research communications
Bis(3,5-dimethoxy-2-{[2-(pyridin-2-yl)ethylimino-κN]methyl}phenolato-κO)bis(dimethyl sulfoxide)manganese(III) perchlorate methanol 0.774-solvate
aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
*Correspondence e-mail: rnegekenze@gmail.com
The title compound, [Mn(C16H17N2O3)2(C2H6OS)2]ClO4·0.774CH3OH, comprises a central octahedrally coordinated MnIII cation, with two bidentate Schiff base ligands occupying the equatorial positions and two dimethyl sulfoxide (DMSO) ligands occupying the axial positions. There are two independant cations in the with the MnIII atoms of both cations being positioned on crystallographic centers of inversion. The perchlorate anion is disordered over two equivalent conformations, with occupancies of 0.744 (3) and 0.226 (3). In addition, there is a methanol solvent molecule in the that is too close to the minor component of the perchlorate anion to be present simultaneously and thus it was refined to have the same occupancy as the major component of this anion. There is a Jahn–Teller distortion which results in Mn—ODMSO axial bond lengths of 2.2365 (12) and 2.2368 (12) Å in the two cations. In the crystal, intermolecular π–π stacking between the non-coordinating pyridine rings of each cation is observed. This π–π stacking, along with extensive O—H⋯O hydrogen bonding and C—H⋯O interactions, link the components into a complex three-dimensional array.
CCDC reference: 1570012
1. Chemical context
Single-molecule magnets (SMMs) are a class of coordination compounds that attract a great deal of scientific attention because they exhibit magnetic bistability at low temperatures (Christou et al., 2000; Gatteschi et al., 2006). These finite size (zero-dimensional) molecules possess a high-spin ground state St and a magnetic anisotropy of the easy-axis type (negative zero-field splitting parameter D), which causes a slow relaxation of the magnetization at low temperatures, resulting in a hysteresis of the magnetization of purely molecular origin (Sessoli et al., 1993a,b; Gatteschi et al., 1994; Aubin et al., 1998; Gatteschi & Sessoli, 2003; Long, 2003; Thomas et al., 1996). SMMs promise access to dynamic random access memory devices for quantum computing and to ultimate high-density memory storage devices in which each bit of digital information is stored on a single molecule (Tejada, 2001; Awschalom et al., 1992; Leuenberger & Loss, 2001; Cornia et al., 2003; Dahlberg & Zhu, 1995).
The archetype of SMMs is the family of dodecanuclear manganese complexes, [Mn12O12(O2CR)16(OH2)4], Mn12 (Lis, 1980; Sessoli et al., 1993a,b; Boyd et al., 1988; Tsai et al., 1994; Sun et al., 1998; Boskovic et al., 2002). Since the discovery of the SMM behavior of Mn12, a lot of synthetic effort has been devoted to the preparation of new molecules with an increased anisotropy barrier. In this respect, it is interesting to note that already a dimeric MnIII salen complex behaves as an SMM (Miyasaka et al., 2004).
An undeveloped field in this chemistry is the use of manganese complexes of Schiff base ligands as precursors in the synthesis of SMMs. In a continuation of our studies in manganese chemistry with Schiff base ligands as precursors to SSMs (Egekenze et al., 2017a,b,c), we report the structure of bis(3,5-dimethoxy-2-{[2-(pyridin-2-yl)ethylimino-κN]methyl}phenolato-κO)bis(dimethyl sulfoxide)manganese(III) perchlorate methanol 0.774-solvate.
2. Structural commentary
In the structure of the title compound (Fig. 1), the cation contains a central octahedrally coordinated MnIII cation, with two bidentate Schiff base ligands occupying the equatorial positions and two dimethyl sulfoxide (DMSO) ligands occupying the axial positions. There are two independant cations in the with the MnIII atoms of both cations being positioned on crystallographic centers of inversion. The perchlorate anion is disordered over two equivalent conformations, with occupancies of 0.744 (3) and 0.226 (3). In addition, there is a disordered methanol solvent molecule in the crystal lattice.
Interestingly, the Schiff base ligand is potentially tridentate as it is the result of the condensation of 3,5-dimethoxysalicylaldehyde with 2-(2-aminoethyl)pyridine. However, the pyridine arm does not coordinate to manganese and the softer Npy-donors have been replaced by the O-donors of the DMSO molecules as the complex was crystallized from DMSO. The Mn—Ophen [1.8757 (11) and 1.8770 (11) Å] and Mn—Nimine bond lengths [2.0335 (13) and 2.0380 (13) Å] are in the normal ranges found for manganese Schiff base complexes. As this is a high-spin d4 cation, there is Jahn–Teller distortion (Jahn & Teller, 1937) which results in Mn—ODMSO axial bond lengths of 2.2365 (12) and 2.2368 (12) Å in the two cations.
A survey of the Cambridge Structural Database (Groom et al., 2016) for compounds of manganese Schiff base complexes with attached DMSO ligands showed only one other example (Glaser et al., 2007) of a bis-DMSO complex of an MnIII Schiff base. In this case, the DMSO ligands were also occupying axial positions. If the search was restricted to a single coordinating DMSO ligand, there was one relevant example (Bermejo et al., 1994), aqua[N,N′-bis(3-bromo-5-nitrosalicylidene)-1,2-diamino-(2-methyl)ethane](dimethyl sulfoxide)manganese(II), which, however, contains both MnII and a tetradentate ligand and therefore no Jahn–Teller distorsion was observed.
3. Supramolecular features
In the π–π stacking between the non-coordinating pyridine rings of each cation is observed with a perpendicular stacking distance of 3.623 Å and a slippage of 1.321 Å (symmetry code 1 − x,, 1 − y, 1 − z). This π–π stacking, along with extensive O—H⋯O hydrogen bonding and C—H⋯O interactions (Fig. 2 and Table 1), link the components into a complex three-dimensional array.
intermolecular4. Database survey
A survey of the Cambridge Structural Database for examples of DMSO ligands coordinating to manganese Schiff base skeletons gave only one example of a bis-DMSO complex (refcode JETYOX) and only five examples with only one attached DMSO ligand (refcodes EBILOQ, FOFWIH, LEJCEI, WADZUZ, and WAFBAJ)
5. Synthesis and crystallization
5.1. Synthesis of 3,5-dimethoxy-2-{[2-(pyridin-2-yl)ethylimino]methyl}phenol
A solution of 1.3985 g (11.4 mmol) of 2-(pyridin-2-yl)ethanamine in 15 ml of methanol was mixed with a solution of 2.0874 g (11.5 mmol) of 4,6-dimethoxysalicylic aldehyde in 15 ml of methanol to obtain a dark-green solution. The solution was refluxed for 4 h. The thick dark-brown oil obtained was recrystallized from dichloromethane by slow evaporation of the solvent (yield: 3.02 g, 87%). Characterization data for C16H18N2O3 are as follows; molecular mass: calculated for [C16H19N2O3]+ = 287.1396, ESI–MS determined m/z = 287.1390. IR (LiTaO3, KBr) (cm−1); 3008 (w), 2932 (w), 2850 (w), 1630 (s), 1610 (s), 1586 (m), 1564 (m), 1537 (s), 1470 (m), 1446 (m-s), 1434 (s), 1403 (w), 1354 (s), 1314 (w), 1290 (w), 1265 (w), 1231 (m), 1217 (s), 1201 (s), 1178 (m), 1144 (s), 1111 (m), 1100 (m), 1040 (m), 1010 (m), 986 (m), 929 (m), 879 (m), 824 (s), 771 (s), 746 (m), 690 (w), 655 (m). UV–Vis {λmax (nm), (MeOH)}: 203 (180.31), 255 (23.19), 262 (25.43), 314 (137.83), 375 (35.61). 1H NMR {CDCl3}: δ 14.25 (s, 1H ArO-H), 8.58, (s, 1H, –CH=N), 5.50, 5.85, 7.25, 7.58, 8.28, (s, 1H ArH); 7.10 (d, 2H); 3.08 (d, 2H, CH2); 3.88 (d, 2H, CH2); 3.70 (m, 6H, 2(OCH3).
5.2. Synthesis of bis(3,5-dimethoxy-2-{[2-(pyridin-2-yl)ethylimino-κN]methyl}phenolato-κO)bis(dimethyl sulfoxide)manganese(III) perchlorate methanol 0.774-solvate
A solution of Mn(ClO4)2·6H2O (1.6965 g, 9.2 mmol) in methanol was added to a mixture of 3,5-dimethoxy-2-{[2-(pyridin-2-yl)ethylimino]methyl}phenol (2.6252 g, 9.2 mmol) and triethylamine (C6H15N; 1.65 ml, 9.2 mmol). The solution turned dark brown. It was refluxed for 4 h and cooled to room temperature. The solvent was reduced with a rotary evaporator and the resulting precipitate was filtered off by suction, washed with diethyl ether and dried in the desiccator. The precipitate was recrystallized from methanol and diethyl ether and crystals suitable for X-ray analysis were grown by slow evaporation of a DMSO solution in a yield of 2.89 g (67%). Characterization data for C32H34MnClN4O10 are: molecular mass: calculated for [C32H34MnN4O6]+ = 625.1859, ESI–MS determined m/z = 625.2094. IR (LiTaO3, KBr) (cm−1): 294 (w), 1588 (s), 1543 (m), 1466 (m), 1450 (m), 1438 (m), 1417 (m), 1392 (w), 1338 (m), 1246 (s), 1220 (s), 1186 (w), 1165 (s), 1123 (m), 1081 (s), 1012 (m), 977 (w), 948 (w), 960 (w), 865 (w), 830 (s), 782 (m), 769 (m), 667 (s). UV–Vis [λmax (nm), (MeOH)]: 204 (20074.07), 263 (9385.37), 307 (11149.44).
6. Refinement
Crystal data, data collection and structure . The perchlorate anion is disordered over two equivalent conformations, with occupancies of 0.744 (3) and 0.226 (3). Both anions were constrained to have similar metrical and displacement parameters using both DFIX and SIMU commands in SHELXL2016 (Sheldrick, 2015). In addition, there is a methanol solvent molecule present. This molecule is too close to the minor component of the perchlorate anion to be present simultaneously and thus it was refined to have the same occupancy as the major component of this anion. This model lowered the R factor by 0.4%. H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H distances ranging from 0.95 to 0.98 Å. Uiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and 1.2 for all other C-bound H atoms. The O—H hydrogen was refined isotropically.
details are summarized in Table 2
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Supporting information
CCDC reference: 1570012
https://doi.org/10.1107/S205698901701204X/im2481sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901701204X/im2481Isup2.hkl
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Mn(C16H17N2O3)2(C2H6OS)2]ClO4·0.774CH4O | Z = 2 |
Mr = 906.10 | F(000) = 947.9 |
Triclinic, P1 | Dx = 1.471 Mg m−3 |
a = 8.0730 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.0143 (4) Å | Cell parameters from 12258 reflections |
c = 23.0453 (7) Å | θ = 3.1–37.6° |
α = 87.540 (3)° | µ = 0.56 mm−1 |
β = 89.175 (3)° | T = 123 K |
γ = 87.729 (3)° | Prism, red-brown |
V = 2045.49 (14) Å3 | 0.71 × 0.40 × 0.24 mm |
Agilent Xcalibur Ruby Gemini diffractometer | 16259 reflections with I > 2σ(I) |
Detector resolution: 10.5081 pixels mm-1 | Rint = 0.031 |
ω scans | θmax = 37.7°, θmin = 3.1° |
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)] | h = −13→13 |
Tmin = 0.754, Tmax = 0.885 | k = −18→18 |
36920 measured reflections | l = −39→37 |
20464 independent reflections |
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)] = 0.060 | Hydrogen site location: mixed |
wR(F2) = 0.149 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0465P)2 + 1.6285P] where P = (Fo2 + 2Fc2)/3 |
20464 reflections | (Δ/σ)max = 0.001 |
577 parameters | Δρmax = 1.16 e Å−3 |
148 restraints | Δρmin = −1.01 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Mn1 | 0.500000 | 0.500000 | 0.500000 | 0.01344 (6) | |
Mn2 | 1.000000 | 0.500000 | 0.000000 | 0.01420 (6) | |
S1A | 0.17543 (5) | 0.65456 (4) | 0.46048 (2) | 0.02256 (8) | |
S1B | 0.67033 (5) | 0.66578 (4) | 0.02599 (2) | 0.02310 (8) | |
Cl1 | 0.30171 (12) | 0.78497 (7) | 0.25281 (4) | 0.03133 (18) | 0.774 (3) |
O11 | 0.3026 (4) | 0.7096 (2) | 0.20426 (11) | 0.0591 (14) | 0.774 (3) |
O12 | 0.2546 (4) | 0.7170 (2) | 0.30416 (11) | 0.0419 (8) | 0.774 (3) |
O13 | 0.1894 (3) | 0.88677 (19) | 0.24370 (10) | 0.0649 (10) | 0.774 (3) |
O14 | 0.4653 (3) | 0.8281 (3) | 0.26037 (13) | 0.0809 (11) | 0.774 (3) |
Cl1A | 0.3726 (7) | 0.7628 (3) | 0.24715 (13) | 0.0490 (10) | 0.226 (3) |
O11A | 0.3059 (10) | 0.7049 (7) | 0.1990 (3) | 0.044 (3) | 0.226 (3) |
O12A | 0.3376 (13) | 0.8908 (3) | 0.2415 (3) | 0.064 (3) | 0.226 (3) |
O13A | 0.5479 (6) | 0.7399 (9) | 0.2486 (4) | 0.096 (4) | 0.226 (3) |
O14A | 0.2998 (11) | 0.7157 (7) | 0.2999 (2) | 0.0313 (19) | 0.226 (3) |
O1A | 0.50038 (15) | 0.34259 (10) | 0.47199 (5) | 0.0179 (2) | |
O2A | 0.2589 (2) | −0.03544 (13) | 0.43949 (7) | 0.0313 (3) | |
O3A | 0.24473 (18) | 0.12275 (12) | 0.62751 (6) | 0.0267 (3) | |
O4A | 0.22922 (15) | 0.52580 (11) | 0.48181 (6) | 0.0217 (2) | |
O1B | 1.01133 (16) | 0.65127 (10) | −0.04028 (5) | 0.0190 (2) | |
O2B | 1.2190 (2) | 1.03701 (12) | −0.09960 (6) | 0.0279 (3) | |
O3B | 1.22953 (19) | 0.90515 (12) | 0.09819 (6) | 0.0255 (3) | |
O4B | 0.72827 (15) | 0.53481 (11) | 0.01510 (6) | 0.0232 (2) | |
N1A | 0.45577 (16) | 0.43169 (12) | 0.58189 (6) | 0.0157 (2) | |
N2A | 0.4453 (2) | 0.76067 (16) | 0.69461 (8) | 0.0294 (3) | |
N1B | 1.04014 (16) | 0.58273 (12) | 0.07568 (6) | 0.0159 (2) | |
N2B | 1.0744 (3) | 0.25942 (16) | 0.20333 (7) | 0.0311 (4) | |
C1A | 0.41715 (19) | 0.24823 (13) | 0.49218 (7) | 0.0158 (2) | |
C2A | 0.3824 (2) | 0.15812 (14) | 0.45271 (7) | 0.0191 (3) | |
H2AA | 0.414312 | 0.167122 | 0.412964 | 0.023* | |
C3A | 0.3007 (2) | 0.05629 (14) | 0.47333 (8) | 0.0218 (3) | |
C4A | 0.2513 (2) | 0.04030 (15) | 0.53187 (8) | 0.0229 (3) | |
H4AA | 0.194402 | −0.029901 | 0.544822 | 0.027* | |
C5A | 0.2869 (2) | 0.12795 (14) | 0.57000 (7) | 0.0193 (3) | |
C6A | 0.36881 (19) | 0.23522 (13) | 0.55126 (7) | 0.0162 (2) | |
C7A | 0.3153 (3) | −0.03191 (19) | 0.38039 (10) | 0.0318 (4) | |
H7AA | 0.276708 | −0.102948 | 0.361093 | 0.048* | |
H7AB | 0.271203 | 0.042507 | 0.360392 | 0.048* | |
H7AC | 0.436765 | −0.032877 | 0.379174 | 0.048* | |
C8A | 0.1632 (3) | 0.0166 (2) | 0.64944 (11) | 0.0411 (5) | |
H8AA | 0.139570 | 0.023690 | 0.691014 | 0.062* | |
H8AB | 0.059117 | 0.009237 | 0.628745 | 0.062* | |
H8AC | 0.235214 | −0.055674 | 0.643549 | 0.062* | |
C9A | 0.40744 (19) | 0.32197 (14) | 0.59325 (7) | 0.0167 (2) | |
H9AA | 0.396694 | 0.296874 | 0.633040 | 0.020* | |
C10A | 0.4913 (2) | 0.50364 (15) | 0.63280 (7) | 0.0185 (3) | |
H10A | 0.584878 | 0.556669 | 0.623176 | 0.022* | |
H10B | 0.525077 | 0.447738 | 0.665681 | 0.022* | |
C11A | 0.3406 (2) | 0.58216 (17) | 0.65116 (8) | 0.0236 (3) | |
H11A | 0.308632 | 0.640228 | 0.618897 | 0.028* | |
H11B | 0.245813 | 0.529760 | 0.659978 | 0.028* | |
C12A | 0.3801 (2) | 0.65134 (16) | 0.70419 (8) | 0.0218 (3) | |
C13A | 0.3539 (3) | 0.60108 (19) | 0.75975 (8) | 0.0296 (4) | |
H13A | 0.307551 | 0.523374 | 0.765017 | 0.036* | |
C14A | 0.3962 (3) | 0.6655 (2) | 0.80748 (9) | 0.0334 (4) | |
H14A | 0.378686 | 0.632966 | 0.845823 | 0.040* | |
C15A | 0.4643 (3) | 0.7779 (2) | 0.79808 (9) | 0.0332 (4) | |
H15A | 0.495327 | 0.824044 | 0.829790 | 0.040* | |
C16A | 0.4863 (3) | 0.8215 (2) | 0.74155 (10) | 0.0350 (4) | |
H16A | 0.533045 | 0.898859 | 0.735357 | 0.042* | |
C17A | 0.0194 (3) | 0.6319 (2) | 0.40838 (9) | 0.0303 (4) | |
H17A | −0.022353 | 0.710897 | 0.392337 | 0.045* | |
H17B | 0.066872 | 0.583731 | 0.376985 | 0.045* | |
H17C | −0.071933 | 0.588592 | 0.427203 | 0.045* | |
C18A | 0.0442 (3) | 0.71209 (18) | 0.51712 (9) | 0.0286 (4) | |
H18A | 0.004811 | 0.795149 | 0.506235 | 0.043* | |
H18B | −0.050952 | 0.660124 | 0.522905 | 0.043* | |
H18C | 0.106810 | 0.712481 | 0.553218 | 0.043* | |
C1B | 1.08105 (19) | 0.75281 (13) | −0.02710 (7) | 0.0160 (2) | |
C2B | 1.1110 (2) | 0.83936 (14) | −0.07256 (7) | 0.0182 (3) | |
H2BA | 1.082866 | 0.823997 | −0.111375 | 0.022* | |
C3B | 1.1824 (2) | 0.94740 (14) | −0.05957 (7) | 0.0196 (3) | |
C4B | 1.2262 (2) | 0.97316 (14) | −0.00270 (7) | 0.0204 (3) | |
H4BA | 1.276857 | 1.047111 | 0.004956 | 0.025* | |
C5B | 1.1944 (2) | 0.88913 (14) | 0.04182 (7) | 0.0182 (3) | |
C6B | 1.12204 (19) | 0.77650 (13) | 0.03091 (7) | 0.0161 (2) | |
C7B | 1.1637 (3) | 1.02612 (19) | −0.15781 (9) | 0.0314 (4) | |
H7BA | 1.198245 | 1.096404 | −0.181871 | 0.047* | |
H7BB | 1.212344 | 0.951376 | −0.173589 | 0.047* | |
H7BC | 1.042495 | 1.023133 | −0.157835 | 0.047* | |
C8B | 1.3098 (3) | 1.01347 (18) | 0.11256 (9) | 0.0296 (4) | |
H8BA | 1.327350 | 1.012738 | 0.154572 | 0.044* | |
H8BB | 1.417031 | 1.016876 | 0.092174 | 0.044* | |
H8BC | 1.240046 | 1.084849 | 0.100772 | 0.044* | |
C9B | 1.08844 (19) | 0.69338 (14) | 0.07878 (7) | 0.0169 (2) | |
H9BA | 1.102943 | 0.722059 | 0.116600 | 0.020* | |
C10B | 1.0104 (2) | 0.51639 (14) | 0.13192 (7) | 0.0182 (3) | |
H10C | 0.917631 | 0.461323 | 0.127936 | 0.022* | |
H10D | 0.978321 | 0.575305 | 0.161728 | 0.022* | |
C11B | 1.1657 (2) | 0.44193 (16) | 0.15167 (7) | 0.0212 (3) | |
H11C | 1.200209 | 0.384829 | 0.121331 | 0.025* | |
H11D | 1.257509 | 0.497173 | 0.157111 | 0.025* | |
C12B | 1.1317 (2) | 0.37149 (15) | 0.20787 (7) | 0.0200 (3) | |
C13B | 1.1580 (2) | 0.42174 (17) | 0.26116 (8) | 0.0248 (3) | |
H13B | 1.200848 | 0.500606 | 0.262816 | 0.030* | |
C14B | 1.1211 (3) | 0.35536 (18) | 0.31177 (8) | 0.0260 (3) | |
H14B | 1.137798 | 0.388033 | 0.348626 | 0.031* | |
C15B | 1.0593 (3) | 0.24032 (19) | 0.30771 (8) | 0.0282 (4) | |
H15B | 1.030838 | 0.193012 | 0.341571 | 0.034* | |
C16B | 1.0403 (3) | 0.1966 (2) | 0.25299 (9) | 0.0371 (5) | |
H16B | 1.000665 | 0.116938 | 0.250348 | 0.045* | |
C17B | 0.5226 (2) | 0.70393 (18) | −0.02905 (9) | 0.0264 (3) | |
H17D | 0.479662 | 0.787575 | −0.024736 | 0.040* | |
H17E | 0.575775 | 0.697021 | −0.067328 | 0.040* | |
H17F | 0.430998 | 0.648204 | −0.025410 | 0.040* | |
C18B | 0.5303 (3) | 0.6533 (3) | 0.08640 (9) | 0.0400 (5) | |
H18D | 0.487442 | 0.734523 | 0.096103 | 0.060* | |
H18E | 0.437993 | 0.603326 | 0.076394 | 0.060* | |
H18F | 0.588691 | 0.615228 | 0.119890 | 0.060* | |
O1S | 0.7366 (3) | 0.6892 (3) | 0.21182 (12) | 0.0490 (6) | 0.774 (3) |
H1S | 0.644 (2) | 0.689 (5) | 0.2281 (13) | 0.073* | 0.774 (3) |
C1S | 0.8497 (6) | 0.7039 (4) | 0.25684 (15) | 0.0523 (9) | 0.774 (3) |
H1SD | 0.958649 | 0.721944 | 0.240058 | 0.078* | 0.774 (3) |
H1SA | 0.858738 | 0.628816 | 0.281184 | 0.078* | 0.774 (3) |
H1SB | 0.810224 | 0.771155 | 0.280573 | 0.078* | 0.774 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01323 (13) | 0.00974 (12) | 0.01742 (13) | −0.00149 (10) | −0.00032 (9) | −0.00011 (9) |
Mn2 | 0.01386 (13) | 0.01008 (12) | 0.01888 (14) | −0.00177 (10) | −0.00235 (10) | −0.00110 (10) |
S1A | 0.01467 (16) | 0.01704 (17) | 0.0354 (2) | 0.00072 (13) | −0.00139 (14) | 0.00494 (14) |
S1B | 0.01565 (17) | 0.01864 (17) | 0.0354 (2) | 0.00003 (13) | −0.00061 (14) | −0.00671 (15) |
Cl1 | 0.0454 (5) | 0.0229 (3) | 0.0253 (3) | 0.0047 (3) | −0.0010 (3) | −0.0018 (2) |
O11 | 0.100 (3) | 0.051 (3) | 0.0289 (16) | −0.013 (2) | −0.0065 (19) | −0.0146 (16) |
O12 | 0.069 (2) | 0.0277 (13) | 0.0291 (13) | −0.0005 (12) | 0.0004 (12) | 0.0017 (10) |
O13 | 0.088 (2) | 0.0512 (16) | 0.0505 (15) | 0.0363 (16) | 0.0060 (15) | 0.0154 (12) |
O14 | 0.0537 (19) | 0.084 (3) | 0.110 (3) | −0.0289 (18) | 0.0138 (18) | −0.045 (2) |
Cl1A | 0.096 (3) | 0.0244 (13) | 0.0278 (12) | −0.0124 (16) | −0.0050 (16) | −0.0059 (9) |
O11A | 0.065 (7) | 0.038 (6) | 0.028 (5) | 0.009 (6) | 0.018 (5) | −0.014 (4) |
O12A | 0.128 (8) | 0.022 (3) | 0.043 (4) | −0.009 (5) | −0.006 (5) | 0.006 (3) |
O13A | 0.072 (8) | 0.117 (10) | 0.101 (8) | −0.004 (8) | 0.007 (7) | −0.017 (8) |
O14A | 0.055 (5) | 0.023 (4) | 0.016 (3) | 0.009 (3) | −0.013 (3) | 0.000 (2) |
O1A | 0.0215 (5) | 0.0115 (4) | 0.0210 (5) | −0.0037 (4) | 0.0028 (4) | −0.0012 (4) |
O2A | 0.0367 (8) | 0.0171 (6) | 0.0415 (8) | −0.0086 (5) | 0.0009 (6) | −0.0113 (5) |
O3A | 0.0313 (7) | 0.0201 (6) | 0.0285 (6) | −0.0068 (5) | 0.0060 (5) | 0.0056 (5) |
O4A | 0.0146 (5) | 0.0153 (5) | 0.0348 (6) | 0.0003 (4) | −0.0022 (4) | 0.0034 (4) |
O1B | 0.0233 (6) | 0.0124 (4) | 0.0218 (5) | −0.0039 (4) | −0.0057 (4) | 0.0001 (4) |
O2B | 0.0399 (8) | 0.0182 (5) | 0.0259 (6) | −0.0097 (5) | −0.0018 (5) | 0.0050 (4) |
O3B | 0.0363 (7) | 0.0190 (5) | 0.0226 (6) | −0.0126 (5) | −0.0047 (5) | −0.0039 (4) |
O4B | 0.0149 (5) | 0.0160 (5) | 0.0390 (7) | −0.0006 (4) | −0.0005 (4) | −0.0043 (5) |
N1A | 0.0147 (5) | 0.0143 (5) | 0.0181 (5) | −0.0013 (4) | −0.0020 (4) | −0.0005 (4) |
N2A | 0.0367 (9) | 0.0231 (7) | 0.0291 (8) | −0.0030 (6) | −0.0023 (6) | −0.0052 (6) |
N1B | 0.0147 (5) | 0.0133 (5) | 0.0197 (5) | −0.0023 (4) | −0.0008 (4) | −0.0005 (4) |
N2B | 0.0472 (11) | 0.0226 (7) | 0.0241 (7) | −0.0117 (7) | −0.0045 (6) | 0.0013 (5) |
C1A | 0.0143 (6) | 0.0102 (5) | 0.0228 (6) | −0.0004 (4) | −0.0011 (5) | −0.0001 (4) |
C2A | 0.0193 (7) | 0.0128 (6) | 0.0254 (7) | −0.0007 (5) | −0.0011 (5) | −0.0031 (5) |
C3A | 0.0202 (7) | 0.0121 (6) | 0.0335 (8) | −0.0015 (5) | −0.0017 (6) | −0.0047 (5) |
C4A | 0.0205 (7) | 0.0117 (6) | 0.0366 (9) | −0.0037 (5) | −0.0002 (6) | 0.0003 (6) |
C5A | 0.0167 (6) | 0.0142 (6) | 0.0268 (7) | −0.0009 (5) | 0.0012 (5) | 0.0034 (5) |
C6A | 0.0147 (6) | 0.0119 (5) | 0.0218 (6) | −0.0015 (4) | −0.0002 (5) | 0.0011 (4) |
C7A | 0.0351 (10) | 0.0231 (8) | 0.0384 (10) | −0.0021 (7) | −0.0053 (8) | −0.0120 (7) |
C8A | 0.0475 (14) | 0.0286 (10) | 0.0466 (13) | −0.0147 (9) | 0.0098 (10) | 0.0142 (9) |
C9A | 0.0152 (6) | 0.0152 (6) | 0.0194 (6) | −0.0009 (5) | −0.0007 (4) | 0.0025 (5) |
C10A | 0.0186 (7) | 0.0185 (6) | 0.0188 (6) | −0.0015 (5) | −0.0040 (5) | −0.0027 (5) |
C11A | 0.0210 (7) | 0.0270 (8) | 0.0234 (7) | 0.0021 (6) | −0.0044 (5) | −0.0082 (6) |
C12A | 0.0204 (7) | 0.0215 (7) | 0.0239 (7) | 0.0012 (6) | −0.0031 (5) | −0.0076 (5) |
C13A | 0.0351 (10) | 0.0295 (9) | 0.0255 (8) | −0.0099 (8) | −0.0023 (7) | −0.0069 (7) |
C14A | 0.0397 (11) | 0.0383 (11) | 0.0235 (8) | −0.0085 (9) | −0.0038 (7) | −0.0074 (7) |
C15A | 0.0343 (10) | 0.0344 (10) | 0.0327 (10) | −0.0048 (8) | −0.0057 (8) | −0.0149 (8) |
C16A | 0.0420 (12) | 0.0241 (9) | 0.0400 (11) | −0.0069 (8) | −0.0043 (9) | −0.0095 (8) |
C17A | 0.0280 (9) | 0.0348 (10) | 0.0272 (9) | 0.0094 (8) | −0.0050 (7) | −0.0014 (7) |
C18A | 0.0282 (9) | 0.0265 (8) | 0.0313 (9) | 0.0070 (7) | −0.0079 (7) | −0.0063 (7) |
C1B | 0.0153 (6) | 0.0112 (5) | 0.0215 (6) | −0.0009 (4) | −0.0019 (5) | −0.0009 (4) |
C2B | 0.0207 (7) | 0.0135 (6) | 0.0204 (6) | −0.0016 (5) | −0.0019 (5) | 0.0002 (5) |
C3B | 0.0214 (7) | 0.0129 (6) | 0.0246 (7) | −0.0025 (5) | −0.0009 (5) | 0.0013 (5) |
C4B | 0.0229 (7) | 0.0132 (6) | 0.0256 (7) | −0.0050 (5) | −0.0016 (5) | −0.0015 (5) |
C5B | 0.0182 (6) | 0.0151 (6) | 0.0216 (7) | −0.0032 (5) | −0.0016 (5) | −0.0025 (5) |
C6B | 0.0164 (6) | 0.0126 (5) | 0.0195 (6) | −0.0024 (5) | −0.0013 (5) | −0.0017 (4) |
C7B | 0.0429 (12) | 0.0257 (8) | 0.0253 (8) | −0.0046 (8) | −0.0002 (7) | 0.0045 (7) |
C8B | 0.0391 (11) | 0.0224 (8) | 0.0288 (9) | −0.0146 (7) | −0.0058 (7) | −0.0045 (6) |
C9B | 0.0166 (6) | 0.0142 (6) | 0.0201 (6) | −0.0017 (5) | −0.0018 (5) | −0.0015 (5) |
C10B | 0.0194 (7) | 0.0157 (6) | 0.0196 (6) | −0.0029 (5) | 0.0013 (5) | 0.0001 (5) |
C11B | 0.0192 (7) | 0.0224 (7) | 0.0218 (7) | −0.0021 (6) | −0.0001 (5) | 0.0034 (5) |
C12B | 0.0198 (7) | 0.0185 (6) | 0.0216 (7) | −0.0019 (5) | −0.0020 (5) | 0.0023 (5) |
C13B | 0.0302 (9) | 0.0204 (7) | 0.0243 (8) | −0.0069 (6) | −0.0030 (6) | 0.0001 (6) |
C14B | 0.0317 (9) | 0.0256 (8) | 0.0209 (7) | −0.0048 (7) | −0.0024 (6) | 0.0003 (6) |
C15B | 0.0344 (10) | 0.0279 (9) | 0.0223 (8) | −0.0080 (7) | −0.0018 (6) | 0.0051 (6) |
C16B | 0.0601 (15) | 0.0241 (9) | 0.0284 (9) | −0.0192 (9) | −0.0044 (9) | 0.0026 (7) |
C17B | 0.0242 (8) | 0.0235 (8) | 0.0310 (9) | 0.0027 (6) | 0.0021 (6) | 0.0020 (6) |
C18B | 0.0375 (12) | 0.0538 (14) | 0.0267 (9) | 0.0186 (10) | 0.0031 (8) | 0.0007 (9) |
O1S | 0.0477 (15) | 0.0439 (14) | 0.0552 (15) | 0.0005 (11) | 0.0035 (11) | −0.0039 (11) |
C1S | 0.077 (3) | 0.0470 (19) | 0.0332 (16) | 0.0012 (19) | 0.0020 (15) | −0.0047 (13) |
Mn1—O1A | 1.8757 (11) | C10A—H10A | 0.9900 |
Mn1—O1Ai | 1.8757 (11) | C10A—H10B | 0.9900 |
Mn1—N1A | 2.0335 (13) | C11A—C12A | 1.512 (2) |
Mn1—N1Ai | 2.0336 (13) | C11A—H11A | 0.9900 |
Mn1—O4A | 2.2365 (12) | C11A—H11B | 0.9900 |
Mn1—O4Ai | 2.2365 (12) | C12A—C13A | 1.390 (3) |
Mn2—O1B | 1.8770 (11) | C13A—C14A | 1.388 (3) |
Mn2—O1Bii | 1.8770 (11) | C13A—H13A | 0.9500 |
Mn2—N1Bii | 2.0380 (13) | C14A—C15A | 1.382 (3) |
Mn2—N1B | 2.0380 (13) | C14A—H14A | 0.9500 |
Mn2—O4Bii | 2.2368 (13) | C15A—C16A | 1.381 (3) |
Mn2—O4B | 2.2368 (13) | C15A—H15A | 0.9500 |
S1A—O4A | 1.5293 (12) | C16A—H16A | 0.9500 |
S1A—C17A | 1.785 (2) | C17A—H17A | 0.9800 |
S1A—C18A | 1.791 (2) | C17A—H17B | 0.9800 |
S1B—O4B | 1.5287 (13) | C17A—H17C | 0.9800 |
S1B—C17B | 1.779 (2) | C18A—H18A | 0.9800 |
S1B—C18B | 1.785 (2) | C18A—H18B | 0.9800 |
Cl1—O11 | 1.4212 (15) | C18A—H18C | 0.9800 |
Cl1—O13 | 1.4241 (14) | C1B—C2B | 1.411 (2) |
Cl1—O12 | 1.4279 (15) | C1B—C6B | 1.419 (2) |
Cl1—O14 | 1.4365 (15) | C2B—C3B | 1.388 (2) |
Cl1A—O11A | 1.4256 (15) | C2B—H2BA | 0.9500 |
Cl1A—O12A | 1.4274 (15) | C3B—C4B | 1.406 (2) |
Cl1A—O14A | 1.4280 (15) | C4B—C5B | 1.380 (2) |
Cl1A—O13A | 1.4285 (15) | C4B—H4BA | 0.9500 |
O1A—C1A | 1.3240 (18) | C5B—C6B | 1.425 (2) |
O2A—C3A | 1.358 (2) | C6B—C9B | 1.433 (2) |
O2A—C7A | 1.429 (3) | C7B—H7BA | 0.9800 |
O3A—C5A | 1.363 (2) | C7B—H7BB | 0.9800 |
O3A—C8A | 1.434 (2) | C7B—H7BC | 0.9800 |
O1B—C1B | 1.3206 (18) | C8B—H8BA | 0.9800 |
O2B—C3B | 1.360 (2) | C8B—H8BB | 0.9800 |
O2B—C7B | 1.431 (2) | C8B—H8BC | 0.9800 |
O3B—C5B | 1.354 (2) | C9B—H9BA | 0.9500 |
O3B—C8B | 1.434 (2) | C10B—C11B | 1.534 (2) |
N1A—C9A | 1.299 (2) | C10B—H10C | 0.9900 |
N1A—C10A | 1.481 (2) | C10B—H10D | 0.9900 |
N2A—C12A | 1.342 (3) | C11B—C12B | 1.508 (2) |
N2A—C16A | 1.349 (3) | C11B—H11C | 0.9900 |
N1B—C9B | 1.299 (2) | C11B—H11D | 0.9900 |
N1B—C10B | 1.481 (2) | C12B—C13B | 1.391 (2) |
N2B—C16B | 1.343 (3) | C13B—C14B | 1.385 (3) |
N2B—C12B | 1.344 (2) | C13B—H13B | 0.9500 |
C1A—C2A | 1.414 (2) | C14B—C15B | 1.387 (3) |
C1A—C6A | 1.414 (2) | C14B—H14B | 0.9500 |
C2A—C3A | 1.387 (2) | C15B—C16B | 1.382 (3) |
C2A—H2AA | 0.9500 | C15B—H15B | 0.9500 |
C3A—C4A | 1.407 (3) | C16B—H16B | 0.9500 |
C4A—C5A | 1.374 (2) | C17B—H17D | 0.9800 |
C4A—H4AA | 0.9500 | C17B—H17E | 0.9800 |
C5A—C6A | 1.425 (2) | C17B—H17F | 0.9800 |
C6A—C9A | 1.435 (2) | C18B—H18D | 0.9800 |
C7A—H7AA | 0.9800 | C18B—H18E | 0.9800 |
C7A—H7AB | 0.9800 | C18B—H18F | 0.9800 |
C7A—H7AC | 0.9800 | O1S—C1S | 1.410 (5) |
C8A—H8AA | 0.9800 | O1S—H1S | 0.830 (10) |
C8A—H8AB | 0.9800 | C1S—H1SD | 0.9800 |
C8A—H8AC | 0.9800 | C1S—H1SA | 0.9800 |
C9A—H9AA | 0.9500 | C1S—H1SB | 0.9800 |
C10A—C11A | 1.530 (2) | ||
O1A—Mn1—O1Ai | 180.0 | H11A—C11A—H11B | 108.1 |
O1A—Mn1—N1A | 90.10 (5) | N2A—C12A—C13A | 122.45 (16) |
O1Ai—Mn1—N1A | 89.90 (5) | N2A—C12A—C11A | 116.68 (16) |
O1A—Mn1—N1Ai | 89.90 (5) | C13A—C12A—C11A | 120.84 (17) |
O1Ai—Mn1—N1Ai | 90.10 (5) | C14A—C13A—C12A | 119.36 (19) |
N1A—Mn1—N1Ai | 180.00 (8) | C14A—C13A—H13A | 120.3 |
O1A—Mn1—O4A | 90.48 (5) | C12A—C13A—H13A | 120.3 |
O1Ai—Mn1—O4A | 89.52 (5) | C15A—C14A—C13A | 118.7 (2) |
N1A—Mn1—O4A | 92.32 (5) | C15A—C14A—H14A | 120.7 |
N1Ai—Mn1—O4A | 87.68 (5) | C13A—C14A—H14A | 120.7 |
O1A—Mn1—O4Ai | 89.52 (5) | C16A—C15A—C14A | 118.46 (18) |
O1Ai—Mn1—O4Ai | 90.48 (5) | C16A—C15A—H15A | 120.8 |
N1A—Mn1—O4Ai | 87.68 (5) | C14A—C15A—H15A | 120.8 |
N1Ai—Mn1—O4Ai | 92.32 (5) | N2A—C16A—C15A | 123.8 (2) |
O4A—Mn1—O4Ai | 180.0 | N2A—C16A—H16A | 118.1 |
O1B—Mn2—O1Bii | 180.00 (8) | C15A—C16A—H16A | 118.1 |
O1B—Mn2—N1Bii | 90.60 (5) | S1A—C17A—H17A | 109.5 |
O1Bii—Mn2—N1Bii | 89.40 (5) | S1A—C17A—H17B | 109.5 |
O1B—Mn2—N1B | 89.40 (5) | H17A—C17A—H17B | 109.5 |
O1Bii—Mn2—N1B | 90.59 (5) | S1A—C17A—H17C | 109.5 |
N1Bii—Mn2—N1B | 180.00 (7) | H17A—C17A—H17C | 109.5 |
O1B—Mn2—O4Bii | 90.15 (5) | H17B—C17A—H17C | 109.5 |
O1Bii—Mn2—O4Bii | 89.85 (5) | S1A—C18A—H18A | 109.5 |
N1Bii—Mn2—O4Bii | 87.99 (5) | S1A—C18A—H18B | 109.5 |
N1B—Mn2—O4Bii | 92.01 (5) | H18A—C18A—H18B | 109.5 |
O1B—Mn2—O4B | 89.85 (5) | S1A—C18A—H18C | 109.5 |
O1Bii—Mn2—O4B | 90.15 (5) | H18A—C18A—H18C | 109.5 |
N1Bii—Mn2—O4B | 92.01 (5) | H18B—C18A—H18C | 109.5 |
N1B—Mn2—O4B | 87.99 (5) | O1B—C1B—C2B | 117.87 (14) |
O4Bii—Mn2—O4B | 180.0 | O1B—C1B—C6B | 121.68 (14) |
O4A—S1A—C17A | 104.11 (9) | C2B—C1B—C6B | 120.43 (14) |
O4A—S1A—C18A | 105.08 (9) | C3B—C2B—C1B | 118.84 (14) |
C17A—S1A—C18A | 98.35 (9) | C3B—C2B—H2BA | 120.6 |
O4B—S1B—C17B | 104.91 (9) | C1B—C2B—H2BA | 120.6 |
O4B—S1B—C18B | 104.63 (10) | O2B—C3B—C2B | 124.31 (15) |
C17B—S1B—C18B | 98.31 (10) | O2B—C3B—C4B | 113.50 (14) |
O11—Cl1—O13 | 110.35 (8) | C2B—C3B—C4B | 122.18 (15) |
O11—Cl1—O12 | 109.97 (8) | C5B—C4B—C3B | 118.84 (14) |
O13—Cl1—O12 | 109.65 (8) | C5B—C4B—H4BA | 120.6 |
O11—Cl1—O14 | 109.25 (8) | C3B—C4B—H4BA | 120.6 |
O13—Cl1—O14 | 108.89 (8) | O3B—C5B—C4B | 123.81 (14) |
O12—Cl1—O14 | 108.71 (8) | O3B—C5B—C6B | 114.89 (14) |
O11A—Cl1A—O12A | 109.64 (9) | C4B—C5B—C6B | 121.30 (14) |
O11A—Cl1A—O14A | 109.60 (9) | C1B—C6B—C5B | 118.39 (14) |
O12A—Cl1A—O14A | 109.38 (9) | C1B—C6B—C9B | 122.46 (13) |
O11A—Cl1A—O13A | 109.48 (9) | C5B—C6B—C9B | 119.13 (14) |
O12A—Cl1A—O13A | 109.41 (9) | O2B—C7B—H7BA | 109.5 |
O14A—Cl1A—O13A | 109.32 (9) | O2B—C7B—H7BB | 109.5 |
C1A—O1A—Mn1 | 128.49 (10) | H7BA—C7B—H7BB | 109.5 |
C3A—O2A—C7A | 117.94 (16) | O2B—C7B—H7BC | 109.5 |
C5A—O3A—C8A | 117.26 (17) | H7BA—C7B—H7BC | 109.5 |
S1A—O4A—Mn1 | 114.48 (7) | H7BB—C7B—H7BC | 109.5 |
C1B—O1B—Mn2 | 131.56 (10) | O3B—C8B—H8BA | 109.5 |
C3B—O2B—C7B | 118.09 (15) | O3B—C8B—H8BB | 109.5 |
C5B—O3B—C8B | 118.46 (14) | H8BA—C8B—H8BB | 109.5 |
S1B—O4B—Mn2 | 116.94 (7) | O3B—C8B—H8BC | 109.5 |
C9A—N1A—C10A | 116.07 (13) | H8BA—C8B—H8BC | 109.5 |
C9A—N1A—Mn1 | 123.36 (11) | H8BB—C8B—H8BC | 109.5 |
C10A—N1A—Mn1 | 120.39 (10) | N1B—C9B—C6B | 126.56 (14) |
C12A—N2A—C16A | 117.25 (18) | N1B—C9B—H9BA | 116.7 |
C9B—N1B—C10B | 115.93 (13) | C6B—C9B—H9BA | 116.7 |
C9B—N1B—Mn2 | 124.38 (11) | N1B—C10B—C11B | 111.19 (13) |
C10B—N1B—Mn2 | 119.67 (10) | N1B—C10B—H10C | 109.4 |
C16B—N2B—C12B | 117.14 (17) | C11B—C10B—H10C | 109.4 |
O1A—C1A—C2A | 117.43 (14) | N1B—C10B—H10D | 109.4 |
O1A—C1A—C6A | 121.76 (14) | C11B—C10B—H10D | 109.4 |
C2A—C1A—C6A | 120.78 (14) | H10C—C10B—H10D | 108.0 |
C3A—C2A—C1A | 118.47 (16) | C12B—C11B—C10B | 110.56 (14) |
C3A—C2A—H2AA | 120.8 | C12B—C11B—H11C | 109.5 |
C1A—C2A—H2AA | 120.8 | C10B—C11B—H11C | 109.5 |
O2A—C3A—C2A | 123.82 (17) | C12B—C11B—H11D | 109.5 |
O2A—C3A—C4A | 113.97 (15) | C10B—C11B—H11D | 109.5 |
C2A—C3A—C4A | 122.21 (15) | H11C—C11B—H11D | 108.1 |
C5A—C4A—C3A | 118.87 (15) | N2B—C12B—C13B | 122.58 (16) |
C5A—C4A—H4AA | 120.6 | N2B—C12B—C11B | 116.46 (15) |
C3A—C4A—H4AA | 120.6 | C13B—C12B—C11B | 120.96 (15) |
O3A—C5A—C4A | 124.17 (15) | C14B—C13B—C12B | 119.18 (17) |
O3A—C5A—C6A | 114.31 (15) | C14B—C13B—H13B | 120.4 |
C4A—C5A—C6A | 121.50 (16) | C12B—C13B—H13B | 120.4 |
C1A—C6A—C5A | 118.15 (14) | C13B—C14B—C15B | 118.85 (17) |
C1A—C6A—C9A | 122.61 (13) | C13B—C14B—H14B | 120.6 |
C5A—C6A—C9A | 119.15 (14) | C15B—C14B—H14B | 120.6 |
O2A—C7A—H7AA | 109.5 | C16B—C15B—C14B | 118.07 (17) |
O2A—C7A—H7AB | 109.5 | C16B—C15B—H15B | 121.0 |
H7AA—C7A—H7AB | 109.5 | C14B—C15B—H15B | 121.0 |
O2A—C7A—H7AC | 109.5 | N2B—C16B—C15B | 124.15 (19) |
H7AA—C7A—H7AC | 109.5 | N2B—C16B—H16B | 117.9 |
H7AB—C7A—H7AC | 109.5 | C15B—C16B—H16B | 117.9 |
O3A—C8A—H8AA | 109.5 | S1B—C17B—H17D | 109.5 |
O3A—C8A—H8AB | 109.5 | S1B—C17B—H17E | 109.5 |
H8AA—C8A—H8AB | 109.5 | H17D—C17B—H17E | 109.5 |
O3A—C8A—H8AC | 109.5 | S1B—C17B—H17F | 109.5 |
H8AA—C8A—H8AC | 109.5 | H17D—C17B—H17F | 109.5 |
H8AB—C8A—H8AC | 109.5 | H17E—C17B—H17F | 109.5 |
N1A—C9A—C6A | 126.02 (14) | S1B—C18B—H18D | 109.5 |
N1A—C9A—H9AA | 117.0 | S1B—C18B—H18E | 109.5 |
C6A—C9A—H9AA | 117.0 | H18D—C18B—H18E | 109.5 |
N1A—C10A—C11A | 111.85 (13) | S1B—C18B—H18F | 109.5 |
N1A—C10A—H10A | 109.2 | H18D—C18B—H18F | 109.5 |
C11A—C10A—H10A | 109.2 | H18E—C18B—H18F | 109.5 |
N1A—C10A—H10B | 109.2 | C1S—O1S—H1S | 105 (2) |
C11A—C10A—H10B | 109.2 | O1S—C1S—H1SD | 109.5 |
H10A—C10A—H10B | 107.9 | O1S—C1S—H1SA | 109.5 |
C12A—C11A—C10A | 110.29 (14) | H1SD—C1S—H1SA | 109.5 |
C12A—C11A—H11A | 109.6 | O1S—C1S—H1SB | 109.5 |
C10A—C11A—H11A | 109.6 | H1SD—C1S—H1SB | 109.5 |
C12A—C11A—H11B | 109.6 | H1SA—C1S—H1SB | 109.5 |
C10A—C11A—H11B | 109.6 | ||
N1A—Mn1—O1A—C1A | 30.38 (13) | N2A—C12A—C13A—C14A | 0.1 (3) |
N1Ai—Mn1—O1A—C1A | −149.62 (13) | C11A—C12A—C13A—C14A | 178.06 (19) |
O4A—Mn1—O1A—C1A | −61.94 (13) | C12A—C13A—C14A—C15A | −0.4 (3) |
O4Ai—Mn1—O1A—C1A | 118.05 (13) | C13A—C14A—C15A—C16A | 0.4 (4) |
C17A—S1A—O4A—Mn1 | 143.32 (9) | C12A—N2A—C16A—C15A | −0.2 (3) |
C18A—S1A—O4A—Mn1 | −113.81 (9) | C14A—C15A—C16A—N2A | −0.1 (4) |
N1Bii—Mn2—O1B—C1B | −157.35 (15) | Mn2—O1B—C1B—C2B | 161.78 (12) |
N1B—Mn2—O1B—C1B | 22.65 (15) | Mn2—O1B—C1B—C6B | −19.5 (2) |
O4Bii—Mn2—O1B—C1B | −69.36 (15) | O1B—C1B—C2B—C3B | 179.24 (15) |
O4B—Mn2—O1B—C1B | 110.64 (15) | C6B—C1B—C2B—C3B | 0.5 (2) |
C17B—S1B—O4B—Mn2 | 122.40 (9) | C7B—O2B—C3B—C2B | 7.4 (3) |
C18B—S1B—O4B—Mn2 | −134.66 (11) | C7B—O2B—C3B—C4B | −173.44 (17) |
Mn1—O1A—C1A—C2A | 154.60 (11) | C1B—C2B—C3B—O2B | 179.24 (16) |
Mn1—O1A—C1A—C6A | −27.4 (2) | C1B—C2B—C3B—C4B | 0.2 (3) |
O1A—C1A—C2A—C3A | 177.68 (15) | O2B—C3B—C4B—C5B | 179.67 (16) |
C6A—C1A—C2A—C3A | −0.4 (2) | C2B—C3B—C4B—C5B | −1.2 (3) |
C7A—O2A—C3A—C2A | 5.8 (3) | C8B—O3B—C5B—C4B | −2.3 (3) |
C7A—O2A—C3A—C4A | −175.16 (17) | C8B—O3B—C5B—C6B | 177.06 (16) |
C1A—C2A—C3A—O2A | 179.19 (16) | C3B—C4B—C5B—O3B | −179.19 (16) |
C1A—C2A—C3A—C4A | 0.2 (2) | C3B—C4B—C5B—C6B | 1.5 (3) |
O2A—C3A—C4A—C5A | −179.80 (16) | O1B—C1B—C6B—C5B | −178.92 (14) |
C2A—C3A—C4A—C5A | −0.7 (3) | C2B—C1B—C6B—C5B | −0.2 (2) |
C8A—O3A—C5A—C4A | 2.2 (3) | O1B—C1B—C6B—C9B | −1.0 (2) |
C8A—O3A—C5A—C6A | −179.41 (17) | C2B—C1B—C6B—C9B | 177.68 (15) |
C3A—C4A—C5A—O3A | 179.69 (16) | O3B—C5B—C6B—C1B | 179.83 (15) |
C3A—C4A—C5A—C6A | 1.4 (3) | C4B—C5B—C6B—C1B | −0.8 (2) |
O1A—C1A—C6A—C5A | −176.92 (14) | O3B—C5B—C6B—C9B | 1.8 (2) |
C2A—C1A—C6A—C5A | 1.1 (2) | C4B—C5B—C6B—C9B | −178.77 (15) |
O1A—C1A—C6A—C9A | −0.6 (2) | C10B—N1B—C9B—C6B | −178.73 (15) |
C2A—C1A—C6A—C9A | 177.41 (14) | Mn2—N1B—C9B—C6B | 0.0 (2) |
O3A—C5A—C6A—C1A | 179.97 (14) | C1B—C6B—C9B—N1B | 10.1 (3) |
C4A—C5A—C6A—C1A | −1.6 (2) | C5B—C6B—C9B—N1B | −172.01 (15) |
O3A—C5A—C6A—C9A | 3.5 (2) | C9B—N1B—C10B—C11B | −93.08 (17) |
C4A—C5A—C6A—C9A | −178.08 (15) | Mn2—N1B—C10B—C11B | 88.15 (14) |
C10A—N1A—C9A—C6A | −178.90 (14) | N1B—C10B—C11B—C12B | −178.01 (13) |
Mn1—N1A—C9A—C6A | −3.8 (2) | C16B—N2B—C12B—C13B | 0.9 (3) |
C1A—C6A—C9A—N1A | 15.9 (2) | C16B—N2B—C12B—C11B | −178.7 (2) |
C5A—C6A—C9A—N1A | −167.76 (15) | C10B—C11B—C12B—N2B | 89.7 (2) |
C9A—N1A—C10A—C11A | −93.76 (17) | C10B—C11B—C12B—C13B | −89.9 (2) |
Mn1—N1A—C10A—C11A | 90.96 (15) | N2B—C12B—C13B—C14B | −1.3 (3) |
N1A—C10A—C11A—C12A | 178.38 (14) | C11B—C12B—C13B—C14B | 178.28 (17) |
C16A—N2A—C12A—C13A | 0.3 (3) | C12B—C13B—C14B—C15B | 0.2 (3) |
C16A—N2A—C12A—C11A | −177.81 (18) | C13B—C14B—C15B—C16B | 1.1 (3) |
C10A—C11A—C12A—N2A | 88.9 (2) | C12B—N2B—C16B—C15B | 0.6 (4) |
C10A—C11A—C12A—C13A | −89.2 (2) | C14B—C15B—C16B—N2B | −1.6 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1S—H1S···O14 | 0.83 (2) | 2.21 (4) | 2.864 (4) | 136 (5) |
O1S—H1S···O13A | 0.83 (2) | 1.06 (3) | 1.813 (7) | 147 (6) |
C7A—H7AA···O12iii | 0.98 | 2.44 | 3.395 (3) | 165 |
C7A—H7AA···O14Aiii | 0.98 | 2.49 | 3.415 (7) | 157 |
C10A—H10B···O12i | 0.99 | 2.57 | 3.408 (3) | 142 |
C10A—H10B···O14Ai | 0.99 | 2.36 | 3.243 (8) | 148 |
C17A—H17B···O12 | 0.98 | 2.69 | 3.173 (4) | 112 |
C9B—H9BA···O11iv | 0.95 | 2.60 | 3.405 (3) | 143 |
C9B—H9BA···O11Aiv | 0.95 | 2.52 | 3.311 (7) | 141 |
C16A—H16A···O12Av | 0.95 | 2.66 | 3.563 (6) | 160 |
C11B—H11D···O11Aiv | 0.99 | 2.57 | 3.380 (8) | 139 |
C17A—H17A···O3Avi | 0.98 | 2.55 | 3.455 (3) | 154 |
C13A—H13A···O1Si | 0.95 | 2.42 | 3.343 (4) | 165 |
C18A—H18B···O4Avi | 0.98 | 2.56 | 3.491 (3) | 160 |
C17B—H17F···O4Bvii | 0.98 | 2.43 | 3.384 (2) | 163 |
C7B—H7BA···O1Sviii | 0.98 | 2.51 | 3.445 (4) | 160 |
C10B—H10D···O1S | 0.99 | 2.57 | 3.428 (3) | 146 |
C18B—H18F···O1S | 0.98 | 2.62 | 3.402 (3) | 137 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) x+1, y, z; (v) −x+1, −y+2, −z+1; (vi) −x, −y+1, −z+1; (vii) −x+1, −y+1, −z; (viii) −x+2, −y+2, −z. |
Acknowledgements
RJB is grateful to the NSF, Partnership for Reduced Dimensional Materials, for partial funding of this research, as well as the Howard University Nanoscience Facility for access to liquid nitrogen. RJB acknowledges the NSF MRI program for funds to purchase an X-ray diffractometer.
Funding information
Funding for this research was provided by: National Science Foundation, Directorate for Mathematical and Physical Sciences (grant Nos. 1205608 and CHE-0619278).
References
Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire, England.
Aubin, S. M. J., Dilley, N. R., Pardi, L., Krzystek, J., Wemple, M. W., Brunel, L. C., Maple, M. B., Christou, G. & Hendrickson, D. N. (1998). J. Am. Chem. Soc. 120, 4991–5004. Web of Science CrossRef CAS
Awschalom, D. D., Di Vincenzo, D. P. & Smyth, J. J. (1992). Science, 258, 414–421. CrossRef PubMed CAS Web of Science
Bermejo, M. R., Garcia-Deibe, A., Sanmartin, J., Sousa, A., Aurangzeb, N., Hulme, C. E., McAuliffe, C. A., Pritchard, R. G. & Watkinson, M. (1994). J. Chem. Soc. Chem. Commun. pp. 645–646. CrossRef Web of Science
Boskovic, C., Brechin, E. K., Streib, W. E., Folting, K., Bollinger, J. C., Hendrickson, D. N. & Christou, G. (2002). J. Am. Chem. Soc. 124, 3725–3736. Web of Science CSD CrossRef PubMed CAS
Boyd, P. D. W., Li, Q. Y., Vincent, J. B., Folting, K., Chang, H. R., Streib, W. E., Huffman, J. C., Christou, G. & Hendrickson, D. N. (1988). J. Am. Chem. Soc. 110, 8537–8539. CSD CrossRef CAS Web of Science
Christou, G., Gatteschi, D., Hendrickson, D. N. & Sessoli, R. (2000). MRS Bull. 25, 66–71. Web of Science CrossRef CAS
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897. CrossRef CAS Web of Science IUCr Journals
Cornia, A., Fabretti, A. C., Pacchioni, M., Zobbi, L., Bonachi, D., Caneschi, A., Gatteschi, D., Biagi, R., Del Pennino, U., De Renzi, V., Gurevich, L. & Van der Zant, H. S. J. (2003). Angew. Chem. Int. Ed. Engl. 42, 1645–1648. Web of Science CrossRef PubMed CAS
Dahlberg, E. D. & Zhu, J.-G. (1995). Phys. Today, 48, 34–40. CrossRef CAS Web of Science
Egekenze, R., Gultneh, Y. & Butcher, R. J. (2017a). Acta Cryst. E73, 1113–1116. Web of Science CSD CrossRef IUCr Journals
Egekenze, R., Gultneh, Y. & Butcher, R. J. (2017b). Inorg. Chim. Acta. Submitted.
Egekenze, R., Gultneh, Y. & Butcher, R. J. (2017c). Polyhedron, Submitted.
Gatteschi, D., Caneschi, A., Pardi, L. & Sessoli, R. (1994). Science, 265, 1054–1058. CrossRef PubMed CAS Web of Science
Gatteschi, D. & Sessoli, R. (2003). Angew. Chem. Int. Ed. Engl. 42, 268–297. Web of Science CrossRef PubMed CAS
Gatteschi, D., Sessoli, R. & Villain, J. (2006). In Molecular Magnets. Oxford University Press.
Glaser, T., Heidemeier, M. & Fröhlich, R. (2007). C. R. Chim. 10, 71–78. Web of Science CSD CrossRef CAS
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals
Jahn, H. A. & Teller, E. (1937). Proc. R. Soc. A, 161, 220–235. CrossRef CAS
Leuenberger, M. N. & Loss, D. (2001). Nature, 410, 789–793. Web of Science CrossRef PubMed CAS
Lis, T. (1980). Acta Cryst. B36, 2042–2046. CSD CrossRef CAS IUCr Journals Web of Science
Long, J. R. (2003). Chemistry of Nanostructured Materials, edited by P. Yang, p. 291. Hong Kong: World Scientific.
Miyasaka, H., Clerac, R., Wernsdorfer, W., Lecren, L., Bonhomme, C., Sugiura, K.-I. & Yamashita, M. (2004). Angew. Chem. Int. Ed. Engl. 43, 2801–2805. Web of Science CSD CrossRef PubMed CAS
Sessoli, R., Gatteschi, D., Caneschi, A. & Novak, M. A. (1993a). Nature, 365, 141–143. CrossRef CAS Web of Science
Sessoli, R., Tsai, H. L., Schake, A. R., Wang, S. Y., Vincent, J. B., Folting, K., Gatteschi, D., Christou, G. & Hendrickson, D. N. (1993b). J. Am. Chem. Soc. 115, 1804–1816. CSD CrossRef CAS Web of Science
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals
Sun, Z. M., Ruiz, D., Rumberger, E., Incarvito, C. D., Folting, K., Rheingold, A. L., Christou, G. & Hendrickson, D. N. (1998). Inorg. Chem. 37, 4758–4759. Web of Science CSD CrossRef PubMed CAS
Tejada, J. (2001). Polyhedron, 20, 1751–1756. Web of Science CrossRef CAS
Thomas, L., Lionti, F., Ballou, R., Gatteschi, D., Sessoli, R. & Barbara, B. (1996). Nature, 383, 145–147. CrossRef CAS Web of Science
Tsai, H. L., Eppley, H. J., Devries, N., Folting, K., Christou, G. & Hendrickson, D. N. (1994). J. Chem. Soc. Chem. Commun. pp. 1745–1746. CrossRef Web of Science
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