Acta Cryst. (2009). E65, m397 [ doi:10.1107/S1600536809008411 ]
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N3)-2-pyridyl-N]benzimidazolato-N}manganese(II)In the title compound, [Mn(C19H12N5)2], each MnII atom lies on a position of site symmetry 222 and has a distorted octahedral coordination geometry made up from six N atoms of two tridentate 2-[6-(1H-benzimidazol-2-yl)-2-pyridyl]benzimidazolate ligands. The complex molecules are linked into layers parallel to (001) by N-H
N hydrogen bonds, with the H atoms disordered over four symmetry-equivalent non-coordinated N atoms.
Manganese nitrate hexahydrate (0.144 g, 0.5 mmol) and 2,6-bis(1H-benzimidazol-2-yl)pyridine (0.1536 g, 1 mmol) were dissolved in ethanol (8 ml). The solution was placed in a 15 ml Teflon-lined stainless steel bomb and heated at 423 K for 96 h. The cooled mixture yielded red block-shaped crystals in about 41% yield. The crystals were washed with ethanol and dried in air.
All H atoms were positioned geometrically (C—H = 0.93 Å, N—H = 0.91 Å) and refined as riding with Uiso(H) = 1.2 Ueq(C or N). The site occupancy of H1 was constrained to 0.5 so that it sums to a total of 2 H atoms disordered over the four symmetry-equivalent N3 atoms.
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bi2351fig1thm.gif)
| Fig. 1. Molecular structure showing 30% probability displacement ellipsoids. H atoms are omitted. Symmetry codes: (A) -x + 2, -y, z; (B) -y + 1, -x + 1, -z; (C) y + 1, x - 1, -z. |
| [Mn(C19H12N5)2] | Dx = 1.380 Mg m−3 |
| Mr = 675.61 | Mo Kα radiation, λ = 0.71073 Å |
| Tetragonal, P4n2 | Cell parameters from 6803 reflections |
| Hall symbol: P -4 -2n | θ = 2.4–26.0° |
| a = 10.1225 (14) Å | µ = 0.45 mm−1 |
| c = 15.865 (3) Å | T = 298 K |
| V = 1625.6 (5) Å3 | Block, red |
| Z = 2 | 0.45 × 0.44 × 0.31 mm |
| F(000) = 694 |
| Bruker SMART 2K CCD diffractometer | 1226 reflections with I > 2<s(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.040 |
| graphite | θmax = 26.0°, θmin = 2.4° |
| φ and ω scans | h = −10→12 |
| 6803 measured reflections | k = −12→11 |
| 1599 independent reflections | l = −19→12 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0482P)2 + 0.3361P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 1599 reflections | Δρmax = 0.18 e Å−3 |
| 113 parameters | Δρmin = −0.21 e Å−3 |
| 0 restraints | Absolute structure: Flack (1983), 701 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.00 (1) |
| [Mn(C19H12N5)2] | Z = 2 |
| Mr = 675.61 | Mo Kα radiation |
| Tetragonal, P4n2 | µ = 0.45 mm−1 |
| a = 10.1225 (14) Å | T = 298 K |
| c = 15.865 (3) Å | 0.45 × 0.44 × 0.31 mm |
| V = 1625.6 (5) Å3 |
| Bruker SMART 2K CCD diffractometer | 1226 reflections with I > 2<s(I) |
| 6803 measured reflections | Rint = 0.040 |
| 1599 independent reflections | θmax = 26.0° |
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.095 | Δρmax = 0.18 e Å−3 |
| S = 1.03 | Δρmin = −0.21 e Å−3 |
| 1599 reflections | Absolute structure: Flack (1983), 701 Friedel pairs |
| 113 parameters | Flack parameter: 0.00 (1) |
| 0 restraints |
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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Mn1 | 0.5000 | 0.0000 | 0.2500 | 0.0372 (2) | |
| C1 | 0.3191 (3) | 0.1985 (3) | 0.12293 (17) | 0.0379 (6) | |
| C2 | 0.2023 (3) | 0.1312 (3) | 0.1090 (2) | 0.0542 (9) | |
| H2 | 0.1913 | 0.0448 | 0.1279 | 0.065* | |
| C3 | 0.1031 (4) | 0.1952 (4) | 0.0668 (3) | 0.0626 (10) | |
| H3 | 0.0234 | 0.1520 | 0.0575 | 0.075* | |
| C4 | 0.1195 (3) | 0.3226 (4) | 0.0376 (2) | 0.0625 (10) | |
| H4 | 0.0511 | 0.3624 | 0.0078 | 0.075* | |
| C5 | 0.2336 (3) | 0.3919 (3) | 0.0513 (2) | 0.0540 (9) | |
| H5 | 0.2432 | 0.4782 | 0.0321 | 0.065* | |
| C6 | 0.3348 (3) | 0.3286 (3) | 0.09494 (19) | 0.0406 (7) | |
| C7 | 0.5083 (3) | 0.2688 (3) | 0.16267 (18) | 0.0366 (7) | |
| C8 | 0.6350 (3) | 0.2666 (3) | 0.2067 (2) | 0.0471 (8) | |
| C9 | 0.7292 (4) | 0.3650 (4) | 0.2072 (3) | 0.0915 (16) | |
| H9 | 0.7147 | 0.4441 | 0.1789 | 0.110* | |
| C10 | 0.8439 (3) | 0.3439 (3) | 0.2500 | 0.128 (3) | |
| H10 | 0.9089 | 0.4089 | 0.2500 | 0.154* | |
| N1 | 0.65540 (18) | 0.15540 (18) | 0.2500 | 0.0381 (7) | |
| N2 | 0.4325 (2) | 0.1611 (2) | 0.16468 (16) | 0.0388 (6) | |
| N3 | 0.4560 (2) | 0.3722 (2) | 0.12179 (17) | 0.0437 (6) | |
| H1 | 0.5082 | 0.4448 | 0.1157 | 0.066* | 0.50 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mn1 | 0.0277 (3) | 0.0277 (3) | 0.0560 (5) | −0.0078 (3) | 0.000 | 0.000 |
| C1 | 0.0366 (16) | 0.0338 (16) | 0.0435 (15) | −0.0021 (11) | −0.0031 (14) | −0.0071 (14) |
| C2 | 0.0514 (19) | 0.0429 (18) | 0.068 (2) | −0.0116 (14) | −0.0116 (18) | −0.0014 (17) |
| C3 | 0.049 (2) | 0.056 (2) | 0.083 (3) | −0.0112 (17) | −0.016 (2) | −0.003 (2) |
| C4 | 0.0494 (19) | 0.062 (2) | 0.076 (3) | 0.0047 (18) | −0.0231 (18) | 0.0033 (19) |
| C5 | 0.053 (2) | 0.0375 (17) | 0.071 (2) | 0.0038 (15) | −0.0036 (17) | 0.0058 (18) |
| C6 | 0.0381 (16) | 0.0316 (16) | 0.0520 (18) | −0.0011 (12) | −0.0007 (14) | −0.0043 (14) |
| C7 | 0.0358 (15) | 0.0240 (13) | 0.0501 (18) | −0.0011 (11) | 0.0004 (15) | 0.0004 (12) |
| C8 | 0.0367 (16) | 0.0352 (16) | 0.069 (2) | −0.0057 (12) | −0.0053 (16) | 0.0089 (15) |
| C9 | 0.066 (2) | 0.051 (2) | 0.158 (4) | −0.0324 (18) | −0.046 (3) | 0.047 (2) |
| C10 | 0.078 (3) | 0.078 (3) | 0.229 (8) | −0.058 (3) | −0.083 (5) | 0.083 (5) |
| N1 | 0.0292 (9) | 0.0292 (9) | 0.0559 (19) | −0.0071 (11) | 0.0007 (15) | −0.0007 (15) |
| N2 | 0.0347 (13) | 0.0285 (11) | 0.0531 (15) | −0.0063 (10) | −0.0047 (11) | −0.0010 (11) |
| N3 | 0.0402 (13) | 0.0285 (12) | 0.0623 (16) | −0.0045 (10) | −0.0046 (13) | 0.0033 (13) |
| Mn1—N1i | 2.225 (3) | C5—C6 | 1.393 (4) |
| Mn1—N1 | 2.225 (3) | C5—H5 | 0.930 |
| Mn1—N2ii | 2.226 (2) | C6—N3 | 1.372 (4) |
| Mn1—N2i | 2.226 (2) | C7—N2 | 1.333 (3) |
| Mn1—N2 | 2.226 (2) | C7—N3 | 1.341 (4) |
| Mn1—N2iii | 2.226 (2) | C7—C8 | 1.461 (4) |
| C1—N2 | 1.378 (3) | C8—N1 | 1.334 (3) |
| C1—C2 | 1.382 (4) | C8—C9 | 1.379 (4) |
| C1—C6 | 1.399 (4) | C9—C10 | 1.362 (4) |
| C2—C3 | 1.370 (5) | C9—H9 | 0.930 |
| C2—H2 | 0.930 | C10—C9iii | 1.362 (4) |
| C3—C4 | 1.380 (5) | C10—H10 | 0.930 |
| C3—H3 | 0.930 | N1—C8iii | 1.334 (3) |
| C4—C5 | 1.369 (5) | N3—H1 | 0.910 |
| C4—H4 | 0.930 | ||
| N1i—Mn1—N1 | 180.00 (13) | C4—C5—C6 | 117.7 (3) |
| N1i—Mn1—N2ii | 72.49 (5) | C4—C5—H5 | 121.2 |
| N1—Mn1—N2ii | 107.51 (5) | C6—C5—H5 | 121.2 |
| N1i—Mn1—N2i | 72.49 (5) | N3—C6—C5 | 131.7 (3) |
| N1—Mn1—N2i | 107.51 (5) | N3—C6—C1 | 107.8 (3) |
| N2ii—Mn1—N2i | 144.99 (11) | C5—C6—C1 | 120.5 (3) |
| N1i—Mn1—N2 | 107.51 (5) | N2—C7—N3 | 115.0 (2) |
| N1—Mn1—N2 | 72.49 (5) | N2—C7—C8 | 118.8 (2) |
| N2ii—Mn1—N2 | 85.43 (12) | N3—C7—C8 | 126.1 (2) |
| N2i—Mn1—N2 | 105.11 (12) | N1—C8—C9 | 120.0 (3) |
| N1i—Mn1—N2iii | 107.51 (5) | N1—C8—C7 | 113.2 (2) |
| N1—Mn1—N2iii | 72.49 (5) | C9—C8—C7 | 126.8 (3) |
| N2ii—Mn1—N2iii | 105.11 (12) | C10—C9—C8 | 118.6 (4) |
| N2i—Mn1—N2iii | 85.43 (12) | C10—C9—H9 | 120.7 |
| N2—Mn1—N2iii | 144.99 (11) | C8—C9—H9 | 120.7 |
| N2—C1—C2 | 130.8 (3) | C9—C10—C9iii | 121.0 (4) |
| N2—C1—C6 | 108.5 (2) | C9—C10—H10 | 119.5 |
| C2—C1—C6 | 120.7 (3) | C9iii—C10—H10 | 119.5 |
| C3—C2—C1 | 118.1 (3) | C8—N1—C8iii | 121.7 (3) |
| C3—C2—H2 | 120.9 | C8—N1—Mn1 | 119.15 (16) |
| C1—C2—H2 | 120.9 | C8iii—N1—Mn1 | 119.15 (16) |
| C2—C3—C4 | 121.2 (3) | C7—N2—C1 | 104.0 (2) |
| C2—C3—H3 | 119.4 | C7—N2—Mn1 | 115.90 (18) |
| C4—C3—H3 | 119.4 | C1—N2—Mn1 | 138.51 (18) |
| C5—C4—C3 | 121.8 (3) | C7—N3—C6 | 104.6 (2) |
| C5—C4—H4 | 119.1 | C7—N3—H1 | 116.9 |
| C3—C4—H4 | 119.1 | C6—N3—H1 | 138.2 |
| Symmetry codes: (i) −x+1, −y, z; (ii) −y+1/2, −x+1/2, −z+1/2; (iii) y+1/2, x−1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H1···N3iv | 0.91 | 1.89 | 2.736 (4) | 154 |
| Symmetry codes: (iv) −x+1, −y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H1···N3i | 0.91 | 1.89 | 2.736 (4) | 154 |
| Symmetry codes: (i) −x+1, −y+1, z. |
We acknowledge financial support by Guangxi Key Laboratory for Advanced Materials and New Preparation Technology (grant No. 0842003–25) and the Young Science Foundation of Guangxi Province of China (grant No. 0832085).
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The 2,6-bis(1H-benzimidazol-2-yl)pyridine ligand is known to form complexes with various transition metal atoms (Harvey et al., 2003; Wang et al., 1994; Yue et al., 2006; Zhang et al., 2007). The title compound, containing MnII, has been reported previously (Shi et al., 2003), with closely comparable cell parameters but refined in space group Pn. Atomic coordinates were not reported and they are not available in the Cambridge Structural Database. However, diagrams of the structure in the paper of Shi et al. (2003) suggest it to be closely comparable to the current reported structure, and it is probable that the previous refinement in Pn is an instance of "missed symmetry".