A one-dimensional chain structure based on unusual tetra­nuclear manganese(II) clusters

The title coordination polymer, poly[bis([mu]₄-biphenyl-2,2'-dicarboxyl­ato)(dipyrido[3,2-a:2',3'-c]­phen­azine)­manganese(II)], [Mn₂(C₁₄H₈O₄)₂(C₁₈H₁₀N₄)]_n, was obtained through the reaction of MnCl₂·4H₂O, biphenyl-2,2'-dicarboxylic acid (H₂dpdc) and dipyrido[3,2-a:2',3'-c]phenazine (L) under hydro­thermal conditions. The asymmetric unit contains two crystallographically unique Mn^II ions, one unique L ligand and two unique dpdc ligands. One Mn ion is six-coordinated by four O atoms from three different dpdc ligands and two N atoms from one L ligand, adopting a distorted octa­hedral coordination geometry. The distortions from ideal octahedral geometry are largely due to the presence of chelating ligands and the resulting acute N-Mn-N and O-Mn-O angles. The second Mn ion is coordinated in a distorted trigonal bipyramidal fashion by five O atoms from four distinct dpdc ligands. Four Mn^II ions are bridged by the carboxyl­ate groups of the dpdc ligands to form an unusual tetra­nuclear Mn^II cluster. Clusters are further connected by the aromatic backbone of the dicarboxyl­ate ligands, forming a one-dimensional chain structure along the b axis. The title compound is the first example of a chain structure based on a tetra­nuclear Mn^II cluster.

S1. Comment

The metal–organic coordination architectures formed with transition metal ions and organic ligands have been a promising topic for many years owing to their intriguing structures and potential applications in catalysis, separation, gas storage, molecular recognition, magnetic devices and nonlinear optical materials (Eddaoudi et al., 2001; Batten & Robson, 1998; Yang et al., 2008). In this regard, chain structures have received much attention in coordination chemistry and materials chemistry (Lehn, 1990; Li et al., 2002; Chen & Liu, 2002; Yang, Li et al., 2007). An appropriate flexible bidentate organic acid bridge could be useful in the formation of chains in the presence of secondary ligands, such as 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen) (Qi et al., 2003). The N atoms from the secondary ligand may occupy two coordination positions of the metal ions. The rest of the coordination positions are available for other carboxylate ligands to allow the formation of a chain.

The use of aromatic carboxylic acids in the syntheses of chain coordination polymers has aroused enormous interest owing to their versatile coordination modes and varieties of structural conformations (Chen & Liu, 2002; Zhang et al., 2003; Fan et al., 2002). So far, aromatic multicarboxylate ligands, such as 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid and 1,4-benzenedicarboxylic acid, have been widely used to construct chain structures with interesting properties (Chen & Liu, 2002). In this regard, biphenyl-2,2'-dicarboxylic acid (H₂dpdc) is also a good ligand in coordination chemistry because of its strong coordination ability and versatile coordination modes, so much attention has been paid to it in the past decade. On the other hand, the phen molecule, as one type of important organic ligand, has been widely utilized in the construction of chain structure complexes. An important derivative of phen, dipyrido[3,2-a:2',3'-c]-phenazine (L) has been widely used to synthesize various Ru^II complexes in order to recognize the secondary structure of DNA (Wu et al., 1997). However, chain coordination polymers based on the ligand L have rarely been documented. In the present study, we selected H₂dpdc as a linker and L as a secondary chelating ligand, forming a new chain coordination polymer, [Mn₂(L)(dpdc)₂], (I), based on unusual tetranuclear Mn^II clusters.

Selected bond lengths and angles for (I) are given in Table 1. As shown in Fig. 1, the asymmetric unit of (I) contains two crystallographically unique Mn^II atoms, one unique L ligand and two unique dpdc ligands. Atom Mn1 is six-coordinated by four O atoms [O1, O3ⁱ, O7ⁱⁱ and O8ⁱⁱ; symmetry codes: (i) -x, -y + 2, -z + 1; (ii) -x, -y + 1, -z + 1] from three different dpdc ligands and two N atoms (N1 and N2) from one L ligand, adopting a distorted octahedral coordination geometry. Atom Mn2 is coordinated in a square-pyramidal fashion by five O atoms (O2, O6, O4ⁱ, O5ⁱⁱ, O7ⁱⁱ) from four distinct dpdc ligands. The average Mn—O and Mn—N distances in (I) are comparable to those observed for [Mn(bza)₂(ppz)₂] [bza is benzoic acid and ppz is 3-(2-pyridyl)pyrazole; Zou et al., 2005]. Two coordination modes for the dpdc ligands have been found: one is bis-bidentate, and the second is bidentate/monodentate–bidentate. In these modes, an unusual tetranuclear Mn^II cluster is formed, where four Mn^II atoms are bridged by the carboxylate groups of the dpdc ligands to form a discrete rod (Fig. 2). Each cluster lies across an inversion centre, with the Mn2 atoms in the middle and the Mn1 atoms on the ends of the rod. As such, each tetranuclear metal cluster is surrounded by eight organic ligands: six bridging dpdc and two chelating L ligands. To the best of our knowledge, the rod-like tetranuclear Mn^II cluster containing the bpy-like chelating ligand L has not been reported so far, although other noncoplanar tetranuclear Cd^II clusters including bpy-like chelating ligands have been reported (Wang et al., 2007).

In the structure of (I), the tetranuclear Mn^II carboxylate clusters act as rod-shaped secondary building units, which are connected together by the aromatic backbone of the dicarboxylate ligands, forming a one-dimensional chain structure along the b axis (Fig. 3). These chains are decorated with L ligands alternately on two sides. It is noteworthy that the structure of (I) presented here is clearly different from that reported for [Pb(dpdc)(L)] (Yang, Ma et al., 2007). This reported compound features a helical chain structure based on mononuclear lead(II) centers, which are connected by strong π–π interactions to result in a three-dimensional supramolecular architecture.

Over the past decade, chain structures have received much attention in coordination chemistry and materials chemistry because of their importantance in advanced materials such as optical devices, enantiomer separation, chiral synthesis, ligand exchange and selective catalysis (Chen & Liu, 2002). Consequently, many chain complexes have been generated by self-assembly processes. However, the reported chain complexes constructed by dicarboxylate and heteroaromatic N-donor chelating ligands are mainly based on the mononuclear metal centers. To the best of our knowledge, (I), constructed from the dicarboxylate anion and aphen derivative, is the first one-dimensional chain structure based on tetranuclear Mn^II clusters.

Related literature

For related literature, see: Batten & Robson (1998); Chen & Liu (2002); Eddaoudi et al. (2001); Fan et al. (2002); Lehn (1990); Li et al. (2002); Qi et al. (2003); Wang et al. (2007); Wu et al. (1997); Yang et al. (2007a, 2007b, 2008); Zhang et al. (2003); Zou et al. (2005).

S2. Experimental

A mixture of MnCl₂^.4H₂O (0.090 g, 0.5 mmol), H₂dpdc (0.062 g, 0.5 mmol) and L (0.145 g, 0.5 mmol) were dissolved in 14 ml of distilled water, followed by addition of triethylamine until the pH value of the system was adjusted to about 5.5. The resulting solution was stirred for about 1 h at room temperature, sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at 413 K for 3 days under autogenous pressure. The reaction system was then cooled slowly to room temperature. Pale-yellow block crystals of (I) suitable for single-crystal X-ray diffraction analysis were collected from the final reaction system by filtration, washed several times with distilled water and dried in air at ambient temperature (yield 44% based on Mn). The compound once formed is insoluble in most solvents, including water.

S3. Refinement

All H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding, with U_iso(H) = 1.2U_eq(carrier).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the local coordination of the Mn^II atoms in (I), showing the atom-numbering scheme. Displacement ellipsoids are shown at the 30% probability level. [Symmetry operations: (i) -x, -y + 2, -z + 1; (ii) -x, -y + 1, -z + 1.]
	Fig. 2. A view of the tetranuclear Mn^II cluster of (I).
	Fig. 3. A view of the one-dimensional chain structure of (I), based on tetranuclear Mn^II clusters.

poly[(µ₄-biphenyl-2,2'-dicarboxylato)(dipyrido[3,2-a:2',3'- c]phenazine)manganese(II)]

Crystal data

[Mn2(C14H8O4)2(C18H10N4)]	Z = 2
Mr = 872.59	F(000) = 888
Triclinic, P1	Dx = 1.511 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.993 (2) Å	Cell parameters from 12518 reflections
b = 13.516 (3) Å	θ = 3.0–27.5°
c = 14.196 (3) Å	µ = 0.72 mm^−1
α = 62.13 (3)°	T = 293 K
β = 70.55 (2)°	Block, pale yellow
γ = 82.24 (3)°	0.31 × 0.24 × 0.21 mm
V = 1917.6 (9) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	8667 independent reflections
Radiation source: rotating anode	5367 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
Detector resolution: 10.0 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scan	h = −15→15
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −17→17
Tmin = 0.794, Tmax = 0.856	l = −18→17
18726 measured 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0616P)^2] where P = (Fo^2 + 2Fc^2)/3
8667 reflections	(Δ/σ)max < 0.001
541 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.37 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
C1	0.2115 (4)	0.9126 (3)	0.1131 (3)	0.0519 (11)
H1	0.1713	0.8438	0.1545	0.062*
C2	0.3123 (5)	0.9251 (4)	0.0251 (4)	0.0704 (15)
H2	0.3391	0.8657	0.0082	0.084*
C3	0.3725 (4)	1.0262 (3)	−0.0373 (4)	0.0610 (13)
H3	0.4404	1.0362	−0.0972	0.073*
C4	0.3305 (4)	1.1138 (3)	−0.0097 (3)	0.0408 (9)
C5	0.3895 (3)	1.2233 (3)	−0.0724 (3)	0.0360 (8)
C6	0.5425 (4)	1.3394 (3)	−0.2102 (3)	0.0438 (9)
C7	0.6465 (4)	1.3597 (4)	−0.3023 (4)	0.0549 (11)
H7	0.6798	1.3018	−0.3197	0.066*
C8	0.6978 (4)	1.4640 (4)	−0.3652 (4)	0.0586 (12)
H8	0.7656	1.4776	−0.4261	0.070*
C9	0.6482 (4)	1.5509 (4)	−0.3380 (4)	0.0608 (12)
H9	0.6845	1.6216	−0.3816	0.073*
C10	0.5489 (4)	1.5358 (3)	−0.2501 (4)	0.0558 (11)
H10	0.5188	1.5947	−0.2331	0.067*
C11	0.4920 (4)	1.4282 (3)	−0.1848 (3)	0.0418 (9)
C12	0.3380 (3)	1.3124 (3)	−0.0450 (3)	0.0378 (8)
C13	0.2292 (3)	1.2902 (3)	0.0483 (3)	0.0375 (8)
C14	0.1732 (4)	1.3732 (3)	0.0803 (4)	0.0567 (12)
H14	0.2024	1.4466	0.0389	0.068*
C15	0.0755 (5)	1.3446 (3)	0.1730 (4)	0.0700 (15)
H15	0.0389	1.3980	0.1964	0.084*
C16	0.0318 (4)	1.2355 (3)	0.2315 (4)	0.0593 (12)
H16	−0.0344	1.2171	0.2945	0.071*
C17	0.1773 (3)	1.1821 (3)	0.1111 (3)	0.0354 (8)
C18	0.2282 (3)	1.0937 (3)	0.0801 (3)	0.0336 (8)
C19	0.1722 (3)	0.8227 (3)	0.4431 (3)	0.0347 (8)
C20	0.2411 (3)	0.8073 (3)	0.5195 (3)	0.0369 (8)
C21	0.2360 (4)	0.7028 (3)	0.6101 (4)	0.0496 (10)
H21	0.1981	0.6434	0.6162	0.060*
C22	0.2860 (5)	0.6848 (4)	0.6921 (4)	0.0699 (15)
H22	0.2831	0.6141	0.7518	0.084*
C23	0.3401 (5)	0.7745 (4)	0.6825 (5)	0.0761 (16)
H23	0.3712	0.7648	0.7381	0.091*
C24	0.3486 (4)	0.8780 (3)	0.5918 (4)	0.0608 (13)
H24	0.3871	0.9367	0.5863	0.073*
C25	0.3009 (3)	0.8967 (3)	0.5082 (3)	0.0386 (9)
C26	0.3284 (3)	1.0066 (3)	0.4047 (3)	0.0394 (9)
C27	0.4237 (4)	1.0080 (4)	0.3157 (4)	0.0605 (13)
H27	0.4609	0.9414	0.3212	0.073*
C28	0.4643 (5)	1.1057 (4)	0.2194 (4)	0.0704 (15)
H28	0.5283	1.1042	0.1610	0.084*
C29	0.4117 (4)	1.2045 (4)	0.2089 (3)	0.0570 (12)
H29	0.4395	1.2704	0.1437	0.068*
C30	0.3169 (4)	1.2062 (3)	0.2956 (3)	0.0439 (9)
H30	0.2803	1.2735	0.2883	0.053*
C31	0.2751 (3)	1.1080 (3)	0.3946 (3)	0.0347 (8)
C32	0.1700 (3)	1.1174 (3)	0.4848 (3)	0.0348 (8)
C33	−0.0088 (3)	0.4637 (3)	0.6570 (3)	0.0335 (8)
C34	−0.0368 (4)	0.3832 (3)	0.7796 (3)	0.0392 (9)
C35	−0.1456 (4)	0.3886 (3)	0.8525 (3)	0.0511 (11)
H35	−0.1972	0.4449	0.8258	0.061*
C36	−0.1782 (5)	0.3113 (4)	0.9642 (3)	0.0667 (15)
H36	−0.2513	0.3156	1.0124	0.080*
C37	−0.1011 (6)	0.2273 (4)	1.0039 (4)	0.0760 (17)
H37	−0.1234	0.1742	1.0787	0.091*
C38	0.0073 (5)	0.2221 (3)	0.9336 (4)	0.0623 (14)
H38	0.0580	0.1653	0.9613	0.075*
C39	0.0435 (4)	0.3014 (3)	0.8201 (3)	0.0461 (10)
C40	0.1657 (4)	0.2989 (3)	0.7485 (4)	0.0489 (11)
C41	0.2042 (4)	0.2157 (3)	0.7143 (4)	0.0482 (10)
C42	0.3201 (4)	0.2147 (4)	0.6504 (4)	0.0644 (13)
H42	0.3443	0.1567	0.6307	0.077*
C43	0.4002 (5)	0.2987 (5)	0.6154 (5)	0.0793 (16)
H43	0.4777	0.2981	0.5720	0.095*
C44	0.3628 (6)	0.3837 (4)	0.6463 (5)	0.0782 (17)
H44	0.4152	0.4419	0.6215	0.094*
C45	0.2492 (5)	0.3831 (4)	0.7132 (4)	0.0645 (14)
H45	0.2269	0.4394	0.7355	0.077*
C46	0.1165 (4)	0.1338 (3)	0.7329 (3)	0.0415 (9)
N1	0.1692 (3)	0.9938 (2)	0.1415 (2)	0.0371 (7)
N2	0.0801 (3)	1.1554 (2)	0.2020 (2)	0.0403 (7)
N3	0.4899 (3)	1.2368 (3)	−0.1534 (3)	0.0452 (8)
N4	0.3902 (3)	1.4130 (2)	−0.0999 (3)	0.0415 (7)
O1	0.1483 (3)	0.9199 (2)	0.3819 (2)	0.0476 (7)
O2	0.1375 (2)	0.7352 (2)	0.4484 (2)	0.0472 (7)
O3	0.1163 (2)	1.0299 (2)	0.5649 (2)	0.0443 (7)
O4	0.1450 (3)	1.2154 (2)	0.4722 (2)	0.0595 (8)
O5	0.0516 (2)	0.42984 (18)	0.58657 (19)	0.0354 (6)
O6	−0.0497 (3)	0.56015 (18)	0.63170 (19)	0.0442 (7)
O7	0.0259 (2)	0.17585 (18)	0.6986 (2)	0.0377 (6)
O8	0.1325 (3)	0.0316 (2)	0.7726 (2)	0.0574 (8)
Mn1	0.02386 (5)	0.97654 (4)	0.29630 (4)	0.03096 (15)
Mn2	−0.02680 (5)	0.68565 (4)	0.46455 (4)	0.02955 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.058 (3)	0.034 (2)	0.053 (2)	−0.0085 (19)	0.005 (2)	−0.024 (2)
C2	0.079 (4)	0.043 (2)	0.076 (3)	−0.014 (2)	0.020 (3)	−0.042 (3)
C3	0.064 (3)	0.046 (2)	0.060 (3)	−0.009 (2)	0.016 (2)	−0.034 (2)
C4	0.041 (2)	0.0358 (18)	0.038 (2)	−0.0055 (17)	0.0019 (17)	−0.0181 (17)
C5	0.037 (2)	0.0328 (18)	0.0341 (18)	−0.0033 (16)	−0.0041 (16)	−0.0153 (16)
C6	0.036 (2)	0.043 (2)	0.046 (2)	−0.0100 (18)	−0.0044 (19)	−0.0182 (19)
C7	0.043 (3)	0.055 (2)	0.054 (3)	−0.009 (2)	0.005 (2)	−0.025 (2)
C8	0.046 (3)	0.062 (3)	0.051 (3)	−0.021 (2)	0.006 (2)	−0.020 (2)
C9	0.050 (3)	0.052 (3)	0.058 (3)	−0.021 (2)	0.001 (2)	−0.013 (2)
C10	0.052 (3)	0.043 (2)	0.057 (3)	−0.018 (2)	0.001 (2)	−0.017 (2)
C11	0.040 (2)	0.0360 (19)	0.041 (2)	−0.0078 (17)	−0.0046 (18)	−0.0133 (18)
C12	0.039 (2)	0.0326 (18)	0.0347 (19)	−0.0061 (16)	−0.0049 (17)	−0.0121 (16)
C13	0.039 (2)	0.0292 (17)	0.0368 (19)	−0.0033 (16)	−0.0016 (17)	−0.0147 (16)
C14	0.059 (3)	0.0314 (19)	0.065 (3)	−0.0066 (19)	0.006 (2)	−0.025 (2)
C15	0.071 (4)	0.040 (2)	0.073 (3)	−0.006 (2)	0.020 (3)	−0.032 (2)
C16	0.056 (3)	0.048 (2)	0.060 (3)	−0.004 (2)	0.013 (2)	−0.033 (2)
C17	0.037 (2)	0.0290 (17)	0.0339 (19)	−0.0029 (15)	−0.0033 (17)	−0.0135 (16)
C18	0.037 (2)	0.0288 (16)	0.0299 (17)	−0.0048 (15)	−0.0041 (16)	−0.0120 (15)
C19	0.029 (2)	0.0348 (18)	0.0368 (19)	−0.0036 (15)	−0.0013 (16)	−0.0181 (17)
C20	0.029 (2)	0.0353 (18)	0.048 (2)	0.0035 (16)	−0.0098 (17)	−0.0219 (18)
C21	0.054 (3)	0.0318 (19)	0.064 (3)	0.0057 (19)	−0.025 (2)	−0.019 (2)
C22	0.089 (4)	0.038 (2)	0.085 (4)	0.010 (3)	−0.055 (3)	−0.014 (2)
C23	0.099 (5)	0.062 (3)	0.092 (4)	0.011 (3)	−0.069 (4)	−0.030 (3)
C24	0.071 (4)	0.043 (2)	0.089 (3)	0.005 (2)	−0.051 (3)	−0.030 (2)
C25	0.033 (2)	0.0342 (18)	0.055 (2)	0.0054 (16)	−0.0142 (19)	−0.0258 (18)
C26	0.034 (2)	0.0406 (19)	0.052 (2)	−0.0028 (17)	−0.0078 (18)	−0.0303 (19)
C27	0.050 (3)	0.053 (3)	0.077 (3)	−0.004 (2)	0.006 (2)	−0.044 (3)
C28	0.061 (3)	0.079 (3)	0.066 (3)	−0.021 (3)	0.023 (3)	−0.051 (3)
C29	0.064 (3)	0.060 (3)	0.041 (2)	−0.030 (2)	0.007 (2)	−0.025 (2)
C30	0.051 (3)	0.0345 (19)	0.038 (2)	−0.0118 (18)	−0.0032 (19)	−0.0139 (17)
C31	0.035 (2)	0.0327 (17)	0.0386 (19)	−0.0023 (15)	−0.0076 (17)	−0.0195 (16)
C32	0.031 (2)	0.0305 (17)	0.0392 (19)	0.0063 (15)	−0.0065 (17)	−0.0171 (16)
C33	0.046 (2)	0.0228 (16)	0.0310 (18)	−0.0047 (15)	−0.0146 (17)	−0.0079 (15)
C34	0.063 (3)	0.0221 (16)	0.0311 (18)	−0.0014 (17)	−0.0168 (19)	−0.0087 (15)
C35	0.078 (4)	0.036 (2)	0.032 (2)	−0.002 (2)	−0.009 (2)	−0.0133 (18)
C36	0.103 (5)	0.045 (2)	0.036 (2)	−0.010 (3)	−0.004 (3)	−0.015 (2)
C37	0.130 (6)	0.054 (3)	0.033 (2)	−0.021 (3)	−0.019 (3)	−0.009 (2)
C38	0.106 (5)	0.031 (2)	0.049 (3)	0.001 (2)	−0.046 (3)	−0.003 (2)
C39	0.073 (3)	0.0280 (18)	0.045 (2)	−0.0029 (19)	−0.032 (2)	−0.0119 (17)
C40	0.065 (3)	0.0293 (18)	0.059 (3)	0.0014 (19)	−0.043 (3)	−0.0097 (19)
C41	0.047 (3)	0.036 (2)	0.061 (3)	0.0004 (19)	−0.029 (2)	−0.013 (2)
C42	0.051 (3)	0.051 (3)	0.094 (4)	0.010 (2)	−0.037 (3)	−0.027 (3)
C43	0.047 (3)	0.077 (4)	0.100 (4)	−0.008 (3)	−0.028 (3)	−0.022 (3)
C44	0.073 (4)	0.047 (3)	0.107 (4)	−0.015 (3)	−0.053 (4)	−0.008 (3)
C45	0.078 (4)	0.043 (2)	0.085 (4)	−0.007 (2)	−0.054 (3)	−0.018 (2)
C46	0.054 (3)	0.0271 (17)	0.040 (2)	0.0005 (17)	−0.017 (2)	−0.0106 (16)
N1	0.040 (2)	0.0265 (14)	0.0372 (16)	−0.0057 (13)	0.0004 (14)	−0.0149 (13)
N2	0.041 (2)	0.0369 (16)	0.0363 (16)	−0.0066 (14)	0.0042 (15)	−0.0199 (15)
N3	0.040 (2)	0.0405 (17)	0.0452 (19)	−0.0063 (15)	0.0015 (16)	−0.0195 (16)
N4	0.043 (2)	0.0318 (15)	0.0386 (17)	−0.0086 (14)	−0.0008 (15)	−0.0125 (14)
O1	0.0525 (19)	0.0403 (15)	0.0495 (16)	−0.0068 (13)	−0.0221 (15)	−0.0137 (13)
O2	0.0416 (18)	0.0413 (14)	0.0688 (19)	−0.0002 (12)	−0.0194 (15)	−0.0311 (15)
O3	0.0435 (18)	0.0322 (13)	0.0432 (15)	−0.0061 (12)	0.0051 (13)	−0.0164 (12)
O4	0.066 (2)	0.0303 (13)	0.0498 (17)	0.0079 (14)	0.0115 (15)	−0.0134 (13)
O5	0.0457 (17)	0.0257 (11)	0.0321 (12)	−0.0003 (11)	−0.0113 (12)	−0.0112 (11)
O6	0.072 (2)	0.0222 (12)	0.0296 (13)	0.0026 (12)	−0.0114 (13)	−0.0078 (11)
O7	0.0451 (17)	0.0260 (12)	0.0386 (13)	−0.0052 (11)	−0.0162 (13)	−0.0081 (11)
O8	0.072 (2)	0.0270 (13)	0.0668 (19)	0.0025 (14)	−0.0300 (18)	−0.0104 (13)
Mn1	0.0346 (3)	0.0224 (2)	0.0266 (3)	−0.0066 (2)	−0.0010 (2)	−0.0075 (2)
Mn2	0.0325 (3)	0.0206 (2)	0.0300 (3)	−0.0013 (2)	−0.0053 (2)	−0.0095 (2)

Geometric parameters (Å, º)

C1—N1	1.323 (4)	C26—C31	1.396 (5)
C1—C2	1.380 (6)	C27—C28	1.375 (6)
C1—H1	0.9300	C27—H27	0.9300
C2—C3	1.371 (6)	C28—C29	1.362 (7)
C2—H2	0.9300	C28—H28	0.9300
C3—C4	1.397 (5)	C29—C30	1.376 (6)
C3—H3	0.9300	C29—H29	0.9300
C4—C18	1.388 (5)	C30—C31	1.398 (5)
C4—C5	1.454 (5)	C30—H30	0.9300
C5—N3	1.321 (5)	C31—C32	1.510 (5)
C5—C12	1.436 (5)	C32—O3	1.252 (4)
C6—N3	1.350 (5)	C32—O4	1.258 (4)
C6—C11	1.414 (5)	C33—O6	1.256 (4)
C6—C7	1.419 (6)	C33—O5	1.261 (4)
C7—C8	1.362 (6)	C33—C34	1.504 (5)
C7—H7	0.9300	C34—C35	1.387 (6)
C8—C9	1.402 (6)	C34—C39	1.403 (5)
C8—H8	0.9300	C35—C36	1.381 (6)
C9—C10	1.362 (6)	C35—H35	0.9300
C9—H9	0.9300	C36—C37	1.388 (7)
C10—C11	1.424 (5)	C36—H36	0.9300
C10—H10	0.9300	C37—C38	1.367 (8)
C11—N4	1.357 (5)	C37—H37	0.9300
C12—N4	1.328 (4)	C38—C39	1.407 (6)
C12—C13	1.459 (5)	C38—H38	0.9300
C13—C17	1.405 (5)	C39—C40	1.487 (6)
C13—C14	1.409 (5)	C40—C41	1.390 (6)
C14—C15	1.369 (6)	C40—C45	1.410 (6)
C14—H14	0.9300	C41—C42	1.387 (7)
C15—C16	1.383 (6)	C41—C46	1.502 (5)
C15—H15	0.9300	C42—C43	1.381 (7)
C16—N2	1.332 (4)	C42—H42	0.9300
C16—H16	0.9300	C43—C44	1.382 (7)
C17—N2	1.353 (5)	C43—H43	0.9300
C17—C18	1.452 (4)	C44—C45	1.377 (8)
C18—N1	1.353 (4)	C44—H44	0.9300
C19—O1	1.249 (4)	C45—H45	0.9300
C19—O2	1.267 (4)	C46—O8	1.239 (4)
C19—C20	1.497 (5)	C46—O7	1.292 (5)
C20—C21	1.387 (5)	Mn1—N1	2.236 (3)
C20—C25	1.406 (5)	Mn1—N2	2.215 (3)
C21—C22	1.389 (6)	Mn1—O1	2.078 (3)
C21—H21	0.9300	Mn2—O2	2.072 (3)
C22—C23	1.383 (6)	Mn1—O3^i	2.095 (3)
C22—H22	0.9300	Mn2—O4^i	2.090 (3)
C23—C24	1.375 (6)	Mn2—O5^ii	2.093 (2)
C23—H23	0.9300	Mn2—O6	2.124 (3)
C24—C25	1.390 (5)	Mn1—O7^ii	2.183 (2)
C24—H24	0.9300	Mn2—O7^ii	2.191 (3)
C25—C26	1.498 (5)	Mn1—O8^ii	2.422 (3)
C26—C27	1.387 (5)
N1—C1—C2	123.2 (4)	C30—C31—C32	117.2 (3)
N1—C1—H1	118.4	O3—C32—O4	125.5 (3)
C2—C1—H1	118.4	O3—C32—C31	119.0 (3)
C3—C2—C1	119.3 (4)	O4—C32—C31	115.5 (3)
C3—C2—H2	120.4	O6—C33—O5	124.2 (3)
C1—C2—H2	120.4	O6—C33—C34	117.3 (3)
C2—C3—C4	119.1 (4)	O5—C33—C34	118.5 (3)
C2—C3—H3	120.4	C35—C34—C39	119.9 (4)
C4—C3—H3	120.4	C35—C34—C33	118.9 (3)
C18—C4—C3	117.7 (3)	C39—C34—C33	121.1 (4)
C18—C4—C5	120.3 (3)	C36—C35—C34	120.8 (4)
C3—C4—C5	122.1 (4)	C36—C35—H35	119.6
N3—C5—C12	122.3 (3)	C34—C35—H35	119.6
N3—C5—C4	118.1 (3)	C35—C36—C37	119.6 (5)
C12—C5—C4	119.6 (3)	C35—C36—H36	120.2
N3—C6—C11	121.6 (4)	C37—C36—H36	120.2
N3—C6—C7	118.7 (3)	C38—C37—C36	120.3 (4)
C11—C6—C7	119.6 (4)	C38—C37—H37	119.8
C8—C7—C6	120.1 (4)	C36—C37—H37	119.8
C8—C7—H7	120.0	C37—C38—C39	121.1 (4)
C6—C7—H7	120.0	C37—C38—H38	119.5
C7—C8—C9	119.8 (4)	C39—C38—H38	119.5
C7—C8—H8	120.1	C34—C39—C38	118.2 (4)
C9—C8—H8	120.1	C34—C39—C40	122.2 (4)
C10—C9—C8	122.6 (4)	C38—C39—C40	119.5 (4)
C10—C9—H9	118.7	C41—C40—C45	117.0 (5)
C8—C9—H9	118.7	C41—C40—C39	123.2 (4)
C9—C10—C11	118.6 (4)	C45—C40—C39	119.8 (4)
C9—C10—H10	120.7	C42—C41—C40	121.3 (4)
C11—C10—H10	120.7	C42—C41—C46	118.2 (4)
N4—C11—C6	121.4 (3)	C40—C41—C46	120.0 (4)
N4—C11—C10	119.3 (3)	C43—C42—C41	120.9 (5)
C6—C11—C10	119.3 (4)	C43—C42—H42	119.6
N4—C12—C5	121.2 (3)	C41—C42—H42	119.6
N4—C12—C13	119.6 (3)	C42—C43—C44	118.7 (6)
C5—C12—C13	119.2 (3)	C42—C43—H43	120.6
C17—C13—C14	117.5 (3)	C44—C43—H43	120.6
C17—C13—C12	119.9 (3)	C45—C44—C43	120.8 (5)
C14—C13—C12	122.6 (3)	C45—C44—H44	119.6
C15—C14—C13	119.4 (4)	C43—C44—H44	119.6
C15—C14—H14	120.3	C44—C45—C40	121.3 (5)
C13—C14—H14	120.3	C44—C45—H45	119.4
C14—C15—C16	119.2 (4)	C40—C45—H45	119.4
C14—C15—H15	120.4	O8—C46—O7	120.9 (3)
C16—C15—H15	120.4	O8—C46—C41	122.5 (4)
N2—C16—C15	123.2 (4)	O7—C46—C41	116.4 (3)
N2—C16—H16	118.4	O8—C46—Mn1^ii	66.4 (2)
C15—C16—H16	118.4	O7—C46—Mn1^ii	55.53 (16)
N2—C17—C13	122.4 (3)	C41—C46—Mn1^ii	163.7 (3)
N2—C17—C18	117.4 (3)	C1—N1—C18	117.8 (3)
C13—C17—C18	120.3 (3)	C1—N1—Mn1	126.2 (3)
N1—C18—C4	123.0 (3)	C18—N1—Mn1	115.4 (2)
N1—C18—C17	116.4 (3)	C16—N2—C17	118.3 (3)
C4—C18—C17	120.6 (3)	C16—N2—Mn1	125.7 (3)
O1—C19—O2	124.1 (3)	C17—N2—Mn1	115.8 (2)
O1—C19—C20	118.4 (3)	C5—N3—C6	116.7 (3)
O2—C19—C20	117.4 (3)	C12—N4—C11	116.9 (3)
C21—C20—C25	119.5 (3)	C19—O1—Mn1	130.5 (2)
C21—C20—C19	118.0 (3)	C19—O2—Mn2	131.8 (2)
C25—C20—C19	122.3 (3)	C32—O3—Mn1^i	125.1 (2)
C20—C21—C22	121.6 (4)	C32—O4—Mn2^i	145.5 (3)
C20—C21—H21	119.2	C33—O5—Mn2^ii	136.0 (2)
C22—C21—H21	119.2	C33—O6—Mn2	123.9 (2)
C23—C22—C21	118.3 (4)	C46—O7—Mn1^ii	95.26 (19)
C23—C22—H22	120.8	C46—O7—Mn2^ii	126.9 (2)
C21—C22—H22	120.8	Mn1^ii—O7—Mn2^ii	107.42 (10)
C24—C23—C22	120.9 (4)	C46—O8—Mn1^ii	85.7 (2)
C24—C23—H23	119.6	O1—Mn1—O3^i	94.57 (11)
C22—C23—H23	119.6	O1—Mn1—O7^ii	102.47 (10)
C23—C24—C25	121.3 (4)	O3^i—Mn1—O7^ii	96.67 (10)
C23—C24—H24	119.3	O1—Mn1—N2	97.39 (12)
C25—C24—H24	119.3	O3^i—Mn1—N2	103.28 (11)
C24—C25—C20	118.3 (4)	O7^ii—Mn1—N2	150.51 (10)
C24—C25—C26	118.0 (3)	O1—Mn1—N1	88.13 (12)
C20—C25—C26	123.3 (3)	O3^i—Mn1—N1	176.37 (11)
C27—C26—C31	118.0 (4)	O7^ii—Mn1—N1	85.08 (10)
C27—C26—C25	115.8 (3)	N2—Mn1—N1	73.93 (11)
C31—C26—C25	125.9 (3)	O1—Mn1—O8^ii	158.69 (10)
C28—C27—C26	121.5 (4)	O3^i—Mn1—O8^ii	83.93 (11)
C28—C27—H27	119.2	O7^ii—Mn1—O8^ii	56.84 (9)
C26—C27—H27	119.2	N2—Mn1—O8^ii	103.65 (11)
C29—C28—C27	120.6 (4)	N1—Mn1—O8^ii	94.43 (11)
C29—C28—H28	119.7	O2—Mn2—O4^i	103.87 (12)
C27—C28—H28	119.7	O2—Mn2—O5^ii	123.95 (10)
C28—C29—C30	119.5 (4)	O4^i—Mn2—O5^ii	132.03 (12)
C28—C29—H29	120.3	O2—Mn2—O6	92.53 (12)
C30—C29—H29	120.3	O4^i—Mn2—O6	88.76 (11)
C29—C30—C31	120.8 (4)	O5^ii—Mn2—O6	92.47 (9)
C29—C30—H30	119.6	O2—Mn2—O7^ii	91.76 (11)
C31—C30—H30	119.6	O4^i—Mn2—O7^ii	83.90 (11)
C26—C31—C30	119.7 (3)	O5^ii—Mn2—O7^ii	90.52 (9)
C26—C31—C32	123.1 (3)	O6—Mn2—O7^ii	172.21 (10)

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