Dichlorido[bis­(2-ethyl-5-methyl-1H-imidazol-4-yl-κN3)methane]­cobalt(II) monohydrate

Qian, X.-M.; Luo, Y.-H.; Li, J.-F.; Mao, S.-L.; Gao, G.

doi:10.1107/S1600536811011032

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page m575

doi:10.1107/S1600536811011032

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Dichlorido[bis(2-ethyl-5-methyl-1H-imidazol-4-yl-κN³)methane]cobalt(II) monohydrate

Xiao-Min Qian,^a ^* Yang-Hui Luo,^a Jin-Feng Li,^a Shu-Lin Mao ^a and Ge Gao ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chmsunbw@seu.edu.cn

(Received 18 January 2011; accepted 24 March 2011; online 13 April 2011)

In the title compound, [CoCl₂(C₁₃H₂₀N₄)]·H₂O, the Co^II atom lies on a mirror plane and is four-coordinated by two N atoms of the imidazole ligand and two Cl atoms in a distorted tetrahedral arrangement. The water molecule participates in the formation of hydrogen bonds, resulting in a three dimensional network involving the Cl atoms and the NH groups. The terminal C atom of the ethyl group is disordered over two sites of equal occupancy.

Related literature

For background to the use of imidazole derivatives as catalyts and biocatalysts for dioxygen transport and electron storage, see: Bouwman et al. (2000 ). For related structures, see: Beznischenko et al. (2007 ); Pajunen (1981 ).

Experimental

Crystal data

[CoCl₂(C₁₃H₂₀N₄)]·H₂O
M_r = 380.18
Monoclinic, P 2₁ /m
a = 8.3927 (7) Å
b = 12.1388 (14) Å
c = 8.5860 (9) Å
β = 97.045 (1)°
V = 868.11 (15) Å³
Z = 2
Mo Kα radiation
μ = 1.30 mm⁻¹
T = 298 K
0.40 × 0.30 × 0.22 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.625, T_max = 0.763
4313 measured reflections
1607 independent reflections
1174 reflections with I > 2.0σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.114
S = 1.03
1607 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1C⋯Cl1	0.85	2.41	3.256 (4)	175
O1—H1D⋯Cl2ⁱ	0.85	2.29	3.139 (4)	175
N2—H2⋯O1ⁱⁱ	0.86	2.12	2.959 (3)	165
Symmetry codes: (i) x, y, z+1; (ii) -x+1, -y, -z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011032/pv2382sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011032/pv2382Isup2.hkl

checkCIF report

Comment top

Imidazole derivatives are used as catalyts and biocatalysts for dioxygen transport and electron storage (Bouwman et al., 2000). As part of our interest in imidazole derivatives, we report here the crystal structure of a new cobalt complex of imidazole derivative.

In the title complex (Fig. 1), the Co^II lies on a mirror plane and displays a tetrahedral coordination with two N atoms of the imidazole ligand and two Cl atoms. The asymmetric unit also contains a solvate water molecule. The distances and angles agree with related structures (Beznischenko et al., 2007; Pajunen, 1981). The terminal C-atom of the ethyl group was disordered over two sites C6 and C6' with equal site occopancy factors.

The water molecule participates in the formation of intricated hydrogen bonds resulting in a three dimensionnal network involving the Cl atoms and the NH groups (Table 1).

Related literature top

For background to the use of imidazole derivatives as catalyts and biocatalysts for dioxygen transport and electron storage, see: Bouwman et al. (2000). For related structures, see: Beznischenko et al. (2007); Pajunen (1981). Scheme - water moleculae better shown as H₂O

Experimental top

The ligand and the title complex were prepared by following the procedures reported in the literature (Bouwman, et al., 2000). Single crystals of the title compound as purule prisms were grown from a solution of ethanol by slow evaporation at room temperature within a few days.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound with atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The terminal C-atom of the ethyl group was disordered over sites C6 and C6'. Symmetry code "A" in the labels: x, -y+1/2, z.

Dichlorido[bis(2-ethyl-5-methyl-1H-imidazol-4-yl- κN³)methane]cobalt(II) monohydrate top

Crystal data top

[CoCl₂(C₁₃H₂₀N₄)]·H₂O	F(000) = 394
M_r = 380.18	D_x = 1.454 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1482 reflections
a = 8.3927 (7) Å	θ = 2.4–25.0°
b = 12.1388 (14) Å	µ = 1.30 mm⁻¹
c = 8.5860 (9) Å	T = 298 K
β = 97.045 (1)°	Prism, violet
V = 868.11 (15) Å³	0.40 × 0.30 × 0.22 mm
Z = 2

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1607 independent reflections
Radiation source: fine-focus sealed tube	1174 reflections with I > 2.0σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 8.192 pixels mm^-1	θ_max = 25.0°, θ_min = 2.4°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −14→13
T_min = 0.625, T_max = 0.763	l = −5→10
4313 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0528P)² + 0.6331P] where P = (F_o² + 2F_c²)/3
1607 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[CoCl₂(C₁₃H₂₀N₄)]·H₂O	V = 868.11 (15) Å³
M_r = 380.18	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 8.3927 (7) Å	µ = 1.30 mm⁻¹
b = 12.1388 (14) Å	T = 298 K
c = 8.5860 (9) Å	0.40 × 0.30 × 0.22 mm
β = 97.045 (1)°

Data collection top

Bruker SMART 1K CCD area-detector diffractometer	1607 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1174 reflections with I > 2.0σ(I)
T_min = 0.625, T_max = 0.763	R_int = 0.039
4313 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.03	Δρ_max = 0.35 e Å⁻³
1607 reflections	Δρ_min = −0.25 e Å⁻³
109 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)
Co1	0.75499 (7)	0.2500	0.32643 (8)	0.0443 (3)
Cl1	0.93574 (14)	0.2500	0.54316 (16)	0.0521 (4)
Cl2	0.88551 (17)	0.2500	0.11144 (17)	0.0656 (4)
O1	0.6677 (4)	0.2500	0.7871 (4)	0.0547 (9)
H1C	0.7331	0.2500	0.7190	0.066*
H1D	0.7215	0.2500	0.8776	0.066*
N1	0.5936 (3)	0.1271 (2)	0.3223 (4)	0.0461 (7)
N2	0.4566 (3)	−0.0235 (3)	0.2690 (4)	0.0525 (8)
H2	0.4344	−0.0904	0.2413	0.063*
C1	0.6018 (4)	0.0241 (3)	0.2763 (5)	0.0503 (10)
C2	0.3496 (4)	0.0527 (3)	0.3131 (4)	0.0446 (9)
C3	0.4343 (4)	0.1455 (3)	0.3473 (4)	0.0423 (8)
C4	0.3821 (6)	0.2500	0.4156 (7)	0.0504 (13)
H4A	0.4209	0.2500	0.5268	0.060*
H4B	0.2658	0.2500	0.4061	0.060*
C5	0.7486 (4)	−0.0350 (4)	0.2383 (7)	0.0751 (14)
H5A	0.8416	0.0099	0.2740	0.090*	0.50
H5B	0.7585	−0.1032	0.2976	0.090*	0.50
H5'A	0.8073	−0.0616	0.3353	0.090*	0.50
H5'B	0.8171	0.0180	0.1941	0.090*	0.50
C6	0.7529 (13)	−0.0595 (9)	0.0839 (15)	0.079 (2)	0.50
H6A	0.6625	−0.1049	0.0469	0.118*	0.50
H6B	0.8504	−0.0982	0.0722	0.118*	0.50
H6C	0.7488	0.0075	0.0240	0.118*	0.50
C6'	0.7231 (13)	−0.1306 (9)	0.1225 (14)	0.079 (2)	0.50
H6'1	0.6592	−0.1062	0.0284	0.118*	0.50
H6'2	0.6688	−0.1895	0.1687	0.118*	0.50
H6'3	0.8252	−0.1562	0.0975	0.118*	0.50
C7	0.1749 (4)	0.0265 (4)	0.3136 (6)	0.0614 (11)
H7A	0.1211	0.0891	0.3512	0.092*
H7B	0.1640	−0.0354	0.3809	0.092*
H7C	0.1279	0.0091	0.2088	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0267 (4)	0.0526 (5)	0.0533 (5)	0.000	0.0037 (3)	0.000
Cl1	0.0388 (7)	0.0628 (8)	0.0534 (8)	0.000	0.0002 (6)	0.000
Cl2	0.0543 (8)	0.0925 (11)	0.0515 (8)	0.000	0.0126 (7)	0.000
O1	0.051 (2)	0.060 (2)	0.053 (2)	0.000	0.0044 (17)	0.000
N1	0.0271 (14)	0.0473 (18)	0.064 (2)	−0.0015 (12)	0.0038 (13)	−0.0029 (16)
N2	0.0347 (15)	0.0457 (18)	0.076 (2)	−0.0011 (14)	0.0010 (15)	−0.0062 (17)
C1	0.0285 (17)	0.053 (2)	0.068 (3)	0.0012 (16)	0.0006 (16)	−0.003 (2)
C2	0.0331 (17)	0.047 (2)	0.054 (2)	0.0014 (15)	0.0033 (15)	0.0048 (19)
C3	0.0319 (17)	0.046 (2)	0.049 (2)	0.0011 (15)	0.0066 (15)	0.0069 (18)
C4	0.041 (3)	0.052 (3)	0.061 (4)	0.000	0.016 (3)	0.000
C5	0.038 (2)	0.061 (3)	0.126 (4)	0.0039 (19)	0.012 (2)	−0.018 (3)
C6	0.069 (4)	0.083 (7)	0.089 (6)	0.009 (5)	0.030 (4)	−0.008 (6)
C6'	0.069 (4)	0.083 (7)	0.089 (6)	0.009 (5)	0.030 (4)	−0.008 (6)
C7	0.036 (2)	0.062 (3)	0.087 (3)	−0.0042 (18)	0.011 (2)	0.007 (2)

Geometric parameters (Å, º) top

Co1—N1	2.012 (3)	C4—H4B	0.9700
Co1—N1ⁱ	2.012 (3)	C5—C6	1.363 (13)
Co1—Cl1	2.2520 (14)	C5—C6'	1.526 (12)
Co1—Cl2	2.2590 (16)	C5—H5A	0.9700
O1—H1C	0.8500	C5—H5B	0.9700
O1—H1D	0.8500	C5—H5'A	0.9700
N1—C1	1.316 (5)	C5—H5'B	0.9700
N1—C3	1.398 (4)	C6—H5'B	1.3943
N2—C1	1.343 (4)	C6—H6A	0.9600
N2—C2	1.374 (4)	C6—H6B	0.9600
N2—H2	0.8600	C6—H6C	0.9600
C1—C5	1.496 (5)	C6'—H6'1	0.9600
C2—C3	1.345 (5)	C6'—H6'2	0.9600
C2—C7	1.500 (5)	C6'—H6'3	0.9600
C3—C4	1.486 (4)	C7—H7A	0.9600
C4—C3ⁱ	1.486 (4)	C7—H7B	0.9600
C4—H4A	0.9700	C7—H7C	0.9600

N1—Co1—N1ⁱ	95.69 (16)	C6—C5—C1	116.0 (6)
N1—Co1—Cl1	113.48 (9)	C1—C5—C6'	117.0 (5)
N1ⁱ—Co1—Cl1	113.48 (9)	C6—C5—H5A	108.3
N1—Co1—Cl2	112.23 (9)	C1—C5—H5A	108.3
N1ⁱ—Co1—Cl2	112.23 (9)	C6—C5—H5B	108.3
Cl1—Co1—Cl2	109.28 (5)	C1—C5—H5B	108.3
H1C—O1—H1D	108.3	H5A—C5—H5B	107.4
C1—N1—C3	106.5 (3)	C1—C5—H5'A	108.5
C1—N1—Co1	130.5 (2)	C6'—C5—H5'A	108.8
C3—N1—Co1	122.3 (2)	C1—C5—H5'B	108.1
C1—N2—C2	108.5 (3)	C6'—C5—H5'B	107.0
C1—N2—H2	125.7	H5'A—C5—H5'B	107.1
C2—N2—H2	125.7	C5—C6—H6A	109.5
N1—C1—N2	110.0 (3)	C5—C6—H6B	109.5
N1—C1—C5	126.6 (3)	C5—C6—H6C	109.5
N2—C1—C5	123.4 (3)	C5—C6'—H6'1	109.5
C3—C2—N2	106.1 (3)	C5—C6'—H6'2	109.5
C3—C2—C7	131.8 (3)	H6'1—C6'—H6'2	109.5
N2—C2—C7	122.0 (3)	C5—C6'—H6'3	109.5
C2—C3—N1	108.8 (3)	H6'1—C6'—H6'3	109.5
C2—C3—C4	128.9 (3)	H6'2—C6'—H6'3	109.5
N1—C3—C4	122.0 (3)	C2—C7—H7A	109.5
C3—C4—C3ⁱ	117.3 (4)	C2—C7—H7B	109.5
C3—C4—H4A	108.0	H7A—C7—H7B	109.5
C3ⁱ—C4—H4A	108.0	C2—C7—H7C	109.5
C3—C4—H4B	108.0	H7A—C7—H7C	109.5
C3ⁱ—C4—H4B	108.0	H7B—C7—H7C	109.5
H4A—C4—H4B	107.2

N1ⁱ—Co1—N1—C1	156.8 (3)	N2—C2—C3—N1	0.8 (4)
Cl1—Co1—N1—C1	−84.6 (4)	C7—C2—C3—N1	−177.8 (4)
Cl2—Co1—N1—C1	39.9 (4)	N2—C2—C3—C4	−173.5 (4)
N1ⁱ—Co1—N1—C3	−12.2 (4)	C7—C2—C3—C4	8.0 (7)
Cl1—Co1—N1—C3	106.5 (3)	C1—N1—C3—C2	−1.0 (4)
Cl2—Co1—N1—C3	−129.0 (3)	Co1—N1—C3—C2	170.3 (2)
C3—N1—C1—N2	0.7 (4)	C1—N1—C3—C4	173.8 (4)
Co1—N1—C1—N2	−169.5 (2)	Co1—N1—C3—C4	−15.0 (5)
C3—N1—C1—C5	−178.7 (4)	C2—C3—C4—C3ⁱ	−138.0 (4)
Co1—N1—C1—C5	11.1 (7)	N1—C3—C4—C3ⁱ	48.3 (7)
C2—N2—C1—N1	−0.3 (5)	N1—C1—C5—C6	−110.0 (7)
C2—N2—C1—C5	179.2 (4)	N2—C1—C5—C6	70.7 (8)
C1—N2—C2—C3	−0.3 (4)	N1—C1—C5—C6'	−153.4 (6)
C1—N2—C2—C7	178.4 (4)	N2—C1—C5—C6'	27.3 (8)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···Cl1	0.85	2.41	3.256 (4)	175
O1—H1D···Cl2ⁱⁱ	0.85	2.29	3.139 (4)	175
N2—H2···O1ⁱⁱⁱ	0.86	2.12	2.959 (3)	165

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

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₁₃H₂₀N₄)]·H₂O
M_r	380.18
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	298
a, b, c (Å)	8.3927 (7), 12.1388 (14), 8.5860 (9)
β (°)	97.045 (1)
V (Å³)	868.11 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.30
Crystal size (mm)	0.40 × 0.30 × 0.22

Data collection
Diffractometer	Bruker SMART 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.625, 0.763
No. of measured, independent and observed [I > 2.0σ(I)] reflections	4313, 1607, 1174
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.114, 1.03
No. of reflections	1607
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.25

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···Cl1	0.85	2.41	3.256 (4)	175
O1—H1D···Cl2ⁱ	0.85	2.29	3.139 (4)	175
N2—H2···O1ⁱⁱ	0.86	2.12	2.959 (3)	165

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

References

Beznischenko, A. O., Makhankova, V. G., Kokozay, V. N., Zubatyuk, R. I. & Shishkin, O. V. (2007). Inorg. Chim. Acta, 10, 1325–1329. CAS Google Scholar
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