2′-(3-Bromo-5-chloro-2-hydroxy­benzyl­idene)isonicotinohydrazide methanol solvate

Tang, C.-B.

doi:10.1107/S1600536808019648

organic compounds

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doi:10.1107/S1600536808019648

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2′-(3-Bromo-5-chloro-2-hydroxybenzylidene)isonicotinohydrazide methanol solvate

Chun-Bao Tang ^a ^*

^aDepartment of Chemistry, Jiaying University, Meizhou 514015, People's Republic of China
^*Correspondence e-mail: chunbao_tang@163.com

(Received 25 June 2008; accepted 27 June 2008; online 5 July 2008)

The title Schiff base compound, C₁₃H₉BrClN₃O₂·CH₄O, was derived from the condensation reaction of 3-bromo-5-chlorosalicylaldehyde with isonicotinohydrazide. The dihedral angle between the benzene and pyridine rings is 5.9 (2)°. In the crystal structure, molecules are linked through N—H⋯O, O—H⋯O, and O—H⋯Br intermolecular hydrogen bonds, forming dimers and chains. There is also an intramolecular O—H⋯N hydrogen bond.

Related literature

For related structures, see: Tang, (2006 ); Tang, (2007a ,b ,c ,d ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₉BrClN₃O₂·CH₄O
M_r = 386.63
Triclinic, $[P \overline 1]$
a = 7.531 (1) Å
b = 8.735 (1) Å
c = 12.130 (2) Å
α = 80.853 (2)°
β = 77.781 (2)°
γ = 86.721 (2)°
V = 769.73 (19) Å³
Z = 2
Mo Kα radiation
μ = 2.86 mm⁻¹
T = 298 (2) K
0.32 × 0.32 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.461, T_max = 0.481 (expected range = 0.407–0.424)
4529 measured reflections
3254 independent reflections
2438 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.093
S = 1.01
3254 reflections
205 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3ⁱ	0.890 (10)	2.005 (15)	2.876 (4)	166 (4)
O3—H3⋯Br1	0.82	3.05	3.641 (3)	131
O3—H3⋯O1	0.82	2.62	3.268 (4)	137
O3—H3⋯O1ⁱⁱ	0.82	2.55	3.114 (4)	127
O1—H1⋯N1	0.82	1.87	2.590 (3)	146
Symmetry codes: (i) x, y-1, z; (ii) -x+2, -y+1, -z+1.

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808019648/at2582sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019648/at2582Isup2.hkl

checkCIF report

Comment top

Recently, the author has reported the structures of several Schiff base compounds (Tang, 2006; Tang, 2007a,b,c,d) and, in continuation of work in this area, reports herein the crystal structure of the title new Schiff base compound, (I).

In the title compound (Fig. 1), the dihedral angle between the benzene ring and the pyridine ring is 5.9 (2)°. The torsion angles C1—C7—N1—N2, C7—N1—N2—C8, and N1—N2—C8—C9 are 0.4 (2), 2.3 (2), and 1.9 (2)°, respectively. All the bond lengths are within normal values (Allen et al., 1987).

In the crystal structure of the compound, molecules are linked through N–H···O, O–H···O, and O–H···Br intermolecular hydrogen bonds (Table 1), forming dimers (Fig. 2).

Related literature top

For related structures, see: Tang, (2006); Tang, (2007a,b,c,d). For reference structural data, see: Allen et al. (1987).

Experimental top

3-Bromo-5-chlorosalicylaldehyde (0.1 mmol, 23.5 mg) and isonicotinohydrazide (0.1 mmol, 13.7 mg) were dissolved in a methanol solution (20 ml). The mixture was stirred at reflux for 10 min to give a clear colourless solution. Colourless block-like crystals of the compound were formed by slow evaporation of the solvent over several days.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Molecular packing of (I) with hydrogen bonds drawn as dashed lines.

2'-(3-Bromo-5-chloro-2-hydroxybenzylidene)isonicotinohydrazide methanol solvate top

Crystal data top

C₁₃H₉BrClN₃O₂·CH₄O	Z = 2
M_r = 386.63	F(000) = 388
Triclinic, P1	D_x = 1.668 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.531 (1) Å	Cell parameters from 1404 reflections
b = 8.735 (1) Å	θ = 2.5–24.3°
c = 12.130 (2) Å	µ = 2.86 mm⁻¹
α = 80.853 (2)°	T = 298 K
β = 77.781 (2)°	Block, colourless
γ = 86.721 (2)°	0.32 × 0.32 × 0.30 mm
V = 769.73 (19) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3254 independent reflections
Radiation source: fine-focus sealed tube	2438 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 27.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.461, T_max = 0.481	k = −11→10
4529 measured reflections	l = −15→13

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0424P)² + 0.2117P] where P = (F_o² + 2F_c²)/3
3254 reflections	(Δ/σ)_max < 0.001
205 parameters	Δρ_max = 0.44 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₃H₉BrClN₃O₂·CH₄O	γ = 86.721 (2)°
M_r = 386.63	V = 769.73 (19) Å³
Triclinic, P1	Z = 2
a = 7.531 (1) Å	Mo Kα radiation
b = 8.735 (1) Å	µ = 2.86 mm⁻¹
c = 12.130 (2) Å	T = 298 K
α = 80.853 (2)°	0.32 × 0.32 × 0.30 mm
β = 77.781 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3254 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2438 reflections with I > 2σ(I)
T_min = 0.461, T_max = 0.481	R_int = 0.018
4529 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.44 e Å⁻³
3254 reflections	Δρ_min = −0.36 e Å⁻³
205 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Br1	1.13987 (5)	0.60600 (4)	0.27243 (3)	0.04953 (14)
Cl1	1.14281 (14)	0.21720 (11)	−0.04331 (7)	0.0585 (3)
O1	0.9336 (4)	0.3429 (3)	0.42960 (18)	0.0492 (6)
H1	0.8805	0.2694	0.4718	0.074*
O2	0.6850 (4)	0.1108 (3)	0.6960 (2)	0.0613 (7)
O3	0.7162 (4)	0.6702 (3)	0.4708 (2)	0.0648 (7)
H3	0.8129	0.6213	0.4678	0.097*
N1	0.7910 (4)	0.0712 (3)	0.4821 (2)	0.0422 (7)
N2	0.7009 (4)	−0.0439 (3)	0.5622 (2)	0.0435 (7)
N3	0.3580 (4)	−0.3481 (4)	0.9325 (3)	0.0541 (8)
C1	0.9409 (4)	0.1661 (4)	0.2938 (3)	0.0376 (7)
C2	0.9789 (4)	0.3099 (3)	0.3219 (2)	0.0356 (7)
C3	1.0695 (4)	0.4184 (3)	0.2357 (3)	0.0371 (7)
C4	1.1193 (4)	0.3917 (3)	0.1240 (3)	0.0383 (7)
H4	1.1788	0.4670	0.0674	0.046*
C5	1.0792 (4)	0.2518 (4)	0.0983 (3)	0.0388 (7)
C6	0.9935 (4)	0.1387 (4)	0.1807 (3)	0.0406 (8)
H6	0.9703	0.0439	0.1615	0.049*
C7	0.8466 (4)	0.0454 (4)	0.3797 (3)	0.0423 (8)
H7	0.8271	−0.0499	0.3599	0.051*
C8	0.6508 (4)	−0.0112 (4)	0.6708 (3)	0.0392 (7)
C9	0.5474 (4)	−0.1341 (3)	0.7577 (3)	0.0353 (7)
C10	0.5137 (5)	−0.2802 (4)	0.7393 (3)	0.0432 (8)
H10	0.5524	−0.3098	0.6675	0.052*
C11	0.4218 (5)	−0.3815 (4)	0.8288 (3)	0.0533 (9)
H11	0.4032	−0.4806	0.8155	0.064*
C12	0.3884 (5)	−0.2064 (5)	0.9486 (3)	0.0601 (10)
H12	0.3433	−0.1788	1.0204	0.072*
C13	0.4825 (5)	−0.0977 (4)	0.8658 (3)	0.0507 (9)
H13	0.5023	−0.0005	0.8825	0.061*
C14	0.6322 (7)	0.6375 (5)	0.3861 (4)	0.0809 (14)
H14A	0.5114	0.6820	0.3967	0.121*
H14B	0.6264	0.5272	0.3902	0.121*
H14C	0.7007	0.6808	0.3127	0.121*
H2	0.689 (6)	−0.136 (2)	0.543 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0660 (3)	0.0388 (2)	0.0409 (2)	−0.01820 (16)	0.00010 (16)	−0.00617 (14)
Cl1	0.0847 (7)	0.0584 (5)	0.0301 (4)	−0.0171 (5)	0.0016 (4)	−0.0118 (4)
O1	0.0672 (17)	0.0464 (14)	0.0289 (12)	−0.0191 (12)	0.0035 (11)	−0.0019 (10)
O2	0.088 (2)	0.0386 (13)	0.0523 (15)	−0.0236 (13)	0.0019 (13)	−0.0050 (11)
O3	0.073 (2)	0.0651 (18)	0.0574 (17)	−0.0025 (15)	−0.0088 (15)	−0.0168 (14)
N1	0.0448 (16)	0.0384 (15)	0.0373 (16)	−0.0112 (12)	−0.0042 (12)	0.0104 (12)
N2	0.0547 (18)	0.0384 (15)	0.0331 (15)	−0.0216 (14)	−0.0030 (13)	0.0063 (12)
N3	0.059 (2)	0.0546 (19)	0.0415 (17)	−0.0192 (15)	0.0025 (14)	0.0047 (14)
C1	0.0376 (18)	0.0377 (17)	0.0344 (17)	−0.0055 (14)	−0.0053 (14)	0.0028 (13)
C2	0.0383 (18)	0.0375 (17)	0.0292 (16)	−0.0064 (14)	−0.0041 (13)	−0.0017 (13)
C3	0.0421 (19)	0.0339 (16)	0.0331 (16)	−0.0103 (14)	−0.0024 (14)	−0.0028 (13)
C4	0.0418 (19)	0.0351 (17)	0.0322 (16)	−0.0098 (14)	0.0003 (14)	0.0048 (13)
C5	0.0451 (19)	0.0439 (18)	0.0256 (15)	−0.0084 (15)	−0.0029 (14)	−0.0028 (13)
C6	0.046 (2)	0.0361 (17)	0.0405 (18)	−0.0097 (14)	−0.0095 (15)	−0.0049 (14)
C7	0.047 (2)	0.0376 (17)	0.0394 (19)	−0.0157 (15)	−0.0047 (15)	0.0022 (14)
C8	0.0424 (19)	0.0341 (17)	0.0374 (18)	−0.0089 (14)	−0.0042 (14)	0.0037 (14)
C9	0.0334 (17)	0.0346 (16)	0.0349 (17)	−0.0086 (13)	−0.0030 (13)	0.0014 (13)
C10	0.052 (2)	0.0387 (18)	0.0335 (17)	−0.0125 (15)	0.0030 (15)	−0.0025 (14)
C11	0.062 (2)	0.0433 (19)	0.049 (2)	−0.0178 (18)	0.0004 (18)	0.0006 (16)
C12	0.068 (3)	0.072 (3)	0.035 (2)	−0.022 (2)	0.0059 (18)	−0.0078 (18)
C13	0.061 (2)	0.0446 (19)	0.043 (2)	−0.0167 (17)	0.0042 (17)	−0.0090 (16)
C14	0.095 (4)	0.077 (3)	0.078 (3)	−0.012 (3)	−0.025 (3)	−0.019 (3)

Geometric parameters (Å, º) top

Br1—C3	1.897 (3)	C4—C5	1.373 (4)
Cl1—C5	1.753 (3)	C4—H4	0.9300
O1—C2	1.351 (3)	C5—C6	1.370 (4)
O1—H1	0.8200	C6—H6	0.9300
O2—C8	1.209 (4)	C7—H7	0.9300
O3—C14	1.388 (5)	C8—C9	1.503 (4)
O3—H3	0.8200	C9—C10	1.377 (4)
N1—C7	1.276 (4)	C9—C13	1.380 (4)
N1—N2	1.380 (3)	C10—C11	1.374 (4)
N2—C8	1.363 (4)	C10—H10	0.9300
N2—H2	0.890 (10)	C11—H11	0.9300
N3—C11	1.320 (5)	C12—C13	1.373 (5)
N3—C12	1.323 (5)	C12—H12	0.9300
C1—C6	1.400 (4)	C13—H13	0.9300
C1—C2	1.412 (4)	C14—H14A	0.9600
C1—C7	1.457 (4)	C14—H14B	0.9600
C2—C3	1.383 (4)	C14—H14C	0.9600
C3—C4	1.380 (4)

C2—O1—H1	109.5	N1—C7—H7	120.2
C14—O3—H3	109.5	C1—C7—H7	120.2
C7—N1—N2	118.9 (3)	O2—C8—N2	122.1 (3)
C8—N2—N1	116.0 (3)	O2—C8—C9	121.6 (3)
C8—N2—H2	124 (3)	N2—C8—C9	116.3 (3)
N1—N2—H2	120 (3)	C10—C9—C13	117.2 (3)
C11—N3—C12	115.9 (3)	C10—C9—C8	125.7 (3)
C6—C1—C2	119.4 (3)	C13—C9—C8	117.0 (3)
C6—C1—C7	118.9 (3)	C11—C10—C9	118.7 (3)
C2—C1—C7	121.6 (3)	C11—C10—H10	120.6
O1—C2—C3	119.5 (3)	C9—C10—H10	120.6
O1—C2—C1	122.3 (3)	N3—C11—C10	124.7 (3)
C3—C2—C1	118.2 (3)	N3—C11—H11	117.6
C4—C3—C2	122.3 (3)	C10—C11—H11	117.6
C4—C3—Br1	118.4 (2)	N3—C12—C13	124.1 (3)
C2—C3—Br1	119.3 (2)	N3—C12—H12	118.0
C5—C4—C3	118.6 (3)	C13—C12—H12	118.0
C5—C4—H4	120.7	C12—C13—C9	119.3 (3)
C3—C4—H4	120.7	C12—C13—H13	120.4
C6—C5—C4	121.6 (3)	C9—C13—H13	120.4
C6—C5—Cl1	119.6 (2)	O3—C14—H14A	109.5
C4—C5—Cl1	118.8 (2)	O3—C14—H14B	109.5
C5—C6—C1	119.9 (3)	H14A—C14—H14B	109.5
C5—C6—H6	120.1	O3—C14—H14C	109.5
C1—C6—H6	120.1	H14A—C14—H14C	109.5
N1—C7—C1	119.6 (3)	H14B—C14—H14C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.89 (1)	2.01 (2)	2.876 (4)	166 (4)
O3—H3···Br1	0.82	3.05	3.641 (3)	131
O3—H3···O1	0.82	2.62	3.268 (4)	137
O3—H3···O1ⁱⁱ	0.82	2.55	3.114 (4)	127
O1—H1···N1	0.82	1.87	2.590 (3)	146

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

Experimental details

Crystal data
Chemical formula	C₁₃H₉BrClN₃O₂·CH₄O
M_r	386.63
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.531 (1), 8.735 (1), 12.130 (2)
α, β, γ (°)	80.853 (2), 77.781 (2), 86.721 (2)
V (Å³)	769.73 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.86
Crystal size (mm)	0.32 × 0.32 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.461, 0.481
No. of measured, independent and observed [I > 2σ(I)] reflections	4529, 3254, 2438
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.093, 1.01
No. of reflections	3254
No. of parameters	205
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.36

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.890 (10)	2.005 (15)	2.876 (4)	166 (4)
O3—H3···Br1	0.82	3.05	3.641 (3)	131.3
O3—H3···O1	0.82	2.62	3.268 (4)	136.6
O3—H3···O1ⁱⁱ	0.82	2.55	3.114 (4)	127.4
O1—H1···N1	0.82	1.87	2.590 (3)	146.0

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

Acknowledgements

Financial support from the Jiaying University research fund is gratefully acknowledged.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2002). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tang, C.-B. (2006). Acta Cryst. E62, m2629–m2630. Web of Science CSD CrossRef IUCr Journals Google Scholar
Tang, C.-B. (2007a). Acta Cryst. E63, m2654. Web of Science CSD CrossRef IUCr Journals Google Scholar
Tang, C.-B. (2007b). Acta Cryst. E63, m2785–m2786. Web of Science CSD CrossRef IUCr Journals Google Scholar
Tang, C.-B. (2007c). Acta Cryst. E63, o4545. Web of Science CSD CrossRef IUCr Journals Google Scholar
Tang, C.-B. (2007d). Acta Cryst. E63, o4841. Web of Science CSD CrossRef IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2′-(3-Bromo-5-chloro-2-hy­droxy­benzyl­­idene)isonicotinohydrazide methanol solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2′-(3-Bromo-5-chloro-2-hydroxybenzylidene)isonicotinohydrazide methanol solvate