(E)-1-Phenyl­butan-2-one (2,4-dinitro­phen­yl)hydrazone

Carlos F R A C Lima; Ligia R Gomes; Luís M N B F Santos; José E Rodriguez-Borges; John Nicolson Low

doi:10.1107/S1600536809041178

. 2009 Oct 17;65(Pt 11):o2729. doi: 10.1107/S1600536809041178

(E)-1-Phenylbutan-2-one (2,4-dinitrophenyl)hydrazone

Carlos F R A C Lima ^a, Ligia R Gomes ^b, Luís M N B F Santos ^a, José E Rodriguez-Borges ^a, John Nicolson Low ^c,^*

PMCID: PMC2971069 PMID: 21578325

Abstract

In the title compound, C₁₆H₁₆N₄O₄, the dihedral angle between the aromatic rings is 79.04 (8)° and an intramolecular N—H⋯O hydrogen bond occurs. In the crystal, weak C—H.·O and C—H..π interactions link the molecules, forming sheets.

Related literature

For the structure of the related 2,4-dinitrophenyl hydrazine, see: Wardell et al. (2006 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₆H₁₆N₄O₄
M _r = 328.33
Monoclinic,
a = 15.8919 (13) Å
b = 4.9446 (3) Å
c = 20.7397 (17) Å
β = 105.267 (5)°
V = 1572.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 120 K
0.30 × 0.05 × 0.02 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.970, T _max = 0.998
14305 measured reflections
3531 independent reflections
2418 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.101
S = 1.01
3531 reflections
218 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809041178/hb5130sup1.cif

e-65-o2729-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809041178/hb5130Isup2.hkl

e-65-o2729-Isup2.hkl^{(173.2KB, 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
N1—H1⋯O122	0.85	1.95	2.5966 (17)	132
C3—H3A⋯O142ⁱ	0.99	2.50	3.432 (2)	158
C32—H32⋯O142ⁱ	0.95	2.52	3.349 (2)	146
C3—H3B⋯Cg2ⁱⁱ	0.99	2.75	3.534 (2)	136

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Symmetry codes: (i) Inline graphic ; (ii) . Cg2 is the centroid of C31–C36 ring.

Acknowledgments

CFRACL also thanks FCT and the European Social Fund (ESF) under the third Community Support Framework (CSF) for the award of a PhD Research Grant (SRFH/BD/29394/2006). LRG thanks the Fundação para o Ensino e Cultura Fernando Pessoa.

supplementary crystallographic information

Comment

The molecular geometry and conformation is as expected taking acount of electronic repulsions and steric effects. The orange colour is caused by the conjugation of the nitrophenyl with the –N—N= group. The backbone of the molecule is essentially planar with only the methyl group, C21, and the phenyl group attached to C3 lying out of the plane of the molecule, Fig. 1.

Atom N1 forms an intramolecular hydrogen bond via H1 with atom O122 so forming an R(6) ring, (Bernstein et al., 1995). Atom O142 acts as a hydrogen bond acceptor from donor atoms C3, via H3B, and C32, via H32, thus forming an R²₁(5) ring which links screw-related molecules into chains running parallel to (101). These chains are linked to form sheets running parallel to the b axis by the C—H···π contact in which C3 acts as a donor atom via H3B to the phenyl ring containing C31, Fig.2.

There is a short intermolecular nitro to nitro group contact between O122···N12(-x + 1.5, y + 1/2, -z + 1/2) of 2.76 Å.

The relevant bonds and angles compare well with those in 2,4-dinitrophenylhydrazine: Wardell et al. 2006.

Experimental

The title compound was obtained from the condensation reaction of 1-phenyl-2-butanone with dinitrophenylhydrazine. The liquid 1-phenyl-2-butanone (2.0 mmol) was added to a warm solution (323 K) of 2,4-dinitrophenylhydrazine (2.5 mmol) in a mixture of 10 ml of ethanol/ 1 ml of HCl (37%) and allowed to react for 30 minutes. The resulting mixture was extracted with ethylacetate. A solid product was obtained after evaporation of the solvent this was first re-crystallized with ethanol and then with ethylacetate. Slow evaporation of a dichloromethane solution gave orange needles of (I).