supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2302    [ doi:10.1107/S1600536807038603 ]

catena-Poly[[manganese(II)-[mu]-[N,N,N',N'-tetrakis(2-pyridylmethyl)hexane-1,6-diamine]] bis(perchlorate) acetone disolvate dihydrate]

I.-C. Hwang and K. Ha

Abstract top

The title compound, [Mn(C30H36N6)](ClO4)2·2C3H6O·2H2O, consists of a cationic complex polymer with counter-anions and solvent molecules. In the cationic polymer, Mn2+ ions are bridged by the hexadentate ligand N,N,N',N'-tetrakis(2-pyridylmethyl)hexane-1,6-diamine (tphn) to form a one-dimensional chain structure along the c axis. The repeat unit of the polymer, MnII(tphn), is disposed about a twofold axis passing through the Mn atom. The coordination geometry around the Mn centre is distorted octahedral.

Comment top

The title compound consists of cationic complex polymer with counter anions (ClO4) and solvents (acetone and water). In the cation polymer, Mn2+ ions are bridged by the hexadentate ligand, N,N,N',N'-tetrakis(2-pyridylmethyl)-1,6-diaminohexane (tphn), and the constitutional repeating unit of the polymer, MnII(tphn), is disposed about a twofold axis passing through the Mn atom (Fig. 1). The Mn ion is six-coordinated in a distorted octahedral structure by three N atoms from one tphn ligand and three N atoms from another tphn ligand in the facial positions, respectively. The Mn—N(pyridyl) bond lengths (2.267 (4) and 2.217 (4) Å) are slightly longer than the Mn—N(amine) bond length (2.369 (4) Å). The polymer reveals a one-dimensional chain structure along the c axis (Fig. 2).

Related literature top

For related literature, see: Jensen et al. (1997).

Experimental top

To a solution of N,N,N',N'-tetrakis(2-pyridylmethyl)-1,6-diaminohexane (0.50 g, 1.04 mmol) in EtOH (15 ml) was added Mn(ClO4)2·6H2O (0.38 g, 1.05 mmol) and stirred for 1 h at room temparature. The formed precipitate was separated by filtration and washed with EtOH and dried, to give a dark yellow powder (0.48 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a acetone/H2O(1:1) solution.

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective carrier atoms [C—H = 0.94 (aromatic), 0.98 (CH2) or 0.97 Å (CH3) and Uiso(H) = 1.2Ueq or 1.5Ueq(methyl C)]. The solvent molecules were highly disordered, and then the atoms of acetone and water were refined with isotropic thermal parameters, as a result it reflects on large value of the R factor. The H atoms of the solvent H2O molecules could neither be located from Fourier difference maps nor added geometrically.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of the constitutional repeating unit of the title compound [Symmetry code: (a) −x, y, 1/2 − z]. Displacement ellipsoids are drawn at the 20% probability level. H atoms and the solvent molecules have been omitted for clarity.
[Figure 2] Fig. 2. View of the unit-cell contents and chain structure of the title compound. H atoms and the solvent molecules have been omitted for clarity.
[Figure 3] Fig. 3. The N,N,N',N'-tetrakis(2-pyridylmethyl)hexane-1,6-diamine ligand.
catena-Poly[[manganese(II)-µ-[N,N,N',N'-tetrakis(2-pyridylmethyl)hexane- 1,6-diamine]] diperchlorate acetone disolvate dihydrate] top
Crystal data top
[Mn(C30H36N6)](ClO4)2·2C3H6O·2H2OF000 = 1860
Mr = 886.68Dx = 1.426 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2085 reflections
a = 18.7266 (16) Åθ = 2.2–21.0º
b = 14.5252 (12) ŵ = 0.52 mm−1
c = 15.2375 (13) ÅT = 243 (2) K
β = 94.782 (2)ºBlock, yellow
V = 4130.3 (6) Å30.20 × 0.18 × 0.15 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer		4248 independent reflections
Radiation source: fine-focus sealed tube2171 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.056
T = 243(2) Kθmax = 26.4º
φ and ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −23→22
Tmin = 0.707, Tmax = 0.926k = −18→18
16555 measured reflectionsl = −19→12
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)] = 0.073H-atom parameters constrained
wR(F2) = 0.227  w = 1/[σ2(Fo2) + (0.132P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.92(Δ/σ)max < 0.001
4248 reflectionsΔρmax = 0.86 e Å−3
230 parametersΔρmin = −0.49 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Mn(C30H36N6)](ClO4)2·2C3H6O·2H2OV = 4130.3 (6) Å3
Mr = 886.68Z = 4
Monoclinic, C2/cMo Kα
a = 18.7266 (16) ŵ = 0.52 mm−1
b = 14.5252 (12) ÅT = 243 (2) K
c = 15.2375 (13) Å0.20 × 0.18 × 0.15 mm
β = 94.782 (2)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		4248 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2171 reflections with I > 2σ(I)
Tmin = 0.707, Tmax = 0.926Rint = 0.056
16555 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.073230 parameters
wR(F2) = 0.227H-atom parameters constrained
S = 0.92Δρmax = 0.86 e Å−3
4248 reflectionsΔρmin = −0.49 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
Mn0.00000.26386 (6)0.25000.0436 (3)
N10.0765 (2)0.2265 (2)0.1478 (2)0.0488 (10)
N20.0500 (2)0.3736 (2)0.3356 (3)0.0509 (10)
N30.1019 (2)0.1940 (3)0.3248 (2)0.0523 (10)
C10.0736 (3)0.2587 (3)0.0651 (3)0.0508 (12)
H10.03800.30220.04780.061*
C20.1189 (3)0.2322 (4)0.0046 (3)0.0588 (13)
H20.11380.2562−0.05290.071*
C30.1713 (3)0.1710 (4)0.0281 (3)0.0688 (15)
H30.20300.1514−0.01280.083*
C40.1773 (3)0.1378 (4)0.1134 (4)0.0661 (15)
H40.21390.09610.13180.079*
C50.1285 (3)0.1670 (3)0.1715 (3)0.0547 (13)
C60.1313 (3)0.1281 (3)0.2638 (3)0.0637 (15)
H6A0.10370.07070.26330.076*
H6B0.18110.11380.28430.076*
C70.0191 (3)0.4531 (3)0.3588 (3)0.0620 (14)
H7−0.02770.46570.33450.074*
C80.0512 (4)0.5154 (4)0.4146 (4)0.0718 (16)
H80.02760.57000.42850.086*
C90.1186 (4)0.4969 (4)0.4502 (4)0.087 (2)
H90.14230.53930.48910.104*
C100.1522 (3)0.4176 (5)0.4301 (4)0.0754 (17)
H100.19860.40450.45560.090*
C110.1176 (3)0.3571 (3)0.3721 (3)0.0551 (13)
C120.1520 (3)0.2711 (4)0.3387 (4)0.0605 (13)
H12A0.17220.28530.28290.073*
H12B0.19150.25250.38110.073*
C130.0935 (3)0.1483 (4)0.4109 (3)0.0632 (14)
H13A0.14110.13070.43690.076*
H13B0.07410.19360.45030.076*
C140.0467 (3)0.0653 (3)0.4084 (3)0.0650 (15)
H14A0.07230.01320.38460.078*
H14B0.00360.07680.36900.078*
C150.0251 (3)0.0406 (3)0.4997 (4)0.0738 (17)
H15A0.06850.02670.53800.089*
H15B0.00200.09410.52440.089*
Cl0.23323 (9)0.43776 (12)0.17809 (10)0.0844 (6)
O10.2592 (2)0.4928 (3)0.1128 (3)0.1020 (15)
O20.2566 (4)0.4597 (4)0.2616 (3)0.150 (3)
O30.1583 (3)0.4373 (6)0.1717 (5)0.193 (4)
O40.2472 (4)0.3424 (4)0.1612 (4)0.154 (2)
O1S0.4558 (3)0.2153 (4)0.3938 (5)0.139 (2)*
C1S0.4137 (6)0.2292 (8)0.3337 (8)0.150 (4)*
C2S0.3836 (7)0.1745 (10)0.2604 (9)0.231 (6)*
H2S10.33930.20250.23580.346*
H2S20.37380.11280.28070.346*
H2S30.41740.17140.21560.346*
C3S0.3406 (7)0.2371 (9)0.3732 (9)0.302 (10)*
H3S10.31510.29060.34880.453*
H3S20.34820.24360.43670.453*
H3S30.31250.18220.35910.453*
O1W0.4390 (7)0.3332 (9)0.2678 (9)0.416 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.0622 (7)0.0285 (5)0.0426 (6)0.0000.0197 (5)0.000
N10.066 (3)0.034 (2)0.048 (2)0.0046 (19)0.0172 (19)0.0045 (17)
N20.072 (3)0.034 (2)0.050 (2)−0.0020 (18)0.023 (2)−0.0016 (17)
N30.077 (3)0.040 (2)0.043 (2)0.013 (2)0.021 (2)0.0066 (17)
C10.069 (3)0.041 (3)0.044 (3)−0.002 (2)0.015 (2)0.003 (2)
C20.077 (4)0.061 (3)0.040 (3)−0.007 (3)0.016 (3)−0.002 (2)
C30.083 (4)0.076 (4)0.052 (3)0.003 (3)0.029 (3)−0.010 (3)
C40.078 (4)0.060 (3)0.063 (4)0.018 (3)0.027 (3)−0.006 (3)
C50.074 (3)0.041 (3)0.052 (3)0.005 (2)0.023 (3)−0.003 (2)
C60.091 (4)0.050 (3)0.054 (3)0.024 (3)0.026 (3)0.003 (2)
C70.090 (4)0.040 (3)0.060 (3)0.001 (3)0.025 (3)−0.004 (2)
C80.120 (5)0.044 (3)0.055 (3)−0.010 (3)0.025 (4)−0.010 (3)
C90.142 (7)0.060 (4)0.061 (4)−0.029 (4)0.018 (4)−0.017 (3)
C100.084 (4)0.084 (4)0.058 (4)−0.024 (3)0.004 (3)−0.007 (3)
C110.073 (4)0.054 (3)0.042 (3)−0.008 (3)0.020 (3)0.004 (2)
C120.065 (3)0.066 (3)0.052 (3)0.004 (3)0.014 (3)0.007 (3)
C130.090 (4)0.058 (3)0.044 (3)0.023 (3)0.020 (3)0.011 (2)
C140.109 (4)0.039 (3)0.051 (3)0.019 (3)0.030 (3)0.010 (2)
C150.128 (5)0.043 (3)0.054 (3)0.024 (3)0.031 (3)0.018 (3)
Cl0.0958 (12)0.0966 (13)0.0642 (10)−0.0439 (9)0.0265 (8)−0.0183 (8)
O10.112 (3)0.128 (4)0.069 (3)−0.052 (3)0.022 (2)−0.005 (3)
O20.236 (7)0.152 (5)0.067 (3)−0.110 (5)0.034 (4)−0.023 (3)
O30.101 (4)0.273 (10)0.208 (8)−0.031 (5)0.041 (4)0.073 (7)
O40.240 (7)0.108 (5)0.124 (5)−0.010 (5)0.079 (5)−0.030 (4)
Geometric parameters (Å, °) top
Mn—N22.217 (4)C9—H90.9400
Mn—N2i2.217 (4)C10—C111.370 (7)
Mn—N1i2.267 (4)C10—H100.9400
Mn—N12.267 (4)C11—C121.514 (7)
Mn—N32.369 (4)C12—H12A0.9800
Mn—N3i2.369 (4)C12—H12B0.9800
N1—C51.331 (6)C13—C141.489 (7)
N1—C11.341 (6)C13—H13A0.9800
N2—C71.352 (6)C13—H13B0.9800
N2—C111.360 (6)C14—C151.524 (7)
N3—C121.465 (6)C14—H14A0.9800
N3—C61.472 (6)C14—H14B0.9800
N3—C131.490 (6)C15—C15ii1.509 (11)
C1—C21.360 (7)C15—H15A0.9800
C1—H10.9400C15—H15B0.9800
C2—C31.350 (7)Cl—O21.349 (5)
C2—H20.9400Cl—O11.395 (4)
C3—C41.382 (7)Cl—O31.399 (6)
C3—H30.9400Cl—O41.437 (6)
C4—C51.390 (6)O1S—C1S1.175 (11)
C4—H40.9400C1S—C2S1.446 (15)
C5—C61.513 (7)C1S—C3S1.546 (15)
C6—H6A0.9800C2S—H2S10.9700
C6—H6B0.9800C2S—H2S20.9700
C7—C81.349 (7)C2S—H2S30.9700
C7—H70.9400C3S—H3S10.9700
C8—C91.359 (8)C3S—H3S20.9700
C8—H80.9400C3S—H3S30.9700
C9—C101.359 (9)
N2—Mn—N2i88.1 (2)C8—C9—C10120.7 (6)
N2—Mn—N1i91.59 (13)C8—C9—H9119.7
N2i—Mn—N1i108.42 (14)C10—C9—H9119.7
N2—Mn—N1108.42 (14)C9—C10—C11119.0 (6)
N2i—Mn—N191.59 (13)C9—C10—H10120.5
N1i—Mn—N1152.33 (19)C11—C10—H10120.5
N2—Mn—N374.99 (14)N2—C11—C10121.7 (5)
N2i—Mn—N3151.06 (14)N2—C11—C12114.5 (4)
N1i—Mn—N395.57 (14)C10—C11—C12123.7 (5)
N1—Mn—N372.42 (13)N3—C12—C11113.2 (4)
N2—Mn—N3i151.06 (14)N3—C12—H12A108.9
N2i—Mn—N3i74.98 (14)C11—C12—H12A108.9
N1i—Mn—N3i72.42 (13)N3—C12—H12B108.9
N1—Mn—N3i95.57 (14)C11—C12—H12B108.9
N3—Mn—N3i129.2 (2)H12A—C12—H12B107.7
C5—N1—C1116.9 (4)C14—C13—N3116.3 (4)
C5—N1—Mn117.4 (3)C14—C13—H13A108.2
C1—N1—Mn125.7 (3)N3—C13—H13A108.2
C7—N2—C11116.6 (4)C14—C13—H13B108.2
C7—N2—Mn126.8 (4)N3—C13—H13B108.2
C11—N2—Mn116.6 (3)H13A—C13—H13B107.4
C12—N3—C6108.7 (4)C13—C14—C15111.6 (5)
C12—N3—C13109.1 (4)C13—C14—H14A109.3
C6—N3—C13109.8 (4)C15—C14—H14A109.3
C12—N3—Mn102.8 (3)C13—C14—H14B109.3
C6—N3—Mn107.7 (3)C15—C14—H14B109.3
C13—N3—Mn118.3 (3)H14A—C14—H14B108.0
N1—C1—C2124.1 (5)C15ii—C15—C14113.7 (6)
N1—C1—H1118.0C15ii—C15—H15A108.8
C2—C1—H1118.0C14—C15—H15A108.8
C3—C2—C1119.2 (5)C15ii—C15—H15B108.8
C3—C2—H2120.4C14—C15—H15B108.8
C1—C2—H2120.4H15A—C15—H15B107.7
C2—C3—C4118.7 (5)O2—Cl—O1115.6 (3)
C2—C3—H3120.7O2—Cl—O3108.1 (5)
C4—C3—H3120.7O1—Cl—O3111.1 (4)
C3—C4—C5119.1 (5)O2—Cl—O4110.3 (4)
C3—C4—H4120.5O1—Cl—O4110.2 (3)
C5—C4—H4120.5O3—Cl—O4100.4 (5)
N1—C5—C4122.1 (5)O1S—C1S—C2S134.4 (12)
N1—C5—C6117.6 (4)O1S—C1S—C3S105.5 (11)
C4—C5—C6120.3 (5)C2S—C1S—C3S92.3 (9)
N3—C6—C5111.0 (4)C1S—C2S—H2S1109.5
N3—C6—H6A109.4C1S—C2S—H2S2109.5
C5—C6—H6A109.4H2S1—C2S—H2S2109.5
N3—C6—H6B109.4C1S—C2S—H2S3109.5
C5—C6—H6B109.4H2S1—C2S—H2S3109.5
H6A—C6—H6B108.0H2S2—C2S—H2S3109.5
C8—C7—N2124.1 (6)C1S—C3S—H3S1109.5
C8—C7—H7118.0C1S—C3S—H3S2109.5
N2—C7—H7118.0H3S1—C3S—H3S2109.5
C7—C8—C9117.9 (6)C1S—C3S—H3S3109.5
C7—C8—H8121.0H3S1—C3S—H3S3109.5
C9—C8—H8121.0H3S2—C3S—H3S3109.5
N2—Mn—N1—C583.1 (4)Mn—N1—C1—C2−177.6 (4)
N2i—Mn—N1—C5171.6 (3)N1—C1—C2—C3−1.2 (8)
N1i—Mn—N1—C5−51.2 (3)C1—C2—C3—C4−0.5 (8)
N3—Mn—N1—C516.1 (3)C2—C3—C4—C51.3 (8)
N3i—Mn—N1—C5−113.4 (3)C1—N1—C5—C4−1.0 (7)
N2—Mn—N1—C1−97.5 (4)Mn—N1—C5—C4178.5 (4)
N2i—Mn—N1—C1−9.0 (4)C1—N1—C5—C6−178.4 (4)
N1i—Mn—N1—C1128.2 (4)Mn—N1—C5—C61.1 (6)
N3—Mn—N1—C1−164.4 (4)C3—C4—C5—N1−0.6 (8)
N3i—Mn—N1—C166.1 (4)C3—C4—C5—C6176.8 (5)
N2i—Mn—N2—C740.4 (3)C12—N3—C6—C5−70.6 (5)
N1i—Mn—N2—C7−67.9 (4)C13—N3—C6—C5170.2 (4)
N1—Mn—N2—C7131.5 (4)Mn—N3—C6—C540.1 (5)
N3—Mn—N2—C7−163.3 (4)N1—C5—C6—N3−29.4 (7)
N3i—Mn—N2—C7−13.0 (5)C4—C5—C6—N3153.2 (5)
N2i—Mn—N2—C11−143.1 (4)C11—N2—C7—C80.3 (7)
N1i—Mn—N2—C11108.5 (3)Mn—N2—C7—C8176.7 (4)
N1—Mn—N2—C11−52.1 (3)N2—C7—C8—C9−0.4 (8)
N3—Mn—N2—C1113.1 (3)C7—C8—C9—C10−0.3 (9)
N3i—Mn—N2—C11163.5 (3)C8—C9—C10—C111.1 (9)
N2—Mn—N3—C12−30.5 (3)C7—N2—C11—C100.6 (7)
N2i—Mn—N3—C1225.7 (4)Mn—N2—C11—C10−176.2 (4)
N1i—Mn—N3—C12−120.7 (3)C7—N2—C11—C12−175.4 (4)
N1—Mn—N3—C1284.8 (3)Mn—N2—C11—C127.8 (5)
N3i—Mn—N3—C12167.5 (3)C9—C10—C11—N2−1.2 (8)
N2—Mn—N3—C6−145.2 (3)C9—C10—C11—C12174.4 (5)
N2i—Mn—N3—C6−89.0 (4)C6—N3—C12—C11159.4 (4)
N1i—Mn—N3—C6124.7 (3)C13—N3—C12—C11−80.9 (5)
N1—Mn—N3—C6−29.8 (3)Mn—N3—C12—C1145.5 (4)
N3i—Mn—N3—C652.8 (3)N2—C11—C12—N3−38.9 (6)
N2—Mn—N3—C1389.7 (3)C10—C11—C12—N3145.2 (5)
N2i—Mn—N3—C13145.9 (3)C12—N3—C13—C14−177.3 (4)
N1i—Mn—N3—C13−0.5 (4)C6—N3—C13—C14−58.3 (6)
N1—Mn—N3—C13−155.0 (4)Mn—N3—C13—C1465.8 (5)
N3i—Mn—N3—C13−72.3 (3)N3—C13—C14—C15−164.0 (4)
C5—N1—C1—C21.9 (7)C13—C14—C15—C15ii177.3 (6)
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, −y, −z+1.
Acknowledgements top

This study was financially supported by Chonnam National University in 2006.

references
References top

Bruker (2000). SADABS (Version 2.03), SMART (Version 5.618) and SAINT (Version 6.02a). Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Jensen, K. B., McKenzie, C. J., Simonsen, O., Toftlund, H. & Hazell, A. (1997). Inorg. Chim. Acta, 257, 163–172.

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

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.