organic compounds
(Z)-4-[2-(2,4-Dimethylphenyl)hydrazinylidene]-3-methylpyrazol-5(1H)-one
aDepartment of Chemistry, P. A. College of Engineering, Mangalore 574 153, India, bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, cDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, dDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, and eDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
*Correspondence e-mail: jjasinski@keene.edu
The molecule of the title compound, C12H14N4O, is roughly planar, with a dihedral angle of 8.0 (8)° between the benzene and pyrazole rings, and an intramolecular N—H⋯O hydrogen bond forms an S(6) ring motif. In the crystal, molecules are linked into an inversion dimer by a pair of N—H⋯O hydrogen bonds, which form an R22(8) ring motif.
Related literature
For the biological activity of pyrazolones, see: Amir & Kumar (2005); Rao et al. (2008); Samshuddin et al. (2011). For the radical scavenging capacity of pyrazol-5-ols, see: Sarojini et al. (2010). For related structures, see: Butcher et al. (2011); Samshuddin et al. (2011). For reference bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
|
|
Data collection: CrysAlis PRO (Agilent, 2012); cell CrysAlis PRO ; data reduction: CrysAlis RED (Agilent, 2012); 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.
Supporting information
10.1107/S1600536813006661/is5254sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813006661/is5254Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813006661/is5254Isup3.cml
Ethyl 2-[2-(2,4-dimethylphenyl)hydrazinylidene]-3-oxobutanoate (2.62 g, 0.01 mol) and hydrazine hydrate (0.75 ml, 0.015 mol) were refluxed in acetic acid for 4–6 h. Then the reaction mixture was cooled to room temperature and the solid product was filtered off. Single crystals were grown by slow evaporation from a mixture of petroleum ether and ethyl acetate (1:3 v/v) (m.p. 421–423 K).
All of the H atoms were placed in their calculated positions and then refined using the riding model with Atom—H lengths of 0.95 Å (CH), 0.98 Å (CH3) or 0.88 Å (NH). Isotropic displacement parameters for these atoms were set to 1.2 (CH, NH) or 1.5 (CH3) times Ueq of the parent atom.
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis RED (Agilent, 2012); 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).C12H14N4O | F(000) = 488 |
Mr = 230.27 | Dx = 1.325 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ybc | Cell parameters from 2088 reflections |
a = 5.2926 (2) Å | θ = 4.0–75.3° |
b = 22.1675 (6) Å | µ = 0.72 mm−1 |
c = 10.0529 (3) Å | T = 123 K |
β = 101.770 (3)° | Long plate, colourless |
V = 1154.64 (6) Å3 | 0.51 × 0.24 × 0.08 mm |
Z = 4 |
Agilent Xcalibur (Ruby, Gemini) diffractometer | 2328 independent reflections |
Radiation source: Enhance (Cu) X-ray Source | 2061 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 10.5081 pixels mm-1 | θmax = 75.5°, θmin = 4.0° |
ω scans | h = −5→6 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | k = −27→26 |
Tmin = 0.538, Tmax = 0.944 | l = −11→12 |
4152 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0699P)2 + 0.3531P] where P = (Fo2 + 2Fc2)/3 |
2328 reflections | (Δ/σ)max < 0.001 |
157 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C12H14N4O | V = 1154.64 (6) Å3 |
Mr = 230.27 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 5.2926 (2) Å | µ = 0.72 mm−1 |
b = 22.1675 (6) Å | T = 123 K |
c = 10.0529 (3) Å | 0.51 × 0.24 × 0.08 mm |
β = 101.770 (3)° |
Agilent Xcalibur (Ruby, Gemini) diffractometer | 2328 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 2061 reflections with I > 2σ(I) |
Tmin = 0.538, Tmax = 0.944 | Rint = 0.024 |
4152 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.124 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.34 e Å−3 |
2328 reflections | Δρmin = −0.27 e Å−3 |
157 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.18460 (18) | 0.45530 (5) | 0.89208 (10) | 0.0213 (2) | |
N1 | 0.2909 (2) | 0.61180 (5) | 0.90296 (12) | 0.0212 (3) | |
N2 | 0.1729 (2) | 0.55870 (5) | 0.93665 (12) | 0.0206 (3) | |
H2A | 0.0590 | 0.5581 | 0.9893 | 0.025* | |
N3 | 0.5733 (2) | 0.50000 (5) | 0.73044 (12) | 0.0190 (3) | |
N4 | 0.5362 (2) | 0.44146 (5) | 0.73009 (12) | 0.0196 (3) | |
H4D | 0.4265 | 0.4266 | 0.7766 | 0.024* | |
C1 | 0.2517 (3) | 0.50879 (6) | 0.88022 (14) | 0.0183 (3) | |
C2 | 0.4380 (3) | 0.53140 (6) | 0.80200 (14) | 0.0186 (3) | |
C3 | 0.4473 (3) | 0.59579 (6) | 0.82398 (14) | 0.0196 (3) | |
C4 | 0.6109 (3) | 0.63998 (6) | 0.76933 (16) | 0.0242 (3) | |
H4A | 0.6007 | 0.6793 | 0.8126 | 0.036* | |
H4B | 0.5497 | 0.6438 | 0.6709 | 0.036* | |
H4C | 0.7903 | 0.6260 | 0.7885 | 0.036* | |
C5 | 0.6657 (3) | 0.40171 (6) | 0.65796 (14) | 0.0187 (3) | |
C6 | 0.6331 (3) | 0.33981 (6) | 0.67717 (14) | 0.0190 (3) | |
C7 | 0.7561 (3) | 0.29989 (6) | 0.60384 (14) | 0.0202 (3) | |
H7A | 0.7338 | 0.2578 | 0.6145 | 0.024* | |
C8 | 0.9106 (3) | 0.31954 (7) | 0.51552 (14) | 0.0208 (3) | |
C9 | 0.9423 (3) | 0.38169 (7) | 0.50101 (15) | 0.0226 (3) | |
H9A | 1.0493 | 0.3960 | 0.4425 | 0.027* | |
C10 | 0.8203 (3) | 0.42275 (6) | 0.57057 (14) | 0.0216 (3) | |
H10A | 0.8416 | 0.4648 | 0.5590 | 0.026* | |
C11 | 0.4740 (3) | 0.31736 (6) | 0.77591 (15) | 0.0229 (3) | |
H11A | 0.2952 | 0.3310 | 0.7465 | 0.034* | |
H11B | 0.5452 | 0.3333 | 0.8667 | 0.034* | |
H11C | 0.4783 | 0.2732 | 0.7785 | 0.034* | |
C12 | 1.0424 (3) | 0.27468 (7) | 0.43960 (16) | 0.0259 (3) | |
H12A | 0.9883 | 0.2337 | 0.4578 | 0.039* | |
H12B | 1.2299 | 0.2783 | 0.4698 | 0.039* | |
H12C | 0.9946 | 0.2829 | 0.3419 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0210 (5) | 0.0191 (5) | 0.0251 (5) | −0.0010 (4) | 0.0078 (4) | −0.0011 (4) |
N1 | 0.0195 (6) | 0.0181 (6) | 0.0257 (6) | 0.0016 (4) | 0.0038 (5) | 0.0009 (5) |
N2 | 0.0192 (6) | 0.0197 (6) | 0.0246 (6) | 0.0005 (4) | 0.0081 (5) | −0.0002 (4) |
N3 | 0.0184 (5) | 0.0176 (6) | 0.0204 (6) | 0.0011 (4) | 0.0024 (4) | 0.0006 (4) |
N4 | 0.0190 (5) | 0.0182 (6) | 0.0226 (6) | −0.0010 (4) | 0.0068 (4) | −0.0005 (4) |
C1 | 0.0155 (6) | 0.0201 (7) | 0.0188 (6) | 0.0016 (5) | 0.0021 (5) | 0.0004 (5) |
C2 | 0.0168 (6) | 0.0190 (6) | 0.0193 (6) | 0.0003 (5) | 0.0023 (5) | 0.0022 (5) |
C3 | 0.0176 (6) | 0.0185 (6) | 0.0214 (6) | 0.0034 (5) | 0.0012 (5) | 0.0014 (5) |
C4 | 0.0228 (7) | 0.0182 (6) | 0.0320 (8) | 0.0026 (5) | 0.0066 (6) | 0.0036 (6) |
C5 | 0.0163 (6) | 0.0203 (7) | 0.0190 (6) | 0.0006 (5) | 0.0023 (5) | −0.0024 (5) |
C6 | 0.0161 (6) | 0.0209 (7) | 0.0190 (6) | −0.0023 (5) | 0.0015 (5) | −0.0010 (5) |
C7 | 0.0184 (6) | 0.0183 (7) | 0.0224 (7) | −0.0018 (5) | 0.0005 (5) | −0.0023 (5) |
C8 | 0.0156 (6) | 0.0242 (7) | 0.0213 (6) | 0.0004 (5) | 0.0010 (5) | −0.0043 (5) |
C9 | 0.0199 (6) | 0.0269 (7) | 0.0223 (7) | −0.0018 (6) | 0.0073 (5) | −0.0003 (6) |
C10 | 0.0228 (7) | 0.0187 (6) | 0.0233 (7) | −0.0010 (5) | 0.0049 (5) | 0.0002 (5) |
C11 | 0.0257 (7) | 0.0190 (6) | 0.0255 (7) | −0.0037 (5) | 0.0085 (6) | −0.0016 (5) |
C12 | 0.0223 (7) | 0.0256 (7) | 0.0309 (7) | −0.0011 (6) | 0.0079 (6) | −0.0080 (6) |
O1—C1 | 1.2504 (17) | C5—C6 | 1.4013 (19) |
N1—C3 | 1.3075 (19) | C6—C7 | 1.395 (2) |
N1—N2 | 1.4059 (16) | C6—C11 | 1.5112 (18) |
N2—C1 | 1.3475 (18) | C7—C8 | 1.394 (2) |
N2—H2A | 0.8800 | C7—H7A | 0.9500 |
N3—N4 | 1.3125 (16) | C8—C9 | 1.399 (2) |
N3—C2 | 1.3135 (18) | C8—C12 | 1.5084 (19) |
N4—C5 | 1.4052 (18) | C9—C10 | 1.385 (2) |
N4—H4D | 0.8800 | C9—H9A | 0.9500 |
C1—C2 | 1.4692 (18) | C10—H10A | 0.9500 |
C2—C3 | 1.4437 (19) | C11—H11A | 0.9800 |
C3—C4 | 1.4850 (19) | C11—H11B | 0.9800 |
C4—H4A | 0.9800 | C11—H11C | 0.9800 |
C4—H4B | 0.9800 | C12—H12A | 0.9800 |
C4—H4C | 0.9800 | C12—H12B | 0.9800 |
C5—C10 | 1.397 (2) | C12—H12C | 0.9800 |
C3—N1—N2 | 106.63 (11) | C7—C6—C11 | 121.39 (13) |
C1—N2—N1 | 113.29 (12) | C5—C6—C11 | 120.92 (12) |
C1—N2—H2A | 123.4 | C8—C7—C6 | 122.40 (13) |
N1—N2—H2A | 123.4 | C8—C7—H7A | 118.8 |
N4—N3—C2 | 115.29 (12) | C6—C7—H7A | 118.8 |
N3—N4—C5 | 122.19 (12) | C7—C8—C9 | 118.22 (13) |
N3—N4—H4D | 118.9 | C7—C8—C12 | 120.53 (13) |
C5—N4—H4D | 118.9 | C9—C8—C12 | 121.24 (13) |
O1—C1—N2 | 128.34 (13) | C10—C9—C8 | 121.07 (13) |
O1—C1—C2 | 127.52 (12) | C10—C9—H9A | 119.5 |
N2—C1—C2 | 104.13 (12) | C8—C9—H9A | 119.5 |
N3—C2—C3 | 127.04 (13) | C9—C10—C5 | 119.43 (13) |
N3—C2—C1 | 127.81 (12) | C9—C10—H10A | 120.3 |
C3—C2—C1 | 105.13 (12) | C5—C10—H10A | 120.3 |
N1—C3—C2 | 110.81 (12) | C6—C11—H11A | 109.5 |
N1—C3—C4 | 122.32 (13) | C6—C11—H11B | 109.5 |
C2—C3—C4 | 126.86 (13) | H11A—C11—H11B | 109.5 |
C3—C4—H4A | 109.5 | C6—C11—H11C | 109.5 |
C3—C4—H4B | 109.5 | H11A—C11—H11C | 109.5 |
H4A—C4—H4B | 109.5 | H11B—C11—H11C | 109.5 |
C3—C4—H4C | 109.5 | C8—C12—H12A | 109.5 |
H4A—C4—H4C | 109.5 | C8—C12—H12B | 109.5 |
H4B—C4—H4C | 109.5 | H12A—C12—H12B | 109.5 |
C10—C5—C6 | 121.18 (13) | C8—C12—H12C | 109.5 |
C10—C5—N4 | 121.68 (13) | H12A—C12—H12C | 109.5 |
C6—C5—N4 | 117.14 (12) | H12B—C12—H12C | 109.5 |
C7—C6—C5 | 117.68 (13) | ||
C3—N1—N2—C1 | −0.01 (15) | N3—N4—C5—C10 | −7.1 (2) |
C2—N3—N4—C5 | 179.75 (12) | N3—N4—C5—C6 | 172.99 (12) |
N1—N2—C1—O1 | 179.22 (13) | C10—C5—C6—C7 | −1.3 (2) |
N1—N2—C1—C2 | −0.17 (15) | N4—C5—C6—C7 | 178.63 (11) |
N4—N3—C2—C3 | 177.63 (12) | C10—C5—C6—C11 | 177.61 (12) |
N4—N3—C2—C1 | −0.2 (2) | N4—C5—C6—C11 | −2.45 (19) |
O1—C1—C2—N3 | −0.9 (2) | C5—C6—C7—C8 | 1.0 (2) |
N2—C1—C2—N3 | 178.50 (13) | C11—C6—C7—C8 | −177.90 (12) |
O1—C1—C2—C3 | −179.13 (13) | C6—C7—C8—C9 | 0.2 (2) |
N2—C1—C2—C3 | 0.28 (14) | C6—C7—C8—C12 | 179.27 (12) |
N2—N1—C3—C2 | 0.20 (15) | C7—C8—C9—C10 | −1.1 (2) |
N2—N1—C3—C4 | −178.85 (12) | C12—C8—C9—C10 | 179.80 (13) |
N3—C2—C3—N1 | −178.55 (13) | C8—C9—C10—C5 | 0.8 (2) |
C1—C2—C3—N1 | −0.30 (15) | C6—C5—C10—C9 | 0.4 (2) |
N3—C2—C3—C4 | 0.5 (2) | N4—C5—C10—C9 | −179.51 (12) |
C1—C2—C3—C4 | 178.70 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.88 | 1.95 | 2.8233 (15) | 172 |
N4—H4D···O1 | 0.88 | 2.00 | 2.7286 (15) | 139 |
Symmetry code: (i) −x, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C12H14N4O |
Mr | 230.27 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 123 |
a, b, c (Å) | 5.2926 (2), 22.1675 (6), 10.0529 (3) |
β (°) | 101.770 (3) |
V (Å3) | 1154.64 (6) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.51 × 0.24 × 0.08 |
Data collection | |
Diffractometer | Agilent Xcalibur (Ruby, Gemini) diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.538, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4152, 2328, 2061 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.124, 1.05 |
No. of reflections | 2328 |
No. of parameters | 157 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.27 |
Computer programs: CrysAlis PRO (Agilent, 2012), CrysAlis RED (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.88 | 1.95 | 2.8233 (15) | 172 |
N4—H4D···O1 | 0.88 | 2.00 | 2.7286 (15) | 139 |
Symmetry code: (i) −x, −y+1, −z+2. |
Acknowledgements
BKS gratefully acknowledges the Department of Atomic Energy (DAE)/BRNS, Government of India, for providing financial assistance in the BRNS Project (No. 2011/34/20-BRNS/0846). RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the X-ray diffractometer.
References
Agilent (2012). CrysAlis PRO and CrysAlis RED. Agilent Technologies, Yarnton, Oxfordshire, England. Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Amir, M. & Kumar, S. (2005). Indian. J. Chem. Sect. B, 44, 2532–2537. Google Scholar
Butcher, R. J., Akkurt, M., Samshuddin, S., Narayana, B. & Yathirajan, H. S. (2011). Acta Cryst. E67, o1019. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rao, B. S., Akberali, P. M., Holla, B. S. & Sarojini, B. K. (2008). J. Pharmacol. Toxicol. 3, 102–103. CrossRef CAS Google Scholar
Samshuddin, S., Narayana, B., Sarojini, B. K., Khan, M. T. H., Yathirajan, H. S., Darshan Raj, C. G. & Raghavendra, R. (2011). Med. Chem. Res. 21, 2012–2022. Web of Science CSD CrossRef Google Scholar
Sarojini, B. K., Vidyagayatri, M., Darshan Raj, C. G., Barath, B. R. & Manjunatha, H. (2010). Lett. Drug Des. Discov. 7, 214–224. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
In view of high medicinal value such as anti-inflammatory, analgesic (Amir & Kumar, 2005), antimicrobial (Samshuddin et al., 2011) and antiproliferative activity (Rao et al. 2008) of pyrazolones, it was thought worthwhile to synthesize compounds based on pyrazolone derivatives. In addition, the radical scavenging capacity and molecular binding of various derivatives of pyrazol-5-ols were reported (Sarojini et al., 2010). Also, the crystal structures of some of the related pyrazoles viz. 3,5-bis(4-bromophenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (Samshuddin et al., 2011) and 5-bis(4-methylphenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (Butcher et al., 2011) have been reported. In view of the importance of pyrazolones, we report herein the crystal structure of the title compound, C12H14N4O, (I).
The asymmetric unit of (I) consists of a 3-methyl-1H-pyrazol-5(4H)-one group bonded to 2,4-(dimethylphenyl)hydrazone in a nearly planar conformation (Fig. 1). The mean plane of the benzene ring is twisted by 8.0 (8)° from that of the pyrazole ring. Bond lengths are in normal ranges (Allen et al., 1987). In the crystal, intermolecular N2—H2A···O1 hydrogen bonds (Table 1) which form R22(8) ring motifs linking the molecule into dimers are observed (Fig. 2). An intramolecular N4—H4D···O1 hydrogen bond is also present.