supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2008). E64, o1988    [ doi:10.1107/S1600536808030031 ]

(E)-4-(4-Hydroxy-3-nitrobenzylideneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one

C.-N. Zhang and M.-H. Yang

Abstract top

In the title compound, C18H16N4O4, the dihedral angles between the central pyrazole ring and the pendant substituted and unsubstituted aromatic rings are 4.73 (12) and 44.24 (14)°, respectively. An intramolecular O-H...O hydrogen bond occurs. In the crystal structure, an intermolecular C-H...O interaction may help to consolidate the packing and a short intramolecular C-H...O contact also occurs.

Comment top

There have been of great interest in the synthesis, characterization, and properties of Schiff bases and Schiff base complexes. (Yan et al., 2006; Zheng et al., 2006) Schiff bases that have solvent dependent UV/vis spectra (solvatochromicity) can be suitable NLO (nonlinear optical active) materials (Alemi et al., 2000). They are also useful in asymmetric oxidation of methyl phenyl sulfide and enantioselective reactions (Kim et al., 1999).

In this paper, we report here the synthesis and crystal structure of the title compound (I), (Fig. 1). The dihedral angles betweem the pyrazole ring and the pendant C13 and C1 aromatic rings are 4.73 (12)° and 44.24 (14)°, respectively. The C12—N3 bond length of 1.281 (3) Å in (I) is indicative of a normal C=N double bond.

The intra- and intermolecular hydrogen bonds in (I) are listed in Table 1.

Related literature top

For selected background literature on Schiff bases, see: Alemi & Shaabani (2000); Kim & Shin (1999); Yan et al. (2006); Zheng et al. (2006).

Experimental top

Under nitrogen, a mixture of 4-hydroxy-3-nitrobenzaldehyde (1.67 g, 10 mmol) and 4-amino-1,2-dihydro-1,5-dimethyl-1-phenylpyrazol-3-one (2.03 g, 10 mmol) in absolute ethanol (80 ml) was refluxed for about 20 h to yield a yellow precipitate. The product was collected by vacuum filtration and washed with ethanol. The crude solid was redissolved in CH2Cl2 (70 ml) and washed with water (2 × 8 ml) and brine (10 ml). After being dried over Na2SO4, the solvent was removed under vacuum, and yellow solid was isolated in a yield of 89% (2.8 g). Colourless blocks of (I) were grown from CH2Cl2 and absolute ethanol (4:1 v/v) by slow evaporation of the solvent at room temperature over a period of about two weeks.

Refinement top

All the H atoms were placed in calculated positions (C—H = 0.93-0.96Å, O—H = 0.82 Å) and refined as riding, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O, methyl C). The maximum difference peak is located 1.41Å from H11C.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of (I): non-H atoms are shown as 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The packing of (I), with C—H···O hydrogen bonds indicated by dotted lines.
(E)-4-(4-Hydroxy-3-nitrobenzylideneamino)-1,5-dimethyl-\ 2-phenyl-1H-pyrazol-3(2H)-one top
Crystal data top
C18H16N4O4F(000) = 736
Mr = 352.35Dx = 1.390 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3012 reflections
a = 7.5000 (15) Åθ = 3.2–25.2°
b = 7.8000 (16) ŵ = 0.10 mm−1
c = 28.900 (6) ÅT = 298 K
β = 95.00 (3)°Block, colourless
V = 1684.2 (6) Å30.29 × 0.22 × 0.18 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer		3012 independent reflections
Radiation source: fine-focus sealed tube1762 reflections with I > 2σ(I)
graphiteRint = 0.063
φ and ω scansθmax = 25.2°, θmin = 3.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.971, Tmax = 0.982k = −9→9
12221 measured reflectionsl = −34→34
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160H-atom parameters constrained
S = 0.83 w = 1/[σ2(Fo2) + (0.1P)2 + 0.3P]
where P = (Fo2 + 2Fc2)/3
3012 reflections(Δ/σ)max < 0.001
238 parametersΔρmax = 0.22 e Å−3
0 restraintsΔρmin = −0.18 e Å−3
Crystal data top
C18H16N4O4V = 1684.2 (6) Å3
Mr = 352.35Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.5000 (15) ŵ = 0.10 mm−1
b = 7.8000 (16) ÅT = 298 K
c = 28.900 (6) Å0.29 × 0.22 × 0.18 mm
β = 95.00 (3)°
Data collection top
Bruker APEXII CCD
diffractometer		3012 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1762 reflections with I > 2σ(I)
Tmin = 0.971, Tmax = 0.982Rint = 0.063
12221 measured reflectionsθmax = 25.2°
Refinement top
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.160Δρmax = 0.22 e Å−3
S = 0.83Δρmin = −0.18 e Å−3
3012 reflectionsAbsolute structure: ?
238 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
N30.1353 (3)0.2354 (3)0.45196 (7)0.0455 (5)
N1−0.0863 (3)0.4373 (3)0.35252 (7)0.0467 (5)
N2−0.1349 (3)0.2664 (3)0.34216 (7)0.0476 (5)
O1−0.0566 (2)−0.0019 (2)0.37369 (6)0.0537 (5)
O20.6074 (3)−0.0082 (3)0.63167 (6)0.0704 (6)
H20.6225−0.10960.63840.106*
O30.5569 (3)−0.3329 (3)0.61887 (8)0.0807 (7)
O40.3986 (4)−0.4244 (3)0.55889 (10)0.1126 (10)
N40.4606 (3)−0.3063 (3)0.58221 (9)0.0648 (7)
C130.2714 (3)0.0531 (3)0.51068 (8)0.0399 (6)
C120.1594 (3)0.0821 (3)0.46713 (8)0.0429 (6)
H120.1064−0.00990.45070.052*
C80.0330 (3)0.2717 (3)0.41051 (8)0.0416 (6)
C90.0055 (3)0.4366 (3)0.39532 (8)0.0459 (6)
C150.4212 (3)−0.1337 (3)0.56753 (8)0.0438 (6)
C140.3086 (3)−0.1094 (3)0.52690 (8)0.0441 (6)
H140.2588−0.20370.51080.053*
C160.4969 (3)0.0046 (4)0.59269 (8)0.0475 (6)
C1−0.1830 (3)0.2178 (3)0.29503 (8)0.0452 (6)
C180.3488 (3)0.1923 (3)0.53588 (8)0.0469 (6)
H180.32550.30320.52520.056*
C170.4577 (3)0.1682 (4)0.57589 (9)0.0532 (7)
H170.50600.26290.59200.064*
C5−0.3461 (4)0.0338 (4)0.24047 (11)0.0689 (9)
H5−0.4215−0.05970.23440.083*
C11−0.2133 (4)0.5723 (4)0.33705 (10)0.0596 (7)
H11A−0.32400.55460.35070.089*
H11B−0.23460.56900.30380.089*
H11C−0.16460.68200.34650.089*
C6−0.2976 (3)0.0829 (4)0.28630 (9)0.0567 (7)
H6−0.34300.02430.31070.068*
C7−0.0519 (3)0.1560 (3)0.37629 (8)0.0426 (6)
C2−0.1161 (3)0.3056 (4)0.25858 (9)0.0541 (7)
H2A−0.03620.39580.26440.065*
C100.0618 (4)0.5984 (4)0.41979 (10)0.0609 (8)
H10A0.10120.67920.39780.091*
H10B0.15800.57470.44300.091*
H10C−0.03760.64560.43430.091*
C4−0.2831 (4)0.1223 (5)0.20437 (10)0.0719 (9)
H4A−0.31760.09070.17390.086*
C3−0.1694 (4)0.2575 (4)0.21333 (10)0.0647 (8)
H3A−0.12730.31790.18880.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N30.0446 (11)0.0477 (13)0.0434 (11)0.0035 (10)−0.0014 (9)0.0012 (10)
N10.0526 (12)0.0365 (12)0.0494 (12)0.0018 (9)−0.0047 (10)0.0019 (10)
N20.0552 (12)0.0400 (12)0.0460 (12)0.0004 (10)−0.0053 (10)−0.0005 (10)
O10.0650 (11)0.0391 (12)0.0553 (11)0.0023 (9)−0.0039 (9)−0.0010 (8)
O20.0653 (12)0.0933 (17)0.0495 (11)0.0028 (12)−0.0130 (9)−0.0004 (11)
O30.0720 (13)0.0872 (17)0.0802 (15)0.0107 (12)−0.0085 (12)0.0363 (13)
O40.156 (3)0.0433 (14)0.128 (2)0.0001 (15)−0.046 (2)0.0050 (15)
N40.0638 (15)0.0563 (17)0.0732 (17)0.0019 (13)−0.0001 (13)0.0142 (14)
C130.0383 (12)0.0411 (15)0.0407 (13)−0.0002 (11)0.0055 (10)−0.0025 (11)
C120.0407 (13)0.0445 (15)0.0432 (13)−0.0011 (11)0.0014 (11)−0.0032 (12)
C80.0411 (13)0.0407 (15)0.0425 (13)0.0012 (11)0.0003 (11)−0.0008 (11)
C90.0463 (13)0.0438 (15)0.0470 (14)0.0001 (12)0.0008 (12)−0.0019 (12)
C150.0439 (13)0.0415 (15)0.0462 (14)0.0022 (11)0.0057 (11)0.0083 (11)
C140.0429 (13)0.0420 (15)0.0474 (14)−0.0048 (11)0.0038 (11)−0.0009 (11)
C160.0443 (13)0.0605 (17)0.0374 (12)0.0003 (13)0.0020 (11)0.0000 (12)
C10.0433 (13)0.0477 (15)0.0429 (14)0.0014 (12)−0.0057 (11)−0.0020 (12)
C180.0521 (14)0.0410 (15)0.0471 (14)0.0015 (12)0.0019 (12)−0.0029 (12)
C170.0552 (15)0.0544 (17)0.0495 (15)−0.0047 (13)0.0017 (12)−0.0136 (13)
C50.0616 (18)0.072 (2)0.0689 (19)−0.0080 (16)−0.0160 (16)−0.0100 (17)
C110.0629 (17)0.0473 (17)0.0666 (18)0.0118 (14)−0.0056 (14)0.0077 (14)
C60.0508 (15)0.0625 (18)0.0556 (16)−0.0043 (14)−0.0018 (13)0.0015 (14)
C70.0412 (13)0.0418 (16)0.0446 (14)0.0027 (11)0.0031 (11)0.0029 (11)
C20.0522 (15)0.0580 (18)0.0510 (15)−0.0007 (13)−0.0020 (12)0.0010 (13)
C100.0699 (18)0.0448 (17)0.0655 (18)0.0009 (14)−0.0083 (15)−0.0039 (14)
C40.078 (2)0.084 (2)0.0497 (17)0.0033 (19)−0.0156 (16)−0.0075 (16)
C30.0688 (18)0.078 (2)0.0468 (16)0.0034 (17)−0.0002 (14)0.0073 (15)
Geometric parameters (Å, °) top
N3—C121.281 (3)C14—H140.9300
N3—C81.394 (3)C16—C171.388 (4)
N1—C91.362 (3)C1—C61.368 (4)
N1—N21.407 (3)C1—C21.387 (4)
N1—C111.464 (3)C18—C171.369 (3)
N2—C71.412 (3)C18—H180.9300
N2—C11.429 (3)C17—H170.9300
O1—C71.235 (3)C5—C41.369 (4)
O2—C161.343 (3)C5—C61.396 (4)
O2—H20.8200C5—H50.9300
O3—N41.246 (3)C11—H11A0.9600
O4—N41.210 (3)C11—H11B0.9600
N4—C151.435 (3)C11—H11C0.9600
C13—C141.372 (3)C6—H60.9300
C13—C181.404 (3)C2—C31.385 (4)
C13—C121.469 (3)C2—H2A0.9300
C12—H120.9300C10—H10A0.9600
C8—C91.369 (3)C10—H10B0.9600
C8—C71.445 (3)C10—H10C0.9600
C9—C101.490 (4)C4—C31.366 (4)
C15—C161.394 (4)C4—H4A0.9300
C15—C141.398 (3)C3—H3A0.9300
C12—N3—C8122.3 (2)C17—C18—H18119.3
C9—N1—N2106.88 (19)C13—C18—H18119.3
C9—N1—C11123.0 (2)C18—C17—C16121.0 (2)
N2—N1—C11117.86 (19)C18—C17—H17119.5
N1—N2—C7109.80 (19)C16—C17—H17119.5
N1—N2—C1119.56 (19)C4—C5—C6120.4 (3)
C7—N2—C1124.3 (2)C4—C5—H5119.8
C16—O2—H2109.5C6—C5—H5119.8
O4—N4—O3120.8 (3)N1—C11—H11A109.5
O4—N4—C15119.4 (2)N1—C11—H11B109.5
O3—N4—C15119.8 (3)H11A—C11—H11B109.5
C14—C13—C18118.4 (2)N1—C11—H11C109.5
C14—C13—C12121.3 (2)H11A—C11—H11C109.5
C18—C13—C12120.3 (2)H11B—C11—H11C109.5
N3—C12—C13119.4 (2)C1—C6—C5119.6 (3)
N3—C12—H12120.3C1—C6—H6120.2
C13—C12—H12120.3C5—C6—H6120.2
C9—C8—N3121.5 (2)O1—C7—N2123.9 (2)
C9—C8—C7108.8 (2)O1—C7—C8132.3 (2)
N3—C8—C7129.6 (2)N2—C7—C8103.8 (2)
N1—C9—C8110.2 (2)C3—C2—C1119.3 (3)
N1—C9—C10121.8 (2)C3—C2—H2A120.3
C8—C9—C10128.0 (2)C1—C2—H2A120.3
C16—C15—C14121.5 (2)C9—C10—H10A109.5
C16—C15—N4120.5 (2)C9—C10—H10B109.5
C14—C15—N4118.0 (2)H10A—C10—H10B109.5
C13—C14—C15120.1 (2)C9—C10—H10C109.5
C13—C14—H14119.9H10A—C10—H10C109.5
C15—C14—H14119.9H10B—C10—H10C109.5
O2—C16—C17117.3 (2)C3—C4—C5119.7 (3)
O2—C16—C15125.0 (2)C3—C4—H4A120.1
C17—C16—C15117.7 (2)C5—C4—H4A120.1
C6—C1—C2120.2 (2)C4—C3—C2120.8 (3)
C6—C1—N2118.8 (2)C4—C3—H3A119.6
C2—C1—N2121.0 (2)C2—C3—H3A119.6
C17—C18—C13121.4 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O30.821.882.583 (3)143
C12—H12···O10.932.453.096 (3)127
C18—H18···O4i0.932.383.079 (4)132
Symmetry codes: (i) x, y+1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O30.821.882.583 (3)143
C12—H12···O10.932.453.096 (3)127
C18—H18···O4i0.932.383.079 (4)132
Symmetry codes: (i) x, y+1, z.
Acknowledgements top

The authors are grateful to the Natural Science Foundation of Zhejiang Province (No. Y407081) for financial support.

references
References top

Alemi, A. A. & Shaabani, B. (2000). Acta Chim. Slov. 47, 363–369.

Bruker (1998). SMART. Bruker AXS Inc, Madison, Wisconsin, USA.

Bruker (1999). SAINT. Bruker AXS Inc, Madison, Wisconsin, USA.

Kim, G. J. & Shin, J. H. (1999). Catal. Lett. 63, 83–89.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yan, G.-B., Yang, M.-H. & Zheng, Y.-F. (2006). Acta Cryst. E62, m3481–m3482.

Zheng, Y.-F., Yan, G.-B. & Gu, Y.-B. (2006). Acta Cryst. E62, o5134–o5135.