Di­aqua­bis(1,10-phenanthroline-κ²N,N′)­manganese(II) thiodiglycolate bis(1,10-phenanthroline-κ²N,N′)(thiodiglycolato-κ²O,O′)­manganese(II) tridecahydrate

The title compound, [Mn(C₁₂H₈N₂)₂(H₂O)₂](C₄H₄O₄S)·[Mn(C₄H₄O₄S)(C₁₂H₈N₂)₂]·13H₂O, contains one dianion of thio­diglycolic acid (tdga²⁻) and two independent man­ganese(II) moieties, viz. [Mn(phen)₂(H₂O)₂]²⁺ and [Mn(tdga)(phen)₂], where phen is 1,10-phenanthroline. The Mn^II atoms are octahedrally coordinated by four N atoms of two bidentate phen ligands [Mn—N = 2.240 (2)–2.3222 (19) Å] and either two water O atoms or two tdga carboxyl O atoms [Mn—O = 2.1214 (17)–2.1512 (17) Å]. The tdga ligand chelates as an O,O′-bidentate ligand, forming an eight-membered ring with one Mn atom. The free tdga²⁻ dianion is hydrogen bonded to an [Mn(phen)₂(H₂O)₂]²⁺ ion, with O...O distances of 2.606 (2) and 2.649 (2) Å. The crystal structure is further stabilized by an extensive network of hydrogen bonds involving 13 water mol­ecules.

S1. Comment

Metal complexes involving the carboxylate group are of interest not only as compounds that can be potentially used for the preparation of precursors applicable in materials chemistry (Devereux et al., 2002), and for their potential biological activity (Geraghty et al., 1999), but also from a structural point of view. Thiodiglycolic acid (tdgaH₂) is dicarboxylic acid containing four O atoms and one S atom in the molecule. These atoms cause coordination variability of tdga²⁻ to metal centers. It has been found that tdga²⁻ is coordinated preferentially as a tridentate O,S,O'-ligand (Drew et al., 1975; Delaunay et al., 1976, 1978; Bonomo et al., 1982). Moreover, it can be also chelated as a bidentate O,S-ligand (Efimenko et al., 1991) and it can form bridges in binuclear complexes (Baggio et al., 1999). Apart from the formation of mononuclear or binuclear compounds, transition metal complexes with tdgaH₂ in the form of polymeric chains (Bonomo et al., 1982) or three-dimensional structures (Kepert et al., 1999; Zhang et al., 2002; Grirrane et al., 2003) have been prepared. Recently, we have prepared and structurally characterized two mixed-ligand binuclear Cu^II complexes in which the tdga dianion acts as a bridge (Kopel et al., 2003). We report here the title compound, (I), which contains the tdga²⁻ ion chelated as a bidentate O,O'-ligand and forms an eight-membered ring with one Mn atom.

The crystal structure of (I) consists of [Mn(phen)₂(tdga)] complex molecules (Fig. 1a), [Mn(phen)₂(H₂O)₂]²⁺ complex cations (Fig. 1 b), tdga²⁻ anions (Fig. 1 b) and water molecules.

The Mn^II ion in the complex molecule adopts a substantially distorted octahedral geometry, defined by four N atoms of two phen ligands and two carboxyl O atoms of a tdga ligand in a cis configuration. While the first bidentate chelating phen ligand (containing atoms N40 and C53) is almost perfectly planar (the angles between its individual six-membered rings are up to 0.8°), the second phen ligand (containing atoms N55 and C68) is significantly deformed from planarity (the angles between its six-membered rings vary from 3.5 to 5.3°). The tdga ligand is chelated as a bidentate O,O'-ligand and forms an eight-membered ring with an Mn atom. The Mn—N and Mn—O distances in this complex vary from 2.240 to 2.322 Å, and from 2.123 to 2.151 Å, respectively. These lengths are comparable to the mean Mn—N and Mn—O distances (2.270 and 2.112 Å) found in related complexes (Cambridge Structural Database, Version 5.24.3; Allen, 2002).

The structure of the [Mn(phen)₂(H₂O)₂]²⁺ complex cation is similar to those of Mn^II-complex ions determined previously (McCann et al., 1997; Geraghty et al., 1998; Devereux et al., 2000a, 2000b, 2002; Zheng et al., 2001). Mn atom is surrounded by four N atoms of two phen ligands and two O atoms of two water molecules. Like the [Mn(phen)₂(tdga)] complex molecule, the cation displays a cis configuration and the Mn atom has a substantially distorted octahedral coordination. The Mn—N and Mn—O distances in the cation vary from 2.252 to 2.284 Å, and from 2.121 to 2.130 Å, respectively.

The positive charge of the cation is compensated by the negative charge of tdga dianion, which is? connected to the [Mn(phen)₂(H₂O)₂]²⁺ ion via O—H···O hydrogen bonds (Fig. 1 b and Table 2). The tdga²⁻ anion is further hydrogen bonded to five water molecules. In the crystal lattice of (I), anions and water molecules are linked by an extensive network of hydrogen bonds, thus forming two-dimensional (101) layers (Fig. 2 and Table 2).

S2. Experimental

TdgaNa₂ (0.19 g), dissolved in distilled water (10 ml), was added to a solution of MnSO₄·4H₂O (0.22 g) in an ethanol:water (1:1) mixture (30 ml). The reaction mixture was stirred for 30 min at room temperature and then phen·H₂O (0.2 g), dissolved in ethanol (20 ml), was added, with stirring, to the solution. The colour of the solution changed to yellow. It was stirred for 1 h and left for crystallization. Yellow crystals suitable for single-crystal X-ray analysis were obtained after several days.

S3. Refinement

Disordered water molecule O99 (atoms O99A–O99C) was refined isotropically. The large value (14.6) of the U_eq(max)/U_eq(min) ratio for O78 and the fact that the highest peak in the electron-density map was close to this atom led us to refine atom 078 as disordered, with two possible positions. The O78A—C76 [1.320 (4) Å] and O78B—C76 [1.189 (8) Å] bond lengths indicate localization of electron density in the carboxyl moiety insted of an electron dellocalization, such as was found around C atoms C71, C81 and C86. H atoms attached to C atoms were positioned geometrically, with U_iso values derived from U_eq of the corresponding C atoms. The H atoms attached to O atoms were refined freely, ?except for O—H distances, which were restrained to 0.95 Å, and two free variables were used to describe the U_iso(H) values. The first free variable describes U_iso values of the four H atoms attached to atoms O29 and O30, and the second describes U_iso values of H atoms attached to uncoordinated water O atoms.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction); cell refinement: CrysAlis RED (Oxford Diffraction); data reduction: CrysAlis RED (Oxford Diffraction); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Johnson & Burnett, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PARST (Nardelli, 1995).

Figures

	Fig. 1. : ORTEPIII (Johnson & Burnett, 1996) plot of (a) the [Mn(phen)2(tdga)] complex moiety and (b) the [Mn(phen)2(H2O)2]^2+ complex cation with the hydrogen-bonded tdga^2− dianion. Non-H atoms are drawn as displacement ellipsoids at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. : Part of the crystal structure of (I), showing the formation of a layer of hydrogen-bonded tdga^2− anions and water molecules. [Mn(phen)2(tdga)] and [Mn(phen)2(H2O)2]^2+ moieties and disordered water molecule O99 have been omitted for clarity. [Symmetry codes: (i) x, y, z − 1; (ii) 1 − x, −y, −z; (iii) −x, −y, −z; (iv) −x, 1 − y, −z.]

Diaqua-bis(1,10-phenanthroline-N,N')manganese(II)] [bis(1,10-phenanthroline-N,N')(thiodiglycolato-O,O')manganese(II)] thiodiglycolate tridecahydrate

Crystal data

[Mn(C12H8N2)2(H2O)2][Mn(C12H8N2)2(C4H4O4S)](C4H4O4S)·13H2O	Z = 2
Mr = 1393.17	F(000) = 1448
Triclinic, P1	Dx = 1.457 Mg m^−3
a = 15.0347 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 15.9870 (7) Å	Cell parameters from 7031 reflections
c = 16.4562 (8) Å	θ = 5.3–56.5°
α = 83.501 (4)°	µ = 0.55 mm^−1
β = 66.004 (5)°	T = 120 K
γ = 61.981 (5)°	Prism, yellow
V = 3175.1 (3) Å^3	0.55 × 0.55 × 0.40 mm

Data collection

Kuma KM4 + CCD diffractometer	9798 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Enhance (Oxford Diffraction) monochromator	θmax = 25.0°, θmin = 3.5°
Detector resolution: 16.3 pixels mm^-1	h = −17→14
rotation method, ω–scan	k = −19→18
16741 measured reflections	l = −19→16
10803 independent reflections

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)] = 0.039	Hydrogen site location: difference Fourier map
wR(F^2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.04P)^2 + 4P] where P = (Fo^2 + 2Fc^2)/3
10803 reflections	(Δ/σ)max = 0.001
901 parameters	Δρmax = 0.87 e Å^−3
26 restraints	Δρmin = −0.73 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.18320 (3)	0.06522 (2)	0.24997 (2)	0.01501 (9)
N1	0.17019 (15)	0.02258 (14)	0.38791 (13)	0.0201 (4)
C2	0.18412 (19)	0.06148 (19)	0.44588 (16)	0.0249 (5)
H2	0.1974	0.1149	0.4303	0.030*
C3	0.1802 (2)	0.0277 (2)	0.52879 (17)	0.0324 (6)
H3	0.1902	0.0580	0.5684	0.039*
C4	0.1619 (2)	−0.0495 (2)	0.55223 (17)	0.0333 (6)
H4	0.1604	−0.0740	0.6079	0.040*
C5	0.14539 (19)	−0.09216 (18)	0.49332 (16)	0.0269 (6)
C6	0.14888 (18)	−0.05261 (17)	0.41172 (16)	0.0203 (5)
C7	0.12875 (18)	−0.09247 (16)	0.35075 (16)	0.0200 (5)
C8	0.10445 (19)	−0.16903 (17)	0.37386 (18)	0.0270 (6)
C9	0.0843 (2)	−0.20464 (18)	0.3125 (2)	0.0326 (6)
H9	0.0673	−0.2561	0.3258	0.039*
C10	0.0894 (2)	−0.16508 (19)	0.2338 (2)	0.0313 (6)
H10	0.0758	−0.1884	0.1919	0.038*
C11	0.1150 (2)	−0.08946 (18)	0.21590 (18)	0.0254 (5)
H11	0.1192	−0.0628	0.1607	0.031*
N12	0.13375 (15)	−0.05321 (14)	0.27208 (13)	0.0198 (4)
C13	0.1227 (2)	−0.1714 (2)	0.51371 (18)	0.0353 (7)
H13	0.1221	−0.1992	0.5680	0.042*
C14	0.1022 (2)	−0.20724 (19)	0.45705 (19)	0.0349 (7)
H14	0.0859	−0.2590	0.4727	0.042*
N15	0.36567 (15)	−0.04088 (13)	0.18322 (13)	0.0178 (4)
C16	0.4342 (2)	−0.08468 (17)	0.22370 (18)	0.0233 (5)
H16	0.4061	−0.0720	0.2866	0.028*
C17	0.5454 (2)	−0.14829 (18)	0.1781 (2)	0.0302 (6)
H17	0.5914	−0.1783	0.2097	0.036*
C18	0.5869 (2)	−0.16671 (17)	0.0880 (2)	0.0299 (6)
H18	0.6625	−0.2098	0.0562	0.036*
C19	0.51780 (19)	−0.12191 (16)	0.04194 (18)	0.0241 (5)
C20	0.40656 (18)	−0.05880 (15)	0.09322 (16)	0.0183 (5)
C21	0.33211 (19)	−0.01171 (15)	0.04966 (15)	0.0178 (5)
C22	0.3712 (2)	−0.03044 (17)	−0.04351 (16)	0.0243 (5)
C23	0.2955 (2)	0.01749 (19)	−0.08317 (17)	0.0289 (6)
H23	0.3184	0.0067	−0.1457	0.035*
C24	0.1888 (2)	0.07971 (18)	−0.03137 (17)	0.0260 (5)
H24	0.1369	0.1126	−0.0573	0.031*
C25	0.1573 (2)	0.09418 (17)	0.06043 (16)	0.0216 (5)
H25	0.0830	0.1377	0.0958	0.026*
N26	0.22579 (16)	0.05029 (13)	0.10076 (13)	0.0177 (4)
C27	0.5550 (2)	−0.13789 (18)	−0.05251 (18)	0.0300 (6)
H27	0.6302	−0.1796	−0.0872	0.036*
C28	0.4851 (2)	−0.09471 (19)	−0.09327 (17)	0.0300 (6)
H28	0.5118	−0.1071	−0.1561	0.036*
O29	0.22594 (14)	0.17202 (11)	0.25822 (11)	0.0214 (3)
O30	0.02314 (13)	0.17738 (11)	0.27078 (11)	0.0203 (3)
Mn2	0.34653 (3)	0.43523 (2)	0.29315 (2)	0.01581 (9)
N40	0.26763 (16)	0.47979 (15)	0.44001 (13)	0.0214 (4)
C41	0.3199 (2)	0.4580 (2)	0.49338 (18)	0.0368 (7)
H41	0.3977	0.4200	0.4685	0.044*
C42	0.2663 (2)	0.4882 (2)	0.58463 (19)	0.0395 (5)
H42	0.3071	0.4697	0.6207	0.047*
C43	0.1562 (3)	0.5438 (3)	0.62124 (18)	0.0437 (8)
H43	0.1192	0.5659	0.6830	0.052*
C44	0.0969 (2)	0.56885 (19)	0.56735 (16)	0.0260 (5)
C45	0.15637 (19)	0.53431 (16)	0.47660 (15)	0.0184 (5)
C46	0.09856 (18)	0.55725 (15)	0.41927 (15)	0.0156 (4)
C47	−0.01711 (18)	0.61422 (16)	0.45524 (16)	0.0207 (5)
C48	−0.0704 (2)	0.63496 (18)	0.39703 (18)	0.0276 (6)
H48	−0.1480	0.6728	0.4186	0.033*
C49	−0.0098 (2)	0.6003 (2)	0.30913 (19)	0.0395 (5)
H49	−0.0444	0.6143	0.2687	0.047*
C50	0.1041 (2)	0.54391 (18)	0.27968 (16)	0.0242 (5)
H50	0.1453	0.5196	0.2185	0.029*
N51	0.15814 (15)	0.52232 (13)	0.33204 (12)	0.0175 (4)
C52	−0.0201 (2)	0.62630 (19)	0.60153 (17)	0.0300 (6)
H52	−0.0600	0.6495	0.6630	0.036*
C53	−0.0743 (2)	0.64789 (18)	0.54822 (17)	0.0283 (6)
H53	−0.1519	0.6862	0.5726	0.034*
N55	0.35629 (15)	0.57270 (13)	0.24967 (13)	0.0193 (4)
C56	0.36060 (19)	0.63276 (18)	0.29592 (18)	0.0260 (5)
H56	0.3547	0.6211	0.3553	0.031*
C57	0.3733 (2)	0.71228 (19)	0.2613 (2)	0.0332 (6)
H57	0.3804	0.7514	0.2952	0.040*
C58	0.3754 (2)	0.73271 (18)	0.1782 (2)	0.0334 (6)
H58	0.3824	0.7873	0.1541	0.040*
C59	0.36728 (19)	0.67312 (17)	0.12770 (18)	0.0258 (5)
C60	0.36158 (17)	0.59181 (16)	0.16553 (16)	0.0189 (5)
C61	0.36112 (17)	0.52457 (16)	0.11454 (15)	0.0189 (5)
C62	0.35871 (18)	0.54472 (18)	0.02987 (16)	0.0233 (5)
C63	0.3566 (2)	0.4774 (2)	−0.01679 (17)	0.0290 (6)
H63	0.3541	0.4884	−0.0739	0.035*
C64	0.35826 (19)	0.39638 (19)	0.02076 (17)	0.0272 (6)
H64	0.3575	0.3503	−0.0103	0.033*
C65	0.36113 (19)	0.38165 (17)	0.10521 (16)	0.0220 (5)
H65	0.3620	0.3250	0.1306	0.026*
N66	0.36277 (15)	0.44346 (13)	0.15136 (12)	0.0166 (4)
C67	0.3653 (2)	0.69149 (19)	0.04129 (19)	0.0334 (6)
H67	0.3680	0.7471	0.0160	0.040*
C68	0.3596 (2)	0.6309 (2)	−0.00502 (18)	0.0316 (6)
H68	0.3562	0.6456	−0.0616	0.038*
O70	0.35115 (13)	0.30005 (11)	0.29756 (11)	0.0220 (4)
C71	0.38647 (18)	0.22302 (16)	0.33183 (15)	0.0178 (5)
O72	0.36138 (14)	0.15854 (12)	0.33165 (12)	0.0251 (4)
C73	0.46707 (19)	0.20517 (18)	0.37318 (16)	0.0230 (5)
H73A	0.4545	0.1680	0.4252	0.028*
H73B	0.4548	0.2667	0.3945	0.028*
S74	0.60761 (5)	0.14039 (5)	0.29155 (5)	0.03045 (16)
C75	0.6150 (2)	0.2293 (2)	0.2141 (2)	0.0393 (7)
H75A	0.6868	0.2012	0.1620	0.047*
H75B	0.5561	0.2502	0.1922	0.047*
C76	0.6021 (2)	0.3144 (2)	0.2593 (2)	0.0381 (7)
O77	0.50852 (13)	0.38588 (13)	0.28891 (13)	0.0304 (4)
O78A	0.6803 (2)	0.3125 (2)	0.2784 (3)	0.0291 (8)	0.713 (6)
O78B	0.6954 (6)	0.2992 (6)	0.2300 (7)	0.0291 (8)	0.287 (6)
O80	0.17557 (14)	0.31646 (13)	0.16440 (12)	0.0289 (4)
C81	0.08885 (18)	0.35378 (16)	0.15197 (14)	0.0170 (5)
O82	0.01625 (13)	0.32668 (12)	0.18017 (11)	0.0219 (4)
C83	0.06868 (18)	0.43952 (16)	0.09804 (15)	0.0175 (5)
H83A	0.0883	0.4826	0.1174	0.021*
H83B	−0.0105	0.4750	0.1097	0.021*
S84	0.14900 (4)	0.40401 (4)	−0.02055 (4)	0.01696 (12)
C85	0.08272 (19)	0.34245 (16)	−0.03763 (15)	0.0181 (5)
H85A	0.0934	0.2872	−0.0018	0.022*
H85B	0.0027	0.3857	−0.0165	0.022*
C86	0.12851 (19)	0.30810 (16)	−0.13558 (15)	0.0196 (5)
O87	0.20858 (14)	0.31790 (13)	−0.19055 (11)	0.0279 (4)
O88	0.07963 (14)	0.27115 (12)	−0.15291 (11)	0.0262 (4)
O101	0.87448 (14)	0.14787 (13)	0.24969 (13)	0.0284 (4)
O102	0.08984 (16)	−0.01325 (14)	−0.13450 (12)	0.0303 (4)
O103	0.12401 (16)	−0.10756 (14)	0.01562 (13)	0.0330 (4)
O105	0.31300 (16)	0.25430 (14)	−0.37118 (13)	0.0328 (4)
O106	0.43171 (15)	0.00191 (14)	0.42144 (13)	0.0332 (4)
O107	−0.16938 (15)	0.37612 (13)	0.14618 (13)	0.0311 (4)
O108	0.5360 (2)	0.5246 (2)	0.36989 (17)	0.0584 (7)
O109	−0.10189 (19)	0.26808 (18)	−0.01633 (16)	0.0493 (6)
O110	0.32419 (17)	0.43080 (15)	−0.21972 (13)	0.0369 (5)
O111	0.17038 (17)	0.09741 (15)	−0.24180 (14)	0.0409 (5)
O112	0.35282 (16)	0.07258 (15)	0.59800 (13)	0.0355 (4)
O113	0.4634 (2)	−0.1918 (2)	0.41123 (18)	0.0636 (7)
O99A	0.3960 (3)	0.6770 (2)	0.5175 (2)	0.0405 (8)*	0.60
O99B	0.3896 (8)	0.6079 (7)	0.5068 (7)	0.039 (2)*	0.20
O99C	0.3811 (7)	0.7609 (6)	0.5542 (6)	0.029 (2)*	0.20
H29V	0.272 (2)	0.174 (2)	0.279 (2)	0.054 (5)*
H29W	0.207 (3)	0.2233 (19)	0.226 (2)	0.054 (5)*
H30W	−0.030 (2)	0.168 (2)	0.263 (2)	0.054 (5)*
H30V	0.024 (3)	0.2296 (19)	0.240 (2)	0.054 (5)*
H01V	0.810 (2)	0.2018 (19)	0.253 (3)	0.065 (2)*
H01W	0.892 (3)	0.104 (2)	0.206 (2)	0.065 (2)*
H02V	0.120 (3)	0.024 (2)	−0.171 (2)	0.065 (2)*
H02W	0.0187 (19)	0.029 (2)	−0.093 (2)	0.065 (2)*
H03W	0.123 (3)	−0.079 (3)	−0.0370 (18)	0.065 (2)*
H03V	0.127 (3)	−0.1653 (17)	0.011 (3)	0.065 (2)*
H5V	0.3833 (19)	0.245 (3)	−0.386 (3)	0.065 (2)*
H5W	0.268 (3)	0.276 (3)	−0.3127 (14)	0.065 (2)*
H6V	0.5072 (16)	−0.027 (3)	0.398 (2)	0.065 (2)*
H6W	0.413 (3)	0.049 (2)	0.384 (2)	0.065 (2)*
H7V	−0.110 (2)	0.361 (3)	0.159 (3)	0.065 (2)*
H7W	−0.206 (3)	0.349 (3)	0.189 (2)	0.065 (2)*
H8V	0.577 (3)	0.4674 (18)	0.340 (3)	0.065 (2)*
H9V	−0.040 (2)	0.267 (3)	−0.062 (2)	0.065 (2)*
H9W	−0.131 (3)	0.310 (2)	0.0331 (19)	0.065 (2)*
H10V	0.294 (3)	0.390 (2)	−0.207 (3)	0.065 (2)*
H10W	0.265 (2)	0.4903 (17)	−0.192 (2)	0.065 (2)*
H11V	0.146 (3)	0.1606 (15)	−0.225 (2)	0.065 (2)*
H11W	0.233 (2)	0.082 (3)	−0.2949 (17)	0.065 (2)*
H12W	0.334 (3)	0.1372 (15)	0.599 (3)	0.065 (2)*
H12V	0.375 (3)	0.050 (3)	0.5398 (15)	0.065 (2)*
H13W	0.439 (3)	−0.1307 (15)	0.422 (3)	0.065 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01477 (17)	0.01444 (17)	0.01604 (17)	−0.00634 (14)	−0.00725 (14)	0.00249 (13)
N1	0.0144 (9)	0.0226 (10)	0.0213 (10)	−0.0072 (8)	−0.0075 (8)	0.0040 (8)
C2	0.0187 (12)	0.0332 (14)	0.0218 (12)	−0.0099 (11)	−0.0088 (10)	−0.0014 (10)
C3	0.0215 (13)	0.0494 (17)	0.0219 (13)	−0.0124 (12)	−0.0087 (11)	−0.0009 (12)
C4	0.0199 (13)	0.0466 (17)	0.0179 (12)	−0.0071 (12)	−0.0053 (10)	0.0088 (12)
C5	0.0141 (11)	0.0303 (13)	0.0204 (12)	−0.0032 (10)	−0.0022 (10)	0.0065 (10)
C6	0.0099 (10)	0.0205 (12)	0.0213 (12)	−0.0029 (9)	−0.0037 (9)	0.0038 (9)
C7	0.0117 (10)	0.0172 (11)	0.0245 (12)	−0.0041 (9)	−0.0050 (9)	0.0042 (9)
C8	0.0164 (12)	0.0198 (12)	0.0335 (14)	−0.0067 (10)	−0.0028 (11)	0.0057 (10)
C9	0.0243 (13)	0.0206 (13)	0.0501 (17)	−0.0136 (11)	−0.0090 (12)	0.0042 (12)
C10	0.0280 (14)	0.0272 (14)	0.0467 (17)	−0.0166 (11)	−0.0176 (13)	0.0023 (12)
C11	0.0239 (13)	0.0247 (13)	0.0335 (14)	−0.0122 (11)	−0.0163 (11)	0.0053 (11)
N12	0.0162 (9)	0.0186 (10)	0.0250 (10)	−0.0075 (8)	−0.0100 (8)	0.0044 (8)
C13	0.0272 (14)	0.0335 (15)	0.0251 (14)	−0.0078 (12)	−0.0028 (11)	0.0142 (12)
C14	0.0268 (14)	0.0245 (14)	0.0372 (16)	−0.0110 (11)	−0.0015 (12)	0.0114 (12)
N15	0.0178 (10)	0.0133 (9)	0.0239 (10)	−0.0078 (8)	−0.0095 (8)	0.0033 (8)
C16	0.0224 (12)	0.0197 (12)	0.0331 (14)	−0.0106 (10)	−0.0161 (11)	0.0069 (10)
C17	0.0224 (13)	0.0206 (12)	0.0516 (17)	−0.0088 (10)	−0.0209 (13)	0.0067 (12)
C18	0.0149 (12)	0.0143 (11)	0.0533 (18)	−0.0052 (10)	−0.0079 (12)	−0.0017 (11)
C19	0.0184 (12)	0.0138 (11)	0.0365 (14)	−0.0095 (10)	−0.0041 (11)	−0.0032 (10)
C20	0.0180 (11)	0.0114 (10)	0.0252 (12)	−0.0096 (9)	−0.0046 (10)	0.0002 (9)
C21	0.0210 (11)	0.0129 (10)	0.0201 (11)	−0.0111 (9)	−0.0046 (10)	−0.0001 (9)
C22	0.0331 (14)	0.0217 (12)	0.0220 (12)	−0.0196 (11)	−0.0058 (11)	−0.0002 (10)
C23	0.0471 (16)	0.0323 (14)	0.0188 (12)	−0.0272 (13)	−0.0137 (12)	0.0038 (10)
C24	0.0393 (15)	0.0261 (13)	0.0251 (13)	−0.0201 (12)	−0.0197 (12)	0.0069 (10)
C25	0.0261 (12)	0.0190 (11)	0.0247 (12)	−0.0117 (10)	−0.0142 (11)	0.0054 (10)
N26	0.0212 (10)	0.0154 (9)	0.0192 (10)	−0.0103 (8)	−0.0088 (8)	0.0034 (8)
C27	0.0225 (13)	0.0215 (13)	0.0345 (14)	−0.0131 (11)	0.0055 (11)	−0.0096 (11)
C28	0.0341 (14)	0.0293 (14)	0.0232 (13)	−0.0216 (12)	0.0026 (11)	−0.0087 (11)
O29	0.0258 (9)	0.0174 (8)	0.0290 (9)	−0.0111 (7)	−0.0178 (8)	0.0054 (7)
O30	0.0170 (8)	0.0195 (8)	0.0237 (9)	−0.0077 (7)	−0.0092 (7)	0.0049 (7)
Mn2	0.01208 (17)	0.01758 (18)	0.01646 (17)	−0.00637 (14)	−0.00530 (14)	0.00197 (13)
N40	0.0182 (10)	0.0328 (11)	0.0189 (10)	−0.0153 (9)	−0.0087 (8)	0.0030 (8)
C41	0.0265 (14)	0.068 (2)	0.0253 (14)	−0.0261 (14)	−0.0153 (12)	0.0071 (13)
C42	0.0314 (11)	0.0687 (15)	0.0294 (10)	−0.0267 (11)	−0.0192 (9)	0.0093 (10)
C43	0.0456 (18)	0.082 (2)	0.0182 (13)	−0.0419 (18)	−0.0093 (13)	−0.0049 (14)
C44	0.0320 (14)	0.0333 (14)	0.0187 (12)	−0.0230 (12)	−0.0053 (11)	−0.0016 (10)
C45	0.0193 (11)	0.0210 (12)	0.0176 (11)	−0.0124 (10)	−0.0060 (9)	0.0000 (9)
C46	0.0157 (11)	0.0132 (10)	0.0184 (11)	−0.0084 (9)	−0.0056 (9)	0.0017 (9)
C47	0.0153 (11)	0.0145 (11)	0.0274 (13)	−0.0067 (9)	−0.0049 (10)	0.0032 (9)
C48	0.0139 (11)	0.0264 (13)	0.0363 (14)	−0.0069 (10)	−0.0089 (11)	0.0091 (11)
C49	0.0314 (11)	0.0687 (15)	0.0294 (10)	−0.0267 (11)	−0.0192 (9)	0.0093 (10)
C50	0.0215 (12)	0.0336 (14)	0.0201 (12)	−0.0131 (11)	−0.0113 (10)	0.0063 (10)
N51	0.0153 (9)	0.0198 (10)	0.0166 (9)	−0.0085 (8)	−0.0057 (8)	0.0023 (8)
C52	0.0313 (14)	0.0292 (14)	0.0205 (12)	−0.0162 (12)	0.0027 (11)	−0.0080 (11)
C53	0.0202 (12)	0.0217 (12)	0.0295 (14)	−0.0085 (10)	0.0022 (11)	−0.0033 (10)
N55	0.0139 (9)	0.0184 (10)	0.0251 (10)	−0.0074 (8)	−0.0068 (8)	−0.0009 (8)
C56	0.0177 (12)	0.0247 (13)	0.0351 (14)	−0.0093 (10)	−0.0084 (11)	−0.0064 (11)
C57	0.0222 (13)	0.0247 (13)	0.0490 (17)	−0.0118 (11)	−0.0063 (12)	−0.0106 (12)
C58	0.0236 (13)	0.0187 (12)	0.0511 (18)	−0.0136 (11)	−0.0037 (12)	0.0001 (12)
C59	0.0154 (11)	0.0177 (12)	0.0347 (14)	−0.0067 (10)	−0.0032 (10)	0.0045 (10)
C60	0.0095 (10)	0.0171 (11)	0.0256 (12)	−0.0055 (9)	−0.0037 (9)	0.0014 (9)
C61	0.0106 (10)	0.0205 (12)	0.0204 (12)	−0.0061 (9)	−0.0033 (9)	0.0031 (9)
C62	0.0132 (11)	0.0298 (13)	0.0214 (12)	−0.0073 (10)	−0.0061 (10)	0.0062 (10)
C63	0.0182 (12)	0.0448 (16)	0.0209 (12)	−0.0113 (11)	−0.0090 (10)	0.0026 (11)
C64	0.0179 (12)	0.0368 (15)	0.0276 (13)	−0.0120 (11)	−0.0082 (11)	−0.0065 (11)
C65	0.0175 (11)	0.0228 (12)	0.0253 (12)	−0.0104 (10)	−0.0056 (10)	−0.0033 (10)
N66	0.0129 (9)	0.0166 (9)	0.0180 (9)	−0.0072 (8)	−0.0035 (8)	0.0008 (8)
C67	0.0238 (13)	0.0261 (14)	0.0409 (16)	−0.0120 (11)	−0.0076 (12)	0.0165 (12)
C68	0.0243 (13)	0.0365 (15)	0.0285 (14)	−0.0126 (12)	−0.0109 (11)	0.0166 (12)
O70	0.0210 (8)	0.0195 (8)	0.0265 (9)	−0.0086 (7)	−0.0125 (7)	0.0066 (7)
C71	0.0155 (11)	0.0197 (12)	0.0157 (11)	−0.0074 (9)	−0.0047 (9)	0.0013 (9)
O72	0.0283 (9)	0.0233 (9)	0.0359 (10)	−0.0154 (8)	−0.0222 (8)	0.0114 (7)
C73	0.0213 (12)	0.0262 (13)	0.0264 (13)	−0.0140 (10)	−0.0123 (10)	0.0088 (10)
S74	0.0180 (3)	0.0213 (3)	0.0480 (4)	−0.0062 (2)	−0.0145 (3)	0.0087 (3)
C75	0.0156 (12)	0.0365 (16)	0.0387 (16)	−0.0036 (11)	0.0015 (12)	0.0112 (13)
C76	0.0158 (13)	0.0325 (15)	0.062 (2)	−0.0146 (12)	−0.0140 (13)	0.0289 (14)
O77	0.0154 (9)	0.0298 (10)	0.0467 (11)	−0.0116 (8)	−0.0142 (8)	0.0130 (8)
O78A	0.0155 (12)	0.0289 (13)	0.047 (2)	−0.0127 (10)	−0.0151 (16)	0.0094 (16)
O78B	0.0155 (12)	0.0289 (13)	0.047 (2)	−0.0127 (10)	−0.0151 (16)	0.0094 (16)
O80	0.0246 (9)	0.0350 (10)	0.0359 (10)	−0.0169 (8)	−0.0205 (8)	0.0201 (8)
C81	0.0173 (11)	0.0177 (11)	0.0134 (10)	−0.0059 (9)	−0.0062 (9)	0.0004 (9)
O82	0.0215 (8)	0.0232 (9)	0.0254 (9)	−0.0129 (7)	−0.0118 (7)	0.0071 (7)
C83	0.0196 (11)	0.0163 (11)	0.0175 (11)	−0.0077 (9)	−0.0092 (9)	0.0019 (9)
S84	0.0172 (3)	0.0196 (3)	0.0161 (3)	−0.0090 (2)	−0.0083 (2)	0.0031 (2)
C85	0.0208 (11)	0.0158 (11)	0.0200 (11)	−0.0086 (9)	−0.0105 (10)	0.0025 (9)
C86	0.0214 (12)	0.0149 (11)	0.0200 (12)	−0.0048 (9)	−0.0105 (10)	0.0023 (9)
O87	0.0293 (10)	0.0333 (10)	0.0208 (9)	−0.0173 (8)	−0.0050 (8)	−0.0035 (7)
O88	0.0324 (10)	0.0294 (9)	0.0239 (9)	−0.0175 (8)	−0.0135 (8)	0.0003 (7)
O101	0.0209 (9)	0.0261 (9)	0.0410 (11)	−0.0084 (8)	−0.0176 (8)	0.0022 (8)
O102	0.0334 (10)	0.0332 (10)	0.0283 (10)	−0.0184 (9)	−0.0130 (8)	0.0046 (8)
O103	0.0400 (11)	0.0341 (11)	0.0305 (10)	−0.0195 (9)	−0.0169 (9)	0.0051 (8)
O105	0.0298 (10)	0.0356 (11)	0.0266 (10)	−0.0126 (9)	−0.0067 (8)	−0.0049 (8)
O106	0.0264 (10)	0.0321 (10)	0.0318 (10)	−0.0078 (8)	−0.0124 (8)	0.0116 (8)
O107	0.0256 (10)	0.0326 (10)	0.0433 (11)	−0.0181 (8)	−0.0175 (9)	0.0098 (9)
O108	0.0597 (16)	0.096 (2)	0.0593 (16)	−0.0590 (16)	−0.0396 (14)	0.0347 (15)
O109	0.0467 (13)	0.0609 (15)	0.0507 (14)	−0.0412 (12)	−0.0063 (11)	−0.0088 (11)
O110	0.0402 (11)	0.0373 (11)	0.0333 (11)	−0.0245 (10)	−0.0067 (9)	0.0015 (9)
O111	0.0394 (12)	0.0326 (11)	0.0379 (11)	−0.0219 (10)	0.0046 (9)	−0.0067 (9)
O112	0.0283 (10)	0.0387 (11)	0.0294 (10)	−0.0123 (9)	−0.0070 (8)	0.0045 (9)
O113	0.0419 (14)	0.0799 (19)	0.0577 (15)	−0.0230 (14)	−0.0092 (12)	−0.0215 (15)

Geometric parameters (Å, º)

Mn1—O29	2.1214 (17)	C49—C50	1.397 (4)
Mn1—O30	2.1302 (16)	C49—H49	0.9500
Mn1—N1	2.2517 (19)	C50—N51	1.327 (3)
Mn1—N26	2.2817 (19)	C50—H50	0.9500
Mn1—N15	2.2823 (19)	C52—C53	1.342 (4)
Mn1—N12	2.284 (2)	C52—H52	0.9500
N1—C2	1.326 (3)	C53—H53	0.9500
N1—C6	1.362 (3)	N55—C56	1.330 (3)
C2—C3	1.398 (4)	N55—C60	1.362 (3)
C2—H2	0.9500	C56—C57	1.398 (4)
C3—C4	1.369 (4)	C56—H56	0.9500
C3—H3	0.9500	C57—C58	1.361 (4)
C4—C5	1.404 (4)	C57—H57	0.9500
C4—H4	0.9500	C58—C59	1.408 (4)
C5—C6	1.410 (3)	C58—H58	0.9500
C5—C13	1.433 (4)	C59—C60	1.401 (3)
C6—C7	1.441 (3)	C59—C67	1.429 (4)
C7—N12	1.363 (3)	C60—C61	1.441 (3)
C7—C8	1.406 (3)	C61—N66	1.361 (3)
C8—C9	1.405 (4)	C61—C62	1.405 (3)
C8—C14	1.429 (4)	C62—C63	1.409 (4)
C9—C10	1.365 (4)	C62—C68	1.436 (4)
C9—H9	0.9500	C63—C64	1.365 (4)
C10—C11	1.401 (4)	C63—H63	0.9500
C10—H10	0.9500	C64—C65	1.398 (4)
C11—N12	1.325 (3)	C64—H64	0.9500
C11—H11	0.9500	C65—N66	1.327 (3)
C13—C14	1.346 (4)	C65—H65	0.9500
C13—H13	0.9500	C67—C68	1.350 (4)
C14—H14	0.9500	C67—H67	0.9500
N15—C16	1.331 (3)	C68—H68	0.9500
N15—C20	1.358 (3)	O70—C71	1.260 (3)
C16—C17	1.395 (4)	C71—O72	1.254 (3)
C16—H16	0.9500	C71—C73	1.521 (3)
C17—C18	1.359 (4)	C73—S74	1.814 (2)
C17—H17	0.9500	C73—H73A	0.9900
C18—C19	1.410 (4)	C73—H73B	0.9900
C18—H18	0.9500	S74—C75	1.811 (3)
C19—C20	1.409 (3)	C75—C76	1.520 (5)
C19—C27	1.429 (4)	C75—H75A	0.9900
C20—C21	1.439 (3)	C75—H75B	0.9900
C21—N26	1.361 (3)	C76—O78B	1.189 (8)
C21—C22	1.411 (3)	C76—O77	1.257 (3)
C22—C23	1.407 (4)	C76—O78A	1.320 (4)
C22—C28	1.434 (4)	O78A—O78B	0.759 (8)
C23—C24	1.368 (4)	O80—C81	1.247 (3)
C23—H23	0.9500	C81—O82	1.257 (3)
C24—C25	1.398 (3)	C81—C83	1.520 (3)
C24—H24	0.9500	C83—S84	1.811 (2)
C25—N26	1.329 (3)	C83—H83A	0.9900
C25—H25	0.9500	C83—H83B	0.9900
C27—C28	1.348 (4)	S84—C85	1.803 (2)
C27—H27	0.9500	C85—C86	1.522 (3)
C28—H28	0.9500	C85—H85A	0.9900
O29—H29V	0.90 (4)	C85—H85B	0.9900
O29—H29W	0.921 (18)	C86—O87	1.245 (3)
O30—H30W	0.94 (4)	C86—O88	1.260 (3)
O30—H30V	0.931 (18)	O101—H01V	0.931 (19)
Mn2—O70	2.1232 (16)	O101—H01W	0.927 (19)
Mn2—O77	2.1512 (17)	O102—H02V	0.93 (4)
Mn2—N66	2.2403 (19)	O102—H02W	0.946 (19)
Mn2—N40	2.240 (2)	O103—H03W	0.934 (19)
Mn2—N55	2.286 (2)	O103—H03V	0.90 (4)
Mn2—N51	2.3222 (19)	O105—H5V	0.92 (4)
N40—C41	1.321 (3)	O105—H5W	0.911 (19)
N40—C45	1.360 (3)	O106—H6V	0.92 (4)
C41—C42	1.397 (4)	O106—H6W	0.929 (19)
C41—H41	0.9500	O107—H7V	0.92 (4)
C42—C43	1.349 (4)	O107—H7W	0.91 (4)
C42—H42	0.9500	O108—H8V	0.885 (19)
C43—C44	1.403 (4)	O109—H9V	0.92 (4)
C43—H43	0.9500	O109—H9W	0.932 (19)
C44—C45	1.404 (3)	O110—H10V	0.92 (4)
C44—C52	1.431 (4)	O110—H10W	0.936 (19)
C45—C46	1.439 (3)	O111—H11V	0.930 (19)
C46—N51	1.357 (3)	O111—H11W	0.934 (19)
C46—C47	1.414 (3)	O112—H12W	0.936 (19)
C47—C48	1.404 (4)	O112—H12V	0.932 (19)
C47—C53	1.432 (4)	O113—H13W	0.879 (19)
C48—C49	1.366 (4)	O99A—O99B	1.190 (11)
C48—H48	0.9500	O99A—O99C	1.417 (10)
O29—Mn1—O30	87.17 (6)	C42—C43—H43	120.3
O29—Mn1—N1	94.00 (7)	C44—C43—H43	120.3
O30—Mn1—N1	104.28 (7)	C43—C44—C45	117.6 (2)
O29—Mn1—N26	101.59 (7)	C43—C44—C52	122.7 (2)
O30—Mn1—N26	90.19 (7)	C45—C44—C52	119.7 (2)
N1—Mn1—N26	159.27 (7)	N40—C45—C44	122.5 (2)
O29—Mn1—N15	89.62 (7)	N40—C45—C46	118.1 (2)
O30—Mn1—N15	161.96 (7)	C44—C45—C46	119.4 (2)
N1—Mn1—N15	93.65 (7)	N51—C46—C47	122.5 (2)
N26—Mn1—N15	73.07 (7)	N51—C46—C45	118.03 (19)
O29—Mn1—N12	167.67 (7)	C47—C46—C45	119.5 (2)
O30—Mn1—N12	95.03 (7)	C48—C47—C46	117.7 (2)
N1—Mn1—N12	73.69 (7)	C48—C47—C53	123.2 (2)
N26—Mn1—N12	90.55 (7)	C46—C47—C53	119.2 (2)
N15—Mn1—N12	91.89 (7)	C49—C48—C47	119.5 (2)
C2—N1—C6	117.9 (2)	C49—C48—H48	120.2
C2—N1—Mn1	126.59 (17)	C47—C48—H48	120.2
C6—N1—Mn1	115.47 (15)	C48—C49—C50	118.8 (2)
N1—C2—C3	123.2 (3)	C48—C49—H49	120.6
N1—C2—H2	118.4	C50—C49—H49	120.6
C3—C2—H2	118.4	N51—C50—C49	123.9 (2)
C4—C3—C2	119.3 (3)	N51—C50—H50	118.1
C4—C3—H3	120.4	C49—C50—H50	118.1
C2—C3—H3	120.4	C50—N51—C46	117.59 (19)
C3—C4—C5	119.4 (2)	C50—N51—Mn2	128.30 (16)
C3—C4—H4	120.3	C46—N51—Mn2	114.06 (14)
C5—C4—H4	120.3	C53—C52—C44	121.1 (2)
C4—C5—C6	117.6 (2)	C53—C52—H52	119.5
C4—C5—C13	123.0 (2)	C44—C52—H52	119.5
C6—C5—C13	119.4 (2)	C52—C53—C47	121.2 (2)
N1—C6—C5	122.6 (2)	C52—C53—H53	119.4
N1—C6—C7	118.2 (2)	C47—C53—H53	119.4
C5—C6—C7	119.2 (2)	C56—N55—C60	117.9 (2)
N12—C7—C8	122.5 (2)	C56—N55—Mn2	127.39 (17)
N12—C7—C6	117.8 (2)	C60—N55—Mn2	114.72 (15)
C8—C7—C6	119.8 (2)	N55—C56—C57	123.1 (3)
C9—C8—C7	117.5 (2)	N55—C56—H56	118.4
C9—C8—C14	123.2 (2)	C57—C56—H56	118.4
C7—C8—C14	119.2 (3)	C58—C57—C56	118.8 (2)
C10—C9—C8	119.8 (2)	C58—C57—H57	120.6
C10—C9—H9	120.1	C56—C57—H57	120.6
C8—C9—H9	120.1	C57—C58—C59	120.1 (2)
C9—C10—C11	118.9 (3)	C57—C58—H58	119.9
C9—C10—H10	120.6	C59—C58—H58	119.9
C11—C10—H10	120.6	C60—C59—C58	117.1 (2)
N12—C11—C10	123.3 (2)	C60—C59—C67	119.5 (2)
N12—C11—H11	118.3	C58—C59—C67	123.4 (2)
C10—C11—H11	118.3	N55—C60—C59	122.8 (2)
C11—N12—C7	118.0 (2)	N55—C60—C61	117.6 (2)
C11—N12—Mn1	127.32 (16)	C59—C60—C61	119.6 (2)
C7—N12—Mn1	114.60 (15)	N66—C61—C62	122.7 (2)
C14—C13—C5	121.0 (2)	N66—C61—C60	117.9 (2)
C14—C13—H13	119.5	C62—C61—C60	119.5 (2)
C5—C13—H13	119.5	C61—C62—C63	117.3 (2)
C13—C14—C8	121.4 (3)	C61—C62—C68	119.2 (2)
C13—C14—H14	119.3	C63—C62—C68	123.5 (2)
C8—C14—H14	119.3	C64—C63—C62	119.5 (2)
C16—N15—C20	118.1 (2)	C64—C63—H63	120.3
C16—N15—Mn1	126.39 (16)	C62—C63—H63	120.3
C20—N15—Mn1	115.48 (14)	C63—C64—C65	119.5 (2)
N15—C16—C17	123.1 (2)	C63—C64—H64	120.2
N15—C16—H16	118.4	C65—C64—H64	120.2
C17—C16—H16	118.4	N66—C65—C64	122.7 (2)
C18—C17—C16	119.1 (2)	N66—C65—H65	118.6
C18—C17—H17	120.4	C64—C65—H65	118.6
C16—C17—H17	120.4	C65—N66—C61	118.2 (2)
C17—C18—C19	120.0 (2)	C65—N66—Mn2	125.31 (16)
C17—C18—H18	120.0	C61—N66—Mn2	116.01 (15)
C19—C18—H18	120.0	C68—C67—C59	121.0 (2)
C20—C19—C18	117.1 (2)	C68—C67—H67	119.5
C20—C19—C27	119.5 (2)	C59—C67—H67	119.5
C18—C19—C27	123.4 (2)	C67—C68—C62	121.0 (2)
N15—C20—C19	122.5 (2)	C67—C68—H68	119.5
N15—C20—C21	118.0 (2)	C62—C68—H68	119.5
C19—C20—C21	119.5 (2)	C71—O70—Mn2	139.78 (15)
N26—C21—C22	122.4 (2)	O72—C71—O70	123.7 (2)
N26—C21—C20	118.0 (2)	O72—C71—C73	117.7 (2)
C22—C21—C20	119.5 (2)	O70—C71—C73	118.6 (2)
C23—C22—C21	117.5 (2)	C71—C73—S74	110.25 (17)
C23—C22—C28	123.3 (2)	C71—C73—H73A	109.6
C21—C22—C28	119.2 (2)	S74—C73—H73A	109.6
C24—C23—C22	119.7 (2)	C71—C73—H73B	109.6
C24—C23—H23	120.1	S74—C73—H73B	109.6
C22—C23—H23	120.1	H73A—C73—H73B	108.1
C23—C24—C25	118.9 (2)	C75—S74—C73	100.71 (12)
C23—C24—H24	120.5	C76—C75—S74	110.5 (2)
C25—C24—H24	120.5	C76—C75—H75A	109.6
N26—C25—C24	123.4 (2)	S74—C75—H75A	109.6
N26—C25—H25	118.3	C76—C75—H75B	109.6
C24—C25—H25	118.3	S74—C75—H75B	109.6
C25—N26—C21	118.0 (2)	H75A—C75—H75B	108.1
C25—N26—Mn1	126.60 (16)	O78B—C76—O77	137.1 (5)
C21—N26—Mn1	115.38 (14)	O77—C76—O78A	118.6 (3)
C28—C27—C19	121.1 (2)	O78B—C76—C75	100.3 (5)
C28—C27—H27	119.4	O77—C76—C75	117.9 (2)
C19—C27—H27	119.4	O78A—C76—C75	123.0 (3)
C27—C28—C22	121.2 (2)	C76—O77—Mn2	139.8 (2)
C27—C28—H28	119.4	O78B—O78A—C76	63.1 (7)
C22—C28—H28	119.4	O78A—O78B—C76	82.2 (8)
Mn1—O29—H29V	133 (2)	O80—C81—O82	125.7 (2)
Mn1—O29—H29W	118 (2)	O80—C81—C83	117.5 (2)
H29V—O29—H29W	108 (3)	O82—C81—C83	116.85 (19)
Mn1—O30—H30W	123 (2)	C81—C83—S84	111.41 (15)
Mn1—O30—H30V	113 (2)	C81—C83—H83A	109.3
H30W—O30—H30V	105 (3)	S84—C83—H83A	109.3
O70—Mn2—O77	96.90 (7)	C81—C83—H83B	109.3
O70—Mn2—N66	92.01 (7)	S84—C83—H83B	109.3
O77—Mn2—N66	106.85 (7)	H83A—C83—H83B	108.0
O70—Mn2—N40	99.33 (7)	C85—S84—C83	98.80 (11)
O77—Mn2—N40	91.89 (7)	C86—C85—S84	111.76 (16)
N66—Mn2—N40	156.80 (7)	C86—C85—H85A	109.3
O70—Mn2—N55	165.15 (7)	S84—C85—H85A	109.3
O77—Mn2—N55	84.55 (7)	C86—C85—H85B	109.3
N66—Mn2—N55	73.50 (7)	S84—C85—H85B	109.3
N40—Mn2—N55	95.38 (7)	H85A—C85—H85B	107.9
O70—Mn2—N51	95.22 (6)	O87—C86—O88	126.0 (2)
O77—Mn2—N51	162.05 (7)	O87—C86—C85	119.2 (2)
N66—Mn2—N51	85.85 (7)	O88—C86—C85	114.8 (2)
N40—Mn2—N51	73.08 (7)	H01V—O101—H01W	108 (3)
N55—Mn2—N51	87.12 (7)	H02V—O102—H02W	108 (3)
C41—N40—C45	117.7 (2)	H03W—O103—H03V	109 (3)
C41—N40—Mn2	125.60 (17)	H5V—O105—H5W	112 (3)
C45—N40—Mn2	116.65 (15)	H6V—O106—H6W	104 (3)
N40—C41—C42	123.1 (3)	H7V—O107—H7W	102 (3)
N40—C41—H41	118.5	H9V—O109—H9W	114 (3)
C42—C41—H41	118.5	H10V—O110—H10W	105 (3)
C43—C42—C41	119.7 (3)	H11V—O111—H11W	105 (3)
C43—C42—H42	120.2	H12W—O112—H12V	109 (3)
C41—C42—H42	120.2	O99B—O99A—O99C	163.9 (7)
C42—C43—C44	119.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O29—H29V···O72	0.90 (4)	1.78 (2)	2.680 (2)	168 (3)
O29—H29W···O80	0.92 (2)	1.69 (2)	2.606 (2)	178 (3)
O30—H30W···O101^i	0.94 (4)	1.71 (4)	2.645 (2)	178 (3)
O30—H30V···O82	0.93 (2)	1.72 (2)	2.649 (2)	174 (3)
O101—H01V···O78A	0.93 (2)	1.84 (2)	2.759 (3)	170 (4)
O101—H01V···O78B	0.93 (2)	1.85 (2)	2.761 (8)	166 (4)
O101—H01W···O102^ii	0.93 (2)	1.82 (4)	2.743 (3)	171 (4)
O102—H02V···O111	0.93 (4)	1.77 (2)	2.698 (3)	177 (4)
O102—H02W···O103^iii	0.95 (2)	1.85 (2)	2.793 (3)	176 (4)
O103—H03W···O102	0.93 (2)	1.93 (2)	2.846 (3)	168 (3)
O103—H03V···O109^iii	0.91 (2)	1.84 (2)	2.736 (3)	168 (4)
O105—H5V···O113^ii	0.92 (4)	1.92 (2)	2.816 (3)	165 (4)
O105—H5W···O87	0.91 (2)	1.89 (2)	2.779 (2)	166 (4)
O106—H6V···O112^iv	0.91 (4)	1.90 (2)	2.763 (3)	155 (4)
O106—H6W···O72	0.93 (2)	1.83 (2)	2.742 (2)	167 (4)
O107—H7V···O82	0.92 (4)	1.88 (4)	2.797 (2)	177 (4)
O107—H7W···O78B^i	0.91 (4)	1.86 (3)	2.690 (8)	150 (3)
O107—H7W···O78A^i	0.91 (4)	2.03 (2)	2.922 (4)	165 (3)
O108—H8V···O78A	0.89 (2)	2.29 (2)	3.173 (5)	174 (4)
O108—H8V···O77	0.89 (2)	2.38 (4)	2.975 (3)	125 (3)
O109—H9V···O88	0.92 (4)	1.84 (2)	2.759 (3)	177 (4)
O109—H9W···O107	0.93 (2)	1.97 (2)	2.891 (3)	168 (4)
O110—H10V···O87	0.92 (4)	2.02 (5)	2.930 (3)	169 (3)
O110—H10V···S84	0.92 (4)	2.91 (4)	3.404 (2)	115 (3)
O110—H10W···O107^v	0.94 (2)	1.95 (2)	2.866 (3)	167 (4)
O111—H11V···O88	0.93 (2)	1.84 (2)	2.730 (3)	160 (4)
O111—H11W···O112^vi	0.93 (2)	1.90 (2)	2.822 (3)	170 (4)
O112—H12W···O105^vii	0.94 (2)	1.83 (2)	2.740 (3)	163 (4)
O112—H12V···O106	0.93 (2)	1.86 (2)	2.794 (3)	175 (4)
O113—H13W···O106	0.88 (2)	2.07 (2)	2.917 (4)	162 (4)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z; (iii) −x, −y, −z; (iv) −x+1, −y, −z+1; (v) −x, −y+1, −z; (vi) x, y, z−1; (vii) x, y, z+1.