Three (E)-2-[(bromo­phen­yl)imino­meth­yl]-4-methoxy­phenols

The title compounds, (E)-2-[(2-bromo­phenyl)imino­methyl]-4-methoxy­phenol, C₁₄H₁₂BrNO₂, (I), (E)-2-[(3-bromo­phenyl)­imino­methyl]-4-methoxy­phenol, C₁₄H₁₂BrNO₂, (II), and (E)-2-[(4-bromo­phenyl)imino­methyl]-4-methoxy­phenol, C₁₄H₁₂BrNO₂, (III), adopt the phenol–imine tautomeric form. In all three structures, there are strong intra­molecular O—H...N hydrogen bonds. Compound (I) has strong inter­molecular hydrogen bonds, while compound (III) has weak inter­molecular hydrogen bonds. In addition to these inter­molecular inter­actions, C—H...π inter­actions in (I) and (III), and π–π inter­actions in (I), play roles in the crystal packing. The dihedral angles between the aromatic rings are 15.34 (12), 6.1 (3) and 39.2 (14)° for (I), (II) and (III), respectively.

S1. Comment

Although Schiff bases have been widely used as ligands in the formation of transition metal complexes and structurally characterized, a relatively small number of free Schiff bases have been similarly characterized (Calligaris & Randaccio, 1987). Schiff bases, however, play an important role in many fields of chemistry and biochemistry (Lozier et al., 1975; Garnovskii et al., 1993). The overall behaviour of these compounds has been defined as a proton-transfer reaction between the phenol–imine and keto–amine tautomers. It is known that the phenol–imine tautomer is dominant in salicylaldimine, while the keto–amine form is preferred in naphthaldimine Schiff bases, depending on the solvent polarities. Moreover, in the solid state, the keto–amine tautomer is present in naphthaldimines (Hökelek et al., 2000; Odabaşoğlu et al., 2003), while the phenol–imine form exists in salicylaldimine Schiff bases (Kaitner & Pavlovic, 1996; Yıldız et al., 1998). As part of a general study of the crystal chemistry of dyes, and to provide templates for molecular-modelling studies, the crystal structures of the title compounds, (I), (II) and (III), have been determined.

The molecular structures of (I), (II) and (III), with the atom-labelling schemes, are shown in Figs. 1, 2 and 3, respectively, and selected bond lengths and angles are given in Table 1. In all three molecules, (I), (II) and (III), the phenol–imine tautomer is favoured over the keto–amine form, as indicated by the C6—O1, C8—N1, C1—C8 and C1—C6 bond lengths (Figs. 1–3 and Table 1). A similar situation was observed for 2-(3-methoxysalicylideneamino)-1H-benzimidazolemonohydrate [C—O = 1.357 (2) Å and C—N = 1.285 (2) Å; Albayrak et al., 2005]. The H atom in all three compounds is located on atom O1, thus confirming a preference for the phenol–imine tautomer in the solid state. The O1—C6 bond lengths are approximately the same, indicating single-bond character, whereas the C8–N1 bond lengths are indicative of significant double-bond character in (I), (II) and (III).

It is known that Schiff bases may exhibit thermochromism or photochromism, depending on the planarity or non-planarity of the molecule, respectively. This planarity of the molecule allows the H atom to be transferred through the hydrogen bond in the ground state with a low energy requirement (Hadjoudis et al., 1987). Therefore, one can expect thermochromic properties in (I) and (II) caused by planarity of the molecules: the dihedral angles between rings A (C1–C6) and B (C9–C14) are 15.34 (12) and 6.1 (3)°, respectively. One can also expect photochromic properties in (III) caused by the non-planarity of the molecule: the dihedral angle between the A and B rings is 39.2 (14)°.

These differences in planarity are also reflected in the C14—C9—N1—C8 torsion angles (Table 1) and are certainly related to the occurrence of intermolecular C—H···O and C—H···π interactions observed in compounds (I) and (III) (Tables 2 and 4), which influence the packing of the molecules of (I) and (III) as shown in Figs. 4–6. Indeed, in compound (II), there is only an intramolecular O—H···N hydrogen bond (Table 3). The higher value of the torsion angle observed in compound (III) [-31.1 (4)°] compared with the lower values observed in (I) and (II) [-20.9 (3)° and -6.6 (9)°] may result from the occurrence of three C—H···π interactions in (III) (Table 4, Fig. 7), whereas only one is present in compound (I) (Table 2, Fig. 5). In (II), there are no C—H···π and π–π interactions, and the only interactions playing a role in the packing are intermolecular van der Waals interactions, resulting in a rather low torsion angle of -6.6 (9)°.

The occurrence of C—H···O hydrogen bonds results in the formation of C(5) and C(8) chains (Bernstein et al., 1995) developing parallel to the c axis in (I) and (III), respectively (Tables 2 and 4, Figs. 4 and 6). In addition to these interactions, only compound (I) presents π–π stacking (Fig. 5). This slipped π–π interaction occurs between Cg1···Cg1ⁱ [Cg1 is the centroid of the C1–C6 ring; symmetry code: (i) 1 - x, 1 - y, 1 - z], with a centroid-to-centroid distance of 3.851 Å and a plane-to-plane separation of 3.486 Å, resulting in an offset angle of 25.2°.

Related literature

For related literature, see: Albayrak et al. (2005); Bernstein et al. (1995); Calligaris & Randaccio (1987); Flack (1983); Garnovskii et al. (1993); Hökelek et al. (2000); Hadjoudis et al. (1987); Kaitner & Pavlovic (1996); Lozier et al. (1975); Odabaşoğlu et al. (2003, 2005); Yıldız, Kılıç & Hökelek (1998).

S2. Experimental

The title compounds were prepared by reported procedures (Odabaşoğlu et al., 2005), using 2-, 3-, and 4-bromoanilines and 5-methoxysalicylaldehyde as starting materials. Well shaped crystals of (I), (II) and (III) were obtained by slow evaporation of ethanol solutions [for (I), yield 72% and m.p. 399–400 K; for (II), yield 86% and m.p. 367–368 K; for (III), yield 78% and m.p. 396–397 K].

S3. Refinement

For all three compounds, all H atoms were refined using a riding model, with C—H distances of 0.93 Å for aromatic H atoms and 0.96 Å for methyl H atoms, and O—H distances of 0.82 Å. and with U_iso(H) = 1.5U_eq(C) for the methyl H atoms or 1.2U_eq(C,O) for the remaining H atoms. For (II), there is a twin by inversion (racemic twin), as suggested by the value of the Flack parameter (Flack, 1983) of 0.47 (2).

Computing details

For all compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1998).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids. The dashed line indicates the hydrogen bond. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. A view of (II), with the atom-numbering scheme and 50% probability displacement ellipsoids. The dashed line indicates the hydrogen bond. H atoms are represented as small spheres of arbitrary radii.
	Fig. 3. A view of (III), with the atom-numbering scheme and 50% probability displacement ellipsoids. The dashed line indicates the hydrogen bond. H atoms are represented as small spheres of arbitrary radii.
	Fig. 4. A partial packing view of (I), showing the formation of the C(5) chain through C—H···O hydrogen bonds (dashed lines). H atoms are represented as small spheres of arbitrary radii. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) x, 3/2 - y, z + 1/2; (ii) x, 3/2 - y, z - 1/2.]
	Fig. 5. A partial packing view of (I), showing the C—H···π and π–π interactions. Dashed lines indicate hydrogen bonds. H atoms are represented as small spheres of arbitrary radii. H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 6. A partial packing view of (III), showing the formation of the C(8) chain through C—H···O hydrogen bonds (dashed lines). H atoms are represented as small spheres of arbitrary radii. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry code: (i) x, y, 1 + z.]
	Fig. 7. A partial packing view of (III). Dashed lines indicates C10–H···π and C13—H···π interactions. H atoms not involved in hydrogen bonding have been omitted for clarity. Cg2 is the centroid of the C9—C14 ring. [Symmetry codes: (i) x, -y, z - 1/2; (ii) x, y + 1/2, z + 1/2.]

(I) (E)-2-[(2-bromophenyl)iminomethyl]-4-methoxyphenol

Crystal data

C14H12BrNO2	F(000) = 616
Mr = 306.16	Dx = 1.600 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17760 reflections
a = 13.3255 (8) Å	θ = 2.9–28.0°
b = 8.7090 (5) Å	µ = 3.23 mm^−1
c = 11.9743 (6) Å	T = 296 K
β = 113.845 (4)°	Prism, red
V = 1271.02 (12) Å^3	0.66 × 0.35 × 0.17 mm
Z = 4

Data collection

Stoe IPDS 2 diffractometer	2500 independent reflections
Radiation source: fine-focus sealed tube	2041 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 2.9°
ω scans	h = −16→16
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	k = −10→10
Tmin = 0.264, Tmax = 0.603	l = −14→14
17760 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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.057	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0246P)^2 + 0.369P] where P = (Fo^2 + 2Fc^2)/3
2500 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. 360 frames, detector distance = 80 mm

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	0.50831 (17)	0.6980 (2)	0.43648 (19)	0.0398 (5)
C2	0.41462 (17)	0.6863 (3)	0.4623 (2)	0.0459 (5)
H2	0.4149	0.7306	0.5331	0.055*
C3	0.32298 (19)	0.6105 (3)	0.3843 (2)	0.0511 (6)
C4	0.3238 (2)	0.5426 (3)	0.2800 (2)	0.0598 (6)
H4	0.2618	0.4905	0.2273	0.072*
C5	0.4143 (2)	0.5512 (3)	0.2533 (2)	0.0560 (6)
H5	0.4135	0.5045	0.1830	0.067*
C6	0.50727 (19)	0.6292 (3)	0.3304 (2)	0.0460 (5)
C7	0.2211 (2)	0.6636 (4)	0.5037 (3)	0.0702 (8)
H7A	0.1506	0.6436	0.5045	0.105*
H7B	0.2313	0.7724	0.5005	0.105*
H7C	0.2775	0.6225	0.5764	0.105*
C8	0.60408 (17)	0.7762 (3)	0.52179 (18)	0.0414 (5)
H8	0.6043	0.8119	0.5951	0.050*
C9	0.78170 (17)	0.8774 (2)	0.57851 (18)	0.0378 (5)
C10	0.88022 (18)	0.8589 (2)	0.5652 (2)	0.0416 (5)
C11	0.97437 (19)	0.9346 (3)	0.6388 (2)	0.0513 (6)
H11	1.0394	0.9184	0.6291	0.062*
C12	0.9720 (2)	1.0342 (3)	0.7265 (2)	0.0576 (6)
H12	1.0354	1.0856	0.7766	0.069*
C13	0.8752 (2)	1.0575 (3)	0.7398 (2)	0.0558 (6)
H13	0.8731	1.1262	0.7983	0.067*
C14	0.78146 (19)	0.9799 (3)	0.6673 (2)	0.0473 (5)
H14	0.7169	0.9964	0.6778	0.057*
N1	0.68871 (14)	0.7972 (2)	0.49842 (16)	0.0404 (4)
O1	0.59561 (14)	0.6341 (2)	0.30092 (15)	0.0580 (4)
H1	0.6451	0.6831	0.3530	0.087*
O2	0.22715 (14)	0.5934 (2)	0.40032 (19)	0.0692 (5)
Br1	0.88677 (2)	0.72396 (3)	0.44408 (2)	0.05510 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0391 (11)	0.0417 (12)	0.0354 (11)	−0.0026 (9)	0.0117 (10)	0.0016 (9)
C2	0.0414 (13)	0.0501 (14)	0.0468 (13)	−0.0039 (9)	0.0186 (12)	−0.0016 (10)
C3	0.0384 (13)	0.0523 (14)	0.0578 (15)	−0.0041 (10)	0.0146 (12)	0.0024 (11)
C4	0.0471 (14)	0.0611 (16)	0.0550 (16)	−0.0128 (12)	0.0040 (13)	−0.0070 (13)
C5	0.0584 (15)	0.0624 (16)	0.0404 (13)	−0.0072 (12)	0.0130 (12)	−0.0109 (11)
C6	0.0483 (13)	0.0489 (13)	0.0400 (12)	−0.0024 (10)	0.0170 (11)	−0.0003 (10)
C7	0.0538 (16)	0.0813 (19)	0.086 (2)	−0.0022 (14)	0.0391 (16)	0.0103 (16)
C8	0.0435 (12)	0.0475 (11)	0.0338 (11)	−0.0030 (10)	0.0164 (10)	0.0001 (9)
C9	0.0389 (11)	0.0387 (11)	0.0333 (11)	−0.0023 (9)	0.0120 (10)	0.0050 (9)
C10	0.0416 (12)	0.0404 (12)	0.0425 (12)	−0.0003 (9)	0.0167 (11)	0.0045 (9)
C11	0.0409 (13)	0.0507 (14)	0.0601 (15)	−0.0056 (10)	0.0180 (12)	0.0001 (12)
C12	0.0480 (15)	0.0595 (16)	0.0540 (16)	−0.0167 (12)	0.0088 (13)	−0.0046 (12)
C13	0.0671 (17)	0.0553 (15)	0.0465 (14)	−0.0149 (12)	0.0244 (13)	−0.0098 (11)
C14	0.0475 (13)	0.0514 (13)	0.0461 (13)	−0.0053 (10)	0.0221 (11)	−0.0013 (10)
N1	0.0375 (9)	0.0449 (10)	0.0377 (9)	−0.0024 (8)	0.0140 (8)	0.0008 (8)
O1	0.0562 (10)	0.0760 (12)	0.0487 (10)	−0.0107 (9)	0.0284 (9)	−0.0156 (8)
O2	0.0407 (10)	0.0810 (13)	0.0865 (14)	−0.0153 (9)	0.0263 (10)	−0.0078 (11)
Br1	0.05384 (15)	0.05616 (14)	0.06409 (16)	−0.00428 (12)	0.03293 (12)	−0.00926 (13)

Geometric parameters (Å, º)

C1—C6	1.399 (3)	C8—N1	1.280 (3)
C1—C2	1.406 (3)	C8—H8	0.9300
C1—C8	1.443 (3)	C9—C14	1.389 (3)
C2—C3	1.370 (3)	C9—C10	1.394 (3)
C2—H2	0.9300	C9—N1	1.408 (3)
C3—O2	1.374 (3)	C10—C11	1.376 (3)
C3—C4	1.386 (4)	C10—Br1	1.896 (2)
C4—C5	1.370 (4)	C11—C12	1.372 (4)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.387 (3)	C12—C13	1.378 (4)
C5—H5	0.9300	C12—H12	0.9300
C6—O1	1.360 (3)	C13—C14	1.376 (3)
C7—O2	1.412 (3)	C13—H13	0.9300
C7—H7A	0.9600	C14—H14	0.9300
C7—H7B	0.9600	O1—H1	0.8200
C7—H7C	0.9600
C6—C1—C2	119.0 (2)	N1—C8—C1	121.20 (19)
C6—C1—C8	121.74 (19)	N1—C8—H8	119.4
C2—C1—C8	119.24 (19)	C1—C8—H8	119.4
C3—C2—C1	120.8 (2)	C14—C9—C10	117.1 (2)
C3—C2—H2	119.6	C14—C9—N1	124.50 (19)
C1—C2—H2	119.6	C10—C9—N1	118.35 (18)
C2—C3—O2	125.5 (2)	C11—C10—C9	121.9 (2)
C2—C3—C4	119.3 (2)	C11—C10—Br1	118.37 (16)
O2—C3—C4	115.2 (2)	C9—C10—Br1	119.72 (16)
C5—C4—C3	121.1 (2)	C12—C11—C10	119.8 (2)
C5—C4—H4	119.5	C12—C11—H11	120.1
C3—C4—H4	119.5	C10—C11—H11	120.1
C4—C5—C6	120.3 (2)	C11—C12—C13	119.6 (2)
C4—C5—H5	119.9	C11—C12—H12	120.2
C6—C5—H5	119.9	C13—C12—H12	120.2
O1—C6—C5	118.4 (2)	C14—C13—C12	120.5 (2)
O1—C6—C1	122.0 (2)	C14—C13—H13	119.7
C5—C6—C1	119.5 (2)	C12—C13—H13	119.7
O2—C7—H7A	109.5	C13—C14—C9	121.1 (2)
O2—C7—H7B	109.5	C13—C14—H14	119.4
H7A—C7—H7B	109.5	C9—C14—H14	119.4
O2—C7—H7C	109.5	C8—N1—C9	122.19 (18)
H7A—C7—H7C	109.5	C6—O1—H1	109.5
H7B—C7—H7C	109.5	C3—O2—C7	117.4 (2)
C6—C1—C2—C3	−0.8 (3)	N1—C9—C10—C11	179.2 (2)
C8—C1—C2—C3	−178.8 (2)	C14—C9—C10—Br1	−178.84 (16)
C1—C2—C3—O2	−179.5 (2)	N1—C9—C10—Br1	−1.6 (3)
C1—C2—C3—C4	1.0 (4)	C9—C10—C11—C12	−1.4 (4)
C2—C3—C4—C5	−0.5 (4)	Br1—C10—C11—C12	179.37 (19)
O2—C3—C4—C5	−180.0 (2)	C10—C11—C12—C13	−0.1 (4)
C3—C4—C5—C6	−0.3 (4)	C11—C12—C13—C14	1.0 (4)
C4—C5—C6—O1	179.6 (2)	C12—C13—C14—C9	−0.4 (4)
C4—C5—C6—C1	0.6 (4)	C10—C9—C14—C13	−1.0 (3)
C2—C1—C6—O1	−179.0 (2)	N1—C9—C14—C13	−178.0 (2)
C8—C1—C6—O1	−1.0 (3)	C1—C8—N1—C9	177.96 (19)
C2—C1—C6—C5	0.0 (3)	C14—C9—N1—C8	−20.9 (3)
C8—C1—C6—C5	178.0 (2)	C10—C9—N1—C8	162.1 (2)
C6—C1—C8—N1	6.2 (3)	C2—C3—O2—C7	2.0 (4)
C2—C1—C8—N1	−175.8 (2)	C4—C3—O2—C7	−178.5 (2)
C14—C9—C10—C11	2.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.88	2.603 (2)	146
O1—H1···Br1	0.82	2.97	3.6368 (17)	139
C12—H12···O2^i	0.93	2.84	3.377 (3)	118
C8—H8···O1^ii	0.93	2.56	3.478 (3)	171
C7—H7B···Cg2^iii	0.96 (1)	2.98 (1)	3.763 (4)	140 (1)

Symmetry codes: (i) x+1, −y+3/2, z+1/2; (ii) x, −y+3/2, z+1/2; (iii) −x+1, −y, −z+1.

(II) (E)-2-[(3-bromophenyl)iminomethyl]-4-methoxyphenol

Crystal data

C14H12BrNO2	F(000) = 308
Mr = 306.16	Dx = 1.600 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 8350 reflections
a = 12.6852 (19) Å	θ = 3.0–27.9°
b = 4.5157 (4) Å	µ = 3.23 mm^−1
c = 12.1383 (18) Å	T = 296 K
β = 113.915 (11)°	Prism, red
V = 635.62 (15) Å^3	0.75 × 0.33 × 0.11 mm
Z = 2

Data collection

Stoe IPDS 2 diffractometer	1259 independent reflections
Radiation source: fine-focus sealed tube	1105 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.086
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 3.4°
ω scans	h = −15→15
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	k = −5→5
Tmin = 0.279, Tmax = 0.723	l = −14→14
8350 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0243P)^2 + 0.2013P] where P = (Fo^2 + 2Fc^2)/3
S = 1.37	(Δ/σ)max < 0.001
2504 reflections	Δρmax = 0.33 e Å^−3
164 parameters	Δρmin = −0.35 e Å^−3
2 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.467 (16)

Special details

Experimental. 360 frames, detector distance = 80 mm

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	0.4760 (5)	−0.0273 (12)	0.3835 (5)	0.0418 (13)
C2	0.3939 (5)	−0.1410 (13)	0.4206 (5)	0.0523 (15)
H2	0.3968	−0.0860	0.4956	0.063*
C3	0.3091 (6)	−0.3309 (17)	0.3509 (6)	0.0519 (19)
C4	0.3068 (5)	−0.4181 (15)	0.2397 (5)	0.0581 (16)
H4	0.2495	−0.5459	0.1907	0.070*
C5	0.3888 (6)	−0.3158 (14)	0.2024 (5)	0.0572 (16)
H5	0.3870	−0.3792	0.1287	0.069*
C6	0.4741 (7)	−0.1214 (14)	0.2713 (7)	0.050 (2)
C7	0.1382 (6)	−0.6010 (19)	0.3252 (7)	0.081 (2)
H7A	0.0765	−0.5806	0.3514	0.122*
H7B	0.1624	−0.8041	0.3327	0.122*
H7C	0.1118	−0.5405	0.2426	0.122*
C8	0.5611 (5)	0.1791 (12)	0.4600 (5)	0.0458 (14)
H8	0.5607	0.2265	0.5343	0.055*
C9	0.7163 (5)	0.5078 (11)	0.5079 (5)	0.0430 (14)
C10	0.8037 (5)	0.6000 (14)	0.4748 (5)	0.0463 (13)
H10	0.8076	0.5284	0.4048	0.056*
C11	0.8843 (5)	0.7977 (13)	0.5466 (5)	0.0472 (14)
C12	0.8812 (5)	0.9152 (15)	0.6492 (5)	0.0505 (14)
H12	0.9361	1.0520	0.6954	0.061*
C13	0.7942 (5)	0.8243 (14)	0.6816 (5)	0.0529 (15)
H13	0.7901	0.9013	0.7508	0.064*
C14	0.7121 (6)	0.6184 (17)	0.6123 (6)	0.0490 (17)
H14	0.6548	0.5558	0.6362	0.059*
Br1	1.00608 (6)	0.91668 (16)	0.50129 (6)	0.0731 (3)
N1	0.6371 (4)	0.2999 (10)	0.4304 (4)	0.0443 (11)
O1	0.5527 (5)	−0.0196 (13)	0.2316 (4)	0.0656 (15)
H1	0.5976	0.0927	0.2820	0.098*
O2	0.2323 (5)	−0.4205 (13)	0.3977 (5)	0.0819 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.054 (3)	0.035 (3)	0.033 (3)	−0.002 (3)	0.014 (2)	−0.002 (2)
C2	0.067 (4)	0.055 (4)	0.040 (3)	−0.006 (3)	0.027 (3)	−0.002 (3)
C3	0.065 (4)	0.044 (4)	0.050 (5)	−0.009 (3)	0.027 (4)	0.002 (3)
C4	0.064 (4)	0.056 (4)	0.046 (3)	−0.012 (4)	0.013 (3)	−0.007 (3)
C5	0.074 (4)	0.057 (4)	0.042 (3)	−0.007 (3)	0.025 (3)	−0.008 (3)
C6	0.063 (4)	0.050 (5)	0.042 (4)	0.003 (3)	0.026 (3)	0.005 (3)
C7	0.072 (4)	0.077 (5)	0.099 (6)	−0.025 (4)	0.039 (4)	−0.009 (5)
C8	0.061 (3)	0.040 (3)	0.038 (3)	0.000 (3)	0.022 (3)	0.002 (3)
C9	0.050 (3)	0.039 (4)	0.036 (3)	0.001 (2)	0.013 (3)	0.000 (3)
C10	0.050 (3)	0.048 (3)	0.043 (3)	0.000 (3)	0.020 (3)	0.000 (3)
C11	0.052 (3)	0.050 (4)	0.041 (3)	−0.005 (3)	0.019 (3)	0.014 (3)
C12	0.050 (3)	0.046 (3)	0.048 (3)	−0.011 (3)	0.013 (3)	−0.001 (3)
C13	0.066 (4)	0.050 (4)	0.043 (3)	−0.006 (3)	0.023 (3)	−0.005 (3)
C14	0.049 (4)	0.052 (4)	0.045 (4)	−0.006 (3)	0.018 (3)	−0.008 (3)
Br1	0.0668 (4)	0.0881 (5)	0.0680 (4)	−0.0187 (6)	0.0312 (3)	0.0094 (6)
N1	0.052 (3)	0.039 (3)	0.042 (3)	−0.002 (2)	0.020 (2)	−0.002 (2)
O1	0.074 (3)	0.086 (4)	0.046 (3)	−0.025 (3)	0.034 (3)	−0.018 (3)
O2	0.084 (4)	0.094 (4)	0.081 (4)	−0.038 (3)	0.046 (3)	−0.021 (3)

Geometric parameters (Å, º)

C1—C2	1.390 (8)	C8—N1	1.278 (6)
C1—C6	1.417 (9)	C8—H8	0.9300
C1—C8	1.444 (8)	C9—C14	1.383 (9)
C2—C3	1.369 (9)	C9—C10	1.387 (7)
C2—H2	0.9300	C9—N1	1.417 (7)
C3—O2	1.373 (8)	C10—C11	1.371 (8)
C3—C4	1.394 (9)	C10—H10	0.9300
C4—C5	1.373 (9)	C11—C12	1.368 (8)
C4—H4	0.9300	C11—Br1	1.915 (5)
C5—C6	1.381 (10)	C12—C13	1.376 (8)
C5—H5	0.9300	C12—H12	0.9300
C6—O1	1.352 (7)	C13—C14	1.395 (9)
C7—O2	1.418 (8)	C13—H13	0.9300
C7—H7A	0.9600	C14—H14	0.9300
C7—H7B	0.9600	O1—H1	0.8200
C7—H7C	0.9600
C2—C1—C6	118.5 (6)	N1—C8—C1	123.2 (5)
C2—C1—C8	119.5 (5)	N1—C8—H8	118.4
C6—C1—C8	121.9 (6)	C1—C8—H8	118.4
C3—C2—C1	122.4 (5)	C14—C9—C10	119.2 (6)
C3—C2—H2	118.8	C14—C9—N1	124.5 (5)
C1—C2—H2	118.8	C10—C9—N1	116.2 (5)
C2—C3—O2	116.1 (6)	C11—C10—C9	119.3 (5)
C2—C3—C4	118.6 (6)	C11—C10—H10	120.4
O2—C3—C4	125.3 (7)	C9—C10—H10	120.4
C5—C4—C3	120.3 (6)	C12—C11—C10	122.8 (5)
C5—C4—H4	119.9	C12—C11—Br1	118.5 (4)
C3—C4—H4	119.9	C10—C11—Br1	118.7 (4)
C4—C5—C6	121.7 (6)	C11—C12—C13	117.8 (6)
C4—C5—H5	119.1	C11—C12—H12	121.1
C6—C5—H5	119.1	C13—C12—H12	121.1
O1—C6—C5	120.7 (6)	C12—C13—C14	121.0 (6)
O1—C6—C1	120.8 (6)	C12—C13—H13	119.5
C5—C6—C1	118.5 (7)	C14—C13—H13	119.5
O2—C7—H7A	109.5	C9—C14—C13	119.8 (6)
O2—C7—H7B	109.5	C9—C14—H14	120.1
H7A—C7—H7B	109.5	C13—C14—H14	120.1
O2—C7—H7C	109.5	C8—N1—C9	120.6 (4)
H7A—C7—H7C	109.5	C6—O1—H1	109.5
H7B—C7—H7C	109.5	C3—O2—C7	118.2 (6)
C6—C1—C2—C3	−2.6 (9)	C14—C9—C10—C11	0.3 (8)
C8—C1—C2—C3	178.1 (6)	N1—C9—C10—C11	−179.1 (5)
C1—C2—C3—O2	−178.6 (6)	C9—C10—C11—C12	−1.5 (9)
C1—C2—C3—C4	1.5 (10)	C9—C10—C11—Br1	178.8 (4)
C2—C3—C4—C5	0.4 (11)	C10—C11—C12—C13	1.3 (9)
O2—C3—C4—C5	−179.5 (7)	Br1—C11—C12—C13	−179.0 (5)
C3—C4—C5—C6	−1.2 (11)	C11—C12—C13—C14	0.2 (10)
C4—C5—C6—O1	−178.8 (6)	C10—C9—C14—C13	1.1 (10)
C4—C5—C6—C1	0.1 (10)	N1—C9—C14—C13	−179.6 (6)
C2—C1—C6—O1	−179.3 (6)	C12—C13—C14—C9	−1.4 (11)
C8—C1—C6—O1	−0.1 (10)	C1—C8—N1—C9	178.1 (5)
C2—C1—C6—C5	1.7 (9)	C14—C9—N1—C8	−6.6 (9)
C8—C1—C6—C5	−179.0 (6)	C10—C9—N1—C8	172.7 (5)
C2—C1—C8—N1	−177.8 (5)	C2—C3—O2—C7	175.7 (7)
C6—C1—C8—N1	2.9 (9)	C4—C3—O2—C7	−4.3 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.91	2.638 (7)	148

(III) (E)-2-[(4-bromophenyl)iminomethyl]-4-methoxyphenol

Crystal data

C14H12BrNO2	F(000) = 308
Mr = 306.16	Dx = 1.603 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 8753 reflections
a = 14.0683 (12) Å	θ = 2.9–28.0°
b = 6.9497 (7) Å	µ = 3.23 mm^−1
c = 6.5553 (6) Å	T = 296 K
β = 98.264 (7)°	Prism, red
V = 634.26 (10) Å^3	0.36 × 0.27 × 0.11 mm
Z = 2

Data collection

Stoe IPDS 2 diffractometer	2785 independent reflections
Radiation source: fine-focus sealed tube	2225 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.075
Detector resolution: 6.67 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ω scans	h = −18→18
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	k = −9→9
Tmin = 0.287, Tmax = 0.732	l = −8→8
8753 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.075	w = 1/[σ^2(Fo^2) + (0.037P)^2 + 0.0074P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
2785 reflections	Δρmax = 0.18 e Å^−3
167 parameters	Δρmin = −0.23 e Å^−3
2 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.015 (9)

Special details

Experimental. 314 frames, detector distance = 80 mm

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	0.4847 (2)	0.2212 (4)	0.2358 (5)	0.0408 (6)
C2	0.3945 (2)	0.2001 (4)	0.3025 (5)	0.0443 (6)
H2	0.3912	0.1579	0.4359	0.053*
C3	0.3111 (3)	0.2414 (5)	0.1722 (7)	0.0467 (8)
C4	0.3161 (3)	0.2975 (5)	−0.0299 (6)	0.0508 (7)
H4	0.2599	0.3227	−0.1189	0.061*
C5	0.4034 (3)	0.3162 (4)	−0.0992 (5)	0.0488 (8)
H5	0.4060	0.3546	−0.2342	0.059*
C6	0.4878 (2)	0.2776 (4)	0.0324 (5)	0.0441 (7)
C7	0.2064 (3)	0.2081 (7)	0.4271 (9)	0.0669 (13)
H7A	0.1389	0.2082	0.4361	0.100*
H7B	0.2370	0.3115	0.5085	0.100*
H7C	0.2339	0.0878	0.4777	0.100*
C8	0.5713 (2)	0.2014 (4)	0.3814 (5)	0.0432 (7)
H8	0.5669	0.1724	0.5182	0.052*
C9	0.7391 (2)	0.2329 (4)	0.4688 (6)	0.0408 (6)
C10	0.8243 (3)	0.1755 (5)	0.4013 (7)	0.0461 (9)
H10	0.8227	0.1262	0.2690	0.055*
C11	0.9105 (2)	0.1909 (4)	0.5284 (6)	0.0547 (8)
H11	0.9670	0.1510	0.4833	0.066*
C12	0.9124 (3)	0.2664 (4)	0.7237 (6)	0.0522 (8)
C13	0.8295 (2)	0.3245 (4)	0.7926 (5)	0.0474 (7)
H13	0.8318	0.3751	0.9245	0.057*
C14	0.7425 (3)	0.3080 (4)	0.6663 (7)	0.0452 (9)
H14	0.6862	0.3470	0.7132	0.054*
N1	0.65442 (19)	0.2233 (3)	0.3245 (4)	0.0444 (6)
O1	0.5720 (2)	0.3005 (4)	−0.0433 (4)	0.0610 (6)
O2	0.22008 (19)	0.2324 (4)	0.2201 (5)	0.0746 (8)
Br1	1.03106 (3)	0.28753 (5)	0.90101 (5)	0.07099 (14)
H1	0.614 (4)	0.282 (5)	0.051 (9)	0.073 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0402 (15)	0.0401 (12)	0.0415 (18)	−0.0001 (12)	0.0037 (13)	0.0008 (12)
C2	0.0385 (16)	0.0527 (15)	0.0410 (17)	−0.0047 (13)	0.0035 (13)	0.0008 (13)
C3	0.0358 (16)	0.0580 (19)	0.045 (2)	−0.0034 (15)	0.0011 (15)	−0.0056 (16)
C4	0.0443 (17)	0.0641 (17)	0.041 (2)	0.0042 (15)	−0.0039 (15)	−0.0060 (15)
C5	0.056 (2)	0.0547 (17)	0.0354 (17)	0.0018 (13)	0.0045 (15)	−0.0007 (12)
C6	0.0433 (16)	0.0445 (13)	0.0457 (19)	−0.0015 (12)	0.0104 (14)	−0.0022 (13)
C7	0.043 (2)	0.095 (3)	0.065 (3)	0.000 (2)	0.018 (2)	0.012 (2)
C8	0.0384 (14)	0.0448 (14)	0.0465 (19)	−0.0006 (12)	0.0059 (15)	0.0025 (13)
C9	0.0342 (16)	0.0392 (13)	0.0490 (19)	0.0021 (11)	0.0058 (14)	0.0007 (12)
C10	0.041 (2)	0.0489 (17)	0.049 (2)	0.0028 (13)	0.0085 (17)	−0.0047 (13)
C11	0.0365 (16)	0.0538 (17)	0.075 (3)	0.0058 (13)	0.0113 (17)	−0.0031 (16)
C12	0.0398 (16)	0.0466 (16)	0.067 (2)	−0.0017 (12)	−0.0034 (16)	0.0021 (14)
C13	0.0442 (17)	0.0505 (17)	0.0466 (18)	0.0029 (12)	0.0039 (15)	−0.0020 (12)
C14	0.0387 (17)	0.0499 (19)	0.049 (2)	0.0056 (13)	0.0132 (16)	−0.0001 (14)
N1	0.0364 (13)	0.0489 (12)	0.0477 (17)	0.0011 (11)	0.0056 (12)	−0.0002 (11)
O1	0.0502 (14)	0.0878 (17)	0.0467 (16)	−0.0038 (12)	0.0125 (13)	0.0074 (12)
O2	0.0333 (12)	0.136 (2)	0.0534 (17)	−0.0049 (14)	0.0012 (13)	−0.0070 (14)
Br1	0.04227 (16)	0.0812 (2)	0.0837 (3)	−0.0039 (4)	−0.01056 (15)	−0.0024 (4)

Geometric parameters (Å, º)

C1—C6	1.397 (4)	C8—N1	1.287 (4)
C1—C2	1.407 (5)	C8—H8	0.9300
C1—C8	1.442 (4)	C9—C14	1.390 (5)
C2—C3	1.379 (5)	C9—C10	1.394 (5)
C2—H2	0.9300	C9—N1	1.413 (4)
C3—O2	1.364 (5)	C10—C11	1.373 (5)
C3—C4	1.392 (6)	C10—H10	0.9300
C4—C5	1.376 (5)	C11—C12	1.381 (6)
C4—H4	0.9300	C11—H11	0.9300
C5—C6	1.389 (5)	C12—C13	1.371 (5)
C5—H5	0.9300	C12—Br1	1.897 (4)
C6—O1	1.358 (4)	C13—C14	1.380 (6)
C7—O2	1.408 (6)	C13—H13	0.9300
C7—H7A	0.9600	C14—H14	0.9300
C7—H7B	0.9600	O1—H1	0.80 (6)
C7—H7C	0.9600
C6—C1—C2	118.6 (3)	N1—C8—C1	120.9 (3)
C6—C1—C8	121.3 (3)	N1—C8—H8	119.5
C2—C1—C8	119.9 (3)	C1—C8—H8	119.5
C3—C2—C1	120.7 (3)	C14—C9—C10	119.2 (3)
C3—C2—H2	119.7	C14—C9—N1	123.7 (3)
C1—C2—H2	119.7	C10—C9—N1	117.0 (3)
O2—C3—C2	126.3 (4)	C11—C10—C9	120.6 (4)
O2—C3—C4	114.2 (4)	C11—C10—H10	119.7
C2—C3—C4	119.5 (4)	C9—C10—H10	119.7
C5—C4—C3	120.7 (3)	C10—C11—C12	119.4 (3)
C5—C4—H4	119.7	C10—C11—H11	120.3
C3—C4—H4	119.7	C12—C11—H11	120.3
C4—C5—C6	120.0 (3)	C13—C12—C11	120.9 (3)
C4—C5—H5	120.0	C13—C12—Br1	119.4 (3)
C6—C5—H5	120.0	C11—C12—Br1	119.7 (3)
O1—C6—C5	117.6 (3)	C12—C13—C14	120.1 (3)
O1—C6—C1	122.0 (3)	C12—C13—H13	120.0
C5—C6—C1	120.4 (3)	C14—C13—H13	120.0
O2—C7—H7A	109.5	C13—C14—C9	119.9 (4)
O2—C7—H7B	109.5	C13—C14—H14	120.1
H7A—C7—H7B	109.5	C9—C14—H14	120.1
O2—C7—H7C	109.5	C8—N1—C9	121.7 (3)
H7A—C7—H7C	109.5	C6—O1—H1	107 (4)
H7B—C7—H7C	109.5	C3—O2—C7	119.4 (3)
C6—C1—C2—C3	−2.5 (4)	C14—C9—C10—C11	0.6 (5)
C8—C1—C2—C3	172.1 (3)	N1—C9—C10—C11	176.2 (3)
C1—C2—C3—O2	−177.9 (3)	C9—C10—C11—C12	−0.8 (5)
C1—C2—C3—C4	2.4 (5)	C10—C11—C12—C13	0.5 (5)
O2—C3—C4—C5	178.9 (3)	C10—C11—C12—Br1	179.7 (2)
C2—C3—C4—C5	−1.4 (5)	C11—C12—C13—C14	0.0 (5)
C3—C4—C5—C6	0.4 (5)	Br1—C12—C13—C14	−179.2 (2)
C4—C5—C6—O1	−179.2 (3)	C12—C13—C14—C9	−0.2 (5)
C4—C5—C6—C1	−0.5 (4)	C10—C9—C14—C13	−0.1 (4)
C2—C1—C6—O1	−179.8 (3)	N1—C9—C14—C13	−175.4 (3)
C8—C1—C6—O1	5.7 (4)	C1—C8—N1—C9	170.4 (2)
C2—C1—C6—C5	1.5 (4)	C14—C9—N1—C8	−31.1 (4)
C8—C1—C6—C5	−173.0 (3)	C10—C9—N1—C8	153.5 (3)
C6—C1—C8—N1	−4.4 (4)	C2—C3—O2—C7	10.6 (6)
C2—C1—C8—N1	−178.8 (3)	C4—C3—O2—C7	−169.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.80 (6)	1.85 (6)	2.577 (4)	151 (6)
C14—H14···O1^i	0.93	2.44	3.270 (5)	148
C7—H7C···O2^ii	0.96	2.76	3.604 (6)	148
C5—H5···Cg1^iii	0.93	2.89	3.538 (3)	129
C10—H10···Cg2^iv	0.93	2.85	3.569 (4)	135
C13—H13···Cg2^v	0.93	2.85	3.572 (2)	136

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