metal-organic compounds
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
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
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 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 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 This is consistent with the presence of seven ethanol molecules per formula unit, which accounts for 182 electrons per Additionally, one ethanol molecule was found to be ordered in the crystal.
Keywords: crystal structure; pyridoxine; manganese; polynuclear complex.
CCDC reference: 2051338
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), unusual symmetries (Hu et al., 2013), and unique supramolecular architectures (Fielden & Cronin, 2005). Often such polymetallic complexes exhibit magnetic properties (Saha et al., 2011a), catalytic properties (Yamada et al., 2015), optical properties (Aboshyan-Sorgho et al., 2012) and biological activities (Kuczer et al., 2013). 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). 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, and This ligand plays the pivotal role as a linker (Stouder et al., 2017).
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. The core of the centrosymmetric complex (Fig. 2), 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) 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.
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). 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 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.
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The 3 in one void per triclinic This is consistent with the presence of seven ethanol molecules per formula unit, which accounts for 182 electrons per Additionally, one ethanol molecule O16/C42/C43 was found to be ordered in the crystal.
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 ÅSynthesis 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 . 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).
details are summarized in Table 2Structural data
CCDC reference: 2051338
https://doi.org/10.1107/S2414314620016430/bh4058sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620016430/bh4058Isup2.hkl
Data collection: CrysAlis PRO (Rigaku OD, 2020); cell
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).[Mn7(C8H9NO3)4(C8H10NO3)4(C2H5O)2(C7H5O2)2O2]·8C2H6O | Z = 1 |
Mr = 2449.71 | F(000) = 1274 |
Triclinic, P1 | Dx = 1.423 Mg m−3 |
a = 12.9774 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.6762 (7) Å | Cell parameters from 12116 reflections |
c = 16.7750 (6) Å | θ = 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) Å3 | 0.09 × 0.08 × 0.06 mm |
Rigaku XtaLAB Synergy, Dualflex, HyPix diffractometer | 10190 independent reflections |
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source | 7884 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.037 |
Detector resolution: 10.0000 pixels mm-1 | θmax = 25.1°, θmin = 2.5° |
ω scans | h = −15→15 |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020) | k = −17→17 |
Tmin = 0.966, Tmax = 1.000 | l = −20→20 |
34399 measured reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-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 parameters | Δρmax = 0.98 e Å−3 |
9 restraints | Δρmin = −0.28 e Å−3 |
Refinement. Hydrogen atoms were attached via the riding model at calculated positions using suitable HFIX commands. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mn1 | 0.72295 (3) | 0.42295 (3) | 0.56146 (3) | 0.03246 (13) | |
Mn2 | 0.72328 (3) | 0.52363 (3) | 0.37463 (3) | 0.03223 (13) | |
Mn3 | 0.500000 | 0.500000 | 0.500000 | 0.02829 (15) | |
Mn4 | 0.49800 (4) | 0.39857 (3) | 0.70324 (3) | 0.03243 (13) | |
O1 | 0.55540 (16) | 0.51184 (14) | 0.60120 (12) | 0.0335 (5) | |
O2 | 0.63608 (16) | 0.43484 (15) | 0.47679 (12) | 0.0346 (5) | |
O3 | 0.64800 (16) | 0.32378 (15) | 0.65648 (13) | 0.0377 (5) | |
O4 | 0.43587 (16) | 0.37094 (14) | 0.62110 (12) | 0.0317 (4) | |
O5 | 0.77496 (16) | 0.54310 (15) | 0.46695 (12) | 0.0340 (5) | |
O6 | 0.54308 (18) | 0.43981 (16) | 0.78180 (13) | 0.0427 (5) | |
O7 | 0.80492 (17) | 0.43486 (16) | 0.63726 (13) | 0.0399 (5) | |
O8 | 0.45964 (18) | 0.27999 (16) | 0.79730 (13) | 0.0429 (5) | |
O9 | 0.80638 (17) | 0.62354 (16) | 0.28792 (12) | 0.0401 (5) | |
O10 | 0.65480 (16) | 0.51228 (16) | 0.29100 (12) | 0.0365 (5) | |
O11 | 0.84197 (18) | 0.40553 (17) | 0.37249 (14) | 0.0450 (5) | |
O12 | 0.84048 (18) | 0.32516 (16) | 0.51759 (14) | 0.0446 (5) | |
O13 | 0.5745 (3) | 0.8308 (2) | 0.5748 (2) | 0.0938 (11) | |
H13 | 0.563029 | 0.867061 | 0.604331 | 0.141* | |
O14 | 0.7656 (3) | 0.0844 (3) | 0.9805 (2) | 0.1267 (17) | |
H14 | 0.722079 | 0.044696 | 1.017122 | 0.190* | |
O15 | 0.7882 (3) | 0.6430 (4) | −0.07481 (18) | 0.1081 (14) | |
H15 | 0.752050 | 0.628887 | −0.103888 | 0.162* | |
O17 | 0.4330 (3) | 0.0810 (3) | 0.5982 (2) | 0.0919 (11) | |
H17 | 0.423053 | 0.094953 | 0.546618 | 0.138* | |
N1 | 0.6795 (3) | 0.6054 (2) | 0.82394 (19) | 0.0565 (8) | |
N2 | 0.8660 (2) | 0.3582 (3) | 0.85144 (18) | 0.0572 (8) | |
H2 | 0.898645 | 0.380528 | 0.880277 | 0.069* | |
N3 | 0.3404 (3) | 0.0499 (2) | 0.8848 (2) | 0.0625 (9) | |
N4 | 0.8846 (3) | 0.7742 (2) | 0.06429 (17) | 0.0541 (8) | |
H4 | 0.919064 | 0.827978 | 0.033777 | 0.065* | |
C1 | 0.5477 (3) | 0.6057 (2) | 0.6102 (2) | 0.0437 (8) | |
H1A | 0.472136 | 0.628671 | 0.620333 | 0.052* | |
H1B | 0.581389 | 0.655189 | 0.554310 | 0.052* | |
C2 | 0.5985 (3) | 0.6023 (2) | 0.68398 (19) | 0.0398 (7) | |
C3 | 0.5897 (2) | 0.5214 (2) | 0.7651 (2) | 0.0383 (7) | |
C4 | 0.6299 (3) | 0.5275 (3) | 0.8349 (2) | 0.0453 (8) | |
C5 | 0.6900 (4) | 0.6800 (3) | 0.7461 (3) | 0.0668 (12) | |
H5 | 0.726298 | 0.734859 | 0.739336 | 0.080* | |
C6 | 0.6519 (3) | 0.6829 (3) | 0.6746 (2) | 0.0541 (9) | |
C7 | 0.6150 (3) | 0.4451 (3) | 0.9227 (2) | 0.0521 (9) | |
H7A | 0.657552 | 0.453886 | 0.960656 | 0.078* | |
H7B | 0.637445 | 0.381370 | 0.915995 | 0.078* | |
H7C | 0.540275 | 0.445717 | 0.949300 | 0.078* | |
C8 | 0.6669 (4) | 0.7730 (3) | 0.5903 (3) | 0.0711 (13) | |
H8A | 0.719651 | 0.813228 | 0.593372 | 0.085* | |
H8B | 0.694921 | 0.751164 | 0.540623 | 0.085* | |
C9 | 0.7070 (3) | 0.2479 (2) | 0.7162 (2) | 0.0480 (8) | |
H9A | 0.759715 | 0.213800 | 0.683475 | 0.058* | |
H9B | 0.658742 | 0.198088 | 0.759588 | 0.058* | |
C10 | 0.7632 (3) | 0.2870 (2) | 0.7647 (2) | 0.0438 (8) | |
C11 | 0.7743 (3) | 0.2318 (3) | 0.8526 (2) | 0.0579 (10) | |
C12 | 0.8258 (3) | 0.2700 (3) | 0.8944 (2) | 0.0657 (12) | |
H12 | 0.832882 | 0.233481 | 0.954365 | 0.079* | |
C13 | 0.8599 (3) | 0.4152 (3) | 0.7668 (2) | 0.0445 (8) | |
C14 | 0.8080 (2) | 0.3788 (2) | 0.72120 (19) | 0.0401 (7) | |
C15 | 0.7288 (3) | 0.1302 (4) | 0.9029 (3) | 0.0804 (15) | |
H15A | 0.650705 | 0.138997 | 0.914161 | 0.096* | |
H15B | 0.749629 | 0.088584 | 0.867154 | 0.096* | |
C16 | 0.9105 (3) | 0.5112 (3) | 0.7254 (2) | 0.0543 (9) | |
H16A | 0.900561 | 0.543147 | 0.768119 | 0.082* | |
H16B | 0.878194 | 0.554992 | 0.674076 | 0.082* | |
H16C | 0.986260 | 0.498703 | 0.706714 | 0.082* | |
C17 | 0.4377 (3) | 0.2715 (2) | 0.62780 (19) | 0.0396 (7) | |
H17A | 0.510846 | 0.250131 | 0.607072 | 0.048* | |
H17B | 0.392631 | 0.270284 | 0.587405 | 0.048* | |
C18 | 0.4011 (3) | 0.1963 (2) | 0.7189 (2) | 0.0404 (7) | |
C19 | 0.4165 (2) | 0.2055 (2) | 0.7954 (2) | 0.0385 (7) | |
C20 | 0.3851 (3) | 0.1288 (2) | 0.8786 (2) | 0.0470 (8) | |
C21 | 0.3266 (4) | 0.0416 (3) | 0.8115 (3) | 0.0703 (12) | |
H21 | 0.295627 | −0.015756 | 0.817061 | 0.084* | |
C22 | 0.3544 (3) | 0.1115 (3) | 0.7281 (2) | 0.0552 (10) | |
C23 | 0.4023 (3) | 0.1353 (3) | 0.9612 (2) | 0.0558 (10) | |
H23A | 0.474186 | 0.108487 | 0.971879 | 0.084* | |
H23B | 0.351217 | 0.096644 | 1.010739 | 0.084* | |
H23C | 0.392797 | 0.205080 | 0.955318 | 0.084* | |
C24 | 0.3357 (4) | 0.0933 (3) | 0.6510 (3) | 0.0709 (13) | |
H24A | 0.296834 | 0.032815 | 0.672004 | 0.085* | |
H24B | 0.291910 | 0.150337 | 0.615491 | 0.085* | |
C25 | 0.8829 (2) | 0.5660 (3) | 0.4548 (2) | 0.0438 (8) | |
H25A | 0.922119 | 0.560551 | 0.399362 | 0.053* | |
H25B | 0.917118 | 0.516849 | 0.503944 | 0.053* | |
C26 | 0.8890 (3) | 0.6662 (3) | 0.4515 (3) | 0.0716 (12) | |
H26A | 0.849209 | 0.714489 | 0.406701 | 0.107* | |
H26B | 0.962998 | 0.682037 | 0.436342 | 0.107* | |
H26C | 0.858678 | 0.669216 | 0.509054 | 0.107* | |
C27 | 0.8156 (2) | 0.6543 (2) | 0.20096 (18) | 0.0347 (7) | |
C28 | 0.8713 (3) | 0.7392 (2) | 0.1522 (2) | 0.0422 (8) | |
C29 | 0.8469 (3) | 0.7298 (3) | 0.0209 (2) | 0.0587 (10) | |
H29 | 0.859961 | 0.755807 | −0.041632 | 0.070* | |
C30 | 0.7901 (3) | 0.6477 (3) | 0.0657 (2) | 0.0488 (9) | |
C31 | 0.7733 (2) | 0.6081 (2) | 0.15795 (19) | 0.0372 (7) | |
C32 | 0.7148 (3) | 0.5151 (3) | 0.20907 (19) | 0.0421 (8) | |
H32A | 0.666870 | 0.509853 | 0.172562 | 0.050* | |
H32B | 0.766723 | 0.456435 | 0.219945 | 0.050* | |
C33 | 0.9166 (3) | 0.7920 (3) | 0.1953 (2) | 0.0531 (9) | |
H33A | 0.947473 | 0.852197 | 0.150287 | 0.080* | |
H33B | 0.971503 | 0.748021 | 0.227416 | 0.080* | |
H33C | 0.860547 | 0.810577 | 0.236486 | 0.080* | |
C34 | 0.7481 (3) | 0.5992 (4) | 0.0152 (2) | 0.0709 (13) | |
H34A | 0.769456 | 0.526970 | 0.037316 | 0.085* | |
H34B | 0.669927 | 0.607750 | 0.024434 | 0.085* | |
C35 | 0.8716 (3) | 0.3350 (2) | 0.4376 (2) | 0.0429 (8) | |
C36 | 0.9487 (3) | 0.2559 (3) | 0.4202 (3) | 0.0499 (9) | |
C37 | 0.9834 (3) | 0.2609 (3) | 0.3344 (3) | 0.0599 (10) | |
H37 | 0.957347 | 0.314580 | 0.286968 | 0.072* | |
C38 | 1.0550 (4) | 0.1889 (4) | 0.3176 (3) | 0.0740 (12) | |
H38 | 1.077694 | 0.193154 | 0.258671 | 0.089* | |
C39 | 1.0935 (4) | 0.1118 (4) | 0.3846 (4) | 0.0821 (14) | |
H39 | 1.142783 | 0.062191 | 0.372524 | 0.099* | |
C40 | 1.0608 (4) | 0.1056 (3) | 0.4700 (4) | 0.0740 (13) | |
H40 | 1.088196 | 0.052042 | 0.516736 | 0.089* | |
C41 | 0.9875 (3) | 0.1777 (3) | 0.4883 (3) | 0.0574 (10) | |
H41 | 0.964559 | 0.172784 | 0.547368 | 0.069* | |
O16 | 0.6762 (5) | 0.2505 (4) | 0.4357 (4) | 0.0752 (16) | 0.5 |
H16 | 0.642396 | 0.290669 | 0.457791 | 0.113* | 0.5 |
C42 | 0.6885 (6) | 0.1580 (6) | 0.5016 (6) | 0.0623 (17) | 0.5 |
H42A | 0.623729 | 0.143483 | 0.546420 | 0.075* | 0.5 |
H42B | 0.748686 | 0.154590 | 0.530817 | 0.075* | 0.5 |
C43 | 0.7077 (7) | 0.0916 (7) | 0.4594 (7) | 0.081 (2) | 0.5 |
H43A | 0.673340 | 0.118745 | 0.407039 | 0.121* | 0.5 |
H43B | 0.679244 | 0.028034 | 0.499495 | 0.121* | 0.5 |
H43C | 0.783989 | 0.081056 | 0.441767 | 0.121* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0324 (3) | 0.0366 (3) | 0.0289 (2) | −0.0128 (2) | −0.00724 (18) | −0.00816 (18) |
Mn2 | 0.0324 (3) | 0.0407 (3) | 0.0269 (2) | −0.0137 (2) | −0.00393 (18) | −0.01295 (19) |
Mn3 | 0.0290 (3) | 0.0337 (3) | 0.0242 (3) | −0.0124 (3) | −0.0051 (2) | −0.0093 (2) |
Mn4 | 0.0368 (3) | 0.0378 (3) | 0.0241 (2) | −0.0140 (2) | −0.00685 (18) | −0.00830 (18) |
O1 | 0.0416 (12) | 0.0341 (11) | 0.0270 (10) | −0.0156 (9) | −0.0040 (8) | −0.0099 (8) |
O2 | 0.0350 (12) | 0.0402 (11) | 0.0317 (10) | −0.0157 (9) | −0.0073 (8) | −0.0114 (9) |
O3 | 0.0363 (12) | 0.0360 (11) | 0.0363 (11) | −0.0132 (9) | −0.0077 (9) | −0.0043 (9) |
O4 | 0.0361 (11) | 0.0345 (11) | 0.0254 (9) | −0.0145 (9) | −0.0056 (8) | −0.0078 (8) |
O5 | 0.0333 (11) | 0.0419 (11) | 0.0284 (10) | −0.0166 (9) | −0.0042 (8) | −0.0107 (8) |
O6 | 0.0535 (14) | 0.0479 (13) | 0.0298 (11) | −0.0168 (11) | −0.0139 (9) | −0.0098 (9) |
O7 | 0.0442 (13) | 0.0449 (12) | 0.0305 (11) | −0.0199 (10) | −0.0099 (9) | −0.0065 (9) |
O8 | 0.0528 (14) | 0.0455 (13) | 0.0274 (10) | −0.0202 (11) | −0.0076 (9) | −0.0044 (9) |
O9 | 0.0459 (13) | 0.0528 (13) | 0.0274 (10) | −0.0247 (11) | −0.0002 (9) | −0.0169 (9) |
O10 | 0.0391 (12) | 0.0462 (12) | 0.0308 (10) | −0.0153 (10) | −0.0038 (8) | −0.0180 (9) |
O11 | 0.0438 (13) | 0.0499 (14) | 0.0467 (13) | −0.0056 (11) | −0.0058 (10) | −0.0241 (11) |
O12 | 0.0411 (13) | 0.0443 (13) | 0.0506 (14) | −0.0055 (10) | −0.0090 (10) | −0.0187 (10) |
O13 | 0.140 (3) | 0.0525 (18) | 0.074 (2) | 0.000 (2) | 0.001 (2) | −0.0191 (15) |
O14 | 0.099 (3) | 0.139 (3) | 0.078 (2) | −0.053 (2) | −0.034 (2) | 0.050 (2) |
O15 | 0.113 (3) | 0.189 (4) | 0.0413 (16) | −0.080 (3) | −0.0050 (16) | −0.044 (2) |
O17 | 0.133 (3) | 0.082 (2) | 0.083 (2) | 0.008 (2) | −0.040 (2) | −0.050 (2) |
N1 | 0.067 (2) | 0.069 (2) | 0.0511 (17) | −0.0224 (17) | −0.0145 (15) | −0.0322 (16) |
N2 | 0.0421 (17) | 0.093 (2) | 0.0352 (15) | −0.0091 (16) | −0.0118 (12) | −0.0189 (16) |
N3 | 0.082 (2) | 0.0445 (17) | 0.0467 (18) | −0.0233 (17) | −0.0100 (16) | 0.0036 (14) |
N4 | 0.070 (2) | 0.0525 (18) | 0.0327 (15) | −0.0244 (16) | −0.0011 (13) | −0.0058 (13) |
C1 | 0.062 (2) | 0.0350 (17) | 0.0387 (17) | −0.0155 (15) | −0.0122 (15) | −0.0127 (13) |
C2 | 0.0406 (18) | 0.0474 (18) | 0.0366 (16) | −0.0100 (15) | −0.0038 (13) | −0.0200 (14) |
C3 | 0.0354 (17) | 0.0479 (18) | 0.0403 (17) | −0.0094 (14) | −0.0082 (13) | −0.0227 (14) |
C4 | 0.048 (2) | 0.060 (2) | 0.0373 (17) | −0.0073 (16) | −0.0081 (14) | −0.0261 (15) |
C5 | 0.093 (3) | 0.064 (2) | 0.057 (2) | −0.037 (2) | −0.017 (2) | −0.025 (2) |
C6 | 0.065 (2) | 0.062 (2) | 0.0480 (19) | −0.0258 (19) | −0.0099 (17) | −0.0268 (17) |
C7 | 0.061 (2) | 0.065 (2) | 0.0404 (18) | −0.0041 (18) | −0.0170 (16) | −0.0265 (17) |
C8 | 0.103 (4) | 0.062 (3) | 0.059 (2) | −0.045 (3) | −0.015 (2) | −0.021 (2) |
C9 | 0.047 (2) | 0.0394 (18) | 0.0468 (18) | −0.0080 (15) | −0.0133 (15) | −0.0004 (14) |
C10 | 0.0345 (18) | 0.0463 (19) | 0.0381 (17) | −0.0076 (14) | −0.0100 (13) | 0.0005 (14) |
C11 | 0.037 (2) | 0.072 (3) | 0.0436 (19) | −0.0102 (18) | −0.0120 (15) | 0.0050 (17) |
C12 | 0.043 (2) | 0.100 (3) | 0.0308 (18) | −0.007 (2) | −0.0095 (15) | 0.0026 (19) |
C13 | 0.0352 (18) | 0.065 (2) | 0.0342 (17) | −0.0054 (16) | −0.0066 (13) | −0.0187 (15) |
C14 | 0.0334 (17) | 0.0497 (19) | 0.0327 (16) | −0.0053 (14) | −0.0083 (13) | −0.0088 (14) |
C15 | 0.056 (3) | 0.098 (3) | 0.052 (2) | −0.020 (2) | −0.0154 (19) | 0.017 (2) |
C16 | 0.057 (2) | 0.068 (2) | 0.054 (2) | −0.0170 (19) | −0.0147 (17) | −0.0313 (18) |
C17 | 0.0459 (19) | 0.0403 (17) | 0.0372 (16) | −0.0132 (14) | −0.0083 (14) | −0.0152 (13) |
C18 | 0.0438 (19) | 0.0339 (16) | 0.0405 (17) | −0.0100 (14) | −0.0091 (14) | −0.0074 (13) |
C19 | 0.0384 (18) | 0.0336 (16) | 0.0374 (16) | −0.0080 (14) | −0.0057 (13) | −0.0056 (13) |
C20 | 0.051 (2) | 0.0399 (18) | 0.0399 (18) | −0.0065 (16) | −0.0060 (15) | −0.0043 (14) |
C21 | 0.101 (4) | 0.042 (2) | 0.063 (3) | −0.035 (2) | −0.021 (2) | 0.0003 (18) |
C22 | 0.076 (3) | 0.0410 (19) | 0.049 (2) | −0.0205 (18) | −0.0168 (18) | −0.0080 (15) |
C23 | 0.071 (3) | 0.047 (2) | 0.0344 (17) | −0.0094 (18) | −0.0035 (16) | −0.0002 (15) |
C24 | 0.105 (4) | 0.047 (2) | 0.065 (3) | −0.034 (2) | −0.021 (2) | −0.0123 (19) |
C25 | 0.0346 (18) | 0.062 (2) | 0.0352 (16) | −0.0206 (16) | −0.0073 (13) | −0.0121 (15) |
C26 | 0.058 (3) | 0.090 (3) | 0.090 (3) | −0.035 (2) | −0.002 (2) | −0.052 (3) |
C27 | 0.0361 (17) | 0.0407 (17) | 0.0291 (15) | −0.0071 (13) | −0.0024 (12) | −0.0150 (12) |
C28 | 0.046 (2) | 0.0444 (18) | 0.0360 (17) | −0.0111 (15) | 0.0003 (14) | −0.0156 (14) |
C29 | 0.068 (3) | 0.074 (3) | 0.0275 (17) | −0.019 (2) | −0.0058 (16) | −0.0087 (16) |
C30 | 0.052 (2) | 0.068 (2) | 0.0324 (17) | −0.0186 (18) | −0.0068 (14) | −0.0208 (16) |
C31 | 0.0332 (17) | 0.0505 (19) | 0.0324 (15) | −0.0076 (14) | −0.0028 (12) | −0.0202 (14) |
C32 | 0.048 (2) | 0.053 (2) | 0.0351 (16) | −0.0161 (16) | −0.0026 (14) | −0.0251 (14) |
C33 | 0.064 (2) | 0.052 (2) | 0.0493 (19) | −0.0304 (18) | 0.0074 (17) | −0.0244 (16) |
C34 | 0.067 (3) | 0.116 (4) | 0.0329 (18) | −0.039 (3) | −0.0045 (17) | −0.023 (2) |
C35 | 0.0377 (18) | 0.0455 (19) | 0.052 (2) | −0.0145 (15) | −0.0017 (15) | −0.0246 (16) |
C36 | 0.041 (2) | 0.0444 (19) | 0.073 (2) | −0.0172 (16) | −0.0055 (17) | −0.0277 (18) |
C37 | 0.050 (2) | 0.060 (2) | 0.082 (3) | −0.0166 (19) | 0.0028 (19) | −0.041 (2) |
C38 | 0.068 (3) | 0.071 (3) | 0.098 (3) | −0.010 (2) | 0.003 (2) | −0.054 (3) |
C39 | 0.066 (3) | 0.070 (3) | 0.128 (4) | −0.003 (2) | −0.006 (3) | −0.062 (3) |
C40 | 0.060 (3) | 0.049 (2) | 0.124 (4) | −0.003 (2) | −0.028 (3) | −0.038 (3) |
C41 | 0.047 (2) | 0.052 (2) | 0.083 (3) | −0.0119 (18) | −0.0090 (19) | −0.033 (2) |
O16 | 0.061 (4) | 0.071 (3) | 0.103 (4) | −0.008 (3) | −0.034 (3) | −0.032 (3) |
C42 | 0.026 (3) | 0.066 (3) | 0.096 (5) | −0.013 (3) | −0.005 (3) | −0.031 (3) |
C43 | 0.054 (5) | 0.077 (4) | 0.123 (7) | 0.017 (4) | −0.031 (5) | −0.050 (5) |
Mn1—Mn2 | 2.8844 (6) | C8—H8B | 0.9900 |
Mn1—Mn3 | 3.1695 (5) | C9—H9A | 0.9900 |
Mn1—O1 | 2.471 (2) | C9—H9B | 0.9900 |
Mn1—O2 | 1.9315 (19) | C9—C10 | 1.506 (5) |
Mn1—O3 | 1.8815 (19) | C10—C11 | 1.398 (4) |
Mn1—O5 | 1.9410 (19) | C10—C14 | 1.400 (5) |
Mn1—O7 | 1.891 (2) | C11—C12 | 1.369 (6) |
Mn1—O12 | 2.154 (2) | C11—C15 | 1.529 (6) |
Mn2—Mn3 | 3.1810 (4) | C12—H12 | 0.9500 |
Mn2—O2 | 1.9428 (19) | C13—C14 | 1.405 (5) |
Mn2—O4i | 2.394 (2) | C13—C16 | 1.486 (5) |
Mn2—O5 | 1.9422 (19) | C15—H15A | 0.9900 |
Mn2—O9 | 1.8853 (19) | C15—H15B | 0.9900 |
Mn2—O10 | 1.881 (2) | C16—H16A | 0.9800 |
Mn2—O11 | 2.145 (2) | C16—H16B | 0.9800 |
Mn3—Mn4i | 3.1274 (4) | C16—H16C | 0.9800 |
Mn3—Mn4 | 3.1274 (4) | C17—H17A | 0.9900 |
Mn3—O1 | 2.0519 (19) | C17—H17B | 0.9900 |
Mn3—O1i | 2.0518 (19) | C17—C18 | 1.515 (4) |
Mn3—O2 | 1.920 (2) | C18—C19 | 1.400 (4) |
Mn3—O2i | 1.920 (2) | C18—C22 | 1.404 (5) |
Mn3—O4i | 2.2620 (18) | C19—C20 | 1.426 (4) |
Mn3—O4 | 2.2620 (18) | C20—C23 | 1.490 (5) |
Mn4—O1 | 1.9563 (18) | C21—H21 | 0.9500 |
Mn4—O3 | 2.239 (2) | C21—C22 | 1.379 (5) |
Mn4—O4 | 1.9286 (19) | C22—C24 | 1.492 (5) |
Mn4—O6 | 1.873 (2) | C23—H23A | 0.9800 |
Mn4—O8 | 1.875 (2) | C23—H23B | 0.9800 |
Mn4—O10i | 2.212 (2) | C23—H23C | 0.9800 |
O1—C1 | 1.432 (4) | C24—H24A | 0.9900 |
O3—C9 | 1.417 (4) | C24—H24B | 0.9900 |
O4—C17 | 1.415 (4) | C25—H25A | 0.9900 |
O5—C25 | 1.445 (3) | C25—H25B | 0.9900 |
O6—C3 | 1.327 (4) | C25—C26 | 1.462 (5) |
O7—C14 | 1.324 (3) | C26—H26A | 0.9800 |
O8—C19 | 1.315 (4) | C26—H26B | 0.9800 |
O9—C27 | 1.329 (3) | C26—H26C | 0.9800 |
O10—C32 | 1.420 (3) | C27—C28 | 1.400 (4) |
O11—C35 | 1.252 (4) | C27—C31 | 1.396 (4) |
O12—C35 | 1.274 (4) | C28—C33 | 1.493 (5) |
O13—H13 | 0.8400 | C29—H29 | 0.9500 |
O13—C8 | 1.368 (6) | C29—C30 | 1.370 (5) |
O14—H14 | 0.8400 | C30—C31 | 1.400 (4) |
O14—C15 | 1.356 (5) | C30—C34 | 1.520 (5) |
O15—H15 | 0.8400 | C31—C32 | 1.511 (4) |
O15—C34 | 1.402 (4) | C32—H32A | 0.9900 |
O17—H17 | 0.8400 | C32—H32B | 0.9900 |
O17—C24 | 1.415 (6) | C33—H33A | 0.9800 |
N1—C4 | 1.327 (4) | C33—H33B | 0.9800 |
N1—C5 | 1.325 (5) | C33—H33C | 0.9800 |
N2—H2 | 0.8800 | C34—H34A | 0.9900 |
N2—C12 | 1.330 (5) | C34—H34B | 0.9900 |
N2—C13 | 1.343 (4) | C35—C36 | 1.493 (5) |
N3—C20 | 1.330 (5) | C36—C37 | 1.390 (5) |
N3—C21 | 1.333 (5) | C36—C41 | 1.379 (5) |
N4—H4 | 0.8800 | C37—H37 | 0.9500 |
N4—C28 | 1.337 (4) | C37—C38 | 1.375 (6) |
N4—C29 | 1.347 (5) | C38—H38 | 0.9500 |
C1—H1A | 0.9900 | C38—C39 | 1.359 (7) |
C1—H1B | 0.9900 | C39—H39 | 0.9500 |
C1—C2 | 1.500 (4) | C39—C40 | 1.377 (7) |
C2—C3 | 1.402 (4) | C40—H40 | 0.9500 |
C2—C6 | 1.400 (5) | C40—C41 | 1.396 (6) |
C3—C4 | 1.416 (4) | C41—H41 | 0.9500 |
C4—C7 | 1.484 (5) | O16—H16 | 0.8400 |
C5—H5 | 0.9500 | O16—C42 | 1.380 (9) |
C5—C6 | 1.373 (5) | C42—H42A | 0.9900 |
C6—C8 | 1.504 (5) | C42—H42B | 0.9900 |
C7—H7A | 0.9800 | C42—C43 | 1.384 (12) |
C7—H7B | 0.9800 | C43—H43A | 0.9800 |
C7—H7C | 0.9800 | C43—H43B | 0.9800 |
C8—H8A | 0.9900 | C43—H43C | 0.9800 |
Mn2—Mn1—Mn3 | 63.190 (13) | C28—N4—H4 | 118.9 |
O1—Mn1—Mn2 | 93.74 (5) | C28—N4—C29 | 122.1 (3) |
O1—Mn1—Mn3 | 40.33 (4) | C29—N4—H4 | 118.9 |
O2—Mn1—Mn2 | 42.04 (6) | O1—C1—H1A | 108.9 |
O2—Mn1—Mn3 | 34.50 (6) | O1—C1—H1B | 108.9 |
O2—Mn1—O1 | 74.81 (8) | O1—C1—C2 | 113.5 (3) |
O2—Mn1—O5 | 81.03 (8) | H1A—C1—H1B | 107.7 |
O2—Mn1—O12 | 92.21 (9) | C2—C1—H1A | 108.9 |
O3—Mn1—Mn2 | 137.18 (6) | C2—C1—H1B | 108.9 |
O3—Mn1—Mn3 | 84.67 (6) | C3—C2—C1 | 121.5 (3) |
O3—Mn1—O1 | 75.72 (8) | C6—C2—C1 | 120.2 (3) |
O3—Mn1—O2 | 95.59 (8) | C6—C2—C3 | 118.2 (3) |
O3—Mn1—O5 | 168.24 (9) | O6—C3—C2 | 124.1 (3) |
O3—Mn1—O7 | 90.81 (9) | O6—C3—C4 | 117.3 (3) |
O3—Mn1—O12 | 97.35 (9) | C2—C3—C4 | 118.6 (3) |
O5—Mn1—Mn2 | 42.05 (6) | N1—C4—C3 | 121.6 (3) |
O5—Mn1—Mn3 | 86.28 (6) | N1—C4—C7 | 119.3 (3) |
O5—Mn1—O1 | 92.52 (8) | C3—C4—C7 | 119.1 (3) |
O5—Mn1—O12 | 94.05 (9) | N1—C5—H5 | 117.9 |
O7—Mn1—Mn2 | 132.02 (6) | N1—C5—C6 | 124.2 (3) |
O7—Mn1—Mn3 | 139.87 (7) | C6—C5—H5 | 117.9 |
O7—Mn1—O1 | 99.97 (8) | C2—C6—C8 | 122.7 (3) |
O7—Mn1—O2 | 170.40 (9) | C5—C6—C2 | 118.3 (3) |
O7—Mn1—O5 | 91.27 (8) | C5—C6—C8 | 119.0 (3) |
O7—Mn1—O12 | 94.07 (9) | C4—C7—H7A | 109.5 |
O12—Mn1—Mn2 | 81.78 (6) | C4—C7—H7B | 109.5 |
O12—Mn1—Mn3 | 126.06 (6) | C4—C7—H7C | 109.5 |
O12—Mn1—O1 | 164.36 (8) | H7A—C7—H7B | 109.5 |
Mn1—Mn2—Mn3 | 62.784 (12) | H7A—C7—H7C | 109.5 |
O2—Mn2—Mn1 | 41.74 (6) | H7B—C7—H7C | 109.5 |
O2—Mn2—Mn3 | 34.32 (6) | O13—C8—C6 | 112.0 (4) |
O2—Mn2—O4i | 79.51 (8) | O13—C8—H8A | 109.2 |
O2—Mn2—O11 | 92.14 (9) | O13—C8—H8B | 109.2 |
O4i—Mn2—Mn1 | 98.83 (5) | C6—C8—H8A | 109.2 |
O4i—Mn2—Mn3 | 45.19 (4) | C6—C8—H8B | 109.2 |
O5—Mn2—Mn1 | 42.02 (6) | H8A—C8—H8B | 107.9 |
O5—Mn2—Mn3 | 85.93 (6) | O3—C9—H9A | 109.0 |
O5—Mn2—O2 | 80.72 (8) | O3—C9—H9B | 109.0 |
O5—Mn2—O4i | 95.70 (8) | O3—C9—C10 | 112.9 (3) |
O5—Mn2—O11 | 92.82 (9) | H9A—C9—H9B | 107.8 |
O9—Mn2—Mn1 | 131.22 (6) | C10—C9—H9A | 109.0 |
O9—Mn2—Mn3 | 140.22 (7) | C10—C9—H9B | 109.0 |
O9—Mn2—O2 | 169.68 (9) | C11—C10—C9 | 121.0 (3) |
O9—Mn2—O4i | 96.07 (8) | C11—C10—C14 | 118.9 (3) |
O9—Mn2—O5 | 90.53 (8) | C14—C10—C9 | 120.1 (3) |
O9—Mn2—O11 | 93.74 (9) | C10—C11—C15 | 121.1 (4) |
O10—Mn2—Mn1 | 136.16 (6) | C12—C11—C10 | 119.2 (3) |
O10—Mn2—Mn3 | 86.99 (6) | C12—C11—C15 | 119.7 (3) |
O10—Mn2—O2 | 95.53 (8) | N2—C12—C11 | 120.3 (3) |
O10—Mn2—O4i | 76.56 (8) | N2—C12—H12 | 119.8 |
O10—Mn2—O5 | 171.95 (9) | C11—C12—H12 | 119.8 |
O10—Mn2—O9 | 92.46 (8) | N2—C13—C14 | 117.5 (3) |
O10—Mn2—O11 | 94.43 (9) | N2—C13—C16 | 119.1 (3) |
O11—Mn2—Mn1 | 80.99 (6) | C14—C13—C16 | 123.4 (3) |
O11—Mn2—Mn3 | 125.98 (6) | O7—C14—C10 | 123.4 (3) |
O11—Mn2—O4i | 166.93 (8) | O7—C14—C13 | 116.7 (3) |
Mn1i—Mn3—Mn1 | 180.0 | C10—C14—C13 | 119.9 (3) |
Mn1—Mn3—Mn2i | 125.975 (11) | O14—C15—C11 | 109.7 (4) |
Mn1—Mn3—Mn2 | 54.026 (11) | O14—C15—H15A | 109.7 |
Mn1i—Mn3—Mn2 | 125.973 (11) | O14—C15—H15B | 109.7 |
Mn1i—Mn3—Mn2i | 54.026 (11) | C11—C15—H15A | 109.7 |
Mn2i—Mn3—Mn2 | 180.0 | C11—C15—H15B | 109.7 |
Mn4i—Mn3—Mn1 | 116.284 (12) | H15A—C15—H15B | 108.2 |
Mn4—Mn3—Mn1i | 116.285 (12) | C13—C16—H16A | 109.5 |
Mn4—Mn3—Mn1 | 63.716 (12) | C13—C16—H16B | 109.5 |
Mn4i—Mn3—Mn1i | 63.715 (12) | C13—C16—H16C | 109.5 |
Mn4i—Mn3—Mn2 | 62.297 (12) | H16A—C16—H16B | 109.5 |
Mn4—Mn3—Mn2i | 62.298 (12) | H16A—C16—H16C | 109.5 |
Mn4i—Mn3—Mn2i | 117.702 (12) | H16B—C16—H16C | 109.5 |
Mn4—Mn3—Mn2 | 117.703 (12) | O4—C17—H17A | 108.3 |
Mn4i—Mn3—Mn4 | 180.0 | O4—C17—H17B | 108.3 |
O1i—Mn3—Mn1i | 51.20 (6) | O4—C17—C18 | 115.8 (3) |
O1—Mn3—Mn1i | 128.80 (6) | H17A—C17—H17B | 107.4 |
O1i—Mn3—Mn1 | 128.80 (6) | C18—C17—H17A | 108.3 |
O1—Mn3—Mn1 | 51.20 (6) | C18—C17—H17B | 108.3 |
O1i—Mn3—Mn2i | 94.51 (6) | C19—C18—C17 | 122.2 (3) |
O1—Mn3—Mn2 | 94.51 (6) | C19—C18—C22 | 118.0 (3) |
O1i—Mn3—Mn2 | 85.49 (6) | C22—C18—C17 | 119.8 (3) |
O1—Mn3—Mn2i | 85.49 (6) | O8—C19—C18 | 125.0 (3) |
O1—Mn3—Mn4i | 142.37 (5) | O8—C19—C20 | 116.1 (3) |
O1—Mn3—Mn4 | 37.63 (5) | C18—C19—C20 | 118.9 (3) |
O1i—Mn3—Mn4i | 37.64 (5) | N3—C20—C19 | 121.4 (3) |
O1i—Mn3—Mn4 | 142.37 (5) | N3—C20—C23 | 118.3 (3) |
O1i—Mn3—O1 | 180.0 | C19—C20—C23 | 120.3 (3) |
O1—Mn3—O4i | 104.56 (7) | N3—C21—H21 | 118.1 |
O1i—Mn3—O4i | 75.44 (7) | N3—C21—C22 | 123.8 (4) |
O1i—Mn3—O4 | 104.56 (7) | C22—C21—H21 | 118.1 |
O1—Mn3—O4 | 75.44 (7) | C18—C22—C24 | 122.5 (3) |
O2i—Mn3—Mn1i | 34.74 (6) | C21—C22—C18 | 118.7 (3) |
O2i—Mn3—Mn1 | 145.26 (6) | C21—C22—C24 | 118.8 (3) |
O2—Mn3—Mn1 | 34.74 (6) | C20—C23—H23A | 109.5 |
O2—Mn3—Mn1i | 145.26 (6) | C20—C23—H23B | 109.5 |
O2i—Mn3—Mn2 | 145.20 (6) | C20—C23—H23C | 109.5 |
O2i—Mn3—Mn2i | 34.80 (6) | H23A—C23—H23B | 109.5 |
O2—Mn3—Mn2 | 34.80 (6) | H23A—C23—H23C | 109.5 |
O2—Mn3—Mn2i | 145.21 (6) | H23B—C23—H23C | 109.5 |
O2—Mn3—Mn4i | 88.58 (6) | O17—C24—C22 | 110.3 (4) |
O2—Mn3—Mn4 | 91.42 (6) | O17—C24—H24A | 109.6 |
O2i—Mn3—Mn4i | 91.42 (6) | O17—C24—H24B | 109.6 |
O2i—Mn3—Mn4 | 88.58 (6) | C22—C24—H24A | 109.6 |
O2—Mn3—O1 | 85.92 (8) | C22—C24—H24B | 109.6 |
O2—Mn3—O1i | 94.08 (8) | H24A—C24—H24B | 108.1 |
O2i—Mn3—O1i | 85.92 (8) | O5—C25—H25A | 109.3 |
O2i—Mn3—O1 | 94.08 (8) | O5—C25—H25B | 109.3 |
O2i—Mn3—O2 | 180.00 (12) | O5—C25—C26 | 111.8 (3) |
O2—Mn3—O4 | 96.56 (8) | H25A—C25—H25B | 107.9 |
O2—Mn3—O4i | 83.44 (8) | C26—C25—H25A | 109.3 |
O2i—Mn3—O4 | 83.45 (8) | C26—C25—H25B | 109.3 |
O2i—Mn3—O4i | 96.55 (8) | C25—C26—H26A | 109.5 |
O4i—Mn3—Mn1 | 94.02 (5) | C25—C26—H26B | 109.5 |
O4—Mn3—Mn1i | 94.02 (5) | C25—C26—H26C | 109.5 |
O4—Mn3—Mn1 | 85.98 (5) | H26A—C26—H26B | 109.5 |
O4i—Mn3—Mn1i | 85.97 (5) | H26A—C26—H26C | 109.5 |
O4—Mn3—Mn2i | 48.66 (5) | H26B—C26—H26C | 109.5 |
O4—Mn3—Mn2 | 131.34 (5) | O9—C27—C28 | 115.6 (3) |
O4i—Mn3—Mn2 | 48.66 (5) | O9—C27—C31 | 124.3 (3) |
O4i—Mn3—Mn2i | 131.34 (5) | C31—C27—C28 | 120.1 (3) |
O4i—Mn3—Mn4i | 37.81 (5) | N4—C28—C27 | 119.1 (3) |
O4—Mn3—Mn4i | 142.19 (5) | N4—C28—C33 | 118.8 (3) |
O4i—Mn3—Mn4 | 142.19 (5) | C27—C28—C33 | 122.1 (3) |
O4—Mn3—Mn4 | 37.81 (5) | N4—C29—H29 | 119.5 |
O4i—Mn3—O4 | 180.0 | N4—C29—C30 | 120.9 (3) |
O1—Mn4—Mn3 | 39.83 (6) | C30—C29—H29 | 119.5 |
O1—Mn4—O3 | 80.23 (8) | C29—C30—C31 | 119.4 (3) |
O1—Mn4—O10i | 88.94 (8) | C29—C30—C34 | 119.9 (3) |
O3—Mn4—Mn3 | 80.49 (5) | C31—C30—C34 | 120.7 (3) |
O4—Mn4—Mn3 | 45.98 (5) | C27—C31—C30 | 118.3 (3) |
O4—Mn4—O1 | 85.80 (8) | C27—C31—C32 | 121.1 (3) |
O4—Mn4—O3 | 86.40 (8) | C30—C31—C32 | 120.6 (3) |
O4—Mn4—O10i | 80.29 (8) | O10—C32—C31 | 114.1 (2) |
O6—Mn4—Mn3 | 131.65 (6) | O10—C32—H32A | 108.7 |
O6—Mn4—O1 | 92.27 (9) | O10—C32—H32B | 108.7 |
O6—Mn4—O3 | 101.04 (9) | C31—C32—H32A | 108.7 |
O6—Mn4—O4 | 171.90 (10) | C31—C32—H32B | 108.7 |
O6—Mn4—O8 | 89.03 (9) | H32A—C32—H32B | 107.6 |
O6—Mn4—O10i | 91.82 (9) | C28—C33—H33A | 109.5 |
O8—Mn4—Mn3 | 139.31 (7) | C28—C33—H33B | 109.5 |
O8—Mn4—O1 | 172.24 (10) | C28—C33—H33C | 109.5 |
O8—Mn4—O3 | 92.02 (9) | H33A—C33—H33B | 109.5 |
O8—Mn4—O4 | 93.95 (9) | H33A—C33—H33C | 109.5 |
O8—Mn4—O10i | 98.67 (9) | H33B—C33—H33C | 109.5 |
O10i—Mn4—Mn3 | 83.17 (5) | O15—C34—C30 | 109.8 (3) |
O10i—Mn4—O3 | 163.43 (7) | O15—C34—H34A | 109.7 |
Mn3—O1—Mn1 | 88.47 (7) | O15—C34—H34B | 109.7 |
Mn4—O1—Mn1 | 96.62 (8) | C30—C34—H34A | 109.7 |
Mn4—O1—Mn3 | 102.54 (8) | C30—C34—H34B | 109.7 |
C1—O1—Mn1 | 124.55 (19) | H34A—C34—H34B | 108.2 |
C1—O1—Mn3 | 120.65 (17) | O11—C35—O12 | 125.0 (3) |
C1—O1—Mn4 | 117.86 (17) | O11—C35—C36 | 117.6 (3) |
Mn1—O2—Mn2 | 96.23 (8) | O12—C35—C36 | 117.5 (3) |
Mn3—O2—Mn1 | 110.77 (10) | C37—C36—C35 | 120.2 (3) |
Mn3—O2—Mn2 | 110.88 (10) | C41—C36—C35 | 120.9 (3) |
Mn1—O3—Mn4 | 107.22 (9) | C41—C36—C37 | 118.9 (4) |
C9—O3—Mn1 | 117.61 (19) | C36—C37—H37 | 119.6 |
C9—O3—Mn4 | 121.6 (2) | C38—C37—C36 | 120.7 (4) |
Mn3—O4—Mn2i | 86.15 (7) | C38—C37—H37 | 119.6 |
Mn4—O4—Mn2i | 97.47 (8) | C37—C38—H38 | 119.8 |
Mn4—O4—Mn3 | 96.21 (8) | C39—C38—C37 | 120.5 (5) |
C17—O4—Mn2i | 123.30 (17) | C39—C38—H38 | 119.8 |
C17—O4—Mn3 | 125.88 (16) | C38—C39—H39 | 120.1 |
C17—O4—Mn4 | 119.61 (17) | C38—C39—C40 | 119.8 (5) |
Mn1—O5—Mn2 | 95.94 (8) | C40—C39—H39 | 120.1 |
C25—O5—Mn1 | 120.45 (18) | C39—C40—H40 | 119.8 |
C25—O5—Mn2 | 120.49 (17) | C39—C40—C41 | 120.4 (5) |
C3—O6—Mn4 | 128.97 (18) | C41—C40—H40 | 119.8 |
C14—O7—Mn1 | 128.61 (19) | C36—C41—C40 | 119.6 (4) |
C19—O8—Mn4 | 127.91 (18) | C36—C41—H41 | 120.2 |
C27—O9—Mn2 | 127.82 (18) | C40—C41—H41 | 120.2 |
Mn2—O10—Mn4i | 105.48 (9) | C42—O16—H16 | 109.5 |
C32—O10—Mn2 | 119.09 (18) | O16—C42—H42A | 110.8 |
C32—O10—Mn4i | 120.87 (19) | O16—C42—H42B | 110.8 |
C35—O11—Mn2 | 127.0 (2) | O16—C42—C43 | 104.9 (8) |
C35—O12—Mn1 | 125.1 (2) | H42A—C42—H42B | 108.8 |
C8—O13—H13 | 109.5 | C43—C42—H42A | 110.8 |
C15—O14—H14 | 109.5 | C43—C42—H42B | 110.8 |
C34—O15—H15 | 109.5 | C42—C43—H43A | 109.5 |
C24—O17—H17 | 109.5 | C42—C43—H43B | 109.5 |
C5—N1—C4 | 119.1 (3) | C42—C43—H43C | 109.5 |
C12—N2—H2 | 117.9 | H43A—C43—H43B | 109.5 |
C12—N2—C13 | 124.1 (3) | H43A—C43—H43C | 109.5 |
C13—N2—H2 | 117.9 | H43B—C43—H43C | 109.5 |
C20—N3—C21 | 119.2 (3) | ||
Mn1—Mn2—O9—C27 | 166.9 (2) | O11—C35—C36—C41 | 177.9 (3) |
Mn1—Mn2—O10—Mn4i | 85.65 (11) | O12—Mn1—O3—Mn4 | −169.09 (9) |
Mn1—Mn2—O10—C32 | −134.58 (19) | O12—Mn1—O3—C9 | 49.5 (2) |
Mn1—O1—C1—C2 | −64.4 (3) | O12—Mn1—O7—C14 | −89.6 (3) |
Mn1—O3—C9—C10 | 63.5 (3) | O12—C35—C36—C37 | 178.2 (3) |
Mn1—O5—C25—C26 | −127.1 (3) | O12—C35—C36—C41 | −2.5 (5) |
Mn1—O7—C14—C10 | 12.5 (5) | N1—C5—C6—C2 | −0.1 (7) |
Mn1—O7—C14—C13 | −167.8 (2) | N1—C5—C6—C8 | 178.7 (4) |
Mn1—O12—C35—O11 | 3.5 (4) | N2—C13—C14—O7 | −178.4 (3) |
Mn1—O12—C35—C36 | −176.0 (2) | N2—C13—C14—C10 | 1.3 (5) |
Mn2—Mn1—O3—Mn4 | −83.27 (12) | N3—C21—C22—C18 | 0.6 (7) |
Mn2—Mn1—O3—C9 | 135.3 (2) | N3—C21—C22—C24 | 179.5 (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—C34 | 179.7 (4) |
Mn2—O5—C25—C26 | 113.8 (3) | C1—C2—C3—O6 | 4.7 (5) |
Mn2—O9—C27—C28 | 171.4 (2) | C1—C2—C3—C4 | −173.4 (3) |
Mn2—O9—C27—C31 | −8.0 (5) | C1—C2—C6—C5 | 174.9 (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—C36 | 174.4 (2) | C2—C3—C4—C7 | 176.2 (3) |
Mn3—Mn1—O3—Mn4 | −43.35 (7) | C2—C6—C8—O13 | 71.6 (5) |
Mn3—Mn1—O3—C9 | 175.2 (2) | C3—C2—C6—C5 | −1.9 (6) |
Mn3—Mn1—O7—C14 | 90.5 (3) | C3—C2—C6—C8 | 179.4 (4) |
Mn3—Mn2—O9—C27 | −97.2 (2) | C4—N1—C5—C6 | 0.5 (7) |
Mn3—Mn2—O10—Mn4i | 41.38 (7) | C5—N1—C4—C3 | 1.1 (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—C4 | 3.4 (5) |
Mn3—O4—C17—C18 | 173.3 (2) | C9—C10—C11—C12 | −179.9 (4) |
Mn4—O1—C1—C2 | 57.1 (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—C18 | 48.9 (3) | C9—C10—C14—C13 | 179.7 (3) |
Mn4—O6—C3—C2 | 11.1 (5) | C10—C11—C12—N2 | −0.9 (6) |
Mn4—O6—C3—C4 | −170.8 (2) | C10—C11—C15—O14 | 169.2 (4) |
Mn4—O8—C19—C18 | 7.3 (5) | C11—C10—C14—O7 | 177.6 (3) |
Mn4—O8—C19—C20 | −173.6 (2) | C11—C10—C14—C13 | −2.1 (5) |
Mn4i—O10—C32—C31 | 76.4 (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—C14 | 83.5 (3) | C13—N2—C12—C11 | 0.0 (6) |
O1—Mn4—O6—C3 | 3.8 (3) | C14—C10—C11—C12 | 1.9 (6) |
O1—C1—C2—C3 | −40.1 (4) | C14—C10—C11—C15 | −178.8 (4) |
O1—C1—C2—C6 | 143.2 (3) | C15—C11—C12—N2 | 179.8 (4) |
O2—Mn1—O3—Mn4 | −76.12 (10) | C16—C13—C14—O7 | −0.4 (5) |
O2—Mn1—O3—C9 | 142.4 (2) | C16—C13—C14—C10 | 179.3 (3) |
O2—Mn2—O9—C27 | −149.7 (5) | C17—C18—C19—O8 | 2.5 (5) |
O2—Mn2—O10—Mn4i | 74.66 (10) | C17—C18—C19—C20 | −176.5 (3) |
O2—Mn2—O10—C32 | −145.6 (2) | C17—C18—C22—C21 | 176.8 (4) |
O3—Mn1—O7—C14 | 7.8 (3) | C17—C18—C22—C24 | −2.0 (6) |
O3—Mn4—O6—C3 | 84.3 (3) | C18—C19—C20—N3 | −1.0 (5) |
O3—Mn4—O8—C19 | −80.0 (3) | C18—C19—C20—C23 | 178.8 (3) |
O3—C9—C10—C11 | 144.1 (3) | C18—C22—C24—O17 | 64.0 (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—C32 | 136.6 (2) | C21—N3—C20—C19 | 1.2 (6) |
O4—Mn4—O8—C19 | 6.6 (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—C22 | 151.0 (3) | C22—C18—C19—O8 | 179.5 (3) |
O5—Mn1—O3—Mn4 | −3.5 (5) | C22—C18—C19—C20 | 0.4 (5) |
O5—Mn1—O3—C9 | −144.9 (4) | C27—C31—C32—O10 | 35.1 (4) |
O5—Mn1—O7—C14 | 176.2 (3) | C28—N4—C29—C30 | 1.9 (6) |
O5—Mn2—O9—C27 | 178.5 (3) | C28—C27—C31—C30 | 1.4 (5) |
O6—Mn4—O8—C19 | 179.0 (3) | C28—C27—C31—C32 | 178.7 (3) |
O6—C3—C4—N1 | 178.7 (3) | C29—N4—C28—C27 | −0.6 (5) |
O6—C3—C4—C7 | −2.0 (5) | C29—N4—C28—C33 | 179.2 (4) |
O7—Mn1—O3—Mn4 | 96.70 (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—C3 | 176.1 (3) | C29—C30—C34—O15 | 7.5 (6) |
O8—C19—C20—N3 | 179.9 (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—C33 | 179.1 (3) |
O9—Mn2—O10—C32 | 41.0 (2) | C31—C30—C34—O15 | −171.2 (4) |
O9—C27—C28—N4 | 179.5 (3) | C34—C30—C31—C27 | 178.6 (4) |
O9—C27—C28—C33 | −0.4 (5) | C34—C30—C31—C32 | 1.3 (5) |
O9—C27—C31—C30 | −179.2 (3) | C35—C36—C37—C38 | 179.5 (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—C40 | 0.3 (5) |
O10i—Mn4—O8—C19 | 87.3 (3) | C37—C38—C39—C40 | −0.1 (7) |
O11—Mn2—O9—C27 | 85.6 (3) | C38—C39—C40—C41 | 0.6 (7) |
O11—Mn2—O10—Mn4i | 167.25 (9) | C39—C40—C41—C36 | −0.7 (6) |
O11—Mn2—O10—C32 | −53.0 (2) | C41—C36—C37—C38 | 0.2 (5) |
O11—C35—C36—C37 | −1.4 (5) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O14—H14···N3ii | 0.84 | 1.80 | 2.619 (4) | 163 |
O15—H15···N1iii | 0.84 | 1.84 | 2.675 (4) | 175 |
O17—H17···O13i | 0.84 | 1.89 | 2.684 (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).
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