Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802023024/na6170sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802023024/na6170Isup2.hkl |
CCDC reference: 204659
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (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
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 [νco 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.
Idealized atomic positions were calculated for the cryptate H atoms [d(C—H) = 0.96 Å, Uiso = 1.2Ueq of the attached atom]. The remaining H atoms were located from a difference Fourier map and refined isotropically.
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.
Fig. 1. The molecular structure of the title compound. Ellipsoids are shown at the 50% probability level. |
[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) Å3 | 0.38 × 0.35 × 0.35 mm |
Z = 2 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.26 | w = 1/[σ2(Fo2) + (0.0552P)2] where P = (Fo2 + 2Fc2)/3 |
9907 reflections | (Δ/σ)max = 0.001 |
376 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
[K(C18H36N2O6)][Mn(C5H6)(CO)3] | γ = 91.279 (1)° |
Mr = 620.66 | V = 1486.98 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.5443 (5) Å | Mo Kα radiation |
b = 11.7528 (5) Å | µ = 0.64 mm−1 |
c = 12.5534 (6) Å | T = 150 K |
α = 110.307 (1)° | 0.38 × 0.35 × 0.35 mm |
β = 109.523 (1)° |
Bruker AXS SMART APEX diffractometer | 9907 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 9068 reflections with I > σ(I) |
Tmin = 0.794, Tmax = 0.808 | Rint = 0.016 |
19143 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.26 | Δρmax = 0.58 e Å−3 |
9907 reflections | Δρmin = −0.18 e Å−3 |
376 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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 |
Experimental details
Crystal data | |
Chemical formula | [K(C18H36N2O6)][Mn(C5H6)(CO)3] |
Mr | 620.66 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 11.5443 (5), 11.7528 (5), 12.5534 (6) |
α, β, γ (°) | 110.307 (1), 109.523 (1), 91.279 (1) |
V (Å3) | 1486.98 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.38 × 0.35 × 0.35 |
Data collection | |
Diffractometer | Bruker AXS SMART APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.794, 0.808 |
No. of measured, independent and observed [I > σ(I)] reflections | 19143, 9907, 9068 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.755 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.101, 1.26 |
No. of reflections | 9907 |
No. of parameters | 376 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.58, −0.18 |
Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXTL (Bruker, 2001), SHELXTL.
Mn—C2 | 1.778 (1) | O2—C2 | 1.166 (2) |
Mn—C3 | 1.780 (1) | O3—C3 | 1.161 (1) |
Mn—C1 | 1.785 (1) | C4—C8 | 1.516 (2) |
Mn—C7 | 2.083 (1) | C4—C5 | 1.516 (2) |
Mn—C6 | 2.088 (1) | C5—C6 | 1.424 (2) |
Mn—C5 | 2.149 (1) | C6—C7 | 1.417 (2) |
Mn—C8 | 2.149 (1) | C7—C8 | 1.424 (2) |
C1—O1 | 1.161 (2) |
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.