Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051847/dn2248sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051847/dn2248Isup2.hkl |
CCDC reference: 667421
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (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
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.
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).
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).
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).
C13H9Cl2N3O | F(000) = 600 |
Mr = 294.13 | Dx = 1.525 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1680 reflections |
a = 8.2208 (5) Å | θ = 2.5–24.1° |
b = 10.9657 (6) Å | µ = 0.50 mm−1 |
c = 14.5206 (8) Å | T = 298 K |
β = 101.881 (1)° | Block, brown |
V = 1280.94 (13) Å3 | 0.23 × 0.22 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2797 independent reflections |
Radiation source: fine-focus sealed tube | 2424 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ω scans | θmax = 27.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −10→10 |
Tmin = 0.894, Tmax = 0.907 | k = −14→14 |
15485 measured reflections | l = −18→18 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H-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 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
C13H9Cl2N3O | V = 1280.94 (13) Å3 |
Mr = 294.13 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.2208 (5) Å | µ = 0.50 mm−1 |
b = 10.9657 (6) Å | T = 298 K |
c = 14.5206 (8) Å | 0.23 × 0.22 × 0.20 mm |
β = 101.881 (1)° |
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 = 0.907 | Rint = 0.019 |
15485 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.28 e Å−3 |
2797 reflections | Δρmin = −0.51 e Å−3 |
172 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 1.09201 (8) | −0.13294 (5) | 0.74298 (4) | 0.0799 (2) | |
Cl2 | 1.19312 (6) | −0.38051 (5) | 0.65624 (4) | 0.06668 (18) | |
O1 | 0.57542 (18) | 0.27617 (12) | 0.51487 (8) | 0.0608 (4) | |
N1 | 0.66161 (15) | 0.05618 (12) | 0.46137 (9) | 0.0414 (3) | |
N2 | 0.54386 (16) | 0.12734 (11) | 0.40476 (9) | 0.0417 (3) | |
H2 | 0.4928 | 0.1020 | 0.3504 | 0.050* | |
N3 | 0.17567 (17) | 0.47619 (12) | 0.25252 (10) | 0.0467 (3) | |
C1 | 0.82342 (18) | −0.12390 (14) | 0.48204 (11) | 0.0395 (3) | |
C2 | 0.89503 (19) | −0.09540 (14) | 0.57476 (11) | 0.0423 (3) | |
H2A | 0.8656 | −0.0235 | 0.6012 | 0.051* | |
C3 | 1.00936 (19) | −0.17281 (15) | 0.62796 (11) | 0.0441 (4) | |
C4 | 1.05440 (19) | −0.27991 (15) | 0.58971 (12) | 0.0459 (4) | |
C5 | 0.9860 (2) | −0.30805 (17) | 0.49746 (14) | 0.0560 (4) | |
H5 | 1.0168 | −0.3795 | 0.4711 | 0.067* | |
C6 | 0.8716 (2) | −0.23040 (17) | 0.44379 (12) | 0.0523 (4) | |
H6 | 0.8266 | −0.2499 | 0.3814 | 0.063* | |
C7 | 0.69846 (19) | −0.04360 (15) | 0.42635 (11) | 0.0425 (3) | |
H7 | 0.6463 | −0.0656 | 0.3656 | 0.051* | |
C8 | 0.51087 (19) | 0.23852 (14) | 0.43734 (10) | 0.0416 (3) | |
C9 | 0.39034 (18) | 0.31667 (13) | 0.37003 (10) | 0.0376 (3) | |
C10 | 0.3369 (2) | 0.42349 (15) | 0.40426 (11) | 0.0450 (4) | |
H10 | 0.3703 | 0.4435 | 0.4676 | 0.054* | |
C11 | 0.2336 (2) | 0.50024 (17) | 0.34363 (12) | 0.0510 (4) | |
H11 | 0.2023 | 0.5733 | 0.3675 | 0.061* | |
C12 | 0.2266 (2) | 0.37254 (15) | 0.22029 (12) | 0.0509 (4) | |
H12 | 0.1879 | 0.3531 | 0.1572 | 0.061* | |
C13 | 0.3341 (2) | 0.29202 (14) | 0.27565 (11) | 0.0492 (4) | |
H13 | 0.3683 | 0.2216 | 0.2494 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0908 (4) | 0.0782 (4) | 0.0522 (3) | 0.0102 (3) | −0.0283 (3) | −0.0046 (2) |
Cl2 | 0.0527 (3) | 0.0613 (3) | 0.0828 (4) | 0.0169 (2) | 0.0066 (2) | 0.0262 (2) |
O1 | 0.0778 (9) | 0.0515 (7) | 0.0407 (6) | 0.0096 (6) | −0.0166 (6) | −0.0042 (5) |
N1 | 0.0412 (7) | 0.0397 (7) | 0.0383 (6) | 0.0008 (5) | −0.0032 (5) | 0.0074 (5) |
N2 | 0.0449 (7) | 0.0380 (7) | 0.0361 (6) | 0.0016 (5) | −0.0057 (5) | 0.0045 (5) |
N3 | 0.0492 (7) | 0.0420 (7) | 0.0440 (7) | 0.0017 (6) | −0.0019 (6) | 0.0076 (6) |
C1 | 0.0390 (7) | 0.0387 (8) | 0.0389 (8) | −0.0011 (6) | 0.0033 (6) | 0.0029 (6) |
C2 | 0.0432 (8) | 0.0379 (7) | 0.0421 (8) | 0.0017 (6) | 0.0006 (6) | −0.0008 (6) |
C3 | 0.0399 (8) | 0.0459 (8) | 0.0421 (8) | −0.0032 (6) | −0.0020 (6) | 0.0046 (7) |
C4 | 0.0374 (7) | 0.0431 (8) | 0.0560 (9) | 0.0040 (6) | 0.0070 (7) | 0.0126 (7) |
C5 | 0.0624 (10) | 0.0453 (9) | 0.0606 (10) | 0.0129 (8) | 0.0131 (8) | −0.0026 (8) |
C6 | 0.0600 (10) | 0.0510 (10) | 0.0425 (9) | 0.0050 (8) | 0.0027 (7) | −0.0058 (7) |
C7 | 0.0425 (8) | 0.0448 (8) | 0.0363 (7) | −0.0008 (6) | −0.0011 (6) | 0.0026 (6) |
C8 | 0.0453 (8) | 0.0396 (8) | 0.0354 (7) | −0.0016 (6) | −0.0019 (6) | 0.0044 (6) |
C9 | 0.0400 (7) | 0.0336 (7) | 0.0358 (7) | −0.0047 (6) | −0.0002 (6) | 0.0053 (6) |
C10 | 0.0523 (9) | 0.0458 (8) | 0.0341 (7) | 0.0045 (7) | 0.0023 (6) | 0.0002 (6) |
C11 | 0.0583 (10) | 0.0476 (9) | 0.0455 (9) | 0.0117 (8) | 0.0073 (7) | 0.0012 (7) |
C12 | 0.0669 (11) | 0.0391 (8) | 0.0375 (8) | −0.0056 (7) | −0.0105 (7) | 0.0022 (6) |
C13 | 0.0683 (11) | 0.0325 (7) | 0.0394 (8) | 0.0023 (7) | −0.0061 (7) | −0.0013 (6) |
Cl1—C3 | 1.7249 (16) | C4—C5 | 1.377 (3) |
Cl2—C4 | 1.7312 (16) | C5—C6 | 1.384 (3) |
O1—C8 | 1.2138 (19) | C5—H5 | 0.9300 |
N1—C7 | 1.269 (2) | C6—H6 | 0.9300 |
N1—N2 | 1.3762 (17) | C7—H7 | 0.9300 |
N2—C8 | 1.355 (2) | C8—C9 | 1.508 (2) |
N2—H2 | 0.8600 | C9—C10 | 1.379 (2) |
N3—C12 | 1.329 (2) | C9—C13 | 1.380 (2) |
N3—C11 | 1.337 (2) | C10—C11 | 1.377 (2) |
C1—C6 | 1.386 (2) | C10—H10 | 0.9300 |
C1—C2 | 1.389 (2) | C11—H11 | 0.9300 |
C1—C7 | 1.464 (2) | C12—C13 | 1.384 (2) |
C2—C3 | 1.379 (2) | C12—H12 | 0.9300 |
C2—H2A | 0.9300 | C13—H13 | 0.9300 |
C3—C4 | 1.382 (2) | ||
C7—N1—N2 | 116.49 (13) | C1—C6—H6 | 119.7 |
C8—N2—N1 | 117.92 (12) | N1—C7—C1 | 119.70 (14) |
C8—N2—H2 | 121.0 | N1—C7—H7 | 120.1 |
N1—N2—H2 | 121.0 | C1—C7—H7 | 120.1 |
C12—N3—C11 | 116.30 (14) | O1—C8—N2 | 123.30 (14) |
C6—C1—C2 | 118.62 (14) | O1—C8—C9 | 120.76 (14) |
C6—C1—C7 | 120.77 (14) | N2—C8—C9 | 115.92 (13) |
C2—C1—C7 | 120.61 (14) | C10—C9—C13 | 117.25 (14) |
C3—C2—C1 | 120.55 (15) | C10—C9—C8 | 117.69 (13) |
C3—C2—H2A | 119.7 | C13—C9—C8 | 125.01 (14) |
C1—C2—H2A | 119.7 | C11—C10—C9 | 119.26 (15) |
C2—C3—C4 | 120.41 (15) | C11—C10—H10 | 120.4 |
C2—C3—Cl1 | 118.27 (13) | C9—C10—H10 | 120.4 |
C4—C3—Cl1 | 121.32 (12) | N3—C11—C10 | 124.01 (16) |
C5—C4—C3 | 119.46 (15) | N3—C11—H11 | 118.0 |
C5—C4—Cl2 | 119.37 (13) | C10—C11—H11 | 118.0 |
C3—C4—Cl2 | 121.16 (13) | N3—C12—C13 | 123.43 (15) |
C4—C5—C6 | 120.28 (16) | N3—C12—H12 | 118.3 |
C4—C5—H5 | 119.9 | C13—C12—H12 | 118.3 |
C6—C5—H5 | 119.9 | C9—C13—C12 | 119.69 (15) |
C5—C6—C1 | 120.66 (16) | C9—C13—H13 | 120.2 |
C5—C6—H6 | 119.7 | C12—C13—H13 | 120.2 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N3i | 0.86 | 2.28 | 3.0859 (18) | 156 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C13H9Cl2N3O |
Mr | 294.13 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 8.2208 (5), 10.9657 (6), 14.5206 (8) |
β (°) | 101.881 (1) |
V (Å3) | 1280.94 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.50 |
Crystal size (mm) | 0.23 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.894, 0.907 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15485, 2797, 2424 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.109, 1.07 |
No. of reflections | 2797 |
No. of parameters | 172 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N3i | 0.86 | 2.28 | 3.0859 (18) | 155.8 |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
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).