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The synthesis and characterization of a new unsymmetrical dinucleating N,O-donor ligand, 2-[N,N-bis­(2-pyridyl­methyl)­amino­methyl]-6-[N-(3,5-di-tert-butyl-2-oxidobenzyl)-N-(2-pyridyl­amino)­aminomethyl]-4-methyl­phenol (H2Ldtb), as well as the X-ray crystal structure of its corresponding mixed-valence diacetate-bridged manganese complex, di-[mu]-acetato-[mu]-{2-[N,N-bis­(2-pyridylmethyl)amino­methyl]-6-[N-(3,5-di-tert-butyl-2-oxidobenzyl)-N-(2-pyridyl­amino)­aminomethyl]-4-methylphenolato}dimanganese(II,III) tetra­phenyl­borate, [MnIIMnIII(C42H49N5O2)(C2H3O2)2](C24H20B), are reported. The complex may be regarded as an inter­esting structural model for the mixed-valence MnII-MnIII state of manganese catalase.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105039910/ta1508sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105039910/ta1508Isup2.hkl
Contains datablock I

CCDC reference: 299614

Comment top

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.

Experimental top

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%).

Refinement top

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]

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level. C atoms are shown as small circles of arbitrary size and H atoms have been omitted for clarity.
di-µ-acetato-µ-{2-[N,N-bis(2-pyridylmethyl)aminomethyl]-6-[N-(3,5-di-tert- butyl-2-oxidobenzyl)-N-(2-pyridylmethylamino)amino]-4- methylphenolato}dimanganese(II,III) tetraphenylborate top
Crystal data top
[Mn2(C42H49N5O2)(C2H3O2)2](C24H20B)F(000) = 2532
Mr = 1203.04Dx = 1.244 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 16.492 (3) ÅCell parameters from 25 reflections
b = 16.804 (3) Åθ = 9.9–13.2°
c = 24.519 (5) ŵ = 0.45 mm1
β = 109.07 (3)°T = 293 K
V = 6422 (2) Å3Irregular block, dark red
Z = 40.47 × 0.40 × 0.13 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
4980 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.052
Graphite monochromatorθmax = 25.0°, θmin = 2.4°
ω/2θ scansh = 019
Absorption correction: ψ scan
(North et al., 1968) and PLATON (Spek, 2003)
k = 190
Tmin = 0.829, Tmax = 0.937l = 2927
11638 measured reflections3 standard reflections every 200 reflections
11223 independent reflections intensity decay: 1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-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 parametersΔρmax = 0.24 e Å3
90 restraintsΔρmin = 0.31 e Å3
Crystal data top
[Mn2(C42H49N5O2)(C2H3O2)2](C24H20B)V = 6422 (2) Å3
Mr = 1203.04Z = 4
Monoclinic, P21/nMo Kα radiation
a = 16.492 (3) ŵ = 0.45 mm1
b = 16.804 (3) ÅT = 293 K
c = 24.519 (5) Å0.47 × 0.40 × 0.13 mm
β = 109.07 (3)°
Data collection top
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 = 0.9373 standard reflections every 200 reflections
11638 measured reflections intensity decay: 1%
11223 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05290 restraints
wR(F2) = 0.127H-atom parameters constrained
S = 0.86Δρmax = 0.24 e Å3
11223 reflectionsΔρmin = 0.31 e Å3
784 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Mn10.27664 (4)0.61150 (4)0.20730 (2)0.05025 (19)
Mn20.30020 (4)0.52920 (3)0.08379 (2)0.04344 (17)
N10.41081 (19)0.64542 (18)0.27223 (12)0.0486 (8)
C20.4785 (2)0.6233 (2)0.24811 (17)0.0590 (11)
H2A0.47400.56690.23910.071*
H2B0.53410.63250.27690.071*
C30.3163 (2)0.6943 (2)0.04364 (15)0.0478 (10)
H3A0.31790.73150.01380.057*
H3B0.26610.70640.05450.057*
N40.30862 (18)0.61064 (17)0.01991 (12)0.0430 (8)
O10.34056 (15)0.60673 (14)0.14322 (9)0.0445 (6)
C110.4731 (2)0.6697 (2)0.19422 (17)0.0492 (10)
C120.4024 (2)0.6607 (2)0.14401 (16)0.0442 (9)
C130.3952 (2)0.7049 (2)0.09510 (16)0.0452 (10)
C140.4607 (3)0.7569 (2)0.09551 (18)0.0555 (11)
H140.45530.78700.06270.067*
C150.5333 (3)0.7654 (3)0.1428 (2)0.0642 (12)
C160.5371 (3)0.7226 (3)0.19229 (19)0.0647 (12)
H160.58430.72970.22540.078*
C170.6070 (3)0.8189 (3)0.1413 (2)0.1016 (18)
H17A0.65200.81670.17800.152*
H17B0.58690.87270.13360.152*
H17C0.62880.80110.11160.152*
C200.4121 (3)0.7313 (2)0.28530 (17)0.0638 (12)
H20A0.47040.75070.29450.077*
H20B0.39500.73850.31930.077*
C210.3543 (3)0.7808 (3)0.23678 (19)0.0604 (12)
N220.2855 (2)0.7453 (2)0.20084 (15)0.0588 (9)
C230.2324 (3)0.7893 (3)0.1579 (2)0.0789 (14)
H230.18460.76440.13240.095*
C240.2444 (5)0.8669 (4)0.1499 (3)0.108 (2)
H240.20630.89450.11930.130*
C250.3128 (5)0.9041 (4)0.1871 (3)0.122 (2)
H250.32130.95820.18300.146*
C260.3703 (4)0.8612 (3)0.2314 (2)0.0954 (17)
H260.41840.88570.25690.114*
C300.4161 (3)0.5980 (2)0.32449 (16)0.0617 (12)
H30A0.46420.61640.35680.074*
H30B0.42590.54250.31770.074*
C310.3348 (3)0.6055 (2)0.33916 (17)0.0530 (10)
N320.2630 (2)0.61887 (19)0.29499 (13)0.0550 (9)
C330.1891 (3)0.6267 (2)0.30575 (19)0.0668 (13)
H330.13940.63700.27500.080*
C340.1832 (3)0.6202 (3)0.3603 (2)0.0748 (14)
H340.13080.62660.36650.090*
C350.2551 (4)0.6044 (3)0.4046 (2)0.0787 (15)
H350.25230.59810.44160.094*
C360.3330 (3)0.5975 (3)0.39530 (18)0.0706 (13)
H360.38310.58760.42580.085*
C400.3845 (2)0.5914 (2)0.00161 (15)0.0498 (10)
H40A0.36870.55060.02800.060*
H40B0.40120.63860.01500.060*
C410.4593 (3)0.5630 (2)0.05101 (16)0.0477 (10)
N420.4397 (2)0.51509 (19)0.08852 (14)0.0519 (8)
C430.5046 (3)0.4856 (3)0.13242 (19)0.0666 (12)
H430.49170.45170.15850.080*
C440.5889 (3)0.5030 (3)0.1407 (2)0.0782 (14)
H440.63220.48120.17160.094*
C450.6082 (3)0.5524 (3)0.1033 (2)0.0733 (14)
H450.66490.56600.10870.088*
C460.5431 (3)0.5825 (3)0.05712 (19)0.0652 (12)
H460.55550.61550.03040.078*
O500.26581 (17)0.45307 (14)0.02796 (10)0.0596 (8)
C500.2279 (2)0.6053 (2)0.03157 (15)0.0499 (10)
H50A0.17940.61890.01930.060*
H50B0.23100.64470.05970.060*
C510.2117 (2)0.5256 (2)0.06032 (16)0.0447 (9)
C520.2265 (2)0.4547 (2)0.02938 (15)0.0445 (10)
C530.2032 (2)0.3805 (2)0.05751 (17)0.0493 (10)
C540.1673 (2)0.3819 (2)0.11706 (17)0.0540 (11)
H540.15140.33370.13620.065*
C550.1536 (2)0.4512 (3)0.15000 (16)0.0542 (11)
C560.1754 (2)0.5229 (3)0.12065 (16)0.0537 (11)
H560.16570.57030.14150.064*
C5310.2167 (3)0.3027 (2)0.02298 (17)0.0572 (11)
C5320.3132 (3)0.2881 (2)0.00730 (19)0.0761 (14)
H53A0.32110.23940.02880.114*
H53B0.33710.33150.03310.114*
H53C0.34170.28450.02110.114*
C5330.1717 (3)0.3068 (3)0.02343 (19)0.0810 (14)
H53D0.18070.25780.04460.121*
H53E0.11140.31530.00500.121*
H53F0.19530.35000.04940.121*
C5340.1814 (3)0.2304 (3)0.06184 (19)0.0895 (15)
H53G0.19090.18310.03870.134*
H53H0.21020.22580.09000.134*
H53I0.12100.23730.08110.134*
C5510.1147 (3)0.4477 (3)0.21623 (19)0.0791 (15)
C5520.1726 (7)0.3937 (6)0.2386 (4)0.123 (4)0.70
H55A0.22820.41830.22710.184*0.70
H55B0.14880.39340.28000.184*0.70
H55C0.17800.34000.22450.184*0.70
C52'0.0803 (17)0.3659 (12)0.2373 (11)0.151 (11)0.30
H52A0.12650.33240.23900.226*0.30
H52B0.03840.37010.27510.226*0.30
H52C0.05410.34320.21120.226*0.30
C5530.1150 (7)0.5291 (5)0.2453 (3)0.106 (3)0.70
H55D0.16930.55620.23360.159*0.70
H55E0.07410.55990.23410.159*0.70
H55F0.09520.52260.28650.159*0.70
C53'0.1783 (11)0.4601 (18)0.2457 (8)0.156 (13)0.30
H53J0.22750.48700.22020.234*0.30
H53K0.15350.49190.27960.234*0.30
H53L0.19550.40960.25660.234*0.30
C5540.0284 (6)0.4089 (10)0.2334 (4)0.172 (7)0.70
H55G0.01190.43580.21920.258*0.70
H55H0.03610.35530.21920.258*0.70
H55I0.00720.40820.27490.258*0.70
C54'0.0331 (14)0.4992 (15)0.2303 (8)0.130 (9)0.30
H54A0.04880.55440.22590.195*0.30
H54B0.00220.48590.20450.195*0.30
H54C0.00270.48940.26930.195*0.30
O610.15018 (18)0.6007 (2)0.15520 (14)0.0888 (11)
O620.17113 (17)0.55955 (18)0.07484 (12)0.0728 (9)
C630.1258 (3)0.5770 (3)0.1042 (2)0.0711 (14)
C640.0301 (3)0.5663 (5)0.0764 (2)0.166 (3)
H64A0.00150.58170.10310.249*
H64B0.01780.51150.06590.249*
H64C0.01020.59890.04240.249*
O710.3040 (2)0.48752 (18)0.22284 (12)0.0734 (9)
O720.31458 (18)0.44148 (15)0.14036 (11)0.0631 (8)
C730.3159 (3)0.4345 (3)0.19154 (19)0.0527 (11)
C740.3335 (3)0.3508 (3)0.21483 (19)0.0885 (16)
H74A0.34130.31650.18560.133*0.50
H74B0.28590.33220.22570.133*0.50
H74C0.38460.35040.24800.133*0.50
H74D0.33320.34960.25390.133*0.50
H74E0.38860.33390.21380.133*0.50
H74F0.29000.31570.19160.133*0.50
B10.2225 (3)0.9234 (3)0.0696 (2)0.0544 (13)
C810.2997 (2)0.9689 (2)0.01888 (16)0.0475 (10)
C820.3369 (3)0.9339 (2)0.03574 (17)0.0565 (11)
H820.31220.88800.04450.068*
C830.4093 (3)0.9651 (3)0.07730 (18)0.0655 (12)
H830.43170.93970.11280.079*
C840.4476 (3)1.0327 (3)0.0665 (2)0.0663 (12)
H840.49691.05270.09370.080*
C850.4121 (3)1.0700 (3)0.0149 (2)0.0659 (12)
H850.43661.11670.00740.079*
C860.3393 (2)1.0392 (2)0.02690 (17)0.0568 (11)
H860.31631.06680.06140.068*
C910.2678 (3)0.8541 (2)0.09741 (17)0.0570 (11)
C920.2203 (3)0.8079 (3)0.1443 (2)0.0989 (18)
H920.16190.81800.16070.119*
C930.2564 (4)0.7473 (3)0.1680 (2)0.109 (2)
H930.22200.71790.19910.131*
C940.3418 (4)0.7311 (3)0.1453 (2)0.0966 (17)
H940.36610.69110.16110.116*
C950.3909 (3)0.7740 (3)0.0997 (2)0.0771 (14)
H950.44920.76320.08380.093*
C960.3543 (3)0.8341 (3)0.07655 (18)0.0633 (12)
H960.38960.86260.04530.076*
C1010.1546 (3)0.8847 (3)0.04075 (19)0.0632 (12)
C1020.1237 (3)0.9299 (3)0.0044 (2)0.0864 (15)
H1020.14440.98160.00370.104*
C1030.0640 (3)0.9038 (4)0.0208 (2)0.1055 (19)
H1030.04490.93760.04410.127*
C1040.0340 (4)0.8278 (5)0.0105 (3)0.125 (3)
H1040.00530.80860.02730.150*
C1050.0625 (4)0.7799 (4)0.0249 (3)0.128 (3)
H1050.04210.72810.03230.154*
C1060.1215 (3)0.8082 (3)0.0496 (2)0.0849 (16)
H1060.13960.77430.07330.102*
C1110.1738 (3)0.9877 (2)0.12023 (17)0.0544 (11)
C1120.2079 (3)1.0117 (3)0.16212 (18)0.0738 (14)
H1120.25790.98680.16300.089*
C1130.1733 (4)1.0700 (3)0.2027 (2)0.0851 (15)
H1130.20091.08450.22880.102*
C1140.0990 (4)1.1059 (3)0.2046 (2)0.0844 (15)
H1140.07411.14410.23240.101*
C1150.0611 (3)1.0847 (3)0.1644 (2)0.0791 (14)
H1150.01071.10940.16440.095*
C1160.0980 (3)1.0268 (3)0.12433 (18)0.0624 (12)
H1160.07031.01290.09820.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0486 (4)0.0591 (4)0.0448 (4)0.0044 (3)0.0177 (3)0.0043 (3)
Mn20.0476 (4)0.0424 (4)0.0428 (3)0.0020 (3)0.0181 (3)0.0020 (3)
N10.050 (2)0.048 (2)0.0448 (19)0.0028 (17)0.0115 (16)0.0038 (16)
C20.046 (3)0.068 (3)0.060 (3)0.001 (2)0.014 (2)0.001 (2)
C30.062 (3)0.038 (2)0.046 (2)0.001 (2)0.021 (2)0.0056 (19)
N40.0432 (19)0.045 (2)0.0416 (18)0.0014 (17)0.0151 (15)0.0033 (16)
O10.0471 (15)0.0444 (15)0.0445 (15)0.0117 (14)0.0183 (12)0.0023 (13)
C110.043 (2)0.045 (3)0.062 (3)0.005 (2)0.020 (2)0.002 (2)
C120.042 (2)0.042 (2)0.052 (2)0.000 (2)0.021 (2)0.003 (2)
C130.051 (3)0.039 (2)0.049 (2)0.003 (2)0.020 (2)0.000 (2)
C140.067 (3)0.046 (3)0.059 (3)0.006 (2)0.029 (2)0.007 (2)
C150.063 (3)0.062 (3)0.077 (3)0.017 (3)0.035 (3)0.005 (3)
C160.050 (3)0.072 (3)0.068 (3)0.016 (2)0.014 (2)0.013 (3)
C170.084 (4)0.116 (4)0.114 (4)0.060 (3)0.044 (3)0.015 (4)
C200.065 (3)0.066 (3)0.059 (3)0.014 (3)0.018 (2)0.008 (2)
C210.074 (3)0.052 (3)0.063 (3)0.004 (3)0.033 (3)0.001 (2)
N220.070 (2)0.056 (2)0.052 (2)0.015 (2)0.0227 (19)0.008 (2)
C230.092 (4)0.084 (4)0.068 (3)0.031 (3)0.036 (3)0.010 (3)
C240.134 (6)0.097 (6)0.101 (5)0.046 (5)0.048 (4)0.037 (4)
C250.176 (8)0.059 (4)0.156 (7)0.026 (5)0.088 (6)0.038 (5)
C260.114 (5)0.055 (4)0.120 (5)0.007 (3)0.042 (4)0.013 (3)
C300.067 (3)0.066 (3)0.046 (2)0.006 (2)0.009 (2)0.008 (2)
C310.073 (3)0.041 (2)0.046 (3)0.002 (2)0.022 (2)0.005 (2)
N320.064 (2)0.055 (2)0.050 (2)0.004 (2)0.0239 (19)0.0016 (18)
C330.073 (3)0.070 (3)0.065 (3)0.008 (3)0.033 (3)0.007 (2)
C340.096 (4)0.072 (3)0.075 (3)0.000 (3)0.053 (3)0.007 (3)
C350.124 (5)0.065 (3)0.060 (3)0.011 (3)0.047 (3)0.007 (3)
C360.093 (4)0.066 (3)0.049 (3)0.000 (3)0.018 (3)0.010 (2)
C400.051 (3)0.056 (3)0.047 (2)0.004 (2)0.021 (2)0.001 (2)
C410.053 (3)0.044 (2)0.053 (3)0.001 (2)0.027 (2)0.002 (2)
N420.049 (2)0.053 (2)0.057 (2)0.0125 (18)0.0211 (18)0.0096 (18)
C430.067 (3)0.067 (3)0.069 (3)0.016 (3)0.027 (3)0.016 (3)
C440.057 (3)0.095 (4)0.076 (3)0.025 (3)0.013 (3)0.010 (3)
C450.048 (3)0.091 (4)0.084 (4)0.008 (3)0.026 (3)0.010 (3)
C460.059 (3)0.076 (3)0.074 (3)0.004 (3)0.039 (3)0.004 (3)
O500.090 (2)0.0441 (17)0.0418 (16)0.0079 (15)0.0171 (15)0.0009 (13)
C500.048 (2)0.050 (3)0.047 (2)0.010 (2)0.009 (2)0.004 (2)
C510.040 (2)0.050 (3)0.045 (2)0.005 (2)0.0149 (19)0.003 (2)
C520.046 (2)0.054 (3)0.034 (2)0.006 (2)0.0147 (19)0.003 (2)
C530.040 (2)0.058 (3)0.054 (3)0.009 (2)0.021 (2)0.006 (2)
C540.051 (3)0.056 (3)0.053 (3)0.010 (2)0.015 (2)0.012 (2)
C550.036 (2)0.075 (3)0.045 (2)0.006 (2)0.0052 (19)0.006 (2)
C560.045 (2)0.069 (3)0.049 (3)0.005 (2)0.017 (2)0.006 (2)
C5310.065 (3)0.046 (3)0.062 (3)0.011 (2)0.022 (2)0.004 (2)
C5320.078 (3)0.056 (3)0.094 (4)0.005 (3)0.028 (3)0.012 (3)
C5330.095 (4)0.074 (3)0.092 (3)0.018 (3)0.055 (3)0.009 (3)
C5340.111 (4)0.065 (3)0.090 (4)0.021 (3)0.028 (3)0.016 (3)
C5510.078 (4)0.099 (4)0.048 (3)0.006 (3)0.005 (3)0.010 (3)
C5520.155 (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)
C5530.113 (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)
C5540.074 (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)
O610.0505 (19)0.143 (3)0.070 (2)0.005 (2)0.0144 (17)0.026 (2)
O620.0433 (18)0.103 (2)0.075 (2)0.0026 (17)0.0233 (16)0.0029 (18)
C630.039 (3)0.102 (4)0.068 (3)0.002 (3)0.011 (3)0.002 (3)
C640.047 (3)0.351 (11)0.094 (4)0.022 (5)0.015 (3)0.075 (6)
O710.116 (3)0.055 (2)0.065 (2)0.0064 (18)0.0508 (19)0.0006 (16)
O720.100 (2)0.0471 (17)0.0468 (17)0.0075 (16)0.0302 (16)0.0049 (14)
C730.056 (3)0.044 (3)0.060 (3)0.011 (2)0.020 (2)0.008 (2)
C740.132 (5)0.066 (3)0.076 (3)0.010 (3)0.047 (3)0.009 (3)
B10.046 (3)0.052 (3)0.060 (3)0.009 (2)0.009 (3)0.007 (3)
C810.047 (2)0.043 (2)0.055 (3)0.002 (2)0.020 (2)0.006 (2)
C820.058 (3)0.053 (3)0.056 (3)0.004 (2)0.016 (2)0.000 (2)
C830.069 (3)0.067 (3)0.056 (3)0.007 (3)0.014 (2)0.005 (3)
C840.055 (3)0.073 (3)0.068 (3)0.008 (3)0.016 (2)0.013 (3)
C850.058 (3)0.067 (3)0.077 (3)0.022 (3)0.029 (3)0.014 (3)
C860.053 (3)0.061 (3)0.058 (3)0.002 (2)0.020 (2)0.004 (2)
C910.061 (3)0.051 (3)0.053 (3)0.001 (2)0.010 (2)0.002 (2)
C920.090 (4)0.089 (4)0.088 (4)0.023 (3)0.011 (3)0.023 (3)
C930.139 (6)0.078 (4)0.080 (4)0.026 (4)0.004 (4)0.034 (3)
C940.133 (5)0.074 (4)0.085 (4)0.037 (4)0.038 (4)0.003 (3)
C950.082 (4)0.086 (4)0.067 (3)0.012 (3)0.029 (3)0.004 (3)
C960.065 (3)0.067 (3)0.061 (3)0.001 (3)0.024 (3)0.006 (2)
C1010.046 (3)0.068 (3)0.067 (3)0.002 (3)0.006 (2)0.009 (3)
C1020.064 (3)0.112 (4)0.086 (4)0.027 (3)0.029 (3)0.002 (3)
C1030.073 (4)0.148 (6)0.105 (4)0.016 (4)0.042 (3)0.015 (4)
C1040.058 (4)0.153 (8)0.166 (7)0.008 (5)0.037 (4)0.064 (6)
C1050.062 (4)0.087 (5)0.226 (8)0.013 (4)0.035 (5)0.065 (5)
C1060.051 (3)0.059 (3)0.135 (5)0.000 (3)0.017 (3)0.018 (3)
C1110.050 (3)0.054 (3)0.057 (3)0.010 (2)0.013 (2)0.010 (2)
C1120.073 (3)0.095 (4)0.053 (3)0.014 (3)0.020 (3)0.013 (3)
C1130.083 (4)0.102 (4)0.064 (3)0.001 (3)0.016 (3)0.012 (3)
C1140.092 (4)0.072 (4)0.069 (3)0.001 (3)0.001 (3)0.007 (3)
C1150.064 (3)0.065 (3)0.096 (4)0.009 (3)0.010 (3)0.008 (3)
C1160.054 (3)0.059 (3)0.070 (3)0.007 (3)0.015 (2)0.007 (3)
Geometric parameters (Å, º) top
Mn1—O612.067 (3)C532—H53C0.9600
Mn1—O712.139 (3)C533—H53D0.9600
Mn1—O12.161 (2)C533—H53E0.9600
Mn1—N322.237 (3)C533—H53F0.9600
Mn1—N222.262 (4)C534—H53G0.9600
Mn1—N12.335 (3)C534—H53H0.9600
Mn2—O501.823 (2)C534—H53I0.9600
Mn2—O11.905 (2)C551—C53'1.470 (12)
Mn2—O721.984 (3)C551—C5541.494 (8)
Mn2—N42.118 (3)C551—C52'1.512 (14)
Mn2—O622.129 (3)C551—C54'1.542 (13)
Mn2—N422.278 (3)C551—C5521.543 (9)
N1—C21.472 (4)C551—C5531.545 (8)
N1—C201.477 (5)C552—H55A0.9600
N1—C301.487 (4)C552—H55B0.9600
C2—C111.511 (5)C552—H55C0.9600
C2—H2A0.9700C52'—H52A0.9600
C2—H2B0.9700C52'—H52B0.9600
C3—C131.499 (5)C52'—H52C0.9600
C3—N41.511 (4)C553—H55D0.9600
C3—H3A0.9700C553—H55E0.9600
C3—H3B0.9700C553—H55F0.9600
N4—C401.497 (4)C53'—H53J0.9600
N4—C501.508 (4)C53'—H53K0.9600
O1—C121.360 (4)C53'—H53L0.9600
C11—C161.394 (5)C554—H55G0.9600
C11—C121.399 (5)C554—H55H0.9600
C12—C131.383 (5)C554—H55I0.9600
C13—C141.386 (5)C54'—H54A0.9600
C14—C151.376 (5)C54'—H54B0.9600
C14—H140.9300C54'—H54C0.9600
C15—C161.394 (5)O61—C631.248 (5)
C15—C171.523 (5)O62—C631.230 (5)
C16—H160.9300C63—C641.512 (6)
C17—H17A0.9600C64—H64A0.9600
C17—H17B0.9600C64—H64B0.9600
C17—H17C0.9600C64—H64C0.9600
C20—C211.508 (5)O71—C731.232 (4)
C20—H20A0.9700O72—C731.254 (4)
C20—H20B0.9700C73—C741.511 (5)
C21—N221.328 (5)C74—H74A0.9600
C21—C261.392 (6)C74—H74B0.9600
N22—C231.348 (5)C74—H74C0.9600
C23—C241.344 (7)C74—H74D0.9600
C23—H230.9300C74—H74E0.9600
C24—C251.349 (8)C74—H74F0.9600
C24—H240.9300B1—C1011.641 (6)
C25—C261.389 (7)B1—C1111.643 (6)
C25—H250.9300B1—C811.648 (6)
C26—H260.9300B1—C911.649 (6)
C30—C311.504 (5)C81—C861.395 (5)
C30—H30A0.9700C81—C821.407 (5)
C30—H30B0.9700C82—C831.394 (5)
C31—N321.336 (5)C82—H820.9300
C31—C361.393 (5)C83—C841.367 (5)
N32—C331.335 (5)C83—H830.9300
C33—C341.377 (6)C84—C851.360 (5)
C33—H330.9300C84—H840.9300
C34—C351.347 (6)C85—C861.398 (5)
C34—H340.9300C85—H850.9300
C35—C361.380 (6)C86—H860.9300
C35—H350.9300C91—C961.389 (5)
C36—H360.9300C91—C921.397 (5)
C40—C411.497 (5)C92—C931.397 (6)
C40—H40A0.9700C92—H920.9300
C40—H40B0.9700C93—C941.362 (6)
C41—N421.339 (4)C93—H930.9300
C41—C461.380 (5)C94—C951.355 (6)
N42—C431.340 (5)C94—H940.9300
C43—C441.370 (6)C95—C961.390 (5)
C43—H430.9300C95—H950.9300
C44—C451.350 (6)C96—H960.9300
C44—H440.9300C101—C1061.386 (6)
C45—C461.376 (5)C101—C1021.388 (6)
C45—H450.9300C102—C1031.393 (6)
C46—H460.9300C102—H1020.9300
O50—C521.342 (4)C103—C1041.364 (8)
C50—C511.496 (5)C103—H1030.9300
C50—H50A0.9700C104—C1051.375 (9)
C50—H50B0.9700C104—H1040.9300
C51—C521.391 (5)C105—C1061.388 (7)
C51—C561.404 (5)C105—H1050.9300
C52—C531.415 (5)C106—H1060.9300
C53—C541.385 (5)C111—C1121.383 (5)
C53—C5311.534 (5)C111—C1161.387 (5)
C54—C551.393 (5)C112—C1131.380 (6)
C54—H540.9300C112—H1120.9300
C55—C561.389 (5)C113—C1141.354 (6)
C55—C5511.540 (6)C113—H1130.9300
C56—H560.9300C114—C1151.374 (6)
C531—C5341.536 (5)C114—H1140.9300
C531—C5321.540 (5)C115—C1161.376 (6)
C531—C5331.550 (5)C115—H1150.9300
C532—H53A0.9600C116—H1160.9300
C532—H53B0.9600
O61—Mn1—O7197.80 (13)C534—C531—C532107.2 (4)
O61—Mn1—O1100.42 (11)C53—C531—C533110.4 (3)
O71—Mn1—O188.22 (10)C534—C531—C533108.4 (3)
O61—Mn1—N32101.59 (13)C532—C531—C533108.7 (3)
O71—Mn1—N3287.95 (11)C531—C532—H53A109.5
O1—Mn1—N32157.97 (11)C531—C532—H53B109.5
O61—Mn1—N2296.88 (14)H53A—C532—H53B109.5
O71—Mn1—N22164.95 (13)C531—C532—H53C109.5
O1—Mn1—N2285.85 (10)H53A—C532—H53C109.5
N32—Mn1—N2292.38 (12)H53B—C532—H53C109.5
O61—Mn1—N1169.30 (13)C531—C533—H53D109.5
O71—Mn1—N191.08 (11)C531—C533—H53E109.5
O1—Mn1—N185.76 (10)H53D—C533—H53E109.5
N32—Mn1—N172.64 (12)C531—C533—H53F109.5
N22—Mn1—N174.71 (13)H53D—C533—H53F109.5
O50—Mn2—O1177.69 (12)H53E—C533—H53F109.5
O50—Mn2—O7286.59 (11)C531—C534—H53G109.5
O1—Mn2—O7292.36 (10)C531—C534—H53H109.5
O50—Mn2—N488.71 (11)H53G—C534—H53H109.5
O1—Mn2—N491.88 (11)C531—C534—H53I109.5
O72—Mn2—N4167.14 (12)H53G—C534—H53I109.5
O50—Mn2—O6292.03 (12)H53H—C534—H53I109.5
O1—Mn2—O6290.15 (11)C53'—C551—C554133.6 (10)
O72—Mn2—O6297.88 (12)C53'—C551—C52'102.1 (12)
N4—Mn2—O6294.24 (11)C53'—C551—C55113.2 (9)
O50—Mn2—N4291.52 (12)C554—C551—C55110.2 (5)
O1—Mn2—N4286.42 (11)C52'—C551—C55112.1 (11)
O72—Mn2—N4289.94 (12)C53'—C551—C54'121.4 (11)
N4—Mn2—N4278.22 (12)C52'—C551—C54'103.4 (11)
O62—Mn2—N42171.59 (12)C55—C551—C54'104.3 (7)
C2—N1—C20112.0 (3)C554—C551—C552106.6 (8)
C2—N1—C30111.8 (3)C55—C551—C552107.7 (5)
C20—N1—C30110.1 (3)C54'—C551—C552148.0 (8)
C2—N1—Mn1109.8 (2)C554—C551—C553113.8 (7)
C20—N1—Mn1109.3 (2)C52'—C551—C553134.9 (11)
C30—N1—Mn1103.4 (2)C55—C551—C553112.9 (4)
N1—C2—C11112.6 (3)C552—C551—C553105.1 (6)
N1—C2—H2A109.1C551—C552—H55A106.6
C11—C2—H2A109.1C551—C552—H55B106.9
N1—C2—H2B109.1H55A—C552—H55B109.5
C11—C2—H2B109.1C551—C552—H55C114.8
H2A—C2—H2B107.8H55A—C552—H55C109.5
C13—C3—N4112.0 (3)H55B—C552—H55C109.5
C13—C3—H3A109.2C551—C52'—H52A109.5
N4—C3—H3A109.2C551—C52'—H52B109.5
C13—C3—H3B109.2H52A—C52'—H52B109.5
N4—C3—H3B109.2C551—C52'—H52C109.5
H3A—C3—H3B107.9H52A—C52'—H52C109.5
C40—N4—C50109.4 (3)H52B—C52'—H52C109.5
C40—N4—C3110.1 (3)C551—C553—H55D115.2
C50—N4—C3108.5 (3)C551—C553—H55E103.6
C40—N4—Mn2110.2 (2)H55D—C553—H55E109.5
C50—N4—Mn2109.1 (2)C551—C553—H55F109.5
C3—N4—Mn2109.5 (2)H55D—C553—H55F109.5
C12—O1—Mn2122.6 (2)H55E—C553—H55F109.5
C12—O1—Mn1120.5 (2)C551—C53'—H53J109.5
Mn2—O1—Mn1116.74 (11)C551—C53'—H53K109.5
C16—C11—C12117.5 (4)H53J—C53'—H53K109.5
C16—C11—C2122.0 (4)C551—C53'—H53L109.5
C12—C11—C2120.5 (3)H53J—C53'—H53L109.5
O1—C12—C13119.6 (3)H53K—C53'—H53L109.5
O1—C12—C11119.3 (3)C551—C554—H55G113.7
C13—C12—C11121.0 (4)C551—C554—H55H107.9
C12—C13—C14119.1 (4)H55G—C554—H55H109.5
C12—C13—C3118.1 (3)C551—C554—H55I106.8
C14—C13—C3122.8 (3)H55G—C554—H55I109.5
C15—C14—C13122.2 (4)H55H—C554—H55I109.5
C15—C14—H14118.9C551—C54'—H54A109.5
C13—C14—H14118.9C551—C54'—H54B109.5
C14—C15—C16117.4 (4)H54A—C54'—H54B109.5
C14—C15—C17121.6 (4)C551—C54'—H54C109.5
C16—C15—C17121.1 (4)H54A—C54'—H54C109.5
C15—C16—C11122.6 (4)H54B—C54'—H54C109.5
C15—C16—H16118.7C63—O61—Mn1125.3 (3)
C11—C16—H16118.7C63—O62—Mn2140.8 (3)
C15—C17—H17A109.5O62—C63—O61127.2 (4)
C15—C17—H17B109.5O62—C63—C64116.9 (4)
H17A—C17—H17B109.5O61—C63—C64115.9 (4)
C15—C17—H17C109.5C63—C64—H64A109.5
H17A—C17—H17C109.5C63—C64—H64B109.5
H17B—C17—H17C109.5H64A—C64—H64B109.5
N1—C20—C21114.0 (3)C63—C64—H64C109.5
N1—C20—H20A108.7H64A—C64—H64C109.5
C21—C20—H20A108.7H64B—C64—H64C109.5
N1—C20—H20B108.7C73—O71—Mn1131.3 (3)
C21—C20—H20B108.7C73—O72—Mn2136.7 (3)
H20A—C20—H20B107.6O71—C73—O72127.0 (4)
N22—C21—C26121.4 (4)O71—C73—C74119.2 (4)
N22—C21—C20117.3 (4)O72—C73—C74113.8 (4)
C26—C21—C20121.3 (5)C73—C74—H74A109.5
C21—N22—C23117.9 (4)C73—C74—H74B109.5
C21—N22—Mn1117.4 (3)H74A—C74—H74B109.5
C23—N22—Mn1124.0 (4)C73—C74—H74C109.5
C24—C23—N22123.9 (5)H74A—C74—H74C109.5
C24—C23—H23118.1H74B—C74—H74C109.5
N22—C23—H23118.1C73—C74—H74D109.5
C23—C24—C25118.8 (6)C73—C74—H74E109.5
C23—C24—H24120.6H74D—C74—H74E109.5
C25—C24—H24120.6C73—C74—H74F109.5
C24—C25—C26119.7 (6)H74D—C74—H74F109.5
C24—C25—H25120.2H74E—C74—H74F109.5
C26—C25—H25120.2C101—B1—C111110.6 (3)
C25—C26—C21118.4 (5)C101—B1—C81109.1 (3)
C25—C26—H26120.8C111—B1—C81109.4 (3)
C21—C26—H26120.8C101—B1—C91111.3 (4)
N1—C30—C31110.8 (3)C111—B1—C91109.1 (3)
N1—C30—H30A109.5C81—B1—C91107.3 (3)
C31—C30—H30A109.5C86—C81—C82114.2 (4)
N1—C30—H30B109.5C86—C81—B1124.6 (4)
C31—C30—H30B109.5C82—C81—B1120.9 (4)
H30A—C30—H30B108.1C83—C82—C81122.8 (4)
N32—C31—C36121.2 (4)C83—C82—H82118.6
N32—C31—C30116.3 (3)C81—C82—H82118.6
C36—C31—C30122.5 (4)C84—C83—C82120.7 (4)
C33—N32—C31118.7 (4)C84—C83—H83119.7
C33—N32—Mn1125.5 (3)C82—C83—H83119.7
C31—N32—Mn1115.4 (3)C85—C84—C83118.5 (4)
N32—C33—C34122.9 (4)C85—C84—H84120.8
N32—C33—H33118.6C83—C84—H84120.8
C34—C33—H33118.6C84—C85—C86121.2 (4)
C35—C34—C33118.4 (5)C84—C85—H85119.4
C35—C34—H34120.8C86—C85—H85119.4
C33—C34—H34120.8C81—C86—C85122.6 (4)
C34—C35—C36120.4 (4)C81—C86—H86118.7
C34—C35—H35119.8C85—C86—H86118.7
C36—C35—H35119.8C96—C91—C92113.6 (4)
C35—C36—C31118.4 (4)C96—C91—B1124.6 (4)
C35—C36—H36120.8C92—C91—B1121.7 (4)
C31—C36—H36120.8C93—C92—C91123.2 (5)
C41—C40—N4112.0 (3)C93—C92—H92118.4
C41—C40—H40A109.2C91—C92—H92118.4
N4—C40—H40A109.2C94—C93—C92120.0 (5)
C41—C40—H40B109.2C94—C93—H93120.0
N4—C40—H40B109.2C92—C93—H93120.0
H40A—C40—H40B107.9C95—C94—C93119.4 (5)
N42—C41—C46121.7 (4)C95—C94—H94120.3
N42—C41—C40115.3 (3)C93—C94—H94120.3
C46—C41—C40122.9 (4)C94—C95—C96120.0 (5)
C41—N42—C43117.7 (4)C94—C95—H95120.0
C41—N42—Mn2111.7 (3)C96—C95—H95120.0
C43—N42—Mn2127.4 (3)C91—C96—C95123.8 (4)
N42—C43—C44123.0 (4)C91—C96—H96118.1
N42—C43—H43118.5C95—C96—H96118.1
C44—C43—H43118.5C106—C101—C102113.6 (5)
C45—C44—C43118.9 (4)C106—C101—B1126.1 (5)
C45—C44—H44120.5C102—C101—B1120.3 (4)
C43—C44—H44120.5C101—C102—C103125.0 (5)
C44—C45—C46119.5 (4)C101—C102—H102117.5
C44—C45—H45120.3C103—C102—H102117.5
C46—C45—H45120.3C104—C103—C102118.7 (6)
C45—C46—C41119.1 (4)C104—C103—H103120.7
C45—C46—H46120.5C102—C103—H103120.7
C41—C46—H46120.5C103—C104—C105119.1 (6)
C52—O50—Mn2134.2 (2)C103—C104—H104120.4
C51—C50—N4114.9 (3)C105—C104—H104120.4
C51—C50—H50A108.6C104—C105—C106120.6 (6)
N4—C50—H50A108.6C104—C105—H105119.7
C51—C50—H50B108.6C106—C105—H105119.7
N4—C50—H50B108.6C101—C106—C105123.1 (6)
H50A—C50—H50B107.5C101—C106—H106118.5
C52—C51—C56119.1 (4)C105—C106—H106118.5
C52—C51—C50122.5 (3)C112—C111—C116112.6 (4)
C56—C51—C50118.3 (4)C112—C111—B1122.5 (4)
O50—C52—C51121.8 (3)C116—C111—B1124.9 (4)
O50—C52—C53117.0 (3)C113—C112—C111124.8 (5)
C51—C52—C53121.2 (3)C113—C112—H112117.6
C54—C53—C52117.0 (4)C111—C112—H112117.6
C54—C53—C531122.1 (4)C114—C113—C112119.8 (5)
C52—C53—C531121.0 (3)C114—C113—H113120.1
C53—C54—C55123.9 (4)C112—C113—H113120.1
C53—C54—H54118.1C113—C114—C115118.6 (5)
C55—C54—H54118.1C113—C114—H114120.7
C56—C55—C54117.4 (3)C115—C114—H114120.7
C56—C55—C551121.9 (4)C114—C115—C116119.7 (5)
C54—C55—C551120.8 (4)C114—C115—H115120.1
C55—C56—C51121.5 (4)C116—C115—H115120.1
C55—C56—H56119.2C115—C116—C111124.4 (4)
C51—C56—H56119.2C115—C116—H116117.8
C53—C531—C534112.0 (3)C111—C116—H116117.8
C53—C531—C532110.0 (3)

Experimental details

Crystal data
Chemical formula[Mn2(C42H49N5O2)(C2H3O2)2](C24H20B)
Mr1203.04
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)16.492 (3), 16.804 (3), 24.519 (5)
β (°) 109.07 (3)
V3)6422 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.45
Crystal size (mm)0.47 × 0.40 × 0.13
Data collection
DiffractometerEnraf–Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968) and PLATON (Spek, 2003)
Tmin, Tmax0.829, 0.937
No. of measured, independent and
observed [I > 2σ(I)] reflections
11638, 11223, 4980
Rint0.052
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.127, 0.86
No. of reflections11223
No. of parameters784
No. of restraints90
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
Mn1—O612.067 (3)Mn2—O501.823 (2)
Mn1—O712.139 (3)Mn2—O11.905 (2)
Mn1—O12.161 (2)Mn2—O721.984 (3)
Mn1—N322.237 (3)Mn2—N42.118 (3)
Mn1—N222.262 (4)Mn2—O622.129 (3)
Mn1—N12.335 (3)Mn2—N422.278 (3)
O61—Mn1—O7197.80 (13)O50—Mn2—O7286.59 (11)
O61—Mn1—O1100.42 (11)O1—Mn2—O7292.36 (10)
O71—Mn1—O188.22 (10)O50—Mn2—N488.71 (11)
O61—Mn1—N32101.59 (13)O1—Mn2—N491.88 (11)
O71—Mn1—N3287.95 (11)O72—Mn2—N4167.14 (12)
O1—Mn1—N32157.97 (11)O50—Mn2—O6292.03 (12)
O61—Mn1—N2296.88 (14)O1—Mn2—O6290.15 (11)
O71—Mn1—N22164.95 (13)O72—Mn2—O6297.88 (12)
O1—Mn1—N2285.85 (10)N4—Mn2—O6294.24 (11)
N32—Mn1—N2292.38 (12)O50—Mn2—N4291.52 (12)
O61—Mn1—N1169.30 (13)O1—Mn2—N4286.42 (11)
O71—Mn1—N191.08 (11)O72—Mn2—N4289.94 (12)
O1—Mn1—N185.76 (10)N4—Mn2—N4278.22 (12)
N32—Mn1—N172.64 (12)O62—Mn2—N42171.59 (12)
N22—Mn1—N174.71 (13)Mn2—O1—Mn1116.74 (11)
O50—Mn2—O1177.69 (12)
 

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