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Acta Cryst. (2008). E64, m204    [ doi:10.1107/S1600536807066512 ]

[mu]-Oxido-bis{chlorido[tris(2-pyridylmethyl)amine]manganese(III)} bis(hexafluoridophosphate)

Q. Meng, L. Wang, Y. Liu and Y. Pang

Abstract top

In the title compound, [Mn2O(C18H18ClN4)2](PF6)2, the Mn atom is chelated by a tetradentate ligand via four N atoms, and further bonded to one chloride ion and one bridging oxide, to give a centrosymmetric cation and distorted octahedral coordination geometry.

Comment top

In recent years, many symmetrical polypyridine ligands and their coordination complexes have been synthesized (Scapin et al., 1997; Okabe et al., 2000; Serre et al., 2005). In this paper, we report the structure of the title compound, (I), containing an unsymmetrical polypyridine ligand.

As shown in Fig. 1, the Mn atom is chelated by the tetradentate ligand via four N atoms, and further bonded to one chloride ion and one bridging oxide, to give a centrosymmetric cation and distorted octahedral coordination geometry.

Related literature top

For related literature, see: Scapin et al. (1997); Okabe et al. (2000); Serre et al. (2005).

Experimental top

A mixture of manganese(III) acetate (1 mmol) and tris(2-pyridylmethyl)amine (1 mmol) in 20 ml me thanol was refluxed for two hours. The cooled solution was filtered and the filtrate allowed to evaporate at room temperature. Two days later, pink blocks of (I) were obtained with a yield of 30%. Anal. Calc. for C36H36Cl2F12Mn2N8OP2: C 40.48, H 3.37, N 10.50%; Found: C 40.42, H 3.38, N 10.44%.

Refinement top

All H atoms were placed in calculated positions with C—H = 0.93Å and refined as riding with Uiso(H) = 1.2Ueq(carrier).

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), drawn with 30% probability displacement ellipsoids for the non-hydrogen atoms.
µ-Oxido-bis{chlorido[tris(2-pyridylmethyl)amine]manganese(III)} bis(hexafluoridophosphate) top
Crystal data top
[Mn2O(C18H18Cl1N4)2](PF6)2Z = 1
Mr = 1067.45F000 = 538
Triclinic, P1Dx = 1.675 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.5517 (12) ÅCell parameters from 4125 reflections
b = 11.3128 (18) Åθ = 3.0–26.0º
c = 12.914 (2) ŵ = 0.89 mm−1
α = 115.51 (2)ºT = 293 (2) K
β = 107.44 (2)ºBlock, pink
γ = 91.49 (2)º0.28 × 0.22 × 0.18 mm
V = 1058.1 (3) Å3
Data collection top
Bruker APEXII CCD
diffractometer		4125 independent reflections
Radiation source: fine-focus sealed tube3801 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 293(2) Kθmax = 26.0º
φ and ω scansθmin = 3.0º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −8→10
Tmin = 0.788, Tmax = 0.856k = −13→13
9180 measured reflectionsl = −15→15
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.029  w = 1/[σ2(Fo2) + (0.0355P)2 + 0.508P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.076(Δ/σ)max = 0.001
S = 1.00Δρmax = 0.27 e Å−3
4125 reflectionsΔρmin = −0.31 e Å−3
287 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0273 (16)
Secondary atom site location: difference Fourier map
Crystal data top
[Mn2O(C18H18Cl1N4)2](PF6)2γ = 91.49 (2)º
Mr = 1067.45V = 1058.1 (3) Å3
Triclinic, P1Z = 1
a = 8.5517 (12) ÅMo Kα
b = 11.3128 (18) ŵ = 0.89 mm−1
c = 12.914 (2) ÅT = 293 (2) K
α = 115.51 (2)º0.28 × 0.22 × 0.18 mm
β = 107.44 (2)º
Data collection top
Bruker APEXII CCD
diffractometer		4125 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		3801 reflections with I > 2σ(I)
Tmin = 0.788, Tmax = 0.856Rint = 0.021
9180 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029287 parameters
wR(F2) = 0.076H-atom parameters constrained
S = 1.00Δρmax = 0.27 e Å−3
4125 reflectionsΔρmin = −0.31 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
Mn11.03744 (3)0.34680 (2)0.39271 (2)0.0591 (3)
C160.9137 (3)0.5294 (2)0.15470 (19)0.0579 (6)
H160.81440.54730.11470.070*
C151.0631 (4)0.5736 (2)0.1515 (2)0.0698 (7)
H151.06560.62400.11090.084*
C120.7465 (3)0.1753 (2)0.14497 (19)0.0547 (5)
H12A0.74510.20110.08220.066*
H12B0.63700.12550.12120.066*
C141.2072 (4)0.5437 (3)0.2077 (2)0.0693 (7)
H141.30800.57230.20480.083*
C131.2008 (3)0.4705 (2)0.2687 (2)0.0586 (5)
H131.29890.44970.30700.070*
C90.9549 (3)−0.1237 (2)0.0608 (2)0.0591 (6)
H90.9333−0.21160.00070.071*
C71.1344 (3)0.0604 (2)0.2403 (2)0.0506 (5)
H71.23760.09590.30260.061*
C100.8352 (3)−0.0448 (2)0.05877 (19)0.0503 (5)
H100.7312−0.0789−0.00270.060*
C81.1067 (3)−0.0700 (2)0.1531 (2)0.0589 (6)
H81.1897−0.12110.15670.071*
C60.6719 (2)0.2876 (2)0.33136 (19)0.0473 (5)
H6A0.56320.23590.27400.057*
H6B0.65640.37600.38210.057*
C30.7291 (3)0.1172 (2)0.5339 (2)0.0583 (5)
H30.66600.07770.56190.070*
C10.9874 (2)0.18989 (19)0.53077 (17)0.0432 (4)
H11.10280.19890.55750.052*
C170.9146 (3)0.45733 (19)0.21901 (16)0.0442 (4)
C20.8988 (3)0.1304 (2)0.57405 (19)0.0509 (5)
H20.95300.09980.62920.061*
C40.6514 (3)0.1631 (2)0.4512 (2)0.0528 (5)
H40.53590.15360.42270.063*
C180.7604 (3)0.41495 (19)0.23735 (18)0.0450 (4)
H18A0.74280.48830.30540.054*
H18B0.66410.39180.16470.054*
C50.7463 (2)0.22291 (18)0.41146 (17)0.0400 (4)
C110.8713 (2)0.08589 (18)0.14917 (16)0.0398 (4)
Cl11.31393 (6)0.35086 (5)0.48444 (5)0.05319 (15)
F30.5826 (2)0.6606 (2)0.1912 (2)0.1062 (6)
F50.6040 (2)0.71991 (18)0.04862 (16)0.0904 (5)
F20.4876 (2)0.84879 (19)0.27957 (14)0.0865 (5)
F10.73275 (18)0.8610 (2)0.24889 (16)0.0976 (6)
F60.5112 (2)0.90781 (15)0.13872 (16)0.0796 (4)
F40.36039 (17)0.71075 (14)0.08069 (13)0.0705 (4)
N31.0566 (2)0.42831 (16)0.27464 (15)0.0455 (4)
N10.77789 (18)0.29832 (15)0.26229 (14)0.0395 (3)
N41.01895 (19)0.13923 (15)0.23967 (14)0.0415 (3)
N20.91299 (18)0.23567 (15)0.45101 (14)0.0386 (3)
O11.00000.50000.50000.0399 (4)
P10.54877 (7)0.78428 (6)0.16552 (5)0.05074 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0639 (6)0.0610 (6)0.0547 (6)0.0008 (4)0.0176 (5)−0.0068 (4)
C160.0825 (17)0.0485 (11)0.0445 (11)0.0145 (11)0.0199 (11)0.0241 (9)
C150.109 (2)0.0528 (13)0.0546 (13)0.0012 (13)0.0329 (14)0.0282 (11)
C120.0490 (12)0.0473 (11)0.0438 (11)0.0091 (9)−0.0021 (9)0.0119 (9)
C140.0823 (18)0.0680 (15)0.0664 (15)−0.0023 (13)0.0354 (14)0.0328 (13)
C130.0575 (13)0.0637 (13)0.0599 (13)0.0039 (10)0.0251 (11)0.0302 (11)
C90.0717 (15)0.0427 (11)0.0615 (13)0.0130 (10)0.0313 (12)0.0171 (10)
C70.0432 (11)0.0545 (11)0.0568 (12)0.0165 (9)0.0196 (9)0.0259 (10)
C100.0524 (12)0.0457 (10)0.0480 (11)0.0023 (9)0.0171 (9)0.0179 (9)
C80.0620 (14)0.0535 (12)0.0700 (14)0.0251 (10)0.0329 (12)0.0285 (11)
C60.0285 (9)0.0554 (11)0.0601 (12)0.0089 (8)0.0103 (8)0.0316 (10)
C30.0582 (13)0.0635 (13)0.0647 (14)0.0047 (10)0.0273 (11)0.0360 (11)
C10.0405 (10)0.0443 (10)0.0450 (10)0.0095 (8)0.0116 (8)0.0226 (8)
C170.0552 (12)0.0401 (9)0.0348 (9)0.0102 (8)0.0153 (8)0.0152 (8)
C20.0555 (12)0.0529 (11)0.0510 (11)0.0101 (9)0.0184 (9)0.0297 (10)
C40.0355 (10)0.0582 (12)0.0680 (13)0.0054 (9)0.0189 (9)0.0314 (11)
C180.0469 (11)0.0461 (10)0.0402 (10)0.0158 (8)0.0092 (8)0.0218 (8)
C50.0315 (9)0.0392 (9)0.0446 (10)0.0053 (7)0.0113 (7)0.0164 (8)
C110.0410 (10)0.0412 (9)0.0388 (9)0.0051 (7)0.0143 (7)0.0197 (8)
Cl10.0309 (2)0.0587 (3)0.0585 (3)0.0126 (2)0.0094 (2)0.0207 (2)
F30.0981 (14)0.1209 (15)0.1660 (19)0.0536 (12)0.0649 (13)0.1092 (15)
F50.0931 (12)0.0951 (12)0.0853 (11)0.0077 (9)0.0564 (10)0.0269 (9)
F20.0790 (11)0.1126 (13)0.0617 (9)0.0061 (9)0.0342 (8)0.0286 (9)
F10.0443 (8)0.1515 (17)0.0847 (11)−0.0079 (9)0.0016 (7)0.0586 (11)
F60.0760 (10)0.0695 (9)0.0981 (11)0.0058 (7)0.0193 (8)0.0500 (9)
F40.0522 (8)0.0690 (8)0.0724 (9)−0.0055 (6)0.0123 (7)0.0238 (7)
N30.0483 (9)0.0479 (9)0.0439 (9)0.0075 (7)0.0187 (7)0.0225 (7)
N10.0332 (8)0.0421 (8)0.0402 (8)0.0094 (6)0.0078 (6)0.0193 (7)
N40.0391 (8)0.0433 (8)0.0436 (8)0.0111 (6)0.0153 (7)0.0205 (7)
N20.0325 (8)0.0400 (8)0.0429 (8)0.0076 (6)0.0113 (6)0.0197 (7)
O10.0350 (9)0.0409 (9)0.0411 (9)0.0076 (7)0.0104 (7)0.0185 (8)
P10.0402 (3)0.0644 (3)0.0516 (3)0.0071 (2)0.0144 (2)0.0312 (3)
Geometric parameters (Å, °) top
Mn1—O11.8034 (5)C6—N11.485 (3)
Mn1—N22.1227 (16)C6—C51.514 (3)
Mn1—N32.1341 (17)C6—H6A0.970
Mn1—N12.2280 (16)C6—H6B0.970
Mn1—N42.2893 (17)C3—C21.367 (3)
Mn1—Cl12.2944 (7)C3—C41.386 (3)
C16—C151.379 (4)C3—H30.930
C16—C171.390 (3)C1—N21.348 (2)
C16—H160.930C1—C21.375 (3)
C15—C141.361 (4)C1—H10.930
C15—H150.930C17—N31.341 (3)
C12—N11.491 (2)C17—C181.509 (3)
C12—C111.495 (3)C2—H20.930
C12—H12A0.970C4—C51.378 (3)
C12—H12B0.970C4—H40.930
C14—C131.377 (3)C18—N11.488 (2)
C14—H140.930C18—H18A0.970
C13—N31.346 (3)C18—H18B0.970
C13—H130.930C5—N21.343 (2)
C9—C81.372 (3)C11—N41.339 (2)
C9—C101.377 (3)F3—P11.5854 (18)
C9—H90.930F5—P11.5906 (16)
C7—N41.348 (3)F2—P11.5908 (16)
C7—C81.375 (3)F1—P11.5799 (16)
C7—H70.930F6—P11.5966 (16)
C10—C111.385 (3)F4—P11.6046 (15)
C10—H100.930O1—Mn1i1.8034 (5)
C8—H80.930
O1—Mn1—N290.82 (4)N2—C1—H1118.8
O1—Mn1—N392.87 (5)C2—C1—H1118.8
N2—Mn1—N3154.78 (6)N3—C17—C16121.2 (2)
O1—Mn1—N191.90 (5)N3—C17—C18116.09 (17)
N2—Mn1—N178.71 (6)C16—C17—C18122.6 (2)
N3—Mn1—N176.24 (6)C1—C2—C3118.3 (2)
O1—Mn1—N4166.67 (4)C1—C2—H2120.8
N2—Mn1—N482.20 (6)C3—C2—H2120.8
N3—Mn1—N488.79 (6)C5—C4—C3119.6 (2)
N1—Mn1—N475.64 (6)C5—C4—H4120.2
O1—Mn1—Cl1102.88 (3)C3—C4—H4120.2
N2—Mn1—Cl1103.45 (5)N1—C18—C17110.49 (15)
N3—Mn1—Cl1100.01 (5)N1—C18—H18A109.6
N1—Mn1—Cl1164.97 (4)C17—C18—H18A109.6
N4—Mn1—Cl189.83 (5)N1—C18—H18B109.6
C15—C16—C17118.5 (2)C17—C18—H18B109.6
C15—C16—H16120.7H18A—C18—H18B108.1
C17—C16—H16120.7N2—C5—C4120.59 (18)
C16—C15—C14120.3 (2)N2—C5—C6116.63 (17)
C16—C15—H15119.9C4—C5—C6122.56 (17)
C14—C15—H15119.9N4—C11—C10122.48 (18)
N1—C12—C11114.72 (15)N4—C11—C12117.29 (16)
N1—C12—H12A108.6C10—C11—C12120.17 (18)
C11—C12—H12A108.6C17—N3—C13119.35 (19)
N1—C12—H12B108.6C17—N3—Mn1114.96 (13)
C11—C12—H12B108.6C13—N3—Mn1124.77 (15)
H12A—C12—H12B107.6C12—N1—C6112.81 (17)
C13—C14—C15118.8 (2)C12—N1—C18109.20 (15)
C13—C14—H14120.6C6—N1—C18112.67 (15)
C15—C14—H14120.6C12—N1—Mn1113.32 (12)
N3—C13—C14121.8 (2)C6—N1—Mn1104.27 (11)
N3—C13—H13119.1C18—N1—Mn1104.25 (11)
C14—C13—H13119.1C7—N4—C11117.38 (17)
C8—C9—C10118.7 (2)C7—N4—Mn1125.96 (14)
C8—C9—H9120.7C11—N4—Mn1116.09 (12)
C10—C9—H9120.7C5—N2—C1119.34 (17)
N4—C7—C8123.0 (2)C5—N2—Mn1114.73 (12)
N4—C7—H7118.5C1—N2—Mn1125.63 (13)
C8—C7—H7118.5Mn1i—O1—Mn1180
C11—C10—C9119.3 (2)F3—P1—F191.72 (12)
C11—C10—H10120.3F3—P1—F290.05 (11)
C9—C10—H10120.3F1—P1—F290.83 (10)
C9—C8—C7119.1 (2)F3—P1—F6179.00 (10)
C9—C8—H8120.4F1—P1—F689.26 (10)
C7—C8—H8120.4F2—P1—F689.71 (10)
N1—C6—C5112.64 (15)F3—P1—F590.98 (11)
N1—C6—H6A109.1F1—P1—F590.78 (10)
C5—C6—H6A109.1F2—P1—F5178.06 (10)
N1—C6—H6B109.1F6—P1—F589.23 (10)
C5—C6—H6B109.1F3—P1—F490.10 (11)
H6A—C6—H6B107.8F1—P1—F4178.14 (11)
C2—C3—C4119.6 (2)F2—P1—F488.82 (9)
C2—C3—H3120.2F6—P1—F488.92 (9)
C4—C3—H3120.2F5—P1—F489.54 (9)
N2—C1—C2122.44 (19)
Symmetry codes: (i) −x+2, −y+1, −z+1.
Acknowledgements top

The authors thank Liaocheng University for financial support and Professor Jianmin Dou for his help.

references
References top

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

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

Okabe, N. & Oya, N. (2000). Acta Cryst. C56, 1416–1417.

Scapin, G., Reddy, S. G., Zheng, R. & Blanchard, J. S. (1997). Biochemistry, 36, 15081–15088.

Serre, C., Marrot, J. & Ferey, G. (2005). Inorg. Chem. 44, 654–658.

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