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Acta Cryst. (2007). E63, m2984-m2985    [ doi:10.1107/S1600536807056310 ]

Poly[[([mu]4-naphthalene-1,4-dicarboxylato-[kappa]4O:O:O:O')([mu]2-naphthalene-1,4-dicarboxylato-[kappa]2O:O')bis(pyrazino[2,3-f][1,10]phenanthroline-[kappa]2N,N')dicopper(II)] tetrahydrate\]

G.-B. Che, C.-B. Liu and S. W. Ng

Abstract top

One naphthalene-1,4-dicarboxylate dianion in the title compound, [Cu2(C12H6O4)2(C14H8N4)2]·4H2O, bridges two N-heterocycle-chelated Cu atoms whereas the other one bridges four N-heterocycle-chelated Cu atoms, linking them into a flat carboxylate-bridged layer. The two independent Cu atoms show square-pyramidal coordination. Water molecules occupy the space between adjacent layers; they are possibly disordered, and their H atoms were not located.

Comment top

The Cambridge Structural Database (Version 5.28, November 2006) lists several examples of metal(II) naphthalene-1,4-dicarboxylates (Maji et al., 2005; Zheng et al., 2004). The dicarboxylate group is rigid, like terephthalic acid. The copper terephthalate complex of the title heterocycle (Wang et al., 2006) has water in the coordination enviroment of the cadmium atom; the compound exists as a linear chain; one carboxyl end is chelating whereas the other is unidentate.

Related literature top

The Cambridge Structural Database (Version 5.28, November 2006) lists several examples of metal(II) naphthalene-1,4-dicarboxylates. For hydrated diaqua(4,4'-bipyridine)-cobalt, -nickel and -copper compounds, see: Maji et al. (2005); Zheng et al. (2004). For the hydrated 1,2-bis(4-pyridyl)ethanecopper compound, see: Maji et al. (2005). For the crystal structure of naphthalene-1,4-dicarboxylic acid, see: Derissen et al. (1979). For the copper terephthalate complex of the N-heterocycle, see: Wang et al. (2006).

Experimental top

Copper chloride dihydrate (0.1 mmol), naphthalene-1,4-dicarboxylic acid (0.1 mmol), pyrazino[2,3-f][1,10]phenanthroline and water (12 ml) were sealed in a 23-ml Teflon-lined Parr bomb, which was heated at 423 K for two days. Blue block crystals were picked from the cool solution by hand in about 30% yield.

Refinement top

As all C–, N– and O-atoms showed somewhat elongated ellipsoids, their anisotropic temperature factors were restrained to be nearly isotropic. The O2, O4, O6 and O8 atoms, which are not involved in coordination, showed large displacement parameters. An attempt was made to refine each atom as two atoms of half site-occupancy each, with the pairs of C–O double-bond distances restrained to within 0.01 Å of each other. However, this treatment required the carboxyl –CO2 group to be approximately planar, so that the O1, O3, O5 and O7 atoms that are involved in coordination would have to be split into two. As the treatment led to only a minor separation between the disorder components, the structure was refined without disorder.

Carbon-bound H atoms were placed in calculated positions [C—H 0.93–0.97 Å and Uiso(H) 1.2–1.5Ueq(C)], and were included in the refinement in the riding-model approximation. The water H-atoms could not be placed in chemically sensible positions on the basis of hydrogen bonding, and were not included.

The final difference Fourier map had a large peak near O3w.

Computing details top

Data collection: RAPID-AUTO (Rigaku Corporation, 1998); cell refinement: RAPID-AUTO (Rigaku Corporation, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); OLEX (Dolomanov et al., 2003); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot of a portion of the chain structure; displacement ellipsoids are drawn at the 50% probability level, and H atoms as spheres of arbitrary radius. (Symmetry codes are given in Table 1.)
[Figure 2] Fig. 2. OLEX (Dolomanov et al., 2003) representation of the layer network.
Poly[[(µ4-naphthalene-1,4-dicarboxylato- κ4O:O:O:O')(µ2-naphthalene-1,4- dicarboxylato-κ2O:O')bis(pyrazino[2,3-f][1,10]phenanthroline-κ2N,N')dicopper(II)] tetrahydrate] top
Crystal data top
[Cu2(C12H6O4)2(C14H8N4)2]·4H2OZ = 2
Mr = 1091.97F(000) = 1116
Triclinic, P1Dx = 1.546 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 12.679 (5) ÅCell parameters from 15645 reflections
b = 14.690 (6) Åθ = 3.0–27.5°
c = 14.833 (7) ŵ = 0.98 mm−1
α = 69.37 (2)°T = 295 K
β = 82.05 (2)°Block, blue
γ = 65.13 (2)°0.38 × 0.27 × 0.16 mm
V = 2346 (2) Å3
Data collection top
Rigaku RAXIS-RAPID
diffractometer		10535 independent reflections
Radiation source: fine-focus sealed tube6887 reflections with I > 2σ(I)
graphiteRint = 0.032
Detector resolution: 10.000 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω–scansh = −16→16
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −18→19
Tmin = 0.618, Tmax = 0.859l = −19→19
22789 measured reflections
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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.190H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.1132P)2]
where P = (Fo2 + 2Fc2)/3
10535 reflections(Δ/σ)max = 0.001
667 parametersΔρmax = 1.03 e Å−3
436 restraintsΔρmin = −0.51 e Å−3
Crystal data top
[Cu2(C12H6O4)2(C14H8N4)2]·4H2Oγ = 65.13 (2)°
Mr = 1091.97V = 2346 (2) Å3
Triclinic, P1Z = 2
a = 12.679 (5) ÅMo Kα radiation
b = 14.690 (6) ŵ = 0.98 mm−1
c = 14.833 (7) ÅT = 295 K
α = 69.37 (2)°0.38 × 0.27 × 0.16 mm
β = 82.05 (2)°
Data collection top
Rigaku RAXIS-RAPID
diffractometer		10535 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		6887 reflections with I > 2σ(I)
Tmin = 0.618, Tmax = 0.859Rint = 0.032
22789 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.190Δρmax = 1.03 e Å−3
S = 1.09Δρmin = −0.51 e Å−3
10535 reflectionsAbsolute structure: ?
667 parametersFlack parameter: ?
436 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.40502 (3)0.45832 (4)0.46309 (3)0.03280 (15)
Cu21.08859 (3)0.04876 (3)0.02766 (3)0.03177 (15)
O10.5140 (2)0.4239 (2)0.3639 (2)0.0448 (7)
O20.4999 (3)0.2724 (3)0.3878 (3)0.0798 (12)
O30.9640 (2)0.1145 (3)0.1032 (2)0.0484 (7)
O40.9801 (3)0.2685 (3)0.0434 (3)0.0950 (14)
O50.5321 (2)0.4001 (2)0.55622 (19)0.0403 (6)
O60.5128 (5)0.2520 (4)0.6161 (4)0.166 (3)
O70.9755 (2)0.0895 (2)0.92765 (18)0.0358 (6)
O81.0457 (3)0.1950 (3)0.8171 (3)0.0884 (14)
O1W0.4320 (7)0.1517 (6)0.3165 (6)0.172 (3)
O2W0.4226 (10)−0.0548 (8)0.4733 (8)0.264 (5)
O3W0.2273 (10)0.2971 (9)0.1769 (10)0.269 (5)
O4W0.0234 (8)0.4201 (7)0.0950 (7)0.199 (3)
N10.2756 (3)0.5119 (3)0.5508 (2)0.0365 (7)
N2−0.1416 (3)0.6969 (3)0.5521 (3)0.0618 (11)
N3−0.1518 (3)0.6744 (3)0.3731 (3)0.0564 (11)
N40.2664 (3)0.5018 (3)0.3791 (2)0.0374 (7)
N51.2335 (3)−0.0271 (3)−0.0366 (2)0.0370 (7)
N61.6504 (3)−0.2026 (4)0.0081 (4)0.0778 (15)
N71.6236 (4)−0.1483 (4)0.1776 (4)0.0813 (16)
N81.2092 (3)0.0200 (3)0.1218 (2)0.0419 (8)
C10.5436 (3)0.3354 (4)0.3488 (3)0.0456 (10)
C20.6396 (4)0.3128 (3)0.2770 (3)0.0410 (9)
C30.6428 (3)0.3867 (3)0.1860 (3)0.0412 (9)
C40.5545 (4)0.4905 (4)0.1521 (3)0.0542 (11)
H40.49290.51220.19240.065*
C50.5566 (5)0.5586 (5)0.0639 (4)0.0773 (17)
H50.49630.62560.04390.093*
C60.6494 (5)0.5291 (5)0.0019 (4)0.0838 (18)
H60.65090.5767−0.05890.101*
C70.7375 (5)0.4303 (5)0.0309 (4)0.0701 (15)
H70.79800.4115−0.01110.084*
C80.7392 (4)0.3555 (4)0.1236 (3)0.0448 (10)
C90.8284 (4)0.2514 (4)0.1551 (3)0.0446 (10)
C100.8216 (4)0.1838 (4)0.2438 (3)0.0497 (11)
H100.88050.11610.26460.060*
C110.7283 (4)0.2133 (4)0.3046 (3)0.0475 (10)
H110.72610.16480.36470.057*
C120.9324 (3)0.2109 (4)0.0949 (3)0.0519 (11)
C130.5642 (3)0.3075 (4)0.6105 (3)0.0597 (14)
C140.6719 (4)0.2660 (3)0.6709 (3)0.0467 (11)
C150.7829 (4)0.2141 (4)0.6364 (3)0.0525 (12)
C160.7986 (5)0.1958 (5)0.5469 (4)0.0658 (14)
H160.73370.21810.50940.079*
C170.9053 (6)0.1467 (5)0.5149 (4)0.0778 (17)
H170.91330.13560.45590.093*
C181.0043 (5)0.1124 (5)0.5705 (5)0.0752 (16)
H181.07770.07790.54850.090*
C190.9937 (4)0.1291 (4)0.6554 (4)0.0594 (13)
H191.06040.10670.69070.071*
C200.8835 (4)0.1799 (3)0.6927 (3)0.0458 (10)
C210.8679 (3)0.1958 (3)0.7835 (3)0.0451 (11)
C220.7598 (4)0.2426 (4)0.8150 (3)0.0497 (11)
H220.75070.25000.87560.060*
C230.6608 (4)0.2801 (4)0.7583 (4)0.0533 (12)
H230.58750.31460.78040.064*
C240.9719 (3)0.1584 (3)0.8466 (3)0.0448 (10)
C250.2843 (4)0.5114 (4)0.6399 (3)0.0494 (11)
H250.35740.48080.66860.059*
C260.1866 (4)0.5557 (4)0.6905 (3)0.0559 (12)
H260.19530.55340.75260.067*
C270.0786 (4)0.6022 (4)0.6508 (4)0.0523 (11)
H270.01350.63270.68460.063*
C280.0674 (3)0.6034 (3)0.5569 (3)0.0418 (9)
C290.1678 (3)0.5570 (3)0.5106 (3)0.0341 (8)
C30−0.0446 (3)0.6484 (3)0.5075 (3)0.0437 (10)
C31−0.2407 (4)0.7337 (4)0.5027 (5)0.0748 (17)
H31−0.31030.76970.52880.090*
C32−0.2450 (4)0.7213 (4)0.4169 (5)0.0688 (16)
H32−0.31710.74710.38810.083*
C33−0.0489 (3)0.6382 (3)0.4184 (3)0.0431 (10)
C340.0568 (3)0.5868 (3)0.3719 (3)0.0372 (9)
C350.1630 (3)0.5495 (3)0.4170 (3)0.0344 (8)
C360.0581 (4)0.5722 (4)0.2839 (3)0.0485 (11)
H36−0.01100.59660.25100.058*
C370.1624 (4)0.5215 (4)0.2462 (3)0.0545 (12)
H370.16470.50980.18820.065*
C380.2649 (4)0.4877 (4)0.2954 (3)0.0461 (10)
H380.33520.45390.26880.055*
C391.2428 (4)−0.0517 (4)−0.1160 (3)0.0507 (11)
H391.1752−0.0320−0.14900.061*
C401.3496 (4)−0.1059 (5)−0.1521 (4)0.0703 (16)
H401.3522−0.1187−0.20970.084*
C411.4494 (4)−0.1399 (4)−0.1038 (4)0.0653 (14)
H411.5206−0.1774−0.12680.078*
C421.4433 (3)−0.1176 (4)−0.0183 (4)0.0500 (11)
C431.3335 (3)−0.0605 (3)0.0128 (3)0.0413 (9)
C441.5449 (4)−0.1491 (4)0.0385 (4)0.0564 (13)
C451.7391 (5)−0.2288 (5)0.0639 (6)0.092 (2)
H451.8138−0.26630.04610.110*
C461.7261 (5)−0.2040 (5)0.1441 (5)0.083 (2)
H461.7928−0.22680.17970.100*
C471.5308 (4)−0.1213 (4)0.1220 (4)0.0596 (14)
C481.4168 (4)−0.0613 (4)0.1527 (3)0.0505 (12)
C491.3201 (3)−0.0329 (3)0.0982 (3)0.0400 (9)
C501.3978 (5)−0.0324 (4)0.2340 (4)0.0670 (16)
H501.4603−0.04860.27150.080*
C511.2862 (5)0.0203 (5)0.2597 (4)0.0687 (15)
H511.27240.03920.31520.082*
C521.1935 (4)0.0454 (4)0.2016 (3)0.0564 (12)
H521.11810.08110.21950.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0200 (2)0.0465 (3)0.0297 (2)−0.00772 (19)−0.00046 (17)−0.0166 (2)
Cu20.0223 (2)0.0404 (3)0.0325 (3)−0.00717 (19)−0.00198 (18)−0.0176 (2)
O10.0337 (14)0.064 (2)0.0453 (16)−0.0163 (13)0.0082 (12)−0.0347 (15)
O20.083 (3)0.069 (3)0.095 (3)−0.041 (2)0.049 (2)−0.039 (2)
O30.0386 (15)0.059 (2)0.0553 (18)−0.0118 (14)0.0079 (13)−0.0397 (15)
O40.080 (3)0.075 (3)0.131 (4)−0.035 (2)0.065 (3)−0.053 (3)
O50.0303 (13)0.0463 (17)0.0372 (14)−0.0089 (12)−0.0103 (11)−0.0097 (12)
O60.147 (4)0.117 (4)0.211 (5)−0.098 (4)−0.135 (4)0.081 (4)
O70.0293 (13)0.0411 (15)0.0345 (13)−0.0118 (11)−0.0063 (11)−0.0097 (11)
O80.066 (2)0.099 (3)0.084 (3)−0.057 (2)−0.035 (2)0.032 (2)
O1W0.197 (6)0.211 (6)0.183 (6)−0.103 (5)0.048 (5)−0.141 (5)
O2W0.328 (9)0.227 (8)0.238 (8)−0.108 (7)−0.058 (7)−0.058 (7)
O3W0.299 (9)0.204 (7)0.322 (10)−0.126 (7)0.007 (7)−0.078 (7)
O4W0.228 (7)0.191 (7)0.233 (7)−0.109 (6)−0.009 (6)−0.096 (5)
N10.0255 (15)0.052 (2)0.0351 (16)−0.0147 (14)0.0023 (13)−0.0198 (15)
N20.0331 (19)0.062 (3)0.081 (3)−0.0132 (17)0.0146 (19)−0.025 (2)
N30.0281 (18)0.054 (2)0.075 (3)−0.0136 (16)−0.0103 (18)−0.006 (2)
N40.0279 (16)0.049 (2)0.0358 (16)−0.0146 (14)−0.0005 (13)−0.0153 (15)
N50.0241 (15)0.0434 (19)0.0405 (17)−0.0082 (13)−0.0024 (13)−0.0160 (14)
N60.0276 (19)0.069 (3)0.107 (4)−0.0112 (19)−0.006 (2)−0.002 (3)
N70.049 (2)0.093 (3)0.081 (3)−0.039 (2)−0.029 (2)0.019 (3)
N80.0455 (19)0.047 (2)0.0385 (17)−0.0212 (16)−0.0095 (15)−0.0123 (15)
C10.037 (2)0.060 (3)0.042 (2)−0.017 (2)0.0058 (18)−0.024 (2)
C20.039 (2)0.050 (2)0.041 (2)−0.0161 (18)0.0030 (17)−0.0263 (18)
C30.038 (2)0.048 (2)0.039 (2)−0.0114 (17)0.0058 (17)−0.0254 (18)
C40.043 (2)0.051 (3)0.055 (3)−0.008 (2)0.010 (2)−0.019 (2)
C50.075 (4)0.055 (3)0.067 (3)−0.004 (3)0.005 (3)−0.010 (3)
C60.087 (4)0.073 (4)0.059 (3)−0.021 (3)0.015 (3)−0.006 (3)
C70.072 (3)0.075 (4)0.051 (3)−0.024 (3)0.020 (2)−0.022 (3)
C80.043 (2)0.053 (3)0.043 (2)−0.0166 (19)0.0082 (18)−0.0264 (19)
C90.039 (2)0.051 (3)0.049 (2)−0.0126 (18)0.0089 (18)−0.032 (2)
C100.050 (2)0.043 (2)0.051 (2)−0.0058 (19)0.006 (2)−0.027 (2)
C110.050 (2)0.052 (3)0.038 (2)−0.013 (2)0.0053 (18)−0.0219 (19)
C120.042 (2)0.059 (3)0.056 (3)−0.016 (2)0.015 (2)−0.031 (2)
C130.045 (2)0.055 (3)0.069 (3)−0.026 (2)−0.033 (2)0.012 (2)
C140.038 (2)0.038 (2)0.052 (2)−0.0141 (18)−0.0200 (19)0.0060 (18)
C150.051 (3)0.054 (3)0.048 (2)−0.030 (2)−0.019 (2)0.005 (2)
C160.064 (3)0.084 (4)0.053 (3)−0.034 (3)−0.012 (2)−0.016 (3)
C170.090 (4)0.088 (4)0.062 (3)−0.041 (3)−0.007 (3)−0.022 (3)
C180.067 (3)0.072 (4)0.080 (4)−0.023 (3)0.007 (3)−0.027 (3)
C190.052 (3)0.057 (3)0.062 (3)−0.023 (2)−0.011 (2)−0.005 (2)
C200.038 (2)0.045 (2)0.047 (2)−0.0190 (18)−0.0133 (19)0.0008 (18)
C210.032 (2)0.042 (2)0.049 (2)−0.0174 (17)−0.0159 (18)0.0078 (18)
C220.040 (2)0.053 (3)0.050 (2)−0.0193 (19)−0.0116 (19)−0.004 (2)
C230.033 (2)0.047 (3)0.068 (3)−0.0118 (18)−0.015 (2)−0.005 (2)
C240.031 (2)0.048 (2)0.045 (2)−0.0144 (18)−0.0130 (18)−0.0004 (18)
C250.033 (2)0.083 (3)0.043 (2)−0.026 (2)0.0028 (17)−0.030 (2)
C260.048 (3)0.093 (4)0.048 (2)−0.034 (2)0.011 (2)−0.043 (2)
C270.042 (2)0.067 (3)0.064 (3)−0.026 (2)0.021 (2)−0.041 (2)
C280.0299 (19)0.047 (2)0.051 (2)−0.0175 (17)0.0084 (17)−0.0198 (19)
C290.0256 (17)0.041 (2)0.0377 (19)−0.0150 (15)0.0030 (15)−0.0147 (16)
C300.0262 (18)0.039 (2)0.061 (3)−0.0124 (16)0.0056 (18)−0.0135 (19)
C310.021 (2)0.073 (4)0.104 (4)−0.005 (2)0.008 (3)−0.019 (3)
C320.030 (2)0.064 (3)0.093 (4)−0.014 (2)−0.011 (3)−0.006 (3)
C330.0269 (19)0.038 (2)0.057 (2)−0.0139 (16)−0.0053 (18)−0.0034 (18)
C340.0268 (18)0.040 (2)0.0400 (19)−0.0135 (16)−0.0072 (16)−0.0044 (16)
C350.0279 (18)0.037 (2)0.0366 (19)−0.0146 (15)0.0003 (15)−0.0075 (16)
C360.044 (2)0.059 (3)0.042 (2)−0.026 (2)−0.0122 (19)−0.0059 (19)
C370.057 (3)0.077 (3)0.036 (2)−0.031 (2)−0.007 (2)−0.017 (2)
C380.036 (2)0.070 (3)0.035 (2)−0.021 (2)0.0015 (17)−0.0209 (19)
C390.035 (2)0.068 (3)0.058 (3)−0.017 (2)0.0049 (19)−0.036 (2)
C400.042 (3)0.099 (4)0.085 (4)−0.024 (3)0.018 (3)−0.060 (3)
C410.034 (2)0.068 (3)0.095 (4)−0.012 (2)0.016 (2)−0.045 (3)
C420.0228 (19)0.046 (2)0.071 (3)−0.0091 (17)−0.0041 (19)−0.012 (2)
C430.0266 (18)0.040 (2)0.052 (2)−0.0137 (16)−0.0056 (17)−0.0069 (18)
C440.029 (2)0.044 (3)0.078 (3)−0.0104 (18)−0.012 (2)0.000 (2)
C450.033 (3)0.083 (4)0.117 (5)−0.015 (3)−0.013 (3)0.009 (4)
C460.037 (3)0.088 (4)0.107 (5)−0.028 (3)−0.031 (3)0.005 (3)
C470.033 (2)0.053 (3)0.077 (3)−0.023 (2)−0.027 (2)0.013 (2)
C480.048 (2)0.048 (3)0.052 (2)−0.025 (2)−0.021 (2)0.002 (2)
C490.035 (2)0.038 (2)0.045 (2)−0.0155 (17)−0.0133 (18)−0.0042 (17)
C500.071 (3)0.071 (3)0.067 (3)−0.040 (3)−0.029 (3)−0.006 (3)
C510.087 (4)0.085 (4)0.049 (3)−0.039 (3)−0.015 (3)−0.028 (3)
C520.061 (3)0.067 (3)0.050 (2)−0.026 (2)−0.006 (2)−0.025 (2)
Geometric parameters (Å, °) top
Cu1—O11.924 (3)C15—C161.416 (7)
Cu1—O51.965 (2)C15—C201.427 (5)
Cu1—O5i2.440 (3)C16—C171.349 (8)
Cu1—N12.012 (3)C16—H160.9300
Cu1—N42.037 (3)C17—C181.404 (8)
Cu2—O31.916 (3)C17—H170.9300
Cu2—O7ii1.964 (2)C18—C191.345 (8)
Cu2—O7iii2.348 (3)C18—H180.9300
Cu2—N52.017 (3)C19—C201.419 (7)
Cu2—N82.024 (3)C19—H190.9300
O1—C11.287 (5)C20—C211.421 (6)
O2—C11.209 (5)C21—C221.352 (6)
O3—C121.262 (6)C21—C241.511 (5)
O4—C121.230 (6)C22—C231.404 (6)
O5—C131.232 (5)C22—H220.9300
O5—Cu1i2.440 (3)C23—H230.9300
O6—C131.216 (6)C25—C261.390 (6)
O7—C241.262 (5)C25—H250.9300
O7—Cu2iv1.964 (2)C26—C271.357 (6)
O7—Cu2iii2.348 (3)C26—H260.9300
O8—C241.224 (5)C27—C281.414 (6)
N1—C251.339 (5)C27—H270.9300
N1—C291.360 (5)C28—C291.384 (6)
N2—C311.347 (6)C28—C301.464 (6)
N2—C301.353 (6)C29—C351.441 (5)
N3—C321.308 (7)C30—C331.393 (6)
N3—C331.357 (5)C31—C321.359 (8)
N4—C381.332 (5)C31—H310.9300
N4—C351.352 (5)C32—H320.9300
N5—C391.325 (5)C33—C341.449 (6)
N5—C431.367 (5)C34—C361.393 (6)
N6—C451.329 (7)C34—C351.391 (5)
N6—C441.344 (7)C36—C371.370 (7)
N7—C461.349 (9)C36—H360.9300
N7—C471.366 (5)C37—C381.389 (6)
N8—C521.329 (6)C37—H370.9300
N8—C491.357 (5)C38—H380.9300
C1—C21.508 (6)C39—C401.396 (6)
C2—C111.376 (6)C39—H390.9300
C2—C31.412 (6)C40—C411.354 (7)
C3—C41.418 (6)C40—H400.9300
C3—C81.441 (6)C41—C421.402 (7)
C4—C51.342 (7)C41—H410.9300
C4—H40.9300C42—C431.402 (6)
C5—C61.404 (8)C42—C441.451 (6)
C5—H50.9300C43—C491.429 (6)
C6—C71.367 (8)C44—C471.403 (8)
C6—H60.9300C45—C461.334 (10)
C7—C81.422 (7)C45—H450.9300
C7—H70.9300C46—H460.9300
C8—C91.423 (6)C47—C481.450 (7)
C9—C101.358 (7)C48—C501.373 (7)
C9—C121.511 (6)C48—C491.391 (5)
C10—C111.396 (6)C50—C511.373 (8)
C10—H100.9300C50—H500.9300
C11—H110.9300C51—C521.396 (6)
C13—C141.515 (5)C51—H510.9300
C14—C231.363 (7)C52—H520.9300
C14—C151.412 (7)
O1—Cu1—O591.2 (1)C20—C19—H19119.1
O1—Cu1—N1171.5 (1)C21—C20—C19123.7 (4)
O5—Cu1—N196.2 (1)C21—C20—C15118.5 (4)
O1—Cu1—N492.4 (1)C19—C20—C15117.7 (4)
O5—Cu1—N4171.8 (1)C22—C21—C20120.1 (4)
N1—Cu1—N480.8 (1)C22—C21—C24119.6 (4)
O1—Cu1—O5i86.7 (1)C20—C21—C24120.3 (3)
O5—Cu1—O5i72.8 (1)C21—C22—C23121.6 (5)
N1—Cu1—O5i91.5 (1)C21—C22—H22119.2
N4—Cu1—O5i114.8 (1)C23—C22—H22119.2
O7ii—Cu2—O389.5 (1)C14—C23—C22120.1 (4)
O7ii—Cu2—N598.1 (1)C14—C23—H23120.0
O3—Cu2—N5172.4 (1)C22—C23—H23120.0
O7ii—Cu2—N8173.9 (1)O8—C24—O7124.7 (3)
O3—Cu2—N891.7 (1)O8—C24—C21119.6 (4)
N5—Cu2—N880.8 (1)O7—C24—C21115.7 (3)
O7ii—Cu2—O7iii74.6 (1)N1—C25—C26121.4 (4)
O3—Cu2—O7iii87.0 (1)N1—C25—H25119.3
N5—Cu2—O7iii94.3 (1)C26—C25—H25119.3
N8—Cu2—O7iii111.4 (1)C27—C26—C25121.1 (4)
C1—O1—Cu1120.8 (3)C27—C26—H26119.5
C12—O3—Cu2120.9 (3)C25—C26—H26119.5
C13—O5—Cu1120.1 (3)C26—C27—C28118.4 (4)
C13—O5—Cu1i132.6 (2)C26—C27—H27120.8
Cu1—O5—Cu1i107.22 (12)C28—C27—H27120.8
C24—O7—Cu2iv121.6 (2)C29—C28—C27117.8 (4)
C24—O7—Cu2iii129.8 (2)C29—C28—C30118.6 (4)
Cu2iv—O7—Cu2iii105.40 (11)C27—C28—C30123.5 (4)
C25—N1—C29118.1 (3)N1—C29—C28123.1 (4)
C25—N1—Cu1128.0 (3)N1—C29—C35115.7 (3)
C29—N1—Cu1113.8 (2)C28—C29—C35121.1 (3)
C31—N2—C30114.0 (5)N2—C30—C33122.1 (4)
C32—N3—C33116.1 (5)N2—C30—C28118.0 (4)
C38—N4—C35117.6 (3)C33—C30—C28119.9 (4)
C38—N4—Cu1129.1 (3)N2—C31—C32123.8 (5)
C35—N4—Cu1113.3 (2)N2—C31—H31118.1
C39—N5—C43117.6 (4)C32—C31—H31118.1
C39—N5—Cu2128.9 (3)N3—C32—C31122.7 (5)
C43—N5—Cu2113.5 (3)N3—C32—H32118.7
C45—N6—C44115.2 (6)C31—C32—H32118.7
C46—N7—C47113.0 (6)N3—C33—C30121.2 (4)
C52—N8—C49117.4 (4)N3—C33—C34118.0 (4)
C52—N8—Cu2128.8 (3)C30—C33—C34120.8 (3)
C49—N8—Cu2113.8 (3)C36—C34—C35117.7 (4)
O2—C1—O1124.3 (4)C36—C34—C33123.5 (4)
O2—C1—C2120.3 (4)C35—C34—C33118.8 (4)
O1—C1—C2115.4 (4)N4—C35—C34123.4 (4)
C11—C2—C3119.7 (4)N4—C35—C29116.0 (3)
C11—C2—C1116.2 (4)C34—C35—C29120.6 (4)
C3—C2—C1124.1 (4)C37—C36—C34119.2 (4)
C2—C3—C4123.1 (4)C37—C36—H36120.4
C2—C3—C8118.9 (4)C34—C36—H36120.4
C4—C3—C8118.0 (4)C36—C37—C38119.5 (4)
C5—C4—C3122.4 (5)C36—C37—H37120.3
C5—C4—H4118.8C38—C37—H37120.3
C3—C4—H4118.8N4—C38—C37122.6 (4)
C4—C5—C6120.3 (5)N4—C38—H38118.7
C4—C5—H5119.9C37—C38—H38118.7
C6—C5—H5119.9N5—C39—C40122.8 (4)
C7—C6—C5120.0 (6)N5—C39—H39118.6
C7—C6—H6120.0C40—C39—H39118.6
C5—C6—H6120.0C41—C40—C39120.3 (5)
C6—C7—C8121.8 (5)C41—C40—H40119.9
C6—C7—H7119.1C39—C40—H40119.9
C8—C7—H7119.1C40—C41—C42118.7 (4)
C7—C8—C9123.2 (4)C40—C41—H41120.6
C7—C8—C3117.5 (4)C42—C41—H41120.6
C9—C8—C3119.3 (4)C41—C42—C43118.1 (4)
C10—C9—C8119.4 (4)C41—C42—C44123.3 (4)
C10—C9—C12117.3 (4)C43—C42—C44118.6 (5)
C8—C9—C12123.3 (4)N5—C43—C42122.4 (4)
C9—C10—C11121.7 (4)N5—C43—C49116.0 (4)
C9—C10—H10119.2C42—C43—C49121.6 (4)
C11—C10—H10119.2N6—C44—C47121.9 (4)
C2—C11—C10121.1 (4)N6—C44—C42118.7 (5)
C2—C11—H11119.5C47—C44—C42119.4 (4)
C10—C11—H11119.5N6—C45—C46123.2 (6)
O4—C12—O3124.6 (4)N6—C45—H45118.4
O4—C12—C9121.6 (4)C46—C45—H45118.4
O3—C12—C9113.8 (4)C45—C46—N7124.9 (5)
O6—C13—O5122.5 (4)C45—C46—H46117.6
O6—C13—C14121.4 (4)N7—C46—H46117.6
O5—C13—C14116.1 (4)N7—C47—C44121.8 (5)
C23—C14—C15120.5 (4)N7—C47—C48116.9 (5)
C23—C14—C13119.3 (4)C44—C47—C48121.3 (4)
C15—C14—C13120.2 (4)C50—C48—C49117.6 (5)
C14—C15—C16122.5 (4)C50—C48—C47123.9 (4)
C14—C15—C20119.1 (4)C49—C48—C47118.6 (4)
C16—C15—C20118.4 (5)N8—C49—C48123.7 (4)
C17—C16—C15121.6 (5)N8—C49—C43115.8 (3)
C17—C16—H16119.2C48—C49—C43120.5 (4)
C15—C16—H16119.2C51—C50—C48119.8 (4)
C16—C17—C18120.1 (6)C51—C50—H50120.1
C16—C17—H17119.9C48—C50—H50120.1
C18—C17—H17119.9C50—C51—C52119.3 (5)
C19—C18—C17120.3 (6)C50—C51—H51120.3
C19—C18—H18119.8C52—C51—H51120.3
C17—C18—H18119.8N8—C52—C51122.3 (5)
C18—C19—C20121.8 (5)N8—C52—H52118.8
C18—C19—H19119.1C51—C52—H52118.8
O5—Cu1—O1—C193.3 (2)Cu2iii—O7—C24—C2133.8 (3)
N4—Cu1—O1—C1−79.3 (2)C22—C21—C24—O8−120.2 (4)
O5i—Cu1—O1—C1166.0 (2)C20—C21—C24—O861.2 (4)
O7ii—Cu2—O3—C12−90.6 (2)C22—C21—C24—O760.2 (4)
N8—Cu2—O3—C1283.4 (2)C20—C21—C24—O7−118.5 (4)
O7iii—Cu2—O3—C12−165.2 (2)C29—N1—C25—C26−0.2 (7)
O1—Cu1—O5—C13−94.3 (3)Cu1—N1—C25—C26177.2 (4)
N1—Cu1—O5—C1389.8 (3)N1—C25—C26—C27−0.8 (8)
O5i—Cu1—O5—C13179.4 (3)C25—C26—C27—C280.9 (8)
O1—Cu1—O5—Cu1i86.21 (14)C26—C27—C28—C29−0.1 (7)
N1—Cu1—O5—Cu1i−89.68 (14)C26—C27—C28—C30178.1 (4)
O5i—Cu1—O5—Cu1i0.0C25—N1—C29—C280.9 (6)
O5—Cu1—N1—C254.6 (4)Cu1—N1—C29—C28−176.8 (3)
N4—Cu1—N1—C25176.9 (4)C25—N1—C29—C35−176.4 (4)
O5i—Cu1—N1—C25−68.3 (4)Cu1—N1—C29—C355.9 (4)
O5—Cu1—N1—C29−178.0 (3)C27—C28—C29—N1−0.8 (6)
N4—Cu1—N1—C29−5.7 (3)C30—C28—C29—N1−179.1 (4)
O5i—Cu1—N1—C29109.2 (3)C27—C28—C29—C35176.4 (4)
O1—Cu1—N4—C3811.1 (4)C30—C28—C29—C35−2.0 (6)
N1—Cu1—N4—C38−174.0 (4)C31—N2—C30—C33−0.1 (7)
O5i—Cu1—N4—C3898.6 (4)C31—N2—C30—C28−178.6 (4)
O1—Cu1—N4—C35−170.4 (3)C29—C28—C30—N2−177.6 (4)
N1—Cu1—N4—C354.5 (3)C27—C28—C30—N24.1 (7)
O5i—Cu1—N4—C35−82.9 (3)C29—C28—C30—C333.8 (6)
O7ii—Cu2—N5—C39−7.6 (4)C27—C28—C30—C33−174.4 (4)
N8—Cu2—N5—C39178.5 (4)C30—N2—C31—C321.8 (8)
O7iii—Cu2—N5—C3967.5 (4)C33—N3—C32—C310.0 (8)
O7ii—Cu2—N5—C43175.6 (3)N2—C31—C32—N3−1.9 (9)
N8—Cu2—N5—C431.6 (3)C32—N3—C33—C301.7 (6)
O7iii—Cu2—N5—C43−109.4 (3)C32—N3—C33—C34−179.3 (4)
O3—Cu2—N8—C52−1.7 (4)N2—C30—C33—N3−1.7 (7)
N5—Cu2—N8—C52179.9 (4)C28—C30—C33—N3176.8 (4)
O7iii—Cu2—N8—C52−89.1 (4)N2—C30—C33—C34179.3 (4)
O3—Cu2—N8—C49178.0 (3)C28—C30—C33—C34−2.2 (6)
N5—Cu2—N8—C49−0.4 (3)N3—C33—C34—C36−0.4 (6)
O7iii—Cu2—N8—C4990.5 (3)C30—C33—C34—C36178.6 (4)
Cu1—O1—C1—O26.7 (3)N3—C33—C34—C35179.8 (4)
Cu1—O1—C1—C2−173.3 (2)C30—C33—C34—C35−1.2 (6)
O2—C1—C2—C11−47.7 (4)C38—N4—C35—C34−2.0 (6)
O1—C1—C2—C11132.3 (4)Cu1—N4—C35—C34179.3 (3)
O2—C1—C2—C3132.6 (4)C38—N4—C35—C29176.0 (4)
O1—C1—C2—C3−47.4 (4)Cu1—N4—C35—C29−2.7 (4)
C11—C2—C3—C4179.7 (4)C36—C34—C35—N41.1 (6)
C1—C2—C3—C4−0.6 (6)C33—C34—C35—N4−179.1 (4)
C11—C2—C3—C80.5 (6)C36—C34—C35—C29−176.8 (4)
C1—C2—C3—C8−179.8 (3)C33—C34—C35—C293.1 (6)
C2—C3—C4—C5−177.5 (5)N1—C29—C35—N4−2.1 (5)
C8—C3—C4—C51.7 (7)C28—C29—C35—N4−179.5 (4)
C3—C4—C5—C6−1.2 (10)N1—C29—C35—C34175.9 (3)
C4—C5—C6—C70.6 (11)C28—C29—C35—C34−1.5 (6)
C5—C6—C7—C8−0.6 (10)C35—C34—C36—C370.6 (6)
C6—C7—C8—C9178.7 (5)C33—C34—C36—C37−179.2 (4)
C6—C7—C8—C31.2 (8)C34—C36—C37—C38−1.4 (7)
C2—C3—C8—C7177.6 (4)C35—N4—C38—C371.1 (7)
C4—C3—C8—C7−1.6 (6)Cu1—N4—C38—C37179.6 (3)
C2—C3—C8—C9−0.1 (6)C36—C37—C38—N40.5 (7)
C4—C3—C8—C9−179.3 (4)C43—N5—C39—C40−2.5 (7)
C7—C8—C9—C10−178.1 (5)Cu2—N5—C39—C40−179.3 (4)
C3—C8—C9—C10−0.6 (6)N5—C39—C40—C412.9 (9)
C7—C8—C9—C122.1 (7)C39—C40—C41—C42−1.4 (9)
C3—C8—C9—C12179.6 (3)C40—C41—C42—C43−0.2 (8)
C8—C9—C10—C110.8 (7)C40—C41—C42—C44−179.1 (5)
C12—C9—C10—C11−179.3 (4)C39—N5—C43—C420.8 (6)
C3—C2—C11—C10−0.3 (6)Cu2—N5—C43—C42178.1 (3)
C1—C2—C11—C10180.0 (4)C39—N5—C43—C49−179.8 (4)
C9—C10—C11—C2−0.4 (7)Cu2—N5—C43—C49−2.6 (4)
Cu2—O3—C12—O4−3.8 (3)C41—C42—C43—N50.5 (7)
Cu2—O3—C12—C9176.4 (2)C44—C42—C43—N5179.5 (4)
C10—C9—C12—O4−142.3 (4)C41—C42—C43—C49−178.8 (4)
C8—C9—C12—O437.5 (4)C44—C42—C43—C490.2 (6)
C10—C9—C12—O337.5 (4)C45—N6—C44—C471.4 (7)
C8—C9—C12—O3−142.7 (4)C45—N6—C44—C42−179.9 (5)
Cu1—O5—C13—O6−7.4 (4)C41—C42—C44—N6−0.2 (7)
Cu1i—O5—C13—O6171.9 (4)C43—C42—C44—N6−179.1 (4)
Cu1—O5—C13—C14172.7 (3)C41—C42—C44—C47178.6 (5)
Cu1i—O5—C13—C14−8.0 (4)C43—C42—C44—C47−0.4 (6)
O6—C13—C14—C23−91.8 (5)C44—N6—C45—C46−0.4 (9)
O5—C13—C14—C2388.0 (5)N6—C45—C46—N7−1.4 (11)
O6—C13—C14—C1588.7 (5)C47—N7—C46—C451.9 (9)
O5—C13—C14—C15−91.4 (5)C46—N7—C47—C44−0.8 (7)
C23—C14—C15—C16178.7 (5)C46—N7—C47—C48179.9 (5)
C13—C14—C15—C16−1.8 (7)N6—C44—C47—N7−0.8 (7)
C23—C14—C15—C20−2.2 (7)C42—C44—C47—N7−179.5 (4)
C13—C14—C15—C20177.2 (4)N6—C44—C47—C48178.5 (4)
C14—C15—C16—C17179.5 (5)C42—C44—C47—C48−0.3 (7)
C20—C15—C16—C170.5 (8)N7—C47—C48—C50−1.1 (7)
C15—C16—C17—C180.0 (9)C44—C47—C48—C50179.6 (5)
C16—C17—C18—C19−0.7 (9)N7—C47—C48—C49−179.7 (4)
C17—C18—C19—C201.0 (9)C44—C47—C48—C491.1 (7)
C18—C19—C20—C21177.7 (5)C52—N8—C49—C48−0.1 (6)
C18—C19—C20—C15−0.5 (7)Cu2—N8—C49—C48−179.8 (3)
C14—C15—C20—C212.4 (6)C52—N8—C49—C43178.9 (4)
C16—C15—C20—C21−178.5 (4)Cu2—N8—C49—C43−0.8 (5)
C14—C15—C20—C19−179.3 (4)C50—C48—C49—N8−0.9 (7)
C16—C15—C20—C19−0.2 (7)C47—C48—C49—N8177.7 (4)
C19—C20—C21—C22−178.3 (4)C50—C48—C49—C43−179.9 (4)
C15—C20—C21—C22−0.1 (6)C47—C48—C49—C43−1.2 (6)
C19—C20—C21—C240.3 (6)N5—C43—C49—N82.2 (5)
C15—C20—C21—C24178.5 (4)C42—C43—C49—N8−178.4 (4)
C20—C21—C22—C23−2.4 (7)N5—C43—C49—C48−178.7 (4)
C24—C21—C22—C23178.9 (4)C42—C43—C49—C480.6 (6)
C15—C14—C23—C22−0.3 (7)C49—C48—C50—C511.5 (7)
C13—C14—C23—C22−179.7 (4)C47—C48—C50—C51−177.1 (5)
C21—C22—C23—C142.7 (7)C48—C50—C51—C52−1.0 (8)
Cu2iv—O7—C24—O810.8 (3)C49—N8—C52—C510.6 (7)
Cu2iii—O7—C24—O8−145.8 (3)Cu2—N8—C52—C51−179.8 (4)
Cu2iv—O7—C24—C21−169.6 (2)C50—C51—C52—N80.0 (8)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z−1; (iii) −x+2, −y, −z+1; (iv) x, y, z+1.
Table 1
Selected geometric parameters (Å) top
Cu1—O11.924 (3)Cu1—N42.037 (3)
Cu1—O51.965 (2)Cu2—O31.916 (3)
Cu1—O5i2.440 (3)Cu2—O7ii1.964 (2)
Cu1—N12.012 (3)Cu2—O7iii2.348 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z−1; (iii) −x+2, −y, −z+1.
Acknowledgements top

The work was supported by the Natural Science Foundation of Jilin Province (No. 20060516), the Doctoral Foundation of Jilin Normal University (No. 2006006), the Science and Technology Institute Foundation of Siping City (No.2005016) and the Subject and Base Construction Foundation of Jilin Normal University (No. 2006041). The authors thank Jilin Normal University and the University of Malaya for supporting this study.

references
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