The title compound, [Mn(C
12H
8N
2)
2(H
2O)
2](C
4H
4O
4S)·[Mn(C
4H
4O
4S)(C
12H
8N
2)
2]·13H
2O, contains one dianion of thiodiglycolic acid (tdga
2−) and two independent manganese(II) moieties,
viz. [Mn(phen)
2(H
2O)
2]
2+ and [Mn(tdga)(phen)
2], where phen is 1,10-phenanthroline. The Mn
II atoms are octahedrally coordinated by four N atoms of two bidentate phen ligands [Mn—N = 2.240 (2)–2.3222 (19) Å] and either two water O atoms or two tdga carboxyl O atoms [Mn—O = 2.1214 (17)–2.1512 (17) Å]. The tdga ligand chelates as an
O,
O′-bidentate ligand, forming an eight-membered ring with one Mn atom. The free tdga
2− dianion is hydrogen bonded to an [Mn(phen)
2(H
2O)
2]
2+ ion, with O
O distances of 2.606 (2) and 2.649 (2) Å. The crystal structure is further stabilized by an extensive network of hydrogen bonds involving 13 water molecules.
Supporting information
CCDC reference: 226090
TdgaNa2 (0.19 g), dissolved in distilled water (10 ml), was added to a solution of MnSO4·4H2O (0.22 g) in an ethanol:water (1:1) mixture (30 ml). The reaction mixture was stirred for 30 min at room temperature and then phen·H2O (0.2 g), dissolved in ethanol (20 ml), was added, with stirring, to the solution. The colour of the solution changed to yellow. It was stirred for 1 h and left for crystallization. Yellow crystals suitable for single-crystal X-ray analysis were obtained after several days.
Disordered water molecule O99 (atoms O99A–O99C) was refined isotropically. The large value (14.6) of the Ueq(max)/Ueq(min) ratio for O78 and the fact that the highest peak in the electron-density map was close to this atom led us to refine atom 078 as disordered, with two possible positions. The O78A—C76 [1.320 (4) Å] and O78B—C76 [1.189 (8) Å] bond lengths indicate localization of electron density in the carboxyl moiety insted of an electron dellocalization, such as was found around C atoms C71, C81 and C86. H atoms attached to C atoms were positioned geometrically, with Uiso values derived from Ueq of the corresponding C atoms. The H atoms attached to O atoms were refined freely, ?except for O—H distances, which were restrained to 0.95 Å, and two free variables were used to describe the Uiso(H) values. The first free variable describes Uiso values of the four H atoms attached to atoms O29 and O30, and the second describes Uiso values of H atoms attached to uncoordinated water O atoms.
Data collection: CrysAlis CCD (Oxford Diffraction); cell refinement: CrysAlis RED (Oxford Diffraction); data reduction: CrysAlis RED (Oxford Diffraction); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Johnson & Burnett, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PARST (Nardelli, 1995).
Diaqua-bis(1,10-phenanthroline-N,
N')manganese(II)] [bis(1,10-phenanthroline-
N,
N')(thiodiglycolato-O,
O')manganese(II)] thiodiglycolate tridecahydrate
top
Crystal data top
[Mn(C12H8N2)2(H2O)2][Mn(C12H8N2)2(C4H4O4S)](C4H4O4S)·13H2O | Z = 2 |
Mr = 1393.17 | F(000) = 1448 |
Triclinic, P1 | Dx = 1.457 Mg m−3 |
a = 15.0347 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 15.9870 (7) Å | Cell parameters from 7031 reflections |
c = 16.4562 (8) Å | θ = 5.3–56.5° |
α = 83.501 (4)° | µ = 0.55 mm−1 |
β = 66.004 (5)° | T = 120 K |
γ = 61.981 (5)° | Prism, yellow |
V = 3175.1 (3) Å3 | 0.55 × 0.55 × 0.40 mm |
Data collection top
Kuma KM4 + CCD diffractometer | 9798 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Enhance (Oxford Diffraction) monochromator | θmax = 25.0°, θmin = 3.5° |
Detector resolution: 16.3 pixels mm-1 | h = −17→14 |
rotation method, ω–scan | k = −19→18 |
16741 measured reflections | l = −19→16 |
10803 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.04P)2 + 4P] where P = (Fo2 + 2Fc2)/3 |
10803 reflections | (Δ/σ)max = 0.001 |
901 parameters | Δρmax = 0.87 e Å−3 |
26 restraints | Δρmin = −0.73 e Å−3 |
Crystal data top
[Mn(C12H8N2)2(H2O)2][Mn(C12H8N2)2(C4H4O4S)](C4H4O4S)·13H2O | γ = 61.981 (5)° |
Mr = 1393.17 | V = 3175.1 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 15.0347 (7) Å | Mo Kα radiation |
b = 15.9870 (7) Å | µ = 0.55 mm−1 |
c = 16.4562 (8) Å | T = 120 K |
α = 83.501 (4)° | 0.55 × 0.55 × 0.40 mm |
β = 66.004 (5)° | |
Data collection top
Kuma KM4 + CCD diffractometer | 9798 reflections with I > 2σ(I) |
16741 measured reflections | Rint = 0.032 |
10803 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.039 | 26 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.87 e Å−3 |
10803 reflections | Δρmin = −0.73 e Å−3 |
901 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Mn1 | 0.18320 (3) | 0.06522 (2) | 0.24997 (2) | 0.01501 (9) | |
N1 | 0.17019 (15) | 0.02258 (14) | 0.38791 (13) | 0.0201 (4) | |
C2 | 0.18412 (19) | 0.06148 (19) | 0.44588 (16) | 0.0249 (5) | |
H2 | 0.1974 | 0.1149 | 0.4303 | 0.030* | |
C3 | 0.1802 (2) | 0.0277 (2) | 0.52879 (17) | 0.0324 (6) | |
H3 | 0.1902 | 0.0580 | 0.5684 | 0.039* | |
C4 | 0.1619 (2) | −0.0495 (2) | 0.55223 (17) | 0.0333 (6) | |
H4 | 0.1604 | −0.0740 | 0.6079 | 0.040* | |
C5 | 0.14539 (19) | −0.09216 (18) | 0.49332 (16) | 0.0269 (6) | |
C6 | 0.14888 (18) | −0.05261 (17) | 0.41172 (16) | 0.0203 (5) | |
C7 | 0.12875 (18) | −0.09247 (16) | 0.35075 (16) | 0.0200 (5) | |
C8 | 0.10445 (19) | −0.16903 (17) | 0.37386 (18) | 0.0270 (6) | |
C9 | 0.0843 (2) | −0.20464 (18) | 0.3125 (2) | 0.0326 (6) | |
H9 | 0.0673 | −0.2561 | 0.3258 | 0.039* | |
C10 | 0.0894 (2) | −0.16508 (19) | 0.2338 (2) | 0.0313 (6) | |
H10 | 0.0758 | −0.1884 | 0.1919 | 0.038* | |
C11 | 0.1150 (2) | −0.08946 (18) | 0.21590 (18) | 0.0254 (5) | |
H11 | 0.1192 | −0.0628 | 0.1607 | 0.031* | |
N12 | 0.13375 (15) | −0.05321 (14) | 0.27208 (13) | 0.0198 (4) | |
C13 | 0.1227 (2) | −0.1714 (2) | 0.51371 (18) | 0.0353 (7) | |
H13 | 0.1221 | −0.1992 | 0.5680 | 0.042* | |
C14 | 0.1022 (2) | −0.20724 (19) | 0.45705 (19) | 0.0349 (7) | |
H14 | 0.0859 | −0.2590 | 0.4727 | 0.042* | |
N15 | 0.36567 (15) | −0.04088 (13) | 0.18322 (13) | 0.0178 (4) | |
C16 | 0.4342 (2) | −0.08468 (17) | 0.22370 (18) | 0.0233 (5) | |
H16 | 0.4061 | −0.0720 | 0.2866 | 0.028* | |
C17 | 0.5454 (2) | −0.14829 (18) | 0.1781 (2) | 0.0302 (6) | |
H17 | 0.5914 | −0.1783 | 0.2097 | 0.036* | |
C18 | 0.5869 (2) | −0.16671 (17) | 0.0880 (2) | 0.0299 (6) | |
H18 | 0.6625 | −0.2098 | 0.0562 | 0.036* | |
C19 | 0.51780 (19) | −0.12191 (16) | 0.04194 (18) | 0.0241 (5) | |
C20 | 0.40656 (18) | −0.05880 (15) | 0.09322 (16) | 0.0183 (5) | |
C21 | 0.33211 (19) | −0.01171 (15) | 0.04966 (15) | 0.0178 (5) | |
C22 | 0.3712 (2) | −0.03044 (17) | −0.04351 (16) | 0.0243 (5) | |
C23 | 0.2955 (2) | 0.01749 (19) | −0.08317 (17) | 0.0289 (6) | |
H23 | 0.3184 | 0.0067 | −0.1457 | 0.035* | |
C24 | 0.1888 (2) | 0.07971 (18) | −0.03137 (17) | 0.0260 (5) | |
H24 | 0.1369 | 0.1126 | −0.0573 | 0.031* | |
C25 | 0.1573 (2) | 0.09418 (17) | 0.06043 (16) | 0.0216 (5) | |
H25 | 0.0830 | 0.1377 | 0.0958 | 0.026* | |
N26 | 0.22579 (16) | 0.05029 (13) | 0.10076 (13) | 0.0177 (4) | |
C27 | 0.5550 (2) | −0.13789 (18) | −0.05251 (18) | 0.0300 (6) | |
H27 | 0.6302 | −0.1796 | −0.0872 | 0.036* | |
C28 | 0.4851 (2) | −0.09471 (19) | −0.09327 (17) | 0.0300 (6) | |
H28 | 0.5118 | −0.1071 | −0.1561 | 0.036* | |
O29 | 0.22594 (14) | 0.17202 (11) | 0.25822 (11) | 0.0214 (3) | |
O30 | 0.02314 (13) | 0.17738 (11) | 0.27078 (11) | 0.0203 (3) | |
Mn2 | 0.34653 (3) | 0.43523 (2) | 0.29315 (2) | 0.01581 (9) | |
N40 | 0.26763 (16) | 0.47979 (15) | 0.44001 (13) | 0.0214 (4) | |
C41 | 0.3199 (2) | 0.4580 (2) | 0.49338 (18) | 0.0368 (7) | |
H41 | 0.3977 | 0.4200 | 0.4685 | 0.044* | |
C42 | 0.2663 (2) | 0.4882 (2) | 0.58463 (19) | 0.0395 (5) | |
H42 | 0.3071 | 0.4697 | 0.6207 | 0.047* | |
C43 | 0.1562 (3) | 0.5438 (3) | 0.62124 (18) | 0.0437 (8) | |
H43 | 0.1192 | 0.5659 | 0.6830 | 0.052* | |
C44 | 0.0969 (2) | 0.56885 (19) | 0.56735 (16) | 0.0260 (5) | |
C45 | 0.15637 (19) | 0.53431 (16) | 0.47660 (15) | 0.0184 (5) | |
C46 | 0.09856 (18) | 0.55725 (15) | 0.41927 (15) | 0.0156 (4) | |
C47 | −0.01711 (18) | 0.61422 (16) | 0.45524 (16) | 0.0207 (5) | |
C48 | −0.0704 (2) | 0.63496 (18) | 0.39703 (18) | 0.0276 (6) | |
H48 | −0.1480 | 0.6728 | 0.4186 | 0.033* | |
C49 | −0.0098 (2) | 0.6003 (2) | 0.30913 (19) | 0.0395 (5) | |
H49 | −0.0444 | 0.6143 | 0.2687 | 0.047* | |
C50 | 0.1041 (2) | 0.54391 (18) | 0.27968 (16) | 0.0242 (5) | |
H50 | 0.1453 | 0.5196 | 0.2185 | 0.029* | |
N51 | 0.15814 (15) | 0.52232 (13) | 0.33204 (12) | 0.0175 (4) | |
C52 | −0.0201 (2) | 0.62630 (19) | 0.60153 (17) | 0.0300 (6) | |
H52 | −0.0600 | 0.6495 | 0.6630 | 0.036* | |
C53 | −0.0743 (2) | 0.64789 (18) | 0.54822 (17) | 0.0283 (6) | |
H53 | −0.1519 | 0.6862 | 0.5726 | 0.034* | |
N55 | 0.35629 (15) | 0.57270 (13) | 0.24967 (13) | 0.0193 (4) | |
C56 | 0.36060 (19) | 0.63276 (18) | 0.29592 (18) | 0.0260 (5) | |
H56 | 0.3547 | 0.6211 | 0.3553 | 0.031* | |
C57 | 0.3733 (2) | 0.71228 (19) | 0.2613 (2) | 0.0332 (6) | |
H57 | 0.3804 | 0.7514 | 0.2952 | 0.040* | |
C58 | 0.3754 (2) | 0.73271 (18) | 0.1782 (2) | 0.0334 (6) | |
H58 | 0.3824 | 0.7873 | 0.1541 | 0.040* | |
C59 | 0.36728 (19) | 0.67312 (17) | 0.12770 (18) | 0.0258 (5) | |
C60 | 0.36158 (17) | 0.59181 (16) | 0.16553 (16) | 0.0189 (5) | |
C61 | 0.36112 (17) | 0.52457 (16) | 0.11454 (15) | 0.0189 (5) | |
C62 | 0.35871 (18) | 0.54472 (18) | 0.02987 (16) | 0.0233 (5) | |
C63 | 0.3566 (2) | 0.4774 (2) | −0.01679 (17) | 0.0290 (6) | |
H63 | 0.3541 | 0.4884 | −0.0739 | 0.035* | |
C64 | 0.35826 (19) | 0.39638 (19) | 0.02076 (17) | 0.0272 (6) | |
H64 | 0.3575 | 0.3503 | −0.0103 | 0.033* | |
C65 | 0.36113 (19) | 0.38165 (17) | 0.10521 (16) | 0.0220 (5) | |
H65 | 0.3620 | 0.3250 | 0.1306 | 0.026* | |
N66 | 0.36277 (15) | 0.44346 (13) | 0.15136 (12) | 0.0166 (4) | |
C67 | 0.3653 (2) | 0.69149 (19) | 0.04129 (19) | 0.0334 (6) | |
H67 | 0.3680 | 0.7471 | 0.0160 | 0.040* | |
C68 | 0.3596 (2) | 0.6309 (2) | −0.00502 (18) | 0.0316 (6) | |
H68 | 0.3562 | 0.6456 | −0.0616 | 0.038* | |
O70 | 0.35115 (13) | 0.30005 (11) | 0.29756 (11) | 0.0220 (4) | |
C71 | 0.38647 (18) | 0.22302 (16) | 0.33183 (15) | 0.0178 (5) | |
O72 | 0.36138 (14) | 0.15854 (12) | 0.33165 (12) | 0.0251 (4) | |
C73 | 0.46707 (19) | 0.20517 (18) | 0.37318 (16) | 0.0230 (5) | |
H73A | 0.4545 | 0.1680 | 0.4252 | 0.028* | |
H73B | 0.4548 | 0.2667 | 0.3945 | 0.028* | |
S74 | 0.60761 (5) | 0.14039 (5) | 0.29155 (5) | 0.03045 (16) | |
C75 | 0.6150 (2) | 0.2293 (2) | 0.2141 (2) | 0.0393 (7) | |
H75A | 0.6868 | 0.2012 | 0.1620 | 0.047* | |
H75B | 0.5561 | 0.2502 | 0.1922 | 0.047* | |
C76 | 0.6021 (2) | 0.3144 (2) | 0.2593 (2) | 0.0381 (7) | |
O77 | 0.50852 (13) | 0.38588 (13) | 0.28891 (13) | 0.0304 (4) | |
O78A | 0.6803 (2) | 0.3125 (2) | 0.2784 (3) | 0.0291 (8) | 0.713 (6) |
O78B | 0.6954 (6) | 0.2992 (6) | 0.2300 (7) | 0.0291 (8) | 0.287 (6) |
O80 | 0.17557 (14) | 0.31646 (13) | 0.16440 (12) | 0.0289 (4) | |
C81 | 0.08885 (18) | 0.35378 (16) | 0.15197 (14) | 0.0170 (5) | |
O82 | 0.01625 (13) | 0.32668 (12) | 0.18017 (11) | 0.0219 (4) | |
C83 | 0.06868 (18) | 0.43952 (16) | 0.09804 (15) | 0.0175 (5) | |
H83A | 0.0883 | 0.4826 | 0.1174 | 0.021* | |
H83B | −0.0105 | 0.4750 | 0.1097 | 0.021* | |
S84 | 0.14900 (4) | 0.40401 (4) | −0.02055 (4) | 0.01696 (12) | |
C85 | 0.08272 (19) | 0.34245 (16) | −0.03763 (15) | 0.0181 (5) | |
H85A | 0.0934 | 0.2872 | −0.0018 | 0.022* | |
H85B | 0.0027 | 0.3857 | −0.0165 | 0.022* | |
C86 | 0.12851 (19) | 0.30810 (16) | −0.13558 (15) | 0.0196 (5) | |
O87 | 0.20858 (14) | 0.31790 (13) | −0.19055 (11) | 0.0279 (4) | |
O88 | 0.07963 (14) | 0.27115 (12) | −0.15291 (11) | 0.0262 (4) | |
O101 | 0.87448 (14) | 0.14787 (13) | 0.24969 (13) | 0.0284 (4) | |
O102 | 0.08984 (16) | −0.01325 (14) | −0.13450 (12) | 0.0303 (4) | |
O103 | 0.12401 (16) | −0.10756 (14) | 0.01562 (13) | 0.0330 (4) | |
O105 | 0.31300 (16) | 0.25430 (14) | −0.37118 (13) | 0.0328 (4) | |
O106 | 0.43171 (15) | 0.00191 (14) | 0.42144 (13) | 0.0332 (4) | |
O107 | −0.16938 (15) | 0.37612 (13) | 0.14618 (13) | 0.0311 (4) | |
O108 | 0.5360 (2) | 0.5246 (2) | 0.36989 (17) | 0.0584 (7) | |
O109 | −0.10189 (19) | 0.26808 (18) | −0.01633 (16) | 0.0493 (6) | |
O110 | 0.32419 (17) | 0.43080 (15) | −0.21972 (13) | 0.0369 (5) | |
O111 | 0.17038 (17) | 0.09741 (15) | −0.24180 (14) | 0.0409 (5) | |
O112 | 0.35282 (16) | 0.07258 (15) | 0.59800 (13) | 0.0355 (4) | |
O113 | 0.4634 (2) | −0.1918 (2) | 0.41123 (18) | 0.0636 (7) | |
O99A | 0.3960 (3) | 0.6770 (2) | 0.5175 (2) | 0.0405 (8)* | 0.60 |
O99B | 0.3896 (8) | 0.6079 (7) | 0.5068 (7) | 0.039 (2)* | 0.20 |
O99C | 0.3811 (7) | 0.7609 (6) | 0.5542 (6) | 0.029 (2)* | 0.20 |
H29V | 0.272 (2) | 0.174 (2) | 0.279 (2) | 0.054 (5)* | |
H29W | 0.207 (3) | 0.2233 (19) | 0.226 (2) | 0.054 (5)* | |
H30W | −0.030 (2) | 0.168 (2) | 0.263 (2) | 0.054 (5)* | |
H30V | 0.024 (3) | 0.2296 (19) | 0.240 (2) | 0.054 (5)* | |
H01V | 0.810 (2) | 0.2018 (19) | 0.253 (3) | 0.065 (2)* | |
H01W | 0.892 (3) | 0.104 (2) | 0.206 (2) | 0.065 (2)* | |
H02V | 0.120 (3) | 0.024 (2) | −0.171 (2) | 0.065 (2)* | |
H02W | 0.0187 (19) | 0.029 (2) | −0.093 (2) | 0.065 (2)* | |
H03W | 0.123 (3) | −0.079 (3) | −0.0370 (18) | 0.065 (2)* | |
H03V | 0.127 (3) | −0.1653 (17) | 0.011 (3) | 0.065 (2)* | |
H5V | 0.3833 (19) | 0.245 (3) | −0.386 (3) | 0.065 (2)* | |
H5W | 0.268 (3) | 0.276 (3) | −0.3127 (14) | 0.065 (2)* | |
H6V | 0.5072 (16) | −0.027 (3) | 0.398 (2) | 0.065 (2)* | |
H6W | 0.413 (3) | 0.049 (2) | 0.384 (2) | 0.065 (2)* | |
H7V | −0.110 (2) | 0.361 (3) | 0.159 (3) | 0.065 (2)* | |
H7W | −0.206 (3) | 0.349 (3) | 0.189 (2) | 0.065 (2)* | |
H8V | 0.577 (3) | 0.4674 (18) | 0.340 (3) | 0.065 (2)* | |
H9V | −0.040 (2) | 0.267 (3) | −0.062 (2) | 0.065 (2)* | |
H9W | −0.131 (3) | 0.310 (2) | 0.0331 (19) | 0.065 (2)* | |
H10V | 0.294 (3) | 0.390 (2) | −0.207 (3) | 0.065 (2)* | |
H10W | 0.265 (2) | 0.4903 (17) | −0.192 (2) | 0.065 (2)* | |
H11V | 0.146 (3) | 0.1606 (15) | −0.225 (2) | 0.065 (2)* | |
H11W | 0.233 (2) | 0.082 (3) | −0.2949 (17) | 0.065 (2)* | |
H12W | 0.334 (3) | 0.1372 (15) | 0.599 (3) | 0.065 (2)* | |
H12V | 0.375 (3) | 0.050 (3) | 0.5398 (15) | 0.065 (2)* | |
H13W | 0.439 (3) | −0.1307 (15) | 0.422 (3) | 0.065 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.01477 (17) | 0.01444 (17) | 0.01604 (17) | −0.00634 (14) | −0.00725 (14) | 0.00249 (13) |
N1 | 0.0144 (9) | 0.0226 (10) | 0.0213 (10) | −0.0072 (8) | −0.0075 (8) | 0.0040 (8) |
C2 | 0.0187 (12) | 0.0332 (14) | 0.0218 (12) | −0.0099 (11) | −0.0088 (10) | −0.0014 (10) |
C3 | 0.0215 (13) | 0.0494 (17) | 0.0219 (13) | −0.0124 (12) | −0.0087 (11) | −0.0009 (12) |
C4 | 0.0199 (13) | 0.0466 (17) | 0.0179 (12) | −0.0071 (12) | −0.0053 (10) | 0.0088 (12) |
C5 | 0.0141 (11) | 0.0303 (13) | 0.0204 (12) | −0.0032 (10) | −0.0022 (10) | 0.0065 (10) |
C6 | 0.0099 (10) | 0.0205 (12) | 0.0213 (12) | −0.0029 (9) | −0.0037 (9) | 0.0038 (9) |
C7 | 0.0117 (10) | 0.0172 (11) | 0.0245 (12) | −0.0041 (9) | −0.0050 (9) | 0.0042 (9) |
C8 | 0.0164 (12) | 0.0198 (12) | 0.0335 (14) | −0.0067 (10) | −0.0028 (11) | 0.0057 (10) |
C9 | 0.0243 (13) | 0.0206 (13) | 0.0501 (17) | −0.0136 (11) | −0.0090 (12) | 0.0042 (12) |
C10 | 0.0280 (14) | 0.0272 (14) | 0.0467 (17) | −0.0166 (11) | −0.0176 (13) | 0.0023 (12) |
C11 | 0.0239 (13) | 0.0247 (13) | 0.0335 (14) | −0.0122 (11) | −0.0163 (11) | 0.0053 (11) |
N12 | 0.0162 (9) | 0.0186 (10) | 0.0250 (10) | −0.0075 (8) | −0.0100 (8) | 0.0044 (8) |
C13 | 0.0272 (14) | 0.0335 (15) | 0.0251 (14) | −0.0078 (12) | −0.0028 (11) | 0.0142 (12) |
C14 | 0.0268 (14) | 0.0245 (14) | 0.0372 (16) | −0.0110 (11) | −0.0015 (12) | 0.0114 (12) |
N15 | 0.0178 (10) | 0.0133 (9) | 0.0239 (10) | −0.0078 (8) | −0.0095 (8) | 0.0033 (8) |
C16 | 0.0224 (12) | 0.0197 (12) | 0.0331 (14) | −0.0106 (10) | −0.0161 (11) | 0.0069 (10) |
C17 | 0.0224 (13) | 0.0206 (12) | 0.0516 (17) | −0.0088 (10) | −0.0209 (13) | 0.0067 (12) |
C18 | 0.0149 (12) | 0.0143 (11) | 0.0533 (18) | −0.0052 (10) | −0.0079 (12) | −0.0017 (11) |
C19 | 0.0184 (12) | 0.0138 (11) | 0.0365 (14) | −0.0095 (10) | −0.0041 (11) | −0.0032 (10) |
C20 | 0.0180 (11) | 0.0114 (10) | 0.0252 (12) | −0.0096 (9) | −0.0046 (10) | 0.0002 (9) |
C21 | 0.0210 (11) | 0.0129 (10) | 0.0201 (11) | −0.0111 (9) | −0.0046 (10) | −0.0001 (9) |
C22 | 0.0331 (14) | 0.0217 (12) | 0.0220 (12) | −0.0196 (11) | −0.0058 (11) | −0.0002 (10) |
C23 | 0.0471 (16) | 0.0323 (14) | 0.0188 (12) | −0.0272 (13) | −0.0137 (12) | 0.0038 (10) |
C24 | 0.0393 (15) | 0.0261 (13) | 0.0251 (13) | −0.0201 (12) | −0.0197 (12) | 0.0069 (10) |
C25 | 0.0261 (12) | 0.0190 (11) | 0.0247 (12) | −0.0117 (10) | −0.0142 (11) | 0.0054 (10) |
N26 | 0.0212 (10) | 0.0154 (9) | 0.0192 (10) | −0.0103 (8) | −0.0088 (8) | 0.0034 (8) |
C27 | 0.0225 (13) | 0.0215 (13) | 0.0345 (14) | −0.0131 (11) | 0.0055 (11) | −0.0096 (11) |
C28 | 0.0341 (14) | 0.0293 (14) | 0.0232 (13) | −0.0216 (12) | 0.0026 (11) | −0.0087 (11) |
O29 | 0.0258 (9) | 0.0174 (8) | 0.0290 (9) | −0.0111 (7) | −0.0178 (8) | 0.0054 (7) |
O30 | 0.0170 (8) | 0.0195 (8) | 0.0237 (9) | −0.0077 (7) | −0.0092 (7) | 0.0049 (7) |
Mn2 | 0.01208 (17) | 0.01758 (18) | 0.01646 (17) | −0.00637 (14) | −0.00530 (14) | 0.00197 (13) |
N40 | 0.0182 (10) | 0.0328 (11) | 0.0189 (10) | −0.0153 (9) | −0.0087 (8) | 0.0030 (8) |
C41 | 0.0265 (14) | 0.068 (2) | 0.0253 (14) | −0.0261 (14) | −0.0153 (12) | 0.0071 (13) |
C42 | 0.0314 (11) | 0.0687 (15) | 0.0294 (10) | −0.0267 (11) | −0.0192 (9) | 0.0093 (10) |
C43 | 0.0456 (18) | 0.082 (2) | 0.0182 (13) | −0.0419 (18) | −0.0093 (13) | −0.0049 (14) |
C44 | 0.0320 (14) | 0.0333 (14) | 0.0187 (12) | −0.0230 (12) | −0.0053 (11) | −0.0016 (10) |
C45 | 0.0193 (11) | 0.0210 (12) | 0.0176 (11) | −0.0124 (10) | −0.0060 (9) | 0.0000 (9) |
C46 | 0.0157 (11) | 0.0132 (10) | 0.0184 (11) | −0.0084 (9) | −0.0056 (9) | 0.0017 (9) |
C47 | 0.0153 (11) | 0.0145 (11) | 0.0274 (13) | −0.0067 (9) | −0.0049 (10) | 0.0032 (9) |
C48 | 0.0139 (11) | 0.0264 (13) | 0.0363 (14) | −0.0069 (10) | −0.0089 (11) | 0.0091 (11) |
C49 | 0.0314 (11) | 0.0687 (15) | 0.0294 (10) | −0.0267 (11) | −0.0192 (9) | 0.0093 (10) |
C50 | 0.0215 (12) | 0.0336 (14) | 0.0201 (12) | −0.0131 (11) | −0.0113 (10) | 0.0063 (10) |
N51 | 0.0153 (9) | 0.0198 (10) | 0.0166 (9) | −0.0085 (8) | −0.0057 (8) | 0.0023 (8) |
C52 | 0.0313 (14) | 0.0292 (14) | 0.0205 (12) | −0.0162 (12) | 0.0027 (11) | −0.0080 (11) |
C53 | 0.0202 (12) | 0.0217 (12) | 0.0295 (14) | −0.0085 (10) | 0.0022 (11) | −0.0033 (10) |
N55 | 0.0139 (9) | 0.0184 (10) | 0.0251 (10) | −0.0074 (8) | −0.0068 (8) | −0.0009 (8) |
C56 | 0.0177 (12) | 0.0247 (13) | 0.0351 (14) | −0.0093 (10) | −0.0084 (11) | −0.0064 (11) |
C57 | 0.0222 (13) | 0.0247 (13) | 0.0490 (17) | −0.0118 (11) | −0.0063 (12) | −0.0106 (12) |
C58 | 0.0236 (13) | 0.0187 (12) | 0.0511 (18) | −0.0136 (11) | −0.0037 (12) | 0.0001 (12) |
C59 | 0.0154 (11) | 0.0177 (12) | 0.0347 (14) | −0.0067 (10) | −0.0032 (10) | 0.0045 (10) |
C60 | 0.0095 (10) | 0.0171 (11) | 0.0256 (12) | −0.0055 (9) | −0.0037 (9) | 0.0014 (9) |
C61 | 0.0106 (10) | 0.0205 (12) | 0.0204 (12) | −0.0061 (9) | −0.0033 (9) | 0.0031 (9) |
C62 | 0.0132 (11) | 0.0298 (13) | 0.0214 (12) | −0.0073 (10) | −0.0061 (10) | 0.0062 (10) |
C63 | 0.0182 (12) | 0.0448 (16) | 0.0209 (12) | −0.0113 (11) | −0.0090 (10) | 0.0026 (11) |
C64 | 0.0179 (12) | 0.0368 (15) | 0.0276 (13) | −0.0120 (11) | −0.0082 (11) | −0.0065 (11) |
C65 | 0.0175 (11) | 0.0228 (12) | 0.0253 (12) | −0.0104 (10) | −0.0056 (10) | −0.0033 (10) |
N66 | 0.0129 (9) | 0.0166 (9) | 0.0180 (9) | −0.0072 (8) | −0.0035 (8) | 0.0008 (8) |
C67 | 0.0238 (13) | 0.0261 (14) | 0.0409 (16) | −0.0120 (11) | −0.0076 (12) | 0.0165 (12) |
C68 | 0.0243 (13) | 0.0365 (15) | 0.0285 (14) | −0.0126 (12) | −0.0109 (11) | 0.0166 (12) |
O70 | 0.0210 (8) | 0.0195 (8) | 0.0265 (9) | −0.0086 (7) | −0.0125 (7) | 0.0066 (7) |
C71 | 0.0155 (11) | 0.0197 (12) | 0.0157 (11) | −0.0074 (9) | −0.0047 (9) | 0.0013 (9) |
O72 | 0.0283 (9) | 0.0233 (9) | 0.0359 (10) | −0.0154 (8) | −0.0222 (8) | 0.0114 (7) |
C73 | 0.0213 (12) | 0.0262 (13) | 0.0264 (13) | −0.0140 (10) | −0.0123 (10) | 0.0088 (10) |
S74 | 0.0180 (3) | 0.0213 (3) | 0.0480 (4) | −0.0062 (2) | −0.0145 (3) | 0.0087 (3) |
C75 | 0.0156 (12) | 0.0365 (16) | 0.0387 (16) | −0.0036 (11) | 0.0015 (12) | 0.0112 (13) |
C76 | 0.0158 (13) | 0.0325 (15) | 0.062 (2) | −0.0146 (12) | −0.0140 (13) | 0.0289 (14) |
O77 | 0.0154 (9) | 0.0298 (10) | 0.0467 (11) | −0.0116 (8) | −0.0142 (8) | 0.0130 (8) |
O78A | 0.0155 (12) | 0.0289 (13) | 0.047 (2) | −0.0127 (10) | −0.0151 (16) | 0.0094 (16) |
O78B | 0.0155 (12) | 0.0289 (13) | 0.047 (2) | −0.0127 (10) | −0.0151 (16) | 0.0094 (16) |
O80 | 0.0246 (9) | 0.0350 (10) | 0.0359 (10) | −0.0169 (8) | −0.0205 (8) | 0.0201 (8) |
C81 | 0.0173 (11) | 0.0177 (11) | 0.0134 (10) | −0.0059 (9) | −0.0062 (9) | 0.0004 (9) |
O82 | 0.0215 (8) | 0.0232 (9) | 0.0254 (9) | −0.0129 (7) | −0.0118 (7) | 0.0071 (7) |
C83 | 0.0196 (11) | 0.0163 (11) | 0.0175 (11) | −0.0077 (9) | −0.0092 (9) | 0.0019 (9) |
S84 | 0.0172 (3) | 0.0196 (3) | 0.0161 (3) | −0.0090 (2) | −0.0083 (2) | 0.0031 (2) |
C85 | 0.0208 (11) | 0.0158 (11) | 0.0200 (11) | −0.0086 (9) | −0.0105 (10) | 0.0025 (9) |
C86 | 0.0214 (12) | 0.0149 (11) | 0.0200 (12) | −0.0048 (9) | −0.0105 (10) | 0.0023 (9) |
O87 | 0.0293 (10) | 0.0333 (10) | 0.0208 (9) | −0.0173 (8) | −0.0050 (8) | −0.0035 (7) |
O88 | 0.0324 (10) | 0.0294 (9) | 0.0239 (9) | −0.0175 (8) | −0.0135 (8) | 0.0003 (7) |
O101 | 0.0209 (9) | 0.0261 (9) | 0.0410 (11) | −0.0084 (8) | −0.0176 (8) | 0.0022 (8) |
O102 | 0.0334 (10) | 0.0332 (10) | 0.0283 (10) | −0.0184 (9) | −0.0130 (8) | 0.0046 (8) |
O103 | 0.0400 (11) | 0.0341 (11) | 0.0305 (10) | −0.0195 (9) | −0.0169 (9) | 0.0051 (8) |
O105 | 0.0298 (10) | 0.0356 (11) | 0.0266 (10) | −0.0126 (9) | −0.0067 (8) | −0.0049 (8) |
O106 | 0.0264 (10) | 0.0321 (10) | 0.0318 (10) | −0.0078 (8) | −0.0124 (8) | 0.0116 (8) |
O107 | 0.0256 (10) | 0.0326 (10) | 0.0433 (11) | −0.0181 (8) | −0.0175 (9) | 0.0098 (9) |
O108 | 0.0597 (16) | 0.096 (2) | 0.0593 (16) | −0.0590 (16) | −0.0396 (14) | 0.0347 (15) |
O109 | 0.0467 (13) | 0.0609 (15) | 0.0507 (14) | −0.0412 (12) | −0.0063 (11) | −0.0088 (11) |
O110 | 0.0402 (11) | 0.0373 (11) | 0.0333 (11) | −0.0245 (10) | −0.0067 (9) | 0.0015 (9) |
O111 | 0.0394 (12) | 0.0326 (11) | 0.0379 (11) | −0.0219 (10) | 0.0046 (9) | −0.0067 (9) |
O112 | 0.0283 (10) | 0.0387 (11) | 0.0294 (10) | −0.0123 (9) | −0.0070 (8) | 0.0045 (9) |
O113 | 0.0419 (14) | 0.0799 (19) | 0.0577 (15) | −0.0230 (14) | −0.0092 (12) | −0.0215 (15) |
Geometric parameters (Å, º) top
Mn1—O29 | 2.1214 (17) | C49—C50 | 1.397 (4) |
Mn1—O30 | 2.1302 (16) | C49—H49 | 0.9500 |
Mn1—N1 | 2.2517 (19) | C50—N51 | 1.327 (3) |
Mn1—N26 | 2.2817 (19) | C50—H50 | 0.9500 |
Mn1—N15 | 2.2823 (19) | C52—C53 | 1.342 (4) |
Mn1—N12 | 2.284 (2) | C52—H52 | 0.9500 |
N1—C2 | 1.326 (3) | C53—H53 | 0.9500 |
N1—C6 | 1.362 (3) | N55—C56 | 1.330 (3) |
C2—C3 | 1.398 (4) | N55—C60 | 1.362 (3) |
C2—H2 | 0.9500 | C56—C57 | 1.398 (4) |
C3—C4 | 1.369 (4) | C56—H56 | 0.9500 |
C3—H3 | 0.9500 | C57—C58 | 1.361 (4) |
C4—C5 | 1.404 (4) | C57—H57 | 0.9500 |
C4—H4 | 0.9500 | C58—C59 | 1.408 (4) |
C5—C6 | 1.410 (3) | C58—H58 | 0.9500 |
C5—C13 | 1.433 (4) | C59—C60 | 1.401 (3) |
C6—C7 | 1.441 (3) | C59—C67 | 1.429 (4) |
C7—N12 | 1.363 (3) | C60—C61 | 1.441 (3) |
C7—C8 | 1.406 (3) | C61—N66 | 1.361 (3) |
C8—C9 | 1.405 (4) | C61—C62 | 1.405 (3) |
C8—C14 | 1.429 (4) | C62—C63 | 1.409 (4) |
C9—C10 | 1.365 (4) | C62—C68 | 1.436 (4) |
C9—H9 | 0.9500 | C63—C64 | 1.365 (4) |
C10—C11 | 1.401 (4) | C63—H63 | 0.9500 |
C10—H10 | 0.9500 | C64—C65 | 1.398 (4) |
C11—N12 | 1.325 (3) | C64—H64 | 0.9500 |
C11—H11 | 0.9500 | C65—N66 | 1.327 (3) |
C13—C14 | 1.346 (4) | C65—H65 | 0.9500 |
C13—H13 | 0.9500 | C67—C68 | 1.350 (4) |
C14—H14 | 0.9500 | C67—H67 | 0.9500 |
N15—C16 | 1.331 (3) | C68—H68 | 0.9500 |
N15—C20 | 1.358 (3) | O70—C71 | 1.260 (3) |
C16—C17 | 1.395 (4) | C71—O72 | 1.254 (3) |
C16—H16 | 0.9500 | C71—C73 | 1.521 (3) |
C17—C18 | 1.359 (4) | C73—S74 | 1.814 (2) |
C17—H17 | 0.9500 | C73—H73A | 0.9900 |
C18—C19 | 1.410 (4) | C73—H73B | 0.9900 |
C18—H18 | 0.9500 | S74—C75 | 1.811 (3) |
C19—C20 | 1.409 (3) | C75—C76 | 1.520 (5) |
C19—C27 | 1.429 (4) | C75—H75A | 0.9900 |
C20—C21 | 1.439 (3) | C75—H75B | 0.9900 |
C21—N26 | 1.361 (3) | C76—O78B | 1.189 (8) |
C21—C22 | 1.411 (3) | C76—O77 | 1.257 (3) |
C22—C23 | 1.407 (4) | C76—O78A | 1.320 (4) |
C22—C28 | 1.434 (4) | O78A—O78B | 0.759 (8) |
C23—C24 | 1.368 (4) | O80—C81 | 1.247 (3) |
C23—H23 | 0.9500 | C81—O82 | 1.257 (3) |
C24—C25 | 1.398 (3) | C81—C83 | 1.520 (3) |
C24—H24 | 0.9500 | C83—S84 | 1.811 (2) |
C25—N26 | 1.329 (3) | C83—H83A | 0.9900 |
C25—H25 | 0.9500 | C83—H83B | 0.9900 |
C27—C28 | 1.348 (4) | S84—C85 | 1.803 (2) |
C27—H27 | 0.9500 | C85—C86 | 1.522 (3) |
C28—H28 | 0.9500 | C85—H85A | 0.9900 |
O29—H29V | 0.90 (4) | C85—H85B | 0.9900 |
O29—H29W | 0.921 (18) | C86—O87 | 1.245 (3) |
O30—H30W | 0.94 (4) | C86—O88 | 1.260 (3) |
O30—H30V | 0.931 (18) | O101—H01V | 0.931 (19) |
Mn2—O70 | 2.1232 (16) | O101—H01W | 0.927 (19) |
Mn2—O77 | 2.1512 (17) | O102—H02V | 0.93 (4) |
Mn2—N66 | 2.2403 (19) | O102—H02W | 0.946 (19) |
Mn2—N40 | 2.240 (2) | O103—H03W | 0.934 (19) |
Mn2—N55 | 2.286 (2) | O103—H03V | 0.90 (4) |
Mn2—N51 | 2.3222 (19) | O105—H5V | 0.92 (4) |
N40—C41 | 1.321 (3) | O105—H5W | 0.911 (19) |
N40—C45 | 1.360 (3) | O106—H6V | 0.92 (4) |
C41—C42 | 1.397 (4) | O106—H6W | 0.929 (19) |
C41—H41 | 0.9500 | O107—H7V | 0.92 (4) |
C42—C43 | 1.349 (4) | O107—H7W | 0.91 (4) |
C42—H42 | 0.9500 | O108—H8V | 0.885 (19) |
C43—C44 | 1.403 (4) | O109—H9V | 0.92 (4) |
C43—H43 | 0.9500 | O109—H9W | 0.932 (19) |
C44—C45 | 1.404 (3) | O110—H10V | 0.92 (4) |
C44—C52 | 1.431 (4) | O110—H10W | 0.936 (19) |
C45—C46 | 1.439 (3) | O111—H11V | 0.930 (19) |
C46—N51 | 1.357 (3) | O111—H11W | 0.934 (19) |
C46—C47 | 1.414 (3) | O112—H12W | 0.936 (19) |
C47—C48 | 1.404 (4) | O112—H12V | 0.932 (19) |
C47—C53 | 1.432 (4) | O113—H13W | 0.879 (19) |
C48—C49 | 1.366 (4) | O99A—O99B | 1.190 (11) |
C48—H48 | 0.9500 | O99A—O99C | 1.417 (10) |
| | | |
O29—Mn1—O30 | 87.17 (6) | C42—C43—H43 | 120.3 |
O29—Mn1—N1 | 94.00 (7) | C44—C43—H43 | 120.3 |
O30—Mn1—N1 | 104.28 (7) | C43—C44—C45 | 117.6 (2) |
O29—Mn1—N26 | 101.59 (7) | C43—C44—C52 | 122.7 (2) |
O30—Mn1—N26 | 90.19 (7) | C45—C44—C52 | 119.7 (2) |
N1—Mn1—N26 | 159.27 (7) | N40—C45—C44 | 122.5 (2) |
O29—Mn1—N15 | 89.62 (7) | N40—C45—C46 | 118.1 (2) |
O30—Mn1—N15 | 161.96 (7) | C44—C45—C46 | 119.4 (2) |
N1—Mn1—N15 | 93.65 (7) | N51—C46—C47 | 122.5 (2) |
N26—Mn1—N15 | 73.07 (7) | N51—C46—C45 | 118.03 (19) |
O29—Mn1—N12 | 167.67 (7) | C47—C46—C45 | 119.5 (2) |
O30—Mn1—N12 | 95.03 (7) | C48—C47—C46 | 117.7 (2) |
N1—Mn1—N12 | 73.69 (7) | C48—C47—C53 | 123.2 (2) |
N26—Mn1—N12 | 90.55 (7) | C46—C47—C53 | 119.2 (2) |
N15—Mn1—N12 | 91.89 (7) | C49—C48—C47 | 119.5 (2) |
C2—N1—C6 | 117.9 (2) | C49—C48—H48 | 120.2 |
C2—N1—Mn1 | 126.59 (17) | C47—C48—H48 | 120.2 |
C6—N1—Mn1 | 115.47 (15) | C48—C49—C50 | 118.8 (2) |
N1—C2—C3 | 123.2 (3) | C48—C49—H49 | 120.6 |
N1—C2—H2 | 118.4 | C50—C49—H49 | 120.6 |
C3—C2—H2 | 118.4 | N51—C50—C49 | 123.9 (2) |
C4—C3—C2 | 119.3 (3) | N51—C50—H50 | 118.1 |
C4—C3—H3 | 120.4 | C49—C50—H50 | 118.1 |
C2—C3—H3 | 120.4 | C50—N51—C46 | 117.59 (19) |
C3—C4—C5 | 119.4 (2) | C50—N51—Mn2 | 128.30 (16) |
C3—C4—H4 | 120.3 | C46—N51—Mn2 | 114.06 (14) |
C5—C4—H4 | 120.3 | C53—C52—C44 | 121.1 (2) |
C4—C5—C6 | 117.6 (2) | C53—C52—H52 | 119.5 |
C4—C5—C13 | 123.0 (2) | C44—C52—H52 | 119.5 |
C6—C5—C13 | 119.4 (2) | C52—C53—C47 | 121.2 (2) |
N1—C6—C5 | 122.6 (2) | C52—C53—H53 | 119.4 |
N1—C6—C7 | 118.2 (2) | C47—C53—H53 | 119.4 |
C5—C6—C7 | 119.2 (2) | C56—N55—C60 | 117.9 (2) |
N12—C7—C8 | 122.5 (2) | C56—N55—Mn2 | 127.39 (17) |
N12—C7—C6 | 117.8 (2) | C60—N55—Mn2 | 114.72 (15) |
C8—C7—C6 | 119.8 (2) | N55—C56—C57 | 123.1 (3) |
C9—C8—C7 | 117.5 (2) | N55—C56—H56 | 118.4 |
C9—C8—C14 | 123.2 (2) | C57—C56—H56 | 118.4 |
C7—C8—C14 | 119.2 (3) | C58—C57—C56 | 118.8 (2) |
C10—C9—C8 | 119.8 (2) | C58—C57—H57 | 120.6 |
C10—C9—H9 | 120.1 | C56—C57—H57 | 120.6 |
C8—C9—H9 | 120.1 | C57—C58—C59 | 120.1 (2) |
C9—C10—C11 | 118.9 (3) | C57—C58—H58 | 119.9 |
C9—C10—H10 | 120.6 | C59—C58—H58 | 119.9 |
C11—C10—H10 | 120.6 | C60—C59—C58 | 117.1 (2) |
N12—C11—C10 | 123.3 (2) | C60—C59—C67 | 119.5 (2) |
N12—C11—H11 | 118.3 | C58—C59—C67 | 123.4 (2) |
C10—C11—H11 | 118.3 | N55—C60—C59 | 122.8 (2) |
C11—N12—C7 | 118.0 (2) | N55—C60—C61 | 117.6 (2) |
C11—N12—Mn1 | 127.32 (16) | C59—C60—C61 | 119.6 (2) |
C7—N12—Mn1 | 114.60 (15) | N66—C61—C62 | 122.7 (2) |
C14—C13—C5 | 121.0 (2) | N66—C61—C60 | 117.9 (2) |
C14—C13—H13 | 119.5 | C62—C61—C60 | 119.5 (2) |
C5—C13—H13 | 119.5 | C61—C62—C63 | 117.3 (2) |
C13—C14—C8 | 121.4 (3) | C61—C62—C68 | 119.2 (2) |
C13—C14—H14 | 119.3 | C63—C62—C68 | 123.5 (2) |
C8—C14—H14 | 119.3 | C64—C63—C62 | 119.5 (2) |
C16—N15—C20 | 118.1 (2) | C64—C63—H63 | 120.3 |
C16—N15—Mn1 | 126.39 (16) | C62—C63—H63 | 120.3 |
C20—N15—Mn1 | 115.48 (14) | C63—C64—C65 | 119.5 (2) |
N15—C16—C17 | 123.1 (2) | C63—C64—H64 | 120.2 |
N15—C16—H16 | 118.4 | C65—C64—H64 | 120.2 |
C17—C16—H16 | 118.4 | N66—C65—C64 | 122.7 (2) |
C18—C17—C16 | 119.1 (2) | N66—C65—H65 | 118.6 |
C18—C17—H17 | 120.4 | C64—C65—H65 | 118.6 |
C16—C17—H17 | 120.4 | C65—N66—C61 | 118.2 (2) |
C17—C18—C19 | 120.0 (2) | C65—N66—Mn2 | 125.31 (16) |
C17—C18—H18 | 120.0 | C61—N66—Mn2 | 116.01 (15) |
C19—C18—H18 | 120.0 | C68—C67—C59 | 121.0 (2) |
C20—C19—C18 | 117.1 (2) | C68—C67—H67 | 119.5 |
C20—C19—C27 | 119.5 (2) | C59—C67—H67 | 119.5 |
C18—C19—C27 | 123.4 (2) | C67—C68—C62 | 121.0 (2) |
N15—C20—C19 | 122.5 (2) | C67—C68—H68 | 119.5 |
N15—C20—C21 | 118.0 (2) | C62—C68—H68 | 119.5 |
C19—C20—C21 | 119.5 (2) | C71—O70—Mn2 | 139.78 (15) |
N26—C21—C22 | 122.4 (2) | O72—C71—O70 | 123.7 (2) |
N26—C21—C20 | 118.0 (2) | O72—C71—C73 | 117.7 (2) |
C22—C21—C20 | 119.5 (2) | O70—C71—C73 | 118.6 (2) |
C23—C22—C21 | 117.5 (2) | C71—C73—S74 | 110.25 (17) |
C23—C22—C28 | 123.3 (2) | C71—C73—H73A | 109.6 |
C21—C22—C28 | 119.2 (2) | S74—C73—H73A | 109.6 |
C24—C23—C22 | 119.7 (2) | C71—C73—H73B | 109.6 |
C24—C23—H23 | 120.1 | S74—C73—H73B | 109.6 |
C22—C23—H23 | 120.1 | H73A—C73—H73B | 108.1 |
C23—C24—C25 | 118.9 (2) | C75—S74—C73 | 100.71 (12) |
C23—C24—H24 | 120.5 | C76—C75—S74 | 110.5 (2) |
C25—C24—H24 | 120.5 | C76—C75—H75A | 109.6 |
N26—C25—C24 | 123.4 (2) | S74—C75—H75A | 109.6 |
N26—C25—H25 | 118.3 | C76—C75—H75B | 109.6 |
C24—C25—H25 | 118.3 | S74—C75—H75B | 109.6 |
C25—N26—C21 | 118.0 (2) | H75A—C75—H75B | 108.1 |
C25—N26—Mn1 | 126.60 (16) | O78B—C76—O77 | 137.1 (5) |
C21—N26—Mn1 | 115.38 (14) | O77—C76—O78A | 118.6 (3) |
C28—C27—C19 | 121.1 (2) | O78B—C76—C75 | 100.3 (5) |
C28—C27—H27 | 119.4 | O77—C76—C75 | 117.9 (2) |
C19—C27—H27 | 119.4 | O78A—C76—C75 | 123.0 (3) |
C27—C28—C22 | 121.2 (2) | C76—O77—Mn2 | 139.8 (2) |
C27—C28—H28 | 119.4 | O78B—O78A—C76 | 63.1 (7) |
C22—C28—H28 | 119.4 | O78A—O78B—C76 | 82.2 (8) |
Mn1—O29—H29V | 133 (2) | O80—C81—O82 | 125.7 (2) |
Mn1—O29—H29W | 118 (2) | O80—C81—C83 | 117.5 (2) |
H29V—O29—H29W | 108 (3) | O82—C81—C83 | 116.85 (19) |
Mn1—O30—H30W | 123 (2) | C81—C83—S84 | 111.41 (15) |
Mn1—O30—H30V | 113 (2) | C81—C83—H83A | 109.3 |
H30W—O30—H30V | 105 (3) | S84—C83—H83A | 109.3 |
O70—Mn2—O77 | 96.90 (7) | C81—C83—H83B | 109.3 |
O70—Mn2—N66 | 92.01 (7) | S84—C83—H83B | 109.3 |
O77—Mn2—N66 | 106.85 (7) | H83A—C83—H83B | 108.0 |
O70—Mn2—N40 | 99.33 (7) | C85—S84—C83 | 98.80 (11) |
O77—Mn2—N40 | 91.89 (7) | C86—C85—S84 | 111.76 (16) |
N66—Mn2—N40 | 156.80 (7) | C86—C85—H85A | 109.3 |
O70—Mn2—N55 | 165.15 (7) | S84—C85—H85A | 109.3 |
O77—Mn2—N55 | 84.55 (7) | C86—C85—H85B | 109.3 |
N66—Mn2—N55 | 73.50 (7) | S84—C85—H85B | 109.3 |
N40—Mn2—N55 | 95.38 (7) | H85A—C85—H85B | 107.9 |
O70—Mn2—N51 | 95.22 (6) | O87—C86—O88 | 126.0 (2) |
O77—Mn2—N51 | 162.05 (7) | O87—C86—C85 | 119.2 (2) |
N66—Mn2—N51 | 85.85 (7) | O88—C86—C85 | 114.8 (2) |
N40—Mn2—N51 | 73.08 (7) | H01V—O101—H01W | 108 (3) |
N55—Mn2—N51 | 87.12 (7) | H02V—O102—H02W | 108 (3) |
C41—N40—C45 | 117.7 (2) | H03W—O103—H03V | 109 (3) |
C41—N40—Mn2 | 125.60 (17) | H5V—O105—H5W | 112 (3) |
C45—N40—Mn2 | 116.65 (15) | H6V—O106—H6W | 104 (3) |
N40—C41—C42 | 123.1 (3) | H7V—O107—H7W | 102 (3) |
N40—C41—H41 | 118.5 | H9V—O109—H9W | 114 (3) |
C42—C41—H41 | 118.5 | H10V—O110—H10W | 105 (3) |
C43—C42—C41 | 119.7 (3) | H11V—O111—H11W | 105 (3) |
C43—C42—H42 | 120.2 | H12W—O112—H12V | 109 (3) |
C41—C42—H42 | 120.2 | O99B—O99A—O99C | 163.9 (7) |
C42—C43—C44 | 119.4 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O29—H29V···O72 | 0.90 (4) | 1.78 (2) | 2.680 (2) | 168 (3) |
O29—H29W···O80 | 0.92 (2) | 1.69 (2) | 2.606 (2) | 178 (3) |
O30—H30W···O101i | 0.94 (4) | 1.71 (4) | 2.645 (2) | 178 (3) |
O30—H30V···O82 | 0.93 (2) | 1.72 (2) | 2.649 (2) | 174 (3) |
O101—H01V···O78A | 0.93 (2) | 1.84 (2) | 2.759 (3) | 170 (4) |
O101—H01V···O78B | 0.93 (2) | 1.85 (2) | 2.761 (8) | 166 (4) |
O101—H01W···O102ii | 0.93 (2) | 1.82 (4) | 2.743 (3) | 171 (4) |
O102—H02V···O111 | 0.93 (4) | 1.77 (2) | 2.698 (3) | 177 (4) |
O102—H02W···O103iii | 0.95 (2) | 1.85 (2) | 2.793 (3) | 176 (4) |
O103—H03W···O102 | 0.93 (2) | 1.93 (2) | 2.846 (3) | 168 (3) |
O103—H03V···O109iii | 0.91 (2) | 1.84 (2) | 2.736 (3) | 168 (4) |
O105—H5V···O113ii | 0.92 (4) | 1.92 (2) | 2.816 (3) | 165 (4) |
O105—H5W···O87 | 0.91 (2) | 1.89 (2) | 2.779 (2) | 166 (4) |
O106—H6V···O112iv | 0.91 (4) | 1.90 (2) | 2.763 (3) | 155 (4) |
O106—H6W···O72 | 0.93 (2) | 1.83 (2) | 2.742 (2) | 167 (4) |
O107—H7V···O82 | 0.92 (4) | 1.88 (4) | 2.797 (2) | 177 (4) |
O107—H7W···O78Bi | 0.91 (4) | 1.86 (3) | 2.690 (8) | 150 (3) |
O107—H7W···O78Ai | 0.91 (4) | 2.03 (2) | 2.922 (4) | 165 (3) |
O108—H8V···O78A | 0.89 (2) | 2.29 (2) | 3.173 (5) | 174 (4) |
O108—H8V···O77 | 0.89 (2) | 2.38 (4) | 2.975 (3) | 125 (3) |
O109—H9V···O88 | 0.92 (4) | 1.84 (2) | 2.759 (3) | 177 (4) |
O109—H9W···O107 | 0.93 (2) | 1.97 (2) | 2.891 (3) | 168 (4) |
O110—H10V···O87 | 0.92 (4) | 2.02 (5) | 2.930 (3) | 169 (3) |
O110—H10V···S84 | 0.92 (4) | 2.91 (4) | 3.404 (2) | 115 (3) |
O110—H10W···O107v | 0.94 (2) | 1.95 (2) | 2.866 (3) | 167 (4) |
O111—H11V···O88 | 0.93 (2) | 1.84 (2) | 2.730 (3) | 160 (4) |
O111—H11W···O112vi | 0.93 (2) | 1.90 (2) | 2.822 (3) | 170 (4) |
O112—H12W···O105vii | 0.94 (2) | 1.83 (2) | 2.740 (3) | 163 (4) |
O112—H12V···O106 | 0.93 (2) | 1.86 (2) | 2.794 (3) | 175 (4) |
O113—H13W···O106 | 0.88 (2) | 2.07 (2) | 2.917 (4) | 162 (4) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z; (iii) −x, −y, −z; (iv) −x+1, −y, −z+1; (v) −x, −y+1, −z; (vi) x, y, z−1; (vii) x, y, z+1. |
Experimental details
Crystal data |
Chemical formula | [Mn(C12H8N2)2(H2O)2][Mn(C12H8N2)2(C4H4O4S)](C4H4O4S)·13H2O |
Mr | 1393.17 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 15.0347 (7), 15.9870 (7), 16.4562 (8) |
α, β, γ (°) | 83.501 (4), 66.004 (5), 61.981 (5) |
V (Å3) | 3175.1 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.55 |
Crystal size (mm) | 0.55 × 0.55 × 0.40 |
|
Data collection |
Diffractometer | Kuma KM4 + CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16741, 10803, 9798 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.099, 1.05 |
No. of reflections | 10803 |
No. of parameters | 901 |
No. of restraints | 26 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.87, −0.73 |
Selected geometric parameters (Å, º) topMn1—O29 | 2.1214 (17) | C73—S74 | 1.814 (2) |
Mn1—O30 | 2.1302 (16) | S74—C75 | 1.811 (3) |
Mn1—N1 | 2.2517 (19) | C75—C76 | 1.520 (5) |
Mn1—N26 | 2.2817 (19) | C76—O78B | 1.189 (8) |
Mn1—N15 | 2.2823 (19) | C76—O77 | 1.257 (3) |
Mn1—N12 | 2.284 (2) | C76—O78A | 1.320 (4) |
Mn2—O70 | 2.1232 (16) | O80—C81 | 1.247 (3) |
Mn2—O77 | 2.1512 (17) | C81—O82 | 1.257 (3) |
Mn2—N66 | 2.2403 (19) | C81—C83 | 1.520 (3) |
Mn2—N40 | 2.240 (2) | C83—S84 | 1.811 (2) |
Mn2—N55 | 2.286 (2) | S84—C85 | 1.803 (2) |
Mn2—N51 | 2.3222 (19) | C85—C86 | 1.522 (3) |
O70—C71 | 1.260 (3) | C86—O87 | 1.245 (3) |
C71—O72 | 1.254 (3) | C86—O88 | 1.260 (3) |
C71—C73 | 1.521 (3) | | |
| | | |
O29—Mn1—O30 | 87.17 (6) | N66—Mn2—N40 | 156.80 (7) |
O29—Mn1—N1 | 94.00 (7) | O70—Mn2—N55 | 165.15 (7) |
O30—Mn1—N1 | 104.28 (7) | O77—Mn2—N55 | 84.55 (7) |
O29—Mn1—N26 | 101.59 (7) | N66—Mn2—N55 | 73.50 (7) |
O30—Mn1—N26 | 90.19 (7) | N40—Mn2—N55 | 95.38 (7) |
N1—Mn1—N26 | 159.27 (7) | O70—Mn2—N51 | 95.22 (6) |
O29—Mn1—N15 | 89.62 (7) | O77—Mn2—N51 | 162.05 (7) |
O30—Mn1—N15 | 161.96 (7) | N66—Mn2—N51 | 85.85 (7) |
N1—Mn1—N15 | 93.65 (7) | N40—Mn2—N51 | 73.08 (7) |
N26—Mn1—N15 | 73.07 (7) | N55—Mn2—N51 | 87.12 (7) |
O29—Mn1—N12 | 167.67 (7) | C71—O70—Mn2 | 139.78 (15) |
O30—Mn1—N12 | 95.03 (7) | O70—C71—C73 | 118.6 (2) |
N1—Mn1—N12 | 73.69 (7) | C71—C73—S74 | 110.25 (17) |
N26—Mn1—N12 | 90.55 (7) | C75—S74—C73 | 100.71 (12) |
N15—Mn1—N12 | 91.89 (7) | C76—C75—S74 | 110.5 (2) |
O70—Mn2—O77 | 96.90 (7) | O77—C76—C75 | 117.9 (2) |
O70—Mn2—N66 | 92.01 (7) | C76—O77—Mn2 | 139.8 (2) |
O77—Mn2—N66 | 106.85 (7) | C81—C83—S84 | 111.41 (15) |
O70—Mn2—N40 | 99.33 (7) | C85—S84—C83 | 98.80 (11) |
O77—Mn2—N40 | 91.89 (7) | C86—C85—S84 | 111.76 (16) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O29—H29V···O72 | 0.90 (4) | 1.78 (2) | 2.680 (2) | 168 (3) |
O29—H29W···O80 | 0.921 (18) | 1.685 (19) | 2.606 (2) | 178 (3) |
O30—H30W···O101i | 0.94 (4) | 1.71 (4) | 2.645 (2) | 178 (3) |
O30—H30V···O82 | 0.931 (18) | 1.722 (19) | 2.649 (2) | 174 (3) |
O101—H01V···O78A | 0.931 (19) | 1.84 (2) | 2.759 (3) | 170 (4) |
O101—H01V···O78B | 0.931 (19) | 1.85 (2) | 2.761 (8) | 166 (4) |
O101—H01W···O102ii | 0.927 (19) | 1.82 (4) | 2.743 (3) | 171 (4) |
O102—H02V···O111 | 0.93 (4) | 1.774 (19) | 2.698 (3) | 177 (4) |
O102—H02W···O103iii | 0.946 (19) | 1.849 (19) | 2.793 (3) | 176 (4) |
O103—H03W···O102 | 0.934 (19) | 1.93 (2) | 2.846 (3) | 168 (3) |
O103—H03V···O109iii | 0.910 (19) | 1.84 (2) | 2.736 (3) | 168 (4) |
O105—H5V···O113ii | 0.92 (4) | 1.92 (2) | 2.816 (3) | 165 (4) |
O105—H5W···O87 | 0.911 (19) | 1.89 (2) | 2.779 (2) | 166 (4) |
O106—H6V···O112iv | 0.91 (4) | 1.90 (2) | 2.763 (3) | 155 (4) |
O106—H6W···O72 | 0.929 (19) | 1.83 (2) | 2.742 (2) | 167 (4) |
O107—H7V···O82 | 0.92 (4) | 1.88 (4) | 2.797 (2) | 177 (4) |
O107—H7W···O78Bi | 0.91 (4) | 1.86 (3) | 2.690 (8) | 150 (3) |
O107—H7W···O78Ai | 0.91 (4) | 2.03 (2) | 2.922 (4) | 165 (3) |
O108—H8V···O78A | 0.885 (19) | 2.29 (2) | 3.173 (5) | 174 (4) |
O108—H8V···O77 | 0.885 (19) | 2.38 (4) | 2.975 (3) | 125 (3) |
O109—H9V···O88 | 0.92 (4) | 1.840 (19) | 2.759 (3) | 177 (4) |
O109—H9W···O107 | 0.932 (19) | 1.97 (2) | 2.891 (3) | 168 (4) |
O110—H10V···O87 | 0.92 (4) | 2.02 (5) | 2.930 (3) | 169 (3) |
O110—H10V···S84 | 0.92 (4) | 2.91 (4) | 3.404 (2) | 115 (3) |
O110—H10W···O107v | 0.936 (19) | 1.95 (2) | 2.866 (3) | 167 (4) |
O111—H11V···O88 | 0.930 (19) | 1.84 (2) | 2.730 (3) | 160 (4) |
O111—H11W···O112vi | 0.934 (19) | 1.90 (2) | 2.822 (3) | 170 (4) |
O112—H12W···O105vii | 0.936 (19) | 1.83 (2) | 2.740 (3) | 163 (4) |
O112—H12V···O106 | 0.932 (19) | 1.864 (19) | 2.794 (3) | 175 (4) |
O113—H13W···O106 | 0.879 (19) | 2.07 (2) | 2.917 (4) | 162 (4) |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z; (iii) −x, −y, −z; (iv) −x+1, −y, −z+1; (v) −x, −y+1, −z; (vi) x, y, z−1; (vii) x, y, z+1. |
Metal complexes involving the carboxylate group are of interest not only as compounds that can be potentially used for the preparation of precursors applicable in materials chemistry (Devereux et al., 2002), and for their potential biological activity (Geraghty et al., 1999), but also from a structural point of view. Thiodiglycolic acid (tdgaH2) is dicarboxylic acid containing four O atoms and one S atom in the molecule. These atoms cause coordination variability of tdga2− to metal centers. It has been found that tdga2− is coordinated preferentially as a tridentate O,S,O'-ligand (Drew et al., 1975; Delaunay et al., 1976, 1978; Bonomo et al., 1982). Moreover, it can be also chelated as a bidentate O,S-ligand (Efimenko et al., 1991) and it can form bridges in binuclear complexes (Baggio et al., 1999). Apart from the formation of mononuclear or binuclear compounds, transition metal complexes with tdgaH2 in the form of polymeric chains (Bonomo et al., 1982) or three-dimensional structures (Kepert et al., 1999; Zhang et al., 2002; Grirrane et al., 2003) have been prepared. Recently, we have prepared and structurally characterized two mixed-ligand binuclear CuII complexes in which the tdga dianion acts as a bridge (Kopel et al., 2003). We report here the title compound, (I), which contains the tdga2− ion chelated as a bidentate O,O'-ligand and forms an eight-membered ring with one Mn atom.
The crystal structure of (I) consists of [Mn(phen)2(tdga)] complex molecules (Fig. 1a), [Mn(phen)2(H2O)2]2+ complex cations (Fig. 1 b), tdga2− anions (Fig. 1 b) and water molecules.
The MnII ion in the complex molecule adopts a substantially distorted octahedral geometry, defined by four N atoms of two phen ligands and two carboxyl O atoms of a tdga ligand in a cis configuration. While the first bidentate chelating phen ligand (containing atoms N40 and C53) is almost perfectly planar (the angles between its individual six-membered rings are up to 0.8°), the second phen ligand (containing atoms N55 and C68) is significantly deformed from planarity (the angles between its six-membered rings vary from 3.5 to 5.3°). The tdga ligand is chelated as a bidentate O,O'-ligand and forms an eight-membered ring with an Mn atom. The Mn—N and Mn—O distances in this complex vary from 2.240 to 2.322 Å, and from 2.123 to 2.151 Å, respectively. These lengths are comparable to the mean Mn—N and Mn—O distances (2.270 and 2.112 Å) found in related complexes (Cambridge Structural Database, Version 5.24.3; Allen, 2002).
The structure of the [Mn(phen)2(H2O)2]2+ complex cation is similar to those of MnII-complex ions determined previously (McCann et al., 1997; Geraghty et al., 1998; Devereux et al., 2000a, 2000b, 2002; Zheng et al., 2001). Mn atom is surrounded by four N atoms of two phen ligands and two O atoms of two water molecules. Like the [Mn(phen)2(tdga)] complex molecule, the cation displays a cis configuration and the Mn atom has a substantially distorted octahedral coordination. The Mn—N and Mn—O distances in the cation vary from 2.252 to 2.284 Å, and from 2.121 to 2.130 Å, respectively.
The positive charge of the cation is compensated by the negative charge of tdga dianion, which is? connected to the [Mn(phen)2(H2O)2]2+ ion via O—H···O hydrogen bonds (Fig. 1 b and Table 2). The tdga2− anion is further hydrogen bonded to five water molecules. In the crystal lattice of (I), anions and water molecules are linked by an extensive network of hydrogen bonds, thus forming two-dimensional (101) layers (Fig. 2 and Table 2).