2-[(4-Bromo­phenyl­imino)­meth­yl]-4,6-di­iodo­phenol

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

doi:10.1107/S160053681200551X

organic compounds

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Volume 68| Part 3| March 2012| Page o788

doi:10.1107/S160053681200551X

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2-[(4-Bromophenylimino)methyl]-4,6-diiodophenol

Hao Ji,^a Hua-Ping Ma,^a Yong-An Yang ^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 7 February 2012; accepted 7 February 2012; online 24 February 2012)

The title compound, C₁₃H₈BrI₂NO, was prepared by the reaction of 3,5-diiodosalicylaldehyde with 4-bromophenylamine in ethanol. There is an intramolecular O—H⋯N hydrogen bond in the molecule, which generates an S(6) ring. The dihedral angle between the benzene rings is 2.6 (3)°.

Related literature

For the biological activities of Schiff bases, see: Chohan et al. (2012 ); Yan et al. (2011 ); Zhang et al. (2011 ). For the coordination of Schiff bases, see: You et al. (2008 ); Xu et al. (2009 ); Chen et al. (2010 ); Cui et al. (2011 ). For reference bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₃H₈BrI₂NO
M_r = 527.91
Triclinic, $[P \overline 1]$
a = 7.9870 (13) Å
b = 8.9811 (14) Å
c = 11.3907 (18) Å
α = 91.093 (2)°
β = 99.873 (2)°
γ = 114.570 (2)°
V = 728.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 7.05 mm⁻¹
T = 298 K
0.17 × 0.15 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.380, T_max = 0.418
6174 measured reflections
3125 independent reflections
2425 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.094
S = 1.07
3125 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 1.26 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—H1⋯N1	0.82	1.85	2.576 (5)	148

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/S160053681200551X/qm2053sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681200551X/qm2053Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681200551X/qm2053Isup3.cml

checkCIF report

Comment top

Schiff bases have been extensively studied for their biological activities (Chohan et al., 2012; Yan et al., 2011; Zhang et al., 2011). In addition, Schiff bases are versatile ligands for the preparation of metal complexes (You et al., 2008; Xu et al., 2009; Chen et al., 2010; Cui et al., 2011). In the present paper, the new title compound is reported.

The molecule of the compound exists in a trans configuration with respect to the methylidene unit (Fig. 1). There is an intramolecular O1—H1···N1 hydrogen bond in the molecule (Table 1). The dihedral angle between the C1–C6 and C8–C13 benzene rings is 2.6 (3)°. The bond distances are within the normal range (Allen et al., 1987).

Related literature top

For the biological activities of Schiff bases, see: Chohan et al. (2012); Yan et al. (2011); Zhang et al. (2011). For the coordination of Schiff bases, see: You et al. (2008); Xu et al. (2009); Chen et al. (2010); Cui et al. (2011). For reference bond lengths, see: Allen et al. (1987).

Experimental top

3,5-Diiodosalicylaldehyde (0.37 g, 1 mmol) and 4-bromophenylamine (0.17 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 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. The intramolecular hydrogen bond is indicated by a dashed line.

2-[(4-Bromophenylimino)methyl]-4,6-diiodophenol top

Crystal data top

C₁₃H₈BrI₂NO	Z = 2
M_r = 527.91	F(000) = 484
Triclinic, P1	D_x = 2.407 Mg m⁻³
a = 7.9870 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9811 (14) Å	Cell parameters from 1027 reflections
c = 11.3907 (18) Å	θ = 2.5–25.1°
α = 91.093 (2)°	µ = 7.05 mm⁻¹
β = 99.873 (2)°	T = 298 K
γ = 114.570 (2)°	Block, yellow
V = 728.4 (2) Å³	0.17 × 0.15 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3125 independent reflections
Radiation source: fine-focus sealed tube	2425 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ω scans	θ_max = 27.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.380, T_max = 0.418	k = −10→11
6174 measured reflections	l = −14→14

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0399P)² + 1.2928P] where P = (F_o² + 2F_c²)/3
3125 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 1.26 e Å⁻³
0 restraints	Δρ_min = −0.76 e Å⁻³

Crystal data top

C₁₃H₈BrI₂NO	γ = 114.570 (2)°
M_r = 527.91	V = 728.4 (2) Å³
Triclinic, P1	Z = 2
a = 7.9870 (13) Å	Mo Kα radiation
b = 8.9811 (14) Å	µ = 7.05 mm⁻¹
c = 11.3907 (18) Å	T = 298 K
α = 91.093 (2)°	0.17 × 0.15 × 0.15 mm
β = 99.873 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3125 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2425 reflections with I > 2σ(I)
T_min = 0.380, T_max = 0.418	R_int = 0.022
6174 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.07	Δρ_max = 1.26 e Å⁻³
3125 reflections	Δρ_min = −0.76 e Å⁻³
164 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	0.87298 (7)	0.30448 (5)	−0.38474 (3)	0.06516 (15)
Br1	0.27660 (10)	0.16630 (8)	0.47166 (5)	0.0712 (2)
I2	1.20768 (6)	1.02378 (4)	−0.20734 (4)	0.06502 (15)
N1	0.6508 (5)	0.3888 (5)	0.0440 (3)	0.0403 (9)
O1	0.7124 (6)	0.2911 (4)	−0.1515 (3)	0.0532 (9)
H1	0.6635	0.2839	−0.0929	0.080*
C1	0.8487 (7)	0.5748 (6)	−0.0729 (4)	0.0390 (10)
C2	0.8205 (6)	0.4496 (6)	−0.1604 (4)	0.0380 (10)
C3	0.9082 (7)	0.4926 (6)	−0.2583 (4)	0.0421 (11)
C4	1.0185 (7)	0.6550 (6)	−0.2713 (4)	0.0444 (11)
H4	1.0764	0.6820	−0.3371	0.053*
C5	1.0422 (7)	0.7773 (6)	−0.1854 (4)	0.0418 (11)
C6	0.9621 (7)	0.7389 (6)	−0.0865 (4)	0.0416 (11)
H6	0.9830	0.8220	−0.0282	0.050*
C7	0.7600 (7)	0.5360 (6)	0.0313 (4)	0.0419 (11)
H7	0.7836	0.6202	0.0894	0.050*
C8	0.5660 (6)	0.3466 (6)	0.1464 (4)	0.0397 (10)
C9	0.5782 (8)	0.4581 (7)	0.2364 (5)	0.0554 (14)
H9	0.6453	0.5703	0.2325	0.066*
C10	0.4912 (8)	0.4041 (7)	0.3323 (5)	0.0548 (14)
H10	0.4986	0.4796	0.3922	0.066*
C11	0.3947 (7)	0.2400 (7)	0.3386 (4)	0.0469 (12)
C12	0.3773 (8)	0.1262 (7)	0.2497 (5)	0.0547 (14)
H12	0.3098	0.0143	0.2545	0.066*
C13	0.4618 (8)	0.1808 (7)	0.1527 (5)	0.0517 (13)
H13	0.4484	0.1048	0.0910	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0980 (3)	0.0439 (2)	0.0485 (2)	0.0182 (2)	0.0335 (2)	0.00210 (15)
Br1	0.0904 (5)	0.0621 (4)	0.0500 (3)	0.0110 (3)	0.0415 (3)	0.0074 (3)
I2	0.0833 (3)	0.0366 (2)	0.0657 (3)	0.01060 (18)	0.0292 (2)	0.01196 (16)
N1	0.041 (2)	0.044 (2)	0.039 (2)	0.0172 (18)	0.0162 (17)	0.0086 (17)
O1	0.067 (2)	0.0355 (18)	0.047 (2)	0.0065 (16)	0.0266 (18)	0.0060 (15)
C1	0.041 (3)	0.042 (3)	0.037 (2)	0.018 (2)	0.0134 (19)	0.0135 (19)
C2	0.039 (2)	0.036 (2)	0.038 (2)	0.0129 (19)	0.0105 (19)	0.0054 (18)
C3	0.049 (3)	0.044 (3)	0.036 (2)	0.020 (2)	0.013 (2)	0.007 (2)
C4	0.053 (3)	0.043 (3)	0.040 (2)	0.019 (2)	0.018 (2)	0.013 (2)
C5	0.047 (3)	0.032 (2)	0.046 (3)	0.013 (2)	0.018 (2)	0.012 (2)
C6	0.044 (3)	0.040 (3)	0.043 (2)	0.019 (2)	0.010 (2)	0.004 (2)
C7	0.049 (3)	0.043 (3)	0.040 (2)	0.022 (2)	0.017 (2)	0.008 (2)
C8	0.037 (2)	0.047 (3)	0.038 (2)	0.017 (2)	0.0153 (19)	0.010 (2)
C9	0.070 (4)	0.041 (3)	0.049 (3)	0.012 (3)	0.028 (3)	0.005 (2)
C10	0.070 (4)	0.047 (3)	0.042 (3)	0.016 (3)	0.022 (3)	−0.002 (2)
C11	0.049 (3)	0.051 (3)	0.038 (2)	0.015 (2)	0.019 (2)	0.007 (2)
C12	0.063 (3)	0.043 (3)	0.053 (3)	0.011 (2)	0.027 (3)	0.007 (2)
C13	0.063 (3)	0.045 (3)	0.049 (3)	0.020 (3)	0.026 (3)	0.005 (2)

Geometric parameters (Å, º) top

I1—C3	2.093 (5)	C5—C6	1.369 (7)
Br1—C11	1.907 (5)	C6—H6	0.9300
I2—C5	2.101 (5)	C7—H7	0.9300
N1—C7	1.273 (6)	C8—C9	1.382 (7)
N1—C8	1.427 (6)	C8—C13	1.382 (7)
O1—C2	1.340 (6)	C9—C10	1.382 (7)
O1—H1	0.8200	C9—H9	0.9300
C1—C6	1.401 (7)	C10—C11	1.360 (8)
C1—C2	1.406 (7)	C10—H10	0.9300
C1—C7	1.460 (6)	C11—C12	1.373 (7)
C2—C3	1.394 (6)	C12—C13	1.385 (7)
C3—C4	1.382 (7)	C12—H12	0.9300
C4—C5	1.387 (7)	C13—H13	0.9300
C4—H4	0.9300

C7—N1—C8	122.4 (4)	N1—C7—H7	119.4
C2—O1—H1	109.5	C1—C7—H7	119.4
C6—C1—C2	119.6 (4)	C9—C8—C13	118.8 (4)
C6—C1—C7	119.6 (4)	C9—C8—N1	125.0 (5)
C2—C1—C7	120.8 (4)	C13—C8—N1	116.1 (4)
O1—C2—C3	119.6 (4)	C8—C9—C10	120.4 (5)
O1—C2—C1	121.7 (4)	C8—C9—H9	119.8
C3—C2—C1	118.7 (4)	C10—C9—H9	119.8
C4—C3—C2	121.2 (4)	C11—C10—C9	119.7 (5)
C4—C3—I1	120.4 (3)	C11—C10—H10	120.1
C2—C3—I1	118.4 (4)	C9—C10—H10	120.1
C3—C4—C5	119.3 (4)	C10—C11—C12	121.3 (5)
C3—C4—H4	120.3	C10—C11—Br1	119.5 (4)
C5—C4—H4	120.3	C12—C11—Br1	119.2 (4)
C6—C5—C4	121.0 (4)	C11—C12—C13	118.9 (5)
C6—C5—I2	120.1 (4)	C11—C12—H12	120.6
C4—C5—I2	118.9 (3)	C13—C12—H12	120.6
C5—C6—C1	120.2 (4)	C8—C13—C12	120.8 (5)
C5—C6—H6	119.9	C8—C13—H13	119.6
C1—C6—H6	119.9	C12—C13—H13	119.6
N1—C7—C1	121.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.85	2.576 (5)	148

Experimental details

Crystal data
Chemical formula	C₁₃H₈BrI₂NO
M_r	527.91
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.9870 (13), 8.9811 (14), 11.3907 (18)
α, β, γ (°)	91.093 (2), 99.873 (2), 114.570 (2)
V (Å³)	728.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	7.05
Crystal size (mm)	0.17 × 0.15 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.380, 0.418
No. of measured, independent and observed [I > 2σ(I)] reflections	6174, 3125, 2425
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.094, 1.07
No. of reflections	3125
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.26, −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—H1···N1	0.82	1.85	2.576 (5)	147.5

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o788

doi:10.1107/S160053681200551X

Open

access