(Z)-4-{1-[(2-Hy­droxy­ethyl)­amino]­ethyl­idene}-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

In the title compound C₁₄H₁₇N₃O₂, the dihedral angle between the rings is 16.68 (13)°. Although the compound crystallizes in the keto form, the possibility of keto-enamine–enol-imine tautomerism is explained by a strong intra­molecular N—H...O hydrogen bond.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.004 Å
• H-atom completeness 83%
• Disorder in main residue
• R factor = 0.055
• wR factor = 0.173
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) .......          1
PLAT430_ALERT_2_B Short Inter D...A Contact  O1     ..  O2A     ..       2.75 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O1     ..  O2B     ..       2.79 Ang.

Alert level C
CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as
            calculated from the _atom_site* data lies outside
            the range 0.99 <> 1.01
           From the CIF: _cell_formula_units_Z                    8
           From the CIF: _chemical_formula_weight           259.31
           TEST: Calculate formula weight from _atom_site_*
           atom     mass    num     sum
           C        12.01   14.00  168.15
           H         1.01   14.00   14.11
           N        14.01    3.00   42.02
           O        16.00    2.00   32.00
           Calculated formula weight              256.28
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........        O2A
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........        O2B
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         11
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ          ?
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT043_ALERT_1_C Check Reported Molecular Weight ................     259.31
PLAT044_ALERT_1_C Calculated and Reported Dx Differ ..............          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C14 H17 N3 O2
            Atom count from the _atom_site data:  C14 H14 N3 O2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    8
           From the CIF: _chemical_formula_sum  C14 H17 N3 O2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        112.00    112.00    0.00
           H        136.00    112.00   24.00
           N         24.00     24.00    0.00
           O         16.00     16.00    0.00
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT Unusually Large.       0.12
PLAT301_ALERT_3_G Note: Main Residue  Disorder ...................       5.00 Perc.
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        273 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        273 K
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C12
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C14

   0 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   9 ALERT level G = General alerts; check

   9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   8 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

The ORTEP diagram for the molecule of the title compound is given in Fig:1. The molecule is almost planar where the phenyl ring is tilted by 17.66° to the rest of the molecule. The planarity is explained by the torsion angles C3—C4—C13—N3(-179.49°) and C13—N3—C15—C16 (173.88°).

The hydroxyl oxygen (O2) shows disorder and hence O2A and O2B were not refined using anisotropic thermal parameters.This disordered nature show a dynamic rotation about C15—C16 single bond.

The hydrogen (H3) of the imino group(N3) forms a strong intra-molecular hydrogen bond with keto oxygen O1 (2.711 Å, 146.56°). Along with this, the double bond character of C13—N3, show the possibility of proton shuttling between O1 and N3.

Though phenyl ring and pyrazol ring can adopt perpendicularity,the weak C11—H11···O1 interaction (2.954 Å, 121.13°) keeps them with near planarity.

The crystal packing diagram in Fig:2.

Related literature

4-Acylpyrazolones are good chelating ligands and also show antibacterial, antifungal, anti-inflammatory, carcino-static and enzyme inhibitory activity, see: Patel et al. (2000, 2001); Chohan & Kausar (2000); Chohan, Jaffery & Supuran (2001); Chohan, Munawar & Supuran (2001); Chohan et al. (2002); Yang et al. (2000). For related literature [on what subject?], see: Gursoy et al. (2000).

S2. Experimental

Ethanolic solution of 3-methyl-1-phenyl-4-acetylpyrazolin-5-ol (0.432 g, 2 mmol) and 2-aminoethanol (0.122 g, 2mmoL) were taken in a round bottom flask and refluxed for 4 h. The solid product was filtered and washed with cold ethanol. The product obtained was pure by TLC and NMR spectroscopy. However, the product was further purified by re-crystallization from ethanol and dried under vacuum. The compound was crystallized by slow evaporation technique using methanol as solvent at room temperature.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The ORTEP diagram of molecule H-atoms are involved in hydrogen bonding are shown as Dashed lines.
	Fig. 2. Crystal Packing Diagram.

(Z)-4-{1-[(2-Hydroxyethyl)amino]ethylidene}-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Crystal data

C14H17N3O2	F(000) = 1104
Mr = 259.31	Dx = 1.282 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2447 reflections
a = 22.4703 (13) Å	θ = 2.7–29.3°
b = 7.0902 (4) Å	µ = 0.09 mm^−1
c = 18.0565 (11) Å	T = 273 K
β = 110.926 (7)°	Monoclinic, colourless
V = 2687.0 (3) Å^3	0.20 × 0.20 × 0.20 mm
Z = 8

Data collection

Oxford Diffraction Xcalibur Eos diffractometer	2353 independent reflections
Radiation source: fine-focus sealed tube	1544 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 15.9821 pixels mm^-1	θmax = 25.0°, θmin = 3.0°
ω scans	h = −26→26
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007)	k = −8→4
Tmin = 0.978, Tmax = 0.982	l = −19→21
4492 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.173	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ^2(Fo^2) + (0.1157P)^2] where P = (Fo^2 + 2Fc^2)/3
2353 reflections	(Δ/σ)max = 0.001
176 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.24 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 > 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	−0.05676 (8)	0.3364 (3)	0.35564 (9)	0.0534 (5)
N1	−0.11378 (9)	0.2982 (3)	0.44012 (10)	0.0384 (5)
N2	−0.10103 (10)	0.2539 (3)	0.51998 (10)	0.0439 (5)
C11	−0.19444 (10)	0.4030 (3)	0.31598 (12)	0.0432 (6)
H11	−0.1628	0.4457	0.2982	0.052*
C10	−0.25819 (11)	0.4237 (4)	0.26886 (14)	0.0523 (7)
H10	−0.2690	0.4794	0.2192	0.063*
N3	0.06883 (10)	0.2770 (3)	0.43754 (13)	0.0500 (6)
C6	−0.17841 (10)	0.3190 (3)	0.38911 (12)	0.0378 (6)
C4	−0.00882 (11)	0.2571 (3)	0.49473 (13)	0.0382 (6)
C9	−0.30523 (12)	0.3635 (4)	0.29449 (15)	0.0586 (8)
H9	−0.3478	0.3793	0.2628	0.070*
C13	0.05492 (11)	0.2441 (3)	0.50051 (13)	0.0397 (6)
C14	0.10798 (12)	0.1939 (4)	0.57534 (14)	0.0539 (7)
H14A	0.1475	0.1930	0.5661	0.081*
H14B	0.1004	0.0711	0.5926	0.081*
H14C	0.1103	0.2852	0.6155	0.081*
C8	−0.28911 (13)	0.2791 (4)	0.36768 (16)	0.0627 (8)
H8	−0.3210	0.2374	0.3852	0.075*
C3	−0.03936 (12)	0.2315 (3)	0.55172 (13)	0.0413 (6)
C7	−0.22638 (12)	0.2558 (4)	0.41503 (14)	0.0510 (7)
H7	−0.2159	0.1980	0.4643	0.061*
C5	−0.05950 (11)	0.3010 (3)	0.42224 (12)	0.0379 (6)
C12	−0.01114 (13)	0.1893 (4)	0.63896 (13)	0.0569 (7)
H12A	−0.0446	0.1807	0.6602	0.085*
H12B	0.0177	0.2884	0.6654	0.085*
H12C	0.0115	0.0718	0.6470	0.085*
C16	0.12548 (15)	0.2950 (5)	0.34639 (18)	0.0694 (9)
C15	0.13080 (13)	0.2678 (5)	0.42954 (18)	0.0677 (8)
H15A	0.1501	0.1461	0.4481	0.081*
H15B	0.1583	0.3644	0.4624	0.081*
O2A	0.08008 (17)	0.1945 (5)	0.2936 (2)	0.0683 (13)*	0.567 (5)
O2B	0.0870 (2)	0.4236 (7)	0.3041 (3)	0.0637 (16)*	0.433 (5)
H	0.0343 (14)	0.315 (4)	0.3970 (16)	0.063 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0487 (10)	0.0768 (13)	0.0344 (9)	0.0027 (9)	0.0143 (8)	0.0094 (8)
N1	0.0392 (11)	0.0452 (11)	0.0299 (10)	0.0004 (8)	0.0115 (8)	0.0011 (8)
N2	0.0461 (12)	0.0548 (13)	0.0294 (10)	−0.0018 (9)	0.0116 (9)	0.0022 (9)
C11	0.0442 (13)	0.0431 (13)	0.0410 (13)	−0.0009 (11)	0.0135 (11)	−0.0001 (10)
C10	0.0544 (15)	0.0531 (15)	0.0421 (14)	0.0072 (12)	0.0084 (12)	0.0011 (12)
N3	0.0375 (12)	0.0651 (15)	0.0450 (13)	0.0036 (10)	0.0120 (10)	0.0048 (11)
C6	0.0441 (13)	0.0344 (12)	0.0336 (12)	0.0012 (10)	0.0122 (10)	−0.0046 (10)
C4	0.0437 (13)	0.0346 (12)	0.0323 (12)	−0.0009 (10)	0.0087 (10)	0.0005 (10)
C9	0.0436 (14)	0.077 (2)	0.0485 (16)	0.0075 (13)	0.0083 (12)	−0.0075 (14)
C13	0.0467 (14)	0.0324 (12)	0.0356 (13)	−0.0027 (10)	0.0093 (11)	−0.0034 (10)
C14	0.0487 (15)	0.0547 (15)	0.0471 (15)	−0.0001 (12)	0.0035 (12)	−0.0006 (12)
C8	0.0467 (16)	0.092 (2)	0.0538 (17)	−0.0024 (14)	0.0234 (13)	−0.0078 (15)
C3	0.0489 (14)	0.0369 (13)	0.0350 (12)	−0.0027 (10)	0.0110 (11)	−0.0003 (10)
C7	0.0445 (14)	0.0710 (19)	0.0388 (14)	−0.0002 (13)	0.0163 (12)	−0.0012 (12)
C5	0.0443 (13)	0.0381 (12)	0.0310 (12)	−0.0007 (10)	0.0131 (10)	0.0014 (9)
C12	0.0632 (17)	0.0698 (18)	0.0328 (13)	−0.0007 (14)	0.0110 (12)	0.0068 (12)
C16	0.0639 (18)	0.091 (2)	0.0568 (18)	−0.0034 (17)	0.0262 (15)	0.0007 (17)
C15	0.0434 (16)	0.094 (2)	0.0663 (19)	0.0048 (14)	0.0208 (14)	0.0060 (16)

Geometric parameters (Å, º)

O1—C5	1.251 (3)	C9—H9	0.9300
N1—C5	1.369 (3)	C13—C14	1.491 (3)
N1—N2	1.402 (2)	C14—H14A	0.9600
N1—C6	1.423 (3)	C14—H14B	0.9600
N2—C3	1.306 (3)	C14—H14C	0.9600
C11—C6	1.374 (3)	C8—C7	1.373 (3)
C11—C10	1.388 (3)	C8—H8	0.9300
C11—H11	0.9300	C3—C12	1.503 (3)
C10—C9	1.365 (4)	C7—H7	0.9300
C10—H10	0.9300	C12—H12A	0.9600
N3—C13	1.303 (3)	C12—H12B	0.9600
N3—C15	1.452 (4)	C12—H12C	0.9600
N3—H	0.90 (3)	C16—O2B	1.300 (5)
C6—C7	1.394 (4)	C16—O2A	1.328 (4)
C4—C13	1.401 (4)	C16—C15	1.476 (4)
C4—C3	1.438 (3)	C15—H15A	0.9700
C4—C5	1.429 (3)	C15—H15B	0.9700
C9—C8	1.376 (4)
C5—N1—N2	111.97 (17)	H14A—C14—H14C	109.5
C5—N1—C6	129.44 (18)	H14B—C14—H14C	109.5
N2—N1—C6	118.40 (18)	C7—C8—C9	120.7 (3)
C3—N2—N1	105.88 (18)	C7—C8—H8	119.7
C6—C11—C10	119.6 (2)	C9—C8—H8	119.7
C6—C11—H11	120.2	N2—C3—C4	111.9 (2)
C10—C11—H11	120.2	N2—C3—C12	117.9 (2)
C9—C10—C11	120.9 (2)	C4—C3—C12	130.1 (2)
C9—C10—H10	119.5	C8—C7—C6	119.8 (2)
C11—C10—H10	119.5	C8—C7—H7	120.1
C13—N3—C15	128.0 (2)	C6—C7—H7	120.1
C13—N3—H	111.0 (18)	O1—C5—N1	125.7 (2)
C15—N3—H	120.9 (18)	O1—C5—C4	128.8 (2)
C11—C6—C7	119.6 (2)	N1—C5—C4	105.45 (19)
C11—C6—N1	121.6 (2)	C3—C12—H12A	109.5
C7—C6—N1	118.8 (2)	C3—C12—H12B	109.5
C13—C4—C3	132.4 (2)	H12A—C12—H12B	109.5
C13—C4—C5	122.8 (2)	C3—C12—H12C	109.5
C3—C4—C5	104.8 (2)	H12A—C12—H12C	109.5
C10—C9—C8	119.4 (2)	H12B—C12—H12C	109.5
C10—C9—H9	120.3	O2B—C16—O2A	77.0 (3)
C8—C9—H9	120.3	O2B—C16—C15	119.0 (3)
N3—C13—C4	118.7 (2)	O2A—C16—C15	114.9 (3)
N3—C13—C14	118.0 (2)	N3—C15—C16	111.3 (2)
C4—C13—C14	123.3 (2)	N3—C15—H15A	109.4
C13—C14—H14A	109.5	C16—C15—H15A	109.4
C13—C14—H14B	109.5	N3—C15—H15B	109.4
H14A—C14—H14B	109.5	C16—C15—H15B	109.4
C13—C14—H14C	109.5	H15A—C15—H15B	108.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H···O1	0.90 (3)	1.92 (3)	2.711 (3)	146 (3)