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Acta Cryst. (2009). E65, m621    [ doi:10.1107/S1600536809016316 ]

catena-Poly[hemi(hexane-1,6-diammonium) [[aquadibromidomanganese(II)]-[mu]-pyridine-2-carboxylato]]

N.-H. Kim, I.-C. Hwang and K. Ha

Abstract top

The asymmetric unit of the title compound, {(C6H18N2)0.5[MnBr2(C6H4NO2)(H2O)]}n, contains the repeat unit of the complex anion and one-half of a hexane-1,6-diammonium cation that is located on a twofold rotation axis. In the anionic polymer, the Mn2+ ions are bridged by the pyridinecarboxylate (pic) anion ligand, forming a chain structure along the c axis. The Mn2+ ion is six-coordinated in a distorted octahedral environment by one N atom of the pyridine ring, two O atoms of the two carboxylate groups, one O atom of the water molecule and two Br atoms. The compound displays intermolecular N-H...O, N-H...Br, O-H...Br and O-H...O hydrogen bonding. There may also be intermolecular [pi]-[pi] interactions between adjacent pyridine rings, with a centroid-centroid distance of 3.992 (4) Å.

Comment top

Complex polymers are attracting great attention because of their potential applications such as in catalysis, magnetism, molecular recognition and other fileds (Huang et al., 2004). The title compound, {(C6H18N2)0.5[MnBr2(C6H4NO2)(H2O)]}n, consists of an anionic complex chain polymer with counter-cations (Fig. 1). In the anionic polymer, symmetry related Mn2+ ions are bridged by pyridinecarboxylate (pic) anion ligands to form one-dimensional zigzag chain structures along the c axis (Fig. 2). The Mn ion is six-coordinated in a distorted octahedral structure by one N atom of the pyridine ring, two O atoms of two carboxylate groups, one O atom of the water molecule and two Br atoms. The three O atoms are disposed in the facial position. The asymmetric unit contains the repeat unit of the polymer, [MnBr2(C6H4NO2)(H2O)]-, and one half of a 1,6-diammoniohexane cation. Cations sit on a 2-fold symmetry axes at 0, y, 1/4 (Wyckoff letter e). The compound displays intermolecular hydrogen bonding (Table 1). There may be also intermolecular π-π interactions between adjacent pyridine rings, with a centroid-centroid distance of 3.992 (4) Å. The structure of the anionic complex polymer is very similar to the structure of the neutral compound [MnCl(pic)(H2O)2]n in which the Mn ions are linked to each other by pyridinecarboxylate bridges in a syn - anti mode (Huang et al., 2004).

Related literature top

For the synthesis and structure of the Mn(III)–pic complex, [Mn(pic)3], see: Figgis et al. (1978); Yamaguchi & Sawyer (1985); Li et al. (2000). For the synthesis and structure of the Mn(II)–pic complex, [Mn(pic)2(H2O)2], see: Okabe & Koizumi (1998); Barandika et al. (1999). For details of mono-, di- and polynuclear Mn(II, III, IV)–pic complexes, see: Huang et al. (2004).

Experimental top

A solution of MnBr2.4H2O (0.116 g, 0.404 mmol), pyridine-2-carboxylic acid (0.101 g, 0.734 mmol) and 1,6-diaminohexane (0.021 g, 0.184 mmol) in H2O (10 ml) was refluxed for 4 h. The solvent was removed under vacuum and the residue was dried at 70 °C, to give a pale yellow film. Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH3CN solution.

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.93 Å (aromatic) or 0.97 Å (CH2) and N—H = 0.89 Å, and Uiso(H) = 1.2Ueq(C) or 1.5Ueq(N)]. The H atoms of the water molecule were located from Fourier difference maps, but not refined.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A structure detail of the title compound, with displacement ellipsoids drawn at the 50% probability level for non-H atoms [Symmetry codes: (a) x, -y, -1/2 + z, (b) x, -y, 1/2 + z, (c) -x, y, 3/2 - z].
[Figure 2] Fig. 2. View of the unit-cell contents and chain structure of the title compound. H atoms have been omitted for clarity.
catena-Poly[hemi(hexane-1,6-diammonium) [[aquadibromidomanganese(II)]-µ-pyridine-2-carboxylato]] top
Crystal data top
(C6H18N2)0.5[MnBr2(C6H4NO2)(H2O)]F000 = 1616
Mr = 413.99Dx = 1.934 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 806 reflections
a = 13.490 (3) Åθ = 2.8–25.3º
b = 21.510 (5) ŵ = 6.55 mm−1
c = 9.803 (2) ÅT = 293 K
β = 91.125 (4)ºStick, colorless
V = 2843.9 (11) Å30.10 × 0.10 × 0.10 mm
Z = 8
Data collection top
Bruker SMART 1000 CCD
diffractometer		2705 independent reflections
Radiation source: fine-focus sealed tube1846 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 293 Kθmax = 25.7º
φ and ω scansθmin = 1.8º
Absorption correction: Multi-scan
(SADABS; Bruker, 2000)		h = −16→15
Tmin = 0.394, Tmax = 0.520k = −26→26
7815 measured reflectionsl = −7→11
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)] = 0.031H-atom parameters constrained
wR(F2) = 0.114  w = 1/[σ2(Fo2) + (0.0606P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max < 0.001
2705 reflectionsΔρmax = 0.68 e Å−3
152 parametersΔρmin = −0.56 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C6H18N2)0.5[MnBr2(C6H4NO2)(H2O)]V = 2843.9 (11) Å3
Mr = 413.99Z = 8
Monoclinic, C2/cMo Kα
a = 13.490 (3) ŵ = 6.55 mm−1
b = 21.510 (5) ÅT = 293 K
c = 9.803 (2) Å0.10 × 0.10 × 0.10 mm
β = 91.125 (4)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		2705 independent reflections
Absorption correction: Multi-scan
(SADABS; Bruker, 2000)		1846 reflections with I > 2σ(I)
Tmin = 0.394, Tmax = 0.520Rint = 0.030
7815 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031152 parameters
wR(F2) = 0.114H-atom parameters constrained
S = 0.94Δρmax = 0.68 e Å−3
2705 reflectionsΔρmin = −0.56 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn10.32935 (6)0.06982 (4)0.41356 (8)0.0340 (2)
Br10.34335 (4)0.15379 (3)0.21825 (6)0.0438 (2)
Br20.13026 (5)0.06928 (3)0.40001 (8)0.0585 (2)
O10.3336 (3)0.01771 (15)0.6076 (4)0.0406 (10)
O20.3331 (3)−0.02393 (17)0.3343 (4)0.0491 (11)
O30.4928 (3)0.06506 (18)0.4217 (5)0.0549 (12)
H3A0.53580.09830.38650.082*
H3B0.53940.04080.43760.082*
N10.3431 (3)0.14114 (19)0.5834 (4)0.0349 (11)
C10.3514 (4)0.2031 (2)0.5714 (6)0.0442 (15)
H10.34880.22030.48440.053*
C20.3634 (5)0.2422 (3)0.6809 (7)0.0519 (16)
H20.36670.28500.66870.062*
C30.3702 (5)0.2168 (3)0.8077 (7)0.0558 (18)
H30.38000.24220.88360.067*
C40.3625 (5)0.1532 (3)0.8234 (6)0.0470 (15)
H40.36670.13510.90950.056*
C50.3488 (4)0.1175 (2)0.7091 (5)0.0318 (12)
C60.3378 (4)0.0470 (3)0.7180 (6)0.0343 (13)
N20.1654 (3)0.06720 (19)1.0558 (5)0.0717 (19)
H2A0.22320.06221.01510.107*
H2B0.12620.03501.03660.107*
H2C0.17540.06961.14570.107*
C70.1177 (3)0.12511 (19)1.0062 (5)0.0564 (18)
H7A0.16540.15881.01220.068*
H7B0.06300.13531.06500.068*
C80.0796 (5)0.1202 (3)0.8624 (7)0.0545 (17)
H8A0.03990.08280.85250.065*
H8B0.13510.11690.80130.065*
C90.0174 (5)0.1762 (3)0.8230 (7)0.065 (2)
H9A−0.04000.17770.88100.078*
H9B0.05600.21360.84000.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0451 (5)0.0302 (4)0.0267 (5)0.0019 (4)0.0001 (4)0.0004 (4)
Br10.0526 (4)0.0416 (3)0.0371 (4)0.0026 (3)0.0016 (3)0.0072 (3)
Br20.0466 (4)0.0593 (4)0.0697 (5)0.0030 (3)0.0012 (3)0.0179 (4)
O10.068 (3)0.0250 (19)0.029 (2)−0.0015 (18)0.001 (2)0.0003 (17)
O20.082 (3)0.036 (2)0.029 (2)0.003 (2)−0.001 (2)−0.0072 (18)
O30.042 (2)0.055 (3)0.068 (3)0.008 (2)0.005 (2)0.021 (2)
N10.045 (3)0.029 (3)0.031 (3)0.002 (2)0.000 (2)0.004 (2)
C10.062 (4)0.028 (3)0.043 (4)−0.002 (3)0.001 (3)0.009 (3)
C20.066 (4)0.029 (3)0.061 (4)0.001 (3)0.003 (4)−0.005 (3)
C30.082 (5)0.034 (3)0.051 (4)−0.004 (3)0.001 (4)−0.015 (3)
C40.069 (4)0.037 (3)0.035 (3)0.001 (3)0.000 (3)−0.001 (3)
C50.038 (3)0.029 (3)0.028 (3)0.004 (2)0.004 (2)0.001 (2)
C60.036 (3)0.038 (3)0.030 (3)−0.002 (2)−0.001 (3)0.005 (3)
N20.092 (5)0.050 (3)0.072 (4)0.012 (3)−0.031 (4)−0.015 (3)
C70.051 (4)0.050 (4)0.067 (5)0.009 (3)−0.016 (4)−0.012 (4)
C80.050 (4)0.060 (4)0.053 (4)0.001 (3)−0.005 (3)−0.003 (3)
C90.079 (5)0.042 (4)0.073 (5)0.007 (4)−0.019 (4)−0.003 (4)
Geometric parameters (Å, °) top
Mn1—O22.162 (4)C4—C51.368 (7)
Mn1—O32.206 (4)C4—H40.93
Mn1—O12.208 (4)C5—C61.526 (7)
Mn1—N12.269 (4)C6—O2ii1.247 (6)
Mn1—Br12.6416 (11)N2—C71.4799
Mn1—Br22.6864 (12)N2—H2A0.89
O1—C61.253 (6)N2—H2B0.89
O2—C6i1.247 (6)N2—H2C0.89
O3—H3A0.99C7—C81.495 (7)
O3—H3B0.83C7—H7A0.97
N1—C51.334 (6)C7—H7B0.97
N1—C11.343 (6)C8—C91.514 (8)
C1—C21.371 (8)C8—H8A0.97
C1—H10.93C8—H8B0.97
C2—C31.359 (9)C9—C9iii1.497 (13)
C2—H20.93C9—H9A0.97
C3—C41.382 (8)C9—H9B0.97
C3—H30.93
O2—Mn1—O386.53 (16)C5—C4—H4120.9
O2—Mn1—O180.53 (14)C3—C4—H4120.9
O3—Mn1—O186.35 (15)N1—C5—C4123.2 (5)
O2—Mn1—N1153.14 (15)N1—C5—C6115.3 (5)
O3—Mn1—N186.42 (16)C4—C5—C6121.5 (5)
O1—Mn1—N173.17 (14)O2ii—C6—O1126.0 (5)
O2—Mn1—Br1112.02 (11)O2ii—C6—C5117.1 (5)
O3—Mn1—Br188.42 (11)O1—C6—C5117.0 (5)
O1—Mn1—Br1166.09 (10)C7—N2—H2A109.5
N1—Mn1—Br193.65 (11)C7—N2—H2B109.5
O2—Mn1—Br290.48 (12)H2A—N2—H2B109.5
O3—Mn1—Br2176.99 (12)C7—N2—H2C109.5
O1—Mn1—Br292.83 (11)H2A—N2—H2C109.5
N1—Mn1—Br296.13 (12)H2B—N2—H2C109.5
Br1—Mn1—Br293.02 (3)N2—C7—C8112.9 (3)
C6—O1—Mn1119.3 (3)N2—C7—H7A109.0
C6i—O2—Mn1134.6 (4)C8—C7—H7A109.0
Mn1—O3—H3A123.2N2—C7—H7B109.0
Mn1—O3—H3B142.1C8—C7—H7B109.0
H3A—O3—H3B94H7A—C7—H7B107.8
C5—N1—C1117.2 (5)C7—C8—C9111.3 (5)
C5—N1—Mn1115.0 (3)C7—C8—H8A109.4
C1—N1—Mn1127.7 (4)C9—C8—H8A109.4
N1—C1—C2123.3 (6)C7—C8—H8B109.4
N1—C1—H1118.4C9—C8—H8B109.4
C2—C1—H1118.4H8A—C8—H8B108.0
C3—C2—C1118.4 (6)C9iii—C9—C8113.9 (5)
C3—C2—H2120.8C9iii—C9—H9A108.8
C1—C2—H2120.8C8—C9—H9A108.8
C2—C3—C4119.7 (6)C9iii—C9—H9B108.8
C2—C3—H3120.2C8—C9—H9B108.8
C4—C3—H3120.2H9A—C9—H9B107.7
C5—C4—C3118.3 (6)
O2—Mn1—O1—C6176.8 (4)C5—N1—C1—C2−1.1 (9)
O3—Mn1—O1—C689.7 (4)Mn1—N1—C1—C2−177.3 (4)
N1—Mn1—O1—C62.3 (4)N1—C1—C2—C32.0 (10)
Br1—Mn1—O1—C621.6 (8)C1—C2—C3—C4−1.6 (10)
Br2—Mn1—O1—C6−93.2 (4)C2—C3—C4—C50.4 (10)
O3—Mn1—O2—C6i−89.0 (6)C1—N1—C5—C4−0.2 (8)
O1—Mn1—O2—C6i−175.9 (6)Mn1—N1—C5—C4176.5 (4)
N1—Mn1—O2—C6i−164.0 (5)C1—N1—C5—C6179.3 (5)
Br1—Mn1—O2—C6i−2.1 (6)Mn1—N1—C5—C6−4.0 (6)
Br2—Mn1—O2—C6i91.3 (5)C3—C4—C5—N10.5 (9)
O2—Mn1—N1—C5−10.9 (6)C3—C4—C5—C6−178.9 (5)
O3—Mn1—N1—C5−86.0 (4)Mn1—O1—C6—O2ii174.2 (4)
O1—Mn1—N1—C51.3 (4)Mn1—O1—C6—C5−5.2 (6)
Br1—Mn1—N1—C5−174.2 (4)N1—C5—C6—O2ii−173.3 (5)
Br2—Mn1—N1—C592.4 (4)C4—C5—C6—O2ii6.3 (8)
O2—Mn1—N1—C1165.3 (4)N1—C5—C6—O16.2 (7)
O3—Mn1—N1—C190.3 (5)C4—C5—C6—O1−174.3 (5)
O1—Mn1—N1—C1177.5 (5)N2—C7—C8—C9171.0 (4)
Br1—Mn1—N1—C12.1 (5)C7—C8—C9—C9iii176.1 (7)
Br2—Mn1—N1—C1−91.4 (5)
Symmetry codes: (i) x, −y, z−1/2; (ii) x, −y, z+1/2; (iii) −x, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1ii0.892.442.949 (6)117
N2—H2A···O2ii0.892.473.300 (6)155
N2—H2B···Br2ii0.892.613.339 (4)139
N2—H2C···Br2iv0.892.583.417 (5)157
O3—H3A···Br1v0.992.283.245 (4)165
O3—H3B···O1vi0.832.182.961 (5)157
Symmetry codes: (ii) x, −y, z+1/2; (iv) x, y, z+1; (v) −x+1, y, −z+1/2; (vi) −x+1, −y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.892.442.949 (6)117
N2—H2A···O2i0.892.473.300 (6)155
N2—H2B···Br2i0.892.613.339 (4)139
N2—H2C···Br2ii0.892.583.417 (5)157
O3—H3A···Br1iii0.992.283.245 (4)165
O3—H3B···O1iv0.832.182.961 (5)157
Symmetry codes: (i) x, −y, z+1/2; (ii) x, y, z+1; (iii) −x+1, y, −z+1/2; (iv) −x+1, −y, −z+1.
Acknowledgements top

This work was supported by the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007–412-J02001).

references
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