N′-[(E)-2-Hy­droxy-5-meth­oxy­benzyl­idene]pyridine-4-carbohydrazide

In the title compound, C₁₄H₁₃N₃O₃, the dihedral angle between the pyridine and benzene rings is 15.17 (18)°. The torsion angle of the –C=N—N—C– system between two aromatic rings is −167.1 (3)°. Intra­molecular O—H...N hydrogen bonding generates S(6) rings. In the crystal structure, neighbouring mol­ecules are linked together along the c axis by weak inter­molecular C—H...O and N—H...O hydrogen bonds, generating R₁²(6) ring motifs.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.046
• wR factor = 0.114
• Data-to-parameter ratio = 8.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          5
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          7

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.53
           From the CIF: _reflns_number_total               1542
           Count of symmetry unique reflns         1547
           Completeness (_total/calc)             99.68%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          2
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.67 mm

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 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
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In the search for new biologically active compounds, isoniazid (isonicotinylhydrazine) derivatives have been found to possess potential tuberculostatic activity (Janin, 2007; Maccari et al., 2005). Here, we present the crystal structure of the title compound, (I).

In the title compound (I), (Fig. 1), the dihedral angle between the pyridine (C10–C14) and benzene (C1–C6) rings is 15.17 (18)°. The C8–N1–N2–C9 torsion angle is -167.1 (3) °.

Intramolecular O1—H1···N1 hydrogen bonding generates S(6) rings (Bernstein et al., 1995) (Table 1, Fig. 2). In the crystal structure, neighbouring molecules are linked together by weak intermolecular C—H···O and N—H···O hydrogen bonds (Table 1, Fig. 2), generating R₁²(6) ring motifs (Bernstein et al., 1995), and linking the molecules along the c axis.

Related literature

For the tuberculostatic activity of isoniazid (isonicotinylhydrazine) derivatives, see: Janin (2007); Maccari et al. (2005). For the synthesis of the isoniazid derivative, see: Lourenco et al. (2008). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the calculation of the Flack parameter, see: Flack (1983).

S2. Experimental

The isoniazid derivative was prepared following procedure reported by Lourenco et al., (2008). 5-methoxysalicylaldehyde (1.0 mmol) was added to isoniazid (1.0 mmol) in ethanol. After stirring for 3 h at reflux condition, the resulting mixture was concentrated at room temperature. The residue was purified by washing with cold ethanol and diethyl ether to give the pure derivative. Colourless single crystals suitable for X-ray analysis were obtained by re-crystallization from methanol.

S3. Refinement

In the absence of significant anomalous dispersion effects, Freidel pairs were merged. The calculation of the Flack (1983) parameter was suppressed by the MERG 4 command in SHELXL97 (Sheldrick, 2008), as the lack of anomalous scatterers did not allow the determination of the absolute configuration from the X-ray measurements. The H atoms of the O—H and N—H groups were found from a difference Fourier map and refined freely [O1—H1 = 0.96 (4) and N2—H2 = 0.88 (4) Å]. The remaining H atoms were placed in idealized positions and allowed to ride on their parent atoms, with C—H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and U_iso(H) = 1.5U_eq(C) for methyl H and U_iso(H) = 1.2U_eq(C) for aromatic H.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The title molecule, with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. The packing and hydrogen bonding interactions of (I), down a axis, showing R1^2(6) ring motifs. All H atoms not involved in hydrogen bonding are omitted for clarity.

N'-[(E)-2-Hydroxy-5-methoxybenzylidene]pyridine-4-carbohydrazide

Crystal data

C14H13N3O3	F(000) = 568
Mr = 271.27	Dx = 1.345 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 7613 reflections
a = 6.1114 (6) Å	θ = 2.8–28.0°
b = 29.489 (3) Å	µ = 0.10 mm^−1
c = 7.4820 (7) Å	T = 296 K
β = 96.696 (8)°	Prism, colourless
V = 1339.2 (2) Å^3	0.67 × 0.34 × 0.12 mm
Z = 4

Data collection

Stoe IPDS 2 diffractometer	1542 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	1166 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.038
Detector resolution: 6.67 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
ω scans	h = −7→7
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −38→35
Tmin = 0.962, Tmax = 0.988	l = −9→8
4353 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0582P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max < 0.001
1542 reflections	Δρmax = 0.13 e Å^−3
191 parameters	Δρmin = −0.16 e Å^−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0090 (19)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
O1	−0.1045 (4)	0.82503 (10)	0.3515 (4)	0.0727 (9)
O2	0.2101 (5)	0.99107 (9)	0.6041 (5)	0.0844 (10)
O3	0.2501 (4)	0.71171 (8)	0.2791 (4)	0.0743 (9)
N1	0.2870 (4)	0.79115 (10)	0.4570 (4)	0.0619 (9)
N2	0.4398 (4)	0.75656 (9)	0.4882 (4)	0.0622 (9)
N3	0.8707 (5)	0.61195 (13)	0.5468 (5)	0.0794 (11)
C1	0.1994 (5)	0.86852 (12)	0.5002 (4)	0.0572 (10)
C2	−0.0172 (5)	0.86497 (12)	0.4151 (5)	0.0599 (11)
C3	−0.1453 (5)	0.90380 (14)	0.3930 (6)	0.0753 (15)
C4	−0.0645 (6)	0.94459 (14)	0.4568 (6)	0.0766 (13)
C5	0.1486 (5)	0.94855 (12)	0.5445 (5)	0.0646 (11)
C6	0.2792 (5)	0.91072 (12)	0.5652 (5)	0.0611 (11)
C7	0.4191 (7)	0.99583 (16)	0.7042 (7)	0.0830 (14)
C8	0.3464 (5)	0.82985 (12)	0.5228 (5)	0.0591 (11)
C9	0.4075 (4)	0.71774 (11)	0.3949 (4)	0.0574 (10)
C10	0.5728 (5)	0.68156 (11)	0.4456 (4)	0.0564 (10)
C11	0.7920 (5)	0.69069 (13)	0.5046 (5)	0.0672 (11)
C12	0.9319 (6)	0.65507 (17)	0.5525 (6)	0.0778 (15)
C13	0.6605 (6)	0.60362 (13)	0.4866 (6)	0.0739 (14)
C14	0.5073 (5)	0.63664 (12)	0.4332 (5)	0.0655 (11)
H1	0.007 (7)	0.8019 (15)	0.363 (6)	0.080 (12)*
H2	0.552 (7)	0.7604 (14)	0.572 (6)	0.079 (11)*
H3	−0.28770	0.90210	0.33400	0.0900*
H4	−0.15340	0.97020	0.44150	0.0920*
H6	0.42200	0.91300	0.62290	0.0730*
H7A	0.53150	0.98860	0.62920	0.1250*
H7B	0.43020	0.97560	0.80540	0.1250*
H7C	0.43790	1.02650	0.74600	0.1250*
H8	0.48570	0.83320	0.58600	0.0710*
H11	0.84350	0.72040	0.51180	0.0810*
H12	1.07860	0.66170	0.59120	0.0940*
H13	0.61430	0.57360	0.48040	0.0880*
H14	0.36330	0.62890	0.38980	0.0790*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0555 (12)	0.0673 (16)	0.0905 (19)	0.0003 (11)	−0.0119 (12)	−0.0055 (13)
O2	0.0782 (15)	0.0598 (16)	0.111 (2)	0.0057 (12)	−0.0066 (15)	−0.0122 (16)
O3	0.0669 (13)	0.0602 (14)	0.0864 (19)	0.0021 (11)	−0.0310 (12)	−0.0050 (13)
N1	0.0523 (12)	0.0570 (17)	0.0721 (19)	0.0056 (12)	−0.0115 (12)	0.0015 (14)
N2	0.0541 (12)	0.0544 (16)	0.0716 (18)	0.0064 (12)	−0.0195 (12)	−0.0042 (14)
N3	0.0687 (18)	0.079 (2)	0.090 (2)	0.0237 (16)	0.0069 (15)	0.0059 (19)
C1	0.0511 (15)	0.061 (2)	0.0581 (19)	0.0045 (13)	0.0008 (13)	0.0026 (15)
C2	0.0478 (14)	0.065 (2)	0.066 (2)	−0.0007 (14)	0.0023 (13)	0.0000 (17)
C3	0.0481 (17)	0.078 (3)	0.097 (3)	0.0108 (16)	−0.0031 (18)	0.003 (2)
C4	0.0616 (18)	0.069 (2)	0.096 (3)	0.0148 (17)	−0.0043 (18)	−0.002 (2)
C5	0.0606 (17)	0.058 (2)	0.074 (2)	0.0017 (15)	0.0028 (15)	−0.0040 (18)
C6	0.0495 (15)	0.062 (2)	0.070 (2)	0.0014 (13)	−0.0011 (14)	−0.0002 (16)
C7	0.081 (2)	0.072 (2)	0.093 (3)	−0.0038 (19)	−0.003 (2)	−0.011 (2)
C8	0.0519 (14)	0.059 (2)	0.063 (2)	0.0013 (13)	−0.0081 (13)	0.0011 (16)
C9	0.0458 (13)	0.0562 (19)	0.066 (2)	−0.0026 (12)	−0.0107 (13)	0.0011 (16)
C10	0.0504 (14)	0.0602 (19)	0.0565 (18)	0.0030 (13)	−0.0027 (13)	−0.0032 (16)
C11	0.0520 (15)	0.070 (2)	0.077 (2)	0.0048 (15)	−0.0028 (15)	−0.0028 (19)
C12	0.0548 (16)	0.090 (3)	0.087 (3)	0.0123 (18)	0.0011 (17)	−0.001 (2)
C13	0.074 (2)	0.061 (2)	0.086 (3)	0.0101 (17)	0.007 (2)	−0.0042 (19)
C14	0.0616 (17)	0.058 (2)	0.076 (2)	0.0017 (14)	0.0039 (16)	−0.0093 (18)

Geometric parameters (Å, º)

O1—C2	1.356 (5)	C5—C6	1.370 (5)
O2—C5	1.369 (5)	C9—C10	1.488 (4)
O2—C7	1.410 (6)	C10—C11	1.387 (4)
O3—C9	1.230 (4)	C10—C14	1.384 (5)
O1—H1	0.96 (4)	C11—C12	1.375 (6)
N1—N2	1.384 (4)	C13—C14	1.377 (5)
N1—C8	1.279 (5)	C3—H3	0.9300
N2—C9	1.343 (4)	C4—H4	0.9300
N3—C13	1.334 (5)	C6—H6	0.9300
N3—C12	1.325 (6)	C7—H7A	0.9600
N2—H2	0.88 (4)	C7—H7B	0.9600
C1—C6	1.403 (5)	C7—H7C	0.9600
C1—C2	1.404 (4)	C8—H8	0.9300
C1—C8	1.449 (5)	C11—H11	0.9300
C2—C3	1.386 (5)	C12—H12	0.9300
C3—C4	1.365 (6)	C13—H13	0.9300
C4—C5	1.393 (5)	C14—H14	0.9300
O1···N1	2.628 (4)	C7···H6	2.5200
O1···C10^i	3.347 (4)	C8···H1	2.42 (4)
O2···C7^ii	3.409 (6)	C11···H2	2.61 (4)
O3···N2^i	2.872 (4)	C12···H3^viii	3.0600
O3···C12^iii	3.418 (5)	C14···H12^iii	3.0900
O3···N1	2.691 (4)	H1···N1	1.80 (4)
O3···C8^i	3.188 (4)	H1···C8	2.42 (4)
O1···H12^iv	2.6100	H2···C11	2.61 (4)
O2···H13^v	2.6500	H2···H8	2.1900
O2···H7B^ii	2.9100	H2···H11	2.2300
O3···H14	2.6400	H2···O3^vi	2.03 (4)
O3···H2^i	2.03 (4)	H3···N3^iv	2.8500
O3···H8^i	2.4300	H3···C12^iv	3.0600
N1···O1	2.628 (4)	H4···H7A^iii	2.5700
N1···O3	2.691 (4)	H6···C7	2.5200
N1···C11^i	3.431 (5)	H6···H7A	2.3300
N2···O3^vi	2.872 (4)	H6···H7B	2.2900
N1···H1	1.80 (4)	H6···H8	2.4100
N2···H11	2.6700	H7A···C6	2.7800
N3···H7C^vii	2.9300	H7A···H4^xi	2.5700
N3···H3^viii	2.8500	H7A···H6	2.3300
C1···C14^ix	3.576 (5)	H7B···C6	2.7100
C5···C7^ii	3.590 (6)	H7B···H6	2.2900
C6···C13^ix	3.344 (6)	H7B···O2^x	2.9100
C7···O2^x	3.409 (6)	H7C···C5^x	3.0900
C7···C5^x	3.590 (6)	H7C···N3^v	2.9300
C8···O3^vi	3.188 (4)	H8···H2	2.1900
C10···O1^vi	3.347 (4)	H8···H6	2.4100
C11···N1^vi	3.431 (5)	H8···O3^vi	2.4300
C12···O3^xi	3.418 (5)	H11···N2	2.6700
C13···C6^xii	3.344 (6)	H11···H2	2.2300
C14···C1^xii	3.576 (5)	H12···C14^xi	3.0900
C5···H7C^ii	3.0900	H12···O1^viii	2.6100
C6···H7A	2.7800	H13···O2^vii	2.6500
C6···H7B	2.7100	H14···O3	2.6400
C5—O2—C7	117.5 (3)	C10—C11—C12	118.9 (3)
C2—O1—H1	110 (3)	N3—C12—C11	124.1 (4)
N2—N1—C8	115.9 (3)	N3—C13—C14	124.3 (4)
N1—N2—C9	119.0 (3)	C10—C14—C13	118.4 (3)
C12—N3—C13	116.4 (4)	C2—C3—H3	120.00
C9—N2—H2	122 (3)	C4—C3—H3	120.00
N1—N2—H2	119 (3)	C3—C4—H4	119.00
C2—C1—C6	119.6 (3)	C5—C4—H4	119.00
C2—C1—C8	122.2 (3)	C1—C6—H6	120.00
C6—C1—C8	118.2 (3)	C5—C6—H6	120.00
O1—C2—C3	118.8 (3)	O2—C7—H7A	109.00
O1—C2—C1	122.4 (3)	O2—C7—H7B	109.00
C1—C2—C3	118.8 (3)	O2—C7—H7C	109.00
C2—C3—C4	120.7 (3)	H7A—C7—H7B	109.00
C3—C4—C5	121.3 (4)	H7A—C7—H7C	109.00
C4—C5—C6	119.0 (3)	H7B—C7—H7C	110.00
O2—C5—C4	115.9 (3)	N1—C8—H8	120.00
O2—C5—C6	125.1 (3)	C1—C8—H8	120.00
C1—C6—C5	120.6 (3)	C10—C11—H11	121.00
N1—C8—C1	120.9 (3)	C12—C11—H11	121.00
O3—C9—N2	123.0 (3)	N3—C12—H12	118.00
O3—C9—C10	121.9 (3)	C11—C12—H12	118.00
N2—C9—C10	115.1 (2)	N3—C13—H13	118.00
C11—C10—C14	117.9 (3)	C14—C13—H13	118.00
C9—C10—C11	122.9 (3)	C10—C14—H14	121.00
C9—C10—C14	119.1 (3)	C13—C14—H14	121.00
C7—O2—C5—C6	−4.1 (6)	O1—C2—C3—C4	179.3 (4)
C7—O2—C5—C4	175.8 (4)	C2—C3—C4—C5	0.5 (6)
N2—N1—C8—C1	−179.4 (3)	C3—C4—C5—O2	−179.3 (4)
C8—N1—N2—C9	−167.1 (3)	C3—C4—C5—C6	0.6 (6)
N1—N2—C9—C10	−176.4 (3)	O2—C5—C6—C1	179.5 (3)
N1—N2—C9—O3	1.7 (5)	C4—C5—C6—C1	−0.4 (5)
C13—N3—C12—C11	1.5 (6)	O3—C9—C10—C14	−30.5 (4)
C12—N3—C13—C14	−0.7 (6)	O3—C9—C10—C11	149.2 (3)
C8—C1—C6—C5	178.8 (3)	N2—C9—C10—C14	147.6 (3)
C6—C1—C2—C3	1.8 (5)	N2—C9—C10—C11	−32.7 (4)
C2—C1—C6—C5	−0.8 (5)	C14—C10—C11—C12	−1.8 (5)
C8—C1—C2—O1	1.3 (5)	C9—C10—C11—C12	178.5 (3)
C8—C1—C2—C3	−177.8 (3)	C9—C10—C14—C13	−177.8 (3)
C6—C1—C2—O1	−179.2 (3)	C11—C10—C14—C13	2.5 (5)
C2—C1—C8—N1	3.7 (5)	C10—C11—C12—N3	−0.3 (6)
C6—C1—C8—N1	−175.9 (3)	N3—C13—C14—C10	−1.4 (6)
C1—C2—C3—C4	−1.6 (6)

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) x, −y+2, z−1/2; (iii) x−1, y, z; (iv) x−3/2, −y+3/2, z−1/2; (v) x−1/2, y+1/2, z; (vi) x+1/2, −y+3/2, z+1/2; (vii) x+1/2, y−1/2, z; (viii) x+3/2, −y+3/2, z+1/2; (ix) x−1/2, −y+3/2, z+1/2; (x) x, −y+2, z+1/2; (xi) x+1, y, z; (xii) x+1/2, −y+3/2, z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.96 (4)	1.80 (4)	2.628 (4)	142 (4)
N2—H2···O3^vi	0.88 (4)	2.03 (4)	2.872 (4)	161 (4)
C8—H8···O3^vi	0.93	2.43	3.188 (4)	139

Symmetry code: (vi) x+1/2, −y+3/2, z+1/2.