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

Li, S.; Wang, S.-B.; Zhang, F.-L.; Tang, K.

doi:10.1107/S1600536807062873

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m76

https://doi.org/10.1107/S1600536807062873

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RETRACTED ARTICLE

This article has been retracted.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

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

Sheng Li,^a ^* Shou-Bin Wang,^b Fu-Li Zhang ^a and Kun Tang ^a

^aCollege of Medicine, Henan University, Kaifeng 475003, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Henan University, Kaifeng 475003, People's Republic of China
^*Correspondence e-mail: lisheng0821@sina.com

(Received 10 November 2007; accepted 24 November 2007; online 6 December 2007)

In the title compound, [Co(N₃)₂(C₆H₆N₄)₂], the Co^II atom lies on a centre of inversion and is bonded to two azide ions and two bidentate 2,2′-biimidizole ligands, giving a slightly distorted octahedral CoN₆ coordination geometry. In the crystal structure, intermolecular N—H⋯N hydrogen bonds exist between the 2,2′-biimidizole ligands and the azide ions, linking the complexes into sheets.

Related literature

For related literature, see: Rees et al. (1983 ); Hardman & Lipscomb (1984 ); Kuo & Makinen (1982 ); Dworschak & Plapp (1977 ).

Experimental

Crystal data

[Co(N₃)₂(C₆H₆N₄)₂]
M_r = 411.29
Monoclinic, C 2/c
a = 12.8085 (10) Å
b = 8.7632 (5) Å
c = 14.4793 (5) Å
β = 91.913 (1)°
V = 1624.30 (17) Å³
Z = 4
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 293 (2) K
0.28 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.750, T_max = 0.811
1961 measured reflections
1501 independent reflections
1246 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.078
S = 1.00
1501 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6A⋯N5ⁱ	0.86	2.01	2.819 (3)	156
N7—H7A⋯N5ⁱ	0.86	2.25	3.012 (3)	148
N7—H7A⋯N3ⁱⁱ	0.86	2.55	3.049 (3)	118
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807062873/bi2265sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062873/bi2265Isup2.hkl

checkCIF report

Comment top

The imidazole moiety is of biochemical importance due to its presence in more than 200 metalloenzymes, such as carboxypeptidase A (CPA), carbonic anhydrase (CA), liver alcohol dehydrogenase (LADH), and superoxide dismutase (SOD) (Rees et al., 1983; Hardman & Lipscomb, 1984; Kuo & Makinen, 1982; Dworschak & Plapp, 1977).

In the title compound, the Co^II atom occupies an inversion centre, and is hexacoordinated by six N atoms from two chelating ligands of H₂bim (2,2'-biimidizole; C₆H₆N₄) and two azide ions, showing a slightly distorted octahedral geometry (Fig. 1). The four N atoms from the chelating H₂bim consist of the base and the other two N atoms from two azide ions ocupy the axial positions. In the crystal, intermolecular N—H···N hydrogen bonds between 2,2'-biimidizole ligands and azide ions link the complexes into sheets lying in the (002) planes (Fig. 2).

Related literature top

For related literature, see: Rees et al. (1983); Hardman & Lipscomb (1984); Kuo & Makinen (1982); Dworschak & Plapp (1977).

Experimental top

A mixture of CoCl₂.2(H₂O) (1 mmol), 2,2'-biimidazoline (2 mmol) and NaN₃ (2 mmol) in 20 ml me thanol was refluxed for two hours. After cooling, the solution was filtered and the filtrate was evaporated naturally at room temperature. Two day later, red blocks of the title compound were obtained with a yield of 22%. Elemental analysis calculated: C 35.04, H 2.92, N 47.69%; found: C 35.01, H 2.96, N 47.65%.

Structure description top

For related literature, see: Rees et al. (1983); Hardman & Lipscomb (1984); Kuo & Makinen (1982); Dworschak & Plapp (1977).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top

	Fig. 1. The molecular structure with 30% probability displacement ellipsoids for non-H atoms. Atoms with suffix I are generated by the symmetry operator -x + 1/2, -y - 1/2, -z + 1.
	Fig. 2. Packing diagram showing intermolecular N—H···N hydrogen bonds.

Diazidobis(2,2'-biimidazole)cobalt(II) top

Crystal data top

[Co(N₃)₂(C₆H₆N₄)₂]	F(000) = 836
M_r = 411.29	D_x = 1.682 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1501 reflections
a = 12.8085 (10) Å	θ = 2.8–25.5°
b = 8.7632 (5) Å	µ = 1.09 mm⁻¹
c = 14.4793 (5) Å	T = 293 K
β = 91.913 (1)°	Block, red
V = 1624.30 (17) Å³	0.28 × 0.22 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1501 independent reflections
Radiation source: fine-focus sealed tube	1246 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 25.5°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −1→15
T_min = 0.750, T_max = 0.811	k = −1→10
1961 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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.032P)² + 0.7528P] where P = (F_o² + 2F_c²)/3
1501 reflections	(Δ/σ)_max = 0.016
124 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

[Co(N₃)₂(C₆H₆N₄)₂]	V = 1624.30 (17) Å³
M_r = 411.29	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.8085 (10) Å	µ = 1.09 mm⁻¹
b = 8.7632 (5) Å	T = 293 K
c = 14.4793 (5) Å	0.28 × 0.22 × 0.20 mm
β = 91.913 (1)°

Data collection top

Bruker APEXII CCD diffractometer	1501 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1246 reflections with I > 2σ(I)
T_min = 0.750, T_max = 0.811	R_int = 0.022
1961 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.00	Δρ_max = 0.24 e Å⁻³
1501 reflections	Δρ_min = −0.21 e Å⁻³
124 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
Co1	0.2500	−0.2500	0.5000	0.04053 (15)
C1	0.08433 (18)	−0.0620 (3)	0.36274 (15)	0.0523 (6)
H1	0.0724	−0.1298	0.3141	0.063*
C2	0.03681 (18)	0.0756 (3)	0.37190 (15)	0.0528 (6)
H2	−0.0126	0.1194	0.3315	0.063*
C3	0.14622 (17)	0.0371 (2)	0.48932 (14)	0.0433 (5)
C4	0.21008 (17)	0.0440 (2)	0.57427 (14)	0.0437 (5)
C5	0.32254 (19)	−0.0319 (3)	0.67815 (16)	0.0535 (6)
H5	0.3710	−0.0924	0.7103	0.064*
C6	0.29414 (19)	0.1097 (3)	0.70284 (16)	0.0556 (6)
H6	0.3182	0.1644	0.7543	0.067*
N1	0.15295 (14)	−0.0854 (2)	0.43678 (12)	0.0463 (4)
N2	0.26893 (14)	−0.0737 (2)	0.59794 (12)	0.0475 (4)
N3	0.38297 (15)	−0.1637 (2)	0.42685 (13)	0.0521 (5)
N4	0.39621 (15)	−0.0323 (2)	0.42133 (13)	0.0507 (5)
N5	0.41050 (18)	0.0987 (2)	0.41471 (16)	0.0668 (6)
N6	0.22221 (15)	0.1566 (2)	0.63634 (12)	0.0506 (5)
H6A	0.1905	0.2432	0.6348	0.061*
N7	0.07654 (14)	0.1364 (2)	0.45280 (12)	0.0484 (4)
H7A	0.0598	0.2230	0.4761	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0437 (2)	0.0363 (2)	0.0409 (2)	0.01142 (17)	−0.00752 (16)	−0.00494 (16)
C1	0.0524 (13)	0.0580 (14)	0.0459 (12)	0.0139 (11)	−0.0072 (10)	−0.0039 (10)
C2	0.0522 (13)	0.0585 (15)	0.0473 (12)	0.0164 (11)	−0.0055 (10)	0.0043 (11)
C3	0.0431 (11)	0.0417 (12)	0.0452 (11)	0.0082 (9)	0.0015 (9)	0.0009 (9)
C4	0.0455 (11)	0.0400 (11)	0.0456 (11)	0.0047 (10)	0.0022 (9)	−0.0028 (9)
C5	0.0556 (13)	0.0536 (14)	0.0503 (12)	0.0048 (11)	−0.0100 (10)	−0.0019 (11)
C6	0.0618 (14)	0.0551 (15)	0.0491 (12)	−0.0004 (12)	−0.0088 (11)	−0.0091 (11)
N1	0.0474 (10)	0.0460 (11)	0.0450 (9)	0.0112 (9)	−0.0048 (8)	−0.0042 (8)
N2	0.0507 (10)	0.0442 (10)	0.0472 (10)	0.0078 (9)	−0.0065 (8)	−0.0044 (8)
N3	0.0554 (11)	0.0401 (11)	0.0605 (11)	0.0096 (9)	−0.0019 (9)	−0.0036 (9)
N4	0.0488 (11)	0.0505 (13)	0.0522 (11)	0.0128 (9)	−0.0073 (9)	−0.0070 (9)
N5	0.0717 (14)	0.0417 (12)	0.0860 (15)	0.0073 (11)	−0.0101 (12)	−0.0065 (11)
N6	0.0588 (11)	0.0415 (11)	0.0514 (10)	0.0074 (9)	−0.0008 (9)	−0.0070 (8)
N7	0.0531 (11)	0.0425 (10)	0.0497 (10)	0.0148 (9)	0.0018 (8)	0.0005 (8)

Geometric parameters (Å, º) top

Co1—N1	2.0945 (17)	C3—C4	1.455 (3)
Co1—N1ⁱ	2.0945 (17)	C4—N2	1.316 (3)
Co1—N2ⁱ	2.1055 (18)	C4—N6	1.341 (3)
Co1—N2	2.1055 (18)	C5—C6	1.344 (3)
Co1—N3	2.172 (2)	C5—N2	1.379 (3)
Co1—N3ⁱ	2.172 (2)	C5—H5	0.930
C1—C2	1.359 (3)	C6—N6	1.373 (3)
C1—N1	1.379 (3)	C6—H6	0.930
C1—H1	0.930	N3—N4	1.167 (3)
C2—N7	1.370 (3)	N4—N5	1.167 (3)
C2—H2	0.930	N6—H6A	0.860
C3—N1	1.320 (3)	N7—H7A	0.860
C3—N7	1.343 (3)

N1—Co1—N1ⁱ	180.00 (8)	N2—C4—N6	110.49 (19)
N1—Co1—N2ⁱ	99.06 (7)	N2—C4—C3	119.23 (19)
N1ⁱ—Co1—N2ⁱ	80.94 (7)	N6—C4—C3	130.3 (2)
N1—Co1—N2	80.94 (7)	C6—C5—N2	109.7 (2)
N1ⁱ—Co1—N2	99.06 (7)	C6—C5—H5	125.1
N2ⁱ—Co1—N2	180.0	N2—C5—H5	125.1
N1—Co1—N3	90.61 (7)	C5—C6—N6	105.7 (2)
N1ⁱ—Co1—N3	89.39 (7)	C5—C6—H6	127.1
N2ⁱ—Co1—N3	90.10 (7)	N6—C6—H6	127.1
N2—Co1—N3	89.90 (7)	C3—N1—C1	105.96 (18)
N1—Co1—N3ⁱ	89.39 (7)	C3—N1—Co1	110.93 (13)
N1ⁱ—Co1—N3ⁱ	90.61 (7)	C1—N1—Co1	142.74 (16)
N2ⁱ—Co1—N3ⁱ	89.90 (7)	C4—N2—C5	106.00 (19)
N2—Co1—N3ⁱ	90.10 (7)	C4—N2—Co1	110.33 (14)
N3—Co1—N3ⁱ	180.00 (6)	C5—N2—Co1	143.64 (16)
C2—C1—N1	109.4 (2)	N4—N3—Co1	119.70 (17)
C2—C1—H1	125.3	N5—N4—N3	179.0 (3)
N1—C1—H1	125.3	C4—N6—C6	108.01 (19)
C1—C2—N7	105.91 (19)	C4—N6—H6A	126.0
C1—C2—H2	127.0	C6—N6—H6A	126.0
N7—C2—H2	127.0	C3—N7—C2	107.90 (18)
N1—C3—N7	110.83 (19)	C3—N7—H7A	126.0
N1—C3—C4	118.37 (18)	C2—N7—H7A	126.1
N7—C3—C4	130.8 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···N5ⁱⁱ	0.86	2.01	2.819 (3)	156
N7—H7A···N5ⁱⁱ	0.86	2.25	3.012 (3)	148
N7—H7A···N3ⁱⁱⁱ	0.86	2.55	3.049 (3)	118

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

Experimental details

Crystal data
Chemical formula	[Co(N₃)₂(C₆H₆N₄)₂]
M_r	411.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	12.8085 (10), 8.7632 (5), 14.4793 (5)
β (°)	91.913 (1)
V (Å³)	1624.30 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.28 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.750, 0.811
No. of measured, independent and observed [I > 2σ(I)] reflections	1961, 1501, 1246
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.078, 1.00
No. of reflections	1501
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···N5ⁱ	0.86	2.01	2.819 (3)	156.1
N7—H7A···N5ⁱ	0.86	2.25	3.012 (3)	148.3
N7—H7A···N3ⁱⁱ	0.86	2.55	3.049 (3)	117.6

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

Acknowledgements

The authors are grateful for financial support from Henan University (grant No. 05YBGG013)

References

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