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Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): m621.
Published online 2009 May 7. doi:  10.1107/S1600536809016316
PMCID: PMC2969818

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

Abstract

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 π–π inter­actions between adjacent pyridine rings, with a centroid–centroid distance of 3.992 (4) Å.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-65-0m621-scheme1.jpg

Experimental

Crystal data

  • (C6H18N2)0.5[MnBr2(C6H4NO2)(H2O)]
  • M r = 413.99
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m621-efi4.jpg
  • a = 13.490 (3) Å
  • b = 21.510 (5) Å
  • c = 9.803 (2) Å
  • β = 91.125 (4)°
  • V = 2843.9 (11) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 6.55 mm−1
  • T = 293 K
  • 0.10 × 0.10 × 0.10 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.394, T max = 0.520
  • 7815 measured reflections
  • 2705 independent reflections
  • 1846 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.114
  • S = 0.94
  • 2705 reflections
  • 152 parameters
  • H-atom parameters constrained
  • Δρmax = 0.68 e Å−3
  • Δρmin = −0.56 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016316/cs2117sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016316/cs2117Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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

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.

Figures

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].
Fig. 2.
View of the unit-cell contents and chain structure of the title compound. H atoms have been omitted for clarity.

Crystal data

(C6H18N2)0.5[MnBr2(C6H4NO2)(H2O)]F(000) = 1616
Mr = 413.99Dx = 1.934 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 806 reflections
a = 13.490 (3) Åθ = 2.8–25.3°
b = 21.510 (5) ŵ = 6.55 mm1
c = 9.803 (2) ÅT = 293 K
β = 91.125 (4)°Stick, colorless
V = 2843.9 (11) Å30.10 × 0.10 × 0.10 mm
Z = 8

Data collection

Bruker SMART 1000 CCD diffractometer2705 independent reflections
Radiation source: fine-focus sealed tube1846 reflections with I > 2σ(I)
graphiteRint = 0.030
[var phi] and ω scansθmax = 25.7°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −16→15
Tmin = 0.394, Tmax = 0.520k = −26→26
7815 measured reflectionsl = −7→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114H-atom parameters constrained
S = 0.94w = 1/[σ2(Fo2) + (0.0606P)2] where P = (Fo2 + 2Fc2)/3
2705 reflections(Δ/σ)max < 0.001
152 parametersΔρmax = 0.68 e Å3
0 restraintsΔρmin = −0.56 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CS2117).

References

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  • Huang, D., Wang, W., Zhang, X., Chen, C., Chen, F., Liu, Q., Liao, D., Li, L. & Sun, L. (2004). Eur. J. Inorg. Chem. pp. 1454–1464.
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