Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105039910/ta1508sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105039910/ta1508Isup2.hkl |
CCDC reference: 299614
The ligand H2Ldtb was prepared as follows. To a dichloromethane solution of 2-[bis-(2-pyridylmethyl)aminomethyl]-6-(2-pyridylmethyl)aminomethyl-4-methylphenol (Greatti et al., 2004) (3.4 g, 8 mmol), triethylamine (1.21 g, 12 mmol) and 2-chloromethyl-4, 6-di-tert-butylphenol (Sokolowski et al., 1997) (3.02 g, 12 mmol) were added. The resulting mixture was allowed to react for 24 h with stirring at room temperature. The product was extracted with aqueous NaHCO3 solution (8 × 50 ml). The organic layers were dried over Na2SO4, the solvent was removed under reduced pressure and a pale-yellow solid was obtained (4.65 g, 7.2 mmol, yield 90%). 1H NMR (Solvent?, δ, p.p.m.): 8.54, 7.61, 7.53, 7.15, 6.97, 6.84 (16H, aromatic H), 3.92, 3.85, 3.84, 3.80 (s, 12H, CH2), 2.23 (s, CH3), 1.42, 1.25 (s, tert-butyl). Complex (I) was prepared by adding Mn(OAc)2·4H2O (1.0 mmol) and NaOAc (1.0 mmol) to a methanolic solution of the ligand H2Ldtb (0.5 mmol) with stirring at 313 K for 20 min. The solution immediately turned dark red and then NaBPh4 (0.5 mmol) was added. After slow evaporation of the solvent, dark-red crystals of (I) suitable for X-ray analysis were isolated (yield 82%).
The crystals of (I) grew from the mother solution as large prisms, but they showed a poor diffraction capacity of the X-ray radiation. Thus, the number of observed reflections in the hkl file is small (44%), giving rise to the consistency values Rint = 0.0518 and Rσ = 0.1572. One tert-butyl group is disordered and its terminal C atoms have two alternative positions, with occupancy factors of 0.7 and 0.3. Some non-H atoms show abnormally high temperature factors, but all these atoms were refined with anisotropic displacement parameters, with a positive definite thermal tensor. This gives high Ueq(max)/Ueq(min) ratios for C and H atoms. H atoms were added in their calculated positions and included in the structure factor calculations, with C—H distances of 0.93–0.96 Å and Uiso(H) = 1.2Ueq(C), or 1.5Ueq(C) for methyl atoms. [Please check added text]
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: SET4 in CAD-4 EXPRESS; data reduction: HELENA (Spek, 1996); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Mn2(C42H49N5O2)(C2H3O2)2](C24H20B) | F(000) = 2532 |
Mr = 1203.04 | Dx = 1.244 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 16.492 (3) Å | Cell parameters from 25 reflections |
b = 16.804 (3) Å | θ = 9.9–13.2° |
c = 24.519 (5) Å | µ = 0.45 mm−1 |
β = 109.07 (3)° | T = 293 K |
V = 6422 (2) Å3 | Irregular block, dark red |
Z = 4 | 0.47 × 0.40 × 0.13 mm |
Enraf–Nonius CAD-4 diffractometer | 4980 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.052 |
Graphite monochromator | θmax = 25.0°, θmin = 2.4° |
ω/2θ scans | h = 0→19 |
Absorption correction: ψ scan (North et al., 1968) and PLATON (Spek, 2003) | k = −19→0 |
Tmin = 0.829, Tmax = 0.937 | l = −29→27 |
11638 measured reflections | 3 standard reflections every 200 reflections |
11223 independent reflections | intensity decay: 1% |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 0.86 | w = 1/[σ2(Fo2) + (0.058P)2] where P = (Fo2 + 2Fc2)/3 |
11223 reflections | (Δ/σ)max < 0.001 |
784 parameters | Δρmax = 0.24 e Å−3 |
90 restraints | Δρmin = −0.31 e Å−3 |
[Mn2(C42H49N5O2)(C2H3O2)2](C24H20B) | V = 6422 (2) Å3 |
Mr = 1203.04 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.492 (3) Å | µ = 0.45 mm−1 |
b = 16.804 (3) Å | T = 293 K |
c = 24.519 (5) Å | 0.47 × 0.40 × 0.13 mm |
β = 109.07 (3)° |
Enraf–Nonius CAD-4 diffractometer | 4980 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) and PLATON (Spek, 2003) | Rint = 0.052 |
Tmin = 0.829, Tmax = 0.937 | 3 standard reflections every 200 reflections |
11638 measured reflections | intensity decay: 1% |
11223 independent reflections |
R[F2 > 2σ(F2)] = 0.052 | 90 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 0.86 | Δρmax = 0.24 e Å−3 |
11223 reflections | Δρmin = −0.31 e Å−3 |
784 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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mn1 | 0.27664 (4) | 0.61150 (4) | 0.20730 (2) | 0.05025 (19) | |
Mn2 | 0.30020 (4) | 0.52920 (3) | 0.08379 (2) | 0.04344 (17) | |
N1 | 0.41081 (19) | 0.64542 (18) | 0.27223 (12) | 0.0486 (8) | |
C2 | 0.4785 (2) | 0.6233 (2) | 0.24811 (17) | 0.0590 (11) | |
H2A | 0.4740 | 0.5669 | 0.2391 | 0.071* | |
H2B | 0.5341 | 0.6325 | 0.2769 | 0.071* | |
C3 | 0.3163 (2) | 0.6943 (2) | 0.04364 (15) | 0.0478 (10) | |
H3A | 0.3179 | 0.7315 | 0.0138 | 0.057* | |
H3B | 0.2661 | 0.7064 | 0.0545 | 0.057* | |
N4 | 0.30862 (18) | 0.61064 (17) | 0.01991 (12) | 0.0430 (8) | |
O1 | 0.34056 (15) | 0.60673 (14) | 0.14322 (9) | 0.0445 (6) | |
C11 | 0.4731 (2) | 0.6697 (2) | 0.19422 (17) | 0.0492 (10) | |
C12 | 0.4024 (2) | 0.6607 (2) | 0.14401 (16) | 0.0442 (9) | |
C13 | 0.3952 (2) | 0.7049 (2) | 0.09510 (16) | 0.0452 (10) | |
C14 | 0.4607 (3) | 0.7569 (2) | 0.09551 (18) | 0.0555 (11) | |
H14 | 0.4553 | 0.7870 | 0.0627 | 0.067* | |
C15 | 0.5333 (3) | 0.7654 (3) | 0.1428 (2) | 0.0642 (12) | |
C16 | 0.5371 (3) | 0.7226 (3) | 0.19229 (19) | 0.0647 (12) | |
H16 | 0.5843 | 0.7297 | 0.2254 | 0.078* | |
C17 | 0.6070 (3) | 0.8189 (3) | 0.1413 (2) | 0.1016 (18) | |
H17A | 0.6520 | 0.8167 | 0.1780 | 0.152* | |
H17B | 0.5869 | 0.8727 | 0.1336 | 0.152* | |
H17C | 0.6288 | 0.8011 | 0.1116 | 0.152* | |
C20 | 0.4121 (3) | 0.7313 (2) | 0.28530 (17) | 0.0638 (12) | |
H20A | 0.4704 | 0.7507 | 0.2945 | 0.077* | |
H20B | 0.3950 | 0.7385 | 0.3193 | 0.077* | |
C21 | 0.3543 (3) | 0.7808 (3) | 0.23678 (19) | 0.0604 (12) | |
N22 | 0.2855 (2) | 0.7453 (2) | 0.20084 (15) | 0.0588 (9) | |
C23 | 0.2324 (3) | 0.7893 (3) | 0.1579 (2) | 0.0789 (14) | |
H23 | 0.1846 | 0.7644 | 0.1324 | 0.095* | |
C24 | 0.2444 (5) | 0.8669 (4) | 0.1499 (3) | 0.108 (2) | |
H24 | 0.2063 | 0.8945 | 0.1193 | 0.130* | |
C25 | 0.3128 (5) | 0.9041 (4) | 0.1871 (3) | 0.122 (2) | |
H25 | 0.3213 | 0.9582 | 0.1830 | 0.146* | |
C26 | 0.3703 (4) | 0.8612 (3) | 0.2314 (2) | 0.0954 (17) | |
H26 | 0.4184 | 0.8857 | 0.2569 | 0.114* | |
C30 | 0.4161 (3) | 0.5980 (2) | 0.32449 (16) | 0.0617 (12) | |
H30A | 0.4642 | 0.6164 | 0.3568 | 0.074* | |
H30B | 0.4259 | 0.5425 | 0.3177 | 0.074* | |
C31 | 0.3348 (3) | 0.6055 (2) | 0.33916 (17) | 0.0530 (10) | |
N32 | 0.2630 (2) | 0.61887 (19) | 0.29499 (13) | 0.0550 (9) | |
C33 | 0.1891 (3) | 0.6267 (2) | 0.30575 (19) | 0.0668 (13) | |
H33 | 0.1394 | 0.6370 | 0.2750 | 0.080* | |
C34 | 0.1832 (3) | 0.6202 (3) | 0.3603 (2) | 0.0748 (14) | |
H34 | 0.1308 | 0.6266 | 0.3665 | 0.090* | |
C35 | 0.2551 (4) | 0.6044 (3) | 0.4046 (2) | 0.0787 (15) | |
H35 | 0.2523 | 0.5981 | 0.4416 | 0.094* | |
C36 | 0.3330 (3) | 0.5975 (3) | 0.39530 (18) | 0.0706 (13) | |
H36 | 0.3831 | 0.5876 | 0.4258 | 0.085* | |
C40 | 0.3845 (2) | 0.5914 (2) | 0.00161 (15) | 0.0498 (10) | |
H40A | 0.3687 | 0.5506 | −0.0280 | 0.060* | |
H40B | 0.4012 | 0.6386 | −0.0150 | 0.060* | |
C41 | 0.4593 (3) | 0.5630 (2) | 0.05101 (16) | 0.0477 (10) | |
N42 | 0.4397 (2) | 0.51509 (19) | 0.08852 (14) | 0.0519 (8) | |
C43 | 0.5046 (3) | 0.4856 (3) | 0.13242 (19) | 0.0666 (12) | |
H43 | 0.4917 | 0.4517 | 0.1585 | 0.080* | |
C44 | 0.5889 (3) | 0.5030 (3) | 0.1407 (2) | 0.0782 (14) | |
H44 | 0.6322 | 0.4812 | 0.1716 | 0.094* | |
C45 | 0.6082 (3) | 0.5524 (3) | 0.1033 (2) | 0.0733 (14) | |
H45 | 0.6649 | 0.5660 | 0.1087 | 0.088* | |
C46 | 0.5431 (3) | 0.5825 (3) | 0.05712 (19) | 0.0652 (12) | |
H46 | 0.5555 | 0.6155 | 0.0304 | 0.078* | |
O50 | 0.26581 (17) | 0.45307 (14) | 0.02796 (10) | 0.0596 (8) | |
C50 | 0.2279 (2) | 0.6053 (2) | −0.03157 (15) | 0.0499 (10) | |
H50A | 0.1794 | 0.6189 | −0.0193 | 0.060* | |
H50B | 0.2310 | 0.6447 | −0.0597 | 0.060* | |
C51 | 0.2117 (2) | 0.5256 (2) | −0.06032 (16) | 0.0447 (9) | |
C52 | 0.2265 (2) | 0.4547 (2) | −0.02938 (15) | 0.0445 (10) | |
C53 | 0.2032 (2) | 0.3805 (2) | −0.05751 (17) | 0.0493 (10) | |
C54 | 0.1673 (2) | 0.3819 (2) | −0.11706 (17) | 0.0540 (11) | |
H54 | 0.1514 | 0.3337 | −0.1362 | 0.065* | |
C55 | 0.1536 (2) | 0.4512 (3) | −0.15000 (16) | 0.0542 (11) | |
C56 | 0.1754 (2) | 0.5229 (3) | −0.12065 (16) | 0.0537 (11) | |
H56 | 0.1657 | 0.5703 | −0.1415 | 0.064* | |
C531 | 0.2167 (3) | 0.3027 (2) | −0.02298 (17) | 0.0572 (11) | |
C532 | 0.3132 (3) | 0.2881 (2) | 0.00730 (19) | 0.0761 (14) | |
H53A | 0.3211 | 0.2394 | 0.0288 | 0.114* | |
H53B | 0.3371 | 0.3315 | 0.0331 | 0.114* | |
H53C | 0.3417 | 0.2845 | −0.0211 | 0.114* | |
C533 | 0.1717 (3) | 0.3068 (3) | 0.02343 (19) | 0.0810 (14) | |
H53D | 0.1807 | 0.2578 | 0.0446 | 0.121* | |
H53E | 0.1114 | 0.3153 | 0.0050 | 0.121* | |
H53F | 0.1953 | 0.3500 | 0.0494 | 0.121* | |
C534 | 0.1814 (3) | 0.2304 (3) | −0.06184 (19) | 0.0895 (15) | |
H53G | 0.1909 | 0.1831 | −0.0387 | 0.134* | |
H53H | 0.2102 | 0.2258 | −0.0900 | 0.134* | |
H53I | 0.1210 | 0.2373 | −0.0811 | 0.134* | |
C551 | 0.1147 (3) | 0.4477 (3) | −0.21623 (19) | 0.0791 (15) | |
C552 | 0.1726 (7) | 0.3937 (6) | −0.2386 (4) | 0.123 (4) | 0.70 |
H55A | 0.2282 | 0.4183 | −0.2271 | 0.184* | 0.70 |
H55B | 0.1488 | 0.3934 | −0.2800 | 0.184* | 0.70 |
H55C | 0.1780 | 0.3400 | −0.2245 | 0.184* | 0.70 |
C52' | 0.0803 (17) | 0.3659 (12) | −0.2373 (11) | 0.151 (11) | 0.30 |
H52A | 0.1265 | 0.3324 | −0.2390 | 0.226* | 0.30 |
H52B | 0.0384 | 0.3701 | −0.2751 | 0.226* | 0.30 |
H52C | 0.0541 | 0.3432 | −0.2112 | 0.226* | 0.30 |
C553 | 0.1150 (7) | 0.5291 (5) | −0.2453 (3) | 0.106 (3) | 0.70 |
H55D | 0.1693 | 0.5562 | −0.2336 | 0.159* | 0.70 |
H55E | 0.0741 | 0.5599 | −0.2341 | 0.159* | 0.70 |
H55F | 0.0952 | 0.5226 | −0.2865 | 0.159* | 0.70 |
C53' | 0.1783 (11) | 0.4601 (18) | −0.2457 (8) | 0.156 (13) | 0.30 |
H53J | 0.2275 | 0.4870 | −0.2202 | 0.234* | 0.30 |
H53K | 0.1535 | 0.4919 | −0.2796 | 0.234* | 0.30 |
H53L | 0.1955 | 0.4096 | −0.2566 | 0.234* | 0.30 |
C554 | 0.0284 (6) | 0.4089 (10) | −0.2334 (4) | 0.172 (7) | 0.70 |
H55G | −0.0119 | 0.4358 | −0.2192 | 0.258* | 0.70 |
H55H | 0.0361 | 0.3553 | −0.2192 | 0.258* | 0.70 |
H55I | 0.0072 | 0.4082 | −0.2749 | 0.258* | 0.70 |
C54' | 0.0331 (14) | 0.4992 (15) | −0.2303 (8) | 0.130 (9) | 0.30 |
H54A | 0.0488 | 0.5544 | −0.2259 | 0.195* | 0.30 |
H54B | 0.0022 | 0.4859 | −0.2045 | 0.195* | 0.30 |
H54C | −0.0027 | 0.4894 | −0.2693 | 0.195* | 0.30 |
O61 | 0.15018 (18) | 0.6007 (2) | 0.15520 (14) | 0.0888 (11) | |
O62 | 0.17113 (17) | 0.55955 (18) | 0.07484 (12) | 0.0728 (9) | |
C63 | 0.1258 (3) | 0.5770 (3) | 0.1042 (2) | 0.0711 (14) | |
C64 | 0.0301 (3) | 0.5663 (5) | 0.0764 (2) | 0.166 (3) | |
H64A | 0.0015 | 0.5817 | 0.1031 | 0.249* | |
H64B | 0.0178 | 0.5115 | 0.0659 | 0.249* | |
H64C | 0.0102 | 0.5989 | 0.0424 | 0.249* | |
O71 | 0.3040 (2) | 0.48752 (18) | 0.22284 (12) | 0.0734 (9) | |
O72 | 0.31458 (18) | 0.44148 (15) | 0.14036 (11) | 0.0631 (8) | |
C73 | 0.3159 (3) | 0.4345 (3) | 0.19154 (19) | 0.0527 (11) | |
C74 | 0.3335 (3) | 0.3508 (3) | 0.21483 (19) | 0.0885 (16) | |
H74A | 0.3413 | 0.3165 | 0.1856 | 0.133* | 0.50 |
H74B | 0.2859 | 0.3322 | 0.2257 | 0.133* | 0.50 |
H74C | 0.3846 | 0.3504 | 0.2480 | 0.133* | 0.50 |
H74D | 0.3332 | 0.3496 | 0.2539 | 0.133* | 0.50 |
H74E | 0.3886 | 0.3339 | 0.2138 | 0.133* | 0.50 |
H74F | 0.2900 | 0.3157 | 0.1916 | 0.133* | 0.50 |
B1 | 0.2225 (3) | 0.9234 (3) | −0.0696 (2) | 0.0544 (13) | |
C81 | 0.2997 (2) | 0.9689 (2) | −0.01888 (16) | 0.0475 (10) | |
C82 | 0.3369 (3) | 0.9339 (2) | 0.03574 (17) | 0.0565 (11) | |
H82 | 0.3122 | 0.8880 | 0.0445 | 0.068* | |
C83 | 0.4093 (3) | 0.9651 (3) | 0.07730 (18) | 0.0655 (12) | |
H83 | 0.4317 | 0.9397 | 0.1128 | 0.079* | |
C84 | 0.4476 (3) | 1.0327 (3) | 0.0665 (2) | 0.0663 (12) | |
H84 | 0.4969 | 1.0527 | 0.0937 | 0.080* | |
C85 | 0.4121 (3) | 1.0700 (3) | 0.0149 (2) | 0.0659 (12) | |
H85 | 0.4366 | 1.1167 | 0.0074 | 0.079* | |
C86 | 0.3393 (2) | 1.0392 (2) | −0.02690 (17) | 0.0568 (11) | |
H86 | 0.3163 | 1.0668 | −0.0614 | 0.068* | |
C91 | 0.2678 (3) | 0.8541 (2) | −0.09741 (17) | 0.0570 (11) | |
C92 | 0.2203 (3) | 0.8079 (3) | −0.1443 (2) | 0.0989 (18) | |
H92 | 0.1619 | 0.8180 | −0.1607 | 0.119* | |
C93 | 0.2564 (4) | 0.7473 (3) | −0.1680 (2) | 0.109 (2) | |
H93 | 0.2220 | 0.7179 | −0.1991 | 0.131* | |
C94 | 0.3418 (4) | 0.7311 (3) | −0.1453 (2) | 0.0966 (17) | |
H94 | 0.3661 | 0.6911 | −0.1611 | 0.116* | |
C95 | 0.3909 (3) | 0.7740 (3) | −0.0997 (2) | 0.0771 (14) | |
H95 | 0.4492 | 0.7632 | −0.0838 | 0.093* | |
C96 | 0.3543 (3) | 0.8341 (3) | −0.07655 (18) | 0.0633 (12) | |
H96 | 0.3896 | 0.8626 | −0.0453 | 0.076* | |
C101 | 0.1546 (3) | 0.8847 (3) | −0.04075 (19) | 0.0632 (12) | |
C102 | 0.1237 (3) | 0.9299 (3) | −0.0044 (2) | 0.0864 (15) | |
H102 | 0.1444 | 0.9816 | 0.0037 | 0.104* | |
C103 | 0.0640 (3) | 0.9038 (4) | 0.0208 (2) | 0.1055 (19) | |
H103 | 0.0449 | 0.9376 | 0.0441 | 0.127* | |
C104 | 0.0340 (4) | 0.8278 (5) | 0.0105 (3) | 0.125 (3) | |
H104 | −0.0053 | 0.8086 | 0.0273 | 0.150* | |
C105 | 0.0625 (4) | 0.7799 (4) | −0.0249 (3) | 0.128 (3) | |
H105 | 0.0421 | 0.7281 | −0.0323 | 0.154* | |
C106 | 0.1215 (3) | 0.8082 (3) | −0.0496 (2) | 0.0849 (16) | |
H106 | 0.1396 | 0.7743 | −0.0733 | 0.102* | |
C111 | 0.1738 (3) | 0.9877 (2) | −0.12023 (17) | 0.0544 (11) | |
C112 | 0.2079 (3) | 1.0117 (3) | −0.16212 (18) | 0.0738 (14) | |
H112 | 0.2579 | 0.9868 | −0.1630 | 0.089* | |
C113 | 0.1733 (4) | 1.0700 (3) | −0.2027 (2) | 0.0851 (15) | |
H113 | 0.2009 | 1.0845 | −0.2288 | 0.102* | |
C114 | 0.0990 (4) | 1.1059 (3) | −0.2046 (2) | 0.0844 (15) | |
H114 | 0.0741 | 1.1441 | −0.2324 | 0.101* | |
C115 | 0.0611 (3) | 1.0847 (3) | −0.1644 (2) | 0.0791 (14) | |
H115 | 0.0107 | 1.1094 | −0.1644 | 0.095* | |
C116 | 0.0980 (3) | 1.0268 (3) | −0.12433 (18) | 0.0624 (12) | |
H116 | 0.0703 | 1.0129 | −0.0982 | 0.075* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0486 (4) | 0.0591 (4) | 0.0448 (4) | −0.0044 (3) | 0.0177 (3) | −0.0043 (3) |
Mn2 | 0.0476 (4) | 0.0424 (4) | 0.0428 (3) | −0.0020 (3) | 0.0181 (3) | 0.0020 (3) |
N1 | 0.050 (2) | 0.048 (2) | 0.0448 (19) | −0.0028 (17) | 0.0115 (16) | 0.0038 (16) |
C2 | 0.046 (3) | 0.068 (3) | 0.060 (3) | −0.001 (2) | 0.014 (2) | 0.001 (2) |
C3 | 0.062 (3) | 0.038 (2) | 0.046 (2) | −0.001 (2) | 0.021 (2) | 0.0056 (19) |
N4 | 0.0432 (19) | 0.045 (2) | 0.0416 (18) | 0.0014 (17) | 0.0151 (15) | 0.0033 (16) |
O1 | 0.0471 (15) | 0.0444 (15) | 0.0445 (15) | −0.0117 (14) | 0.0183 (12) | −0.0023 (13) |
C11 | 0.043 (2) | 0.045 (3) | 0.062 (3) | −0.005 (2) | 0.020 (2) | 0.002 (2) |
C12 | 0.042 (2) | 0.042 (2) | 0.052 (2) | 0.000 (2) | 0.021 (2) | −0.003 (2) |
C13 | 0.051 (3) | 0.039 (2) | 0.049 (2) | −0.003 (2) | 0.020 (2) | 0.000 (2) |
C14 | 0.067 (3) | 0.046 (3) | 0.059 (3) | −0.006 (2) | 0.029 (2) | 0.007 (2) |
C15 | 0.063 (3) | 0.062 (3) | 0.077 (3) | −0.017 (3) | 0.035 (3) | −0.005 (3) |
C16 | 0.050 (3) | 0.072 (3) | 0.068 (3) | −0.016 (2) | 0.014 (2) | −0.013 (3) |
C17 | 0.084 (4) | 0.116 (4) | 0.114 (4) | −0.060 (3) | 0.044 (3) | −0.015 (4) |
C20 | 0.065 (3) | 0.066 (3) | 0.059 (3) | −0.014 (3) | 0.018 (2) | −0.008 (2) |
C21 | 0.074 (3) | 0.052 (3) | 0.063 (3) | 0.004 (3) | 0.033 (3) | 0.001 (2) |
N22 | 0.070 (2) | 0.056 (2) | 0.052 (2) | 0.015 (2) | 0.0227 (19) | 0.008 (2) |
C23 | 0.092 (4) | 0.084 (4) | 0.068 (3) | 0.031 (3) | 0.036 (3) | 0.010 (3) |
C24 | 0.134 (6) | 0.097 (6) | 0.101 (5) | 0.046 (5) | 0.048 (4) | 0.037 (4) |
C25 | 0.176 (8) | 0.059 (4) | 0.156 (7) | 0.026 (5) | 0.088 (6) | 0.038 (5) |
C26 | 0.114 (5) | 0.055 (4) | 0.120 (5) | −0.007 (3) | 0.042 (4) | 0.013 (3) |
C30 | 0.067 (3) | 0.066 (3) | 0.046 (2) | 0.006 (2) | 0.009 (2) | 0.008 (2) |
C31 | 0.073 (3) | 0.041 (2) | 0.046 (3) | −0.002 (2) | 0.022 (2) | 0.005 (2) |
N32 | 0.064 (2) | 0.055 (2) | 0.050 (2) | −0.004 (2) | 0.0239 (19) | −0.0016 (18) |
C33 | 0.073 (3) | 0.070 (3) | 0.065 (3) | −0.008 (3) | 0.033 (3) | −0.007 (2) |
C34 | 0.096 (4) | 0.072 (3) | 0.075 (3) | 0.000 (3) | 0.053 (3) | −0.007 (3) |
C35 | 0.124 (5) | 0.065 (3) | 0.060 (3) | −0.011 (3) | 0.047 (3) | −0.007 (3) |
C36 | 0.093 (4) | 0.066 (3) | 0.049 (3) | 0.000 (3) | 0.018 (3) | 0.010 (2) |
C40 | 0.051 (3) | 0.056 (3) | 0.047 (2) | −0.004 (2) | 0.021 (2) | 0.001 (2) |
C41 | 0.053 (3) | 0.044 (2) | 0.053 (3) | 0.001 (2) | 0.027 (2) | −0.002 (2) |
N42 | 0.049 (2) | 0.053 (2) | 0.057 (2) | 0.0125 (18) | 0.0211 (18) | 0.0096 (18) |
C43 | 0.067 (3) | 0.067 (3) | 0.069 (3) | 0.016 (3) | 0.027 (3) | 0.016 (3) |
C44 | 0.057 (3) | 0.095 (4) | 0.076 (3) | 0.025 (3) | 0.013 (3) | 0.010 (3) |
C45 | 0.048 (3) | 0.091 (4) | 0.084 (4) | 0.008 (3) | 0.026 (3) | −0.010 (3) |
C46 | 0.059 (3) | 0.076 (3) | 0.074 (3) | −0.004 (3) | 0.039 (3) | −0.004 (3) |
O50 | 0.090 (2) | 0.0441 (17) | 0.0418 (16) | −0.0079 (15) | 0.0171 (15) | −0.0009 (13) |
C50 | 0.048 (2) | 0.050 (3) | 0.047 (2) | 0.010 (2) | 0.009 (2) | 0.004 (2) |
C51 | 0.040 (2) | 0.050 (3) | 0.045 (2) | 0.005 (2) | 0.0149 (19) | 0.003 (2) |
C52 | 0.046 (2) | 0.054 (3) | 0.034 (2) | −0.006 (2) | 0.0147 (19) | −0.003 (2) |
C53 | 0.040 (2) | 0.058 (3) | 0.054 (3) | −0.009 (2) | 0.021 (2) | −0.006 (2) |
C54 | 0.051 (3) | 0.056 (3) | 0.053 (3) | −0.010 (2) | 0.015 (2) | −0.012 (2) |
C55 | 0.036 (2) | 0.075 (3) | 0.045 (2) | −0.006 (2) | 0.0052 (19) | −0.006 (2) |
C56 | 0.045 (2) | 0.069 (3) | 0.049 (3) | 0.005 (2) | 0.017 (2) | 0.006 (2) |
C531 | 0.065 (3) | 0.046 (3) | 0.062 (3) | −0.011 (2) | 0.022 (2) | −0.004 (2) |
C532 | 0.078 (3) | 0.056 (3) | 0.094 (4) | 0.005 (3) | 0.028 (3) | 0.012 (3) |
C533 | 0.095 (4) | 0.074 (3) | 0.092 (3) | −0.018 (3) | 0.055 (3) | 0.009 (3) |
C534 | 0.111 (4) | 0.065 (3) | 0.090 (4) | −0.021 (3) | 0.028 (3) | −0.016 (3) |
C551 | 0.078 (4) | 0.099 (4) | 0.048 (3) | −0.006 (3) | 0.005 (3) | −0.010 (3) |
C552 | 0.155 (10) | 0.152 (9) | 0.064 (6) | −0.034 (8) | 0.040 (6) | −0.014 (7) |
C52' | 0.13 (2) | 0.26 (3) | 0.074 (14) | −0.08 (2) | 0.041 (18) | −0.042 (17) |
C553 | 0.113 (8) | 0.145 (9) | 0.045 (4) | −0.024 (6) | 0.006 (5) | 0.011 (5) |
C53' | 0.096 (17) | 0.34 (4) | 0.028 (9) | −0.09 (2) | 0.016 (10) | 0.02 (2) |
C554 | 0.074 (8) | 0.36 (2) | 0.058 (6) | −0.128 (11) | −0.006 (6) | −0.034 (10) |
C54' | 0.126 (19) | 0.150 (19) | 0.057 (12) | 0.025 (17) | −0.047 (13) | −0.012 (13) |
O61 | 0.0505 (19) | 0.143 (3) | 0.070 (2) | −0.005 (2) | 0.0144 (17) | −0.026 (2) |
O62 | 0.0433 (18) | 0.103 (2) | 0.075 (2) | −0.0026 (17) | 0.0233 (16) | −0.0029 (18) |
C63 | 0.039 (3) | 0.102 (4) | 0.068 (3) | −0.002 (3) | 0.011 (3) | −0.002 (3) |
C64 | 0.047 (3) | 0.351 (11) | 0.094 (4) | −0.022 (5) | 0.015 (3) | −0.075 (6) |
O71 | 0.116 (3) | 0.055 (2) | 0.065 (2) | −0.0064 (18) | 0.0508 (19) | −0.0006 (16) |
O72 | 0.100 (2) | 0.0471 (17) | 0.0468 (17) | −0.0075 (16) | 0.0302 (16) | 0.0049 (14) |
C73 | 0.056 (3) | 0.044 (3) | 0.060 (3) | −0.011 (2) | 0.020 (2) | 0.008 (2) |
C74 | 0.132 (5) | 0.066 (3) | 0.076 (3) | −0.010 (3) | 0.047 (3) | 0.009 (3) |
B1 | 0.046 (3) | 0.052 (3) | 0.060 (3) | −0.009 (2) | 0.009 (3) | −0.007 (3) |
C81 | 0.047 (2) | 0.043 (2) | 0.055 (3) | −0.002 (2) | 0.020 (2) | −0.006 (2) |
C82 | 0.058 (3) | 0.053 (3) | 0.056 (3) | −0.004 (2) | 0.016 (2) | 0.000 (2) |
C83 | 0.069 (3) | 0.067 (3) | 0.056 (3) | 0.007 (3) | 0.014 (2) | −0.005 (3) |
C84 | 0.055 (3) | 0.073 (3) | 0.068 (3) | −0.008 (3) | 0.016 (2) | −0.013 (3) |
C85 | 0.058 (3) | 0.067 (3) | 0.077 (3) | −0.022 (3) | 0.029 (3) | −0.014 (3) |
C86 | 0.053 (3) | 0.061 (3) | 0.058 (3) | −0.002 (2) | 0.020 (2) | −0.004 (2) |
C91 | 0.061 (3) | 0.051 (3) | 0.053 (3) | −0.001 (2) | 0.010 (2) | 0.002 (2) |
C92 | 0.090 (4) | 0.089 (4) | 0.088 (4) | 0.023 (3) | −0.011 (3) | −0.023 (3) |
C93 | 0.139 (6) | 0.078 (4) | 0.080 (4) | 0.026 (4) | −0.004 (4) | −0.034 (3) |
C94 | 0.133 (5) | 0.074 (4) | 0.085 (4) | 0.037 (4) | 0.038 (4) | −0.003 (3) |
C95 | 0.082 (4) | 0.086 (4) | 0.067 (3) | 0.012 (3) | 0.029 (3) | −0.004 (3) |
C96 | 0.065 (3) | 0.067 (3) | 0.061 (3) | −0.001 (3) | 0.024 (3) | −0.006 (2) |
C101 | 0.046 (3) | 0.068 (3) | 0.067 (3) | −0.002 (3) | 0.006 (2) | 0.009 (3) |
C102 | 0.064 (3) | 0.112 (4) | 0.086 (4) | −0.027 (3) | 0.029 (3) | −0.002 (3) |
C103 | 0.073 (4) | 0.148 (6) | 0.105 (4) | −0.016 (4) | 0.042 (3) | 0.015 (4) |
C104 | 0.058 (4) | 0.153 (8) | 0.166 (7) | −0.008 (5) | 0.037 (4) | 0.064 (6) |
C105 | 0.062 (4) | 0.087 (5) | 0.226 (8) | −0.013 (4) | 0.035 (5) | 0.065 (5) |
C106 | 0.051 (3) | 0.059 (3) | 0.135 (5) | 0.000 (3) | 0.017 (3) | 0.018 (3) |
C111 | 0.050 (3) | 0.054 (3) | 0.057 (3) | −0.010 (2) | 0.013 (2) | −0.010 (2) |
C112 | 0.073 (3) | 0.095 (4) | 0.053 (3) | 0.014 (3) | 0.020 (3) | 0.013 (3) |
C113 | 0.083 (4) | 0.102 (4) | 0.064 (3) | 0.001 (3) | 0.016 (3) | 0.012 (3) |
C114 | 0.092 (4) | 0.072 (4) | 0.069 (3) | 0.001 (3) | −0.001 (3) | 0.007 (3) |
C115 | 0.064 (3) | 0.065 (3) | 0.096 (4) | 0.009 (3) | 0.010 (3) | −0.008 (3) |
C116 | 0.054 (3) | 0.059 (3) | 0.070 (3) | −0.007 (3) | 0.015 (2) | 0.007 (3) |
Mn1—O61 | 2.067 (3) | C532—H53C | 0.9600 |
Mn1—O71 | 2.139 (3) | C533—H53D | 0.9600 |
Mn1—O1 | 2.161 (2) | C533—H53E | 0.9600 |
Mn1—N32 | 2.237 (3) | C533—H53F | 0.9600 |
Mn1—N22 | 2.262 (4) | C534—H53G | 0.9600 |
Mn1—N1 | 2.335 (3) | C534—H53H | 0.9600 |
Mn2—O50 | 1.823 (2) | C534—H53I | 0.9600 |
Mn2—O1 | 1.905 (2) | C551—C53' | 1.470 (12) |
Mn2—O72 | 1.984 (3) | C551—C554 | 1.494 (8) |
Mn2—N4 | 2.118 (3) | C551—C52' | 1.512 (14) |
Mn2—O62 | 2.129 (3) | C551—C54' | 1.542 (13) |
Mn2—N42 | 2.278 (3) | C551—C552 | 1.543 (9) |
N1—C2 | 1.472 (4) | C551—C553 | 1.545 (8) |
N1—C20 | 1.477 (5) | C552—H55A | 0.9600 |
N1—C30 | 1.487 (4) | C552—H55B | 0.9600 |
C2—C11 | 1.511 (5) | C552—H55C | 0.9600 |
C2—H2A | 0.9700 | C52'—H52A | 0.9600 |
C2—H2B | 0.9700 | C52'—H52B | 0.9600 |
C3—C13 | 1.499 (5) | C52'—H52C | 0.9600 |
C3—N4 | 1.511 (4) | C553—H55D | 0.9600 |
C3—H3A | 0.9700 | C553—H55E | 0.9600 |
C3—H3B | 0.9700 | C553—H55F | 0.9600 |
N4—C40 | 1.497 (4) | C53'—H53J | 0.9600 |
N4—C50 | 1.508 (4) | C53'—H53K | 0.9600 |
O1—C12 | 1.360 (4) | C53'—H53L | 0.9600 |
C11—C16 | 1.394 (5) | C554—H55G | 0.9600 |
C11—C12 | 1.399 (5) | C554—H55H | 0.9600 |
C12—C13 | 1.383 (5) | C554—H55I | 0.9600 |
C13—C14 | 1.386 (5) | C54'—H54A | 0.9600 |
C14—C15 | 1.376 (5) | C54'—H54B | 0.9600 |
C14—H14 | 0.9300 | C54'—H54C | 0.9600 |
C15—C16 | 1.394 (5) | O61—C63 | 1.248 (5) |
C15—C17 | 1.523 (5) | O62—C63 | 1.230 (5) |
C16—H16 | 0.9300 | C63—C64 | 1.512 (6) |
C17—H17A | 0.9600 | C64—H64A | 0.9600 |
C17—H17B | 0.9600 | C64—H64B | 0.9600 |
C17—H17C | 0.9600 | C64—H64C | 0.9600 |
C20—C21 | 1.508 (5) | O71—C73 | 1.232 (4) |
C20—H20A | 0.9700 | O72—C73 | 1.254 (4) |
C20—H20B | 0.9700 | C73—C74 | 1.511 (5) |
C21—N22 | 1.328 (5) | C74—H74A | 0.9600 |
C21—C26 | 1.392 (6) | C74—H74B | 0.9600 |
N22—C23 | 1.348 (5) | C74—H74C | 0.9600 |
C23—C24 | 1.344 (7) | C74—H74D | 0.9600 |
C23—H23 | 0.9300 | C74—H74E | 0.9600 |
C24—C25 | 1.349 (8) | C74—H74F | 0.9600 |
C24—H24 | 0.9300 | B1—C101 | 1.641 (6) |
C25—C26 | 1.389 (7) | B1—C111 | 1.643 (6) |
C25—H25 | 0.9300 | B1—C81 | 1.648 (6) |
C26—H26 | 0.9300 | B1—C91 | 1.649 (6) |
C30—C31 | 1.504 (5) | C81—C86 | 1.395 (5) |
C30—H30A | 0.9700 | C81—C82 | 1.407 (5) |
C30—H30B | 0.9700 | C82—C83 | 1.394 (5) |
C31—N32 | 1.336 (5) | C82—H82 | 0.9300 |
C31—C36 | 1.393 (5) | C83—C84 | 1.367 (5) |
N32—C33 | 1.335 (5) | C83—H83 | 0.9300 |
C33—C34 | 1.377 (6) | C84—C85 | 1.360 (5) |
C33—H33 | 0.9300 | C84—H84 | 0.9300 |
C34—C35 | 1.347 (6) | C85—C86 | 1.398 (5) |
C34—H34 | 0.9300 | C85—H85 | 0.9300 |
C35—C36 | 1.380 (6) | C86—H86 | 0.9300 |
C35—H35 | 0.9300 | C91—C96 | 1.389 (5) |
C36—H36 | 0.9300 | C91—C92 | 1.397 (5) |
C40—C41 | 1.497 (5) | C92—C93 | 1.397 (6) |
C40—H40A | 0.9700 | C92—H92 | 0.9300 |
C40—H40B | 0.9700 | C93—C94 | 1.362 (6) |
C41—N42 | 1.339 (4) | C93—H93 | 0.9300 |
C41—C46 | 1.380 (5) | C94—C95 | 1.355 (6) |
N42—C43 | 1.340 (5) | C94—H94 | 0.9300 |
C43—C44 | 1.370 (6) | C95—C96 | 1.390 (5) |
C43—H43 | 0.9300 | C95—H95 | 0.9300 |
C44—C45 | 1.350 (6) | C96—H96 | 0.9300 |
C44—H44 | 0.9300 | C101—C106 | 1.386 (6) |
C45—C46 | 1.376 (5) | C101—C102 | 1.388 (6) |
C45—H45 | 0.9300 | C102—C103 | 1.393 (6) |
C46—H46 | 0.9300 | C102—H102 | 0.9300 |
O50—C52 | 1.342 (4) | C103—C104 | 1.364 (8) |
C50—C51 | 1.496 (5) | C103—H103 | 0.9300 |
C50—H50A | 0.9700 | C104—C105 | 1.375 (9) |
C50—H50B | 0.9700 | C104—H104 | 0.9300 |
C51—C52 | 1.391 (5) | C105—C106 | 1.388 (7) |
C51—C56 | 1.404 (5) | C105—H105 | 0.9300 |
C52—C53 | 1.415 (5) | C106—H106 | 0.9300 |
C53—C54 | 1.385 (5) | C111—C112 | 1.383 (5) |
C53—C531 | 1.534 (5) | C111—C116 | 1.387 (5) |
C54—C55 | 1.393 (5) | C112—C113 | 1.380 (6) |
C54—H54 | 0.9300 | C112—H112 | 0.9300 |
C55—C56 | 1.389 (5) | C113—C114 | 1.354 (6) |
C55—C551 | 1.540 (6) | C113—H113 | 0.9300 |
C56—H56 | 0.9300 | C114—C115 | 1.374 (6) |
C531—C534 | 1.536 (5) | C114—H114 | 0.9300 |
C531—C532 | 1.540 (5) | C115—C116 | 1.376 (6) |
C531—C533 | 1.550 (5) | C115—H115 | 0.9300 |
C532—H53A | 0.9600 | C116—H116 | 0.9300 |
C532—H53B | 0.9600 | ||
O61—Mn1—O71 | 97.80 (13) | C534—C531—C532 | 107.2 (4) |
O61—Mn1—O1 | 100.42 (11) | C53—C531—C533 | 110.4 (3) |
O71—Mn1—O1 | 88.22 (10) | C534—C531—C533 | 108.4 (3) |
O61—Mn1—N32 | 101.59 (13) | C532—C531—C533 | 108.7 (3) |
O71—Mn1—N32 | 87.95 (11) | C531—C532—H53A | 109.5 |
O1—Mn1—N32 | 157.97 (11) | C531—C532—H53B | 109.5 |
O61—Mn1—N22 | 96.88 (14) | H53A—C532—H53B | 109.5 |
O71—Mn1—N22 | 164.95 (13) | C531—C532—H53C | 109.5 |
O1—Mn1—N22 | 85.85 (10) | H53A—C532—H53C | 109.5 |
N32—Mn1—N22 | 92.38 (12) | H53B—C532—H53C | 109.5 |
O61—Mn1—N1 | 169.30 (13) | C531—C533—H53D | 109.5 |
O71—Mn1—N1 | 91.08 (11) | C531—C533—H53E | 109.5 |
O1—Mn1—N1 | 85.76 (10) | H53D—C533—H53E | 109.5 |
N32—Mn1—N1 | 72.64 (12) | C531—C533—H53F | 109.5 |
N22—Mn1—N1 | 74.71 (13) | H53D—C533—H53F | 109.5 |
O50—Mn2—O1 | 177.69 (12) | H53E—C533—H53F | 109.5 |
O50—Mn2—O72 | 86.59 (11) | C531—C534—H53G | 109.5 |
O1—Mn2—O72 | 92.36 (10) | C531—C534—H53H | 109.5 |
O50—Mn2—N4 | 88.71 (11) | H53G—C534—H53H | 109.5 |
O1—Mn2—N4 | 91.88 (11) | C531—C534—H53I | 109.5 |
O72—Mn2—N4 | 167.14 (12) | H53G—C534—H53I | 109.5 |
O50—Mn2—O62 | 92.03 (12) | H53H—C534—H53I | 109.5 |
O1—Mn2—O62 | 90.15 (11) | C53'—C551—C554 | 133.6 (10) |
O72—Mn2—O62 | 97.88 (12) | C53'—C551—C52' | 102.1 (12) |
N4—Mn2—O62 | 94.24 (11) | C53'—C551—C55 | 113.2 (9) |
O50—Mn2—N42 | 91.52 (12) | C554—C551—C55 | 110.2 (5) |
O1—Mn2—N42 | 86.42 (11) | C52'—C551—C55 | 112.1 (11) |
O72—Mn2—N42 | 89.94 (12) | C53'—C551—C54' | 121.4 (11) |
N4—Mn2—N42 | 78.22 (12) | C52'—C551—C54' | 103.4 (11) |
O62—Mn2—N42 | 171.59 (12) | C55—C551—C54' | 104.3 (7) |
C2—N1—C20 | 112.0 (3) | C554—C551—C552 | 106.6 (8) |
C2—N1—C30 | 111.8 (3) | C55—C551—C552 | 107.7 (5) |
C20—N1—C30 | 110.1 (3) | C54'—C551—C552 | 148.0 (8) |
C2—N1—Mn1 | 109.8 (2) | C554—C551—C553 | 113.8 (7) |
C20—N1—Mn1 | 109.3 (2) | C52'—C551—C553 | 134.9 (11) |
C30—N1—Mn1 | 103.4 (2) | C55—C551—C553 | 112.9 (4) |
N1—C2—C11 | 112.6 (3) | C552—C551—C553 | 105.1 (6) |
N1—C2—H2A | 109.1 | C551—C552—H55A | 106.6 |
C11—C2—H2A | 109.1 | C551—C552—H55B | 106.9 |
N1—C2—H2B | 109.1 | H55A—C552—H55B | 109.5 |
C11—C2—H2B | 109.1 | C551—C552—H55C | 114.8 |
H2A—C2—H2B | 107.8 | H55A—C552—H55C | 109.5 |
C13—C3—N4 | 112.0 (3) | H55B—C552—H55C | 109.5 |
C13—C3—H3A | 109.2 | C551—C52'—H52A | 109.5 |
N4—C3—H3A | 109.2 | C551—C52'—H52B | 109.5 |
C13—C3—H3B | 109.2 | H52A—C52'—H52B | 109.5 |
N4—C3—H3B | 109.2 | C551—C52'—H52C | 109.5 |
H3A—C3—H3B | 107.9 | H52A—C52'—H52C | 109.5 |
C40—N4—C50 | 109.4 (3) | H52B—C52'—H52C | 109.5 |
C40—N4—C3 | 110.1 (3) | C551—C553—H55D | 115.2 |
C50—N4—C3 | 108.5 (3) | C551—C553—H55E | 103.6 |
C40—N4—Mn2 | 110.2 (2) | H55D—C553—H55E | 109.5 |
C50—N4—Mn2 | 109.1 (2) | C551—C553—H55F | 109.5 |
C3—N4—Mn2 | 109.5 (2) | H55D—C553—H55F | 109.5 |
C12—O1—Mn2 | 122.6 (2) | H55E—C553—H55F | 109.5 |
C12—O1—Mn1 | 120.5 (2) | C551—C53'—H53J | 109.5 |
Mn2—O1—Mn1 | 116.74 (11) | C551—C53'—H53K | 109.5 |
C16—C11—C12 | 117.5 (4) | H53J—C53'—H53K | 109.5 |
C16—C11—C2 | 122.0 (4) | C551—C53'—H53L | 109.5 |
C12—C11—C2 | 120.5 (3) | H53J—C53'—H53L | 109.5 |
O1—C12—C13 | 119.6 (3) | H53K—C53'—H53L | 109.5 |
O1—C12—C11 | 119.3 (3) | C551—C554—H55G | 113.7 |
C13—C12—C11 | 121.0 (4) | C551—C554—H55H | 107.9 |
C12—C13—C14 | 119.1 (4) | H55G—C554—H55H | 109.5 |
C12—C13—C3 | 118.1 (3) | C551—C554—H55I | 106.8 |
C14—C13—C3 | 122.8 (3) | H55G—C554—H55I | 109.5 |
C15—C14—C13 | 122.2 (4) | H55H—C554—H55I | 109.5 |
C15—C14—H14 | 118.9 | C551—C54'—H54A | 109.5 |
C13—C14—H14 | 118.9 | C551—C54'—H54B | 109.5 |
C14—C15—C16 | 117.4 (4) | H54A—C54'—H54B | 109.5 |
C14—C15—C17 | 121.6 (4) | C551—C54'—H54C | 109.5 |
C16—C15—C17 | 121.1 (4) | H54A—C54'—H54C | 109.5 |
C15—C16—C11 | 122.6 (4) | H54B—C54'—H54C | 109.5 |
C15—C16—H16 | 118.7 | C63—O61—Mn1 | 125.3 (3) |
C11—C16—H16 | 118.7 | C63—O62—Mn2 | 140.8 (3) |
C15—C17—H17A | 109.5 | O62—C63—O61 | 127.2 (4) |
C15—C17—H17B | 109.5 | O62—C63—C64 | 116.9 (4) |
H17A—C17—H17B | 109.5 | O61—C63—C64 | 115.9 (4) |
C15—C17—H17C | 109.5 | C63—C64—H64A | 109.5 |
H17A—C17—H17C | 109.5 | C63—C64—H64B | 109.5 |
H17B—C17—H17C | 109.5 | H64A—C64—H64B | 109.5 |
N1—C20—C21 | 114.0 (3) | C63—C64—H64C | 109.5 |
N1—C20—H20A | 108.7 | H64A—C64—H64C | 109.5 |
C21—C20—H20A | 108.7 | H64B—C64—H64C | 109.5 |
N1—C20—H20B | 108.7 | C73—O71—Mn1 | 131.3 (3) |
C21—C20—H20B | 108.7 | C73—O72—Mn2 | 136.7 (3) |
H20A—C20—H20B | 107.6 | O71—C73—O72 | 127.0 (4) |
N22—C21—C26 | 121.4 (4) | O71—C73—C74 | 119.2 (4) |
N22—C21—C20 | 117.3 (4) | O72—C73—C74 | 113.8 (4) |
C26—C21—C20 | 121.3 (5) | C73—C74—H74A | 109.5 |
C21—N22—C23 | 117.9 (4) | C73—C74—H74B | 109.5 |
C21—N22—Mn1 | 117.4 (3) | H74A—C74—H74B | 109.5 |
C23—N22—Mn1 | 124.0 (4) | C73—C74—H74C | 109.5 |
C24—C23—N22 | 123.9 (5) | H74A—C74—H74C | 109.5 |
C24—C23—H23 | 118.1 | H74B—C74—H74C | 109.5 |
N22—C23—H23 | 118.1 | C73—C74—H74D | 109.5 |
C23—C24—C25 | 118.8 (6) | C73—C74—H74E | 109.5 |
C23—C24—H24 | 120.6 | H74D—C74—H74E | 109.5 |
C25—C24—H24 | 120.6 | C73—C74—H74F | 109.5 |
C24—C25—C26 | 119.7 (6) | H74D—C74—H74F | 109.5 |
C24—C25—H25 | 120.2 | H74E—C74—H74F | 109.5 |
C26—C25—H25 | 120.2 | C101—B1—C111 | 110.6 (3) |
C25—C26—C21 | 118.4 (5) | C101—B1—C81 | 109.1 (3) |
C25—C26—H26 | 120.8 | C111—B1—C81 | 109.4 (3) |
C21—C26—H26 | 120.8 | C101—B1—C91 | 111.3 (4) |
N1—C30—C31 | 110.8 (3) | C111—B1—C91 | 109.1 (3) |
N1—C30—H30A | 109.5 | C81—B1—C91 | 107.3 (3) |
C31—C30—H30A | 109.5 | C86—C81—C82 | 114.2 (4) |
N1—C30—H30B | 109.5 | C86—C81—B1 | 124.6 (4) |
C31—C30—H30B | 109.5 | C82—C81—B1 | 120.9 (4) |
H30A—C30—H30B | 108.1 | C83—C82—C81 | 122.8 (4) |
N32—C31—C36 | 121.2 (4) | C83—C82—H82 | 118.6 |
N32—C31—C30 | 116.3 (3) | C81—C82—H82 | 118.6 |
C36—C31—C30 | 122.5 (4) | C84—C83—C82 | 120.7 (4) |
C33—N32—C31 | 118.7 (4) | C84—C83—H83 | 119.7 |
C33—N32—Mn1 | 125.5 (3) | C82—C83—H83 | 119.7 |
C31—N32—Mn1 | 115.4 (3) | C85—C84—C83 | 118.5 (4) |
N32—C33—C34 | 122.9 (4) | C85—C84—H84 | 120.8 |
N32—C33—H33 | 118.6 | C83—C84—H84 | 120.8 |
C34—C33—H33 | 118.6 | C84—C85—C86 | 121.2 (4) |
C35—C34—C33 | 118.4 (5) | C84—C85—H85 | 119.4 |
C35—C34—H34 | 120.8 | C86—C85—H85 | 119.4 |
C33—C34—H34 | 120.8 | C81—C86—C85 | 122.6 (4) |
C34—C35—C36 | 120.4 (4) | C81—C86—H86 | 118.7 |
C34—C35—H35 | 119.8 | C85—C86—H86 | 118.7 |
C36—C35—H35 | 119.8 | C96—C91—C92 | 113.6 (4) |
C35—C36—C31 | 118.4 (4) | C96—C91—B1 | 124.6 (4) |
C35—C36—H36 | 120.8 | C92—C91—B1 | 121.7 (4) |
C31—C36—H36 | 120.8 | C93—C92—C91 | 123.2 (5) |
C41—C40—N4 | 112.0 (3) | C93—C92—H92 | 118.4 |
C41—C40—H40A | 109.2 | C91—C92—H92 | 118.4 |
N4—C40—H40A | 109.2 | C94—C93—C92 | 120.0 (5) |
C41—C40—H40B | 109.2 | C94—C93—H93 | 120.0 |
N4—C40—H40B | 109.2 | C92—C93—H93 | 120.0 |
H40A—C40—H40B | 107.9 | C95—C94—C93 | 119.4 (5) |
N42—C41—C46 | 121.7 (4) | C95—C94—H94 | 120.3 |
N42—C41—C40 | 115.3 (3) | C93—C94—H94 | 120.3 |
C46—C41—C40 | 122.9 (4) | C94—C95—C96 | 120.0 (5) |
C41—N42—C43 | 117.7 (4) | C94—C95—H95 | 120.0 |
C41—N42—Mn2 | 111.7 (3) | C96—C95—H95 | 120.0 |
C43—N42—Mn2 | 127.4 (3) | C91—C96—C95 | 123.8 (4) |
N42—C43—C44 | 123.0 (4) | C91—C96—H96 | 118.1 |
N42—C43—H43 | 118.5 | C95—C96—H96 | 118.1 |
C44—C43—H43 | 118.5 | C106—C101—C102 | 113.6 (5) |
C45—C44—C43 | 118.9 (4) | C106—C101—B1 | 126.1 (5) |
C45—C44—H44 | 120.5 | C102—C101—B1 | 120.3 (4) |
C43—C44—H44 | 120.5 | C101—C102—C103 | 125.0 (5) |
C44—C45—C46 | 119.5 (4) | C101—C102—H102 | 117.5 |
C44—C45—H45 | 120.3 | C103—C102—H102 | 117.5 |
C46—C45—H45 | 120.3 | C104—C103—C102 | 118.7 (6) |
C45—C46—C41 | 119.1 (4) | C104—C103—H103 | 120.7 |
C45—C46—H46 | 120.5 | C102—C103—H103 | 120.7 |
C41—C46—H46 | 120.5 | C103—C104—C105 | 119.1 (6) |
C52—O50—Mn2 | 134.2 (2) | C103—C104—H104 | 120.4 |
C51—C50—N4 | 114.9 (3) | C105—C104—H104 | 120.4 |
C51—C50—H50A | 108.6 | C104—C105—C106 | 120.6 (6) |
N4—C50—H50A | 108.6 | C104—C105—H105 | 119.7 |
C51—C50—H50B | 108.6 | C106—C105—H105 | 119.7 |
N4—C50—H50B | 108.6 | C101—C106—C105 | 123.1 (6) |
H50A—C50—H50B | 107.5 | C101—C106—H106 | 118.5 |
C52—C51—C56 | 119.1 (4) | C105—C106—H106 | 118.5 |
C52—C51—C50 | 122.5 (3) | C112—C111—C116 | 112.6 (4) |
C56—C51—C50 | 118.3 (4) | C112—C111—B1 | 122.5 (4) |
O50—C52—C51 | 121.8 (3) | C116—C111—B1 | 124.9 (4) |
O50—C52—C53 | 117.0 (3) | C113—C112—C111 | 124.8 (5) |
C51—C52—C53 | 121.2 (3) | C113—C112—H112 | 117.6 |
C54—C53—C52 | 117.0 (4) | C111—C112—H112 | 117.6 |
C54—C53—C531 | 122.1 (4) | C114—C113—C112 | 119.8 (5) |
C52—C53—C531 | 121.0 (3) | C114—C113—H113 | 120.1 |
C53—C54—C55 | 123.9 (4) | C112—C113—H113 | 120.1 |
C53—C54—H54 | 118.1 | C113—C114—C115 | 118.6 (5) |
C55—C54—H54 | 118.1 | C113—C114—H114 | 120.7 |
C56—C55—C54 | 117.4 (3) | C115—C114—H114 | 120.7 |
C56—C55—C551 | 121.9 (4) | C114—C115—C116 | 119.7 (5) |
C54—C55—C551 | 120.8 (4) | C114—C115—H115 | 120.1 |
C55—C56—C51 | 121.5 (4) | C116—C115—H115 | 120.1 |
C55—C56—H56 | 119.2 | C115—C116—C111 | 124.4 (4) |
C51—C56—H56 | 119.2 | C115—C116—H116 | 117.8 |
C53—C531—C534 | 112.0 (3) | C111—C116—H116 | 117.8 |
C53—C531—C532 | 110.0 (3) |
Experimental details
Crystal data | |
Chemical formula | [Mn2(C42H49N5O2)(C2H3O2)2](C24H20B) |
Mr | 1203.04 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 16.492 (3), 16.804 (3), 24.519 (5) |
β (°) | 109.07 (3) |
V (Å3) | 6422 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.45 |
Crystal size (mm) | 0.47 × 0.40 × 0.13 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) and PLATON (Spek, 2003) |
Tmin, Tmax | 0.829, 0.937 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11638, 11223, 4980 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.127, 0.86 |
No. of reflections | 11223 |
No. of parameters | 784 |
No. of restraints | 90 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.31 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), SET4 in CAD-4 EXPRESS, HELENA (Spek, 1996), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
Mn1—O61 | 2.067 (3) | Mn2—O50 | 1.823 (2) |
Mn1—O71 | 2.139 (3) | Mn2—O1 | 1.905 (2) |
Mn1—O1 | 2.161 (2) | Mn2—O72 | 1.984 (3) |
Mn1—N32 | 2.237 (3) | Mn2—N4 | 2.118 (3) |
Mn1—N22 | 2.262 (4) | Mn2—O62 | 2.129 (3) |
Mn1—N1 | 2.335 (3) | Mn2—N42 | 2.278 (3) |
O61—Mn1—O71 | 97.80 (13) | O50—Mn2—O72 | 86.59 (11) |
O61—Mn1—O1 | 100.42 (11) | O1—Mn2—O72 | 92.36 (10) |
O71—Mn1—O1 | 88.22 (10) | O50—Mn2—N4 | 88.71 (11) |
O61—Mn1—N32 | 101.59 (13) | O1—Mn2—N4 | 91.88 (11) |
O71—Mn1—N32 | 87.95 (11) | O72—Mn2—N4 | 167.14 (12) |
O1—Mn1—N32 | 157.97 (11) | O50—Mn2—O62 | 92.03 (12) |
O61—Mn1—N22 | 96.88 (14) | O1—Mn2—O62 | 90.15 (11) |
O71—Mn1—N22 | 164.95 (13) | O72—Mn2—O62 | 97.88 (12) |
O1—Mn1—N22 | 85.85 (10) | N4—Mn2—O62 | 94.24 (11) |
N32—Mn1—N22 | 92.38 (12) | O50—Mn2—N42 | 91.52 (12) |
O61—Mn1—N1 | 169.30 (13) | O1—Mn2—N42 | 86.42 (11) |
O71—Mn1—N1 | 91.08 (11) | O72—Mn2—N42 | 89.94 (12) |
O1—Mn1—N1 | 85.76 (10) | N4—Mn2—N42 | 78.22 (12) |
N32—Mn1—N1 | 72.64 (12) | O62—Mn2—N42 | 171.59 (12) |
N22—Mn1—N1 | 74.71 (13) | Mn2—O1—Mn1 | 116.74 (11) |
O50—Mn2—O1 | 177.69 (12) |
Catalases are enzymes responsible for hydrogen peroxide dismutation, according to the reaction 2H2O2 → O2 + 2H2O. The dimanganese catalase extracted from Thermus thermophilus was recently characterized by X-ray diffraction analysis, which confirmed the existence of a dinuclear manganese centre in the active site situated in a cavity rich in hydrophobic residues (see scheme) (Barynin et al., 1997; Antonyuk et al., 2000). The Mn···Mn distance is 3.18 Å in the reduced form (Mn2II) and 3.14 Å in the oxidized form (Mn2III). On the other hand, the mixed-valence MnII–MnIII oxidation state is the least well characterized, and the L. [Please give genus name in full] plantarum enzyme has not been shown to form a stable MnII–MnIII form (Waldo et al., 1995; Khangulov et al., 1990). In fact, the design of biomimetic systems aiming to help in the understanding of the mechanism of H2O2 disproportionation by manganese catalases has attracted many research groups (Wu et al., 2004).
Here, we report on the synthesis and X-ray structure of the title novel mixed-valence MnII–MnIII complex, (I), containing the unsymmetrical dinucleating ligand Ldtb2− and acetate bridges, as a further interesting structural model for mixed-valence MnII–MnIII catalase.
The asymmetric unit of (I) consists of a discrete [MnIIMnIII(Ldtb)(µ-OAc)2]+ cation complex and a tetraphenylborate counterion. In the crystal structure, the packing arrangement is governed by electrostatic forces between ion pairs. The molecular structure of (I) (Fig. 1) shows that, in the dinuclear [MnIIIMnII(Ldtb)(µ-OAc)2]+ unit, the MnIII and MnII ions are bridged by the phenolate atom O1 of the Ldtb2− ligand and by two carboxylate groups of the acetate ligands. The charge distribution is the major contributor to the enhanced stability of the mixed valent species, as observed by Dubois et al. (2003). The three N atoms, N1, N22 and N32, from the tertiary amine and two pyridine groups (soft side) complete the octahedral coordination sphere of Mn1, typical of high spin MnII (Karsten, Neves, Bortoluzzi, Stähle & Maichle-Mössmer, 2002). A comparison of the bond lengths around the six-coordinated MnII ion (Table 1, mean 2.201 Å) are in good agreement compared with those reported by Karsten, Neves, Bortoluzzi, Stähle & Maichle-Mössmer (2002) for the compound [MnIIMnIIIbpbpmp(OAc)2]BF4, (II), where H2bpbpmp is the ligand {2-[N,N-bis(2-pyridylmethyl)aminomethyl]-6-[(2-hydroxybenzyl)(2-pyridylmethyl)]aminomethyl}-4-methylphenol, and by Karsten, Neves, Bortoluzzi, Lanznaster & Drago, (2002) in the compound [MnIIFeIIIbpbpmp(OAc)2](ClO4), (III).
The distances around MnII average 2.210 Å in (II) and 2.206 Å in (III), with the same N3O3 environment as (I). The distances from the pyridine N atom to Mn1, in (I), are quite similar [2.237 (3) and 2.262 (4) Å], while the distance of the N atom trans to the oxygen bridge is slightly longer, reflecting the weak trans effect of the phenolate group. The longest bond on the N3O3 side is that to the tertiary amine atom N1, with 2.335 (3) Å. This value is rather similar to those found in (II) and (III) [2.313 (2) and 2.279 (3) Å, respectively].
The coordination sphere of Mn2 is complemented by two N atoms, N4 and N42, from the tertiary amine and the pyridine group, and atom O50 from the terminal phenolate (hard side). The bond lengths around MnIII (mean 2.041 Å) are quite similar to those found in (II) (mean 2.052 Å), and the longer axial bond lengths [Mn2—N42 = 2.278 (3) Å and Mn2—O62 = 2.129 (3) Å] are consistent with a Jahn–Teller distortion of this high-spin d4 ion. The terminal MnIII—Ophenolate bond [1.825 (3) Å] and the Mn···Mn distance [3.466 (1) Å] are slightly shorter than those found in (II) [1.852 (2) and 3.497 Å, respectively], as expected, due to the effect caused by the tert-butyl substituents.
The Mn1—O1—Mn2 bridging angle of 116.8 (1)° falls within the range found for similarly coordinated mixed-valence manganese dimers with the structural [MnIIIMnII(µ-phenoxo)(µ-OAc)2] unit. In (II), this angle is 116.6°, in [Mn2(L-Im)(µ-OAc)2]+ it is 116.8° [HL-Im is 2,6-bis({bis[(1-methylimidazol-2-yl)methyl]amino}methyl)-4-methylphenol; Buchanan et al., 1988], in [Mn2(bpmp)(µ-OAc)2]+ it is 114.4° {Hbpmp is 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol; Diril et al., 1989} and in [Mn2(µ-L)(µ-OAc)2(H2O)]2+ it is 115.59° {HL is 2-[N-bis(2-pyridylmethyl)aminomethyl]-6-[N-(benzyl)(2- pyridylmethyl)aminomethyl]-4-methylphenol; Dubois et al., 2003}. [Please check references have been added to correct place in text]
Redox potentials are strongly dependent on the electronic character of the ligand substituent and on the asymmetry of the ligand. It is interesting to note that, despite the similarities of the averaged bond lengths and angles in the isostructural complexes (I) and (II), the E1/2 value of the redox couple [MnIIMnIII]/[MnIIMnII] is cathodically shifted by 55 mV, a result which is consistent with the electron-donating effect of the tert-butyl groups and the slightly shorter MnIII—Ophenolate bond length in complex (I), as described above. As reported by Miyasaka et al. (2003), the redox potentials can exhibit a linear correlation with the Hammett substituent constant σp.
In summary, a new unsymmetrical mixed-valence MnII–MnIII complex has been structurally characterized and provides the possibility of studies of peroxide disproportionation and of correlating the redox potential and ligand field contribution to the rate and efficiency of this catalytic process.