Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055304/ci2507sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055304/ci2507Isup2.hkl |
CCDC reference: 672837
A solution of 5-bromosalicylaldehyde (0.05 g, 0.25 mmol) in ethanol (20 ml) was added to a solution of 2-hydroxy-5-nitroaniline (0.038 g 0.25 mmol) in ethanol (20 ml). The reaction mixture was stirred for 1 h under reflux. Single crystals of the title compound suitable for X-ray analysis were obtained from ethanol by slow evaporation (yield 71%; m.p. 456–459 K).
Atom H1 was located in a difference map and refined freely. The remaining H atoms were placed in calculated positions and constrained to ride on their parents atoms, with C—H = 0.93–0.96 Å and Uiso(H) = kUeq(parent atom), where k = 1.5 for methyl and hydroxyl H atoms, and 1.2 for other H atoms.
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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C14H12BrNO2 | F(000) = 616 |
Mr = 306.16 | Dx = 1.548 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P2ac 2ab | Cell parameters from 5730 reflections |
a = 8.2763 (8) Å | θ = 2.2–29.5° |
b = 8.4451 (9) Å | µ = 3.12 mm−1 |
c = 18.795 (2) Å | T = 296 K |
V = 1313.7 (2) Å3 | Prism, brown |
Z = 4 | 0.80 × 0.37 × 0.13 mm |
Stoe IPDS II diffractometer | 2549 independent reflections |
Radiation source: fine-focus sealed tube | 1541 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.2° |
rotation method scans | h = −10→10 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −10→6 |
Tmin = 0.289, Tmax = 0.680 | l = −23→23 |
6028 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)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.0287P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.91 | (Δ/σ)max = 0.001 |
2549 reflections | Δρmax = 0.31 e Å−3 |
167 parameters | Δρmin = −0.30 e Å−3 |
0 restraints | Absolute structure: Flack (1983); 1052 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.010 (15) |
C14H12BrNO2 | V = 1313.7 (2) Å3 |
Mr = 306.16 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.2763 (8) Å | µ = 3.12 mm−1 |
b = 8.4451 (9) Å | T = 296 K |
c = 18.795 (2) Å | 0.80 × 0.37 × 0.13 mm |
Stoe IPDS II diffractometer | 2549 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 1541 reflections with I > 2σ(I) |
Tmin = 0.289, Tmax = 0.680 | Rint = 0.073 |
6028 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.084 | Δρmax = 0.31 e Å−3 |
S = 0.91 | Δρmin = −0.30 e Å−3 |
2549 reflections | Absolute structure: Flack (1983); 1052 Friedel pairs |
167 parameters | Absolute structure parameter: −0.010 (15) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.5123 (5) | 0.4814 (6) | 0.6768 (3) | 0.0472 (11) | |
C2 | 0.4416 (5) | 0.6051 (8) | 0.6358 (2) | 0.0529 (15) | |
C3 | 0.2843 (5) | 0.6545 (7) | 0.6554 (3) | 0.0558 (15) | |
H3 | 0.2355 | 0.7366 | 0.6304 | 0.067* | |
C4 | 0.2033 (6) | 0.5854 (7) | 0.7097 (3) | 0.0551 (16) | |
H4 | 0.0991 | 0.6185 | 0.7207 | 0.066* | |
C5 | 0.2749 (6) | 0.4652 (7) | 0.7491 (2) | 0.0509 (14) | |
C6 | 0.4245 (6) | 0.4155 (7) | 0.7336 (2) | 0.0558 (16) | |
H6 | 0.4712 | 0.3359 | 0.7609 | 0.067* | |
C7 | 0.6666 (6) | 0.4226 (6) | 0.6601 (2) | 0.0526 (13) | |
H7 | 0.7082 | 0.3397 | 0.6870 | 0.063* | |
C8 | 0.9084 (5) | 0.4353 (7) | 0.5857 (2) | 0.0450 (13) | |
C9 | 0.9898 (6) | 0.3034 (7) | 0.6103 (2) | 0.0498 (13) | |
H9 | 0.9424 | 0.2399 | 0.6449 | 0.060* | |
C10 | 1.1407 (7) | 0.2646 (7) | 0.5841 (3) | 0.0591 (14) | |
C11 | 1.2065 (6) | 0.3619 (10) | 0.5315 (3) | 0.0684 (17) | |
H11 | 1.3066 | 0.3364 | 0.5121 | 0.082* | |
C12 | 1.1267 (6) | 0.4950 (8) | 0.5073 (2) | 0.0607 (15) | |
H12 | 1.1738 | 0.5589 | 0.4727 | 0.073* | |
C13 | 0.9777 (6) | 0.5331 (7) | 0.5346 (2) | 0.0497 (13) | |
C14 | 1.2316 (7) | 0.1219 (9) | 0.6121 (3) | 0.086 (2) | |
H14A | 1.2118 | 0.1107 | 0.6622 | 0.129* | |
H14B | 1.3453 | 0.1361 | 0.6041 | 0.129* | |
H14C | 1.1954 | 0.0285 | 0.5878 | 0.129* | |
N1 | 0.7527 (5) | 0.4790 (6) | 0.6088 (2) | 0.0493 (12) | |
H1 | 0.703 (6) | 0.544 (7) | 0.585 (2) | 0.059* | |
O1 | 0.5191 (4) | 0.6667 (5) | 0.58287 (17) | 0.0631 (12) | |
O2 | 0.8903 (4) | 0.6614 (5) | 0.51439 (17) | 0.0657 (11) | |
H2 | 0.9404 | 0.7111 | 0.4841 | 0.098* | |
Br1 | 0.15523 (6) | 0.36922 (9) | 0.82415 (3) | 0.0725 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.045 (2) | 0.043 (3) | 0.053 (2) | 0.004 (2) | 0.001 (3) | 0.009 (3) |
C2 | 0.058 (3) | 0.049 (5) | 0.052 (3) | −0.008 (3) | −0.014 (2) | 0.001 (3) |
C3 | 0.059 (3) | 0.036 (4) | 0.072 (3) | 0.009 (3) | −0.016 (2) | 0.003 (3) |
C4 | 0.047 (3) | 0.057 (5) | 0.061 (3) | 0.005 (3) | −0.004 (2) | −0.008 (3) |
C5 | 0.054 (3) | 0.048 (4) | 0.051 (3) | 0.002 (3) | −0.001 (2) | 0.001 (3) |
C6 | 0.054 (3) | 0.053 (5) | 0.060 (3) | 0.005 (3) | 0.000 (2) | 0.014 (3) |
C7 | 0.059 (3) | 0.051 (3) | 0.047 (3) | 0.000 (3) | −0.001 (2) | 0.020 (2) |
C8 | 0.050 (3) | 0.042 (4) | 0.043 (2) | −0.004 (2) | −0.002 (2) | 0.006 (2) |
C9 | 0.058 (3) | 0.044 (4) | 0.048 (3) | −0.003 (3) | 0.009 (2) | 0.008 (2) |
C10 | 0.068 (3) | 0.040 (4) | 0.069 (3) | −0.003 (3) | 0.009 (3) | −0.006 (3) |
C11 | 0.071 (3) | 0.067 (5) | 0.067 (3) | 0.000 (4) | 0.028 (3) | −0.019 (4) |
C12 | 0.075 (4) | 0.055 (4) | 0.052 (3) | −0.014 (3) | 0.010 (3) | 0.004 (3) |
C13 | 0.059 (3) | 0.039 (4) | 0.051 (3) | −0.006 (3) | −0.001 (2) | 0.004 (3) |
C14 | 0.085 (4) | 0.056 (5) | 0.117 (5) | 0.022 (4) | 0.025 (3) | 0.016 (5) |
N1 | 0.047 (2) | 0.046 (3) | 0.054 (3) | 0.004 (2) | −0.0036 (19) | 0.013 (2) |
O1 | 0.064 (2) | 0.056 (3) | 0.069 (2) | 0.003 (2) | −0.0036 (17) | 0.031 (2) |
O2 | 0.073 (2) | 0.058 (3) | 0.0655 (19) | 0.003 (2) | 0.0138 (17) | 0.030 (2) |
Br1 | 0.0639 (3) | 0.0783 (5) | 0.0753 (3) | −0.0022 (4) | 0.0147 (3) | 0.0103 (4) |
C1—C6 | 1.406 (6) | C8—N1 | 1.409 (6) |
C1—C7 | 1.406 (6) | C9—C10 | 1.382 (7) |
C1—C2 | 1.424 (7) | C9—H9 | 0.93 |
C2—O1 | 1.293 (6) | C10—C11 | 1.397 (8) |
C2—C3 | 1.415 (7) | C10—C14 | 1.515 (8) |
C3—C4 | 1.354 (7) | C11—C12 | 1.380 (9) |
C3—H3 | 0.93 | C11—H11 | 0.93 |
C4—C5 | 1.389 (7) | C12—C13 | 1.373 (7) |
C4—H4 | 0.93 | C12—H12 | 0.93 |
C5—C6 | 1.340 (6) | C13—O2 | 1.357 (6) |
C5—Br1 | 1.905 (5) | C14—H14A | 0.96 |
C6—H6 | 0.93 | C14—H14B | 0.96 |
C7—N1 | 1.289 (6) | C14—H14C | 0.96 |
C7—H7 | 0.93 | N1—H1 | 0.82 (5) |
C8—C9 | 1.381 (7) | O2—H2 | 0.82 |
C8—C13 | 1.390 (7) | ||
C6—C1—C7 | 119.9 (5) | C8—C9—H9 | 119.6 |
C6—C1—C2 | 119.3 (4) | C10—C9—H9 | 119.6 |
C7—C1—C2 | 120.8 (4) | C9—C10—C11 | 117.7 (5) |
O1—C2—C3 | 122.5 (5) | C9—C10—C14 | 121.0 (5) |
O1—C2—C1 | 120.5 (4) | C11—C10—C14 | 121.4 (5) |
C3—C2—C1 | 117.0 (5) | C12—C11—C10 | 121.7 (5) |
C4—C3—C2 | 121.6 (5) | C12—C11—H11 | 119.1 |
C4—C3—H3 | 119.2 | C10—C11—H11 | 119.1 |
C2—C3—H3 | 119.2 | C13—C12—C11 | 119.8 (5) |
C3—C4—C5 | 120.4 (5) | C13—C12—H12 | 120.1 |
C3—C4—H4 | 119.8 | C11—C12—H12 | 120.1 |
C5—C4—H4 | 119.8 | O2—C13—C12 | 124.1 (5) |
C6—C5—C4 | 120.5 (5) | O2—C13—C8 | 116.6 (4) |
C6—C5—Br1 | 120.5 (4) | C12—C13—C8 | 119.3 (5) |
C4—C5—Br1 | 118.9 (4) | C10—C14—H14A | 109.5 |
C5—C6—C1 | 121.2 (5) | C10—C14—H14B | 109.5 |
C5—C6—H6 | 119.4 | H14A—C14—H14B | 109.5 |
C1—C6—H6 | 119.4 | C10—C14—H14C | 109.5 |
N1—C7—C1 | 122.6 (5) | H14A—C14—H14C | 109.5 |
N1—C7—H7 | 118.7 | H14B—C14—H14C | 109.5 |
C1—C7—H7 | 118.7 | C7—N1—C8 | 129.7 (5) |
C9—C8—C13 | 120.6 (5) | C7—N1—H1 | 112 (3) |
C9—C8—N1 | 123.6 (5) | C8—N1—H1 | 118 (3) |
C13—C8—N1 | 115.8 (5) | C13—O2—H2 | 109.5 |
C8—C9—C10 | 120.9 (5) | ||
C6—C1—C2—O1 | −179.4 (5) | N1—C8—C9—C10 | 178.3 (5) |
C7—C1—C2—O1 | −0.7 (8) | C8—C9—C10—C11 | −0.9 (8) |
C6—C1—C2—C3 | 0.0 (8) | C8—C9—C10—C14 | 178.7 (5) |
C7—C1—C2—C3 | 178.6 (5) | C9—C10—C11—C12 | 1.8 (9) |
O1—C2—C3—C4 | 178.0 (5) | C14—C10—C11—C12 | −177.8 (6) |
C1—C2—C3—C4 | −1.3 (8) | C10—C11—C12—C13 | −1.0 (9) |
C2—C3—C4—C5 | 1.5 (8) | C11—C12—C13—O2 | 179.8 (5) |
C3—C4—C5—C6 | −0.4 (8) | C11—C12—C13—C8 | −0.7 (8) |
C3—C4—C5—Br1 | −179.2 (4) | C9—C8—C13—O2 | −178.9 (4) |
C4—C5—C6—C1 | −0.9 (8) | N1—C8—C13—O2 | 1.9 (6) |
Br1—C5—C6—C1 | 177.8 (4) | C9—C8—C13—C12 | 1.6 (7) |
C7—C1—C6—C5 | −177.5 (5) | N1—C8—C13—C12 | −177.6 (5) |
C2—C1—C6—C5 | 1.1 (8) | C1—C7—N1—C8 | 179.4 (5) |
C6—C1—C7—N1 | −179.6 (5) | C9—C8—N1—C7 | 9.0 (8) |
C2—C1—C7—N1 | 1.7 (8) | C13—C8—N1—C7 | −171.8 (5) |
C13—C8—C9—C10 | −0.8 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 1.75 | 2.566 (5) | 171 |
N1—H1···O1 | 0.82 (5) | 1.84 (5) | 2.547 (6) | 144 (5) |
Symmetry code: (i) x+1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C14H12BrNO2 |
Mr | 306.16 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 296 |
a, b, c (Å) | 8.2763 (8), 8.4451 (9), 18.795 (2) |
V (Å3) | 1313.7 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.12 |
Crystal size (mm) | 0.80 × 0.37 × 0.13 |
Data collection | |
Diffractometer | Stoe IPDS II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.289, 0.680 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6028, 2549, 1541 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.084, 0.91 |
No. of reflections | 2549 |
No. of parameters | 167 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.30 |
Absolute structure | Flack (1983); 1052 Friedel pairs |
Absolute structure parameter | −0.010 (15) |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.82 | 1.75 | 2.566 (5) | 171 |
N1—H1···O1 | 0.82 (5) | 1.84 (5) | 2.547 (6) | 144 (5) |
Symmetry code: (i) x+1/2, −y+3/2, −z+1. |
Schiff bases have been extensively used as ligands in the field of coordination chemistry (Calligaris et al., 1972). There are two characteristic properties of Schiff bases, viz. photochromism and thermochromism (Cohen et al., 1964). These properties result from proton transfer from the hydroxyl O atom to the imine N atom (Hadjoudis et al., 1987). Schiff bases display two possible tautomeric forms, namely the phenol-imine and keto-amine forms. In the solid state, the keto-amine tautomer has been found in naphthaldimine (Hökelek et al., 2000). Nevertheless, in the solid state, it has been established that there is keto-amine tautomerism in naphthaldimine, while the phenol-imine form exists in salicylaldimine Schiff bases (Dey et al., 2001). Our investigations show that compound (I) exists in a zwitterionic form.
An ORTEP-3 (Farrugia, 1997) plot of the molecule of (I) is shown in Fig.1. The C1—C7, C7═N1 and N1—C8 bond lengths are 1.406 (6), 1.289 (6) and 1.409 (6) Å, respectively (Table 1), and agree with the corresponding distances in (Z)-6-[(2-fluorophenyliminio)methylene]-2,3-dihydroxyphenolate [1.419 (3), 1.295 (2) and 1.412 (2) Å; Petek et al., 2006]. In the zwitterionic form, the molecule of the title compound is nearly planar, with a dihedral angle between the aromatic rings of 9.3 (3)°.
Fig.1 also shows a strong intramolecular hydrogen bond (N1—H1···O1) can be described as an S(6) motif (Bernstein et al., 1995). Atom O2 in the reference molecule at (x, y, z) acts as a hydrogen-bond donor, via H2, to O1 in the molecule at (1/2 + x, 3/2 - y, 1 - z), so forming a C(8) chain running parallel to the [100] direction (Fig.2).