(E)-Benzaldehyde (2,4,6-trichloro­phen­yl)hydrazone

Huang, Y.-L.; Li, D.-F.; Sun, J.; Gao, J.-H.; Shan, S.

doi:10.1107/S160053681100328X

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o528

doi:10.1107/S160053681100328X

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(E)-Benzaldehyde (2,4,6-trichlorophenyl)hydrazone

Yan-Lan Huang,^a Deng-Feng Li,^a Jian Sun,^a Jin-Hua Gao ^a and Shang Shan ^a ^*

^aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, People's Republic of China
^*Correspondence e-mail: shanshang@mail.hz.zj.cn

(Received 22 January 2011; accepted 25 January 2011; online 29 January 2011)

The title compound, C₁₃H₉Cl₃N₂, was obtained from a condensation reaction of benzaldehyde and 2,4,6-trichlorophenylhydrazine. The molecule assumes an E configuration with the phenyl ring and trichlorophenyl ring located on opposite sides of the C=N bond. The phenyl ring is oriented at a dihedral angle of 42.58 (12)° with respect to the tricholorophenyl ring. In the crystal, the molecules are linked via N—H⋯N hydrogen bonds, forming supramolecular chains running along the c axis. π–π stacking is present between parallel trichlorophenyl rings of adjacent molecules, the face-to-face and centroid–centroid distances being 3.369 (14) and 3.724 (2) Å, respectively.

Related literature

For the biological activity of phenylhydrazone derivatives, see: Okabe et al. (1993 ). For related structures, see: Shan et al. (2003 ); Fan et al. (2005 ); Bolte & Dill (1998 ).

Experimental

Crystal data

C₁₃H₉Cl₃N₂
M_r = 299.57
Monoclinic, P 2₁ /c
a = 13.913 (6) Å
b = 12.867 (5) Å
c = 7.652 (3) Å
β = 98.739 (5)°
V = 1353.9 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.66 mm⁻¹
T = 295 K
0.36 × 0.30 × 0.26 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.86, T_max = 0.92
11730 measured reflections
2436 independent reflections
1936 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.105
S = 1.06
2436 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N2ⁱ	0.95	2.44	3.183 (3)	134
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100328X/xu5149sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100328X/xu5149Isup2.hkl

checkCIF report

Comment top

As some phenylhydrazone derivatives have been shown to be potential DNA-damaging or mutagenic agents (Okabe et al., 1993), a series of phenylhydrazone derivatives has been synthesized in our laboratory in order to investigate the structure/bioactivity relationship (Shan et al. 2003; Fan et al. 2005).

The title molecule crystallizes in an E conformation, with the C1-phenyl ring and C8-benzene ring on opposite sides of the C7═N2 double bond. This agrees with the configuration commonly found in phenylhydrazone derivatives (Bolte & Dill, 1998). In the molecule, the phenyl ring is oriented with respect to the tricholorophenyl ring at a dihedral angle of 42.58 (12)°. In the crystal structure, the molecules are linked via N—H···N hydrogen bonds to form the supra-molecular chains running along the c axis. π-π stacking is present between parallel tricholorophenyl rings of adjacent molecules, the face-to-face distance being 3.369 (14) Å.

Related literature top

For the biological activity of phenylhydrazone derivatives, see: Okabe et al. (1993). For related compounds, see: Shan et al. (2003); Fan et al. (2005); Bolte & Dill (1998).

Experimental top

2,4,6-Trichlorophenylhydrazine (0.21 g,1 mmol) was dissolved in ethanol (18 ml) and acetic acid (0.3 ml) was added slowly with stirring. The solution was heated at about 333 K for several minutes until it became clear. Benzaldehyde (0.11 g, 1 mmol) was added dropwise with continuous stirring, and the mixture solution was refluxed for 2 h. When the solution cooled to room temperature, microcrystals appeared. The microcrystals were separated from the solution and washed with cold water three times. Recrystallization was performed twice with an absolute ethanol to obtain single crystals of the title compound.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The structure of (I) with 50% probability displacement ellipsoids.

(E)-Benzaldehyde (2,4,6-trichlorophenyl)hydrazone top

Crystal data top

C₁₃H₉Cl₃N₂	F(000) = 608
M_r = 299.57	D_x = 1.470 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4171 reflections
a = 13.913 (6) Å	θ = 2.8–26.3°
b = 12.867 (5) Å	µ = 0.66 mm⁻¹
c = 7.652 (3) Å	T = 295 K
β = 98.739 (5)°	Prism, colorless
V = 1353.9 (9) Å³	0.36 × 0.30 × 0.26 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2436 independent reflections
Radiation source: fine-focus sealed tube	1936 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 10.0 pixels mm^-1	θ_max = 25.2°, θ_min = 3.0°
ω scans	h = −16→16
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −15→15
T_min = 0.86, T_max = 0.92	l = −9→9
11730 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0449P)² + 0.4002P] where P = (F_o² + 2F_c²)/3
2436 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₃H₉Cl₃N₂	V = 1353.9 (9) Å³
M_r = 299.57	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.913 (6) Å	µ = 0.66 mm⁻¹
b = 12.867 (5) Å	T = 295 K
c = 7.652 (3) Å	0.36 × 0.30 × 0.26 mm
β = 98.739 (5)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	2436 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1936 reflections with I > 2σ(I)
T_min = 0.86, T_max = 0.92	R_int = 0.028
11730 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.06	Δρ_max = 0.18 e Å⁻³
2436 reflections	Δρ_min = −0.32 e Å⁻³
163 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
Cl1	0.82868 (5)	0.03185 (5)	0.52523 (10)	0.0786 (2)
Cl2	1.16441 (5)	0.21670 (7)	0.78646 (11)	0.0897 (3)
Cl3	0.85826 (6)	0.45120 (5)	0.53336 (10)	0.0877 (3)
N1	0.75114 (15)	0.24687 (17)	0.4714 (3)	0.0746 (6)
H1N	0.7271	0.1962	0.3849	0.089*
N2	0.69094 (13)	0.30372 (14)	0.5622 (2)	0.0566 (5)
C1	0.84849 (16)	0.24097 (18)	0.5442 (3)	0.0557 (6)
C2	0.89458 (15)	0.14534 (18)	0.5762 (3)	0.0548 (5)
C3	0.99117 (16)	0.13659 (19)	0.6484 (3)	0.0595 (6)
H3	1.0203	0.0717	0.6674	0.071*
C4	1.04329 (16)	0.2259 (2)	0.6915 (3)	0.0612 (6)
C5	1.00210 (17)	0.3222 (2)	0.6597 (3)	0.0638 (6)
H5	1.0386	0.3821	0.6883	0.077*
C6	0.90617 (18)	0.32876 (19)	0.5850 (3)	0.0603 (6)
C7	0.59985 (17)	0.29350 (17)	0.5147 (3)	0.0582 (6)
H7	0.5769	0.2464	0.4258	0.070*
C8	0.53090 (15)	0.35459 (18)	0.5976 (3)	0.0535 (5)
C9	0.56026 (17)	0.44135 (18)	0.6979 (3)	0.0561 (5)
H9	0.6254	0.4608	0.7146	0.067*
C10	0.4942 (2)	0.4996 (2)	0.7737 (3)	0.0760 (7)
H10	0.5151	0.5578	0.8411	0.091*
C11	0.3983 (2)	0.4720 (3)	0.7501 (4)	0.0934 (10)
H11	0.3539	0.5115	0.8011	0.112*
C12	0.3676 (2)	0.3869 (3)	0.6520 (5)	0.0952 (10)
H12	0.3022	0.3683	0.6369	0.114*
C13	0.43269 (18)	0.3272 (2)	0.5741 (4)	0.0758 (7)
H13	0.4110	0.2694	0.5066	0.091*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0633 (4)	0.0709 (4)	0.1004 (5)	−0.0018 (3)	0.0087 (4)	−0.0148 (3)
Cl2	0.0506 (4)	0.1110 (6)	0.1040 (6)	−0.0073 (3)	0.0007 (3)	0.0177 (4)
Cl3	0.0985 (5)	0.0642 (4)	0.0989 (5)	0.0182 (4)	0.0100 (4)	0.0040 (4)
N1	0.0620 (12)	0.0951 (16)	0.0601 (12)	0.0270 (11)	−0.0114 (10)	−0.0335 (11)
N2	0.0565 (11)	0.0629 (11)	0.0472 (10)	0.0140 (9)	−0.0023 (9)	−0.0060 (8)
C1	0.0581 (13)	0.0691 (15)	0.0397 (11)	0.0130 (11)	0.0065 (10)	−0.0078 (10)
C2	0.0520 (12)	0.0631 (14)	0.0509 (12)	0.0030 (10)	0.0124 (10)	−0.0055 (10)
C3	0.0505 (13)	0.0658 (14)	0.0639 (14)	0.0065 (11)	0.0144 (11)	0.0089 (11)
C4	0.0470 (12)	0.0816 (17)	0.0564 (13)	0.0007 (11)	0.0131 (11)	0.0108 (12)
C5	0.0634 (15)	0.0684 (15)	0.0606 (14)	−0.0047 (12)	0.0130 (12)	−0.0005 (12)
C6	0.0697 (15)	0.0612 (14)	0.0501 (12)	0.0092 (12)	0.0093 (11)	−0.0009 (11)
C7	0.0608 (14)	0.0596 (13)	0.0492 (12)	0.0031 (11)	−0.0081 (11)	−0.0046 (10)
C8	0.0478 (12)	0.0649 (14)	0.0455 (11)	0.0044 (10)	−0.0002 (9)	0.0120 (10)
C9	0.0554 (13)	0.0670 (14)	0.0447 (11)	0.0102 (11)	0.0039 (10)	0.0081 (11)
C10	0.0832 (19)	0.0897 (18)	0.0567 (15)	0.0249 (15)	0.0159 (14)	0.0066 (13)
C11	0.077 (2)	0.130 (3)	0.081 (2)	0.030 (2)	0.0352 (17)	0.023 (2)
C12	0.0486 (15)	0.136 (3)	0.104 (2)	0.0061 (17)	0.0195 (16)	0.042 (2)
C13	0.0581 (15)	0.0892 (19)	0.0758 (17)	−0.0089 (14)	−0.0034 (13)	0.0176 (14)

Geometric parameters (Å, º) top

Cl1—C2	1.737 (2)	C5—H5	0.9300
Cl2—C4	1.735 (2)	C7—C8	1.458 (3)
Cl3—C6	1.733 (2)	C7—H7	0.9300
N1—N2	1.377 (3)	C8—C9	1.381 (3)
N1—C1	1.386 (3)	C8—C13	1.396 (3)
N1—H1N	0.9526	C9—C10	1.380 (3)
N2—C7	1.271 (3)	C9—H9	0.9300
C1—C2	1.392 (3)	C10—C11	1.367 (4)
C1—C6	1.393 (3)	C10—H10	0.9300
C2—C3	1.378 (3)	C11—C12	1.359 (5)
C3—C4	1.372 (3)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.389 (4)
C4—C5	1.372 (3)	C12—H12	0.9300
C5—C6	1.372 (3)	C13—H13	0.9300

N2—N1—C1	117.26 (18)	N2—C7—C8	120.9 (2)
N2—N1—H1N	122.5	N2—C7—H7	119.6
C1—N1—H1N	117.4	C8—C7—H7	119.6
C7—N2—N1	117.19 (19)	C9—C8—C13	118.5 (2)
N1—C1—C2	121.0 (2)	C9—C8—C7	121.3 (2)
N1—C1—C6	122.7 (2)	C13—C8—C7	120.3 (2)
C2—C1—C6	116.3 (2)	C10—C9—C8	120.9 (2)
C3—C2—C1	122.5 (2)	C10—C9—H9	119.6
C3—C2—Cl1	118.09 (18)	C8—C9—H9	119.6
C1—C2—Cl1	119.38 (18)	C11—C10—C9	120.2 (3)
C4—C3—C2	118.4 (2)	C11—C10—H10	119.9
C4—C3—H3	120.8	C9—C10—H10	119.9
C2—C3—H3	120.8	C12—C11—C10	120.1 (3)
C3—C4—C5	121.5 (2)	C12—C11—H11	120.0
C3—C4—Cl2	119.22 (19)	C10—C11—H11	120.0
C5—C4—Cl2	119.3 (2)	C11—C12—C13	120.8 (3)
C4—C5—C6	118.9 (2)	C11—C12—H12	119.6
C4—C5—H5	120.6	C13—C12—H12	119.6
C6—C5—H5	120.6	C12—C13—C8	119.7 (3)
C5—C6—C1	122.3 (2)	C12—C13—H13	120.2
C5—C6—Cl3	117.8 (2)	C8—C13—H13	120.2
C1—C6—Cl3	119.84 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2ⁱ	0.95	2.44	3.183 (3)	134

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₉Cl₃N₂
M_r	299.57
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	13.913 (6), 12.867 (5), 7.652 (3)
β (°)	98.739 (5)
V (Å³)	1353.9 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.36 × 0.30 × 0.26

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.86, 0.92
No. of measured, independent and observed [I > 2σ(I)] reflections	11730, 2436, 1936
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.105, 1.06
No. of reflections	2436
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.32

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2ⁱ	0.95	2.44	3.183 (3)	134

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

The work was supported by the Natural Science Foundation of Zhejiang Province of China (No. M203027).

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