Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807050891/av3116sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807050891/av3116Isup2.hkl |
CCDC reference: 660426
1-Amino-1-methylpropanol (0.285 g, 3.20 mmol) was added to the solution of ethyl acetate containing 4-hydroxybenzaldehyde (0.345 g, 2.50 mmol). After keeping stirred at room temperature for 1 h, the precipitated yellow solid was then filtrated. Recrystallization from the mixture solvents (methanol:ethtyl acetate = 1:4) provided a yellow needle as the salen compound. Yield: 85%. 1H NMR (300 MHz, CDCl3) δ: 8.20 (s, 1H), 7.13 (d, J = 7.9 Hz, 1H), 6.12 (d, J = 7.9 Hz, 1H), 6.05 (s, 1H), 4.45 (s, 1H), 3.53 (s, 2H), 3.32 (s, 1H), 1.40 (s, 6H). 13C NMR (75 MHz, CDCl3) δ: 177.27, 166.35, 135.76, 110.06, 106.62, 68.86, 58.14, 22.52. IR (KBr, cm-1): 3061, 2972, 2900, 1636, 1229, 1072. Analysis found: C 63.41, H 7.50, N 6.72%; C11H15NO3 requires: C 63.14, H 7.23, N 6.69%.
The salen ligand (0.230 g, 1.1 mmol) was dissolved in 10 ml me thanol. The other 10 ml of methanol solution containing 0.20 g copper acetate (1.0 mmol) was then slowly added when keeping stirred at room temperature. After two hours, the resulting green solid was filtrated and washed by methanol for 4–6 times. Drying in vacuum provied the tetranuclear CuII complex. Crystals suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared. Analysis found: C 47.56, H 5.52, N 4.17%; C48H68N4O16Cu4 requires: C 47.60, H 5.66, N 4.63%.
H atoms were visible in diference maps and were subsequently treated as riding atoms with distances C—H = 0.98 (CH3), 0.99 (CH2) or 1.00 Å (CH) and O—H = 0.84 Å.
Data collection: SMART; cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Cu4(C11H13NO3)4]·4CH4O | F(000) = 1252 |
Mr = 1211.27 | Dx = 1.496 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 13.260 (1) Å | Cell parameters from 198 reflections |
b = 15.3170 (11) Å | θ = 2.8–23.6° |
c = 13.266 (1) Å | µ = 1.63 mm−1 |
β = 94.936 (1)° | T = 293 K |
V = 2684.4 (3) Å3 | Block, green |
Z = 2 | 0.27 × 0.21 × 0.19 mm |
Bruker SMART CCD area-detector diffractometer | 5500 independent reflections |
Radiation source: fine-focus sealed tube | 4143 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
ω scans | θmax = 26.4°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −16→16 |
Tmin = 0.667, Tmax = 0.747 | k = −16→19 |
15163 measured reflections | l = −14→16 |
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) = 0.089 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0467P)2 + 0.7871P] where P = (Fo2 + 2Fc2)/3 |
5500 reflections | (Δ/σ)max = 0.001 |
335 parameters | Δρmax = 0.46 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
[Cu4(C11H13NO3)4]·4CH4O | V = 2684.4 (3) Å3 |
Mr = 1211.27 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.260 (1) Å | µ = 1.63 mm−1 |
b = 15.3170 (11) Å | T = 293 K |
c = 13.266 (1) Å | 0.27 × 0.21 × 0.19 mm |
β = 94.936 (1)° |
Bruker SMART CCD area-detector diffractometer | 5500 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 4143 reflections with I > 2σ(I) |
Tmin = 0.667, Tmax = 0.747 | Rint = 0.032 |
15163 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.46 e Å−3 |
5500 reflections | Δρmin = −0.31 e Å−3 |
335 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 | ||
Cu1 | −0.03362 (3) | 0.14760 (2) | 0.40100 (2) | 0.03335 (10) | |
Cu2 | 0.10141 (2) | −0.02196 (2) | 0.43998 (3) | 0.03326 (11) | |
N1 | 0.23637 (17) | −0.06909 (14) | 0.43062 (18) | 0.0355 (5) | |
N2 | −0.06058 (17) | 0.13685 (14) | 0.25524 (17) | 0.0343 (5) | |
O1 | 0.35289 (19) | 0.33567 (14) | 0.3623 (2) | 0.0738 (8) | |
H1 | 0.3034 | 0.3627 | 0.3786 | 0.111* | |
O2 | 0.14247 (14) | 0.09726 (11) | 0.42952 (15) | 0.0395 (5) | |
O3 | 0.06112 (14) | −0.14255 (11) | 0.45695 (14) | 0.0336 (4) | |
O4 | −0.1033 (2) | 0.55741 (12) | 0.27462 (17) | 0.0581 (6) | |
H4 | −0.0864 | 0.5698 | 0.3338 | 0.087* | |
O5 | −0.02680 (16) | 0.27247 (12) | 0.39976 (14) | 0.0412 (5) | |
O6 | −0.03814 (13) | 0.01988 (11) | 0.40057 (14) | 0.0329 (4) | |
O7 | −0.08781 (19) | 0.65603 (14) | 0.44334 (18) | 0.0563 (6) | |
H7A | −0.0479 | 0.6758 | 0.4883 | 0.084* | |
O8 | 0.1988 (2) | 0.43416 (18) | 0.4108 (3) | 0.0982 (11) | |
H8 | 0.1642 | 0.4167 | 0.4550 | 0.147* | |
C1 | 0.3369 (2) | 0.2493 (2) | 0.3721 (3) | 0.0483 (8) | |
C2 | 0.2451 (2) | 0.21476 (18) | 0.3931 (2) | 0.0404 (7) | |
H2 | 0.1907 | 0.2523 | 0.3986 | 0.048* | |
C3 | 0.2311 (2) | 0.12554 (17) | 0.4062 (2) | 0.0342 (6) | |
C4 | 0.3151 (2) | 0.06916 (18) | 0.3953 (2) | 0.0368 (6) | |
C5 | 0.4071 (2) | 0.1072 (2) | 0.3714 (3) | 0.0511 (8) | |
H5 | 0.4618 | 0.0708 | 0.3629 | 0.061* | |
C6 | 0.4190 (3) | 0.1945 (2) | 0.3605 (3) | 0.0571 (9) | |
H6 | 0.4808 | 0.2174 | 0.3454 | 0.068* | |
C7 | 0.3133 (2) | −0.02352 (18) | 0.4083 (2) | 0.0397 (7) | |
H7 | 0.3728 | −0.0537 | 0.3999 | 0.048* | |
C8 | 0.2431 (2) | −0.16499 (17) | 0.4481 (2) | 0.0411 (7) | |
C9 | 0.1356 (2) | −0.19766 (18) | 0.4189 (2) | 0.0407 (7) | |
H9A | 0.1242 | −0.2005 | 0.3457 | 0.049* | |
H9B | 0.1285 | −0.2562 | 0.4452 | 0.049* | |
C10 | 0.2748 (3) | −0.1798 (2) | 0.5603 (3) | 0.0549 (9) | |
H10A | 0.3433 | −0.1604 | 0.5754 | 0.082* | |
H10B | 0.2702 | −0.2408 | 0.5756 | 0.082* | |
H10C | 0.2309 | −0.1474 | 0.6003 | 0.082* | |
C11 | 0.3168 (3) | −0.2113 (2) | 0.3827 (3) | 0.0659 (11) | |
H11A | 0.3052 | −0.1916 | 0.3140 | 0.099* | |
H11B | 0.3063 | −0.2732 | 0.3854 | 0.099* | |
H11C | 0.3851 | −0.1980 | 0.4079 | 0.099* | |
C12 | −0.0571 (2) | 0.32373 (17) | 0.3224 (2) | 0.0341 (6) | |
C13 | −0.0653 (2) | 0.41317 (17) | 0.3394 (2) | 0.0386 (7) | |
H13 | −0.0501 | 0.4351 | 0.4043 | 0.046* | |
C14 | −0.0956 (2) | 0.46972 (18) | 0.2615 (2) | 0.0406 (7) | |
C15 | −0.1183 (3) | 0.43913 (19) | 0.1646 (2) | 0.0475 (8) | |
H15 | −0.1381 | 0.4776 | 0.1124 | 0.057* | |
C16 | −0.1115 (2) | 0.35204 (19) | 0.1458 (2) | 0.0454 (7) | |
H16 | −0.1270 | 0.3318 | 0.0802 | 0.055* | |
C17 | −0.0816 (2) | 0.29170 (17) | 0.2229 (2) | 0.0354 (6) | |
C18 | −0.0791 (2) | 0.20114 (18) | 0.1946 (2) | 0.0373 (6) | |
H18 | −0.0921 | 0.1881 | 0.1262 | 0.045* | |
C19 | −0.0595 (2) | 0.04485 (17) | 0.2171 (2) | 0.0406 (7) | |
C20 | −0.0882 (2) | −0.01003 (18) | 0.3081 (2) | 0.0422 (7) | |
H20A | −0.1608 | −0.0070 | 0.3121 | 0.051* | |
H20B | −0.0704 | −0.0706 | 0.2977 | 0.051* | |
C21 | 0.0475 (3) | 0.0259 (2) | 0.1897 (3) | 0.0572 (9) | |
H21A | 0.0620 | 0.0613 | 0.1330 | 0.086* | |
H21B | 0.0530 | −0.0346 | 0.1724 | 0.086* | |
H21C | 0.0949 | 0.0392 | 0.2464 | 0.086* | |
C22 | −0.1361 (3) | 0.0277 (2) | 0.1279 (3) | 0.0657 (10) | |
H22A | −0.2011 | 0.0495 | 0.1427 | 0.098* | |
H22B | −0.1407 | −0.0340 | 0.1154 | 0.098* | |
H22C | −0.1152 | 0.0567 | 0.0690 | 0.098* | |
C23 | −0.1332 (3) | 0.7280 (2) | 0.3820 (3) | 0.0661 (10) | |
H23A | −0.1480 | 0.7756 | 0.4254 | 0.099* | |
H23B | −0.1945 | 0.7083 | 0.3454 | 0.099* | |
H23C | −0.0866 | 0.7472 | 0.3351 | 0.099* | |
C24 | 0.1820 (3) | 0.5212 (3) | 0.3951 (4) | 0.0832 (13) | |
H24A | 0.2104 | 0.5535 | 0.4528 | 0.125* | |
H24B | 0.1105 | 0.5319 | 0.3854 | 0.125* | |
H24C | 0.2134 | 0.5395 | 0.3360 | 0.125* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0420 (2) | 0.02276 (17) | 0.0347 (2) | 0.00045 (14) | −0.00022 (15) | 0.00095 (14) |
Cu2 | 0.03172 (18) | 0.02416 (18) | 0.0440 (2) | 0.00098 (13) | 0.00402 (15) | 0.00292 (14) |
N1 | 0.0353 (13) | 0.0261 (12) | 0.0450 (14) | 0.0032 (10) | 0.0037 (11) | −0.0022 (10) |
N2 | 0.0388 (13) | 0.0281 (12) | 0.0351 (13) | 0.0046 (10) | −0.0017 (10) | −0.0032 (10) |
O1 | 0.0655 (17) | 0.0387 (14) | 0.121 (2) | −0.0166 (11) | 0.0278 (17) | 0.0148 (14) |
O2 | 0.0327 (10) | 0.0263 (10) | 0.0598 (13) | −0.0008 (8) | 0.0068 (9) | 0.0032 (9) |
O3 | 0.0392 (10) | 0.0250 (9) | 0.0367 (11) | 0.0015 (8) | 0.0044 (8) | −0.0006 (8) |
O4 | 0.0942 (19) | 0.0263 (11) | 0.0519 (15) | 0.0109 (11) | −0.0045 (14) | 0.0002 (9) |
O5 | 0.0641 (13) | 0.0240 (10) | 0.0337 (11) | −0.0001 (9) | −0.0068 (10) | 0.0023 (8) |
O6 | 0.0331 (10) | 0.0240 (9) | 0.0408 (11) | 0.0002 (8) | −0.0017 (8) | 0.0014 (8) |
O7 | 0.0670 (16) | 0.0447 (13) | 0.0548 (15) | −0.0046 (11) | −0.0084 (12) | −0.0100 (11) |
O8 | 0.089 (2) | 0.0605 (19) | 0.151 (3) | −0.0021 (16) | 0.043 (2) | 0.0052 (18) |
C1 | 0.0504 (19) | 0.0382 (17) | 0.058 (2) | −0.0107 (15) | 0.0113 (16) | 0.0073 (15) |
C2 | 0.0427 (17) | 0.0323 (16) | 0.0465 (18) | −0.0005 (12) | 0.0065 (14) | 0.0049 (13) |
C3 | 0.0345 (15) | 0.0329 (15) | 0.0349 (16) | −0.0060 (12) | 0.0014 (12) | 0.0000 (12) |
C4 | 0.0350 (15) | 0.0362 (16) | 0.0400 (16) | −0.0024 (12) | 0.0070 (13) | 0.0013 (12) |
C5 | 0.0402 (18) | 0.052 (2) | 0.063 (2) | −0.0013 (15) | 0.0153 (16) | 0.0037 (16) |
C6 | 0.049 (2) | 0.052 (2) | 0.073 (3) | −0.0119 (16) | 0.0196 (18) | 0.0070 (17) |
C7 | 0.0341 (15) | 0.0399 (17) | 0.0455 (18) | 0.0033 (13) | 0.0060 (13) | −0.0051 (13) |
C8 | 0.0414 (17) | 0.0262 (15) | 0.056 (2) | 0.0068 (12) | 0.0070 (14) | −0.0037 (13) |
C9 | 0.0479 (17) | 0.0268 (15) | 0.0480 (18) | 0.0004 (13) | 0.0081 (14) | −0.0084 (13) |
C10 | 0.052 (2) | 0.0418 (18) | 0.068 (2) | 0.0065 (15) | −0.0090 (17) | 0.0088 (16) |
C11 | 0.058 (2) | 0.0398 (19) | 0.103 (3) | 0.0079 (16) | 0.025 (2) | −0.0133 (19) |
C12 | 0.0356 (15) | 0.0281 (14) | 0.0388 (16) | 0.0028 (11) | 0.0044 (12) | 0.0043 (12) |
C13 | 0.0509 (18) | 0.0282 (15) | 0.0360 (16) | 0.0023 (13) | 0.0010 (13) | −0.0017 (12) |
C14 | 0.0476 (18) | 0.0290 (15) | 0.0454 (18) | 0.0059 (13) | 0.0052 (14) | 0.0027 (13) |
C15 | 0.069 (2) | 0.0336 (17) | 0.0382 (18) | 0.0074 (15) | −0.0038 (16) | 0.0078 (13) |
C16 | 0.061 (2) | 0.0393 (17) | 0.0344 (17) | 0.0060 (15) | −0.0024 (15) | 0.0018 (13) |
C17 | 0.0431 (16) | 0.0282 (15) | 0.0349 (16) | 0.0041 (12) | 0.0025 (13) | 0.0014 (12) |
C18 | 0.0421 (16) | 0.0369 (16) | 0.0328 (16) | 0.0031 (13) | 0.0020 (13) | −0.0020 (12) |
C19 | 0.0521 (18) | 0.0269 (15) | 0.0420 (17) | 0.0067 (13) | −0.0013 (14) | −0.0084 (12) |
C20 | 0.0442 (17) | 0.0297 (15) | 0.0508 (19) | −0.0040 (13) | −0.0064 (14) | −0.0055 (13) |
C21 | 0.071 (2) | 0.0448 (19) | 0.058 (2) | 0.0162 (17) | 0.0179 (18) | −0.0056 (16) |
C22 | 0.090 (3) | 0.046 (2) | 0.056 (2) | 0.0023 (19) | −0.023 (2) | −0.0132 (16) |
C23 | 0.076 (3) | 0.054 (2) | 0.065 (3) | 0.0069 (19) | −0.008 (2) | −0.0059 (18) |
C24 | 0.075 (3) | 0.069 (3) | 0.107 (4) | 0.002 (2) | 0.018 (3) | 0.018 (2) |
Cu1—O5 | 1.9150 (18) | C8—C10 | 1.528 (4) |
Cu1—N2 | 1.943 (2) | C8—C9 | 1.530 (4) |
Cu1—O3i | 1.9515 (18) | C8—C11 | 1.535 (4) |
Cu1—O6 | 1.9572 (17) | C9—H9A | 0.9700 |
Cu1—Cu2i | 3.0477 (5) | C9—H9B | 0.9700 |
Cu2—O2 | 1.9139 (18) | C10—H10A | 0.9600 |
Cu2—O3 | 1.9414 (17) | C10—H10B | 0.9600 |
Cu2—N1 | 1.944 (2) | C10—H10C | 0.9600 |
Cu2—O6 | 1.9853 (17) | C11—H11A | 0.9600 |
Cu2—O6i | 2.3419 (18) | C11—H11B | 0.9600 |
Cu2—Cu1i | 3.0477 (5) | C11—H11C | 0.9600 |
N1—C7 | 1.291 (3) | C12—C13 | 1.394 (4) |
N2—C18 | 1.282 (3) | C13—H13 | 0.9300 |
N2—C19 | 1.498 (3) | C14—C15 | 1.377 (4) |
O1—C1 | 1.348 (3) | C14—C13 | 1.382 (4) |
O1—H1 | 0.8200 | C15—H15 | 0.9300 |
O2—C3 | 1.314 (3) | C16—C15 | 1.361 (4) |
O3—C9 | 1.424 (3) | C16—H16 | 0.9300 |
O3—Cu1i | 1.9515 (18) | C17—C16 | 1.410 (4) |
O4—C14 | 1.359 (3) | C17—C12 | 1.420 (4) |
O4—H4 | 0.8200 | C17—C18 | 1.438 (4) |
O5—C12 | 1.327 (3) | C18—H18 | 0.9300 |
O6—C20 | 1.420 (3) | C19—C22 | 1.515 (4) |
O6—Cu2i | 2.3419 (18) | C19—C20 | 1.546 (4) |
O7—C23 | 1.468 (4) | C20—H20A | 0.9700 |
O7—H7A | 0.8200 | C20—H20B | 0.9700 |
O8—C24 | 1.365 (4) | C21—C19 | 1.522 (4) |
O8—H8 | 0.8200 | C21—H21A | 0.9600 |
C1—C2 | 1.378 (4) | C21—H21B | 0.9600 |
C1—C6 | 1.393 (5) | C21—H21C | 0.9600 |
C2—H2 | 0.9300 | C22—H22A | 0.9600 |
C3—C2 | 1.392 (4) | C22—H22B | 0.9600 |
C3—C4 | 1.427 (4) | C22—H22C | 0.9600 |
C4—C5 | 1.411 (4) | C23—H23A | 0.9600 |
C5—H5 | 0.9300 | C23—H23B | 0.9600 |
C6—C5 | 1.356 (4) | C23—H23C | 0.9600 |
C6—H6 | 0.9300 | C24—H24A | 0.9600 |
C7—C4 | 1.430 (4) | C24—H24B | 0.9600 |
C7—H7 | 0.9300 | C24—H24C | 0.9600 |
C8—N1 | 1.488 (3) | ||
O5—Cu1—N2 | 94.64 (8) | C7—N1—C8 | 122.1 (2) |
O5—Cu1—O3i | 93.48 (8) | C7—N1—Cu2 | 124.30 (19) |
N2—Cu1—O3i | 157.52 (9) | C8—N1—Cu2 | 113.59 (17) |
O5—Cu1—O6 | 178.80 (8) | O5—C12—C13 | 118.6 (2) |
N2—Cu1—O6 | 84.80 (8) | O5—C12—C17 | 123.0 (2) |
O3i—Cu1—O6 | 87.42 (7) | C13—C12—C17 | 118.4 (2) |
O5—Cu1—Cu2i | 130.81 (6) | C8—C10—H10A | 109.5 |
N2—Cu1—Cu2i | 126.54 (7) | C8—C10—H10B | 109.5 |
O3i—Cu1—Cu2i | 38.36 (5) | H10A—C10—H10B | 109.5 |
O6—Cu1—Cu2i | 50.21 (5) | C8—C10—H10C | 109.5 |
O2—Cu2—O3 | 177.49 (8) | H10A—C10—H10C | 109.5 |
O2—Cu2—N1 | 94.62 (8) | H10B—C10—H10C | 109.5 |
O3—Cu2—N1 | 85.30 (8) | O1—C1—C2 | 123.1 (3) |
O2—Cu2—O6 | 86.42 (8) | O1—C1—C6 | 116.8 (3) |
O3—Cu2—O6 | 94.48 (7) | C2—C1—C6 | 120.2 (3) |
N1—Cu2—O6 | 161.01 (9) | N2—C19—C22 | 113.7 (2) |
O2—Cu2—O6i | 100.30 (7) | N2—C19—C21 | 107.2 (2) |
O3—Cu2—O6i | 77.56 (7) | C22—C19—C21 | 110.9 (3) |
N1—Cu2—O6i | 117.78 (8) | N2—C19—C20 | 103.7 (2) |
O6—Cu2—O6i | 80.52 (7) | C22—C19—C20 | 108.8 (3) |
O2—Cu2—Cu1i | 139.05 (6) | C21—C19—C20 | 112.3 (3) |
O3—Cu2—Cu1i | 38.59 (5) | C5—C6—C1 | 118.9 (3) |
N1—Cu2—Cu1i | 97.91 (7) | C5—C6—H6 | 120.5 |
O6—Cu2—Cu1i | 93.57 (5) | C1—C6—H6 | 120.5 |
O6i—Cu2—Cu1i | 39.95 (4) | C16—C15—C14 | 119.5 (3) |
C9—O3—Cu2 | 108.47 (16) | C16—C15—H15 | 120.3 |
C9—O3—Cu1i | 120.79 (17) | C14—C15—H15 | 120.3 |
Cu2—O3—Cu1i | 103.05 (8) | C14—C13—C12 | 121.1 (3) |
C14—O4—H4 | 109.5 | C14—C13—H13 | 119.4 |
C3—O2—Cu2 | 126.69 (17) | C12—C13—H13 | 119.4 |
C20—O6—Cu1 | 109.69 (15) | O6—C20—C19 | 111.8 (2) |
C20—O6—Cu2 | 118.65 (16) | O6—C20—H20A | 109.3 |
Cu1—O6—Cu2 | 107.11 (8) | C19—C20—H20A | 109.3 |
C20—O6—Cu2i | 127.42 (16) | O6—C20—H20B | 109.3 |
Cu1—O6—Cu2i | 89.83 (7) | C19—C20—H20B | 109.3 |
Cu2—O6—Cu2i | 99.48 (7) | H20A—C20—H20B | 107.9 |
C1—O1—H1 | 109.5 | N1—C7—C4 | 125.9 (3) |
C12—O5—Cu1 | 125.90 (17) | N1—C7—H7 | 117.0 |
C18—N2—C19 | 121.1 (2) | C4—C7—H7 | 117.0 |
C18—N2—Cu1 | 124.65 (19) | C5—C4—C3 | 118.1 (3) |
C19—N2—Cu1 | 114.20 (17) | C5—C4—C7 | 117.4 (3) |
C16—C17—C12 | 118.4 (2) | C3—C4—C7 | 124.5 (2) |
C16—C17—C18 | 117.0 (3) | C1—C2—C3 | 122.2 (3) |
C12—C17—C18 | 124.6 (2) | C1—C2—H2 | 118.9 |
O2—C3—C2 | 119.0 (2) | C3—C2—H2 | 118.9 |
O2—C3—C4 | 123.1 (2) | C6—C5—C4 | 122.8 (3) |
C2—C3—C4 | 117.9 (2) | C6—C5—H5 | 118.6 |
O4—C14—C15 | 116.3 (3) | C4—C5—H5 | 118.6 |
O4—C14—C13 | 122.9 (3) | C19—C22—H22A | 109.5 |
C15—C14—C13 | 120.7 (3) | C19—C22—H22B | 109.5 |
N1—C8—C10 | 107.8 (2) | H22A—C22—H22B | 109.5 |
N1—C8—C9 | 104.0 (2) | C19—C22—H22C | 109.5 |
C10—C8—C9 | 111.7 (3) | H22A—C22—H22C | 109.5 |
N1—C8—C11 | 113.6 (3) | H22B—C22—H22C | 109.5 |
C10—C8—C11 | 110.3 (3) | C8—C11—H11A | 109.5 |
C9—C8—C11 | 109.3 (3) | C8—C11—H11B | 109.5 |
C19—C21—H21A | 109.5 | H11A—C11—H11B | 109.5 |
C19—C21—H21B | 109.5 | C8—C11—H11C | 109.5 |
H21A—C21—H21B | 109.5 | H11A—C11—H11C | 109.5 |
C19—C21—H21C | 109.5 | H11B—C11—H11C | 109.5 |
H21A—C21—H21C | 109.5 | C23—O7—H7A | 109.5 |
H21B—C21—H21C | 109.5 | C24—O8—H8 | 109.5 |
N2—C18—C17 | 125.8 (3) | O7—C23—H23A | 109.5 |
N2—C18—H18 | 117.1 | O7—C23—H23B | 109.5 |
C17—C18—H18 | 117.1 | H23A—C23—H23B | 109.5 |
O3—C9—C8 | 112.1 (2) | O7—C23—H23C | 109.5 |
O3—C9—H9A | 109.2 | H23A—C23—H23C | 109.5 |
C8—C9—H9A | 109.2 | H23B—C23—H23C | 109.5 |
O3—C9—H9B | 109.2 | O8—C24—H24A | 109.5 |
C8—C9—H9B | 109.2 | O8—C24—H24B | 109.5 |
H9A—C9—H9B | 107.9 | H24A—C24—H24B | 109.5 |
C15—C16—C17 | 121.9 (3) | O8—C24—H24C | 109.5 |
C15—C16—H16 | 119.1 | H24A—C24—H24C | 109.5 |
C17—C16—H16 | 119.1 | H24B—C24—H24C | 109.5 |
O2—Cu2—O3—C9 | −108.5 (17) | C11—C8—C9—O3 | −164.9 (3) |
N1—Cu2—O3—C9 | −20.22 (18) | C12—C17—C16—C15 | −0.7 (5) |
O6—Cu2—O3—C9 | 140.72 (17) | C18—C17—C16—C15 | 178.8 (3) |
O6i—Cu2—O3—C9 | −140.02 (18) | C10—C8—N1—C7 | 88.9 (3) |
Cu1i—Cu2—O3—C9 | −129.2 (2) | C9—C8—N1—C7 | −152.4 (3) |
O2—Cu2—O3—Cu1i | 20.7 (18) | C11—C8—N1—C7 | −33.6 (4) |
N1—Cu2—O3—Cu1i | 108.93 (10) | C10—C8—N1—Cu2 | −93.2 (2) |
O6—Cu2—O3—Cu1i | −90.12 (9) | C9—C8—N1—Cu2 | 25.5 (3) |
O6i—Cu2—O3—Cu1i | −10.87 (7) | C11—C8—N1—Cu2 | 144.3 (2) |
O3—Cu2—O2—C3 | 97.8 (17) | O2—Cu2—N1—C7 | −9.0 (2) |
N1—Cu2—O2—C3 | 9.8 (2) | O3—Cu2—N1—C7 | 173.5 (2) |
O6—Cu2—O2—C3 | −151.2 (2) | O6—Cu2—N1—C7 | 83.4 (3) |
O6i—Cu2—O2—C3 | 129.1 (2) | O6i—Cu2—N1—C7 | −113.2 (2) |
Cu1i—Cu2—O2—C3 | 117.5 (2) | Cu1i—Cu2—N1—C7 | −150.0 (2) |
O5—Cu1—O6—C20 | −81 (4) | O2—Cu2—N1—C8 | 173.09 (19) |
N2—Cu1—O6—C20 | −18.51 (17) | O3—Cu2—N1—C8 | −4.39 (19) |
O3i—Cu1—O6—C20 | 140.38 (17) | O6—Cu2—N1—C8 | −94.5 (3) |
Cu2i—Cu1—O6—C20 | 130.12 (18) | O6i—Cu2—N1—C8 | 68.9 (2) |
O5—Cu1—O6—Cu2 | 49 (4) | Cu1i—Cu2—N1—C8 | 32.17 (19) |
N2—Cu1—O6—Cu2 | 111.50 (10) | Cu1—O5—C12—C13 | 167.74 (19) |
O3i—Cu1—O6—Cu2 | −89.61 (9) | Cu1—O5—C12—C17 | −12.3 (4) |
Cu2i—Cu1—O6—Cu2 | −99.87 (9) | C16—C17—C12—O5 | −179.0 (3) |
O5—Cu1—O6—Cu2i | 149 (4) | C18—C17—C12—O5 | 1.6 (4) |
N2—Cu1—O6—Cu2i | −148.62 (8) | C16—C17—C12—C13 | 1.0 (4) |
O3i—Cu1—O6—Cu2i | 10.26 (7) | C18—C17—C12—C13 | −178.4 (3) |
O2—Cu2—O6—C20 | 116.44 (18) | C18—N2—C19—C22 | −34.7 (4) |
O3—Cu2—O6—C20 | −65.91 (18) | Cu1—N2—C19—C22 | 144.6 (2) |
N1—Cu2—O6—C20 | 22.7 (3) | C18—N2—C19—C21 | 88.3 (3) |
O6i—Cu2—O6—C20 | −142.5 (2) | Cu1—N2—C19—C21 | −92.4 (2) |
Cu1i—Cu2—O6—C20 | −104.59 (17) | C18—N2—C19—C20 | −152.7 (3) |
O2—Cu2—O6—Cu1 | −8.30 (9) | Cu1—N2—C19—C20 | 26.6 (3) |
O3—Cu2—O6—Cu1 | 169.35 (9) | O1—C1—C6—C5 | 178.9 (3) |
N1—Cu2—O6—Cu1 | −102.1 (2) | C2—C1—C6—C5 | −0.9 (5) |
O6i—Cu2—O6—Cu1 | 92.77 (9) | C17—C16—C15—C14 | −0.1 (5) |
Cu1i—Cu2—O6—Cu1 | 130.67 (7) | O4—C14—C15—C16 | 179.6 (3) |
O2—Cu2—O6—Cu2i | −101.07 (8) | C13—C14—C15—C16 | 0.5 (5) |
O3—Cu2—O6—Cu2i | 76.58 (7) | O4—C14—C13—C12 | −179.2 (3) |
N1—Cu2—O6—Cu2i | 165.1 (2) | C15—C14—C13—C12 | −0.2 (5) |
O6i—Cu2—O6—Cu2i | 0.0 | O5—C12—C13—C14 | 179.4 (3) |
Cu1i—Cu2—O6—Cu2i | 37.90 (5) | C17—C12—C13—C14 | −0.5 (4) |
N2—Cu1—O5—C12 | 13.6 (2) | Cu1—O6—C20—C19 | 39.3 (3) |
O3i—Cu1—O5—C12 | −145.4 (2) | Cu2—O6—C20—C19 | −84.1 (2) |
O6—Cu1—O5—C12 | 76 (4) | Cu2i—O6—C20—C19 | 145.01 (18) |
Cu2i—Cu1—O5—C12 | −135.60 (19) | N2—C19—C20—O6 | −42.4 (3) |
O5—Cu1—N2—C18 | −8.0 (2) | C22—C19—C20—O6 | −163.7 (2) |
O3i—Cu1—N2—C18 | 102.8 (3) | C21—C19—C20—O6 | 73.1 (3) |
O6—Cu1—N2—C18 | 173.0 (2) | C8—N1—C7—C4 | −176.7 (3) |
Cu2i—Cu1—N2—C18 | 143.2 (2) | Cu2—N1—C7—C4 | 5.7 (4) |
O5—Cu1—N2—C19 | 172.70 (19) | O2—C3—C4—C5 | −179.2 (3) |
O3i—Cu1—N2—C19 | −76.5 (3) | C2—C3—C4—C5 | −0.3 (4) |
O6—Cu1—N2—C19 | −6.23 (18) | O2—C3—C4—C7 | −0.1 (4) |
Cu2i—Cu1—N2—C19 | −36.1 (2) | C2—C3—C4—C7 | 178.8 (3) |
Cu2—O2—C3—C2 | 174.26 (19) | N1—C7—C4—C5 | 179.7 (3) |
Cu2—O2—C3—C4 | −6.9 (4) | N1—C7—C4—C3 | 0.6 (5) |
C19—N2—C18—C17 | −179.7 (3) | O1—C1—C2—C3 | −177.9 (3) |
Cu1—N2—C18—C17 | 1.1 (4) | C6—C1—C2—C3 | 1.9 (5) |
C16—C17—C18—N2 | −175.0 (3) | O2—C3—C2—C1 | 177.7 (3) |
C12—C17—C18—N2 | 4.4 (5) | C4—C3—C2—C1 | −1.3 (4) |
Cu2—O3—C9—C8 | 41.2 (3) | C1—C6—C5—C4 | −0.7 (5) |
Cu1i—O3—C9—C8 | −77.2 (3) | C3—C4—C5—C6 | 1.2 (5) |
N1—C8—C9—O3 | −43.3 (3) | C7—C4—C5—C6 | −177.9 (3) |
C10—C8—C9—O3 | 72.7 (3) |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu4(C11H13NO3)4]·4CH4O |
Mr | 1211.27 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 13.260 (1), 15.3170 (11), 13.266 (1) |
β (°) | 94.936 (1) |
V (Å3) | 2684.4 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.63 |
Crystal size (mm) | 0.27 × 0.21 × 0.19 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.667, 0.747 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15163, 5500, 4143 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.089, 1.01 |
No. of reflections | 5500 |
No. of parameters | 335 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.46, −0.31 |
Computer programs: SMART, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
There has been continuous interest in high-nuclearity transition-metal complexes in order to elucidate the fundamentals of magnetic interactions (Kahn O., 1993; Kahn O., 1995; Gatteschi D., 1994). Especially, polynuclear metal complexes including O-bridges arising from O-alkoxo moieties have attracted intense interest (Paap et al., 1981; Atkins et al., 1993). Generally, the flexibility of the coordination sphere around CuII with varied distortions due to a pseudo-Jahn-Teller effect leads to its tremendous structral diversity. It has been exemplied that contruction of the polynuclear CuII complexes from the polydentate Schiff-based ligands represents a promising route, because the ligands can function in both bridging and chelating modes (Liu et al., 2005; Xie et al., 2007). Here we report a new tetranuclear CuII complex constructed from the salen ligand with alkoxo moieties, N-(2,5-dihyroxyphenylmethylene)-1-amino-1-methylpropanol.
As shown in Fig. 1, X-ray single-crystal analysis reveals the existance of a tetranulear CuII molecular skeleton in compound. In an ansymmetry unit, there are two CuII atoms, two ligands and two solvent methanol molecules. The tetranuclear complex contains two kinds of CuII center. Two Cu1 atoms each coordinate to the NO2 (a phenolic oxygen atom, an alcoholic oxygen atom and an imine N atom) chelator unit in one ligand and an alcohol oxygen atom from the other ligand, forming a distorted planar coordination sphere. While two Cu2 each coordinate in a pyramidal geometry. Its distorted basal plane is also formed by the N2O unit and the alcohol oxygen atom from the second ligand, and an alcohol oxygen atom from the third ligand occupies the axial position with the Cu—O distance as 2.34 Å. Two of the four alcohol oxygen atoms O3 in the ligands act as one µ2 bridged atom and the other two O6 act as µ3 bridge to link to Cu atoms together, resulting in the tetranuclear structure. Such structure can be described as two Cu—Cu cores (separated in 3.05 Å) linked by two µ3 bridged alcohol oxygen O6 and O6A atoms to form a centrosymmetric dimer of dicopper(II) moieties.