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Acta Cryst. (2009). E65, m149    [ doi:10.1107/S1600536808042906 ]

Hexakis(1-methyl-1H-imidazole-[kappa]N3)cobalt(II) dibromide dihydrate

R. Yao

Abstract top

The asymmetric unit of the title compound, [Co(C4H6N2)6]Br2·2H2O, contains one-half of the centrosymmetric cation, one Br atom and one water molecule. The CoII atom, lying on an inversion center, has a distorted octahedral geometry, defined by six N atoms from six 1-methylimidazole ligands. In the crystal structure, intra- and intermolecular O-H...Br hydrogen bonds link pairs of uncoordinated water molecules and bromide anions.

Comment top

Ionothermal synthesis of novel organic-inorganic hybrid materials are not accessible by traditional hydro- or solvothermal reactions (Rogers & Seddon, 2003, Xie et al., 2008, Lin et al., 2007). We report herein the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) contains one-half of the centrosymmetric cation, one Br atom and one water molecule. The CoII atom lying on the inversion center of the centrosymmetric cation has a distorted octahedral geometry (Table 1). It is coordinated by six N atoms from six 1-methylimidazole ligands, where N3, N3i, N5 and N5i atoms comprise the equatorial plane, and the other two N atoms, N1 and N1i, occupy the axial positions [symmetry code: (i) 1 - x, 2 - y, 1 - z]. The Co-N bonds [average value = 2.1877 (2) Å] are longer than the Ni-N bonds [average value = 2.065 Å] in the reported Ni complex with the same ligand (Baca et al., 2005).

In the crystal structure, intra- and intermolecular O-H···Br hydrogen bonds (Table 2) link the pairs of uncoordinated water and bromide anions (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Lin et al. (2007); Rogers & Seddon (2003); Xie et al. (2008). For a related structure, see: Baca et al. (2005).

Experimental top

CO(NO3)2.6H2O (0.9 g) and N-methyl imidazole (0.5 g) were placed in a Teflon-line stainless-steel autoclave (25 ml) mixed with 1-ethyl-3-methyl- imidazolium (EMIBr)(1.0 g). The mixtures were heated at 423 K for 3 d, followed by cooling slowly to room temperature. The red block crystals were collected.

Refinement top

H atoms were positioned geometrically, with O-H = 0.8544 and 0.8553 Å (for H2O) and C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,O), where x = 1.2 for aromatic H and x = 1.5 for all other H atoms.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level [symmetry code: (i) 1 - x, 2 - y, 1 - z].
[Figure 2] Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
Hexakis(1-methyl-1H-imidazole-κN3)cobalt(II) dibromide dihydrate top
Crystal data top
[Co(C4H6N2)6]Br2·2H2OF(000) = 762
Mr = 747.41Dx = 1.47 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7560 reflections
a = 8.182 (2) Åθ = 2.5–27.1°
b = 13.573 (2) ŵ = 2.93 mm−1
c = 16.2340 (19) ÅT = 298 K
β = 111.12 (4)°Block, red
V = 1681.8 (7) Å30.40 × 0.30 × 0.30 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		3294 independent reflections
Radiation source: fine-focus sealed tube2710 reflections with I > 2σ(I)
graphiteRint = 0.071
φ and ω scansθmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −9→10
Tmin = 0.363, Tmax = 0.416k = −15→16
16985 measured reflectionsl = −20→20
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0649P)2 + 0.2015P]
where P = (Fo2 + 2Fc2)/3
3294 reflections(Δ/σ)max = 0.001
187 parametersΔρmax = 0.86 e Å−3
0 restraintsΔρmin = −0.36 e Å−3
Crystal data top
[Co(C4H6N2)6]Br2·2H2OV = 1681.8 (7) Å3
Mr = 747.41Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.182 (2) ŵ = 2.93 mm−1
b = 13.573 (2) ÅT = 298 K
c = 16.2340 (19) Å0.40 × 0.30 × 0.30 mm
β = 111.12 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3294 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2710 reflections with I > 2σ(I)
Tmin = 0.363, Tmax = 0.416Rint = 0.071
16985 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.103Δρmax = 0.86 e Å−3
S = 1.03Δρmin = −0.36 e Å−3
3294 reflectionsAbsolute structure: ?
187 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Co10.50000.50000.50000.03601 (15)
Br10.78110 (4)0.87845 (2)0.56859 (2)0.05972 (14)
O1W0.4155 (4)0.9171 (2)0.3940 (2)0.1105 (11)
H1WA0.38880.97720.39830.166*
H1WB0.49470.90120.44330.166*
N10.3436 (3)0.62856 (14)0.51072 (14)0.0415 (5)
N20.2626 (3)0.77351 (16)0.54359 (16)0.0490 (5)
N30.7232 (3)0.54470 (15)0.61490 (13)0.0419 (5)
N40.9664 (3)0.61811 (16)0.70086 (15)0.0504 (6)
N50.4033 (3)0.41844 (16)0.58900 (13)0.0433 (5)
N60.3497 (3)0.30035 (18)0.66980 (15)0.0539 (6)
C10.3966 (3)0.71343 (19)0.54940 (17)0.0449 (6)
H1A0.51380.73020.57770.054*
C20.1629 (4)0.6342 (2)0.4783 (2)0.0543 (7)
H2A0.08730.58450.44740.065*
C30.1130 (4)0.7236 (2)0.4986 (2)0.0567 (7)
H3A−0.00120.74630.48450.068*
C40.2759 (5)0.8748 (2)0.5786 (3)0.0792 (12)
H4A0.39710.89200.60750.119*
H4B0.21730.87850.62020.119*
H4C0.22200.91980.53090.119*
C50.8328 (3)0.61851 (19)0.62204 (17)0.0444 (6)
H5A0.81950.66510.57810.053*
C60.7915 (4)0.4943 (2)0.69380 (18)0.0521 (7)
H6A0.74190.43860.70850.063*
C70.9419 (4)0.5382 (2)0.74685 (19)0.0564 (7)
H7A1.01370.51810.80300.068*
C81.1066 (5)0.6909 (3)0.7314 (3)0.0799 (10)
H8A1.09260.73860.68570.120*
H8B1.21780.65860.74570.120*
H8C1.10170.72340.78300.120*
C90.4120 (4)0.3232 (2)0.60596 (17)0.0480 (6)
H9A0.45610.27700.57710.058*
C100.3301 (4)0.4577 (2)0.6465 (2)0.0626 (8)
H10A0.30630.52420.65020.075*
C110.2980 (5)0.3862 (2)0.6964 (2)0.0663 (9)
H11A0.25020.39400.74000.080*
C120.3336 (6)0.2008 (3)0.7011 (2)0.0862 (12)
H12A0.38050.15390.67130.129*
H12B0.21230.18630.68900.129*
H12C0.39730.19700.76360.129*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0387 (3)0.0319 (3)0.0416 (2)0.00008 (18)0.0197 (2)0.00050 (18)
Br10.0506 (2)0.0458 (2)0.0787 (2)−0.00077 (12)0.01838 (17)−0.01020 (13)
O1W0.099 (2)0.096 (2)0.109 (2)0.0179 (17)0.0042 (18)−0.0335 (18)
N10.0405 (12)0.0390 (12)0.0502 (11)0.0004 (9)0.0227 (10)−0.0009 (9)
N20.0508 (14)0.0370 (12)0.0683 (13)0.0033 (9)0.0325 (11)−0.0024 (10)
N30.0450 (12)0.0370 (11)0.0444 (11)0.0026 (9)0.0168 (9)0.0005 (9)
N40.0388 (12)0.0544 (14)0.0536 (13)0.0033 (10)0.0112 (11)0.0010 (10)
N50.0483 (13)0.0421 (12)0.0465 (11)−0.0038 (10)0.0255 (10)−0.0006 (9)
N60.0603 (15)0.0592 (15)0.0490 (12)−0.0095 (12)0.0278 (11)0.0090 (11)
C10.0404 (14)0.0441 (14)0.0560 (14)0.0005 (11)0.0244 (12)−0.0027 (12)
C20.0385 (15)0.0564 (17)0.0677 (17)0.0003 (12)0.0185 (13)−0.0103 (14)
C30.0411 (15)0.0606 (18)0.0697 (17)0.0099 (13)0.0217 (13)−0.0048 (14)
C40.083 (3)0.0403 (18)0.130 (3)0.0009 (15)0.057 (3)−0.0167 (17)
C50.0403 (14)0.0454 (15)0.0463 (14)0.0014 (11)0.0143 (12)0.0047 (11)
C60.0621 (18)0.0408 (15)0.0522 (15)0.0038 (13)0.0191 (14)0.0072 (12)
C70.0588 (19)0.0551 (17)0.0480 (15)0.0161 (14)0.0104 (14)0.0064 (13)
C80.056 (2)0.083 (3)0.082 (2)−0.0173 (18)0.0011 (17)−0.0009 (19)
C90.0593 (17)0.0474 (16)0.0450 (13)−0.0076 (12)0.0284 (12)0.0002 (11)
C100.076 (2)0.0598 (18)0.0685 (18)0.0081 (16)0.0465 (17)0.0004 (15)
C110.074 (2)0.080 (2)0.0643 (18)0.0034 (17)0.0493 (17)0.0025 (16)
C120.121 (3)0.071 (2)0.082 (2)−0.017 (2)0.056 (2)0.0216 (19)
Geometric parameters (Å, °) top
Co1—N3i2.174 (2)N6—C121.466 (4)
Co1—N32.174 (2)C1—H1A0.9300
Co1—N52.182 (2)C2—C31.359 (4)
Co1—N5i2.182 (2)C2—H2A0.9300
Co1—N1i2.207 (2)C3—H3A0.9300
Co1—N12.207 (2)C4—H4A0.9600
O1W—H1WA0.8544C4—H4B0.9600
O1W—H1WB0.8553C4—H4C0.9600
N1—C11.309 (3)C5—H5A0.9300
N1—C21.381 (4)C6—C71.359 (4)
N2—C11.342 (3)C6—H6A0.9300
N2—C31.359 (4)C7—H7A0.9300
N2—C41.477 (4)C8—H8A0.9600
N3—C51.322 (3)C8—H8B0.9600
N3—C61.380 (3)C8—H8C0.9600
N4—C51.351 (3)C9—H9A0.9300
N4—C71.372 (4)C10—C111.349 (4)
N4—C81.458 (4)C10—H10A0.9300
N5—C91.319 (4)C11—H11A0.9300
N5—C101.384 (3)C12—H12A0.9600
N6—C91.346 (3)C12—H12B0.9600
N6—C111.362 (4)C12—H12C0.9600
N3i—Co1—N3180.0N2—C3—C2106.5 (2)
N3i—Co1—N591.93 (8)N2—C3—H3A126.8
N3—Co1—N588.07 (8)C2—C3—H3A126.8
N3i—Co1—N5i88.07 (8)N2—C4—H4A109.5
N3—Co1—N5i91.93 (8)N2—C4—H4B109.5
N5—Co1—N5i180.0H4A—C4—H4B109.5
N3i—Co1—N1i92.48 (8)N2—C4—H4C109.5
N3—Co1—N1i87.52 (8)H4A—C4—H4C109.5
N5—Co1—N1i90.57 (8)H4B—C4—H4C109.5
N5i—Co1—N1i89.43 (8)N3—C5—N4111.9 (2)
N3i—Co1—N187.52 (8)N3—C5—H5A124.1
N3—Co1—N192.48 (8)N4—C5—H5A124.1
N5—Co1—N189.43 (8)C7—C6—N3110.1 (3)
N5i—Co1—N190.57 (8)C7—C6—H6A125.0
N1i—Co1—N1180.00 (11)N3—C6—H6A125.0
H1WA—O1W—H1WB107.2C6—C7—N4106.2 (2)
C1—N1—C2105.0 (2)C6—C7—H7A126.9
C1—N1—Co1129.22 (18)N4—C7—H7A126.9
C2—N1—Co1125.80 (17)N4—C8—H8A109.5
C1—N2—C3106.9 (2)N4—C8—H8B109.5
C1—N2—C4126.4 (2)H8A—C8—H8B109.5
C3—N2—C4126.7 (2)N4—C8—H8C109.5
C5—N3—C6105.0 (2)H8A—C8—H8C109.5
C5—N3—Co1128.35 (17)H8B—C8—H8C109.5
C6—N3—Co1126.31 (18)N5—C9—N6112.3 (2)
C5—N4—C7106.9 (2)N5—C9—H9A123.8
C5—N4—C8126.1 (3)N6—C9—H9A123.8
C7—N4—C8127.0 (3)C11—C10—N5110.7 (3)
C9—N5—C10103.9 (2)C11—C10—H10A124.7
C9—N5—Co1129.10 (17)N5—C10—H10A124.7
C10—N5—Co1126.8 (2)C10—C11—N6106.0 (2)
C9—N6—C11107.1 (2)C10—C11—H11A127.0
C9—N6—C12125.8 (3)N6—C11—H11A127.0
C11—N6—C12127.0 (2)N6—C12—H12A109.5
N1—C1—N2112.3 (2)N6—C12—H12B109.5
N1—C1—H1A123.8H12A—C12—H12B109.5
N2—C1—H1A123.8N6—C12—H12C109.5
C3—C2—N1109.4 (3)H12A—C12—H12C109.5
C3—C2—H2A125.3H12B—C12—H12C109.5
N1—C2—H2A125.3
N3i—Co1—N1—C1−157.5 (2)C3—N2—C1—N10.5 (3)
N3—Co1—N1—C122.5 (2)C4—N2—C1—N1−178.9 (3)
N5—Co1—N1—C1110.5 (2)C1—N1—C2—C30.3 (3)
N5i—Co1—N1—C1−69.5 (2)Co1—N1—C2—C3178.83 (19)
N3i—Co1—N1—C224.3 (2)C1—N2—C3—C2−0.3 (3)
N3—Co1—N1—C2−155.7 (2)C4—N2—C3—C2179.1 (3)
N5—Co1—N1—C2−67.7 (2)N1—C2—C3—N20.0 (3)
N5i—Co1—N1—C2112.3 (2)C6—N3—C5—N4−0.1 (3)
N5—Co1—N3—C5−161.6 (2)Co1—N3—C5—N4−173.74 (17)
N5i—Co1—N3—C518.4 (2)C7—N4—C5—N30.7 (3)
N1i—Co1—N3—C5107.7 (2)C8—N4—C5—N3−177.7 (3)
N1—Co1—N3—C5−72.3 (2)C5—N3—C6—C7−0.5 (3)
N5—Co1—N3—C626.0 (2)Co1—N3—C6—C7173.29 (18)
N5i—Co1—N3—C6−154.0 (2)N3—C6—C7—N40.9 (3)
N1i—Co1—N3—C6−64.6 (2)C5—N4—C7—C6−0.9 (3)
N1—Co1—N3—C6115.4 (2)C8—N4—C7—C6177.4 (3)
N3i—Co1—N5—C978.8 (2)C10—N5—C9—N6−0.1 (3)
N3—Co1—N5—C9−101.2 (2)Co1—N5—C9—N6175.28 (18)
N1i—Co1—N5—C9−13.7 (2)C11—N6—C9—N5−0.3 (3)
N1—Co1—N5—C9166.3 (2)C12—N6—C9—N5177.0 (3)
N3i—Co1—N5—C10−106.8 (2)C9—N5—C10—C110.4 (4)
N3—Co1—N5—C1073.2 (2)Co1—N5—C10—C11−175.1 (2)
N1i—Co1—N5—C10160.7 (2)N5—C10—C11—N6−0.6 (4)
N1—Co1—N5—C10−19.3 (2)C9—N6—C11—C100.5 (4)
C2—N1—C1—N2−0.4 (3)C12—N6—C11—C10−176.8 (3)
Co1—N1—C1—N2−178.95 (16)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···Br1ii0.852.573.371 (3)157
O1W—H1WB···Br10.862.513.338 (3)164
Symmetry codes: (ii) −x+1, −y+2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Co1—N32.174 (2)Co1—N12.207 (2)
Co1—N52.182 (2)
N3i—Co1—N3180.0N3—Co1—N192.48 (8)
N3—Co1—N588.07 (8)N5—Co1—N189.43 (8)
N3—Co1—N5i91.93 (8)N5i—Co1—N190.57 (8)
N5—Co1—N5i180.0N1i—Co1—N1180.00 (11)
N3i—Co1—N187.52 (8)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···Br1ii0.852.573.371 (3)157
O1W—H1WB···Br10.862.513.338 (3)164
Symmetry codes: (ii) −x+1, −y+2, −z+1.
Acknowledgements top

This work was supported by the National Natural Science Foundation of China (grant No. 20871039).

references
References top

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