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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.039
• wR factor = 0.093
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT431_ALERT_2_B Short Inter HL..A Contact  Br1    ..  O2      ..       2.98 Ang.

Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.18
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.88
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT180_ALERT_4_C Check Cell Rounding: # of Values Ending with 0 =          3
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3     ..  BR1     ..       3.05 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3     ..  O1      ..       2.62 Ang.

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      0.882
            Tmax scaled      0.424 Tmin scaled      0.407
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   4 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 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

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

S2. Experimental

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.

S3. Refinement

H2 was located from a difference Fourier map and refined isotropically, with U_iso restrained to 0.08Ų. Other H atoms were constrained to ideal geometries, with d(C–H) = 0.93–0.96 Å, d(O–H) = 0.82 Å, and with U_iso(H) = 1.2U_eq(C), 1.5U_eq(C14, O1 and O3).

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, 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

	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

Crystal data

C13H9BrClN3O2·CH4O	Z = 2
Mr = 386.63	F(000) = 388
Triclinic, P1	Dx = 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) Å^3

Data collection

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

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0424P)^2 + 0.2117P] where P = (Fo^2 + 2Fc^2)/3
3254 reflections	(Δ/σ)max < 0.001
205 parameters	Δρmax = 0.44 e Å^−3
1 restraint	Δρmin = −0.36 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3^i	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···O1^ii	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.