2′-(4-Methoxy­benzyl­idene)isonicotinohydrazide monohydrate

The title compound, C₁₄H₁₃N₃O₂·H₂O, was prepared from pyridine-4-carboxylic acid hydrazide and 4-methoxy­benzaldehyde. In the crystal structure, the water mol­ecules participate in O—H...O, O—H...N and N—H...O hydrogen bonds with the hydrazide mol­ecules; these inter­actions contribute to the stability of the structure.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.034
• wR factor = 0.097
• Data-to-parameter ratio = 16.5

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S1. Comment

The syntheses and structures of Schiff bases have attracted much attention, because their metal complexes have been studied extensively as model compounds of active centres in various proteins and enzymes (Santos et al., 2001). In order to investigate the physical and chemical properties, we report the synthesis and molecular structure of the title compound, (I) (Fig. 1).

The C7—C8, C7—N3 and N2—N3 bond lengths of 1.4623 (14), 1.2734 (14) and 1.3881 (12) Å, respectively, are consistent with those in related structures (Jing et al., 2005; Yu et al., 2005). The central system (C7–C14/N2/N3/O2) is planar, the r.m.s. deviation of fitted atoms being 0.0308 Å, and the pyridine moiety (C1—C6/N1) is planar with an r.m.s. deviation of 0.0214 Å. The dihedral angle between the two planes is 36.78 (3)°. It should be noted that the water molecules participate in O—H···O, O—H···N and N—H···O hydrogen bonds with the hydrazide molecules (Table 1); these interactions play a key role in stabilization of the solid state (Fig. 2).

S2. Experimental

An anhydrous ethanol solution of pyridine-4-carboxylic acid hydrazide (1.37 g, 10 mmol) was added to an anhydrous ethanol solution of 4-methoxybenzaldehyde (1.36 g, 10 mmol), and the mixture was stirred at 350 K for 5 h under nitrogen. A white precipitate appeared. The product was isolated and recrystallized from ethanol, and then dried in vacuo to give the pure compound in 89% yield. Bright-white single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

S3. Refinement

Atom H2A attached to N2 and atoms H3A and H3B attached to O3 were located in a difference Fourier map. Atom H2A was refined freely, while for H3A and H3B the positions were refined with U_iso(H) = U_eq(O). Other H atoms were included in calculated positions (C—H = 0.93–0.96 Å) and refined using the riding-model approximation, with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. An view of the title compound, with 30% probability displacement ellipsoids.
	Fig. 2. Intermolecular hydrogen bonds in (I), shown as dashed lines. Please replace with figure including unit cell outline if possible.

2'-(4-Methoxybenzylidene)isonicotinohydrazide monohydrate

Crystal data

C14H15N3O3	F(000) = 576
Mr = 273.29	Dx = 1.351 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.3660 (15) Å	Cell parameters from 3520 reflections
b = 12.422 (3) Å	θ = 2.8–27.8°
c = 14.785 (3) Å	µ = 0.10 mm^−1
β = 96.699 (2)°	T = 294 K
V = 1343.6 (5) Å^3	Block, white
Z = 4	0.24 × 0.14 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3186 independent reflections
Radiation source: fine-focus sealed tube	2585 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
ϕ and ω scans	θmax = 27.9°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→9
Tmin = 0.960, Tmax = 0.990	k = −16→14
8826 measured reflections	l = −19→19

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)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0495P)^2 + 0.2087P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
3186 reflections	Δρmax = 0.24 e Å^−3
193 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.032 (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
O1	0.14970 (14)	0.85670 (7)	0.75409 (6)	0.0497 (2)
O2	0.42901 (12)	0.90937 (7)	0.19088 (5)	0.0430 (2)
N1	0.13542 (16)	1.14173 (10)	0.99454 (7)	0.0515 (3)
N2	0.16625 (13)	1.01320 (8)	0.67597 (6)	0.0332 (2)
H2A	0.1608 (17)	1.0855 (12)	0.6762 (8)	0.041 (3)*
N3	0.20217 (13)	0.96112 (7)	0.59692 (6)	0.0346 (2)
C1	0.03866 (15)	1.11721 (9)	0.83583 (7)	0.0353 (2)
H1	−0.0272	1.1430	0.7828	0.042*
C2	0.04175 (17)	1.17389 (10)	0.91639 (8)	0.0438 (3)
H2	−0.0247	1.2376	0.9162	0.053*
C3	0.2242 (2)	1.04846 (12)	0.99370 (8)	0.0528 (3)
H3	0.2878	1.0243	1.0479	0.063*
C4	0.22717 (18)	0.98561 (11)	0.91682 (8)	0.0447 (3)
H4	0.2898	0.9205	0.9197	0.054*
C5	0.13479 (15)	1.02155 (8)	0.83507 (7)	0.0328 (2)
C6	0.14838 (15)	0.95531 (9)	0.75097 (7)	0.0334 (2)
C7	0.22619 (15)	1.02495 (9)	0.53198 (7)	0.0343 (2)
H7	0.2108	1.0984	0.5407	0.041*
C8	0.27683 (14)	0.98822 (9)	0.44437 (7)	0.0318 (2)
C9	0.32203 (17)	0.88243 (9)	0.42683 (7)	0.0381 (3)
H9	0.3166	0.8306	0.4719	0.046*
C10	0.37512 (16)	0.85238 (9)	0.34352 (7)	0.0380 (3)
H10	0.4058	0.7812	0.3329	0.046*
C11	0.38215 (14)	0.92938 (9)	0.27610 (7)	0.0327 (2)
C12	0.33716 (17)	1.03505 (9)	0.29215 (7)	0.0389 (3)
H12	0.3411	1.0866	0.2468	0.047*
C13	0.28637 (16)	1.06381 (9)	0.37568 (8)	0.0386 (3)
H13	0.2579	1.1353	0.3863	0.046*
C14	0.47768 (19)	0.80181 (10)	0.16954 (8)	0.0476 (3)
H14A	0.5799	0.7789	0.2113	0.071*
H14B	0.5101	0.7994	0.1085	0.071*
H14C	0.3758	0.7548	0.1744	0.071*
O3	0.12918 (15)	0.25235 (7)	0.15969 (6)	0.0524 (3)
H3A	0.132 (2)	0.2167 (15)	0.1064 (13)	0.079*
H3B	0.043 (3)	0.2202 (15)	0.1837 (12)	0.079*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0757 (6)	0.0331 (5)	0.0436 (5)	0.0038 (4)	0.0213 (4)	0.0025 (3)
O2	0.0585 (5)	0.0437 (5)	0.0294 (4)	0.0024 (4)	0.0153 (4)	−0.0026 (3)
N1	0.0640 (7)	0.0597 (7)	0.0329 (5)	−0.0139 (6)	0.0142 (5)	−0.0099 (5)
N2	0.0434 (5)	0.0311 (5)	0.0262 (4)	−0.0011 (4)	0.0084 (4)	−0.0029 (3)
N3	0.0403 (5)	0.0376 (5)	0.0268 (4)	−0.0012 (4)	0.0080 (4)	−0.0049 (4)
C1	0.0388 (6)	0.0376 (6)	0.0305 (5)	−0.0030 (4)	0.0087 (4)	0.0006 (4)
C2	0.0504 (7)	0.0420 (6)	0.0419 (6)	−0.0061 (5)	0.0178 (5)	−0.0071 (5)
C3	0.0631 (8)	0.0673 (9)	0.0274 (5)	−0.0066 (7)	0.0022 (5)	0.0035 (5)
C4	0.0519 (7)	0.0495 (7)	0.0328 (6)	0.0038 (5)	0.0061 (5)	0.0075 (5)
C5	0.0367 (5)	0.0357 (6)	0.0274 (5)	−0.0046 (4)	0.0094 (4)	0.0016 (4)
C6	0.0358 (5)	0.0345 (5)	0.0311 (5)	0.0007 (4)	0.0086 (4)	0.0002 (4)
C7	0.0391 (6)	0.0347 (6)	0.0299 (5)	0.0000 (4)	0.0066 (4)	−0.0035 (4)
C8	0.0325 (5)	0.0366 (6)	0.0266 (5)	−0.0019 (4)	0.0045 (4)	−0.0029 (4)
C9	0.0519 (7)	0.0342 (6)	0.0287 (5)	−0.0014 (5)	0.0073 (5)	0.0030 (4)
C10	0.0518 (7)	0.0298 (5)	0.0332 (5)	0.0007 (4)	0.0082 (5)	−0.0028 (4)
C11	0.0335 (5)	0.0388 (6)	0.0264 (5)	−0.0027 (4)	0.0058 (4)	−0.0031 (4)
C12	0.0512 (7)	0.0357 (6)	0.0310 (5)	0.0022 (5)	0.0106 (5)	0.0055 (4)
C13	0.0494 (6)	0.0317 (6)	0.0364 (5)	0.0041 (5)	0.0118 (5)	−0.0004 (4)
C14	0.0590 (8)	0.0465 (7)	0.0402 (6)	−0.0032 (6)	0.0181 (5)	−0.0119 (5)
O3	0.0795 (7)	0.0408 (5)	0.0398 (5)	−0.0099 (4)	0.0196 (4)	−0.0081 (4)

Geometric parameters (Å, º)

O1—C6	1.2257 (14)	C7—C8	1.4623 (14)
O2—C11	1.3676 (12)	C7—H7	0.9300
O2—C14	1.4281 (15)	C8—C9	1.3875 (16)
N1—C3	1.3312 (19)	C8—C13	1.3910 (15)
N1—C2	1.3359 (17)	C9—C10	1.3864 (15)
N2—C6	1.3410 (14)	C9—H9	0.9300
N2—N3	1.3881 (12)	C10—C11	1.3868 (15)
N2—H2A	0.899 (14)	C10—H10	0.9300
N3—C7	1.2734 (14)	C11—C12	1.3811 (16)
C1—C2	1.3815 (15)	C12—C13	1.3787 (15)
C1—C5	1.3840 (15)	C12—H12	0.9300
C1—H1	0.9300	C13—H13	0.9300
C2—H2	0.9300	C14—H14A	0.9600
C3—C4	1.3812 (18)	C14—H14B	0.9600
C3—H3	0.9300	C14—H14C	0.9600
C4—C5	1.3899 (16)	O3—H3A	0.905 (19)
C4—H4	0.9300	O3—H3B	0.861 (19)
C5—C6	1.5041 (14)
C11—O2—C14	118.06 (9)	C8—C7—H7	118.5
C3—N1—C2	117.19 (11)	C9—C8—C13	117.99 (9)
C6—N2—N3	119.54 (9)	C9—C8—C7	123.55 (10)
C6—N2—H2A	121.6 (8)	C13—C8—C7	118.42 (10)
N3—N2—H2A	118.8 (8)	C10—C9—C8	121.32 (10)
C7—N3—N2	113.68 (9)	C10—C9—H9	119.3
C2—C1—C5	119.18 (11)	C8—C9—H9	119.3
C2—C1—H1	120.4	C9—C10—C11	119.41 (10)
C5—C1—H1	120.4	C9—C10—H10	120.3
N1—C2—C1	123.24 (12)	C11—C10—H10	120.3
N1—C2—H2	118.4	O2—C11—C12	114.99 (10)
C1—C2—H2	118.4	O2—C11—C10	124.85 (10)
N1—C3—C4	123.68 (12)	C12—C11—C10	120.14 (10)
N1—C3—H3	118.2	C13—C12—C11	119.73 (10)
C4—C3—H3	118.2	C13—C12—H12	120.1
C3—C4—C5	118.75 (12)	C11—C12—H12	120.1
C3—C4—H4	120.6	C12—C13—C8	121.41 (10)
C5—C4—H4	120.6	C12—C13—H13	119.3
C1—C5—C4	117.89 (10)	C8—C13—H13	119.3
C1—C5—C6	124.05 (9)	O2—C14—H14A	109.5
C4—C5—C6	118.04 (10)	O2—C14—H14B	109.5
O1—C6—N2	124.47 (10)	H14A—C14—H14B	109.5
O1—C6—C5	121.11 (10)	O2—C14—H14C	109.5
N2—C6—C5	114.37 (9)	H14A—C14—H14C	109.5
N3—C7—C8	123.09 (10)	H14B—C14—H14C	109.5
N3—C7—H7	118.5	H3A—O3—H3B	102.8 (16)
C6—N2—N3—C7	−176.33 (10)	N2—N3—C7—C8	176.10 (9)
C3—N1—C2—C1	−2.25 (18)	N3—C7—C8—C9	−6.98 (17)
C5—C1—C2—N1	0.82 (18)	N3—C7—C8—C13	175.28 (11)
C2—N1—C3—C4	1.4 (2)	C13—C8—C9—C10	−0.03 (17)
N1—C3—C4—C5	0.9 (2)	C7—C8—C9—C10	−177.78 (11)
C2—C1—C5—C4	1.51 (16)	C8—C9—C10—C11	−0.42 (18)
C2—C1—C5—C6	−177.26 (10)	C14—O2—C11—C12	179.83 (10)
C3—C4—C5—C1	−2.30 (18)	C14—O2—C11—C10	−1.16 (16)
C3—C4—C5—C6	176.54 (11)	C9—C10—C11—O2	−178.74 (10)
N3—N2—C6—O1	−4.99 (17)	C9—C10—C11—C12	0.22 (17)
N3—N2—C6—C5	172.25 (9)	O2—C11—C12—C13	179.48 (10)
C1—C5—C6—O1	−143.49 (12)	C10—C11—C12—C13	0.42 (18)
C4—C5—C6—O1	37.74 (16)	C11—C12—C13—C8	−0.89 (18)
C1—C5—C6—N2	39.17 (15)	C9—C8—C13—C12	0.68 (17)
C4—C5—C6—N2	−139.59 (11)	C7—C8—C13—C12	178.56 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O1^i	0.861 (19)	2.02 (2)	2.8794 (14)	176.9 (17)
O3—H3A···N1^ii	0.905 (19)	1.902 (19)	2.8071 (14)	179.7 (18)
N2—H2A···O3^iii	0.899 (14)	2.039 (15)	2.9324 (15)	172.2 (12)

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