5-Bromo-N′-(4-hydroxy­benzyl­idene)­nicotinohydrazide

The title Schiff base compound, C₁₃H₁₀BrN₃O₂, was derived from the condensation reaction of 4-hydroxy­benzaldehyde with 5-bromo­nicotinohydrazide. The dihedral angle between the benzene and pyridine rings is 15.2 (3)°. In the crystal structure, mol­ecules are linked through inter­molecular N—H...O, O—H...O and C—H...O hydrogen bonds, forming chains running along the a axis.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.038
• wR factor = 0.093
• Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.88
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.879
            Tmax scaled      0.419 Tmin scaled      0.391
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Recently, the author has reported a few Schiff base complexes (Tang, 2006, 2007a,b). As a continuation of work in this area, the author reports herein the crystal structure of the title new Schiff base compound.

In the title compound (Fig. 1), the dihedral angle between the benzene ring and the pyridine ring is 15.2 (3)°. The torsion angles C6—C7—N1—N2, C7—N1—N2—C8, and N1—N2—C8—C9 are 0.1 (3), 6.4 (3), and 7.5 (3)°, 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 C—H···O intermolecular hydrogen bonds (Table 1), forming chains running along the a axis (Fig. 2).

Related literature

For related literature, see: Tang (2006, 2007a,b); Allen et al. (1987).

S2. Experimental

4-Hydroxybenzaldehyde (0.1 mmol, 12.2 mg) and 5-bromonicotinic acid hydrazide (0.1 mmol, 21.6 mg) were dissolved in an ethanol solution (20 ml). The mixture was stirred at reflux for 10 min to give a clear yellowish solution. Yellowish needle-like crystals of the compound were formed by slow evaporation of the solvent for a few days.

S3. Refinement

H2A was located from a difference Fourier map and refined isotropically, with N—H distance restrained to 0.90 (1) Å, and with the U_iso(H) fixed at 0.08 Ų. Other H atoms were constrained to ideal geometries, with C—H = 0.93 Å, and with U_iso(H) set to 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997a).

Figures

	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 the compound as viewd down the b direction.

5-Bromo-N'-(4-hydroxybenzylidene)nicotinohydrazide

Crystal data

C13H10BrN3O2	Dx = 1.665 Mg m^−3
Mr = 320.15	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3414 reflections
a = 10.868 (2) Å	θ = 2.3–24.5°
b = 8.0470 (16) Å	µ = 3.22 mm^−1
c = 29.209 (6) Å	T = 298 K
V = 2554.5 (9) Å^3	Cut from needle, yellow
Z = 8	0.30 × 0.27 × 0.27 mm
F(000) = 1280

Data collection

Bruker SMART CCD area-detector diffractometer	2635 independent reflections
Radiation source: fine-focus sealed tube	1985 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
ω scans	θmax = 26.5°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.445, Tmax = 0.477	k = −10→10
19259 measured reflections	l = −36→36

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 1.4703P] where P = (Fo^2 + 2Fc^2)/3
2635 reflections	(Δ/σ)max < 0.001
176 parameters	Δρmax = 0.47 e Å^−3
1 restraint	Δρmin = −0.41 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.52751 (3)	0.13520 (5)	0.591535 (11)	0.05060 (15)
O1	0.9032 (2)	0.2855 (3)	0.13604 (7)	0.0557 (7)
H1	0.9699	0.2569	0.1256	0.084*
O2	0.62259 (18)	0.2733 (2)	0.41182 (6)	0.0358 (5)
N1	0.7749 (2)	0.1576 (3)	0.34578 (8)	0.0354 (6)
N2	0.7782 (2)	0.1014 (3)	0.39053 (8)	0.0327 (6)
N3	0.8556 (2)	0.0176 (3)	0.53001 (8)	0.0411 (6)
C1	0.9661 (3)	0.0851 (4)	0.24568 (11)	0.0391 (7)
H1A	1.0241	0.0159	0.2593	0.047*
C2	0.9798 (3)	0.1293 (4)	0.20024 (10)	0.0396 (7)
H2	1.0463	0.0900	0.1833	0.048*
C3	0.8936 (3)	0.2329 (4)	0.18014 (10)	0.0362 (7)
C4	0.7925 (3)	0.2873 (4)	0.20510 (10)	0.0408 (7)
H4	0.7333	0.3539	0.1913	0.049*
C5	0.7802 (3)	0.2427 (4)	0.25011 (10)	0.0366 (7)
H5	0.7126	0.2802	0.2667	0.044*
C6	0.8670 (3)	0.1424 (4)	0.27146 (9)	0.0343 (6)
C7	0.8575 (3)	0.0957 (4)	0.31978 (10)	0.0370 (7)
H7	0.9129	0.0192	0.3318	0.044*
C8	0.7029 (3)	0.1711 (3)	0.42159 (9)	0.0292 (6)
C9	0.7235 (3)	0.1184 (3)	0.47016 (9)	0.0301 (6)
C10	0.6278 (3)	0.1405 (3)	0.50138 (9)	0.0326 (6)
H10	0.5519	0.1825	0.4922	0.039*
C11	0.6498 (3)	0.0980 (4)	0.54622 (9)	0.0341 (7)
C12	0.7616 (3)	0.0351 (4)	0.55927 (10)	0.0387 (7)
H12	0.7726	0.0033	0.5896	0.046*
C13	0.8356 (3)	0.0611 (4)	0.48648 (10)	0.0356 (7)
H13	0.9006	0.0524	0.4659	0.043*
H2A	0.824 (3)	0.011 (3)	0.3966 (13)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0535 (2)	0.0622 (3)	0.0361 (2)	0.00292 (17)	0.01472 (14)	0.00424 (16)
O1	0.0568 (15)	0.0783 (17)	0.0319 (12)	0.0191 (14)	0.0142 (11)	0.0169 (12)
O2	0.0381 (11)	0.0381 (11)	0.0312 (11)	0.0066 (10)	−0.0035 (9)	0.0020 (9)
N1	0.0356 (14)	0.0440 (15)	0.0266 (12)	0.0001 (11)	0.0021 (10)	0.0039 (10)
N2	0.0334 (14)	0.0394 (15)	0.0254 (12)	0.0045 (11)	0.0020 (10)	0.0037 (10)
N3	0.0397 (14)	0.0521 (16)	0.0313 (13)	0.0064 (12)	−0.0068 (11)	−0.0029 (12)
C1	0.0324 (16)	0.0488 (18)	0.0361 (16)	0.0071 (14)	−0.0007 (13)	0.0044 (15)
C2	0.0330 (16)	0.052 (2)	0.0337 (16)	0.0038 (15)	0.0067 (13)	−0.0034 (14)
C3	0.0399 (18)	0.0411 (18)	0.0277 (15)	−0.0024 (14)	0.0041 (13)	0.0029 (13)
C4	0.0372 (17)	0.0499 (19)	0.0354 (16)	0.0101 (15)	0.0043 (13)	0.0087 (14)
C5	0.0326 (16)	0.0429 (17)	0.0343 (16)	0.0048 (14)	0.0076 (13)	0.0000 (14)
C6	0.0338 (16)	0.0394 (17)	0.0298 (15)	−0.0006 (14)	0.0032 (12)	0.0012 (13)
C7	0.0362 (17)	0.0427 (18)	0.0322 (16)	0.0040 (14)	0.0022 (13)	0.0029 (13)
C8	0.0299 (15)	0.0293 (15)	0.0284 (14)	−0.0053 (12)	−0.0013 (11)	0.0022 (11)
C9	0.0325 (15)	0.0290 (15)	0.0288 (14)	−0.0021 (12)	−0.0024 (11)	−0.0007 (11)
C10	0.0310 (15)	0.0377 (16)	0.0291 (15)	0.0021 (13)	0.0002 (12)	0.0008 (13)
C11	0.0379 (16)	0.0362 (16)	0.0282 (14)	−0.0015 (13)	0.0041 (12)	−0.0007 (12)
C12	0.0460 (18)	0.0444 (18)	0.0256 (14)	0.0012 (14)	−0.0060 (13)	−0.0032 (13)
C13	0.0329 (16)	0.0420 (17)	0.0320 (15)	0.0005 (13)	−0.0011 (12)	−0.0024 (13)

Geometric parameters (Å, º)

Br1—C11	1.900 (3)	C3—C4	1.389 (4)
O1—C3	1.360 (3)	C4—C5	1.369 (4)
O1—H1	0.8200	C4—H4	0.9300
O2—C8	1.232 (3)	C5—C6	1.389 (4)
N1—C7	1.277 (4)	C5—H5	0.9300
N1—N2	1.384 (3)	C6—C7	1.464 (4)
N2—C8	1.344 (4)	C7—H7	0.9300
N2—H2A	0.90 (3)	C8—C9	1.498 (4)
N3—C13	1.337 (4)	C9—C13	1.387 (4)
N3—C12	1.339 (4)	C9—C10	1.395 (4)
C1—C2	1.382 (4)	C10—C11	1.375 (4)
C1—C6	1.393 (4)	C10—H10	0.9300
C1—H1A	0.9300	C11—C12	1.370 (4)
C2—C3	1.385 (4)	C12—H12	0.9300
C2—H2	0.9300	C13—H13	0.9300
C3—O1—H1	109.5	C1—C6—C7	119.4 (3)
C7—N1—N2	114.6 (2)	N1—C7—C6	121.5 (3)
C8—N2—N1	119.1 (2)	N1—C7—H7	119.3
C8—N2—H2A	123 (3)	C6—C7—H7	119.3
N1—N2—H2A	118 (3)	O2—C8—N2	123.6 (3)
C13—N3—C12	117.1 (3)	O2—C8—C9	120.9 (2)
C2—C1—C6	121.1 (3)	N2—C8—C9	115.5 (2)
C2—C1—H1A	119.4	C13—C9—C10	118.2 (3)
C6—C1—H1A	119.4	C13—C9—C8	123.4 (3)
C1—C2—C3	119.3 (3)	C10—C9—C8	118.2 (2)
C1—C2—H2	120.4	C11—C10—C9	117.5 (3)
C3—C2—H2	120.4	C11—C10—H10	121.3
O1—C3—C2	122.5 (3)	C9—C10—H10	121.3
O1—C3—C4	117.4 (3)	C12—C11—C10	120.8 (3)
C2—C3—C4	120.2 (3)	C12—C11—Br1	119.0 (2)
C5—C4—C3	119.9 (3)	C10—C11—Br1	120.2 (2)
C5—C4—H4	120.1	N3—C12—C11	122.5 (3)
C3—C4—H4	120.1	N3—C12—H12	118.7
C4—C5—C6	121.2 (3)	C11—C12—H12	118.7
C4—C5—H5	119.4	N3—C13—C9	123.8 (3)
C6—C5—H5	119.4	N3—C13—H13	118.1
C5—C6—C1	118.3 (3)	C9—C13—H13	118.1
C5—C6—C7	122.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2^i	0.90 (3)	2.05 (2)	2.919 (3)	163 (4)
O1—H1···O2^ii	0.82	1.99	2.766 (3)	157
C12—H12···O1^iii	0.93	2.60	3.079 (3)	113

Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x+1/2, y, −z+1/2; (iii) x, −y+1/2, z+1/2.