Acta Cryst. (2008). E64, m308 [ doi:10.1107/S160053680706833X ]
There are independent cations and four chloride anions in the crystal structure of the title complex, [Co(C6H6N4)2(H2O)2]Cl2. In each cation, the CoII cation is coordinated by four N atoms from two biimidazole and two O atoms of two water molecules; one Co atom is at a position of site symmetry m, the other at a position of site symmetry 2/m. All Cl- ions and water molecules are also located on the mirror plane. Each structural unit is connected through O-H
Cl and N-HCl intermolecular hydrogen bonds, forming a three-dimensional supramolecular structure.
The 2,2'–biimidazole was prepared according to (Fieselmann et al., 1978). 2,2'–Biimidazole (0.1 mmol) was mixed with 0.1 mmol CoCl2.6H2O in solution. After 10 min of stirring, the precipitate was filtered off, the resulting clear solution was allowed to stand at room temperature, after a few days yellow block–shaped crystals were obtained.
H atoms of water molecules are located in a difference map and refined with distance restraints of O—H = 0.86 (1) Å.
Data collection: SMART (Bruker, 2001); cell refinement: SMART (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 (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
![[Figure 1]](./rk2059fig1thm.gif)
| Fig. 1. The molecular structure of the title complex with the atom labeling scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as small spheres of arbitrary radius. |
![[Figure 2]](./rk2059fig2thm.gif)
| Fig. 2. The packing diagram of title complex - viewed down the b axis. Dashed lines show hydrogen bonds. |
| [Co(C6H6N4)2(H2O)2]Cl2 | F000 = 1326 |
| Mr = 434.16 | Dx = 1.633 Mg m−3 |
| Monoclinic, C2/m | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2y | Cell parameters from 2062 reflections |
| a = 22.037 (3) Å | θ = 2.7–26.7º |
| b = 12.5321 (17) Å | µ = 1.30 mm−1 |
| c = 9.6421 (13) Å | T = 298 (2) K |
| β = 95.848 (2)º | Block, yellow |
| V = 2649.0 (6) Å3 | 0.16 × 0.12 × 0.08 mm |
| Z = 6 |
| Bruker SMART CCD area-detector diffractometer | 3205 independent reflections |
| Radiation source: fine–focus sealed tube | 2291 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.026 |
| T = 298(2) K | θmax = 27.7º |
| φ and ω scans | θmin = 1.9º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −24→28 |
| Tmin = 0.819, Tmax = 0.903 | k = −16→15 |
| 8119 measured reflections | l = −11→12 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.033 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0613P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max = 0.001 |
| 3205 reflections | Δρmax = 0.29 e Å−3 |
| 200 parameters | Δρmin = −0.24 e Å−3 |
| 6 restraints | Extinction correction: none |
| Primary atom site location: structure-invariant direct methods |
| [Co(C6H6N4)2(H2O)2]Cl2 | V = 2649.0 (6) Å3 |
| Mr = 434.16 | Z = 6 |
| Monoclinic, C2/m | Mo Kα |
| a = 22.037 (3) Å | µ = 1.30 mm−1 |
| b = 12.5321 (17) Å | T = 298 (2) K |
| c = 9.6421 (13) Å | 0.16 × 0.12 × 0.08 mm |
| β = 95.848 (2)º |
| Bruker SMART CCD area-detector diffractometer | 3205 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2291 reflections with I > 2σ(I) |
| Tmin = 0.819, Tmax = 0.903 | Rint = 0.026 |
| 8119 measured reflections |
| R[F2 > 2σ(F2)] = 0.033 | 6 restraints |
| wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.05 | Δρmax = 0.29 e Å−3 |
| 3205 reflections | Δρmin = −0.24 e Å−3 |
| 200 parameters |
Geometry. All s.u.'s (except the s.u.'s in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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. |
| x | y | z | Uiso*/Ueq | ||
| Co1 | 0.0000 | 0.0000 | 0.5000 | 0.03508 (16) | |
| Co2 | 0.332770 (17) | 0.0000 | 0.08867 (4) | 0.03888 (14) | |
| O1W | 0.09155 (10) | 0.0000 | 0.5815 (2) | 0.0493 (6) | |
| H1A | 0.1231 (9) | 0.0000 | 0.536 (3) | 0.049 (10)* | |
| H1B | 0.0984 (16) | 0.0000 | 0.6706 (11) | 0.071 (12)* | |
| O2W | 0.42387 (11) | 0.0000 | 0.0446 (2) | 0.0836 (10) | |
| H2B | 0.4517 (13) | 0.0000 | 0.114 (3) | 0.090 (14)* | |
| H2C | 0.4321 (16) | 0.0000 | −0.0407 (16) | 0.074 (12)* | |
| O3W | 0.24136 (10) | 0.0000 | 0.1289 (2) | 0.0544 (6) | |
| H3B | 0.2314 (15) | 0.0000 | 0.2127 (16) | 0.065 (12)* | |
| H3C | 0.2115 (12) | 0.0000 | 0.064 (3) | 0.083 (13)* | |
| N1 | 0.01986 (7) | 0.10903 (15) | 0.33535 (16) | 0.0378 (4) | |
| N2 | 0.35622 (8) | 0.10868 (16) | 0.25695 (16) | 0.0413 (4) | |
| N3 | 0.30994 (8) | 0.10867 (16) | −0.07959 (16) | 0.0420 (4) | |
| N4 | 0.05671 (8) | 0.12463 (16) | 0.13273 (17) | 0.0458 (5) | |
| H4B | 0.0719 | 0.1074 | 0.0571 | 0.055* | |
| N5 | 0.38823 (8) | 0.12580 (16) | 0.47968 (18) | 0.0471 (5) | |
| H5B | 0.4007 | 0.1093 | 0.5644 | 0.056* | |
| N6 | 0.27788 (8) | 0.12601 (17) | −0.30166 (17) | 0.0494 (5) | |
| H6B | 0.2653 | 0.1097 | −0.3864 | 0.059* | |
| C1 | 0.04173 (8) | 0.05762 (17) | 0.23184 (19) | 0.0363 (5) | |
| C2 | 0.02053 (10) | 0.2150 (2) | 0.2986 (2) | 0.0446 (5) | |
| H2A | 0.0073 | 0.2710 | 0.3511 | 0.054* | |
| C3 | 0.04345 (11) | 0.2251 (2) | 0.1741 (2) | 0.0516 (6) | |
| H3A | 0.0490 | 0.2883 | 0.1264 | 0.062* | |
| C4 | 0.37410 (9) | 0.05749 (18) | 0.37374 (19) | 0.0379 (5) | |
| C5 | 0.35969 (10) | 0.2148 (2) | 0.2901 (2) | 0.0509 (6) | |
| H5A | 0.3502 | 0.2704 | 0.2277 | 0.061* | |
| C6 | 0.37892 (11) | 0.2268 (2) | 0.4267 (2) | 0.0546 (6) | |
| H6A | 0.3847 | 0.2907 | 0.4752 | 0.066* | |
| C7 | 0.29209 (9) | 0.05720 (19) | −0.19698 (19) | 0.0397 (5) | |
| C8 | 0.30664 (10) | 0.2147 (2) | −0.1125 (2) | 0.0526 (6) | |
| H8A | 0.3164 | 0.2702 | −0.0501 | 0.063* | |
| C9 | 0.28699 (10) | 0.2271 (2) | −0.2492 (3) | 0.0564 (6) | |
| H9A | 0.2809 | 0.2910 | −0.2976 | 0.068* | |
| Cl1 | 0.12670 (4) | 0.0000 | 0.90521 (8) | 0.0602 (3) | |
| Cl2 | 0.21127 (4) | 0.0000 | 0.43563 (7) | 0.0551 (2) | |
| Cl3 | 0.04319 (4) | 0.5000 | 0.25997 (7) | 0.0501 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Co1 | 0.0382 (3) | 0.0427 (4) | 0.0243 (3) | 0.000 | 0.0025 (2) | 0.000 |
| Co2 | 0.0385 (2) | 0.0531 (3) | 0.0243 (2) | 0.000 | −0.00013 (16) | 0.000 |
| O1W | 0.0386 (13) | 0.0814 (19) | 0.0279 (12) | 0.000 | 0.0031 (10) | 0.000 |
| O2W | 0.0386 (14) | 0.181 (3) | 0.0307 (14) | 0.000 | 0.0011 (11) | 0.000 |
| O3W | 0.0406 (13) | 0.093 (2) | 0.0289 (12) | 0.000 | 0.0017 (10) | 0.000 |
| N1 | 0.0417 (10) | 0.0429 (12) | 0.0285 (8) | −0.0017 (8) | 0.0025 (7) | −0.0009 (8) |
| N2 | 0.0435 (10) | 0.0495 (13) | 0.0293 (9) | −0.0028 (9) | −0.0034 (7) | 0.0027 (8) |
| N3 | 0.0447 (10) | 0.0503 (13) | 0.0304 (9) | −0.0030 (9) | 0.0008 (7) | 0.0019 (8) |
| N4 | 0.0582 (12) | 0.0493 (13) | 0.0309 (9) | −0.0039 (10) | 0.0096 (8) | 0.0030 (8) |
| N5 | 0.0574 (12) | 0.0506 (13) | 0.0307 (9) | −0.0015 (10) | −0.0080 (8) | −0.0006 (9) |
| N6 | 0.0546 (12) | 0.0630 (15) | 0.0296 (9) | −0.0007 (10) | −0.0002 (8) | 0.0054 (9) |
| C1 | 0.0365 (11) | 0.0453 (13) | 0.0265 (10) | −0.0024 (9) | 0.0003 (8) | 0.0024 (9) |
| C2 | 0.0488 (13) | 0.0448 (15) | 0.0397 (12) | −0.0014 (11) | 0.0018 (9) | −0.0037 (10) |
| C3 | 0.0629 (15) | 0.0451 (16) | 0.0468 (14) | −0.0034 (13) | 0.0055 (11) | 0.0066 (11) |
| C4 | 0.0372 (11) | 0.0476 (13) | 0.0283 (10) | −0.0022 (10) | −0.0003 (8) | −0.0015 (9) |
| C5 | 0.0551 (14) | 0.0509 (16) | 0.0445 (13) | −0.0044 (12) | −0.0059 (10) | 0.0076 (11) |
| C6 | 0.0637 (15) | 0.0473 (16) | 0.0504 (14) | −0.0053 (13) | −0.0066 (11) | −0.0051 (12) |
| C7 | 0.0364 (11) | 0.0540 (14) | 0.0287 (10) | 0.0006 (10) | 0.0030 (8) | 0.0037 (9) |
| C8 | 0.0546 (14) | 0.0570 (18) | 0.0459 (13) | −0.0091 (12) | 0.0040 (11) | 0.0014 (12) |
| C9 | 0.0639 (16) | 0.0559 (18) | 0.0489 (14) | −0.0009 (13) | 0.0032 (12) | 0.0097 (12) |
| Cl1 | 0.0536 (5) | 0.0994 (8) | 0.0274 (4) | 0.000 | 0.0029 (3) | 0.000 |
| Cl2 | 0.0528 (5) | 0.0848 (7) | 0.0280 (4) | 0.000 | 0.0056 (3) | 0.000 |
| Cl3 | 0.0622 (5) | 0.0554 (6) | 0.0305 (4) | 0.000 | −0.0065 (3) | 0.000 |
| Co1—O1W | 2.089 (2) | N3—C8 | 1.366 (3) |
| Co1—O1Wi | 2.089 (2) | N4—C1 | 1.338 (3) |
| Co1—N1ii | 2.1727 (17) | N4—C3 | 1.362 (3) |
| Co1—N1i | 2.1727 (17) | N4—H4B | 0.8600 |
| Co1—N1iii | 2.1727 (17) | N5—C4 | 1.345 (3) |
| Co1—N1 | 2.1727 (17) | N5—C6 | 1.372 (3) |
| Co2—O3W | 2.090 (2) | N5—H5B | 0.8600 |
| Co2—O2W | 2.094 (2) | N6—C7 | 1.340 (3) |
| Co2—N3iii | 2.1386 (18) | N6—C9 | 1.371 (3) |
| Co2—N3 | 2.1386 (18) | N6—H6B | 0.8600 |
| Co2—N2 | 2.1410 (18) | C1—C1iii | 1.444 (4) |
| Co2—N2iii | 2.1410 (18) | C2—C3 | 1.355 (3) |
| O1W—H1A | 0.857 (10) | C2—H2A | 0.9300 |
| O1W—H1B | 0.857 (10) | C3—H3A | 0.9300 |
| O2W—H2B | 0.86 (3) | C4—C4iii | 1.441 (4) |
| O2W—H2C | 0.860 (10) | C5—C6 | 1.351 (3) |
| O3W—H3B | 0.859 (10) | C5—H5A | 0.9300 |
| O3W—H3C | 0.86 (3) | C6—H6A | 0.9300 |
| N1—C1 | 1.320 (2) | C7—C7iii | 1.434 (5) |
| N1—C2 | 1.374 (3) | C8—C9 | 1.354 (3) |
| N2—C4 | 1.321 (3) | C8—H8A | 0.9300 |
| N2—C5 | 1.368 (3) | C9—H9A | 0.9300 |
| N3—C7 | 1.327 (3) | ||
| O1W—Co1—O1Wi | 180.00 (4) | C4—N2—C5 | 105.57 (17) |
| O1W—Co1—N1ii | 89.08 (6) | C4—N2—Co2 | 111.42 (15) |
| O1Wi—Co1—N1ii | 90.92 (6) | C5—N2—Co2 | 143.01 (14) |
| O1W—Co1—N1i | 89.08 (6) | C7—N3—C8 | 105.70 (18) |
| O1Wi—Co1—N1i | 90.92 (6) | C7—N3—Co2 | 111.34 (16) |
| N1ii—Co1—N1i | 77.93 (9) | C8—N3—Co2 | 142.96 (15) |
| O1W—Co1—N1iii | 90.92 (6) | C1—N4—C3 | 107.16 (18) |
| O1Wi—Co1—N1iii | 89.08 (6) | C1—N4—H4B | 126.4 |
| N1ii—Co1—N1iii | 180.0 | C3—N4—H4B | 126.4 |
| N1i—Co1—N1iii | 102.07 (9) | C4—N5—C6 | 106.87 (18) |
| O1W—Co1—N1 | 90.92 (6) | C4—N5—H5B | 126.6 |
| O1Wi—Co1—N1 | 89.08 (6) | C6—N5—H5B | 126.6 |
| N1ii—Co1—N1 | 102.07 (9) | C7—N6—C9 | 107.62 (19) |
| N1i—Co1—N1 | 180.0 | C7—N6—H6B | 126.2 |
| N1iii—Co1—N1 | 77.93 (9) | C9—N6—H6B | 126.2 |
| O3W—Co2—O2W | 179.00 (9) | N1—C1—N4 | 111.7 (2) |
| O3W—Co2—N3iii | 89.09 (6) | N1—C1—C1iii | 119.22 (12) |
| O2W—Co2—N3iii | 90.14 (7) | N4—C1—C1iii | 128.86 (12) |
| O3W—Co2—N3 | 89.09 (6) | C3—C2—N1 | 109.5 (2) |
| O2W—Co2—N3 | 90.14 (7) | C3—C2—H2A | 125.2 |
| N3iii—Co2—N3 | 79.11 (10) | N1—C2—H2A | 125.2 |
| O3W—Co2—N2 | 91.27 (7) | C2—C3—N4 | 106.4 (2) |
| O2W—Co2—N2 | 89.50 (7) | C2—C3—H3A | 126.8 |
| N3iii—Co2—N2 | 179.64 (7) | N4—C3—H3A | 126.8 |
| N3—Co2—N2 | 100.94 (7) | N2—C4—N5 | 111.4 (2) |
| O3W—Co2—N2iii | 91.27 (7) | N2—C4—C4iii | 119.06 (12) |
| O2W—Co2—N2iii | 89.50 (7) | N5—C4—C4iii | 129.54 (12) |
| N3iii—Co2—N2iii | 100.94 (7) | C6—C5—N2 | 109.9 (2) |
| N3—Co2—N2iii | 179.64 (7) | C6—C5—H5A | 125.0 |
| N2—Co2—N2iii | 79.01 (10) | N2—C5—H5A | 125.0 |
| Co1—O1W—H1A | 128 (2) | C5—C6—N5 | 106.3 (2) |
| Co1—O1W—H1B | 116 (2) | C5—C6—H6A | 126.9 |
| H1A—O1W—H1B | 116 (3) | N5—C6—H6A | 126.9 |
| Co2—O2W—H2B | 118 (3) | N3—C7—N6 | 110.8 (2) |
| Co2—O2W—H2C | 120 (2) | N3—C7—C7iii | 119.08 (13) |
| H2B—O2W—H2C | 123 (4) | N6—C7—C7iii | 130.05 (13) |
| Co2—O3W—H3B | 121 (2) | C9—C8—N3 | 110.0 (2) |
| Co2—O3W—H3C | 123 (3) | C9—C8—H8A | 125.0 |
| H3B—O3W—H3C | 116 (3) | N3—C8—H8A | 125.0 |
| C1—N1—C2 | 105.19 (17) | C8—C9—N6 | 105.8 (2) |
| C1—N1—Co1 | 111.22 (14) | C8—C9—H9A | 127.1 |
| C2—N1—Co1 | 143.52 (14) | N6—C9—H9A | 127.1 |
| Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y, −z+1; (iii) x, −y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4B···Cl1iv | 0.86 | 2.40 | 3.213 (2) | 157 |
| N5—H5B···Cl3v | 0.86 | 2.42 | 3.2091 (19) | 153 |
| N6—H6B···Cl2iv | 0.86 | 2.42 | 3.210 (2) | 154 |
| O3W—H3C···Cl1iv | 0.86 (3) | 2.29 (3) | 3.150 (2) | 175 (4) |
| O2W—H2B···Cl3vi | 0.86 (3) | 2.34 (3) | 3.180 (3) | 166 (4) |
| O2W—H2C···Cl3vii | 0.860 (10) | 2.236 (11) | 3.096 (3) | 178 (3) |
| O1W—H1A···Cl2 | 0.857 (10) | 2.259 (11) | 3.114 (2) | 175 (3) |
| O1W—H1B···Cl1 | 0.857 (10) | 2.285 (11) | 3.139 (2) | 174 (3) |
| O3W—H3B···Cl2 | 0.859 (10) | 2.239 (11) | 3.096 (2) | 177 (3) |
| Symmetry codes: (iv) x, y, z−1; (v) −x+1/2, −y+1/2, −z+1; (vi) x+1/2, y−1/2, z; (vii) −x+1/2, −y+1/2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4B···Cl1i | 0.86 | 2.40 | 3.213 (2) | 157 |
| N5—H5B···Cl3ii | 0.86 | 2.42 | 3.2091 (19) | 153 |
| N6—H6B···Cl2i | 0.86 | 2.42 | 3.210 (2) | 154 |
| O3W—H3C···Cl1i | 0.86 (3) | 2.29 (3) | 3.150 (2) | 175 (4) |
| O2W—H2B···Cl3iii | 0.86 (3) | 2.34 (3) | 3.180 (3) | 166 (4) |
| O2W—H2C···Cl3iv | 0.860 (10) | 2.236 (11) | 3.096 (3) | 178 (3) |
| O1W—H1A···Cl2 | 0.857 (10) | 2.259 (11) | 3.114 (2) | 175 (3) |
| O1W—H1B···Cl1 | 0.857 (10) | 2.285 (11) | 3.139 (2) | 174 (3) |
| O3W—H3B···Cl2 | 0.859 (10) | 2.239 (11) | 3.096 (2) | 177 (3) |
| Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, −y+1/2, −z+1; (iii) x+1/2, y−1/2, z; (iv) −x+1/2, −y+1/2, −z. |
Barquin, M., Gonzalez Garmendia, M. J. & Bellido, V. (2003). Transition Met. Chem. 28, 356–360.
Bruker (1997). SHELXTL. Version 5.10. Bruker AXS inc., Madison, Wisconsin, USA.
Bruker (2001). SAINT and SMART. Bruker AXS inc., Madison, Wisconsin, USA.
Fieselmann, B. F., Hendrickson, D. N. & Stucky, G. D. (1978). Inorg. Chem. 17, 333–334.
Hirotoshi, M. & Eisaku, M. (2005). J. Theor. Cancer Chem. 4, 2078–2084.
Roth, J. P., Lovell, S. & Mayer, J. M. (2000). J. Am. Chem. Soc. 122, 5486–5498.
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Tadokoro, M. & Nakasuji, K. (2000). Coord. Chem. Rev. 198, 205–218.
The imidazole coordinated complexes have various structures and extensive uses in the field of catalysis, materials and bioactivity (Barquin et al., 2003; Hirotoshi & Eisaku, 2005). The bis(2,2'–biimidazole)dihydrate cobalt dichloride was synthesized. The 2,2'–biimidazole is an interesting dicyclo–ligand of containing four N atoms: the two N atoms forming coordinate bonds and the other two - uncoordinated N atoms of biimidazole form N—H···Cl hydrogen bonds. This crystal structure are constructed by intermolecular hydrogen bonds (Tadokoro & Nakasuji, 2000; Roth et al., 2000).
The average bond distance Co—N is of 2.1563 (18) Å, the average bond angle N—Co—N is 101.50 (8)°, the average bond distance Co—O is 2.091 (2) Å. These parameters show, that the polihedron configuration is distorted octahedron (Fig. 1.). The biimidazole moieties and Cl atoms are linked by N—H···Cl and the water molecules and Cl atoms are linked by O—H···Cl hydrogen bonds, which shown on Fig. 2.