A potassium cryptate-2,2,2 salt of tri­carbonyl(η⁴-cyclo­penta­diene)manganese

Use of [Mn(η⁴-C₆H₆)(CO)₃]⁻ prepared by anthracenide reduction of [Mn(η⁶-C₆H₆)(CO)₃]PF₆ provides access to the title compound, (4,7,13,16,21,24-hexaoxa-1,l0-di­aza­bi­cyclo­­[8.8.8]­hexa­cosane)­potassium tri­carbonyl­(cyclo­penta­di­ene)­manganate(I), [K(C₁₈H₃₆N₂O₆)][Mn(C₅H₆)(CO)₃], by reaction of [Mn(η⁴-C₆H₆)(CO)₃]⁻ with excess of the cyclo­penta­diene monomer (C₅H₆) at 195 K. In the title compound, there is octacoordination of potassium by two N and six O atoms of the 4,7,13,16,21,24-hexaoxa-1,l0-di­aza­bi­cyclo­[8.8.8]­hexa­co­sane and η⁴-coordination of the diene in an envelope conformation to the Mn(CO)₃⁻ center, with the methyl­ene group folded out of the coordination plane.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.101
• Data-to-parameter ratio = 26.3

checkCIF results

No syntax errors found



ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           32.47
         From the CIF: _reflns_number_total               9907
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns        10733
         Completeness (_total/calc)             92.30%
          Alert C: < 95% complete


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

We have previously reported that the η⁴-benzene ligand in [Mn(η⁴-C₆H₆)(CO)₃]⁻ is activated with respect to substitution of the η⁴-benzene by polyaromatic hydrocarbons to give products such as the η⁴-naphthalene complex [Mn(η⁴-C₁₀H₈)(CO)₃]⁻ (Thompson et al., 1991). η⁴-Benzene substitution by anthracene is much slower than substitution by naphthalene (Lee et al., 1995), and [Mn(η⁴-C₆H₆)(CO)₃]⁻ prepared by anthracenide reduction can therefore provide access to the title compound, (4,7,13,16,21,24-hexaoxa-1,l0-diazabicyclo[8.8.8]hexacosane)potassium tricarbonyl(cyclopentadiene)manganese(I), by competitive substitution with excess cyclopentadiene monomer (C₅H₆). To the best of our knowledge, while there are several crystal structures of η⁴-complexes of heterosubstituted cyclic dienes with manganese(I) (Lindner et al., 1979, 1981a,b, 1988, 1996; Chen et al., 1996), the title compound, (I), is the first crystallographically characterized [Mn(η⁴-diene)(CO)₃]⁻ complex of an aliphatic diene (Fig. 1), although a methyl-substituted analog has been spectroscopically characterized prior to this study (Lee & Cooper, 1991).

The C₅H₆ ligand coordinated to Mn(CO)₃⁻ has an envelope conformation (Duax et al., 1976) with the CH₂ bent out of the plane by 34.6 (1)°. There is a plane of symmetry that includes the CH₂ group and the Mn center. This contrasts sharply with the structure of uncoordinated C₅H₆ (Liebling & Marsh, 1965) in which the C₅H₆ ring is almost planar but lacks a plane of symmetry that would render the methylene H atoms equivalent.

S2. Experimental

Reactions and manipulations were carried out under a dry oxygen-free nitrogen atmosphere using standard Schlenk and cannula techniques or a dry box. A 0.2 M potassium anthracenide/THF solution (7.3 ml, 1.46 mmol, 2.1 equivalents per Mn metal) was added into a slurry of 0.25 g (0.69 mmol) [Mn(η⁶-C₆H₆)(CO)₃]PF₆ in 15 ml THF at 195 K to form a yellow–green slurry. After 15 min, excess distilled cyclopentadiene C₅H₆ monomer (2.0 ml) was added to the stirred solution to give a yellow slurry. The yellow solution was collected by filtration at 195 K and mixed with 0.21 g (0.56 mmol) 4,7,13,16,21,24-hexaoxa-1,l0-diazabicyclo[8.8.8]hexacosane. Solvent THF was removed under vacuum at ambient temperature, and the residue rinsed with pentane (50 ml) and toluene (50 ml), and then redissolved into a small amount of DME and layered with Et₂O to give orange crystals suitable for diffraction studies (0.26 g, yield 41%) at 243 K. IR absorptions for the title compound [ν_co only, THF, 1925 (s), 1830 (s), 1811(s) cm⁻¹] are in the same range as those of [Mn(η⁴-cyclohexadiene)(CO)₃]⁻ (Brookhart et al., 1983) and [Mn(η⁴-butadiene)(CO)₃]⁻ (Brookhart et al., 1987), while the ¹H NMR spectrum of (I) has three peaks [in CD₃CN, 273 K, δ 5.0 (s, 2CH), 2.70 (s, 2CH), 1.86 (s, CH₂)] for the C₅H₆ ligand. This implies that the endo- and exo-H of the CH₂ cannot be distinguished. A similar observation has been reported for [Mn(η⁴-cyclohexadiene)(CO)₃]⁻. In the ¹³C–¹H-coupled NMR spectrum, the different coupling constants (121.3 and 136.6 Hz) of the two H atoms on the CH₂ peak (δ 46.03), did, however, finally distinguish between the endo- and exo-H.

S3. Refinement

Idealized atomic positions were calculated for the cryptate H atoms [d(C—H) = 0.96 Å, U_iso = 1.2U_eq of the attached atom]. The remaining H atoms were located from a difference Fourier map and refined isotropically.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of the title compound. Ellipsoids are shown at the 50% probability level.

Cyclopentadienylmangenesetricarbonyl

Crystal data

[K(C18H36N2O6)][Mn(C5H6)(CO)3]	F(000) = 656
Mr = 620.66	Dx = 1.386 Mg m^−3
Triclinic, P1	Melting point: not measured K
a = 11.5443 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.7528 (5) Å	Cell parameters from 6417 reflections
c = 12.5534 (6) Å	θ = 2.0–30.0°
α = 110.307 (1)°	µ = 0.64 mm^−1
β = 109.523 (1)°	T = 150 K
γ = 91.279 (1)°	Block, yellow
V = 1486.98 (11) Å^3	0.38 × 0.35 × 0.35 mm
Z = 2

Data collection

Bruker AXS SMART APEX diffractometer	9907 independent reflections
Radiation source: fine-focus sealed tube	9068 reflections with I > σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 32.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.794, Tmax = 0.808	k = −17→17
19143 measured reflections	l = −18→18

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	w = 1/[σ^2(Fo^2) + (0.0552P)^2] where P = (Fo^2 + 2Fc^2)/3
9907 reflections	(Δ/σ)max = 0.001
376 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.18 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
Mn	0.073656 (14)	0.328066 (14)	0.185712 (14)	0.02325 (5)
K	−0.311026 (19)	−0.023124 (19)	0.341090 (18)	0.02019 (5)
N1	−0.22965 (9)	0.23896 (8)	0.52244 (9)	0.02416 (17)
C1	0.20342 (12)	0.39963 (12)	0.17244 (11)	0.0358 (3)
O1	0.29054 (11)	0.44537 (13)	0.16734 (11)	0.0599 (3)
N2	−0.39412 (8)	−0.28671 (8)	0.16344 (8)	0.02378 (17)
O2	0.16087 (10)	0.08856 (10)	0.12744 (11)	0.0505 (3)
C2	0.12828 (11)	0.18434 (12)	0.15126 (11)	0.0326 (2)
O3	0.16474 (9)	0.41558 (8)	0.45338 (8)	0.03592 (19)
C3	0.12936 (10)	0.38160 (9)	0.34776 (10)	0.0260 (2)
O4	−0.45540 (8)	0.16178 (7)	0.29975 (7)	0.02735 (16)
C4	−0.13604 (11)	0.40260 (11)	0.21725 (12)	0.0298 (2)
H4A	−0.1047 (15)	0.4391 (14)	0.3076 (15)	0.036 (4)*
H4B	−0.2252 (15)	0.4125 (14)	0.1839 (14)	0.035 (4)*
C5	−0.05629 (11)	0.45414 (11)	0.16505 (11)	0.0299 (2)
H5	−0.0424 (15)	0.5420 (15)	0.1844 (14)	0.034 (4)*
O5	−0.50114 (7)	−0.07602 (8)	0.11340 (7)	0.02846 (16)
C6	−0.06702 (12)	0.36331 (12)	0.05066 (11)	0.0336 (2)
H6	−0.0525 (16)	0.3766 (16)	−0.0110 (16)	0.043 (4)*
O6	−0.28242 (7)	0.03294 (7)	0.58491 (7)	0.02385 (15)
C7	−0.10192 (11)	0.24805 (11)	0.05290 (11)	0.0320 (2)
H7	−0.1115 (16)	0.1737 (16)	−0.0121 (16)	0.043 (4)*
O7	−0.39506 (7)	−0.20819 (7)	0.41324 (7)	0.02394 (14)
C8	−0.11232 (10)	0.27155 (10)	0.16822 (11)	0.0286 (2)
H8	−0.1380 (14)	0.2085 (14)	0.1931 (14)	0.033 (4)*
O8	−0.09608 (7)	0.10738 (7)	0.36839 (8)	0.02576 (15)
O9	−0.14773 (7)	−0.14620 (7)	0.22804 (7)	0.02495 (15)
C9	−0.33522 (11)	0.30661 (10)	0.50031 (11)	0.0302 (2)
H9A	−0.3048	0.3954	0.5476	0.036*
H9B	−0.3961	0.2809	0.5307	0.036*
C10	−0.40056 (13)	0.28671 (11)	0.36766 (12)	0.0338 (2)
H10A	−0.4657	0.3399	0.3597	0.041*
H10B	−0.3401	0.3092	0.3352	0.041*
C11	−0.51163 (13)	0.13878 (13)	0.17287 (11)	0.0361 (3)
H11A	−0.4464	0.1486	0.1404	0.043*
H11B	−0.5682	0.1991	0.1611	0.043*
C12	−0.58308 (11)	0.01210 (13)	0.10510 (10)	0.0344 (3)
H12A	−0.6461	0.0011	0.1397	0.041*
H12B	−0.6271	−0.0005	0.0184	0.041*
C13	−0.57018 (10)	−0.19619 (12)	0.06483 (10)	0.0312 (2)
H13A	−0.6368	−0.2099	−0.0145	0.037*
H13B	−0.6097	−0.2045	0.1212	0.037*
C14	−0.48529 (11)	−0.28994 (11)	0.04777 (10)	0.0300 (2)
H14A	−0.5359	−0.3727	0.0025	0.036*
H14B	−0.4404	−0.2757	−0.0024	0.036*
C15	−0.19019 (11)	0.24063 (10)	0.64683 (10)	0.0281 (2)
H15A	−0.1844	0.3255	0.7038	0.034*
H15B	−0.1060	0.2174	0.6688	0.034*
C16	−0.27630 (11)	0.15566 (10)	0.66364 (10)	0.0273 (2)
H16A	−0.2452	0.1620	0.7495	0.033*
H16B	−0.3604	0.1793	0.6445	0.033*
C17	−0.35049 (11)	−0.05164 (10)	0.60892 (10)	0.0276 (2)
H17A	−0.4395	−0.0423	0.5832	0.033*
H17B	−0.3189	−0.0344	0.6975	0.033*
C18	−0.33667 (10)	−0.17979 (10)	0.54075 (10)	0.0257 (2)
H18A	−0.2473	−0.1873	0.5611	0.031*
H18B	−0.3757	−0.2382	0.5644	0.031*
C19	−0.38644 (12)	−0.33098 (10)	0.34606 (11)	0.0305 (2)
H19A	−0.4249	−0.3886	0.3710	0.037*
H19B	−0.2980	−0.3410	0.3626	0.037*
C20	−0.45295 (12)	−0.35864 (10)	0.21229 (10)	0.0305 (2)
H20A	−0.4568	−0.4471	0.1663	0.037*
H20B	−0.5395	−0.3424	0.1985	0.037*
C21	−0.12411 (11)	0.29466 (10)	0.50661 (11)	0.0293 (2)
H21A	−0.0791	0.3675	0.5814	0.035*
H21B	−0.1565	0.3231	0.4381	0.035*
C22	−0.03412 (10)	0.20761 (10)	0.48144 (11)	0.0283 (2)
H22A	0.0377	0.2510	0.4773	0.034*
H22B	−0.0027	0.1766	0.5481	0.034*
C23	−0.00880 (10)	0.04312 (10)	0.32326 (11)	0.0290 (2)
H23A	0.0448	0.0120	0.3837	0.035*
H23B	0.0450	0.0994	0.3098	0.035*
C24	−0.07702 (11)	−0.06175 (10)	0.20605 (11)	0.0294 (2)
H24A	−0.1331	−0.0310	0.1467	0.035*
H24B	−0.0170	−0.1035	0.1712	0.035*
C25	−0.20205 (11)	−0.25426 (10)	0.12142 (10)	0.0274 (2)
H25A	−0.1358	−0.2974	0.0994	0.033*
H25B	−0.2522	−0.2320	0.0525	0.033*
C26	−0.28375 (11)	−0.33746 (10)	0.14462 (11)	0.0281 (2)
H26A	−0.3115	−0.4170	0.0744	0.034*
H26B	−0.2339	−0.3536	0.2177	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.01901 (8)	0.02373 (9)	0.02428 (9)	0.00295 (6)	0.00686 (6)	0.00688 (6)
K	0.01859 (10)	0.02118 (10)	0.02170 (10)	0.00230 (7)	0.00824 (7)	0.00831 (7)
N1	0.0245 (4)	0.0192 (4)	0.0297 (4)	0.0018 (3)	0.0134 (3)	0.0071 (3)
C1	0.0328 (6)	0.0391 (6)	0.0293 (5)	−0.0028 (5)	0.0126 (5)	0.0049 (5)
O1	0.0490 (6)	0.0704 (8)	0.0513 (6)	−0.0204 (6)	0.0275 (5)	0.0054 (6)
N2	0.0244 (4)	0.0230 (4)	0.0220 (4)	0.0004 (3)	0.0091 (3)	0.0057 (3)
O2	0.0419 (6)	0.0417 (5)	0.0573 (6)	0.0237 (5)	0.0151 (5)	0.0081 (5)
C2	0.0215 (5)	0.0373 (6)	0.0325 (6)	0.0076 (4)	0.0080 (4)	0.0070 (5)
O3	0.0470 (5)	0.0296 (4)	0.0280 (4)	0.0056 (4)	0.0081 (4)	0.0125 (3)
C3	0.0244 (5)	0.0200 (4)	0.0324 (5)	0.0041 (4)	0.0078 (4)	0.0109 (4)
O4	0.0329 (4)	0.0294 (4)	0.0258 (4)	0.0100 (3)	0.0129 (3)	0.0150 (3)
C4	0.0236 (5)	0.0281 (5)	0.0386 (6)	0.0079 (4)	0.0120 (4)	0.0126 (5)
C5	0.0269 (5)	0.0263 (5)	0.0370 (6)	0.0060 (4)	0.0087 (4)	0.0152 (4)
O5	0.0208 (3)	0.0372 (4)	0.0267 (4)	0.0100 (3)	0.0075 (3)	0.0121 (3)
C6	0.0297 (6)	0.0418 (6)	0.0286 (5)	0.0066 (5)	0.0065 (4)	0.0164 (5)
O6	0.0275 (4)	0.0226 (3)	0.0231 (3)	0.0000 (3)	0.0135 (3)	0.0067 (3)
C7	0.0221 (5)	0.0309 (6)	0.0308 (5)	0.0033 (4)	0.0020 (4)	0.0047 (4)
O7	0.0279 (4)	0.0223 (3)	0.0222 (3)	0.0038 (3)	0.0082 (3)	0.0099 (3)
C8	0.0198 (5)	0.0246 (5)	0.0393 (6)	0.0038 (4)	0.0074 (4)	0.0129 (4)
O8	0.0187 (3)	0.0238 (3)	0.0338 (4)	0.0017 (3)	0.0130 (3)	0.0066 (3)
O9	0.0265 (4)	0.0235 (3)	0.0256 (3)	0.0011 (3)	0.0136 (3)	0.0064 (3)
C9	0.0303 (5)	0.0223 (5)	0.0391 (6)	0.0060 (4)	0.0170 (5)	0.0087 (4)
C10	0.0379 (6)	0.0285 (5)	0.0439 (7)	0.0106 (5)	0.0183 (5)	0.0205 (5)
C11	0.0477 (7)	0.0464 (7)	0.0292 (5)	0.0264 (6)	0.0209 (5)	0.0243 (5)
C12	0.0302 (6)	0.0535 (7)	0.0223 (5)	0.0221 (5)	0.0106 (4)	0.0157 (5)
C13	0.0200 (5)	0.0449 (6)	0.0250 (5)	0.0017 (4)	0.0064 (4)	0.0108 (5)
C14	0.0295 (5)	0.0328 (5)	0.0210 (5)	0.0006 (4)	0.0074 (4)	0.0041 (4)
C15	0.0281 (5)	0.0243 (5)	0.0262 (5)	−0.0021 (4)	0.0105 (4)	0.0028 (4)
C16	0.0302 (5)	0.0269 (5)	0.0236 (5)	0.0022 (4)	0.0140 (4)	0.0044 (4)
C17	0.0313 (5)	0.0317 (5)	0.0229 (5)	−0.0021 (4)	0.0134 (4)	0.0109 (4)
C18	0.0259 (5)	0.0283 (5)	0.0245 (5)	0.0008 (4)	0.0066 (4)	0.0145 (4)
C19	0.0426 (6)	0.0224 (5)	0.0320 (5)	0.0065 (4)	0.0176 (5)	0.0126 (4)
C20	0.0366 (6)	0.0219 (5)	0.0295 (5)	−0.0050 (4)	0.0139 (5)	0.0045 (4)
C21	0.0308 (5)	0.0188 (4)	0.0389 (6)	−0.0017 (4)	0.0176 (5)	0.0072 (4)
C22	0.0215 (5)	0.0258 (5)	0.0343 (5)	−0.0029 (4)	0.0115 (4)	0.0066 (4)
C23	0.0199 (5)	0.0288 (5)	0.0407 (6)	0.0032 (4)	0.0165 (4)	0.0105 (4)
C24	0.0305 (5)	0.0281 (5)	0.0360 (6)	0.0039 (4)	0.0213 (5)	0.0108 (4)
C25	0.0289 (5)	0.0259 (5)	0.0268 (5)	0.0045 (4)	0.0146 (4)	0.0049 (4)
C26	0.0316 (5)	0.0207 (4)	0.0311 (5)	0.0049 (4)	0.0142 (4)	0.0060 (4)

Geometric parameters (Å, º)

Mn—C2	1.778 (1)	O9—C24	1.4256 (13)
Mn—C3	1.780 (1)	C9—C10	1.5096 (18)
Mn—C1	1.785 (1)	C9—H9A	0.9900
Mn—C7	2.083 (1)	C9—H9B	0.9900
Mn—C6	2.088 (1)	C10—H10A	0.9900
Mn—C5	2.149 (1)	C10—H10B	0.9900
Mn—C8	2.149 (1)	C11—C12	1.489 (2)
K—O8	2.7431 (8)	C11—H11A	0.9900
K—O6	2.7976 (8)	C11—H11B	0.9900
K—O5	2.8082 (8)	C12—H12A	0.9900
K—O4	2.8524 (8)	C12—H12B	0.9900
K—O9	2.8539 (8)	C13—C14	1.4982 (17)
K—O7	2.8901 (8)	C13—H13A	0.9900
K—N1	3.0212 (9)	C13—H13B	0.9900
K—N2	3.0220 (9)	C14—H14A	0.9900
N1—C15	1.4659 (15)	C14—H14B	0.9900
N1—C9	1.4713 (14)	C15—C16	1.5074 (15)
N1—C21	1.4728 (13)	C15—H15A	0.9900
C1—O1	1.161 (2)	C15—H15B	0.9900
N2—C14	1.4684 (14)	C16—H16A	0.9900
N2—C20	1.4713 (14)	C16—H16B	0.9900
N2—C26	1.4739 (14)	C17—C18	1.4945 (16)
O2—C2	1.166 (2)	C17—H17A	0.9900
O3—C3	1.161 (1)	C17—H17B	0.9900
O4—C10	1.419 (2)	C18—H18A	0.9900
O4—C11	1.4261 (14)	C18—H18B	0.9900
C4—C8	1.516 (2)	C19—C20	1.5045 (17)
C4—C5	1.516 (2)	C19—H19A	0.9900
C4—H4A	0.992 (16)	C19—H19B	0.9900
C4—H4B	1.000 (16)	C20—H20A	0.9900
C5—C6	1.424 (2)	C20—H20B	0.9900
C5—H5	0.972 (16)	C21—C22	1.5061 (16)
O5—C13	1.4244 (15)	C21—H21A	0.9900
O5—C12	1.4251 (14)	C21—H21B	0.9900
C6—C7	1.417 (2)	C22—H22A	0.9900
C6—H6	0.907 (17)	C22—H22B	0.9900
O6—C16	1.4218 (13)	C23—C24	1.4925 (17)
O6—C17	1.4240 (12)	C23—H23A	0.9900
C7—C8	1.424 (2)	C23—H23B	0.9900
C7—H7	0.939 (17)	C24—H24A	0.9900
O7—C19	1.4218 (13)	C24—H24B	0.9900
O7—C18	1.4233 (12)	C25—C26	1.5069 (15)
C8—H8	0.974 (15)	C25—H25A	0.9900
O8—C23	1.4230 (13)	C25—H25B	0.9900
O8—C22	1.4272 (13)	C26—H26A	0.9900
O9—C25	1.4217 (13)	C26—H26B	0.9900
C2—Mn—C3	100.39 (5)	C25—O9—K	116.91 (6)
C2—Mn—C1	91.43 (6)	C24—O9—K	109.99 (6)
C3—Mn—C1	97.59 (5)	N1—C9—C10	113.67 (9)
C2—Mn—C7	91.42 (5)	N1—C9—H9A	108.8
C3—Mn—C7	131.99 (5)	C10—C9—H9A	108.8
C1—Mn—C7	128.71 (6)	N1—C9—H9B	108.8
C2—Mn—C6	120.19 (5)	C10—C9—H9B	108.8
C3—Mn—C6	135.92 (5)	H9A—C9—H9B	107.7
C1—Mn—C6	97.84 (6)	O4—C10—C9	109.86 (9)
C7—Mn—C6	39.72 (5)	O4—C10—H10A	109.7
C2—Mn—C5	156.57 (5)	C9—C10—H10A	109.7
C3—Mn—C5	97.12 (5)	O4—C10—H10B	109.7
C1—Mn—C5	101.60 (6)	C9—C10—H10B	109.7
C7—Mn—C5	65.23 (5)	H10A—C10—H10B	108.2
C6—Mn—C5	39.25 (5)	O4—C11—C12	110.40 (10)
C2—Mn—C8	100.57 (5)	O4—C11—H11A	109.6
C3—Mn—C8	92.72 (5)	C12—C11—H11A	109.6
C1—Mn—C8	162.53 (6)	O4—C11—H11B	109.6
C7—Mn—C8	39.27 (5)	C12—C11—H11B	109.6
C6—Mn—C8	65.17 (5)	H11A—C11—H11B	108.1
C5—Mn—C8	62.97 (4)	O5—C12—C11	110.15 (10)
O8—K—O6	100.91 (2)	O5—C12—H12A	109.6
O8—K—O5	113.35 (3)	C11—C12—H12A	109.6
O6—K—O5	139.47 (2)	O5—C12—H12B	109.6
O8—K—O4	92.97 (2)	C11—C12—H12B	109.6
O6—K—O4	98.11 (2)	H12A—C12—H12B	108.1
O5—K—O4	60.50 (2)	O5—C13—C14	109.76 (9)
O8—K—O9	60.32 (2)	O5—C13—H13A	109.7
O6—K—O9	125.20 (2)	C14—C13—H13A	109.7
O5—K—O9	91.49 (2)	O5—C13—H13B	109.7
O4—K—O9	131.07 (2)	C14—C13—H13B	109.7
O8—K—O7	140.79 (2)	H13A—C13—H13B	108.2
O6—K—O7	59.98 (2)	N2—C14—C13	113.05 (9)
O5—K—O7	100.31 (2)	N2—C14—H14A	109.0
O4—K—O7	121.87 (2)	C13—C14—H14A	109.0
O9—K—O7	100.87 (2)	N2—C14—H14B	109.0
O8—K—N1	60.67 (2)	C13—C14—H14B	109.0
O6—K—N1	59.68 (2)	H14A—C14—H14B	107.8
O5—K—N1	119.72 (3)	N1—C15—C16	113.87 (9)
O4—K—N1	60.19 (3)	N1—C15—H15A	108.8
O9—K—N1	120.25 (2)	C16—C15—H15A	108.8
O7—K—N1	119.00 (2)	N1—C15—H15B	108.8
O8—K—N2	120.26 (2)	C16—C15—H15B	108.8
O6—K—N2	119.16 (2)	H15A—C15—H15B	107.7
O5—K—N2	60.85 (2)	O6—C16—C15	109.30 (8)
O4—K—N2	120.15 (3)	O6—C16—H16A	109.8
O9—K—N2	60.54 (2)	C15—C16—H16A	109.8
O7—K—N2	59.81 (2)	O6—C16—H16B	109.8
N1—K—N2	178.80 (2)	C15—C16—H16B	109.8
C15—N1—C9	109.83 (9)	H16A—C16—H16B	108.3
C15—N1—C21	109.16 (9)	O6—C17—C18	109.56 (8)
C9—N1—C21	110.61 (9)	O6—C17—H17A	109.8
C15—N1—K	109.66 (6)	C18—C17—H17A	109.8
C9—N1—K	108.66 (6)	O6—C17—H17B	109.8
C21—N1—K	108.91 (6)	C18—C17—H17B	109.8
O1—C1—Mn	177.58 (14)	H17A—C17—H17B	108.2
C14—N2—C20	108.79 (9)	O7—C18—C17	109.22 (9)
C14—N2—C26	110.47 (9)	O7—C18—H18A	109.8
C20—N2—C26	110.18 (9)	C17—C18—H18A	109.8
C14—N2—K	109.09 (6)	O7—C18—H18B	109.8
C20—N2—K	110.17 (6)	C17—C18—H18B	109.8
C26—N2—K	108.13 (6)	H18A—C18—H18B	108.3
O2—C2—Mn	178.20 (11)	O7—C19—C20	108.77 (9)
O3—C3—Mn	179.26 (11)	O7—C19—H19A	109.9
C10—O4—C11	111.06 (9)	C20—C19—H19A	109.9
C10—O4—K	118.38 (7)	O7—C19—H19B	109.9
C11—O4—K	111.57 (6)	C20—C19—H19B	109.9
C8—C4—C5	95.52 (9)	H19A—C19—H19B	108.3
C8—C4—H4A	112.8 (9)	N2—C20—C19	114.00 (9)
C5—C4—H4A	112.5 (9)	N2—C20—H20A	108.8
C8—C4—H4B	113.8 (9)	C19—C20—H20A	108.8
C5—C4—H4B	112.2 (9)	N2—C20—H20B	108.8
H4A—C4—H4B	109.5 (12)	C19—C20—H20B	108.8
C6—C5—C4	108.30 (10)	H20A—C20—H20B	107.6
C6—C5—Mn	68.07 (7)	N1—C21—C22	113.10 (9)
C4—C5—Mn	93.19 (7)	N1—C21—H21A	109.0
C6—C5—H5	123.9 (9)	C22—C21—H21A	109.0
C4—C5—H5	120.0 (9)	N1—C21—H21B	109.0
Mn—C5—H5	130.6 (9)	C22—C21—H21B	109.0
C13—O5—C12	110.45 (9)	H21A—C21—H21B	107.8
C13—O5—K	112.78 (6)	O8—C22—C21	109.17 (9)
C12—O5—K	116.61 (7)	O8—C22—H22A	109.8
C7—C6—C5	106.86 (11)	C21—C22—H22A	109.8
C7—C6—Mn	69.96 (7)	O8—C22—H22B	109.8
C5—C6—Mn	72.69 (7)	C21—C22—H22B	109.8
C7—C6—H6	126.6 (11)	H22A—C22—H22B	108.3
C5—C6—H6	126.5 (11)	O8—C23—C24	109.35 (9)
Mn—C6—H6	121.4 (11)	O8—C23—H23A	109.8
C16—O6—C17	110.89 (8)	C24—C23—H23A	109.8
C16—O6—K	120.98 (6)	O8—C23—H23B	109.8
C17—O6—K	116.61 (6)	C24—C23—H23B	109.8
C6—C7—C8	106.94 (11)	H23A—C23—H23B	108.3
C6—C7—Mn	70.33 (7)	O9—C24—C23	109.28 (9)
C8—C7—Mn	72.86 (7)	O9—C24—H24A	109.8
C6—C7—H7	122.2 (10)	C23—C24—H24A	109.8
C8—C7—H7	130.8 (10)	O9—C24—H24B	109.8
Mn—C7—H7	120.0 (10)	C23—C24—H24B	109.8
C19—O7—C18	110.46 (8)	H24A—C24—H24B	108.3
C19—O7—K	115.45 (6)	O9—C25—C26	109.54 (8)
C18—O7—K	111.81 (6)	O9—C25—H25A	109.8
C7—C8—C4	108.35 (10)	C26—C25—H25A	109.8
C7—C8—Mn	67.87 (6)	O9—C25—H25B	109.8
C4—C8—Mn	93.17 (7)	C26—C25—H25B	109.8
C7—C8—H8	124.3 (9)	H25A—C25—H25B	108.2
C4—C8—H8	122.0 (9)	N2—C26—C25	113.64 (9)
Mn—C8—H8	126.3 (9)	N2—C26—H26A	108.8
C23—O8—C22	110.95 (8)	C25—C26—H26A	108.8
C23—O8—K	119.14 (6)	N2—C26—H26B	108.8
C22—O8—K	117.77 (6)	C25—C26—H26B	108.8
C25—O9—C24	110.79 (8)	H26A—C26—H26B	107.7