supplementary materials
Bis(2-aminobenzonitrile)tetraaquacobalt(II) dichloride
A mixture of 2-aminobenzonitrile (0.1 mmol) and CoCl2 (0.1 mmol) and water
(1 ml) sealed in a glass tube were maintained at 343 K. Crystals suitable for
X-ray analysis were obtained after 5 d.
H atoms attached to C atoms were located geometrically and treated as riding
with C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C).
H atoms bonded to O and N atoms were located in a difference Fourier map
and refined with distance restraints of O—H = 0.85±0.03 and N—H =
0.89±0.03 Å, Uiso(H) = 1.5Ueq(O,N).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Bis(2-aminobenzonitrile)tetraaquacobalt(II) dichloride
top
Crystal data top
| [Co(C7H6N2)2(H2O)4]Cl2 | F(000) = 450 |
| Mr = 438.17 | Dx = 1.486 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 1872 reflections |
| a = 12.492 (3) Å | θ = 3.4–27.5° |
| b = 6.5864 (13) Å | µ = 1.17 mm−1 |
| c = 12.608 (3) Å | T = 298 K |
| β = 109.24 (3)° | Block, red |
| V = 979.4 (3) Å3 | 0.35 × 0.30 × 0.15 mm |
| Z = 2 | |
Data collection top
Rigaku Mercury2
diffractometer | 2227 independent reflections |
| Radiation source: fine-focus sealed tube | 1872 reflections with I > 2σ(I) |
| graphite | Rint = 0.038 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 27.5°, θmin = 3.4° |
| ω scan | h = −16→16 |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005) | k = −8→8 |
| Tmin = 0.732, Tmax = 0.871 | l = −16→16 |
| 9255 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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.072 | H-atom parameters constrained |
| S = 1.13 | w = 1/[σ2(Fo2) + (0.0216P)2 + 0.2674P]
where P = (Fo2 + 2Fc2)/3 |
| 2227 reflections | (Δ/σ)max < 0.001 |
| 115 parameters | Δρmax = 0.30 e Å−3 |
| 4 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
| [Co(C7H6N2)2(H2O)4]Cl2 | V = 979.4 (3) Å3 |
| Mr = 438.17 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 12.492 (3) Å | µ = 1.17 mm−1 |
| b = 6.5864 (13) Å | T = 298 K |
| c = 12.608 (3) Å | 0.35 × 0.30 × 0.15 mm |
| β = 109.24 (3)° | |
Data collection top
Rigaku Mercury2
diffractometer | 2227 independent reflections |
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005) | 1872 reflections with I > 2σ(I) |
| Tmin = 0.732, Tmax = 0.871 | Rint = 0.038 |
| 9255 measured reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
| wR(F2) = 0.072 | Δρmax = 0.30 e Å−3 |
| S = 1.13 | Δρmin = −0.35 e Å−3 |
| 2227 reflections | Absolute structure: ? |
| 115 parameters | Flack parameter: ? |
| 4 restraints | Rogers 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| | x | y | z | Uiso*/Ueq | |
| Co1 | 0.0000 | 0.0000 | 0.5000 | 0.02435 (11) | |
| Cl1 | 0.62659 (4) | 0.99536 (7) | 0.26701 (4) | 0.04265 (15) | |
| O1W | −0.10877 (11) | 0.0642 (2) | 0.33800 (10) | 0.0348 (3) | |
| H1WA | −0.1770 | 0.0308 | 0.3213 | 0.052* | |
| H1WB | −0.1014 | 0.1829 | 0.3137 | 0.052* | |
| N2 | 0.26587 (14) | 0.6024 (3) | 0.55539 (14) | 0.0406 (4) | |
| H2A | 0.2560 | 0.4991 | 0.5944 | 0.061* | |
| H2B | 0.2997 | 0.7116 | 0.5990 | 0.061* | |
| O2W | 0.03539 (12) | −0.2770 (2) | 0.44423 (12) | 0.0469 (4) | |
| H2WA | 0.1036 | −0.3409 | 0.4710 | 0.070* | |
| H2WB | −0.0087 | −0.3427 | 0.3854 | 0.070* | |
| C7 | 0.33808 (16) | 0.3068 (3) | 0.33515 (15) | 0.0366 (4) | |
| H7 | 0.3225 | 0.1808 | 0.3001 | 0.044* | |
| C2 | 0.28925 (14) | 0.3621 (3) | 0.41754 (14) | 0.0281 (4) | |
| C3 | 0.31432 (14) | 0.5491 (3) | 0.47396 (15) | 0.0292 (4) | |
| N1 | 0.14159 (13) | 0.1374 (2) | 0.46523 (13) | 0.0365 (4) | |
| C5 | 0.43102 (16) | 0.6305 (4) | 0.35985 (18) | 0.0451 (5) | |
| H5 | 0.4774 | 0.7220 | 0.3393 | 0.054* | |
| C4 | 0.38513 (16) | 0.6849 (3) | 0.44191 (17) | 0.0389 (5) | |
| H4 | 0.4012 | 0.8116 | 0.4760 | 0.047* | |
| C1 | 0.20887 (15) | 0.2307 (3) | 0.44319 (15) | 0.0297 (4) | |
| C6 | 0.40921 (17) | 0.4417 (4) | 0.30739 (17) | 0.0436 (5) | |
| H6 | 0.4424 | 0.4067 | 0.2539 | 0.052* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Co1 | 0.02442 (18) | 0.02295 (18) | 0.02613 (18) | −0.00363 (13) | 0.00896 (14) | −0.00016 (13) |
| Cl1 | 0.0385 (3) | 0.0368 (3) | 0.0443 (3) | −0.0048 (2) | 0.0024 (2) | −0.0060 (2) |
| O1W | 0.0330 (7) | 0.0356 (7) | 0.0326 (7) | −0.0032 (6) | 0.0067 (6) | 0.0048 (6) |
| N2 | 0.0416 (9) | 0.0438 (10) | 0.0384 (9) | −0.0046 (8) | 0.0157 (8) | −0.0119 (8) |
| O2W | 0.0411 (8) | 0.0367 (8) | 0.0517 (9) | 0.0072 (6) | 0.0001 (7) | −0.0150 (7) |
| C7 | 0.0305 (10) | 0.0490 (12) | 0.0309 (10) | 0.0002 (9) | 0.0110 (8) | −0.0040 (9) |
| C2 | 0.0214 (8) | 0.0363 (10) | 0.0270 (9) | −0.0044 (8) | 0.0084 (7) | 0.0020 (8) |
| C3 | 0.0222 (9) | 0.0344 (10) | 0.0284 (9) | 0.0000 (7) | 0.0049 (7) | 0.0017 (7) |
| N1 | 0.0336 (8) | 0.0413 (9) | 0.0365 (9) | −0.0094 (8) | 0.0139 (7) | 0.0002 (7) |
| C5 | 0.0287 (10) | 0.0601 (14) | 0.0461 (12) | −0.0085 (10) | 0.0117 (9) | 0.0209 (11) |
| C4 | 0.0295 (10) | 0.0354 (10) | 0.0467 (12) | −0.0068 (8) | 0.0058 (9) | 0.0047 (9) |
| C1 | 0.0286 (9) | 0.0333 (10) | 0.0270 (9) | −0.0031 (8) | 0.0089 (8) | −0.0022 (7) |
| C6 | 0.0325 (10) | 0.0703 (15) | 0.0325 (11) | 0.0001 (10) | 0.0167 (9) | 0.0073 (10) |
Geometric parameters (Å, °) top
| Co1—O1W | 2.0899 (14) | C7—C6 | 1.381 (3) |
| Co1—O1Wi | 2.0899 (14) | C7—C2 | 1.415 (2) |
| Co1—O2W | 2.0550 (13) | C7—H7 | 0.9300 |
| Co1—O2Wi | 2.0550 (13) | C2—C3 | 1.405 (3) |
| Co1—N1 | 2.1566 (15) | C2—C1 | 1.441 (2) |
| Co1—N1i | 2.1566 (15) | C3—C4 | 1.408 (3) |
| O1W—H1WA | 0.8377 | N1—C1 | 1.147 (2) |
| O1W—H1WB | 0.8551 | C5—C4 | 1.385 (3) |
| N2—C3 | 1.398 (2) | C5—C6 | 1.392 (3) |
| N2—H2A | 0.8715 | C5—H5 | 0.9300 |
| N2—H2B | 0.9196 | C4—H4 | 0.9300 |
| O2W—H2WA | 0.9097 | C6—H6 | 0.9300 |
| O2W—H2WB | 0.8784 | | |
| | | |
| O2W—Co1—O2Wi | 180.00 (8) | Co1—O2W—H2WB | 125.5 |
| O2W—Co1—O1W | 89.38 (5) | H2WA—O2W—H2WB | 109.6 |
| O2Wi—Co1—O1W | 90.62 (5) | C6—C7—C2 | 119.31 (19) |
| O2W—Co1—O1Wi | 90.62 (5) | C6—C7—H7 | 120.3 |
| O2Wi—Co1—O1Wi | 89.38 (5) | C2—C7—H7 | 120.3 |
| O1W—Co1—O1Wi | 180.00 (5) | C3—C2—C7 | 121.28 (16) |
| O2W—Co1—N1 | 91.13 (6) | C3—C2—C1 | 117.92 (15) |
| O2Wi—Co1—N1 | 88.87 (6) | C7—C2—C1 | 120.75 (17) |
| O1W—Co1—N1 | 91.66 (6) | N2—C3—C2 | 120.91 (16) |
| O1Wi—Co1—N1 | 88.34 (6) | N2—C3—C4 | 121.11 (17) |
| O2W—Co1—N1i | 88.87 (6) | C2—C3—C4 | 117.90 (17) |
| O2Wi—Co1—N1i | 91.13 (6) | C1—N1—Co1 | 171.82 (16) |
| O1W—Co1—N1i | 88.34 (6) | C4—C5—C6 | 121.43 (18) |
| O1Wi—Co1—N1i | 91.66 (6) | C4—C5—H5 | 119.3 |
| N1—Co1—N1i | 180.0 | C6—C5—H5 | 119.3 |
| Co1—O1W—H1WA | 118.2 | C5—C4—C3 | 120.27 (19) |
| Co1—O1W—H1WB | 115.0 | C5—C4—H4 | 119.9 |
| H1WA—O1W—H1WB | 111.8 | C3—C4—H4 | 119.9 |
| C3—N2—H2A | 113.3 | N1—C1—C2 | 175.48 (19) |
| C3—N2—H2B | 114.3 | C7—C6—C5 | 119.73 (18) |
| H2A—N2—H2B | 113.3 | C7—C6—H6 | 120.1 |
| Co1—O2W—H2WA | 124.4 | C5—C6—H6 | 120.1 |
| Symmetry codes: (i) −x, −y, −z+1. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1WA···Cl1ii | 0.84 | 2.33 | 3.1600 (16) | 170 |
| O1W—H1WB···Cl1iii | 0.86 | 2.27 | 3.1099 (15) | 167 |
| O2W—H2WA···N2iv | 0.91 | 1.99 | 2.868 (2) | 162 |
| O2W—H2WB···Cl1v | 0.88 | 2.27 | 3.1438 (17) | 178 |
| N2—H2B···Cl1vi | 0.92 | 2.53 | 3.4433 (18) | 172 |
| Symmetry codes: (ii) x−1, y−1, z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) x, y−1, z; (v) −x+1/2, y−3/2, −z+1/2; (vi) −x+1, −y+2, −z+1. |
Table 1
Selected geometric parameters (Å) top| Co1—O1W | 2.0899 (14) | Co1—N1 | 2.1566 (15) |
| Co1—O2W | 2.0550 (13) | | |
Table 2
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1WA···Cl1i | 0.84 | 2.33 | 3.1600 (16) | 170 |
| O1W—H1WB···Cl1ii | 0.86 | 2.27 | 3.1099 (15) | 167 |
| O2W—H2WA···N2iii | 0.91 | 1.99 | 2.868 (2) | 162 |
| O2W—H2WB···Cl1iv | 0.88 | 2.27 | 3.1438 (17) | 178 |
| N2—H2B···Cl1v | 0.92 | 2.53 | 3.4433 (18) | 172 |
| Symmetry codes: (i) x−1, y−1, z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x, y−1, z; (iv) −x+1/2, y−3/2, −z+1/2; (v) −x+1, −y+2, −z+1. |
This work was supported by a start-up grant from Anyang Institute of
Technology, China.
Brewis, M., Helliwell, M. & McKeown, N. B. (2003). Tetrahedron, 59, 3863–3872.
Fu, D.-W. & Zhao, H. (2007). Acta Cryst. E63, o3206.
Jin, Z., Nolan, K., McArthur, C. R., Lever, A. B. P. & Leznoff, C. C. (1994). J. Organomet. Chem. 468, 205–212.
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Cl and N-H![[Figure 1]](./xu2671fig1thm.gif)
Nitrile derivatives have found wide range of applications in industry and coordination chemistry as ligands. For example, phthalonitriles have been used as starting materials for phthalocyanines (Jin et al., 1994), which are important components for dyes, pigments, gas sensors, optical limiters and liquid crystals, and which are also used in medicine, as singlet oxygen photosensitisers for photodynamic therapy (Brewis et al., 2003). Recently, we have reported a few benzonitrile compounds (Fu & Zhao, 2007). As an extension of our work on the structural characterization, we report here the crystal structure of the title compound tetra-aqua-bis(2-aminobenzonitrile)-cobalt(II) dichloride.
The crystal data show that in the title compound, the Co(II) lies on an inversion center. The distorted octahedral Co(II) environment contains two N atoms from two planar trans-related 2-aminobenzonitrile ligands in the axial positions and four aqua O atoms in the equatorial plane. In the crystal, O—H···Cl, N—H···Cl and O—H···N hydrogen bonds generate an infinite two-dimensional network (Fig.1).