6-Chloro-N′-(2,4-dichloro­benzyl­idene)nicotinohydrazide

The title compound, C₁₃H₈Cl₃N₃O, was synthesized by the condensation reaction of 2,4-dichloro­benzaldehyde with 6-chloro­nicotinic acid hydrazide in a methanol solution. The Schiff base mol­ecule displays a trans configuration with respect to the C=N and C—N bonds. The dihedral angle between the benzene and pyridine rings is 5.5 (3)°. The crystal structure is stabilized by inter­molecular N—H...O, C—H...O and C—H...N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.086
• wR factor = 0.190
• Data-to-parameter ratio = 15.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         40 Perc.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 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
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Schiff base compounds have been widely investigated over a century (Fan et al., 2007; Kim et al., 2005; Nimitsiriwat et al., 2004). Some of the compounds have been found to have pharmacological and antibacterial activity (Chen et al., 1997; Ren et al., 2002). In this paper, the crystal structure of a new Schiff base compound derived from the condensation reaction of 2,4-dichlorobenzaldehyde with 6-chloronicotinic acid hydrazide is reported.

The Schiff base molecule of the compound displays a trans configuration with respect to the C═N and C—N bonds (Fig. 1). The dihedral angle between the C1—C6 phenyl ring and the C9—C13/N3 pyridine ring is 5.5 (3)°. All the bond lengths are within normal ranges (Allen et al., 1987). The crystal structure is stabilized by intermolecular N–H···O, C–H···O and C–H···N hydrogen bonds (Table 1 and Fig. 2).

Related literature

For related literature, see: Allen et al. (1987); Chen et al. (1997); Fan et al. (2007); Kim et al. (2005); Nimitsiriwat et al. (2004); Ren et al. (2002).

S2. Experimental

2,4-Dichlorobenzaldehyde (0.1 mmol, 17.5 mg) and 6-chloronicotinic acid hydrazide (0.1 mmol, 17.1 mg) were dissolved in a methanol solution (10 ml). The mixture was stirred at room temperature to give a clear yellow solution. Crystals of the title compound were formed by gradual evaporation of the solvent for 5 days at room temperature.

S3. Refinement

Atom H2 was located from a difference Fourier map and refined isotropically, with N–H distance restrained to 0.90 (1) Å. Other H atoms were constrained to ideal geometries, with C–H = 0.93 Å, and with U_iso(H) set to 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997a).

Figures

	Fig. 1. The structure of (I) at the 30% probability level.
	Fig. 2. Molecular packing of (I), viewed along the b axis. Intermolecular hydrogen bonds are shown as dashed lines.

6-Chloro-N'-(2,4-dichlorobenzylidene)nicotinohydrazide

Crystal data

C13H8Cl3N3O	Z = 2
Mr = 328.57	F(000) = 332
Triclinic, P1	Dx = 1.563 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.6670 (9) Å	Cell parameters from 872 reflections
b = 12.202 (2) Å	θ = 2.5–24.7°
c = 12.935 (3) Å	µ = 0.65 mm^−1
α = 106.70 (3)°	T = 298 K
β = 92.36 (3)°	Block, yellow
γ = 96.94 (3)°	0.27 × 0.23 × 0.22 mm
V = 698.1 (2) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	2827 independent reflections
Radiation source: fine-focus sealed tube	1141 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
ω scans	θmax = 26.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
Tmin = 0.843, Tmax = 0.870	k = −15→15
5653 measured reflections	l = −15→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.086	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.190	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0596P)^2] where P = (Fo^2 + 2Fc^2)/3
2827 reflections	(Δ/σ)max < 0.001
184 parameters	Δρmax = 0.29 e Å^−3
1 restraint	Δρmin = −0.34 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.3082 (4)	0.10650 (15)	0.49252 (14)	0.0547 (6)
Cl2	−0.3745 (5)	0.04955 (17)	0.13214 (15)	0.0752 (7)
Cl3	0.3929 (5)	0.79974 (18)	1.24132 (15)	0.0810 (8)
O1	−0.3459 (9)	0.5648 (4)	0.7653 (3)	0.0499 (13)
N1	−0.0622 (11)	0.4126 (4)	0.6298 (4)	0.0408 (14)
N2	0.0597 (10)	0.4785 (5)	0.7306 (4)	0.0396 (14)
N3	0.3450 (11)	0.6333 (5)	1.0617 (4)	0.0488 (15)
C1	−0.0062 (13)	0.2716 (5)	0.4667 (5)	0.0347 (15)
C2	0.0704 (12)	0.1627 (5)	0.4208 (5)	0.0378 (16)
C3	−0.0399 (15)	0.0942 (6)	0.3192 (5)	0.055 (2)
H3	0.0146	0.0214	0.2908	0.066*
C4	−0.2311 (15)	0.1346 (6)	0.2602 (5)	0.0475 (18)
C5	−0.3120 (14)	0.2426 (6)	0.3028 (5)	0.0504 (19)
H5	−0.4419	0.2696	0.2628	0.060*
C6	−0.2010 (13)	0.3109 (5)	0.4046 (5)	0.0452 (18)
H6	−0.2560	0.3837	0.4324	0.054*
C7	0.1035 (14)	0.3441 (6)	0.5761 (5)	0.0439 (18)
H7	0.2863	0.3405	0.6053	0.053*
C8	−0.1012 (14)	0.5535 (5)	0.7941 (5)	0.0390 (17)
C9	0.0401 (13)	0.6207 (6)	0.9038 (5)	0.0382 (16)
C10	−0.0519 (14)	0.7242 (6)	0.9563 (5)	0.0504 (19)
H10	−0.1877	0.7541	0.9215	0.061*
C11	0.0586 (15)	0.7831 (6)	1.0609 (5)	0.056 (2)
H11	0.0034	0.8537	1.0979	0.067*
C12	0.2527 (15)	0.7327 (6)	1.1074 (5)	0.0494 (19)
C13	0.2408 (13)	0.5797 (6)	0.9598 (5)	0.0445 (18)
H13	0.3066	0.5108	0.9243	0.053*
H2	0.251 (4)	0.493 (6)	0.750 (5)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0553 (12)	0.0540 (12)	0.0534 (12)	0.0200 (9)	−0.0092 (9)	0.0104 (9)
Cl2	0.1053 (17)	0.0664 (14)	0.0410 (12)	0.0000 (12)	−0.0214 (11)	0.0042 (10)
Cl3	0.1154 (18)	0.0737 (15)	0.0401 (12)	0.0009 (13)	−0.0198 (12)	0.0035 (11)
O1	0.029 (3)	0.067 (3)	0.051 (3)	0.014 (2)	−0.003 (2)	0.010 (3)
N1	0.037 (3)	0.040 (3)	0.038 (3)	−0.006 (3)	−0.010 (3)	0.006 (3)
N2	0.029 (3)	0.045 (3)	0.038 (3)	0.009 (3)	−0.008 (3)	0.002 (3)
N3	0.054 (4)	0.053 (4)	0.037 (4)	0.008 (3)	−0.002 (3)	0.011 (3)
C1	0.033 (4)	0.042 (4)	0.031 (4)	0.003 (3)	0.005 (3)	0.015 (3)
C2	0.032 (4)	0.039 (4)	0.040 (4)	0.007 (3)	−0.007 (3)	0.009 (3)
C3	0.069 (5)	0.049 (5)	0.045 (5)	0.008 (4)	0.001 (4)	0.011 (4)
C4	0.059 (5)	0.040 (4)	0.036 (4)	−0.007 (4)	−0.009 (4)	0.007 (3)
C5	0.057 (5)	0.049 (5)	0.048 (5)	0.004 (4)	−0.015 (4)	0.022 (4)
C6	0.052 (4)	0.032 (4)	0.047 (5)	0.003 (3)	−0.002 (4)	0.007 (3)
C7	0.033 (4)	0.044 (4)	0.051 (5)	0.006 (3)	−0.001 (3)	0.008 (4)
C8	0.031 (4)	0.033 (4)	0.052 (5)	0.006 (3)	0.013 (3)	0.009 (3)
C9	0.034 (4)	0.040 (4)	0.036 (4)	0.003 (3)	−0.002 (3)	0.005 (3)
C10	0.046 (4)	0.054 (5)	0.050 (5)	0.018 (4)	−0.010 (4)	0.010 (4)
C11	0.065 (5)	0.050 (5)	0.042 (5)	0.014 (4)	−0.005 (4)	−0.004 (4)
C12	0.067 (5)	0.042 (5)	0.036 (4)	0.001 (4)	0.000 (4)	0.008 (4)
C13	0.045 (4)	0.043 (4)	0.045 (5)	0.004 (4)	0.003 (3)	0.014 (4)

Geometric parameters (Å, º)

Cl1—C2	1.740 (6)	C3—H3	0.9300
Cl2—C4	1.739 (6)	C4—C5	1.380 (9)
Cl3—C12	1.750 (7)	C5—C6	1.380 (8)
O1—C8	1.223 (7)	C5—H5	0.9300
N1—C7	1.283 (7)	C6—H6	0.9300
N1—N2	1.377 (6)	C7—H7	0.9300
N2—C8	1.364 (7)	C8—C9	1.498 (8)
N2—H2	0.90 (3)	C9—C10	1.379 (8)
N3—C12	1.319 (8)	C9—C13	1.386 (8)
N3—C13	1.332 (7)	C10—C11	1.380 (8)
C1—C2	1.388 (8)	C10—H10	0.9300
C1—C6	1.403 (8)	C11—C12	1.365 (9)
C1—C7	1.469 (8)	C11—H11	0.9300
C2—C3	1.378 (8)	C13—H13	0.9300
C3—C4	1.373 (8)
C7—N1—N2	113.6 (5)	C1—C6—H6	119.6
C8—N2—N1	117.9 (5)	N1—C7—C1	117.5 (6)
C8—N2—H2	115 (5)	N1—C7—H7	121.2
N1—N2—H2	124 (4)	C1—C7—H7	121.2
C12—N3—C13	115.9 (6)	O1—C8—N2	123.0 (6)
C2—C1—C6	117.1 (6)	O1—C8—C9	121.6 (6)
C2—C1—C7	122.9 (6)	N2—C8—C9	115.4 (6)
C6—C1—C7	120.0 (6)	C10—C9—C13	117.7 (6)
C3—C2—C1	122.3 (6)	C10—C9—C8	118.7 (6)
C3—C2—Cl1	117.5 (5)	C13—C9—C8	123.4 (6)
C1—C2—Cl1	120.2 (5)	C9—C10—C11	119.7 (6)
C4—C3—C2	119.4 (7)	C9—C10—H10	120.2
C4—C3—H3	120.3	C11—C10—H10	120.2
C2—C3—H3	120.3	C12—C11—C10	116.8 (7)
C3—C4—C5	120.1 (6)	C12—C11—H11	121.6
C3—C4—Cl2	120.3 (6)	C10—C11—H11	121.6
C5—C4—Cl2	119.7 (6)	N3—C12—C11	126.1 (6)
C6—C5—C4	120.3 (6)	N3—C12—Cl3	114.4 (5)
C6—C5—H5	119.9	C11—C12—Cl3	119.5 (6)
C4—C5—H5	119.9	N3—C13—C9	123.8 (6)
C5—C6—C1	120.8 (6)	N3—C13—H13	118.1
C5—C6—H6	119.6	C9—C13—H13	118.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.90 (3)	1.95 (3)	2.816 (6)	160 (6)
C5—H5···O1^ii	0.93	2.46	3.291 (6)	148
C13—H13···N3^iii	0.93	2.57	3.379 (6)	145

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