(E)-4-Bromo-2-[(2-hydroxy­phen­yl)iminiometh­yl]phenolate

Eltayeb, N.E.; Teoh, S.G.; Fun, H.-K.; Chantrapromma, S.

doi:10.1107/S1600536810015230

(E)-4-Bromo-2-[(2-hydroxyphenyl)iminiomethyl]phenolate

N. E. Eltayeb, S. G. Teoh, H.-K. Fun and S. Chantrapromma

The title compound, C₁₃H₁₀BrNO₂, crystallizes in a zwitterionic form. The zwitterion exists in a trans configuration about the C=N bond and is almost planar, the dihedral angle between the two benzene rings being 2.29 (9)°. An intramolecular N—H

O hydrogen bond formed between the iminium NH⁺ and the phenolate O⁻ atoms generates an S(6) ring motif. In the crystal, the zwitterions are linked through O—H

O hydrogen bonds into chains along [101] and these chains are further connected through C—H

Br interactions into a two-dimensional network perpendicular to (101). C

C [3.572 (3)–3.592 (3) Å] and C

Br [3.5633 (19)–3.7339 (18) Å] short contacts are observed. The crystal studied was a twin with twin law $\overline{1}$ 00, 0 $\overline{1}$ 0, 001 with a domain ratio of 0.09919 (2):0.90081 (2).

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810015230/rz2436sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810015230/rz2436Isup2.hkl Contains datablock I

CCDC reference: 781267

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
R factor = 0.018
wR factor = 0.041
Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level C
CHEMW01_ALERT_1_C  The difference between the given and expected weight for
            compound is greater 1 mass unit. Check that all hydrogen
            atoms have been taken into account.
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.04
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.00 Ratio
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........         O1
PLAT432_ALERT_2_C Short Inter X...Y Contact  C7     ..  C9      ..       3.18 Ang.
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          2

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           30.00
           From the CIF: _reflns_number_total               3120
           Count of symmetry unique reflns         1645
           Completeness (_total/calc)            189.67%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1475
           Fraction of Friedel pairs measured     0.897
           Are heavy atom types Z>Si present        yes
PLAT164_ALERT_4_G Nr. of Refined C-H H-Atoms in Heavy-Atom Struct.          8
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2
PLAT931_ALERT_5_G Check Twin Law ( 1 0  0)[       ] Estimated BASF       0.10
PLAT931_ALERT_5_G Check Twin Law (       )[ 1 0  0] Estimated BASF       0.10

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

Much attention has been given to Schiff base ligands due to their applications such as in coordination chemistry (Kagkelari et al., 2009), chelated boron catalyst (Wei & Atwood, 1998), pharmacological activities, anticancer (Dao et al., 2000), anti-HIV (Sriram et al., 2006), antibacterial and antifungal (Karthikeyan et al., 2006) activities. We have reported the crystal structures of Schiff base ligands which existed in a zwitterionic form i.e 2-((E)-{2-[(E)-2,3-dihydroxybenzylideneamino]-5-methylphenyl}- iminiomethyl)-6-hydroxyphenolate (Eltayeb et al., 2009) and (E)-4-allyl-2-{[(2-hydroxyphenyl)iminio]methyl}-6-methoxyphenolate (Eltayeb et al., 2010). Herein we report the crystal structure of the title zwitterionic Schiff base ligand (I).

The molecule of (I) (Fig. 1), C₁₃H₉BrNO₂, crystallizes in a zwitterionic form with cationic iminium and anionic enolate, and exists in a trans configuration about the C═N bond [1.310 (2) Å]; the torsion angle C8–N1–C7–C6 is 179.25 (17)°. The molecule is almost planar with the dihedral angle between the two benzene rings of 2.31 (9)°. The hydroxy group is co-planar with the attached C8–C13 benzene ring with the r.m.s. of 0.0102 (2) Å for the seven non H atoms. Intramolecular N—H···O hydrogen bond between the NH⁺ and the phenolate O^- generates an S(6) ring motif (Fig. 1; Table 1) which help to stabilize the planarity of the molecule (Bernstein et al., 1995). The bond distances are in normal ranges (Allen et al., 1987) and comparable with those found in related structures (Eltayeb et al., 2009, 2010; Tan & Liu, 2009).

In the crystal packing (Fig. 2), the zwitterions are linked through O2–H1O2···O1 hydrogen bonds into chains along the [101] and these chains are further connected through C11—H11A···Br1 interactions into a 2-D network perpendicular to the (101)-plane. The crystal is stabilized by O—H···O and weak C—H···Br interactions (Table 1). C···C [3.572 (3)-3.592 (3) Å] and C···Br [3.5633 (19)-3.7339 (18) Å] short contacts are observed.

Related literature top

For bond-length data, see: Allen et al. (1987). For hydrogen-bond motifs, see: Bernstein et al. (1995). For background to Schiff bases and their applications, see: Dao et al. (2000); Kagkelari et al. (2009); Karthikeyan et al. (2006); Sriram et al. (2006); Wei & Atwood (1998). For related structures, see: Eltayeb et al. (2009; 2010); Tan & Liu (2009). For the stability of the temperature controller used in the data collection, see Cosier & Glazer, (1986).

Experimental top

The title compound was synthesized by adding 5-bromo-2-hydroxybenzaldehyde (0.402 g, 2 mmol) to a solution of 2-aminophenol (0.218 g, 2 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for half an hour. The resultant yellow solution was filtered and the filtrate was evaporated to give a yellow solid product. Yellow needle-shaped single crystals of the title compound suitable for x-ray structure determination were obtained from ethanol by slow evaporation at room temperature after nine days.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with 50% probability displacement ellipsoids and the atom-numbering scheme. Hydrogen bond is shown as dashed lines.
	Fig. 2. The crystal packing showing 2-D networks perpendicular to the (101)-plane.

(E)-4-Bromo-2-[(2-hydroxyphenyl)iminiomethyl]phenolate top

Crystal data top

C₁₃H₁₀BrNO₂	F(000) = 292
M_r = 291.12	D_x = 1.773 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3120 reflections
a = 4.6387 (3) Å	θ = 1.1–30.0°
b = 18.9379 (13) Å	µ = 3.74 mm⁻¹
c = 6.2270 (4) Å	T = 100 K
β = 90.144 (3)°	Needle, yellow
V = 547.02 (6) Å³	0.43 × 0.14 × 0.14 mm
Z = 2

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3120 independent reflections
Radiation source: sealed tube	3034 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 30.0°, θ_min = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −6→6
T_min = 0.295, T_max = 0.628	k = −26→26
8575 measured reflections	l = −8→8

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)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.041	w = 1/[σ²(F_o²) + (0.0035P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3120 reflections	Δρ_max = 0.59 e Å⁻³
191 parameters	Δρ_min = −0.29 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1480 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.027 (7)

Crystal data top

C₁₃H₁₀BrNO₂	V = 547.02 (6) Å³
M_r = 291.12	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.6387 (3) Å	µ = 3.74 mm⁻¹
b = 18.9379 (13) Å	T = 100 K
c = 6.2270 (4) Å	0.43 × 0.14 × 0.14 mm
β = 90.144 (3)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	3120 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	3034 reflections with I > 2σ(I)
T_min = 0.295, T_max = 0.628	R_int = 0.026
8575 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.018	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.041	Δρ_max = 0.59 e Å⁻³
S = 1.02	Δρ_min = −0.29 e Å⁻³
3120 reflections	Absolute structure: Flack (1983), 1480 Friedel pairs
191 parameters	Absolute structure parameter: 0.027 (7)
1 restraint

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.00526 (4)	0.442840 (15)	0.87673 (2)	0.01554 (4)
O1	0.5191 (3)	0.66300 (7)	0.29008 (19)	0.0152 (2)
O2	1.1314 (3)	0.70088 (8)	1.0194 (2)	0.0166 (3)
H1O2	1.2697	0.6925	1.0976	0.025*
N1	0.8565 (3)	0.69973 (8)	0.6076 (2)	0.0121 (3)
H1N1	0.802 (6)	0.6976 (16)	0.470 (5)	0.026 (7)*
C1	0.4132 (4)	0.61426 (10)	0.4149 (3)	0.0126 (3)
C2	0.1934 (4)	0.56695 (10)	0.3446 (3)	0.0140 (3)
H2A	0.133 (6)	0.5756 (14)	0.207 (4)	0.020 (6)*
C3	0.0797 (4)	0.51628 (10)	0.4781 (3)	0.0138 (3)
H3A	−0.064 (6)	0.4852 (14)	0.440 (4)	0.021 (6)*
C4	0.1776 (4)	0.51058 (9)	0.6919 (3)	0.0129 (3)
C5	0.3894 (4)	0.55482 (9)	0.7685 (3)	0.0125 (3)
H5A	0.450 (6)	0.5535 (16)	0.905 (4)	0.026 (7)*
C6	0.5112 (4)	0.60653 (9)	0.6331 (3)	0.0122 (3)
C7	0.7261 (4)	0.65154 (9)	0.7227 (3)	0.0123 (3)
H7A	0.787 (5)	0.6470 (12)	0.868 (4)	0.009 (5)*
C8	1.0707 (4)	0.74911 (9)	0.6695 (3)	0.0117 (3)
C9	1.2064 (4)	0.74952 (9)	0.8722 (3)	0.0125 (3)
C10	1.4149 (4)	0.80132 (10)	0.9137 (3)	0.0148 (3)
H10A	1.494 (6)	0.8047 (15)	1.048 (5)	0.022 (6)*
C11	1.4940 (4)	0.84982 (10)	0.7569 (3)	0.0159 (3)
H11A	1.639 (6)	0.8847 (13)	0.786 (4)	0.018 (6)*
C12	1.3635 (4)	0.84799 (10)	0.5548 (3)	0.0160 (3)
H12A	1.427 (7)	0.8788 (17)	0.453 (5)	0.036 (8)*
C13	1.1523 (4)	0.79797 (9)	0.5130 (3)	0.0139 (3)
H13A	1.045 (5)	0.7956 (13)	0.368 (3)	0.014 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01876 (7)	0.01522 (7)	0.01262 (6)	−0.00425 (9)	−0.00307 (5)	0.00324 (8)
O1	0.0161 (6)	0.0183 (6)	0.0113 (5)	−0.0031 (5)	−0.0034 (5)	0.0033 (5)
O2	0.0167 (6)	0.0224 (7)	0.0106 (6)	−0.0044 (5)	−0.0054 (5)	0.0042 (5)
N1	0.0122 (7)	0.0140 (7)	0.0102 (7)	−0.0004 (5)	−0.0033 (5)	0.0003 (5)
C1	0.0122 (7)	0.0150 (8)	0.0106 (7)	0.0001 (6)	−0.0012 (5)	−0.0002 (6)
C2	0.0156 (8)	0.0172 (8)	0.0092 (8)	−0.0007 (6)	−0.0030 (6)	−0.0007 (6)
C3	0.0136 (8)	0.0141 (8)	0.0137 (8)	−0.0022 (6)	−0.0024 (6)	−0.0018 (6)
C4	0.0142 (8)	0.0120 (7)	0.0126 (8)	−0.0007 (6)	−0.0003 (6)	0.0015 (6)
C5	0.0150 (8)	0.0137 (8)	0.0087 (8)	0.0011 (6)	−0.0030 (6)	0.0007 (6)
C6	0.0116 (7)	0.0140 (7)	0.0109 (7)	0.0014 (6)	−0.0014 (6)	−0.0021 (6)
C7	0.0123 (8)	0.0139 (8)	0.0108 (8)	0.0003 (6)	−0.0020 (6)	−0.0007 (6)
C8	0.0114 (7)	0.0114 (7)	0.0122 (7)	0.0001 (6)	−0.0033 (5)	−0.0010 (6)
C9	0.0127 (7)	0.0146 (8)	0.0103 (7)	0.0003 (6)	−0.0012 (6)	−0.0007 (6)
C10	0.0146 (8)	0.0174 (9)	0.0123 (8)	−0.0012 (6)	−0.0044 (6)	−0.0020 (6)
C11	0.0141 (8)	0.0154 (8)	0.0182 (8)	−0.0021 (7)	−0.0016 (7)	−0.0017 (6)
C12	0.0172 (9)	0.0147 (8)	0.0161 (8)	−0.0007 (7)	−0.0011 (6)	0.0022 (7)
C13	0.0128 (8)	0.0160 (8)	0.0129 (8)	0.0008 (6)	−0.0026 (6)	0.0011 (6)

Geometric parameters (Å, º) top

Br1—C4	1.9011 (18)	C5—C6	1.411 (2)
O1—C1	1.304 (2)	C5—H5A	0.89 (2)
O2—C9	1.346 (2)	C6—C7	1.424 (2)
O2—H1O2	0.8200	C7—H7A	0.95 (2)
N1—C7	1.310 (2)	C8—C13	1.397 (2)
N1—C8	1.417 (2)	C8—C9	1.409 (2)
N1—H1N1	0.89 (3)	C9—C10	1.401 (2)
C1—C2	1.425 (2)	C10—C11	1.391 (3)
C1—C6	1.439 (2)	C10—H10A	0.92 (3)
C2—C3	1.376 (3)	C11—C12	1.396 (3)
C2—H2A	0.91 (3)	C11—H11A	0.96 (3)
C3—C4	1.409 (2)	C12—C13	1.387 (3)
C3—H3A	0.92 (3)	C12—H12A	0.91 (3)
C4—C5	1.376 (3)	C13—H13A	1.03 (2)

C9—O2—H1O2	109.5	N1—C7—C6	121.74 (16)
C7—N1—C8	129.42 (16)	N1—C7—H7A	116.6 (14)
C7—N1—H1N1	111.3 (19)	C6—C7—H7A	121.6 (14)
C8—N1—H1N1	119.2 (18)	C13—C8—C9	120.02 (16)
O1—C1—C2	122.15 (15)	C13—C8—N1	115.98 (15)
O1—C1—C6	121.08 (16)	C9—C8—N1	123.97 (16)
C2—C1—C6	116.76 (16)	O2—C9—C10	122.23 (15)
C3—C2—C1	121.85 (16)	O2—C9—C8	119.39 (15)
C3—C2—H2A	125.0 (16)	C10—C9—C8	118.39 (16)
C1—C2—H2A	113.1 (17)	C11—C10—C9	121.08 (16)
C2—C3—C4	120.08 (16)	C11—C10—H10A	119.3 (18)
C2—C3—H3A	124.6 (16)	C9—C10—H10A	119.6 (17)
C4—C3—H3A	115.3 (16)	C10—C11—C12	120.15 (17)
C5—C4—C3	120.59 (16)	C10—C11—H11A	120.5 (15)
C5—C4—Br1	120.14 (13)	C12—C11—H11A	119.4 (15)
C3—C4—Br1	119.24 (13)	C13—C12—C11	119.38 (17)
C4—C5—C6	120.14 (16)	C13—C12—H12A	122 (2)
C4—C5—H5A	122 (2)	C11—C12—H12A	118 (2)
C6—C5—H5A	118 (2)	C12—C13—C8	120.94 (16)
C5—C6—C7	117.51 (15)	C12—C13—H13A	122.2 (13)
C5—C6—C1	120.57 (16)	C8—C13—H13A	116.8 (13)
C7—C6—C1	121.89 (16)

O1—C1—C2—C3	−179.04 (17)	C1—C6—C7—N1	−3.8 (3)
C6—C1—C2—C3	0.1 (3)	C7—N1—C8—C13	−175.04 (17)
C1—C2—C3—C4	0.8 (3)	C7—N1—C8—C9	7.1 (3)
C2—C3—C4—C5	−0.8 (3)	C13—C8—C9—O2	−178.12 (16)
C2—C3—C4—Br1	177.31 (14)	N1—C8—C9—O2	−0.3 (3)
C3—C4—C5—C6	0.0 (3)	C13—C8—C9—C10	2.3 (3)
Br1—C4—C5—C6	−178.09 (13)	N1—C8—C9—C10	−179.92 (17)
C4—C5—C6—C7	178.93 (16)	O2—C9—C10—C11	178.26 (18)
C4—C5—C6—C1	0.8 (3)	C8—C9—C10—C11	−2.1 (3)
O1—C1—C6—C5	178.25 (17)	C9—C10—C11—C12	0.6 (3)
C2—C1—C6—C5	−0.8 (2)	C10—C11—C12—C13	0.8 (3)
O1—C1—C6—C7	0.2 (3)	C11—C12—C13—C8	−0.6 (3)
C2—C1—C6—C7	−178.85 (16)	C9—C8—C13—C12	−0.9 (3)
C8—N1—C7—C6	179.25 (17)	N1—C8—C13—C12	−178.91 (16)
C5—C6—C7—N1	178.12 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H1O2···O1ⁱ	0.82	1.76	2.5641 (19)	169
N1—H1N1···O1	0.89 (3)	1.84 (3)	2.6129 (18)	143 (3)
C7—H7A···O2	0.95 (2)	2.12 (2)	2.794 (2)	127.1 (18)
C11—H11A···Br1ⁱⁱ	0.96 (3)	2.89 (3)	3.6982 (19)	143.1 (19)

Symmetry codes: (i) x+1, y, z+1; (ii) −x+2, y+1/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₀BrNO₂
M_r	291.12
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	4.6387 (3), 18.9379 (13), 6.2270 (4)
β (°)	90.144 (3)
V (Å³)	547.02 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.74
Crystal size (mm)	0.43 × 0.14 × 0.14

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.295, 0.628
No. of measured, independent and observed [I > 2σ(I)] reflections	8575, 3120, 3034
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.041, 1.02
No. of reflections	3120
No. of parameters	191
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)	0.59, −0.29
Absolute structure	Flack (1983), 1480 Friedel pairs
Absolute structure parameter	0.027 (7)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).