(E)-4-Bromo-2-[(2-hydroxy-phen-yl)iminiometh-yl]phenolate.

The title compound, C(13)H(10)BrNO(2), 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 intra-molecular 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 inter-actions 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 00, 00, 001 with a domain ratio of 0.09919 (2):0.90081 (2).

Related literature

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

Crystal data

C13H10BrNO2

M = 291.12

Monoclinic,

a = 4.6387 (3) Å

b = 18.9379 (13) Å

c = 6.2270 (4) Å

β = 90.144 (3)°

V = 547.02 (6) Å3

Z = 2

Mo Kα radiation

μ = 3.74 mm−1

T = 100 K

0.43 × 0.14 × 0.14 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.295, T max = 0.628

8575 measured reflections

3120 independent reflections

3034 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.041

S = 1.02

3120 reflections

191 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.59 e Å−3

Δρmin = −0.29 e Å−3

Absolute structure: Flack (1983 ▶), 1480 Friedel pairs

Flack parameter: 0.027 (7)

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810015230/rz2436sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810015230/rz2436Isup2.hkl

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

C13H10BrNO2	F(000) = 292
Mr = 291.12	Dx = 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

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

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(Fo2) + (0.0035P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
3120 reflections	Δρmax = 0.59 e Å−3
191 parameters	Δρmin = −0.29 e Å−3
1 restraint	Absolute structure: Flack (1983), 1480 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.027 (7)

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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)

Table 1

Hydrogen-bond geometry (Å, °)

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) ; (ii) .