(E)-4-Bromo-2-[2-(hydroxy­meth­yl)phenyl­imino­meth­yl]phenol

The title compound, C₁₄H₁₂BrNO₂, adopt the phenol–imine tautomeric form. The dihedral angle between the aromatic rings is 27.49 (2)°. In the structure, there are O—H...O inter­molecular hydrogen bonds and O—H...N and C—H...O intra­molecular hydrogen bonds. The phenol H atom forms a strong intra­molecular hydrogen bond with the imine N atom.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.083
• wR factor = 0.164
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level B
RINTA01_ALERT_3_B  The value of Rint is greater than 0.15
            Rint given   0.158
PLAT020_ALERT_3_B The value of Rint is greater than 0.10 .........       0.16
PLAT417_ALERT_2_B Short Inter D-H..H-D       H2     ..  H2      ..       1.21 Ang.

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT245_ALERT_2_C U(iso) H1      Smaller than U(eq) O1      by ...       0.02 AngSq
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

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

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S1. Comment

The H atom in the compound is located on atom O1 thus confirming a preference for the phenol-imine tautomer in the solid state, it is consisted with the related structure (Özek et al., 2007). It is known that schiff bases may exhibit thermochromism depending on the planarity or non-planarity, respectively (Moustakali-Mavridis et al., 1978). The title compound stabilezed by inter and intramolecular hydrogen bonds, nameyl, O2—H2···O2 (symmetry code: -x + 1,-y,-z), O1—H1···N1 and C12—H12···O2.

Related literature

For related literature, see: Özek et al., 2007; Moustakali-Mavridis, Hadjoudis & Mavridis (1978).

S2. Experimental

The compound (E)-2-[(2-Hydroxymethylphenylimino)methyl]-4-bromophenol was prepared by reflux a mixture of a solution containing 5-bromosalicylaldehyde (0.05 g 0.25 mmol) in 20 ml e thanol and a solution containing 2-Hydroxymethylaniline (0.03 g 0.25 mmol) in 20 ml e thanol. The reaction mixture was stirred for 1 h under reflux. The crystals of (E)-2-[(2-Hydroxymethylphenylimino)methyl]-4-bromophenol suitable for X-ray analysis were obtained from ethylalcohol by slow evaporation (yield % 61; m.p.387–389°K).

S3. Refinement

For the title compound(I), the structure was solved by direct methods and refined by full-matrix least-square techniques. All H atoms were located geometrically and refined using a riding model, except for atom H1 bonded to atom O1, fixing the aromatic C—H distance at 0.93 Å,the C—H₂ distance 0.97 Å. The intensity data collected for the title structure are generally weak, so the R-int lies outside the normal range.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999) and PARST (Nardelli, 1995).

Figures

Fig. 1. An ORTEP view of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids.

(E)-4-Bromo-2-[2-(hydroxymethyl)phenyliminomethyl]phenol

Crystal data

C14H12BrNO2	F(000) = 616
Mr = 306.16	Dx = 1.608 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7218 reflections
a = 6.4356 (13) Å	θ = 3.2–29.3°
b = 4.6361 (5) Å	µ = 3.24 mm^−1
c = 42.693 (8) Å	T = 293 K
β = 96.904 (16)°	Plate, brown
V = 1264.5 (4) Å^3	0.59 × 0.32 × 0.03 mm
Z = 4

Data collection

STOE IPDS 2 diffractometer	2418 independent reflections
Radiation source: fine-focus sealed tube	1281 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.158
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 3.2°
ω scan	h = −7→7
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −5→5
Tmin = 0.435, Tmax = 0.827	l = −52→52
8887 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.083	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0669P)^2] where P = (Fo^2 + 2Fc^2)/3
2418 reflections	(Δ/σ)max = 0.001
167 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3539 (8)	0.5546 (12)	0.15615 (15)	0.0442 (15)
C2	0.5621 (8)	0.6418 (13)	0.15407 (17)	0.0499 (16)
C3	0.6531 (9)	0.8446 (15)	0.17555 (18)	0.0569 (19)
H3	0.7895	0.9046	0.1741	0.068*
C4	0.5485 (10)	0.9571 (15)	0.19847 (19)	0.0622 (18)
H4	0.6127	1.0933	0.2124	0.075*
C5	0.3446 (10)	0.8679 (14)	0.20100 (17)	0.0527 (17)
C6	0.2488 (9)	0.6722 (13)	0.17980 (16)	0.0471 (15)
H6	0.1113	0.6174	0.1813	0.056*
C7	0.2448 (8)	0.3595 (12)	0.13302 (16)	0.0422 (14)
H7	0.1063	0.3119	0.1348	0.051*
C8	0.2096 (8)	0.0736 (12)	0.08767 (15)	0.0413 (14)
C9	0.0395 (9)	−0.0889 (12)	0.09518 (17)	0.0499 (16)
H9	0.0003	−0.0846	0.1154	0.060*
C10	−0.0702 (9)	−0.2571 (13)	0.07177 (19)	0.0546 (18)
H10	−0.1835	−0.3665	0.0765	0.066*
C11	−0.0134 (9)	−0.2637 (13)	0.04185 (18)	0.0540 (18)
H11	−0.0887	−0.3762	0.0264	0.065*
C12	0.1539 (9)	−0.1049 (12)	0.03464 (17)	0.0496 (16)
H12	0.1916	−0.1122	0.0143	0.060*
C13	0.2691 (8)	0.0679 (11)	0.05727 (16)	0.0419 (15)
C14	0.4530 (8)	0.2478 (13)	0.04907 (17)	0.0497 (16)
H14A	0.4368	0.4441	0.0562	0.060*
H14B	0.5813	0.1712	0.0603	0.060*
N1	0.3306 (7)	0.2525 (10)	0.11061 (12)	0.0424 (12)
O1	0.6734 (7)	0.5367 (11)	0.13205 (13)	0.0666 (14)
O2	0.4709 (8)	0.2513 (10)	0.01635 (13)	0.0743 (15)
H2	0.4878	0.0863	0.0102	0.111*
Br1	0.19493 (12)	1.02961 (17)	0.232551 (19)	0.0751 (4)
H1	0.589 (9)	0.427 (13)	0.1214 (17)	0.05 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.042 (3)	0.045 (3)	0.045 (4)	0.000 (3)	0.001 (3)	0.004 (3)
C2	0.043 (3)	0.059 (4)	0.048 (5)	0.002 (3)	0.008 (3)	0.000 (4)
C3	0.044 (3)	0.067 (4)	0.059 (5)	−0.005 (3)	0.004 (3)	−0.017 (4)
C4	0.064 (4)	0.060 (4)	0.059 (5)	−0.007 (4)	−0.006 (4)	−0.001 (4)
C5	0.065 (4)	0.049 (4)	0.043 (4)	0.012 (3)	0.002 (3)	0.001 (3)
C6	0.049 (3)	0.048 (3)	0.045 (4)	0.004 (3)	0.007 (3)	0.001 (3)
C7	0.040 (3)	0.045 (3)	0.043 (4)	−0.007 (3)	0.011 (3)	0.003 (3)
C8	0.038 (3)	0.043 (3)	0.044 (4)	0.002 (2)	0.008 (3)	0.003 (3)
C9	0.046 (3)	0.054 (4)	0.051 (4)	−0.004 (3)	0.011 (3)	0.002 (3)
C10	0.046 (3)	0.052 (4)	0.065 (5)	−0.009 (3)	0.004 (3)	0.005 (4)
C11	0.053 (3)	0.057 (4)	0.050 (5)	−0.010 (3)	−0.005 (3)	−0.006 (4)
C12	0.056 (3)	0.049 (3)	0.043 (4)	0.002 (3)	0.004 (3)	−0.007 (3)
C13	0.039 (3)	0.039 (3)	0.048 (4)	0.004 (2)	0.006 (3)	−0.001 (3)
C14	0.049 (3)	0.049 (3)	0.052 (5)	−0.001 (3)	0.011 (3)	−0.003 (3)
N1	0.045 (2)	0.046 (3)	0.036 (3)	0.001 (2)	0.005 (2)	0.000 (3)
O1	0.051 (2)	0.083 (3)	0.069 (4)	−0.013 (3)	0.022 (2)	−0.023 (3)
O2	0.108 (4)	0.071 (3)	0.050 (4)	−0.024 (3)	0.039 (3)	−0.014 (3)
Br1	0.1005 (6)	0.0744 (5)	0.0545 (5)	0.0018 (4)	0.0262 (4)	−0.0133 (4)

Geometric parameters (Å, º)

C1—C6	1.392 (9)	C8—N1	1.439 (7)
C1—C2	1.412 (8)	C9—C10	1.391 (9)
C1—C7	1.456 (8)	C9—H9	0.9300
C2—O1	1.340 (8)	C10—C11	1.371 (10)
C2—C3	1.392 (9)	C10—H10	0.9300
C3—C4	1.357 (10)	C11—C12	1.370 (8)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.392 (9)	C12—C13	1.397 (8)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.374 (9)	C13—C14	1.523 (8)
C5—Br1	1.902 (7)	C14—O2	1.415 (8)
C6—H6	0.9300	C14—H14A	0.9700
C7—N1	1.262 (8)	C14—H14B	0.9700
C7—H7	0.9300	O1—H1	0.84 (6)
C8—C9	1.398 (8)	O2—H2	0.8200
C8—C13	1.396 (9)
C6—C1—C2	118.7 (5)	C10—C9—C8	118.8 (7)
C6—C1—C7	119.9 (5)	C10—C9—H9	120.6
C2—C1—C7	121.3 (6)	C8—C9—H9	120.6
O1—C2—C3	119.3 (5)	C11—C10—C9	120.9 (6)
O1—C2—C1	122.1 (6)	C11—C10—H10	119.6
C3—C2—C1	118.6 (6)	C9—C10—H10	119.6
C4—C3—C2	121.9 (6)	C10—C11—C12	120.2 (6)
C4—C3—H3	119.0	C10—C11—H11	119.9
C2—C3—H3	119.0	C12—C11—H11	119.9
C3—C4—C5	119.7 (6)	C11—C12—C13	121.2 (7)
C3—C4—H4	120.2	C11—C12—H12	119.4
C5—C4—H4	120.2	C13—C12—H12	119.4
C6—C5—C4	119.8 (7)	C12—C13—C8	118.2 (5)
C6—C5—Br1	120.1 (5)	C12—C13—C14	121.1 (6)
C4—C5—Br1	120.0 (5)	C8—C13—C14	120.7 (5)
C5—C6—C1	121.2 (6)	O2—C14—C13	113.0 (5)
C5—C6—H6	119.4	O2—C14—H14A	109.0
C1—C6—H6	119.4	C13—C14—H14A	109.0
N1—C7—C1	122.6 (5)	O2—C14—H14B	109.0
N1—C7—H7	118.7	C13—C14—H14B	109.0
C1—C7—H7	118.7	H14A—C14—H14B	107.8
C9—C8—C13	120.8 (6)	C7—N1—C8	119.5 (5)
C9—C8—N1	121.9 (6)	C2—O1—H1	103 (5)
C13—C8—N1	117.2 (5)	C14—O2—H2	109.5
C6—C1—C2—O1	179.6 (6)	N1—C8—C9—C10	−180.0 (5)
C7—C1—C2—O1	−4.2 (9)	C8—C9—C10—C11	−0.1 (9)
C6—C1—C2—C3	−0.7 (9)	C9—C10—C11—C12	0.4 (9)
C7—C1—C2—C3	175.5 (6)	C10—C11—C12—C13	−0.5 (9)
O1—C2—C3—C4	−179.6 (7)	C11—C12—C13—C8	0.3 (8)
C1—C2—C3—C4	0.8 (10)	C11—C12—C13—C14	−179.1 (5)
C2—C3—C4—C5	0.4 (11)	C9—C8—C13—C12	−0.1 (8)
C3—C4—C5—C6	−1.7 (10)	N1—C8—C13—C12	179.9 (4)
C3—C4—C5—Br1	−178.9 (6)	C9—C8—C13—C14	179.3 (5)
C4—C5—C6—C1	1.7 (9)	N1—C8—C13—C14	−0.7 (7)
Br1—C5—C6—C1	178.9 (5)	C12—C13—C14—O2	8.7 (8)
C2—C1—C6—C5	−0.5 (9)	C8—C13—C14—O2	−170.7 (5)
C7—C1—C6—C5	−176.7 (6)	C1—C7—N1—C8	−176.7 (5)
C6—C1—C7—N1	178.1 (6)	C9—C8—N1—C7	−28.5 (8)
C2—C1—C7—N1	2.0 (9)	C13—C8—N1—C7	151.5 (5)
C13—C8—C9—C10	0.0 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.84 (6)	1.86 (6)	2.638 (7)	155 (7)
C12—H12···O2	0.93	2.46	2.807 (8)	102
O2—H2···O2^i	0.82	1.97	2.765 (10)	163

Symmetry code: (i) −x+1, −y, −z.