supplementary materials


Acta Cryst. (2007). E63, m2301    [ doi:10.1107/S1600536807038202 ]

[8,17-Bis(5-nitro-2-oxidobenzyl-[kappa]O)-5,6:19,20-dibenzo-1,4,11,14-tetraoxa-8,17-diazacycloeicosane-[kappa]4N,N']copper(II) chloroform solvate

T.-T. Han, J.-F. Ma, G.-J. Ping and Z.-F. Jia

Abstract top

In the title compound, C36H38CuN4O10·CHCl3, the CuII atom is coordinated by two phenolate O atoms and two amine N atoms and displays a distorted square-planar coordination geometry. The complex molecule has approximate C2 symmetry. The chloroform solvent molecule is disordered equally over two positions.

Comment top

In the last few decades, the modification of the macrocycles to control and tune properties of coordinated metal centers has been the subject of much interest (Meyerstein, 1990). We are involved in studies of oxaaza-macrocycles and their metal coordination compounds (Ma et al., 2005). In this paper, we report the preparation and crystal structure of the title macrocyclic complex of CuII.

In the reported crystal structure, the CuII atom is four-coordinated by two phenolate O atoms and two N atoms from the macrocyclic ligand forming a distorted square planar coordination geometry (Fig. 1). The title molecule has an approximate C2 symmetry. The geometry around the Cu atom is normal (Ma & Zhu, 2002). The chloroform molecule is disordered.

Related literature top

For related literature, see: Ma et al. (2005); Ma & Zhu (2002); Meyerstein (1990). For synthesis, see: López-Deber et al. (2005).

Experimental top

5,6:19,20-Dibenzo-1,4,11,14-tetraoxa-8,17-diazacycloeicosane (L2) was synthesized according to the reported method (López-Deber et al., 2005). An anhydrous toluene solution (200 ml) containing L2 (0.76 g, 2.00 mmol), paraformaldehyde (0.15 g, 5.00 mmol), and 4-nitrophenol (0.56 g, 4.00 mmol) was refluxed for 24 h. The solvent was evaporated by rotatory evaporation, and the yellow solid consisting of the title ligand H2L was obtained.

A solution of Cu(NO3)2·3H2O (0.024 g, 0.10 mmol) in 5 ml e thanol was added dropwise to a solution of H2L (0.068 g, 0.10 mmol) in 6 ml chloroform. After stirring for 30 min, the mixture was filtered. Green crystals of of the title compound were obtained by evaporating the filtrate at room temperature (yield 50%).

Refinement top

The H atoms bonded C atoms were placed at their idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97Å and Uiso(H) = 1.2Ueq(C) for methylene and aromatic H atoms. The chloroform molecule is disordered over two positions. It was refined with no restraints imposed on the molecular geometry and with the assumed occupancy factor of 0.5. The high residual peak on the final differnce map is located 0.70 Å from Cl2' atom. The H atom of the chloroform molecule was not localized and is not included in the structural model.

Computing details top

Data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the molecule the title molecule. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity, Only one orintation of CHCl3 is shown.
[8,17-Bis(5-nitro-2-oxidobenzyl-κO)-5,6:19,20-dibenzo-1,4,11,14-tetraoxa-8,17- diazacycloeicosane-κ4N,N']copper(II) chloroform solvate top
Crystal data top
C36H38CuN4O10·CHCl3Z = 2
Mr = 869.61F000 = 898
Triclinic, P1Dx = 1.490 Mg m3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71069 Å
a = 12.055 (3) ÅCell parameters from 13446 reflections
b = 12.819 (4) Åθ = 3.1–27.4º
c = 13.409 (4) ŵ = 0.83 mm1
α = 82.532 (12)ºT = 293 (2) K
β = 82.378 (11)ºBlock, green
γ = 71.364 (9)º0.23 × 0.22 × 0.15 mm
V = 1937.7 (10) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer
8707 independent reflections
Radiation source: rotor target6756 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
Detector resolution: 10.0 pixels mm-1θmax = 27.4º
T = 293(2) Kθmin = 3.1º
ω scansh = 15→15
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 16→16
Tmin = 0.826, Tmax = 0.883l = 17→17
18759 measured reflections
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)] = 0.056H-atom parameters constrained
wR(F2) = 0.148  w = 1/[σ2(Fo2) + (0.0646P)2 + 1.7805P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.001
8707 reflectionsΔρmax = 1.33 e Å3
527 parametersΔρmin = 1.03 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C36H38CuN4O10·CHCl3γ = 71.364 (9)º
Mr = 869.61V = 1937.7 (10) Å3
Triclinic, P1Z = 2
a = 12.055 (3) ÅMo Kα
b = 12.819 (4) ŵ = 0.83 mm1
c = 13.409 (4) ÅT = 293 (2) K
α = 82.532 (12)º0.23 × 0.22 × 0.15 mm
β = 82.378 (11)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer
8707 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
6756 reflections with I > 2σ(I)
Tmin = 0.826, Tmax = 0.883Rint = 0.027
18759 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056527 parameters
wR(F2) = 0.148H-atom parameters constrained
S = 1.07Δρmax = 1.33 e Å3
8707 reflectionsΔρmin = 1.03 e Å3
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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.71823 (3)0.20288 (3)0.27584 (3)0.03486 (12)
C10.3790 (3)0.3280 (4)0.6013 (3)0.0620 (10)
H10.29970.34500.62470.074*
C20.4616 (4)0.2550 (4)0.6590 (3)0.0695 (11)
H20.43860.22380.72170.083*
C30.5793 (3)0.2283 (3)0.6231 (3)0.0554 (9)
H30.63520.17920.66250.067*
C40.6155 (3)0.2732 (3)0.5297 (2)0.0411 (7)
C50.5300 (3)0.3481 (3)0.4729 (2)0.0405 (7)
C60.4121 (3)0.3763 (3)0.5092 (3)0.0514 (8)
H60.35570.42740.47160.062*
C70.4897 (3)0.4700 (3)0.3214 (3)0.0495 (8)
H7A0.45180.53570.35660.059*
H7B0.42960.43990.30760.059*
C80.5560 (3)0.4981 (3)0.2251 (3)0.0503 (8)
H8A0.50760.56330.18830.060*
H8B0.62640.51260.23890.060*
C90.6373 (3)0.4149 (3)0.0713 (2)0.0443 (7)
C100.6663 (4)0.5075 (3)0.0251 (3)0.0596 (9)
H100.65350.56860.06060.072*
C110.7148 (4)0.5071 (4)0.0752 (3)0.0704 (12)
H110.73420.56900.10630.084*
C120.7345 (3)0.4184 (4)0.1290 (3)0.0633 (10)
H120.76680.41960.19590.076*
C130.7055 (3)0.3267 (3)0.0819 (3)0.0519 (8)
H130.71850.26600.11810.062*
C140.6576 (3)0.3229 (3)0.0180 (2)0.0399 (7)
C150.6212 (2)0.2252 (3)0.0668 (2)0.0375 (6)
H15A0.61060.18530.01400.045*
H15B0.54550.25220.10550.045*
C160.7440 (3)0.2485 (3)0.4927 (2)0.0395 (6)
H16A0.75710.31680.46170.047*
H16B0.78910.22440.55080.047*
C170.8248 (2)0.1088 (3)0.0779 (2)0.0395 (7)
H17A0.84630.17430.05060.047*
H17B0.81900.07160.02110.047*
C180.9229 (3)0.0329 (3)0.1370 (2)0.0429 (7)
H18A0.99800.03360.10080.052*
H18B0.91760.06040.20210.052*
C191.0058 (3)0.1512 (3)0.2126 (3)0.0511 (8)
H19A1.06790.11860.21430.061*
H19B1.04020.21980.18110.061*
C200.9581 (4)0.1763 (3)0.3186 (3)0.0608 (10)
H20A0.88900.19900.31700.073*
H20B1.01660.23760.35100.073*
C210.8062 (3)0.0388 (3)0.4051 (3)0.0487 (8)
H21A0.77700.09640.44200.058*
H21B0.76560.01340.34450.058*
C220.7783 (3)0.0561 (3)0.4694 (2)0.0430 (7)
H22A0.69770.07020.49940.052*
H22B0.82850.03270.52420.052*
C230.5085 (2)0.1334 (3)0.3020 (2)0.0370 (6)
C240.3935 (3)0.1536 (3)0.3514 (2)0.0470 (8)
H240.37200.19490.40690.056*
C250.3129 (3)0.1135 (3)0.3194 (2)0.0455 (7)
H250.23740.12770.35230.055*
C260.3459 (3)0.0513 (3)0.2372 (2)0.0417 (7)
C270.4568 (3)0.0326 (2)0.1851 (2)0.0389 (6)
H270.47610.00750.12880.047*
C280.5387 (2)0.0730 (2)0.2159 (2)0.0347 (6)
C290.9426 (2)0.2571 (2)0.3520 (2)0.0371 (6)
C300.8940 (2)0.3123 (3)0.2616 (2)0.0375 (6)
C310.9198 (3)0.4091 (3)0.2205 (3)0.0506 (8)
H310.88900.44590.16110.061*
C320.9903 (3)0.4512 (3)0.2668 (3)0.0547 (9)
H321.00780.51490.23820.066*
C331.0340 (3)0.3977 (3)0.3554 (3)0.0476 (8)
C341.0106 (2)0.3018 (3)0.3984 (2)0.0427 (7)
H341.04070.26730.45880.051*
C350.9206 (2)0.1509 (2)0.3955 (2)0.0376 (6)
H35A0.95890.12500.45720.045*
H35B0.95560.09550.34800.045*
C360.6608 (2)0.0469 (2)0.1620 (2)0.0358 (6)
H36A0.71450.00840.20420.043*
H36B0.66150.01480.10010.043*
C370.8037 (11)0.2229 (8)0.0476 (7)0.056 (3)0.50
C37'0.8568 (17)0.239 (2)0.0380 (19)0.161 (12)0.50
N10.70559 (19)0.1447 (2)0.13594 (17)0.0332 (5)
N20.79173 (19)0.16288 (19)0.41818 (17)0.0339 (5)
N31.1055 (3)0.4422 (3)0.4063 (3)0.0629 (9)
N40.2629 (3)0.0064 (3)0.2054 (2)0.0550 (7)
O10.57237 (18)0.38994 (18)0.38185 (16)0.0439 (5)
O20.5863 (2)0.40529 (18)0.16771 (16)0.0485 (5)
O30.9184 (2)0.07739 (19)0.1522 (2)0.0542 (6)
O40.9275 (2)0.0835 (2)0.3771 (2)0.0641 (7)
O50.58314 (18)0.1697 (2)0.33764 (16)0.0462 (5)
O60.82833 (19)0.27311 (19)0.21482 (15)0.0439 (5)
O70.1678 (2)0.0182 (3)0.2558 (2)0.0804 (9)
O80.2898 (3)0.0447 (3)0.1304 (2)0.0853 (10)
O91.1372 (3)0.3971 (3)0.4884 (3)0.0845 (10)
O101.1309 (3)0.5246 (3)0.3661 (3)0.0926 (11)
Cl10.8225 (5)0.3148 (4)0.1526 (4)0.1063 (18)0.50
Cl1'0.9885 (4)0.3439 (4)0.0298 (3)0.1373 (14)0.50
Cl20.6560 (2)0.19588 (18)0.0184 (2)0.0889 (8)0.50
Cl2'0.7794 (7)0.2300 (6)0.0623 (6)0.209 (2)*0.50
Cl30.8917 (5)0.2601 (4)0.0603 (4)0.177 (2)0.50
Cl3'0.7727 (5)0.2745 (5)0.1465 (5)0.147 (2)0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0335 (2)0.0416 (2)0.03340 (19)0.01475 (15)0.00599 (13)0.00648 (14)
C10.046 (2)0.074 (3)0.064 (2)0.0170 (18)0.0112 (17)0.023 (2)
C20.074 (3)0.071 (3)0.057 (2)0.024 (2)0.021 (2)0.007 (2)
C30.058 (2)0.052 (2)0.0466 (19)0.0075 (16)0.0037 (15)0.0049 (16)
C40.0439 (17)0.0411 (16)0.0385 (16)0.0113 (13)0.0002 (12)0.0127 (13)
C50.0388 (16)0.0427 (17)0.0411 (16)0.0096 (13)0.0046 (12)0.0147 (13)
C60.0414 (18)0.060 (2)0.053 (2)0.0092 (15)0.0051 (14)0.0194 (16)
C70.0468 (18)0.0446 (18)0.0496 (19)0.0039 (14)0.0150 (14)0.0130 (15)
C80.064 (2)0.0349 (16)0.0484 (19)0.0048 (14)0.0174 (16)0.0056 (14)
C90.0452 (17)0.0453 (18)0.0415 (17)0.0124 (14)0.0113 (13)0.0021 (14)
C100.072 (2)0.048 (2)0.063 (2)0.0260 (18)0.0138 (19)0.0038 (18)
C110.078 (3)0.064 (3)0.068 (3)0.032 (2)0.007 (2)0.025 (2)
C120.059 (2)0.073 (3)0.050 (2)0.0189 (19)0.0008 (17)0.0120 (19)
C130.0490 (19)0.059 (2)0.0424 (18)0.0105 (16)0.0049 (14)0.0011 (15)
C140.0354 (15)0.0438 (17)0.0380 (16)0.0089 (12)0.0086 (12)0.0018 (13)
C150.0340 (15)0.0454 (17)0.0348 (15)0.0117 (12)0.0080 (11)0.0060 (12)
C160.0381 (16)0.0432 (16)0.0372 (15)0.0089 (12)0.0069 (12)0.0099 (13)
C170.0337 (15)0.0486 (18)0.0362 (15)0.0124 (13)0.0015 (11)0.0088 (13)
C180.0362 (16)0.0467 (18)0.0481 (18)0.0134 (13)0.0041 (13)0.0105 (14)
C190.0394 (18)0.0458 (19)0.064 (2)0.0026 (14)0.0097 (15)0.0117 (16)
C200.076 (3)0.045 (2)0.062 (2)0.0166 (18)0.0013 (19)0.0196 (17)
C210.0496 (19)0.0390 (17)0.057 (2)0.0115 (14)0.0107 (15)0.0037 (15)
C220.0452 (17)0.0409 (17)0.0412 (17)0.0126 (13)0.0030 (13)0.0006 (13)
C230.0345 (15)0.0444 (16)0.0371 (15)0.0179 (12)0.0021 (11)0.0082 (12)
C240.0417 (17)0.061 (2)0.0436 (17)0.0217 (15)0.0056 (13)0.0199 (15)
C250.0344 (16)0.057 (2)0.0483 (18)0.0198 (14)0.0020 (13)0.0085 (15)
C260.0410 (16)0.0474 (18)0.0447 (17)0.0232 (14)0.0071 (13)0.0049 (14)
C270.0435 (16)0.0413 (16)0.0368 (15)0.0183 (13)0.0042 (12)0.0077 (13)
C280.0353 (15)0.0355 (15)0.0350 (15)0.0132 (12)0.0027 (11)0.0045 (12)
C290.0305 (14)0.0424 (16)0.0386 (15)0.0096 (12)0.0058 (11)0.0063 (12)
C300.0333 (15)0.0445 (16)0.0374 (15)0.0146 (12)0.0034 (11)0.0065 (12)
C310.060 (2)0.055 (2)0.0447 (18)0.0293 (17)0.0127 (15)0.0052 (15)
C320.060 (2)0.061 (2)0.056 (2)0.0377 (18)0.0046 (16)0.0030 (17)
C330.0377 (17)0.064 (2)0.0500 (19)0.0253 (15)0.0017 (13)0.0161 (16)
C340.0305 (15)0.0555 (19)0.0436 (17)0.0121 (13)0.0069 (12)0.0096 (14)
C350.0289 (14)0.0417 (16)0.0412 (16)0.0070 (12)0.0078 (11)0.0057 (13)
C360.0366 (15)0.0363 (15)0.0368 (15)0.0129 (12)0.0005 (11)0.0100 (12)
C370.101 (9)0.042 (4)0.041 (4)0.044 (5)0.014 (5)0.001 (3)
C37'0.134 (17)0.22 (2)0.168 (19)0.111 (17)0.097 (15)0.076 (16)
N10.0304 (12)0.0388 (13)0.0323 (12)0.0122 (10)0.0023 (9)0.0064 (10)
N20.0313 (12)0.0359 (13)0.0335 (12)0.0082 (9)0.0053 (9)0.0035 (10)
N30.0547 (18)0.091 (3)0.060 (2)0.0433 (18)0.0025 (15)0.0228 (18)
N40.0504 (17)0.070 (2)0.0574 (18)0.0332 (15)0.0080 (13)0.0104 (15)
O10.0414 (12)0.0473 (12)0.0393 (12)0.0066 (9)0.0080 (9)0.0048 (9)
O20.0642 (15)0.0424 (12)0.0399 (12)0.0164 (11)0.0056 (10)0.0066 (10)
O30.0479 (13)0.0438 (13)0.0744 (17)0.0114 (10)0.0230 (11)0.0069 (11)
O40.0591 (16)0.0587 (16)0.0785 (18)0.0153 (12)0.0020 (13)0.0331 (14)
O50.0412 (12)0.0688 (15)0.0393 (11)0.0275 (11)0.0017 (9)0.0220 (11)
O60.0500 (12)0.0559 (13)0.0354 (11)0.0286 (10)0.0116 (9)0.0009 (10)
O70.0516 (16)0.124 (3)0.088 (2)0.0548 (17)0.0049 (14)0.0307 (19)
O80.080 (2)0.122 (3)0.085 (2)0.063 (2)0.0053 (16)0.052 (2)
O90.081 (2)0.122 (3)0.076 (2)0.058 (2)0.0289 (16)0.0100 (19)
O100.112 (3)0.123 (3)0.081 (2)0.091 (2)0.0047 (18)0.015 (2)
Cl10.145 (4)0.089 (3)0.103 (3)0.058 (3)0.064 (3)0.034 (2)
Cl1'0.136 (3)0.143 (3)0.107 (3)0.010 (2)0.020 (2)0.035 (2)
Cl20.1068 (19)0.0546 (12)0.114 (2)0.0205 (12)0.0597 (16)0.0009 (12)
Cl30.186 (5)0.160 (4)0.168 (4)0.063 (3)0.127 (4)0.076 (3)
Cl3'0.138 (5)0.117 (4)0.192 (6)0.070 (3)0.070 (4)0.048 (4)
Geometric parameters (Å, °) top
Cu1—O51.874 (2)C20—H20B0.9700
Cu1—O61.878 (2)C21—O41.407 (4)
Cu1—N22.144 (2)C21—C221.507 (5)
Cu1—N12.147 (2)C21—H21A0.9700
C1—C21.374 (6)C21—H21B0.9700
C1—C61.377 (5)C22—N21.497 (4)
C1—H10.9300C22—H22A0.9700
C2—C31.383 (5)C22—H22B0.9700
C2—H20.9300C23—O51.301 (3)
C3—C41.386 (5)C23—C241.414 (4)
C3—H30.9300C23—C281.416 (4)
C4—C51.397 (4)C24—C251.371 (4)
C4—C161.506 (4)C24—H240.9300
C5—O11.371 (4)C25—C261.384 (5)
C5—C61.386 (4)C25—H250.9300
C6—H60.9300C26—C271.387 (4)
C7—O11.431 (4)C26—N41.436 (4)
C7—C81.491 (5)C27—C281.381 (4)
C7—H7A0.9700C27—H270.9300
C7—H7B0.9700C28—C361.506 (4)
C8—O21.424 (4)C29—C341.384 (4)
C8—H8A0.9700C29—C301.419 (4)
C8—H8B0.9700C29—C351.499 (4)
C9—O21.365 (4)C30—O61.318 (3)
C9—C101.389 (5)C30—C311.402 (4)
C9—C141.396 (5)C31—C321.385 (5)
C10—C111.394 (6)C31—H310.9300
C10—H100.9300C32—C331.373 (5)
C11—C121.366 (6)C32—H320.9300
C11—H110.9300C33—C341.384 (5)
C12—C131.384 (5)C33—N31.452 (4)
C12—H120.9300C34—H340.9300
C13—C141.389 (5)C35—N21.505 (3)
C13—H130.9300C35—H35A0.9700
C14—C151.500 (4)C35—H35B0.9700
C15—N11.512 (4)C36—N11.502 (4)
C15—H15A0.9700C36—H36A0.9700
C15—H15B0.9700C36—H36B0.9700
C16—N21.504 (4)C37—C37'0.61 (2)
C16—H16A0.9700C37—Cl3'1.460 (12)
C16—H16B0.9700C37—Cl2'1.560 (12)
C17—N11.503 (3)C37—Cl31.702 (11)
C17—C181.512 (4)C37—Cl11.705 (11)
C17—H17A0.9700C37—Cl21.788 (12)
C17—H17B0.9700C37'—Cl31.36 (3)
C18—O31.420 (4)C37'—Cl2'1.71 (2)
C18—H18A0.9700C37'—Cl1'1.72 (2)
C18—H18B0.9700C37'—Cl3'1.75 (2)
C19—O31.432 (4)C37'—Cl11.78 (2)
C19—C201.495 (5)N3—O91.223 (4)
C19—H19A0.9700N3—O101.231 (4)
C19—H19B0.9700N4—O81.223 (4)
C20—O41.433 (4)N4—O71.226 (4)
C20—H20A0.9700
O5—Cu1—O6165.47 (10)C25—C24—C23121.5 (3)
O5—Cu1—N289.60 (9)C25—C24—H24119.3
O6—Cu1—N294.16 (9)C23—C24—H24119.3
O5—Cu1—N192.40 (9)C24—C25—C26118.8 (3)
O6—Cu1—N192.16 (9)C24—C25—H25120.6
N2—Cu1—N1146.51 (9)C26—C25—H25120.6
C2—C1—C6120.8 (3)C25—C26—C27121.3 (3)
C2—C1—H1119.6C25—C26—N4119.0 (3)
C6—C1—H1119.6C27—C26—N4119.7 (3)
C1—C2—C3119.5 (4)C28—C27—C26120.5 (3)
C1—C2—H2120.3C28—C27—H27119.7
C3—C2—H2120.3C26—C27—H27119.7
C2—C3—C4121.2 (4)C27—C28—C23119.2 (3)
C2—C3—H3119.4C27—C28—C36119.9 (3)
C4—C3—H3119.4C23—C28—C36120.8 (2)
C3—C4—C5118.2 (3)C34—C29—C30119.5 (3)
C3—C4—C16121.3 (3)C34—C29—C35120.9 (3)
C5—C4—C16120.3 (3)C30—C29—C35119.7 (3)
O1—C5—C6124.3 (3)O6—C30—C31119.9 (3)
O1—C5—C4114.9 (3)O6—C30—C29121.7 (3)
C6—C5—C4120.7 (3)C31—C30—C29118.4 (3)
C1—C6—C5119.5 (3)C32—C31—C30121.3 (3)
C1—C6—H6120.3C32—C31—H31119.3
C5—C6—H6120.3C30—C31—H31119.3
O1—C7—C8107.5 (3)C33—C32—C31119.1 (3)
O1—C7—H7A110.2C33—C32—H32120.5
C8—C7—H7A110.2C31—C32—H32120.5
O1—C7—H7B110.2C32—C33—C34121.4 (3)
C8—C7—H7B110.2C32—C33—N3119.8 (3)
H7A—C7—H7B108.5C34—C33—N3118.8 (3)
O2—C8—C7106.8 (3)C33—C34—C29120.3 (3)
O2—C8—H8A110.4C33—C34—H34119.9
C7—C8—H8A110.4C29—C34—H34119.9
O2—C8—H8B110.4C29—C35—N2112.7 (2)
C7—C8—H8B110.4C29—C35—H35A109.1
H8A—C8—H8B108.6N2—C35—H35A109.1
O2—C9—C10125.1 (3)C29—C35—H35B109.1
O2—C9—C14114.6 (3)N2—C35—H35B109.1
C10—C9—C14120.4 (3)H35A—C35—H35B107.8
C9—C10—C11118.9 (4)N1—C36—C28114.4 (2)
C9—C10—H10120.5N1—C36—H36A108.7
C11—C10—H10120.5C28—C36—H36A108.7
C12—C11—C10121.8 (4)N1—C36—H36B108.7
C12—C11—H11119.1C28—C36—H36B108.7
C10—C11—H11119.1H36A—C36—H36B107.6
C11—C12—C13118.7 (4)C37'—C37—Cl3'109 (3)
C11—C12—H12120.7C37'—C37—Cl2'93 (3)
C13—C12—H12120.7Cl3'—C37—Cl2'133.9 (8)
C12—C13—C14121.6 (4)C37'—C37—Cl347 (3)
C12—C13—H13119.2Cl3'—C37—Cl3138.6 (8)
C14—C13—H13119.2Cl2'—C37—Cl346.2 (4)
C13—C14—C9118.6 (3)C37'—C37—Cl187 (3)
C13—C14—C15121.2 (3)Cl2'—C37—Cl1133.2 (6)
C9—C14—C15120.1 (3)Cl3—C37—Cl1118.4 (7)
C14—C15—N1115.7 (2)C37'—C37—Cl2153 (3)
C14—C15—H15A108.3Cl3'—C37—Cl288.9 (7)
N1—C15—H15A108.3Cl2'—C37—Cl260.2 (5)
C14—C15—H15B108.3Cl3—C37—Cl2106.3 (6)
N1—C15—H15B108.3Cl1—C37—Cl2107.0 (6)
H15A—C15—H15B107.4C37—C37'—Cl3114 (3)
N2—C16—C4116.3 (2)C37—C37'—Cl2'66 (2)
N2—C16—H16A108.2Cl3—C37'—Cl2'48.0 (7)
C4—C16—H16A108.2C37—C37'—Cl1'152 (3)
N2—C16—H16B108.2Cl3—C37'—Cl1'70.0 (13)
C4—C16—H16B108.2Cl2'—C37'—Cl1'111.5 (16)
H16A—C16—H16B107.4C37—C37'—Cl3'52 (2)
N1—C17—C18115.9 (2)Cl3—C37'—Cl3'143.3 (15)
N1—C17—H17A108.3Cl2'—C37'—Cl3'106.9 (10)
C18—C17—H17A108.3Cl1'—C37'—Cl3'107.1 (12)
N1—C17—H17B108.3C37—C37'—Cl173 (3)
C18—C17—H17B108.3Cl3—C37'—Cl1136.9 (18)
H17A—C17—H17B107.4Cl2'—C37'—Cl1118.6 (10)
O3—C18—C17112.2 (2)Cl1'—C37'—Cl185.7 (10)
O3—C18—H18A109.2C36—N1—C17109.0 (2)
C17—C18—H18A109.2C36—N1—C15105.9 (2)
O3—C18—H18B109.2C17—N1—C15108.3 (2)
C17—C18—H18B109.2C36—N1—Cu1107.17 (16)
H18A—C18—H18B107.9C17—N1—Cu1110.15 (16)
O3—C19—C20113.2 (3)C15—N1—Cu1116.07 (17)
O3—C19—H19A108.9C22—N2—C16107.6 (2)
C20—C19—H19A108.9C22—N2—C35109.0 (2)
O3—C19—H19B108.9C16—N2—C35106.1 (2)
C20—C19—H19B108.9C22—N2—Cu1111.25 (18)
H19A—C19—H19B107.8C16—N2—Cu1116.04 (17)
O4—C20—C19112.6 (3)C35—N2—Cu1106.49 (17)
O4—C20—H20A109.1O9—N3—O10122.4 (3)
C19—C20—H20A109.1O9—N3—C33118.7 (3)
O4—C20—H20B109.1O10—N3—C33119.0 (3)
C19—C20—H20B109.1O8—N4—O7121.9 (3)
H20A—C20—H20B107.8O8—N4—C26119.2 (3)
O4—C21—C22112.8 (3)O7—N4—C26118.8 (3)
O4—C21—H21A109.0C5—O1—C7117.8 (2)
C22—C21—H21A109.0C9—O2—C8118.1 (3)
O4—C21—H21B109.0C18—O3—C19114.2 (2)
C22—C21—H21B109.0C21—O4—C20114.6 (3)
H21A—C21—H21B107.8C23—O5—Cu1131.38 (19)
N2—C22—C21117.1 (3)C30—O6—Cu1126.55 (19)
N2—C22—H22A108.0Cl3'—Cl1—C3757.5 (9)
C21—C22—H22A108.0Cl3'—Cl1—C37'77.0 (11)
N2—C22—H22B108.0Cl3'—Cl1—Cl1'122.8 (10)
C21—C22—H22B108.0C37—Cl1—Cl1'65.3 (5)
H22A—C22—H22B107.3C37'—Cl1—Cl1'46.1 (8)
O5—C23—C24119.1 (3)C37'—Cl1'—Cl345.6 (8)
O5—C23—C28122.3 (3)C37'—Cl1'—Cl148.2 (8)
C24—C23—C28118.6 (3)
C6—C1—C2—C31.2 (6)Cl2'—C37—C37'—Cl3'138.8 (15)
C1—C2—C3—C40.4 (6)Cl3—C37—C37'—Cl3'140.0 (16)
C2—C3—C4—C51.1 (5)Cl1—C37—C37'—Cl3'5.6 (12)
C2—C3—C4—C16177.0 (3)Cl2—C37—C37'—Cl3'128 (7)
C3—C4—C5—O1179.4 (3)Cl3'—C37—C37'—Cl15.6 (12)
C16—C4—C5—O13.4 (4)Cl2'—C37—C37'—Cl1133.1 (6)
C3—C4—C5—C60.2 (5)Cl3—C37—C37'—Cl1134 (2)
C16—C4—C5—C6176.2 (3)Cl2—C37—C37'—Cl1123 (6)
C2—C1—C6—C52.1 (6)C28—C36—N1—C17177.0 (2)
O1—C5—C6—C1179.1 (3)C28—C36—N1—C1560.7 (3)
C4—C5—C6—C11.4 (5)C28—C36—N1—Cu163.8 (3)
O1—C7—C8—O272.7 (3)C18—C17—N1—C3668.8 (3)
O2—C9—C10—C11178.0 (3)C18—C17—N1—C15176.5 (2)
C14—C9—C10—C110.5 (5)C18—C17—N1—Cu148.6 (3)
C9—C10—C11—C120.0 (6)C14—C15—N1—C36171.3 (2)
C10—C11—C12—C130.1 (6)C14—C15—N1—C1754.4 (3)
C11—C12—C13—C140.2 (6)C14—C15—N1—Cu170.0 (3)
C12—C13—C14—C90.7 (5)O5—Cu1—N1—C3636.01 (18)
C12—C13—C14—C15177.1 (3)O6—Cu1—N1—C36157.78 (17)
O2—C9—C14—C13177.8 (3)N2—Cu1—N1—C3656.9 (2)
C10—C9—C14—C130.9 (5)O5—Cu1—N1—C17154.52 (19)
O2—C9—C14—C151.4 (4)O6—Cu1—N1—C1739.28 (19)
C10—C9—C14—C15177.3 (3)N2—Cu1—N1—C1761.6 (3)
C13—C14—C15—N1101.8 (3)O5—Cu1—N1—C1582.01 (19)
C9—C14—C15—N181.9 (3)O6—Cu1—N1—C1584.20 (19)
C3—C4—C16—N2100.6 (3)N2—Cu1—N1—C15174.92 (17)
C5—C4—C16—N283.6 (4)C21—C22—N2—C16172.5 (3)
N1—C17—C18—O376.9 (3)C21—C22—N2—C3572.8 (3)
O3—C19—C20—O470.6 (4)C21—C22—N2—Cu144.3 (3)
O4—C21—C22—N272.0 (4)C4—C16—N2—C2261.8 (3)
O5—C23—C24—C25177.4 (3)C4—C16—N2—C35178.4 (3)
C28—C23—C24—C251.8 (5)C4—C16—N2—Cu163.5 (3)
C23—C24—C25—C260.4 (5)C29—C35—N2—C22175.1 (2)
C24—C25—C26—C272.4 (5)C29—C35—N2—C1659.4 (3)
C24—C25—C26—N4178.1 (3)C29—C35—N2—Cu164.8 (3)
C25—C26—C27—C282.0 (5)O5—Cu1—N2—C2246.72 (19)
N4—C26—C27—C28178.5 (3)O6—Cu1—N2—C22147.32 (19)
C26—C27—C28—C230.3 (4)N1—Cu1—N2—C2247.0 (3)
C26—C27—C28—C36176.7 (3)O5—Cu1—N2—C1676.8 (2)
O5—C23—C28—C27177.0 (3)O6—Cu1—N2—C1689.2 (2)
C24—C23—C28—C272.2 (4)N1—Cu1—N2—C16170.52 (18)
O5—C23—C28—C360.6 (4)O5—Cu1—N2—C35165.42 (18)
C24—C23—C28—C36178.5 (3)O6—Cu1—N2—C3528.63 (18)
C34—C29—C30—O6179.8 (3)N1—Cu1—N2—C3571.7 (2)
C35—C29—C30—O60.7 (4)C32—C33—N3—O9175.3 (4)
C34—C29—C30—C312.0 (4)C34—C33—N3—O94.1 (5)
C35—C29—C30—C31177.5 (3)C32—C33—N3—O103.8 (5)
O6—C30—C31—C32178.8 (3)C34—C33—N3—O10176.8 (4)
C29—C30—C31—C320.5 (5)C25—C26—N4—O8177.0 (4)
C30—C31—C32—C331.0 (6)C27—C26—N4—O82.5 (5)
C31—C32—C33—C341.0 (6)C25—C26—N4—O74.7 (5)
C31—C32—C33—N3178.4 (3)C27—C26—N4—O7175.8 (3)
C32—C33—C34—C290.5 (5)C6—C5—O1—C71.6 (4)
N3—C33—C34—C29179.9 (3)C4—C5—O1—C7178.0 (3)
C30—C29—C34—C332.0 (4)C8—C7—O1—C5177.3 (3)
C35—C29—C34—C33177.5 (3)C10—C9—O2—C82.4 (5)
C34—C29—C35—N2122.6 (3)C14—C9—O2—C8176.2 (3)
C30—C29—C35—N257.9 (4)C7—C8—O2—C9173.4 (3)
C27—C28—C36—N1133.4 (3)C17—C18—O3—C19176.8 (3)
C23—C28—C36—N150.3 (4)C20—C19—O3—C18103.1 (3)
Cl3'—C37—C37'—Cl3140.0 (16)C22—C21—O4—C20178.1 (3)
Cl2'—C37—C37'—Cl31(3)C19—C20—O4—C21112.7 (4)
Cl1—C37—C37'—Cl3134 (2)C24—C23—O5—Cu1156.6 (2)
Cl2—C37—C37'—Cl312 (8)C28—C23—O5—Cu124.3 (5)
Cl3'—C37—C37'—Cl2'138.8 (15)O6—Cu1—O5—C23103.5 (4)
Cl3—C37—C37'—Cl2'1(3)N2—Cu1—O5—C23151.3 (3)
Cl1—C37—C37'—Cl2'133.1 (6)N1—Cu1—O5—C234.7 (3)
Cl2—C37—C37'—Cl2'11 (5)C31—C30—O6—Cu1144.3 (3)
Cl3'—C37—C37'—Cl1'48 (8)C29—C30—O6—Cu137.4 (4)
Cl2'—C37—C37'—Cl1'91 (7)O5—Cu1—O6—C3084.9 (4)
Cl3—C37—C37'—Cl1'92 (7)N2—Cu1—O6—C3019.7 (3)
Cl1—C37—C37'—Cl1'42 (7)N1—Cu1—O6—C30166.8 (3)
Cl2—C37—C37'—Cl1'80 (10)
Table 1
Selected geometric parameters (Å, °)
top
Cu1—O51.874 (2)Cu1—N22.144 (2)
Cu1—O61.878 (2)Cu1—N12.147 (2)
O5—Cu1—O6165.47 (10)O5—Cu1—N192.40 (9)
O5—Cu1—N289.60 (9)O6—Cu1—N192.16 (9)
O6—Cu1—N294.16 (9)N2—Cu1—N1146.51 (9)
Acknowledgements top

We thank the National Natural Science Foundation of China (No. 20471014), the Program for New Century Excellent Talents in Chinese Universities (NCET-05–0320), the Fok Ying Tung Education Foundation, and the Analysis and Testing Foundation of Northeast Normal University for support.

references
References top

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