3-{[2-(Trifluoro­meth­yl)phenyl]­hydrazono}pentane-2,4-dione

Odabaşoğlu, M.; Büyükgüngör, O.; Sarojini, B.K.; Narayana, B.

doi:10.1107/S1600536807045631

3-{[2-(Trifluoromethyl)phenyl]hydrazono}pentane-2,4-dione

M. Odabaşoğlu, O. Büyükgüngör, B. K. Sarojini and B. Narayana

The crystal structure of the title compound, C₁₂H₁₁F₃N₂O₂, is stabilized by one N—H

O and two N—H

F intramolecular hydrogen bonds, and by one C—H

F and two C—H

O intermolecular hydrogen bonds. These hydrogen bonds generate R₄⁴(13)S(6)S(6)S(6)R₃³(20) ring motifs in the ac plane. Except for four H atoms of the methyl groups and two F atoms of three trifluoromethyl groups, all atoms are almost in the same plane, and the N—N=C—C(OCH₃) torsion angles are 4.1 (3) and −175.25 (14)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045631/at2398sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045631/at2398Isup2.hkl Contains datablock I

CCDC reference: 663820

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.044
wR factor = 0.145
Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    F3     -   C7      ..       7.55 su
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         C7

Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.65 mm
PLAT230_ALERT_2_C Hirshfeld Test Diff for    F2     -   C7      ..       6.49 su
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3     ..  O1      ..       2.63 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5     ..  O2      ..       2.62 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12C   ..  F1      ..       2.75 Ang.

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

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

Comment top

The title compound is used as an intermediate in the synthesis of acetyl cinnoline derivative. Cinnoline derivatives are known for their pharmacological activities (Narayana et al., 2006). The title compound synthesized by coupling 2-trifluoro methyl benzene diazoniumchloride with acetyl acetone [Fig. 4] which further underwent cyclization to yield cinnoline derivative. Recently, fluorinated organic compounds have attracted attention due to the ability of fluorine to act as polar hydrogen or hydroxyl mimic. Therefore, substitution of hydrogen by fluorine has been a strategy in designing molecules for biological activity studies (Filler & Kabayashi, 1992). Owing to the importance of title compound (I), the present paper reports the synthesis and crystal structure of the title compound.

Phenylhydrazono-1,3-diones can exist in four tautomeric forms [Fig. 3]. Our investigations show that, in the solid state, the molecular structure of (I) adopts the keto-hydrazo B form with three intramolecular hydrogen bonds (Fig. 1). This is also indicated by the N—N and C—N bond lengths (Table 1). In (I), the C1—N1, C10—N2 and N1—N2 bond lengths are 1.402 (2) Å, 1.310 (2) Å and 1.3161 (19) Å, respectively. These bonds lengths are common feature of similar systems (Odabaşoğlu et al., 2005a,b; Alpaslan et al., 2005a,b; Alpaslan et al., 2005; Alpaslan, Özdamar et al., 2006; Alpaslan, Odabaşoğlu et al., 2006; Alpaslan et al., 2007a,b).

The N1—N2 single bond of 1.3161 (19) Å is shorter than that observed in 1,2-bis-[1-(3-pyridyl)3-methyltriazen-3-yl]ethane [1.326 (3) Å; Vaughan et al., 2004] and other triazines (Pottie et al., 1998; Hooper et al., 1998). This shortening in the hydrazone group is consistent with the resonance structures shown in Fig. 3, which give to the N1—N2 bond some double-bond character.

The crystal packing is stabilized N—H···F, N—H···O intramolecular and C—H···O, C—H···F intermolecular hydrogen bonds. These hydrogen bonds generate edge-fussed R₄⁴(13)S(6)S(6)S(6)R₃³(20) ring motifs in xz plane (Fig. 2) (Etter, 1990). Except the four protons of methyl groups and two fluour atoms of three fluourmethyl group, all atoms are almost in the same plane and the dihedral angle between the aromatic ring and N1/N2/C10/C9 plane in substituted group is 3.77 (8)°. There is no C—H···π and π···π interaction in crystal packing.

Related literature top

For related structures, see: 2-bromo-N'-[(E)-4-hydroxybenzylidene]-5-methoxybenzohydrazide (Sarojini et al., 2007); bis{4-[(2-hydroxybenzylidine)hydrazino]-8-(trifluoro-methyl)quinolinium}sulfate tetrahydrate (Yathirajan et al., 2007); ethyl 4-chloro-2-[(2-nitrophenyl)hydrazono]-3-oxobutyrate (Odabaşoğlu et al., 2005a); ethyl 4-chloro-2-[(4-nitrophenyl)hydrazono]-3-oxobutyrate (Odabaşoğlu et al., 2005b). For related literature, see: Filler & Kabayashi (1992); Sreekumar et al. (2003); Narayana et al. (2006); Alpaslan et al., 2005a,b; Alpaslan et al., 2005; Alpaslan, Özdamar et al., 2006; Alpaslan, Odabaşoğlu et al., 2006; Alpaslan et al. (2007a,b); Etter (1990); Hooper et al. (1998); Pottie et al. (1998); Vaughan et al. (2004).

Experimental top

The title compound (I) was synthesized according to the reported method (Sreekumar et al., 2003) with a yield of 85% (Fig. 4). The compound was purified by recrystallization from ethanol. The initially formed 3-{(E)-[2-(trifluoromethyl)phenyl]diazenyl}pentane-2,4-dione underwent enolization to form pentane-2,3,4-trione 3-{[2-(trifluoromethyl)phenyl] hydrazone}. The crystal growth was done in a 8:2 mixture of toluene–acetone by slow evaporation technique [m.p.: 373–375 K]. Analysis for C₁₂H₁₁F₃N₂O₂: Found (Calculated): C 52.75 (52.94), H 4.20 (4.04), N 10.39% (10.29%).

Structure description top

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level..
	Fig. 2. Part of the crystal structure of (I), showing the formation of R₄⁴(13)S(6)S(6)S(6)R₃³(20) motifs. [Symmetry codes: (i) x - 1, y, z; (ii) x, 1/2 - y,z + 1/2; (iii) x + 1, 1/2 - y, z + 1/2; (iv) x + 1, y, z; (v) x, 1/2 - y, z - 1/2; (vi) x - 1, 1/2 - y, z - 1/2].
	Fig. 3. Tautomerism in the title compound.
	Fig. 4. The formation of the title compound.

3-{[2-(Trifluoromethyl)phenyl]hydrazono}pentane-2,4-dione top

Crystal data top

C₁₂H₁₁F₃N₂O₂	F(000) = 560
M_r = 272.23	D_x = 1.466 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15716 reflections
a = 8.2941 (4) Å	θ = 1.9–28.0°
b = 7.0893 (5) Å	µ = 0.13 mm⁻¹
c = 22.2665 (11) Å	T = 296 K
β = 109.545 (4)°	Prism, yellow
V = 1233.81 (12) Å³	0.65 × 0.57 × 0.44 mm
Z = 4

Data collection top

Stoe IPDS-2 diffractometer	2433 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1919 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.040
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.0°, θ_min = 1.9°
ω scans	h = −10→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −8→8
T_min = 0.925, T_max = 0.952	l = −27→27
15716 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.145	w = 1/[σ²(F_o²) + (0.0769P)² + 0.1968P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
2433 reflections	Δρ_max = 0.33 e Å⁻³
179 parameters	Δρ_min = −0.22 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (3)

Crystal data top

C₁₂H₁₁F₃N₂O₂	V = 1233.81 (12) Å³
M_r = 272.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.2941 (4) Å	µ = 0.13 mm⁻¹
b = 7.0893 (5) Å	T = 296 K
c = 22.2665 (11) Å	0.65 × 0.57 × 0.44 mm
β = 109.545 (4)°

Data collection top

Stoe IPDS-2 diffractometer	2433 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	1919 reflections with I > 2σ(I)
T_min = 0.925, T_max = 0.952	R_int = 0.040
15716 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.145	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.33 e Å⁻³
2433 reflections	Δρ_min = −0.22 e Å⁻³
179 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.4714 (2)	0.2443 (2)	0.48094 (7)	0.0492 (4)
C2	0.6472 (2)	0.2478 (2)	0.49847 (8)	0.0564 (4)
H2	0.7125	0.2667	0.5410	0.068*
C3	0.7275 (3)	0.2239 (3)	0.45425 (10)	0.0658 (5)
H3	0.8463	0.2264	0.4670	0.079*
C4	0.6326 (3)	0.1961 (3)	0.39106 (9)	0.0674 (5)
H4	0.6872	0.1793	0.3611	0.081*
C5	0.4580 (3)	0.1934 (3)	0.37252 (8)	0.0625 (5)
H5	0.3944	0.1747	0.3298	0.075*
C6	0.3743 (2)	0.2181 (2)	0.41629 (8)	0.0530 (4)
C7	0.1812 (3)	0.2184 (3)	0.39347 (8)	0.0637 (5)
C8	0.1589 (3)	0.2857 (4)	0.67265 (11)	0.0830 (7)
H8A	0.0433	0.2401	0.6574	0.100*
H8B	0.1613	0.4092	0.6906	0.100*
H8C	0.2283	0.2015	0.7047	0.100*
C9	0.2271 (2)	0.2953 (3)	0.61862 (9)	0.0603 (5)
C10	0.4125 (2)	0.3127 (2)	0.63042 (8)	0.0513 (4)
C11	0.5375 (2)	0.3573 (3)	0.69423 (8)	0.0580 (5)
C12	0.7209 (3)	0.3113 (4)	0.70645 (10)	0.0794 (6)
H12A	0.7591	0.3724	0.6751	0.095*
H12B	0.7338	0.1773	0.7039	0.095*
H12C	0.7881	0.3545	0.7482	0.095*
N1	0.3891 (2)	0.2659 (2)	0.52622 (7)	0.0523 (4)
N2	0.48311 (18)	0.29271 (19)	0.58622 (6)	0.0504 (4)
O1	0.12893 (18)	0.2806 (3)	0.56407 (7)	0.0824 (5)
O2	0.49197 (19)	0.4327 (2)	0.73475 (6)	0.0792 (5)
F1	0.1151 (2)	0.2002 (3)	0.33166 (6)	0.1288 (7)
F2	0.11712 (17)	0.0876 (2)	0.42020 (8)	0.1040 (5)
F3	0.12016 (18)	0.3783 (2)	0.40798 (8)	0.1052 (5)
H1	0.277 (3)	0.266 (3)	0.5163 (10)	0.073 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0549 (9)	0.0472 (8)	0.0424 (8)	−0.0006 (7)	0.0123 (7)	0.0008 (6)
C2	0.0553 (10)	0.0638 (10)	0.0458 (9)	−0.0007 (8)	0.0109 (7)	−0.0002 (7)
C3	0.0573 (11)	0.0793 (13)	0.0619 (11)	0.0006 (9)	0.0215 (9)	0.0030 (9)
C4	0.0770 (14)	0.0767 (12)	0.0549 (10)	0.0007 (10)	0.0308 (9)	0.0011 (9)
C5	0.0763 (13)	0.0656 (11)	0.0428 (8)	−0.0012 (9)	0.0161 (8)	−0.0008 (8)
C6	0.0583 (10)	0.0537 (9)	0.0420 (8)	−0.0020 (7)	0.0101 (7)	0.0009 (6)
C7	0.0643 (11)	0.0732 (12)	0.0431 (9)	−0.0004 (9)	0.0040 (8)	0.0012 (8)
C8	0.0678 (13)	0.1169 (19)	0.0717 (14)	−0.0016 (12)	0.0332 (11)	0.0008 (12)
C9	0.0582 (10)	0.0658 (11)	0.0568 (10)	0.0031 (8)	0.0193 (8)	−0.0002 (8)
C10	0.0531 (9)	0.0557 (9)	0.0437 (8)	0.0006 (7)	0.0145 (7)	0.0014 (7)
C11	0.0640 (11)	0.0647 (10)	0.0431 (8)	−0.0043 (8)	0.0152 (8)	0.0035 (7)
C12	0.0618 (12)	0.1099 (17)	0.0566 (11)	−0.0018 (11)	0.0067 (9)	−0.0074 (11)
N1	0.0498 (8)	0.0624 (9)	0.0411 (7)	−0.0011 (6)	0.0103 (6)	−0.0028 (6)
N2	0.0545 (8)	0.0528 (8)	0.0406 (7)	−0.0012 (6)	0.0115 (6)	−0.0007 (5)
O1	0.0520 (8)	0.1283 (14)	0.0622 (8)	−0.0022 (8)	0.0131 (7)	−0.0069 (8)
O2	0.0871 (10)	0.1029 (12)	0.0496 (7)	−0.0062 (8)	0.0253 (7)	−0.0131 (7)
F1	0.0765 (9)	0.237 (2)	0.0541 (7)	−0.0064 (11)	−0.0032 (7)	−0.0179 (10)
F2	0.0668 (8)	0.1121 (12)	0.1195 (12)	−0.0202 (7)	0.0130 (8)	0.0208 (9)
F3	0.0728 (9)	0.1024 (11)	0.1225 (12)	0.0224 (7)	0.0087 (8)	−0.0039 (9)

Geometric parameters (Å, º) top

C1—C2	1.378 (3)	C8—C9	1.493 (3)
C1—N1	1.402 (2)	C8—H8A	0.9600
C1—C6	1.407 (2)	C8—H8B	0.9600
C2—C3	1.371 (3)	C8—H8C	0.9600
C2—H2	0.9300	C9—O1	1.220 (2)
C3—C4	1.377 (3)	C9—C10	1.476 (3)
C3—H3	0.9300	C10—N2	1.310 (2)
C4—C5	1.367 (3)	C10—C11	1.486 (2)
C4—H4	0.9300	C11—O2	1.213 (2)
C5—C6	1.384 (3)	C11—C12	1.489 (3)
C5—H5	0.9300	C12—H12A	0.9600
C6—C7	1.509 (3)	C12—H12B	0.9600
C7—F1	1.306 (2)	C12—H12C	0.9600
C7—F2	1.307 (2)	N1—N2	1.3161 (19)
C7—F3	1.325 (2)	N1—H1	0.88 (2)

C2—C1—N1	121.20 (15)	C9—C8—H8B	109.5
C2—C1—C6	118.76 (16)	H8A—C8—H8B	109.5
N1—C1—C6	120.04 (16)	C9—C8—H8C	109.5
C3—C2—C1	121.10 (17)	H8A—C8—H8C	109.5
C3—C2—H2	119.4	H8B—C8—H8C	109.5
C1—C2—H2	119.4	O1—C9—C10	119.55 (17)
C2—C3—C4	120.17 (19)	O1—C9—C8	119.46 (18)
C2—C3—H3	119.9	C10—C9—C8	120.91 (17)
C4—C3—H3	119.9	N2—C10—C9	123.91 (15)
C5—C4—C3	119.73 (18)	N2—C10—C11	113.40 (15)
C5—C4—H4	120.1	C9—C10—C11	122.69 (15)
C3—C4—H4	120.1	O2—C11—C10	120.92 (17)
C4—C5—C6	121.07 (17)	O2—C11—C12	120.94 (17)
C4—C5—H5	119.5	C10—C11—C12	118.12 (16)
C6—C5—H5	119.5	C11—C12—H12A	109.5
C5—C6—C1	119.16 (17)	C11—C12—H12B	109.5
C5—C6—C7	119.25 (16)	H12A—C12—H12B	109.5
C1—C6—C7	121.58 (15)	C11—C12—H12C	109.5
F1—C7—F2	108.57 (18)	H12A—C12—H12C	109.5
F1—C7—F3	106.34 (18)	H12B—C12—H12C	109.5
F2—C7—F3	104.40 (19)	N2—N1—C1	118.68 (15)
F1—C7—C6	112.27 (17)	N2—N1—H1	118.2 (14)
F2—C7—C6	113.16 (16)	C1—N1—H1	123.1 (14)
F3—C7—C6	111.60 (16)	C10—N2—N1	121.07 (15)
C9—C8—H8A	109.5

N1—C1—C2—C3	179.00 (16)	C5—C6—C7—F3	−121.40 (19)
C6—C1—C2—C3	−0.8 (3)	C1—C6—C7—F3	57.9 (2)
C1—C2—C3—C4	0.1 (3)	O1—C9—C10—N2	−7.9 (3)
C2—C3—C4—C5	0.3 (3)	C8—C9—C10—N2	169.00 (19)
C3—C4—C5—C6	0.0 (3)	O1—C9—C10—C11	171.41 (18)
C4—C5—C6—C1	−0.7 (3)	C8—C9—C10—C11	−11.7 (3)
C4—C5—C6—C7	178.65 (18)	N2—C10—C11—O2	158.23 (18)
C2—C1—C6—C5	1.1 (2)	C9—C10—C11—O2	−21.1 (3)
N1—C1—C6—C5	−178.74 (15)	N2—C10—C11—C12	−20.2 (2)
C2—C1—C6—C7	−178.23 (16)	C9—C10—C11—C12	160.42 (18)
N1—C1—C6—C7	2.0 (2)	C2—C1—N1—N2	1.1 (2)
C5—C6—C7—F1	−2.1 (3)	C6—C1—N1—N2	−179.10 (14)
C1—C6—C7—F1	177.18 (18)	C9—C10—N2—N1	4.1 (3)
C5—C6—C7—F2	121.19 (19)	C11—C10—N2—N1	−175.25 (14)
C1—C6—C7—F2	−59.5 (2)	C1—N1—N2—C10	−179.68 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.88 (2)	1.88 (2)	2.568 (2)	133.8 (19)
N1—H1···F3	0.88 (2)	2.46 (2)	2.935 (2)	114.4 (17)
N1—H1···F2	0.88 (2)	2.46 (2)	2.949 (2)	115.9 (17)
C3—H3···O1ⁱ	0.93	2.63	3.432 (3)	145
C5—H5···O2ⁱⁱ	0.93	2.62	3.297 (2)	130
C12—H12C···F1ⁱⁱⁱ	0.96	2.75	3.517 (2)	137

Symmetry codes: (i) x+1, y, z; (ii) x, −y+1/2, z−1/2; (iii) x+1, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₁F₃N₂O₂
M_r	272.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.2941 (4), 7.0893 (5), 22.2665 (11)
β (°)	109.545 (4)
V (Å³)	1233.81 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.65 × 0.57 × 0.44

Data collection
Diffractometer	Stoe IPDS2
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.925, 0.952
No. of measured, independent and observed [I > 2σ(I)] reflections	15716, 2433, 1919
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.145, 1.10
No. of reflections	2433
No. of parameters	179
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.22

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).