N′-[(E)-4-Methyl­benzyl­idene]pyridine-4-carbo­hydrazide monohydrate

Pereira Almeida, W.; Paes Koury, I.; Simoni, D. de A.

doi:10.1107/S2414314616007525

organic compounds

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ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160752

doi:10.1107/S2414314616007525

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N′-[(E)-4-Methylbenzylidene]pyridine-4-carbohydrazide monohydrate

Wanda Pereira Almeida,^a,^b Isabela Paes Koury ^a and Deborah de Alencar Simoni ^c ^*

^aLaboratory of Drug Design and Development, Institute of Chemistry, University of Campinas, PO Box 6154 – 13083-970, Campinas, SP, Brazil, ^bFaculty of Pharmaceutical Sciences, University of Campinas, PO Box 6029 – 13083-859, Campinas, SP, Brazil, and ^cLaboratory of Single Crystal X-Ray Diffraction, Institute of Chemistry, University of Campinas, PO Box 6154 – 13083-970, Campinas, SP, Brazil
^*Correspondence e-mail: wanda.almeida@fcf.unicamp.br

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 20 April 2016; accepted 4 May 2016; online 10 May 2016)

In the title hydrate, C₁₄H₁₃N₃O·H₂O, the C=N double bond adopts an E conformation and the dihedral angle between the aromatic rings is 16.36 (10)°. In the crystal, N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds link the components into (001) sheets.

Keywords: crystal structure; acylhydrazone; hydrate; hydrogen bonding.

CCDC reference: 1478220

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Chemical scheme

Structure description

N-Acylhydrazone (NAH) derivatives show various biological properties including antitumor (Maia et al., 2014 ), antimalarial (Melnyk et al., 2006 ) and anti-inflammatory (Moldovan et al., 2011 ) activities and, therefore, are potential therapeutic agents.

The method of synthesis of the title compound was a condensation reaction between a hydrazide and an aldehyde, and the asymmetric unit of the crystal structure is made up of one molecule of N′-[(E)-(4-methylphenyl) methylidene] pyridine-4-carbohydrazide and one water molecule (Fig. 1).

Figure 1
The molecular structure of the title compound with 50% probability displacement ellipsoids. Hydrogen bonds are shown as dashed lines

The title compound presents an (E) conformation relative to the C8=N2 bond, with the pyridine ring and the central spacer unit (C4–C8–N2–N1–C9–C10) being essentially planar (r.m.s. deviations of 0.006 and 0.066 Å, respectively), as in other reported NAH derivatives (Bhat et al., 2012 ; de Souza et al., 2007 ; Shafiq et al., 2009 ). The dihedral angle between the pyridine ring and the spacer unit is 16.36 (10)° and the structure shows the following torsion angles: C5—C4—C8—N2 = −169.34 (18)°, C4—C8—N2—N1 = −172.76 (15)°, C8—N2—N1—C9 = −173.08 (17)°, N2—N1—C9—C10 = −172.66 (16)° and N1—C9—C10—C11 = −33.6 (3)°.

In the crystal, hydrogen bonds occur between the NAH and water molecules (Table 1). The N1—H1⋯O2 bond is nearly linear (173°) as is observed in analogous monohydrated NAH structures bearing different phenyl substituents (Bhat et al., 2012; de Souza et al., 2007). The present compound has O2—H2A⋯N3 and N1—H1⋯O2 hydrogen bonds forming a chain in the [010] direction, while another chain is built along [100] from O2—H2B⋯N2, O2—H2B⋯O1 and N1—H1⋯O2 hydrogen bonds (Fig. 2). Taken together, (001) sheets arise.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.85 (2)	1.93 (2)	2.775 (2)	173 (2)
O2—H2A⋯N3ⁱⁱ	0.87 (3)	1.97 (3)	2.832 (2)	169 (2)
O2—H2B⋯O1	0.84 (3)	2.25 (3)	2.919 (2)	136 (2)
O2—H2B⋯N2	0.84 (3)	2.44 (3)	3.184 (2)	147 (2)
Symmetry codes: (i) x-1, y, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Crystal packing of the title compound, showing hydrogen-bonding interactions as dashed lines.

Synthesis and crystallization

An equimolar mixture of isonicotinic acid hydrazide and 4-methylbenzaldehyde were refluxed in ethanol for 10 h, followed by solvent removal in a rotatory evaporator. The residue was washed three times with a hot 1:1 mixture of hexane–ethyl acetate and the residual solvent was removed by filtration. Light brown needles (m.p. 192–194°C) were obtained by recrystallization from reagent-grade ethanol (ethanol/water, 97:3 v/v) solution.

¹H NMR (d₆-DMSO, 500 MHz) d 12.04 (s, 1H, H1); 8.46 (s, 1H, H8); 8.79 (dd, J = 1.6 and 4.5 Hz, 2H, H12 and H13); 7.85 (dd, J = 1.6 and 4.5 Hz, 2H, H11 and H14); 7.66 (d, J = 8 Hz, 2H, H3 and H5); 7.30 (d, J = 8 Hz, 2H, H2 and H6); 2.37 (s, 3H, H7).

¹³C NMR (d₆-DMSO, 125 MHz) d 161.9 (C9), 150.78 (C12, C13), 149.53 (C8), 141.02 (C10), 140.77 (C4), 131.84 (C1), 129.99 (C3, C5), 127.71 (C2, C6), 122.05 (C11, C14), 21.53 (C7).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₃N₃O·H₂O
M_r	257.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	150
a, b, c (Å)	6.3268 (8), 7.2868 (10), 28.272 (4)
V (Å³)	1303.4 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.23 × 0.11

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2010 )
T_min, T_max	0.701, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	13953, 2546, 2426
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 1.06
No. of reflections	2546
No. of parameters	182
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15
Computer programs: APEX2 and SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2006 ), OLEX2 (Dolomanov et al., 2003 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1478220

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616007525/hb4039sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616007525/hb4039Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616007525/hb4039Isup3.cdx

Supporting information file. DOI: 10.1107/S2414314616007525/hb4039Isup4.cml

checkCIF report

Structure description top

N-Acylhydrazone (NAH) derivatives show various biological properties including antitumor (Maia et al., 2014), antimalarial (Melnyk et al., 2006) and anti-inflammatory (Moldovan et al., 2011) activities and, therefore, are potential therapeutic agents.

The method of synthesis of the title compound was a condensation reaction between a hydrazide and an aldehyde, and the asymmetric unit of the crystal structure is made up of one molecule of N'-[(E)-(4-methylphenyl) methylidene] pyridine-4-carbohydrazide and one water molecule (Fig. 1).

The title compound presents an (E) conformation relative to the C8=N2 bond, with the pyridine ring and the central spacer unit (C4—C8—N2—N1—C9—C10) being essentially planar (rms deviations of 0.006 Å and 0.066 Å, respectively), as in other reported NAH derivatives (Bhat et al., 2012; de Souza et al., 2007; Shafiq et al., 2009). The dihedral angle between the pyridine ring and the spacer unit is 16.36 (10)° and the structure shows the following torsion angles: C5—C4—C8—N2 (-169.34 (18)°), C4—C8—N2—N1 (-172.76 (15)°), C8—N2—N1—C9 (-173.08 (17)°), N2—N1—C9—C10 (-172.66 (16)°), N1—C9—C10—C11 (-33.6 (3)°).

In the crystal, hydrogen bonds occur between the NAH and water molecules (Tab. 1). The N1—H1···O2 bond is nearly linear (173°) as it is observed in analogous monohydrated NAH structures bearing different phenyl substituents (Bhat et al., 2012; de Souza et al., 2007). The present compound has O2—H2A···N3 and N1—H1···O2 hydrogen bonds forming a chain in the [010] direction, while another chain is built along [100] from O2—H2B···N2, O2—H2B···O1 and N1—H1···O2 hydrogen bonds (Fig. 2). Taken together, (001) sheets arise.

Synthesis and crystallization xperimental top

An equimolar mixture of isonicotinic acid hydrazide and 4-methylbenzaldehyde were refluxed in ethanol for 10 hours, followed by solvent removal in a rotatory evaporator. The residue was washed three times with a hot 1:1 mixture of hexane-ethyl acetate and the residual solvent was removed by filtration. Light brown needles (mp 192 - 194 °C) were obtained by recrystallization from reagent-grade ethanol (ethanol/water, 97:3 - v/v) solution.

¹H NMR (d₆-DMSO, 500 MHz) d 12.04 (s, 1H, H1); 8.46 (s, 1H, H8); 8.79 (dd, J = 1.6 and 4.5 Hz, 2H, H12 and H13); 7.85 (dd, J = 1.6 and 4.5 Hz, 2H, H11 and H14); 7.66 (d, J = 8Hz, 2H, H3 and H5); 7.30 (d, J = 8 Hz, 2H, H2 and H6); 2.37 (s, 3H, H7);

¹³C NMR (d₆-DMSO, 125 MHz) d 161.9 (C9), 150.78 (C12, C13), 149.53 (C8), 141.02 (C10), 140.77 (C4), 131.84 (C1), 129.99 (C3, C5), 127.71 (C2, C6), 122.05 (C11, C14), 21.53 (C7).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms attached to N and O atoms were placed in the difference Fourier map and refined freely (O – H = 0.87 (3) and 0.84 (3) Å and N – H = 0.85 (2)Å), with Uiso(H) = 1.5Ueq(O) and Uiso(H) = 1.2Ueq(N). H atoms in C—H bond were located in idealized positions and treated by riding model, with Uiso(H) = 1.5Ueq(C) (C – H = 0.96 Å) or Uiso(H) = 1.2Ueq(C) (C – H = 0.93 Å). A rotating-group model was applied to the methyl group.

Related literature top

For chemical and structural details, therapeutic profile and perspective of the application of N-acylhydrazones, see: Maia, Tesch & Fraga et al. (2014), Melnyk et al. (2006) and Moldovan et al. (2011). For other reported NAH derivatives, see Bhat et al. (2012), de Souza et al. (2007) and Shafiq et al. (2009).

Experimental top

An equimolar mixture of isonicotinic acid hydrazide and 4-methylbenzaldehyde were refluxed in ethanol for 10 h, followed by solvent removal in a rotatory evaporator. The residue was washed three times with a hot 1:1 mixture of hexane–ethyl acetate and the residual solvent was removed by filtration. Light brown needles (m.p. 192-194°C) were obtained by recrystallization from reagent-grade ethanol (ethanol/water, 97:3 v/v) solution.

¹³C NMR (d₆-DMSO, 125 MHz) d 161.9 (C9), 150.78 (C12, C13), 149.53 (C8), 141.02 (C10), 140.77 (C4), 131.84 (C1), 129.99 (C3, C5), 127.71 (C2, C6), 122.05 (C11, C14), 21.53 (C7).

Structure description top

N-Acylhydrazone (NAH) derivatives show various biological properties including antitumor (Maia et al., 2014), antimalarial (Melnyk et al., 2006) and anti-inflammatory (Moldovan et al., 2011) activities and, therefore, are potential therapeutic agents.

The method of synthesis of the title compound was a condensation reaction between a hydrazide and an aldehyde, and the asymmetric unit of the crystal structure is made up of one molecule of N'-[(E)-(4-methylphenyl) methylidene] pyridine-4-carbohydrazide and one water molecule (Fig. 1).

The title compound presents an (E) conformation relative to the C8=N2 bond, with the pyridine ring and the central spacer unit (C4–C8–N2–N1–C9–C10) being essentially planar (r.m.s. deviations of 0.006 and 0.066 Å, respectively), as in other reported NAH derivatives (Bhat et al., 2012; de Souza et al., 2007; Shafiq et al., 2009). The dihedral angle between the pyridine ring and the spacer unit is 16.36 (10)° and the structure shows the following torsion angles: C5—C4—C8—N2 = -169.34 (18)°, C4—C8—N2—N1 = -172.76 (15)°, C8—N2—N1—C9 = -173.08 (17)°, N2—N1—C9—C10 = -172.66 (16)° and N1—C9—C10—C11 = -33.6 (3)°.

In the crystal, hydrogen bonds occur between the NAH and water molecules (Table 1). The N1—H1···O2 bond is nearly linear (173°) as is observed in analogous monohydrated NAH structures bearing different phenyl substituents (Bhat et al., 2012; de Souza et al., 2007). The present compound has O2—H2A···N3 and N1—H1···O2 hydrogen bonds forming a chain in the [010] direction, while another chain is built along [100] from O2—H2B···N2, O2—H2B···O1 and N1—H1···O2 hydrogen bonds (Fig. 2). Taken together, (001) sheets arise.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2003) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound with 50% probability displacement ellipsoids. Hydrogen bonds are shown as dashed lines
	Fig. 2. Crystal packing of the title compound, showing hydrogen-bonding interactions as dashed lines.

N'-[(E)-4-Methylbenzylidene]pyridine-4-carbohydrazide monohydrate top

Crystal data top

C₁₄H₁₃N₃O·H₂O	D_x = 1.311 Mg m⁻³
M_r = 257.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 6782 reflections
a = 6.3268 (8) Å	θ = 2.9–28.1°
b = 7.2868 (10) Å	µ = 0.09 mm⁻¹
c = 28.272 (4) Å	T = 150 K
V = 1303.4 (3) Å³	Block, light brown
Z = 4	0.30 × 0.23 × 0.11 mm
F(000) = 544

Data collection top

Bruker APEX CCD diffractometer	2546 independent reflections
Radiation source: fine-focus sealed tube	2426 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm^-1	R_int = 0.023
phi and ω scans	θ_max = 26.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −7→5
T_min = 0.701, T_max = 0.746	k = −8→8
13953 measured reflections	l = −34→34

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.030	H-atom parameters not refined
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.0433P)² + 0.2529P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2546 reflections	Δρ_max = 0.17 e Å⁻³
182 parameters	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₄H₁₃N₃O·H₂O	V = 1303.4 (3) Å³
M_r = 257.29	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.3268 (8) Å	µ = 0.09 mm⁻¹
b = 7.2868 (10) Å	T = 150 K
c = 28.272 (4) Å	0.30 × 0.23 × 0.11 mm

Data collection top

Bruker APEX CCD diffractometer	2546 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2010)	2426 reflections with I > 2σ(I)
T_min = 0.701, T_max = 0.746	R_int = 0.023
13953 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.079	H-atom parameters not refined
S = 1.06	Δρ_max = 0.17 e Å⁻³
2546 reflections	Δρ_min = −0.15 e Å⁻³
182 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.6820 (2)	0.1768 (2)	0.82914 (5)	0.0324 (4)
N1	0.3922 (3)	0.2683 (2)	0.87038 (5)	0.0191 (3)
H1	0.264 (4)	0.305 (3)	0.8707 (7)	0.023*
N2	0.5160 (2)	0.3223 (2)	0.90852 (5)	0.0198 (3)
N3	0.1151 (3)	0.0996 (3)	0.70795 (6)	0.0287 (4)
C1	0.7141 (3)	0.6081 (3)	1.06567 (7)	0.0243 (4)
C2	0.8199 (3)	0.5942 (3)	1.02236 (7)	0.0239 (4)
H2	0.9561	0.6410	1.0195	0.029*
C3	0.7252 (3)	0.5121 (3)	0.98366 (7)	0.0208 (4)
H3	0.7981	0.5045	0.9552	0.025*
C4	0.5213 (3)	0.4408 (2)	0.98708 (6)	0.0189 (4)
C5	0.4149 (3)	0.4541 (3)	1.03019 (6)	0.0221 (4)
H5	0.2787	0.4073	1.0331	0.027*
C6	0.5113 (3)	0.5370 (3)	1.06885 (7)	0.0248 (4)
H6	0.4385	0.5448	1.0974	0.030*
C7	0.8197 (4)	0.6995 (3)	1.10712 (7)	0.0340 (5)
H7A	0.9438	0.6316	1.1158	0.051*
H7B	0.7237	0.7029	1.1334	0.051*
H7C	0.8589	0.8225	1.0986	0.051*
C8	0.4135 (3)	0.3616 (2)	0.94615 (6)	0.0194 (4)
H8	0.2689	0.3396	0.9475	0.023*
C9	0.4911 (3)	0.2065 (3)	0.83144 (6)	0.0209 (4)
C10	0.3516 (3)	0.1727 (3)	0.78939 (7)	0.0198 (4)
C11	0.1448 (3)	0.1115 (3)	0.79248 (7)	0.0213 (4)
H11	0.0809	0.0950	0.8218	0.026*
C12	0.0350 (3)	0.0753 (3)	0.75110 (7)	0.0246 (4)
H12	−0.1027	0.0314	0.7536	0.030*
C13	0.3135 (3)	0.1616 (3)	0.70536 (7)	0.0308 (5)
H13	0.3714	0.1810	0.6755	0.037*
C14	0.4377 (3)	0.1987 (3)	0.74447 (7)	0.0265 (4)
H14	0.5758	0.2401	0.7409	0.032*
O2	0.9875 (2)	0.4131 (2)	0.87689 (5)	0.0234 (3)
H2A	0.972 (4)	0.478 (3)	0.8513 (9)	0.035*
H2B	0.878 (4)	0.348 (4)	0.8789 (8)	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0160 (7)	0.0502 (10)	0.0311 (7)	0.0006 (7)	−0.0008 (6)	−0.0098 (7)
N1	0.0147 (7)	0.0234 (9)	0.0190 (8)	0.0002 (6)	−0.0037 (6)	−0.0016 (6)
N2	0.0182 (7)	0.0210 (8)	0.0201 (8)	−0.0004 (6)	−0.0052 (6)	0.0000 (6)
N3	0.0286 (9)	0.0357 (10)	0.0218 (8)	−0.0023 (8)	−0.0022 (7)	−0.0051 (8)
C1	0.0321 (10)	0.0163 (9)	0.0244 (9)	0.0019 (8)	−0.0099 (8)	0.0015 (7)
C2	0.0220 (9)	0.0185 (10)	0.0312 (10)	−0.0016 (9)	−0.0060 (8)	0.0010 (8)
C3	0.0222 (9)	0.0188 (10)	0.0214 (9)	0.0003 (8)	0.0003 (7)	0.0012 (7)
C4	0.0209 (9)	0.0151 (9)	0.0206 (9)	0.0029 (8)	−0.0033 (7)	0.0018 (7)
C5	0.0202 (8)	0.0216 (10)	0.0246 (9)	−0.0001 (8)	−0.0011 (8)	0.0034 (8)
C6	0.0329 (10)	0.0230 (10)	0.0185 (8)	0.0023 (9)	−0.0006 (8)	0.0011 (7)
C7	0.0471 (13)	0.0257 (11)	0.0292 (11)	−0.0039 (10)	−0.0114 (10)	−0.0015 (9)
C8	0.0187 (8)	0.0182 (10)	0.0212 (9)	−0.0002 (7)	−0.0039 (7)	0.0036 (7)
C9	0.0178 (9)	0.0216 (9)	0.0232 (9)	−0.0013 (8)	0.0001 (7)	−0.0005 (7)
C10	0.0197 (9)	0.0181 (9)	0.0215 (9)	0.0016 (7)	0.0002 (7)	−0.0020 (8)
C11	0.0200 (9)	0.0240 (10)	0.0199 (9)	−0.0001 (7)	0.0020 (7)	−0.0009 (8)
C12	0.0198 (9)	0.0282 (10)	0.0259 (9)	−0.0023 (8)	−0.0001 (8)	−0.0048 (9)
C13	0.0333 (10)	0.0412 (13)	0.0179 (9)	−0.0055 (9)	0.0050 (9)	0.0001 (9)
C14	0.0216 (9)	0.0311 (11)	0.0268 (10)	−0.0054 (8)	0.0043 (8)	0.0000 (9)
O2	0.0171 (6)	0.0320 (8)	0.0211 (7)	−0.0004 (6)	−0.0024 (5)	0.0034 (6)

Geometric parameters (Å, º) top

O1—C9	1.228 (2)	C5—H5	0.9300
N1—C9	1.344 (2)	C6—H6	0.9300
N1—N2	1.390 (2)	C7—H7A	0.9600
N1—H1	0.85 (2)	C7—H7B	0.9600
N2—C8	1.278 (2)	C7—H7C	0.9600
N3—C12	1.333 (3)	C8—H8	0.9300
N3—C13	1.337 (3)	C9—C10	1.501 (3)
C1—C6	1.387 (3)	C10—C11	1.385 (3)
C1—C2	1.399 (3)	C10—C14	1.395 (3)
C1—C7	1.504 (3)	C11—C12	1.386 (3)
C2—C3	1.383 (3)	C11—H11	0.9300
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.394 (3)	C13—C14	1.383 (3)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.396 (3)	C14—H14	0.9300
C4—C8	1.462 (2)	O2—H2A	0.87 (3)
C5—C6	1.390 (3)	O2—H2B	0.84 (3)

C9—N1—N2	117.89 (15)	C1—C7—H7C	109.5
C9—N1—H1	123.9 (14)	H7A—C7—H7C	109.5
N2—N1—H1	115.9 (14)	H7B—C7—H7C	109.5
C8—N2—N1	115.04 (15)	N2—C8—C4	120.71 (17)
C12—N3—C13	116.90 (17)	N2—C8—H8	119.6
C6—C1—C2	118.19 (18)	C4—C8—H8	119.6
C6—C1—C7	121.7 (2)	O1—C9—N1	124.07 (18)
C2—C1—C7	120.07 (19)	O1—C9—C10	120.47 (17)
C3—C2—C1	121.08 (18)	N1—C9—C10	115.46 (16)
C3—C2—H2	119.5	C11—C10—C14	118.06 (17)
C1—C2—H2	119.5	C11—C10—C9	123.94 (17)
C2—C3—C4	120.45 (18)	C14—C10—C9	117.97 (16)
C2—C3—H3	119.8	C10—C11—C12	118.80 (18)
C4—C3—H3	119.8	C10—C11—H11	120.6
C3—C4—C5	118.76 (17)	C12—C11—H11	120.6
C3—C4—C8	121.58 (17)	N3—C12—C11	123.81 (17)
C5—C4—C8	119.58 (16)	N3—C12—H12	118.1
C6—C5—C4	120.34 (18)	C11—C12—H12	118.1
C6—C5—H5	119.8	N3—C13—C14	123.77 (19)
C4—C5—H5	119.8	N3—C13—H13	118.1
C1—C6—C5	121.17 (19)	C14—C13—H13	118.1
C1—C6—H6	119.4	C13—C14—C10	118.65 (17)
C5—C6—H6	119.4	C13—C14—H14	120.7
C1—C7—H7A	109.5	C10—C14—H14	120.7
C1—C7—H7B	109.5	H2A—O2—H2B	106 (2)
H7A—C7—H7B	109.5

C9—N1—N2—C8	−173.08 (17)	N2—N1—C9—O1	7.9 (3)
C6—C1—C2—C3	0.1 (3)	N2—N1—C9—C10	−172.66 (16)
C7—C1—C2—C3	−179.5 (2)	O1—C9—C10—C11	145.9 (2)
C1—C2—C3—C4	−0.1 (3)	N1—C9—C10—C11	−33.6 (3)
C2—C3—C4—C5	0.1 (3)	O1—C9—C10—C14	−32.0 (3)
C2—C3—C4—C8	176.90 (18)	N1—C9—C10—C14	148.60 (19)
C3—C4—C5—C6	0.0 (3)	C14—C10—C11—C12	1.4 (3)
C8—C4—C5—C6	−176.91 (17)	C9—C10—C11—C12	−176.45 (18)
C2—C1—C6—C5	−0.1 (3)	C13—N3—C12—C11	0.4 (3)
C7—C1—C6—C5	179.5 (2)	C10—C11—C12—N3	−1.5 (3)
C4—C5—C6—C1	0.0 (3)	C12—N3—C13—C14	0.8 (3)
N1—N2—C8—C4	−172.76 (15)	N3—C13—C14—C10	−0.9 (3)
C3—C4—C8—N2	13.9 (3)	C11—C10—C14—C13	−0.2 (3)
C5—C4—C8—N2	−169.34 (18)	C9—C10—C14—C13	177.69 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.85 (2)	1.93 (2)	2.775 (2)	173 (2)
O2—H2A···N3ⁱⁱ	0.87 (3)	1.97 (3)	2.832 (2)	169 (2)
O2—H2B···O1	0.84 (3)	2.25 (3)	2.919 (2)	136 (2)
O2—H2B···N2	0.84 (3)	2.44 (3)	3.184 (2)	147 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.85 (2)	1.93 (2)	2.775 (2)	173 (2)
O2—H2A···N3ⁱⁱ	0.87 (3)	1.97 (3)	2.832 (2)	169 (2)
O2—H2B···O1	0.84 (3)	2.25 (3)	2.919 (2)	136 (2)
O2—H2B···N2	0.84 (3)	2.44 (3)	3.184 (2)	147 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃N₃O·H₂O
M_r	257.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	150
a, b, c (Å)	6.3268 (8), 7.2868 (10), 28.272 (4)
V (Å³)	1303.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.23 × 0.11

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2010)
T_min, T_max	0.701, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	13953, 2546, 2426
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.079, 1.06
No. of reflections	2546
No. of parameters	182
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.15

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), Mercury (Macrae et al., 2006), OLEX2 (Dolomanov et al., 2003) and publCIF (Westrip, 2010).

Acknowledgements

The authors are grateful to the Fundação de Amparo a Pesquisa do Estado de São Paulo (FAPESP 2009/51602–5 and 2013/18203–5) for financial support and to the Programa Institucional de Bolsas de Iniciação Científica of the Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (PIBIC-CNPq) for a fellowship for IPK.

References

Bhat, M. A., Abdel-Aziz, H. A., Ghabbour, H. A., Hemamalini, M. & Fun, H.-K. (2012). Acta Cryst. E68, o1002. CSD CrossRef IUCr Journals Google Scholar
Bruker (2010). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Blake, A. J., Champness, N. R. & Schröder, M. (2003). J. Appl. Cryst. 36, 1283–1284. Web of Science CrossRef CAS IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Maia, R. D., do C., Tesch, R. & Fraga, C. A. M. (2014). Expert Opin. Ther. Pat. 24, 1161–1170. Google Scholar
Melnyk, P., Leroux, V., Sergheraert, C. & Grellier, P. (2006). Bioorg. Med. Chem. Lett. 16, 31–35. Web of Science CrossRef PubMed CAS Google Scholar
Moldovan, C. M., Oniga, O., Pârvu, A., Tiperciuc, B., Verite, P., Pîrnău, A., Crişan, O., Bojiţă, M. & Pop, R. (2011). Eur. J. Med. Chem. 46, 526–534. Web of Science CrossRef CAS PubMed Google Scholar
Shafiq, Z., Yaqub, M., Tahir, M. N., Hussain, A. & Iqbal, M. S. (2009). Acta Cryst. E65, o2899. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Souza, M. V. N. de, Wardell, S. M. S. V., Wardell, J. L., Low, J. N. & Glidewell, C. (2007). Acta Cryst. C63, o166–o168. Web of Science CSD CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 1| Part 5| May 2016| x160752

doi:10.1107/S2414314616007525

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

N′-[(E)-4-Methyl­benzyl­­idene]pyridine-4-carbo­hydrazide monohydrate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

N′-[(E)-4-Methylbenzylidene]pyridine-4-carbohydrazide monohydrate