Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019599/gk2068sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019599/gk2068Isup2.hkl |
CCDC reference: 646657
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.041
- wR factor = 0.106
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl1 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl2 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 Cl O4
Alert level G FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C32 H28 Cl2 Cu2 N6 O12 Atom count from _chemical_formula_moiety:C32 H28 Cl4 Cu2 N6 O20 PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Some complexes based on di-2-pyridylketone hydrolysed derivative have been already isolated and structurally characterized (Lalioti et al., 2001; Papaefstathiou & Perlepes, 2002; Boudalis et al., 2003, 2004; Steel & Sumby, 2003; Tong et al., 2002; Serna et al., 2000; Li et al., 2006; Breeze et al., 1996).
The title compound was synthesized by refluxing a 20 ml EtOH/H2O solution (3:1, v/v) of Cu(OAc)2.H2O (0.257 g, 1.3 mmol), di-2-pyridylketone (0.185 g, 1 mmol) and pyridine (2.6 ml) for 1 h with stirring. After cooing, the solid NaClO4.H2O (0.210 g, 1.5 mmol) was added and the solution filtered. Blue prism crystals of (I) were obtained by slow evaporation of the blue filtrate for several days. Yield: 47.4% based on di-2-pyridylketone (0.210 g). (Anal. Calc. for C32H28Cl2Cu2N6O12: C, 43.35; H, 3.18; N 9.48. Found: C, 43.11; H, 2.97; N 9.49%).
All H atoms were positioned geometrically and were treated as riding, with C—H distances of 0.93 Å and O—H distances of 0.82 Å, with Uiso(H) = 1.2 Ueq(C, N). The highest electron density peak in a difference Fourier map is located near the O11 atom from the perchlorate anion.
Di-2-pyridylketone [(C5H4N2)CO] and its hydrolyzed derivative, di-2-pyridylmethanediol [(C5H4N)2C(OH)2], are considered as excellent ligands because of their various coordination modes. Some complexes based on the monoanion and dianion of di-2-pyridylmethanediol have been reported (Lalioti et al., 2001; Papaefstathiou & Perlepes, 2002; Boudalis et al., 2004; Steel & Sumby, 2003; Tong et al., 2002; Serna et al., 2000; Li et al., 2006). However, it is seldom reported that these ligands chelate the metal ion in N,N',O,O-tridentate mode (Breeze et al., 1996; Boudalis et al., 2003). Herein we present the crystal structure of the dinuclear compoud, (I), containing N,N',O,O-tridentate hydroxy-di-2-pyridylmethnolato ligand.
The structure of (I) consists of the cation, [bispyridyl-bis(hydroxy-di-2-pyridylmethanolato)]dicopper, and two percholrate anions (Fig. 1). In the cation, the two copper atoms, chelated by two N,N',O,O-tridentate hydroxy-di-2-pyridylmethanolato ligands, are not crystallographically equivalent. Each copper atom is also bound to one nitrogen atom from pyridine, resulting in a distorted square pyramidal coordination geometry. The Cu···Cu distance is 3.0375 (4) Å. The Cu—N and Cu—O bond lengths are 2.002 (2)—2.034 (2) Å and 1.9208 (17)—2.2837 (18) Å, respectively.
It is also noteworthy that the dinuclear structure is stabilized by intramolecular pyridine-pyridine π···π interation (the interplanar distance of 3.40 Å) and CH···π interaction (C14—H···the pyridine N5 centroid of 2.80 Å) (Fig. 2).
Some complexes based on di-2-pyridylketone hydrolysed derivative have been already isolated and structurally characterized (Lalioti et al., 2001; Papaefstathiou & Perlepes, 2002; Boudalis et al., 2003, 2004; Steel & Sumby, 2003; Tong et al., 2002; Serna et al., 2000; Li et al., 2006; Breeze et al., 1996).
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Cu2(C11H9N2O2)2(C5H5N)2](ClO4)2 | F(000) = 1800 |
Mr = 886.58 | Dx = 1.754 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.2269 (6) Å | Cell parameters from 8489 reflections |
b = 15.7136 (8) Å | θ = 3.2–27.5° |
c = 19.6142 (12) Å | µ = 1.50 mm−1 |
β = 104.034 (3)° | T = 293 K |
V = 3357.0 (3) Å3 | Prism, blue |
Z = 4 | 0.40 × 0.20 × 0.15 mm |
Rigaku Mercury CCD diffractometer | 7663 independent reflections |
Radiation source: fine-focus sealed tube | 6773 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
ω scans | θmax = 27.5°, θmin = 3.2° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | h = −14→13 |
Tmin = 0.657, Tmax = 0.798 | k = −20→20 |
25710 measured reflections | l = −20→25 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0526P)2 + 2.8234P] where P = (Fo2 + 2Fc2)/3 |
7663 reflections | (Δ/σ)max = 0.001 |
487 parameters | Δρmax = 1.21 e Å−3 |
0 restraints | Δρmin = −0.72 e Å−3 |
[Cu2(C11H9N2O2)2(C5H5N)2](ClO4)2 | V = 3357.0 (3) Å3 |
Mr = 886.58 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.2269 (6) Å | µ = 1.50 mm−1 |
b = 15.7136 (8) Å | T = 293 K |
c = 19.6142 (12) Å | 0.40 × 0.20 × 0.15 mm |
β = 104.034 (3)° |
Rigaku Mercury CCD diffractometer | 7663 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000) | 6773 reflections with I > 2σ(I) |
Tmin = 0.657, Tmax = 0.798 | Rint = 0.042 |
25710 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.08 | Δρmax = 1.21 e Å−3 |
7663 reflections | Δρmin = −0.72 e Å−3 |
487 parameters |
Experimental. IR (KBr pellet, cm-1): v(OH) 3449, v(C–O) 1605, v(C?N, C?C) 1473, 1448, 1384, v(ClO4-)1089, 624. |
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 | ||
Cu1 | 0.64841 (3) | 0.670160 (18) | 0.367839 (15) | 0.01667 (9) | |
Cu2 | 0.50841 (3) | 0.561750 (18) | 0.246451 (15) | 0.01642 (9) | |
Cl1 | 1.17153 (6) | 0.51344 (4) | 0.15172 (4) | 0.02879 (16) | |
Cl2 | 0.99762 (6) | 0.75509 (4) | 0.45799 (3) | 0.02225 (14) | |
N1 | 0.7087 (2) | 0.59111 (13) | 0.45118 (11) | 0.0176 (4) | |
N2 | 0.5160 (2) | 0.43867 (13) | 0.27837 (11) | 0.0181 (4) | |
N3 | 0.6030 (2) | 0.54674 (13) | 0.17214 (11) | 0.0182 (4) | |
N4 | 0.6705 (2) | 0.75622 (13) | 0.29634 (11) | 0.0182 (4) | |
N5 | 0.42158 (19) | 0.66984 (13) | 0.20679 (11) | 0.0168 (4) | |
N6 | 0.5364 (2) | 0.73951 (13) | 0.41114 (11) | 0.0175 (4) | |
O1 | 0.26025 (16) | 0.63617 (11) | 0.32037 (9) | 0.0192 (4) | |
H1A | 0.2443 | 0.5952 | 0.2938 | 0.029* | |
O2 | 0.46562 (16) | 0.60058 (10) | 0.33105 (9) | 0.0164 (3) | |
O3 | 0.70453 (16) | 0.59285 (11) | 0.30647 (9) | 0.0177 (4) | |
O4 | 0.88631 (16) | 0.62564 (12) | 0.27555 (10) | 0.0226 (4) | |
H3A | 0.9115 | 0.6493 | 0.3136 | 0.034* | |
O5 | 1.2489 (3) | 0.48847 (19) | 0.2173 (2) | 0.1021 (16) | |
O6 | 1.0668 (2) | 0.45880 (17) | 0.13553 (15) | 0.0496 (7) | |
O7 | 1.2369 (4) | 0.5094 (3) | 0.1002 (2) | 0.125 (2) | |
O8 | 1.1369 (2) | 0.59838 (14) | 0.16146 (16) | 0.0527 (7) | |
O9 | 1.0527 (3) | 0.7139 (2) | 0.52231 (13) | 0.0615 (8) | |
O10 | 0.8692 (2) | 0.77013 (15) | 0.45334 (13) | 0.0391 (5) | |
O11 | 1.0113 (2) | 0.6996 (2) | 0.40201 (13) | 0.0566 (8) | |
O12 | 1.0597 (2) | 0.83263 (15) | 0.4540 (2) | 0.0697 (10) | |
C1 | 0.6436 (2) | 0.57286 (16) | 0.49830 (13) | 0.0203 (5) | |
H11A | 0.5737 | 0.6048 | 0.4979 | 0.024* | |
C2 | 0.6760 (3) | 0.50846 (17) | 0.54751 (13) | 0.0226 (5) | |
H10A | 0.6289 | 0.4975 | 0.5795 | 0.027* | |
C3 | 0.7797 (3) | 0.46070 (17) | 0.54814 (14) | 0.0256 (6) | |
H28A | 0.8035 | 0.4169 | 0.5805 | 0.031* | |
C4 | 0.8474 (3) | 0.47919 (18) | 0.49981 (15) | 0.0264 (6) | |
H29A | 0.9172 | 0.4477 | 0.4989 | 0.032* | |
C5 | 0.8100 (2) | 0.54520 (17) | 0.45283 (14) | 0.0220 (5) | |
H12A | 0.8570 | 0.5582 | 0.4212 | 0.026* | |
C6 | 0.5483 (3) | 0.42389 (16) | 0.34787 (14) | 0.0220 (5) | |
H14A | 0.5774 | 0.4690 | 0.3780 | 0.026* | |
C7 | 0.5400 (3) | 0.34432 (17) | 0.37629 (16) | 0.0272 (6) | |
H13A | 0.5639 | 0.3360 | 0.4246 | 0.033* | |
C8 | 0.4958 (3) | 0.27754 (17) | 0.33183 (17) | 0.0293 (6) | |
H16A | 0.4868 | 0.2238 | 0.3497 | 0.035* | |
C9 | 0.4653 (3) | 0.29174 (17) | 0.26040 (16) | 0.0276 (6) | |
H17A | 0.4377 | 0.2472 | 0.2294 | 0.033* | |
C10 | 0.4761 (3) | 0.37286 (17) | 0.23539 (15) | 0.0240 (6) | |
H15A | 0.4550 | 0.3821 | 0.1871 | 0.029* | |
C11 | 0.5641 (3) | 0.50168 (16) | 0.11228 (13) | 0.0219 (5) | |
H9A | 0.4838 | 0.4816 | 0.1005 | 0.026* | |
C12 | 0.6394 (3) | 0.48436 (16) | 0.06794 (14) | 0.0231 (6) | |
H31A | 0.6104 | 0.4526 | 0.0273 | 0.028* | |
C13 | 0.7584 (3) | 0.51476 (16) | 0.08466 (14) | 0.0240 (6) | |
H8A | 0.8108 | 0.5035 | 0.0556 | 0.029* | |
C14 | 0.7984 (3) | 0.56241 (16) | 0.14549 (14) | 0.0221 (5) | |
H7A | 0.8778 | 0.5843 | 0.1574 | 0.026* | |
C15 | 0.7190 (2) | 0.57706 (15) | 0.18827 (13) | 0.0179 (5) | |
C16 | 0.7557 (2) | 0.62835 (16) | 0.25636 (13) | 0.0185 (5) | |
C17 | 0.7140 (2) | 0.72213 (15) | 0.24421 (13) | 0.0167 (5) | |
C18 | 0.7191 (2) | 0.76819 (16) | 0.18493 (13) | 0.0209 (5) | |
H2A | 0.7470 | 0.7431 | 0.1488 | 0.025* | |
C19 | 0.6816 (3) | 0.85284 (17) | 0.18036 (14) | 0.0237 (6) | |
H32A | 0.6843 | 0.8851 | 0.1410 | 0.028* | |
C20 | 0.6404 (3) | 0.88850 (17) | 0.23488 (15) | 0.0249 (6) | |
H4A | 0.6159 | 0.9452 | 0.2330 | 0.030* | |
C21 | 0.6363 (3) | 0.83846 (16) | 0.29222 (14) | 0.0229 (5) | |
H3B | 0.6091 | 0.8624 | 0.3291 | 0.027* | |
C22 | 0.4119 (3) | 0.70408 (17) | 0.14300 (13) | 0.0213 (5) | |
H26A | 0.4423 | 0.6738 | 0.1101 | 0.026* | |
C23 | 0.3584 (3) | 0.78284 (18) | 0.12438 (14) | 0.0237 (6) | |
H30A | 0.3511 | 0.8045 | 0.0794 | 0.028* | |
C24 | 0.3160 (3) | 0.82844 (17) | 0.17371 (14) | 0.0245 (6) | |
H27A | 0.2822 | 0.8823 | 0.1630 | 0.029* | |
C25 | 0.3242 (2) | 0.79327 (16) | 0.23946 (13) | 0.0196 (5) | |
H25A | 0.2955 | 0.8229 | 0.2733 | 0.024* | |
C26 | 0.3760 (2) | 0.71316 (15) | 0.25385 (12) | 0.0159 (5) | |
C27 | 0.3808 (2) | 0.66539 (15) | 0.32260 (13) | 0.0159 (5) | |
C28 | 0.4148 (2) | 0.72546 (15) | 0.38598 (12) | 0.0175 (5) | |
C29 | 0.3283 (3) | 0.76266 (16) | 0.41599 (13) | 0.0211 (5) | |
H20A | 0.2452 | 0.7516 | 0.3983 | 0.025* | |
C30 | 0.3675 (3) | 0.81696 (17) | 0.47304 (14) | 0.0244 (6) | |
H22A | 0.3109 | 0.8424 | 0.4942 | 0.029* | |
C31 | 0.4911 (3) | 0.83256 (16) | 0.49771 (14) | 0.0240 (6) | |
H21A | 0.5188 | 0.8694 | 0.5353 | 0.029* | |
C32 | 0.5734 (3) | 0.79289 (16) | 0.46606 (13) | 0.0220 (5) | |
H18A | 0.6569 | 0.8033 | 0.4831 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02118 (17) | 0.01560 (15) | 0.01365 (15) | 0.00121 (11) | 0.00500 (12) | 0.00078 (11) |
Cu2 | 0.02116 (17) | 0.01498 (15) | 0.01423 (15) | 0.00170 (11) | 0.00645 (12) | −0.00007 (11) |
Cl1 | 0.0244 (3) | 0.0229 (3) | 0.0364 (4) | 0.0040 (3) | 0.0022 (3) | −0.0075 (3) |
Cl2 | 0.0254 (3) | 0.0222 (3) | 0.0198 (3) | 0.0008 (2) | 0.0069 (2) | 0.0008 (2) |
N1 | 0.0193 (11) | 0.0180 (10) | 0.0153 (10) | −0.0013 (8) | 0.0035 (8) | −0.0002 (8) |
N2 | 0.0185 (11) | 0.0162 (10) | 0.0210 (11) | −0.0015 (8) | 0.0075 (9) | −0.0014 (8) |
N3 | 0.0220 (11) | 0.0172 (10) | 0.0157 (10) | 0.0010 (8) | 0.0052 (8) | 0.0016 (8) |
N4 | 0.0207 (11) | 0.0170 (10) | 0.0163 (10) | −0.0020 (8) | 0.0035 (8) | −0.0003 (8) |
N5 | 0.0182 (10) | 0.0181 (10) | 0.0144 (10) | −0.0006 (8) | 0.0047 (8) | −0.0001 (8) |
N6 | 0.0234 (11) | 0.0146 (9) | 0.0143 (9) | 0.0022 (8) | 0.0045 (8) | 0.0009 (8) |
O1 | 0.0206 (9) | 0.0190 (8) | 0.0198 (9) | −0.0028 (7) | 0.0084 (7) | −0.0012 (7) |
O2 | 0.0223 (9) | 0.0136 (8) | 0.0136 (8) | 0.0031 (7) | 0.0050 (7) | 0.0008 (6) |
O3 | 0.0237 (9) | 0.0165 (8) | 0.0135 (8) | 0.0008 (7) | 0.0059 (7) | 0.0016 (6) |
O4 | 0.0174 (9) | 0.0272 (9) | 0.0225 (9) | −0.0001 (7) | 0.0038 (7) | −0.0011 (8) |
O5 | 0.078 (2) | 0.0474 (17) | 0.133 (3) | −0.0171 (16) | −0.067 (2) | 0.0420 (19) |
O6 | 0.0327 (13) | 0.0512 (14) | 0.0619 (17) | −0.0109 (11) | 0.0056 (12) | −0.0258 (13) |
O7 | 0.138 (4) | 0.130 (4) | 0.151 (4) | −0.078 (3) | 0.119 (3) | −0.098 (3) |
O8 | 0.0483 (15) | 0.0254 (11) | 0.0778 (19) | 0.0152 (11) | 0.0027 (14) | −0.0088 (12) |
O9 | 0.072 (2) | 0.081 (2) | 0.0336 (13) | 0.0340 (16) | 0.0159 (13) | 0.0261 (14) |
O10 | 0.0263 (11) | 0.0409 (12) | 0.0534 (14) | 0.0024 (10) | 0.0162 (10) | 0.0030 (11) |
O11 | 0.0406 (14) | 0.093 (2) | 0.0338 (13) | 0.0099 (14) | 0.0051 (11) | −0.0287 (14) |
O12 | 0.0335 (14) | 0.0254 (12) | 0.149 (3) | −0.0024 (10) | 0.0194 (17) | 0.0098 (15) |
C1 | 0.0226 (13) | 0.0207 (12) | 0.0185 (12) | 0.0016 (10) | 0.0065 (10) | 0.0002 (10) |
C2 | 0.0274 (14) | 0.0229 (12) | 0.0194 (12) | −0.0041 (11) | 0.0093 (11) | 0.0012 (10) |
C3 | 0.0320 (16) | 0.0234 (13) | 0.0209 (13) | 0.0018 (11) | 0.0058 (11) | 0.0078 (10) |
C4 | 0.0230 (14) | 0.0280 (14) | 0.0292 (14) | 0.0067 (11) | 0.0081 (11) | 0.0067 (11) |
C5 | 0.0188 (13) | 0.0276 (13) | 0.0202 (13) | 0.0005 (10) | 0.0057 (10) | 0.0044 (10) |
C6 | 0.0261 (14) | 0.0184 (12) | 0.0237 (13) | 0.0013 (10) | 0.0101 (11) | −0.0005 (10) |
C7 | 0.0342 (16) | 0.0221 (13) | 0.0288 (14) | 0.0045 (12) | 0.0146 (12) | 0.0049 (11) |
C8 | 0.0304 (15) | 0.0159 (12) | 0.0472 (18) | 0.0000 (11) | 0.0199 (14) | 0.0022 (12) |
C9 | 0.0245 (14) | 0.0189 (12) | 0.0413 (17) | −0.0015 (11) | 0.0115 (12) | −0.0085 (12) |
C10 | 0.0244 (14) | 0.0220 (13) | 0.0257 (13) | −0.0004 (11) | 0.0064 (11) | −0.0062 (11) |
C11 | 0.0289 (14) | 0.0205 (12) | 0.0160 (11) | −0.0015 (11) | 0.0050 (10) | −0.0009 (10) |
C12 | 0.0331 (15) | 0.0200 (12) | 0.0168 (12) | 0.0013 (11) | 0.0075 (11) | −0.0009 (10) |
C13 | 0.0341 (15) | 0.0210 (12) | 0.0211 (13) | 0.0035 (11) | 0.0146 (11) | 0.0023 (10) |
C14 | 0.0274 (14) | 0.0188 (12) | 0.0237 (13) | −0.0010 (10) | 0.0134 (11) | 0.0027 (10) |
C15 | 0.0245 (13) | 0.0143 (11) | 0.0161 (11) | 0.0022 (10) | 0.0072 (10) | 0.0037 (9) |
C16 | 0.0186 (12) | 0.0195 (11) | 0.0180 (12) | −0.0006 (10) | 0.0056 (10) | 0.0004 (9) |
C17 | 0.0150 (12) | 0.0170 (11) | 0.0173 (11) | −0.0035 (9) | 0.0027 (9) | 0.0013 (9) |
C18 | 0.0218 (13) | 0.0222 (12) | 0.0193 (12) | −0.0040 (10) | 0.0063 (10) | 0.0028 (10) |
C19 | 0.0249 (14) | 0.0219 (12) | 0.0234 (13) | −0.0042 (11) | 0.0043 (11) | 0.0074 (10) |
C20 | 0.0270 (14) | 0.0165 (11) | 0.0299 (14) | −0.0008 (10) | 0.0044 (12) | 0.0030 (10) |
C21 | 0.0260 (14) | 0.0182 (12) | 0.0233 (13) | −0.0028 (10) | 0.0038 (11) | −0.0016 (10) |
C22 | 0.0249 (14) | 0.0243 (13) | 0.0160 (12) | 0.0015 (11) | 0.0074 (10) | 0.0027 (10) |
C23 | 0.0262 (14) | 0.0285 (13) | 0.0173 (12) | 0.0036 (11) | 0.0067 (11) | 0.0086 (10) |
C24 | 0.0277 (14) | 0.0213 (12) | 0.0239 (13) | 0.0044 (11) | 0.0053 (11) | 0.0061 (10) |
C25 | 0.0201 (13) | 0.0207 (12) | 0.0185 (12) | 0.0007 (10) | 0.0057 (10) | 0.0002 (10) |
C26 | 0.0148 (12) | 0.0180 (11) | 0.0151 (11) | −0.0016 (9) | 0.0039 (9) | −0.0004 (9) |
C27 | 0.0190 (12) | 0.0144 (11) | 0.0149 (11) | 0.0011 (9) | 0.0055 (9) | 0.0007 (9) |
C28 | 0.0243 (13) | 0.0150 (11) | 0.0135 (11) | 0.0008 (10) | 0.0052 (10) | 0.0029 (9) |
C29 | 0.0257 (14) | 0.0210 (12) | 0.0176 (12) | 0.0031 (10) | 0.0073 (10) | 0.0011 (10) |
C30 | 0.0347 (16) | 0.0224 (12) | 0.0189 (12) | 0.0048 (11) | 0.0118 (11) | −0.0015 (10) |
C31 | 0.0350 (15) | 0.0197 (12) | 0.0169 (12) | 0.0010 (11) | 0.0056 (11) | −0.0053 (10) |
C32 | 0.0260 (14) | 0.0201 (12) | 0.0177 (12) | −0.0004 (10) | 0.0009 (10) | −0.0013 (10) |
Cu1—O3 | 1.9208 (17) | C6—C7 | 1.381 (4) |
Cu1—N6 | 2.002 (2) | C6—H14A | 0.9300 |
Cu1—N4 | 2.007 (2) | C7—C8 | 1.378 (4) |
Cu1—N1 | 2.034 (2) | C7—H13A | 0.9300 |
Cu1—O2 | 2.2824 (18) | C8—C9 | 1.377 (4) |
Cu1—Cu2 | 3.0375 (4) | C8—H16A | 0.9300 |
Cu2—O2 | 1.9348 (17) | C9—C10 | 1.382 (4) |
Cu2—N3 | 2.014 (2) | C9—H17A | 0.9300 |
Cu2—N5 | 2.018 (2) | C10—H15A | 0.9300 |
Cu2—N2 | 2.028 (2) | C11—C12 | 1.379 (4) |
Cu2—O3 | 2.2837 (18) | C11—H9A | 0.9300 |
Cl1—O7 | 1.386 (3) | C12—C13 | 1.381 (4) |
Cl1—O8 | 1.416 (2) | C12—H31A | 0.9300 |
Cl1—O5 | 1.421 (3) | C13—C14 | 1.388 (4) |
Cl1—O6 | 1.428 (2) | C13—H8A | 0.9300 |
Cl2—O12 | 1.415 (2) | C14—C15 | 1.384 (4) |
Cl2—O9 | 1.419 (2) | C14—H7A | 0.9300 |
Cl2—O11 | 1.439 (2) | C15—C16 | 1.528 (3) |
Cl2—O10 | 1.442 (2) | C16—C17 | 1.547 (3) |
N1—C1 | 1.341 (3) | C17—C18 | 1.383 (3) |
N1—C5 | 1.341 (3) | C18—C19 | 1.391 (4) |
N2—C10 | 1.341 (3) | C18—H2A | 0.9300 |
N2—C6 | 1.343 (3) | C19—C20 | 1.383 (4) |
N3—C11 | 1.350 (3) | C19—H32A | 0.9300 |
N3—C15 | 1.351 (3) | C20—C21 | 1.382 (4) |
N4—C21 | 1.345 (3) | C20—H4A | 0.9300 |
N4—C17 | 1.346 (3) | C21—H3B | 0.9300 |
N5—C22 | 1.342 (3) | C22—C23 | 1.386 (4) |
N5—C26 | 1.344 (3) | C22—H26A | 0.9300 |
N6—C32 | 1.349 (3) | C23—C24 | 1.378 (4) |
N6—C28 | 1.353 (3) | C23—H30A | 0.9300 |
O1—C27 | 1.420 (3) | C24—C25 | 1.385 (4) |
O1—H1A | 0.8200 | C24—H27A | 0.9300 |
O2—C27 | 1.377 (3) | C25—C26 | 1.387 (3) |
O3—C16 | 1.372 (3) | C25—H25A | 0.9300 |
O4—C16 | 1.423 (3) | C26—C27 | 1.533 (3) |
O4—H3A | 0.8200 | C27—C28 | 1.534 (3) |
C1—C2 | 1.385 (4) | C28—C29 | 1.382 (4) |
C1—H11A | 0.9300 | C29—C30 | 1.391 (4) |
C2—C3 | 1.383 (4) | C29—H20A | 0.9300 |
C2—H10A | 0.9300 | C30—C31 | 1.376 (4) |
C3—C4 | 1.382 (4) | C30—H22A | 0.9300 |
C3—H28A | 0.9300 | C31—C32 | 1.381 (4) |
C4—C5 | 1.383 (4) | C31—H21A | 0.9300 |
C4—H29A | 0.9300 | C32—H18A | 0.9300 |
C5—H12A | 0.9300 | ||
O3—Cu1—N6 | 160.98 (8) | C7—C6—H14A | 118.7 |
O3—Cu1—N4 | 82.71 (8) | C8—C7—C6 | 118.9 (3) |
N6—Cu1—N4 | 97.27 (9) | C8—C7—H13A | 120.5 |
O3—Cu1—N1 | 91.24 (8) | C6—C7—H13A | 120.5 |
N6—Cu1—N1 | 96.45 (8) | C9—C8—C7 | 118.9 (3) |
N4—Cu1—N1 | 154.14 (9) | C9—C8—H16A | 120.6 |
O3—Cu1—O2 | 84.57 (7) | C7—C8—H16A | 120.6 |
N6—Cu1—O2 | 77.64 (8) | C8—C9—C10 | 119.3 (3) |
N4—Cu1—O2 | 110.87 (7) | C8—C9—H17A | 120.4 |
N1—Cu1—O2 | 93.44 (7) | C10—C9—H17A | 120.4 |
O3—Cu1—Cu2 | 48.71 (5) | N2—C10—C9 | 122.2 (3) |
N6—Cu1—Cu2 | 112.28 (6) | N2—C10—H15A | 118.9 |
N4—Cu1—Cu2 | 87.62 (6) | C9—C10—H15A | 118.9 |
N1—Cu1—Cu2 | 107.19 (6) | N3—C11—C12 | 122.3 (3) |
O2—Cu1—Cu2 | 39.54 (4) | N3—C11—H9A | 118.9 |
O2—Cu2—N3 | 160.32 (8) | C12—C11—H9A | 118.9 |
O2—Cu2—N5 | 82.41 (8) | C11—C12—C13 | 119.2 (2) |
N3—Cu2—N5 | 96.30 (8) | C11—C12—H31A | 120.4 |
O2—Cu2—N2 | 92.09 (8) | C13—C12—H31A | 120.4 |
N3—Cu2—N2 | 96.99 (8) | C12—C13—C14 | 118.9 (3) |
N5—Cu2—N2 | 154.38 (9) | C12—C13—H8A | 120.5 |
O2—Cu2—O3 | 84.22 (7) | C14—C13—H8A | 120.5 |
N3—Cu2—O3 | 77.68 (8) | C15—C14—C13 | 119.3 (3) |
N5—Cu2—O3 | 109.50 (7) | C15—C14—H7A | 120.4 |
N2—Cu2—O3 | 94.70 (7) | C13—C14—H7A | 120.4 |
O2—Cu2—Cu1 | 48.68 (5) | N3—C15—C14 | 121.7 (2) |
N3—Cu2—Cu1 | 111.69 (6) | N3—C15—C16 | 115.5 (2) |
N5—Cu2—Cu1 | 86.55 (6) | C14—C15—C16 | 122.7 (2) |
N2—Cu2—Cu1 | 108.53 (6) | O3—C16—O4 | 112.5 (2) |
O3—Cu2—Cu1 | 39.19 (4) | O3—C16—C15 | 109.9 (2) |
O7—Cl1—O8 | 110.6 (2) | O4—C16—C15 | 104.9 (2) |
O7—Cl1—O5 | 109.3 (3) | O3—C16—C17 | 109.5 (2) |
O8—Cl1—O5 | 105.4 (2) | O4—C16—C17 | 108.9 (2) |
O7—Cl1—O6 | 111.3 (2) | C15—C16—C17 | 111.1 (2) |
O8—Cl1—O6 | 111.02 (16) | N4—C17—C18 | 121.8 (2) |
O5—Cl1—O6 | 108.96 (18) | N4—C17—C16 | 114.5 (2) |
O12—Cl2—O9 | 109.1 (2) | C18—C17—C16 | 123.7 (2) |
O12—Cl2—O11 | 109.6 (2) | C17—C18—C19 | 118.8 (2) |
O9—Cl2—O11 | 107.33 (18) | C17—C18—H2A | 120.6 |
O12—Cl2—O10 | 110.69 (15) | C19—C18—H2A | 120.6 |
O9—Cl2—O10 | 110.15 (16) | C20—C19—C18 | 119.4 (2) |
O11—Cl2—O10 | 109.94 (15) | C20—C19—H32A | 120.3 |
C1—N1—C5 | 118.0 (2) | C18—C19—H32A | 120.3 |
C1—N1—Cu1 | 123.64 (18) | C21—C20—C19 | 118.8 (2) |
C5—N1—Cu1 | 117.58 (17) | C21—C20—H4A | 120.6 |
C10—N2—C6 | 118.1 (2) | C19—C20—H4A | 120.6 |
C10—N2—Cu2 | 123.97 (19) | N4—C21—C20 | 122.0 (3) |
C6—N2—Cu2 | 117.32 (17) | N4—C21—H3B | 119.0 |
C11—N3—C15 | 118.6 (2) | C20—C21—H3B | 119.0 |
C11—N3—Cu2 | 125.09 (19) | N5—C22—C23 | 122.4 (2) |
C15—N3—Cu2 | 115.90 (16) | N5—C22—H26A | 118.8 |
C21—N4—C17 | 119.2 (2) | C23—C22—H26A | 118.8 |
C21—N4—Cu1 | 127.41 (19) | C24—C23—C22 | 118.7 (2) |
C17—N4—Cu1 | 113.06 (16) | C24—C23—H30A | 120.6 |
C22—N5—C26 | 118.6 (2) | C22—C23—H30A | 120.6 |
C22—N5—Cu2 | 128.24 (18) | C23—C24—C25 | 119.3 (2) |
C26—N5—Cu2 | 112.97 (16) | C23—C24—H27A | 120.3 |
C32—N6—C28 | 118.7 (2) | C25—C24—H27A | 120.3 |
C32—N6—Cu1 | 125.03 (18) | C24—C25—C26 | 118.8 (2) |
C28—N6—Cu1 | 116.01 (16) | C24—C25—H25A | 120.6 |
C27—O1—H1A | 109.5 | C26—C25—H25A | 120.6 |
C27—O2—Cu2 | 116.00 (14) | N5—C26—C25 | 122.0 (2) |
C27—O2—Cu1 | 103.08 (13) | N5—C26—C27 | 114.7 (2) |
Cu2—O2—Cu1 | 91.77 (7) | C25—C26—C27 | 123.2 (2) |
C16—O3—Cu1 | 116.75 (15) | O2—C27—O1 | 113.01 (19) |
C16—O3—Cu2 | 103.70 (14) | O2—C27—C26 | 110.1 (2) |
Cu1—O3—Cu2 | 92.10 (7) | O1—C27—C26 | 107.54 (19) |
C16—O4—H3A | 109.5 | O2—C27—C28 | 109.19 (19) |
N1—C1—C2 | 122.8 (2) | O1—C27—C28 | 105.80 (19) |
N1—C1—H11A | 118.6 | C26—C27—C28 | 111.12 (19) |
C2—C1—H11A | 118.6 | N6—C28—C29 | 121.8 (2) |
C3—C2—C1 | 118.8 (3) | N6—C28—C27 | 115.3 (2) |
C3—C2—H10A | 120.6 | C29—C28—C27 | 122.9 (2) |
C1—C2—H10A | 120.6 | C28—C29—C30 | 119.0 (3) |
C4—C3—C2 | 118.8 (2) | C28—C29—H20A | 120.5 |
C4—C3—H28A | 120.6 | C30—C29—H20A | 120.5 |
C2—C3—H28A | 120.6 | C31—C30—C29 | 119.2 (3) |
C3—C4—C5 | 119.1 (3) | C31—C30—H22A | 120.4 |
C3—C4—H29A | 120.5 | C29—C30—H22A | 120.4 |
C5—C4—H29A | 120.5 | C30—C31—C32 | 119.3 (2) |
N1—C5—C4 | 122.6 (3) | C30—C31—H21A | 120.4 |
N1—C5—H12A | 118.7 | C32—C31—H21A | 120.4 |
C4—C5—H12A | 118.7 | N6—C32—C31 | 122.0 (3) |
N2—C6—C7 | 122.5 (3) | N6—C32—H18A | 119.0 |
N2—C6—H14A | 118.7 | C31—C32—H18A | 119.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O5i | 0.82 | 2.26 | 3.060 (5) | 165 |
O4—H3A···O11 | 0.82 | 1.99 | 2.790 (3) | 166 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C11H9N2O2)2(C5H5N)2](ClO4)2 |
Mr | 886.58 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.2269 (6), 15.7136 (8), 19.6142 (12) |
β (°) | 104.034 (3) |
V (Å3) | 3357.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.50 |
Crystal size (mm) | 0.40 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2000) |
Tmin, Tmax | 0.657, 0.798 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25710, 7663, 6773 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.106, 1.08 |
No. of reflections | 7663 |
No. of parameters | 487 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.21, −0.72 |
Computer programs: CrystalClear (Rigaku, 2000), CrystalClear, SHELXTL (Sheldrick, 1997), SHELXTL.
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Di-2-pyridylketone [(C5H4N2)CO] and its hydrolyzed derivative, di-2-pyridylmethanediol [(C5H4N)2C(OH)2], are considered as excellent ligands because of their various coordination modes. Some complexes based on the monoanion and dianion of di-2-pyridylmethanediol have been reported (Lalioti et al., 2001; Papaefstathiou & Perlepes, 2002; Boudalis et al., 2004; Steel & Sumby, 2003; Tong et al., 2002; Serna et al., 2000; Li et al., 2006). However, it is seldom reported that these ligands chelate the metal ion in N,N',O,O-tridentate mode (Breeze et al., 1996; Boudalis et al., 2003). Herein we present the crystal structure of the dinuclear compoud, (I), containing N,N',O,O-tridentate hydroxy-di-2-pyridylmethnolato ligand.
The structure of (I) consists of the cation, [bispyridyl-bis(hydroxy-di-2-pyridylmethanolato)]dicopper, and two percholrate anions (Fig. 1). In the cation, the two copper atoms, chelated by two N,N',O,O-tridentate hydroxy-di-2-pyridylmethanolato ligands, are not crystallographically equivalent. Each copper atom is also bound to one nitrogen atom from pyridine, resulting in a distorted square pyramidal coordination geometry. The Cu···Cu distance is 3.0375 (4) Å. The Cu—N and Cu—O bond lengths are 2.002 (2)—2.034 (2) Å and 1.9208 (17)—2.2837 (18) Å, respectively.
It is also noteworthy that the dinuclear structure is stabilized by intramolecular pyridine-pyridine π···π interation (the interplanar distance of 3.40 Å) and CH···π interaction (C14—H···the pyridine N5 centroid of 2.80 Å) (Fig. 2).