Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029091/lh2427sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029091/lh2427Isup2.hkl |
CCDC reference: 654791
For the preparation of the ligand H2biqb, a slightly modified method by Nam et al. was used (Nam et al., 2006). To a stirred solution of 1–isoquinolinecarboxylic acid (1.73 g, 10 mmol) in pyridine (10 ml), a solution of 1,2–phenylenediamine (0.54 g, 5 mmol) in pyridine (5 ml) was added drop by drop. The solution was stirred for 15 min and triphenyl phosphite (2.70 ml, 10 mmol) was slowly added. The reaction mixture was warmed up to 393 K, and the mixture was stirred for 4 h. The volume of the solution was then reduced to 2 ml and kept in air. Crystallization from an aqueous solution afforded a pale–yellow powder, which was washed with ethanol. For the preparation of the title complex, equimolar quantities of CoCl2.6H2O (0.12 g, 0.5 mmol) and H2biqb (0.21 g, 0.5 mmol) were dissolved in DMF, and triethylamine (0.14 ml, 1 mmol) and tetraethylammonium chloride hydrate (0.17 g, 1 mmol) were added to the reaction solution. After the solution was refluxed for 4 h, brown precipitate was obtained. Dark brown crystals were obtained from an acetonitrile–diethyl ether solution at room temperature by slow evaporation for X–ray experiments.
H atoms were placed in calculated positions with C—H distances of 0.95Å (isoquinoline and benzene), 0.99Å (methylene) and 0.98Å (methyl).They were included in the refinement in riding–motion approximation with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(C) for methyl H atoms.
Selective hydroxylation of hydrocarbons is an important but still very difficult chemical transformation process. A great deal of effort has been made to develop efficient catalysts for the hydrocarbon oxidation in synthetic organic chemistry and industrial chemistry (Barton & Doller, 1992, Sawyer et al., 1996). While much attention has been paid to heme and nonheme iron complexes due to their high catalytic activity and biological relevance (Nam et al., 2000, Kaizer et al., 2004), cobalt complexes have attracted less attention in the oxidation chemistry (Jain & Sain, 2003). In order to study the catalytic oxidation reactions of hydrocarbons with new cobalt complexes, we have synthesized the title complex by the reaction of cobalt(II) chloride with 1,2-bis(isoquinoline-2-carboxamido)benzene (H2biqb).
The four N atoms of the biqb2- ligand form the equatorial plane of the distorted octahedral coordination geometry of the CoIII ion, and two chloro ligands are axially coordinated to the CoIII ion (Fig. 1). The two Co—Namide distances are significantly shorter than the Co—Npyridyl distances. The anion is not planar with a dihedral angle of 25.72 (7)° between two isoqunoline rings. In the crystal structure, there are inter-molecular C(cation)-H···Cl and C(isoquinoline)-H···Cl hydrogen bonds as shown in Fig. 2.
The corresponding [Et4N][Co(bpb)Cl2] (H2bpb = 1,2–bis(2–pyridine–2–carboxamido)benzene) complex has distorted octahedral geometry (Seo et al., 2004) with chloro axial ligands having long Co—Cl bonds.
For related literature, see: Barton & Doller (1992); Jain & Sain (2003); Kaizer et al. (2004); Nam et al. (2000, 2006); Sawyer et al. (1996).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
(C8H20N)[Co(C26H16N4O2)Cl2] | F(000) = 1408 |
Mr = 676.51 | Dx = 1.490 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 813 reflections |
a = 12.921 (2) Å | θ = 2.2–17.4° |
b = 16.646 (3) Å | µ = 0.79 mm−1 |
c = 14.022 (2) Å | T = 100 K |
β = 90.625 (4)° | Block, dark brown |
V = 3015.7 (9) Å3 | 0.15 × 0.10 × 0.10 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 5913 independent reflections |
Radiation source: fine-focus sealed tube | 3440 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.085 |
φ and ω scans | θmax = 26.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −15→14 |
Tmin = 0.910, Tmax = 0.924 | k = −20→20 |
16659 measured reflections | l = −12→17 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 0.89 | w = 1/[σ2(Fo2) + (0.0407P)2] where P = (Fo2 + 2Fc2)/3 |
5913 reflections | (Δ/σ)max = 0.001 |
401 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
(C8H20N)[Co(C26H16N4O2)Cl2] | V = 3015.7 (9) Å3 |
Mr = 676.51 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.921 (2) Å | µ = 0.79 mm−1 |
b = 16.646 (3) Å | T = 100 K |
c = 14.022 (2) Å | 0.15 × 0.10 × 0.10 mm |
β = 90.625 (4)° |
Bruker SMART CCD diffractometer | 5913 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 3440 reflections with I > 2σ(I) |
Tmin = 0.910, Tmax = 0.924 | Rint = 0.085 |
16659 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 0.89 | Δρmax = 0.42 e Å−3 |
5913 reflections | Δρmin = −0.43 e Å−3 |
401 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 | 0.36201 (4) | 0.65718 (3) | 0.46734 (4) | 0.01553 (14) | |
Cl1 | 0.31747 (7) | 0.52714 (5) | 0.44809 (7) | 0.0203 (2) | |
Cl2 | 0.42351 (7) | 0.78286 (5) | 0.49397 (7) | 0.0235 (2) | |
N1 | 0.4901 (2) | 0.63953 (16) | 0.3961 (2) | 0.0167 (7) | |
N2 | 0.3095 (2) | 0.67995 (16) | 0.3450 (2) | 0.0138 (7) | |
N3 | 0.2300 (2) | 0.68338 (16) | 0.5085 (2) | 0.0160 (7) | |
N4 | 0.3827 (2) | 0.63030 (16) | 0.6027 (2) | 0.0153 (7) | |
O1 | 0.33359 (18) | 0.64480 (15) | 0.18733 (17) | 0.0247 (6) | |
O2 | 0.12527 (18) | 0.69526 (14) | 0.64086 (17) | 0.0204 (6) | |
C1 | 0.5880 (3) | 0.6354 (2) | 0.4333 (3) | 0.0194 (9) | |
H1 | 0.5977 | 0.6389 | 0.5004 | 0.023* | |
C2 | 0.6715 (3) | 0.6266 (2) | 0.3770 (3) | 0.0209 (9) | |
H2 | 0.7384 | 0.6225 | 0.4053 | 0.025* | |
C3 | 0.6608 (3) | 0.6233 (2) | 0.2774 (3) | 0.0191 (9) | |
C4 | 0.7456 (3) | 0.6157 (2) | 0.2165 (3) | 0.0229 (9) | |
H4 | 0.8134 | 0.6114 | 0.2429 | 0.027* | |
C5 | 0.7324 (3) | 0.6146 (2) | 0.1204 (3) | 0.0241 (9) | |
H5 | 0.7908 | 0.6095 | 0.0803 | 0.029* | |
C6 | 0.6330 (3) | 0.6208 (2) | 0.0800 (3) | 0.0238 (9) | |
H6 | 0.6247 | 0.6200 | 0.0126 | 0.029* | |
C7 | 0.5475 (3) | 0.6281 (2) | 0.1367 (3) | 0.0193 (9) | |
H7 | 0.4806 | 0.6323 | 0.1083 | 0.023* | |
C8 | 0.5586 (3) | 0.6295 (2) | 0.2369 (3) | 0.0162 (8) | |
C9 | 0.4755 (3) | 0.6390 (2) | 0.3014 (3) | 0.0170 (9) | |
C10 | 0.3649 (3) | 0.6539 (2) | 0.2705 (3) | 0.0170 (8) | |
C11 | 0.2027 (3) | 0.6964 (2) | 0.3431 (3) | 0.0162 (8) | |
C12 | 0.1406 (3) | 0.70987 (19) | 0.2625 (3) | 0.0178 (9) | |
H12 | 0.1705 | 0.7097 | 0.2009 | 0.021* | |
C13 | 0.0357 (3) | 0.7234 (2) | 0.2724 (3) | 0.0195 (9) | |
H13 | −0.0065 | 0.7323 | 0.2174 | 0.023* | |
C14 | −0.0084 (3) | 0.7241 (2) | 0.3624 (3) | 0.0178 (9) | |
H14 | −0.0807 | 0.7327 | 0.3685 | 0.021* | |
C15 | 0.0525 (3) | 0.7121 (2) | 0.4438 (3) | 0.0205 (9) | |
H15 | 0.0220 | 0.7133 | 0.5051 | 0.025* | |
C16 | 0.1581 (3) | 0.69848 (19) | 0.4351 (3) | 0.0153 (8) | |
C17 | 0.2091 (3) | 0.6808 (2) | 0.6022 (3) | 0.0156 (8) | |
C18 | 0.3032 (3) | 0.6515 (2) | 0.6576 (2) | 0.0136 (8) | |
C19 | 0.3040 (3) | 0.63931 (19) | 0.7576 (3) | 0.0157 (8) | |
C20 | 0.2256 (3) | 0.6671 (2) | 0.8204 (3) | 0.0197 (9) | |
H20 | 0.1676 | 0.6953 | 0.7950 | 0.024* | |
C21 | 0.2325 (3) | 0.6540 (2) | 0.9165 (3) | 0.0241 (9) | |
H21 | 0.1798 | 0.6736 | 0.9572 | 0.029* | |
C22 | 0.3169 (3) | 0.6118 (2) | 0.9555 (3) | 0.0248 (10) | |
H22 | 0.3204 | 0.6022 | 1.0223 | 0.030* | |
C23 | 0.3939 (3) | 0.5843 (2) | 0.8982 (3) | 0.0206 (9) | |
H23 | 0.4508 | 0.5560 | 0.9255 | 0.025* | |
C24 | 0.3900 (3) | 0.5975 (2) | 0.7989 (3) | 0.0168 (9) | |
C25 | 0.4678 (3) | 0.5711 (2) | 0.7364 (3) | 0.0195 (9) | |
H25 | 0.5244 | 0.5407 | 0.7608 | 0.023* | |
C26 | 0.4627 (3) | 0.58839 (19) | 0.6426 (3) | 0.0172 (9) | |
H26 | 0.5171 | 0.5706 | 0.6027 | 0.021* | |
N5 | 0.9072 (2) | 0.54941 (17) | 0.7444 (2) | 0.0207 (8) | |
C51 | 0.9003 (3) | 0.6357 (2) | 0.7087 (3) | 0.0259 (10) | |
H51A | 0.8780 | 0.6702 | 0.7622 | 0.031* | |
H51B | 0.9705 | 0.6534 | 0.6904 | 0.031* | |
C52 | 0.8280 (3) | 0.6497 (2) | 0.6252 (3) | 0.0344 (11) | |
H52A | 0.8498 | 0.6168 | 0.5711 | 0.052* | |
H52B | 0.8298 | 0.7066 | 0.6073 | 0.052* | |
H52C | 0.7574 | 0.6349 | 0.6431 | 0.052* | |
C53 | 0.9412 (3) | 0.4925 (2) | 0.6655 (3) | 0.0220 (9) | |
H53A | 0.9425 | 0.4372 | 0.6914 | 0.026* | |
H53B | 0.8884 | 0.4939 | 0.6138 | 0.026* | |
C54 | 1.0459 (3) | 0.5102 (2) | 0.6225 (3) | 0.0240 (10) | |
H54A | 1.0443 | 0.5632 | 0.5921 | 0.036* | |
H54B | 1.0621 | 0.4692 | 0.5748 | 0.036* | |
H54C | 1.0991 | 0.5098 | 0.6729 | 0.036* | |
C55 | 0.9856 (3) | 0.5497 (2) | 0.8262 (3) | 0.0290 (10) | |
H55A | 1.0535 | 0.5669 | 0.8012 | 0.035* | |
H55B | 0.9639 | 0.5901 | 0.8738 | 0.035* | |
C56 | 0.9994 (3) | 0.4697 (2) | 0.8761 (3) | 0.0363 (11) | |
H56A | 0.9344 | 0.4544 | 0.9066 | 0.055* | |
H56B | 1.0542 | 0.4742 | 0.9246 | 0.055* | |
H56C | 1.0184 | 0.4286 | 0.8294 | 0.055* | |
C57 | 0.8029 (3) | 0.5188 (2) | 0.7762 (3) | 0.0215 (9) | |
H57A | 0.7559 | 0.5170 | 0.7200 | 0.026* | |
H57B | 0.8115 | 0.4631 | 0.7995 | 0.026* | |
C58 | 0.7518 (3) | 0.5675 (2) | 0.8531 (3) | 0.0283 (10) | |
H58A | 0.7995 | 0.5734 | 0.9075 | 0.042* | |
H58B | 0.6888 | 0.5399 | 0.8739 | 0.042* | |
H58C | 0.7337 | 0.6206 | 0.8281 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0159 (3) | 0.0166 (3) | 0.0141 (3) | 0.0011 (2) | 0.0008 (2) | −0.0001 (2) |
Cl1 | 0.0210 (5) | 0.0199 (5) | 0.0200 (5) | 0.0001 (4) | −0.0003 (4) | 0.0000 (4) |
Cl2 | 0.0269 (6) | 0.0211 (5) | 0.0226 (6) | 0.0003 (4) | 0.0024 (4) | 0.0002 (4) |
N1 | 0.0166 (17) | 0.0153 (17) | 0.0182 (18) | −0.0005 (13) | −0.0015 (13) | 0.0003 (14) |
N2 | 0.0152 (17) | 0.0142 (16) | 0.0122 (17) | −0.0006 (13) | 0.0028 (13) | 0.0046 (13) |
N3 | 0.0162 (17) | 0.0181 (17) | 0.0137 (18) | 0.0010 (13) | 0.0032 (13) | −0.0008 (14) |
N4 | 0.0165 (17) | 0.0105 (16) | 0.0189 (18) | −0.0012 (13) | −0.0007 (14) | 0.0002 (13) |
O1 | 0.0240 (15) | 0.0355 (17) | 0.0145 (15) | 0.0012 (13) | −0.0005 (12) | −0.0026 (13) |
O2 | 0.0184 (15) | 0.0237 (15) | 0.0192 (15) | 0.0001 (12) | 0.0050 (12) | 0.0008 (12) |
C1 | 0.019 (2) | 0.025 (2) | 0.014 (2) | −0.0001 (17) | −0.0027 (17) | 0.0014 (17) |
C2 | 0.017 (2) | 0.024 (2) | 0.022 (2) | 0.0020 (17) | −0.0023 (18) | 0.0044 (18) |
C3 | 0.021 (2) | 0.016 (2) | 0.020 (2) | 0.0001 (17) | 0.0050 (17) | 0.0026 (17) |
C4 | 0.015 (2) | 0.025 (2) | 0.028 (3) | 0.0023 (18) | 0.0026 (18) | 0.0024 (19) |
C5 | 0.020 (2) | 0.022 (2) | 0.031 (3) | 0.0033 (18) | 0.0093 (19) | 0.0036 (19) |
C6 | 0.030 (2) | 0.020 (2) | 0.021 (2) | −0.0023 (19) | 0.0082 (19) | 0.0003 (18) |
C7 | 0.026 (2) | 0.015 (2) | 0.017 (2) | 0.0027 (17) | 0.0004 (18) | 0.0037 (17) |
C8 | 0.014 (2) | 0.0089 (18) | 0.025 (2) | −0.0007 (15) | 0.0062 (17) | 0.0038 (17) |
C9 | 0.021 (2) | 0.014 (2) | 0.016 (2) | −0.0003 (16) | 0.0020 (17) | −0.0005 (16) |
C10 | 0.018 (2) | 0.0136 (19) | 0.019 (2) | −0.0051 (17) | 0.0004 (17) | 0.0055 (18) |
C11 | 0.018 (2) | 0.017 (2) | 0.014 (2) | 0.0006 (16) | −0.0006 (16) | −0.0053 (17) |
C12 | 0.024 (2) | 0.014 (2) | 0.015 (2) | −0.0007 (17) | 0.0026 (17) | −0.0017 (16) |
C13 | 0.017 (2) | 0.019 (2) | 0.022 (2) | 0.0026 (17) | −0.0056 (17) | −0.0016 (18) |
C14 | 0.015 (2) | 0.014 (2) | 0.024 (2) | 0.0019 (16) | −0.0040 (17) | −0.0001 (17) |
C15 | 0.027 (2) | 0.018 (2) | 0.017 (2) | 0.0034 (17) | 0.0029 (17) | 0.0009 (17) |
C16 | 0.017 (2) | 0.0096 (19) | 0.020 (2) | 0.0019 (16) | −0.0010 (16) | 0.0007 (17) |
C17 | 0.021 (2) | 0.0092 (19) | 0.017 (2) | −0.0023 (16) | 0.0022 (17) | 0.0031 (16) |
C18 | 0.015 (2) | 0.0093 (18) | 0.016 (2) | 0.0007 (16) | 0.0002 (16) | 0.0012 (16) |
C19 | 0.024 (2) | 0.0096 (19) | 0.014 (2) | −0.0057 (16) | −0.0017 (16) | 0.0010 (16) |
C20 | 0.023 (2) | 0.020 (2) | 0.016 (2) | −0.0042 (18) | 0.0033 (17) | −0.0008 (18) |
C21 | 0.031 (2) | 0.023 (2) | 0.018 (2) | −0.0042 (19) | 0.0071 (18) | −0.0033 (19) |
C22 | 0.037 (3) | 0.024 (2) | 0.014 (2) | −0.0088 (19) | 0.0039 (19) | −0.0001 (18) |
C23 | 0.020 (2) | 0.021 (2) | 0.021 (2) | −0.0058 (17) | −0.0048 (18) | 0.0065 (19) |
C24 | 0.024 (2) | 0.0086 (19) | 0.018 (2) | −0.0074 (16) | 0.0007 (17) | −0.0012 (16) |
C25 | 0.019 (2) | 0.020 (2) | 0.019 (2) | 0.0008 (17) | −0.0052 (17) | 0.0016 (18) |
C26 | 0.020 (2) | 0.0109 (19) | 0.021 (2) | 0.0004 (16) | 0.0017 (17) | −0.0008 (17) |
N5 | 0.0215 (18) | 0.0186 (17) | 0.0219 (19) | 0.0028 (14) | 0.0034 (14) | −0.0076 (15) |
C51 | 0.024 (2) | 0.019 (2) | 0.036 (3) | −0.0016 (18) | 0.0102 (19) | −0.0051 (19) |
C52 | 0.037 (3) | 0.021 (2) | 0.045 (3) | 0.004 (2) | 0.007 (2) | 0.003 (2) |
C53 | 0.027 (2) | 0.017 (2) | 0.022 (2) | 0.0025 (17) | 0.0027 (18) | −0.0064 (18) |
C54 | 0.025 (2) | 0.019 (2) | 0.027 (2) | 0.0052 (18) | 0.0011 (18) | −0.0072 (19) |
C55 | 0.017 (2) | 0.040 (3) | 0.030 (3) | 0.0039 (19) | −0.0034 (18) | −0.020 (2) |
C56 | 0.034 (3) | 0.047 (3) | 0.028 (3) | 0.013 (2) | −0.008 (2) | −0.013 (2) |
C57 | 0.017 (2) | 0.025 (2) | 0.022 (2) | −0.0045 (17) | 0.0036 (17) | −0.0028 (18) |
C58 | 0.020 (2) | 0.039 (3) | 0.025 (3) | 0.0012 (19) | 0.0027 (18) | −0.010 (2) |
Co1—N3 | 1.859 (3) | C18—C19 | 1.417 (5) |
Co1—N2 | 1.877 (3) | C19—C24 | 1.428 (5) |
Co1—N1 | 1.965 (3) | C19—C20 | 1.428 (5) |
Co1—N4 | 1.965 (3) | C20—C21 | 1.367 (5) |
Co1—Cl1 | 2.2552 (11) | C20—H20 | 0.9500 |
Co1—Cl2 | 2.2674 (11) | C21—C22 | 1.404 (5) |
N1—C9 | 1.340 (4) | C21—H21 | 0.9500 |
N1—C1 | 1.363 (4) | C22—C23 | 1.365 (5) |
N2—C10 | 1.345 (4) | C22—H22 | 0.9500 |
N2—C11 | 1.407 (4) | C23—C24 | 1.410 (5) |
N3—C17 | 1.344 (4) | C23—H23 | 0.9500 |
N3—C16 | 1.402 (4) | C24—C25 | 1.410 (5) |
N4—C18 | 1.338 (4) | C25—C26 | 1.348 (5) |
N4—C26 | 1.362 (4) | C25—H25 | 0.9500 |
O1—C10 | 1.239 (4) | C26—H26 | 0.9500 |
O2—C17 | 1.241 (4) | N5—C57 | 1.512 (4) |
C1—C2 | 1.352 (5) | N5—C55 | 1.522 (4) |
C1—H1 | 0.9500 | N5—C51 | 1.523 (4) |
C2—C3 | 1.403 (5) | N5—C53 | 1.524 (4) |
C2—H2 | 0.9500 | C51—C52 | 1.508 (5) |
C3—C4 | 1.402 (5) | C51—H51A | 0.9900 |
C3—C8 | 1.435 (5) | C51—H51B | 0.9900 |
C4—C5 | 1.355 (5) | C52—H52A | 0.9800 |
C4—H4 | 0.9500 | C52—H52B | 0.9800 |
C5—C6 | 1.401 (5) | C52—H52C | 0.9800 |
C5—H5 | 0.9500 | C53—C54 | 1.516 (5) |
C6—C7 | 1.373 (5) | C53—H53A | 0.9900 |
C6—H6 | 0.9500 | C53—H53B | 0.9900 |
C7—C8 | 1.412 (5) | C54—H54A | 0.9800 |
C7—H7 | 0.9500 | C54—H54B | 0.9800 |
C8—C9 | 1.420 (5) | C54—H54C | 0.9800 |
C9—C10 | 1.509 (5) | C55—C56 | 1.515 (5) |
C11—C12 | 1.397 (5) | C55—H55A | 0.9900 |
C11—C16 | 1.418 (5) | C55—H55B | 0.9900 |
C12—C13 | 1.383 (5) | C56—H56A | 0.9800 |
C12—H12 | 0.9500 | C56—H56B | 0.9800 |
C13—C14 | 1.391 (5) | C56—H56C | 0.9800 |
C13—H13 | 0.9500 | C57—C58 | 1.507 (5) |
C14—C15 | 1.393 (4) | C57—H57A | 0.9900 |
C14—H14 | 0.9500 | C57—H57B | 0.9900 |
C15—C16 | 1.389 (5) | C58—H58A | 0.9800 |
C15—H15 | 0.9500 | C58—H58B | 0.9800 |
C17—C18 | 1.516 (5) | C58—H58C | 0.9800 |
N3—Co1—N2 | 85.00 (12) | C19—C18—C17 | 123.4 (3) |
N3—Co1—N1 | 166.97 (12) | C18—C19—C24 | 118.0 (3) |
N2—Co1—N1 | 82.18 (12) | C18—C19—C20 | 124.5 (3) |
N3—Co1—N4 | 82.49 (12) | C24—C19—C20 | 117.5 (3) |
N2—Co1—N4 | 166.62 (12) | C21—C20—C19 | 121.2 (3) |
N1—Co1—N4 | 110.48 (12) | C21—C20—H20 | 119.4 |
N3—Co1—Cl1 | 91.63 (9) | C19—C20—H20 | 119.4 |
N2—Co1—Cl1 | 89.73 (9) | C20—C21—C22 | 120.4 (4) |
N1—Co1—Cl1 | 90.64 (8) | C20—C21—H21 | 119.8 |
N4—Co1—Cl1 | 85.93 (8) | C22—C21—H21 | 119.8 |
N3—Co1—Cl2 | 93.07 (9) | C23—C22—C21 | 120.5 (4) |
N2—Co1—Cl2 | 94.97 (9) | C23—C22—H22 | 119.8 |
N1—Co1—Cl2 | 85.75 (8) | C21—C22—H22 | 119.8 |
N4—Co1—Cl2 | 90.41 (8) | C22—C23—C24 | 120.7 (3) |
Cl1—Co1—Cl2 | 173.62 (4) | C22—C23—H23 | 119.6 |
C9—N1—C1 | 119.9 (3) | C24—C23—H23 | 119.6 |
C9—N1—Co1 | 113.2 (2) | C25—C24—C23 | 123.1 (3) |
C1—N1—Co1 | 126.6 (3) | C25—C24—C19 | 117.1 (3) |
C10—N2—C11 | 125.4 (3) | C23—C24—C19 | 119.7 (3) |
C10—N2—Co1 | 117.0 (2) | C26—C25—C24 | 120.8 (3) |
C11—N2—Co1 | 113.6 (2) | C26—C25—H25 | 119.6 |
C17—N3—C16 | 125.8 (3) | C24—C25—H25 | 119.6 |
C17—N3—Co1 | 119.4 (2) | C25—C26—N4 | 122.6 (3) |
C16—N3—Co1 | 114.6 (2) | C25—C26—H26 | 118.7 |
C18—N4—C26 | 118.9 (3) | N4—C26—H26 | 118.7 |
C18—N4—Co1 | 113.5 (2) | C57—N5—C55 | 111.5 (3) |
C26—N4—Co1 | 127.5 (3) | C57—N5—C51 | 111.4 (3) |
C2—C1—N1 | 121.7 (3) | C55—N5—C51 | 106.3 (3) |
C2—C1—H1 | 119.2 | C57—N5—C53 | 105.6 (3) |
N1—C1—H1 | 119.2 | C55—N5—C53 | 110.7 (3) |
C1—C2—C3 | 121.0 (3) | C51—N5—C53 | 111.3 (3) |
C1—C2—H2 | 119.5 | C52—C51—N5 | 115.8 (3) |
C3—C2—H2 | 119.5 | C52—C51—H51A | 108.3 |
C4—C3—C2 | 122.7 (3) | N5—C51—H51A | 108.3 |
C4—C3—C8 | 119.2 (3) | C52—C51—H51B | 108.3 |
C2—C3—C8 | 118.1 (3) | N5—C51—H51B | 108.3 |
C5—C4—C3 | 121.0 (3) | H51A—C51—H51B | 107.4 |
C5—C4—H4 | 119.5 | C51—C52—H52A | 109.5 |
C3—C4—H4 | 119.5 | C51—C52—H52B | 109.5 |
C4—C5—C6 | 120.4 (4) | H52A—C52—H52B | 109.5 |
C4—C5—H5 | 119.8 | C51—C52—H52C | 109.5 |
C6—C5—H5 | 119.8 | H52A—C52—H52C | 109.5 |
C7—C6—C5 | 120.8 (4) | H52B—C52—H52C | 109.5 |
C7—C6—H6 | 119.6 | C54—C53—N5 | 115.7 (3) |
C5—C6—H6 | 119.6 | C54—C53—H53A | 108.4 |
C6—C7—C8 | 120.2 (3) | N5—C53—H53A | 108.4 |
C6—C7—H7 | 119.9 | C54—C53—H53B | 108.4 |
C8—C7—H7 | 119.9 | N5—C53—H53B | 108.4 |
C7—C8—C9 | 124.5 (3) | H53A—C53—H53B | 107.4 |
C7—C8—C3 | 118.4 (3) | C53—C54—H54A | 109.5 |
C9—C8—C3 | 117.1 (3) | C53—C54—H54B | 109.5 |
N1—C9—C8 | 122.2 (3) | H54A—C54—H54B | 109.5 |
N1—C9—C10 | 114.0 (3) | C53—C54—H54C | 109.5 |
C8—C9—C10 | 123.7 (3) | H54A—C54—H54C | 109.5 |
O1—C10—N2 | 126.8 (3) | H54B—C54—H54C | 109.5 |
O1—C10—C9 | 123.3 (3) | C56—C55—N5 | 114.8 (3) |
N2—C10—C9 | 109.9 (3) | C56—C55—H55A | 108.6 |
C12—C11—N2 | 126.9 (3) | N5—C55—H55A | 108.6 |
C12—C11—C16 | 119.8 (3) | C56—C55—H55B | 108.6 |
N2—C11—C16 | 113.3 (3) | N5—C55—H55B | 108.6 |
C13—C12—C11 | 120.0 (3) | H55A—C55—H55B | 107.6 |
C13—C12—H12 | 120.0 | C55—C56—H56A | 109.5 |
C11—C12—H12 | 120.0 | C55—C56—H56B | 109.5 |
C12—C13—C14 | 120.2 (3) | H56A—C56—H56B | 109.5 |
C12—C13—H13 | 119.9 | C55—C56—H56C | 109.5 |
C14—C13—H13 | 119.9 | H56A—C56—H56C | 109.5 |
C13—C14—C15 | 120.6 (3) | H56B—C56—H56C | 109.5 |
C13—C14—H14 | 119.7 | C58—C57—N5 | 115.4 (3) |
C15—C14—H14 | 119.7 | C58—C57—H57A | 108.4 |
C16—C15—C14 | 119.8 (4) | N5—C57—H57A | 108.4 |
C16—C15—H15 | 120.1 | C58—C57—H57B | 108.4 |
C14—C15—H15 | 120.1 | N5—C57—H57B | 108.4 |
C15—C16—N3 | 127.4 (3) | H57A—C57—H57B | 107.5 |
C15—C16—C11 | 119.5 (3) | C57—C58—H58A | 109.5 |
N3—C16—C11 | 113.0 (3) | C57—C58—H58B | 109.5 |
O2—C17—N3 | 127.3 (3) | H58A—C58—H58B | 109.5 |
O2—C17—C18 | 122.5 (3) | C57—C58—H58C | 109.5 |
N3—C17—C18 | 110.0 (3) | H58A—C58—H58C | 109.5 |
N4—C18—C19 | 122.3 (3) | H58B—C58—H58C | 109.5 |
N4—C18—C17 | 114.0 (3) | ||
N3—Co1—N1—C9 | −20.2 (6) | N1—C9—C10—O1 | −169.8 (3) |
N2—Co1—N1—C9 | −9.8 (2) | C8—C9—C10—O1 | 13.5 (5) |
N4—Co1—N1—C9 | 165.7 (2) | N1—C9—C10—N2 | 12.1 (4) |
Cl1—Co1—N1—C9 | 79.8 (2) | C8—C9—C10—N2 | −164.6 (3) |
Cl2—Co1—N1—C9 | −105.4 (2) | C10—N2—C11—C12 | −18.5 (5) |
N3—Co1—N1—C1 | 153.6 (5) | Co1—N2—C11—C12 | −175.3 (3) |
N2—Co1—N1—C1 | 164.1 (3) | C10—N2—C11—C16 | 161.4 (3) |
N4—Co1—N1—C1 | −20.4 (3) | Co1—N2—C11—C16 | 4.6 (4) |
Cl1—Co1—N1—C1 | −106.3 (3) | N2—C11—C12—C13 | 178.4 (3) |
Cl2—Co1—N1—C1 | 68.4 (3) | C16—C11—C12—C13 | −1.5 (5) |
N3—Co1—N2—C10 | −164.5 (3) | C11—C12—C13—C14 | 0.3 (5) |
N1—Co1—N2—C10 | 17.9 (2) | C12—C13—C14—C15 | 0.8 (5) |
N4—Co1—N2—C10 | −143.7 (5) | C13—C14—C15—C16 | −0.8 (5) |
Cl1—Co1—N2—C10 | −72.8 (2) | C14—C15—C16—N3 | −178.2 (3) |
Cl2—Co1—N2—C10 | 102.9 (2) | C14—C15—C16—C11 | −0.4 (5) |
N3—Co1—N2—C11 | −5.6 (2) | C17—N3—C16—C15 | −1.2 (5) |
N1—Co1—N2—C11 | 176.7 (2) | Co1—N3—C16—C15 | 173.7 (3) |
N4—Co1—N2—C11 | 15.2 (6) | C17—N3—C16—C11 | −179.2 (3) |
Cl1—Co1—N2—C11 | 86.1 (2) | Co1—N3—C16—C11 | −4.3 (4) |
Cl2—Co1—N2—C11 | −98.3 (2) | C12—C11—C16—C15 | 1.5 (5) |
N2—Co1—N3—C17 | −179.2 (3) | N2—C11—C16—C15 | −178.4 (3) |
N1—Co1—N3—C17 | −168.8 (4) | C12—C11—C16—N3 | 179.7 (3) |
N4—Co1—N3—C17 | 5.5 (2) | N2—C11—C16—N3 | −0.3 (4) |
Cl1—Co1—N3—C17 | 91.2 (2) | C16—N3—C17—O2 | −4.2 (6) |
Cl2—Co1—N3—C17 | −84.5 (2) | Co1—N3—C17—O2 | −178.9 (3) |
N2—Co1—N3—C16 | 5.5 (2) | C16—N3—C17—C18 | 172.1 (3) |
N1—Co1—N3—C16 | 15.9 (7) | Co1—N3—C17—C18 | −2.6 (4) |
N4—Co1—N3—C16 | −169.7 (2) | C26—N4—C18—C19 | 6.7 (5) |
Cl1—Co1—N3—C16 | −84.1 (2) | Co1—N4—C18—C19 | −178.3 (2) |
Cl2—Co1—N3—C16 | 100.2 (2) | C26—N4—C18—C17 | −167.0 (3) |
N3—Co1—N4—C18 | −7.5 (2) | Co1—N4—C18—C17 | 8.0 (3) |
N2—Co1—N4—C18 | −28.3 (6) | O2—C17—C18—N4 | 172.7 (3) |
N1—Co1—N4—C18 | 171.2 (2) | N3—C17—C18—N4 | −3.8 (4) |
Cl1—Co1—N4—C18 | −99.7 (2) | O2—C17—C18—C19 | −0.9 (5) |
Cl2—Co1—N4—C18 | 85.6 (2) | N3—C17—C18—C19 | −177.4 (3) |
N3—Co1—N4—C26 | 167.0 (3) | N4—C18—C19—C24 | −4.7 (5) |
N2—Co1—N4—C26 | 146.1 (5) | C17—C18—C19—C24 | 168.4 (3) |
N1—Co1—N4—C26 | −14.4 (3) | N4—C18—C19—C20 | 174.2 (3) |
Cl1—Co1—N4—C26 | 74.8 (3) | C17—C18—C19—C20 | −12.7 (5) |
Cl2—Co1—N4—C26 | −100.0 (3) | C18—C19—C20—C21 | −179.1 (3) |
C9—N1—C1—C2 | −3.5 (5) | C24—C19—C20—C21 | −0.2 (5) |
Co1—N1—C1—C2 | −177.0 (3) | C19—C20—C21—C22 | −0.7 (5) |
N1—C1—C2—C3 | 1.7 (5) | C20—C21—C22—C23 | 1.0 (6) |
C1—C2—C3—C4 | 178.8 (3) | C21—C22—C23—C24 | −0.3 (5) |
C1—C2—C3—C8 | −0.1 (5) | C22—C23—C24—C25 | 179.5 (3) |
C2—C3—C4—C5 | −178.6 (3) | C22—C23—C24—C19 | −0.7 (5) |
C8—C3—C4—C5 | 0.3 (5) | C18—C19—C24—C25 | −0.3 (5) |
C3—C4—C5—C6 | −0.1 (5) | C20—C19—C24—C25 | −179.3 (3) |
C4—C5—C6—C7 | −0.1 (5) | C18—C19—C24—C23 | 179.9 (3) |
C5—C6—C7—C8 | 0.0 (5) | C20—C19—C24—C23 | 0.9 (5) |
C6—C7—C8—C9 | 178.3 (3) | C23—C24—C25—C26 | −177.0 (3) |
C6—C7—C8—C3 | 0.2 (5) | C19—C24—C25—C26 | 3.2 (5) |
C4—C3—C8—C7 | −0.3 (5) | C24—C25—C26—N4 | −1.3 (5) |
C2—C3—C8—C7 | 178.6 (3) | C18—N4—C26—C25 | −3.7 (5) |
C4—C3—C8—C9 | −178.6 (3) | Co1—N4—C26—C25 | −177.9 (2) |
C2—C3—C8—C9 | 0.3 (5) | C57—N5—C51—C52 | −59.6 (4) |
C1—N1—C9—C8 | 3.8 (5) | C55—N5—C51—C52 | 178.7 (3) |
Co1—N1—C9—C8 | 178.1 (3) | C53—N5—C51—C52 | 58.0 (4) |
C1—N1—C9—C10 | −173.0 (3) | C57—N5—C53—C54 | −179.1 (3) |
Co1—N1—C9—C10 | 1.3 (3) | C55—N5—C53—C54 | −58.2 (4) |
C7—C8—C9—N1 | 179.7 (3) | C51—N5—C53—C54 | 59.8 (4) |
C3—C8—C9—N1 | −2.2 (5) | C57—N5—C55—C56 | 54.9 (4) |
C7—C8—C9—C10 | −3.9 (5) | C51—N5—C55—C56 | 176.5 (3) |
C3—C8—C9—C10 | 174.3 (3) | C53—N5—C55—C56 | −62.4 (4) |
C11—N2—C10—O1 | 4.9 (6) | C55—N5—C57—C58 | 61.2 (4) |
Co1—N2—C10—O1 | 161.0 (3) | C51—N5—C57—C58 | −57.4 (4) |
C11—N2—C10—C9 | −177.1 (3) | C53—N5—C57—C58 | −178.5 (3) |
Co1—N2—C10—C9 | −21.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C53—H53B···Cl1i | 0.99 | 2.81 | 3.701 (4) | 150 |
C57—H57A···Cl1i | 0.99 | 2.64 | 3.576 (4) | 159 |
C55—H55B···Cl2ii | 0.99 | 2.76 | 3.740 (4) | 172 |
C5—H5···Cl2iii | 0.95 | 2.77 | 3.501 (4) | 135 |
C26—H26···Cl1i | 0.95 | 2.79 | 3.669 (4) | 155 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+3/2, z+1/2; (iii) x+1/2, −y+3/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | (C8H20N)[Co(C26H16N4O2)Cl2] |
Mr | 676.51 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 12.921 (2), 16.646 (3), 14.022 (2) |
β (°) | 90.625 (4) |
V (Å3) | 3015.7 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.79 |
Crystal size (mm) | 0.15 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.910, 0.924 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16659, 5913, 3440 |
Rint | 0.085 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.102, 0.89 |
No. of reflections | 5913 |
No. of parameters | 401 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.42, −0.43 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C53—H53B···Cl1i | 0.99 | 2.81 | 3.701 (4) | 149.9 |
C57—H57A···Cl1i | 0.99 | 2.64 | 3.576 (4) | 158.7 |
C55—H55B···Cl2ii | 0.99 | 2.76 | 3.740 (4) | 171.7 |
C5—H5···Cl2iii | 0.95 | 2.77 | 3.501 (4) | 134.5 |
C26—H26···Cl1i | 0.95 | 2.79 | 3.669 (4) | 155.1 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+3/2, z+1/2; (iii) x+1/2, −y+3/2, z−1/2. |
Selective hydroxylation of hydrocarbons is an important but still very difficult chemical transformation process. A great deal of effort has been made to develop efficient catalysts for the hydrocarbon oxidation in synthetic organic chemistry and industrial chemistry (Barton & Doller, 1992, Sawyer et al., 1996). While much attention has been paid to heme and nonheme iron complexes due to their high catalytic activity and biological relevance (Nam et al., 2000, Kaizer et al., 2004), cobalt complexes have attracted less attention in the oxidation chemistry (Jain & Sain, 2003). In order to study the catalytic oxidation reactions of hydrocarbons with new cobalt complexes, we have synthesized the title complex by the reaction of cobalt(II) chloride with 1,2-bis(isoquinoline-2-carboxamido)benzene (H2biqb).
The four N atoms of the biqb2- ligand form the equatorial plane of the distorted octahedral coordination geometry of the CoIII ion, and two chloro ligands are axially coordinated to the CoIII ion (Fig. 1). The two Co—Namide distances are significantly shorter than the Co—Npyridyl distances. The anion is not planar with a dihedral angle of 25.72 (7)° between two isoqunoline rings. In the crystal structure, there are inter-molecular C(cation)-H···Cl and C(isoquinoline)-H···Cl hydrogen bonds as shown in Fig. 2.