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Acta Cryst. (2008). E64, m543    [ doi:10.1107/S1600536808003577 ]

Bis{[mu]-2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolato}bis[(thiocyanato)manganese(III)]

S.-B. Wang, K. Tang, B.-H. Yang and S. Li

Abstract top

The reported structure is a monoclinic polymorph of the title compound, [Mn2(C16H14N2O2)2(NCS)2], which has been characterized previously in an orthorhombic form. Each MnIII atom is chelated by a tetradentate 2,2'-[ethane-1,2-diylbis(nitrilomethylidyne)]diphenolate ligand and by the N atom of a thiocyanate anion, in a square-pyramidal arrangement. The complexes form centrosymmetric dimers, with an Mn-O contact of 2.557 (3) Å trans to each thiocyanate anion, completing a distorted octahedral coordination geometry.

Comment top

As shown in Fig. 1, the Mn atom is chelated by two N and two O atoms of the N,N'-ethylenebis(salicylideneamine) ligand and by the N atom of the thiocyanate anion in the apical site. The Mn—N and Mn—O bond lengths are in the range of 1.979 (4)–2.181 (5) and 1.874 (3)–1.902 (3) %A, respectively (Table 1).

Related literature top

For the orthorhombic polymorph, see: Mikuriya et al. (1992); Li et al. (1997).

Experimental top

A mixture of manganese(III) acetate (1 mmol) and N,N'-bis(2-hydroxybenzyl)ethylenediamine (1 mmol) in 20 ml me thanol was refluxed for several hours. The solution was then cooled and filtered, and the filtrate was left to evaporate at room temperature. Pink blocks of the title compound were obtained after 2 days with a yield of 12%. Elemental analysis calculated: C 53.72, H 3.67, N 5.49%; found: C 53.78, H 3.69, N 5.54%.

Refinement top

H atoms were placed in calculated positions and refined as riding with Uiso(H) = 1.2 Ueq(C). The phenyl rings were constrained to have regular hexagonal geometry.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Asymmetric unit drawn with 30% probability displacement ellipsoids for the non-H atoms.
Bis{µ-2,2'-[ethane-1,2- diylbis(nitrilomethylidyne)]diphenolato}bis[(thiocyanato)manganese(III)] top
Crystal data top
[Mn2(C16H14N2O2)2(NCS)2]F000 = 776
Mr = 758.62Dx = 1.387 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4497 reflections
a = 9.0026 (10) Åθ = 2.4–24.4º
b = 14.0629 (16) ŵ = 0.86 mm−1
c = 14.9884 (17) ÅT = 293 (2) K
β = 106.848 (1)ºBlock, pink
V = 1816.1 (4) Å30.43 × 0.28 × 0.22 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer		3296 independent reflections
Radiation source: fine-focus sealed tube2627 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
T = 295(2) Kθmax = 25.3º
φ and ω scansθmin = 2.4º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −10→10
Tmin = 0.710, Tmax = 0.834k = −16→16
13254 measured reflectionsl = −18→17
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) = 0.231  w = 1/[σ2(Fo2) + (0.147P)2 + 2.2875P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.013
3296 reflectionsΔρmax = 1.47 e Å−3
193 parametersΔρmin = −0.33 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn2(C16H14N2O2)2(NCS)2]V = 1816.1 (4) Å3
Mr = 758.62Z = 2
Monoclinic, P21/nMo Kα
a = 9.0026 (10) ŵ = 0.86 mm−1
b = 14.0629 (16) ÅT = 293 (2) K
c = 14.9884 (17) Å0.43 × 0.28 × 0.22 mm
β = 106.848 (1)º
Data collection top
Bruker APEXII CCD
diffractometer		3296 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2627 reflections with I > 2σ(I)
Tmin = 0.710, Tmax = 0.834Rint = 0.023
13254 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.066193 parameters
wR(F2) = 0.231H-atom parameters constrained
S = 1.00Δρmax = 1.47 e Å−3
3296 reflectionsΔρmin = −0.33 e Å−3
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
xyzUiso*/Ueq
Mn10.64485 (8)0.01038 (5)0.10349 (5)0.0575 (3)
C10.8655 (4)0.1314 (2)0.0466 (3)0.0705 (14)
C20.9625 (5)0.1411 (3)−0.0101 (3)0.093 (2)
H20.97660.0902−0.04650.112*
C31.0384 (5)0.2267 (4)−0.0124 (4)0.124 (3)
H31.10330.2332−0.05030.148*
C41.0173 (6)0.3027 (3)0.0420 (4)0.146 (4)
H41.06810.36000.04040.175*
C50.9204 (6)0.2931 (3)0.0987 (4)0.128 (3)
H50.90630.34390.13510.153*
C60.8445 (5)0.2074 (3)0.1010 (3)0.0848 (17)
C70.9436 (7)−0.0871 (3)0.2500 (4)0.0640 (12)
C80.7500 (9)0.2027 (5)0.1635 (4)0.098 (2)
H80.74660.25680.19860.117*
C90.5841 (12)0.1325 (5)0.2457 (5)0.117 (3)
H9A0.56290.19770.25920.140*
H9B0.64510.10270.30300.140*
C100.4299 (12)0.0775 (6)0.2049 (7)0.125 (3)
H10A0.38260.06160.25350.150*
H10B0.35710.11470.15740.150*
C110.4148 (7)−0.0916 (5)0.1681 (4)0.0801 (16)
H110.3420−0.09520.20110.096*
C120.4489 (4)−0.1778 (2)0.1251 (2)0.0686 (13)
C130.4001 (5)−0.2635 (3)0.1534 (3)0.0921 (19)
H130.3496−0.26410.19940.110*
C140.4266 (6)−0.3482 (2)0.1127 (3)0.106 (2)
H140.3939−0.40550.13160.128*
C150.5020 (5)−0.34726 (18)0.0439 (3)0.0937 (19)
H150.5197−0.40400.01670.112*
C160.5508 (4)−0.2616 (2)0.0156 (2)0.0723 (14)
H160.6013−0.2610−0.03040.087*
C170.5243 (4)−0.17685 (18)0.0563 (2)0.0592 (11)
N10.6693 (7)0.1302 (3)0.1756 (3)0.0799 (13)
N20.4777 (6)−0.0108 (3)0.1639 (3)0.0737 (12)
N30.8165 (6)−0.0691 (4)0.2100 (4)0.0823 (13)
O10.7880 (4)0.0494 (3)0.0418 (3)0.0692 (9)
O20.5682 (4)−0.0941 (2)0.0227 (2)0.0574 (8)
S11.11942 (18)−0.11754 (13)0.30794 (13)0.0894 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0669 (5)0.0504 (5)0.0598 (5)0.0061 (3)0.0259 (4)−0.0011 (3)
C10.057 (3)0.066 (3)0.080 (3)−0.005 (2)0.005 (2)0.012 (3)
C20.061 (3)0.089 (4)0.127 (6)−0.007 (3)0.023 (3)0.022 (4)
C30.076 (4)0.120 (7)0.159 (8)−0.037 (4)0.010 (4)0.042 (6)
C40.117 (7)0.112 (7)0.162 (9)−0.061 (6)−0.034 (6)0.028 (6)
C50.133 (7)0.085 (5)0.123 (6)−0.041 (5)−0.029 (5)0.002 (4)
C60.091 (4)0.068 (3)0.075 (4)−0.012 (3)−0.009 (3)−0.001 (3)
C70.080 (3)0.051 (3)0.066 (3)0.006 (2)0.029 (3)0.010 (2)
C80.130 (6)0.064 (4)0.071 (4)0.009 (4)−0.015 (4)−0.016 (3)
C90.190 (9)0.082 (5)0.090 (5)0.030 (5)0.058 (5)−0.015 (4)
C100.169 (8)0.110 (6)0.130 (6)0.039 (6)0.098 (6)−0.011 (5)
C110.079 (3)0.105 (5)0.067 (3)0.013 (3)0.037 (3)0.023 (3)
C120.061 (3)0.079 (3)0.066 (3)0.000 (2)0.018 (2)0.020 (3)
C130.090 (4)0.102 (5)0.084 (4)−0.019 (4)0.025 (3)0.030 (4)
C140.111 (5)0.073 (4)0.124 (6)−0.021 (4)0.017 (5)0.035 (4)
C150.090 (4)0.058 (3)0.126 (6)0.000 (3)0.021 (4)0.010 (3)
C160.070 (3)0.053 (3)0.093 (4)0.003 (2)0.021 (3)0.005 (2)
C170.055 (2)0.054 (2)0.068 (3)0.001 (2)0.017 (2)0.006 (2)
N10.114 (4)0.061 (3)0.061 (3)0.016 (3)0.020 (2)−0.006 (2)
N20.085 (3)0.079 (3)0.070 (3)0.015 (2)0.043 (2)0.006 (2)
N30.085 (3)0.078 (3)0.082 (3)0.016 (3)0.020 (3)0.011 (2)
O10.069 (2)0.060 (2)0.084 (2)−0.0027 (16)0.0313 (18)−0.0004 (17)
O20.0661 (19)0.0491 (16)0.0641 (18)0.0026 (14)0.0302 (15)0.0026 (14)
S10.0697 (9)0.0979 (12)0.1010 (12)0.0079 (8)0.0256 (8)0.0270 (9)
Geometric parameters (Å, °) top
Mn1—O11.874 (3)C9—N11.469 (9)
Mn1—O21.902 (3)C9—C101.552 (13)
Mn1—N11.979 (4)C9—H9A0.970
Mn1—N21.990 (5)C9—H9B0.970
Mn1—N32.181 (5)C10—N21.503 (8)
Mn1—O2i2.557 (3)C10—H10A0.970
C1—O11.339 (4)C10—H10B0.970
C1—C21.390C11—N21.280 (8)
C1—C61.390C11—C121.447 (7)
C2—C31.390C11—H110.930
C2—H20.930C12—C131.390
C3—C41.390C12—C171.390
C3—H30.930C13—C141.390
C4—C51.390C13—H130.930
C4—H40.930C14—C151.390
C5—C61.390C14—H140.930
C5—H50.930C15—C161.390
C6—C81.439 (9)C15—H150.930
C7—N31.155 (7)C16—C171.390
C7—S11.627 (6)C16—H160.930
C8—N11.295 (9)C17—O21.371 (4)
C8—H80.930
O1—Mn1—O294.95 (14)N1—C9—H9B110.2
O1—Mn1—N192.1 (2)C10—C9—H9B110.2
O1—Mn1—N2170.90 (17)H9A—C9—H9B108.5
O1—Mn1—N393.94 (18)N2—C10—C9104.1 (6)
O1—Mn1—O2i88.62 (15)N2—C10—H10A110.9
O2—Mn1—N1165.40 (19)C9—C10—H10A110.9
O2—Mn1—N289.51 (17)N2—C10—H10B110.9
O2—Mn1—N396.85 (17)C9—C10—H10B110.9
O2—Mn1—O2i80.14 (14)H10A—C10—H10B109.0
N1—Mn1—N281.9 (2)N2—C11—C12124.6 (5)
N1—Mn1—N395.4 (2)N2—C11—H11117.7
N1—Mn1—O2i87.29 (16)C12—C11—H11117.7
N2—Mn1—N393.4 (2)C13—C12—C17120.0
N2—Mn1—O2i84.35 (17)C13—C12—C11117.6 (3)
N3—Mn1—O2i176.24 (17)C17—C12—C11122.3 (3)
O1—C1—C2117.4 (3)C12—C13—C14120.0
O1—C1—C6122.4 (3)C12—C13—H13120.0
C2—C1—C6120.0C14—C13—H13120.0
C3—C2—C1120.0C13—C14—C15120.0
C3—C2—H2120.0C13—C14—H14120.0
C1—C2—H2120.0C15—C14—H14120.0
C2—C3—C4120.0C14—C15—C16120.0
C2—C3—H3120.0C14—C15—H15120.0
C4—C3—H3120.0C16—C15—H15120.0
C5—C4—C3120.0C17—C16—C15120.0
C5—C4—H4120.0C17—C16—H16120.0
C3—C4—H4120.0C15—C16—H16120.0
C4—C5—C6120.0O2—C17—C16117.5 (2)
C4—C5—H5120.0O2—C17—C12122.4 (2)
C6—C5—H5120.0C16—C17—C12120.0
C5—C6—C1120.0C8—N1—C9120.8 (6)
C5—C6—C8116.3 (4)C8—N1—Mn1124.9 (4)
C1—C6—C8123.6 (4)C9—N1—Mn1114.2 (4)
N3—C7—S1177.1 (5)C11—N2—C10122.0 (6)
N1—C8—C6126.1 (5)C11—N2—Mn1124.0 (4)
N1—C8—H8117.0C10—N2—Mn1114.0 (5)
C6—C8—H8117.0C7—N3—Mn1151.3 (5)
N1—C9—C10107.5 (6)C1—O1—Mn1130.4 (3)
N1—C9—H9A110.2C17—O2—Mn1120.8 (2)
C10—C9—H9A110.2
Symmetry codes: (i) −x+1, −y, −z.
Table 1
Selected geometric parameters (Å, °) top
Mn1—O11.874 (3)Mn1—N21.990 (5)
Mn1—O21.902 (3)Mn1—N32.181 (5)
Mn1—N11.979 (4)Mn1—O2i2.557 (3)
O1—Mn1—O294.95 (14)O2—Mn1—O2i80.14 (14)
O1—Mn1—N192.1 (2)N1—Mn1—N281.9 (2)
O1—Mn1—N2170.90 (17)N1—Mn1—N395.4 (2)
O1—Mn1—N393.94 (18)N1—Mn1—O2i87.29 (16)
O1—Mn1—O2i88.62 (15)N2—Mn1—N393.4 (2)
O2—Mn1—N1165.40 (19)N2—Mn1—O2i84.35 (17)
O2—Mn1—N289.51 (17)N3—Mn1—O2i176.24 (17)
O2—Mn1—N396.85 (17)
Symmetry codes: (i) −x+1, −y, −z.
Acknowledgements top

The authors are grateful for financial support from Henan University (grant No. 05YBGG013).

references
References top

Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Li, H., Zhong, Z. J., Duan, C.-Y., You, X.-Z., Mak, T. C. W. & Wu, B. (1997). J. Coord. Chem. 41, 183–189.

Mikuriya, M., Yamato, Y. & Tokii, T. (1992). Bull. Chem. Soc. Jpn, 65, 1466–1468.

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