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
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.
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).