Crystal structure of (E)-N′-(5-bromo-2-hy­droxy­benzyl­idene)nicotinohydrazide monohydrate

Sravya, S.; Sruthy, S.; Aiswarya, N.; Sithambaresan, M.; Kurup, M.R.P.

doi:10.1107/S2056989015009627

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ISSN: 2056-9890

Volume 71| Part 7| July 2015| Pages 734-736

doi:10.1107/S2056989015009627

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Crystal structure of (E)-N′-(5-bromo-2-hydroxybenzylidene)nicotinohydrazide monohydrate

S. Sravya,^a S. Sruthy,^a N. Aiswarya,^b M. Sithambaresan ^c ^* and M. R. Prathapachandra Kurup ^b

^aDepartment of Chemistry, Amrita Vishwa Vidyapeetham, Clappana PO, Kollam 690 525, India, ^bDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India, and ^cDepartment of Chemistry, Faculty of Science, Eastern University, Chenkalady, Sri Lanka
^*Correspondence e-mail: msithambaresan@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 4 May 2015; accepted 19 May 2015; online 3 June 2015)

In the title compound, C₁₃H₁₀BrN₃O₂·H₂O, the conformation about the azomethine double bond is E. The molecule exists in the amido form with a C=O bond length of 1.229 (2) Å. There is an intramolecular O—H⋯N hydrogen bond forming an S(6) ring motif. The whole molecule is almost planar, with an r.m.s. deviation of 0.021 Å for all non-H atoms, and the dihedral angle between the planes of the pyridine and benzene rings is 0.74 (12)°. In the crystal, the water molecule of crystallization links the organic molecules via Ow—H⋯O, Ow—H⋯N and N—H⋯Ow hydrogen bonds and short C—H⋯Ow contacts, forming sheets lying parallel to (100). Within the sheets there is a weak π–π interaction involving the pyridine and benzene rings [centroid-to-centroid distance = 3.8473 (15) Å]. The sheets are linked via C—H⋯Br interactions, forming a three-dimensional network.

Keywords: crystal structure; aroylhydrazone; carbohydrazide; nicotinohydrazide; hydrogen bonding.

CCDC reference: 1401825

1. Chemical context

Aroylhydrazones can coordinate to transition metals either in the amido form (Bessy Raj & Kurup, 2007 ) or in the iminolato form (Ghosh et al., 2005 ; Galić et al., 2011 ), leading to the formation of two types of complexes. Hydrazones derived from isonicotinoyl hydrazides are potential drugs for the treatment of the iron-overload associated diseases (Macková et al., 2012 ). They are associated with a broad spectrum of biological activities, and studies have shown that nicotinic acid hydrazones could be considered as anti-inflammatory and analgesic agents (Navidpour et al., 2014 ; Kheradmand et al., 2013 ) and as a novel pharmacophore in the design of anticonvulsant drugs (Sinha et al., 2011 ). Hydrazones have been used in chemical processes, in non-linear optics and as sensors as well as in catalytic processes (Hosseini-Monfared et al., 2013 ; Du & Hong, 2014 ). Their potential as analytical reagents (Galić et al., 2011) and their uses as molecular switches, metallo-assemblies and sensors have also been reported (Su & Aprahamian, 2014 ). Salicylaldehyde isonicotinoylhydrazone has also been used for the spectrophotometric determination of gallium(III) and indium(III) (Reddy et al., 2011 ).

2. Structural commentary

The title compound, Fig. 1, exists in the amido form with a C8=O2 bond length of 1.229 (2) Å. The molecule has an E conformation with respect to the azomethine bond, which is confirmed by the torsion angle C6—C7=N1—N2 of 179.09 (19)°. The two aromatic rings (C1–C6 and N3/C9–C13), are inclined to the almost planar hydrazone moiety [O2/C8/N2/N1/C7; planar to within 0.006 (2) Å] by 2.12 (9) and 1.40 (8)°, respectively, and to each other by 0.74 (12)°. There is an intramolecular O—H⋯N hydrogen bond present in the molecule that involves the phenolic oxygen, O1 and the azomethine nitrogen atom, N1, forming an S(6) ring motif (Table 1 and Fig. 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.86 (1)	1.91 (2)	2.641 (2)	143 (3)
O1W—H1A⋯O2	0.85 (1)	1.91 (1)	2.756 (2)	172 (3)
O1W—H1B⋯N3ⁱ	0.85 (1)	2.03 (1)	2.845 (3)	162 (2)
N2—H2′⋯O1Wⁱⁱ	0.87 (1)	1.95 (1)	2.806 (3)	169 (3)
C7—H7⋯O1Wⁱⁱ	0.93	2.49	3.263 (3)	140
C10—H10⋯O1Wⁱⁱ	0.93	2.45	3.362 (3)	165
C11—H11⋯Br1ⁱⁱⁱ	0.93	2.93	3.825 (3)	162
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x-1, y, z-1.

Figure 1
A view of the molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, the water molecule forms three hydrogen bonds with three different nicotinic hydrazone molecules (Table 1 and Fig. 2). This compound is an example of a system where a single atom acts both as donor and acceptor. There are also C—H⋯O(water) contacts present enclosing R₂¹(6) and R₂¹(7) ring motifs (Fig. 2). Finally sheets are formed lying parallel to (100). There are weak π–π interactions within the sheets involving the bromine-bearing aromatic ring of one molecule and the pyridine ring of another, with a centroid–centroid distance of 3.8473 (15) Å (Fig. 2). The sheets are linked via C—H⋯Br interactions, forming a three-dimensional network (Table 1 and Fig. 3).

Figure 2
Hydrogen bonds (dashed lines) and a weak π–π interaction (in blue) in the crystal of the title compound [symmetry codes: (i) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (ii) −x, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ].

Figure 3
A view along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1

for details) and H atoms not involved in hydrogen bonding have been omitted for clarity.

4. Database survey

A search of the Cambridge Structural Database (Version 5.36, update Feb. 2015; Groom & Allen, 2014 ) yielded 22 hits for the substructure N′-(2-hydroxybenzylidene)nicotinohydrazide. The crystal structure of N′-(2-hydroxybenzylidene)nicotinohydrazide itself is reported as a monohydrate (IDASUB; Galić et al., 2001 ), and the crystal structure of the chloro derivative of the title compound, which crystallized with two independent molecules in the asymmetric unit, has also been reported (MOZPIB; Ren, 2009 ). In these two compounds, an intramolecular O—H⋯N hydrogen bond is also present. The molecules are also relatively planar, with the benzene and pyridine rings being inclined to one another by ca 4.2° in IDASUB, and by ca 12.8 and 1.9° in the two independent molecules of MOZPIB. This last dihedral angle is similar to that in the title compound [cf. 0.74 (12)°]. In the crystal structure of N′-(2-hydroxybenzylidene)nicotinohydrazide monohydrate (IDASUB), the water molecule forms three hydrogen bonds and is another example of a system where a single atom acts both as donor and acceptor.

5. Synthesis and crystallization

The title compound was prepared by adapting a reported procedure (Mathew & Kurup, 2011 ). A methanolic solution of 5-bromosalicylaldehyde (0.10051 g, 0.5 mmol) and nicotinic hydrazide (0.06857 g, 0.5 mmol) was refluxed for 3 h with two drops of glacial acetic acid. Light-yellow block-shaped crystals of the title compound were obtained by slow evaporation of the solvent. The crystals were filtered, washed with minimum quantity of methanol and dried over P₄O₁₀ in vacuo (yield: 0.22 g, 68.5%; m.p.: 480 K). Elemental analysis calculated for C₁₃H₁₀N₃O₂Br·H₂O: C, 46.17, H, 3.58, N, 12.43%; found: C, 46.14, H, 3.57, N, 12.44%. IR FT–IR (KBr, cm⁻¹) 3059 (NH), 3269(OH), 1680 (C=O), 1584 (C=N).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The water, hydroxyl and NH H atoms were located in difference Fourier maps and refined with distances restraints: O—H = 0.86 (1) Å and N—H = 0.88 (1) Å. All C-bound H atoms were placed in calculated positions and refined as riding: C—H = 0.93 Å with U_iso(H) = 1.2U_eq(C). Three reflections were omitted owing to bad agreement, viz. 100, 110 and 200.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₀BrN₃O₂·H₂O
M_r	338.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.1623 (7), 12.5953 (9), 13.2510 (8)
β (°)	90.226 (3)
V (Å³)	1362.28 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.03
Crystal size (mm)	0.42 × 0.12 × 0.11

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.349, 0.356
No. of measured, independent and observed [I > 2σ(I)] reflections	7570, 3331, 2233
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.102, 0.99
No. of reflections	3331
No. of parameters	198
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.35
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SHELXS2014 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2010 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1401825

Crystal structure: contains datablock I. DOI: 10.1107/S2056989015009627/su5132sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015009627/su5132Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015009627/su5132Isup3.cml

checkCIF report

Chemical context top

Aroylhydrazones can coordinate to transition metals either in the amido form (Bessy Raj & Kurup, 2007) or in the iminolato form (Ghosh et al., 2005: Galić et al., 2011), leading to the formation of two types of complexes. Hydrazones derived from isonicotinoyl hydrazides are potential drugs for the treatment of the iron-overload associated diseases (Macková et al., 2012). They are associated with a broad spectrum of biological activities, and studies have shown that nicotinic acid hydrazones could be considered as anti-inflammatory and analgesic agents (Navidpour et al., 2014; Kheradmand et al., 2013) and as a novel pharmacophore in the design of anticonvulsant drugs (Sinha et al., 2011). Hydrazones have been used in chemical processes like non-linear optics and as sensors as well as in catalytic processes (Hosseini-Monfared et al., 2013; Du & Hong, 2014). Their potential as analytical reagents (Galić et al., 2011) and their uses as molecular switches, metallo-assemblies and sensors have also been reported (Su & Aprahamian, 2014). Salicylaldehyde isonicotinoylhydrazone has also been used for the spectrophotometric determination of gallium(III) and indium(III) (Reddy et al., 2011).

Structural commentary top

The title compound, Fig. 1, exists in the amido form with a C8═O2 bond length of 1.229 (2) Å. The molecule has an E conformation with respect to the azomethine bond, which is confirmed by the torsion angle C6—C7═ N1—N2 of 179.09 (19)°. The two aromatic rings (C1–C6 and N3/C9–C13), are inclined to the planar hydrazone moiety [O2/C8/N2/N1/C7; planar to within 0.006 (2) Å] by 2.12 (9) and 1.40 (8)°, respectively, and to each other by 0.74 (12)°. There is an intramolecular O—H···N hydrogen bond present in the molecule that involves the phenolic oxygen, O1, and the azomethine nitrogen atom, N1, forming an S(6) ring motif (Table 1 and Fig. 1). As the molecule is planar there are also two short intramolecular C—H···O contacts present, involving the water molecule and the CH groups C7—H7 and C10—H10 (Table 1 and Fig. 2).

Supramolecular features top

In the crystal, the water molecule forms three hydrogen bonds with three different nicotinic hydrazone molecules (Table 1 and Fig. 2). This compound is an example of a system where a single atom acts both as donor and acceptor. There are also C—H···Owater contacts present enclosing R₂¹(6) and R₂¹(7) ring motifs (Fig. 2). Finally sheets are formed lying parallel to (100). There are weak π–π interactions within the sheets involving the bromine-bearing aromatic ring of one molecule and the pyridine ring of another, with a centroid–centroid distance of 3.8473 (15) Å (Fig. 2). The sheets are linked via C—H···Br interactions, forming a three-dimensional framework (Table 1 and Fig. 3).

Database survey top

A search of the Cambridge Structural Database (Version 5.36, update Feb. 2015; Groom & Allen, 2014) yielded 22 hits for the substructure N'-(2-hydroxybenzylidene)nicotinohydrazide. The crystal structure of N'-(2-hydroxybenzylidene)nicotinohydrazide itself is reported as a monohydrate (IDASUB; Galić et al., 2001), and the crystal structure of the chloro derivative of the title compound, which crystallized with two independent molecules in the asymmetric unit, has also been reported (MOZPIB; Ren, 2009). In these two compounds, an intramolecular O—H···N hydrogen bond is also present. The molecules are also relatively planar with the benzene and pyridine rings being inclined to one another by ca 4.16° in IDASUB, and by ca 12.79 and 1.86° in the two independent molecules of MOZPIB. This last dihedral angle is similar to that in the title compound [cf. 0.74 (12)°]. In the crystal structure of N'-(2-hydroxybenzylidene)nicotinohydrazide monohydrate (IDASUB), the water molecule forms three hydrogen bonds and is another example of a system where a single atom acts both as donor and acceptor.

Synthesis and crystallization top

The title compound was prepared by adapting a reported procedure (Mathew & Kurup, 2011). A methanolic solution of 5-bromosalicylaldehyde (0.10051 g, 0.5 mmol) and nicotinic hydrazide (0.06857 g, 0.5 mmol) was refluxed for 3 h with two drops of glacial acetic acid. Light-yellow block-shaped crystals of the title compound were obtained by slow evaporation of the solvent. The crystals were filtered, washed with minimum quantity of methanol and dried over P₄O₁₀ in vacuo (yield: 0.22 g, 68.5%; m.p.: 480 K). Elemental analysis calculated for C₁₃H₁₀N₃O₂Br·H₂O: C, 46.17, H, 3.58, N, 12.43 %; found: C, 46.14, H, 3.57, N, 12.44 %. IR FT–IR (KBr, cm^-1) 3059 (NH), 3269(OH), 1680 (C=O), 1584 (C=N).

Refinement top

Related literature top

For related literature, see: Bessy & Kurup (2007); Du & Hong (2015); Galić et al. (2001, 2011); Ghosh et al. (2005); Groom & Allen (2014); Kheradmand et al. (2013); Macková et al. (2012); Mathew & Kurup (2011); Hosseini-Monfared et al. (2013); Navidpour et al. (2014); Reddy et al. (2011); Ren (2009); Sinha et al. (2011); Su & Aprahamian (2014).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2010) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. A view of the molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Hydrogen bonds (dashed lines) and a weak π–π interaction (in blue) in the crystal of the title compound [symmetry codes: (i) x, -y + 1/2, z + 1/2; (ii) -x, y + 1/2, -z + 1/2].
	Fig. 3. A view along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 for details) and H atoms not involved in hydrogen bonding have been omitted for clarity.

(E)-N'-(5-Bromo-2-hydroxybenzylidene)nicotinohydrazide monohydrate top

Crystal data top

C₁₃H₁₀BrN₃O₂·H₂O	F(000) = 680
M_r = 338.17	D_x = 1.649 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.1623 (7) Å	Cell parameters from 2267 reflections
b = 12.5953 (9) Å	θ = 2.9–25.5°
c = 13.2510 (8) Å	µ = 3.03 mm⁻¹
β = 90.226 (3)°	T = 296 K
V = 1362.28 (17) Å³	Needle, yellow
Z = 4	0.42 × 0.12 × 0.11 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	2233 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
ω and ϕ scan	θ_max = 28.3°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→4
T_min = 0.349, T_max = 0.356	k = −16→16
7570 measured reflections	l = −16→17
3331 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0557P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.102	(Δ/σ)_max < 0.001
S = 0.99	Δρ_max = 0.46 e Å⁻³
3331 reflections	Δρ_min = −0.35 e Å⁻³
198 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
5 restraints	Extinction coefficient: 0.0129 (13)

Crystal data top

C₁₃H₁₀BrN₃O₂·H₂O	V = 1362.28 (17) Å³
M_r = 338.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1623 (7) Å	µ = 3.03 mm⁻¹
b = 12.5953 (9) Å	T = 296 K
c = 13.2510 (8) Å	0.42 × 0.12 × 0.11 mm
β = 90.226 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3331 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2233 reflections with I > 2σ(I)
T_min = 0.349, T_max = 0.356	R_int = 0.028
7570 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	5 restraints
wR(F²) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.46 e Å⁻³
3331 reflections	Δρ_min = −0.35 e Å⁻³
198 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
C1	0.3276 (3)	0.35310 (19)	0.45911 (17)	0.0442 (6)
C2	0.4115 (4)	0.3763 (2)	0.54807 (18)	0.0527 (7)
H2	0.4272	0.4467	0.5667	0.063*
C3	0.4712 (3)	0.2969 (2)	0.60856 (16)	0.0499 (6)
H3	0.5276	0.3134	0.6676	0.060*
C4	0.4471 (3)	0.19134 (19)	0.58114 (15)	0.0443 (6)
C5	0.3653 (3)	0.16695 (19)	0.49313 (15)	0.0441 (6)
H5	0.3499	0.0962	0.4753	0.053*
C6	0.3057 (3)	0.24637 (18)	0.43065 (15)	0.0401 (5)
C7	0.2191 (3)	0.21655 (19)	0.33854 (15)	0.0431 (6)
H7	0.2084	0.1452	0.3219	0.052*
C8	0.0128 (3)	0.32662 (17)	0.13365 (15)	0.0385 (5)
C9	−0.0754 (3)	0.28892 (17)	0.04153 (15)	0.0358 (5)
C10	−0.0990 (3)	0.18419 (18)	0.01526 (15)	0.0450 (6)
H10	−0.0591	0.1321	0.0586	0.054*
C11	−0.2332 (4)	0.2286 (2)	−0.12925 (19)	0.0560 (7)
H11	−0.2880	0.2083	−0.1878	0.067*
C12	−0.2160 (3)	0.3349 (2)	−0.10981 (18)	0.0580 (7)
H12	−0.2581	0.3852	−0.1542	0.070*
C13	−0.1355 (3)	0.36555 (19)	−0.02368 (18)	0.0487 (6)
H13	−0.1214	0.4372	−0.0092	0.058*
N1	0.1580 (2)	0.28694 (15)	0.28050 (12)	0.0426 (5)
N2	0.0760 (3)	0.25244 (15)	0.19557 (13)	0.0403 (4)
N3	−0.1758 (3)	0.15309 (16)	−0.06888 (13)	0.0524 (6)
O1	0.2713 (3)	0.43501 (14)	0.40347 (14)	0.0634 (6)
O2	0.0235 (3)	0.42215 (12)	0.15145 (12)	0.0586 (6)
O1W	−0.0975 (3)	0.53043 (13)	0.31578 (13)	0.0641 (6)
Br1	0.52655 (4)	0.08150 (2)	0.66553 (2)	0.06576 (15)
H1	0.218 (4)	0.412 (2)	0.3516 (16)	0.079 (11)*
H2'	0.075 (3)	0.1842 (9)	0.1847 (18)	0.060 (8)*
H1A	−0.053 (4)	0.4947 (19)	0.2684 (15)	0.087 (11)*
H1B	−0.129 (3)	0.4858 (16)	0.3591 (15)	0.065 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0439 (15)	0.0460 (13)	0.0426 (11)	−0.0079 (11)	0.0002 (10)	−0.0046 (10)
C2	0.0600 (18)	0.0505 (14)	0.0477 (13)	−0.0140 (13)	0.0000 (12)	−0.0154 (11)
C3	0.0470 (16)	0.0603 (15)	0.0423 (12)	−0.0117 (12)	−0.0076 (11)	−0.0122 (11)
C4	0.0385 (14)	0.0545 (14)	0.0399 (11)	0.0016 (11)	−0.0018 (10)	−0.0070 (10)
C5	0.0429 (15)	0.0446 (13)	0.0446 (12)	−0.0009 (11)	−0.0008 (10)	−0.0131 (10)
C6	0.0364 (13)	0.0462 (13)	0.0378 (11)	−0.0056 (10)	0.0010 (9)	−0.0113 (9)
C7	0.0467 (15)	0.0435 (13)	0.0391 (11)	−0.0050 (11)	−0.0024 (10)	−0.0104 (10)
C8	0.0475 (15)	0.0335 (12)	0.0346 (10)	−0.0053 (10)	0.0043 (9)	−0.0044 (8)
C9	0.0387 (13)	0.0339 (11)	0.0349 (10)	−0.0006 (9)	0.0038 (9)	−0.0037 (8)
C10	0.0599 (17)	0.0366 (12)	0.0384 (11)	−0.0042 (11)	−0.0085 (11)	−0.0012 (9)
C11	0.0588 (18)	0.0624 (17)	0.0469 (13)	−0.0008 (13)	−0.0150 (12)	−0.0026 (11)
C12	0.0626 (19)	0.0557 (17)	0.0556 (14)	0.0138 (14)	−0.0201 (13)	0.0040 (11)
C13	0.0533 (17)	0.0363 (13)	0.0564 (14)	0.0067 (11)	−0.0034 (12)	0.0000 (10)
N1	0.0479 (13)	0.0449 (11)	0.0348 (9)	−0.0106 (9)	−0.0022 (8)	−0.0090 (8)
N2	0.0510 (13)	0.0350 (11)	0.0348 (9)	−0.0064 (9)	−0.0039 (8)	−0.0069 (7)
N3	0.0667 (16)	0.0464 (12)	0.0439 (11)	−0.0042 (11)	−0.0110 (10)	−0.0066 (9)
O1	0.0871 (16)	0.0443 (11)	0.0587 (11)	−0.0099 (9)	−0.0178 (11)	−0.0052 (8)
O2	0.0956 (17)	0.0328 (9)	0.0472 (9)	−0.0063 (8)	−0.0065 (10)	−0.0094 (6)
O1W	0.1112 (19)	0.0316 (9)	0.0494 (10)	0.0065 (10)	0.0025 (11)	0.0023 (8)
Br1	0.0773 (3)	0.0634 (2)	0.0564 (2)	0.00894 (15)	−0.01868 (14)	−0.00546 (12)

Geometric parameters (Å, º) top

C1—O1	1.348 (3)	C8—C9	1.492 (3)
C1—C2	1.392 (3)	C9—C10	1.378 (3)
C1—C6	1.407 (3)	C9—C13	1.384 (3)
C2—C3	1.370 (4)	C10—N3	1.336 (3)
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.392 (3)	C11—N3	1.327 (3)
C3—H3	0.9300	C11—C12	1.370 (4)
C4—C5	1.376 (3)	C11—H11	0.9300
C4—Br1	1.892 (2)	C12—C13	1.370 (3)
C5—C6	1.386 (3)	C12—H12	0.9300
C5—H5	0.9300	C13—H13	0.9300
C6—C7	1.457 (3)	N1—N2	1.378 (2)
C7—N1	1.274 (3)	N2—H2'	0.872 (10)
C7—H7	0.9300	O1—H1	0.858 (10)
C8—O2	1.229 (2)	O1W—H1A	0.854 (10)
C8—N2	1.345 (3)	O1W—H1B	0.845 (9)

O1—C1—C2	117.9 (2)	N2—C8—C9	117.42 (18)
O1—C1—C6	122.8 (2)	C10—C9—C13	117.5 (2)
C2—C1—C6	119.3 (2)	C10—C9—C8	125.3 (2)
C3—C2—C1	121.0 (2)	C13—C9—C8	117.22 (19)
C3—C2—H2	119.5	N3—C10—C9	123.8 (2)
C1—C2—H2	119.5	N3—C10—H10	118.1
C2—C3—C4	119.6 (2)	C9—C10—H10	118.1
C2—C3—H3	120.2	N3—C11—C12	123.4 (2)
C4—C3—H3	120.2	N3—C11—H11	118.3
C5—C4—C3	120.1 (2)	C12—C11—H11	118.3
C5—C4—Br1	120.11 (18)	C13—C12—C11	118.7 (2)
C3—C4—Br1	119.75 (17)	C13—C12—H12	120.6
C4—C5—C6	120.9 (2)	C11—C12—H12	120.6
C4—C5—H5	119.6	C12—C13—C9	119.4 (2)
C6—C5—H5	119.6	C12—C13—H13	120.3
C5—C6—C1	119.1 (2)	C9—C13—H13	120.3
C5—C6—C7	118.8 (2)	C7—N1—N2	117.49 (18)
C1—C6—C7	122.1 (2)	C8—N2—N1	117.59 (18)
N1—C7—C6	120.9 (2)	C8—N2—H2'	125.4 (19)
N1—C7—H7	119.5	N1—N2—H2'	116.9 (19)
C6—C7—H7	119.5	C11—N3—C10	117.2 (2)
O2—C8—N2	122.4 (2)	C1—O1—H1	111 (2)
O2—C8—C9	120.1 (2)	H1A—O1W—H1B	106 (2)

O1—C1—C2—C3	179.6 (2)	N2—C8—C9—C10	0.7 (3)
C6—C1—C2—C3	−0.7 (4)	O2—C8—C9—C13	3.2 (3)
C1—C2—C3—C4	−0.4 (4)	N2—C8—C9—C13	−177.9 (2)
C2—C3—C4—C5	0.8 (4)	C13—C9—C10—N3	0.1 (4)
C2—C3—C4—Br1	−179.05 (19)	C8—C9—C10—N3	−178.6 (2)
C3—C4—C5—C6	−0.1 (4)	N3—C11—C12—C13	0.0 (5)
Br1—C4—C5—C6	179.72 (18)	C11—C12—C13—C9	−0.6 (4)
C4—C5—C6—C1	−1.0 (3)	C10—C9—C13—C12	0.6 (4)
C4—C5—C6—C7	−179.7 (2)	C8—C9—C13—C12	179.4 (2)
O1—C1—C6—C5	−179.0 (2)	C6—C7—N1—N2	−179.09 (19)
C2—C1—C6—C5	1.4 (4)	O2—C8—N2—N1	−1.4 (3)
O1—C1—C6—C7	−0.3 (4)	C9—C8—N2—N1	179.77 (18)
C2—C1—C6—C7	−180.0 (2)	C7—N1—N2—C8	−179.3 (2)
C5—C6—C7—N1	177.9 (2)	C12—C11—N3—C10	0.7 (4)
C1—C6—C7—N1	−0.8 (3)	C9—C10—N3—C11	−0.7 (4)
O2—C8—C9—C10	−178.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.86 (1)	1.91 (2)	2.641 (2)	143 (3)
O1W—H1A···O2	0.85 (1)	1.91 (1)	2.756 (2)	172 (3)
O1W—H1B···N3ⁱ	0.85 (1)	2.03 (1)	2.845 (3)	162 (2)
N2—H2′···O1Wⁱⁱ	0.87 (1)	1.95 (1)	2.806 (3)	169 (3)
C7—H7···O1Wⁱⁱ	0.93	2.49	3.263 (3)	140
C10—H10···O1Wⁱⁱ	0.93	2.45	3.362 (3)	165
C11—H11···Br1ⁱⁱⁱ	0.93	2.93	3.825 (3)	162

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.86 (1)	1.905 (19)	2.641 (2)	143 (3)
O1W—H1A···O2	0.85 (1)	1.907 (11)	2.756 (2)	172 (3)
O1W—H1B···N3ⁱ	0.85 (1)	2.030 (13)	2.845 (3)	162 (2)
N2—H2'···O1Wⁱⁱ	0.87 (1)	1.946 (12)	2.806 (3)	169 (3)
C7—H7···O1Wⁱⁱ	0.93	2.49	3.263 (3)	140
C10—H10···O1Wⁱⁱ	0.93	2.45	3.362 (3)	165
C11—H11···Br1ⁱⁱⁱ	0.93	2.93	3.825 (3)	162

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀BrN₃O₂·H₂O
M_r	338.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.1623 (7), 12.5953 (9), 13.2510 (8)
β (°)	90.226 (3)
V (Å³)	1362.28 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.03
Crystal size (mm)	0.42 × 0.12 × 0.11

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.349, 0.356
No. of measured, independent and observed [I > 2σ(I)] reflections	7570, 3331, 2233
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.102, 0.99
No. of reflections	3331
No. of parameters	198
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.35

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS2014 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2010) and Mercury (Macrae et al., 2008), SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

NA is grateful to the UGC, New Delhi, India, for the award of a Senior Research Fellowship. MRPK is grateful to the UGC, New Delhi, India, for a UGC–BSR one-time grant to Faculty. We also thank the Sophisticated Analytical Instruments Facility, Cochin University of S&T, Kochi-22, India, for the diffraction measurements.

References

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Volume 71| Part 7| July 2015| Pages 734-736

doi:10.1107/S2056989015009627

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of (E)-N′-(5-bromo-2-hy­dr­oxy­benzyl­­idene)nicotinohydrazide monohydrate

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of (E)-N′-(5-bromo-2-hydroxybenzylidene)nicotinohydrazide monohydrate

3. Supramolecular features