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
Key indicators
- Single-crystal X-ray study
- T = 93 K
- Mean (C-C) = 0.007 Å
- Disorder in solvent or counterion
- R factor = 0.047
- wR factor = 0.122
- Data-to-parameter ratio = 13.0
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT415_ALERT_2_A Short Inter D-H..H-X H24A .. H55A .. 1.87 Ang.
Alert level B PLAT417_ALERT_2_B Short Inter D-H..H-D H51B .. H55A .. 1.46 Ang. PLAT417_ALERT_2_B Short Inter D-H..H-D H51B .. H54B .. 1.88 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact O1 .. C26 .. 2.91 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact O4 .. C15 .. 2.83 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact O4 .. C16 .. 2.86 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact O5 .. C12 .. 2.84 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact O9 .. C16 .. 2.84 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact O16 .. C5 .. 2.77 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact O16 .. C4A .. 2.90 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact O54 .. C5 .. 2.88 Ang.
Alert level C STRVA01_ALERT_4_C Flack test results are ambiguous. From the CIF: _refine_ls_abs_structure_Flack 0.517 From the CIF: _refine_ls_abs_structure_Flack_su 0.014 PLAT033_ALERT_2_C Flack Parameter Value Deviates 2 * su from zero. 0.52 PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... O51 PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... O52 PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... O53 PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... O54 PLAT161_ALERT_4_C Missing or Zero su (esd) on x-coordinate for ... O55 PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... O51 PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... O52 PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... O53 PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... O54 PLAT162_ALERT_4_C Missing or Zero su (esd) on y-coordinate for ... O55 PLAT163_ALERT_4_C Missing or Zero su (esd) on z-coordinate for ... O51 PLAT163_ALERT_4_C Missing or Zero su (esd) on z-coordinate for ... O52 PLAT163_ALERT_4_C Missing or Zero su (esd) on z-coordinate for ... O53 PLAT163_ALERT_4_C Missing or Zero su (esd) on z-coordinate for ... O54 PLAT163_ALERT_4_C Missing or Zero su (esd) on z-coordinate for ... O55 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.70 Ratio PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.74 Ratio PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl2 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 3.00 Perc. PLAT333_ALERT_2_C Large Average Benzene C-C Dist. C11A -C20A 1.46 Ang. PLAT333_ALERT_2_C Large Average Benzene C-C Dist. C21A -C30A 1.45 Ang. PLAT335_ALERT_2_C Large Benzene C-C Range ....... C21A -C30A 0.16 Ang. PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7 PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C5 - C6 ... 1.53 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C15 - C16 ... 1.54 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C25 - C26 ... 1.54 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O1 .. C25 .. 2.92 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O1 .. C24A .. 2.96 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O6 .. C3 .. 2.98 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O7 .. C22 .. 2.93 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O9 .. C15 .. 2.98 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O54 .. C6 .. 3.00 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O55 .. C24 .. 2.95 Ang. PLAT757_ALERT_4_C D...A Calc 2.93811, Rep 2.937(5) ...... Senseless su O51 -O10 1.555 1.555 PLAT757_ALERT_4_C D...A Calc 2.80922, Rep 2.810(3) ...... Senseless su O52 -O15 1.555 2.665 PLAT757_ALERT_4_C D...A Calc 2.95566, Rep 2.956(3) ...... Senseless su O53 -O2 1.555 1.555 PLAT757_ALERT_4_C D...A Calc 2.87866, Rep 2.878(3) ...... Senseless su O53 -O26 1.555 1.555
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.35 From the CIF: _reflns_number_total 6940 Count of symmetry unique reflns 3897 Completeness (_total/calc) 178.09% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 3043 Fraction of Friedel pairs measured 0.781 Are heavy atom types Z>Si present yes
1 ALERT level A = In general: serious problem 10 ALERT level B = Potentially serious problem 42 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 27 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 23 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Majumdar et al. (1998); Hadadzadeh et al. (2006); Wang et al. (2007); Mansouri et al. (2007).
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. |
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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).