metal-organic compounds
catena-Poly[hemi(hexane-1,6-diammonium) [[aquadibromidomanganese(II)]-μ-pyridine-2-carboxylato]]
aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea, and bInstitute of Basic Sciences, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
*Correspondence e-mail: hakwang@chonnam.ac.kr
The 6H18N2)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.
of the title compound, {(CRelated literature
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
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; 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.
Supporting information
10.1107/S1600536809016316/cs2117sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809016316/cs2117Isup2.hkl
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.
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.
Data collection: SMART (Bruker, 2000); cell
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).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. |
(C6H18N2)0.5[MnBr2(C6H4NO2)(H2O)] | F(000) = 1616 |
Mr = 413.99 | Dx = 1.934 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 806 reflections |
a = 13.490 (3) Å | θ = 2.8–25.3° |
b = 21.510 (5) Å | µ = 6.55 mm−1 |
c = 9.803 (2) Å | T = 293 K |
β = 91.125 (4)° | Stick, colorless |
V = 2843.9 (11) Å3 | 0.10 × 0.10 × 0.10 mm |
Z = 8 |
Bruker SMART 1000 CCD diffractometer | 2705 independent reflections |
Radiation source: fine-focus sealed tube | 1846 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 25.7°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −16→15 |
Tmin = 0.394, Tmax = 0.520 | k = −26→26 |
7815 measured reflections | l = −7→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0606P)2] where P = (Fo2 + 2Fc2)/3 |
2705 reflections | (Δ/σ)max < 0.001 |
152 parameters | Δρmax = 0.68 e Å−3 |
0 restraints | Δρmin = −0.56 e Å−3 |
(C6H18N2)0.5[MnBr2(C6H4NO2)(H2O)] | V = 2843.9 (11) Å3 |
Mr = 413.99 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.490 (3) Å | µ = 6.55 mm−1 |
b = 21.510 (5) Å | T = 293 K |
c = 9.803 (2) Å | 0.10 × 0.10 × 0.10 mm |
β = 91.125 (4)° |
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 = 0.520 | Rint = 0.030 |
7815 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.68 e Å−3 |
2705 reflections | Δρmin = −0.56 e Å−3 |
152 parameters |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.32935 (6) | 0.06982 (4) | 0.41356 (8) | 0.0340 (2) | |
Br1 | 0.34335 (4) | 0.15379 (3) | 0.21825 (6) | 0.0438 (2) | |
Br2 | 0.13026 (5) | 0.06928 (3) | 0.40001 (8) | 0.0585 (2) | |
O1 | 0.3336 (3) | 0.01771 (15) | 0.6076 (4) | 0.0406 (10) | |
O2 | 0.3331 (3) | −0.02393 (17) | 0.3343 (4) | 0.0491 (11) | |
O3 | 0.4928 (3) | 0.06506 (18) | 0.4217 (5) | 0.0549 (12) | |
H3A | 0.5358 | 0.0983 | 0.3865 | 0.082* | |
H3B | 0.5394 | 0.0408 | 0.4376 | 0.082* | |
N1 | 0.3431 (3) | 0.14114 (19) | 0.5834 (4) | 0.0349 (11) | |
C1 | 0.3514 (4) | 0.2031 (2) | 0.5714 (6) | 0.0442 (15) | |
H1 | 0.3488 | 0.2203 | 0.4844 | 0.053* | |
C2 | 0.3634 (5) | 0.2422 (3) | 0.6809 (7) | 0.0519 (16) | |
H2 | 0.3667 | 0.2850 | 0.6687 | 0.062* | |
C3 | 0.3702 (5) | 0.2168 (3) | 0.8077 (7) | 0.0558 (18) | |
H3 | 0.3800 | 0.2422 | 0.8836 | 0.067* | |
C4 | 0.3625 (5) | 0.1532 (3) | 0.8234 (6) | 0.0470 (15) | |
H4 | 0.3667 | 0.1351 | 0.9095 | 0.056* | |
C5 | 0.3488 (4) | 0.1175 (2) | 0.7091 (5) | 0.0318 (12) | |
C6 | 0.3378 (4) | 0.0470 (3) | 0.7180 (6) | 0.0343 (13) | |
N2 | 0.1654 (3) | 0.06720 (19) | 1.0558 (5) | 0.0717 (19) | |
H2A | 0.2232 | 0.0622 | 1.0151 | 0.107* | |
H2B | 0.1262 | 0.0350 | 1.0366 | 0.107* | |
H2C | 0.1754 | 0.0696 | 1.1457 | 0.107* | |
C7 | 0.1177 (3) | 0.12511 (19) | 1.0062 (5) | 0.0564 (18) | |
H7A | 0.1654 | 0.1588 | 1.0122 | 0.068* | |
H7B | 0.0630 | 0.1353 | 1.0650 | 0.068* | |
C8 | 0.0796 (5) | 0.1202 (3) | 0.8624 (7) | 0.0545 (17) | |
H8A | 0.0399 | 0.0828 | 0.8525 | 0.065* | |
H8B | 0.1351 | 0.1169 | 0.8013 | 0.065* | |
C9 | 0.0174 (5) | 0.1762 (3) | 0.8230 (7) | 0.065 (2) | |
H9A | −0.0400 | 0.1777 | 0.8810 | 0.078* | |
H9B | 0.0560 | 0.2136 | 0.8400 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0451 (5) | 0.0302 (4) | 0.0267 (5) | 0.0019 (4) | 0.0001 (4) | 0.0004 (4) |
Br1 | 0.0526 (4) | 0.0416 (3) | 0.0371 (4) | 0.0026 (3) | 0.0016 (3) | 0.0072 (3) |
Br2 | 0.0466 (4) | 0.0593 (4) | 0.0697 (5) | 0.0030 (3) | 0.0012 (3) | 0.0179 (4) |
O1 | 0.068 (3) | 0.0250 (19) | 0.029 (2) | −0.0015 (18) | 0.001 (2) | 0.0003 (17) |
O2 | 0.082 (3) | 0.036 (2) | 0.029 (2) | 0.003 (2) | −0.001 (2) | −0.0072 (18) |
O3 | 0.042 (2) | 0.055 (3) | 0.068 (3) | 0.008 (2) | 0.005 (2) | 0.021 (2) |
N1 | 0.045 (3) | 0.029 (3) | 0.031 (3) | 0.002 (2) | 0.000 (2) | 0.004 (2) |
C1 | 0.062 (4) | 0.028 (3) | 0.043 (4) | −0.002 (3) | 0.001 (3) | 0.009 (3) |
C2 | 0.066 (4) | 0.029 (3) | 0.061 (4) | 0.001 (3) | 0.003 (4) | −0.005 (3) |
C3 | 0.082 (5) | 0.034 (3) | 0.051 (4) | −0.004 (3) | 0.001 (4) | −0.015 (3) |
C4 | 0.069 (4) | 0.037 (3) | 0.035 (3) | 0.001 (3) | 0.000 (3) | −0.001 (3) |
C5 | 0.038 (3) | 0.029 (3) | 0.028 (3) | 0.004 (2) | 0.004 (2) | 0.001 (2) |
C6 | 0.036 (3) | 0.038 (3) | 0.030 (3) | −0.002 (2) | −0.001 (3) | 0.005 (3) |
N2 | 0.092 (5) | 0.050 (3) | 0.072 (4) | 0.012 (3) | −0.031 (4) | −0.015 (3) |
C7 | 0.051 (4) | 0.050 (4) | 0.067 (5) | 0.009 (3) | −0.016 (4) | −0.012 (4) |
C8 | 0.050 (4) | 0.060 (4) | 0.053 (4) | 0.001 (3) | −0.005 (3) | −0.003 (3) |
C9 | 0.079 (5) | 0.042 (4) | 0.073 (5) | 0.007 (4) | −0.019 (4) | −0.003 (4) |
Mn1—O2 | 2.162 (4) | C4—C5 | 1.368 (7) |
Mn1—O3 | 2.206 (4) | C4—H4 | 0.93 |
Mn1—O1 | 2.208 (4) | C5—C6 | 1.526 (7) |
Mn1—N1 | 2.269 (4) | C6—O2ii | 1.247 (6) |
Mn1—Br1 | 2.6416 (11) | N2—C7 | 1.4799 |
Mn1—Br2 | 2.6864 (12) | N2—H2A | 0.89 |
O1—C6 | 1.253 (6) | N2—H2B | 0.89 |
O2—C6i | 1.247 (6) | N2—H2C | 0.89 |
O3—H3A | 0.99 | C7—C8 | 1.495 (7) |
O3—H3B | 0.83 | C7—H7A | 0.97 |
N1—C5 | 1.334 (6) | C7—H7B | 0.97 |
N1—C1 | 1.343 (6) | C8—C9 | 1.514 (8) |
C1—C2 | 1.371 (8) | C8—H8A | 0.97 |
C1—H1 | 0.93 | C8—H8B | 0.97 |
C2—C3 | 1.359 (9) | C9—C9iii | 1.497 (13) |
C2—H2 | 0.93 | C9—H9A | 0.97 |
C3—C4 | 1.382 (8) | C9—H9B | 0.97 |
C3—H3 | 0.93 | ||
O2—Mn1—O3 | 86.53 (16) | C5—C4—H4 | 120.9 |
O2—Mn1—O1 | 80.53 (14) | C3—C4—H4 | 120.9 |
O3—Mn1—O1 | 86.35 (15) | N1—C5—C4 | 123.2 (5) |
O2—Mn1—N1 | 153.14 (15) | N1—C5—C6 | 115.3 (5) |
O3—Mn1—N1 | 86.42 (16) | C4—C5—C6 | 121.5 (5) |
O1—Mn1—N1 | 73.17 (14) | O2ii—C6—O1 | 126.0 (5) |
O2—Mn1—Br1 | 112.02 (11) | O2ii—C6—C5 | 117.1 (5) |
O3—Mn1—Br1 | 88.42 (11) | O1—C6—C5 | 117.0 (5) |
O1—Mn1—Br1 | 166.09 (10) | C7—N2—H2A | 109.5 |
N1—Mn1—Br1 | 93.65 (11) | C7—N2—H2B | 109.5 |
O2—Mn1—Br2 | 90.48 (12) | H2A—N2—H2B | 109.5 |
O3—Mn1—Br2 | 176.99 (12) | C7—N2—H2C | 109.5 |
O1—Mn1—Br2 | 92.83 (11) | H2A—N2—H2C | 109.5 |
N1—Mn1—Br2 | 96.13 (12) | H2B—N2—H2C | 109.5 |
Br1—Mn1—Br2 | 93.02 (3) | N2—C7—C8 | 112.9 (3) |
C6—O1—Mn1 | 119.3 (3) | N2—C7—H7A | 109.0 |
C6i—O2—Mn1 | 134.6 (4) | C8—C7—H7A | 109.0 |
Mn1—O3—H3A | 123.2 | N2—C7—H7B | 109.0 |
Mn1—O3—H3B | 142.1 | C8—C7—H7B | 109.0 |
H3A—O3—H3B | 94 | H7A—C7—H7B | 107.8 |
C5—N1—C1 | 117.2 (5) | C7—C8—C9 | 111.3 (5) |
C5—N1—Mn1 | 115.0 (3) | C7—C8—H8A | 109.4 |
C1—N1—Mn1 | 127.7 (4) | C9—C8—H8A | 109.4 |
N1—C1—C2 | 123.3 (6) | C7—C8—H8B | 109.4 |
N1—C1—H1 | 118.4 | C9—C8—H8B | 109.4 |
C2—C1—H1 | 118.4 | H8A—C8—H8B | 108.0 |
C3—C2—C1 | 118.4 (6) | C9iii—C9—C8 | 113.9 (5) |
C3—C2—H2 | 120.8 | C9iii—C9—H9A | 108.8 |
C1—C2—H2 | 120.8 | C8—C9—H9A | 108.8 |
C2—C3—C4 | 119.7 (6) | C9iii—C9—H9B | 108.8 |
C2—C3—H3 | 120.2 | C8—C9—H9B | 108.8 |
C4—C3—H3 | 120.2 | H9A—C9—H9B | 107.7 |
C5—C4—C3 | 118.3 (6) | ||
O2—Mn1—O1—C6 | 176.8 (4) | C5—N1—C1—C2 | −1.1 (9) |
O3—Mn1—O1—C6 | 89.7 (4) | Mn1—N1—C1—C2 | −177.3 (4) |
N1—Mn1—O1—C6 | 2.3 (4) | N1—C1—C2—C3 | 2.0 (10) |
Br1—Mn1—O1—C6 | 21.6 (8) | C1—C2—C3—C4 | −1.6 (10) |
Br2—Mn1—O1—C6 | −93.2 (4) | C2—C3—C4—C5 | 0.4 (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—C4 | 176.5 (4) |
N1—Mn1—O2—C6i | −164.0 (5) | C1—N1—C5—C6 | 179.3 (5) |
Br1—Mn1—O2—C6i | −2.1 (6) | Mn1—N1—C5—C6 | −4.0 (6) |
Br2—Mn1—O2—C6i | 91.3 (5) | C3—C4—C5—N1 | 0.5 (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—O2ii | 174.2 (4) |
O1—Mn1—N1—C5 | 1.3 (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—C5 | 92.4 (4) | C4—C5—C6—O2ii | 6.3 (8) |
O2—Mn1—N1—C1 | 165.3 (4) | N1—C5—C6—O1 | 6.2 (7) |
O3—Mn1—N1—C1 | 90.3 (5) | C4—C5—C6—O1 | −174.3 (5) |
O1—Mn1—N1—C1 | 177.5 (5) | N2—C7—C8—C9 | 171.0 (4) |
Br1—Mn1—N1—C1 | 2.1 (5) | C7—C8—C9—C9iii | 176.1 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1ii | 0.89 | 2.44 | 2.949 (6) | 117 |
N2—H2A···O2ii | 0.89 | 2.47 | 3.300 (6) | 155 |
N2—H2B···Br2ii | 0.89 | 2.61 | 3.339 (4) | 139 |
N2—H2C···Br2iv | 0.89 | 2.58 | 3.417 (5) | 157 |
O3—H3A···Br1v | 0.99 | 2.28 | 3.245 (4) | 165 |
O3—H3B···O1vi | 0.83 | 2.18 | 2.961 (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. |
Experimental details
Crystal data | |
Chemical formula | (C6H18N2)0.5[MnBr2(C6H4NO2)(H2O)] |
Mr | 413.99 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.490 (3), 21.510 (5), 9.803 (2) |
β (°) | 91.125 (4) |
V (Å3) | 2843.9 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 6.55 |
Crystal size (mm) | 0.10 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.394, 0.520 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7815, 2705, 1846 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.114, 0.94 |
No. of reflections | 2705 |
No. of parameters | 152 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.68, −0.56 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.89 | 2.44 | 2.949 (6) | 117 |
N2—H2A···O2i | 0.89 | 2.47 | 3.300 (6) | 155 |
N2—H2B···Br2i | 0.89 | 2.61 | 3.339 (4) | 139 |
N2—H2C···Br2ii | 0.89 | 2.58 | 3.417 (5) | 157 |
O3—H3A···Br1iii | 0.99 | 2.28 | 3.245 (4) | 165 |
O3—H3B···O1iv | 0.83 | 2.18 | 2.961 (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
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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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).