Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680101193X/cf6099sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680101193X/cf6099Isup2.hkl |
CCDC reference: 170875
Key indicators
- Single-crystal X-ray study
- T = 130 K
- Mean (C-C) = 0.019 Å
- R factor = 0.099
- wR factor = 0.299
- Data-to-parameter ratio = 10.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.5419
Author response: The value of sine(theta_max)/wavelength is 0.542 due to instrument limitations. |
Alert Level C:
RFACR_01 Alert C The value of the weighted R factor is > 0.25 Weighted R factor given 0.299 PLAT_213 Alert C Atom Co has ADP max/min Ratio ........... 3.10 PLAT_213 Alert C Atom N3 has ADP max/min Ratio ........... 3.10 PLAT_213 Alert C Atom C13 has ADP max/min Ratio ........... 3.10
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
4 Alert Level C = Please check
[Co(bpb)(OOtBu)(pyridine)] was synthesized by following the procedure outlined by Saussine et al. (1985); pyridine was used in place of 4-methylpyridine. Single crystals of [Co(bpb)(Cl)(pyridine)] were obtained directly from [Co(bpb)(OOtBu)(pyridine)] when the parent compound was dissolved in freshly distilled CHCl3 and the solution was stored for a period of approx 20 min.
Data collection: P3/P4-PC (Siemens, 1991); cell refinement: P3/P4-PC; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL XP (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.
C23H17ClCoN5O2·2CHCl3 | Z = 2 |
Mr = 728.53 | F(000) = 732 |
Triclinic, P1 | Dx = 1.669 Mg m−3 |
a = 8.374 (5) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 12.762 (10) Å | Cell parameters from 45 reflections |
c = 14.381 (9) Å | θ = 8–25° |
α = 98.08 (6)° | µ = 10.87 mm−1 |
β = 90.12 (5)° | T = 130 K |
γ = 107.44 (5)° | Plate, yellow |
V = 1450.1 (17) Å3 | 0.52 × 0.16 × 0.01 mm |
Siemens P4 diffractometer | 2389 reflections with I > 2σ(I) |
Radiation source: Siemens rotating-anode | Rint = 0.075 |
Nickel filter monochromator | θmax = 56.7°, θmin = 3.1° |
2θ–ω scans | h = −9→9 |
Absorption correction: empirical (using intensity measurements) (XABS2, Parkin et al., 1995) | k = −13→13 |
Tmin = 0.070, Tmax = 0.899 | l = 0→15 |
3802 measured reflections | 2 standard reflections every 198 reflections |
3802 independent reflections | intensity decay: <2.0% |
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)] = 0.099 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.299 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.1923P)2 + 3.7422P] where P = (Fo2 + 2Fc2)/3 |
3802 reflections | (Δ/σ)max = 0.002 |
361 parameters | Δρmax = 1.09 e Å−3 |
180 restraints | Δρmin = −1.01 e Å−3 |
C23H17ClCoN5O2·2CHCl3 | γ = 107.44 (5)° |
Mr = 728.53 | V = 1450.1 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.374 (5) Å | Cu Kα radiation |
b = 12.762 (10) Å | µ = 10.87 mm−1 |
c = 14.381 (9) Å | T = 130 K |
α = 98.08 (6)° | 0.52 × 0.16 × 0.01 mm |
β = 90.12 (5)° |
Siemens P4 diffractometer | 2389 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (XABS2, Parkin et al., 1995) | Rint = 0.075 |
Tmin = 0.070, Tmax = 0.899 | θmax = 56.7° |
3802 measured reflections | 2 standard reflections every 198 reflections |
3802 independent reflections | intensity decay: <2.0% |
R[F2 > 2σ(F2)] = 0.099 | 180 restraints |
wR(F2) = 0.299 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.09 e Å−3 |
3802 reflections | Δρmin = −1.01 e Å−3 |
361 parameters |
Experimental. Selected IR frequencies (KBr disk, cm-1): 3422 (s), 1630 (s), 1598 (s), 1571 (m), 1475 (m), 1388 (m), 1292 (w), 1153 (w), 759 (m), 680 (m), 518 (w). |
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. |
x | y | z | Uiso*/Ueq | ||
Co | 0.1672 (2) | 0.52429 (17) | 0.70291 (12) | 0.0281 (6) | |
Cl1 | 0.2222 (3) | 0.4175 (3) | 0.57623 (18) | 0.0348 (8) | |
O1 | −0.0149 (10) | 0.2395 (8) | 0.8033 (6) | 0.040 (2) | |
O2 | 0.6467 (10) | 0.7136 (7) | 0.7331 (6) | 0.039 (2) | |
N1 | −0.0760 (12) | 0.4480 (9) | 0.6802 (6) | 0.030 (2) | |
N2 | 0.1554 (12) | 0.4084 (8) | 0.7737 (6) | 0.026 (2) | |
N3 | 0.3941 (11) | 0.5756 (8) | 0.7442 (6) | 0.028 (2) | |
N4 | 0.2348 (11) | 0.6530 (9) | 0.6313 (6) | 0.029 (2) | |
N5 | 0.1084 (12) | 0.6176 (9) | 0.8111 (6) | 0.032 (2) | |
C1 | −0.1968 (14) | 0.4766 (11) | 0.6364 (8) | 0.029 (3) | |
H1 | −0.1666 | 0.5441 | 0.6105 | 0.035* | |
C2 | −0.3596 (15) | 0.4124 (11) | 0.6280 (9) | 0.037 (3) | |
H2 | −0.4408 | 0.4359 | 0.5976 | 0.045* | |
C3 | −0.4082 (15) | 0.3117 (12) | 0.6641 (9) | 0.039 (3) | |
H3 | −0.5205 | 0.2641 | 0.6569 | 0.047* | |
C4 | −0.2840 (16) | 0.2852 (12) | 0.7107 (9) | 0.040 (3) | |
H4 | −0.3125 | 0.2193 | 0.7387 | 0.048* | |
C5 | −0.1236 (13) | 0.3510 (10) | 0.7173 (7) | 0.024 (3) | |
C6 | 0.0157 (15) | 0.3273 (11) | 0.7694 (8) | 0.033 (3) | |
C7 | 0.3129 (15) | 0.4166 (11) | 0.8165 (8) | 0.031 (3) | |
C8 | 0.3423 (16) | 0.3412 (11) | 0.8698 (8) | 0.036 (3) | |
H8 | 0.2549 | 0.2758 | 0.8771 | 0.044* | |
C9 | 0.5013 (16) | 0.3619 (11) | 0.9128 (8) | 0.035 (3) | |
H9 | 0.5226 | 0.3108 | 0.9495 | 0.042* | |
C10 | 0.6293 (16) | 0.4596 (12) | 0.9008 (9) | 0.038 (3) | |
H10 | 0.7372 | 0.4740 | 0.9299 | 0.046* | |
C11 | 0.6001 (15) | 0.5340 (11) | 0.8477 (8) | 0.035 (3) | |
H11 | 0.6856 | 0.6007 | 0.8414 | 0.042* | |
C12 | 0.4417 (14) | 0.5095 (10) | 0.8030 (8) | 0.029 (3) | |
C13 | 0.4931 (15) | 0.6676 (11) | 0.7152 (8) | 0.030 (3) | |
C14 | 0.3991 (15) | 0.7114 (12) | 0.6526 (9) | 0.039 (3) | |
C15 | 0.4713 (17) | 0.8052 (11) | 0.6127 (9) | 0.038 (3) | |
H15 | 0.5860 | 0.8454 | 0.6270 | 0.046* | |
C16 | 0.3784 (16) | 0.8415 (12) | 0.5518 (9) | 0.041 (3) | |
H16 | 0.4270 | 0.9083 | 0.5267 | 0.049* | |
C17 | 0.2141 (16) | 0.7792 (11) | 0.5282 (8) | 0.033 (3) | |
H17 | 0.1484 | 0.8008 | 0.4850 | 0.040* | |
C18 | 0.1481 (15) | 0.6849 (11) | 0.5690 (7) | 0.030 (3) | |
H18 | 0.0359 | 0.6409 | 0.5519 | 0.036* | |
C19 | 0.1409 (15) | 0.6083 (11) | 0.9022 (8) | 0.037 (3) | |
H19 | 0.1929 | 0.5544 | 0.9139 | 0.045* | |
C20 | 0.1022 (15) | 0.6727 (11) | 0.9768 (8) | 0.035 (3) | |
H20 | 0.1251 | 0.6624 | 1.0390 | 0.042* | |
C21 | 0.0312 (15) | 0.7511 (11) | 0.9623 (8) | 0.036 (3) | |
H21 | 0.0037 | 0.7961 | 1.0143 | 0.043* | |
C22 | −0.0017 (14) | 0.7660 (11) | 0.8718 (8) | 0.036 (3) | |
H22 | −0.0510 | 0.8213 | 0.8601 | 0.043* | |
C23 | 0.0396 (14) | 0.6980 (10) | 0.7992 (8) | 0.029 (3) | |
H23 | 0.0182 | 0.7082 | 0.7367 | 0.035* | |
C24 | 0.1005 (18) | 0.0457 (13) | 0.6934 (11) | 0.054 (4) | |
H24 | 0.0536 | 0.0969 | 0.7362 | 0.064* | |
Cl2 | 0.1501 (5) | 0.1012 (4) | 0.5887 (3) | 0.0734 (14) | |
Cl3 | 0.2805 (5) | 0.0364 (3) | 0.7491 (2) | 0.0588 (11) | |
Cl4 | −0.0525 (4) | −0.0854 (3) | 0.6714 (2) | 0.0514 (10) | |
C25 | 0.6529 (15) | 0.9103 (11) | 0.8887 (9) | 0.035 (3) | |
H25 | 0.6842 | 0.8539 | 0.8430 | 0.043* | |
Cl5 | 0.4354 (4) | 0.8709 (4) | 0.8949 (3) | 0.0640 (12) | |
Cl6 | 0.7282 (5) | 1.0403 (3) | 0.8512 (2) | 0.0620 (12) | |
Cl7 | 0.7483 (5) | 0.9173 (4) | 1.0009 (2) | 0.0627 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0206 (11) | 0.0509 (14) | 0.0117 (10) | 0.0111 (9) | −0.0089 (8) | 0.0012 (8) |
Cl1 | 0.0242 (15) | 0.059 (2) | 0.0185 (15) | 0.0107 (14) | −0.0080 (12) | 0.0025 (13) |
O1 | 0.032 (5) | 0.042 (6) | 0.036 (5) | 0.000 (4) | −0.008 (4) | 0.005 (4) |
O2 | 0.023 (5) | 0.050 (6) | 0.034 (5) | 0.002 (4) | −0.016 (4) | −0.003 (4) |
N1 | 0.025 (5) | 0.046 (6) | 0.016 (4) | 0.011 (4) | −0.009 (4) | −0.004 (4) |
N2 | 0.033 (5) | 0.036 (5) | 0.012 (4) | 0.016 (4) | −0.006 (4) | 0.003 (4) |
N3 | 0.025 (5) | 0.036 (5) | 0.016 (4) | 0.001 (4) | −0.015 (4) | −0.001 (4) |
N4 | 0.025 (5) | 0.048 (6) | 0.010 (4) | 0.005 (4) | −0.004 (4) | −0.001 (4) |
N5 | 0.029 (5) | 0.050 (6) | 0.016 (5) | 0.009 (5) | −0.008 (4) | 0.007 (4) |
C1 | 0.029 (6) | 0.036 (6) | 0.021 (5) | 0.005 (5) | 0.004 (5) | 0.008 (5) |
C2 | 0.026 (6) | 0.049 (7) | 0.034 (6) | 0.012 (5) | −0.009 (5) | −0.003 (5) |
C3 | 0.017 (5) | 0.052 (7) | 0.040 (6) | 0.003 (5) | −0.001 (5) | −0.003 (5) |
C4 | 0.037 (6) | 0.052 (7) | 0.034 (6) | 0.020 (6) | 0.005 (5) | 0.002 (5) |
C5 | 0.017 (5) | 0.030 (6) | 0.019 (5) | 0.000 (5) | −0.009 (4) | −0.004 (4) |
C6 | 0.025 (6) | 0.040 (7) | 0.028 (6) | 0.006 (5) | 0.002 (5) | −0.001 (5) |
C7 | 0.028 (6) | 0.046 (7) | 0.021 (5) | 0.013 (5) | −0.005 (5) | 0.009 (5) |
C8 | 0.036 (6) | 0.045 (7) | 0.027 (6) | 0.011 (5) | −0.001 (5) | 0.002 (5) |
C9 | 0.042 (6) | 0.046 (7) | 0.026 (6) | 0.026 (6) | −0.009 (5) | 0.005 (5) |
C10 | 0.029 (6) | 0.059 (7) | 0.031 (6) | 0.021 (6) | −0.007 (5) | 0.005 (5) |
C11 | 0.030 (6) | 0.046 (7) | 0.028 (6) | 0.012 (5) | −0.011 (5) | 0.000 (5) |
C12 | 0.026 (6) | 0.039 (6) | 0.022 (5) | 0.011 (5) | −0.006 (5) | 0.005 (5) |
C13 | 0.028 (6) | 0.043 (7) | 0.015 (5) | 0.012 (5) | −0.014 (5) | −0.010 (5) |
C14 | 0.023 (6) | 0.047 (7) | 0.038 (6) | 0.003 (5) | −0.003 (5) | −0.002 (5) |
C15 | 0.035 (6) | 0.037 (7) | 0.039 (6) | 0.005 (5) | −0.009 (5) | 0.006 (5) |
C16 | 0.041 (7) | 0.044 (7) | 0.037 (6) | 0.007 (6) | −0.005 (5) | 0.015 (5) |
C17 | 0.041 (6) | 0.038 (6) | 0.023 (6) | 0.014 (5) | −0.009 (5) | 0.005 (5) |
C18 | 0.028 (6) | 0.046 (7) | 0.015 (5) | 0.009 (5) | −0.014 (5) | 0.001 (5) |
C19 | 0.034 (6) | 0.051 (7) | 0.028 (6) | 0.012 (5) | −0.007 (5) | 0.009 (5) |
C20 | 0.032 (6) | 0.052 (7) | 0.022 (6) | 0.016 (5) | −0.007 (5) | 0.003 (5) |
C21 | 0.026 (6) | 0.050 (7) | 0.024 (6) | 0.002 (5) | −0.003 (5) | 0.005 (5) |
C22 | 0.025 (6) | 0.053 (7) | 0.027 (6) | 0.012 (5) | −0.009 (5) | −0.003 (5) |
C23 | 0.025 (6) | 0.042 (6) | 0.018 (5) | 0.007 (5) | −0.009 (5) | −0.001 (5) |
C24 | 0.050 (7) | 0.059 (8) | 0.055 (7) | 0.019 (6) | −0.003 (6) | 0.014 (6) |
Cl2 | 0.063 (3) | 0.092 (3) | 0.050 (2) | −0.008 (2) | −0.026 (2) | 0.029 (2) |
Cl3 | 0.055 (2) | 0.076 (3) | 0.046 (2) | 0.021 (2) | −0.0265 (18) | 0.0033 (18) |
Cl4 | 0.045 (2) | 0.057 (2) | 0.049 (2) | 0.0117 (18) | −0.0047 (16) | 0.0072 (17) |
C25 | 0.034 (6) | 0.037 (6) | 0.033 (6) | 0.007 (5) | −0.007 (5) | 0.008 (5) |
Cl5 | 0.033 (2) | 0.071 (3) | 0.078 (3) | 0.0089 (19) | −0.0001 (18) | −0.008 (2) |
Cl6 | 0.078 (3) | 0.054 (3) | 0.037 (2) | −0.002 (2) | −0.0026 (19) | 0.0027 (16) |
Cl7 | 0.075 (3) | 0.087 (3) | 0.035 (2) | 0.042 (2) | −0.0150 (18) | 0.0011 (18) |
Co—N3 | 1.879 (9) | C9—H9 | 0.950 |
Co—N2 | 1.890 (9) | C10—C11 | 1.374 (18) |
Co—N5 | 1.978 (10) | C10—H10 | 0.950 |
Co—N1 | 1.980 (10) | C11—C12 | 1.401 (16) |
Co—N4 | 2.000 (11) | C11—H11 | 0.950 |
Co—Cl1 | 2.252 (4) | C13—C14 | 1.465 (19) |
O1—C6 | 1.242 (15) | C14—C15 | 1.373 (19) |
O2—C13 | 1.252 (14) | C15—C16 | 1.383 (18) |
N1—C1 | 1.356 (15) | C15—H15 | 0.950 |
N1—C5 | 1.366 (15) | C16—C17 | 1.381 (17) |
N2—C6 | 1.304 (15) | C16—H16 | 0.950 |
N2—C7 | 1.423 (15) | C17—C18 | 1.378 (17) |
N3—C13 | 1.340 (16) | C17—H17 | 0.950 |
N3—C12 | 1.409 (16) | C18—H18 | 0.950 |
N4—C18 | 1.332 (15) | C19—C20 | 1.358 (17) |
N4—C14 | 1.365 (15) | C19—H19 | 0.950 |
N5—C23 | 1.349 (16) | C20—C21 | 1.346 (18) |
N5—C19 | 1.365 (15) | C20—H20 | 0.950 |
C1—C2 | 1.359 (17) | C21—C22 | 1.380 (17) |
C1—H1 | 0.950 | C21—H21 | 0.950 |
C2—C3 | 1.400 (19) | C22—C23 | 1.374 (17) |
C2—H2 | 0.950 | C22—H22 | 0.950 |
C3—C4 | 1.385 (18) | C23—H23 | 0.950 |
C3—H3 | 0.950 | C24—Cl2 | 1.750 (15) |
C4—C5 | 1.349 (17) | C24—Cl3 | 1.749 (15) |
C4—H4 | 0.950 | C24—Cl4 | 1.762 (16) |
C5—C6 | 1.511 (17) | C24—H24 | 1.000 |
C7—C12 | 1.381 (17) | C25—Cl5 | 1.744 (13) |
C7—C8 | 1.386 (18) | C25—Cl6 | 1.751 (13) |
C8—C9 | 1.402 (17) | C25—Cl7 | 1.778 (12) |
C8—H8 | 0.950 | C25—H25 | 1.000 |
C9—C10 | 1.412 (19) | ||
N3—Co—N2 | 84.6 (4) | C10—C9—H9 | 120.4 |
N3—Co—N5 | 90.9 (4) | C11—C10—C9 | 121.0 (12) |
N2—Co—N5 | 92.4 (4) | C11—C10—H10 | 119.5 |
N3—Co—N1 | 167.4 (4) | C9—C10—H10 | 119.5 |
N2—Co—N1 | 83.0 (4) | C10—C11—C12 | 118.7 (12) |
N5—Co—N1 | 87.2 (4) | C10—C11—H11 | 120.7 |
N3—Co—N4 | 83.0 (4) | C12—C11—H11 | 120.7 |
N2—Co—N4 | 167.2 (4) | C7—C12—C11 | 121.3 (11) |
N5—Co—N4 | 91.1 (4) | C7—C12—N3 | 113.3 (10) |
N1—Co—N4 | 109.5 (4) | C11—C12—N3 | 125.4 (12) |
N3—Co—Cl1 | 91.7 (3) | O2—C13—N3 | 128.4 (11) |
N2—Co—Cl1 | 88.7 (3) | O2—C13—C14 | 120.7 (12) |
N5—Co—Cl1 | 177.2 (3) | N3—C13—C14 | 110.9 (10) |
N1—Co—Cl1 | 90.4 (3) | N4—C14—C15 | 119.7 (12) |
N4—Co—Cl1 | 88.3 (3) | N4—C14—C13 | 117.5 (12) |
C1—N1—C5 | 117.5 (10) | C15—C14—C13 | 122.7 (11) |
C1—N1—Co | 131.1 (9) | C14—C15—C16 | 120.6 (12) |
C5—N1—Co | 111.4 (7) | C14—C15—H15 | 119.7 |
C6—N2—C7 | 128.4 (11) | C16—C15—H15 | 119.7 |
C6—N2—Co | 118.4 (8) | C17—C16—C15 | 119.0 (13) |
C7—N2—Co | 112.8 (8) | C17—C16—H16 | 120.5 |
C13—N3—C12 | 126.9 (10) | C15—C16—H16 | 120.5 |
C13—N3—Co | 118.6 (8) | C18—C17—C16 | 118.2 (11) |
C12—N3—Co | 114.5 (8) | C18—C17—H17 | 120.9 |
C18—N4—C14 | 119.5 (11) | C16—C17—H17 | 120.9 |
C18—N4—Co | 130.7 (8) | N4—C18—C17 | 122.8 (11) |
C14—N4—Co | 109.8 (8) | N4—C18—H18 | 118.6 |
C23—N5—C19 | 115.6 (10) | C17—C18—H18 | 118.6 |
C23—N5—Co | 121.7 (7) | C20—C19—N5 | 122.9 (12) |
C19—N5—Co | 122.6 (9) | C20—C19—H19 | 118.5 |
N1—C1—C2 | 122.4 (12) | N5—C19—H19 | 118.5 |
N1—C1—H1 | 118.8 | C21—C20—C19 | 119.8 (12) |
C2—C1—H1 | 118.8 | C21—C20—H20 | 120.1 |
C1—C2—C3 | 120.4 (12) | C19—C20—H20 | 120.1 |
C1—C2—H2 | 119.8 | C20—C21—C22 | 120.0 (12) |
C3—C2—H2 | 119.8 | C20—C21—H21 | 120.0 |
C4—C3—C2 | 116.4 (12) | C22—C21—H21 | 120.0 |
C4—C3—H3 | 121.8 | C23—C22—C21 | 117.4 (13) |
C2—C3—H3 | 121.8 | C23—C22—H22 | 121.3 |
C5—C4—C3 | 121.5 (13) | C21—C22—H22 | 121.3 |
C5—C4—H4 | 119.3 | N5—C23—C22 | 124.1 (11) |
C3—C4—H4 | 119.3 | N5—C23—H23 | 117.9 |
C4—C5—N1 | 121.8 (11) | C22—C23—H23 | 117.9 |
C4—C5—C6 | 123.5 (12) | Cl2—C24—Cl3 | 110.5 (8) |
N1—C5—C6 | 114.6 (10) | Cl2—C24—Cl4 | 110.6 (8) |
O1—C6—N2 | 129.0 (12) | Cl3—C24—Cl4 | 110.7 (9) |
O1—C6—C5 | 119.1 (11) | Cl2—C24—H24 | 108.3 |
N2—C6—C5 | 111.9 (11) | Cl3—C24—H24 | 108.3 |
C12—C7—C8 | 120.0 (11) | Cl4—C24—H24 | 108.3 |
C12—C7—N2 | 114.8 (10) | Cl5—C25—Cl6 | 110.9 (7) |
C8—C7—N2 | 125.2 (11) | Cl5—C25—Cl7 | 110.2 (7) |
C7—C8—C9 | 119.8 (12) | Cl6—C25—Cl7 | 108.8 (7) |
C7—C8—H8 | 120.1 | Cl5—C25—H25 | 109.0 |
C9—C8—H8 | 120.1 | Cl6—C25—H25 | 109.0 |
C8—C9—C10 | 119.2 (12) | Cl7—C25—H25 | 109.0 |
C8—C9—H9 | 120.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H24···O1 | 1.00 | 2.17 | 3.144 (19) | 164 |
C25—H25···O2 | 1.00 | 2.16 | 3.107 (16) | 157 |
Experimental details
Crystal data | |
Chemical formula | C23H17ClCoN5O2·2CHCl3 |
Mr | 728.53 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 130 |
a, b, c (Å) | 8.374 (5), 12.762 (10), 14.381 (9) |
α, β, γ (°) | 98.08 (6), 90.12 (5), 107.44 (5) |
V (Å3) | 1450.1 (17) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 10.87 |
Crystal size (mm) | 0.52 × 0.16 × 0.01 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (XABS2, Parkin et al., 1995) |
Tmin, Tmax | 0.070, 0.899 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3802, 3802, 2389 |
Rint | 0.075 |
θmax (°) | 56.7 |
(sin θ/λ)max (Å−1) | 0.542 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.099, 0.299, 1.03 |
No. of reflections | 3802 |
No. of parameters | 361 |
No. of restraints | 180 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.09, −1.01 |
Computer programs: P3/P4-PC (Siemens, 1991), P3/P4-PC, XDISK (Siemens, 1991), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL XP (Sheldrick, 1994), SHELXL97.
Co—N3 | 1.879 (9) | Co—N1 | 1.980 (10) |
Co—N2 | 1.890 (9) | Co—N4 | 2.000 (11) |
Co—N5 | 1.978 (10) | Co—Cl1 | 2.252 (4) |
N3—Co—N2 | 84.6 (4) | N5—Co—N4 | 91.1 (4) |
N3—Co—N5 | 90.9 (4) | N1—Co—N4 | 109.5 (4) |
N2—Co—N5 | 92.4 (4) | N3—Co—Cl1 | 91.7 (3) |
N3—Co—N1 | 167.4 (4) | N2—Co—Cl1 | 88.7 (3) |
N2—Co—N1 | 83.0 (4) | N5—Co—Cl1 | 177.2 (3) |
N5—Co—N1 | 87.2 (4) | N1—Co—Cl1 | 90.4 (3) |
N3—Co—N4 | 83.0 (4) | N4—Co—Cl1 | 88.3 (3) |
N2—Co—N4 | 167.2 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C24—H24···O1 | 1.00 | 2.17 | 3.144 (19) | 164.3 |
C25—H25···O2 | 1.00 | 2.16 | 3.107 (16) | 157.3 |
When the complex [Co(bpb)(OOtBu)(pyridine)] was stored for a brief amount of time in CHCl3 at room temperature, the title compound [Co(bpb)(Cl)(pyridine)], (I), crystallized out as yellow plates. The mechanism for the incorporation of the chloride ion into the cobalt(III) complex remains unknown at this time, although it is clear that the source of the chloride ion is the solvent CHCl3. The mechanism of decomposition of various cobalt(III) alkylperoxides in many solvents has been discussed by Chavez et al. (1998). The decomposition of Co(bpb)(OOtBu)(pyridine) may proceed through a similar reaction pathway.
Since the initial report by Chapman & Vagg (1979), the ligand N,N'-bis(2'-pyridinecarboxamide)-1,2-benzene (bpbH2) has been extensively employed as a tetradentate diamide ligand for various transition metal ions. This ligand was designed exclusively to investigate the unique bonding properties of deprotonated carboxamido N atoms toward Mn+ ions. The square-planar cobalt(II) complex [Co(bpb)].H2O was reported in the initial account by Chapman & Vagg (1979). Later, bpbH2 was utilized by Saussine et al. (1985) to stabilize the cobalt(III) alkylperoxide complex [Co(bpb)(OOtBu)(4-Mepy)] (4-Mepy = 4-methylpyridine). Although this cobalt(III) alkylperoxide complex was not structurally characterized by X-ray diffraction, its activity as a catalyst for the oxidation of various hydrocarbon substrates in the presence of excess alkyhydroperoxide was investigated in detail. The role of cobalt(III) alkylperoxide complexes in the oxidation of hydrocarbons has recently been highlighted in a review by Chavez & Mascharak (2000).
The structure of [Co(bpb)(Cl)(pyridine)] is presented in Fig. 1. The cobalt(III) center resides in an octahedral geometry with the bpb2- ligand occupying the equatorial plane of the octahedron. The remaining coordination sites are occupied by one chloride and one pyridine ligand. The Co—N(amido) ditances are similar in length [Co—N2, 1.890 (9) Å, Co—N3, 1.879 (9) Å] while the Co—N(py) distances are 1.980 (10) Å and 2.000 (11) Å. The single pyridine is coordinated to the cobalt(III) center at a distance of 1.978 (10) Å. The Co—Cl distance [2.251 (4) Å] is well within the range of CoIII—Cl distances. For example, the Co—Cl bond distances in [Co(NH3)5(Cl)]Cl2 and [Co(Metrenen)(Cl)](ClO4)2 are 2.286 (2) and 2.248 (5) Å, respectively (Messmer & Amma, 1968; Buckingham et al., 1972). As expected, the bpb2- ligand frame remains completely planar in the complex. The structure reveals (Table 2) two CHCl3 molecules of solvation which form weak hydrogen bonds with the carbonyl-O atoms of the bpb2- ligand.