The molecule of the former title compound, C
13H
9ClN
2O
2, (I), is nearly planar, with an intramolecular O
O hydrogen bond of 2.692 (2) Å. The latter title compound, C
17H
18ClN
3O
4, (II), exists in the keto–amine tautomeric form, with a strong intramolecular hydrogen bond of 2.640 (2) Å between the O and N atoms, the H atom being bonded to the N atom. The azobenzene moieties of both molecules have
trans configurations, and the dihedral angle between the planes of the two aromatic rings is 4.1 (1)° in (I) and 9.9 (1)° in (II). The N—H
O hydrogen-bonded rings are almost planar and coupled with the cyclohexadiene rings in (II).
Supporting information
CCDC references: 241224; 241225
The title compounds were obtained as described in our previous work (Odabaşoǧlu, Albayrak, Büyükgüngör & Goesmann, 2003) using 2-chloroaniline, salicylaldehyde and tris(hydroxymethyl)aminomethane as starting materials. Suitable single crystals of (I) were obtained by slow evaporation from ethyl alcohol (yield 85%; m.p. 424–426 K) and of (II) from acetonitrile (yield 72%; m.p. 479–481 K).
All H atoms were refined freely. For (I), the refined C—H distances are in the range 0.87 (2)–1.00 (2) Å and Uiso(H) values are in the range 0.031 (5)–0.052 (6) Å2. For (II), the refined C—H distances are in the range 0.92 (2)–1.02 (2) Å and Uiso(H) values are in the range 0.024 (4)–0.054 (6) Å2.
For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); 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).
(I) 5-(2-chlorophenyldiazenyl)salicylaldehyde
top
Crystal data top
C13H9ClN2O2 | F(000) = 536 |
Mr = 260.67 | Dx = 1.490 Mg m−3 |
Monoclinic, P21/n | Melting point = 424–426 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 6.9938 (11) Å | Cell parameters from 2275 reflections |
b = 21.636 (3) Å | θ = 1.9–26.0° |
c = 8.1078 (13) Å | µ = 0.32 mm−1 |
β = 108.724 (3)° | T = 213 K |
V = 1161.9 (3) Å3 | Prism, dark red |
Z = 4 | 0.40 × 0.40 × 0.30 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2275 independent reflections |
Radiation source: fine-focus sealed tube | 1783 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | h = −8→8 |
Tmin = 0.882, Tmax = 0.909 | k = −19→26 |
6246 measured reflections | l = −9→9 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.108 | All H-atom parameters refined |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0571P)2 + 0.066P] where P = (Fo2 + 2Fc2)/3 |
2275 reflections | (Δ/σ)max < 0.001 |
199 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
Crystal data top
C13H9ClN2O2 | V = 1161.9 (3) Å3 |
Mr = 260.67 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.9938 (11) Å | µ = 0.32 mm−1 |
b = 21.636 (3) Å | T = 213 K |
c = 8.1078 (13) Å | 0.40 × 0.40 × 0.30 mm |
β = 108.724 (3)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2275 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 1783 reflections with I > 2σ(I) |
Tmin = 0.882, Tmax = 0.909 | Rint = 0.051 |
6246 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.108 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.27 e Å−3 |
2275 reflections | Δρmin = −0.23 e Å−3 |
199 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.45370 (9) | 0.73574 (3) | 0.37535 (7) | 0.0478 (2) | |
O2 | 0.6761 (3) | 0.49762 (7) | 1.42581 (19) | 0.0538 (5) | |
O1 | 0.3429 (3) | 0.56209 (8) | 1.2524 (2) | 0.0497 (4) | |
N1 | 0.6563 (2) | 0.64782 (7) | 0.65391 (19) | 0.0322 (4) | |
N2 | 0.7496 (3) | 0.61509 (7) | 0.7823 (2) | 0.0339 (4) | |
C1 | 0.7677 (3) | 0.65952 (8) | 0.5374 (2) | 0.0288 (4) | |
C2 | 0.6824 (3) | 0.69980 (8) | 0.3986 (2) | 0.0307 (4) | |
C3 | 0.7794 (3) | 0.71250 (10) | 0.2781 (3) | 0.0376 (5) | |
C4 | 0.9624 (4) | 0.68577 (11) | 0.2960 (3) | 0.0423 (5) | |
C5 | 1.0512 (3) | 0.64630 (11) | 0.4339 (3) | 0.0422 (5) | |
C6 | 0.9541 (3) | 0.63332 (10) | 0.5525 (3) | 0.0357 (5) | |
C7 | 0.6397 (3) | 0.60346 (8) | 0.8993 (2) | 0.0305 (4) | |
C8 | 0.7354 (3) | 0.56687 (9) | 1.0417 (2) | 0.0338 (5) | |
C9 | 0.6395 (3) | 0.55229 (9) | 1.1644 (2) | 0.0332 (5) | |
C10 | 0.4460 (3) | 0.57486 (9) | 1.1418 (2) | 0.0360 (5) | |
C11 | 0.3513 (4) | 0.61266 (10) | 0.9987 (3) | 0.0396 (5) | |
C12 | 0.4476 (3) | 0.62651 (10) | 0.8804 (3) | 0.0354 (5) | |
C13 | 0.7464 (4) | 0.51422 (10) | 1.3144 (3) | 0.0413 (5) | |
H1 | 0.430 (5) | 0.5356 (14) | 1.338 (4) | 0.085 (10)* | |
H3 | 0.715 (4) | 0.7389 (10) | 0.183 (3) | 0.046 (6)* | |
H4 | 1.024 (3) | 0.6941 (10) | 0.220 (3) | 0.047 (6)* | |
H5 | 1.174 (4) | 0.6275 (10) | 0.440 (3) | 0.047 (6)* | |
H6 | 1.005 (3) | 0.6082 (10) | 0.639 (3) | 0.045 (6)* | |
H8 | 0.873 (3) | 0.5501 (9) | 1.058 (2) | 0.031 (5)* | |
H11 | 0.223 (4) | 0.6258 (10) | 0.985 (3) | 0.042 (6)* | |
H12 | 0.383 (3) | 0.6545 (11) | 0.788 (3) | 0.052 (6)* | |
H13 | 0.887 (4) | 0.5055 (10) | 1.323 (3) | 0.045 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0455 (4) | 0.0533 (4) | 0.0447 (3) | 0.0163 (3) | 0.0148 (3) | 0.0162 (2) |
O2 | 0.0785 (13) | 0.0497 (10) | 0.0362 (8) | 0.0009 (9) | 0.0225 (9) | 0.0148 (7) |
O1 | 0.0620 (11) | 0.0554 (10) | 0.0426 (9) | 0.0067 (8) | 0.0319 (9) | 0.0097 (7) |
N1 | 0.0356 (10) | 0.0344 (9) | 0.0252 (8) | −0.0013 (7) | 0.0078 (7) | 0.0025 (7) |
N2 | 0.0349 (10) | 0.0365 (9) | 0.0283 (9) | −0.0011 (7) | 0.0072 (8) | 0.0056 (7) |
C1 | 0.0306 (11) | 0.0291 (10) | 0.0248 (9) | −0.0050 (8) | 0.0062 (8) | −0.0020 (7) |
C2 | 0.0312 (11) | 0.0300 (10) | 0.0286 (10) | −0.0016 (8) | 0.0064 (9) | −0.0005 (8) |
C3 | 0.0427 (13) | 0.0389 (12) | 0.0285 (10) | −0.0066 (10) | 0.0077 (10) | 0.0024 (9) |
C4 | 0.0451 (14) | 0.0527 (14) | 0.0331 (11) | −0.0102 (11) | 0.0180 (10) | −0.0003 (10) |
C5 | 0.0332 (13) | 0.0532 (14) | 0.0406 (12) | 0.0014 (11) | 0.0123 (11) | −0.0041 (10) |
C6 | 0.0340 (12) | 0.0407 (12) | 0.0290 (10) | 0.0009 (9) | 0.0054 (9) | 0.0016 (9) |
C7 | 0.0322 (11) | 0.0316 (10) | 0.0253 (9) | −0.0023 (8) | 0.0060 (8) | −0.0002 (8) |
C8 | 0.0370 (12) | 0.0327 (11) | 0.0292 (10) | 0.0017 (9) | 0.0073 (9) | 0.0021 (8) |
C9 | 0.0435 (13) | 0.0284 (10) | 0.0258 (10) | −0.0005 (9) | 0.0083 (9) | 0.0014 (8) |
C10 | 0.0472 (13) | 0.0343 (11) | 0.0296 (10) | −0.0027 (9) | 0.0166 (10) | −0.0023 (8) |
C11 | 0.0363 (13) | 0.0474 (13) | 0.0360 (11) | 0.0074 (10) | 0.0127 (10) | 0.0020 (9) |
C12 | 0.0360 (12) | 0.0377 (11) | 0.0286 (10) | 0.0030 (9) | 0.0049 (9) | 0.0046 (9) |
C13 | 0.0515 (16) | 0.0360 (12) | 0.0336 (11) | 0.0015 (10) | 0.0096 (11) | 0.0048 (9) |
Geometric parameters (Å, º) top
Cl1—C2 | 1.733 (2) | C5—C6 | 1.373 (3) |
O2—C13 | 1.213 (2) | C5—H5 | 0.94 (2) |
O1—C10 | 1.348 (2) | C6—H6 | 0.87 (2) |
O1—H1 | 0.95 (3) | C7—C8 | 1.383 (3) |
N1—N2 | 1.255 (2) | C7—C12 | 1.395 (3) |
N1—C1 | 1.427 (2) | C8—C9 | 1.402 (3) |
N2—C7 | 1.422 (2) | C8—H8 | 1.00 (2) |
C1—C6 | 1.391 (3) | C9—C10 | 1.395 (3) |
C1—C2 | 1.397 (3) | C9—C13 | 1.461 (3) |
C2—C3 | 1.384 (3) | C10—C11 | 1.400 (3) |
C3—C4 | 1.369 (3) | C11—C12 | 1.370 (3) |
C3—H3 | 0.95 (2) | C11—H11 | 0.92 (2) |
C4—C5 | 1.386 (3) | C12—H12 | 0.96 (2) |
C4—H4 | 0.88 (2) | C13—H13 | 0.98 (2) |
| | | |
C10—O1—H1 | 104.6 (17) | C8—C7—C12 | 119.2 (2) |
N2—N1—C1 | 113.6 (2) | C8—C7—N2 | 115.95 (18) |
N1—N2—C7 | 113.9 (2) | C12—C7—N2 | 124.8 (2) |
C6—C1—C2 | 118.1 (2) | C7—C8—C9 | 120.5 (2) |
C6—C1—N1 | 124.4 (2) | C7—C8—H8 | 120.6 (11) |
C2—C1—N1 | 117.5 (2) | C9—C8—H8 | 119.0 (11) |
C3—C2—C1 | 120.87 (18) | C10—C9—C8 | 119.55 (18) |
C3—C2—Cl1 | 118.6 (2) | C10—C9—C13 | 121.49 (18) |
C1—C2—Cl1 | 120.5 (1) | C8—C9—C13 | 119.0 (2) |
C4—C3—C2 | 119.7 (2) | O1—C10—C9 | 123.0 (2) |
C4—C3—H3 | 121.5 (14) | O1—C10—C11 | 117.4 (2) |
C2—C3—H3 | 118.8 (14) | C9—C10—C11 | 119.6 (2) |
C3—C4—C5 | 120.48 (19) | C12—C11—C10 | 120.0 (2) |
C3—C4—H4 | 119.5 (15) | C12—C11—H11 | 122.2 (13) |
C5—C4—H4 | 120.0 (15) | C10—C11—H11 | 117.8 (13) |
C6—C5—C4 | 119.8 (2) | C11—C12—C7 | 121.15 (19) |
C6—C5—H5 | 121.7 (14) | C11—C12—H12 | 118.3 (13) |
C4—C5—H5 | 118.4 (14) | C7—C12—H12 | 120.4 (13) |
C5—C6—C1 | 121.0 (2) | O2—C13—C9 | 124.5 (2) |
C5—C6—H6 | 122.0 (15) | O2—C13—H13 | 121.6 (13) |
C1—C6—H6 | 117.0 (15) | C9—C13—H13 | 113.8 (13) |
| | | |
C1—N1—N2—C7 | 179.8 (2) | C12—C7—C8—C9 | 1.0 (3) |
N2—N1—C1—C6 | 5.5 (3) | N2—C7—C8—C9 | −179.56 (17) |
N2—N1—C1—C2 | −174.78 (16) | C7—C8—C9—C10 | 0.1 (3) |
C6—C1—C2—C3 | 1.0 (3) | C7—C8—C9—C13 | −179.17 (19) |
N1—C1—C2—C3 | −178.71 (17) | C8—C9—C10—O1 | 178.95 (18) |
C6—C1—C2—Cl1 | −178.20 (15) | C13—C9—C10—O1 | −1.8 (3) |
N1—C1—C2—Cl1 | 2.1 (2) | C8—C9—C10—C11 | −1.1 (3) |
C1—C2—C3—C4 | −0.7 (3) | C13—C9—C10—C11 | 178.2 (2) |
Cl1—C2—C3—C4 | 178.50 (16) | O1—C10—C11—C12 | −179.07 (19) |
C2—C3—C4—C5 | −0.2 (3) | C9—C10—C11—C12 | 1.0 (3) |
C3—C4—C5—C6 | 0.7 (3) | C10—C11—C12—C7 | 0.1 (3) |
C4—C5—C6—C1 | −0.4 (3) | C8—C7—C12—C11 | −1.1 (3) |
C2—C1—C6—C5 | −0.4 (3) | N2—C7—C12—C11 | 179.48 (19) |
N1—C1—C6—C5 | 179.25 (18) | C10—C9—C13—O2 | 2.6 (3) |
N1—N2—C7—C8 | 179.18 (17) | C8—C9—C13—O2 | −178.1 (2) |
N1—N2—C7—C12 | −1.4 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.95 (3) | 1.83 (3) | 2.692 (2) | 149 (2) |
O1—H1···O2i | 0.95 (3) | 2.38 (3) | 2.952 (2) | 118 (2) |
Symmetry code: (i) −x+1, −y+1, −z+3. |
(II) 4-(2-chlorophenyldiazenyl)-2- {[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2
H)-one
top
Crystal data top
C17H18ClN3O4 | F(000) = 760 |
Mr = 363.79 | Dx = 1.430 Mg m−3 |
Monoclinic, P21/c | Melting point = 479–481 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 16.122 (3) Å | Cell parameters from 3332 reflections |
b = 8.3847 (12) Å | θ = 1.4–26.0° |
c = 13.359 (2) Å | µ = 0.25 mm−1 |
β = 110.689 (3)° | T = 213 K |
V = 1689.4 (5) Å3 | Prism, orange |
Z = 4 | 0.35 × 0.25 × 0.10 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3332 independent reflections |
Radiation source: fine-focus sealed tube | 2501 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 26.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | h = −19→15 |
Tmin = 0.916, Tmax = 0.975 | k = −8→10 |
10407 measured reflections | l = −16→16 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.109 | All H-atom parameters refined |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0674P)2 + 0.0074P] where P = (Fo2 + 2Fc2)/3 |
3332 reflections | (Δ/σ)max < 0.001 |
298 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Crystal data top
C17H18ClN3O4 | V = 1689.4 (5) Å3 |
Mr = 363.79 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.122 (3) Å | µ = 0.25 mm−1 |
b = 8.3847 (12) Å | T = 213 K |
c = 13.359 (2) Å | 0.35 × 0.25 × 0.10 mm |
β = 110.689 (3)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 3332 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995) | 2501 reflections with I > 2σ(I) |
Tmin = 0.916, Tmax = 0.975 | Rint = 0.026 |
10407 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.109 | All H-atom parameters refined |
S = 1.09 | Δρmax = 0.22 e Å−3 |
3332 reflections | Δρmin = −0.33 e Å−3 |
298 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.60359 (4) | 0.35489 (7) | 0.52771 (5) | 0.0584 (2) | |
O1 | 0.10407 (7) | 0.35993 (13) | 0.06417 (9) | 0.0268 (3) | |
O2 | −0.12329 (9) | 0.32805 (15) | −0.06353 (9) | 0.0319 (3) | |
O4 | −0.13144 (9) | 0.27918 (16) | 0.23544 (10) | 0.0364 (3) | |
O3 | −0.05874 (9) | −0.11636 (15) | 0.08949 (10) | 0.0341 (3) | |
N1 | 0.42847 (9) | 0.21133 (18) | 0.47415 (11) | 0.0314 (3) | |
N2 | 0.34956 (9) | 0.16842 (18) | 0.45484 (11) | 0.0323 (3) | |
N3 | −0.01545 (9) | 0.20702 (16) | 0.12104 (10) | 0.0217 (3) | |
C1 | 0.48879 (11) | 0.1572 (2) | 0.57426 (13) | 0.0303 (4) | |
C2 | 0.57490 (12) | 0.2178 (2) | 0.60750 (14) | 0.0360 (4) | |
C3 | 0.63803 (14) | 0.1710 (3) | 0.70347 (16) | 0.0450 (5) | |
C4 | 0.61604 (14) | 0.0615 (3) | 0.76676 (16) | 0.0482 (5) | |
C5 | 0.53168 (15) | −0.0016 (3) | 0.73474 (16) | 0.0466 (5) | |
C6 | 0.46863 (13) | 0.0447 (2) | 0.63908 (15) | 0.0378 (4) | |
C7 | 0.29029 (11) | 0.2201 (2) | 0.35382 (13) | 0.0278 (4) | |
C8 | 0.20345 (11) | 0.1748 (2) | 0.32736 (14) | 0.0283 (4) | |
C9 | 0.13867 (11) | 0.21684 (19) | 0.22878 (13) | 0.0244 (3) | |
C10 | 0.16284 (11) | 0.31197 (18) | 0.15440 (13) | 0.0240 (3) | |
C11 | 0.25369 (12) | 0.3535 (2) | 0.18322 (14) | 0.0319 (4) | |
C12 | 0.31529 (12) | 0.3103 (2) | 0.27925 (14) | 0.0326 (4) | |
C13 | 0.04935 (11) | 0.16657 (19) | 0.20657 (13) | 0.0248 (4) | |
C14 | −0.10832 (10) | 0.15382 (18) | 0.08636 (12) | 0.0215 (3) | |
C15 | −0.16372 (12) | 0.2836 (2) | 0.01114 (13) | 0.0268 (4) | |
C17 | −0.13889 (12) | 0.1321 (2) | 0.18129 (13) | 0.0255 (4) | |
C16 | −0.11721 (12) | −0.00217 (19) | 0.02397 (13) | 0.0274 (4) | |
H22 | −0.1163 (15) | 0.430 (3) | −0.0611 (18) | 0.055 (7)* | |
H44 | −0.1297 (17) | 0.259 (3) | 0.292 (2) | 0.060 (8)* | |
H33 | −0.0689 (15) | −0.202 (3) | 0.0509 (18) | 0.052 (7)* | |
H1 | −0.0041 (14) | 0.272 (3) | 0.0764 (16) | 0.047 (6)* | |
H3 | 0.6928 (17) | 0.213 (3) | 0.7243 (18) | 0.054 (6)* | |
H4 | 0.6577 (15) | 0.029 (3) | 0.8299 (18) | 0.053 (6)* | |
H5 | 0.5206 (15) | −0.083 (3) | 0.7765 (18) | 0.052 (6)* | |
H6 | 0.4108 (15) | −0.002 (2) | 0.6123 (16) | 0.049 (6)* | |
H8 | 0.1903 (14) | 0.111 (2) | 0.3787 (17) | 0.043 (6)* | |
H11 | 0.2715 (13) | 0.421 (2) | 0.1317 (15) | 0.037 (5)* | |
H12 | 0.3755 (14) | 0.343 (2) | 0.2979 (15) | 0.037 (5)* | |
H13 | 0.0387 (12) | 0.099 (2) | 0.2605 (15) | 0.033 (5)* | |
H15A | −0.1704 (11) | 0.378 (2) | 0.0528 (14) | 0.027 (5)* | |
H15B | −0.2240 (14) | 0.242 (2) | −0.0289 (15) | 0.037 (5)* | |
H17A | −0.2007 (13) | 0.097 (2) | 0.1530 (14) | 0.028 (4)* | |
H17B | −0.1059 (12) | 0.051 (2) | 0.2260 (14) | 0.024 (4)* | |
H16A | −0.1818 (13) | −0.037 (2) | 0.0041 (14) | 0.033 (5)* | |
H16B | −0.1029 (12) | 0.018 (2) | −0.0409 (15) | 0.036 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0344 (3) | 0.0714 (4) | 0.0619 (4) | −0.0117 (3) | 0.0077 (2) | 0.0179 (3) |
O1 | 0.0286 (6) | 0.0264 (6) | 0.0249 (6) | −0.0011 (5) | 0.0087 (5) | 0.0033 (4) |
O2 | 0.0483 (8) | 0.0267 (7) | 0.0230 (6) | 0.0023 (6) | 0.0154 (5) | 0.0044 (5) |
O4 | 0.0523 (9) | 0.0369 (7) | 0.0241 (7) | 0.0017 (6) | 0.0187 (6) | −0.0041 (5) |
O3 | 0.0429 (8) | 0.0259 (7) | 0.0312 (7) | 0.0060 (5) | 0.0100 (6) | 0.0003 (5) |
N1 | 0.0246 (8) | 0.0366 (8) | 0.0305 (8) | 0.0021 (6) | 0.0063 (6) | −0.0017 (6) |
N2 | 0.0242 (8) | 0.0396 (9) | 0.0313 (8) | 0.0023 (6) | 0.0075 (6) | 0.0012 (6) |
N3 | 0.0243 (7) | 0.0231 (7) | 0.0194 (7) | −0.0014 (5) | 0.0097 (6) | 0.0007 (5) |
C1 | 0.0246 (9) | 0.0380 (10) | 0.0281 (9) | 0.0048 (7) | 0.0088 (7) | −0.0054 (7) |
C2 | 0.0288 (9) | 0.0443 (11) | 0.0334 (10) | 0.0028 (8) | 0.0092 (8) | −0.0015 (8) |
C3 | 0.0278 (10) | 0.0608 (14) | 0.0387 (11) | 0.0012 (10) | 0.0024 (9) | −0.0060 (9) |
C4 | 0.0408 (12) | 0.0668 (15) | 0.0289 (10) | 0.0147 (11) | 0.0024 (9) | 0.0043 (10) |
C5 | 0.0459 (12) | 0.0597 (14) | 0.0346 (10) | 0.0090 (10) | 0.0148 (9) | 0.0105 (9) |
C6 | 0.0291 (10) | 0.0495 (12) | 0.0353 (10) | 0.0032 (9) | 0.0120 (8) | 0.0023 (8) |
C7 | 0.0247 (8) | 0.0286 (9) | 0.0285 (8) | 0.0025 (7) | 0.0072 (7) | 0.0010 (7) |
C8 | 0.0277 (9) | 0.0293 (9) | 0.0273 (9) | −0.0007 (7) | 0.0088 (7) | 0.0043 (7) |
C9 | 0.0243 (8) | 0.0235 (8) | 0.0256 (8) | −0.0006 (6) | 0.0092 (7) | −0.0014 (6) |
C10 | 0.0269 (8) | 0.0205 (8) | 0.0244 (8) | 0.0009 (6) | 0.0088 (7) | −0.0021 (6) |
C11 | 0.0289 (9) | 0.0357 (10) | 0.0337 (9) | −0.0032 (7) | 0.0141 (8) | 0.0043 (8) |
C12 | 0.0234 (9) | 0.0367 (10) | 0.0373 (10) | −0.0020 (7) | 0.0104 (8) | 0.0014 (8) |
C13 | 0.0270 (9) | 0.0250 (8) | 0.0234 (8) | −0.0015 (7) | 0.0102 (7) | 0.0006 (6) |
C14 | 0.0217 (8) | 0.0240 (8) | 0.0185 (7) | −0.0021 (6) | 0.0067 (6) | −0.0008 (6) |
C15 | 0.0295 (9) | 0.0278 (9) | 0.0227 (8) | 0.0025 (7) | 0.0087 (7) | 0.0023 (7) |
C17 | 0.0256 (9) | 0.0300 (9) | 0.0227 (8) | −0.0017 (7) | 0.0109 (7) | 0.0006 (7) |
C16 | 0.0308 (9) | 0.0260 (9) | 0.0234 (8) | −0.0008 (7) | 0.0071 (7) | −0.0023 (6) |
Geometric parameters (Å, º) top
Cl1—C2 | 1.737 (2) | C5—H5 | 0.93 (2) |
O1—C10 | 1.306 (2) | C6—H6 | 0.96 (2) |
O2—C15 | 1.421 (2) | C7—C8 | 1.371 (2) |
O2—H22 | 0.86 (3) | C7—C12 | 1.418 (2) |
O4—C17 | 1.413 (2) | C8—C9 | 1.406 (2) |
O4—H44 | 0.77 (3) | C8—H8 | 0.95 (2) |
O3—C16 | 1.410 (2) | C9—C13 | 1.427 (2) |
O3—H33 | 0.86 (2) | C9—C10 | 1.431 (2) |
N1—N2 | 1.258 (2) | C10—C11 | 1.420 (2) |
N1—C1 | 1.422 (2) | C11—C12 | 1.365 (2) |
N2—C7 | 1.418 (2) | C11—H11 | 1.01 (2) |
N3—C13 | 1.292 (2) | C12—H12 | 0.95 (2) |
N3—C14 | 1.471 (2) | C13—H13 | 0.98 (2) |
N3—H1 | 0.87 (2) | C14—C17 | 1.525 (2) |
C1—C6 | 1.394 (3) | C14—C16 | 1.530 (2) |
C1—C2 | 1.396 (2) | C14—C15 | 1.535 (2) |
C2—C3 | 1.383 (3) | C15—H15A | 0.995 (18) |
C3—C4 | 1.376 (3) | C15—H15B | 0.99 (2) |
C3—H3 | 0.90 (2) | C17—H17A | 0.98 (2) |
C4—C5 | 1.379 (3) | C17—H17B | 0.94 (2) |
C4—H4 | 0.92 (2) | C16—H16A | 1.02 (2) |
C5—C6 | 1.378 (3) | C16—H16B | 0.99 (2) |
| | | |
C15—O2—H22 | 108.7 (15) | O1—C10—C9 | 121.7 (2) |
C17—O4—H44 | 106.3 (19) | C11—C10—C9 | 117.14 (15) |
C16—O3—H33 | 104.3 (15) | C12—C11—C10 | 121.86 (16) |
N2—N1—C1 | 114.1 (2) | C12—C11—H11 | 120.2 (11) |
N1—N2—C7 | 113.6 (1) | C10—C11—H11 | 117.9 (11) |
C13—N3—C14 | 127.9 (1) | C11—C12—C7 | 120.59 (16) |
C13—N3—H1 | 117.9 (14) | C11—C12—H12 | 120.2 (12) |
C14—N3—H1 | 114.2 (14) | C7—C12—H12 | 119.2 (12) |
C6—C1—C2 | 118.2 (2) | N3—C13—C9 | 123.2 (2) |
C6—C1—N1 | 124.6 (2) | N3—C13—H13 | 120.4 (11) |
C2—C1—N1 | 117.1 (2) | C9—C13—H13 | 116.4 (11) |
C3—C2—C1 | 121.01 (19) | N3—C14—C17 | 111.5 (1) |
C3—C2—Cl1 | 119.2 (2) | N3—C14—C16 | 108.6 (1) |
C1—C2—Cl1 | 119.8 (1) | C17—C14—C16 | 110.80 (13) |
C4—C3—C2 | 119.6 (2) | N3—C14—C15 | 106.5 (1) |
C4—C3—H3 | 120.5 (15) | C17—C14—C15 | 110.17 (13) |
C2—C3—H3 | 119.9 (15) | C16—C14—C15 | 109.18 (13) |
C3—C4—C5 | 120.35 (19) | O2—C15—C14 | 109.9 (1) |
C3—C4—H4 | 120.2 (14) | O2—C15—H15A | 110.6 (10) |
C5—C4—H4 | 119.4 (14) | C14—C15—H15A | 110.5 (10) |
C6—C5—C4 | 120.2 (2) | O2—C15—H15B | 108.6 (11) |
C6—C5—H5 | 121.6 (14) | C14—C15—H15B | 109.6 (11) |
C4—C5—H5 | 118.0 (14) | H15A—C15—H15B | 107.6 (15) |
C5—C6—C1 | 120.61 (19) | O4—C17—C14 | 109.1 (1) |
C5—C6—H6 | 122.3 (13) | O4—C17—H17A | 110.4 (10) |
C1—C6—H6 | 117.0 (12) | C14—C17—H17A | 107.4 (10) |
C8—C7—C12 | 118.9 (2) | O4—C17—H17B | 112.4 (10) |
C8—C7—N2 | 116.4 (2) | C14—C17—H17B | 109.8 (10) |
C12—C7—N2 | 124.6 (2) | H17A—C17—H17B | 107.5 (15) |
C7—C8—C9 | 121.66 (16) | O3—C16—C14 | 109.2 (1) |
C7—C8—H8 | 115.9 (13) | O3—C16—H16A | 111.4 (10) |
C9—C8—H8 | 122.4 (13) | C14—C16—H16A | 106.0 (10) |
C8—C9—C13 | 118.79 (15) | O3—C16—H16B | 110.4 (11) |
C8—C9—C10 | 119.70 (15) | C14—C16—H16B | 109.0 (11) |
C13—C9—C10 | 121.49 (15) | H16A—C16—H16B | 110.7 (14) |
O1—C10—C11 | 121.1 (1) | | |
| | | |
C1—N1—N2—C7 | −178.7 (1) | C8—C9—C10—C11 | 2.7 (2) |
N2—N1—C1—C6 | 10.7 (2) | C13—C9—C10—C11 | −178.97 (15) |
N2—N1—C1—C2 | −171.56 (15) | O1—C10—C11—C12 | 177.08 (16) |
C6—C1—C2—C3 | −1.7 (3) | C9—C10—C11—C12 | −2.4 (3) |
N1—C1—C2—C3 | −179.62 (17) | C10—C11—C12—C7 | 0.6 (3) |
C6—C1—C2—Cl1 | 178.56 (14) | C8—C7—C12—C11 | 1.0 (3) |
N1—C1—C2—Cl1 | 0.6 (2) | N2—C7—C12—C11 | 179.33 (17) |
C1—C2—C3—C4 | 0.7 (3) | C14—N3—C13—C9 | 175.38 (14) |
Cl1—C2—C3—C4 | −179.51 (16) | C8—C9—C13—N3 | 175.93 (15) |
C2—C3—C4—C5 | 0.2 (3) | C10—C9—C13—N3 | −2.4 (2) |
C3—C4—C5—C6 | −0.1 (3) | C13—N3—C14—C17 | 36.1 (2) |
C4—C5—C6—C1 | −0.9 (3) | C13—N3—C14—C16 | −86.32 (18) |
C2—C1—C6—C5 | 1.8 (3) | C13—N3—C14—C15 | 156.22 (15) |
N1—C1—C6—C5 | 179.51 (17) | N3—C14—C15—O2 | 46.31 (17) |
N1—N2—C7—C8 | 178.97 (15) | C17—C14—C15—O2 | 167.32 (13) |
N1—N2—C7—C12 | 0.6 (2) | C16—C14—C15—O2 | −70.79 (17) |
C12—C7—C8—C9 | −0.6 (3) | N3—C14—C17—O4 | 60.08 (17) |
N2—C7—C8—C9 | −179.10 (15) | C16—C14—C17—O4 | −178.79 (13) |
C7—C8—C9—C13 | −179.63 (15) | C15—C14—C17—O4 | −57.86 (18) |
C7—C8—C9—C10 | −1.3 (3) | N3—C14—C16—O3 | 57.76 (17) |
C8—C9—C10—O1 | −176.76 (15) | C17—C14—C16—O3 | −65.03 (18) |
C13—C9—C10—O1 | 1.6 (2) | C15—C14—C16—O3 | 173.46 (13) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H22···O1i | 0.86 (3) | 1.78 (3) | 2.635 (2) | 177 (2) |
O4—H44···O2ii | 0.77 (3) | 2.03 (3) | 2.791 (2) | 172 (3) |
O3—H33···O1iii | 0.86 (2) | 1.96 (2) | 2.803 (2) | 167 (2) |
N3—H1···O1 | 0.87 (2) | 1.95 (2) | 2.640 (2) | 134.6 (19) |
N3—H1···O2 | 0.87 (2) | 2.21 (2) | 2.665 (2) | 112.4 (18) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+1/2, z+1/2; (iii) −x, −y, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C13H9ClN2O2 | C17H18ClN3O4 |
Mr | 260.67 | 363.79 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/c |
Temperature (K) | 213 | 213 |
a, b, c (Å) | 6.9938 (11), 21.636 (3), 8.1078 (13) | 16.122 (3), 8.3847 (12), 13.359 (2) |
β (°) | 108.724 (3) | 110.689 (3) |
V (Å3) | 1161.9 (3) | 1689.4 (5) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.32 | 0.25 |
Crystal size (mm) | 0.40 × 0.40 × 0.30 | 0.35 × 0.25 × 0.10 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995) | Multi-scan (SADABS; Blessing, 1995) |
Tmin, Tmax | 0.882, 0.909 | 0.916, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6246, 2275, 1783 | 10407, 3332, 2501 |
Rint | 0.051 | 0.026 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.108, 1.04 | 0.034, 0.109, 1.09 |
No. of reflections | 2275 | 3332 |
No. of parameters | 199 | 298 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.27, −0.23 | 0.22, −0.33 |
Selected geometric parameters (Å, º) for (I) topCl1—C2 | 1.733 (2) | N2—C7 | 1.422 (2) |
O2—C13 | 1.213 (2) | C7—C8 | 1.383 (3) |
O1—C10 | 1.348 (2) | C9—C10 | 1.395 (3) |
N1—N2 | 1.255 (2) | C9—C13 | 1.461 (3) |
N1—C1 | 1.427 (2) | C11—C12 | 1.370 (3) |
| | | |
N2—N1—C1 | 113.6 (2) | O1—C10—C9 | 123.0 (2) |
N1—N2—C7 | 113.9 (2) | O2—C13—C9 | 124.5 (2) |
| | | |
C1—N1—N2—C7 | 179.8 (2) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.95 (3) | 1.83 (3) | 2.692 (2) | 149 (2) |
O1—H1···O2i | 0.95 (3) | 2.38 (3) | 2.952 (2) | 118 (2) |
Symmetry code: (i) −x+1, −y+1, −z+3. |
Selected geometric parameters (Å, º) for (II) topO1—C10 | 1.306 (2) | C7—C8 | 1.371 (2) |
N1—N2 | 1.258 (2) | C9—C13 | 1.427 (2) |
N1—C1 | 1.422 (2) | C9—C10 | 1.431 (2) |
N2—C7 | 1.418 (2) | C11—C12 | 1.365 (2) |
N3—C13 | 1.292 (2) | | |
| | | |
N2—N1—C1 | 114.1 (2) | O1—C10—C9 | 121.7 (2) |
N1—N2—C7 | 113.6 (1) | N3—C13—C9 | 123.2 (2) |
C8—C7—N2 | 116.4 (2) | | |
| | | |
C1—N1—N2—C7 | −178.7 (1) | C10—C9—C13—N3 | −2.4 (2) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H22···O1i | 0.86 (3) | 1.78 (3) | 2.635 (2) | 177 (2) |
O4—H44···O2ii | 0.77 (3) | 2.03 (3) | 2.791 (2) | 172 (3) |
O3—H33···O1iii | 0.86 (2) | 1.96 (2) | 2.803 (2) | 167 (2) |
N3—H1···O1 | 0.87 (2) | 1.95 (2) | 2.640 (2) | 134.6 (19) |
N3—H1···O2 | 0.87 (2) | 2.21 (2) | 2.665 (2) | 112.4 (18) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, −y+1/2, z+1/2; (iii) −x, −y, −z. |
Azo compounds are the most widely used class of dyes, due to their versatile application in various fields, such as the dyeing of textiles and fibres, the colouring of different materials, and high-technology areas, such as electro-optical devices and ink-jet printers (Peters & Freeman, 1991). Schiff bases have been used extensively as ligands in the field of coordination chemistry (Garnovskii et al., 1993). There is considerable interest in Schiff base complexes due to their striking antitumour activities (Zhou et al., 2000). Schiff base compounds show photochromism and thermochromism in the solid state by proton transfer from the hydroxyl O atom to the imine N atom (Hadjoudis et al., 1987). Photochromic compounds are of great interest for the control and measurement of radiation intensity, optical computers and display systems (Dürr & Bouas-Laurent, 1990). Azo-azomethine compounds are also widely used in the textile industry as synthetic colouring materials (Kamel et al., 1971).
2-Hydroxy Schiff base ligands are of interest mainly due to the existence of O—H···N and N—H···O hydrogen bonds and tautomerism between enol and keto forms. In the aldimine compounds made from 2-hydroxy-1-naphthaldehyde, both types of hydrogen bonds were found (Fernández et al., 2001). The structures of Schiff bases derived from salicylaldehyde generally exist in the phenol-imine form (Elmalı et al., 1999; Filarowski et al., 1999). In contrast, the structures of Schiff bases derived from the condensation of salicylaldehyde and substituted salicylaldehyde with tris(hydroxymethyl)aminomethane only exist in the keto-amine form (Odabaşoǧlu, Albayrak, Büyükgüngör & Lönnecke, 2003).
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) and (II), have been determined. The molecular structures of (I) and (II), with the atom-labelling schemes, are shown in Figs. 1 and 2, respectively, and selected bond lengths and angles are shown in Tables 1 and 3, respectively. \sch
In (I), the aromatic rings, which adopt a trans configuration about the N═N double bond, are nearly coplanar, with a dihedral angle of 4.1 (1)°. A significant intramolecular interaction is noted, involving the phenolic atom H1 and carbonyl atom O2, such that a six-membered ring is formed (Table 2). The C—Cl bond distance in (I) is consistent with that in 4-[(3-chlorophenyl)diazenyl]-2- {[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one (Odabaşoǧlu, Albayrak, Büyükgüngör & Goesmann, 2003). The C13—O2 bond distance in (I) is also consistent with the value of a C═O double bond for carbonyl compounds (Loudon, 2002).
In compound (II), the azobenzene moieties of the molecules have the trans configuration, and the dihedral angle between the planes of the two aromatic rings is 9.9 (1)°. In our previous work, the same dihedral angle was 20.47 (10)° in 4-(3-chlorophenyldiazenyl)-2-{[tris (hydroxymethyl)methyl]aminomethylene} cyclohexa-3,5-dien-1(2H)-one (Odabaşoǧlu, Albayrak, Büyükgüngör & Goesmann, 2003). The present X-ray structure determination reveals that, in the solid state, the keto-amine tautomer exists in the molecule of (II). This is evident from the observed contraction of the C10—O1, C9—C13, C7—C8 and C11—C12 distances and the elongation of C8—C9, C9—C10 and C10—C11, relative to the starting material, (I) (Tables 1 and 3). Furthermore, the C13—N3 bond in (II) is elongated relative to the C═N bond [1.275 (2) Å] in 2-[2-(hydroxymethyl)phenyliminokethyl]phenol, which exists in the phenol-imine form (Ersanlı et al., 2004). The N1═N2, N1—C1 and N2—C7 bond lengths are approximately the same in both (I) and (II). That is to say, transforming to the keto-amine form of the salicylidene ring does not affect bond distances but slightly changes the torsion angle (C1—N1—N2—C7) in the azo moiety.
The intra- and intermolecular hydrogen-bonding for (II) is shown in Fig.3 and the geometric values are given in Table 4. Atom H33 bonded to N3 forms a strong intramolecular hydrogen bond with atom O1 [2.640 (2) Å], as in our previous work (Odabaşoğlu, Albayrak, Büyükgüngör & Goesmann, 2003; Odabaşoğlu, Albayrak, Büyükgüngör & Lönnecke, 2003).