Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104007668/av1176sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104007668/av1176Isup2.hkl |
CCDC reference: 241217
All chemicals were of reagent grade and commercially available from the Beijing Chemical Reagents Company of China, and were used without further purification. DTPB was synthesized by refluxing diethylenetriaminepentaacetic acid and 1,2-diaminobenzene in a 1:5 molar ratio in glycol for 30 h, followed by precipitation of the crude product with water and purification by recrystallization from hot absolute ethanol. DTPB (0.1 mmol) was dissolved in methanol (8 ml) and MnCl2 (0.2 mmol) was dissolved in water (2 ml). The two solutions were mixed and stirred 30 min at room temperature. After filtration, the filtrate was left at room temperature and crystals of (I) appeared from the solution after three months, by slow evaporation of the mixed solvent.
H atoms attached to C, N and methanol O atoms were placed in geometrically idealized positions, with Csp3—H = 0.97 (0.96 for methanol), Csp2—H = 0.93, Nsp2—H = 0.86 and Osp3—H = 0.82 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(parent atom) [1.5Ueq(C) for methanol]. H atoms attached to water O atoms were located from difference Fourier maps and their global Uiso values were refined. The O—H distances are in the range 0.814–0.824 Å. After several cycles, these H atoms were constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(O).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2000); program(s) used to refine structure: SHELXL97 (Sheldrick, 2000); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.
[Mn2Cl4(C44H43N15)]·5CH4O·4H2O | Z = 2 |
Mr = 1237.87 | F(000) = 1292 |
Triclinic, P1 | Dx = 1.372 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 14.254 (3) Å | Cell parameters from 3090 reflections |
b = 15.173 (3) Å | θ = 2.2–27.1° |
c = 15.852 (3) Å | µ = 0.66 mm−1 |
α = 72.882 (3)° | T = 183 K |
β = 67.976 (2)° | Block, light yellow |
γ = 75.191 (3)° | 0.30 × 0.30 × 0.20 mm |
V = 2996.5 (10) Å3 |
Bruker SMART 1K CCD area-detector diffractometer | 10238 independent reflections |
Radiation source: fine-focus sealed tube | 6528 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −16→16 |
Tmin = 0.826, Tmax = 0.879 | k = −16→18 |
12285 measured reflections | l = −11→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.075 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.199 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.1017P)2] where P = (Fo2 + 2Fc2)/3 |
10238 reflections | (Δ/σ)max < 0.001 |
704 parameters | Δρmax = 1.23 e Å−3 |
1 restraint | Δρmin = −0.93 e Å−3 |
[Mn2Cl4(C44H43N15)]·5CH4O·4H2O | γ = 75.191 (3)° |
Mr = 1237.87 | V = 2996.5 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 14.254 (3) Å | Mo Kα radiation |
b = 15.173 (3) Å | µ = 0.66 mm−1 |
c = 15.852 (3) Å | T = 183 K |
α = 72.882 (3)° | 0.30 × 0.30 × 0.20 mm |
β = 67.976 (2)° |
Bruker SMART 1K CCD area-detector diffractometer | 10238 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 6528 reflections with I > 2σ(I) |
Tmin = 0.826, Tmax = 0.879 | Rint = 0.033 |
12285 measured reflections |
R[F2 > 2σ(F2)] = 0.075 | 1 restraint |
wR(F2) = 0.199 | H-atom parameters constrained |
S = 1.00 | Δρmax = 1.23 e Å−3 |
10238 reflections | Δρmin = −0.93 e Å−3 |
704 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.75434 (6) | −0.04090 (5) | 0.27722 (5) | 0.0258 (2) | |
Mn2 | 0.36591 (6) | 0.27709 (6) | 0.01460 (6) | 0.0294 (2) | |
N1 | 0.8325 (3) | −0.0142 (3) | 0.1248 (3) | 0.0265 (10) | |
N2 | 0.8705 (3) | −0.0546 (3) | −0.0093 (3) | 0.0335 (11) | |
H2 | 0.8797 | −0.0888 | −0.0474 | 0.040* | |
N3 | 0.8587 (3) | −0.1660 (3) | 0.3236 (3) | 0.0299 (10) | |
N4 | 0.9012 (4) | −0.3207 (3) | 0.3588 (3) | 0.0406 (12) | |
H4A | 0.8985 | −0.3786 | 0.3665 | 0.049* | |
N5 | 0.6209 (3) | −0.0781 (3) | 0.4049 (3) | 0.0297 (10) | |
N6 | 0.4571 (3) | −0.0964 (3) | 0.4645 (3) | 0.0300 (10) | |
H6A | 0.3935 | −0.0887 | 0.4698 | 0.036* | |
N7 | 0.7351 (3) | −0.1708 (3) | 0.2296 (3) | 0.0261 (10) | |
N8 | 0.5995 (3) | 0.0161 (3) | 0.2289 (3) | 0.0240 (9) | |
N9 | 0.5320 (3) | 0.2132 (3) | 0.0394 (3) | 0.0262 (10) | |
N10 | 0.4045 (3) | 0.3842 (3) | 0.0581 (3) | 0.0290 (10) | |
N11 | 0.5049 (4) | 0.4215 (3) | 0.1162 (3) | 0.0340 (11) | |
H11 | 0.5589 | 0.4214 | 0.1284 | 0.041* | |
N12 | 0.4939 (3) | 0.2787 (3) | −0.1264 (3) | 0.0273 (10) | |
N13 | 0.6285 (3) | 0.1885 (3) | −0.2042 (3) | 0.0338 (11) | |
H13A | 0.6817 | 0.1458 | −0.2144 | 0.041* | |
Cl1 | 0.79568 (13) | 0.08677 (11) | 0.30929 (10) | 0.0471 (4) | |
Cl2 | 0.23334 (13) | 0.37411 (12) | −0.04861 (13) | 0.0565 (5) | |
Cl3 | 0.35238 (11) | 0.11576 (10) | 0.02164 (9) | 0.0368 (4) | |
Cl4 | 0.24673 (13) | 0.24651 (12) | 0.19224 (12) | 0.0554 (5) | |
C1 | 0.8391 (4) | −0.0815 (4) | 0.0846 (4) | 0.0306 (13) | |
C2 | 0.8146 (4) | −0.1758 (4) | 0.1382 (4) | 0.0316 (13) | |
H2A | 0.7905 | −0.2023 | 0.1028 | 0.038* | |
H2B | 0.8762 | −0.2165 | 0.1476 | 0.038* | |
C3 | 0.8612 (4) | 0.0618 (4) | 0.0520 (4) | 0.0299 (13) | |
C4 | 0.8850 (4) | 0.0363 (4) | −0.0334 (4) | 0.0332 (13) | |
C5 | 0.9118 (4) | 0.1005 (4) | −0.1189 (4) | 0.0423 (15) | |
H5 | 0.9273 | 0.0835 | −0.1750 | 0.051* | |
C6 | 0.9140 (5) | 0.1880 (5) | −0.1166 (4) | 0.0461 (16) | |
H6 | 0.9312 | 0.2322 | −0.1724 | 0.055* | |
C7 | 0.8911 (4) | 0.2145 (4) | −0.0322 (4) | 0.0434 (15) | |
H7 | 0.8941 | 0.2754 | −0.0338 | 0.052* | |
C8 | 0.8640 (4) | 0.1513 (4) | 0.0537 (4) | 0.0355 (14) | |
H8 | 0.8486 | 0.1689 | 0.1096 | 0.043* | |
C9 | 0.8382 (4) | −0.2463 (4) | 0.3273 (4) | 0.0315 (13) | |
C10 | 0.7527 (4) | −0.2540 (4) | 0.2989 (4) | 0.0343 (13) | |
H10A | 0.7704 | −0.3089 | 0.2731 | 0.041* | |
H10B | 0.6910 | −0.2599 | 0.3527 | 0.041* | |
C11 | 0.9434 (4) | −0.1883 (4) | 0.3552 (3) | 0.0296 (12) | |
C12 | 0.9710 (4) | −0.2855 (4) | 0.3762 (4) | 0.0365 (14) | |
C13 | 1.0552 (5) | −0.3291 (5) | 0.4053 (5) | 0.0494 (17) | |
H13 | 1.0747 | −0.3937 | 0.4172 | 0.059* | |
C14 | 1.1079 (5) | −0.2714 (5) | 0.4156 (5) | 0.0536 (18) | |
H14 | 1.1638 | −0.2979 | 0.4368 | 0.064* | |
C15 | 1.0812 (5) | −0.1749 (5) | 0.3955 (4) | 0.0483 (17) | |
H15 | 1.1203 | −0.1392 | 0.4032 | 0.058* | |
C16 | 0.9991 (4) | −0.1295 (4) | 0.3644 (4) | 0.0380 (14) | |
H16 | 0.9819 | −0.0647 | 0.3506 | 0.046* | |
C17 | 0.5297 (4) | −0.0527 (4) | 0.3941 (3) | 0.0275 (12) | |
C18 | 0.5089 (4) | 0.0190 (4) | 0.3138 (3) | 0.0299 (12) | |
H18A | 0.4506 | 0.0077 | 0.3032 | 0.036* | |
H18B | 0.4920 | 0.0804 | 0.3275 | 0.036* | |
C19 | 0.6060 (4) | −0.1442 (4) | 0.4909 (3) | 0.0320 (13) | |
C20 | 0.5039 (4) | −0.1557 (4) | 0.5267 (4) | 0.0322 (13) | |
C21 | 0.4665 (5) | −0.2188 (4) | 0.6095 (4) | 0.0438 (15) | |
H21 | 0.3981 | −0.2269 | 0.6330 | 0.053* | |
C22 | 0.5358 (6) | −0.2692 (4) | 0.6557 (4) | 0.0493 (17) | |
H22 | 0.5143 | −0.3135 | 0.7106 | 0.059* | |
C23 | 0.6366 (5) | −0.2543 (4) | 0.6209 (4) | 0.0500 (17) | |
H23 | 0.6807 | −0.2873 | 0.6546 | 0.060* | |
C24 | 0.6731 (5) | −0.1928 (4) | 0.5392 (4) | 0.0424 (15) | |
H24 | 0.7411 | −0.1839 | 0.5166 | 0.051* | |
C25 | 0.6309 (4) | −0.1528 (4) | 0.2239 (4) | 0.0313 (13) | |
H25A | 0.5827 | −0.1682 | 0.2862 | 0.038* | |
H25B | 0.6279 | −0.1935 | 0.1881 | 0.038* | |
C26 | 0.5988 (4) | −0.0521 (3) | 0.1788 (4) | 0.0285 (12) | |
H26A | 0.6448 | −0.0380 | 0.1152 | 0.034* | |
H26B | 0.5303 | −0.0449 | 0.1763 | 0.034* | |
C27 | 0.6044 (4) | 0.1097 (3) | 0.1667 (3) | 0.0267 (12) | |
H27A | 0.6641 | 0.1053 | 0.1115 | 0.032* | |
H27B | 0.6143 | 0.1507 | 0.1983 | 0.032* | |
C28 | 0.5101 (4) | 0.1547 (4) | 0.1355 (3) | 0.0267 (12) | |
H28A | 0.4752 | 0.1055 | 0.1402 | 0.032* | |
H28B | 0.4635 | 0.1931 | 0.1785 | 0.032* | |
C29 | 0.4969 (4) | 0.3669 (3) | 0.0667 (3) | 0.0269 (12) | |
C30 | 0.5787 (4) | 0.2938 (4) | 0.0279 (4) | 0.0299 (12) | |
H30A | 0.6288 | 0.2750 | 0.0604 | 0.036* | |
H30B | 0.6134 | 0.3175 | −0.0377 | 0.036* | |
C31 | 0.3479 (4) | 0.4552 (4) | 0.1065 (4) | 0.0340 (13) | |
C32 | 0.4105 (5) | 0.4778 (4) | 0.1440 (4) | 0.0333 (13) | |
C33 | 0.3744 (6) | 0.5429 (4) | 0.1986 (4) | 0.0500 (18) | |
H33 | 0.4157 | 0.5571 | 0.2247 | 0.060* | |
C34 | 0.2738 (6) | 0.5857 (4) | 0.2124 (5) | 0.0554 (19) | |
H34 | 0.2466 | 0.6301 | 0.2488 | 0.067* | |
C35 | 0.2127 (6) | 0.5652 (4) | 0.1744 (5) | 0.0558 (19) | |
H35 | 0.1456 | 0.5967 | 0.1848 | 0.067* | |
C36 | 0.2481 (5) | 0.4988 (4) | 0.1210 (4) | 0.0473 (16) | |
H36 | 0.2060 | 0.4844 | 0.0959 | 0.057* | |
C37 | 0.5705 (4) | 0.2106 (4) | −0.1213 (4) | 0.0286 (12) | |
C38 | 0.5925 (4) | 0.1593 (4) | −0.0324 (3) | 0.0300 (13) | |
H38A | 0.5740 | 0.0974 | −0.0128 | 0.036* | |
H38B | 0.6650 | 0.1525 | −0.0419 | 0.036* | |
C39 | 0.5023 (4) | 0.3050 (4) | −0.2211 (4) | 0.0323 (13) | |
C40 | 0.5852 (4) | 0.2484 (4) | −0.2696 (4) | 0.0337 (13) | |
C41 | 0.6122 (5) | 0.2539 (5) | −0.3650 (4) | 0.0474 (17) | |
H41 | 0.6669 | 0.2141 | −0.3964 | 0.057* | |
C42 | 0.5502 (5) | 0.3241 (5) | −0.4094 (4) | 0.0526 (18) | |
H42 | 0.5646 | 0.3318 | −0.4732 | 0.063* | |
C43 | 0.4684 (5) | 0.3827 (5) | −0.3625 (4) | 0.0484 (17) | |
H43 | 0.4302 | 0.4289 | −0.3955 | 0.058* | |
C44 | 0.4421 (5) | 0.3738 (4) | −0.2666 (4) | 0.0401 (15) | |
H44 | 0.3865 | 0.4125 | −0.2347 | 0.048* | |
C45 | 0.0647 (7) | 0.1034 (6) | 0.3753 (6) | 0.077 (2) | |
H45A | 0.0333 | 0.0528 | 0.4210 | 0.116* | |
H45B | 0.0445 | 0.1162 | 0.3210 | 0.116* | |
H45C | 0.0431 | 0.1581 | 0.4009 | 0.116* | |
O1 | 0.1669 (5) | 0.0800 (4) | 0.3516 (4) | 0.0801 (16) | |
H1 | 0.1935 | 0.1265 | 0.3214 | 0.120* | |
C46 | 0.7616 (9) | 0.3675 (8) | 0.1622 (11) | 0.169 (6) | |
H46A | 0.7501 | 0.3578 | 0.2277 | 0.254* | |
H46B | 0.8265 | 0.3880 | 0.1273 | 0.254* | |
H46C | 0.7619 | 0.3099 | 0.1483 | 0.254* | |
O2 | 0.6825 (4) | 0.4362 (4) | 0.1377 (5) | 0.0879 (18) | |
H2C | 0.6930 | 0.4882 | 0.1337 | 0.132* | |
C47 | 0.7277 (7) | 0.5237 (6) | 0.5200 (6) | 0.086 (3) | |
H47A | 0.7401 | 0.4863 | 0.5764 | 0.129* | |
H47B | 0.6738 | 0.5035 | 0.5117 | 0.129* | |
H47C | 0.7078 | 0.5881 | 0.5240 | 0.129* | |
O3 | 0.8176 (6) | 0.5137 (5) | 0.4437 (5) | 0.121 (2) | |
H3 | 0.8025 | 0.5234 | 0.3963 | 0.182* | |
C48 | 0.9806 (6) | 0.7502 (5) | 0.8627 (6) | 0.074 (2) | |
H48A | 1.0456 | 0.7715 | 0.8360 | 0.111* | |
H48B | 0.9734 | 0.7190 | 0.8214 | 0.111* | |
H48C | 0.9769 | 0.7076 | 0.9217 | 0.111* | |
O4 | 0.9034 (4) | 0.8251 (4) | 0.8753 (4) | 0.0767 (16) | |
H4 | 0.8505 | 0.8120 | 0.8766 | 0.115* | |
C49 | 0.0954 (9) | 0.3903 (8) | 0.3668 (7) | 0.119 (4) | |
H49A | 0.0447 | 0.4386 | 0.3933 | 0.178* | |
H49B | 0.1592 | 0.4132 | 0.3326 | 0.178* | |
H49C | 0.1049 | 0.3373 | 0.4157 | 0.178* | |
O5 | 0.0635 (5) | 0.3641 (6) | 0.3079 (7) | 0.129 (3) | |
H5A | 0.1112 | 0.3310 | 0.2772 | 0.194* | |
O6 | 0.2518 (3) | 0.9373 (3) | 0.4754 (3) | 0.0537 (12) | |
H6B | 0.2214 | 0.9829 | 0.4475 | 0.064* | |
H6C | 0.2435 | 0.8893 | 0.4680 | 0.064* | |
O7 | 0.7564 (4) | 0.0200 (3) | 0.7917 (3) | 0.0893 (18) | |
H7A | 0.7111 | 0.0157 | 0.7734 | 0.107* | |
H7B | 0.7480 | −0.0113 | 0.8449 | 0.107* | |
O8 | 0.8282 (9) | 0.3373 (13) | 0.3674 (6) | 0.336 (11) | |
H8A | 0.8784 | 0.3558 | 0.3653 | 0.404* | |
H8B | 0.8338 | 0.2803 | 0.3857 | 0.404* | |
O9 | 0.9522 (9) | 0.5630 (13) | 0.1464 (10) | 0.313 (9) | |
H9A | 0.9595 | 0.6155 | 0.1134 | 0.375* | |
H9B | 0.9866 | 0.5234 | 0.1163 | 0.375* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0300 (5) | 0.0262 (5) | 0.0223 (4) | −0.0085 (3) | −0.0084 (4) | −0.0038 (3) |
Mn2 | 0.0303 (5) | 0.0286 (5) | 0.0304 (5) | −0.0063 (4) | −0.0102 (4) | −0.0066 (4) |
N1 | 0.028 (2) | 0.029 (3) | 0.023 (2) | −0.009 (2) | −0.007 (2) | −0.0043 (19) |
N2 | 0.037 (3) | 0.038 (3) | 0.024 (3) | −0.004 (2) | −0.007 (2) | −0.012 (2) |
N3 | 0.031 (3) | 0.033 (3) | 0.024 (2) | −0.006 (2) | −0.008 (2) | −0.0032 (19) |
N4 | 0.047 (3) | 0.028 (3) | 0.048 (3) | −0.003 (2) | −0.023 (3) | −0.003 (2) |
N5 | 0.038 (3) | 0.032 (3) | 0.018 (2) | −0.007 (2) | −0.012 (2) | 0.0004 (19) |
N6 | 0.030 (2) | 0.034 (3) | 0.023 (2) | −0.010 (2) | −0.006 (2) | −0.002 (2) |
N7 | 0.028 (2) | 0.026 (2) | 0.024 (2) | −0.0074 (19) | −0.010 (2) | −0.0001 (19) |
N8 | 0.029 (2) | 0.025 (2) | 0.019 (2) | −0.0060 (19) | −0.009 (2) | −0.0032 (18) |
N9 | 0.030 (2) | 0.022 (2) | 0.022 (2) | −0.0069 (19) | −0.006 (2) | 0.0004 (18) |
N10 | 0.034 (3) | 0.026 (2) | 0.027 (2) | −0.005 (2) | −0.011 (2) | −0.0039 (19) |
N11 | 0.047 (3) | 0.033 (3) | 0.028 (3) | −0.022 (2) | −0.013 (2) | −0.001 (2) |
N12 | 0.033 (3) | 0.027 (3) | 0.021 (2) | −0.008 (2) | −0.008 (2) | −0.0023 (19) |
N13 | 0.034 (3) | 0.039 (3) | 0.024 (2) | −0.002 (2) | −0.006 (2) | −0.009 (2) |
Cl1 | 0.0639 (10) | 0.0434 (9) | 0.0406 (9) | −0.0236 (8) | −0.0128 (8) | −0.0119 (7) |
Cl2 | 0.0513 (10) | 0.0547 (11) | 0.0662 (12) | −0.0077 (8) | −0.0313 (9) | −0.0021 (9) |
Cl3 | 0.0460 (8) | 0.0365 (8) | 0.0325 (8) | −0.0132 (7) | −0.0114 (7) | −0.0104 (6) |
Cl4 | 0.0505 (10) | 0.0609 (11) | 0.0517 (10) | −0.0143 (8) | −0.0068 (8) | −0.0164 (8) |
C1 | 0.025 (3) | 0.035 (3) | 0.032 (3) | −0.001 (2) | −0.011 (3) | −0.008 (3) |
C2 | 0.033 (3) | 0.030 (3) | 0.035 (3) | −0.003 (2) | −0.012 (3) | −0.013 (2) |
C3 | 0.018 (3) | 0.039 (3) | 0.027 (3) | −0.001 (2) | −0.004 (2) | −0.004 (2) |
C4 | 0.024 (3) | 0.036 (3) | 0.031 (3) | −0.002 (2) | −0.002 (3) | −0.006 (3) |
C5 | 0.040 (4) | 0.046 (4) | 0.024 (3) | −0.005 (3) | 0.000 (3) | 0.002 (3) |
C6 | 0.040 (4) | 0.053 (4) | 0.028 (3) | −0.015 (3) | −0.001 (3) | 0.010 (3) |
C7 | 0.040 (4) | 0.038 (4) | 0.048 (4) | −0.013 (3) | −0.011 (3) | 0.000 (3) |
C8 | 0.037 (3) | 0.039 (4) | 0.030 (3) | −0.018 (3) | −0.006 (3) | −0.003 (3) |
C9 | 0.035 (3) | 0.030 (3) | 0.028 (3) | −0.006 (3) | −0.010 (3) | −0.002 (2) |
C10 | 0.047 (3) | 0.027 (3) | 0.031 (3) | −0.012 (3) | −0.017 (3) | 0.000 (2) |
C11 | 0.028 (3) | 0.042 (3) | 0.018 (3) | −0.007 (3) | −0.008 (2) | −0.005 (2) |
C12 | 0.037 (3) | 0.037 (4) | 0.037 (3) | −0.002 (3) | −0.015 (3) | −0.009 (3) |
C13 | 0.050 (4) | 0.043 (4) | 0.059 (4) | 0.004 (3) | −0.031 (4) | −0.008 (3) |
C14 | 0.040 (4) | 0.068 (5) | 0.055 (4) | 0.010 (3) | −0.027 (3) | −0.017 (4) |
C15 | 0.036 (4) | 0.073 (5) | 0.044 (4) | −0.012 (3) | −0.015 (3) | −0.018 (3) |
C16 | 0.038 (3) | 0.046 (4) | 0.028 (3) | −0.012 (3) | −0.007 (3) | −0.006 (3) |
C17 | 0.029 (3) | 0.032 (3) | 0.021 (3) | −0.004 (2) | −0.009 (2) | −0.005 (2) |
C18 | 0.030 (3) | 0.031 (3) | 0.023 (3) | −0.005 (2) | −0.005 (2) | −0.002 (2) |
C19 | 0.048 (4) | 0.028 (3) | 0.018 (3) | −0.007 (3) | −0.010 (3) | −0.001 (2) |
C20 | 0.039 (3) | 0.033 (3) | 0.022 (3) | −0.010 (3) | −0.005 (3) | −0.004 (2) |
C21 | 0.057 (4) | 0.038 (4) | 0.027 (3) | −0.017 (3) | 0.000 (3) | −0.004 (3) |
C22 | 0.073 (5) | 0.032 (4) | 0.029 (3) | −0.007 (3) | −0.009 (4) | 0.002 (3) |
C23 | 0.062 (5) | 0.052 (4) | 0.025 (3) | 0.009 (3) | −0.018 (3) | −0.005 (3) |
C24 | 0.046 (4) | 0.052 (4) | 0.026 (3) | −0.001 (3) | −0.014 (3) | −0.007 (3) |
C25 | 0.036 (3) | 0.029 (3) | 0.037 (3) | −0.012 (3) | −0.016 (3) | −0.007 (2) |
C26 | 0.029 (3) | 0.034 (3) | 0.028 (3) | −0.008 (2) | −0.013 (3) | −0.007 (2) |
C27 | 0.030 (3) | 0.026 (3) | 0.021 (3) | −0.008 (2) | −0.008 (2) | 0.001 (2) |
C28 | 0.029 (3) | 0.030 (3) | 0.019 (3) | −0.012 (2) | −0.005 (2) | −0.001 (2) |
C29 | 0.037 (3) | 0.024 (3) | 0.018 (3) | −0.015 (2) | −0.006 (2) | 0.003 (2) |
C30 | 0.028 (3) | 0.031 (3) | 0.028 (3) | −0.008 (2) | −0.010 (3) | 0.000 (2) |
C31 | 0.042 (3) | 0.025 (3) | 0.027 (3) | −0.003 (3) | −0.006 (3) | −0.003 (2) |
C32 | 0.047 (4) | 0.024 (3) | 0.026 (3) | −0.019 (3) | −0.004 (3) | −0.001 (2) |
C33 | 0.084 (5) | 0.037 (4) | 0.034 (4) | −0.037 (4) | −0.009 (4) | −0.006 (3) |
C34 | 0.076 (5) | 0.034 (4) | 0.044 (4) | −0.016 (4) | 0.004 (4) | −0.015 (3) |
C35 | 0.057 (4) | 0.035 (4) | 0.053 (4) | 0.002 (3) | 0.000 (4) | −0.011 (3) |
C36 | 0.047 (4) | 0.035 (4) | 0.050 (4) | −0.004 (3) | −0.007 (3) | −0.010 (3) |
C37 | 0.031 (3) | 0.030 (3) | 0.025 (3) | −0.014 (3) | −0.006 (3) | −0.005 (2) |
C38 | 0.033 (3) | 0.026 (3) | 0.025 (3) | −0.003 (2) | −0.008 (3) | 0.000 (2) |
C39 | 0.037 (3) | 0.034 (3) | 0.031 (3) | −0.019 (3) | −0.015 (3) | 0.002 (3) |
C40 | 0.037 (3) | 0.042 (4) | 0.027 (3) | −0.019 (3) | −0.007 (3) | −0.009 (3) |
C41 | 0.051 (4) | 0.069 (5) | 0.024 (3) | −0.030 (4) | −0.002 (3) | −0.009 (3) |
C42 | 0.068 (5) | 0.072 (5) | 0.025 (3) | −0.032 (4) | −0.017 (4) | −0.001 (3) |
C43 | 0.070 (5) | 0.049 (4) | 0.036 (4) | −0.024 (4) | −0.031 (4) | 0.007 (3) |
C44 | 0.046 (4) | 0.044 (4) | 0.034 (3) | −0.021 (3) | −0.015 (3) | −0.002 (3) |
C45 | 0.087 (7) | 0.076 (6) | 0.059 (5) | −0.032 (5) | −0.009 (5) | −0.005 (4) |
O1 | 0.091 (4) | 0.068 (4) | 0.059 (4) | −0.015 (3) | −0.012 (3) | 0.003 (3) |
C46 | 0.203 (15) | 0.108 (10) | 0.211 (16) | −0.029 (11) | −0.105 (13) | −0.004 (10) |
O2 | 0.074 (4) | 0.075 (4) | 0.122 (5) | −0.040 (3) | −0.020 (4) | −0.025 (4) |
C47 | 0.087 (6) | 0.079 (6) | 0.072 (6) | −0.021 (5) | −0.006 (5) | −0.007 (5) |
O3 | 0.153 (7) | 0.073 (4) | 0.103 (5) | −0.036 (4) | 0.004 (5) | −0.013 (4) |
C48 | 0.048 (4) | 0.074 (6) | 0.110 (7) | 0.004 (4) | −0.028 (5) | −0.045 (5) |
O4 | 0.053 (3) | 0.093 (4) | 0.102 (4) | −0.011 (3) | −0.018 (3) | −0.059 (3) |
C49 | 0.112 (9) | 0.126 (10) | 0.086 (8) | −0.011 (7) | 0.004 (7) | −0.030 (7) |
O5 | 0.094 (5) | 0.142 (7) | 0.157 (8) | −0.007 (5) | −0.021 (5) | −0.077 (6) |
O6 | 0.053 (3) | 0.057 (3) | 0.057 (3) | −0.007 (2) | −0.026 (2) | −0.011 (2) |
O7 | 0.099 (4) | 0.055 (3) | 0.061 (3) | −0.002 (3) | 0.009 (3) | 0.008 (3) |
O8 | 0.214 (12) | 0.63 (3) | 0.093 (7) | 0.153 (14) | −0.050 (8) | −0.160 (11) |
O9 | 0.176 (10) | 0.56 (3) | 0.355 (17) | −0.050 (13) | −0.132 (12) | −0.277 (18) |
Mn1—N1 | 2.209 (4) | C20—C21 | 1.386 (7) |
Mn1—N3 | 2.217 (4) | C21—C22 | 1.387 (9) |
Mn1—N5 | 2.241 (4) | C21—H21 | 0.9300 |
Mn1—Cl1 | 2.3972 (16) | C22—C23 | 1.384 (9) |
Mn1—N7 | 2.416 (4) | C22—H22 | 0.9300 |
Mn1—N8 | 2.472 (4) | C23—C24 | 1.360 (8) |
Mn2—N10 | 2.195 (4) | C23—H23 | 0.9300 |
Mn2—N12 | 2.293 (4) | C24—H24 | 0.9300 |
Mn2—Cl2 | 2.4231 (17) | C25—C26 | 1.517 (7) |
Mn2—N9 | 2.450 (4) | C25—H25A | 0.9700 |
Mn2—Cl3 | 2.4710 (16) | C25—H25B | 0.9700 |
Mn2—Cl4 | 2.6604 (19) | C26—H26A | 0.9700 |
N1—C1 | 1.322 (7) | C26—H26B | 0.9700 |
N1—C3 | 1.390 (6) | C27—C28 | 1.532 (7) |
N2—C1 | 1.349 (6) | C27—H27A | 0.9700 |
N2—C4 | 1.368 (7) | C27—H27B | 0.9700 |
N2—H2 | 0.8600 | C28—H28A | 0.9700 |
N3—C9 | 1.304 (7) | C28—H28B | 0.9700 |
N3—C11 | 1.402 (6) | C29—C30 | 1.474 (7) |
N4—C9 | 1.347 (7) | C30—H30A | 0.9700 |
N4—C12 | 1.384 (7) | C30—H30B | 0.9700 |
N4—H4A | 0.8600 | C31—C36 | 1.370 (8) |
N5—C17 | 1.320 (6) | C31—C32 | 1.393 (7) |
N5—C19 | 1.412 (6) | C32—C33 | 1.378 (8) |
N6—C17 | 1.343 (6) | C33—C34 | 1.378 (9) |
N6—C20 | 1.374 (6) | C33—H33 | 0.9300 |
N6—H6A | 0.8600 | C34—C35 | 1.363 (9) |
N7—C10 | 1.446 (6) | C34—H34 | 0.9300 |
N7—C25 | 1.472 (6) | C35—C36 | 1.382 (9) |
N7—C2 | 1.476 (6) | C35—H35 | 0.9300 |
N8—C18 | 1.477 (6) | C36—H36 | 0.9300 |
N8—C27 | 1.472 (6) | C37—C38 | 1.501 (7) |
N8—C26 | 1.482 (6) | C38—H38A | 0.9700 |
N9—C28 | 1.482 (6) | C38—H38B | 0.9700 |
N9—C38 | 1.470 (7) | C39—C44 | 1.382 (8) |
N9—C30 | 1.471 (6) | C39—C40 | 1.383 (8) |
N10—C29 | 1.325 (6) | C40—C41 | 1.395 (8) |
N10—C31 | 1.408 (7) | C41—C42 | 1.399 (9) |
N11—C29 | 1.346 (6) | C41—H41 | 0.9300 |
N11—C32 | 1.387 (7) | C42—C43 | 1.383 (9) |
N11—H11 | 0.8600 | C42—H42 | 0.9300 |
N12—C37 | 1.306 (6) | C43—C44 | 1.396 (8) |
N12—C39 | 1.402 (6) | C43—H43 | 0.9300 |
N13—C37 | 1.351 (7) | C44—H44 | 0.9300 |
N13—C40 | 1.386 (7) | C45—O1 | 1.339 (9) |
N13—H13A | 0.8600 | C45—H45A | 0.9600 |
C1—C2 | 1.487 (7) | C45—H45B | 0.9600 |
C2—H2A | 0.9700 | C45—H45C | 0.9600 |
C2—H2B | 0.9700 | O1—H1 | 0.8200 |
C3—C8 | 1.378 (8) | C46—O2 | 1.413 (5) |
C3—C4 | 1.411 (8) | C46—H46A | 0.9600 |
C4—C5 | 1.399 (7) | C46—H46B | 0.9600 |
C5—C6 | 1.348 (9) | C46—H46C | 0.9600 |
C5—H5 | 0.9300 | O2—H2C | 0.8200 |
C6—C7 | 1.406 (9) | C47—O3 | 1.405 (10) |
C6—H6 | 0.9300 | C47—H47A | 0.9600 |
C7—C8 | 1.397 (8) | C47—H47B | 0.9600 |
C7—H7 | 0.9300 | C47—H47C | 0.9600 |
C8—H8 | 0.9300 | O3—H3 | 0.8200 |
C9—C10 | 1.489 (7) | C48—O4 | 1.368 (8) |
C10—H10A | 0.9700 | C48—H48A | 0.9600 |
C10—H10B | 0.9700 | C48—H48B | 0.9600 |
C11—C16 | 1.404 (8) | C48—H48C | 0.9600 |
C11—C12 | 1.398 (7) | O4—H4 | 0.8200 |
C12—C13 | 1.387 (8) | C49—O5 | 1.366 (12) |
C13—C14 | 1.367 (9) | C49—H49A | 0.9600 |
C13—H13 | 0.9300 | C49—H49B | 0.9600 |
C14—C15 | 1.386 (9) | C49—H49C | 0.9600 |
C14—H14 | 0.9300 | O5—H5A | 0.8200 |
C15—C16 | 1.381 (8) | O6—H6B | 0.8199 |
C15—H15 | 0.9300 | O6—H6C | 0.8143 |
C16—H16 | 0.9300 | O7—H7A | 0.8237 |
C17—C18 | 1.482 (7) | O7—H7B | 0.8175 |
C18—H18A | 0.9700 | O8—H8A | 0.8193 |
C18—H18B | 0.9700 | O8—H8B | 0.8204 |
C19—C24 | 1.378 (7) | O9—H9A | 0.8229 |
C19—C20 | 1.387 (7) | O9—H9B | 0.8188 |
N1—Mn1—N3 | 100.34 (16) | N8—C18—H18B | 109.6 |
N1—Mn1—N5 | 152.36 (15) | C17—C18—H18B | 109.6 |
N3—Mn1—N5 | 92.41 (15) | H18A—C18—H18B | 108.1 |
N1—Mn1—Cl1 | 98.83 (12) | C24—C19—C20 | 120.6 (5) |
N3—Mn1—Cl1 | 105.20 (12) | C24—C19—N5 | 131.1 (5) |
N5—Mn1—Cl1 | 101.34 (12) | C20—C19—N5 | 108.3 (4) |
N1—Mn1—N7 | 75.06 (14) | C21—C20—N6 | 131.6 (5) |
N3—Mn1—N7 | 71.96 (15) | C21—C20—C19 | 121.8 (5) |
N5—Mn1—N7 | 85.94 (15) | N6—C20—C19 | 106.7 (4) |
Cl1—Mn1—N7 | 172.38 (11) | C20—C21—C22 | 116.8 (6) |
N1—Mn1—N8 | 82.27 (14) | C20—C21—H21 | 121.6 |
N3—Mn1—N8 | 145.44 (15) | C22—C21—H21 | 121.6 |
N5—Mn1—N8 | 73.55 (14) | C21—C22—C23 | 120.8 (6) |
Cl1—Mn1—N8 | 108.44 (11) | C21—C22—H22 | 119.6 |
N7—Mn1—N8 | 75.60 (13) | C23—C22—H22 | 119.6 |
N10—Mn2—N12 | 99.01 (15) | C24—C23—C22 | 122.1 (6) |
N10—Mn2—Cl2 | 98.56 (12) | C24—C23—H23 | 118.9 |
N12—Mn2—Cl2 | 95.94 (12) | C22—C23—H23 | 118.9 |
N10—Mn2—N9 | 73.46 (15) | C23—C24—C19 | 117.9 (6) |
N12—Mn2—N9 | 70.17 (14) | C23—C24—H24 | 121.1 |
Cl2—Mn2—N9 | 162.09 (10) | C19—C24—H24 | 121.1 |
N10—Mn2—Cl3 | 154.63 (12) | N7—C25—C26 | 112.8 (4) |
N12—Mn2—Cl3 | 89.55 (11) | N7—C25—H25A | 109.0 |
Cl2—Mn2—Cl3 | 104.28 (6) | C26—C25—H25A | 109.0 |
N9—Mn2—Cl3 | 87.33 (10) | N7—C25—H25B | 109.0 |
N10—Mn2—Cl4 | 81.38 (12) | C26—C25—H25B | 109.0 |
N12—Mn2—Cl4 | 167.53 (12) | H25A—C25—H25B | 107.8 |
Cl2—Mn2—Cl4 | 96.32 (6) | N8—C26—C25 | 113.5 (4) |
N9—Mn2—Cl4 | 98.23 (10) | N8—C26—H26A | 108.9 |
Cl3—Mn2—Cl4 | 85.25 (5) | C25—C26—H26A | 108.9 |
C1—N1—C3 | 105.5 (4) | N8—C26—H26B | 108.9 |
C1—N1—Mn1 | 115.3 (3) | C25—C26—H26B | 108.9 |
C3—N1—Mn1 | 137.7 (4) | H26A—C26—H26B | 107.7 |
C1—N2—C4 | 108.0 (5) | N8—C27—C28 | 115.4 (4) |
C1—N2—H2 | 126.0 | N8—C27—H27A | 108.4 |
C4—N2—H2 | 126.0 | C28—C27—H27A | 108.4 |
C9—N3—C11 | 105.1 (4) | N8—C27—H27B | 108.4 |
C9—N3—Mn1 | 115.7 (3) | C28—C27—H27B | 108.4 |
C11—N3—Mn1 | 139.2 (4) | H27A—C27—H27B | 107.5 |
C9—N4—C12 | 106.5 (5) | N9—C28—C27 | 115.1 (4) |
C9—N4—H4A | 126.7 | N9—C28—H28A | 108.5 |
C12—N4—H4A | 126.7 | C27—C28—H28A | 108.5 |
C17—N5—C19 | 104.8 (4) | N9—C28—H28B | 108.5 |
C17—N5—Mn1 | 116.1 (3) | C27—C28—H28B | 108.5 |
C19—N5—Mn1 | 136.3 (4) | H28A—C28—H28B | 107.5 |
C17—N6—C20 | 107.0 (4) | N10—C29—N11 | 112.3 (5) |
C17—N6—H6A | 126.5 | N10—C29—C30 | 122.5 (5) |
C20—N6—H6A | 126.5 | N11—C29—C30 | 125.1 (5) |
C10—N7—C25 | 112.6 (4) | C29—C30—N9 | 108.5 (4) |
C10—N7—C2 | 110.2 (4) | C29—C30—H30A | 110.0 |
C25—N7—C2 | 111.9 (4) | N9—C30—H30A | 110.0 |
C10—N7—Mn1 | 106.8 (3) | C29—C30—H30B | 110.0 |
C25—N7—Mn1 | 107.8 (3) | N9—C30—H30B | 110.0 |
C2—N7—Mn1 | 107.2 (3) | H30A—C30—H30B | 108.4 |
C18—N8—C27 | 110.5 (4) | C36—C31—C32 | 121.0 (6) |
C18—N8—C26 | 111.4 (4) | C36—C31—N10 | 130.5 (6) |
C27—N8—C26 | 110.3 (4) | C32—C31—N10 | 108.6 (5) |
C18—N8—Mn1 | 108.1 (3) | C33—C32—N11 | 132.5 (6) |
C27—N8—Mn1 | 110.4 (3) | C33—C32—C31 | 121.7 (6) |
C26—N8—Mn1 | 106.0 (3) | N11—C32—C31 | 105.9 (5) |
C28—N9—C38 | 113.0 (4) | C32—C33—C34 | 116.4 (6) |
C28—N9—C30 | 112.2 (4) | C32—C33—H33 | 121.8 |
C38—N9—C30 | 111.6 (4) | C34—C33—H33 | 121.8 |
C28—N9—Mn2 | 106.5 (3) | C35—C34—C33 | 122.2 (6) |
C38—N9—Mn2 | 106.5 (3) | C35—C34—H34 | 118.9 |
C30—N9—Mn2 | 106.5 (3) | C33—C34—H34 | 118.9 |
C29—N10—C31 | 105.6 (4) | C34—C35—C36 | 121.6 (7) |
C29—N10—Mn2 | 116.2 (3) | C34—C35—H35 | 119.2 |
C31—N10—Mn2 | 135.1 (4) | C36—C35—H35 | 119.2 |
C29—N11—C32 | 107.7 (4) | C31—C36—C35 | 117.2 (7) |
C29—N11—H11 | 126.2 | C31—C36—H36 | 121.4 |
C32—N11—H11 | 126.2 | C35—C36—H36 | 121.4 |
C37—N12—C39 | 104.8 (4) | N12—C37—N13 | 113.8 (5) |
C37—N12—Mn2 | 112.2 (3) | N12—C37—C38 | 124.1 (5) |
C39—N12—Mn2 | 137.5 (3) | N13—C37—C38 | 122.1 (5) |
C37—N13—C40 | 106.3 (5) | N9—C38—C37 | 108.3 (4) |
C37—N13—H13A | 126.8 | N9—C38—H38A | 110.0 |
C40—N13—H13A | 126.8 | C37—C38—H38A | 110.0 |
N1—C1—N2 | 112.5 (5) | N9—C38—H38B | 110.0 |
N1—C1—C2 | 123.0 (5) | C37—C38—H38B | 110.0 |
N2—C1—C2 | 124.5 (5) | H38A—C38—H38B | 108.4 |
N7—C2—C1 | 110.9 (4) | C44—C39—C40 | 120.8 (5) |
N7—C2—H2A | 109.5 | C44—C39—N12 | 130.0 (6) |
C1—C2—H2A | 109.5 | C40—C39—N12 | 109.2 (4) |
N7—C2—H2B | 109.5 | N13—C40—C39 | 105.9 (5) |
C1—C2—H2B | 109.5 | N13—C40—C41 | 130.4 (6) |
H2A—C2—H2B | 108.0 | C39—C40—C41 | 123.7 (6) |
N1—C3—C8 | 130.3 (5) | C42—C41—C40 | 114.4 (6) |
N1—C3—C4 | 108.8 (5) | C42—C41—H41 | 122.8 |
C8—C3—C4 | 120.8 (5) | C40—C41—H41 | 122.8 |
N2—C4—C5 | 133.0 (6) | C41—C42—C43 | 122.7 (6) |
N2—C4—C3 | 105.3 (4) | C41—C42—H42 | 118.6 |
C5—C4—C3 | 121.6 (6) | C43—C42—H42 | 118.6 |
C6—C5—C4 | 117.2 (6) | C42—C43—C44 | 121.3 (6) |
C6—C5—H5 | 121.4 | C42—C43—H43 | 119.4 |
C4—C5—H5 | 121.4 | C44—C43—H43 | 119.4 |
C5—C6—C7 | 122.0 (5) | C39—C44—C43 | 117.1 (6) |
C5—C6—H6 | 119.0 | C39—C44—H44 | 121.5 |
C7—C6—H6 | 119.0 | C43—C44—H44 | 121.5 |
C8—C7—C6 | 121.5 (6) | O1—C45—H45A | 109.5 |
C8—C7—H7 | 119.2 | O1—C45—H45B | 109.5 |
C6—C7—H7 | 119.2 | H45A—C45—H45B | 109.5 |
C7—C8—C3 | 116.9 (6) | O1—C45—H45C | 109.5 |
C7—C8—H8 | 121.6 | H45A—C45—H45C | 109.5 |
C3—C8—H8 | 121.6 | H45B—C45—H45C | 109.5 |
N3—C9—N4 | 113.9 (5) | C45—O1—H1 | 109.5 |
N3—C9—C10 | 122.5 (5) | O2—C46—H46A | 109.5 |
N4—C9—C10 | 123.6 (5) | O2—C46—H46B | 109.5 |
N7—C10—C9 | 108.5 (4) | H46A—C46—H46B | 109.5 |
N7—C10—H10A | 110.0 | O2—C46—H46C | 109.5 |
C9—C10—H10A | 110.0 | H46A—C46—H46C | 109.5 |
N7—C10—H10B | 110.0 | H46B—C46—H46C | 109.5 |
C9—C10—H10B | 110.0 | C46—O2—H2C | 109.5 |
H10A—C10—H10B | 108.4 | O3—C47—H47A | 109.5 |
C16—C11—N3 | 130.1 (5) | O3—C47—H47B | 109.5 |
C16—C11—C12 | 121.3 (5) | H47A—C47—H47B | 109.5 |
N3—C11—C12 | 108.6 (5) | O3—C47—H47C | 109.5 |
N4—C12—C13 | 131.9 (6) | H47A—C47—H47C | 109.5 |
N4—C12—C11 | 105.8 (5) | H47B—C47—H47C | 109.5 |
C13—C12—C11 | 122.3 (5) | C47—O3—H3 | 109.5 |
C14—C13—C12 | 116.0 (6) | O4—C48—H48A | 109.5 |
C14—C13—H13 | 122.0 | O4—C48—H48B | 109.5 |
C12—C13—H13 | 122.0 | H48A—C48—H48B | 109.5 |
C13—C14—C15 | 122.3 (6) | O4—C48—H48C | 109.5 |
C13—C14—H14 | 118.8 | H48A—C48—H48C | 109.5 |
C15—C14—H14 | 118.8 | H48B—C48—H48C | 109.5 |
C14—C15—C16 | 122.9 (6) | C48—O4—H4 | 109.5 |
C14—C15—H15 | 118.5 | O5—C49—H49A | 109.5 |
C16—C15—H15 | 118.5 | O5—C49—H49B | 109.5 |
C11—C16—C15 | 115.1 (6) | H49A—C49—H49B | 109.5 |
C11—C16—H16 | 122.4 | O5—C49—H49C | 109.5 |
C15—C16—H16 | 122.4 | H49A—C49—H49C | 109.5 |
N5—C17—N6 | 113.2 (4) | H49B—C49—H49C | 109.5 |
N5—C17—C18 | 123.3 (5) | C49—O5—H5A | 109.5 |
N6—C17—C18 | 123.5 (4) | H6B—O6—H6C | 110.2 |
N8—C18—C17 | 110.4 (4) | H7A—O7—H7B | 109.4 |
N8—C18—H18A | 109.6 | H8A—O8—H8B | 110.8 |
C17—C18—H18A | 109.6 | H9A—O9—H9B | 109.8 |
N3—Mn1—N1—C1 | 62.5 (4) | Mn1—N3—C9—C10 | 2.2 (7) |
N5—Mn1—N1—C1 | −53.7 (5) | C12—N4—C9—N3 | −1.0 (7) |
Cl1—Mn1—N1—C1 | 169.8 (3) | C12—N4—C9—C10 | 179.0 (5) |
N7—Mn1—N1—C1 | −5.6 (3) | C25—N7—C10—C9 | −157.3 (4) |
N8—Mn1—N1—C1 | −82.6 (4) | C2—N7—C10—C9 | 77.0 (5) |
N3—Mn1—N1—C3 | −134.0 (5) | Mn1—N7—C10—C9 | −39.1 (5) |
N5—Mn1—N1—C3 | 109.9 (5) | N3—C9—C10—N7 | 27.8 (7) |
Cl1—Mn1—N1—C3 | −26.7 (5) | N4—C9—C10—N7 | −152.1 (5) |
N7—Mn1—N1—C3 | 158.0 (5) | C9—N3—C11—C16 | 178.8 (5) |
N8—Mn1—N1—C3 | 80.9 (5) | Mn1—N3—C11—C16 | −3.8 (9) |
N1—Mn1—N3—C9 | −88.9 (4) | C9—N3—C11—C12 | 0.6 (6) |
N5—Mn1—N3—C9 | 66.5 (4) | Mn1—N3—C11—C12 | 178.0 (4) |
Cl1—Mn1—N3—C9 | 168.9 (3) | C9—N4—C12—C13 | −176.7 (6) |
N7—Mn1—N3—C9 | −18.5 (4) | C9—N4—C12—C11 | 1.2 (6) |
N8—Mn1—N3—C9 | 2.5 (5) | C16—C11—C12—N4 | −179.5 (5) |
N1—Mn1—N3—C11 | 93.9 (5) | N3—C11—C12—N4 | −1.1 (6) |
N5—Mn1—N3—C11 | −110.7 (5) | C16—C11—C12—C13 | −1.3 (9) |
Cl1—Mn1—N3—C11 | −8.3 (5) | N3—C11—C12—C13 | 177.1 (5) |
N7—Mn1—N3—C11 | 164.3 (5) | N4—C12—C13—C14 | 180.0 (6) |
N8—Mn1—N3—C11 | −174.7 (4) | C11—C12—C13—C14 | 2.3 (9) |
N1—Mn1—N5—C17 | −30.6 (6) | C12—C13—C14—C15 | −1.9 (10) |
N3—Mn1—N5—C17 | −148.4 (4) | C13—C14—C15—C16 | 0.6 (10) |
Cl1—Mn1—N5—C17 | 105.5 (4) | N3—C11—C16—C15 | −178.2 (5) |
N7—Mn1—N5—C17 | −76.7 (4) | C12—C11—C16—C15 | −0.1 (8) |
N8—Mn1—N5—C17 | −0.6 (4) | C14—C15—C16—C11 | 0.5 (9) |
N1—Mn1—N5—C19 | 127.3 (5) | C19—N5—C17—N6 | −0.4 (6) |
N3—Mn1—N5—C19 | 9.4 (5) | Mn1—N5—C17—N6 | 164.0 (3) |
Cl1—Mn1—N5—C19 | −96.6 (5) | C19—N5—C17—C18 | 177.8 (5) |
N7—Mn1—N5—C19 | 81.2 (5) | Mn1—N5—C17—C18 | −17.8 (7) |
N8—Mn1—N5—C19 | 157.3 (5) | C20—N6—C17—N5 | −0.3 (6) |
N1—Mn1—N7—C10 | 138.1 (3) | C20—N6—C17—C18 | −178.5 (5) |
N3—Mn1—N7—C10 | 31.7 (3) | C27—N8—C18—C17 | −149.7 (4) |
N5—Mn1—N7—C10 | −62.2 (3) | C26—N8—C18—C17 | 87.3 (5) |
N8—Mn1—N7—C10 | −136.3 (3) | Mn1—N8—C18—C17 | −28.7 (5) |
N1—Mn1—N7—C25 | −100.7 (3) | N5—C17—C18—N8 | 33.4 (7) |
N3—Mn1—N7—C25 | 152.9 (3) | N6—C17—C18—N8 | −148.6 (5) |
N5—Mn1—N7—C25 | 59.0 (3) | C17—N5—C19—C24 | −178.3 (6) |
N8—Mn1—N7—C25 | −15.0 (3) | Mn1—N5—C19—C24 | 22.2 (9) |
N1—Mn1—N7—C2 | 19.9 (3) | C17—N5—C19—C20 | 0.9 (6) |
N3—Mn1—N7—C2 | −86.5 (3) | Mn1—N5—C19—C20 | −158.6 (4) |
N5—Mn1—N7—C2 | 179.7 (3) | C17—N6—C20—C21 | −178.0 (6) |
N8—Mn1—N7—C2 | 105.6 (3) | C17—N6—C20—C19 | 0.9 (6) |
N1—Mn1—N8—C18 | −176.9 (3) | C24—C19—C20—C21 | −2.8 (9) |
N3—Mn1—N8—C18 | 86.1 (4) | N5—C19—C20—C21 | 177.9 (5) |
N5—Mn1—N8—C18 | 16.6 (3) | C24—C19—C20—N6 | 178.2 (5) |
Cl1—Mn1—N8—C18 | −80.1 (3) | N5—C19—C20—N6 | −1.1 (6) |
N7—Mn1—N8—C18 | 106.6 (3) | N6—C20—C21—C22 | 179.5 (6) |
N1—Mn1—N8—C27 | −55.9 (3) | C19—C20—C21—C22 | 0.8 (9) |
N3—Mn1—N8—C27 | −152.9 (3) | C20—C21—C22—C23 | 1.8 (9) |
N5—Mn1—N8—C27 | 137.6 (3) | C21—C22—C23—C24 | −2.5 (10) |
Cl1—Mn1—N8—C27 | 40.9 (3) | C22—C23—C24—C19 | 0.5 (10) |
N7—Mn1—N8—C27 | −132.4 (3) | C20—C19—C24—C23 | 2.1 (9) |
N1—Mn1—N8—C26 | 63.6 (3) | N5—C19—C24—C23 | −178.8 (6) |
N3—Mn1—N8—C26 | −33.5 (4) | C10—N7—C25—C26 | 159.8 (4) |
N5—Mn1—N8—C26 | −102.9 (3) | C2—N7—C25—C26 | −75.4 (5) |
Cl1—Mn1—N8—C26 | 160.3 (3) | Mn1—N7—C25—C26 | 42.2 (5) |
N7—Mn1—N8—C26 | −12.9 (3) | C18—N8—C26—C25 | −77.1 (5) |
N10—Mn2—N9—C28 | 95.7 (3) | C27—N8—C26—C25 | 159.8 (4) |
N12—Mn2—N9—C28 | −157.9 (3) | Mn1—N8—C26—C25 | 40.3 (5) |
Cl2—Mn2—N9—C28 | 161.3 (3) | N7—C25—C26—N8 | −59.4 (6) |
Cl3—Mn2—N9—C28 | −67.5 (3) | C18—N8—C27—C28 | −57.6 (6) |
Cl4—Mn2—N9—C28 | 17.3 (3) | C26—N8—C27—C28 | 66.0 (6) |
N10—Mn2—N9—C38 | −143.4 (3) | Mn1—N8—C27—C28 | −177.2 (3) |
N12—Mn2—N9—C38 | −37.1 (3) | C38—N9—C28—C27 | 65.0 (6) |
Cl2—Mn2—N9—C38 | −77.8 (5) | C30—N9—C28—C27 | −62.3 (6) |
Cl3—Mn2—N9—C38 | 53.4 (3) | Mn2—N9—C28—C27 | −178.4 (4) |
Cl4—Mn2—N9—C38 | 138.2 (3) | N8—C27—C28—N9 | −145.3 (4) |
N10—Mn2—N9—C30 | −24.1 (3) | C31—N10—C29—N11 | −0.5 (6) |
N12—Mn2—N9—C30 | 82.2 (3) | Mn2—N10—C29—N11 | −163.5 (3) |
Cl2—Mn2—N9—C30 | 41.5 (6) | C31—N10—C29—C30 | 177.8 (4) |
Cl3—Mn2—N9—C30 | 172.7 (3) | Mn2—N10—C29—C30 | 14.8 (6) |
Cl4—Mn2—N9—C30 | −102.5 (3) | C32—N11—C29—N10 | 1.2 (6) |
N12—Mn2—N10—C29 | −59.9 (4) | C32—N11—C29—C30 | −177.0 (5) |
Cl2—Mn2—N10—C29 | −157.4 (3) | N10—C29—C30—N9 | −37.5 (6) |
N9—Mn2—N10—C29 | 6.2 (3) | N11—C29—C30—N9 | 140.6 (5) |
Cl3—Mn2—N10—C29 | 48.5 (5) | C28—N9—C30—C29 | −79.5 (5) |
Cl4—Mn2—N10—C29 | 107.5 (3) | C38—N9—C30—C29 | 152.5 (4) |
N12—Mn2—N10—C31 | 143.5 (5) | Mn2—N9—C30—C29 | 36.7 (4) |
Cl2—Mn2—N10—C31 | 46.1 (5) | C29—N10—C31—C36 | −179.2 (6) |
N9—Mn2—N10—C31 | −150.4 (5) | Mn2—N10—C31—C36 | −21.0 (9) |
Cl3—Mn2—N10—C31 | −108.1 (5) | C29—N10—C31—C32 | −0.4 (5) |
Cl4—Mn2—N10—C31 | −49.1 (4) | Mn2—N10—C31—C32 | 157.8 (4) |
N10—Mn2—N12—C37 | 99.2 (4) | C29—N11—C32—C33 | 176.8 (6) |
Cl2—Mn2—N12—C37 | −161.1 (3) | C29—N11—C32—C31 | −1.4 (5) |
N9—Mn2—N12—C37 | 30.5 (3) | C36—C31—C32—C33 | 1.6 (8) |
Cl3—Mn2—N12—C37 | −56.8 (3) | N10—C31—C32—C33 | −177.3 (5) |
Cl4—Mn2—N12—C37 | 8.4 (8) | C36—C31—C32—N11 | −180.0 (5) |
N10—Mn2—N12—C39 | −112.3 (5) | N10—C31—C32—N11 | 1.1 (5) |
Cl2—Mn2—N12—C39 | −12.6 (5) | N11—C32—C33—C34 | −179.3 (5) |
N9—Mn2—N12—C39 | 179.1 (5) | C31—C32—C33—C34 | −1.4 (8) |
Cl3—Mn2—N12—C39 | 91.7 (5) | C32—C33—C34—C35 | 0.0 (9) |
Cl4—Mn2—N12—C39 | 157.0 (4) | C33—C34—C35—C36 | 1.1 (10) |
C3—N1—C1—N2 | 0.2 (6) | C32—C31—C36—C35 | −0.4 (8) |
Mn1—N1—C1—N2 | 168.8 (3) | N10—C31—C36—C35 | 178.2 (5) |
C3—N1—C1—C2 | −179.9 (4) | C34—C35—C36—C31 | −0.9 (9) |
Mn1—N1—C1—C2 | −11.3 (6) | C39—N12—C37—N13 | −0.7 (6) |
C4—N2—C1—N1 | −0.4 (6) | Mn2—N12—C37—N13 | 158.0 (3) |
C4—N2—C1—C2 | 179.7 (5) | C39—N12—C37—C38 | −179.5 (5) |
C10—N7—C2—C1 | −146.1 (4) | Mn2—N12—C37—C38 | −20.9 (6) |
C25—N7—C2—C1 | 87.7 (5) | C40—N13—C37—N12 | 0.1 (6) |
Mn1—N7—C2—C1 | −30.3 (5) | C40—N13—C37—C38 | 179.0 (4) |
N1—C1—C2—N7 | 30.4 (7) | C28—N9—C38—C37 | 154.6 (4) |
N2—C1—C2—N7 | −149.8 (5) | C30—N9—C38—C37 | −77.8 (5) |
C1—N1—C3—C8 | 176.9 (5) | Mn2—N9—C38—C37 | 38.0 (4) |
Mn1—N1—C3—C8 | 12.3 (8) | N12—C37—C38—N9 | −14.2 (7) |
C1—N1—C3—C4 | 0.0 (6) | N13—C37—C38—N9 | 167.0 (4) |
Mn1—N1—C3—C4 | −164.6 (4) | C37—N12—C39—C44 | −179.6 (5) |
C1—N2—C4—C5 | −176.3 (6) | Mn2—N12—C39—C44 | 30.4 (8) |
C1—N2—C4—C3 | 0.4 (6) | C37—N12—C39—C40 | 1.0 (5) |
N1—C3—C4—N2 | −0.3 (6) | Mn2—N12—C39—C40 | −149.0 (4) |
C8—C3—C4—N2 | −177.5 (4) | C37—N13—C40—C39 | 0.6 (5) |
N1—C3—C4—C5 | 176.9 (5) | C37—N13—C40—C41 | −177.6 (6) |
C8—C3—C4—C5 | −0.4 (8) | C44—C39—C40—N13 | 179.6 (5) |
N2—C4—C5—C6 | 176.4 (6) | N12—C39—C40—N13 | −1.0 (6) |
C3—C4—C5—C6 | 0.1 (8) | C44—C39—C40—C41 | −2.1 (8) |
C4—C5—C6—C7 | 0.3 (9) | N12—C39—C40—C41 | 177.4 (5) |
C5—C6—C7—C8 | −0.5 (9) | N13—C40—C41—C42 | 179.9 (5) |
C6—C7—C8—C3 | 0.3 (8) | C39—C40—C41—C42 | 2.1 (8) |
N1—C3—C8—C7 | −176.4 (5) | C40—C41—C42—C43 | −0.5 (9) |
C4—C3—C8—C7 | 0.2 (8) | C41—C42—C43—C44 | −1.0 (10) |
C11—N3—C9—N4 | 0.3 (6) | C40—C39—C44—C43 | 0.5 (8) |
Mn1—N3—C9—N4 | −177.9 (4) | N12—C39—C44—C43 | −178.9 (5) |
C11—N3—C9—C10 | −179.7 (5) | C42—C43—C44—C39 | 1.0 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7B···Cl3i | 0.82 | 2.44 | 3.163 (5) | 148 |
O6—H6B···O1ii | 0.82 | 2.02 | 2.819 (7) | 166 |
O5—H5A···Cl4 | 0.82 | 2.23 | 3.053 (8) | 177 |
O4—H4···Cl4iii | 0.82 | 2.50 | 3.240 (5) | 152 |
O2—H2C···Cl2iv | 0.82 | 2.39 | 3.134 (6) | 152 |
O1—H1···Cl4 | 0.82 | 2.33 | 3.101 (5) | 157 |
N13—H13A···O7v | 0.86 | 1.93 | 2.737 (7) | 156 |
N11—H11···O2 | 0.86 | 1.90 | 2.749 (7) | 171 |
N6—H6A···O6vi | 0.86 | 1.93 | 2.786 (6) | 176 |
N4—H4A···O3vi | 0.86 | 2.06 | 2.808 (8) | 146 |
N2—H2···O4vii | 0.86 | 1.93 | 2.788 (7) | 175 |
O8—H8A···O5viii | 0.82 | 2.47 | 3.225 (17) | 154 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) x, y, z−1; (vi) x, y−1, z; (vii) x, y−1, z−1; (viii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Mn2Cl4(C44H43N15)]·5CH4O·4H2O |
Mr | 1237.87 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 183 |
a, b, c (Å) | 14.254 (3), 15.173 (3), 15.852 (3) |
α, β, γ (°) | 72.882 (3), 67.976 (2), 75.191 (3) |
V (Å3) | 2996.5 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.66 |
Crystal size (mm) | 0.30 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.826, 0.879 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12285, 10238, 6528 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.075, 0.199, 1.00 |
No. of reflections | 10238 |
No. of parameters | 704 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.23, −0.93 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 2000), SHELXL97 (Sheldrick, 2000), SHELXTL/PC (Sheldrick, 1999), SHELXTL/PC.
Mn1—N1 | 2.209 (4) | Mn2—N10 | 2.195 (4) |
Mn1—N3 | 2.217 (4) | Mn2—N12 | 2.293 (4) |
Mn1—N5 | 2.241 (4) | Mn2—Cl2 | 2.4231 (17) |
Mn1—Cl1 | 2.3972 (16) | Mn2—N9 | 2.450 (4) |
Mn1—N7 | 2.416 (4) | Mn2—Cl3 | 2.4710 (16) |
Mn1—N8 | 2.472 (4) | Mn2—Cl4 | 2.6604 (19) |
N1—Mn1—N3 | 100.34 (16) | N10—Mn2—N12 | 99.01 (15) |
N1—Mn1—N5 | 152.36 (15) | N10—Mn2—Cl2 | 98.56 (12) |
N3—Mn1—N5 | 92.41 (15) | N12—Mn2—Cl2 | 95.94 (12) |
N1—Mn1—Cl1 | 98.83 (12) | N10—Mn2—N9 | 73.46 (15) |
N3—Mn1—Cl1 | 105.20 (12) | N12—Mn2—N9 | 70.17 (14) |
N5—Mn1—Cl1 | 101.34 (12) | Cl2—Mn2—N9 | 162.09 (10) |
N1—Mn1—N7 | 75.06 (14) | N10—Mn2—Cl3 | 154.63 (12) |
N3—Mn1—N7 | 71.96 (15) | N12—Mn2—Cl3 | 89.55 (11) |
N5—Mn1—N7 | 85.94 (15) | Cl2—Mn2—Cl3 | 104.28 (6) |
Cl1—Mn1—N7 | 172.38 (11) | N9—Mn2—Cl3 | 87.33 (10) |
N1—Mn1—N8 | 82.27 (14) | N10—Mn2—Cl4 | 81.38 (12) |
N3—Mn1—N8 | 145.44 (15) | N12—Mn2—Cl4 | 167.53 (12) |
N5—Mn1—N8 | 73.55 (14) | Cl2—Mn2—Cl4 | 96.32 (6) |
Cl1—Mn1—N8 | 108.44 (11) | N9—Mn2—Cl4 | 98.23 (10) |
N7—Mn1—N8 | 75.60 (13) | Cl3—Mn2—Cl4 | 85.25 (5) |
Mn1—N8—C27—C28 | −177.2 (3) | N8—C27—C28—N9 | −145.3 (4) |
Mn2—N9—C28—C27 | −178.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7B···Cl3i | 0.82 | 2.44 | 3.163 (5) | 148 |
O6—H6B···O1ii | 0.82 | 2.02 | 2.819 (7) | 166 |
O5—H5A···Cl4 | 0.82 | 2.23 | 3.053 (8) | 177 |
O4—H4···Cl4iii | 0.82 | 2.50 | 3.240 (5) | 152 |
O2—H2C···Cl2iv | 0.82 | 2.39 | 3.134 (6) | 152 |
O1—H1···Cl4 | 0.82 | 2.33 | 3.101 (5) | 157 |
N13—H13A···O7v | 0.86 | 1.93 | 2.737 (7) | 156 |
N11—H11···O2 | 0.86 | 1.90 | 2.749 (7) | 171 |
N6—H6A···O6vi | 0.86 | 1.93 | 2.786 (6) | 176 |
N4—H4A···O3vi | 0.86 | 2.06 | 2.808 (8) | 146 |
N2—H2···O4vii | 0.86 | 1.93 | 2.788 (7) | 175 |
O8—H8A···O5viii | 0.82 | 2.47 | 3.225 (17) | 154 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y+1, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y+1, −z; (v) x, y, z−1; (vi) x, y−1, z; (vii) x, y−1, z−1; (viii) x+1, y, z. |
In recent years, multinuclear metal complexes contaning multi-benzimidazole have attracted great attention in relation to the superoxide dismutase (SOD) enzyme and nuclease mimics (Liao et al., 2001; Liu et al., 2004). Previous research has showed that some DTPB metal complexes can cleave DNA by a hydrolytic mechanism (Liu et al., 2002). Although the DTPB ligand was first synthesized at a very early date (Reference?), only the complex Zn2(DTPB)Cl4·3H2O has been crystallographically characterized to date (Birker et al., 1981). As a result of the current interest in DTPB-metal complexes, we have crystallized the title MnII—DTPB complex, (I), and we report its crystal structure here. \sch
The geometric parameters of (I) are listed in Table 1 and the molecular conformation is illustrated in Fig. 1. The compound contains an asymmetric dinuclear MnII—DTPB complex with an intra-ligand bridging group (–NCH2CH2N–), as well as several solvate molecules (methanol and water). In this asymmetric dinuclear complex, both MnII cations have similar distorted octahedral coordination geometries. Atom Mn1 is coordinated by a Cl− anion and five N atoms, from three benzimidazole groups and two aliphatic amine groups of the DTPB ligand, leading to a positive charge at the Mn1 coordination moiety. Atom Mn2 is coordinated by three Cl− anions and three N atoms, from the remaining two benzimidazole groups and an aliphatic amine group, giving rise to a negative charge at the Mn2 coordination moiety. Therefore, the whole complex is polar. This is somewhat different from what is seen with Zn2(DTPB)Cl4·3H2O in which the two ZnII atoms have different coordination geometries, one being five-coordinated and the other six-coordinated, resulting in a cationic complex (Birker et al., 1981).
The Mn—N distances in (I) vary to a large extent. The Mn—N bonds between MnII cations and aliphatic amine groups range from 2.416 (4) to 2.472 (4) Å, and these are significantly longer than the Mn—N bonds between MnII cations and benzimidazole groups, with lengths from 2.209 (4) to 2.293 (4) Å. The Mn—Cl bonds towards the apical positions in both octahedra are approximately the same [2.397 (2) and 2.423 (2) Å]. However, in the equatorial plane of the Mn2 octahedron, the two Mn—Cl bonds differ, with lengths of 2.471 (2) and 2.660 (2) Å. All these differences are probably the result of the steric requirements for coordination between the ligand and the two MnII cations. The Mn···Mn distance is 7.94 Å.
The hydrogen-bonding geometry in (I) is listed in Table 2. and illustrated in Fig 2. The crystal structure of (I) is stabilized by many N—H···O, O—H···Cl and O—H···O hydrogen bonds. Each complex links indirectly to neighbouring complexes via Cl2···H—O2i···H—N11i, Cl3···H—O7ii···H—N13iii and Cl4···H—O4iv···H—N2iii hydrogen bonds involving methanol or water molecules [symmetry codes: (i) 1 − x, 1 − y, −z; (ii) 1 − x, −y, 1 − z; (iii) 1 − x, −y, −z; (iv) 1 − x, 1 − y, 1 − z]. The hydrogen bonds focus mainly on the Mn2 coordination moiety compared with the Mn1 coordination moiety. It is worth mentioning that a Cl4···H—O1···H—O6B···H—N6 hydrogen-bond chain is observed, connecting the two parts of complex (I) [symmetry code: (v) x, y − 1, z]. Therefore, complex (I) is not only bridged by an intra-ligand group (–NCH2CH2N–), but also by this hydrogen-bond chain, forming a large ring of 14 atoms and making the complex more stable.