(E)-3-[(3-Bromo-phen-yl)imino-meth-yl]benzene-1,2-diol: a combined X-ray and computational structural study.

The title compound, C(13)H(10)BrNO(2), exists as an enol-imine form in the crystal and adopts an E configuration with respect to the C=N double bond. The mol-ecule is close to planar, with a dihedral angle of 6.88 (14)° between the aromatic rings. Intra-molecular O-H⋯N and O-H⋯O hydrogen bonds generate S(6) and S(5) ring motifs, respectively. The crystal structure is stabilized by inter-molecular O-H⋯O hydrogen-bond inter-actions, forming R(2) (2)(10) and R(2) (2)(20) chains along [100]. ab initio Hartree-Fock (HF), density-functional theory (DFT) and semi-empirical (AM1 and PM3) calculations and full-geometry optimizations were also performed. Although there are some discrepancies between the experimental and calculated parameters, caused presumably by the O-H⋯O hydrogen-bond inter-actions, there is an acceptable general agreement between them.

Related literature

For general background to Schiff base compounds in coordination chemistry, see: Chen et al. (2008 ▶); May et al. (2004 ▶); Weber et al. (2007 ▶). For background to DFT calculations, see: Becke (1988 ▶, 1993 ▶); Lee et al. (1988 ▶); Schmidt & Polik et al. (2007 ▶); Friesner et al. (2005 ▶); Liu et al. (2004 ▶). For a related structure, see: Cao et al. (2009 ▶); Temel et al. (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C13H10BrNO2

M = 292.13

Orthorhombic,

a = 4.7411 (2) Å

b = 18.9447 (6) Å

c = 26.1417 (10) Å

V = 2348.01 (15) Å3

Z = 8

Mo Kα radiation

μ = 3.50 mm−1

T = 296 K

0.66 × 0.38 × 0.10 mm

Data collection

Stoe IPDS-II diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.229, T max = 0.735

7185 measured reflections

2212 independent reflections

1764 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.078

S = 1.05

2212 reflections

162 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.42 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and GAUSSIAN (Frisch et al., 2004 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035053/si2198sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035053/si2198Isup2.hkl

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

C13H10BrNO2	F(000) = 1168
Mr = 292.13	Dx = 1.653 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7185 reflections
a = 4.7411 (2) Å	θ = 1.3–26.2°
b = 18.9447 (6) Å	µ = 3.50 mm−1
c = 26.1417 (10) Å	T = 296 K
V = 2348.01 (15) Å3	Plate, red
Z = 8	0.66 × 0.38 × 0.10 mm

Stoe IPDS-II diffractometer	2212 independent reflections
Radiation source: fine-focus sealed tube	1764 reflections with I > 2σ(I)
graphite	Rint = 0.040
Detector resolution: 6.67 pixels mm-1	θmax = 25.6°, θmin = 1.6°
rotation method scans	h = −5→5
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −22→22
Tmin = 0.229, Tmax = 0.735	l = −31→31
7185 measured reflections

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)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078	w = 1/[σ2(Fo2) + (0.0356P)2 + 0.8167P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.002
2212 reflections	Δρmax = 0.33 e Å−3
162 parameters	Δρmin = −0.42 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0

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
C1	0.2287 (5)	0.59650 (12)	0.38493 (9)	0.0430 (5)
C2	0.1687 (5)	0.56587 (13)	0.33762 (9)	0.0441 (5)
C3	−0.0340 (6)	0.51215 (13)	0.33440 (10)	0.0480 (6)
C4	−0.1727 (6)	0.49065 (14)	0.37771 (11)	0.0543 (7)
H4	−0.3082	0.4553	0.3753	0.065*
C5	−0.1148 (6)	0.52049 (15)	0.42490 (11)	0.0556 (7)
H5	−0.2106	0.5052	0.4539	0.067*
C6	0.0848 (6)	0.57283 (14)	0.42865 (10)	0.0524 (6)
H6	0.1248	0.5927	0.4603	0.063*
C7	0.4352 (5)	0.65240 (13)	0.38933 (9)	0.0451 (6)
H7	0.4674	0.6726	0.4212	0.054*
C8	0.7753 (5)	0.72987 (12)	0.35557 (9)	0.0409 (5)
C9	0.8643 (5)	0.75859 (13)	0.40177 (9)	0.0461 (6)
H9	0.7918	0.7419	0.4325	0.055*
C10	1.0603 (6)	0.81192 (13)	0.40147 (9)	0.0475 (6)
C11	1.1712 (6)	0.83889 (14)	0.35705 (10)	0.0520 (6)
H11	1.3031	0.8752	0.3578	0.062*
C12	1.0810 (6)	0.81048 (15)	0.31139 (10)	0.0572 (7)
H12	1.1510	0.8283	0.2808	0.069*
C13	0.8888 (6)	0.75614 (15)	0.31054 (10)	0.0513 (6)
H13	0.8342	0.7368	0.2794	0.062*
N1	0.5747 (4)	0.67489 (11)	0.35080 (8)	0.0442 (5)
O1	0.2990 (5)	0.58565 (11)	0.29377 (7)	0.0583 (5)
O2	−0.0900 (5)	0.48050 (12)	0.28892 (8)	0.0684 (6)
Br1	1.18395 (9)	0.85040 (2)	0.464746 (12)	0.08086 (16)
H1	0.415 (8)	0.619 (2)	0.3026 (13)	0.088 (12)*
H2	−0.007 (10)	0.499 (2)	0.2666 (14)	0.113 (16)*

	U11	U22	U33	U12	U13	U23
C1	0.0352 (13)	0.0422 (12)	0.0517 (13)	0.0035 (10)	−0.0009 (10)	0.0026 (10)
C2	0.0396 (13)	0.0415 (13)	0.0513 (13)	−0.0004 (11)	0.0019 (11)	0.0055 (11)
C3	0.0454 (14)	0.0416 (13)	0.0570 (14)	−0.0023 (11)	−0.0068 (12)	0.0033 (11)
C4	0.0431 (15)	0.0433 (14)	0.0764 (18)	−0.0048 (12)	0.0014 (13)	0.0124 (13)
C5	0.0503 (16)	0.0549 (16)	0.0616 (16)	−0.0008 (13)	0.0088 (13)	0.0107 (13)
C6	0.0495 (15)	0.0553 (15)	0.0525 (14)	0.0032 (13)	0.0019 (12)	0.0019 (12)
C7	0.0432 (13)	0.0457 (13)	0.0465 (12)	0.0027 (11)	−0.0039 (11)	−0.0036 (10)
C8	0.0359 (12)	0.0393 (12)	0.0476 (12)	0.0023 (10)	−0.0044 (10)	0.0006 (9)
C9	0.0475 (15)	0.0472 (14)	0.0436 (12)	−0.0054 (12)	−0.0012 (11)	0.0028 (10)
C10	0.0485 (15)	0.0441 (14)	0.0498 (13)	−0.0009 (12)	−0.0058 (12)	−0.0038 (11)
C11	0.0490 (15)	0.0440 (14)	0.0630 (15)	−0.0050 (12)	0.0027 (13)	−0.0010 (11)
C12	0.0615 (18)	0.0578 (16)	0.0524 (14)	−0.0089 (14)	0.0103 (13)	0.0035 (12)
C13	0.0551 (16)	0.0548 (16)	0.0441 (13)	−0.0062 (13)	−0.0012 (12)	−0.0012 (11)
N1	0.0396 (11)	0.0440 (11)	0.0490 (11)	−0.0024 (9)	−0.0028 (9)	0.0001 (9)
O1	0.0626 (12)	0.0612 (12)	0.0512 (10)	−0.0231 (10)	0.0022 (9)	−0.0014 (9)
O2	0.0769 (15)	0.0665 (14)	0.0618 (12)	−0.0291 (12)	−0.0049 (11)	−0.0011 (10)
Br1	0.1009 (3)	0.0846 (2)	0.05706 (19)	−0.0355 (2)	−0.01118 (17)	−0.01177 (16)

C1—C2	1.395 (3)	C8—C13	1.387 (3)
C1—C6	1.405 (4)	C8—C9	1.390 (3)
C1—C7	1.447 (4)	C8—N1	1.416 (3)
C2—O1	1.355 (3)	C9—C10	1.373 (4)
C2—C3	1.402 (3)	C9—H9	0.9300
C3—O2	1.358 (3)	C10—C11	1.373 (4)
C3—C4	1.371 (4)	C10—Br1	1.900 (2)
C4—C5	1.384 (4)	C11—C12	1.377 (4)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.374 (4)	C12—C13	1.375 (4)
C5—H5	0.9300	C12—H12	0.9300
C6—H6	0.9300	C13—H13	0.9300
C7—N1	1.278 (3)	O1—H1	0.87 (4)
C7—H7	0.9300	O2—H2	0.78 (4)
C2—C1—C6	119.3 (2)	C13—C8—C9	118.6 (2)
C2—C1—C7	120.9 (2)	C13—C8—N1	116.7 (2)
C6—C1—C7	119.8 (2)	C9—C8—N1	124.6 (2)
O1—C2—C1	122.8 (2)	C10—C9—C8	119.2 (2)
O1—C2—C3	117.5 (2)	C10—C9—H9	120.4
C1—C2—C3	119.7 (2)	C8—C9—H9	120.4
O2—C3—C4	119.9 (2)	C9—C10—C11	122.5 (2)
O2—C3—C2	120.5 (2)	C9—C10—Br1	119.09 (19)
C4—C3—C2	119.7 (2)	C11—C10—Br1	118.4 (2)
C3—C4—C5	121.3 (3)	C10—C11—C12	117.9 (2)
C3—C4—H4	119.4	C10—C11—H11	121.0
C5—C4—H4	119.3	C12—C11—H11	121.0
C6—C5—C4	119.6 (3)	C13—C12—C11	120.8 (3)
C6—C5—H5	120.2	C13—C12—H12	119.6
C4—C5—H5	120.2	C11—C12—H12	119.6
C5—C6—C1	120.5 (3)	C12—C13—C8	120.8 (2)
C5—C6—H6	119.8	C12—C13—H13	119.6
C1—C6—H6	119.8	C8—C13—H13	119.6
N1—C7—C1	122.1 (2)	C7—N1—C8	121.6 (2)
N1—C7—H7	118.9	C2—O1—H1	105 (2)
C1—C7—H7	118.9	C3—O2—H2	111 (3)
C6—C1—C2—O1	−179.8 (2)	C6—C1—C7—N1	178.8 (2)
C7—C1—C2—O1	0.6 (4)	C13—C8—C9—C10	0.1 (4)
C6—C1—C2—C3	0.1 (4)	N1—C8—C9—C10	−179.9 (2)
C7—C1—C2—C3	−179.5 (2)	C8—C9—C10—C11	0.7 (4)
O1—C2—C3—O2	1.6 (4)	C8—C9—C10—Br1	−179.41 (19)
C1—C2—C3—O2	−178.3 (2)	C9—C10—C11—C12	−0.4 (4)
O1—C2—C3—C4	−179.6 (2)	Br1—C10—C11—C12	179.8 (2)
C1—C2—C3—C4	0.5 (4)	C10—C11—C12—C13	−0.9 (4)
O2—C3—C4—C5	178.2 (3)	C11—C12—C13—C8	1.7 (4)
C2—C3—C4—C5	−0.6 (4)	C9—C8—C13—C12	−1.3 (4)
C3—C4—C5—C6	0.2 (4)	N1—C8—C13—C12	178.7 (2)
C4—C5—C6—C1	0.4 (4)	C1—C7—N1—C8	179.7 (2)
C2—C1—C6—C5	−0.5 (4)	C13—C8—N1—C7	−172.2 (2)
C7—C1—C6—C5	179.0 (2)	C9—C8—N1—C7	7.9 (4)
C2—C1—C7—N1	−1.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.87 (4)	1.81 (4)	2.606 (3)	151 (3)
O2—H2···O1	0.78 (4)	2.31 (5)	2.718 (3)	113 (4)
O2—H2···O2i	0.78 (4)	2.48 (5)	3.124 (3)	141 (5)
O2—H2···O1ii	0.78 (4)	2.46 (4)	2.986 (3)	126 (4)

Parameters	X-ray	AM1	PM3	HF*	DFT/B3LYP*
C1—C7	1.447 (4)	1.4659	1.4592	1.4655	1.4472
C8—N1	1.416 (3)	1.4103	1.431	1.4082	1.4071
C7—N1	1.278 (3)	1.2923	1.3028	1.2626	1.2947
C2—O1	1.355 (3)	1.3711	1.3612	1.3414	1.35
C3—O2	1.358 (3)	1.3749	1.3695	1.3472	1.3601
C10—Br1	1.900 (2)	1.8743	1.8676	1.899	1.9138
O1—C2—C1	122.8 (2)	126.384	124.0177	124.2818	123.5134
N1—C7—C1	122.1 (2)	123.752	119.6344	123.297	121.9975
O2—C3—C4	119.9 (2)	117.2553	115.9182	119.9887	120.7548
O1—C2—C3	117.5 (2)	113.7932	116.4985	115.8053	116.4318
O2—C3—C2	120.5 (2)	122.181	123.9237	119.978	119.4331
C7—N1—C8	121.6 (2)	121.8246	122.1744	120.3634	121.3341
C12—C13—H13	119.6	119.7856	119.8376	120.8687	121.0058
C8—C13—H13	119.6	120.1274	120.1469	119.0149	118.759
C1—C7—N1—C8	179.7 (2)	-179.2308	179.9974	-178.6515	-177.5099
C9—C8—N1—C7	7.9 (4)	34.1092	0.0009	44.5418	35.1166
C2—C1—C7—N1	-1.6 (4)	2.6542	0.0087	0.8066	0.3196
N1—C8—C9—C10	-179.9 (2)	-177.3895	179.9976	179.3862	179.4699
C8—C9—C10—Br1	-179.41 (19)	-179.8397	-180.0011	-179.9136	-179.7804

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.87 (4)	1.81 (4)	2.606 (3)	151 (3)
O2—H2⋯O1	0.78 (4)	2.31 (5)	2.718 (3)	113 (4)
O2—H2⋯O2i	0.78 (4)	2.48 (5)	3.124 (3)	141 (5)
O2—H2⋯O1ii	0.78 (4)	2.46 (4)	2.986 (3)	126 (4)

Symmetry codes: (i) ; (ii) .

Parameters	X-ray	AM1	PM3	HF*	DFT/B3LYP*
C1—C7	1.447 (4)	1.4659	1.4592	1.4655	1.4472
C8—N1	1.416 (3)	1.4103	1.431	1.4082	1.4071
C7—N1	1.278 (3)	1.2923	1.3028	1.2626	1.2947
C2—O1	1.355 (3)	1.3711	1.3612	1.3414	1.35
C3—O2	1.358 (3)	1.3749	1.3695	1.3472	1.3601
C10—Br1	1.900 (2)	1.8743	1.8676	1.899	1.9138

O1—C2—C1	122.8 (2)	126.384	124.0177	124.2818	123.5134
N1—C7—C1	122.1 (2)	123.752	119.6344	123.297	121.9975
O2—C3—C4	119.9 (2)	117.2553	115.9182	119.9887	120.7548
O1—C2—C3	117.5 (2)	113.7932	116.4985	115.8053	116.4318
O2—C3—C2	120.5 (2)	122.181	123.9237	119.978	119.4331
C7—N1—C8	121.6 (2)	121.8246	122.1744	120.3634	121.3341

C12—C13—H13	119.6	119.7856	119.8376	120.8687	121.0058
C8—C13—H13	119.6	120.1274	120.1469	119.0149	118.759
C1—C7—N1—C8	179.7 (2)	−179.2308	179.9974	−178.6515	−177.5099
C9—C8—N1—C7	7.9 (4)	34.1092	0.0009	44.5418	35.1166
C2—C1—C7—N1	−1.6 (4)	2.6542	0.0087	0.8066	0.3196
N1—C8—C9—C10	−179.9 (2)	−177.3895	179.9976	179.3862	179.4699
C8—C9—C10—Br1	−179.41 (19)	−179.8397	−180.0011	−179.9136	−179.7804

*6-31G(d,p).