheme. Intramolecular N—H···O hydrogen bonds are shown as dotted lines. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of a molecule of (I) in the same orientation as in Fig. 1, showing part of the local hydrogen-bonding network. [Symmetry codes: (i) -y + 1/2, x, -z - 1/2; (ii) -x, -y + 1, -z + 1; (iii) -y + 1/2, x, -z - 1/2; (iv) y, -x + 1/2, -z - 1/2.]
[Figure 3] Fig. 3. The three-dimensional hydrogen-bonded network in (I), viewed along the c axis. The R44(12) motif comprising only N and H atoms is disposed around a site of 4 symmetry. Intramolecular N—H···O hydrogen bonds and H atoms not involved in the network have been omitted for clarity.
(1Z,3Z)-1,3-dihydrazinylidene-1H-inden-2(3H)-one top
Crystal data top
C9H8N4ODx = 1.422 Mg m3
Mr = 188.19Melting point = 517–518 K
Tetragonal, P42/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 4bcCell parameters from 2364 reflections
a = 13.808 (6) Åθ = 2.7–27.5°
c = 9.219 (4) ŵ = 0.10 mm1
V = 1757.7 (13) Å3T = 150 K
Z = 8Block, pale yellow
F(000) = 7840.22 × 0.19 × 0.09 mm
Data collection top
Bruker SMART1000 CCD area-detector
diffractometer
1275 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.071
Graphite monochromatorθmax = 27.6°, θmin = 2.1°
Detector resolution: 8.336 pixels mm-1h = 1217
ω scansk = 1617
11027 measured reflectionsl = 1111
2006 independent reflections
Refinement top
Refinement on F20 constraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 0.92 w = 1/[σ2(Fo2) + (0.052P)2]
where P = (Fo2 + 2Fc2)/3
2006 reflections(Δ/σ)max < 0.001
139 parametersΔρmax = 0.18 e Å3
4 restraintsΔρmin = 0.15 e Å3
Crystal data top
C9H8N4OZ = 8
Mr = 188.19Mo Kα radiation
Tetragonal, P42/nµ = 0.10 mm1
a = 13.808 (6) ÅT = 150 K
c = 9.219 (4) Å0.22 × 0.19 × 0.09 mm
V = 1757.7 (13) Å3
Data collection top
Bruker SMART1000 CCD area-detector
diffractometer
1275 reflections with I > 2σ(I)
11027 measured reflectionsRint = 0.071
2006 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0394 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 0.92Δρmax = 0.18 e Å3
2006 reflectionsΔρmin = 0.15 e Å3
139 parameters
Special details top

Refinement. The N—H H atoms were refined with restraints of 0.88 (1) Å on the N—H distances.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.12468 (10)0.38955 (11)0.00914 (16)0.0286 (4)
C20.09595 (11)0.36494 (11)0.14018 (17)0.0299 (4)
O20.08356 (9)0.28287 (8)0.19053 (12)0.0385 (3)
C30.08281 (11)0.45781 (11)0.21813 (17)0.0304 (4)
C40.10809 (11)0.53580 (11)0.11763 (17)0.0292 (4)
C50.13211 (11)0.49525 (11)0.01863 (16)0.0288 (4)
C60.10800 (12)0.63560 (12)0.13719 (19)0.0369 (4)
H60.09210.66290.22870.044*
C70.13161 (12)0.69448 (13)0.0207 (2)0.0419 (4)
H70.13250.76280.03290.050*
C80.15400 (13)0.65477 (12)0.1140 (2)0.0418 (4)
H80.16920.69640.19280.050*
C90.15444 (12)0.55537 (12)0.13482 (18)0.0350 (4)
H90.16980.52880.22700.042*
N100.05134 (10)0.47118 (10)0.34980 (14)0.0353 (4)
N110.03183 (12)0.39269 (12)0.43159 (16)0.0445 (4)
H11A0.0300 (15)0.3365 (10)0.384 (2)0.067*
H11B0.0002 (14)0.4046 (15)0.5128 (15)0.067*
N120.13888 (9)0.33026 (9)0.11777 (14)0.0301 (3)
N130.12666 (11)0.23621 (10)0.09558 (15)0.0359 (3)
H13A0.1120 (13)0.2143 (14)0.0066 (13)0.054*
H13B0.1391 (13)0.1970 (12)0.1695 (15)0.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0257 (8)0.0327 (9)0.0274 (8)0.0007 (7)0.0020 (6)0.0038 (7)
C20.0287 (9)0.0332 (9)0.0278 (9)0.0011 (7)0.0011 (7)0.0022 (7)
O20.0515 (8)0.0323 (7)0.0318 (7)0.0001 (5)0.0066 (5)0.0006 (5)
C30.0271 (8)0.0371 (9)0.0270 (8)0.0016 (7)0.0014 (6)0.0047 (7)
C40.0221 (8)0.0331 (9)0.0325 (9)0.0008 (6)0.0002 (6)0.0038 (7)
C50.0229 (8)0.0328 (9)0.0309 (9)0.0003 (7)0.0016 (6)0.0025 (7)
C60.0324 (9)0.0359 (10)0.0424 (10)0.0010 (7)0.0039 (7)0.0093 (8)
C70.0387 (10)0.0299 (9)0.0569 (12)0.0030 (8)0.0051 (9)0.0031 (8)
C80.0387 (10)0.0370 (10)0.0496 (11)0.0044 (8)0.0071 (9)0.0063 (8)
C90.0324 (9)0.0375 (10)0.0351 (9)0.0028 (7)0.0059 (7)0.0006 (8)
N100.0366 (8)0.0407 (8)0.0286 (8)0.0043 (6)0.0019 (6)0.0037 (6)
N110.0632 (11)0.0415 (9)0.0288 (9)0.0065 (8)0.0124 (7)0.0003 (7)
N120.0289 (7)0.0312 (8)0.0303 (7)0.0001 (6)0.0029 (6)0.0045 (6)
N130.0447 (9)0.0321 (8)0.0310 (8)0.0007 (7)0.0065 (7)0.0065 (6)
Geometric parameters (Å, º) top
C1—C21.472 (2)C7—C81.392 (2)
C1—C51.466 (2)C7—H70.9500
C1—N121.308 (2)C8—C91.386 (2)
C2—O21.2365 (19)C8—H80.9500
C2—C31.481 (2)C9—H90.9500
C3—N101.302 (2)N10—N111.347 (2)
C3—C41.463 (2)N11—H11A0.891 (9)
C4—C61.390 (2)N11—H11B0.885 (9)
C4—C51.415 (2)N12—N131.325 (2)
C5—C91.390 (2)N13—H13A0.897 (9)
C6—C71.386 (2)N13—H13B0.888 (9)
C6—H60.9500
N12—C1—C5124.54 (14)C6—C7—C8120.82 (16)
N12—C1—C2127.71 (14)C6—C7—H7119.6
C5—C1—C2107.73 (13)C8—C7—H7119.6
O2—C2—C1126.86 (14)C9—C8—C7120.98 (16)
O2—C2—C3126.47 (15)C9—C8—H8119.5
C1—C2—C3106.67 (14)C7—C8—H8119.5
N10—C3—C4124.44 (14)C8—C9—C5118.93 (15)
N10—C3—C2128.01 (15)C8—C9—H9120.5
C4—C3—C2107.51 (14)C5—C9—H9120.5
C6—C4—C5120.52 (14)C3—N10—N11118.31 (14)
C6—C4—C3130.36 (15)N10—N11—H11A115.6 (14)
C5—C4—C3109.08 (14)N10—N11—H11B115.1 (14)
C9—C5—C4120.00 (15)H11A—N11—H11B124 (2)
C9—C5—C1131.02 (14)C1—N12—N13118.42 (13)
C4—C5—C1108.95 (13)N12—N13—H13A120.0 (13)
C7—C6—C4118.74 (15)N12—N13—H13B117.1 (13)
C7—C6—H6120.6H13A—N13—H13B122.7 (19)
C4—C6—H6120.6
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11A···O20.89 (1)2.07 (2)2.784 (2)136 (2)
N13—H13A···O20.90 (1)2.09 (2)2.780 (2)133 (2)
N13—H13B···N12i0.89 (1)2.16 (1)3.024 (2)164 (2)
N11—H11B···N10ii0.89 (1)2.25 (2)2.986 (2)141 (2)
N13—H13A···N11iii0.90 (1)2.61 (2)3.213 (3)125 (2)
Symmetry codes: (i) y+1/2, x, z1/2; (ii) x, y+1, z+1; (iii) y+1/2, x, z+1/2.

Experimental details

Crystal data
Chemical formulaC9H8N4O
Mr188.19
Crystal system, space groupTetragonal, P42/n
Temperature (K)150
a, c (Å)13.808 (6), 9.219 (4)
V3)1757.7 (13)
Z8
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.22 × 0.19 × 0.09
Data collection
DiffractometerBruker SMART1000 CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
11027, 2006, 1275
Rint0.071
(sin θ/λ)max1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.098, 0.92
No. of reflections2006
No. of parameters139
No. of restraints4
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.18, 0.15

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002) and SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top
C1—C21.472 (2)C4—C51.415 (2)
C1—C51.466 (2)C5—C91.390 (2)
C1—N121.308 (2)C6—C71.386 (2)
C2—O21.2365 (19)C7—C81.392 (2)
C2—C31.481 (2)C8—C91.386 (2)
C3—N101.302 (2)N10—N111.347 (2)
C3—C41.463 (2)N12—N131.325 (2)
C4—C61.390 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11A···O20.891 (9)2.070 (16)2.784 (2)136 (2)
N13—H13A···O20.897 (9)2.087 (16)2.780 (2)133 (2)
N13—H13B···N12i0.888 (9)2.161 (11)3.024 (2)164 (2)
N11—H11B···N10ii0.885 (9)2.246 (15)2.986 (2)141 (2)
N13—H13A···N11iii0.897 (9)2.614 (17)3.213 (3)125 (2)
Symmetry codes: (i) y+1/2, x, z1/2; (ii) x, y+1, z+1; (iii) y+1/2, x, z+1/2.
 

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