Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107021920/av3088sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107021920/av3088Isup2.hkl |
CCDC reference: 652525
The ligand 2,6-bis(hydrazinocarbonyl)pyridine was prepared by the following reaction. Diethyl-2,6-pyridinecarboxylate ester (1.95 g, 10 mmol) and hydrazine hydrate (10 ml, 85%) were reacted in a 100 ml reaction flask in chloroform (Volume?). The product was recrystallized from a large amount of water as colourless needles (75% yield).
The ligand 2,6-bis[(2-hydroxy-3-methoxybenzylidene)hydrazinecarbonyl]pyridine was synthesized as follows. 2,6-Bis(hydrazinocarbonyl)pyridine (1.95 g, 10 mmol), 2-hydroxy-3-methoxybenzaldehyde (3.04 g, 20 mmol) and p-toluenesulfonic acid as catalyst were added to a 100 ml reaction flask with ethanol (60 ml). The mixture was stirred magnetically and refluxed for about 3 h. After filtration, and removal of the ethanol by rotary evaporation, the crude product was obtained and was recrystallized from methanol (85% yield).
C-bound H atoms were positioned geometrically, with C—H = 0.93–0.96 Å, and refined as riding, with Uiso(H) = 1.2Ueq(C), or 1.2Ueq(methyl C). N-bound H atoms were found in difference maps, relocated in idealized positions with N—H = 0.89 Å, and refined as riding, with Uiso(H) = 1.2Ueq(N). Water and hydroxyl H atoms were found in difference maps, relocated in idealized positions with O—H = 0.82 Å, and refined as riding atoms with Uiso(H) = 1.2Ueq(O).
Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.
C23H21N5O6·H2O | Z = 2 |
Mr = 481.46 | F(000) = 504 |
Triclinic, P1 | Dx = 1.424 Mg m−3 |
Hall symbol: -p 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.184 (2) Å | Cell parameters from 102 reflections |
b = 10.842 (1) Å | θ = 1.9–27.1° |
c = 11.034 (2) Å | µ = 0.11 mm−1 |
α = 98.72 (3)° | T = 291 K |
β = 110.42 (2)° | Block, colourless |
γ = 92.42 (3)° | 0.30 × 0.20 × 0.20 mm |
V = 1122.6 (4) Å3 |
Bruker SMART APEXII CCD area-detector diffractometer | 5177 independent reflections |
Radiation source: fine-focus sealed tube | 4150 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.003 |
ϕ and ω scans | θmax = 27.5°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −13→13 |
Tmin = 0.968, Tmax = 0.973 | k = 0→14 |
5277 measured reflections | l = −14→14 |
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)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0715P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.007 |
5177 reflections | Δρmax = 0.21 e Å−3 |
317 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0098 (18) |
C23H21N5O6·H2O | γ = 92.42 (3)° |
Mr = 481.46 | V = 1122.6 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.184 (2) Å | Mo Kα radiation |
b = 10.842 (1) Å | µ = 0.11 mm−1 |
c = 11.034 (2) Å | T = 291 K |
α = 98.72 (3)° | 0.30 × 0.20 × 0.20 mm |
β = 110.42 (2)° |
Bruker SMART APEXII CCD area-detector diffractometer | 5177 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 4150 reflections with I > 2σ(I) |
Tmin = 0.968, Tmax = 0.973 | Rint = 0.003 |
5277 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.139 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.21 e Å−3 |
5177 reflections | Δρmin = −0.20 e Å−3 |
317 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 | 0.19884 (18) | 0.34160 (17) | 0.4560 (2) | 0.0381 (6) | |
C2 | 0.0625 (2) | 0.3316 (2) | 0.4553 (2) | 0.0507 (7) | |
H2A | 0.0014 | 0.3903 | 0.4237 | 0.061* | |
C3 | 0.0192 (2) | 0.2335 (2) | 0.5023 (2) | 0.0612 (8) | |
H3 | −0.0720 | 0.2245 | 0.5025 | 0.073* | |
C4 | 0.11283 (19) | 0.1481 (2) | 0.5493 (2) | 0.0485 (6) | |
H4A | 0.0862 | 0.0806 | 0.5815 | 0.058* | |
C5 | 0.24745 (18) | 0.16595 (18) | 0.54719 (19) | 0.0364 (5) | |
C6 | 0.35072 (19) | 0.07563 (18) | 0.5996 (2) | 0.0383 (5) | |
C7 | 0.71717 (19) | 0.09205 (19) | 0.70697 (19) | 0.0421 (6) | |
H7A | 0.7332 | 0.1719 | 0.6906 | 0.051* | |
C8 | 0.83587 (19) | 0.02501 (18) | 0.76564 (19) | 0.0386 (6) | |
C9 | 0.9736 (2) | 0.0783 (2) | 0.7935 (2) | 0.0504 (7) | |
H9 | 0.9876 | 0.1571 | 0.7738 | 0.060* | |
C10 | 1.0867 (2) | 0.0165 (2) | 0.8489 (2) | 0.0550 (7) | |
H10 | 1.1770 | 0.0539 | 0.8675 | 0.066* | |
C11 | 1.0688 (2) | −0.1017 (2) | 0.8780 (2) | 0.0535 (7) | |
H11 | 1.1467 | −0.1437 | 0.9148 | 0.064* | |
C12 | 0.9351 (2) | −0.15635 (19) | 0.8522 (2) | 0.0433 (6) | |
C13 | 0.81783 (18) | −0.09329 (19) | 0.79588 (19) | 0.0387 (6) | |
C14 | 1.0176 (2) | −0.3454 (2) | 0.9237 (3) | 0.0809 (9) | |
H14A | 0.9818 | −0.4247 | 0.9345 | 0.121* | |
H14B | 1.0820 | −0.3015 | 1.0070 | 0.121* | |
H14C | 1.0656 | −0.3590 | 0.8626 | 0.121* | |
C15 | 0.24496 (19) | 0.44445 (19) | 0.3995 (2) | 0.0421 (6) | |
C16 | 0.5142 (2) | 0.49243 (19) | 0.2783 (2) | 0.0439 (6) | |
H16 | 0.5721 | 0.4337 | 0.3155 | 0.053* | |
C17 | 0.55434 (19) | 0.56697 (18) | 0.1965 (2) | 0.0396 (6) | |
C18 | 0.6858 (2) | 0.5582 (2) | 0.1820 (2) | 0.0514 (7) | |
H18 | 0.7469 | 0.5052 | 0.2269 | 0.062* | |
C19 | 0.7251 (2) | 0.6259 (2) | 0.1037 (2) | 0.0550 (7) | |
H19 | 0.8131 | 0.6198 | 0.0966 | 0.066* | |
C20 | 0.6339 (2) | 0.7040 (2) | 0.0344 (2) | 0.0541 (7) | |
H20 | 0.6603 | 0.7491 | −0.0201 | 0.065* | |
C21 | 0.5040 (2) | 0.7146 (2) | 0.0463 (2) | 0.0454 (6) | |
C22 | 0.46500 (18) | 0.64702 (18) | 0.1278 (2) | 0.0390 (6) | |
C23 | 0.4325 (3) | 0.8464 (2) | −0.1146 (3) | 0.0858 (9) | |
H23A | 0.3552 | 0.8927 | −0.1538 | 0.103* | |
H23B | 0.4434 | 0.7840 | −0.1812 | 0.103* | |
H23C | 0.5174 | 0.9027 | −0.0739 | 0.103* | |
N1 | 0.29100 (15) | 0.26075 (14) | 0.50166 (15) | 0.0356 (4) | |
N2 | 0.48504 (16) | 0.11625 (14) | 0.62165 (17) | 0.0415 (5) | |
H2B | 0.5027 | 0.1883 | 0.5979 | 0.050* | |
N3 | 0.59051 (16) | 0.04457 (15) | 0.67688 (16) | 0.0412 (5) | |
N4 | 0.36241 (16) | 0.42826 (14) | 0.37266 (17) | 0.0416 (5) | |
H4B | 0.4161 | 0.3685 | 0.4019 | 0.050* | |
N5 | 0.39901 (16) | 0.50634 (15) | 0.30027 (17) | 0.0421 (5) | |
O1 | 0.31393 (14) | −0.02534 (13) | 0.62118 (15) | 0.0538 (4) | |
O2 | 0.68928 (13) | −0.15184 (13) | 0.77465 (14) | 0.0486 (4) | |
H2 | 0.6281 | −0.1074 | 0.7419 | 0.073* | |
O3 | 0.90350 (14) | −0.27240 (14) | 0.87475 (16) | 0.0599 (5) | |
O4 | 0.18031 (14) | 0.53748 (13) | 0.38126 (17) | 0.0587 (5) | |
O5 | 0.33579 (13) | 0.66089 (13) | 0.13551 (14) | 0.0518 (4) | |
H5 | 0.3229 | 0.6168 | 0.1853 | 0.078* | |
O6 | 0.40564 (16) | 0.78740 (16) | −0.01889 (16) | 0.0710 (5) | |
O7 | 0.60588 (14) | 0.26205 (13) | 0.46378 (16) | 0.0578 (5) | |
H7B | 0.6343 | 0.1989 | 0.4345 | 0.069* | |
H7C | 0.6832 | 0.3008 | 0.5065 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0374 (9) | 0.0329 (10) | 0.0390 (12) | 0.0007 (9) | 0.0106 (9) | 0.0002 (9) |
C2 | 0.0402 (10) | 0.0493 (12) | 0.0642 (15) | 0.0075 (10) | 0.0181 (10) | 0.0158 (11) |
C3 | 0.0391 (10) | 0.0674 (15) | 0.0832 (17) | 0.0024 (11) | 0.0263 (11) | 0.0219 (13) |
C4 | 0.0459 (10) | 0.0436 (12) | 0.0612 (14) | −0.0032 (10) | 0.0243 (10) | 0.0153 (11) |
C5 | 0.0392 (9) | 0.0341 (10) | 0.0369 (11) | −0.0024 (8) | 0.0165 (8) | 0.0046 (9) |
C6 | 0.0461 (10) | 0.0345 (11) | 0.0393 (11) | 0.0036 (9) | 0.0211 (8) | 0.0075 (9) |
C7 | 0.0506 (10) | 0.0400 (11) | 0.0380 (12) | 0.0027 (9) | 0.0175 (9) | 0.0097 (9) |
C8 | 0.0521 (10) | 0.0406 (11) | 0.0349 (11) | 0.0028 (9) | 0.0148 (8) | 0.0074 (9) |
C9 | 0.0531 (11) | 0.0449 (13) | 0.0529 (14) | −0.0023 (10) | 0.0197 (10) | 0.0081 (11) |
C10 | 0.0368 (10) | 0.0601 (15) | 0.0636 (15) | −0.0041 (11) | 0.0162 (10) | 0.0045 (12) |
C11 | 0.0393 (10) | 0.0637 (15) | 0.0518 (14) | 0.0098 (10) | 0.0100 (10) | 0.0070 (12) |
C12 | 0.0448 (10) | 0.0425 (12) | 0.0405 (12) | 0.0056 (10) | 0.0119 (9) | 0.0087 (10) |
C13 | 0.0442 (9) | 0.0446 (12) | 0.0365 (12) | 0.0023 (9) | 0.0131 (8) | 0.0050 (9) |
C14 | 0.0741 (14) | 0.0699 (15) | 0.095 (2) | 0.0361 (12) | 0.0131 (14) | 0.0396 (14) |
C15 | 0.0360 (10) | 0.0385 (11) | 0.0488 (13) | 0.0014 (9) | 0.0116 (9) | 0.0081 (10) |
C16 | 0.0406 (11) | 0.0346 (11) | 0.0402 (13) | 0.0024 (9) | 0.0089 (9) | 0.0081 (10) |
C17 | 0.0416 (10) | 0.0365 (11) | 0.0378 (12) | −0.0022 (9) | 0.0132 (9) | 0.0020 (10) |
C18 | 0.0432 (10) | 0.0523 (13) | 0.0577 (15) | 0.0076 (10) | 0.0177 (10) | 0.0074 (12) |
C19 | 0.0432 (11) | 0.0585 (15) | 0.0664 (16) | 0.0019 (11) | 0.0248 (10) | 0.0090 (12) |
C20 | 0.0588 (12) | 0.0526 (14) | 0.0533 (14) | 0.0021 (11) | 0.0273 (10) | 0.0047 (12) |
C21 | 0.0520 (10) | 0.0440 (12) | 0.0463 (12) | 0.0045 (10) | 0.0240 (9) | 0.0051 (10) |
C22 | 0.0412 (9) | 0.0358 (11) | 0.0412 (12) | 0.0029 (9) | 0.0179 (9) | 0.0034 (9) |
C23 | 0.1134 (17) | 0.0934 (18) | 0.0901 (17) | 0.0406 (15) | 0.0655 (13) | 0.0558 (14) |
N1 | 0.0401 (8) | 0.0302 (8) | 0.0361 (9) | 0.0001 (7) | 0.0137 (7) | 0.0049 (7) |
N2 | 0.0422 (8) | 0.0338 (9) | 0.0503 (10) | 0.0065 (7) | 0.0152 (7) | 0.0151 (8) |
N3 | 0.0444 (8) | 0.0391 (9) | 0.0410 (10) | 0.0111 (8) | 0.0137 (7) | 0.0116 (8) |
N4 | 0.0415 (8) | 0.0346 (9) | 0.0534 (10) | 0.0062 (7) | 0.0172 (7) | 0.0208 (8) |
N5 | 0.0439 (8) | 0.0351 (9) | 0.0487 (10) | 0.0021 (7) | 0.0201 (7) | 0.0106 (8) |
O1 | 0.0604 (7) | 0.0417 (8) | 0.0726 (10) | 0.0074 (7) | 0.0346 (7) | 0.0234 (7) |
O2 | 0.0378 (7) | 0.0493 (8) | 0.0623 (9) | 0.0065 (6) | 0.0173 (6) | 0.0219 (7) |
O3 | 0.0537 (8) | 0.0516 (9) | 0.0729 (11) | 0.0121 (7) | 0.0138 (8) | 0.0265 (8) |
O4 | 0.0478 (7) | 0.0402 (8) | 0.0532 (12) | 0.0057 (6) | 0.0209 (7) | 0.0202 (8) |
O5 | 0.0485 (7) | 0.0568 (8) | 0.0641 (9) | 0.0165 (6) | 0.0302 (6) | 0.0254 (7) |
O6 | 0.0794 (9) | 0.0835 (11) | 0.0773 (11) | 0.0287 (8) | 0.0452 (8) | 0.0485 (9) |
O7 | 0.0470 (7) | 0.0436 (8) | 0.0820 (11) | 0.0088 (7) | 0.0210 (7) | 0.0133 (8) |
C1—N1 | 1.333 (2) | C14—H14C | 0.9600 |
C1—C2 | 1.386 (3) | C15—O4 | 1.232 (2) |
C1—C15 | 1.491 (3) | C15—N4 | 1.341 (3) |
C2—C3 | 1.371 (3) | C16—N5 | 1.288 (3) |
C2—H2A | 0.9300 | C16—C17 | 1.445 (3) |
C3—C4 | 1.382 (3) | C16—H16 | 0.9300 |
C3—H3 | 0.9300 | C17—C22 | 1.393 (3) |
C4—C5 | 1.385 (3) | C17—C18 | 1.407 (3) |
C4—H4A | 0.9300 | C18—C19 | 1.362 (3) |
C5—N1 | 1.334 (3) | C18—H18 | 0.9300 |
C5—C6 | 1.495 (3) | C19—C20 | 1.390 (3) |
C6—O1 | 1.226 (2) | C19—H19 | 0.9300 |
C6—N2 | 1.345 (2) | C20—C21 | 1.382 (3) |
C7—N3 | 1.278 (2) | C20—H20 | 0.9300 |
C7—C8 | 1.442 (3) | C21—O6 | 1.371 (3) |
C7—H7A | 0.9300 | C21—C22 | 1.389 (3) |
C8—C13 | 1.394 (3) | C22—O5 | 1.361 (2) |
C8—C9 | 1.404 (3) | C23—O6 | 1.411 (3) |
C9—C10 | 1.359 (3) | C23—H23A | 0.9600 |
C9—H9 | 0.9300 | C23—H23B | 0.9600 |
C10—C11 | 1.387 (3) | C23—H23C | 0.9600 |
C10—H10 | 0.9300 | N2—N3 | 1.373 (2) |
C11—C12 | 1.377 (3) | N2—H2B | 0.8913 |
C11—H11 | 0.9300 | N4—N5 | 1.371 (3) |
C12—O3 | 1.366 (3) | N4—H4B | 0.8904 |
C12—C13 | 1.400 (3) | O2—H2 | 0.8200 |
C13—O2 | 1.357 (2) | O5—H5 | 0.8200 |
C14—O3 | 1.427 (3) | O7—H7B | 0.8198 |
C14—H14A | 0.9600 | O7—H7C | 0.8193 |
C14—H14B | 0.9600 | ||
N1—C1—C2 | 122.9 (2) | O4—C15—N4 | 123.2 (2) |
N1—C1—C15 | 117.72 (17) | O4—C15—C1 | 121.95 (19) |
C2—C1—C15 | 119.32 (17) | N4—C15—C1 | 114.84 (17) |
C3—C2—C1 | 118.86 (19) | N5—C16—C17 | 120.79 (19) |
C3—C2—H2A | 120.6 | N5—C16—H16 | 119.6 |
C1—C2—H2A | 120.6 | C17—C16—H16 | 119.6 |
C2—C3—C4 | 119.1 (2) | C22—C17—C18 | 117.9 (2) |
C2—C3—H3 | 120.5 | C22—C17—C16 | 121.88 (18) |
C4—C3—H3 | 120.5 | C18—C17—C16 | 120.16 (19) |
C3—C4—C5 | 118.2 (2) | C19—C18—C17 | 121.3 (2) |
C3—C4—H4A | 120.9 | C19—C18—H18 | 119.3 |
C5—C4—H4A | 120.9 | C17—C18—H18 | 119.3 |
N1—C5—C4 | 123.41 (17) | C18—C19—C20 | 120.0 (2) |
N1—C5—C6 | 117.74 (17) | C18—C19—H19 | 120.0 |
C4—C5—C6 | 118.85 (19) | C20—C19—H19 | 120.0 |
O1—C6—N2 | 124.09 (17) | C21—C20—C19 | 120.1 (2) |
O1—C6—C5 | 121.92 (17) | C21—C20—H20 | 119.9 |
N2—C6—C5 | 113.99 (17) | C19—C20—H20 | 119.9 |
N3—C7—C8 | 121.70 (19) | O6—C21—C20 | 124.8 (2) |
N3—C7—H7A | 119.1 | O6—C21—C22 | 115.44 (19) |
C8—C7—H7A | 119.1 | C20—C21—C22 | 119.7 (2) |
C13—C8—C9 | 118.32 (18) | O5—C22—C21 | 117.21 (18) |
C13—C8—C7 | 121.47 (18) | O5—C22—C17 | 121.9 (2) |
C9—C8—C7 | 120.20 (19) | C21—C22—C17 | 120.85 (18) |
C10—C9—C8 | 121.0 (2) | O6—C23—H23A | 109.5 |
C10—C9—H9 | 119.5 | O6—C23—H23B | 109.5 |
C8—C9—H9 | 119.5 | H23A—C23—H23B | 109.5 |
C9—C10—C11 | 120.7 (2) | O6—C23—H23C | 109.5 |
C9—C10—H10 | 119.6 | H23A—C23—H23C | 109.5 |
C11—C10—H10 | 119.6 | H23B—C23—H23C | 109.5 |
C12—C11—C10 | 119.67 (19) | C1—N1—C5 | 117.51 (17) |
C12—C11—H11 | 120.2 | C6—N2—N3 | 119.38 (17) |
C10—C11—H11 | 120.2 | C6—N2—H2B | 118.8 |
O3—C12—C11 | 125.31 (18) | N3—N2—H2B | 121.8 |
O3—C12—C13 | 114.57 (18) | C7—N3—N2 | 117.11 (17) |
C11—C12—C13 | 120.1 (2) | C15—N4—N5 | 118.69 (16) |
O2—C13—C8 | 122.79 (17) | C15—N4—H4B | 120.7 |
O2—C13—C12 | 117.05 (19) | N5—N4—H4B | 120.6 |
C8—C13—C12 | 120.16 (18) | C16—N5—N4 | 118.21 (17) |
O3—C14—H14A | 109.5 | C13—O2—H2 | 109.5 |
O3—C14—H14B | 109.5 | C12—O3—C14 | 117.50 (17) |
H14A—C14—H14B | 109.5 | C22—O5—H5 | 109.5 |
O3—C14—H14C | 109.5 | C21—O6—C23 | 117.85 (18) |
H14A—C14—H14C | 109.5 | H7B—O7—H7C | 97.2 |
H14B—C14—H14C | 109.5 | ||
N1—C1—C2—C3 | −0.8 (3) | N5—C16—C17—C18 | 174.76 (18) |
C15—C1—C2—C3 | 177.2 (2) | C22—C17—C18—C19 | 0.1 (3) |
C1—C2—C3—C4 | 0.3 (3) | C16—C17—C18—C19 | 178.87 (19) |
C2—C3—C4—C5 | 0.2 (3) | C17—C18—C19—C20 | −1.1 (3) |
C3—C4—C5—N1 | −0.3 (3) | C18—C19—C20—C21 | 1.0 (3) |
C3—C4—C5—C6 | 179.1 (2) | C19—C20—C21—O6 | −179.0 (2) |
N1—C5—C6—O1 | −166.65 (19) | C19—C20—C21—C22 | 0.0 (3) |
C4—C5—C6—O1 | 13.9 (3) | O6—C21—C22—O5 | −0.7 (3) |
N1—C5—C6—N2 | 14.1 (3) | C20—C21—C22—O5 | −179.83 (18) |
C4—C5—C6—N2 | −165.28 (18) | O6—C21—C22—C17 | 178.19 (17) |
N3—C7—C8—C13 | −2.0 (3) | C20—C21—C22—C17 | −0.9 (3) |
N3—C7—C8—C9 | 177.9 (2) | C18—C17—C22—O5 | 179.72 (17) |
C13—C8—C9—C10 | −0.2 (3) | C16—C17—C22—O5 | 1.0 (3) |
C7—C8—C9—C10 | 179.9 (2) | C18—C17—C22—C21 | 0.9 (3) |
C8—C9—C10—C11 | 0.7 (4) | C16—C17—C22—C21 | −177.85 (18) |
C9—C10—C11—C12 | −0.9 (4) | C2—C1—N1—C5 | 0.7 (3) |
C10—C11—C12—O3 | 179.2 (2) | C15—C1—N1—C5 | −177.36 (17) |
C10—C11—C12—C13 | 0.5 (3) | C4—C5—N1—C1 | −0.1 (3) |
C9—C8—C13—O2 | 178.94 (19) | C6—C5—N1—C1 | −179.50 (17) |
C7—C8—C13—O2 | −1.2 (3) | O1—C6—N2—N3 | −2.9 (3) |
C9—C8—C13—C12 | −0.2 (3) | C5—C6—N2—N3 | 176.31 (17) |
C7—C8—C13—C12 | 179.7 (2) | C8—C7—N3—N2 | 179.90 (18) |
O3—C12—C13—O2 | 2.0 (3) | C6—N2—N3—C7 | −173.80 (19) |
C11—C12—C13—O2 | −179.14 (19) | O4—C15—N4—N5 | −12.1 (3) |
O3—C12—C13—C8 | −178.76 (19) | C1—C15—N4—N5 | 168.92 (16) |
C11—C12—C13—C8 | 0.1 (3) | C17—C16—N5—N4 | 176.45 (16) |
N1—C1—C15—O4 | −164.14 (18) | C15—N4—N5—C16 | 177.98 (17) |
C2—C1—C15—O4 | 17.7 (3) | C11—C12—O3—C14 | −2.9 (3) |
N1—C1—C15—N4 | 14.9 (3) | C13—C12—O3—C14 | 175.8 (2) |
C2—C1—C15—N4 | −163.24 (18) | C20—C21—O6—C23 | 6.4 (3) |
N5—C16—C17—C22 | −6.6 (3) | C22—C21—O6—C23 | −172.66 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N3 | 0.82 | 1.90 | 2.613 (2) | 146 |
N2—H2B···O7 | 0.89 | 2.30 | 3.035 (2) | 139 |
N4—H4B···O7 | 0.89 | 2.25 | 3.097 (2) | 160 |
O5—H5···N5 | 0.82 | 1.87 | 2.593 (2) | 146 |
O7—H7B···O1i | 0.82 | 2.04 | 2.848 (2) | 170 |
O7—H7C···O4ii | 0.82 | 2.12 | 2.875 (2) | 154 |
C14—H14B···O5iii | 0.96 | 2.56 | 3.258 (3) | 130 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y−1, z+1. |
Experimental details
Crystal data | |
Chemical formula | C23H21N5O6·H2O |
Mr | 481.46 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 291 |
a, b, c (Å) | 10.184 (2), 10.842 (1), 11.034 (2) |
α, β, γ (°) | 98.72 (3), 110.42 (2), 92.42 (3) |
V (Å3) | 1122.6 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.968, 0.973 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5277, 5177, 4150 |
Rint | 0.003 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.139, 1.01 |
No. of reflections | 5177 |
No. of parameters | 317 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.20 |
Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004), SHELXTL.
N2—N3 | 1.373 (2) | N4—N5 | 1.371 (3) |
C5—C6—N2—N3 | 176.31 (17) | C1—C15—N4—N5 | 168.92 (16) |
C8—C7—N3—N2 | 179.90 (18) | C17—C16—N5—N4 | 176.45 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···N3 | 0.82 | 1.90 | 2.613 (2) | 146 |
N2—H2B···O7 | 0.89 | 2.30 | 3.035 (2) | 139 |
N4—H4B···O7 | 0.89 | 2.25 | 3.097 (2) | 160 |
O5—H5···N5 | 0.82 | 1.87 | 2.593 (2) | 146 |
O7—H7B···O1i | 0.82 | 2.04 | 2.848 (2) | 170 |
O7—H7C···O4ii | 0.82 | 2.12 | 2.875 (2) | 154 |
C14—H14B···O5iii | 0.96 | 2.56 | 3.258 (3) | 130 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y−1, z+1. |
As part of our synthetic study of Schiff base systems, we are now focusing on the synthesis of propeller-shaped amido-containing organic compounds, which are important multidentate ligands for the construction of coordination complexes with metal centres (Wang et al., 2005). In 1985, Paolucci and co-workers first reported the 5-H-substituted 2,6-bis(salicylidenehydrazinocarbonyl)pyridine as a potential mono-, di- and tri-nucleating ligand towards uranyl ions (Paolucci et al., 1985). More recently, Chen and co-workers reported a series of 5-substituted 2,6-bis(salicylidenehydrazinocarbonyl)pyridine ligands (see scheme) and their copper(II) complexes (Chen et al., 1996; Chen et al., 1997). However, the researchers only paid attention to the synthesis of their coordination complexes, and did not report the crystal structures of the organic ligands. In this report, we have synthesized the title 3-methoxy derivative compound with a propeller shape, (I), and describe its crystal structure. For convenience, we denote the benzene ring containing atom C8 as B, the benzene ring containing atom C17 as C and the pyridine ring as A.
In compound (I), the two hydrazine components (N2 and N3, and N4 and N5) have essentially planar coordination, and the N—N bond distances (Table 1) have values typical for hydrazine, with both N atoms having planar coordination [mean value 1.401 (3) Å; Allen et al., 1987]. The fragments C5—C6(═O1)—N2—N3, C1—C15(═O4)—N4—N5, C8—C7—N3—N2 and C17—C16—N5—N4 are essentially planar, as shown by the key torsion angles. The dihedral angles between pyridine ring A and the two benzene rings, B and C, are 17.6 (1) and 17.72 (9)°, respectively. The dihedral angle between two benzene rings is 33.48 (9)°.
Within the selected asymmetric unit (Fig. 1), two hydroxyl O atoms (O2 and O5) act as hydrogen-bond donors, via atoms H2 and H5, respectively, to atoms N3 and N5, thereby generating intramolecular hydrogen bonds of R11(6) motif (Bernstein et al., 1995). Hydrazine atoms N2 and N4 act as hydrogen-bond acceptors, forming intermolecular hydrogen bonds of R11(10) motifs to water atom O7. The solvent water molecule O7 also donates two H atoms to carboxyl atoms O1 and O4 of two different molecules to form relatively strong O—H···O hydrogen bonds.
Through the two intermolecular O—H···O hydrogen bonds and two N—H···O hydrogen bonds to water molecules, compound (I) is linked into a one-dimensional chain along the [010] direction (Fig. 2). It is noteworthy that π–π stacking interactions play an important role in building the one-dimensional chains into two-dimensional layers parallel to (100) (Fig. 3). In the chains, the molecules are antiparallel to each other and the pyridine ring A at (x, y, z) is sandwiched by benzene rings B at (1 - x, -y, 1 - z) and C at (1 - x, 1 - y, 1 - z). The mean interplanar distances are 3.697 (3) and 3.749 (3) Å, respectievly, indicating efficient π–π stacking interactions. Between adjacent chains, the benzene ring plane C at (x, y, z) is antiparallel to the benzene ring C at (1 - x, 1 - y, -z), with an interplanar distance of 3.492 (3) Å. Additional C—H···O hydrogen bonds (Table 2) help to stabilize the layer structure.