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Acta Cryst. (2009). E65, m162    [ doi:10.1107/S1600536809000166 ]

[[mu]-10,22-Dichloro-3,6-bis(2-furylmethyl)-3,6,14,18-tetraazatricyclo[18.3.1.18,12]pentacosa-1(23),8,10,12(25),13,18,20(24),21-octaene-24,25-diolato-[kappa]8N3,N6,O24,O25:N14,N18,O24:O25]bis[chloridocopper(II)] acetonitrile solvate

C. Chen, Y. Cheng, P. Liu, H. Zhou and Z.-Q. Pan

Abstract top

The title compound, [Cu2(C31H30Cl2N4O4)Cl2]·CH3CN, was synthesized by cyclocondensation between N,N'-bis(2-furyl)-N,N'-bis(3-formyl-5-chlorosalicylaldehyde)ethylenediamine and 1,3-diaminopropane in the presence of CuII ions. It is an unsymmetrical dinuclear CuII complex. The coordination geometry for each CuII atom can be discribed as distorted square-pyramidal. The two Cu atoms are bridged by two phenolate O atoms with a Cu...Cu distance of 3.0274 (9) Å.

Comment top

The design and synthesis of phenol-based macrocyclic ligands with N(amino)2O2 and N(imino)2O2 metal-binding sites sharing two phenolate O atoms have drawn increasing attention for their potential unique properties (Hori et al., 2001; Karunakaran & Kandaswamy, 1994; McCollum et al., 1994; Okawa et al., 1998; Sun et al., 2001). In this paper, we report a new unsymmetrical homodinuclear complex of N(amino)2N(imino)2O2-type macrocycle.

The structure of the title compound is shown in Fig. 1. Tne Cu1 atom is five-coordinated by two imino N atoms and two phenolate O atoms from the macrocyclic ligand and one Cl atom. The Cu2 atom is also five-coordinated by two amino N atoms and two phenolate O atoms from the macrocyclic ligand and one Cl atom. The coordination geometry for each CuII atom can be described as distorted square-pyramidal. The basal plane of Cu1 is composed of N3, N4, O1, O2 with a mean plane deviation of 0.0096 Å. The distances between Cu1 and the coordinated atoms in the basal plane are in a range of 1.971 (4)–1.987 (3) Å (Table 1). The mean plane deviation of the basal plane of Cu2 composed of N1, N2, O1, O2 is 0.0185 Å, with the distances between Cu2 and coordinated atoms in the basal plane in a range of 1.940 (3)–2.104 (3) Å. The difference in the distances of Cu1–coordinated atoms and Cu2–coordinated atoms is attributed to the dissimilar size of imino and amino groups. The two Cu atoms are bridged by two phenolate O atoms from the macrocyclic ligand. Two Cl atoms occupy the axial positions, respectively.

Related literature top

For general background, see: Hori et al. (2001); Karunakaran & Kandaswamy (1994); McCollum et al. (1994); Okawa et al. (1998); Sun et al. (2001). For the synthesis of N,N'-bis(2-furyl)-1,2-diaminoethane, see: Rameau (1938).

Experimental top

N,N'-bis(2-furyl)-1,2-diaminoethane was prepared using a variant of the method suggested by Rameau (1938). The precursor ligand N,N'-bis(2-furyl)-N,N'-bis(3-formyl-5-chlorosalicylaldehyde)ethylenediamine (H2L) was prepared through the Mannich reaction between 5-chlorosalicyladehyde (0.2 mol), polyformaldehyde (0.2 mol) and N,N'-bis(2-furyl)-1,2-diaminoethane (0.1 mol). The title compound was synthesized by stepwise template method through the reaction of the methanol solution of H2L (0.5 mmol) with the methanol solution of 1,3-diaminopropane (0.5 mmol), Cu(CH3CO2)2.H2O (0.5 mmol), and NiCl2.6H2O (0.5 mmol). The blue crystals of the title compound suitable for X-ray diffraction were obtained by the evaporation of the mother solution in about a month.

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (CH), 0.97 (CH2) and 0.96 (CH3) Å and with Uiso(H) = 1.2(or 1.5 for methyl)Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
[µ-10,22-Dichloro-3,6-bis(2-furylmethyl)-3,6,14,18- tetraazatricyclo[18.3.1.18,12]pentacosa-1(23),8,10,12 (25),13,18,20 (24),21- octaene-24,25-diolato- κ8N3,N6,O24,O25:N14,N18,O24:O25]bis[chloridocopper(II)] acetonitrile solvate top
Crystal data top
[Cu2(C31H30Cl2N4O4)Cl2]·C2H3NZ = 2
Mr = 832.52F(000) = 848
Triclinic, P1Dx = 1.593 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.4439 (19) ÅCell parameters from 2324 reflections
b = 13.083 (4) Åθ = 2.2–25.3°
c = 14.319 (3) ŵ = 1.58 mm−1
α = 112.039 (3)°T = 291 K
β = 100.290 (4)°Block, blue
γ = 98.259 (3)°0.30 × 0.26 × 0.24 mm
V = 1736.2 (7) Å3
Data collection top
Bruker APEX CCD
diffractometer		6662 independent reflections
Radiation source: sealed tube4514 reflections with I > 2σ(I)
graphiteRint = 0.036
φ and ω scansθmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −12→12
Tmin = 0.63, Tmax = 0.69k = −13→16
9923 measured reflectionsl = −17→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.05P)2 + 0.55P]
where P = (Fo2 + 2Fc2)/3
6662 reflections(Δ/σ)max < 0.001
434 parametersΔρmax = 0.51 e Å−3
0 restraintsΔρmin = −0.45 e Å−3
Crystal data top
[Cu2(C31H30Cl2N4O4)Cl2]·C2H3Nγ = 98.259 (3)°
Mr = 832.52V = 1736.2 (7) Å3
Triclinic, P1Z = 2
a = 10.4439 (19) ÅMo Kα radiation
b = 13.083 (4) ŵ = 1.58 mm−1
c = 14.319 (3) ÅT = 291 K
α = 112.039 (3)°0.30 × 0.26 × 0.24 mm
β = 100.290 (4)°
Data collection top
Bruker APEX CCD
diffractometer		6662 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		4514 reflections with I > 2σ(I)
Tmin = 0.63, Tmax = 0.69Rint = 0.036
9923 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.111Δρmax = 0.51 e Å−3
S = 1.01Δρmin = −0.45 e Å−3
6662 reflectionsAbsolute structure: ?
434 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1−0.0844 (4)0.8642 (3)0.2679 (3)0.0342 (9)
C2−0.1625 (5)0.9063 (3)0.3379 (3)0.0383 (9)
C3−0.2650 (5)0.8331 (4)0.3466 (4)0.0542 (12)
H3−0.31520.86090.39400.065*
C4−0.2920 (5)0.7183 (4)0.2841 (4)0.0524 (12)
C5−0.2168 (5)0.6747 (4)0.2146 (4)0.0495 (11)
H5−0.23590.59720.17370.059*
C6−0.1104 (5)0.7485 (4)0.2057 (3)0.0398 (10)
C7−0.0367 (4)0.6997 (3)0.1234 (3)0.0357 (9)
H7A−0.06980.61810.08960.043*
H7B−0.05580.72930.07090.043*
C80.1739 (5)0.6779 (3)0.0826 (3)0.0379 (9)
H8A0.10920.61420.02610.045*
H8B0.24810.64970.10690.045*
C90.2251 (4)0.7658 (3)0.0416 (3)0.0335 (9)
H9A0.27650.7339−0.00780.040*
H9B0.14950.78380.00570.040*
C100.3374 (4)0.9594 (3)0.0903 (3)0.0325 (9)
H10A0.25660.95610.04270.039*
H10B0.40390.94270.05080.039*
C110.3021 (4)1.1280 (3)0.2317 (3)0.0338 (8)
C120.3870 (4)1.0792 (3)0.1723 (3)0.0362 (9)
C130.5049 (5)1.1461 (4)0.1761 (4)0.0490 (12)
H130.56161.11320.13660.059*
C140.5390 (5)1.2602 (4)0.2373 (4)0.0504 (11)
C150.4540 (5)1.3103 (3)0.2983 (3)0.0414 (10)
H150.47631.38760.34040.050*
C160.3379 (5)1.2431 (3)0.2945 (3)0.0404 (10)
C170.2583 (5)1.3048 (3)0.3594 (3)0.0432 (11)
H170.29121.38280.39470.052*
C180.0773 (6)1.3532 (4)0.4257 (5)0.0617 (14)
H18A0.04961.38600.37710.074*
H18B0.14421.41230.48460.074*
C19−0.0426 (6)1.3263 (4)0.4654 (5)0.0640 (14)
H19A−0.04241.39210.52650.077*
H19B−0.12351.31160.41240.077*
C20−0.0452 (6)1.2255 (4)0.4931 (4)0.0636 (14)
H20A−0.11681.22120.52730.076*
H20B0.03811.23980.54350.076*
C21−0.1399 (5)1.0223 (3)0.4035 (3)0.0440 (11)
H21−0.18721.03830.45440.053*
C220.1495 (4)0.6856 (3)0.2501 (3)0.0371 (9)
H22A0.24570.71030.27820.044*
H22B0.10920.72260.30610.044*
C230.1124 (4)0.5656 (3)0.2207 (3)0.0390 (9)
C24−0.0014 (5)0.5072 (4)0.2283 (4)0.0487 (11)
H24−0.07180.53710.25010.058*
C250.0068 (5)0.3975 (4)0.1981 (4)0.0561 (12)
H25−0.05600.34010.19920.067*
C260.1152 (6)0.3844 (4)0.1672 (4)0.0525 (12)
H260.14300.31710.14130.063*
C270.4391 (4)0.8521 (4)0.1754 (3)0.0388 (9)
H27A0.49430.92610.22360.047*
H27B0.42170.80900.21590.047*
C280.5147 (4)0.7964 (4)0.1059 (3)0.0398 (9)
C290.6172 (5)0.8350 (5)0.0721 (4)0.0562 (12)
H290.66260.91030.09650.067*
C300.6425 (5)0.7448 (5)−0.0037 (4)0.0631 (15)
H300.70320.7477−0.04340.076*
C310.5636 (6)0.6517 (4)−0.0096 (4)0.0615 (14)
H310.56430.5773−0.05030.074*
C320.5514 (6)0.1983 (4)0.4781 (4)0.0675 (16)
H32A0.58890.16530.52290.101*
H32B0.56260.15910.40950.101*
H32C0.45780.19220.47480.101*
C330.6194 (6)0.3177 (5)0.5190 (5)0.0705 (16)
Cl1−0.11526 (12)1.10354 (8)0.15969 (8)0.0413 (2)
Cl20.30948 (13)0.95565 (9)0.38563 (8)0.0497 (3)
Cl3−0.42396 (18)0.62659 (12)0.29107 (15)0.0837 (5)
Cl40.68796 (15)1.34258 (11)0.24439 (13)0.0706 (4)
Cu10.05232 (6)1.10190 (4)0.30743 (4)0.03763 (14)
Cu20.17812 (5)0.90346 (4)0.21979 (4)0.03578 (14)
N10.1122 (4)0.7269 (3)0.1669 (2)0.0364 (8)
N20.3080 (3)0.8683 (3)0.1268 (2)0.0345 (7)
N30.1460 (4)1.2632 (3)0.3737 (3)0.0502 (10)
N4−0.0640 (5)1.1100 (3)0.4042 (3)0.0547 (11)
N50.6739 (6)0.4137 (4)0.5554 (4)0.0875 (17)
O10.0144 (3)0.9354 (2)0.2580 (2)0.0398 (7)
O20.1891 (3)1.06154 (19)0.22835 (19)0.0350 (6)
O30.1847 (3)0.4960 (3)0.1811 (2)0.0505 (8)
O40.4820 (3)0.6849 (3)0.0544 (3)0.0586 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.051 (2)0.040 (2)0.0213 (18)0.0135 (18)0.0152 (17)0.0188 (16)
C20.062 (3)0.036 (2)0.033 (2)0.022 (2)0.029 (2)0.0204 (17)
C30.063 (3)0.054 (3)0.061 (3)0.012 (2)0.034 (3)0.032 (2)
C40.058 (3)0.049 (3)0.068 (3)0.015 (2)0.031 (3)0.036 (2)
C50.072 (3)0.028 (2)0.050 (3)0.010 (2)0.023 (2)0.0145 (19)
C60.058 (3)0.043 (2)0.026 (2)0.015 (2)0.0180 (19)0.0175 (17)
C70.057 (3)0.035 (2)0.0240 (19)0.0244 (19)0.0156 (18)0.0140 (15)
C80.066 (3)0.0089 (15)0.037 (2)0.0089 (16)0.021 (2)0.0045 (14)
C90.060 (3)0.0257 (18)0.0210 (17)0.0159 (17)0.0191 (17)0.0096 (14)
C100.052 (2)0.041 (2)0.0163 (16)0.0254 (19)0.0118 (16)0.0168 (15)
C110.048 (2)0.0252 (18)0.035 (2)0.0149 (17)0.0100 (18)0.0170 (16)
C120.056 (3)0.0266 (18)0.030 (2)0.0124 (18)0.0135 (18)0.0139 (16)
C130.074 (3)0.041 (2)0.052 (3)0.014 (2)0.036 (2)0.031 (2)
C140.062 (3)0.043 (2)0.059 (3)0.018 (2)0.022 (2)0.030 (2)
C150.060 (3)0.0237 (19)0.047 (2)0.0096 (19)0.020 (2)0.0182 (17)
C160.057 (3)0.029 (2)0.044 (2)0.0118 (19)0.013 (2)0.0239 (18)
C170.080 (3)0.0129 (16)0.037 (2)0.0040 (19)0.021 (2)0.0097 (15)
C180.086 (4)0.026 (2)0.076 (4)0.017 (2)0.035 (3)0.018 (2)
C190.076 (4)0.054 (3)0.073 (4)0.030 (3)0.030 (3)0.026 (3)
C200.077 (4)0.043 (3)0.074 (4)0.022 (3)0.039 (3)0.017 (3)
C210.082 (3)0.032 (2)0.035 (2)0.025 (2)0.040 (2)0.0166 (17)
C220.055 (3)0.0221 (17)0.030 (2)−0.0007 (17)0.0118 (18)0.0093 (15)
C230.055 (3)0.031 (2)0.039 (2)0.0122 (19)0.013 (2)0.0219 (17)
C240.061 (3)0.039 (2)0.056 (3)0.015 (2)0.027 (2)0.023 (2)
C250.069 (3)0.033 (2)0.065 (3)0.003 (2)0.022 (3)0.019 (2)
C260.080 (4)0.042 (2)0.045 (3)0.025 (2)0.023 (2)0.020 (2)
C270.064 (3)0.042 (2)0.0280 (19)0.023 (2)0.0159 (19)0.0272 (17)
C280.049 (3)0.048 (2)0.035 (2)0.021 (2)0.0125 (19)0.0257 (19)
C290.047 (3)0.074 (3)0.057 (3)0.018 (3)0.015 (2)0.035 (3)
C300.045 (3)0.086 (4)0.049 (3)0.006 (3)0.018 (2)0.017 (3)
C310.069 (3)0.051 (3)0.072 (4)0.030 (3)0.035 (3)0.021 (3)
C320.081 (4)0.039 (3)0.060 (3)−0.014 (2)−0.022 (3)0.024 (2)
C330.078 (4)0.067 (4)0.067 (4)0.024 (3)0.002 (3)0.033 (3)
Cl10.0676 (7)0.0326 (5)0.0326 (5)0.0175 (5)0.0229 (5)0.0163 (4)
Cl20.0790 (8)0.0370 (5)0.0312 (5)0.0088 (5)0.0142 (5)0.0134 (4)
Cl30.0998 (12)0.0533 (8)0.1164 (13)0.0147 (8)0.0643 (11)0.0393 (8)
Cl40.0689 (8)0.0489 (7)0.1056 (12)0.0101 (6)0.0410 (8)0.0372 (8)
Cu10.0614 (3)0.0294 (2)0.0267 (3)0.0145 (2)0.0220 (2)0.01025 (19)
Cu20.0611 (3)0.0225 (2)0.0300 (3)0.0136 (2)0.0219 (2)0.01146 (18)
N10.058 (2)0.0252 (16)0.0264 (16)0.0156 (15)0.0164 (15)0.0060 (13)
N20.0452 (19)0.0303 (17)0.0317 (17)0.0143 (15)0.0119 (15)0.0137 (14)
N30.085 (3)0.0265 (17)0.045 (2)0.0112 (18)0.033 (2)0.0137 (15)
N40.084 (3)0.038 (2)0.052 (2)0.019 (2)0.039 (2)0.0176 (18)
N50.109 (4)0.050 (3)0.069 (3)−0.013 (3)0.000 (3)0.009 (2)
O10.0621 (19)0.0240 (13)0.0334 (15)0.0056 (13)0.0229 (14)0.0085 (11)
O20.0628 (18)0.0175 (12)0.0296 (14)0.0101 (12)0.0228 (13)0.0096 (10)
O30.066 (2)0.0504 (18)0.0445 (17)0.0207 (16)0.0284 (16)0.0206 (14)
O40.062 (2)0.0493 (19)0.059 (2)0.0233 (16)0.0244 (17)0.0084 (16)
Geometric parameters (Å, °) top
C1—O11.352 (5)C20—N41.524 (6)
C1—C61.394 (6)C20—H20A0.9700
C1—C21.408 (5)C20—H20B0.9700
C2—C31.385 (6)C21—N41.293 (6)
C2—C211.410 (5)C21—H210.9300
C3—C41.384 (7)C22—C231.436 (5)
C3—H30.9300C22—N11.498 (5)
C4—C51.384 (6)C22—H22A0.9700
C4—Cl31.736 (5)C22—H22B0.9700
C5—C61.419 (6)C23—O31.298 (5)
C5—H50.9300C23—C241.362 (6)
C6—C71.514 (5)C24—C251.355 (6)
C7—N11.504 (5)C24—H240.9300
C7—H7A0.9700C25—C261.298 (7)
C7—H7B0.9700C25—H250.9300
C8—N11.449 (5)C26—O31.457 (6)
C8—C91.548 (5)C26—H260.9300
C8—H8A0.9700C27—C281.431 (6)
C8—H8B0.9700C27—N21.503 (5)
C9—N21.448 (5)C27—H27A0.9700
C9—H9A0.9700C27—H27B0.9700
C9—H9B0.9700C28—O41.322 (5)
C10—N21.486 (5)C28—C291.359 (6)
C10—C121.507 (5)C29—C301.369 (7)
C10—H10A0.9700C29—H290.9300
C10—H10B0.9700C30—C311.334 (7)
C11—O21.343 (5)C30—H300.9300
C11—C161.385 (5)C31—O41.357 (6)
C11—C121.394 (5)C31—H310.9300
C12—C131.384 (6)C32—C331.460 (8)
C13—C141.370 (6)C32—H32A0.9600
C13—H130.9300C32—H32B0.9600
C14—C151.414 (6)C32—H32C0.9600
C14—Cl41.724 (5)C33—N51.171 (7)
C15—C161.371 (6)Cu1—Cl12.5022 (13)
C15—H150.9300Cu1—O11.974 (3)
C16—C171.453 (6)Cu1—O21.987 (3)
C17—N31.304 (6)Cu1—N31.971 (4)
C17—H170.9300Cu1—N41.984 (4)
C18—N31.494 (6)Cu2—Cl22.3104 (13)
C18—C191.513 (7)Cu2—O11.940 (3)
C18—H18A0.9700Cu2—O22.010 (2)
C18—H18B0.9700Cu2—N12.104 (3)
C19—C201.511 (7)Cu2—N22.047 (3)
C19—H19A0.9700Cu1—Cu23.0274 (9)
C19—H19B0.9700
O1—C1—C6119.1 (3)C24—C23—C22126.5 (4)
O1—C1—C2120.7 (4)C25—C24—C23107.5 (4)
C6—C1—C2120.2 (4)C25—C24—H24126.3
C3—C2—C1120.4 (4)C23—C24—H24126.3
C3—C2—C21116.9 (4)C26—C25—C24109.8 (5)
C1—C2—C21122.7 (4)C26—C25—H25125.1
C4—C3—C2119.5 (4)C24—C25—H25125.1
C4—C3—H3120.3C25—C26—O3106.5 (4)
C2—C3—H3120.3C25—C26—H26126.8
C5—C4—C3121.3 (4)O3—C26—H26126.8
C5—C4—Cl3118.9 (4)C28—C27—N2116.7 (3)
C3—C4—Cl3119.8 (4)C28—C27—H27A108.1
C4—C5—C6119.9 (4)N2—C27—H27A108.1
C4—C5—H5120.1C28—C27—H27B108.1
C6—C5—H5120.1N2—C27—H27B108.1
C1—C6—C5118.7 (4)H27A—C27—H27B107.3
C1—C6—C7122.4 (4)O4—C28—C29106.5 (4)
C5—C6—C7118.7 (4)O4—C28—C27120.3 (4)
N1—C7—C6113.0 (3)C29—C28—C27133.1 (4)
N1—C7—H7A109.0C28—C29—C30108.7 (5)
C6—C7—H7A109.0C28—C29—H29125.7
N1—C7—H7B109.0C30—C29—H29125.7
C6—C7—H7B109.0C31—C30—C29106.9 (5)
H7A—C7—H7B107.8C31—C30—H30126.6
N1—C8—C9111.5 (3)C29—C30—H30126.6
N1—C8—H8A109.3C30—C31—O4107.8 (4)
C9—C8—H8A109.3C30—C31—H31126.1
N1—C8—H8B109.3O4—C31—H31126.1
C9—C8—H8B109.3C33—C32—H32A109.5
H8A—C8—H8B108.0C33—C32—H32B109.5
N2—C9—C8110.5 (3)H32A—C32—H32B109.5
N2—C9—H9A109.5C33—C32—H32C109.5
C8—C9—H9A109.5H32A—C32—H32C109.5
N2—C9—H9B109.5H32B—C32—H32C109.5
C8—C9—H9B109.5N5—C33—C32177.6 (7)
H9A—C9—H9B108.1N3—Cu1—O1162.13 (16)
N2—C10—C12117.2 (3)N3—Cu1—N496.87 (15)
N2—C10—H10A108.0O1—Cu1—N490.00 (13)
C12—C10—H10A108.0N3—Cu1—O291.60 (13)
N2—C10—H10B108.0O1—Cu1—O277.66 (10)
C12—C10—H10B108.0N4—Cu1—O2162.26 (14)
H10A—C10—H10B107.2N3—Cu1—Cl199.50 (12)
O2—C11—C16121.8 (4)O1—Cu1—Cl195.76 (9)
O2—C11—C12119.0 (3)N4—Cu1—Cl198.40 (14)
C16—C11—C12119.2 (4)O2—Cu1—Cl195.51 (9)
C13—C12—C11119.9 (4)N3—Cu1—Cu2125.95 (12)
C13—C12—C10120.2 (4)O1—Cu1—Cu238.94 (8)
C11—C12—C10119.0 (4)N4—Cu1—Cu2123.12 (11)
C14—C13—C12120.7 (4)O2—Cu1—Cu241.06 (7)
C14—C13—H13119.6Cl1—Cu1—Cu2107.70 (3)
C12—C13—H13119.6O1—Cu2—O277.90 (11)
C13—C14—C15119.9 (4)O1—Cu2—N2157.52 (13)
C13—C14—Cl4120.6 (4)O2—Cu2—N294.21 (11)
C15—C14—Cl4119.5 (4)O1—Cu2—N194.20 (12)
C16—C15—C14118.9 (4)O2—Cu2—N1160.26 (13)
C16—C15—H15120.6N2—Cu2—N186.31 (13)
C14—C15—H15120.6O1—Cu2—Cl297.67 (9)
C15—C16—C11121.5 (4)O2—Cu2—Cl296.32 (8)
C15—C16—C17113.6 (4)N2—Cu2—Cl2104.15 (10)
C11—C16—C17124.9 (4)N1—Cu2—Cl2102.70 (10)
N3—C17—C16127.4 (3)O1—Cu2—Cu139.76 (8)
N3—C17—H17116.3O2—Cu2—Cu140.49 (7)
C16—C17—H17116.3N2—Cu2—Cu1134.50 (9)
N3—C18—C19121.2 (4)N1—Cu2—Cu1133.94 (10)
N3—C18—H18A107.0Cl2—Cu2—Cu188.50 (3)
C19—C18—H18A107.0C8—N1—C22110.7 (3)
N3—C18—H18B107.0C8—N1—C7109.0 (3)
C19—C18—H18B107.0C22—N1—C7112.1 (3)
H18A—C18—H18B106.8C8—N1—Cu2105.5 (2)
C20—C19—C18113.4 (4)C22—N1—Cu2113.0 (2)
C20—C19—H19A108.9C7—N1—Cu2106.2 (2)
C18—C19—H19A108.9C9—N2—C10110.4 (3)
C20—C19—H19B108.9C9—N2—C27113.1 (3)
C18—C19—H19B108.9C10—N2—C27107.8 (3)
H19A—C19—H19B107.7C9—N2—Cu299.3 (2)
C19—C20—N4117.2 (4)C10—N2—Cu2110.3 (2)
C19—C20—H20A108.0C27—N2—Cu2115.6 (2)
N4—C20—H20A108.0C17—N3—C18112.3 (4)
C19—C20—H20B108.0C17—N3—Cu1125.0 (3)
N4—C20—H20B108.0C18—N3—Cu1121.2 (3)
H20A—C20—H20B107.2C21—N4—C20119.3 (4)
N4—C21—C2130.5 (4)C21—N4—Cu1123.8 (3)
N4—C21—H21114.7C20—N4—Cu1116.2 (3)
C2—C21—H21114.7C1—O1—Cu2127.6 (2)
C23—C22—N1117.1 (3)C1—O1—Cu1129.8 (2)
C23—C22—H22A108.0Cu2—O1—Cu1101.30 (12)
N1—C22—H22A108.0C11—O2—Cu1129.2 (2)
C23—C22—H22B108.0C11—O2—Cu2123.0 (2)
N1—C22—H22B108.0Cu1—O2—Cu298.45 (11)
H22A—C22—H22B107.3C23—O3—C26106.4 (3)
O3—C23—C24109.7 (4)C28—O4—C31109.9 (4)
O3—C23—C22123.8 (4)
O1—C1—C2—C3179.0 (4)C8—C9—N2—C10−170.1 (3)
C6—C1—C2—C30.7 (6)C8—C9—N2—C2768.9 (4)
O1—C1—C2—C21−2.5 (6)C8—C9—N2—Cu2−54.2 (3)
C6—C1—C2—C21179.3 (4)C12—C10—N2—C9162.6 (3)
C1—C2—C3—C4−1.5 (7)C12—C10—N2—C27−73.3 (4)
C21—C2—C3—C4179.9 (5)C12—C10—N2—Cu253.8 (4)
C2—C3—C4—C51.4 (8)C28—C27—N2—C948.9 (5)
C2—C3—C4—Cl3−177.7 (4)C28—C27—N2—C10−73.5 (4)
C3—C4—C5—C6−0.6 (8)C28—C27—N2—Cu2162.5 (3)
Cl3—C4—C5—C6178.5 (4)O1—Cu2—N2—C9−57.1 (4)
O1—C1—C6—C5−178.2 (4)O2—Cu2—N2—C9−125.3 (2)
C2—C1—C6—C50.0 (6)N1—Cu2—N2—C934.9 (2)
O1—C1—C6—C7−3.1 (6)Cl2—Cu2—N2—C9137.1 (2)
C2—C1—C6—C7175.2 (4)Cu1—Cu2—N2—C9−120.8 (2)
C4—C5—C6—C1−0.1 (7)O1—Cu2—N2—C1058.9 (4)
C4—C5—C6—C7−175.4 (4)O2—Cu2—N2—C10−9.3 (3)
C1—C6—C7—N158.5 (5)N1—Cu2—N2—C10150.9 (3)
C5—C6—C7—N1−126.4 (4)Cl2—Cu2—N2—C10−106.9 (2)
N1—C8—C9—N251.4 (5)Cu1—Cu2—N2—C10−4.8 (3)
O2—C11—C12—C13−179.0 (4)O1—Cu2—N2—C27−178.5 (3)
C16—C11—C12—C13−0.5 (6)O2—Cu2—N2—C27113.4 (3)
O2—C11—C12—C1012.2 (5)N1—Cu2—N2—C27−86.4 (3)
C16—C11—C12—C10−169.3 (3)Cl2—Cu2—N2—C2715.8 (3)
N2—C10—C12—C13126.0 (4)Cu1—Cu2—N2—C27117.9 (2)
N2—C10—C12—C11−65.1 (5)C16—C17—N3—C18−167.2 (4)
C11—C12—C13—C14−0.3 (7)C16—C17—N3—Cu1−1.0 (7)
C10—C12—C13—C14168.4 (4)C19—C18—N3—C17−170.1 (5)
C12—C13—C14—C150.7 (7)C19—C18—N3—Cu123.1 (7)
C12—C13—C14—Cl4178.4 (4)O1—Cu1—N3—C1750.6 (7)
C13—C14—C15—C16−0.2 (7)N4—Cu1—N3—C17162.6 (4)
Cl4—C14—C15—C16−177.9 (3)O2—Cu1—N3—C17−1.8 (4)
C14—C15—C16—C11−0.6 (6)Cl1—Cu1—N3—C17−97.7 (4)
C14—C15—C16—C17−179.1 (4)Cu2—Cu1—N3—C1722.5 (5)
O2—C11—C16—C15179.4 (4)O1—Cu1—N3—C18−144.3 (4)
C12—C11—C16—C150.9 (6)N4—Cu1—N3—C18−32.4 (4)
O2—C11—C16—C17−2.2 (6)O2—Cu1—N3—C18163.2 (4)
C12—C11—C16—C17179.3 (4)Cl1—Cu1—N3—C1867.4 (4)
C15—C16—C17—N3−177.8 (4)Cu2—Cu1—N3—C18−172.5 (3)
C11—C16—C17—N33.7 (7)C2—C21—N4—C20−172.4 (5)
N3—C18—C19—C2026.6 (8)C2—C21—N4—Cu1−1.7 (8)
C18—C19—C20—N4−66.3 (7)C19—C20—N4—C21−140.0 (5)
C3—C2—C21—N4−170.7 (5)C19—C20—N4—Cu148.6 (6)
C1—C2—C21—N410.6 (8)N3—Cu1—N4—C21−172.5 (4)
N1—C22—C23—O386.0 (5)O1—Cu1—N4—C21−9.0 (4)
N1—C22—C23—C24−93.4 (5)O2—Cu1—N4—C21−54.5 (8)
O3—C23—C24—C254.2 (6)Cl1—Cu1—N4—C2186.8 (4)
C22—C23—C24—C25−176.4 (4)Cu2—Cu1—N4—C21−30.8 (5)
C23—C24—C25—C26−3.4 (6)N3—Cu1—N4—C20−1.5 (4)
C24—C25—C26—O31.5 (6)O1—Cu1—N4—C20161.9 (4)
N2—C27—C28—O4−78.7 (5)O2—Cu1—N4—C20116.5 (5)
N2—C27—C28—C2996.3 (6)Cl1—Cu1—N4—C20−102.2 (4)
O4—C28—C29—C302.2 (5)Cu2—Cu1—N4—C20140.2 (3)
C27—C28—C29—C30−173.3 (5)C6—C1—O1—Cu2−31.0 (5)
C28—C29—C30—C31−4.9 (6)C2—C1—O1—Cu2150.7 (3)
C29—C30—C31—O45.7 (6)C6—C1—O1—Cu1164.7 (3)
N3—Cu1—Cu2—O1166.69 (19)C2—C1—O1—Cu1−13.6 (5)
N4—Cu1—Cu2—O136.2 (2)O2—Cu2—O1—C1175.7 (3)
O2—Cu1—Cu2—O1−154.57 (18)N2—Cu2—O1—C1104.5 (4)
Cl1—Cu1—Cu2—O1−76.86 (13)N1—Cu2—O1—C114.0 (3)
N3—Cu1—Cu2—O2−38.75 (18)Cl2—Cu2—O1—C1−89.5 (3)
O1—Cu1—Cu2—O2154.57 (18)Cu1—Cu2—O1—C1−167.8 (4)
N4—Cu1—Cu2—O2−169.3 (2)O2—Cu2—O1—Cu1−16.57 (11)
Cl1—Cu1—Cu2—O277.71 (13)N2—Cu2—O1—Cu1−87.8 (3)
N3—Cu1—Cu2—N2−45.7 (2)N1—Cu2—O1—Cu1−178.28 (13)
O1—Cu1—Cu2—N2147.61 (19)Cl2—Cu2—O1—Cu178.29 (11)
N4—Cu1—Cu2—N2−176.2 (2)N3—Cu1—O1—C1129.9 (5)
O2—Cu1—Cu2—N2−6.96 (18)N4—Cu1—O1—C117.0 (3)
Cl1—Cu1—Cu2—N270.75 (14)O2—Cu1—O1—C1−175.9 (3)
N3—Cu1—Cu2—N1169.07 (18)Cl1—Cu1—O1—C1−81.5 (3)
O1—Cu1—Cu2—N12.38 (18)Cu2—Cu1—O1—C1167.4 (4)
N4—Cu1—Cu2—N138.6 (2)N3—Cu1—O1—Cu2−37.4 (5)
O2—Cu1—Cu2—N1−152.19 (17)N4—Cu1—O1—Cu2−150.37 (17)
Cl1—Cu1—Cu2—N1−74.48 (13)O2—Cu1—O1—Cu216.78 (12)
N3—Cu1—Cu2—Cl262.80 (14)Cl1—Cu1—O1—Cu2111.19 (10)
O1—Cu1—Cu2—Cl2−103.89 (13)C16—C11—O2—Cu1−1.7 (5)
N4—Cu1—Cu2—Cl2−67.72 (16)C12—C11—O2—Cu1176.8 (3)
O2—Cu1—Cu2—Cl2101.54 (13)C16—C11—O2—Cu2−140.9 (3)
Cl1—Cu1—Cu2—Cl2179.25 (4)C12—C11—O2—Cu237.6 (5)
C9—C8—N1—C22−139.9 (3)N3—Cu1—O2—C113.2 (3)
C9—C8—N1—C796.4 (4)O1—Cu1—O2—C11−162.4 (3)
C9—C8—N1—Cu2−17.3 (4)N4—Cu1—O2—C11−115.5 (5)
C23—C22—N1—C8−60.1 (5)Cl1—Cu1—O2—C11102.9 (3)
C23—C22—N1—C761.8 (5)Cu2—Cu1—O2—C11−146.3 (4)
C23—C22—N1—Cu2−178.1 (3)N3—Cu1—O2—Cu2149.55 (15)
C6—C7—N1—C8−179.5 (3)O1—Cu1—O2—Cu2−16.04 (12)
C6—C7—N1—C2257.6 (4)N4—Cu1—O2—Cu230.8 (5)
C6—C7—N1—Cu2−66.3 (3)Cl1—Cu1—O2—Cu2−110.75 (9)
O1—Cu2—N1—C8147.6 (3)O1—Cu2—O2—C11165.5 (3)
O2—Cu2—N1—C882.3 (4)N2—Cu2—O2—C11−35.8 (3)
N2—Cu2—N1—C8−9.9 (3)N1—Cu2—O2—C11−126.5 (4)
Cl2—Cu2—N1—C8−113.6 (3)Cl2—Cu2—O2—C1169.0 (3)
Cu1—Cu2—N1—C8146.1 (2)Cu1—Cu2—O2—C11149.2 (3)
O1—Cu2—N1—C22−91.3 (3)O1—Cu2—O2—Cu116.31 (12)
O2—Cu2—N1—C22−156.6 (3)N2—Cu2—O2—Cu1175.03 (13)
N2—Cu2—N1—C22111.2 (3)N1—Cu2—O2—Cu184.2 (3)
Cl2—Cu2—N1—C227.5 (3)Cl2—Cu2—O2—Cu1−80.21 (10)
Cu1—Cu2—N1—C22−92.9 (3)C24—C23—O3—C26−3.2 (5)
O1—Cu2—N1—C732.0 (2)C22—C23—O3—C26177.4 (4)
O2—Cu2—N1—C7−33.3 (5)C25—C26—O3—C231.1 (5)
N2—Cu2—N1—C7−125.4 (2)C29—C28—O4—C311.4 (5)
Cl2—Cu2—N1—C7130.9 (2)C27—C28—O4—C31177.6 (4)
Cu1—Cu2—N1—C730.5 (3)C30—C31—O4—C28−4.5 (6)
Table 1
Selected geometric parameters (Å) top
Cu1—Cl12.5022 (13)Cu2—Cl22.3104 (13)
Cu1—O11.974 (3)Cu2—O11.940 (3)
Cu1—O21.987 (3)Cu2—O22.010 (2)
Cu1—N31.971 (4)Cu2—N12.104 (3)
Cu1—N41.984 (4)Cu2—N22.047 (3)
Acknowledgements top

We are grateful for financial support from the Foundation of the Excellent Middle-Young Innovation Group of the Education Department of Hubei Province, China (grant No. T200802) and the Key Foundation of the Education Department of Hubei Province, China (grant No. D20081503).

references
References top

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Hori, A., Yonemura, M., Ohba, M. & Okawa, H. (2001). Bull. Chem. Soc. Jpn, 74, 495–503.

Karunakaran, S. & Kandaswamy, M. (1994). J. Chem. Soc. Dalton Trans. pp. 1595–1598.

McCollum, D. G., Fraser, C., Ostrander, R., Rheingold, A. L. & Bosnich, B. (1994). Inorg. Chem. 33, 2383–2392.

Okawa, H., Furutachi, H. & Fenton, D. E. (1998). Coord. Chem. Rev. 174, 51–75.

Rameau, J. Th. L. B. (1938). Rev. Trav. Chim. 57, 192–214.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Sun, G.-C., He, Z.-H., Li, Z.-J., Yuan, X.-D., Yang, Z.-J., Wang, G.-X., Wang, L.-F. & Liu, C.-R. (2001). Molecules, 6, 1001–1005.