Studying the axial ligation behavior of metalloporphyrins with nitrogenous bases helps to better understand not only the biological function of heme-based protein systems, but also the catalytic properties of porphyrin-based reaction sites in other biomimetic synthetic support environments. Unlike iron porphyrin complexes, little is known about the axial ligation behavior of Mn porphyrins, particularly in the solid state with Mn in the +3 oxidation state. Here, we present the syntheses and crystal and molecular structures of three new high-spin manganese(III) porphyrin complexes with the different amine-based axial ligands imidazole (im), piperidine (pip), and 1,4-diazabicyclo[2.2.2]octane (DABCO), namely bis(imidazole)(5,10,15,20-tetraphenylporphyrinato)manganese(III) chloride chloroform disolvate, [Mn(C44H28N4)(C3H4N2)2]Cl·2CHCl3 or [Mn(TPP)(im)2]Cl·2CHCl3 (TPP = 5,10,15,20-tetraphenylporphyrin), (I), bis(piperidine)(5,10,15,20-tetraphenylporphyrinato)manganese(III) chloride, [Mn(C44H28N4)(C5H11N)2]Cl or [Mn(TPP)(pip)2]Cl, (II), and chlorido(1,4-diazabicyclo[2.2.2]octane)(5,10,15,20-tetraphenylporphyrin)manganese(III)–1,4-diazabicyclo[2.2.2]octane–toluene–water (4/4/4/1), [Mn(C44H28N4)Cl(C6H12N2)]·C6H12N2·C7H8·0.25H2O or [Mn(TPP)Cl(DABCO)]·(DABCO)·(toluene)·0.25H2O, (IV). A fourth complex, chlorido(pyridine)(5,10,15,20-tetraphenylporphryinato)manganese(III) pyridine disolvate, [Mn(C44H28N4)Cl(C5H5N)]·2C5H5N or [Mn(TPP)Cl(py)]·2(py), (III), acquired using different crystallization methods from published data, is also reported and compared to the previous structures.
Supporting information
CCDC references: 1860177; 1860175; 1860171; 1860170
For all structures, data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Bis(imidazole)(5,10,15,20-tetraphenylporphyrinato)manganese(III) chloride
chloroform disolvate (I_Imidazole)
top
Crystal data top
[Mn(C44H28N4)(C3H4N2)2]Cl·2CHCl3 | Z = 2 |
Mr = 1077.99 | F(000) = 1100 |
Triclinic, P1 | Dx = 1.452 Mg m−3 |
a = 11.3475 (2) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 14.2479 (3) Å | Cell parameters from 9842 reflections |
c = 16.4138 (4) Å | θ = 2.7–68.9° |
α = 92.510 (1)° | µ = 6.03 mm−1 |
β = 99.529 (1)° | T = 100 K |
γ = 108.699 (1)° | Block, black |
V = 2465.63 (9) Å3 | 0.43 × 0.31 × 0.22 mm |
Data collection top
Bruker SMART CCD APEXII area-detector diffractometer | 8162 independent reflections |
Radiation source: fine-focus sealed tube | 7785 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
φ and ω scans | θmax = 66.6°, θmin = 2.7° |
Absorption correction: numerical (SADABS; Krause et al., 2015) | h = −13→13 |
Tmin = 0.168, Tmax = 0.447 | k = −16→17 |
23350 measured reflections | l = −19→19 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.111 | w = 1/[σ2(Fo2) + (0.0545P)2 + 3.7406P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
8162 reflections | Δρmax = 1.24 e Å−3 |
614 parameters | Δρmin = −1.02 e Å−3 |
0 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00056 (9) |
Special details top
Experimental. Crystal mounted on a Cryoloop using Paratone-N. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mn1 | 0.61658 (3) | 0.75403 (3) | 0.23878 (2) | 0.01308 (11) | |
Cl1 | 0.71735 (6) | 0.26873 (4) | 0.20734 (4) | 0.02189 (15) | |
Cl5 | 0.84687 (7) | 0.31994 (5) | 0.47894 (4) | 0.03372 (17) | |
Cl7 | 0.81761 (11) | 0.50249 (6) | 0.42514 (5) | 0.0589 (3) | |
Cl6 | 0.99856 (10) | 0.42242 (10) | 0.36517 (6) | 0.0815 (4) | |
Cl3 | 1.04132 (11) | 0.87957 (8) | 0.74718 (8) | 0.0683 (3) | |
Cl2 | 0.85271 (9) | 0.69728 (7) | 0.76379 (9) | 0.0731 (4) | |
Cl4 | 1.03780 (13) | 0.81017 (12) | 0.90833 (7) | 0.0862 (4) | |
N2 | 0.49991 (18) | 0.75920 (14) | 0.13354 (12) | 0.0149 (4) | |
N4 | 0.73304 (19) | 0.75133 (15) | 0.34578 (12) | 0.0160 (4) | |
N3 | 0.76885 (18) | 0.81946 (15) | 0.18701 (12) | 0.0158 (4) | |
N7 | 0.62805 (19) | 0.90946 (15) | 0.28887 (13) | 0.0178 (4) | |
N1 | 0.46442 (19) | 0.68853 (15) | 0.28989 (12) | 0.0159 (4) | |
N5 | 0.6077 (2) | 0.60020 (15) | 0.18634 (13) | 0.0195 (4) | |
N6 | 0.6432 (2) | 0.45814 (16) | 0.17264 (14) | 0.0263 (5) | |
H6 | 0.6778 | 0.4116 | 0.1822 | 0.032* | |
N8 | 0.6573 (2) | 1.06948 (16) | 0.29042 (15) | 0.0272 (5) | |
H8 | 0.6597 | 1.1272 | 0.2724 | 0.033* | |
C26 | 0.6751 (2) | 0.89127 (18) | −0.02842 (15) | 0.0171 (5) | |
C6 | 0.5358 (2) | 0.79889 (17) | 0.06254 (14) | 0.0153 (5) | |
C15 | 0.6970 (2) | 0.72608 (18) | 0.42076 (15) | 0.0172 (5) | |
C3 | 0.3694 (2) | 0.71654 (17) | 0.11515 (15) | 0.0158 (5) | |
C16 | 0.5732 (2) | 0.68833 (17) | 0.43352 (15) | 0.0171 (5) | |
C17 | 0.4658 (2) | 0.66810 (17) | 0.37143 (15) | 0.0174 (5) | |
C1 | 0.3391 (2) | 0.65538 (18) | 0.25074 (15) | 0.0175 (5) | |
C7 | 0.6594 (2) | 0.84512 (17) | 0.05122 (14) | 0.0163 (5) | |
C8 | 0.7672 (2) | 0.85280 (18) | 0.10910 (15) | 0.0174 (5) | |
C12 | 0.8634 (2) | 0.79152 (18) | 0.36229 (15) | 0.0179 (5) | |
C4 | 0.3244 (2) | 0.72934 (18) | 0.03097 (15) | 0.0188 (5) | |
H4 | 0.2387 | 0.7057 | 0.0026 | 0.023* | |
C2 | 0.2928 (2) | 0.66728 (18) | 0.16903 (15) | 0.0174 (5) | |
C5 | 0.4258 (2) | 0.78106 (18) | −0.00095 (15) | 0.0169 (5) | |
H5 | 0.4244 | 0.8017 | −0.0553 | 0.020* | |
C47 | 0.6232 (3) | 0.98242 (19) | 0.24380 (17) | 0.0247 (6) | |
H47 | 0.5983 | 0.9743 | 0.1850 | 0.030* | |
C20 | 0.1524 (2) | 0.6255 (2) | 0.13778 (15) | 0.0219 (5) | |
C38 | 0.5535 (2) | 0.67505 (19) | 0.52093 (15) | 0.0194 (5) | |
C10 | 0.9728 (2) | 0.8942 (2) | 0.16775 (16) | 0.0227 (5) | |
H10 | 1.0628 | 0.9188 | 0.1781 | 0.027* | |
C11 | 0.8943 (2) | 0.84568 (18) | 0.22446 (15) | 0.0183 (5) | |
C18 | 0.3385 (2) | 0.62031 (18) | 0.38290 (15) | 0.0202 (5) | |
H18 | 0.3134 | 0.5988 | 0.4333 | 0.024* | |
C9 | 0.8951 (2) | 0.8985 (2) | 0.09725 (16) | 0.0221 (5) | |
H9 | 0.9202 | 0.9265 | 0.0488 | 0.027* | |
C44 | 0.6782 (3) | 0.54772 (19) | 0.21640 (16) | 0.0237 (6) | |
H44 | 0.7455 | 0.5703 | 0.2632 | 0.028* | |
C012 | 0.9396 (2) | 0.83396 (19) | 0.30606 (15) | 0.0187 (5) | |
C32 | 1.0799 (2) | 0.8778 (2) | 0.33851 (15) | 0.0199 (5) | |
C39 | 0.5884 (3) | 0.6041 (2) | 0.56547 (16) | 0.0249 (6) | |
H39 | 0.6231 | 0.5606 | 0.5398 | 0.030* | |
C14 | 0.8084 (2) | 0.75014 (19) | 0.48440 (15) | 0.0213 (5) | |
H14 | 0.8105 | 0.7403 | 0.5414 | 0.026* | |
C33 | 1.1309 (3) | 0.9760 (2) | 0.37447 (17) | 0.0258 (6) | |
H33 | 1.0766 | 1.0140 | 0.3785 | 0.031* | |
C13 | 0.9095 (2) | 0.78917 (19) | 0.44854 (16) | 0.0215 (5) | |
H13 | 0.9959 | 0.8112 | 0.4756 | 0.026* | |
C48 | 0.6690 (3) | 0.9537 (2) | 0.36959 (17) | 0.0264 (6) | |
H48 | 0.6823 | 0.9200 | 0.4171 | 0.032* | |
C27 | 0.6559 (3) | 0.9819 (2) | −0.03807 (16) | 0.0237 (6) | |
H27 | 0.6373 | 1.0158 | 0.0067 | 0.028* | |
C31 | 0.7041 (3) | 0.8432 (2) | −0.09420 (16) | 0.0244 (6) | |
H31 | 0.7189 | 0.7817 | −0.0880 | 0.029* | |
C43 | 0.5016 (2) | 0.7374 (2) | 0.55957 (16) | 0.0225 (5) | |
H43 | 0.4745 | 0.7843 | 0.5291 | 0.027* | |
C25 | 0.0827 (3) | 0.6876 (2) | 0.11540 (17) | 0.0284 (6) | |
H25 | 0.1239 | 0.7576 | 0.1200 | 0.034* | |
C29 | 0.6900 (2) | 0.9744 (2) | −0.17855 (16) | 0.0251 (6) | |
H29 | 0.6934 | 1.0022 | −0.2300 | 0.030* | |
C30 | 0.7115 (3) | 0.8853 (2) | −0.16916 (16) | 0.0276 (6) | |
H30 | 0.7314 | 0.8524 | −0.2139 | 0.033* | |
C42 | 0.4893 (3) | 0.7313 (2) | 0.64198 (17) | 0.0290 (6) | |
H42 | 0.4561 | 0.7753 | 0.6683 | 0.035* | |
C35 | 1.3393 (3) | 0.9636 (2) | 0.39936 (16) | 0.0269 (6) | |
H35 | 1.4277 | 0.9929 | 0.4201 | 0.032* | |
C37 | 1.1602 (3) | 0.8230 (2) | 0.33359 (17) | 0.0265 (6) | |
H37 | 1.1267 | 0.7558 | 0.3093 | 0.032* | |
C19 | 0.2609 (2) | 0.61147 (19) | 0.30899 (16) | 0.0206 (5) | |
H19 | 0.1712 | 0.5818 | 0.2976 | 0.025* | |
C46 | 0.5239 (3) | 0.5405 (2) | 0.11954 (19) | 0.0322 (7) | |
H46 | 0.4606 | 0.5583 | 0.0845 | 0.039* | |
C41 | 0.5252 (3) | 0.6615 (2) | 0.68571 (17) | 0.0318 (7) | |
H41 | 0.5174 | 0.6578 | 0.7423 | 0.038* | |
C34 | 1.2593 (3) | 1.0187 (2) | 0.40433 (17) | 0.0290 (6) | |
H34 | 1.2930 | 1.0860 | 0.4283 | 0.035* | |
C28 | 0.6636 (3) | 1.0233 (2) | −0.11298 (17) | 0.0273 (6) | |
H28 | 0.6506 | 1.0855 | −0.1191 | 0.033* | |
C21 | 0.0906 (3) | 0.5233 (2) | 0.13120 (17) | 0.0309 (6) | |
H21 | 0.1376 | 0.4800 | 0.1459 | 0.037* | |
C40 | 0.5726 (3) | 0.5968 (2) | 0.64761 (17) | 0.0307 (6) | |
H40 | 0.5944 | 0.5472 | 0.6775 | 0.037* | |
C45 | 0.5449 (3) | 0.4526 (2) | 0.11112 (19) | 0.0314 (6) | |
H45 | 0.4998 | 0.3980 | 0.0703 | 0.038* | |
C36 | 1.2901 (3) | 0.8660 (2) | 0.36418 (18) | 0.0291 (6) | |
H36 | 1.3447 | 0.8281 | 0.3608 | 0.035* | |
C24 | −0.0477 (3) | 0.6475 (3) | 0.08616 (18) | 0.0371 (7) | |
H24 | −0.0952 | 0.6901 | 0.0705 | 0.045* | |
C49 | 0.6875 (3) | 1.0525 (2) | 0.37068 (18) | 0.0292 (6) | |
H49 | 0.7159 | 1.1003 | 0.4181 | 0.035* | |
C23 | −0.1075 (3) | 0.5459 (3) | 0.08009 (18) | 0.0407 (8) | |
H23 | −0.1962 | 0.5186 | 0.0598 | 0.049* | |
C22 | −0.0396 (3) | 0.4841 (3) | 0.10318 (19) | 0.0409 (8) | |
H22 | −0.0817 | 0.4143 | 0.1000 | 0.049* | |
C50 | 1.0095 (3) | 0.7741 (3) | 0.8023 (2) | 0.0419 (8) | |
H50 | 1.0676 | 0.7369 | 0.7917 | 0.050* | |
C51 | 0.8508 (3) | 0.3941 (2) | 0.39582 (19) | 0.0407 (8) | |
H51 | 0.7835 | 0.3552 | 0.3479 | 0.049* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.0131 (2) | 0.0142 (2) | 0.01221 (19) | 0.00489 (15) | 0.00221 (14) | 0.00284 (15) |
Cl1 | 0.0307 (3) | 0.0188 (3) | 0.0172 (3) | 0.0116 (2) | 0.0004 (2) | 0.0018 (2) |
Cl5 | 0.0334 (4) | 0.0333 (4) | 0.0349 (4) | 0.0129 (3) | 0.0045 (3) | 0.0013 (3) |
Cl7 | 0.0950 (7) | 0.0317 (4) | 0.0341 (4) | 0.0130 (4) | −0.0149 (4) | 0.0031 (3) |
Cl6 | 0.0509 (6) | 0.1128 (9) | 0.0390 (5) | −0.0325 (6) | 0.0203 (4) | −0.0172 (5) |
Cl3 | 0.0716 (7) | 0.0542 (6) | 0.0908 (8) | 0.0306 (5) | 0.0227 (6) | 0.0277 (6) |
Cl2 | 0.0357 (5) | 0.0450 (5) | 0.1375 (11) | 0.0153 (4) | 0.0120 (6) | 0.0007 (6) |
Cl4 | 0.0984 (9) | 0.1468 (12) | 0.0482 (6) | 0.0889 (9) | 0.0132 (6) | 0.0091 (7) |
N2 | 0.0159 (10) | 0.0147 (9) | 0.0144 (9) | 0.0058 (8) | 0.0021 (8) | 0.0017 (8) |
N4 | 0.0168 (10) | 0.0173 (10) | 0.0152 (10) | 0.0071 (8) | 0.0029 (8) | 0.0029 (8) |
N3 | 0.0150 (10) | 0.0182 (10) | 0.0144 (10) | 0.0059 (8) | 0.0018 (8) | 0.0027 (8) |
N7 | 0.0185 (10) | 0.0161 (10) | 0.0185 (10) | 0.0060 (8) | 0.0026 (8) | 0.0016 (8) |
N1 | 0.0169 (10) | 0.0162 (10) | 0.0142 (10) | 0.0047 (8) | 0.0028 (8) | 0.0035 (8) |
N5 | 0.0251 (11) | 0.0163 (10) | 0.0190 (10) | 0.0087 (9) | 0.0056 (9) | 0.0027 (8) |
N6 | 0.0393 (14) | 0.0187 (11) | 0.0302 (12) | 0.0162 (10) | 0.0168 (10) | 0.0099 (10) |
N8 | 0.0378 (14) | 0.0147 (10) | 0.0318 (13) | 0.0110 (10) | 0.0089 (10) | 0.0055 (9) |
C26 | 0.0129 (11) | 0.0212 (12) | 0.0158 (12) | 0.0031 (10) | 0.0036 (9) | 0.0040 (10) |
C6 | 0.0198 (12) | 0.0136 (11) | 0.0131 (11) | 0.0065 (10) | 0.0025 (9) | 0.0008 (9) |
C15 | 0.0230 (13) | 0.0162 (11) | 0.0144 (11) | 0.0091 (10) | 0.0032 (10) | 0.0032 (9) |
C3 | 0.0164 (12) | 0.0141 (11) | 0.0156 (11) | 0.0043 (10) | 0.0016 (9) | 0.0005 (9) |
C16 | 0.0229 (13) | 0.0146 (11) | 0.0156 (12) | 0.0079 (10) | 0.0042 (10) | 0.0044 (9) |
C17 | 0.0216 (13) | 0.0140 (11) | 0.0180 (12) | 0.0067 (10) | 0.0059 (10) | 0.0032 (10) |
C1 | 0.0177 (12) | 0.0152 (11) | 0.0187 (12) | 0.0038 (10) | 0.0040 (10) | 0.0021 (10) |
C7 | 0.0189 (12) | 0.0167 (11) | 0.0152 (11) | 0.0079 (10) | 0.0041 (9) | 0.0018 (10) |
C8 | 0.0183 (12) | 0.0183 (12) | 0.0169 (12) | 0.0067 (10) | 0.0053 (10) | 0.0027 (10) |
C12 | 0.0171 (12) | 0.0192 (12) | 0.0184 (12) | 0.0090 (10) | 0.0006 (9) | 0.0009 (10) |
C4 | 0.0172 (12) | 0.0197 (12) | 0.0165 (12) | 0.0046 (10) | −0.0012 (10) | 0.0000 (10) |
C2 | 0.0160 (12) | 0.0160 (11) | 0.0181 (12) | 0.0037 (10) | 0.0015 (9) | 0.0007 (10) |
C5 | 0.0188 (12) | 0.0181 (12) | 0.0135 (11) | 0.0060 (10) | 0.0024 (9) | 0.0020 (9) |
C47 | 0.0319 (15) | 0.0214 (13) | 0.0227 (13) | 0.0124 (12) | 0.0029 (11) | 0.0024 (11) |
C20 | 0.0181 (13) | 0.0296 (14) | 0.0144 (11) | 0.0029 (11) | 0.0029 (10) | 0.0031 (10) |
C38 | 0.0189 (12) | 0.0195 (12) | 0.0161 (12) | 0.0016 (10) | 0.0025 (10) | 0.0017 (10) |
C10 | 0.0149 (12) | 0.0305 (14) | 0.0223 (13) | 0.0062 (11) | 0.0043 (10) | 0.0048 (11) |
C11 | 0.0161 (12) | 0.0198 (12) | 0.0198 (12) | 0.0072 (10) | 0.0031 (10) | 0.0033 (10) |
C18 | 0.0228 (13) | 0.0195 (12) | 0.0181 (12) | 0.0049 (10) | 0.0068 (10) | 0.0053 (10) |
C9 | 0.0188 (13) | 0.0282 (14) | 0.0191 (12) | 0.0059 (11) | 0.0058 (10) | 0.0074 (11) |
C44 | 0.0312 (15) | 0.0231 (13) | 0.0223 (13) | 0.0144 (12) | 0.0081 (11) | 0.0070 (11) |
C012 | 0.0165 (12) | 0.0205 (12) | 0.0198 (12) | 0.0083 (10) | 0.0014 (10) | 0.0004 (10) |
C32 | 0.0165 (12) | 0.0282 (13) | 0.0147 (11) | 0.0073 (11) | 0.0014 (9) | 0.0059 (10) |
C39 | 0.0305 (15) | 0.0213 (13) | 0.0194 (13) | 0.0057 (11) | 0.0007 (11) | 0.0021 (11) |
C14 | 0.0254 (14) | 0.0253 (13) | 0.0145 (11) | 0.0107 (11) | 0.0022 (10) | 0.0052 (10) |
C33 | 0.0241 (14) | 0.0278 (14) | 0.0265 (14) | 0.0107 (12) | 0.0037 (11) | 0.0016 (12) |
C13 | 0.0192 (13) | 0.0260 (13) | 0.0191 (12) | 0.0097 (11) | −0.0017 (10) | 0.0030 (11) |
C48 | 0.0362 (16) | 0.0228 (13) | 0.0200 (13) | 0.0102 (12) | 0.0037 (11) | 0.0015 (11) |
C27 | 0.0285 (14) | 0.0239 (13) | 0.0210 (13) | 0.0095 (11) | 0.0089 (11) | 0.0043 (11) |
C31 | 0.0300 (14) | 0.0248 (13) | 0.0217 (13) | 0.0112 (12) | 0.0089 (11) | 0.0039 (11) |
C43 | 0.0199 (13) | 0.0248 (13) | 0.0210 (13) | 0.0051 (11) | 0.0038 (10) | 0.0024 (11) |
C25 | 0.0193 (13) | 0.0368 (16) | 0.0267 (14) | 0.0073 (12) | 0.0027 (11) | 0.0010 (12) |
C29 | 0.0183 (13) | 0.0351 (15) | 0.0191 (12) | 0.0039 (11) | 0.0039 (10) | 0.0102 (11) |
C30 | 0.0291 (15) | 0.0363 (15) | 0.0180 (13) | 0.0101 (13) | 0.0080 (11) | 0.0013 (12) |
C42 | 0.0261 (14) | 0.0341 (15) | 0.0238 (14) | 0.0050 (12) | 0.0080 (11) | −0.0023 (12) |
C35 | 0.0179 (13) | 0.0376 (16) | 0.0202 (13) | 0.0036 (12) | 0.0002 (10) | 0.0082 (12) |
C37 | 0.0209 (13) | 0.0284 (14) | 0.0301 (14) | 0.0096 (12) | 0.0018 (11) | 0.0024 (12) |
C19 | 0.0173 (12) | 0.0212 (12) | 0.0211 (12) | 0.0027 (10) | 0.0044 (10) | 0.0036 (10) |
C46 | 0.0344 (16) | 0.0275 (15) | 0.0333 (15) | 0.0154 (13) | −0.0048 (12) | −0.0068 (12) |
C41 | 0.0325 (16) | 0.0366 (16) | 0.0178 (13) | −0.0017 (13) | 0.0079 (11) | 0.0016 (12) |
C34 | 0.0276 (15) | 0.0297 (15) | 0.0239 (14) | 0.0036 (12) | 0.0016 (11) | −0.0009 (12) |
C28 | 0.0306 (15) | 0.0265 (14) | 0.0274 (14) | 0.0108 (12) | 0.0080 (11) | 0.0116 (12) |
C21 | 0.0278 (15) | 0.0310 (15) | 0.0241 (14) | −0.0016 (12) | 0.0003 (12) | 0.0056 (12) |
C40 | 0.0392 (17) | 0.0252 (14) | 0.0212 (13) | 0.0032 (13) | 0.0012 (12) | 0.0081 (11) |
C45 | 0.0356 (16) | 0.0219 (14) | 0.0363 (16) | 0.0097 (12) | 0.0075 (13) | −0.0043 (12) |
C36 | 0.0189 (13) | 0.0373 (16) | 0.0334 (15) | 0.0131 (12) | 0.0026 (11) | 0.0082 (13) |
C24 | 0.0200 (14) | 0.060 (2) | 0.0296 (15) | 0.0131 (14) | 0.0022 (12) | 0.0028 (15) |
C49 | 0.0356 (16) | 0.0219 (13) | 0.0269 (14) | 0.0077 (12) | 0.0025 (12) | −0.0041 (11) |
C23 | 0.0158 (14) | 0.069 (2) | 0.0236 (14) | −0.0042 (15) | 0.0020 (11) | 0.0035 (15) |
C22 | 0.0320 (17) | 0.0433 (18) | 0.0269 (15) | −0.0121 (15) | −0.0022 (13) | 0.0070 (14) |
C50 | 0.0363 (18) | 0.0446 (19) | 0.051 (2) | 0.0232 (15) | 0.0044 (15) | 0.0067 (16) |
C51 | 0.0429 (19) | 0.0390 (17) | 0.0236 (14) | −0.0060 (15) | 0.0025 (13) | −0.0046 (13) |
Geometric parameters (Å, º) top
Mn1—N2 | 2.015 (2) | C10—C11 | 1.440 (4) |
Mn1—N1 | 2.018 (2) | C10—H10 | 0.9500 |
Mn1—N3 | 2.025 (2) | C11—C012 | 1.390 (4) |
Mn1—N4 | 2.025 (2) | C18—C19 | 1.351 (4) |
Mn1—N7 | 2.284 (2) | C18—H18 | 0.9500 |
Mn1—N5 | 2.285 (2) | C9—H9 | 0.9500 |
Cl5—C51 | 1.759 (3) | C44—H44 | 0.9500 |
Cl7—C51 | 1.769 (4) | C012—C32 | 1.504 (3) |
Cl6—C51 | 1.758 (3) | C32—C37 | 1.386 (4) |
Cl3—C50 | 1.756 (4) | C32—C33 | 1.391 (4) |
Cl2—C50 | 1.755 (4) | C39—C40 | 1.393 (4) |
Cl4—C50 | 1.740 (4) | C39—H39 | 0.9500 |
N2—C6 | 1.382 (3) | C14—C13 | 1.347 (4) |
N2—C3 | 1.383 (3) | C14—H14 | 0.9500 |
N4—C12 | 1.378 (3) | C33—C34 | 1.380 (4) |
N4—C15 | 1.386 (3) | C33—H33 | 0.9500 |
N3—C11 | 1.376 (3) | C13—H13 | 0.9500 |
N3—C8 | 1.383 (3) | C48—C49 | 1.354 (4) |
N7—C47 | 1.312 (3) | C48—H48 | 0.9500 |
N7—C48 | 1.380 (3) | C27—C28 | 1.391 (4) |
N1—C1 | 1.378 (3) | C27—H27 | 0.9500 |
N1—C17 | 1.381 (3) | C31—C30 | 1.396 (4) |
N5—C44 | 1.315 (3) | C31—H31 | 0.9500 |
N5—C46 | 1.373 (4) | C43—C42 | 1.386 (4) |
N6—C44 | 1.343 (3) | C43—H43 | 0.9500 |
N6—C45 | 1.354 (4) | C25—C24 | 1.395 (4) |
N6—H6 | 0.8800 | C25—H25 | 0.9500 |
N8—C47 | 1.336 (3) | C29—C30 | 1.378 (4) |
N8—C49 | 1.358 (4) | C29—C28 | 1.382 (4) |
N8—H8 | 0.8800 | C29—H29 | 0.9500 |
C26—C27 | 1.388 (4) | C30—H30 | 0.9500 |
C26—C31 | 1.393 (4) | C42—C41 | 1.378 (4) |
C26—C7 | 1.500 (3) | C42—H42 | 0.9500 |
C6—C7 | 1.393 (3) | C35—C36 | 1.379 (4) |
C6—C5 | 1.432 (3) | C35—C34 | 1.387 (4) |
C15—C16 | 1.390 (4) | C35—H35 | 0.9500 |
C15—C14 | 1.435 (3) | C37—C36 | 1.396 (4) |
C3—C2 | 1.396 (3) | C37—H37 | 0.9500 |
C3—C4 | 1.432 (3) | C19—H19 | 0.9500 |
C16—C17 | 1.394 (4) | C46—C45 | 1.354 (4) |
C16—C38 | 1.499 (3) | C46—H46 | 0.9500 |
C17—C18 | 1.434 (4) | C41—C40 | 1.381 (4) |
C1—C2 | 1.395 (4) | C41—H41 | 0.9500 |
C1—C19 | 1.439 (3) | C34—H34 | 0.9500 |
C7—C8 | 1.390 (3) | C28—H28 | 0.9500 |
C8—C9 | 1.437 (4) | C21—C22 | 1.390 (4) |
C12—C012 | 1.394 (4) | C21—H21 | 0.9500 |
C12—C13 | 1.432 (3) | C40—H40 | 0.9500 |
C4—C5 | 1.353 (4) | C45—H45 | 0.9500 |
C4—H4 | 0.9500 | C36—H36 | 0.9500 |
C2—C20 | 1.500 (3) | C24—C23 | 1.379 (5) |
C5—H5 | 0.9500 | C24—H24 | 0.9500 |
C47—H47 | 0.9500 | C49—H49 | 0.9500 |
C20—C25 | 1.388 (4) | C23—C22 | 1.371 (5) |
C20—C21 | 1.390 (4) | C23—H23 | 0.9500 |
C38—C39 | 1.393 (4) | C22—H22 | 0.9500 |
C38—C43 | 1.395 (4) | C50—H50 | 1.0000 |
C10—C9 | 1.350 (4) | C51—H51 | 1.0000 |
| | | |
N2—Mn1—N1 | 89.59 (8) | N6—C44—H44 | 124.3 |
N2—Mn1—N3 | 90.21 (8) | C11—C012—C12 | 124.7 (2) |
N1—Mn1—N3 | 179.75 (9) | C11—C012—C32 | 117.9 (2) |
N2—Mn1—N4 | 178.75 (8) | C12—C012—C32 | 117.2 (2) |
N1—Mn1—N4 | 90.10 (8) | C37—C32—C33 | 119.0 (2) |
N3—Mn1—N4 | 90.11 (8) | C37—C32—C012 | 121.8 (2) |
N2—Mn1—N7 | 91.37 (8) | C33—C32—C012 | 119.3 (2) |
N1—Mn1—N7 | 92.09 (8) | C38—C39—C40 | 120.0 (3) |
N3—Mn1—N7 | 88.05 (8) | C38—C39—H39 | 120.0 |
N4—Mn1—N7 | 87.43 (8) | C40—C39—H39 | 120.0 |
N2—Mn1—N5 | 88.13 (8) | C13—C14—C15 | 107.5 (2) |
N1—Mn1—N5 | 89.17 (8) | C13—C14—H14 | 126.2 |
N3—Mn1—N5 | 90.69 (8) | C15—C14—H14 | 126.2 |
N4—Mn1—N5 | 93.08 (8) | C34—C33—C32 | 120.8 (3) |
N7—Mn1—N5 | 178.65 (7) | C34—C33—H33 | 119.6 |
C6—N2—C3 | 106.27 (19) | C32—C33—H33 | 119.6 |
C6—N2—Mn1 | 126.44 (16) | C14—C13—C12 | 107.7 (2) |
C3—N2—Mn1 | 127.08 (16) | C14—C13—H13 | 126.2 |
C12—N4—C15 | 106.4 (2) | C12—C13—H13 | 126.2 |
C12—N4—Mn1 | 126.27 (16) | C49—C48—N7 | 109.6 (2) |
C15—N4—Mn1 | 126.29 (16) | C49—C48—H48 | 125.2 |
C11—N3—C8 | 106.43 (19) | N7—C48—H48 | 125.2 |
C11—N3—Mn1 | 126.75 (16) | C26—C27—C28 | 120.3 (2) |
C8—N3—Mn1 | 126.69 (16) | C26—C27—H27 | 119.8 |
C47—N7—C48 | 104.9 (2) | C28—C27—H27 | 119.8 |
C47—N7—Mn1 | 125.51 (17) | C26—C31—C30 | 120.0 (2) |
C48—N7—Mn1 | 128.14 (17) | C26—C31—H31 | 120.0 |
C1—N1—C17 | 106.45 (19) | C30—C31—H31 | 120.0 |
C1—N1—Mn1 | 127.05 (16) | C42—C43—C38 | 120.6 (3) |
C17—N1—Mn1 | 126.50 (16) | C42—C43—H43 | 119.7 |
C44—N5—C46 | 105.1 (2) | C38—C43—H43 | 119.7 |
C44—N5—Mn1 | 127.14 (18) | C20—C25—C24 | 120.2 (3) |
C46—N5—Mn1 | 127.67 (18) | C20—C25—H25 | 119.9 |
C44—N6—C45 | 107.5 (2) | C24—C25—H25 | 119.9 |
C44—N6—H6 | 126.3 | C30—C29—C28 | 119.9 (2) |
C45—N6—H6 | 126.3 | C30—C29—H29 | 120.0 |
C47—N8—C49 | 107.4 (2) | C28—C29—H29 | 120.0 |
C47—N8—H8 | 126.3 | C29—C30—C31 | 120.3 (2) |
C49—N8—H8 | 126.3 | C29—C30—H30 | 119.9 |
C27—C26—C31 | 119.2 (2) | C31—C30—H30 | 119.9 |
C27—C26—C7 | 119.5 (2) | C41—C42—C43 | 119.9 (3) |
C31—C26—C7 | 121.3 (2) | C41—C42—H42 | 120.0 |
N2—C6—C7 | 126.3 (2) | C43—C42—H42 | 120.0 |
N2—C6—C5 | 109.6 (2) | C36—C35—C34 | 119.8 (3) |
C7—C6—C5 | 124.0 (2) | C36—C35—H35 | 120.1 |
N4—C15—C16 | 125.8 (2) | C34—C35—H35 | 120.1 |
N4—C15—C14 | 109.0 (2) | C32—C37—C36 | 120.3 (3) |
C16—C15—C14 | 125.2 (2) | C32—C37—H37 | 119.8 |
N2—C3—C2 | 125.9 (2) | C36—C37—H37 | 119.8 |
N2—C3—C4 | 109.2 (2) | C18—C19—C1 | 107.3 (2) |
C2—C3—C4 | 124.9 (2) | C18—C19—H19 | 126.3 |
C15—C16—C17 | 124.5 (2) | C1—C19—H19 | 126.3 |
C15—C16—C38 | 117.7 (2) | C45—C46—N5 | 109.8 (3) |
C17—C16—C38 | 117.6 (2) | C45—C46—H46 | 125.1 |
N1—C17—C16 | 126.1 (2) | N5—C46—H46 | 125.1 |
N1—C17—C18 | 109.4 (2) | C42—C41—C40 | 120.3 (3) |
C16—C17—C18 | 124.5 (2) | C42—C41—H41 | 119.9 |
N1—C1—C2 | 126.1 (2) | C40—C41—H41 | 119.9 |
N1—C1—C19 | 109.3 (2) | C33—C34—C35 | 120.1 (3) |
C2—C1—C19 | 124.5 (2) | C33—C34—H34 | 120.0 |
C8—C7—C6 | 124.4 (2) | C35—C34—H34 | 120.0 |
C8—C7—C26 | 118.7 (2) | C29—C28—C27 | 120.3 (3) |
C6—C7—C26 | 116.9 (2) | C29—C28—H28 | 119.9 |
N3—C8—C7 | 125.8 (2) | C27—C28—H28 | 119.9 |
N3—C8—C9 | 109.4 (2) | C20—C21—C22 | 120.2 (3) |
C7—C8—C9 | 124.8 (2) | C20—C21—H21 | 119.9 |
N4—C12—C012 | 126.1 (2) | C22—C21—H21 | 119.9 |
N4—C12—C13 | 109.3 (2) | C41—C40—C39 | 120.1 (3) |
C012—C12—C13 | 124.4 (2) | C41—C40—H40 | 119.9 |
C5—C4—C3 | 107.8 (2) | C39—C40—H40 | 119.9 |
C5—C4—H4 | 126.1 | C46—C45—N6 | 106.2 (2) |
C3—C4—H4 | 126.1 | C46—C45—H45 | 126.9 |
C1—C2—C3 | 123.8 (2) | N6—C45—H45 | 126.9 |
C1—C2—C20 | 117.9 (2) | C35—C36—C37 | 120.1 (3) |
C3—C2—C20 | 118.3 (2) | C35—C36—H36 | 120.0 |
C4—C5—C6 | 107.1 (2) | C37—C36—H36 | 120.0 |
C4—C5—H5 | 126.4 | C23—C24—C25 | 119.8 (3) |
C6—C5—H5 | 126.4 | C23—C24—H24 | 120.1 |
N7—C47—N8 | 111.9 (2) | C25—C24—H24 | 120.1 |
N7—C47—H47 | 124.0 | C48—C49—N8 | 106.2 (2) |
N8—C47—H47 | 124.0 | C48—C49—H49 | 126.9 |
C25—C20—C21 | 119.2 (3) | N8—C49—H49 | 126.9 |
C25—C20—C2 | 120.9 (2) | C22—C23—C24 | 120.4 (3) |
C21—C20—C2 | 119.9 (3) | C22—C23—H23 | 119.8 |
C39—C38—C43 | 119.0 (2) | C24—C23—H23 | 119.8 |
C39—C38—C16 | 122.0 (2) | C23—C22—C21 | 120.2 (3) |
C43—C38—C16 | 119.0 (2) | C23—C22—H22 | 119.9 |
C9—C10—C11 | 107.5 (2) | C21—C22—H22 | 119.9 |
C9—C10—H10 | 126.3 | Cl4—C50—Cl2 | 112.8 (2) |
C11—C10—H10 | 126.3 | Cl4—C50—Cl3 | 110.1 (2) |
N3—C11—C012 | 125.9 (2) | Cl2—C50—Cl3 | 108.20 (18) |
N3—C11—C10 | 109.4 (2) | Cl4—C50—H50 | 108.5 |
C012—C11—C10 | 124.6 (2) | Cl2—C50—H50 | 108.5 |
C19—C18—C17 | 107.5 (2) | Cl3—C50—H50 | 108.5 |
C19—C18—H18 | 126.3 | Cl6—C51—Cl5 | 109.7 (2) |
C17—C18—H18 | 126.3 | Cl6—C51—Cl7 | 112.12 (18) |
C10—C9—C8 | 107.3 (2) | Cl5—C51—Cl7 | 109.62 (17) |
C10—C9—H9 | 126.4 | Cl6—C51—H51 | 108.4 |
C8—C9—H9 | 126.4 | Cl5—C51—H51 | 108.4 |
N5—C44—N6 | 111.5 (2) | Cl7—C51—H51 | 108.4 |
N5—C44—H44 | 124.3 | | |
Bis(piperidine)(5,10,15,20-tetraphenylporphyrinato)manganese(III)
dichloride (II_Piperidine)
top
Crystal data top
[Mn(C44H28N4)(C5H11N)2]Cl | Z = 1 |
Mr = 873.39 | F(000) = 475 |
Triclinic, P1 | Dx = 1.068 Mg m−3 |
a = 10.5211 (1) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 11.9123 (1) Å | Cell parameters from 9895 reflections |
c = 12.6355 (1) Å | θ = 3.9–68.8° |
α = 66.1342 (5)° | µ = 3.04 mm−1 |
β = 78.3107 (5)° | T = 100 K |
γ = 89.5778 (6)° | Plate, green |
V = 1413.24 (2) Å3 | 0.48 × 0.26 × 0.24 mm |
Data collection top
Bruker SMART CCD APEXII area-detector diffractometer | 4750 independent reflections |
Radiation source: fine-focus sealed tube | 4719 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
φ and ω scans | θmax = 69.2°, θmin = 3.9° |
Absorption correction: numerical (SADABS; Krause et al., 2015) | h = −12→12 |
Tmin = 0.406, Tmax = 0.572 | k = −14→14 |
13568 measured reflections | l = −14→15 |
Refinement top
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0548P)2 + 1.6375P] where P = (Fo2 + 2Fc2)/3 |
4750 reflections | (Δ/σ)max < 0.001 |
286 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −1.00 e Å−3 |
Special details top
Experimental. Crystal mounted on a Cryoloop using Paratone-N. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mn1 | 0.0000 | 0.0000 | 0.0000 | 0.01474 (13) | |
N1 | 0.01241 (17) | −0.12201 (16) | 0.16365 (15) | 0.0169 (4) | |
N2 | 0.08899 (17) | 0.13330 (16) | 0.02570 (15) | 0.0171 (4) | |
C5 | 0.1288 (2) | 0.0124 (2) | 0.22581 (18) | 0.0179 (4) | |
N3 | −0.20868 (17) | 0.04247 (16) | 0.08114 (16) | 0.0193 (4) | |
H4 | −0.2523 | −0.0381 | 0.1433 | 0.023* | |
C4 | 0.0683 (2) | −0.09966 (19) | 0.24354 (18) | 0.0180 (4) | |
C9 | 0.1172 (2) | 0.25531 (19) | −0.05315 (18) | 0.0180 (4) | |
C1 | −0.0261 (2) | −0.24636 (19) | 0.21445 (18) | 0.0187 (4) | |
C2 | 0.0052 (2) | −0.3012 (2) | 0.32931 (19) | 0.0227 (5) | |
H2 | −0.0110 | −0.3856 | 0.3826 | 0.027* | |
C7 | 0.2035 (2) | 0.2348 (2) | 0.10181 (19) | 0.0198 (4) | |
H6 | 0.2480 | 0.2500 | 0.1537 | 0.024* | |
C3 | 0.0613 (2) | −0.2119 (2) | 0.34786 (19) | 0.0221 (5) | |
H3 | 0.0907 | −0.2211 | 0.4170 | 0.026* | |
C6 | 0.1391 (2) | 0.1199 (2) | 0.12281 (18) | 0.0178 (4) | |
C8 | 0.1894 (2) | 0.3177 (2) | −0.00536 (19) | 0.0208 (5) | |
H7 | 0.2216 | 0.4020 | −0.0423 | 0.025* | |
C11 | 0.1889 (2) | 0.01770 (19) | 0.32161 (18) | 0.0203 (5) | |
C12 | 0.3024 (2) | −0.0395 (2) | 0.3443 (2) | 0.0272 (5) | |
H12 | 0.3409 | −0.0844 | 0.3005 | 0.033* | |
C16 | 0.1336 (2) | 0.0817 (2) | 0.3880 (2) | 0.0245 (5) | |
H16 | 0.0557 | 0.1202 | 0.3738 | 0.029* | |
C13 | 0.3593 (2) | −0.0306 (3) | 0.4315 (2) | 0.0370 (7) | |
H13 | 0.4366 | −0.0698 | 0.4469 | 0.044* | |
C14 | 0.3044 (3) | 0.0345 (3) | 0.4954 (2) | 0.0378 (7) | |
H14 | 0.3446 | 0.0412 | 0.5537 | 0.045* | |
C15 | 0.1909 (3) | 0.0900 (2) | 0.4747 (2) | 0.0322 (6) | |
H15 | 0.1521 | 0.1338 | 0.5196 | 0.039* | |
C10 | 0.0841 (2) | 0.31042 (19) | −0.16334 (18) | 0.0183 (4) | |
C27 | −0.2056 (2) | 0.1249 (2) | 0.1419 (2) | 0.0278 (5) | |
H26A | −0.1604 | 0.2054 | 0.0839 | 0.033* | |
H26B | −0.1547 | 0.0892 | 0.2040 | 0.033* | |
C23 | −0.2936 (2) | 0.0884 (2) | −0.0057 (2) | 0.0271 (5) | |
H22A | −0.3005 | 0.0282 | −0.0403 | 0.033* | |
H22B | −0.2519 | 0.1668 | −0.0709 | 0.033* | |
C25 | −0.4250 (2) | 0.1950 (3) | 0.1089 (3) | 0.0349 (6) | |
H24A | −0.3888 | 0.2783 | 0.0496 | 0.042* | |
H24B | −0.5142 | 0.2015 | 0.1489 | 0.042* | |
C26 | −0.3409 (2) | 0.1459 (3) | 0.1992 (2) | 0.0339 (6) | |
H25A | −0.3831 | 0.0673 | 0.2637 | 0.041* | |
H25B | −0.3326 | 0.2054 | 0.2344 | 0.041* | |
C24 | −0.4303 (2) | 0.1098 (3) | 0.0472 (2) | 0.0319 (6) | |
H23A | −0.4789 | 0.1464 | −0.0166 | 0.038* | |
H23B | −0.4772 | 0.0299 | 0.1049 | 0.038* | |
C18 | 0.0443 (2) | 0.5239 (2) | −0.1815 (2) | 0.0227 (5) | |
H18 | −0.0176 | 0.4891 | −0.1082 | 0.027* | |
C17 | 0.1110 (2) | 0.44701 (19) | −0.22903 (18) | 0.0190 (4) | |
C22 | 0.2013 (2) | 0.4992 (2) | −0.33633 (19) | 0.0213 (5) | |
H22 | 0.2472 | 0.4477 | −0.3692 | 0.026* | |
C20 | 0.1581 (2) | 0.7025 (2) | −0.3484 (2) | 0.0244 (5) | |
H20 | 0.1738 | 0.7894 | −0.3893 | 0.029* | |
C21 | 0.2248 (2) | 0.6266 (2) | −0.3957 (2) | 0.0235 (5) | |
H21 | 0.2868 | 0.6617 | −0.4689 | 0.028* | |
C19 | 0.0682 (2) | 0.6506 (2) | −0.2410 (2) | 0.0252 (5) | |
H19 | 0.0228 | 0.7023 | −0.2082 | 0.030* | |
Cl1 | 0.62779 (10) | 0.79940 (7) | 0.31554 (8) | 0.0748 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.0192 (2) | 0.0113 (2) | 0.0121 (2) | 0.00178 (18) | −0.00382 (18) | −0.00305 (18) |
N1 | 0.0204 (9) | 0.0136 (8) | 0.0151 (8) | 0.0016 (7) | −0.0042 (7) | −0.0041 (7) |
N2 | 0.0207 (9) | 0.0146 (9) | 0.0131 (8) | 0.0029 (7) | −0.0026 (7) | −0.0034 (7) |
C5 | 0.0173 (10) | 0.0193 (11) | 0.0160 (10) | 0.0036 (8) | −0.0027 (8) | −0.0068 (8) |
N3 | 0.0199 (9) | 0.0178 (9) | 0.0194 (9) | 0.0027 (7) | −0.0031 (7) | −0.0076 (7) |
C4 | 0.0185 (10) | 0.0189 (11) | 0.0150 (10) | 0.0037 (8) | −0.0033 (8) | −0.0055 (8) |
C9 | 0.0194 (10) | 0.0152 (10) | 0.0165 (10) | 0.0023 (8) | −0.0005 (8) | −0.0053 (8) |
C1 | 0.0204 (10) | 0.0154 (10) | 0.0172 (10) | 0.0029 (8) | −0.0030 (8) | −0.0043 (8) |
C2 | 0.0284 (12) | 0.0160 (11) | 0.0179 (10) | 0.0026 (9) | −0.0068 (9) | −0.0004 (9) |
C7 | 0.0206 (10) | 0.0207 (11) | 0.0191 (10) | 0.0000 (9) | −0.0049 (9) | −0.0088 (9) |
C3 | 0.0267 (11) | 0.0220 (11) | 0.0159 (10) | 0.0037 (9) | −0.0082 (9) | −0.0045 (9) |
C6 | 0.0168 (10) | 0.0200 (11) | 0.0169 (10) | 0.0049 (8) | −0.0034 (8) | −0.0080 (9) |
C8 | 0.0233 (11) | 0.0169 (11) | 0.0196 (10) | −0.0020 (9) | −0.0014 (9) | −0.0065 (9) |
C11 | 0.0210 (10) | 0.0170 (10) | 0.0172 (10) | −0.0039 (9) | −0.0052 (9) | −0.0007 (8) |
C12 | 0.0190 (11) | 0.0294 (13) | 0.0229 (11) | −0.0002 (10) | −0.0020 (9) | −0.0015 (10) |
C16 | 0.0292 (12) | 0.0211 (11) | 0.0230 (11) | 0.0004 (10) | −0.0091 (10) | −0.0073 (9) |
C13 | 0.0192 (11) | 0.0420 (15) | 0.0325 (13) | −0.0072 (11) | −0.0119 (10) | 0.0052 (12) |
C14 | 0.0389 (15) | 0.0416 (15) | 0.0270 (13) | −0.0165 (12) | −0.0143 (12) | −0.0046 (11) |
C15 | 0.0441 (15) | 0.0278 (13) | 0.0251 (12) | −0.0076 (11) | −0.0109 (11) | −0.0095 (10) |
C10 | 0.0191 (10) | 0.0156 (10) | 0.0171 (10) | 0.0019 (8) | −0.0004 (8) | −0.0054 (8) |
C27 | 0.0232 (11) | 0.0355 (13) | 0.0359 (13) | 0.0074 (10) | −0.0090 (10) | −0.0248 (11) |
C23 | 0.0231 (11) | 0.0364 (14) | 0.0264 (12) | 0.0059 (10) | −0.0082 (10) | −0.0165 (11) |
C25 | 0.0250 (12) | 0.0409 (15) | 0.0493 (16) | 0.0134 (11) | −0.0104 (12) | −0.0282 (13) |
C26 | 0.0253 (12) | 0.0513 (16) | 0.0426 (15) | 0.0114 (11) | −0.0090 (11) | −0.0363 (13) |
C24 | 0.0244 (12) | 0.0419 (15) | 0.0365 (14) | 0.0079 (11) | −0.0098 (11) | −0.0218 (12) |
C18 | 0.0254 (11) | 0.0192 (11) | 0.0203 (11) | 0.0028 (9) | −0.0024 (9) | −0.0060 (9) |
C17 | 0.0230 (11) | 0.0166 (11) | 0.0163 (10) | 0.0025 (9) | −0.0069 (9) | −0.0044 (9) |
C22 | 0.0251 (11) | 0.0184 (11) | 0.0191 (10) | 0.0032 (9) | −0.0054 (9) | −0.0060 (9) |
C20 | 0.0284 (12) | 0.0137 (10) | 0.0274 (12) | −0.0007 (9) | −0.0092 (10) | −0.0033 (9) |
C21 | 0.0245 (11) | 0.0201 (11) | 0.0194 (11) | −0.0006 (9) | −0.0043 (9) | −0.0018 (9) |
C19 | 0.0301 (12) | 0.0193 (11) | 0.0282 (12) | 0.0050 (10) | −0.0067 (10) | −0.0116 (10) |
Cl1 | 0.0919 (7) | 0.0278 (4) | 0.0688 (6) | −0.0020 (4) | 0.0379 (5) | −0.0096 (4) |
Geometric parameters (Å, º) top
Mn1—N2i | 2.0164 (17) | C7—C8 | 1.352 (3) |
Mn1—N2 | 2.0164 (17) | C7—C6 | 1.432 (3) |
Mn1—N1 | 2.0199 (17) | C11—C16 | 1.391 (3) |
Mn1—N1i | 2.0199 (17) | C11—C12 | 1.393 (3) |
Mn1—N3i | 2.3704 (17) | C12—C13 | 1.395 (4) |
Mn1—N3 | 2.3704 (17) | C16—C15 | 1.389 (3) |
N1—C4 | 1.377 (3) | C13—C14 | 1.379 (4) |
N1—C1 | 1.380 (3) | C14—C15 | 1.380 (4) |
N2—C9 | 1.381 (3) | C10—C1i | 1.392 (3) |
N2—C6 | 1.383 (3) | C10—C17 | 1.495 (3) |
C5—C6 | 1.393 (3) | C27—C26 | 1.528 (3) |
C5—C4 | 1.397 (3) | C23—C24 | 1.523 (3) |
C5—C11 | 1.497 (3) | C25—C26 | 1.513 (4) |
N3—C27 | 1.475 (3) | C25—C24 | 1.516 (3) |
N3—C23 | 1.485 (3) | C18—C19 | 1.384 (3) |
C4—C3 | 1.437 (3) | C18—C17 | 1.400 (3) |
C9—C10 | 1.395 (3) | C17—C22 | 1.390 (3) |
C9—C8 | 1.432 (3) | C22—C21 | 1.391 (3) |
C1—C10i | 1.392 (3) | C20—C21 | 1.387 (3) |
C1—C2 | 1.437 (3) | C20—C19 | 1.388 (3) |
C2—C3 | 1.343 (3) | | |
| | | |
N2i—Mn1—N2 | 180.00 (11) | N1—C1—C2 | 109.10 (18) |
N2i—Mn1—N1 | 90.22 (7) | C10i—C1—C2 | 124.7 (2) |
N2—Mn1—N1 | 89.78 (7) | C3—C2—C1 | 107.84 (19) |
N2i—Mn1—N1i | 89.78 (7) | C8—C7—C6 | 107.44 (19) |
N2—Mn1—N1i | 90.22 (7) | C2—C3—C4 | 107.14 (19) |
N1—Mn1—N1i | 180.00 (16) | N2—C6—C5 | 125.96 (19) |
N2i—Mn1—N3i | 91.99 (6) | N2—C6—C7 | 109.31 (18) |
N2—Mn1—N3i | 88.01 (6) | C5—C6—C7 | 124.72 (19) |
N1—Mn1—N3i | 90.59 (7) | C7—C8—C9 | 107.55 (19) |
N1i—Mn1—N3i | 89.41 (7) | C16—C11—C12 | 118.9 (2) |
N2i—Mn1—N3 | 88.01 (6) | C16—C11—C5 | 120.6 (2) |
N2—Mn1—N3 | 91.99 (6) | C12—C11—C5 | 120.5 (2) |
N1—Mn1—N3 | 89.41 (7) | C11—C12—C13 | 119.8 (2) |
N1i—Mn1—N3 | 90.59 (7) | C15—C16—C11 | 120.9 (2) |
N3i—Mn1—N3 | 180.00 (11) | C14—C13—C12 | 120.6 (2) |
C4—N1—C1 | 106.32 (17) | C13—C14—C15 | 120.0 (2) |
C4—N1—Mn1 | 126.99 (14) | C14—C15—C16 | 119.8 (2) |
C1—N1—Mn1 | 126.58 (14) | C1i—C10—C9 | 124.0 (2) |
C9—N2—C6 | 106.39 (17) | C1i—C10—C17 | 118.44 (19) |
C9—N2—Mn1 | 126.52 (14) | C9—C10—C17 | 117.53 (19) |
C6—N2—Mn1 | 127.03 (14) | N3—C27—C26 | 113.36 (19) |
C6—C5—C4 | 123.91 (19) | N3—C23—C24 | 113.92 (19) |
C6—C5—C11 | 117.60 (18) | C26—C25—C24 | 110.1 (2) |
C4—C5—C11 | 118.48 (18) | C25—C26—C27 | 111.0 (2) |
C27—N3—C23 | 110.07 (17) | C25—C24—C23 | 110.9 (2) |
C27—N3—Mn1 | 114.10 (13) | C19—C18—C17 | 120.1 (2) |
C23—N3—Mn1 | 113.57 (13) | C22—C17—C18 | 119.31 (19) |
N1—C4—C5 | 126.17 (19) | C22—C17—C10 | 121.30 (19) |
N1—C4—C3 | 109.57 (18) | C18—C17—C10 | 119.39 (19) |
C5—C4—C3 | 124.18 (19) | C17—C22—C21 | 120.2 (2) |
N2—C9—C10 | 126.23 (19) | C21—C20—C19 | 119.6 (2) |
N2—C9—C8 | 109.27 (18) | C20—C21—C22 | 120.3 (2) |
C10—C9—C8 | 124.49 (19) | C18—C19—C20 | 120.4 (2) |
N1—C1—C10i | 126.20 (19) | | |
Symmetry code: (i) −x, −y, −z. |
Chlorido(pyridine)(5,10,15,20-tetraphenylporphryinato)manganese(III)
pyridine disolvate (III_Pyridine)
top
Crystal data top
[Mn(C44H28N4)Cl(C5H5N)]·2C5H5N | Z = 2 |
Mr = 940.39 | F(000) = 976 |
Triclinic, P1 | Dx = 1.345 Mg m−3 |
a = 11.0499 (1) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 12.1051 (1) Å | Cell parameters from 9885 reflections |
c = 18.5362 (2) Å | θ = 2.4–68.6° |
α = 90.177 (1)° | µ = 3.22 mm−1 |
β = 90.324 (1)° | T = 100 K |
γ = 110.537 (1)° | Block, black |
V = 2321.76 (4) Å3 | 0.30 × 0.26 × 0.24 mm |
Data collection top
Bruker SMART CCD APEXII area-detector diffractometer | 7797 independent reflections |
Radiation source: fine-focus sealed tube | 7543 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
φ and ω scans | θmax = 68.7°, θmin = 2.4° |
Absorption correction: numerical (SADABS; Krause et al., 2015) | h = −12→12 |
Tmin = 0.501, Tmax = 0.653 | k = −14→14 |
21813 measured reflections | l = −21→20 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.038P)2 + 0.7188P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.002 |
7797 reflections | Δρmax = 0.25 e Å−3 |
614 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00110 (9) |
Special details top
Experimental. Crystal mounted on a Cryoloop using Paratone-N. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Mn1 | 0.25000 (2) | 0.25259 (2) | 0.26425 (2) | 0.01129 (7) | |
Cl1 | 0.05275 (3) | 0.07601 (3) | 0.27497 (2) | 0.01823 (9) | |
N3 | 0.28699 (11) | 0.18844 (10) | 0.17020 (6) | 0.0131 (2) | |
N2 | 0.16611 (11) | 0.35000 (10) | 0.21006 (6) | 0.0138 (2) | |
N4 | 0.35308 (11) | 0.17105 (10) | 0.31700 (6) | 0.0129 (2) | |
N1 | 0.23015 (11) | 0.33306 (10) | 0.35623 (6) | 0.0136 (2) | |
N5 | 0.45322 (12) | 0.41540 (11) | 0.25495 (6) | 0.0170 (3) | |
N6 | 0.59232 (13) | 0.39758 (12) | −0.04010 (8) | 0.0276 (3) | |
C19 | 0.35666 (13) | 0.15735 (12) | 0.39042 (8) | 0.0135 (3) | |
C16 | 0.42241 (13) | 0.10803 (12) | 0.28697 (8) | 0.0134 (3) | |
C14 | 0.36984 (13) | 0.12807 (12) | 0.15901 (7) | 0.0136 (3) | |
C9 | 0.11901 (13) | 0.33012 (12) | 0.14042 (8) | 0.0148 (3) | |
C39 | 0.33748 (14) | 0.20485 (12) | 0.51979 (8) | 0.0154 (3) | |
C6 | 0.13100 (13) | 0.44033 (12) | 0.23724 (8) | 0.0151 (3) | |
C4 | 0.20063 (13) | 0.43432 (12) | 0.36279 (8) | 0.0148 (3) | |
C27 | 0.09681 (14) | 0.25070 (13) | 0.01496 (8) | 0.0152 (3) | |
C15 | 0.43798 (13) | 0.09316 (12) | 0.21294 (8) | 0.0136 (3) | |
C11 | 0.23185 (13) | 0.19582 (12) | 0.10456 (7) | 0.0139 (3) | |
C1 | 0.26374 (13) | 0.30786 (13) | 0.42388 (8) | 0.0146 (3) | |
C33 | 0.53214 (14) | 0.03633 (13) | 0.19083 (7) | 0.0150 (3) | |
C7 | 0.05806 (14) | 0.47601 (13) | 0.18378 (8) | 0.0178 (3) | |
H7 | 0.0228 | 0.5367 | 0.1888 | 0.021* | |
C17 | 0.46955 (14) | 0.05208 (13) | 0.34355 (8) | 0.0165 (3) | |
H17 | 0.5210 | 0.0042 | 0.3375 | 0.020* | |
C20 | 0.31388 (13) | 0.22013 (12) | 0.44175 (8) | 0.0145 (3) | |
C5 | 0.15543 (13) | 0.48713 (12) | 0.30716 (8) | 0.0152 (3) | |
C35 | 0.75424 (15) | 0.04324 (15) | 0.18735 (8) | 0.0233 (3) | |
H35 | 0.8427 | 0.0817 | 0.1998 | 0.028* | |
C28 | 0.00599 (15) | 0.14826 (13) | −0.01309 (8) | 0.0191 (3) | |
H28 | −0.0316 | 0.0825 | 0.0175 | 0.023* | |
N7 | 0.26832 (14) | 0.70063 (14) | 0.56772 (9) | 0.0359 (4) | |
C12 | 0.28312 (14) | 0.13959 (13) | 0.05048 (8) | 0.0161 (3) | |
H12 | 0.2601 | 0.1313 | 0.0008 | 0.019* | |
C8 | 0.04876 (14) | 0.40704 (13) | 0.12464 (8) | 0.0173 (3) | |
H8 | 0.0042 | 0.4093 | 0.0810 | 0.021* | |
C49 | 0.47837 (15) | 0.49069 (14) | 0.19981 (8) | 0.0207 (3) | |
H49 | 0.4153 | 0.4775 | 0.1626 | 0.025* | |
C40 | 0.23800 (15) | 0.14101 (13) | 0.56488 (8) | 0.0201 (3) | |
H40 | 0.1530 | 0.1058 | 0.5458 | 0.024* | |
C21 | 0.12741 (14) | 0.59728 (12) | 0.32143 (8) | 0.0157 (3) | |
C18 | 0.42704 (14) | 0.08038 (13) | 0.40676 (8) | 0.0163 (3) | |
H18 | 0.4410 | 0.0543 | 0.4533 | 0.020* | |
C3 | 0.21752 (14) | 0.47356 (13) | 0.43655 (8) | 0.0177 (3) | |
H3 | 0.2055 | 0.5420 | 0.4553 | 0.021* | |
C34 | 0.66264 (14) | 0.09132 (14) | 0.20836 (8) | 0.0196 (3) | |
H34 | 0.6894 | 0.1630 | 0.2352 | 0.024* | |
C13 | 0.37026 (14) | 0.10065 (13) | 0.08331 (8) | 0.0159 (3) | |
H13 | 0.4219 | 0.0624 | 0.0607 | 0.019* | |
C38 | 0.49484 (14) | −0.06955 (13) | 0.15206 (8) | 0.0176 (3) | |
H38 | 0.4063 | −0.1093 | 0.1405 | 0.021* | |
C2 | 0.25384 (14) | 0.39468 (13) | 0.47430 (8) | 0.0179 (3) | |
H2 | 0.2698 | 0.3964 | 0.5248 | 0.021* | |
C10 | 0.14712 (13) | 0.25626 (12) | 0.09031 (8) | 0.0143 (3) | |
C22 | 0.19665 (15) | 0.70084 (13) | 0.28517 (8) | 0.0189 (3) | |
H22 | 0.2637 | 0.7015 | 0.2531 | 0.023* | |
C32 | 0.14656 (14) | 0.34803 (13) | −0.03030 (8) | 0.0194 (3) | |
H32 | 0.2069 | 0.4195 | −0.0117 | 0.023* | |
C26 | 0.03019 (14) | 0.59893 (13) | 0.36883 (8) | 0.0197 (3) | |
H26 | −0.0170 | 0.5298 | 0.3947 | 0.024* | |
C23 | 0.16871 (16) | 0.80310 (13) | 0.29541 (9) | 0.0224 (3) | |
H23 | 0.2174 | 0.8733 | 0.2709 | 0.027* | |
C41 | 0.26093 (16) | 0.12787 (14) | 0.63777 (8) | 0.0231 (3) | |
H41 | 0.1923 | 0.0830 | 0.6680 | 0.028* | |
C31 | 0.10873 (15) | 0.34110 (14) | −0.10188 (8) | 0.0216 (3) | |
H31 | 0.1427 | 0.4080 | −0.1321 | 0.026* | |
C29 | −0.03044 (15) | 0.14082 (14) | −0.08518 (9) | 0.0229 (3) | |
H29 | −0.0911 | 0.0696 | −0.1039 | 0.027* | |
C42 | 0.38407 (16) | 0.18045 (14) | 0.66576 (8) | 0.0214 (3) | |
H42 | 0.4005 | 0.1714 | 0.7154 | 0.026* | |
C36 | 0.71595 (16) | −0.06108 (15) | 0.14808 (8) | 0.0232 (3) | |
H36 | 0.7782 | −0.0941 | 0.1334 | 0.028* | |
C37 | 0.58662 (16) | −0.11725 (14) | 0.13029 (8) | 0.0212 (3) | |
H37 | 0.5606 | −0.1886 | 0.1031 | 0.025* | |
C30 | 0.02151 (15) | 0.23702 (15) | −0.12989 (8) | 0.0222 (3) | |
H30 | −0.0024 | 0.2318 | −0.1794 | 0.027* | |
C25 | 0.00217 (15) | 0.70140 (14) | 0.37823 (9) | 0.0244 (3) | |
H25 | −0.0644 | 0.7016 | 0.4104 | 0.029* | |
C44 | 0.46069 (15) | 0.25817 (15) | 0.54889 (8) | 0.0235 (3) | |
H44 | 0.5296 | 0.3030 | 0.5188 | 0.028* | |
C24 | 0.07045 (16) | 0.80309 (14) | 0.34114 (9) | 0.0244 (4) | |
H24 | 0.0498 | 0.8724 | 0.3471 | 0.029* | |
C46 | 0.65926 (16) | 0.53058 (14) | 0.30564 (9) | 0.0250 (4) | |
H46 | 0.7206 | 0.5422 | 0.3436 | 0.030* | |
C56 | 0.12331 (16) | 0.75725 (15) | 0.64284 (9) | 0.0274 (4) | |
H56 | 0.0799 | 0.7496 | 0.6876 | 0.033* | |
C45 | 0.54398 (15) | 0.43615 (14) | 0.30688 (8) | 0.0219 (3) | |
H45 | 0.5281 | 0.3833 | 0.3464 | 0.026* | |
C47 | 0.68391 (16) | 0.60767 (14) | 0.24838 (9) | 0.0265 (4) | |
H47 | 0.7623 | 0.6735 | 0.2462 | 0.032* | |
C43 | 0.48364 (16) | 0.24635 (16) | 0.62149 (9) | 0.0271 (4) | |
H43 | 0.5680 | 0.2836 | 0.6410 | 0.032* | |
C57 | 0.10590 (16) | 0.83005 (15) | 0.58995 (9) | 0.0290 (4) | |
H57 | 0.0499 | 0.8733 | 0.5972 | 0.035* | |
C48 | 0.59169 (16) | 0.58689 (14) | 0.19408 (9) | 0.0267 (4) | |
H48 | 0.6060 | 0.6378 | 0.1536 | 0.032* | |
C54 | 0.68179 (17) | 0.35615 (16) | −0.06430 (10) | 0.0321 (4) | |
H54 | 0.6999 | 0.3617 | −0.1145 | 0.039* | |
C58 | 0.17241 (18) | 0.83840 (16) | 0.52590 (10) | 0.0335 (4) | |
H58 | 0.1644 | 0.8889 | 0.4885 | 0.040* | |
C50 | 0.57007 (16) | 0.38918 (14) | 0.03096 (9) | 0.0270 (4) | |
H50 | 0.5070 | 0.4183 | 0.0496 | 0.032* | |
C51 | 0.63330 (17) | 0.34079 (16) | 0.07861 (10) | 0.0318 (4) | |
H51 | 0.6149 | 0.3377 | 0.1287 | 0.038* | |
C55 | 0.20516 (16) | 0.69548 (15) | 0.62960 (10) | 0.0307 (4) | |
H55 | 0.2172 | 0.6464 | 0.6668 | 0.037* | |
C59 | 0.25042 (18) | 0.77214 (17) | 0.51750 (10) | 0.0361 (4) | |
H59 | 0.2944 | 0.7778 | 0.4730 | 0.043* | |
C53 | 0.74970 (17) | 0.30561 (17) | −0.02065 (12) | 0.0381 (5) | |
H53 | 0.8127 | 0.2775 | −0.0404 | 0.046* | |
C52 | 0.72378 (17) | 0.29689 (16) | 0.05232 (11) | 0.0377 (5) | |
H52 | 0.7675 | 0.2613 | 0.0838 | 0.045* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.01350 (12) | 0.01365 (13) | 0.00933 (13) | 0.00804 (9) | −0.00088 (8) | 0.00011 (8) |
Cl1 | 0.01423 (17) | 0.01765 (18) | 0.0226 (2) | 0.00532 (13) | 0.00011 (13) | 0.00237 (13) |
N3 | 0.0144 (6) | 0.0150 (6) | 0.0113 (6) | 0.0068 (5) | −0.0005 (5) | 0.0013 (4) |
N2 | 0.0158 (6) | 0.0147 (6) | 0.0124 (6) | 0.0073 (5) | −0.0010 (5) | 0.0002 (4) |
N4 | 0.0147 (6) | 0.0144 (6) | 0.0109 (6) | 0.0067 (5) | −0.0006 (5) | −0.0002 (4) |
N1 | 0.0162 (6) | 0.0149 (6) | 0.0119 (6) | 0.0080 (5) | 0.0000 (5) | 0.0011 (4) |
N5 | 0.0182 (6) | 0.0178 (6) | 0.0159 (7) | 0.0076 (5) | 0.0010 (5) | 0.0000 (5) |
N6 | 0.0254 (7) | 0.0258 (7) | 0.0295 (8) | 0.0063 (6) | −0.0029 (6) | −0.0037 (6) |
C19 | 0.0144 (7) | 0.0150 (7) | 0.0119 (7) | 0.0061 (6) | −0.0008 (5) | 0.0021 (5) |
C16 | 0.0123 (6) | 0.0128 (7) | 0.0159 (7) | 0.0053 (5) | −0.0010 (5) | −0.0007 (5) |
C14 | 0.0128 (7) | 0.0140 (7) | 0.0140 (7) | 0.0045 (5) | 0.0006 (5) | −0.0006 (5) |
C9 | 0.0144 (7) | 0.0160 (7) | 0.0140 (8) | 0.0051 (6) | −0.0007 (5) | 0.0022 (5) |
C39 | 0.0227 (7) | 0.0163 (7) | 0.0123 (7) | 0.0132 (6) | 0.0002 (6) | 0.0004 (5) |
C6 | 0.0142 (7) | 0.0135 (7) | 0.0186 (8) | 0.0061 (6) | 0.0007 (6) | 0.0015 (5) |
C4 | 0.0147 (7) | 0.0147 (7) | 0.0169 (8) | 0.0073 (6) | 0.0004 (5) | −0.0009 (5) |
C27 | 0.0167 (7) | 0.0190 (7) | 0.0133 (7) | 0.0106 (6) | −0.0018 (6) | −0.0005 (5) |
C15 | 0.0120 (7) | 0.0131 (7) | 0.0154 (7) | 0.0039 (5) | −0.0005 (5) | −0.0009 (5) |
C11 | 0.0145 (7) | 0.0149 (7) | 0.0111 (7) | 0.0038 (6) | −0.0010 (5) | 0.0005 (5) |
C1 | 0.0150 (7) | 0.0174 (7) | 0.0121 (7) | 0.0066 (6) | 0.0012 (5) | 0.0016 (5) |
C33 | 0.0180 (7) | 0.0192 (7) | 0.0108 (7) | 0.0105 (6) | −0.0001 (5) | 0.0011 (5) |
C7 | 0.0188 (7) | 0.0177 (7) | 0.0209 (8) | 0.0112 (6) | −0.0023 (6) | 0.0007 (6) |
C17 | 0.0190 (7) | 0.0168 (7) | 0.0171 (8) | 0.0106 (6) | −0.0028 (6) | −0.0008 (6) |
C20 | 0.0146 (7) | 0.0164 (7) | 0.0127 (7) | 0.0058 (6) | −0.0003 (5) | 0.0012 (5) |
C5 | 0.0148 (7) | 0.0149 (7) | 0.0171 (8) | 0.0067 (6) | 0.0002 (5) | 0.0009 (5) |
C35 | 0.0177 (7) | 0.0361 (9) | 0.0193 (8) | 0.0136 (7) | −0.0017 (6) | 0.0018 (6) |
C28 | 0.0216 (7) | 0.0185 (8) | 0.0177 (8) | 0.0077 (6) | −0.0017 (6) | 0.0014 (6) |
N7 | 0.0282 (8) | 0.0327 (9) | 0.0457 (10) | 0.0095 (7) | −0.0001 (7) | −0.0166 (7) |
C12 | 0.0183 (7) | 0.0199 (8) | 0.0103 (7) | 0.0071 (6) | −0.0010 (6) | −0.0008 (5) |
C8 | 0.0184 (7) | 0.0199 (8) | 0.0156 (8) | 0.0094 (6) | −0.0044 (6) | 0.0016 (6) |
C49 | 0.0214 (8) | 0.0234 (8) | 0.0202 (8) | 0.0116 (6) | 0.0006 (6) | 0.0024 (6) |
C40 | 0.0221 (8) | 0.0205 (8) | 0.0175 (8) | 0.0073 (6) | 0.0003 (6) | 0.0013 (6) |
C21 | 0.0174 (7) | 0.0153 (7) | 0.0166 (8) | 0.0085 (6) | −0.0061 (6) | −0.0020 (5) |
C18 | 0.0212 (7) | 0.0162 (7) | 0.0137 (7) | 0.0094 (6) | −0.0029 (6) | 0.0019 (5) |
C3 | 0.0221 (7) | 0.0177 (8) | 0.0162 (8) | 0.0109 (6) | −0.0001 (6) | −0.0024 (6) |
C34 | 0.0193 (8) | 0.0239 (8) | 0.0171 (8) | 0.0094 (6) | −0.0026 (6) | −0.0022 (6) |
C13 | 0.0162 (7) | 0.0183 (7) | 0.0144 (7) | 0.0074 (6) | 0.0012 (6) | −0.0015 (5) |
C38 | 0.0199 (7) | 0.0201 (8) | 0.0147 (8) | 0.0096 (6) | −0.0011 (6) | −0.0012 (6) |
C2 | 0.0232 (8) | 0.0224 (8) | 0.0111 (7) | 0.0120 (6) | −0.0006 (6) | −0.0016 (6) |
C10 | 0.0152 (7) | 0.0152 (7) | 0.0115 (7) | 0.0040 (6) | −0.0013 (5) | 0.0024 (5) |
C22 | 0.0209 (7) | 0.0199 (8) | 0.0160 (8) | 0.0074 (6) | −0.0056 (6) | −0.0006 (6) |
C32 | 0.0193 (7) | 0.0192 (8) | 0.0181 (8) | 0.0049 (6) | −0.0026 (6) | 0.0007 (6) |
C26 | 0.0191 (7) | 0.0159 (7) | 0.0248 (8) | 0.0071 (6) | −0.0015 (6) | −0.0024 (6) |
C23 | 0.0293 (8) | 0.0144 (7) | 0.0218 (8) | 0.0056 (6) | −0.0114 (6) | 0.0000 (6) |
C41 | 0.0317 (9) | 0.0236 (8) | 0.0152 (8) | 0.0110 (7) | 0.0058 (6) | 0.0042 (6) |
C31 | 0.0228 (8) | 0.0267 (8) | 0.0169 (8) | 0.0105 (7) | −0.0003 (6) | 0.0072 (6) |
C29 | 0.0207 (8) | 0.0236 (8) | 0.0237 (9) | 0.0071 (6) | −0.0066 (6) | −0.0069 (6) |
C42 | 0.0356 (9) | 0.0261 (8) | 0.0108 (7) | 0.0212 (7) | −0.0008 (6) | 0.0005 (6) |
C36 | 0.0276 (8) | 0.0353 (9) | 0.0159 (8) | 0.0224 (7) | 0.0029 (6) | 0.0023 (6) |
C37 | 0.0300 (8) | 0.0243 (8) | 0.0152 (8) | 0.0169 (7) | −0.0001 (6) | −0.0026 (6) |
C30 | 0.0212 (8) | 0.0346 (9) | 0.0140 (8) | 0.0139 (7) | −0.0052 (6) | −0.0017 (6) |
C25 | 0.0225 (8) | 0.0241 (8) | 0.0309 (9) | 0.0135 (7) | −0.0027 (7) | −0.0069 (7) |
C44 | 0.0191 (8) | 0.0355 (9) | 0.0162 (8) | 0.0098 (7) | 0.0013 (6) | 0.0045 (6) |
C24 | 0.0316 (9) | 0.0178 (8) | 0.0287 (9) | 0.0151 (7) | −0.0126 (7) | −0.0072 (6) |
C46 | 0.0228 (8) | 0.0278 (9) | 0.0219 (9) | 0.0057 (7) | −0.0018 (6) | −0.0068 (6) |
C56 | 0.0224 (8) | 0.0258 (9) | 0.0293 (9) | 0.0025 (7) | 0.0018 (7) | −0.0078 (7) |
C45 | 0.0221 (8) | 0.0246 (8) | 0.0182 (8) | 0.0075 (7) | −0.0013 (6) | −0.0004 (6) |
C47 | 0.0228 (8) | 0.0195 (8) | 0.0336 (10) | 0.0029 (7) | 0.0066 (7) | −0.0058 (7) |
C43 | 0.0241 (8) | 0.0419 (10) | 0.0180 (9) | 0.0153 (7) | −0.0051 (6) | −0.0001 (7) |
C57 | 0.0255 (9) | 0.0294 (9) | 0.0326 (10) | 0.0104 (7) | 0.0003 (7) | −0.0084 (7) |
C48 | 0.0291 (9) | 0.0221 (8) | 0.0295 (9) | 0.0095 (7) | 0.0077 (7) | 0.0082 (7) |
C54 | 0.0284 (9) | 0.0296 (9) | 0.0325 (10) | 0.0029 (8) | 0.0013 (7) | −0.0083 (7) |
C58 | 0.0366 (10) | 0.0327 (10) | 0.0294 (10) | 0.0100 (8) | 0.0009 (8) | −0.0079 (7) |
C50 | 0.0242 (8) | 0.0231 (9) | 0.0314 (10) | 0.0052 (7) | 0.0022 (7) | −0.0001 (7) |
C51 | 0.0263 (9) | 0.0292 (9) | 0.0328 (10) | 0.0006 (7) | 0.0005 (7) | 0.0082 (7) |
C55 | 0.0268 (9) | 0.0237 (9) | 0.0390 (11) | 0.0057 (7) | −0.0038 (7) | −0.0076 (7) |
C59 | 0.0319 (10) | 0.0374 (11) | 0.0345 (11) | 0.0067 (8) | 0.0061 (8) | −0.0153 (8) |
C53 | 0.0236 (9) | 0.0314 (10) | 0.0591 (13) | 0.0096 (8) | 0.0042 (8) | −0.0043 (9) |
C52 | 0.0246 (9) | 0.0309 (10) | 0.0544 (13) | 0.0057 (8) | −0.0043 (8) | 0.0134 (9) |
Geometric parameters (Å, º) top
Mn1—N4 | 2.0024 (12) | C21—C22 | 1.395 (2) |
Mn1—N2 | 2.0056 (12) | C21—C26 | 1.397 (2) |
Mn1—N3 | 2.0081 (12) | C18—H18 | 0.9500 |
Mn1—N1 | 2.0119 (12) | C3—C2 | 1.354 (2) |
Mn1—N5 | 2.4203 (12) | C3—H3 | 0.9500 |
Mn1—Cl1 | 2.4693 (4) | C34—H34 | 0.9500 |
N3—C14 | 1.3732 (18) | C13—H13 | 0.9500 |
N3—C11 | 1.3747 (19) | C38—C37 | 1.392 (2) |
N2—C6 | 1.3771 (18) | C38—H38 | 0.9500 |
N2—C9 | 1.3776 (19) | C2—H2 | 0.9500 |
N4—C19 | 1.3735 (18) | C22—C23 | 1.390 (2) |
N4—C16 | 1.3752 (18) | C22—H22 | 0.9500 |
N1—C1 | 1.3709 (19) | C32—C31 | 1.382 (2) |
N1—C4 | 1.3798 (18) | C32—H32 | 0.9500 |
N5—C49 | 1.336 (2) | C26—C25 | 1.390 (2) |
N5—C45 | 1.344 (2) | C26—H26 | 0.9500 |
N6—C54 | 1.335 (2) | C23—C24 | 1.381 (2) |
N6—C50 | 1.339 (2) | C23—H23 | 0.9500 |
C19—C20 | 1.400 (2) | C41—C42 | 1.381 (2) |
C19—C18 | 1.439 (2) | C41—H41 | 0.9500 |
C16—C15 | 1.403 (2) | C31—C30 | 1.387 (2) |
C16—C17 | 1.441 (2) | C31—H31 | 0.9500 |
C14—C15 | 1.401 (2) | C29—C30 | 1.384 (2) |
C14—C13 | 1.4413 (19) | C29—H29 | 0.9500 |
C9—C10 | 1.397 (2) | C42—C43 | 1.385 (2) |
C9—C8 | 1.436 (2) | C42—H42 | 0.9500 |
C39—C40 | 1.387 (2) | C36—C37 | 1.387 (2) |
C39—C44 | 1.391 (2) | C36—H36 | 0.9500 |
C39—C20 | 1.492 (2) | C37—H37 | 0.9500 |
C6—C5 | 1.399 (2) | C30—H30 | 0.9500 |
C6—C7 | 1.434 (2) | C25—C24 | 1.384 (2) |
C4—C5 | 1.394 (2) | C25—H25 | 0.9500 |
C4—C3 | 1.436 (2) | C44—C43 | 1.385 (2) |
C27—C28 | 1.390 (2) | C44—H44 | 0.9500 |
C27—C32 | 1.397 (2) | C24—H24 | 0.9500 |
C27—C10 | 1.493 (2) | C46—C47 | 1.379 (2) |
C15—C33 | 1.493 (2) | C46—C45 | 1.382 (2) |
C11—C10 | 1.400 (2) | C46—H46 | 0.9500 |
C11—C12 | 1.4360 (19) | C56—C57 | 1.377 (3) |
C1—C20 | 1.399 (2) | C56—C55 | 1.383 (2) |
C1—C2 | 1.437 (2) | C56—H56 | 0.9500 |
C33—C34 | 1.396 (2) | C45—H45 | 0.9500 |
C33—C38 | 1.396 (2) | C47—C48 | 1.386 (2) |
C7—C8 | 1.357 (2) | C47—H47 | 0.9500 |
C7—H7 | 0.9500 | C43—H43 | 0.9500 |
C17—C18 | 1.352 (2) | C57—C58 | 1.385 (2) |
C17—H17 | 0.9500 | C57—H57 | 0.9500 |
C5—C21 | 1.494 (2) | C48—H48 | 0.9500 |
C35—C36 | 1.385 (2) | C54—C53 | 1.382 (3) |
C35—C34 | 1.390 (2) | C54—H54 | 0.9500 |
C35—H35 | 0.9500 | C58—C59 | 1.377 (3) |
C28—C29 | 1.387 (2) | C58—H58 | 0.9500 |
C28—H28 | 0.9500 | C50—C51 | 1.376 (3) |
N7—C59 | 1.333 (3) | C50—H50 | 0.9500 |
N7—C55 | 1.336 (2) | C51—C52 | 1.377 (3) |
C12—C13 | 1.354 (2) | C51—H51 | 0.9500 |
C12—H12 | 0.9500 | C55—H55 | 0.9500 |
C8—H8 | 0.9500 | C59—H59 | 0.9500 |
C49—C48 | 1.384 (2) | C53—C52 | 1.381 (3) |
C49—H49 | 0.9500 | C53—H53 | 0.9500 |
C40—C41 | 1.393 (2) | C52—H52 | 0.9500 |
C40—H40 | 0.9500 | | |
| | | |
N4—Mn1—N2 | 173.35 (5) | C2—C3—H3 | 126.4 |
N4—Mn1—N3 | 90.21 (5) | C4—C3—H3 | 126.4 |
N2—Mn1—N3 | 89.54 (5) | C35—C34—C33 | 121.25 (14) |
N4—Mn1—N1 | 90.24 (5) | C35—C34—H34 | 119.4 |
N2—Mn1—N1 | 89.27 (5) | C33—C34—H34 | 119.4 |
N3—Mn1—N1 | 173.61 (5) | C12—C13—C14 | 107.10 (13) |
N4—Mn1—N5 | 85.07 (4) | C12—C13—H13 | 126.4 |
N2—Mn1—N5 | 88.27 (4) | C14—C13—H13 | 126.4 |
N3—Mn1—N5 | 89.41 (4) | C37—C38—C33 | 120.44 (14) |
N1—Mn1—N5 | 84.28 (4) | C37—C38—H38 | 119.8 |
N4—Mn1—Cl1 | 90.71 (3) | C33—C38—H38 | 119.8 |
N2—Mn1—Cl1 | 95.93 (3) | C3—C2—C1 | 107.32 (13) |
N3—Mn1—Cl1 | 88.82 (3) | C3—C2—H2 | 126.3 |
N1—Mn1—Cl1 | 97.55 (3) | C1—C2—H2 | 126.3 |
N5—Mn1—Cl1 | 175.42 (3) | C9—C10—C11 | 123.38 (13) |
C14—N3—C11 | 107.03 (11) | C9—C10—C27 | 119.06 (13) |
C14—N3—Mn1 | 127.07 (9) | C11—C10—C27 | 117.21 (12) |
C11—N3—Mn1 | 125.89 (9) | C23—C22—C21 | 120.75 (15) |
C6—N2—C9 | 106.58 (11) | C23—C22—H22 | 119.6 |
C6—N2—Mn1 | 126.97 (9) | C21—C22—H22 | 119.6 |
C9—N2—Mn1 | 126.07 (9) | C31—C32—C27 | 120.51 (14) |
C19—N4—C16 | 106.88 (11) | C31—C32—H32 | 119.7 |
C19—N4—Mn1 | 125.96 (9) | C27—C32—H32 | 119.7 |
C16—N4—Mn1 | 126.85 (9) | C25—C26—C21 | 120.27 (15) |
C1—N1—C4 | 106.58 (11) | C25—C26—H26 | 119.9 |
C1—N1—Mn1 | 125.58 (9) | C21—C26—H26 | 119.9 |
C4—N1—Mn1 | 127.11 (9) | C24—C23—C22 | 120.25 (15) |
C49—N5—C45 | 117.15 (13) | C24—C23—H23 | 119.9 |
C49—N5—Mn1 | 121.86 (10) | C22—C23—H23 | 119.9 |
C45—N5—Mn1 | 120.95 (10) | C42—C41—C40 | 119.59 (15) |
C54—N6—C50 | 116.48 (15) | C42—C41—H41 | 120.2 |
N4—C19—C20 | 125.37 (13) | C40—C41—H41 | 120.2 |
N4—C19—C18 | 109.31 (12) | C32—C31—C30 | 120.41 (14) |
C20—C19—C18 | 124.83 (13) | C32—C31—H31 | 119.8 |
N4—C16—C15 | 125.87 (13) | C30—C31—H31 | 119.8 |
N4—C16—C17 | 109.21 (12) | C30—C29—C28 | 120.05 (14) |
C15—C16—C17 | 124.79 (13) | C30—C29—H29 | 120.0 |
N3—C14—C15 | 125.52 (12) | C28—C29—H29 | 120.0 |
N3—C14—C13 | 109.16 (12) | C41—C42—C43 | 119.98 (14) |
C15—C14—C13 | 125.25 (13) | C41—C42—H42 | 120.0 |
N2—C9—C10 | 125.25 (13) | C43—C42—H42 | 120.0 |
N2—C9—C8 | 109.46 (12) | C35—C36—C37 | 119.95 (14) |
C10—C9—C8 | 124.94 (14) | C35—C36—H36 | 120.0 |
C40—C39—C44 | 118.83 (14) | C37—C36—H36 | 120.0 |
C40—C39—C20 | 121.35 (13) | C36—C37—C38 | 120.28 (14) |
C44—C39—C20 | 119.79 (13) | C36—C37—H37 | 119.9 |
N2—C6—C5 | 126.20 (13) | C38—C37—H37 | 119.9 |
N2—C6—C7 | 109.42 (12) | C29—C30—C31 | 119.56 (14) |
C5—C6—C7 | 124.29 (13) | C29—C30—H30 | 120.2 |
N1—C4—C5 | 125.30 (13) | C31—C30—H30 | 120.2 |
N1—C4—C3 | 109.42 (12) | C24—C25—C26 | 120.57 (15) |
C5—C4—C3 | 125.22 (13) | C24—C25—H25 | 119.7 |
C28—C27—C32 | 118.52 (14) | C26—C25—H25 | 119.7 |
C28—C27—C10 | 121.58 (13) | C43—C44—C39 | 120.45 (15) |
C32—C27—C10 | 119.80 (13) | C43—C44—H44 | 119.8 |
C14—C15—C16 | 123.67 (13) | C39—C44—H44 | 119.8 |
C14—C15—C33 | 118.51 (12) | C23—C24—C25 | 119.59 (14) |
C16—C15—C33 | 117.83 (12) | C23—C24—H24 | 120.2 |
N3—C11—C10 | 126.26 (13) | C25—C24—H24 | 120.2 |
N3—C11—C12 | 109.18 (12) | C47—C46—C45 | 118.98 (15) |
C10—C11—C12 | 124.37 (13) | C47—C46—H46 | 120.5 |
N1—C1—C20 | 126.55 (13) | C45—C46—H46 | 120.5 |
N1—C1—C2 | 109.51 (12) | C57—C56—C55 | 118.85 (16) |
C20—C1—C2 | 123.60 (14) | C57—C56—H56 | 120.6 |
C34—C33—C38 | 118.41 (13) | C55—C56—H56 | 120.6 |
C34—C33—C15 | 119.22 (13) | N5—C45—C46 | 123.24 (15) |
C38—C33—C15 | 122.36 (13) | N5—C45—H45 | 118.4 |
C8—C7—C6 | 107.38 (13) | C46—C45—H45 | 118.4 |
C8—C7—H7 | 126.3 | C46—C47—C48 | 118.46 (15) |
C6—C7—H7 | 126.3 | C46—C47—H47 | 120.8 |
C18—C17—C16 | 107.28 (13) | C48—C47—H47 | 120.8 |
C18—C17—H17 | 126.4 | C42—C43—C44 | 120.23 (15) |
C16—C17—H17 | 126.4 | C42—C43—H43 | 119.9 |
C1—C20—C19 | 123.38 (14) | C44—C43—H43 | 119.9 |
C1—C20—C39 | 117.16 (12) | C56—C57—C58 | 118.07 (17) |
C19—C20—C39 | 118.99 (13) | C56—C57—H57 | 121.0 |
C4—C5—C6 | 123.12 (13) | C58—C57—H57 | 121.0 |
C4—C5—C21 | 119.95 (13) | C49—C48—C47 | 118.84 (15) |
C6—C5—C21 | 116.91 (12) | C49—C48—H48 | 120.6 |
C36—C35—C34 | 119.66 (15) | C47—C48—H48 | 120.6 |
C36—C35—H35 | 120.2 | N6—C54—C53 | 123.86 (17) |
C34—C35—H35 | 120.2 | N6—C54—H54 | 118.1 |
C29—C28—C27 | 120.88 (14) | C53—C54—H54 | 118.1 |
C29—C28—H28 | 119.6 | C59—C58—C57 | 118.74 (19) |
C27—C28—H28 | 119.6 | C59—C58—H58 | 120.6 |
C59—N7—C55 | 116.02 (16) | C57—C58—H58 | 120.6 |
C13—C12—C11 | 107.45 (13) | N6—C50—C51 | 123.76 (17) |
C13—C12—H12 | 126.3 | N6—C50—H50 | 118.1 |
C11—C12—H12 | 126.3 | C51—C50—H50 | 118.1 |
C7—C8—C9 | 107.11 (13) | C50—C51—C52 | 118.78 (17) |
C7—C8—H8 | 126.4 | C50—C51—H51 | 120.6 |
C9—C8—H8 | 126.4 | C52—C51—H51 | 120.6 |
N5—C49—C48 | 123.33 (15) | N7—C55—C56 | 123.99 (18) |
N5—C49—H49 | 118.3 | N7—C55—H55 | 118.0 |
C48—C49—H49 | 118.3 | C56—C55—H55 | 118.0 |
C39—C40—C41 | 120.90 (14) | N7—C59—C58 | 124.31 (17) |
C39—C40—H40 | 119.6 | N7—C59—H59 | 117.8 |
C41—C40—H40 | 119.6 | C58—C59—H59 | 117.8 |
C22—C21—C26 | 118.55 (13) | C52—C53—C54 | 118.43 (18) |
C22—C21—C5 | 119.75 (13) | C52—C53—H53 | 120.8 |
C26—C21—C5 | 121.67 (13) | C54—C53—H53 | 120.8 |
C17—C18—C19 | 107.27 (13) | C51—C52—C53 | 118.67 (17) |
C17—C18—H18 | 126.4 | C51—C52—H52 | 120.7 |
C19—C18—H18 | 126.4 | C53—C52—H52 | 120.7 |
C2—C3—C4 | 107.15 (13) | | |
(1,4-Diazabicyclo[2.2.2]octane)(5,10,15,20-tetraphenylporphyrin)manganese(III)
chloride–1,4-diazabicyclo[2.2.2]octane–toluene–water (4/4/4/1) (IV_DABCO)
top
Crystal data top
[Mn(C44H28N4)(C6H12N2)]Cl·C6H12N2·C7H8·0.25H2O | Z = 2 |
Mr = 1023.58 | F(000) = 1076 |
Triclinic, P1 | Dx = 1.310 Mg m−3 |
a = 11.4402 (2) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 13.4019 (3) Å | Cell parameters from 9495 reflections |
c = 18.6407 (4) Å | θ = 2.4–68.6° |
α = 95.774 (1)° | µ = 2.95 mm−1 |
β = 92.199 (1)° | T = 100 K |
γ = 113.630 (1)° | Block, black |
V = 2595.35 (9) Å3 | 0.24 × 0.22 × 0.18 mm |
Data collection top
Bruker SMART CCD APEXII area-detector diffractometer | 8538 independent reflections |
Radiation source: fine-focus sealed tube | 6596 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
φ and ω scans | θmax = 66.7°, θmin = 2.4° |
Absorption correction: numerical (SADABS; Krause et al., 2015) | h = −13→13 |
Tmin = 0.540, Tmax = 0.737 | k = −15→15 |
24215 measured reflections | l = −22→22 |
Refinement top
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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.180 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0887P)2 + 3.2657P] where P = (Fo2 + 2Fc2)/3 |
8538 reflections | (Δ/σ)max = 0.001 |
668 parameters | Δρmax = 1.30 e Å−3 |
12 restraints | Δρmin = −0.68 e Å−3 |
Special details top
Experimental. Crystal mounted on a Cryoloop using Paratone-N. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Mn1 | 0.51095 (5) | 0.78380 (4) | 0.74011 (3) | 0.02184 (17) | |
Cl1 | 0.71084 (8) | 0.84537 (7) | 0.68325 (5) | 0.0299 (2) | |
N1 | 0.5974 (3) | 0.8617 (2) | 0.83868 (15) | 0.0241 (6) | |
N4 | 0.5218 (3) | 0.6448 (2) | 0.76577 (15) | 0.0246 (6) | |
N3 | 0.4063 (3) | 0.7013 (2) | 0.64754 (15) | 0.0227 (6) | |
N2 | 0.4790 (3) | 0.9171 (2) | 0.72023 (15) | 0.0230 (6) | |
N5 | 0.2951 (3) | 0.7187 (2) | 0.80052 (15) | 0.0241 (6) | |
N6 | 0.0798 (3) | 0.6573 (3) | 0.86100 (16) | 0.0321 (7) | |
N7 | 0.0925 (4) | −0.0075 (4) | 0.8352 (2) | 0.0681 (13) | |
N8 | 0.0735 (3) | 0.1114 (3) | 0.7378 (2) | 0.0455 (9) | |
C1 | 0.6483 (3) | 0.8203 (3) | 0.89055 (18) | 0.0256 (8) | |
C2 | 0.7086 (4) | 0.9037 (3) | 0.95052 (19) | 0.0307 (9) | |
H2 | 0.749984 | 0.895859 | 0.993447 | 0.037* | |
C3 | 0.6963 (4) | 0.9951 (3) | 0.93523 (19) | 0.0300 (8) | |
H3 | 0.727219 | 1.063612 | 0.965252 | 0.036* | |
C4 | 0.6272 (3) | 0.9697 (3) | 0.86469 (18) | 0.0260 (8) | |
C5 | 0.5972 (3) | 1.0441 (3) | 0.82930 (18) | 0.0239 (8) | |
C6 | 0.5266 (3) | 1.0177 (3) | 0.76185 (18) | 0.0241 (8) | |
C7 | 0.4909 (3) | 1.0933 (3) | 0.72672 (19) | 0.0262 (8) | |
H7 | 0.511609 | 1.167980 | 0.744252 | 0.031* | |
C8 | 0.4224 (3) | 1.0379 (3) | 0.66416 (18) | 0.0250 (8) | |
H8 | 0.385364 | 1.066486 | 0.629486 | 0.030* | |
C9 | 0.4153 (3) | 0.9279 (3) | 0.65924 (18) | 0.0229 (8) | |
C10 | 0.3558 (3) | 0.8469 (3) | 0.60109 (18) | 0.0230 (8) | |
C11 | 0.3521 (3) | 0.7413 (3) | 0.59601 (18) | 0.0234 (8) | |
C12 | 0.2889 (3) | 0.6571 (3) | 0.53708 (19) | 0.0272 (8) | |
H12 | 0.244693 | 0.664015 | 0.494965 | 0.033* | |
C13 | 0.3034 (3) | 0.5658 (3) | 0.55202 (19) | 0.0277 (8) | |
H13 | 0.271269 | 0.496746 | 0.522537 | 0.033* | |
C14 | 0.3767 (3) | 0.5930 (3) | 0.62093 (18) | 0.0247 (8) | |
C15 | 0.4094 (3) | 0.5189 (3) | 0.65521 (19) | 0.0250 (8) | |
C16 | 0.4760 (3) | 0.5440 (3) | 0.72338 (18) | 0.0243 (8) | |
C17 | 0.5094 (3) | 0.4684 (3) | 0.75952 (19) | 0.0284 (8) | |
H17 | 0.488191 | 0.393590 | 0.742074 | 0.034* | |
C18 | 0.5764 (4) | 0.5228 (3) | 0.82292 (19) | 0.0297 (8) | |
H18 | 0.611820 | 0.493668 | 0.858012 | 0.036* | |
C19 | 0.5840 (3) | 0.6333 (3) | 0.82736 (18) | 0.0258 (8) | |
C20 | 0.6438 (3) | 0.7142 (3) | 0.88563 (18) | 0.0271 (8) | |
C21 | 0.6423 (4) | 1.1597 (3) | 0.8654 (2) | 0.0323 (9) | |
C22 | 0.7412 (4) | 1.2438 (3) | 0.8391 (3) | 0.0444 (11) | |
H22 | 0.780718 | 1.227563 | 0.798261 | 0.053* | |
C23 | 0.7834 (5) | 1.3525 (4) | 0.8721 (4) | 0.0723 (19) | |
H23 | 0.851122 | 1.410154 | 0.854017 | 0.087* | |
C24 | 0.7248 (6) | 1.3741 (5) | 0.9313 (3) | 0.0717 (16) | |
H24 | 0.752198 | 1.447355 | 0.954056 | 0.086* | |
C25 | 0.6306 (6) | 1.2939 (5) | 0.9568 (3) | 0.0686 (15) | |
H25 | 0.592420 | 1.311210 | 0.997902 | 0.082* | |
C26 | 0.5855 (5) | 1.1843 (4) | 0.9250 (2) | 0.0485 (12) | |
H26 | 0.517525 | 1.128069 | 0.944019 | 0.058* | |
C27 | 0.2853 (3) | 0.8727 (3) | 0.54106 (18) | 0.0247 (8) | |
C28 | 0.3384 (4) | 0.8999 (3) | 0.47622 (19) | 0.0302 (8) | |
H28 | 0.420825 | 0.901419 | 0.468882 | 0.036* | |
C29 | 0.2716 (4) | 0.9249 (3) | 0.4221 (2) | 0.0349 (9) | |
H29 | 0.309295 | 0.945009 | 0.378289 | 0.042* | |
C30 | 0.1512 (4) | 0.9207 (3) | 0.4314 (2) | 0.0375 (10) | |
H30 | 0.105489 | 0.937224 | 0.394089 | 0.045* | |
C31 | 0.0966 (4) | 0.8924 (3) | 0.4957 (2) | 0.0371 (10) | |
H31 | 0.013096 | 0.888772 | 0.502224 | 0.044* | |
C32 | 0.1641 (4) | 0.8694 (3) | 0.5501 (2) | 0.0313 (9) | |
H32 | 0.126861 | 0.851068 | 0.594199 | 0.038* | |
C33 | 0.3693 (3) | 0.4058 (3) | 0.61587 (19) | 0.0263 (8) | |
C34 | 0.4381 (4) | 0.3869 (3) | 0.5602 (2) | 0.0363 (9) | |
H34 | 0.513657 | 0.445091 | 0.549228 | 0.044* | |
C35 | 0.3976 (4) | 0.2839 (3) | 0.5207 (2) | 0.0425 (11) | |
H35 | 0.444561 | 0.272277 | 0.482170 | 0.051* | |
C36 | 0.2898 (4) | 0.1983 (3) | 0.5369 (2) | 0.0370 (9) | |
H36 | 0.262277 | 0.127797 | 0.509711 | 0.044* | |
C37 | 0.2223 (4) | 0.2155 (3) | 0.5925 (2) | 0.0400 (10) | |
H37 | 0.148237 | 0.156393 | 0.604102 | 0.048* | |
C38 | 0.2613 (4) | 0.3187 (3) | 0.6320 (2) | 0.0342 (9) | |
H38 | 0.213669 | 0.329673 | 0.670291 | 0.041* | |
C39 | 0.7114 (4) | 0.6876 (3) | 0.94673 (19) | 0.0291 (8) | |
C40 | 0.6449 (4) | 0.6311 (4) | 1.0004 (2) | 0.0426 (11) | |
H40 | 0.554349 | 0.605848 | 0.997893 | 0.051* | |
C41 | 0.7092 (4) | 0.6107 (4) | 1.0582 (2) | 0.0492 (12) | |
H41 | 0.662338 | 0.572561 | 1.095114 | 0.059* | |
C42 | 0.8383 (4) | 0.6449 (3) | 1.0622 (2) | 0.0389 (10) | |
H42 | 0.881857 | 0.631267 | 1.101911 | 0.047* | |
C43 | 0.9051 (5) | 0.6988 (5) | 1.0089 (3) | 0.0668 (17) | |
H43 | 0.995369 | 0.721698 | 1.011094 | 0.080* | |
C44 | 0.8421 (4) | 0.7206 (5) | 0.9513 (2) | 0.0626 (16) | |
H44 | 0.889896 | 0.758751 | 0.914631 | 0.075* | |
C45 | 0.2690 (4) | 0.6167 (3) | 0.8338 (2) | 0.0342 (9) | |
H45A | 0.339340 | 0.629538 | 0.871047 | 0.041* | |
H45B | 0.265816 | 0.557631 | 0.796285 | 0.041* | |
C46 | 0.1399 (4) | 0.5800 (3) | 0.8691 (2) | 0.0371 (9) | |
H46A | 0.081325 | 0.505850 | 0.846032 | 0.045* | |
H46B | 0.155155 | 0.576024 | 0.921172 | 0.045* | |
C47 | 0.1698 (4) | 0.7664 (3) | 0.8940 (2) | 0.0364 (9) | |
H47A | 0.186825 | 0.764978 | 0.946269 | 0.044* | |
H47B | 0.130994 | 0.819722 | 0.889045 | 0.044* | |
C48 | 0.2977 (4) | 0.8044 (3) | 0.8581 (2) | 0.0315 (9) | |
H48A | 0.312470 | 0.872944 | 0.837038 | 0.038* | |
H48B | 0.369175 | 0.819931 | 0.895132 | 0.038* | |
C49 | 0.1853 (3) | 0.6960 (4) | 0.7466 (2) | 0.0359 (9) | |
H49A | 0.180423 | 0.637517 | 0.708103 | 0.043* | |
H49B | 0.198861 | 0.762954 | 0.723848 | 0.043* | |
C50 | 0.0578 (4) | 0.6592 (4) | 0.7833 (2) | 0.0380 (10) | |
H50A | 0.016902 | 0.710424 | 0.775924 | 0.046* | |
H50B | −0.001253 | 0.585078 | 0.760461 | 0.046* | |
C51 | 0.0607 (5) | 0.0037 (4) | 0.7062 (3) | 0.0498 (12) | |
H51A | 0.127814 | 0.011943 | 0.672437 | 0.060* | |
H51B | −0.023754 | −0.035163 | 0.678219 | 0.060* | |
C52 | 0.0730 (6) | −0.0631 (5) | 0.7638 (3) | 0.0715 (16) | |
H52A | −0.005730 | −0.131730 | 0.760045 | 0.086* | |
H52B | 0.145729 | −0.083579 | 0.754976 | 0.086* | |
C53 | 0.2081 (5) | 0.0972 (6) | 0.8398 (3) | 0.0713 (18) | |
H53A | 0.284777 | 0.080947 | 0.834764 | 0.086* | |
H53B | 0.218279 | 0.139760 | 0.887974 | 0.086* | |
C54 | 0.1989 (4) | 0.1656 (4) | 0.7813 (3) | 0.0508 (12) | |
H54A | 0.209416 | 0.239033 | 0.803937 | 0.061* | |
H54B | 0.268723 | 0.175449 | 0.749233 | 0.061* | |
C55 | −0.0164 (5) | 0.0252 (6) | 0.8457 (3) | 0.0781 (19) | |
H55A | −0.004217 | 0.066668 | 0.894471 | 0.094* | |
H55B | −0.097327 | −0.041375 | 0.842633 | 0.094* | |
C56 | −0.0256 (5) | 0.0971 (4) | 0.7877 (3) | 0.0602 (14) | |
H56A | −0.110991 | 0.061971 | 0.760447 | 0.072* | |
H56B | −0.015550 | 0.169821 | 0.811607 | 0.072* | |
C57 | 0.1392 (4) | 0.4445 (4) | 0.3826 (2) | 0.0523 (12) | |
C58 | 0.0359 (4) | 0.4653 (3) | 0.4037 (2) | 0.0349 (9) | |
H58 | −0.025931 | 0.413510 | 0.429001 | 0.042* | |
C59 | 0.0188 (5) | 0.5552 (5) | 0.3903 (3) | 0.0572 (13) | |
H59 | −0.054486 | 0.565123 | 0.405611 | 0.069* | |
C60 | 0.1086 (5) | 0.6351 (4) | 0.3537 (3) | 0.0634 (15) | |
H60 | 0.097246 | 0.698703 | 0.343230 | 0.076* | |
C61 | 0.2132 (6) | 0.6167 (6) | 0.3338 (3) | 0.089 (2) | |
H61 | 0.277761 | 0.670680 | 0.311188 | 0.107* | |
C62 | 0.2276 (4) | 0.5205 (5) | 0.3458 (2) | 0.0543 (13) | |
H62 | 0.298163 | 0.507744 | 0.328615 | 0.065* | |
C63 | 0.1530 (6) | 0.3430 (4) | 0.3959 (3) | 0.0683 (16) | |
H63A | 0.122515 | 0.322792 | 0.442918 | 0.102* | |
H63B | 0.243394 | 0.355104 | 0.395798 | 0.102* | |
H63C | 0.102399 | 0.283603 | 0.357671 | 0.102* | |
O1 | 0.074 (2) | 0.3331 (16) | 0.7725 (9) | 0.094 (6) | 0.25 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.0264 (3) | 0.0240 (3) | 0.0171 (3) | 0.0120 (3) | 0.0008 (2) | 0.0046 (2) |
Cl1 | 0.0300 (5) | 0.0331 (5) | 0.0276 (4) | 0.0127 (4) | 0.0072 (4) | 0.0076 (4) |
N1 | 0.0274 (15) | 0.0284 (17) | 0.0200 (14) | 0.0141 (14) | 0.0024 (12) | 0.0062 (13) |
N4 | 0.0276 (15) | 0.0269 (17) | 0.0210 (14) | 0.0124 (14) | 0.0027 (13) | 0.0048 (13) |
N3 | 0.0247 (15) | 0.0235 (16) | 0.0218 (14) | 0.0111 (13) | 0.0030 (12) | 0.0053 (13) |
N2 | 0.0249 (15) | 0.0238 (16) | 0.0207 (14) | 0.0109 (13) | −0.0003 (12) | 0.0018 (13) |
N5 | 0.0273 (15) | 0.0266 (16) | 0.0201 (14) | 0.0126 (14) | 0.0003 (12) | 0.0041 (13) |
N6 | 0.0319 (17) | 0.0373 (19) | 0.0305 (16) | 0.0159 (15) | 0.0066 (14) | 0.0108 (15) |
N7 | 0.071 (3) | 0.090 (4) | 0.051 (3) | 0.036 (3) | 0.005 (2) | 0.034 (3) |
N8 | 0.045 (2) | 0.050 (2) | 0.045 (2) | 0.0221 (19) | 0.0035 (18) | 0.0084 (19) |
C1 | 0.0297 (18) | 0.033 (2) | 0.0178 (16) | 0.0152 (17) | 0.0037 (15) | 0.0077 (16) |
C2 | 0.040 (2) | 0.038 (2) | 0.0180 (17) | 0.0197 (19) | −0.0003 (16) | 0.0066 (17) |
C3 | 0.038 (2) | 0.034 (2) | 0.0191 (17) | 0.0169 (18) | −0.0012 (16) | 0.0009 (17) |
C4 | 0.0273 (18) | 0.031 (2) | 0.0207 (17) | 0.0129 (17) | 0.0016 (15) | 0.0009 (16) |
C5 | 0.0257 (18) | 0.028 (2) | 0.0185 (16) | 0.0115 (16) | 0.0048 (15) | 0.0029 (16) |
C6 | 0.0248 (18) | 0.028 (2) | 0.0226 (17) | 0.0131 (16) | 0.0056 (15) | 0.0040 (16) |
C7 | 0.0306 (19) | 0.025 (2) | 0.0243 (18) | 0.0129 (17) | 0.0025 (16) | 0.0037 (16) |
C8 | 0.0292 (18) | 0.025 (2) | 0.0227 (17) | 0.0124 (16) | 0.0015 (15) | 0.0058 (16) |
C9 | 0.0238 (17) | 0.027 (2) | 0.0197 (16) | 0.0115 (16) | 0.0037 (15) | 0.0067 (16) |
C10 | 0.0224 (17) | 0.027 (2) | 0.0187 (16) | 0.0079 (16) | 0.0045 (14) | 0.0080 (16) |
C11 | 0.0229 (17) | 0.028 (2) | 0.0184 (16) | 0.0093 (16) | 0.0011 (14) | 0.0040 (16) |
C12 | 0.0259 (18) | 0.030 (2) | 0.0228 (17) | 0.0081 (17) | −0.0004 (15) | 0.0053 (17) |
C13 | 0.0269 (18) | 0.028 (2) | 0.0246 (18) | 0.0082 (17) | 0.0009 (16) | 0.0011 (17) |
C14 | 0.0229 (17) | 0.027 (2) | 0.0232 (17) | 0.0087 (16) | 0.0032 (15) | 0.0049 (16) |
C15 | 0.0230 (17) | 0.027 (2) | 0.0267 (18) | 0.0103 (16) | 0.0079 (15) | 0.0067 (16) |
C16 | 0.0238 (17) | 0.027 (2) | 0.0240 (17) | 0.0114 (16) | 0.0056 (15) | 0.0069 (16) |
C17 | 0.036 (2) | 0.028 (2) | 0.0275 (18) | 0.0174 (18) | 0.0100 (17) | 0.0095 (17) |
C18 | 0.039 (2) | 0.033 (2) | 0.0260 (18) | 0.0219 (18) | 0.0031 (17) | 0.0106 (17) |
C19 | 0.0275 (18) | 0.032 (2) | 0.0218 (17) | 0.0144 (17) | 0.0082 (15) | 0.0104 (17) |
C20 | 0.0314 (19) | 0.034 (2) | 0.0194 (17) | 0.0153 (18) | 0.0048 (16) | 0.0094 (17) |
C21 | 0.040 (2) | 0.033 (2) | 0.0268 (19) | 0.0199 (19) | −0.0111 (17) | −0.0028 (18) |
C22 | 0.041 (2) | 0.033 (2) | 0.057 (3) | 0.014 (2) | −0.011 (2) | 0.000 (2) |
C23 | 0.059 (3) | 0.036 (3) | 0.107 (5) | 0.007 (3) | −0.044 (3) | 0.014 (3) |
C24 | 0.0757 (18) | 0.0698 (18) | 0.0716 (18) | 0.0327 (11) | −0.0008 (10) | 0.0074 (10) |
C25 | 0.0731 (17) | 0.0694 (17) | 0.0666 (17) | 0.0331 (11) | 0.0027 (10) | 0.0064 (10) |
C26 | 0.090 (4) | 0.051 (3) | 0.025 (2) | 0.052 (3) | −0.003 (2) | −0.004 (2) |
C27 | 0.0288 (18) | 0.0205 (19) | 0.0240 (17) | 0.0096 (16) | −0.0023 (15) | 0.0019 (16) |
C28 | 0.0307 (19) | 0.033 (2) | 0.0250 (18) | 0.0103 (18) | 0.0009 (16) | 0.0083 (17) |
C29 | 0.041 (2) | 0.035 (2) | 0.0257 (19) | 0.0105 (19) | −0.0015 (17) | 0.0107 (18) |
C30 | 0.041 (2) | 0.038 (2) | 0.034 (2) | 0.017 (2) | −0.0102 (19) | 0.0080 (19) |
C31 | 0.032 (2) | 0.042 (2) | 0.038 (2) | 0.0176 (19) | −0.0053 (18) | 0.003 (2) |
C32 | 0.031 (2) | 0.036 (2) | 0.0255 (18) | 0.0137 (18) | −0.0006 (16) | 0.0030 (18) |
C33 | 0.0256 (18) | 0.027 (2) | 0.0278 (18) | 0.0113 (16) | 0.0015 (16) | 0.0066 (17) |
C34 | 0.030 (2) | 0.029 (2) | 0.045 (2) | 0.0075 (18) | 0.0131 (19) | 0.001 (2) |
C35 | 0.039 (2) | 0.033 (2) | 0.050 (3) | 0.011 (2) | 0.011 (2) | −0.006 (2) |
C36 | 0.041 (2) | 0.025 (2) | 0.042 (2) | 0.0120 (19) | −0.002 (2) | 0.0022 (19) |
C37 | 0.038 (2) | 0.029 (2) | 0.041 (2) | 0.0002 (19) | −0.003 (2) | 0.009 (2) |
C38 | 0.032 (2) | 0.035 (2) | 0.034 (2) | 0.0101 (18) | 0.0090 (18) | 0.0103 (19) |
C39 | 0.040 (2) | 0.035 (2) | 0.0206 (17) | 0.0227 (19) | 0.0026 (16) | 0.0054 (17) |
C40 | 0.036 (2) | 0.048 (3) | 0.037 (2) | 0.007 (2) | −0.0026 (19) | 0.020 (2) |
C41 | 0.052 (3) | 0.047 (3) | 0.034 (2) | 0.002 (2) | −0.003 (2) | 0.024 (2) |
C42 | 0.056 (3) | 0.043 (3) | 0.0257 (19) | 0.029 (2) | −0.0085 (19) | 0.0041 (19) |
C43 | 0.053 (3) | 0.129 (5) | 0.047 (3) | 0.061 (3) | 0.012 (2) | 0.034 (3) |
C44 | 0.050 (3) | 0.128 (5) | 0.040 (2) | 0.057 (3) | 0.022 (2) | 0.048 (3) |
C45 | 0.037 (2) | 0.036 (2) | 0.036 (2) | 0.0188 (19) | 0.0135 (18) | 0.0126 (19) |
C46 | 0.038 (2) | 0.038 (2) | 0.038 (2) | 0.015 (2) | 0.0080 (19) | 0.015 (2) |
C47 | 0.037 (2) | 0.041 (2) | 0.036 (2) | 0.019 (2) | 0.0116 (18) | 0.008 (2) |
C48 | 0.030 (2) | 0.036 (2) | 0.0296 (19) | 0.0154 (18) | 0.0070 (17) | 0.0013 (18) |
C49 | 0.0265 (19) | 0.051 (3) | 0.0261 (19) | 0.0109 (19) | −0.0001 (16) | 0.0090 (19) |
C50 | 0.029 (2) | 0.053 (3) | 0.032 (2) | 0.014 (2) | 0.0057 (17) | 0.015 (2) |
C51 | 0.050 (3) | 0.052 (3) | 0.052 (3) | 0.026 (2) | 0.006 (2) | 0.006 (2) |
C52 | 0.095 (4) | 0.051 (3) | 0.079 (4) | 0.040 (3) | 0.010 (3) | 0.006 (3) |
C53 | 0.040 (3) | 0.123 (5) | 0.036 (3) | 0.017 (3) | −0.005 (2) | 0.014 (3) |
C54 | 0.037 (2) | 0.058 (3) | 0.055 (3) | 0.017 (2) | 0.006 (2) | 0.005 (3) |
C55 | 0.054 (3) | 0.111 (5) | 0.057 (3) | 0.019 (3) | 0.027 (3) | 0.013 (4) |
C56 | 0.057 (3) | 0.063 (3) | 0.072 (3) | 0.034 (3) | 0.022 (3) | 0.008 (3) |
C57 | 0.045 (3) | 0.065 (3) | 0.039 (2) | 0.020 (3) | −0.009 (2) | −0.012 (2) |
C58 | 0.028 (2) | 0.040 (2) | 0.031 (2) | 0.0102 (19) | −0.0005 (17) | −0.0047 (19) |
C59 | 0.052 (3) | 0.065 (3) | 0.053 (3) | 0.026 (3) | −0.006 (2) | −0.003 (3) |
C60 | 0.060 (3) | 0.050 (3) | 0.069 (4) | 0.013 (3) | −0.019 (3) | 0.009 (3) |
C61 | 0.064 (4) | 0.104 (5) | 0.052 (3) | −0.018 (4) | −0.008 (3) | 0.032 (4) |
C62 | 0.033 (2) | 0.079 (4) | 0.040 (3) | 0.011 (3) | 0.008 (2) | 0.007 (3) |
C63 | 0.073 (4) | 0.053 (3) | 0.076 (4) | 0.032 (3) | −0.019 (3) | −0.025 (3) |
O1 | 0.138 (16) | 0.107 (14) | 0.069 (10) | 0.077 (13) | 0.025 (11) | 0.023 (10) |
Geometric parameters (Å, º) top
Mn1—N3 | 2.008 (3) | C29—H29 | 0.9500 |
Mn1—N4 | 2.019 (3) | C30—C31 | 1.388 (6) |
Mn1—N1 | 2.023 (3) | C30—H30 | 0.9500 |
Mn1—N2 | 2.027 (3) | C31—C32 | 1.383 (5) |
Mn1—Cl1 | 2.4255 (10) | C31—H31 | 0.9500 |
N1—C4 | 1.376 (5) | C32—H32 | 0.9500 |
N1—C1 | 1.381 (4) | C33—C38 | 1.386 (5) |
N4—C19 | 1.382 (4) | C33—C34 | 1.389 (5) |
N4—C16 | 1.382 (5) | C34—C35 | 1.386 (6) |
N3—C14 | 1.384 (5) | C34—H34 | 0.9500 |
N3—C11 | 1.385 (4) | C35—C36 | 1.375 (6) |
N2—C6 | 1.373 (5) | C35—H35 | 0.9500 |
N2—C9 | 1.378 (4) | C36—C37 | 1.371 (6) |
N5—C48 | 1.480 (5) | C36—H36 | 0.9500 |
N5—C45 | 1.484 (5) | C37—C38 | 1.388 (6) |
N5—C49 | 1.488 (4) | C37—H37 | 0.9500 |
N6—C47 | 1.464 (5) | C38—H38 | 0.9500 |
N6—C50 | 1.465 (5) | C39—C44 | 1.375 (6) |
N6—C46 | 1.471 (5) | C39—C40 | 1.379 (5) |
N7—C52 | 1.421 (7) | C40—C41 | 1.391 (6) |
N7—C53 | 1.484 (7) | C40—H40 | 0.9500 |
N7—C55 | 1.491 (7) | C41—C42 | 1.356 (6) |
N8—C51 | 1.451 (6) | C41—H41 | 0.9500 |
N8—C56 | 1.459 (6) | C42—C43 | 1.361 (7) |
N8—C54 | 1.484 (6) | C42—H42 | 0.9500 |
C1—C20 | 1.396 (5) | C43—C44 | 1.389 (6) |
C1—C2 | 1.430 (5) | C43—H43 | 0.9500 |
C2—C3 | 1.345 (5) | C44—H44 | 0.9500 |
C2—H2 | 0.9500 | C45—C46 | 1.554 (5) |
C3—C4 | 1.444 (5) | C45—H45A | 0.9900 |
C3—H3 | 0.9500 | C45—H45B | 0.9900 |
C4—C5 | 1.392 (5) | C46—H46A | 0.9900 |
C5—C6 | 1.401 (5) | C46—H46B | 0.9900 |
C5—C21 | 1.497 (5) | C47—C48 | 1.547 (5) |
C6—C7 | 1.438 (5) | C47—H47A | 0.9900 |
C7—C8 | 1.347 (5) | C47—H47B | 0.9900 |
C7—H7 | 0.9500 | C48—H48A | 0.9900 |
C8—C9 | 1.438 (5) | C48—H48B | 0.9900 |
C8—H8 | 0.9500 | C49—C50 | 1.552 (5) |
C9—C10 | 1.389 (5) | C49—H49A | 0.9900 |
C10—C11 | 1.393 (5) | C49—H49B | 0.9900 |
C10—C27 | 1.501 (5) | C50—H50A | 0.9900 |
C11—C12 | 1.427 (5) | C50—H50B | 0.9900 |
C12—C13 | 1.354 (5) | C51—C52 | 1.502 (7) |
C12—H12 | 0.9500 | C51—H51A | 0.9900 |
C13—C14 | 1.436 (5) | C51—H51B | 0.9900 |
C13—H13 | 0.9500 | C52—H52A | 0.9900 |
C14—C15 | 1.393 (5) | C52—H52B | 0.9900 |
C15—C16 | 1.394 (5) | C53—C54 | 1.521 (7) |
C15—C33 | 1.496 (5) | C53—H53A | 0.9900 |
C16—C17 | 1.433 (5) | C53—H53B | 0.9900 |
C17—C18 | 1.351 (5) | C54—H54A | 0.9900 |
C17—H17 | 0.9500 | C54—H54B | 0.9900 |
C18—C19 | 1.442 (5) | C55—C56 | 1.546 (8) |
C18—H18 | 0.9500 | C55—H55A | 0.9900 |
C19—C20 | 1.391 (5) | C55—H55B | 0.9900 |
C20—C39 | 1.503 (5) | C56—H56A | 0.9900 |
C21—C26 | 1.385 (6) | C56—H56B | 0.9900 |
C21—C22 | 1.386 (6) | C57—C62 | 1.378 (7) |
C22—C23 | 1.403 (7) | C57—C58 | 1.381 (6) |
C22—H22 | 0.9500 | C57—C63 | 1.475 (7) |
C23—C24 | 1.378 (8) | C58—C59 | 1.341 (7) |
C23—H23 | 0.9500 | C58—H58 | 0.9500 |
C24—C25 | 1.325 (8) | C59—C60 | 1.410 (7) |
C24—H24 | 0.9500 | C59—H59 | 0.9500 |
C25—C26 | 1.404 (7) | C60—C61 | 1.372 (9) |
C25—H25 | 0.9500 | C60—H60 | 0.9500 |
C26—H26 | 0.9500 | C61—C62 | 1.401 (9) |
C27—C32 | 1.387 (5) | C61—H61 | 0.9500 |
C27—C28 | 1.389 (5) | C62—H62 | 0.9500 |
C28—C29 | 1.390 (5) | C63—H63A | 0.9800 |
C28—H28 | 0.9500 | C63—H63B | 0.9800 |
C29—C30 | 1.375 (6) | C63—H63C | 0.9800 |
| | | |
N3—Mn1—N4 | 89.89 (12) | C38—C33—C15 | 121.4 (3) |
N3—Mn1—N1 | 173.48 (11) | C34—C33—C15 | 120.1 (3) |
N4—Mn1—N1 | 89.87 (12) | C35—C34—C33 | 120.6 (4) |
N3—Mn1—N2 | 89.66 (11) | C35—C34—H34 | 119.7 |
N4—Mn1—N2 | 172.80 (11) | C33—C34—H34 | 119.7 |
N1—Mn1—N2 | 89.76 (12) | C36—C35—C34 | 120.4 (4) |
N3—Mn1—Cl1 | 93.35 (8) | C36—C35—H35 | 119.8 |
N4—Mn1—Cl1 | 94.32 (9) | C34—C35—H35 | 119.8 |
N1—Mn1—Cl1 | 93.17 (9) | C37—C36—C35 | 119.6 (4) |
N2—Mn1—Cl1 | 92.88 (9) | C37—C36—H36 | 120.2 |
C4—N1—C1 | 106.3 (3) | C35—C36—H36 | 120.2 |
C4—N1—Mn1 | 126.7 (2) | C36—C37—C38 | 120.5 (4) |
C1—N1—Mn1 | 126.8 (2) | C36—C37—H37 | 119.8 |
C19—N4—C16 | 106.1 (3) | C38—C37—H37 | 119.8 |
C19—N4—Mn1 | 126.7 (2) | C33—C38—C37 | 120.5 (4) |
C16—N4—Mn1 | 127.0 (2) | C33—C38—H38 | 119.7 |
C14—N3—C11 | 105.7 (3) | C37—C38—H38 | 119.7 |
C14—N3—Mn1 | 126.9 (2) | C44—C39—C40 | 118.0 (4) |
C11—N3—Mn1 | 127.4 (2) | C44—C39—C20 | 120.8 (3) |
C6—N2—C9 | 106.4 (3) | C40—C39—C20 | 121.2 (3) |
C6—N2—Mn1 | 126.6 (2) | C39—C40—C41 | 120.6 (4) |
C9—N2—Mn1 | 126.8 (2) | C39—C40—H40 | 119.7 |
C48—N5—C45 | 107.8 (3) | C41—C40—H40 | 119.7 |
C48—N5—C49 | 108.1 (3) | C42—C41—C40 | 120.5 (4) |
C45—N5—C49 | 107.3 (3) | C42—C41—H41 | 119.8 |
C47—N6—C50 | 109.0 (3) | C40—C41—H41 | 119.8 |
C47—N6—C46 | 108.1 (3) | C41—C42—C43 | 119.6 (4) |
C50—N6—C46 | 107.3 (3) | C41—C42—H42 | 120.2 |
C52—N7—C53 | 108.6 (4) | C43—C42—H42 | 120.2 |
C52—N7—C55 | 107.3 (4) | C42—C43—C44 | 120.4 (4) |
C53—N7—C55 | 105.4 (5) | C42—C43—H43 | 119.8 |
C51—N8—C56 | 108.4 (4) | C44—C43—H43 | 119.8 |
C51—N8—C54 | 108.0 (4) | C39—C44—C43 | 120.8 (4) |
C56—N8—C54 | 107.1 (4) | C39—C44—H44 | 119.6 |
N1—C1—C20 | 125.8 (3) | C43—C44—H44 | 119.6 |
N1—C1—C2 | 109.5 (3) | N5—C45—C46 | 110.7 (3) |
C20—C1—C2 | 124.7 (3) | N5—C45—H45A | 109.5 |
C3—C2—C1 | 107.7 (3) | C46—C45—H45A | 109.5 |
C3—C2—H2 | 126.1 | N5—C45—H45B | 109.5 |
C1—C2—H2 | 126.1 | C46—C45—H45B | 109.5 |
C2—C3—C4 | 107.2 (3) | H45A—C45—H45B | 108.1 |
C2—C3—H3 | 126.4 | N6—C46—C45 | 111.0 (3) |
C4—C3—H3 | 126.4 | N6—C46—H46A | 109.4 |
N1—C4—C5 | 126.2 (3) | C45—C46—H46A | 109.4 |
N1—C4—C3 | 109.3 (3) | N6—C46—H46B | 109.4 |
C5—C4—C3 | 124.5 (3) | C45—C46—H46B | 109.4 |
C4—C5—C6 | 124.1 (3) | H46A—C46—H46B | 108.0 |
C4—C5—C21 | 118.3 (3) | N6—C47—C48 | 111.5 (3) |
C6—C5—C21 | 117.5 (3) | N6—C47—H47A | 109.3 |
N2—C6—C5 | 126.0 (3) | C48—C47—H47A | 109.3 |
N2—C6—C7 | 109.9 (3) | N6—C47—H47B | 109.3 |
C5—C6—C7 | 124.1 (3) | C48—C47—H47B | 109.3 |
C8—C7—C6 | 106.8 (3) | H47A—C47—H47B | 108.0 |
C8—C7—H7 | 126.6 | N5—C48—C47 | 110.6 (3) |
C6—C7—H7 | 126.6 | N5—C48—H48A | 109.5 |
C7—C8—C9 | 107.8 (3) | C47—C48—H48A | 109.5 |
C7—C8—H8 | 126.1 | N5—C48—H48B | 109.5 |
C9—C8—H8 | 126.1 | C47—C48—H48B | 109.5 |
N2—C9—C10 | 126.0 (3) | H48A—C48—H48B | 108.1 |
N2—C9—C8 | 109.1 (3) | N5—C49—C50 | 110.7 (3) |
C10—C9—C8 | 124.8 (3) | N5—C49—H49A | 109.5 |
C9—C10—C11 | 124.4 (3) | C50—C49—H49A | 109.5 |
C9—C10—C27 | 118.1 (3) | N5—C49—H49B | 109.5 |
C11—C10—C27 | 117.4 (3) | C50—C49—H49B | 109.5 |
N3—C11—C10 | 125.5 (3) | H49A—C49—H49B | 108.1 |
N3—C11—C12 | 109.8 (3) | N6—C50—C49 | 111.1 (3) |
C10—C11—C12 | 124.7 (3) | N6—C50—H50A | 109.4 |
C13—C12—C11 | 107.7 (3) | C49—C50—H50A | 109.4 |
C13—C12—H12 | 126.2 | N6—C50—H50B | 109.4 |
C11—C12—H12 | 126.2 | C49—C50—H50B | 109.4 |
C12—C13—C14 | 107.0 (3) | H50A—C50—H50B | 108.0 |
C12—C13—H13 | 126.5 | N8—C51—C52 | 111.0 (4) |
C14—C13—H13 | 126.5 | N8—C51—H51A | 109.4 |
N3—C14—C15 | 126.2 (3) | C52—C51—H51A | 109.4 |
N3—C14—C13 | 109.9 (3) | N8—C51—H51B | 109.4 |
C15—C14—C13 | 123.9 (3) | C52—C51—H51B | 109.4 |
C14—C15—C16 | 124.0 (3) | H51A—C51—H51B | 108.0 |
C14—C15—C33 | 117.3 (3) | N7—C52—C51 | 113.6 (4) |
C16—C15—C33 | 118.8 (3) | N7—C52—H52A | 108.8 |
N4—C16—C15 | 125.8 (3) | C51—C52—H52A | 108.8 |
N4—C16—C17 | 109.7 (3) | N7—C52—H52B | 108.8 |
C15—C16—C17 | 124.6 (3) | C51—C52—H52B | 108.8 |
C18—C17—C16 | 107.5 (3) | H52A—C52—H52B | 107.7 |
C18—C17—H17 | 126.2 | N7—C53—C54 | 111.5 (4) |
C16—C17—H17 | 126.2 | N7—C53—H53A | 109.3 |
C17—C18—C19 | 107.2 (3) | C54—C53—H53A | 109.3 |
C17—C18—H18 | 126.4 | N7—C53—H53B | 109.3 |
C19—C18—H18 | 126.4 | C54—C53—H53B | 109.3 |
N4—C19—C20 | 126.1 (3) | H53A—C53—H53B | 108.0 |
N4—C19—C18 | 109.5 (3) | N8—C54—C53 | 110.8 (4) |
C20—C19—C18 | 124.5 (3) | N8—C54—H54A | 109.5 |
C19—C20—C1 | 124.3 (3) | C53—C54—H54A | 109.5 |
C19—C20—C39 | 118.4 (3) | N8—C54—H54B | 109.5 |
C1—C20—C39 | 117.3 (3) | C53—C54—H54B | 109.5 |
C26—C21—C22 | 119.2 (4) | H54A—C54—H54B | 108.1 |
C26—C21—C5 | 120.6 (4) | N7—C55—C56 | 110.8 (4) |
C22—C21—C5 | 120.2 (4) | N7—C55—H55A | 109.5 |
C21—C22—C23 | 120.7 (5) | C56—C55—H55A | 109.5 |
C21—C22—H22 | 119.7 | N7—C55—H55B | 109.5 |
C23—C22—H22 | 119.7 | C56—C55—H55B | 109.5 |
C24—C23—C22 | 118.6 (6) | H55A—C55—H55B | 108.1 |
C24—C23—H23 | 120.7 | N8—C56—C55 | 110.7 (4) |
C22—C23—H23 | 120.7 | N8—C56—H56A | 109.5 |
C25—C24—C23 | 120.9 (6) | C55—C56—H56A | 109.5 |
C25—C24—H24 | 119.6 | N8—C56—H56B | 109.5 |
C23—C24—H24 | 119.6 | C55—C56—H56B | 109.5 |
C24—C25—C26 | 122.0 (6) | H56A—C56—H56B | 108.1 |
C24—C25—H25 | 119.0 | C62—C57—C58 | 117.5 (5) |
C26—C25—H25 | 119.0 | C62—C57—C63 | 120.6 (5) |
C21—C26—C25 | 118.6 (5) | C58—C57—C63 | 121.9 (5) |
C21—C26—H26 | 120.7 | C59—C58—C57 | 123.1 (5) |
C25—C26—H26 | 120.7 | C59—C58—H58 | 118.4 |
C32—C27—C28 | 118.8 (3) | C57—C58—H58 | 118.4 |
C32—C27—C10 | 119.6 (3) | C58—C59—C60 | 120.6 (5) |
C28—C27—C10 | 121.6 (3) | C58—C59—H59 | 119.7 |
C27—C28—C29 | 120.3 (4) | C60—C59—H59 | 119.7 |
C27—C28—H28 | 119.9 | C61—C60—C59 | 116.9 (5) |
C29—C28—H28 | 119.9 | C61—C60—H60 | 121.5 |
C30—C29—C28 | 120.4 (4) | C59—C60—H60 | 121.5 |
C30—C29—H29 | 119.8 | C60—C61—C62 | 121.9 (5) |
C28—C29—H29 | 119.8 | C60—C61—H61 | 119.1 |
C29—C30—C31 | 119.8 (4) | C62—C61—H61 | 119.1 |
C29—C30—H30 | 120.1 | C57—C62—C61 | 119.9 (5) |
C31—C30—H30 | 120.1 | C57—C62—H62 | 120.1 |
C32—C31—C30 | 119.8 (4) | C61—C62—H62 | 120.1 |
C32—C31—H31 | 120.1 | C57—C63—H63A | 109.5 |
C30—C31—H31 | 120.1 | C57—C63—H63B | 109.5 |
C31—C32—C27 | 120.9 (4) | H63A—C63—H63B | 109.5 |
C31—C32—H32 | 119.5 | C57—C63—H63C | 109.5 |
C27—C32—H32 | 119.5 | H63A—C63—H63C | 109.5 |
C38—C33—C34 | 118.4 (4) | H63B—C63—H63C | 109.5 |
Comparison of bond lengths and angles for structures (I)–(IV) and
associated literature top | (I) | (II) | (III) | (IV) | MnClTPP (Boucher, 1972) | MnClTPP-Py (Kirner & Scheidt, 1975) |
Porphyrin angles (°) | | | | | | |
N1—Mn1—N3 | 179.75 (9) | | 173.58 (5) | 173.4 (1) | 166.9 (3) | 172.8 (2) |
N2—Mn1—N4 | 178.75 (8) | | 173.32 (5) | 172.8 (1) | 161.7 (3) | 173.6 (2) |
N1—Mn1—N1A | | 180.00 (15) | | | | |
N2—Mn1—N2A | | 180.00 (11) | | | | |
| | | | | | |
Ligand–Mn1–ligand angles (°) | | | | | | |
N5—Mn1—N7 | 178.65 (7) | | | | | |
N3—Mn1—N3A | | 180.00 (11) | | | | |
N5—Mn1—Cl1 | | | 175.43 (3) | 179.41 (6) | | 175.5 (1) |
| | | | | | |
Ruffle angles (°) | | | | | | |
C1→C5—N1—C15→C20—N4 | | | | | | |
C5→C9—N2—C10→C15—N3 | 5.64 (5) | | 19.66 (3) | 1.63 (9) | | |
| | | | | | |
C5→C9—N2—C10—C11A→C5A—N1A | | | | | | |
C5→C1—N1—C10—C10A→C5A—N2A | | 0.00 (4) | | | | |
| | | | | | |
C20—C1→C4—N1—C5→C10—N2 | | | | | | |
C10→C14—N3—C15→C20—N4 | 6.79 (5) | | 21.66 (4) | 0.42 (7) | | |
| | | | | | |
C10A—C1→C4—N1—C5→C10-N2 | | | | | | |
C10—C1A→C4A—N1A—C5A→C10A-N2A | | 0.00 (0) | | | | |
| | | | | | |
`Swayback' angles (°) | | | | | | |
C27—C10—Mn1 | | | | | | |
C39—C20—Mn1 | 1.64 (9) | | 6.34 (7) | 3.0 (2) | | |
| | | | | | |
C17—C10—Mn1 | | | | | | |
C17A—C10A—Mn1 | | 0.00 (6) | | | | |
| | | | | | |
C11—C5—Mn1 | | | | | | |
C11A—C5A—Mn1 | | 0.00 (6) | | | | |
| | | | | | |
C21—C5—Mn1 | | | | | | |
C33—C15—Mn1 | 6.27 (9) | | 3.07 (8) | 1.78 (4) | | |
| | | | | | |
Phenyl angles to porphyrin ring (°) | | | | | | |
C21→C26 | 66.87 (7) | | 60.40 (4) | 72.61 (8) | 54.2 | 59.8 |
C27→C32 | 88.75 (7) | | 67.95 (3) | 80.6 (1) | 123.5 | 79.1 |
C33→C38 | 77.94 (7) | | 61.72 (4) | 79.51 (8) | 49.7 | 69.1 |
C39→C44 | 64.48 (8) | | 74.79 (3) | 80.29 (11) | 77.4 | 72 |
C11→C16 | | 70.13 (7) | | | | |
C17→C22 | | 64.49 (6) | | | | |
| | | | | | |
Mn1-to-ligand distances (Å) | | | | | | |
Mn1—N1 | 2.018 (2) | 2.0199 (17) | 2.0124 (12) | 2.022 (3) | 1.999 (7) | 2.022 (4) |
Mn1—N2 | 2.025 (2) | 2.0164 (17) | 2.0060 (12) | 2.026 (3) | 2.0212 (7) | 2.006 (4) |
Mn1—N3 | 2.025 (2) | 2.3704 (17) | 2.0083 (12) | 2.007 (2) | 1.992 (7) | 2.010 (3) |
Mn1—N4 | 2.015 (2) | | 2.0025 (12) | 2.019 (3) | 2.022 (7) | 2.000 (4) |
Mn1—N5 | 2.285 (2) | | 2.4203 (12) | 2.612 (3) | | 2.444 (4) |
Mn1—N7 | 2.284 (2) | | | | | |
Mn1—Cl1 | | | 2.4693 (4) | 2.4253 (9) | 2.363 (3) | 2.467 (1) |
| | | | | | |
Mn atom displacement from the N1/N2/N3/N4 plane (Å) | -0.0075 (8) | 0.0000 (0) | -0.0913 (5) | -0.097 (1) | 0.27 | 0.145 |
Plane N1/N2/N3/N4/Mn1 versus Cl1 angle (°) | | | 93.77 (6) | 93.44 (14) | 4.7 (175.3) | |
Plane N1/N2/N3/N4/Mn1 versus N5 angle (°) | | | 86.73 (8) | 86.56 (18) | | |