N′-[(E)-Furan-2-ylmethyl­idene]-4-hydroxy­benzohydrazide

Datta, R.; Ramya, V.; Sithambaresan, M.; Kurup, M.R.P.

doi:10.1107/S1600536814001822

organic compounds

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Volume 70| Part 3| March 2014| Page o242

doi:10.1107/S1600536814001822

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N′-[(E)-Furan-2-ylmethylidene]-4-hydroxybenzohydrazide

Riya Datta,^a V. Ramya,^a M. Sithambaresan ^b ^* and M. R. Prathapachandra Kurup ^c

^aDepartment of Chemistry, Christ University, Hosur Road, Bangalore 560 029, India, ^bDepartment of Chemistry, Faculty of Science, Eastern University, Sri Lanka, Chenkalady, Sri Lanka, and ^cDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India
^*Correspondence e-mail: eesans@yahoo.com

(Received 13 December 2013; accepted 25 January 2014; online 5 February 2014)

The title compound, C₁₂H₁₀N₂O₃, exists in the E conformation. The five-membered ring and the phenyl rings form dihedral angles of 36.73 (10) and 12.22 (10)°, respectively, with the central C(=O)N₂C unit. The crystal packing is dominated by strong N—H⋯O and O—H⋯N hydrogen bonds. Together with weaker C—H⋯O interactions, these establish a three-dimensional supramolecular network.

CCDC reference: 983574

Related literature

For biological applications of benzohydrazones and derivatives, see: Sreeja et al. (2004 ); Rakha et al. (1996 ). For the synthesis of related compounds, see: Emmanuel et al. (2011 ). For a related structure, see: Datta et al. (2013 ).

Experimental

Crystal data

C₁₂H₁₀N₂O₃
M_r = 230.22
Orthorhombic, P n a 2₁
a = 9.5934 (3) Å
b = 11.1939 (4) Å
c = 10.3332 (3) Å
V = 1109.66 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.25 × 0.20 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.975, T_max = 0.984
3425 measured reflections
1014 independent reflections
992 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.064
S = 1.05
1014 reflections
163 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.10 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2′⋯O2ⁱ	0.88 (1)	2.09 (1)	2.9187 (19)	157 (2)
O3—H3′⋯N1ⁱⁱ	0.85 (1)	2.13 (1)	2.971 (2)	169 (3)
C5—H5⋯O2ⁱ	0.93	2.35	3.160 (2)	145
C11—H11⋯O3ⁱⁱⁱ	0.93	2.42	3.202 (2)	142
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (ii) $[-x+2, -y+2, z-{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, z]$ .

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: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 983574

Crystal structure: contains datablocks Global, I. DOI: 10.1107/S1600536814001822/fj2657sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814001822/fj2657Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814001822/fj2657Isup3.cml

checkCIF report

Comment top

Hydrazones and their derivatives show excellent biological activities (Sreeja et al., 2004). The great potential applications of aryl- hydrazones as antineoplastic, antiviral and antiinflammatory agents, hammered on the investigations of their derivatives (Rakha et al., 1996). As a continuous work on hydrazone compounds, a new hydrazone derivative, N'-[(E)-4,5-dihydrofuran-2-ylmethylidene]-4-hydroxybenzohydrazide, was prepared and structurally characterized. The ORTEP view of the title compound is shown in Fig. 1.

The compound crystallizes in orthorhombic space group Pna2₁. This molecule adopts an E configuration with respect to the C5=N1 bond and it exists in the amido form with a C6=O2 bond length of 1.232 (2) Å which is very close to the reported C=O bond length of similar structure (Datta et al., 2013). The O2 and N1 atoms are in Z configuration with respect to C6–N2 having a torsion angle of 3.7 (3)°. The central C(=O)N₂C unit has dihedral angles of 36.73 (10) and 12.22 (10)°, respectively with the five-membered ring and the phenyl ring.

There are two classical intermolecular N2–H2'···O2 and O3–H3'···N1 hydrogen bond interactions (Fig. 2) between the neighbouring molecule with D···A distances of 2.9187 (19) and 2.971 (2) Å respectively (Table 1). Two weak C–H···O hydrogen bond interactions (Fig. 3) between the H atoms attached at the C5 & C11 and O2 & O3 atoms of neighbouring molecules with D···A distances of 3.160 (2) and 3.202 (2) Å respectively, also promote the classical hydrogen bond interactions forming a supramolecular three-dimensional-hydrogen bonding network in the lattice. Notwithstanding that there are very weak short ring interactions found in the crystal system, they are not significant to support the network since centroid-centroid distances are above 4 Å. Fig. 4 shows a packing diagram of the title compound viewed along a axis.

Related literature top

For biological applications of benzohydrazones and derivatives, see: Sreeja et al. (2004); Rakha et al. (1996). For the synthesis of related compounds, see: Emmanuel et al. (2011). For a related structure, see: Datta et al. (2013).

Experimental top

The title compound was prepared by adapting a reported procedure (Emmanuel et al., 2011). A solution of furan-2-carbaldehyde (0.096 g, 1 mmol) in methanol/DMF 2:1 (10 ml) was mixed with a methanol/DMF solution (10 ml) of 4-hydroxybenzhydrazide (0.152 g, 1 mmol). The mixture was refluxed for 6 h and then cooled to room temperature. Light orange colored crystals were formed which were recrystallized in methanol/DMF (2:1 v/v). Block shaped crystals, suitable for SXRD studies, were obtained after slow evaporation of the solution in air for a few days.

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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. ORTEP view of the title compound drawn with 50% probability displacement ellipsoids for the non-H atoms.
	Fig. 2. Classical hydrogen-bonding interactions in the crystal structure of C₁₂H₁₀N₂O₃.
	Fig. 3. Hydrogen-bonding interactions in the crystal structure of C₁₂H₁₀N₂O₃.
	Fig. 4. Packing diagram of the compound along the a axis.

N'-[(E)-Furan-2-ylmethylidene]-4-hydroxybenzohydrazide top

Crystal data top

C₁₂H₁₀N₂O₃	F(000) = 480
M_r = 230.22	D_x = 1.378 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	θ = 2.7–28.4°
a = 9.5934 (3) Å	µ = 0.10 mm⁻¹
b = 11.1939 (4) Å	T = 298 K
c = 10.3332 (3) Å	Block, light orange
V = 1109.66 (6) Å³	0.25 × 0.20 × 0.16 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1014 independent reflections
Radiation source: fine-focus sealed tube	992 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
Detector resolution: 8.33 pixels mm^-1	θ_max = 25.0°, θ_min = 2.7°
phi and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −13→9
T_min = 0.975, T_max = 0.984	l = −10→12
3425 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.0363P)² + 0.1774P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1014 reflections	Δρ_max = 0.13 e Å⁻³
163 parameters	Δρ_min = −0.10 e Å⁻³
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.046 (5)

Crystal data top

C₁₂H₁₀N₂O₃	V = 1109.66 (6) Å³
M_r = 230.22	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 9.5934 (3) Å	µ = 0.10 mm⁻¹
b = 11.1939 (4) Å	T = 298 K
c = 10.3332 (3) Å	0.25 × 0.20 × 0.16 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1014 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	992 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.984	R_int = 0.015
3425 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	3 restraints
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.13 e Å⁻³
1014 reflections	Δρ_min = −0.10 e Å⁻³
163 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	1.10537 (16)	0.44042 (12)	0.85962 (16)	0.0487 (4)
O2	1.15292 (13)	0.82491 (12)	0.64988 (16)	0.0454 (4)
O3	0.79142 (15)	1.25293 (13)	0.43449 (17)	0.0509 (4)
N1	1.00354 (16)	0.64857 (13)	0.74734 (17)	0.0346 (4)
N2	0.94150 (15)	0.74797 (14)	0.69195 (18)	0.0357 (4)
C1	1.1354 (3)	0.3230 (2)	0.8813 (3)	0.0609 (7)
H1	1.2119	0.2956	0.9279	0.073*
C2	1.0401 (3)	0.2529 (2)	0.8265 (3)	0.0655 (7)
H2	1.0390	0.1698	0.8271	0.079*
C3	0.9410 (3)	0.32850 (19)	0.7673 (3)	0.0528 (6)
H3	0.8614	0.3054	0.7224	0.063*
C4	0.9853 (2)	0.44092 (17)	0.7889 (2)	0.0394 (5)
C5	0.9330 (2)	0.55207 (17)	0.7401 (2)	0.0389 (5)
H5	0.8452	0.5539	0.7019	0.047*
C6	1.02519 (18)	0.83589 (16)	0.64733 (19)	0.0332 (4)
C7	0.95845 (19)	0.94475 (16)	0.5952 (2)	0.0327 (4)
C8	0.81588 (19)	0.96915 (18)	0.6015 (2)	0.0422 (5)
H8	0.7566	0.9156	0.6428	0.051*
C9	0.7622 (2)	1.07164 (18)	0.5474 (2)	0.0464 (5)
H9	0.6670	1.0866	0.5525	0.056*
C10	0.8484 (2)	1.15259 (16)	0.48562 (19)	0.0363 (5)
C11	0.9907 (2)	1.13042 (17)	0.4805 (2)	0.0400 (5)
H11	1.0502	1.1850	0.4410	0.048*
C12	1.04335 (19)	1.02759 (17)	0.5340 (2)	0.0383 (5)
H12	1.1387	1.0131	0.5291	0.046*
H2'	0.8518 (11)	0.7474 (18)	0.676 (2)	0.041 (6)*
H3'	0.853 (2)	1.288 (2)	0.389 (2)	0.062 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0473 (8)	0.0475 (9)	0.0515 (9)	0.0037 (7)	−0.0047 (7)	0.0042 (8)
O2	0.0233 (6)	0.0449 (8)	0.0679 (10)	0.0008 (5)	−0.0012 (7)	0.0128 (8)
O3	0.0378 (8)	0.0491 (9)	0.0657 (11)	0.0131 (7)	0.0115 (9)	0.0196 (8)
N1	0.0280 (7)	0.0328 (8)	0.0428 (9)	0.0011 (6)	0.0003 (7)	0.0026 (7)
N2	0.0235 (7)	0.0349 (8)	0.0488 (10)	0.0005 (6)	−0.0024 (8)	0.0037 (7)
C1	0.0719 (16)	0.0551 (15)	0.0556 (14)	0.0205 (13)	0.0011 (14)	0.0138 (12)
C2	0.098 (2)	0.0364 (12)	0.0621 (15)	0.0059 (13)	0.0102 (16)	0.0116 (12)
C3	0.0609 (14)	0.0396 (11)	0.0578 (14)	−0.0100 (10)	0.0026 (12)	0.0031 (11)
C4	0.0360 (9)	0.0397 (10)	0.0426 (11)	−0.0017 (8)	0.0032 (9)	0.0006 (9)
C5	0.0302 (9)	0.0388 (10)	0.0478 (12)	−0.0020 (7)	−0.0008 (10)	−0.0004 (9)
C6	0.0261 (8)	0.0356 (9)	0.0380 (10)	−0.0006 (7)	−0.0014 (8)	−0.0012 (8)
C7	0.0271 (9)	0.0337 (9)	0.0372 (10)	−0.0006 (7)	−0.0001 (9)	−0.0020 (8)
C8	0.0283 (9)	0.0430 (10)	0.0554 (12)	0.0004 (8)	0.0087 (10)	0.0099 (11)
C9	0.0260 (9)	0.0519 (12)	0.0614 (13)	0.0090 (8)	0.0089 (11)	0.0101 (12)
C10	0.0328 (10)	0.0362 (10)	0.0399 (12)	0.0054 (8)	0.0017 (9)	0.0015 (9)
C11	0.0295 (10)	0.0416 (10)	0.0488 (13)	−0.0036 (8)	0.0037 (9)	0.0084 (10)
C12	0.0227 (9)	0.0419 (10)	0.0504 (13)	0.0010 (7)	0.0001 (9)	0.0044 (9)

Geometric parameters (Å, º) top

O1—C4	1.364 (3)	C3—H3	0.9300
O1—C1	1.364 (3)	C4—C5	1.433 (3)
O2—C6	1.232 (2)	C5—H5	0.9300
O3—C10	1.356 (2)	C6—C7	1.478 (2)
O3—H3'	0.847 (10)	C7—C12	1.387 (2)
N1—C5	1.277 (2)	C7—C8	1.396 (3)
N1—N2	1.386 (2)	C8—C9	1.376 (3)
N2—C6	1.351 (2)	C8—H8	0.9300
N2—H2'	0.876 (10)	C9—C10	1.383 (3)
C1—C2	1.331 (4)	C9—H9	0.9300
C1—H1	0.9300	C10—C11	1.389 (3)
C2—C3	1.412 (4)	C11—C12	1.373 (3)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.347 (3)	C12—H12	0.9300

C4—O1—C1	105.67 (19)	O2—C6—N2	120.73 (17)
C10—O3—H3'	108.7 (18)	O2—C6—C7	121.39 (16)
C5—N1—N2	115.31 (16)	N2—C6—C7	117.87 (15)
C6—N2—N1	118.08 (14)	C12—C7—C8	117.77 (17)
C6—N2—H2'	121.6 (14)	C12—C7—C6	117.59 (15)
N1—N2—H2'	119.6 (14)	C8—C7—C6	124.63 (17)
C2—C1—O1	110.7 (2)	C9—C8—C7	120.71 (19)
C2—C1—H1	124.7	C9—C8—H8	119.6
O1—C1—H1	124.7	C7—C8—H8	119.6
C1—C2—C3	107.1 (2)	C8—C9—C10	120.64 (17)
C1—C2—H2	126.5	C8—C9—H9	119.7
C3—C2—H2	126.5	C10—C9—H9	119.7
C4—C3—C2	106.0 (2)	O3—C10—C9	118.77 (17)
C4—C3—H3	127.0	O3—C10—C11	121.97 (18)
C2—C3—H3	127.0	C9—C10—C11	119.24 (18)
C3—C4—O1	110.59 (19)	C12—C11—C10	119.74 (18)
C3—C4—C5	129.9 (2)	C12—C11—H11	120.1
O1—C4—C5	119.19 (18)	C10—C11—H11	120.1
N1—C5—C4	121.89 (19)	C11—C12—C7	121.88 (16)
N1—C5—H5	119.1	C11—C12—H12	119.1
C4—C5—H5	119.1	C7—C12—H12	119.1

C5—N1—N2—C6	−152.8 (2)	N2—C6—C7—C12	−171.64 (19)
C4—O1—C1—C2	0.4 (3)	O2—C6—C7—C8	−172.9 (2)
O1—C1—C2—C3	−0.9 (3)	N2—C6—C7—C8	7.4 (3)
C1—C2—C3—C4	1.0 (3)	C12—C7—C8—C9	0.7 (3)
C2—C3—C4—O1	−0.8 (3)	C6—C7—C8—C9	−178.4 (2)
C2—C3—C4—C5	173.0 (2)	C7—C8—C9—C10	0.0 (4)
C1—O1—C4—C3	0.2 (3)	C8—C9—C10—O3	−179.5 (2)
C1—O1—C4—C5	−174.3 (2)	C8—C9—C10—C11	−1.1 (3)
N2—N1—C5—C4	177.85 (18)	O3—C10—C11—C12	179.84 (19)
C3—C4—C5—N1	−164.8 (3)	C9—C10—C11—C12	1.5 (3)
O1—C4—C5—N1	8.5 (3)	C10—C11—C12—C7	−0.8 (3)
N1—N2—C6—O2	3.7 (3)	C8—C7—C12—C11	−0.3 (3)
N1—N2—C6—C7	−176.57 (16)	C6—C7—C12—C11	178.9 (2)
O2—C6—C7—C12	8.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2′···O2ⁱ	0.88 (1)	2.09 (1)	2.9187 (19)	157 (2)
O3—H3′···N1ⁱⁱ	0.85 (1)	2.13 (1)	2.971 (2)	169 (3)
C5—H5···O2ⁱ	0.93	2.35	3.160 (2)	145
C11—H11···O3ⁱⁱⁱ	0.93	2.42	3.202 (2)	142

Symmetry codes: (i) x−1/2, −y+3/2, z; (ii) −x+2, −y+2, z−1/2; (iii) x+1/2, −y+5/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2'···O2ⁱ	0.876 (10)	2.090 (12)	2.9187 (19)	157.4 (18)
O3—H3'···N1ⁱⁱ	0.847 (10)	2.134 (12)	2.971 (2)	169 (3)
C5—H5···O2ⁱ	0.9300	2.35	3.160 (2)	145
C11—H11···O3ⁱⁱⁱ	0.9300	2.42	3.202 (2)	142

Symmetry codes: (i) x−1/2, −y+3/2, z; (ii) −x+2, −y+2, z−1/2; (iii) x+1/2, −y+5/2, z.

Acknowledgements

The authors are grateful to the Department of Chemistry, IIT Madras, Chennai, India, for providing the single-crystal X-ray diffraction data. RV and RD thank Christ University, Hosur Road, Bangalore 560029, India, for financial support.

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