A penta­nuclear bimetallic complex of manganese(II) and aluminium(III) ions: tetra-μ₂-iodido-iodidobis­(μ₃-2-methoxy­ethano­lato)bis­(μ₂-2-methoxy­ethano­lato)dimeth­yl(tetra­hydro­furan-κO)aluminium(III)tetra­manganese(II)

The mol­ecule of the title compound, [Mn₄Al(CH₃)₂(C₃H₇O₂)₄I₅(C₄H₈O)], contains one Al^III and four Mn^II ions. Two Mn atoms are five-coordinate in the form of a trigonal bipyramid or a square pyramid. The two other Mn atoms are six-­coordinate with an octa­hedral geometry. The four­coordinate Al atom is linked to the manganese core by μ-O_alkoxo bridges, forming an almost planar five-membered ring.

S1. Comment

Alkylaluminum alkoxides have been investigated as components of Ziegler–Natta catalyst systems (Lin et al., 1999; Rhine et al., 1999; Sobota, 2004; Lewinski et al., 2005). To date, several heterometallic aluminium complexes have been synthesized and characterized (Evans et al., 1998; Sobota et al., 2000, 2002; Utko et al., 2004; Jerzykiewicz et al., 2006). In continuation of our systematic study in this field, a new heterometallic aluminium complex with functional alcohols has been prepared. The title compound, (I), crystallizes in the centrosymmetric space group P2₁/c. The molecular structure of (I) is shown in Fig. 1, and selected bond lengths and angles are given in Table 1.

The crystal structure consists of a tetranuclear manganese(II) unit linked to an Al(CH₃)₂ group. In the tetramer, there are two types of Mn atoms [five-coordinate (T5) Mn1 and Mn2, and six-coordinate (T6) Mn3 and Mn4], linked by µ₃-O_alkoxo and µ-I bridges. The Al atom is connected to the manganese core by µ-O_alkoxo bridges, forming an almost planar Al1/O31/Mn3/Mn4/O41 system[the largest deviation of atoms from the mean plane is 0.014 (2) Å]. This planar arrangement of a five-membered trimetallic ring containing aluminium is comparable to that found in a chloro analogue, [Mn₃Al(µ₃-OCH₂CH₂OCH₃)(µ-Cl)₃(µ-OCH₂CH₂OCH₃)₂(THF)₂(CH₃)₂Cl] (Jerzykiewicz et al., 2006; THF is tetrahydrofuran), but different from that in another heterometallic aluminium compound with alkoxides {[(CH₃)₃Al(µ-η²-OCH₂CH₂OCH₃)Eu(µ-η²-OCH₂CH₂OCH₃)₂Al(CH₃)₂]₂; Evans et al., 1998}.

The five-coordinated Mn atoms have trigonal–bipyramidal (Mn1) and square-pyramidal (Mn2) geometries with the value of the parameter τ equal to 0.73 and 0.02, respectively [τ = (ß - α)/60, where ß and α are the largest coordination angles; for square-pyramidal geometry τ = 0, and for trigonal–bipyramidal geometry τ = 1 (Addison et al., 1984)]. To date only a few examples of complexes containing two Mn^II ions with different geometries around the central atoms have been described [e.g. Na₂(H₂en)₂{(VO)₁₀[B₁₄O₃₀(OH)₂]₂}{Mn₄(C₂O₄)[B₂O₄(OH)₂]₂}Mn(H₂O)₂·(H₃O)₁₂(H₂O)₁₉, where τ = 0.25 and 0.58 (Cao et al., 2005)], in spite of the fact that double square-pyramidal geometries are frequently observed (Kitajima et al., 1991; Evans et al., 1998; Pajunen et al., 1998; Crewdson et al., 2003; Bieller et al., 2005).

The surroundings of the six-coordinated Mn3 and Mn4 atoms are both significantly distorted from regular octahedral geometry, as is clearly evident from the deformation of the O—Mn—O, I—Mn—O and I—Mn—I bond angles, which range from 77.88 (15)° for the chelating ligand to 100.76 (11)° for bridging O_alkoxide and I ligands.

The Al atom has a distorted tetrahedral geometry. The X—Al1—X angles (X = CH₃ or O_alkoxo; 102.5 (2)–117.3 (3)°) are similar to those found in Mn₃Al(CH₃)₂Cl₄(OCH₂CH₂OCH₃)₃(THF)₂ [102.11 (10)–112.25 (16)°]. The Al—C and Al—O bond distances are in the range observed previously for four-coordinate aluminium compounds (Kumar et al., 1994; Schumann et al., 1996).

The Mn—O bond lengths are similar to those observed for the corresponding manganese compounds (Nihei et al., 2002; Crewdson et al., 2003; Jerzykiewicz et al., 2006) and range from 2.108 (4) to 2.281 (4) Å. These distances can be grouped into six distinct categories (Table 3). The terminal Mn—I distance of 2.688 (2) Å is significantly shorter than the bridging Mn—I distances, which range from 2.773 (2) to 3.033 (2) Å, as expected (Beagley et al., 1984, 1990; Mantel et al., 2004). The closest Mn···Mn distances are in the range 3.152 (2)–3.570 (3) Å.

Only very weak intermolecular hydrogen bonds, formed between the terminal I5 atom and one of the H atoms of a methyl group, have been found (Table 2).

Related literature

For related literature, see: Addison et al. (1984); Beagley et al. (1990); Beagley et al. (1984); Bieller et al. (2005); Cao et al. (2005); Crewdson et al. (2003); Evans et al. (1998); Jerzykiewicz et al. (2006); Kitajima et al. (1991); Kumar et al. (1994); Lewinski et al. (2005); Lin et al. (1999); Mantel et al. (2004); Nihei et al. (2002); Pajunen et al. (1998); Rhine et al. (1999); Schumann et al. (1996); Sobota (2004); Sobota et al. (2000, 2002); Utko et al. (2004).

S2. Experimental

All procedures were carried out under a nitrogen atmosphere using a standard Schlenk line. A Schlenk flask was charged with [Mn₄I₄(CH₃OCH₂CH₂O)₄(CH₃OCH₂CH₂OH)₄] (1.63 g, 1.22 mmol), C₆H₅CH₃ (60 ml) and THF (20 ml). The clear solution was stirred vigorously at 253 K and Al(CH₃)₃ (8.5 ml, 2.0 M solution in C₆H₅CH₃, 17.0 mmol) was added dropwise. The mixture was warmed to room temperature and stirred for 48 h. The resulting white precipitate was filtered off, and the filtrate was concentrated until a slight turbidity was observed; the solution was then warmed to 333–343 K until it lost its turbidity. The clear solution was then layered with hexanes (20 ml). After a few weeks, crystals of (I) (0.62 g, 0.48 mmol, 40%) were taken directly from the solution.

S3. Refinement

All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H distances of 0.98 Å (CH₃) and 0.99 Å (CH₂), and with U_iso(H) values of 1.5 or 1.2 times U_eq(C), respectively.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL (Bruker, 2003); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXTL (Bruker, 2003) PLATON (Version 1.081; Spek, 2003) enCIFer (Version 1.2; Allen et al., 2004) publCIF (Westrip, 2007).

Figures

Fig. 1. A view of the title compound, with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

tetra-µ₂-iodido-iodido-bis(µ₃-2-methoxyethanolato)bis(µ₂-2-methoxyethanolato)dimethyl(tetrahydrofuran-κO)aluminium(III)tetramanganese(II)

Crystal data

[Mn4Al(CH3)2(C3H7O2)4I5(C4H8O)]	F(000) = 2400
Mr = 1283.76	Dx = 2.302 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4193 reflections
a = 7.896 (4) Å	θ = 3–26°
b = 14.899 (4) Å	µ = 5.56 mm^−1
c = 31.516 (8) Å	T = 100 K
β = 92.26 (4)°	Column, colourless
V = 3705 (2) Å^3	0.12 × 0.08 × 0.04 mm
Z = 4

Data collection

Kuma KM-4 CCD κ-axis diffractometer	8496 independent reflections
Radiation source: fine-focus sealed tube	6775 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
ω scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: analytical (CrysAlis CCD; Oxford Diffraction, 2006) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid.	h = −10→10
Tmin = 0.321, Tmax = 0.666	k = −19→19
49961 measured reflections	l = −40→38

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0403P)^2 + 0.5642P] where P = (Fo^2 + 2Fc^2)/3
8496 reflections	(Δ/σ)max = 0.002
340 parameters	Δρmax = 0.89 e Å^−3
0 restraints	Δρmin = −2.01 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
Mn1	0.72478 (10)	0.54431 (5)	0.85621 (2)	0.01835 (17)
Mn2	0.59229 (10)	0.32910 (5)	0.82151 (2)	0.01574 (16)
Mn3	0.66114 (10)	0.35044 (5)	0.92019 (2)	0.01454 (16)
Mn4	0.70821 (10)	0.14425 (5)	0.87014 (2)	0.01659 (17)
I1	0.91581 (4)	0.48949 (2)	0.927243 (11)	0.02155 (9)
I2	0.78082 (4)	0.45517 (2)	0.777257 (10)	0.01826 (8)
I3	0.40198 (4)	0.20908 (2)	0.901589 (11)	0.01958 (8)
I4	0.56617 (5)	0.16489 (2)	0.779859 (10)	0.02154 (9)
I5	0.52690 (5)	0.68950 (3)	0.864787 (14)	0.03275 (10)
Al1	0.8482 (2)	0.16252 (11)	0.98106 (5)	0.0184 (3)
O10	0.3471 (5)	0.3827 (3)	0.79769 (11)	0.0225 (8)
O11	0.5450 (4)	0.4324 (2)	0.86817 (11)	0.0170 (8)
O20	0.9590 (5)	0.1357 (2)	0.84075 (11)	0.0196 (8)
O21	0.7787 (4)	0.2832 (2)	0.86722 (10)	0.0144 (7)
O30	0.5115 (5)	0.3981 (3)	0.97437 (11)	0.0206 (8)
O31	0.7666 (5)	0.2750 (2)	0.97130 (11)	0.0195 (8)
O40	0.6645 (5)	−0.0009 (2)	0.87269 (12)	0.0249 (9)
O41	0.8308 (5)	0.1120 (2)	0.92879 (11)	0.0198 (8)
O50	0.9459 (5)	0.6367 (3)	0.84196 (11)	0.0250 (9)
C1	0.6963 (8)	0.0983 (4)	1.01954 (18)	0.0283 (13)
H1A	0.5802	0.0989	1.0073	0.042*
H1B	0.6989	0.1282	1.0473	0.042*
H1C	0.7347	0.0361	1.0231	0.042*
C2	1.0887 (7)	0.1757 (4)	1.00013 (19)	0.0292 (13)
H2A	1.1412	0.2235	0.9838	0.044*
H2B	1.1486	0.1191	0.9957	0.044*
H2C	1.0954	0.1911	1.0304	0.044*
C11	0.3654 (6)	0.4549 (4)	0.86505 (17)	0.0195 (11)
H11A	0.3454	0.5114	0.8806	0.023*
H11B	0.2988	0.4067	0.8782	0.023*
C12	0.3085 (7)	0.4659 (4)	0.81907 (18)	0.0235 (12)
H12A	0.1853	0.4782	0.8167	0.028*
H12B	0.3692	0.5166	0.8062	0.028*
C13	0.3016 (8)	0.3874 (4)	0.75340 (18)	0.0298 (14)
H13A	0.1785	0.3940	0.7496	0.045*
H13B	0.3376	0.3323	0.7394	0.045*
H13C	0.3576	0.4391	0.7408	0.045*
C21	0.9598 (6)	0.2891 (4)	0.86129 (16)	0.0167 (10)
H21A	1.0221	0.2755	0.8884	0.020*
H21B	0.9893	0.3510	0.8527	0.020*
C22	1.0122 (7)	0.2234 (4)	0.82740 (16)	0.0199 (11)
H22A	0.9570	0.2390	0.7996	0.024*
H22B	1.1366	0.2249	0.8246	0.024*
C23	1.0149 (8)	0.0662 (4)	0.81287 (19)	0.0324 (14)
H23A	1.1382	0.0699	0.8106	0.049*
H23B	0.9600	0.0740	0.7847	0.049*
H23C	0.9846	0.0074	0.8243	0.049*
C31	0.7369 (8)	0.3231 (4)	1.01004 (16)	0.0248 (13)
H31A	0.8061	0.3785	1.0112	0.030*
H31B	0.7710	0.2853	1.0348	0.030*
C32	0.5556 (8)	0.3464 (4)	1.01180 (17)	0.0260 (13)
H32A	0.4859	0.2912	1.0125	0.031*
H32B	0.5352	0.3819	1.0377	0.031*
C33	0.3347 (7)	0.4214 (4)	0.97218 (18)	0.0257 (13)
H33A	0.3060	0.4535	0.9981	0.039*
H33B	0.2664	0.3666	0.9696	0.039*
H33C	0.3110	0.4598	0.9474	0.039*
C41	0.8817 (8)	0.0188 (4)	0.92630 (19)	0.0301 (14)
H41A	0.9278	−0.0019	0.9543	0.036*
H41B	0.9709	0.0118	0.9053	0.036*
C42	0.7283 (9)	−0.0362 (4)	0.91299 (18)	0.0314 (14)
H42A	0.7598	−0.1001	0.9100	0.038*
H42B	0.6406	−0.0315	0.9345	0.038*
C43	0.5052 (9)	−0.0417 (4)	0.8595 (2)	0.0367 (15)
H43A	0.5207	−0.1066	0.8565	0.055*
H43B	0.4655	−0.0162	0.8323	0.055*
H43C	0.4212	−0.0300	0.8809	0.055*
C51	0.9678 (9)	0.6767 (4)	0.8004 (2)	0.0370 (16)
H51A	0.8566	0.6929	0.7870	0.044*
H51B	1.0254	0.6342	0.7816	0.044*
C52	1.0737 (8)	0.7588 (4)	0.8078 (2)	0.0360 (15)
H52A	1.1960	0.7447	0.8067	0.043*
H52B	1.0445	0.8059	0.7867	0.043*
C53	1.0291 (10)	0.7873 (5)	0.8514 (2)	0.0460 (19)
H53A	0.9225	0.8224	0.8506	0.055*
H53B	1.1208	0.8238	0.8650	0.055*
C54	1.0080 (8)	0.6984 (4)	0.87442 (19)	0.0308 (14)
H54A	1.1177	0.6776	0.8872	0.037*
H54B	0.9257	0.7044	0.8972	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0201 (4)	0.0173 (4)	0.0178 (4)	0.0003 (3)	0.0020 (3)	−0.0004 (3)
Mn2	0.0168 (4)	0.0139 (4)	0.0164 (4)	0.0012 (3)	−0.0013 (3)	0.0005 (3)
Mn3	0.0155 (4)	0.0147 (4)	0.0136 (4)	0.0017 (3)	0.0022 (3)	0.0000 (3)
Mn4	0.0211 (4)	0.0123 (4)	0.0165 (4)	0.0023 (3)	0.0023 (3)	0.0006 (3)
I1	0.01992 (18)	0.02253 (19)	0.02214 (18)	−0.00132 (14)	0.00012 (14)	−0.00085 (14)
I2	0.02194 (18)	0.01659 (17)	0.01653 (16)	−0.00133 (13)	0.00435 (13)	0.00103 (13)
I3	0.01570 (17)	0.01868 (18)	0.02447 (18)	0.00021 (13)	0.00208 (13)	−0.00186 (14)
I4	0.0301 (2)	0.01691 (18)	0.01728 (17)	−0.00229 (15)	−0.00242 (14)	−0.00298 (13)
I5	0.0329 (2)	0.0235 (2)	0.0419 (2)	0.00390 (17)	0.00185 (18)	0.00082 (17)
Al1	0.0211 (8)	0.0177 (8)	0.0164 (8)	0.0028 (7)	0.0008 (6)	0.0049 (6)
O10	0.019 (2)	0.023 (2)	0.025 (2)	0.0001 (16)	−0.0032 (16)	0.0040 (16)
O11	0.0162 (18)	0.0132 (18)	0.0217 (19)	0.0024 (14)	0.0025 (15)	0.0019 (14)
O20	0.027 (2)	0.0144 (19)	0.0179 (18)	0.0071 (16)	0.0067 (15)	−0.0025 (14)
O21	0.0102 (17)	0.0150 (18)	0.0183 (17)	0.0015 (14)	0.0028 (14)	−0.0011 (14)
O30	0.0197 (19)	0.023 (2)	0.0193 (19)	0.0024 (16)	0.0043 (15)	−0.0014 (15)
O31	0.024 (2)	0.019 (2)	0.0153 (18)	0.0039 (16)	−0.0009 (15)	0.0002 (14)
O40	0.036 (2)	0.016 (2)	0.023 (2)	0.0027 (17)	0.0013 (17)	0.0042 (16)
O41	0.029 (2)	0.0145 (19)	0.0161 (18)	0.0064 (16)	0.0013 (15)	0.0025 (14)
O50	0.032 (2)	0.024 (2)	0.0186 (19)	−0.0039 (18)	0.0015 (17)	−0.0002 (16)
C1	0.034 (3)	0.024 (3)	0.027 (3)	0.002 (3)	0.010 (3)	0.002 (2)
C2	0.027 (3)	0.030 (3)	0.031 (3)	0.003 (3)	−0.004 (3)	0.011 (3)
C11	0.015 (3)	0.019 (3)	0.024 (3)	0.005 (2)	0.006 (2)	0.001 (2)
C12	0.016 (3)	0.021 (3)	0.034 (3)	0.004 (2)	0.000 (2)	0.008 (2)
C13	0.033 (3)	0.030 (3)	0.025 (3)	0.003 (3)	−0.013 (3)	0.002 (2)
C21	0.011 (2)	0.020 (3)	0.019 (3)	0.001 (2)	0.001 (2)	−0.001 (2)
C22	0.021 (3)	0.020 (3)	0.019 (3)	0.002 (2)	0.008 (2)	0.002 (2)
C23	0.042 (4)	0.027 (3)	0.030 (3)	0.011 (3)	0.013 (3)	−0.008 (3)
C31	0.040 (3)	0.023 (3)	0.011 (2)	0.006 (3)	−0.004 (2)	−0.002 (2)
C32	0.037 (3)	0.025 (3)	0.017 (3)	0.001 (3)	0.010 (2)	0.002 (2)
C33	0.018 (3)	0.030 (3)	0.030 (3)	0.003 (2)	0.007 (2)	−0.008 (2)
C41	0.043 (4)	0.021 (3)	0.026 (3)	0.015 (3)	0.002 (3)	0.006 (2)
C42	0.055 (4)	0.017 (3)	0.022 (3)	0.004 (3)	0.002 (3)	0.006 (2)
C43	0.047 (4)	0.022 (3)	0.042 (4)	−0.010 (3)	0.001 (3)	0.002 (3)
C51	0.052 (4)	0.028 (4)	0.031 (3)	−0.009 (3)	0.001 (3)	0.009 (3)
C52	0.033 (4)	0.037 (4)	0.039 (4)	−0.005 (3)	0.000 (3)	0.012 (3)
C53	0.053 (5)	0.032 (4)	0.055 (5)	−0.013 (3)	0.016 (4)	−0.012 (3)
C54	0.037 (4)	0.028 (3)	0.027 (3)	−0.013 (3)	0.006 (3)	−0.008 (3)

Geometric parameters (Å, º)

Mn1—I1	2.773 (2)	C52—C53	1.494 (9)
Mn3—I1	2.890 (2)	C53—C54	1.523 (9)
Mn1—I2	2.870 (2)	C1—H1A	0.98
Mn2—I2	2.802 (2)	C1—H1B	0.98
Mn3—I3	2.979 (2)	C1—H1C	0.98
Mn4—I3	2.820 (2)	C2—H2A	0.98
Mn2—I4	2.780 (2)	C2—H2B	0.98
Mn4—I4	3.033 (2)	C2—H2C	0.98
Mn1—I5	2.688 (2)	C11—H11A	0.99
Mn1—O11	2.232 (3)	C11—H11B	0.99
Mn1—O50	2.282 (4)	C12—H12A	0.99
Mn2—O10	2.199 (4)	C12—H12B	0.99
Mn2—O11	2.171 (3)	C13—H13A	0.98
Mn2—O21	2.131 (3)	C13—H13B	0.98
Mn3—O11	2.214 (4)	C13—H13C	0.98
Mn3—O21	2.185 (3)	C21—H21A	0.99
Mn3—O30	2.231 (4)	C21—H21B	0.99
Mn3—O31	2.109 (4)	C22—H22A	0.99
Mn4—O20	2.223 (4)	C22—H22B	0.99
Mn4—O21	2.147 (3)	C23—H23A	0.98
Mn4—O40	2.192 (3)	C23—H23B	0.98
Mn4—O41	2.108 (4)	C23—H23C	0.98
Al1—O31	1.817 (4)	C31—H31A	0.99
Al1—O41	1.811 (4)	C31—H31B	0.99
Al1—C1	1.985 (6)	C32—H32A	0.99
Al1—C2	1.979 (6)	C32—H32B	0.99
O10—C12	1.449 (7)	C33—H33A	0.98
O10—C13	1.429 (7)	C33—H33B	0.98
O11—C11	1.457 (6)	C33—H33C	0.98
O20—C22	1.440 (7)	C41—H41A	0.99
O20—C23	1.439 (7)	C41—H41B	0.99
O21—C21	1.452 (6)	C42—H42A	0.99
O30—C32	1.440 (7)	C42—H42B	0.99
O30—C33	1.438 (7)	C43—H43A	0.98
O31—C31	1.443 (6)	C43—H43B	0.98
O40—C42	1.447 (7)	C43—H43C	0.98
O40—C43	1.443 (8)	C51—H51A	0.99
O41—C41	1.449 (7)	C51—H51B	0.99
O50—C51	1.456 (7)	C52—H52A	0.99
O50—C54	1.447 (7)	C52—H52B	0.99
C11—C12	1.509 (8)	C53—H53A	0.99
C21—C22	1.518 (8)	C53—H53B	0.99
C31—C32	1.476 (9)	C54—H54A	0.99
C41—C42	1.508 (9)	C54—H54B	0.99
C51—C52	1.495 (9)
Mn1—I1—Mn3	78.13 (5)	O50—C51—C52	106.3 (5)
Mn1—I2—Mn2	77.03 (5)	C51—C52—C53	103.0 (5)
Mn3—I3—Mn4	73.70 (5)	C52—C53—C54	103.0 (5)
Mn2—I4—Mn4	68.19 (5)	O50—C54—C53	104.9 (5)
I1—Mn1—I2	117.78 (5)	Al1—C1—H1A	109
I1—Mn1—I5	117.11 (5)	Al1—C1—H1B	110
I1—Mn1—O11	88.45 (10)	Al1—C1—H1C	110
I1—Mn1—O50	86.59 (10)	H1A—C1—H1B	109
I2—Mn1—I5	124.72 (5)	H1A—C1—H1C	110
I2—Mn1—O11	85.50 (10)	H1B—C1—H1C	109
I2—Mn1—O50	87.89 (10)	Al1—C2—H2A	109
I5—Mn1—O11	102.01 (9)	Al1—C2—H2B	110
I5—Mn1—O50	89.23 (12)	Al1—C2—H2C	109
O11—Mn1—O50	168.75 (14)	H2A—C2—H2B	110
I2—Mn2—I4	112.69 (5)	H2A—C2—H2C	109
I2—Mn2—O10	93.70 (12)	H2B—C2—H2C	109
I2—Mn2—O11	88.33 (10)	O11—C11—H11A	110
I2—Mn2—O21	100.67 (10)	O11—C11—H11B	110
I4—Mn2—O10	96.34 (12)	C12—C11—H11A	110
I4—Mn2—O11	158.75 (10)	C12—C11—H11B	110
I4—Mn2—O21	94.20 (9)	H11A—C11—H11B	108
O10—Mn2—O11	78.53 (14)	O10—C12—H12A	110
O10—Mn2—O21	157.31 (14)	O10—C12—H12B	110
O11—Mn2—O21	84.39 (13)	C11—C12—H12A	110
I1—Mn3—I3	173.07 (5)	C11—C12—H12B	110
I1—Mn3—O11	85.88 (9)	H12A—C12—H12B	109
I1—Mn3—O21	94.14 (9)	O10—C13—H13A	110
I1—Mn3—O30	95.79 (12)	O10—C13—H13B	109
I1—Mn3—O31	94.06 (11)	O10—C13—H13C	110
I3—Mn3—O11	89.02 (9)	H13A—C13—H13B	109
I3—Mn3—O21	80.49 (9)	H13A—C13—H13C	109
I3—Mn3—O30	89.73 (12)	H13B—C13—H13C	109
I3—Mn3—O31	91.20 (11)	O21—C21—H21A	110
O11—Mn3—O21	82.14 (13)	O21—C21—H21B	110
O11—Mn3—O30	100.07 (14)	C22—C21—H21A	110
O11—Mn3—O31	177.94 (14)	C22—C21—H21B	110
O21—Mn3—O30	169.96 (15)	H21A—C21—H21B	108
O21—Mn3—O31	99.93 (13)	O20—C22—H22A	110
O30—Mn3—O31	77.88 (15)	O20—C22—H22B	110
I3—Mn4—I4	90.26 (5)	C21—C22—H22A	110
I3—Mn4—O20	163.05 (9)	C21—C22—H22B	110
I3—Mn4—O21	84.96 (10)	H22A—C22—H22B	109
I3—Mn4—O40	100.76 (11)	O20—C23—H23A	109
I3—Mn4—O41	98.07 (11)	O20—C23—H23B	109
I4—Mn4—O20	85.26 (10)	O20—C23—H23C	109
I4—Mn4—O21	87.07 (10)	H23A—C23—H23B	109
I4—Mn4—O40	94.68 (11)	H23A—C23—H23C	110
I4—Mn4—O41	170.37 (11)	H23B—C23—H23C	109
O20—Mn4—O21	78.50 (12)	O31—C31—H31A	110
O20—Mn4—O40	95.91 (14)	O31—C31—H31B	110
O20—Mn4—O41	88.08 (15)	C32—C31—H31A	110
O21—Mn4—O40	174.00 (14)	C32—C31—H31B	110
O21—Mn4—O41	98.43 (13)	H31A—C31—H31B	108
O40—Mn4—O41	79.08 (14)	O30—C32—H32A	110
O31—Al1—O41	102.5 (2)	O30—C32—H32B	110
O31—Al1—C1	109.2 (2)	C31—C32—H32A	110
O31—Al1—C2	106.8 (2)	C31—C32—H32B	110
O41—Al1—C1	109.2 (2)	H32A—C32—H32B	108
O41—Al1—C2	110.8 (2)	O30—C33—H33A	109
C1—Al1—C2	117.3 (3)	O30—C33—H33B	109
Mn2—O10—C12	110.5 (3)	O30—C33—H33C	109
Mn2—O10—C13	122.4 (3)	H33A—C33—H33B	109
C12—O10—C13	111.3 (4)	H33A—C33—H33C	110
Mn1—O11—Mn2	106.72 (15)	H33B—C33—H33C	109
Mn1—O11—Mn3	106.83 (14)	O41—C41—H41A	110
Mn1—O11—C11	116.2 (3)	O41—C41—H41B	110
Mn2—O11—Mn3	91.91 (12)	C42—C41—H41A	110
Mn2—O11—C11	108.1 (3)	C42—C41—H41B	110
Mn3—O11—C11	123.4 (3)	H41A—C41—H41B	108
Mn4—O20—C22	110.2 (3)	O40—C42—H42A	110
Mn4—O20—C23	126.6 (3)	O40—C42—H42B	110
C22—O20—C23	112.0 (4)	C41—C42—H42A	110
Mn2—O21—Mn3	93.81 (13)	C41—C42—H42B	110
Mn2—O21—Mn4	99.50 (14)	H42A—C42—H42B	109
Mn2—O21—C21	123.4 (3)	O40—C43—H43A	109
Mn3—O21—Mn4	106.90 (14)	O40—C43—H43B	110
Mn3—O21—C21	121.4 (3)	O40—C43—H43C	109
Mn4—O21—C21	108.8 (3)	H43A—C43—H43B	110
Mn3—O30—C32	109.8 (3)	H43A—C43—H43C	109
Mn3—O30—C33	125.7 (3)	H43B—C43—H43C	109
C32—O30—C33	111.8 (4)	O50—C51—H51A	110
Mn3—O31—Al1	138.4 (2)	O50—C51—H51B	111
Mn3—O31—C31	108.0 (3)	C52—C51—H51A	110
Al1—O31—C31	112.5 (3)	C52—C51—H51B	110
Mn4—O40—C42	109.9 (3)	H51A—C51—H51B	109
Mn4—O40—C43	122.8 (3)	C51—C52—H52A	111
C42—O40—C43	111.7 (4)	C51—C52—H52B	111
Mn4—O41—Al1	135.93 (19)	C53—C52—H52A	111
Mn4—O41—C41	106.9 (3)	C53—C52—H52B	111
Al1—O41—C41	115.9 (3)	H52A—C52—H52B	109
Mn1—O50—C51	122.9 (3)	C52—C53—H53A	111
Mn1—O50—C54	119.0 (3)	C52—C53—H53B	111
C51—O50—C54	109.1 (4)	C54—C53—H53A	111
O11—C11—C12	110.0 (4)	C54—C53—H53B	111
O10—C12—C11	107.1 (5)	H53A—C53—H53B	109
O21—C21—C22	110.4 (4)	O50—C54—H54A	111
O20—C22—C21	106.8 (4)	O50—C54—H54B	111
O31—C31—C32	109.8 (5)	C53—C54—H54A	111
O30—C32—C31	107.4 (5)	C53—C54—H54B	111
O41—C41—C42	108.3 (5)	H54A—C54—H54B	109
O40—C42—C41	107.1 (5)
Mn3—I1—Mn1—I2	−78.54 (5)	I3—Mn3—O30—C33	−52.5 (4)
Mn3—I1—Mn1—I5	108.26 (5)	O11—Mn3—O30—C32	174.5 (3)
Mn3—I1—Mn1—O11	5.55 (9)	O11—Mn3—O30—C33	36.4 (4)
Mn3—I1—Mn1—O50	−164.35 (11)	O31—Mn3—O30—C32	−5.8 (3)
Mn1—I1—Mn3—O31	176.47 (11)	O31—Mn3—O30—C33	−143.8 (4)
Mn1—I1—Mn3—O30	−105.33 (11)	I1—Mn3—O31—Al1	−122.3 (3)
Mn1—I1—Mn3—O11	−5.60 (10)	I1—Mn3—O31—C31	71.1 (3)
Mn1—I1—Mn3—O21	76.19 (9)	I3—Mn3—O31—Al1	53.2 (3)
Mn2—I2—Mn1—O11	−10.09 (9)	I3—Mn3—O31—C31	−113.4 (3)
Mn1—I2—Mn2—O10	88.74 (11)	O21—Mn3—O31—Al1	−27.4 (3)
Mn2—I2—Mn1—O50	160.80 (11)	O21—Mn3—O31—C31	166.0 (3)
Mn1—I2—Mn2—I4	−172.80 (5)	O30—Mn3—O31—Al1	142.6 (3)
Mn2—I2—Mn1—I5	−111.60 (6)	O30—Mn3—O31—C31	−24.0 (3)
Mn2—I2—Mn1—I1	75.77 (5)	O30—Mn3—O11—Mn1	102.29 (16)
Mn1—I2—Mn2—O11	10.35 (10)	O30—Mn3—O11—Mn2	−149.61 (14)
Mn1—I2—Mn2—O21	−73.63 (10)	O30—Mn3—O11—C11	−36.4 (4)
Mn4—I3—Mn3—O31	−76.35 (11)	I1—Mn3—O21—Mn2	−106.17 (10)
Mn4—I3—Mn3—O11	105.70 (10)	I1—Mn3—O21—Mn4	152.69 (12)
Mn4—I3—Mn3—O21	23.52 (9)	I1—Mn3—O21—C21	27.3 (3)
Mn3—I3—Mn4—O21	−23.71 (10)	I3—Mn3—O21—Mn2	69.42 (10)
Mn3—I3—Mn4—O40	154.44 (11)	I3—Mn3—O21—Mn4	−31.72 (11)
Mn3—I3—Mn4—O41	74.11 (10)	I4—Mn4—O20—C22	75.4 (3)
Mn3—I3—Mn4—I4	−110.75 (5)	I4—Mn4—O20—C23	−64.9 (4)
Mn4—I3—Mn3—O30	−154.22 (11)	O21—Mn4—O20—C22	−12.6 (3)
Mn2—I4—Mn4—O20	−100.32 (9)	O21—Mn4—O20—C23	−152.9 (4)
Mn4—I4—Mn2—O21	21.83 (10)	O40—Mn4—O20—C22	169.6 (3)
Mn4—I4—Mn2—I2	125.24 (5)	O40—Mn4—O20—C23	29.3 (4)
Mn4—I4—Mn2—O10	−138.05 (11)	O41—Mn4—O20—C22	−111.6 (3)
Mn4—I4—Mn2—O11	−63.5 (3)	O41—Mn4—O20—C23	108.2 (4)
Mn2—I4—Mn4—I3	63.31 (5)	I3—Mn4—O21—Mn2	−63.61 (11)
Mn2—I4—Mn4—O21	−21.63 (10)	I3—Mn4—O21—Mn3	33.36 (12)
Mn2—I4—Mn4—O40	164.12 (11)	I3—Mn4—O21—C21	166.1 (3)
I5—Mn1—O11—C11	17.3 (3)	I4—Mn4—O21—Mn2	26.91 (11)
I2—Mn1—O11—Mn2	13.31 (12)	I4—Mn4—O21—Mn3	123.88 (12)
I2—Mn1—O11—Mn3	110.62 (12)	I4—Mn4—O21—C21	−103.4 (3)
I2—Mn1—O11—C11	−107.3 (3)	O20—Mn4—O21—Mn2	112.67 (15)
I5—Mn1—O11—Mn2	137.88 (11)	O20—Mn4—O21—Mn3	−150.36 (16)
I5—Mn1—O11—Mn3	−124.82 (11)	O20—Mn4—O21—C21	−17.7 (3)
I5—Mn1—O50—C51	−80.3 (4)	O41—Mn4—O21—Mn2	−161.04 (14)
I1—Mn1—O11—Mn3	−7.41 (12)	O41—Mn4—O21—Mn3	−64.07 (17)
I1—Mn1—O11—C11	134.7 (3)	O41—Mn4—O21—C21	68.6 (3)
I1—Mn1—O50—C51	162.5 (4)	I3—Mn4—O40—C42	−91.6 (4)
I1—Mn1—O50—C54	−54.0 (4)	I3—Mn4—O40—C43	42.9 (4)
I2—Mn1—O50—C51	44.5 (4)	I4—Mn4—O40—C42	177.2 (4)
I2—Mn1—O50—C54	−172.0 (4)	I4—Mn4—O40—C43	−48.3 (4)
I5—Mn1—O50—C54	63.2 (4)	O20—Mn4—O40—C42	91.5 (4)
I1—Mn1—O11—Mn2	−104.72 (12)	O20—Mn4—O40—C43	−134.0 (4)
I2—Mn2—O10—C12	−75.2 (3)	O41—Mn4—O40—C42	4.6 (4)
I2—Mn2—O11—C11	112.0 (3)	O41—Mn4—O40—C43	139.1 (4)
I4—Mn2—O11—Mn1	174.45 (15)	I3—Mn4—O41—Al1	−40.0 (3)
I4—Mn2—O11—Mn3	66.2 (3)	I3—Mn4—O41—C41	125.5 (3)
I4—Mn2—O11—C11	−59.9 (4)	O20—Mn4—O41—Al1	124.1 (3)
O10—Mn2—O11—Mn1	−107.71 (17)	O20—Mn4—O41—C41	−70.4 (3)
O10—Mn2—O11—Mn3	144.08 (15)	O21—Mn4—O41—Al1	46.1 (3)
O10—Mn2—O11—C11	17.9 (3)	O21—Mn4—O41—C41	−148.4 (3)
I2—Mn2—O11—Mn3	−121.81 (10)	O40—Mn4—O41—Al1	−139.5 (3)
I4—Mn2—O21—C21	90.5 (3)	O40—Mn4—O41—C41	26.0 (3)
O10—Mn2—O21—Mn3	−19.9 (4)	O41—Al1—O31—Mn3	2.5 (4)
O10—Mn2—O21—Mn4	87.9 (4)	O41—Al1—O31—C31	168.6 (4)
O10—Mn2—O21—C21	−151.9 (4)	C1—Al1—O31—Mn3	−113.3 (3)
O11—Mn2—O21—Mn3	21.24 (12)	C1—Al1—O31—C31	52.9 (4)
O11—Mn2—O21—Mn4	129.09 (14)	C2—Al1—O31—Mn3	119.0 (3)
O11—Mn2—O21—C21	−110.8 (4)	C2—Al1—O31—C31	−74.8 (4)
I2—Mn2—O10—C13	58.9 (4)	O31—Al1—O41—Mn4	−13.3 (3)
I4—Mn2—O10—C12	171.5 (3)	O31—Al1—O41—C41	−177.9 (4)
I4—Mn2—O10—C13	−54.4 (4)	C1—Al1—O41—Mn4	102.4 (3)
O11—Mn2—O10—C12	12.4 (3)	C1—Al1—O41—C41	−62.1 (4)
O11—Mn2—O10—C13	146.4 (4)	C2—Al1—O41—Mn4	−126.9 (3)
O21—Mn2—O10—C12	54.3 (6)	C2—Al1—O41—C41	68.5 (4)
O21—Mn2—O10—C13	−171.6 (4)	Mn2—O10—C12—C11	−39.1 (5)
I2—Mn2—O11—Mn1	−13.60 (12)	C13—O10—C12—C11	−178.5 (4)
I4—Mn2—O21—Mn3	−137.48 (9)	Mn1—O11—C11—C12	74.4 (5)
I4—Mn2—O21—Mn4	−29.63 (12)	Mn2—O11—C11—C12	−45.4 (5)
O21—Mn2—O11—Mn1	87.30 (15)	Mn3—O11—C11—C12	−150.3 (3)
O21—Mn2—O11—Mn3	−20.91 (12)	Mn4—O20—C22—C21	38.7 (4)
O21—Mn2—O11—C11	−147.1 (3)	C23—O20—C22—C21	−175.0 (4)
I2—Mn2—O21—Mn3	108.47 (10)	Mn2—O21—C21—C22	−70.5 (5)
I2—Mn2—O21—Mn4	−143.68 (10)	Mn3—O21—C21—C22	169.7 (3)
I2—Mn2—O21—C21	−23.6 (3)	Mn4—O21—C21—C22	45.2 (4)
O21—Mn3—O11—C11	133.7 (4)	Mn3—O30—C32—C31	33.6 (5)
I1—Mn3—O11—C11	−131.6 (3)	C33—O30—C32—C31	177.8 (5)
I3—Mn3—O11—Mn1	−168.17 (12)	Mn3—O31—C31—C32	51.6 (5)
I3—Mn3—O11—Mn2	−60.06 (10)	Al1—O31—C31—C32	−118.8 (4)
I3—Mn3—O11—C11	53.2 (3)	Mn4—O40—C42—C41	−33.1 (5)
O21—Mn3—O11—Mn1	−87.64 (15)	C43—O40—C42—C41	−173.0 (5)
O21—Mn3—O11—Mn2	20.47 (12)	Mn4—O41—C41—C42	−53.0 (5)
I1—Mn3—O11—Mn1	7.12 (12)	Al1—O41—C41—C42	115.9 (4)
I1—Mn3—O11—Mn2	115.23 (10)	Mn1—O50—C51—C52	156.4 (4)
I3—Mn3—O21—C21	−157.2 (3)	C54—O50—C51—C52	9.7 (6)
O11—Mn3—O21—Mn2	−20.91 (12)	Mn1—O50—C54—C53	−134.6 (4)
O11—Mn3—O21—Mn4	−122.05 (15)	C51—O50—C54—C53	13.5 (6)
O11—Mn3—O21—C21	112.5 (3)	O11—C11—C12—O10	57.1 (5)
O31—Mn3—O21—Mn2	158.98 (13)	O21—C21—C22—O20	−56.7 (5)
O31—Mn3—O21—Mn4	57.84 (17)	O31—C31—C32—O30	−57.2 (6)
O31—Mn3—O21—C21	−67.6 (3)	O41—C41—C42—O40	58.0 (6)
I1—Mn3—O30—C32	−98.7 (3)	O50—C51—C52—C53	−29.3 (6)
I1—Mn3—O30—C33	123.3 (4)	C51—C52—C53—C54	36.9 (7)
I3—Mn3—O30—C32	85.5 (3)	C52—C53—C54—O50	−31.5 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C43—H43A···I5^i	0.98	3.05	4.012 (6)	168

Symmetry code: (i) x, y−1, z.