(1Z)-1-[(2E)-3-(4-Bromo-phen-yl)-1-(4-fluoro-phen-yl)prop-2-en-1-yl-idene]-2-(2,4-dinitro-phen-yl)hydrazine.

In the title mol-ecule, C(21)H(14)BrFN(4)O(4), the mean planes of the two nitro groups form dihedral angles of 3.1 (2) and 7.1 (5)° with the benzene ring to which they are attached. The dinitro-substituted ring forms dihedral angles of 8.6 (2) and 71.9 (2)° with the bromo- and fluoro-substituted benzene rings, respectively. The dihedral angle between the bromo- and fluoro-substituted benzene rings is 80.6 (2)°. There is an intra-molecular N-H⋯O hydrogen bond. In the crystal, pairs of weak C-H⋯O hydrogen bonds form inversion dimers. In addition, π-π stacking inter-actions between the bromo- and dinitro-substituted rings [centroid-centroid separation = 3.768 (2) Å] are observed.

Related literature

For applications of hydrazone derivatives, see: Rollas et al. (2007 ▶); Singh et al. (1982 ▶). For the synthesis, see: Jasinski et al. (2010 ▶). For a related structure, see: Yin et al. (2009 ▶).

Experimental

Crystal data

C21H14BrFN4O4

M = 485.27

Monoclinic,

a = 15.0738 (12) Å

b = 10.6511 (5) Å

c = 14.3353 (8) Å

β = 116.010 (9)°

V = 2068.5 (2) Å3

Z = 4

Mo Kα radiation

μ = 2.03 mm−1

T = 293 K

0.3 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.889, T max = 1.000

15619 measured reflections

4058 independent reflections

2232 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.141

S = 1.01

4058 reflections

280 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.40 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812027328/lh5491sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027328/lh5491Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812027328/lh5491Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H14BrFN4O4	F(000) = 976
Mr = 485.27	Dx = 1.558 Mg m−3
Monoclinic, P21/c	Melting point = 416–414 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 15.0738 (12) Å	Cell parameters from 3762 reflections
b = 10.6511 (5) Å	θ = 3.6–29.0°
c = 14.3353 (8) Å	µ = 2.03 mm−1
β = 116.010 (9)°	T = 293 K
V = 2068.5 (2) Å3	Plate, red
Z = 4	0.3 × 0.2 × 0.1 mm

Oxford Diffraction Xcalibur Sapphire3 diffractometer	4058 independent reflections
Radiation source: fine-focus sealed tube	2232 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 16.1049 pixels mm-1	θmax = 26.0°, θmin = 3.6°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −13→13
Tmin = 0.889, Tmax = 1.000	l = −17→17
15619 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0533P)2 + 0.8232P] where P = (Fo2 + 2Fc2)/3
4058 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

	x	y	z	Uiso*/Ueq
Br1	0.10475 (5)	1.47051 (5)	0.45912 (4)	0.1080 (3)
F1	0.0359 (3)	0.6564 (3)	−0.06938 (19)	0.1523 (14)
N2	0.3279 (2)	0.5513 (3)	0.3799 (2)	0.0541 (7)
H21	0.3030	0.5395	0.3139	0.065*
O1	0.3072 (2)	0.3913 (3)	0.23628 (19)	0.0930 (10)
O2	0.3459 (3)	0.1980 (3)	0.2728 (2)	0.0946 (10)
O3	0.4846 (3)	0.0425 (4)	0.6152 (3)	0.1316 (16)
O4	0.5243 (3)	0.1687 (4)	0.7432 (3)	0.1200 (13)
N3	0.3419 (3)	0.3052 (4)	0.2993 (2)	0.0700 (9)
N1	0.3238 (2)	0.6688 (3)	0.4176 (2)	0.0581 (8)
N4	0.4898 (3)	0.1471 (5)	0.6501 (4)	0.0932 (12)
C1	0.1384 (3)	1.3158 (4)	0.4190 (3)	0.0624 (10)
C2	0.1915 (3)	1.2297 (4)	0.4951 (3)	0.0620 (10)
H2	0.2122	1.2492	0.5648	0.074*
C3	0.2135 (3)	1.1146 (4)	0.4666 (3)	0.0615 (10)
H3	0.2490	1.0559	0.5173	0.074*
C4	0.1829 (3)	1.0855 (3)	0.3623 (3)	0.0574 (9)
C5	0.1301 (3)	1.1750 (4)	0.2885 (3)	0.0655 (10)
H5	0.1090	1.1564	0.2186	0.079*
C6	0.1080 (3)	1.2911 (4)	0.3162 (3)	0.0692 (11)
H6	0.0732	1.3507	0.2660	0.083*
C7	0.2021 (3)	0.9630 (3)	0.3285 (3)	0.0621 (10)
H7	0.1672	0.9451	0.2581	0.074*
C8	0.2633 (3)	0.8747 (3)	0.3863 (3)	0.0613 (10)
H8	0.3046	0.8936	0.4553	0.074*
C9	0.2700 (3)	0.7506 (3)	0.3489 (3)	0.0560 (9)
C10	0.2108 (3)	0.7207 (3)	0.2368 (3)	0.0523 (9)
C11	0.2375 (4)	0.7628 (4)	0.1622 (3)	0.0780 (12)
H11	0.2958	0.8080	0.1816	0.094*
C12	0.1792 (5)	0.7388 (5)	0.0598 (4)	0.0965 (17)
H12	0.1981	0.7659	0.0095	0.116*
C13	0.0950 (5)	0.6765 (5)	0.0324 (3)	0.0895 (16)
C14	0.0659 (3)	0.6315 (5)	0.1030 (4)	0.0905 (14)
H14	0.0074	0.5864	0.0822	0.109*
C15	0.1253 (3)	0.6545 (4)	0.2068 (3)	0.0695 (11)
H15	0.1068	0.6246	0.2566	0.083*
C16	0.3702 (2)	0.4545 (3)	0.4448 (2)	0.0495 (8)
C17	0.4066 (3)	0.4703 (4)	0.5530 (2)	0.0565 (9)
H17	0.4031	0.5488	0.5797	0.068*
C18	0.4465 (3)	0.3722 (4)	0.6188 (3)	0.0643 (11)
H18	0.4705	0.3840	0.6900	0.077*
C19	0.4517 (3)	0.2545 (4)	0.5802 (3)	0.0614 (10)
C20	0.4187 (3)	0.2341 (4)	0.4765 (3)	0.0614 (10)
H20	0.4231	0.1549	0.4516	0.074*
C21	0.3786 (2)	0.3336 (4)	0.4092 (2)	0.0537 (9)

	U11	U22	U33	U12	U13	U23
Br1	0.1532 (6)	0.0716 (4)	0.1080 (4)	0.0292 (3)	0.0652 (4)	−0.0073 (3)
F1	0.197 (3)	0.147 (3)	0.0548 (16)	0.047 (3)	0.0025 (18)	−0.0091 (17)
N2	0.0666 (19)	0.0520 (18)	0.0393 (15)	0.0087 (15)	0.0193 (14)	0.0017 (14)
O1	0.145 (3)	0.077 (2)	0.0458 (15)	0.027 (2)	0.0320 (17)	0.0036 (16)
O2	0.142 (3)	0.073 (2)	0.079 (2)	0.022 (2)	0.0581 (19)	−0.0100 (16)
O3	0.181 (4)	0.087 (3)	0.122 (3)	0.061 (3)	0.062 (3)	0.047 (2)
O4	0.114 (3)	0.140 (3)	0.074 (2)	0.031 (2)	0.0118 (19)	0.046 (2)
N3	0.085 (2)	0.072 (2)	0.058 (2)	0.015 (2)	0.0360 (18)	−0.0049 (19)
N1	0.0656 (19)	0.0526 (18)	0.0520 (17)	0.0019 (16)	0.0219 (15)	−0.0028 (16)
N4	0.084 (3)	0.099 (3)	0.086 (3)	0.026 (3)	0.028 (2)	0.040 (3)
C1	0.072 (3)	0.051 (2)	0.068 (2)	0.001 (2)	0.034 (2)	−0.003 (2)
C2	0.073 (3)	0.060 (2)	0.050 (2)	−0.002 (2)	0.025 (2)	−0.0078 (19)
C3	0.070 (3)	0.054 (2)	0.054 (2)	0.002 (2)	0.0223 (19)	0.0022 (19)
C4	0.066 (2)	0.049 (2)	0.054 (2)	−0.0019 (19)	0.0235 (19)	−0.0034 (18)
C5	0.084 (3)	0.055 (2)	0.051 (2)	−0.001 (2)	0.024 (2)	−0.0016 (19)
C6	0.081 (3)	0.062 (3)	0.057 (2)	0.010 (2)	0.023 (2)	0.005 (2)
C7	0.079 (3)	0.051 (2)	0.055 (2)	−0.004 (2)	0.028 (2)	−0.0027 (19)
C8	0.072 (3)	0.050 (2)	0.056 (2)	−0.004 (2)	0.022 (2)	−0.0055 (19)
C9	0.062 (2)	0.051 (2)	0.057 (2)	−0.0016 (19)	0.0279 (19)	0.0011 (19)
C10	0.066 (2)	0.0431 (19)	0.050 (2)	0.0094 (18)	0.0277 (19)	0.0034 (16)
C11	0.102 (3)	0.075 (3)	0.069 (3)	−0.005 (3)	0.049 (3)	0.003 (2)
C12	0.165 (6)	0.078 (3)	0.064 (3)	0.017 (4)	0.066 (4)	0.011 (3)
C13	0.120 (4)	0.080 (3)	0.042 (3)	0.036 (3)	0.011 (3)	−0.003 (2)
C14	0.073 (3)	0.096 (4)	0.081 (3)	0.009 (3)	0.013 (3)	−0.014 (3)
C15	0.072 (3)	0.077 (3)	0.058 (2)	0.003 (2)	0.026 (2)	0.001 (2)
C16	0.045 (2)	0.057 (2)	0.0428 (19)	0.0024 (17)	0.0162 (16)	0.0023 (17)
C17	0.058 (2)	0.061 (2)	0.046 (2)	−0.0004 (19)	0.0180 (18)	−0.0017 (18)
C18	0.051 (2)	0.091 (3)	0.0410 (19)	−0.002 (2)	0.0110 (17)	0.006 (2)
C19	0.050 (2)	0.071 (3)	0.058 (2)	0.013 (2)	0.0180 (19)	0.019 (2)
C20	0.058 (2)	0.061 (2)	0.065 (2)	0.0100 (19)	0.0274 (19)	0.007 (2)
C21	0.054 (2)	0.062 (2)	0.047 (2)	0.0077 (19)	0.0236 (17)	0.0017 (18)

Br1—C1	1.886 (4)	C7—H7	0.9300
F1—C13	1.352 (5)	C8—C9	1.447 (5)
N2—C16	1.347 (4)	C8—H8	0.9300
N2—N1	1.376 (4)	C9—C10	1.491 (5)
N2—H21	0.8600	C10—C15	1.363 (5)
O1—N3	1.231 (4)	C10—C11	1.372 (5)
O2—N3	1.213 (4)	C11—C12	1.365 (6)
O3—N4	1.209 (5)	C11—H11	0.9300
O4—N4	1.223 (5)	C12—C13	1.330 (7)
N3—C21	1.455 (4)	C12—H12	0.9300
N1—C9	1.298 (4)	C13—C14	1.356 (7)
N4—C19	1.463 (5)	C14—C15	1.381 (5)
C1—C6	1.363 (5)	C14—H14	0.9300
C1—C2	1.381 (5)	C15—H15	0.9300
C2—C3	1.378 (5)	C16—C21	1.411 (5)
C2—H2	0.9300	C16—C17	1.411 (4)
C3—C4	1.393 (5)	C17—C18	1.359 (5)
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.386 (5)	C18—C19	1.386 (5)
C4—C7	1.464 (5)	C18—H18	0.9300
C5—C6	1.384 (5)	C19—C20	1.361 (5)
C5—H5	0.9300	C20—C21	1.381 (5)
C6—H6	0.9300	C20—H20	0.9300
C7—C8	1.324 (5)
C16—N2—N1	120.9 (3)	C15—C10—C11	118.9 (4)
C16—N2—H21	119.5	C15—C10—C9	119.1 (3)
N1—N2—H21	119.5	C11—C10—C9	121.9 (4)
O2—N3—O1	122.3 (3)	C12—C11—C10	120.4 (5)
O2—N3—C21	119.1 (3)	C12—C11—H11	119.8
O1—N3—C21	118.6 (3)	C10—C11—H11	119.8
C9—N1—N2	115.6 (3)	C13—C12—C11	119.6 (4)
O3—N4—O4	123.0 (4)	C13—C12—H12	120.2
O3—N4—C19	120.1 (4)	C11—C12—H12	120.2
O4—N4—C19	116.9 (5)	C12—C13—F1	119.3 (6)
C6—C1—C2	122.0 (4)	C12—C13—C14	122.3 (4)
C6—C1—Br1	119.4 (3)	F1—C13—C14	118.3 (6)
C2—C1—Br1	118.6 (3)	C13—C14—C15	118.2 (5)
C3—C2—C1	119.2 (3)	C13—C14—H14	120.9
C3—C2—H2	120.4	C15—C14—H14	120.9
C1—C2—H2	120.4	C10—C15—C14	120.6 (4)
C2—C3—C4	120.5 (3)	C10—C15—H15	119.7
C2—C3—H3	119.8	C14—C15—H15	119.7
C4—C3—H3	119.8	N2—C16—C21	122.7 (3)
C5—C4—C3	118.4 (3)	N2—C16—C17	120.4 (3)
C5—C4—C7	119.4 (3)	C21—C16—C17	116.9 (3)
C3—C4—C7	122.2 (3)	C18—C17—C16	120.8 (4)
C6—C5—C4	121.7 (3)	C18—C17—H17	119.6
C6—C5—H5	119.2	C16—C17—H17	119.6
C4—C5—H5	119.2	C17—C18—C19	120.3 (3)
C1—C6—C5	118.3 (4)	C17—C18—H18	119.9
C1—C6—H6	120.9	C19—C18—H18	119.9
C5—C6—H6	120.9	C20—C19—C18	121.5 (3)
C8—C7—C4	127.6 (3)	C20—C19—N4	118.0 (4)
C8—C7—H7	116.2	C18—C19—N4	120.5 (4)
C4—C7—H7	116.2	C19—C20—C21	118.6 (4)
C7—C8—C9	124.0 (3)	C19—C20—H20	120.7
C7—C8—H8	118.0	C21—C20—H20	120.7
C9—C8—H8	118.0	C20—C21—C16	122.0 (3)
N1—C9—C8	116.9 (3)	C20—C21—N3	116.1 (3)
N1—C9—C10	123.7 (3)	C16—C21—N3	121.9 (3)
C8—C9—C10	119.3 (3)
C16—N2—N1—C9	−171.1 (3)	F1—C13—C14—C15	−178.6 (4)
C6—C1—C2—C3	−0.8 (6)	C11—C10—C15—C14	−0.8 (6)
Br1—C1—C2—C3	177.7 (3)	C9—C10—C15—C14	176.3 (4)
C1—C2—C3—C4	0.3 (6)	C13—C14—C15—C10	0.0 (6)
C2—C3—C4—C5	0.0 (6)	N1—N2—C16—C21	−178.0 (3)
C2—C3—C4—C7	−178.1 (4)	N1—N2—C16—C17	3.5 (5)
C3—C4—C5—C6	0.3 (6)	N2—C16—C17—C18	177.9 (3)
C7—C4—C5—C6	178.4 (4)	C21—C16—C17—C18	−0.7 (5)
C2—C1—C6—C5	1.1 (6)	C16—C17—C18—C19	−0.3 (5)
Br1—C1—C6—C5	−177.4 (3)	C17—C18—C19—C20	1.0 (6)
C4—C5—C6—C1	−0.9 (6)	C17—C18—C19—N4	−176.7 (3)
C5—C4—C7—C8	168.4 (4)	O3—N4—C19—C20	−5.6 (6)
C3—C4—C7—C8	−13.6 (6)	O4—N4—C19—C20	175.9 (4)
C4—C7—C8—C9	172.9 (4)	O3—N4—C19—C18	172.3 (5)
N2—N1—C9—C8	179.3 (3)	O4—N4—C19—C18	−6.3 (6)
N2—N1—C9—C10	3.5 (5)	C18—C19—C20—C21	−0.6 (6)
C7—C8—C9—N1	−171.1 (4)	N4—C19—C20—C21	177.2 (3)
C7—C8—C9—C10	4.9 (6)	C19—C20—C21—C16	−0.5 (5)
N1—C9—C10—C15	75.0 (5)	C19—C20—C21—N3	−178.2 (3)
C8—C9—C10—C15	−100.7 (4)	N2—C16—C21—C20	−177.4 (3)
N1—C9—C10—C11	−108.0 (4)	C17—C16—C21—C20	1.1 (5)
C8—C9—C10—C11	76.3 (5)	N2—C16—C21—N3	0.2 (5)
C15—C10—C11—C12	0.1 (6)	C17—C16—C21—N3	178.7 (3)
C9—C10—C11—C12	−176.9 (4)	O2—N3—C21—C20	1.9 (5)
C10—C11—C12—C13	1.4 (7)	O1—N3—C21—C20	−178.6 (3)
C11—C12—C13—F1	177.9 (4)	O2—N3—C21—C16	−175.8 (4)
C11—C12—C13—C14	−2.3 (8)	O1—N3—C21—C16	3.7 (5)
C12—C13—C14—C15	1.6 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O1	0.86	1.95	2.584 (4)	130
C11—H11···O4i	0.93	2.45	3.316 (7)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1	0.86	1.95	2.584 (4)	130
C11—H11⋯O4i	0.93	2.45	3.316 (7)	154

Symmetry code: (i) .