A dodeca­nuclear manganese(II,III) complex of penta­erythritol

The mol­ecule of the title compound, tetra-[mu]₂-acetato-diaquadi-[mu]₂-chloro-tetra­chloro­tetra­kis[[mu]₄-3-hydroxy-2,2-bis­(oxido­meth­yl)propanol­ato]­tetra­methanoldi-[mu]₃-methanolato-di-[mu]₅-oxo-octa­manganese(II)­tetra­manganese(III), [Mn₄^IIIMn₈^II(CH₃O)₂(C₂H₃O₂)₄(C₅H₉O₄)₄Cl₆O₂(CH₄O)₄(H₂O)₂], displays a centre of symmetry. The structure of the {Mn₄^IIIMn₈^IIO₁₈Cl₂}^10- core is composed of three layers and features two oxo ligands binding in a rare [mu]₅-mode.

S1. Comment

Studying the structural aspects of new polynuclear transition metal complexes is of considerable interest because of their potential to act as single-molecule magnets (Gatteschi & Sessoli, 2003; Christou et al., 2000; Sessoli et al., 1993). We are presently exploring the solvothermal reactions of simple transition metal salts with polyalcohol-containing proligands in an effort to synthesize new polynuclear complexes with interesting magnetic properties (Labat et al., 2005; Alley et al., 2006). The complex [Mn^III₄Mn^II ₈(O)₂(Cl)₆(OMe)₂(HPeol)₄(O₂CMe)₄(MeOH)₄ (H₂O)₂], (I) (H₄peol is pentaerythritol), is a neutral mixed-valent species that was synthesized by solvothermal methods (Laye & McInnes, 2004) at 393 K and obtained in high yield (see scheme). The presence of chloro ligands in (I) is due to the decomposition of dichloroethane (Park et al., 2000; Walter et al., 1994; Petrosius et al., 1993) as a result of the high temperature and autogenous pressure. The methanol employed in the reaction as a solvent acts as the source of the methoxide ligand in the complex. Crystals could not be obtained upon changing the composition of the solvent mixture.

Complex (I) crystallizes in the centrosymmetric triclinic space group P1; An ORTEP (Farrugia, 1997) diagram is provided in Fig. 1. The structure of the {Mn^III₄Mn^II₈O₁₈Cl₂}^10- core can be considered to consist of three layers. The central layer has two Mn^III (Mn2 and Mn3) and four Mn^II centers (Mn1 and Mn4–Mn6; Fig. 2) bridged by eight O atoms, while the peripheral layers each contain one Mn^III and two Mn^II centers bridged by five O atoms and one Cl atom. All the manganese (Mn^II/Mn^III) atoms are six coordinate. The three layers are linked through the bridging O and Cl atoms. While the atoms within the central layer are essentially coplanar, the atoms in the two peripheral layers deviate more substantially from planarity.

The two oxo ligands (O9) bind in a rare µ₅ mode, displaying a square-pyramidal geometry (Fig. 2) (Khan et al., 1992; Murugesu et al., 2006) with one long bond (Mn5—O9) at 2.625 (3) Å. Of the four O atoms of the Hpeol^3- ligands, one remains as a pendant alcohol group (i.e. O8), two coordinate in a µ₃ manner (i.e. O5 and O6) and the remaining one (i.e. O7) binds two Mn^II ions in a µ₂ fashion (Fig. 1). Two MeO^- and two Cl^- ligands bridge Mn centers in µ₃ and µ₂ modes, respectively. Two of the acetate ligands contribute O atoms to the core of complex (I), binding in a η¹,η²,µ₂ fashion, while the other two bind in the common syn,syn,µ₂ manner. The peripheral ligation is completed by terminally bound MeOH, H₂O and chloro ligands. The average Mn^II··· Mn^II, Mn^II··· Mn^III and Mn^III··· Mn^III distances are 3.535, 3.365 and 3.035 Å, respectively. Each of the Mn^II ions are coordinated to five O atoms and one Cl atom, in contrast to the Mn^III centers that possess six O atoms in their coordination sphere. The Mn^II ions (Mn1, Mn4, Mn5, Mn6) display an average Mn—O distance of 2.22 (2) Å, with little difference between intra-layer and inter-layer connectivities. The intra- and inter-layer Mn—O distances for the Mn^III ions are in the ranges 1.91 (2)–1.94 (2) Å and 2.16 (2)–2.29 (2) Å respectively. Thus the Jahn–Teller elongated axes of the Mn^III centers are essentially parallel and aligned along the inter-layer vector. The average bridging and terminal Mn^II—Cl distances are 2.48 (1) and 2.44 (1) Å, respectively.

There has recently been a report of a structure of similar formulation and architecture (Murugesu et al., 2006). However, this compound is obtained from an entirely different synthetic route and has no chloro ligands. The Mn centers bridged by Cl atoms in complex (I) are bridged by the O atoms of carboxylate ligands in the literature compound. In addition, while all of the Mn centers in complex (I) are six-coordinate, two of the Mn^II centers in the literature compound are seven-coordinate. Differences in the magnetic behaviour will likely result from these different magnetic exchange pathways. The literature compound displays the slow magnetic relaxation characteristic of a single-molecule magnet and thus it is of interest to probe the magnetic properties of complex (I) in the future.

Related literature

For related literature, see: Alley et al. (2006); Christou et al. (2000); Farrugia (1997); Gatteschi & Sessoli (2003); Khan et al. (1992); Labat et al. (2005); Laye & McInnes (2004); Murugesu et al. (2006); Park et al. (2000); Petrosius et al. (1993); Sessoli et al. (1993); Walter et al. (1994).

S2. Experimental

Mn^III(O₂CMe)₃·2H₂O (0.248 g, 0.90 mmol), pentaerythritol (0.061 g, 0.45 mmol) and 10 ml of an 8:2 v/v dichloroethane–methanol solution were combined in a Teflon-lined solvothermal reaction vessel. The mixture was heated at 393 K for 48 h and then cooled at 2 K h^-1. Brown crystalline blocks coated the walls and bottom of the Teflon vessel (yield 0.090 g, 0.047 mmol, 60%). Elemental analysis calculated for C₃₄H₇₄Cl₆Mn₁₂O₃₄: C 21.51, H 3.93%; found C 21.47, H 3.87%. IR (KBr): 3384 (br, s), 2914 (br), 2868 (m), 1630 (m), 1601 (s), 1552 (s), 1448 (s), 1429 (s), 1356 (m), 1113 (s), 1064 (m), 1012 (s), 989 (m), 686 (m), 649 (s), 580 (vs), 547 (m), 508 (m), 474 (m), 451 (w) cm^-1.

S3. Refinement

H on the hetero atoms were located from difference Fourier maps and were refined with individual isotropic displacement parameters. All other H atoms were constrained at geometrical estimates with isotropic displacement parameters of 1.2–1.5 times those of the parent Catom.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART [OR SAINT??]; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Diamond (Brandenburg, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. An ORTEP-3 (Farrugia, 1997) diagram of complex (I), with labelling of the atoms in the asymmetric unit (except atoms C14, C15, C16 and C17, and the pendant atom O17 of the second Hpeol unit lying at the back in the figure). Displacement ellipsoids are shown at the ??% probability level.
	Fig. 2. A labeled ball and stick diagram of the core of complex (I) (colour code for the online version: Mn^III dark blue, Mn^II light blue, O red, Cl green).

tetra-µ₂-acetato-diaquadi-µ₂-chloro-tetrachlorotetrakis[µ₄– 3-hydroxy-2,2-bis(oxidomethyl)propanolato]tetramethanoldi-µ₅-oxo- octamanganese(II)tetramanganese(III), [Mn^III₄Mn^II₈Cl₆O₂(CH₃O)₂(C₂H₃O₂)₄(C₃H₅O₄)₄(CH₄MeO)₄(H₂O)₂]

Crystal data

[Mn12(CH3O)2(C2H3O2)4(C5H9O4)4Cl6O2(CH4O)4(H2O)2]	Z = 1
Mr = 1898.91	F(000) = 952
Triclinic, P1	Dx = 2.015 Mg m^−3
a = 11.3575 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.6949 (7) Å	Cell parameters from 6015 reflections
c = 13.8332 (8) Å	θ = 2.7–27°
α = 101.753 (1)°	µ = 2.68 mm^−1
β = 107.337 (1)°	T = 130 K
γ = 108.916 (1)°	Cubic, brown
V = 1564.76 (16) Å^3	0.37 × 0.25 × 0.21 mm

Data collection

Bruker SMART APEX CCD area -etector diffractometer	6251 independent reflections
Radiation source: fine-focus sealed tube	5762 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
Detector resolution: 0.3 pixels mm^-1	θmax = 26.4°, θmin = 1.6°
ϕ and ω scans	h = −14→13
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick 1997)	k = −14→12
Tmin = 0.544, Tmax = 0.774	l = −17→16
9180 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.044P)^2 + 1.886P] where P = (Fo^2 + 2Fc^2)/3
6251 reflections	(Δ/σ)max = 0.009
415 parameters	Δρmax = 0.83 e Å^−3
0 restraints	Δρmin = −0.83 e Å^−3

Special details

Experimental. The intensity data for complex I were measured in frames with Increasing ω (width 0.3 °/frame) at a scan speed of 20 s/frame with a Bruker SMART APEX CCD diffractometer equipped with a low temperature device (Oxford Crysostream). The SMART and the SAINT software packagewas used for data acquisition and processing of raw data respectively. The absorption correction was made using SADABS program. Finally, the program generated the reflection file (.hkl file) and the atom list file (.ins file) were used in WinGX suite for structure solution (Farrugia, 1999) and refinement using SHELX (Sheldrick, 1997) set of programs.

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
Mn1	0.12054 (4)	0.25549 (4)	0.40364 (3)	0.01754 (10)
Mn2	−0.07602 (4)	0.04669 (3)	0.17234 (3)	0.01305 (9)
Mn3	0.04107 (4)	−0.09390 (3)	0.03284 (3)	0.01253 (9)
Mn4	0.25138 (4)	0.11067 (4)	0.25377 (3)	0.01571 (9)
Mn5	0.15519 (4)	0.33175 (4)	0.18574 (3)	0.01545 (9)
Mn6	0.32260 (4)	0.17875 (4)	0.02231 (3)	0.01663 (10)
Cl1	0.26893 (7)	0.24419 (7)	0.56562 (5)	0.02924 (16)
Cl2	0.44541 (6)	0.16536 (6)	0.19785 (5)	0.01953 (13)
Cl3	0.19976 (7)	0.55324 (6)	0.27827 (5)	0.02371 (14)
O1	0.1592 (3)	0.4552 (2)	0.46275 (18)	0.0331 (5)
H1	0.181 (4)	0.498 (3)	0.429 (3)	0.032 (10)*
O2	−0.0646 (2)	0.1931 (2)	0.42616 (18)	0.0301 (5)
H21	−0.088 (4)	0.214 (4)	0.479 (3)	0.048 (11)*
H22	−0.120 (4)	0.135 (4)	0.384 (3)	0.037 (11)*
O3	−0.22595 (18)	0.00436 (18)	0.24102 (14)	0.0204 (4)
O4	−0.40081 (19)	−0.14694 (18)	0.09756 (15)	0.0229 (4)
O5	−0.20074 (17)	0.03422 (16)	0.03673 (13)	0.0143 (3)
O6	−0.01677 (17)	0.22940 (16)	0.23279 (13)	0.0147 (3)
O7	−0.00205 (17)	0.26828 (16)	0.03677 (13)	0.0142 (3)
O8	−0.2435 (2)	0.4426 (2)	0.12992 (19)	0.0316 (5)
H8	−0.305 (5)	0.464 (5)	0.126 (4)	0.077 (16)*
O9	0.07810 (17)	0.08493 (16)	0.09593 (13)	0.0138 (3)
O10	0.26057 (17)	0.29429 (17)	0.32112 (14)	0.0169 (4)
O11	0.3720 (2)	0.1135 (2)	0.41404 (16)	0.0247 (4)
H11	0.348 (4)	0.141 (4)	0.455 (3)	0.037 (11)*
O12	0.29894 (18)	0.35074 (18)	0.11315 (14)	0.0212 (4)
O13	0.4653 (2)	0.38462 (19)	0.06301 (17)	0.0273 (4)
O14	0.12364 (17)	0.13253 (16)	−0.09996 (13)	0.0141 (3)
O15	−0.16279 (17)	0.08396 (16)	−0.16663 (13)	0.0147 (3)
O16	−0.06452 (18)	−0.05687 (16)	−0.29779 (14)	0.0154 (3)
O17	−0.1030 (2)	0.26004 (19)	−0.39621 (15)	0.0232 (4)
H17	−0.135 (4)	0.305 (4)	−0.369 (3)	0.053 (12)*
C1	0.1938 (5)	0.5371 (3)	0.5670 (3)	0.0478 (9)
H1A	0.1432	0.5909	0.5622	0.072*
H1B	0.2911	0.5916	0.5992	0.072*
H1C	0.1710	0.4853	0.6116	0.072*
C2	−0.3489 (3)	−0.0765 (3)	0.1936 (2)	0.0193 (5)
C3	−0.4354 (3)	−0.0866 (3)	0.2584 (2)	0.0285 (6)
H3A	−0.3860	−0.0903	0.3283	0.043*
H3B	−0.5194	−0.1645	0.2199	0.043*
H3C	−0.4569	−0.0115	0.2692	0.043*
C4	−0.2795 (2)	0.1094 (2)	0.0326 (2)	0.0163 (5)
H4A	−0.3462	0.0777	0.0641	0.020*
H4B	−0.3306	0.0959	−0.0435	0.020*
C5	−0.1962 (2)	0.2527 (2)	0.0915 (2)	0.0156 (5)
C6	−0.1182 (2)	0.2810 (2)	0.2112 (2)	0.0161 (5)
H6A	−0.0735	0.3750	0.2475	0.019*
H6B	−0.1835	0.2449	0.2426	0.019*
C7	−0.1068 (2)	0.3123 (2)	0.0348 (2)	0.0157 (5)
H7A	−0.1652	0.2929	−0.0410	0.019*
H7B	−0.0644	0.4066	0.0693	0.019*
C8	−0.3030 (3)	0.3081 (2)	0.0808 (2)	0.0199 (5)
H8A	−0.3583	0.2859	0.0038	0.024*
H8B	−0.3640	0.2688	0.1145	0.024*
C9	0.3950 (4)	0.3924 (4)	0.3843 (3)	0.0526 (10)
H9A	0.4383	0.3696	0.4456	0.079*
H9B	0.3898	0.4744	0.4105	0.079*
H9C	0.4483	0.4002	0.3400	0.079*
C10	0.5157 (3)	0.1611 (4)	0.4675 (3)	0.0437 (9)
H10A	0.5382	0.1491	0.5377	0.065*
H10B	0.5571	0.2526	0.4773	0.065*
H10C	0.5503	0.1143	0.4241	0.065*
C11	0.4006 (3)	0.4271 (3)	0.1095 (2)	0.0233 (6)
C12	0.4462 (3)	0.5682 (3)	0.1578 (3)	0.0354 (7)
H12A	0.4997	0.6130	0.1224	0.053*
H12B	0.5019	0.5958	0.2346	0.053*
H12C	0.3671	0.5883	0.1483	0.053*
C13	0.1234 (3)	0.2220 (2)	−0.1581 (2)	0.0163 (5)
H13A	0.1980	0.2355	−0.1835	0.020*
H13B	0.1412	0.3054	−0.1084	0.020*
C14	−0.0089 (3)	0.1780 (2)	−0.25411 (19)	0.0157 (5)
C15	−0.1262 (3)	0.1748 (2)	−0.2192 (2)	0.0169 (5)
H15A	−0.1010	0.2613	−0.1703	0.020*
H15B	−0.2067	0.1558	−0.2836	0.020*
C16	−0.0395 (3)	0.0507 (2)	−0.3365 (2)	0.0176 (5)
H16A	−0.1198	0.0310	−0.4013	0.021*
H16B	0.0380	0.0618	−0.3581	0.021*
C17	0.0155 (3)	0.2813 (3)	−0.3079 (2)	0.0198 (5)
H17A	0.0466	0.3661	−0.2539	0.024*
H17B	0.0883	0.2830	−0.3337	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0201 (2)	0.0172 (2)	0.01429 (19)	0.00764 (16)	0.00734 (16)	0.00249 (15)
Mn2	0.01410 (19)	0.01237 (18)	0.01235 (18)	0.00543 (15)	0.00551 (15)	0.00303 (14)
Mn3	0.01419 (19)	0.01247 (18)	0.01199 (18)	0.00633 (15)	0.00579 (15)	0.00381 (14)
Mn4	0.0159 (2)	0.01481 (19)	0.01600 (19)	0.00637 (16)	0.00664 (16)	0.00364 (15)
Mn5	0.01465 (19)	0.01623 (19)	0.01530 (19)	0.00622 (16)	0.00662 (15)	0.00399 (15)
Mn6	0.0168 (2)	0.01477 (19)	0.01622 (19)	0.00571 (16)	0.00574 (16)	0.00343 (15)
Cl1	0.0322 (4)	0.0393 (4)	0.0172 (3)	0.0190 (3)	0.0074 (3)	0.0077 (3)
Cl2	0.0159 (3)	0.0227 (3)	0.0199 (3)	0.0074 (2)	0.0070 (2)	0.0076 (2)
Cl3	0.0285 (3)	0.0175 (3)	0.0276 (3)	0.0107 (3)	0.0146 (3)	0.0050 (3)
O1	0.0557 (15)	0.0223 (11)	0.0270 (11)	0.0163 (11)	0.0233 (11)	0.0083 (9)
O2	0.0246 (11)	0.0370 (13)	0.0173 (11)	0.0046 (10)	0.0102 (9)	−0.0030 (10)
O3	0.0201 (10)	0.0216 (9)	0.0194 (9)	0.0073 (8)	0.0105 (8)	0.0050 (8)
O4	0.0192 (9)	0.0235 (10)	0.0215 (10)	0.0041 (8)	0.0092 (8)	0.0047 (8)
O5	0.0148 (8)	0.0137 (8)	0.0144 (8)	0.0070 (7)	0.0056 (7)	0.0033 (7)
O6	0.0151 (8)	0.0142 (8)	0.0150 (8)	0.0070 (7)	0.0059 (7)	0.0039 (7)
O7	0.0133 (8)	0.0137 (8)	0.0172 (9)	0.0067 (7)	0.0071 (7)	0.0046 (7)
O8	0.0235 (11)	0.0207 (10)	0.0465 (13)	0.0115 (9)	0.0113 (10)	0.0027 (9)
O9	0.0148 (8)	0.0142 (8)	0.0140 (8)	0.0072 (7)	0.0066 (7)	0.0044 (7)
O10	0.0148 (9)	0.0167 (9)	0.0167 (9)	0.0053 (7)	0.0052 (7)	0.0040 (7)
O11	0.0247 (11)	0.0295 (11)	0.0192 (10)	0.0127 (9)	0.0074 (9)	0.0061 (9)
O12	0.0184 (9)	0.0230 (10)	0.0179 (9)	0.0122 (8)	0.0038 (8)	−0.0024 (8)
O13	0.0259 (11)	0.0254 (10)	0.0354 (12)	0.0105 (9)	0.0181 (9)	0.0104 (9)
O14	0.0163 (9)	0.0129 (8)	0.0142 (8)	0.0060 (7)	0.0066 (7)	0.0057 (7)
O15	0.0158 (9)	0.0151 (8)	0.0136 (8)	0.0067 (7)	0.0056 (7)	0.0053 (7)
O16	0.0174 (9)	0.0149 (8)	0.0146 (8)	0.0070 (7)	0.0064 (7)	0.0052 (7)
O17	0.0329 (11)	0.0276 (10)	0.0174 (9)	0.0196 (9)	0.0119 (8)	0.0089 (8)
C1	0.079 (3)	0.0277 (17)	0.0349 (19)	0.0176 (18)	0.0290 (19)	0.0033 (15)
C2	0.0214 (13)	0.0191 (13)	0.0228 (14)	0.0110 (11)	0.0110 (11)	0.0101 (11)
C3	0.0284 (15)	0.0323 (16)	0.0295 (15)	0.0134 (13)	0.0161 (13)	0.0110 (13)
C4	0.0139 (12)	0.0170 (12)	0.0191 (12)	0.0080 (10)	0.0067 (10)	0.0051 (10)
C5	0.0151 (12)	0.0150 (12)	0.0180 (12)	0.0080 (10)	0.0074 (10)	0.0038 (10)
C6	0.0159 (12)	0.0172 (12)	0.0180 (12)	0.0096 (10)	0.0079 (10)	0.0050 (10)
C7	0.0166 (12)	0.0161 (12)	0.0185 (12)	0.0097 (10)	0.0081 (10)	0.0071 (10)
C8	0.0181 (13)	0.0189 (13)	0.0246 (14)	0.0101 (11)	0.0092 (11)	0.0055 (11)
C9	0.053 (2)	0.050 (2)	0.049 (2)	0.022 (2)	0.015 (2)	0.0134 (19)
C10	0.0293 (17)	0.065 (2)	0.0312 (18)	0.0205 (17)	0.0065 (14)	0.0123 (17)
C11	0.0317 (16)	0.0240 (14)	0.0176 (13)	0.0161 (13)	0.0085 (12)	0.0075 (11)
C12	0.0396 (18)	0.0256 (16)	0.0419 (19)	0.0101 (14)	0.0230 (16)	0.0083 (14)
C13	0.0194 (13)	0.0139 (12)	0.0178 (12)	0.0071 (10)	0.0090 (10)	0.0069 (10)
C14	0.0203 (13)	0.0150 (12)	0.0139 (12)	0.0076 (10)	0.0085 (10)	0.0054 (10)
C15	0.0201 (13)	0.0182 (12)	0.0177 (12)	0.0104 (11)	0.0095 (10)	0.0091 (10)
C16	0.0231 (13)	0.0165 (12)	0.0156 (12)	0.0083 (11)	0.0093 (10)	0.0071 (10)
C17	0.0237 (14)	0.0199 (13)	0.0186 (13)	0.0097 (11)	0.0100 (11)	0.0081 (11)

Geometric parameters (Å, º)

Mn1—O2	2.131 (2)	O8—H8	0.81 (5)
Mn1—O1	2.158 (2)	O9—Mn3^i	1.9358 (17)
Mn1—O10	2.2054 (18)	O10—C9	1.439 (4)
Mn1—O16^i	2.2462 (18)	O11—C10	1.430 (4)
Mn1—O6	2.3049 (17)	O11—H11	0.76 (4)
Mn1—Cl1	2.4275 (8)	O12—C11	1.231 (4)
Mn1—Mn2	3.1953 (5)	O13—C11	1.261 (3)
Mn2—O16^i	1.9275 (17)	O14—C13	1.444 (3)
Mn2—O5	1.9282 (17)	O14—Mn2^i	1.9431 (17)
Mn2—O6	1.9293 (17)	O14—Mn3^i	2.2855 (17)
Mn2—O14^i	1.9431 (17)	O15—C15	1.428 (3)
Mn2—O3	2.1580 (18)	O15—Mn3^i	1.9060 (17)
Mn2—O9	2.2735 (16)	O15—Mn4^i	2.0787 (17)
Mn2—Mn3^i	3.1123 (5)	O16—C16	1.444 (3)
Mn2—Mn3	3.1384 (5)	O16—Mn2^i	1.9275 (17)
Mn2—Mn6^i	3.1419 (5)	O16—Mn1^i	2.2462 (18)
Mn3—O15^i	1.9060 (17)	O16—Mn4^i	2.3089 (17)
Mn3—O7^i	1.9085 (17)	O17—C17	1.430 (3)
Mn3—O9^i	1.9358 (17)	O17—H17	0.82 (4)
Mn3—O9	1.9442 (17)	C1—H1A	0.9800
Mn3—O5^i	2.2793 (17)	C1—H1B	0.9800
Mn3—O14^i	2.2855 (17)	C1—H1C	0.9800
Mn3—Mn3^i	2.8558 (7)	C2—C3	1.509 (4)
Mn3—Mn2^i	3.1123 (5)	C3—H3A	0.9800
Mn3—Mn4	3.1201 (5)	C3—H3B	0.9800
Mn3—Mn5^i	3.2226 (5)	C3—H3C	0.9800
Mn4—O15^i	2.0787 (17)	C4—C5	1.524 (3)
Mn4—O10	2.1147 (18)	C4—H4A	0.9900
Mn4—O11	2.219 (2)	C4—H4B	0.9900
Mn4—O16^i	2.3089 (17)	C5—C6	1.533 (3)
Mn4—O9	2.3491 (17)	C5—C8	1.535 (3)
Mn4—Cl2	2.4834 (7)	C5—C7	1.540 (3)
Mn5—O7	2.0763 (17)	C6—H6A	0.9900
Mn5—O10	2.1143 (18)	C6—H6B	0.9900
Mn5—O12	2.1344 (19)	C7—H7A	0.9900
Mn5—O6	2.2869 (17)	C7—H7B	0.9900
Mn5—Cl3	2.4531 (7)	C8—H8A	0.9900
Mn5—Mn3^i	3.2226 (5)	C8—H8B	0.9900
Mn6—O4^i	2.1256 (19)	C9—H9A	0.9800
Mn6—O14	2.1948 (17)	C9—H9B	0.9800
Mn6—O5^i	2.2470 (17)	C9—H9C	0.9800
Mn6—O13	2.262 (2)	C10—H10A	0.9800
Mn6—O12	2.2845 (18)	C10—H10B	0.9800
Mn6—Cl2	2.4788 (7)	C10—H10C	0.9800
Mn6—C11	2.635 (3)	C11—C12	1.493 (4)
Mn6—Mn2^i	3.1419 (5)	C12—H12A	0.9800
O1—C1	1.416 (4)	C12—H12B	0.9800
O1—H1	0.78 (4)	C12—H12C	0.9800
O2—H21	0.87 (4)	C13—C14	1.522 (3)
O2—H22	0.74 (4)	C13—H13A	0.9900
O3—C2	1.273 (3)	C13—H13B	0.9900
O4—C2	1.250 (3)	C14—C17	1.537 (3)
O4—Mn6^i	2.1256 (19)	C14—C16	1.540 (3)
O5—C4	1.441 (3)	C14—C15	1.538 (3)
O5—Mn6^i	2.2470 (17)	C15—H15A	0.9900
O5—Mn3^i	2.2793 (17)	C15—H15B	0.9900
O6—C6	1.449 (3)	C16—H16A	0.9900
O7—C7	1.437 (3)	C16—H16B	0.9900
O7—Mn3^i	1.9085 (17)	C17—H17A	0.9900
O8—C8	1.412 (3)	C17—H17B	0.9900
O2—Mn1—O1	92.89 (9)	O4^i—Mn6—C11	109.11 (8)
O2—Mn1—O10	159.70 (8)	O14—Mn6—C11	99.32 (8)
O1—Mn1—O10	92.58 (8)	O5^i—Mn6—C11	161.61 (8)
O2—Mn1—O16^i	91.04 (8)	O13—Mn6—C11	28.57 (8)
O1—Mn1—O16^i	163.94 (8)	O12—Mn6—C11	27.85 (8)
O10—Mn1—O16^i	78.71 (6)	Cl2—Mn6—C11	90.86 (6)
O2—Mn1—O6	83.91 (8)	O4^i—Mn6—Mn2^i	76.01 (5)
O1—Mn1—O6	92.78 (8)	O14—Mn6—Mn2^i	37.69 (4)
O10—Mn1—O6	76.31 (6)	O5^i—Mn6—Mn2^i	37.50 (4)
O16^i—Mn1—O6	72.15 (6)	O13—Mn6—Mn2^i	139.95 (6)
O2—Mn1—Cl1	99.49 (7)	O12—Mn6—Mn2^i	121.28 (5)
O1—Mn1—Cl1	98.13 (7)	Cl2—Mn6—Mn2^i	126.37 (2)
O10—Mn1—Cl1	99.07 (5)	C11—Mn6—Mn2^i	136.79 (6)
O16^i—Mn1—Cl1	96.57 (5)	Mn6—Cl2—Mn4	96.50 (2)
O6—Mn1—Cl1	168.36 (5)	C1—O1—Mn1	131.5 (2)
O2—Mn1—Mn2	80.12 (7)	C1—O1—H1	108 (3)
O1—Mn1—Mn2	129.32 (6)	Mn1—O1—H1	117 (3)
O10—Mn1—Mn2	81.30 (5)	Mn1—O2—H21	134 (3)
O16^i—Mn1—Mn2	36.49 (4)	Mn1—O2—H22	116 (3)
O6—Mn1—Mn2	36.76 (4)	H21—O2—H22	110 (4)
Cl1—Mn1—Mn2	132.54 (2)	C2—O3—Mn2	127.09 (16)
O16^i—Mn2—O5	172.17 (7)	C2—O4—Mn6^i	133.62 (17)
O16^i—Mn2—O6	88.05 (7)	C4—O5—Mn2	120.68 (14)
O5—Mn2—O6	93.85 (7)	C4—O5—Mn6^i	114.78 (14)
O16^i—Mn2—O14^i	93.43 (7)	Mn2—O5—Mn6^i	97.32 (7)
O5—Mn2—O14^i	83.78 (7)	C4—O5—Mn3^i	113.58 (14)
O6—Mn2—O14^i	172.85 (7)	Mn2—O5—Mn3^i	95.05 (7)
O16^i—Mn2—O3	93.11 (7)	Mn6^i—O5—Mn3^i	113.14 (7)
O5—Mn2—O3	94.38 (7)	C6—O6—Mn2	117.81 (14)
O6—Mn2—O3	92.99 (7)	C6—O6—Mn5	110.59 (13)
O14^i—Mn2—O3	93.92 (7)	Mn2—O6—Mn5	109.00 (7)
O16^i—Mn2—O9	87.66 (7)	C6—O6—Mn1	123.27 (14)
O5—Mn2—O9	84.79 (7)	Mn2—O6—Mn1	97.59 (7)
O6—Mn2—O9	88.70 (7)	Mn5—O6—Mn1	95.82 (6)
O14^i—Mn2—O9	84.37 (7)	C7—O7—Mn3^i	122.29 (15)
O3—Mn2—O9	178.16 (7)	C7—O7—Mn5	115.36 (14)
O16^i—Mn2—Mn3^i	125.80 (5)	Mn3^i—O7—Mn5	107.87 (8)
O5—Mn2—Mn3^i	46.85 (5)	C8—O8—H8	106 (4)
O6—Mn2—Mn3^i	87.24 (5)	Mn3^i—O9—Mn3	94.79 (7)
O14^i—Mn2—Mn3^i	86.22 (5)	Mn3^i—O9—Mn2	95.02 (7)
O3—Mn2—Mn3^i	141.05 (5)	Mn3—O9—Mn2	95.85 (7)
O9—Mn2—Mn3^i	38.29 (4)	Mn3^i—O9—Mn4	169.31 (9)
O16^i—Mn2—Mn3	87.77 (5)	Mn3—O9—Mn4	92.74 (6)
O5—Mn2—Mn3	85.00 (5)	Mn2—O9—Mn4	91.74 (6)
O6—Mn2—Mn3	126.70 (5)	C9—O10—Mn5	113.43 (19)
O14^i—Mn2—Mn3	46.46 (5)	C9—O10—Mn4	115.00 (19)
O3—Mn2—Mn3	140.29 (5)	Mn5—O10—Mn4	103.13 (8)
O9—Mn2—Mn3	38.04 (4)	C9—O10—Mn1	116.66 (19)
Mn3^i—Mn2—Mn3	54.369 (13)	Mn5—O10—Mn1	104.14 (7)
O16^i—Mn2—Mn6^i	134.68 (5)	Mn4—O10—Mn1	102.86 (7)
O5—Mn2—Mn6^i	45.18 (5)	C10—O11—Mn4	128.88 (19)
O6—Mn2—Mn6^i	136.48 (5)	C10—O11—H11	106 (3)
O14^i—Mn2—Mn6^i	43.68 (5)	Mn4—O11—H11	109 (3)
O3—Mn2—Mn6^i	79.15 (5)	C11—O12—Mn5	144.22 (18)
O9—Mn2—Mn6^i	99.13 (5)	C11—O12—Mn6	92.09 (16)
Mn3^i—Mn2—Mn6^i	74.311 (13)	Mn5—O12—Mn6	122.72 (9)
Mn3—Mn2—Mn6^i	72.476 (13)	C11—O13—Mn6	92.38 (17)
O16^i—Mn2—Mn1	43.87 (5)	C13—O14—Mn2^i	121.48 (14)
O5—Mn2—Mn1	139.25 (5)	C13—O14—Mn6	114.15 (14)
O6—Mn2—Mn1	45.64 (5)	Mn2^i—O14—Mn6	98.62 (7)
O14^i—Mn2—Mn1	136.97 (5)	C13—O14—Mn3^i	113.18 (13)
O3—Mn2—Mn1	85.20 (5)	Mn2^i—O14—Mn3^i	95.50 (7)
O9—Mn2—Mn1	96.51 (5)	Mn6—O14—Mn3^i	111.90 (7)
Mn3^i—Mn2—Mn1	120.183 (15)	C15—O15—Mn3^i	122.25 (15)
Mn3—Mn2—Mn1	120.145 (15)	C15—O15—Mn4^i	119.28 (14)
Mn6^i—Mn2—Mn1	164.236 (16)	Mn3^i—O15—Mn4^i	102.99 (8)
O15^i—Mn3—O7^i	94.23 (7)	C16—O16—Mn2^i	118.13 (15)
O15^i—Mn3—O9^i	173.88 (7)	C16—O16—Mn1^i	121.67 (14)
O7^i—Mn3—O9^i	91.88 (7)	Mn2^i—O16—Mn1^i	99.63 (7)
O15^i—Mn3—O9	88.67 (7)	C16—O16—Mn4^i	115.05 (14)
O7^i—Mn3—O9	176.80 (7)	Mn2^i—O16—Mn4^i	102.76 (7)
O9^i—Mn3—O9	85.21 (7)	Mn1^i—O16—Mn4^i	95.73 (7)
O15^i—Mn3—O5^i	95.52 (7)	C17—O17—H17	103 (3)
O7^i—Mn3—O5^i	88.29 (7)	O1—C1—H1A	109.5
O9^i—Mn3—O5^i	84.46 (7)	O1—C1—H1B	109.5
O9—Mn3—O5^i	90.10 (7)	H1A—C1—H1B	109.5
O15^i—Mn3—O14^i	88.03 (7)	O1—C1—H1C	109.5
O7^i—Mn3—O14^i	97.41 (7)	H1A—C1—H1C	109.5
O9^i—Mn3—O14^i	91.38 (6)	H1B—C1—H1C	109.5
O9—Mn3—O14^i	84.01 (6)	O4—C2—O3	123.8 (2)
O5^i—Mn3—O14^i	173.06 (6)	O4—C2—C3	119.0 (2)
O15^i—Mn3—Mn3^i	131.16 (5)	O3—C2—C3	117.2 (2)
O7^i—Mn3—Mn3^i	134.59 (5)	C2—C3—H3A	109.5
O9^i—Mn3—Mn3^i	42.72 (5)	C2—C3—H3B	109.5
O9—Mn3—Mn3^i	42.49 (5)	H3A—C3—H3B	109.5
O5^i—Mn3—Mn3^i	86.31 (4)	C2—C3—H3C	109.5
O14^i—Mn3—Mn3^i	86.87 (4)	H3A—C3—H3C	109.5
O15^i—Mn3—Mn2^i	133.62 (5)	H3B—C3—H3C	109.5
O7^i—Mn3—Mn2^i	85.74 (5)	O5—C4—C5	114.3 (2)
O9^i—Mn3—Mn2^i	46.69 (5)	O5—C4—H4A	108.7
O9—Mn3—Mn2^i	91.29 (5)	C5—C4—H4A	108.7
O5^i—Mn3—Mn2^i	38.11 (4)	O5—C4—H4B	108.7
O14^i—Mn3—Mn2^i	138.07 (4)	C5—C4—H4B	108.7
Mn3^i—Mn3—Mn2^i	63.282 (14)	H4A—C4—H4B	107.6
O15^i—Mn3—Mn4	40.48 (5)	C4—C5—C6	111.5 (2)
O7^i—Mn3—Mn4	133.91 (5)	C4—C5—C8	103.8 (2)
O9^i—Mn3—Mn4	133.46 (5)	C6—C5—C8	108.1 (2)
O9—Mn3—Mn4	48.77 (5)	C4—C5—C7	111.3 (2)
O5^i—Mn3—Mn4	88.54 (4)	C6—C5—C7	113.9 (2)
O14^i—Mn3—Mn4	90.32 (4)	C8—C5—C7	107.7 (2)
Mn3^i—Mn3—Mn4	91.005 (18)	O6—C6—C5	113.95 (19)
Mn2^i—Mn3—Mn4	117.226 (15)	O6—C6—H6A	108.8
O15^i—Mn3—Mn2	85.11 (5)	C5—C6—H6A	108.8
O7^i—Mn3—Mn2	135.44 (5)	O6—C6—H6B	108.8
O9^i—Mn3—Mn2	90.67 (5)	C5—C6—H6B	108.8
O9—Mn3—Mn2	46.11 (5)	H6A—C6—H6B	107.7
O5^i—Mn3—Mn2	136.20 (4)	O7—C7—C5	114.29 (19)
O14^i—Mn3—Mn2	38.04 (4)	O7—C7—H7A	108.7
Mn3^i—Mn3—Mn2	62.349 (14)	C5—C7—H7A	108.7
Mn2^i—Mn3—Mn2	125.631 (13)	O7—C7—H7B	108.7
Mn4—Mn3—Mn2	64.040 (12)	C5—C7—H7B	108.7
O15^i—Mn3—Mn5^i	131.56 (5)	H7A—C7—H7B	107.6
O7^i—Mn3—Mn5^i	37.82 (5)	O8—C8—C5	111.9 (2)
O9^i—Mn3—Mn5^i	54.54 (5)	O8—C8—H8A	109.2
O9—Mn3—Mn5^i	139.47 (5)	C5—C8—H8A	109.2
O5^i—Mn3—Mn5^i	90.43 (4)	O8—C8—H8B	109.2
O14^i—Mn3—Mn5^i	91.67 (4)	C5—C8—H8B	109.2
Mn3^i—Mn3—Mn5^i	97.133 (18)	H8A—C8—H8B	107.9
Mn2^i—Mn3—Mn5^i	65.728 (12)	O10—C9—H9A	109.5
Mn4—Mn3—Mn5^i	171.715 (16)	O10—C9—H9B	109.5
Mn2—Mn3—Mn5^i	121.374 (15)	H9A—C9—H9B	109.5
O15^i—Mn4—O10	157.54 (7)	O10—C9—H9C	109.5
O15^i—Mn4—O11	101.40 (7)	H9A—C9—H9C	109.5
O10—Mn4—O11	91.22 (7)	H9B—C9—H9C	109.5
O15^i—Mn4—O16^i	82.70 (6)	O11—C10—H10A	109.5
O10—Mn4—O16^i	79.18 (7)	O11—C10—H10B	109.5
O11—Mn4—O16^i	88.23 (7)	H10A—C10—H10B	109.5
O15^i—Mn4—O9	74.57 (6)	O11—C10—H10C	109.5
O10—Mn4—O9	88.61 (6)	H10A—C10—H10C	109.5
O11—Mn4—O9	165.64 (7)	H10B—C10—H10C	109.5
O16^i—Mn4—O9	77.63 (6)	O12—C11—O13	119.1 (3)
O15^i—Mn4—Cl2	96.09 (5)	O12—C11—C12	120.9 (3)
O10—Mn4—Cl2	101.46 (5)	O13—C11—C12	120.0 (3)
O11—Mn4—Cl2	94.23 (6)	O12—C11—Mn6	60.06 (14)
O16^i—Mn4—Cl2	177.43 (5)	O13—C11—Mn6	59.06 (14)
O9—Mn4—Cl2	99.87 (4)	C12—C11—Mn6	179.0 (2)
O15^i—Mn4—Mn3	36.53 (5)	C11—C12—H12A	109.5
O10—Mn4—Mn3	126.68 (5)	C11—C12—H12B	109.5
O11—Mn4—Mn3	137.60 (6)	H12A—C12—H12B	109.5
O16^i—Mn4—Mn3	82.13 (4)	C11—C12—H12C	109.5
O9—Mn4—Mn3	38.49 (4)	H12A—C12—H12C	109.5
Cl2—Mn4—Mn3	95.54 (2)	H12B—C12—H12C	109.5
O7—Mn5—O10	150.12 (7)	O14—C13—C14	113.61 (19)
O7—Mn5—O12	91.04 (7)	O14—C13—H13A	108.8
O10—Mn5—O12	97.71 (7)	C14—C13—H13A	108.8
O7—Mn5—O6	82.55 (6)	O14—C13—H13B	108.8
O10—Mn5—O6	78.49 (6)	C14—C13—H13B	108.8
O12—Mn5—O6	157.49 (7)	H13A—C13—H13B	107.7
O7—Mn5—Cl3	107.96 (5)	C13—C14—C17	105.1 (2)
O10—Mn5—Cl3	97.51 (5)	C13—C14—C16	111.2 (2)
O12—Mn5—Cl3	104.27 (5)	C17—C14—C16	107.32 (19)
O6—Mn5—Cl3	98.24 (5)	C13—C14—C15	111.8 (2)
O7—Mn5—Mn3^i	34.31 (5)	C17—C14—C15	107.4 (2)
O10—Mn5—Mn3^i	118.35 (5)	C16—C14—C15	113.5 (2)
O12—Mn5—Mn3^i	83.46 (5)	O15—C15—C14	115.27 (19)
O6—Mn5—Mn3^i	79.11 (4)	O15—C15—H15A	108.5
Cl3—Mn5—Mn3^i	142.23 (2)	C14—C15—H15A	108.5
O4^i—Mn6—O14	91.20 (7)	O15—C15—H15B	108.5
O4^i—Mn6—O5^i	87.23 (7)	C14—C15—H15B	108.5
O14—Mn6—O5^i	71.16 (6)	H15A—C15—H15B	107.5
O4^i—Mn6—O13	82.58 (7)	O16—C16—C14	114.21 (19)
O14—Mn6—O13	111.03 (7)	O16—C16—H16A	108.7
O5^i—Mn6—O13	169.59 (7)	C14—C16—H16A	108.7
O4^i—Mn6—O12	134.00 (7)	O16—C16—H16B	108.7
O14—Mn6—O12	85.85 (6)	C14—C16—H16B	108.7
O5^i—Mn6—O12	133.81 (7)	H16A—C16—H16B	107.6
O13—Mn6—O12	56.41 (7)	O17—C17—C14	112.8 (2)
O4^i—Mn6—Cl2	116.35 (6)	O17—C17—H17A	109.0
O14—Mn6—Cl2	145.68 (5)	C14—C17—H17A	109.0
O5^i—Mn6—Cl2	89.19 (5)	O17—C17—H17B	109.0
O13—Mn6—Cl2	93.43 (6)	C14—C17—H17B	109.0
O12—Mn6—Cl2	88.42 (5)	H17A—C17—H17B	107.8

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl3	0.78 (4)	2.35 (4)	3.097 (2)	159 (3)
O2—H21···O17^ii	0.87 (4)	1.77 (4)	2.630 (3)	169 (4)
O2—H22···O3	0.74 (4)	1.96 (4)	2.658 (3)	158 (4)
O8—H8···O13^iii	0.81 (5)	2.27 (5)	2.952 (3)	142 (5)
O11—H11···Cl1	0.76 (4)	2.32 (4)	3.069 (2)	172 (4)
O17—H17···Cl3^iv	0.82 (4)	2.32 (4)	3.132 (2)	173 (4)

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