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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoIUCrDATA
ISSN: 2414-3146
Volume 6| Part 1| January 2021| x201643
https://doi.org/10.1107/S2414314620016430

Di-μ-benzoato-di-μ-ethano­lato-tetra­kis­[μ3-5-(hy­dr­oxy­meth­yl)-2-methyl-4-(oxidometh­yl)pyridin-1-ium-3-olato]tetra­kis­[μ3-5-(hy­dr­oxy­meth­yl)-2-methyl-4-(oxidometh­yl)pyridin-3-olato]di-μ3-oxido-hepta­manganese(II,III) ethanol octa­solvate

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Arpita Saha,a* Clifford W. Padgett,a Pierre LeMagueres,b Kiana Moncura and Glory Onajobia

aGeorgia Southern University, 521 C.O.E. Dr., Department of Chemistry and Biochemistry, Statesboro GA 30458, USA, and bRigaku Americas Corporation, 9009 New Trails Drive, The Woodlands TX 77381, USA
*Correspondence e-mail: asaha@georgiasouthern.edu

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 21 October 2020; accepted 18 December 2020; online 5 January 2021)

Our work in the area of synthesis of polynuclear manganese complexes and their magnetic properties led to the synthesis and crystallization of the title compound, [Mn7(C8H9NO3)4(C8H10NO3)4(C2H5O)2(C7H5O2)2O2]·8C2H5OH. Herein, we report the molecular and crystal structure of the title compound, which was synthesized by the reaction of Mn(C6H5COO)2 with pyridoxine (PNH2, C8H11NO3) followed by the addition of tetra­methyl­ammonium hydroxide (TMAOH). The core of this centrosymmetric complex is a cage-like structure consisting of six MnIII ions and one MnII ion bound together through Mn—O bonds. The compound crystallizes in hydrogen-bonded layers formed by O—H⋯N hydrogen bonds involving the aromatic amine group of the ligand PN2− with the neighboring O atoms from the PNH− ligand. The crystal structure has large voids present in which highly disordered solvent mol­ecules (ethanol) sit. A solvent mask was calculated and 181 electrons were found in a volume of 843 Å3 in one void per triclinic unit cell. This is consistent with the presence of seven ethanol mol­ecules per formula unit, which accounts for 182 electrons per unit cell. Additionally, one ethanol mol­ecule was found to be ordered in the crystal.

CCDC reference: 2051338

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[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The heptanuclear title compound is [Mn7(PN)4(PNH)4(EtO)2(O)2(C6H5CO2)2]·8(C2H6O), where PN2− refers to the doubly deprotonated ligand pyridoxine (PNH2, C8H11NO3) and PNH− refers to the singly deprotonated ligand. Polynuclear 3d metal complexes are known to display aesthetically pleasing structures (Tasiopoulos et al., 2004[Tasiopoulos, A. J., Vinslava, A., Wernsdorfer, W., Abboud, K. A. & Christou, G. (2004). Angew. Chem. Int. Ed. 43, 2117-2121.]), unusual symmetries (Hu et al., 2013[Hu, Y.-Q., Zeng, M.-H., Zhang, K., Hu, S., Zhou, F.-F. & Kurmoo, M. (2013). J. Am. Chem. Soc. 135, 7901-7908.]), and unique supra­molecular architectures (Fielden & Cronin, 2005[Fielden, J. & Cronin, L. (2005). In Encyclopedia of Supramolecular Chemistry. London: Taylor & Francis.]). Often such polymetallic complexes exhibit magnetic properties (Saha et al., 2011a[Saha, A., Thompson, M., Abboud, K. A., Wernsdorfer, W. & Christou, G. (2011a). Inorg. Chem. 50, 10476-10485.]), catalytic properties (Yamada et al., 2015[Yamada, Y., Oyama, K., Gates, R. & Fukuzumi, S. (2015). Angew. Chem. Int. Ed. 54, 5613-5617.]), optical properties (Aboshyan-Sorgho et al., 2012[Aboshyan-Sorgho, L., Nozary, H., Aebischer, A., Bünzli, J.-C. G., Morgantini, P.-Y., Kittilstved, K. R., Hauser, A., Eliseeva, S. V., Petoud, S. & Piguet, C. (2012). J. Am. Chem. Soc. 134, 12675-12684.]) and biological activities (Kuczer et al., 2013[Kuczer, M., Błaszak, M., Czarniewska, E., Rosiński, G. & Kowalik-Jankowska, T. (2013). Inorg. Chem. 52, 5951-5961.]). In order to support the network of three-dimensional polymetallic units, alkoxide-based ligands play an important role since this functionality is an excellent bridging group that fosters higher nuclearity products formation (Saha et al., 2011b[Saha, A., Abboud, K. A. & Christou, G. (2011b). Inorg. Chem. 50, 12774-12784.]). Herein, we explore the coordination chemistry of pyridoxine (PNH2, IUPAC name: 5-hy­droxy-6-methyl-3,4-pyridinedi­methanol), a water-soluble, naturally occurring vitamer of Vitamin B6 involved in the metabolism of all three macronutrients, namely proteins, lipids, and carbohydrates. This ligand plays the pivotal role as a linker (Stouder et al., 2017[Stouder, C. E., Warren, K. J., Perdue, O. F., Stewart, A. L., Padgett, C. W., Amonette, A. J. & Saha, A. (2017). Inorg. Chim. Acta, 464, 172-181.]).

The PNH2 ligand is comprised of aliphatic and aromatic alkoxide groups, and those in principle can adopt both bridging and chelating modes while binding with metals. The partially labeled molecular structure of the title compound is shown in Fig. 1[link]. The core of the centrosymmetric complex (Fig. 2[link]), is comprised of three triangular Mn3 units connected via the Mn3 atom at the center of this cage-like structure. The core consists of six MnIII (Mn1, Mn2, Mn4) ions and one MnII (Mn3) ion. The central Mn3 ion is connected to Mn1 and Mn2 via a μ3-O oxido ion (O2) and to Mn4 via μ3-O atoms (O1, O4) coming from the alkoxide arm of a PN2− group that is chelating to Mn4. Apart from that, Mn1 and Mn2 are connected via a bridging μ-O atom from the ethoxide group (O5) and a carboxyl­ate group (O11, O12). Mn1 is further connected to Mn4 via a bridging μ-O (O3) from the alkoxide arm of a PNH− group and a μ3-O atom (O1) from the alkoxide arm of a PN2− group. Similarly, Mn2 is connected to Mn4 via a bridging μ-O (O10) from the alkoxide arms of the PNH− group and a μ3-O atom (O4) from the alkoxide arm of a PN2− group. The neutral complex is thus comprised of six MnIII ions, one MnII ion, two oxide ions, two ethoxide ions, two carboxyl­ate ions, four doubly deprotonated, and four singly deprotonated ligands. All Mn ions possess octa­hedral environments. Bond-valence sum (BVS) calculations (Brese & O'Keeffe, 1991[Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.]) show that one of the alkoxide arms of all eight PNH2 ligands is deprotonated; however, four of the ligands, namely PNH−, exist in the zwitterionic form where the aromatic amine functionality is protonated. BVS calculations also confirmed that Mn1, Mn2, and Mn4 are MnIII ions.

[Figure 1]
Figure 1
A view of the mol­ecular structure of the title compound, with selected atoms labeled. Hydrogen atoms and solvent mol­ecules are omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2]
Figure 2
A view of the core of the complex, with the atom labeling. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) −x + 1, −y + 1, −z + 1.]

Inspection of the crystal packing of the complex shows that the Mn7 unit relates to its four neighboring units by O—H⋯N hydrogen bonds involving the aromatic amine (N1, N3) group of the ligand PN2− with the neighboring O atoms (O15, O14) from the PNH− ligand (Fig. 3[link]). In addition to the hydrogen bonds between neighboring molecules, there is also an O—H⋯O hydrogen bond between two OH groups on adjacent ligands (O17, O13). Table 1[link] gives details of these hydrogen-bonding inter­actions. The solid-state structural analysis of such complexes can give us valuable insights on potential uses of such materials for catalytic, magnetic and/or biological activity.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O14—H14⋯N3i 0.84 1.80 2.619 (4) 163
O15—H15⋯N1ii 0.84 1.84 2.675 (4) 175
O17—H17⋯O13iii 0.84 1.89 2.684 (5) 158
Symmetry codes: (i) [-x+1, -y, -z+2]; (ii) [x, y, z-1]; (iii) [-x+1, -y+1, -z+1].
[Figure 3]
Figure 3
Crystal packing diagram of the title compound viewed along [100]. Hydrogen bonds are colored red.

The crystal structure has large voids present in which highly disordered solvent mol­ecules (ethanol) sit. A solvent mask was calculated and 181 electrons were found in a volume of 843 Å3 in one void per triclinic unit cell. This is consistent with the presence of seven ethanol mol­ecules per formula unit, which accounts for 182 electrons per unit cell. Additionally, one ethanol mol­ecule O16/C42/C43 was found to be ordered in the crystal.

Synthesis and crystallization

The reaction was carried out in presence of air. To a stirred solution of Mn(C6H5COO)2 (0.17 g, 1.0 mmol) in 12 ml of ethanol, pyridoxine (PNH2, 0.10 g, 1.0 mmol) was added at 343 K. The solution turned from pink to light brown after the addition of the PNH2, which is an indication of oxidation of MnII to MnIII by the atmospheric O2. After 30 min, TMAOH (0.09 g, 1.0 mmol) was added to the stirred solution. Heating was ceased and the reaction was set to stir for 3 h, after which the dark-brown solution was filtered and set for slow diffusion with Et2O. X-ray quality crystals grew after two weeks with a yield of 23%. The crystals were stored in the mother solvent until X-ray study.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. Disordered mol­ecules of ethanol were tentatively added to the model. Only one ethanol mol­ecule, with 50% occupancy, refined well without breaking up when anisotropic temperature factors were included, and was kept. The contribution from the other seven disordered ethanol solvent mol­ecules to the structure factors was calculated using the solvent mask tool in OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Table 2
Experimental details

Crystal data
Chemical formula [Mn7(C8H9NO3)4(C8H10NO3)4(C2H5O)2(C7H5O2)2O2]·8C2H6O
Mr 2449.71
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 100
a, b, c (Å) 12.9774 (5), 14.6762 (7), 16.7750 (6)
α, β, γ (°) 66.578 (4), 77.956 (3), 81.343 (4)
V (Å3) 2859.0 (2)
Z 1
Radiation type Mo Kα
μ (mm−1) 0.83
Crystal size (mm) 0.09 × 0.08 × 0.06
 
Data collection
Diffractometer Rigaku XtaLAB Synergy, Dualflex, HyPix
Absorption correction Multi-scan (CrysAlis PRO; Rigaku OD, 2020[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.])
Tmin, Tmax 0.966, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 34399, 10190, 7884
Rint 0.037
(sin θ/λ)max (Å−1) 0.597
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.141, 1.07
No. of reflections 10190
No. of parameters 621
No. of restraints 9
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.98, −0.28
Computer programs: CrysAlis PRO (Rigaku OD, 2020[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]), SHELXT (Sheldrick, 2015a[Sheldrick, G. M. (2015a). Acta Cryst. A71, 3-8.]), SHELXL2018/1 (Sheldrick, 2015b[Sheldrick, G. M. (2015b). Acta Cryst. C71, 3-8.]) and OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

Structural data

CCDC reference: 2051338

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620016430/bh4058sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620016430/bh4058Isup2.hkl

checkCIF report


Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2020); cell refinement: CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Di-µ-benzoato-di-µ-ethanolato-tetrakis[µ3-5-(hydroxymethyl)-2-methyl-4-(oxidomethyl)pyridin-1-ium-3-olato]tetrakis[µ3-5-(hydroxymethyl)-2-methyl-4-(oxidomethyl)pyridin-3-olato]di-µ3-oxido-heptamanganese(II,III) ethanol octasolvate top
Crystal data top
[Mn7(C8H9NO3)4(C8H10NO3)4(C2H5O)2(C7H5O2)2O2]·8C2H6OZ = 1
Mr = 2449.71F(000) = 1274
Triclinic, P1Dx = 1.423 Mg m−3
a = 12.9774 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 14.6762 (7) ÅCell parameters from 12116 reflections
c = 16.7750 (6) Åθ = 2.6–30.1°
α = 66.578 (4)°µ = 0.83 mm−1
β = 77.956 (3)°T = 100 K
γ = 81.343 (4)°Block, green
V = 2859.0 (2) Å30.09 × 0.08 × 0.06 mm
Data collection top
Rigaku XtaLAB Synergy, Dualflex, HyPix
diffractometer		10190 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source7884 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.037
Detector resolution: 10.0000 pixels mm-1θmax = 25.1°, θmin = 2.5°
ω scansh = −15→15
Absorption correction: multi-scan
(CrysAlisPro; Rigaku OD, 2020)		k = −17→17
Tmin = 0.966, Tmax = 1.000l = −20→20
34399 measured reflections
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0847P)2 + 0.6047P]
where P = (Fo2 + 2Fc2)/3
10190 reflections(Δ/σ)max = 0.001
621 parametersΔρmax = 0.98 e Å−3
9 restraintsΔρmin = −0.28 e Å−3
Special details top

Refinement. Hydrogen atoms were attached via the riding model at calculated positions using suitable HFIX commands.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Mn10.72295 (3)0.42295 (3)0.56146 (3)0.03246 (13)
Mn20.72328 (3)0.52363 (3)0.37463 (3)0.03223 (13)
Mn30.5000000.5000000.5000000.02829 (15)
Mn40.49800 (4)0.39857 (3)0.70324 (3)0.03243 (13)
O10.55540 (16)0.51184 (14)0.60120 (12)0.0335 (5)
O20.63608 (16)0.43484 (15)0.47679 (12)0.0346 (5)
O30.64800 (16)0.32378 (15)0.65648 (13)0.0377 (5)
O40.43587 (16)0.37094 (14)0.62110 (12)0.0317 (4)
O50.77496 (16)0.54310 (15)0.46695 (12)0.0340 (5)
O60.54308 (18)0.43981 (16)0.78180 (13)0.0427 (5)
O70.80492 (17)0.43486 (16)0.63726 (13)0.0399 (5)
O80.45964 (18)0.27999 (16)0.79730 (13)0.0429 (5)
O90.80638 (17)0.62354 (16)0.28792 (12)0.0401 (5)
O100.65480 (16)0.51228 (16)0.29100 (12)0.0365 (5)
O110.84197 (18)0.40553 (17)0.37249 (14)0.0450 (5)
O120.84048 (18)0.32516 (16)0.51759 (14)0.0446 (5)
O130.5745 (3)0.8308 (2)0.5748 (2)0.0938 (11)
H130.5630290.8670610.6043310.141*
O140.7656 (3)0.0844 (3)0.9805 (2)0.1267 (17)
H140.7220790.0446961.0171220.190*
O150.7882 (3)0.6430 (4)−0.07481 (18)0.1081 (14)
H150.7520500.628887−0.1038880.162*
O170.4330 (3)0.0810 (3)0.5982 (2)0.0919 (11)
H170.4230530.0949530.5466180.138*
N10.6795 (3)0.6054 (2)0.82394 (19)0.0565 (8)
N20.8660 (2)0.3582 (3)0.85144 (18)0.0572 (8)
H20.8986450.3805280.8802770.069*
N30.3404 (3)0.0499 (2)0.8848 (2)0.0625 (9)
N40.8846 (3)0.7742 (2)0.06429 (17)0.0541 (8)
H40.9190640.8279780.0337770.065*
C10.5477 (3)0.6057 (2)0.6102 (2)0.0437 (8)
H1A0.4721360.6286710.6203330.052*
H1B0.5813890.6551890.5543100.052*
C20.5985 (3)0.6023 (2)0.68398 (19)0.0398 (7)
C30.5897 (2)0.5214 (2)0.7651 (2)0.0383 (7)
C40.6299 (3)0.5275 (3)0.8349 (2)0.0453 (8)
C50.6900 (4)0.6800 (3)0.7461 (3)0.0668 (12)
H50.7262980.7348590.7393360.080*
C60.6519 (3)0.6829 (3)0.6746 (2)0.0541 (9)
C70.6150 (3)0.4451 (3)0.9227 (2)0.0521 (9)
H7A0.6575520.4538860.9606560.078*
H7B0.6374450.3813700.9159950.078*
H7C0.5402750.4457170.9493000.078*
C80.6669 (4)0.7730 (3)0.5903 (3)0.0711 (13)
H8A0.7196510.8132280.5933720.085*
H8B0.6949210.7511640.5406230.085*
C90.7070 (3)0.2479 (2)0.7162 (2)0.0480 (8)
H9A0.7597150.2138000.6834750.058*
H9B0.6587420.1980880.7595880.058*
C100.7632 (3)0.2870 (2)0.7647 (2)0.0438 (8)
C110.7743 (3)0.2318 (3)0.8526 (2)0.0579 (10)
C120.8258 (3)0.2700 (3)0.8944 (2)0.0657 (12)
H120.8328820.2334810.9543650.079*
C130.8599 (3)0.4152 (3)0.7668 (2)0.0445 (8)
C140.8080 (2)0.3788 (2)0.72120 (19)0.0401 (7)
C150.7288 (3)0.1302 (4)0.9029 (3)0.0804 (15)
H15A0.6507050.1389970.9141610.096*
H15B0.7496290.0885840.8671540.096*
C160.9105 (3)0.5112 (3)0.7254 (2)0.0543 (9)
H16A0.9005610.5431470.7681190.082*
H16B0.8781940.5549920.6740760.082*
H16C0.9862600.4987030.7067140.082*
C170.4377 (3)0.2715 (2)0.62780 (19)0.0396 (7)
H17A0.5108460.2501310.6070720.048*
H17B0.3926310.2702840.5874050.048*
C180.4011 (3)0.1963 (2)0.7189 (2)0.0404 (7)
C190.4165 (2)0.2055 (2)0.7954 (2)0.0385 (7)
C200.3851 (3)0.1288 (2)0.8786 (2)0.0470 (8)
C210.3266 (4)0.0416 (3)0.8115 (3)0.0703 (12)
H210.295627−0.0157560.8170610.084*
C220.3544 (3)0.1115 (3)0.7281 (2)0.0552 (10)
C230.4023 (3)0.1353 (3)0.9612 (2)0.0558 (10)
H23A0.4741860.1084870.9718790.084*
H23B0.3512170.0966441.0107390.084*
H23C0.3927970.2050800.9553180.084*
C240.3357 (4)0.0933 (3)0.6510 (3)0.0709 (13)
H24A0.2968340.0328150.6720040.085*
H24B0.2919100.1503370.6154910.085*
C250.8829 (2)0.5660 (3)0.4548 (2)0.0438 (8)
H25A0.9221190.5605510.3993620.053*
H25B0.9171180.5168490.5039440.053*
C260.8890 (3)0.6662 (3)0.4515 (3)0.0716 (12)
H26A0.8492090.7144890.4067010.107*
H26B0.9629980.6820370.4363420.107*
H26C0.8586780.6692160.5090540.107*
C270.8156 (2)0.6543 (2)0.20096 (18)0.0347 (7)
C280.8713 (3)0.7392 (2)0.1522 (2)0.0422 (8)
C290.8469 (3)0.7298 (3)0.0209 (2)0.0587 (10)
H290.8599610.755807−0.0416320.070*
C300.7901 (3)0.6477 (3)0.0657 (2)0.0488 (9)
C310.7733 (2)0.6081 (2)0.15795 (19)0.0372 (7)
C320.7148 (3)0.5151 (3)0.20907 (19)0.0421 (8)
H32A0.6668700.5098530.1725620.050*
H32B0.7667230.4564350.2199450.050*
C330.9166 (3)0.7920 (3)0.1953 (2)0.0531 (9)
H33A0.9474730.8521970.1502870.080*
H33B0.9715030.7480210.2274160.080*
H33C0.8605470.8105770.2364860.080*
C340.7481 (3)0.5992 (4)0.0152 (2)0.0709 (13)
H34A0.7694560.5269700.0373160.085*
H34B0.6699270.6077500.0244340.085*
C350.8716 (3)0.3350 (2)0.4376 (2)0.0429 (8)
C360.9487 (3)0.2559 (3)0.4202 (3)0.0499 (9)
C370.9834 (3)0.2609 (3)0.3344 (3)0.0599 (10)
H370.9573470.3145800.2869680.072*
C381.0550 (4)0.1889 (4)0.3176 (3)0.0740 (12)
H381.0776940.1931540.2586710.089*
C391.0935 (4)0.1118 (4)0.3846 (4)0.0821 (14)
H391.1427830.0621910.3725240.099*
C401.0608 (4)0.1056 (3)0.4700 (4)0.0740 (13)
H401.0881960.0520420.5167360.089*
C410.9875 (3)0.1777 (3)0.4883 (3)0.0574 (10)
H410.9645590.1727840.5473680.069*
O160.6762 (5)0.2505 (4)0.4357 (4)0.0752 (16)0.5
H160.6423960.2906690.4577910.113*0.5
C420.6885 (6)0.1580 (6)0.5016 (6)0.0623 (17)0.5
H42A0.6237290.1434830.5464200.075*0.5
H42B0.7486860.1545900.5308170.075*0.5
C430.7077 (7)0.0916 (7)0.4594 (7)0.081 (2)0.5
H43A0.6733400.1187450.4070390.121*0.5
H43B0.6792440.0280340.4994950.121*0.5
H43C0.7839890.0810560.4417670.121*0.5
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0324 (3)0.0366 (3)0.0289 (2)−0.0128 (2)−0.00724 (18)−0.00816 (18)
Mn20.0324 (3)0.0407 (3)0.0269 (2)−0.0137 (2)−0.00393 (18)−0.01295 (19)
Mn30.0290 (3)0.0337 (3)0.0242 (3)−0.0124 (3)−0.0051 (2)−0.0093 (2)
Mn40.0368 (3)0.0378 (3)0.0241 (2)−0.0140 (2)−0.00685 (18)−0.00830 (18)
O10.0416 (12)0.0341 (11)0.0270 (10)−0.0156 (9)−0.0040 (8)−0.0099 (8)
O20.0350 (12)0.0402 (11)0.0317 (10)−0.0157 (9)−0.0073 (8)−0.0114 (9)
O30.0363 (12)0.0360 (11)0.0363 (11)−0.0132 (9)−0.0077 (9)−0.0043 (9)
O40.0361 (11)0.0345 (11)0.0254 (9)−0.0145 (9)−0.0056 (8)−0.0078 (8)
O50.0333 (11)0.0419 (11)0.0284 (10)−0.0166 (9)−0.0042 (8)−0.0107 (8)
O60.0535 (14)0.0479 (13)0.0298 (11)−0.0168 (11)−0.0139 (9)−0.0098 (9)
O70.0442 (13)0.0449 (12)0.0305 (11)−0.0199 (10)−0.0099 (9)−0.0065 (9)
O80.0528 (14)0.0455 (13)0.0274 (10)−0.0202 (11)−0.0076 (9)−0.0044 (9)
O90.0459 (13)0.0528 (13)0.0274 (10)−0.0247 (11)−0.0002 (9)−0.0169 (9)
O100.0391 (12)0.0462 (12)0.0308 (10)−0.0153 (10)−0.0038 (8)−0.0180 (9)
O110.0438 (13)0.0499 (14)0.0467 (13)−0.0056 (11)−0.0058 (10)−0.0241 (11)
O120.0411 (13)0.0443 (13)0.0506 (14)−0.0055 (10)−0.0090 (10)−0.0187 (10)
O130.140 (3)0.0525 (18)0.074 (2)0.000 (2)0.001 (2)−0.0191 (15)
O140.099 (3)0.139 (3)0.078 (2)−0.053 (2)−0.034 (2)0.050 (2)
O150.113 (3)0.189 (4)0.0413 (16)−0.080 (3)−0.0050 (16)−0.044 (2)
O170.133 (3)0.082 (2)0.083 (2)0.008 (2)−0.040 (2)−0.050 (2)
N10.067 (2)0.069 (2)0.0511 (17)−0.0224 (17)−0.0145 (15)−0.0322 (16)
N20.0421 (17)0.093 (2)0.0352 (15)−0.0091 (16)−0.0118 (12)−0.0189 (16)
N30.082 (2)0.0445 (17)0.0467 (18)−0.0233 (17)−0.0100 (16)0.0036 (14)
N40.070 (2)0.0525 (18)0.0327 (15)−0.0244 (16)−0.0011 (13)−0.0058 (13)
C10.062 (2)0.0350 (17)0.0387 (17)−0.0155 (15)−0.0122 (15)−0.0127 (13)
C20.0406 (18)0.0474 (18)0.0366 (16)−0.0100 (15)−0.0038 (13)−0.0200 (14)
C30.0354 (17)0.0479 (18)0.0403 (17)−0.0094 (14)−0.0082 (13)−0.0227 (14)
C40.048 (2)0.060 (2)0.0373 (17)−0.0073 (16)−0.0081 (14)−0.0261 (15)
C50.093 (3)0.064 (2)0.057 (2)−0.037 (2)−0.017 (2)−0.025 (2)
C60.065 (2)0.062 (2)0.0480 (19)−0.0258 (19)−0.0099 (17)−0.0268 (17)
C70.061 (2)0.065 (2)0.0404 (18)−0.0041 (18)−0.0170 (16)−0.0265 (17)
C80.103 (4)0.062 (3)0.059 (2)−0.045 (3)−0.015 (2)−0.021 (2)
C90.047 (2)0.0394 (18)0.0468 (18)−0.0080 (15)−0.0133 (15)−0.0004 (14)
C100.0345 (18)0.0463 (19)0.0381 (17)−0.0076 (14)−0.0100 (13)0.0005 (14)
C110.037 (2)0.072 (3)0.0436 (19)−0.0102 (18)−0.0120 (15)0.0050 (17)
C120.043 (2)0.100 (3)0.0308 (18)−0.007 (2)−0.0095 (15)0.0026 (19)
C130.0352 (18)0.065 (2)0.0342 (17)−0.0054 (16)−0.0066 (13)−0.0187 (15)
C140.0334 (17)0.0497 (19)0.0327 (16)−0.0053 (14)−0.0083 (13)−0.0088 (14)
C150.056 (3)0.098 (3)0.052 (2)−0.020 (2)−0.0154 (19)0.017 (2)
C160.057 (2)0.068 (2)0.054 (2)−0.0170 (19)−0.0147 (17)−0.0313 (18)
C170.0459 (19)0.0403 (17)0.0372 (16)−0.0132 (14)−0.0083 (14)−0.0152 (13)
C180.0438 (19)0.0339 (16)0.0405 (17)−0.0100 (14)−0.0091 (14)−0.0074 (13)
C190.0384 (18)0.0336 (16)0.0374 (16)−0.0080 (14)−0.0057 (13)−0.0056 (13)
C200.051 (2)0.0399 (18)0.0399 (18)−0.0065 (16)−0.0060 (15)−0.0043 (14)
C210.101 (4)0.042 (2)0.063 (3)−0.035 (2)−0.021 (2)0.0003 (18)
C220.076 (3)0.0410 (19)0.049 (2)−0.0205 (18)−0.0168 (18)−0.0080 (15)
C230.071 (3)0.047 (2)0.0344 (17)−0.0094 (18)−0.0035 (16)−0.0002 (15)
C240.105 (4)0.047 (2)0.065 (3)−0.034 (2)−0.021 (2)−0.0123 (19)
C250.0346 (18)0.062 (2)0.0352 (16)−0.0206 (16)−0.0073 (13)−0.0121 (15)
C260.058 (3)0.090 (3)0.090 (3)−0.035 (2)−0.002 (2)−0.052 (3)
C270.0361 (17)0.0407 (17)0.0291 (15)−0.0071 (13)−0.0024 (12)−0.0150 (12)
C280.046 (2)0.0444 (18)0.0360 (17)−0.0111 (15)0.0003 (14)−0.0156 (14)
C290.068 (3)0.074 (3)0.0275 (17)−0.019 (2)−0.0058 (16)−0.0087 (16)
C300.052 (2)0.068 (2)0.0324 (17)−0.0186 (18)−0.0068 (14)−0.0208 (16)
C310.0332 (17)0.0505 (19)0.0324 (15)−0.0076 (14)−0.0028 (12)−0.0202 (14)
C320.048 (2)0.053 (2)0.0351 (16)−0.0161 (16)−0.0026 (14)−0.0251 (14)
C330.064 (2)0.052 (2)0.0493 (19)−0.0304 (18)0.0074 (17)−0.0244 (16)
C340.067 (3)0.116 (4)0.0329 (18)−0.039 (3)−0.0045 (17)−0.023 (2)
C350.0377 (18)0.0455 (19)0.052 (2)−0.0145 (15)−0.0017 (15)−0.0246 (16)
C360.041 (2)0.0444 (19)0.073 (2)−0.0172 (16)−0.0055 (17)−0.0277 (18)
C370.050 (2)0.060 (2)0.082 (3)−0.0166 (19)0.0028 (19)−0.041 (2)
C380.068 (3)0.071 (3)0.098 (3)−0.010 (2)0.003 (2)−0.054 (3)
C390.066 (3)0.070 (3)0.128 (4)−0.003 (2)−0.006 (3)−0.062 (3)
C400.060 (3)0.049 (2)0.124 (4)−0.003 (2)−0.028 (3)−0.038 (3)
C410.047 (2)0.052 (2)0.083 (3)−0.0119 (18)−0.0090 (19)−0.033 (2)
O160.061 (4)0.071 (3)0.103 (4)−0.008 (3)−0.034 (3)−0.032 (3)
C420.026 (3)0.066 (3)0.096 (5)−0.013 (3)−0.005 (3)−0.031 (3)
C430.054 (5)0.077 (4)0.123 (7)0.017 (4)−0.031 (5)−0.050 (5)
Geometric parameters (Å, º) top
Mn1—Mn22.8844 (6)C8—H8B0.9900
Mn1—Mn33.1695 (5)C9—H9A0.9900
Mn1—O12.471 (2)C9—H9B0.9900
Mn1—O21.9315 (19)C9—C101.506 (5)
Mn1—O31.8815 (19)C10—C111.398 (4)
Mn1—O51.9410 (19)C10—C141.400 (5)
Mn1—O71.891 (2)C11—C121.369 (6)
Mn1—O122.154 (2)C11—C151.529 (6)
Mn2—Mn33.1810 (4)C12—H120.9500
Mn2—O21.9428 (19)C13—C141.405 (5)
Mn2—O4i2.394 (2)C13—C161.486 (5)
Mn2—O51.9422 (19)C15—H15A0.9900
Mn2—O91.8853 (19)C15—H15B0.9900
Mn2—O101.881 (2)C16—H16A0.9800
Mn2—O112.145 (2)C16—H16B0.9800
Mn3—Mn4i3.1274 (4)C16—H16C0.9800
Mn3—Mn43.1274 (4)C17—H17A0.9900
Mn3—O12.0519 (19)C17—H17B0.9900
Mn3—O1i2.0518 (19)C17—C181.515 (4)
Mn3—O21.920 (2)C18—C191.400 (4)
Mn3—O2i1.920 (2)C18—C221.404 (5)
Mn3—O4i2.2620 (18)C19—C201.426 (4)
Mn3—O42.2620 (18)C20—C231.490 (5)
Mn4—O11.9563 (18)C21—H210.9500
Mn4—O32.239 (2)C21—C221.379 (5)
Mn4—O41.9286 (19)C22—C241.492 (5)
Mn4—O61.873 (2)C23—H23A0.9800
Mn4—O81.875 (2)C23—H23B0.9800
Mn4—O10i2.212 (2)C23—H23C0.9800
O1—C11.432 (4)C24—H24A0.9900
O3—C91.417 (4)C24—H24B0.9900
O4—C171.415 (4)C25—H25A0.9900
O5—C251.445 (3)C25—H25B0.9900
O6—C31.327 (4)C25—C261.462 (5)
O7—C141.324 (3)C26—H26A0.9800
O8—C191.315 (4)C26—H26B0.9800
O9—C271.329 (3)C26—H26C0.9800
O10—C321.420 (3)C27—C281.400 (4)
O11—C351.252 (4)C27—C311.396 (4)
O12—C351.274 (4)C28—C331.493 (5)
O13—H130.8400C29—H290.9500
O13—C81.368 (6)C29—C301.370 (5)
O14—H140.8400C30—C311.400 (4)
O14—C151.356 (5)C30—C341.520 (5)
O15—H150.8400C31—C321.511 (4)
O15—C341.402 (4)C32—H32A0.9900
O17—H170.8400C32—H32B0.9900
O17—C241.415 (6)C33—H33A0.9800
N1—C41.327 (4)C33—H33B0.9800
N1—C51.325 (5)C33—H33C0.9800
N2—H20.8800C34—H34A0.9900
N2—C121.330 (5)C34—H34B0.9900
N2—C131.343 (4)C35—C361.493 (5)
N3—C201.330 (5)C36—C371.390 (5)
N3—C211.333 (5)C36—C411.379 (5)
N4—H40.8800C37—H370.9500
N4—C281.337 (4)C37—C381.375 (6)
N4—C291.347 (5)C38—H380.9500
C1—H1A0.9900C38—C391.359 (7)
C1—H1B0.9900C39—H390.9500
C1—C21.500 (4)C39—C401.377 (7)
C2—C31.402 (4)C40—H400.9500
C2—C61.400 (5)C40—C411.396 (6)
C3—C41.416 (4)C41—H410.9500
C4—C71.484 (5)O16—H160.8400
C5—H50.9500O16—C421.380 (9)
C5—C61.373 (5)C42—H42A0.9900
C6—C81.504 (5)C42—H42B0.9900
C7—H7A0.9800C42—C431.384 (12)
C7—H7B0.9800C43—H43A0.9800
C7—H7C0.9800C43—H43B0.9800
C8—H8A0.9900C43—H43C0.9800
Mn2—Mn1—Mn363.190 (13)C28—N4—H4118.9
O1—Mn1—Mn293.74 (5)C28—N4—C29122.1 (3)
O1—Mn1—Mn340.33 (4)C29—N4—H4118.9
O2—Mn1—Mn242.04 (6)O1—C1—H1A108.9
O2—Mn1—Mn334.50 (6)O1—C1—H1B108.9
O2—Mn1—O174.81 (8)O1—C1—C2113.5 (3)
O2—Mn1—O581.03 (8)H1A—C1—H1B107.7
O2—Mn1—O1292.21 (9)C2—C1—H1A108.9
O3—Mn1—Mn2137.18 (6)C2—C1—H1B108.9
O3—Mn1—Mn384.67 (6)C3—C2—C1121.5 (3)
O3—Mn1—O175.72 (8)C6—C2—C1120.2 (3)
O3—Mn1—O295.59 (8)C6—C2—C3118.2 (3)
O3—Mn1—O5168.24 (9)O6—C3—C2124.1 (3)
O3—Mn1—O790.81 (9)O6—C3—C4117.3 (3)
O3—Mn1—O1297.35 (9)C2—C3—C4118.6 (3)
O5—Mn1—Mn242.05 (6)N1—C4—C3121.6 (3)
O5—Mn1—Mn386.28 (6)N1—C4—C7119.3 (3)
O5—Mn1—O192.52 (8)C3—C4—C7119.1 (3)
O5—Mn1—O1294.05 (9)N1—C5—H5117.9
O7—Mn1—Mn2132.02 (6)N1—C5—C6124.2 (3)
O7—Mn1—Mn3139.87 (7)C6—C5—H5117.9
O7—Mn1—O199.97 (8)C2—C6—C8122.7 (3)
O7—Mn1—O2170.40 (9)C5—C6—C2118.3 (3)
O7—Mn1—O591.27 (8)C5—C6—C8119.0 (3)
O7—Mn1—O1294.07 (9)C4—C7—H7A109.5
O12—Mn1—Mn281.78 (6)C4—C7—H7B109.5
O12—Mn1—Mn3126.06 (6)C4—C7—H7C109.5
O12—Mn1—O1164.36 (8)H7A—C7—H7B109.5
Mn1—Mn2—Mn362.784 (12)H7A—C7—H7C109.5
O2—Mn2—Mn141.74 (6)H7B—C7—H7C109.5
O2—Mn2—Mn334.32 (6)O13—C8—C6112.0 (4)
O2—Mn2—O4i79.51 (8)O13—C8—H8A109.2
O2—Mn2—O1192.14 (9)O13—C8—H8B109.2
O4i—Mn2—Mn198.83 (5)C6—C8—H8A109.2
O4i—Mn2—Mn345.19 (4)C6—C8—H8B109.2
O5—Mn2—Mn142.02 (6)H8A—C8—H8B107.9
O5—Mn2—Mn385.93 (6)O3—C9—H9A109.0
O5—Mn2—O280.72 (8)O3—C9—H9B109.0
O5—Mn2—O4i95.70 (8)O3—C9—C10112.9 (3)
O5—Mn2—O1192.82 (9)H9A—C9—H9B107.8
O9—Mn2—Mn1131.22 (6)C10—C9—H9A109.0
O9—Mn2—Mn3140.22 (7)C10—C9—H9B109.0
O9—Mn2—O2169.68 (9)C11—C10—C9121.0 (3)
O9—Mn2—O4i96.07 (8)C11—C10—C14118.9 (3)
O9—Mn2—O590.53 (8)C14—C10—C9120.1 (3)
O9—Mn2—O1193.74 (9)C10—C11—C15121.1 (4)
O10—Mn2—Mn1136.16 (6)C12—C11—C10119.2 (3)
O10—Mn2—Mn386.99 (6)C12—C11—C15119.7 (3)
O10—Mn2—O295.53 (8)N2—C12—C11120.3 (3)
O10—Mn2—O4i76.56 (8)N2—C12—H12119.8
O10—Mn2—O5171.95 (9)C11—C12—H12119.8
O10—Mn2—O992.46 (8)N2—C13—C14117.5 (3)
O10—Mn2—O1194.43 (9)N2—C13—C16119.1 (3)
O11—Mn2—Mn180.99 (6)C14—C13—C16123.4 (3)
O11—Mn2—Mn3125.98 (6)O7—C14—C10123.4 (3)
O11—Mn2—O4i166.93 (8)O7—C14—C13116.7 (3)
Mn1i—Mn3—Mn1180.0C10—C14—C13119.9 (3)
Mn1—Mn3—Mn2i125.975 (11)O14—C15—C11109.7 (4)
Mn1—Mn3—Mn254.026 (11)O14—C15—H15A109.7
Mn1i—Mn3—Mn2125.973 (11)O14—C15—H15B109.7
Mn1i—Mn3—Mn2i54.026 (11)C11—C15—H15A109.7
Mn2i—Mn3—Mn2180.0C11—C15—H15B109.7
Mn4i—Mn3—Mn1116.284 (12)H15A—C15—H15B108.2
Mn4—Mn3—Mn1i116.285 (12)C13—C16—H16A109.5
Mn4—Mn3—Mn163.716 (12)C13—C16—H16B109.5
Mn4i—Mn3—Mn1i63.715 (12)C13—C16—H16C109.5
Mn4i—Mn3—Mn262.297 (12)H16A—C16—H16B109.5
Mn4—Mn3—Mn2i62.298 (12)H16A—C16—H16C109.5
Mn4i—Mn3—Mn2i117.702 (12)H16B—C16—H16C109.5
Mn4—Mn3—Mn2117.703 (12)O4—C17—H17A108.3
Mn4i—Mn3—Mn4180.0O4—C17—H17B108.3
O1i—Mn3—Mn1i51.20 (6)O4—C17—C18115.8 (3)
O1—Mn3—Mn1i128.80 (6)H17A—C17—H17B107.4
O1i—Mn3—Mn1128.80 (6)C18—C17—H17A108.3
O1—Mn3—Mn151.20 (6)C18—C17—H17B108.3
O1i—Mn3—Mn2i94.51 (6)C19—C18—C17122.2 (3)
O1—Mn3—Mn294.51 (6)C19—C18—C22118.0 (3)
O1i—Mn3—Mn285.49 (6)C22—C18—C17119.8 (3)
O1—Mn3—Mn2i85.49 (6)O8—C19—C18125.0 (3)
O1—Mn3—Mn4i142.37 (5)O8—C19—C20116.1 (3)
O1—Mn3—Mn437.63 (5)C18—C19—C20118.9 (3)
O1i—Mn3—Mn4i37.64 (5)N3—C20—C19121.4 (3)
O1i—Mn3—Mn4142.37 (5)N3—C20—C23118.3 (3)
O1i—Mn3—O1180.0C19—C20—C23120.3 (3)
O1—Mn3—O4i104.56 (7)N3—C21—H21118.1
O1i—Mn3—O4i75.44 (7)N3—C21—C22123.8 (4)
O1i—Mn3—O4104.56 (7)C22—C21—H21118.1
O1—Mn3—O475.44 (7)C18—C22—C24122.5 (3)
O2i—Mn3—Mn1i34.74 (6)C21—C22—C18118.7 (3)
O2i—Mn3—Mn1145.26 (6)C21—C22—C24118.8 (3)
O2—Mn3—Mn134.74 (6)C20—C23—H23A109.5
O2—Mn3—Mn1i145.26 (6)C20—C23—H23B109.5
O2i—Mn3—Mn2145.20 (6)C20—C23—H23C109.5
O2i—Mn3—Mn2i34.80 (6)H23A—C23—H23B109.5
O2—Mn3—Mn234.80 (6)H23A—C23—H23C109.5
O2—Mn3—Mn2i145.21 (6)H23B—C23—H23C109.5
O2—Mn3—Mn4i88.58 (6)O17—C24—C22110.3 (4)
O2—Mn3—Mn491.42 (6)O17—C24—H24A109.6
O2i—Mn3—Mn4i91.42 (6)O17—C24—H24B109.6
O2i—Mn3—Mn488.58 (6)C22—C24—H24A109.6
O2—Mn3—O185.92 (8)C22—C24—H24B109.6
O2—Mn3—O1i94.08 (8)H24A—C24—H24B108.1
O2i—Mn3—O1i85.92 (8)O5—C25—H25A109.3
O2i—Mn3—O194.08 (8)O5—C25—H25B109.3
O2i—Mn3—O2180.00 (12)O5—C25—C26111.8 (3)
O2—Mn3—O496.56 (8)H25A—C25—H25B107.9
O2—Mn3—O4i83.44 (8)C26—C25—H25A109.3
O2i—Mn3—O483.45 (8)C26—C25—H25B109.3
O2i—Mn3—O4i96.55 (8)C25—C26—H26A109.5
O4i—Mn3—Mn194.02 (5)C25—C26—H26B109.5
O4—Mn3—Mn1i94.02 (5)C25—C26—H26C109.5
O4—Mn3—Mn185.98 (5)H26A—C26—H26B109.5
O4i—Mn3—Mn1i85.97 (5)H26A—C26—H26C109.5
O4—Mn3—Mn2i48.66 (5)H26B—C26—H26C109.5
O4—Mn3—Mn2131.34 (5)O9—C27—C28115.6 (3)
O4i—Mn3—Mn248.66 (5)O9—C27—C31124.3 (3)
O4i—Mn3—Mn2i131.34 (5)C31—C27—C28120.1 (3)
O4i—Mn3—Mn4i37.81 (5)N4—C28—C27119.1 (3)
O4—Mn3—Mn4i142.19 (5)N4—C28—C33118.8 (3)
O4i—Mn3—Mn4142.19 (5)C27—C28—C33122.1 (3)
O4—Mn3—Mn437.81 (5)N4—C29—H29119.5
O4i—Mn3—O4180.0N4—C29—C30120.9 (3)
O1—Mn4—Mn339.83 (6)C30—C29—H29119.5
O1—Mn4—O380.23 (8)C29—C30—C31119.4 (3)
O1—Mn4—O10i88.94 (8)C29—C30—C34119.9 (3)
O3—Mn4—Mn380.49 (5)C31—C30—C34120.7 (3)
O4—Mn4—Mn345.98 (5)C27—C31—C30118.3 (3)
O4—Mn4—O185.80 (8)C27—C31—C32121.1 (3)
O4—Mn4—O386.40 (8)C30—C31—C32120.6 (3)
O4—Mn4—O10i80.29 (8)O10—C32—C31114.1 (2)
O6—Mn4—Mn3131.65 (6)O10—C32—H32A108.7
O6—Mn4—O192.27 (9)O10—C32—H32B108.7
O6—Mn4—O3101.04 (9)C31—C32—H32A108.7
O6—Mn4—O4171.90 (10)C31—C32—H32B108.7
O6—Mn4—O889.03 (9)H32A—C32—H32B107.6
O6—Mn4—O10i91.82 (9)C28—C33—H33A109.5
O8—Mn4—Mn3139.31 (7)C28—C33—H33B109.5
O8—Mn4—O1172.24 (10)C28—C33—H33C109.5
O8—Mn4—O392.02 (9)H33A—C33—H33B109.5
O8—Mn4—O493.95 (9)H33A—C33—H33C109.5
O8—Mn4—O10i98.67 (9)H33B—C33—H33C109.5
O10i—Mn4—Mn383.17 (5)O15—C34—C30109.8 (3)
O10i—Mn4—O3163.43 (7)O15—C34—H34A109.7
Mn3—O1—Mn188.47 (7)O15—C34—H34B109.7
Mn4—O1—Mn196.62 (8)C30—C34—H34A109.7
Mn4—O1—Mn3102.54 (8)C30—C34—H34B109.7
C1—O1—Mn1124.55 (19)H34A—C34—H34B108.2
C1—O1—Mn3120.65 (17)O11—C35—O12125.0 (3)
C1—O1—Mn4117.86 (17)O11—C35—C36117.6 (3)
Mn1—O2—Mn296.23 (8)O12—C35—C36117.5 (3)
Mn3—O2—Mn1110.77 (10)C37—C36—C35120.2 (3)
Mn3—O2—Mn2110.88 (10)C41—C36—C35120.9 (3)
Mn1—O3—Mn4107.22 (9)C41—C36—C37118.9 (4)
C9—O3—Mn1117.61 (19)C36—C37—H37119.6
C9—O3—Mn4121.6 (2)C38—C37—C36120.7 (4)
Mn3—O4—Mn2i86.15 (7)C38—C37—H37119.6
Mn4—O4—Mn2i97.47 (8)C37—C38—H38119.8
Mn4—O4—Mn396.21 (8)C39—C38—C37120.5 (5)
C17—O4—Mn2i123.30 (17)C39—C38—H38119.8
C17—O4—Mn3125.88 (16)C38—C39—H39120.1
C17—O4—Mn4119.61 (17)C38—C39—C40119.8 (5)
Mn1—O5—Mn295.94 (8)C40—C39—H39120.1
C25—O5—Mn1120.45 (18)C39—C40—H40119.8
C25—O5—Mn2120.49 (17)C39—C40—C41120.4 (5)
C3—O6—Mn4128.97 (18)C41—C40—H40119.8
C14—O7—Mn1128.61 (19)C36—C41—C40119.6 (4)
C19—O8—Mn4127.91 (18)C36—C41—H41120.2
C27—O9—Mn2127.82 (18)C40—C41—H41120.2
Mn2—O10—Mn4i105.48 (9)C42—O16—H16109.5
C32—O10—Mn2119.09 (18)O16—C42—H42A110.8
C32—O10—Mn4i120.87 (19)O16—C42—H42B110.8
C35—O11—Mn2127.0 (2)O16—C42—C43104.9 (8)
C35—O12—Mn1125.1 (2)H42A—C42—H42B108.8
C8—O13—H13109.5C43—C42—H42A110.8
C15—O14—H14109.5C43—C42—H42B110.8
C34—O15—H15109.5C42—C43—H43A109.5
C24—O17—H17109.5C42—C43—H43B109.5
C5—N1—C4119.1 (3)C42—C43—H43C109.5
C12—N2—H2117.9H43A—C43—H43B109.5
C12—N2—C13124.1 (3)H43A—C43—H43C109.5
C13—N2—H2117.9H43B—C43—H43C109.5
C20—N3—C21119.2 (3)
Mn1—Mn2—O9—C27166.9 (2)O11—C35—C36—C41177.9 (3)
Mn1—Mn2—O10—Mn4i85.65 (11)O12—Mn1—O3—Mn4−169.09 (9)
Mn1—Mn2—O10—C32−134.58 (19)O12—Mn1—O3—C949.5 (2)
Mn1—O1—C1—C2−64.4 (3)O12—Mn1—O7—C14−89.6 (3)
Mn1—O3—C9—C1063.5 (3)O12—C35—C36—C37178.2 (3)
Mn1—O5—C25—C26−127.1 (3)O12—C35—C36—C41−2.5 (5)
Mn1—O7—C14—C1012.5 (5)N1—C5—C6—C2−0.1 (7)
Mn1—O7—C14—C13−167.8 (2)N1—C5—C6—C8178.7 (4)
Mn1—O12—C35—O113.5 (4)N2—C13—C14—O7−178.4 (3)
Mn1—O12—C35—C36−176.0 (2)N2—C13—C14—C101.3 (5)
Mn2—Mn1—O3—Mn4−83.27 (12)N3—C21—C22—C180.6 (7)
Mn2—Mn1—O3—C9135.3 (2)N3—C21—C22—C24179.5 (4)
Mn2—Mn1—O7—C14−172.2 (2)N4—C29—C30—C31−1.5 (6)
Mn2i—O4—C17—C18−74.6 (3)N4—C29—C30—C34179.7 (4)
Mn2—O5—C25—C26113.8 (3)C1—C2—C3—O64.7 (5)
Mn2—O9—C27—C28171.4 (2)C1—C2—C3—C4−173.4 (3)
Mn2—O9—C27—C31−8.0 (5)C1—C2—C6—C5174.9 (4)
Mn2—O10—C32—C31−57.1 (3)C1—C2—C6—C8−3.8 (6)
Mn2—O11—C35—O12−5.1 (5)C2—C3—C4—N1−3.1 (5)
Mn2—O11—C35—C36174.4 (2)C2—C3—C4—C7176.2 (3)
Mn3—Mn1—O3—Mn4−43.35 (7)C2—C6—C8—O1371.6 (5)
Mn3—Mn1—O3—C9175.2 (2)C3—C2—C6—C5−1.9 (6)
Mn3—Mn1—O7—C1490.5 (3)C3—C2—C6—C8179.4 (4)
Mn3—Mn2—O9—C27−97.2 (2)C4—N1—C5—C60.5 (7)
Mn3—Mn2—O10—Mn4i41.38 (7)C5—N1—C4—C31.1 (6)
Mn3—Mn2—O10—C32−178.9 (2)C5—N1—C4—C7−178.2 (4)
Mn3—Mn4—O6—C3−2.7 (3)C5—C6—C8—O13−107.1 (5)
Mn3—Mn4—O8—C19−2.2 (3)C6—C2—C3—O6−178.5 (3)
Mn3—O1—C1—C2−176.10 (19)C6—C2—C3—C43.4 (5)
Mn3—O4—C17—C18173.3 (2)C9—C10—C11—C12−179.9 (4)
Mn4—O1—C1—C257.1 (3)C9—C10—C11—C15−0.6 (6)
Mn4—O3—C9—C10−72.1 (3)C9—C10—C14—O7−0.6 (5)
Mn4—O4—C17—C1848.9 (3)C9—C10—C14—C13179.7 (3)
Mn4—O6—C3—C211.1 (5)C10—C11—C12—N2−0.9 (6)
Mn4—O6—C3—C4−170.8 (2)C10—C11—C15—O14169.2 (4)
Mn4—O8—C19—C187.3 (5)C11—C10—C14—O7177.6 (3)
Mn4—O8—C19—C20−173.6 (2)C11—C10—C14—C13−2.1 (5)
Mn4i—O10—C32—C3176.4 (3)C12—N2—C13—C14−0.3 (5)
O1—Mn1—O3—Mn4−3.38 (7)C12—N2—C13—C16−178.4 (4)
O1—Mn1—O3—C9−144.8 (2)C12—C11—C15—O14−11.5 (6)
O1—Mn1—O7—C1483.5 (3)C13—N2—C12—C110.0 (6)
O1—Mn4—O6—C33.8 (3)C14—C10—C11—C121.9 (6)
O1—C1—C2—C3−40.1 (4)C14—C10—C11—C15−178.8 (4)
O1—C1—C2—C6143.2 (3)C15—C11—C12—N2179.8 (4)
O2—Mn1—O3—Mn4−76.12 (10)C16—C13—C14—O7−0.4 (5)
O2—Mn1—O3—C9142.4 (2)C16—C13—C14—C10179.3 (3)
O2—Mn2—O9—C27−149.7 (5)C17—C18—C19—O82.5 (5)
O2—Mn2—O10—Mn4i74.66 (10)C17—C18—C19—C20−176.5 (3)
O2—Mn2—O10—C32−145.6 (2)C17—C18—C22—C21176.8 (4)
O3—Mn1—O7—C147.8 (3)C17—C18—C22—C24−2.0 (6)
O3—Mn4—O6—C384.3 (3)C18—C19—C20—N3−1.0 (5)
O3—Mn4—O8—C19−80.0 (3)C18—C19—C20—C23178.8 (3)
O3—C9—C10—C11144.1 (3)C18—C22—C24—O1764.0 (5)
O3—C9—C10—C14−37.7 (5)C19—C18—C22—C21−0.2 (6)
O4i—Mn2—O9—C27−85.7 (3)C19—C18—C22—C24−179.1 (4)
O4i—Mn2—O10—Mn4i−3.14 (7)C20—N3—C21—C22−1.1 (7)
O4i—Mn2—O10—C32136.6 (2)C21—N3—C20—C191.2 (6)
O4—Mn4—O8—C196.6 (3)C21—N3—C20—C23−178.5 (4)
O4—C17—C18—C19−32.1 (5)C21—C22—C24—O17−114.8 (4)
O4—C17—C18—C22151.0 (3)C22—C18—C19—O8179.5 (3)
O5—Mn1—O3—Mn4−3.5 (5)C22—C18—C19—C200.4 (5)
O5—Mn1—O3—C9−144.9 (4)C27—C31—C32—O1035.1 (4)
O5—Mn1—O7—C14176.2 (3)C28—N4—C29—C301.9 (6)
O5—Mn2—O9—C27178.5 (3)C28—C27—C31—C301.4 (5)
O6—Mn4—O8—C19179.0 (3)C28—C27—C31—C32178.7 (3)
O6—C3—C4—N1178.7 (3)C29—N4—C28—C27−0.6 (5)
O6—C3—C4—C7−2.0 (5)C29—N4—C28—C33179.2 (4)
O7—Mn1—O3—Mn496.70 (10)C29—C30—C31—C27−0.1 (5)
O7—Mn1—O3—C9−44.7 (2)C29—C30—C31—C32−177.5 (4)
O8—Mn4—O6—C3176.1 (3)C29—C30—C34—O157.5 (6)
O8—C19—C20—N3179.9 (3)C30—C31—C32—O10−147.7 (3)
O8—C19—C20—C23−0.4 (5)C31—C27—C28—N4−1.1 (5)
O9—Mn2—O10—Mn4i−98.80 (10)C31—C27—C28—C33179.1 (3)
O9—Mn2—O10—C3241.0 (2)C31—C30—C34—O15−171.2 (4)
O9—C27—C28—N4179.5 (3)C34—C30—C31—C27178.6 (4)
O9—C27—C28—C33−0.4 (5)C34—C30—C31—C321.3 (5)
O9—C27—C31—C30−179.2 (3)C35—C36—C37—C38179.5 (3)
O9—C27—C31—C32−1.9 (5)C35—C36—C41—C40−179.0 (3)
O10—Mn2—O9—C27−9.0 (3)C36—C37—C38—C39−0.3 (6)
O10i—Mn4—O6—C3−85.2 (3)C37—C36—C41—C400.3 (5)
O10i—Mn4—O8—C1987.3 (3)C37—C38—C39—C40−0.1 (7)
O11—Mn2—O9—C2785.6 (3)C38—C39—C40—C410.6 (7)
O11—Mn2—O10—Mn4i167.25 (9)C39—C40—C41—C36−0.7 (6)
O11—Mn2—O10—C32−53.0 (2)C41—C36—C37—C380.2 (5)
O11—C35—C36—C37−1.4 (5)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O14—H14···N3ii0.841.802.619 (4)163
O15—H15···N1iii0.841.842.675 (4)175
O17—H17···O13i0.841.892.684 (5)158
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+2; (iii) x, y, z−1.
 

Funding information

Funding for this research was provided by: National Science Foundation (grant No. 1359229).

References

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ISSN: 2414-3146
Volume 6| Part 1| January 2021| x201643
https://doi.org/10.1107/S2414314620016430
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