Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104016877/av1186sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104016877/av1186Isup2.hkl |
CCDC reference: 251287
The title complex was prepared using the method previously reported by Hirotsu et al. (1996). Single crystals of (I) were obtained by slow evaporation of a dichloromethane-ethanol solution (Ratio?).
The H atoms of the three methyl groups were refined as idealized CH3 groups with a rotating motion. All other H atoms were placed in fixed positions by assuming C—H distances of 0.97 (CH2), 0.98 (CH) or 0.93 Å (imidazole CH). All H atoms were treated as riding, with Uiso(H) = 1.2Ueq(C). Please check added text. The absolute structure was set by reference to the known chirality of the enantiopure diamine employed.
Data collection: Rigaku/AFC Diffractometer Control Software (Rigaku, 1995); cell refinement: Rigaku/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: TEXSAN.
Fig. 1. A drawing of the cation of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. |
[Co(C29H24N2O2)(C4H6N2)2]ClO4 | Dx = 1.422 Mg m−3 |
Mr = 755.10 | Mo Kα radiation, λ = 0.71069 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 14.334 (2) Å | θ = 14.7–15.0° |
b = 17.766 (3) Å | µ = 0.62 mm−1 |
c = 13.849 (2) Å | T = 298 K |
V = 3526.9 (9) Å3 | Prism, red |
Z = 4 | 0.62 × 0.45 × 0.23 mm |
F(000) = 1568.00 |
Rigaku AFC-7S diffractometer | 4120 reflections with F > 4σ(F) |
Radiation source: sealed X-ray tube | Rint = 0.012 |
Graphite monochromator | θmax = 30.0°, θmin = 4.1° |
ω/2θ scans | h = 0→20 |
Absorption correction: ψ scan (North et al., 1968) | k = −12→24 |
Tmin = 0.783, Tmax = 0.867 | l = −10→19 |
6564 measured reflections | 3 standard reflections every 150 reflections |
5671 independent reflections | intensity decay: 0.0% |
Refinement on F2 | w = 1/[σ2(Fo2) + (0.0589P)2 + 0.3625P] where P = (Fo2 + 2Fc2)/3 |
Least-squares matrix: full | (Δ/σ)max = −0.007 |
R[F2 > 2σ(F2)] = 0.038 | Δρmax = 0.31 e Å−3 |
wR(F2) = 0.115 | Δρmin = −0.52 e Å−3 |
S = 1.04 | Extinction correction: SHELXL97 (Sheldrick, 1997) |
5671 reflections | Extinction coefficient: 0.0011 |
464 parameters | Absolute structure: Flack (1983) |
H-atom parameters constrained | Absolute structure parameter: −0.01 (3) |
[Co(C29H24N2O2)(C4H6N2)2]ClO4 | V = 3526.9 (9) Å3 |
Mr = 755.10 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 14.334 (2) Å | µ = 0.62 mm−1 |
b = 17.766 (3) Å | T = 298 K |
c = 13.849 (2) Å | 0.62 × 0.45 × 0.23 mm |
Rigaku AFC-7S diffractometer | 4120 reflections with F > 4σ(F) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.012 |
Tmin = 0.783, Tmax = 0.867 | 3 standard reflections every 150 reflections |
6564 measured reflections | intensity decay: 0.0% |
5671 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.115 | Δρmax = 0.31 e Å−3 |
S = 1.04 | Δρmin = −0.52 e Å−3 |
5671 reflections | Absolute structure: Flack (1983) |
464 parameters | Absolute structure parameter: −0.01 (3) |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.41553 (2) | 0.49768 (3) | 0.22197 (2) | 0.0294 (1) | |
Cl1 | 0.59513 (8) | 0.5028 (1) | 0.79937 (7) | 0.0793 (3) | |
O1 | 0.3563 (2) | 0.4238 (1) | 0.2975 (2) | 0.0356 (6) | |
O2 | 0.3522 (2) | 0.5702 (1) | 0.2970 (2) | 0.0376 (7) | |
O3 | 0.5016 (3) | 0.5009 (3) | 0.8335 (3) | 0.105 (1) | |
O4 | 0.6102 (6) | 0.4371 (3) | 0.7454 (4) | 0.154 (3) | |
O5 | 0.6051 (5) | 0.5648 (3) | 0.7354 (4) | 0.140 (3) | |
O6 | 0.6536 (3) | 0.5101 (6) | 0.8777 (3) | 0.199 (4) | |
N1 | 0.4788 (2) | 0.4260 (2) | 0.1442 (3) | 0.0322 (8) | |
N2 | 0.4755 (2) | 0.5711 (2) | 0.1452 (3) | 0.0324 (8) | |
N3 | 0.5164 (2) | 0.5004 (2) | 0.3165 (2) | 0.0354 (4) | |
N4 | 0.3118 (2) | 0.4965 (2) | 0.1334 (1) | 0.0330 (4) | |
N5 | 0.6147 (3) | 0.4666 (2) | 0.4300 (3) | 0.0431 (9) | |
N6 | 0.1680 (2) | 0.4977 (3) | 0.0821 (2) | 0.0424 (5) | |
C1 | 0.3301 (3) | 0.3591 (2) | 0.2622 (3) | 0.0342 (9) | |
C2 | 0.2578 (3) | 0.3200 (2) | 0.3116 (4) | 0.045 (1) | |
C3 | 0.2294 (4) | 0.2494 (2) | 0.2823 (5) | 0.059 (1) | |
C4 | 0.2675 (4) | 0.2161 (3) | 0.2018 (5) | 0.061 (2) | |
C5 | 0.3364 (3) | 0.2533 (2) | 0.1521 (4) | 0.050 (1) | |
C6 | 0.3698 (3) | 0.3247 (2) | 0.1796 (3) | 0.0379 (10) | |
C7 | 0.4492 (3) | 0.3582 (2) | 0.1278 (3) | 0.0337 (9) | |
C8 | 0.4931 (3) | 0.3104 (2) | 0.0510 (3) | 0.038 (1) | |
C9 | 0.5472 (4) | 0.2479 (2) | 0.0758 (4) | 0.048 (1) | |
C10 | 0.5852 (5) | 0.2027 (2) | 0.0055 (4) | 0.059 (1) | |
C11 | 0.5694 (5) | 0.2182 (3) | −0.0896 (4) | 0.065 (2) | |
C12 | 0.5185 (4) | 0.2799 (3) | −0.1153 (4) | 0.061 (2) | |
C13 | 0.4790 (4) | 0.3263 (2) | −0.0462 (3) | 0.050 (1) | |
C14 | 0.3258 (3) | 0.6354 (2) | 0.2617 (3) | 0.0368 (10) | |
C15 | 0.2544 (3) | 0.6743 (2) | 0.3112 (3) | 0.048 (1) | |
C16 | 0.2248 (4) | 0.7437 (2) | 0.2829 (5) | 0.054 (1) | |
C17 | 0.2611 (3) | 0.7774 (3) | 0.2007 (5) | 0.057 (1) | |
C18 | 0.3294 (3) | 0.7411 (2) | 0.1498 (4) | 0.050 (1) | |
C19 | 0.3650 (3) | 0.6700 (2) | 0.1787 (3) | 0.0359 (9) | |
C20 | 0.4446 (3) | 0.6385 (2) | 0.1271 (3) | 0.0333 (9) | |
C21 | 0.4906 (3) | 0.6864 (2) | 0.0517 (3) | 0.036 (1) | |
C22 | 0.5456 (4) | 0.7463 (2) | 0.0779 (4) | 0.046 (1) | |
C23 | 0.5817 (5) | 0.7935 (2) | 0.0071 (4) | 0.059 (1) | |
C24 | 0.5657 (5) | 0.7799 (3) | −0.0883 (4) | 0.060 (2) | |
C25 | 0.5112 (5) | 0.7181 (3) | −0.1147 (4) | 0.072 (2) | |
C26 | 0.4746 (4) | 0.6717 (3) | −0.0450 (3) | 0.053 (1) | |
C27 | 0.5607 (3) | 0.4574 (2) | 0.0906 (3) | 0.0354 (9) | |
C28 | 0.5632 (4) | 0.5425 (2) | 0.1057 (4) | 0.046 (1) | |
C29 | 0.6525 (3) | 0.4234 (2) | 0.1236 (4) | 0.069 (1) | |
C30 | 0.5500 (3) | 0.4432 (2) | 0.3663 (4) | 0.041 (1) | |
C31 | 0.6230 (4) | 0.5426 (3) | 0.4180 (4) | 0.054 (1) | |
C32 | 0.5616 (4) | 0.5626 (2) | 0.3501 (4) | 0.049 (1) | |
C33 | 0.6651 (3) | 0.4207 (3) | 0.4992 (3) | 0.060 (1) | |
C34 | 0.2239 (2) | 0.4963 (3) | 0.1597 (2) | 0.0374 (6) | |
C35 | 0.2231 (2) | 0.4977 (3) | 0.0014 (2) | 0.0473 (7) | |
C36 | 0.3120 (2) | 0.4979 (3) | 0.0339 (2) | 0.0411 (6) | |
C37 | 0.0658 (2) | 0.4975 (3) | 0.0841 (3) | 0.0632 (9) | |
H1 | 0.6521 | 0.3702 | 0.1115 | 0.0694* | |
H2 | 0.6605 | 0.4322 | 0.1915 | 0.0694* | |
H3 | 0.7030 | 0.4462 | 0.0888 | 0.0694* | |
H4 | 0.6348 | 0.3727 | 0.5054 | 0.0603* | |
H5 | 0.6658 | 0.4455 | 0.5608 | 0.0603* | |
H6 | 0.7279 | 0.4134 | 0.4773 | 0.0603* | |
H7 | 0.0433 | 0.5484 | 0.0844 | 0.0632* | |
H8 | 0.0446 | 0.4721 | 0.1412 | 0.0632* | |
H9 | 0.0425 | 0.4718 | 0.0281 | 0.0632* | |
H10 | 0.2291 | 0.3425 | 0.3646 | 0.0545* | |
H11 | 0.1840 | 0.2240 | 0.3174 | 0.0705* | |
H12 | 0.2469 | 0.1691 | 0.1813 | 0.0738* | |
H13 | 0.3622 | 0.2303 | 0.0979 | 0.0595* | |
H14 | 0.5576 | 0.2368 | 0.1406 | 0.0573* | |
H15 | 0.6218 | 0.1616 | 0.0227 | 0.0703* | |
H16 | 0.5934 | 0.1866 | −0.1370 | 0.0775* | |
H17 | 0.5102 | 0.2910 | −0.1804 | 0.0726* | |
H18 | 0.4433 | 0.3676 | −0.0646 | 0.0604* | |
H19 | 0.2268 | 0.6519 | 0.3647 | 0.0577* | |
H20 | 0.1799 | 0.7688 | 0.3190 | 0.0645* | |
H21 | 0.2392 | 0.8241 | 0.1805 | 0.0689* | |
H22 | 0.3532 | 0.7638 | 0.0945 | 0.0603* | |
H23 | 0.5586 | 0.7552 | 0.1427 | 0.0555* | |
H24 | 0.6172 | 0.8349 | 0.0252 | 0.0705* | |
H25 | 0.5907 | 0.8114 | −0.1353 | 0.0722* | |
H26 | 0.4997 | 0.7082 | −0.1796 | 0.0865* | |
H27 | 0.4389 | 0.6302 | −0.0628 | 0.0638* | |
H28 | 0.5526 | 0.4470 | 0.0216 | 0.0424* | |
H29 | 0.5748 | 0.5667 | 0.0440 | 0.0550* | |
H30 | 0.6134 | 0.5545 | 0.1500 | 0.0550* | |
H31 | 0.5314 | 0.3934 | 0.3584 | 0.0491* | |
H32 | 0.6636 | 0.5744 | 0.4509 | 0.0648* | |
H33 | 0.5513 | 0.6116 | 0.3289 | 0.0593* | |
H34 | 0.2032 | 0.4954 | 0.2234 | 0.0448* | |
H35 | 0.2034 | 0.4976 | −0.0625 | 0.0568* | |
H36 | 0.3650 | 0.4988 | −0.0048 | 0.0493* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0318 (2) | 0.0317 (2) | 0.0246 (2) | −0.0016 (3) | 0.0009 (1) | 0.0008 (3) |
Cl1 | 0.0819 (7) | 0.1039 (9) | 0.0523 (5) | −0.001 (1) | −0.0008 (5) | −0.006 (1) |
O1 | 0.041 (2) | 0.039 (1) | 0.027 (1) | −0.007 (1) | 0.005 (1) | 0.002 (1) |
O2 | 0.046 (2) | 0.037 (1) | 0.030 (1) | 0.002 (1) | 0.001 (1) | 0.000 (1) |
O3 | 0.086 (2) | 0.124 (3) | 0.105 (3) | 0.004 (4) | 0.007 (2) | −0.006 (4) |
O4 | 0.218 (8) | 0.132 (4) | 0.113 (4) | 0.074 (5) | 0.036 (5) | −0.020 (4) |
O5 | 0.158 (6) | 0.142 (4) | 0.119 (4) | −0.048 (4) | −0.025 (5) | 0.038 (4) |
O6 | 0.102 (3) | 0.43 (1) | 0.066 (2) | −0.009 (8) | −0.021 (2) | −0.021 (7) |
N1 | 0.033 (2) | 0.034 (1) | 0.029 (2) | 0.000 (1) | 0.000 (2) | 0.003 (1) |
N2 | 0.034 (2) | 0.034 (1) | 0.030 (2) | −0.002 (1) | 0.003 (2) | 0.000 (1) |
N3 | 0.038 (1) | 0.037 (1) | 0.0315 (10) | −0.001 (2) | −0.0022 (8) | −0.002 (2) |
N4 | 0.037 (1) | 0.036 (1) | 0.0260 (9) | 0.004 (2) | −0.0011 (8) | 0.001 (2) |
N5 | 0.041 (2) | 0.051 (2) | 0.038 (2) | 0.000 (2) | −0.008 (2) | −0.002 (1) |
N6 | 0.037 (1) | 0.048 (1) | 0.042 (1) | −0.001 (2) | −0.0065 (10) | −0.004 (2) |
C1 | 0.033 (2) | 0.037 (2) | 0.033 (2) | −0.001 (2) | 0.003 (2) | 0.005 (2) |
C2 | 0.035 (3) | 0.048 (2) | 0.053 (3) | −0.007 (2) | 0.009 (3) | 0.008 (2) |
C3 | 0.044 (3) | 0.048 (2) | 0.084 (4) | −0.015 (2) | 0.016 (3) | 0.006 (3) |
C4 | 0.047 (3) | 0.040 (2) | 0.097 (5) | −0.005 (2) | 0.006 (4) | −0.006 (3) |
C5 | 0.047 (3) | 0.042 (2) | 0.060 (3) | −0.008 (2) | 0.002 (3) | −0.009 (2) |
C6 | 0.032 (2) | 0.040 (2) | 0.041 (2) | 0.002 (2) | −0.003 (2) | 0.000 (2) |
C7 | 0.037 (2) | 0.034 (2) | 0.030 (2) | 0.002 (2) | 0.000 (2) | 0.000 (2) |
C8 | 0.038 (3) | 0.039 (2) | 0.037 (3) | 0.002 (2) | 0.002 (2) | −0.003 (2) |
C9 | 0.057 (3) | 0.039 (2) | 0.047 (3) | 0.006 (2) | −0.006 (3) | 0.004 (2) |
C10 | 0.060 (4) | 0.047 (2) | 0.068 (4) | 0.019 (3) | −0.002 (4) | −0.013 (2) |
C11 | 0.080 (5) | 0.056 (3) | 0.058 (3) | 0.009 (3) | 0.019 (4) | −0.019 (3) |
C12 | 0.089 (4) | 0.064 (3) | 0.029 (3) | 0.000 (3) | 0.009 (3) | −0.009 (2) |
C13 | 0.064 (3) | 0.047 (2) | 0.041 (3) | 0.002 (2) | −0.015 (3) | −0.004 (2) |
C14 | 0.037 (2) | 0.032 (2) | 0.041 (2) | −0.002 (2) | −0.007 (2) | −0.006 (2) |
C15 | 0.047 (3) | 0.049 (2) | 0.048 (3) | 0.004 (2) | 0.007 (3) | −0.003 (2) |
C16 | 0.045 (3) | 0.048 (2) | 0.068 (3) | 0.005 (2) | 0.004 (3) | −0.010 (2) |
C17 | 0.051 (3) | 0.042 (2) | 0.079 (4) | 0.013 (2) | 0.005 (3) | 0.008 (2) |
C18 | 0.045 (3) | 0.041 (2) | 0.065 (3) | 0.000 (2) | 0.000 (3) | 0.009 (2) |
C19 | 0.039 (2) | 0.030 (2) | 0.038 (2) | 0.003 (2) | 0.000 (2) | −0.001 (2) |
C20 | 0.036 (2) | 0.033 (2) | 0.031 (2) | −0.006 (2) | −0.006 (2) | 0.001 (2) |
C21 | 0.045 (3) | 0.030 (2) | 0.033 (2) | 0.000 (2) | 0.001 (2) | 0.005 (2) |
C22 | 0.058 (3) | 0.047 (2) | 0.034 (2) | −0.014 (2) | 0.006 (2) | 0.007 (2) |
C23 | 0.068 (4) | 0.051 (2) | 0.057 (3) | −0.016 (3) | 0.016 (4) | 0.005 (2) |
C24 | 0.076 (4) | 0.054 (2) | 0.050 (3) | 0.005 (3) | 0.017 (4) | 0.016 (2) |
C25 | 0.108 (6) | 0.065 (3) | 0.043 (3) | −0.008 (3) | −0.009 (4) | 0.010 (3) |
C26 | 0.071 (4) | 0.052 (2) | 0.037 (3) | −0.016 (3) | 0.004 (3) | 0.004 (2) |
C27 | 0.033 (2) | 0.034 (2) | 0.039 (2) | 0.001 (2) | 0.013 (2) | 0.001 (1) |
C28 | 0.049 (3) | 0.042 (2) | 0.046 (2) | 0.000 (2) | 0.008 (2) | 0.005 (2) |
C29 | 0.038 (2) | 0.052 (2) | 0.118 (4) | 0.003 (2) | 0.011 (2) | 0.015 (3) |
C30 | 0.047 (2) | 0.035 (2) | 0.041 (2) | −0.004 (2) | −0.004 (2) | 0.003 (2) |
C31 | 0.052 (3) | 0.050 (2) | 0.060 (3) | −0.014 (2) | −0.018 (2) | −0.003 (2) |
C32 | 0.054 (3) | 0.040 (2) | 0.054 (3) | −0.006 (2) | −0.018 (2) | 0.003 (2) |
C33 | 0.065 (3) | 0.066 (3) | 0.049 (2) | 0.010 (2) | −0.019 (2) | 0.003 (2) |
C34 | 0.038 (1) | 0.043 (1) | 0.031 (1) | 0.001 (2) | −0.0012 (10) | 0.004 (2) |
C35 | 0.056 (2) | 0.054 (2) | 0.032 (1) | 0.004 (3) | −0.010 (1) | −0.003 (3) |
C36 | 0.050 (1) | 0.047 (1) | 0.027 (1) | −0.001 (3) | 0.001 (1) | −0.007 (2) |
C37 | 0.038 (2) | 0.076 (2) | 0.075 (2) | 0.006 (3) | −0.013 (2) | −0.005 (4) |
Co1—O1 | 1.880 (3) | C20—C21 | 1.501 (6) |
Co1—O2 | 1.887 (3) | C21—C22 | 1.372 (6) |
Co1—N1 | 1.898 (3) | C21—C26 | 1.383 (6) |
Co1—N2 | 1.889 (3) | C22—C23 | 1.390 (7) |
Co1—N3 | 1.950 (2) | C23—C24 | 1.364 (8) |
Co1—N4 | 1.927 (2) | C24—C25 | 1.396 (8) |
Cl1—O3 | 1.421 (4) | C25—C26 | 1.373 (8) |
Cl1—O4 | 1.402 (6) | C27—C28 | 1.527 (6) |
Cl1—O5 | 1.421 (6) | C27—C29 | 1.519 (6) |
Cl1—O6 | 1.377 (4) | C31—C32 | 1.336 (8) |
O1—C1 | 1.305 (4) | C35—C36 | 1.351 (4) |
O2—C14 | 1.314 (4) | C2—H10 | 0.930 |
N1—C7 | 1.298 (5) | C3—H11 | 0.930 |
N1—C27 | 1.497 (6) | C4—H12 | 0.930 |
N2—C20 | 1.300 (4) | C5—H13 | 0.930 |
N2—C28 | 1.464 (6) | C9—H14 | 0.930 |
N3—C30 | 1.320 (5) | C10—H15 | 0.930 |
N3—C32 | 1.363 (6) | C11—H16 | 0.930 |
N4—C34 | 1.312 (4) | C12—H17 | 0.930 |
N4—C36 | 1.378 (3) | C13—H18 | 0.930 |
N5—C30 | 1.346 (6) | C15—H19 | 0.930 |
N5—C31 | 1.366 (6) | C16—H20 | 0.930 |
N5—C33 | 1.452 (6) | C17—H21 | 0.930 |
N6—C34 | 1.342 (4) | C18—H22 | 0.930 |
N6—C35 | 1.368 (4) | C22—H23 | 0.930 |
N6—C37 | 1.465 (4) | C23—H24 | 0.930 |
C1—C2 | 1.422 (6) | C24—H25 | 0.930 |
C1—C6 | 1.417 (6) | C25—H26 | 0.930 |
C2—C3 | 1.380 (6) | C26—H27 | 0.930 |
C3—C4 | 1.376 (9) | C27—H28 | 0.980 |
C4—C5 | 1.373 (8) | C28—H29 | 0.970 |
C5—C6 | 1.408 (6) | C28—H30 | 0.970 |
C6—C7 | 1.471 (6) | C29—H1 | 0.960 |
C7—C8 | 1.498 (6) | C29—H2 | 0.960 |
C8—C9 | 1.397 (6) | C29—H3 | 0.960 |
C8—C13 | 1.391 (7) | C30—H31 | 0.930 |
C9—C10 | 1.375 (8) | C31—H32 | 0.930 |
C10—C11 | 1.364 (9) | C32—H33 | 0.930 |
C11—C12 | 1.363 (8) | C33—H4 | 0.960 |
C12—C13 | 1.385 (7) | C33—H5 | 0.960 |
C14—C15 | 1.412 (6) | C33—H6 | 0.960 |
C14—C19 | 1.420 (6) | C34—H34 | 0.930 |
C15—C16 | 1.362 (6) | C35—H35 | 0.930 |
C16—C17 | 1.386 (9) | C36—H36 | 0.930 |
C17—C18 | 1.367 (7) | C37—H7 | 0.960 |
C18—C19 | 1.421 (6) | C37—H8 | 0.960 |
C19—C20 | 1.458 (6) | C37—H9 | 0.960 |
O1···C35i | 3.349 (4) | N5···C37i | 3.414 (6) |
O2···C35i | 3.261 (4) | C1···C22iv | 3.478 (6) |
O3···C26ii | 3.491 (7) | C2···C23iv | 3.438 (8) |
O3···C13ii | 3.537 (7) | C2···C22iv | 3.465 (7) |
O3···C37i | 3.586 (6) | C3···C11v | 3.566 (9) |
O4···C37i | 3.564 (8) | C4···C11v | 3.441 (9) |
O5···C37i | 3.408 (8) | C9···C15iv | 3.499 (7) |
O6···C33iii | 3.332 (7) | C9···C14iv | 3.518 (7) |
O6···C27ii | 3.368 (7) | C10···C15iv | 3.462 (8) |
O6···C31iii | 3.383 (8) | C16···C24vi | 3.555 (9) |
O6···N5iii | 3.425 (6) | C17···C24vi | 3.362 (8) |
O6···C28ii | 3.460 (7) | ||
O1—Co1—O2 | 87.3 (1) | N1—C27—C29 | 112.5 (3) |
O1—Co1—N1 | 93.6 (1) | C28—C27—C29 | 109.4 (4) |
O1—Co1—N2 | 179.4 (1) | N2—C28—C27 | 112.0 (4) |
O1—Co1—N3 | 88.8 (1) | N3—C30—N5 | 110.8 (3) |
O1—Co1—N4 | 89.9 (1) | N5—C31—C32 | 106.9 (4) |
O2—Co1—N1 | 178.8 (1) | N3—C32—C31 | 109.8 (4) |
O2—Co1—N2 | 93.3 (1) | N4—C34—N6 | 110.6 (2) |
O2—Co1—N3 | 88.3 (1) | N6—C35—C36 | 105.8 (2) |
O2—Co1—N4 | 89.3 (1) | N4—C36—C35 | 109.4 (2) |
N1—Co1—N2 | 85.8 (1) | C1—C2—H10 | 119.5 |
N1—Co1—N3 | 92.5 (1) | C3—C2—H10 | 119.4 |
N1—Co1—N4 | 90.0 (1) | C2—C3—H11 | 119.6 |
N2—Co1—N3 | 91.3 (1) | C4—C3—H11 | 119.6 |
N2—Co1—N4 | 90.0 (1) | C3—C4—H12 | 120.5 |
N3—Co1—N4 | 177.25 (10) | C5—C4—H12 | 120.5 |
O3—Cl1—O4 | 107.7 (4) | C4—C5—H13 | 118.6 |
O3—Cl1—O5 | 108.6 (4) | C6—C5—H13 | 118.6 |
O3—Cl1—O6 | 108.3 (2) | C8—C9—H14 | 119.7 |
O4—Cl1—O5 | 107.3 (3) | C10—C9—H14 | 119.7 |
O4—Cl1—O6 | 113.9 (5) | C9—C10—H15 | 120.0 |
O5—Cl1—O6 | 110.9 (5) | C11—C10—H15 | 120.0 |
Co1—O1—C1 | 122.5 (3) | C10—C11—H16 | 119.9 |
Co1—O2—C14 | 122.4 (3) | C12—C11—H16 | 119.9 |
Co1—N1—C7 | 124.5 (3) | C11—C12—H17 | 119.4 |
Co1—N1—C27 | 114.0 (2) | C13—C12—H17 | 119.4 |
C7—N1—C27 | 121.0 (3) | C8—C13—H18 | 120.4 |
Co1—N2—C20 | 126.1 (3) | C12—C13—H18 | 120.4 |
Co1—N2—C28 | 111.2 (2) | C14—C15—H19 | 119.0 |
C20—N2—C28 | 122.7 (3) | C16—C15—H19 | 119.0 |
Co1—N3—C30 | 127.0 (3) | C15—C16—H20 | 119.7 |
Co1—N3—C32 | 127.0 (3) | C17—C16—H20 | 119.7 |
C30—N3—C32 | 105.8 (3) | C16—C17—H21 | 120.4 |
Co1—N4—C34 | 124.3 (2) | C18—C17—H21 | 120.4 |
Co1—N4—C36 | 129.4 (2) | C17—C18—H22 | 119.0 |
C34—N4—C36 | 106.2 (2) | C19—C18—H22 | 119.0 |
C30—N5—C31 | 106.7 (4) | C21—C22—H23 | 120.2 |
C30—N5—C33 | 127.0 (3) | C23—C22—H23 | 120.2 |
C31—N5—C33 | 126.3 (4) | C22—C23—H24 | 119.5 |
C34—N6—C35 | 108.0 (2) | C24—C23—H24 | 119.5 |
C34—N6—C37 | 125.6 (3) | C23—C24—H25 | 120.4 |
C35—N6—C37 | 126.4 (3) | C25—C24—H25 | 120.4 |
O1—C1—C2 | 117.4 (4) | C24—C25—H26 | 119.9 |
O1—C1—C6 | 124.5 (4) | C26—C25—H26 | 119.9 |
C2—C1—C6 | 118.1 (3) | C21—C26—H27 | 119.9 |
C1—C2—C3 | 121.1 (4) | C25—C26—H27 | 119.9 |
C2—C3—C4 | 120.9 (5) | N1—C27—H28 | 108.7 |
C3—C4—C5 | 118.9 (4) | C28—C27—H28 | 108.7 |
C4—C5—C6 | 122.9 (5) | C29—C27—H28 | 108.7 |
C1—C6—C5 | 118.0 (4) | N2—C28—H29 | 108.8 |
C1—C6—C7 | 122.1 (3) | N2—C28—H30 | 108.8 |
C5—C6—C7 | 119.7 (4) | C27—C28—H29 | 108.8 |
N1—C7—C6 | 122.8 (4) | C27—C28—H30 | 108.8 |
N1—C7—C8 | 120.9 (4) | H29—C28—H30 | 109.5 |
C6—C7—C8 | 116.3 (3) | C27—C29—H1 | 109.5 |
C7—C8—C9 | 120.6 (4) | C27—C29—H2 | 109.5 |
C7—C8—C13 | 120.7 (4) | C27—C29—H3 | 109.5 |
C9—C8—C13 | 118.7 (4) | H1—C29—H2 | 109.5 |
C8—C9—C10 | 120.7 (5) | H1—C29—H3 | 109.5 |
C9—C10—C11 | 120.0 (5) | H2—C29—H3 | 109.5 |
C10—C11—C12 | 120.2 (5) | N3—C30—H31 | 124.6 |
C11—C12—C13 | 121.1 (5) | N5—C30—H31 | 124.6 |
C8—C13—C12 | 119.2 (4) | N5—C31—H32 | 126.6 |
O2—C14—C15 | 117.4 (4) | C32—C31—H32 | 126.6 |
O2—C14—C19 | 124.7 (4) | N3—C32—H33 | 125.1 |
C15—C14—C19 | 117.9 (3) | C31—C32—H33 | 125.1 |
C14—C15—C16 | 121.9 (4) | N5—C33—H4 | 109.5 |
C15—C16—C17 | 120.7 (5) | N5—C33—H5 | 109.5 |
C16—C17—C18 | 119.3 (4) | N5—C33—H6 | 109.5 |
C17—C18—C19 | 122.0 (5) | H4—C33—H5 | 109.5 |
C14—C19—C18 | 118.1 (4) | H4—C33—H6 | 109.5 |
C14—C19—C20 | 122.7 (3) | H5—C33—H6 | 109.5 |
C18—C19—C20 | 119.0 (4) | N4—C34—H34 | 124.7 |
N2—C20—C19 | 121.7 (4) | N6—C34—H34 | 124.7 |
N2—C20—C21 | 120.4 (4) | N6—C35—H35 | 127.1 |
C19—C20—C21 | 117.8 (3) | C36—C35—H35 | 127.1 |
C20—C21—C22 | 120.6 (4) | N4—C36—H36 | 125.3 |
C20—C21—C26 | 119.5 (4) | C35—C36—H36 | 125.3 |
C22—C21—C26 | 119.9 (4) | N6—C37—H7 | 109.5 |
C21—C22—C23 | 119.7 (5) | N6—C37—H8 | 109.5 |
C22—C23—C24 | 120.9 (5) | N6—C37—H9 | 109.5 |
C23—C24—C25 | 119.1 (5) | H7—C37—H8 | 109.5 |
C24—C25—C26 | 120.1 (5) | H7—C37—H9 | 109.5 |
C21—C26—C25 | 120.2 (5) | H8—C37—H9 | 109.5 |
N1—C27—C28 | 108.6 (4) | ||
Co1—O1—C1—C2 | −157.1 (3) | N3—C32—C31—N5 | −1.8 (6) |
Co1—O1—C1—C6 | 24.1 (5) | N4—Co1—O1—C1 | 56.3 (3) |
Co1—O2—C14—C15 | 159.7 (3) | N4—Co1—O2—C14 | −58.4 (3) |
Co1—O2—C14—C19 | −21.6 (6) | N4—Co1—N1—C7 | −63.0 (3) |
Co1—N1—C7—C6 | −9.6 (6) | N4—Co1—N1—C27 | 108.8 (3) |
Co1—N1—C7—C8 | 168.1 (3) | N4—Co1—N2—C20 | 62.3 (4) |
Co1—N1—C27—C28 | −6.5 (4) | N4—Co1—N2—C28 | −116.8 (3) |
Co1—N1—C27—C29 | 114.8 (3) | N4—C34—N6—C35 | 0.8 (6) |
Co1—N2—C20—C19 | 10.7 (6) | N4—C34—N6—C37 | 179.5 (5) |
Co1—N2—C20—C21 | −169.5 (3) | N4—C36—C35—N6 | 1.2 (6) |
Co1—N2—C28—C27 | 29.3 (4) | N5—C30—N3—C32 | 0.0 (5) |
Co1—N3—C30—N5 | −175.5 (3) | N6—C34—N4—C36 | −0.1 (5) |
Co1—N3—C32—C31 | 176.6 (3) | C1—C2—C3—C4 | −2.9 (8) |
Co1—N4—C34—N6 | 178.1 (3) | C1—C6—C5—C4 | 0.0 (7) |
Co1—N4—C36—C35 | −178.8 (3) | C1—C6—C7—C8 | 171.2 (4) |
O1—Co1—O2—C14 | −148.3 (3) | C2—C1—C6—C5 | −1.0 (6) |
O1—Co1—N1—C7 | 26.8 (4) | C2—C1—C6—C7 | −175.7 (4) |
O1—Co1—N1—C27 | −161.4 (3) | C2—C3—C4—C5 | 1.8 (8) |
O1—Co1—N3—C30 | 35.4 (3) | C3—C2—C1—C6 | 2.5 (7) |
O1—Co1—N3—C32 | −139.1 (3) | C3—C4—C5—C6 | −0.4 (8) |
O1—Co1—N4—C34 | 44.6 (4) | C4—C5—C6—C7 | 174.8 (5) |
O1—Co1—N4—C36 | −137.7 (4) | C5—C6—C7—C8 | −3.4 (6) |
O1—C1—C2—C3 | −176.4 (4) | C6—C7—N1—C27 | 179.2 (4) |
O1—C1—C6—C5 | 177.8 (4) | C6—C7—C8—C9 | −72.1 (6) |
O1—C1—C6—C7 | 3.1 (6) | C6—C7—C8—C13 | 106.2 (5) |
O2—Co1—O1—C1 | 145.5 (3) | C7—N1—C27—C28 | 165.7 (4) |
O2—Co1—N2—C20 | −27.0 (4) | C7—N1—C27—C29 | −73.1 (5) |
O2—Co1—N2—C28 | 153.9 (3) | C7—C8—C9—C10 | 178.0 (5) |
O2—Co1—N3—C30 | 122.7 (3) | C7—C8—C13—C12 | −178.3 (5) |
O2—Co1—N3—C32 | −51.8 (3) | C8—C7—N1—C27 | −3.1 (6) |
O2—Co1—N4—C34 | −42.7 (4) | C8—C9—C10—C11 | −0.8 (9) |
O2—Co1—N4—C36 | 135.1 (4) | C8—C13—C12—C11 | 1.3 (9) |
O2—C14—C15—C16 | 177.1 (4) | C9—C8—C13—C12 | 0.1 (7) |
O2—C14—C19—C18 | −179.5 (4) | C9—C10—C11—C12 | 2.2 (10) |
O2—C14—C19—C20 | −4.4 (7) | C10—C9—C8—C13 | −0.4 (7) |
N1—Co1—O1—C1 | −33.7 (3) | C10—C11—C12—C13 | −2.5 (10) |
N1—Co1—N2—C20 | 152.3 (4) | C14—C15—C16—C17 | 3.2 (8) |
N1—Co1—N2—C28 | −26.8 (3) | C14—C19—C18—C17 | 1.9 (7) |
N1—Co1—N3—C30 | −58.2 (3) | C14—C19—C20—C21 | −169.3 (4) |
N1—Co1—N3—C32 | 127.3 (3) | C15—C14—C19—C18 | −0.8 (6) |
N1—Co1—N4—C34 | 138.2 (4) | C15—C14—C19—C20 | 174.3 (4) |
N1—Co1—N4—C36 | −44.0 (4) | C15—C16—C17—C18 | −2.1 (8) |
N1—C7—C6—C1 | −11.0 (6) | C16—C15—C14—C19 | −1.7 (7) |
N1—C7—C6—C5 | 174.4 (4) | C16—C17—C18—C19 | −0.4 (8) |
N1—C7—C8—C9 | 110.0 (5) | C17—C18—C19—C20 | −173.4 (4) |
N1—C7—C8—C13 | −71.6 (6) | C18—C19—C20—C21 | 5.7 (6) |
N1—C27—C28—N2 | −14.4 (5) | C19—C20—N2—C28 | −170.3 (4) |
N2—Co1—O2—C14 | 31.6 (3) | C19—C20—C21—C22 | 73.5 (6) |
N2—Co1—N1—C7 | −153.1 (4) | C19—C20—C21—C26 | −104.1 (5) |
N2—Co1—N1—C27 | 18.7 (3) | C20—N2—C28—C27 | −149.8 (4) |
N2—Co1—N3—C30 | −144.0 (3) | C20—C21—C22—C23 | −175.0 (5) |
N2—Co1—N3—C32 | 41.5 (3) | C20—C21—C26—C25 | 175.7 (5) |
N2—Co1—N4—C34 | −136.0 (4) | C21—C20—N2—C28 | 9.5 (6) |
N2—Co1—N4—C36 | 41.8 (4) | C21—C22—C23—C24 | −2.1 (9) |
N2—C20—C19—C14 | 10.5 (6) | C21—C26—C25—C24 | 0.7 (9) |
N2—C20—C19—C18 | −174.4 (4) | C22—C21—C26—C25 | −1.9 (8) |
N2—C20—C21—C22 | −106.3 (5) | C22—C23—C24—C25 | 0.8 (9) |
N2—C20—C21—C26 | 76.1 (6) | C23—C22—C21—C26 | 2.6 (7) |
N2—C28—C27—C29 | −137.6 (4) | C23—C24—C25—C26 | −0.1 (10) |
N3—Co1—O1—C1 | −126.1 (3) | C30—N3—C32—C31 | 1.2 (5) |
N3—Co1—O2—C14 | 122.8 (3) | C30—N5—C31—C32 | 1.8 (6) |
N3—Co1—N1—C7 | 115.8 (3) | C32—C31—N5—C33 | −177.4 (4) |
N3—Co1—N1—C27 | −72.4 (3) | C34—N4—C36—C35 | −0.7 (5) |
N3—Co1—N2—C20 | −115.3 (4) | C34—N6—C35—C36 | −1.2 (6) |
N3—Co1—N2—C28 | 65.6 (3) | C36—C35—N6—C37 | −179.9 (5) |
N3—C30—N5—C31 | −1.1 (5) | C36—C35—N6—C37 | −179.9 (5) |
N3—C30—N5—C33 | 178.0 (4) |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) x, y, z+1; (iii) −x+3/2, −y+1, z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x−1/2, −y+1/2, −z; (vi) x−1/2, −y+3/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C33iii—H6iii···O6 | 0.96 | 2.58 | 3.332 (7) | 136 |
C37i—H8i···O5 | 0.96 | 2.60 | 3.408 (8) | 143 |
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (iii) −x+3/2, −y+1, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C29H24N2O2)(C4H6N2)2]ClO4 |
Mr | 755.10 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 14.334 (2), 17.766 (3), 13.849 (2) |
V (Å3) | 3526.9 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.62 |
Crystal size (mm) | 0.62 × 0.45 × 0.23 |
Data collection | |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.783, 0.867 |
No. of measured, independent and observed [F > 4σ(F)] reflections | 6564, 5671, 4120 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.115, 1.04 |
No. of reflections | 5671 |
No. of parameters | 464 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.52 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.01 (3) |
Computer programs: Rigaku/AFC Diffractometer Control Software (Rigaku, 1995), Rigaku/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), TEXSAN.
Co1—O1 | 1.880 (3) | Co1—N2 | 1.889 (3) |
Co1—O2 | 1.887 (3) | Co1—N3 | 1.950 (2) |
Co1—N1 | 1.898 (3) | Co1—N4 | 1.927 (2) |
O1—Co1—O2 | 87.3 (1) | O2—Co1—N4 | 89.3 (1) |
O1—Co1—N1 | 93.6 (1) | N1—Co1—N2 | 85.8 (1) |
O1—Co1—N2 | 179.4 (1) | N1—Co1—N3 | 92.5 (1) |
O1—Co1—N3 | 88.8 (1) | N1—Co1—N4 | 90.0 (1) |
O1—Co1—N4 | 89.9 (1) | N2—Co1—N3 | 91.3 (1) |
O2—Co1—N1 | 178.8 (1) | N2—Co1—N4 | 90.0 (1) |
O2—Co1—N2 | 93.3 (1) | N3—Co1—N4 | 177.25 (10) |
O2—Co1—N3 | 88.3 (1) | ||
N1—C27—C28—N2 | −14.4 (5) |
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Cobalt(II) schiff base complexes have been extensively utilized as catalysts for the oxidation reaction of organic molecules (Mukaiyama & Yamada, 1995; Fiammengo et al., 2002). It has been recognized that the formal potential of the CoIII/CoII couple is an important factor which determines the catalytic activity (Förster et al., 1996). The redox potential of a CoII or CoIII Schiff base complex is affected not only by the electronic effect, but also by the steric effect of the substituent on the Schiff base ligand (Kitaura et al., 1987; Nishinaga et al., 1991; Hirotsu et al., 1994, 1996). In CoII complexes with N,N'-bis(salicylidene)-1,2-ethanediamine derivatives, an axially oriented substituent on the central ethylene backbone affords a more positive value of the redox potential compared with a complex with an equatorially oriented one. This was rationally demonstrated by investigating the intramolecular steric interactions of the related CoIII Schiff base complexes with two apical ligands, L, [Co(Schiff base)(L)2]+ (Hirotsu et al., 1996). For the title complex, (I), [Co{7-Phsal-(R)-pn}(Meim)2]ClO4 [H2{7-Phsal-(R)-pn} is (R)—N,N'-bis(α-phenylsalicylidene)-1,2-propanediamine and Meim is 1-methylimidazole], it has been reported that the central N—N chelate adopts the δ gauche conformation and the methyl group on the ethylene backbone is axially oriented, on the basis of circular dichroism and 1H NMR spectra in an acetonitrile solution. To clarify the intramolecular steric interactions, we have determined the single-crystal structure of (I) by X-ray analysis and present the results here. \sch
The X-ray analysis of (I) confirmed the presence of a univalent [Co{7-Phsal-(R)-pn}(Meim)2]+ complex cation and a perchlorate anion. The space group P212121 is consistent with the fact that the complex has an optically active ligand derived from (R)-1,2-propanediamine. The absolute structure was chosen on the basis of the R configuration of the optically pure diamine employed.
In the complex cation, the CoIII ion is bound to two O and two N atoms of a Schiff base dianion, to form the equatorial plane. Two apical sites are occupied by N atoms of two 1-methylimidazole ligands, to complete the six-coordinate octahedral structure. The CoIII ion is in the equatorial coordination plane with no significant deviation. The coordination bond distances are comparable with those in the related CoIII Schiff base complex with two 1-methylimidazole ligands, [Co{sal-(meso)-stien}(Meim)2]ClO4 [mean Co—O 1.898 (4), Co—Nequatorial 1.903 (4) and Co—Napical 1.957 (4) Å; Hirotsu et al., 1996].
The central N—N chelate ring has an envelope-type structure with an N1—C27—C28—N2 torsion angle of −14.4 (5)°, which is much smaller than the corresponding angle in [Co{sal-(meso)-stien}(Meim)2]+ [42.5 (6)°]. The negative sign of this torsion angle in the cation of (I) is indicative of the λ conformation, which differs from the predominant solution structure containing the δ gauche conformation with the axially disposed methyl group. This suggests that the chelate conformation inverts rapidly in solution. The envelope structure and the δ gauche conformation are probably in equilibrium. A λ gauche conformation is unfavourable because of the steric repulsion between the equatorially disposed methyl group on the ethylene backbone and the phenyl group. The envelope structure may have a slightly higher energy than that of the δ gauche conformation, which largely contributes to the circular dichroism and 1H NMR spectra in solution.