[Mn₁₂O₁₂(O₂CMe)₁₂(NO₃)₄(H₂O)₄]: facile synthesis of a new type of Mn₁₂ complex

The title dodeca­nuclear Mn complex, namely dodeca-μ₂-acetato-κ²⁴O:O′-tetra­aqua­tetra-μ₂-nitrato-κ⁸O:O′-tetra-μ₄-oxido-octa-μ₃-oxido-tetra­manganese(IV)octa­manganese(III) nitro­methane tetra­solvate, [Mn₁₂(CH₃COO)₁₂(NO₃)₄O₁₂(H₂O)₄]·4CH₃NO₂, was synthesized by the reaction of Mn²⁺ and Ce⁴⁺ sources in nitro­methane with an excess of acetic acid. This compound is distinct from the previously known single-mol­ecule magnet [Mn₁₂O₁₂(O₂CMe)₁₆(H₂O)₄], synthesized by Lis [Acta Cryst. (1980), B36, 2042–2044]. It is the first Mn₁₂-type mol­ecule containing nitrate ligands to be directly synthesized without the use of a preformed cluster. Additionally, this mol­ecule is distinct from all other known Mn₁₂ complexes due to inter­molecular hydrogen bonds between the nitrate and water ligands, which give rise to a three-dimensional network. The complex is compared to other known Mn₁₂ mol­ecules in terms of its structural parameters and symmetry.

S1. Introduction

The original `Mn<sub>12</sub>' molecule was first synthesized in 1980 and has garnered much inter­est in the scientific community, especially in the field of single-molecule magnets (SMMs; Lis, 1980). Herein, the term `Mn₁₂' will be used to describe all structures containing a core similar to the molecule synthesized by Lis, which contains four Mn^IV ions surrounded by a ring of eight Mn^III ions bridged by 12 oxide (O^2-) ions. SMMs are molecules that behave as molecular supra­paramagnets below a certain blocking temperature, T_B, and exhibit slow magnetic relaxation, and consequently magnetic hysteresis (Bagai & Christou, 2009). The SMM properties in manganese complexes arise from the combination of a large ground-state spin, S, due to the ferromagnetic coupling of Mn^III ions and large negative anisotropy, D, which arises from the Jahn–Teller distortion of the Mn^III ions. Many studies have focused on changing the carboxyl­ate R groups of the complex to see their effect on the structural and magnetic properties (Sessoli et al., 1993). Herein, the structure of a new Mn₁₂ molecule containing 12 acetate ligands, four water ligands, and four nitrate ligands is presented. This complex has been characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction.

S2. Experimental

S2.1. Synthesis and crystallization

The title Mn₁₂ complex was synthesized using an excess of acetic acid, manganese(II) acetate, and cerium(IV) ammonium nitrate in 20:8:4 ratio in a 20 ml solution of warm nitro­methane. The solution was filtered and the filtrate left undisturbed for 3 d, during which time brown crystals of the title complex formed in approximately 40% yield. The identity of the complex was also confirmed by IR spectroscopy and elemental analysis, which were both in good agreement with the crystal structure analysis.

S2.2. IR spectroscopy and elemental analysis

The identity of the complex was confirmed by IR spectroscopy and elemental analysis, which were both in good agreement with the crystal structure analysis. Selected IR data (KBr, cm^-1): 3598 (s), 3380 (b), 1709 (s), 1627 (m), 1384 (s), 1388 (s), 1333 (s), 1256 (w), 1042 (s), 741 (s), 813 (s), 673 (s), 641 (m), 610 (m), 563 (m), 518 (w). Analysis calculated for C₂₈H₅₆Mn₁₂N₈O₆₀: C 15.83, H 2.66, N 5.28%; found: C 15.92, H 2.73, N 5.33%.

S2.3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The Mn₁₂ cluster is located on a 4 symmetry element at (0.5, 0.25, 0.375). Consequently, a quarter of the Mn₁₂ cluster exists in the asymmetric unit, along with a nitro­methane solvent molecule. The latter has the nitro group disordered and was refined in two parts with their site-occupation factors dependently refined to values of 0.526 (5) and 0.474 (5). All methyl H atoms were allowed to rotate around the vicinal C—C bonds and to ride, with U_iso(H) = 1.5U_eq(C). Water atoms H13A and H13B were located in a difference Fourier map and refined freely.

S3. Results and discussion

Many derivatives of the Mn₁₂ molecule have been synthesized with different bridging groups, including benzoate (Sessoli et al., 1993), and its derivatives (Aubin et al., 1999), tert-butyl acetate (Sun et al., 1998), pivalate, phosphinate (Brockman et al., 2003), sulfonate (Chakov et al., 2003), and di­chloro­acetate (Eppley & Christou, 2002), to name a few. These molecules have all retained similar properties in terms of magnetic character, but have crystallized in a wide variety of symmetries and space groups. There are four main types of symmetry that can be considered when classifying these Mn₁₂ molecules, i.e. S₄, D₂, C₂, and C₁ (Bagai & Christou, 2007). The title compound crystallizes in the tetra­gonal crystal system and has S₄ symmetry similar to the original Mn₁₂ sythesized by Lis (1980).

Further experiments to study Mn₁₂ have included changing the environment of these Mn₁₂ moieties to include partial ligand substitution where the equatorial and axial ligands are different (Soler, Artus et al., 2001; OR Soler, Chandra et al., 2001), single (Tasiopoulos et al., 2004) or multiple reductions of the Mn^III ions in the outer shell of the core (Soler, Artus et al., 2001; OR Soler, Chandra et al., 2001), and attempts to add nitrates to a preformed Mn₁₂ cluster using nitric acid (Artus et al., 2001). Inclusion of nitrate ligands in such a structure has proven difficult resulting in low synthetic yield, likely due to the weak nature of the nitrate ligand compared to carboxyl­ates and other bridging ligands. The title material, however, contains nitrate ligands and crystallizes from a facile procedure.

A search of the Cambridge Structural Database (Version ???; Groom & Allen, 2014) for similar structures yielded only two similar complexes, namely the original [Mn₁₂O₁₂(O₂CMe)₁₆(H₂O)₄] (Lis, 1980) and [Mn₁₂O₁₂(O₂CCH₂^tBu)₁₂(NO₃)₄(H₂O)₄] (Artus et al., 2001). Many other Mn₁₂ derivatives exist, and most can be found in a review article by Bagai & Christou (2009).

Similar to other Mn₁₂ complexes, the title molecule, (I), contains a roughly cubic core of four Mn^IV ions and four µ₄-O^2- ions centered in a ring of eight Mn^III ions bound by eight µ₃-O^2- bridges, as shown in Fig. 1 and 2. The oxidation states of the Mn atoms were determined by bond-length considerations (Table 2), and the observation of Jahn–Teller elongation axes in the Mn^III ions. Atoms Mn1 and Mn2 were both assigned as Mn^III and Mn3 was assigned as an Mn^IV ion, as shown in Fig. 2. The periphery surrounding the core is completed by 12 acetate ligands, four aqua ligands, and four nitrate ligands. As expected, all Mn centers are six-coordinate and all of the acetate and nitrate ligands bridge pairs of Mn centers in a µ₂-κO:κO' fashion.

Similar to other Mn₁₂ derivatives, the title molecule is highly symmetric. However, unlike any other Mn₁₂ molecule, it contains both inter- and intra­molecular hydrogen bonds (Table 3). On the molecular level, water atom H13A inter­acts with atoms O11 and O12 of the neighboring nitrate ligand. The extended structure exhibits hydrogen-bonding inter­actions between water atom H13B and nitrate atom O12^iv of a neighboring molecule, as shown in Fig. 3 [symmetry code: (iv) -y+3/4, x+1/4, z+1/4].

The three-dimensional network mediated by O—H···O hydrogen bonds between the water ligand on one molecule and the nitrate ligand on a neighboring molecule distinguishes this system from any other Mn₁₂ derivative. To our knowledge, this is the first linked network of Mn₁₂ molecules despite the many derivatives previously synthesized (Bagai & Christou, 2009). This type of network, in addition to being structurally fascinating, promises other inter­esting physical properties including higher-level magnetic ordering in the solid state and unique solution dynamics resulting from the labile ligand sphere.

Computing details

Data collection: APEX2 (Bruker, 2013); cell refinement: APEX2 (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXTL2013 (Sheldrick, 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL2013 (Sheldrick, 2015); software used to prepare material for publication: SHELXTL2013 (Sheldrick, 2015).

Figures

	Fig. 1. The structure of the title Mn12 molecule, with methyl H atoms omitted for clarity. Color key: Mn^III green, Mn^IV purple, O red, N blue, C grey and H white.
	Fig. 2. Displacement ellipsoid drawing (40% probability) of the title Mn12 molecule with the reference asymmetric unit labelled. Methyl H atoms and the solvent molecules have been omitted for clarity. [Symmetry codes: (A) y+1/4, -x+3/4, -z+3/4; (B) -y+3/4, x-1/4, -z+3/4; (C) -x+1, -y+1/2, z.]
	Fig. 3. Packing diagram of the Mn12 clusters along the b axis, showing the intermolecular hydrogen-bonding network (drawn as dashed lines).

Dodeca-µ₂-acetato-κ²⁴-O:O'-tetraaquatetra-µ₂-nitro-κ⁸O:O'-octa-µ₃-oxido-tetra-µ₂-oxido-tetramanganese(IV)octamanganese(III) nitromethane tetrasolvate

Crystal data

[Mn12(C2H3O2)12O12(NO3)4(H2O)4]·4CH3NO2	Dx = 2.044 Mg m^−3
Mr = 2124.08	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 9809 reflections
a = 15.7293 (8) Å	θ = 2.0–28.0°
c = 27.9010 (14) Å	µ = 2.24 mm^−1
V = 6903.0 (8) Å^3	T = 100 K
Z = 4	Blocks, brown
F(000) = 4240	0.16 × 0.10 × 0.04 mm

Data collection

Bruker APEX-II DUO diffractometer	3287 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.053
phi and/or ω scans	θmax = 27.5°, θmin = 1.5°
Absorption correction: analytical based on measured indexed crystal faces, Bruker SHELXTL v6.14 (Bruker 2013)	h = −20→20
Tmin = 0.816, Tmax = 0.929	k = −20→20
85988 measured reflections	l = −36→36
3974 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0358P)^2 + 5.382P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3974 reflections	Δρmax = 0.93 e Å^−3
254 parameters	Δρmin = −0.71 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. All H atoms were positioned geometrically (C—H = 0.93/1.00 Å) and allowed to ride with U_iso(H)= 1.2/1.5U_eq(C). Methyl H atoms were allowed to rotate around the corresponding C—C.

The water ligand protons were obtained from a difference Fourier map and refined freely.

The Mn12 cluster methyl protons were refined using AFIX 137 in the least-squares refinement, while the solvent disordered methyl protons were constrained to the calculated positions using AFIX 33. The disorder of the methyl protons is a direct result of the disorder in the NO2 group which was refined in two parts with their site occupation factors dependently refined.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Mn1	0.35701 (2)	0.47156 (2)	0.37492 (2)	0.01492 (8)
Mn2	0.24107 (2)	0.30827 (2)	0.41895 (2)	0.01474 (8)
Mn3	0.41075 (2)	0.26971 (2)	0.41044 (2)	0.01080 (8)
O1	0.42256 (8)	0.26785 (8)	0.34230 (5)	0.0112 (3)
O2	0.34443 (8)	0.36865 (8)	0.40876 (5)	0.0138 (3)
O3	0.46181 (8)	0.44239 (8)	0.34623 (5)	0.0140 (3)
O4	0.25146 (10)	0.51348 (9)	0.40287 (6)	0.0257 (4)
O5	0.17971 (9)	0.40843 (9)	0.43986 (6)	0.0208 (3)
O6	0.13643 (9)	0.24322 (9)	0.42220 (6)	0.0213 (3)
O7	0.17142 (9)	0.10596 (9)	0.41062 (6)	0.0213 (3)
O8	0.27101 (9)	0.28661 (9)	0.49300 (5)	0.0206 (3)
O9	0.40972 (9)	0.26266 (9)	0.47841 (5)	0.0157 (3)
O10	0.28826 (10)	0.42650 (10)	0.30911 (6)	0.0247 (4)
O11	0.19940 (9)	0.33803 (10)	0.34334 (6)	0.0223 (3)
O12	0.20524 (11)	0.34684 (12)	0.26682 (6)	0.0339 (4)
O13	0.41571 (11)	0.54253 (11)	0.43325 (7)	0.0255 (4)
H13A	0.474 (2)	0.558 (2)	0.4331 (12)	0.052 (10)*
H13B	0.4134 (18)	0.5217 (18)	0.4589 (11)	0.033 (9)*
N1	0.23166 (11)	0.37124 (12)	0.30634 (7)	0.0212 (4)
C1	0.19674 (14)	0.48579 (14)	0.43236 (9)	0.0231 (5)
C2	0.14995 (19)	0.55029 (16)	0.46142 (12)	0.0437 (8)
H2A	0.1419	0.6020	0.4424	0.066*
H2B	0.1828	0.5638	0.4903	0.066*
H2C	0.0944	0.5274	0.4707	0.066*
C11	0.12084 (13)	0.16401 (13)	0.42315 (8)	0.0186 (4)
C12	0.03467 (13)	0.13741 (14)	0.44059 (9)	0.0238 (5)
H12A	0.0295	0.0754	0.4385	0.036*
H12B	−0.0092	0.1641	0.4207	0.036*
H12C	0.0274	0.1553	0.4740	0.036*
C21	0.34451 (14)	0.26868 (13)	0.50633 (8)	0.0182 (4)
C22	0.36202 (16)	0.25121 (15)	0.55825 (8)	0.0240 (5)
H22A	0.3342	0.2946	0.5780	0.036*
H22B	0.4235	0.2527	0.5639	0.036*
H22C	0.3398	0.1950	0.5667	0.036*
C31	0.13368 (16)	0.62208 (18)	0.31265 (10)	0.0352 (6)
H31A	0.1204	0.6673	0.2897	0.053*	0.526 (5)
H31B	0.1803	0.6406	0.3335	0.053*	0.526 (5)
H31C	0.1508	0.5707	0.2953	0.053*	0.526 (5)
H31D	0.1559	0.5830	0.3370	0.053*	0.474 (5)
H31E	0.1440	0.5984	0.2807	0.053*	0.474 (5)
H31F	0.1624	0.6771	0.3155	0.053*	0.474 (5)
N32	0.0535 (3)	0.6026 (3)	0.34366 (19)	0.0359 (11)*	0.526 (5)
O33	0.0556 (2)	0.5501 (2)	0.37364 (14)	0.0408 (11)*	0.526 (5)
O34	−0.0101 (3)	0.6413 (3)	0.33603 (19)	0.0645 (15)*	0.526 (5)
N42	0.0467 (3)	0.6330 (3)	0.31944 (19)	0.0293 (11)*	0.474 (5)
O43	0.0154 (3)	0.5940 (3)	0.35468 (18)	0.0464 (13)*	0.474 (5)
O44	0.0055 (3)	0.6782 (3)	0.29394 (18)	0.0540 (15)*	0.474 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.01221 (15)	0.01047 (15)	0.02207 (18)	0.00176 (11)	0.00208 (12)	0.00434 (12)
Mn2	0.01200 (15)	0.01139 (15)	0.02082 (17)	0.00170 (11)	0.00553 (12)	0.00148 (12)
Mn3	0.01111 (14)	0.00945 (14)	0.01184 (15)	0.00102 (11)	0.00147 (11)	0.00041 (11)
O1	0.0093 (6)	0.0134 (7)	0.0109 (7)	−0.0005 (5)	0.0006 (5)	0.0004 (5)
O2	0.0133 (7)	0.0107 (6)	0.0173 (8)	0.0024 (5)	0.0030 (6)	0.0019 (5)
O3	0.0117 (7)	0.0122 (7)	0.0182 (7)	−0.0003 (5)	−0.0001 (6)	0.0041 (6)
O4	0.0209 (8)	0.0152 (7)	0.0409 (10)	0.0060 (6)	0.0112 (7)	0.0065 (7)
O5	0.0191 (8)	0.0157 (7)	0.0277 (9)	0.0037 (6)	0.0084 (6)	0.0012 (6)
O6	0.0147 (7)	0.0160 (7)	0.0332 (9)	0.0015 (6)	0.0079 (7)	0.0028 (7)
O7	0.0143 (7)	0.0166 (7)	0.0331 (9)	−0.0006 (6)	0.0084 (6)	−0.0003 (7)
O8	0.0218 (8)	0.0203 (8)	0.0198 (8)	0.0036 (6)	0.0078 (6)	0.0010 (6)
O9	0.0203 (7)	0.0145 (7)	0.0123 (7)	0.0036 (6)	0.0021 (6)	−0.0002 (6)
O10	0.0213 (8)	0.0270 (8)	0.0257 (9)	−0.0065 (7)	−0.0044 (7)	0.0077 (7)
O11	0.0166 (7)	0.0261 (8)	0.0241 (8)	−0.0021 (6)	0.0000 (6)	0.0067 (7)
O12	0.0314 (10)	0.0464 (11)	0.0239 (9)	−0.0075 (8)	−0.0072 (8)	−0.0001 (8)
O13	0.0265 (9)	0.0212 (8)	0.0288 (10)	0.0035 (7)	−0.0011 (8)	−0.0026 (7)
N1	0.0146 (9)	0.0249 (10)	0.0241 (10)	0.0035 (7)	−0.0031 (8)	0.0034 (8)
C1	0.0193 (11)	0.0185 (11)	0.0315 (13)	0.0042 (8)	0.0050 (9)	0.0014 (9)
C2	0.0451 (16)	0.0210 (12)	0.065 (2)	0.0078 (11)	0.0288 (15)	−0.0027 (13)
C11	0.0140 (10)	0.0191 (10)	0.0227 (12)	0.0003 (8)	0.0028 (8)	0.0036 (9)
C12	0.0146 (10)	0.0202 (11)	0.0368 (14)	0.0013 (8)	0.0089 (10)	0.0073 (10)
C21	0.0267 (11)	0.0107 (9)	0.0170 (11)	0.0001 (8)	0.0067 (9)	−0.0006 (8)
C22	0.0335 (13)	0.0225 (11)	0.0160 (11)	0.0029 (9)	0.0047 (10)	0.0009 (9)
C31	0.0317 (14)	0.0384 (15)	0.0353 (15)	−0.0062 (11)	−0.0001 (11)	−0.0068 (12)

Geometric parameters (Å, º)

Mn1—O2	1.8843 (14)	O8—C21	1.247 (3)
Mn1—O3	1.8891 (14)	O9—C21	1.291 (2)
Mn1—O4	1.9492 (15)	O10—N1	1.247 (2)
Mn1—O7^i	1.9538 (14)	O11—N1	1.263 (2)
Mn1—O13	2.1787 (18)	O12—N1	1.239 (2)
Mn1—O10	2.2458 (16)	O13—H13A	0.95 (3)
Mn2—O3^ii	1.8913 (14)	O13—H13B	0.79 (3)
Mn2—O2	1.9043 (14)	C1—C2	1.493 (3)
Mn2—O5	1.9375 (15)	C2—H2A	0.9800
Mn2—O6	1.9401 (15)	C2—H2B	0.9800
Mn2—O8	2.1463 (16)	C2—H2C	0.9800
Mn2—O11	2.2583 (16)	C11—C12	1.500 (3)
Mn2—Mn3	2.7473 (4)	C12—H12A	0.9800
Mn3—O3^ii	1.8697 (14)	C12—H12B	0.9800
Mn3—O2	1.8742 (13)	C12—H12C	0.9800
Mn3—O1^ii	1.8979 (13)	C21—C22	1.500 (3)
Mn3—O9	1.8998 (14)	C22—H22A	0.9800
Mn3—O1	1.9104 (14)	C22—H22B	0.9800
Mn3—O1^i	1.9154 (13)	C22—H22C	0.9800
Mn3—Mn3^i	2.8361 (5)	C31—N42	1.392 (5)
Mn3—Mn3^ii	2.8361 (5)	C31—N32	1.560 (6)
Mn3—Mn3^iii	2.8753 (6)	C31—H31A	0.9800
O1—Mn3^i	1.8979 (13)	C31—H31B	0.9800
O1—Mn3^ii	1.9154 (13)	C31—H31C	0.9800
O3—Mn3^i	1.8697 (14)	C31—H31D	0.9800
O3—Mn2^i	1.8913 (14)	C31—H31E	0.9800
O4—C1	1.268 (3)	C31—H31F	0.9800
O5—C1	1.263 (3)	N32—O33	1.176 (6)
O6—C11	1.270 (3)	N32—O34	1.191 (8)
O7—C11	1.260 (3)	N42—O44	1.196 (7)
O7—Mn1^ii	1.9538 (14)	N42—O43	1.258 (8)
O2—Mn1—O3	95.47 (6)	O9—Mn3—Mn3^iii	89.76 (4)
O2—Mn1—O4	90.04 (6)	O1—Mn3—Mn3^iii	84.36 (4)
O3—Mn1—O4	174.24 (6)	O1^i—Mn3—Mn3^iii	40.83 (4)
O2—Mn1—O7^i	173.48 (6)	Mn2—Mn3—Mn3^iii	175.026 (9)
O3—Mn1—O7^i	90.09 (6)	Mn3^i—Mn3—Mn3^iii	59.541 (6)
O4—Mn1—O7^i	84.52 (6)	Mn3^ii—Mn3—Mn3^iii	59.540 (6)
O2—Mn1—O13	96.34 (7)	Mn3^i—O1—Mn3	96.27 (6)
O3—Mn1—O13	94.08 (7)	Mn3^i—O1—Mn3^ii	97.88 (6)
O4—Mn1—O13	83.61 (7)	Mn3—O1—Mn3^ii	95.69 (6)
O7^i—Mn1—O13	86.63 (7)	Mn3—O2—Mn1	131.87 (8)
O2—Mn1—O10	95.05 (6)	Mn3—O2—Mn2	93.28 (6)
O3—Mn1—O10	89.83 (6)	Mn1—O2—Mn2	126.37 (7)
O4—Mn1—O10	91.36 (7)	Mn3^i—O3—Mn1	132.68 (7)
O7^i—Mn1—O10	81.54 (6)	Mn3^i—O3—Mn2^i	93.85 (6)
O13—Mn1—O10	167.55 (6)	Mn1—O3—Mn2^i	131.34 (8)
O3^ii—Mn2—O2	83.93 (6)	C1—O4—Mn1	136.19 (14)
O3^ii—Mn2—O5	174.53 (7)	C1—O5—Mn2	128.88 (14)
O2—Mn2—O5	93.71 (6)	C11—O6—Mn2	133.01 (13)
O3^ii—Mn2—O6	93.26 (6)	C11—O7—Mn1^ii	132.72 (14)
O2—Mn2—O6	173.88 (7)	C21—O8—Mn2	121.77 (13)
O5—Mn2—O6	89.55 (6)	C21—O9—Mn3	127.20 (14)
O3^ii—Mn2—O8	88.10 (6)	N1—O10—Mn1	127.92 (14)
O2—Mn2—O8	92.04 (6)	N1—O11—Mn2	137.10 (13)
O5—Mn2—O8	87.05 (6)	Mn1—O13—H13A	122 (2)
O6—Mn2—O8	93.30 (6)	Mn1—O13—H13B	116 (2)
O3^ii—Mn2—O11	96.76 (6)	H13A—O13—H13B	99 (3)
O2—Mn2—O11	90.27 (6)	O12—N1—O10	120.70 (19)
O5—Mn2—O11	88.17 (6)	O12—N1—O11	117.66 (18)
O6—Mn2—O11	84.65 (6)	O10—N1—O11	121.64 (19)
O8—Mn2—O11	174.82 (6)	O5—C1—O4	125.6 (2)
O3^ii—Mn2—Mn3	42.77 (4)	O5—C1—C2	117.4 (2)
O2—Mn2—Mn3	42.93 (4)	O4—C1—C2	117.0 (2)
O5—Mn2—Mn3	133.59 (5)	C1—C2—H2A	109.5
O6—Mn2—Mn3	135.38 (4)	C1—C2—H2B	109.5
O8—Mn2—Mn3	80.50 (4)	H2A—C2—H2B	109.5
O11—Mn2—Mn3	104.29 (4)	C1—C2—H2C	109.5
O3^ii—Mn3—O2	85.36 (6)	H2A—C2—H2C	109.5
O3^ii—Mn3—O1^ii	96.73 (6)	H2B—C2—H2C	109.5
O2—Mn3—O1^ii	175.52 (6)	O7—C11—O6	125.66 (19)
O3^ii—Mn3—O9	93.64 (6)	O7—C11—C12	117.28 (19)
O2—Mn3—O9	93.94 (6)	O6—C11—C12	117.06 (18)
O1^ii—Mn3—O9	89.90 (6)	C11—C12—H12A	109.5
O3^ii—Mn3—O1	88.74 (6)	C11—C12—H12B	109.5
O2—Mn3—O1	92.40 (6)	H12A—C12—H12B	109.5
O1^ii—Mn3—O1	83.69 (6)	C11—C12—H12C	109.5
O9—Mn3—O1	173.39 (6)	H12A—C12—H12C	109.5
O3^ii—Mn3—O1^i	171.95 (6)	H12B—C12—H12C	109.5
O2—Mn3—O1^i	95.44 (6)	O8—C21—O9	125.0 (2)
O1^ii—Mn3—O1^i	81.93 (6)	O8—C21—C22	119.98 (19)
O9—Mn3—O1^i	94.30 (6)	O9—C21—C22	115.05 (19)
O1—Mn3—O1^i	83.23 (6)	C21—C22—H22A	109.5
O3^ii—Mn3—Mn2	43.38 (4)	C21—C22—H22B	109.5
O2—Mn3—Mn2	43.79 (4)	H22A—C22—H22B	109.5
O1^ii—Mn3—Mn2	139.12 (4)	C21—C22—H22C	109.5
O9—Mn3—Mn2	85.31 (4)	H22A—C22—H22C	109.5
O1—Mn3—Mn2	100.60 (4)	H22B—C22—H22C	109.5
O1^i—Mn3—Mn2	138.87 (4)	N32—C31—H31A	109.5
O3^ii—Mn3—Mn3^i	130.01 (5)	N32—C31—H31B	109.5
O2—Mn3—Mn3^i	89.92 (4)	H31A—C31—H31B	109.5
O1^ii—Mn3—Mn3^i	85.70 (4)	N32—C31—H31C	109.5
O9—Mn3—Mn3^i	136.36 (5)	H31A—C31—H31C	109.5
O1—Mn3—Mn3^i	41.70 (4)	H31B—C31—H31C	109.5
O1^i—Mn3—Mn3^i	42.09 (4)	N42—C31—H31D	109.5
Mn2—Mn3—Mn3^i	124.210 (15)	N42—C31—H31E	109.5
O3^ii—Mn3—Mn3^ii	88.34 (4)	H31D—C31—H31E	109.5
O2—Mn3—Mn3^ii	134.35 (5)	N42—C31—H31F	109.5
O1^ii—Mn3—Mn3^ii	42.03 (4)	H31D—C31—H31F	109.5
O9—Mn3—Mn3^ii	131.61 (4)	H31E—C31—H31F	109.5
O1—Mn3—Mn3^ii	42.22 (4)	O33—N32—O34	120.7 (6)
O1^i—Mn3—Mn3^ii	85.38 (4)	O33—N32—C31	120.7 (4)
Mn2—Mn3—Mn3^ii	124.639 (16)	O34—N32—C31	118.6 (5)
Mn3^i—Mn3—Mn3^ii	60.916 (12)	O44—N42—O43	122.8 (5)
O3^ii—Mn3—Mn3^iii	137.92 (4)	O44—N42—C31	121.7 (5)
O2—Mn3—Mn3^iii	136.27 (4)	O43—N42—C31	115.5 (5)
O1^ii—Mn3—Mn3^iii	41.29 (4)

Symmetry codes: (i) y+1/4, −x+3/4, −z+3/4; (ii) −y+3/4, x−1/4, −z+3/4; (iii) −x+1, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13A···O11^i	0.95 (3)	1.94 (3)	2.813 (2)	152 (3)
O13—H13A···O12^i	0.95 (3)	2.39 (3)	3.172 (3)	139 (3)
O13—H13B···O12^iv	0.79 (3)	1.93 (3)	2.713 (3)	171 (3)

Symmetry codes: (i) y+1/4, −x+3/4, −z+3/4; (iv) −y+3/4, x+1/4, z+1/4.