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

Bai, X.-Q.; Zhang, S.-H.

doi:10.1107/S1600536809008411

metal-organic compounds

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Volume 65| Part 4| April 2009| Page m397

doi:10.1107/S1600536809008411

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

Xian-Qun Bai ^a,^b and Shu-Hua Zhang ^a ^*

^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 Mn^II 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 ). For other comparable transition-metal complexes, see: Harvey et al. (2003 ); Wang et al. (1994 ); Yue et al. (2006 ); Zhang et al. (2007 ).

Experimental

Crystal data

[Mn(C₁₉H₁₂N₅)₂]
M_r = 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)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.095
S = 1.04
1599 reflections
113 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 701 Friedel pairs
Flack parameter: 0.00 (1)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008411/bi2351sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008411/bi2351Isup2.hkl

checkCIF report

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 Mn^II, 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.

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

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]	D_x = 1.380 Mg m⁻³
M_r = 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

Data collection top

Bruker SMART 2K CCD diffractometer	1226 reflections with I > 2<s(I)
Radiation source: fine-focus sealed tube	R_int = 0.040
Graphite monochromator	θ_max = 26.0°, θ_min = 2.4°
ϕ and ω scans	h = −10→12
6803 measured reflections	k = −12→11
1599 independent reflections	l = −19→12

Refinement top

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(F_o²) + (0.0482P)² + 0.3361P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1599 reflections	Δρ_max = 0.18 e Å⁻³
113 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 701 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (1)

Crystal data top

[Mn(C₁₉H₁₂N₅)₂]	Z = 2
M_r = 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

Data collection top

Bruker SMART 2K CCD diffractometer	1226 reflections with I > 2<s(I)
6803 measured reflections	R_int = 0.040
1599 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.095	Δρ_max = 0.18 e Å⁻³
S = 1.04	Δρ_min = −0.21 e Å⁻³
1599 reflections	Absolute structure: Flack (1983), 701 Friedel pairs
113 parameters	Absolute 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

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···N3^iv	0.91	1.89	2.736 (4)	154

Symmetry code: (iv) −x+1, −y+1, z.

Experimental details

Crystal data
Chemical formula	[Mn(C₁₉H₁₂N₅)₂]
M_r	675.61
Crystal system, space group	Tetragonal, P4n2
Temperature (K)	298
a, c (Å)	10.1225 (14), 15.865 (3)
V (Å³)	1625.6 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.45 × 0.44 × 0.31

Data collection
Diffractometer	Bruker SMART 2K CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2<s(I)] reflections	6803, 1599, 1226
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.095, 1.04
No. of reflections	1599
No. of parameters	113
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.21
Absolute structure	Flack (1983), 701 Friedel pairs
Absolute structure parameter	0.00 (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···A	D—H	H···A	D···A	D—H···A
N3—H1···N3ⁱ	0.91	1.89	2.736 (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

Bruker (2003). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harvey, 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
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shi, 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
Wang, S., Cui, Y., Ran, R. & Luo, A. (1994). Polyhedron, 13, 1661–1668. CSD CrossRef CAS Web of Science Google Scholar
Yue, 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
Zhang, S.-H., Zeng, M.-H. & Liang, H. (2007). Acta Cryst. E63, m1055–m1056. Web of Science CSD CrossRef IUCr Journals Google Scholar

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