Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034678/ez2087sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034678/ez2087Isup2.hkl |
CCDC reference: 657608
A mixture of copper acetate (0.5 mmol, 0.149 g), 3,3,4,4-benzophenone tetracarboxylic acid (0.5 mmol, 0.162 g), and 1,10-phenanthroline (0.5 mmol, 0.10 g) in 20 ml of a 1:1 solution of water and ethanol was sealed in a 30 ml Teflon-lined stainless steel autoclave, and kept at 150 °C for 2 days. Green, block-shaped crystals were obtained at a yield of 20% after slowly cooling to room temperature. Anal. Calc. for C41H28CuN4O11: C 60.28, H 3.43, N 6.86, Cu 7.84%; Found: C 60.33, H 3.49, N 6.81, Cu 7.80%.
The H atoms of the water molecule were located from difference density maps and were refined with distance restraints of d(H–H) = 1.38 (2) Å, d(O—H) = 0.88 (2) Å, and with a fixed Uiso of 0.80 Å2. All other H atoms were placed in calculated positions with a C—H bond distance of 0.93 Å and Uiso(H) = 1.2Ueq of the carrier atom.
In recent years, carboxylic acids have been widely used as polydentate ligands that can coordinate to transition or rare earth ions, yielding complexes with interesting properties that are useful in materials science (Church & Halvorson, 1959; Chung et al., 1971) and in biological systems (Okabe & Oya, 2000; Serre et al., 2005; Pocker & Fong, 1980; Scapin et al., 1997). For example, Kim et al. (2001) focused on the syntheses of transition metal complexes containing benzene carboxylate and rigid aromatic pyridine ligands in order to study their electronic conductivity and magnetic properties. The importance of transition metal dicarboxylate complexes motivated us to pursue synthetic strategies for these compounds, using 3,3,4,4-benzophenone tetracarboxylate as a polydentate ligand. Here we report the synthesis and X-ray crystal structure analysis of the title compound.
The molecular structure of the title compound is shown in Fig. 1. The Cu(II) ion is hexa-coordinated, with two carboxylate oxygen atoms from the 3,3,4,4-benzophenone tetracarboxylate and four nitrogen atoms from two 1,10-phenanthrolines, showing a slightly distorted octahedral geometry. The Cu—O bond and Cu—N distances are in the ranges 2.378 (2)–2.0837 (19) and 2.114 (3)–2.179 (3) Å, respectively.
For uses of carboxylic acids in materials science, see: Church & Halvorson (1959). For uses in biological systems, see: Chung et al. (1971); Okabe & Oya (2000); Serre et al. (2005); Pocker & Fong (1980); Scapin et al. (1997); Kim et al. (2001).
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
Fig. 1. A view of the the title compound, showing the atomic numbering scheme and 30% probability displacement ellipsoids. |
[Cu(C17H8O9)(C12H8N2)2]·2H2O | F(000) = 1676 |
Mr = 816.21 | Dx = 1.523 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6912 reflections |
a = 14.3011 (9) Å | θ = 1.5–26.0° |
b = 16.9401 (10) Å | µ = 0.69 mm−1 |
c = 14.9839 (9) Å | T = 293 K |
β = 101.371 (1)° | Block, green |
V = 3558.8 (4) Å3 | 0.15 × 0.15 × 0.15 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 6912 independent reflections |
Radiation source: fine-focus sealed tube | 3976 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
φ and ω scans | θmax = 26.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −16→17 |
Tmin = 0.904, Tmax = 0.904 | k = −20→20 |
17576 measured reflections | l = −9→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.127 | w = 1/[σ2(Fo2) + (0.0662P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
6912 reflections | Δρmax = 0.86 e Å−3 |
528 parameters | Δρmin = −0.84 e Å−3 |
6 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997) |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00 |
[Cu(C17H8O9)(C12H8N2)2]·2H2O | V = 3558.8 (4) Å3 |
Mr = 816.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.3011 (9) Å | µ = 0.69 mm−1 |
b = 16.9401 (10) Å | T = 293 K |
c = 14.9839 (9) Å | 0.15 × 0.15 × 0.15 mm |
β = 101.371 (1)° |
Bruker APEXII CCD area-detector diffractometer | 6912 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 3976 reflections with I > 2σ(I) |
Tmin = 0.904, Tmax = 0.904 | Rint = 0.061 |
17576 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 6 restraints |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.86 e Å−3 |
6912 reflections | Δρmin = −0.84 e Å−3 |
528 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.8370 (3) | 0.4926 (3) | 0.2632 (3) | 0.0593 (11) | |
H1 | 0.7917 | 0.4526 | 0.2510 | 0.071* | |
C2 | 0.9332 (3) | 0.4719 (3) | 0.2790 (3) | 0.0715 (13) | |
H2 | 0.9509 | 0.4193 | 0.2771 | 0.086* | |
C3 | 1.0000 (3) | 0.5284 (3) | 0.2971 (3) | 0.0723 (13) | |
H3 | 1.0642 | 0.5148 | 0.3062 | 0.087* | |
C4 | 0.9735 (3) | 0.6076 (3) | 0.3024 (3) | 0.0625 (12) | |
C5 | 1.0388 (3) | 0.6732 (3) | 0.3252 (3) | 0.0756 (14) | |
H5 | 1.1040 | 0.6635 | 0.3379 | 0.091* | |
C6 | 1.0082 (3) | 0.7460 (3) | 0.3285 (3) | 0.0752 (14) | |
H6 | 1.0525 | 0.7865 | 0.3426 | 0.090* | |
C7 | 0.9086 (3) | 0.7648 (3) | 0.3108 (3) | 0.0588 (11) | |
C8 | 0.8728 (3) | 0.8412 (3) | 0.3158 (3) | 0.0691 (12) | |
H8 | 0.9144 | 0.8836 | 0.3295 | 0.083* | |
C9 | 0.7774 (3) | 0.8531 (3) | 0.3006 (3) | 0.0644 (12) | |
H9 | 0.7529 | 0.9035 | 0.3049 | 0.077* | |
C10 | 0.7162 (3) | 0.7889 (2) | 0.2785 (3) | 0.0573 (11) | |
H10 | 0.6508 | 0.7980 | 0.2677 | 0.069* | |
C11 | 0.8423 (2) | 0.7034 (2) | 0.2890 (3) | 0.0486 (10) | |
C12 | 0.8751 (2) | 0.6237 (2) | 0.2842 (3) | 0.0497 (10) | |
C13 | 0.4743 (3) | 0.7042 (3) | 0.2495 (3) | 0.0657 (12) | |
H13 | 0.5002 | 0.7128 | 0.3107 | 0.079* | |
C14 | 0.3821 (3) | 0.7304 (3) | 0.2149 (4) | 0.0725 (13) | |
H14 | 0.3469 | 0.7549 | 0.2531 | 0.087* | |
C15 | 0.3435 (3) | 0.7201 (2) | 0.1253 (3) | 0.0622 (12) | |
H15 | 0.2826 | 0.7388 | 0.1014 | 0.075* | |
C16 | 0.3957 (2) | 0.6813 (2) | 0.0699 (3) | 0.0490 (10) | |
C17 | 0.3613 (3) | 0.6667 (2) | −0.0247 (3) | 0.0604 (12) | |
H17 | 0.3008 | 0.6841 | −0.0520 | 0.072* | |
C18 | 0.4146 (3) | 0.6282 (2) | −0.0746 (3) | 0.0573 (11) | |
H18 | 0.3899 | 0.6187 | −0.1359 | 0.069* | |
C19 | 0.5088 (3) | 0.6014 (2) | −0.0358 (3) | 0.0479 (9) | |
C20 | 0.5678 (3) | 0.5606 (2) | −0.0853 (3) | 0.0567 (11) | |
H20 | 0.5466 | 0.5503 | −0.1469 | 0.068* | |
C21 | 0.6558 (3) | 0.5365 (2) | −0.0428 (3) | 0.0584 (11) | |
H21 | 0.6948 | 0.5087 | −0.0746 | 0.070* | |
C22 | 0.6866 (3) | 0.5537 (2) | 0.0485 (3) | 0.0523 (10) | |
H22 | 0.7475 | 0.5374 | 0.0766 | 0.063* | |
C23 | 0.5450 (2) | 0.6154 (2) | 0.0557 (3) | 0.0390 (8) | |
C24 | 0.4882 (2) | 0.6564 (2) | 0.1100 (3) | 0.0418 (9) | |
C25 | 0.5931 (2) | 0.5078 (2) | 0.3286 (3) | 0.0412 (9) | |
C26 | 0.5346 (2) | 0.45871 (19) | 0.3815 (2) | 0.0358 (8) | |
C27 | 0.5710 (2) | 0.40717 (19) | 0.4523 (2) | 0.0367 (8) | |
C28 | 0.6751 (2) | 0.3964 (2) | 0.4895 (3) | 0.0428 (9) | |
C29 | 0.5087 (2) | 0.3617 (2) | 0.4913 (2) | 0.0377 (8) | |
H29 | 0.5335 | 0.3274 | 0.5386 | 0.045* | |
C30 | 0.4100 (2) | 0.36606 (19) | 0.4614 (2) | 0.0339 (8) | |
C31 | 0.3744 (2) | 0.4195 (2) | 0.3933 (2) | 0.0392 (9) | |
H31 | 0.3088 | 0.4247 | 0.3740 | 0.047* | |
C32 | 0.4356 (2) | 0.4653 (2) | 0.3536 (2) | 0.0427 (9) | |
H32 | 0.4104 | 0.5008 | 0.3079 | 0.051* | |
C33 | 0.3490 (2) | 0.3106 (2) | 0.5019 (2) | 0.0361 (8) | |
C34 | 0.2422 (2) | 0.31950 (19) | 0.4831 (2) | 0.0360 (8) | |
C35 | 0.1875 (2) | 0.2517 (2) | 0.4652 (2) | 0.0410 (9) | |
H35 | 0.2185 | 0.2039 | 0.4617 | 0.049* | |
C36 | 0.0881 (2) | 0.2516 (2) | 0.4520 (3) | 0.0433 (9) | |
C37 | 0.0438 (3) | 0.1704 (2) | 0.4357 (3) | 0.0600 (12) | |
C38 | 0.0422 (2) | 0.3247 (2) | 0.4594 (3) | 0.0392 (8) | |
C39 | −0.0641 (2) | 0.3395 (2) | 0.4486 (3) | 0.0541 (11) | |
C40 | 0.0981 (2) | 0.3921 (2) | 0.4798 (3) | 0.0411 (9) | |
H40 | 0.0681 | 0.4398 | 0.4866 | 0.049* | |
C41 | 0.1964 (2) | 0.39093 (19) | 0.4903 (3) | 0.0385 (8) | |
H41 | 0.2313 | 0.4374 | 0.5019 | 0.046* | |
Cu1 | 0.66501 (3) | 0.61130 (3) | 0.23968 (3) | 0.04183 (16) | |
N1 | 0.8075 (2) | 0.5662 (2) | 0.2648 (2) | 0.0497 (8) | |
N2 | 0.7463 (2) | 0.71606 (18) | 0.2723 (2) | 0.0472 (8) | |
N3 | 0.5263 (2) | 0.66769 (19) | 0.1986 (2) | 0.0494 (8) | |
N4 | 0.63421 (19) | 0.59196 (16) | 0.0981 (2) | 0.0451 (8) | |
O1 | 0.62329 (16) | 0.57379 (14) | 0.35849 (17) | 0.0443 (6) | |
O2 | 0.60284 (18) | 0.48301 (17) | 0.25289 (18) | 0.0618 (8) | |
O3 | 0.72864 (16) | 0.42358 (16) | 0.4347 (2) | 0.0560 (7) | |
H3A | 0.7832 | 0.4069 | 0.4508 | 0.084* | |
O4 | 0.70660 (18) | 0.3663 (2) | 0.5624 (2) | 0.0740 (8) | |
O5 | 0.38447 (16) | 0.25576 (14) | 0.54750 (18) | 0.0476 (5) | |
O6 | 0.0945 (2) | 0.11279 (17) | 0.4451 (3) | 0.0797 (9) | |
O7 | −0.04731 (19) | 0.16318 (18) | 0.4096 (3) | 0.0849 (9) | |
H7 | −0.0719 | 0.2071 | 0.4039 | 0.153* | |
O8 | −0.12265 (18) | 0.28825 (19) | 0.4100 (3) | 0.1021 (12) | |
O9 | −0.09096 (16) | 0.40276 (15) | 0.4745 (2) | 0.0529 (6) | |
O10 | 0.7694 (4) | 0.4462 (5) | 0.7582 (5) | 0.072 (3) | |
O11 | 0.1075 (10) | 0.9558 (9) | 0.4964 (13) | 0.071 (3) | |
H1W | 0.7161 (12) | 0.443 (3) | 0.771 (3) | 0.080* | |
H2W | 0.8127 (19) | 0.447 (4) | 0.8053 (19) | 0.080* | |
H3W | 0.096 (3) | 0.933 (4) | 0.4435 (16) | 0.080* | |
H4W | 0.158 (2) | 0.980 (3) | 0.516 (2) | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.055 (2) | 0.065 (3) | 0.062 (3) | 0.012 (2) | 0.022 (2) | 0.010 (2) |
C2 | 0.064 (3) | 0.074 (3) | 0.083 (4) | 0.024 (2) | 0.030 (3) | 0.017 (3) |
C3 | 0.045 (2) | 0.102 (4) | 0.074 (3) | 0.022 (2) | 0.021 (2) | 0.019 (3) |
C4 | 0.040 (2) | 0.090 (3) | 0.059 (3) | 0.009 (2) | 0.015 (2) | 0.017 (3) |
C5 | 0.034 (2) | 0.119 (4) | 0.075 (4) | −0.007 (3) | 0.012 (2) | 0.014 (3) |
C6 | 0.052 (3) | 0.092 (4) | 0.085 (4) | −0.015 (3) | 0.020 (3) | 0.006 (3) |
C7 | 0.050 (2) | 0.076 (3) | 0.051 (3) | −0.010 (2) | 0.011 (2) | 0.011 (2) |
C8 | 0.076 (3) | 0.070 (3) | 0.062 (3) | −0.017 (3) | 0.014 (3) | 0.005 (2) |
C9 | 0.075 (3) | 0.058 (3) | 0.060 (3) | −0.002 (2) | 0.014 (2) | 0.006 (2) |
C10 | 0.058 (2) | 0.064 (3) | 0.052 (3) | 0.007 (2) | 0.013 (2) | 0.014 (2) |
C11 | 0.040 (2) | 0.067 (3) | 0.040 (2) | −0.0021 (18) | 0.0122 (18) | 0.011 (2) |
C12 | 0.0363 (19) | 0.068 (3) | 0.048 (3) | 0.0039 (18) | 0.0166 (18) | 0.013 (2) |
C13 | 0.050 (2) | 0.093 (3) | 0.057 (3) | 0.015 (2) | 0.017 (2) | −0.007 (3) |
C14 | 0.052 (3) | 0.091 (3) | 0.075 (4) | 0.017 (2) | 0.015 (3) | −0.014 (3) |
C15 | 0.043 (2) | 0.065 (3) | 0.073 (3) | 0.011 (2) | 0.001 (2) | 0.002 (3) |
C16 | 0.041 (2) | 0.046 (2) | 0.057 (3) | 0.0018 (17) | 0.002 (2) | 0.007 (2) |
C17 | 0.046 (2) | 0.059 (3) | 0.066 (3) | −0.002 (2) | −0.014 (2) | 0.006 (2) |
C18 | 0.061 (3) | 0.056 (3) | 0.048 (3) | −0.009 (2) | −0.005 (2) | 0.003 (2) |
C19 | 0.057 (2) | 0.041 (2) | 0.046 (3) | −0.0150 (18) | 0.011 (2) | 0.0048 (19) |
C20 | 0.075 (3) | 0.051 (2) | 0.048 (3) | −0.018 (2) | 0.020 (2) | −0.006 (2) |
C21 | 0.067 (3) | 0.058 (3) | 0.058 (3) | −0.010 (2) | 0.031 (2) | −0.008 (2) |
C22 | 0.045 (2) | 0.055 (2) | 0.062 (3) | −0.0040 (18) | 0.022 (2) | 0.002 (2) |
C23 | 0.0411 (19) | 0.0355 (18) | 0.040 (2) | −0.0067 (15) | 0.0076 (17) | 0.0052 (17) |
C24 | 0.0393 (19) | 0.039 (2) | 0.046 (3) | −0.0018 (16) | 0.0061 (18) | 0.0069 (18) |
C25 | 0.0253 (17) | 0.055 (2) | 0.043 (2) | 0.0009 (16) | 0.0065 (16) | 0.000 (2) |
C26 | 0.0303 (17) | 0.044 (2) | 0.035 (2) | −0.0038 (15) | 0.0109 (15) | −0.0096 (17) |
C27 | 0.0267 (16) | 0.043 (2) | 0.042 (2) | 0.0000 (14) | 0.0091 (16) | −0.0068 (17) |
C28 | 0.0290 (17) | 0.047 (2) | 0.053 (3) | 0.0011 (16) | 0.0092 (18) | 0.003 (2) |
C29 | 0.0290 (17) | 0.0428 (19) | 0.041 (2) | 0.0045 (14) | 0.0071 (16) | 0.0004 (17) |
C30 | 0.0245 (15) | 0.0402 (19) | 0.038 (2) | 0.0002 (14) | 0.0091 (15) | −0.0085 (17) |
C31 | 0.0231 (16) | 0.050 (2) | 0.043 (2) | 0.0017 (15) | 0.0019 (15) | −0.0027 (19) |
C32 | 0.0320 (18) | 0.054 (2) | 0.042 (2) | 0.0042 (16) | 0.0065 (17) | 0.0023 (18) |
C33 | 0.0315 (17) | 0.0329 (19) | 0.044 (2) | 0.0052 (15) | 0.0080 (16) | −0.0049 (17) |
C34 | 0.0258 (16) | 0.043 (2) | 0.042 (2) | −0.0015 (14) | 0.0128 (15) | 0.0025 (17) |
C35 | 0.0352 (19) | 0.039 (2) | 0.053 (2) | 0.0023 (15) | 0.0181 (18) | −0.0023 (18) |
C36 | 0.0333 (18) | 0.043 (2) | 0.055 (3) | −0.0053 (15) | 0.0130 (18) | −0.0004 (19) |
C37 | 0.044 (2) | 0.051 (3) | 0.090 (4) | −0.012 (2) | 0.025 (2) | −0.007 (2) |
C38 | 0.0257 (16) | 0.043 (2) | 0.049 (2) | −0.0027 (15) | 0.0073 (16) | 0.0004 (18) |
C39 | 0.0286 (19) | 0.055 (3) | 0.079 (3) | −0.0022 (18) | 0.013 (2) | 0.004 (2) |
C40 | 0.0273 (16) | 0.042 (2) | 0.054 (2) | 0.0053 (15) | 0.0098 (16) | 0.0020 (18) |
C41 | 0.0265 (16) | 0.0373 (19) | 0.052 (2) | −0.0009 (14) | 0.0095 (16) | −0.0010 (18) |
Cu1 | 0.0311 (2) | 0.0549 (3) | 0.0406 (3) | 0.0029 (2) | 0.00990 (19) | 0.0077 (2) |
N1 | 0.0458 (18) | 0.058 (2) | 0.048 (2) | 0.0079 (16) | 0.0166 (16) | 0.0102 (17) |
N2 | 0.0412 (17) | 0.057 (2) | 0.044 (2) | 0.0050 (15) | 0.0109 (15) | 0.0135 (16) |
N3 | 0.0429 (17) | 0.064 (2) | 0.041 (2) | 0.0053 (15) | 0.0077 (16) | −0.0010 (17) |
N4 | 0.0384 (16) | 0.0452 (18) | 0.055 (2) | −0.0019 (13) | 0.0172 (15) | 0.0076 (15) |
O1 | 0.0424 (13) | 0.0413 (14) | 0.0509 (17) | −0.0039 (11) | 0.0135 (12) | −0.0007 (13) |
O2 | 0.0624 (17) | 0.087 (2) | 0.0431 (17) | −0.0233 (15) | 0.0275 (14) | −0.0160 (16) |
O3 | 0.0252 (12) | 0.0642 (17) | 0.081 (2) | 0.0072 (12) | 0.0155 (14) | 0.0142 (15) |
O4 | 0.0324 (13) | 0.119 (2) | 0.0676 (17) | 0.0069 (14) | 0.0020 (12) | 0.0308 (16) |
O5 | 0.0314 (12) | 0.0411 (13) | 0.0703 (14) | 0.0044 (9) | 0.0100 (10) | 0.0081 (11) |
O6 | 0.0604 (18) | 0.0370 (14) | 0.140 (3) | −0.0056 (13) | 0.0168 (18) | −0.0061 (15) |
O7 | 0.0422 (16) | 0.0554 (17) | 0.158 (3) | −0.0182 (13) | 0.0219 (17) | −0.0232 (18) |
O8 | 0.0266 (14) | 0.0729 (19) | 0.198 (4) | −0.0097 (13) | 0.0017 (17) | −0.043 (2) |
O9 | 0.0250 (12) | 0.0535 (14) | 0.0808 (17) | 0.0039 (10) | 0.0122 (11) | −0.0022 (12) |
O10 | 0.065 (6) | 0.083 (7) | 0.061 (7) | 0.008 (6) | 0.017 (5) | 0.018 (6) |
O11 | 0.072 (6) | 0.067 (6) | 0.080 (8) | 0.001 (5) | 0.032 (5) | 0.004 (6) |
C1—N1 | 1.318 (5) | C24—N3 | 1.345 (5) |
C1—C2 | 1.393 (5) | C25—O2 | 1.244 (4) |
C1—H1 | 0.9300 | C25—O1 | 1.249 (4) |
C2—C3 | 1.341 (6) | C25—C26 | 1.511 (5) |
C2—H2 | 0.9300 | C25—Cu1 | 2.539 (4) |
C3—C4 | 1.401 (6) | C26—C27 | 1.392 (5) |
C3—H3 | 0.9300 | C26—C32 | 1.400 (4) |
C4—C12 | 1.407 (5) | C27—C29 | 1.391 (5) |
C4—C5 | 1.448 (6) | C27—C28 | 1.495 (5) |
C5—C6 | 1.311 (6) | C28—O4 | 1.209 (4) |
C5—H5 | 0.9300 | C28—O3 | 1.311 (4) |
C6—C7 | 1.433 (6) | C29—C30 | 1.396 (4) |
C6—H6 | 0.9300 | C29—H29 | 0.9300 |
C7—C8 | 1.400 (6) | C30—C31 | 1.383 (5) |
C7—C11 | 1.401 (5) | C30—C33 | 1.491 (4) |
C8—C9 | 1.354 (6) | C31—C32 | 1.388 (5) |
C8—H8 | 0.9300 | C31—H31 | 0.9300 |
C9—C10 | 1.393 (6) | C32—H32 | 0.9300 |
C9—H9 | 0.9300 | C33—O5 | 1.205 (4) |
C10—N2 | 1.316 (5) | C33—C34 | 1.504 (4) |
C10—H10 | 0.9300 | C34—C35 | 1.386 (4) |
C11—N2 | 1.364 (4) | C34—C41 | 1.390 (4) |
C11—C12 | 1.436 (5) | C35—C36 | 1.396 (4) |
C12—N1 | 1.363 (5) | C35—H35 | 0.9300 |
C13—N3 | 1.321 (5) | C36—C38 | 1.417 (5) |
C13—C14 | 1.391 (5) | C36—C37 | 1.514 (5) |
C13—H13 | 0.9300 | C37—O6 | 1.207 (4) |
C14—C15 | 1.358 (6) | C37—O7 | 1.290 (4) |
C14—H14 | 0.9300 | C38—C40 | 1.393 (4) |
C15—C16 | 1.386 (5) | C38—C39 | 1.518 (4) |
C15—H15 | 0.9300 | C39—O9 | 1.226 (4) |
C16—C24 | 1.406 (5) | C39—O8 | 1.264 (4) |
C16—C17 | 1.427 (6) | C40—C41 | 1.384 (4) |
C17—C18 | 1.337 (6) | C40—H40 | 0.9300 |
C17—H17 | 0.9300 | C41—H41 | 0.9300 |
C18—C19 | 1.432 (5) | Cu1—O1 | 2.085 (2) |
C18—H18 | 0.9300 | Cu1—N4 | 2.106 (3) |
C19—C23 | 1.387 (5) | Cu1—N2 | 2.125 (3) |
C19—C20 | 1.410 (5) | Cu1—N1 | 2.139 (3) |
C20—C21 | 1.356 (6) | Cu1—N3 | 2.178 (3) |
C20—H20 | 0.9300 | Cu1—O2 | 2.371 (3) |
C21—C22 | 1.383 (6) | O3—H3A | 0.8200 |
C21—H21 | 0.9300 | O7—H7 | 0.8200 |
C22—N4 | 1.325 (4) | O10—H1W | 0.821 (11) |
C22—H22 | 0.9300 | O10—H2W | 0.84 (3) |
C23—N4 | 1.366 (4) | O11—H3W | 0.87 (3) |
C23—C24 | 1.438 (5) | O11—H4W | 0.83 (4) |
N1—C1—C2 | 122.9 (4) | C26—C27—C28 | 123.8 (3) |
N1—C1—H1 | 118.6 | O4—C28—O3 | 123.7 (3) |
C2—C1—H1 | 118.5 | O4—C28—C27 | 123.7 (3) |
C3—C2—C1 | 119.7 (4) | O3—C28—C27 | 112.7 (3) |
C3—C2—H2 | 120.2 | C27—C29—C30 | 121.8 (3) |
C1—C2—H2 | 120.1 | C27—C29—H29 | 119.1 |
C2—C3—C4 | 120.3 (4) | C30—C29—H29 | 119.1 |
C2—C3—H3 | 119.8 | C31—C30—C29 | 118.3 (3) |
C4—C3—H3 | 119.9 | C31—C30—C33 | 123.5 (3) |
C3—C4—C12 | 116.5 (4) | C29—C30—C33 | 118.2 (3) |
C3—C4—C5 | 125.5 (4) | C30—C31—C32 | 120.7 (3) |
C12—C4—C5 | 118.1 (4) | C30—C31—H31 | 119.6 |
C6—C5—C4 | 121.8 (4) | C32—C31—H31 | 119.7 |
C6—C5—H5 | 119.1 | C31—C32—C26 | 120.9 (3) |
C4—C5—H5 | 119.1 | C31—C32—H32 | 119.5 |
C5—C6—C7 | 121.9 (4) | C26—C32—H32 | 119.6 |
C5—C6—H6 | 119.1 | O5—C33—C30 | 120.1 (3) |
C7—C6—H6 | 119.0 | O5—C33—C34 | 118.8 (3) |
C8—C7—C11 | 117.4 (4) | C30—C33—C34 | 121.0 (3) |
C8—C7—C6 | 123.8 (4) | C35—C34—C41 | 118.6 (3) |
C11—C7—C6 | 118.7 (4) | C35—C34—C33 | 117.8 (3) |
C9—C8—C7 | 119.7 (4) | C41—C34—C33 | 123.3 (3) |
C9—C8—H8 | 120.2 | C34—C35—C36 | 123.3 (3) |
C7—C8—H8 | 120.1 | C34—C35—H35 | 118.4 |
C8—C9—C10 | 119.3 (4) | C36—C35—H35 | 118.3 |
C8—C9—H9 | 120.5 | C35—C36—C38 | 117.5 (3) |
C10—C9—H9 | 120.3 | C35—C36—C37 | 114.0 (3) |
N2—C10—C9 | 123.3 (4) | C38—C36—C37 | 128.4 (3) |
N2—C10—H10 | 118.2 | O6—C37—O7 | 120.5 (4) |
C9—C10—H10 | 118.4 | O6—C37—C36 | 119.5 (3) |
N2—C11—C7 | 122.5 (4) | O7—C37—C36 | 120.0 (4) |
N2—C11—C12 | 117.7 (3) | C40—C38—C36 | 118.6 (3) |
C7—C11—C12 | 119.8 (3) | C40—C38—C39 | 114.0 (3) |
N1—C12—C4 | 122.9 (4) | C36—C38—C39 | 127.3 (3) |
N1—C12—C11 | 117.3 (3) | O9—C39—O8 | 121.6 (3) |
C4—C12—C11 | 119.7 (4) | O9—C39—C38 | 118.7 (3) |
N3—C13—C14 | 122.3 (4) | O8—C39—C38 | 119.6 (4) |
N3—C13—H13 | 118.8 | C41—C40—C38 | 122.7 (3) |
C14—C13—H13 | 118.9 | C41—C40—H40 | 118.7 |
C15—C14—C13 | 119.8 (4) | C38—C40—H40 | 118.7 |
C15—C14—H14 | 120.0 | C40—C41—C34 | 119.2 (3) |
C13—C14—H14 | 120.1 | C40—C41—H41 | 120.4 |
C14—C15—C16 | 119.5 (4) | C34—C41—H41 | 120.4 |
C14—C15—H15 | 120.3 | O1—Cu1—N4 | 140.77 (10) |
C16—C15—H15 | 120.2 | O1—Cu1—N2 | 107.09 (11) |
C15—C16—C24 | 117.3 (4) | N4—Cu1—N2 | 110.97 (11) |
C15—C16—C17 | 123.9 (4) | O1—Cu1—N1 | 99.44 (11) |
C24—C16—C17 | 118.9 (4) | N4—Cu1—N1 | 97.14 (11) |
C18—C17—C16 | 121.2 (4) | N2—Cu1—N1 | 78.41 (12) |
C18—C17—H17 | 119.4 | O1—Cu1—N3 | 88.70 (11) |
C16—C17—H17 | 119.4 | N4—Cu1—N3 | 77.60 (12) |
C17—C18—C19 | 121.4 (4) | N2—Cu1—N3 | 97.19 (12) |
C17—C18—H18 | 119.3 | N1—Cu1—N3 | 171.58 (12) |
C19—C18—H18 | 119.3 | O1—Cu1—O2 | 58.28 (9) |
C23—C19—C20 | 117.2 (4) | N4—Cu1—O2 | 86.22 (10) |
C23—C19—C18 | 119.1 (4) | N2—Cu1—O2 | 160.63 (11) |
C20—C19—C18 | 123.7 (4) | N1—Cu1—O2 | 91.00 (11) |
C21—C20—C19 | 119.8 (4) | N3—Cu1—O2 | 95.17 (11) |
C21—C20—H20 | 120.1 | O1—Cu1—C25 | 29.28 (10) |
C19—C20—H20 | 120.1 | N4—Cu1—C25 | 113.30 (12) |
C20—C21—C22 | 119.1 (4) | N2—Cu1—C25 | 135.70 (12) |
C20—C21—H21 | 120.4 | N1—Cu1—C25 | 97.53 (11) |
C22—C21—H21 | 120.5 | N3—Cu1—C25 | 90.63 (11) |
N4—C22—C21 | 123.5 (4) | O2—Cu1—C25 | 29.08 (10) |
N4—C22—H22 | 118.2 | C1—N1—C12 | 117.6 (3) |
C21—C22—H22 | 118.3 | C1—N1—Cu1 | 129.3 (3) |
N4—C23—C19 | 122.9 (3) | C12—N1—Cu1 | 113.1 (2) |
N4—C23—C24 | 117.2 (3) | C10—N2—C11 | 117.7 (3) |
C19—C23—C24 | 119.9 (3) | C10—N2—Cu1 | 128.9 (3) |
N3—C24—C16 | 122.9 (4) | C11—N2—Cu1 | 113.4 (3) |
N3—C24—C23 | 117.5 (3) | C13—N3—C24 | 118.1 (3) |
C16—C24—C23 | 119.5 (4) | C13—N3—Cu1 | 128.9 (3) |
O2—C25—O1 | 122.5 (3) | C24—N3—Cu1 | 112.7 (2) |
O2—C25—C26 | 117.8 (3) | C22—N4—C23 | 117.5 (3) |
O1—C25—C26 | 119.5 (3) | C22—N4—Cu1 | 127.7 (3) |
O2—C25—Cu1 | 67.9 (2) | C23—N4—Cu1 | 114.4 (2) |
O1—C25—Cu1 | 54.76 (18) | C25—O1—Cu1 | 96.0 (2) |
C26—C25—Cu1 | 168.3 (2) | C25—O2—Cu1 | 83.0 (2) |
C27—C26—C32 | 118.8 (3) | C28—O3—H3A | 109.6 |
C27—C26—C25 | 125.6 (3) | C37—O7—H7 | 109.4 |
C32—C26—C25 | 115.6 (3) | H1W—O10—H2W | 112 (3) |
C29—C27—C26 | 119.5 (3) | H3W—O11—H4W | 122 (4) |
C29—C27—C28 | 116.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H4W···O6i | 0.83 (4) | 2.58 (5) | 2.764 (14) | 94 (4) |
O3—H3A···O8ii | 0.82 | 2.56 | 3.198 (4) | 136 |
O3—H3A···O9ii | 0.82 | 1.77 | 2.555 (3) | 161 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C17H8O9)(C12H8N2)2]·2H2O |
Mr | 816.21 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 14.3011 (9), 16.9401 (10), 14.9839 (9) |
β (°) | 101.371 (1) |
V (Å3) | 3558.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.15 × 0.15 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.904, 0.904 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17576, 6912, 3976 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.618 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.127, 1.00 |
No. of reflections | 6912 |
No. of parameters | 528 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.86, −0.84 |
Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H4W···O6i | 0.83 (4) | 2.58 (5) | 2.764 (14) | 94 (4) |
O3—H3A···O8ii | 0.82 | 2.56 | 3.198 (4) | 135.7 |
O3—H3A···O9ii | 0.82 | 1.77 | 2.555 (3) | 161.1 |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z. |
In recent years, carboxylic acids have been widely used as polydentate ligands that can coordinate to transition or rare earth ions, yielding complexes with interesting properties that are useful in materials science (Church & Halvorson, 1959; Chung et al., 1971) and in biological systems (Okabe & Oya, 2000; Serre et al., 2005; Pocker & Fong, 1980; Scapin et al., 1997). For example, Kim et al. (2001) focused on the syntheses of transition metal complexes containing benzene carboxylate and rigid aromatic pyridine ligands in order to study their electronic conductivity and magnetic properties. The importance of transition metal dicarboxylate complexes motivated us to pursue synthetic strategies for these compounds, using 3,3,4,4-benzophenone tetracarboxylate as a polydentate ligand. Here we report the synthesis and X-ray crystal structure analysis of the title compound.
The molecular structure of the title compound is shown in Fig. 1. The Cu(II) ion is hexa-coordinated, with two carboxylate oxygen atoms from the 3,3,4,4-benzophenone tetracarboxylate and four nitrogen atoms from two 1,10-phenanthrolines, showing a slightly distorted octahedral geometry. The Cu—O bond and Cu—N distances are in the ranges 2.378 (2)–2.0837 (19) and 2.114 (3)–2.179 (3) Å, respectively.