Download citation
Download citation
link to html
The mol­ecule of the title compound, C13H9Cl2N3O, is roughly planar, the largest deviation from the mean plane being 0.168 (1) Å at the N atom next to the carbonyl group. Mol­ecules are linked by N—H...N hydrogen bonds to form a zigzag chain.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051847/dn2248sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051847/dn2248Isup2.hkl
Contains datablock I

CCDC reference: 667421

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C)= 0.002 Å
  • R factor = 0.038
  • wR factor = 0.109
  • Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

Comment top

The chemistry of Schiff bases has attracted much interest in recent years. These compounds play an important role in the development of various proteins and enzymes(Kahwa et al., 1986; Santos et al., 2001). As part of our interest in the study of the coordination chemistry of Schiff bases, we have synthesized the title compound (I) and its cyrstal structure is reported here.

The molecule of the title compound, C13H9Cl2N3O, is roughly planar with the largest deviation from the mean plane being 0.168 (1) Å at N2 (Fig. 1). The molecules are linked by N—H···N hydrogen bonds to form a zigzag like chain (Table 1, Fig.2).

Related literature top

For related literature, see: Kahwa et al. (1986); Santos et al. (2001).

Experimental top

Pyridine-4-carboxylic acid (1 mmol, 0.137 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, 3,4-dichlorobenzyaldehyde (1 mmol 0.175 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 dichloromethane, brown single crystals of (I) was obtained after 5 d.

Refinement top

All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) and N—H =0.86 Å with Uiso(H) = 1.2Ueq(C or N).

Structure description top

The chemistry of Schiff bases has attracted much interest in recent years. These compounds play an important role in the development of various proteins and enzymes(Kahwa et al., 1986; Santos et al., 2001). As part of our interest in the study of the coordination chemistry of Schiff bases, we have synthesized the title compound (I) and its cyrstal structure is reported here.

The molecule of the title compound, C13H9Cl2N3O, is roughly planar with the largest deviation from the mean plane being 0.168 (1) Å at N2 (Fig. 1). The molecules are linked by N—H···N hydrogen bonds to form a zigzag like chain (Table 1, Fig.2).

For related literature, see: Kahwa et al. (1986); Santos et al. (2001).

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) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Molecular view of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Partial packing view of compound (I), showing the formation of the zigzag like chain through N—H···N hydrogen bonds. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted. [symmetry codes: (i) -x + 1/2, y-/2, -z + 1/2].
N'-(3,4-Dichlorobenzylidene)isonicotinohydrazide top
Crystal data top
C13H9Cl2N3OF(000) = 600
Mr = 294.13Dx = 1.525 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1680 reflections
a = 8.2208 (5) Åθ = 2.5–24.1°
b = 10.9657 (6) ŵ = 0.50 mm1
c = 14.5206 (8) ÅT = 298 K
β = 101.881 (1)°Block, brown
V = 1280.94 (13) Å30.23 × 0.22 × 0.20 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2797 independent reflections
Radiation source: fine-focus sealed tube2424 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω scansθmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 1010
Tmin = 0.894, Tmax = 0.907k = 1414
15485 measured reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0562P)2 + 0.3525P]
where P = (Fo2 + 2Fc2)/3
2797 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
C13H9Cl2N3OV = 1280.94 (13) Å3
Mr = 294.13Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.2208 (5) ŵ = 0.50 mm1
b = 10.9657 (6) ÅT = 298 K
c = 14.5206 (8) Å0.23 × 0.22 × 0.20 mm
β = 101.881 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2797 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
2424 reflections with I > 2σ(I)
Tmin = 0.894, Tmax = 0.907Rint = 0.019
15485 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 1.07Δρmax = 0.28 e Å3
2797 reflectionsΔρmin = 0.51 e Å3
172 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
xyzUiso*/Ueq
Cl11.09201 (8)0.13294 (5)0.74298 (4)0.0799 (2)
Cl21.19312 (6)0.38051 (5)0.65624 (4)0.06668 (18)
O10.57542 (18)0.27617 (12)0.51487 (8)0.0608 (4)
N10.66161 (15)0.05618 (12)0.46137 (9)0.0414 (3)
N20.54386 (16)0.12734 (11)0.40476 (9)0.0417 (3)
H20.49280.10200.35040.050*
N30.17567 (17)0.47619 (12)0.25252 (10)0.0467 (3)
C10.82342 (18)0.12390 (14)0.48204 (11)0.0395 (3)
C20.89503 (19)0.09540 (14)0.57476 (11)0.0423 (3)
H2A0.86560.02350.60120.051*
C31.00936 (19)0.17281 (15)0.62796 (11)0.0441 (4)
C41.05440 (19)0.27991 (15)0.58971 (12)0.0459 (4)
C50.9860 (2)0.30805 (17)0.49746 (14)0.0560 (4)
H51.01680.37950.47110.067*
C60.8716 (2)0.23040 (17)0.44379 (12)0.0523 (4)
H60.82660.24990.38140.063*
C70.69846 (19)0.04360 (15)0.42635 (11)0.0425 (3)
H70.64630.06560.36560.051*
C80.51087 (19)0.23852 (14)0.43734 (10)0.0416 (3)
C90.39034 (18)0.31667 (13)0.37003 (10)0.0376 (3)
C100.3369 (2)0.42349 (15)0.40426 (11)0.0450 (4)
H100.37030.44350.46760.054*
C110.2336 (2)0.50024 (17)0.34363 (12)0.0510 (4)
H110.20230.57330.36750.061*
C120.2266 (2)0.37254 (15)0.22029 (12)0.0509 (4)
H120.18790.35310.15720.061*
C130.3341 (2)0.29202 (14)0.27565 (11)0.0492 (4)
H130.36830.22160.24940.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0908 (4)0.0782 (4)0.0522 (3)0.0102 (3)0.0283 (3)0.0046 (2)
Cl20.0527 (3)0.0613 (3)0.0828 (4)0.0169 (2)0.0066 (2)0.0262 (2)
O10.0778 (9)0.0515 (7)0.0407 (6)0.0096 (6)0.0166 (6)0.0042 (5)
N10.0412 (7)0.0397 (7)0.0383 (6)0.0008 (5)0.0032 (5)0.0074 (5)
N20.0449 (7)0.0380 (7)0.0361 (6)0.0016 (5)0.0057 (5)0.0045 (5)
N30.0492 (7)0.0420 (7)0.0440 (7)0.0017 (6)0.0019 (6)0.0076 (6)
C10.0390 (7)0.0387 (8)0.0389 (8)0.0011 (6)0.0033 (6)0.0029 (6)
C20.0432 (8)0.0379 (7)0.0421 (8)0.0017 (6)0.0006 (6)0.0008 (6)
C30.0399 (8)0.0459 (8)0.0421 (8)0.0032 (6)0.0020 (6)0.0046 (7)
C40.0374 (7)0.0431 (8)0.0560 (9)0.0040 (6)0.0070 (7)0.0126 (7)
C50.0624 (10)0.0453 (9)0.0606 (10)0.0129 (8)0.0131 (8)0.0026 (8)
C60.0600 (10)0.0510 (10)0.0425 (9)0.0050 (8)0.0027 (7)0.0058 (7)
C70.0425 (8)0.0448 (8)0.0363 (7)0.0008 (6)0.0011 (6)0.0026 (6)
C80.0453 (8)0.0396 (8)0.0354 (7)0.0016 (6)0.0019 (6)0.0044 (6)
C90.0400 (7)0.0336 (7)0.0358 (7)0.0047 (6)0.0002 (6)0.0053 (6)
C100.0523 (9)0.0458 (8)0.0341 (7)0.0045 (7)0.0023 (6)0.0002 (6)
C110.0583 (10)0.0476 (9)0.0455 (9)0.0117 (8)0.0073 (7)0.0012 (7)
C120.0669 (11)0.0391 (8)0.0375 (8)0.0056 (7)0.0105 (7)0.0022 (6)
C130.0683 (11)0.0325 (7)0.0394 (8)0.0023 (7)0.0061 (7)0.0013 (6)
Geometric parameters (Å, º) top
Cl1—C31.7249 (16)C4—C51.377 (3)
Cl2—C41.7312 (16)C5—C61.384 (3)
O1—C81.2138 (19)C5—H50.9300
N1—C71.269 (2)C6—H60.9300
N1—N21.3762 (17)C7—H70.9300
N2—C81.355 (2)C8—C91.508 (2)
N2—H20.8600C9—C101.379 (2)
N3—C121.329 (2)C9—C131.380 (2)
N3—C111.337 (2)C10—C111.377 (2)
C1—C61.386 (2)C10—H100.9300
C1—C21.389 (2)C11—H110.9300
C1—C71.464 (2)C12—C131.384 (2)
C2—C31.379 (2)C12—H120.9300
C2—H2A0.9300C13—H130.9300
C3—C41.382 (2)
C7—N1—N2116.49 (13)C1—C6—H6119.7
C8—N2—N1117.92 (12)N1—C7—C1119.70 (14)
C8—N2—H2121.0N1—C7—H7120.1
N1—N2—H2121.0C1—C7—H7120.1
C12—N3—C11116.30 (14)O1—C8—N2123.30 (14)
C6—C1—C2118.62 (14)O1—C8—C9120.76 (14)
C6—C1—C7120.77 (14)N2—C8—C9115.92 (13)
C2—C1—C7120.61 (14)C10—C9—C13117.25 (14)
C3—C2—C1120.55 (15)C10—C9—C8117.69 (13)
C3—C2—H2A119.7C13—C9—C8125.01 (14)
C1—C2—H2A119.7C11—C10—C9119.26 (15)
C2—C3—C4120.41 (15)C11—C10—H10120.4
C2—C3—Cl1118.27 (13)C9—C10—H10120.4
C4—C3—Cl1121.32 (12)N3—C11—C10124.01 (16)
C5—C4—C3119.46 (15)N3—C11—H11118.0
C5—C4—Cl2119.37 (13)C10—C11—H11118.0
C3—C4—Cl2121.16 (13)N3—C12—C13123.43 (15)
C4—C5—C6120.28 (16)N3—C12—H12118.3
C4—C5—H5119.9C13—C12—H12118.3
C6—C5—H5119.9C9—C13—C12119.69 (15)
C5—C6—C1120.66 (16)C9—C13—H13120.2
C5—C6—H6119.7C12—C13—H13120.2
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N3i0.862.283.0859 (18)156
Symmetry code: (i) x+1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC13H9Cl2N3O
Mr294.13
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)8.2208 (5), 10.9657 (6), 14.5206 (8)
β (°) 101.881 (1)
V3)1280.94 (13)
Z4
Radiation typeMo Kα
µ (mm1)0.50
Crystal size (mm)0.23 × 0.22 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.894, 0.907
No. of measured, independent and
observed [I > 2σ(I)] reflections
15485, 2797, 2424
Rint0.019
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.109, 1.07
No. of reflections2797
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.51

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N3i0.862.283.0859 (18)155.8
Symmetry code: (i) x+1/2, y1/2, z+1/2.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds