Bis[S-6-(2,2:6',2''-terpyridin-4'-yloxy)hexyl thioacetate]manganese(II) bis(hexafluorophosphate)
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010804016X/sq3166sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010804016X/sq3166Isup2.hkl |
CCDC reference: 718104
For related literature, see: Albrecht, Moth-Poulsen, Christensen, Hjelm, Bjørnholm & Ulstrup (2006); Bhula & Weatherburn (1991); Constable et al. (1999, 2000); Erre et al. (2000); Figgins & Busch (1961); Freire et al. (2001); Jeitler et al. (2003); Park, Coulomb blockade & the Kondo effect in single-atom transistors (2002); Pelascini et al. (2004).
Synthesis of the title compound was accomplished by combining the ligand, 4'-(6-acetylsulfanylhexyloxy)-2,2':6',2''-terpyridine (Albrecht, Moth-Poulsen, Guckian et al., 2006 and/or??? Albrecht, Moth-Poulsen, Christensen et al., 2006) and manganese(II) acetate in an acetone/water mixture. The compound was precipitated as a white powder by the addition of an aqueous solution of potassium hexafluorophosphate. Crystals suitable for X-ray study were obtained by slow diffusion of water into an acetonitrile solution of the compound.
Most H atoms were identified in a difference Fourier map. All H atoms were subsequently placed in idealized positions with Uiso(H) parameters constrained to 1.2Ueq of the connected non-H atom in all cases. Disorder of the hexafluorophosphate ions was modelled with two different orientations but identical structures for each of the sites. The major populations were refined to 0.814 (7) and 0.842 (7). Short F12A···F12A inter-cell distances of 2.23 Å indicate that the disorder modelling could be simplified and that long-range correlations between the orientations of the anions could be relevant.
Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg & Schreurs, 1989–2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003).
[Mn(C23H25N3O2S)2](PF6)2 | Z = 2 |
Mr = 1159.94 | F(000) = 1190 |
Triclinic, P1 | Dx = 1.504 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1270 (16) Å | Cell parameters from 24366 reflections |
b = 11.403 (3) Å | θ = 1.6–28.5° |
c = 25.822 (2) Å | µ = 0.49 mm−1 |
α = 96.302 (12)° | T = 122 K |
β = 94.287 (11)° | Needle, colorless |
γ = 105.312 (14)° | 0.63 × 0.14 × 0.03 mm |
V = 2561.2 (8) Å3 |
Nonius KappaCCD diffractometer | 12876 independent reflections |
Radiation source: fine-focus sealed tube | 9290 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.102 |
θ and ϕ scans | θmax = 28.5°, θmin = 1.6° |
Absorption correction: gaussian (Coppens, 1970) | h = −11→12 |
Tmin = 0.717, Tmax = 0.979 | k = −15→15 |
55194 measured reflections | l = −34→34 |
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)] = 0.068 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.185 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0597P)2 + 6.2908P] where P = (Fo2 + 2Fc2)/3 |
12876 reflections | (Δ/σ)max = 0.007 |
692 parameters | Δρmax = 1.93 e Å−3 |
12 restraints | Δρmin = −0.99 e Å−3 |
[Mn(C23H25N3O2S)2](PF6)2 | γ = 105.312 (14)° |
Mr = 1159.94 | V = 2561.2 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.1270 (16) Å | Mo Kα radiation |
b = 11.403 (3) Å | µ = 0.49 mm−1 |
c = 25.822 (2) Å | T = 122 K |
α = 96.302 (12)° | 0.63 × 0.14 × 0.03 mm |
β = 94.287 (11)° |
Nonius KappaCCD diffractometer | 12876 independent reflections |
Absorption correction: gaussian (Coppens, 1970) | 9290 reflections with I > 2σ(I) |
Tmin = 0.717, Tmax = 0.979 | Rint = 0.102 |
55194 measured reflections |
R[F2 > 2σ(F2)] = 0.068 | 12 restraints |
wR(F2) = 0.185 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.93 e Å−3 |
12876 reflections | Δρmin = −0.99 e Å−3 |
692 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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.6283 (0.0029) x + 7.9014 (0.0040) y - 13.7646 (0.0122) z = 6.8068 (0.0059) * 0.0488 (0.0031) C9 * -0.0397 (0.0036) C10 * -0.0975 (0.0042) C11 * -0.0592 (0.0040) C12 * 0.0195 (0.0031) C13 * 0.0196 (0.0029) C14 * 0.0052 (0.0029) C15 * 0.0044 (0.0028) C16 * 0.0246 (0.0029) C17 * 0.0300 (0.0029) C18 * 0.0233 (0.0030) C19 * -0.0391 (0.0037) C20 * -0.0712 (0.0041) C21 * -0.0607 (0.0036) C22 * 0.0121 (0.0033) C23 * 0.0755 (0.0026) N24 * 0.0431 (0.0025) N25 * 0.0611 (0.0027) N26 Rms deviation of fitted atoms = 0.0480 - 8.2411 (0.0024) x + 6.7811 (0.0032) y - 5.1448 (0.0129) z = 0.9849 (0.0033) Angle to previous plane (with approximate esd) = 88.06 ( 0.03 ) * -0.0483 (0.0030) C27 * -0.0138 (0.0032) C28 * 0.0365 (0.0033) C29 * 0.0778 (0.0031) C30 * 0.0225 (0.0029) C31 * 0.0241 (0.0028) C32 * 0.0139 (0.0029) C33 * -0.0374 (0.0028) C34 * -0.0573 (0.0029) C35 * -0.0266 (0.0029) C36 * -0.0270 (0.0029) C37 * 0.0166 (0.0032) C38 * 0.0596 (0.0032) C39 * 0.0467 (0.0030) C40 * -0.0111 (0.0028) C41 * -0.0414 (0.0026) N42 * 0.0137 (0.0025) N43 * -0.0485 (0.0025) N44 Rms deviation of fitted atoms = 0.0392 |
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 | Occ. (<1) | |
Mn1 | 0.55805 (5) | 0.94328 (4) | 0.173146 (17) | 0.02023 (12) | |
P2 | 0.90119 (11) | 0.67886 (9) | 0.05315 (3) | 0.0305 (2) | |
S57 | 0.69834 (12) | 1.89143 (9) | 0.57218 (4) | 0.0395 (2) | |
S59 | 0.32543 (16) | 0.29891 (11) | −0.38146 (4) | 0.0551 (3) | |
N26 | 0.3554 (3) | 1.0217 (3) | 0.18127 (10) | 0.0238 (5) | |
N25 | 0.5845 (3) | 1.0394 (2) | 0.25306 (9) | 0.0206 (5) | |
N24 | 0.7580 (3) | 0.9030 (2) | 0.21815 (9) | 0.0221 (5) | |
N44 | 0.7056 (3) | 1.0992 (3) | 0.13657 (10) | 0.0235 (5) | |
N43 | 0.5482 (3) | 0.8812 (2) | 0.08919 (9) | 0.0214 (5) | |
O45 | 0.5584 (3) | 0.7650 (2) | −0.06636 (9) | 0.0346 (6) | |
N42 | 0.4061 (3) | 0.7524 (3) | 0.15775 (10) | 0.0249 (6) | |
O46 | 0.6489 (3) | 1.2520 (2) | 0.39649 (9) | 0.0300 (5) | |
F16 | 0.8352 (3) | 0.6842 (3) | −0.00507 (8) | 0.0522 (7) | |
C18 | 0.4876 (4) | 1.1061 (3) | 0.26678 (11) | 0.0211 (6) | |
C19 | 0.3570 (4) | 1.0948 (3) | 0.22635 (12) | 0.0233 (6) | |
C31 | 0.3821 (4) | 0.6947 (3) | 0.10768 (12) | 0.0232 (6) | |
C13 | 0.8008 (4) | 0.9624 (3) | 0.26765 (12) | 0.0234 (6) | |
C33 | 0.4613 (4) | 0.7205 (3) | 0.01658 (12) | 0.0274 (7) | |
H33 | 0.4005 | 0.6402 | 0.0029 | 0.033* | |
C14 | 0.7039 (3) | 1.0409 (3) | 0.28715 (11) | 0.0209 (6) | |
C17 | 0.5105 (4) | 1.1786 (3) | 0.31483 (12) | 0.0244 (6) | |
H17 | 0.4427 | 1.2264 | 0.3237 | 0.029* | |
C32 | 0.4655 (4) | 0.7670 (3) | 0.06909 (12) | 0.0227 (6) | |
C16 | 0.6347 (4) | 1.1803 (3) | 0.35003 (12) | 0.0239 (6) | |
C9 | 0.8376 (4) | 0.8292 (3) | 0.19869 (12) | 0.0284 (7) | |
H9 | 0.8073 | 0.7881 | 0.1640 | 0.034* | |
C37 | 0.7180 (4) | 1.0783 (3) | 0.08486 (12) | 0.0235 (6) | |
C36 | 0.6321 (4) | 0.9537 (3) | 0.05827 (12) | 0.0233 (6) | |
F15 | 0.9678 (4) | 0.6740 (4) | 0.11137 (9) | 0.0845 (12) | |
C47 | 0.7790 (4) | 1.2616 (3) | 0.43435 (12) | 0.0311 (7) | |
H47A | 0.8753 | 1.3030 | 0.4208 | 0.037* | |
H47B | 0.7838 | 1.1791 | 0.4415 | 0.037* | |
C15 | 0.7339 (4) | 1.1107 (3) | 0.33614 (11) | 0.0231 (6) | |
H15 | 0.8195 | 1.1110 | 0.3596 | 0.028* | |
C41 | 0.7766 (4) | 1.2108 (3) | 0.16257 (13) | 0.0263 (7) | |
H41 | 0.7679 | 1.2258 | 0.1990 | 0.032* | |
C49 | 0.7524 (5) | 1.4664 (3) | 0.47756 (13) | 0.0315 (8) | |
H49A | 0.6641 | 1.4632 | 0.4522 | 0.038* | |
H49B | 0.8466 | 1.5086 | 0.4631 | 0.038* | |
C38 | 0.8033 (4) | 1.1682 (3) | 0.05833 (13) | 0.0304 (7) | |
H38 | 0.8117 | 1.1509 | 0.0220 | 0.037* | |
C48 | 0.7563 (5) | 1.3366 (3) | 0.48413 (13) | 0.0321 (8) | |
H48A | 0.6591 | 1.2935 | 0.4967 | 0.039* | |
H48B | 0.8400 | 1.3405 | 0.5115 | 0.039* | |
C35 | 0.6353 (4) | 0.9135 (3) | 0.00600 (12) | 0.0271 (7) | |
H35 | 0.6957 | 0.9656 | −0.0153 | 0.033* | |
C51 | 0.7312 (5) | 1.6698 (3) | 0.52399 (13) | 0.0325 (8) | |
H51A | 0.8224 | 1.7138 | 0.5084 | 0.039* | |
H51B | 0.6397 | 1.6659 | 0.5000 | 0.039* | |
C50 | 0.7397 (5) | 1.5397 (3) | 0.52948 (13) | 0.0328 (8) | |
H50A | 0.6472 | 1.4956 | 0.5444 | 0.039* | |
H50B | 0.8294 | 1.5442 | 0.5545 | 0.039* | |
C55 | 0.4489 (5) | 0.5283 (3) | −0.23963 (13) | 0.0345 (8) | |
H55A | 0.4169 | 0.5983 | −0.2515 | 0.041* | |
H55B | 0.5603 | 0.5450 | −0.2415 | 0.041* | |
C54 | 0.4173 (5) | 0.5209 (3) | −0.18231 (13) | 0.0332 (8) | |
H54A | 0.3067 | 0.5083 | −0.1796 | 0.040* | |
H54B | 0.4470 | 0.4503 | −0.1701 | 0.040* | |
C30 | 0.2866 (4) | 0.5767 (3) | 0.09438 (14) | 0.0304 (7) | |
H30 | 0.2691 | 0.5382 | 0.0591 | 0.036* | |
C40 | 0.8622 (4) | 1.3052 (3) | 0.13867 (14) | 0.0312 (7) | |
H40 | 0.9106 | 1.3833 | 0.1582 | 0.037* | |
C22 | 0.1205 (4) | 1.0586 (4) | 0.14935 (15) | 0.0399 (9) | |
H22 | 0.0388 | 1.0438 | 0.1223 | 0.048* | |
C34 | 0.5491 (4) | 0.7956 (3) | −0.01511 (12) | 0.0280 (7) | |
C20 | 0.2435 (4) | 1.1530 (4) | 0.23438 (15) | 0.0352 (8) | |
H20 | 0.2468 | 1.2044 | 0.2662 | 0.042* | |
C52 | 0.4823 (5) | 0.6408 (3) | −0.09062 (13) | 0.0342 (8) | |
H52A | 0.3718 | 0.6200 | −0.0865 | 0.041* | |
H52B | 0.5270 | 0.5812 | −0.0747 | 0.041* | |
C23 | 0.2386 (4) | 1.0040 (3) | 0.14384 (13) | 0.0321 (8) | |
H23 | 0.2366 | 0.9519 | 0.1123 | 0.039* | |
C39 | 0.8755 (4) | 1.2829 (4) | 0.08557 (14) | 0.0346 (8) | |
H39 | 0.9335 | 1.3457 | 0.0681 | 0.041* | |
C11 | 1.0066 (5) | 0.8696 (4) | 0.27709 (15) | 0.0455 (11) | |
H11 | 1.0914 | 0.8577 | 0.2974 | 0.055* | |
C28 | 0.2397 (4) | 0.5745 (4) | 0.18449 (15) | 0.0374 (8) | |
H28 | 0.1912 | 0.5346 | 0.2116 | 0.045* | |
C27 | 0.3347 (4) | 0.6927 (3) | 0.19485 (14) | 0.0311 (7) | |
H27 | 0.3502 | 0.7336 | 0.2297 | 0.037* | |
C53 | 0.5078 (5) | 0.6392 (3) | −0.14791 (12) | 0.0326 (8) | |
H53A | 0.6180 | 0.6508 | −0.1511 | 0.039* | |
H53B | 0.4789 | 0.7092 | −0.1611 | 0.039* | |
C29 | 0.2174 (4) | 0.5161 (4) | 0.13350 (16) | 0.0368 (8) | |
H29 | 0.1543 | 0.4342 | 0.1253 | 0.044* | |
C10 | 0.9626 (5) | 0.8093 (4) | 0.22666 (14) | 0.0378 (9) | |
H10 | 1.0164 | 0.7557 | 0.2116 | 0.045* | |
C56 | 0.3675 (5) | 0.4125 (4) | −0.27706 (14) | 0.0385 (9) | |
H56A | 0.2555 | 0.3974 | −0.2775 | 0.046* | |
H56B | 0.3957 | 0.3410 | −0.2651 | 0.046* | |
C12 | 0.9260 (4) | 0.9473 (4) | 0.29768 (13) | 0.0381 (9) | |
H12 | 0.9558 | 0.9902 | 0.3321 | 0.046* | |
C21 | 0.1247 (5) | 1.1345 (4) | 0.19480 (17) | 0.0450 (10) | |
H21 | 0.0465 | 1.1744 | 0.1992 | 0.054* | |
P61 | 0.01947 (13) | 0.42903 (13) | 0.30770 (4) | 0.0532 (3) | |
O74 | 0.9949 (3) | 1.9364 (3) | 0.56851 (11) | 0.0435 (7) | |
C69 | 0.8858 (5) | 1.9774 (3) | 0.56676 (13) | 0.0345 (8) | |
F26 | 0.0141 (4) | 0.5463 (3) | 0.28187 (15) | 0.0846 (11) | |
C60 | 0.7232 (5) | 1.7401 (3) | 0.57669 (14) | 0.0357 (8) | |
H60A | 0.8185 | 1.7487 | 0.5996 | 0.043* | |
H60B | 0.6371 | 1.6920 | 0.5934 | 0.043* | |
O73 | 0.5460 (5) | 0.2198 (4) | −0.33727 (16) | 0.0758 (11) | |
F25 | 0.0266 (4) | 0.3093 (5) | 0.33281 (19) | 0.136 (2) | |
C68 | 0.4138 (6) | 0.4283 (4) | −0.33258 (16) | 0.0500 (11) | |
H68A | 0.5261 | 0.4441 | −0.3313 | 0.060* | |
H68B | 0.3873 | 0.5014 | −0.3434 | 0.060* | |
C70 | 0.8984 (6) | 2.1101 (4) | 0.56038 (18) | 0.0488 (10) | |
H70A | 1.0051 | 2.1531 | 0.5576 | 0.059* | |
H70B | 0.8632 | 2.1495 | 0.5909 | 0.059* | |
H70C | 0.8349 | 2.1135 | 0.5286 | 0.059* | |
C71 | 0.4460 (6) | 0.2051 (5) | −0.37387 (18) | 0.0551 (12) | |
C72 | 0.4123 (7) | 0.0988 (4) | −0.4187 (2) | 0.0653 (15) | |
H72A | 0.4821 | 0.0481 | −0.4132 | 0.078* | |
H72B | 0.4265 | 0.1316 | −0.4521 | 0.078* | |
H72C | 0.3066 | 0.0487 | −0.4196 | 0.078* | |
F11 | 0.9234 (8) | 0.8226 (4) | 0.06539 (19) | 0.102 (2) | 0.814 (7) |
F12 | 1.0668 (4) | 0.6989 (5) | 0.03434 (15) | 0.0623 (14) | 0.814 (7) |
F13 | 0.8762 (6) | 0.5368 (3) | 0.04328 (17) | 0.0744 (14) | 0.814 (7) |
F14 | 0.7403 (5) | 0.6622 (6) | 0.07469 (15) | 0.091 (2) | 0.814 (7) |
F21 | −0.0336 (7) | 0.4759 (8) | 0.35922 (18) | 0.158 (3) | 0.842 (7) |
F22 | 0.1939 (4) | 0.4813 (6) | 0.3256 (2) | 0.119 (2) | 0.842 (7) |
F23 | 0.0673 (6) | 0.3695 (3) | 0.25374 (14) | 0.0692 (13) | 0.842 (7) |
F24 | −0.1549 (4) | 0.3626 (4) | 0.28576 (17) | 0.0726 (15) | 0.842 (7) |
F11A | 1.0580 (17) | 0.7618 (14) | 0.0557 (7) | 0.052 (4)* | 0.186 (7) |
F12A | 0.9546 (17) | 0.5648 (14) | 0.0255 (6) | 0.047 (4)* | 0.186 (7) |
F13A | 0.7239 (15) | 0.5861 (13) | 0.0454 (6) | 0.050 (4)* | 0.186 (7) |
F14A | 0.8245 (15) | 0.7747 (13) | 0.0711 (5) | 0.034 (3)* | 0.186 (7) |
F21A | 0.101 (3) | 0.536 (2) | 0.3607 (10) | 0.109 (10)* | 0.158 (7) |
F22A | 0.181 (3) | 0.441 (2) | 0.2884 (11) | 0.085 (8)* | 0.158 (7) |
F23A | −0.046 (3) | 0.350 (3) | 0.2612 (10) | 0.109 (10)* | 0.158 (7) |
F24A | −0.1438 (18) | 0.4247 (16) | 0.3253 (7) | 0.053 (5)* | 0.158 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0235 (2) | 0.0246 (2) | 0.0125 (2) | 0.00785 (19) | 0.00074 (17) | −0.00029 (17) |
P2 | 0.0385 (5) | 0.0348 (5) | 0.0220 (4) | 0.0197 (4) | −0.0008 (4) | −0.0015 (3) |
S57 | 0.0491 (6) | 0.0324 (5) | 0.0417 (5) | 0.0190 (4) | 0.0104 (4) | 0.0023 (4) |
S59 | 0.0818 (9) | 0.0530 (7) | 0.0261 (5) | 0.0199 (6) | −0.0089 (5) | −0.0070 (4) |
N26 | 0.0227 (13) | 0.0286 (14) | 0.0195 (12) | 0.0072 (11) | −0.0005 (10) | 0.0015 (10) |
N25 | 0.0240 (13) | 0.0232 (13) | 0.0146 (11) | 0.0072 (11) | 0.0014 (10) | 0.0010 (9) |
N24 | 0.0276 (14) | 0.0268 (14) | 0.0142 (11) | 0.0119 (11) | 0.0035 (10) | 0.0009 (10) |
N44 | 0.0236 (13) | 0.0305 (14) | 0.0168 (12) | 0.0089 (11) | 0.0005 (10) | 0.0027 (10) |
N43 | 0.0243 (13) | 0.0264 (13) | 0.0138 (11) | 0.0094 (11) | −0.0011 (10) | 0.0001 (10) |
O45 | 0.0565 (16) | 0.0354 (14) | 0.0140 (10) | 0.0181 (12) | 0.0039 (10) | −0.0016 (9) |
N42 | 0.0268 (14) | 0.0293 (14) | 0.0190 (12) | 0.0087 (12) | 0.0019 (10) | 0.0028 (11) |
O46 | 0.0373 (13) | 0.0344 (13) | 0.0186 (11) | 0.0164 (11) | −0.0013 (9) | −0.0082 (9) |
F16 | 0.0635 (16) | 0.0714 (17) | 0.0249 (11) | 0.0347 (14) | −0.0126 (11) | −0.0073 (11) |
C18 | 0.0240 (15) | 0.0219 (15) | 0.0183 (14) | 0.0079 (12) | 0.0044 (11) | 0.0017 (11) |
C19 | 0.0224 (15) | 0.0261 (16) | 0.0215 (15) | 0.0074 (13) | 0.0012 (12) | 0.0026 (12) |
C31 | 0.0234 (15) | 0.0272 (16) | 0.0199 (14) | 0.0100 (13) | −0.0008 (12) | 0.0011 (12) |
C13 | 0.0272 (16) | 0.0281 (16) | 0.0168 (14) | 0.0121 (13) | 0.0028 (12) | 0.0000 (12) |
C33 | 0.0378 (18) | 0.0287 (17) | 0.0168 (14) | 0.0152 (15) | −0.0036 (13) | −0.0027 (12) |
C14 | 0.0226 (15) | 0.0248 (15) | 0.0164 (13) | 0.0088 (12) | 0.0011 (11) | 0.0026 (11) |
C17 | 0.0275 (16) | 0.0261 (16) | 0.0217 (15) | 0.0119 (13) | 0.0052 (12) | −0.0001 (12) |
C32 | 0.0252 (15) | 0.0286 (16) | 0.0169 (14) | 0.0137 (13) | −0.0016 (11) | 0.0013 (12) |
C16 | 0.0307 (17) | 0.0238 (15) | 0.0159 (14) | 0.0064 (13) | 0.0032 (12) | −0.0014 (11) |
C9 | 0.0362 (18) | 0.0336 (18) | 0.0184 (15) | 0.0159 (15) | 0.0050 (13) | −0.0004 (13) |
C37 | 0.0213 (15) | 0.0315 (17) | 0.0181 (14) | 0.0088 (13) | −0.0014 (11) | 0.0040 (12) |
C36 | 0.0261 (16) | 0.0299 (17) | 0.0176 (14) | 0.0140 (13) | −0.0004 (12) | 0.0054 (12) |
F15 | 0.114 (3) | 0.157 (3) | 0.0230 (12) | 0.109 (3) | 0.0069 (14) | 0.0119 (16) |
C47 | 0.041 (2) | 0.0334 (18) | 0.0189 (15) | 0.0163 (16) | −0.0046 (14) | −0.0050 (13) |
C15 | 0.0259 (16) | 0.0295 (16) | 0.0136 (13) | 0.0086 (13) | 0.0001 (11) | −0.0004 (11) |
C41 | 0.0228 (15) | 0.0321 (17) | 0.0219 (15) | 0.0064 (13) | −0.0021 (12) | 0.0002 (13) |
C49 | 0.048 (2) | 0.0276 (17) | 0.0184 (15) | 0.0119 (16) | 0.0015 (14) | −0.0037 (13) |
C38 | 0.0280 (17) | 0.0393 (19) | 0.0226 (16) | 0.0056 (15) | 0.0007 (13) | 0.0085 (14) |
C48 | 0.048 (2) | 0.0300 (18) | 0.0173 (15) | 0.0134 (16) | −0.0034 (14) | −0.0044 (13) |
C35 | 0.0358 (18) | 0.0358 (18) | 0.0158 (14) | 0.0176 (15) | 0.0057 (13) | 0.0084 (13) |
C51 | 0.045 (2) | 0.0299 (18) | 0.0228 (16) | 0.0121 (16) | 0.0028 (15) | −0.0008 (13) |
C50 | 0.049 (2) | 0.0269 (17) | 0.0224 (16) | 0.0132 (16) | 0.0009 (15) | −0.0012 (13) |
C55 | 0.054 (2) | 0.0324 (19) | 0.0177 (15) | 0.0158 (17) | −0.0007 (15) | 0.0002 (13) |
C54 | 0.047 (2) | 0.0349 (19) | 0.0197 (15) | 0.0177 (17) | 0.0004 (14) | 0.0005 (13) |
C30 | 0.0272 (17) | 0.0329 (18) | 0.0280 (17) | 0.0074 (14) | −0.0044 (13) | −0.0011 (14) |
C40 | 0.0262 (17) | 0.0300 (18) | 0.0321 (18) | 0.0018 (14) | −0.0052 (14) | 0.0021 (14) |
C22 | 0.0308 (19) | 0.051 (2) | 0.036 (2) | 0.0142 (17) | −0.0108 (16) | 0.0000 (17) |
C34 | 0.0379 (18) | 0.0367 (19) | 0.0136 (14) | 0.0196 (15) | −0.0013 (13) | 0.0009 (13) |
C20 | 0.0337 (19) | 0.041 (2) | 0.0330 (19) | 0.0190 (16) | 0.0001 (15) | −0.0031 (15) |
C52 | 0.053 (2) | 0.0364 (19) | 0.0169 (15) | 0.0219 (17) | 0.0020 (15) | −0.0005 (13) |
C23 | 0.0299 (18) | 0.039 (2) | 0.0241 (16) | 0.0087 (15) | −0.0056 (13) | 0.0002 (14) |
C39 | 0.0280 (17) | 0.040 (2) | 0.0328 (18) | 0.0009 (15) | 0.0002 (14) | 0.0145 (16) |
C11 | 0.048 (2) | 0.073 (3) | 0.0282 (18) | 0.043 (2) | −0.0026 (17) | −0.0008 (18) |
C28 | 0.0313 (19) | 0.042 (2) | 0.038 (2) | 0.0052 (16) | 0.0081 (16) | 0.0136 (17) |
C27 | 0.0322 (18) | 0.0372 (19) | 0.0262 (17) | 0.0119 (15) | 0.0071 (14) | 0.0059 (14) |
C53 | 0.051 (2) | 0.0361 (19) | 0.0158 (14) | 0.0222 (17) | 0.0025 (14) | 0.0001 (13) |
C29 | 0.0278 (18) | 0.0326 (19) | 0.045 (2) | 0.0007 (15) | −0.0015 (16) | 0.0057 (16) |
C10 | 0.043 (2) | 0.051 (2) | 0.0300 (18) | 0.0319 (19) | 0.0068 (16) | 0.0004 (16) |
C56 | 0.053 (2) | 0.036 (2) | 0.0223 (17) | 0.0064 (18) | −0.0012 (16) | 0.0021 (14) |
C12 | 0.042 (2) | 0.059 (2) | 0.0184 (15) | 0.0299 (19) | −0.0037 (14) | −0.0059 (15) |
C21 | 0.032 (2) | 0.056 (3) | 0.051 (2) | 0.0250 (19) | −0.0052 (17) | −0.001 (2) |
P61 | 0.0407 (6) | 0.0810 (9) | 0.0285 (5) | −0.0035 (6) | 0.0030 (4) | 0.0173 (5) |
O74 | 0.0451 (16) | 0.0456 (16) | 0.0392 (15) | 0.0164 (13) | −0.0069 (12) | 0.0011 (12) |
C69 | 0.046 (2) | 0.037 (2) | 0.0200 (16) | 0.0154 (17) | −0.0029 (15) | 0.0003 (14) |
F26 | 0.098 (3) | 0.0549 (18) | 0.115 (3) | 0.0282 (18) | 0.057 (2) | 0.0231 (18) |
C60 | 0.056 (2) | 0.0293 (18) | 0.0264 (17) | 0.0184 (17) | 0.0098 (16) | 0.0022 (14) |
O73 | 0.082 (3) | 0.071 (3) | 0.071 (3) | 0.023 (2) | −0.009 (2) | 0.003 (2) |
F25 | 0.0511 (19) | 0.213 (5) | 0.166 (4) | 0.017 (2) | 0.008 (2) | 0.164 (4) |
C68 | 0.073 (3) | 0.033 (2) | 0.033 (2) | 0.001 (2) | −0.010 (2) | 0.0017 (16) |
C70 | 0.061 (3) | 0.037 (2) | 0.047 (2) | 0.012 (2) | 0.002 (2) | 0.0090 (18) |
C71 | 0.068 (3) | 0.052 (3) | 0.039 (2) | 0.005 (2) | 0.004 (2) | 0.005 (2) |
C72 | 0.102 (4) | 0.044 (3) | 0.052 (3) | 0.018 (3) | 0.027 (3) | 0.007 (2) |
F11 | 0.159 (6) | 0.038 (2) | 0.098 (3) | 0.046 (3) | −0.077 (4) | −0.033 (2) |
F12 | 0.0390 (18) | 0.108 (4) | 0.048 (2) | 0.0210 (19) | 0.0088 (15) | 0.043 (2) |
F13 | 0.108 (4) | 0.0299 (17) | 0.083 (3) | 0.013 (2) | 0.012 (3) | 0.0140 (17) |
F14 | 0.061 (2) | 0.189 (6) | 0.048 (2) | 0.072 (3) | 0.0154 (18) | 0.016 (3) |
F21 | 0.126 (5) | 0.260 (8) | 0.051 (3) | −0.006 (5) | 0.048 (3) | −0.021 (4) |
F22 | 0.041 (2) | 0.156 (5) | 0.118 (5) | −0.035 (3) | −0.012 (2) | 0.009 (4) |
F23 | 0.111 (4) | 0.0441 (19) | 0.058 (2) | 0.028 (2) | 0.018 (2) | 0.0100 (16) |
F24 | 0.051 (2) | 0.071 (3) | 0.084 (3) | −0.0035 (18) | −0.0251 (19) | 0.033 (2) |
Mn1—N25 | 2.192 (2) | C55—C56 | 1.525 (5) |
Mn1—N43 | 2.193 (2) | C55—C54 | 1.536 (5) |
Mn1—N42 | 2.226 (3) | C55—H55A | 0.9900 |
Mn1—N24 | 2.266 (3) | C55—H55B | 0.9900 |
Mn1—N26 | 2.270 (3) | C54—C53 | 1.526 (5) |
Mn1—N44 | 2.272 (3) | C54—H54A | 0.9900 |
P2—F11A | 1.485 (14) | C54—H54B | 0.9900 |
P2—F14A | 1.497 (12) | C30—C29 | 1.384 (5) |
P2—F13 | 1.564 (3) | C30—H30 | 0.9500 |
P2—F14 | 1.581 (4) | C40—C39 | 1.387 (5) |
P2—F12 | 1.588 (3) | C40—H40 | 0.9500 |
P2—F11 | 1.590 (4) | C22—C21 | 1.371 (6) |
P2—F16 | 1.591 (2) | C22—C23 | 1.388 (5) |
P2—F15 | 1.591 (3) | C22—H22 | 0.9500 |
P2—F12A | 1.619 (13) | C20—C21 | 1.389 (5) |
P2—F13A | 1.667 (13) | C20—H20 | 0.9500 |
S57—C69 | 1.757 (4) | C52—C53 | 1.513 (4) |
S57—C60 | 1.814 (4) | C52—H52A | 0.9900 |
S59—C71 | 1.741 (6) | C52—H52B | 0.9900 |
S59—C68 | 1.797 (4) | C23—H23 | 0.9500 |
N26—C23 | 1.342 (4) | C39—H39 | 0.9500 |
N26—C19 | 1.352 (4) | C11—C12 | 1.381 (5) |
N25—C14 | 1.344 (4) | C11—C10 | 1.382 (5) |
N25—C18 | 1.352 (4) | C11—H11 | 0.9500 |
N24—C9 | 1.332 (4) | C28—C27 | 1.381 (5) |
N24—C13 | 1.357 (4) | C28—C29 | 1.384 (6) |
N44—C41 | 1.342 (4) | C28—H28 | 0.9500 |
N44—C37 | 1.349 (4) | C27—H27 | 0.9500 |
N43—C32 | 1.345 (4) | C53—H53A | 0.9900 |
N43—C36 | 1.345 (4) | C53—H53B | 0.9900 |
O45—C34 | 1.346 (4) | C29—H29 | 0.9500 |
O45—C52 | 1.450 (4) | C10—H10 | 0.9500 |
N42—C27 | 1.345 (4) | C56—C68 | 1.541 (5) |
N42—C31 | 1.359 (4) | C56—H56A | 0.9900 |
O46—C16 | 1.352 (4) | C56—H56B | 0.9900 |
O46—C47 | 1.453 (4) | C12—H12 | 0.9500 |
C18—C17 | 1.383 (4) | C21—H21 | 0.9500 |
C18—C19 | 1.494 (4) | P61—F23A | 1.41 (2) |
C19—C20 | 1.387 (5) | P61—F21 | 1.538 (5) |
C31—C30 | 1.386 (5) | P61—F22 | 1.559 (4) |
C31—C32 | 1.488 (4) | P61—F26 | 1.569 (3) |
C13—C12 | 1.392 (5) | P61—F22A | 1.57 (2) |
C13—C14 | 1.491 (4) | P61—F24A | 1.580 (16) |
C33—C34 | 1.391 (5) | P61—F25 | 1.588 (4) |
C33—C32 | 1.395 (4) | P61—F24 | 1.601 (3) |
C33—H33 | 0.9500 | P61—F23 | 1.622 (4) |
C14—C15 | 1.386 (4) | P61—F21A | 1.71 (2) |
C17—C16 | 1.394 (4) | O74—C69 | 1.207 (5) |
C17—H17 | 0.9500 | C69—C70 | 1.515 (5) |
C16—C15 | 1.395 (4) | C60—H60A | 0.9900 |
C9—C10 | 1.387 (5) | C60—H60B | 0.9900 |
C9—H9 | 0.9500 | O73—C71 | 1.228 (6) |
C37—C38 | 1.392 (5) | C68—H68A | 0.9900 |
C37—C36 | 1.490 (5) | C68—H68B | 0.9900 |
C36—C35 | 1.382 (4) | C70—H70A | 0.9800 |
C47—C48 | 1.523 (4) | C70—H70B | 0.9800 |
C47—H47A | 0.9900 | C70—H70C | 0.9800 |
C47—H47B | 0.9900 | C71—C72 | 1.531 (7) |
C15—H15 | 0.9500 | C72—H72A | 0.9800 |
C41—C40 | 1.387 (5) | C72—H72B | 0.9800 |
C41—H41 | 0.9500 | C72—H72C | 0.9800 |
C49—C48 | 1.517 (5) | F11—F14A | 0.955 (12) |
C49—C50 | 1.529 (4) | F11—F11A | 1.584 (16) |
C49—H49A | 0.9900 | F12—F11A | 0.880 (15) |
C49—H49B | 0.9900 | F12—F12A | 1.582 (15) |
C38—C39 | 1.384 (5) | F13—F12A | 0.885 (14) |
C38—H38 | 0.9500 | F13—F13A | 1.633 (14) |
C48—H48A | 0.9900 | F14—F13A | 1.057 (14) |
C48—H48B | 0.9900 | F14—F14A | 1.327 (13) |
C35—C34 | 1.392 (5) | F21—F21A | 1.23 (3) |
C35—H35 | 0.9500 | F21—F24A | 1.251 (18) |
C51—C60 | 1.519 (5) | F22—F22A | 1.00 (2) |
C51—C50 | 1.527 (5) | F22—F21A | 1.48 (3) |
C51—H51A | 0.9900 | F23—F23A | 1.04 (3) |
C51—H51B | 0.9900 | F23—F22A | 1.34 (3) |
C50—H50A | 0.9900 | F24—F24A | 1.158 (18) |
C50—H50B | 0.9900 | F24—F23A | 1.24 (3) |
N25—Mn1—N43 | 169.40 (10) | C21—C22—C23 | 118.4 (3) |
N25—Mn1—N42 | 117.30 (10) | C21—C22—H22 | 120.8 |
N43—Mn1—N42 | 72.83 (10) | C23—C22—H22 | 120.8 |
N25—Mn1—N24 | 72.45 (9) | O45—C34—C33 | 125.4 (3) |
N43—Mn1—N24 | 110.53 (9) | O45—C34—C35 | 115.0 (3) |
N42—Mn1—N24 | 97.74 (10) | C33—C34—C35 | 119.7 (3) |
N25—Mn1—N26 | 72.48 (10) | C19—C20—C21 | 118.5 (3) |
N43—Mn1—N26 | 105.32 (9) | C19—C20—H20 | 120.7 |
N42—Mn1—N26 | 91.66 (10) | C21—C20—H20 | 120.7 |
N24—Mn1—N26 | 144.13 (9) | O45—C52—C53 | 105.3 (3) |
N25—Mn1—N44 | 97.60 (10) | O45—C52—H52A | 110.7 |
N43—Mn1—N44 | 72.21 (10) | C53—C52—H52A | 110.7 |
N42—Mn1—N44 | 145.03 (10) | O45—C52—H52B | 110.7 |
N24—Mn1—N44 | 94.61 (10) | C53—C52—H52B | 110.7 |
N26—Mn1—N44 | 97.20 (10) | H52A—C52—H52B | 108.8 |
F11A—P2—F14A | 97.2 (8) | N26—C23—C22 | 122.7 (3) |
F11A—P2—F13 | 119.4 (6) | N26—C23—H23 | 118.7 |
F14A—P2—F13 | 142.4 (6) | C22—C23—H23 | 118.7 |
F11A—P2—F14 | 144.7 (7) | C38—C39—C40 | 119.2 (3) |
F14A—P2—F14 | 51.0 (5) | C38—C39—H39 | 120.4 |
F13—P2—F14 | 91.5 (3) | C40—C39—H39 | 120.4 |
F11A—P2—F12 | 33.1 (6) | C12—C11—C10 | 119.3 (3) |
F14A—P2—F12 | 127.8 (5) | C12—C11—H11 | 120.3 |
F13—P2—F12 | 89.8 (2) | C10—C11—H11 | 120.3 |
F14—P2—F12 | 177.1 (2) | C27—C28—C29 | 118.0 (3) |
F11A—P2—F11 | 61.9 (6) | C27—C28—H28 | 121.0 |
F14A—P2—F11 | 35.9 (5) | C29—C28—H28 | 121.0 |
F13—P2—F11 | 177.6 (3) | N42—C27—C28 | 122.9 (3) |
F14—P2—F11 | 86.7 (3) | N42—C27—H27 | 118.5 |
F12—P2—F11 | 92.0 (3) | C28—C27—H27 | 118.5 |
F11A—P2—F16 | 101.1 (6) | C52—C53—C54 | 113.7 (3) |
F14A—P2—F16 | 87.7 (5) | C52—C53—H53A | 108.8 |
F13—P2—F16 | 93.09 (19) | C54—C53—H53A | 108.8 |
F14—P2—F16 | 93.31 (18) | C52—C53—H53B | 108.8 |
F12—P2—F16 | 89.20 (16) | C54—C53—H53B | 108.8 |
F11—P2—F16 | 88.53 (18) | H53A—C53—H53B | 107.7 |
F11A—P2—F15 | 78.7 (7) | C28—C29—C30 | 120.1 (3) |
F14A—P2—F15 | 92.2 (5) | C28—C29—H29 | 119.9 |
F13—P2—F15 | 87.1 (2) | C30—C29—H29 | 119.9 |
F14—P2—F15 | 86.87 (19) | C11—C10—C9 | 118.2 (3) |
F12—P2—F15 | 90.62 (17) | C11—C10—H10 | 120.9 |
F11—P2—F15 | 91.3 (2) | C9—C10—H10 | 120.9 |
F16—P2—F15 | 179.8 (2) | C55—C56—C68 | 109.4 (3) |
F11A—P2—F12A | 91.3 (8) | C55—C56—H56A | 109.8 |
F14A—P2—F12A | 168.8 (7) | C68—C56—H56A | 109.8 |
F13—P2—F12A | 32.2 (5) | C55—C56—H56B | 109.8 |
F14—P2—F12A | 122.6 (6) | C68—C56—H56B | 109.8 |
F12—P2—F12A | 59.1 (6) | H56A—C56—H56B | 108.3 |
F11—P2—F12A | 149.9 (6) | C11—C12—C13 | 119.6 (3) |
F16—P2—F12A | 83.4 (5) | C11—C12—H12 | 120.2 |
F15—P2—F12A | 96.7 (5) | C13—C12—H12 | 120.2 |
F11A—P2—F13A | 175.6 (8) | C22—C21—C20 | 120.0 (4) |
F14A—P2—F13A | 83.6 (7) | C22—C21—H21 | 120.0 |
F13—P2—F13A | 60.6 (5) | C20—C21—H21 | 120.0 |
F14—P2—F13A | 37.9 (5) | F23A—P61—F21 | 137.6 (13) |
F12—P2—F13A | 144.6 (6) | F23A—P61—F22 | 125.9 (13) |
F11—P2—F13A | 118.2 (5) | F21—P61—F22 | 95.8 (3) |
F16—P2—F13A | 74.6 (5) | F23A—P61—F26 | 92.4 (13) |
F15—P2—F13A | 105.6 (5) | F21—P61—F26 | 93.5 (4) |
F12A—P2—F13A | 87.4 (7) | F22—P61—F26 | 92.0 (3) |
C69—S57—C60 | 101.76 (19) | F23A—P61—F22A | 89.0 (14) |
C71—S59—C68 | 101.9 (2) | F21—P61—F22A | 133.1 (11) |
C23—N26—C19 | 118.5 (3) | F22—P61—F22A | 37.3 (9) |
C23—N26—Mn1 | 124.5 (2) | F26—P61—F22A | 88.0 (9) |
C19—N26—Mn1 | 117.0 (2) | F23A—P61—F24A | 91.1 (13) |
C14—N25—C18 | 119.6 (3) | F21—P61—F24A | 47.3 (7) |
C14—N25—Mn1 | 120.4 (2) | F22—P61—F24A | 143.0 (7) |
C18—N25—Mn1 | 119.82 (19) | F26—P61—F24A | 88.0 (6) |
C9—N24—C13 | 118.8 (3) | F22A—P61—F24A | 175.9 (11) |
C9—N24—Mn1 | 124.5 (2) | F23A—P61—F25 | 86.8 (13) |
C13—N24—Mn1 | 116.6 (2) | F21—P61—F25 | 87.7 (4) |
C41—N44—C37 | 118.4 (3) | F22—P61—F25 | 87.7 (3) |
C41—N44—Mn1 | 124.4 (2) | F26—P61—F25 | 178.8 (3) |
C37—N44—Mn1 | 117.2 (2) | F22A—P61—F25 | 91.1 (9) |
C32—N43—C36 | 119.6 (3) | F24A—P61—F25 | 93.0 (6) |
C32—N43—Mn1 | 119.8 (2) | F23A—P61—F24 | 48.4 (12) |
C36—N43—Mn1 | 120.4 (2) | F21—P61—F24 | 89.5 (3) |
C34—O45—C52 | 118.7 (3) | F22—P61—F24 | 173.5 (3) |
C27—N42—C31 | 118.6 (3) | F26—P61—F24 | 91.3 (2) |
C27—N42—Mn1 | 123.7 (2) | F22A—P61—F24 | 137.4 (10) |
C31—N42—Mn1 | 117.7 (2) | F24A—P61—F24 | 42.7 (7) |
C16—O46—C47 | 118.5 (3) | F25—P61—F24 | 88.84 (19) |
N25—C18—C17 | 121.5 (3) | F23A—P61—F23 | 39.3 (12) |
N25—C18—C19 | 114.9 (3) | F21—P61—F23 | 175.7 (3) |
C17—C18—C19 | 123.6 (3) | F22—P61—F23 | 86.8 (3) |
N26—C19—C20 | 121.9 (3) | F26—P61—F23 | 89.80 (18) |
N26—C19—C18 | 115.2 (3) | F22A—P61—F23 | 49.7 (10) |
C20—C19—C18 | 122.9 (3) | F24A—P61—F23 | 130.2 (7) |
N42—C31—C30 | 121.5 (3) | F25—P61—F23 | 89.0 (3) |
N42—C31—C32 | 115.2 (3) | F24—P61—F23 | 87.7 (2) |
C30—C31—C32 | 123.3 (3) | F23A—P61—F21A | 174.5 (16) |
N24—C13—C12 | 120.9 (3) | F21—P61—F21A | 44.3 (9) |
N24—C13—C14 | 115.7 (3) | F22—P61—F21A | 53.8 (9) |
C12—C13—C14 | 123.4 (3) | F26—P61—F21A | 82.2 (10) |
C34—C33—C32 | 117.8 (3) | F22A—P61—F21A | 89.9 (12) |
C34—C33—H33 | 121.1 | F24A—P61—F21A | 89.6 (11) |
C32—C33—H33 | 121.1 | F25—P61—F21A | 98.6 (10) |
N25—C14—C15 | 122.3 (3) | F24—P61—F21A | 132.2 (10) |
N25—C14—C13 | 114.4 (3) | F23—P61—F21A | 139.2 (10) |
C15—C14—C13 | 123.2 (3) | O74—C69—C70 | 122.7 (4) |
C18—C17—C16 | 118.7 (3) | O74—C69—S57 | 124.0 (3) |
C18—C17—H17 | 120.6 | C70—C69—S57 | 113.3 (3) |
C16—C17—H17 | 120.6 | C51—C60—S57 | 113.5 (2) |
N43—C32—C33 | 122.3 (3) | C51—C60—H60A | 108.9 |
N43—C32—C31 | 114.4 (3) | S57—C60—H60A | 108.9 |
C33—C32—C31 | 123.3 (3) | C51—C60—H60B | 108.9 |
O46—C16—C17 | 115.6 (3) | S57—C60—H60B | 108.9 |
O46—C16—C15 | 124.6 (3) | H60A—C60—H60B | 107.7 |
C17—C16—C15 | 119.8 (3) | C56—C68—S59 | 114.6 (3) |
N24—C9—C10 | 123.2 (3) | C56—C68—H68A | 108.6 |
N24—C9—H9 | 118.4 | S59—C68—H68A | 108.6 |
C10—C9—H9 | 118.4 | C56—C68—H68B | 108.6 |
N44—C37—C38 | 121.9 (3) | S59—C68—H68B | 108.6 |
N44—C37—C36 | 115.4 (3) | H68A—C68—H68B | 107.6 |
C38—C37—C36 | 122.7 (3) | C69—C70—H70A | 109.5 |
N43—C36—C35 | 121.4 (3) | C69—C70—H70B | 109.5 |
N43—C36—C37 | 114.7 (3) | H70A—C70—H70B | 109.5 |
C35—C36—C37 | 123.9 (3) | C69—C70—H70C | 109.5 |
O46—C47—C48 | 106.7 (3) | H70A—C70—H70C | 109.5 |
O46—C47—H47A | 110.4 | H70B—C70—H70C | 109.5 |
C48—C47—H47A | 110.4 | O73—C71—C72 | 123.1 (5) |
O46—C47—H47B | 110.4 | O73—C71—S59 | 125.3 (4) |
C48—C47—H47B | 110.4 | C72—C71—S59 | 111.7 (4) |
H47A—C47—H47B | 108.6 | C71—C72—H72A | 109.5 |
C14—C15—C16 | 118.0 (3) | C71—C72—H72B | 109.5 |
C14—C15—H15 | 121.0 | H72A—C72—H72B | 109.5 |
C16—C15—H15 | 121.0 | C71—C72—H72C | 109.5 |
N44—C41—C40 | 123.0 (3) | H72A—C72—H72C | 109.5 |
N44—C41—H41 | 118.5 | H72B—C72—H72C | 109.5 |
C40—C41—H41 | 118.5 | F14A—F11—F11A | 121.4 (9) |
C48—C49—C50 | 111.9 (3) | F14A—F11—P2 | 66.7 (7) |
C48—C49—H49A | 109.2 | F11A—F11—P2 | 55.8 (5) |
C50—C49—H49A | 109.2 | F11A—F12—F12A | 126.5 (11) |
C48—C49—H49B | 109.2 | F11A—F12—P2 | 67.0 (10) |
C50—C49—H49B | 109.2 | F12A—F12—P2 | 61.4 (5) |
H49A—C49—H49B | 107.9 | F12A—F13—P2 | 77.3 (9) |
C39—C38—C37 | 119.1 (3) | F12A—F13—F13A | 126.2 (11) |
C39—C38—H38 | 120.4 | P2—F13—F13A | 62.8 (5) |
C37—C38—H38 | 120.4 | F13A—F14—F14A | 124.4 (10) |
C49—C48—C47 | 114.3 (3) | F13A—F14—P2 | 75.5 (7) |
C49—C48—H48A | 108.7 | F14A—F14—P2 | 61.2 (5) |
C47—C48—H48A | 108.7 | F21A—F21—F24A | 137.9 (15) |
C49—C48—H48B | 108.7 | F21A—F21—P61 | 75.1 (11) |
C47—C48—H48B | 108.7 | F24A—F21—P61 | 68.1 (8) |
H48A—C48—H48B | 107.6 | F22A—F22—F21A | 136.7 (17) |
C36—C35—C34 | 119.2 (3) | F22A—F22—P61 | 71.9 (12) |
C36—C35—H35 | 120.4 | F21A—F22—P61 | 68.2 (10) |
C34—C35—H35 | 120.4 | F23A—F23—F22A | 122.1 (17) |
C60—C51—C50 | 111.4 (3) | F23A—F23—P61 | 59.0 (13) |
C60—C51—H51A | 109.3 | F22A—F23—P61 | 63.1 (9) |
C50—C51—H51A | 109.4 | F24A—F24—F23A | 125.3 (14) |
C60—C51—H51B | 109.4 | F24A—F24—P61 | 67.7 (8) |
C50—C51—H51B | 109.3 | F23A—F24—P61 | 57.6 (11) |
H51A—C51—H51B | 108.0 | F12—F11A—P2 | 80.0 (11) |
C51—C50—C49 | 113.3 (3) | F12—F11A—F11 | 134.2 (14) |
C51—C50—H50A | 108.9 | P2—F11A—F11 | 62.3 (6) |
C49—C50—H50A | 108.9 | F13—F12A—F12 | 126.5 (13) |
C51—C50—H50B | 108.9 | F13—F12A—P2 | 70.5 (9) |
C49—C50—H50B | 108.9 | F12—F12A—P2 | 59.5 (5) |
H50A—C50—H50B | 107.7 | F14—F13A—F13 | 111.9 (10) |
C56—C55—C54 | 114.1 (3) | F14—F13A—P2 | 66.7 (7) |
C56—C55—H55A | 108.7 | F13—F13A—P2 | 56.6 (4) |
C54—C55—H55A | 108.7 | F11—F14A—F14 | 144.6 (12) |
C56—C55—H55B | 108.7 | F11—F14A—P2 | 77.4 (8) |
C54—C55—H55B | 108.7 | F14—F14A—P2 | 67.8 (6) |
H55A—C55—H55B | 107.6 | F21—F21A—F22 | 115.2 (17) |
C53—C54—C55 | 110.0 (3) | F21—F21A—P61 | 60.6 (10) |
C53—C54—H54A | 109.7 | F22—F21A—P61 | 58.0 (8) |
C55—C54—H54A | 109.7 | F22—F22A—F23 | 137.4 (19) |
C53—C54—H54B | 109.7 | F22—F22A—P61 | 70.8 (12) |
C55—C54—H54B | 109.7 | F23—F22A—P61 | 67.2 (10) |
H54A—C54—H54B | 108.2 | F23—F23A—F24 | 155 (2) |
C29—C30—C31 | 118.7 (3) | F23—F23A—P61 | 81.7 (16) |
C29—C30—H30 | 120.6 | F24—F23A—P61 | 74.0 (13) |
C31—C30—H30 | 120.6 | F24—F24A—F21 | 133.0 (14) |
C41—C40—C39 | 118.4 (3) | F24—F24A—P61 | 69.6 (8) |
C41—C40—H40 | 120.8 | F21—F24A—P61 | 64.6 (7) |
C39—C40—H40 | 120.8 |
Experimental details
Crystal data | |
Chemical formula | [Mn(C23H25N3O2S)2](PF6)2 |
Mr | 1159.94 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 122 |
a, b, c (Å) | 9.1270 (16), 11.403 (3), 25.822 (2) |
α, β, γ (°) | 96.302 (12), 94.287 (11), 105.312 (14) |
V (Å3) | 2561.2 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.49 |
Crystal size (mm) | 0.63 × 0.14 × 0.03 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Gaussian (Coppens, 1970) |
Tmin, Tmax | 0.717, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 55194, 12876, 9290 |
Rint | 0.102 |
(sin θ/λ)max (Å−1) | 0.672 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.185, 1.04 |
No. of reflections | 12876 |
No. of parameters | 692 |
No. of restraints | 12 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.93, −0.99 |
Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg & Schreurs, 1989–2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).
Mn1—N25 | 2.192 (2) | Mn1—N24 | 2.266 (3) |
Mn1—N43 | 2.193 (2) | Mn1—N26 | 2.270 (3) |
Mn1—N42 | 2.226 (3) | Mn1—N44 | 2.272 (3) |
N25—Mn1—N43 | 169.40 (10) | N43—Mn1—N24 | 110.53 (9) |
N43—Mn1—N42 | 72.83 (10) | N42—Mn1—N24 | 97.74 (10) |
N25—Mn1—N24 | 72.45 (9) |
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Transition metal complexes of terpyrine have recently attracted attention as robust and geometrically well defined systems for the study of electron transport at the single-molecule level (Park, 2002; Albrecht, Moth-Poulsen, Guckian et al., 2006; Albrecht, Moth-Poulsen, Christensen et al., 2006). The title compound, (I), was functionalized with an acetyl-protected thiol via a 6-acetylsulfanylhexyloxy ether linkage to the 4-position of the central pyridine ring to facilitate attachment to gold surfaces and leads. The acetyl-protected thiol has been shown to be stable at room temperature and permits the formation of self-assembled monolayers of the compound on a gold surface (Albrecht, Moth-Poulsen, Guckian et al., 2006; Albrecht, Moth-Poulsen, Christensen et al., 2006). The coordination around the manganese(II) center is distorted octahedral, governed by the steric requirements of the terpyridine units (Fig. 1). The terpyridine ligands are quite rigid and, accordingly, the manganese–nitrogen bond lengths (Table 1) deviate only slightly from the values reported for the dithionate, (II), and triiodide, (III), salts of the parent bis(2,2':6',2''-terpyridine-N,N',N'')manganese(II) ion (Bhula & Weatherburn, 1991; Freire et al., 2001). In (II) and (III), the outer Mn—N bond lengths are 2.249 (11) and 2.249 (7) Å, respectively while the central Mn—N bond lengths are 2.192 (6) and 2.186 (6) Å. Whereas the bond lengths are effectively fixed in terpyridine complexes of a given central metal ion, angular distortions are frequently observed. For example, the angles between trans-situated donor atoms include some significant distortions: N42—Mn1—N44 = 145.03 (10)° and N24—Mn1—N26 = 144.13 (9)°.
In Fig. 2, the magnitudes of the two most common low-symmetry distortions of bis-terpyridine complexes, the wag and the twist, are shown for all monomeric MnII, FeII and ZnII bis-terpyridine complexes in the Cambridge Structural Database (CSD;Version 5.29, update of 2 August 2008; Allen, 2002). Only systems without bulky ortho-substituents have been included to isolate the importance of the electronic structure of the metal in determining its coordination geometry. MnII and ZnII have spherical d-electron density and no ligand field stabilization energy (LFSE), while FeII has maximal LFSE among the divalent transition metals. The plot illustrates that the two distortion modes have a mutually quenching relationship, with relatively few systems falling on the diagonal. It also shows, most importantly, that all three metal centers deliver examples of systems with nearly idealized D2d symmetry as well as significantly distorted complexes. For manganese(II) a couple of systems that contain 4'-substituted terpyridines with wag angles of more than 15° particularly stand out (Jeitler et al., 2003).
In the title compound, the terpyridine ligands are both close to planar. The r.m.s. deviation from planarity in the C9—C23/N24–N26 ring system is 0.0480 Å, with a largest deviation (for atom C11) of 0.098 (4) Å, while C27—C41/N42–N44 system has an r.m.s. deviation from planarity of 0.0392 Å and a largest deviation (C30) of 0.0778 (31) Å. The two ligand planes are almost perpendicular [88.06 (3)°], amounting to a twist angle of 1.94°. In this respect, the present complex differs significantly from the close analog bis(4'-methylthio-2,2':6',2''-terpyridine)manganese(II) perchlorate (Jeitler et al., 2003), which is significantly more distorted with twist angles of 23.8 and 15.1° for the two independent molecules. The wag angle in the present system is relatively large at 10.6°, but is exceeded by that in at least one FeII system with a similar substitution pattern (Constable et al., 2000). In the study by Jeitler et al. structures were determined for the MnII, FeII and NiII complexes, and it was found that the absolute differences in bond lengths between the outer and inner pyridine rings were 0.06–0.12 Å, with the manganese complex having the smallest bond-length difference. If one considers systems with substituents in the ortho positions to the nitrogen ligators, larger distortions are also found for FeII systems (Constable et al., 1999; Pelascini et al., 2004) than for MnII, albeit with different substituents.
Contrary to the common assumption that the large ionic radius of the manganese(II) ion and the lack of ligand field stabilization in high-spin d5 systems result in pronounced deviations from idealized geometries (Erre et al., 2000; Figgins & Busch 1961), the crystallographically characterized bis-terpyridine manganese(II) complexes do not constitute a structurally distinct class, but span the full range from undistorted to highly distorted. The title compound differs significantly from other 4'-substituted bis-terpyridine manganese(II) complexes by its low twist angle. It may be speculated that the fairly dense packing (cf. Fig. 3) of the long side chains in the present system suppresses this degree of freedom and thus contributes to the quite symmetrical coordination of the manganese(II) centre.
In conclusion, comparison between bis-terpyridine complexes of different divalent transition metal centers need not treat manganese(II) as a special case owing to the lack of LFSE.