1-(2,4-Dinitro­phen­yl)-2-(3-phenyl­allyl­idene)hydrazine pyridine hemisolvate

Yin, Z.-G.; Qian, H.-Y.; Chen, Y.-Z.; Feng, Y.-L.

doi:10.1107/S1600536807055444

1-(2,4-Dinitrophenyl)-2-(3-phenylallylidene)hydrazine pyridine hemisolvate

Z.-G. Yin, H.-Y. Qian, Y.-Z. Chen and Y.-L. Feng

The principal molecule of the title compound, C₁₅H₁₂N₄O₄·0.5C₅H₅N, is nearly planar, the largest deviation from the mean plane being 0.094 (2) Å. The pyridine solvent molecule lies on a twofold axis and is connected to the 1-(2,4-dinitrophenyl)-2-(3-phenylallylidene)hydrazine through weak C—H

O hydrogen bonding. An intramolecular N—H

O hydrogen bond helps to stabilize the molecular structure.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055444/dn2254sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055444/dn2254Isup2.hkl Contains datablock I

CCDC reference: 672879

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.003 Å
R factor = 0.064
wR factor = 0.143
Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT480_ALERT_4_C Long H...A H-Bond Reported H18    ..  O2      ..       2.68 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 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
   0 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

2,4-Dinitrophenylhydrazine has applications in organic synthesis and some of its derivatives have been shown to be potentially DNA-damaging and mutagenic agents (Okabe et al.,1993). Some phenylhydrazone derivatives have been synthesized in our laboratory. As part of our work, we report the synthesis and crystal structure of the title compound(I).

The title molecule is nearly planar with the largest deviation from the mean plane containing the two benzene rings and the C3—N2 chain,being 0.094 (2) Å at C3 (Fig. 1). The two nitro groups, O1/N1/O2 and O3/N2/O4 are slightly twisted with respect to this plane by 11.2 (2)° and 14.4 (2)° respectively. The pyridine ring is roughly perpendicular to this plane making a dihedral angle of 73.85 (9)° with it.

The Pyridine is linked to the title compound through weak intermolecular C—H···O hydrogen bonds (Table 1). An intramolecular N—H···O hydrogen bond is also observed and helps to stablize the conformation of the molecule (Table 1, Fig.1).

Related literature top

For related literature, see: Okabe et al. (1993).

Experimental top

2,4-Dinitrophenylhydrazine (1 mmol, 0.198 g) was dissolved in anhydrous methanol, H₂SO₄ (98% 0.5 ml) was added to this, the mixture was stirred for several minitutes at 351 K, cinnamaldehyde (1 mmol 0.132 g) in methanol (8 ml) was added dropwise and the mixture was stirred at refluxing temperature for 2 h. The product was isolated and recrystallized in pyridine, brown single crystals of (I) was obtained after two weeks.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. Molecular view of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.

1-(2,4-Dinitrophenyl)-2-(3-phenylallylidene)hydrazine pyridine solvate top

Crystal data top

C₁₅H₁₂N₄O₄·0.5C₅H₅N	F(000) = 1464
M_r = 351.78	D_x = 1.432 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1160 reflections
a = 17.970 (4) Å	θ = 2.1–25.5°
b = 7.1370 (14) Å	µ = 0.11 mm⁻¹
c = 26.305 (5) Å	T = 298 K
β = 104.73 (3)°	Block, red
V = 3262.8 (11) Å³	0.27 × 0.23 × 0.23 mm
Z = 8

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3328 independent reflections
Radiation source: sealed tube	2372 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 26.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −22→22
T_min = 0.966, T_max = 0.972	k = −8→8
7279 measured reflections	l = −30→32

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0521P)² + 1.2883P] where P = (F_o² + 2F_c²)/3
3328 reflections	(Δ/σ)_max < 0.001
236 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₅H₁₂N₄O₄·0.5C₅H₅N	V = 3262.8 (11) Å³
M_r = 351.78	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 17.970 (4) Å	µ = 0.11 mm⁻¹
b = 7.1370 (14) Å	T = 298 K
c = 26.305 (5) Å	0.27 × 0.23 × 0.23 mm
β = 104.73 (3)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3328 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	2372 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.972	R_int = 0.030
7279 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.13	Δρ_max = 0.18 e Å⁻³
3328 reflections	Δρ_min = −0.19 e Å⁻³
236 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
O1	0.74691 (9)	0.6036 (3)	0.22779 (7)	0.0714 (6)
O2	0.63086 (9)	0.6562 (3)	0.22975 (6)	0.0565 (5)
O3	0.84516 (12)	0.7909 (4)	0.08715 (10)	0.0985 (8)
O4	0.77336 (12)	0.9361 (3)	0.02160 (8)	0.0815 (7)
N1	0.68219 (10)	0.6592 (3)	0.20666 (7)	0.0457 (5)
N2	0.78311 (14)	0.8491 (3)	0.06274 (10)	0.0637 (6)
N3	0.52874 (9)	0.7524 (3)	0.14416 (7)	0.0447 (5)
H3	0.5347	0.7200	0.1764	0.054*
N4	0.45643 (10)	0.7859 (3)	0.11322 (7)	0.0478 (5)
N5	0.5000	−0.0289 (4)	0.2500	0.0600 (8)
C1	0.59055 (12)	0.7698 (3)	0.12459 (9)	0.0391 (5)
C2	0.66606 (12)	0.7276 (3)	0.15397 (8)	0.0386 (5)
C3	0.72816 (12)	0.7493 (3)	0.13259 (9)	0.0441 (6)
H3A	0.7775	0.7186	0.1521	0.053*
C4	0.71660 (13)	0.8154 (3)	0.08307 (9)	0.0455 (6)
C5	0.64336 (14)	0.8555 (3)	0.05233 (9)	0.0482 (6)
H5	0.6365	0.8991	0.0181	0.058*
C6	0.58213 (13)	0.8303 (3)	0.07269 (9)	0.0441 (6)
H6	0.5330	0.8539	0.0517	0.053*
C7	0.40318 (12)	0.7550 (3)	0.13646 (9)	0.0455 (6)
H7	0.4160	0.7122	0.1710	0.055*
C8	0.32407 (12)	0.7854 (3)	0.11005 (9)	0.0453 (6)
H8	0.3116	0.8288	0.0756	0.054*
C9	0.26760 (12)	0.7532 (3)	0.13355 (9)	0.0408 (5)
H9	0.2826	0.7125	0.1682	0.049*
C10	0.18547 (11)	0.7746 (3)	0.11100 (8)	0.0360 (5)
C11	0.15505 (12)	0.8241 (3)	0.05934 (9)	0.0443 (6)
H11	0.1878	0.8455	0.0377	0.053*
C12	0.07709 (13)	0.8425 (3)	0.03930 (10)	0.0509 (6)
H12	0.0574	0.8765	0.0043	0.061*
C13	0.02810 (13)	0.8108 (4)	0.07090 (10)	0.0538 (7)
H13	−0.0248	0.8228	0.0573	0.065*
C14	0.05713 (13)	0.7617 (4)	0.12213 (10)	0.0511 (6)
H14	0.0241	0.7405	0.1436	0.061*
C15	0.13524 (12)	0.7434 (3)	0.14219 (9)	0.0434 (6)
H15	0.1546	0.7095	0.1772	0.052*
C17	0.5000	0.3582 (5)	0.2500	0.0517 (9)
H17	0.5000	0.4885	0.2500	0.062*
C18	0.56730 (13)	0.2605 (4)	0.26336 (9)	0.0539 (7)
H18	0.6142	0.3230	0.2727	0.065*
C19	0.56465 (13)	0.0702 (4)	0.26284 (10)	0.0557 (7)
H19	0.6110	0.0053	0.2720	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0396 (10)	0.1113 (17)	0.0603 (11)	0.0149 (10)	0.0073 (9)	0.0132 (11)
O2	0.0419 (9)	0.0822 (14)	0.0499 (10)	0.0000 (9)	0.0198 (8)	0.0096 (9)
O3	0.0558 (13)	0.130 (2)	0.127 (2)	0.0015 (13)	0.0540 (14)	0.0153 (16)
O4	0.1057 (16)	0.0824 (15)	0.0755 (14)	−0.0282 (12)	0.0583 (13)	−0.0061 (12)
N1	0.0336 (10)	0.0547 (13)	0.0491 (12)	−0.0027 (9)	0.0109 (9)	−0.0006 (10)
N2	0.0654 (16)	0.0642 (16)	0.0760 (17)	−0.0164 (13)	0.0448 (14)	−0.0116 (13)
N3	0.0313 (10)	0.0592 (13)	0.0442 (11)	−0.0005 (9)	0.0108 (8)	0.0028 (9)
N4	0.0327 (10)	0.0595 (14)	0.0498 (12)	−0.0014 (9)	0.0082 (9)	−0.0032 (10)
N5	0.0417 (17)	0.060 (2)	0.078 (2)	0.000	0.0158 (15)	0.000
C1	0.0364 (12)	0.0363 (13)	0.0463 (13)	−0.0034 (10)	0.0137 (10)	−0.0058 (10)
C2	0.0359 (12)	0.0400 (13)	0.0416 (12)	−0.0038 (10)	0.0129 (10)	−0.0017 (10)
C3	0.0346 (12)	0.0441 (14)	0.0559 (15)	−0.0021 (10)	0.0156 (11)	−0.0084 (11)
C4	0.0481 (14)	0.0398 (14)	0.0565 (15)	−0.0089 (11)	0.0275 (12)	−0.0078 (11)
C5	0.0606 (16)	0.0451 (15)	0.0426 (13)	−0.0076 (12)	0.0198 (12)	−0.0032 (11)
C6	0.0422 (13)	0.0454 (14)	0.0442 (13)	−0.0032 (11)	0.0103 (10)	−0.0028 (11)
C7	0.0357 (12)	0.0506 (15)	0.0498 (14)	−0.0024 (11)	0.0101 (11)	−0.0034 (12)
C8	0.0355 (12)	0.0523 (16)	0.0464 (13)	−0.0040 (11)	0.0073 (10)	−0.0019 (11)
C9	0.0379 (12)	0.0444 (14)	0.0386 (12)	−0.0004 (10)	0.0067 (10)	−0.0016 (10)
C10	0.0334 (11)	0.0334 (12)	0.0405 (12)	−0.0022 (9)	0.0085 (9)	−0.0021 (10)
C11	0.0389 (12)	0.0445 (14)	0.0504 (14)	−0.0009 (10)	0.0133 (10)	0.0059 (11)
C12	0.0431 (13)	0.0526 (16)	0.0515 (14)	0.0029 (12)	0.0022 (11)	0.0111 (12)
C13	0.0320 (12)	0.0588 (17)	0.0671 (17)	0.0021 (11)	0.0063 (12)	−0.0009 (13)
C14	0.0408 (13)	0.0570 (17)	0.0606 (16)	−0.0016 (12)	0.0222 (12)	−0.0064 (13)
C15	0.0389 (12)	0.0505 (15)	0.0422 (13)	−0.0017 (11)	0.0127 (10)	−0.0022 (11)
C17	0.053 (2)	0.057 (2)	0.046 (2)	0.000	0.0150 (16)	0.000
C18	0.0394 (13)	0.0649 (19)	0.0561 (16)	−0.0073 (13)	0.0099 (12)	0.0081 (13)
C19	0.0351 (13)	0.069 (2)	0.0623 (17)	0.0045 (13)	0.0117 (12)	0.0127 (14)

Geometric parameters (Å, º) top

O1—N1	1.221 (2)	C7—H7	0.9300
O2—N1	1.227 (2)	C8—C9	1.336 (3)
O3—N2	1.210 (3)	C8—H8	0.9300
O4—N2	1.221 (3)	C9—C10	1.452 (3)
N1—C2	1.428 (3)	C9—H9	0.9300
N2—C4	1.448 (3)	C10—C11	1.376 (3)
N3—C1	1.343 (3)	C10—C15	1.383 (3)
N3—N4	1.368 (2)	C11—C12	1.372 (3)
N3—H3	0.8600	C11—H11	0.9300
N4—C7	1.279 (3)	C12—C13	1.375 (3)
N5—C19	1.328 (3)	C12—H12	0.9300
N5—C19ⁱ	1.328 (3)	C13—C14	1.361 (3)
C1—C6	1.403 (3)	C13—H13	0.9300
C1—C2	1.413 (3)	C14—C15	1.374 (3)
C2—C3	1.380 (3)	C14—H14	0.9300
C3—C4	1.351 (3)	C15—H15	0.9300
C3—H3A	0.9300	C17—C18ⁱ	1.362 (3)
C4—C5	1.388 (3)	C17—C18	1.362 (3)
C5—C6	1.353 (3)	C17—H17	0.9300
C5—H5	0.9300	C18—C19	1.359 (4)
C6—H6	0.9300	C18—H18	0.9300
C7—C8	1.431 (3)	C19—H19	0.9300

O1—N1—O2	121.2 (2)	C9—C8—H8	119.1
O1—N1—C2	119.20 (18)	C7—C8—H8	119.1
O2—N1—C2	119.59 (18)	C8—C9—C10	127.3 (2)
O3—N2—O4	123.4 (2)	C8—C9—H9	116.4
O3—N2—C4	118.9 (3)	C10—C9—H9	116.4
O4—N2—C4	117.8 (3)	C11—C10—C15	118.2 (2)
C1—N3—N4	120.60 (19)	C11—C10—C9	122.5 (2)
C1—N3—H3	119.7	C15—C10—C9	119.3 (2)
N4—N3—H3	119.7	C12—C11—C10	121.0 (2)
C7—N4—N3	113.50 (19)	C12—C11—H11	119.5
C19—N5—C19ⁱ	115.7 (3)	C10—C11—H11	119.5
N3—C1—C6	120.4 (2)	C11—C12—C13	120.0 (2)
N3—C1—C2	122.9 (2)	C11—C12—H12	120.0
C6—C1—C2	116.67 (19)	C13—C12—H12	120.0
C3—C2—C1	121.1 (2)	C14—C13—C12	119.9 (2)
C3—C2—N1	116.63 (19)	C14—C13—H13	120.1
C1—C2—N1	122.24 (18)	C12—C13—H13	120.1
C4—C3—C2	119.3 (2)	C13—C14—C15	120.1 (2)
C4—C3—H3A	120.3	C13—C14—H14	120.0
C2—C3—H3A	120.3	C15—C14—H14	120.0
C3—C4—C5	121.6 (2)	C14—C15—C10	120.9 (2)
C3—C4—N2	118.4 (2)	C14—C15—H15	119.5
C5—C4—N2	120.0 (2)	C10—C15—H15	119.5
C6—C5—C4	119.2 (2)	C18ⁱ—C17—C18	118.4 (4)
C6—C5—H5	120.4	C18ⁱ—C17—H17	120.8
C4—C5—H5	120.4	C18—C17—H17	120.8
C5—C6—C1	121.9 (2)	C19—C18—C17	118.8 (3)
C5—C6—H6	119.0	C19—C18—H18	120.6
C1—C6—H6	119.0	C17—C18—H18	120.6
N4—C7—C8	120.9 (2)	N5—C19—C18	124.1 (3)
N4—C7—H7	119.6	N5—C19—H19	117.9
C8—C7—H7	119.6	C18—C19—H19	117.9
C9—C8—C7	121.8 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···O2	0.93	2.68	3.252 (3)	120
N3—H3···O2	0.86	1.98	2.609 (3)	129

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂N₄O₄·0.5C₅H₅N
M_r	351.78
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	17.970 (4), 7.1370 (14), 26.305 (5)
β (°)	104.73 (3)
V (Å³)	3262.8 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.27 × 0.23 × 0.23

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.966, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	7279, 3328, 2372
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.143, 1.13
No. of reflections	3328
No. of parameters	236
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.