Dichlorido[bis­(2-ethyl-5-methyl-1H-imidazol-4-yl-κN ³)methane]­cobalt(II) monohydrate

Abstract

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,

• a = 8.3927 (7) Å

• b = 12.1388 (14) Å

• c = 8.5860 (9) Å

• β = 97.045 (1)°

• V = 868.11 (15) ų

• 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[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Although the atoms were visible in difference Fourier maps, they were included in the subsequent refinement using restraints. The hydrogen atoms were placed geometrically and treated as riding, with O–H = 0.85 Å, N–H = 0.86 Å, and C–H = 0.96 (methyl) or 0.97 Å (methylene) with U_iso(H) = 1.5U_eq(methyl C) or 1.2U_eq (the rest of the parent atoms).

Figures

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.

Crystal data

[CoCl2(C13H20N4)]·H2O	F(000) = 394
Mr = 380.18	Dx = 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

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

Refinement

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(Fo2) + (0.0528P)2 + 0.6331P] where P = (Fo2 + 2Fc2)/3
1607 reflections	(Δ/σ)max < 0.001
109 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	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 (Ų)

	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, °)

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 codes: (i) x, −y+1/2, z.

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···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.