N′-[(E)-3-Bromo-5-chloro-2-hy­droxy­benzyl­idene]furan-2-carbohydrazide

Sundar, A.; Ranjith, S.; Rajagopal, G.

doi:10.1107/S160053681401085X

organic compounds

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ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page o670

doi:10.1107/S160053681401085X

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N′-[(E)-3-Bromo-5-chloro-2-hydroxybenzylidene]furan-2-carbohydrazide

A. Sundar,^a S. Ranjith ^b and G. Rajagopal ^a ^*

^aDepartment of Chemistry, Madras Medical College, Chennai 600 003, India, and ^bDepartment of Physics, SRM University, Ramapuram Campus, Chennai 600 005, India
^*Correspondence e-mail: rajagopal18@yahoo.com

(Received 7 May 2014; accepted 12 May 2014; online 17 May 2014)

In the title compound, C₁₂H₈BrClN₂O₃, the furan ring makes a dihedral angle of 17.2 (2)° with the six-membered ring. An intramolecular O–H⋯N hydrogen bond stabilizes the molecular conformation. In the crystal, N–H⋯O hydrogen bonds connect the molecules into chains running along the c-axis direction. The crystal packing is additionally stabilized by C—H⋯O interactions into a three-dimensional supramolecular architecture.

CCDC reference: 1002445

Related literature

Heterocyclic carbohydrazides form stable metal chelates which find applications in molecular sensing, see: Bakir & Brown (2002 ). For the biological activity of hydrazones derived from isoniazid (systematic name: isonicotinohydrazide), see: Rollas & Kucukguzel (2007 ). For related structures, see: Prabhu et al. (2011 ); Bikas et al. (2010 ); Prasanna et al. (2013 ).

Experimental

Crystal data

C₁₂H₈BrClN₂O₃
M_r = 343.56
Monoclinic, P 2₁ /c
a = 16.7237 (9) Å
b = 7.7455 (4) Å
c = 10.1868 (5) Å
β = 93.557 (2)°
V = 1316.99 (12) Å³
Z = 4
Mo Kα radiation
μ = 3.33 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker AAPEXII CCD Diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.324, T_max = 0.435
13728 measured reflections
2996 independent reflections
2029 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.085
S = 1.02
2996 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.86	2.14	2.953 (2)	157
C3—H3⋯O1ⁱⁱ	0.93	2.44	3.324 (3)	159
C6—H6⋯O2ⁱ	0.93	2.50	3.263 (3)	139
O3—H3A⋯N2	0.82	1.84	2.564 (3)	146
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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 ); software used to prepare material for publication: PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1002445

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681401085X/bt6980sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681401085X/bt6980Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681401085X/bt6980Isup3.cml

checkCIF report

Comment top

Heterocyclic carbohydrazides are compounds with a wide spectrum of biological and analytical applications. They form stable metal chelates which find applications in molecular sensing (Bakir & Brown, 2002). A number of hydrazones derived from isoniazid were reported to be active antitubercular agents and were found to be less toxic than isoniazid (Rollas & Kucukguzel, 2007). Against this background, and in order to obtain detailed information on the molecular conformation in the solid state, an X-ray study of the title compound was carried out.

The X-ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The molecule exists in a E configuration with respect to the C6=N2 bond, with the C7—C6—N2—N1 torsion angle of 179.1 (2)°. The bond lengths and angles in the carbohydrazide group of the title compound can be compared with the related structures (Prabhu et al., 2011; Bikas et al., 2010). The furan ring makes a dihedral angle of 17.2 (2)° with the six-membered ring. The N2—N1—C5—O2 torsion angle of -0.1 (4)° indicates the cis configuration of the O2 atom with respect to the hydrazine nitrogen atom N2. The bond distances C6═N2 [1.275 (3) Å] and C5═O2 [1.224 (3) Å] are very close to the formal double C═N and C═O bond lengths (Prasanna, et al., 2013) confirming that the carbohydrazide exists in solid state as an amido tautomer. An intramolecular O–H···N hydrogen bond stabilized the molecular conformation. Intermolecular N–H···O hydrogen bonds connect the molecules to chains running along the c axis. The crystal packing is further stabilized by C–H···O hydrogen bonds.

Related literature top

Heterocyclic carbohydrazides form stable metal chelates which find

applications in molecular sensing, see: Bakir & Brown (2002). For the biological activity of hydrazones derived from isoniazid (systematic name: isonicotinohydrazide), see: Rollas & Kucukguzel (2007). For related structures, see: Prabhu et al. (2011); Bikas et al. (2010); Prasanna et al. (2013).

Experimental top

N'-[(E)-(3-bromo-5-chloro-2-hydroxyphenyl)methylidene]furan-2-carbohydrazide, ligand was synthesized by Schiff-base condensation furan-2-carbohydrazide and 3-bromo-5-chlorosalicylaldehyde as shown in Scheme-1. 3-bromo-5-chloro salicylaldehyde (3.0 mmol) in methanol (0.75 g) was stirred in a round bottom flask followed by drop wise addition of methanolic solution of furan-2-carbohydrazide (3.0 mmol). The reaction mixture was stirred for 3 h. The resulting white solid was removed by filtration and washed with cold ethanol and dried in vacuum over anhydrous CaCl₂·M.p:180°C, yield: 80%. Single crystals suitable for the X-ray diffraction are obtained by slow evaporation of a solution of the title compound in DMF at room temperature.

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); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atomic numbering and displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The crystal structure showing the R₂²(10) motif and also the formation of bifurcated R¹₂(6) ring motif. For the sake of clarity, the H atoms not involved in the motif have been omitted.

N'-[(E)-3-Bromo-5-chloro-2-hydroxybenzylidene]furan-2-carbohydrazide top

Crystal data top

C₁₂H₈BrClN₂O₃	F(000) = 680
M_r = 343.56	D_x = 1.733 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4049 reflections
a = 16.7237 (9) Å	θ = 2.8–24.5°
b = 7.7455 (4) Å	µ = 3.33 mm⁻¹
c = 10.1868 (5) Å	T = 293 K
β = 93.557 (2)°	Block, yellow
V = 1316.99 (12) Å³	0.35 × 0.30 × 0.25 mm
Z = 4

Data collection top

Bruker AAPEXII CCD Diffractometer	2996 independent reflections
Radiation source: fine-focus sealed tube	2029 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω and ϕ scan	θ_max = 27.4°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −21→21
T_min = 0.324, T_max = 0.435	k = −10→8
13728 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0346P)² + 0.5776P] where P = (F_o² + 2F_c²)/3
2996 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₂H₈BrClN₂O₃	V = 1316.99 (12) Å³
M_r = 343.56	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.7237 (9) Å	µ = 3.33 mm⁻¹
b = 7.7455 (4) Å	T = 293 K
c = 10.1868 (5) Å	0.35 × 0.30 × 0.25 mm
β = 93.557 (2)°

Data collection top

Bruker AAPEXII CCD Diffractometer	2996 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2029 reflections with I > 2σ(I)
T_min = 0.324, T_max = 0.435	R_int = 0.032
13728 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.02	Δρ_max = 0.39 e Å⁻³
2996 reflections	Δρ_min = −0.34 e Å⁻³
172 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
C1	0.30900 (18)	0.0948 (4)	0.5312 (4)	0.0704 (9)
H1	0.2756	0.0562	0.5947	0.084*
C2	0.28824 (18)	0.1059 (4)	0.4065 (3)	0.0678 (8)
H2	0.2389	0.0761	0.3657	0.081*
C3	0.35486 (17)	0.1718 (4)	0.3450 (2)	0.0558 (7)
H3	0.3579	0.1954	0.2560	0.067*
C4	0.41272 (14)	0.1937 (3)	0.4394 (2)	0.0386 (5)
C5	0.49358 (14)	0.2608 (3)	0.4308 (2)	0.0388 (5)
C6	0.66294 (15)	0.3109 (3)	0.6435 (2)	0.0410 (6)
H6	0.6461	0.2574	0.7187	0.049*
C7	0.74492 (14)	0.3741 (3)	0.6395 (2)	0.0377 (5)
C8	0.76987 (14)	0.4658 (3)	0.5306 (2)	0.0383 (5)
C9	0.84795 (15)	0.5274 (3)	0.5343 (2)	0.0467 (6)
C10	0.90118 (15)	0.4977 (3)	0.6409 (3)	0.0516 (7)
H10	0.9531	0.5410	0.6421	0.062*
C11	0.87656 (16)	0.4041 (3)	0.7446 (2)	0.0484 (6)
C12	0.79961 (15)	0.3424 (3)	0.7459 (2)	0.0458 (6)
H12	0.7839	0.2796	0.8178	0.055*
N1	0.53833 (11)	0.2682 (3)	0.54589 (17)	0.0418 (5)
H1A	0.5194	0.2354	0.6184	0.050*
N2	0.61464 (12)	0.3296 (2)	0.54270 (18)	0.0410 (5)
O1	0.38640 (12)	0.1475 (3)	0.55681 (17)	0.0626 (5)
O2	0.51905 (11)	0.3068 (3)	0.32640 (15)	0.0575 (5)
O3	0.72099 (10)	0.4955 (2)	0.42286 (14)	0.0485 (4)
H3A	0.6769	0.4528	0.4330	0.073*
Cl1	0.94376 (5)	0.36440 (11)	0.87885 (8)	0.0748 (2)
Br1	0.881917 (19)	0.65331 (5)	0.38959 (3)	0.07798 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0489 (18)	0.075 (2)	0.090 (2)	−0.0171 (16)	0.0222 (16)	0.0091 (18)
C2	0.0467 (18)	0.069 (2)	0.086 (2)	−0.0055 (15)	−0.0126 (16)	−0.0198 (17)
C3	0.0533 (17)	0.081 (2)	0.0322 (12)	0.0000 (15)	−0.0055 (11)	−0.0015 (12)
C4	0.0414 (14)	0.0433 (14)	0.0314 (11)	−0.0011 (11)	0.0038 (10)	−0.0031 (10)
C5	0.0415 (14)	0.0453 (14)	0.0299 (11)	0.0020 (11)	0.0034 (10)	−0.0031 (10)
C6	0.0397 (14)	0.0484 (15)	0.0350 (12)	0.0023 (11)	0.0024 (10)	0.0026 (10)
C7	0.0378 (13)	0.0383 (13)	0.0367 (12)	0.0038 (10)	−0.0010 (9)	−0.0033 (10)
C8	0.0379 (13)	0.0399 (14)	0.0369 (11)	0.0030 (11)	−0.0006 (10)	−0.0007 (10)
C9	0.0444 (15)	0.0466 (15)	0.0493 (13)	0.0000 (12)	0.0038 (11)	0.0031 (11)
C10	0.0383 (15)	0.0494 (16)	0.0663 (17)	−0.0004 (12)	−0.0044 (12)	−0.0011 (13)
C11	0.0464 (15)	0.0478 (15)	0.0487 (14)	0.0079 (12)	−0.0145 (11)	−0.0041 (12)
C12	0.0480 (15)	0.0473 (15)	0.0411 (13)	0.0043 (12)	−0.0045 (11)	0.0035 (11)
N1	0.0348 (11)	0.0605 (13)	0.0302 (9)	−0.0051 (10)	0.0035 (8)	0.0000 (9)
N2	0.0353 (11)	0.0491 (12)	0.0385 (10)	−0.0011 (9)	0.0028 (8)	−0.0032 (9)
O1	0.0529 (12)	0.0929 (15)	0.0428 (10)	−0.0065 (11)	0.0091 (8)	0.0075 (9)
O2	0.0502 (11)	0.0906 (14)	0.0323 (9)	−0.0104 (10)	0.0073 (8)	0.0032 (9)
O3	0.0406 (10)	0.0673 (12)	0.0368 (8)	−0.0025 (8)	−0.0027 (7)	0.0072 (8)
Cl1	0.0626 (5)	0.0837 (6)	0.0734 (5)	0.0051 (4)	−0.0337 (4)	0.0057 (4)
Br1	0.0531 (2)	0.1004 (3)	0.0810 (2)	−0.01171 (17)	0.00947 (15)	0.03418 (18)

Geometric parameters (Å, º) top

C1—C2	1.299 (4)	C7—C12	1.396 (3)
C1—O1	1.367 (4)	C7—C8	1.403 (3)
C1—H1	0.9300	C8—O3	1.347 (3)
C2—C3	1.407 (4)	C8—C9	1.388 (3)
C2—H2	0.9300	C9—C10	1.380 (3)
C3—C4	1.332 (3)	C9—Br1	1.885 (2)
C3—H3	0.9300	C10—C11	1.366 (4)
C4—O1	1.348 (3)	C10—H10	0.9300
C4—C5	1.456 (3)	C11—C12	1.373 (4)
C5—O2	1.224 (3)	C11—Cl1	1.743 (2)
C5—N1	1.352 (3)	C12—H12	0.9300
C6—N2	1.275 (3)	N1—N2	1.364 (3)
C6—C7	1.459 (3)	N1—H1A	0.8600
C6—H6	0.9300	O3—H3A	0.8200

C2—C1—O1	111.1 (3)	O3—C8—C9	119.1 (2)
C2—C1—H1	124.5	O3—C8—C7	122.4 (2)
O1—C1—H1	124.5	C9—C8—C7	118.5 (2)
C1—C2—C3	106.7 (3)	C10—C9—C8	121.6 (2)
C1—C2—H2	126.6	C10—C9—Br1	119.4 (2)
C3—C2—H2	126.6	C8—C9—Br1	119.00 (18)
C4—C3—C2	106.6 (2)	C11—C10—C9	119.1 (2)
C4—C3—H3	126.7	C11—C10—H10	120.5
C2—C3—H3	126.7	C9—C10—H10	120.5
C3—C4—O1	110.1 (2)	C10—C11—C12	121.3 (2)
C3—C4—C5	129.7 (2)	C10—C11—Cl1	119.3 (2)
O1—C4—C5	120.2 (2)	C12—C11—Cl1	119.3 (2)
O2—C5—N1	122.5 (2)	C11—C12—C7	120.0 (2)
O2—C5—C4	122.0 (2)	C11—C12—H12	120.0
N1—C5—C4	115.4 (2)	C7—C12—H12	120.0
N2—C6—C7	119.3 (2)	C5—N1—N2	117.55 (19)
N2—C6—H6	120.4	C5—N1—H1A	121.2
C7—C6—H6	120.4	N2—N1—H1A	121.2
C12—C7—C8	119.4 (2)	C6—N2—N1	119.2 (2)
C12—C7—C6	119.4 (2)	C4—O1—C1	105.5 (2)
C8—C7—C6	121.2 (2)	C8—O3—H3A	109.5

O1—C1—C2—C3	−0.8 (4)	C7—C8—C9—Br1	−179.23 (17)
C1—C2—C3—C4	0.9 (4)	C8—C9—C10—C11	0.7 (4)
C2—C3—C4—O1	−0.7 (3)	Br1—C9—C10—C11	−179.00 (19)
C2—C3—C4—C5	−178.9 (3)	C9—C10—C11—C12	−1.5 (4)
C3—C4—C5—O2	−0.6 (4)	C9—C10—C11—Cl1	179.38 (19)
O1—C4—C5—O2	−178.7 (2)	C10—C11—C12—C7	0.4 (4)
C3—C4—C5—N1	179.5 (3)	Cl1—C11—C12—C7	179.61 (18)
O1—C4—C5—N1	1.4 (3)	C8—C7—C12—C11	1.4 (4)
N2—C6—C7—C12	−175.3 (2)	C6—C7—C12—C11	−178.7 (2)
N2—C6—C7—C8	4.6 (3)	O2—C5—N1—N2	−0.1 (4)
C12—C7—C8—O3	177.6 (2)	C4—C5—N1—N2	179.77 (19)
C6—C7—C8—O3	−2.3 (3)	C7—C6—N2—N1	179.1 (2)
C12—C7—C8—C9	−2.1 (3)	C5—N1—N2—C6	−167.9 (2)
C6—C7—C8—C9	178.0 (2)	C3—C4—O1—C1	0.2 (3)
O3—C8—C9—C10	−178.6 (2)	C5—C4—O1—C1	178.6 (2)
C7—C8—C9—C10	1.1 (4)	C2—C1—O1—C4	0.4 (4)
O3—C8—C9—Br1	1.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.14	2.953 (2)	157
C3—H3···O1ⁱⁱ	0.93	2.44	3.324 (3)	159
C6—H6···O2ⁱ	0.93	2.50	3.263 (3)	139
O3—H3A···N2	0.82	1.84	2.564 (3)	146

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.86	2.14	2.953 (2)	156.6
C3—H3···O1ⁱⁱ	0.93	2.44	3.324 (3)	159.3
C6—H6···O2ⁱ	0.93	2.50	3.263 (3)	139.4
O3—H3A···N2	0.82	1.84	2.564 (3)	146.3

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

Acknowledgements

The authors wish to acknowledge the SAIF, IIT Madras, for the data collection.

References

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