Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112020938/sk3437sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112020938/sk3437Isup2.hkl |
CCDC reference: 779405
For related literature, see: Abe et al. (2006); Allen (2002); Becke (1988, 1993); Ben Zid, Khedher & Ghorbel (2010); Boghaei & Mohebi (2002); Bu et al. (1996); Dey et al. (2001); Fairhurst et al. (1995); Frisch (2010); Homden et al. (2008); Jing et al. (2005); Kruszewski & Krygowski (1973); Krygowski (1993); Krygowski et al. (2010); Kurzak et al. (2011); Lee et al. (1988); Meshkini & Yazdanparast (2010); Nakajima et al. (1996); Palusiak et al. (2009); Rayati et al. (2008); Riley et al. (1986); Thompson et al. (1999); Tsuchimoto et al. (2000); Uemura et al. (2000); Xie et al. (2007).
Compound (I) was prepared according to the literature procedure of Boghaei & Mohebi (2002) under ambient conditions. To a hot solution of H2L (7.7 mmol) with triethylamine (10 drops) in methanol (200 ml), a hot solution of oxovanadium(IV) sulfate (7.7 mmol) in methanol (120 ml) was added. The mixture was heated on a hotplate. The resulting red precipitate was collected by filtration, washed with methanol and dried in a vacuum (yield 64%, m.p. 461–462 K). Analysis, found: C 56.68, H 5.44, N 5.47%; C24H26N2O7V requires: C 57.03, H 5.18, N 5.54%. IR (Medium?, ν, cm-1): 3428 (NH), 1320 (CO), 1613 (C═N), 481 (V—N), 348 (V—O) and 861 (V═O).
Based on the solid-state geometry, the molecular structures of H2L and (I) were optimized using the B3LYP hybrid function (Becke, 1988, 1993; Lee et al., 1988) at the 6-311+G(d,p) level of theory. All species correspond to minima at the B3LYP/6-311+G(d,p) level with no imaginary frequencies. All calculations were performed using the GAUSSIAN09 program package (Frisch et al., 2010).
All H atoms were generated in idealized positions, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, C—H = 0.98 Å and Uiso(H) = 1.2Ueq(C) for C(sp4)-H [?], C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for methylene H atoms and C—H = 0.96Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms, and their parameters were not refined. For O—H groups, O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O) and all parameters were refined.
Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); 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: SHELXL97 (Sheldrick, 2008).
[V(C23H20N2O4)O(CH4O)]·H2O | F(000) = 1052 |
Mr = 505.41 | Dx = 1.437 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3633 reflections |
a = 6.9808 (2) Å | θ = 2.9–25.0° |
b = 34.6243 (12) Å | µ = 0.47 mm−1 |
c = 9.6740 (4) Å | T = 290 K |
β = 92.774 (4)° | Prism, red |
V = 2335.52 (14) Å3 | 0.35 × 0.17 × 0.15 mm |
Z = 4 |
Oxford Xcalibur diffractometer | 3635 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.033 |
Graphite monochromator | θmax = 25.0°, θmin = 2.9° |
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm-1 | h = −5→8 |
ω scans | k = −41→41 |
14484 measured reflections | l = −11→11 |
4113 independent 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.20 | w = 1/[σ2(Fo2) + (0.0276P)2 + 1.8956P] where P = (Fo2 + 2Fc2)/3 |
4113 reflections | (Δ/σ)max = 0.001 |
319 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
[V(C23H20N2O4)O(CH4O)]·H2O | V = 2335.52 (14) Å3 |
Mr = 505.41 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.9808 (2) Å | µ = 0.47 mm−1 |
b = 34.6243 (12) Å | T = 290 K |
c = 9.6740 (4) Å | 0.35 × 0.17 × 0.15 mm |
β = 92.774 (4)° |
Oxford Xcalibur diffractometer | 3635 reflections with I > 2σ(I) |
14484 measured reflections | Rint = 0.033 |
4113 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.20 | Δρmax = 0.32 e Å−3 |
4113 reflections | Δρmin = −0.30 e Å−3 |
319 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 | ||
V1 | 0.97255 (6) | 0.387804 (12) | 0.48332 (4) | 0.02581 (13) | |
O1 | 0.8415 (2) | 0.33856 (5) | 0.43211 (18) | 0.0347 (4) | |
O2 | 0.8394 (2) | 0.38952 (5) | 0.65745 (16) | 0.0309 (4) | |
O3 | 0.8531 (2) | 0.41606 (5) | 0.38142 (18) | 0.0364 (4) | |
O4 | 1.1675 (3) | 0.34808 (6) | 0.6282 (2) | 0.0438 (5) | |
H4A | 1.282 (5) | 0.3436 (10) | 0.622 (3) | 0.059 (11)* | |
O5 | 0.5681 (3) | 0.28915 (6) | 0.3721 (2) | 0.0511 (5) | |
O6 | 0.6404 (3) | 0.37030 (7) | 0.8650 (2) | 0.0591 (6) | |
N1 | 1.1898 (3) | 0.37296 (6) | 0.3514 (2) | 0.0309 (5) | |
N2 | 1.1545 (3) | 0.43249 (6) | 0.5625 (2) | 0.0290 (5) | |
C1 | 0.8540 (4) | 0.31939 (7) | 0.3157 (3) | 0.0321 (6) | |
C2 | 0.7092 (4) | 0.29164 (8) | 0.2791 (3) | 0.0392 (7) | |
C3 | 0.7171 (5) | 0.26968 (9) | 0.1613 (3) | 0.0548 (9) | |
H3 | 0.6228 | 0.2513 | 0.1409 | 0.066* | |
C4 | 0.8658 (6) | 0.27485 (10) | 0.0721 (4) | 0.0652 (10) | |
H4 | 0.8687 | 0.2605 | −0.0089 | 0.078* | |
C5 | 1.0066 (5) | 0.30089 (9) | 0.1035 (3) | 0.0562 (9) | |
H5 | 1.1061 | 0.3039 | 0.0439 | 0.067* | |
C6 | 1.0049 (4) | 0.32343 (8) | 0.2249 (3) | 0.0388 (6) | |
C7 | 1.1682 (4) | 0.34804 (8) | 0.2542 (3) | 0.0386 (7) | |
H7 | 1.2696 | 0.3455 | 0.1959 | 0.046* | |
C8 | 1.3765 (4) | 0.39329 (8) | 0.3678 (3) | 0.0368 (6) | |
H8A | 1.4588 | 0.3851 | 0.2953 | 0.044* | |
H8B | 1.4389 | 0.3864 | 0.4561 | 0.044* | |
C9 | 1.3501 (3) | 0.43633 (7) | 0.3608 (3) | 0.0320 (6) | |
C10 | 1.4272 (4) | 0.45807 (8) | 0.2570 (3) | 0.0402 (7) | |
H10 | 1.4931 | 0.4458 | 0.1882 | 0.048* | |
C11 | 1.4078 (4) | 0.49788 (9) | 0.2538 (3) | 0.0454 (8) | |
H11 | 1.4543 | 0.5120 | 0.1808 | 0.054* | |
C12 | 1.3193 (4) | 0.51644 (8) | 0.3592 (3) | 0.0445 (7) | |
H12 | 1.3135 | 0.5433 | 0.3605 | 0.053* | |
C13 | 1.2388 (4) | 0.49533 (8) | 0.4633 (3) | 0.0377 (6) | |
H13 | 1.1770 | 0.5079 | 0.5334 | 0.045* | |
C14 | 1.2507 (3) | 0.45532 (7) | 0.4626 (3) | 0.0297 (6) | |
C15 | 1.1606 (4) | 0.44426 (8) | 0.6887 (3) | 0.0386 (6) | |
H15 | 1.2444 | 0.4645 | 0.7101 | 0.046* | |
C16 | 1.0530 (4) | 0.42972 (8) | 0.8002 (3) | 0.0385 (6) | |
C17 | 1.0969 (5) | 0.44444 (11) | 0.9340 (3) | 0.0562 (9) | |
H17 | 1.1983 | 0.4617 | 0.9472 | 0.067* | |
C18 | 0.9944 (5) | 0.43402 (11) | 1.0441 (3) | 0.0582 (9) | |
H18 | 1.0270 | 0.4437 | 1.1318 | 0.070* | |
C19 | 0.8411 (4) | 0.40888 (9) | 1.0245 (3) | 0.0483 (8) | |
H19 | 0.7709 | 0.4017 | 1.0996 | 0.058* | |
C20 | 0.7916 (4) | 0.39445 (8) | 0.8957 (3) | 0.0382 (6) | |
C21 | 0.8971 (4) | 0.40403 (7) | 0.7784 (2) | 0.0306 (6) | |
C22 | 1.0899 (5) | 0.31710 (10) | 0.7033 (4) | 0.0625 (10) | |
H22A | 1.1910 | 0.3043 | 0.7562 | 0.094* | |
H22B | 1.0288 | 0.2991 | 0.6399 | 0.094* | |
H22C | 0.9973 | 0.3269 | 0.7645 | 0.094* | |
C23 | 0.4237 (5) | 0.26023 (10) | 0.3509 (4) | 0.0650 (10) | |
H23A | 0.3347 | 0.2618 | 0.4233 | 0.097* | |
H23B | 0.4825 | 0.2352 | 0.3522 | 0.097* | |
H23C | 0.3568 | 0.2643 | 0.2631 | 0.097* | |
C24 | 0.5148 (5) | 0.36129 (12) | 0.9703 (4) | 0.0717 (11) | |
H24A | 0.4164 | 0.3442 | 0.9343 | 0.107* | |
H24B | 0.4573 | 0.3846 | 1.0026 | 0.107* | |
H24C | 0.5854 | 0.3490 | 1.0457 | 0.107* | |
O7 | 0.5371 (3) | 0.32793 (8) | 0.6284 (3) | 0.0480 (6) | |
H7A | 0.588 (6) | 0.3436 (13) | 0.674 (5) | 0.090 (17)* | |
H7B | 0.582 (6) | 0.3239 (12) | 0.561 (5) | 0.080 (16)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
V1 | 0.0255 (2) | 0.0267 (2) | 0.0254 (2) | −0.00361 (18) | 0.00338 (15) | −0.00116 (18) |
O1 | 0.0381 (10) | 0.0331 (10) | 0.0332 (10) | −0.0124 (8) | 0.0062 (8) | −0.0075 (8) |
O2 | 0.0316 (9) | 0.0351 (9) | 0.0261 (9) | −0.0046 (8) | 0.0044 (7) | −0.0021 (8) |
O3 | 0.0349 (10) | 0.0401 (10) | 0.0340 (10) | 0.0002 (8) | −0.0009 (8) | 0.0018 (8) |
O4 | 0.0306 (11) | 0.0472 (12) | 0.0541 (13) | 0.0031 (9) | 0.0062 (9) | 0.0151 (10) |
O5 | 0.0521 (13) | 0.0449 (12) | 0.0559 (13) | −0.0227 (10) | −0.0026 (10) | −0.0053 (10) |
O6 | 0.0647 (14) | 0.0747 (15) | 0.0400 (12) | −0.0282 (12) | 0.0253 (11) | −0.0080 (11) |
N1 | 0.0323 (12) | 0.0266 (11) | 0.0344 (12) | −0.0037 (9) | 0.0088 (9) | −0.0016 (9) |
N2 | 0.0256 (11) | 0.0310 (11) | 0.0307 (11) | −0.0054 (9) | 0.0032 (9) | −0.0022 (9) |
C1 | 0.0428 (15) | 0.0235 (13) | 0.0294 (14) | −0.0047 (11) | −0.0039 (11) | −0.0002 (11) |
C2 | 0.0498 (17) | 0.0302 (14) | 0.0367 (15) | −0.0053 (12) | −0.0071 (13) | 0.0020 (12) |
C3 | 0.070 (2) | 0.0401 (17) | 0.053 (2) | −0.0132 (16) | −0.0145 (17) | −0.0107 (15) |
C4 | 0.091 (3) | 0.057 (2) | 0.048 (2) | −0.009 (2) | −0.0003 (19) | −0.0250 (17) |
C5 | 0.078 (2) | 0.0506 (19) | 0.0408 (17) | −0.0060 (18) | 0.0141 (16) | −0.0136 (15) |
C6 | 0.0535 (18) | 0.0302 (14) | 0.0328 (15) | −0.0025 (13) | 0.0031 (13) | −0.0046 (11) |
C7 | 0.0482 (17) | 0.0346 (15) | 0.0345 (15) | −0.0005 (12) | 0.0169 (13) | −0.0012 (12) |
C8 | 0.0303 (14) | 0.0362 (15) | 0.0451 (16) | −0.0017 (11) | 0.0133 (12) | −0.0012 (12) |
C9 | 0.0241 (13) | 0.0363 (14) | 0.0354 (14) | −0.0063 (11) | −0.0007 (11) | 0.0014 (11) |
C10 | 0.0355 (15) | 0.0495 (17) | 0.0358 (15) | −0.0119 (13) | 0.0045 (12) | 0.0018 (13) |
C11 | 0.0364 (17) | 0.0511 (18) | 0.0478 (18) | −0.0158 (13) | −0.0069 (14) | 0.0198 (14) |
C12 | 0.0322 (15) | 0.0344 (15) | 0.066 (2) | −0.0067 (12) | −0.0066 (14) | 0.0117 (14) |
C13 | 0.0269 (14) | 0.0343 (15) | 0.0515 (17) | −0.0027 (11) | −0.0025 (12) | −0.0019 (13) |
C14 | 0.0232 (12) | 0.0327 (14) | 0.0329 (14) | −0.0074 (10) | −0.0008 (10) | 0.0001 (11) |
C15 | 0.0325 (14) | 0.0448 (16) | 0.0385 (16) | −0.0134 (12) | 0.0007 (12) | −0.0087 (13) |
C16 | 0.0360 (15) | 0.0495 (17) | 0.0300 (14) | −0.0055 (13) | 0.0006 (11) | −0.0046 (12) |
C17 | 0.0526 (19) | 0.078 (2) | 0.0375 (17) | −0.0177 (17) | −0.0008 (14) | −0.0149 (16) |
C18 | 0.059 (2) | 0.088 (3) | 0.0272 (15) | −0.0067 (19) | 0.0002 (14) | −0.0120 (16) |
C19 | 0.0542 (19) | 0.064 (2) | 0.0275 (14) | 0.0019 (16) | 0.0108 (13) | 0.0021 (14) |
C20 | 0.0401 (15) | 0.0424 (16) | 0.0326 (14) | −0.0014 (13) | 0.0084 (12) | −0.0002 (12) |
C21 | 0.0314 (14) | 0.0345 (14) | 0.0259 (13) | 0.0039 (11) | 0.0018 (11) | 0.0002 (11) |
C22 | 0.0482 (19) | 0.058 (2) | 0.081 (3) | 0.0003 (16) | 0.0042 (18) | 0.0316 (19) |
C23 | 0.058 (2) | 0.056 (2) | 0.079 (3) | −0.0291 (17) | −0.0130 (19) | 0.0020 (18) |
C24 | 0.076 (3) | 0.086 (3) | 0.056 (2) | −0.028 (2) | 0.0360 (19) | −0.0046 (19) |
O7 | 0.0355 (12) | 0.0557 (15) | 0.0531 (15) | −0.0024 (10) | 0.0070 (11) | −0.0058 (12) |
V1—O3 | 1.5951 (18) | C9—C10 | 1.385 (4) |
V1—O2 | 1.9640 (16) | C9—C14 | 1.396 (4) |
V1—O1 | 1.9865 (17) | C10—C11 | 1.385 (4) |
V1—N1 | 2.092 (2) | C10—H10 | 0.9300 |
V1—N2 | 2.121 (2) | C11—C12 | 1.376 (4) |
V1—O4 | 2.350 (2) | C11—H11 | 0.9300 |
O1—C1 | 1.314 (3) | C12—C13 | 1.385 (4) |
O2—C21 | 1.318 (3) | C12—H12 | 0.9300 |
O4—C22 | 1.418 (4) | C13—C14 | 1.388 (4) |
O4—H4A | 0.82 (3) | C13—H13 | 0.9300 |
O5—C2 | 1.369 (3) | C15—C16 | 1.435 (4) |
O5—C23 | 1.429 (3) | C15—H15 | 0.9300 |
O6—C20 | 1.368 (3) | C16—C17 | 1.411 (4) |
O6—C24 | 1.411 (3) | C16—C21 | 1.414 (4) |
N1—C7 | 1.280 (3) | C17—C18 | 1.360 (4) |
N1—C8 | 1.483 (3) | C17—H17 | 0.9300 |
N2—C15 | 1.285 (3) | C18—C19 | 1.386 (4) |
N2—C14 | 1.440 (3) | C18—H18 | 0.9300 |
C1—C6 | 1.411 (4) | C19—C20 | 1.371 (4) |
C1—C2 | 1.427 (4) | C19—H19 | 0.9300 |
C2—C3 | 1.373 (4) | C20—C21 | 1.422 (4) |
C3—C4 | 1.393 (5) | C22—H22A | 0.9600 |
C3—H3 | 0.9300 | C22—H22B | 0.9600 |
C4—C5 | 1.357 (5) | C22—H22C | 0.9600 |
C4—H4 | 0.9300 | C23—H23A | 0.9600 |
C5—C6 | 1.410 (4) | C23—H23B | 0.9600 |
C5—H5 | 0.9300 | C23—H23C | 0.9600 |
C6—C7 | 1.441 (4) | C24—H24A | 0.9600 |
C7—H7 | 0.9300 | C24—H24B | 0.9600 |
C8—C9 | 1.503 (4) | C24—H24C | 0.9600 |
C8—H8A | 0.9700 | O7—H7A | 0.78 (5) |
C8—H8B | 0.9700 | O7—H7B | 0.75 (4) |
O3—V1—O2 | 104.86 (8) | C14—C9—C8 | 120.0 (2) |
O3—V1—O1 | 98.73 (9) | C9—C10—C11 | 121.1 (3) |
O2—V1—O1 | 90.49 (7) | C9—C10—H10 | 119.5 |
O3—V1—N1 | 98.42 (9) | C11—C10—H10 | 119.5 |
O2—V1—N1 | 156.56 (8) | C12—C11—C10 | 119.7 (3) |
O1—V1—N1 | 88.61 (8) | C12—C11—H11 | 120.2 |
O3—V1—N2 | 93.54 (9) | C10—C11—H11 | 120.2 |
O2—V1—N2 | 88.17 (7) | C11—C12—C13 | 120.3 (3) |
O1—V1—N2 | 167.58 (8) | C11—C12—H12 | 119.9 |
N1—V1—N2 | 87.73 (8) | C13—C12—H12 | 119.9 |
O3—V1—O4 | 176.12 (8) | C12—C13—C14 | 119.8 (3) |
O2—V1—O4 | 77.93 (7) | C12—C13—H13 | 120.1 |
O1—V1—O4 | 83.85 (7) | C14—C13—H13 | 120.1 |
N1—V1—O4 | 78.69 (8) | C13—C14—C9 | 120.4 (2) |
N2—V1—O4 | 83.80 (8) | C13—C14—N2 | 121.0 (2) |
C1—O1—V1 | 126.76 (16) | C9—C14—N2 | 118.6 (2) |
C21—O2—V1 | 129.47 (15) | N2—C15—C16 | 127.4 (2) |
C22—O4—V1 | 121.57 (18) | N2—C15—H15 | 116.3 |
C22—O4—H4A | 107 (2) | C16—C15—H15 | 116.3 |
V1—O4—H4A | 127 (2) | C17—C16—C21 | 119.7 (3) |
C2—O5—C23 | 118.4 (2) | C17—C16—C15 | 117.7 (3) |
C20—O6—C24 | 118.6 (2) | C21—C16—C15 | 122.4 (2) |
C7—N1—C8 | 118.0 (2) | C18—C17—C16 | 121.6 (3) |
C7—N1—V1 | 123.43 (18) | C18—C17—H17 | 119.2 |
C8—N1—V1 | 118.53 (16) | C16—C17—H17 | 119.2 |
C15—N2—C14 | 117.9 (2) | C17—C18—C19 | 119.4 (3) |
C15—N2—V1 | 124.47 (18) | C17—C18—H18 | 120.3 |
C14—N2—V1 | 116.65 (15) | C19—C18—H18 | 120.3 |
O1—C1—C6 | 124.5 (2) | C20—C19—C18 | 120.8 (3) |
O1—C1—C2 | 118.5 (2) | C20—C19—H19 | 119.6 |
C6—C1—C2 | 116.9 (2) | C18—C19—H19 | 119.6 |
O5—C2—C3 | 124.7 (3) | O6—C20—C19 | 125.3 (3) |
O5—C2—C1 | 113.8 (2) | O6—C20—C21 | 113.2 (2) |
C3—C2—C1 | 121.5 (3) | C19—C20—C21 | 121.5 (3) |
C2—C3—C4 | 120.2 (3) | O2—C21—C16 | 124.9 (2) |
C2—C3—H3 | 119.9 | O2—C21—C20 | 118.1 (2) |
C4—C3—H3 | 119.9 | C16—C21—C20 | 116.9 (2) |
C5—C4—C3 | 120.0 (3) | O4—C22—H22A | 109.5 |
C5—C4—H4 | 120.0 | O4—C22—H22B | 109.5 |
C3—C4—H4 | 120.0 | H22A—C22—H22B | 109.5 |
C4—C5—C6 | 121.3 (3) | O4—C22—H22C | 109.5 |
C4—C5—H5 | 119.4 | H22A—C22—H22C | 109.5 |
C6—C5—H5 | 119.4 | H22B—C22—H22C | 109.5 |
C5—C6—C1 | 120.0 (3) | O5—C23—H23A | 109.5 |
C5—C6—C7 | 116.9 (3) | O5—C23—H23B | 109.5 |
C1—C6—C7 | 122.9 (2) | H23A—C23—H23B | 109.5 |
N1—C7—C6 | 127.4 (2) | O5—C23—H23C | 109.5 |
N1—C7—H7 | 116.3 | H23A—C23—H23C | 109.5 |
C6—C7—H7 | 116.3 | H23B—C23—H23C | 109.5 |
N1—C8—C9 | 111.1 (2) | O6—C24—H24A | 109.5 |
N1—C8—H8A | 109.4 | O6—C24—H24B | 109.5 |
C9—C8—H8A | 109.4 | H24A—C24—H24B | 109.5 |
N1—C8—H8B | 109.4 | O6—C24—H24C | 109.5 |
C9—C8—H8B | 109.4 | H24A—C24—H24C | 109.5 |
H8A—C8—H8B | 108.0 | H24B—C24—H24C | 109.5 |
C10—C9—C14 | 118.6 (2) | H7A—O7—H7B | 115 (4) |
C10—C9—C8 | 121.4 (2) | ||
O3—V1—O1—C1 | 71.1 (2) | C2—C1—C6—C5 | 0.7 (4) |
O2—V1—O1—C1 | 176.2 (2) | O1—C1—C6—C7 | 3.2 (4) |
N1—V1—O1—C1 | −27.2 (2) | C2—C1—C6—C7 | −174.9 (3) |
N2—V1—O1—C1 | −100.1 (4) | C8—N1—C7—C6 | 175.9 (3) |
O4—V1—O1—C1 | −106.0 (2) | V1—N1—C7—C6 | −6.3 (4) |
O3—V1—O2—C21 | −112.0 (2) | C5—C6—C7—N1 | 174.0 (3) |
O1—V1—O2—C21 | 148.8 (2) | C1—C6—C7—N1 | −10.3 (5) |
N1—V1—O2—C21 | 61.2 (3) | C7—N1—C8—C9 | 123.6 (3) |
N2—V1—O2—C21 | −18.9 (2) | V1—N1—C8—C9 | −54.2 (3) |
O4—V1—O2—C21 | 65.2 (2) | N1—C8—C9—C10 | −117.2 (3) |
O2—V1—O4—C22 | 51.8 (2) | N1—C8—C9—C14 | 64.7 (3) |
O1—V1—O4—C22 | −40.0 (2) | C14—C9—C10—C11 | 0.3 (4) |
N1—V1—O4—C22 | −129.9 (3) | C8—C9—C10—C11 | −177.8 (3) |
N2—V1—O4—C22 | 141.2 (2) | C9—C10—C11—C12 | 3.4 (4) |
O3—V1—N1—C7 | −78.8 (2) | C10—C11—C12—C13 | −4.2 (4) |
O2—V1—N1—C7 | 107.9 (3) | C11—C12—C13—C14 | 1.2 (4) |
O1—V1—N1—C7 | 19.8 (2) | C12—C13—C14—C9 | 2.6 (4) |
N2—V1—N1—C7 | −172.0 (2) | C12—C13—C14—N2 | −174.6 (2) |
O4—V1—N1—C7 | 103.8 (2) | C10—C9—C14—C13 | −3.4 (4) |
O3—V1—N1—C8 | 98.95 (19) | C8—C9—C14—C13 | 174.8 (2) |
O2—V1—N1—C8 | −74.4 (3) | C10—C9—C14—N2 | 174.0 (2) |
O1—V1—N1—C8 | −162.43 (18) | C8—C9—C14—N2 | −7.9 (3) |
N2—V1—N1—C8 | 5.71 (18) | C15—N2—C14—C13 | −42.0 (3) |
O4—V1—N1—C8 | −78.43 (18) | V1—N2—C14—C13 | 127.3 (2) |
O3—V1—N2—C15 | 115.2 (2) | C15—N2—C14—C9 | 140.7 (3) |
O2—V1—N2—C15 | 10.4 (2) | V1—N2—C14—C9 | −50.0 (3) |
O1—V1—N2—C15 | −73.6 (4) | C14—N2—C15—C16 | 169.9 (3) |
N1—V1—N2—C15 | −146.5 (2) | V1—N2—C15—C16 | 1.5 (4) |
O4—V1—N2—C15 | −67.7 (2) | N2—C15—C16—C17 | 173.7 (3) |
O3—V1—N2—C14 | −53.36 (18) | N2—C15—C16—C21 | −11.6 (5) |
O2—V1—N2—C14 | −158.14 (17) | C21—C16—C17—C18 | 1.1 (5) |
O1—V1—N2—C14 | 117.9 (3) | C15—C16—C17—C18 | 176.0 (3) |
N1—V1—N2—C14 | 44.94 (17) | C16—C17—C18—C19 | −1.1 (6) |
O4—V1—N2—C14 | 123.81 (17) | C17—C18—C19—C20 | −0.1 (5) |
V1—O1—C1—C6 | 20.7 (4) | C24—O6—C20—C19 | 4.9 (5) |
V1—O1—C1—C2 | −161.21 (18) | C24—O6—C20—C21 | −174.7 (3) |
C23—O5—C2—C3 | 3.9 (4) | C18—C19—C20—O6 | −178.3 (3) |
C23—O5—C2—C1 | −175.3 (3) | C18—C19—C20—C21 | 1.3 (5) |
O1—C1—C2—O5 | 1.5 (3) | V1—O2—C21—C16 | 15.6 (4) |
C6—C1—C2—O5 | 179.7 (2) | V1—O2—C21—C20 | −166.85 (18) |
O1—C1—C2—C3 | −177.8 (3) | C17—C16—C21—O2 | 177.7 (3) |
C6—C1—C2—C3 | 0.5 (4) | C15—C16—C21—O2 | 3.1 (4) |
O5—C2—C3—C4 | 179.1 (3) | C17—C16—C21—C20 | 0.1 (4) |
C1—C2—C3—C4 | −1.7 (5) | C15—C16—C21—C20 | −174.5 (3) |
C2—C3—C4—C5 | 1.9 (5) | O6—C20—C21—O2 | 0.6 (4) |
C3—C4—C5—C6 | −0.7 (6) | C19—C20—C21—O2 | −179.0 (3) |
C4—C5—C6—C1 | −0.5 (5) | O6—C20—C21—C16 | 178.4 (2) |
C4—C5—C6—C7 | 175.3 (3) | C19—C20—C21—C16 | −1.2 (4) |
O1—C1—C6—C5 | 178.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O7i | 0.82 (3) | 1.86 (4) | 2.672 (3) | 171 (3) |
O7—H7B···O1 | 0.75 (4) | 2.31 (4) | 2.941 (3) | 143 (4) |
O7—H7B···O5 | 0.75 (4) | 2.19 (4) | 2.838 (4) | 146 (4) |
O7—H7A···O2 | 0.78 (5) | 2.38 (4) | 3.004 (3) | 138 (4) |
O7—H7A···O6 | 0.78 (5) | 2.08 (5) | 2.783 (4) | 151 (4) |
C12—H12···O2ii | 0.93 | 2.56 | 3.440 (3) | 158 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [V(C23H20N2O4)O(CH4O)]·H2O |
Mr | 505.41 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 290 |
a, b, c (Å) | 6.9808 (2), 34.6243 (12), 9.6740 (4) |
β (°) | 92.774 (4) |
V (Å3) | 2335.52 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.47 |
Crystal size (mm) | 0.35 × 0.17 × 0.15 |
Data collection | |
Diffractometer | Oxford Xcalibur diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14484, 4113, 3635 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.098, 1.20 |
No. of reflections | 4113 |
No. of parameters | 319 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.30 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O7i | 0.82 (3) | 1.86 (4) | 2.672 (3) | 171 (3) |
O7—H7B···O1 | 0.75 (4) | 2.31 (4) | 2.941 (3) | 143 (4) |
O7—H7B···O5 | 0.75 (4) | 2.19 (4) | 2.838 (4) | 146 (4) |
O7—H7A···O2 | 0.78 (5) | 2.38 (4) | 3.004 (3) | 138 (4) |
O7—H7A···O6 | 0.78 (5) | 2.08 (5) | 2.783 (4) | 151 (4) |
C12—H12···O2ii | 0.93 | 2.56 | 3.440 (3) | 158 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z+1. |
H2L X-ray | H2L DFT | (I) X-ray | (I) DFT | |
O1—C1 | 1.344 (2) | 1.339 | 1.313 (3) | 1.306 |
C1—C6 | 1.395 (2) | 1.411 | 1.411 (4) | 1.419 |
C6–C7 | 1.450 (2) | 1.456 | 1.441 (4) | 1.434 |
C7–N1 | 1.263 (2) | 1.281 | 1.280 (3) | 1.294 |
N1–C8 | 1.454 (2) | 1.452 | 1.484 (3) | 1.473 |
C8–C9 | 1.503 (2) | 1.519 | 1.502 (4) | 1.509 |
C9–C14 | 1.394 (2) | 1.411 | 1.397 (4) | 1.404 |
C14–N2 | 1.417 (2) | 1.410 | 1.440 (3) | 1.426 |
N2–C15 | 1.278 (2) | 1.289 | 1.286 (3) | 1.303 |
C15–C16 | 1.447 (2) | 1.450 | 1.435 (4) | 1.428 |
C16–C21 | 1.397 (2) | 1.413 | 1.414 (4) | 1.422 |
C21–O2 | 1.348 (2) | 1.339 | 1.319 (3) | 1.296 |
N1–V1 | 2.093 (2) | 2.095 | ||
N2–V1 | 2.121 (2) | 2.137 | ||
O1–V1 | 1.987 (2) | 1.974 | ||
O2–V1 | 1.964 (2) | 1.951 | ||
O3–V1 | 1.595 (2) | 1.578 | ||
O4–V1 | 2.350 (2) | 3.487 | ||
O1–C1–C6 | 122.4 (1) | 122.4 | 124.5 (2) | 123.2 |
C1–C6–C7 | 120.8 (1) | 120.6 | 122.9 (2) | 120.4 |
C6–C7–N1 | 122.8 (2) | 123.0 | 127.4 (3) | 127.0 |
C7–N1–C8 | 117.9 (2) | 119.1 | 118.0 (2) | 117.7 |
N1–C8–C9 | 112.9 (1) | 113.4 | 111.1 (2) | 111.8 |
C8–C9–C14 | 118.7 (1) | 119.1 | 119.9 (2) | 119.8 |
C9–C14–N2 | 116.8 (1) | 118.4 | 118.6 (2) | 118.6 |
C14–N2–C15 | 122.2 (1) | 120.9 | 117.9 (2) | 117.5 |
N2–C15–C16 | 121.7 (2) | 122.9 | 127.4 (3) | 127.5 |
C15–C16–C21 | 121.0 (1) | 120.8 | 122.5 (2) | 121.5 |
C16–C21–O2 | 122.0 (1) | 122.4 | 124.9 (2) | 123.9 |
O1–V1–O2 | 90.49 (7) | 86.47 | ||
O1–V1–N1 | 88.61 (7) | 84.66 | ||
O2–V1–N2 | 88.18 (7) | 85.63 | ||
N1–V1–N2 | 87.73 (8) | 87.20 | ||
O3–V1–O4 | 176.14 (8) | 175.56 | ||
O1–C1–C6–C7 | -1.0 (2) | -0.1 | 3.1 (4) | 4.6 |
C1–C6–C7–N1 | 5.0 (2) | 1.0 | -10.2 (5) | -14.9 |
C6–C7–N1–C8 | 179.8 (1) | -178.4 | 175.9 (3) | 171.1 |
C7–N1–C8–C9 | -110.0 (2) | -123.1 | 123.6 (3) | 124.1 |
N1–C8–C9–C14 | -177.9 (1) | -173.3 | 64.8 (3) | 60.8 |
C8–C9–C14–N2 | -1.0 (2) | -1.2 | -7.9 (4) | -0.8 |
C9–C14–N2–C15 | 159.0 (1) | 141.1 | 140.6 (3) | 135.3 |
C14–N2–C15–C16 | 176.7 (1) | 176.6 | 169.8 (3) | 176.6 |
N2–C15–C16–C21 | 3.4 (2) | -0.9 | -11.5 (5) | -0.6 |
C15–C16–C21–O2 | -2.2 (2) | 0.1 | 3.1 (4) | -3.2 |
A/B | 78.1 | 117.7 | 49.7 (1) | 49.3 |
B/C | 22.0 | 43.2 | 56.6 (1) | 48.7 |
A/C | 64.4 | 133.2 | 19.8 (2) | 21.7 |
D—H···A | Method | D—H | H···A | D···A | D—H···A |
O1—H1···N1 | X-ray | 0.91 (2) | 1.79 (2) | 2.614 (2) | 149 (2) |
O1—H1···N1 | DFT | 0.995 | 1.732 | 2.627 | 147 |
O2—H2···N2 | X-ray | 0.89 (2) | 1.75 (2) | 2.585 (2) | 154 (2) |
O2—H2···N2 | DFT | 0.993 | 1.736 | 2.631 | 148 |
O7—H7B···O1 | X-ray | 0.75 (4) | 2.31 (4) | 2.941 (3) | 143 (4) |
O7—H7B···O1 | DFT | 0.97 | 1.94 | 2.846 | 154 |
O7—H7B···O5 | X-ray | 0.75 (4) | 2.19 (4) | 2.838 (4) | 146 (4) |
O7—H7B···O5 | DFT | 0.97 | 2.80 | 3.619 | 142 |
O7—H7A···O2 | X-ray | 0.78 (5) | 2.38 (4) | 3.004 (3) | 138 (4) |
O7—H7A···O2 | DFT | 0.97 | 2.50 | 2.990 | 111 |
O7—H7A'···O6 | X-ray | 0.78 (5) | 2.08 (5) | 2.783 (4) | 151 (4) |
O7—H7A'···O6 | DFT | 0.97 | 2.03 | 3.000 | 179 |
O4—H4···O7 | DFT | 0.98 | 1.86 | 2.834 | 175 |
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Schiff bases and their complexes with various metal ions are a very interesting class of compounds, covering coordination chemistry, chemical biology and medical science. Oxovanadium(IV) complexes of Schiff bases are now established as an important class of drugs because of their medical importance due to their insulin-like effect (Thompson et al., 1999). Additionally, these complexes are used in some chemical processes (Ben Zid et al., 2010) as catalysts, and also as biological models in understanding the structure of biomolecular and biological processes (Meshkini & Yazdanparast, 2010). Furthermore, vanadium compounds are interesting because of their adverse effect on the hydroprocessing catalysts used in refining crude oil (Bu et al., 1996).
We have recently described the crystal structure of the oxovanadium(IV) complex of a tetradentate Schiff base, [VO(acetph)], where H2acetph is N,N'-bis(salicylidene)-1,2-phenylenediamine (Kurzak et al., 2011). Oxovanadium(IV) compounds with this ligand are essentially five-coordinated and form monomeric green crystals containing square-pyramidal coordination structures (Abe et al., 2006; Homden et al., 2008). However, orange polynuclear linear chain structures (V═O···V═O···) have been observed in the solid state for Schiff base oxovanadium(IV) complexes (Nakajima et al., 1996; Tsuchimoto et al., 2000; Fairhurst et al., 1995). Additionally, there is a rare group of oxovanadium(IV) complexes with a weak coordination of solvent molecules. Among these are complexes where the solvent is coordinated in equatorial (Fairhurst et al., 1995; Rayati et al., 2008) or axial positions (Jing et al., 2005; Uemura et al., 2000; Xie et al., 2007). In this article, the title oxovanadium(IV) complex with both a Schiff base and a coordinated methanol molecule (at the 6-position trans to the vanadyl O atom), (I), has been structurally characterized.
The molecular structure of (I) in the solid state and of its ligand [N,N'-bis(3-methoxysalicylidene)-2-aminobenzamine (H2L); Dey et al., 2001] are presented in Figs. 1(a) and 1(b). In order to extend the structural studies, the molecular geometries of (I) and H2L were optimized using quantum-mechanical density functional theory (DFT) calculations. The DFT-calculated molecular structures of (I) and H2L are presented in Figs. 1(c) and 1(d). Selected interatomic distances and bond and torsion angles for the studied compounds, obtained by X-ray diffraction analysis and calculated by DFT, are given in Table 1. Some geometric parameters of H2L (Dey et al., 2001) are presented for comparison.
In the solid state, (I) contains a distorted octahedral VO+2 species, with the terminal oxide (atom O3) and the coordinated methanol molecule (atom O4) occupying the axial positions. The bond angles around the VV centre formed by the N2O2 donor atoms from the Schiff base are almost 90°, so its deviation from strict planarity is quite small. The VV cation is 0.322 (1) Å above the average plane defined by the N2O2 donor atoms and shifted towards vanadyl atom O3. In similar complexes found in the Cambridge Structural Database (CSD; CONQUEST, Version 1.13; Allen, 2002), the mean value of this displacement is 0.3 Å, and the value in (I) is about half that observed in unambiguously five-coordinate species such as [VO(acteph)] [0.6328 (7) Å; Kurzak et al., 2011].
The V═O bond distance and the in-plane V—O distances are comparable with those found in analogous six-coordinated derivatives (Allen, 2002), whereas in the case of the five-coordinated complex [VO(salen)], namely [N,N'-bis(salicylidene)ethane-1,2-diaminato]oxovanadium(IV), the corresponding distances are shorter (Riley et al., 1986).
The axial V1—O4(methanol) distance is similar to the average literature value of 2.3 Å for oxovanadium(IV) complexes with coordinated solvent molecules (Jing et al., 2005; Uemura et al., 2000; Xie et al., 2007).
Comparison of the V—N bond lengths in (I) with the corresponding values reported for six-coordinated complexes, where the solvent molecule occupies the axial position, shows that they are in the same range.
The axis of the V═O bond is tilted by 3.7 (1)° from the normal to the plane defined by the N2O2 donor atoms; in analogous six-coordinated oxovanadium(IV) complexes this parameter is in the range 2.3–6.7° (Allen, 2002).
The axis of the V1—O4 bond is tilted by only 0.2 (1)°. In this case, the average value in similar structures is 1.77° (Allen, 2002). In the DFT-calculated structure of (I) this angle increases to 4.5°; the value of the V1—O4 bond distance is longer than 3 Å and the displacement of the V atom from the N2O2 plane increases by more than 0.2 Å. In consequence, the V atom in the DFT-calculated structure of (I) adopts the features of five-coordination.
In the DFT structure of (I) there is an O4—H4···O7 hydrogen bond between the solvent molecules (MeOH and H2O). This interaction in the solid-state structure of (I) concerns a water molecule bonded to a neighbouring complex molecule [O4—H4···O7i; symmetry code: (i) x+1, y, z], in view of the shorter distance between the atoms constituting this interaction. Otherwise, there are no significant differences between the values of the bond lengths and angles of (I) in the solid-state and calculated structures; the differences do not exceed 0.05 Å for bond distances and 3° for bond angles. However, the formation of the complex results in changes in the geometry of the ligand molecule, and there are three places in the structure where the differences in the torsion angles are particularly marked, i.e. rotation around the N1—C8, C8—C9 and C14—N2 bonds.
Three planar fragments may be distinguished in (I): plane A, formed by atoms C1–C6 (the benzene ring connected to atom O1), plane B, formed by atoms C9–C14 (the benzene ring connected to the atom N2), and plane C, formed by atoms C16–C21 (the benzene ring connected to atom O2). The values of the A/B, A/C and B/C angles are collected in Table 1. Based on these data, it can be concluded that the ligand molecule adopts a more coplanar conformation in the solid state than in the gas phase, as well as during complex formation.
The molecular structure of H2L is partly stabilized by intramolecular O—H···N hydrogen bonds (Table 2), forming five-membered quasi-rings. An extra quasi-ring can be considered as a quasi-aromatic ring, which contains an H atom in the ligand or a metal ion in the complex. The resulting rings can be investigated as molecular patterns of intramolecular resonance-assisted hydrogen bonds. The position of the extra ring formed by the substituent interacting through the hydrogen bond is found to influence both the strength of that hydrogen bond and the local aromaticity of the polycyclic aromatic hydrocarbon (PAH) skeleton. Relatively speaking, a greater loss of aromaticity of the ipso-ring (benzene ring) can be observed for these kinked structures because of the greater participation of ipso-ring π-electrons in the formation of the quasi-ring (Krygowski et al., 2010; Palusiak et al., 2009).
The harmonic oscillator model of aromaticity (HOMA; Kruszewski & Krygowski, 1973; Krygowski, 1993) is a leading method for the quantitative determination of cyclic π-electron delocalization (aromaticity) in chemical compounds. It is based on the geometric criterion of aromaticity, which stipulates that bond lengths in aromatic systems are between the values typical for single and double bonds. The HOMA values calculated for (I) and H2L are collected in Table 3. It can be seen that π-electronic effects play an important role in the stabilization of the molecular structures of these chemical species and, additionally, that the hydrogen-bonded quasi-ring can partially adopt the role of a typical aromatic ring. The aromatic characters of benzene rings A and C in the ligand molecule are almost identical and slightly smaller than in ring B. This loss of aromaticity of the ipso-rings (benzene rings A and C) is a result of the participation of π-electrons from the respective rings in the quasi-rings formed by the intramolecular O—H···N hydrogen bonds. The formation of the complex leads to a subsequent loss of aromaticity for rings A and B due to more effective π-electron communication with the quasi-rings. Due to the isolation of ring B by sp3 atom C8, its π-electrons have limited access to the quasi-ring.
A crystal packing diagram for (I) is shown in Fig. 2. Due to the additional O atom of the water molecule, the hydrogen-bond network is enriched in the solid-state structure of (I). The parameters of these interactions are given in Table 4. The two strong intermolecular hydrogen bonds O4—H4A···O7i and C12—H12···O2ii [symmetry code: (ii) -x + 2, -y + 1, -z + 1] form chains along the a axis. The V···V distance between neighbouring molecules in the crystal structure is 6.9808 (7) Å.