A trinuclear mixed-valence manganese carboxyl­ate: tris­(acetic acid-κO)-μ₃-oxo-hexa­kis(μ₂-trichloro­acetato-κ²O:O′)trimanganese(II,III,III)

The title mixed-valence manganese carboxyl­ate, [Mn₃(C₂Cl₃O₂)₆O(C₂H₄O₂)₃], was synthesized starting from an acetic acid solution of Mn(CCl₃COO)₂·3H₂O, CCl₃COOH and KMnO₄. The mol­ecule features a planar trinuclear μ₃-oxo-centered manganese(II,III,III) complex. Differences in the geometric parameters of the Mn atoms due to strong Jahn–Teller effects in the Mn³⁺ ions allow the metal atoms with oxidation states +2 and +3 to be distinguished.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.054
• wR factor = 0.097
• Data-to-parameter ratio = 18.6

checkCIF/PLATON results

No syntax errors found



Alert level C
DENSX01_ALERT_1_C  The ratio of the calculated to measured crystal density
            lies outside the range 0.95 <> 1.05
            Calculated density =      2.047
            Measured density   =      1.943
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       2.83 Ratio
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl13   ..  O42     ..       3.14 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl33   ..  O52     ..       3.24 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl41   ..  O21     ..       3.21 Ang.
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl63   ..  O41     ..       3.24 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: enCIFer (Allen et al., 2004).

tris(acetic acid-κO)-µ₃-oxo-hexakis(µ₂-trichloroacetato- κ²O:O')trimanganese(II,III,III)

Crystal data

[Mn3(C2Cl3O2)6O(C2H4O2)3]	Z = 2
Mr = 1335.20	F(000) = 1306
Triclinic, P1	Dx = 2.047 Mg m^−3 Dm = 1.943 Mg m^−3 Dm measured by flotation
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.121 (3) Å	Cell parameters from 18242 reflections
b = 10.424 (3) Å	θ = 0–27.6°
c = 22.891 (5) Å	µ = 2.04 mm^−1
α = 88.01 (3)°	T = 100 K
β = 79.45 (3)°	Parallelepiped, dark brown
γ = 65.94 (3)°	0.2 × 0.2 × 0.05 mm
V = 2165.8 (12) Å^3

Data collection

Kuma KM-4 CCD κ-geometry diffractometer	9906 independent reflections
Radiation source: long fine focus sealed tube	8642 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω–2θ scans	θmax = 27.6°, θmin = 3.1°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2003)	h = −13→12
Tmin = 0.691, Tmax = 0.899	k = −13→13
30649 measured reflections	l = −29→29

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.16	w = 1/[σ^2(Fo^2) + (0.0043P)^2 + 12.065P] where P = (Fo^2 + 2Fc^2)/3
9906 reflections	(Δ/σ)max = 0.001
532 parameters	Δρmax = 0.64 e Å^−3
0 restraints	Δρmin = −0.55 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	0.69672 (6)	0.17138 (6)	0.25769 (3)	0.00843 (12)
Mn2	0.97456 (6)	0.21472 (6)	0.28833 (3)	0.00837 (12)
Mn3	0.73499 (6)	0.47241 (6)	0.21352 (3)	0.00915 (12)
Cl11	1.26888 (12)	−0.27124 (12)	0.18781 (5)	0.0233 (2)
Cl12	1.06140 (15)	−0.12506 (14)	0.11193 (5)	0.0327 (3)
Cl13	0.99502 (13)	−0.30211 (12)	0.20187 (6)	0.0272 (3)
Cl21	0.58104 (12)	0.10169 (12)	0.47254 (5)	0.0196 (2)
Cl22	0.75838 (13)	0.25078 (13)	0.48664 (5)	0.0250 (2)
Cl23	0.89466 (12)	−0.05113 (13)	0.46058 (5)	0.0236 (2)
Cl31	1.19043 (12)	0.42299 (13)	0.07144 (5)	0.0274 (3)
Cl32	1.27315 (13)	0.13067 (12)	0.09810 (5)	0.0261 (3)
Cl33	1.35384 (11)	0.30987 (13)	0.16485 (5)	0.0235 (2)
Cl41	0.72961 (17)	0.81369 (12)	0.35604 (6)	0.0337 (3)
Cl42	0.85534 (14)	0.60474 (12)	0.43831 (5)	0.0262 (3)
Cl43	0.57796 (14)	0.64312 (18)	0.40811 (7)	0.0425 (4)
Cl51	0.71097 (14)	0.08130 (12)	0.04108 (5)	0.0240 (2)
Cl52	0.93105 (12)	0.19383 (14)	0.03650 (5)	0.0255 (2)
Cl53	0.63743 (13)	0.37306 (12)	0.01974 (5)	0.0248 (2)
Cl61	0.24622 (12)	0.71116 (11)	0.34557 (5)	0.0236 (2)
Cl62	0.35107 (13)	0.45018 (13)	0.40540 (5)	0.0253 (2)
Cl63	0.18499 (12)	0.48050 (13)	0.31160 (5)	0.0240 (2)
O1	0.8088 (3)	0.2719 (3)	0.25548 (12)	0.0100 (5)
O11	0.8624 (3)	−0.0108 (3)	0.23794 (13)	0.0128 (6)
O12	1.0735 (3)	0.0082 (3)	0.24231 (13)	0.0153 (6)
O21	0.6839 (3)	0.1371 (3)	0.35147 (12)	0.0139 (6)
O22	0.8968 (3)	0.1461 (3)	0.36144 (13)	0.0156 (6)
O31	1.0926 (3)	0.2720 (3)	0.22234 (12)	0.0138 (6)
O32	0.9552 (3)	0.4109 (3)	0.15956 (13)	0.0136 (6)
O41	0.8969 (3)	0.4103 (3)	0.34092 (13)	0.0132 (6)
O42	0.7881 (3)	0.5745 (3)	0.27944 (13)	0.0143 (6)
O51	0.6841 (3)	0.3873 (3)	0.14049 (13)	0.0150 (6)
O52	0.7061 (3)	0.1692 (3)	0.16087 (12)	0.0131 (6)
O61	0.5209 (3)	0.5430 (3)	0.26928 (13)	0.0141 (6)
O62	0.5069 (3)	0.3338 (3)	0.27940 (13)	0.0134 (6)
O71	0.5714 (3)	0.0653 (3)	0.26212 (12)	0.0126 (6)
O72	0.6205 (4)	−0.0377 (3)	0.17107 (14)	0.0205 (7)
H72	0.656 (7)	0.016 (6)	0.165 (3)	0.031*
O81	1.1535 (3)	0.1542 (3)	0.32471 (13)	0.0128 (6)
O82	1.0811 (4)	0.2750 (3)	0.41261 (14)	0.0187 (7)
H82	1.009 (7)	0.316 (6)	0.404 (3)	0.028*
O91	0.6679 (3)	0.6515 (3)	0.15823 (13)	0.0159 (6)
O92	0.8317 (4)	0.5976 (4)	0.07311 (15)	0.0282 (8)
H92	0.883 (7)	0.562 (7)	0.093 (3)	0.042*
C11	1.0013 (4)	−0.0503 (4)	0.22658 (17)	0.0115 (8)
C12	1.0821 (5)	−0.1857 (5)	0.18463 (19)	0.0158 (8)
C21	0.7769 (4)	0.1339 (4)	0.37980 (18)	0.0121 (8)
C22	0.7521 (4)	0.1097 (4)	0.44757 (18)	0.0133 (8)
C31	1.0726 (4)	0.3337 (4)	0.17443 (17)	0.0100 (7)
C32	1.2175 (4)	0.3034 (4)	0.12863 (18)	0.0143 (8)
C41	0.8214 (4)	0.5336 (4)	0.32749 (18)	0.0122 (8)
C42	0.7527 (5)	0.6457 (5)	0.3807 (2)	0.0183 (9)
C51	0.7039 (4)	0.2667 (4)	0.12671 (18)	0.0111 (8)
C52	0.7424 (5)	0.2294 (4)	0.05845 (18)	0.0143 (8)
C61	0.4629 (4)	0.4639 (4)	0.29003 (18)	0.0112 (8)
C62	0.3157 (4)	0.5266 (4)	0.33616 (19)	0.0152 (8)
C71	0.5578 (4)	−0.0164 (4)	0.22697 (19)	0.0130 (8)
C72	0.4644 (5)	−0.0938 (5)	0.2479 (2)	0.0187 (9)
H72A	0.4974	−0.1479	0.2822	0.028*
H72B	0.4725	−0.1580	0.2158	0.028*
H72C	0.3616	−0.0267	0.2594	0.028*
C81	1.1753 (5)	0.1769 (4)	0.37398 (18)	0.0138 (8)
C82	1.3175 (5)	0.0934 (5)	0.3935 (2)	0.0230 (10)
H82A	1.3414	−0.0071	0.3886	0.035*
H82B	1.3089	0.1173	0.4355	0.035*
H82C	1.3957	0.1151	0.3694	0.035*
C91	0.6995 (5)	0.6677 (4)	0.10538 (19)	0.0149 (8)
C92	0.5922 (5)	0.7670 (5)	0.0710 (2)	0.0219 (10)
H92A	0.5179	0.7317	0.0671	0.033*
H92B	0.6439	0.7750	0.0314	0.033*
H92C	0.5439	0.8596	0.0918	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0075 (3)	0.0084 (3)	0.0097 (3)	−0.0037 (2)	−0.0013 (2)	0.0004 (2)
Mn2	0.0071 (3)	0.0097 (3)	0.0088 (3)	−0.0038 (2)	−0.0018 (2)	0.0006 (2)
Mn3	0.0086 (3)	0.0087 (3)	0.0094 (3)	−0.0032 (2)	−0.0007 (2)	0.0002 (2)
Cl11	0.0140 (5)	0.0188 (5)	0.0332 (6)	−0.0025 (4)	−0.0034 (4)	−0.0057 (5)
Cl12	0.0370 (7)	0.0350 (7)	0.0140 (5)	−0.0026 (6)	−0.0041 (5)	−0.0018 (5)
Cl13	0.0217 (5)	0.0144 (5)	0.0459 (7)	−0.0086 (4)	−0.0026 (5)	−0.0054 (5)
Cl21	0.0179 (5)	0.0316 (6)	0.0140 (5)	−0.0157 (5)	−0.0012 (4)	0.0034 (4)
Cl22	0.0293 (6)	0.0326 (6)	0.0187 (5)	−0.0202 (5)	0.0024 (4)	−0.0100 (5)
Cl23	0.0223 (5)	0.0267 (6)	0.0211 (5)	−0.0082 (5)	−0.0086 (4)	0.0096 (5)
Cl31	0.0179 (5)	0.0344 (7)	0.0203 (5)	−0.0049 (5)	0.0036 (4)	0.0125 (5)
Cl32	0.0239 (6)	0.0215 (6)	0.0261 (6)	−0.0053 (5)	0.0042 (5)	−0.0102 (5)
Cl33	0.0124 (5)	0.0368 (6)	0.0239 (6)	−0.0132 (5)	−0.0020 (4)	0.0000 (5)
Cl41	0.0579 (8)	0.0129 (5)	0.0327 (7)	−0.0101 (5)	−0.0242 (6)	−0.0007 (5)
Cl42	0.0384 (7)	0.0201 (5)	0.0184 (5)	−0.0067 (5)	−0.0131 (5)	−0.0022 (4)
Cl43	0.0227 (6)	0.0616 (10)	0.0386 (8)	−0.0182 (6)	0.0137 (5)	−0.0277 (7)
Cl51	0.0411 (7)	0.0220 (6)	0.0150 (5)	−0.0186 (5)	−0.0051 (5)	−0.0030 (4)
Cl52	0.0169 (5)	0.0377 (7)	0.0184 (5)	−0.0096 (5)	0.0022 (4)	−0.0033 (5)
Cl53	0.0333 (6)	0.0219 (6)	0.0176 (5)	−0.0062 (5)	−0.0140 (5)	0.0063 (4)
Cl61	0.0196 (5)	0.0155 (5)	0.0285 (6)	−0.0031 (4)	0.0046 (4)	−0.0054 (4)
Cl62	0.0312 (6)	0.0296 (6)	0.0140 (5)	−0.0130 (5)	−0.0003 (4)	0.0025 (4)
Cl63	0.0124 (5)	0.0297 (6)	0.0310 (6)	−0.0106 (4)	−0.0013 (4)	−0.0023 (5)
O1	0.0118 (13)	0.0094 (13)	0.0111 (13)	−0.0067 (11)	−0.0024 (10)	0.0015 (11)
O11	0.0122 (13)	0.0107 (14)	0.0147 (14)	−0.0047 (11)	−0.0005 (11)	−0.0019 (11)
O12	0.0114 (14)	0.0135 (14)	0.0202 (15)	−0.0039 (12)	−0.0035 (12)	−0.0026 (12)
O21	0.0158 (14)	0.0196 (15)	0.0103 (13)	−0.0110 (12)	−0.0031 (11)	0.0010 (12)
O22	0.0139 (14)	0.0226 (16)	0.0118 (14)	−0.0092 (13)	−0.0025 (11)	0.0046 (12)
O31	0.0095 (13)	0.0215 (15)	0.0099 (14)	−0.0066 (12)	−0.0012 (11)	0.0048 (12)
O32	0.0119 (14)	0.0146 (14)	0.0126 (14)	−0.0042 (12)	−0.0018 (11)	0.0026 (11)
O41	0.0131 (14)	0.0117 (14)	0.0138 (14)	−0.0031 (11)	−0.0044 (11)	−0.0018 (11)
O42	0.0175 (14)	0.0131 (14)	0.0153 (15)	−0.0086 (12)	−0.0050 (12)	−0.0001 (12)
O51	0.0189 (15)	0.0137 (14)	0.0142 (14)	−0.0075 (12)	−0.0048 (12)	−0.0014 (12)
O52	0.0187 (14)	0.0118 (14)	0.0091 (13)	−0.0064 (12)	−0.0027 (11)	0.0002 (11)
O61	0.0111 (13)	0.0113 (14)	0.0166 (15)	−0.0028 (11)	0.0008 (11)	0.0003 (12)
O62	0.0087 (13)	0.0107 (14)	0.0194 (15)	−0.0031 (11)	−0.0004 (11)	−0.0021 (12)
O71	0.0111 (13)	0.0153 (14)	0.0126 (14)	−0.0070 (11)	−0.0009 (11)	−0.0020 (11)
O72	0.0313 (18)	0.0199 (17)	0.0169 (16)	−0.0177 (15)	−0.0030 (13)	0.0010 (13)
O81	0.0118 (13)	0.0138 (14)	0.0132 (14)	−0.0056 (11)	−0.0025 (11)	0.0020 (11)
O82	0.0154 (15)	0.0207 (17)	0.0174 (16)	−0.0033 (13)	−0.0064 (12)	0.0001 (13)
O91	0.0214 (15)	0.0092 (14)	0.0158 (15)	−0.0049 (12)	−0.0033 (12)	0.0000 (12)
O92	0.0174 (17)	0.039 (2)	0.0185 (17)	−0.0023 (16)	−0.0035 (13)	0.0116 (15)
C11	0.0121 (18)	0.0114 (19)	0.0097 (18)	−0.0032 (15)	−0.0027 (15)	0.0031 (15)
C12	0.0115 (19)	0.017 (2)	0.015 (2)	−0.0025 (16)	−0.0016 (15)	0.0019 (17)
C21	0.0126 (18)	0.0071 (18)	0.0134 (19)	−0.0016 (15)	−0.0002 (15)	0.0010 (15)
C22	0.0151 (19)	0.017 (2)	0.0105 (19)	−0.0093 (17)	−0.0023 (15)	0.0008 (16)
C31	0.0093 (17)	0.0086 (18)	0.0105 (18)	−0.0028 (15)	0.0002 (14)	−0.0017 (15)
C32	0.0111 (18)	0.017 (2)	0.0128 (19)	−0.0046 (16)	−0.0001 (15)	0.0016 (16)
C41	0.0104 (18)	0.0130 (19)	0.015 (2)	−0.0071 (16)	−0.0016 (15)	−0.0015 (16)
C42	0.021 (2)	0.015 (2)	0.018 (2)	−0.0054 (17)	−0.0049 (17)	−0.0031 (17)
C51	0.0061 (17)	0.015 (2)	0.0120 (19)	−0.0039 (15)	−0.0024 (14)	0.0005 (15)
C52	0.018 (2)	0.014 (2)	0.0117 (19)	−0.0078 (17)	−0.0007 (16)	0.0015 (16)
C61	0.0057 (17)	0.0147 (19)	0.0121 (19)	−0.0025 (15)	−0.0027 (14)	0.0004 (15)
C62	0.0128 (19)	0.016 (2)	0.016 (2)	−0.0064 (16)	0.0012 (16)	0.0004 (17)
C71	0.0125 (19)	0.0088 (18)	0.017 (2)	−0.0033 (15)	−0.0037 (15)	−0.0012 (16)
C72	0.017 (2)	0.018 (2)	0.024 (2)	−0.0131 (18)	0.0038 (17)	−0.0057 (18)
C81	0.0151 (19)	0.016 (2)	0.0137 (19)	−0.0106 (17)	−0.0024 (15)	0.0039 (16)
C82	0.016 (2)	0.030 (3)	0.022 (2)	−0.0064 (19)	−0.0080 (18)	0.008 (2)
C91	0.018 (2)	0.014 (2)	0.017 (2)	−0.0087 (17)	−0.0070 (16)	0.0001 (16)
C92	0.025 (2)	0.024 (2)	0.013 (2)	−0.0040 (19)	−0.0064 (18)	0.0028 (18)

Geometric parameters (Å, º)

Mn1—O1	1.826 (3)	O11—C11	1.271 (5)
Mn1—O11	1.952 (3)	O12—C11	1.228 (5)
Mn1—O62	1.965 (3)	O21—C21	1.227 (5)
Mn1—O71	1.983 (3)	O22—C21	1.265 (5)
Mn1—O21	2.153 (3)	O31—C31	1.258 (5)
Mn1—O52	2.201 (3)	O32—C31	1.235 (5)
Mn2—O1	1.830 (3)	O41—C41	1.260 (5)
Mn2—O22	1.956 (3)	O42—C41	1.221 (5)
Mn2—O31	1.981 (3)	O51—C51	1.233 (5)
Mn2—O81	1.989 (3)	O52—C51	1.256 (5)
Mn2—O41	2.178 (3)	O61—C61	1.232 (5)
Mn2—O12	2.182 (3)	O62—C61	1.260 (5)
Mn3—O42	2.139 (3)	O71—C71	1.255 (5)
Mn3—O61	2.149 (3)	O72—C71	1.303 (5)
Mn3—O51	2.153 (3)	O72—H72	0.78 (6)
Mn3—O91	2.160 (3)	O81—C81	1.237 (5)
Mn3—O1	2.167 (3)	O82—C81	1.302 (5)
Mn3—O32	2.188 (3)	O82—H82	0.75 (6)
Mn1—Mn2	3.2223 (12)	O91—C91	1.218 (5)
Mn1—Mn3	3.4126 (13)	O92—C91	1.322 (5)
Mn2—Mn3	3.4521 (16)	O92—H92	0.72 (7)
Cl11—C12	1.745 (4)	C11—C12	1.565 (6)
Cl12—C12	1.778 (4)	C21—C22	1.554 (6)
Cl13—C12	1.766 (5)	C31—C32	1.560 (5)
Cl21—C22	1.755 (4)	C41—C42	1.569 (6)
Cl22—C22	1.777 (4)	C51—C52	1.562 (6)
Cl23—C22	1.770 (4)	C61—C62	1.562 (5)
Cl31—C32	1.756 (4)	C71—C72	1.484 (6)
Cl32—C32	1.779 (4)	C72—H72A	0.9800
Cl33—C32	1.759 (4)	C72—H72B	0.9800
Cl41—C42	1.757 (5)	C72—H72C	0.9800
Cl42—C42	1.760 (5)	C81—C82	1.489 (6)
Cl43—C42	1.776 (5)	C82—H82A	0.9800
Cl51—C52	1.769 (4)	C82—H82B	0.9800
Cl52—C52	1.766 (4)	C82—H82C	0.9800
Cl53—C52	1.764 (4)	C91—C92	1.487 (6)
Cl61—C62	1.764 (4)	C92—H92A	0.9800
Cl62—C62	1.778 (5)	C92—H92B	0.9800
Cl63—C62	1.762 (4)	C92—H92C	0.9800
O1—Mn1—O11	95.63 (12)	O11—C11—C12	112.9 (3)
O1—Mn1—O62	95.31 (12)	C11—C12—Cl11	112.7 (3)
O11—Mn1—O62	169.02 (12)	C11—C12—Cl13	110.1 (3)
O1—Mn1—O71	178.40 (12)	Cl11—C12—Cl13	110.1 (2)
O11—Mn1—O71	85.54 (12)	C11—C12—Cl12	104.9 (3)
O62—Mn1—O71	83.50 (12)	Cl11—C12—Cl12	109.7 (2)
O1—Mn1—O21	94.76 (12)	Cl13—C12—Cl12	109.2 (2)
O11—Mn1—O21	91.62 (12)	O21—C21—O22	128.9 (4)
O62—Mn1—O21	86.55 (13)	O21—C21—C22	118.6 (3)
O71—Mn1—O21	84.11 (12)	O22—C21—C22	112.5 (4)
O1—Mn1—O52	94.51 (12)	C21—C22—Cl21	111.6 (3)
O11—Mn1—O52	82.32 (12)	C21—C22—Cl23	108.0 (3)
O62—Mn1—O52	97.73 (12)	Cl21—C22—Cl23	109.4 (2)
O71—Mn1—O52	86.71 (12)	C21—C22—Cl22	108.8 (3)
O21—Mn1—O52	169.38 (11)	Cl21—C22—Cl22	108.9 (2)
O1—Mn1—Mn2	28.23 (9)	Cl23—C22—Cl22	110.1 (2)
O11—Mn1—Mn2	75.24 (9)	O32—C31—O31	128.5 (4)
O62—Mn1—Mn2	114.68 (9)	O32—C31—C32	117.7 (3)
O71—Mn1—Mn2	151.83 (9)	O31—C31—C32	113.8 (3)
O21—Mn1—Mn2	76.18 (8)	C31—C32—Cl31	112.1 (3)
O52—Mn1—Mn2	110.38 (8)	C31—C32—Cl33	110.1 (3)
O1—Mn2—O22	96.73 (12)	Cl31—C32—Cl33	109.4 (2)
O1—Mn2—O31	95.98 (12)	C31—C32—Cl32	105.8 (3)
O22—Mn2—O31	167.29 (12)	Cl31—C32—Cl32	109.5 (2)
O1—Mn2—O81	179.38 (13)	Cl33—C32—Cl32	109.9 (2)
O22—Mn2—O81	83.02 (12)	O42—C41—O41	128.3 (4)
O31—Mn2—O81	84.27 (12)	O42—C41—C42	116.4 (4)
O1—Mn2—O41	93.53 (12)	O41—C41—C42	115.2 (4)
O22—Mn2—O41	84.29 (12)	C41—C42—Cl42	113.5 (3)
O31—Mn2—O41	94.51 (12)	C41—C42—Cl41	110.9 (3)
O81—Mn2—O41	85.88 (12)	Cl42—C42—Cl41	109.4 (2)
O1—Mn2—O12	93.38 (12)	C41—C42—Cl43	104.1 (3)
O22—Mn2—O12	93.38 (13)	Cl42—C42—Cl43	109.1 (3)
O31—Mn2—O12	86.29 (12)	Cl41—C42—Cl43	109.7 (2)
O81—Mn2—O12	87.20 (12)	O51—C51—O52	127.6 (4)
O41—Mn2—O12	172.92 (11)	O51—C51—C52	115.3 (4)
O1—Mn2—Mn1	28.15 (9)	O52—C51—C52	116.9 (3)
O22—Mn2—Mn1	75.69 (9)	C51—C52—Cl53	110.5 (3)
O31—Mn2—Mn1	116.43 (9)	C51—C52—Cl52	105.9 (3)
O81—Mn2—Mn1	152.03 (9)	Cl53—C52—Cl52	109.5 (2)
O41—Mn2—Mn1	109.44 (8)	C51—C52—Cl51	112.4 (3)
O12—Mn2—Mn1	76.32 (8)	Cl53—C52—Cl51	108.5 (2)
O42—Mn3—O61	85.28 (12)	Cl52—C52—Cl51	110.0 (2)
O42—Mn3—O51	173.55 (11)	O61—C61—O62	128.5 (4)
O61—Mn3—O51	97.21 (12)	O61—C61—C62	118.5 (4)
O42—Mn3—O91	95.39 (11)	O62—C61—C62	113.0 (3)
O61—Mn3—O91	92.84 (12)	C61—C62—Cl61	112.6 (3)
O51—Mn3—O91	78.58 (12)	C61—C62—Cl63	108.4 (3)
O42—Mn3—O1	93.47 (11)	Cl61—C62—Cl63	109.5 (2)
O61—Mn3—O1	91.65 (11)	C61—C62—Cl62	107.7 (3)
O51—Mn3—O1	92.41 (11)	Cl61—C62—Cl62	109.0 (2)
O91—Mn3—O1	170.37 (11)	Cl63—C62—Cl62	109.7 (2)
O42—Mn3—O32	91.30 (12)	O71—C71—O72	123.6 (4)
O61—Mn3—O32	176.36 (12)	O71—C71—C72	120.3 (4)
O51—Mn3—O32	86.06 (12)	O72—C71—C72	116.0 (4)
O91—Mn3—O32	86.22 (12)	C71—C72—H72A	109.5
O1—Mn3—O32	89.82 (11)	C71—C72—H72B	109.5
Mn1—O1—Mn2	123.61 (15)	H72A—C72—H72B	109.5
Mn1—O1—Mn3	117.18 (14)	C71—C72—H72C	109.5
Mn2—O1—Mn3	119.18 (14)	H72A—C72—H72C	109.5
C11—O11—Mn1	133.7 (3)	H72B—C72—H72C	109.5
C11—O12—Mn2	123.4 (3)	O81—C81—O82	124.6 (4)
C21—O21—Mn1	124.3 (3)	O81—C81—C82	121.5 (4)
C21—O22—Mn2	133.2 (3)	O82—C81—C82	113.9 (4)
C31—O31—Mn2	137.0 (3)	C81—C82—H82A	109.5
C31—O32—Mn3	126.3 (3)	C81—C82—H82B	109.5
C41—O41—Mn2	128.6 (3)	H82A—C82—H82B	109.5
C41—O42—Mn3	129.4 (3)	C81—C82—H82C	109.5
C51—O51—Mn3	132.2 (3)	H82A—C82—H82C	109.5
C51—O52—Mn1	127.0 (3)	H82B—C82—H82C	109.5
C61—O61—Mn3	123.9 (3)	O91—C91—O92	123.2 (4)
C61—O62—Mn1	137.2 (3)	O91—C91—C92	123.0 (4)
C71—O71—Mn1	134.7 (3)	O92—C91—C92	113.8 (4)
C71—O72—H72	106 (4)	C91—C92—H92A	109.5
C81—O81—Mn2	133.7 (3)	C91—C92—H92B	109.5
C81—O82—H82	115 (5)	H92A—C92—H92B	109.5
C91—O91—Mn3	133.7 (3)	C91—C92—H92C	109.5
C91—O92—H92	109 (5)	H92A—C92—H92C	109.5
O12—C11—O11	127.8 (4)	H92B—C92—H92C	109.5
O12—C11—C12	119.2 (3)
O11—Mn1—Mn2—O1	134.8 (2)	O32—Mn3—O42—C41	−101.3 (3)
O62—Mn1—Mn2—O1	−50.2 (2)	O61—Mn3—O51—C51	−97.7 (4)
O71—Mn1—Mn2—O1	−176.6 (3)	O91—Mn3—O51—C51	170.9 (4)
O21—Mn1—Mn2—O1	−129.7 (2)	O1—Mn3—O51—C51	−5.7 (4)
O52—Mn1—Mn2—O1	59.0 (2)	O32—Mn3—O51—C51	84.0 (4)
O1—Mn1—Mn2—O22	137.1 (2)	O1—Mn1—O52—C51	−37.1 (3)
O11—Mn1—Mn2—O22	−88.03 (13)	O11—Mn1—O52—C51	−132.2 (3)
O62—Mn1—Mn2—O22	86.98 (14)	O62—Mn1—O52—C51	58.9 (3)
O71—Mn1—Mn2—O22	−39.5 (2)	O71—Mn1—O52—C51	141.9 (3)
O21—Mn1—Mn2—O22	7.42 (12)	O21—Mn1—O52—C51	172.2 (5)
O52—Mn1—Mn2—O22	−163.83 (12)	Mn2—Mn1—O52—C51	−61.1 (3)
O1—Mn1—Mn2—O31	−47.0 (2)	O42—Mn3—O61—C61	−122.6 (3)
O11—Mn1—Mn2—O31	87.87 (14)	O51—Mn3—O61—C61	63.4 (3)
O62—Mn1—Mn2—O31	−97.13 (14)	O91—Mn3—O61—C61	142.2 (3)
O71—Mn1—Mn2—O31	136.4 (2)	O1—Mn3—O61—C61	−29.3 (3)
O21—Mn1—Mn2—O31	−176.68 (13)	O1—Mn1—O62—C61	−0.9 (4)
O52—Mn1—Mn2—O31	12.07 (13)	O11—Mn1—O62—C61	174.2 (6)
O1—Mn1—Mn2—O81	178.7 (3)	O71—Mn1—O62—C61	178.0 (4)
O11—Mn1—Mn2—O81	−46.4 (2)	O21—Mn1—O62—C61	93.6 (4)
O62—Mn1—Mn2—O81	128.6 (2)	O52—Mn1—O62—C61	−96.2 (4)
O71—Mn1—Mn2—O81	2.1 (3)	Mn2—Mn1—O62—C61	20.5 (4)
O21—Mn1—Mn2—O81	49.0 (2)	O11—Mn1—O71—C71	−56.0 (4)
O52—Mn1—Mn2—O81	−122.2 (2)	O62—Mn1—O71—C71	124.7 (4)
O1—Mn1—Mn2—O41	58.6 (2)	O21—Mn1—O71—C71	−148.1 (4)
O11—Mn1—Mn2—O41	−166.56 (12)	O52—Mn1—O71—C71	26.5 (4)
O62—Mn1—Mn2—O41	8.45 (13)	Mn2—Mn1—O71—C71	−102.6 (4)
O71—Mn1—Mn2—O41	−118.0 (2)	O22—Mn2—O81—C81	−51.1 (4)
O21—Mn1—Mn2—O41	−71.11 (12)	O31—Mn2—O81—C81	128.6 (4)
O52—Mn1—Mn2—O41	117.64 (12)	O41—Mn2—O81—C81	33.7 (4)
O1—Mn1—Mn2—O12	−125.7 (2)	O12—Mn2—O81—C81	−144.8 (4)
O11—Mn1—Mn2—O12	9.14 (12)	Mn1—Mn2—O81—C81	−91.5 (4)
O62—Mn1—Mn2—O12	−175.86 (13)	O42—Mn3—O91—C91	129.6 (4)
O71—Mn1—Mn2—O12	57.7 (2)	O61—Mn3—O91—C91	−144.9 (4)
O21—Mn1—Mn2—O12	104.59 (12)	O51—Mn3—O91—C91	−48.1 (4)
O52—Mn1—Mn2—O12	−66.66 (12)	O32—Mn3—O91—C91	38.6 (4)
O11—Mn1—O1—Mn2	−43.55 (19)	Mn2—O12—C11—O11	−6.7 (6)
O62—Mn1—O1—Mn2	135.52 (18)	Mn2—O12—C11—C12	169.7 (3)
O21—Mn1—O1—Mn2	48.56 (19)	Mn1—O11—C11—O12	24.9 (7)
O52—Mn1—O1—Mn2	−126.26 (18)	Mn1—O11—C11—C12	−151.7 (3)
O11—Mn1—O1—Mn3	138.22 (15)	O12—C11—C12—Cl11	22.3 (5)
O62—Mn1—O1—Mn3	−42.70 (16)	O11—C11—C12—Cl11	−160.8 (3)
O21—Mn1—O1—Mn3	−129.67 (15)	O12—C11—C12—Cl13	145.8 (3)
O52—Mn1—O1—Mn3	55.51 (15)	O11—C11—C12—Cl13	−37.3 (4)
Mn2—Mn1—O1—Mn3	−178.2 (3)	O12—C11—C12—Cl12	−96.9 (4)
O22—Mn2—O1—Mn1	−41.59 (19)	O11—C11—C12—Cl12	80.0 (4)
O31—Mn2—O1—Mn1	138.84 (18)	Mn1—O21—C21—O22	−1.8 (6)
O41—Mn2—O1—Mn1	−126.25 (18)	Mn1—O21—C21—C22	179.4 (3)
O12—Mn2—O1—Mn1	52.22 (18)	Mn2—O22—C21—O21	15.9 (7)
O22—Mn2—O1—Mn3	136.60 (16)	Mn2—O22—C21—C22	−165.2 (3)
O31—Mn2—O1—Mn3	−42.97 (17)	O21—C21—C22—Cl21	−3.8 (5)
O41—Mn2—O1—Mn3	51.94 (16)	O22—C21—C22—Cl21	177.1 (3)
O12—Mn2—O1—Mn3	−129.59 (15)	O21—C21—C22—Cl23	116.4 (4)
Mn1—Mn2—O1—Mn3	178.2 (3)	O22—C21—C22—Cl23	−62.6 (4)
O42—Mn3—O1—Mn1	139.22 (15)	O21—C21—C22—Cl22	−124.0 (3)
O61—Mn3—O1—Mn1	53.85 (16)	O22—C21—C22—Cl22	56.9 (4)
O51—Mn3—O1—Mn1	−43.44 (16)	Mn3—O32—C31—O31	1.3 (6)
O32—Mn3—O1—Mn1	−129.49 (16)	Mn3—O32—C31—C32	179.9 (2)
O42—Mn3—O1—Mn2	−39.09 (16)	Mn2—O31—C31—O32	19.9 (7)
O61—Mn3—O1—Mn2	−124.46 (16)	Mn2—O31—C31—C32	−158.8 (3)
O51—Mn3—O1—Mn2	138.25 (16)	O32—C31—C32—Cl31	16.1 (5)
O32—Mn3—O1—Mn2	52.20 (16)	O31—C31—C32—Cl31	−165.1 (3)
O1—Mn1—O11—C11	−0.6 (4)	O32—C31—C32—Cl33	138.1 (3)
O62—Mn1—O11—C11	−175.8 (6)	O31—C31—C32—Cl33	−43.1 (4)
O71—Mn1—O11—C11	−179.6 (4)	O32—C31—C32—Cl32	−103.2 (4)
O21—Mn1—O11—C11	−95.6 (4)	O31—C31—C32—Cl32	75.6 (4)
O52—Mn1—O11—C11	93.2 (4)	Mn3—O42—C41—O41	36.2 (6)
Mn2—Mn1—O11—C11	−20.3 (3)	Mn3—O42—C41—C42	−139.0 (3)
O1—Mn2—O12—C11	−27.3 (3)	Mn2—O41—C41—O42	−9.2 (6)
O22—Mn2—O12—C11	69.6 (3)	Mn2—O41—C41—C42	166.0 (3)
O31—Mn2—O12—C11	−123.1 (3)	O42—C41—C42—Cl42	−156.2 (3)
O81—Mn2—O12—C11	152.5 (3)	O41—C41—C42—Cl42	28.0 (5)
Mn1—Mn2—O12—C11	−4.7 (3)	O42—C41—C42—Cl41	−32.6 (5)
O1—Mn1—O21—C21	−27.0 (3)	O41—C41—C42—Cl41	151.6 (3)
O11—Mn1—O21—C21	68.8 (3)	O42—C41—C42—Cl43	85.4 (4)
O62—Mn1—O21—C21	−122.0 (3)	O41—C41—C42—Cl43	−90.4 (4)
O71—Mn1—O21—C21	154.2 (3)	Mn3—O51—C51—O52	30.6 (6)
O52—Mn1—O21—C21	123.8 (6)	Mn3—O51—C51—C52	−144.4 (3)
Mn2—Mn1—O21—C21	−5.5 (3)	Mn1—O52—C51—O51	−6.4 (6)
O1—Mn2—O22—C21	4.5 (4)	Mn1—O52—C51—C52	168.5 (2)
O31—Mn2—O22—C21	−177.4 (5)	O51—C51—C52—Cl53	−39.4 (4)
O81—Mn2—O22—C21	−176.1 (4)	O52—C51—C52—Cl53	145.1 (3)
O41—Mn2—O22—C21	97.4 (4)	O51—C51—C52—Cl52	79.0 (4)
O12—Mn2—O22—C21	−89.3 (4)	O52—C51—C52—Cl52	−96.5 (4)
Mn1—Mn2—O22—C21	−14.4 (4)	O51—C51—C52—Cl51	−160.8 (3)
O1—Mn2—O31—C31	3.9 (4)	O52—C51—C52—Cl51	23.7 (5)
O22—Mn2—O31—C31	−174.2 (5)	Mn3—O61—C61—O62	−7.0 (6)
O81—Mn2—O31—C31	−175.5 (4)	Mn3—O61—C61—C62	172.5 (3)
O41—Mn2—O31—C31	−90.1 (4)	Mn1—O62—C61—O61	30.8 (7)
O12—Mn2—O31—C31	96.9 (4)	Mn1—O62—C61—C62	−148.7 (3)
Mn1—Mn2—O31—C31	24.2 (4)	O61—C61—C62—Cl61	5.9 (5)
O42—Mn3—O32—C31	61.9 (3)	O62—C61—C62—Cl61	−174.5 (3)
O51—Mn3—O32—C31	−124.0 (3)	O61—C61—C62—Cl63	127.2 (3)
O91—Mn3—O32—C31	157.2 (3)	O62—C61—C62—Cl63	−53.3 (4)
O1—Mn3—O32—C31	−31.6 (3)	O61—C61—C62—Cl62	−114.3 (4)
O1—Mn2—O41—C41	−35.6 (3)	O62—C61—C62—Cl62	65.3 (4)
O22—Mn2—O41—C41	−132.0 (3)	Mn1—O71—C71—O72	−9.1 (6)
O31—Mn2—O41—C41	60.7 (3)	Mn1—O71—C71—C72	171.9 (3)
O81—Mn2—O41—C41	144.6 (3)	Mn2—O81—C81—O82	−14.4 (6)
Mn1—Mn2—O41—C41	−59.4 (3)	Mn2—O81—C81—C82	167.1 (3)
O61—Mn3—O42—C41	80.0 (3)	Mn3—O91—C91—O92	−34.0 (6)
O91—Mn3—O42—C41	172.4 (3)	Mn3—O91—C91—C92	145.1 (4)
O1—Mn3—O42—C41	−11.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O72—H72···O52	0.78 (6)	1.85 (6)	2.621 (4)	168 (6)
O82—H82···O41	0.75 (6)	1.98 (6)	2.641 (4)	149 (6)
O92—H92···O32	0.72 (7)	2.16 (7)	2.815 (5)	151 (7)
C72—H72B···O91^i	0.98	2.37	3.142 (5)	135
C72—H72C···O81^ii	0.98	2.46	3.367 (5)	155
C92—H92C···O72^iii	0.98	2.52	3.243 (6)	130

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