PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): o2238.
Published online 2009 August 26. doi:  10.1107/S1600536809033091
PMCID: PMC2970043

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

Abstract

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 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2238-scheme1.jpg

Experimental

Crystal data

  • C14H9I2N3O4·CH4O
  • M r = 569.08
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2238-efi1.jpg
  • 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 [triangle]) 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[F 2 > 2σ(F 2)] = 0.028
  • wR(F 2) = 0.068
  • S = 1.11
  • 4015 reflections
  • 232 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.44 e Å−3
  • Δρmin = −1.02 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The imino H atom was located in a difference map and its positional parameters were refined with a fixed isotropic thermal parameter of 0.08 Å2. Other H atoms were positioned geometrically and refined as riding with C—H = 0.93 Å (aromatic) and 0.96 Å (methyl), O—H = 0.82 å, and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(C15 and O).

Figures

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.

Crystal data

C14H9I2N3O4·CH4OF(000) = 2160
Mr = 569.08Dx = 2.045 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 5751 reflections
a = 19.5041 (12) Åθ = 2.5–30.0°
b = 10.2306 (7) ŵ = 3.43 mm1
c = 19.9474 (14) ÅT = 298 K
β = 111.764 (4)°Block, colorless
V = 3696.6 (4) Å30.20 × 0.20 × 0.18 mm
Z = 8

Data collection

Bruker SMART CCD diffractometer4015 independent reflections
Radiation source: fine-focus sealed tube3394 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −24→22
Tmin = 0.547, Tmax = 0.577k = −13→10
11057 measured reflectionsl = −25→25

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 1.11w = 1/[σ2(Fo2) + (0.0318P)2 + 0.9087P] where P = (Fo2 + 2Fc2)/3
4015 reflections(Δ/σ)max = 0.001
232 parametersΔρmax = 0.44 e Å3
1 restraintΔρmin = −1.02 e Å3

Special details

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)

xyzUiso*/Ueq
I10.143857 (13)0.30042 (2)−0.138167 (11)0.05559 (9)
I20.067514 (12)0.86426 (2)−0.123056 (11)0.05414 (9)
N10.25171 (13)0.6839 (2)0.15211 (12)0.0419 (6)
N20.29927 (14)0.6742 (2)0.22329 (12)0.0418 (6)
N30.42504 (16)0.9532 (3)0.35060 (14)0.0540 (7)
O10.16625 (13)0.8109 (2)0.03922 (11)0.0512 (6)
H10.19610.80280.08070.077*
O20.27120 (13)0.8790 (2)0.24931 (11)0.0546 (6)
O30.42749 (16)0.9390 (3)0.29089 (12)0.0736 (8)
O40.4402 (2)1.0549 (3)0.38515 (16)0.0940 (10)
O50.63153 (13)0.4225 (2)0.24221 (12)0.0578 (6)
H50.67000.40740.23600.087*
C10.19975 (15)0.5847 (3)0.03648 (14)0.0380 (6)
C20.16300 (16)0.6994 (3)0.00277 (14)0.0369 (6)
C30.12219 (15)0.6956 (3)−0.07147 (14)0.0385 (6)
C40.11739 (16)0.5834 (3)−0.11097 (14)0.0413 (7)
H40.09000.5829−0.16030.050*
C50.15337 (16)0.4712 (3)−0.07701 (15)0.0425 (7)
C60.19422 (16)0.4716 (3)−0.00401 (14)0.0417 (7)
H60.21830.39590.01840.050*
C70.24533 (16)0.5819 (3)0.11310 (14)0.0415 (7)
H70.27000.50560.13380.050*
C80.30522 (15)0.7759 (3)0.26755 (14)0.0385 (6)
C90.35442 (16)0.7502 (3)0.34453 (14)0.0377 (6)
C100.40679 (17)0.8399 (3)0.38486 (15)0.0410 (6)
C110.4469 (2)0.8220 (3)0.45769 (16)0.0533 (8)
H110.48140.88380.48390.064*
C120.4346 (2)0.7113 (4)0.49031 (17)0.0621 (10)
H120.46140.69740.53910.075*
C130.3837 (2)0.6215 (4)0.45209 (17)0.0640 (10)
H130.37600.54690.47500.077*
C140.34329 (19)0.6404 (3)0.37922 (16)0.0491 (8)
H140.30850.57860.35360.059*
C150.5718 (2)0.3661 (4)0.1857 (2)0.0800 (13)
H15A0.52700.38060.19400.120*
H15B0.58000.27390.18380.120*
H15C0.56780.40540.14070.120*
H20.324 (2)0.600 (2)0.237 (2)0.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
I10.06140 (16)0.04922 (14)0.04793 (13)−0.00025 (10)0.01070 (11)−0.01635 (9)
I20.05556 (15)0.05314 (15)0.04538 (13)0.01490 (9)0.00901 (10)0.01138 (9)
N10.0382 (13)0.0469 (14)0.0291 (11)0.0020 (10)−0.0010 (10)−0.0033 (10)
N20.0445 (14)0.0384 (13)0.0290 (11)0.0081 (11)−0.0021 (10)−0.0019 (10)
N30.0567 (17)0.0532 (17)0.0405 (14)−0.0102 (13)0.0046 (12)0.0001 (12)
O10.0615 (15)0.0400 (12)0.0383 (11)0.0108 (10)0.0024 (10)−0.0057 (9)
O20.0569 (14)0.0436 (13)0.0481 (12)0.0149 (10)0.0019 (10)−0.0024 (10)
O30.089 (2)0.0819 (19)0.0490 (14)−0.0147 (15)0.0246 (14)0.0089 (13)
O40.139 (3)0.0533 (17)0.0708 (17)−0.0332 (17)0.0174 (18)−0.0079 (14)
O50.0566 (14)0.0457 (13)0.0594 (13)−0.0042 (11)0.0080 (11)−0.0033 (11)
C10.0361 (15)0.0392 (15)0.0316 (13)0.0014 (12)0.0042 (11)−0.0010 (11)
C20.0370 (15)0.0358 (15)0.0341 (13)0.0011 (11)0.0087 (12)−0.0009 (11)
C30.0348 (15)0.0436 (16)0.0343 (13)0.0068 (12)0.0095 (12)0.0049 (11)
C40.0363 (15)0.0511 (18)0.0315 (13)−0.0004 (12)0.0068 (11)−0.0037 (12)
C50.0426 (16)0.0430 (16)0.0368 (14)−0.0011 (13)0.0088 (12)−0.0069 (12)
C60.0419 (16)0.0368 (15)0.0379 (14)0.0019 (12)0.0051 (12)−0.0026 (12)
C70.0436 (16)0.0370 (15)0.0339 (14)0.0039 (12)0.0029 (12)−0.0002 (12)
C80.0338 (14)0.0400 (16)0.0343 (13)0.0025 (12)0.0041 (11)−0.0033 (11)
C90.0405 (15)0.0387 (15)0.0316 (13)0.0051 (12)0.0107 (11)−0.0038 (12)
C100.0454 (17)0.0392 (16)0.0336 (13)0.0016 (12)0.0090 (12)−0.0024 (12)
C110.061 (2)0.0546 (19)0.0320 (14)0.0020 (16)0.0024 (14)−0.0109 (14)
C120.082 (3)0.066 (2)0.0297 (15)0.0082 (19)0.0103 (16)0.0026 (15)
C130.090 (3)0.057 (2)0.0406 (17)−0.0001 (19)0.0190 (18)0.0088 (15)
C140.059 (2)0.0411 (17)0.0441 (16)−0.0029 (14)0.0157 (15)−0.0033 (13)
C150.074 (3)0.058 (2)0.074 (3)−0.0091 (19)−0.012 (2)0.0031 (19)

Geometric parameters (Å, °)

I1—C52.099 (3)C4—C51.384 (4)
I2—C32.088 (3)C4—H40.9300
N1—C71.280 (4)C5—C61.377 (4)
N1—N21.382 (3)C6—H60.9300
N2—C81.341 (4)C7—H70.9300
N2—H20.891 (10)C8—C91.502 (4)
N3—O31.218 (3)C9—C141.378 (4)
N3—O41.222 (4)C9—C101.386 (4)
N3—C101.456 (4)C10—C111.383 (4)
O1—C21.341 (3)C11—C121.371 (5)
O1—H10.8200C11—H110.9300
O2—C81.227 (3)C12—C131.360 (5)
O5—C151.410 (4)C12—H120.9300
O5—H50.8200C13—C141.386 (4)
C1—C61.392 (4)C13—H130.9300
C1—C21.409 (4)C14—H140.9300
C1—C71.456 (4)C15—H15A0.9600
C2—C31.398 (4)C15—H15B0.9600
C3—C41.376 (4)C15—H15C0.9600
C7—N1—N2116.3 (2)C1—C7—H7119.8
C8—N2—N1118.8 (2)O2—C8—N2124.5 (3)
C8—N2—H2124 (3)O2—C8—C9121.6 (3)
N1—N2—H2117 (3)N2—C8—C9113.8 (2)
O3—N3—O4124.4 (3)C14—C9—C10117.8 (3)
O3—N3—C10117.9 (3)C14—C9—C8119.7 (3)
O4—N3—C10117.6 (3)C10—C9—C8122.1 (3)
C2—O1—H1109.5C11—C10—C9122.0 (3)
C15—O5—H5109.5C11—C10—N3117.2 (3)
C6—C1—C2119.9 (2)C9—C10—N3120.7 (2)
C6—C1—C7118.6 (3)C12—C11—C10118.5 (3)
C2—C1—C7121.5 (3)C12—C11—H11120.8
O1—C2—C3119.5 (2)C10—C11—H11120.8
O1—C2—C1122.4 (2)C13—C12—C11120.8 (3)
C3—C2—C1118.1 (3)C13—C12—H12119.6
C4—C3—C2121.4 (3)C11—C12—H12119.6
C4—C3—I2119.6 (2)C12—C13—C14120.4 (3)
C2—C3—I2119.0 (2)C12—C13—H13119.8
C3—C4—C5119.8 (2)C14—C13—H13119.8
C3—C4—H4120.1C9—C14—C13120.4 (3)
C5—C4—H4120.1C9—C14—H14119.8
C6—C5—C4120.3 (3)C13—C14—H14119.8
C6—C5—I1120.6 (2)O5—C15—H15A109.5
C4—C5—I1119.09 (19)O5—C15—H15B109.5
C5—C6—C1120.4 (3)H15A—C15—H15B109.5
C5—C6—H6119.8O5—C15—H15C109.5
C1—C6—H6119.8H15A—C15—H15C109.5
N1—C7—C1120.4 (3)H15B—C15—H15C109.5
N1—C7—H7119.8

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O5—H5···O2i0.821.912.711 (4)164
O1—H1···N10.821.882.599 (3)146
N2—H2···O5ii0.89 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5054).

References

  • Bruker (2001). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Qian, H.-Y. & Qu, D.-P. (2009). Acta Cryst. E65, o2237. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography