2,2'-[5-Bromo-o-phenyl-enebis(nitrilo-methyl-idyne)]diphenol.

A new tetra-dentate unsymmetrical Schiff base, C(20)H(15)BrN(2)O(2), has been synthesized from 4-bromo-o-phenyl-enediamine and salicylaldehyde in refluxing ethanol. The dihedral angles between the two hydroxy-phenyl rings and the bromo-o-phenyl-enediiminatoin group are 68.6 (1) and 8.7 (1)°; the dihedral angle between the two hydroxy-phenyl rings is 70.3 (1)°. There are two relatively strong intra-molecular 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 = 395.25

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.141

S = 1.00

3009 reflections

228 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.78 e Å−3

Δρmin = −0.62 e Å−3

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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011581/fl2239sup1.cif

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

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

C20H15BrN2O2	F(000) = 800
Mr = 395.25	Dx = 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 = 2.42 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

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

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(Fo2) + (0.085P)2 + 0.9153P] where P = (Fo2 + 2Fc2)/3
3009 reflections	(Δ/σ)max = 0.002
228 parameters	Δρmax = 0.78 e Å−3
2 restraints	Δρmin = −0.62 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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

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