Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109042127/sf3119sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109042127/sf3119I_180Ksup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109042127/sf3119I_295Ksup3.hkl |
CCDC references: 760072; 760073
N,N'-Bis-2-picolylethylenediamine (bispicene) was prepared according to literature procedures (Glerup et al., 1994; Goodwin & Lions, 1960). Manganese(II) perchlorate hexahydrate (747 mg, 2 mmol) in water (1 ml) was then added to bispicene (501 mg, 2 mmol) in water (2 ml). The initially pale-yellow solution turned green, and black crystals of (I) were deposited overnight.
For both structures, H atoms bound to C or N atoms were placed in calculated positions and allowed to ride during subsequent refinement, with Uiso(H) = 1.2Ueq(C,N). At 180 K, C—H = 0.95 Å for Csp2 or 0.99 Å for Csp3 and N—H = 0.93 Å. At 295 K, C—H = 0.93 Å for Csp2 or 0.97 Å for Csp3 and N—H = 0.91 Å. In the LT structure, the H atoms of the water molecules were placed so as to form a reasonable hydrogen-bond network, with O—H = 0.85 Å, and then allowed to ride on their parent O atoms, with Uiso(H) = 1.5Ueq(O). In the HT structure, the H atoms of the water molecules were placed by comparison with the LT structure, and then refined in the same way. One water molecule site is omitted from the HT structure (corresponding to O6W in the LT structure), so that the atom count sums to four water molecules per unit cell less than the stated formula. All perchlorate anions were refined with their Cl—O distances restrained to a common refined value and O···O distances restrained to be 1.633 times that value. At 180 K, perchlorate anion Cl2 is modelled as disordered over two orientations with equal site occupancy, with atom O2A common to both orientations. The O atoms of this anion were refined with anisotropic displacement parameters restrained to resemble isotropic behaviour. For some of these atoms (particularly O2C), the anisotropic displacement parameters are nonetheless elongated, but this was considered to be acceptable in the context of the rotational disorder. At 295 K, perchlorate anion Cl2 was modelled as rotationally disordered over two orientations. In this case, all O atoms were given a common refined isotropic displacement parameter. At 180 K, the highest peak in the difference density is located in the vicinity of the solvent water molecules, ca 1.65 Å from atom H4. At 295 K, the highest residual peak is associated with the rotationally disordered perchlorate anion Cl2.
For both compounds, data collection: APEX2 (Bruker Nonius, 2004); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Mn2O2(C14H18N4)2](ClO4)3·6H2O | F(000) = 2132 |
Mr = 1032.97 | Dx = 1.631 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9164 reflections |
a = 15.1204 (9) Å | θ = 2.2–26.1° |
b = 12.2337 (7) Å | µ = 0.88 mm−1 |
c = 23.6514 (16) Å | T = 180 K |
β = 105.912 (2)° | Plate, brown |
V = 4207.4 (5) Å3 | 0.25 × 0.20 × 0.05 mm |
Z = 4 |
Bruker Nonius X8 APEXII CCD area-detector diffractometer | 8600 independent reflections |
Radiation source: fine-focus sealed tube | 6203 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
thin–slice ω and ϕ scans | θmax = 26.4°, θmin = 3.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −18→17 |
Tmin = 0.874, Tmax = 0.957 | k = −15→14 |
82186 measured reflections | l = −29→28 |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.158 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0826P)2 + 4.7043P] where P = (Fo2 + 2Fc2)/3 |
8600 reflections | (Δ/σ)max < 0.001 |
578 parameters | Δρmax = 1.19 e Å−3 |
57 restraints | Δρmin = −0.83 e Å−3 |
[Mn2O2(C14H18N4)2](ClO4)3·6H2O | V = 4207.4 (5) Å3 |
Mr = 1032.97 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 15.1204 (9) Å | µ = 0.88 mm−1 |
b = 12.2337 (7) Å | T = 180 K |
c = 23.6514 (16) Å | 0.25 × 0.20 × 0.05 mm |
β = 105.912 (2)° |
Bruker Nonius X8 APEXII CCD area-detector diffractometer | 8600 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 6203 reflections with I > 2σ(I) |
Tmin = 0.874, Tmax = 0.957 | Rint = 0.036 |
82186 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 57 restraints |
wR(F2) = 0.158 | H-atom parameters constrained |
S = 1.09 | Δρmax = 1.19 e Å−3 |
8600 reflections | Δρmin = −0.83 e Å−3 |
578 parameters |
Experimental. One perchlorate anion modelled as disordered. ADPs are anisotropic, but with ISOR constraints applied. Atom O2A is common to both orientations. H atoms on water molecules placed so as to form a reasonable H-bond network and allowed to ride during subsequent refinement. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mn1 | 0.49969 (3) | 0.41996 (4) | 0.253395 (19) | 0.01791 (14) | |
Mn2 | 0.50311 (3) | 0.20276 (4) | 0.254490 (19) | 0.01730 (14) | |
O1 | 0.41960 (14) | 0.30623 (16) | 0.25654 (9) | 0.0209 (5) | |
O2 | 0.58198 (14) | 0.30965 (16) | 0.25184 (9) | 0.0198 (5) | |
N1 | 0.54010 (18) | 0.4430 (2) | 0.35218 (12) | 0.0250 (6) | |
N2 | 0.59674 (17) | 0.5454 (2) | 0.27016 (12) | 0.0232 (6) | |
H2B | 0.6236 | 0.5501 | 0.2392 | 0.028* | |
N3 | 0.40536 (18) | 0.5509 (2) | 0.23345 (12) | 0.0251 (6) | |
H3B | 0.3771 | 0.5591 | 0.2635 | 0.030* | |
N4 | 0.46285 (17) | 0.4401 (2) | 0.15499 (12) | 0.0225 (6) | |
N5 | 0.55890 (18) | 0.1774 (2) | 0.34143 (12) | 0.0233 (6) | |
N6 | 0.42180 (19) | 0.0734 (2) | 0.26675 (13) | 0.0263 (6) | |
H6C | 0.3622 | 0.0859 | 0.2435 | 0.032* | |
N7 | 0.59111 (18) | 0.0811 (2) | 0.24230 (12) | 0.0231 (6) | |
H7C | 0.6492 | 0.0956 | 0.2671 | 0.028* | |
N8 | 0.45115 (18) | 0.1777 (2) | 0.16735 (11) | 0.0222 (6) | |
C1 | 0.4970 (2) | 0.4069 (3) | 0.39170 (16) | 0.0316 (8) | |
H1A | 0.4375 | 0.3757 | 0.3777 | 0.038* | |
C2 | 0.5358 (3) | 0.4135 (3) | 0.45097 (17) | 0.0406 (9) | |
H2A | 0.5039 | 0.3872 | 0.4777 | 0.049* | |
C3 | 0.6229 (3) | 0.4594 (3) | 0.47146 (17) | 0.0435 (10) | |
H3A | 0.6515 | 0.4650 | 0.5125 | 0.052* | |
C4 | 0.6669 (3) | 0.4965 (3) | 0.43170 (16) | 0.0368 (9) | |
H4A | 0.7262 | 0.5287 | 0.4448 | 0.044* | |
C5 | 0.6241 (2) | 0.4867 (3) | 0.37223 (15) | 0.0270 (7) | |
C6 | 0.6690 (2) | 0.5209 (3) | 0.32554 (14) | 0.0268 (7) | |
H6A | 0.7074 | 0.5866 | 0.3387 | 0.032* | |
H6B | 0.7092 | 0.4615 | 0.3186 | 0.032* | |
C7 | 0.5489 (2) | 0.6501 (3) | 0.27481 (16) | 0.0295 (8) | |
H7A | 0.5870 | 0.7126 | 0.2689 | 0.035* | |
H7B | 0.5392 | 0.6566 | 0.3144 | 0.035* | |
C8 | 0.4578 (2) | 0.6517 (3) | 0.22874 (16) | 0.0307 (8) | |
H8A | 0.4222 | 0.7169 | 0.2343 | 0.037* | |
H8B | 0.4679 | 0.6559 | 0.1892 | 0.037* | |
C9 | 0.3350 (2) | 0.5284 (3) | 0.17747 (15) | 0.0295 (8) | |
H9A | 0.2995 | 0.5957 | 0.1633 | 0.035* | |
H9B | 0.2918 | 0.4719 | 0.1838 | 0.035* | |
C10 | 0.3813 (2) | 0.4891 (3) | 0.13232 (15) | 0.0259 (7) | |
C11 | 0.3446 (2) | 0.5017 (3) | 0.07254 (16) | 0.0362 (9) | |
H11A | 0.2877 | 0.5385 | 0.0575 | 0.043* | |
C12 | 0.3914 (3) | 0.4603 (3) | 0.03498 (17) | 0.0400 (9) | |
H12A | 0.3664 | 0.4669 | −0.0064 | 0.048* | |
C13 | 0.4754 (2) | 0.4089 (3) | 0.05795 (16) | 0.0343 (8) | |
H13A | 0.5092 | 0.3801 | 0.0328 | 0.041* | |
C14 | 0.5086 (2) | 0.4006 (3) | 0.11826 (15) | 0.0270 (7) | |
H14A | 0.5660 | 0.3655 | 0.1344 | 0.032* | |
C15 | 0.6430 (2) | 0.2127 (3) | 0.37120 (15) | 0.0278 (7) | |
H15A | 0.6761 | 0.2591 | 0.3521 | 0.033* | |
C16 | 0.6820 (3) | 0.1832 (3) | 0.42869 (16) | 0.0387 (9) | |
H16A | 0.7412 | 0.2092 | 0.4494 | 0.046* | |
C17 | 0.6330 (3) | 0.1146 (4) | 0.45585 (18) | 0.0497 (11) | |
H17A | 0.6585 | 0.0933 | 0.4956 | 0.060* | |
C18 | 0.5471 (3) | 0.0772 (4) | 0.42502 (17) | 0.0458 (10) | |
H18A | 0.5131 | 0.0302 | 0.4432 | 0.055* | |
C19 | 0.5117 (2) | 0.1093 (3) | 0.36742 (15) | 0.0296 (8) | |
C20 | 0.4199 (2) | 0.0733 (3) | 0.32918 (15) | 0.0316 (8) | |
H20A | 0.4058 | −0.0011 | 0.3407 | 0.038* | |
H20B | 0.3714 | 0.1235 | 0.3343 | 0.038* | |
C21 | 0.4558 (2) | −0.0291 (3) | 0.24596 (16) | 0.0307 (8) | |
H21A | 0.4288 | −0.0368 | 0.2030 | 0.037* | |
H21B | 0.4364 | −0.0928 | 0.2655 | 0.037* | |
C22 | 0.5598 (2) | −0.0264 (3) | 0.25991 (16) | 0.0308 (8) | |
H22A | 0.5871 | −0.0381 | 0.3026 | 0.037* | |
H22B | 0.5811 | −0.0861 | 0.2386 | 0.037* | |
C23 | 0.5968 (2) | 0.0896 (3) | 0.18094 (15) | 0.0280 (7) | |
H23A | 0.6170 | 0.0188 | 0.1684 | 0.034* | |
H23B | 0.6426 | 0.1459 | 0.1784 | 0.034* | |
C24 | 0.5046 (2) | 0.1197 (3) | 0.14122 (15) | 0.0259 (7) | |
C25 | 0.4753 (3) | 0.0936 (3) | 0.08242 (16) | 0.0396 (9) | |
H25A | 0.5141 | 0.0540 | 0.0642 | 0.048* | |
C26 | 0.3884 (3) | 0.1259 (3) | 0.05031 (17) | 0.0440 (10) | |
H26A | 0.3667 | 0.1083 | 0.0097 | 0.053* | |
C27 | 0.3337 (3) | 0.1839 (3) | 0.07762 (17) | 0.0376 (9) | |
H27A | 0.2737 | 0.2061 | 0.0561 | 0.045* | |
C28 | 0.3665 (2) | 0.2093 (3) | 0.13607 (15) | 0.0276 (7) | |
H28A | 0.3290 | 0.2499 | 0.1548 | 0.033* | |
Cl1 | 0.90154 (8) | 0.29185 (9) | 0.37978 (5) | 0.0535 (3) | |
O1A | 0.9867 (2) | 0.3260 (3) | 0.37174 (16) | 0.0674 (9) | |
O1B | 0.9055 (3) | 0.1879 (3) | 0.4052 (2) | 0.1034 (16) | |
O1C | 0.8615 (3) | 0.3712 (3) | 0.40745 (17) | 0.0911 (13) | |
O1D | 0.8382 (3) | 0.2842 (3) | 0.32045 (15) | 0.0832 (12) | |
Cl2 | 0.09877 (7) | 0.27260 (9) | 0.11002 (5) | 0.0501 (3) | |
O2A | 0.1156 (4) | 0.1625 (3) | 0.1005 (2) | 0.131 (2) | |
O2B | 0.0229 (5) | 0.3020 (6) | 0.0591 (4) | 0.103 (3) | 0.50 |
O2C | 0.0719 (8) | 0.2812 (8) | 0.1600 (4) | 0.158 (7) | 0.50 |
O2D | 0.1720 (4) | 0.3434 (4) | 0.1079 (3) | 0.0446 (14) | 0.50 |
O2E | 0.1787 (5) | 0.3113 (7) | 0.1557 (5) | 0.116 (3) | 0.50 |
O2F | 0.0236 (4) | 0.3027 (8) | 0.1308 (3) | 0.074 (3) | 0.50 |
O2G | 0.0951 (9) | 0.3303 (9) | 0.0592 (4) | 0.166 (5) | 0.50 |
Cl3 | 0.74394 (6) | 0.30989 (8) | 0.10183 (4) | 0.0397 (2) | |
O3A | 0.7493 (2) | 0.3076 (3) | 0.16349 (13) | 0.0599 (8) | |
O3B | 0.6680 (2) | 0.2426 (4) | 0.07414 (17) | 0.0893 (13) | |
O3C | 0.8242 (2) | 0.2642 (3) | 0.09321 (17) | 0.0866 (13) | |
O3D | 0.7292 (3) | 0.4181 (3) | 0.08285 (19) | 0.1063 (16) | |
O1W | 0.71849 (17) | 0.5493 (2) | 0.19164 (12) | 0.0442 (7) | |
H1 | 0.6930 | 0.6004 | 0.1685 | 0.066* | |
H2 | 0.7201 | 0.4951 | 0.1695 | 0.066* | |
O2W | 0.26715 (18) | 0.5511 (3) | 0.30134 (13) | 0.0543 (8) | |
H3 | 0.2877 | 0.5893 | 0.3322 | 0.081* | |
H4 | 0.2496 | 0.4915 | 0.3133 | 0.081* | |
O3W | 0.2578 (2) | 0.3181 (4) | 0.2926 (2) | 0.1074 (17) | |
H5 | 0.3058 | 0.3034 | 0.2819 | 0.161* | |
H6 | 0.2712 | 0.3007 | 0.3287 | 0.161* | |
O4W | 0.1638 (3) | 0.3465 (4) | 0.45987 (17) | 0.0958 (14) | |
H7 | 0.1290 | 0.3098 | 0.4320 | 0.144* | |
H8 | 0.1517 | 0.3235 | 0.4908 | 0.144* | |
O5W | 0.3862 (5) | 0.1516 (5) | 0.4923 (3) | 0.169 (3) | |
H9 | 0.3666 | 0.1767 | 0.5202 | 0.253* | |
H10 | 0.4435 | 0.1649 | 0.5023 | 0.253* | |
O6W | 0.2918 (5) | 0.2699 (8) | 0.4087 (3) | 0.212 (4) | |
H11 | 0.3319 | 0.2335 | 0.4339 | 0.319* | |
H12 | 0.2533 | 0.2943 | 0.4258 | 0.319* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0180 (2) | 0.0148 (2) | 0.0218 (3) | −0.00078 (17) | 0.00694 (19) | −0.00056 (18) |
Mn2 | 0.0186 (3) | 0.0150 (2) | 0.0188 (3) | −0.00046 (17) | 0.00613 (19) | −0.00054 (18) |
O1 | 0.0186 (10) | 0.0197 (11) | 0.0261 (12) | −0.0010 (8) | 0.0090 (9) | −0.0022 (9) |
O2 | 0.0194 (10) | 0.0187 (11) | 0.0220 (11) | 0.0002 (8) | 0.0069 (9) | 0.0012 (9) |
N1 | 0.0271 (14) | 0.0214 (13) | 0.0278 (15) | 0.0002 (11) | 0.0097 (12) | −0.0040 (11) |
N2 | 0.0239 (13) | 0.0212 (13) | 0.0265 (15) | −0.0030 (11) | 0.0100 (11) | −0.0023 (11) |
N3 | 0.0254 (13) | 0.0207 (13) | 0.0325 (16) | 0.0017 (11) | 0.0135 (12) | −0.0017 (11) |
N4 | 0.0236 (13) | 0.0200 (13) | 0.0246 (15) | −0.0013 (11) | 0.0076 (11) | 0.0030 (11) |
N5 | 0.0281 (14) | 0.0196 (13) | 0.0228 (14) | 0.0026 (11) | 0.0080 (11) | 0.0000 (11) |
N6 | 0.0277 (14) | 0.0206 (14) | 0.0328 (16) | −0.0037 (11) | 0.0117 (12) | 0.0004 (12) |
N7 | 0.0245 (13) | 0.0200 (13) | 0.0245 (15) | 0.0027 (11) | 0.0061 (11) | −0.0008 (11) |
N8 | 0.0239 (13) | 0.0208 (13) | 0.0226 (14) | −0.0020 (11) | 0.0074 (11) | 0.0006 (11) |
C1 | 0.0352 (19) | 0.0273 (18) | 0.038 (2) | 0.0032 (15) | 0.0201 (16) | −0.0016 (15) |
C2 | 0.058 (3) | 0.037 (2) | 0.033 (2) | 0.0112 (18) | 0.0229 (19) | 0.0041 (17) |
C3 | 0.060 (3) | 0.045 (2) | 0.023 (2) | 0.009 (2) | 0.0074 (18) | −0.0023 (17) |
C4 | 0.038 (2) | 0.036 (2) | 0.031 (2) | 0.0005 (16) | 0.0005 (16) | −0.0055 (16) |
C5 | 0.0278 (17) | 0.0204 (16) | 0.0314 (19) | 0.0014 (13) | 0.0059 (14) | −0.0020 (14) |
C6 | 0.0230 (16) | 0.0257 (17) | 0.0312 (19) | −0.0046 (13) | 0.0066 (14) | −0.0048 (14) |
C7 | 0.0329 (18) | 0.0171 (16) | 0.039 (2) | −0.0010 (14) | 0.0104 (16) | −0.0020 (14) |
C8 | 0.0338 (19) | 0.0186 (16) | 0.040 (2) | 0.0006 (14) | 0.0110 (16) | 0.0003 (15) |
C9 | 0.0216 (16) | 0.0277 (18) | 0.038 (2) | 0.0053 (13) | 0.0061 (14) | 0.0036 (15) |
C10 | 0.0230 (16) | 0.0198 (16) | 0.0326 (19) | −0.0013 (13) | 0.0035 (14) | 0.0043 (14) |
C11 | 0.0334 (19) | 0.034 (2) | 0.036 (2) | 0.0007 (15) | 0.0009 (16) | 0.0080 (16) |
C12 | 0.044 (2) | 0.044 (2) | 0.027 (2) | −0.0046 (18) | 0.0010 (17) | 0.0074 (17) |
C13 | 0.040 (2) | 0.038 (2) | 0.028 (2) | −0.0083 (16) | 0.0128 (16) | 0.0002 (16) |
C14 | 0.0262 (16) | 0.0261 (17) | 0.0294 (19) | −0.0038 (13) | 0.0091 (14) | 0.0021 (14) |
C15 | 0.0301 (18) | 0.0238 (17) | 0.0281 (19) | 0.0029 (13) | 0.0058 (14) | −0.0036 (14) |
C16 | 0.036 (2) | 0.048 (2) | 0.028 (2) | 0.0064 (17) | 0.0027 (16) | −0.0023 (17) |
C17 | 0.057 (3) | 0.064 (3) | 0.024 (2) | 0.012 (2) | 0.0039 (19) | 0.0064 (19) |
C18 | 0.058 (3) | 0.053 (3) | 0.031 (2) | 0.000 (2) | 0.021 (2) | 0.0117 (19) |
C19 | 0.040 (2) | 0.0243 (17) | 0.0282 (19) | 0.0027 (15) | 0.0160 (16) | 0.0011 (14) |
C20 | 0.0365 (19) | 0.0317 (19) | 0.031 (2) | −0.0055 (15) | 0.0172 (16) | 0.0033 (15) |
C21 | 0.041 (2) | 0.0170 (16) | 0.036 (2) | −0.0044 (14) | 0.0133 (16) | −0.0016 (14) |
C22 | 0.042 (2) | 0.0181 (16) | 0.034 (2) | 0.0049 (14) | 0.0134 (16) | 0.0008 (14) |
C23 | 0.0276 (17) | 0.0285 (18) | 0.0309 (19) | 0.0036 (14) | 0.0132 (15) | −0.0031 (14) |
C24 | 0.0299 (17) | 0.0225 (16) | 0.0272 (18) | −0.0026 (13) | 0.0110 (14) | 0.0028 (14) |
C25 | 0.053 (2) | 0.042 (2) | 0.026 (2) | −0.0033 (18) | 0.0141 (18) | −0.0062 (17) |
C26 | 0.054 (2) | 0.050 (2) | 0.023 (2) | −0.008 (2) | 0.0016 (18) | −0.0019 (18) |
C27 | 0.037 (2) | 0.039 (2) | 0.032 (2) | −0.0081 (16) | 0.0001 (16) | 0.0062 (17) |
C28 | 0.0249 (17) | 0.0253 (17) | 0.0312 (19) | −0.0046 (13) | 0.0055 (14) | 0.0043 (14) |
Cl1 | 0.0676 (7) | 0.0434 (6) | 0.0613 (7) | 0.0021 (5) | 0.0376 (6) | 0.0074 (5) |
O1A | 0.054 (2) | 0.078 (2) | 0.073 (2) | 0.0048 (17) | 0.0227 (18) | 0.0100 (19) |
O1B | 0.121 (4) | 0.077 (3) | 0.115 (4) | 0.019 (2) | 0.038 (3) | 0.058 (3) |
O1C | 0.125 (3) | 0.087 (3) | 0.085 (3) | 0.031 (3) | 0.068 (3) | 0.013 (2) |
O1D | 0.087 (3) | 0.094 (3) | 0.063 (2) | −0.025 (2) | 0.011 (2) | 0.007 (2) |
Cl2 | 0.0516 (6) | 0.0412 (6) | 0.0636 (7) | −0.0021 (5) | 0.0258 (5) | −0.0031 (5) |
O2A | 0.159 (5) | 0.052 (2) | 0.135 (4) | 0.009 (3) | −0.040 (3) | −0.029 (3) |
O2B | 0.054 (5) | 0.107 (7) | 0.132 (9) | 0.004 (4) | 0.002 (5) | 0.035 (6) |
O2C | 0.275 (16) | 0.166 (11) | 0.090 (8) | −0.176 (12) | 0.145 (10) | −0.107 (8) |
O2D | 0.045 (3) | 0.048 (3) | 0.045 (3) | −0.009 (3) | 0.019 (3) | −0.005 (3) |
O2E | 0.067 (5) | 0.097 (6) | 0.161 (8) | 0.013 (4) | −0.008 (5) | −0.061 (6) |
O2F | 0.063 (4) | 0.107 (6) | 0.056 (5) | −0.033 (4) | 0.024 (4) | −0.030 (4) |
O2G | 0.193 (9) | 0.204 (9) | 0.133 (8) | 0.022 (8) | 0.097 (7) | 0.068 (7) |
Cl3 | 0.0304 (5) | 0.0397 (5) | 0.0474 (6) | 0.0056 (4) | 0.0083 (4) | 0.0052 (4) |
O3A | 0.064 (2) | 0.063 (2) | 0.052 (2) | 0.0015 (16) | 0.0144 (16) | 0.0001 (15) |
O3B | 0.063 (2) | 0.132 (4) | 0.076 (3) | −0.043 (2) | 0.0247 (19) | −0.049 (3) |
O3C | 0.062 (2) | 0.111 (3) | 0.104 (3) | 0.037 (2) | 0.051 (2) | 0.035 (3) |
O3D | 0.132 (4) | 0.063 (2) | 0.110 (3) | 0.016 (2) | 0.008 (3) | 0.055 (2) |
O1W | 0.0329 (14) | 0.0619 (18) | 0.0386 (16) | −0.0032 (13) | 0.0111 (12) | −0.0034 (13) |
O2W | 0.0409 (16) | 0.072 (2) | 0.0528 (19) | 0.0079 (15) | 0.0182 (14) | −0.0045 (16) |
O3W | 0.047 (2) | 0.133 (4) | 0.155 (4) | 0.013 (2) | 0.049 (3) | 0.057 (3) |
O4W | 0.084 (3) | 0.126 (4) | 0.067 (3) | −0.022 (3) | 0.003 (2) | 0.028 (2) |
O5W | 0.192 (6) | 0.166 (6) | 0.189 (7) | 0.010 (5) | 0.120 (6) | −0.027 (5) |
O6W | 0.187 (7) | 0.331 (11) | 0.170 (7) | −0.102 (7) | 0.136 (6) | −0.087 (7) |
Mn1—O2 | 1.843 (2) | C13—C14 | 1.380 (5) |
Mn1—O1 | 1.859 (2) | C13—H13A | 0.950 |
Mn1—N2 | 2.085 (3) | C14—H14A | 0.950 |
Mn1—N3 | 2.111 (3) | C15—C16 | 1.374 (5) |
Mn1—N4 | 2.253 (3) | C15—H15A | 0.950 |
Mn1—N1 | 2.265 (3) | C16—C17 | 1.388 (6) |
Mn1—Mn2 | 2.6576 (6) | C16—H16A | 0.950 |
Mn2—O2 | 1.782 (2) | C17—C18 | 1.381 (6) |
Mn2—O1 | 1.798 (2) | C17—H17A | 0.950 |
Mn2—N8 | 2.018 (3) | C18—C19 | 1.377 (5) |
Mn2—N5 | 2.021 (3) | C18—H18A | 0.950 |
Mn2—N7 | 2.068 (3) | C19—C20 | 1.500 (5) |
Mn2—N6 | 2.072 (3) | C20—H20A | 0.990 |
N1—C5 | 1.340 (4) | C20—H20B | 0.990 |
N1—C1 | 1.351 (4) | C21—C22 | 1.517 (5) |
N2—C6 | 1.488 (4) | C21—H21A | 0.990 |
N2—C7 | 1.490 (4) | C21—H21B | 0.990 |
N2—H2B | 0.930 | C22—H22A | 0.990 |
N3—C9 | 1.479 (4) | C22—H22B | 0.990 |
N3—C8 | 1.486 (4) | C23—C24 | 1.499 (5) |
N3—H3B | 0.930 | C23—H23A | 0.990 |
N4—C14 | 1.340 (4) | C23—H23B | 0.990 |
N4—C10 | 1.344 (4) | C24—C25 | 1.376 (5) |
N5—C15 | 1.345 (4) | C25—C26 | 1.383 (6) |
N5—C19 | 1.349 (4) | C25—H25A | 0.950 |
N6—C20 | 1.485 (4) | C26—C27 | 1.379 (6) |
N6—C21 | 1.489 (4) | C26—H26A | 0.950 |
N6—H6C | 0.930 | C27—C28 | 1.370 (5) |
N7—C23 | 1.481 (4) | C27—H27A | 0.950 |
N7—C22 | 1.496 (4) | C28—H28A | 0.950 |
N7—H7C | 0.930 | Cl1—O1C | 1.398 (3) |
N8—C24 | 1.346 (4) | Cl1—O1B | 1.401 (3) |
N8—C28 | 1.347 (4) | Cl1—O1A | 1.416 (3) |
C1—C2 | 1.366 (5) | Cl1—O1D | 1.469 (3) |
C1—H1A | 0.950 | Cl2—O2C | 1.355 (5) |
C2—C3 | 1.391 (6) | Cl2—O2G | 1.383 (6) |
C2—H2A | 0.950 | Cl2—O2A | 1.401 (4) |
C3—C4 | 1.370 (6) | Cl2—O2F | 1.406 (6) |
C3—H3A | 0.950 | Cl2—O2D | 1.417 (4) |
C4—C5 | 1.383 (5) | Cl2—O2B | 1.461 (6) |
C4—H4A | 0.950 | Cl2—O2E | 1.462 (6) |
C5—C6 | 1.505 (5) | Cl3—O3D | 1.396 (3) |
C6—H6A | 0.990 | Cl3—O3C | 1.401 (3) |
C6—H6B | 0.990 | Cl3—O3B | 1.418 (3) |
C7—C8 | 1.504 (5) | Cl3—O3A | 1.438 (3) |
C7—H7A | 0.990 | O1W—H1 | 0.85 |
C7—H7B | 0.990 | O1W—H2 | 0.85 |
C8—H8A | 0.990 | O2W—H3 | 0.85 |
C8—H8B | 0.990 | O2W—H4 | 0.85 |
C9—C10 | 1.507 (5) | O3W—H5 | 0.85 |
C9—H9A | 0.990 | O3W—H6 | 0.85 |
C9—H9B | 0.990 | O4W—H7 | 0.85 |
C10—C11 | 1.379 (5) | O4W—H8 | 0.85 |
C11—C12 | 1.375 (5) | O5W—H9 | 0.85 |
C11—H11A | 0.950 | O5W—H10 | 0.85 |
C12—C13 | 1.388 (5) | O6W—H11 | 0.85 |
C12—H12A | 0.950 | O6W—H12 | 0.85 |
O2—Mn1—O1 | 84.46 (9) | C7—C8—H8A | 109.7 |
O2—Mn1—N2 | 95.69 (10) | N3—C8—H8B | 109.7 |
O1—Mn1—N2 | 167.26 (10) | C7—C8—H8B | 109.7 |
O2—Mn1—N3 | 165.94 (10) | H8A—C8—H8B | 108.2 |
O1—Mn1—N3 | 99.75 (10) | N3—C9—C10 | 109.5 (2) |
N2—Mn1—N3 | 83.16 (11) | N3—C9—H9A | 109.8 |
O2—Mn1—N4 | 92.09 (9) | C10—C9—H9A | 109.8 |
O1—Mn1—N4 | 98.27 (9) | N3—C9—H9B | 109.8 |
N2—Mn1—N4 | 94.46 (10) | C10—C9—H9B | 109.8 |
N3—Mn1—N4 | 74.08 (10) | H9A—C9—H9B | 108.2 |
O2—Mn1—N1 | 96.85 (9) | N4—C10—C11 | 121.7 (3) |
O1—Mn1—N1 | 92.67 (10) | N4—C10—C9 | 114.4 (3) |
N2—Mn1—N1 | 74.65 (10) | C11—C10—C9 | 123.9 (3) |
N3—Mn1—N1 | 96.35 (10) | C12—C11—C10 | 119.3 (3) |
N4—Mn1—N1 | 166.50 (10) | C12—C11—H11A | 120.4 |
O2—Mn1—Mn2 | 41.97 (6) | C10—C11—H11A | 120.4 |
O1—Mn1—Mn2 | 42.49 (6) | C11—C12—C13 | 119.5 (3) |
N2—Mn1—Mn2 | 136.33 (7) | C11—C12—H12A | 120.3 |
N3—Mn1—Mn2 | 140.47 (7) | C13—C12—H12A | 120.3 |
N4—Mn1—Mn2 | 96.78 (7) | C14—C13—C12 | 118.1 (3) |
N1—Mn1—Mn2 | 96.64 (7) | C14—C13—H13A | 120.9 |
O2—Mn2—O1 | 88.05 (10) | C12—C13—H13A | 120.9 |
O2—Mn2—N8 | 98.78 (10) | N4—C14—C13 | 122.6 (3) |
O1—Mn2—N8 | 93.15 (10) | N4—C14—H14A | 118.7 |
O2—Mn2—N5 | 92.98 (10) | C13—C14—H14A | 118.7 |
O1—Mn2—N5 | 100.43 (10) | N5—C15—C16 | 121.4 (3) |
N8—Mn2—N5 | 162.33 (11) | N5—C15—H15A | 119.3 |
O2—Mn2—N7 | 93.48 (10) | C16—C15—H15A | 119.3 |
O1—Mn2—N7 | 173.53 (10) | C15—C16—C17 | 118.6 (4) |
N8—Mn2—N7 | 80.42 (11) | C15—C16—H16A | 120.7 |
N5—Mn2—N7 | 85.77 (10) | C17—C16—H16A | 120.7 |
O2—Mn2—N6 | 173.40 (10) | C18—C17—C16 | 120.0 (4) |
O1—Mn2—N6 | 94.92 (10) | C18—C17—H17A | 120.0 |
N8—Mn2—N6 | 86.96 (11) | C16—C17—H17A | 120.0 |
N5—Mn2—N6 | 80.70 (11) | C19—C18—C17 | 118.8 (4) |
N7—Mn2—N6 | 84.22 (11) | C19—C18—H18A | 120.6 |
O2—Mn2—Mn1 | 43.75 (6) | C17—C18—H18A | 120.6 |
O1—Mn2—Mn1 | 44.31 (6) | N5—C19—C18 | 121.1 (3) |
N8—Mn2—Mn1 | 98.10 (7) | N5—C19—C20 | 115.1 (3) |
N5—Mn2—Mn1 | 99.51 (7) | C18—C19—C20 | 123.8 (3) |
N7—Mn2—Mn1 | 136.84 (7) | N6—C20—C19 | 109.4 (3) |
N6—Mn2—Mn1 | 138.93 (8) | N6—C20—H20A | 109.8 |
Mn2—O1—Mn1 | 93.20 (9) | C19—C20—H20A | 109.8 |
Mn2—O2—Mn1 | 94.28 (9) | N6—C20—H20B | 109.8 |
C5—N1—C1 | 118.4 (3) | C19—C20—H20B | 109.8 |
C5—N1—Mn1 | 112.1 (2) | H20A—C20—H20B | 108.2 |
C1—N1—Mn1 | 128.9 (2) | N6—C21—C22 | 110.0 (3) |
C6—N2—C7 | 111.3 (3) | N6—C21—H21A | 109.7 |
C6—N2—Mn1 | 109.11 (19) | C22—C21—H21A | 109.7 |
C7—N2—Mn1 | 108.43 (19) | N6—C21—H21B | 109.7 |
C6—N2—H2B | 109.3 | C22—C21—H21B | 109.7 |
C7—N2—H2B | 109.3 | H21A—C21—H21B | 108.2 |
Mn1—N2—H2B | 109.3 | N7—C22—C21 | 110.3 (3) |
C9—N3—C8 | 110.8 (3) | N7—C22—H22A | 109.6 |
C9—N3—Mn1 | 109.53 (19) | C21—C22—H22A | 109.6 |
C8—N3—Mn1 | 107.74 (19) | N7—C22—H22B | 109.6 |
C9—N3—H3B | 109.6 | C21—C22—H22B | 109.6 |
C8—N3—H3B | 109.6 | H22A—C22—H22B | 108.1 |
Mn1—N3—H3B | 109.6 | N7—C23—C24 | 109.7 (3) |
C14—N4—C10 | 118.9 (3) | N7—C23—H23A | 109.7 |
C14—N4—Mn1 | 127.2 (2) | C24—C23—H23A | 109.7 |
C10—N4—Mn1 | 113.6 (2) | N7—C23—H23B | 109.7 |
C15—N5—C19 | 120.1 (3) | C24—C23—H23B | 109.7 |
C15—N5—Mn2 | 123.6 (2) | H23A—C23—H23B | 108.2 |
C19—N5—Mn2 | 115.7 (2) | N8—C24—C25 | 121.3 (3) |
C20—N6—C21 | 115.5 (3) | N8—C24—C23 | 114.5 (3) |
C20—N6—Mn2 | 108.29 (19) | C25—C24—C23 | 124.2 (3) |
C21—N6—Mn2 | 108.98 (19) | C24—C25—C26 | 118.8 (4) |
C20—N6—H6C | 108.0 | C24—C25—H25A | 120.6 |
C21—N6—H6C | 108.0 | C26—C25—H25A | 120.6 |
Mn2—N6—H6C | 108.0 | C27—C26—C25 | 119.5 (4) |
C23—N7—C22 | 116.2 (3) | C27—C26—H26A | 120.3 |
C23—N7—Mn2 | 107.40 (18) | C25—C26—H26A | 120.3 |
C22—N7—Mn2 | 109.24 (19) | C28—C27—C26 | 119.4 (4) |
C23—N7—H7C | 107.9 | C28—C27—H27A | 120.3 |
C22—N7—H7C | 107.9 | C26—C27—H27A | 120.3 |
Mn2—N7—H7C | 107.9 | N8—C28—C27 | 121.1 (3) |
C24—N8—C28 | 119.9 (3) | N8—C28—H28A | 119.5 |
C24—N8—Mn2 | 115.8 (2) | C27—C28—H28A | 119.5 |
C28—N8—Mn2 | 124.2 (2) | O1C—Cl1—O1B | 113.7 (3) |
N1—C1—C2 | 122.6 (3) | O1C—Cl1—O1A | 112.6 (2) |
N1—C1—H1A | 118.7 | O1B—Cl1—O1A | 113.1 (3) |
C2—C1—H1A | 118.7 | O1C—Cl1—O1D | 103.8 (3) |
C1—C2—C3 | 118.7 (4) | O1B—Cl1—O1D | 107.0 (3) |
C1—C2—H2A | 120.6 | O1A—Cl1—O1D | 105.6 (2) |
C3—C2—H2A | 120.6 | O2C—Cl2—O2A | 109.1 (5) |
C4—C3—C2 | 119.1 (4) | O2C—Cl2—O2D | 114.0 (4) |
C4—C3—H3A | 120.4 | O2A—Cl2—O2D | 113.8 (3) |
C2—C3—H3A | 120.4 | O2C—Cl2—O2B | 110.1 (6) |
C3—C4—C5 | 119.3 (4) | O2A—Cl2—O2B | 103.9 (4) |
C3—C4—H4A | 120.3 | O2D—Cl2—O2B | 105.4 (4) |
C5—C4—H4A | 120.3 | O2G—Cl2—O2A | 108.4 (5) |
N1—C5—C4 | 121.9 (3) | O2G—Cl2—O2F | 109.1 (5) |
N1—C5—C6 | 115.2 (3) | O2A—Cl2—O2F | 120.6 (4) |
C4—C5—C6 | 122.9 (3) | O2G—Cl2—O2E | 107.8 (6) |
N2—C6—C5 | 109.4 (2) | O2A—Cl2—O2E | 106.3 (4) |
N2—C6—H6A | 109.8 | O2F—Cl2—O2E | 103.9 (4) |
C5—C6—H6A | 109.8 | O3D—Cl3—O3C | 113.6 (3) |
N2—C6—H6B | 109.8 | O3D—Cl3—O3B | 111.3 (3) |
C5—C6—H6B | 109.8 | O3C—Cl3—O3B | 109.0 (3) |
H6A—C6—H6B | 108.2 | O3D—Cl3—O3A | 107.7 (2) |
N2—C7—C8 | 108.9 (3) | O3C—Cl3—O3A | 109.3 (2) |
N2—C7—H7A | 109.9 | O3B—Cl3—O3A | 105.7 (2) |
C8—C7—H7A | 109.9 | H1—O1W—H2 | 105.2 |
N2—C7—H7B | 109.9 | H3—O2W—H4 | 105.1 |
C8—C7—H7B | 109.9 | H5—O3W—H6 | 105.1 |
H7A—C7—H7B | 108.3 | H7—O4W—H8 | 105.0 |
N3—C8—C7 | 109.7 (3) | H9—O5W—H10 | 105.1 |
N3—C8—H8A | 109.7 | H11—O6W—H12 | 107.3 |
O1—Mn1—Mn2—O2 | −179.56 (13) | O1—Mn2—N5—C19 | 82.3 (2) |
N2—Mn1—Mn2—O2 | −18.18 (15) | N8—Mn2—N5—C19 | −57.4 (4) |
N3—Mn1—Mn2—O2 | 158.71 (16) | N7—Mn2—N5—C19 | −95.9 (2) |
N4—Mn1—Mn2—O2 | 85.58 (12) | N6—Mn2—N5—C19 | −11.1 (2) |
N1—Mn1—Mn2—O2 | −92.87 (12) | Mn1—Mn2—N5—C19 | 127.3 (2) |
O2—Mn1—Mn2—O1 | 179.56 (13) | O1—Mn2—N6—C20 | −74.2 (2) |
N2—Mn1—Mn2—O1 | 161.38 (15) | N8—Mn2—N6—C20 | −167.1 (2) |
N3—Mn1—Mn2—O1 | −21.73 (16) | N5—Mn2—N6—C20 | 25.6 (2) |
N4—Mn1—Mn2—O1 | −94.86 (12) | N7—Mn2—N6—C20 | 112.3 (2) |
N1—Mn1—Mn2—O1 | 86.69 (12) | Mn1—Mn2—N6—C20 | −68.2 (2) |
O2—Mn1—Mn2—N8 | −94.25 (12) | O1—Mn2—N6—C21 | 159.5 (2) |
O1—Mn1—Mn2—N8 | 86.19 (12) | N8—Mn2—N6—C21 | 66.6 (2) |
N2—Mn1—Mn2—N8 | −112.43 (13) | N5—Mn2—N6—C21 | −100.7 (2) |
N3—Mn1—Mn2—N8 | 64.46 (14) | N7—Mn2—N6—C21 | −14.1 (2) |
N4—Mn1—Mn2—N8 | −8.67 (10) | Mn1—Mn2—N6—C21 | 165.45 (16) |
N1—Mn1—Mn2—N8 | 172.88 (10) | O2—Mn2—N7—C23 | −70.2 (2) |
O2—Mn1—Mn2—N5 | 84.33 (13) | N8—Mn2—N7—C23 | 28.2 (2) |
O1—Mn1—Mn2—N5 | −95.24 (13) | N5—Mn2—N7—C23 | −162.9 (2) |
N2—Mn1—Mn2—N5 | 66.14 (14) | N6—Mn2—N7—C23 | 116.0 (2) |
N3—Mn1—Mn2—N5 | −116.96 (14) | Mn1—Mn2—N7—C23 | −63.5 (2) |
N4—Mn1—Mn2—N5 | 169.90 (10) | O2—Mn2—N7—C22 | 163.0 (2) |
N1—Mn1—Mn2—N5 | −8.54 (10) | N8—Mn2—N7—C22 | −98.7 (2) |
O2—Mn1—Mn2—N7 | −9.65 (14) | N5—Mn2—N7—C22 | 70.2 (2) |
O1—Mn1—Mn2—N7 | 170.79 (14) | N6—Mn2—N7—C22 | −10.8 (2) |
N2—Mn1—Mn2—N7 | −27.83 (16) | Mn1—Mn2—N7—C22 | 169.62 (16) |
N3—Mn1—Mn2—N7 | 149.06 (16) | O2—Mn2—N8—C24 | 77.9 (2) |
N4—Mn1—Mn2—N7 | 75.93 (13) | O1—Mn2—N8—C24 | 166.4 (2) |
N1—Mn1—Mn2—N7 | −102.52 (13) | N5—Mn2—N8—C24 | −53.3 (4) |
O2—Mn1—Mn2—N6 | 171.05 (16) | N7—Mn2—N8—C24 | −14.2 (2) |
O1—Mn1—Mn2—N6 | −8.51 (15) | N6—Mn2—N8—C24 | −98.9 (2) |
N2—Mn1—Mn2—N6 | 152.87 (17) | Mn1—Mn2—N8—C24 | 122.1 (2) |
N3—Mn1—Mn2—N6 | −30.24 (18) | O2—Mn2—N8—C28 | −106.2 (2) |
N4—Mn1—Mn2—N6 | −103.37 (14) | O1—Mn2—N8—C28 | −17.7 (3) |
N1—Mn1—Mn2—N6 | 78.18 (14) | N5—Mn2—N8—C28 | 122.7 (3) |
O2—Mn2—O1—Mn1 | 0.30 (9) | N7—Mn2—N8—C28 | 161.7 (3) |
N8—Mn2—O1—Mn1 | −98.38 (10) | N6—Mn2—N8—C28 | 77.1 (3) |
N5—Mn2—O1—Mn1 | 92.97 (11) | Mn1—Mn2—N8—C28 | −62.0 (2) |
N6—Mn2—O1—Mn1 | 174.40 (10) | C5—N1—C1—C2 | 0.2 (5) |
O2—Mn1—O1—Mn2 | −0.29 (9) | Mn1—N1—C1—C2 | 170.5 (3) |
N2—Mn1—O1—Mn2 | −91.6 (4) | N1—C1—C2—C3 | 0.2 (5) |
N3—Mn1—O1—Mn2 | 166.17 (10) | C1—C2—C3—C4 | 0.0 (6) |
N4—Mn1—O1—Mn2 | 91.02 (10) | C2—C3—C4—C5 | −0.5 (6) |
N1—Mn1—O1—Mn2 | −96.92 (10) | C1—N1—C5—C4 | −0.7 (5) |
O1—Mn2—O2—Mn1 | −0.31 (9) | Mn1—N1—C5—C4 | −172.6 (3) |
N8—Mn2—O2—Mn1 | 92.58 (10) | C1—N1—C5—C6 | 177.7 (3) |
N5—Mn2—O2—Mn1 | −100.66 (10) | Mn1—N1—C5—C6 | 5.8 (3) |
N7—Mn2—O2—Mn1 | 173.40 (10) | C3—C4—C5—N1 | 0.9 (5) |
O1—Mn1—O2—Mn2 | 0.30 (9) | C3—C4—C5—C6 | −177.4 (3) |
N2—Mn1—O2—Mn2 | 167.50 (10) | C7—N2—C6—C5 | 72.7 (3) |
N3—Mn1—O2—Mn2 | −108.0 (4) | Mn1—N2—C6—C5 | −46.9 (3) |
N4—Mn1—O2—Mn2 | −97.81 (10) | N1—C5—C6—N2 | 25.7 (4) |
N1—Mn1—O2—Mn2 | 92.33 (10) | C4—C5—C6—N2 | −155.9 (3) |
O2—Mn1—N1—C5 | 69.2 (2) | C6—N2—C7—C8 | −160.0 (3) |
O1—Mn1—N1—C5 | 154.0 (2) | Mn1—N2—C7—C8 | −40.0 (3) |
N2—Mn1—N1—C5 | −24.8 (2) | C9—N3—C8—C7 | −158.2 (3) |
N3—Mn1—N1—C5 | −105.9 (2) | Mn1—N3—C8—C7 | −38.4 (3) |
N4—Mn1—N1—C5 | −61.9 (5) | N2—C7—C8—N3 | 53.0 (4) |
Mn2—Mn1—N1—C5 | 111.5 (2) | C8—N3—C9—C10 | 72.3 (3) |
O2—Mn1—N1—C1 | −101.6 (3) | Mn1—N3—C9—C10 | −46.5 (3) |
O1—Mn1—N1—C1 | −16.9 (3) | C14—N4—C10—C11 | −1.4 (5) |
N2—Mn1—N1—C1 | 164.4 (3) | Mn1—N4—C10—C11 | −175.6 (3) |
N3—Mn1—N1—C1 | 83.3 (3) | C14—N4—C10—C9 | 178.8 (3) |
N4—Mn1—N1—C1 | 127.3 (4) | Mn1—N4—C10—C9 | 4.7 (3) |
Mn2—Mn1—N1—C1 | −59.3 (3) | N3—C9—C10—N4 | 26.5 (4) |
O2—Mn1—N2—C6 | −57.9 (2) | N3—C9—C10—C11 | −153.3 (3) |
O1—Mn1—N2—C6 | 32.1 (5) | N4—C10—C11—C12 | 1.9 (5) |
N3—Mn1—N2—C6 | 136.2 (2) | C9—C10—C11—C12 | −178.3 (3) |
N4—Mn1—N2—C6 | −150.5 (2) | C10—C11—C12—C13 | −1.4 (5) |
N1—Mn1—N2—C6 | 37.64 (19) | C11—C12—C13—C14 | 0.5 (5) |
Mn2—Mn1—N2—C6 | −45.8 (2) | C10—N4—C14—C13 | 0.5 (5) |
O2—Mn1—N2—C7 | −179.2 (2) | Mn1—N4—C14—C13 | 173.7 (2) |
O1—Mn1—N2—C7 | −89.2 (5) | C12—C13—C14—N4 | 0.0 (5) |
N3—Mn1—N2—C7 | 14.8 (2) | C19—N5—C15—C16 | −1.6 (5) |
N4—Mn1—N2—C7 | 88.2 (2) | Mn2—N5—C15—C16 | −172.7 (3) |
N1—Mn1—N2—C7 | −83.7 (2) | N5—C15—C16—C17 | 0.6 (5) |
Mn2—Mn1—N2—C7 | −167.14 (16) | C15—C16—C17—C18 | 0.3 (6) |
O2—Mn1—N3—C9 | 47.4 (5) | C16—C17—C18—C19 | 0.0 (6) |
O1—Mn1—N3—C9 | −59.1 (2) | C15—N5—C19—C18 | 1.8 (5) |
N2—Mn1—N3—C9 | 133.4 (2) | Mn2—N5—C19—C18 | 173.6 (3) |
N4—Mn1—N3—C9 | 36.8 (2) | C15—N5—C19—C20 | −178.4 (3) |
N1—Mn1—N3—C9 | −152.9 (2) | Mn2—N5—C19—C20 | −6.6 (4) |
Mn2—Mn1—N3—C9 | −44.4 (3) | C17—C18—C19—N5 | −1.0 (6) |
O2—Mn1—N3—C8 | −73.2 (5) | C17—C18—C19—C20 | 179.2 (4) |
O1—Mn1—N3—C8 | −179.7 (2) | C21—N6—C20—C19 | 87.2 (3) |
N2—Mn1—N3—C8 | 12.8 (2) | Mn2—N6—C20—C19 | −35.3 (3) |
N4—Mn1—N3—C8 | −83.8 (2) | N5—C19—C20—N6 | 28.4 (4) |
N1—Mn1—N3—C8 | 86.5 (2) | C18—C19—C20—N6 | −151.8 (3) |
Mn2—Mn1—N3—C8 | −165.02 (16) | C20—N6—C21—C22 | −85.8 (3) |
O2—Mn1—N4—C14 | −14.5 (3) | Mn2—N6—C21—C22 | 36.2 (3) |
O1—Mn1—N4—C14 | −99.2 (3) | C23—N7—C22—C21 | −88.0 (3) |
N2—Mn1—N4—C14 | 81.4 (3) | Mn2—N7—C22—C21 | 33.7 (3) |
N3—Mn1—N4—C14 | 162.9 (3) | N6—C21—C22—N7 | −46.8 (4) |
N1—Mn1—N4—C14 | 117.0 (4) | C22—N7—C23—C24 | 85.3 (3) |
Mn2—Mn1—N4—C14 | −56.4 (3) | Mn2—N7—C23—C24 | −37.4 (3) |
O2—Mn1—N4—C10 | 159.0 (2) | C28—N8—C24—C25 | 1.4 (5) |
O1—Mn1—N4—C10 | 74.3 (2) | Mn2—N8—C24—C25 | 177.5 (3) |
N2—Mn1—N4—C10 | −105.1 (2) | C28—N8—C24—C23 | −179.9 (3) |
N3—Mn1—N4—C10 | −23.5 (2) | Mn2—N8—C24—C23 | −3.7 (3) |
N1—Mn1—N4—C10 | −69.4 (4) | N7—C23—C24—N8 | 28.0 (4) |
Mn2—Mn1—N4—C10 | 117.2 (2) | N7—C23—C24—C25 | −153.3 (3) |
O2—Mn2—N5—C15 | −17.7 (3) | N8—C24—C25—C26 | −1.4 (5) |
O1—Mn2—N5—C15 | −106.3 (2) | C23—C24—C25—C26 | 179.9 (3) |
N8—Mn2—N5—C15 | 114.1 (4) | C24—C25—C26—C27 | 0.5 (6) |
N7—Mn2—N5—C15 | 75.6 (3) | C25—C26—C27—C28 | 0.5 (6) |
N6—Mn2—N5—C15 | 160.4 (3) | C24—N8—C28—C27 | −0.4 (5) |
Mn1—Mn2—N5—C15 | −61.2 (2) | Mn2—N8—C28—C27 | −176.1 (2) |
O2—Mn2—N5—C19 | 170.8 (2) | C26—C27—C28—N8 | −0.6 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O1W | 0.93 | 2.05 | 2.952 (4) | 162 |
N3—H3B···O2W | 0.93 | 2.09 | 2.964 (4) | 155 |
N6—H6C···O2Wi | 0.93 | 2.00 | 2.882 (4) | 158 |
N7—H7C···O1Wii | 0.93 | 2.05 | 2.901 (4) | 151 |
O1W—H2···O3A | 0.85 | 2.35 | 3.094 (4) | 147 |
O1W—H2···O3D | 0.85 | 2.29 | 3.075 (6) | 153 |
O1W—H1···O1Biii | 0.85 | 2.23 | 3.047 (6) | 161 |
O1W—H1···O1Diii | 0.85 | 2.33 | 2.990 (5) | 135 |
O2W—H4···O3W | 0.85 | 2.19 | 2.858 (6) | 136 |
O2W—H3···O2Aiv | 0.85 | 2.05 | 2.852 (6) | 157 |
O3W—H6···O6W | 0.85 | 1.87 | 2.716 (9) | 175 |
O3W—H5···O1 | 0.85 | 1.97 | 2.806 (4) | 167 |
O4W—H7···O1Av | 0.85 | 2.24 | 2.918 (5) | 137 |
O4W—H8···O3Bvi | 0.85 | 2.08 | 2.899 (5) | 161 |
O5W—H9···O3Cvi | 0.85 | 2.13 | 2.977 (7) | 177 |
O5W—H10···O2Gvii | 0.85 | 2.32 | 3.129 (15) | 160 |
O6W—H12···O4W | 0.85 | 1.87 | 2.717 (8) | 177 |
O6W—H11···O5W | 0.85 | 1.72 | 2.548 (12) | 164 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) x−1, y, z; (vi) x−1/2, −y+1/2, z+1/2; (vii) x+1/2, −y+1/2, z+1/2. |
[Mn2O2(C14H18N4)2](ClO4)3·6H2O | F(000) = 2132 |
Mr = 1032.97 | Dx = 1.591 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5239 reflections |
a = 15.4488 (7) Å | θ = 2.5–25.7° |
b = 12.2792 (5) Å | µ = 0.86 mm−1 |
c = 23.7512 (10) Å | T = 295 K |
β = 106.852 (2)° | Plate, brown |
V = 4312.1 (3) Å3 | 0.25 × 0.20 × 0.05 mm |
Z = 4 |
Bruker Nonius X8 APEXII CCD area-detector diffractometer | 4424 independent reflections |
Radiation source: fine-focus sealed tube | 3026 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.069 |
thin–slice ω and ϕ scans | θmax = 26.4°, θmin = 3.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −19→19 |
Tmin = 0.832, Tmax = 0.958 | k = −15→15 |
34341 measured reflections | l = −29→29 |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.235 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1669P)2] where P = (Fo2 + 2Fc2)/3 |
4424 reflections | (Δ/σ)max < 0.001 |
298 parameters | Δρmax = 0.92 e Å−3 |
30 restraints | Δρmin = −0.70 e Å−3 |
[Mn2O2(C14H18N4)2](ClO4)3·6H2O | V = 4312.1 (3) Å3 |
Mr = 1032.97 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 15.4488 (7) Å | µ = 0.86 mm−1 |
b = 12.2792 (5) Å | T = 295 K |
c = 23.7512 (10) Å | 0.25 × 0.20 × 0.05 mm |
β = 106.852 (2)° |
Bruker Nonius X8 APEXII CCD area-detector diffractometer | 4424 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3026 reflections with I > 2σ(I) |
Tmin = 0.832, Tmax = 0.958 | Rint = 0.069 |
34341 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 30 restraints |
wR(F2) = 0.235 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.92 e Å−3 |
4424 reflections | Δρmin = −0.70 e Å−3 |
298 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Water molecule O1W is fully occupied. Perchlorate Cl2 is fully occupied (although rotationally disordered). Perchlorate Cl3 is has site occupancy 0.5. When perchlorate Cl3 is not present, water molecules O3W, O4W and O5W are present [One further half-occupied water molecule is implied by analogy with the LT structure]. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mn1 | 0.5000 | 0.41233 (6) | 0.2500 | 0.0374 (3) | |
Mn2 | 0.5000 | 0.19590 (6) | 0.2500 | 0.0380 (3) | |
O1 | 0.42079 (18) | 0.3023 (2) | 0.25150 (13) | 0.0445 (7) | |
N3 | 0.4057 (2) | 0.5398 (3) | 0.23301 (15) | 0.0480 (8) | |
H3A | 0.3805 | 0.5454 | 0.2631 | 0.058* | |
N4 | 0.4607 (2) | 0.4345 (3) | 0.15462 (16) | 0.0483 (8) | |
N7 | 0.5820 (3) | 0.0693 (3) | 0.23683 (17) | 0.0547 (9) | |
H7B | 0.6387 | 0.0820 | 0.2609 | 0.066* | |
N8 | 0.4464 (2) | 0.1675 (3) | 0.16031 (16) | 0.0493 (8) | |
C8 | 0.4541 (3) | 0.6435 (4) | 0.2277 (2) | 0.0628 (12) | |
H8A | 0.4193 | 0.7053 | 0.2345 | 0.075* | |
H8B | 0.4604 | 0.6496 | 0.1884 | 0.075* | |
C9 | 0.3354 (3) | 0.5164 (4) | 0.1780 (2) | 0.0597 (11) | |
H9A | 0.2991 | 0.5809 | 0.1646 | 0.072* | |
H9B | 0.2960 | 0.4590 | 0.1843 | 0.072* | |
C10 | 0.3807 (3) | 0.4811 (3) | 0.13250 (18) | 0.0508 (10) | |
C11 | 0.3424 (4) | 0.4955 (5) | 0.0721 (2) | 0.0746 (15) | |
H11A | 0.2866 | 0.5295 | 0.0572 | 0.090* | |
C12 | 0.3906 (5) | 0.4570 (5) | 0.0350 (2) | 0.0816 (17) | |
H12A | 0.3666 | 0.4636 | −0.0055 | 0.098* | |
C13 | 0.4710 (4) | 0.4110 (4) | 0.0575 (2) | 0.0753 (15) | |
H13A | 0.5033 | 0.3861 | 0.0326 | 0.090* | |
C14 | 0.5066 (3) | 0.3999 (4) | 0.1169 (2) | 0.0629 (12) | |
H14A | 0.5633 | 0.3681 | 0.1319 | 0.076* | |
C22 | 0.5508 (4) | −0.0323 (4) | 0.2561 (3) | 0.0797 (16) | |
H22A | 0.5792 | −0.0419 | 0.2979 | 0.096* | |
H22B | 0.5685 | −0.0929 | 0.2357 | 0.096* | |
C23 | 0.5869 (3) | 0.0754 (4) | 0.1763 (2) | 0.0659 (13) | |
H23A | 0.6043 | 0.0049 | 0.1646 | 0.079* | |
H23B | 0.6327 | 0.1279 | 0.1741 | 0.079* | |
C24 | 0.4986 (4) | 0.1079 (4) | 0.1359 (2) | 0.0617 (12) | |
C25 | 0.4695 (5) | 0.0790 (6) | 0.0775 (3) | 0.094 (2) | |
H25A | 0.5057 | 0.0375 | 0.0606 | 0.112* | |
C26 | 0.3854 (6) | 0.1133 (7) | 0.0449 (3) | 0.109 (2) | |
H26A | 0.3653 | 0.0975 | 0.0049 | 0.130* | |
C27 | 0.3298 (5) | 0.1715 (6) | 0.0708 (3) | 0.091 (2) | |
H27A | 0.2712 | 0.1904 | 0.0494 | 0.110* | |
C28 | 0.3630 (4) | 0.1998 (4) | 0.1279 (2) | 0.0656 (14) | |
H28A | 0.3280 | 0.2422 | 0.1454 | 0.079* | |
O1W | 0.7267 (3) | 0.5398 (5) | 0.1949 (2) | 0.1158 (16) | |
H1 | 0.7013 | 0.5908 | 0.1718 | 0.174* | |
H2 | 0.7282 | 0.4857 | 0.1728 | 0.174* | |
Cl2 | 0.09937 (13) | 0.27040 (16) | 0.11200 (9) | 0.1021 (6) | |
O2A | 0.1324 (9) | 0.1704 (8) | 0.0969 (6) | 0.1634 (18)* | 0.50 |
O2B | 0.0310 (7) | 0.3051 (9) | 0.0599 (5) | 0.1634 (18)* | 0.50 |
O2C | 0.0664 (9) | 0.2663 (10) | 0.1576 (5) | 0.1634 (18)* | 0.50 |
O2D | 0.1705 (7) | 0.3451 (10) | 0.1186 (5) | 0.1634 (18)* | 0.50 |
O2E | 0.1603 (8) | 0.2705 (10) | 0.1749 (4) | 0.1634 (18)* | 0.50 |
O2F | 0.0918 (9) | 0.1650 (7) | 0.0973 (6) | 0.1634 (18)* | 0.50 |
O2G | 0.0203 (7) | 0.3117 (9) | 0.1223 (6) | 0.1634 (18)* | 0.50 |
O2H | 0.1438 (8) | 0.3434 (10) | 0.0889 (5) | 0.1634 (18)* | 0.50 |
Cl3 | 0.7457 (2) | 0.3103 (3) | 0.10074 (18) | 0.0931 (10) | 0.50 |
O3A | 0.7548 (11) | 0.3046 (9) | 0.1633 (4) | 0.176 (6) | 0.50 |
O3B | 0.6804 (8) | 0.2308 (10) | 0.0774 (7) | 0.192 (8) | 0.50 |
O3C | 0.8279 (7) | 0.2797 (11) | 0.0949 (8) | 0.209 (9) | 0.50 |
O3D | 0.7182 (9) | 0.4109 (8) | 0.0839 (6) | 0.203 (8) | 0.50 |
O3W | 0.2552 (10) | 0.2812 (15) | 0.2718 (9) | 0.202 (8) | 0.50 |
H5 | 0.3046 | 0.2844 | 0.2629 | 0.303* | 0.50 |
H6 | 0.2521 | 0.2870 | 0.3068 | 0.303* | 0.50 |
O4W | 0.1731 (14) | 0.3384 (18) | 0.4569 (8) | 0.197 (7) | 0.50 |
H7 | 0.1298 | 0.3102 | 0.4303 | 0.296* | 0.50 |
H8 | 0.1559 | 0.3263 | 0.4873 | 0.296* | 0.50 |
O5W | 0.3653 (19) | 0.164 (2) | 0.4794 (17) | 0.314 (18) | 0.50 |
H9 | 0.3358 | 0.1873 | 0.5022 | 0.471* | 0.50 |
H10 | 0.4146 | 0.2000 | 0.4898 | 0.471* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0374 (5) | 0.0343 (5) | 0.0415 (5) | 0.000 | 0.0132 (3) | 0.000 |
Mn2 | 0.0384 (5) | 0.0342 (5) | 0.0420 (5) | 0.000 | 0.0124 (3) | 0.000 |
O1 | 0.0369 (14) | 0.0480 (17) | 0.0513 (17) | −0.0020 (10) | 0.0167 (12) | −0.0060 (11) |
N3 | 0.0528 (19) | 0.0400 (19) | 0.054 (2) | 0.0064 (14) | 0.0205 (15) | 0.0007 (15) |
N4 | 0.0500 (19) | 0.0399 (19) | 0.057 (2) | 0.0003 (15) | 0.0177 (16) | 0.0019 (15) |
N7 | 0.061 (2) | 0.040 (2) | 0.067 (2) | 0.0090 (16) | 0.0241 (18) | 0.0001 (17) |
N8 | 0.055 (2) | 0.0417 (18) | 0.051 (2) | −0.0048 (16) | 0.0155 (16) | 0.0024 (16) |
C8 | 0.072 (3) | 0.035 (2) | 0.081 (3) | 0.008 (2) | 0.022 (2) | 0.003 (2) |
C9 | 0.048 (2) | 0.052 (3) | 0.077 (3) | 0.0151 (19) | 0.014 (2) | 0.012 (2) |
C10 | 0.049 (2) | 0.044 (2) | 0.055 (2) | 0.0012 (18) | 0.0090 (18) | 0.0039 (19) |
C11 | 0.080 (3) | 0.068 (3) | 0.065 (3) | 0.002 (3) | 0.004 (3) | 0.010 (3) |
C12 | 0.110 (5) | 0.078 (4) | 0.052 (3) | −0.012 (3) | 0.015 (3) | 0.005 (3) |
C13 | 0.106 (4) | 0.066 (3) | 0.066 (3) | −0.017 (3) | 0.046 (3) | −0.005 (3) |
C14 | 0.066 (3) | 0.049 (3) | 0.082 (4) | −0.005 (2) | 0.034 (3) | −0.004 (2) |
C22 | 0.101 (4) | 0.046 (3) | 0.101 (4) | 0.015 (3) | 0.043 (4) | 0.008 (3) |
C23 | 0.075 (3) | 0.058 (3) | 0.073 (3) | 0.010 (2) | 0.035 (3) | −0.010 (2) |
C24 | 0.078 (3) | 0.056 (3) | 0.056 (3) | −0.007 (2) | 0.027 (2) | −0.002 (2) |
C25 | 0.116 (5) | 0.114 (5) | 0.057 (3) | −0.004 (4) | 0.033 (3) | −0.019 (3) |
C26 | 0.151 (7) | 0.120 (6) | 0.049 (3) | −0.031 (5) | 0.019 (4) | −0.004 (4) |
C27 | 0.094 (4) | 0.096 (5) | 0.066 (4) | −0.021 (4) | −0.006 (3) | 0.020 (3) |
C28 | 0.068 (3) | 0.057 (3) | 0.065 (3) | −0.011 (2) | 0.010 (2) | 0.014 (2) |
O1W | 0.085 (3) | 0.141 (4) | 0.122 (4) | −0.015 (3) | 0.031 (3) | 0.010 (3) |
Cl2 | 0.1151 (14) | 0.0906 (11) | 0.1132 (14) | 0.0029 (10) | 0.0529 (11) | −0.0102 (10) |
Cl3 | 0.0742 (19) | 0.095 (3) | 0.112 (3) | 0.0242 (16) | 0.0296 (18) | 0.0190 (18) |
O3A | 0.202 (16) | 0.140 (12) | 0.166 (15) | 0.035 (10) | 0.022 (12) | 0.018 (9) |
O3B | 0.158 (16) | 0.189 (17) | 0.26 (2) | 0.007 (14) | 0.108 (16) | 0.054 (16) |
O3C | 0.114 (10) | 0.183 (15) | 0.34 (3) | 0.050 (10) | 0.078 (14) | 0.074 (15) |
O3D | 0.201 (15) | 0.130 (12) | 0.31 (2) | 0.029 (11) | 0.122 (15) | 0.088 (13) |
O3W | 0.094 (8) | 0.29 (2) | 0.24 (2) | 0.004 (10) | 0.082 (11) | 0.066 (15) |
O4W | 0.233 (19) | 0.231 (18) | 0.124 (12) | −0.005 (17) | 0.045 (12) | 0.017 (12) |
O5W | 0.21 (3) | 0.23 (3) | 0.50 (6) | 0.01 (2) | 0.11 (3) | −0.12 (3) |
Mn1—O1 | 1.830 (3) | C14—H14A | 0.930 |
Mn1—O1i | 1.830 (3) | C22—C22i | 1.511 (11) |
Mn1—N3i | 2.096 (3) | C22—H22A | 0.970 |
Mn1—N3 | 2.096 (3) | C22—H22B | 0.970 |
Mn1—N4 | 2.186 (4) | C23—C24 | 1.478 (7) |
Mn1—N4i | 2.186 (4) | C23—H23A | 0.970 |
Mn1—Mn2 | 2.6575 (11) | C23—H23B | 0.970 |
Mn2—O1i | 1.798 (3) | C24—C25 | 1.376 (7) |
Mn2—O1 | 1.798 (3) | C25—C26 | 1.371 (10) |
Mn2—N8i | 2.079 (4) | C25—H25A | 0.930 |
Mn2—N8 | 2.079 (4) | C26—C27 | 1.392 (11) |
Mn2—N7 | 2.086 (3) | C26—H26A | 0.930 |
Mn2—N7i | 2.086 (3) | C27—C28 | 1.348 (8) |
N3—C9 | 1.465 (6) | C27—H27A | 0.930 |
N3—C8 | 1.499 (6) | C28—H28A | 0.930 |
N3—H3A | 0.910 | Cl2—O2C | 1.325 (8) |
N4—C10 | 1.324 (5) | Cl2—O2F | 1.337 (8) |
N4—C14 | 1.362 (6) | Cl2—O2H | 1.339 (8) |
N7—C22 | 1.459 (6) | Cl2—O2D | 1.404 (8) |
N7—C23 | 1.462 (6) | Cl2—O2G | 1.409 (8) |
N7—H7B | 0.910 | Cl2—O2A | 1.416 (8) |
N8—C24 | 1.338 (6) | Cl2—O2B | 1.438 (8) |
N8—C28 | 1.354 (6) | Cl2—O2E | 1.518 (8) |
C8—C8i | 1.504 (10) | Cl3—O3D | 1.330 (8) |
C8—H8A | 0.970 | Cl3—O3C | 1.369 (8) |
C8—H8B | 0.970 | Cl3—O3B | 1.397 (9) |
C9—C10 | 1.512 (6) | Cl3—O3A | 1.454 (9) |
C9—H9A | 0.970 | O1W—H1 | 0.85 |
C9—H9B | 0.970 | O1W—H2 | 0.85 |
C10—C11 | 1.396 (6) | O3W—H5 | 0.85 |
C11—C12 | 1.391 (8) | O3W—H6 | 0.85 |
C11—H11A | 0.930 | O4W—H7 | 0.85 |
C12—C13 | 1.327 (8) | O4W—H8 | 0.85 |
C12—H12A | 0.930 | O5W—H9 | 0.85 |
C13—C14 | 1.364 (7) | O5W—H10 | 0.85 |
C13—H13A | 0.930 | ||
O1—Mn1—O1i | 84.86 (16) | C10—C9—H9A | 110.0 |
O1—Mn1—N3i | 168.16 (13) | N3—C9—H9B | 110.0 |
O1i—Mn1—N3i | 97.11 (13) | C10—C9—H9B | 110.0 |
O1—Mn1—N3 | 97.11 (13) | H9A—C9—H9B | 108.4 |
O1i—Mn1—N3 | 168.17 (13) | N4—C10—C11 | 122.1 (4) |
N3i—Mn1—N3 | 83.37 (19) | N4—C10—C9 | 114.3 (3) |
O1—Mn1—N4 | 97.20 (13) | C11—C10—C9 | 123.5 (4) |
O1i—Mn1—N4 | 93.34 (13) | C12—C11—C10 | 117.5 (5) |
N3i—Mn1—N4 | 94.34 (13) | C12—C11—H11A | 121.2 |
N3—Mn1—N4 | 74.85 (13) | C10—C11—H11A | 121.3 |
O1—Mn1—N4i | 93.34 (13) | C13—C12—C11 | 120.0 (5) |
O1i—Mn1—N4i | 97.20 (13) | C13—C12—H12A | 120.0 |
N3i—Mn1—N4i | 74.85 (13) | C11—C12—H12A | 120.0 |
N3—Mn1—N4i | 94.34 (13) | C12—C13—C14 | 120.6 (5) |
N4—Mn1—N4i | 165.71 (18) | C12—C13—H13A | 119.7 |
O1—Mn1—Mn2 | 42.43 (8) | C14—C13—H13A | 119.7 |
O1i—Mn1—Mn2 | 42.43 (8) | N4—C14—C13 | 121.2 (5) |
N3i—Mn1—Mn2 | 138.32 (9) | N4—C14—H14A | 119.4 |
N3—Mn1—Mn2 | 138.32 (9) | C13—C14—H14A | 119.4 |
N4—Mn1—Mn2 | 97.14 (9) | N7—C22—C22i | 111.1 (4) |
N4i—Mn1—Mn2 | 97.14 (9) | N7—C22—H22A | 109.4 |
O1i—Mn2—O1 | 86.73 (17) | C22i—C22—H22A | 109.4 |
O1i—Mn2—N8i | 94.07 (14) | N7—C22—H22B | 109.4 |
O1—Mn2—N8i | 99.96 (14) | C22i—C22—H22B | 109.4 |
O1i—Mn2—N8 | 99.96 (14) | H22A—C22—H22B | 108.0 |
O1—Mn2—N8 | 94.07 (14) | N7—C23—C24 | 110.5 (4) |
N8i—Mn2—N8 | 160.7 (2) | N7—C23—H23A | 109.5 |
O1i—Mn2—N7 | 95.28 (14) | C24—C23—H23A | 109.5 |
O1—Mn2—N7 | 172.51 (13) | N7—C23—H23B | 109.5 |
N8i—Mn2—N7 | 87.12 (15) | C24—C23—H23B | 109.5 |
N8—Mn2—N7 | 78.48 (15) | H23A—C23—H23B | 108.1 |
O1i—Mn2—N7i | 172.51 (13) | N8—C24—C25 | 121.1 (5) |
O1—Mn2—N7i | 95.28 (15) | N8—C24—C23 | 115.2 (4) |
N8i—Mn2—N7i | 78.48 (15) | C25—C24—C23 | 123.7 (5) |
N8—Mn2—N7i | 87.12 (15) | C26—C25—C24 | 118.0 (6) |
N7—Mn2—N7i | 83.6 (2) | C26—C25—H25A | 121.0 |
O1i—Mn2—Mn1 | 43.37 (8) | C24—C25—H25A | 121.0 |
O1—Mn2—Mn1 | 43.37 (8) | C25—C26—C27 | 120.8 (6) |
N8i—Mn2—Mn1 | 99.65 (10) | C25—C26—H26A | 119.6 |
N8—Mn2—Mn1 | 99.65 (10) | C27—C26—H26A | 119.6 |
N7—Mn2—Mn1 | 138.18 (11) | C28—C27—C26 | 118.3 (6) |
N7i—Mn2—Mn1 | 138.18 (11) | C28—C27—H27A | 120.9 |
Mn2—O1—Mn1 | 94.20 (13) | C26—C27—H27A | 120.9 |
C9—N3—C8 | 110.5 (3) | C27—C28—N8 | 121.2 (6) |
C9—N3—Mn1 | 108.6 (2) | C27—C28—H28A | 119.4 |
C8—N3—Mn1 | 108.4 (2) | N8—C28—H28A | 119.4 |
C9—N3—H3A | 109.8 | O2C—Cl2—O2A | 115.2 (7) |
C8—N3—H3A | 109.8 | O2D—Cl2—O2A | 105.5 (6) |
Mn1—N3—H3A | 109.8 | O2C—Cl2—O2B | 110.8 (6) |
C10—N4—C14 | 118.5 (4) | O2D—Cl2—O2B | 104.9 (6) |
C10—N4—Mn1 | 114.4 (3) | O2A—Cl2—O2B | 105.5 (6) |
C14—N4—Mn1 | 127.0 (3) | O2C—Cl2—O2D | 114.0 (7) |
C22—N7—C23 | 117.9 (4) | O2F—Cl2—O2G | 112.3 (6) |
C22—N7—Mn2 | 108.7 (3) | O2H—Cl2—O2G | 113.8 (6) |
C23—N7—Mn2 | 108.4 (3) | O2F—Cl2—O2E | 103.9 (6) |
C22—N7—H7B | 107.1 | O2H—Cl2—O2E | 99.1 (6) |
C23—N7—H7B | 107.1 | O2G—Cl2—O2E | 98.6 (6) |
Mn2—N7—H7B | 107.1 | O2F—Cl2—O2H | 123.9 (7) |
C24—N8—C28 | 120.4 (4) | O3D—Cl3—O3C | 116.7 (7) |
C24—N8—Mn2 | 115.1 (3) | O3D—Cl3—O3B | 113.4 (7) |
C28—N8—Mn2 | 124.3 (4) | O3C—Cl3—O3B | 110.7 (7) |
N3—C8—C8i | 109.4 (3) | O3D—Cl3—O3A | 106.2 (7) |
N3—C8—H8A | 109.8 | O3C—Cl3—O3A | 105.8 (7) |
C8i—C8—H8A | 109.8 | O3B—Cl3—O3A | 102.6 (7) |
N3—C8—H8B | 109.8 | H1—O1W—H2 | 105.5 |
C8i—C8—H8B | 109.8 | H5—O3W—H6 | 123.1 |
H8A—C8—H8B | 108.2 | H7—O4W—H8 | 100.8 |
N3—C9—C10 | 108.4 (3) | H9—O5W—H10 | 104.4 |
N3—C9—H9A | 110.0 | ||
O1—Mn1—Mn2—O1i | 180.0 | O1i—Mn1—N4—C14 | −18.4 (4) |
N3i—Mn1—Mn2—O1i | −17.67 (19) | N3i—Mn1—N4—C14 | 79.0 (3) |
N3—Mn1—Mn2—O1i | 162.33 (19) | N3—Mn1—N4—C14 | 161.0 (4) |
N4—Mn1—Mn2—O1i | 87.13 (16) | N4i—Mn1—N4—C14 | 119.2 (3) |
N4i—Mn1—Mn2—O1i | −92.88 (16) | Mn2—Mn1—N4—C14 | −60.8 (3) |
O1i—Mn1—Mn2—O1 | 180.0 | O1i—Mn2—N7—C22 | 160.2 (3) |
N3i—Mn1—Mn2—O1 | 162.33 (19) | N8i—Mn2—N7—C22 | 66.4 (4) |
N3—Mn1—Mn2—O1 | −17.67 (19) | N8—Mn2—N7—C22 | −100.7 (4) |
N4—Mn1—Mn2—O1 | −92.87 (16) | N7i—Mn2—N7—C22 | −12.3 (3) |
N4i—Mn1—Mn2—O1 | 87.13 (16) | Mn1—Mn2—N7—C22 | 167.7 (3) |
O1—Mn1—Mn2—N8i | −94.32 (17) | O1i—Mn2—N7—C23 | −70.5 (3) |
O1i—Mn1—Mn2—N8i | 85.68 (17) | O1—Mn2—N7—C23 | 34.8 (11) |
N3i—Mn1—Mn2—N8i | 68.01 (17) | N8i—Mn2—N7—C23 | −164.4 (3) |
N3—Mn1—Mn2—N8i | −111.99 (17) | N8—Mn2—N7—C23 | 28.6 (3) |
N4—Mn1—Mn2—N8i | 172.81 (12) | N7i—Mn2—N7—C23 | 116.9 (4) |
N4i—Mn1—Mn2—N8i | −7.20 (12) | Mn1—Mn2—N7—C23 | −63.1 (4) |
O1—Mn1—Mn2—N8 | 85.68 (17) | O1i—Mn2—N8—C24 | 78.1 (3) |
O1i—Mn1—Mn2—N8 | −94.32 (17) | O1—Mn2—N8—C24 | 165.5 (3) |
N3i—Mn1—Mn2—N8 | −111.99 (17) | N8i—Mn2—N8—C24 | −57.8 (3) |
N3—Mn1—Mn2—N8 | 68.01 (17) | N7—Mn2—N8—C24 | −15.3 (3) |
N4—Mn1—Mn2—N8 | −7.19 (12) | N7i—Mn2—N8—C24 | −99.4 (3) |
N4i—Mn1—Mn2—N8 | 172.80 (12) | Mn1—Mn2—N8—C24 | 122.2 (3) |
O1—Mn1—Mn2—N7 | 169.16 (19) | O1i—Mn2—N8—C28 | −105.6 (3) |
O1i—Mn1—Mn2—N7 | −10.84 (19) | O1—Mn2—N8—C28 | −18.3 (4) |
N3i—Mn1—Mn2—N7 | −28.5 (2) | N8i—Mn2—N8—C28 | 118.4 (3) |
N3—Mn1—Mn2—N7 | 151.5 (2) | N7—Mn2—N8—C28 | 160.9 (4) |
N4—Mn1—Mn2—N7 | 76.28 (18) | N7i—Mn2—N8—C28 | 76.8 (4) |
N4i—Mn1—Mn2—N7 | −103.72 (18) | Mn1—Mn2—N8—C28 | −61.6 (3) |
O1—Mn1—Mn2—N7i | −10.85 (19) | C9—N3—C8—C8i | −157.3 (5) |
O1i—Mn1—Mn2—N7i | 169.16 (19) | Mn1—N3—C8—C8i | −38.4 (5) |
N3i—Mn1—Mn2—N7i | 151.5 (2) | C8—N3—C9—C10 | 72.2 (4) |
N3—Mn1—Mn2—N7i | −28.5 (2) | Mn1—N3—C9—C10 | −46.6 (4) |
N4—Mn1—Mn2—N7i | −103.72 (18) | C14—N4—C10—C11 | 0.2 (6) |
N4i—Mn1—Mn2—N7i | 76.28 (18) | Mn1—N4—C10—C11 | −176.0 (4) |
O1i—Mn2—O1—Mn1 | 0.0 | C14—N4—C10—C9 | 180.0 (4) |
N8i—Mn2—O1—Mn1 | 93.56 (14) | Mn1—N4—C10—C9 | 3.8 (5) |
N8—Mn2—O1—Mn1 | −99.76 (14) | N3—C9—C10—N4 | 27.8 (5) |
N7i—Mn2—O1—Mn1 | 172.76 (13) | N3—C9—C10—C11 | −152.4 (4) |
O1i—Mn1—O1—Mn2 | 0.0 | N4—C10—C11—C12 | 1.1 (7) |
N3i—Mn1—O1—Mn2 | −100.2 (6) | C9—C10—C11—C12 | −178.6 (5) |
N3—Mn1—O1—Mn2 | 168.26 (13) | C10—C11—C12—C13 | −1.6 (8) |
N4—Mn1—O1—Mn2 | 92.73 (13) | C11—C12—C13—C14 | 0.7 (9) |
N4i—Mn1—O1—Mn2 | −96.94 (14) | C10—N4—C14—C13 | −1.1 (6) |
O1—Mn1—N3—C9 | −58.3 (3) | Mn1—N4—C14—C13 | 174.5 (3) |
O1i—Mn1—N3—C9 | 40.6 (7) | C12—C13—C14—N4 | 0.7 (8) |
N3i—Mn1—N3—C9 | 133.6 (3) | C23—N7—C22—C22i | −89.3 (6) |
N4—Mn1—N3—C9 | 37.3 (3) | Mn2—N7—C22—C22i | 34.5 (7) |
N4i—Mn1—N3—C9 | −152.2 (3) | C22—N7—C23—C24 | 86.1 (5) |
Mn2—Mn1—N3—C9 | −46.4 (3) | Mn2—N7—C23—C24 | −37.8 (5) |
O1—Mn1—N3—C8 | −178.4 (3) | C28—N8—C24—C25 | 0.7 (7) |
O1i—Mn1—N3—C8 | −79.5 (7) | Mn2—N8—C24—C25 | 177.1 (4) |
N3i—Mn1—N3—C8 | 13.5 (2) | C28—N8—C24—C23 | −178.4 (4) |
N4—Mn1—N3—C8 | −82.8 (3) | Mn2—N8—C24—C23 | −2.0 (5) |
N4i—Mn1—N3—C8 | 87.7 (3) | N7—C23—C24—N8 | 26.9 (6) |
Mn2—Mn1—N3—C8 | −166.5 (2) | N7—C23—C24—C25 | −152.2 (5) |
O1—Mn1—N4—C10 | 72.2 (3) | N8—C24—C25—C26 | 0.2 (9) |
O1i—Mn1—N4—C10 | 157.4 (3) | C23—C24—C25—C26 | 179.1 (6) |
N3i—Mn1—N4—C10 | −105.2 (3) | C24—C25—C26—C27 | −2.8 (11) |
N3—Mn1—N4—C10 | −23.3 (3) | C25—C26—C27—C28 | 4.5 (10) |
N4i—Mn1—N4—C10 | −65.0 (3) | C26—C27—C28—N8 | −3.6 (8) |
Mn2—Mn1—N4—C10 | 114.9 (3) | C24—N8—C28—C27 | 1.1 (7) |
O1—Mn1—N4—C14 | −103.6 (3) | Mn2—N8—C28—C27 | −174.9 (4) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
(I_180K) | (I_295K) | |
Crystal data | ||
Chemical formula | [Mn2O2(C14H18N4)2](ClO4)3·6H2O | [Mn2O2(C14H18N4)2](ClO4)3·6H2O |
Mr | 1032.97 | 1032.97 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, C2/c |
Temperature (K) | 180 | 295 |
a, b, c (Å) | 15.1204 (9), 12.2337 (7), 23.6514 (16) | 15.4488 (7), 12.2792 (5), 23.7512 (10) |
β (°) | 105.912 (2) | 106.852 (2) |
V (Å3) | 4207.4 (5) | 4312.1 (3) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.88 | 0.86 |
Crystal size (mm) | 0.25 × 0.20 × 0.05 | 0.25 × 0.20 × 0.05 |
Data collection | ||
Diffractometer | Bruker Nonius X8 APEXII CCD area-detector diffractometer | Bruker Nonius X8 APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.874, 0.957 | 0.832, 0.958 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 82186, 8600, 6203 | 34341, 4424, 3026 |
Rint | 0.036 | 0.069 |
(sin θ/λ)max (Å−1) | 0.626 | 0.626 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.158, 1.09 | 0.067, 0.235, 1.07 |
No. of reflections | 8600 | 4424 |
No. of parameters | 578 | 298 |
No. of restraints | 57 | 30 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.19, −0.83 | 0.92, −0.70 |
Computer programs: APEX2 (Bruker Nonius, 2004), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O1W | 0.93 | 2.05 | 2.952 (4) | 162.2 |
N3—H3B···O2W | 0.93 | 2.09 | 2.964 (4) | 155.1 |
N6—H6C···O2Wi | 0.93 | 2.00 | 2.882 (4) | 158.0 |
N7—H7C···O1Wii | 0.93 | 2.05 | 2.901 (4) | 151.3 |
O1W—H2···O3A | 0.85 | 2.35 | 3.094 (4) | 146.8 |
O1W—H2···O3D | 0.85 | 2.29 | 3.075 (6) | 153.0 |
O1W—H1···O1Biii | 0.85 | 2.23 | 3.047 (6) | 160.5 |
O1W—H1···O1Diii | 0.85 | 2.33 | 2.990 (5) | 135.1 |
O2W—H4···O3W | 0.85 | 2.19 | 2.858 (6) | 135.7 |
O2W—H3···O2Aiv | 0.85 | 2.05 | 2.852 (6) | 157.2 |
O3W—H6···O6W | 0.85 | 1.87 | 2.716 (9) | 175.1 |
O3W—H5···O1 | 0.85 | 1.97 | 2.806 (4) | 166.8 |
O4W—H7···O1Av | 0.85 | 2.24 | 2.918 (5) | 136.8 |
O4W—H8···O3Bvi | 0.85 | 2.08 | 2.899 (5) | 161.2 |
O5W—H9···O3Cvi | 0.85 | 2.13 | 2.977 (7) | 176.8 |
O5W—H10···O2Gvii | 0.85 | 2.32 | 3.129 (15) | 159.7 |
O6W—H12···O4W | 0.85 | 1.87 | 2.717 (8) | 177.0 |
O6W—H11···O5W | 0.85 | 1.72 | 2.548 (12) | 163.6 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) x−1, y, z; (vi) x−1/2, −y+1/2, z+1/2; (vii) x+1/2, −y+1/2, z+1/2. |
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The crystal structure of the title compound, (I), at 295 K has been reported previously (Collins et al., 1987). The compound was described as a trihydrate in space group C2/c, with the MnIII/MnIV complex lying on a twofold rotation axis passing through both of its Mn atoms. In that description, one perchlorate anion and one solvent water molecule have 0.50 site occupancy, which prompted Collins et al. to comment that there must be either `significant thermal motion or some disorder' in the crystal structure. We have synthesized (I) in the course of our research concerning dinuclear Mn complexes (see, for example, Poulsen et al., 2005), and we have observed that the compound undergoes an order–disorder phase transition, adopting an ordered structure in the subgroup P21/n at 180 K.
In the P21/n description (referred to hereinafter as the LT structure), the MnIII/MnIV complexes (Fig. 1) are sited on general positions and each perchlorate anion is fully occupied, although one exhibits rotational disorder typical for this pseudo-spherical anion. Six solvent water molecules are clearly evident per formula unit, so that (I) should be described as a hexahydrate rather than as a trihydrate. In the C2/c description (referred to hereinafter as the HT structure), the additional crystallographic twofold axes (running parallel to b) pass through both Mn atoms of each MnIII/MnIV complex. The primitive lattice of the LT structure is indicated unambiguously by the X-ray data at 180 K, with 2388 out of 4520 unique h+k odd reflections observed at the 3σ(I) level. For the same crystal at 295 K, only 98 such reflections are observed [mean I/σ(I) = 0.6], indicating that the C2/c structure is appropriate at room temperature.
The origin of the disorder in the HT structure is clarified by comparison with the LT structure. The MnIII/MnIV complexes are essentially indistinguishable at the two temperatures (Fig. 2), i.e. the complex maintains twofold rotational symmetry in the LT structure, but the twofold rotation axes are not operators of the P21/n space group. The perchlorate anions containing atoms Cl1 and Cl2 in the LT structure correspond to atoms Cl2i and Cl2 in the HT structure [symmetry code: (i) 1 - x, y, 1/2 - z; Fig. 3]. The anion containing atom Cl3 in the LT structure corresponds to atom Cl3 in the HT structure. However, the symmetry-generated atom Cl3i in the HT structure has no corresponding anion in the LT structure. Hence, the perchlorate anion containing atom Cl3 must have half-occupancy in the C2/c description.
In their work, Collins et al. (1987) located only some of the solvent water molecules. Atoms O1W and O2W in the LT structure correspond to the full-occupancy water molecule in the Collins HT structure, while atom O5W in the LT structure corresponds to the half-occupancy water molecule. The remainder of the solvent water molecules are situated around the site of the `missing' perchlorate anion in the LT structure [close to (0.254, 0.310, 0.399)], which would correspond to the site of atom Cl3i in the HT structure. Thus, these water molecules appear in the HT structure as partial atoms in the vicinity of the perchlorate anion containing atom Cl3. Under these circumstances, it is understandable that they were not included by Collins et al. In our 295 K data, all of the O atoms identified in the LT structure are evident in difference Fourier maps, with the exception of atom O6W, which lies close to the Cl3—O3B bond (ca 0.7 Å from atom Cl3; Fig. 3). We note, however, that our interpretation of the HT Fourier maps to identify these water molecules could only be made with knowledge of the LT structure. The positions of the solvent water molecules in the final refined HT structure closely resemble those in the LT structure, suggesting that the O—H···O hydrogen-bond network (Table 1) remains comparable at 180 and 295 K.
As implied by the statement of Collins et al. (1987), averaging of the LT structure to give the HT structure could in principle originate from static disorder of perchlorate anion Cl3 and several of the water molecules. However, the fact that the same single crystal displays the order–disorder transition, and that it is reversible, shows that the averaging must be a result of thermal motion. Since the geometry of the MnIII/MnIV complex does not change significantly from 180 to 295 K, and the positions of the solvent water molecules also appear to be comparable at the two temperatures, the significant factor must be the thermal motion of the perchlorate anions. For the anions containing atoms Cl1 and Cl2, which are inequivalent in the LT structure but become equivalent in the HT structure, the movement required for this is very slight. The most important group in the system is the perchlorate anion containing atom Cl3. In principle, this continues to break the C2/c symmetry in the HT structure, but its influence is apparently diminished by the scattering contributions of solvent water molecules O3W, O4W, O5W and O6W in the symmetry-related site near to (0.254, 0.310, 0.399). At 180 K, the difference between these two sites is detectable. At 295 K, where the thermal motion of both the perchlorate anions and the solvent water molecules is greater, the sites appear from the X-ray data to be effectively equivalent.