3-[(2,4-Dinitro­phen­yl)hydrazono]-4,4,4-trifluoro-1-phenyl­butan-1-one

Jing, Z.-L.; Zhang, S.-J.; Yang, N.; Feng, S.-C.

doi:10.1107/S1600536807028747

3-[(2,4-Dinitrophenyl)hydrazono]-4,4,4-trifluoro-1-phenylbutan-1-one

Z.-L. Jing, S.-J. Zhang, N. Yang and S.-C. Feng

The crystal structure of the title compound, C₁₆H₁₁F₃N₄O₅, contains two aromatic rings, which are bridged by a C=N unit. The molecular structure is stabilized by intramolecular N—H

O hydrogen bonds. The chains are linked through weak intermolecular interactions, resulting in a zigzag packing arrangement.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807028747/at2327sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807028747/at2327Isup2.hkl Contains datablock I

CCDC reference: 654947

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.003 Å
R factor = 0.040
wR factor = 0.118
Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O2     -   N3      ..       5.01 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT431_ALERT_2_C Short Inter HL..A Contact  F1     ..  O2      ..       2.90 Ang.

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

   1 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
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988), the synthesis of new and designed crystal structures has become a major strand of modern chemistry. Metal complexes based on Schiff bases have attracted much attention because they can be utilized as model compounds of active centres in various proteins and enzymes (Kahwa et al., 1986; Santos et al., 2001). As part of an investigation of the coordination properties of Shiff bases functioning as ligands, we report the synthesis and structure of the title compound, (I). In the molecular structure of the title compound, (I) (Fig. 1), the expected geometric parameters are observed.

The 4,4,4-trifluoro-1-phenyl-butane-1,3-dione ring system (C1—C6) is planar, with an r.m.s. deviation for the fitted atoms of 0.0023 (4) Å, as are the (2,4-dinitro-phenyl)-hydrazine group (C11—C16), with an r.m.s. deviation of 0.0150 (3) Å, and the dihedral angles formed between these planes is 82.74 (6)°. Intramolecular N—H···O hydrogen bond stabilizes the molecular conformation, and the molecules are linked via weak intermolecular N—H···O hydrogen bonds to forming a zigzag packing arrangement.

Related literature top

For general background, see: Belloni et al. (2005); Kahwa et al. (1986); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).

Experimental top

An anhydrous ethanol solution (50 ml) of 4,4,4-trifluoro-1-phenyl- butane-1,3-dione (2.16 g, 10 mmol) was added to an anhydrous ethanol solution (50 ml) of (2,4-dinitro-phenyl)-hydrazine (1.98 g, 10 mmol) and the mixture was stirred at 350 K for 6 h under N₂, whereupon a red solution appeared. The solvent was removed and the residue recrystallized from anhydrous ethanol. The product was isolated and then dried in vacuo to give pure (I) in 84% yield. Red single crystals suitable for X-ray analysis were obtained by slow evaporation of an anhydrous ethanol solution of (I).

Structure description top

For general background, see: Belloni et al. (2005); Kahwa et al. (1986); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).

Computing details top

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, 1997); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Packing view of (I), showing the intermolecular hydrogen bonds (dashed lines).

3-[(2,4-Dinitrophenyl)hydrazono]-4,4,4-trifluoro-1-phenylbutan-1-one top

Crystal data top

C₁₆H₁₁F₃N₄O₅	F(000) = 808
M_r = 396.29	D_x = 1.558 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2407 reflections
a = 12.670 (2) Å	θ = 2.7–23.2°
b = 8.8499 (14) Å	µ = 0.14 mm⁻¹
c = 15.846 (3) Å	T = 294 K
β = 108.080 (3)°	Block, red
V = 1689.0 (5) Å³	0.22 × 0.20 × 0.16 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3451 independent reflections
Radiation source: fine-focus sealed tube	2112 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
φ and ω scans	θ_max = 26.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→15
T_min = 0.970, T_max = 0.978	k = −11→10
9400 measured reflections	l = −19→13

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0539P)² + 0.2886P] where P = (F_o² + 2F_c²)/3
3451 reflections	(Δ/σ)_max = 0.001
253 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₆H₁₁F₃N₄O₅	V = 1689.0 (5) Å³
M_r = 396.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.670 (2) Å	µ = 0.14 mm⁻¹
b = 8.8499 (14) Å	T = 294 K
c = 15.846 (3) Å	0.22 × 0.20 × 0.16 mm
β = 108.080 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3451 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2112 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.978	R_int = 0.031
9400 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 0.98	Δρ_max = 0.17 e Å⁻³
3451 reflections	Δρ_min = −0.19 e Å⁻³
253 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
F1	0.52280 (12)	0.60190 (15)	0.76335 (10)	0.0816 (5)
F2	0.41425 (12)	0.78857 (19)	0.72284 (12)	0.1009 (6)
F3	0.46161 (13)	0.71459 (19)	0.85655 (11)	0.1002 (6)
O1	0.79723 (12)	0.77365 (17)	0.77580 (10)	0.0630 (4)
O2	0.90737 (12)	1.09368 (18)	0.89456 (11)	0.0637 (4)
O3	1.00769 (13)	1.2392 (2)	0.99578 (12)	0.0780 (5)
O4	0.92171 (15)	1.3453 (2)	1.25985 (12)	0.0799 (5)
O5	0.83158 (16)	1.1765 (2)	1.30921 (11)	0.0870 (6)
N1	0.64300 (13)	0.86642 (18)	0.89153 (11)	0.0476 (4)
N2	0.73460 (13)	0.95719 (18)	0.91460 (11)	0.0497 (4)
H2	0.7683	0.9782	0.8766	0.060*
N3	0.93045 (14)	1.1511 (2)	0.96872 (12)	0.0515 (4)
N4	0.86534 (16)	1.2290 (2)	1.25123 (13)	0.0619 (5)
C1	0.84995 (17)	0.8257 (2)	0.61940 (15)	0.0527 (5)
H1	0.8928	0.7563	0.6597	0.063*
C2	0.8773 (2)	0.8615 (3)	0.54414 (16)	0.0668 (7)
H2A	0.9378	0.8154	0.5334	0.080*
C3	0.8150 (2)	0.9655 (3)	0.48503 (17)	0.0743 (7)
H3	0.8338	0.9900	0.4345	0.089*
C4	0.7249 (2)	1.0337 (3)	0.50012 (15)	0.0693 (7)
H4	0.6832	1.1042	0.4599	0.083*
C5	0.69638 (19)	0.9972 (2)	0.57511 (14)	0.0558 (5)
H5	0.6352	1.0429	0.5850	0.067*
C6	0.75850 (15)	0.8929 (2)	0.63559 (13)	0.0439 (5)
C7	0.73331 (16)	0.8507 (2)	0.71830 (13)	0.0439 (5)
C8	0.62590 (16)	0.9075 (2)	0.73105 (13)	0.0458 (5)
H8A	0.6309	1.0164	0.7380	0.055*
H8B	0.5654	0.8861	0.6774	0.055*
C9	0.59704 (16)	0.8416 (2)	0.80879 (14)	0.0450 (5)
C10	0.49893 (19)	0.7371 (3)	0.78885 (16)	0.0568 (6)
C11	0.77211 (15)	1.0141 (2)	0.99852 (12)	0.0433 (5)
C12	0.86413 (15)	1.1134 (2)	1.02618 (13)	0.0435 (5)
C13	0.89433 (16)	1.1825 (2)	1.10864 (13)	0.0474 (5)
H13	0.9537	1.2496	1.1250	0.057*
C14	0.83583 (17)	1.1508 (2)	1.16547 (13)	0.0482 (5)
C15	0.74946 (18)	1.0470 (2)	1.14354 (14)	0.0536 (5)
H15	0.7135	1.0222	1.1847	0.064*
C16	0.71734 (18)	0.9813 (2)	1.06135 (14)	0.0518 (5)
H16	0.6582	0.9137	1.0467	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0895 (10)	0.0567 (8)	0.1060 (12)	−0.0184 (7)	0.0410 (9)	−0.0213 (8)
F2	0.0541 (9)	0.1086 (12)	0.1215 (14)	−0.0132 (8)	0.0002 (9)	0.0215 (10)
F3	0.0975 (11)	0.1294 (13)	0.0980 (12)	−0.0536 (10)	0.0659 (10)	−0.0294 (10)
O1	0.0653 (10)	0.0730 (10)	0.0542 (9)	0.0225 (8)	0.0235 (8)	0.0121 (8)
O2	0.0675 (10)	0.0758 (11)	0.0578 (10)	−0.0087 (8)	0.0342 (9)	−0.0039 (8)
O3	0.0616 (10)	0.0989 (13)	0.0766 (12)	−0.0297 (10)	0.0259 (9)	−0.0022 (10)
O4	0.0753 (11)	0.0800 (12)	0.0771 (12)	−0.0021 (10)	0.0130 (9)	−0.0242 (10)
O5	0.0947 (13)	0.1202 (16)	0.0483 (10)	0.0047 (11)	0.0251 (10)	−0.0046 (10)
N1	0.0494 (10)	0.0469 (10)	0.0513 (11)	−0.0034 (8)	0.0226 (9)	−0.0026 (8)
N2	0.0531 (10)	0.0553 (10)	0.0455 (10)	−0.0096 (8)	0.0222 (8)	−0.0023 (8)
N3	0.0457 (10)	0.0551 (11)	0.0560 (12)	0.0005 (9)	0.0191 (9)	0.0110 (9)
N4	0.0583 (12)	0.0754 (14)	0.0483 (12)	0.0172 (11)	0.0113 (10)	−0.0016 (11)
C1	0.0468 (12)	0.0590 (13)	0.0552 (13)	−0.0029 (10)	0.0198 (10)	−0.0034 (11)
C2	0.0639 (15)	0.0778 (17)	0.0712 (17)	−0.0067 (13)	0.0390 (13)	−0.0081 (14)
C3	0.0924 (19)	0.0799 (18)	0.0636 (16)	−0.0149 (15)	0.0434 (15)	−0.0004 (14)
C4	0.0914 (18)	0.0643 (15)	0.0580 (15)	0.0050 (13)	0.0318 (14)	0.0112 (12)
C5	0.0642 (14)	0.0529 (12)	0.0528 (13)	0.0058 (11)	0.0219 (11)	0.0007 (11)
C6	0.0462 (11)	0.0414 (10)	0.0456 (11)	−0.0060 (9)	0.0167 (9)	−0.0055 (9)
C7	0.0492 (11)	0.0385 (10)	0.0457 (12)	−0.0003 (9)	0.0171 (10)	−0.0039 (9)
C8	0.0470 (11)	0.0447 (11)	0.0470 (12)	0.0034 (9)	0.0168 (9)	−0.0010 (9)
C9	0.0455 (11)	0.0427 (11)	0.0520 (13)	0.0019 (9)	0.0227 (10)	−0.0017 (9)
C10	0.0562 (13)	0.0592 (14)	0.0601 (14)	−0.0081 (11)	0.0254 (12)	−0.0046 (11)
C11	0.0466 (11)	0.0439 (11)	0.0411 (11)	0.0039 (9)	0.0162 (9)	0.0046 (9)
C12	0.0421 (10)	0.0458 (11)	0.0440 (11)	0.0047 (9)	0.0156 (9)	0.0080 (9)
C13	0.0415 (11)	0.0485 (12)	0.0483 (12)	0.0048 (9)	0.0084 (9)	0.0047 (10)
C14	0.0489 (12)	0.0512 (12)	0.0423 (12)	0.0092 (10)	0.0109 (10)	0.0024 (10)
C15	0.0613 (13)	0.0597 (13)	0.0463 (12)	0.0061 (11)	0.0262 (11)	0.0092 (10)
C16	0.0562 (12)	0.0526 (12)	0.0515 (13)	−0.0067 (10)	0.0237 (10)	0.0037 (10)

Geometric parameters (Å, º) top

F1—C10	1.328 (3)	C3—H3	0.9300
F2—C10	1.325 (3)	C4—C5	1.383 (3)
F3—C10	1.315 (2)	C4—H4	0.9300
O1—C7	1.222 (2)	C5—C6	1.386 (3)
O2—N3	1.229 (2)	C5—H5	0.9300
O3—N3	1.221 (2)	C6—C7	1.490 (3)
O4—N4	1.235 (2)	C7—C8	1.522 (3)
O5—N4	1.220 (2)	C8—C9	1.507 (3)
N1—C9	1.278 (2)	C8—H8A	0.9700
N1—N2	1.365 (2)	C8—H8B	0.9700
N2—C11	1.362 (2)	C9—C10	1.502 (3)
N2—H2	0.8600	C11—C16	1.409 (3)
N3—C12	1.456 (2)	C11—C12	1.417 (3)
N4—C14	1.466 (3)	C12—C13	1.385 (3)
C1—C2	1.378 (3)	C13—C14	1.361 (3)
C1—C6	1.395 (3)	C13—H13	0.9300
C1—H1	0.9300	C14—C15	1.388 (3)
C2—C3	1.374 (3)	C15—C16	1.368 (3)
C2—H2A	0.9300	C15—H15	0.9300
C3—C4	1.375 (3)	C16—H16	0.9300

C9—N1—N2	117.07 (16)	C9—C8—H8A	108.3
C11—N2—N1	119.28 (16)	C7—C8—H8A	108.3
C11—N2—H2	120.4	C9—C8—H8B	108.3
N1—N2—H2	120.4	C7—C8—H8B	108.3
O3—N3—O2	121.79 (17)	H8A—C8—H8B	107.4
O3—N3—C12	118.81 (19)	N1—C9—C10	113.94 (18)
O2—N3—C12	119.40 (17)	N1—C9—C8	128.54 (18)
O5—N4—O4	124.1 (2)	C10—C9—C8	117.47 (18)
O5—N4—C14	118.0 (2)	F3—C10—F2	106.75 (19)
O4—N4—C14	117.9 (2)	F3—C10—F1	106.58 (19)
C2—C1—C6	120.5 (2)	F2—C10—F1	105.94 (19)
C2—C1—H1	119.8	F3—C10—C9	113.91 (19)
C6—C1—H1	119.8	F2—C10—C9	111.65 (18)
C3—C2—C1	119.9 (2)	F1—C10—C9	111.53 (18)
C3—C2—H2A	120.0	N2—C11—C16	120.96 (18)
C1—C2—H2A	120.0	N2—C11—C12	122.39 (17)
C2—C3—C4	120.5 (2)	C16—C11—C12	116.59 (18)
C2—C3—H3	119.8	C13—C12—C11	121.73 (18)
C4—C3—H3	119.8	C13—C12—N3	116.41 (18)
C3—C4—C5	119.9 (2)	C11—C12—N3	121.84 (18)
C3—C4—H4	120.0	C14—C13—C12	119.04 (19)
C5—C4—H4	120.0	C14—C13—H13	120.5
C4—C5—C6	120.4 (2)	C12—C13—H13	120.5
C4—C5—H5	119.8	C13—C14—C15	121.31 (19)
C6—C5—H5	119.8	C13—C14—N4	118.8 (2)
C5—C6—C1	118.84 (19)	C15—C14—N4	119.93 (19)
C5—C6—C7	122.99 (18)	C16—C15—C14	119.89 (19)
C1—C6—C7	118.16 (18)	C16—C15—H15	120.1
O1—C7—C6	121.51 (17)	C14—C15—H15	120.1
O1—C7—C8	119.90 (17)	C15—C16—C11	121.3 (2)
C6—C7—C8	118.58 (17)	C15—C16—H16	119.4
C9—C8—C7	115.74 (16)	C11—C16—H16	119.4

C9—N1—N2—C11	165.70 (17)	C8—C9—C10—F1	75.6 (2)
C6—C1—C2—C3	0.8 (3)	N1—N2—C11—C16	−0.4 (3)
C1—C2—C3—C4	−0.4 (4)	N1—N2—C11—C12	−177.63 (16)
C2—C3—C4—C5	−0.2 (4)	N2—C11—C12—C13	173.26 (17)
C3—C4—C5—C6	0.4 (4)	C16—C11—C12—C13	−4.1 (3)
C4—C5—C6—C1	0.0 (3)	N2—C11—C12—N3	−5.3 (3)
C4—C5—C6—C7	178.9 (2)	C16—C11—C12—N3	177.36 (17)
C2—C1—C6—C5	−0.6 (3)	O3—N3—C12—C13	0.2 (3)
C2—C1—C6—C7	−179.60 (19)	O2—N3—C12—C13	−179.73 (17)
C5—C6—C7—O1	−170.44 (19)	O3—N3—C12—C11	178.87 (18)
C1—C6—C7—O1	8.5 (3)	O2—N3—C12—C11	−1.1 (3)
C5—C6—C7—C8	8.7 (3)	C11—C12—C13—C14	1.8 (3)
C1—C6—C7—C8	−172.37 (17)	N3—C12—C13—C14	−179.53 (17)
O1—C7—C8—C9	−9.9 (3)	C12—C13—C14—C15	2.3 (3)
C6—C7—C8—C9	170.94 (17)	C12—C13—C14—N4	−177.54 (17)
N2—N1—C9—C10	178.27 (16)	O5—N4—C14—C13	−163.28 (19)
N2—N1—C9—C8	−4.3 (3)	O4—N4—C14—C13	17.7 (3)
C7—C8—C9—N1	71.9 (3)	O5—N4—C14—C15	16.9 (3)
C7—C8—C9—C10	−110.8 (2)	O4—N4—C14—C15	−162.20 (19)
N1—C9—C10—F3	14.0 (3)	C13—C14—C15—C16	−4.0 (3)
C8—C9—C10—F3	−163.70 (18)	N4—C14—C15—C16	175.84 (19)
N1—C9—C10—F2	135.0 (2)	C14—C15—C16—C11	1.5 (3)
C8—C9—C10—F2	−42.7 (3)	N2—C11—C16—C15	−175.03 (18)
N1—C9—C10—F1	−106.7 (2)	C12—C11—C16—C15	2.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	1.98	2.604 (2)	129
N2—H2···O1	0.86	2.52	3.031 (2)	119

Experimental details

Crystal data
Chemical formula	C₁₆H₁₁F₃N₄O₅
M_r	396.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	12.670 (2), 8.8499 (14), 15.846 (3)
β (°)	108.080 (3)
V (Å³)	1689.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.22 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.970, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	9400, 3451, 2112
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.118, 0.98
No. of reflections	3451
No. of parameters	253
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.19

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.