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Acta Cryst. (2007). E63, m2932    [ doi:10.1107/S1600536807050891 ]

A tetranuclear copper(II) complex constructed from the salen ligand with alkoxo groups

M.-S. Zhang, J.-Y. Jin, X. Wu, K.-Z. Shao and Z.-M. Su

Abstract top

In the title compound, tetrakis[[mu]3-2-(5-hydroxy-2-oxidobenzylideneamino)-2-methylpropanolato]tetracopper(II) methanol tetrasolvate, [Cu4(C11H13NO3)4]·4CH3OH, two Cu2 cores are linked by two [mu]3-bridging alkoxo O atoms to form a centrosymmetric dimer of dicopper(II) units. Two Cu atoms coordinate to the NO2 (a phenolic O atom, an alcoholic O atom and an imine N atom) chelator unit of one ligand and an alcohol O atom of the other ligand, forming a distorted planar coordination configure. The remaining Cu atoms coordinate in a pyramidal geometry. The distorted basal plane is also formed by the N2O unit and the alcohol O atom from the second ligand, while an alcohol O atom from a third ligand occupies the axial position.

Comment top

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.

Related literature top

For related literature, see: Atkins et al. (1993); Gatteschi (1994); Kahn (1993, 1995); Liu et al. (2005); Xie et al. (2007); Paap et al. (1985).

Experimental top

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%.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. ORTEP drawing of the tetranuclear CuII complex, showing the non-hydrogen atoms as 50% probability thermal ellipsoids. The hydrogen atoms and solvent molecules are omitted for clarity. (Symmetry code (A): −x, −y, 1 − z).
tetrakis[µ3-2-(5-hydroxy-2-oxidobenzylideneamino)-2- methylpropanolato]tetracopper(II) methanol tetrasolvate top
Crystal data top
[Cu4(C11H13N1O3)4]·4CH4OF000 = 1252
Mr = 1211.27Dx = 1.496 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71069 Å
a = 13.2600 (10) ÅCell parameters from 198 reflections
b = 15.3170 (11) Åθ = 2.8–23.6º
c = 13.2660 (10) ŵ = 1.63 mm−1
β = 94.9360 (10)ºT = 293 (2) K
V = 2684.4 (3) Å3Block, green
Z = 20.27 × 0.21 × 0.19 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		5500 independent reflections
Radiation source: fine-focus sealed tube4143 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.032
T = 293(2) Kθmax = 26.4º
ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −16→16
Tmin = 0.667, Tmax = 0.747k = −16→19
15163 measured reflectionsl = −14→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.089  w = 1/[σ2(Fo2) + (0.0467P)2 + 0.7871P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
5500 reflectionsΔρmax = 0.46 e Å−3
335 parametersΔρmin = −0.31 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu4(C11H13N1O3)4]·4CH4OV = 2684.4 (3) Å3
Mr = 1211.27Z = 2
Monoclinic, P21/nMo Kα
a = 13.2600 (10) ŵ = 1.63 mm−1
b = 15.3170 (11) ÅT = 293 (2) K
c = 13.2660 (10) Å0.27 × 0.21 × 0.19 mm
β = 94.9360 (10)º
Data collection top
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 = 0.747Rint = 0.032
15163 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035335 parameters
wR(F2) = 0.089H-atom parameters constrained
S = 1.01Δρmax = 0.46 e Å−3
5500 reflectionsΔρmin = −0.31 e Å−3
Special details top

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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu1−0.03362 (3)0.14760 (2)0.40100 (2)0.03335 (10)
Cu20.10141 (2)−0.02196 (2)0.43998 (3)0.03326 (11)
N10.23637 (17)−0.06909 (14)0.43062 (18)0.0355 (5)
N2−0.06058 (17)0.13685 (14)0.25524 (17)0.0343 (5)
O10.35289 (19)0.33567 (14)0.3623 (2)0.0738 (8)
H10.30340.36270.37860.111*
O20.14247 (14)0.09726 (11)0.42952 (15)0.0395 (5)
O30.06112 (14)−0.14255 (11)0.45695 (14)0.0336 (4)
O4−0.1033 (2)0.55741 (12)0.27462 (17)0.0581 (6)
H4−0.08640.56980.33380.087*
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−0.04790.67580.48830.084*
O80.1988 (2)0.43416 (18)0.4108 (3)0.0982 (11)
H80.16420.41670.45500.147*
C10.3369 (2)0.2493 (2)0.3721 (3)0.0483 (8)
C20.2451 (2)0.21476 (18)0.3931 (2)0.0404 (7)
H20.19070.25230.39860.048*
C30.2311 (2)0.12554 (17)0.4062 (2)0.0342 (6)
C40.3151 (2)0.06916 (18)0.3953 (2)0.0368 (6)
C50.4071 (2)0.1072 (2)0.3714 (3)0.0511 (8)
H50.46180.07080.36290.061*
C60.4190 (3)0.1945 (2)0.3605 (3)0.0571 (9)
H60.48080.21740.34540.068*
C70.3133 (2)−0.02352 (18)0.4083 (2)0.0397 (7)
H70.3728−0.05370.39990.048*
C80.2431 (2)−0.16499 (17)0.4481 (2)0.0411 (7)
C90.1356 (2)−0.19766 (18)0.4189 (2)0.0407 (7)
H9A0.1242−0.20050.34570.049*
H9B0.1285−0.25620.44520.049*
C100.2748 (3)−0.1798 (2)0.5603 (3)0.0549 (9)
H10A0.3433−0.16040.57540.082*
H10B0.2702−0.24080.57560.082*
H10C0.2309−0.14740.60030.082*
C110.3168 (3)−0.2113 (2)0.3827 (3)0.0659 (11)
H11A0.3052−0.19160.31400.099*
H11B0.3063−0.27320.38540.099*
H11C0.3851−0.19800.40790.099*
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)
H13−0.05010.43510.40430.046*
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)
H15−0.13810.47760.11240.057*
C16−0.1115 (2)0.35204 (19)0.1458 (2)0.0454 (7)
H16−0.12700.33180.08020.055*
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)
H18−0.09210.18810.12620.045*
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−0.1608−0.00700.31210.051*
H20B−0.0704−0.07060.29770.051*
C210.0475 (3)0.0259 (2)0.1897 (3)0.0572 (9)
H21A0.06200.06130.13300.086*
H21B0.0530−0.03460.17240.086*
H21C0.09490.03920.24640.086*
C22−0.1361 (3)0.0277 (2)0.1279 (3)0.0657 (10)
H22A−0.20110.04950.14270.098*
H22B−0.1407−0.03400.11540.098*
H22C−0.11520.05670.06900.098*
C23−0.1332 (3)0.7280 (2)0.3820 (3)0.0661 (10)
H23A−0.14800.77560.42540.099*
H23B−0.19450.70830.34540.099*
H23C−0.08660.74720.33510.099*
C240.1820 (3)0.5212 (3)0.3951 (4)0.0832 (13)
H24A0.21040.55350.45280.125*
H24B0.11050.53190.38540.125*
H24C0.21340.53950.33600.125*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0420 (2)0.02276 (17)0.0347 (2)0.00045 (14)−0.00022 (15)0.00095 (14)
Cu20.03172 (18)0.02416 (18)0.0440 (2)0.00098 (13)0.00402 (15)0.00292 (14)
N10.0353 (13)0.0261 (12)0.0450 (14)0.0032 (10)0.0037 (11)−0.0022 (10)
N20.0388 (13)0.0281 (12)0.0351 (13)0.0046 (10)−0.0017 (10)−0.0032 (10)
O10.0655 (17)0.0387 (14)0.121 (2)−0.0166 (11)0.0278 (17)0.0148 (14)
O20.0327 (10)0.0263 (10)0.0598 (13)−0.0008 (8)0.0068 (9)0.0032 (9)
O30.0392 (10)0.0250 (9)0.0367 (11)0.0015 (8)0.0044 (8)−0.0006 (8)
O40.0942 (19)0.0263 (11)0.0519 (15)0.0109 (11)−0.0045 (14)0.0002 (9)
O50.0641 (13)0.0240 (10)0.0337 (11)−0.0001 (9)−0.0068 (10)0.0023 (8)
O60.0331 (10)0.0240 (9)0.0408 (11)0.0002 (8)−0.0017 (8)0.0014 (8)
O70.0670 (16)0.0447 (13)0.0548 (15)−0.0046 (11)−0.0084 (12)−0.0100 (11)
O80.089 (2)0.0605 (19)0.151 (3)−0.0021 (16)0.043 (2)0.0052 (18)
C10.0504 (19)0.0382 (17)0.058 (2)−0.0107 (15)0.0113 (16)0.0073 (15)
C20.0427 (17)0.0323 (16)0.0465 (18)−0.0005 (12)0.0065 (14)0.0049 (13)
C30.0345 (15)0.0329 (15)0.0349 (16)−0.0060 (12)0.0014 (12)0.0000 (12)
C40.0350 (15)0.0362 (16)0.0400 (16)−0.0024 (12)0.0070 (13)0.0013 (12)
C50.0402 (18)0.052 (2)0.063 (2)−0.0013 (15)0.0153 (16)0.0037 (16)
C60.049 (2)0.052 (2)0.073 (3)−0.0119 (16)0.0196 (18)0.0070 (17)
C70.0341 (15)0.0399 (17)0.0455 (18)0.0033 (13)0.0060 (13)−0.0051 (13)
C80.0414 (17)0.0262 (15)0.056 (2)0.0068 (12)0.0070 (14)−0.0037 (13)
C90.0479 (17)0.0268 (15)0.0480 (18)0.0004 (13)0.0081 (14)−0.0084 (13)
C100.052 (2)0.0418 (18)0.068 (2)0.0065 (15)−0.0090 (17)0.0088 (16)
C110.058 (2)0.0398 (19)0.103 (3)0.0079 (16)0.025 (2)−0.0133 (19)
C120.0356 (15)0.0281 (14)0.0388 (16)0.0028 (11)0.0044 (12)0.0043 (12)
C130.0509 (18)0.0282 (15)0.0360 (16)0.0023 (13)0.0010 (13)−0.0017 (12)
C140.0476 (18)0.0290 (15)0.0454 (18)0.0059 (13)0.0052 (14)0.0027 (13)
C150.069 (2)0.0336 (17)0.0382 (18)0.0074 (15)−0.0038 (16)0.0078 (13)
C160.061 (2)0.0393 (17)0.0344 (17)0.0060 (15)−0.0024 (15)0.0018 (13)
C170.0431 (16)0.0282 (15)0.0349 (16)0.0041 (12)0.0025 (13)0.0014 (12)
C180.0421 (16)0.0369 (16)0.0328 (16)0.0031 (13)0.0020 (13)−0.0020 (12)
C190.0521 (18)0.0269 (15)0.0420 (17)0.0067 (13)−0.0013 (14)−0.0084 (12)
C200.0442 (17)0.0297 (15)0.0508 (19)−0.0040 (13)−0.0064 (14)−0.0055 (13)
C210.071 (2)0.0448 (19)0.058 (2)0.0162 (17)0.0179 (18)−0.0056 (16)
C220.090 (3)0.046 (2)0.056 (2)0.0023 (19)−0.023 (2)−0.0132 (16)
C230.076 (3)0.054 (2)0.065 (3)0.0069 (19)−0.008 (2)−0.0059 (18)
C240.075 (3)0.069 (3)0.107 (4)0.002 (2)0.018 (3)0.018 (2)
Geometric parameters (Å, °) top
Cu1—O51.9150 (18)C8—C101.528 (4)
Cu1—N21.943 (2)C8—C91.530 (4)
Cu1—O3i1.9515 (18)C8—C111.535 (4)
Cu1—O61.9572 (17)C9—H9A0.9700
Cu1—Cu2i3.0477 (5)C9—H9B0.9700
Cu2—O21.9139 (18)C10—H10A0.9600
Cu2—O31.9414 (17)C10—H10B0.9600
Cu2—N11.944 (2)C10—H10C0.9600
Cu2—O61.9853 (17)C11—H11A0.9600
Cu2—O6i2.3419 (18)C11—H11B0.9600
Cu2—Cu1i3.0477 (5)C11—H11C0.9600
N1—C71.291 (3)C12—C131.394 (4)
N2—C181.282 (3)C13—H130.9300
N2—C191.498 (3)C14—C151.377 (4)
O1—C11.348 (3)C14—C131.382 (4)
O1—H10.8200C15—H150.9300
O2—C31.314 (3)C16—C151.361 (4)
O3—C91.424 (3)C16—H160.9300
O3—Cu1i1.9515 (18)C17—C161.410 (4)
O4—C141.359 (3)C17—C121.420 (4)
O4—H40.8200C17—C181.438 (4)
O5—C121.327 (3)C18—H180.9300
O6—C201.420 (3)C19—C221.515 (4)
O6—Cu2i2.3419 (18)C19—C201.546 (4)
O7—C231.468 (4)C20—H20A0.9700
O7—H7A0.8200C20—H20B0.9700
O8—C241.365 (4)C21—C191.522 (4)
O8—H80.8200C21—H21A0.9600
C1—C21.378 (4)C21—H21B0.9600
C1—C61.393 (5)C21—H21C0.9600
C2—H20.9300C22—H22A0.9600
C3—C21.392 (4)C22—H22B0.9600
C3—C41.427 (4)C22—H22C0.9600
C4—C51.411 (4)C23—H23A0.9600
C5—H50.9300C23—H23B0.9600
C6—C51.356 (4)C23—H23C0.9600
C6—H60.9300C24—H24A0.9600
C7—C41.430 (4)C24—H24B0.9600
C7—H70.9300C24—H24C0.9600
C8—N11.488 (3)
O5—Cu1—N294.64 (8)C7—N1—C8122.1 (2)
O5—Cu1—O3i93.48 (8)C7—N1—Cu2124.30 (19)
N2—Cu1—O3i157.52 (9)C8—N1—Cu2113.59 (17)
O5—Cu1—O6178.80 (8)O5—C12—C13118.6 (2)
N2—Cu1—O684.80 (8)O5—C12—C17123.0 (2)
O3i—Cu1—O687.42 (7)C13—C12—C17118.4 (2)
O5—Cu1—Cu2i130.81 (6)C8—C10—H10A109.5
N2—Cu1—Cu2i126.54 (7)C8—C10—H10B109.5
O3i—Cu1—Cu2i38.36 (5)H10A—C10—H10B109.5
O6—Cu1—Cu2i50.21 (5)C8—C10—H10C109.5
O2—Cu2—O3177.49 (8)H10A—C10—H10C109.5
O2—Cu2—N194.62 (8)H10B—C10—H10C109.5
O3—Cu2—N185.30 (8)O1—C1—C2123.1 (3)
O2—Cu2—O686.42 (8)O1—C1—C6116.8 (3)
O3—Cu2—O694.48 (7)C2—C1—C6120.2 (3)
N1—Cu2—O6161.01 (9)N2—C19—C22113.7 (2)
O2—Cu2—O6i100.30 (7)N2—C19—C21107.2 (2)
O3—Cu2—O6i77.56 (7)C22—C19—C21110.9 (3)
N1—Cu2—O6i117.78 (8)N2—C19—C20103.7 (2)
O6—Cu2—O6i80.52 (7)C22—C19—C20108.8 (3)
O2—Cu2—Cu1i139.05 (6)C21—C19—C20112.3 (3)
O3—Cu2—Cu1i38.59 (5)C5—C6—C1118.9 (3)
N1—Cu2—Cu1i97.91 (7)C5—C6—H6120.5
O6—Cu2—Cu1i93.57 (5)C1—C6—H6120.5
O6i—Cu2—Cu1i39.95 (4)C16—C15—C14119.5 (3)
C9—O3—Cu2108.47 (16)C16—C15—H15120.3
C9—O3—Cu1i120.79 (17)C14—C15—H15120.3
Cu2—O3—Cu1i103.05 (8)C14—C13—C12121.1 (3)
C14—O4—H4109.5C14—C13—H13119.4
C3—O2—Cu2126.69 (17)C12—C13—H13119.4
C20—O6—Cu1109.69 (15)O6—C20—C19111.8 (2)
C20—O6—Cu2118.65 (16)O6—C20—H20A109.3
Cu1—O6—Cu2107.11 (8)C19—C20—H20A109.3
C20—O6—Cu2i127.42 (16)O6—C20—H20B109.3
Cu1—O6—Cu2i89.83 (7)C19—C20—H20B109.3
Cu2—O6—Cu2i99.48 (7)H20A—C20—H20B107.9
C1—O1—H1109.5N1—C7—C4125.9 (3)
C12—O5—Cu1125.90 (17)N1—C7—H7117.0
C18—N2—C19121.1 (2)C4—C7—H7117.0
C18—N2—Cu1124.65 (19)C5—C4—C3118.1 (3)
C19—N2—Cu1114.20 (17)C5—C4—C7117.4 (3)
C16—C17—C12118.4 (2)C3—C4—C7124.5 (2)
C16—C17—C18117.0 (3)C1—C2—C3122.2 (3)
C12—C17—C18124.6 (2)C1—C2—H2118.9
O2—C3—C2119.0 (2)C3—C2—H2118.9
O2—C3—C4123.1 (2)C6—C5—C4122.8 (3)
C2—C3—C4117.9 (2)C6—C5—H5118.6
O4—C14—C15116.3 (3)C4—C5—H5118.6
O4—C14—C13122.9 (3)C19—C22—H22A109.5
C15—C14—C13120.7 (3)C19—C22—H22B109.5
N1—C8—C10107.8 (2)H22A—C22—H22B109.5
N1—C8—C9104.0 (2)C19—C22—H22C109.5
C10—C8—C9111.7 (3)H22A—C22—H22C109.5
N1—C8—C11113.6 (3)H22B—C22—H22C109.5
C10—C8—C11110.3 (3)C8—C11—H11A109.5
C9—C8—C11109.3 (3)C8—C11—H11B109.5
C19—C21—H21A109.5H11A—C11—H11B109.5
C19—C21—H21B109.5C8—C11—H11C109.5
H21A—C21—H21B109.5H11A—C11—H11C109.5
C19—C21—H21C109.5H11B—C11—H11C109.5
H21A—C21—H21C109.5C23—O7—H7A109.5
H21B—C21—H21C109.5C24—O8—H8109.5
N2—C18—C17125.8 (3)O7—C23—H23A109.5
N2—C18—H18117.1O7—C23—H23B109.5
C17—C18—H18117.1H23A—C23—H23B109.5
O3—C9—C8112.1 (2)O7—C23—H23C109.5
O3—C9—H9A109.2H23A—C23—H23C109.5
C8—C9—H9A109.2H23B—C23—H23C109.5
O3—C9—H9B109.2O8—C24—H24A109.5
C8—C9—H9B109.2O8—C24—H24B109.5
H9A—C9—H9B107.9H24A—C24—H24B109.5
C15—C16—C17121.9 (3)O8—C24—H24C109.5
C15—C16—H16119.1H24A—C24—H24C109.5
C17—C16—H16119.1H24B—C24—H24C109.5
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—C9140.72 (17)C18—C17—C16—C15178.8 (3)
O6i—Cu2—O3—C9−140.02 (18)C10—C8—N1—C788.9 (3)
Cu1i—Cu2—O3—C9−129.2 (2)C9—C8—N1—C7−152.4 (3)
O2—Cu2—O3—Cu1i20.7 (18)C11—C8—N1—C7−33.6 (4)
N1—Cu2—O3—Cu1i108.93 (10)C10—C8—N1—Cu2−93.2 (2)
O6—Cu2—O3—Cu1i−90.12 (9)C9—C8—N1—Cu225.5 (3)
O6i—Cu2—O3—Cu1i−10.87 (7)C11—C8—N1—Cu2144.3 (2)
O3—Cu2—O2—C397.8 (17)O2—Cu2—N1—C7−9.0 (2)
N1—Cu2—O2—C39.8 (2)O3—Cu2—N1—C7173.5 (2)
O6—Cu2—O2—C3−151.2 (2)O6—Cu2—N1—C783.4 (3)
O6i—Cu2—O2—C3129.1 (2)O6i—Cu2—N1—C7−113.2 (2)
Cu1i—Cu2—O2—C3117.5 (2)Cu1i—Cu2—N1—C7−150.0 (2)
O5—Cu1—O6—C20−81 (4)O2—Cu2—N1—C8173.09 (19)
N2—Cu1—O6—C20−18.51 (17)O3—Cu2—N1—C8−4.39 (19)
O3i—Cu1—O6—C20140.38 (17)O6—Cu2—N1—C8−94.5 (3)
Cu2i—Cu1—O6—C20130.12 (18)O6i—Cu2—N1—C868.9 (2)
O5—Cu1—O6—Cu249 (4)Cu1i—Cu2—N1—C832.17 (19)
N2—Cu1—O6—Cu2111.50 (10)Cu1—O5—C12—C13167.74 (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—Cu2i149 (4)C18—C17—C12—O51.6 (4)
N2—Cu1—O6—Cu2i−148.62 (8)C16—C17—C12—C131.0 (4)
O3i—Cu1—O6—Cu2i10.26 (7)C18—C17—C12—C13−178.4 (3)
O2—Cu2—O6—C20116.44 (18)C18—N2—C19—C22−34.7 (4)
O3—Cu2—O6—C20−65.91 (18)Cu1—N2—C19—C22144.6 (2)
N1—Cu2—O6—C2022.7 (3)C18—N2—C19—C2188.3 (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—C2026.6 (3)
O3—Cu2—O6—Cu1169.35 (9)O1—C1—C6—C5178.9 (3)
N1—Cu2—O6—Cu1−102.1 (2)C2—C1—C6—C5−0.9 (5)
O6i—Cu2—O6—Cu192.77 (9)C17—C16—C15—C14−0.1 (5)
Cu1i—Cu2—O6—Cu1130.67 (7)O4—C14—C15—C16179.6 (3)
O2—Cu2—O6—Cu2i−101.07 (8)C13—C14—C15—C160.5 (5)
O3—Cu2—O6—Cu2i76.58 (7)O4—C14—C13—C12−179.2 (3)
N1—Cu2—O6—Cu2i165.1 (2)C15—C14—C13—C12−0.2 (5)
O6i—Cu2—O6—Cu2i0.0O5—C12—C13—C14179.4 (3)
Cu1i—Cu2—O6—Cu2i37.90 (5)C17—C12—C13—C14−0.5 (4)
N2—Cu1—O5—C1213.6 (2)Cu1—O6—C20—C1939.3 (3)
O3i—Cu1—O5—C12−145.4 (2)Cu2—O6—C20—C19−84.1 (2)
O6—Cu1—O5—C1276 (4)Cu2i—O6—C20—C19145.01 (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—C18102.8 (3)C21—C19—C20—O673.1 (3)
O6—Cu1—N2—C18173.0 (2)C8—N1—C7—C4−176.7 (3)
Cu2i—Cu1—N2—C18143.2 (2)Cu2—N1—C7—C45.7 (4)
O5—Cu1—N2—C19172.70 (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—C7178.8 (3)
Cu2—O2—C3—C2174.26 (19)N1—C7—C4—C5179.7 (3)
Cu2—O2—C3—C4−6.9 (4)N1—C7—C4—C30.6 (5)
C19—N2—C18—C17−179.7 (3)O1—C1—C2—C3−177.9 (3)
Cu1—N2—C18—C171.1 (4)C6—C1—C2—C31.9 (5)
C16—C17—C18—N2−175.0 (3)O2—C3—C2—C1177.7 (3)
C12—C17—C18—N24.4 (5)C4—C3—C2—C1−1.3 (4)
Cu2—O3—C9—C841.2 (3)C1—C6—C5—C4−0.7 (5)
Cu1i—O3—C9—C8−77.2 (3)C3—C4—C5—C61.2 (5)
N1—C8—C9—O3−43.3 (3)C7—C4—C5—C6−177.9 (3)
C10—C8—C9—O372.7 (3)
Symmetry codes: (i) −x, −y, −z+1.
Acknowledgements top

Authors acknowledge helpful discussion from Dr Cheng He of Dalian University of Technology, China. JY also acknowledges financial support from the Open Project Program of the Key Laboratory of Organism Functional Factors of the Changbai Mountains of the Ministry of Education, China (No. 200605).

references
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