Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047691/cv2305sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047691/cv2305Isup2.hkl |
CCDC reference: 667124
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.044
- wR factor = 0.073
- Data-to-parameter ratio = 15.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 40 Perc. PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn - O5 .. 7.65 su PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for N5
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn (4) 5.13
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For general background, see: Collins et al. (1990, 1991); Cavallo & Jacobsen (2003); Linde et al. (1999). For the use of similar compounds as model compounds in PSII, see: Weng et al. (2004). The oxidation state of the Mn atom was verified according to Brown & Altermatt (1985) and Brown (1996).
The title compound was synthesized following literature procedures (Collins et al., 1990; 1991) and recrystallized from a CH2Cl2 solution by adding benzene as a layer upon the original solution and letting the benzene mix with the original solution by diffusion.
All hydrogen atoms were geometrically positioned (C—H 0.93–0.97 Å) and refined in riding mode approximation, with Uiso(H) = 1.5Ueq(C) for the CH3 and 1.2Ueq(C) for the CH2 and aromatic CH.
The title complex was prepared with the intention of testing a mechanism for oxygen-transfer discussed by e.g. Cavallo & Jacobsen (2003) as well as Linde et al. (1999) were the spin-state of the Mn-oxo species is supposed to dictate whether the reaction will proceed via a radical (from the triplet state) or metallacyclic intermediate (from the quintet-state). Since the title compound is isolated in a stable singlet-state it might be possible to selectively excite it to form either one or possibly both of these spin-states. Similar compounds have also been used as model complexes in the study of the water oxidizing enzyme, PSII (Weng et al., 2004). The oxidation state of the MnV atom was verified with bond valence calculations (Brown & Altermatt, 1985; Brown, 1996).
For general background, see: Collins et al. (1990, 1991); Cavallo & Jacobsen (2003); Linde et al. (1999). For the use of similar compounds as model compounds in PSII, see: Weng et al. (2004). The oxidation state of the Mn atom was verified according to Brown & Altermatt (1985) and Brown (1996).
Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: PLATON (Spek, 2003).
Fig. 1. The content of asymmetric part of the title compound with the atom numbering scheme and displacement ellipsoids drawn at the 50% probability level. |
(C8H20N)[Mn(C21H26N4O4)O] | Z = 4 |
Mr = 599.65 | F(000) = 1280 |
Monoclinic, P21/c | Dx = 1.290 Mg m−3 |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 11.2606 (11) Å | θ = 3.8–33.4° |
b = 15.5269 (15) Å | µ = 0.47 mm−1 |
c = 17.7586 (17) Å | T = 293 K |
β = 96.024 (8)° | Prism, red |
V = 3087.8 (5) Å3 | 0.20 × 0.15 × 0.10 mm |
Oxford Diffraction Xcalibur-3 kappa diffractometer with SapphireIII CCD | 5454 independent reflections |
Radiation source: fine-focus sealed tube | 2197 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.078 |
Detector resolution: 12 pixels mm-1 | θmax = 25.0°, θmin = 1.8° |
ω scans at different φ | h = −13→13 |
Absorption correction: numerical (X-RED; Stoe & Cie, 1997) | k = −18→18 |
Tmin = 0.899, Tmax = 0.960 | l = −21→21 |
18232 measured reflections |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 0.82 | w = 1/[σ2(Fo2) + (0.0259P)2] where P = (Fo2 + 2Fc2)/3 |
5454 reflections | (Δ/σ)max < 0.001 |
361 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
(C8H20N)[Mn(C21H26N4O4)O] | V = 3087.8 (5) Å3 |
Mr = 599.65 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.2606 (11) Å | µ = 0.47 mm−1 |
b = 15.5269 (15) Å | T = 293 K |
c = 17.7586 (17) Å | 0.20 × 0.15 × 0.10 mm |
β = 96.024 (8)° |
Oxford Diffraction Xcalibur-3 kappa diffractometer with SapphireIII CCD | 5454 independent reflections |
Absorption correction: numerical (X-RED; Stoe & Cie, 1997) | 2197 reflections with I > 2σ(I) |
Tmin = 0.899, Tmax = 0.960 | Rint = 0.078 |
18232 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 0.82 | Δρmax = 0.24 e Å−3 |
5454 reflections | Δρmin = −0.26 e Å−3 |
361 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.0713 (3) | 0.1659 (2) | 0.64612 (19) | 0.0536 (10) | |
C2 | −0.0228 (3) | 0.1642 (2) | 0.70234 (19) | 0.0494 (9) | |
C3 | 0.0040 (4) | 0.1197 (2) | 0.77932 (18) | 0.0487 (10) | |
C4 | 0.1351 (3) | 0.0566 (2) | 0.88100 (16) | 0.0473 (9) | |
C5 | 0.2652 (3) | 0.0322 (2) | 0.89271 (19) | 0.0566 (10) | |
C6 | 0.4369 (3) | 0.00699 (19) | 0.82099 (19) | 0.0470 (9) | |
C7 | 0.5237 (3) | −0.0231 (2) | 0.87699 (19) | 0.0574 (10) | |
H7 | 0.5044 | −0.0341 | 0.9257 | 0.069* | |
C8 | 0.6371 (3) | −0.0360 (2) | 0.8587 (2) | 0.0671 (11) | |
H8 | 0.6950 | −0.0555 | 0.8960 | 0.080* | |
C9 | 0.6687 (3) | −0.0210 (2) | 0.7866 (2) | 0.0698 (12) | |
H9 | 0.7465 | −0.0312 | 0.7757 | 0.084* | |
C10 | 0.5833 (3) | 0.0093 (2) | 0.73066 (19) | 0.0575 (10) | |
H10 | 0.6033 | 0.0198 | 0.6820 | 0.069* | |
C11 | 0.4679 (3) | 0.0237 (2) | 0.74835 (19) | 0.0474 (9) | |
C12 | 0.3802 (4) | 0.0999 (2) | 0.63519 (19) | 0.0578 (11) | |
C13 | 0.2646 (3) | 0.1429 (2) | 0.60455 (18) | 0.0539 (10) | |
C14 | 0.2923 (3) | 0.2382 (2) | 0.59448 (17) | 0.0780 (12) | |
H14A | 0.2208 | 0.2679 | 0.5750 | 0.117* | |
H14B | 0.3514 | 0.2442 | 0.5596 | 0.117* | |
H14C | 0.3221 | 0.2625 | 0.6425 | 0.117* | |
C15 | 0.2206 (3) | 0.0987 (2) | 0.52830 (16) | 0.0861 (13) | |
H15A | 0.1475 | 0.1250 | 0.5072 | 0.129* | |
H15B | 0.2072 | 0.0386 | 0.5369 | 0.129* | |
H15C | 0.2801 | 0.1050 | 0.4937 | 0.129* | |
C16 | −0.1365 (3) | 0.1231 (2) | 0.66216 (18) | 0.0666 (11) | |
H16A | −0.1984 | 0.1242 | 0.6963 | 0.080* | |
H16B | −0.1639 | 0.1579 | 0.6183 | 0.080* | |
C17 | −0.1203 (3) | 0.0311 (2) | 0.63653 (18) | 0.0866 (12) | |
H17A | −0.1945 | 0.0099 | 0.6119 | 0.130* | |
H17B | −0.0955 | −0.0042 | 0.6797 | 0.130* | |
H17C | −0.0606 | 0.0295 | 0.6018 | 0.130* | |
C18 | −0.0493 (3) | 0.2593 (2) | 0.72047 (19) | 0.0738 (12) | |
H18A | −0.0758 | 0.2890 | 0.6736 | 0.089* | |
H18B | −0.1142 | 0.2612 | 0.7523 | 0.089* | |
C19 | 0.0576 (4) | 0.3070 (2) | 0.7601 (2) | 0.0905 (14) | |
H19A | 0.0354 | 0.3653 | 0.7697 | 0.136* | |
H19B | 0.1216 | 0.3066 | 0.7285 | 0.136* | |
H19C | 0.0831 | 0.2790 | 0.8073 | 0.136* | |
C20 | 0.1145 (3) | 0.1258 (2) | 0.93946 (15) | 0.0658 (11) | |
H20A | 0.0320 | 0.1427 | 0.9338 | 0.099* | |
H20B | 0.1636 | 0.1750 | 0.9318 | 0.099* | |
H20C | 0.1351 | 0.1034 | 0.9895 | 0.099* | |
C21 | 0.0643 (3) | −0.0252 (2) | 0.89443 (17) | 0.0766 (12) | |
H21A | −0.0196 | −0.0126 | 0.8878 | 0.115* | |
H21B | 0.0860 | −0.0456 | 0.9450 | 0.115* | |
H21C | 0.0820 | −0.0687 | 0.8589 | 0.115* | |
N1 | 0.1796 (3) | 0.12924 (16) | 0.66200 (13) | 0.0449 (7) | |
N2 | 0.3707 (2) | 0.05739 (16) | 0.70151 (14) | 0.0455 (7) | |
N3 | 0.3167 (2) | 0.02626 (15) | 0.82645 (13) | 0.0447 (7) | |
N4 | 0.1136 (2) | 0.08759 (15) | 0.80135 (13) | 0.0429 (7) | |
O3 | 0.3189 (2) | 0.01663 (18) | 0.95520 (12) | 0.1030 (10) | |
O4 | 0.4708 (2) | 0.10505 (17) | 0.60263 (13) | 0.0946 (10) | |
O5 | 0.16898 (18) | −0.04408 (13) | 0.70485 (9) | 0.0552 (6) | |
O1 | 0.0409 (2) | 0.20457 (16) | 0.58588 (13) | 0.0806 (8) | |
O2 | −0.0786 (2) | 0.11887 (14) | 0.82048 (12) | 0.0658 (7) | |
Mn | 0.21949 (5) | 0.04441 (3) | 0.73523 (2) | 0.04636 (17) | |
N5 | 0.6263 (3) | 0.24009 (18) | 0.40445 (14) | 0.0504 (8) | |
C22 | 0.5082 (3) | 0.1965 (2) | 0.40647 (19) | 0.0751 (12) | |
H22A | 0.5030 | 0.1753 | 0.4574 | 0.090* | |
H22B | 0.5053 | 0.1470 | 0.3730 | 0.090* | |
C23 | 0.3988 (3) | 0.2534 (3) | 0.3835 (2) | 0.1245 (18) | |
H23A | 0.3273 | 0.2204 | 0.3862 | 0.187* | |
H23B | 0.4016 | 0.2736 | 0.3326 | 0.187* | |
H23C | 0.3991 | 0.3017 | 0.4172 | 0.187* | |
C24 | 0.6415 (4) | 0.3134 (2) | 0.46178 (18) | 0.0798 (13) | |
H24A | 0.7159 | 0.3428 | 0.4558 | 0.096* | |
H24B | 0.5772 | 0.3544 | 0.4499 | 0.096* | |
C25 | 0.6422 (4) | 0.2870 (2) | 0.54408 (16) | 0.0951 (14) | |
H25A | 0.6528 | 0.3371 | 0.5758 | 0.143* | |
H25B | 0.7066 | 0.2474 | 0.5571 | 0.143* | |
H25C | 0.5678 | 0.2598 | 0.5514 | 0.143* | |
C26 | 0.7197 (3) | 0.1717 (2) | 0.42219 (18) | 0.0657 (11) | |
H26A | 0.7043 | 0.1438 | 0.4691 | 0.079* | |
H26B | 0.7098 | 0.1286 | 0.3825 | 0.079* | |
C27 | 0.8479 (3) | 0.2010 (3) | 0.43007 (19) | 0.0993 (14) | |
H27A | 0.8994 | 0.1524 | 0.4414 | 0.149* | |
H27B | 0.8603 | 0.2423 | 0.4703 | 0.149* | |
H27C | 0.8659 | 0.2270 | 0.3835 | 0.149* | |
C28 | 0.6357 (3) | 0.2807 (2) | 0.32739 (16) | 0.0650 (11) | |
H28A | 0.5786 | 0.3276 | 0.3206 | 0.078* | |
H28B | 0.7148 | 0.3054 | 0.3274 | 0.078* | |
C29 | 0.6142 (3) | 0.2206 (2) | 0.26035 (16) | 0.0801 (13) | |
H29A | 0.6226 | 0.2518 | 0.2146 | 0.120* | |
H29B | 0.5350 | 0.1973 | 0.2584 | 0.120* | |
H29C | 0.6714 | 0.1746 | 0.2656 | 0.120* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.054 (3) | 0.056 (3) | 0.048 (2) | −0.004 (2) | −0.007 (2) | 0.0051 (19) |
C2 | 0.046 (3) | 0.044 (3) | 0.056 (2) | 0.000 (2) | −0.004 (2) | −0.0021 (19) |
C3 | 0.058 (3) | 0.043 (2) | 0.044 (2) | −0.001 (2) | 0.001 (2) | −0.0091 (18) |
C4 | 0.047 (2) | 0.055 (3) | 0.039 (2) | 0.010 (2) | 0.0029 (18) | 0.0039 (19) |
C5 | 0.054 (3) | 0.071 (3) | 0.044 (2) | 0.013 (2) | 0.003 (2) | 0.001 (2) |
C6 | 0.047 (3) | 0.044 (2) | 0.049 (2) | 0.000 (2) | −0.001 (2) | −0.0018 (18) |
C7 | 0.055 (3) | 0.059 (3) | 0.055 (2) | 0.003 (2) | −0.006 (2) | 0.0045 (19) |
C8 | 0.052 (3) | 0.070 (3) | 0.076 (3) | 0.007 (3) | −0.009 (2) | 0.004 (2) |
C9 | 0.042 (3) | 0.078 (3) | 0.090 (3) | 0.005 (2) | 0.009 (3) | −0.011 (2) |
C10 | 0.051 (3) | 0.063 (3) | 0.059 (2) | −0.002 (2) | 0.008 (2) | −0.0031 (19) |
C11 | 0.039 (2) | 0.049 (3) | 0.054 (2) | 0.001 (2) | 0.004 (2) | −0.0086 (19) |
C12 | 0.058 (3) | 0.067 (3) | 0.049 (2) | 0.000 (2) | 0.010 (2) | −0.001 (2) |
C13 | 0.058 (3) | 0.062 (3) | 0.041 (2) | −0.001 (2) | 0.000 (2) | 0.0075 (19) |
C14 | 0.082 (3) | 0.073 (3) | 0.080 (3) | −0.006 (3) | 0.008 (2) | 0.029 (2) |
C15 | 0.097 (3) | 0.117 (3) | 0.043 (2) | −0.008 (3) | 0.004 (2) | −0.006 (2) |
C16 | 0.056 (3) | 0.076 (3) | 0.064 (2) | 0.003 (3) | −0.009 (2) | 0.003 (2) |
C17 | 0.079 (3) | 0.095 (4) | 0.082 (3) | −0.020 (3) | −0.006 (2) | −0.021 (3) |
C18 | 0.072 (3) | 0.060 (3) | 0.087 (3) | 0.012 (3) | −0.002 (3) | 0.005 (2) |
C19 | 0.084 (3) | 0.056 (3) | 0.129 (4) | −0.003 (3) | −0.005 (3) | −0.015 (3) |
C20 | 0.067 (3) | 0.090 (3) | 0.041 (2) | −0.001 (2) | 0.007 (2) | −0.013 (2) |
C21 | 0.095 (3) | 0.072 (3) | 0.063 (2) | −0.007 (3) | 0.012 (2) | 0.009 (2) |
N1 | 0.0452 (19) | 0.0511 (19) | 0.0373 (16) | 0.0060 (17) | −0.0008 (15) | 0.0063 (13) |
N2 | 0.0458 (19) | 0.0526 (19) | 0.0380 (15) | 0.0024 (17) | 0.0044 (15) | 0.0053 (15) |
N3 | 0.0414 (19) | 0.053 (2) | 0.0387 (16) | 0.0088 (16) | −0.0007 (14) | 0.0012 (14) |
N4 | 0.043 (2) | 0.051 (2) | 0.0339 (15) | 0.0022 (16) | 0.0008 (15) | 0.0016 (13) |
O3 | 0.090 (2) | 0.176 (3) | 0.0399 (14) | 0.044 (2) | −0.0057 (14) | 0.0171 (16) |
O4 | 0.074 (2) | 0.134 (2) | 0.0805 (19) | 0.0175 (19) | 0.0307 (18) | 0.0368 (17) |
O5 | 0.0587 (15) | 0.0472 (14) | 0.0583 (13) | −0.0089 (14) | −0.0008 (11) | −0.0127 (13) |
O1 | 0.072 (2) | 0.102 (2) | 0.0652 (16) | 0.0138 (17) | −0.0053 (15) | 0.0302 (15) |
O2 | 0.0459 (16) | 0.0950 (19) | 0.0568 (15) | 0.0063 (15) | 0.0070 (13) | 0.0018 (14) |
Mn | 0.0484 (3) | 0.0494 (4) | 0.0399 (3) | 0.0004 (3) | −0.0018 (2) | −0.0004 (3) |
N5 | 0.059 (2) | 0.041 (2) | 0.0513 (18) | 0.0051 (18) | 0.0048 (16) | 0.0071 (15) |
C22 | 0.060 (3) | 0.095 (3) | 0.071 (3) | 0.000 (3) | 0.011 (2) | 0.017 (2) |
C23 | 0.062 (3) | 0.193 (5) | 0.121 (4) | 0.028 (4) | 0.017 (3) | 0.043 (3) |
C24 | 0.115 (4) | 0.052 (3) | 0.071 (3) | 0.012 (3) | 0.002 (3) | −0.006 (2) |
C25 | 0.139 (4) | 0.098 (3) | 0.047 (2) | 0.019 (3) | 0.006 (3) | −0.010 (2) |
C26 | 0.069 (3) | 0.063 (3) | 0.065 (2) | 0.014 (3) | 0.008 (2) | 0.007 (2) |
C27 | 0.062 (3) | 0.159 (4) | 0.075 (3) | 0.004 (3) | −0.003 (2) | 0.021 (3) |
C28 | 0.074 (3) | 0.067 (3) | 0.054 (2) | 0.001 (2) | 0.001 (2) | 0.019 (2) |
C29 | 0.089 (3) | 0.098 (3) | 0.052 (2) | −0.003 (3) | 0.002 (2) | 0.000 (2) |
C1—O1 | 1.243 (3) | C18—H18A | 0.9700 |
C1—N1 | 1.348 (4) | C18—H18B | 0.9700 |
C1—C2 | 1.531 (4) | C19—H19A | 0.9600 |
C2—C3 | 1.533 (4) | C19—H19B | 0.9600 |
C2—C16 | 1.537 (4) | C19—H19C | 0.9600 |
C2—C18 | 1.548 (4) | C20—H20A | 0.9600 |
C3—O2 | 1.242 (3) | C20—H20B | 0.9600 |
C3—N4 | 1.350 (4) | C20—H20C | 0.9600 |
C4—N4 | 1.490 (3) | C21—H21A | 0.9600 |
C4—C5 | 1.507 (4) | C21—H21B | 0.9600 |
C4—C20 | 1.529 (4) | C21—H21C | 0.9600 |
C4—C21 | 1.531 (4) | N1—Mn | 1.872 (2) |
C5—O3 | 1.231 (3) | N2—Mn | 1.874 (2) |
C5—N3 | 1.369 (3) | N3—Mn | 1.879 (2) |
C6—C11 | 1.396 (4) | N4—Mn | 1.882 (2) |
C6—N3 | 1.399 (4) | O5—Mn | 1.561 (2) |
C6—C7 | 1.399 (4) | N5—C22 | 1.495 (4) |
C7—C8 | 1.365 (4) | N5—C26 | 1.505 (4) |
C7—H7 | 0.9300 | N5—C28 | 1.521 (3) |
C8—C9 | 1.384 (4) | N5—C24 | 1.525 (4) |
C8—H8 | 0.9300 | C22—C23 | 1.536 (4) |
C9—C10 | 1.391 (4) | C22—H22A | 0.9700 |
C9—H9 | 0.9300 | C22—H22B | 0.9700 |
C10—C11 | 1.386 (4) | C23—H23A | 0.9600 |
C10—H10 | 0.9300 | C23—H23B | 0.9600 |
C11—N2 | 1.405 (4) | C23—H23C | 0.9600 |
C12—O4 | 1.227 (4) | C24—C25 | 1.517 (4) |
C12—N2 | 1.364 (4) | C24—H24A | 0.9700 |
C12—C13 | 1.513 (4) | C24—H24B | 0.9700 |
C13—N1 | 1.486 (4) | C25—H25A | 0.9600 |
C13—C14 | 1.526 (4) | C25—H25B | 0.9600 |
C13—C15 | 1.552 (4) | C25—H25C | 0.9600 |
C14—H14A | 0.9600 | C26—C27 | 1.507 (4) |
C14—H14B | 0.9600 | C26—H26A | 0.9700 |
C14—H14C | 0.9600 | C26—H26B | 0.9700 |
C15—H15A | 0.9600 | C27—H27A | 0.9600 |
C15—H15B | 0.9600 | C27—H27B | 0.9600 |
C15—H15C | 0.9600 | C27—H27C | 0.9600 |
C16—C17 | 1.516 (4) | C28—C29 | 1.512 (4) |
C16—H16A | 0.9700 | C28—H28A | 0.9700 |
C16—H16B | 0.9700 | C28—H28B | 0.9700 |
C17—H17A | 0.9600 | C29—H29A | 0.9600 |
C17—H17B | 0.9600 | C29—H29B | 0.9600 |
C17—H17C | 0.9600 | C29—H29C | 0.9600 |
C18—C19 | 1.521 (4) | ||
O1—C1—N1 | 123.1 (3) | H20A—C20—H20B | 109.5 |
O1—C1—C2 | 115.0 (3) | C4—C20—H20C | 109.5 |
N1—C1—C2 | 121.9 (3) | H20A—C20—H20C | 109.5 |
C1—C2—C3 | 120.3 (3) | H20B—C20—H20C | 109.5 |
C1—C2—C16 | 107.8 (3) | C4—C21—H21A | 109.5 |
C3—C2—C16 | 107.7 (3) | C4—C21—H21B | 109.5 |
C1—C2—C18 | 106.3 (3) | H21A—C21—H21B | 109.5 |
C3—C2—C18 | 105.6 (3) | C4—C21—H21C | 109.5 |
C16—C2—C18 | 108.8 (3) | H21A—C21—H21C | 109.5 |
O2—C3—N4 | 123.0 (3) | H21B—C21—H21C | 109.5 |
O2—C3—C2 | 116.1 (3) | C1—N1—C13 | 115.4 (3) |
N4—C3—C2 | 120.9 (3) | C1—N1—Mn | 126.1 (2) |
N4—C4—C5 | 105.7 (3) | C13—N1—Mn | 116.9 (2) |
N4—C4—C20 | 113.3 (3) | C12—N2—C11 | 124.3 (3) |
C5—C4—C20 | 107.3 (3) | C12—N2—Mn | 119.0 (2) |
N4—C4—C21 | 112.4 (3) | C11—N2—Mn | 116.7 (2) |
C5—C4—C21 | 106.6 (3) | C5—N3—C6 | 125.0 (3) |
C20—C4—C21 | 111.0 (3) | C5—N3—Mn | 118.0 (2) |
O3—C5—N3 | 123.3 (3) | C6—N3—Mn | 116.9 (2) |
O3—C5—C4 | 123.5 (3) | C3—N4—C4 | 116.5 (3) |
N3—C5—C4 | 113.1 (3) | C3—N4—Mn | 124.8 (2) |
C11—C6—N3 | 111.2 (3) | C4—N4—Mn | 115.3 (2) |
C11—C6—C7 | 119.7 (3) | O5—Mn—N1 | 109.08 (10) |
N3—C6—C7 | 129.1 (3) | O5—Mn—N2 | 107.12 (10) |
C8—C7—C6 | 118.8 (3) | N1—Mn—N2 | 82.09 (12) |
C8—C7—H7 | 120.6 | O5—Mn—N3 | 108.91 (10) |
C6—C7—H7 | 120.6 | N1—Mn—N3 | 141.27 (11) |
C7—C8—C9 | 122.2 (3) | N2—Mn—N3 | 79.91 (12) |
C7—C8—H8 | 118.9 | O5—Mn—N4 | 107.30 (10) |
C9—C8—H8 | 118.9 | N1—Mn—N4 | 93.50 (12) |
C8—C9—C10 | 119.5 (3) | N2—Mn—N4 | 144.80 (11) |
C8—C9—H9 | 120.3 | N3—Mn—N4 | 82.27 (12) |
C10—C9—H9 | 120.3 | C22—N5—C26 | 106.2 (3) |
C11—C10—C9 | 119.1 (3) | C22—N5—C28 | 110.9 (3) |
C11—C10—H10 | 120.4 | C26—N5—C28 | 111.6 (3) |
C9—C10—H10 | 120.4 | C22—N5—C24 | 111.1 (3) |
C10—C11—C6 | 120.7 (3) | C26—N5—C24 | 111.1 (3) |
C10—C11—N2 | 128.1 (3) | C28—N5—C24 | 106.1 (2) |
C6—C11—N2 | 111.2 (3) | N5—C22—C23 | 115.0 (3) |
O4—C12—N2 | 125.6 (4) | N5—C22—H22A | 108.5 |
O4—C12—C13 | 121.9 (3) | C23—C22—H22A | 108.5 |
N2—C12—C13 | 112.4 (3) | N5—C22—H22B | 108.5 |
N1—C13—C12 | 106.4 (3) | C23—C22—H22B | 108.5 |
N1—C13—C14 | 111.9 (3) | H22A—C22—H22B | 107.5 |
C12—C13—C14 | 106.9 (3) | C22—C23—H23A | 109.5 |
N1—C13—C15 | 111.5 (3) | C22—C23—H23B | 109.5 |
C12—C13—C15 | 107.5 (3) | H23A—C23—H23B | 109.5 |
C14—C13—C15 | 112.2 (3) | C22—C23—H23C | 109.5 |
C13—C14—H14A | 109.5 | H23A—C23—H23C | 109.5 |
C13—C14—H14B | 109.5 | H23B—C23—H23C | 109.5 |
H14A—C14—H14B | 109.5 | C25—C24—N5 | 115.5 (3) |
C13—C14—H14C | 109.5 | C25—C24—H24A | 108.4 |
H14A—C14—H14C | 109.5 | N5—C24—H24A | 108.4 |
H14B—C14—H14C | 109.5 | C25—C24—H24B | 108.4 |
C13—C15—H15A | 109.5 | N5—C24—H24B | 108.4 |
C13—C15—H15B | 109.5 | H24A—C24—H24B | 107.5 |
H15A—C15—H15B | 109.5 | C24—C25—H25A | 109.5 |
C13—C15—H15C | 109.5 | C24—C25—H25B | 109.5 |
H15A—C15—H15C | 109.5 | H25A—C25—H25B | 109.5 |
H15B—C15—H15C | 109.5 | C24—C25—H25C | 109.5 |
C17—C16—C2 | 114.1 (3) | H25A—C25—H25C | 109.5 |
C17—C16—H16A | 108.7 | H25B—C25—H25C | 109.5 |
C2—C16—H16A | 108.7 | C27—C26—N5 | 116.6 (3) |
C17—C16—H16B | 108.7 | C27—C26—H26A | 108.1 |
C2—C16—H16B | 108.7 | N5—C26—H26A | 108.1 |
H16A—C16—H16B | 107.6 | C27—C26—H26B | 108.1 |
C16—C17—H17A | 109.5 | N5—C26—H26B | 108.1 |
C16—C17—H17B | 109.5 | H26A—C26—H26B | 107.3 |
H17A—C17—H17B | 109.5 | C26—C27—H27A | 109.5 |
C16—C17—H17C | 109.5 | C26—C27—H27B | 109.5 |
H17A—C17—H17C | 109.5 | H27A—C27—H27B | 109.5 |
H17B—C17—H17C | 109.5 | C26—C27—H27C | 109.5 |
C19—C18—C2 | 113.6 (3) | H27A—C27—H27C | 109.5 |
C19—C18—H18A | 108.9 | H27B—C27—H27C | 109.5 |
C2—C18—H18A | 108.9 | C29—C28—N5 | 115.6 (3) |
C19—C18—H18B | 108.9 | C29—C28—H28A | 108.4 |
C2—C18—H18B | 108.9 | N5—C28—H28A | 108.4 |
H18A—C18—H18B | 107.7 | C29—C28—H28B | 108.4 |
C18—C19—H19A | 109.5 | N5—C28—H28B | 108.4 |
C18—C19—H19B | 109.5 | H28A—C28—H28B | 107.4 |
H19A—C19—H19B | 109.5 | C28—C29—H29A | 109.5 |
C18—C19—H19C | 109.5 | C28—C29—H29B | 109.5 |
H19A—C19—H19C | 109.5 | H29A—C29—H29B | 109.5 |
H19B—C19—H19C | 109.5 | C28—C29—H29C | 109.5 |
C4—C20—H20A | 109.5 | H29A—C29—H29C | 109.5 |
C4—C20—H20B | 109.5 | H29B—C29—H29C | 109.5 |
O1—C1—C2—C3 | −179.1 (3) | O3—C5—N3—Mn | 175.7 (3) |
N1—C1—C2—C3 | −0.2 (5) | C4—C5—N3—Mn | −2.3 (4) |
O1—C1—C2—C16 | 57.1 (4) | C11—C6—N3—C5 | −167.2 (3) |
N1—C1—C2—C16 | −124.0 (3) | C7—C6—N3—C5 | 11.2 (5) |
O1—C1—C2—C18 | −59.4 (4) | C11—C6—N3—Mn | 13.3 (3) |
N1—C1—C2—C18 | 119.5 (3) | C7—C6—N3—Mn | −168.3 (3) |
C1—C2—C3—O2 | −177.8 (3) | O2—C3—N4—C4 | −4.7 (5) |
C16—C2—C3—O2 | −54.0 (4) | C2—C3—N4—C4 | 171.9 (3) |
C18—C2—C3—O2 | 62.2 (4) | O2—C3—N4—Mn | 153.3 (2) |
C1—C2—C3—N4 | 5.4 (5) | C2—C3—N4—Mn | −30.1 (4) |
C16—C2—C3—N4 | 129.3 (3) | C5—C4—N4—C3 | −175.0 (3) |
C18—C2—C3—N4 | −114.6 (3) | C20—C4—N4—C3 | −57.8 (4) |
N4—C4—C5—O3 | 168.2 (3) | C21—C4—N4—C3 | 69.2 (4) |
C20—C4—C5—O3 | 47.0 (5) | C5—C4—N4—Mn | 24.9 (3) |
C21—C4—C5—O3 | −72.1 (4) | C20—C4—N4—Mn | 142.2 (2) |
N4—C4—C5—N3 | −13.9 (4) | C21—C4—N4—Mn | −90.9 (3) |
C20—C4—C5—N3 | −135.1 (3) | C1—N1—Mn—O5 | 76.3 (3) |
C21—C4—C5—N3 | 105.9 (3) | C13—N1—Mn—O5 | −88.5 (2) |
C11—C6—C7—C8 | −0.5 (5) | C1—N1—Mn—N2 | −178.3 (3) |
N3—C6—C7—C8 | −178.8 (3) | C13—N1—Mn—N2 | 16.9 (2) |
C6—C7—C8—C9 | −0.6 (5) | C1—N1—Mn—N3 | −115.4 (3) |
C7—C8—C9—C10 | 0.9 (5) | C13—N1—Mn—N3 | 79.8 (3) |
C8—C9—C10—C11 | −0.2 (5) | C1—N1—Mn—N4 | −33.4 (3) |
C9—C10—C11—C6 | −0.9 (5) | C13—N1—Mn—N4 | 161.8 (2) |
C9—C10—C11—N2 | 177.0 (3) | C12—N2—Mn—O5 | 93.0 (2) |
N3—C6—C11—C10 | 179.8 (3) | C11—N2—Mn—O5 | −88.5 (2) |
C7—C6—C11—C10 | 1.2 (5) | C12—N2—Mn—N1 | −14.6 (2) |
N3—C6—C11—N2 | 1.5 (4) | C11—N2—Mn—N1 | 163.9 (2) |
C7—C6—C11—N2 | −177.0 (3) | C12—N2—Mn—N3 | −160.2 (2) |
O4—C12—C13—N1 | −175.0 (3) | C11—N2—Mn—N3 | 18.3 (2) |
N2—C12—C13—N1 | 4.2 (4) | C12—N2—Mn—N4 | −99.4 (3) |
O4—C12—C13—C14 | −55.3 (4) | C11—N2—Mn—N4 | 79.0 (3) |
N2—C12—C13—C14 | 124.0 (3) | C5—N3—Mn—O5 | −92.2 (2) |
O4—C12—C13—C15 | 65.4 (5) | C6—N3—Mn—O5 | 87.3 (2) |
N2—C12—C13—C15 | −115.3 (3) | C5—N3—Mn—N1 | 99.5 (3) |
C1—C2—C16—C17 | 61.3 (4) | C6—N3—Mn—N1 | −81.0 (3) |
C3—C2—C16—C17 | −69.8 (4) | C5—N3—Mn—N2 | 163.0 (2) |
C18—C2—C16—C17 | 176.2 (3) | C6—N3—Mn—N2 | −17.4 (2) |
C1—C2—C18—C19 | −63.9 (4) | C5—N3—Mn—N4 | 13.5 (2) |
C3—C2—C18—C19 | 65.0 (4) | C6—N3—Mn—N4 | −166.9 (2) |
C16—C2—C18—C19 | −179.7 (3) | C3—N4—Mn—O5 | −72.7 (3) |
O1—C1—N1—C13 | 4.0 (5) | C4—N4—Mn—O5 | 85.6 (2) |
C2—C1—N1—C13 | −174.9 (3) | C3—N4—Mn—N1 | 38.6 (3) |
O1—C1—N1—Mn | −161.0 (2) | C4—N4—Mn—N1 | −163.2 (2) |
C2—C1—N1—Mn | 20.1 (4) | C3—N4—Mn—N2 | 119.8 (3) |
C12—C13—N1—C1 | 177.7 (3) | C4—N4—Mn—N2 | −82.0 (3) |
C14—C13—N1—C1 | 61.2 (4) | C3—N4—Mn—N3 | 179.9 (3) |
C15—C13—N1—C1 | −65.3 (4) | C4—N4—Mn—N3 | −21.9 (2) |
C12—C13—N1—Mn | −15.9 (3) | C26—N5—C22—C23 | −175.3 (3) |
C14—C13—N1—Mn | −132.3 (2) | C28—N5—C22—C23 | −53.9 (4) |
C15—C13—N1—Mn | 101.1 (3) | C24—N5—C22—C23 | 63.8 (4) |
O4—C12—N2—C11 | 9.9 (5) | C22—N5—C24—C25 | 62.8 (4) |
C13—C12—N2—C11 | −169.4 (3) | C26—N5—C24—C25 | −55.2 (4) |
O4—C12—N2—Mn | −171.8 (3) | C28—N5—C24—C25 | −176.6 (3) |
C13—C12—N2—Mn | 9.0 (4) | C22—N5—C26—C27 | −175.1 (3) |
C10—C11—N2—C12 | −15.6 (5) | C28—N5—C26—C27 | 64.0 (4) |
C6—C11—N2—C12 | 162.5 (3) | C24—N5—C26—C27 | −54.2 (4) |
C10—C11—N2—Mn | 166.0 (3) | C22—N5—C28—C29 | −55.0 (4) |
C6—C11—N2—Mn | −15.9 (3) | C26—N5—C28—C29 | 63.1 (4) |
O3—C5—N3—C6 | −3.8 (5) | C24—N5—C28—C29 | −175.7 (3) |
C4—C5—N3—C6 | 178.2 (3) |
Experimental details
Crystal data | |
Chemical formula | (C8H20N)[Mn(C21H26N4O4)O] |
Mr | 599.65 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.2606 (11), 15.5269 (15), 17.7586 (17) |
β (°) | 96.024 (8) |
V (Å3) | 3087.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.47 |
Crystal size (mm) | 0.20 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur-3 kappa diffractometer with SapphireIII CCD |
Absorption correction | Numerical (X-RED; Stoe & Cie, 1997) |
Tmin, Tmax | 0.899, 0.960 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18232, 5454, 2197 |
Rint | 0.078 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.074, 0.82 |
No. of reflections | 5454 |
No. of parameters | 361 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.26 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Bergerhoff, 1996), PLATON (Spek, 2003).
N1—Mn | 1.872 (2) | N4—Mn | 1.882 (2) |
N2—Mn | 1.874 (2) | O5—Mn | 1.561 (2) |
N3—Mn | 1.879 (2) | ||
O5—Mn—N1 | 109.08 (10) | N2—Mn—N3 | 79.91 (12) |
O5—Mn—N2 | 107.12 (10) | O5—Mn—N4 | 107.30 (10) |
N1—Mn—N2 | 82.09 (12) | N1—Mn—N4 | 93.50 (12) |
O5—Mn—N3 | 108.91 (10) | N2—Mn—N4 | 144.80 (11) |
N1—Mn—N3 | 141.27 (11) | N3—Mn—N4 | 82.27 (12) |
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The title complex was prepared with the intention of testing a mechanism for oxygen-transfer discussed by e.g. Cavallo & Jacobsen (2003) as well as Linde et al. (1999) were the spin-state of the Mn-oxo species is supposed to dictate whether the reaction will proceed via a radical (from the triplet state) or metallacyclic intermediate (from the quintet-state). Since the title compound is isolated in a stable singlet-state it might be possible to selectively excite it to form either one or possibly both of these spin-states. Similar compounds have also been used as model complexes in the study of the water oxidizing enzyme, PSII (Weng et al., 2004). The oxidation state of the MnV atom was verified with bond valence calculations (Brown & Altermatt, 1985; Brown, 1996).