2-(1H-1,2,3-Benzotriazol-1-yl)-N′-(2-chloro­benzyl­idene)acetohydrazide

He, G.-F.; Shi, Z.-Q.

doi:10.1107/S1600536810050440

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 1| January 2011| Page o48

https://doi.org/10.1107/S1600536810050440

Open

access

2-(1H-1,2,3-Benzotriazol-1-yl)-N′-(2-chlorobenzylidene)acetohydrazide

Guo-Fang He ^a ^* and Zhi-Qiang Shi ^a

^aDepartment of Materials Science and Chemical Engineering, Taishan University, 271021 Taian, Shandong, People's Republic of China
^*Correspondence e-mail: tsuhgf@163.com

(Received 26 November 2010; accepted 2 December 2010; online 8 December 2010)

In the title compound, C₁₅H₁₂ClN₅O, the mean planes of the benzotriazole and chlorophenyl fragments form a dihedral angle of 70.8 (1)°. In the crystal, molecules are linked into infinite chains along the a axis by N—H⋯O hydrogen bonds. Weak intermolecular C—H⋯N hydrogen bonds further link these chains into layers parallel to the ab plane. The crystal studied was a racemic twin.

Related literature

For related structures, see: Shi et al. (2007a ,b ); Ji & Shi (2008 ).

Experimental

Crystal data

C₁₅H₁₂ClN₅O
M_r = 313.75
Monoclinic, P 2₁
a = 4.6777 (16) Å
b = 11.726 (4) Å
c = 13.328 (5) Å
β = 94.224 (7)°
V = 729.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 295 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.968, T_max = 0.979
3851 measured reflections
1902 independent reflections
1370 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.089
S = 1.01
1902 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 544 Flack pairs
Flack parameter: 0.55 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯O1ⁱ	0.86	2.04	2.841 (4)	154
C7—H7A⋯N3ⁱⁱ	0.97	2.48	3.320 (6)	145
Symmetry codes: (i) x+1, y, z; (ii) $[-x+2, y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810050440/cv5009sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810050440/cv5009Isup2.hkl

checkCIF report

Comment top

In continuation of our structural studies of benzotriazole derivatives (Shi et al., 2007a,b; Ji et al., 2008), herewith we present the crystal structure of the title compound, (I).

In (I) (Fig. 1), the bond lengths and angles are normal and in a good agreement with those observed in the related compounds (Shi et al., 2007a,b; Ji et al., 2008). The mean planes of the benzotriazole and chlorophenyl fragments form a dihedral angle of 70.8 (1)°.

In the crystal structure, the molecules are linked into infinite chains along the a axis by N—H···O hydrogen bonds (Table 1; Fig. 2). Weak intermolecular C—H···N hydrogen bonds (Table 1) link further these chains into layers parallel to ab plane.

Related literature top

For related structures, see: Shi et al. (2007a,b); Ji et al. (2008).

Experimental top

The title compound was synthesized by the reaction of 2-(1H-1,2,3-benzotriazol-1-yl)acetohydrazide (1 mmol, 191.2 mg) with 2-chlorobenzaldehyde(1 mmol, 140.6 mg) in ethanol(20 ml)under reflux conditions (348 K) for 5 h. The solvent was removed and the solid product recrystallized from tetrahydrofuran. After five days colourless crystals suitable for X-ray diffraction study were obtained.

Structure description top

In continuation of our structural studies of benzotriazole derivatives (Shi et al., 2007a,b; Ji et al., 2008), herewith we present the crystal structure of the title compound, (I).

For related structures, see: Shi et al. (2007a,b); Ji et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Hydrogen-bonded (dashed lines) chain in (I). H atoms not included in hydrogen bonding have been omitted for clarity.

2-(1H-1,2,3-Benzotriazol-1-yl)-N'-(2- chlorobenzylidene)acetohydrazide top

Crystal data top

C₁₅H₁₂ClN₅O	F(000) = 324
M_r = 313.75	D_x = 1.429 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 676 reflections
a = 4.6777 (16) Å	θ = 2.3–18.9°
b = 11.726 (4) Å	µ = 0.27 mm⁻¹
c = 13.328 (5) Å	T = 295 K
β = 94.224 (7)°	Block, colourless
V = 729.0 (4) Å³	0.12 × 0.10 × 0.08 mm
Z = 2

Data collection top

Bruker APEXII CCD area-detector diffractometer	1902 independent reflections
Radiation source: fine-focus sealed tube	1370 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
phi and ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −5→5
T_min = 0.968, T_max = 0.979	k = −9→13
3851 measured reflections	l = −15→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0267P)² + 0.1806P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1902 reflections	Δρ_max = 0.16 e Å⁻³
199 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 544 Flack pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.55 (11)

Crystal data top

C₁₅H₁₂ClN₅O	V = 729.0 (4) Å³
M_r = 313.75	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.6777 (16) Å	µ = 0.27 mm⁻¹
b = 11.726 (4) Å	T = 295 K
c = 13.328 (5) Å	0.12 × 0.10 × 0.08 mm
β = 94.224 (7)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1902 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1370 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.979	R_int = 0.039
3851 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.089	Δρ_max = 0.16 e Å⁻³
S = 1.01	Δρ_min = −0.17 e Å⁻³
1902 reflections	Absolute structure: Flack (1983), 544 Flack pairs
199 parameters	Absolute structure parameter: 0.55 (11)
0 restraints

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	1.5224 (3)	0.95422 (11)	0.46424 (9)	0.0660 (4)
O1	0.7318 (6)	0.5815 (3)	0.17718 (18)	0.0473 (8)
N1	0.9309 (7)	0.4707 (3)	0.0172 (2)	0.0377 (8)
N2	0.9247 (9)	0.3561 (3)	0.0325 (3)	0.0523 (10)
N3	0.7297 (9)	0.3113 (3)	−0.0307 (3)	0.0561 (11)
N4	1.1772 (7)	0.6360 (3)	0.2368 (2)	0.0413 (9)
H4	1.3555	0.6412	0.2257	0.050*
N5	1.0786 (8)	0.6779 (3)	0.3252 (2)	0.0391 (9)
C1	0.7313 (9)	0.5002 (4)	−0.0583 (3)	0.0361 (10)
C2	0.6509 (10)	0.6045 (4)	−0.1011 (3)	0.0466 (11)
H2	0.7386	0.6726	−0.0805	0.056*
C3	0.4329 (11)	0.6000 (5)	−0.1759 (3)	0.0619 (14)
H3	0.3692	0.6677	−0.2063	0.074*
C4	0.3028 (11)	0.4976 (6)	−0.2083 (3)	0.0632 (15)
H4A	0.1586	0.4996	−0.2602	0.076*
C5	0.3809 (10)	0.3947 (5)	−0.1661 (3)	0.0585 (14)
H5	0.2931	0.3269	−0.1874	0.070*
C6	0.6035 (10)	0.3978 (4)	−0.0881 (3)	0.0437 (11)
C7	1.1297 (9)	0.5398 (4)	0.0782 (3)	0.0427 (11)
H7A	1.1955	0.6024	0.0383	0.051*
H7B	1.2950	0.4943	0.1011	0.051*
C8	0.9886 (9)	0.5868 (4)	0.1684 (3)	0.0354 (9)
C9	1.2636 (10)	0.7317 (3)	0.3822 (3)	0.0421 (11)
H9	1.4451	0.7469	0.3612	0.050*
C10	1.1839 (9)	0.7691 (4)	0.4815 (3)	0.0406 (10)
C11	1.2939 (9)	0.8682 (4)	0.5275 (3)	0.0446 (11)
C12	1.2219 (10)	0.8998 (4)	0.6219 (3)	0.0564 (13)
H12	1.2975	0.9660	0.6516	0.068*
C13	1.0391 (12)	0.8333 (5)	0.6715 (3)	0.0608 (15)
H13	0.9924	0.8544	0.7355	0.073*
C14	0.9219 (11)	0.7351 (4)	0.6283 (3)	0.0569 (14)
H14	0.7953	0.6908	0.6623	0.068*
C15	0.9967 (10)	0.7035 (4)	0.5332 (3)	0.0481 (12)
H15	0.9198	0.6374	0.5038	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0682 (8)	0.0536 (7)	0.0772 (8)	−0.0105 (7)	0.0128 (7)	−0.0064 (7)
O1	0.0283 (18)	0.071 (2)	0.0436 (17)	−0.0008 (16)	0.0071 (13)	−0.0112 (15)
N1	0.042 (2)	0.032 (2)	0.0409 (19)	−0.0015 (18)	0.0082 (16)	−0.0021 (16)
N2	0.063 (3)	0.038 (2)	0.057 (2)	0.001 (2)	0.010 (2)	0.001 (2)
N3	0.071 (3)	0.038 (2)	0.059 (2)	−0.006 (2)	0.005 (2)	−0.006 (2)
N4	0.033 (2)	0.055 (2)	0.0374 (19)	0.0000 (18)	0.0100 (16)	−0.0138 (17)
N5	0.038 (2)	0.047 (2)	0.033 (2)	0.0031 (18)	0.0092 (17)	−0.0054 (17)
C1	0.035 (3)	0.039 (2)	0.036 (2)	0.000 (2)	0.0133 (19)	−0.0049 (19)
C2	0.051 (3)	0.041 (3)	0.049 (3)	0.003 (2)	0.014 (2)	0.002 (2)
C3	0.058 (4)	0.075 (4)	0.053 (3)	0.014 (3)	0.005 (3)	0.009 (3)
C4	0.051 (3)	0.096 (5)	0.042 (3)	0.007 (3)	0.004 (2)	−0.006 (3)
C5	0.051 (3)	0.079 (4)	0.046 (3)	−0.012 (3)	0.006 (2)	−0.020 (3)
C6	0.053 (3)	0.040 (3)	0.040 (2)	−0.002 (2)	0.014 (2)	−0.009 (2)
C7	0.043 (3)	0.052 (3)	0.035 (2)	−0.006 (2)	0.012 (2)	−0.009 (2)
C8	0.039 (3)	0.037 (2)	0.030 (2)	0.001 (2)	0.0049 (19)	0.0016 (18)
C9	0.041 (3)	0.046 (3)	0.040 (2)	−0.004 (2)	0.006 (2)	−0.007 (2)
C10	0.044 (3)	0.046 (3)	0.032 (2)	0.008 (2)	0.002 (2)	−0.0024 (19)
C11	0.044 (3)	0.046 (3)	0.044 (2)	0.004 (2)	0.002 (2)	−0.003 (2)
C12	0.067 (3)	0.054 (3)	0.048 (3)	0.008 (3)	−0.001 (2)	−0.016 (2)
C13	0.077 (4)	0.071 (4)	0.035 (3)	0.023 (3)	0.010 (3)	−0.007 (3)
C14	0.068 (4)	0.063 (3)	0.042 (3)	0.010 (3)	0.017 (2)	0.002 (2)
C15	0.051 (3)	0.049 (3)	0.044 (3)	0.003 (2)	0.005 (2)	−0.004 (2)

Geometric parameters (Å, º) top

Cl1—C11	1.733 (4)	C4—H4A	0.9300
O1—C8	1.217 (4)	C5—C6	1.416 (6)
N1—N2	1.359 (5)	C5—H5	0.9300
N1—C1	1.366 (5)	C7—C8	1.517 (5)
N1—C7	1.440 (5)	C7—H7A	0.9700
N2—N3	1.306 (5)	C7—H7B	0.9700
N3—C6	1.377 (5)	C9—C10	1.468 (5)
N4—C8	1.350 (5)	C9—H9	0.9300
N4—N5	1.387 (4)	C10—C15	1.386 (6)
N4—H4	0.8600	C10—C11	1.394 (5)
N5—C9	1.275 (5)	C11—C12	1.377 (5)
C1—C6	1.387 (5)	C12—C13	1.364 (6)
C1—C2	1.389 (6)	C12—H12	0.9300
C2—C3	1.374 (6)	C13—C14	1.383 (7)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.399 (7)	C14—C15	1.390 (6)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.370 (7)	C15—H15	0.9300

N2—N1—C1	109.9 (4)	C8—C7—H7A	109.5
N2—N1—C7	119.5 (4)	N1—C7—H7B	109.5
C1—N1—C7	130.6 (3)	C8—C7—H7B	109.5
N3—N2—N1	108.8 (4)	H7A—C7—H7B	108.1
N2—N3—C6	108.2 (3)	O1—C8—N4	123.9 (4)
C8—N4—N5	118.9 (3)	O1—C8—C7	123.2 (4)
C8—N4—H4	120.5	N4—C8—C7	112.9 (4)
N5—N4—H4	120.5	N5—C9—C10	118.5 (4)
C9—N5—N4	115.3 (3)	N5—C9—H9	120.7
N1—C1—C6	104.4 (3)	C10—C9—H9	120.7
N1—C1—C2	132.5 (4)	C15—C10—C11	118.0 (3)
C6—C1—C2	123.1 (4)	C15—C10—C9	119.6 (4)
C3—C2—C1	115.4 (5)	C11—C10—C9	122.4 (4)
C3—C2—H2	122.3	C12—C11—C10	121.3 (4)
C1—C2—H2	122.3	C12—C11—Cl1	119.3 (4)
C2—C3—C4	122.6 (5)	C10—C11—Cl1	119.5 (3)
C2—C3—H3	118.7	C13—C12—C11	119.6 (4)
C4—C3—H3	118.7	C13—C12—H12	120.2
C5—C4—C3	122.2 (5)	C11—C12—H12	120.2
C5—C4—H4A	118.9	C12—C13—C14	121.2 (4)
C3—C4—H4A	118.9	C12—C13—H13	119.4
C4—C5—C6	116.0 (5)	C14—C13—H13	119.4
C4—C5—H5	122.0	C13—C14—C15	118.8 (5)
C6—C5—H5	122.0	C13—C14—H14	120.6
N3—C6—C1	108.7 (4)	C15—C14—H14	120.6
N3—C6—C5	130.6 (4)	C10—C15—C14	121.1 (4)
C1—C6—C5	120.7 (4)	C10—C15—H15	119.4
N1—C7—C8	110.6 (3)	C14—C15—H15	119.4
N1—C7—H7A	109.5

C1—N1—N2—N3	0.4 (4)	N2—N1—C7—C8	−93.6 (4)
C7—N1—N2—N3	179.9 (3)	C1—N1—C7—C8	85.8 (5)
N1—N2—N3—C6	−0.5 (5)	N5—N4—C8—O1	3.6 (6)
C8—N4—N5—C9	−174.3 (4)	N5—N4—C8—C7	−177.1 (3)
N2—N1—C1—C6	−0.1 (4)	N1—C7—C8—O1	−11.3 (6)
C7—N1—C1—C6	−179.6 (4)	N1—C7—C8—N4	169.5 (3)
N2—N1—C1—C2	179.1 (4)	N4—N5—C9—C10	−174.2 (3)
C7—N1—C1—C2	−0.4 (7)	N5—C9—C10—C15	33.0 (6)
N1—C1—C2—C3	−178.9 (4)	N5—C9—C10—C11	−148.1 (4)
C6—C1—C2—C3	0.2 (6)	C15—C10—C11—C12	0.7 (6)
C1—C2—C3—C4	−1.0 (6)	C9—C10—C11—C12	−178.2 (4)
C2—C3—C4—C5	1.2 (8)	C15—C10—C11—Cl1	−178.6 (3)
C3—C4—C5—C6	−0.5 (7)	C9—C10—C11—Cl1	2.6 (6)
N2—N3—C6—C1	0.5 (5)	C10—C11—C12—C13	−0.2 (7)
N2—N3—C6—C5	−179.5 (4)	Cl1—C11—C12—C13	179.1 (4)
N1—C1—C6—N3	−0.2 (4)	C11—C12—C13—C14	−0.7 (7)
C2—C1—C6—N3	−179.5 (4)	C12—C13—C14—C15	0.9 (7)
N1—C1—C6—C5	179.7 (3)	C11—C10—C15—C14	−0.4 (6)
C2—C1—C6—C5	0.4 (6)	C9—C10—C15—C14	178.5 (4)
C4—C5—C6—N3	179.7 (5)	C13—C14—C15—C10	−0.4 (7)
C4—C5—C6—C1	−0.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O1ⁱ	0.86	2.04	2.841 (4)	154
C7—H7A···N3ⁱⁱ	0.97	2.48	3.320 (6)	145

Symmetry codes: (i) x+1, y, z; (ii) −x+2, y+1/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂ClN₅O
M_r	313.75
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	295
a, b, c (Å)	4.6777 (16), 11.726 (4), 13.328 (5)
β (°)	94.224 (7)
V (Å³)	729.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.968, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	3851, 1902, 1370
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.089, 1.01
No. of reflections	1902
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.17
Absolute structure	Flack (1983), 544 Flack pairs
Absolute structure parameter	0.55 (11)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O1ⁱ	0.86	2.04	2.841 (4)	154.0
C7—H7A···N3ⁱⁱ	0.97	2.48	3.320 (6)	145.3

Symmetry codes: (i) x+1, y, z; (ii) −x+2, y+1/2, −z.

Acknowledgements

This work was supported by Taian City Science and Technology Bureau (grant No. 20081009).

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ji, N.-N. & Shi, Z.-Q. (2008). Acta Cryst. E64, o2141. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, Z.-Q., Ji, N.-N., Zheng, Z.-B. & Li, J.-K. (2007a). Acta Cryst. E63, o4561. Web of Science CSD CrossRef IUCr Journals Google Scholar
Shi, Z.-Q., Ji, N.-N., Zheng, Z.-B. & Li, J.-K. (2007b). Acta Cryst. E63, o4642. Web of Science CSD CrossRef IUCr Journals Google Scholar