Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106017252/hj1092sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106017252/hj1092Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106017252/hj1092IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106017252/hj1092IIIsup4.hkl |
CCDC references: 616135; 616136; 616137
All three title compounds were prepared as described by Odabasoglu et al. (2003) using as starting materials 3-ethoxysalicylaldehyde and tris(hydroxymethyl)aminomethane for (I) (yield 92%, m.p. 437–439 K). 5-nitrosalicylaldehyde and tris(hydroxymethyl)aminomethane for (II) (yield 95%, m.p. 508–510 K), and salicylaldehyde and (R)-(-)-2-amino-1-butanol for (III) (yield 85%, m.p. 329–331 K).
For (I): Except the attached ones to N, all the H atoms were refined using a riding model with C—H distance of 0.93 A and Uiso values equal to 1.2Ueq of the parent atom.
For (II): Except the attached ones to O5 and O6, all H-atom parameters were freely refined, with C—H distance in the range 0.92 (2)–1.13 (2) Å and Uiso(H) values in the range 0.053 (6)–0.161 (15) Å2.
For (III): Except the attached ones to O1 and O2, all the H atoms were
refined using a riding model with C—H distance of 0.93 A and Uiso values equal to 1.2Ueq of the parent atom.
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).
C13H19NO5 | Z = 4 |
Mr = 269.29 | F(000) = 576 |
Triclinic, P1 | Dx = 1.348 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.7424 (8) Å | Cell parameters from 22555 reflections |
b = 10.6073 (8) Å | θ = 2.1–29.0° |
c = 14.4820 (11) Å | µ = 0.10 mm−1 |
α = 102.592 (6)° | T = 296 K |
β = 104.459 (6)° | Prism, yellow |
γ = 105.840 (6)° | 0.43 × 0.31 × 0.19 mm |
V = 1326.7 (2) Å3 |
Stoe IPDS-II diffractometer | 6080 independent reflections |
Radiation source: fine-focus sealed tube | 3597 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.051 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.5°, θmin = 2.1° |
ω scans | h = −12→12 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −13→13 |
Tmin = 0.946, Tmax = 0.988 | l = −18→18 |
22555 measured reflections |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.88 | w = 1/[σ2(Fo2) + (0.0498P)2] where P = (Fo2 + 2Fc2)/3 |
6080 reflections | (Δ/σ)max < 0.001 |
361 parameters | Δρmax = 0.14 e Å−3 |
6 restraints | Δρmin = −0.17 e Å−3 |
C13H19NO5 | γ = 105.840 (6)° |
Mr = 269.29 | V = 1326.7 (2) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.7424 (8) Å | Mo Kα radiation |
b = 10.6073 (8) Å | µ = 0.10 mm−1 |
c = 14.4820 (11) Å | T = 296 K |
α = 102.592 (6)° | 0.43 × 0.31 × 0.19 mm |
β = 104.459 (6)° |
Stoe IPDS-II diffractometer | 6080 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 3597 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.988 | Rint = 0.051 |
22555 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 6 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.88 | Δρmax = 0.14 e Å−3 |
6080 reflections | Δρmin = −0.17 e Å−3 |
361 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 | ||
C1A | 0.30620 (17) | 0.78245 (16) | 0.35738 (11) | 0.0350 (3) | |
C1B | −0.02877 (16) | −0.34129 (15) | 0.12329 (11) | 0.0340 (3) | |
C2A | 0.33266 (17) | 0.65711 (15) | 0.35498 (11) | 0.0347 (3) | |
C2B | −0.04911 (16) | −0.21183 (15) | 0.13568 (11) | 0.0339 (3) | |
C3A | 0.23044 (17) | 0.55769 (16) | 0.38209 (11) | 0.0375 (3) | |
C3B | 0.06703 (17) | −0.10185 (16) | 0.12875 (11) | 0.0357 (3) | |
C4A | 0.10705 (18) | 0.58075 (17) | 0.40102 (12) | 0.0437 (4) | |
H2A | 0.0409 | 0.5144 | 0.4172 | 0.052* | |
C4B | 0.19155 (17) | −0.12250 (16) | 0.11010 (12) | 0.0393 (4) | |
H2B | 0.2656 | −0.0498 | 0.1053 | 0.047* | |
C5A | 0.07808 (18) | 0.70205 (17) | 0.39664 (12) | 0.0432 (4) | |
H8A | −0.0082 | 0.7142 | 0.4076 | 0.052* | |
C5B | 0.20934 (17) | −0.25151 (17) | 0.09813 (12) | 0.0393 (4) | |
H8B | 0.2945 | −0.2637 | 0.0853 | 0.047* | |
C6A | 0.17592 (17) | 0.80151 (17) | 0.37635 (11) | 0.0390 (4) | |
H6A | 0.1577 | 0.8828 | 0.3748 | 0.047* | |
C6B | 0.10276 (17) | −0.35794 (16) | 0.10520 (11) | 0.0366 (3) | |
H6B | 0.1157 | −0.4428 | 0.0981 | 0.044* | |
C7A | 0.40902 (17) | 0.89210 (16) | 0.34174 (11) | 0.0367 (3) | |
H7A | 0.3856 | 0.9714 | 0.3418 | 0.044* | |
C7B | −0.13550 (17) | −0.45466 (16) | 0.13292 (11) | 0.0367 (3) | |
H7B | −0.1152 | −0.5361 | 0.1279 | 0.044* | |
C8A | 0.64885 (16) | 0.99457 (15) | 0.30974 (11) | 0.0347 (3) | |
C8B | −0.37344 (16) | −0.55637 (15) | 0.16759 (11) | 0.0359 (3) | |
C9A | 0.64241 (18) | 1.13715 (16) | 0.34918 (12) | 0.0406 (4) | |
H9A | 0.6462 | 1.1545 | 0.4185 | 0.049* | |
H9B | 0.7292 | 1.2060 | 0.3466 | 0.049* | |
C9B | −0.3673 (2) | −0.69896 (16) | 0.12986 (13) | 0.0468 (4) | |
H9C | −0.4519 | −0.7668 | 0.1357 | 0.056* | |
H9D | −0.3752 | −0.7194 | 0.0597 | 0.056* | |
C10A | 0.61801 (17) | 0.95061 (16) | 0.19595 (11) | 0.0378 (3) | |
H10A | 0.6046 | 0.8537 | 0.1728 | 0.045* | |
H10B | 0.5248 | 0.9623 | 0.1627 | 0.045* | |
C10B | −0.33988 (17) | −0.50974 (16) | 0.28126 (12) | 0.0386 (3) | |
H10C | −0.2462 | −0.5210 | 0.3141 | 0.046* | |
H10D | −0.3263 | −0.4127 | 0.3035 | 0.046* | |
C11A | 0.80283 (18) | 0.99254 (17) | 0.36695 (13) | 0.0434 (4) | |
H11A | 0.8810 | 1.0539 | 0.3509 | 0.052* | |
H11B | 0.8213 | 1.0269 | 0.4383 | 0.052* | |
C11B | −0.52858 (18) | −0.55692 (17) | 0.11089 (13) | 0.0436 (4) | |
H11C | −0.5475 | −0.5917 | 0.0395 | 0.052* | |
H11D | −0.6053 | −0.6190 | 0.1275 | 0.052* | |
C22A | 0.1902 (2) | 0.35134 (19) | 0.42777 (15) | 0.0569 (5) | |
H22A | 0.0841 | 0.3104 | 0.3875 | 0.068* | |
H22B | 0.1983 | 0.4003 | 0.4949 | 0.068* | |
C22B | 0.14276 (18) | 0.13258 (16) | 0.12848 (14) | 0.0442 (4) | |
H22C | 0.1514 | 0.1077 | 0.0622 | 0.053* | |
H22D | 0.2419 | 0.1593 | 0.1778 | 0.053* | |
C33A | 0.2592 (3) | 0.2417 (2) | 0.43089 (17) | 0.0743 (6) | |
H33A | 0.2077 | 0.1780 | 0.4596 | 0.112* | |
H33B | 0.3641 | 0.2832 | 0.4710 | 0.112* | |
H33C | 0.2501 | 0.1935 | 0.3641 | 0.112* | |
C33B | 0.0829 (2) | 0.24890 (18) | 0.14170 (14) | 0.0509 (4) | |
H33D | 0.1501 | 0.3272 | 0.1332 | 0.076* | |
H33E | 0.0754 | 0.2729 | 0.2077 | 0.076* | |
H33F | −0.0153 | 0.2211 | 0.0927 | 0.076* | |
N1A | 0.53427 (14) | 0.88833 (14) | 0.32724 (10) | 0.0369 (3) | |
N1B | −0.25991 (14) | −0.45078 (14) | 0.14838 (10) | 0.0372 (3) | |
O1A | 0.44364 (12) | 0.63210 (11) | 0.33041 (9) | 0.0443 (3) | |
O1B | −0.16637 (12) | −0.19203 (11) | 0.15402 (9) | 0.0452 (3) | |
O2A | 0.26921 (13) | 0.44390 (11) | 0.38499 (9) | 0.0463 (3) | |
O2B | 0.03846 (12) | 0.01887 (11) | 0.14138 (9) | 0.0452 (3) | |
O3A | 0.50771 (13) | 1.14768 (12) | 0.29112 (9) | 0.0467 (3) | |
O3B | −0.23044 (15) | −0.70647 (13) | 0.18605 (12) | 0.0638 (4) | |
O4A | 0.73646 (13) | 1.02752 (12) | 0.16903 (9) | 0.0486 (3) | |
O4B | −0.45729 (13) | −0.58538 (11) | 0.31012 (9) | 0.0464 (3) | |
O5A | 0.81233 (14) | 0.85944 (13) | 0.34382 (9) | 0.0492 (3) | |
O5B | −0.54130 (14) | −0.42492 (13) | 0.13334 (10) | 0.0516 (3) | |
H1A | 0.5467 (19) | 0.809 (2) | 0.3255 (13) | 0.050 (5)* | |
H1B | −0.272 (2) | −0.370 (2) | 0.1517 (13) | 0.055 (5)* | |
H3A | 0.519 (2) | 1.2337 (17) | 0.3025 (16) | 0.082* | |
H3B | −0.240 (3) | −0.7900 (17) | 0.1760 (17) | 0.082* | |
H4A | 0.791 (2) | 0.981 (2) | 0.1612 (17) | 0.082* | |
H4B | −0.505 (2) | −0.531 (2) | 0.3254 (16) | 0.082* | |
H5A | 0.831 (3) | 0.843 (2) | 0.2897 (13) | 0.082* | |
H5B | −0.556 (3) | −0.408 (2) | 0.1893 (13) | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0372 (8) | 0.0371 (8) | 0.0345 (8) | 0.0136 (7) | 0.0160 (7) | 0.0126 (6) |
C1B | 0.0356 (8) | 0.0318 (8) | 0.0381 (8) | 0.0120 (6) | 0.0168 (7) | 0.0118 (6) |
C2A | 0.0371 (8) | 0.0346 (8) | 0.0354 (8) | 0.0130 (7) | 0.0163 (7) | 0.0107 (6) |
C2B | 0.0336 (8) | 0.0354 (8) | 0.0367 (8) | 0.0123 (7) | 0.0171 (7) | 0.0117 (6) |
C3A | 0.0429 (9) | 0.0329 (8) | 0.0374 (8) | 0.0114 (7) | 0.0159 (7) | 0.0114 (7) |
C3B | 0.0373 (8) | 0.0333 (8) | 0.0392 (8) | 0.0130 (7) | 0.0156 (7) | 0.0118 (7) |
C4A | 0.0394 (9) | 0.0444 (10) | 0.0478 (9) | 0.0081 (7) | 0.0212 (8) | 0.0157 (8) |
C4B | 0.0323 (8) | 0.0390 (9) | 0.0487 (9) | 0.0085 (7) | 0.0179 (7) | 0.0174 (7) |
C5A | 0.0365 (9) | 0.0515 (11) | 0.0459 (9) | 0.0174 (8) | 0.0189 (8) | 0.0142 (8) |
C5B | 0.0330 (8) | 0.0458 (9) | 0.0444 (9) | 0.0164 (7) | 0.0178 (7) | 0.0148 (7) |
C6A | 0.0402 (9) | 0.0399 (9) | 0.0422 (9) | 0.0185 (7) | 0.0165 (7) | 0.0133 (7) |
C6B | 0.0390 (8) | 0.0363 (9) | 0.0397 (8) | 0.0173 (7) | 0.0170 (7) | 0.0115 (7) |
C7A | 0.0426 (9) | 0.0349 (8) | 0.0400 (8) | 0.0181 (7) | 0.0180 (7) | 0.0149 (7) |
C7B | 0.0404 (9) | 0.0334 (8) | 0.0434 (9) | 0.0162 (7) | 0.0202 (7) | 0.0137 (7) |
C8A | 0.0346 (8) | 0.0286 (8) | 0.0461 (9) | 0.0118 (6) | 0.0175 (7) | 0.0152 (7) |
C8B | 0.0361 (8) | 0.0310 (8) | 0.0474 (9) | 0.0114 (7) | 0.0218 (7) | 0.0165 (7) |
C9A | 0.0411 (9) | 0.0337 (9) | 0.0490 (9) | 0.0147 (7) | 0.0161 (8) | 0.0132 (7) |
C9B | 0.0564 (11) | 0.0317 (9) | 0.0625 (11) | 0.0152 (8) | 0.0351 (9) | 0.0162 (8) |
C10A | 0.0370 (8) | 0.0357 (9) | 0.0480 (9) | 0.0148 (7) | 0.0202 (7) | 0.0169 (7) |
C10B | 0.0402 (8) | 0.0351 (9) | 0.0490 (9) | 0.0161 (7) | 0.0209 (7) | 0.0180 (7) |
C11A | 0.0400 (9) | 0.0393 (9) | 0.0515 (10) | 0.0164 (7) | 0.0129 (8) | 0.0143 (8) |
C11B | 0.0420 (9) | 0.0418 (10) | 0.0498 (10) | 0.0123 (7) | 0.0184 (8) | 0.0187 (8) |
C22A | 0.0726 (13) | 0.0482 (11) | 0.0600 (11) | 0.0163 (10) | 0.0334 (10) | 0.0286 (9) |
C22B | 0.0368 (8) | 0.0374 (9) | 0.0595 (11) | 0.0089 (7) | 0.0161 (8) | 0.0217 (8) |
C33A | 0.0993 (17) | 0.0591 (13) | 0.0844 (15) | 0.0330 (13) | 0.0381 (14) | 0.0441 (12) |
C33B | 0.0499 (10) | 0.0393 (10) | 0.0654 (12) | 0.0151 (8) | 0.0180 (9) | 0.0212 (9) |
N1A | 0.0408 (7) | 0.0301 (7) | 0.0478 (8) | 0.0150 (6) | 0.0214 (6) | 0.0161 (6) |
N1B | 0.0394 (7) | 0.0293 (7) | 0.0520 (8) | 0.0134 (6) | 0.0243 (6) | 0.0171 (6) |
O1A | 0.0489 (7) | 0.0378 (6) | 0.0642 (7) | 0.0222 (5) | 0.0351 (6) | 0.0223 (5) |
O1B | 0.0432 (6) | 0.0365 (6) | 0.0724 (8) | 0.0186 (5) | 0.0367 (6) | 0.0226 (6) |
O2A | 0.0521 (7) | 0.0372 (6) | 0.0596 (7) | 0.0156 (5) | 0.0283 (6) | 0.0228 (5) |
O2B | 0.0427 (6) | 0.0337 (6) | 0.0693 (8) | 0.0146 (5) | 0.0290 (6) | 0.0212 (6) |
O3A | 0.0442 (6) | 0.0345 (6) | 0.0673 (8) | 0.0194 (5) | 0.0177 (6) | 0.0204 (6) |
O3B | 0.0626 (8) | 0.0407 (7) | 0.1151 (12) | 0.0304 (7) | 0.0481 (8) | 0.0391 (8) |
O4A | 0.0557 (7) | 0.0402 (7) | 0.0764 (8) | 0.0264 (6) | 0.0434 (7) | 0.0318 (6) |
O4B | 0.0622 (8) | 0.0371 (7) | 0.0639 (7) | 0.0252 (6) | 0.0422 (6) | 0.0273 (6) |
O5A | 0.0564 (7) | 0.0472 (7) | 0.0597 (8) | 0.0318 (6) | 0.0244 (6) | 0.0230 (6) |
O5B | 0.0542 (7) | 0.0562 (8) | 0.0627 (8) | 0.0315 (6) | 0.0265 (6) | 0.0292 (7) |
C1A—C7A | 1.414 (2) | C9A—H9B | 0.9700 |
C1A—C2A | 1.417 (2) | C9B—O3B | 1.411 (2) |
C1A—C6A | 1.420 (2) | C9B—H9C | 0.9700 |
C1B—C7B | 1.418 (2) | C9B—H9D | 0.9700 |
C1B—C6B | 1.4188 (19) | C10A—O4A | 1.4138 (17) |
C1B—C2B | 1.420 (2) | C10A—H10A | 0.9700 |
C2A—O1A | 1.2936 (16) | C10A—H10B | 0.9700 |
C2A—C3A | 1.435 (2) | C10B—O4B | 1.4180 (17) |
C2B—O1B | 1.2952 (16) | C10B—H10C | 0.9700 |
C2B—C3B | 1.428 (2) | C10B—H10D | 0.9700 |
C3A—O2A | 1.3653 (18) | C11A—O5A | 1.4123 (19) |
C3A—C4A | 1.370 (2) | C11A—H11A | 0.9700 |
C3B—O2B | 1.3669 (18) | C11A—H11B | 0.9700 |
C3B—C4B | 1.370 (2) | C11B—O5B | 1.413 (2) |
C4A—C5A | 1.402 (2) | C11B—H11C | 0.9700 |
C4A—H2A | 0.9300 | C11B—H11D | 0.9700 |
C4B—C5B | 1.405 (2) | C22A—O2A | 1.4252 (18) |
C4B—H2B | 0.9300 | C22A—C33A | 1.497 (3) |
C5A—C6A | 1.354 (2) | C22A—H22A | 0.9700 |
C5A—H8A | 0.9300 | C22A—H22B | 0.9700 |
C5B—C6B | 1.352 (2) | C22B—O2B | 1.4304 (18) |
C5B—H8B | 0.9300 | C22B—C33B | 1.498 (2) |
C6A—H6A | 0.9300 | C22B—H22C | 0.9700 |
C6B—H6B | 0.9300 | C22B—H22D | 0.9700 |
C7A—N1A | 1.2983 (18) | C33A—H33A | 0.9600 |
C7A—H7A | 0.9300 | C33A—H33B | 0.9600 |
C7B—N1B | 1.2960 (18) | C33A—H33C | 0.9600 |
C7B—H7B | 0.9300 | C33B—H33D | 0.9600 |
C8A—N1A | 1.4695 (18) | C33B—H33E | 0.9600 |
C8A—C9A | 1.520 (2) | C33B—H33F | 0.9600 |
C8A—C11A | 1.530 (2) | N1A—H1A | 0.878 (19) |
C8A—C10A | 1.538 (2) | N1B—H1B | 0.887 (19) |
C8B—N1B | 1.4726 (18) | O3A—H3A | 0.861 (16) |
C8B—C9B | 1.515 (2) | O3B—H3B | 0.841 (16) |
C8B—C11B | 1.527 (2) | O4A—H4A | 0.831 (15) |
C8B—C10B | 1.533 (2) | O4B—H4B | 0.860 (15) |
C9A—O3A | 1.4183 (19) | O5A—H5A | 0.839 (15) |
C9A—H9A | 0.9700 | O5B—H5B | 0.845 (15) |
C7A—C1A—C2A | 121.01 (13) | C8B—C9B—H9D | 109.6 |
C7A—C1A—C6A | 118.26 (14) | H9C—C9B—H9D | 108.1 |
C2A—C1A—C6A | 120.73 (13) | O4A—C10A—C8A | 112.39 (13) |
C7B—C1B—C6B | 118.58 (13) | O4A—C10A—H10A | 109.1 |
C7B—C1B—C2B | 121.00 (13) | C8A—C10A—H10A | 109.1 |
C6B—C1B—C2B | 120.37 (13) | O4A—C10A—H10B | 109.1 |
O1A—C2A—C1A | 122.40 (13) | C8A—C10A—H10B | 109.1 |
O1A—C2A—C3A | 120.81 (13) | H10A—C10A—H10B | 107.9 |
C1A—C2A—C3A | 116.78 (13) | O4B—C10B—C8B | 112.23 (13) |
O1B—C2B—C1B | 122.15 (13) | O4B—C10B—H10C | 109.2 |
O1B—C2B—C3B | 120.62 (13) | C8B—C10B—H10C | 109.2 |
C1B—C2B—C3B | 117.23 (12) | O4B—C10B—H10D | 109.2 |
O2A—C3A—C4A | 126.12 (14) | C8B—C10B—H10D | 109.2 |
O2A—C3A—C2A | 113.46 (13) | H10C—C10B—H10D | 107.9 |
C4A—C3A—C2A | 120.41 (14) | O5A—C11A—C8A | 112.59 (13) |
O2B—C3B—C4B | 125.92 (13) | O5A—C11A—H11A | 109.1 |
O2B—C3B—C2B | 113.45 (12) | C8A—C11A—H11A | 109.1 |
C4B—C3B—C2B | 120.63 (14) | O5A—C11A—H11B | 109.1 |
C3A—C4A—C5A | 121.55 (14) | C8A—C11A—H11B | 109.1 |
C3A—C4A—H2A | 119.2 | H11A—C11A—H11B | 107.8 |
C5A—C4A—H2A | 119.2 | O5B—C11B—C8B | 112.84 (14) |
C3B—C4B—C5B | 121.17 (14) | O5B—C11B—H11C | 109.0 |
C3B—C4B—H2B | 119.4 | C8B—C11B—H11C | 109.0 |
C5B—C4B—H2B | 119.4 | O5B—C11B—H11D | 109.0 |
C6A—C5A—C4A | 119.86 (14) | C8B—C11B—H11D | 109.0 |
C6A—C5A—H8A | 120.1 | H11C—C11B—H11D | 107.8 |
C4A—C5A—H8A | 120.1 | O2A—C22A—C33A | 108.00 (15) |
C6B—C5B—C4B | 120.06 (14) | O2A—C22A—H22A | 110.1 |
C6B—C5B—H8B | 120.0 | C33A—C22A—H22A | 110.1 |
C4B—C5B—H8B | 120.0 | O2A—C22A—H22B | 110.1 |
C5A—C6A—C1A | 120.39 (14) | C33A—C22A—H22B | 110.1 |
C5A—C6A—H6A | 119.8 | H22A—C22A—H22B | 108.4 |
C1A—C6A—H6A | 119.8 | O2B—C22B—C33B | 107.19 (13) |
C5B—C6B—C1B | 120.54 (14) | O2B—C22B—H22C | 110.3 |
C5B—C6B—H6B | 119.7 | C33B—C22B—H22C | 110.3 |
C1B—C6B—H6B | 119.7 | O2B—C22B—H22D | 110.3 |
N1A—C7A—C1A | 123.74 (14) | C33B—C22B—H22D | 110.3 |
N1A—C7A—H7A | 118.1 | H22C—C22B—H22D | 108.5 |
C1A—C7A—H7A | 118.1 | C22A—C33A—H33A | 109.5 |
N1B—C7B—C1B | 123.48 (14) | C22A—C33A—H33B | 109.5 |
N1B—C7B—H7B | 118.3 | H33A—C33A—H33B | 109.5 |
C1B—C7B—H7B | 118.3 | C22A—C33A—H33C | 109.5 |
N1A—C8A—C9A | 111.76 (12) | H33A—C33A—H33C | 109.5 |
N1A—C8A—C11A | 106.66 (12) | H33B—C33A—H33C | 109.5 |
C9A—C8A—C11A | 108.67 (13) | C22B—C33B—H33D | 109.5 |
N1A—C8A—C10A | 105.68 (12) | C22B—C33B—H33E | 109.5 |
C9A—C8A—C10A | 112.46 (12) | H33D—C33B—H33E | 109.5 |
C11A—C8A—C10A | 111.46 (12) | C22B—C33B—H33F | 109.5 |
N1B—C8B—C9B | 112.15 (12) | H33D—C33B—H33F | 109.5 |
N1B—C8B—C11B | 107.17 (12) | H33E—C33B—H33F | 109.5 |
C9B—C8B—C11B | 108.17 (14) | C7A—N1A—C8A | 128.68 (13) |
N1B—C8B—C10B | 105.30 (12) | C7A—N1A—H1A | 112.9 (11) |
C9B—C8B—C10B | 112.26 (13) | C8A—N1A—H1A | 118.4 (11) |
C11B—C8B—C10B | 111.70 (12) | C7B—N1B—C8B | 128.84 (13) |
O3A—C9A—C8A | 110.41 (13) | C7B—N1B—H1B | 113.0 (11) |
O3A—C9A—H9A | 109.6 | C8B—N1B—H1B | 118.0 (11) |
C8A—C9A—H9A | 109.6 | C3A—O2A—C22A | 117.20 (12) |
O3A—C9A—H9B | 109.6 | C3B—O2B—C22B | 117.69 (11) |
C8A—C9A—H9B | 109.6 | C9A—O3A—H3A | 108.0 (15) |
H9A—C9A—H9B | 108.1 | C9B—O3B—H3B | 108.1 (16) |
O3B—C9B—C8B | 110.13 (14) | C10A—O4A—H4A | 107.9 (16) |
O3B—C9B—H9C | 109.6 | C10B—O4B—H4B | 106.3 (15) |
C8B—C9B—H9C | 109.6 | C11A—O5A—H5A | 108.4 (16) |
O3B—C9B—H9D | 109.6 | C11B—O5B—H5B | 108.0 (16) |
C7A—C1A—C2A—O1A | −5.9 (2) | N1A—C8A—C9A—O3A | −68.60 (16) |
C6A—C1A—C2A—O1A | 174.57 (14) | C11A—C8A—C9A—O3A | 173.97 (12) |
C7A—C1A—C2A—C3A | 173.62 (14) | C10A—C8A—C9A—O3A | 50.08 (16) |
C6A—C1A—C2A—C3A | −5.9 (2) | N1B—C8B—C9B—O3B | 66.88 (17) |
C7B—C1B—C2B—O1B | −1.5 (2) | C11B—C8B—C9B—O3B | −175.14 (12) |
C6B—C1B—C2B—O1B | −178.79 (14) | C10B—C8B—C9B—O3B | −51.45 (16) |
C7B—C1B—C2B—C3B | 177.49 (14) | N1A—C8A—C10A—O4A | −168.39 (12) |
C6B—C1B—C2B—C3B | 0.2 (2) | C9A—C8A—C10A—O4A | 69.42 (16) |
O1A—C2A—C3A—O2A | 3.9 (2) | C11A—C8A—C10A—O4A | −52.90 (16) |
C1A—C2A—C3A—O2A | −175.58 (13) | N1B—C8B—C10B—O4B | 168.24 (12) |
O1A—C2A—C3A—C4A | −175.30 (15) | C9B—C8B—C10B—O4B | −69.46 (16) |
C1A—C2A—C3A—C4A | 5.2 (2) | C11B—C8B—C10B—O4B | 52.24 (16) |
O1B—C2B—C3B—O2B | −1.1 (2) | N1A—C8A—C11A—O5A | 52.16 (17) |
C1B—C2B—C3B—O2B | 179.89 (13) | C9A—C8A—C11A—O5A | 172.80 (12) |
O1B—C2B—C3B—C4B | 179.52 (14) | C10A—C8A—C11A—O5A | −62.72 (17) |
C1B—C2B—C3B—C4B | 0.5 (2) | N1B—C8B—C11B—O5B | −53.05 (16) |
O2A—C3A—C4A—C5A | 179.56 (15) | C9B—C8B—C11B—O5B | −174.17 (12) |
C2A—C3A—C4A—C5A | −1.3 (2) | C10B—C8B—C11B—O5B | 61.80 (16) |
O2B—C3B—C4B—C5B | −179.86 (15) | C1A—C7A—N1A—C8A | 179.63 (15) |
C2B—C3B—C4B—C5B | −0.5 (2) | C9A—C8A—N1A—C7A | 22.5 (2) |
C3A—C4A—C5A—C6A | −2.1 (2) | C11A—C8A—N1A—C7A | 141.16 (16) |
C3B—C4B—C5B—C6B | −0.2 (2) | C10A—C8A—N1A—C7A | −100.12 (17) |
C4A—C5A—C6A—C1A | 1.3 (2) | C1B—C7B—N1B—C8B | −174.65 (15) |
C7A—C1A—C6A—C5A | −176.76 (15) | C9B—C8B—N1B—C7B | −22.1 (2) |
C2A—C1A—C6A—C5A | 2.8 (2) | C11B—C8B—N1B—C7B | −140.72 (16) |
C4B—C5B—C6B—C1B | 0.9 (2) | C10B—C8B—N1B—C7B | 100.22 (17) |
C7B—C1B—C6B—C5B | −178.26 (15) | C4A—C3A—O2A—C22A | −11.4 (2) |
C2B—C1B—C6B—C5B | −0.9 (2) | C2A—C3A—O2A—C22A | 169.38 (14) |
C2A—C1A—C7A—N1A | −2.0 (2) | C33A—C22A—O2A—C3A | −175.37 (16) |
C6A—C1A—C7A—N1A | 177.53 (14) | C4B—C3B—O2B—C22B | 3.8 (2) |
C6B—C1B—C7B—N1B | −179.21 (14) | C2B—C3B—O2B—C22B | −175.52 (13) |
C2B—C1B—C7B—N1B | 3.5 (2) | C33B—C22B—O2B—C3B | 177.54 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3A—H3A···O4Bi | 0.86 (2) | 1.85 (2) | 2.7011 (15) | 173 (2) |
O3B—H3B···O4Aii | 0.84 (2) | 1.86 (2) | 2.6994 (16) | 173 (2) |
O4A—H4A···O1Biii | 0.83 (2) | 1.98 (2) | 2.7300 (15) | 150 (2) |
O4A—H4A···O2Biii | 0.83 (2) | 2.43 (2) | 3.0894 (15) | 137 (2) |
O4B—H4B···O1Aiv | 0.86 (2) | 1.92 (2) | 2.7205 (15) | 154 (2) |
O4B—H4B···O2Aiv | 0.86 (2) | 2.52 (2) | 3.1811 (15) | 134 (2) |
O5A—H5A···O1Biii | 0.84 (2) | 1.93 (2) | 2.7548 (16) | 169 (2) |
O5B—H5B···O1Aiv | 0.85 (2) | 2.00 (2) | 2.8351 (16) | 171 (2) |
N1A—H1A···O1A | 0.878 (19) | 1.898 (19) | 2.6331 (17) | 140.3 (15) |
N1B—H1B···O1B | 0.887 (19) | 1.876 (19) | 2.6210 (17) | 140.4 (16) |
C9A—H9A···Cg1v | 0.97 | 2.84 | 3.7045 (17) | 149 |
C33B—H33F···Cg2vi | 0.96 | 2.97 | 3.628 (2) | 127 |
Symmetry codes: (i) x+1, y+2, z; (ii) x−1, y−2, z; (iii) x+1, y+1, z; (iv) x−1, y−1, z; (v) −x+1, −y+2, −z+1; (vi) −x+2, −y+2, −z. |
C11H14N2O6·H2O | F(000) = 608 |
Mr = 288.26 | Dx = 1.482 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 11553 reflections |
a = 16.9205 (11) Å | θ = 1.9–28.8° |
b = 10.7034 (6) Å | µ = 0.13 mm−1 |
c = 7.2308 (5) Å | T = 296 K |
β = 99.518 (5)° | Plate, yellow |
V = 1291.52 (14) Å3 | 0.38 × 0.25 × 0.08 mm |
Z = 4 |
Stoe IPDS-II diffractometer | 2877 independent reflections |
Radiation source: fine-focus sealed tube | 1898 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.059 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
ω scans | h = −21→21 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −13→13 |
Tmin = 0.955, Tmax = 0.989 | l = −9→9 |
11553 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.107 | w = 1/[σ2(Fo2) + (0.0623P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.93 | (Δ/σ)max < 0.001 |
2877 reflections | Δρmax = 0.30 e Å−3 |
214 parameters | Δρmin = −0.32 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: 0.053 (4) |
C11H14N2O6·H2O | V = 1291.52 (14) Å3 |
Mr = 288.26 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.9205 (11) Å | µ = 0.13 mm−1 |
b = 10.7034 (6) Å | T = 296 K |
c = 7.2308 (5) Å | 0.38 × 0.25 × 0.08 mm |
β = 99.518 (5)° |
Stoe IPDS-II diffractometer | 2877 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 1898 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.989 | Rint = 0.059 |
11553 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 2 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.93 | Δρmax = 0.30 e Å−3 |
2877 reflections | Δρmin = −0.32 e Å−3 |
214 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 | 0.14865 (9) | 0.67746 (12) | 0.3596 (2) | 0.0316 (3) | |
C2 | 0.18202 (9) | 0.79887 (14) | 0.3327 (2) | 0.0341 (4) | |
C3 | 0.12911 (11) | 0.90282 (15) | 0.3381 (3) | 0.0405 (4) | |
C4 | 0.05203 (11) | 0.88724 (15) | 0.3619 (3) | 0.0400 (4) | |
C5 | 0.02170 (9) | 0.76740 (14) | 0.3870 (2) | 0.0352 (4) | |
C6 | 0.06965 (9) | 0.66455 (14) | 0.3869 (2) | 0.0344 (4) | |
C7 | 0.19745 (9) | 0.56849 (14) | 0.3731 (2) | 0.0332 (4) | |
C8 | 0.33033 (9) | 0.46906 (13) | 0.3950 (2) | 0.0319 (3) | |
C9 | 0.28957 (9) | 0.34190 (14) | 0.3605 (3) | 0.0389 (4) | |
H9A | 0.2485 | 0.3327 | 0.4386 | 0.047* | |
H9B | 0.2644 | 0.3347 | 0.2303 | 0.047* | |
C10 | 0.36916 (9) | 0.48493 (14) | 0.6009 (2) | 0.0364 (4) | |
H10A | 0.4121 | 0.4246 | 0.6311 | 0.044* | |
H10B | 0.3923 | 0.5679 | 0.6189 | 0.044* | |
C11 | 0.39198 (10) | 0.48684 (15) | 0.2657 (3) | 0.0421 (4) | |
H11A | 0.4368 | 0.4305 | 0.3020 | 0.051* | |
H11B | 0.3680 | 0.4679 | 0.1375 | 0.051* | |
N1 | 0.27144 (8) | 0.57004 (12) | 0.3532 (2) | 0.0331 (3) | |
N2 | −0.05935 (8) | 0.75260 (14) | 0.4191 (2) | 0.0435 (4) | |
O1 | 0.25388 (7) | 0.81207 (10) | 0.30752 (19) | 0.0454 (3) | |
O2 | −0.10117 (8) | 0.84614 (14) | 0.4203 (3) | 0.0681 (5) | |
O3 | −0.08391 (8) | 0.64744 (13) | 0.4466 (2) | 0.0622 (4) | |
O4 | 0.34854 (7) | 0.24826 (10) | 0.40463 (19) | 0.0483 (3) | |
H4A | 0.3276 | 0.1792 | 0.3879 | 0.072* | |
O5 | 0.31300 (7) | 0.46812 (10) | 0.72336 (17) | 0.0419 (3) | |
H5A | 0.2769 | 0.5196 | 0.6989 | 0.063* | |
O6 | 0.41917 (8) | 0.61161 (11) | 0.2783 (2) | 0.0506 (4) | |
O7 | 0.48561 (10) | 0.68839 (15) | −0.0087 (3) | 0.0630 (4) | |
H1 | 0.2918 (12) | 0.640 (2) | 0.327 (3) | 0.051 (6)* | |
H2 | 0.1488 (13) | 0.982 (2) | 0.319 (3) | 0.065 (6)* | |
H3 | 0.0153 (12) | 0.952 (2) | 0.360 (3) | 0.058 (6)* | |
H4 | 0.0493 (12) | 0.5849 (18) | 0.410 (3) | 0.050 (5)* | |
H5 | 0.1737 (10) | 0.4898 (17) | 0.408 (3) | 0.040 (5)* | |
H6 | 0.4431 (16) | 0.632 (2) | 0.183 (4) | 0.076 (8)* | |
H7A | 0.4601 (15) | 0.747 (2) | −0.062 (4) | 0.082 (9)* | |
H7B | 0.5317 (12) | 0.714 (3) | 0.030 (4) | 0.098 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0350 (7) | 0.0262 (7) | 0.0340 (8) | 0.0018 (6) | 0.0073 (7) | 0.0010 (6) |
C2 | 0.0393 (8) | 0.0301 (7) | 0.0344 (9) | 0.0008 (6) | 0.0108 (7) | 0.0039 (6) |
C3 | 0.0500 (10) | 0.0272 (7) | 0.0465 (10) | 0.0029 (6) | 0.0143 (8) | 0.0050 (6) |
C4 | 0.0454 (9) | 0.0323 (8) | 0.0434 (10) | 0.0099 (7) | 0.0107 (8) | 0.0014 (7) |
C5 | 0.0330 (8) | 0.0377 (8) | 0.0353 (9) | 0.0036 (6) | 0.0066 (7) | −0.0008 (6) |
C6 | 0.0348 (8) | 0.0307 (7) | 0.0374 (9) | −0.0003 (6) | 0.0051 (7) | −0.0001 (6) |
C7 | 0.0321 (7) | 0.0285 (7) | 0.0391 (9) | −0.0011 (6) | 0.0066 (7) | −0.0006 (6) |
C8 | 0.0302 (7) | 0.0245 (7) | 0.0422 (9) | 0.0024 (5) | 0.0099 (7) | −0.0022 (6) |
C9 | 0.0371 (8) | 0.0268 (7) | 0.0526 (11) | 0.0014 (6) | 0.0068 (8) | −0.0038 (7) |
C10 | 0.0363 (8) | 0.0317 (7) | 0.0428 (9) | 0.0027 (6) | 0.0106 (7) | −0.0027 (6) |
C11 | 0.0433 (9) | 0.0366 (8) | 0.0500 (11) | −0.0010 (7) | 0.0183 (8) | −0.0052 (7) |
N1 | 0.0333 (7) | 0.0252 (6) | 0.0418 (8) | 0.0002 (5) | 0.0090 (6) | 0.0027 (5) |
N2 | 0.0350 (7) | 0.0455 (8) | 0.0496 (9) | 0.0046 (6) | 0.0064 (6) | −0.0078 (6) |
O1 | 0.0429 (6) | 0.0311 (6) | 0.0668 (9) | −0.0014 (5) | 0.0223 (6) | 0.0083 (5) |
O2 | 0.0422 (7) | 0.0560 (8) | 0.1087 (14) | 0.0142 (6) | 0.0204 (8) | −0.0125 (8) |
O3 | 0.0424 (7) | 0.0506 (8) | 0.0972 (12) | −0.0077 (6) | 0.0219 (7) | −0.0022 (7) |
O4 | 0.0487 (7) | 0.0265 (5) | 0.0667 (9) | 0.0057 (5) | 0.0010 (6) | −0.0081 (5) |
O5 | 0.0534 (7) | 0.0289 (5) | 0.0478 (7) | 0.0077 (5) | 0.0217 (6) | 0.0049 (5) |
O6 | 0.0548 (8) | 0.0435 (7) | 0.0598 (9) | −0.0127 (6) | 0.0279 (7) | −0.0041 (6) |
O7 | 0.0572 (9) | 0.0626 (9) | 0.0728 (11) | 0.0036 (8) | 0.0215 (8) | 0.0215 (8) |
C1—C6 | 1.390 (2) | C9—O4 | 1.4131 (18) |
C1—C7 | 1.423 (2) | C9—H9A | 0.9700 |
C1—C2 | 1.443 (2) | C9—H9B | 0.9700 |
C2—O1 | 1.2666 (19) | C10—O5 | 1.414 (2) |
C2—C3 | 1.433 (2) | C10—H10A | 0.9700 |
C3—C4 | 1.354 (3) | C10—H10B | 0.9700 |
C3—H2 | 0.93 (2) | C11—O6 | 1.4105 (19) |
C4—C5 | 1.404 (2) | C11—H11A | 0.9700 |
C4—H3 | 0.93 (2) | C11—H11B | 0.9700 |
C5—C6 | 1.368 (2) | N1—H1 | 0.86 (2) |
C5—N2 | 1.437 (2) | N2—O2 | 1.2269 (19) |
C6—H4 | 0.94 (2) | N2—O3 | 1.227 (2) |
C7—N1 | 1.284 (2) | O4—H4A | 0.8200 |
C7—H5 | 0.983 (18) | O5—H5A | 0.8200 |
C8—N1 | 1.4673 (18) | O6—H6 | 0.88 (3) |
C8—C11 | 1.524 (2) | O7—H7A | 0.819 (17) |
C8—C9 | 1.528 (2) | O7—H7B | 0.829 (18) |
C8—C10 | 1.534 (2) | ||
C6—C1—C7 | 118.00 (13) | O4—C9—H9A | 110.1 |
C6—C1—C2 | 121.04 (13) | C8—C9—H9A | 110.1 |
C7—C1—C2 | 120.79 (14) | O4—C9—H9B | 110.1 |
O1—C2—C3 | 122.44 (14) | C8—C9—H9B | 110.1 |
O1—C2—C1 | 121.75 (13) | H9A—C9—H9B | 108.4 |
C3—C2—C1 | 115.82 (14) | O5—C10—C8 | 111.68 (13) |
C4—C3—C2 | 121.82 (15) | O5—C10—H10A | 109.3 |
C4—C3—H2 | 120.5 (14) | C8—C10—H10A | 109.3 |
C2—C3—H2 | 117.7 (14) | O5—C10—H10B | 109.3 |
C3—C4—C5 | 120.63 (15) | C8—C10—H10B | 109.3 |
C3—C4—H3 | 124.0 (13) | H10A—C10—H10B | 107.9 |
C5—C4—H3 | 115.4 (13) | O6—C11—C8 | 109.13 (13) |
C6—C5—C4 | 120.36 (15) | O6—C11—H11A | 109.9 |
C6—C5—N2 | 119.57 (14) | C8—C11—H11A | 109.9 |
C4—C5—N2 | 120.04 (14) | O6—C11—H11B | 109.9 |
C5—C6—C1 | 120.31 (14) | C8—C11—H11B | 109.9 |
C5—C6—H4 | 119.6 (12) | H11A—C11—H11B | 108.3 |
C1—C6—H4 | 120.1 (12) | C7—N1—C8 | 127.51 (13) |
N1—C7—C1 | 123.18 (14) | C7—N1—H1 | 118.1 (13) |
N1—C7—H5 | 119.1 (10) | C8—N1—H1 | 113.8 (13) |
C1—C7—H5 | 117.5 (10) | O2—N2—O3 | 122.43 (16) |
N1—C8—C11 | 106.98 (13) | O2—N2—C5 | 118.55 (15) |
N1—C8—C9 | 110.47 (12) | O3—N2—C5 | 119.01 (14) |
C11—C8—C9 | 110.33 (13) | C9—O4—H4A | 109.5 |
N1—C8—C10 | 106.61 (12) | C10—O5—H5A | 109.5 |
C11—C8—C10 | 110.78 (13) | C11—O6—H6 | 111.4 (16) |
C9—C8—C10 | 111.51 (13) | H7A—O7—H7B | 107 (3) |
O4—C9—C8 | 108.19 (12) | ||
C6—C1—C2—O1 | −179.94 (16) | C11—C8—C9—O4 | 62.53 (18) |
C7—C1—C2—O1 | 4.9 (2) | C10—C8—C9—O4 | −61.02 (17) |
C6—C1—C2—C3 | 0.6 (2) | N1—C8—C10—O5 | 64.27 (15) |
C7—C1—C2—C3 | −174.57 (15) | C11—C8—C10—O5 | −179.68 (12) |
O1—C2—C3—C4 | 178.85 (17) | C9—C8—C10—O5 | −56.38 (16) |
C1—C2—C3—C4 | −1.7 (3) | N1—C8—C11—O6 | 50.34 (17) |
C2—C3—C4—C5 | 1.6 (3) | C9—C8—C11—O6 | 170.55 (13) |
C3—C4—C5—C6 | −0.3 (3) | C10—C8—C11—O6 | −65.48 (17) |
C3—C4—C5—N2 | 177.69 (17) | C1—C7—N1—C8 | 168.79 (15) |
C4—C5—C6—C1 | −0.8 (2) | C11—C8—N1—C7 | 152.37 (16) |
N2—C5—C6—C1 | −178.79 (15) | C9—C8—N1—C7 | 32.3 (2) |
C7—C1—C6—C5 | 175.90 (15) | C10—C8—N1—C7 | −89.06 (19) |
C2—C1—C6—C5 | 0.6 (2) | C6—C5—N2—O2 | 179.38 (17) |
C6—C1—C7—N1 | −178.96 (16) | C4—C5—N2—O2 | 1.4 (3) |
C2—C1—C7—N1 | −3.6 (3) | C6—C5—N2—O3 | 0.3 (2) |
N1—C8—C9—O4 | −179.39 (14) | C4—C5—N2—O3 | −177.72 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O5i | 0.82 | 1.97 | 2.6801 (15) | 145 |
O5—H5A···O1ii | 0.82 | 2.03 | 2.6661 (15) | 134 |
O7—H7A···O6iii | 0.82 (2) | 1.96 (2) | 2.765 (2) | 167 (3) |
O7—H7B···O4iv | 0.83 (2) | 2.04 (2) | 2.855 (2) | 169 (3) |
N1—H1···O1 | 0.86 (2) | 1.95 (2) | 2.6221 (17) | 134.6 (18) |
O6—H6···O7 | 0.88 (3) | 1.77 (3) | 2.649 (2) | 173 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2. |
C11H15NO2 | Dx = 1.039 Mg m−3 |
Mr = 193.24 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 2997 reflections |
Hall symbol: R3 | θ = 1.7–25.7° |
a = 23.561 (4) Å | µ = 0.07 mm−1 |
c = 5.7823 (8) Å | T = 296 K |
V = 2779.8 (8) Å3 | Prism, yellow |
Z = 9 | 0.50 × 0.37 × 0.23 mm |
F(000) = 936 |
Stoe IPDS-II diffractometer | 1209 independent reflections |
Radiation source: fine-focus sealed tube | 646 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.039 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 1.7° |
ω scans | h = −29→29 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −29→29 |
Tmin = 0.967, Tmax = 0.982 | l = −7→7 |
2997 measured reflections |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.81 | w = 1/[σ2(Fo2) + (0.055P)2] where P = (Fo2 + 2Fc2)/3 |
1209 reflections | (Δ/σ)max < 0.001 |
134 parameters | Δρmax = 0.08 e Å−3 |
3 restraints | Δρmin = −0.10 e Å−3 |
C11H15NO2 | Z = 9 |
Mr = 193.24 | Mo Kα radiation |
Trigonal, R3 | µ = 0.07 mm−1 |
a = 23.561 (4) Å | T = 296 K |
c = 5.7823 (8) Å | 0.50 × 0.37 × 0.23 mm |
V = 2779.8 (8) Å3 |
Stoe IPDS-II diffractometer | 1209 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 646 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.982 | Rint = 0.039 |
2997 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 3 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.81 | Δρmax = 0.08 e Å−3 |
1209 reflections | Δρmin = −0.10 e Å−3 |
134 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 | 0.33506 (16) | 0.15248 (14) | 0.5014 (4) | 0.0752 (7) | |
C2 | 0.32212 (17) | 0.12026 (13) | 0.7141 (5) | 0.0847 (8) | |
C3 | 0.3604 (3) | 0.09421 (18) | 0.7873 (6) | 0.1054 (11) | |
H3 | 0.3516 | 0.0722 | 0.9280 | 0.127* | |
C4 | 0.4103 (3) | 0.1006 (2) | 0.6558 (8) | 0.1214 (13) | |
H4 | 0.4360 | 0.0835 | 0.7091 | 0.146* | |
C5 | 0.4246 (2) | 0.1317 (2) | 0.4446 (7) | 0.1153 (12) | |
H5 | 0.4587 | 0.1347 | 0.3540 | 0.138* | |
C6 | 0.38714 (18) | 0.15821 (18) | 0.3707 (5) | 0.0966 (9) | |
H6 | 0.3970 | 0.1804 | 0.2303 | 0.116* | |
C7 | 0.29508 (16) | 0.17864 (14) | 0.4153 (5) | 0.0782 (7) | |
H7 | 0.3050 | 0.1995 | 0.2723 | 0.094* | |
C8 | 0.20890 (17) | 0.20209 (19) | 0.4316 (6) | 0.0984 (10) | |
H8 | 0.2262 | 0.2206 | 0.2787 | 0.118* | |
C9 | 0.2165 (2) | 0.2560 (2) | 0.5928 (6) | 0.1102 (12) | |
H9A | 0.1873 | 0.2715 | 0.5427 | 0.132* | |
H9B | 0.2032 | 0.2381 | 0.7471 | 0.132* | |
C10 | 0.1372 (2) | 0.1489 (3) | 0.4093 (10) | 0.1527 (17) | |
H10A | 0.1212 | 0.1284 | 0.5589 | 0.183* | |
H10B | 0.1116 | 0.1688 | 0.3627 | 0.183* | |
C11 | 0.1276 (3) | 0.0972 (4) | 0.2357 (14) | 0.221 (3) | |
H11A | 0.0818 | 0.0654 | 0.2240 | 0.331* | |
H11B | 0.1513 | 0.0759 | 0.2849 | 0.331* | |
H11C | 0.1437 | 0.1172 | 0.0875 | 0.331* | |
N1 | 0.24712 (13) | 0.17407 (13) | 0.5286 (4) | 0.0845 (7) | |
O1 | 0.27283 (14) | 0.11369 (12) | 0.8504 (3) | 0.1060 (7) | |
O2 | 0.28091 (17) | 0.30953 (13) | 0.6018 (5) | 0.1139 (8) | |
H2 | 0.307 (2) | 0.302 (2) | 0.733 (8) | 0.144 (14)* | |
H1 | 0.246 (3) | 0.130 (3) | 0.757 (11) | 0.21 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.092 (2) | 0.0631 (15) | 0.0793 (16) | 0.0452 (15) | −0.0077 (15) | −0.0074 (13) |
C2 | 0.109 (2) | 0.0676 (18) | 0.0850 (18) | 0.0494 (18) | −0.0133 (18) | −0.0070 (15) |
C3 | 0.150 (4) | 0.093 (2) | 0.100 (2) | 0.081 (3) | −0.023 (2) | −0.0047 (17) |
C4 | 0.152 (4) | 0.128 (3) | 0.130 (3) | 0.103 (3) | −0.038 (3) | −0.014 (3) |
C5 | 0.129 (3) | 0.129 (3) | 0.128 (3) | 0.094 (3) | −0.006 (2) | −0.015 (2) |
C6 | 0.113 (3) | 0.094 (2) | 0.101 (2) | 0.066 (2) | −0.0005 (19) | −0.0005 (17) |
C7 | 0.092 (2) | 0.0701 (18) | 0.0796 (15) | 0.0456 (16) | −0.0056 (16) | −0.0011 (13) |
C8 | 0.094 (2) | 0.115 (2) | 0.109 (2) | 0.069 (2) | −0.0024 (17) | 0.0146 (19) |
C9 | 0.128 (3) | 0.138 (4) | 0.107 (2) | 0.099 (3) | 0.010 (2) | 0.013 (2) |
C10 | 0.102 (3) | 0.165 (4) | 0.194 (4) | 0.070 (3) | −0.021 (3) | 0.005 (4) |
C11 | 0.164 (5) | 0.203 (7) | 0.269 (8) | 0.072 (5) | −0.068 (5) | −0.072 (6) |
N1 | 0.0905 (17) | 0.0840 (17) | 0.0882 (14) | 0.0505 (15) | 0.0017 (14) | 0.0077 (12) |
O1 | 0.132 (2) | 0.1028 (17) | 0.0945 (13) | 0.0675 (16) | 0.0155 (14) | 0.0245 (12) |
O2 | 0.143 (3) | 0.1032 (19) | 0.1137 (16) | 0.075 (2) | 0.0041 (18) | 0.0095 (14) |
C1—C6 | 1.389 (4) | C8—C9 | 1.513 (5) |
C1—C2 | 1.397 (4) | C8—C10 | 1.524 (6) |
C1—C7 | 1.448 (4) | C8—H8 | 0.9800 |
C2—O1 | 1.347 (4) | C9—O2 | 1.408 (5) |
C2—C3 | 1.387 (5) | C9—H9A | 0.9700 |
C3—C4 | 1.344 (6) | C9—H9B | 0.9700 |
C3—H3 | 0.9300 | C10—C11 | 1.506 (8) |
C4—C5 | 1.377 (6) | C10—H10A | 0.9700 |
C4—H4 | 0.9300 | C10—H10B | 0.9700 |
C5—C6 | 1.380 (5) | C11—H11A | 0.9600 |
C5—H5 | 0.9300 | C11—H11B | 0.9600 |
C6—H6 | 0.9300 | C11—H11C | 0.9600 |
C7—N1 | 1.263 (4) | O1—H1 | 1.04 (7) |
C7—H7 | 0.9300 | O2—H2 | 1.04 (5) |
C8—N1 | 1.468 (4) | ||
C6—C1—C2 | 118.3 (3) | N1—C8—H8 | 109.5 |
C6—C1—C7 | 120.2 (3) | C9—C8—H8 | 109.5 |
C2—C1—C7 | 121.5 (3) | C10—C8—H8 | 109.5 |
O1—C2—C3 | 119.0 (3) | O2—C9—C8 | 113.4 (3) |
O1—C2—C1 | 121.3 (3) | O2—C9—H9A | 108.9 |
C3—C2—C1 | 119.7 (3) | C8—C9—H9A | 108.9 |
C4—C3—C2 | 120.3 (4) | O2—C9—H9B | 108.9 |
C4—C3—H3 | 119.9 | C8—C9—H9B | 108.9 |
C2—C3—H3 | 119.9 | H9A—C9—H9B | 107.7 |
C3—C4—C5 | 122.0 (3) | C11—C10—C8 | 112.2 (5) |
C3—C4—H4 | 119.0 | C11—C10—H10A | 109.2 |
C5—C4—H4 | 119.0 | C8—C10—H10A | 109.2 |
C4—C5—C6 | 118.3 (4) | C11—C10—H10B | 109.2 |
C4—C5—H5 | 120.9 | C8—C10—H10B | 109.2 |
C6—C5—H5 | 120.9 | H10A—C10—H10B | 107.9 |
C5—C6—C1 | 121.4 (3) | C10—C11—H11A | 109.5 |
C5—C6—H6 | 119.3 | C10—C11—H11B | 109.5 |
C1—C6—H6 | 119.3 | H11A—C11—H11B | 109.5 |
N1—C7—C1 | 122.0 (3) | C10—C11—H11C | 109.5 |
N1—C7—H7 | 119.0 | H11A—C11—H11C | 109.5 |
C1—C7—H7 | 119.0 | H11B—C11—H11C | 109.5 |
N1—C8—C9 | 107.5 (3) | C7—N1—C8 | 119.2 (3) |
N1—C8—C10 | 109.8 (3) | C2—O1—H1 | 107 (3) |
C9—C8—C10 | 111.1 (4) | C9—O2—H2 | 110 (2) |
C6—C1—C2—O1 | 179.2 (3) | C7—C1—C6—C5 | −177.6 (3) |
C7—C1—C2—O1 | −1.7 (4) | C6—C1—C7—N1 | 179.6 (3) |
C6—C1—C2—C3 | −1.0 (4) | C2—C1—C7—N1 | 0.5 (4) |
C7—C1—C2—C3 | 178.1 (3) | N1—C8—C9—O2 | 65.7 (4) |
O1—C2—C3—C4 | −179.4 (3) | C10—C8—C9—O2 | −174.1 (3) |
C1—C2—C3—C4 | 0.8 (5) | N1—C8—C10—C11 | −65.6 (6) |
C2—C3—C4—C5 | −1.2 (6) | C9—C8—C10—C11 | 175.6 (5) |
C3—C4—C5—C6 | 1.6 (6) | C1—C7—N1—C8 | 179.6 (3) |
C4—C5—C6—C1 | −1.8 (5) | C9—C8—N1—C7 | −116.9 (3) |
C2—C1—C6—C5 | 1.4 (5) | C10—C8—N1—C7 | 122.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O2i | 1.04 (5) | 1.65 (5) | 2.675 (4) | 170 (4) |
O1—H1···N1 | 1.04 (7) | 1.67 (7) | 2.591 (3) | 145 (5) |
Symmetry code: (i) −y+2/3, x−y+1/3, z+1/3. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C13H19NO5 | C11H14N2O6·H2O | C11H15NO2 |
Mr | 269.29 | 288.26 | 193.24 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c | Trigonal, R3 |
Temperature (K) | 296 | 296 | 296 |
a, b, c (Å) | 9.7424 (8), 10.6073 (8), 14.4820 (11) | 16.9205 (11), 10.7034 (6), 7.2308 (5) | 23.561 (4), 23.561 (4), 5.7823 (8) |
α, β, γ (°) | 102.592 (6), 104.459 (6), 105.840 (6) | 90, 99.518 (5), 90 | 90, 90, 120 |
V (Å3) | 1326.7 (2) | 1291.52 (14) | 2779.8 (8) |
Z | 4 | 4 | 9 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.13 | 0.07 |
Crystal size (mm) | 0.43 × 0.31 × 0.19 | 0.38 × 0.25 × 0.08 | 0.50 × 0.37 × 0.23 |
Data collection | |||
Diffractometer | Stoe IPDS-II diffractometer | Stoe IPDS-II diffractometer | Stoe IPDS-II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) | Integration (X-RED32; Stoe & Cie, 2002) | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.946, 0.988 | 0.955, 0.989 | 0.967, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22555, 6080, 3597 | 11553, 2877, 1898 | 2997, 1209, 646 |
Rint | 0.051 | 0.059 | 0.039 |
(sin θ/λ)max (Å−1) | 0.650 | 0.649 | 0.618 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.095, 0.88 | 0.040, 0.107, 0.93 | 0.035, 0.093, 0.81 |
No. of reflections | 6080 | 2877 | 1209 |
No. of parameters | 361 | 214 | 134 |
No. of restraints | 6 | 2 | 3 |
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) | 0.14, −0.17 | 0.30, −0.32 | 0.08, −0.10 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
C7A—N1A | 1.2983 (18) | C8A—N1A | 1.4695 (18) |
C7B—N1B | 1.2960 (18) | C8B—N1B | 1.4726 (18) |
N1B—C7B—C1B | 123.48 (14) | N1B—C8B—C10B | 105.30 (12) |
N1A—C8A—C9A | 111.76 (12) | O2A—C22A—C33A | 108.00 (15) |
N1A—C8A—C11A | 106.66 (12) | O2B—C22B—C33B | 107.19 (13) |
N1A—C8A—C10A | 105.68 (12) | C7A—N1A—C8A | 128.68 (13) |
N1B—C8B—C9B | 112.15 (12) | C7B—N1B—C8B | 128.84 (13) |
N1B—C8B—C11B | 107.17 (12) | ||
C7A—C1A—C2A—O1A | −5.9 (2) | C6A—C1A—C7A—N1A | 177.53 (14) |
C6A—C1A—C2A—O1A | 174.57 (14) | C6B—C1B—C7B—N1B | −179.21 (14) |
C7B—C1B—C2B—O1B | −1.5 (2) | C2B—C1B—C7B—N1B | 3.5 (2) |
C6B—C1B—C2B—O1B | −178.79 (14) | C9A—C8A—N1A—C7A | 22.5 (2) |
O1A—C2A—C3A—O2A | 3.9 (2) | C11A—C8A—N1A—C7A | 141.16 (16) |
C1B—C2B—C3B—O2B | 179.89 (13) | C10A—C8A—N1A—C7A | −100.12 (17) |
C2A—C1A—C7A—N1A | −2.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3A—H3A···O4Bi | 0.861 (16) | 1.845 (16) | 2.7011 (15) | 173 (2) |
O3B—H3B···O4Aii | 0.841 (16) | 1.863 (16) | 2.6994 (16) | 173 (2) |
O4A—H4A···O1Biii | 0.831 (15) | 1.977 (18) | 2.7300 (15) | 150 (2) |
O4A—H4A···O2Biii | 0.831 (15) | 2.430 (19) | 3.0894 (15) | 137 (2) |
O4B—H4B···O1Aiv | 0.860 (15) | 1.921 (17) | 2.7205 (15) | 154 (2) |
O4B—H4B···O2Aiv | 0.860 (15) | 2.523 (19) | 3.1811 (15) | 133.9 (18) |
O5A—H5A···O1Biii | 0.839 (15) | 1.927 (16) | 2.7548 (16) | 169 (2) |
O5B—H5B···O1Aiv | 0.845 (15) | 1.998 (16) | 2.8351 (16) | 171 (2) |
N1A—H1A···O1A | 0.878 (19) | 1.898 (19) | 2.6331 (17) | 140.3 (15) |
N1B—H1B···O1B | 0.887 (19) | 1.876 (19) | 2.6210 (17) | 140.4 (16) |
C9A—H9A···Cg1v | 0.970 | 2.8426 | 3.7045 (17) | 148.49 |
C33B—H33F···Cg2vi | 0.960 | 2.9722 | 3.628 (2) | 126.61 |
Symmetry codes: (i) x+1, y+2, z; (ii) x−1, y−2, z; (iii) x+1, y+1, z; (iv) x−1, y−1, z; (v) −x+1, −y+2, −z+1; (vi) −x+2, −y+2, −z. |
C5—N2 | 1.437 (2) | C8—N1 | 1.4673 (18) |
C7—N1 | 1.284 (2) | ||
O1—C2—C1 | 121.75 (13) | N1—C8—C11 | 106.98 (13) |
C6—C5—N2 | 119.57 (14) | N1—C8—C9 | 110.47 (12) |
N1—C7—C1 | 123.18 (14) | N1—C8—C10 | 106.61 (12) |
C6—C1—C7—N1 | −178.96 (16) | C10—C8—N1—C7 | −89.06 (19) |
N1—C8—C9—O4 | −179.39 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O5i | 0.82 | 1.97 | 2.6801 (15) | 145.1 |
O5—H5A···O1ii | 0.82 | 2.03 | 2.6661 (15) | 134.2 |
O7—H7A···O6iii | 0.819 (17) | 1.961 (18) | 2.765 (2) | 167 (3) |
O7—H7B···O4iv | 0.829 (18) | 2.037 (19) | 2.855 (2) | 169 (3) |
N1—H1···O1 | 0.86 (2) | 1.95 (2) | 2.6221 (17) | 134.6 (18) |
O6—H6···O7 | 0.88 (3) | 1.77 (3) | 2.649 (2) | 173 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2. |
C7—N1 | 1.263 (4) | C8—N1 | 1.468 (4) |
N1—C7—C1 | 122.0 (3) | N1—C8—C10 | 109.8 (3) |
N1—C8—C9 | 107.5 (3) | C7—N1—C8 | 119.2 (3) |
C7—C1—C2—O1 | −1.7 (4) | C1—C7—N1—C8 | 179.6 (3) |
N1—C8—C9—O2 | 65.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O2i | 1.04 (5) | 1.65 (5) | 2.675 (4) | 170 (4) |
O1—H1···N1 | 1.04 (7) | 1.67 (7) | 2.591 (3) | 145 (5) |
Symmetry code: (i) −y+2/3, x−y+1/3, z+1/3. |
Compound | Cg–Cgi,ii | dcentroids | dperpendicular |
I | Cg1–Cg2i | 4,056 (10) | 3,243 |
II | Cg1–Cg1ii | 3,684 (10) | 3,508 |
III | Cg1–Cg1iii | 4,951 (3) | 4,929 |
III | Cg1–Cg1iv | 5,971 (3) | 4,012 |
Symmetry codes: (i) −1 + x, y, z; (ii) x, 3/2 − y, −1/2 + z; (iii) 1/3 − y, −1/3 + x-y, −1/3 + z; (iv) 2/3 − x + y, 1/3 − x,-2/3 + z. |
Compound | C1—C2 | C2—O1 | C1—C7 | C7—N1 |
(IA) | 1.417 (2) | 1.2936 (16) | 1.414 (2) | 1.2983 (18) |
(IB) | 1.420 (2) | 1.2952 (16) | 1.418 (2) | 1.2960 (18) |
(II) | 1.443 (2) | 1.2666 (19) | 1.423 (2) | 1.284 (2) |
(III) | 1.397 (4) | 1.347 (4) | 1.448 (4) | 1.263 (4) |
There is considerable interest in Schiff base ligands and their complexes because of their striking antitumour activities (Zhou et al., 2000). Schiff base compounds show photochromism and thermochromism in the solid state by proton transfer from the hydroxyl O atom to the imine N atom (Cohen et al., 1964), i.e. phenol–imine keto–amine tautomerism. It is known that the phenol–imine tautomer is dominant in salicylaldimine, while the keto–amine form is preferred in the naphthaldimine Schiff bases depending on the solvent polarities. Moreover, o-hydroxy Schiff bases can exist in different tautomeric forms. The configurations of these compounds are controlled by steric and electronic effects (Filarowski et al., 2002), and the phenol–imine (molecular or phenol) and keto–amine (or keto) tautomeric forms are the most common. The subtituents on the phenol ring affect the tautomeric equilibrium. The existence of electron attracting groups on the o- and p-positions to the OH increase the acidity and the stability of the keto amine form with the mesomeric and inductive effects (Filarowski et al., 2002) Studies made so far show that o-hydroxy Schiff bases with electron-attracting groups like Cl and NO2 at the o- or p-position exhibit the keto–amine form (Wozniak et al., 1995). The zwitterionic form is rarely seen in the solid state (Krygowski et al., 1997).
In compound (I) (Fig. 1), there are two molecules in the asymmetric unit. Fig. 3 shows (II), with a water molecule of crystallization in the asymmetric unit, and Fig. 5 shows (III). By analysing the C1—C2, C2—O1, C1—C7 and C7—N1 bonds in Table 8, it can be concluded that the C1—C2 bond lengths in (I) and (II) are longer than that in compound (III), whilst the C2—O1 bond length of in compound (II) is longer than those in other two compounds. The longest C1—C7 bond is in compound (III), and those of (I) and (II) are nearly equal. The C7—N1 bond lengths in all three compounds indicate that these bonds are C=N double bonds. As a result of this analysis, it can be said that the structure of compounds (I), (II) and (III) are closest to (Ia) (scheme 2), (IIb) (scheme 3) and (IIIa) (scheme 4), respectively. For compound (I), the comparisons of the C—O and N—C bond distances with the corresponding values of Allen et al. (1987) and also the existence of three hydrogen bonds formed by the negative O1 atom show that the zwitterionic form is very important (Scheme 2). In (II), evaluating the N—C and C—O bonds, it can be concluded that the aroused zwitterionic form (IIb) is important, arising from the resonating effect of the nitro group (scheme 3). In the solid state, the phenol–imine tautomeric form exists in salicylaldimine Schiff bases (Kaitner & Pavlovic, 1996; Yıldız et al., 1998). Also, the position of proton and the bond distances of C—N and C—O indicate that the compound (III) is in phenol–imine tautomeric form, (IIIa) (scheme 4).
In compound (I), each molecule in the asymmetric unit has an intramolecular N—H···O hydrogen bond. In addition, molecules A and B in the asymmetric unit are linked by intermolecular O—H···O hydrogen bonds forming a three-dimensional network, as shown in Fig. 2; this figure also shows the two five-membered pseudo-rings formed by the two intermolecular hydrogen bonds (O4A—H4A···O1B and O4A—H4A···O2B; and O4B—H4B···O1A and O4B—H4B···O2A). In (II), there are two intramolecular hydrogen bonds, N1—H1···O1 and O6—H6···O7, and the water molecules form intermolecular hydrogen bonds with O4 and O6 (Table 4, Fig. 4). Compound (III) has one intramolecular hydrogen bond, O1—H1···N1, which is shown in Fig. 5 and there is also an intermolecular hydrogen bond, O2—H2···O2 (Table 6 and Fig. 6). In all three compounds, in addition to the intermolecular hydrogen bonds, there are π–π interactions (Table 7), leading to a three-dimensional network. Cg1 and Cg2 given in Table 2 and Table 7 are the centroids of the C1A–C6A and C1B–C6B rings for compound (I); Cg1 is the centroid of the C1–C6 ring for (II) and (III).