N′-[(E)-2-Hy­droxy-3,5-diiodo­benzyl­idene]cyclo­hexa­ne-1-carbohydrazide

Thirugnanasundar, A.; Suresh, J.; Meenakshi, C.; Chakkaravarthi, G.; Rajagopal, G.

doi:10.1107/S1600536811036488

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2620

https://doi.org/10.1107/S1600536811036488

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N′-[(E)-2-Hydroxy-3,5-diiodobenzylidene]cyclohexane-1-carbohydrazide

A. Thirugnanasundar,^a J. Suresh,^b C. Meenakshi,^c G. Chakkaravarthi ^d ^* and G. Rajagopal ^e ^*

^aDepartment of Chemistry, Velalar College of Engineering and Technology, Erode 638 009, India, ^bDepartment of Physics, The Madura College, Madurai 625 011, India, ^cDepartment of Chemistry, Government Arts College for Women (Autonomous), Madurai 625 002, India, ^dDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, and ^eDepartment of Chemistry, Government Arts College, Melur 625 106, India
^*Correspondence e-mail: chakkaravarthi_2005@yahoo.com, rajagopal18@yahoo.com

(Received 5 September 2011; accepted 7 September 2011; online 14 September 2011)

In the title compound, C₁₄H₁₀I₂N₂O₂, the two aromatic rings are inclined at a dihedral angle of 16.72 (33)°. The molecular structure is stabilized by an intramolecular O—H⋯N hydrogen bond. In the crystal, intermolecular N—H⋯O interactions link the molecules into chains running along the c axis. C—H⋯O interactions also occur. The crystal used for the structure determination was a non-merohedral twin with a domain ratio of 0.972 (2):0.028 (2).

Related literature

For the biological activity of Schiff base derivatives, see: Daier et al. (2004 ); Golcu et al. (2005 ); Liu & Yang (2010 ); Zgierski & Grabowska (2000 ). For related structures, see: Manvizhi et al. (2011 ); Thirugnanasundar et al. (2011 ).

Experimental

Crystal data

C₁₄H₁₀I₂N₂O₂
M_r = 492.04
Monoclinic, P 2₁ /c
a = 17.7495 (13) Å
b = 9.4273 (6) Å
c = 9.4684 (7) Å
β = 103.052 (3)°
V = 1543.42 (19) Å³
Z = 4
Mo Kα radiation
μ = 4.08 mm⁻¹
T = 295 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.496, T_max = 0.686
13146 measured reflections
2708 independent reflections
2349 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.172
S = 1.11
2708 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 1.48 e Å⁻³
Δρ_min = −1.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N2	0.85	1.84	2.586 (13)	145
N1—H1⋯O1ⁱ	0.86	2.02	2.824 (14)	155
C3—H3⋯O2ⁱⁱ	0.93	2.53	3.365 (19)	150
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811036488/bt5637sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811036488/bt5637Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811036488/bt5637Isup3.cml

checkCIF report

Comment top

Schiff base ligands play an important role in the development of coordination chemistry and possess important properties such as biological activity (Golcu et al., 2005; Liu & Yang, 2010), catalytic activity (Daier et al., 2004) and photochromic properties (Zgierski & Grabowska, 2000).

The goemetric parameters of the title compound (Fig. 1) agree well with related structures (Manvizhi et al., 2011; Thirugnanasundar et al., 2011). The two aromatic rings are inclined at an angle of 16.72 (33)°.

The molecular structure is stabilized by an intramolecular O-H···N hydrogen bond. The crystal structure is controlled by intermolecular N-H···O and C—H···O (Fig. 2 & Table 1) interactions.

Related literature top

For the biological activity of Schiff base derivatives, see: Daier et al. (2004); Golcu et al. (2005); Liu & Yang (2010); Zgierski & Grabowska (2000). For related structures, see: Manvizhi et al. (2011); Thirugnanasundar et al. (2011).

Experimental top

A methanolic solution (10 ml) of benzoicacid hydrazide (5 mmol) was magnetically stirred in a round bottom flask followed by drop wise addition of methanolic solution of 3,5-diiodosalicylaldehyde (5 mmol). The reaction mixture was then refluxed for three hours and upon cooling to 278 K, a yellow crystalline solid precipitates from the mixture. The solid which is separated out was filtered washed with ice cold ethanol and dried in vaccuo over anhydrous CaCl₂. Single crystals suitable for the X-ray diffraction were obtained by slow evaporation of a solution of the title compound in DMF at room temperature. Melting Point : 485 K.

Structure description top

The molecular structure is stabilized by an intramolecular O-H···N hydrogen bond. The crystal structure is controlled by intermolecular N-H···O and C—H···O (Fig. 2 & Table 1) interactions.

For the biological activity of Schiff base derivatives, see: Daier et al. (2004); Golcu et al. (2005); Liu & Yang (2010); Zgierski & Grabowska (2000). For related structures, see: Manvizhi et al. (2011); Thirugnanasundar et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing of (I), viewed down b axis. Intermolecular Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

N'-[(E)-2-Hydroxy-3,5-diiodobenzylidene]cyclohexane-1- carbohydrazide top

Crystal data top

C₁₄H₁₀I₂N₂O₂	F(000) = 920
M_r = 492.04	D_x = 2.118 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13146 reflections
a = 17.7495 (13) Å	θ = 2.2–25.0°
b = 9.4273 (6) Å	µ = 4.08 mm⁻¹
c = 9.4684 (7) Å	T = 295 K
β = 103.052 (3)°	Block, yellow
V = 1543.42 (19) Å³	0.20 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker Kappa APEXII diffractometer	2708 independent reflections
Radiation source: fine-focus sealed tube	2349 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and φ scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→21
T_min = 0.496, T_max = 0.686	k = −11→8
13146 measured reflections	l = −11→11

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0412P)² + 42.3729P] where P = (F_o² + 2F_c²)/3
2708 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 1.48 e Å⁻³
0 restraints	Δρ_min = −1.52 e Å⁻³

Crystal data top

C₁₄H₁₀I₂N₂O₂	V = 1543.42 (19) Å³
M_r = 492.04	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.7495 (13) Å	µ = 4.08 mm⁻¹
b = 9.4273 (6) Å	T = 295 K
c = 9.4684 (7) Å	0.20 × 0.10 × 0.10 mm
β = 103.052 (3)°

Data collection top

Bruker Kappa APEXII diffractometer	2708 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2349 reflections with I > 2σ(I)
T_min = 0.496, T_max = 0.686	R_int = 0.029
13146 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0412P)² + 42.3729P] where P = (F_o² + 2F_c²)/3
2708 reflections	Δρ_max = 1.48 e Å⁻³
182 parameters	Δρ_min = −1.52 e Å⁻³

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

	x	y	z	U_iso*/U_eq
I1	0.89740 (5)	0.16968 (10)	0.83785 (10)	0.0458 (3)
I2	0.91863 (7)	−0.18253 (14)	1.36905 (13)	0.0777 (5)
O1	0.5247 (5)	0.3352 (11)	0.8089 (10)	0.052 (3)
O2	0.7346 (5)	0.2255 (10)	0.9018 (10)	0.044 (2)
H2A	0.6895	0.2404	0.9145	0.065*
N1	0.5428 (6)	0.2182 (13)	1.0250 (11)	0.043 (3)
H1	0.5244	0.1906	1.0969	0.052*
N2	0.6169 (6)	0.1863 (12)	1.0158 (11)	0.040 (3)
C1	0.4189 (7)	0.3296 (14)	0.9272 (12)	0.036 (3)
C2	0.3821 (7)	0.4436 (15)	0.8509 (13)	0.043 (3)
H2	0.4075	0.4988	0.7950	0.052*
C3	0.3079 (9)	0.4755 (18)	0.8577 (16)	0.057 (4)
H3	0.2836	0.5541	0.8082	0.068*
C4	0.2694 (8)	0.3939 (16)	0.9356 (15)	0.047 (3)
H4	0.2185	0.4156	0.9369	0.057*
C5	0.3052 (7)	0.2777 (15)	1.0138 (13)	0.041 (3)
H5	0.2790	0.2217	1.0678	0.049*
C6	0.3807 (7)	0.2479 (15)	1.0092 (14)	0.041 (3)
H6	0.4060	0.1719	1.0621	0.049*
C7	0.4996 (7)	0.2964 (14)	0.9137 (11)	0.035 (3)
C8	0.6579 (7)	0.1120 (14)	1.1159 (12)	0.036 (3)
H8	0.6375	0.0800	1.1924	0.043*
C9	0.7375 (7)	0.0770 (13)	1.1107 (13)	0.034 (3)
C10	0.7797 (7)	−0.0131 (15)	1.2142 (14)	0.042 (3)
H10	0.7576	−0.0486	1.2872	0.051*
C11	0.8534 (8)	−0.0503 (15)	1.2102 (14)	0.043 (3)
C12	0.8881 (7)	0.0029 (13)	1.1027 (14)	0.040 (3)
H12	0.9385	−0.0225	1.1010	0.048*
C13	0.8471 (7)	0.0932 (13)	0.9997 (13)	0.034 (3)
C14	0.7710 (6)	0.1333 (13)	1.0022 (12)	0.031 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0346 (4)	0.0620 (6)	0.0442 (5)	0.0048 (4)	0.0159 (4)	0.0154 (4)
I2	0.0733 (8)	0.0933 (9)	0.0714 (8)	0.0406 (7)	0.0266 (6)	0.0484 (7)
O1	0.041 (5)	0.074 (7)	0.047 (6)	0.002 (5)	0.021 (4)	0.010 (5)
O2	0.034 (4)	0.048 (5)	0.051 (5)	0.007 (4)	0.015 (4)	0.015 (4)
N1	0.032 (5)	0.064 (7)	0.036 (6)	0.015 (5)	0.015 (4)	0.005 (5)
N2	0.024 (5)	0.058 (7)	0.042 (6)	0.002 (5)	0.017 (4)	−0.006 (5)
C1	0.026 (6)	0.053 (8)	0.025 (6)	0.003 (5)	−0.001 (5)	−0.006 (5)
C2	0.041 (7)	0.054 (8)	0.034 (7)	0.006 (6)	0.006 (6)	0.000 (6)
C3	0.052 (9)	0.066 (10)	0.051 (8)	0.018 (8)	0.010 (7)	0.002 (8)
C4	0.036 (7)	0.055 (9)	0.054 (8)	0.007 (6)	0.016 (6)	−0.002 (7)
C5	0.035 (6)	0.059 (8)	0.033 (6)	0.003 (6)	0.016 (5)	0.003 (6)
C6	0.034 (6)	0.046 (8)	0.046 (7)	0.008 (6)	0.013 (6)	0.010 (6)
C7	0.031 (6)	0.057 (8)	0.017 (5)	0.001 (5)	0.007 (4)	0.001 (5)
C8	0.034 (6)	0.052 (8)	0.023 (6)	0.005 (6)	0.011 (5)	−0.005 (5)
C9	0.034 (6)	0.039 (7)	0.031 (6)	0.003 (5)	0.010 (5)	−0.002 (5)
C10	0.042 (7)	0.053 (8)	0.036 (7)	0.007 (6)	0.016 (6)	0.006 (6)
C11	0.046 (7)	0.048 (8)	0.034 (6)	0.007 (6)	0.008 (6)	0.006 (6)
C12	0.042 (7)	0.037 (7)	0.044 (7)	0.011 (6)	0.016 (6)	0.004 (5)
C13	0.033 (6)	0.037 (7)	0.032 (6)	0.003 (5)	0.008 (5)	−0.002 (5)
C14	0.031 (6)	0.033 (6)	0.028 (6)	0.006 (5)	0.006 (5)	−0.003 (5)

Geometric parameters (Å, º) top

I1—C13	2.070 (12)	C4—C5	1.393 (19)
I2—C11	2.090 (13)	C4—H4	0.9300
O1—C7	1.231 (14)	C5—C6	1.379 (17)
O2—C14	1.342 (14)	C5—H5	0.9300
O2—H2A	0.8480	C6—H6	0.9300
N1—C7	1.370 (15)	C8—C9	1.463 (16)
N1—N2	1.370 (13)	C8—H8	0.9300
N1—H1	0.8600	C9—C10	1.382 (17)
N2—C8	1.268 (16)	C9—C14	1.402 (16)
C1—C2	1.375 (18)	C10—C11	1.363 (18)
C1—C6	1.376 (18)	C10—H10	0.9300
C1—C7	1.500 (16)	C11—C12	1.397 (18)
C2—C3	1.366 (19)	C12—C13	1.373 (17)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.35 (2)	C13—C14	1.409 (16)
C3—H3	0.9300

C14—O2—H2A	108.9	O1—C7—C1	122.2 (11)
C7—N1—N2	116.6 (10)	N1—C7—C1	115.2 (10)
C7—N1—H1	121.7	N2—C8—C9	119.7 (11)
N2—N1—H1	121.7	N2—C8—H8	120.1
C8—N2—N1	118.1 (10)	C9—C8—H8	120.1
C2—C1—C6	119.8 (11)	C10—C9—C14	120.1 (11)
C2—C1—C7	117.9 (12)	C10—C9—C8	119.2 (11)
C6—C1—C7	122.2 (11)	C14—C9—C8	120.8 (11)
C3—C2—C1	119.8 (14)	C11—C10—C9	120.5 (12)
C3—C2—H2	120.1	C11—C10—H10	119.7
C1—C2—H2	120.1	C9—C10—H10	119.7
C4—C3—C2	120.7 (14)	C10—C11—C12	120.8 (12)
C4—C3—H3	119.6	C10—C11—I2	120.9 (10)
C2—C3—H3	119.6	C12—C11—I2	118.3 (9)
C3—C4—C5	120.7 (13)	C13—C12—C11	119.4 (11)
C3—C4—H4	119.6	C13—C12—H12	120.3
C5—C4—H4	119.6	C11—C12—H12	120.3
C6—C5—C4	118.3 (12)	C12—C13—C14	120.7 (11)
C6—C5—H5	120.9	C12—C13—I1	119.6 (9)
C4—C5—H5	120.9	C14—C13—I1	119.7 (9)
C1—C6—C5	120.7 (12)	O2—C14—C9	123.3 (10)
C1—C6—H6	119.7	O2—C14—C13	118.1 (10)
C5—C6—H6	119.7	C9—C14—C13	118.5 (11)
O1—C7—N1	122.6 (11)

C7—N1—N2—C8	−178.8 (12)	N2—C8—C9—C14	4.9 (19)
C6—C1—C2—C3	0 (2)	C14—C9—C10—C11	−1 (2)
C7—C1—C2—C3	178.5 (12)	C8—C9—C10—C11	178.5 (13)
C1—C2—C3—C4	−2 (2)	C9—C10—C11—C12	1 (2)
C2—C3—C4—C5	2 (2)	C9—C10—C11—I2	178.5 (10)
C3—C4—C5—C6	0 (2)	C10—C11—C12—C13	0 (2)
C2—C1—C6—C5	1 (2)	I2—C11—C12—C13	−178.1 (10)
C7—C1—C6—C5	−177.0 (12)	C11—C12—C13—C14	0.5 (19)
C4—C5—C6—C1	−1 (2)	C11—C12—C13—I1	−178.9 (10)
N2—N1—C7—O1	1.0 (19)	C10—C9—C14—O2	−177.3 (12)
N2—N1—C7—C1	−179.9 (11)	C8—C9—C14—O2	2.8 (18)
C2—C1—C7—O1	−22.7 (18)	C10—C9—C14—C13	1.5 (18)
C6—C1—C7—O1	155.4 (13)	C8—C9—C14—C13	−178.4 (11)
C2—C1—C7—N1	158.2 (12)	C12—C13—C14—O2	177.8 (11)
C6—C1—C7—N1	−23.7 (18)	I1—C13—C14—O2	−2.8 (15)
N1—N2—C8—C9	−179.4 (11)	C12—C13—C14—C9	−1.1 (18)
N2—C8—C9—C10	−175.0 (13)	I1—C13—C14—C9	178.3 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N2	0.85	1.84	2.586 (13)	145
N1—H1···O1ⁱ	0.86	2.02	2.824 (14)	155
C3—H3···O2ⁱⁱ	0.93	2.53	3.365 (19)	150

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀I₂N₂O₂
M_r	492.04
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	17.7495 (13), 9.4273 (6), 9.4684 (7)
β (°)	103.052 (3)
V (Å³)	1543.42 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.08
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.496, 0.686
No. of measured, independent and observed [I > 2σ(I)] reflections	13146, 2708, 2349
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.172, 1.11
No. of reflections	2708
No. of parameters	182
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0412P)² + 42.3729P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.48, −1.52

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N2	0.85	1.84	2.586 (13)	145
N1—H1···O1ⁱ	0.86	2.02	2.824 (14)	155
C3—H3···O2ⁱⁱ	0.93	2.53	3.365 (19)	150

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

Acknowledgements

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

References

Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Daier, V., Biava, H., Palopoli, C., Shove, S., Tuchagues, J. P. & Signorella, S. (2004). J. Inorg. Biochem. 98, 1806–1817. Web of Science CSD CrossRef PubMed CAS Google Scholar
Golcu, A., Tumer, M., Demirelli, H. & Wheatley, R. A. (2005). Inorg. Chim. Acta, 358, 1785–1797. Web of Science CrossRef CAS Google Scholar
Liu, Y.-C. & Yang, Z.-Y. (2010). J. Biochem. 147, 381–391. Web of Science CSD CrossRef PubMed CAS Google Scholar
Manvizhi, K., Chakkaravarthi, G., Anbalagan, G. & Rajagopal, G. (2011). Acta Cryst. E67, o2500. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Thirugnanasundar, A., Suresh, J., Ramu, A. & RajaGopal, G. (2011). Acta Cryst. E67, o2303. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zgierski, M. Z. & Grabowska, A. (2000). J. Chem. Phys. 113, 7845–7852. Web of Science CrossRef CAS Google Scholar