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The title compounds, (
Z)-4-(2,6-dichlorophenyldiazenyl)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxycyclohexa-2,4-dienone, C
18H
19Cl
2N
3O
5, (I), (
Z)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxy-4-(3-methoxyphenyldiazenyl)cyclohexa-2,4-dienone, C
19H
23N
3O
6, (II), and (
Z)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxy-4-(4-methoxyphenyldiazenyl)cyclohexa-2,4-dienone, C
19H
23N
3O
6, (III), all adopt the keto–amine tautomeric form, and the hydroxy H atoms are located on the N atom in all three compounds. Strong intramolecular N—H
O hydrogen bonds arise as a result of the shifts achieved by the hydroxy H atoms of the Schiff bases to the N atoms. Positional disorder was observed in molecules (II) and (III). In all three compounds, C—H
π and π–π interactions affect the packing of the molecules. The compounds exhibit
trans geometry with respect to the azo N=N double bond, and the molecules are linked by O—H
O hydrogen bonds to form three-dimensional networks.
Supporting information
CCDC references: 605679; 605680; 605681
Compounds (I), (II) and (III) were prepared as described in the literature (Odabaşoǧlu et al., Albayrak, Büyükgüngör & Lönnecke, 2003)?????? using o-vanillin, 2.6-dichloroaniline for (I), 3-methoxyaniline for (II), 4-methoxyaniline for (III) and tris(hydroxymethyl)aminomethane as starting materials. The product was crystallized from ethanol, and well shaped crystals were obtained by slow evaporation of a ethanol solution [yield 74%, m.p. 480–482 K for (I); yield 76%, m.p. 462–463 K for (II);
yield 78%, m.p. 489–490 K for (III)].
H atoms attached to N and O atoms were refined freely. All remaining H atoms were refined using a riding model, with C—H distances of 0.93–0.97 Å. In (III), the H atoms of C18 were refined at two different positions owing to disorder, with 0.5 occupancy for each component. The Uiso(H) values are 1.5Ueq(C) for the methyl H atoms and 1.2Ueq(C) for the remaining C-bound H atoms.
For all 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, 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) (
Z)-4-(2,6-dichlorophenyldiazenyl)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan- 2-ylamino]methylene}-2-methoxycyclohexa-2,4-dienone
top
Crystal data top
C18H19Cl2N3O5 | F(000) = 888 |
Mr = 428.26 | Dx = 1.474 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 12750 reflections |
a = 16.8445 (15) Å | θ = 1.9–28.4° |
b = 10.7259 (5) Å | µ = 0.37 mm−1 |
c = 11.1126 (9) Å | T = 296 K |
β = 106.037 (7)° | Stick, red |
V = 1929.6 (2) Å3 | 0.78 × 0.33 × 0.05 mm |
Z = 4 | |
Data collection top
STOE IPDS-II diffractometer | 3782 independent reflections |
Radiation source: fine-focus sealed tube | 2715 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.3° |
ω scans | h = −20→20 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −11→13 |
Tmin = 0.871, Tmax = 0.977 | l = −13→12 |
10068 measured reflections | |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0754P)2 + 0.1273P] where P = (Fo2 + 2Fc2)/3 |
3782 reflections | (Δ/σ)max < 0.001 |
269 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C18H19Cl2N3O5 | V = 1929.6 (2) Å3 |
Mr = 428.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.8445 (15) Å | µ = 0.37 mm−1 |
b = 10.7259 (5) Å | T = 296 K |
c = 11.1126 (9) Å | 0.78 × 0.33 × 0.05 mm |
β = 106.037 (7)° | |
Data collection top
STOE IPDS-II diffractometer | 3782 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 2715 reflections with I > 2σ(I) |
Tmin = 0.871, Tmax = 0.977 | Rint = 0.056 |
10068 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.132 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.31 e Å−3 |
3782 reflections | Δρmin = −0.36 e Å−3 |
269 parameters | |
Special details top
Experimental. 135 frames, detector distance = 110 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 (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.58033 (15) | 0.5549 (2) | 0.2111 (2) | 0.0460 (6) | |
C2 | 0.50018 (17) | 0.5839 (3) | 0.2154 (3) | 0.0551 (7) | |
C3 | 0.44778 (19) | 0.6504 (3) | 0.1201 (3) | 0.0706 (9) | |
H3 | 0.3948 | 0.6698 | 0.1243 | 0.085* | |
C4 | 0.4730 (2) | 0.6877 (3) | 0.0203 (3) | 0.0801 (10) | |
H4 | 0.4375 | 0.7343 | −0.0425 | 0.096* | |
C5 | 0.5509 (2) | 0.6575 (3) | 0.0099 (3) | 0.0690 (8) | |
H5 | 0.5677 | 0.6820 | −0.0595 | 0.083* | |
C6 | 0.60314 (17) | 0.5899 (3) | 0.1060 (2) | 0.0544 (6) | |
C7 | 0.70689 (13) | 0.4967 (2) | 0.5165 (2) | 0.0389 (5) | |
C8 | 0.71827 (13) | 0.5702 (2) | 0.6250 (2) | 0.0405 (5) | |
H8 | 0.6919 | 0.6470 | 0.6195 | 0.049* | |
C9 | 0.76720 (13) | 0.5310 (2) | 0.7379 (2) | 0.0393 (5) | |
C10 | 0.80919 (12) | 0.4135 (2) | 0.7498 (2) | 0.0350 (5) | |
C11 | 0.80026 (13) | 0.3442 (2) | 0.6365 (2) | 0.0362 (5) | |
C12 | 0.74816 (14) | 0.3857 (2) | 0.5217 (2) | 0.0399 (5) | |
H12 | 0.7417 | 0.3382 | 0.4496 | 0.048* | |
C13 | 0.84882 (13) | 0.2351 (2) | 0.6384 (2) | 0.0373 (5) | |
H13 | 0.8428 | 0.1909 | 0.5644 | 0.045* | |
C14 | 0.95897 (13) | 0.09159 (19) | 0.75662 (19) | 0.0340 (4) | |
C15 | 0.96751 (14) | 0.0380 (2) | 0.6337 (2) | 0.0399 (5) | |
H15A | 0.9701 | 0.1060 | 0.5774 | 0.048* | |
H15B | 1.0189 | −0.0082 | 0.6499 | 0.048* | |
C16 | 0.92724 (14) | −0.0049 (2) | 0.8336 (2) | 0.0389 (5) | |
H16A | 0.9245 | 0.0315 | 0.9122 | 0.047* | |
H16B | 0.8722 | −0.0321 | 0.7880 | 0.047* | |
C17 | 1.04417 (13) | 0.1429 (2) | 0.8285 (2) | 0.0403 (5) | |
H17A | 1.0817 | 0.0740 | 0.8587 | 0.048* | |
H17B | 1.0664 | 0.1924 | 0.7723 | 0.048* | |
C18 | 0.7495 (2) | 0.7156 (3) | 0.8462 (3) | 0.0683 (8) | |
H18A | 0.7598 | 0.7457 | 0.9305 | 0.102* | |
H18B | 0.6910 | 0.7121 | 0.8078 | 0.102* | |
H18C | 0.7745 | 0.7710 | 0.7994 | 0.102* | |
Cl1 | 0.46378 (5) | 0.52727 (10) | 0.33563 (8) | 0.0797 (3) | |
Cl2 | 0.70005 (5) | 0.54926 (9) | 0.09348 (8) | 0.0764 (3) | |
N1 | 0.63785 (13) | 0.4885 (2) | 0.31082 (19) | 0.0498 (5) | |
N2 | 0.65194 (12) | 0.55064 (18) | 0.40892 (19) | 0.0435 (5) | |
N3 | 0.90058 (11) | 0.19559 (17) | 0.73893 (18) | 0.0352 (4) | |
O1 | 0.78373 (12) | 0.59483 (17) | 0.84753 (16) | 0.0551 (5) | |
O3 | 0.85420 (10) | 0.37752 (14) | 0.85661 (14) | 0.0420 (4) | |
O4 | 1.03869 (11) | 0.21784 (17) | 0.93174 (15) | 0.0443 (4) | |
O5 | 0.98183 (12) | −0.10746 (16) | 0.85653 (19) | 0.0531 (5) | |
O6 | 0.90118 (12) | −0.04188 (16) | 0.57467 (18) | 0.0471 (4) | |
H33 | 0.9027 (16) | 0.237 (3) | 0.799 (3) | 0.051 (8)* | |
H44 | 1.0575 (17) | 0.280 (3) | 0.929 (3) | 0.050 (8)* | |
H55 | 0.979 (2) | −0.140 (3) | 0.920 (3) | 0.068 (10)* | |
H66 | 0.8821 (17) | −0.022 (3) | 0.513 (3) | 0.043 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0480 (13) | 0.0433 (13) | 0.0390 (12) | −0.0016 (10) | −0.0010 (10) | −0.0006 (10) |
C2 | 0.0516 (14) | 0.0561 (15) | 0.0520 (15) | −0.0015 (12) | 0.0052 (12) | −0.0032 (12) |
C3 | 0.0573 (17) | 0.0675 (19) | 0.075 (2) | 0.0084 (14) | −0.0016 (15) | 0.0042 (17) |
C4 | 0.083 (2) | 0.066 (2) | 0.068 (2) | 0.0027 (17) | −0.0173 (17) | 0.0144 (17) |
C5 | 0.083 (2) | 0.0666 (18) | 0.0476 (16) | −0.0127 (16) | 0.0010 (14) | 0.0128 (14) |
C6 | 0.0557 (14) | 0.0570 (15) | 0.0447 (14) | −0.0117 (12) | 0.0042 (11) | −0.0016 (12) |
C7 | 0.0376 (11) | 0.0376 (11) | 0.0389 (12) | 0.0030 (9) | 0.0060 (9) | 0.0064 (10) |
C8 | 0.0388 (11) | 0.0363 (11) | 0.0444 (13) | 0.0076 (9) | 0.0084 (9) | 0.0028 (10) |
C9 | 0.0399 (11) | 0.0387 (12) | 0.0391 (12) | 0.0051 (9) | 0.0107 (9) | −0.0013 (9) |
C10 | 0.0335 (10) | 0.0360 (11) | 0.0352 (11) | 0.0001 (8) | 0.0093 (8) | 0.0016 (9) |
C11 | 0.0391 (11) | 0.0331 (10) | 0.0349 (11) | 0.0014 (9) | 0.0076 (8) | 0.0016 (9) |
C12 | 0.0433 (12) | 0.0390 (12) | 0.0343 (11) | 0.0014 (9) | 0.0056 (9) | −0.0010 (9) |
C13 | 0.0429 (11) | 0.0336 (10) | 0.0346 (11) | 0.0022 (9) | 0.0091 (9) | −0.0014 (9) |
C14 | 0.0403 (11) | 0.0279 (10) | 0.0331 (11) | 0.0047 (8) | 0.0092 (8) | 0.0025 (8) |
C15 | 0.0478 (12) | 0.0375 (11) | 0.0354 (11) | 0.0075 (9) | 0.0130 (9) | 0.0024 (9) |
C16 | 0.0497 (12) | 0.0339 (11) | 0.0335 (11) | 0.0009 (9) | 0.0118 (9) | 0.0023 (9) |
C17 | 0.0434 (12) | 0.0372 (11) | 0.0397 (12) | 0.0016 (9) | 0.0106 (9) | 0.0034 (9) |
C18 | 0.096 (2) | 0.0484 (15) | 0.0555 (16) | 0.0269 (15) | 0.0134 (15) | −0.0101 (13) |
Cl1 | 0.0630 (5) | 0.1070 (7) | 0.0731 (5) | −0.0062 (4) | 0.0257 (4) | 0.0000 (5) |
Cl2 | 0.0646 (5) | 0.1003 (6) | 0.0664 (5) | −0.0108 (4) | 0.0216 (4) | −0.0097 (4) |
N1 | 0.0538 (12) | 0.0466 (11) | 0.0432 (11) | 0.0050 (9) | 0.0037 (9) | −0.0004 (9) |
N2 | 0.0414 (10) | 0.0441 (10) | 0.0408 (11) | −0.0002 (8) | 0.0042 (8) | 0.0021 (9) |
N3 | 0.0419 (10) | 0.0309 (9) | 0.0326 (9) | 0.0049 (7) | 0.0097 (7) | 0.0002 (8) |
O1 | 0.0714 (11) | 0.0492 (10) | 0.0392 (9) | 0.0244 (8) | 0.0062 (8) | −0.0073 (8) |
O3 | 0.0496 (9) | 0.0415 (9) | 0.0326 (8) | 0.0110 (7) | 0.0073 (7) | 0.0013 (7) |
O4 | 0.0562 (10) | 0.0336 (9) | 0.0402 (9) | −0.0076 (8) | 0.0082 (7) | 0.0001 (7) |
O5 | 0.0787 (13) | 0.0352 (9) | 0.0476 (10) | 0.0140 (8) | 0.0212 (9) | 0.0115 (8) |
O6 | 0.0642 (11) | 0.0398 (9) | 0.0318 (9) | 0.0029 (8) | 0.0042 (8) | −0.0021 (7) |
Geometric parameters (Å, º) top
C1—C6 | 1.378 (4) | C13—N3 | 1.284 (3) |
C1—C2 | 1.399 (4) | C13—H13 | 0.9300 |
C1—N1 | 1.443 (3) | C14—N3 | 1.464 (3) |
C2—C3 | 1.375 (4) | C14—C15 | 1.525 (3) |
C2—Cl1 | 1.727 (3) | C14—C16 | 1.530 (3) |
C3—C4 | 1.354 (5) | C14—C17 | 1.538 (3) |
C3—H3 | 0.9300 | C15—O6 | 1.417 (3) |
C4—C5 | 1.387 (5) | C15—H15A | 0.9700 |
C4—H4 | 0.9300 | C15—H15B | 0.9700 |
C5—C6 | 1.386 (4) | C16—O5 | 1.411 (3) |
C5—H5 | 0.9300 | C16—H16A | 0.9700 |
C6—Cl2 | 1.732 (3) | C16—H16B | 0.9700 |
C7—C12 | 1.372 (3) | C17—O4 | 1.425 (3) |
C7—C8 | 1.409 (3) | C17—H17A | 0.9700 |
C7—N2 | 1.417 (3) | C17—H17B | 0.9700 |
C8—C9 | 1.364 (3) | C18—O1 | 1.417 (3) |
C8—H8 | 0.9300 | C18—H18A | 0.9600 |
C9—O1 | 1.357 (3) | C18—H18B | 0.9600 |
C9—C10 | 1.434 (3) | C18—H18C | 0.9600 |
C10—O3 | 1.279 (3) | N1—N2 | 1.243 (3) |
C10—C11 | 1.434 (3) | N3—H33 | 0.79 (3) |
C11—C12 | 1.406 (3) | O4—H44 | 0.74 (3) |
C11—C13 | 1.425 (3) | O5—H55 | 0.80 (4) |
C12—H12 | 0.9300 | O6—H66 | 0.70 (3) |
| | | |
C6—C1—C2 | 117.8 (2) | N3—C14—C15 | 113.15 (17) |
C6—C1—N1 | 120.0 (2) | N3—C14—C16 | 105.37 (17) |
C2—C1—N1 | 122.2 (2) | C15—C14—C16 | 112.28 (18) |
C3—C2—C1 | 120.6 (3) | N3—C14—C17 | 107.04 (17) |
C3—C2—Cl1 | 119.2 (2) | C15—C14—C17 | 107.13 (18) |
C1—C2—Cl1 | 120.0 (2) | C16—C14—C17 | 111.82 (18) |
C4—C3—C2 | 120.3 (3) | O6—C15—C14 | 112.68 (19) |
C4—C3—H3 | 119.9 | O6—C15—H15A | 109.1 |
C2—C3—H3 | 119.9 | C14—C15—H15A | 109.1 |
C3—C4—C5 | 121.2 (3) | O6—C15—H15B | 109.1 |
C3—C4—H4 | 119.4 | C14—C15—H15B | 109.1 |
C5—C4—H4 | 119.4 | H15A—C15—H15B | 107.8 |
C6—C5—C4 | 118.2 (3) | O5—C16—C14 | 108.52 (19) |
C6—C5—H5 | 120.9 | O5—C16—H16A | 110.0 |
C4—C5—H5 | 120.9 | C14—C16—H16A | 110.0 |
C1—C6—C5 | 122.0 (3) | O5—C16—H16B | 110.0 |
C1—C6—Cl2 | 119.3 (2) | C14—C16—H16B | 110.0 |
C5—C6—Cl2 | 118.8 (3) | H16A—C16—H16B | 108.4 |
C12—C7—C8 | 120.16 (19) | O4—C17—C14 | 111.17 (18) |
C12—C7—N2 | 126.5 (2) | O4—C17—H17A | 109.4 |
C8—C7—N2 | 113.35 (19) | C14—C17—H17A | 109.4 |
C9—C8—C7 | 121.3 (2) | O4—C17—H17B | 109.4 |
C9—C8—H8 | 119.3 | C14—C17—H17B | 109.4 |
C7—C8—H8 | 119.3 | H17A—C17—H17B | 108.0 |
O1—C9—C8 | 126.3 (2) | O1—C18—H18A | 109.5 |
O1—C9—C10 | 112.76 (19) | O1—C18—H18B | 109.5 |
C8—C9—C10 | 120.9 (2) | H18A—C18—H18B | 109.5 |
O3—C10—C9 | 120.1 (2) | O1—C18—H18C | 109.5 |
O3—C10—C11 | 123.37 (19) | H18A—C18—H18C | 109.5 |
C9—C10—C11 | 116.44 (18) | H18B—C18—H18C | 109.5 |
C12—C11—C13 | 119.0 (2) | N2—N1—C1 | 109.5 (2) |
C12—C11—C10 | 121.38 (19) | N1—N2—C7 | 116.28 (19) |
C13—C11—C10 | 119.47 (18) | C13—N3—C14 | 129.6 (2) |
C7—C12—C11 | 119.6 (2) | C13—N3—H33 | 114 (2) |
C7—C12—H12 | 120.2 | C14—N3—H33 | 116 (2) |
C11—C12—H12 | 120.2 | C9—O1—C18 | 118.02 (19) |
N3—C13—C11 | 122.2 (2) | C17—O4—H44 | 111 (2) |
N3—C13—H13 | 118.9 | C16—O5—H55 | 107 (2) |
C11—C13—H13 | 118.9 | C15—O6—H66 | 111 (2) |
| | | |
C6—C1—C2—C3 | −3.1 (4) | C8—C7—C12—C11 | 1.6 (3) |
N1—C1—C2—C3 | 178.2 (3) | N2—C7—C12—C11 | −179.4 (2) |
C6—C1—C2—Cl1 | 172.6 (2) | C13—C11—C12—C7 | −174.0 (2) |
N1—C1—C2—Cl1 | −6.2 (3) | C10—C11—C12—C7 | 2.1 (3) |
C1—C2—C3—C4 | 0.6 (5) | C12—C11—C13—N3 | 176.5 (2) |
Cl1—C2—C3—C4 | −175.1 (3) | C10—C11—C13—N3 | 0.3 (3) |
C2—C3—C4—C5 | 1.6 (5) | N3—C14—C15—O6 | −78.6 (2) |
C3—C4—C5—C6 | −1.2 (5) | C16—C14—C15—O6 | 40.5 (2) |
C2—C1—C6—C5 | 3.4 (4) | C17—C14—C15—O6 | 163.68 (17) |
N1—C1—C6—C5 | −177.7 (2) | N3—C14—C16—O5 | −178.82 (18) |
C2—C1—C6—Cl2 | −176.9 (2) | C15—C14—C16—O5 | 57.6 (2) |
N1—C1—C6—Cl2 | 1.9 (3) | C17—C14—C16—O5 | −62.9 (2) |
C4—C5—C6—C1 | −1.4 (4) | N3—C14—C17—O4 | 46.1 (2) |
C4—C5—C6—Cl2 | 179.0 (2) | C15—C14—C17—O4 | 167.76 (17) |
C12—C7—C8—C9 | −2.9 (4) | C16—C14—C17—O4 | −68.8 (2) |
N2—C7—C8—C9 | 178.0 (2) | C6—C1—N1—N2 | 119.3 (3) |
C7—C8—C9—O1 | 178.7 (2) | C2—C1—N1—N2 | −62.0 (3) |
C7—C8—C9—C10 | 0.3 (4) | C1—N1—N2—C7 | 179.2 (2) |
O1—C9—C10—O3 | 2.1 (3) | C12—C7—N2—N1 | 2.7 (4) |
C8—C9—C10—O3 | −179.3 (2) | C8—C7—N2—N1 | −178.3 (2) |
O1—C9—C10—C11 | −175.4 (2) | C11—C13—N3—C14 | −175.4 (2) |
C8—C9—C10—C11 | 3.2 (3) | C15—C14—N3—C13 | 10.7 (3) |
O3—C10—C11—C12 | 178.1 (2) | C16—C14—N3—C13 | −112.3 (2) |
C9—C10—C11—C12 | −4.5 (3) | C17—C14—N3—C13 | 128.5 (2) |
O3—C10—C11—C13 | −5.7 (3) | C8—C9—O1—C18 | −2.0 (4) |
C9—C10—C11—C13 | 171.7 (2) | C10—C9—O1—C18 | 176.5 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H33···O3 | 0.79 (3) | 1.90 (3) | 2.587 (2) | 144 (3) |
O4—H44···O6i | 0.74 (3) | 2.04 (3) | 2.777 (3) | 174 (3) |
O5—H55···O4ii | 0.80 (4) | 1.94 (4) | 2.740 (3) | 176 (3) |
O6—H66···O1iii | 0.70 (3) | 2.25 (3) | 2.802 (2) | 137 (3) |
O6—H66···O3iii | 0.70 (3) | 2.28 (3) | 2.923 (2) | 153 (3) |
C17—H17A···G1iv | 0.97 (1) | 2.95 (1) | 3.798 (2) | 147 (1) |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, −y, −z+2; (iii) x, −y+1/2, z−1/2; (iv) −x, y+1/2, −z+1/2. |
(II) (
Z)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxy- 4-(3-methoxyphenyldiazenyl)cyclohexa-2,4-dienone
top
Crystal data top
C19H23N3O6 | F(000) = 824 |
Mr = 389.40 | Dx = 1.352 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 13037 reflections |
a = 16.3722 (11) Å | θ = 1.8–28.9° |
b = 10.4506 (5) Å | µ = 0.10 mm−1 |
c = 11.3239 (7) Å | T = 296 K |
β = 99.180 (5)° | Prism, red |
V = 1912.7 (2) Å3 | 0.42 × 0.33 × 0.25 mm |
Z = 4 | |
Data collection top
STOE IPDS-II diffractometer | 3744 independent reflections |
Radiation source: fine-focus sealed tube | 2778 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.3° |
ω scans | h = −20→20 |
Absorption correction: integration STOE X-RED (Stoe & Cie, 2002) | k = −12→12 |
Tmin = 0.970, Tmax = 0.982 | l = −13→13 |
13464 measured reflections | |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.160 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0982P)2 + 0.2314P] where P = (Fo2 + 2Fc2)/3 |
3744 reflections | (Δ/σ)max < 0.001 |
280 parameters | Δρmax = 0.83 e Å−3 |
3 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
C19H23N3O6 | V = 1912.7 (2) Å3 |
Mr = 389.40 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.3722 (11) Å | µ = 0.10 mm−1 |
b = 10.4506 (5) Å | T = 296 K |
c = 11.3239 (7) Å | 0.42 × 0.33 × 0.25 mm |
β = 99.180 (5)° | |
Data collection top
STOE IPDS-II diffractometer | 3744 independent reflections |
Absorption correction: integration STOE X-RED (Stoe & Cie, 2002) | 2778 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.982 | Rint = 0.040 |
13464 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 3 restraints |
wR(F2) = 0.160 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.83 e Å−3 |
3744 reflections | Δρmin = −0.32 e Å−3 |
280 parameters | |
Special details top
Experimental. 180 frames, detector distance = 100 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 (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.52543 (13) | 0.3349 (2) | 0.4226 (2) | 0.0519 (5) | |
C2 | 0.48686 (16) | 0.2193 (3) | 0.4415 (3) | 0.0682 (7) | |
H2 | 0.5041 | 0.1736 | 0.5115 | 0.082* | |
C3 | 0.42448 (17) | 0.1724 (3) | 0.3592 (3) | 0.0748 (8) | |
C4 | 0.39987 (16) | 0.2401 (3) | 0.2573 (3) | 0.0801 (9) | |
H4 | 0.3571 | 0.2089 | 0.2006 | 0.096* | |
C5 | 0.43803 (17) | 0.3562 (4) | 0.2363 (3) | 0.0793 (9) | |
H5 | 0.4209 | 0.4008 | 0.1656 | 0.095* | |
C6 | 0.50125 (15) | 0.4050 (3) | 0.3205 (2) | 0.0623 (6) | |
H6 | 0.5264 | 0.4825 | 0.3081 | 0.075* | |
C7 | 0.69341 (12) | 0.49355 (19) | 0.59813 (17) | 0.0418 (4) | |
C8 | 0.70470 (13) | 0.4220 (2) | 0.70539 (19) | 0.0479 (5) | |
H8 | 0.6738 | 0.3481 | 0.7104 | 0.058* | |
C9 | 0.75977 (13) | 0.4594 (2) | 0.80069 (17) | 0.0454 (5) | |
C10 | 0.80727 (11) | 0.57554 (17) | 0.79880 (16) | 0.0380 (4) | |
C11 | 0.79952 (12) | 0.64124 (17) | 0.68721 (16) | 0.0370 (4) | |
C12 | 0.74184 (12) | 0.59894 (19) | 0.58899 (17) | 0.0423 (4) | |
H12 | 0.7366 | 0.6432 | 0.5169 | 0.051* | |
C13 | 0.84989 (12) | 0.74918 (17) | 0.67492 (16) | 0.0387 (4) | |
H13 | 0.8448 | 0.7902 | 0.6013 | 0.046* | |
C14 | 0.96009 (12) | 0.89996 (16) | 0.76805 (15) | 0.0361 (4) | |
C15 | 1.04588 (12) | 0.85128 (18) | 0.82383 (17) | 0.0415 (4) | |
H15A | 1.0686 | 0.7993 | 0.7659 | 0.050* | |
H15B | 1.0825 | 0.9236 | 0.8444 | 0.050* | |
C16 | 0.92688 (13) | 0.99893 (17) | 0.84776 (16) | 0.0416 (4) | |
H16A | 0.8722 | 1.0269 | 0.8108 | 0.050* | |
H16B | 0.9224 | 0.9611 | 0.9247 | 0.050* | |
C17 | 0.96765 (13) | 0.95486 (18) | 0.64533 (16) | 0.0415 (4) | |
H17A | 1.0184 | 1.0040 | 0.6516 | 0.050* | |
H17B | 0.9714 | 0.8849 | 0.5902 | 0.050* | |
C18A | 0.7450 (17) | 0.268 (2) | 0.9174 (13) | 0.094 (4) | 0.64 (7) |
H18A | 0.7616 | 0.2370 | 0.9975 | 0.141* | 0.64 (7) |
H18B | 0.7667 | 0.2125 | 0.8623 | 0.141* | 0.64 (7) |
H18C | 0.6857 | 0.2693 | 0.8990 | 0.141* | 0.64 (7) |
C18B | 0.725 (2) | 0.298 (4) | 0.9220 (17) | 0.081 (6) | 0.36 (7) |
H18D | 0.7413 | 0.2606 | 0.9997 | 0.121* | 0.36 (7) |
H18E | 0.7286 | 0.2343 | 0.8617 | 0.121* | 0.36 (7) |
H18F | 0.6695 | 0.3288 | 0.9147 | 0.121* | 0.36 (7) |
C19 | 0.3212 (2) | 0.0104 (4) | 0.3150 (4) | 0.1198 (15) | |
H19A | 0.2745 | 0.0641 | 0.3211 | 0.180* | |
H19B | 0.3098 | −0.0753 | 0.3381 | 0.180* | |
H19C | 0.3315 | 0.0104 | 0.2339 | 0.180* | |
N1 | 0.58852 (11) | 0.36940 (18) | 0.51846 (16) | 0.0505 (4) | |
N2 | 0.63259 (11) | 0.46281 (16) | 0.49844 (15) | 0.0462 (4) | |
N3 | 0.90261 (10) | 0.79222 (14) | 0.76302 (14) | 0.0372 (4) | |
O1 | 0.39043 (17) | 0.0567 (3) | 0.3900 (2) | 0.1122 (9) | |
O2 | 0.77720 (12) | 0.39743 (16) | 0.90751 (15) | 0.0679 (5) | |
O3 | 0.85535 (9) | 0.61238 (13) | 0.89346 (11) | 0.0445 (4) | |
O4 | 1.04182 (10) | 0.77718 (13) | 0.92855 (12) | 0.0459 (4) | |
O5 | 0.98120 (11) | 1.10454 (13) | 0.86388 (13) | 0.0543 (4) | |
O6 | 0.90017 (10) | 1.03429 (13) | 0.59828 (12) | 0.0483 (4) | |
H33 | 0.9020 (14) | 0.751 (2) | 0.828 (2) | 0.049 (6)* | |
H44 | 1.0605 (16) | 0.7055 (19) | 0.919 (2) | 0.070 (8)* | |
H55 | 0.9770 (17) | 1.144 (2) | 0.9268 (19) | 0.072 (8)* | |
H66 | 0.8772 (16) | 1.003 (3) | 0.5358 (19) | 0.070 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0416 (11) | 0.0629 (14) | 0.0513 (12) | −0.0114 (10) | 0.0075 (9) | −0.0190 (10) |
C2 | 0.0619 (15) | 0.0732 (16) | 0.0691 (15) | −0.0238 (13) | 0.0099 (12) | −0.0196 (13) |
C3 | 0.0614 (15) | 0.0865 (19) | 0.0757 (18) | −0.0238 (15) | 0.0090 (14) | −0.0278 (16) |
C4 | 0.0463 (13) | 0.099 (2) | 0.091 (2) | −0.0131 (14) | 0.0005 (13) | −0.0468 (18) |
C5 | 0.0619 (16) | 0.113 (2) | 0.0592 (15) | 0.0141 (17) | −0.0016 (12) | −0.0168 (15) |
C6 | 0.0509 (13) | 0.0771 (16) | 0.0573 (13) | −0.0010 (12) | 0.0039 (11) | −0.0133 (12) |
C7 | 0.0417 (10) | 0.0415 (10) | 0.0405 (10) | −0.0043 (8) | 0.0009 (8) | −0.0045 (8) |
C8 | 0.0480 (11) | 0.0414 (10) | 0.0527 (12) | −0.0118 (9) | 0.0027 (9) | 0.0007 (9) |
C9 | 0.0467 (11) | 0.0434 (10) | 0.0439 (10) | −0.0076 (9) | 0.0009 (9) | 0.0083 (8) |
C10 | 0.0399 (10) | 0.0355 (9) | 0.0373 (9) | −0.0010 (8) | 0.0026 (8) | −0.0005 (7) |
C11 | 0.0416 (10) | 0.0316 (8) | 0.0363 (9) | −0.0024 (8) | 0.0014 (8) | −0.0009 (7) |
C12 | 0.0496 (11) | 0.0402 (10) | 0.0353 (9) | −0.0041 (8) | 0.0008 (8) | −0.0002 (8) |
C13 | 0.0489 (11) | 0.0324 (9) | 0.0333 (9) | −0.0022 (8) | 0.0024 (8) | 0.0003 (7) |
C14 | 0.0461 (10) | 0.0282 (8) | 0.0330 (8) | −0.0047 (7) | 0.0027 (7) | −0.0007 (7) |
C15 | 0.0462 (11) | 0.0354 (9) | 0.0412 (9) | −0.0037 (8) | 0.0020 (8) | −0.0010 (8) |
C16 | 0.0564 (12) | 0.0324 (9) | 0.0350 (9) | −0.0014 (8) | 0.0047 (8) | −0.0012 (7) |
C17 | 0.0534 (11) | 0.0355 (9) | 0.0351 (9) | −0.0057 (8) | 0.0055 (8) | 0.0014 (7) |
C18A | 0.092 (8) | 0.058 (7) | 0.118 (8) | −0.037 (6) | −0.023 (4) | 0.044 (4) |
C18B | 0.122 (14) | 0.055 (10) | 0.054 (8) | −0.021 (9) | −0.020 (6) | 0.041 (5) |
C19 | 0.081 (2) | 0.133 (3) | 0.146 (4) | −0.050 (2) | 0.018 (2) | −0.049 (3) |
N1 | 0.0474 (10) | 0.0517 (10) | 0.0511 (10) | −0.0107 (8) | 0.0041 (8) | −0.0117 (8) |
N2 | 0.0455 (9) | 0.0452 (9) | 0.0463 (9) | −0.0083 (8) | 0.0028 (7) | −0.0094 (7) |
N3 | 0.0469 (9) | 0.0308 (8) | 0.0324 (8) | −0.0044 (7) | 0.0017 (7) | 0.0013 (6) |
O1 | 0.1119 (18) | 0.1044 (18) | 0.1134 (19) | −0.0588 (16) | −0.0033 (15) | −0.0215 (14) |
O2 | 0.0788 (11) | 0.0611 (10) | 0.0564 (9) | −0.0313 (9) | −0.0118 (8) | 0.0256 (8) |
O3 | 0.0502 (8) | 0.0441 (8) | 0.0364 (7) | −0.0094 (6) | −0.0021 (6) | 0.0035 (6) |
O4 | 0.0633 (9) | 0.0330 (7) | 0.0384 (7) | 0.0060 (7) | −0.0009 (6) | −0.0010 (6) |
O5 | 0.0830 (11) | 0.0341 (7) | 0.0461 (8) | −0.0134 (7) | 0.0113 (8) | −0.0103 (6) |
O6 | 0.0701 (10) | 0.0361 (7) | 0.0342 (7) | −0.0017 (7) | −0.0058 (7) | 0.0013 (6) |
Geometric parameters (Å, º) top
C1—C6 | 1.372 (4) | C14—C16 | 1.529 (3) |
C1—C2 | 1.396 (3) | C14—C15 | 1.532 (3) |
C1—N1 | 1.420 (3) | C15—O4 | 1.427 (2) |
C2—C3 | 1.359 (4) | C15—H15A | 0.9700 |
C2—H2 | 0.9300 | C15—H15B | 0.9700 |
C3—C4 | 1.359 (5) | C16—O5 | 1.411 (2) |
C3—O1 | 1.399 (4) | C16—H16A | 0.9700 |
C4—C5 | 1.403 (5) | C16—H16B | 0.9700 |
C4—H4 | 0.9300 | C17—O6 | 1.416 (3) |
C5—C6 | 1.387 (4) | C17—H17A | 0.9700 |
C5—H5 | 0.9300 | C17—H17B | 0.9700 |
C6—H6 | 0.9300 | C18A—O2 | 1.463 (16) |
C7—C12 | 1.371 (3) | C18A—H18A | 0.9600 |
C7—C8 | 1.413 (3) | C18A—H18B | 0.9600 |
C7—N2 | 1.418 (3) | C18A—H18C | 0.9600 |
C8—C9 | 1.349 (3) | C18B—O2 | 1.37 (2) |
C8—H8 | 0.9300 | C18B—H18D | 0.9600 |
C9—O2 | 1.362 (2) | C18B—H18E | 0.9600 |
C9—C10 | 1.443 (3) | C18B—H18F | 0.9600 |
C10—O3 | 1.284 (2) | C19—O1 | 1.391 (4) |
C10—C11 | 1.426 (3) | C19—H19A | 0.9600 |
C11—C12 | 1.410 (3) | C19—H19B | 0.9600 |
C11—C13 | 1.417 (3) | C19—H19C | 0.9600 |
C12—H12 | 0.9300 | N1—N2 | 1.256 (2) |
C13—N3 | 1.291 (2) | N3—H33 | 0.86 (2) |
C13—H13 | 0.9300 | O4—H44 | 0.824 (17) |
C14—N3 | 1.463 (2) | O5—H55 | 0.836 (17) |
C14—C17 | 1.527 (2) | O6—H66 | 0.815 (17) |
| | | |
C6—C1—C2 | 121.0 (2) | O4—C15—H15A | 109.4 |
C6—C1—N1 | 125.8 (2) | C14—C15—H15A | 109.4 |
C2—C1—N1 | 113.2 (2) | O4—C15—H15B | 109.4 |
C3—C2—C1 | 121.0 (3) | C14—C15—H15B | 109.4 |
C3—C2—H2 | 119.5 | H15A—C15—H15B | 108.0 |
C1—C2—H2 | 119.5 | O5—C16—C14 | 109.24 (16) |
C4—C3—C2 | 118.9 (3) | O5—C16—H16A | 109.8 |
C4—C3—O1 | 125.8 (3) | C14—C16—H16A | 109.8 |
C2—C3—O1 | 115.2 (3) | O5—C16—H16B | 109.8 |
C3—C4—C5 | 120.9 (2) | C14—C16—H16B | 109.8 |
C3—C4—H4 | 119.5 | H16A—C16—H16B | 108.3 |
C5—C4—H4 | 119.5 | O6—C17—C14 | 113.02 (16) |
C6—C5—C4 | 120.3 (3) | O6—C17—H17A | 109.0 |
C6—C5—H5 | 119.8 | C14—C17—H17A | 109.0 |
C4—C5—H5 | 119.8 | O6—C17—H17B | 109.0 |
C1—C6—C5 | 117.8 (3) | C14—C17—H17B | 109.0 |
C1—C6—H6 | 121.1 | H17A—C17—H17B | 107.8 |
C5—C6—H6 | 121.1 | O2—C18A—H18A | 109.5 |
C12—C7—C8 | 119.48 (18) | O2—C18A—H18B | 109.5 |
C12—C7—N2 | 117.59 (17) | H18A—C18A—H18B | 109.5 |
C8—C7—N2 | 122.92 (18) | O2—C18A—H18C | 109.5 |
C9—C8—C7 | 120.88 (19) | H18A—C18A—H18C | 109.5 |
C9—C8—H8 | 119.6 | H18B—C18A—H18C | 109.5 |
C7—C8—H8 | 119.6 | O2—C18B—H18D | 109.5 |
C8—C9—O2 | 126.24 (18) | O2—C18B—H18E | 109.5 |
C8—C9—C10 | 121.66 (18) | H18D—C18B—H18E | 109.5 |
O2—C9—C10 | 112.10 (17) | O2—C18B—H18F | 109.5 |
O3—C10—C11 | 123.48 (16) | H18D—C18B—H18F | 109.5 |
O3—C10—C9 | 119.99 (16) | H18E—C18B—H18F | 109.5 |
C11—C10—C9 | 116.49 (16) | O1—C19—H19A | 109.5 |
C12—C11—C13 | 119.93 (17) | O1—C19—H19B | 109.5 |
C12—C11—C10 | 120.11 (17) | H19A—C19—H19B | 109.5 |
C13—C11—C10 | 119.96 (16) | O1—C19—H19C | 109.5 |
C7—C12—C11 | 121.00 (17) | H19A—C19—H19C | 109.5 |
C7—C12—H12 | 119.5 | H19B—C19—H19C | 109.5 |
C11—C12—H12 | 119.5 | N2—N1—C1 | 115.35 (19) |
N3—C13—C11 | 121.94 (17) | N1—N2—C7 | 112.53 (17) |
N3—C13—H13 | 119.0 | C13—N3—C14 | 130.15 (16) |
C11—C13—H13 | 119.0 | C13—N3—H33 | 113.0 (15) |
N3—C14—C17 | 113.51 (15) | C14—N3—H33 | 116.9 (16) |
N3—C14—C16 | 104.87 (15) | C19—O1—C3 | 117.8 (3) |
C17—C14—C16 | 111.80 (15) | C9—O2—C18B | 114.9 (9) |
N3—C14—C15 | 107.59 (14) | C9—O2—C18A | 118.8 (6) |
C17—C14—C15 | 107.33 (15) | C15—O4—H44 | 108.2 (19) |
C16—C14—C15 | 111.73 (15) | C16—O5—H55 | 111 (2) |
O4—C15—C14 | 111.20 (16) | C17—O6—H66 | 108 (2) |
| | | |
C6—C1—C2—C3 | 0.3 (4) | C12—C11—C13—N3 | 178.97 (18) |
N1—C1—C2—C3 | 179.4 (2) | C10—C11—C13—N3 | −1.1 (3) |
C1—C2—C3—C4 | 0.0 (4) | N3—C14—C15—O4 | −46.68 (19) |
C1—C2—C3—O1 | −179.1 (2) | C17—C14—C15—O4 | −169.18 (15) |
C2—C3—C4—C5 | 0.2 (4) | C16—C14—C15—O4 | 67.92 (19) |
O1—C3—C4—C5 | 179.3 (3) | N3—C14—C16—O5 | 176.68 (15) |
C3—C4—C5—C6 | −0.8 (4) | C17—C14—C16—O5 | −59.9 (2) |
C2—C1—C6—C5 | −0.8 (4) | C15—C14—C16—O5 | 60.41 (19) |
N1—C1—C6—C5 | −179.8 (2) | N3—C14—C17—O6 | 77.8 (2) |
C4—C5—C6—C1 | 1.0 (4) | C16—C14—C17—O6 | −40.6 (2) |
C12—C7—C8—C9 | 3.1 (3) | C15—C14—C17—O6 | −163.42 (15) |
N2—C7—C8—C9 | −175.8 (2) | C6—C1—N1—N2 | −10.5 (3) |
C7—C8—C9—O2 | −178.6 (2) | C2—C1—N1—N2 | 170.4 (2) |
C7—C8—C9—C10 | 2.1 (3) | C1—N1—N2—C7 | 179.06 (17) |
C8—C9—C10—O3 | 175.70 (19) | C12—C7—N2—N1 | −176.11 (18) |
O2—C9—C10—O3 | −3.7 (3) | C8—C7—N2—N1 | 2.8 (3) |
C8—C9—C10—C11 | −6.5 (3) | C11—C13—N3—C14 | 179.28 (17) |
O2—C9—C10—C11 | 174.16 (18) | C17—C14—N3—C13 | −10.9 (3) |
O3—C10—C11—C12 | −176.37 (18) | C16—C14—N3—C13 | 111.4 (2) |
C9—C10—C11—C12 | 5.9 (3) | C15—C14—N3—C13 | −129.5 (2) |
O3—C10—C11—C13 | 3.7 (3) | C4—C3—O1—C19 | −5.2 (5) |
C9—C10—C11—C13 | −174.08 (17) | C2—C3—O1—C19 | 173.8 (3) |
C8—C7—C12—C11 | −3.6 (3) | C8—C9—O2—C18B | −9 (2) |
N2—C7—C12—C11 | 175.32 (18) | C10—C9—O2—C18B | 170 (2) |
C13—C11—C12—C7 | 178.93 (18) | C8—C9—O2—C18A | 10.9 (16) |
C10—C11—C12—C7 | −1.0 (3) | C10—C9—O2—C18A | −169.8 (16) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H33···O3 | 0.86 (2) | 1.84 (2) | 2.584 (2) | 144 (2) |
O4—H44···O6i | 0.82 (2) | 1.92 (2) | 2.744 (2) | 177 (3) |
O5—H55···O4ii | 0.84 (2) | 1.90 (2) | 2.734 (2) | 174 (3) |
O6—H66···O3iii | 0.82 (2) | 2.00 (2) | 2.7792 (19) | 160 (3) |
O6—H66···O2iii | 0.82 (2) | 2.26 (3) | 2.800 (2) | 124 (2) |
C15—H15B···G1iv | 0.93 (1) | 3.05) | 3.861 (2) | 142 (1) |
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, −y+2, −z+2; (iii) x, −y+3/2, z−1/2; (iv) −x, y−1/2, −z+1/2. |
(III) (
Z)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxy- 4-(4-methoxyphenyldiazenyl)cyclohexa-2,4-dienone
top
Crystal data top
C19H23N3O6 | F(000) = 824 |
Mr = 389.40 | Dx = 1.369 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 17273 reflections |
a = 16.9333 (9) Å | θ = 1.9–28.8° |
b = 10.7124 (6) Å | µ = 0.10 mm−1 |
c = 10.5476 (6) Å | T = 296 K |
β = 98.966 (4)° | Plate, red |
V = 1889.92 (18) Å3 | 0.35 × 0.23 × 0.09 mm |
Z = 4 | |
Data collection top
STOE IPD-II diffractometer | 3714 independent reflections |
Radiation source: fine-focus sealed tube | 2438 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.116 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.3° |
ω scans | h = −20→20 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −13→13 |
Tmin = 0.973, Tmax = 0.993 | l = −12→12 |
17746 measured 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)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.0684P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.99 | (Δ/σ)max < 0.001 |
3714 reflections | Δρmax = 0.23 e Å−3 |
311 parameters | Δρmin = −0.18 e Å−3 |
42 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.009 (2) |
Crystal data top
C19H23N3O6 | V = 1889.92 (18) Å3 |
Mr = 389.40 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.9333 (9) Å | µ = 0.10 mm−1 |
b = 10.7124 (6) Å | T = 296 K |
c = 10.5476 (6) Å | 0.35 × 0.23 × 0.09 mm |
β = 98.966 (4)° | |
Data collection top
STOE IPD-II diffractometer | 3714 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 2438 reflections with I > 2σ(I) |
Tmin = 0.973, Tmax = 0.993 | Rint = 0.116 |
17746 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 42 restraints |
wR(F2) = 0.135 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.23 e Å−3 |
3714 reflections | Δρmin = −0.18 e Å−3 |
311 parameters | |
Special details top
Experimental. 243 frames, detector distance = 100 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 (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.47825 (17) | 0.4219 (2) | 0.6766 (3) | 0.0612 (7) | |
C2A | 0.5108 (8) | 0.3170 (11) | 0.7251 (11) | 0.137 (2) | 0.409 (7) |
H2A | 0.4955 | 0.2430 | 0.6822 | 0.164* | 0.409 (7) |
C2B | 0.5420 (3) | 0.3368 (6) | 0.6687 (5) | 0.0555 (14) | 0.591 (7) |
H2B | 0.5410 | 0.2848 | 0.5979 | 0.067* | 0.591 (7) |
C3A | 0.5666 (9) | 0.3103 (10) | 0.8364 (13) | 0.1364 (6) | 0.409 (7) |
H3A | 0.5778 | 0.2347 | 0.8788 | 0.164* | 0.409 (7) |
C3B | 0.6052 (3) | 0.3334 (5) | 0.7687 (5) | 0.0588 (14) | 0.591 (7) |
H3B | 0.6483 | 0.2804 | 0.7653 | 0.071* | 0.591 (7) |
C4 | 0.6036 (2) | 0.4146 (3) | 0.8809 (3) | 0.0800 (10) | |
C5A | 0.5640 (6) | 0.5219 (10) | 0.8497 (8) | 0.067 (2) | 0.591 (7) |
H5A | 0.5776 | 0.5933 | 0.8985 | 0.081* | 0.591 (7) |
C5B | 0.5440 (8) | 0.4927 (14) | 0.8831 (12) | 0.062 (3) | 0.409 (7) |
H5B | 0.5441 | 0.5468 | 0.9521 | 0.075* | 0.409 (7) |
C6A | 0.5031 (5) | 0.5271 (8) | 0.7457 (8) | 0.067 (2) | 0.591 (7) |
H6A | 0.4786 | 0.6032 | 0.7222 | 0.080* | 0.591 (7) |
C6B | 0.4811 (8) | 0.4942 (11) | 0.7822 (10) | 0.060 (3) | 0.409 (7) |
H6B | 0.4385 | 0.5478 | 0.7873 | 0.073* | 0.409 (7) |
C7 | 0.30538 (15) | 0.5163 (2) | 0.46511 (19) | 0.0447 (5) | |
C8 | 0.29236 (15) | 0.4275 (2) | 0.3637 (2) | 0.0462 (6) | |
H8 | 0.3224 | 0.3544 | 0.3689 | 0.055* | |
C9 | 0.23633 (15) | 0.44917 (18) | 0.25949 (18) | 0.0403 (5) | |
C10 | 0.19049 (13) | 0.56275 (18) | 0.24400 (17) | 0.0355 (5) | |
C11 | 0.20056 (13) | 0.64624 (17) | 0.35168 (18) | 0.0371 (5) | |
C12 | 0.25884 (15) | 0.6205 (2) | 0.45999 (19) | 0.0456 (6) | |
H12 | 0.2655 | 0.6757 | 0.5289 | 0.055* | |
C13 | 0.15416 (13) | 0.75538 (18) | 0.35053 (18) | 0.0373 (5) | |
H13 | 0.1626 | 0.8073 | 0.4221 | 0.045* | |
C14 | 0.04710 (13) | 0.89617 (16) | 0.24302 (16) | 0.0327 (5) | |
C15 | −0.03672 (13) | 0.85092 (18) | 0.18749 (17) | 0.0366 (5) | |
H15A | −0.0591 | 0.8050 | 0.2527 | 0.044* | |
H15B | −0.0708 | 0.9224 | 0.1626 | 0.044* | |
C16 | 0.08007 (14) | 0.98723 (17) | 0.15268 (17) | 0.0385 (5) | |
H16A | 0.1347 | 1.0095 | 0.1870 | 0.046* | |
H16B | 0.0795 | 0.9491 | 0.0691 | 0.046* | |
C17 | 0.04120 (14) | 0.95798 (17) | 0.37162 (16) | 0.0350 (5) | |
H17A | −0.0080 | 1.0056 | 0.3634 | 0.042* | |
H17B | 0.0385 | 0.8935 | 0.4353 | 0.042* | |
C18 | 0.6817 (2) | 0.4947 (5) | 1.0700 (3) | 0.1046 (13) | |
H18A | 0.7079 | 0.4688 | 1.1532 | 0.157* | 0.50 |
H18B | 0.6413 | 0.5554 | 1.0799 | 0.157* | 0.50 |
H18C | 0.7201 | 0.5310 | 1.0231 | 0.157* | 0.50 |
H18D | 0.6717 | 0.5680 | 1.0176 | 0.157* | 0.50 |
H18E | 0.7383 | 0.4814 | 1.0909 | 0.157* | 0.50 |
H18F | 0.6594 | 0.5058 | 1.1476 | 0.157* | 0.50 |
C19 | 0.2502 (2) | 0.2484 (3) | 0.1693 (3) | 0.0892 (12) | |
H19A | 0.2320 | 0.2019 | 0.0925 | 0.134* | |
H19B | 0.2339 | 0.2067 | 0.2415 | 0.134* | |
H19C | 0.3075 | 0.2544 | 0.1816 | 0.134* | |
N1 | 0.41502 (15) | 0.42043 (19) | 0.5698 (2) | 0.0607 (6) | |
N2 | 0.36663 (13) | 0.50856 (18) | 0.57222 (18) | 0.0521 (5) | |
N3 | 0.10037 (11) | 0.78718 (14) | 0.25490 (15) | 0.0347 (4) | |
O1A | 0.6473 (7) | 0.3947 (13) | 1.0053 (11) | 0.096 (4) | 0.409 (7) |
O1B | 0.6754 (4) | 0.4066 (9) | 0.9636 (7) | 0.0733 (17) | 0.591 (7) |
O2 | 0.21672 (12) | 0.36987 (14) | 0.15796 (15) | 0.0579 (5) | |
O3 | 0.14223 (10) | 0.58546 (12) | 0.14174 (12) | 0.0414 (4) | |
O4 | −0.03509 (11) | 0.77273 (13) | 0.07885 (12) | 0.0418 (4) | |
O5 | 0.03106 (13) | 1.09466 (13) | 0.14145 (15) | 0.0539 (5) | |
O6 | 0.10637 (10) | 1.03845 (12) | 0.41583 (12) | 0.0415 (4) | |
H33 | 0.0970 (16) | 0.732 (2) | 0.188 (2) | 0.056 (7)* | |
H44 | −0.0647 (17) | 0.711 (2) | 0.085 (3) | 0.074 (10)* | |
H55 | 0.035 (2) | 1.136 (3) | 0.078 (3) | 0.114 (14)* | |
H66 | 0.1294 (15) | 1.017 (2) | 0.4899 (18) | 0.055 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0573 (18) | 0.0550 (14) | 0.0635 (15) | 0.0142 (13) | −0.0151 (13) | 0.0064 (11) |
C2A | 0.150 | 0.071 (7) | 0.150 | 0.044 (8) | −0.101 (6) | −0.037 (7) |
C2B | 0.047 (3) | 0.048 (3) | 0.070 (3) | 0.008 (2) | 0.004 (2) | 0.004 (2) |
C3A | 0.150 | 0.070 | 0.150 | 0.039 (6) | −0.099 (6) | 0.000 (7) |
C3B | 0.041 (3) | 0.053 (3) | 0.078 (3) | 0.009 (2) | −0.006 (2) | 0.007 (2) |
C4 | 0.072 (2) | 0.0658 (18) | 0.087 (2) | 0.0112 (16) | −0.0337 (17) | 0.0044 (15) |
C5A | 0.057 (6) | 0.087 (5) | 0.053 (5) | 0.009 (4) | −0.003 (3) | −0.008 (4) |
C5B | 0.042 (6) | 0.104 (9) | 0.040 (5) | 0.023 (6) | 0.004 (4) | 0.004 (4) |
C6A | 0.062 (5) | 0.068 (4) | 0.064 (5) | 0.014 (4) | −0.012 (3) | 0.006 (3) |
C6B | 0.052 (6) | 0.082 (8) | 0.046 (5) | 0.025 (5) | 0.002 (4) | 0.006 (4) |
C7 | 0.0486 (14) | 0.0419 (11) | 0.0390 (10) | 0.0070 (10) | −0.0075 (10) | 0.0019 (8) |
C8 | 0.0500 (15) | 0.0373 (11) | 0.0488 (12) | 0.0090 (10) | −0.0007 (11) | 0.0008 (9) |
C9 | 0.0485 (14) | 0.0329 (10) | 0.0378 (10) | 0.0025 (9) | 0.0019 (9) | −0.0062 (8) |
C10 | 0.0379 (12) | 0.0327 (10) | 0.0336 (9) | −0.0005 (9) | −0.0018 (9) | −0.0001 (7) |
C11 | 0.0434 (13) | 0.0309 (9) | 0.0338 (9) | 0.0037 (9) | −0.0039 (9) | −0.0024 (7) |
C12 | 0.0541 (15) | 0.0407 (11) | 0.0369 (10) | 0.0059 (10) | −0.0084 (10) | −0.0041 (8) |
C13 | 0.0432 (13) | 0.0325 (10) | 0.0328 (9) | 0.0016 (9) | −0.0045 (9) | −0.0032 (7) |
C14 | 0.0452 (13) | 0.0262 (9) | 0.0248 (8) | 0.0061 (8) | −0.0009 (8) | 0.0005 (7) |
C15 | 0.0453 (13) | 0.0311 (9) | 0.0313 (9) | 0.0027 (9) | −0.0006 (9) | 0.0006 (7) |
C16 | 0.0535 (14) | 0.0332 (10) | 0.0275 (9) | −0.0001 (9) | 0.0022 (9) | 0.0013 (7) |
C17 | 0.0462 (13) | 0.0309 (9) | 0.0266 (8) | 0.0042 (9) | 0.0021 (8) | −0.0002 (7) |
C18 | 0.074 (2) | 0.156 (4) | 0.073 (2) | 0.018 (3) | −0.0236 (18) | −0.018 (2) |
C19 | 0.118 (3) | 0.0473 (15) | 0.092 (2) | 0.0254 (17) | −0.016 (2) | −0.0311 (15) |
N1 | 0.0623 (15) | 0.0518 (12) | 0.0608 (12) | 0.0145 (11) | −0.0129 (11) | 0.0036 (9) |
N2 | 0.0528 (13) | 0.0497 (11) | 0.0479 (10) | 0.0122 (10) | −0.0102 (9) | 0.0042 (8) |
N3 | 0.0449 (11) | 0.0283 (8) | 0.0288 (8) | 0.0039 (7) | −0.0006 (7) | −0.0021 (6) |
O1A | 0.088 (9) | 0.094 (5) | 0.086 (7) | 0.013 (6) | −0.049 (5) | 0.007 (5) |
O1B | 0.048 (3) | 0.079 (3) | 0.084 (4) | 0.010 (3) | −0.019 (2) | 0.007 (3) |
O2 | 0.0773 (14) | 0.0408 (8) | 0.0499 (9) | 0.0161 (8) | −0.0084 (8) | −0.0161 (7) |
O3 | 0.0488 (10) | 0.0393 (7) | 0.0318 (7) | 0.0061 (7) | −0.0073 (6) | −0.0055 (5) |
O4 | 0.0608 (11) | 0.0299 (7) | 0.0314 (7) | −0.0069 (7) | −0.0031 (7) | −0.0011 (5) |
O5 | 0.0885 (14) | 0.0326 (8) | 0.0411 (8) | 0.0127 (8) | 0.0114 (8) | 0.0100 (6) |
O6 | 0.0592 (11) | 0.0341 (7) | 0.0266 (6) | −0.0020 (7) | −0.0070 (7) | −0.0005 (5) |
Geometric parameters (Å, º) top
C1—C2A | 1.319 (11) | C12—H12 | 0.9300 |
C1—C6B | 1.352 (13) | C13—N3 | 1.295 (3) |
C1—C6A | 1.372 (9) | C13—H13 | 0.9300 |
C1—C2B | 1.425 (7) | C14—N3 | 1.469 (2) |
C1—N1 | 1.428 (3) | C14—C17 | 1.527 (2) |
C2A—C3A | 1.389 (13) | C14—C15 | 1.528 (3) |
C2A—H2A | 0.9300 | C14—C16 | 1.529 (3) |
C2B—C3B | 1.381 (7) | C15—O4 | 1.423 (2) |
C2B—H2B | 0.9300 | C15—H15A | 0.9700 |
C3A—C4 | 1.331 (12) | C15—H15B | 0.9700 |
C3A—H3A | 0.9300 | C16—O5 | 1.413 (3) |
C3B—C4 | 1.472 (6) | C16—H16A | 0.9700 |
C3B—H3B | 0.9300 | C16—H16B | 0.9700 |
C4—C5B | 1.314 (15) | C17—O6 | 1.420 (3) |
C4—C5A | 1.346 (11) | C17—H17A | 0.9700 |
C4—O1B | 1.385 (9) | C17—H17B | 0.9700 |
C4—O1A | 1.419 (11) | C18—O1A | 1.353 (14) |
C5A—C6A | 1.385 (14) | C18—O1B | 1.458 (10) |
C5A—H5A | 0.9300 | C18—H18A | 0.9600 |
C5B—C6B | 1.38 (2) | C18—H18B | 0.9600 |
C5B—H5B | 0.9300 | C18—H18C | 0.9600 |
C6A—H6A | 0.9300 | C18—H18D | 0.9600 |
C6B—H6B | 0.9300 | C18—H18E | 0.9600 |
C7—C12 | 1.363 (3) | C18—H18F | 0.9600 |
C7—N2 | 1.412 (3) | C19—O2 | 1.417 (3) |
C7—C8 | 1.422 (3) | C19—H19A | 0.9600 |
C8—C9 | 1.356 (3) | C19—H19B | 0.9600 |
C8—H8 | 0.9300 | C19—H19C | 0.9600 |
C9—O2 | 1.367 (2) | N1—N2 | 1.253 (3) |
C9—C10 | 1.439 (3) | N3—H33 | 0.92 (3) |
C10—O3 | 1.271 (2) | O4—H44 | 0.837 (18) |
C10—C11 | 1.435 (3) | O5—H55 | 0.815 (19) |
C11—C13 | 1.408 (3) | O6—H66 | 0.850 (17) |
C11—C12 | 1.416 (3) | | |
| | | |
C2A—C1—C6B | 102.1 (7) | C17—C14—C15 | 107.03 (18) |
C2A—C1—C6A | 114.8 (6) | N3—C14—C16 | 106.34 (16) |
C6B—C1—C2B | 119.0 (6) | C17—C14—C16 | 110.97 (15) |
C6A—C1—C2B | 112.6 (5) | C15—C14—C16 | 111.79 (15) |
C2A—C1—N1 | 120.9 (5) | O4—C15—C14 | 111.23 (18) |
C6B—C1—N1 | 125.6 (6) | O4—C15—H15A | 109.4 |
C6A—C1—N1 | 123.9 (4) | C14—C15—H15A | 109.4 |
C2B—C1—N1 | 115.3 (3) | O4—C15—H15B | 109.4 |
C1—C2A—C3A | 124.1 (10) | C14—C15—H15B | 109.4 |
C1—C2A—H2A | 118.0 | H15A—C15—H15B | 108.0 |
C3A—C2A—H2A | 118.0 | O5—C16—C14 | 107.77 (17) |
C3B—C2B—C1 | 118.4 (5) | O5—C16—H16A | 110.2 |
C3B—C2B—H2B | 120.8 | C14—C16—H16A | 110.2 |
C1—C2B—H2B | 120.8 | O5—C16—H16B | 110.2 |
C4—C3A—C2A | 118.4 (9) | C14—C16—H16B | 110.2 |
C4—C3A—H3A | 120.8 | H16A—C16—H16B | 108.5 |
C2A—C3A—H3A | 120.8 | O6—C17—C14 | 113.57 (17) |
C2B—C3B—C4 | 119.3 (5) | O6—C17—H17A | 108.9 |
C2B—C3B—H3B | 120.3 | C14—C17—H17A | 108.9 |
C4—C3B—H3B | 120.3 | O6—C17—H17B | 108.9 |
C5B—C4—C3A | 102.7 (10) | C14—C17—H17B | 108.9 |
C3A—C4—C5A | 116.2 (6) | H17A—C17—H17B | 107.7 |
C5B—C4—O1B | 129.1 (8) | O1A—C18—H18A | 109.5 |
C3A—C4—O1B | 119.3 (6) | O1B—C18—H18A | 118.9 |
C5A—C4—O1B | 124.2 (6) | O1A—C18—H18B | 109.5 |
C5B—C4—O1A | 111.8 (9) | O1B—C18—H18B | 123.6 |
C3A—C4—O1A | 110.4 (8) | H18A—C18—H18B | 109.5 |
C5A—C4—O1A | 121.5 (8) | O1A—C18—H18C | 109.5 |
C5B—C4—C3B | 120.0 (7) | O1B—C18—H18C | 80.7 |
C5A—C4—C3B | 112.3 (5) | H18A—C18—H18C | 109.5 |
O1B—C4—C3B | 110.2 (5) | H18B—C18—H18C | 109.5 |
O1A—C4—C3B | 125.6 (6) | O1A—C18—H18D | 109.5 |
C4—C5A—C6A | 120.6 (9) | O1B—C18—H18D | 95.7 |
C4—C5A—H5A | 119.7 | H18A—C18—H18D | 141.1 |
C6A—C5A—H5A | 119.7 | H18B—C18—H18D | 56.3 |
C4—C5B—C6B | 119.7 (13) | H18C—C18—H18D | 56.3 |
C4—C5B—H5B | 120.2 | O1A—C18—H18E | 109.5 |
C6B—C5B—H5B | 120.2 | O1B—C18—H18E | 91.7 |
C1—C6A—C5A | 121.1 (8) | H18A—C18—H18E | 56.3 |
C1—C6A—H6A | 119.5 | H18B—C18—H18E | 141.1 |
C5A—C6A—H6A | 119.5 | H18C—C18—H18E | 56.3 |
C1—C6B—C5B | 123.5 (11) | H18D—C18—H18E | 109.5 |
C1—C6B—H6B | 118.3 | O1A—C18—H18F | 109.5 |
C5B—C6B—H6B | 118.3 | O1B—C18—H18F | 138.2 |
C12—C7—N2 | 115.33 (19) | H18A—C18—H18F | 56.3 |
C12—C7—C8 | 119.8 (2) | H18B—C18—H18F | 56.3 |
N2—C7—C8 | 124.8 (2) | H18C—C18—H18F | 141.1 |
C9—C8—C7 | 120.1 (2) | H18D—C18—H18F | 109.5 |
C9—C8—H8 | 119.9 | H18E—C18—H18F | 109.5 |
C7—C8—H8 | 119.9 | O2—C19—H19A | 109.5 |
C8—C9—O2 | 125.7 (2) | O2—C19—H19B | 109.5 |
C8—C9—C10 | 122.27 (18) | H19A—C19—H19B | 109.5 |
O2—C9—C10 | 112.07 (18) | O2—C19—H19C | 109.5 |
O3—C10—C11 | 122.26 (18) | H19A—C19—H19C | 109.5 |
O3—C10—C9 | 121.49 (17) | H19B—C19—H19C | 109.5 |
C11—C10—C9 | 116.22 (17) | N2—N1—C1 | 112.8 (2) |
C13—C11—C12 | 119.13 (17) | N1—N2—C7 | 115.4 (2) |
C13—C11—C10 | 120.90 (18) | C13—N3—C14 | 128.58 (16) |
C12—C11—C10 | 119.96 (18) | C13—N3—H33 | 112.5 (17) |
C7—C12—C11 | 121.18 (19) | C14—N3—H33 | 118.9 (17) |
C7—C12—H12 | 119.4 | C18—O1A—C4 | 118.0 (10) |
C11—C12—H12 | 119.4 | C4—O1B—C18 | 113.3 (6) |
N3—C13—C11 | 123.31 (18) | C9—O2—C19 | 117.35 (19) |
N3—C13—H13 | 118.3 | C15—O4—H44 | 109 (2) |
C11—C13—H13 | 118.3 | C16—O5—H55 | 113 (3) |
N3—C14—C17 | 113.17 (15) | C17—O6—H66 | 110.9 (18) |
N3—C14—C15 | 107.58 (15) | | |
| | | |
C6B—C1—C2A—C3A | −27.9 (15) | C8—C9—C10—C11 | −7.0 (3) |
C6A—C1—C2A—C3A | −0.6 (16) | O2—C9—C10—C11 | 173.55 (19) |
C2B—C1—C2A—C3A | 94.7 (17) | O3—C10—C11—C13 | 2.9 (3) |
N1—C1—C2A—C3A | −173.2 (11) | C9—C10—C11—C13 | −175.1 (2) |
C2A—C1—C2B—C3B | −71.7 (9) | O3—C10—C11—C12 | −175.9 (2) |
C6B—C1—C2B—C3B | −1.3 (8) | C9—C10—C11—C12 | 6.0 (3) |
C6A—C1—C2B—C3B | 29.9 (6) | N2—C7—C12—C11 | 173.6 (2) |
N1—C1—C2B—C3B | 179.9 (4) | C8—C7—C12—C11 | −3.8 (4) |
C1—C2A—C3A—C4 | −16 (2) | C13—C11—C12—C7 | −179.7 (2) |
C1—C2B—C3B—C4 | 1.7 (7) | C10—C11—C12—C7 | −0.9 (4) |
C2A—C3A—C4—C5B | 50.5 (15) | C12—C11—C13—N3 | 179.0 (2) |
C2A—C3A—C4—C5A | 26.2 (17) | C10—C11—C13—N3 | 0.2 (3) |
C2A—C3A—C4—O1B | −159.3 (10) | N3—C14—C15—O4 | −47.77 (19) |
C2A—C3A—C4—O1A | 169.9 (11) | C17—C14—C15—O4 | −169.68 (14) |
C2A—C3A—C4—C3B | −69.7 (12) | C16—C14—C15—O4 | 68.62 (19) |
C2B—C3B—C4—C5B | −2.6 (9) | N3—C14—C16—O5 | −178.70 (16) |
C2B—C3B—C4—C3A | 74.4 (7) | C17—C14—C16—O5 | −55.2 (2) |
C2B—C3B—C4—C5A | −31.0 (8) | C15—C14—C16—O5 | 64.2 (2) |
C2B—C3B—C4—O1B | −173.9 (5) | N3—C14—C17—O6 | 80.6 (2) |
C2B—C3B—C4—O1A | 157.7 (7) | C15—C14—C17—O6 | −161.11 (15) |
C5B—C4—C5A—C6A | −85 (3) | C16—C14—C17—O6 | −38.9 (2) |
C3A—C4—C5A—C6A | −20.7 (13) | C2A—C1—N1—N2 | 147.9 (8) |
O1B—C4—C5A—C6A | 165.1 (7) | C6B—C1—N1—N2 | 11.1 (7) |
O1A—C4—C5A—C6A | −160.1 (8) | C6A—C1—N1—N2 | −24.0 (6) |
C3B—C4—C5A—C6A | 28.2 (9) | C2B—C1—N1—N2 | −170.2 (3) |
C3A—C4—C5B—C6B | −41.5 (13) | C1—N1—N2—C7 | 176.4 (2) |
C5A—C4—C5B—C6B | 83 (2) | C12—C7—N2—N1 | −172.2 (2) |
O1B—C4—C5B—C6B | 172.4 (8) | C8—C7—N2—N1 | 5.0 (4) |
O1A—C4—C5B—C6B | −159.9 (10) | C11—C13—N3—C14 | 178.5 (2) |
C3B—C4—C5B—C6B | 2.9 (13) | C17—C14—N3—C13 | −16.8 (3) |
C2A—C1—C6A—C5A | 6.6 (11) | C15—C14—N3—C13 | −134.9 (2) |
C6B—C1—C6A—C5A | 75.4 (15) | C16—C14—N3—C13 | 105.2 (2) |
C2B—C1—C6A—C5A | −34.1 (8) | O1B—C18—O1A—C4 | −66.7 (14) |
N1—C1—C6A—C5A | 178.9 (5) | C5B—C4—O1A—C18 | −59.5 (13) |
C4—C5A—C6A—C1 | 4.1 (11) | C3A—C4—O1A—C18 | −173.2 (10) |
C2A—C1—C6B—C5B | 37.3 (13) | C5A—C4—O1A—C18 | −31.8 (14) |
C6A—C1—C6B—C5B | −82.7 (19) | O1B—C4—O1A—C18 | 73.0 (17) |
C2B—C1—C6B—C5B | 1.7 (13) | C3B—C4—O1A—C18 | 138.8 (8) |
N1—C1—C6B—C5B | −179.7 (8) | C5B—C4—O1B—C18 | 3.3 (11) |
C4—C5B—C6B—C1 | −2.6 (16) | C3A—C4—O1B—C18 | −138.1 (10) |
C12—C7—C8—C9 | 3.0 (4) | C5A—C4—O1B—C18 | 36.0 (9) |
N2—C7—C8—C9 | −174.1 (2) | O1A—C4—O1B—C18 | −58.6 (16) |
C7—C8—C9—O2 | −178.0 (2) | C3B—C4—O1B—C18 | 173.6 (4) |
C7—C8—C9—C10 | 2.5 (4) | O1A—C18—O1B—C4 | 64.8 (14) |
C8—C9—C10—O3 | 175.0 (2) | C8—C9—O2—C19 | 8.4 (4) |
O2—C9—C10—O3 | −4.5 (3) | C10—C9—O2—C19 | −172.1 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H33···O3 | 0.92 (3) | 1.84 (3) | 2.619 (2) | 141 (2) |
O5—H55···O4i | 0.82 (2) | 1.92 (2) | 2.733 (2) | 174 (4) |
O4—H44···O6ii | 0.84 (2) | 1.98 (2) | 2.789 (2) | 163 (3) |
O6—H66···O3iii | 0.85 (2) | 1.92 (2) | 2.7125 (18) | 154 (2) |
O6—H66···O2iii | 0.85 (2) | 2.45 (2) | 3.081 (2) | 132 (2) |
C3—H3···G1iv | 0.93 (1) | 3.32 (1) | 3.463 (7) | 91 (1) |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x, y−1/2, −z+1/2; (iii) x, −y+3/2, z+1/2; (iv) −x+1, −y+1, −z+1. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C18H19Cl2N3O5 | C19H23N3O6 | C19H23N3O6 |
Mr | 428.26 | 389.40 | 389.40 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 296 | 296 | 296 |
a, b, c (Å) | 16.8445 (15), 10.7259 (5), 11.1126 (9) | 16.3722 (11), 10.4506 (5), 11.3239 (7) | 16.9333 (9), 10.7124 (6), 10.5476 (6) |
α, β, γ (°) | 90, 106.037 (7), 90 | 90, 99.180 (5), 90 | 90, 98.966 (4), 90 |
V (Å3) | 1929.6 (2) | 1912.7 (2) | 1889.92 (18) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.37 | 0.10 | 0.10 |
Crystal size (mm) | 0.78 × 0.33 × 0.05 | 0.42 × 0.33 × 0.25 | 0.35 × 0.23 × 0.09 |
|
Data collection |
Diffractometer | STOE IPDS-II diffractometer | STOE IPDS-II diffractometer | STOE IPD-II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) | Integration STOE X-RED (Stoe & Cie, 2002) | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.871, 0.977 | 0.970, 0.982 | 0.973, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10068, 3782, 2715 | 13464, 3744, 2778 | 17746, 3714, 2438 |
Rint | 0.056 | 0.040 | 0.116 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.132, 1.02 | 0.053, 0.160, 1.06 | 0.050, 0.135, 0.99 |
No. of reflections | 3782 | 3744 | 3714 |
No. of parameters | 269 | 280 | 311 |
No. of restraints | 0 | 3 | 42 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.36 | 0.83, −0.32 | 0.23, −0.18 |
Selected geometric parameters (Å, º) for (I) topC1—N1 | 1.443 (3) | C10—O3 | 1.279 (3) |
C2—Cl1 | 1.727 (3) | C10—C11 | 1.434 (3) |
C6—Cl2 | 1.732 (3) | C11—C12 | 1.406 (3) |
C7—C12 | 1.372 (3) | C11—C13 | 1.425 (3) |
C7—C8 | 1.409 (3) | C13—N3 | 1.284 (3) |
C7—N2 | 1.417 (3) | C14—N3 | 1.464 (3) |
C8—C9 | 1.364 (3) | C18—O1 | 1.417 (3) |
C9—O1 | 1.357 (3) | N1—N2 | 1.243 (3) |
C9—C10 | 1.434 (3) | | |
| | | |
C6—C1—N1 | 120.0 (2) | O3—C10—C11 | 123.37 (19) |
C2—C1—N1 | 122.2 (2) | N3—C13—C11 | 122.2 (2) |
C8—C7—N2 | 113.35 (19) | C15—C14—C17 | 107.13 (18) |
O1—C9—C8 | 126.3 (2) | C13—N3—C14 | 129.6 (2) |
| | | |
C10—C11—C13—N3 | 0.3 (3) | C1—N1—N2—C7 | 179.2 (2) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H33···O3 | 0.79 (3) | 1.90 (3) | 2.587 (2) | 144 (3) |
O4—H44···O6i | 0.74 (3) | 2.04 (3) | 2.777 (3) | 174 (3) |
O5—H55···O4ii | 0.80 (4) | 1.94 (4) | 2.740 (3) | 176 (3) |
O6—H66···O1iii | 0.70 (3) | 2.25 (3) | 2.802 (2) | 137 (3) |
O6—H66···O3iii | 0.70 (3) | 2.28 (3) | 2.923 (2) | 153 (3) |
C17—H17A···G1iv | 0.97 (0) | 2.9471 (0) | 3.798 (2) | 147.06 (0) |
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, −y, −z+2; (iii) x, −y+1/2, z−1/2; (iv) −x, y+1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (II) topC1—N1 | 1.420 (3) | C10—O3 | 1.284 (2) |
C3—O1 | 1.399 (4) | C10—C11 | 1.426 (3) |
C7—C12 | 1.371 (3) | C11—C12 | 1.410 (3) |
C7—C8 | 1.413 (3) | C11—C13 | 1.417 (3) |
C7—N2 | 1.418 (3) | C13—N3 | 1.291 (2) |
C8—C9 | 1.349 (3) | C14—N3 | 1.463 (2) |
C9—O2 | 1.362 (2) | N1—N2 | 1.256 (2) |
C9—C10 | 1.443 (3) | | |
| | | |
C6—C1—N1 | 125.8 (2) | O3—C10—C11 | 123.48 (16) |
C2—C1—N1 | 113.2 (2) | N3—C13—C11 | 121.94 (17) |
C2—C3—O1 | 115.2 (3) | C17—C14—C15 | 107.33 (15) |
C8—C7—N2 | 122.92 (18) | C13—N3—C14 | 130.15 (16) |
C8—C9—O2 | 126.24 (18) | | |
| | | |
C10—C11—C13—N3 | −1.1 (3) | C1—N1—N2—C7 | 179.06 (17) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H33···O3 | 0.86 (2) | 1.84 (2) | 2.584 (2) | 144 (2) |
O4—H44···O6i | 0.824 (17) | 1.921 (18) | 2.744 (2) | 177 (3) |
O5—H55···O4ii | 0.836 (17) | 1.901 (18) | 2.734 (2) | 174 (3) |
O6—H66···O3iii | 0.815 (17) | 1.999 (19) | 2.7792 (19) | 160 (3) |
O6—H66···O2iii | 0.815 (17) | 2.26 (3) | 2.800 (2) | 124 (2) |
C15—H15B···G1iv | 0.93 (0) | 3.05210) | 3.861 (2) | 141.74 (0) |
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, −y+2, −z+2; (iii) x, −y+3/2, z−1/2; (iv) −x, y−1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (III) topC1—N1 | 1.428 (3) | C10—C11 | 1.435 (3) |
C7—C12 | 1.363 (3) | C11—C13 | 1.408 (3) |
C7—N2 | 1.412 (3) | C11—C12 | 1.416 (3) |
C7—C8 | 1.422 (3) | C13—N3 | 1.295 (3) |
C8—C9 | 1.356 (3) | C14—N3 | 1.469 (2) |
C9—O2 | 1.367 (2) | C19—O2 | 1.417 (3) |
C9—C10 | 1.439 (3) | N1—N2 | 1.253 (3) |
C10—O3 | 1.271 (2) | | |
| | | |
C12—C7—N2 | 115.33 (19) | O3—C10—C11 | 122.26 (18) |
C12—C7—C8 | 119.8 (2) | N3—C13—C11 | 123.31 (18) |
N2—C7—C8 | 124.8 (2) | C17—C14—C15 | 107.03 (18) |
C8—C9—O2 | 125.7 (2) | C13—N3—C14 | 128.58 (16) |
| | | |
C10—C11—C13—N3 | 0.2 (3) | C1—N1—N2—C7 | 176.4 (2) |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H33···O3 | 0.92 (3) | 1.84 (3) | 2.619 (2) | 141 (2) |
O5—H55···O4i | 0.815 (19) | 1.92 (2) | 2.733 (2) | 174 (4) |
O4—H44···O6ii | 0.837 (18) | 1.98 (2) | 2.789 (2) | 163 (3) |
O6—H66···O3iii | 0.850 (17) | 1.924 (19) | 2.7125 (18) | 154 (2) |
O6—H66···O2iii | 0.850 (17) | 2.45 (2) | 3.081 (2) | 132 (2) |
C3—H3···G1iv | 0.93 (0) | 3.322 (0) | 3.463 (7) | 90.82 (0) |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x, y−1/2, −z+1/2; (iii) x, −y+3/2, z+1/2; (iv) −x+1, −y+1, −z+1. |
The observed 'π–p' interaction distances (Å) for (I), (II) and (III). topCompound | Cg-Cgi,ii | dcentroids | dperpendicular |
I | Cg1-Cg1i | 3,556 (2) | 3,38 |
II | Cg1-Cg2ii | 3,937 (1) | 3,57 |
III | Cg1-Cg2ii | 3,996 (3) | 3,66 |
Cg1, Cg2 are the centroid of the C1–C6 and C7–C12 rings, respectively. [Symmetry codes: (i) 1 − x, 1 − y, 2 − z; (ii) 1 − x, 1 − y, 1 − z.] |
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Azo compounds are the most widely used class of dyes owing to their versatile application in various fields, such as the dyeing of textiles and fibers, the coloring of different materials, and high-technology areas, such as electro-optical devices and ink-jet printers (Peters & Freeman, 1991). Most Schiff bases have antibacterial, anticancer, antinflammatory and antitoxic properties (Williams, 1972). Two characteristic properties of Schiff bases are photochromism and thermochromism (Cohen et al., 1964; Moustakali-Mavridis et al., 1978). These properties are caused by proton transfer from the hydroxy O atom to the imine N atom (Hadjoudis et al., 1987; Xu et al., 1994). 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 Tables 1, 3 and 5, respectively.
In all three molecules (I), (II) and (III), the keto–amine tautomer is favoured over the phenol–imine form, as indicated by the C10—O3, C13—N3, C11—C13 and C10—C11 bond lengths (Figs. 1, 2 and 3, and Tables 1, 3 and 5). Furthermore, these data show that there are significant elongations of the C13—N3 bond and contraction of the C10—O3 bond. A similar effect was observed for 4-[(3-chloropheny)diazeniyl]-2-{[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one [C10—O3 = 1.286 (2) Å, C13—N3 = 1.298 (3) Å, C11—C13 = 1.411 (3) Å and C10—C11 = 1.436 (3) Å; Odabaşoǧlu et al., 2003]. The H atom was located on N1, thus confirming a preference for the keto–amine tautomer in the solid state. The N1—C1 and N2—C7 bond lengths are approximately the same in (I), (II) and (III), and these lengths indicate single-bond character, whereas the N═N bond lengths are indicative of significant double-bond character. The high s.u. values and high displacement parameters of some atoms in the molecules of both (II) and (III) are probably caused by positional and orientational disorder. In (II), C18 is observed at two different positions owing to a positional disorder, with occupancy factors of 0.64 (7) and 0.36 (7). In (III), atom O1 shows positional disorder with occupancy factors of 0.409 (7) and 0.591 (7). At the same time, the phenyl rings also show orientational disorder with the same occupancy factors (Fig. 3).
In (I), the C—Cl bond distance is consistent with that in 5-(2-chlorophenyldiazenyl)salicylaldehyde and 4-(2-chlorophenyldiazenyl)- 2-{[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one (Albayrak et al., 2004). The dihedral angles between the C1–C6 and C7–C12 rings are 58.91 (13), 8.89 (11) and 21.57 (3)° (the average of the two angles for the orientationally disordered phenyl ring) for (I), (II) and (III), respectively.
The intra- and intermolecular hydrogen bonds are shown in the packing diagram of (I), (II) and (III) in Figs. 4–6, respectively. In all three structure, these O—H···O hydrogen bonds generate edge-fused R22(5), R32(19) and R22(12) rings. Atom H33 bonded to N3 form a strong intramolecular hydrogen bond with atom O3, as observed in similar compounds (Odabaşoǧlu et al., 2003; Albayrak et al., 2004). In (I), (II) and (III), the molecules are linked by C—H···π interactions (Tables 2, 4 and 6, and Figs. 4–6). In addition to these interactions, all three compounds contain π–π interactions. Details of these π–π interactions are given in Table 7 and they are shown in Figs. 4–6.