Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109006696/fn3012sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109006696/fn3012Isup2.hkl |
CCDC reference: 730088
For related literature, see: Costamagna et al. (1992); Diehl et al. (1950); Dudek & Dudek (1966); Dudek & Holm (1962); Fita et al. (2005); Gavranic et al. (1996); Kaitner & Pavlovic (1996); Ottolenghi & McClure (1967); Pavlovic & Sosa (2000); Salman et al. (1991); Xu et al. (1994); Yildiz et al. (1998).
Compound (I) was prepared according to a literature method (Diehl et al., 1950). 2,4-Dihydroxyacetophenone (2.00 g, 13.2 mmol) and hydrazine hydrate (4.00 g, 40 mmol) were dissolved in ethanol (40 ml), and four drops of methanoic acid were added. The mixture was stirred at room temperature for 5 h. A yellow powder [4-(1-hydrazonoethyl)benzene-1,3-diol] was filtered off, washed with ethanol and dried in a vacuum. 4-(1-Hydrazonoethyl)benzene-1,3-diol (0.20 g, 1.3 mmol) and p-dimethylaminobenzaldehyde (0.19 g, 1.3 mmol) were dissolved in ethanol (20 ml), and then four drops of methanoic acid were added and the mixture was stirred at room temperature for 5 h. The resulting yellow powder was filtered off, washed several times with ethanol and then dried in a vacuum (yield 89%, m.p. 482.7–483.9 K. Well shaped crystals were obtained by slow evaporation from ethanol solutions. [Cystal description in CIF is `plan'; this is not a valid description; should it be `plate'?]
H atoms attached to C atoms were idealized and included as riding atoms [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) (for CH H atoms), and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) (for CH3)]. H atoms attached to N and O atoms were located in a difference map and refined isotropically with O—H and N—H distance restraints of 0.XX (X) and 0.92 (X) Å [please give actual restraints (with s.u. values) rather than the final obtained distances]; the refined distances are given in Table 1.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
C17H19N3O2·C17H19N3O2 | F(000) = 1264 |
Mr = 594.70 | Dx = 1.278 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.872 (3) Å | Cell parameters from 1943 reflections |
b = 9.630 (2) Å | θ = 2.3–21.0° |
c = 28.441 (7) Å | µ = 0.09 mm−1 |
β = 71.932 (4)° | T = 298 K |
V = 3091.4 (12) Å3 | Plate, orange |
Z = 4 | 0.49 × 0.40 × 0.06 mm |
Bruker SMART CCD area-detector diffractometer | 3429 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 25.0°, θmin = 1.8° |
phi and ω scans | h = −14→14 |
12702 measured reflections | k = −11→10 |
5461 independent reflections | l = −27→33 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0566P)2 + 0.1177P] where P = (Fo2 + 2Fc2)/3 |
5461 reflections | (Δ/σ)max < 0.001 |
413 parameters | Δρmax = 0.20 e Å−3 |
2 restraints | Δρmin = −0.18 e Å−3 |
C17H19N3O2·C17H19N3O2 | V = 3091.4 (12) Å3 |
Mr = 594.70 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.872 (3) Å | µ = 0.09 mm−1 |
b = 9.630 (2) Å | T = 298 K |
c = 28.441 (7) Å | 0.49 × 0.40 × 0.06 mm |
β = 71.932 (4)° |
Bruker SMART CCD area-detector diffractometer | 3429 reflections with I > 2σ(I) |
12702 measured reflections | Rint = 0.041 |
5461 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 2 restraints |
wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.20 e Å−3 |
5461 reflections | Δρmin = −0.18 e Å−3 |
413 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.66544 (18) | −0.3883 (2) | 0.19607 (8) | 0.0441 (6) | |
C2 | 0.5671 (2) | −0.3095 (3) | 0.21925 (9) | 0.0561 (7) | |
H2 | 0.5248 | −0.3257 | 0.2522 | 0.067* | |
C3 | 0.53180 (19) | −0.2066 (2) | 0.19339 (8) | 0.0535 (6) | |
H3 | 0.4646 | −0.1551 | 0.2094 | 0.064* | |
C4 | 0.59269 (18) | −0.1763 (2) | 0.14404 (8) | 0.0421 (5) | |
C5 | 0.69385 (19) | −0.2573 (2) | 0.12171 (8) | 0.0488 (6) | |
C6 | 0.72850 (19) | −0.3609 (2) | 0.14765 (8) | 0.0500 (6) | |
H6 | 0.7957 | −0.4131 | 0.1321 | 0.060* | |
C7 | 0.55474 (19) | −0.0661 (2) | 0.11686 (8) | 0.0457 (6) | |
C8 | 0.4417 (2) | 0.0110 (3) | 0.13970 (9) | 0.0659 (7) | |
H8A | 0.4313 | 0.0793 | 0.1168 | 0.099* | |
H8B | 0.4448 | 0.0561 | 0.1694 | 0.099* | |
H8C | 0.3765 | −0.0529 | 0.1476 | 0.099* | |
C9 | 0.6653 (2) | 0.0844 (2) | 0.00433 (9) | 0.0570 (7) | |
H9 | 0.7335 | 0.0303 | −0.0041 | 0.068* | |
C10 | 0.6529 (2) | 0.1869 (2) | −0.03110 (8) | 0.0492 (6) | |
C11 | 0.7386 (2) | 0.2015 (3) | −0.07621 (9) | 0.0603 (7) | |
H11 | 0.8050 | 0.1444 | −0.0836 | 0.072* | |
C12 | 0.7301 (2) | 0.2965 (3) | −0.11067 (9) | 0.0618 (7) | |
H12 | 0.7898 | 0.3018 | −0.1409 | 0.074* | |
C13 | 0.6326 (2) | 0.3859 (3) | −0.10098 (8) | 0.0531 (6) | |
C14 | 0.7002 (3) | 0.4777 (3) | −0.18513 (9) | 0.0806 (9) | |
H14A | 0.7816 | 0.4816 | −0.1860 | 0.121* | |
H14B | 0.6833 | 0.5543 | −0.2035 | 0.121* | |
H14C | 0.6858 | 0.3920 | −0.1996 | 0.121* | |
C15 | 0.5191 (3) | 0.5692 (3) | −0.12500 (10) | 0.0815 (9) | |
H15A | 0.4530 | 0.5110 | −0.1243 | 0.122* | |
H15B | 0.5303 | 0.6372 | −0.1507 | 0.122* | |
H15C | 0.5040 | 0.6153 | −0.0937 | 0.122* | |
C16 | 0.5459 (2) | 0.3706 (3) | −0.05555 (9) | 0.0622 (7) | |
H16 | 0.4794 | 0.4276 | −0.0478 | 0.075* | |
C17 | 0.5558 (2) | 0.2739 (3) | −0.02184 (9) | 0.0604 (7) | |
H17 | 0.4955 | 0.2665 | 0.0081 | 0.072* | |
C18 | 0.02962 (19) | 0.2198 (2) | 0.24745 (8) | 0.0440 (6) | |
C19 | 0.1294 (2) | 0.1635 (2) | 0.21285 (8) | 0.0497 (6) | |
H19 | 0.1760 | 0.0986 | 0.2224 | 0.060* | |
C20 | 0.1576 (2) | 0.2050 (2) | 0.16492 (8) | 0.0505 (6) | |
H20 | 0.2236 | 0.1658 | 0.1420 | 0.061* | |
C21 | 0.09179 (18) | 0.3043 (2) | 0.14838 (7) | 0.0388 (5) | |
C22 | −0.01123 (17) | 0.3607 (2) | 0.18416 (7) | 0.0384 (5) | |
C23 | −0.03927 (19) | 0.3138 (2) | 0.23280 (8) | 0.0453 (6) | |
H23 | −0.1072 | 0.3476 | 0.2561 | 0.054* | |
C24 | 0.13295 (18) | 0.3544 (2) | 0.09840 (8) | 0.0427 (5) | |
C25 | 0.2407 (2) | 0.3001 (3) | 0.06073 (9) | 0.0617 (7) | |
H25A | 0.2333 | 0.3127 | 0.0283 | 0.093* | |
H25B | 0.2493 | 0.2030 | 0.0665 | 0.093* | |
H25C | 0.3090 | 0.3494 | 0.0630 | 0.093* | |
C26 | 0.0544 (2) | 0.6194 (2) | 0.03315 (8) | 0.0474 (6) | |
H26 | −0.0114 | 0.6468 | 0.0590 | 0.057* | |
C27 | 0.08499 (19) | 0.6960 (2) | −0.01250 (8) | 0.0439 (6) | |
C28 | 0.1809 (2) | 0.6598 (2) | −0.05314 (8) | 0.0516 (6) | |
H28 | 0.2278 | 0.5844 | −0.0508 | 0.062* | |
C29 | 0.2077 (2) | 0.7325 (3) | −0.09636 (8) | 0.0539 (6) | |
H29 | 0.2721 | 0.7051 | −0.1229 | 0.065* | |
C30 | 0.1403 (2) | 0.8476 (2) | −0.10176 (8) | 0.0472 (6) | |
C31 | 0.0435 (2) | 0.8831 (2) | −0.06110 (8) | 0.0533 (6) | |
H31 | −0.0040 | 0.9581 | −0.0633 | 0.064* | |
C32 | 0.0176 (2) | 0.8085 (2) | −0.01791 (8) | 0.0520 (6) | |
H32 | −0.0473 | 0.8345 | 0.0086 | 0.062* | |
C33 | 0.2675 (2) | 0.8834 (3) | −0.18645 (9) | 0.0777 (9) | |
H33A | 0.3365 | 0.8734 | −0.1760 | 0.117* | |
H33B | 0.2810 | 0.9547 | −0.2112 | 0.117* | |
H33C | 0.2515 | 0.7971 | −0.2001 | 0.117* | |
C34 | 0.0931 (3) | 1.0315 (3) | −0.15178 (10) | 0.0798 (9) | |
H34A | 0.0146 | 0.9966 | −0.1468 | 0.120* | |
H34B | 0.1244 | 1.0676 | −0.1847 | 0.120* | |
H34C | 0.0906 | 1.1041 | −0.1283 | 0.120* | |
H1 | 0.727 (2) | −0.170 (2) | 0.0640 (11) | 0.109 (12)* | |
H4 | 0.0071 (13) | 0.481 (2) | 0.1112 (6) | 0.059 (7)* | |
H2A | 0.777 (2) | −0.521 (3) | 0.2036 (10) | 0.094 (10)* | |
H4A | 0.037 (2) | 0.122 (3) | 0.3024 (10) | 0.086 (11)* | |
N1 | 0.58825 (17) | 0.0640 (2) | 0.04627 (7) | 0.0569 (5) | |
N2 | 0.62388 (17) | −0.0408 (2) | 0.07282 (7) | 0.0548 (5) | |
N3 | 0.11490 (16) | 0.5147 (2) | 0.03936 (6) | 0.0483 (5) | |
N4 | 0.07528 (17) | 0.45527 (19) | 0.08550 (7) | 0.0444 (5) | |
N5 | 0.16810 (19) | 0.9205 (2) | −0.14490 (7) | 0.0630 (6) | |
N6 | 0.6246 (2) | 0.4852 (2) | −0.13444 (8) | 0.0680 (6) | |
O1 | 0.76141 (17) | −0.2369 (2) | 0.07466 (6) | 0.0812 (6) | |
O2 | 0.69755 (15) | −0.49159 (18) | 0.22200 (6) | 0.0567 (5) | |
O3 | −0.07616 (12) | 0.45663 (15) | 0.17199 (5) | 0.0453 (4) | |
O4 | −0.00307 (16) | 0.18630 (18) | 0.29578 (6) | 0.0592 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0369 (13) | 0.0488 (14) | 0.0461 (14) | −0.0023 (11) | −0.0122 (11) | 0.0028 (11) |
C2 | 0.0448 (14) | 0.0713 (18) | 0.0435 (14) | 0.0054 (13) | −0.0012 (12) | 0.0088 (12) |
C3 | 0.0407 (13) | 0.0604 (16) | 0.0504 (15) | 0.0097 (12) | −0.0011 (12) | −0.0006 (12) |
C4 | 0.0366 (12) | 0.0442 (13) | 0.0429 (13) | 0.0017 (10) | −0.0086 (11) | −0.0028 (10) |
C5 | 0.0437 (13) | 0.0589 (15) | 0.0378 (13) | 0.0069 (12) | −0.0040 (11) | 0.0013 (12) |
C6 | 0.0401 (13) | 0.0566 (16) | 0.0475 (14) | 0.0122 (11) | −0.0053 (11) | −0.0002 (12) |
C7 | 0.0405 (13) | 0.0482 (15) | 0.0475 (14) | 0.0011 (11) | −0.0121 (11) | −0.0049 (11) |
C8 | 0.0570 (16) | 0.0705 (18) | 0.0659 (18) | 0.0210 (14) | −0.0130 (14) | 0.0011 (14) |
C9 | 0.0547 (15) | 0.0580 (17) | 0.0567 (17) | 0.0054 (13) | −0.0149 (14) | −0.0011 (13) |
C10 | 0.0485 (14) | 0.0559 (16) | 0.0418 (14) | 0.0013 (12) | −0.0118 (12) | −0.0011 (11) |
C11 | 0.0556 (16) | 0.0686 (18) | 0.0518 (16) | 0.0099 (13) | −0.0094 (13) | −0.0010 (13) |
C12 | 0.0582 (16) | 0.0740 (19) | 0.0454 (15) | −0.0043 (15) | −0.0049 (13) | −0.0007 (13) |
C13 | 0.0578 (16) | 0.0596 (16) | 0.0425 (14) | −0.0078 (13) | −0.0163 (13) | 0.0010 (12) |
C14 | 0.103 (2) | 0.092 (2) | 0.0466 (17) | −0.0282 (18) | −0.0228 (16) | 0.0141 (15) |
C15 | 0.097 (2) | 0.074 (2) | 0.083 (2) | −0.0003 (18) | −0.0419 (18) | 0.0164 (16) |
C16 | 0.0572 (16) | 0.0722 (19) | 0.0522 (16) | 0.0125 (14) | −0.0095 (13) | 0.0083 (14) |
C17 | 0.0516 (15) | 0.0772 (19) | 0.0445 (14) | 0.0061 (14) | −0.0035 (12) | 0.0071 (13) |
C18 | 0.0493 (14) | 0.0414 (14) | 0.0417 (14) | −0.0053 (11) | −0.0148 (12) | 0.0057 (10) |
C19 | 0.0485 (14) | 0.0473 (14) | 0.0527 (15) | 0.0071 (11) | −0.0148 (12) | 0.0107 (11) |
C20 | 0.0415 (13) | 0.0518 (15) | 0.0524 (15) | 0.0090 (12) | −0.0062 (11) | 0.0030 (12) |
C21 | 0.0390 (12) | 0.0383 (13) | 0.0380 (12) | 0.0015 (10) | −0.0104 (10) | 0.0001 (10) |
C22 | 0.0382 (12) | 0.0363 (13) | 0.0408 (13) | −0.0006 (10) | −0.0126 (10) | −0.0016 (10) |
C23 | 0.0437 (13) | 0.0475 (14) | 0.0391 (13) | 0.0049 (11) | −0.0046 (11) | 0.0004 (11) |
C24 | 0.0389 (12) | 0.0439 (14) | 0.0439 (13) | −0.0009 (11) | −0.0109 (11) | −0.0035 (10) |
C25 | 0.0534 (15) | 0.0732 (18) | 0.0492 (15) | 0.0109 (13) | −0.0025 (12) | −0.0017 (13) |
C26 | 0.0516 (14) | 0.0511 (15) | 0.0357 (13) | −0.0039 (12) | −0.0081 (11) | −0.0008 (11) |
C27 | 0.0475 (14) | 0.0470 (14) | 0.0355 (12) | −0.0073 (11) | −0.0102 (11) | 0.0010 (10) |
C28 | 0.0512 (14) | 0.0559 (16) | 0.0451 (14) | 0.0051 (12) | −0.0113 (12) | 0.0015 (12) |
C29 | 0.0515 (14) | 0.0653 (17) | 0.0373 (13) | 0.0011 (13) | −0.0026 (11) | 0.0024 (12) |
C30 | 0.0525 (15) | 0.0493 (15) | 0.0393 (13) | −0.0101 (12) | −0.0133 (12) | 0.0039 (11) |
C31 | 0.0561 (15) | 0.0487 (15) | 0.0497 (15) | 0.0056 (12) | −0.0085 (12) | 0.0025 (12) |
C32 | 0.0525 (14) | 0.0519 (15) | 0.0440 (14) | 0.0043 (12) | −0.0039 (12) | −0.0004 (11) |
C33 | 0.091 (2) | 0.089 (2) | 0.0424 (16) | −0.0192 (17) | −0.0057 (15) | 0.0125 (14) |
C34 | 0.099 (2) | 0.073 (2) | 0.072 (2) | −0.0115 (18) | −0.0329 (17) | 0.0286 (15) |
N1 | 0.0558 (13) | 0.0599 (14) | 0.0529 (13) | 0.0041 (10) | −0.0140 (11) | 0.0081 (10) |
N2 | 0.0531 (12) | 0.0579 (13) | 0.0527 (13) | 0.0078 (10) | −0.0154 (11) | 0.0066 (10) |
N3 | 0.0525 (12) | 0.0549 (13) | 0.0349 (11) | −0.0044 (10) | −0.0099 (9) | 0.0048 (9) |
N4 | 0.0463 (12) | 0.0475 (12) | 0.0355 (11) | 0.0003 (10) | −0.0071 (9) | 0.0023 (9) |
N5 | 0.0734 (15) | 0.0670 (15) | 0.0436 (13) | −0.0035 (12) | −0.0112 (11) | 0.0149 (10) |
N6 | 0.0805 (16) | 0.0718 (16) | 0.0534 (14) | −0.0054 (13) | −0.0232 (12) | 0.0121 (11) |
O1 | 0.0731 (13) | 0.1037 (16) | 0.0476 (11) | 0.0424 (12) | 0.0094 (10) | 0.0199 (10) |
O2 | 0.0474 (10) | 0.0652 (12) | 0.0526 (11) | 0.0044 (9) | −0.0083 (9) | 0.0133 (8) |
O3 | 0.0444 (9) | 0.0489 (9) | 0.0409 (9) | 0.0124 (7) | −0.0106 (7) | 0.0006 (7) |
O4 | 0.0723 (12) | 0.0577 (12) | 0.0431 (10) | 0.0095 (10) | −0.0112 (9) | 0.0104 (8) |
C1—O2 | 1.361 (3) | C19—C20 | 1.359 (3) |
C1—C6 | 1.374 (3) | C19—H19 | 0.9300 |
C1—C2 | 1.377 (3) | C20—C21 | 1.405 (3) |
C2—C3 | 1.375 (3) | C20—H20 | 0.9300 |
C2—H2 | 0.9300 | C21—C22 | 1.433 (3) |
C3—C4 | 1.396 (3) | C21—C24 | 1.436 (3) |
C3—H3 | 0.9300 | C22—O3 | 1.316 (2) |
C4—C5 | 1.407 (3) | C22—C23 | 1.394 (3) |
C4—C7 | 1.464 (3) | C23—H23 | 0.9300 |
C5—O1 | 1.344 (3) | C24—N4 | 1.305 (3) |
C5—C6 | 1.378 (3) | C24—C25 | 1.486 (3) |
C6—H6 | 0.9300 | C25—H25A | 0.9600 |
C7—N2 | 1.290 (3) | C25—H25B | 0.9600 |
C7—C8 | 1.494 (3) | C25—H25C | 0.9600 |
C8—H8A | 0.9600 | C26—N3 | 1.282 (3) |
C8—H8B | 0.9600 | C26—C27 | 1.438 (3) |
C8—H8C | 0.9600 | C26—H26 | 0.9300 |
C9—N1 | 1.273 (3) | C27—C32 | 1.384 (3) |
C9—C10 | 1.450 (3) | C27—C28 | 1.392 (3) |
C9—H9 | 0.9300 | C28—C29 | 1.364 (3) |
C10—C11 | 1.376 (3) | C28—H28 | 0.9300 |
C10—C17 | 1.383 (3) | C29—C30 | 1.403 (3) |
C11—C12 | 1.367 (3) | C29—H29 | 0.9300 |
C11—H11 | 0.9300 | C30—N5 | 1.363 (3) |
C12—C13 | 1.400 (3) | C30—C31 | 1.397 (3) |
C12—H12 | 0.9300 | C31—C32 | 1.373 (3) |
C13—N6 | 1.373 (3) | C31—H31 | 0.9300 |
C13—C16 | 1.388 (3) | C32—H32 | 0.9300 |
C14—N6 | 1.444 (3) | C33—N5 | 1.432 (3) |
C14—H14A | 0.9600 | C33—H33A | 0.9600 |
C14—H14B | 0.9600 | C33—H33B | 0.9600 |
C14—H14C | 0.9600 | C33—H33C | 0.9600 |
C15—N6 | 1.445 (3) | C34—N5 | 1.442 (3) |
C15—H15A | 0.9600 | C34—H34A | 0.9600 |
C15—H15B | 0.9600 | C34—H34B | 0.9600 |
C15—H15C | 0.9600 | C34—H34C | 0.9600 |
C16—C17 | 1.367 (3) | N1—N2 | 1.403 (3) |
C16—H16 | 0.9300 | N3—N4 | 1.374 (2) |
C17—H17 | 0.9300 | N4—H4 | 0.940 (9) |
C18—O4 | 1.346 (2) | O1—H1 | 0.864 (10) |
C18—C23 | 1.369 (3) | O2—H2A | 0.96 (3) |
C18—C19 | 1.394 (3) | O4—H4A | 0.84 (3) |
O2—C1—C6 | 121.8 (2) | C21—C20—H20 | 118.4 |
O2—C1—C2 | 118.8 (2) | C20—C21—C22 | 117.45 (19) |
C6—C1—C2 | 119.4 (2) | C20—C21—C24 | 120.42 (19) |
C3—C2—C1 | 119.7 (2) | C22—C21—C24 | 121.93 (19) |
C3—C2—H2 | 120.2 | O3—C22—C23 | 120.61 (18) |
C1—C2—H2 | 120.2 | O3—C22—C21 | 121.32 (18) |
C2—C3—C4 | 122.7 (2) | C23—C22—C21 | 118.05 (19) |
C2—C3—H3 | 118.7 | C18—C23—C22 | 122.3 (2) |
C4—C3—H3 | 118.7 | C18—C23—H23 | 118.8 |
C3—C4—C5 | 116.2 (2) | C22—C23—H23 | 118.8 |
C3—C4—C7 | 122.3 (2) | N4—C24—C21 | 118.78 (19) |
C5—C4—C7 | 121.5 (2) | N4—C24—C25 | 117.9 (2) |
O1—C5—C6 | 117.0 (2) | C21—C24—C25 | 123.3 (2) |
O1—C5—C4 | 122.0 (2) | C24—C25—H25A | 109.5 |
C6—C5—C4 | 121.0 (2) | C24—C25—H25B | 109.5 |
C1—C6—C5 | 121.1 (2) | H25A—C25—H25B | 109.5 |
C1—C6—H6 | 119.5 | C24—C25—H25C | 109.5 |
C5—C6—H6 | 119.5 | H25A—C25—H25C | 109.5 |
N2—C7—C4 | 116.24 (19) | H25B—C25—H25C | 109.5 |
N2—C7—C8 | 122.9 (2) | N3—C26—C27 | 122.2 (2) |
C4—C7—C8 | 120.8 (2) | N3—C26—H26 | 118.9 |
C7—C8—H8A | 109.5 | C27—C26—H26 | 118.9 |
C7—C8—H8B | 109.5 | C32—C27—C28 | 117.1 (2) |
H8A—C8—H8B | 109.5 | C32—C27—C26 | 120.6 (2) |
C7—C8—H8C | 109.5 | C28—C27—C26 | 122.3 (2) |
H8A—C8—H8C | 109.5 | C29—C28—C27 | 121.5 (2) |
H8B—C8—H8C | 109.5 | C29—C28—H28 | 119.3 |
N1—C9—C10 | 123.9 (2) | C27—C28—H28 | 119.3 |
N1—C9—H9 | 118.1 | C28—C29—C30 | 121.5 (2) |
C10—C9—H9 | 118.1 | C28—C29—H29 | 119.2 |
C11—C10—C17 | 116.6 (2) | C30—C29—H29 | 119.2 |
C11—C10—C9 | 120.8 (2) | N5—C30—C31 | 121.8 (2) |
C17—C10—C9 | 122.6 (2) | N5—C30—C29 | 121.3 (2) |
C12—C11—C10 | 122.6 (2) | C31—C30—C29 | 117.0 (2) |
C12—C11—H11 | 118.7 | C32—C31—C30 | 120.7 (2) |
C10—C11—H11 | 118.7 | C32—C31—H31 | 119.6 |
C11—C12—C13 | 120.7 (2) | C30—C31—H31 | 119.6 |
C11—C12—H12 | 119.6 | C31—C32—C27 | 122.2 (2) |
C13—C12—H12 | 119.6 | C31—C32—H32 | 118.9 |
N6—C13—C16 | 121.9 (2) | C27—C32—H32 | 118.9 |
N6—C13—C12 | 121.5 (2) | N5—C33—H33A | 109.5 |
C16—C13—C12 | 116.6 (2) | N5—C33—H33B | 109.5 |
N6—C14—H14A | 109.5 | H33A—C33—H33B | 109.5 |
N6—C14—H14B | 109.5 | N5—C33—H33C | 109.5 |
H14A—C14—H14B | 109.5 | H33A—C33—H33C | 109.5 |
N6—C14—H14C | 109.5 | H33B—C33—H33C | 109.5 |
H14A—C14—H14C | 109.5 | N5—C34—H34A | 109.5 |
H14B—C14—H14C | 109.5 | N5—C34—H34B | 109.5 |
N6—C15—H15A | 109.5 | H34A—C34—H34B | 109.5 |
N6—C15—H15B | 109.5 | N5—C34—H34C | 109.5 |
H15A—C15—H15B | 109.5 | H34A—C34—H34C | 109.5 |
N6—C15—H15C | 109.5 | H34B—C34—H34C | 109.5 |
H15A—C15—H15C | 109.5 | C9—N1—N2 | 111.5 (2) |
H15B—C15—H15C | 109.5 | C7—N2—N1 | 116.83 (19) |
C17—C16—C13 | 121.7 (2) | C26—N3—N4 | 114.76 (18) |
C17—C16—H16 | 119.2 | C24—N4—N3 | 121.64 (19) |
C13—C16—H16 | 119.2 | C24—N4—H4 | 112.0 (13) |
C16—C17—C10 | 121.8 (2) | N3—N4—H4 | 126.3 (14) |
C16—C17—H17 | 119.1 | C30—N5—C33 | 121.4 (2) |
C10—C17—H17 | 119.1 | C30—N5—C34 | 121.1 (2) |
O4—C18—C23 | 117.3 (2) | C33—N5—C34 | 117.3 (2) |
O4—C18—C19 | 122.7 (2) | C13—N6—C14 | 120.1 (2) |
C23—C18—C19 | 120.0 (2) | C13—N6—C15 | 120.2 (2) |
C20—C19—C18 | 119.0 (2) | C14—N6—C15 | 116.6 (2) |
C20—C19—H19 | 120.5 | C5—O1—H1 | 105 (2) |
C18—C19—H19 | 120.5 | C1—O2—H2A | 108.2 (16) |
C19—C20—C21 | 123.1 (2) | C18—O4—H4A | 113.7 (19) |
C19—C20—H20 | 118.4 | ||
O2—C1—C2—C3 | −178.6 (2) | C24—C21—C22—C23 | −174.86 (19) |
C6—C1—C2—C3 | 1.5 (3) | O4—C18—C23—C22 | 177.19 (19) |
C1—C2—C3—C4 | −0.9 (4) | C19—C18—C23—C22 | −2.4 (3) |
C2—C3—C4—C5 | −0.2 (3) | O3—C22—C23—C18 | −176.38 (19) |
C2—C3—C4—C7 | −179.7 (2) | C21—C22—C23—C18 | 1.9 (3) |
C3—C4—C5—O1 | −178.8 (2) | C20—C21—C24—N4 | −174.0 (2) |
C7—C4—C5—O1 | 0.7 (3) | C22—C21—C24—N4 | 0.7 (3) |
C3—C4—C5—C6 | 0.6 (3) | C20—C21—C24—C25 | 4.0 (3) |
C7—C4—C5—C6 | −179.9 (2) | C22—C21—C24—C25 | 178.7 (2) |
O2—C1—C6—C5 | 179.1 (2) | N3—C26—C27—C32 | 180.0 (2) |
C2—C1—C6—C5 | −1.1 (3) | N3—C26—C27—C28 | 1.2 (3) |
O1—C5—C6—C1 | 179.4 (2) | C32—C27—C28—C29 | 0.3 (3) |
C4—C5—C6—C1 | 0.0 (3) | C26—C27—C28—C29 | 179.1 (2) |
C3—C4—C7—N2 | 174.5 (2) | C27—C28—C29—C30 | 0.4 (4) |
C5—C4—C7—N2 | −5.0 (3) | C28—C29—C30—N5 | 179.5 (2) |
C3—C4—C7—C8 | −5.6 (3) | C28—C29—C30—C31 | −0.9 (3) |
C5—C4—C7—C8 | 174.9 (2) | N5—C30—C31—C32 | −179.7 (2) |
N1—C9—C10—C11 | −178.7 (2) | C29—C30—C31—C32 | 0.8 (3) |
N1—C9—C10—C17 | 1.1 (4) | C30—C31—C32—C27 | −0.1 (4) |
C17—C10—C11—C12 | 0.0 (4) | C28—C27—C32—C31 | −0.5 (3) |
C9—C10—C11—C12 | 179.8 (2) | C26—C27—C32—C31 | −179.3 (2) |
C10—C11—C12—C13 | 0.9 (4) | C10—C9—N1—N2 | −179.7 (2) |
C11—C12—C13—N6 | 177.7 (2) | C4—C7—N2—N1 | 179.66 (18) |
C11—C12—C13—C16 | −1.1 (3) | C8—C7—N2—N1 | −0.2 (3) |
N6—C13—C16—C17 | −178.3 (2) | C9—N1—N2—C7 | 177.1 (2) |
C12—C13—C16—C17 | 0.5 (4) | C27—C26—N3—N4 | 178.59 (18) |
C13—C16—C17—C10 | 0.4 (4) | C21—C24—N4—N3 | 175.20 (18) |
C11—C10—C17—C16 | −0.7 (4) | C25—C24—N4—N3 | −2.9 (3) |
C9—C10—C17—C16 | 179.6 (2) | C26—N3—N4—C24 | −174.93 (19) |
O4—C18—C19—C20 | −178.7 (2) | C31—C30—N5—C33 | −179.9 (2) |
C23—C18—C19—C20 | 0.9 (3) | C29—C30—N5—C33 | −0.4 (3) |
C18—C19—C20—C21 | 1.0 (4) | C31—C30—N5—C34 | −4.8 (3) |
C19—C20—C21—C22 | −1.5 (3) | C29—C30—N5—C34 | 174.8 (2) |
C19—C20—C21—C24 | 173.5 (2) | C16—C13—N6—C14 | −165.4 (2) |
C20—C21—C22—O3 | 178.32 (18) | C12—C13—N6—C14 | 15.9 (3) |
C24—C21—C22—O3 | 3.4 (3) | C16—C13—N6—C15 | −5.8 (4) |
C20—C21—C22—C23 | 0.1 (3) | C12—C13—N6—C15 | 175.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.86 (1) | 1.71 (2) | 2.507 (3) | 152 (3) |
N4—H4···O3 | 0.94 (1) | 1.72 (2) | 2.557 (2) | 147 (2) |
O2—H2A···O3i | 0.96 (3) | 1.71 (3) | 2.668 (2) | 170 (2) |
O4—H4A···O3ii | 0.84 (3) | 1.87 (3) | 2.674 (2) | 161 (3) |
Symmetry codes: (i) x+1, y−1, z; (ii) −x, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C17H19N3O2·C17H19N3O2 |
Mr | 594.70 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 11.872 (3), 9.630 (2), 28.441 (7) |
β (°) | 71.932 (4) |
V (Å3) | 3091.4 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.49 × 0.40 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12702, 5461, 3429 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.137, 1.02 |
No. of reflections | 5461 |
No. of parameters | 413 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.18 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.864 (10) | 1.711 (17) | 2.507 (3) | 152 (3) |
N4—H4···O3 | 0.940 (9) | 1.720 (15) | 2.557 (2) | 146.6 (19) |
O2—H2A···O3i | 0.96 (3) | 1.71 (3) | 2.668 (2) | 170 (2) |
O4—H4A···O3ii | 0.84 (3) | 1.87 (3) | 2.674 (2) | 161 (3) |
Symmetry codes: (i) x+1, y−1, z; (ii) −x, y−1/2, −z+1/2. |
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Schiff base ligands are of interest mainly because of the existence of typical hydrogen bonds and tautomerism between the phenol–imine and keto–amine forms (Costamagna et al., 1992; Sridharan et al., 2004; Fita et al., 2005). Tautomerism in o-hydroxy Schiff bases both in solution and in the solid state has been investigated using IR (Ledbetter, 1977; Yildiz et al., 1998), UV (Ottolenghi & McClure, 1967), 1H NMR (Dudek & Holm, 1962; Dudek & Dudek, 1966), 13C NMR (Salman et al., 1991) and X-ray crystallographic techniques (Gavranic et al., 1996; Kaitner & Pavlovic, 1996).
We have synthesized a new Schiff base compound, (I) (Fig. 1). This Schiff base compound undergoes tautomerism by proton transfer between the hydroxy O atom and the imine N atom, forming two tautomers, (Ia) and (Ib), and the two different tautomeric forms of the same molecule co-crystallized in a 1:1 ratio. Form (Ia) is the phenol–imine tautomeric form, while (Ib) is the keto–amine tautomer.
The compound crystallizes in the monoclinic form in space group P21/c. The tautomerism of the compound causes a series of differences between (Ia) and (Ib). When the phenol–imine form is transformed into the keto–amine form, an appreciable increase in the C—N distance is observed [C7—N2 = 1.290 (3) Å versus C24—N4 = 1.305 (3) Å]. A concomitant decrease in the C—O distance is also noted [C5—O1 = 1.344 (3) Å versus C22—O3 = 1.316 (2) Å]. The C7—N2 and C5—O1 distances are similar to the corresponding distances in 2,2'-azinodimethyldiphenol [1.285 (7) and 1.364 (8) Å; Xu et al., 1994] and 2,2'-[(1,2-ethanediyl)bis(nitrilopropylidyne)]bisphenol [1.295 (3) and 1.351 (3) Å; Corden et al., 1997], which exist in the phenol–imine tautomeric form. Likewise, the C24—N4 and C22—O3 bond lengths are similar to the corresponding distances in 2-{[tris(hydroxymethyl)methyl]aminomethylene)cyclohexa-3,5-dien-1(2H)-one [1.2952 (18) and 1.3025 (18) Å, respectively; Odabaşoǧlu et al., 2003] and 3-[(2-oxo-1-naphthylidene)methylamino]benzoic acid [1.319 (3) and 1.290 (2) Å; Pavlović & Sosa, 2000], which show the keto–amine tautomeric form. Hence, the C—O and C—N bond lengths verify the phenol–imine form of (Ia) and keto–amine form of (Ib). In addition, the degrees of planarity for the two molecules in the asymmetric unit are different. The maximum dihedral angle of (Ia) is 7.06 (9)°, for the dihedral angle between the C3-containing benzene ring and the C10-containing benzene ring, while the corresponding dihedral angle of (Ib) is 11.62 (7)°.
Both intramolecular and intermolecular hydrogen bonds are found in the crystal structures of the tautomers (Fig. 2). The intramolecular hydrogen bonds (O—H···N and N—H···O) of the two tautomeric forms are rather short, as expected [O1···N2 = 2.507 (3) Å and N4···O3 = 2.557 (2) Å; Table 1], with respective angles of 146.5 and 138.4° [these are different from the angles given in Table 1]. In (Ia), the hydrogen-bonded ring is nearly coplanar with the adjacent ring, with a dihedral angle of 1.37 (7)°, while (Ib) is not quite as planar, with a dihedral angle of 5.46 (7)° between the two corresponding rings. The two tautomers are connected via intermolecular O—H···O hydrogen bonds (Table 1) into a one-dimensional zigzag chain extended along the crystallographic b axis.
In conclusion, a new Schiff base has been synthesized and characterized by X-ray diffraction analysis. Two different tautomeric forms are found in the solid state, and these are hydrogen bonded to one another to form an infinite chain.