(E)-N′-(3,4-Dichloro­benzyl­idene)nicotino­hydrazide monohydrate

Bao, F.-Y.; Zhou, Y.-X.; Zhang, H.-Y.; Hui, S.

doi:10.1107/S1600536809034552

organic compounds

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Volume 65| Part 10| October 2009| Page o2336

doi:10.1107/S1600536809034552

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(E)-N′-(3,4-Dichlorobenzylidene)nicotinohydrazide monohydrate

Feng-Yu Bao,^a ^* Ying-Xia Zhou,^a Hai-Yan Zhang ^a and Su Hui ^a

^aDepartment of Applied Chemistry, College of Sciences, Henan Agricultural University, Zhengzhou 450002, People's Republic of China
^*Correspondence e-mail: bfyu2008@126.com

(Received 21 August 2009; accepted 28 August 2009; online 5 September 2009)

In the title compound, C₁₃H₉Cl₂N₃O·H₂O, the 3,4-dichlorobenzene ring is nearly coplanar with the pyridine ring, making a dihedral angle of 4.78 (8)°. Intermolecular O—H⋯O, O—H⋯N, N—H⋯O and weak C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For applications of Schiff base compounds, see: Kahwa et al. (1986 ); Santos et al. (2001 ).

Experimental

Crystal data

C₁₃H₉Cl₂N₃O·H₂O
M_r = 312.15
Monoclinic, P 2₁ /c
a = 8.2080 (3) Å
b = 12.3294 (4) Å
c = 13.7089 (4) Å
β = 91.522 (2)°
V = 1386.85 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 296 K
0.40 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.893, T_max = 0.954
20965 measured reflections
3032 independent reflections
2150 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.100
S = 1.02
3032 reflections
189 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O	0.85 (2)	1.995 (16)	2.8059 (19)	160 (2)
O1—H1B⋯N3ⁱ	0.85 (2)	2.079 (12)	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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); 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: 10.1107/S1600536809034552/xu2600sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034552/xu2600Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

For applications of Schiff base compounds, see: Kahwa et al. (1986); Santos et al. (2001).

Experimental top

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.

Computing details top

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).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The unit cell packing diagram showing the intermolecular hydrogen bonding as dashed lines.

(E)-N'-(3,4-Dichlorobenzylidene)nicotinohydrazide monohydrate top

Crystal data top

C₁₃H₉Cl₂N₃O·H₂O	F(000) = 640
M_r = 312.15	D_x = 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 monochromator	R_int = 0.042
ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→10
T_min = 0.893, T_max = 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(F_o²) + (0.0432P)² + 0.3048P] where P = (F_o² + 2F_c²)/3
3032 reflections	(Δ/σ)_max = 0.022
189 parameters	Δρ_max = 0.15 e Å⁻³
3 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₃H₉Cl₂N₃O·H₂O	V = 1386.85 (8) Å³
M_r = 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)
T_min = 0.893, T_max = 0.954	R_int = 0.042
20965 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	3 restraints
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.15 e Å⁻³
3032 reflections	Δρ_min = −0.20 e Å⁻³
189 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

	x	y	z	U_iso*/U_eq
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, º) 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, º) 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.

Experimental details

Crystal data
Chemical formula	C₁₃H₉Cl₂N₃O·H₂O
M_r	312.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.2080 (3), 12.3294 (4), 13.7089 (4)
β (°)	91.522 (2)
V (Å³)	1386.85 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.47
Crystal size (mm)	0.40 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.893, 0.954
No. of measured, independent and observed [I > 2σ(I)] reflections	20965, 3032, 2150
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.100, 1.02
No. of reflections	3032
No. of parameters	189
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.20

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O	0.85 (2)	1.995 (16)	2.8059 (19)	160 (2)
O1—H1B···N3ⁱ	0.85 (2)	2.079 (12)	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.

References

Bruker (1998). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kahwa, I. A., Selbin, I., Hsieh, T. C. Y. & Laine, R. A. (1986). Inorg. Chim. Acta, 118, 179–185. CrossRef CAS Web of Science Google Scholar
Santos, M. L. P., Bagatin, I. A., Pereira, E. M. & Ferreira, A. M. D. C. (2001). J. Chem. Soc. Dalton Trans. pp. 838–844. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2336

doi:10.1107/S1600536809034552

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