Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052348/br2056sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052348/br2056Isup2.hkl |
CCDC reference: 667240
1 was prepared by the reaction of Cu(ClO4)2 (37 mg, 0.1 mmol) and (phen-dione) (62 mg, 0.3 mmol) in a mixture CH3CN–H2O (2:1 v/v, 6 ml) at 298 K. After allowing the resulting green solution to stand at 298 K for 3 days, green crystals of the product were formed.
H atoms were included in calculated positions (O—H distances are 0.98 Å, C—H distances are 0.98 Å for methyl H atoms, 0.99 Å for methylene H atoms and 0.95 Å for aryl H atoms) and were refined as riding atoms with Uiso(H) = 1.2Ueq(parent atom, O, methylene and aryl H atoms) or Uiso(H) = 1.5Ueq(parent atom, methyl H atoms). O55 was refined as 0.5 occupancy to be compatable with microanlaytical data.
Metal complexes with 1,10-phenantroline-5,6-dione (phen-dione) as a ligand have been increasingly studied over recent years (Hadadzadeh et al., 2006; Mansouri et al., 2007). The structure of monomeric hexacoordinated tris-chelated complexes of copper(II) have been reported previously (Majumdar et al., 1998 Wang et al., 2007). The six-coordinate copper center in the the title complex has distorted octahedral geometry (Fig. 1) being slightly tetragonally elongated due to the Jahn–Teller elongation of two Cu—N bonds in trans positions (average Cu—Neq = 2.05 and Cu—Nax = 2.27 Å) and the contraction of three of the N—Cu—N angles (average chelate angle N—Cu—N = 78°) from the ideal octahedral values, imposed by the three chelate ligands (Majumdar et al., 1998).
For related literature, see: Majumdar et al. (1998); Hadadzadeh et al. (2006); Wang et al. (2007); Mansouri et al. (2007).
Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear (Rigaku, 2004); data reduction: CrystalClear (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2003).
Fig. 1. The structure of (1) with displacement ellipsoids drawn at the 50% probability level. |
[Cu(C12H6N2O2)3](ClO4)2·4.5H2O | F(000) = 1984 |
Mr = 974.08 | Dx = 1.696 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 12591 reflections |
a = 13.136 (2) Å | θ = 1.6–28.8° |
b = 14.071 (2) Å | µ = 0.81 mm−1 |
c = 20.636 (3) Å | T = 93 K |
V = 3814.2 (10) Å3 | Prism, green |
Z = 4 | 0.10 × 0.10 × 0.10 mm |
Rigaku Mercury CCD diffractometer | 6940 independent reflections |
Radiation source: rotating anode | 6206 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.061 |
ω and φ scans | θmax = 25.4°, θmin = 2.1° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2004) | h = −11→15 |
Tmin = 0.920, Tmax = 0.923 | k = −16→16 |
24980 measured reflections | l = −23→24 |
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)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.066P)2 + 2.3835P] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max = 0.016 |
6940 reflections | Δρmax = 0.53 e Å−3 |
534 parameters | Δρmin = −0.45 e Å−3 |
0 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.517 (14) |
[Cu(C12H6N2O2)3](ClO4)2·4.5H2O | V = 3814.2 (10) Å3 |
Mr = 974.08 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 13.136 (2) Å | µ = 0.81 mm−1 |
b = 14.071 (2) Å | T = 93 K |
c = 20.636 (3) Å | 0.10 × 0.10 × 0.10 mm |
Rigaku Mercury CCD diffractometer | 6940 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2004) | 6206 reflections with I > 2σ(I) |
Tmin = 0.920, Tmax = 0.923 | Rint = 0.061 |
24980 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.122 | Δρmax = 0.53 e Å−3 |
S = 0.95 | Δρmin = −0.45 e Å−3 |
6940 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
534 parameters | Absolute structure parameter: 0.517 (14) |
0 restraints |
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 | Occ. (<1) | |
Cu1 | 0.80991 (4) | 0.51514 (3) | −0.06737 (2) | 0.02531 (13) | |
C1A | 0.6817 (3) | 0.3910 (3) | 0.00640 (17) | 0.0245 (8) | |
N1 | 0.7794 (3) | 0.4193 (2) | 0.00456 (15) | 0.0246 (8) | |
C2 | 0.8461 (4) | 0.3783 (3) | 0.04414 (19) | 0.0293 (10) | |
H2A | 0.9149 | 0.3989 | 0.0429 | 0.035* | |
C3 | 0.8192 (4) | 0.3058 (3) | 0.08770 (18) | 0.0296 (9) | |
H3A | 0.8680 | 0.2788 | 0.1162 | 0.036* | |
C4 | 0.7188 (4) | 0.2751 (3) | 0.0875 (2) | 0.0326 (11) | |
H4A | 0.6978 | 0.2250 | 0.1154 | 0.039* | |
C4A | 0.6494 (4) | 0.3183 (3) | 0.04634 (19) | 0.0292 (9) | |
C5 | 0.5416 (4) | 0.2886 (3) | 0.0463 (2) | 0.0311 (10) | |
O5 | 0.5114 (3) | 0.2206 (2) | 0.07747 (16) | 0.0402 (8) | |
C6 | 0.4668 (4) | 0.3469 (3) | 0.0055 (2) | 0.0318 (10) | |
O6 | 0.3748 (3) | 0.3364 (2) | 0.01319 (15) | 0.0411 (8) | |
C6A | 0.5092 (3) | 0.4159 (3) | −0.04171 (19) | 0.0271 (9) | |
C7 | 0.4487 (4) | 0.4575 (3) | −0.0889 (2) | 0.0339 (10) | |
H7A | 0.3783 | 0.4428 | −0.0919 | 0.041* | |
C8 | 0.4929 (3) | 0.5202 (3) | −0.13128 (19) | 0.0340 (10) | |
H8A | 0.4534 | 0.5492 | −0.1644 | 0.041* | |
C9 | 0.5950 (4) | 0.5410 (3) | −0.1255 (2) | 0.0323 (10) | |
H9A | 0.6244 | 0.5856 | −0.1546 | 0.039* | |
N10 | 0.6545 (2) | 0.5005 (2) | −0.08031 (14) | 0.0252 (7) | |
C10A | 0.6118 (3) | 0.4370 (3) | −0.03969 (19) | 0.0259 (9) | |
C11A | 0.8654 (3) | 0.4356 (3) | −0.19842 (18) | 0.0231 (8) | |
N11 | 0.8339 (3) | 0.4002 (2) | −0.14182 (15) | 0.0264 (8) | |
C12 | 0.8182 (4) | 0.3058 (3) | −0.1370 (2) | 0.0296 (9) | |
H12A | 0.7941 | 0.2808 | −0.0971 | 0.035* | |
C13 | 0.8357 (4) | 0.2443 (3) | −0.1878 (2) | 0.0354 (11) | |
H13A | 0.8227 | 0.1782 | −0.1831 | 0.042* | |
C14 | 0.8727 (4) | 0.2803 (3) | −0.2457 (2) | 0.0318 (10) | |
H14A | 0.8868 | 0.2392 | −0.2812 | 0.038* | |
C14A | 0.8887 (3) | 0.3774 (3) | −0.25086 (19) | 0.0284 (9) | |
C15 | 0.9276 (3) | 0.4188 (3) | −0.3117 (2) | 0.0303 (10) | |
O15 | 0.9565 (3) | 0.3708 (2) | −0.35700 (14) | 0.0399 (8) | |
C16 | 0.9344 (3) | 0.5279 (3) | −0.31652 (18) | 0.0285 (9) | |
O16 | 0.9674 (2) | 0.5632 (2) | −0.36579 (14) | 0.0354 (7) | |
C16A | 0.9003 (3) | 0.5846 (3) | −0.26048 (19) | 0.0264 (9) | |
C17 | 0.8983 (3) | 0.6839 (3) | −0.2627 (2) | 0.0299 (10) | |
H17A | 0.9181 | 0.7163 | −0.3011 | 0.036* | |
C18 | 0.8676 (4) | 0.7345 (3) | −0.2094 (2) | 0.0308 (10) | |
H18A | 0.8641 | 0.8019 | −0.2106 | 0.037* | |
C19 | 0.8418 (3) | 0.6850 (3) | −0.1536 (2) | 0.0286 (10) | |
H19A | 0.8233 | 0.7202 | −0.1161 | 0.034* | |
N20 | 0.8418 (3) | 0.5896 (2) | −0.15016 (15) | 0.0252 (8) | |
C20A | 0.8708 (3) | 0.5402 (3) | −0.20334 (19) | 0.0262 (9) | |
C21A | 0.9652 (4) | 0.6034 (3) | 0.0173 (2) | 0.0406 (12) | |
N21 | 0.9543 (3) | 0.5403 (3) | −0.03255 (16) | 0.0378 (10) | |
C22 | 1.0360 (4) | 0.4910 (3) | −0.0517 (2) | 0.0401 (11) | |
H22A | 1.0288 | 0.4475 | −0.0867 | 0.048* | |
C23 | 1.1302 (4) | 0.5004 (4) | −0.0230 (2) | 0.0560 (14) | |
H23A | 1.1860 | 0.4629 | −0.0373 | 0.067* | |
C24 | 1.1423 (5) | 0.5650 (5) | 0.0266 (3) | 0.0622 (17) | |
H24A | 1.2070 | 0.5743 | 0.0462 | 0.075* | |
C24A | 1.0580 (5) | 0.6160 (4) | 0.0474 (2) | 0.0503 (14) | |
C25 | 1.0674 (5) | 0.6847 (4) | 0.1013 (3) | 0.0605 (17) | |
O25 | 1.1476 (4) | 0.7083 (4) | 0.1246 (2) | 0.0977 (19) | |
C26 | 0.9694 (5) | 0.7303 (3) | 0.1277 (2) | 0.0470 (14) | |
O26 | 0.9727 (3) | 0.7770 (2) | 0.17717 (15) | 0.0567 (11) | |
C26A | 0.8755 (4) | 0.7166 (3) | 0.0904 (2) | 0.0411 (13) | |
C27 | 0.7863 (5) | 0.7642 (3) | 0.1079 (2) | 0.0474 (15) | |
H27A | 0.7860 | 0.8066 | 0.1437 | 0.057* | |
C28 | 0.6988 (5) | 0.7487 (3) | 0.0725 (2) | 0.0492 (14) | |
H28A | 0.6370 | 0.7802 | 0.0829 | 0.059* | |
C29 | 0.7045 (5) | 0.6855 (4) | 0.0211 (2) | 0.0452 (13) | |
H29A | 0.6441 | 0.6740 | −0.0030 | 0.054* | |
N30 | 0.7889 (4) | 0.6394 (3) | 0.00283 (17) | 0.0392 (10) | |
C30A | 0.8739 (4) | 0.6550 (3) | 0.0371 (2) | 0.0387 (12) | |
Cl1 | 0.86111 (8) | 0.51099 (7) | 0.19790 (4) | 0.0303 (2) | |
O1 | 0.9516 (2) | 0.5291 (2) | 0.15943 (14) | 0.0410 (8) | |
O2 | 0.8557 (3) | 0.5791 (2) | 0.25014 (14) | 0.0388 (8) | |
O3 | 0.8655 (3) | 0.4168 (2) | 0.22383 (14) | 0.0427 (9) | |
O4 | 0.7724 (2) | 0.5215 (2) | 0.15703 (12) | 0.0348 (7) | |
Cl2 | 0.32975 (8) | 0.49483 (7) | 0.29448 (4) | 0.0328 (2) | |
O7 | 0.3919 (3) | 0.4244 (2) | 0.32687 (16) | 0.0408 (8) | |
O8 | 0.3279 (6) | 0.5780 (3) | 0.3307 (2) | 0.115 (3) | |
O9 | 0.3686 (3) | 0.5139 (3) | 0.23209 (16) | 0.0647 (11) | |
O10 | 0.2305 (3) | 0.4562 (4) | 0.2882 (2) | 0.0905 (17) | |
O51 | 0.1547 | 0.4507 | 0.1543 | 0.067 | |
H51A | 0.1842 | 0.4394 | 0.1973 | 0.080* | |
H51B | 0.2066 | 0.4371 | 0.1215 | 0.080* | |
O52 | 0.4579 | 0.6529 | 0.0193 | 0.107 | |
H52A | 0.5011 | 0.6369 | 0.0564 | 0.128* | |
H52B | 0.3868 | 0.6411 | 0.0314 | 0.128* | |
O53 | 1.0080 | 0.7094 | 0.3069 | 0.066 | |
H53A | 0.9624 | 0.6593 | 0.2913 | 0.079* | |
H53B | 1.0080 | 0.7595 | 0.2739 | 0.079* | |
O54 | 0.9179 | 0.7872 | 0.4193 | 0.051 | |
H54A | 0.9425 | 0.7758 | 0.3751 | 0.061* | |
H54B | 0.8740 | 0.8435 | 0.4185 | 0.061* | |
O55 | 0.3445 | 0.5341 | 0.0856 | 0.095 | 0.50 |
H55A | 0.2844 | 0.5078 | 0.1073 | 0.114* | 0.50 |
H55B | 0.3979 | 0.5094 | 0.1141 | 0.114* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0312 (3) | 0.0204 (2) | 0.0243 (2) | −0.0016 (2) | 0.00168 (19) | 0.00085 (19) |
C1A | 0.028 (2) | 0.0215 (19) | 0.0244 (18) | 0.0010 (19) | 0.0033 (17) | −0.0046 (15) |
N1 | 0.029 (2) | 0.0223 (17) | 0.0220 (15) | 0.0037 (15) | −0.0006 (14) | −0.0029 (13) |
C2 | 0.031 (2) | 0.029 (2) | 0.0281 (19) | 0.000 (2) | 0.0021 (18) | −0.0007 (17) |
C3 | 0.039 (3) | 0.028 (2) | 0.0227 (18) | 0.001 (2) | 0.0014 (19) | −0.0005 (16) |
C4 | 0.048 (3) | 0.019 (2) | 0.031 (2) | −0.001 (2) | 0.010 (2) | 0.0009 (17) |
C4A | 0.034 (3) | 0.0209 (19) | 0.032 (2) | 0.0024 (19) | 0.0056 (19) | 0.0002 (17) |
C5 | 0.038 (3) | 0.021 (2) | 0.034 (2) | 0.000 (2) | 0.0068 (19) | −0.0006 (18) |
O5 | 0.0390 (19) | 0.0274 (16) | 0.0543 (19) | −0.0054 (15) | 0.0096 (16) | 0.0076 (15) |
C6 | 0.033 (3) | 0.031 (2) | 0.032 (2) | 0.000 (2) | 0.0015 (19) | −0.0103 (18) |
O6 | 0.033 (2) | 0.048 (2) | 0.0424 (17) | −0.0055 (16) | 0.0050 (15) | −0.0027 (15) |
C6A | 0.025 (2) | 0.024 (2) | 0.0323 (19) | 0.0042 (19) | 0.0040 (18) | −0.0040 (17) |
C7 | 0.032 (2) | 0.033 (2) | 0.037 (2) | 0.002 (2) | −0.0027 (19) | −0.0071 (19) |
C8 | 0.036 (2) | 0.032 (2) | 0.034 (2) | 0.004 (2) | −0.0058 (18) | −0.004 (2) |
C9 | 0.041 (3) | 0.028 (2) | 0.0287 (19) | 0.002 (2) | −0.0001 (19) | −0.0019 (17) |
N10 | 0.0296 (18) | 0.0210 (17) | 0.0249 (14) | 0.0011 (16) | 0.0003 (13) | −0.0015 (13) |
C10A | 0.031 (2) | 0.0173 (18) | 0.0291 (19) | 0.0027 (18) | 0.0038 (18) | −0.0038 (16) |
C11A | 0.021 (2) | 0.0203 (19) | 0.0281 (19) | −0.0011 (17) | −0.0015 (18) | 0.0020 (16) |
N11 | 0.029 (2) | 0.0197 (16) | 0.0307 (17) | −0.0023 (15) | −0.0020 (15) | 0.0051 (14) |
C12 | 0.034 (2) | 0.022 (2) | 0.033 (2) | 0.000 (2) | −0.002 (2) | 0.0076 (16) |
C13 | 0.039 (3) | 0.026 (2) | 0.041 (2) | 0.000 (2) | −0.006 (2) | 0.0050 (19) |
C14 | 0.035 (3) | 0.029 (2) | 0.031 (2) | 0.003 (2) | −0.0039 (19) | −0.0046 (18) |
C14A | 0.028 (2) | 0.026 (2) | 0.032 (2) | 0.0008 (19) | −0.0014 (18) | 0.0006 (18) |
C15 | 0.030 (2) | 0.030 (2) | 0.031 (2) | 0.004 (2) | −0.0082 (19) | −0.0008 (19) |
O15 | 0.051 (2) | 0.0372 (18) | 0.0319 (15) | 0.0018 (17) | 0.0037 (15) | −0.0037 (14) |
C16 | 0.024 (2) | 0.034 (2) | 0.028 (2) | 0.006 (2) | −0.0018 (16) | 0.0024 (19) |
O16 | 0.0331 (18) | 0.0413 (18) | 0.0317 (15) | 0.0030 (15) | 0.0064 (14) | 0.0067 (14) |
C16A | 0.021 (2) | 0.026 (2) | 0.033 (2) | −0.0038 (18) | −0.0024 (18) | 0.0060 (17) |
C17 | 0.031 (2) | 0.028 (2) | 0.031 (2) | −0.007 (2) | 0.0001 (19) | 0.0129 (18) |
C18 | 0.033 (3) | 0.019 (2) | 0.040 (2) | −0.0010 (19) | 0.001 (2) | 0.0044 (18) |
C19 | 0.033 (3) | 0.0178 (19) | 0.035 (2) | 0.0027 (18) | 0.0045 (19) | 0.0016 (17) |
N20 | 0.0241 (19) | 0.0213 (16) | 0.0304 (17) | −0.0018 (15) | 0.0005 (14) | 0.0012 (14) |
C20A | 0.024 (2) | 0.024 (2) | 0.0300 (19) | 0.0020 (17) | 0.0019 (18) | −0.0004 (16) |
C21A | 0.061 (3) | 0.030 (2) | 0.031 (2) | −0.023 (3) | 0.013 (2) | −0.0012 (19) |
N21 | 0.058 (3) | 0.027 (2) | 0.0290 (18) | −0.0123 (19) | 0.0061 (18) | −0.0039 (15) |
C22 | 0.047 (3) | 0.033 (2) | 0.040 (2) | −0.015 (2) | 0.014 (2) | −0.006 (2) |
C23 | 0.049 (3) | 0.064 (4) | 0.054 (3) | −0.008 (3) | 0.024 (3) | −0.008 (3) |
C24 | 0.044 (3) | 0.088 (4) | 0.055 (3) | −0.033 (3) | 0.011 (3) | −0.009 (3) |
C24A | 0.052 (3) | 0.054 (3) | 0.045 (3) | −0.031 (3) | 0.010 (2) | −0.010 (2) |
C25 | 0.071 (4) | 0.063 (4) | 0.047 (3) | −0.039 (3) | 0.013 (3) | −0.017 (3) |
O25 | 0.067 (3) | 0.141 (5) | 0.084 (3) | −0.064 (3) | 0.010 (3) | −0.054 (3) |
C26 | 0.069 (4) | 0.036 (3) | 0.036 (2) | −0.024 (3) | 0.007 (3) | 0.000 (2) |
O26 | 0.098 (3) | 0.039 (2) | 0.0333 (17) | −0.022 (2) | −0.0034 (19) | −0.0107 (15) |
C26A | 0.068 (4) | 0.027 (2) | 0.028 (2) | −0.018 (3) | 0.011 (2) | −0.0004 (18) |
C27 | 0.081 (4) | 0.028 (2) | 0.033 (2) | −0.008 (3) | 0.015 (3) | 0.003 (2) |
C28 | 0.075 (4) | 0.035 (2) | 0.037 (2) | −0.003 (3) | 0.015 (3) | 0.006 (2) |
C29 | 0.062 (4) | 0.038 (3) | 0.036 (2) | 0.000 (3) | 0.004 (2) | 0.002 (2) |
N30 | 0.057 (3) | 0.031 (2) | 0.0296 (18) | −0.008 (2) | 0.0066 (19) | −0.0013 (15) |
C30A | 0.062 (4) | 0.024 (2) | 0.029 (2) | −0.015 (2) | 0.006 (2) | 0.0004 (18) |
Cl1 | 0.0333 (5) | 0.0283 (5) | 0.0293 (4) | −0.0004 (5) | 0.0005 (4) | −0.0001 (4) |
O1 | 0.0320 (17) | 0.050 (2) | 0.0408 (16) | −0.0003 (16) | 0.0051 (13) | 0.0053 (16) |
O2 | 0.0432 (19) | 0.0342 (16) | 0.0392 (16) | 0.0003 (15) | −0.0021 (15) | −0.0133 (14) |
O3 | 0.069 (3) | 0.0270 (16) | 0.0323 (16) | 0.0022 (17) | −0.0044 (17) | 0.0060 (13) |
O4 | 0.0352 (16) | 0.0389 (17) | 0.0301 (14) | 0.0020 (15) | −0.0035 (12) | 0.0009 (14) |
Cl2 | 0.0358 (6) | 0.0303 (5) | 0.0323 (5) | 0.0006 (5) | 0.0008 (4) | −0.0055 (4) |
O7 | 0.046 (2) | 0.0279 (16) | 0.0488 (18) | 0.0069 (16) | 0.0003 (16) | 0.0036 (14) |
O8 | 0.224 (7) | 0.045 (2) | 0.077 (3) | 0.066 (3) | −0.080 (4) | −0.037 (2) |
O9 | 0.079 (3) | 0.059 (2) | 0.056 (2) | 0.018 (2) | 0.030 (2) | 0.0241 (19) |
O10 | 0.035 (2) | 0.133 (4) | 0.104 (3) | −0.023 (3) | −0.009 (2) | 0.065 (3) |
O51 | 0.060 | 0.080 | 0.060 | 0.018 | −0.008 | −0.015 |
O52 | 0.131 | 0.119 | 0.070 | 0.039 | −0.033 | 0.004 |
O53 | 0.081 | 0.068 | 0.049 | −0.021 | −0.009 | 0.007 |
O54 | 0.042 | 0.052 | 0.058 | −0.005 | −0.007 | 0.013 |
O55 | 0.078 | 0.130 | 0.078 | 0.012 | −0.018 | 0.026 |
Cu1—N1 | 2.045 (3) | C17—H17A | 0.9500 |
Cu1—N20 | 2.047 (3) | C18—C19 | 1.387 (6) |
Cu1—N21 | 2.059 (4) | C18—H18A | 0.9500 |
Cu1—N10 | 2.069 (3) | C19—N20 | 1.345 (5) |
Cu1—N11 | 2.253 (3) | C19—H19A | 0.9500 |
Cu1—N30 | 2.288 (4) | N20—C20A | 1.353 (5) |
C1A—N1 | 1.344 (5) | C21A—C24A | 1.380 (8) |
C1A—C4A | 1.380 (6) | C21A—N21 | 1.367 (5) |
C1A—C10A | 1.473 (6) | C21A—C30A | 1.460 (8) |
N1—C2 | 1.330 (5) | N21—C22 | 1.338 (6) |
C2—C3 | 1.404 (6) | C22—C23 | 1.378 (7) |
C2—H2A | 0.9500 | C22—H22A | 0.9500 |
C3—C4 | 1.389 (7) | C23—C24 | 1.378 (8) |
C3—H3A | 0.9500 | C23—H23A | 0.9500 |
C4—C4A | 1.386 (6) | C24—C24A | 1.387 (9) |
C4—H4A | 0.9500 | C24—H24A | 0.9500 |
C4A—C5 | 1.476 (7) | C24A—C25 | 1.480 (7) |
C5—O5 | 1.218 (5) | C25—O25 | 1.205 (7) |
C5—C6 | 1.532 (6) | C25—C26 | 1.538 (9) |
C6—O6 | 1.228 (6) | C26—O26 | 1.215 (6) |
C6—C6A | 1.485 (6) | C26—C26A | 1.466 (8) |
C6A—C10A | 1.381 (6) | C26A—C27 | 1.397 (8) |
C6A—C7 | 1.387 (6) | C26A—C30A | 1.400 (6) |
C7—C8 | 1.371 (6) | C27—C28 | 1.379 (8) |
C7—H7A | 0.9500 | C27—H27A | 0.9500 |
C8—C9 | 1.377 (6) | C28—C29 | 1.386 (7) |
C8—H8A | 0.9500 | C28—H28A | 0.9500 |
C9—N10 | 1.344 (5) | C29—N30 | 1.338 (7) |
C9—H9A | 0.9500 | C29—H29A | 0.9500 |
N10—C10A | 1.347 (5) | N30—C30A | 1.340 (7) |
C11A—N11 | 1.336 (5) | Cl1—O3 | 1.430 (3) |
C11A—C14A | 1.391 (6) | Cl1—O2 | 1.444 (3) |
C11A—C20A | 1.477 (5) | Cl1—O4 | 1.446 (3) |
N11—C12 | 1.347 (5) | Cl1—O1 | 1.452 (3) |
C12—C13 | 1.378 (6) | Cl2—O8 | 1.389 (4) |
C12—H12A | 0.9500 | Cl2—O9 | 1.410 (3) |
C13—C14 | 1.387 (6) | Cl2—O10 | 1.418 (4) |
C13—H13A | 0.9500 | Cl2—O7 | 1.448 (3) |
C14—C14A | 1.387 (6) | O51—H51A | 0.9799 |
C14—H14A | 0.9500 | O51—H51B | 0.9801 |
C14A—C15 | 1.476 (6) | O52—H52A | 0.9799 |
C15—O15 | 1.214 (5) | O52—H52B | 0.9799 |
C15—C16 | 1.541 (6) | O53—H53A | 0.9801 |
C16—O16 | 1.212 (5) | O53—H53B | 0.9799 |
C16—C16A | 1.475 (6) | O54—H54A | 0.9800 |
C16A—C20A | 1.389 (5) | O54—H54B | 0.9801 |
C16A—C17 | 1.399 (6) | O55—H55A | 0.9800 |
C17—C18 | 1.372 (6) | O55—H55B | 0.9800 |
N1—Cu1—N20 | 169.47 (13) | O16—C16—C15 | 118.9 (4) |
N1—Cu1—N21 | 92.32 (14) | C16A—C16—C15 | 118.1 (4) |
N20—Cu1—N21 | 90.84 (14) | C20A—C16A—C17 | 118.2 (4) |
N1—Cu1—N10 | 80.48 (13) | C20A—C16A—C16 | 120.5 (4) |
N20—Cu1—N10 | 98.36 (13) | C17—C16A—C16 | 121.3 (4) |
N21—Cu1—N10 | 166.19 (13) | C18—C17—C16A | 119.8 (4) |
N1—Cu1—N11 | 92.81 (12) | C18—C17—H17A | 120.1 |
N20—Cu1—N11 | 76.69 (12) | C16A—C17—H17A | 120.1 |
N21—Cu1—N11 | 103.45 (14) | C17—C18—C19 | 118.5 (4) |
N10—Cu1—N11 | 88.75 (13) | C17—C18—H18A | 120.8 |
N1—Cu1—N30 | 91.19 (12) | C19—C18—H18A | 120.8 |
N20—Cu1—N30 | 99.32 (13) | N20—C19—C18 | 123.1 (4) |
N21—Cu1—N30 | 76.04 (16) | N20—C19—H19A | 118.5 |
N10—Cu1—N30 | 92.24 (15) | C18—C19—H19A | 118.5 |
N11—Cu1—N30 | 175.99 (13) | C19—N20—C20A | 118.0 (3) |
N1—C1A—C4A | 122.0 (4) | C19—N20—Cu1 | 123.7 (3) |
N1—C1A—C10A | 116.5 (4) | C20A—N20—Cu1 | 118.1 (3) |
C4A—C1A—C10A | 121.3 (4) | N20—C20A—C16A | 122.4 (4) |
C2—N1—C1A | 118.9 (4) | N20—C20A—C11A | 116.2 (4) |
C2—N1—Cu1 | 127.1 (3) | C16A—C20A—C11A | 121.3 (4) |
C1A—N1—Cu1 | 113.8 (3) | C24A—C21A—N21 | 120.9 (5) |
N1—C2—C3 | 122.9 (4) | C24A—C21A—C30A | 122.4 (4) |
N1—C2—H2A | 118.6 | N21—C21A—C30A | 116.6 (5) |
C3—C2—H2A | 118.6 | C22—N21—C21A | 118.4 (4) |
C4—C3—C2 | 117.6 (4) | C22—N21—Cu1 | 123.1 (3) |
C4—C3—H3A | 121.2 | C21A—N21—Cu1 | 118.1 (3) |
C2—C3—H3A | 121.2 | N21—C22—C23 | 122.9 (4) |
C4A—C4—C3 | 119.3 (4) | N21—C22—H22A | 118.5 |
C4A—C4—H4A | 120.3 | C23—C22—H22A | 118.5 |
C3—C4—H4A | 120.3 | C22—C23—C24 | 119.1 (5) |
C1A—C4A—C4 | 119.2 (4) | C22—C23—H23A | 120.4 |
C1A—C4A—C5 | 120.3 (4) | C24—C23—H23A | 120.4 |
C4—C4A—C5 | 120.4 (4) | C24A—C24—C23 | 118.6 (5) |
O5—C5—C4A | 122.3 (4) | C24A—C24—H24A | 120.7 |
O5—C5—C6 | 120.0 (4) | C23—C24—H24A | 120.7 |
C4A—C5—C6 | 117.6 (4) | C21A—C24A—C24 | 120.0 (5) |
O6—C6—C6A | 122.1 (4) | C21A—C24A—C25 | 119.7 (6) |
O6—C6—C5 | 119.8 (4) | C24—C24A—C25 | 120.3 (5) |
C6A—C6—C5 | 118.0 (4) | O25—C25—C24A | 123.6 (6) |
C10A—C6A—C7 | 119.3 (4) | O25—C25—C26 | 118.4 (5) |
C10A—C6A—C6 | 119.2 (4) | C24A—C25—C26 | 118.0 (5) |
C7—C6A—C6 | 121.5 (4) | O26—C26—C26A | 122.9 (6) |
C8—C7—C6A | 118.4 (4) | O26—C26—C25 | 119.5 (5) |
C8—C7—H7A | 120.8 | C26A—C26—C25 | 117.6 (4) |
C6A—C7—H7A | 120.8 | C27—C26A—C30A | 119.1 (5) |
C7—C8—C9 | 119.6 (4) | C27—C26A—C26 | 120.5 (4) |
C7—C8—H8A | 120.2 | C30A—C26A—C26 | 120.4 (5) |
C9—C8—H8A | 120.2 | C28—C27—C26A | 119.1 (4) |
N10—C9—C8 | 122.4 (4) | C28—C27—H27A | 120.4 |
N10—C9—H9A | 118.8 | C26A—C27—H27A | 120.4 |
C8—C9—H9A | 118.8 | C27—C28—C29 | 117.4 (6) |
C9—N10—C10A | 118.1 (4) | C27—C28—H28A | 121.3 |
C9—N10—Cu1 | 128.4 (3) | C29—C28—H28A | 121.3 |
C10A—N10—Cu1 | 113.4 (3) | N30—C29—C28 | 124.8 (6) |
N10—C10A—C6A | 122.0 (4) | N30—C29—H29A | 117.6 |
N10—C10A—C1A | 115.7 (4) | C28—C29—H29A | 117.6 |
C6A—C10A—C1A | 122.2 (4) | C30A—N30—C29 | 117.6 (4) |
N11—C11A—C14A | 121.9 (4) | C30A—N30—Cu1 | 111.0 (3) |
N11—C11A—C20A | 116.6 (4) | C29—N30—Cu1 | 130.4 (4) |
C14A—C11A—C20A | 121.5 (4) | N30—C30A—C26A | 121.9 (5) |
C11A—N11—C12 | 118.7 (3) | N30—C30A—C21A | 117.1 (4) |
C11A—N11—Cu1 | 111.8 (2) | C26A—C30A—C21A | 121.0 (5) |
C12—N11—Cu1 | 129.5 (3) | O3—Cl1—O2 | 109.71 (18) |
N11—C12—C13 | 122.5 (4) | O3—Cl1—O4 | 110.2 (2) |
N11—C12—H12A | 118.7 | O2—Cl1—O4 | 109.14 (19) |
C13—C12—H12A | 118.7 | O3—Cl1—O1 | 109.5 (2) |
C14—C13—C12 | 119.0 (4) | O2—Cl1—O1 | 109.4 (2) |
C14—C13—H13A | 120.5 | O4—Cl1—O1 | 108.86 (16) |
C12—C13—H13A | 120.5 | O8—Cl2—O9 | 109.8 (3) |
C13—C14—C14A | 118.6 (4) | O8—Cl2—O10 | 110.8 (4) |
C13—C14—H14A | 120.7 | O9—Cl2—O10 | 108.8 (3) |
C14A—C14—H14A | 120.7 | O8—Cl2—O7 | 109.8 (2) |
C11A—C14A—C14 | 119.2 (4) | O9—Cl2—O7 | 110.3 (2) |
C11A—C14A—C15 | 120.4 (4) | O10—Cl2—O7 | 107.3 (2) |
C14—C14A—C15 | 120.4 (4) | H51A—O51—H51B | 108.5 |
O15—C15—C14A | 122.9 (4) | H52A—O52—H52B | 108.3 |
O15—C15—C16 | 119.1 (4) | H53A—O53—H53B | 106.8 |
C14A—C15—C16 | 117.9 (4) | H54A—O54—H54B | 108.2 |
O16—C16—C16A | 123.0 (4) | H55A—O55—H55B | 99.7 |
D—H···A | D—H | H···A | D···A | D—H···A |
O51—H51A···O10 | 0.98 | 1.99 | 2.937 (5) | 162.8 |
O51—H51B···O55 | 0.98 | 2.39 | 3.099 | 129.1 |
O52—H52A···O15i | 0.98 | 1.87 | 2.810 (3) | 158.6 |
O52—H52B···O55 | 0.98 | 1.96 | 2.623 | 123.1 |
O53—H53A···O2 | 0.98 | 1.99 | 2.956 (3) | 168.3 |
O53—H53B···O26 | 0.98 | 2.06 | 2.878 (3) | 139.3 |
O54—H54A···O53 | 0.98 | 1.90 | 2.824 | 157.1 |
O54—H54B···O51ii | 0.98 | 2.16 | 2.917 | 132.6 |
O55—H55A···O51 | 0.98 | 2.12 | 3.099 | 179.9 |
O55—H55B···O16i | 0.98 | 2.08 | 2.998 (3) | 154.4 |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C12H6N2O2)3](ClO4)2·4.5H2O |
Mr | 974.08 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 93 |
a, b, c (Å) | 13.136 (2), 14.071 (2), 20.636 (3) |
V (Å3) | 3814.2 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.10 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2004) |
Tmin, Tmax | 0.920, 0.923 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24980, 6940, 6206 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.122, 0.95 |
No. of reflections | 6940 |
No. of parameters | 534 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.53, −0.45 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | 0.517 (14) |
Computer programs: CrystalClear (Rigaku, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2003).
Cu1—N1 | 2.045 (3) | Cu1—N10 | 2.069 (3) |
Cu1—N20 | 2.047 (3) | Cu1—N11 | 2.253 (3) |
Cu1—N21 | 2.059 (4) | Cu1—N30 | 2.288 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O51—H51A···O10 | 0.98 | 1.99 | 2.937 (5) | 162.8 |
O51—H51B···O55 | 0.98 | 2.39 | 3.099 | 129.1 |
O52—H52A···O15i | 0.98 | 1.87 | 2.810 (3) | 158.6 |
O52—H52B···O55 | 0.98 | 1.96 | 2.623 | 123.1 |
O53—H53A···O2 | 0.98 | 1.99 | 2.956 (3) | 168.3 |
O53—H53B···O26 | 0.98 | 2.06 | 2.878 (3) | 139.3 |
O54—H54A···O53 | 0.98 | 1.90 | 2.824 | 157.1 |
O54—H54B···O51ii | 0.98 | 2.16 | 2.917 | 132.6 |
O55—H55A···O51 | 0.98 | 2.12 | 3.099 | 179.9 |
O55—H55B···O16i | 0.98 | 2.08 | 2.998 (3) | 154.4 |
Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+1, y+1/2, −z+1/2. |
Metal complexes with 1,10-phenantroline-5,6-dione (phen-dione) as a ligand have been increasingly studied over recent years (Hadadzadeh et al., 2006; Mansouri et al., 2007). The structure of monomeric hexacoordinated tris-chelated complexes of copper(II) have been reported previously (Majumdar et al., 1998 Wang et al., 2007). The six-coordinate copper center in the the title complex has distorted octahedral geometry (Fig. 1) being slightly tetragonally elongated due to the Jahn–Teller elongation of two Cu—N bonds in trans positions (average Cu—Neq = 2.05 and Cu—Nax = 2.27 Å) and the contraction of three of the N—Cu—N angles (average chelate angle N—Cu—N = 78°) from the ideal octahedral values, imposed by the three chelate ligands (Majumdar et al., 1998).