(E)-1-(4-Nitro­phen­yl)-2-(4-{[(E)-2-(4-nitro­phen­yl)hydrazinyl­idene]meth­yl}benzyl­idene)hydrazine dihydrate

Edward R T Tiekink; James L Wardell; Solange M S V Wardell

doi:10.1107/S1600536809053963

. 2009 Dec 19;66(Pt 1):o191–o192. doi: 10.1107/S1600536809053963

(E)-1-(4-Nitrophenyl)-2-(4-{[(E)-2-(4-nitrophenyl)hydrazinylidene]methyl}benzylidene)hydrazine dihydrate

Edward R T Tiekink ^a,^*, James L Wardell ^b,^‡, Solange M S V Wardell ^c

PMCID: PMC2980149 PMID: 21580076

Abstract

The 30 non-H atoms in title dihydrazine compound, C₂₀H₁₆N₆O₄·2H₂O, are close to coplanar, the r.m.s. deviation for these atoms being 0.096 Å. The conformation about each of the C=N bonds is E, and the molecule has non-crystallographic 2/m symmetry. The presence of O—H⋯O and N—H⋯O hydrogen bonding leads to a three-dimensional network in the crystal structure. A highly disordered solvent molecule is present within a molecular cavity defined by the organic and water molecules. Its contribution to the electron density was removed from the observed data in the final cycles of refinement and the formula, molecular weight and density are given without taking into account the contribution of the solvent molecule.

Related literature

For background to the structural chemistry of hydrazones, see: Baddeley et al. (2009 ▶); Ferguson et al. (2005 ▶); Glidewell et al. (2006 ▶); Low et al. (2006 ▶); Wardell et al. (2005 ▶, 2006 ▶). For the synthesis, see: Bengelsdorf (1958 ▶).

Experimental

Crystal data

C₂₀H₁₆N₆O₄·2H₂O
M _r = 440.42
Triclinic,
a = 7.7549 (4) Å
b = 9.3245 (7) Å
c = 15.3374 (11) Å
α = 100.749 (3)°
β = 90.533 (4)°
γ = 103.131 (5)°
V = 1059.56 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 120 K
0.38 × 0.22 × 0.07 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.770, T _max = 1.000
16566 measured reflections
3688 independent reflections
2638 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.177
S = 1.09
3688 reflections
301 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053963/hg2618sup1.cif

e-66-0o191-sup1.cif^{(21.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053963/hg2618Isup2.hkl

e-66-0o191-Isup2.hkl^{(213.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1w⋯O4ⁱ	0.83 (2)	2.32 (2)	3.084 (2)	153 (2)
O1W—H2w⋯O2wⁱⁱ	0.83 (2)	2.01 (2)	2.808 (3)	163 (3)
N5—H5n⋯O1w	0.88	2.17	3.021 (3)	163
O2W—H3w⋯O1wⁱⁱⁱ	0.84 (3)	1.98 (3)	2.800 (3)	165 (3)
O2W—H4w⋯O1^iv	0.84 (2)	2.28 (2)	3.061 (3)	156 (3)
O2W—H4w⋯O2^iv	0.84 (2)	2.45 (2)	3.204 (3)	150 (3)
N2—H2n⋯O2w^v	0.88	2.09	2.959 (3)	172
C7—H7⋯O2^vi	0.95	2.48	3.374 (3)	157
C14—H14⋯O3ⁱ	0.95	2.45	3.338 (3)	156

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CAPES (Brazil).

supplementary crystallographic information

Comment

In connection with on-going studies into the structural chemistry of hydrazones (Baddeley et al., 2009; Ferguson et al., 2005; Glidewell et al., 2006; Low et al., 2006; Wardell et al., 2005; Wardell et al., 2006), we now report the structure of the title compound, (I).

The molecule in (I) is essentially planar with the r.m.s. of the 30 non-hydrogen atoms being 0.096 Å. The maximum deviations from the least-squares plane are 0.243 (2) Å for atom O3 and -0.140 (3) Å for atom C13; the former deviation arises as the N6-nitro group is slightly twisted out of the plane of the benzene ring to which it is attached: the C17–C18–N6–O3 torsion angle is 7.1 (3)°. The conformation about each of the C7═ N3 [1.288 (3) Å] and C14═N4 [1.280 (3) Å] bonds is E. Overall, to a first approximation, the molecule has non-crystallographic 2/m symmetry.

The water molecules are involved in a number of hydrogen bonding interactions and stabilize a double layer arrangement. As illustrated in Fig. 2, molecules are arranged into a layer being connected by O–H···O and N–H···O hydrogen bonds as well as C–H···O contacts, Table 1. Each of the hydrazine-H atoms forms a donor interaction to a water molecule. The O1w water molecule forms a donor hydrogen bond with a O2w water molecule in the plane, Fig. 2, as well as with a nitro-O4 atom. The O2w water molecule accepts a hydrogen bond from the O1w atom as described above, and forms two donor interactions with the nitro-O1 and O2 atoms via a bifurcated H4w atom. Each of the nitro O1 and O2 atoms forms a C–H···O contact. The aforementioned interactions stabilize a 2-D array. Each of the O1w (acceptor) and O2w (donor) molecules forms one further hydrogen bond to a water molecule of a centrosymmetrically related layer to form a double layer as well as eight-membered {···O—H}₄ synthons. Further stability to the double layers is afforded by weak π···π interactions [ring centroid(C16–C6)···ring centroid(C15—C20)ⁱ = 3.6716 (16) Å with a dihedral angle between planes = 2.31 (12) ° for symmetry operation i: 1 - x, -y, 2 - z]. Layers stack in the crystal structure as illustrated in Fig. 3. As noted in the Experimental, ill-defined solvent, most probably methanol, was present in the crystal structure. These are located in the vicinity of the voids within the double layer.

Experimental

Solutions of 4-nitrophenylhydrazine (0.306 g, 2 mmol) in MeOH (25 ml) and 1,4-benzenedicarboxaldehyde (0.134 g, 1 mmol) in MeOH (15 ml) were mixed, and refluxed for 30 min. The reaction mixture was rotary evaporated and the residue was chromatographed on alumina using hexane/ethyl acetate [4:1] as eluent. The collected fraction of 1,4-bis-2-(4-nitrophenyl)hydrazone 1,4-benzenedicarboxaldehyde was recrystallized from MeOH, m.pt. 566–568 K. lit value 567–568 K (Bengelsdorf, 1958). IR (KBr, cm^-1): ν 3261, 1608, 1587, 1556, 1498, 1469, 1321, 1309, 1293, 1271, 1173, 1105, 1086, 998, 929, 839, 750, 694, 585, 530, 489, 435.