supplementary materials
(E)-N'-(3,4-Dichlorobenzylidene)nicotinohydrazide monohydrate
Nicotinohydrazide (1 mmol, 0.137 g) was dissolved in ethanol (15 ml). The
solution was stirred for several minitutes at 351 K, then the
3,4-dichlorobenzaldehyde (1 mmol, 0.175 g) in ethanol (8 ml) was added
dropwise, and the mixture was stirred at refluxing temperature for 2 h. The
solid product was isolated and recrystallized from methanol-water solution.
Colourless single crystals were obtained after 3 d.
H atoms of water molecule are located in a difference Fourier map and refined
isotropically, with O—H and H···H distances restrained to 0.85 (2) and
1.37 (2) Å. Other H atoms were positioned geometrically and refined as riding
with C—H = 0.93 (aromatic) and N—H = 0.86 Å, Uiso(H) =
1.2Ueq(C,N).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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).
(
E)-
N'-(3,4-Dichlorobenzylidene)nicotinohydrazide monohydrate
top
Crystal data top
| C13H9Cl2N3O·H2O | F(000) = 640 |
| Mr = 312.15 | Dx = 1.495 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 3887 reflections |
| a = 8.2080 (3) Å | θ = 2.5–27.0° |
| b = 12.3294 (4) Å | µ = 0.47 mm−1 |
| c = 13.7089 (4) Å | T = 296 K |
| β = 91.522 (2)° | Block, colourless |
| V = 1386.85 (8) Å3 | 0.40 × 0.20 × 0.10 mm |
| Z = 4 | |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 3032 independent reflections |
| Radiation source: fine-focus sealed tube | 2150 reflections with I > 2σ(I) |
| graphite | Rint = 0.042 |
| ω scans | θmax = 27.0°, θmin = 2.2° |
Absorption correction: multi-scan
(SADABS; Bruker, 1998) | h = −10→10 |
| Tmin = 0.893, Tmax = 0.954 | k = −15→15 |
| 20965 measured reflections | l = −17→17 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.0432P)2 + 0.3048P]
where P = (Fo2 + 2Fc2)/3 |
| 3032 reflections | (Δ/σ)max = 0.022 |
| 189 parameters | Δρmax = 0.15 e Å−3 |
| 3 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
| C13H9Cl2N3O·H2O | V = 1386.85 (8) Å3 |
| Mr = 312.15 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.2080 (3) Å | µ = 0.47 mm−1 |
| b = 12.3294 (4) Å | T = 296 K |
| c = 13.7089 (4) Å | 0.40 × 0.20 × 0.10 mm |
| β = 91.522 (2)° | |
Data collection top
Bruker SMART CCD area-detector
diffractometer | 3032 independent reflections |
Absorption correction: multi-scan
(SADABS; Bruker, 1998) | 2150 reflections with I > 2σ(I) |
| Tmin = 0.893, Tmax = 0.954 | Rint = 0.042 |
| 20965 measured reflections | θmax = 27.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.100 | Δρmax = 0.15 e Å−3 |
| S = 1.02 | Δρmin = −0.20 e Å−3 |
| 3032 reflections | Absolute structure: ? |
| 189 parameters | Flack parameter: ? |
| 3 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| Cl1 | −0.01836 (7) | 0.35397 (5) | 0.67808 (4) | 0.07194 (19) | |
| Cl2 | 0.02126 (7) | 0.10476 (5) | 0.62576 (4) | 0.0725 (2) | |
| N2 | 0.46330 (18) | 0.25736 (12) | 0.18259 (10) | 0.0462 (4) | |
| H2A | 0.4694 | 0.1892 | 0.1698 | 0.055* | |
| N1 | 0.38507 (18) | 0.29373 (12) | 0.26366 (10) | 0.0471 (4) | |
| O | 0.52773 (19) | 0.42935 (10) | 0.14108 (9) | 0.0657 (4) | |
| C6 | 0.2369 (2) | 0.25413 (14) | 0.40566 (13) | 0.0448 (4) | |
| C8 | 0.5303 (2) | 0.33162 (14) | 0.12366 (12) | 0.0457 (4) | |
| C4 | 0.0960 (2) | 0.20492 (15) | 0.55082 (13) | 0.0482 (4) | |
| C3 | 0.0803 (2) | 0.31321 (16) | 0.57470 (13) | 0.0487 (4) | |
| C10 | 0.6343 (2) | 0.18316 (14) | 0.01178 (13) | 0.0501 (4) | |
| H10A | 0.5992 | 0.1314 | 0.0559 | 0.060* | |
| C2 | 0.1439 (2) | 0.39176 (15) | 0.51490 (14) | 0.0527 (5) | |
| H2 | 0.1344 | 0.4646 | 0.5315 | 0.063* | |
| C9 | 0.6100 (2) | 0.29128 (13) | 0.03370 (12) | 0.0420 (4) | |
| C13 | 0.6619 (2) | 0.36685 (15) | −0.03277 (13) | 0.0519 (5) | |
| H13A | 0.6463 | 0.4404 | −0.0214 | 0.062* | |
| C5 | 0.1740 (2) | 0.17586 (15) | 0.46627 (13) | 0.0483 (4) | |
| H5A | 0.1841 | 0.1029 | 0.4501 | 0.058* | |
| C7 | 0.3221 (2) | 0.22160 (15) | 0.31757 (13) | 0.0480 (4) | |
| H7A | 0.3301 | 0.1487 | 0.3011 | 0.058* | |
| C1 | 0.2212 (2) | 0.36294 (14) | 0.43093 (14) | 0.0508 (5) | |
| H1 | 0.2632 | 0.4164 | 0.3909 | 0.061* | |
| O1 | 0.5421 (2) | 0.52708 (11) | 0.32595 (11) | 0.0651 (4) | |
| N3 | 0.7054 (2) | 0.14870 (12) | −0.06903 (11) | 0.0564 (4) | |
| C11 | 0.7563 (2) | 0.22393 (16) | −0.13096 (14) | 0.0558 (5) | |
| H11A | 0.8077 | 0.2014 | −0.1871 | 0.067* | |
| C12 | 0.7366 (3) | 0.33289 (16) | −0.11592 (14) | 0.0575 (5) | |
| H12A | 0.7731 | 0.3830 | −0.1611 | 0.069* | |
| H1B | 0.599 (3) | 0.4849 (16) | 0.3622 (14) | 0.092 (9)* | |
| H1A | 0.515 (3) | 0.4919 (18) | 0.2749 (11) | 0.102 (10)* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cl1 | 0.0761 (4) | 0.0845 (4) | 0.0562 (3) | 0.0074 (3) | 0.0190 (3) | −0.0066 (3) |
| Cl2 | 0.0856 (4) | 0.0646 (3) | 0.0679 (3) | −0.0098 (3) | 0.0148 (3) | 0.0166 (3) |
| N2 | 0.0585 (9) | 0.0371 (7) | 0.0434 (8) | 0.0010 (7) | 0.0081 (7) | −0.0042 (6) |
| N1 | 0.0519 (9) | 0.0439 (8) | 0.0458 (8) | 0.0025 (7) | 0.0058 (6) | −0.0041 (7) |
| O | 0.1088 (12) | 0.0353 (7) | 0.0541 (8) | 0.0024 (7) | 0.0196 (7) | −0.0034 (6) |
| C6 | 0.0423 (10) | 0.0429 (9) | 0.0492 (9) | −0.0002 (8) | 0.0026 (7) | −0.0017 (8) |
| C8 | 0.0558 (11) | 0.0386 (9) | 0.0427 (9) | 0.0027 (8) | 0.0004 (8) | −0.0014 (7) |
| C4 | 0.0463 (11) | 0.0494 (10) | 0.0490 (10) | −0.0031 (8) | 0.0013 (8) | 0.0069 (8) |
| C3 | 0.0436 (10) | 0.0562 (11) | 0.0466 (10) | 0.0029 (9) | 0.0052 (8) | −0.0032 (8) |
| C10 | 0.0666 (12) | 0.0379 (9) | 0.0461 (10) | 0.0021 (9) | 0.0079 (8) | 0.0030 (8) |
| C2 | 0.0546 (12) | 0.0435 (10) | 0.0603 (11) | 0.0024 (9) | 0.0084 (9) | −0.0050 (9) |
| C9 | 0.0466 (10) | 0.0379 (9) | 0.0414 (9) | −0.0006 (8) | −0.0016 (7) | −0.0014 (7) |
| C13 | 0.0654 (12) | 0.0379 (9) | 0.0527 (10) | −0.0046 (8) | 0.0061 (9) | −0.0011 (8) |
| C5 | 0.0502 (11) | 0.0411 (9) | 0.0535 (10) | −0.0017 (8) | 0.0018 (8) | −0.0016 (8) |
| C7 | 0.0508 (11) | 0.0424 (10) | 0.0509 (10) | −0.0001 (8) | 0.0040 (8) | −0.0050 (8) |
| C1 | 0.0528 (11) | 0.0413 (10) | 0.0590 (11) | −0.0007 (8) | 0.0119 (9) | 0.0013 (8) |
| O1 | 0.1057 (13) | 0.0364 (7) | 0.0533 (8) | 0.0038 (8) | 0.0052 (8) | −0.0022 (7) |
| N3 | 0.0752 (11) | 0.0435 (9) | 0.0512 (9) | 0.0039 (8) | 0.0131 (8) | −0.0031 (7) |
| C11 | 0.0632 (13) | 0.0558 (12) | 0.0490 (10) | −0.0018 (10) | 0.0123 (9) | −0.0050 (9) |
| C12 | 0.0703 (13) | 0.0488 (11) | 0.0541 (11) | −0.0098 (10) | 0.0163 (10) | 0.0021 (9) |
Geometric parameters (Å, °) top
| Cl1—C3 | 1.7255 (18) | C10—H10A | 0.9300 |
| Cl2—C4 | 1.7291 (18) | C2—C1 | 1.376 (2) |
| N2—C8 | 1.348 (2) | C2—H2 | 0.9300 |
| N2—N1 | 1.3736 (19) | C9—C13 | 1.378 (2) |
| N2—H2A | 0.8600 | C13—C12 | 1.374 (3) |
| N1—C7 | 1.275 (2) | C13—H13A | 0.9300 |
| O—C8 | 1.229 (2) | C5—H5A | 0.9300 |
| C6—C5 | 1.383 (2) | C7—H7A | 0.9300 |
| C6—C1 | 1.392 (2) | C1—H1 | 0.9300 |
| C6—C7 | 1.467 (2) | O1—H1B | 0.85 (2) |
| C8—C9 | 1.497 (2) | O1—H1A | 0.85 (2) |
| C4—C3 | 1.381 (3) | N3—C11 | 1.332 (2) |
| C4—C5 | 1.386 (2) | C11—C12 | 1.369 (3) |
| C3—C2 | 1.380 (3) | C11—H11A | 0.9300 |
| C10—N3 | 1.335 (2) | C12—H12A | 0.9300 |
| C10—C9 | 1.382 (2) | | |
| | | |
| C8—N2—N1 | 118.04 (14) | C13—C9—C8 | 118.00 (15) |
| C8—N2—H2A | 121.0 | C10—C9—C8 | 124.65 (15) |
| N1—N2—H2A | 121.0 | C12—C13—C9 | 119.66 (17) |
| C7—N1—N2 | 116.54 (15) | C12—C13—H13A | 120.2 |
| C5—C6—C1 | 118.97 (17) | C9—C13—H13A | 120.2 |
| C5—C6—C7 | 119.85 (16) | C6—C5—C4 | 120.70 (17) |
| C1—C6—C7 | 121.15 (16) | C6—C5—H5A | 119.7 |
| O—C8—N2 | 122.71 (16) | C4—C5—H5A | 119.7 |
| O—C8—C9 | 119.75 (16) | N1—C7—C6 | 119.73 (16) |
| N2—C8—C9 | 117.54 (15) | N1—C7—H7A | 120.1 |
| C3—C4—C5 | 119.74 (16) | C6—C7—H7A | 120.1 |
| C3—C4—Cl2 | 120.84 (14) | C2—C1—C6 | 120.31 (17) |
| C5—C4—Cl2 | 119.42 (14) | C2—C1—H1 | 119.8 |
| C4—C3—C2 | 119.88 (16) | C6—C1—H1 | 119.8 |
| C4—C3—Cl1 | 121.65 (14) | H1B—O1—H1A | 107.2 (18) |
| C2—C3—Cl1 | 118.47 (15) | C11—N3—C10 | 117.30 (16) |
| N3—C10—C9 | 123.78 (17) | N3—C11—C12 | 123.14 (17) |
| N3—C10—H10A | 118.1 | N3—C11—H11A | 118.4 |
| C9—C10—H10A | 118.1 | C12—C11—H11A | 118.4 |
| C1—C2—C3 | 120.39 (17) | C11—C12—C13 | 118.75 (18) |
| C1—C2—H2 | 119.8 | C11—C12—H12A | 120.6 |
| C3—C2—H2 | 119.8 | C13—C12—H12A | 120.6 |
| C13—C9—C10 | 117.35 (16) | | |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···O | 0.85 (2) | 2.00 (2) | 2.8059 (19) | 160 (2) |
| O1—H1B···N3i | 0.85 (2) | 2.08 (1) | 2.909 (2) | 166 (2) |
| N2—H2A···O1ii | 0.86 | 2.00 | 2.842 (2) | 165 |
| C7—H7A···O1ii | 0.93 | 2.55 | 3.314 (2) | 140 |
| C10—H10A···O1ii | 0.93 | 2.39 | 3.304 (2) | 167 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1A···O | 0.85 (2) | 2.00 (2) | 2.8059 (19) | 160 (2) |
| O1—H1B···N3i | 0.85 (2) | 2.08 (1) | 2.909 (2) | 166 (2) |
| N2—H2A···O1ii | 0.86 | 2.00 | 2.842 (2) | 165 |
| C7—H7A···O1ii | 0.93 | 2.55 | 3.314 (2) | 140 |
| C10—H10A···O1ii | 0.93 | 2.39 | 3.304 (2) | 167 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Kahwa, I. A., Selbin, I., Hsieh, T. C. Y. & Laine, R. A. (1986). Inorg. Chim. Acta, 118, 179–185.
Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J. Chem. Soc. Dalton Trans. pp. 838–844.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
O, O-H![[Figure 1]](./xu2600fig1thm.gif)
![[Figure 2]](./xu2600fig2thm.gif)
The chemistry of Schiff bases has attracted a great deal of 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 coordination chemistry of Schiff bases, we have synthesized the title compound and report here its crystal structure.
The title molecule crystallizes in the E conformation (Fig. 1), with the N2—N1—C7—C6 torsion angle of 179.81 (15)°. The molecule structure is nearly planar, the dihedral angle between the 3,4-dichlorobenzene ring and the pyridine ring is 4.78 (8)°. The extensive intermolecular classic O—H···O, O—H···N, N—H···O and weak C—H···O hydrogen bonding is present in the crystal structure (Table 1 and Fig. 2).