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Single crystal neutron diffraction analysis of photo-exposed(3-cyanopropyl-d2α,α)-[(R)-1-phenylethylamine-d11]bis(dimethylglyoximato-d14)cobalt(III) was carried out in order to clarify the mechanism of the crystalline-state photoisomerization of the 3-cyanopropyl group bonded to the Co atom in some cobaloxime complexes. Before irradiation the two H atoms bonded to the C1 atom of the 3-cyanopropyl group were exchanged with the D atoms such as —CH2CH2CD2CN. On exposure to a xenon lamp, the cell dimensions of the crystal were gradually changed. After 7 d exposure the change became insignificantly small. The structure was analyzed by neutron diffraction. The 3-cyanopropyl group was transformed to the 1-cyanopropyl group such as —CD(CN)C(H1/2,D1/2)2CH3 with retention of the single-crystal form. This indicates that one of the D atoms bonded to C1 migrates to either position bonded to C2. The other atoms of the complex remained unchanged. These results indicate that photoisomerization proceeded in two steps: the 3-cyanopropyl group was isomerized to the 2-cyanopropyl group in the first place and then the 2-cyanopropyl group was transformed to the 1-cyanopropyl group. Moreover, it was made clear that the second-step isomerization was irreversible, since one of the D atoms was retained. The disordered structure at C2 is estimated to be caused by the interconversion between the 1-cyanopropyl group produced and its dehydrogenated olefin after the photoisomerization.
Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768199012008/se0292sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S0108768199012008/se02921bXinsup2.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108768199012008/se02921bXirrsup3.hkl |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108768199012008/se02921bNirrsup4.hkl |
CCDC references: 144358; 144359; 144360
Computing details top
Data collection: SMART (Siemens, 1995) for 1bXin, 1bXirr; local program for 1bNirr. Cell refinement: SMART (Siemens, 1995) for 1bXin, 1bXirr; local program for 1bNirr. Data reduction: SAINT (Siemens, 1995) for 1bXin, 1bXirr; local program for 1bNirr. Program(s) used to solve structure: SIR97 (Altomare et al., 1999) for 1bXin, 1bXirr; initial structure was determined by X-ray for 1bNirr. Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for 1bXin, 1bXirr; SHELXL93 (Sheldrick, 1993) for 1bNirr. For all compounds, molecular graphics: ORTEP-III (Burnet & Johnson, 1996).
(1bXin) (3-cyanopropyl)[(R)-1-phenylethylamine]cobaloxime top
Crystal data top
| [Co(C4D7N2O2)2(C4H4D2N)(C8D11N)] | F(000) = 504 |
| Mr = 504.00 | Dx = 1.329 Mg m−3 |
| Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
| a = 9.6772 (1) Å | Cell parameters from 512 reflections |
| b = 13.8988 (2) Å | θ = 3–30° |
| c = 8.9432 (1) Å | µ = 0.75 mm−1 |
| β = 96.322 (1)° | T = 293 K |
| V = 1195.56 (3) Å3 | Plate, red |
| Z = 2 | 0.4 × 0.3 × 0.15 mm |
Data collection top
| Siemens SMART CCD diffractometer | 7077 independent reflections |
| Radiation source: rotate anode | 6573 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.015 |
| ω scans | θmax = 30.5°, θmin = 2.1° |
| Absorption correction: empirical SADABS (Sheldrick, 1996) | h = −13→13 |
| Tmin = 0.696, Tmax = 0.801 | k = −19→19 |
| 14136 measured reflections | l = −12→12 |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.026 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.070 | w = 1/[σ2(Fo2) + (0.0505P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max = 0.001 |
| 7077 reflections | Δρmax = 0.27 e Å−3 |
| 341 parameters | Δρmin = −0.24 e Å−3 |
| 1 restraint | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.007 (7) |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| Co1 | 0.256156 (15) | 0.113672 (14) | 0.024048 (16) | 0.03261 (5) | |
| O1 | 0.52541 (11) | 0.09926 (10) | −0.07695 (13) | 0.0510 (3) | |
| HO1 | 0.437 (2) | 0.0286 (17) | −0.148 (2) | 0.061* | |
| O2 | 0.16804 (14) | 0.23517 (11) | 0.25068 (14) | 0.0588 (3) | |
| O3 | −0.01697 (13) | 0.13261 (12) | 0.11562 (15) | 0.0609 (4) | |
| HO3 | 0.055 (3) | 0.184 (2) | 0.177 (3) | 0.073* | |
| O4 | 0.34393 (12) | −0.00833 (9) | −0.20320 (15) | 0.0504 (2) | |
| N1 | 0.44538 (12) | 0.14316 (8) | 0.01808 (14) | 0.0384 (2) | |
| N2 | 0.27354 (17) | 0.21022 (11) | 0.17332 (17) | 0.0424 (3) | |
| N3 | 0.06481 (12) | 0.08761 (9) | 0.02331 (14) | 0.0415 (3) | |
| N4 | 0.23817 (15) | 0.01859 (9) | −0.12765 (17) | 0.0373 (3) | |
| C1 | 0.49706 (15) | 0.21084 (10) | 0.10705 (17) | 0.0420 (3) | |
| C2 | 0.39483 (19) | 0.24996 (12) | 0.20164 (17) | 0.0433 (3) | |
| C3 | 0.01228 (16) | 0.02162 (12) | −0.06899 (17) | 0.0445 (3) | |
| C4 | 0.11444 (17) | −0.01880 (11) | −0.15998 (18) | 0.0437 (3) | |
| C5 | 0.64421 (19) | 0.24506 (14) | 0.1154 (3) | 0.0601 (4) | |
| H5A | 0.6894 | 0.2151 | 0.0372 | 0.090* | |
| H5B | 0.6923 | 0.2284 | 0.2116 | 0.090* | |
| H5C | 0.6454 | 0.3136 | 0.1029 | 0.090* | |
| C6 | 0.4281 (3) | 0.32462 (17) | 0.3191 (2) | 0.0681 (5) | |
| H6A | 0.3434 | 0.3514 | 0.3476 | 0.102* | |
| H6B | 0.4824 | 0.3746 | 0.2801 | 0.102* | |
| H6C | 0.4801 | 0.2960 | 0.4055 | 0.102* | |
| C7 | −0.13617 (19) | −0.01104 (19) | −0.0803 (3) | 0.0668 (5) | |
| H7A | −0.1912 | 0.0368 | −0.0369 | 0.100* | |
| H7B | −0.1417 | −0.0707 | −0.0271 | 0.100* | |
| H7C | −0.1706 | −0.0201 | −0.1842 | 0.100* | |
| C8 | 0.0801 (2) | −0.08929 (16) | −0.2847 (3) | 0.0652 (5) | |
| H8A | 0.1554 | −0.0921 | −0.3461 | 0.098* | |
| H8B | −0.0031 | −0.0693 | −0.3450 | 0.098* | |
| H8C | 0.0661 | −0.1518 | −0.2432 | 0.098* | |
| N5 | 0.29388 (18) | 0.00904 (13) | 0.1900 (2) | 0.0490 (4) | |
| HN5A | 0.238 (3) | −0.0364 (18) | 0.169 (3) | 0.059* | |
| HN5B | 0.273 (2) | 0.0306 (18) | 0.273 (3) | 0.059* | |
| C9 | 0.4293 (2) | −0.04391 (12) | 0.2185 (2) | 0.0474 (3) | |
| H9 | 0.460 (2) | −0.0514 (17) | 0.119 (3) | 0.057* | |
| C10 | 0.4085 (3) | −0.14519 (16) | 0.2788 (3) | 0.0725 (6) | |
| H10A | 0.490 (3) | −0.179 (3) | 0.291 (4) | 0.109* | |
| H10B | 0.349 (4) | −0.179 (3) | 0.222 (4) | 0.109* | |
| H10C | 0.380 (3) | −0.140 (3) | 0.386 (4) | 0.109* | |
| C11 | 0.53274 (16) | 0.01142 (11) | 0.32492 (16) | 0.0438 (3) | |
| C12 | 0.6681 (2) | 0.02219 (17) | 0.2919 (2) | 0.0622 (5) | |
| H12 | 0.686 (3) | 0.004 (2) | 0.207 (3) | 0.075* | |
| C13 | 0.7673 (2) | 0.0687 (2) | 0.3909 (3) | 0.0795 (7) | |
| H13 | 0.862 (3) | 0.071 (2) | 0.360 (4) | 0.095* | |
| C14 | 0.7319 (3) | 0.1053 (3) | 0.5235 (3) | 0.0805 (7) | |
| H14 | 0.813 (3) | 0.138 (2) | 0.588 (3) | 0.097* | |
| C15 | 0.5994 (3) | 0.09561 (18) | 0.5590 (2) | 0.0735 (6) | |
| H15 | 0.573 (3) | 0.109 (3) | 0.657 (3) | 0.088* | |
| C16 | 0.4996 (2) | 0.04796 (15) | 0.4616 (2) | 0.0559 (4) | |
| H16 | 0.407 (2) | 0.0432 (19) | 0.479 (3) | 0.067* | |
| C17 | 0.2077 (2) | 0.22140 (13) | −0.1233 (2) | 0.0425 (4) | |
| H17A | 0.280 (2) | 0.2686 (16) | −0.105 (2) | 0.051* | |
| H17B | 0.137 (2) | 0.2516 (17) | −0.095 (3) | 0.051* | |
| C18 | 0.0311 (2) | 0.34409 (16) | −0.3366 (2) | 0.0640 (5) | |
| C19 | 0.1737 (2) | 0.19685 (13) | −0.28737 (17) | 0.0531 (4) | |
| H19A | 0.095 (2) | 0.1544 (19) | −0.312 (3) | 0.064* | |
| H19B | 0.258 (2) | 0.1686 (18) | −0.321 (3) | 0.064* | |
| C20 | 0.1443 (2) | 0.28780 (14) | −0.38536 (18) | 0.0590 (4) | |
| H20A | 0.123 (2) | 0.2730 (18) | −0.488 (3) | 0.071* | |
| H20B | 0.227 (3) | 0.3313 (19) | −0.373 (3) | 0.071* | |
| N6 | −0.0537 (3) | 0.3886 (2) | −0.2937 (4) | 0.1081 (9) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.03561 (7) | 0.03340 (7) | 0.02865 (7) | 0.00139 (7) | 0.00285 (4) | 0.00076 (8) |
| O1 | 0.0434 (5) | 0.0553 (8) | 0.0565 (6) | 0.0010 (5) | 0.0160 (4) | −0.0053 (5) |
| O2 | 0.0650 (7) | 0.0688 (8) | 0.0451 (6) | 0.0020 (6) | 0.0168 (5) | −0.0182 (5) |
| O3 | 0.0466 (5) | 0.0830 (13) | 0.0555 (6) | 0.0040 (6) | 0.0175 (5) | −0.0144 (6) |
| O4 | 0.0491 (6) | 0.0437 (5) | 0.0600 (6) | 0.0053 (5) | 0.0136 (5) | −0.0145 (5) |
| N1 | 0.0393 (5) | 0.0377 (5) | 0.0384 (5) | −0.0004 (4) | 0.0055 (4) | 0.0032 (4) |
| N2 | 0.0519 (8) | 0.0445 (7) | 0.0307 (6) | 0.0018 (6) | 0.0047 (5) | −0.0025 (5) |
| N3 | 0.0386 (5) | 0.0489 (7) | 0.0376 (5) | 0.0024 (4) | 0.0064 (4) | −0.0013 (4) |
| N4 | 0.0415 (6) | 0.0318 (5) | 0.0383 (6) | 0.0038 (5) | 0.0030 (5) | −0.0018 (4) |
| C1 | 0.0456 (7) | 0.0374 (6) | 0.0417 (7) | −0.0037 (5) | −0.0009 (5) | 0.0054 (5) |
| C2 | 0.0578 (9) | 0.0379 (7) | 0.0329 (6) | −0.0039 (6) | −0.0003 (6) | −0.0001 (5) |
| C3 | 0.0409 (7) | 0.0488 (7) | 0.0427 (7) | −0.0026 (6) | −0.0004 (5) | 0.0023 (6) |
| C4 | 0.0474 (7) | 0.0383 (7) | 0.0436 (7) | −0.0013 (6) | −0.0024 (6) | −0.0015 (5) |
| C5 | 0.0507 (9) | 0.0507 (9) | 0.0771 (12) | −0.0126 (7) | −0.0007 (8) | 0.0046 (8) |
| C6 | 0.0845 (14) | 0.0633 (12) | 0.0547 (10) | −0.0191 (10) | −0.0001 (9) | −0.0183 (9) |
| C7 | 0.0450 (8) | 0.0839 (13) | 0.0706 (12) | −0.0140 (9) | 0.0020 (8) | −0.0059 (10) |
| C8 | 0.0659 (11) | 0.0584 (10) | 0.0689 (12) | −0.0056 (9) | −0.0041 (9) | −0.0254 (9) |
| N5 | 0.0461 (8) | 0.0533 (9) | 0.0469 (8) | −0.0033 (6) | 0.0022 (6) | 0.0185 (7) |
| C9 | 0.0560 (9) | 0.0430 (8) | 0.0421 (7) | 0.0071 (6) | −0.0005 (6) | 0.0076 (6) |
| C10 | 0.0972 (16) | 0.0438 (9) | 0.0705 (12) | −0.0017 (10) | −0.0180 (12) | 0.0129 (9) |
| C11 | 0.0476 (7) | 0.0442 (7) | 0.0395 (6) | 0.0068 (5) | 0.0041 (5) | 0.0107 (5) |
| C12 | 0.0545 (10) | 0.0747 (12) | 0.0591 (10) | 0.0118 (8) | 0.0135 (8) | 0.0127 (9) |
| C13 | 0.0508 (10) | 0.0912 (16) | 0.0946 (17) | −0.0083 (10) | 0.0002 (10) | 0.0214 (13) |
| C14 | 0.0811 (13) | 0.0833 (17) | 0.0716 (12) | −0.0212 (14) | −0.0159 (10) | 0.0183 (13) |
| C15 | 0.0964 (15) | 0.0737 (16) | 0.0490 (9) | −0.0083 (11) | 0.0014 (9) | −0.0023 (9) |
| C16 | 0.0596 (9) | 0.0628 (9) | 0.0464 (8) | −0.0005 (8) | 0.0115 (7) | 0.0014 (7) |
| C17 | 0.0536 (9) | 0.0382 (7) | 0.0350 (7) | 0.0072 (6) | 0.0019 (6) | 0.0031 (5) |
| C18 | 0.0739 (12) | 0.0626 (11) | 0.0539 (9) | 0.0237 (9) | 0.0004 (9) | 0.0079 (8) |
| C19 | 0.0787 (11) | 0.0477 (8) | 0.0323 (6) | 0.0200 (8) | 0.0040 (7) | 0.0006 (6) |
| C20 | 0.0881 (13) | 0.0553 (9) | 0.0343 (7) | 0.0244 (9) | 0.0099 (7) | 0.0088 (6) |
| N6 | 0.1041 (17) | 0.1114 (19) | 0.112 (2) | 0.0585 (16) | 0.0251 (15) | 0.0089 (16) |
Geometric parameters (Å, º) top
| Co1—N1 | 1.8829 (12) | C3—C4 | 1.460 (2) |
| Co1—N3 | 1.8861 (12) | C3—C7 | 1.499 (2) |
| Co1—N2 | 1.8872 (15) | C4—C8 | 1.494 (2) |
| Co1—N4 | 1.8882 (14) | N5—C9 | 1.500 (2) |
| Co1—C17 | 2.0155 (17) | C9—C11 | 1.513 (2) |
| Co1—N5 | 2.0813 (16) | C9—C10 | 1.528 (3) |
| O1—N1 | 1.3562 (16) | C11—C12 | 1.383 (3) |
| O2—N2 | 1.341 (2) | C11—C16 | 1.393 (2) |
| O3—N3 | 1.3575 (16) | C12—C13 | 1.391 (3) |
| O4—N4 | 1.3402 (18) | C13—C14 | 1.368 (5) |
| N1—C1 | 1.2964 (19) | C14—C15 | 1.361 (4) |
| N2—C2 | 1.297 (2) | C15—C16 | 1.395 (3) |
| N3—C3 | 1.299 (2) | C17—C19 | 1.507 (2) |
| N4—C4 | 1.308 (2) | C18—N6 | 1.128 (3) |
| C1—C2 | 1.475 (2) | C18—C20 | 1.452 (3) |
| C1—C5 | 1.495 (2) | C19—C20 | 1.547 (2) |
| C2—C6 | 1.487 (2) | ||
| N1—Co1—N3 | 177.64 (6) | N1—C1—C5 | 124.23 (16) |
| N1—Co1—N2 | 81.61 (6) | C2—C1—C5 | 123.32 (15) |
| N3—Co1—N2 | 98.63 (6) | N2—C2—C1 | 112.39 (14) |
| N1—Co1—N4 | 98.33 (6) | N2—C2—C6 | 123.82 (18) |
| N3—Co1—N4 | 81.39 (6) | C1—C2—C6 | 123.77 (16) |
| N2—Co1—N4 | 179.09 (7) | N3—C3—C4 | 112.58 (13) |
| N1—Co1—C17 | 88.67 (7) | N3—C3—C7 | 124.16 (17) |
| N3—Co1—C17 | 89.01 (7) | C4—C3—C7 | 123.25 (15) |
| N2—Co1—C17 | 86.02 (8) | N4—C4—C3 | 112.55 (14) |
| N4—Co1—C17 | 93.08 (5) | N4—C4—C8 | 123.24 (17) |
| N1—Co1—N5 | 94.45 (6) | C3—C4—C8 | 124.05 (15) |
| N3—Co1—N5 | 87.90 (6) | C9—N5—Co1 | 123.05 (12) |
| N2—Co1—N5 | 89.85 (6) | N5—C9—C11 | 111.26 (15) |
| N4—Co1—N5 | 91.05 (8) | N5—C9—C10 | 111.41 (19) |
| C17—Co1—N5 | 174.42 (9) | C11—C9—C10 | 110.50 (15) |
| C1—N1—O1 | 120.18 (12) | C12—C11—C16 | 117.58 (17) |
| C1—N1—Co1 | 116.82 (11) | C12—C11—C9 | 119.84 (16) |
| O1—N1—Co1 | 122.96 (9) | C16—C11—C9 | 122.47 (16) |
| C2—N2—O2 | 120.89 (15) | C11—C12—C13 | 121.2 (2) |
| C2—N2—Co1 | 116.70 (13) | C14—C13—C12 | 120.2 (2) |
| O2—N2—Co1 | 122.37 (12) | C15—C14—C13 | 119.9 (2) |
| C3—N3—O3 | 119.86 (13) | C14—C15—C16 | 120.4 (2) |
| C3—N3—Co1 | 116.94 (11) | C11—C16—C15 | 120.74 (19) |
| O3—N3—Co1 | 123.18 (10) | C19—C17—Co1 | 118.59 (12) |
| C4—N4—O4 | 120.59 (14) | N6—C18—C20 | 177.3 (3) |
| C4—N4—Co1 | 116.52 (12) | C17—C19—C20 | 111.93 (15) |
| O4—N4—Co1 | 122.86 (10) | C18—C20—C19 | 111.59 (16) |
| N1—C1—C2 | 112.44 (13) |
(1bXirr) (3-cyanopropyl)[(R)-1-phenylethylamine]cobaloxime top
Crystal data top
| [Co(C4D7N2O2)2(C4H4D2N)(C8D11N)] | F(000) = 504 |
| Mr = 504.00 | Dx = 1.359 Mg m−3 |
| Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
| a = 9.1579 (1) Å | Cell parameters from 512 reflections |
| b = 13.9694 (2) Å | θ = 2–30° |
| c = 9.2757 (1) Å | µ = 0.77 mm−1 |
| β = 99.954 (1)° | T = 293 K |
| V = 1168.78 (2) Å3 | Plate, red |
| Z = 2 | 0.5 × 0.3 × 0.1 mm |
Data collection top
| Siemens SMART CCD diffractometer | 6655 independent reflections |
| Radiation source: rotate anode | 5273 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.041 |
| ω scans | θmax = 30.8°, θmin = 2.2° |
| Absorption correction: empirical (SADABS; Sheldrick, 1996) | h = −12→13 |
| Tmin = 0.461, Tmax = 0.753 | k = −19→18 |
| 10177 measured reflections | l = −13→7 |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.047 | Riding model |
| wR(F2) = 0.118 | Calculated w = 1/[s2(Fo2) + ( 0.0501P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.98 | (Δ/σ)max = −0.004 |
| 6655 reflections | Δρmax = 0.84 e Å−3 |
| 281 parameters | Δρmin = −1.19 e Å−3 |
| 3 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.042 (13) |
Special details top
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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Co1 | 0.76676 (2) | 0.55709 (2) | 0.98039 (2) | 0.02746 (5) | |
| O1 | 0.48655 (14) | 0.55803 (13) | 1.07735 (15) | 0.0458 (3) | |
| H1 | 0.53448 (14) | 0.51715 (13) | 1.12856 (15) | 0.069* | |
| O2 | 0.8499 (2) | 0.65930 (12) | 0.7428 (2) | 0.0500 (4) | |
| O3 | 1.04775 (15) | 0.55363 (14) | 0.8825 (2) | 0.0508 (4) | |
| H3 | 0.99799 (15) | 0.59158 (14) | 0.8270 (2) | 0.076* | |
| O4 | 0.6759 (2) | 0.44606 (10) | 1.2081 (2) | 0.0443 (4) | |
| N1 | 0.5682 (2) | 0.59327 (10) | 0.9817 (2) | 0.0331 (4) | |
| N2 | 0.7441 (2) | 0.64585 (12) | 0.8234 (2) | 0.0349 (4) | |
| N3 | 0.9675 (2) | 0.52194 (11) | 0.9828 (2) | 0.0357 (4) | |
| N4 | 0.7874 (2) | 0.46755 (10) | 1.1354 (2) | 0.0324 (4) | |
| N5 | 0.7161 (2) | 0.44517 (12) | 0.8329 (2) | 0.0385 (5) | |
| H5NA | 0.7484 (2) | 0.46313 (12) | 0.7507 (2) | 0.046* | |
| H5NB | 0.7733 (2) | 0.39559 (12) | 0.8699 (2) | 0.046* | |
| C1 | 0.5122 (2) | 0.65919 (13) | 0.8903 (2) | 0.0374 (5) | |
| C2 | 0.6145 (3) | 0.68846 (13) | 0.7933 (2) | 0.0383 (5) | |
| C3 | 1.0246 (2) | 0.46090 (13) | 1.0822 (2) | 0.0382 (5) | |
| C4 | 0.9199 (3) | 0.42945 (13) | 1.1734 (2) | 0.0396 (5) | |
| C5 | 0.3585 (3) | 0.6992 (2) | 0.8810 (3) | 0.0529 (6)* | |
| H5A | 0.3098 (8) | 0.668 (1) | 0.9519 (15) | 0.079* | |
| H5B | 0.3031 (7) | 0.6884 (12) | 0.7847 (7) | 0.079* | |
| H5C | 0.3643 (3) | 0.7667 (3) | 0.901 (2) | 0.079* | |
| C6 | 0.5725 (3) | 0.7558 (2) | 0.6689 (3) | 0.0564 (7) | |
| H6A | 0.6587 (5) | 0.7714 (11) | 0.6276 (14) | 0.085* | |
| H6B | 0.532 (2) | 0.8131 (6) | 0.7032 (5) | 0.085* | |
| H6C | 0.4997 (17) | 0.7262 (6) | 0.5954 (10) | 0.085* | |
| C7 | 1.1808 (3) | 0.4246 (2) | 1.0956 (3) | 0.0614 (8) | |
| H7A | 1.1972 (8) | 0.4018 (14) | 1.0021 (6) | 0.092* | |
| H7B | 1.1960 (8) | 0.3733 (10) | 1.1654 (18) | 0.092* | |
| H7C | 1.2489 (3) | 0.4756 (4) | 1.128 (2) | 0.092* | |
| C8 | 0.9574 (3) | 0.3623 (2) | 1.2996 (3) | 0.0556 (7) | |
| H8A | 0.8726 (7) | 0.3542 (11) | 1.3464 (13) | 0.083* | |
| H8B | 1.0381 (14) | 0.3881 (7) | 1.3686 (10) | 0.083* | |
| H8C | 0.986 (2) | 0.3015 (5) | 1.2651 (4) | 0.083* | |
| C9 | 0.5627 (3) | 0.40518 (15) | 0.7849 (2) | 0.0425 (5) | |
| H9 | 0.5136 (3) | 0.40241 (15) | 0.8707 (2) | 0.051* | |
| C10 | 0.5746 (4) | 0.3017 (2) | 0.7279 (3) | 0.0721 (9) | |
| H10A | 0.627 (2) | 0.2626 (4) | 0.8048 (8) | 0.108* | |
| H10B | 0.627 (2) | 0.3024 (3) | 0.6467 (16) | 0.108* | |
| H10C | 0.4769 (4) | 0.2761 (6) | 0.697 (2) | 0.108* | |
| C11 | 0.4683 (2) | 0.46659 (14) | 0.6697 (2) | 0.0391 (5) | |
| C12 | 0.3252 (3) | 0.4907 (2) | 0.6838 (3) | 0.0545 (7) | |
| H12 | 0.2901 (3) | 0.4738 (2) | 0.7686 (3) | 0.065* | |
| C13 | 0.2329 (3) | 0.5398 (2) | 0.5741 (3) | 0.0669 (8) | |
| H13 | 0.1357 (3) | 0.5533 (2) | 0.5841 (3) | 0.080* | |
| C14 | 0.2845 (3) | 0.5683 (2) | 0.4515 (3) | 0.0674 (8) | |
| H14 | 0.2239 (3) | 0.6031 (2) | 0.3793 (3) | 0.081* | |
| C15 | 0.4289 (3) | 0.5449 (2) | 0.4354 (3) | 0.0610 (7) | |
| H15 | 0.4644 (3) | 0.5632 (2) | 0.3515 (3) | 0.073* | |
| C16 | 0.5187 (3) | 0.4945 (2) | 0.5437 (3) | 0.0491 (6) | |
| H16 | 0.6147 (3) | 0.4790 (2) | 0.5320 (3) | 0.059* | |
| C17 | 0.8276 (3) | 0.66919 (15) | 1.1215 (3) | 0.0319 (5) | 0.8484 (9) |
| H17 | 0.7489 (3) | 0.71719 (15) | 1.0994 (3) | 0.038* | 0.8484 (9) |
| C18 | 0.9645 (3) | 0.7151 (2) | 1.0899 (3) | 0.0372 (5)* | 0.8484 (9) |
| C19 | 0.8433 (4) | 0.6484 (2) | 1.2834 (3) | 0.0498 (7) | 0.8484 (9) |
| H19A | 0.9199 (4) | 0.6005 (2) | 1.3097 (3) | 0.060* | 0.8484 (9) |
| H19B | 0.7509 (4) | 0.6217 (2) | 1.3029 (3) | 0.060* | 0.8484 (9) |
| C20 | 0.8825 (2) | 0.73728 (13) | 1.3808 (2) | 0.0695 (10) | 0.8484 (9) |
| H20A | 0.8909 (2) | 0.71937 (13) | 1.4818 (2) | 0.104* | 0.8484 (9) |
| H20B | 0.8060 (2) | 0.78452 (13) | 1.3572 (2) | 0.104* | 0.8484 (9) |
| H20C | 0.9751 (2) | 0.76334 (13) | 1.3640 (2) | 0.104* | 0.8484 (9) |
| N6 | 1.0694 (2) | 0.75457 (13) | 1.0676 (2) | 0.0568 (7) | 0.8484 (9) |
| C17B | 0.8794 (2) | 0.64970 (13) | 1.1592 (2) | 0.023 (6)* | 0.0604 (11) |
| H17B | 0.9408 (2) | 0.61317 (13) | 1.2373 (2) | 0.028* | 0.0604 (11) |
| C18B | 0.9637 (2) | 0.71520 (13) | 1.0896 (2) | 0.050* | 0.0604 (11) |
| C19B | 0.7791 (2) | 0.70510 (13) | 1.2094 (2) | 0.018 (5)* | 0.0604 (11) |
| H19C | 0.6960 (2) | 0.66529 (13) | 1.2237 (2) | 0.022* | 0.0604 (11) |
| H19D | 0.7423 (2) | 0.75202 (13) | 1.1348 (2) | 0.022* | 0.0604 (11) |
| C20B | 0.8390 (2) | 0.76080 (13) | 1.3600 (2) | 0.052 (10)* | 0.0604 (11) |
| H20D | 0.7603 (2) | 0.79832 (13) | 1.3872 (2) | 0.078* | 0.0604 (11) |
| H20E | 0.9194 (2) | 0.80211 (13) | 1.3468 (2) | 0.078* | 0.0604 (11) |
| H20F | 0.8731 (2) | 0.71519 (13) | 1.4358 (2) | 0.078* | 0.0604 (11) |
| N6B | 1.0386 (2) | 0.76894 (13) | 1.0359 (2) | 0.089 (17)* | 0.0604 (11) |
| C17C | 0.8280 (2) | 0.66824 (13) | 1.1224 (2) | 0.050* | 0.0909 (12) |
| H17A | 0.9220 (2) | 0.69292 (13) | 1.1039 (2) | 0.060* | 0.0909 (12) |
| H17C | 0.7554 (2) | 0.71894 (13) | 1.0990 (2) | 0.060* | 0.0909 (12) |
| C19C | 0.8440 (2) | 0.64738 (13) | 1.2845 (2) | 0.050* | 0.0909 (12) |
| H19E | 0.9212 (2) | 0.59988 (13) | 1.3111 (2) | 0.060* | 0.0909 (12) |
| H19F | 0.7519 (2) | 0.62040 (13) | 1.3044 (2) | 0.060* | 0.0909 (12) |
| C20C | 0.8825 (2) | 0.73728 (13) | 1.3808 (2) | 0.050* | 0.0909 (12) |
| H20G | 0.7958 (2) | 0.77831 (13) | 1.3688 (2) | 0.060* | 0.0909 (12) |
| H20H | 0.9031 (2) | 0.71727 (13) | 1.4824 (2) | 0.060* | 0.0909 (12) |
| C18C | 0.9993 (2) | 0.79001 (13) | 1.3530 (2) | 0.056 (7)* | 0.0909 (12) |
| N6C | 1.0792 (2) | 0.83321 (13) | 1.3093 (2) | 0.093 (10)* | 0.0909 (12) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.03300 (9) | 0.02454 (8) | 0.02433 (8) | −0.00201 (11) | 0.00352 (7) | 0.00015 (11) |
| O1 | 0.0427 (6) | 0.0494 (7) | 0.0482 (7) | 0.0021 (10) | 0.0162 (6) | 0.0063 (10) |
| O2 | 0.0556 (9) | 0.0599 (9) | 0.0370 (7) | −0.0068 (8) | 0.0149 (7) | 0.0132 (7) |
| O3 | 0.0449 (7) | 0.0581 (7) | 0.0540 (8) | 0.0032 (10) | 0.0214 (6) | 0.0115 (11) |
| O4 | 0.0548 (9) | 0.0373 (7) | 0.0445 (8) | −0.0036 (6) | 0.0190 (7) | 0.0084 (6) |
| N1 | 0.0387 (8) | 0.0288 (6) | 0.0317 (8) | −0.0028 (6) | 0.0057 (7) | −0.0010 (6) |
| N2 | 0.0407 (9) | 0.0335 (7) | 0.0297 (8) | −0.0042 (7) | 0.0042 (7) | 0.0019 (7) |
| N3 | 0.0382 (9) | 0.0338 (7) | 0.0349 (8) | −0.0027 (6) | 0.0059 (7) | −0.0007 (7) |
| N4 | 0.0437 (9) | 0.0250 (6) | 0.0298 (7) | −0.0022 (6) | 0.0099 (7) | −0.0001 (6) |
| N5 | 0.0472 (10) | 0.0367 (8) | 0.0303 (8) | −0.0013 (8) | 0.0031 (8) | −0.0071 (7) |
| C1 | 0.043 (1) | 0.0286 (8) | 0.0374 (10) | 0.0018 (8) | −0.0023 (9) | −0.0045 (8) |
| C2 | 0.0485 (11) | 0.0300 (8) | 0.0322 (10) | −0.0013 (8) | −0.0049 (9) | −0.0003 (8) |
| C3 | 0.0395 (10) | 0.0304 (8) | 0.0413 (11) | 0.0036 (8) | −0.0021 (9) | −0.0030 (8) |
| C4 | 0.0501 (12) | 0.0284 (8) | 0.0362 (10) | 0.0026 (8) | −0.0038 (10) | −0.0003 (8) |
| C6 | 0.0688 (15) | 0.0458 (11) | 0.0465 (12) | −0.0021 (11) | −0.0128 (12) | 0.0152 (10) |
| C7 | 0.0468 (13) | 0.0520 (13) | 0.081 (2) | 0.0140 (11) | −0.0027 (14) | 0.0010 (13) |
| C8 | 0.070 (2) | 0.0432 (11) | 0.0482 (13) | 0.0081 (11) | −0.0034 (13) | 0.0119 (10) |
| C9 | 0.0493 (12) | 0.0406 (10) | 0.036 (1) | −0.0138 (9) | 0.0028 (10) | −0.0061 (9) |
| C10 | 0.094 (2) | 0.0389 (11) | 0.070 (2) | −0.0078 (12) | −0.025 (2) | −0.0071 (12) |
| C11 | 0.0434 (10) | 0.0390 (9) | 0.0330 (9) | −0.0071 (8) | 0.0017 (9) | −0.0091 (8) |
| C12 | 0.0551 (14) | 0.0628 (13) | 0.0462 (13) | −0.0078 (12) | 0.0100 (11) | −0.0085 (11) |
| C13 | 0.0513 (13) | 0.073 (2) | 0.070 (2) | 0.0084 (12) | −0.0064 (13) | −0.0142 (15) |
| C14 | 0.0711 (15) | 0.067 (2) | 0.0541 (13) | 0.0110 (15) | −0.0181 (12) | −0.002 (2) |
| C15 | 0.081 (2) | 0.0581 (14) | 0.0401 (11) | −0.0035 (14) | −0.0001 (12) | 0.0010 (12) |
| C16 | 0.0511 (13) | 0.0568 (12) | 0.0389 (11) | 0.0025 (11) | 0.0066 (10) | −0.0051 (10) |
| C17 | 0.0399 (12) | 0.0256 (9) | 0.0286 (10) | −0.0033 (9) | 0.001 (1) | −0.0033 (8) |
| C19 | 0.070 (2) | 0.0431 (12) | 0.0370 (13) | −0.0150 (12) | 0.0109 (13) | −0.0066 (11) |
| C20 | 0.108 (3) | 0.057 (2) | 0.043 (2) | −0.018 (2) | 0.011 (2) | −0.0204 (13) |
| N6 | 0.0503 (12) | 0.0486 (12) | 0.071 (2) | −0.0164 (10) | 0.0093 (13) | −0.0014 (12) |
Geometric parameters (Å, º) top
| Co1—N1 | 1.889 (2) | C4—C8 | 1.493 (3) |
| Co1—N4 | 1.890 (2) | C9—C11 | 1.519 (3) |
| Co1—N2 | 1.897 (2) | C9—C10 | 1.549 (3) |
| Co1—N3 | 1.899 (2) | C11—C12 | 1.382 (3) |
| Co1—C17C | 2.051 (2) | C11—C16 | 1.384 (3) |
| Co1—C17 | 2.055 (2) | C12—C13 | 1.386 (4) |
| Co1—N5 | 2.076 (2) | C13—C14 | 1.364 (4) |
| Co1—C17B | 2.213 (2) | C14—C15 | 1.395 (4) |
| O1—N1 | 1.348 (2) | C15—C16 | 1.377 (3) |
| O2—N2 | 1.336 (3) | C17—C18 | 1.482 (4) |
| O3—N3 | 1.356 (2) | C17—C19 | 1.512 (3) |
| O4—N4 | 1.351 (2) | C18—N6 | 1.156 (3) |
| N1—C1 | 1.296 (2) | C19—C20 | 1.541 (3) |
| N2—C2 | 1.314 (3) | C17B—C19B | 1.34 |
| N3—C3 | 1.298 (2) | C17B—C18B | 1.42 |
| N4—C4 | 1.316 (3) | C18B—N6B | 1.18 |
| N5—C9 | 1.506 (3) | C19B—C20B | 1.61 |
| C1—C2 | 1.465 (3) | C17C—C19C | 1.51 |
| C1—C5 | 1.503 (3) | C19C—C20C | 1.55 |
| C2—C6 | 1.487 (3) | C20C—C18C | 1.36 |
| C3—C4 | 1.452 (3) | C18C—N6C | 1.08 |
| C3—C7 | 1.502 (3) | ||
| N1—Co1—N4 | 98.15 (7) | N1—C1—C2 | 112.1 (2) |
| N1—Co1—N2 | 81.50 (7) | N1—C1—C5 | 124.2 (2) |
| N4—Co1—N2 | 179.22 (7) | C2—C1—C5 | 123.6 (2) |
| N1—Co1—N3 | 178.85 (7) | N2—C2—C1 | 113.2 (2) |
| N4—Co1—N3 | 81.42 (8) | N2—C2—C6 | 123.6 (2) |
| N2—Co1—N3 | 98.94 (8) | C1—C2—C6 | 123.1 (2) |
| N1—Co1—C17C | 87.13 (7) | N3—C3—C4 | 112.8 (2) |
| N4—Co1—C17C | 91.84 (7) | N3—C3—C7 | 122.8 (2) |
| N2—Co1—C17C | 88.85 (8) | C4—C3—C7 | 124.4 (2) |
| N3—Co1—C17C | 91.81 (8) | N4—C4—C3 | 113.1 (2) |
| N1—Co1—C17 | 86.98 (8) | N4—C4—C8 | 122.7 (2) |
| N4—Co1—C17 | 92.26 (8) | C3—C4—C8 | 124.1 (2) |
| N2—Co1—C17 | 88.43 (8) | N5—C9—C11 | 112.7 (2) |
| N3—Co1—C17 | 91.96 (9) | N5—C9—C10 | 109.3 (2) |
| N1—Co1—N5 | 95.74 (7) | C11—C9—C10 | 110.6 (2) |
| N4—Co1—N5 | 89.10 (7) | C12—C11—C16 | 118.1 (2) |
| N2—Co1—N5 | 90.23 (7) | C12—C11—C9 | 120.3 (2) |
| N3—Co1—N5 | 85.33 (7) | C16—C11—C9 | 121.4 (2) |
| C17C—Co1—N5 | 176.83 (8) | C11—C12—C13 | 121.3 (3) |
| C17—Co1—N5 | 176.77 (10) | C14—C13—C12 | 120.1 (3) |
| N1—Co1—C17B | 99.40 (7) | C13—C14—C15 | 119.5 (2) |
| N4—Co1—C17B | 81.06 (7) | C16—C15—C14 | 120.0 (3) |
| N2—Co1—C17B | 99.69 (7) | C15—C16—C11 | 121.0 (2) |
| N3—Co1—C17B | 79.48 (7) | C18—C17—C19 | 110.0 (2) |
| N5—Co1—C17B | 162.95 (7) | C18—C17—Co1 | 110.4 (2) |
| C1—N1—O1 | 119.2 (2) | C19—C17—Co1 | 117.1 (2) |
| C1—N1—Co1 | 117.3 (2) | N6—C18—C17 | 177.1 (2) |
| O1—N1—Co1 | 123.39 (12) | C17—C19—C20 | 113.6 (2) |
| C2—N2—O2 | 122.3 (2) | C19B—C17B—C18B | 104.1 |
| C2—N2—Co1 | 115.7 (2) | C19B—C17B—Co1 | 109.77 (5) |
| O2—N2—Co1 | 121.87 (13) | C18B—C17B—Co1 | 104.81 (5) |
| C3—N3—O3 | 120.2 (2) | N6B—C18B—C17B | 177.4 |
| C3—N3—Co1 | 116.6 (2) | C17B—C19B—C20B | 115.3 |
| O3—N3—Co1 | 123.10 (12) | C19C—C17C—Co1 | 117.46 (6) |
| C4—N4—O4 | 121.2 (2) | C17C—C19C—C20C | 113.0 |
| C4—N4—Co1 | 116.0 (2) | C18C—C20C—C19C | 116.1 |
| O4—N4—Co1 | 122.82 (12) | N6C—C18C—C20C | 168.6 |
| C9—N5—Co1 | 124.40 (15) |
(1bNirr) (3-cyanopropyl)[(R)-1-phenylethylamine]cobaloxime top
Crystal data top
| [Co(C4D7N2O2)2(C4H4D2N)(C8D11N)] | F(000) = 504 |
| Mr = 504.00 | Dx = 1.359 Mg m−3 |
| Monoclinic, P21 | Neutron radiation, λ = 1.060 Å |
| a = 9.1579 (1) Å | Cell parameters from not refined reflections |
| b = 13.9694 (2) Å | µ = 0.00 mm−1 |
| c = 9.2757 (1) Å | T = 293 K |
| β = 99.954 (1)° | Plate, red |
| V = 1168.78 (2) Å3 | 3.5 × 3.5 × 0.7 mm |
| Z = 2 |
Data collection top
| BIX-I diffractometer | 1497 reflections with I > 2σ(I) |
| Radiation source: JRR-3M atomic reactor | Rint = 0.068 |
| Bent Si crystal monochromator | θmax = 43.4°, θmin = 3.3° |
| 0.2deg ω step scan | h = −11→9 |
| 2540 measured reflections | k = −14→1 |
| 1509 independent reflections | l = −11→10 |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.107 | D-fourier |
| wR(F2) = 0.285 | Calculated w = 1/[s2(Fo2) + ( 0.2366P)2 + 0.144P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.11 | (Δ/σ)max = −0.024 |
| 1509 reflections | Δρmax = 0.15 e Å−3 |
| 422 parameters | Δρmin = −0.11 e Å−3 |
| 3 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
| Primary atom site location: determined by X-ray diffraction study | Absolute structure parameter: 9.99 (999) |
Special details top
Experimental. The cell parameters were determined by single-crystal X-ray diffraction. |
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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Co1 | 0.7668 | 0.5571 | 0.9804 | 0.0573 (14)* | |
| O1 | 0.4865 | 0.5580 | 1.0773 | 0.0548 (9) | |
| O2 | 0.8499 | 0.6593 | 0.7428 | 0.0657 (11) | |
| O3 | 1.0478 | 0.5536 | 0.8825 | 0.0713 (12) | |
| O4 | 0.6759 | 0.4461 | 1.2081 | 0.0610 (9) | |
| N1 | 0.5682 | 0.5933 | 0.9817 | 0.0515 (5) | |
| N2 | 0.7441 | 0.6458 | 0.8234 | 0.0530 (6) | |
| N3 | 0.9675 | 0.5219 | 0.9828 | 0.0482 (5) | |
| N4 | 0.7874 | 0.4675 | 1.1354 | 0.0491 (5) | |
| N5 | 0.7161 | 0.4452 | 0.8329 | 0.0580 (6) | |
| DN5A | 0.7579 (5) | 0.4683 (5) | 0.7409 (5) | 0.104 (2) | |
| DN5B | 0.7850 (6) | 0.3914 (3) | 0.8750 (5) | 0.095 (2) | |
| C1 | 0.5122 | 0.6592 | 0.8903 | 0.0535 (8) | |
| C2 | 0.6145 | 0.6885 | 0.7933 | 0.0533 (8) | |
| C3 | 1.0246 | 0.4609 | 1.0822 | 0.0522 (8) | |
| C4 | 0.9199 | 0.4294 | 1.1734 | 0.0516 (8) | |
| C5 | 0.3584 | 0.6992 | 0.8810 | 0.0677 (10) | |
| D5A | 0.2986 (6) | 0.6642 (6) | 0.9520 (9) | 0.171 (3) | |
| D5B | 0.3002 (5) | 0.6941 (6) | 0.7705 (6) | 0.144 (2) | |
| D5C | 0.3585 (6) | 0.7746 (4) | 0.8894 (9) | 0.126 (2) | |
| C6 | 0.5725 | 0.7558 | 0.6689 | 0.0687 (10) | |
| D6A | 0.6632 (8) | 0.7722 (5) | 0.6204 (7) | 0.162 (2) | |
| D6B | 0.5270 (12) | 0.8229 (5) | 0.7010 (8) | 0.176 (4) | |
| D6C | 0.4893 (9) | 0.7252 (5) | 0.5917 (6) | 0.149 (2) | |
| C7 | 1.1808 | 0.4246 | 1.0956 | 0.0685 (10) | |
| D7A | 1.2244 (7) | 0.4374 (10) | 1.0082 (10) | 0.297 (4) | |
| D7B | 1.1892 (6) | 0.3574 (6) | 1.1084 (15) | 0.198 (5) | |
| D7C | 1.2508 (7) | 0.4588 (7) | 1.1470 (16) | 0.315 (4) | |
| C8 | 0.9574 | 0.3623 | 1.2996 | 0.0751 (10) | |
| D8A | 0.8713 (6) | 0.3468 (5) | 1.3549 (6) | 0.144 (2) | |
| D8B | 1.0424 (9) | 0.3819 (5) | 1.3685 (7) | 0.167 (2) | |
| D8C | 0.9991 (8) | 0.2952 (4) | 1.2641 (6) | 0.133 (2) | |
| C9 | 0.5627 | 0.4052 | 0.7849 | 0.0603 (9) | |
| D9 | 0.5152 (5) | 0.4052 (3) | 0.8860 (4) | 0.0806 (12) | |
| C10 | 0.5746 | 0.3017 | 0.7279 | 0.0870 (13) | |
| D10A | 0.6241 (8) | 0.3013 (4) | 0.6324 (6) | 0.122 (2) | |
| D10B | 0.6415 (10) | 0.2598 (4) | 0.8116 (7) | 0.131 (3) | |
| D10C | 0.4633 (8) | 0.2721 (5) | 0.7020 (9) | 0.132 (2) | |
| C11 | 0.4683 | 0.4666 | 0.6697 | 0.0593 (8) | |
| C12 | 0.3252 | 0.4908 | 0.6838 | 0.0705 (11) | |
| D12 | 0.2800 (5) | 0.4742 (5) | 0.7786 (5) | 0.109 (2) | |
| C13 | 0.2329 | 0.5398 | 0.5741 | 0.0817 (13) | |
| D13 | 0.1176 (5) | 0.5589 (6) | 0.5848 (7) | 0.128 (2) | |
| C14 | 0.2845 | 0.5683 | 0.4515 | 0.0823 (13) | |
| D14 | 0.2070 (7) | 0.6102 (5) | 0.3697 (7) | 0.136 (2) | |
| C15 | 0.4289 | 0.5449 | 0.4354 | 0.0770 (12) | |
| D15 | 0.4693 (7) | 0.5678 (5) | 0.3359 (5) | 0.113 (2) | |
| C16 | 0.5187 | 0.4945 | 0.5437 | 0.0656 (10) | |
| D16 | 0.6302 (5) | 0.4751 (5) | 0.5230 (5) | 0.102 (2) | |
| C17 | 0.8276 | 0.6692 | 1.1215 | 0.0430 (8) | 0.8432 (2) |
| D17 | 0.7384 (5) | 0.7208 (3) | 1.0835 (6) | 0.0712 (13) | 0.8432 (2) |
| C18 | 0.9645 | 0.7151 | 1.0899 | 0.0557 (10) | 0.8432 (2) |
| C19 | 0.8433 | 0.6484 | 1.2834 | 0.0656 (12) | 0.8432 (2) |
| H19A | 0.9262 | 0.5966 | 1.3119 | 0.100* | 0.4346 (4) |
| D19A | 0.9262 | 0.5966 | 1.3119 | 0.100* | 0.4087 (4) |
| H19B | 0.7434 | 0.6195 | 1.3045 | 0.100* | 0.4026 (4) |
| D19B | 0.7434 | 0.6195 | 1.3045 | 0.100* | 0.4407 (4) |
| C20 | 0.8825 | 0.7373 | 1.3808 | 0.0829 (14) | 0.8432 (2) |
| H20A | 0.9832 (11) | 0.7641 (8) | 1.3721 (11) | 0.089 (2)* | 0.8432 (2) |
| H20B | 0.8078 (13) | 0.788 (1) | 1.3633 (14) | 0.105 (3)* | 0.8432 (2) |
| H20C | 0.8841 (19) | 0.7253 (14) | 1.4809 (19) | 0.141 (5)* | 0.8432 (2) |
| N6 | 1.0694 | 0.7546 | 1.0676 | 0.0761 (10) | 0.8432 (2) |
| C17B | 0.8794 | 0.6497 | 1.1592 | 0.050* | 0.0686 (4) |
| D17B | 0.9408 | 0.6132 | 1.2373 | 0.060* | 0.0686 (4) |
| C18B | 0.9637 | 0.7152 | 1.0896 | 0.050* | 0.0686 (4) |
| C19B | 0.7791 | 0.7051 | 1.2094 | 0.022 (5)* | 0.0686 (4) |
| C20B | 0.8390 | 0.7608 | 1.3600 | 0.031 (6)* | 0.0686 (4) |
| N6B | 1.0386 | 0.7689 | 1.0359 | 0.084 (11)* | 0.0686 (4) |
| C17C | 0.8280 | 0.6682 | 1.1224 | 0.050* | 0.0882 (4) |
| H17C | 0.9220 | 0.6929 | 1.1039 | 0.060* | 0.0882 (4) |
| H17D | 0.7554 | 0.7189 | 1.0989 | 0.060* | 0.0882 (4) |
| C19C | 0.8440 | 0.6474 | 1.2845 | 0.050* | 0.0882 (4) |
| H19E | 0.9212 | 0.5999 | 1.3111 | 0.060* | 0.0882 (4) |
| H19F | 0.7519 | 0.6204 | 1.3043 | 0.060* | 0.0882 (4) |
| C20C | 0.8825 | 0.7373 | 1.3808 | 0.050* | 0.0882 (4) |
| D20G | 0.7958 | 0.7783 | 1.3689 | 0.060* | 0.0882 (4) |
| D20H | 0.9030 | 0.7173 | 1.4824 | 0.060* | 0.0882 (4) |
| C18C | 0.9993 | 0.7900 | 1.3530 | 0.062 (8)* | 0.0882 (4) |
| N6C | 1.0792 | 0.8332 | 1.3093 | 0.095 (10)* | 0.0882 (4) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0614 (15) | 0.049 (2) | 0.0561 (15) | −0.0044 (14) | 0.0150 (13) | 0.0004 (14) |
| O2 | 0.0556 (15) | 0.091 (2) | 0.053 (2) | −0.015 (2) | 0.0166 (13) | 0.012 (2) |
| O3 | 0.060 (2) | 0.090 (3) | 0.065 (2) | −0.002 (2) | 0.0156 (15) | 0.009 (2) |
| O4 | 0.0667 (15) | 0.057 (2) | 0.068 (2) | −0.0070 (14) | 0.0348 (12) | 0.0125 (14) |
| N1 | 0.0499 (8) | 0.0512 (10) | 0.0527 (9) | 0.0039 (8) | 0.0073 (8) | 0.0045 (8) |
| N2 | 0.0683 (10) | 0.0405 (10) | 0.0462 (9) | −0.0026 (9) | −0.0013 (9) | 0.0024 (8) |
| N3 | 0.0480 (8) | 0.0452 (10) | 0.0529 (9) | −0.0006 (7) | 0.0129 (7) | 0.0023 (8) |
| N4 | 0.0542 (8) | 0.0496 (10) | 0.0436 (8) | −0.0018 (8) | 0.0088 (7) | 0.0054 (8) |
| N5 | 0.0689 (11) | 0.0454 (11) | 0.0571 (10) | −0.0014 (9) | 0.0039 (9) | −0.0036 (9) |
| DN5A | 0.097 (3) | 0.134 (4) | 0.077 (2) | −0.019 (3) | 0.005 (2) | 0.000 (3) |
| DN5B | 0.120 (3) | 0.070 (2) | 0.091 (3) | −0.006 (2) | 0.009 (2) | −0.017 (2) |
| C1 | 0.0513 (12) | 0.0386 (13) | 0.068 (2) | 0.0000 (11) | 0.0024 (12) | −0.0041 (12) |
| C2 | 0.0686 (15) | 0.0419 (14) | 0.0457 (13) | 0.0066 (12) | −0.0004 (12) | 0.0045 (11) |
| C3 | 0.0548 (12) | 0.0506 (14) | 0.0489 (12) | −0.0089 (12) | 0.0022 (11) | 0.0054 (12) |
| C4 | 0.0577 (13) | 0.0335 (12) | 0.0601 (15) | 0.0011 (11) | 0.0006 (12) | −0.0024 (11) |
| C5 | 0.0546 (13) | 0.057 (2) | 0.091 (2) | 0.0183 (13) | 0.0131 (15) | 0.015 (2) |
| D5A | 0.113 (3) | 0.187 (5) | 0.238 (5) | 0.066 (3) | 0.099 (3) | 0.104 (4) |
| D5B | 0.087 (2) | 0.209 (6) | 0.112 (4) | 0.067 (3) | −0.048 (2) | −0.024 (4) |
| D5C | 0.100 (3) | 0.068 (2) | 0.197 (6) | 0.030 (2) | −0.015 (3) | −0.023 (3) |
| C6 | 0.079 (2) | 0.057 (2) | 0.060 (2) | −0.007 (2) | −0.0167 (15) | 0.0179 (13) |
| D6A | 0.123 (4) | 0.210 (4) | 0.155 (3) | 0.026 (4) | 0.030 (3) | 0.126 (3) |
| D6B | 0.301 (9) | 0.103 (3) | 0.128 (4) | 0.066 (5) | 0.046 (5) | 0.060 (3) |
| D6C | 0.196 (5) | 0.139 (4) | 0.089 (3) | −0.050 (4) | −0.043 (3) | 0.045 (3) |
| C7 | 0.0600 (14) | 0.062 (2) | 0.077 (2) | 0.0144 (14) | −0.0055 (15) | −0.003 (2) |
| D7A | 0.131 (3) | 0.514 (11) | 0.276 (6) | 0.175 (4) | 0.121 (3) | 0.262 (6) |
| D7B | 0.084 (2) | 0.108 (4) | 0.414 (13) | 0.037 (2) | 0.075 (4) | 0.021 (6) |
| D7C | 0.073 (3) | 0.231 (5) | 0.623 (12) | −0.007 (4) | 0.012 (5) | −0.286 (5) |
| C8 | 0.072 (2) | 0.088 (2) | 0.059 (2) | −0.008 (2) | −0.0075 (15) | 0.0343 (15) |
| D8A | 0.107 (3) | 0.178 (4) | 0.155 (3) | 0.016 (3) | 0.046 (2) | 0.111 (2) |
| D8B | 0.185 (4) | 0.152 (4) | 0.127 (3) | −0.067 (4) | −0.071 (3) | 0.084 (3) |
| D8C | 0.212 (5) | 0.080 (3) | 0.116 (3) | 0.067 (3) | 0.056 (3) | 0.038 (2) |
| C9 | 0.0684 (15) | 0.053 (2) | 0.0571 (15) | −0.0078 (14) | 0.0033 (13) | −0.0056 (13) |
| D9 | 0.088 (2) | 0.089 (2) | 0.058 (2) | −0.020 (2) | −0.005 (2) | 0.007 (2) |
| C10 | 0.111 (3) | 0.049 (2) | 0.086 (2) | −0.006 (2) | −0.024 (2) | −0.003 (2) |
| D10A | 0.191 (5) | 0.082 (3) | 0.080 (3) | 0.027 (3) | −0.009 (3) | −0.028 (2) |
| D10B | 0.203 (7) | 0.082 (3) | 0.098 (3) | −0.008 (4) | −0.005 (4) | 0.000 (3) |
| D10C | 0.136 (4) | 0.095 (3) | 0.153 (5) | −0.032 (3) | −0.009 (4) | −0.006 (3) |
| C11 | 0.0645 (14) | 0.058 (2) | 0.0576 (14) | −0.0096 (13) | 0.0163 (11) | −0.0123 (13) |
| C12 | 0.0603 (15) | 0.091 (2) | 0.061 (2) | 0.000 (2) | 0.0126 (13) | −0.010 (2) |
| D12 | 0.088 (2) | 0.165 (5) | 0.081 (2) | 0.012 (3) | 0.037 (2) | 0.027 (3) |
| C13 | 0.068 (2) | 0.105 (3) | 0.067 (2) | 0.007 (2) | −0.002 (2) | 0.001 (2) |
| D13 | 0.064 (2) | 0.180 (5) | 0.143 (4) | 0.029 (3) | 0.024 (2) | 0.013 (4) |
| C14 | 0.074 (2) | 0.078 (2) | 0.085 (2) | 0.002 (2) | −0.015 (2) | 0.000 (2) |
| D14 | 0.124 (3) | 0.110 (4) | 0.145 (4) | 0.031 (3) | −0.055 (3) | 0.003 (4) |
| C15 | 0.094 (2) | 0.081 (2) | 0.056 (2) | 0.008 (2) | 0.012 (2) | 0.000 (2) |
| D15 | 0.134 (4) | 0.135 (4) | 0.071 (2) | 0.031 (3) | 0.023 (2) | 0.023 (3) |
| C16 | 0.073 (2) | 0.080 (2) | 0.0442 (14) | −0.001 (2) | 0.0118 (13) | 0.0015 (14) |
| D16 | 0.095 (2) | 0.145 (4) | 0.068 (2) | 0.025 (3) | 0.015 (2) | −0.001 (3) |
| C17 | 0.0383 (12) | 0.057 (2) | 0.0324 (12) | −0.0010 (13) | 0.0033 (10) | −0.0044 (12) |
| D17 | 0.064 (2) | 0.054 (2) | 0.098 (3) | −0.004 (2) | 0.019 (2) | −0.003 (2) |
| C18 | 0.0428 (13) | 0.052 (2) | 0.070 (2) | −0.0077 (13) | 0.0046 (14) | 0.000 (2) |
| C19 | 0.086 (2) | 0.061 (2) | 0.050 (2) | −0.019 (2) | 0.011 (2) | −0.011 (2) |
| C20 | 0.120 (3) | 0.064 (2) | 0.060 (2) | −0.009 (2) | 0.000 (2) | −0.032 (2) |
| N6 | 0.0652 (14) | 0.075 (2) | 0.089 (2) | −0.0053 (14) | 0.0159 (13) | −0.008 (2) |
Geometric parameters (Å, º) top
| Co1—N1 | 1.8898 (1) | C8—D8C | 1.085 (6) |
| Co1—N4 | 1.8909 (1) | C9—D9 | 1.100 (4) |
| Co1—N2 | 1.8959 (1) | C9—C11 | 1.5184 (1) |
| Co1—N3 | 1.8990 (1) | C9—C10 | 1.5498 (1) |
| Co1—C17C | 2.0500 (1) | C10—D10A | 1.063 (7) |
| Co1—C17 | 2.0551 (1) | C10—D10B | 1.076 (7) |
| Co1—N5 | 2.0764 (1) | C10—D10C | 1.088 (7) |
| Co1—C17B | 2.2127 (1) | C11—C12 | 1.3813 (1) |
| O1—N1 | 1.3486 (1) | C11—C16 | 1.3847 (1) |
| O2—N2 | 1.3356 (1) | C12—D12 | 1.060 (5) |
| O3—N3 | 1.3561 (1) | C12—C13 | 1.3860 (1) |
| O4—N4 | 1.3509 (1) | C13—D13 | 1.110 (5) |
| N1—C1 | 1.2957 (1) | C13—C14 | 1.3641 (1) |
| N2—C2 | 1.3145 (1) | C14—D14 | 1.111 (6) |
| N3—C3 | 1.2973 (1) | C14—C15 | 1.3951 (1) |
| N4—C4 | 1.3161 (1) | C15—D15 | 1.099 (5) |
| N5—DN5B | 1.015 (5) | C15—C16 | 1.3768 (1) |
| N5—DN5A | 1.045 (5) | C16—D16 | 1.105 (5) |
| N5—C9 | 1.5059 (1) | C17—D17 | 1.101 (4) |
| C1—C2 | 1.4650 (1) | C17—C18 | 1.4818 (1) |
| C1—C5 | 1.5038 (1) | C17—C19 | 1.5118 (1) |
| C2—C6 | 1.4865 (1) | C18—N6 | 1.1571 (1) |
| C3—C4 | 1.4523 (1) | C19—D19A | 1.0487 (1) |
| C3—C7 | 1.5025 (1) | C19—D19B | 1.0487 (1) |
| C4—C8 | 1.4926 (1) | C19—C20 | 1.5412 (1) |
| C5—D5A | 1.048 (8) | C17B—D17B | 0.9800 (1) |
| C5—D5C | 1.056 (5) | C17B—C19B | 1.3444 (1) |
| C5—D5B | 1.073 (5) | C17B—C18B | 1.4221 (1) |
| C6—D6A | 1.036 (7) | C18B—N6B | 1.1830 (1) |
| C6—D6C | 1.043 (7) | C19B—C20B | 1.6102 (1) |
| C6—D6B | 1.089 (8) | C17C—C19C | 1.5134 (1) |
| C7—D7C | 0.873 (9) | C19C—C20C | 1.5461 (1) |
| C7—D7B | 0.947 (8) | C20C—D20H | 0.9700 (1) |
| C7—D7A | 0.980 (9) | C20C—D20G | 0.9700 (1) |
| C8—D8B | 0.957 (7) | C20C—C18C | 1.3594 (1) |
| C8—D8A | 1.035 (6) | C18C—N6C | 1.0800 (1) |
| N1—Co1—N4 | 98.159 (3) | D7C—C7—C3 | 117.3 (6) |
| N1—Co1—N2 | 81.498 (3) | D7B—C7—C3 | 113.6 (4) |
| N4—Co1—N2 | 179.2 | D7A—C7—C3 | 112.8 (5) |
| N1—Co1—N3 | 178.9 | D8B—C8—D8A | 109.3 (5) |
| N4—Co1—N3 | 81.404 (3) | D8B—C8—D8C | 99.3 (6) |
| N2—Co1—N3 | 98.953 (3) | D8A—C8—D8C | 108.0 (5) |
| N1—Co1—C17C | 87.125 (4) | D8B—C8—C4 | 113.2 (4) |
| N4—Co1—C17C | 91.854 (1) | D8A—C8—C4 | 115.3 (3) |
| N2—Co1—C17C | 88.867 (2) | D8C—C8—C4 | 110.5 (3) |
| N3—Co1—C17C | 91.830 (4) | D9—C9—N5 | 103.6 (2) |
| N1—Co1—C17 | 86.969 (3) | D9—C9—C11 | 109.8 (2) |
| N4—Co1—C17 | 92.276 (2) | N5—C9—C11 | 112.769 (3) |
| N2—Co1—C17 | 88.444 (2) | D9—C9—C10 | 110.6 (3) |
| N3—Co1—C17 | 91.989 (4) | N5—C9—C10 | 109.270 (4) |
| N1—Co1—N5 | 95.729 (4) | C11—C9—C10 | 110.608 (4) |
| N4—Co1—N5 | 89.096 (1) | D10A—C10—D10B | 109.1 (6) |
| N2—Co1—N5 | 90.204 (2) | D10A—C10—D10C | 109.4 (6) |
| N3—Co1—N5 | 85.327 (3) | D10B—C10—D10C | 110.4 (6) |
| C17C—Co1—N5 | 176.8 | D10A—C10—C9 | 110.8 (3) |
| C17—Co1—N5 | 176.8 | D10B—C10—C9 | 109.1 (3) |
| N1—Co1—C17B | 99.387 (3) | D10C—C10—C9 | 108.1 (4) |
| N4—Co1—C17B | 81.069 (2) | C12—C11—C16 | 118.108 (2) |
| N2—Co1—C17B | 99.710 (2) | C12—C11—C9 | 120.377 (2) |
| N3—Co1—C17B | 79.507 (3) | C16—C11—C9 | 121.378 (2) |
| N5—Co1—C17B | 162.971 (1) | D12—C12—C11 | 122.5 (3) |
| C1—N1—O1 | 119.221 (4) | D12—C12—C13 | 116.2 (3) |
| C1—N1—Co1 | 117.287 (3) | C11—C12—C13 | 121.301 (3) |
| O1—N1—Co1 | 123.388 (3) | D13—C13—C14 | 118.4 (4) |
| C2—N2—O2 | 122.195 (3) | D13—C13—C12 | 121.5 (4) |
| C2—N2—Co1 | 115.773 (4) | C14—C13—C12 | 120.065 (2) |
| O2—N2—Co1 | 121.899 (2) | D14—C14—C13 | 116.8 (4) |
| C3—N3—O3 | 120.153 (2) | D14—C14—C15 | 123.8 (4) |
| C3—N3—Co1 | 116.668 (3) | C13—C14—C15 | 119.487 (2) |
| O3—N3—Co1 | 123.089 (3) | D15—C15—C16 | 121.1 (3) |
| C4—N4—O4 | 121.218 (2) | D15—C15—C14 | 119.0 (3) |
| C4—N4—Co1 | 115.946 (3) | C16—C15—C14 | 119.962 (3) |
| O4—N4—Co1 | 122.777 (3) | D16—C16—C15 | 116.9 (3) |
| DN5B—N5—DN5A | 104.6 (4) | D16—C16—C11 | 122.1 (3) |
| DN5B—N5—C9 | 109.0 (3) | C15—C16—C11 | 121.036 (2) |
| DN5A—N5—C9 | 109.1 (3) | D17—C17—C18 | 105.0 (2) |
| DN5B—N5—Co1 | 104.5 (3) | D17—C17—C19 | 112.5 (3) |
| DN5A—N5—Co1 | 103.5 (3) | C18—C17—C19 | 109.950 (2) |
| C9—N5—Co1 | 124.408 (3) | D17—C17—Co1 | 101.0 (2) |
| N1—C1—C2 | 112.181 (3) | C18—C17—Co1 | 110.431 (3) |
| N1—C1—C5 | 124.220 (3) | C19—C17—Co1 | 117.061 (3) |
| C2—C1—C5 | 123.573 (2) | N6—C18—C17 | 177.041 (2) |
| N2—C2—C1 | 113.114 (2) | D19A—C19—D19B | 107.705 (2) |
| N2—C2—C6 | 123.700 (3) | D19A—C19—C17 | 108.853 (4) |
| C1—C2—C6 | 123.113 (3) | D19B—C19—C17 | 108.851 (3) |
| N3—C3—C4 | 112.794 (3) | D19A—C19—C20 | 108.849 (2) |
| N3—C3—C7 | 122.789 (3) | D19B—C19—C20 | 108.849 (4) |
| C4—C3—C7 | 124.372 (2) | C17—C19—C20 | 113.575 (4) |
| N4—C4—C3 | 113.107 (3) | D17B—C17B—C19B | 112.528 (4) |
| N4—C4—C8 | 122.719 (3) | D17B—C17B—C18B | 112.528 (2) |
| C3—C4—C8 | 124.163 (2) | C19B—C17B—C18B | 104.116 (2) |
| D5A—C5—D5C | 114.4 (6) | D17B—C17B—Co1 | 112.523 (1) |
| D5A—C5—D5B | 110.0 (5) | C19B—C17B—Co1 | 109.777 (3) |
| D5C—C5—D5B | 97.5 (6) | C18B—C17B—Co1 | 104.780 (3) |
| D5A—C5—C1 | 112.1 (4) | N6B—C18B—C17B | 177.365 (1) |
| D5C—C5—C1 | 112.2 (3) | C17B—C19B—C20B | 115.338 (2) |
| D5B—C5—C1 | 109.6 (3) | C19C—C17C—Co1 | 117.499 (3) |
| D6A—C6—D6C | 109.7 (6) | C17C—C19C—C20C | 113.033 (4) |
| D6A—C6—D6B | 107.6 (7) | D20H—C20C—D20G | 107.392 (4) |
| D6C—C6—D6B | 105.8 (7) | D20H—C20C—C18C | 108.282 (3) |
| D6A—C6—C2 | 110.9 (4) | D20G—C20C—C18C | 108.279 (1) |
| D6C—C6—C2 | 109.5 (4) | D20H—C20C—C19C | 108.281 (4) |
| D6B—C6—C2 | 113.1 (4) | D20G—C20C—C19C | 108.282 (4) |
| D7C—C7—D7B | 116.0 (8) | C18C—C20C—C19C | 116.016 (3) |
| D7C—C7—D7A | 89.2 (11) | N6C—C18C—C20C | 168.566 (2) |
| D7B—C7—D7A | 104.4 (11) |
