The two title molecules, both C
15H
14N
2O
3, are roughly planar and display a
trans conformation with respect to the –N=N– double bond, as found for other diazene derivatives. In both compounds, there are intramolecular O—H
O hydrogen bonds and the crystal packing is governed by weak intermolecular C—H
O hydrogen bonds and π–π stacking.
Supporting information
CCDC references: 243625; 243626
Compounds (I) and (II) were prepared as described by Odabaşoǧlu et al. (2003) using o-vanilline and 4-methylaniline for (I), and o-vanilline and 2-methylaniline for (II), as starting materials. Well shaped crystals of (I) and (II) were obtained by slow evaporation from acetic acid [m.p. 407–409 K, yield 83% for (I); m.p. 381–383 K, yield 82% for (II)].
For (I), C—H distances are in the range 0.94 (1)–1.01 (1) Å, and Uiso(H) values are in the range 0.049 (4)–0.072 (5) Å2. For the hydroxy H atom, the O—H distance is 0.97 (2) Å. The remaining H atoms were positioned geometrically and treated using a riding model, fixing the bond lengths at 0.96 Å for atoms C14 and C15. The Uiso (H) values were constrained as 1.5Ueq(Cmethyl). For (II), all H atoms were positioned geometrically and refined as riding, with C—H distances of 0.93–0.96 Å and O—H distances of 0.82 Å. The Uiso(H) values were constrained as 1.2Ueq(C) [1.5Ueq(Cmethyl)]. Owing to the absence of atoms heavier than Si and to the use of Mo Kα radiation, the absolute structure could not be determined reliably and Friedel pairs were merged, resulting in a low data/parameter ratio.
For both compounds, 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, 1990); 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) 3-Methoxy-5-(4-methylphenyldiazenyl)salicylaldehyde
top
Crystal data top
C15H14N2O3 | F(000) = 568 |
Mr = 270.28 | Dx = 1.366 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 5746 reflections |
a = 6.746 (5) Å | θ = 1.6–28.7° |
b = 12.529 (5) Å | µ = 0.10 mm−1 |
c = 15.556 (5) Å | T = 293 K |
β = 91.842 (5)° | Prism, yellow |
V = 1314.1 (12) Å3 | 0.50 × 0.35 × 0.25 mm |
Z = 4 | |
Data collection top
Stoe IPDS-II diffractometer | 1784 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.119 |
Plane graphite monochromator | θmax = 28.7°, θmin = 2.1° |
Detector resolution: 6.67 pixels mm-1 | h = −9→7 |
ω scans | k = −16→16 |
10018 measured reflections | l = −20→20 |
3361 independent reflections | |
Refinement top
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)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0583P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.84 | (Δ/σ)max < 0.001 |
3361 reflections | Δρmax = 0.32 e Å−3 |
216 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.013 (3) |
Crystal data top
C15H14N2O3 | V = 1314.1 (12) Å3 |
Mr = 270.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.746 (5) Å | µ = 0.10 mm−1 |
b = 12.529 (5) Å | T = 293 K |
c = 15.556 (5) Å | 0.50 × 0.35 × 0.25 mm |
β = 91.842 (5)° | |
Data collection top
Stoe IPDS-II diffractometer | 1784 reflections with I > 2σ(I) |
10018 measured reflections | Rint = 0.119 |
3361 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.84 | Δρmax = 0.32 e Å−3 |
3361 reflections | Δρmin = −0.20 e Å−3 |
216 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 | |
C1 | 0.33622 (19) | 0.36193 (9) | 0.40389 (8) | 0.0444 (3) | |
C2 | 0.3628 (2) | 0.25298 (10) | 0.39561 (9) | 0.0504 (3) | |
C3 | 0.2200 (2) | 0.18339 (10) | 0.42316 (9) | 0.0510 (3) | |
C4 | 0.04802 (19) | 0.22003 (10) | 0.45914 (8) | 0.0470 (3) | |
C5 | 0.0219 (2) | 0.32943 (11) | 0.46570 (9) | 0.0536 (3) | |
C6 | 0.1636 (2) | 0.39996 (11) | 0.43900 (9) | 0.0524 (3) | |
C7 | 0.62022 (19) | 0.59095 (10) | 0.35405 (8) | 0.0456 (3) | |
C8 | 0.79107 (19) | 0.55422 (10) | 0.31816 (8) | 0.0469 (3) | |
C9 | 0.93263 (19) | 0.62663 (9) | 0.29046 (8) | 0.0444 (3) | |
C10 | 0.90115 (19) | 0.73650 (9) | 0.29936 (8) | 0.0448 (3) | |
C11 | 0.72723 (19) | 0.77318 (9) | 0.33588 (8) | 0.0459 (3) | |
C12 | 0.5900 (2) | 0.70062 (10) | 0.36292 (8) | 0.0475 (3) | |
C13 | 1.1077 (2) | 0.58737 (12) | 0.24961 (9) | 0.0529 (3) | |
C14 | 0.5280 (2) | 0.92439 (11) | 0.36598 (11) | 0.0680 (4) | |
H14A | 0.5054 | 0.9061 | 0.4248 | 0.102* | |
H14B | 0.4232 | 0.8957 | 0.3297 | 0.102* | |
H14C | 0.5310 | 1.0006 | 0.3601 | 0.102* | |
C15 | −0.1063 (2) | 0.14499 (11) | 0.49108 (10) | 0.0640 (4) | |
H15A | −0.0742 | 0.1259 | 0.5497 | 0.096* | |
H15B | −0.1097 | 0.0818 | 0.4561 | 0.096* | |
H15C | −0.2337 | 0.1792 | 0.4879 | 0.096* | |
N1 | 0.49277 (16) | 0.42766 (8) | 0.37451 (7) | 0.0501 (3) | |
N2 | 0.46433 (16) | 0.52530 (8) | 0.38410 (7) | 0.0502 (3) | |
O1 | 1.23469 (15) | 0.64489 (8) | 0.21944 (7) | 0.0635 (3) | |
O2 | 1.03377 (15) | 0.80895 (7) | 0.27247 (6) | 0.0574 (3) | |
O3 | 0.71129 (14) | 0.88132 (7) | 0.34145 (7) | 0.0599 (3) | |
H2 | 0.480 (2) | 0.2281 (11) | 0.3673 (9) | 0.057 (4)* | |
H2O | 1.130 (3) | 0.7604 (15) | 0.2488 (12) | 0.092 (6)* | |
H3 | 0.242 (2) | 0.1069 (12) | 0.4148 (9) | 0.064 (4)* | |
H5 | −0.103 (3) | 0.3568 (11) | 0.4890 (10) | 0.072 (5)* | |
H6 | 0.147 (2) | 0.4743 (13) | 0.4463 (9) | 0.066 (4)* | |
H8 | 0.816 (2) | 0.4810 (11) | 0.3113 (8) | 0.053 (4)* | |
H12 | 0.469 (2) | 0.7224 (11) | 0.3879 (8) | 0.049 (4)* | |
H13 | 1.119 (2) | 0.5073 (12) | 0.2452 (9) | 0.059 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0442 (7) | 0.0411 (7) | 0.0480 (7) | −0.0020 (5) | 0.0058 (6) | 0.0025 (5) |
C2 | 0.0463 (8) | 0.0453 (7) | 0.0602 (8) | 0.0037 (6) | 0.0122 (7) | 0.0005 (6) |
C3 | 0.0536 (8) | 0.0367 (6) | 0.0632 (8) | −0.0005 (6) | 0.0098 (7) | 0.0016 (6) |
C4 | 0.0474 (8) | 0.0457 (7) | 0.0480 (7) | −0.0046 (6) | 0.0041 (6) | 0.0036 (5) |
C5 | 0.0478 (8) | 0.0497 (7) | 0.0641 (9) | 0.0026 (6) | 0.0147 (7) | −0.0010 (6) |
C6 | 0.0535 (9) | 0.0394 (7) | 0.0650 (8) | 0.0006 (6) | 0.0121 (7) | 0.0002 (6) |
C7 | 0.0443 (7) | 0.0445 (7) | 0.0482 (7) | −0.0048 (5) | 0.0036 (6) | 0.0032 (5) |
C8 | 0.0496 (8) | 0.0395 (7) | 0.0518 (7) | −0.0013 (6) | 0.0033 (6) | 0.0002 (5) |
C9 | 0.0437 (7) | 0.0435 (6) | 0.0461 (7) | 0.0003 (5) | 0.0039 (6) | −0.0001 (5) |
C10 | 0.0427 (7) | 0.0442 (7) | 0.0478 (7) | −0.0051 (5) | 0.0045 (6) | 0.0031 (5) |
C11 | 0.0476 (8) | 0.0373 (6) | 0.0531 (7) | −0.0005 (5) | 0.0069 (6) | 0.0016 (5) |
C12 | 0.0432 (7) | 0.0451 (7) | 0.0546 (8) | −0.0004 (6) | 0.0098 (6) | 0.0015 (5) |
C13 | 0.0489 (8) | 0.0524 (8) | 0.0578 (8) | 0.0015 (6) | 0.0083 (6) | −0.0004 (6) |
C14 | 0.0586 (9) | 0.0451 (7) | 0.1017 (12) | 0.0062 (7) | 0.0248 (9) | 0.0010 (7) |
C15 | 0.0595 (9) | 0.0587 (9) | 0.0747 (10) | −0.0115 (7) | 0.0141 (8) | 0.0086 (7) |
N1 | 0.0486 (7) | 0.0434 (6) | 0.0589 (7) | −0.0038 (5) | 0.0074 (5) | 0.0028 (5) |
N2 | 0.0514 (7) | 0.0417 (6) | 0.0580 (7) | −0.0048 (5) | 0.0077 (5) | 0.0028 (5) |
O1 | 0.0515 (6) | 0.0663 (6) | 0.0738 (7) | 0.0011 (5) | 0.0178 (5) | 0.0043 (5) |
O2 | 0.0503 (6) | 0.0477 (5) | 0.0752 (7) | −0.0065 (4) | 0.0191 (5) | 0.0029 (4) |
O3 | 0.0533 (6) | 0.0383 (4) | 0.0894 (7) | 0.0003 (4) | 0.0233 (5) | 0.0015 (4) |
Geometric parameters (Å, º) top
C1—C2 | 1.3832 (18) | C9—C13 | 1.446 (2) |
C1—C6 | 1.387 (2) | C10—O2 | 1.350 (2) |
C1—N1 | 1.426 (2) | C10—C11 | 1.3976 (19) |
C2—C3 | 1.3779 (19) | C11—O3 | 1.362 (2) |
C2—H2 | 0.971 (15) | C11—C12 | 1.3731 (19) |
C3—C4 | 1.383 (2) | C12—H12 | 0.957 (14) |
C3—H3 | 0.979 (15) | C13—O1 | 1.224 (2) |
C4—C5 | 1.3861 (19) | C13—H13 | 1.009 (14) |
C4—C15 | 1.4991 (19) | C14—O3 | 1.413 (2) |
C5—C6 | 1.375 (2) | C14—H14A | 0.9600 |
C5—H5 | 0.989 (17) | C14—H14B | 0.9600 |
C6—H6 | 0.945 (16) | C14—H14C | 0.9600 |
C7—C8 | 1.3760 (19) | C15—H15A | 0.9600 |
C7—C12 | 1.3965 (19) | C15—H15B | 0.9600 |
C7—N2 | 1.426 (2) | C15—H15C | 0.9600 |
C8—C9 | 1.3954 (18) | N1—N2 | 1.248 (2) |
C8—H8 | 0.940 (13) | O2—H2O | 0.973 (19) |
C9—C10 | 1.4004 (18) | | |
| | | |
C2—C1—C6 | 119.27 (12) | O2—C10—C9 | 121.7 (2) |
C2—C1—N1 | 116.1 (1) | C11—C10—C9 | 119.7 (1) |
C6—C1—N1 | 124.6 (1) | O3—C11—C12 | 125.7 (2) |
C3—C2—C1 | 120.09 (13) | O3—C11—C10 | 114.9 (2) |
C3—C2—H2 | 121.8 (8) | C12—C11—C10 | 119.33 (12) |
C1—C2—H2 | 118.0 (8) | C11—C12—C7 | 121.28 (13) |
C2—C3—C4 | 121.34 (13) | C11—C12—H12 | 122.0 (8) |
C2—C3—H3 | 118.0 (8) | C7—C12—H12 | 116.7 (8) |
C4—C3—H3 | 120.7 (8) | O1—C13—C9 | 124.1 (1) |
C3—C4—C5 | 117.91 (12) | O1—C13—H13 | 120.2 (8) |
C3—C4—C15 | 121.77 (12) | C9—C13—H13 | 115.7 (8) |
C5—C4—C15 | 120.31 (13) | O3—C14—H14A | 109.5 |
C6—C5—C4 | 121.48 (14) | O3—C14—H14B | 109.5 |
C6—C5—H5 | 119.7 (9) | H14A—C14—H14B | 109.5 |
C4—C5—H5 | 118.8 (9) | O3—C14—H14C | 109.5 |
C5—C6—C1 | 119.90 (13) | H14A—C14—H14C | 109.5 |
C5—C6—H6 | 120.8 (9) | H14B—C14—H14C | 109.5 |
C1—C6—H6 | 119.3 (9) | C4—C15—H15A | 109.5 |
C8—C7—C12 | 119.73 (12) | C4—C15—H15B | 109.5 |
C8—C7—N2 | 125.2 (1) | H15A—C15—H15B | 109.5 |
C12—C7—N2 | 115.1 (1) | C4—C15—H15C | 109.5 |
C7—C8—C9 | 119.89 (12) | H15A—C15—H15C | 109.5 |
C7—C8—H8 | 121.9 (8) | H15B—C15—H15C | 109.5 |
C9—C8—H8 | 118.2 (8) | N2—N1—C1 | 114.2 (2) |
C8—C9—C10 | 120.07 (12) | N1—N2—C7 | 114.1 (2) |
C8—C9—C13 | 119.44 (12) | C10—O2—H2O | 98.9 (10) |
C10—C9—C13 | 120.44 (11) | C11—O3—C14 | 117.9 (2) |
O2—C10—C11 | 118.6 (2) | | |
| | | |
C6—C1—C2—C3 | −0.9 (2) | O2—C10—C11—O3 | −0.79 (17) |
N1—C1—C2—C3 | 179.32 (12) | C9—C10—C11—O3 | −179.93 (11) |
C1—C2—C3—C4 | 0.2 (2) | O2—C10—C11—C12 | 179.46 (12) |
C2—C3—C4—C5 | 0.9 (2) | C9—C10—C11—C12 | 0.32 (19) |
C2—C3—C4—C15 | −178.64 (14) | O3—C11—C12—C7 | 179.80 (12) |
C3—C4—C5—C6 | −1.3 (2) | C10—C11—C12—C7 | −0.48 (19) |
C15—C4—C5—C6 | 178.25 (14) | C8—C7—C12—C11 | 0.48 (19) |
C4—C5—C6—C1 | 0.6 (2) | N2—C7—C12—C11 | −179.34 (12) |
C2—C1—C6—C5 | 0.5 (2) | C8—C9—C13—O1 | 176.18 (13) |
N1—C1—C6—C5 | −179.73 (13) | C10—C9—C13—O1 | −1.4 (2) |
C12—C7—C8—C9 | −0.31 (19) | C2—C1—N1—N2 | −179.12 (12) |
N2—C7—C8—C9 | 179.50 (12) | C6—C1—N1—N2 | 1.09 (18) |
C7—C8—C9—C10 | 0.16 (18) | C1—N1—N2—C7 | −179.51 (10) |
C7—C8—C9—C13 | −177.45 (12) | C8—C7—N2—N1 | −0.78 (18) |
C8—C9—C10—O2 | −179.28 (12) | C12—C7—N2—N1 | 179.04 (11) |
C13—C9—C10—O2 | −1.69 (19) | C12—C11—O3—C14 | −9.2 (2) |
C8—C9—C10—C11 | −0.16 (18) | C10—C11—O3—C14 | 171.02 (12) |
C13—C9—C10—C11 | 177.43 (12) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O3i | 1.01 (2) | 2.39 (1) | 3.205 (2) | 137.3 (10) |
C2—H2···O1i | 0.97 (2) | 2.60 (2) | 3.567 (2) | 172.7 (11) |
O2—H2O···O1 | 0.97 (2) | 1.68 (2) | 2.611 (2) | 159.1 (16) |
Symmetry code: (i) −x+2, y−1/2, −z+1/2. |
(II) 3-Methoxy-5-(2-methylphenyldiazenyl)salicylaldehyde
top
Crystal data top
C15H14N2O3 | F(000) = 568 |
Mr = 270.28 | Dx = 1.336 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: C -2yc | Cell parameters from 8228 reflections |
a = 10.734 (5) Å | θ = 2.4–25.9° |
b = 14.786 (5) Å | µ = 0.10 mm−1 |
c = 8.533 (5) Å | T = 293 K |
β = 97.053 (5)° | Prism, light brown |
V = 1344.0 (11) Å3 | 0.60 × 0.33 × 0.13 mm |
Z = 4 | |
Data collection top
Stoe IPDS-II diffractometer | 1052 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.077 |
Plane graphite monochromator | θmax = 25.9°, θmin = 2.4° |
Detector resolution: 6.67 pixels mm-1 | h = −13→13 |
ω scans | k = −18→18 |
9238 measured reflections | l = −9→10 |
1307 independent reflections | |
Refinement top
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)] = 0.031 | H-atom parameters constrained |
wR(F2) = 0.078 | w = 1/[σ2(Fo2) + (0.0546P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.93 | (Δ/σ)max < 0.001 |
1307 reflections | Δρmax = 0.12 e Å−3 |
185 parameters | Δρmin = −0.11 e Å−3 |
2 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.016 (3) |
Crystal data top
C15H14N2O3 | V = 1344.0 (11) Å3 |
Mr = 270.28 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 10.734 (5) Å | µ = 0.10 mm−1 |
b = 14.786 (5) Å | T = 293 K |
c = 8.533 (5) Å | 0.60 × 0.33 × 0.13 mm |
β = 97.053 (5)° | |
Data collection top
Stoe IPDS-II diffractometer | 1052 reflections with I > 2σ(I) |
9238 measured reflections | Rint = 0.077 |
1307 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 2 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 0.93 | Δρmax = 0.12 e Å−3 |
1307 reflections | Δρmin = −0.11 e Å−3 |
185 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 | |
C1 | 0.4664 (2) | 0.68612 (19) | 0.0209 (3) | 0.0527 (6) | |
C2 | 0.4365 (2) | 0.75242 (19) | −0.0941 (3) | 0.0556 (6) | |
C3 | 0.3836 (3) | 0.7244 (2) | −0.2425 (3) | 0.0664 (7) | |
H3 | 0.3625 | 0.7677 | −0.3204 | 0.080* | |
C4 | 0.3614 (3) | 0.6350 (2) | −0.2780 (3) | 0.0729 (8) | |
H4 | 0.3262 | 0.6182 | −0.3789 | 0.088* | |
C5 | 0.3912 (3) | 0.5700 (2) | −0.1637 (3) | 0.0707 (7) | |
H5 | 0.3764 | 0.5093 | −0.1871 | 0.085* | |
C6 | 0.4432 (2) | 0.59563 (19) | −0.0147 (3) | 0.0615 (6) | |
H6 | 0.4629 | 0.5519 | 0.0627 | 0.074* | |
C7 | 0.6021 (2) | 0.68796 (18) | 0.4218 (3) | 0.0534 (6) | |
C8 | 0.6450 (2) | 0.62257 (18) | 0.5293 (3) | 0.0606 (6) | |
H8 | 0.6385 | 0.5619 | 0.5005 | 0.073* | |
C9 | 0.6981 (2) | 0.64610 (19) | 0.6809 (3) | 0.0588 (6) | |
C10 | 0.7070 (2) | 0.73696 (19) | 0.7241 (3) | 0.0563 (6) | |
C11 | 0.6614 (2) | 0.80367 (17) | 0.6145 (3) | 0.0539 (6) | |
C12 | 0.6097 (2) | 0.77953 (19) | 0.4657 (3) | 0.0551 (6) | |
H12 | 0.5796 | 0.8239 | 0.3936 | 0.066* | |
C13 | 0.7415 (3) | 0.5760 (2) | 0.7913 (3) | 0.0774 (8) | |
H13 | 0.7316 | 0.5163 | 0.7577 | 0.093* | |
C14 | 0.6149 (3) | 0.95977 (18) | 0.5744 (4) | 0.0775 (8) | |
H14A | 0.6526 | 0.9629 | 0.4782 | 0.116* | |
H14B | 0.6258 | 1.0166 | 0.6289 | 0.116* | |
H14C | 0.5270 | 0.9470 | 0.5504 | 0.116* | |
C15 | 0.4623 (3) | 0.85087 (19) | −0.0605 (4) | 0.0704 (7) | |
H15A | 0.4317 | 0.8671 | 0.0368 | 0.106* | |
H15B | 0.4206 | 0.8867 | −0.1450 | 0.106* | |
H15C | 0.5511 | 0.8616 | −0.0518 | 0.106* | |
N1 | 0.51716 (18) | 0.71794 (15) | 0.1733 (2) | 0.0548 (5) | |
N2 | 0.55309 (19) | 0.65674 (15) | 0.2695 (2) | 0.0595 (6) | |
O1 | 0.7909 (2) | 0.58971 (17) | 0.9275 (3) | 0.0962 (7) | |
O2 | 0.75812 (19) | 0.76390 (15) | 0.8682 (3) | 0.0735 (6) | |
H2O | 0.7810 | 0.7195 | 0.9217 | 0.110* | |
O3 | 0.67369 (16) | 0.88961 (13) | 0.6724 (3) | 0.0670 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0500 (12) | 0.0627 (16) | 0.0452 (14) | −0.0024 (10) | 0.0045 (10) | −0.0027 (10) |
C2 | 0.0518 (13) | 0.0649 (15) | 0.0508 (14) | 0.0001 (11) | 0.0082 (11) | 0.0038 (12) |
C3 | 0.0654 (15) | 0.085 (2) | 0.0459 (15) | −0.0036 (14) | −0.0036 (11) | 0.0082 (14) |
C4 | 0.0704 (16) | 0.097 (2) | 0.0488 (14) | −0.0109 (13) | −0.0031 (12) | −0.0044 (13) |
C5 | 0.0771 (18) | 0.0750 (18) | 0.0585 (14) | −0.0143 (14) | 0.0025 (12) | −0.0115 (14) |
C6 | 0.0697 (15) | 0.0621 (16) | 0.0512 (13) | −0.0037 (12) | 0.0010 (10) | −0.0018 (12) |
C7 | 0.0567 (12) | 0.0593 (15) | 0.0429 (13) | −0.0020 (10) | 0.0007 (10) | −0.0012 (10) |
C8 | 0.0625 (14) | 0.0627 (14) | 0.0547 (15) | 0.0014 (12) | 0.0003 (11) | −0.0007 (12) |
C9 | 0.0557 (14) | 0.0678 (15) | 0.0510 (14) | 0.0009 (11) | −0.0012 (11) | 0.0045 (12) |
C10 | 0.0493 (13) | 0.0737 (17) | 0.0437 (14) | −0.0007 (11) | −0.0027 (11) | −0.0038 (11) |
C11 | 0.0527 (12) | 0.0572 (14) | 0.0510 (14) | −0.0026 (11) | 0.0027 (10) | −0.0053 (11) |
C12 | 0.0557 (12) | 0.0632 (14) | 0.0455 (12) | −0.0005 (10) | 0.0024 (10) | 0.0021 (11) |
C13 | 0.0857 (19) | 0.0783 (18) | 0.0630 (17) | 0.0070 (14) | −0.0115 (14) | 0.0101 (13) |
C14 | 0.0849 (18) | 0.0590 (15) | 0.0838 (19) | 0.0010 (13) | −0.0080 (15) | −0.0041 (14) |
C15 | 0.0812 (19) | 0.0616 (16) | 0.0679 (17) | 0.0006 (13) | 0.0073 (13) | 0.0054 (13) |
N1 | 0.0573 (12) | 0.0608 (13) | 0.0446 (12) | −0.0028 (9) | −0.0009 (9) | −0.0025 (10) |
N2 | 0.0663 (12) | 0.0658 (15) | 0.0442 (11) | −0.0012 (9) | −0.0023 (9) | −0.0014 (10) |
O1 | 0.1105 (17) | 0.0988 (16) | 0.0702 (13) | 0.0086 (12) | −0.0259 (11) | 0.0164 (11) |
O2 | 0.0771 (12) | 0.0870 (14) | 0.0513 (12) | 0.0015 (10) | −0.0128 (9) | −0.0051 (9) |
O3 | 0.0770 (11) | 0.0604 (10) | 0.0602 (10) | −0.0031 (8) | −0.0057 (8) | −0.0075 (8) |
Geometric parameters (Å, º) top
C1—C6 | 1.388 (4) | C9—C13 | 1.439 (4) |
C1—C2 | 1.396 (4) | C10—O2 | 1.344 (4) |
C1—N1 | 1.427 (3) | C10—C11 | 1.405 (4) |
C2—C3 | 1.386 (4) | C11—O3 | 1.364 (3) |
C2—C15 | 1.503 (4) | C11—C12 | 1.369 (4) |
C3—C4 | 1.372 (5) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C13—O1 | 1.234 (4) |
C4—C5 | 1.378 (4) | C13—H13 | 0.9300 |
C4—H4 | 0.9300 | C14—O3 | 1.429 (4) |
C5—C6 | 1.377 (4) | C14—H14A | 0.9600 |
C5—H5 | 0.9300 | C14—H14B | 0.9600 |
C6—H6 | 0.9300 | C14—H14C | 0.9600 |
C7—C8 | 1.373 (4) | C15—H15A | 0.9600 |
C7—C12 | 1.405 (4) | C15—H15B | 0.9600 |
C7—N2 | 1.418 (3) | C15—H15C | 0.9600 |
C8—C9 | 1.393 (4) | N1—N2 | 1.251 (3) |
C8—H8 | 0.9300 | O2—H2O | 0.8200 |
C9—C10 | 1.393 (4) | | |
| | | |
C6—C1—C2 | 120.2 (3) | O2—C10—C11 | 118.1 (3) |
C6—C1—N1 | 123.7 (2) | C9—C10—C11 | 119.6 (2) |
C2—C1—N1 | 116.0 (2) | O3—C11—C12 | 126.1 (2) |
C3—C2—C1 | 117.7 (3) | O3—C11—C10 | 113.8 (2) |
C3—C2—C15 | 120.6 (2) | C12—C11—C10 | 120.2 (2) |
C1—C2—C15 | 121.7 (3) | C11—C12—C7 | 120.2 (2) |
C4—C3—C2 | 122.0 (3) | C11—C12—H12 | 119.9 |
C4—C3—H3 | 119.0 | C7—C12—H12 | 119.9 |
C2—C3—H3 | 119.0 | O1—C13—C9 | 124.5 (3) |
C3—C4—C5 | 119.8 (3) | O1—C13—H13 | 117.8 |
C3—C4—H4 | 120.1 | C9—C13—H13 | 117.8 |
C5—C4—H4 | 120.1 | O3—C14—H14A | 109.5 |
C6—C5—C4 | 119.6 (3) | O3—C14—H14B | 109.5 |
C6—C5—H5 | 120.2 | H14A—C14—H14B | 109.5 |
C4—C5—H5 | 120.2 | O3—C14—H14C | 109.5 |
C5—C6—C1 | 120.5 (3) | H14A—C14—H14C | 109.5 |
C5—C6—H6 | 119.7 | H14B—C14—H14C | 109.5 |
C1—C6—H6 | 119.7 | C2—C15—H15A | 109.5 |
C8—C7—C12 | 119.8 (2) | C2—C15—H15B | 109.5 |
C8—C7—N2 | 116.1 (2) | H15A—C15—H15B | 109.5 |
C12—C7—N2 | 124.2 (2) | C2—C15—H15C | 109.5 |
C7—C8—C9 | 120.7 (2) | H15A—C15—H15C | 109.5 |
C7—C8—H8 | 119.7 | H15B—C15—H15C | 109.5 |
C9—C8—H8 | 119.7 | N2—N1—C1 | 114.4 (2) |
C8—C9—C10 | 119.6 (2) | N1—N2—C7 | 114.6 (2) |
C8—C9—C13 | 119.4 (3) | C10—O2—H2O | 109.5 |
C10—C9—C13 | 121.0 (2) | C11—O3—C14 | 116.6 (2) |
O2—C10—C9 | 122.3 (2) | | |
| | | |
C6—C1—C2—C3 | 0.0 (4) | C13—C9—C10—C11 | −178.7 (2) |
N1—C1—C2—C3 | −178.2 (2) | O2—C10—C11—O3 | −1.2 (3) |
C6—C1—C2—C15 | −179.0 (2) | C9—C10—C11—O3 | 178.9 (2) |
N1—C1—C2—C15 | 2.8 (4) | O2—C10—C11—C12 | 179.3 (2) |
C1—C2—C3—C4 | −0.4 (4) | C9—C10—C11—C12 | −0.6 (4) |
C15—C2—C3—C4 | 178.6 (3) | O3—C11—C12—C7 | −179.5 (2) |
C2—C3—C4—C5 | 0.4 (5) | C10—C11—C12—C7 | −0.1 (4) |
C3—C4—C5—C6 | 0.0 (5) | C8—C7—C12—C11 | 1.0 (4) |
C4—C5—C6—C1 | −0.4 (4) | N2—C7—C12—C11 | −178.3 (2) |
C2—C1—C6—C5 | 0.4 (4) | C8—C9—C13—O1 | 179.3 (3) |
N1—C1—C6—C5 | 178.5 (2) | C10—C9—C13—O1 | −1.6 (4) |
C12—C7—C8—C9 | −1.1 (4) | C6—C1—N1—N2 | 7.8 (3) |
N2—C7—C8—C9 | 178.2 (2) | C2—C1—N1—N2 | −174.02 (19) |
C7—C8—C9—C10 | 0.4 (4) | C1—N1—N2—C7 | −179.2 (2) |
C7—C8—C9—C13 | 179.6 (2) | C8—C7—N2—N1 | −178.6 (2) |
C8—C9—C10—O2 | −179.5 (2) | C12—C7—N2—N1 | 0.7 (3) |
C13—C9—C10—O2 | 1.4 (4) | C12—C11—O3—C14 | 7.2 (4) |
C8—C9—C10—C11 | 0.4 (4) | C10—C11—O3—C14 | −172.2 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O1 | 0.82 | 1.92 | 2.640 (3) | 146 |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C15H14N2O3 | C15H14N2O3 |
Mr | 270.28 | 270.28 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, Cc |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 6.746 (5), 12.529 (5), 15.556 (5) | 10.734 (5), 14.786 (5), 8.533 (5) |
β (°) | 91.842 (5) | 97.053 (5) |
V (Å3) | 1314.1 (12) | 1344.0 (11) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 |
Crystal size (mm) | 0.50 × 0.35 × 0.25 | 0.60 × 0.33 × 0.13 |
|
Data collection |
Diffractometer | Stoe IPDS-II diffractometer | Stoe IPDS-II diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10018, 3361, 1784 | 9238, 1307, 1052 |
Rint | 0.119 | 0.077 |
(sin θ/λ)max (Å−1) | 0.676 | 0.615 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.098, 0.84 | 0.031, 0.078, 0.93 |
No. of reflections | 3361 | 1307 |
No. of parameters | 216 | 185 |
No. of restraints | 0 | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.20 | 0.12, −0.11 |
Selected geometric parameters (Å, º) for (I) topC1—N1 | 1.426 (2) | C13—O1 | 1.224 (2) |
C7—N2 | 1.426 (2) | C14—O3 | 1.413 (2) |
C10—O2 | 1.350 (2) | N1—N2 | 1.248 (2) |
C11—O3 | 1.362 (2) | | |
| | | |
C2—C1—N1 | 116.1 (1) | O3—C11—C12 | 125.7 (2) |
C6—C1—N1 | 124.6 (1) | O3—C11—C10 | 114.9 (2) |
C8—C7—N2 | 125.2 (1) | O1—C13—C9 | 124.1 (1) |
C12—C7—N2 | 115.1 (1) | N2—N1—C1 | 114.2 (2) |
O2—C10—C11 | 118.6 (2) | N1—N2—C7 | 114.1 (2) |
O2—C10—C9 | 121.7 (2) | C11—O3—C14 | 117.9 (2) |
C11—C10—C9 | 119.7 (1) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13···O3i | 1.01 (2) | 2.39 (1) | 3.205 (2) | 137.3 (10) |
C2—H2···O1i | 0.97 (2) | 2.60 (2) | 3.567 (2) | 172.7 (11) |
O2—H2O···O1 | 0.97 (2) | 1.68 (2) | 2.611 (2) | 159.1 (16) |
Symmetry code: (i) −x+2, y−1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (II) topC1—N1 | 1.427 (3) | C13—O1 | 1.234 (4) |
C7—N2 | 1.418 (3) | C14—O3 | 1.429 (4) |
C10—O2 | 1.344 (4) | N1—N2 | 1.251 (3) |
C11—O3 | 1.364 (3) | | |
| | | |
C6—C1—N1 | 123.7 (2) | O3—C11—C12 | 126.1 (2) |
C2—C1—N1 | 116.0 (2) | O3—C11—C10 | 113.8 (2) |
C8—C7—N2 | 116.1 (2) | O1—C13—C9 | 124.5 (3) |
C12—C7—N2 | 124.2 (2) | N2—N1—C1 | 114.4 (2) |
O2—C10—C9 | 122.3 (2) | N1—N2—C7 | 114.6 (2) |
O2—C10—C11 | 118.1 (3) | C11—O3—C14 | 116.6 (2) |
C9—C10—C11 | 119.6 (2) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2O···O1 | 0.82 | 1.92 | 2.640 (3) | 146 |
Diazenes have been the most widely used class of dyes owing to their versatile applications in various fields, such as dyeing textile fibres, colouring different materials, plastics, biological–medical studies, lasers, liquid crystalline displays, electro-optical devices and ink-jet printers in high-technology areas (Catino & Farris, 1985; Gregory, 1991). As part of a general study of the crystal chemistry of dyes and to provide templates for molecular modelling studies, the crystal structure of the yellow dye (I) and light-brown dye (II) have been determined.
In the azo frame, the N1—C1 and N2—C7 bond lengths [1.426 (2) and 1.426 (2) Å in (I), and 1.424 (3) and 1.421 (3) Å in (II), respectively] indicate significant single-bond character, whereas the –N=N– bond lengths [1.248 (2) Å in (I) and 1.250 (2) Å in (II)] are indicative of significant double-bond character. Similar values have been observed in other trans-azo compounds (Alder et al., 1999; Alder et al., 2001; Dimmock et al., 1997; Odabaşoǧlu et al., 2003; Ersanlı, Albayrak et al., 2004; Ersanlı, Odabaşoǧlu et al., 2004; Koşar et al., 2004). The aromatic rings are in a trans conformation with respect to the azo double-bond. The C14—O3 bond length [1.413 (2) in (I) and 1.429 (3) Å in (II)] is approximately equal to that usually associated with a methyl C—O bond in a methoxy group attached to an aromatic ring (1.424 Å; Allen et al., 1987).
The structures of both (I) and (II) contain two essentially planar fragments, viz. one monosubstituted (C1–C6) and one trisubstituted phenyl ring (C7–C12). The largest deviations from the mean plane of these rings are 0.007 (1) and 0.002 (3) Å for (I), and 0.002 (1) and 0.006 (2) Å for (II), respectively. In (I), the dihedral angle, θ1, between the mean planes of the C1–C6 phenyl ring and the C1—N1=N2—C7 azo bridge is 1.24 (7)° and the angle, θ2, between the C1—N1=N2—C7 azo group and the substituted C7–C12 phenyl ring is 1.06 (6)°. The angle, θ3, between the two rings is 0.53 (4)°, i.e. the phenyl rings are nearly coplanar. Compound (I) has strong intramolecular O—H···O [O···O=2.611 (2) Å] and weak intermolecular C—H···O [C···O=3.205 (2) Å and C···O=3.567 (2) Å] hydrogen bonds (see Table 2 for details). The weak π–π stacking involves the p-tolyl ring (centroid Cg2). The weak intermolecular hydorgen bonds result in the formation of layers parallel to the (010) plane (Fig. 3). π–π stacking interactions between these layers form a three-dimensionnal network. The ring in the molecule at (x, y, z) stacks above the ring at (1 − x, −y, −z), with a distance of 3.812 (3) Å between the ring centroids and a perpendicular distance between the rings of 3.479 (1) Å. In (II), the dihedral angle, θ1, between the mean planes of the C1–C6 phenyl ring and the C1—N1=N2—C7 azo bridge is 7.05 (2)°, and the angle, θ2, between the C1—N1=N2—C7 azo group and the substituted C7—C12 phenyl ring is 1.70 (1)°. The dihedral angle, θ3, between the two rings, 8.23 (7)°, is larger than that in (I), and the two phenyl rings are slightly twisted with respect to one another. As in (I), compound (II) has a strong intramolecular O—H···O [O···O=2.611 (2) Å] hydrogen bond (see Table 4 for details). The weak π–π stacking involves the o-tolyl ring (centroid Cg2). The ring in the molecule at (x, y, z) stacks above the ring at (x, y, 1 + z), with a distance of 3.917 (3) Å between the ring centroids and a perpendicular distance between the rings of 3.410 (1) Å.