Structure of a penta­manganese(II)–phenoxide cluster with a central five-coordinate oxide: Mn^II₅(μ-OPh)₆(μ₃-OPh)₂(μ₅-O)(Py)₆·Py (Py is pyridine)

Polynuclear metal clusters frequently feature geometric structural features not common in traditional coordination chemistry. These structures are of particular inter­est to bioinorganic chemists studying metallocluster enzymes, which frequently possess remarkably unusual inorganic structures. The structure of the manganese cluster μ₅-oxido-di-μ₃-phenoxido-hexa-μ-phen­oxido-hexa­kis­(pyridine-κN)hexa­manganese(II) pyridine monosolvate, [Mn₅(C₆H₅O)₈O(C₅H₅N)₆]·C₅H₅N or Mn^II₅(μ-OPh)₆(μ₃-OPh)₂(μ₅-O)(Py)₆·Py, con­taining an unusual trigonal bipyramidal central oxide, is described. The compound was isolated from a reaction mixture containing bis­(tri­methyl­silyl­amido)­man­ganese(II) and phenol. The central O atom is presumed to have originated as adventitious water. The mol­ecule crystalizes in a primitive monoclinic crystal system and is presented in the centrosymetric P2/n space group. The mol­ecule possesses crystallographically imposed twofold symmetry, with the central O atom centred on the twofold axis and surrounded by a distorted trigonal bipyramidal arrangement of Mn atoms, which are further bridged by phenoxide ligands, and terminally ligated by pyridine. A pyridine solvent mol­ecule resides nearby, also situated on a crystallographic twofold axis. The cluster is compared to three closely related previously reported structures.

Computing details

Data collection: COSMO (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

µ₅-Oxido-di-µ₃-phenoxido-hexa-µ-phenoxido-hexakis(pyridine-κN)hexamanganese(II) pyridine monosolvate

Crystal data

[Mn5(C6H5O)8O(C5H5N)6]·C5H5N	F(000) = 1638
Mr = 1589.20	Dx = 1.415 Mg m^−3
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.027 (5) Å	Cell parameters from 4515 reflections
b = 13.520 (5) Å	θ = 2.2–24.0°
c = 21.233 (8) Å	µ = 0.89 mm^−1
β = 94.025 (9)°	T = 173 K
V = 3731 (2) Å^3	Plate, yellow
Z = 2	0.08 × 0.06 × 0.03 mm

Data collection

Bruker Kappa APEXII DUO diffractometer	6571 independent reflections
Radiation source: sealed tube	4142 reflections with I > 2σ(I)
Detector resolution: 8.333 pixels mm^-1	Rint = 0.087
φ, ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2013)	h = −15→11
Tmin = 0.679, Tmax = 0.745	k = −13→16
23595 measured reflections	l = −25→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0332P)^2] where P = (Fo^2 + 2Fc^2)/3
6571 reflections	(Δ/σ)max = 0.001
471 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.88779 (4)	0.76988 (4)	0.19612 (2)	0.02507 (14)
Mn2	0.67949 (4)	0.86327 (4)	0.18672 (2)	0.02527 (14)
Mn3	0.7500	0.60383 (5)	0.2500	0.0288 (2)
O1	0.7500	0.7550 (2)	0.2500	0.0232 (7)
O2	0.84475 (16)	0.92765 (16)	0.21881 (11)	0.0309 (6)
O3	0.77377 (16)	0.80796 (18)	0.11682 (11)	0.0360 (6)
O4	0.53526 (15)	0.79289 (16)	0.20761 (10)	0.0279 (6)
O5	0.88131 (17)	0.61442 (16)	0.19442 (12)	0.0383 (6)
N1	1.0304 (2)	0.7992 (2)	0.14663 (14)	0.0332 (7)
N2	0.5953 (2)	0.9768 (2)	0.12566 (13)	0.0293 (7)
N3	0.6664 (2)	0.4896 (2)	0.18966 (14)	0.0336 (7)
C1	0.8739 (2)	1.0148 (3)	0.19520 (18)	0.0302 (9)
C2	0.9084 (3)	1.0215 (3)	0.13495 (19)	0.0413 (10)
H2	0.9135	0.9630	0.1106	0.050*
C3	0.9357 (3)	1.1114 (4)	0.1093 (2)	0.0553 (12)
H3	0.9603	1.1136	0.0683	0.066*
C4	0.9273 (3)	1.1976 (3)	0.1434 (3)	0.0594 (14)
H4	0.9444	1.2595	0.1258	0.071*
C5	0.8938 (3)	1.1920 (3)	0.2032 (2)	0.0535 (12)
H5	0.8877	1.2510	0.2269	0.064*
C6	0.8689 (2)	1.1028 (3)	0.2295 (2)	0.0374 (10)
H6	0.8480	1.1010	0.2714	0.045*
C7	0.7575 (2)	0.7753 (3)	0.05841 (17)	0.0309 (9)
C8	0.8003 (3)	0.8232 (3)	0.00802 (18)	0.0409 (10)
H8	0.8415	0.8804	0.0161	0.049*
C9	0.7840 (3)	0.7889 (4)	−0.05378 (19)	0.0531 (12)
H9	0.8140	0.8227	−0.0871	0.064*
C10	0.7251 (3)	0.7070 (4)	−0.0666 (2)	0.0594 (14)
H10	0.7137	0.6839	−0.1088	0.071*
C11	0.6823 (3)	0.6581 (3)	−0.0181 (2)	0.0569 (13)
H11	0.6414	0.6009	−0.0268	0.068*
C12	0.6983 (3)	0.6918 (3)	0.0438 (2)	0.0428 (10)
H12	0.6681	0.6570	0.0767	0.051*
C13	0.4636 (3)	0.7448 (3)	0.17266 (17)	0.0318 (9)
C14	0.4666 (3)	0.7354 (3)	0.10731 (18)	0.0398 (10)
H14	0.5190	0.7688	0.0868	0.048*
C15	0.3958 (3)	0.6791 (3)	0.0714 (2)	0.0496 (11)
H15	0.4014	0.6733	0.0272	0.059*
C16	0.3166 (3)	0.6310 (3)	0.0996 (2)	0.0498 (11)
H16	0.2686	0.5911	0.0754	0.060*
C17	0.3096 (3)	0.6424 (3)	0.1628 (2)	0.0432 (10)
H17	0.2546	0.6114	0.1824	0.052*
C18	0.3806 (3)	0.6981 (3)	0.19956 (18)	0.0359 (9)
H18	0.3730	0.7048	0.2435	0.043*
C19	0.9304 (3)	0.5524 (2)	0.15714 (18)	0.0315 (9)
C20	1.0297 (3)	0.5192 (3)	0.17409 (19)	0.0420 (10)
H20	1.0630	0.5391	0.2133	0.050*
C21	1.0804 (3)	0.4576 (3)	0.1346 (2)	0.0463 (11)
H21	1.1485	0.4365	0.1467	0.056*
C22	1.0341 (3)	0.4268 (3)	0.0785 (2)	0.0464 (11)
H22	1.0696	0.3846	0.0516	0.056*
C23	0.9356 (3)	0.4574 (3)	0.06122 (19)	0.0448 (10)
H23	0.9023	0.4357	0.0224	0.054*
C24	0.8848 (3)	0.5196 (3)	0.10014 (18)	0.0391 (10)
H24	0.8168	0.5404	0.0875	0.047*
C25	1.0445 (3)	0.7656 (3)	0.08908 (18)	0.0422 (10)
H25	0.9976	0.7182	0.0707	0.051*
C26	1.1249 (4)	0.7971 (4)	0.0551 (2)	0.0604 (13)
H26	1.1336	0.7716	0.0141	0.073*
C27	1.1923 (4)	0.8664 (4)	0.0819 (3)	0.0705 (15)
H27	1.2468	0.8908	0.0588	0.085*
C28	1.1804 (3)	0.9000 (3)	0.1418 (2)	0.0605 (13)
H28	1.2275	0.9459	0.1616	0.073*
C29	1.0982 (3)	0.8651 (3)	0.1722 (2)	0.0447 (10)
H29	1.0887	0.8889	0.2135	0.054*
C30	0.6354 (3)	1.0268 (3)	0.07941 (16)	0.0328 (9)
H30	0.7053	1.0152	0.0715	0.039*
C31	0.5799 (3)	1.0951 (3)	0.04210 (17)	0.0382 (9)
H31	0.6115	1.1295	0.0096	0.046*
C32	0.4788 (3)	1.1124 (3)	0.05266 (17)	0.0373 (10)
H32	0.4389	1.1582	0.0274	0.045*
C33	0.4368 (3)	1.0620 (3)	0.10039 (18)	0.0379 (10)
H33	0.3670	1.0728	0.1090	0.046*
C34	0.4965 (3)	0.9956 (3)	0.13595 (17)	0.0354 (9)
H34	0.4666	0.9615	0.1692	0.042*
C35	0.7089 (3)	0.4044 (3)	0.17204 (18)	0.0410 (10)
H35	0.7806	0.3955	0.1815	0.049*
C36	0.6553 (3)	0.3297 (3)	0.1414 (2)	0.0545 (12)
H36	0.6884	0.2702	0.1304	0.065*
C37	0.5523 (4)	0.3436 (3)	0.1270 (2)	0.0749 (16)
H37	0.5127	0.2937	0.1052	0.090*
C38	0.5069 (3)	0.4294 (3)	0.1442 (2)	0.0659 (14)
H38	0.4353	0.4398	0.1348	0.079*
C39	0.5664 (3)	0.5004 (3)	0.17519 (19)	0.0455 (11)
H39	0.5344	0.5601	0.1869	0.055*
N4	0.2500	0.0923 (4)	0.2500	0.0848 (19)
C40	0.1641 (3)	0.1445 (4)	0.2377 (2)	0.0723 (15)
H40	0.1016	0.1096	0.2282	0.087*
C41	0.1611 (3)	0.2452 (4)	0.2379 (2)	0.0684 (14)
H41	0.0975	0.2788	0.2296	0.082*
C42	0.2500	0.2979 (5)	0.2500	0.068 (2)
H42	0.2500	0.3681	0.2500	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0233 (3)	0.0266 (3)	0.0257 (3)	0.0007 (2)	0.0047 (2)	−0.0009 (2)
Mn2	0.0251 (3)	0.0261 (3)	0.0246 (3)	0.0028 (2)	0.0022 (2)	0.0039 (2)
Mn3	0.0312 (4)	0.0195 (4)	0.0366 (5)	0.000	0.0087 (4)	0.000
O1	0.0230 (16)	0.0220 (19)	0.0246 (19)	0.000	0.0012 (14)	0.000
O2	0.0381 (14)	0.0239 (14)	0.0309 (15)	−0.0065 (11)	0.0043 (11)	0.0019 (11)
O3	0.0340 (14)	0.0491 (17)	0.0248 (15)	0.0078 (12)	0.0017 (11)	0.0002 (12)
O4	0.0197 (12)	0.0381 (15)	0.0252 (14)	−0.0022 (10)	−0.0023 (10)	0.0038 (11)
O5	0.0401 (14)	0.0251 (14)	0.0518 (17)	0.0017 (12)	0.0183 (13)	−0.0030 (12)
N1	0.0300 (17)	0.039 (2)	0.0311 (19)	0.0019 (15)	0.0070 (14)	0.0024 (15)
N2	0.0323 (17)	0.0276 (18)	0.0281 (18)	0.0057 (14)	0.0023 (14)	0.0033 (14)
N3	0.0364 (18)	0.0268 (18)	0.038 (2)	0.0005 (15)	0.0034 (15)	0.0010 (15)
C1	0.0174 (18)	0.030 (2)	0.043 (3)	−0.0018 (16)	−0.0006 (16)	0.0103 (19)
C2	0.033 (2)	0.047 (3)	0.044 (3)	−0.0073 (19)	0.0021 (19)	0.012 (2)
C3	0.037 (2)	0.071 (3)	0.058 (3)	−0.010 (2)	0.002 (2)	0.033 (3)
C4	0.041 (3)	0.046 (3)	0.089 (4)	−0.009 (2)	−0.007 (3)	0.033 (3)
C5	0.040 (2)	0.029 (2)	0.091 (4)	−0.002 (2)	−0.003 (2)	0.007 (2)
C6	0.027 (2)	0.026 (2)	0.059 (3)	−0.0022 (17)	0.0003 (18)	0.004 (2)
C7	0.0228 (18)	0.038 (2)	0.031 (2)	0.0122 (17)	−0.0030 (16)	0.0019 (19)
C8	0.031 (2)	0.058 (3)	0.034 (3)	0.0082 (19)	0.0024 (18)	−0.001 (2)
C9	0.039 (2)	0.091 (4)	0.031 (3)	0.028 (3)	0.008 (2)	0.003 (2)
C10	0.045 (3)	0.095 (4)	0.037 (3)	0.040 (3)	−0.010 (2)	−0.023 (3)
C11	0.046 (3)	0.055 (3)	0.066 (3)	0.021 (2)	−0.024 (2)	−0.027 (3)
C12	0.037 (2)	0.043 (3)	0.048 (3)	0.011 (2)	−0.0029 (19)	0.001 (2)
C13	0.0284 (19)	0.033 (2)	0.033 (2)	0.0103 (18)	0.0000 (17)	0.0072 (18)
C14	0.042 (2)	0.044 (2)	0.033 (2)	0.000 (2)	0.0042 (18)	0.0045 (19)
C15	0.057 (3)	0.049 (3)	0.041 (3)	0.004 (2)	−0.007 (2)	−0.003 (2)
C16	0.046 (3)	0.046 (3)	0.054 (3)	−0.003 (2)	−0.014 (2)	−0.004 (2)
C17	0.028 (2)	0.044 (3)	0.058 (3)	−0.0010 (19)	0.0030 (19)	0.001 (2)
C18	0.029 (2)	0.039 (2)	0.040 (2)	0.0004 (18)	0.0060 (17)	0.0007 (19)
C19	0.032 (2)	0.022 (2)	0.042 (3)	0.0043 (17)	0.0132 (18)	0.0008 (18)
C20	0.036 (2)	0.040 (2)	0.050 (3)	0.0037 (19)	0.0022 (19)	−0.007 (2)
C21	0.034 (2)	0.045 (3)	0.061 (3)	0.015 (2)	0.012 (2)	0.004 (2)
C22	0.058 (3)	0.033 (3)	0.050 (3)	0.011 (2)	0.022 (2)	0.001 (2)
C23	0.057 (3)	0.046 (3)	0.032 (2)	0.006 (2)	0.006 (2)	0.001 (2)
C24	0.039 (2)	0.042 (2)	0.037 (3)	0.0127 (19)	0.0103 (19)	0.009 (2)
C25	0.044 (2)	0.050 (3)	0.033 (2)	0.016 (2)	0.0056 (19)	0.005 (2)
C26	0.069 (3)	0.071 (4)	0.045 (3)	0.024 (3)	0.025 (3)	0.015 (2)
C27	0.055 (3)	0.075 (4)	0.086 (4)	−0.001 (3)	0.045 (3)	0.022 (3)
C28	0.038 (2)	0.061 (3)	0.084 (4)	−0.003 (2)	0.021 (2)	0.012 (3)
C29	0.036 (2)	0.050 (3)	0.049 (3)	0.000 (2)	0.013 (2)	0.007 (2)
C30	0.035 (2)	0.033 (2)	0.031 (2)	0.0060 (18)	0.0084 (17)	0.0017 (18)
C31	0.052 (2)	0.034 (2)	0.030 (2)	0.008 (2)	0.0102 (19)	0.0063 (18)
C32	0.049 (2)	0.028 (2)	0.033 (2)	0.0174 (19)	−0.0067 (19)	0.0004 (18)
C33	0.031 (2)	0.036 (2)	0.047 (3)	0.0074 (18)	0.0010 (19)	0.006 (2)
C34	0.032 (2)	0.036 (2)	0.038 (2)	0.0037 (18)	0.0060 (18)	0.0115 (18)
C35	0.043 (2)	0.030 (2)	0.051 (3)	0.0057 (19)	0.005 (2)	−0.005 (2)
C36	0.059 (3)	0.039 (3)	0.064 (3)	0.006 (2)	−0.012 (2)	−0.023 (2)
C37	0.069 (3)	0.051 (3)	0.099 (4)	0.010 (3)	−0.036 (3)	−0.043 (3)
C38	0.053 (3)	0.056 (3)	0.084 (4)	0.014 (2)	−0.031 (3)	−0.030 (3)
C39	0.051 (3)	0.032 (2)	0.052 (3)	0.012 (2)	−0.006 (2)	−0.006 (2)
N4	0.069 (4)	0.066 (4)	0.114 (6)	0.000	−0.026 (4)	0.000
C40	0.053 (3)	0.077 (4)	0.085 (4)	−0.011 (3)	−0.012 (3)	0.025 (3)
C41	0.046 (3)	0.084 (4)	0.073 (4)	0.006 (3)	−0.010 (2)	0.009 (3)
C42	0.066 (5)	0.068 (5)	0.066 (5)	0.000	−0.022 (4)	0.000

Geometric parameters (Å, º)

Mn1—O1	2.2044 (8)	C14—H14	0.9500
Mn1—O2	2.266 (2)	C14—C15	1.382 (5)
Mn1—O3	2.226 (2)	C15—H15	0.9500
Mn1—O4^i	2.234 (2)	C15—C16	1.391 (5)
Mn1—O5	2.104 (2)	C16—H16	0.9500
Mn1—N1	2.233 (3)	C16—C17	1.359 (5)
Mn2—O1	2.149 (2)	C17—H17	0.9500
Mn2—O2	2.377 (2)	C17—C18	1.390 (5)
Mn2—O2^i	2.229 (2)	C18—H18	0.9500
Mn2—O3	2.128 (2)	C19—C20	1.393 (5)
Mn2—O4	2.179 (2)	C19—C24	1.383 (5)
Mn2—N2	2.245 (3)	C20—H20	0.9500
Mn3—Mn1^i	3.1400 (10)	C20—C21	1.383 (5)
Mn3—O1	2.043 (3)	C21—H21	0.9500
Mn3—O5	2.150 (2)	C21—C22	1.362 (5)
Mn3—O5^i	2.150 (2)	C22—H22	0.9500
Mn3—N3	2.240 (3)	C22—C23	1.374 (5)
Mn3—N3^i	2.240 (3)	C23—H23	0.9500
O1—Mn1^i	2.2044 (8)	C23—C24	1.380 (5)
O1—Mn2^i	2.149 (2)	C24—H24	0.9500
O2—Mn2^i	2.229 (2)	C25—H25	0.9500
O2—C1	1.345 (4)	C25—C26	1.380 (5)
O3—C7	1.319 (4)	C26—H26	0.9500
O4—Mn1^i	2.234 (2)	C26—C27	1.379 (6)
O4—C13	1.322 (4)	C27—H27	0.9500
O5—C19	1.345 (4)	C27—C28	1.370 (6)
N1—C25	1.328 (4)	C28—H28	0.9500
N1—C29	1.342 (5)	C28—C29	1.372 (5)
N2—C30	1.329 (4)	C29—H29	0.9500
N2—C34	1.344 (4)	C30—H30	0.9500
N3—C35	1.342 (4)	C30—C31	1.387 (5)
N3—C39	1.324 (4)	C31—H31	0.9500
C1—C2	1.389 (5)	C31—C32	1.372 (5)
C1—C6	1.399 (5)	C32—H32	0.9500
C2—H2	0.9500	C32—C33	1.366 (5)
C2—C3	1.387 (5)	C33—H33	0.9500
C3—H3	0.9500	C33—C34	1.379 (5)
C3—C4	1.380 (6)	C34—H34	0.9500
C4—H4	0.9500	C35—H35	0.9500
C4—C5	1.373 (6)	C35—C36	1.367 (5)
C5—H5	0.9500	C36—H36	0.9500
C5—C6	1.378 (5)	C36—C37	1.367 (5)
C6—H6	0.9500	C37—H37	0.9500
C7—C8	1.399 (5)	C37—C38	1.363 (5)
C7—C12	1.390 (5)	C38—H38	0.9500
C8—H8	0.9500	C38—C39	1.373 (5)
C8—C9	1.394 (5)	C39—H39	0.9500
C9—H9	0.9500	N4—C40^ii	1.334 (5)
C9—C10	1.363 (6)	N4—C40	1.334 (5)
C10—H10	0.9500	C40—H40	0.9500
C10—C11	1.375 (6)	C40—C41	1.362 (6)
C11—H11	0.9500	C41—H41	0.9500
C11—C12	1.393 (5)	C41—C42	1.368 (5)
C12—H12	0.9500	C42—C41^ii	1.368 (5)
C13—C14	1.397 (5)	C42—H42	0.9500
C13—C18	1.407 (5)
O1—Mn1—O2	75.72 (9)	C7—C8—H8	119.2
O1—Mn1—O3	83.65 (7)	C9—C8—C7	121.5 (4)
O1—Mn1—O4^i	82.38 (6)	C9—C8—H8	119.2
O1—Mn1—N1	174.30 (11)	C8—C9—H9	119.8
O3—Mn1—O2	77.36 (9)	C10—C9—C8	120.3 (4)
O3—Mn1—O4^i	153.19 (9)	C10—C9—H9	119.8
O3—Mn1—N1	97.82 (10)	C9—C10—H10	120.2
O4^i—Mn1—O2	77.07 (8)	C9—C10—C11	119.5 (4)
O5—Mn1—O1	83.36 (10)	C11—C10—H10	120.2
O5—Mn1—O2	159.06 (8)	C10—C11—H11	119.7
O5—Mn1—O3	101.20 (10)	C10—C11—C12	120.6 (4)
O5—Mn1—O4^i	99.77 (9)	C12—C11—H11	119.7
O5—Mn1—N1	101.69 (10)	C7—C12—C11	121.3 (4)
N1—Mn1—O2	99.18 (10)	C7—C12—H12	119.4
N1—Mn1—O4^i	94.08 (10)	C11—C12—H12	119.4
O1—Mn2—O2^i	77.58 (8)	O4—C13—C14	122.4 (3)
O1—Mn2—O2	74.44 (7)	O4—C13—C18	121.7 (3)
O1—Mn2—O4	84.95 (7)	C14—C13—C18	115.9 (3)
O1—Mn2—N2	175.41 (7)	C13—C14—H14	118.8
O2^i—Mn2—O2	77.40 (9)	C15—C14—C13	122.3 (4)
O2^i—Mn2—N2	99.11 (9)	C15—C14—H14	118.8
O3—Mn2—O1	87.38 (7)	C14—C15—H15	119.8
O3—Mn2—O2	76.89 (9)	C14—C15—C16	120.4 (4)
O3—Mn2—O2^i	152.89 (9)	C16—C15—H15	119.8
O3—Mn2—O4	122.46 (9)	C15—C16—H16	120.8
O3—Mn2—N2	96.89 (10)	C17—C16—C15	118.3 (4)
O4—Mn2—O2	151.40 (8)	C17—C16—H16	120.8
O4—Mn2—O2^i	78.97 (8)	C16—C17—H17	119.1
O4—Mn2—N2	91.31 (9)	C16—C17—C18	121.8 (4)
N2—Mn2—O2	108.12 (9)	C18—C17—H17	119.1
Mn1^i—Mn3—Mn1	88.71 (4)	C13—C18—H18	119.5
O1—Mn3—Mn1	44.356 (18)	C17—C18—C13	121.0 (4)
O1—Mn3—Mn1^i	44.354 (18)	C17—C18—H18	119.5
O1—Mn3—O5^i	86.18 (6)	O5—C19—C20	121.3 (3)
O1—Mn3—O5	86.18 (6)	O5—C19—C24	121.5 (3)
O1—Mn3—N3^i	133.59 (8)	C24—C19—C20	117.1 (3)
O1—Mn3—N3	133.59 (8)	C19—C20—H20	119.6
O5^i—Mn3—Mn1	130.51 (7)	C21—C20—C19	120.8 (4)
O5—Mn3—Mn1	41.86 (6)	C21—C20—H20	119.6
O5—Mn3—Mn1^i	130.51 (7)	C20—C21—H21	119.6
O5^i—Mn3—Mn1^i	41.86 (6)	C22—C21—C20	120.9 (4)
O5^i—Mn3—O5	172.36 (12)	C22—C21—H21	119.6
O5^i—Mn3—N3^i	96.06 (10)	C21—C22—H22	120.3
O5—Mn3—N3^i	89.21 (10)	C21—C22—C23	119.3 (4)
O5^i—Mn3—N3	89.21 (10)	C23—C22—H22	120.3
O5—Mn3—N3	96.07 (10)	C22—C23—H23	119.9
N3^i—Mn3—Mn1	115.72 (8)	C22—C23—C24	120.1 (4)
N3^i—Mn3—Mn1^i	123.51 (8)	C24—C23—H23	119.9
N3—Mn3—Mn1	123.51 (8)	C19—C24—H24	119.1
N3—Mn3—Mn1^i	115.72 (8)	C23—C24—C19	121.7 (4)
N3^i—Mn3—N3	92.82 (15)	C23—C24—H24	119.1
Mn1^i—O1—Mn1	169.49 (15)	N1—C25—H25	118.8
Mn2^i—O1—Mn1	86.23 (6)	N1—C25—C26	122.3 (4)
Mn2—O1—Mn1	86.62 (6)	C26—C25—H25	118.8
Mn2—O1—Mn1^i	86.23 (6)	C25—C26—H26	120.7
Mn2^i—O1—Mn1^i	86.62 (6)	C27—C26—C25	118.5 (4)
Mn2^i—O1—Mn2	94.11 (12)	C27—C26—H26	120.7
Mn3—O1—Mn1	95.25 (7)	C26—C27—H27	120.1
Mn3—O1—Mn1^i	95.26 (7)	C28—C27—C26	119.9 (4)
Mn3—O1—Mn2^i	132.94 (6)	C28—C27—H27	120.1
Mn3—O1—Mn2	132.95 (6)	C27—C28—H28	121.1
Mn1—O2—Mn2	80.03 (7)	C27—C28—C29	117.8 (4)
Mn2^i—O2—Mn1	82.90 (8)	C29—C28—H28	121.1
Mn2^i—O2—Mn2	86.11 (8)	N1—C29—C28	123.5 (4)
C1—O2—Mn1	131.7 (2)	N1—C29—H29	118.3
C1—O2—Mn2	119.16 (19)	C28—C29—H29	118.3
C1—O2—Mn2^i	137.6 (2)	N2—C30—H30	118.5
Mn2—O3—Mn1	86.60 (9)	N2—C30—C31	123.0 (3)
C7—O3—Mn1	133.5 (2)	C31—C30—H30	118.5
C7—O3—Mn2	135.3 (2)	C30—C31—H31	120.4
Mn2—O4—Mn1^i	84.79 (8)	C32—C31—C30	119.3 (3)
C13—O4—Mn1^i	134.3 (2)	C32—C31—H31	120.4
C13—O4—Mn2	133.3 (2)	C31—C32—H32	120.8
Mn1—O5—Mn3	95.14 (9)	C33—C32—C31	118.4 (3)
C19—O5—Mn1	127.8 (2)	C33—C32—H32	120.8
C19—O5—Mn3	135.3 (2)	C32—C33—H33	120.3
C25—N1—Mn1	123.1 (3)	C32—C33—C34	119.4 (3)
C25—N1—C29	118.0 (3)	C34—C33—H33	120.3
C29—N1—Mn1	118.2 (2)	N2—C34—C33	123.0 (3)
C30—N2—Mn2	124.9 (2)	N2—C34—H34	118.5
C30—N2—C34	117.0 (3)	C33—C34—H34	118.5
C34—N2—Mn2	118.0 (2)	N3—C35—H35	118.0
C35—N3—Mn3	123.9 (2)	N3—C35—C36	124.1 (4)
C39—N3—Mn3	119.2 (2)	C36—C35—H35	118.0
C39—N3—C35	116.6 (3)	C35—C36—H36	121.1
O2—C1—C2	121.3 (3)	C35—C36—C37	117.7 (4)
O2—C1—C6	121.8 (3)	C37—C36—H36	121.1
C2—C1—C6	117.0 (3)	C36—C37—H37	120.2
C1—C2—H2	119.1	C38—C37—C36	119.7 (4)
C3—C2—C1	121.8 (4)	C38—C37—H37	120.2
C3—C2—H2	119.1	C37—C38—H38	120.6
C2—C3—H3	119.9	C37—C38—C39	118.8 (4)
C4—C3—C2	120.1 (4)	C39—C38—H38	120.6
C4—C3—H3	119.9	N3—C39—C38	123.2 (4)
C3—C4—H4	120.6	N3—C39—H39	118.4
C5—C4—C3	118.7 (4)	C38—C39—H39	118.4
C5—C4—H4	120.6	C40^ii—N4—C40	116.1 (6)
C4—C5—H5	119.3	N4—C40—H40	118.3
C4—C5—C6	121.5 (4)	N4—C40—C41	123.5 (5)
C6—C5—H5	119.3	C41—C40—H40	118.3
C1—C6—H6	119.6	C40—C41—H41	120.1
C5—C6—C1	120.9 (4)	C40—C41—C42	119.8 (5)
C5—C6—H6	119.6	C42—C41—H41	120.1
O3—C7—C8	121.2 (3)	C41^ii—C42—C41	117.3 (7)
O3—C7—C12	122.1 (3)	C41—C42—H42	121.4
C12—C7—C8	116.8 (4)	C41^ii—C42—H42	121.4
Mn1—O2—C1—C2	24.7 (4)	C4—C5—C6—C1	−2.0 (6)
Mn1—O2—C1—C6	−156.5 (2)	C6—C1—C2—C3	−0.7 (5)
Mn1—O3—C7—C8	−94.5 (4)	C7—C8—C9—C10	0.1 (6)
Mn1—O3—C7—C12	84.9 (4)	C8—C7—C12—C11	−0.3 (5)
Mn1^i—O4—C13—C14	−142.7 (3)	C8—C9—C10—C11	−0.3 (6)
Mn1^i—O4—C13—C18	36.0 (5)	C9—C10—C11—C12	0.2 (6)
Mn1—O5—C19—C20	86.9 (4)	C10—C11—C12—C7	0.0 (6)
Mn1—O5—C19—C24	−92.5 (4)	C12—C7—C8—C9	0.2 (5)
Mn1—N1—C25—C26	169.3 (3)	C13—C14—C15—C16	1.5 (6)
Mn1—N1—C29—C28	−170.1 (3)	C14—C13—C18—C17	3.0 (5)
Mn2^i—O2—C1—C2	161.6 (2)	C14—C15—C16—C17	1.3 (6)
Mn2—O2—C1—C2	−78.6 (3)	C15—C16—C17—C18	−1.8 (6)
Mn2^i—O2—C1—C6	−19.7 (5)	C16—C17—C18—C13	−0.4 (6)
Mn2—O2—C1—C6	100.1 (3)	C18—C13—C14—C15	−3.5 (5)
Mn2—O3—C7—C8	118.1 (3)	C19—C20—C21—C22	−0.9 (6)
Mn2—O3—C7—C12	−62.5 (5)	C20—C19—C24—C23	−0.7 (5)
Mn2—O4—C13—C14	−4.5 (5)	C20—C21—C22—C23	−0.1 (6)
Mn2—O4—C13—C18	174.2 (2)	C21—C22—C23—C24	0.7 (6)
Mn2—N2—C30—C31	178.8 (3)	C22—C23—C24—C19	−0.3 (6)
Mn2—N2—C34—C33	−178.4 (3)	C24—C19—C20—C21	1.3 (5)
Mn3—O5—C19—C20	−112.3 (4)	C25—N1—C29—C28	0.5 (5)
Mn3—O5—C19—C24	68.3 (5)	C25—C26—C27—C28	2.1 (7)
Mn3—N3—C35—C36	172.3 (3)	C26—C27—C28—C29	−2.3 (7)
Mn3—N3—C39—C38	−173.0 (3)	C27—C28—C29—N1	1.1 (6)
O2—C1—C2—C3	178.0 (3)	C29—N1—C25—C26	−0.8 (5)
O2—C1—C6—C5	−176.5 (3)	C30—N2—C34—C33	1.0 (5)
O3—C7—C8—C9	179.7 (3)	C30—C31—C32—C33	0.8 (5)
O3—C7—C12—C11	−179.7 (3)	C31—C32—C33—C34	−0.4 (5)
O4—C13—C14—C15	175.2 (3)	C32—C33—C34—N2	−0.5 (6)
O4—C13—C18—C17	−175.7 (3)	C34—N2—C30—C31	−0.6 (5)
O5—C19—C20—C21	−178.2 (3)	C35—N3—C39—C38	0.4 (6)
O5—C19—C24—C23	178.8 (3)	C35—C36—C37—C38	−0.9 (7)
N1—C25—C26—C27	−0.4 (6)	C36—C37—C38—C39	0.5 (8)
N2—C30—C31—C32	−0.3 (6)	C37—C38—C39—N3	−0.3 (7)
N3—C35—C36—C37	1.0 (7)	C39—N3—C35—C36	−0.8 (6)
C1—C2—C3—C4	−1.1 (6)	N4—C40—C41—C42	1.3 (7)
C2—C1—C6—C5	2.3 (5)	C40^ii—N4—C40—C41	−0.7 (4)
C2—C3—C4—C5	1.4 (6)	C40—C41—C42—C41^ii	−0.6 (3)
C3—C4—C5—C6	0.1 (6)

Symmetry codes: (i) −x+3/2, y, −z+1/2; (ii) −x+1/2, y, −z+1/2.