metal-organic compounds
catena-Poly[[(2,2′-bipyridine-κ2N,N′)manganese(II)]-di-μ-bromido]
aChonnam National University, School of Chemical Engineering, Research Institute of Catalysis, Gwangju, Republic of Korea
*Correspondence e-mail: hakwang@chonnam.ac.kr
In the polymeric title complex, [MnBr2(C10H8N2)]n, the MnII ion, situated on a twofold axis of symmetry, is six-coordinated in a distorted octahedral coordination geometry defined by two N atoms from the chelating 2,2′-bipyridine ligand and four bridging Br− anions. The crystal reveals a one-dimensional Br-bridged chain along the c-axis direction with a zigzag topology. In the crystals, contacts between chains include π–π interactions between pyridyl rings [inter-centroid separation = 4.082 (1) Å]
CCDC reference: 2058386
Structure description
With reference to the title complex, [MnBr2(bipy)]n (bipy = 2,2′-bipyridine), the crystal structures of related MnII complexes, namely [MnCl2(bipy)]n (Lubben et al., 1995) and [MnBr2(bipy)2] (Hwang & Ha, 2007) have been determined previously.
In the title complex, the central MnII cation is six-coordinated within a distorted octahedral coordination geometry defined by two N atoms from chelating bipy ligand and four bridging Br− anions (Fig. 1). The maximum deviation from the ideal octahedral angles is seen in the N1—Mn—N1i chelate angle of 73.08 (7)°; (i): −x, y, −z + . The Mn ions are bridged by four bromido ligands to form a zigzag chain (glide symmetry) structure along the c-axis direction so the of the polymer contains one half of the repeat unit, i.e. MnBr2(bipy); the MnII cation is situated on a twofold axis of symmetry. The Mn—Br bond lengths are somewhat different: the Mn—Br(trans to Br) distance of 2.7975 (2) Å is longer than the Mn—Br(trans to N) distance of 2.6373 (3) Å. The distance between adjacent Mn atoms is relatively short with the separation being 3.9656 (3) Å. The complex molecules are stacked in columns along the a axis (Fig. 2). In the columns, several intermolecular π–π interactions between adjacent pyridine rings are present. The closest contact involves Cg1 (the centroid of ring N1,C1–C5) and Cg1ii [symmetry code: (ii) x, −y + 1, z + ], the centroid–centroid distance is 4.082 (1) Å and the dihedral angle between the ring planes is 8.79 (9)°.
Synthesis and crystallization
To a solution of [MnBr2(bipy)2] (0.2713 g, 0.515 mmol) in 2-methoxyethanol (30 ml) was added MnBr2·4H2O (0.1491 g, 0.520 mmol), followed by reflux for 2 h. After cooling, the formed precipitate was separated by filtration, washed with ethanol and ether, and dried at 323 K, to give a pale-yellow powder (0.2671 g). Pale-yellow crystals of the product suitable for X-ray analysis were obtained by slow evaporation from its 2-methoxyethanol solution at room temperature.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 1Structural data
CCDC reference: 2058386
https://doi.org/10.1107/S2414314621000833/tk4066sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621000833/tk4066Isup2.hkl
Data collection: APEX2 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT2014/7 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014/7 (Sheldrick, 2015b).[MnBr2(C10H8N2)] | F(000) = 708 |
Mr = 370.94 | Dx = 2.201 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 17.3039 (9) Å | Cell parameters from 9930 reflections |
b = 9.5255 (5) Å | θ = 3.6–26.0° |
c = 7.1852 (3) Å | µ = 8.28 mm−1 |
β = 109.0347 (15)° | T = 223 K |
V = 1119.57 (10) Å3 | Block, pale yellow |
Z = 4 | 0.29 × 0.14 × 0.05 mm |
PHOTON 100 CMOS detector diffractometer | 1037 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.038 |
φ and ω scans | θmax = 26.0°, θmin = 3.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | h = −21→21 |
Tmin = 0.373, Tmax = 0.745 | k = −11→11 |
14090 measured reflections | l = −8→8 |
1068 independent reflections |
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)] = 0.013 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.034 | All H-atom parameters refined |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0095P)2 + 1.0722P] where P = (Fo2 + 2Fc2)/3 |
1068 reflections | (Δ/σ)max < 0.001 |
85 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. All H atoms were located from Fourier difference maps and refined isotropically; C—H = 0.93 (2)–0.97 (2) Å. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.0000 | 0.08813 (3) | 0.2500 | 0.02456 (9) | |
Br1 | −0.09377 (2) | −0.09461 (2) | 0.00183 (2) | 0.02780 (8) | |
N1 | 0.07232 (8) | 0.27734 (14) | 0.39308 (19) | 0.0259 (3) | |
C1 | 0.14754 (10) | 0.2716 (2) | 0.5270 (3) | 0.0339 (4) | |
C2 | 0.19474 (12) | 0.3903 (2) | 0.5944 (3) | 0.0411 (4) | |
C3 | 0.16249 (12) | 0.5191 (2) | 0.5240 (3) | 0.0416 (4) | |
C4 | 0.08538 (12) | 0.52703 (19) | 0.3900 (3) | 0.0354 (4) | |
C5 | 0.04134 (10) | 0.40425 (15) | 0.3247 (2) | 0.0251 (3) | |
H1 | 0.1647 (13) | 0.178 (3) | 0.573 (3) | 0.046 (6)* | |
H2 | 0.2483 (15) | 0.379 (2) | 0.692 (3) | 0.043 (6)* | |
H3 | 0.1942 (17) | 0.599 (2) | 0.561 (4) | 0.053 (7)* | |
H4 | 0.0607 (15) | 0.612 (2) | 0.333 (4) | 0.049 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.02373 (17) | 0.02100 (17) | 0.02314 (17) | 0.000 | −0.00031 (13) | 0.000 |
Br1 | 0.02714 (10) | 0.02824 (11) | 0.02510 (10) | −0.00752 (6) | 0.00451 (7) | −0.00407 (5) |
N1 | 0.0229 (6) | 0.0269 (7) | 0.0271 (6) | −0.0011 (5) | 0.0070 (5) | −0.0057 (5) |
C1 | 0.0246 (8) | 0.0390 (10) | 0.0346 (9) | 0.0008 (7) | 0.0047 (7) | −0.0101 (7) |
C2 | 0.0284 (9) | 0.0578 (12) | 0.0360 (10) | −0.0106 (8) | 0.0091 (8) | −0.0203 (8) |
C3 | 0.0470 (10) | 0.0427 (11) | 0.0395 (10) | −0.0210 (9) | 0.0203 (8) | −0.0179 (8) |
C4 | 0.0487 (10) | 0.0276 (9) | 0.0365 (9) | −0.0090 (8) | 0.0227 (8) | −0.0072 (7) |
C5 | 0.0299 (8) | 0.0251 (8) | 0.0262 (8) | −0.0030 (6) | 0.0173 (7) | −0.0040 (6) |
Mn1—N1i | 2.2433 (13) | C1—C2 | 1.386 (3) |
Mn1—N1 | 2.2433 (13) | C1—H1 | 0.97 (2) |
Mn1—Br1i | 2.6373 (3) | C2—C3 | 1.375 (3) |
Mn1—Br1 | 2.6373 (3) | C2—H2 | 0.97 (2) |
Mn1—Br1ii | 2.7975 (2) | C3—C4 | 1.369 (3) |
Mn1—Br1iii | 2.7975 (2) | C3—H3 | 0.93 (2) |
Br1—Mn1ii | 2.7975 (2) | C4—C5 | 1.391 (2) |
N1—C1 | 1.344 (2) | C4—H4 | 0.95 (2) |
N1—C5 | 1.348 (2) | C5—C5i | 1.482 (3) |
N1i—Mn1—N1 | 73.08 (7) | C1—N1—Mn1 | 124.10 (11) |
N1i—Mn1—Br1i | 165.56 (4) | C5—N1—Mn1 | 117.21 (10) |
N1—Mn1—Br1i | 95.29 (3) | N1—C1—C2 | 122.67 (18) |
N1i—Mn1—Br1 | 95.29 (3) | N1—C1—H1 | 113.6 (13) |
N1—Mn1—Br1 | 165.56 (4) | C2—C1—H1 | 123.7 (13) |
Br1i—Mn1—Br1 | 97.395 (13) | C3—C2—C1 | 118.50 (18) |
N1i—Mn1—Br1ii | 92.32 (3) | C3—C2—H2 | 122.7 (13) |
N1—Mn1—Br1ii | 85.65 (3) | C1—C2—H2 | 118.8 (13) |
Br1i—Mn1—Br1ii | 95.344 (7) | C4—C3—C2 | 119.58 (17) |
Br1—Mn1—Br1ii | 86.331 (6) | C4—C3—H3 | 120.3 (16) |
N1i—Mn1—Br1iii | 85.65 (3) | C2—C3—H3 | 120.0 (16) |
N1—Mn1—Br1iii | 92.31 (3) | C3—C4—C5 | 119.46 (18) |
Br1i—Mn1—Br1iii | 86.331 (6) | C3—C4—H4 | 123.3 (15) |
Br1—Mn1—Br1iii | 95.344 (7) | C5—C4—H4 | 117.1 (15) |
Br1ii—Mn1—Br1iii | 177.470 (13) | N1—C5—C4 | 121.44 (16) |
Mn1—Br1—Mn1ii | 93.669 (6) | N1—C5—C5i | 116.04 (9) |
C1—N1—C5 | 118.32 (14) | C4—C5—C5i | 122.51 (11) |
C5—N1—C1—C2 | −1.2 (2) | Mn1—N1—C5—C4 | −173.49 (11) |
Mn1—N1—C1—C2 | 171.71 (13) | C1—N1—C5—C5i | 179.20 (16) |
N1—C1—C2—C3 | 1.3 (3) | Mn1—N1—C5—C5i | 5.8 (2) |
C1—C2—C3—C4 | −0.1 (3) | C3—C4—C5—N1 | 1.2 (2) |
C2—C3—C4—C5 | −1.1 (3) | C3—C4—C5—C5i | −178.03 (18) |
C1—N1—C5—C4 | −0.1 (2) |
Symmetry codes: (i) −x, y, −z+1/2; (ii) −x, −y, −z; (iii) x, −y, z+1/2. |
Acknowledgements
The author thanks the KBSI, Seoul Center, for the X-ray data collection.
Funding information
This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (grant No. 2018R1D1A1B07050550).
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