metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Bis{2-[6-(1H-benzimidazol-2-yl-κN3)-2-pyridyl-κN]benzimidazolato-κN}manganese(II)

aKey Laboratory of Non-ferrous Metal Materials and Processing Technology, Department of Materials and Chemistry Engineering, Guilin University of Technology, Ministry of Education, Guilin 541004, People's Republic of China, and bCollege of Pharmacy, Guilin Medical University, Guilin 541004, People's Republic of China
*Correspondence e-mail: zsh720108@21cn.com

(Received 11 February 2009; accepted 7 March 2009; online 14 March 2009)

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.

Related literature

For a previous report of this complex, see: Shi et al. (2003[Shi, W., Li, W., Shen, P.-P., Xu, Y.-K., Wang, H.-M., Shi, M. & Liu, Y. (2003). Chin. J. Chem. 21, 659-664.]). For other comparable transition-metal complexes, see: Harvey et al. (2003[Harvey, M. A., Baggio, S., Muñoz, J. C. & Baggio, R. (2003). Acta Cryst. C59, m283-m285.]); Wang et al. (1994[Wang, S., Cui, Y., Ran, R. & Luo, A. (1994). Polyhedron, 13, 1661-1668.]); Yue et al. (2006[Yue, S.-M., Xu, H.-B., Ma, J.-F., Su, Z.-M., Kan, Y.-H. & Zhang, H.-J. (2006). Polyhedron, 25, 635-644.]); Zhang et al. (2007[Zhang, S.-H., Zeng, M.-H. & Liang, H. (2007). Acta Cryst. E63, m1055-m1056.]).

[Scheme 1]

Experimental

Crystal data
  • [Mn(C19H12N5)2]

  • Mr = 675.61

  • Tetragonal, [P \overline 4n 2]

  • a = 10.1225 (14) Å

  • c = 15.865 (3) Å

  • V = 1625.6 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.45 mm−1

  • T = 298 K

  • 0.45 × 0.44 × 0.31 mm

Data collection
  • Bruker SMART 2K CCD diffractometer

  • Absorption correction: none

  • 6803 measured reflections

  • 1599 independent reflections

  • 1226 reflections with I > 2σ(I)

  • Rint = 0.040

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.095

  • S = 1.04

  • 1599 reflections

  • 113 parameters

  • H-atom parameters constrained

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.21 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 701 Friedel pairs

  • Flack parameter: 0.00 (1)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N3—H1⋯N3i 0.91 1.89 2.736 (4) 154
Symmetry code: (i) -x+1, -y+1, z.

Data collection: SMART (Bruker, 2003[Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2003[Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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".

Related literature top

For a previous report of this complex, see: Shi et al. (2003). For other comparable transition-metal complexes, see: Harvey et al. (2003); Wang et al. (1994); Yue et al. (2006); Zhang et al. (2007).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] 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.
Bis{2-[6-(1H-benzimidazol-2-yl-κN3)-2-pyridyl- κN]benzimidazolato-κN}manganese(II) top
Crystal data top
[Mn(C19H12N5)2]Dx = 1.380 Mg m3
Mr = 675.61Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4n2Cell parameters from 6803 reflections
Hall symbol: P -4 -2nθ = 2.4–26.0°
a = 10.1225 (14) ŵ = 0.45 mm1
c = 15.865 (3) ÅT = 298 K
V = 1625.6 (5) Å3Block, red
Z = 20.45 × 0.44 × 0.31 mm
F(000) = 694
Data collection top
Bruker SMART 2K CCD
diffractometer
1226 reflections with I > 2<s(I)
Radiation source: fine-focus sealed tubeRint = 0.040
Graphite monochromatorθmax = 26.0°, θmin = 2.4°
ϕ and ω scansh = 1012
6803 measured reflectionsk = 1211
1599 independent reflectionsl = 1912
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)] = 0.035H-atom parameters constrained
wR(F2) = 0.095 w = 1/[σ2(Fo2) + (0.0482P)2 + 0.3361P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1599 reflectionsΔρmax = 0.18 e Å3
113 parametersΔρmin = 0.21 e Å3
0 restraintsAbsolute structure: Flack (1983), 701 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.00 (1)
Crystal data top
[Mn(C19H12N5)2]Z = 2
Mr = 675.61Mo Kα radiation
Tetragonal, P4n2µ = 0.45 mm1
a = 10.1225 (14) ÅT = 298 K
c = 15.865 (3) Å0.45 × 0.44 × 0.31 mm
V = 1625.6 (5) Å3
Data collection top
Bruker SMART 2K CCD
diffractometer
1226 reflections with I > 2<s(I)
6803 measured reflectionsRint = 0.040
1599 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.095Δρmax = 0.18 e Å3
S = 1.04Δρmin = 0.21 e Å3
1599 reflectionsAbsolute structure: Flack (1983), 701 Friedel pairs
113 parametersAbsolute structure parameter: 0.00 (1)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Mn10.50000.00000.25000.0372 (2)
C10.3191 (3)0.1985 (3)0.12293 (17)0.0379 (6)
C20.2023 (3)0.1312 (3)0.1090 (2)0.0542 (9)
H20.19130.04480.12790.065*
C30.1031 (4)0.1952 (4)0.0668 (3)0.0626 (10)
H30.02340.15200.05750.075*
C40.1195 (3)0.3226 (4)0.0376 (2)0.0625 (10)
H40.05110.36240.00780.075*
C50.2336 (3)0.3919 (3)0.0513 (2)0.0540 (9)
H50.24320.47820.03210.065*
C60.3348 (3)0.3286 (3)0.09494 (19)0.0406 (7)
C70.5083 (3)0.2688 (3)0.16267 (18)0.0366 (7)
C80.6350 (3)0.2666 (3)0.2067 (2)0.0471 (8)
C90.7292 (4)0.3650 (4)0.2072 (3)0.0915 (16)
H90.71470.44410.17890.110*
C100.8439 (3)0.3439 (3)0.25000.128 (3)
H100.90890.40890.25000.154*
N10.65540 (18)0.15540 (18)0.25000.0381 (7)
N20.4325 (2)0.1611 (2)0.16468 (16)0.0388 (6)
N30.4560 (2)0.3722 (2)0.12179 (17)0.0437 (6)
H10.50820.44480.11570.066*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0277 (3)0.0277 (3)0.0560 (5)0.0078 (3)0.0000.000
C10.0366 (16)0.0338 (16)0.0435 (15)0.0021 (11)0.0031 (14)0.0071 (14)
C20.0514 (19)0.0429 (18)0.068 (2)0.0116 (14)0.0116 (18)0.0014 (17)
C30.049 (2)0.056 (2)0.083 (3)0.0112 (17)0.016 (2)0.003 (2)
C40.0494 (19)0.062 (2)0.076 (3)0.0047 (18)0.0231 (18)0.0033 (19)
C50.053 (2)0.0375 (17)0.071 (2)0.0038 (15)0.0036 (17)0.0058 (18)
C60.0381 (16)0.0316 (16)0.0520 (18)0.0011 (12)0.0007 (14)0.0043 (14)
C70.0358 (15)0.0240 (13)0.0501 (18)0.0011 (11)0.0004 (15)0.0004 (12)
C80.0367 (16)0.0352 (16)0.069 (2)0.0057 (12)0.0053 (16)0.0089 (15)
C90.066 (2)0.051 (2)0.158 (4)0.0324 (18)0.046 (3)0.047 (2)
C100.078 (3)0.078 (3)0.229 (8)0.058 (3)0.083 (5)0.083 (5)
N10.0292 (9)0.0292 (9)0.0559 (19)0.0071 (11)0.0007 (15)0.0007 (15)
N20.0347 (13)0.0285 (11)0.0531 (15)0.0063 (10)0.0047 (11)0.0010 (11)
N30.0402 (13)0.0285 (12)0.0623 (16)0.0045 (10)0.0046 (13)0.0033 (13)
Geometric parameters (Å, º) top
Mn1—N1i2.225 (3)C5—C61.393 (4)
Mn1—N12.225 (3)C5—H50.930
Mn1—N2ii2.226 (2)C6—N31.372 (4)
Mn1—N2i2.226 (2)C7—N21.333 (3)
Mn1—N22.226 (2)C7—N31.341 (4)
Mn1—N2iii2.226 (2)C7—C81.461 (4)
C1—N21.378 (3)C8—N11.334 (3)
C1—C21.382 (4)C8—C91.379 (4)
C1—C61.399 (4)C9—C101.362 (4)
C2—C31.370 (5)C9—H90.930
C2—H20.930C10—C9iii1.362 (4)
C3—C41.380 (5)C10—H100.930
C3—H30.930N1—C8iii1.334 (3)
C4—C51.369 (5)N3—H10.910
C4—H40.930
N1i—Mn1—N1180.00 (13)C4—C5—C6117.7 (3)
N1i—Mn1—N2ii72.49 (5)C4—C5—H5121.2
N1—Mn1—N2ii107.51 (5)C6—C5—H5121.2
N1i—Mn1—N2i72.49 (5)N3—C6—C5131.7 (3)
N1—Mn1—N2i107.51 (5)N3—C6—C1107.8 (3)
N2ii—Mn1—N2i144.99 (11)C5—C6—C1120.5 (3)
N1i—Mn1—N2107.51 (5)N2—C7—N3115.0 (2)
N1—Mn1—N272.49 (5)N2—C7—C8118.8 (2)
N2ii—Mn1—N285.43 (12)N3—C7—C8126.1 (2)
N2i—Mn1—N2105.11 (12)N1—C8—C9120.0 (3)
N1i—Mn1—N2iii107.51 (5)N1—C8—C7113.2 (2)
N1—Mn1—N2iii72.49 (5)C9—C8—C7126.8 (3)
N2ii—Mn1—N2iii105.11 (12)C10—C9—C8118.6 (4)
N2i—Mn1—N2iii85.43 (12)C10—C9—H9120.7
N2—Mn1—N2iii144.99 (11)C8—C9—H9120.7
N2—C1—C2130.8 (3)C9—C10—C9iii121.0 (4)
N2—C1—C6108.5 (2)C9—C10—H10119.5
C2—C1—C6120.7 (3)C9iii—C10—H10119.5
C3—C2—C1118.1 (3)C8—N1—C8iii121.7 (3)
C3—C2—H2120.9C8—N1—Mn1119.15 (16)
C1—C2—H2120.9C8iii—N1—Mn1119.15 (16)
C2—C3—C4121.2 (3)C7—N2—C1104.0 (2)
C2—C3—H3119.4C7—N2—Mn1115.90 (18)
C4—C3—H3119.4C1—N2—Mn1138.51 (18)
C5—C4—C3121.8 (3)C7—N3—C6104.6 (2)
C5—C4—H4119.1C7—N3—H1116.9
C3—C4—H4119.1C6—N3—H1138.2
Symmetry codes: (i) x+1, y, z; (ii) y+1/2, x+1/2, z+1/2; (iii) y+1/2, x1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1···N3iv0.911.892.736 (4)154
Symmetry code: (iv) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula[Mn(C19H12N5)2]
Mr675.61
Crystal system, space groupTetragonal, P4n2
Temperature (K)298
a, c (Å)10.1225 (14), 15.865 (3)
V3)1625.6 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.45
Crystal size (mm)0.45 × 0.44 × 0.31
Data collection
DiffractometerBruker SMART 2K CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2<s(I)] reflections
6803, 1599, 1226
Rint0.040
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.095, 1.04
No. of reflections1599
No. of parameters113
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.18, 0.21
Absolute structureFlack (1983), 701 Friedel pairs
Absolute structure parameter0.00 (1)

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H1···N3i0.911.892.736 (4)153.8
Symmetry code: (i) x+1, y+1, z.
 

Acknowledgements

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).

References

First citationBruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationHarvey, M. A., Baggio, S., Muñoz, J. C. & Baggio, R. (2003). Acta Cryst. C59, m283–m285.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationShi, W., Li, W., Shen, P.-P., Xu, Y.-K., Wang, H.-M., Shi, M. & Liu, Y. (2003). Chin. J. Chem. 21, 659–664.  CAS Google Scholar
First citationWang, S., Cui, Y., Ran, R. & Luo, A. (1994). Polyhedron, 13, 1661–1668.  CSD CrossRef CAS Web of Science Google Scholar
First citationYue, S.-M., Xu, H.-B., Ma, J.-F., Su, Z.-M., Kan, Y.-H. & Zhang, H.-J. (2006). Polyhedron, 25, 635–644.  Web of Science CSD CrossRef CAS Google Scholar
First citationZhang, S.-H., Zeng, M.-H. & Liang, H. (2007). Acta Cryst. E63, m1055–m1056.  Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds