A candidate for a single-chain magnet: [Mn₃(OAc)₆(py)₂(H₂O)₂]_n (OAc is acetate and py is pyridine)

The title complex, catena-poly[di-[mu]₃-acetato-[kappa]⁶O:O:O'-tetra-[mu]₂-acetato-[kappa]⁴O:O;[kappa]⁴O:O'-di­aqua­bis­(pyridine-[kappa]N)trimanganese(II)], [Mn₃(CH₃COO)₆(C₆H₅N)₂(H₂O)₂]_n, is a true one-dimensional coordination polymer, in which the Mn^II centres form a zigzag chain along [010]. The asymmetric unit contains two metal centres, one of which (Mn1) lies on an inversion centre, while the other (Mn2) is placed close to an inversion centre on a general position. Since all the acetates behave as bridging ligands, although with different [mu]₂- and [mu]₃-coordination modes, a one-dimensional polymeric structure is formed, based on trinuclear repeat units (Mn1...Mn2...Mn2'), in which the Mn2 and Mn2' sites are related by an inversion centre. Within this monomeric block, the metal-metal separ­ations are Mn1...Mn2 = 3.36180 (18) Å and Mn2...Mn2' = 4.4804 (3) Å. Cation Mn1, located on an inversion centre, displays an [MnO₆] coordination sphere, while Mn2, on a general position, has a slightly stronger [MnO₅N] ligand field, as the sixth coordination site is occupied by a pyridine mol­ecule. Both centres approximate an octa­hedral ligand field. The chains are parallel in the crystal structure and inter­act via hydrogen bonds involving coordinated water mol­ecules. However, the shortest metal-metal separation between two chains [5.3752 (3) Å] is large compared with the intra­chain inter­actions. These structural features are compatible with a single-chain magnet behaviour, as confirmed by preliminary magnetic studies.

S1. Introduction

Manganese carboxyl­ate cluster chemistry is now widely recognized as a field from which materials suitable for qubit-based computation could emerge. That chemistry was pioneered by George Christou and David Hendrickson, among others, with the fruitful Mn₁₂ line of compounds, including the emblematic cluster [Mn₁₂O₁₂(O₂CPh)₁₆(H₂O)₄] (Boyd et al., 1988; Sessoli et al., 1993). This mixed-valence cluster displays the two essential features required for a single-molecule magnet (SMM), i.e. a high-spin ground state and a large negative magnetic anisotropy. However, the most impressive behaviour reported for these clusters is the resonant quantum tunnelling of magnetization, which is a key property for molecular spintronics (Perenboom et al., 1998; Hill et al., 2003, 2010). Like SMM clusters, some chain-shaped molecules also exhibit bis­tability and slow relaxation of their magnetization. These compounds, termed single-chain magnets (SCM), have their magnetic behaviour affected not only by the magnetic anisotropy of the spins but also by their intra­chain magnetic inter­actions (Coronado et al., 2003; Brooker & Kitchen, 2009; Zhang et al., 2013).

Although many synthetic approaches have been described in the literature, the rational design of a synthesis for a given manganese carboxyl­ate cluster is hindered by the fine tuning of the following parameters: the oxidation states of the metal centres; the suitability of the symmetry of the ligand field for the 3d orbitals centred on the metals; the coordination modes of the carboxyl­ate ligands; and competition with ancillary ligands. Moreover, both the nuclearity and dimensionality of the resulting structure are quite unpredi­cta­ble, with a large range of possibilities, from isolated SMMs, which may be described as zero-dimensional nanoparticles, to three-dimensional polymeric architectures, which may be considered as bulk materials.

While working on the synthesis of such compounds, we obtained a one-dimensional polymer, namely [Mn₃(OAc)₆(py)₂(H₂O)₂]_n (OAc is acetate and py is pyridine), (I), which is a candidate for a new SCM.

S2. Results and discussion

Although the synthesis of (I) was carried out under aerobic conditions, the complex is an Mn^II species with the formula [Mn₃(OAc)₆(H₂O)₂(py)₂]_∞, where OAc and py are acetate and pyridine ligands, respectively. One manganese ion, Mn1, is located on an inversion centre in the triclinic unit cell, and the other, Mn2, is located in a general position, close to an inversion centre. Three acetate ligands are bonded to Mn1, using three coordination modes (Fig. 1). The first acetate (atoms O1/O2) bridges independent Mn centres in the common 2.11 syn–syn mode [for Harris coordination nomenclature, see Coxall et al. (2000)], found, for example, in the starting material manganese di­acetate, Mn(OAc)₂.4H₂O (Bertaut et al., 1974; Nicolaï et al., 2001), and also in Co(OAc)₂.H₂O (Zhang et al., 2010) and other simple divalent metal salts. Acetate O5/O6 bridges the same metal centres Mn1 and Mn2 in the 2.20 coordination mode, which is much less frequently observed. For Mn-based polymers, only two cases have been reported to date including this coordination mode for OAc, viz. [Mn₃(OAc)₆(H₂O)₄].2H₂O (Cheng & Wang, 1991) and a complex polymer with a chain-like structure (Xu et al., 2009). Finally, the polymeric nature of (I) is fixed by the third acetate, O3/O4, in the 3.12 coordination mode, between Mn1 and Mn2 in the asymmetric unit and a symmetry-related Mn2ⁱ site [symmetry code: (i) -x + 1, -y + 1, -z + 1]. This arrangement for polymerization is identical to that found in Mn(OAc)₂.4H₂O (Bertaut et al., 1974) and α-Mn(OAc)₂ (Lin et al., 2009), and in more complex polymeric compounds with various dimensionalities (e.g. Zartilas et al., 2008; Weng et al., 2008; Wan et al., 2010). These different µ₂- and µ₃-bridging modes are reflected in the IR spectrum of (I): the ν_asym and ν_sym vibration modes for the COO^- groups are split into two or three bands around 1557 and 1414 cm^-1, respectively.

The arrangement of the acetate ligands completes the o­cta­hedral coordination environment for the Mn1 centre. This metal centre presents an [MnO₆] ligand field with the symmetry lowered from o­cta­hedral to C_i, because the Mn1—O bond lengths for each acetate are significantly different: Mn1—O1 = 2.1369 (9), Mn1—O3 = 2.1997 (8) and Mn1—O5 = 2.2277 (8) Å. The coordination environment for Mn2, which is in a general position, is completed with neutral ligands, H₂O and pyridine, present in the reaction media. Mn2 thus has an [MnO₅N] coordination, with a ligand field probably slightly stronger than that for Mn1, and a large deviation from o­cta­hedral symmetry: the coordination bond lengths for Mn2 are in the range 2.0995 (9)–2.2946 (10) Å and the trans angles are in the range 164.84 (4)–176.87 (4)°.

The one-dimensional polymeric chain of (I), formed via inversion centres, runs in the [010] direction (Fig. 2). Within the asymmetric unit, the Mn1···Mn2 separation is 3.36180 (18) Å and the Mn2···Mn2ⁱ distance, allowing polymerization, is longer, at 4.4804 (3) Å. Both distances are unexceptional, considering that, in Mn–acetate-based polymers, they span a large range, ca 2.5–5.2 Å, allowing a variety of magnetic ground states for these materials. In the present case, long metal–metal separations alternate along the chain with dimers of short separation. Parallel chains are packed in the crystal structure, and the cohesion is maintained through O—H···O hydrogen bonds of moderate strength, using the coordinated water molecules as donors (Fig. 2 and Table 2). The graph set (Bernstein et al., 1995) resulting from two inversion-related inter­chain hydrogen bonds is R₂²(8), common in water–acetate systems. The metal–metal distance in the R(8) [Should this be R₂²(8)?] ring is Mn2···Mn2ⁱⁱ = 5.3752 (3) Å [symmetry code: (ii) -x + 2, -y + 1, -z + 1]. Since this distance is much longer than the metal–metal inter­actions along the chain, (I) should be considered as a true low-dimensional one-dimensional polymer, rather than a two-dimensional material. In spite of its low dimensionality, this material is a densely packed system, reaching a high Kitaigorodski packing coefficient of C_K = 0.733 (PLATON; Spek, 2009).

The above-described geometric features are encouraging and make (I) a candidate for being an Ising one-dimensional system behaving as a ferri- or ferromagnet. Assuming a weak enough crystal-field splitting, high-spin d⁵ electronic configurations may be expected for the Mn^II centres. The anisotropic trinuclear units (Mn1···Mn2···Mn2ⁱ) have distances between the magnetic sites that are suitable for ferromagnetic inter­actions. Indeed, these distances, of 3.36 and 4.48 Å, may be compared with those observed in the first heterometallic Mn^III–Ni^II polymeric SCM synthesized in 2002: Mn^III···Mn^III = 3.42 Å and Mn^III···Ni^II = 5.06 Å (Clérac et al., 2002). Thus, the actual nature of the magnetic behaviour for the title Mn^II polymer should be defined mainly by inter­chain contacts resulting from the R(8) [Should this be R₂²(8)?] ring motifs. A search of the Cambridge Structural Database (Version 5.35, updated May 2014; Allen, 2002) retrieved 139 similar R₂²(8) rings in Mn compounds, with coordinated water molecules as donors and carboxyl­ate O atoms as acceptors. Most of them are associated with first-level centrosymmetric patterns R(_a^a), as in (I), and the others belong to second-level patterns R(_a^b), in Motherwell's graph-set nomenclature (Motherwell et al., 2000). The important feature to be considered, bearing the magnetic properties in mind, is the poor flexibility of this ring: for R(_a^a) patterns, the ring has a chair conformation and the metal–metal inter­action is determined mainly by the puckering parameters, while R(_a^b) patterns may adopt a folded conformation, allowing shorter metal–metal inter­actions. In the subset of 139 hits, regardless of the Mn oxidation state and the dimensionality of the crystal structure, the Mn···Mn separation in R₂²(8) rings is in the range 4.77–6.32 Å. Inter­estingly, the shortest separation was reported for a complex Mn₂₂ cluster, in which the R(8) [Should this be R₂²(8)?] ring links two molecules. This mixed-valence compound is an SMM with quantum tunnelling of magnetization (Brockman et al., 2007). Thus, it may be inferred that the R(8) [Should this be R₂²(8)?] ring in (I) is not an efficient exchange pathway, making a strong anti­ferromagnetic inter­chain coupling unlikely.

Preliminary magnetic measurements of (I) are in agreement with this structural description. At room temperature, the title complex shows a χ_mT value of 13.15 cm³ mol^-1 K, which is very close to that calculated for three non-inter­acting S_i = 5/2 centres, 13.12 cm³ mol^-1 K, assuming a spin-only model (g_Mn = 2.00; Christian et al., 2004). A plot of M versus T shows different magnetization pathways below a critical temperature T_C = 50 K, pointing to superparamagnetic behaviour [Might it help the reader to have this plot available in the supporting information?]. On the other hand, a hysteresis loop in the M(H) plot is observed (Fig. 3), indicative of ferromagnetic exchange inter­actions (Bertotti, 1998). Experimentally, an SCM shows both superparamagnet-like properties with frequency-dependent out-of-phase signals in AC susceptibility measurements, and hysteresis in M versus applied DC field measurements (King et al., 2004; Brockman et al., 2007). Therefore, AC magnetic susceptibility measurements are currently being carried out, in order to characterize further the potential SCM behaviour of this new polymer.

S3. Synthesis, crystallization and SQUID magnetometry

All synthetic and post-synthetic work was carried out under aerobic conditions. The reagents and solvents were obtained from commercial sources and used without further purification. IR analyses were performed using a Nicolet Nexus 6700 FT–IR spectrometer in the 4000–600 cm^-1 range. Compound (I) was prepared by the addition of excess pyridine (12.41 mmol, 1 ml) to a hot solution of Mn(OAc)₂.4H₂O (1 mmol, 0.245 g) in EtOH (95%; 5 ml). The solution was stirred for 30 min and filtered, [and then layered with Et₂O?]. After 1 d, colourless crystals of (I) were obtained from this solution by slow diffusion of Et₂O (yield 48%). Spectroscopic analysis: IR ([Medium?], ν_max, cm^-1): 3252 (br), 2943 (s), 2878 (s), 1557 (m), 1414 (m), 1004 (st), 877 (m), 658 (m), 606 (m). Magnetic susceptibility measurements on powdered crystals were carried out using a Quantum Design SQUID magnetometer at 2 K under an applied field H of -50000 to 50000 Oe, and in the temperature range 2–300 K at H = 1000 Oe. Correction for the diamagnetic contribution of the constituent atoms was applied using Pascal's constants.

S4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The collection of diffraction data (work done in Canada) and the final structure refinement (work done in Mexico) were routine works. All C-bound H atoms were placed in calculated positions, with C—H = 0.95 (pyridine) or 0.98 Å (methyl acetate). Methyl groups were considered as rigid tetra­hedral groups free to rotate about their C—C bonds. Isotropic displacement parameters for these H atoms were calculated as U_iso(H) = 1.2U_eq(C) for the pyridine molecule and U_iso(H) = 1.5U_eq(C) for the methyl groups. Atoms H71 and H72 of the water molecule were clearly detected in a difference map and were refined with free coordinates and isotropic displacement parameters.

Related literature

For related literature, see: Allen (2002); Bernstein et al. (1995); Bertaut et al. (1974); Bertotti (1998); Boyd et al. (1988); Brockman et al. (2007); Brooker & Kitchen (2009); Cheng & Wang (1991); Christian et al. (2004); Clérac et al. (2002); Coronado et al. (2003); Coxall et al. (2000); Hill et al. (2003, 2010); King et al. (2004); Lin et al. (2009); Motherwell et al. (2000); Nicolaï et al. (2001); Perenboom et al. (1998); Sessoli et al. (1993); Spek (2009); Wan et al. (2010); Weng et al. (2008); Xu et al. (2009); Zartilas et al. (2008); Zhang et al. (2010, 2013).

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); data reduction: XPREP (Bruker, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008).

Figures

	Fig. 1. Part of the polymeric chain of (I), limited to a couple of [Mn1···Mn2] units related by an inversion centre. Coordination spheres for the [Mn1···Mn2···Mn2^i] monomer are complete, and the asymmetric unit is labelled. Nonlabelled atoms are generated by the symmetry operator (1 - x, 1 - y, 1 - z). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Part of the crystal structure of (I), showing three chains in the [010] direction and the R(8) rings connecting the chains (dashed bonds). For the sake of clarity, pyridine ligands bonded to Mn2 centres are drawn with a single N atom (blue spheres), and all methyl H atoms have been omitted.
	Fig. 3. Magnetization (M) versus applied magnetic field (H) hysteresis loop for (I) at T = 2 K. The inset focuses on the experimental data in the -3000 to 3000 Oe range.

catena-Poly[di-µ₃-acetato-κ⁶O:O:O'-tetra-µ₂-acetato-κ⁴O:O;κ⁴O:O'-diaquabis(pyridine-κN)trimanganese(II)]

Crystal data

[Mn3(C2H3O2)6(C6H5N)2(H2O)2]	F(000) = 365
Mr = 713.31	Dx = 1.665 Mg m^−3
Triclinic, P1	Melting point: 493 K
a = 8.1153 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0404 (2) Å	Cell parameters from 9432 reflections
c = 10.0759 (2) Å	θ = 2.3–28.3°
α = 83.160 (1)°	µ = 1.38 mm^−1
β = 81.994 (1)°	T = 200 K
γ = 77.423 (1)°	Block, colourless
V = 711.43 (3) Å^3	0.15 × 0.12 × 0.12 mm
Z = 1

Data collection

Bruker APEXII CCD area-detector diffractometer	3514 independent reflections
Radiation source: fine-focus sealed tube	3269 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.012
ϕ and ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.820, Tmax = 0.852	k = −12→12
11780 measured reflections	l = −13→13

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.057	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.031P)^2 + 0.2663P] where P = (Fo^2 + 2Fc^2)/3
3514 reflections	(Δ/σ)max = 0.001
198 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3
0 constraints

Special details

Experimental. Data collection was performed with four batch runs at phi = 0.00° (600 frames), at phi = 90.00° (600 frames), at phi = 180.00° (600 frames) and at phi = 270.00° (600 frames). A fifth batch run was collected at phi = 0.00° (50 frames) to monitor crystal and diffractometer stability. Frame width = 0.30° in omega. Data were merged, corrected for decay (if any), and treated with multi-scan absorption corrections (if required).

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

	x	y	z	Uiso*/Ueq
Mn1	0.5000	1.0000	0.5000	0.01484 (6)
Mn2	0.67310 (2)	0.63019 (2)	0.56849 (2)	0.01492 (6)
N1	0.49468 (13)	0.58131 (12)	0.75859 (11)	0.0203 (2)
O1	0.69813 (11)	0.93862 (10)	0.34097 (9)	0.02220 (18)
O2	0.81744 (11)	0.69304 (9)	0.38176 (9)	0.02006 (17)
O3	0.43984 (10)	0.77516 (9)	0.49460 (9)	0.01721 (16)
O4	0.30799 (13)	0.58516 (10)	0.49762 (11)	0.0290 (2)
O5	0.66602 (11)	0.85585 (9)	0.64449 (9)	0.01837 (17)
O6	0.83746 (14)	0.78614 (12)	0.80527 (11)	0.0335 (2)
O7	0.89280 (13)	0.53570 (12)	0.67585 (11)	0.0269 (2)
H71	0.908 (3)	0.601 (3)	0.718 (2)	0.046 (6)*
H72	0.980 (3)	0.482 (2)	0.659 (2)	0.041 (5)*
C1	0.80320 (14)	0.81979 (13)	0.31196 (12)	0.0176 (2)
C2	0.92106 (19)	0.83031 (17)	0.18292 (15)	0.0327 (3)
H2A	1.0210	0.7471	0.1864	0.049*
H2B	0.9572	0.9281	0.1719	0.049*
H2C	0.8615	0.8225	0.1066	0.049*
C3	0.30526 (14)	0.72234 (13)	0.49728 (11)	0.0164 (2)
C4	0.13774 (16)	0.83251 (15)	0.50462 (17)	0.0306 (3)
H4A	0.0509	0.7845	0.4793	0.046*
H4B	0.1475	0.9232	0.4427	0.046*
H4C	0.1053	0.8619	0.5967	0.046*
C5	0.72135 (15)	0.87587 (13)	0.75330 (12)	0.0192 (2)
C6	0.6347 (2)	1.01701 (16)	0.82145 (15)	0.0323 (3)
H6A	0.7028	1.0322	0.8898	0.048*
H6B	0.5218	1.0051	0.8644	0.048*
H6C	0.6232	1.1054	0.7544	0.048*
C7	0.50630 (18)	0.43829 (15)	0.81537 (14)	0.0264 (3)
H7A	0.6018	0.3634	0.7860	0.032*
C8	0.3863 (2)	0.39423 (17)	0.91456 (15)	0.0332 (3)
H8A	0.3998	0.2916	0.9527	0.040*
C9	0.2468 (2)	0.5017 (2)	0.95705 (15)	0.0371 (3)
H9A	0.1618	0.4746	1.0246	0.044*
C10	0.23278 (19)	0.6499 (2)	0.89948 (15)	0.0356 (3)
H10A	0.1372	0.7262	0.9261	0.043*
C11	0.36003 (17)	0.68556 (15)	0.80251 (13)	0.0259 (3)
H11A	0.3516	0.7883	0.7655	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01447 (12)	0.00843 (11)	0.01996 (12)	−0.00059 (8)	0.00022 (9)	−0.00054 (8)
Mn2	0.01320 (9)	0.00939 (9)	0.02067 (10)	−0.00066 (6)	0.00036 (6)	−0.00119 (6)
N1	0.0203 (5)	0.0181 (5)	0.0210 (5)	−0.0024 (4)	−0.0005 (4)	−0.0009 (4)
O1	0.0210 (4)	0.0158 (4)	0.0257 (4)	0.0004 (3)	0.0040 (3)	−0.0012 (3)
O2	0.0184 (4)	0.0155 (4)	0.0233 (4)	−0.0004 (3)	0.0024 (3)	−0.0013 (3)
O3	0.0136 (4)	0.0121 (4)	0.0250 (4)	−0.0018 (3)	−0.0013 (3)	−0.0009 (3)
O4	0.0309 (5)	0.0144 (4)	0.0435 (6)	−0.0071 (4)	−0.0014 (4)	−0.0084 (4)
O5	0.0205 (4)	0.0134 (4)	0.0210 (4)	−0.0016 (3)	−0.0036 (3)	−0.0026 (3)
O6	0.0365 (6)	0.0294 (5)	0.0333 (5)	0.0076 (4)	−0.0169 (4)	−0.0090 (4)
O7	0.0199 (5)	0.0234 (5)	0.0353 (5)	0.0055 (4)	−0.0067 (4)	−0.0077 (4)
C1	0.0148 (5)	0.0180 (5)	0.0196 (5)	−0.0031 (4)	−0.0002 (4)	−0.0030 (4)
C2	0.0317 (7)	0.0305 (7)	0.0275 (7)	0.0002 (6)	0.0113 (6)	0.0015 (5)
C3	0.0173 (5)	0.0139 (5)	0.0181 (5)	−0.0030 (4)	−0.0016 (4)	−0.0023 (4)
C4	0.0151 (6)	0.0221 (6)	0.0538 (9)	−0.0011 (5)	−0.0061 (6)	−0.0023 (6)
C5	0.0206 (6)	0.0163 (5)	0.0202 (5)	−0.0039 (4)	−0.0003 (4)	−0.0018 (4)
C6	0.0425 (8)	0.0253 (7)	0.0275 (7)	0.0034 (6)	−0.0074 (6)	−0.0115 (5)
C7	0.0326 (7)	0.0196 (6)	0.0253 (6)	−0.0049 (5)	0.0002 (5)	−0.0003 (5)
C8	0.0452 (8)	0.0298 (7)	0.0267 (7)	−0.0178 (6)	−0.0018 (6)	0.0047 (5)
C9	0.0303 (7)	0.0543 (10)	0.0262 (7)	−0.0171 (7)	0.0027 (6)	0.0065 (6)
C10	0.0250 (7)	0.0472 (9)	0.0264 (7)	0.0041 (6)	0.0042 (5)	0.0007 (6)
C11	0.0248 (6)	0.0257 (6)	0.0217 (6)	0.0026 (5)	0.0000 (5)	0.0018 (5)

Geometric parameters (Å, º)

Mn1—O1	2.1369 (9)	O7—H72	0.78 (2)
Mn1—O1^i	2.1369 (9)	C1—C2	1.5094 (17)
Mn1—O3	2.1997 (8)	C2—H2A	0.9800
Mn1—O3^i	2.1997 (8)	C2—H2B	0.9800
Mn1—O5^i	2.2277 (8)	C2—H2C	0.9800
Mn1—O5	2.2277 (8)	C3—C4	1.4985 (17)
Mn2—O4^ii	2.0995 (9)	C4—H4A	0.9800
Mn2—O2	2.1579 (9)	C4—H4B	0.9800
Mn2—O7	2.1755 (10)	C4—H4C	0.9800
Mn2—O3	2.2215 (8)	C5—C6	1.5092 (17)
Mn2—O5	2.2494 (8)	C6—H6A	0.9800
Mn2—N1	2.2946 (10)	C6—H6B	0.9800
N1—C7	1.3392 (16)	C6—H6C	0.9800
N1—C11	1.3395 (16)	C7—C8	1.3819 (19)
O1—C1	1.2542 (14)	C7—H7A	0.9500
O2—C1	1.2625 (14)	C8—C9	1.376 (2)
O3—C3	1.2796 (14)	C8—H8A	0.9500
O4—C3	1.2352 (14)	C9—C10	1.383 (2)
O4—Mn2^ii	2.0995 (9)	C9—H9A	0.9500
O5—C5	1.2870 (15)	C10—C11	1.3833 (19)
O6—C5	1.2343 (16)	C10—H10A	0.9500
O7—H71	0.81 (2)	C11—H11A	0.9500
O1—Mn1—O1^i	180.0	H71—O7—H72	108 (2)
O1—Mn1—O3	86.76 (3)	O1—C1—O2	125.21 (11)
O1^i—Mn1—O3	93.24 (3)	O1—C1—C2	116.92 (11)
O1—Mn1—O3^i	93.24 (3)	O2—C1—C2	117.87 (11)
O1^i—Mn1—O3^i	86.76 (3)	C1—C2—H2A	109.5
O3—Mn1—O3^i	180.0	C1—C2—H2B	109.5
O1—Mn1—O5^i	91.39 (3)	H2A—C2—H2B	109.5
O1^i—Mn1—O5^i	88.61 (3)	C1—C2—H2C	109.5
O3—Mn1—O5^i	101.79 (3)	H2A—C2—H2C	109.5
O3^i—Mn1—O5^i	78.21 (3)	H2B—C2—H2C	109.5
O1—Mn1—O5	88.61 (3)	O4—C3—O3	122.80 (11)
O1^i—Mn1—O5	91.39 (3)	O4—C3—C4	119.24 (11)
O3—Mn1—O5	78.21 (3)	O3—C3—C4	117.94 (10)
O3^i—Mn1—O5	101.79 (3)	C3—C4—H4A	109.5
O5^i—Mn1—O5	180.0	C3—C4—H4B	109.5
O4^ii—Mn2—O2	88.84 (4)	H4A—C4—H4B	109.5
O4^ii—Mn2—O7	88.67 (4)	C3—C4—H4C	109.5
O2—Mn2—O7	95.57 (4)	H4A—C4—H4C	109.5
O4^ii—Mn2—O3	105.82 (4)	H4B—C4—H4C	109.5
O2—Mn2—O3	89.30 (3)	O6—C5—O5	124.09 (11)
O7—Mn2—O3	164.84 (4)	O6—C5—C6	118.89 (12)
O4^ii—Mn2—O5	176.87 (4)	O5—C5—C6	117.01 (11)
O2—Mn2—O5	91.19 (3)	C5—C6—H6A	109.5
O7—Mn2—O5	88.22 (4)	C5—C6—H6B	109.5
O3—Mn2—O5	77.31 (3)	H6A—C6—H6B	109.5
O4^ii—Mn2—N1	93.24 (4)	C5—C6—H6C	109.5
O2—Mn2—N1	173.79 (3)	H6A—C6—H6C	109.5
O7—Mn2—N1	90.33 (4)	H6B—C6—H6C	109.5
O3—Mn2—N1	84.51 (3)	N1—C7—C8	123.28 (13)
O5—Mn2—N1	87.05 (3)	N1—C7—H7A	118.4
C7—N1—C11	117.44 (11)	C8—C7—H7A	118.4
C7—N1—Mn2	119.52 (9)	C9—C8—C7	118.76 (13)
C11—N1—Mn2	122.07 (8)	C9—C8—H8A	120.6
C1—O1—Mn1	135.91 (8)	C7—C8—H8A	120.6
C1—O2—Mn2	129.37 (8)	C8—C9—C10	118.72 (13)
C3—O3—Mn1	136.43 (7)	C8—C9—H9A	120.6
C3—O3—Mn2	120.89 (7)	C10—C9—H9A	120.6
Mn1—O3—Mn2	98.99 (3)	C9—C10—C11	119.02 (14)
C3—O4—Mn2^ii	161.58 (10)	C9—C10—H10A	120.5
C5—O5—Mn1	135.62 (7)	C11—C10—H10A	120.5
C5—O5—Mn2	126.01 (7)	N1—C11—C10	122.75 (13)
Mn1—O5—Mn2	97.33 (3)	N1—C11—H11A	118.6
Mn2—O7—H71	107.7 (15)	C10—C11—H11A	118.6
Mn2—O7—H72	134.9 (15)
Mn1—O1—C1—O2	−1.0 (2)	Mn2—O5—C5—O6	27.84 (17)
Mn1—O1—C1—C2	178.82 (10)	Mn1—O5—C5—C6	14.66 (17)
Mn2—O2—C1—O1	0.83 (18)	Mn2—O5—C5—C6	−150.87 (9)
Mn2—O2—C1—C2	−178.99 (9)	C11—N1—C7—C8	0.8 (2)
Mn2^ii—O4—C3—O3	−85.5 (3)	Mn2—N1—C7—C8	−168.22 (11)
Mn2^ii—O4—C3—C4	96.5 (3)	N1—C7—C8—C9	0.5 (2)
Mn1—O3—C3—O4	−177.30 (9)	C7—C8—C9—C10	−0.4 (2)
Mn2—O3—C3—O4	−24.02 (16)	C8—C9—C10—C11	−0.8 (2)
Mn1—O3—C3—C4	0.76 (18)	C7—N1—C11—C10	−2.0 (2)
Mn2—O3—C3—C4	154.04 (9)	Mn2—N1—C11—C10	166.62 (11)
Mn1—O5—C5—O6	−166.63 (10)	C9—C10—C11—N1	2.1 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O7—H71···O6	0.81 (2)	1.92 (2)	2.6694 (15)	154 (2)
O7—H72···O2^iii	0.78 (2)	2.05 (2)	2.8162 (13)	169 (2)

Symmetry code: (iii) −x+2, −y+1, −z+1.