supplementary materials


cv5353 scheme

Acta Cryst. (2012). E68, m1484-m1485    [ doi:10.1107/S1600536812046041 ]

Poly[[[mu]-aqua-diaquabis([mu]-furan-2,5-dicarboxylato-[kappa]2O2:O5)bis(1,10-phenanthroline-[kappa]2N,N')dicopper(II)] N,N-dimethylformamide monosolvate]

Y.-F. Li, X.-L. Qin, Y. Xu, Y.-P. Yuan and W.-Y. Gao

Abstract top

The asymmetric unit of the title compound, {[Cu2(C6H2O5)2(C12H8N2)2(H2O)3]·C3H7NO}n, contains two CuII atoms, two furan-2,5-dicarboxylate (L) ligands, two 1,10-phenanthroline (phen) ligands, three coordinating water molecules and one N,N-dimethylformamide solvent molecule. Each CuII atom is coordinated by two N atoms from one phen ligand, two O atoms from two L ligands and two water molecules in a distorted octahedral geometry. The main difference between the environments of the two independent Cu atoms is in the Cu-Owater distances, which are 2.415 (2) and 2.639 (2) Å for one CuII atom and 2.3560 (19) and 2.911 (4) Å for the other. Ligands L and one independent water molecule bridge the CuII atoms, forming corrugated polymeric layers parallel to the ab plane. Intermolecular O-H...O and C-H...O hydrogen bonds consolidate the crystal packing.

Comment top

As the analogous structure of BDC (benzene-1,4-dicarboxyl acid), FDA (furan-2,5-dicarboxyl acid) attracts attention owing to the bond angle of two carboxyl groups about 126°. Recently, we utilized furan-2,5-dicarboxyl acid as the ligand to construct coordination polymers (Li et al., 2012). As an extension of that work, herewith we present the crystal structure of the title compound, [[CuL(H2O)(phen)]2.H2O]n .nDMFA (L = furan-2,5-dicarboxylato, phen = 1,10-phenanthroline, DMFA = N,N-dimethylformamide) (I).

The asymmetric unit of (I) contains two CuII cations, two anionic ligands L, two ligands phen, three coordinated water molecules and one DMFA solvent molecule (Fig.1). Each copper center is coordinated by two N atoms from one phen ligand, two O atoms from two ligands L and two water molecules in a distorted octahedral geometry. The main difference in environment of two independent Cu atoms is the difference in Cu—Owater distances, which are equal to 2.415 (2) and 2.639 (2) Å for one Cu atom and 2.3560 (19) and 2.911 (4) Å for another. Ligands L and one independent water molecule bridge copper centers into corrugated polymeric layers prallel to ab plane (Fig.2). Intermolecular O—H···O and C—H···O hydrogen bonds (Table 1) consolidate the crystal packing.

Related literature top

For a related structure, see: Li et al. (2012).

Experimental top

Furan-2,5-dicarboxyl acid (0.0156 g, 0.10 mmol), Cu(NO3)2.3H2O (0.0244 g, 0.10 mmol), and 1,10-phenanthroline (0.0180, 0.10 mmol) were dissolved in DMFA (5 ml, 75 mmol) under stirring. The mixture with molar ratio of 1 (furan-2,5-dicarboxyl acid): 1 (Cu(NO3)2.3H2O): 1 (1,10-phenanthroline): 750 DMFA was layed under room temperature for 8 days. The blue block product was collected as a single phase.

Refinement top

Water H atoms were located in a difference Fourier map and refined with restraints O—H = 0.86 (2) Å, and Uiso(H) = 1.2Ueq(O). C-bound H-atoms were placed in calculated positions (C—H 0.93–0.96 Å), and were included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of (I), showing the atomic labelling scheme and displacement ellipsoids drawn at the 50% probability level [symmetry codes: (i) 1 + x, y, z; (ii) 1 - x, 0.5 + y, 0.5 - z.]
[Figure 2] Fig. 2. A portion of the crystal packing of (I) viewed along the c axis and showing the coordination environment of Cu centers as polyhedron.
Poly[[µ-aqua-diaquabis(µ-furan-2,5-dicarboxylato- κ2O2:O5)bis(1,10-phenanthroline- κ2N,N')dicopper(II)] N,N-dimethylformamide monosolvate] top
Crystal data top
[Cu2(C6H2O5)2(C12H8N2)2(H2O)3]·C3H7NOF(000) = 1888
Mr = 922.78Dx = 1.578 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2000 reflections
a = 16.620 (3) Åθ = 1.2–27.5°
b = 11.600 (2) ŵ = 1.17 mm1
c = 20.168 (4) ÅT = 293 K
β = 92.41 (3)°Block, blue
V = 3884.6 (13) Å30.35 × 0.20 × 0.17 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
8855 independent reflections
Radiation source: fine-focus sealed tube6642 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 1.2°
ω scansh = 2021
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 1515
Tmin = 0.685, Tmax = 0.826l = 2626
36308 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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0551P)2 + 1.1821P]
where P = (Fo2 + 2Fc2)/3
8855 reflections(Δ/σ)max = 0.001
561 parametersΔρmax = 0.65 e Å3
13 restraintsΔρmin = 0.35 e Å3
Crystal data top
[Cu2(C6H2O5)2(C12H8N2)2(H2O)3]·C3H7NOV = 3884.6 (13) Å3
Mr = 922.78Z = 4
Monoclinic, P21/cMo Kα radiation
a = 16.620 (3) ŵ = 1.17 mm1
b = 11.600 (2) ÅT = 293 K
c = 20.168 (4) Å0.35 × 0.20 × 0.17 mm
β = 92.41 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
8855 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
6642 reflections with I > 2σ(I)
Tmin = 0.685, Tmax = 0.826Rint = 0.047
36308 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110Δρmax = 0.65 e Å3
S = 1.05Δρmin = 0.35 e Å3
8855 reflectionsAbsolute structure: ?
561 parametersFlack parameter: ?
13 restraintsRogers parameter: ?
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*/Ueq
Cu10.262045 (16)0.46824 (3)0.095417 (14)0.03123 (9)
Cu20.778317 (16)0.54556 (3)0.415298 (14)0.03424 (10)
O10.34174 (10)0.45626 (16)0.16869 (9)0.0380 (4)
O20.40602 (11)0.62411 (17)0.15533 (10)0.0467 (5)
O30.51971 (10)0.55941 (14)0.25061 (8)0.0325 (4)
O40.68947 (10)0.49579 (18)0.35584 (9)0.0412 (4)
O50.64533 (13)0.66569 (18)0.31577 (12)0.0610 (6)
C10.39872 (14)0.5275 (2)0.17983 (11)0.0313 (5)
C20.46290 (13)0.4827 (2)0.22686 (11)0.0298 (5)
C30.47776 (14)0.3759 (2)0.25122 (12)0.0350 (5)
H30.44780.30950.24250.042*
C40.54854 (14)0.3858 (2)0.29291 (12)0.0348 (5)
H40.57400.32670.31690.042*
C50.57159 (14)0.4961 (2)0.29108 (11)0.0305 (5)
C60.64101 (15)0.5605 (2)0.32343 (12)0.0345 (5)
O60.17981 (10)0.52844 (16)0.15262 (9)0.0369 (4)
O70.10622 (13)0.36742 (18)0.15767 (12)0.0588 (6)
O80.00890 (10)0.46740 (14)0.24548 (8)0.0315 (4)
O90.14260 (11)0.57111 (16)0.34843 (10)0.0405 (4)
O100.11593 (13)0.39158 (18)0.31678 (12)0.0612 (6)
C70.12146 (14)0.4682 (2)0.17212 (12)0.0323 (5)
C80.06639 (13)0.5318 (2)0.21566 (12)0.0300 (5)
C90.05879 (15)0.6436 (2)0.23144 (13)0.0376 (6)
H90.09080.70410.21760.045*
C100.00770 (15)0.6518 (2)0.27353 (13)0.0377 (6)
H100.02770.71850.29240.045*
C110.03577 (13)0.5440 (2)0.28061 (11)0.0297 (5)
C120.10354 (14)0.4955 (2)0.31801 (12)0.0323 (5)
N10.19302 (12)0.4938 (2)0.01174 (11)0.0373 (5)
N20.34234 (12)0.4163 (2)0.02842 (11)0.0367 (5)
C130.11996 (16)0.5389 (3)0.00524 (16)0.0502 (7)
H130.09450.56300.04300.060*
C140.07967 (19)0.5515 (3)0.05710 (18)0.0649 (10)
H140.02850.58410.06020.078*
C150.1155 (2)0.5162 (4)0.11220 (18)0.0689 (10)
H150.08870.52340.15340.083*
C160.1937 (2)0.4683 (3)0.10785 (15)0.0551 (8)
C170.2383 (3)0.4298 (4)0.16290 (16)0.0724 (11)
H170.21490.43400.20550.087*
C180.3126 (3)0.3879 (3)0.15429 (16)0.0687 (10)
H180.33990.36370.19110.082*
C190.35201 (19)0.3792 (3)0.08942 (15)0.0514 (7)
C200.4306 (2)0.3379 (3)0.07688 (19)0.0665 (10)
H200.46100.31240.11160.080*
C210.4615 (2)0.3356 (3)0.0137 (2)0.0688 (10)
H210.51320.30730.00500.083*
C220.41626 (16)0.3754 (3)0.03824 (16)0.0526 (8)
H220.43880.37320.08120.063*
C230.31052 (16)0.4169 (2)0.03446 (13)0.0385 (6)
C240.23022 (17)0.4602 (2)0.04374 (13)0.0396 (6)
N30.70653 (14)0.5346 (2)0.49399 (11)0.0441 (6)
N40.85693 (13)0.6052 (2)0.48709 (12)0.0446 (5)
C250.63292 (18)0.4888 (4)0.49529 (17)0.0615 (9)
H250.60800.46310.45590.074*
C260.5921 (2)0.4784 (4)0.5545 (2)0.0810 (13)
H260.54120.44510.55420.097*
C270.6266 (3)0.5165 (4)0.6111 (2)0.0846 (14)
H270.59870.51140.65000.101*
C280.7044 (3)0.5642 (3)0.61325 (16)0.0701 (11)
C290.7473 (3)0.6017 (4)0.67048 (18)0.0837 (14)
H290.72290.59890.71110.100*
C300.8223 (3)0.6412 (3)0.66776 (16)0.0811 (14)
H300.84840.66740.70660.097*
C310.8645 (3)0.6449 (3)0.60622 (18)0.0682 (10)
C320.9437 (3)0.6788 (4)0.5992 (2)0.0887 (14)
H320.97380.70380.63640.106*
C330.9790 (3)0.6765 (4)0.5388 (3)0.0861 (14)
H331.03230.69910.53510.103*
C340.9324 (2)0.6387 (3)0.48203 (19)0.0639 (9)
H340.95540.63750.44080.077*
C350.8235 (2)0.6091 (3)0.54787 (13)0.0497 (7)
C360.74293 (19)0.5699 (3)0.55125 (13)0.0478 (7)
O1W0.23887 (10)0.26884 (16)0.10600 (9)0.0363 (4)
H1A0.2766 (12)0.245 (2)0.1317 (12)0.044*
H1B0.1959 (11)0.275 (3)0.1272 (12)0.044*
O2W0.81807 (12)0.34807 (19)0.43587 (11)0.0526 (5)
H2A0.8410 (17)0.3280 (17)0.3991 (11)0.063*
H2B0.7755 (13)0.3099 (16)0.4451 (15)0.063*
O3W0.30778 (18)0.6991 (3)0.05478 (13)0.0923 (10)
H3A0.346 (2)0.725 (2)0.0796 (14)0.111*
H3B0.324 (2)0.696 (2)0.0140 (10)0.111*
O410.6377 (2)0.3137 (3)0.07231 (14)0.1025 (10)
C410.6527 (3)0.2954 (4)0.1319 (2)0.0811 (12)
H410.61380.31700.16140.097*
N410.71914 (18)0.2478 (3)0.15731 (15)0.0652 (8)
C420.7841 (3)0.2158 (4)0.1167 (2)0.0884 (13)
H42A0.79540.13520.12240.106*
H42B0.83110.25990.12950.106*
H42C0.76930.23090.07100.106*
C430.7313 (3)0.2344 (5)0.2284 (2)0.1029 (17)
H43A0.77280.28620.24440.123*
H43B0.74710.15650.23840.123*
H43C0.68210.25170.24970.123*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02015 (14)0.04554 (19)0.02800 (15)0.00042 (11)0.00089 (11)0.00221 (13)
Cu20.02092 (15)0.0551 (2)0.02665 (15)0.00089 (12)0.00027 (11)0.00304 (13)
O10.0264 (8)0.0488 (11)0.0381 (9)0.0065 (7)0.0071 (7)0.0013 (8)
O20.0433 (10)0.0450 (11)0.0507 (11)0.0018 (9)0.0121 (9)0.0099 (9)
O30.0292 (8)0.0323 (9)0.0350 (9)0.0030 (7)0.0098 (7)0.0003 (7)
O40.0298 (9)0.0540 (11)0.0388 (10)0.0016 (8)0.0115 (8)0.0034 (9)
O50.0560 (13)0.0407 (12)0.0833 (16)0.0055 (10)0.0351 (12)0.0044 (11)
C10.0266 (11)0.0412 (14)0.0259 (11)0.0018 (10)0.0007 (9)0.0059 (10)
C20.0228 (10)0.0384 (13)0.0280 (11)0.0051 (9)0.0003 (9)0.0043 (10)
C30.0319 (12)0.0349 (13)0.0380 (13)0.0050 (10)0.0016 (10)0.0012 (11)
C40.0323 (12)0.0369 (13)0.0350 (12)0.0014 (10)0.0027 (10)0.0044 (11)
C50.0252 (11)0.0370 (13)0.0288 (11)0.0002 (10)0.0050 (9)0.0004 (10)
C60.0302 (12)0.0430 (15)0.0296 (12)0.0007 (11)0.0058 (10)0.0038 (11)
O60.0271 (8)0.0448 (11)0.0395 (9)0.0021 (7)0.0106 (7)0.0035 (8)
O70.0561 (13)0.0419 (12)0.0816 (16)0.0090 (10)0.0394 (12)0.0160 (11)
O80.0282 (8)0.0338 (9)0.0334 (8)0.0005 (7)0.0106 (7)0.0026 (7)
O90.0346 (9)0.0388 (10)0.0494 (11)0.0030 (8)0.0188 (8)0.0034 (8)
O100.0621 (13)0.0383 (11)0.0867 (16)0.0095 (10)0.0429 (13)0.0124 (11)
C70.0280 (11)0.0409 (14)0.0283 (11)0.0035 (10)0.0040 (9)0.0012 (11)
C80.0229 (10)0.0362 (13)0.0313 (11)0.0007 (9)0.0056 (9)0.0054 (10)
C90.0326 (12)0.0360 (14)0.0448 (14)0.0007 (10)0.0086 (11)0.0062 (11)
C100.0361 (13)0.0332 (13)0.0448 (14)0.0054 (10)0.0130 (11)0.0004 (11)
C110.0249 (11)0.0349 (13)0.0295 (11)0.0041 (9)0.0043 (9)0.0009 (10)
C120.0268 (11)0.0376 (14)0.0328 (12)0.0001 (10)0.0045 (10)0.0025 (11)
N10.0281 (10)0.0477 (13)0.0360 (11)0.0030 (9)0.0001 (9)0.0071 (10)
N20.0289 (10)0.0427 (12)0.0391 (11)0.0007 (9)0.0068 (9)0.0002 (10)
C130.0308 (13)0.065 (2)0.0545 (17)0.0023 (13)0.0026 (12)0.0159 (15)
C140.0389 (16)0.085 (3)0.069 (2)0.0039 (16)0.0200 (16)0.0269 (19)
C150.063 (2)0.090 (3)0.0510 (19)0.016 (2)0.0246 (17)0.0140 (19)
C160.063 (2)0.062 (2)0.0390 (15)0.0121 (16)0.0092 (14)0.0043 (14)
C170.102 (3)0.084 (3)0.0308 (15)0.016 (2)0.0045 (18)0.0045 (16)
C180.098 (3)0.076 (3)0.0338 (16)0.009 (2)0.0204 (18)0.0112 (16)
C190.0619 (19)0.0504 (18)0.0436 (16)0.0086 (14)0.0227 (14)0.0066 (13)
C200.064 (2)0.070 (2)0.069 (2)0.0006 (17)0.0360 (19)0.0154 (18)
C210.0406 (17)0.081 (3)0.086 (3)0.0116 (16)0.0205 (17)0.012 (2)
C220.0337 (14)0.067 (2)0.0572 (18)0.0096 (13)0.0067 (13)0.0044 (16)
C230.0420 (14)0.0387 (14)0.0354 (13)0.0076 (11)0.0082 (11)0.0020 (11)
C240.0449 (15)0.0433 (15)0.0304 (12)0.0112 (12)0.0012 (11)0.0015 (11)
N30.0367 (12)0.0621 (16)0.0340 (11)0.0132 (11)0.0054 (9)0.0039 (11)
N40.0375 (12)0.0483 (14)0.0468 (13)0.0019 (10)0.0143 (10)0.0010 (11)
C250.0352 (15)0.094 (3)0.0561 (19)0.0088 (16)0.0133 (14)0.0140 (18)
C260.052 (2)0.128 (4)0.065 (2)0.020 (2)0.0275 (19)0.022 (2)
C270.074 (3)0.121 (4)0.062 (2)0.042 (3)0.038 (2)0.019 (2)
C280.106 (3)0.071 (2)0.0335 (15)0.039 (2)0.0108 (18)0.0031 (15)
C290.125 (4)0.086 (3)0.0391 (19)0.035 (3)0.002 (2)0.0050 (19)
C300.144 (4)0.067 (2)0.0304 (16)0.027 (3)0.026 (2)0.0117 (15)
C310.095 (3)0.0497 (19)0.057 (2)0.0103 (19)0.035 (2)0.0083 (16)
C320.123 (4)0.070 (3)0.069 (3)0.008 (3)0.049 (3)0.005 (2)
C330.065 (2)0.071 (3)0.118 (4)0.017 (2)0.044 (2)0.003 (3)
C340.0469 (18)0.068 (2)0.075 (2)0.0107 (16)0.0198 (16)0.0042 (18)
C350.073 (2)0.0410 (15)0.0330 (14)0.0157 (15)0.0177 (14)0.0027 (12)
C360.0608 (19)0.0508 (17)0.0318 (13)0.0207 (15)0.0020 (13)0.0019 (12)
O1W0.0258 (8)0.0385 (10)0.0445 (10)0.0016 (8)0.0001 (7)0.0031 (8)
O2W0.0401 (11)0.0572 (13)0.0609 (13)0.0075 (9)0.0050 (10)0.0044 (11)
O3W0.087 (2)0.128 (3)0.0601 (16)0.0616 (19)0.0142 (14)0.0162 (17)
O410.115 (2)0.133 (3)0.0584 (17)0.014 (2)0.0119 (16)0.0129 (18)
C410.077 (3)0.102 (3)0.065 (2)0.016 (2)0.005 (2)0.004 (2)
N410.0630 (17)0.074 (2)0.0591 (17)0.0050 (15)0.0052 (14)0.0023 (15)
C420.085 (3)0.072 (3)0.111 (3)0.008 (2)0.033 (3)0.013 (3)
C430.090 (3)0.149 (5)0.069 (3)0.038 (3)0.004 (2)0.002 (3)
Geometric parameters (Å, º) top
Cu1—O11.9475 (18)C17—C181.332 (6)
Cu1—O61.9542 (17)C17—H170.9300
Cu1—N12.022 (2)C18—C191.442 (5)
Cu1—N22.030 (2)C18—H180.9300
Cu1—O1W2.3560 (19)C19—C231.400 (4)
Cu1—O3W2.911 (4)C19—C201.404 (5)
Cu2—O9i1.9449 (18)C20—C211.353 (5)
Cu2—O41.9501 (18)C20—H200.9300
Cu2—N32.029 (2)C21—C221.394 (4)
Cu2—N42.031 (2)C21—H210.9300
Cu2—O2W2.415 (2)C22—H220.9300
Cu2—O1Wii2.639 (2)C23—C241.431 (4)
O1—C11.270 (3)N3—C251.335 (4)
O2—C11.232 (3)N3—C361.345 (4)
O3—C21.369 (3)N4—C341.321 (4)
O3—C51.375 (3)N4—C351.368 (4)
O4—C61.263 (3)C25—C261.403 (4)
O5—C61.233 (3)C25—H250.9300
C1—O21.232 (3)C26—C271.332 (6)
C1—C21.491 (3)C26—H260.9300
C2—C31.352 (3)C27—C281.405 (6)
C3—C41.422 (3)C27—H270.9300
C3—H30.9300C28—C291.400 (6)
C4—C51.337 (4)C28—C361.430 (4)
C4—H40.9300C29—C301.332 (6)
C5—C61.501 (3)C29—H290.9300
C6—O41.263 (3)C30—C311.453 (6)
O6—C71.271 (3)C30—H300.9300
O7—C71.228 (3)C31—C321.386 (6)
O8—C81.371 (3)C31—C351.398 (4)
O8—C111.373 (3)C32—C331.374 (6)
O9—C121.265 (3)C32—H320.9300
O10—C121.223 (3)C33—C341.424 (5)
C7—O71.228 (3)C33—H330.9300
C7—C81.490 (3)C34—H340.9300
C8—C91.343 (4)C35—C361.419 (5)
C9—C101.425 (3)O1W—H1A0.843 (16)
C9—H90.9300O1W—H1B0.851 (16)
C10—C111.345 (4)O2W—H2A0.880 (16)
C10—H100.9300O2W—H2B0.862 (16)
C11—C121.491 (3)O3W—H3A0.846 (17)
N1—C131.324 (3)O3W—H3B0.878 (18)
N1—C241.358 (3)O41—C411.236 (5)
N2—C221.324 (3)C41—N411.319 (5)
N2—C231.353 (3)C41—H410.9300
C13—C141.407 (4)N41—C421.431 (5)
C13—H130.9300N41—C431.449 (5)
C14—C151.347 (5)C42—H42A0.9600
C14—H140.9300C42—H42B0.9600
C15—C161.413 (5)C42—H42C0.9600
C15—H150.9300C43—H43A0.9600
C16—C241.408 (4)C43—H43B0.9600
C16—C171.432 (5)C43—H43C0.9600
O1—Cu1—O692.74 (8)C16—C15—H15119.8
O1—Cu1—N1170.97 (8)C24—C16—C15116.3 (3)
O6—Cu1—N193.10 (8)C24—C16—C17118.3 (3)
O1—Cu1—N292.22 (8)C15—C16—C17125.4 (3)
O6—Cu1—N2174.04 (9)C18—C17—C16121.3 (3)
N1—Cu1—N281.59 (9)C18—C17—H17119.3
O1—Cu1—O1W88.27 (7)C16—C17—H17119.3
O6—Cu1—O1W100.15 (7)C17—C18—C19121.8 (3)
N1—Cu1—O1W97.48 (8)C17—C18—H18119.1
N2—Cu1—O1W83.30 (8)C19—C18—H18119.1
O1—Cu1—O3W95.85 (8)C23—C19—C20116.7 (3)
O6—Cu1—O3W92.00 (7)C23—C19—C18118.5 (3)
N1—Cu1—O3W77.06 (8)C20—C19—C18124.8 (3)
N2—Cu1—O3W84.21 (8)C21—C20—C19119.3 (3)
O1W—Cu1—O3W166.98 (7)C21—C20—H20120.3
O9i—Cu2—O497.76 (8)C19—C20—H20120.3
O9i—Cu2—O497.76 (8)C20—C21—C22120.3 (3)
O4—Cu2—O40.00 (13)C20—C21—H21119.8
O9i—Cu2—N3171.30 (9)C22—C21—H21119.8
O4—Cu2—N390.43 (9)N2—C22—C21122.2 (3)
O4—Cu2—N390.43 (9)N2—C22—H22118.9
O9i—Cu2—N490.52 (9)C21—C22—H22118.9
O4—Cu2—N4170.84 (9)N2—C23—C19123.7 (3)
O4—Cu2—N4170.84 (9)N2—C23—C24116.7 (2)
N3—Cu2—N481.11 (10)C19—C23—C24119.6 (3)
O9i—Cu2—O2W94.34 (7)N1—C24—C16123.0 (3)
O4—Cu2—O2W91.11 (8)N1—C24—C23116.6 (2)
O4—Cu2—O2W91.11 (8)C16—C24—C23120.5 (3)
N3—Cu2—O2W88.39 (9)C25—N3—C36118.9 (3)
N4—Cu2—O2W92.15 (9)C25—N3—Cu2127.6 (2)
O9i—Cu2—O1Wii79.01 (7)C36—N3—Cu2113.2 (2)
O4—Cu2—O1Wii96.69 (7)C34—N4—C35118.8 (3)
O4—Cu2—O1Wii96.69 (7)C34—N4—Cu2129.0 (2)
N3—Cu2—O1Wii97.21 (8)C35—N4—Cu2112.15 (19)
N4—Cu2—O1Wii81.01 (8)N3—C25—C26121.8 (4)
O2W—Cu2—O1Wii170.34 (6)N3—C25—H25119.1
C1—O1—Cu1124.47 (16)C26—C25—H25119.1
C2—O3—C5105.45 (18)C27—C26—C25119.7 (4)
C6—O4—Cu2126.33 (18)C27—C26—H26120.2
O2—C1—O1127.3 (2)C25—C26—H26120.2
O2—C1—O1127.3 (2)C26—C27—C28121.3 (3)
O2—C1—C2119.5 (2)C26—C27—H27119.4
O2—C1—C2119.5 (2)C28—C27—H27119.4
O1—C1—C2113.2 (2)C29—C28—C27125.7 (4)
C3—C2—O3110.8 (2)C29—C28—C36118.4 (4)
C3—C2—C1131.7 (2)C27—C28—C36115.9 (3)
O3—C2—C1117.4 (2)C30—C29—C28121.2 (4)
C2—C3—C4106.0 (2)C30—C29—H29119.4
C2—C3—H3127.0C28—C29—H29119.4
C4—C3—H3127.0C29—C30—C31122.2 (3)
C5—C4—C3107.0 (2)C29—C30—H30118.9
C5—C4—H4126.5C31—C30—H30118.9
C3—C4—H4126.5C32—C31—C35115.4 (4)
C4—C5—O3110.8 (2)C32—C31—C30126.2 (4)
C4—C5—C6132.9 (2)C35—C31—C30118.3 (4)
O3—C5—C6116.3 (2)C33—C32—C31121.8 (4)
O5—C6—O4127.9 (2)C33—C32—H32119.1
O5—C6—O4127.9 (2)C31—C32—H32119.1
O5—C6—C5119.1 (2)C32—C33—C34118.7 (4)
O4—C6—C5113.0 (2)C32—C33—H33120.6
O4—C6—C5113.0 (2)C34—C33—H33120.6
C7—O6—Cu1123.21 (16)N4—C34—C33120.9 (4)
C8—O8—C11106.02 (18)N4—C34—H34119.5
C12—O9—Cu2iii127.33 (17)C33—C34—H34119.5
O7—C7—O6127.0 (2)N4—C35—C31124.2 (3)
O7—C7—O6127.0 (2)N4—C35—C36116.9 (2)
O7—C7—C8119.0 (2)C31—C35—C36118.9 (3)
O7—C7—C8119.0 (2)N3—C36—C35116.6 (2)
O6—C7—C8113.9 (2)N3—C36—C28122.3 (3)
C9—C8—O8110.3 (2)C35—C36—C28121.0 (3)
C9—C8—C7133.2 (2)Cu1—O1W—H1A105 (2)
O8—C8—C7116.5 (2)Cu1—O1W—H1B96 (2)
C8—C9—C10106.8 (2)H1A—O1W—H1B110 (2)
C8—C9—H9126.6Cu2—O2W—H2A103.3 (14)
C10—C9—H9126.6Cu2—O2W—H2B107.6 (14)
C11—C10—C9106.4 (2)H2A—O2W—H2B116 (2)
C11—C10—H10126.8Cu1—O3W—H3A111.3 (17)
C9—C10—H10126.8Cu1—O3W—H3B108.4 (16)
C10—C11—O8110.5 (2)H3A—O3W—H3B108 (2)
C10—C11—C12132.6 (2)O41—C41—N41125.6 (4)
O8—C11—C12117.0 (2)O41—C41—H41117.2
O10—C12—O9127.1 (2)N41—C41—H41117.2
O10—C12—C11119.4 (2)C41—N41—C42121.7 (4)
O9—C12—C11113.5 (2)C41—N41—C43120.6 (3)
C13—N1—C24118.6 (2)C42—N41—C43117.5 (4)
C13—N1—Cu1128.8 (2)N41—C42—H42A109.5
C24—N1—Cu1112.57 (17)N41—C42—H42B109.5
C22—N2—C23117.8 (2)H42A—C42—H42B109.5
C22—N2—Cu1129.7 (2)N41—C42—H42C109.5
C23—N2—Cu1112.34 (17)H42A—C42—H42C109.5
N1—C13—C14122.0 (3)H42B—C42—H42C109.5
N1—C13—H13119.0N41—C43—H43A109.5
C14—C13—H13119.0N41—C43—H43B109.5
C15—C14—C13119.7 (3)H43A—C43—H43B109.5
C15—C14—H14120.2N41—C43—H43C109.5
C13—C14—H14120.2H43A—C43—H43C109.5
C14—C15—C16120.4 (3)H43B—C43—H43C109.5
C14—C15—H15119.8
O6—Cu1—O1—C1101.97 (19)C13—C14—C15—C161.0 (6)
N2—Cu1—O1—C174.7 (2)C14—C15—C16—C240.1 (5)
O1W—Cu1—O1—C1157.95 (19)C14—C15—C16—C17178.8 (4)
O3W—Cu1—O1—C19.7 (2)C24—C16—C17—C180.4 (6)
O9i—Cu2—O4—O40.00 (13)C15—C16—C17—C18178.5 (4)
N3—Cu2—O4—O40.00 (12)C16—C17—C18—C190.0 (6)
O2W—Cu2—O4—O40.00 (12)C17—C18—C19—C230.5 (5)
O1Wii—Cu2—O4—O40.00 (13)C17—C18—C19—C20178.9 (4)
O9i—Cu2—O4—C683.2 (2)C23—C19—C20—C210.5 (5)
O4—Cu2—O4—C60 (17)C18—C19—C20—C21178.9 (4)
N3—Cu2—O4—C693.9 (2)C19—C20—C21—C220.9 (6)
O2W—Cu2—O4—C6177.7 (2)C23—N2—C22—C211.0 (5)
O1Wii—Cu2—O4—C63.4 (2)Cu1—N2—C22—C21175.2 (3)
O2—O2—C1—O10.0 (2)C20—C21—C22—N20.2 (6)
O2—O2—C1—C20.0 (3)C22—N2—C23—C191.4 (4)
Cu1—O1—C1—O213.8 (4)Cu1—N2—C23—C19176.6 (2)
Cu1—O1—C1—O213.8 (4)C22—N2—C23—C24179.3 (3)
Cu1—O1—C1—C2164.53 (15)Cu1—N2—C23—C244.1 (3)
C5—O3—C2—C30.2 (3)C20—C19—C23—N20.7 (4)
C5—O3—C2—C1178.82 (19)C18—C19—C23—N2177.8 (3)
O2—C1—C2—C3166.5 (3)C20—C19—C23—C24179.9 (3)
O2—C1—C2—C3166.5 (3)C18—C19—C23—C241.4 (4)
O1—C1—C2—C311.9 (4)C13—N1—C24—C161.8 (4)
O2—C1—C2—O312.3 (3)Cu1—N1—C24—C16179.2 (2)
O2—C1—C2—O312.3 (3)C13—N1—C24—C23177.2 (3)
O1—C1—C2—O3169.3 (2)Cu1—N1—C24—C231.8 (3)
O3—C2—C3—C40.1 (3)C15—C16—C24—N11.3 (4)
C1—C2—C3—C4178.7 (2)C17—C16—C24—N1179.7 (3)
C2—C3—C4—C50.0 (3)C15—C16—C24—C23177.6 (3)
C3—C4—C5—O30.2 (3)C17—C16—C24—C231.4 (4)
C3—C4—C5—C6179.4 (3)N2—C23—C24—N11.6 (4)
C2—O3—C5—C40.2 (3)C19—C23—C24—N1179.1 (3)
C2—O3—C5—C6179.4 (2)N2—C23—C24—C16177.4 (3)
O4—O4—C6—O50.0 (2)C19—C23—C24—C161.9 (4)
Cu2—O4—C6—O510.0 (4)O4—Cu2—N3—C259.8 (3)
Cu2—O4—C6—O40 (100)O4—Cu2—N3—C259.8 (3)
O4—O4—C6—C50.00 (13)N4—Cu2—N3—C25173.8 (3)
Cu2—O4—C6—C5170.59 (15)O2W—Cu2—N3—C2581.3 (3)
C4—C5—C6—O5176.0 (3)O1Wii—Cu2—N3—C25106.6 (3)
O3—C5—C6—O54.5 (4)O4—Cu2—N3—C36176.3 (2)
C4—C5—C6—O44.5 (4)O4—Cu2—N3—C36176.3 (2)
O3—C5—C6—O4175.0 (2)N4—Cu2—N3—C360.2 (2)
C4—C5—C6—O44.5 (4)O2W—Cu2—N3—C3692.6 (2)
O3—C5—C6—O4175.0 (2)O1Wii—Cu2—N3—C3679.5 (2)
O1—Cu1—O6—C7104.07 (19)O9i—Cu2—N4—C343.3 (3)
N1—Cu1—O6—C782.8 (2)N3—Cu2—N4—C34179.1 (3)
O1W—Cu1—O6—C715.3 (2)O2W—Cu2—N4—C3491.1 (3)
O3W—Cu1—O6—C7159.97 (19)O1Wii—Cu2—N4—C3482.1 (3)
O7—O7—C7—O60.0 (3)O9i—Cu2—N4—C35176.79 (19)
O7—O7—C7—C80.0 (2)N3—Cu2—N4—C350.81 (19)
Cu1—O6—C7—O72.0 (4)O2W—Cu2—N4—C3588.8 (2)
Cu1—O6—C7—O72.0 (4)O1Wii—Cu2—N4—C3598.01 (19)
Cu1—O6—C7—C8179.69 (15)C36—N3—C25—C261.1 (5)
C11—O8—C8—C90.3 (3)Cu2—N3—C25—C26174.8 (3)
C11—O8—C8—C7177.9 (2)N3—C25—C26—C271.0 (6)
O7—C7—C8—C9167.6 (3)C25—C26—C27—C281.8 (7)
O7—C7—C8—C9167.6 (3)C26—C27—C28—C29176.9 (4)
O6—C7—C8—C910.9 (4)C26—C27—C28—C360.5 (6)
O7—C7—C8—O810.1 (4)C27—C28—C29—C30177.0 (4)
O7—C7—C8—O810.1 (4)C36—C28—C29—C300.3 (6)
O6—C7—C8—O8171.4 (2)C28—C29—C30—C311.8 (7)
O8—C8—C9—C100.3 (3)C29—C30—C31—C32176.4 (4)
C7—C8—C9—C10177.5 (3)C29—C30—C31—C352.2 (6)
C8—C9—C10—C110.2 (3)C35—C31—C32—C330.3 (6)
C9—C10—C11—O80.0 (3)C30—C31—C32—C33178.4 (4)
C9—C10—C11—C12180.0 (3)C31—C32—C33—C340.4 (6)
C8—O8—C11—C100.2 (3)C35—N4—C34—C331.0 (5)
C8—O8—C11—C12179.8 (2)Cu2—N4—C34—C33178.9 (3)
Cu2iii—O9—C12—O1012.0 (4)C32—C33—C34—N40.7 (6)
Cu2iii—O9—C12—C11167.91 (16)C34—N4—C35—C311.0 (5)
C10—C11—C12—O10179.1 (3)Cu2—N4—C35—C31178.9 (2)
O8—C11—C12—O100.9 (4)C34—N4—C35—C36178.6 (3)
C10—C11—C12—O90.8 (4)Cu2—N4—C35—C361.3 (3)
O8—C11—C12—O9179.1 (2)C32—C31—C35—N40.7 (5)
O6—Cu1—N1—C131.5 (3)C30—C31—C35—N4178.1 (3)
N2—Cu1—N1—C13175.8 (3)C32—C31—C35—C36178.2 (3)
O1W—Cu1—N1—C13102.2 (3)C30—C31—C35—C360.6 (5)
O3W—Cu1—N1—C1389.8 (3)C25—N3—C36—C35175.0 (3)
O6—Cu1—N1—C24179.65 (18)Cu2—N3—C36—C350.4 (3)
N2—Cu1—N1—C243.06 (18)C25—N3—C36—C282.4 (4)
O1W—Cu1—N1—C2478.98 (18)Cu2—N3—C36—C28177.0 (2)
O3W—Cu1—N1—C2489.01 (18)N4—C35—C36—N31.2 (4)
O1—Cu1—N2—C228.2 (3)C31—C35—C36—N3178.9 (3)
N1—Cu1—N2—C22178.4 (3)N4—C35—C36—C28176.3 (3)
O1W—Cu1—N2—C2279.8 (3)C31—C35—C36—C281.5 (4)
O3W—Cu1—N2—C22103.9 (3)C29—C28—C36—N3179.3 (3)
O1—Cu1—N2—C23177.29 (18)C27—C28—C36—N31.6 (5)
N1—Cu1—N2—C233.90 (18)C29—C28—C36—C352.0 (5)
O1W—Cu1—N2—C2394.72 (18)C27—C28—C36—C35175.7 (3)
O3W—Cu1—N2—C2381.63 (18)O41—O41—C41—N410.0 (3)
C24—N1—C13—C140.9 (4)O41—C41—N41—C422.6 (7)
Cu1—N1—C13—C14179.6 (2)O41—C41—N41—C43177.8 (5)
N1—C13—C14—C150.5 (5)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y+1/2, z+1/2; (iii) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···O5iv0.84 (2)1.88 (2)2.715 (3)170 (3)
O1W—H1B···O70.85 (2)1.96 (2)2.729 (3)151 (3)
O2W—H2A···O10i0.88 (2)1.98 (2)2.729 (3)143 (2)
O2W—H2B···O3Wiv0.86 (2)1.89 (2)2.726 (3)163 (3)
O3W—H3A···O20.85 (2)2.14 (3)2.694 (3)123 (2)
O3W—H3B···O41v0.88 (2)1.88 (2)2.758 (4)178 (4)
C3—H3···O5iv0.932.533.424 (3)161
C4—H4···O2iv0.932.443.287 (3)152
C9—H9···O10vi0.932.333.193 (3)155
C10—H10···O7vi0.932.413.324 (3)168
C15—H15···O8vii0.932.423.327 (4)166
C18—H18···O5v0.932.563.416 (4)154
C20—H20···O2v0.932.523.230 (4)133
C21—H21···O410.932.543.349 (5)146
C33—H33···O2Wviii0.932.593.402 (5)146
Symmetry codes: (i) x+1, y, z; (iv) x+1, y1/2, z+1/2; (v) x+1, y+1, z; (vi) x, y+1/2, z+1/2; (vii) x, y+1, z; (viii) x+2, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···O5i0.843 (16)1.880 (17)2.715 (3)170 (3)
O1W—H1B···O70.851 (16)1.955 (19)2.729 (3)151 (3)
O2W—H2A···O10ii0.880 (16)1.98 (2)2.729 (3)142.6 (18)
O2W—H2B···O3Wi0.862 (16)1.889 (18)2.726 (3)163 (3)
O3W—H3A···O20.846 (17)2.14 (3)2.694 (3)123 (2)
O3W—H3B···O41iii0.878 (18)1.880 (18)2.758 (4)178 (4)
C3—H3···O5i0.932.533.424 (3)161.1
C4—H4···O2i0.932.443.287 (3)152.3
C9—H9···O10iv0.932.333.193 (3)155.1
C10—H10···O7iv0.932.413.324 (3)167.5
C15—H15···O8v0.932.423.327 (4)166.4
C18—H18···O5iii0.932.563.416 (4)153.5
C20—H20···O2iii0.932.523.230 (4)133.1
C21—H21···O410.932.543.349 (5)146.0
C33—H33···O2Wvi0.932.593.402 (5)146.2
Symmetry codes: (i) x+1, y1/2, z+1/2; (ii) x+1, y, z; (iii) x+1, y+1, z; (iv) x, y+1/2, z+1/2; (v) x, y+1, z; (vi) x+2, y+1, z+1.
Acknowledgements top

This project was sponsored by the Scientific Research Foundation for the Returned Overseas Team, Chinese Education Ministry.

references
References top

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Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.

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