supplementary materials


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

rk2087 scheme

Acta Cryst. (2008). E64, m774    [ doi:10.1107/S1600536808012518 ]

Hexa-[mu]2-benzoato-bis(2,2'-bipyridyl)trimanganese(II) monohydrate

H.-C. Yao, N. Wang, L. Zhang and Z.-J. Li

Abstract top

The complex molecule of the title compound, [Mn3(C7H5O2)6(C10H8N2)2]·H2O, contains a linear array of divalent manganese ions. The central MnII atom, which is located on a crystallographic inversion center, is coordinated octahedrally by six benzoate O atoms. The two terminal MnII ions are six-coordinated by four benzoate O atoms and two N atoms of 2,2'-bipyridyl. The central MnII atom and the terminal MnII ions are bridged by four benzoate ligands in a bidentate fashion, whereas the other two carboxylate ligands form bridges through one O atom only and chelate the terminal MnII atom. The molecules pack together via van der Waals attractions and C-H...O hydrogen bonds.

Comment top

The chemistry of manganese in various states and various nuclearities has received much attention since the discovery of their potential as models for the oxygen–evolving complex of photosystem II (Mukhopadhyay et al., 2002 and references therein) and as single–domain nanoscale magnetic particles (Gatteschi et al., 2003 and references therein). We have previously reported the crystal structure of manganese complexes with benzoate, phosphonate and 2,2'–bipyridyl ligands (Yao et al., 2006; Ma et al., 2007). In this paper, we report the crystal structure of a Mn3–complex with benzoate and 2,2'–bipyridyl ligands.

The structure of the title compound is composed of a linear array of trimanganese ions and a water molecule (Fig. 1). The linear complex includes a central, octahedral MnII ion [Mn1] that is located on a crystallographic inversion center. Its coordination sphere is composed of six oxygen atoms from six different benzoates. The central Mn1 ion is flanked by two octahedrally distorted MnII ion [Mn2]. For the Mn2 atom, four of its six coordination positions are occupied by the oxygen atoms O1, O2, O4 and O5 from the benzoate ligands. The remaining two positions are filled with the nitrogen atoms from the 2,2'–bipyridyl ligand. The Mn—N bond lengths are 2.259 (3)Å and 2.271 (3)Å. The Mn—O bond lengths are in the range of 2.075 (2)–2.300 (2) Å. The bond lengths and angles may be compared with the corresponding values in similar complexe of MnII: Mn3(AcO)6(bipy)2 (Ménage et al., 1991), Mn3(AcO)6(pybim)2 (Tangoulis et al., 1996) and [Mn3(µ–ClCH2COO)6(bipy)2] (Fernández et al., 2002). The Mn1 and Mn2 atoms are bridged by six benzoate ligands, four of which show the common µ2–η1:η1 coordination mode while the other two adopt the µ3–η2:η1 coordination mode (Scheme).

The oxidation state assignments for Mn ions as MnII are based on the following observations. The trinuclear molecules is neutral and is composed of six monoanionic benzoate donors (e.g. benzoates) and two neutral 2,2'–bipyridyl ligands. Additional support for this oxidation level is provided by the almost equal distances of the Mn—O and Mn—N bond lengths, which is typical for a d5 system (Ménage et al., 1991; Fernαndez et al., 2002).

The hydrogen–bond parameters of the title compound are listed in Table. The molecule shows C—H···O intramolecular H bond with C···O distance of 3.149 (5)Å and 3.458 (5)Å and C—H···O angle of > 115° (dashed line in Fig. 1). The distance and angle values are typical for these types of hydrogen bonds (Desiraju et al., 2002 and references therein). The title compound packed together via van der Waals attractions as well as intermolecular C9—H9···O2ii hydrogen bonds (dashed line in Fig. 2). Symmetry codes: (ii) 2-x, 2-y, 1-z.

Related literature top

For general background, see: Mukhopadhyay et al. (2002) and references therein; Gatteschi et al. (2003) and references therein; Yao et al. (2006); Ma et al. (2007). For related literature, see: Desiraju et al. (2002) and references therein. For related structures, see: Ménage et al. (1991); Tangoulis et al. (1996); Fernández et al. (2002).

Experimental top

[Mn3O(PhCO2)6(py)2.(H2O)] (0.1079 g, 0.01 mmol) (where is py = pyridine) was dissolved in 10 ml CH3CN, to which a solution of 1,1,1–tris(hydroxymethyl)methylamine (0.0121 g, 0.01 mmol) and 2,2'–bipyridyl (0.0156 g, 0.01 mmol) in dichloromethane (10 ml) was added. After stirring at room temperature for half an hour, the solution was filtered and the filtrate was allowed to evaporate slowly in air. A small crop of the dark–brown X–ray quality crystals of the title compound was formed in several days. Anal. Calc. for C62H46Mn3N4O12.H2O (C62H48Mn3N4O13): C 60.94%, H 3.96%, N 4.59%. Found: C 60.69%, H 3.83%, N 4.68%. FT–IR (KBr pellet, cm-1): 3440 br, 3062 w, 2361 w, 1610s, 1570 s, 1492 w, 1470 w, 1446 w, 1391 s, 1173 w, 1067 w, 1025 w, 836 w, 768 w, 718 m, 674 w, 640 w, 463 w. Thermogravimetric analysis of the title compound shows one step weight loss in the temperature range 323–473 K. The total weight loss (1.8%) is slightly higher than the calculated value of 1.5% for the removal of one free water molecule.

Refinement top

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). H atoms of the water molecule were located in difference Fourier maps and included in the subsequent refinement using restraint (O—H = 0.85 (1) Å) with Uiso(H) = 1.2Ueq(O). In the last stage of refinement, it was treated as riding on the O atom. The free water molecule in the crystal lattice was treated as disorder with 50% occupation rate.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Perspective view of the title compound, with the atom numbering scheme. The displacement ellipsoids are drawn at the 30% probability level. The H atoms are presented as a small spheres of arbitrary radius. The intramolecular H–bonds are drawn as dashed lines. Symmetry codes: (i) 1-x, 2-y, 1-z.
[Figure 2] Fig. 2. The intermolecular C—H···O hydrogen bond between the molecule units. H atoms not included in the hydrogen bond were omitted for clarify. Symmetry codes: (ii) 2-x, 2-y, 1-z.
Hexa-µ2-benzoato-bis(2,2'-bipyridyl)trimanganese(II) monohydrate top
Crystal data top
[Mn3(C7H5O2)6(C10H8N2)2]·H2OZ = 1
Mr = 1221.86F000 = 627
Triclinic, P1Dx = 1.428 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 11.2312 (5) ÅCell parameters from 4735 reflections
b = 11.7544 (2) Åθ = 2.1–26.5º
c = 11.994 (3) ŵ = 0.73 mm−1
α = 72.046 (3)ºT = 291 (2) K
β = 71.0940 (10)ºBlock, dark–brown
γ = 80.418 (2)º0.30 × 0.20 × 0.10 mm
V = 1421.1 (4) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer		5553 independent reflections
Radiation source: Sealed tube4007 reflections with I > 2σ(I)
Monochromator: GgraphiteRint = 0.036
T = 291(2) Kθmax = 26.0º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −13→13
Tmin = 0.841, Tmax = 0.932k = −14→14
11367 measured reflectionsl = −14→14
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)] = 0.060H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.138  w = 1/[σ2(Fo2) + (0.07P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
5553 reflectionsΔρmax = 0.29 e Å−3
382 parametersΔρmin = −0.70 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn3(C7H5O2)6(C10H8N2)2]·H2Oγ = 80.418 (2)º
Mr = 1221.86V = 1421.1 (4) Å3
Triclinic, P1Z = 1
a = 11.2312 (5) ÅMo Kα
b = 11.7544 (2) ŵ = 0.73 mm−1
c = 11.994 (3) ÅT = 291 (2) K
α = 72.046 (3)º0.30 × 0.20 × 0.10 mm
β = 71.0940 (10)º
Data collection top
Bruker SMART APEX CCD
diffractometer		5553 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		4007 reflections with I > 2σ(I)
Tmin = 0.841, Tmax = 0.932Rint = 0.036
11367 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.060382 parameters
wR(F2) = 0.138H atoms treated by a mixture of
independent and constrained refinement
S = 1.08Δρmax = 0.29 e Å−3
5553 reflectionsΔρmin = −0.70 e Å−3
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
xyzUiso*/UeqOcc. (<1)
C10.7698 (3)0.7996 (3)0.3087 (3)0.0385 (8)
C20.8860 (4)0.7842 (4)0.2269 (4)0.0525 (10)
H20.95900.79440.24230.063*
C30.8943 (4)0.7532 (4)0.1208 (4)0.0589 (11)
H30.97240.74490.06440.071*
C40.7860 (4)0.7353 (4)0.1005 (4)0.0572 (10)
H40.79140.71390.03040.069*
C50.6702 (4)0.7485 (4)0.1825 (4)0.0546 (10)
H50.59800.73510.16780.066*
C60.6594 (4)0.7815 (3)0.2865 (4)0.0496 (9)
H60.58050.79160.34110.060*
C70.7607 (3)0.8311 (3)0.4229 (3)0.0369 (7)
C80.7418 (3)1.2525 (3)0.5247 (3)0.0364 (7)
C90.8542 (3)1.2741 (3)0.5377 (4)0.0454 (9)
H90.90841.20990.56410.054*
C100.8856 (4)1.3894 (4)0.5120 (4)0.0489 (9)
H100.96131.40290.51990.059*
C110.8053 (4)1.4850 (3)0.4745 (4)0.0503 (9)
H110.82511.56300.45980.060*
C120.6939 (4)1.4641 (3)0.4587 (4)0.0519 (10)
H120.64101.52840.43010.062*
C130.6621 (3)1.3488 (3)0.4851 (3)0.0401 (8)
H130.58671.33550.47630.048*
C140.7122 (3)1.1261 (3)0.5471 (3)0.0312 (6)
C150.3814 (3)0.9013 (3)0.9078 (3)0.0361 (7)
C160.4312 (4)0.8754 (3)1.0053 (3)0.0448 (8)
H160.51710.85380.99260.054*
C170.3569 (4)0.8806 (3)1.1204 (3)0.0471 (9)
H170.39200.86271.18470.056*
C180.2299 (4)0.9127 (4)1.1389 (3)0.0513 (10)
H180.17880.91671.21630.062*
C190.1785 (4)0.9388 (4)1.0444 (3)0.0513 (10)
H190.09260.96031.05760.062*
C200.2541 (3)0.9332 (3)0.9284 (3)0.0450 (8)
H200.21850.95110.86440.054*
C210.4675 (3)0.9023 (3)0.7814 (3)0.0355 (7)
C220.9965 (3)0.8848 (4)0.6997 (3)0.0449 (8)
H220.97830.96600.66640.054*
C231.1066 (4)0.8490 (4)0.7370 (4)0.0521 (9)
H231.16060.90510.72860.063*
C241.1315 (4)0.7329 (4)0.7846 (4)0.0543 (10)
H241.20290.70720.81140.065*
C251.0518 (4)0.6497 (4)0.7947 (4)0.0577 (11)
H251.07050.56820.82640.069*
C260.9434 (4)0.6893 (4)0.7568 (4)0.0491 (9)
C270.8531 (4)0.6079 (3)0.7629 (4)0.0534 (10)
C280.8616 (5)0.4857 (4)0.8167 (4)0.0660 (12)
H280.92590.45060.85220.079*
C290.7743 (4)0.4173 (4)0.8172 (4)0.0615 (12)
H290.77900.33520.85400.074*
C300.6809 (4)0.4675 (4)0.7648 (4)0.0605 (11)
H300.62160.42100.76490.073*
C310.6762 (4)0.5914 (4)0.7106 (4)0.0562 (10)
H310.61190.62730.67540.067*
Mn10.50001.00000.50000.03159 (18)
Mn20.74951 (5)0.86247 (4)0.63436 (5)0.03183 (15)
N10.9164 (3)0.8058 (3)0.7104 (3)0.0423 (7)
N20.7615 (3)0.6596 (3)0.7081 (3)0.0508 (8)
O10.6536 (2)0.8502 (2)0.4961 (2)0.0391 (5)
O20.8604 (2)0.8344 (2)0.4472 (2)0.0439 (6)
O30.6136 (2)1.1124 (2)0.5272 (2)0.0458 (6)
O40.7876 (2)1.0433 (2)0.5852 (2)0.0423 (6)
O50.5826 (2)0.8747 (2)0.7718 (2)0.0441 (6)
O60.4186 (2)0.9293 (2)0.6956 (2)0.0419 (6)
O1W0.4239 (7)0.4880 (6)0.9786 (6)0.0601 (16)0.50
H1A0.477 (11)0.463 (9)1.019 (11)0.072*0.50
H1B0.369 (10)0.538 (9)1.009 (9)0.072*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0372 (17)0.0400 (18)0.0360 (18)0.0098 (15)−0.0094 (14)−0.0151 (15)
C20.049 (2)0.050 (2)0.046 (2)0.0097 (18)−0.0083 (17)−0.0080 (18)
C30.058 (3)0.064 (3)0.048 (2)0.016 (2)−0.015 (2)−0.018 (2)
C40.057 (2)0.052 (2)0.055 (2)0.0120 (19)−0.015 (2)−0.013 (2)
C50.058 (2)0.051 (2)0.053 (2)0.0051 (19)−0.015 (2)−0.0171 (19)
C60.051 (2)0.050 (2)0.050 (2)−0.0006 (18)−0.0131 (18)−0.0185 (18)
C70.0314 (17)0.0371 (17)0.0416 (18)0.0034 (13)−0.0111 (14)−0.0123 (15)
C80.0300 (16)0.0370 (17)0.0381 (17)−0.0062 (14)−0.0056 (13)−0.0073 (14)
C90.0373 (19)0.043 (2)0.057 (2)−0.0079 (16)−0.0130 (17)−0.0125 (17)
C100.051 (2)0.052 (2)0.053 (2)−0.0175 (18)−0.0137 (18)−0.0209 (18)
C110.058 (2)0.037 (2)0.058 (2)−0.0135 (18)−0.0113 (19)−0.0169 (17)
C120.053 (2)0.037 (2)0.054 (2)0.0064 (18)−0.0139 (19)−0.0031 (17)
C130.045 (2)0.0393 (18)0.0344 (18)−0.0028 (15)−0.0203 (15)0.0019 (14)
C140.0278 (15)0.0362 (16)0.0293 (16)−0.0020 (13)−0.0063 (12)−0.0109 (13)
C150.0365 (18)0.0329 (16)0.0335 (16)−0.0069 (14)−0.0056 (13)−0.0040 (13)
C160.046 (2)0.051 (2)0.0355 (18)0.0003 (17)−0.0087 (16)−0.0147 (16)
C170.057 (2)0.051 (2)0.0338 (18)−0.0042 (18)−0.0148 (17)−0.0104 (16)
C180.057 (2)0.052 (2)0.0324 (19)0.0003 (19)0.0024 (17)−0.0137 (17)
C190.046 (2)0.055 (2)0.038 (2)0.0038 (18)−0.0014 (16)−0.0083 (17)
C200.0410 (19)0.054 (2)0.0337 (19)−0.0038 (16)−0.0095 (15)−0.0038 (16)
C210.0381 (18)0.0377 (17)0.0316 (17)−0.0053 (14)−0.0087 (14)−0.0109 (13)
C220.0337 (18)0.058 (2)0.045 (2)−0.0045 (16)−0.0126 (16)−0.0150 (18)
C230.044 (2)0.055 (2)0.055 (2)−0.0048 (18)−0.0130 (18)−0.0110 (19)
C240.049 (2)0.055 (2)0.051 (2)0.0158 (19)−0.0130 (18)−0.0155 (19)
C250.050 (2)0.056 (2)0.052 (2)0.014 (2)−0.0111 (19)−0.0068 (19)
C260.046 (2)0.055 (2)0.043 (2)0.0117 (18)−0.0175 (17)−0.0133 (18)
C270.053 (2)0.038 (2)0.057 (2)0.0160 (18)−0.0121 (19)−0.0095 (18)
C280.066 (3)0.048 (2)0.069 (3)−0.004 (2)−0.023 (2)0.007 (2)
C290.061 (3)0.049 (2)0.059 (3)−0.011 (2)−0.020 (2)0.013 (2)
C300.052 (2)0.051 (2)0.067 (3)−0.017 (2)−0.018 (2)0.006 (2)
C310.059 (3)0.054 (2)0.056 (3)−0.014 (2)−0.026 (2)−0.002 (2)
Mn10.0309 (4)0.0296 (4)0.0336 (4)−0.0016 (3)−0.0084 (3)−0.0091 (3)
Mn20.0282 (3)0.0330 (3)0.0353 (3)0.00136 (19)−0.0123 (2)−0.0091 (2)
N10.0362 (16)0.0501 (18)0.0422 (16)0.0069 (13)−0.0157 (13)−0.0155 (14)
N20.0525 (19)0.0386 (17)0.057 (2)−0.0001 (15)−0.0145 (16)−0.0105 (15)
O10.0311 (12)0.0478 (14)0.0392 (13)0.0059 (10)−0.0112 (10)−0.0167 (11)
O20.0318 (12)0.0555 (15)0.0466 (14)0.0069 (11)−0.0138 (11)−0.0200 (12)
O30.0367 (13)0.0517 (15)0.0519 (15)−0.0090 (11)−0.0094 (11)−0.0190 (12)
O40.0375 (13)0.0357 (13)0.0546 (16)−0.0019 (10)−0.0179 (12)−0.0095 (11)
O50.0388 (14)0.0503 (15)0.0379 (13)0.0044 (11)−0.0074 (10)−0.0124 (11)
O60.0432 (13)0.0556 (15)0.0260 (12)−0.0107 (11)−0.0074 (10)−0.0091 (11)
O1W0.060 (4)0.049 (3)0.064 (4)−0.005 (3)−0.009 (3)−0.015 (3)
Geometric parameters (Å, °) top
C1—C21.378 (5)C19—H190.9300
C1—C61.411 (5)C20—H200.9300
C1—C71.494 (5)C21—O61.251 (4)
C2—C31.400 (6)C21—O51.256 (4)
C2—H20.9300C22—N11.348 (5)
C3—C41.375 (6)C22—C231.406 (5)
C3—H30.9300C22—H220.9300
C4—C51.372 (6)C23—C241.327 (6)
C4—H40.9300C23—H230.9300
C5—C61.380 (6)C24—C251.386 (6)
C5—H50.9300C24—H240.9300
C6—H60.9300C25—C261.395 (6)
C7—O21.254 (4)C25—H250.9300
C7—O11.271 (4)C26—N11.334 (5)
C7—Mn22.634 (4)C26—C271.478 (6)
C8—C131.384 (5)C27—N21.358 (5)
C8—C91.394 (5)C27—C281.382 (6)
C8—C141.499 (5)C28—C291.365 (7)
C9—C101.374 (5)C28—H280.9300
C9—H90.9300C29—C301.355 (6)
C10—C111.375 (6)C29—H290.9300
C10—H100.9300C30—C311.400 (6)
C11—C121.396 (6)C30—H300.9300
C11—H110.9300C31—N21.334 (5)
C12—C131.374 (5)C31—H310.9300
C12—H120.9300Mn1—O3i2.139 (2)
C13—H130.9300Mn1—O32.139 (2)
C14—O31.251 (4)Mn1—O6i2.166 (2)
C14—O41.254 (4)Mn1—O62.166 (2)
C15—C201.377 (5)Mn1—O12.251 (2)
C15—C161.385 (5)Mn1—O1i2.251 (2)
C15—C211.509 (5)Mn2—O52.075 (2)
C16—C171.377 (5)Mn2—O42.101 (2)
C16—H160.9300Mn2—N12.259 (3)
C17—C181.376 (6)Mn2—N22.271 (3)
C17—H170.9300Mn2—O22.282 (3)
C18—C191.366 (6)Mn2—O12.300 (2)
C18—H180.9300O1W—H1A0.85 (13)
C19—C201.390 (5)O1W—H1B0.85 (10)
C2—C1—C6119.8 (3)C25—C24—H24119.7
C2—C1—C7120.3 (3)C24—C25—C26119.3 (4)
C6—C1—C7119.9 (3)C24—C25—H25120.4
C1—C2—C3120.1 (4)C26—C25—H25120.4
C1—C2—H2120.0N1—C26—C25120.8 (4)
C3—C2—H2120.0N1—C26—C27115.7 (3)
C4—C3—C2119.5 (4)C25—C26—C27123.5 (4)
C4—C3—H3120.2N2—C27—C28120.9 (4)
C2—C3—H3120.2N2—C27—C26115.9 (3)
C5—C4—C3120.7 (4)C28—C27—C26123.2 (4)
C5—C4—H4119.6C29—C28—C27119.2 (4)
C3—C4—H4119.6C29—C28—H28120.4
C4—C5—C6120.8 (4)C27—C28—H28120.4
C4—C5—H5119.6C30—C29—C28120.8 (4)
C6—C5—H5119.6C30—C29—H29119.6
C5—C6—C1119.0 (4)C28—C29—H29119.6
C5—C6—H6120.5C29—C30—C31118.2 (4)
C1—C6—H6120.5C29—C30—H30120.9
O2—C7—O1120.7 (3)C31—C30—H30120.9
O2—C7—C1118.8 (3)N2—C31—C30121.8 (4)
O1—C7—C1120.5 (3)N2—C31—H31119.1
O2—C7—Mn260.01 (18)C30—C31—H31119.1
O1—C7—Mn260.82 (17)O3i—Mn1—O3180.0
C1—C7—Mn2174.0 (2)O3i—Mn1—O6i91.63 (10)
C13—C8—C9119.1 (3)O3—Mn1—O6i88.37 (10)
C13—C8—C14121.0 (3)O3i—Mn1—O688.37 (10)
C9—C8—C14119.8 (3)O3—Mn1—O691.63 (10)
C10—C9—C8120.6 (4)O6i—Mn1—O6180.000 (1)
C10—C9—H9119.7O3i—Mn1—O187.97 (9)
C8—C9—H9119.7O3—Mn1—O192.03 (9)
C9—C10—C11120.2 (4)O6i—Mn1—O188.49 (9)
C9—C10—H10119.9O6—Mn1—O191.51 (9)
C11—C10—H10119.9O3i—Mn1—O1i92.03 (9)
C10—C11—C12119.6 (3)O3—Mn1—O1i87.97 (9)
C10—C11—H11120.2O6i—Mn1—O1i91.51 (9)
C12—C11—H11120.2O6—Mn1—O1i88.49 (9)
C13—C12—C11120.3 (3)O1—Mn1—O1i180.000 (1)
C13—C12—H12119.9O5—Mn2—O496.34 (10)
C11—C12—H12119.9O5—Mn2—N1111.32 (11)
C12—C13—C8120.3 (3)O4—Mn2—N190.61 (11)
C12—C13—H13119.9O5—Mn2—N290.34 (11)
C8—C13—H13119.9O4—Mn2—N2162.30 (11)
O3—C14—O4125.6 (3)N1—Mn2—N271.69 (12)
O3—C14—C8116.9 (3)O5—Mn2—O2152.16 (10)
O4—C14—C8117.5 (3)O4—Mn2—O294.63 (10)
C20—C15—C16118.3 (3)N1—Mn2—O294.03 (10)
C20—C15—C21121.6 (3)N2—Mn2—O286.83 (11)
C16—C15—C21120.0 (3)O5—Mn2—O195.16 (9)
C17—C16—C15121.7 (4)O4—Mn2—O1105.17 (9)
C17—C16—H16119.2N1—Mn2—O1147.59 (9)
C15—C16—H16119.2N2—Mn2—O190.47 (11)
C18—C17—C16119.1 (4)O2—Mn2—O157.22 (8)
C18—C17—H17120.4O5—Mn2—C7123.82 (10)
C16—C17—H17120.4O4—Mn2—C7102.37 (11)
C19—C18—C17120.3 (4)N1—Mn2—C7120.78 (10)
C19—C18—H18119.8N2—Mn2—C787.25 (12)
C17—C18—H18119.8O2—Mn2—C728.41 (9)
C18—C19—C20120.3 (4)O1—Mn2—C728.86 (9)
C18—C19—H19119.8C26—N1—C22118.7 (3)
C20—C19—H19119.8C26—N1—Mn2118.9 (3)
C15—C20—C19120.3 (4)C22—N1—Mn2122.1 (2)
C15—C20—H20119.9C31—N2—C27119.1 (4)
C19—C20—H20119.9C31—N2—Mn2123.1 (3)
O6—C21—O5125.6 (3)C27—N2—Mn2117.4 (3)
O6—C21—C15117.7 (3)C7—O1—Mn1136.2 (2)
O5—C21—C15116.7 (3)C7—O1—Mn290.3 (2)
N1—C22—C23122.5 (4)Mn1—O1—Mn2104.10 (9)
N1—C22—H22118.8C7—O2—Mn291.6 (2)
C23—C22—H22118.8C14—O3—Mn1149.7 (2)
C24—C23—C22118.2 (4)C14—O4—Mn2121.3 (2)
C24—C23—H23120.9C21—O5—Mn2138.0 (2)
C22—C23—H23120.9C21—O6—Mn1130.7 (2)
C23—C24—C25120.5 (4)H1A—O1W—H1B109 (10)
C23—C24—H24119.7
Symmetry codes: (i) −x+1, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O3i0.932.563.458 (5)161
C9—H9···O2ii0.932.533.287 (5)139
C22—H22···O40.932.553.149 (5)122
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C6—H6···O3i0.932.563.458 (5)161
C9—H9···O2ii0.932.533.287 (5)139
C22—H22···O40.932.553.149 (5)122
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+2, −y+2, −z+1.
Acknowledgements top

Financial support from the Basic Research Program of Henan Province (grant No. 072300420040) is gratefully acknowledged.

references
References top

Bruker (2000). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Desiraju, G. R. (2002). Acc. Chem. Res. 35, 565–573.

Fernández, G., Corbella, M., Mahía, J. & Maestro, M. A. (2002). Eur. J. Inorg. Chem. pp. 2502–2510.

Gatteschi, D. & Sessoli, R. (2003). Angew. Chem. Int. Ed. 42, 268–197.

Ma, Y.-S., Yao, H.-C., Hua, W.-J., Li, S.-H., Li, Y.-Z. & Zheng, L.-M. (2007). Inorg. Chim. Acta, 360, 1645–1650.

Ménage, S., Vitols, S. E., Bergerat, P., Codjovi, E., Kahn, O., Girerd, J.-J., Guillot, M., Solans, X. & Calvet, T. (1991). Inorg. Chem. 30, 2666–2671.

Mukhopadhyay, S., Staples, R. J. & Armstrong, W. A. (2002). Chem. Commun. pp. 864–865.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Tangoulis, V., Malamatari, D. A., Soulti, K., Stergiou, V., Raptopoulou, C. P., Terzis, A., Kabanos, T. A. & Kessissoglou, D. P. (1996). Inorg. Chem. 35, 4974–4983.

Yao, H.-C., Li, Y.-Z., Song, Y., Ma, Y.-S., Zheng, L.-M. & Xin, X.-Q. (2006). Inorg. Chem. 45, 59–65.