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Acta Cryst. (2008). E64, m1506    [ doi:10.1107/S1600536808035551 ]

[[mu]-10,21-Dimethyl-3,6,14,17-tetrazatricyclo[17.3.1.18,12]tetracosa-1(23),2,6,8,10,12 (24),13,17,19,21-decaene-23,24-diolato-[kappa]4N3,N6,O23,O24:[kappa]4N14,N17,O23,O24]bis(perchlorato-[kappa]O)dimanganese(II)

J. Liu, Z.-Q. Pan, H. Zhou and Y.-Z. Li

Abstract top

In the centrosymmetric and dinuclear title complex, [Mn2(C22H22N4O2)(ClO4)2], the two Mn atoms are bridged by two phenolate O atoms of the N4O2 macrocycle with an Mn...Mn distance of 2.9228 (11) Å. The distorted square-pyramidal N2O3 coordination geometry is completed by an O atom derived from a perchlorate anion.

Comment top

Schiff base macrocyclic complexes, derived from the cyclocondensation of 2,6-di-formyl-4-phenol and alkylenediamine in the presence of metal ions, have been extensively studied (Ki et al., 2006; Brooker & Croucher, 1997). The properties of the complexes vary with the differences in the macrocyclic structures and in the nature of the metal ions (Tei et al., 2001; Jong et al., 2006; Venegas-Yazigi et al., 2006). Although the same macrocyclic ligand featured in the title complex, (I), exists in the literature (Bai et al., 2007; Chattopadhyay et al., 2007), the dinuclear Mn(II) complex is novel; the structure is reported herein.

The dinuclear and centrosymmetric structure of (I), Fig. 1, is constructed about a Mn2O2 core. The macrocyclic ligand is hexadentate forming an N4O2 donor set. The Mn ion is coordinated by two endogenous phenolic-O atoms and two azomethine-N atoms that form an approximately square planar geometry. The distorted square pyramidal geometry is completed by a weakly coordinated O atom derived from the perchlorate anion, 2.390 (3) Å. The latter distance is greater than the range of the other Mn-(donor atom) distances, i.e. 1.888 (3) to 1.909 (3) Å. The Mn—Mn distance is 2.9228 (11) Å.

Related literature top

For related literature, see: Bai et al. (2007); Venegas-Yazigi et al. (2006); Jong et al. (2006); Ki et al. (2006); Tei et al. (2001); Brooker & Croucher (1997); Chattopadhyay et al. (2007). For synthesis, see: Taniguchi (1984).

Experimental top

2,6-Di-formyl-4-methylphenol was prepared according to the literature method (Taniguchi, 1984). Ethylenediamine (0.8 mmol, 0.048 g) in absolute methanol (10 ml) was added to a methanol solution (10 ml) containing 2,6-di-formyl-4-methylphenol (0.8 mmol, 0.13 g). The solution was stirred vigorously for 3 h in a ice-bath. Afterwards, a methanol solution (5 ml) of Mn(OAc)2.4H2O (0.4 mmol, 0.1 g) was added dropwise over a period of 1 h at room temperature. The mixture was stirred for a further 12 h at ambient temperature. Finally, Mn(ClO4)2.6H2O (0.4 mmol, 0.15 g) dissolved in methanol (5 ml) was added to the mixture and stirred for 8 h at room temperature. The dark-red block-shaped crystals suitable for X-ray diffraction precipitated by slow volatilization over a period of one month.

Refinement top

All C-bound H atoms were placed in calculated positions with 0.93–0.97 Å, and included in the refinement in the riding-model approximation, with U(H) set to 1.2–1.5Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (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. A view of (I), showing the labeling of the non-H atoms and 30% probability ellipsoids. H atoms have been omitted for clarity.
[µ-10,21-Dimethyl-3,6,14,17-tetrazatricyclo[17.3.1.18,12]tetracosa-1(23),2, 6,8,10,12 (24),13,17,19,21-decaene-23,24-diolato-κ4N3,N6, O23,O24:κ4N14,N17,O23,\ O24]bis(perchlorato-κO)dimanganese(II) top
Crystal data top
[Mn2(C22H22N4O2)(ClO4)2]Z = 1
Mr = 683.22F(000) = 346
Triclinic, P1Dx = 1.796 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.3129 (10) ÅCell parameters from 1608 reflections
b = 8.3759 (11) Åθ = 2.5–25.7°
c = 9.9712 (12) ŵ = 1.28 mm−1
α = 81.484 (2)°T = 291 K
β = 68.520 (3)°Block, red
γ = 78.838 (2)°0.31 × 0.21 × 0.15 mm
V = 631.56 (14) Å3
Data collection top
Bruker SMART APEX CCD
diffractometer		2439 independent reflections
Radiation source: sealed tube1701 reflections with I > 2σ(I)
graphiteRint = 0.029
φ and ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −6→10
Tmin = 0.73, Tmax = 0.83k = −9→10
3663 measured reflectionsl = −12→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0643P)2]
where P = (Fo2 + 2Fc2)/3
2439 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 0.56 e Å−3
0 restraintsΔρmin = −0.58 e Å−3
Crystal data top
[Mn2(C22H22N4O2)(ClO4)2]γ = 78.838 (2)°
Mr = 683.22V = 631.56 (14) Å3
Triclinic, P1Z = 1
a = 8.3129 (10) ÅMo Kα radiation
b = 8.3759 (11) ŵ = 1.28 mm−1
c = 9.9712 (12) ÅT = 291 K
α = 81.484 (2)°0.31 × 0.21 × 0.15 mm
β = 68.520 (3)°
Data collection top
Bruker SMART APEX CCD
diffractometer		2439 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1701 reflections with I > 2σ(I)
Tmin = 0.73, Tmax = 0.83Rint = 0.029
3663 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.118Δρmax = 0.56 e Å−3
S = 0.99Δρmin = −0.58 e Å−3
2439 reflectionsAbsolute structure: ?
182 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
C10.7059 (6)0.6449 (6)0.4901 (5)0.0464 (10)
C20.5527 (5)0.6225 (5)0.6085 (5)0.0419 (9)
C30.3922 (6)0.7068 (5)0.6049 (4)0.0400 (9)
H30.29080.68550.68060.048*
C40.3786 (6)0.8204 (5)0.4932 (5)0.0458 (10)
C50.5336 (6)0.8403 (6)0.3738 (5)0.0475 (11)
H50.52780.91070.29380.057*
C60.6944 (6)0.7556 (5)0.3752 (5)0.0413 (9)
C70.5468 (6)0.5007 (6)0.7344 (5)0.0476 (10)
H70.43690.48300.79910.057*
C80.8486 (5)0.7881 (5)0.2457 (4)0.0335 (8)
H80.82850.86620.17460.040*
C90.8484 (6)0.2595 (5)0.9110 (5)0.0494 (11)
H9A0.84020.33790.97660.059*
H9B0.86680.15070.95740.059*
C100.6753 (5)0.2848 (5)0.8787 (4)0.0425 (10)
H10A0.66160.18450.84920.051*
H10B0.57660.31240.96550.051*
C110.2057 (6)0.9079 (6)0.4876 (5)0.0494 (11)
H11A0.11310.86520.56670.074*
H11B0.19530.89230.39780.074*
H11C0.19801.02240.49460.074*
Cl10.82655 (13)0.75907 (13)0.86577 (11)0.0428 (3)
Mn10.91488 (7)0.43436 (7)0.64841 (6)0.0349 (2)
N10.6784 (5)0.4187 (4)0.7614 (4)0.0475 (9)
N20.9957 (5)0.2803 (4)0.7770 (4)0.0469 (9)
O10.8573 (4)0.5649 (4)0.4947 (3)0.0449 (7)
O20.9409 (4)0.6619 (4)0.7542 (3)0.0523 (8)
O30.9142 (4)0.8814 (4)0.8771 (3)0.0457 (7)
O40.7776 (4)0.6558 (4)0.9924 (3)0.0476 (7)
O50.6808 (4)0.8267 (4)0.8254 (3)0.0551 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.036 (2)0.059 (3)0.043 (2)0.0015 (19)−0.0149 (18)−0.010 (2)
C20.037 (2)0.039 (2)0.049 (2)−0.0074 (17)−0.0145 (19)−0.0029 (18)
C30.038 (2)0.044 (2)0.042 (2)−0.0069 (17)−0.0163 (17)−0.0121 (17)
C40.052 (3)0.041 (2)0.050 (2)0.0047 (19)−0.028 (2)−0.0122 (19)
C50.038 (2)0.067 (3)0.041 (2)0.005 (2)−0.0200 (19)−0.014 (2)
C60.043 (2)0.0331 (19)0.045 (2)−0.0020 (17)−0.0115 (18)−0.0112 (17)
C70.039 (2)0.055 (3)0.045 (2)−0.012 (2)−0.0046 (19)−0.010 (2)
C80.042 (2)0.0357 (19)0.0332 (19)−0.0088 (16)−0.0277 (17)0.0084 (15)
C90.036 (2)0.042 (2)0.058 (3)0.0016 (18)−0.009 (2)0.008 (2)
C100.043 (2)0.049 (3)0.039 (2)−0.0161 (19)−0.0178 (19)0.0065 (18)
C110.048 (3)0.055 (3)0.044 (2)0.002 (2)−0.016 (2)−0.010 (2)
Cl10.0484 (6)0.0439 (5)0.0378 (5)−0.0173 (4)−0.0121 (4)−0.0020 (4)
Mn10.0334 (3)0.0348 (3)0.0293 (3)−0.0010 (2)−0.0074 (2)0.0043 (2)
N10.042 (2)0.044 (2)0.051 (2)−0.0087 (17)−0.0114 (17)0.0014 (16)
N20.049 (2)0.045 (2)0.0361 (18)0.0054 (17)−0.0119 (16)0.0038 (16)
O10.0312 (14)0.0499 (17)0.0430 (16)0.0020 (12)−0.0097 (12)0.0100 (13)
O20.0483 (18)0.0482 (17)0.0523 (18)−0.0217 (14)0.0020 (15)−0.0113 (14)
O30.0583 (18)0.0484 (17)0.0359 (15)−0.0247 (14)−0.0123 (13)−0.0094 (12)
O40.0412 (16)0.0527 (18)0.0475 (17)−0.0193 (13)−0.0142 (13)0.0133 (14)
O50.0497 (18)0.0483 (18)0.0445 (17)0.0108 (14)−0.0063 (14)0.0157 (14)
Geometric parameters (Å, °) top
C1—O11.321 (5)C9—H9B0.9700
C1—C61.383 (6)C10—N11.492 (5)
C1—C21.406 (6)C10—H10A0.9700
C2—C31.393 (6)C10—H10B0.9700
C2—C71.488 (6)C11—H11A0.9600
C3—C41.376 (6)C11—H11B0.9600
C3—H30.9300C11—H11C0.9600
C4—C51.417 (6)Cl1—O41.394 (3)
C4—C111.499 (6)Cl1—O51.405 (3)
C5—C61.390 (6)Cl1—O31.406 (3)
C5—H50.9300Cl1—O21.413 (3)
C6—C81.485 (6)Mn1—N21.888 (3)
C7—N11.269 (6)Mn1—N11.893 (4)
C7—H70.9300Mn1—O11.900 (3)
C8—N2i1.262 (5)Mn1—O1i1.909 (3)
C8—H80.9300Mn1—O22.391 (3)
C9—N21.460 (5)Mn1—Mn1i2.9228 (11)
C9—C101.556 (6)N2—C8i1.262 (5)
C9—H9A0.9700O1—Mn1i1.909 (3)
O1—C1—C6121.9 (4)C4—C11—H11B109.5
O1—C1—C2119.0 (4)H11A—C11—H11B109.5
C6—C1—C2119.0 (4)C4—C11—H11C109.5
C3—C2—C1119.4 (4)H11A—C11—H11C109.5
C3—C2—C7116.3 (4)H11B—C11—H11C109.5
C1—C2—C7124.0 (4)O4—Cl1—O5110.61 (18)
C4—C3—C2122.3 (4)O4—Cl1—O3112.37 (19)
C4—C3—H3118.8O5—Cl1—O3111.3 (2)
C2—C3—H3118.8O4—Cl1—O2107.3 (2)
C3—C4—C5117.5 (4)O5—Cl1—O2106.4 (2)
C3—C4—C11122.3 (4)O3—Cl1—O2108.58 (18)
C5—C4—C11119.9 (4)N2—Mn1—N191.90 (16)
C6—C5—C4120.6 (4)N2—Mn1—O1170.28 (14)
C6—C5—H5119.7N1—Mn1—O193.45 (14)
C4—C5—H5119.7N2—Mn1—O1i93.60 (13)
C1—C6—C5120.9 (4)N1—Mn1—O1i168.66 (16)
C1—C6—C8123.0 (4)O1—Mn1—O1i79.78 (13)
C5—C6—C8116.1 (4)N2—Mn1—O293.10 (15)
N1—C7—C2125.8 (4)N1—Mn1—O297.47 (14)
N1—C7—H7117.1O1—Mn1—O294.23 (13)
C2—C7—H7117.1O1i—Mn1—O292.12 (12)
N2i—C8—C6126.1 (3)N2—Mn1—Mn1i132.98 (11)
N2i—C8—H8117.0N1—Mn1—Mn1i132.81 (12)
C6—C8—H8117.0O1—Mn1—Mn1i40.01 (8)
N2—C9—C10110.2 (4)O1i—Mn1—Mn1i39.77 (8)
N2—C9—H9A109.6O2—Mn1—Mn1i94.14 (8)
C10—C9—H9A109.6C7—N1—C10126.4 (4)
N2—C9—H9B109.6C7—N1—Mn1125.2 (3)
C10—C9—H9B109.6C10—N1—Mn1108.2 (3)
H9A—C9—H9B108.1C8i—N2—C9125.4 (3)
N1—C10—C9109.9 (3)C8i—N2—Mn1126.2 (3)
N1—C10—H10A109.7C9—N2—Mn1108.3 (3)
C9—C10—H10A109.7C1—O1—Mn1130.6 (3)
N1—C10—H10B109.7C1—O1—Mn1i129.0 (3)
C9—C10—H10B109.7Mn1—O1—Mn1i100.22 (13)
H10A—C10—H10B108.2Cl1—O2—Mn1134.41 (17)
C4—C11—H11A109.5
Symmetry codes: (i) −x+2, −y+1, −z+1.
Acknowledgements top

The authors thank the National Science Foundation of China (grant No. 20271039).

references
References top

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