metal-organic papers l 3 -Oxo-hexa-l 2 -pivalato-(pivalic acid-jo)- bis(pyridine-jn)trimanganese(iii,iii,ii) Comment Musa Sarı, a * Mehmet Poyraz, b

Transcription

1 metal-organic papers Acta Crystallographica Section E Structure Reports Online ISSN l 3 -Oxo-hexa-l 2 -pivalato-(pivalic acid-jo)- bis(pyridine-jn)trimanganese(iii,iii,ii) Musa Sarı, a * Mehmet Poyraz, b Orhan Büyükgüngör c and Roderick D. Cannon d a Gazi University, Department of Physics Education, Beşevler, Ankara, Turkey, b Afyon Kocatepe University, Department of Chemistry, Science and Literature Faculty, Afyonkarahisar, Turkey, c Department of Physics, Science and Literature Faculty, Ondokuz Mayıs University, TR-55139, kurupelit Samsun, Turkey, and d School of Chemical Sciences, University of East Anglia, Norwich NR4 7TJ, England Correspondence msari@gazi.edu.tr Key indicators Single-crystal X-ray study T = 150 K Mean (C C) = Å Disorder in main residue R factor = wr factor = Data-to-parameter ratio = 16.5 The asymmetric unit of the title compound, [Mn 3 (C 5 H 9 O 2 ) 6 O(C 5 H 5 N) 2 (C 5 H 10 O 2 )], comprises two independent and similar [Mn III 2Mn II O{(CH 3 ) 3 CCO 2 } 6 (py) 2 - (CH 3 ) 3 CCOOH] (py = pyridine) molecules each with an Mn 3 ( 3 -O) core. In each molecule, the Mn atoms have octahedral geometry with two coordinated pyridines bonded to two Mn III and a terminal pivalic acid coordinated to the Mn II atom. Comment Oxo-centered triangular Mn complexes, Mn 3 ( 3 -O), have been considered as effective models for studying M M interactions in mixed-metal clusters, and electron delocalization in mixed-valence clusters. A wide variety of mixed-metal combinations and mixed-valency combinations have been reported (Cannon & White, 1988; Jayasooriya et al., 1989; Wu et al., 1998). In the Mn 3 ( 3 -O) systems, the geometry of the central core remains relatively constant throughout the series and is often close to having threefold symmetry with a planar M 3 O unit (Wu et al., 1998). Received 27 September 2006 Accepted 13 November 2006 For details of how these key indicators were automatically derived from the article, see # 2006 International Union of Crystallography All rights reserved In (I), the three Mn atoms form a regular triangular geometry and are linked by a central 3 -O atom (Fig. 1). The asymmetric unit consists of two independent and similar molecules (A and B), [Mn III 2Mn II O{(CH 3 ) 3 CCO 2 } 6 (py) 2 - (CH 3 ) 3 CCO- doi: /s Sarı et al. [Mn 3 (C 5 H 9 O 2 ) 6 O(C 5 H 5 N) 2 (C 5 H 10 O 2 )] m3439

2 metal-organic papers then the mixture was left to cool and filtered. Two layers in the flask were separated and after several days black crystals from the organic layer were collected, washed thoroughly with water and dried in air. Figure 1 The molecular structure and atomic labelling scheme of molecule A in (I). Displacement ellipsoids are drawn at the 20% probability level. The tertbutyl methyl groups and H atoms, except for those of the pivalic acid ligands, have been omitted for clarity and open dashed lines indicate hydrogen bonds. Crystal data [Mn 3 (C 5 H 9 O 2 ) 6 O(C 5 H 5 N) 2 - (C 5 H 10 O 2 )] M r = Monoclinic, P2 1 =c a = (7) Å b = (4) Å c = (5) Å = (2) Data collection Stoe IPDS-2 diffractometer Rotation method scans Absorption correction: integration (X-RED32; Stoe & Cie, 2002) T min = 0.759, T max = Refinement Refinement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 1220 parameters H-atom parameters constrained V = (5) Å 3 Z =8 D x = Mg m 3 Mo K radiation = 0.72 mm 1 T = 150 (2) K Prism, black mm measured reflections independent reflections reflections with I > 2(I) R int = max = 25.1 w = 1/[ 2 (F o 2 ) + (0.0596P) 2 ] where P =(F o 2 +2F c 2 )/3 (/) max = max = 0.62 e Å 3 min = 0.41 e Å 3 Extinction correction: SHELXL97 Extinction coefficient: none OH]. The Mn atoms in both molecules have two different types of Mn ( 3 -O) bond lengths (Table 1). The Mn 3 triangle is isosceles and clearly indicates that one Mn atom differs from the other two. This is most logically interpreted in terms of identifying Mn3A and Mn3B as having different oxidation states from the other Mn atoms. This asymmetry is most noticeable in the Mn 3 O central core, with longer Mn3A O1 and Mn3B O16 distances. The planes of the coordinated pyridines are almost orthogonal to the central Mn 3 O core. The Mn N bond lengths in A and B are quite similar and in the range (3) to (4) Å: these bond lengths agree with Mn III N for related Mn 3 ( 3 -O) complexes [2.061 (10) (7) Å; Baikie et al., 1978; Baikie et al., 1980; Vincent et al., 1987; Wu et al., 1998]. Other selected bond lengths and angles agree well with the literature values (see previous references). In both molecules, the Mn III atoms show a typical Jahn Teller distortion, with two longer and two shorter Mn O bonds. The long pair form a long axis in a pseudo-octahedral coordination (Wu et al., 1998). The crystal structure is stabilized by intermolecular O HO hydrogen bonds involving the H atoms of terminal pivalic acid groups and O atoms of the pivalate groups (Table 2). Experimental A mixture of molten pivalic acid (60 ml), pyridine (40 ml) and water (20 ml) was added to a mixture of ground MnCl 2 4H 2 O (8.8 g, 44 mmol) and finely ground KMnO 4 (0.81 g, 5.2 mmol) in a 250 ml conical flask. The mixture was heated at K with stirring and Table 1 Selected geometric parameters (Å, ). Mn1A O (3) Mn1A O (3) Mn1A O (3) Mn1A O (3) Mn1A O (3) Mn2A O (3) Mn2A O (3) Mn2A O (3) Mn2A O (3) Mn2A O (3) Mn3A O (3) Mn3A O (3) Mn3A O (3) Mn3A O (4) Mn3A O (4) Mn3A O (3) O1 Mn1A N (13) O1 Mn2A N (15) Mn1A O1 Mn2A (15) Mn1A O1 Mn3A (14) Mn2A O1 Mn3A (14) Table 2 Hydrogen-bond geometry (Å, ). Mn1B O (3) Mn1B O (3) Mn1B O (3) Mn1B O (3) Mn1B O (3) Mn2B O (3) Mn2B O (3) Mn2B O (3) Mn2B O (3) Mn2B O (3) Mn3B O (3) Mn3B O (3) Mn3B O (3) Mn3B O (3) Mn3B O (3) Mn3B O (3) O16 Mn1B N (14) O16 Mn2B N (14) Mn1B O16 Mn2B (15) Mn1B O16 Mn3B (13) Mn2B O16 Mn3B (14) D HA D H HA DA D HA O11 H11O (5) 172 O26 H26O (4) 170 Ten tert-butyl groups are disordered, giving unrealistically anisotropic displacement parameters and bond lengths. The refinement was performed with soft restraints for the split C atom sites, leading to m3440 Sarı et al. [Mn 3 (C 5 H 9 O 2 ) 6 O(C 5 H 5 N) 2 (C 5 H 10 O 2 )]

3 metal-organic papers satisfactory refinement results. For the disordered tert-butyl groups the C CH 3 distances were constrained to 1.52 (2) Å. Fixed occupancy factors of 0.5 were applied for both positions initially as it was possible to obtain reasonable refined values for related pairs: these were subsequently allowed to vary but constrained to sum to unit occupancy. All non-h atoms, except for the disordered C atoms, were assigned anisotropic displacement parameters. The H atoms were placed in idealized positions and refined using a riding model, with distances in the range Å and U iso (H) = 1.2U eq (C,O) or 1.5U eq (methyl C). Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X- AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97. The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for use of the Stoe IPDS2 diffractometer purchased under grant F.279 of the University Research Fund and also thank Gazi University Scientific Research Unit (BAP-04/ ) for financial support for this study. References Baikie, A. R. E., Hursthouse, M. B., New, D. B. & Thornton, P. (1978). J. Chem. Soc. Chem. Commun. pp Baikie, A. R. E., Hursthouse, M. B., New, L., Thornton, P. & White, R. G. (1980). J. Chem. Soc. Chem. Commun. pp Cannon, R. D. & White, R. P. (1988). Prog. Inorg. Chem. 36, Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Jayasooriya, U. A., Cannon, R. D., White, R. P. & Kearley, G. J. (1989). Angew. Chem. Int. Ed. Engl. 28, Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Stoe & Cie (2002). X-AREA (Version 1.18) and X-RED32 (Version 1.04). Stoe & Cie, Darmstadt, Germany. Vincent, J. B., Chang, H. R., Folting, K., Huffman, J. C., Christou, G. & Hendrickson, D. N. (1987). J. Am. Chem. Soc. 109, Wu, R., Poyraz, M., Sowrey, F. E., Anson, C. E., Wocaldo, S., Powell, A. K., Jayasooriya, U. A., Cannon, D. R., Nakamoto, T., Katada, M. & Sano, H. (1998). Inorg. Chem. 37, Sarı et al. [Mn 3 (C 5 H 9 O 2 ) 6 O(C 5 H 5 N) 2 (C 5 H 10 O 2 )] m3441

4 supporting information [ µ 3 -Oxo-hexa-µ 2 -pivalato-(pivalic acid-κo)bis(pyridineκn)trimanganese(iii,iii,ii) Musa Sarı, Mehmet Poyraz, Orhan Büyükgüngör and Roderick D. Cannon µ 3 -Oxo-hexa-µ 2 -pivalato-(pivalic acid-κo)bis(pyridine- κn)trimanganese(iii,iii,ii) Crystal data [Mn 3 (C 5 H 9 O 2 ) 6 O(C 5 H 5 N) 2 (C 5 H 10 O 2 )] M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (7) Å b = (4) Å c = (5) Å β = (2) V = (5) Å 3 Z = 8 Data collection Stoe IPDS-2 diffractometer Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus Plane graphite monochromator φ? ω? scans Absorption correction: integration (X-RED32; Stoe & Cie, 2002) T min = 0.759, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 1220 parameters 171 restraints Primary atom site location: structure-invariant direct methods F(000) = 4424 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 25 reflections θ = µ = 0.72 mm 1 T = 150 K Prism, black mm measured reflections independent reflections reflections with I > 2σ(I) R int = θ max = 25.1, θ min = 1.3 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0596P) 2 ] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.62 e Å 3 Δρ min = 0.41 e Å 3 Extinction correction: SHELXL97 Extinction coefficient: none sup-1

5 Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Occ. (<1) Mn1A (3) (3) (3) (16) Mn2A (3) (3) (3) (16) Mn3A (3) (4) (3) (18) O (11) (14) (12) (7) O (13) (15) (14) (8) O (13) (16) (13) (8) O (13) (16) (13) (8) O (12) (16) (13) (8) O (13) (17) (14) (8) O (12) (19) (14) (9) O (12) (16) (13) (8) O (14) (17) (15) (9) O (16) (2) (17) (10) O (18) (3) (2) (17) H * O (14) (17) (15) (9) O (12) (15) (14) (7) O (12) (17) (14) (8) O (12) (15) (13) (7) N (15) (18) (15) (9) N (15) (19) (16) (9) C (2) (3) (2) (13) H * C (2) (3) (3) (16) H * C (3) (3) (2) (16) H * C (3) (3) (2) (16) H * C (2) (2) (2) (13) H * C (2) (2) (2) (12) C (2) (2) (2) (18) C8A (6) (5) (5) (5)* (15) H8A * (15) H8B * (15) H8C * (15) C9A (4) (6) (5) (4)* (15) H9A * (15) H9B * (15) H9C * (15) C10A (5) (7) (7) (5)* (15) H10A * (15) H10B * (15) H10C * (15) sup-2

6 C8C (6) (5) (6) (4)* (15) H8D * (15) H8E * (15) H8F * (15) C9C (7) (8) (4) (6)* (15) H9D * (15) H9E * (15) H9F * (15) C10C (4) (8) (8) (5)* (15) H10D * (15) H10E * (15) H10F * (15) C (19) (2) (2) (11) C (19) (3) (2) (13) C (2) (4) (3) (2) H13A * H13B * H13C * C (2) (4) (3) (2) H14A * H14B * H14C * C (2) (4) (2) (19) H15A * H15B * H15C * C (2) (3) (2) (12) H * C (2) (3) (2) (14) H * C (2) (3) (2) (15) H * C (2) (3) (2) (14) H * C (2) (3) (2) (12) H * C (18) (3) (2) (12) C (2) (3) (2) (17) C23A (4) (5) (4) (3)* (11) H23A * (11) H23B * (11) H23C * (11) C24A (3) (6) (4) (4)* (11) H24A * (11) H24B * (11) H24C * (11) C25A (4) (4) (5) (4)* (11) H25A * (11) sup-3

7 H25B * (11) H25C * (11) C23C (7) (10) (5) (6)* (11) H23D * (11) H23E * (11) H23F * (11) C24C (7) (9) (8) (9)* (11) H24D * (11) H24E * (11) H24F * (11) C25C (7) (7) (9) (8)* (11) H25D * (11) H25E * (11) H25F * (11) C (19) (2) (2) (11) C (2) (3) (2) (15) C28A (6) (7) (7) (5)* (11) H28A * (11) H28B * (11) H28C * (11) C29A (4) (6) (6) (3)* (11) H29A * (11) H29B * (11) H29C * (11) C30A (5) (5) (5) (3)* (11) H30A * (11) H30B * (11) H30C * (11) C28C (7) (7) (5) (5)* (11) H28D * (11) H28E * (11) H28F * (11) C29C (4) (11) (10) (8)* (11) H29D * (11) H29E * (11) H29F * (11) C30C (8) (9) (9) (7)* (11) H30D * (11) H30E * (11) H30F * (11) C (3) (3) (3) (17) C (2) (3) (3) (2) C33A (4) (8) (5) (4)* 0.73 (2) H33A * 0.73 (2) H33B * 0.73 (2) H33C * 0.73 (2) C34A (5) (6) (5) (4)* 0.73 (2) H34A * 0.73 (2) sup-4

8 H34B * 0.73 (2) H34C * 0.73 (2) C35A (4) (4) (4) (4)* 0.73 (2) H35A * 0.73 (2) H35B * 0.73 (2) H35C * 0.73 (2) C33C (7) (17) (7) (8)* 0.27 (2) H33D * 0.27 (2) H33E * 0.27 (2) H33F * 0.27 (2) C34C (17) (11) (13) (18)* 0.27 (2) H34D * 0.27 (2) H34E * 0.27 (2) H34F * 0.27 (2) C35C (13) (2) (14) 0.21 (11)* 0.27 (2) H35D * 0.27 (2) H35E * 0.27 (2) H35F * 0.27 (2) C (2) (3) (2) (11) C (2) (3) (2) (13) C (3) (3) (3) (17) H38A * H38B * H38C * C (2) (3) (3) (16) H39A * H39B * H39C * C (2) (3) (3) (15) H40A * H40B * H40C * C (19) (3) (2) (12) C (2) (3) (3) (2) C43A (5) (4) (6) (4)* (12) H43A * (12) H43B * (12) H43C * (12) C44A (5) (7) (4) (5)* (12) H44A * (12) H44B * (12) H44C * (12) C45A (4) (7) (7) (6)* (12) H45A * (12) H45B * (12) H45C * (12) C43C (7) (8) (10) (8)* (12) H43D * (12) sup-5

9 H43E * (12) H43F * (12) C44C (5) (10) (8) (8)* (12) H44D * (12) H44E * (12) H44F * (12) C45C (8) (11) (7) (10)* (12) H45D * (12) H45E * (12) H45F * (12) Mn1B (3) (3) (3) (16) Mn2B (2) (3) (3) (15) Mn3B (3) (3) (3) (16) O (11) (13) (12) (7) O (12) (15) (13) (7) O (12) (14) (12) (7) O (12) (15) (13) (7) O (12) (14) (13) (7) O (11) (15) (12) (7) O (12) (15) (14) (8) O (11) (15) (13) (7) O (13) (15) (14) (8) O (13) (15) (13) (8) O (15) (16) (15) (9) H * O (13) (15) (14) (8) O (12) (16) (13) (8) O (13) (16) (14) (8) O (13) (16) (15) (8) N (15) (19) (19) (10) N (14) (17) (15) (9) C (2) (3) (3) (14) H * C (2) (4) (3) (2) H * C (3) (4) (4) (2) H * C (3) (3) (4) (19) H * C (2) (3) (3) (14) H * C (19) (2) (18) (10) C (17) (2) (2) (13) C53A (5) (7) (5) (4)* (13) H53A * (13) H53B * (13) H53C * (13) C54A (4) (4) (5) (4)* (13) sup-6

10 H54A * (13) H54B * (13) H54C * (13) C55A (3) (7) (5) (3)* (13) H55A * (13) H55B * (13) H55C * (13) C53C (5) (5) (4) (4)* (13) H53D * (13) H53E * (13) H53F * (13) C54C (4) (7) (7) (5)* (13) H54D * (13) H54E * (13) H54F * (13) C55C (4) (6) (5) (3)* (13) H55D * (13) H55E * (13) H55F * (13) C (19) (2) (19) (11) C (2) (2) (2) (12) C (2) (4) (3) (19) H58A * H58B * H58C * C (2) (3) (2) (16) H59A * H59B * H59C * C (2) (3) (2) (16) H60A * H60B * H60C * C (19) (2) (2) (11) H * C (2) (2) (2) (13) H * C (2) (3) (3) (14) H * C (2) (3) (2) (14) H * C (19) (2) (2) (12) H * C (17) (2) (19) (10) C (19) (2) (2) (13) C68A (5) (5) (4) (4)* (10) H68A * (10) H68B * (10) sup-7

11 H68C * (10) C69A (4) (7) (6) (5)* (10) H69A * (10) H69B * (10) H69C * (10) C70A (4) (4) (4) (3)* (10) H70A * (10) H70B * (10) H70C * (10) C68C (7) (10) (5) (7)* (10) H68D * (10) H68E * (10) H68F * (10) C69C (5) (7) (7) (5)* (10) H69D * (10) H69E * (10) H69F * (10) C70C (7) (7) (9) (9)* (10) H70D * (10) H70E * (10) H70F * (10) C (17) (2) (19) (10) C (18) (2) (19) (11) C (2) (3) (2) (14) H73A * H73B * H73C * C (2) (3) (3) (15) H74A * H74B * H74C * C (2) (3) (2) (14) H75A * H75B * H75C * C (19) (2) (2) (12) C (2) (2) (2) (15) C78A (3) (4) (4) (3)* (11) H78A * (11) H78B * (11) H78C * (11) C79A (4) (5) (4) (3)* (11) H79A * (11) H79B * (11) H79C * (11) C80A (3) (4) (4) (2)* (11) H80A * (11) H80B * (11) sup-8

12 H80C * (11) C78C (8) (10) (14) (15)* (11) H78D * (11) H78E * (11) H78F * (11) C79C (7) (10) (7) (7)* (11) H79D * (11) H79E * (11) H79F * (11) C80C (9) (9) (7) (7)* (11) H80D * (11) H80E * (11) H80F * (11) C (18) (2) (2) (11) C (19) (3) (2) (14) C83A (6) (6) (5) (5)* (12) H83A * (12) H83B * (12) H83C * (12) C84A (3) (7) (6) (4)* (12) H84A * (12) H84B * (12) H84C * (12) C85A (5) (5) (6) (5)* (12) H85A * (12) H85B * (12) H85C * (12) C83C (5) (6) (6) (5)* (12) H83D * (12) H83E * (12) H83F * (12) C84C (6) (8) (7) (7)* (12) H84D * (12) H84E * (12) H84F * (12) C85C (5) (8) (6) (6)* (12) H85D * (12) H85E * (12) H85F * (12) C (19) (2) (19) (11) C (19) (2) (2) (14) C88A (5) (6) (4) (4)* (14) H88A * (14) H88B * (14) H88C * (14) C89A (3) (8) (7) (5)* (14) H89A * (14) H89B * (14) sup-9

13 H89C * (14) C90A (4) (4) (4) (3)* (14) H90A * (14) H90B * (14) H90C * (14) C88C (8) (4) (5) (7)* (14) H88D * (14) H88E * (14) H88F * (14) C89C (4) (8) (6) (5)* (14) H89D * (14) H89E * (14) H89F * (14) C90C (6) (6) (8) (5)* (14) H90D * (14) H90E * (14) H90F * (14) Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Mn1A (4) (3) (3) (3) (3) (3) Mn2A (4) (4) (3) (3) (3) (3) Mn3A (4) (4) (4) (3) (3) (3) O (18) (16) (15) (13) (13) (12) O (2) (17) (18) (16) (17) (14) O (2) (19) (17) (16) (15) (14) O (2) (19) (17) (16) (15) (14) O (19) (19) (18) (15) (14) (14) O (2) (2) (18) (17) (16) (15) O (2) (3) (19) (18) (15) (17) O (2) (18) (17) (16) (15) (14) O (2) (2) (2) (17) (17) (16) O (3) (3) (2) (2) (19) (2) O (3) (5) (3) (3) (2) (3) O (2) (2) (2) (18) (17) (16) O (2) (18) (18) (15) (15) (14) O (2) (2) (18) (16) (15) (15) O (19) (19) (16) (14) (14) (13) N (2) (2) (2) (17) (17) (16) N (2) (2) (2) (19) (18) (17) C (3) (3) (3) (3) (3) (2) C (4) (4) (4) (3) (3) (3) C (4) (4) (3) (3) (3) (3) C (5) (3) (3) (3) (3) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (6) (3) (3) (3) (4) (2) sup-10

14 C (3) (2) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (3) C (4) (6) (4) (4) (3) (4) C (4) (5) (5) (4) (3) (4) C (4) (5) (3) (4) (3) (3) C (3) (3) (3) (2) (2) (2) C (4) (4) (3) (3) (3) (3) C (4) (4) (3) (3) (3) (3) C (4) (4) (3) (3) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (5) (4) (3) (3) (3) C (3) (3) (3) (2) (2) (2) C (4) (3) (3) (3) (3) (2) C (5) (5) (4) (4) (4) (3) C (4) (5) (4) (4) (3) (4) C (3) (3) (2) (2) (2) (2) C (3) (3) (3) (3) (3) (2) C (5) (3) (4) (3) (4) (3) C (4) (4) (4) (3) (3) (3) C (4) (4) (4) (3) (3) (3) C (3) (3) (3) (2) (2) (2) C (4) (4) (5) (3) (3) (3) Mn1B (4) (3) (4) (3) (3) (3) Mn2B (4) (3) (3) (3) (3) (3) Mn3B (4) (3) (3) (3) (3) (3) O (17) (15) (15) (12) (13) (12) O (2) (17) (17) (14) (15) (13) O (19) (17) (16) (14) (14) (13) O (19) (17) (17) (15) (15) (14) O (19) (17) (17) (14) (15) (13) O (18) (17) (16) (14) (13) (13) O (2) (17) (18) (15) (15) (14) O (18) (17) (16) (14) (13) (14) O (2) (17) (18) (15) (16) (14) O (2) (17) (17) (15) (15) (14) O (3) (18) (19) (18) (19) (15) O (2) (18) (18) (15) (16) (14) O (19) (19) (17) (15) (14) (14) O (2) (19) (19) (16) (16) (15) O (2) (18) (2) (15) (16) (15) N (2) (2) (3) (18) (2) (19) N (2) (19) (19) (17) (16) (15) C (3) (3) (3) (3) (3) (3) C (4) (5) (5) (3) (3) (4) C (4) (6) (7) (4) (4) (5) C (4) (4) (6) (3) (4) (4) C (4) (3) (4) (3) (3) (3) sup-11

15 C (3) (2) (2) (2) (2) (18) C (3) (3) (3) (2) (2) (2) C (3) (2) (2) (2) (2) (18) C (3) (3) (2) (2) (2) (2) C (4) (6) (3) (4) (3) (3) C (5) (3) (3) (3) (3) (2) C (5) (3) (3) (3) (3) (2) C (3) (3) (2) (2) (2) (2) C (3) (3) (3) (3) (3) (2) C (4) (3) (4) (3) (3) (3) C (3) (3) (3) (3) (3) (3) C (3) (3) (3) (2) (2) (2) C (3) (3) (2) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (2) (2) (19) (19) (18) C (3) (2) (2) (2) (2) (19) C (4) (3) (3) (3) (3) (2) C (4) (3) (4) (3) (3) (3) C (4) (3) (3) (3) (3) (2) C (3) (3) (3) (2) (2) (2) C (4) (3) (3) (3) (3) (2) C (3) (3) (3) (2) (2) (2) C (3) (4) (3) (3) (2) (3) C (3) (3) (2) (2) (2) (2) C (4) (3) (3) (3) (3) (3) Geometric parameters (Å, º) Mn1A O (3) Mn1B O (3) Mn1A O (3) Mn1B O (3) Mn1A O (3) Mn1B O (3) Mn1A O (3) Mn1B O (3) Mn1A O (3) Mn1B O (3) Mn1A N (4) Mn1B N (4) Mn1A Mn2A (9) Mn1B Mn2B (9) Mn2A O (3) Mn2B O (3) Mn2A O (3) Mn2B O (3) Mn2A O (3) Mn2B O (3) Mn2A O (3) Mn2B O (3) Mn2A O (3) Mn2B O (3) Mn2A N (3) Mn2B N (4) Mn3A O (3) Mn3B O (3) Mn3A O (3) Mn3B O (3) Mn3A O (3) Mn3B O (3) Mn3A O (4) Mn3B O (3) Mn3A O (4) Mn3B O (3) Mn3A O (3) Mn3B O (3) O2 C (6) O17 C (5) sup-12

16 O3 C (6) O18 C (5) O4 C (5) O19 C (5) O5 C (5) O20 C (5) O6 C (5) O21 C (5) O7 C (5) O22 C (5) O8 C (5) O23 C (5) O9 C (5) O24 C (5) O10 C (7) O25 C (5) O11 C (7) O26 C (5) O11 H O26 H O12 C (6) O27 C (5) O13 C (5) O28 C (5) O14 C (6) O29 C (5) O15 C (5) O30 C (5) N1 C (6) N3 C (7) N1 C (6) N3 C (6) N2 C (6) N4 C (6) N2 C (6) N4 C (5) C1 C (7) C46 C (8) C1 H C46 H C2 C (8) C47 C (10) C2 H C47 H C3 C (8) C48 C (10) C3 H C48 H C4 C (7) C49 C (8) C4 H C49 H C5 H C50 H C6 C (6) C51 C (6) C7 C9C (8) C52 C53A (8) C7 C10A (8) C52 C54C (8) C7 C8A (8) C52 C55C (7) C7 C8C (8) C52 C55A (7) C7 C10C (8) C52 C53C (8) C7 C9A (8) C52 C54A (7) C8A H8A C53A H53A C8A H8B C53A H53B C8A H8C C53A H53C C9A H9A C54A H54A C9A H9B C54A H54B C9A H9C C54A H54C C10A H10A C55A H55A C10A H10B C55A H55B C10A H10C C55A H55C C8C H8D C53C H53D C8C H8E C53C H53E C8C H8F C53C H53F C9C H9D C54C H54D C9C H9E C54C H54E sup-13

17 C9C H9F C54C H54F C10C H10D C55C H55D C10C H10E C55C H55E C10C H10F C55C H55F C11 C (7) C56 C (6) C12 C (8) C57 C (7) C12 C (7) C57 C (7) C12 C (7) C57 C (7) C13 H13A C58 H58A C13 H13B C58 H58B C13 H13C C58 H58C C14 H14A C59 H59A C14 H14B C59 H59B C14 H14C C59 H59C C15 H15A C60 H60A C15 H15B C60 H60B C15 H15C C60 H60C C16 C (6) C61 C (6) C16 H C61 H C17 C (7) C62 C (7) C17 H C62 H C18 C (8) C63 C (7) C18 H C63 H C19 C (6) C64 C (7) C19 H C64 H C20 H C65 H C21 C (7) C66 C (6) C22 C24A (7) C67 C68C (8) C22 C25C (8) C67 C69A (8) C22 C23C (8) C67 C69C (8) C22 C23A (7) C67 C70A (7) C22 C24C (9) C67 C70C (9) C22 C25A (8) C67 C68A (7) C23A H23A C68A H68A C23A H23B C68A H68B C23A H23C C68A H68C C24A H24A C69A H69A C24A H24B C69A H69B C24A H24C C69A H69C C25A H25A C70A H70A C25A H25B C70A H70B C25A H25C C70A H70C C23C H23D C68C H68D C23C H23E C68C H68E C23C H23F C68C H68F C24C H24D C69C H69D C24C H24E C69C H69E C24C H24F C69C H69F sup-14

18 C25C H25D C70C H70D C25C H25E C70C H70E C25C H25F C70C H70F C26 C (7) C71 C (6) C27 C28A (13) C72 C (6) C27 C29C (9) C72 C (6) C27 C30C (9) C72 C (6) C27 C28C (8) C73 H73A C27 C30A (10) C73 H73B C27 C29A (12) C73 H73C C28A H28A C74 H74A C28A H28B C74 H74B C28A H28C C74 H74C C29A H29A C75 H75A C29A H29B C75 H75B C29A H29C C75 H75C C30A H30A C76 C (6) C30A H30B C77 C79A (9) C30A H30C C77 C80A (7) C28C H28D C77 C78C (7) C28C H28E C77 C80C (9) C28C H28F C77 C79C (9) C29C H29D C77 C78A (7) C29C H29E C78A H78A C29C H29F C78A H78B C30C H30D C78A H78C C30C H30E C79A H79A C30C H30F C79A H79B C31 C (8) C79A H79C C32 C35C (9) C80A H80A C32 C34A (10) C80A H80B C32 C33C (7) C80A H80C C32 C35A (7) C78C H78D C32 C34C (9) C78C H78E C32 C33A (8) C78C H78F C33A H33A C79C H79D C33A H33B C79C H79E C33A H33C C79C H79F C34A H34A C80C H80D C34A H34B C80C H80E C34A H34C C80C H80F C35A H35A C81 C (6) C35A H35B C82 C83A (8) C35A H35C C82 C84C (8) C33C H33D C82 C85C (8) C33C H33E C82 C84A (8) C33C H33F C82 C85A (8) C34C H34D C82 C83C (8) sup-15

19 C34C H34E C83A H83A C34C H34F C83A H83B C35C H35D C83A H83C C35C H35E C84A H84A C35C H35F C84A H84B C36 C (7) C84A H84C C37 C (7) C85A H85A C37 C (7) C85A H85B C37 C (7) C85A H85C C38 H38A C83C H83D C38 H38B C83C H83E C38 H38C C83C H83F C39 H39A C84C H84D C39 H39B C84C H84E C39 H39C C84C H84F C40 H40A C85C H85D C40 H40B C85C H85E C40 H40C C85C H85F C41 C (7) C86 C (6) C42 C44C (8) C87 C89A (8) C42 C43A (8) C87 C88C (7) C42 C45A (8) C87 C90C (8) C42 C43C (9) C87 C90A (6) C42 C45C (9) C87 C88A (7) C42 C44A (8) C87 C89C (8) C43A H43A C88A H88A C43A H43B C88A H88B C43A H43C C88A H88C C44A H44A C89A H89A C44A H44B C89A H89B C44A H44C C89A H89C C45A H45A C90A H90A C45A H45B C90A H90B C45A H45C C90A H90C C43C H43D C88C H88D C43C H43E C88C H88E C43C H43F C88C H88F C44C H44D C89C H89D C44C H44E C89C H89E C44C H44F C89C H89F C45C H45D C90C H90D C45C H45E C90C H90E C45C H45F C90C H90F O1 Mn1A O (12) O16 Mn1B O (13) O1 Mn1A O (13) O16 Mn1B O (12) O5 Mn1A O (13) O28 Mn1B O (13) O1 Mn1A O (12) O16 Mn1B N (14) sup-16

20 O5 Mn1A O (13) O28 Mn1B N (14) O15 Mn1A O (12) O19 Mn1B N (14) O1 Mn1A N (13) O16 Mn1B O (12) O5 Mn1A N (13) O28 Mn1B O (13) O15 Mn1A N (13) O19 Mn1B O (12) O13 Mn1A N (13) N3 Mn1B O (14) O1 Mn1A O (13) O16 Mn1B O (12) O5 Mn1A O (13) O28 Mn1B O (12) O15 Mn1A O (12) O19 Mn1B O (12) O13 Mn1A O (13) N3 Mn1B O (14) N1 Mn1A O (14) O30 Mn1B O (13) O1 Mn1A Mn2A (8) O16 Mn1B Mn2B (8) O5 Mn1A Mn2A (9) O28 Mn1B Mn2B (10) O15 Mn1A Mn2A (9) O19 Mn1B Mn2B (9) O13 Mn1A Mn2A (9) N3 Mn1B Mn2B (11) N1 Mn1A Mn2A (10) O30 Mn1B Mn2B (9) O2 Mn1A Mn2A (9) O17 Mn1B Mn2B (8) O1 Mn2A O (12) O16 Mn2B O (12) O1 Mn2A O (12) O16 Mn2B O (12) O8 Mn2A O (12) O21 Mn2B O (13) O1 Mn2A N (15) O16 Mn2B N (14) O8 Mn2A N (14) O21 Mn2B N (13) O3 Mn2A N (13) O18 Mn2B N (12) O1 Mn2A O (12) O16 Mn2B O (12) O8 Mn2A O (13) O21 Mn2B O (12) O3 Mn2A O (13) O18 Mn2B O (12) N2 Mn2A O (13) N4 Mn2B O (13) O1 Mn2A O (12) O16 Mn2B O (12) O8 Mn2A O (13) O21 Mn2B O (12) O3 Mn2A O (13) O18 Mn2B O (12) N2 Mn2A O (13) N4 Mn2B O (13) O6 Mn2A O (12) O20 Mn2B O (11) O1 Mn2A Mn1A (9) O16 Mn2B Mn1B (9) O8 Mn2A Mn1A (9) O21 Mn2B Mn1B (9) O3 Mn2A Mn1A (9) O18 Mn2B Mn1B (9) N2 Mn2A Mn1A (11) N4 Mn2B Mn1B (10) O6 Mn2A Mn1A (9) O20 Mn2B Mn1B (8) O4 Mn2A Mn1A (8) O23 Mn2B Mn1B (8) O1 Mn3A O (12) O16 Mn3B O (12) O1 Mn3A O (11) O16 Mn3B O (11) O12 Mn3A O (14) O29 Mn3B O (12) O1 Mn3A O (11) O16 Mn3B O (11) O12 Mn3A O (13) O29 Mn3B O (12) O9 Mn3A O (14) O22 Mn3B O (12) O1 Mn3A O (12) O16 Mn3B O (11) O12 Mn3A O (13) O29 Mn3B O (12) O9 Mn3A O (14) O22 Mn3B O (12) O14 Mn3A O (13) O27 Mn3B O (12) sup-17

21 O1 Mn3A O (13) O16 Mn3B O (11) O12 Mn3A O (14) O29 Mn3B O (12) O9 Mn3A O (13) O22 Mn3B O (11) O14 Mn3A O (13) O27 Mn3B O (11) O7 Mn3A O (14) O24 Mn3B O (11) Mn1A O1 Mn2A (15) Mn1B O16 Mn2B (15) Mn1A O1 Mn3A (14) Mn1B O16 Mn3B (13) Mn2A O1 Mn3A (14) Mn2B O16 Mn3B (14) C6 O2 Mn1A (3) C51 O17 Mn1B (3) C6 O3 Mn2A (3) C51 O18 Mn2B (3) C11 O4 Mn2A (3) C56 O19 Mn1B (3) C11 O5 Mn1A (3) C56 O20 Mn2B (3) C21 O6 Mn2A (3) C66 O21 Mn2B (3) C21 O7 Mn3A (3) C66 O22 Mn3B (3) C26 O8 Mn2A (3) C71 O23 Mn2B (3) C26 O9 Mn3A (3) C71 O24 Mn3B (3) C31 O10 Mn3A (4) C76 O25 Mn3B (3) C31 O11 H C76 O26 H C36 O12 Mn3A (3) C81 O27 Mn3B (3) C36 O13 Mn1A (3) C81 O28 Mn1B (3) C41 O14 Mn3A (3) C86 O29 Mn3B (3) C41 O15 Mn1A (3) C86 O30 Mn1B (3) C5 N1 C (4) C50 N3 C (5) C5 N1 Mn1A (3) C50 N3 Mn1B (4) C1 N1 Mn1A (3) C46 N3 Mn1B (4) C16 N2 C (4) C65 N4 C (4) C16 N2 Mn2A (3) C65 N4 Mn2B (3) C20 N2 Mn2A (3) C61 N4 Mn2B (3) N1 C1 C (5) N3 C46 C (6) N1 C1 H N3 C46 H C2 C1 H C47 C46 H C3 C2 C (6) C46 C47 C (6) C3 C2 H C46 C47 H C1 C2 H C48 C47 H C2 C3 C (5) C49 C48 C (6) C2 C3 H C49 C48 H C4 C3 H C47 C48 H C3 C4 C (5) C48 C49 C (7) C3 C4 H C48 C49 H C5 C4 H C50 C49 H N1 C5 C (5) N3 C50 C (6) N1 C5 H N3 C50 H C4 C5 H C49 C50 H O2 C6 O (4) O17 C51 O (4) O2 C6 C (4) O17 C51 C (4) O3 C6 C (4) O18 C51 C (4) C9C C7 C10A 69.4 (8) C53A C52 C54C 69.1 (7) C9C C7 C8A (9) C53A C52 C55C (7) sup-18

22 C10A C7 C8A (8) C54C C52 C55C (7) C9C C7 C (7) C53A C52 C55A (7) C10A C7 C (6) C54C C52 C55A (7) C8A C7 C (6) C53A C52 C (6) C9C C7 C8C (8) C54C C52 C (6) C10A C7 C8C (8) C55C C52 C (5) C6 C7 C8C (6) C55A C52 C (5) C9C C7 C10C (8) C54C C52 C53C (7) C8A C7 C10C 90.2 (8) C55C C52 C53C (6) C6 C7 C10C (6) C55A C52 C53C 86.6 (7) C8C C7 C10C (8) C51 C52 C53C (5) C10A C7 C9A (7) C53A C52 C54A (7) C8A C7 C9A (7) C55C C52 C54A 86.1 (6) C6 C7 C9A (5) C55A C52 C54A (6) C8C C7 C9A 92.5 (7) C51 C52 C54A (5) C10C C7 C9A (7) C53C C52 C54A (7) C7 C8A H8A C52 C53A H53A C7 C8A H8B C52 C53A H53B C7 C8A H8C C52 C53A H53C C7 C9A H9A C52 C54A H54A C7 C9A H9B C52 C54A H54B C7 C9A H9C C52 C54A H54C C7 C10A H10A C52 C55A H55A C7 C10A H10B C52 C55A H55B C7 C10A H10C C52 C55A H55C C7 C8C H8D C52 C53C H53D C7 C8C H8E C52 C53C H53E H8D C8C H8E H53D C53C H53E C7 C8C H8F C52 C53C H53F H8D C8C H8F H53D C53C H53F H8E C8C H8F H53E C53C H53F C7 C9C H9D C52 C54C H54D C7 C9C H9E C52 C54C H54E H9D C9C H9E H54D C54C H54E C7 C9C H9F C52 C54C H54F H9D C9C H9F H54D C54C H54F H9E C9C H9F H54E C54C H54F C7 C10C H10D C52 C55C H55D C7 C10C H10E C52 C55C H55E H10D C10C H10E H55D C55C H55E C7 C10C H10F C52 C55C H55F H10D C10C H10F H55D C55C H55F H10E C10C H10F H55E C55C H55F O4 C11 O (4) O20 C56 O (4) O4 C11 C (4) O20 C56 C (4) O5 C11 C (4) O19 C56 C (4) C13 C12 C (5) C58 C57 C (5) C13 C12 C (5) C58 C57 C (4) sup-19

23 C15 C12 C (4) C59 C57 C (4) C13 C12 C (5) C58 C57 C (5) C15 C12 C (5) C59 C57 C (4) C11 C12 C (4) C56 C57 C (4) C12 C13 H13A C57 C58 H58A C12 C13 H13B C57 C58 H58B H13A C13 H13B H58A C58 H58B C12 C13 H13C C57 C58 H58C H13A C13 H13C H58A C58 H58C H13B C13 H13C H58B C58 H58C C12 C14 H14A C57 C59 H59A C12 C14 H14B C57 C59 H59B H14A C14 H14B H59A C59 H59B C12 C14 H14C C57 C59 H59C H14A C14 H14C H59A C59 H59C H14B C14 H14C H59B C59 H59C C12 C15 H15A C57 C60 H60A C12 C15 H15B C57 C60 H60B H15A C15 H15B H60A C60 H60B C12 C15 H15C C57 C60 H60C H15A C15 H15C H60A C60 H60C H15B C15 H15C H60B C60 H60C N2 C16 C (5) N4 C61 C (5) N2 C16 H N4 C61 H C17 C16 H C62 C61 H C18 C17 C (5) C63 C62 C (5) C18 C17 H C63 C62 H C16 C17 H C61 C62 H C17 C18 C (5) C62 C63 C (5) C17 C18 H C62 C63 H C19 C18 H C64 C63 H C20 C19 C (5) C63 C64 C (5) C20 C19 H C63 C64 H C18 C19 H C65 C64 H N2 C20 C (5) N4 C65 C (4) N2 C20 H N4 C65 H C19 C20 H C64 C65 H O6 C21 O (4) O22 C66 O (4) O6 C21 C (4) O22 C66 C (4) O7 C21 C (4) O21 C66 C (4) C24A C22 C25C 49.7 (8) C68C C67 C69A (9) C24A C22 C23C (9) C68C C67 C69C (9) C25C C22 C23C (10) C68C C67 C (7) C24A C22 C (6) C69A C67 C (6) C25C C22 C (8) C69C C67 C (6) C23C C22 C (7) C68C C67 C70A 58.9 (8) C24A C22 C23A (7) C69A C67 C70A (7) C25C C22 C23A (9) C69C C67 C70A (7) sup-20