metal-organic compounds
(μ2-Chlorido)-(μ2-pyridine-2-carboxylato-1:2κN,O:O)-dichlorido(ethanol-κO)bis[N-hydroxy-1-(pyridin-2-yl)methanimine-κ2N,N′]dicobalt(II)
aShandong Provincial Key Laboratory of Soil Conservation and Environmental Protection, Business School, Linyi University, Linyi 276005, People's Republic of China
*Correspondence e-mail: lytucl@126.com
The dinuclear title compound, [Co2Cl3(C6H4NO2)(C6H6N2O)2(C2H5OH)], contains two six-coordinate CoII atoms with different octahedral coordination environments. One CoII atom is coordinated by two N atoms from one pyridine-2-carbaldehyde oxime ligand, by one terminal and one bridging Cl− ion, by one O atom from an ethanol molecule, and by one O atom from a bridging pyridine-2-carboxylate (picolinate) anion. The second CoII atom is coordinated by two N atoms from another pyridine-2-carbaldehyde oxime ligand, one N and one O atom from the bridging picolinate anion, and by one terminal Cl− and one bridging Cl− anion. The structure displays intramolecular O—H⋯O and O—H⋯Cl hydrogen bonds. Weak C—H⋯Cl hydrogen-bonding interactions connect the molecules into a three-dimensional network.
Related literature
For examples of CoII complexes with pyridine-2-carbaldehyde oxime ligands, see: Stamatatos et al. (2005a,b, 2009); Ross et al. (2001). For the isostructural NiII analogue, see: Zheng et al. (2011).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812041736/wm2687sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812041736/wm2687Isup2.hkl
A mixture of CoCl2.6H2O (0.0476 g, 0.20 mmol), pyridine-2-carbaldehyde oxime (0.0246 g, 0.20 mmol), pyridine-2-carboxylic acid (0.0250 g, 0.20 mmol) and ethanol (4 ml) was sealed into a 10 ml sample bottle reactor and heated at 393 K for 3 d under autogenous pressure, and then cooled to room temperature. Brown block-shaped crystals of the title compound were isolated, washed with distilled water, and dried in air (yield: 25%).
All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H = 0.93 Å for aromatic H atoms, 0.96 Å for CH3 type H atoms and 0.97 Å for CH2 type H atoms, respectively. Uiso(H) values were set at 1.5Ueq(C) for methyl H atoms, and 1.2Ueq(C) for the rest of the H atoms. H atoms bound to O atoms were found from difference maps and were refined with O—H = 0.85 Å and Uiso(H) = 1.2Ueq(O) for ethanol, and O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O) for the oxime H atoms.
Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids. | |
Fig. 2. The packing within the structure of compound (I) showing intermolecular C—H···Cl hydrogen bonding interactions. |
[Co2Cl3(C6H4NO2)(C6H6N2O)2(C2H6O)] | F(000) = 1288 |
Mr = 636.64 | char |
Monoclinic, P21/c | Dx = 1.622 Mg m−3 |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 8.7443 (17) Å | Cell parameters from 3510 reflections |
b = 18.144 (4) Å | θ = 2.6–25.3° |
c = 16.643 (3) Å | µ = 1.62 mm−1 |
β = 99.23 (3)° | T = 293 K |
V = 2606.4 (9) Å3 | Block, brown |
Z = 4 | 0.30 × 0.25 × 0.21 mm |
Bruker APEXII CCD diffractometer | 4520 independent reflections |
Radiation source: fine-focus sealed tube | 3778 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −10→7 |
Tmin = 0.642, Tmax = 0.727 | k = −21→17 |
17261 measured reflections | l = −18→19 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.18 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
4520 reflections | (Δ/σ)max = 0.035 |
319 parameters | Δρmax = 1.09 e Å−3 |
14 restraints | Δρmin = −1.31 e Å−3 |
[Co2Cl3(C6H4NO2)(C6H6N2O)2(C2H6O)] | V = 2606.4 (9) Å3 |
Mr = 636.64 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.7443 (17) Å | µ = 1.62 mm−1 |
b = 18.144 (4) Å | T = 293 K |
c = 16.643 (3) Å | 0.30 × 0.25 × 0.21 mm |
β = 99.23 (3)° |
Bruker APEXII CCD diffractometer | 4520 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 3778 reflections with I > 2σ(I) |
Tmin = 0.642, Tmax = 0.727 | Rint = 0.026 |
17261 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 14 restraints |
wR(F2) = 0.165 | H-atom parameters constrained |
S = 1.18 | Δρmax = 1.09 e Å−3 |
4520 reflections | Δρmin = −1.31 e Å−3 |
319 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.24774 (6) | 0.45656 (2) | 0.21872 (3) | 0.0402 (2) | |
O3 | 0.2615 (3) | 0.34808 (12) | 0.26096 (15) | 0.0431 (5) | |
Co2 | 0.14638 (5) | 0.27859 (2) | 0.16890 (3) | 0.0375 (2) | |
N1 | 0.2554 (3) | 0.56337 (14) | 0.16917 (18) | 0.0390 (7) | |
Cl3 | 0.08768 (10) | 0.39748 (4) | 0.09972 (5) | 0.0428 (3) | |
N5 | 0.1902 (3) | 0.20948 (15) | 0.27256 (18) | 0.0405 (7) | |
Cl4 | 0.38894 (10) | 0.25504 (5) | 0.12436 (5) | 0.0446 (3) | |
N2 | 0.4077 (4) | 0.51273 (17) | 0.3068 (2) | 0.0532 (8) | |
Cl5 | 0.04241 (13) | 0.47676 (5) | 0.29287 (7) | 0.0599 (3) | |
C13 | 0.2646 (4) | 0.24129 (18) | 0.3398 (2) | 0.0422 (8) | |
C5 | 0.1754 (4) | 0.58864 (19) | 0.1008 (2) | 0.0452 (8) | |
H5 | 0.1081 | 0.5569 | 0.0686 | 0.054* | |
O5 | 0.4324 (4) | 0.42495 (16) | 0.1587 (2) | 0.0755 (9) | |
H5A | 0.4181 | 0.3816 | 0.1395 | 0.091* | |
N3 | 0.0182 (4) | 0.20307 (16) | 0.0874 (2) | 0.0474 (7) | |
C17 | 0.1477 (5) | 0.13908 (19) | 0.2775 (3) | 0.0499 (9) | |
H17 | 0.0967 | 0.1159 | 0.2309 | 0.060* | |
N4 | −0.0840 (4) | 0.28758 (17) | 0.1948 (2) | 0.0508 (8) | |
C6 | 0.4351 (5) | 0.5793 (2) | 0.2900 (3) | 0.0539 (10) | |
H6 | 0.5061 | 0.6073 | 0.3248 | 0.065* | |
C1 | 0.3537 (4) | 0.61002 (19) | 0.2159 (2) | 0.0436 (8) | |
C2 | 0.3710 (5) | 0.6820 (2) | 0.1930 (3) | 0.0533 (10) | |
H2 | 0.4399 | 0.7130 | 0.2253 | 0.064* | |
C18 | 0.3098 (5) | 0.32080 (19) | 0.3299 (2) | 0.0473 (7) | |
O4 | 0.3859 (5) | 0.35214 (16) | 0.3880 (2) | 0.0806 (10) | |
O2 | −0.1396 (4) | 0.33138 (18) | 0.2505 (2) | 0.0702 (9) | |
H2A | −0.0851 | 0.3682 | 0.2592 | 0.105* | |
C14 | 0.2986 (5) | 0.2054 (2) | 0.4128 (2) | 0.0534 (10) | |
H14 | 0.3518 | 0.2291 | 0.4585 | 0.064* | |
C11 | 0.0707 (6) | 0.1604 (2) | 0.0337 (3) | 0.0619 (11) | |
H11 | 0.1747 | 0.1640 | 0.0285 | 0.074* | |
O1 | 0.4862 (5) | 0.48710 (18) | 0.3784 (2) | 0.0836 (11) | |
H1 | 0.4460 | 0.4488 | 0.3908 | 0.125* | |
C15 | 0.2517 (5) | 0.1328 (2) | 0.4166 (3) | 0.0560 (11) | |
H15 | 0.2716 | 0.1069 | 0.4655 | 0.067* | |
C7 | −0.1329 (5) | 0.1977 (2) | 0.0940 (3) | 0.0527 (10) | |
C16 | 0.1765 (5) | 0.0998 (2) | 0.3486 (3) | 0.0546 (10) | |
H16 | 0.1448 | 0.0510 | 0.3502 | 0.065* | |
C3 | 0.2871 (6) | 0.7074 (2) | 0.1233 (3) | 0.0618 (12) | |
H3 | 0.2966 | 0.7563 | 0.1080 | 0.074* | |
C4 | 0.1879 (5) | 0.6610 (2) | 0.0751 (3) | 0.0572 (10) | |
H4 | 0.1304 | 0.6776 | 0.0266 | 0.069* | |
C19 | 0.5751 (6) | 0.4495 (3) | 0.1537 (4) | 0.0872 (12) | |
H19A | 0.6444 | 0.4338 | 0.2021 | 0.105* | |
H19B | 0.5732 | 0.5029 | 0.1539 | 0.105* | |
C12 | −0.1848 (5) | 0.2464 (2) | 0.1537 (3) | 0.0571 (11) | |
H12 | −0.2878 | 0.2473 | 0.1613 | 0.068* | |
C8 | −0.2318 (6) | 0.1499 (3) | 0.0475 (3) | 0.0752 (14) | |
H8 | −0.3356 | 0.1474 | 0.0535 | 0.090* | |
C10 | −0.0215 (7) | 0.1106 (3) | −0.0154 (3) | 0.0793 (15) | |
H10 | 0.0197 | 0.0812 | −0.0524 | 0.095* | |
C20 | 0.6395 (7) | 0.4247 (3) | 0.0818 (4) | 0.0869 (17) | |
H20A | 0.6291 | 0.3722 | 0.0766 | 0.130* | |
H20B | 0.7471 | 0.4379 | 0.0879 | 0.130* | |
H20C | 0.5842 | 0.4479 | 0.0339 | 0.130* | |
C9 | −0.1751 (7) | 0.1058 (3) | −0.0078 (4) | 0.0886 (17) | |
H9 | −0.2401 | 0.0730 | −0.0399 | 0.106* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0441 (3) | 0.0344 (3) | 0.0410 (3) | −0.00033 (19) | 0.0033 (3) | −0.00025 (17) |
O3 | 0.0526 (13) | 0.0361 (11) | 0.0379 (12) | 0.0020 (10) | −0.0012 (11) | 0.0034 (9) |
Co2 | 0.0386 (3) | 0.0373 (3) | 0.0360 (3) | −0.00170 (18) | 0.0039 (3) | 0.00143 (17) |
N1 | 0.0405 (16) | 0.0351 (13) | 0.0410 (17) | −0.0009 (12) | 0.0053 (14) | −0.0003 (12) |
Cl3 | 0.0450 (5) | 0.0427 (5) | 0.0389 (5) | −0.0019 (4) | 0.0013 (4) | 0.0037 (3) |
N5 | 0.0423 (16) | 0.0403 (14) | 0.0388 (17) | 0.0020 (12) | 0.0059 (14) | 0.0061 (12) |
Cl4 | 0.0408 (5) | 0.0464 (5) | 0.0470 (6) | 0.0052 (4) | 0.0082 (4) | −0.0003 (4) |
N2 | 0.060 (2) | 0.0443 (17) | 0.049 (2) | −0.0008 (15) | −0.0098 (17) | 0.0022 (14) |
Cl5 | 0.0740 (7) | 0.0520 (5) | 0.0591 (7) | 0.0109 (5) | 0.0272 (6) | 0.0026 (4) |
C13 | 0.050 (2) | 0.0398 (16) | 0.038 (2) | 0.0077 (16) | 0.0088 (18) | 0.0047 (14) |
C5 | 0.046 (2) | 0.0465 (18) | 0.041 (2) | −0.0026 (16) | 0.0009 (18) | −0.0007 (15) |
O5 | 0.0564 (16) | 0.0550 (15) | 0.124 (3) | −0.0128 (13) | 0.0415 (18) | −0.0243 (16) |
N3 | 0.0502 (19) | 0.0450 (15) | 0.0437 (18) | −0.0074 (14) | −0.0024 (16) | 0.0040 (13) |
C17 | 0.054 (2) | 0.0426 (19) | 0.053 (2) | −0.0017 (17) | 0.007 (2) | 0.0066 (16) |
N4 | 0.0475 (19) | 0.0470 (16) | 0.061 (2) | 0.0025 (15) | 0.0181 (18) | 0.0093 (15) |
C6 | 0.061 (2) | 0.0441 (19) | 0.052 (2) | −0.0105 (18) | −0.004 (2) | −0.0081 (17) |
C1 | 0.044 (2) | 0.0435 (18) | 0.043 (2) | −0.0015 (15) | 0.0060 (17) | −0.0062 (15) |
C2 | 0.063 (2) | 0.0456 (19) | 0.051 (2) | −0.0122 (18) | 0.007 (2) | −0.0038 (17) |
C18 | 0.0573 (18) | 0.0397 (15) | 0.0412 (16) | 0.0055 (14) | −0.0031 (16) | 0.0011 (13) |
O4 | 0.128 (3) | 0.0466 (15) | 0.0528 (19) | −0.0108 (18) | −0.029 (2) | 0.0031 (13) |
O2 | 0.0638 (19) | 0.0657 (19) | 0.088 (2) | 0.0002 (15) | 0.0337 (19) | −0.0059 (16) |
C14 | 0.067 (3) | 0.055 (2) | 0.039 (2) | 0.0097 (19) | 0.009 (2) | 0.0035 (16) |
C11 | 0.071 (3) | 0.059 (2) | 0.055 (3) | −0.009 (2) | 0.008 (2) | −0.0079 (19) |
O1 | 0.108 (3) | 0.0595 (19) | 0.066 (2) | −0.0138 (18) | −0.037 (2) | 0.0093 (15) |
C15 | 0.070 (3) | 0.053 (2) | 0.049 (2) | 0.008 (2) | 0.020 (2) | 0.0179 (18) |
C7 | 0.047 (2) | 0.053 (2) | 0.055 (3) | −0.0141 (18) | −0.002 (2) | 0.0151 (18) |
C16 | 0.056 (2) | 0.049 (2) | 0.060 (3) | 0.0027 (18) | 0.016 (2) | 0.0178 (18) |
C3 | 0.082 (3) | 0.0406 (19) | 0.062 (3) | −0.008 (2) | 0.009 (3) | 0.0075 (19) |
C4 | 0.068 (3) | 0.048 (2) | 0.052 (2) | −0.001 (2) | −0.001 (2) | 0.0091 (17) |
C19 | 0.062 (2) | 0.077 (2) | 0.130 (3) | −0.0157 (18) | 0.038 (2) | −0.028 (2) |
C12 | 0.039 (2) | 0.060 (2) | 0.073 (3) | −0.0074 (19) | 0.011 (2) | 0.013 (2) |
C8 | 0.064 (3) | 0.078 (3) | 0.078 (3) | −0.027 (3) | −0.007 (3) | 0.006 (3) |
C10 | 0.104 (4) | 0.068 (3) | 0.063 (3) | −0.021 (3) | 0.005 (3) | −0.020 (2) |
C20 | 0.082 (4) | 0.077 (3) | 0.112 (5) | −0.012 (3) | 0.048 (4) | −0.013 (3) |
C9 | 0.099 (4) | 0.077 (3) | 0.079 (4) | −0.040 (3) | −0.018 (3) | −0.004 (3) |
Co1—O3 | 2.087 (2) | C6—H6 | 0.9300 |
Co1—O5 | 2.110 (3) | C1—C2 | 1.376 (5) |
Co1—N1 | 2.111 (3) | C2—C3 | 1.350 (6) |
Co1—N2 | 2.118 (4) | C2—H2 | 0.9300 |
Co1—Cl5 | 2.3648 (11) | C18—O4 | 1.223 (5) |
Co1—Cl3 | 2.4781 (12) | O2—H2A | 0.8200 |
O3—C18 | 1.258 (4) | C14—C15 | 1.384 (5) |
O3—Co2 | 2.111 (3) | C14—H14 | 0.9300 |
Co2—N3 | 2.118 (3) | C11—C10 | 1.388 (7) |
Co2—N5 | 2.117 (3) | C11—H11 | 0.9300 |
Co2—N4 | 2.133 (3) | O1—H1 | 0.8200 |
Co2—Cl4 | 2.3948 (10) | C15—C16 | 1.354 (6) |
Co2—Cl3 | 2.4603 (10) | C15—H15 | 0.9300 |
N1—C5 | 1.319 (5) | C7—C8 | 1.372 (6) |
N1—C1 | 1.358 (5) | C7—C12 | 1.455 (6) |
N5—C17 | 1.337 (4) | C16—H16 | 0.9300 |
N5—C13 | 1.333 (5) | C3—C4 | 1.371 (6) |
N2—C6 | 1.271 (5) | C3—H3 | 0.9300 |
N2—O1 | 1.359 (5) | C4—H4 | 0.9300 |
C13—C14 | 1.369 (5) | C19—C20 | 1.473 (7) |
C13—C18 | 1.512 (5) | C19—H19A | 0.9700 |
C5—C4 | 1.391 (5) | C19—H19B | 0.9700 |
C5—H5 | 0.9300 | C12—H12 | 0.9300 |
O5—C19 | 1.339 (5) | C8—C9 | 1.371 (8) |
O5—H5A | 0.8499 | C8—H8 | 0.9300 |
N3—C11 | 1.319 (5) | C10—C9 | 1.371 (8) |
N3—C7 | 1.347 (5) | C10—H10 | 0.9300 |
C17—C16 | 1.370 (6) | C20—H20A | 0.9600 |
C17—H17 | 0.9300 | C20—H20B | 0.9600 |
N4—C12 | 1.269 (6) | C20—H20C | 0.9600 |
N4—O2 | 1.368 (4) | C9—H9 | 0.9300 |
C6—C1 | 1.435 (6) | ||
O3—Co1—O5 | 84.04 (11) | O2—N4—Co2 | 129.1 (3) |
O3—Co1—N1 | 173.45 (10) | N2—C6—C1 | 118.2 (4) |
O5—Co1—N1 | 89.42 (12) | N2—C6—H6 | 120.9 |
O3—Co1—N2 | 102.98 (11) | C1—C6—H6 | 120.9 |
O5—Co1—N2 | 89.32 (14) | N1—C1—C2 | 121.4 (4) |
N1—Co1—N2 | 76.69 (12) | N1—C1—C6 | 115.5 (3) |
O3—Co1—Cl5 | 88.74 (7) | C2—C1—C6 | 123.1 (4) |
O5—Co1—Cl5 | 172.77 (9) | C3—C2—C1 | 119.5 (4) |
N1—Co1—Cl5 | 97.81 (8) | C3—C2—H2 | 120.2 |
N2—Co1—Cl5 | 92.09 (10) | C1—C2—H2 | 120.2 |
O3—Co1—Cl3 | 81.72 (7) | O4—C18—O3 | 126.8 (3) |
O5—Co1—Cl3 | 83.16 (10) | O4—C18—C13 | 118.4 (3) |
N1—Co1—Cl3 | 97.71 (9) | O3—C18—C13 | 114.8 (3) |
N2—Co1—Cl3 | 170.71 (10) | N4—O2—H2A | 109.5 |
Cl5—Co1—Cl3 | 96.05 (4) | C13—C14—C15 | 118.0 (4) |
C18—O3—Co1 | 132.1 (2) | C13—C14—H14 | 121.0 |
C18—O3—Co2 | 118.5 (2) | C15—C14—H14 | 121.0 |
Co1—O3—Co2 | 108.89 (11) | N3—C11—C10 | 123.3 (4) |
O3—Co2—N3 | 173.23 (10) | N3—C11—H11 | 118.3 |
O3—Co2—N5 | 76.08 (11) | C10—C11—H11 | 118.3 |
N3—Co2—N5 | 98.43 (12) | N2—O1—H1 | 109.5 |
O3—Co2—N4 | 99.41 (12) | C16—C15—C14 | 119.3 (4) |
N3—Co2—N4 | 76.05 (13) | C16—C15—H15 | 120.3 |
N5—Co2—N4 | 86.20 (12) | C14—C15—H15 | 120.3 |
O3—Co2—Cl4 | 89.33 (7) | N3—C7—C8 | 122.5 (4) |
N3—Co2—Cl4 | 95.19 (9) | N3—C7—C12 | 115.4 (4) |
N5—Co2—Cl4 | 95.35 (8) | C8—C7—C12 | 122.1 (4) |
N4—Co2—Cl4 | 171.24 (10) | C15—C16—C17 | 119.3 (4) |
O3—Co2—Cl3 | 81.68 (7) | C15—C16—H16 | 120.3 |
N3—Co2—Cl3 | 102.62 (9) | C17—C16—H16 | 120.3 |
N5—Co2—Cl3 | 153.82 (8) | C2—C3—C4 | 119.9 (4) |
N4—Co2—Cl3 | 83.95 (9) | C2—C3—H3 | 120.0 |
Cl4—Co2—Cl3 | 98.06 (3) | C4—C3—H3 | 120.0 |
C5—N1—C1 | 118.5 (3) | C3—C4—C5 | 118.2 (4) |
C5—N1—Co1 | 127.6 (2) | C3—C4—H4 | 120.9 |
C1—N1—Co1 | 113.9 (2) | C5—C4—H4 | 120.9 |
Co2—Cl3—Co1 | 87.51 (4) | O5—C19—C20 | 115.5 (5) |
C17—N5—C13 | 117.7 (3) | O5—C19—H19A | 108.4 |
C17—N5—Co2 | 126.9 (3) | C20—C19—H19A | 108.4 |
C13—N5—Co2 | 115.3 (2) | O5—C19—H19B | 108.4 |
C6—N2—O1 | 115.6 (4) | C20—C19—H19B | 108.4 |
C6—N2—Co1 | 115.6 (3) | H19A—C19—H19B | 107.5 |
O1—N2—Co1 | 128.9 (2) | N4—C12—C7 | 117.4 (4) |
N5—C13—C14 | 123.2 (3) | N4—C12—H12 | 121.3 |
N5—C13—C18 | 115.0 (3) | C7—C12—H12 | 121.3 |
C14—C13—C18 | 121.9 (4) | C9—C8—C7 | 119.0 (5) |
N1—C5—C4 | 122.5 (4) | C9—C8—H8 | 120.5 |
N1—C5—H5 | 118.8 | C7—C8—H8 | 120.5 |
C4—C5—H5 | 118.8 | C9—C10—C11 | 118.1 (5) |
C19—O5—Co1 | 136.9 (3) | C9—C10—H10 | 120.9 |
C19—O5—H5A | 111.5 | C11—C10—H10 | 120.9 |
Co1—O5—H5A | 110.5 | C19—C20—H20A | 109.5 |
C11—N3—C7 | 117.7 (4) | C19—C20—H20B | 109.5 |
C11—N3—Co2 | 127.4 (3) | H20A—C20—H20B | 109.5 |
C7—N3—Co2 | 114.8 (3) | C19—C20—H20C | 109.5 |
N5—C17—C16 | 122.4 (4) | H20A—C20—H20C | 109.5 |
N5—C17—H17 | 118.8 | H20B—C20—H20C | 109.5 |
C16—C17—H17 | 118.8 | C10—C9—C8 | 119.3 (5) |
C12—N4—O2 | 114.6 (3) | C10—C9—H9 | 120.3 |
C12—N4—Co2 | 116.3 (3) | C8—C9—H9 | 120.3 |
O5—Co1—O3—C18 | 107.7 (3) | N5—Co2—N3—C11 | −95.8 (4) |
N2—Co1—O3—C18 | 19.8 (3) | N4—Co2—N3—C11 | −179.7 (4) |
Cl5—Co1—O3—C18 | −72.1 (3) | Cl4—Co2—N3—C11 | 0.4 (3) |
Cl3—Co1—O3—C18 | −168.4 (3) | Cl3—Co2—N3—C11 | 99.9 (3) |
O5—Co1—O3—Co2 | −80.18 (14) | N5—Co2—N3—C7 | 82.3 (3) |
N2—Co1—O3—Co2 | −168.10 (12) | N4—Co2—N3—C7 | −1.6 (3) |
Cl5—Co1—O3—Co2 | 100.04 (10) | Cl4—Co2—N3—C7 | 178.5 (3) |
Cl3—Co1—O3—Co2 | 3.74 (8) | Cl3—Co2—N3—C7 | −82.0 (3) |
C18—O3—Co2—N5 | 3.5 (3) | C13—N5—C17—C16 | 0.8 (5) |
Co1—O3—Co2—N5 | −169.85 (13) | Co2—N5—C17—C16 | −177.4 (3) |
C18—O3—Co2—N4 | 87.2 (3) | O3—Co2—N4—C12 | −174.2 (3) |
Co1—O3—Co2—N4 | −86.18 (13) | N3—Co2—N4—C12 | 0.7 (3) |
C18—O3—Co2—Cl4 | −92.2 (3) | N5—Co2—N4—C12 | −99.0 (3) |
Co1—O3—Co2—Cl4 | 94.47 (9) | Cl3—Co2—N4—C12 | 105.3 (3) |
C18—O3—Co2—Cl3 | 169.6 (3) | O3—Co2—N4—O2 | 5.2 (3) |
Co1—O3—Co2—Cl3 | −3.77 (8) | N3—Co2—N4—O2 | −179.9 (3) |
O5—Co1—N1—C5 | 92.3 (3) | N5—Co2—N4—O2 | 80.4 (3) |
N2—Co1—N1—C5 | −178.2 (3) | Cl3—Co2—N4—O2 | −75.3 (3) |
Cl5—Co1—N1—C5 | −87.9 (3) | O1—N2—C6—C1 | −178.9 (3) |
Cl3—Co1—N1—C5 | 9.3 (3) | Co1—N2—C6—C1 | 1.8 (5) |
O5—Co1—N1—C1 | −88.9 (2) | C5—N1—C1—C2 | −0.3 (5) |
N2—Co1—N1—C1 | 0.5 (2) | Co1—N1—C1—C2 | −179.1 (3) |
Cl5—Co1—N1—C1 | 90.8 (2) | C5—N1—C1—C6 | 179.0 (3) |
Cl3—Co1—N1—C1 | −171.9 (2) | Co1—N1—C1—C6 | 0.2 (4) |
O3—Co2—Cl3—Co1 | 3.01 (7) | N2—C6—C1—N1 | −1.3 (5) |
N3—Co2—Cl3—Co1 | 177.68 (9) | N2—C6—C1—C2 | 178.0 (4) |
N5—Co2—Cl3—Co1 | 35.0 (2) | N1—C1—C2—C3 | 1.0 (6) |
N4—Co2—Cl3—Co1 | 103.47 (11) | C6—C1—C2—C3 | −178.3 (4) |
Cl4—Co2—Cl3—Co1 | −85.12 (4) | Co1—O3—C18—O4 | −12.9 (6) |
O3—Co1—Cl3—Co2 | −3.04 (7) | Co2—O3—C18—O4 | 175.5 (4) |
O5—Co1—Cl3—Co2 | 81.89 (10) | Co1—O3—C18—C13 | 166.0 (2) |
N1—Co1—Cl3—Co2 | 170.37 (8) | Co2—O3—C18—C13 | −5.5 (4) |
Cl5—Co1—Cl3—Co2 | −90.87 (4) | N5—C13—C18—O4 | −176.1 (4) |
O3—Co2—N5—C17 | 177.6 (3) | C14—C13—C18—O4 | 3.9 (6) |
N3—Co2—N5—C17 | 1.7 (3) | N5—C13—C18—O3 | 4.9 (5) |
N4—Co2—N5—C17 | 76.9 (3) | C14—C13—C18—O3 | −175.2 (3) |
Cl4—Co2—N5—C17 | −94.4 (3) | N5—C13—C14—C15 | −0.7 (6) |
Cl3—Co2—N5—C17 | 145.0 (2) | C18—C13—C14—C15 | 179.4 (3) |
O3—Co2—N5—C13 | −0.5 (2) | C7—N3—C11—C10 | −0.4 (7) |
N3—Co2—N5—C13 | −176.5 (2) | Co2—N3—C11—C10 | 177.7 (4) |
N4—Co2—N5—C13 | −101.2 (3) | C13—C14—C15—C16 | 0.9 (6) |
Cl4—Co2—N5—C13 | 87.4 (2) | C11—N3—C7—C8 | 0.2 (6) |
Cl3—Co2—N5—C13 | −33.2 (4) | Co2—N3—C7—C8 | −178.1 (3) |
O3—Co1—N2—C6 | 172.0 (3) | C11—N3—C7—C12 | −179.5 (4) |
O5—Co1—N2—C6 | 88.3 (3) | Co2—N3—C7—C12 | 2.2 (4) |
N1—Co1—N2—C6 | −1.2 (3) | C14—C15—C16—C17 | −0.4 (6) |
Cl5—Co1—N2—C6 | −98.8 (3) | N5—C17—C16—C15 | −0.5 (6) |
O3—Co1—N2—O1 | −7.2 (4) | C1—C2—C3—C4 | −1.3 (6) |
O5—Co1—N2—O1 | −90.9 (4) | C2—C3—C4—C5 | 0.9 (6) |
N1—Co1—N2—O1 | 179.5 (4) | N1—C5—C4—C3 | −0.2 (6) |
Cl5—Co1—N2—O1 | 82.0 (4) | Co1—O5—C19—C20 | −158.8 (4) |
C17—N5—C13—C14 | −0.2 (5) | O2—N4—C12—C7 | −179.2 (3) |
Co2—N5—C13—C14 | 178.2 (3) | Co2—N4—C12—C7 | 0.3 (5) |
C17—N5—C13—C18 | 179.8 (3) | N3—C7—C12—N4 | −1.7 (6) |
Co2—N5—C13—C18 | −1.9 (4) | C8—C7—C12—N4 | 178.7 (4) |
C1—N1—C5—C4 | −0.1 (5) | N3—C7—C8—C9 | 0.0 (7) |
Co1—N1—C5—C4 | 178.6 (3) | C12—C7—C8—C9 | 179.6 (5) |
O3—Co1—O5—C19 | −126.6 (6) | N3—C11—C10—C9 | 0.4 (8) |
N1—Co1—O5—C19 | 53.2 (6) | C11—C10—C9—C8 | −0.2 (8) |
N2—Co1—O5—C19 | −23.5 (6) | C7—C8—C9—C10 | 0.0 (8) |
Cl3—Co1—O5—C19 | 151.0 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···Cl5 | 0.82 | 2.29 | 3.103 (3) | 172 |
O1—H1···O4 | 0.82 | 1.83 | 2.615 (4) | 160 |
O5—H5A···Cl4 | 0.85 | 2.32 | 3.147 (3) | 164 |
C12—H12···Cl4i | 0.93 | 2.80 | 3.684 (4) | 160 |
C10—H10···Cl5ii | 0.93 | 2.82 | 3.684 (5) | 156 |
C14—H14···Cl4iii | 0.93 | 2.74 | 3.556 (4) | 147 |
C2—H2···Cl4iv | 0.93 | 2.81 | 3.654 (5) | 152 |
C17—H17···Cl5v | 0.93 | 2.80 | 3.491 (4) | 132 |
Symmetry codes: (i) x−1, y, z; (ii) x, −y+1/2, z−1/2; (iii) x, −y+1/2, z+1/2; (iv) −x+1, y+1/2, −z+1/2; (v) −x, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co2Cl3(C6H4NO2)(C6H6N2O)2(C2H6O)] |
Mr | 636.64 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 8.7443 (17), 18.144 (4), 16.643 (3) |
β (°) | 99.23 (3) |
V (Å3) | 2606.4 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.62 |
Crystal size (mm) | 0.30 × 0.25 × 0.21 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.642, 0.727 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17261, 4520, 3778 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.165, 1.18 |
No. of reflections | 4520 |
No. of parameters | 319 |
No. of restraints | 14 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.09, −1.31 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).
Co1—O3 | 2.087 (2) | O3—Co2 | 2.111 (3) |
Co1—O5 | 2.110 (3) | Co2—N3 | 2.118 (3) |
Co1—N1 | 2.111 (3) | Co2—N5 | 2.117 (3) |
Co1—N2 | 2.118 (4) | Co2—N4 | 2.133 (3) |
Co1—Cl5 | 2.3648 (11) | Co2—Cl4 | 2.3948 (10) |
Co1—Cl3 | 2.4781 (12) | Co2—Cl3 | 2.4603 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2A···Cl5 | 0.82 | 2.29 | 3.103 (3) | 172.4 |
O1—H1···O4 | 0.82 | 1.83 | 2.615 (4) | 159.9 |
O5—H5A···Cl4 | 0.85 | 2.32 | 3.147 (3) | 164.4 |
C12—H12···Cl4i | 0.93 | 2.80 | 3.684 (4) | 159.6 |
C10—H10···Cl5ii | 0.93 | 2.82 | 3.684 (5) | 155.6 |
C14—H14···Cl4iii | 0.93 | 2.74 | 3.556 (4) | 146.5 |
C2—H2···Cl4iv | 0.93 | 2.81 | 3.654 (5) | 152.1 |
C17—H17···Cl5v | 0.93 | 2.80 | 3.491 (4) | 131.6 |
Symmetry codes: (i) x−1, y, z; (ii) x, −y+1/2, z−1/2; (iii) x, −y+1/2, z+1/2; (iv) −x+1, y+1/2, −z+1/2; (v) −x, y−1/2, −z+1/2. |
Acknowledgements
The Ministry of Education, Humanities and Social Sciences (project No. 10YJC790024) and the Shandong Province Natural Science Foundation (project No. ZR2011GL013) are acknowledged for support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Pyridine-2-carbaldehyde oxime is a frequently used ligand in synthesis of metal complexes. A large number of cobalt complexes based on pyridine-2-carbaldehyde oxime have been reported, such as mononuclear Co complexes (Stamatatos et al., 2005a), mixed-valence complexes with trinuclear Co3 clusters (Stamatatos et al., 2009), mixed-valence cobalt(III/II/III) complexes with a linear arrangement (Stamatatos et al., 2005a), mixed-valence 12-metallacrown-4 complexes (Stamatatos et al., 2005b) and some heterodinuclear complexes (Ross et al., 2001). Some of these complexes exhibit interesting magnetic properties (Ross et al., 2001; Stamatatos et al., 2005b, 2009). We are interested in the coordination chemistry of cobalt in combination with pyridine-2-carbaldehyde oxime and carboxylic acids. Here, we report a new mixed-bridged binuclear cobalt(II) complex, [Co2Cl3(C6H4NO2)(C6H6N2O)2(C2H5OH)], (I).
Compound (I) is isostructural with its Ni(II) analogue (Zheng et al., 2011). There are two six-coordinate Co(II) atoms with different coordination environments present in the structure (Fig. 1). The coordination sphere around each Co(II) atom is distorted octahedral. The two Co(II) cations are bridged through one Cl- ion and one carboxylic oxygen atom (O3) from the picolinate anion. The coordination sphere around Co1 is completed by two N atoms from one pyridine-2-carbaldehyde oxime ligand, by one terminal Cl- ion and by one O atom from an ethanol molecule. For Co2 the coordination sphere contains also two N atoms from another pyridine-2-carbaldehyde oxime ligand, one N from the bridging picolinate anion, and one terminal Cl- anion. The Co···Co distance in the dinuclear species is 3.4153 (9) Å.
Intramolecular O—H···O and O—H···Cl hydrogen bonds consolidate the conformation of the complex whereas weak C—H···Cl hydrogen bonding interactions connect the molecules into a three-dimensional network. (Table 2; Fig. 2).