2,2′-[5-Bromo-o-phenyl­enebis(nitrilo­methyl­idyne)]diphenol

Gao, J.; Cheng, Y.

doi:10.1107/S1600536809011581

organic compounds

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Volume 65| Part 5| May 2009| Page o979

doi:10.1107/S1600536809011581

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2,2′-[5-Bromo-o-phenylenebis(nitrilomethylidyne)]diphenol

Jing Gao ^a ^* and Yan Cheng ^a

^aDepartment of Pharmacy, Mudanjiang Medical University, Mudanjiang 157011, People's Republic of China
^*Correspondence e-mail: gaojing_mmu@163.com

(Received 6 March 2009; accepted 29 March 2009; online 8 April 2009)

A new tetradentate unsymmetrical Schiff base, C₂₀H₁₅BrN₂O₂, has been synthesized from 4-bromo-o-phenylenediamine and salicylaldehyde in refluxing ethanol. The dihedral angles between the two hydroxyphenyl rings and the bromo-o-phenylenediiminatoin group are 68.6 (1) and 8.7 (1)°; the dihedral angle between the two hydroxyphenyl rings is 70.3 (1)°. There are two relatively strong intramolecular of O—H⋯N hydrogen bonds.

Related literature

For the biological activity of Schiff bases, see: Boskovic et al. (2003 ); Koizumi et al. (2005 ); Oshiob et al. (2005 ). For related structures, see: Kannappan et al. (2005 ); Zhang et al. (2003 ).

Experimental

Crystal data

C₂₀H₁₅BrN₂O₂
M_r = 395.25
Monoclinic, P 2₁ /c
a = 12.8744 (10) Å
b = 5.9968 (10) Å
c = 22.106 (2) Å
β = 91.221 (1)°
V = 1706.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.43 mm⁻¹
T = 297 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.760, T_max = 0.830
8088 measured reflections
3009 independent reflections
2140 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.141
S = 1.00
3009 reflections
228 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N2	0.82	1.87	2.578 (4)	145
O1—H1⋯N3	0.82	1.90	2.614 (5)	145

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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 I, global. DOI: 10.1107/S1600536809011581/fl2239sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011581/fl2239Isup2.hkl

checkCIF report

Comment top

During the past decades, Schiff bases have been intensively studied due to their strong coordination capability as well

as their diverse biological activities, such as antibacterial, antitumor, etc. (Koizumi et al., 2005; Boskovic et al., 2003; Oshiob et al., 2005). The halide groups in schiff base ligands can effectively optimize the properties of the coordination complexes.

X-ray diffraction analysis indicates that (I) is a unsymmetrical Schiff (Fig. 1). The imide bond lengths of 1.276 (5) and 1.280 (5) Å for C(7)—N(3) and C(14)—N(2) are slightly longer than that found in 4-Bromo-2-(2-pyridylmethyliminomethyl)phenol (1.269 (4) Å) (Zhang et al., 2003) .There are two relatively strong intramolecular hydrogen bonds (Table 1), which are similar to its derivative 4-Bromo-2-(2-pyridylmethyliminomethyl)phenol (Zhang et al.,2003).

Related literature top

For the biological activity of Schiff bases, see: Boskovic et al. (2003); Koizumi et al. (2005); Oshiob et al. (2005). For related structures, see: Kannappan et al. (2005); Zhang et al. (2003).

Experimental top

(I) was prepared according to the method reported in the literature (Kannappan et al., 2005). 4-bromo-o-phenylenediamine (2.16 g, 0.02 mol) was added to a stirred ethanol solution of salicylaldehyde (3.04 g, 0.02 mol (10 ml). The reaction mixture was stirred for about 3 h and then the mixture was allowed to stand at room temperature for about two days. Yellow cystals suitable for X-ray diffraction analysis were then collected with a yield of 25%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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. A view of the structure of (I), showing the atmoic numbering scheme and 30% probability displacement ellipsoids.

2,2'-[5-Bromo-o-phenylenebis(nitrilomethylidyne)]diphenol top

Crystal data top

C₂₀H₁₅BrN₂O₂	F(000) = 800
M_r = 395.25	D_x = 1.539 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3171 reflections
a = 12.8744 (10) Å	θ = 1.6–25.5°
b = 5.9968 (10) Å	µ = 2.43 mm⁻¹
c = 22.106 (2) Å	T = 297 K
β = 91.221 (1)°	Block, yellow
V = 1706.3 (3) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	3009 independent reflections
Radiation source: fine-focus sealed tube	2140 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→15
T_min = 0.760, T_max = 0.830	k = −6→7
8088 measured reflections	l = −24→26

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.085P)² + 0.9153P] where P = (F_o² + 2F_c²)/3
3009 reflections	(Δ/σ)_max = 0.002
228 parameters	Δρ_max = 0.78 e Å⁻³
2 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

C₂₀H₁₅BrN₂O₂	V = 1706.3 (3) Å³
M_r = 395.25	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.8744 (10) Å	µ = 2.43 mm⁻¹
b = 5.9968 (10) Å	T = 297 K
c = 22.106 (2) Å	0.12 × 0.10 × 0.08 mm
β = 91.221 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3009 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2140 reflections with I > 2σ(I)
T_min = 0.760, T_max = 0.830	R_int = 0.027
8088 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	2 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.00	Δρ_max = 0.78 e Å⁻³
3009 reflections	Δρ_min = −0.62 e Å⁻³
228 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
Br1	0.27473 (4)	0.20430 (9)	1.05914 (2)	0.0635 (2)
C1	0.1838 (3)	0.8216 (6)	0.94539 (16)	0.0417 (9)
C2	0.1078 (2)	0.7023 (5)	0.97413 (14)	0.0317 (8)
H2	0.0386	0.7461	0.9718	0.038*
C3	0.1377 (3)	0.5168 (5)	1.00639 (16)	0.0481 (10)
H3	0.0878	0.4316	1.0255	0.058*
C4	0.2398 (3)	0.4554 (7)	1.01079 (17)	0.0447 (9)
C5	0.3167 (3)	0.5727 (7)	0.98216 (18)	0.0486 (10)
H5	0.3860	0.5298	0.9853	0.058*
C6	0.2863 (3)	0.7566 (7)	0.94862 (18)	0.0446 (10)
C7	0.4151 (3)	0.7950 (7)	0.87700 (19)	0.0464 (10)
H7	0.4002	0.6486	0.8660	0.056*
C8	0.4988 (3)	0.9113 (7)	0.84710 (18)	0.0449 (9)
C9	0.5316 (3)	1.1220 (8)	0.8668 (2)	0.0517 (10)
C10	0.6197 (4)	1.2177 (9)	0.8394 (2)	0.0662 (13)
H10	0.6438	1.3558	0.8528	0.079*
C11	0.6688 (4)	1.1140 (10)	0.7950 (2)	0.0676 (13)
H11	0.7260	1.1814	0.7776	0.081*
C12	0.6359 (4)	0.9088 (10)	0.7746 (2)	0.0663 (13)
H12	0.6706	0.8387	0.7434	0.080*
C13	0.5525 (3)	0.8076 (8)	0.79998 (19)	0.0547 (11)
H13	0.5309	0.6685	0.7860	0.066*
C14	0.0595 (3)	1.0603 (7)	0.90197 (16)	0.0425 (9)
H14	0.0075	0.9705	0.9174	0.051*
C15	0.0308 (3)	1.2554 (7)	0.86720 (17)	0.0436 (9)
C16	0.1076 (3)	1.3984 (7)	0.84457 (16)	0.0485 (10)
C17	0.0765 (4)	1.5884 (8)	0.81293 (19)	0.0637 (13)
H17	0.1263	1.6840	0.7975	0.076*
C18	−0.0274 (5)	1.6360 (8)	0.8042 (2)	0.0671 (14)
H18	−0.0468	1.7656	0.7839	0.081*
C19	−0.1025 (4)	1.4960 (8)	0.8251 (2)	0.0629 (12)
H19	−0.1724	1.5278	0.8180	0.076*
C20	−0.0733 (3)	1.3075 (7)	0.85666 (19)	0.0525 (10)
H20	−0.1243	1.2131	0.8713	0.063*
N2	0.1546 (2)	1.0078 (6)	0.91204 (14)	0.0425 (8)
N3	0.3615 (2)	0.8877 (6)	0.91782 (16)	0.0501 (8)
O1	0.4841 (3)	1.2338 (6)	0.91170 (19)	0.0761 (11)
H1	0.4403	1.1533	0.9269	0.114*
O2	0.2093 (2)	1.3554 (6)	0.85188 (15)	0.0654 (9)
H2A	0.2175	1.2538	0.8764	0.098*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0748 (4)	0.0534 (3)	0.0618 (3)	0.0087 (2)	−0.0108 (2)	0.0073 (2)
C1	0.040 (2)	0.041 (2)	0.044 (2)	−0.0021 (17)	−0.0003 (16)	−0.0050 (18)
C2	0.0219 (16)	0.037 (2)	0.0360 (18)	−0.0026 (15)	0.0033 (14)	0.0062 (16)
C3	0.045 (2)	0.051 (3)	0.049 (2)	−0.0092 (19)	−0.0011 (18)	0.002 (2)
C4	0.049 (2)	0.040 (2)	0.045 (2)	−0.0010 (18)	−0.0053 (18)	−0.0017 (18)
C5	0.045 (2)	0.045 (3)	0.056 (2)	0.0010 (19)	0.0008 (19)	−0.007 (2)
C6	0.043 (2)	0.043 (2)	0.048 (2)	−0.0090 (18)	0.0065 (18)	−0.0074 (18)
C7	0.039 (2)	0.040 (2)	0.060 (3)	−0.0005 (18)	−0.0018 (19)	0.003 (2)
C8	0.038 (2)	0.044 (2)	0.052 (2)	0.0042 (18)	−0.0049 (17)	0.0056 (19)
C9	0.037 (2)	0.049 (3)	0.069 (3)	−0.0003 (19)	0.002 (2)	0.005 (2)
C10	0.049 (3)	0.060 (3)	0.089 (4)	−0.011 (2)	0.000 (3)	0.012 (3)
C11	0.047 (3)	0.085 (4)	0.071 (3)	−0.005 (3)	0.008 (2)	0.015 (3)
C12	0.055 (3)	0.092 (4)	0.053 (3)	0.005 (3)	0.011 (2)	0.007 (3)
C13	0.050 (2)	0.066 (3)	0.049 (2)	0.002 (2)	0.001 (2)	0.001 (2)
C14	0.046 (2)	0.040 (2)	0.042 (2)	−0.0061 (18)	0.0042 (17)	0.0001 (17)
C15	0.056 (2)	0.039 (2)	0.036 (2)	−0.0036 (18)	0.0029 (18)	−0.0023 (16)
C16	0.065 (3)	0.046 (2)	0.035 (2)	−0.011 (2)	0.0036 (19)	−0.0024 (19)
C17	0.103 (4)	0.048 (3)	0.041 (2)	−0.018 (3)	0.010 (2)	0.004 (2)
C18	0.109 (4)	0.045 (3)	0.046 (3)	0.010 (3)	−0.013 (3)	0.005 (2)
C19	0.074 (3)	0.056 (3)	0.058 (3)	0.012 (3)	−0.006 (2)	0.003 (2)
C20	0.057 (3)	0.050 (3)	0.051 (2)	0.000 (2)	0.000 (2)	0.001 (2)
N2	0.0408 (18)	0.0416 (19)	0.0453 (18)	−0.0045 (14)	0.0014 (14)	0.0006 (15)
N3	0.0393 (18)	0.046 (2)	0.065 (2)	−0.0065 (16)	0.0084 (16)	−0.0063 (18)
O1	0.063 (2)	0.052 (2)	0.114 (3)	−0.0116 (16)	0.028 (2)	−0.021 (2)
O2	0.060 (2)	0.072 (2)	0.065 (2)	−0.0218 (17)	0.0083 (16)	0.0092 (17)

Geometric parameters (Å, º) top

Br1—C4	1.895 (4)	C11—C12	1.375 (8)
C1—C6	1.377 (6)	C11—H11	0.9300
C1—C2	1.378 (5)	C12—C13	1.364 (6)
C1—N2	1.385 (5)	C12—H12	0.9300
C2—C3	1.372 (4)	C13—H13	0.9300
C2—H2	0.9300	C14—N2	1.279 (5)
C3—C4	1.367 (5)	C14—C15	1.443 (5)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.379 (6)	C15—C20	1.391 (6)
C5—C6	1.381 (6)	C15—C16	1.409 (6)
C5—H5	0.9300	C16—O2	1.341 (5)
C6—N3	1.430 (5)	C16—C17	1.391 (6)
C7—N3	1.275 (5)	C17—C18	1.377 (7)
C7—C8	1.454 (6)	C17—H17	0.9300
C7—H7	0.9300	C18—C19	1.367 (7)
C8—C9	1.399 (6)	C18—H18	0.9300
C8—C13	1.408 (6)	C19—C20	1.377 (6)
C9—O1	1.354 (5)	C19—H19	0.9300
C9—C10	1.419 (6)	C20—H20	0.9300
C10—C11	1.333 (7)	O1—H1	0.8200
C10—H10	0.9300	O2—H2A	0.8200

C6—C1—C2	121.2 (3)	C12—C11—H11	119.6
C6—C1—N2	120.3 (3)	C13—C12—C11	120.2 (5)
C2—C1—N2	118.5 (3)	C13—C12—H12	119.9
C3—C2—C1	117.8 (3)	C11—C12—H12	119.9
C3—C2—H2	121.1	C12—C13—C8	120.7 (5)
C1—C2—H2	121.1	C12—C13—H13	119.6
C4—C3—C2	121.0 (3)	C8—C13—H13	119.6
C4—C3—H3	119.5	N2—C14—C15	121.7 (4)
C2—C3—H3	119.5	N2—C14—H14	119.2
C3—C4—C5	121.9 (4)	C15—C14—H14	119.2
C3—C4—Br1	118.1 (3)	C20—C15—C16	119.0 (4)
C5—C4—Br1	120.0 (3)	C20—C15—C14	120.4 (4)
C4—C5—C6	117.1 (4)	C16—C15—C14	120.6 (4)
C4—C5—H5	121.4	O2—C16—C17	119.2 (4)
C6—C5—H5	121.4	O2—C16—C15	122.1 (4)
C1—C6—C5	121.0 (3)	C17—C16—C15	118.7 (4)
C1—C6—N3	118.5 (4)	C18—C17—C16	120.6 (4)
C5—C6—N3	120.5 (4)	C18—C17—H17	119.7
N3—C7—C8	122.0 (4)	C16—C17—H17	119.7
N3—C7—H7	119.0	C19—C18—C17	121.1 (5)
C8—C7—H7	119.0	C19—C18—H18	119.4
C9—C8—C13	118.7 (4)	C17—C18—H18	119.4
C9—C8—C7	120.9 (4)	C18—C19—C20	119.2 (5)
C13—C8—C7	120.3 (4)	C18—C19—H19	120.4
O1—C9—C8	122.5 (4)	C20—C19—H19	120.4
O1—C9—C10	119.3 (4)	C19—C20—C15	121.4 (4)
C8—C9—C10	118.1 (4)	C19—C20—H20	119.3
C11—C10—C9	121.5 (5)	C15—C20—H20	119.3
C11—C10—H10	119.3	C14—N2—C1	122.6 (3)
C9—C10—H10	119.3	C7—N3—C6	118.6 (4)
C10—C11—C12	120.8 (5)	C9—O1—H1	109.5
C10—C11—H11	119.6	C16—O2—H2A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N2	0.82	1.87	2.578 (4)	145
O1—H1···N3	0.82	1.90	2.614 (5)	145

Experimental details

Crystal data
Chemical formula	C₂₀H₁₅BrN₂O₂
M_r	395.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	297
a, b, c (Å)	12.8744 (10), 5.9968 (10), 22.106 (2)
β (°)	91.221 (1)
V (Å³)	1706.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.43
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.760, 0.830
No. of measured, independent and observed [I > 2σ(I)] reflections	8088, 3009, 2140
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.141, 1.00
No. of reflections	3009
No. of parameters	228
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.78, −0.62

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), 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
O2—H2A···N2	0.82	1.87	2.578 (4)	144.7
O1—H1···N3	0.82	1.90	2.614 (5)	145.3

Acknowledgements

The authors acknowledge financial support from Mudanjiang Medical University.

References

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