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

Zhang, X.; Wei, P.; Li, B.

doi:10.1107/S1600536808017984

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m934

doi:10.1107/S1600536808017984

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RETRACTED ARTICLE

This article has been retracted. To view the retraction notice, click here.

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

Xiutang Zhang,^a Peihai Wei ^a ^* and Bin Li ^a

^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 ).

Experimental

Crystal data

[Mn(N₃)₂(C₆H₆N₄)₂]
M_r = 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 ) T_min = 0.723, T_max = 0.846
1966 measured reflections
1505 independent reflections
1250 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.49 e Å⁻³
Δρ_min = −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	D⋯A	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); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S1600536808017984/hb2744sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808017984/hb2744Isup2.hkl

checkCIF report

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%.

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

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
M_r = 407.30	D_x = 1.705 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1505 reflections
a = 12.5097 (10) Å	θ = 2.8–25.9°
b = 8.9728 (5) Å	µ = 0.87 mm⁻¹
c = 14.1416 (10) Å	T = 293 K
β = 91.883 (10)°	Block, yellow
V = 1586.50 (19) Å³	0.40 × 0.26 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1505 independent reflections
Radiation source: fine-focus sealed tube	1250 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 25.9°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −1→15
T_min = 0.723, T_max = 0.846	k = −1→10
1966 measured reflections	l = −17→17

Refinement top

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.081P)² + 1.7249P] where P = (F_o² + 2F_c²)/3
1505 reflections	(Δ/σ)_max = 0.024
131 parameters	Δρ_max = 0.49 e Å⁻³
2 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Mn(N₃)₂(C₆H₆N₄)₂]	V = 1586.50 (19) Å³
M_r = 407.30	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.5097 (10) Å	µ = 0.87 mm⁻¹
b = 8.9728 (5) Å	T = 293 K
c = 14.1416 (10) Å	0.40 × 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)
T_min = 0.723, T_max = 0.846	R_int = 0.022
1966 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	2 restraints
wR(F²) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.49 e Å⁻³
1505 reflections	Δρ_min = −0.25 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Mn1	0.7500	0.7500	0.5000	0.0486 (5)
C1	0.5842 (3)	0.5617 (4)	0.3628 (2)	0.0572 (8)
H1	0.5711	0.6280	0.3132	0.069*
C2	0.5366 (3)	0.4245 (4)	0.3721 (2)	0.0585 (9)
H2	0.4865	0.3819	0.3303	0.070*
C3	0.6462 (2)	0.4631 (4)	0.4891 (2)	0.0482 (7)
C4	0.7106 (2)	0.4562 (4)	0.5744 (2)	0.0489 (7)
C5	0.8223 (3)	0.5322 (4)	0.6783 (2)	0.0580 (8)
H5	0.8713	0.5915	0.7118	0.070*
C6	0.7940 (3)	0.3903 (4)	0.7030 (2)	0.0610 (9)
H6	0.8195	0.3369	0.7554	0.073*
N1	0.5763 (2)	0.3633 (3)	0.45300 (18)	0.0534 (7)
H1A	0.546 (3)	0.270 (3)	0.474 (3)	0.064*
N2	0.6529 (2)	0.5851 (3)	0.43706 (17)	0.0520 (7)
N3	0.7688 (2)	0.5733 (3)	0.59802 (18)	0.0525 (7)
N4	0.7220 (2)	0.3432 (3)	0.63640 (19)	0.0551 (7)
H4	0.680 (3)	0.255 (3)	0.634 (3)	0.066*
N5	0.8833 (2)	0.6634 (3)	0.4268 (2)	0.0529 (7)
N6	0.8963 (2)	0.5320 (3)	0.4212 (2)	0.0552 (7)
N7	0.9109 (3)	0.4018 (3)	0.4143 (2)	0.0723 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0504 (12)	0.0400 (13)	0.0550 (13)	0.0096 (10)	−0.0016 (10)	−0.0034 (10)
C1	0.0542 (18)	0.069 (2)	0.0481 (17)	−0.0156 (16)	−0.0081 (14)	0.0038 (15)
C2	0.0551 (18)	0.070 (2)	0.0495 (17)	−0.0171 (16)	−0.0056 (14)	−0.0031 (15)
C3	0.0485 (16)	0.0500 (18)	0.0462 (15)	−0.0087 (13)	0.0012 (12)	−0.0003 (13)
C4	0.0481 (15)	0.0480 (17)	0.0503 (16)	−0.0051 (13)	0.0012 (13)	0.0026 (13)
C5	0.0598 (19)	0.061 (2)	0.0527 (17)	−0.0041 (16)	−0.0095 (14)	0.0033 (15)
C6	0.064 (2)	0.067 (2)	0.0510 (18)	−0.0005 (18)	−0.0087 (15)	0.0092 (16)
N1	0.0539 (15)	0.0539 (16)	0.0525 (15)	−0.0158 (13)	0.0020 (12)	−0.0012 (12)
N2	0.0512 (14)	0.0569 (17)	0.0477 (14)	−0.0117 (13)	−0.0035 (11)	0.0045 (12)
N3	0.0519 (15)	0.0543 (16)	0.0508 (14)	−0.0088 (13)	−0.0063 (11)	0.0042 (12)
N4	0.0600 (16)	0.0524 (16)	0.0524 (14)	−0.0079 (13)	−0.0021 (12)	0.0077 (12)
N5	0.0585 (16)	0.0552 (17)	0.0444 (14)	−0.0006 (14)	−0.0080 (12)	−0.0089 (12)
N6	0.0525 (15)	0.0540 (18)	0.0585 (16)	−0.0129 (13)	−0.0071 (12)	0.0069 (13)
N7	0.073 (2)	0.0512 (18)	0.092 (2)	−0.0078 (15)	−0.0108 (17)	0.0073 (16)

Geometric parameters (Å, º) top

Mn1—N2	2.094 (3)	C3—C4	1.430 (4)
Mn1—N2ⁱ	2.094 (3)	C4—N3	1.315 (4)
Mn1—N3ⁱ	2.114 (3)	C4—N4	1.345 (4)
Mn1—N3	2.114 (3)	C5—N3	1.350 (4)
Mn1—N5	2.138 (3)	C5—C6	1.370 (5)
Mn1—N5ⁱ	2.138 (3)	C5—H5	0.9300
C1—N2	1.351 (4)	C6—N4	1.350 (4)
C1—C2	1.375 (5)	C6—H6	0.9300
C1—H1	0.9300	N1—H1A	0.966 (18)
C2—N1	1.349 (4)	N4—H4	0.952 (19)
C2—H2	0.9300	N5—N6	1.193 (4)
C3—N2	1.323 (4)	N6—N7	1.187 (4)
C3—N1	1.340 (4)

N2—Mn1—N2ⁱ	180.0)	N3—C4—N4	113.0 (3)
N2—Mn1—N3ⁱ	101.59 (10)	N3—C4—C3	118.2 (3)
N2ⁱ—Mn1—N3ⁱ	78.41 (10)	N4—C4—C3	128.8 (3)
N2—Mn1—N3	78.41 (10)	N3—C5—C6	110.1 (3)
N2ⁱ—Mn1—N3	101.59 (10)	N3—C5—H5	125.0
N3ⁱ—Mn1—N3	180.0	C6—C5—H5	125.0
N2—Mn1—N5	89.31 (11)	N4—C6—C5	106.5 (3)
N2ⁱ—Mn1—N5	90.69 (11)	N4—C6—H6	126.7
N3ⁱ—Mn1—N5	91.53 (11)	C5—C6—H6	126.7
N3—Mn1—N5	88.47 (11)	C3—N1—C2	105.6 (3)
N2—Mn1—N5ⁱ	90.69 (11)	C3—N1—H1A	135 (3)
N2ⁱ—Mn1—N5ⁱ	89.31 (11)	C2—N1—H1A	119 (3)
N3ⁱ—Mn1—N5ⁱ	88.47 (11)	C3—N2—C1	104.7 (3)
N3—Mn1—N5ⁱ	91.53 (11)	C3—N2—Mn1	113.26 (19)
N5—Mn1—N5ⁱ	180.0	C1—N2—Mn1	141.7 (2)
N2—C1—C2	109.3 (3)	C4—N3—C5	104.5 (3)
N2—C1—H1	125.3	C4—N3—Mn1	112.6 (2)
C2—C1—H1	125.3	C5—N3—Mn1	142.9 (2)
N1—C2—C1	107.3 (3)	C4—N4—C6	105.8 (3)
N1—C2—H2	126.4	C4—N4—H4	124 (3)
C1—C2—H2	126.4	C6—N4—H4	130 (3)
N2—C3—N1	113.1 (3)	N6—N5—Mn1	120.1 (2)
N2—C3—C4	117.4 (3)	N7—N6—N5	178.6 (4)
N1—C3—C4	129.5 (3)

Symmetry code: (i) −x+3/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N7ⁱⁱ	0.97 (2)	2.26 (3)	3.031 (4)	136 (3)
N1—H1A···N5ⁱⁱⁱ	0.97 (2)	2.33 (4)	3.021 (4)	127 (3)
N4—H4···N7ⁱⁱ	0.95 (2)	1.92 (2)	2.834 (4)	160 (4)

Symmetry codes: (ii) −x+3/2, −y+1/2, −z+1; (iii) x−1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	[Mn(N₃)₂(C₆H₆N₄)₂]
M_r	407.30
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	12.5097 (10), 8.9728 (5), 14.1416 (10)
β (°)	91.883 (10)
V (Å³)	1586.50 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.87
Crystal size (mm)	0.40 × 0.26 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.723, 0.846
No. of measured, independent and observed [I > 2σ(I)] reflections	1966, 1505, 1250
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.614

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.131, 1.00
No. of reflections	1505
No. of parameters	131
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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—N2	2.094 (3)	Mn1—N5	2.138 (3)
Mn1—N3	2.114 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+3/2, −y+1/2, −z+1; (ii) x−1/2, y−1/2, z.

Acknowledgements

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

References

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