organic papers
o1704
Ivo Vencatoet al. C11H12ClN3O DOI: 10.1107/S1600536804020124 Acta Cryst.(2004). E60, o1704±o1706 Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
The azo±enaminone 4-(
E
)-amino-3-[(
E
)-2-chloro-phenyldiazenyl]pent-3-en-2-one
Ivo Vencato,a* Silvio Cunha,b
Valeria Rocha,b Zenis Novais da
Rochaband Carlito Lariuccia
aInstituto de FõÂsica - UFG, 74001-970 - GoiaÃnia,
GO, Brazil, andbInstituto de QuõÂmica - UFBA,
Campus de Ondina, 40170-290 - Salvador, BA, Brazil
Correspondence e-mail: vencato@if.ufg.br
Key indicators
Single-crystal X-ray study T= 293 K
Mean(C±C) = 0.004 AÊ Rfactor = 0.060 wRfactor = 0.185
Data-to-parameter ratio = 13.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, C11H12ClN3O, is composed of a planar
azoenamine skeleton, which forms a six-membered ring through an intramolecular hydrogen bond. In the solid state only the azoenamine tautomer was observed. The molecular packing is through adjacent molecules linked by NÐH O bonds, resulting in a two-dimensional sheet structure.
Comment
Although a number of X-ray structural investigations invol-ving simple enaminones have been reported (Cunha et al., 2003; Cunhaet al., 2002; Gilliet al., 2000; Kubickiet al., 2000; Dannhardt et al., 1998; Bertolasi et al., 1998), structural analyses of azo-enaminones are relatively scarce (Simuneket al., 2002, Rodrigueset al., 1996; Kettmannet al., 2001). Studies of the molecular packing of enaminones in the solid state are of particular interest because azo-enaminones are compounds with potential non-linear optical properties (Figueiredo & Kascheres, 1997; Oliveira et al., 2003). In addition, azo-en-aminones can exist in hydrazoimino/azoenamine tautomeric forms in both solution and the solid state (Kettmann et al., 2001; Simunek et al., 2002). Thus, we prepared the azo-en-aminone 4-(E)-amino-3-[(E )-2-chlorophenylazo]-3-penten-2-one, (I), and undertook its structural analysis. An ORTEP
(Farrugia, 1997) plot of the molecule and the atomic numbering is shown in Fig. 1. Selected bond distances and angles are given in Table 1. The compound contains an NH2
hydrogen-bond-donor group, with a Cl atom attached to the aromatic ring.
With regard to the tautomeric equilibrium, (I) exists predominantly in the azoenamine form in the solid state, as can be seen from the bond lengths along C6ÐN3ÐN2ÐC3Ð C4ÐN1 (see Table 1), which are in agreement with others previously reported for azo-enaminones containing an NH2
group (Rodrigueset al., 1996; Kettmannet al., 2001; Simunek
et al., 2002).
According to NMR spectroscopy, no evidence was found for the existence of tautomer (II) in the solution state.
However, in the structure determination, the distances N3Ð N2 = 1.276 (3), N2ÐC3 = 1.370 (3), C3ÐC4 = 1.423 (3) and C4ÐN1 = 1.306 (3) AÊ are closest to the single and double bonds CÐN, N N and C C, respectively, in agreement with structural analyses described for analogous azo-enaminones (Kettmann et al., 2001. These small differences made us suspect the presence of a small amount of the tautomer (II) in the structure. However, unequivocal evidence for tautomer (II) was not found in a search for either occupational and
orientational/occupational disorder, as re¯ected by peaks at distances about 0.5 AÊ from the atoms, while attempts to re®ne a weak peak located near atom N3 in the difference map as a disordered H-atom site did not improve the model signi®-cantly.
Atom H2 on N1 is involved in a strong intramolecular [2.559 (3) AÊ] hydrogen bond directed towards N3 of the azo group (Table 2). Atom N1 is ÿ0.099 (4) AÊ from the least-squares plane through atoms C6, N3, N2, C3 and C4. Intra-molecular hydrogen bonds therefore contribute to the planarity of this conjugated moiety of (I). In addition, the aromatic ring is coplanar with the enaminone moiety, as indicated by the C7ÐC6ÐN3ÐN2 torsion angle ofÿ0.3 (3). The molecular packing of (I) occurs through a hydrogen-bonded network (Figs. 2 and 3, Table 2). In this network, two-dimensional head-to-head molecular-orientated chains are observed, which involve only the enaminone moiety (the head) and not the aromatic ring (the tail).
Experimental
Compound (I) was prepared through the reaction of 4-aminopent-3-en-2-one with the diazonium salt of 2-chloroaniline, in a method analogous to that used previously in the synthesis of other azo-en-aminones (Simuneket al., 2002; Kettmannet al., 2001; Figueiredo & Kascheres, 1997). To a solution of 1.2830 g (10 mmol) of 2-chloro-aniline in 6 ml of 6 N HCl in 10 ml of water was added dropwise a solution of 0.9771 g (14 mmol) of NaNO2in 15 ml of water under
vigorous magnetic stirring and ice-bath cooling. 26.2 mg of urea was added and the solution was neutralized by the addition of solid Na2CO3. 15 ml of CH2Cl2was added, followed by 0.9960 g (10 mmol)
of 4-aminopent-3-en-2-one in 20 ml of CH2Cl2. The resulting solid
was collected by ®ltration and recrystallized from ethanol, giving 0.9324 g (39% yield) of 4-(E)-amino-3-[(E)-2-chlorophenylazo]-3-penten-2-one as yellow crystals, m.p. 462±464 K. IR (KBr): 3459, 3224, 1634, 1570, 1442, 1363 cmÿ1.1H NMR (CDCl
3, 300 Hz):2.58
(3H,s); 2.60 (3H,s); 7.18 (1H,t,J= 8.1 Hz); 7.32 (1H,t,J= 6.6 Hz); 7.60 (1H,d,J= 6.6 Hz); 7.79 (1H,d,J= 8.1 Hz); 14.0 (1H, broad). Crystal data
C11H12ClN3O
Mr= 237.69
Monoclinic,P21=c
a= 7.673 (6) AÊ b= 12.887 (1) AÊ c= 11.598 (1) AÊ
= 91.28 (2) V= 1146.5 (9) AÊ3
Z= 4
Dx= 1.377 Mg mÿ3
CuKradiation Cell parameters from 25
re¯ections
= 11.6±30.0
= 2.81 mmÿ1
T= 293 (2) K Irregular, pale yellow 0.350.130.12 mm
organic papers
Acta Cryst.(2004). E60, o1704±o1706 Ivo Vencatoet al. C11H12ClN3O
o1705
Figure 3
Packing diagram, viewed down thebaxis, showing the two-dimensional sheet structure formed by the hydrogen bonding network (dashed lines).
Figure 1
The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
Figure 2
Data collection
Nonius CAD-4 diffractometer
!±2scans
Absorption correction: scan Northet al.(1968) Tmin= 0.649,Tmax= 0.714
2335 measured re¯ections 2038 independent re¯ections 1756 re¯ections withI> 2(I)
Rint= 0.058
max= 67.0
h=ÿ9!8 k= 0!15 l=ÿ1!13 3 standard re¯ections
frequency: 120 min intensity decay:<1.0% Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.061
wR(F2) = 0.185
S= 1.06 2038 re¯ections 153 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.1286P)2
+ 0.3565P]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001
max= 0.50 e AÊÿ3
min=ÿ0.49 e AÊÿ3
Extinction correction:SHELXL Extinction coef®cient: 0.033 (3)
Table 1
Selected geometric parameters (AÊ,).
ClÐC11 1.737 (3)
N1ÐC4 1.306 (3)
N2ÐN3 1.276 (3)
N2ÐC3 1.370 (3)
N3ÐC6 1.416 (3)
C3ÐC4 1.423 (3)
C4ÐN1ÐH1 121 (2)
C4ÐN1ÐH2 114.4 (19)
H1ÐN1ÐH2 124 (3)
N3ÐN2ÐC3 118.7 (2)
N2ÐN3ÐC6 113.78 (19)
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N1ÐH2 N3 0.94 (3) 1.79 (3) 2.559 (3) 137 (3)
N1ÐH1 O1i 0.82 (3) 2.10 (3) 2.862 (3) 155 (3)
Symmetry code: (i) 1ÿx;1
2y;ÿ12ÿz.
All phenyl H atoms were placed in calculated positions using a riding model [CÐH = 0.93 AÊ,Uiso(H) = 1.2Ueq(C) for Csp2]; the H
atoms on N1 were found in the difference Fourier map and re®ned withUiso(H) = 1.2Ueq(N). The H atoms of the Csp3atoms C1 and C5
= were placed in calculated positions (CÐH = 0.96 AÊ) and re®ned as riding, withUiso(H) = 1.5Ueq(C).
Data collection:CAD-4/PC(Enraf±Nonius, 1993); cell re®nement: CAD-4/PC; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:ORTEP-3 for Windows(Farrugia, 1997); soft-ware used to prepare material for publication:WinGX publication routines (Farrugia, 1999).
The authors thank the Brazilian Agencies for fellowships to VR (CAPES) and IV (CNPq).
References
Bertolasi, V., Gilli, P., Ferretti, V. & Gilli, G. (1998).Acta Cryst.B54, 50±65. Cunha, S., Rodovalho, W., Azevedo, N. R., Mendonca, M. O., Lariucci, C. &
Vencato, I. (2002).J. Braz.Chem. Soc.13, 629±634.
Cunha, S., Silva, V. C. da, Napolitano, H. B., Lariucci, C. & Vencato, I. (2003). J. Braz.Chem. Soc.14, 107±112.
Dannhardt, G., Bauer, A. & Nowe, U. (1998).J. Prakt. Chem.340, 259±263. Enraf±Nonius (1993). CAD-4/PC. Version 1.2. Enraf±Nonius, Delft, The
Netherlands.
Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±838.
Figueiredo, L. J. O. & Kascheres, C. (1997).J. Org. Chem.62, 1164±1167. Gilli, P., Bertolasi, V., Ferretti, V. & Gilli, G. (2000).J. Am. Chem. Soc.122,
10405±10417.
Harms, K. & Wocadlo, S. (1995).XCAD4. University of Marburg, Germany. Kettmann, V., Lokaj, J., Simunek, P. & Machacek, V. (2001).Acta Cryst.C57,
737±739.
Kubicki, M., Bassyouni, H. A. R. & Codding, P. W. (2000).J. Mol. Struct.525, 141±152.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst, A24, 351± 359.
Oliveira, H. C. B., Fonseca, T. L., Castro, M. A., Amaral, O. V. A. & Cunha, S. (2003).J. Chem. Phys.119, 8417±8423.
Rodrigues, B. L., Gambardella, M. T. P., Figueiredo, L. J. O. & Kascheres, C. (1996).Acta Cryst.C52, 705±707.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Simunek, P., Bertolasi, V. & Machacek, V. (2002).J. Mol. Struct.642, 41±51.
organic papers
supporting information
sup-1 Acta Cryst. (2004). E60, o1704–o1706
supporting information
Acta Cryst. (2004). E60, o1704–o1706 [https://doi.org/10.1107/S1600536804020124]
The azo
–
enaminone 4-(
E
)-amino-3-[(
E
)-2-chlorophenyldiazenyl]pent-3-en-2-one
Ivo Vencato, Silvio Cunha, Valeria Rocha, Zenis Novais da Rocha and Carlito Lariucci
4-(E)-amino-3-[(E)-2-chlorophenylazo]-3-penten-2-one
Crystal data
C11H12ClN3O
Mr = 237.69 Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 7.673 (6) Å
b = 12.887 (1) Å
c = 11.598 (1) Å
β = 91.28 (2)°
V = 1146.5 (9) Å3
Z = 4
F(000) = 496
Dx = 1.377 Mg m−3
Melting point = 462–464 K Cu Kα radiation, λ = 1.54180 Å Cell parameters from 25 reflections
θ = 11.6–30.0°
µ = 2.81 mm−1
T = 293 K
Irregular, pale yellow 0.35 × 0.13 × 0.12 mm
Data collection
Nonius CAD-4 diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
ω–2θ scans
Absorption correction: ψ scan North, Phillips & Mathews (1968)
Tmin = 0.649, Tmax = 0.714
2335 measured reflections
2038 independent reflections 1756 reflections with I > 2σ(I)
Rint = 0.058
θmax = 67.0°, θmin = 5.1°
h = −9→8
k = 0→15
l = −1→13
3 standard reflections every 120 min intensity decay: <1.0%
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.061
wR(F2) = 0.185
S = 1.06 2038 reflections 153 parameters 1 restraint
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(F
o2) + (0.1286P)2 + 0.3565P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.50 e Å−3
Δρmin = −0.49 e Å−3
Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
supporting information
sup-2 Acta Cryst. (2004). E60, o1704–o1706
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Cl 0.76190 (10) 0.75900 (5) 0.07214 (6) 0.0604 (4) N1 0.5838 (3) 0.59484 (17) −0.1783 (2) 0.0528 (6) N2 0.7365 (2) 0.44633 (15) −0.02338 (16) 0.0410 (5) N3 0.7441 (3) 0.54109 (15) 0.00814 (16) 0.0437 (5) O1 0.6051 (3) 0.27355 (15) −0.24254 (17) 0.0628 (6)
C1 0.7304 (4) 0.2404 (2) −0.0583 (3) 0.0589 (8)
H1A 0.7211 0.1698 −0.0840 0.088*
H1B 0.6634 0.2495 0.0099 0.088*
H1C 0.8504 0.2565 −0.0412 0.088*
C2 0.6619 (3) 0.31199 (19) −0.1518 (2) 0.0445 (6) C3 0.6642 (3) 0.42316 (19) −0.12936 (18) 0.0406 (6) C4 0.5927 (3) 0.49726 (19) −0.2081 (2) 0.0432 (6)
C5 0.5275 (4) 0.4708 (2) −0.3268 (2) 0.0568 (7)
H5A 0.4905 0.5330 −0.3658 0.085*
H5B 0.4308 0.4238 −0.3219 0.085*
H5C 0.6192 0.4386 −0.3689 0.085*
C6 0.8233 (3) 0.55584 (19) 0.11834 (19) 0.0431 (6)
C7 0.8875 (4) 0.4765 (2) 0.1883 (2) 0.0523 (7)
H7 0.8799 0.4081 0.1633 0.063*
C8 0.9627 (4) 0.4986 (2) 0.2949 (2) 0.0587 (7)
H8 1.0067 0.4450 0.3407 0.070*
C9 0.9729 (4) 0.5993 (3) 0.3338 (2) 0.0610 (8)
H9 1.0226 0.6134 0.4060 0.073*
C10 0.9096 (4) 0.6793 (2) 0.2662 (2) 0.0578 (7)
H10 0.9158 0.7474 0.2926 0.069*
C11 0.8369 (3) 0.65778 (19) 0.1588 (2) 0.0465 (6)
H1 0.537 (4) 0.638 (2) −0.220 (3) 0.056*
H2 0.626 (4) 0.609 (2) −0.104 (3) 0.056*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3 Acta Cryst. (2004). E60, o1704–o1706
O1 0.0869 (15) 0.0459 (12) 0.0552 (11) −0.0094 (9) −0.0064 (10) −0.0093 (8) C1 0.0722 (19) 0.0370 (16) 0.0673 (18) 0.0036 (11) −0.0037 (14) 0.0019 (11) C2 0.0461 (13) 0.0399 (14) 0.0477 (13) −0.0014 (9) 0.0050 (10) −0.0032 (10) C3 0.0436 (12) 0.0392 (13) 0.0391 (11) 0.0021 (9) 0.0043 (9) −0.0010 (9) C4 0.0437 (12) 0.0426 (14) 0.0433 (12) 0.0009 (9) 0.0054 (10) 0.0023 (9) C5 0.0681 (17) 0.0561 (17) 0.0459 (14) 0.0046 (13) −0.0044 (12) 0.0010 (11) C6 0.0456 (12) 0.0419 (13) 0.0421 (12) −0.0007 (9) 0.0060 (9) −0.0028 (9) C7 0.0620 (15) 0.0449 (15) 0.0497 (14) 0.0028 (11) −0.0009 (11) −0.0016 (11) C8 0.0590 (16) 0.0663 (19) 0.0506 (15) 0.0035 (13) −0.0034 (12) 0.0021 (12) C9 0.0586 (16) 0.076 (2) 0.0483 (14) −0.0071 (13) −0.0039 (11) −0.0087 (13) C10 0.0619 (16) 0.0577 (17) 0.0540 (15) −0.0104 (12) 0.0050 (12) −0.0167 (12) C11 0.0477 (13) 0.0423 (14) 0.0500 (13) −0.0038 (10) 0.0088 (10) −0.0047 (10)
Geometric parameters (Å, º)
Cl—C11 1.737 (3) C4—C5 1.494 (3)
N1—C4 1.306 (3) C5—H5A 0.9600
N1—H1 0.82 (3) C5—H5B 0.9600
N1—H2 0.94 (3) C5—H5C 0.9600
N2—N3 1.276 (3) C6—C7 1.389 (4)
N2—C3 1.370 (3) C6—C11 1.398 (3)
N3—C6 1.416 (3) C7—C8 1.382 (4)
O1—C2 1.234 (3) C7—H7 0.9300
C1—C2 1.509 (4) C8—C9 1.376 (4)
C1—H1A 0.9600 C8—H8 0.9300
C1—H1B 0.9600 C9—C10 1.378 (4)
C1—H1C 0.9600 C9—H9 0.9300
C2—C3 1.456 (3) C10—C11 1.381 (4)
C3—C4 1.423 (3) C10—H10 0.9300
C4—N1—H1 121 (2) H5A—C5—H5B 109.5
C4—N1—H2 114.4 (19) C4—C5—H5C 109.5
H1—N1—H2 124 (3) H5A—C5—H5C 109.5
N3—N2—C3 118.7 (2) H5B—C5—H5C 109.5
N2—N3—C6 113.78 (19) C7—C6—C11 118.2 (2)
C2—C1—H1A 109.5 C7—C6—N3 124.6 (2)
C2—C1—H1B 109.5 C11—C6—N3 117.2 (2)
H1A—C1—H1B 109.5 C8—C7—C6 120.5 (3)
C2—C1—H1C 109.5 C8—C7—H7 119.8
H1A—C1—H1C 109.5 C6—C7—H7 119.8
H1B—C1—H1C 109.5 C9—C8—C7 120.5 (3)
O1—C2—C3 123.4 (2) C9—C8—H8 119.8
O1—C2—C1 118.6 (2) C7—C8—H8 119.8
C3—C2—C1 118.0 (2) C8—C9—C10 120.2 (2)
N2—C3—C4 124.9 (2) C8—C9—H9 119.9
N2—C3—C2 112.2 (2) C10—C9—H9 119.9
C4—C3—C2 122.9 (2) C9—C10—C11 119.6 (3)
supporting information
sup-4 Acta Cryst. (2004). E60, o1704–o1706
N1—C4—C5 116.4 (2) C11—C10—H10 120.2
C3—C4—C5 123.7 (2) C10—C11—C6 121.1 (2)
C4—C5—H5A 109.5 C10—C11—Cl 119.5 (2)
C4—C5—H5B 109.5 C6—C11—Cl 119.36 (19)
C3—N2—N3—C6 −179.21 (18) N2—N3—C6—C11 179.8 (2)
N3—N2—C3—C4 −1.2 (3) C11—C6—C7—C8 0.0 (4)
N3—N2—C3—C2 −178.9 (2) N3—C6—C7—C8 −179.9 (2)
O1—C2—C3—N2 −179.0 (2) C6—C7—C8—C9 0.9 (4)
C1—C2—C3—N2 2.0 (3) C7—C8—C9—C10 −0.7 (4)
O1—C2—C3—C4 3.3 (4) C8—C9—C10—C11 −0.4 (4)
C1—C2—C3—C4 −175.8 (2) C9—C10—C11—C6 1.2 (4)
N2—C3—C4—N1 −4.0 (4) C9—C10—C11—Cl −178.5 (2)
C2—C3—C4—N1 173.5 (2) C7—C6—C11—C10 −1.0 (4)
N2—C3—C4—C5 175.0 (2) N3—C6—C11—C10 178.9 (2)
C2—C3—C4—C5 −7.5 (4) C7—C6—C11—Cl 178.68 (18)
N2—N3—C6—C7 −0.3 (3) N3—C6—C11—Cl −1.4 (3)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N1—H2···N3 0.94 (3) 1.79 (3) 2.559 (3) 137 (3)
N1—H1···O1i 0.82 (3) 2.10 (3) 2.862 (3) 155 (3)
