supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

bh2151 scheme

Acta Cryst. (2008). E64, m161    [ doi:10.1107/S1600536807065269 ]

Tetrakis([mu]-phenoxyacetato-[kappa]2O:O')bis[(1,10-phenanthroline-[kappa]2N,N')manganese(II)] methanol hemisolvate

D.-H. Wu, J. Shi, Y.-J. Shi and G.-Q. Jiang

Abstract top

The title complex, [Mn2(C8H7O3)4(C12H8N2)2]·0.5CH3OH, is a carboxylate-bridged dinuclear MnII complex with four phenoxyacetate ions and two 1,10-phenanthroline molecules as ligands. Each of the four phenoxyacetate anions bridges the pair of Mn atoms. The asymmetric unit is completed by a half-occupancy methanol solvent molecule. Face-to-face [pi]-[pi] stacking interactions between the aromatic rings of 1,10-phenanthroline molecules belonging to adjacent Mn2 complexes, with an interplanar separation of circa 3.4 Å, and weak C-H...O hydrogen bonds connect the dinuclear units into a three-dimensional supramolecular framework.

Comment top

The rational design, synthesis and characterization of novel supramolecular frameworks are currently of great interest. One of the greatest challenges in this area is the construction of porous materials from metal ions and organic ligands as building blocks (Yaghi et al., 1997). As part of our search for new porous metal-organic frameworks, we are studying complexes of transition metals with phenoxyacetate ligands (Jiang et al., 2005, 2006). Here, the title compound, (I), a novel dinuclear MnII complex with 1,10-phenanthroline as co-ligands, is reported.

Complex (I) exists as a dinuclear unit, with four bidentate phenoxyacetate anions bridging the pair of MnII atoms (Fig. 1). Two N atoms from 1,10-phenanthroline molecules bind to the MnII atoms, and both MnII atoms thus possess a distorted octahedral coordination geometry. The asymmetric unit is completed by 1/2 methanol solvate. The Mn—O distances are in the range 2.087 (2) to 2.351 (3) Å, and the average distance for Mn—N bonds is 2.31 Å. The planes of two coordinated phenanthroline molecules are set approximately perpendicular to each other.

Interestingly, The Mn2 units further link to each other into a microporous framework (Fig. 2) by π-stacking from the plane of 1,10-phenanthroline of symmetry-related molecules and C—H···O hydrogen bond interactions between alternating molecules. These supramolecular interactions are illustrated in Fig. 3. The C—H···O hydrogen bonds that exist in the peripheral ligands of adjacent Mn2 complexes are formed via the H donor atoms from phenyl group and acceptor O atoms of OCH2 groups of phenoxyacetate ligands. It is noteworthy that the contacts are almost linear (C—H···O: 174.9°). The structural significance is that the dipole-monopole and dipole-dipole contributions to electrostatic energy are maximum at 180° and zero at 90°. Therefore, this interaction may be considered as an efficient C—H···O hydrogen bond.

The overall three-dimensional supramolecular structure is also stabilized by significant offset face-to-face π···π stacking interactions between the aromatic rings of 1,10-phenanthroline molecules belonging to adjacent Mn2 complexes, with an interplanar separation of ca 3.4 Å and θ = 21.9° (Fig. 3).

Related literature top

For related literature, see: Jiang et al. (2005, 2006); Sessoli et al. (1993); Yaghi et al. (1997).

Experimental top

[Mn3O(O2CCH2OPh)6(pyridine)2(H2O)] was synthesized according to the literature method of Sessoli et al., (1993). To a solution of [Mn3O(O2CCH2OPh)6(pyridine)2(H2O)] (0.15 mmol 0.18 g) in MeCN (8 ml) and CH3OH (2 ml), powdered 1,10-phenanthroline (0.15 mmol 0.030 g) was added. The resulting solution was stirred for 0.5 h., filtered and layered with two volumes of Et2O. After two weeks, light brown crystals of (I) were collected by filtration, washed with Et2O, and dried in vacuo. The yield was approximately 20%.

Refinement top

Carbon-bound H atoms were positioned geometrically, with C—H = 0.97 Å for methylene groups, 0.93 Å for aromatic groups, and 0.96 Å for the methyl groups of MeOH. They were refined using a riding model, with Uiso(H) = 1.2Ueq(carrier C) for the complex and Uiso(H) = 1.5Ueq(C57) for the MeOH molecule. The hydroxyl H atom H13a was positioned geometrically and freely refined. Occupancy for the methanol molecule was refined in preliminary cycles and fixed to 1/2 for final refinement. Finally, geometry for phenyl ring C1···C6 was constrained by fitting the six C atoms to a regular hexagon with C?C bond lengths of 1.39 Å.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. The structure of (I), with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted.
[Figure 2] Fig. 2. View of the microporous network of (I) along [001]. The guest CH3OH molecules and H atoms are omitted for clarity.
[Figure 3] Fig. 3. The π···π interactions and C—H···O hydrogen interactions in (I) are shown (dashed lines). Cg1 is the centroid of the interacting aromatic ring of 1,10-phenanthroline molecule in the asymmetric unit.
Tetrakis(µ-phenoxyacetato-κ2O:O')bis[(1,10- phenanthroline-κ2N,N')manganese(II)] methanol hemisolvate top
Crystal data top
[Mn2(C8H7O3)4(C12H8N2)2]·0.5CH4OZ = 2
Mr = 1090.86F000 = 1126.0
Triclinic, P1Dx = 1.363 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 12.4627 (10) ÅCell parameters from 14596 reflections
b = 12.8334 (10) Åθ = 2.4–28.1º
c = 17.1377 (13) ŵ = 0.54 mm−1
α = 77.421 (1)ºT = 193 (2) K
β = 87.635 (1)ºPrism, light brown
γ = 84.629 (1)º0.30 × 0.24 × 0.22 mm
V = 2662.8 (4) Å3
Data collection top
Bruker SMART APEX CCD area detector
diffractometer		10273 independent reflections
Radiation source: fine-focus sealed tube6679 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 193(2) Kθmax = 26.0º
φ and ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −12→15
Tmin = 0.848, Tmax = 0.879k = −15→15
14596 measured reflectionsl = −21→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.149  w = 1/[σ2(Fo2) + (0.0726P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
10273 reflectionsΔρmax = 0.97 e Å−3
675 parametersΔρmin = −0.53 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn2(C8H7O3)4(C12H8N2)2]·0.5CH4Oγ = 84.629 (1)º
Mr = 1090.86V = 2662.8 (4) Å3
Triclinic, P1Z = 2
a = 12.4627 (10) ÅMo Kα
b = 12.8334 (10) ŵ = 0.54 mm−1
c = 17.1377 (13) ÅT = 193 (2) K
α = 77.421 (1)º0.30 × 0.24 × 0.22 mm
β = 87.635 (1)º
Data collection top
Bruker SMART APEX CCD area detector
diffractometer		10273 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		6679 reflections with I > 2σ(I)
Tmin = 0.848, Tmax = 0.879Rint = 0.030
14596 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.066675 parameters
wR(F2) = 0.149H-atom parameters constrained
S = 1.08Δρmax = 0.97 e Å−3
10273 reflectionsΔρmin = −0.53 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C1−0.14992 (18)0.29242 (18)0.19427 (14)0.0413 (8)
C2−0.2086 (2)0.29890 (17)0.12587 (12)0.0528 (10)
H2−0.19870.35320.08110.063*
C3−0.28204 (19)0.2243 (2)0.12443 (12)0.0400 (8)
H3−0.32130.22860.07870.048*
C4−0.29687 (19)0.14321 (18)0.19139 (14)0.0448 (9)
H4−0.34600.09330.19040.054*
C5−0.2382 (2)0.13673 (19)0.25979 (12)0.0525 (11)
H5−0.24810.08250.30460.063*
C6−0.1647 (2)0.2113 (2)0.26123 (12)0.0533 (11)
H6−0.12550.20700.30700.064*
C7−0.0082 (3)0.3575 (3)0.2531 (2)0.0420 (9)
H7A0.03710.29110.25580.050*
H7B−0.04860.35210.30320.050*
C80.0627 (3)0.4501 (3)0.24232 (19)0.0309 (7)
C90.5655 (3)0.5993 (3)0.1346 (2)0.0354 (7)
C100.6748 (3)0.5765 (3)0.1533 (2)0.0393 (8)
H100.70770.50770.15600.047*
C110.7337 (3)0.6559 (3)0.1676 (2)0.0408 (8)
H110.80640.64020.17920.049*
C120.6876 (3)0.7566 (3)0.1652 (2)0.0445 (9)
H120.72880.80950.17410.053*
C130.5785 (3)0.7801 (3)0.1493 (2)0.0399 (8)
H130.54580.84830.14900.048*
C140.5185 (3)0.7011 (3)0.1337 (2)0.0442 (9)
H140.44570.71720.12260.053*
C150.4190 (3)0.5449 (3)0.0745 (2)0.0389 (8)
H15A0.40780.48730.04800.047*
H15B0.42830.60860.03330.047*
C160.3174 (3)0.5660 (3)0.1243 (2)0.0310 (7)
C170.3770 (3)1.0392 (3)0.1738 (2)0.0393 (8)
C180.3870 (3)1.0841 (3)0.2409 (2)0.0452 (9)
H180.37411.04490.29230.054*
C190.4157 (3)1.1856 (3)0.2287 (2)0.0438 (9)
H190.41901.21660.27270.053*
C200.4399 (3)1.2444 (3)0.1549 (2)0.0480 (10)
H200.46201.31300.14850.058*
C210.4307 (3)1.1994 (4)0.0907 (3)0.0535 (11)
H210.44511.23890.03970.064*
C220.4008 (3)1.0974 (4)0.0996 (2)0.0508 (10)
H220.39671.06780.05490.061*
C230.3286 (4)0.8737 (3)0.2547 (2)0.0484 (11)
H23A0.28000.91260.28620.058*
H23B0.39690.85620.28190.058*
C240.2811 (3)0.7703 (3)0.2477 (2)0.0335 (7)
C25−0.1736 (4)0.7864 (3)0.4493 (2)0.0498 (10)
C26−0.2615 (3)0.8525 (3)0.4155 (3)0.0514 (10)
H26−0.26770.87090.36020.062*
C27−0.3402 (3)0.8912 (3)0.4640 (2)0.0439 (9)
H27−0.39790.93740.44120.053*
C28−0.3331 (3)0.8612 (3)0.5466 (2)0.0410 (8)
H28−0.38570.88740.57930.049*
C29−0.2472 (3)0.7921 (3)0.5800 (2)0.0440 (9)
H29−0.24300.77080.63530.053*
C30−0.1684 (3)0.7548 (4)0.5324 (2)0.0461 (9)
H30−0.11110.70820.55560.055*
C31−0.0959 (3)0.7740 (3)0.3230 (2)0.0464 (9)
H31A−0.09510.85110.30610.056*
H31B−0.16330.75440.30630.056*
C32−0.0029 (3)0.7204 (3)0.28230 (19)0.0360 (8)
C330.1833 (3)0.9173 (3)0.0287 (2)0.0370 (8)
H330.23240.90840.06950.044*
C340.1832 (3)1.0099 (3)−0.0315 (2)0.0450 (9)
H340.23071.0612−0.03040.054*
C350.1116 (3)1.0241 (3)−0.0925 (2)0.0446 (9)
H350.10991.0854−0.13310.054*
C360.0412 (3)0.9455 (3)−0.0928 (2)0.0389 (8)
C370.0465 (3)0.8542 (3)−0.02921 (19)0.0313 (7)
C38−0.0349 (3)0.9524 (3)−0.1547 (2)0.0484 (10)
H38−0.03971.0125−0.19640.058*
C39−0.0986 (3)0.8749 (3)−0.1535 (2)0.0400 (9)
H39−0.14800.8822−0.19400.048*
C40−0.0930 (3)0.7803 (3)−0.0912 (2)0.0404 (9)
C41−0.0215 (3)0.7696 (3)−0.0285 (2)0.0341 (7)
C42−0.1555 (3)0.6923 (3)−0.0897 (2)0.0398 (8)
H42−0.20460.6951−0.12960.048*
C43−0.1425 (3)0.6043 (4)−0.0292 (2)0.0494 (10)
H43−0.18040.5451−0.02870.059*
C44−0.0725 (3)0.6034 (3)0.0315 (2)0.0420 (8)
H44−0.06730.54390.07370.050*
C450.4660 (3)0.4104 (3)0.3261 (2)0.0489 (10)
H450.46300.42430.27060.059*
C460.5584 (3)0.3533 (4)0.3622 (2)0.0520 (11)
H460.61510.32900.33190.062*
C470.5625 (4)0.3341 (3)0.4441 (3)0.0555 (12)
H470.62320.29660.46970.067*
C480.4771 (3)0.3700 (3)0.4897 (3)0.0520 (11)
C490.4763 (3)0.3541 (3)0.5763 (3)0.0514 (11)
H490.53640.31930.60420.062*
C500.3923 (3)0.3878 (3)0.6161 (2)0.0427 (9)
H500.39400.37560.67150.051*
C510.2991 (3)0.4425 (3)0.5758 (2)0.0429 (9)
C520.2071 (3)0.4781 (3)0.6160 (2)0.0407 (9)
H520.20500.46600.67150.049*
C530.1195 (3)0.5313 (3)0.5726 (2)0.0430 (9)
H530.05740.55370.59860.052*
C540.1259 (4)0.5508 (4)0.4887 (2)0.0514 (10)
H540.06740.58790.45990.062*
C550.2979 (3)0.4632 (3)0.4909 (2)0.0407 (9)
C560.3875 (3)0.4251 (3)0.4477 (2)0.0396 (9)
C570.0849 (6)0.9332 (6)0.4635 (5)0.0479 (19)0.50
H57A0.03560.92780.42330.072*0.50
H57B0.11321.00220.45020.072*0.50
H57C0.04780.92500.51440.072*0.50
Mn10.10626 (4)0.68940 (4)0.13078 (3)0.03282 (14)
Mn20.23017 (4)0.55146 (4)0.31185 (3)0.03575 (15)
N10.1173 (2)0.8407 (2)0.03126 (18)0.0357 (6)
N2−0.0120 (2)0.6833 (2)0.03250 (16)0.0330 (6)
N30.3823 (3)0.4459 (2)0.36634 (18)0.0380 (7)
N40.2115 (3)0.5187 (2)0.44880 (17)0.0392 (7)
O10.0482 (2)0.5285 (2)0.18646 (15)0.0429 (6)
O20.1310 (2)0.4354 (2)0.29637 (15)0.0419 (6)
O30.23937 (19)0.6113 (2)0.08234 (13)0.0364 (5)
O40.3193 (2)0.5381 (2)0.19865 (14)0.0407 (6)
O50.2302 (2)0.7683 (2)0.18841 (14)0.0422 (6)
O60.2997 (2)0.6956 (2)0.30779 (14)0.0421 (6)
O7−0.0072 (2)0.7512 (2)0.20771 (14)0.0419 (6)
O80.0669 (2)0.6563 (2)0.32082 (14)0.0429 (6)
O9−0.0808 (2)0.3710 (2)0.18956 (16)0.0488 (7)
O100.5155 (2)0.5172 (2)0.11822 (17)0.0502 (7)
O110.34476 (19)0.93894 (19)0.17765 (14)0.0364 (5)
O12−0.0909 (2)0.7446 (2)0.40745 (14)0.0436 (6)
O130.1737 (5)0.8490 (6)0.4676 (4)0.0653 (17)0.50
H13A0.14930.79180.46780.098*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0321 (18)0.047 (2)0.048 (2)−0.0083 (16)0.0017 (16)−0.0154 (17)
C20.039 (2)0.064 (3)0.059 (3)−0.0034 (19)−0.0030 (19)−0.020 (2)
C30.041 (2)0.047 (2)0.0373 (19)−0.0152 (16)−0.0023 (16)−0.0153 (16)
C40.052 (2)0.048 (2)0.040 (2)−0.0109 (18)0.0000 (17)−0.0187 (17)
C50.047 (2)0.069 (3)0.041 (2)−0.036 (2)0.0106 (18)−0.0006 (19)
C60.054 (2)0.063 (3)0.042 (2)−0.028 (2)−0.0052 (19)−0.0007 (19)
C70.046 (2)0.040 (2)0.038 (2)−0.0128 (17)−0.0056 (16)−0.0006 (16)
C80.0352 (18)0.0359 (18)0.0220 (16)−0.0106 (14)0.0027 (13)−0.0045 (13)
C90.0341 (18)0.0407 (19)0.0306 (18)−0.0041 (14)0.0080 (14)−0.0066 (14)
C100.0315 (18)0.041 (2)0.043 (2)0.0055 (15)0.0025 (15)−0.0088 (16)
C110.0355 (19)0.055 (2)0.0354 (19)−0.0203 (17)0.0029 (15)−0.0103 (16)
C120.043 (2)0.039 (2)0.051 (2)−0.0162 (17)0.0105 (18)−0.0062 (17)
C130.040 (2)0.0389 (19)0.0410 (19)−0.0214 (15)0.0001 (15)−0.0022 (15)
C140.041 (2)0.052 (2)0.036 (2)−0.0127 (17)0.0000 (16)0.0011 (17)
C150.046 (2)0.0366 (19)0.0373 (19)−0.0051 (15)0.0008 (16)−0.0141 (15)
C160.0316 (17)0.0262 (16)0.0341 (19)−0.0034 (13)−0.0061 (14)−0.0027 (13)
C170.0369 (19)0.0340 (19)0.046 (2)−0.0066 (14)−0.0044 (16)−0.0050 (15)
C180.044 (2)0.048 (2)0.051 (2)−0.0303 (18)0.0025 (18)−0.0148 (18)
C190.0401 (19)0.055 (2)0.050 (2)−0.0270 (17)0.0058 (16)−0.0336 (19)
C200.063 (3)0.035 (2)0.045 (2)−0.0208 (18)0.0022 (19)−0.0008 (16)
C210.040 (2)0.060 (3)0.052 (2)−0.0241 (19)−0.0029 (18)0.014 (2)
C220.054 (2)0.058 (3)0.042 (2)−0.022 (2)0.0002 (18)−0.0060 (18)
C230.078 (3)0.035 (2)0.0332 (19)−0.0255 (19)−0.0205 (19)0.0022 (15)
C240.0406 (19)0.0219 (16)0.0368 (19)−0.0077 (13)−0.0052 (15)−0.0008 (14)
C250.057 (2)0.049 (2)0.042 (2)−0.0091 (19)0.0114 (18)−0.0055 (17)
C260.050 (2)0.041 (2)0.058 (3)0.0090 (18)0.0098 (19)−0.0052 (18)
C270.041 (2)0.042 (2)0.046 (2)0.0180 (16)0.0153 (17)−0.0147 (17)
C280.043 (2)0.042 (2)0.039 (2)−0.0013 (16)0.0110 (16)−0.0127 (16)
C290.047 (2)0.045 (2)0.043 (2)−0.0116 (17)0.0154 (17)−0.0158 (17)
C300.038 (2)0.064 (3)0.038 (2)−0.0127 (18)0.0077 (16)−0.0131 (18)
C310.049 (2)0.050 (2)0.038 (2)−0.0007 (18)0.0033 (17)−0.0077 (17)
C320.047 (2)0.0372 (19)0.0220 (16)−0.0050 (15)−0.0011 (14)−0.0018 (14)
C330.0399 (19)0.0396 (19)0.0289 (17)−0.0075 (15)−0.0081 (14)0.0014 (14)
C340.047 (2)0.041 (2)0.042 (2)−0.0131 (17)−0.0026 (17)0.0049 (16)
C350.047 (2)0.044 (2)0.035 (2)−0.0064 (17)−0.0016 (17)0.0102 (16)
C360.046 (2)0.040 (2)0.0242 (17)0.0077 (16)−0.0019 (15)0.0005 (14)
C370.0304 (17)0.0383 (18)0.0235 (16)0.0053 (14)0.0006 (13)−0.0070 (13)
C380.054 (2)0.050 (2)0.034 (2)0.0077 (19)−0.0127 (17)0.0049 (17)
C390.042 (2)0.044 (2)0.0320 (18)0.0144 (17)−0.0149 (15)−0.0081 (15)
C400.0336 (18)0.060 (2)0.0252 (17)0.0065 (17)−0.0031 (14)−0.0077 (16)
C410.0268 (16)0.0376 (19)0.0351 (18)−0.0027 (13)−0.0019 (13)−0.0017 (14)
C420.0388 (19)0.048 (2)0.041 (2)−0.0062 (16)−0.0086 (16)−0.0249 (17)
C430.044 (2)0.062 (3)0.044 (2)−0.0156 (19)−0.0107 (18)−0.0097 (19)
C440.043 (2)0.052 (2)0.0322 (19)−0.0139 (17)−0.0020 (16)−0.0065 (16)
C450.058 (3)0.045 (2)0.045 (2)−0.0003 (19)−0.022 (2)−0.0084 (18)
C460.052 (2)0.061 (3)0.044 (2)0.008 (2)−0.0162 (19)−0.015 (2)
C470.061 (3)0.045 (2)0.059 (3)−0.0033 (19)−0.044 (2)0.0002 (19)
C480.049 (2)0.041 (2)0.063 (3)−0.0059 (18)−0.028 (2)0.0015 (19)
C490.033 (2)0.053 (2)0.060 (3)−0.0105 (17)−0.0170 (19)0.011 (2)
C500.036 (2)0.044 (2)0.041 (2)−0.0145 (16)−0.0165 (16)0.0147 (16)
C510.045 (2)0.047 (2)0.0339 (19)−0.0225 (17)−0.0198 (16)0.0090 (16)
C520.040 (2)0.043 (2)0.039 (2)−0.0278 (16)−0.0008 (16)0.0012 (16)
C530.051 (2)0.042 (2)0.037 (2)−0.0132 (17)−0.0002 (17)−0.0077 (16)
C540.058 (3)0.062 (3)0.0269 (19)−0.006 (2)−0.0062 (17)0.0067 (17)
C550.048 (2)0.0348 (18)0.0367 (19)−0.0167 (16)−0.0159 (16)0.0060 (15)
C560.053 (2)0.0313 (18)0.0329 (18)−0.0128 (16)−0.0225 (17)0.0052 (14)
C570.035 (4)0.043 (4)0.055 (5)−0.009 (3)−0.008 (3)0.016 (3)
Mn10.0289 (3)0.0314 (3)0.0355 (3)−0.0038 (2)−0.0041 (2)0.0000 (2)
Mn20.0364 (3)0.0314 (3)0.0366 (3)−0.0078 (2)−0.0083 (2)0.0024 (2)
N10.0320 (15)0.0337 (15)0.0381 (16)0.0000 (12)−0.0022 (12)−0.0015 (12)
N20.0281 (14)0.0394 (16)0.0318 (15)−0.0061 (12)−0.0016 (12)−0.0064 (12)
N30.0462 (17)0.0304 (15)0.0382 (16)−0.0065 (13)−0.0141 (14)−0.0050 (12)
N40.0487 (18)0.0388 (17)0.0282 (15)−0.0106 (14)−0.0076 (13)0.0009 (12)
O10.0521 (15)0.0384 (14)0.0366 (14)−0.0138 (12)−0.0076 (12)0.0012 (11)
O20.0519 (15)0.0366 (14)0.0357 (13)−0.0156 (11)−0.0117 (12)0.0026 (10)
O30.0327 (12)0.0483 (15)0.0283 (12)0.0008 (11)−0.0049 (10)−0.0093 (10)
O40.0439 (14)0.0495 (15)0.0262 (13)0.0004 (11)−0.0043 (10)−0.0038 (11)
O50.0565 (16)0.0384 (14)0.0318 (13)−0.0130 (12)−0.0175 (12)−0.0012 (10)
O60.0509 (15)0.0380 (14)0.0333 (13)−0.0109 (11)−0.0137 (11)0.0066 (11)
O70.0435 (14)0.0519 (16)0.0258 (13)0.0047 (12)−0.0031 (10)−0.0016 (11)
O80.0459 (15)0.0510 (16)0.0263 (12)0.0064 (12)−0.0057 (11)0.0000 (11)
O90.0467 (15)0.0524 (16)0.0472 (16)−0.0239 (13)−0.0109 (12)−0.0003 (12)
O100.0340 (14)0.0604 (18)0.0550 (17)0.0028 (12)−0.0024 (12)−0.0129 (14)
O110.0392 (13)0.0359 (13)0.0351 (13)−0.0214 (10)−0.0053 (10)−0.0017 (10)
O120.0621 (17)0.0379 (14)0.0248 (12)0.0096 (12)0.0077 (11)−0.0011 (10)
O130.055 (4)0.069 (4)0.077 (5)−0.015 (3)0.019 (3)−0.026 (4)
Geometric parameters (Å, °) top
C1—O91.374 (3)C31—H31B0.9700
C1—C21.3900C32—O81.243 (4)
C1—C61.3900C32—O71.255 (4)
C2—C31.3900C33—N11.332 (5)
C2—H20.9300C33—C341.394 (5)
C3—C41.3900C33—H330.9300
C3—H30.9300C34—C351.372 (5)
C4—C51.3900C34—H340.9300
C4—H40.9300C35—C361.399 (6)
C5—C61.3900C35—H350.9300
C5—H50.9300C36—C371.415 (5)
C6—H60.9300C36—C381.434 (5)
C7—O91.415 (4)C37—N11.361 (4)
C7—C81.521 (5)C37—C411.436 (5)
C7—H7A0.9700C38—C391.327 (6)
C7—H7B0.9700C38—H380.9300
C8—O11.234 (4)C39—C401.429 (5)
C8—O21.256 (4)C39—H390.9300
C9—O101.358 (5)C40—C411.400 (5)
C9—C141.378 (5)C40—C421.425 (5)
C9—C101.402 (5)C41—N21.347 (4)
C10—C111.379 (5)C42—C431.358 (6)
C10—H100.9300C42—H420.9300
C11—C121.356 (5)C43—C441.382 (5)
C11—H110.9300C43—H430.9300
C12—C131.390 (5)C44—N21.332 (5)
C12—H120.9300C44—H440.9300
C13—C141.391 (5)C45—N31.327 (5)
C13—H130.9300C45—C461.396 (5)
C14—H140.9300C45—H450.9300
C15—O101.418 (4)C46—C471.374 (6)
C15—C161.533 (5)C46—H460.9300
C15—H15A0.9700C47—C481.397 (7)
C15—H15B0.9700C47—H470.9300
C16—O41.247 (4)C48—C561.401 (5)
C16—O31.254 (4)C48—C491.452 (6)
C17—C221.364 (6)C49—C501.315 (6)
C17—O111.371 (4)C49—H490.9300
C17—C181.408 (5)C50—C511.422 (5)
C18—C191.354 (5)C50—H500.9300
C18—H180.9300C51—C521.405 (6)
C19—C201.364 (6)C51—C551.421 (5)
C19—H190.9300C52—C531.385 (5)
C20—C211.361 (6)C52—H520.9300
C20—H200.9300C53—C541.405 (5)
C21—C221.369 (6)C53—H530.9300
C21—H210.9300C54—N41.324 (5)
C22—H220.9300C54—H540.9300
C23—O111.419 (4)C55—N41.373 (5)
C23—C241.532 (5)C55—C561.421 (6)
C23—H23A0.9700C56—N31.365 (5)
C23—H23B0.9700C57—O131.465 (10)
C24—O51.227 (4)C57—H57A0.9600
C24—O61.257 (4)C57—H57B0.9600
C25—O121.366 (5)C57—H57C0.9600
C25—C261.385 (6)Mn1—O12.250 (3)
C25—C301.397 (6)Mn1—O32.094 (2)
C26—C271.386 (5)Mn1—O52.289 (2)
C26—H260.9300Mn1—O72.112 (3)
C27—C281.388 (5)Mn1—N12.299 (3)
C27—H270.9300Mn1—N22.302 (3)
C28—C291.382 (6)Mn2—O22.087 (2)
C28—H280.9300Mn2—O42.227 (3)
C29—C301.369 (5)Mn2—O62.102 (2)
C29—H290.9300Mn2—O82.351 (3)
C30—H300.9300Mn2—N32.327 (3)
C31—O121.417 (4)Mn2—N42.299 (3)
C31—C321.515 (5)O13—H13A0.8200
C31—H31A0.9700
O9—C1—C2115.15 (19)N1—C37—C41117.6 (3)
O9—C1—C6124.84 (19)C36—C37—C41120.0 (3)
C2—C1—C6120.0C39—C38—C36121.3 (4)
C3—C2—C1120.0C39—C38—H38119.3
C3—C2—H2120.0C36—C38—H38119.3
C1—C2—H2120.0C38—C39—C40121.4 (3)
C2—C3—C4120.0C38—C39—H39119.3
C2—C3—H3120.0C40—C39—H39119.3
C4—C3—H3120.0C41—C40—C42116.6 (3)
C3—C4—C5120.0C41—C40—C39120.0 (4)
C3—C4—H4120.0C42—C40—C39123.4 (3)
C5—C4—H4120.0N2—C41—C40123.4 (3)
C6—C5—C4120.0N2—C41—C37117.9 (3)
C6—C5—H5120.0C40—C41—C37118.7 (3)
C4—C5—H5120.0C43—C42—C40119.3 (3)
C5—C6—C1120.0C43—C42—H42120.4
C5—C6—H6120.0C40—C42—H42120.4
C1—C6—H6120.0C42—C43—C44119.6 (4)
O9—C7—C8111.8 (3)C42—C43—H43120.2
O9—C7—H7A109.3C44—C43—H43120.2
C8—C7—H7A109.3N2—C44—C43123.3 (4)
O9—C7—H7B109.3N2—C44—H44118.3
C8—C7—H7B109.3C43—C44—H44118.3
H7A—C7—H7B107.9N3—C45—C46123.8 (4)
O1—C8—O2127.6 (3)N3—C45—H45118.1
O1—C8—C7120.6 (3)C46—C45—H45118.1
O2—C8—C7111.9 (3)C47—C46—C45117.6 (4)
O10—C9—C14125.8 (3)C47—C46—H46121.2
O10—C9—C10115.7 (3)C45—C46—H46121.2
C14—C9—C10118.4 (3)C46—C47—C48121.3 (4)
C11—C10—C9120.0 (3)C46—C47—H47119.4
C11—C10—H10120.0C48—C47—H47119.4
C9—C10—H10120.0C47—C48—C56116.6 (4)
C12—C11—C10121.3 (4)C47—C48—C49124.4 (4)
C12—C11—H11119.3C56—C48—C49119.0 (4)
C10—C11—H11119.3C50—C49—C48121.5 (4)
C11—C12—C13119.6 (3)C50—C49—H49119.2
C11—C12—H12120.2C48—C49—H49119.2
C13—C12—H12120.2C49—C50—C51121.2 (4)
C12—C13—C14119.7 (4)C49—C50—H50119.4
C12—C13—H13120.2C51—C50—H50119.4
C14—C13—H13120.2C52—C51—C55117.8 (3)
C9—C14—C13120.9 (4)C52—C51—C50123.0 (3)
C9—C14—H14119.6C55—C51—C50119.2 (4)
C13—C14—H14119.6C53—C52—C51119.7 (3)
O10—C15—C16115.2 (3)C53—C52—H52120.1
O10—C15—H15A108.5C51—C52—H52120.1
C16—C15—H15A108.5C52—C53—C54118.9 (4)
O10—C15—H15B108.5C52—C53—H53120.6
C16—C15—H15B108.5C54—C53—H53120.6
H15A—C15—H15B107.5N4—C54—C53123.0 (4)
O4—C16—O3127.3 (3)N4—C54—H54118.5
O4—C16—C15119.7 (3)C53—C54—H54118.5
O3—C16—C15113.0 (3)N4—C55—C56118.6 (3)
C22—C17—O11116.7 (3)N4—C55—C51121.6 (4)
C22—C17—C18119.2 (4)C56—C55—C51119.8 (3)
O11—C17—C18124.1 (3)N3—C56—C48123.1 (4)
C19—C18—C17118.3 (4)N3—C56—C55117.7 (3)
C19—C18—H18120.8C48—C56—C55119.2 (4)
C17—C18—H18120.8O13—C57—H57A109.5
C18—C19—C20122.9 (3)O13—C57—H57B109.5
C18—C19—H19118.6H57A—C57—H57B109.5
C20—C19—H19118.6O13—C57—H57C109.5
C21—C20—C19117.9 (4)H57A—C57—H57C109.5
C21—C20—H20121.1H57B—C57—H57C109.5
C19—C20—H20121.1O3—Mn1—O7165.10 (9)
C20—C21—C22121.6 (4)O3—Mn1—O189.02 (10)
C20—C21—H21119.2O7—Mn1—O185.90 (10)
C22—C21—H21119.2O3—Mn1—O585.75 (10)
C17—C22—C21120.0 (4)O7—Mn1—O585.38 (10)
C17—C22—H22120.0O1—Mn1—O5123.41 (9)
C21—C22—H22120.0O3—Mn1—N191.36 (10)
O11—C23—C24110.2 (3)O7—Mn1—N199.24 (10)
O11—C23—H23A109.6O1—Mn1—N1154.47 (10)
C24—C23—H23A109.6O5—Mn1—N182.06 (9)
O11—C23—H23B109.6O3—Mn1—N296.27 (9)
C24—C23—H23B109.6O7—Mn1—N296.98 (10)
H23A—C23—H23B108.1O1—Mn1—N282.86 (10)
O5—C24—O6127.7 (3)O5—Mn1—N2153.72 (10)
O5—C24—C23119.8 (3)N1—Mn1—N271.72 (10)
O6—C24—C23112.5 (3)O2—Mn2—O6164.69 (10)
O12—C25—C26125.1 (4)O2—Mn2—O490.14 (10)
O12—C25—C30115.6 (4)O6—Mn2—O488.70 (10)
C26—C25—C30119.2 (4)O2—Mn2—N495.76 (10)
C25—C26—C27120.1 (4)O6—Mn2—N492.14 (10)
C25—C26—H26120.0O4—Mn2—N4153.09 (11)
C27—C26—H26120.0O2—Mn2—N3101.55 (10)
C26—C27—C28120.2 (4)O6—Mn2—N393.36 (10)
C26—C27—H27119.9O4—Mn2—N381.30 (10)
C28—C27—H27119.9N4—Mn2—N371.79 (11)
C29—C28—C27119.4 (3)O2—Mn2—O884.33 (10)
C29—C28—H28120.3O6—Mn2—O883.89 (10)
C27—C28—H28120.3O4—Mn2—O8125.25 (9)
C30—C29—C28120.7 (4)N4—Mn2—O881.54 (10)
C30—C29—H29119.6N3—Mn2—O8153.09 (10)
C28—C29—H29119.6C33—N1—C37117.5 (3)
C29—C30—C25120.3 (4)C33—N1—Mn1126.4 (2)
C29—C30—H30119.9C37—N1—Mn1116.1 (2)
C25—C30—H30119.9C44—N2—C41117.7 (3)
O12—C31—C32112.3 (3)C44—N2—Mn1125.9 (2)
O12—C31—H31A109.1C41—N2—Mn1116.4 (2)
C32—C31—H31A109.1C45—N3—C56117.7 (3)
O12—C31—H31B109.1C45—N3—Mn2126.5 (2)
C32—C31—H31B109.1C56—N3—Mn2115.7 (3)
H31A—C31—H31B107.9C54—N4—C55118.9 (3)
O8—C32—O7127.1 (3)C54—N4—Mn2125.1 (2)
O8—C32—C31122.1 (3)C55—N4—Mn2116.0 (3)
O7—C32—C31110.8 (3)C8—O1—Mn1143.6 (2)
N1—C33—C34123.9 (3)C8—O2—Mn2123.9 (2)
N1—C33—H33118.0C16—O3—Mn1121.8 (2)
C34—C33—H33118.0C16—O4—Mn2144.6 (2)
C35—C34—C33118.8 (4)C24—O5—Mn1148.5 (2)
C35—C34—H34120.6C24—O6—Mn2117.4 (2)
C33—C34—H34120.6C32—O7—Mn1121.6 (2)
C34—C35—C36119.4 (3)C32—O8—Mn2145.0 (2)
C34—C35—H35120.3C1—O9—C7116.4 (3)
C36—C35—H35120.3C9—O10—C15116.7 (3)
C35—C36—C37118.0 (3)C17—O11—C23117.4 (3)
C35—C36—C38123.4 (3)C25—O12—C31116.4 (3)
C37—C36—C38118.6 (4)C57—O13—H13A109.5
N1—C37—C36122.3 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C20—H20···O10i0.932.703.627 (5)175
Symmetry codes: (i) x, y+1, z.
Table 1
Selected geometric parameters (Å) top
Mn1—O12.250 (3)Mn2—O22.087 (2)
Mn1—O32.094 (2)Mn2—O42.227 (3)
Mn1—O52.289 (2)Mn2—O62.102 (2)
Mn1—O72.112 (3)Mn2—O82.351 (3)
Mn1—N12.299 (3)Mn2—N32.327 (3)
Mn1—N22.302 (3)Mn2—N42.299 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C20—H20···O10i0.932.703.627 (5)175
Symmetry codes: (i) x, y+1, z.
Acknowledgements top

This work was supported by the Natural Science Foundation of JiangSu Education Department (grant No. 06KJD150154).

references
References top

Bruker (2000). SMART (Version 5.0), SAINT (Version 6.02a), SADABS (Version 2.01) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.

Jiang, G.-Q., Li, Y.-Z., Hua, W.-J., Song, Y., Bai, J.-F., Li, S.-H., Scheer, M. & You, X.-Z. (2006). CrystEngComm, 8, 384–387.

Jiang, G.-Q., Li, Y.-Z., Wang, S.-N., Li, F.-F., Xu, Z.-J. & Bai, J.-F. (2005). Acta Cryst. E61, m1517–m1519.

Sessoli, R., Tsai, H. L., Schake, A. R., Wang, S., Vincent, J. B., Folting, K., Gatteschi, D., Christou, G. & Hendrickson, D. N. (1993). J. Am. Chem. Soc. 115, 1804–1816.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Yaghi, O. M., Davis, C. E., Li, G. & Li, H. (1997). J. Am. Chem. Soc. 119, 2861–2868.