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RETRACTED ARTICLE

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Di­azido­bis­(2,2′-bi­imidazole)manganese(II)

aDepartment of Chemistry and Chemical Engineering, ShanDong Institute of Education, Jinan 250013, People's Republic of China
*Correspondence e-mail: weipeihai@yahoo.com.cn

(Received 9 June 2008; accepted 12 June 2008; online 19 June 2008)

In the title compound, [Mn(N3)2(C6H6N4)2], the Mn atom (site symmetry [\overline{1}]) is bonded to two azide ions and two bidentate biimidizole ligands, resulting in a slightly distorted octa­hedral MnN6 geometry for the metal ion. In the crystal structure, N—H⋯N hydrogen bonds help to consolidate the packing.

Related literature

For a related structure, see: Hester et al. (1997[Hester, C. A., Baughman, R. G. & Collier, H. L. (1997). Polyhedron, 16, 2893-2895.]).

[Scheme 1]

Experimental

Crystal data
  • [Mn(N3)2(C6H6N4)2]

  • Mr = 407.30

  • Monoclinic, C 2/c

  • a = 12.5097 (10) Å

  • b = 8.9728 (5) Å

  • c = 14.1416 (10) Å

  • β = 91.883 (10)°

  • V = 1586.50 (19) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.87 mm−1

  • T = 293 (2) K

  • 0.40 × 0.26 × 0.20 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2004[Bruker (2004). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.723, Tmax = 0.846

  • 1966 measured reflections

  • 1505 independent reflections

  • 1250 reflections with I > 2σ(I)

  • Rint = 0.022

Refinement
  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.131

  • S = 1.00

  • 1505 reflections

  • 131 parameters

  • 2 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.49 e Å−3

  • Δρmin = −0.25 e Å−3

Table 1
Selected bond lengths (Å)

Mn1—N2 2.094 (3)
Mn1—N3 2.114 (3)
Mn1—N5 2.138 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯N7i 0.966 (18) 2.26 (3) 3.031 (4) 136 (3)
N1—H1A⋯N5ii 0.966 (18) 2.33 (4) 3.021 (4) 127 (3)
N4—H4⋯N7i 0.952 (19) 1.92 (2) 2.834 (4) 160 (4)
Symmetry codes: (i) [-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]; (ii) [x-{\script{1\over 2}}, y-{\script{1\over 2}}, z].

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2004[Bruker (2004). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; 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 study of coordination compounds including one-, two- and three-dimensional infinite frameworks has been expanding rapidly because of their fascinating structural diversity and potential application as functional materials. To date, much of the work has been focused on coordination polymers with semi-rigid ligands, such as 4,4'-bipyridine, pyrazine and their analogues. In this paper, we report the structure of the molecular title compound, (I), with the use of the 2,2'-biimidazole bridging ligand (Hester et al., 1997).

As shown in Fig. 1, the Mn ion in (I) occupies an inversion centre, and is hexacoordinated by six N atoms from two chelating ligands of H2bim (biimidizole; C6H6N4) and two azide ions, showing a slightly distorted MnN6 octahedral geometry (Table 1).

In the crystal of (I), N—H···N hydrogen bonds, one of which is bifurcated (Table 2), help to consolidate the packing.

Related literature top

For a related structure, see: Hester et al. (1997).

Experimental top

A mixture of manganese(II) perchlorate hexahydrate (1 mmol), 2,2'-biimidazoline (2 mmol) and Na3N3 (2 mmol) in 20 ml ethanol was reflued for several hours. The cooled solution was filtered and the filtrate was kept in an ice box for about one week. Yellow blocks of (I) were obtained with a yield of 10%. Anal. Calc. for C12H12MnN14: C 35.35, H 2.95, N 48.12%; Found: C 35.31, H 2.92, N 48.06%.

Refinement top

The N-bound H atoms were located in a difference map and their positions were freely refined with Uiso(H) = 1.2Ueq(N). The C-bound H atoms were placed in calculated positions (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); 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. The molecular structure of (I), drawn with 30% probability displacement ellipsoids for the non-hydrogen atoms. Symmetry code: (i) 3/2-x, 3/2-y, 1-z.
Diazidobis(2,2'-biimidazole)manganese(II) top
Crystal data top
[Mn(N3)2(C6H6N4)2]F(000) = 828
Mr = 407.30Dx = 1.705 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1505 reflections
a = 12.5097 (10) Åθ = 2.8–25.9°
b = 8.9728 (5) ŵ = 0.87 mm1
c = 14.1416 (10) ÅT = 293 K
β = 91.883 (10)°Block, yellow
V = 1586.50 (19) Å30.40 × 0.26 × 0.20 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer
1505 independent reflections
Radiation source: fine-focus sealed tube1250 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ϕ and ω scansθmax = 25.9°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 115
Tmin = 0.723, Tmax = 0.846k = 110
1966 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.081P)2 + 1.7249P]
where P = (Fo2 + 2Fc2)/3
1505 reflections(Δ/σ)max = 0.024
131 parametersΔρmax = 0.49 e Å3
2 restraintsΔρmin = 0.25 e Å3
Crystal data top
[Mn(N3)2(C6H6N4)2]V = 1586.50 (19) Å3
Mr = 407.30Z = 4
Monoclinic, C2/cMo Kα radiation
a = 12.5097 (10) ŵ = 0.87 mm1
b = 8.9728 (5) ÅT = 293 K
c = 14.1416 (10) Å0.40 × 0.26 × 0.20 mm
β = 91.883 (10)°
Data collection top
Bruker APEXII CCD
diffractometer
1505 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
1250 reflections with I > 2σ(I)
Tmin = 0.723, Tmax = 0.846Rint = 0.022
1966 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0382 restraints
wR(F2) = 0.131H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.49 e Å3
1505 reflectionsΔρmin = 0.25 e Å3
131 parameters
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*/Ueq
Mn10.75000.75000.50000.0486 (5)
C10.5842 (3)0.5617 (4)0.3628 (2)0.0572 (8)
H10.57110.62800.31320.069*
C20.5366 (3)0.4245 (4)0.3721 (2)0.0585 (9)
H20.48650.38190.33030.070*
C30.6462 (2)0.4631 (4)0.4891 (2)0.0482 (7)
C40.7106 (2)0.4562 (4)0.5744 (2)0.0489 (7)
C50.8223 (3)0.5322 (4)0.6783 (2)0.0580 (8)
H50.87130.59150.71180.070*
C60.7940 (3)0.3903 (4)0.7030 (2)0.0610 (9)
H60.81950.33690.75540.073*
N10.5763 (2)0.3633 (3)0.45300 (18)0.0534 (7)
H1A0.546 (3)0.270 (3)0.474 (3)0.064*
N20.6529 (2)0.5851 (3)0.43706 (17)0.0520 (7)
N30.7688 (2)0.5733 (3)0.59802 (18)0.0525 (7)
N40.7220 (2)0.3432 (3)0.63640 (19)0.0551 (7)
H40.680 (3)0.255 (3)0.634 (3)0.066*
N50.8833 (2)0.6634 (3)0.4268 (2)0.0529 (7)
N60.8963 (2)0.5320 (3)0.4212 (2)0.0552 (7)
N70.9109 (3)0.4018 (3)0.4143 (2)0.0723 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0504 (12)0.0400 (13)0.0550 (13)0.0096 (10)0.0016 (10)0.0034 (10)
C10.0542 (18)0.069 (2)0.0481 (17)0.0156 (16)0.0081 (14)0.0038 (15)
C20.0551 (18)0.070 (2)0.0495 (17)0.0171 (16)0.0056 (14)0.0031 (15)
C30.0485 (16)0.0500 (18)0.0462 (15)0.0087 (13)0.0012 (12)0.0003 (13)
C40.0481 (15)0.0480 (17)0.0503 (16)0.0051 (13)0.0012 (13)0.0026 (13)
C50.0598 (19)0.061 (2)0.0527 (17)0.0041 (16)0.0095 (14)0.0033 (15)
C60.064 (2)0.067 (2)0.0510 (18)0.0005 (18)0.0087 (15)0.0092 (16)
N10.0539 (15)0.0539 (16)0.0525 (15)0.0158 (13)0.0020 (12)0.0012 (12)
N20.0512 (14)0.0569 (17)0.0477 (14)0.0117 (13)0.0035 (11)0.0045 (12)
N30.0519 (15)0.0543 (16)0.0508 (14)0.0088 (13)0.0063 (11)0.0042 (12)
N40.0600 (16)0.0524 (16)0.0524 (14)0.0079 (13)0.0021 (12)0.0077 (12)
N50.0585 (16)0.0552 (17)0.0444 (14)0.0006 (14)0.0080 (12)0.0089 (12)
N60.0525 (15)0.0540 (18)0.0585 (16)0.0129 (13)0.0071 (12)0.0069 (13)
N70.073 (2)0.0512 (18)0.092 (2)0.0078 (15)0.0108 (17)0.0073 (16)
Geometric parameters (Å, º) top
Mn1—N22.094 (3)C3—C41.430 (4)
Mn1—N2i2.094 (3)C4—N31.315 (4)
Mn1—N3i2.114 (3)C4—N41.345 (4)
Mn1—N32.114 (3)C5—N31.350 (4)
Mn1—N52.138 (3)C5—C61.370 (5)
Mn1—N5i2.138 (3)C5—H50.9300
C1—N21.351 (4)C6—N41.350 (4)
C1—C21.375 (5)C6—H60.9300
C1—H10.9300N1—H1A0.966 (18)
C2—N11.349 (4)N4—H40.952 (19)
C2—H20.9300N5—N61.193 (4)
C3—N21.323 (4)N6—N71.187 (4)
C3—N11.340 (4)
N2—Mn1—N2i180.0)N3—C4—N4113.0 (3)
N2—Mn1—N3i101.59 (10)N3—C4—C3118.2 (3)
N2i—Mn1—N3i78.41 (10)N4—C4—C3128.8 (3)
N2—Mn1—N378.41 (10)N3—C5—C6110.1 (3)
N2i—Mn1—N3101.59 (10)N3—C5—H5125.0
N3i—Mn1—N3180.0C6—C5—H5125.0
N2—Mn1—N589.31 (11)N4—C6—C5106.5 (3)
N2i—Mn1—N590.69 (11)N4—C6—H6126.7
N3i—Mn1—N591.53 (11)C5—C6—H6126.7
N3—Mn1—N588.47 (11)C3—N1—C2105.6 (3)
N2—Mn1—N5i90.69 (11)C3—N1—H1A135 (3)
N2i—Mn1—N5i89.31 (11)C2—N1—H1A119 (3)
N3i—Mn1—N5i88.47 (11)C3—N2—C1104.7 (3)
N3—Mn1—N5i91.53 (11)C3—N2—Mn1113.26 (19)
N5—Mn1—N5i180.0C1—N2—Mn1141.7 (2)
N2—C1—C2109.3 (3)C4—N3—C5104.5 (3)
N2—C1—H1125.3C4—N3—Mn1112.6 (2)
C2—C1—H1125.3C5—N3—Mn1142.9 (2)
N1—C2—C1107.3 (3)C4—N4—C6105.8 (3)
N1—C2—H2126.4C4—N4—H4124 (3)
C1—C2—H2126.4C6—N4—H4130 (3)
N2—C3—N1113.1 (3)N6—N5—Mn1120.1 (2)
N2—C3—C4117.4 (3)N7—N6—N5178.6 (4)
N1—C3—C4129.5 (3)
Symmetry code: (i) x+3/2, y+3/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N7ii0.97 (2)2.26 (3)3.031 (4)136 (3)
N1—H1A···N5iii0.97 (2)2.33 (4)3.021 (4)127 (3)
N4—H4···N7ii0.95 (2)1.92 (2)2.834 (4)160 (4)
Symmetry codes: (ii) x+3/2, y+1/2, z+1; (iii) x1/2, y1/2, z.

Experimental details

Crystal data
Chemical formula[Mn(N3)2(C6H6N4)2]
Mr407.30
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)12.5097 (10), 8.9728 (5), 14.1416 (10)
β (°) 91.883 (10)
V3)1586.50 (19)
Z4
Radiation typeMo Kα
µ (mm1)0.87
Crystal size (mm)0.40 × 0.26 × 0.20
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2004)
Tmin, Tmax0.723, 0.846
No. of measured, independent and
observed [I > 2σ(I)] reflections
1966, 1505, 1250
Rint0.022
(sin θ/λ)max1)0.614
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.131, 1.00
No. of reflections1505
No. of parameters131
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.49, 0.25

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
Mn1—N22.094 (3)Mn1—N52.138 (3)
Mn1—N32.114 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N7i0.966 (18)2.26 (3)3.031 (4)136 (3)
N1—H1A···N5ii0.966 (18)2.33 (4)3.021 (4)127 (3)
N4—H4···N7i0.952 (19)1.92 (2)2.834 (4)160 (4)
Symmetry codes: (i) x+3/2, y+1/2, z+1; (ii) x1/2, y1/2, z.
 

Acknowledgements

The authors thank the National Ministry of Science and Technology of China (grant No. 2001CB6105-07).

References

First citationBruker (2004). APEX2, SADABS and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHester, C. A., Baughman, R. G. & Collier, H. L. (1997). Polyhedron, 16, 2893–2895.  CSD CrossRef CAS Web of Science Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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