Literature DB >> 21754502

(E)-1-(2,4-Dinitro-phen-yl)-2-(2-fluoro-benzyl-idene)hydrazine.

Jerry P Jasinski, Adam N Braley, C S Chidan Kumar, H S Yathirajan, A N Mayekar.

Abstract

In the title compound, C(13)H(9)FN(4)O(4), the dihedral angle between the mean planes of the two benzene rings of the nearly planar mol-ecule is 6.6 (9)°. The dihedral angles between the mean planes of the benzene ring and its two attached nitro groups are 6.7 (7) and 7.2 (9)°. Crystal packing is stabilized by N-H⋯O hydrogen bonds, weak C-H⋯O and C-H⋯F inter-molecular inter-actions and centroid-centroid π-ring stacking inter-actions.

Entities: Chemical Disease Species

Year: 2011 PMID： 21754502 PMCID： PMC3089184 DOI： 10.1107/S1600536811014383

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For Schiff base propeties, see: Liang (2007 ▶). For nonlinear optical and crystalline properties, see: Baughman et al. (2004 ▶). For DNA-damaging and mutagenic agents, see: Okabe et al. (1993 ▶). For related structures, see: Bolte & Dill (1998 ▶); Shan et al. (2002 ▶); Fan et al. (2004 ▶); Motherwell & Ramsay, (2007 ▶); Shi et al. (2008 ▶); Ji et al. (2010 ▶); Kia et al. (2009 ▶); Jasinski et al. (2010 ▶).

Experimental

Crystal data

C13H9FN4O4 M = 304.24 Triclinic, a = 7.0961 (8) Å b = 8.2714 (9) Å c = 11.7230 (8) Å α = 88.614 (7)° β = 80.544 (8)° γ = 71.368 (10)° V = 642.86 (11) Å3 Z = 2 Mo Kα radiation μ = 0.13 mm−1 T = 173 K 0.20 × 0.18 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.967, T max = 1.000 6346 measured reflections 3466 independent reflections 2802 reflections with I > 2σ(I) R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.045 wR(F 2) = 0.143 S = 1.09 3466 reflections 199 parameters H-atom parameters constrained Δρmax = 0.31 e Å−3 Δρmin = −0.17 e Å−3 Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007 ▶); 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. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811014383/ng5151sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014383/ng5151Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₃H₉FN₄O₄	Z = 2
M_r = 304.24	F(000) = 312
Triclinic, P1	D_x = 1.572 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0961 (8) Å	Cell parameters from 3528 reflections
b = 8.2714 (9) Å	θ = 3.1–32.2°
c = 11.7230 (8) Å	µ = 0.13 mm⁻¹
α = 88.614 (7)°	T = 173 K
β = 80.544 (8)°	Block, orange-red
γ = 71.368 (10)°	0.20 × 0.18 × 0.15 mm
V = 642.86 (11) Å³

Oxford Diffraction Xcalibur Eos Gemini diffractometer	3466 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2802 reflections with I > 2σ(I)
graphite	R_int = 0.016
Detector resolution: 16.1500 pixels mm^-1	θ_max = 29.1°, θ_min = 3.1°
φ and ω scans	h = −9→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −11→11
T_min = 0.967, T_max = 1.000	l = −16→15
6346 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0733P)² + 0.0845P] where P = (F_o² + 2F_c²)/3
3466 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

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	U_iso*/U_eq
F1	1.25967 (13)	0.08268 (12)	0.46347 (7)	0.0542 (3)
O1	0.33061 (16)	0.49706 (16)	0.46244 (9)	0.0576 (3)
O2	0.04251 (15)	0.62057 (14)	0.41195 (9)	0.0539 (3)
O3	0.0526 (2)	0.21724 (19)	−0.01824 (12)	0.0791 (4)
O4	−0.15820 (15)	0.42413 (15)	0.08977 (10)	0.0561 (3)
N1	0.79790 (15)	0.14775 (14)	0.28682 (9)	0.0377 (2)
N2	0.61603 (16)	0.26801 (15)	0.32453 (9)	0.0391 (3)
H2A	0.5959	0.3291	0.3884	0.047*
N3	0.00969 (19)	0.32023 (16)	0.06233 (11)	0.0443 (3)
N4	0.20937 (16)	0.51447 (14)	0.39505 (10)	0.0393 (3)
C1	1.2885 (2)	−0.02327 (17)	0.37123 (11)	0.0381 (3)
C2	1.4763 (2)	−0.1424 (2)	0.33969 (14)	0.0499 (3)
H2B	1.5823	−0.1511	0.3819	0.060*
C3	1.5057 (2)	−0.2487 (2)	0.24485 (15)	0.0534 (4)
H3A	1.6336	−0.3321	0.2214	0.064*
C4	1.3510 (2)	−0.23481 (18)	0.18385 (13)	0.0482 (3)
H4A	1.3727	−0.3086	0.1187	0.058*
C5	1.1651 (2)	−0.11396 (17)	0.21735 (11)	0.0404 (3)
H5A	1.0595	−0.1052	0.1747	0.049*
C6	1.12930 (18)	−0.00419 (15)	0.31287 (10)	0.0332 (3)
C7	0.93392 (18)	0.12582 (16)	0.34949 (11)	0.0358 (3)
H7A	0.9091	0.1924	0.4185	0.043*
C8	0.46749 (17)	0.29040 (15)	0.26058 (10)	0.0329 (3)
C9	0.26980 (18)	0.40469 (15)	0.29198 (10)	0.0324 (3)
C10	0.12047 (18)	0.41764 (14)	0.22616 (10)	0.0336 (3)
H10A	−0.0115	0.4954	0.2487	0.040*
C11	0.16630 (19)	0.31661 (15)	0.12820 (11)	0.0345 (3)
C12	0.3609 (2)	0.20726 (17)	0.09136 (11)	0.0396 (3)
H12A	0.3909	0.1412	0.0216	0.048*
C13	0.50799 (19)	0.19515 (17)	0.15534 (11)	0.0390 (3)
H13A	0.6408	0.1213	0.1290	0.047*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0485 (5)	0.0679 (6)	0.0446 (5)	−0.0099 (4)	−0.0184 (4)	−0.0156 (4)
O1	0.0428 (6)	0.0767 (7)	0.0512 (6)	−0.0123 (5)	−0.0111 (5)	−0.0292 (5)
O2	0.0424 (6)	0.0553 (6)	0.0517 (6)	0.0007 (5)	−0.0030 (4)	−0.0189 (5)
O3	0.0686 (8)	0.0871 (9)	0.0790 (9)	−0.0060 (7)	−0.0370 (7)	−0.0388 (7)
O4	0.0380 (5)	0.0613 (7)	0.0664 (7)	−0.0057 (5)	−0.0209 (5)	−0.0032 (5)
N1	0.0290 (5)	0.0430 (6)	0.0384 (6)	−0.0080 (4)	−0.0046 (4)	−0.0036 (4)
N2	0.0292 (5)	0.0480 (6)	0.0373 (5)	−0.0077 (4)	−0.0053 (4)	−0.0108 (4)
N3	0.0440 (6)	0.0463 (6)	0.0455 (6)	−0.0131 (5)	−0.0174 (5)	−0.0022 (5)
N4	0.0348 (5)	0.0427 (6)	0.0392 (6)	−0.0121 (4)	−0.0013 (4)	−0.0110 (4)
C1	0.0385 (6)	0.0426 (6)	0.0338 (6)	−0.0116 (5)	−0.0102 (5)	−0.0005 (5)
C2	0.0391 (7)	0.0540 (8)	0.0529 (8)	−0.0048 (6)	−0.0174 (6)	0.0011 (6)
C3	0.0407 (7)	0.0461 (7)	0.0613 (9)	0.0020 (6)	−0.0060 (6)	−0.0041 (7)
C4	0.0529 (8)	0.0415 (7)	0.0455 (8)	−0.0103 (6)	−0.0031 (6)	−0.0091 (6)
C5	0.0408 (7)	0.0430 (7)	0.0393 (7)	−0.0136 (5)	−0.0107 (5)	−0.0040 (5)
C6	0.0317 (6)	0.0357 (6)	0.0329 (6)	−0.0113 (5)	−0.0061 (4)	0.0007 (4)
C7	0.0333 (6)	0.0418 (6)	0.0331 (6)	−0.0129 (5)	−0.0054 (5)	−0.0042 (5)
C8	0.0286 (5)	0.0363 (6)	0.0339 (6)	−0.0108 (5)	−0.0044 (4)	−0.0034 (4)
C9	0.0313 (6)	0.0335 (5)	0.0318 (6)	−0.0103 (4)	−0.0027 (4)	−0.0058 (4)
C10	0.0298 (6)	0.0313 (5)	0.0382 (6)	−0.0076 (4)	−0.0056 (4)	−0.0021 (4)
C11	0.0354 (6)	0.0335 (6)	0.0363 (6)	−0.0104 (5)	−0.0115 (5)	−0.0006 (5)
C12	0.0394 (7)	0.0403 (6)	0.0361 (6)	−0.0071 (5)	−0.0077 (5)	−0.0092 (5)
C13	0.0316 (6)	0.0416 (6)	0.0385 (6)	−0.0044 (5)	−0.0045 (5)	−0.0090 (5)

F1—C1	1.3555 (15)	C3—H3A	0.9500
O1—N4	1.2343 (15)	C4—C5	1.3785 (19)
O2—N4	1.2161 (15)	C4—H4A	0.9500
O3—N3	1.2204 (16)	C5—C6	1.3967 (17)
O4—N3	1.2225 (15)	C5—H5A	0.9500
N1—C7	1.2724 (16)	C6—C7	1.4618 (17)
N1—N2	1.3653 (15)	C7—H7A	0.9500
N2—C8	1.3548 (16)	C8—C9	1.4131 (17)
N2—H2A	0.8800	C8—C13	1.4181 (16)
N3—C11	1.4463 (16)	C9—C10	1.3863 (16)
N4—C9	1.4500 (15)	C10—C11	1.3685 (17)
C1—C2	1.3783 (19)	C10—H10A	0.9500
C1—C6	1.3800 (17)	C11—C12	1.3916 (18)
C2—C3	1.381 (2)	C12—C13	1.3597 (18)
C2—H2B	0.9500	C12—H12A	0.9500
C3—C4	1.379 (2)	C13—H13A	0.9500

C7—N1—N2	117.04 (11)	C1—C6—C5	116.70 (11)
C8—N2—N1	117.99 (10)	C1—C6—C7	121.17 (11)
C8—N2—H2A	121.0	C5—C6—C7	122.12 (11)
N1—N2—H2A	121.0	N1—C7—C6	118.51 (11)
O3—N3—O4	123.15 (12)	N1—C7—H7A	120.7
O3—N3—C11	117.69 (12)	C6—C7—H7A	120.7
O4—N3—C11	119.16 (11)	N2—C8—C9	123.98 (11)
O2—N4—O1	122.32 (11)	N2—C8—C13	119.48 (11)
O2—N4—C9	119.24 (11)	C9—C8—C13	116.55 (11)
O1—N4—C9	118.44 (11)	C10—C9—C8	121.82 (10)
F1—C1—C2	118.20 (12)	C10—C9—N4	115.72 (11)
F1—C1—C6	118.24 (11)	C8—C9—N4	122.45 (11)
C2—C1—C6	123.55 (12)	C11—C10—C9	118.91 (11)
C1—C2—C3	118.00 (13)	C11—C10—H10A	120.5
C1—C2—H2B	121.0	C9—C10—H10A	120.5
C3—C2—H2B	121.0	C10—C11—C12	121.27 (11)
C4—C3—C2	120.60 (14)	C10—C11—N3	119.78 (11)
C4—C3—H3A	119.7	C12—C11—N3	118.93 (11)
C2—C3—H3A	119.7	C13—C12—C11	119.89 (11)
C5—C4—C3	120.00 (13)	C13—C12—H12A	120.1
C5—C4—H4A	120.0	C11—C12—H12A	120.1
C3—C4—H4A	120.0	C12—C13—C8	121.44 (11)
C4—C5—C6	121.14 (12)	C12—C13—H13A	119.3
C4—C5—H5A	119.4	C8—C13—H13A	119.3
C6—C5—H5A	119.4

C7—N1—N2—C8	−178.38 (11)	N2—C8—C9—N4	2.32 (19)
F1—C1—C2—C3	−179.24 (13)	C13—C8—C9—N4	−177.74 (11)
C6—C1—C2—C3	−0.3 (2)	O2—N4—C9—C10	−6.98 (17)
C1—C2—C3—C4	0.2 (2)	O1—N4—C9—C10	173.40 (12)
C2—C3—C4—C5	0.0 (2)	O2—N4—C9—C8	173.56 (12)
C3—C4—C5—C6	−0.1 (2)	O1—N4—C9—C8	−6.07 (19)
F1—C1—C6—C5	179.17 (11)	C8—C9—C10—C11	0.07 (18)
C2—C1—C6—C5	0.3 (2)	N4—C9—C10—C11	−179.40 (11)
F1—C1—C6—C7	−0.39 (18)	C9—C10—C11—C12	−2.71 (19)
C2—C1—C6—C7	−179.28 (13)	C9—C10—C11—N3	176.08 (11)
C4—C5—C6—C1	0.0 (2)	O3—N3—C11—C10	−173.46 (14)
C4—C5—C6—C7	179.51 (12)	O4—N3—C11—C10	6.06 (19)
N2—N1—C7—C6	178.86 (10)	O3—N3—C11—C12	5.4 (2)
C1—C6—C7—N1	173.99 (12)	O4—N3—C11—C12	−175.12 (12)
C5—C6—C7—N1	−5.54 (19)	C10—C11—C12—C13	2.3 (2)
N1—N2—C8—C9	177.09 (11)	N3—C11—C12—C13	−176.51 (12)
N1—N2—C8—C13	−2.85 (18)	C11—C12—C13—C8	0.8 (2)
N2—C8—C9—C10	−177.12 (11)	N2—C8—C13—C12	176.68 (12)
C13—C8—C9—C10	2.82 (18)	C9—C8—C13—C12	−3.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.88	2.02	2.6317 (15)	126.
N2—H2A···O1ⁱ	0.88	2.51	3.3424 (15)	158.
C2—H2B···F1ⁱⁱ	0.95	2.45	3.3386 (17)	156.
C3—H3A···O4ⁱⁱⁱ	0.95	2.48	3.3177 (19)	148.
C5—H5A···O3^iv	0.95	2.43	3.2694 (17)	148.

CgI···CgJ	Cg···Cg (Å)	Cg I_Perp (Å)	CgJ_Perp (Å)
Cg1···Cg2ⁱ	3.6916 (10)	-3.4632 (6)	3.3267 (5)
Cg2···Cg1ⁱⁱ	3.6916 (10)	3.3267 (5)	-3.4632 (6)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.88	2.02	2.6317 (15)	126
N2—H2A⋯O1ⁱ	0.88	2.51	3.3424 (15)	158
C2—H2B⋯F1ⁱⁱ	0.95	2.45	3.3386 (17)	156
C3—H3A⋯O4ⁱⁱⁱ	0.95	2.48	3.3177 (19)	148
C5—H5A⋯O3^iv	0.95	2.43	3.2694 (17)	148

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

Table 2

Cg⋯Cg π-ring stacking interactions

Cg1 and Cg2 are the centroids of rings C1–C6 and C8–C13, respectively.

CgI⋯CgJ	Cg⋯Cg (Å)	CgI_Perp (Å)	CgJ_Perp (Å)
Cg1⋯Cg2ⁱ	3.6916 (10)	−3.4632 (6)	3.3267 (5)
Cg2⋯Cg1ⁱⁱ	3.6916 (10)	3.3267 (5)	−3.4632 (6)

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

5 in total

(E)-1-(2,4-Dinitro-phen-yl)-2-(2-fluoro-benzyl-idene)hydrazine.

Related literature

Experimental

Crystal data

Data collection

Refinement

1. 2,4-Dinitrophenylhydrazones of 2,4-dihydroxybenzaldehyde, 2,4-dihydroxyacetophenone and 2,4-dihydroxybenzophenone.

2. A short history of SHELX.

3. N-(2,4-Dinitro-phen-yl)-N'-(1-p-tolyl-ethyl-idene)hydrazine.

4. (1E)-1-(3-Bromo-phen-yl)ethanone 2,4-di-nitro-phenyl-hydrazone.

5. 1-(2-Chloro-benzyl-idene)-2-(2,4-dinitro-phen-yl)hydrazine.