2-[(2-Chloro­phen­yl)imino­meth­yl]-4,6-di­iodo­phenol

Ji, H.; Yang, Y.-A.; Ma, H.-P.; Zhu, H.-L.

doi:10.1107/S1600536812007325

organic compounds

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Volume 68| Part 3| March 2012| Page o841

doi:10.1107/S1600536812007325

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2-[(2-Chlorophenyl)iminomethyl]-4,6-diiodophenol

Hao Ji,^a Yong-An Yang,^a Hua-Ping Ma ^a and Hai-Liang Zhu ^a ^*

^aState Key Laboratory of Pharmaceutical Biotechnology, Nanjing University, Nanjing 210093, People's Republic of China, and Jiangsu Tiansheng Pharmaceutical Company Limited, Jurong Jiangsu 212415, People's Republic of China
^*Correspondence e-mail: hailiang_zhu@163.com

(Received 8 February 2012; accepted 18 February 2012; online 24 February 2012)

The asymmetric unit of the title compound, C₁₃H₈ClI₂NO, contains half of the molecule situated on a mirror plane. The hydroxy group is involved in the formation of an intramolecular O—H⋯N hydrogen bond. π–π interactions between the benzene rings of neighbouring molecules [centroid–centroid distance = 3.629 (3) Å] form stacks along the b axis. In the crystal, weak C—H⋯O and C—H⋯Cl interactions are observed.

Related literature

For standard bond distances, see: Allen et al. (1987 ). For the crystal structures of related compounds, see: Francis et al. (2003 ); Weiser et al. (2006 ); Barba et al. (2009 ).

Experimental

Crystal data

C₁₃H₈ClI₂NO
M_r = 483.45
Orthorhombic, P n m a
a = 15.8432 (17) Å
b = 6.9942 (8) Å
c = 13.1975 (14) Å
V = 1462.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 4.47 mm⁻¹
T = 296 K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.468, T_max = 0.663
9861 measured reflections
1829 independent reflections
1659 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.144
S = 0.98
1829 reflections
113 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.13 e Å⁻³
Δρ_min = −0.76 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N1	0.84 (2)	1.95 (8)	2.568 (8)	130 (9)
C11—H11A⋯O1ⁱ	0.93	2.57	3.496 (8)	178
C12—H12A⋯Cl1ⁱ	0.93	2.83	3.640 (8)	147
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812007325/cv5247sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007325/cv5247Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812007325/cv5247Isup3.cml

checkCIF report

Comment top

Schiff bases have been extensively studied for their structures and applications. In the present paper, we present the title compound (I) (Fig. 1) - a new Schiff base compound.

The asymmetric unit of (I) contains a half of the molecule situated on a mirror plane. The molecule of the compound adopts an E configuration with respect to the C=N bond. The hydroxy group is involved in formation of intramolecular O—H···N hydrogen bond (Table 1). Bond distances are within normal values (Allen et al., 1987), and are comparable with those reported in the literature for related compounds (Weiser et al., 2006; Barba et al., 2009; Francis et al., 2003).

π–π Interactions between the benzene rings of the neighbouring molecules [centroid-centroid distance = 3.629 (3) Å] form stacks along axis b. Weak intermolecular C—H···O and C—H···Cl interactions (Table 1) consolidate further the crystal packing.

Related literature top

For standard bond distances, see: Allen et al. (1987). For the crystal structures of related compounds, see: Francis et al. (2003); Weiser et al. (2006); Barba et al. (2009).

Experimental top

3,5-Diiodosalicylaldehyde (0.37 g, 1 mmol) and 2-chlorophenylamine (0.13 g, 1 mmol) were mixed in ethanol (20 ml). The mixture was stirred at room temperature for 30 min to give a yellow solution. Yellow block-shaped single crystals were obtained by slow evaporation of the solution containing the compound in air.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (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 the title compound, showing the atom labelling scheme. The displacement ellipsoids are drawn at the 30% probability level. Intramolecular hydrogen bond is indicated by a dashed line.

2-[(2-Chlorophenyl)iminomethyl]-4,6-diiodophenol top

Crystal data top

C₁₃H₈ClI₂NO	D_x = 2.196 Mg m⁻³
M_r = 483.45	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 897 reflections
a = 15.8432 (17) Å	θ = 2.4–24.5°
b = 6.9942 (8) Å	µ = 4.47 mm⁻¹
c = 13.1975 (14) Å	T = 296 K
V = 1462.4 (3) Å³	Block, yellow
Z = 4	0.20 × 0.10 × 0.10 mm
F(000) = 896

Data collection top

Bruker SMART CCD area-detector diffractometer	1829 independent reflections
Radiation source: fine-focus sealed tube	1659 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −20→20
T_min = 0.468, T_max = 0.663	k = −9→9
9861 measured reflections	l = −17→17

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.144	w = 1/[σ²(F_o²) + (0.1P)² + 4.5P] where P = (F_o² + 2F_c²)/3
S = 0.98	(Δ/σ)_max < 0.001
1829 reflections	Δρ_max = 1.13 e Å⁻³
113 parameters	Δρ_min = −0.76 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0030 (6)

Crystal data top

C₁₃H₈ClI₂NO	V = 1462.4 (3) Å³
M_r = 483.45	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 15.8432 (17) Å	µ = 4.47 mm⁻¹
b = 6.9942 (8) Å	T = 296 K
c = 13.1975 (14) Å	0.20 × 0.10 × 0.10 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1829 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1659 reflections with I > 2σ(I)
T_min = 0.468, T_max = 0.663	R_int = 0.029
9861 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 1.13 e Å⁻³
1829 reflections	Δρ_min = −0.76 e Å⁻³
113 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	0.19354 (3)	0.2500	0.09648 (5)	0.0692 (3)
I2	0.44288 (3)	0.2500	0.43751 (4)	0.0582 (3)
C3	0.3198 (4)	0.2500	0.1448 (5)	0.0444 (16)
C2	0.3847 (4)	0.2500	0.0744 (6)	0.0470 (17)
C5	0.4191 (4)	0.2500	0.2817 (5)	0.0403 (14)
O1	0.3668 (3)	0.2500	−0.0237 (4)	0.076 (2)
C4	0.3362 (4)	0.2500	0.2491 (5)	0.0395 (13)
H4A	0.2921	0.2500	0.2956	0.047*
C6	0.4851 (4)	0.2500	0.2125 (5)	0.0404 (14)
H6A	0.5406	0.2500	0.2352	0.048*
Cl1	0.46567 (14)	0.2500	−0.26597 (17)	0.0654 (6)
C10	0.6308 (6)	0.2500	−0.3086 (7)	0.056 (2)
H10A	0.6146	0.2500	−0.3764	0.068*
N1	0.5265 (4)	0.2500	−0.0572 (4)	0.0456 (14)
C12	0.7400 (5)	0.2500	−0.1822 (9)	0.073 (3)
H12A	0.7968	0.2500	−0.1647	0.088*
C13	0.6773 (5)	0.2500	−0.1049 (8)	0.065 (2)
H13A	0.6932	0.2500	−0.0370	0.078*
C8	0.5925 (4)	0.2500	−0.1305 (6)	0.0437 (15)
C1	0.4679 (4)	0.2500	0.1090 (5)	0.0353 (13)
C9	0.5697 (4)	0.2500	−0.2316 (6)	0.0442 (15)
C11	0.7168 (7)	0.2500	−0.2820 (9)	0.078 (3)
H11A	0.7579	0.2500	−0.3323	0.094*
C7	0.5388 (4)	0.2500	0.0385 (6)	0.0432 (15)
H7A	0.5937	0.2500	0.0635	0.052*
H1A	0.404 (5)	0.2500	−0.069 (6)	0.06 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0239 (3)	0.1386 (7)	0.0450 (4)	0.000	−0.00480 (18)	0.000
I2	0.0463 (3)	0.0979 (5)	0.0303 (3)	0.000	−0.00509 (18)	0.000
C3	0.025 (3)	0.078 (5)	0.030 (3)	0.000	−0.005 (2)	0.000
C2	0.024 (3)	0.079 (5)	0.037 (4)	0.000	−0.006 (3)	0.000
C5	0.028 (3)	0.065 (4)	0.027 (3)	0.000	−0.004 (2)	0.000
O1	0.027 (3)	0.171 (7)	0.029 (3)	0.000	−0.002 (2)	0.000
C4	0.032 (3)	0.055 (4)	0.031 (3)	0.000	0.001 (2)	0.000
C6	0.025 (3)	0.054 (4)	0.043 (4)	0.000	−0.006 (2)	0.000
Cl1	0.0433 (10)	0.1094 (18)	0.0435 (11)	0.000	−0.0023 (8)	0.000
C10	0.057 (5)	0.067 (5)	0.046 (4)	0.000	0.024 (4)	0.000
N1	0.032 (3)	0.070 (4)	0.035 (3)	0.000	0.008 (2)	0.000
C12	0.018 (3)	0.122 (8)	0.081 (7)	0.000	0.010 (4)	0.000
C13	0.028 (3)	0.107 (7)	0.060 (6)	0.000	0.004 (3)	0.000
C8	0.033 (3)	0.058 (4)	0.041 (4)	0.000	0.011 (3)	0.000
C1	0.023 (3)	0.049 (3)	0.034 (3)	0.000	−0.002 (2)	0.000
C9	0.033 (3)	0.060 (4)	0.039 (4)	0.000	0.008 (3)	0.000
C11	0.070 (6)	0.091 (7)	0.075 (7)	0.000	0.050 (6)	0.000
C7	0.023 (3)	0.061 (4)	0.046 (4)	0.000	0.003 (3)	0.000

Geometric parameters (Å, º) top

I1—C3	2.100 (6)	C10—C11	1.407 (15)
I2—C5	2.090 (6)	C10—H10A	0.9300
C3—C2	1.386 (10)	N1—C7	1.278 (10)
C3—C4	1.400 (9)	N1—C8	1.425 (8)
C2—O1	1.325 (9)	C12—C11	1.368 (16)
C2—C1	1.395 (9)	C12—C13	1.424 (13)
C5—C4	1.383 (9)	C12—H12A	0.9300
C5—C6	1.388 (9)	C13—C8	1.385 (11)
O1—H1A	0.84 (2)	C13—H13A	0.9300
C4—H4A	0.9300	C8—C9	1.382 (11)
C6—C1	1.393 (9)	C1—C7	1.459 (9)
C6—H6A	0.9300	C11—H11A	0.9300
Cl1—C9	1.709 (7)	C7—H7A	0.9300
C10—C9	1.404 (9)

C2—C3—C4	121.4 (6)	C11—C12—H12A	119.9
C2—C3—I1	120.2 (5)	C13—C12—H12A	119.9
C4—C3—I1	118.4 (5)	C8—C13—C12	120.1 (9)
O1—C2—C3	119.8 (6)	C8—C13—H13A	120.0
O1—C2—C1	121.5 (6)	C12—C13—H13A	120.0
C3—C2—C1	118.8 (6)	C9—C8—C13	119.3 (7)
C4—C5—C6	120.7 (6)	C9—C8—N1	117.6 (6)
C4—C5—I2	118.5 (5)	C13—C8—N1	123.0 (7)
C6—C5—I2	120.8 (5)	C6—C1—C2	120.4 (6)
C2—O1—H1A	123 (7)	C6—C1—C7	118.4 (6)
C5—C4—C3	118.9 (6)	C2—C1—C7	121.3 (6)
C5—C4—H4A	120.6	C8—C9—C10	121.2 (7)
C3—C4—H4A	120.6	C8—C9—Cl1	120.6 (5)
C5—C6—C1	119.9 (6)	C10—C9—Cl1	118.2 (7)
C5—C6—H6A	120.0	C12—C11—C10	120.0 (8)
C1—C6—H6A	120.0	C12—C11—H11A	120.0
C9—C10—C11	119.1 (8)	C10—C11—H11A	120.0
C9—C10—H10A	120.4	N1—C7—C1	120.8 (6)
C11—C10—H10A	120.4	N1—C7—H7A	119.6
C7—N1—C8	124.0 (6)	C1—C7—H7A	119.6
C11—C12—C13	120.2 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.84 (2)	1.95 (8)	2.568 (8)	130 (9)
C11—H11A···O1ⁱ	0.93	2.57	3.496 (8)	178
C12—H12A···Cl1ⁱ	0.93	2.83	3.640 (8)	147

Symmetry code: (i) x+1/2, −y+1/2, −z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₈ClI₂NO
M_r	483.45
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	296
a, b, c (Å)	15.8432 (17), 6.9942 (8), 13.1975 (14)
V (Å³)	1462.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.47
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.468, 0.663
No. of measured, independent and observed [I > 2σ(I)] reflections	9861, 1829, 1659
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.144, 0.98
No. of reflections	1829
No. of parameters	113
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)	1.13, −0.76

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.84 (2)	1.95 (8)	2.568 (8)	130 (9)
C11—H11A···O1ⁱ	0.93	2.57	3.496 (8)	178
C12—H12A···Cl1ⁱ	0.93	2.83	3.640 (8)	147

Symmetry code: (i) x+1/2, −y+1/2, −z−1/2.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Barba, V., Hernandez, R., Hopfl, H., Santillan, R. & Farfan, N. (2009). J. Organomet. Chem. 694, 2127–2133. Web of Science CSD CrossRef CAS Google Scholar
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Francis, S., Muthiah, P. T., Venkatachalam, G. & Ramesh, R. (2003). Acta Cryst. E59, o1045–o1047. 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
Weiser, M.-S., Wesolek, M. & Mulhaupt, R. (2006). J. Organomet. Chem. 691, 2945–2952. Web of Science CSD CrossRef CAS Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o841

doi:10.1107/S1600536812007325

Open

access