(E)-N′-(2-Hydr­oxy-3,5-diiodo­benzyl­idene)-2-nitro­benzohydrazide methanol solvate

Qian, H.-Y.; Qu, D.-P.

doi:10.1107/S1600536809033091

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2238

doi:10.1107/S1600536809033091

Open

access

(E)-N′-(2-Hydroxy-3,5-diiodobenzylidene)-2-nitrobenzohydrazide methanol solvate

Heng-Yu Qian ^a ^* and Da-Ping Qu ^b

^aKey Laboratory of Surface and Interface Science of Henan, School of Material & Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, People's Republic of China, and ^bDepartment of Chemistry, Dalian Teacher College, Dalian 116000, People's Republic of China
^*Correspondence e-mail: hengyu_qian@126.com

(Received 19 August 2009; accepted 19 August 2009; online 26 August 2009)

In the title compound, C₁₄H₉I₂N₃O₄·CH₃OH, the Schiff base molecule adopts an E geometry with respect to the C=N bond and the dihedral angle between the benzene rings is 45.0 (2)°; an intramolecular O—H⋯N hydrogen bond is present. In the crystal, adjacent Schiff base molecules are linked by methanol solvent molecules through intermolecular N—H⋯O and O—H⋯O hydrogen bonds, forming dimers.

Related literature

For a related structure and background, see: Qian & Qu (2009 ).

Experimental

Crystal data

C₁₄H₉I₂N₃O₄·CH₄O
M_r = 569.08
Monoclinic, C 2/c
a = 19.5041 (12) Å
b = 10.2306 (7) Å
c = 19.9474 (14) Å
β = 111.764 (4)°
V = 3696.6 (4) Å³
Z = 8
Mo Kα radiation
μ = 3.43 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.547, T_max = 0.577
11057 measured reflections
4015 independent reflections
3394 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.068
S = 1.11
4015 reflections
232 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −1.02 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.88	2.599 (3)	146
O5—H5⋯O2ⁱ	0.82	1.91	2.711 (4)	164
N2—H2⋯O5ⁱⁱ	0.891 (10)	1.985 (12)	2.870 (3)	172 (4)
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033091/hb5054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033091/hb5054Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies of Schiff bases (Qian & Qu, 2009), we now report the synthsis and structure of the title compound, (I), (Fig. 1).

The Schiff base molecule adopts an E geometry with respect to the C=N bond, and there forms an intramolecular O—H···N hydrogen bond. The two benzene rings forms a dihedral angle of 45.0 (2)°. The dihedral angle between the O3/N3/O4 plane and the C9—C14 benzene ring is 39.2 (2)°. In the crystal structure, the adjacent two Schiff base molecules are linked by a methanol molecule through intermolecular N—H···O and O—H···O hydrogen bonds (Table 1) to form a dimer (Fig. 2).

Related literature top

For a related structure and background, see: Qian & Qu (2009).

Experimental top

2-Nitrobenzohydrazide (1 mmol, 0.181 g) and 3,5-diiodosalicylaldehyde (1 mmol, 0.374 g) were dissolved in anhydrous methanol (15 ml). The mixture was stirred for several minutes at room temperature. The product was isolated and recrystallized from methanol, colorless blocks of (I) were obtained after 3 days.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonding is shown by dashed lines.
	Fig. 2. The molecular packing of the title compound, viewed along the b axis. Hydrogen bonding is shown in dashed lines.

(E)-N'-(2-Hydroxy-3,5-diiodobenzylidene)-2-nitrobenzohydrazide methanol solvate top

Crystal data top

C₁₄H₉I₂N₃O₄·CH₄O	F(000) = 2160
M_r = 569.08	D_x = 2.045 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5751 reflections
a = 19.5041 (12) Å	θ = 2.5–30.0°
b = 10.2306 (7) Å	µ = 3.43 mm⁻¹
c = 19.9474 (14) Å	T = 298 K
β = 111.764 (4)°	Block, colorless
V = 3696.6 (4) Å³	0.20 × 0.20 × 0.18 mm
Z = 8

Data collection top

Bruker SMART CCD diffractometer	4015 independent reflections
Radiation source: fine-focus sealed tube	3394 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω scans	θ_max = 27.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −24→22
T_min = 0.547, T_max = 0.577	k = −13→10
11057 measured reflections	l = −25→25

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.0318P)² + 0.9087P] where P = (F_o² + 2F_c²)/3
4015 reflections	(Δ/σ)_max = 0.001
232 parameters	Δρ_max = 0.44 e Å⁻³
1 restraint	Δρ_min = −1.02 e Å⁻³

Crystal data top

C₁₄H₉I₂N₃O₄·CH₄O	V = 3696.6 (4) Å³
M_r = 569.08	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 19.5041 (12) Å	µ = 3.43 mm⁻¹
b = 10.2306 (7) Å	T = 298 K
c = 19.9474 (14) Å	0.20 × 0.20 × 0.18 mm
β = 111.764 (4)°

Data collection top

Bruker SMART CCD diffractometer	4015 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3394 reflections with I > 2σ(I)
T_min = 0.547, T_max = 0.577	R_int = 0.027
11057 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	1 restraint
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.44 e Å⁻³
4015 reflections	Δρ_min = −1.02 e Å⁻³
232 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
I1	0.143857 (13)	0.30042 (2)	−0.138167 (11)	0.05559 (9)
I2	0.067514 (12)	0.86426 (2)	−0.123056 (11)	0.05414 (9)
N1	0.25171 (13)	0.6839 (2)	0.15211 (12)	0.0419 (6)
N2	0.29927 (14)	0.6742 (2)	0.22329 (12)	0.0418 (6)
N3	0.42504 (16)	0.9532 (3)	0.35060 (14)	0.0540 (7)
O1	0.16625 (13)	0.8109 (2)	0.03922 (11)	0.0512 (6)
H1	0.1961	0.8028	0.0807	0.077*
O2	0.27120 (13)	0.8790 (2)	0.24931 (11)	0.0546 (6)
O3	0.42749 (16)	0.9390 (3)	0.29089 (12)	0.0736 (8)
O4	0.4402 (2)	1.0549 (3)	0.38515 (16)	0.0940 (10)
O5	0.63153 (13)	0.4225 (2)	0.24221 (12)	0.0578 (6)
H5	0.6700	0.4074	0.2360	0.087*
C1	0.19975 (15)	0.5847 (3)	0.03648 (14)	0.0380 (6)
C2	0.16300 (16)	0.6994 (3)	0.00277 (14)	0.0369 (6)
C3	0.12219 (15)	0.6956 (3)	−0.07147 (14)	0.0385 (6)
C4	0.11739 (16)	0.5834 (3)	−0.11097 (14)	0.0413 (7)
H4	0.0900	0.5829	−0.1603	0.050*
C5	0.15337 (16)	0.4712 (3)	−0.07701 (15)	0.0425 (7)
C6	0.19422 (16)	0.4716 (3)	−0.00401 (14)	0.0417 (7)
H6	0.2183	0.3959	0.0184	0.050*
C7	0.24533 (16)	0.5819 (3)	0.11310 (14)	0.0415 (7)
H7	0.2700	0.5056	0.1338	0.050*
C8	0.30522 (15)	0.7759 (3)	0.26755 (14)	0.0385 (6)
C9	0.35442 (16)	0.7502 (3)	0.34453 (14)	0.0377 (6)
C10	0.40679 (17)	0.8399 (3)	0.38486 (15)	0.0410 (6)
C11	0.4469 (2)	0.8220 (3)	0.45769 (16)	0.0533 (8)
H11	0.4814	0.8838	0.4839	0.064*
C12	0.4346 (2)	0.7113 (4)	0.49031 (17)	0.0621 (10)
H12	0.4614	0.6974	0.5391	0.075*
C13	0.3837 (2)	0.6215 (4)	0.45209 (17)	0.0640 (10)
H13	0.3760	0.5469	0.4750	0.077*
C14	0.34329 (19)	0.6404 (3)	0.37922 (16)	0.0491 (8)
H14	0.3085	0.5786	0.3536	0.059*
C15	0.5718 (2)	0.3661 (4)	0.1857 (2)	0.0800 (13)
H15A	0.5270	0.3806	0.1940	0.120*
H15B	0.5800	0.2739	0.1838	0.120*
H15C	0.5678	0.4054	0.1407	0.120*
H2	0.324 (2)	0.600 (2)	0.237 (2)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.06140 (16)	0.04922 (14)	0.04793 (13)	−0.00025 (10)	0.01070 (11)	−0.01635 (9)
I2	0.05556 (15)	0.05314 (15)	0.04538 (13)	0.01490 (9)	0.00901 (10)	0.01138 (9)
N1	0.0382 (13)	0.0469 (14)	0.0291 (11)	0.0020 (10)	−0.0010 (10)	−0.0033 (10)
N2	0.0445 (14)	0.0384 (13)	0.0290 (11)	0.0081 (11)	−0.0021 (10)	−0.0019 (10)
N3	0.0567 (17)	0.0532 (17)	0.0405 (14)	−0.0102 (13)	0.0046 (12)	0.0001 (12)
O1	0.0615 (15)	0.0400 (12)	0.0383 (11)	0.0108 (10)	0.0024 (10)	−0.0057 (9)
O2	0.0569 (14)	0.0436 (13)	0.0481 (12)	0.0149 (10)	0.0019 (10)	−0.0024 (10)
O3	0.089 (2)	0.0819 (19)	0.0490 (14)	−0.0147 (15)	0.0246 (14)	0.0089 (13)
O4	0.139 (3)	0.0533 (17)	0.0708 (17)	−0.0332 (17)	0.0174 (18)	−0.0079 (14)
O5	0.0566 (14)	0.0457 (13)	0.0594 (13)	−0.0042 (11)	0.0080 (11)	−0.0033 (11)
C1	0.0361 (15)	0.0392 (15)	0.0316 (13)	0.0014 (12)	0.0042 (11)	−0.0010 (11)
C2	0.0370 (15)	0.0358 (15)	0.0341 (13)	0.0011 (11)	0.0087 (12)	−0.0009 (11)
C3	0.0348 (15)	0.0436 (16)	0.0343 (13)	0.0068 (12)	0.0095 (12)	0.0049 (11)
C4	0.0363 (15)	0.0511 (18)	0.0315 (13)	−0.0004 (12)	0.0068 (11)	−0.0037 (12)
C5	0.0426 (16)	0.0430 (16)	0.0368 (14)	−0.0011 (13)	0.0088 (12)	−0.0069 (12)
C6	0.0419 (16)	0.0368 (15)	0.0379 (14)	0.0019 (12)	0.0051 (12)	−0.0026 (12)
C7	0.0436 (16)	0.0370 (15)	0.0339 (14)	0.0039 (12)	0.0029 (12)	−0.0002 (12)
C8	0.0338 (14)	0.0400 (16)	0.0343 (13)	0.0025 (12)	0.0041 (11)	−0.0033 (11)
C9	0.0405 (15)	0.0387 (15)	0.0316 (13)	0.0051 (12)	0.0107 (11)	−0.0038 (12)
C10	0.0454 (17)	0.0392 (16)	0.0336 (13)	0.0016 (12)	0.0090 (12)	−0.0024 (12)
C11	0.061 (2)	0.0546 (19)	0.0320 (14)	0.0020 (16)	0.0024 (14)	−0.0109 (14)
C12	0.082 (3)	0.066 (2)	0.0297 (15)	0.0082 (19)	0.0103 (16)	0.0026 (15)
C13	0.090 (3)	0.057 (2)	0.0406 (17)	−0.0001 (19)	0.0190 (18)	0.0088 (15)
C14	0.059 (2)	0.0411 (17)	0.0441 (16)	−0.0029 (14)	0.0157 (15)	−0.0033 (13)
C15	0.074 (3)	0.058 (2)	0.074 (3)	−0.0091 (19)	−0.012 (2)	0.0031 (19)

Geometric parameters (Å, º) top

I1—C5	2.099 (3)	C4—C5	1.384 (4)
I2—C3	2.088 (3)	C4—H4	0.9300
N1—C7	1.280 (4)	C5—C6	1.377 (4)
N1—N2	1.382 (3)	C6—H6	0.9300
N2—C8	1.341 (4)	C7—H7	0.9300
N2—H2	0.891 (10)	C8—C9	1.502 (4)
N3—O3	1.218 (3)	C9—C14	1.378 (4)
N3—O4	1.222 (4)	C9—C10	1.386 (4)
N3—C10	1.456 (4)	C10—C11	1.383 (4)
O1—C2	1.341 (3)	C11—C12	1.371 (5)
O1—H1	0.8200	C11—H11	0.9300
O2—C8	1.227 (3)	C12—C13	1.360 (5)
O5—C15	1.410 (4)	C12—H12	0.9300
O5—H5	0.8200	C13—C14	1.386 (4)
C1—C6	1.392 (4)	C13—H13	0.9300
C1—C2	1.409 (4)	C14—H14	0.9300
C1—C7	1.456 (4)	C15—H15A	0.9600
C2—C3	1.398 (4)	C15—H15B	0.9600
C3—C4	1.376 (4)	C15—H15C	0.9600

C7—N1—N2	116.3 (2)	C1—C7—H7	119.8
C8—N2—N1	118.8 (2)	O2—C8—N2	124.5 (3)
C8—N2—H2	124 (3)	O2—C8—C9	121.6 (3)
N1—N2—H2	117 (3)	N2—C8—C9	113.8 (2)
O3—N3—O4	124.4 (3)	C14—C9—C10	117.8 (3)
O3—N3—C10	117.9 (3)	C14—C9—C8	119.7 (3)
O4—N3—C10	117.6 (3)	C10—C9—C8	122.1 (3)
C2—O1—H1	109.5	C11—C10—C9	122.0 (3)
C15—O5—H5	109.5	C11—C10—N3	117.2 (3)
C6—C1—C2	119.9 (2)	C9—C10—N3	120.7 (2)
C6—C1—C7	118.6 (3)	C12—C11—C10	118.5 (3)
C2—C1—C7	121.5 (3)	C12—C11—H11	120.8
O1—C2—C3	119.5 (2)	C10—C11—H11	120.8
O1—C2—C1	122.4 (2)	C13—C12—C11	120.8 (3)
C3—C2—C1	118.1 (3)	C13—C12—H12	119.6
C4—C3—C2	121.4 (3)	C11—C12—H12	119.6
C4—C3—I2	119.6 (2)	C12—C13—C14	120.4 (3)
C2—C3—I2	119.0 (2)	C12—C13—H13	119.8
C3—C4—C5	119.8 (2)	C14—C13—H13	119.8
C3—C4—H4	120.1	C9—C14—C13	120.4 (3)
C5—C4—H4	120.1	C9—C14—H14	119.8
C6—C5—C4	120.3 (3)	C13—C14—H14	119.8
C6—C5—I1	120.6 (2)	O5—C15—H15A	109.5
C4—C5—I1	119.09 (19)	O5—C15—H15B	109.5
C5—C6—C1	120.4 (3)	H15A—C15—H15B	109.5
C5—C6—H6	119.8	O5—C15—H15C	109.5
C1—C6—H6	119.8	H15A—C15—H15C	109.5
N1—C7—C1	120.4 (3)	H15B—C15—H15C	109.5
N1—C7—H7	119.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2ⁱ	0.82	1.91	2.711 (4)	164
O1—H1···N1	0.82	1.88	2.599 (3)	146
N2—H2···O5ⁱⁱ	0.89 (1)	1.99 (1)	2.870 (3)	172 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₉I₂N₃O₄·CH₄O
M_r	569.08
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	19.5041 (12), 10.2306 (7), 19.9474 (14)
β (°)	111.764 (4)
V (Å³)	3696.6 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.43
Crystal size (mm)	0.20 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.547, 0.577
No. of measured, independent and observed [I > 2σ(I)] reflections	11057, 4015, 3394
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.068, 1.11
No. of reflections	4015
No. of parameters	232
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −1.02

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2ⁱ	0.82	1.91	2.711 (4)	164
O1—H1···N1	0.82	1.88	2.599 (3)	146
N2—H2···O5ⁱⁱ	0.891 (10)	1.985 (12)	2.870 (3)	172 (4)

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

References

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Qian, H.-Y. & Qu, D.-P. (2009). Acta Cryst. E65, o2237. 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

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2238

doi:10.1107/S1600536809033091

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

(E)-N′-(2-Hydr­­oxy-3,5-di­iodo­benzyl­­idene)-2-nitro­benzohydrazide methanol solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

(E)-N′-(2-Hydroxy-3,5-diiodobenzylidene)-2-nitrobenzohydrazide methanol solvate