organic papers
Acta Cryst.(2006). E62, o755–o756 doi:10.1107/S1600536806002352 Zhenget al. C
18H16N4O3
o755
Acta Crystallographica Section E Structure Reports
Online
ISSN 1600-5368
1,5-Dimethyl-4-(3-nitrobenzylideneamino)-2-phenylpyrazolidin-3-one
Chun-Sheng Zheng, Mei Li, Nan Yang and Zuo-Liang Jing*
College of Sciences, Tianjin University of Science and Technology, Tianjin 300222, People’s Republic of China
Correspondence e-mail: jzl74@tust.edu.cn
Key indicators
Single-crystal X-ray study T= 294 K
Mean(C–C) = 0.005 A˚ Rfactor = 0.062 wRfactor = 0.225
Data-to-parameter ratio = 12.6
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
Received 10 October 2005 Accepted 19 January 2006
#2006 International Union of Crystallography All rights reserved
The title compound, C18H16N4O3, was prepared by the reaction of 3-nitrobenzaldehyde and 4-amino-1,5-dimethyl-2-phenyl-pyrazol-3-one. The crystal structure displays an intra-molecular C—H O hydrogen bond, which may stabilize the conformation of the molecule, as well as intermolecular C— H O hydrogen bonds.
Comment
The syntheses and structures of Schiff bases have attracted much attention, because their metal complexes have been studied extensively as model compounds of biologically active compounds (Kahwaet al., 1986; Santoset al., 2001). As part of this investigation, we report here the synthesis and crystal structure of the title compound, (I).
A view of the molecular structure of (I) is shown in Fig. 1. The pyrazolidinone group C8–C10/N1–N3/O3 is planar, with an r.m.s. deviation for the fitted atoms of 0.0409 A˚ . This plane makes a dihedral angle of 48.55 (11) with the phenyl ring
(C13–C18) and a dihedral angle of 10.07 (11) with the
nitrobenzene ring (C1–C7/N4).
The intramolecular C—H O hydrogen bond (Table 1), may help to stabilize the observed conformation of the mol-ecule. In the crystal structure, the molecules are associatedvia
weak C—H O intermolecular hydrogen bonds (Table 1) to form a layer structure (Fig. 2).
Experimental
Crystal data
C18H16N4O3
Mr= 336.35
Monoclinic, P21=c
a= 7.645 (11) A˚
b= 7.839 (11) A˚
c= 28.24 (4) A˚ = 96.349 (19)
V= 1682 (4) A˚3
Z= 4
Dx= 1.328 Mg m 3 MoKradiation Cell parameters from 1975
reflections = 2.7–25.8
= 0.09 mm1
T= 294 (2) K Block, yellow 0.320.220.16 mm
Data collection
Bruker SMART CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.962,Tmax= 0.985 8161 measured reflections
2891 independent reflections 1817 reflections withI> 2(I)
Rint= 0.044
max= 25.0
h=6!9
k=9!9
l=33!33
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.062
wR(F2) = 0.225
S= 1.00 2891 reflections 229 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.1519P)2] whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001
max= 0.30 e A˚ 3
min=0.27 e A˚ 3
Extinction correction:SHELXL97
(Sheldrick, 1997)
Extinction coefficient: 0.008 (3)
Table 1
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
C7—H7 O3 0.93 2.45 3.094 (5) 126
C1—H1 O2i
0.93 2.44 3.125 (6) 131
Symmetry code: (i)x;yþ1;z.
H atoms were included in calculated positions and refined using a riding-model approximation, with C—H = 0.93 A˚ and Uiso(H) = 1.2Ueq(C) for aromatic CH, and C—H = 0.96 A˚ and Uiso(H) = 1.5Ueq(C) for methyl CH3.
Data collection:SMART(Bruker, 1999); cell refinement:SAINT
(Bruker, 1999); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Bruker, 1999); software used to prepare material for publication:SHELXTL.
References
Bruker (1999).SHELXTL(Version 5.10),SMART(Version 5.0) andSAINT
(Version 4.0) for Windows NT. Bruker AXS Inc., Madison, Wisconsin, USA.
Kahwa, I. A., Selbin, J., Hsieh, T. C.-Y. & Laine, R. A. (1986).Inorg. Chim. Acta,118, 179–185.
Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001).J. Chem. Soc. Dalton Trans.pp. 838–844.
Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
[image:2.610.45.295.73.209.2]Go¨ttingen, Germany.
Figure 1
[image:2.610.47.293.253.460.2]The structure of (I), with displacement ellipsoids drawn at the 30% probability level.
Figure 2
supporting information
sup-1 Acta Cryst. (2006). E62, o755–o756
supporting information
Acta Cryst. (2006). E62, o755–o756 [https://doi.org/10.1107/S1600536806002352]
1,5-Dimethyl-4-(3-nitrobenzylideneamino)-2-phenylpyrazolidin-3-one
Chun-Sheng Zheng, Mei Li, Nan Yang and Zuo-Liang Jing
1,5-Dimethyl-4-(3-nitrobenzylideneamino)-2-phenylpyrazolidin-3-one
Crystal data
C18H16N4O3
Mr = 336.35 Monoclinic, P21/c Hall symbol: -P 2ybc
a = 7.645 (11) Å
b = 7.839 (11) Å
c = 28.24 (4) Å
β = 96.349 (19)°
V = 1682 (4) Å3
Z = 4
F(000) = 704
Dx = 1.328 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1975 reflections
θ = 2.7–25.8°
µ = 0.09 mm−1
T = 294 K Block, yellow
0.32 × 0.22 × 0.16 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin = 0.962, Tmax = 0.985
8161 measured reflections 2891 independent reflections 1817 reflections with I > 2σ(I)
Rint = 0.044
θmax = 25.0°, θmin = 2.7°
h = −6→9
k = −9→9
l = −33→33
Refinement
Refinement on F2 Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.062
wR(F2) = 0.225
S = 1.00 2891 reflections 229 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.1519P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001
Δρmax = 0.30 e Å−3 Δρmin = −0.27 e Å−3
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 > 2σ(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
O1 −0.0706 (3) −0.3117 (4) 0.37073 (10) 0.0874 (9)
O2 0.0851 (4) −0.4100 (4) 0.43196 (10) 0.0972 (9)
O3 0.5298 (2) 0.0113 (3) 0.62512 (7) 0.0561 (6)
N1 0.3568 (3) 0.2501 (3) 0.54245 (8) 0.0447 (6)
N2 0.5883 (3) 0.4478 (3) 0.64409 (8) 0.0460 (6)
N3 0.6268 (3) 0.2768 (3) 0.65602 (8) 0.0483 (6)
N4 0.0214 (3) −0.2920 (4) 0.40760 (11) 0.0626 (8)
C1 0.1226 (3) 0.2042 (4) 0.45898 (10) 0.0467 (7)
H1 0.1421 0.3145 0.4705 0.056*
C2 0.0073 (3) 0.1791 (4) 0.41846 (10) 0.0528 (8)
H2 −0.0483 0.2720 0.4028 0.063*
C3 −0.0260 (3) 0.0154 (4) 0.40105 (10) 0.0495 (8)
H3 −0.1044 −0.0039 0.3740 0.059*
C4 0.0608 (3) −0.1174 (4) 0.42522 (10) 0.0437 (7)
C5 0.1783 (3) −0.0957 (4) 0.46550 (9) 0.0433 (7)
H5 0.2347 −0.1893 0.4806 0.052*
C6 0.2113 (3) 0.0686 (3) 0.48331 (9) 0.0393 (7)
C7 0.3291 (3) 0.0975 (4) 0.52683 (9) 0.0423 (7)
H7 0.3841 0.0057 0.5432 0.051*
C8 0.4610 (3) 0.2837 (4) 0.58478 (9) 0.0400 (7)
C9 0.5375 (3) 0.1684 (4) 0.62124 (9) 0.0440 (7)
C10 0.4976 (3) 0.4477 (4) 0.59996 (10) 0.0448 (7)
C11 0.7171 (4) 0.5779 (4) 0.66175 (11) 0.0587 (8)
H11A 0.8292 0.5514 0.6513 0.088*
H11B 0.7278 0.5801 0.6959 0.088*
H11C 0.6785 0.6876 0.6496 0.088*
C12 0.4502 (4) 0.6105 (4) 0.57326 (11) 0.0618 (9)
H12A 0.4287 0.6988 0.5954 0.093*
H12B 0.3462 0.5927 0.5515 0.093*
H12C 0.5455 0.6438 0.5558 0.093*
C13 0.6757 (3) 0.2279 (4) 0.70437 (10) 0.0473 (8)
C14 0.7889 (3) 0.0909 (4) 0.71342 (11) 0.0569 (8)
H14 0.8334 0.0341 0.6884 0.068*
C15 0.8350 (4) 0.0397 (5) 0.75975 (12) 0.0675 (9)
supporting information
sup-3 Acta Cryst. (2006). E62, o755–o756
C16 0.7746 (4) 0.1288 (5) 0.79758 (12) 0.0682 (10)
H16 0.8084 0.0954 0.8289 0.082*
C17 0.6643 (4) 0.2667 (4) 0.78813 (11) 0.0611 (9)
H17 0.6246 0.3270 0.8132 0.073*
C18 0.6126 (3) 0.3158 (4) 0.74208 (10) 0.0537 (8)
H18 0.5358 0.4072 0.7360 0.064*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.0801 (15) 0.086 (2) 0.092 (2) −0.0087 (13) −0.0116 (14) −0.0386 (15)
O2 0.128 (2) 0.0525 (19) 0.105 (2) −0.0018 (15) −0.0151 (18) −0.0050 (16)
O3 0.0726 (13) 0.0446 (15) 0.0494 (14) −0.0037 (10) −0.0013 (10) 0.0039 (10) N1 0.0422 (11) 0.0510 (17) 0.0408 (14) −0.0023 (10) 0.0041 (10) 0.0029 (11) N2 0.0499 (12) 0.0415 (16) 0.0457 (14) −0.0009 (10) 0.0010 (10) 0.0019 (11) N3 0.0543 (13) 0.0482 (17) 0.0403 (14) −0.0002 (10) −0.0033 (10) 0.0020 (11)
N4 0.0575 (14) 0.058 (2) 0.072 (2) −0.0064 (13) 0.0074 (14) −0.0139 (16)
C1 0.0472 (14) 0.0413 (18) 0.0514 (18) −0.0031 (12) 0.0044 (12) 0.0014 (13)
C2 0.0499 (14) 0.055 (2) 0.0524 (19) 0.0023 (13) −0.0016 (13) 0.0100 (15)
C3 0.0417 (13) 0.065 (2) 0.0407 (16) −0.0051 (13) 0.0003 (11) −0.0006 (15)
C4 0.0403 (12) 0.0473 (19) 0.0448 (16) −0.0046 (12) 0.0101 (11) −0.0073 (13)
C5 0.0395 (12) 0.0443 (18) 0.0472 (17) 0.0029 (11) 0.0091 (11) 0.0042 (13)
C6 0.0367 (12) 0.0427 (18) 0.0395 (16) −0.0008 (11) 0.0082 (10) 0.0048 (12)
C7 0.0381 (12) 0.0477 (19) 0.0412 (17) 0.0009 (11) 0.0049 (11) 0.0047 (13)
C8 0.0372 (12) 0.0453 (18) 0.0371 (16) −0.0029 (11) 0.0025 (11) 0.0005 (12)
C9 0.0428 (13) 0.051 (2) 0.0390 (17) −0.0027 (12) 0.0067 (11) 0.0026 (13)
C10 0.0386 (12) 0.053 (2) 0.0433 (17) 0.0010 (11) 0.0061 (11) 0.0026 (13)
C11 0.0564 (16) 0.057 (2) 0.061 (2) −0.0106 (14) −0.0018 (13) −0.0050 (15)
C12 0.0635 (17) 0.057 (2) 0.064 (2) 0.0017 (15) 0.0019 (15) 0.0077 (17)
C13 0.0422 (13) 0.058 (2) 0.0408 (17) −0.0037 (12) −0.0009 (11) 0.0027 (13)
C14 0.0509 (15) 0.066 (2) 0.0515 (19) 0.0041 (14) −0.0022 (13) 0.0000 (16)
C15 0.0633 (18) 0.072 (3) 0.062 (2) 0.0109 (16) −0.0144 (15) 0.0078 (18)
C16 0.075 (2) 0.085 (3) 0.0409 (19) −0.0098 (18) −0.0121 (15) 0.0035 (18)
C17 0.0677 (18) 0.072 (3) 0.044 (2) −0.0018 (16) 0.0036 (14) −0.0064 (16)
C18 0.0537 (15) 0.063 (2) 0.0439 (18) 0.0036 (13) 0.0021 (12) −0.0032 (14)
Geometric parameters (Å, º)
O1—N4 1.200 (4) C7—H7 0.9300
O2—N4 1.221 (4) C8—C10 1.374 (4)
O3—C9 1.239 (4) C8—C9 1.444 (4)
N1—C7 1.285 (4) C10—C12 1.506 (4)
N1—C8 1.386 (4) C11—H11A 0.9600
N2—C10 1.357 (4) C11—H11B 0.9600
N2—N3 1.405 (4) C11—H11C 0.9600
N2—C11 1.466 (4) C12—H12A 0.9600
N3—C9 1.415 (4) C12—H12B 0.9600
N4—C4 1.476 (4) C13—C14 1.385 (4)
C1—C2 1.379 (4) C13—C18 1.398 (4)
C1—C6 1.399 (4) C14—C15 1.377 (5)
C1—H1 0.9300 C14—H14 0.9300
C2—C3 1.388 (5) C15—C16 1.397 (5)
C2—H2 0.9300 C15—H15 0.9300
C3—C4 1.374 (4) C16—C17 1.378 (5)
C3—H3 0.9300 C16—H16 0.9300
C4—C5 1.380 (4) C17—C18 1.372 (4)
C5—C6 1.396 (4) C17—H17 0.9300
C5—H5 0.9300 C18—H18 0.9300
C6—C7 1.459 (4)
C7—N1—C8 122.0 (2) O3—C9—C8 131.7 (3)
C10—N2—N3 107.0 (2) N3—C9—C8 104.2 (3)
C10—N2—C11 124.6 (2) N2—C10—C8 110.6 (2)
N3—N2—C11 117.9 (2) N2—C10—C12 122.0 (3)
N2—N3—C9 109.5 (2) C8—C10—C12 127.4 (3)
N2—N3—C13 120.7 (2) N2—C11—H11A 109.5
C9—N3—C13 123.9 (3) N2—C11—H11B 109.5
O1—N4—O2 123.4 (3) H11A—C11—H11B 109.5
O1—N4—C4 119.3 (3) N2—C11—H11C 109.5
O2—N4—C4 117.3 (3) H11A—C11—H11C 109.5
C2—C1—C6 122.0 (3) H11B—C11—H11C 109.5
C2—C1—H1 119.0 C10—C12—H12A 109.5
C6—C1—H1 119.0 C10—C12—H12B 109.5
C1—C2—C3 120.1 (3) H12A—C12—H12B 109.5
C1—C2—H2 120.0 C10—C12—H12C 109.5
C3—C2—H2 120.0 H12A—C12—H12C 109.5
C4—C3—C2 117.7 (3) H12B—C12—H12C 109.5
C4—C3—H3 121.2 C14—C13—C18 120.2 (3)
C2—C3—H3 121.2 C14—C13—N3 118.5 (3)
C3—C4—C5 123.4 (3) C18—C13—N3 121.4 (3)
C3—C4—N4 117.7 (3) C15—C14—C13 119.4 (3)
C5—C4—N4 118.8 (3) C15—C14—H14 120.3
C4—C5—C6 119.1 (3) C13—C14—H14 120.3
C4—C5—H5 120.5 C14—C15—C16 120.6 (3)
C6—C5—H5 120.5 C14—C15—H15 119.7
C5—C6—C1 117.8 (3) C16—C15—H15 119.7
C5—C6—C7 121.1 (2) C17—C16—C15 119.4 (3)
C1—C6—C7 121.1 (3) C17—C16—H16 120.3
N1—C7—C6 119.8 (2) C15—C16—H16 120.3
N1—C7—H7 120.1 C18—C17—C16 120.6 (3)
C6—C7—H7 120.1 C18—C17—H17 119.7
C10—C8—N1 121.6 (2) C16—C17—H17 119.7
C10—C8—C9 108.1 (3) C17—C18—C13 119.7 (3)
N1—C8—C9 130.2 (3) C17—C18—H18 120.1
supporting information
sup-5 Acta Cryst. (2006). E62, o755–o756
C10—N2—N3—C9 −8.0 (3) C13—N3—C9—C8 159.9 (2)
C11—N2—N3—C9 −154.4 (2) C10—C8—C9—O3 174.6 (2)
C10—N2—N3—C13 −162.0 (2) N1—C8—C9—O3 −1.1 (4)
C11—N2—N3—C13 51.6 (3) C10—C8—C9—N3 −3.2 (2)
C6—C1—C2—C3 1.0 (4) N1—C8—C9—N3 −179.0 (2)
C1—C2—C3—C4 −0.7 (4) N3—N2—C10—C8 5.9 (3)
C2—C3—C4—C5 −0.1 (4) C11—N2—C10—C8 149.4 (2)
C2—C3—C4—N4 178.2 (2) N3—N2—C10—C12 −173.5 (2)
O1—N4—C4—C3 7.0 (4) C11—N2—C10—C12 −30.0 (4)
O2—N4—C4—C3 −172.7 (3) N1—C8—C10—N2 174.5 (2)
O1—N4—C4—C5 −174.6 (2) C9—C8—C10—N2 −1.6 (3)
O2—N4—C4—C5 5.6 (4) N1—C8—C10—C12 −6.1 (4)
C3—C4—C5—C6 0.5 (4) C9—C8—C10—C12 177.7 (2)
N4—C4—C5—C6 −177.7 (2) N2—N3—C13—C14 −149.3 (2)
C4—C5—C6—C1 −0.1 (3) C9—N3—C13—C14 60.5 (3)
C4—C5—C6—C7 177.6 (2) N2—N3—C13—C18 30.3 (4)
C2—C1—C6—C5 −0.6 (3) C9—N3—C13—C18 −119.9 (3)
C2—C1—C6—C7 −178.3 (2) C18—C13—C14—C15 1.6 (4)
C8—N1—C7—C6 176.90 (19) N3—C13—C14—C15 −178.8 (3)
C5—C6—C7—N1 −179.8 (2) C13—C14—C15—C16 −2.7 (5)
C1—C6—C7—N1 −2.2 (3) C14—C15—C16—C17 1.6 (5)
C7—N1—C8—C10 176.4 (2) C15—C16—C17—C18 0.6 (5)
C7—N1—C8—C9 −8.3 (4) C16—C17—C18—C13 −1.6 (5)
N2—N3—C9—O3 −171.2 (2) C14—C13—C18—C17 0.5 (4)
C13—N3—C9—O3 −18.2 (4) N3—C13—C18—C17 −179.1 (3)
N2—N3—C9—C8 6.8 (2)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
C7—H7···O3 0.93 2.45 3.094 (5) 126
C1—H1···O2i 0.93 2.44 3.125 (6) 131
