Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112031964/fg3263sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270112031964/fg3263Isup2.hkl |
CCDC reference: 899062
For related literature, see: Allen (2002); Chavan et al. (1986); Denisova et al. (2003, 2006); Fedotova et al. (2008); Fuma & Ebihara (2006); Lee et al. (2002); Mandel et al. (1977); Mironov (1999); Werner (1910); Williams et al. (1999).
Co(ClO4)2.6H2O (0.203 g) and pyridine (0.5 ml) were dissolved in acetonitrile (15 ml) and heated to 333 K. To this solution was added dropwise 30% by weight H2O2 (0.6 ml) which resulted in a change in color of the solution from pink to dark red. The resulting solution was heated under reflux for 1 h, allowed to cool to room temperature and diethyl ether added until the solution became cloudy. After 1 d, large, red, needle-shaped crystals (yield 0.073 g, 33.6%) were obtained.
Two H atoms involved in hydrogen bonding were refined freely. The other H atoms were placed at calculated positions, with C—H = 0.95 (aromatic) or 0.98 Å (methyl) and refined using a riding model, with Uiso(H) = 1.5Ueq(C) for methyl groups and 1.2Ueq(C) otherwise.
Data collection: SAINT [or APEX2?] (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SORTAV (Blessing, 1995); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).
[Co2(C2H4NO)2(OH)2(C5H5N)4](ClO4)2·2C2H3N | F(000) = 888 |
Mr = 865.41 | Dx = 1.602 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4635 reflections |
a = 10.6198 (7) Å | θ = 2.3–29.2° |
b = 10.2440 (7) Å | µ = 1.15 mm−1 |
c = 16.503 (1) Å | T = 100 K |
β = 92.167 (1)° | Prism, red |
V = 1794.1 (2) Å3 | 0.46 × 0.22 × 0.17 mm |
Z = 2 |
Bruker APEXII CCD diffractometer | 5809 independent reflections |
Radiation source: sealed x-ray tube | 4796 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ϕ or ω oscillation scans | θmax = 31.9°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −15→15 |
Tmin = 0.652, Tmax = 0.746 | k = −15→15 |
21140 measured reflections | l = −24→24 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0329P)2 + 1.1062P] where P = (Fo2 + 2Fc2)/3 |
5809 reflections | (Δ/σ)max = 0.001 |
245 parameters | Δρmax = 0.73 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
[Co2(C2H4NO)2(OH)2(C5H5N)4](ClO4)2·2C2H3N | V = 1794.1 (2) Å3 |
Mr = 865.41 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.6198 (7) Å | µ = 1.15 mm−1 |
b = 10.2440 (7) Å | T = 100 K |
c = 16.503 (1) Å | 0.46 × 0.22 × 0.17 mm |
β = 92.167 (1)° |
Bruker APEXII CCD diffractometer | 5809 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 4796 reflections with I > 2σ(I) |
Tmin = 0.652, Tmax = 0.746 | Rint = 0.037 |
21140 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.73 e Å−3 |
5809 reflections | Δρmin = −0.45 e Å−3 |
245 parameters |
Experimental. IR (cm-1): 3393.0 (w), 3314.4 (m), 2251.7 (w), 1606.8 (m), 1549.7 (br), 1476.2 (m), 1449.0 (s), 1238.1 (m), 1214.2 (s), 1154.9 (w), 1092.7 (sh), 1064.7 (vs), 941.4 (m), 898.0 (m), 771.2 (sh), 760.8 (s), 693.5 (vs). |
Geometry. All s.u.'s (except the s.u. 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 | 0.46912 (2) | 0.55025 (2) | 0.426797 (13) | 0.01179 (6) | |
O1 | 0.38651 (11) | 0.45010 (11) | 0.50391 (7) | 0.0131 (2) | |
H1A | 0.336 (2) | 0.488 (3) | 0.5203 (16) | 0.033 (7)* | |
N1 | 0.42416 (13) | 0.70022 (13) | 0.48763 (8) | 0.0135 (3) | |
H1B | 0.399 (2) | 0.772 (2) | 0.4665 (13) | 0.021 (5)* | |
O2 | 0.47517 (11) | 0.61555 (11) | 0.61550 (7) | 0.0145 (2) | |
N2 | 0.31450 (13) | 0.54632 (13) | 0.36017 (8) | 0.0135 (3) | |
C1 | 0.25497 (16) | 0.43048 (16) | 0.35255 (10) | 0.0163 (3) | |
H1 | 0.2946 | 0.3546 | 0.3746 | 0.02* | |
C2 | 0.13793 (17) | 0.41899 (17) | 0.31358 (11) | 0.0190 (3) | |
H2 | 0.0972 | 0.3366 | 0.3097 | 0.023* | |
C3 | 0.08103 (17) | 0.52900 (18) | 0.28036 (11) | 0.0217 (4) | |
H3 | 0.0004 | 0.5233 | 0.2536 | 0.026* | |
C4 | 0.14303 (17) | 0.64758 (18) | 0.28664 (11) | 0.0209 (3) | |
H4 | 0.1063 | 0.7241 | 0.2634 | 0.025* | |
C5 | 0.25940 (16) | 0.65295 (16) | 0.32729 (10) | 0.0167 (3) | |
H5 | 0.3016 | 0.7345 | 0.3321 | 0.02* | |
N3 | 0.56135 (13) | 0.64926 (14) | 0.34850 (8) | 0.0147 (3) | |
C6 | 0.55776 (16) | 0.61638 (17) | 0.26919 (10) | 0.0186 (3) | |
H6 | 0.5088 | 0.5432 | 0.2519 | 0.022* | |
C7 | 0.62304 (18) | 0.68584 (19) | 0.21237 (11) | 0.0230 (4) | |
H7 | 0.6184 | 0.661 | 0.1569 | 0.028* | |
C8 | 0.69538 (18) | 0.79237 (19) | 0.23758 (12) | 0.0249 (4) | |
H8 | 0.74 | 0.8422 | 0.1995 | 0.03* | |
C9 | 0.70130 (18) | 0.82470 (18) | 0.31919 (12) | 0.0234 (4) | |
H9 | 0.7514 | 0.8961 | 0.3381 | 0.028* | |
C10 | 0.63306 (16) | 0.75143 (17) | 0.37290 (11) | 0.0189 (3) | |
H10 | 0.637 | 0.774 | 0.4288 | 0.023* | |
C11 | 0.44008 (14) | 0.70913 (16) | 0.56673 (10) | 0.0140 (3) | |
C12 | 0.41864 (17) | 0.83912 (16) | 0.60668 (11) | 0.0187 (3) | |
H12A | 0.4972 | 0.8895 | 0.6081 | 0.028* | |
H12B | 0.3916 | 0.8251 | 0.6621 | 0.028* | |
H12C | 0.3532 | 0.8873 | 0.5758 | 0.028* | |
N4 | 0.15243 (16) | 0.58853 (18) | 0.54242 (11) | 0.0284 (4) | |
C41 | 0.07223 (18) | 0.64581 (19) | 0.51135 (12) | 0.0243 (4) | |
C42 | −0.0309 (2) | 0.7190 (2) | 0.47192 (14) | 0.0314 (4) | |
H42A | −0.0668 | 0.6683 | 0.4263 | 0.047* | |
H42B | 0.001 | 0.8023 | 0.452 | 0.047* | |
H42C | −0.0963 | 0.7355 | 0.511 | 0.047* | |
Cl1 | 0.21490 (4) | 1.00646 (4) | 0.41599 (3) | 0.02444 (10) | |
O3 | 0.12447 (17) | 0.94963 (19) | 0.35856 (11) | 0.0484 (5) | |
O4 | 0.33574 (13) | 0.94539 (13) | 0.40484 (9) | 0.0255 (3) | |
O5 | 0.2253 (2) | 1.14318 (15) | 0.40122 (13) | 0.0582 (6) | |
O6 | 0.17453 (14) | 0.98297 (16) | 0.49681 (9) | 0.0336 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01319 (10) | 0.01015 (10) | 0.01196 (10) | −0.00040 (8) | −0.00044 (7) | 0.00032 (8) |
O1 | 0.0135 (5) | 0.0121 (5) | 0.0137 (5) | 0.0004 (4) | 0.0006 (4) | 0.0008 (4) |
N1 | 0.0147 (6) | 0.0103 (6) | 0.0154 (6) | 0.0006 (5) | −0.0007 (5) | 0.0002 (5) |
O2 | 0.0165 (5) | 0.0128 (5) | 0.0142 (5) | 0.0006 (4) | −0.0003 (4) | −0.0007 (4) |
N2 | 0.0149 (6) | 0.0128 (6) | 0.0127 (6) | −0.0009 (5) | 0.0004 (5) | 0.0002 (5) |
C1 | 0.0182 (8) | 0.0138 (7) | 0.0167 (7) | −0.0012 (6) | −0.0006 (6) | −0.0003 (6) |
C2 | 0.0203 (8) | 0.0166 (8) | 0.0199 (8) | −0.0052 (6) | −0.0028 (6) | −0.0001 (6) |
C3 | 0.0178 (8) | 0.0248 (9) | 0.0221 (9) | −0.0017 (7) | −0.0055 (7) | 0.0030 (7) |
C4 | 0.0219 (8) | 0.0189 (8) | 0.0215 (8) | 0.0020 (7) | −0.0044 (7) | 0.0037 (7) |
C5 | 0.0196 (8) | 0.0141 (7) | 0.0163 (7) | −0.0001 (6) | 0.0000 (6) | 0.0012 (6) |
N3 | 0.0150 (6) | 0.0135 (6) | 0.0157 (6) | 0.0011 (5) | 0.0005 (5) | 0.0027 (5) |
C6 | 0.0189 (8) | 0.0190 (8) | 0.0181 (8) | 0.0027 (6) | 0.0007 (6) | 0.0011 (6) |
C7 | 0.0239 (9) | 0.0278 (9) | 0.0176 (8) | 0.0063 (7) | 0.0047 (7) | 0.0055 (7) |
C8 | 0.0240 (9) | 0.0218 (9) | 0.0295 (10) | 0.0047 (7) | 0.0110 (7) | 0.0096 (7) |
C9 | 0.0226 (9) | 0.0175 (8) | 0.0304 (10) | −0.0016 (7) | 0.0064 (7) | 0.0033 (7) |
C10 | 0.0193 (8) | 0.0162 (8) | 0.0212 (8) | −0.0008 (6) | 0.0023 (6) | 0.0017 (6) |
C11 | 0.0113 (7) | 0.0127 (7) | 0.0180 (7) | −0.0005 (5) | 0.0009 (6) | −0.0008 (6) |
C12 | 0.0207 (8) | 0.0138 (7) | 0.0216 (8) | 0.0014 (6) | 0.0000 (6) | −0.0046 (6) |
N4 | 0.0230 (8) | 0.0286 (9) | 0.0338 (9) | −0.0015 (7) | 0.0035 (7) | −0.0061 (7) |
C41 | 0.0233 (9) | 0.0211 (9) | 0.0290 (10) | −0.0030 (7) | 0.0078 (7) | −0.0067 (7) |
C42 | 0.0283 (10) | 0.0259 (10) | 0.0402 (12) | 0.0043 (8) | 0.0037 (9) | 0.0023 (9) |
Cl1 | 0.0294 (2) | 0.01517 (19) | 0.0289 (2) | 0.00356 (16) | 0.00293 (18) | 0.00678 (16) |
O3 | 0.0392 (10) | 0.0630 (13) | 0.0417 (10) | 0.0070 (9) | −0.0158 (8) | 0.0016 (9) |
O4 | 0.0263 (7) | 0.0184 (6) | 0.0320 (7) | 0.0024 (5) | 0.0031 (6) | 0.0036 (5) |
O5 | 0.0781 (14) | 0.0132 (7) | 0.0863 (15) | 0.0087 (8) | 0.0437 (12) | 0.0129 (8) |
O6 | 0.0324 (8) | 0.0392 (9) | 0.0296 (8) | 0.0022 (7) | 0.0051 (6) | 0.0089 (7) |
Co1—O1 | 1.8777 (12) | C6—C7 | 1.384 (2) |
Co1—N1 | 1.9059 (14) | C6—H6 | 0.95 |
Co1—O2i | 1.9374 (12) | C7—C8 | 1.389 (3) |
Co1—N3 | 1.9374 (14) | C7—H7 | 0.95 |
Co1—N2 | 1.9418 (14) | C8—C9 | 1.386 (3) |
Co1—Co1i | 2.6847 (4) | C8—H8 | 0.95 |
O1—H1A | 0.72 (3) | C9—C10 | 1.387 (2) |
N1—C11 | 1.313 (2) | C9—H9 | 0.95 |
N1—H1B | 0.85 (2) | C10—H10 | 0.95 |
O2—C11 | 1.2973 (19) | C11—C12 | 1.507 (2) |
N2—C5 | 1.344 (2) | C12—H12A | 0.98 |
N2—C1 | 1.348 (2) | C12—H12B | 0.98 |
C1—C2 | 1.383 (2) | C12—H12C | 0.98 |
C1—H1 | 0.95 | N4—C41 | 1.140 (3) |
C2—C3 | 1.382 (2) | C41—C42 | 1.460 (3) |
C2—H2 | 0.95 | C42—H42A | 0.98 |
C3—C4 | 1.384 (3) | C42—H42B | 0.98 |
C3—H3 | 0.95 | C42—H42C | 0.98 |
C4—C5 | 1.385 (2) | Cl1—O5 | 1.4265 (16) |
C4—H4 | 0.95 | Cl1—O6 | 1.4367 (16) |
C5—H5 | 0.95 | Cl1—O4 | 1.4456 (14) |
N3—C10 | 1.347 (2) | Cl1—O3 | 1.4459 (18) |
N3—C6 | 1.351 (2) | ||
O1—Co1—O1i | 88.73 (5) | N2—C5—H5 | 119 |
O1—Co1—N1 | 87.17 (6) | C4—C5—H5 | 119 |
O1i—Co1—N1 | 84.02 (6) | C10—N3—C6 | 118.58 (15) |
O1—Co1—O2i | 85.53 (5) | C10—N3—Co1 | 120.12 (12) |
O1i—Co1—O2i | 87.96 (5) | C6—N3—Co1 | 121.28 (12) |
N1—Co1—O2i | 169.26 (6) | N3—C6—C7 | 122.13 (17) |
O1—Co1—N3 | 177.39 (6) | N3—C6—H6 | 118.9 |
O1i—Co1—N3 | 89.17 (5) | C7—C6—H6 | 118.9 |
N1—Co1—N3 | 94.15 (6) | C6—C7—C8 | 119.11 (17) |
O2i—Co1—N3 | 92.85 (5) | C6—C7—H7 | 120.4 |
O1—Co1—N2 | 88.03 (5) | C8—C7—H7 | 120.4 |
O1i—Co1—N2 | 176.71 (5) | C9—C8—C7 | 118.87 (17) |
N1—Co1—N2 | 95.26 (6) | C9—C8—H8 | 120.6 |
O2i—Co1—N2 | 92.35 (5) | C7—C8—H8 | 120.6 |
N3—Co1—N2 | 94.08 (6) | C8—C9—C10 | 119.09 (18) |
O1—Co1—Co1i | 44.37 (4) | C8—C9—H9 | 120.5 |
N1—Co1—Co1i | 83.83 (4) | C10—C9—H9 | 120.5 |
O2i—Co1—Co1i | 85.44 (3) | N3—C10—C9 | 122.19 (17) |
N3—Co1—Co1i | 133.51 (4) | N3—C10—H10 | 118.9 |
N2—Co1—Co1i | 132.39 (4) | C9—C10—H10 | 118.9 |
Co1—O1—Co1i | 91.27 (5) | O2—C11—N1 | 126.06 (15) |
Co1—O1—H1A | 109 (2) | O2—C11—C12 | 115.22 (14) |
Co1i—O1—H1A | 112 (2) | N1—C11—C12 | 118.71 (15) |
C11—N1—Co1 | 123.66 (11) | C11—C12—H12A | 109.5 |
C11—N1—H1B | 111.9 (14) | C11—C12—H12B | 109.5 |
Co1—N1—H1B | 124.1 (14) | H12A—C12—H12B | 109.5 |
C11—O2—Co1i | 120.58 (10) | C11—C12—H12C | 109.5 |
C5—N2—C1 | 118.84 (14) | H12A—C12—H12C | 109.5 |
C5—N2—Co1 | 123.90 (11) | H12B—C12—H12C | 109.5 |
C1—N2—Co1 | 117.04 (11) | N4—C41—C42 | 179.7 (2) |
N2—C1—C2 | 121.90 (16) | C41—C42—H42A | 109.5 |
N2—C1—H1 | 119.1 | C41—C42—H42B | 109.5 |
C2—C1—H1 | 119.1 | H42A—C42—H42B | 109.5 |
C3—C2—C1 | 119.13 (16) | C41—C42—H42C | 109.5 |
C3—C2—H2 | 120.4 | H42A—C42—H42C | 109.5 |
C1—C2—H2 | 120.4 | H42B—C42—H42C | 109.5 |
C2—C3—C4 | 119.11 (16) | O5—Cl1—O6 | 110.53 (11) |
C2—C3—H3 | 120.4 | O5—Cl1—O4 | 109.18 (10) |
C4—C3—H3 | 120.4 | O6—Cl1—O4 | 110.07 (9) |
C3—C4—C5 | 118.98 (16) | O5—Cl1—O3 | 109.69 (13) |
C3—C4—H4 | 120.5 | O6—Cl1—O3 | 109.08 (11) |
C5—C4—H4 | 120.5 | O4—Cl1—O3 | 108.25 (10) |
N2—C5—C4 | 122.02 (16) | ||
O1i—Co1—O1—Co1i | 0 | C1—N2—C5—C4 | 0.7 (2) |
N1—Co1—O1—Co1i | −84.07 (6) | Co1—N2—C5—C4 | −173.72 (13) |
O2i—Co1—O1—Co1i | 88.05 (5) | C3—C4—C5—N2 | 0.6 (3) |
N2—Co1—O1—Co1i | −179.44 (6) | O1i—Co1—N3—C10 | −44.90 (13) |
O1—Co1—N1—C11 | 47.42 (13) | N1—Co1—N3—C10 | 39.04 (13) |
O1i—Co1—N1—C11 | −41.60 (13) | O2i—Co1—N3—C10 | −132.81 (13) |
O2i—Co1—N1—C11 | 0.2 (4) | N2—Co1—N3—C10 | 134.63 (13) |
N3—Co1—N1—C11 | −130.33 (13) | Co1i—Co1—N3—C10 | −46.39 (15) |
N2—Co1—N1—C11 | 135.18 (13) | O1i—Co1—N3—C6 | 133.65 (13) |
Co1i—Co1—N1—C11 | 3.03 (13) | N1—Co1—N3—C6 | −142.42 (13) |
O1—Co1—N2—C5 | 129.66 (14) | O2i—Co1—N3—C6 | 45.73 (13) |
N1—Co1—N2—C5 | 42.69 (14) | N2—Co1—N3—C6 | −46.83 (13) |
O2i—Co1—N2—C5 | −144.89 (13) | Co1i—Co1—N3—C6 | 132.15 (11) |
N3—Co1—N2—C5 | −51.87 (14) | C10—N3—C6—C7 | −1.4 (2) |
Co1i—Co1—N2—C5 | 129.13 (12) | Co1—N3—C6—C7 | −179.96 (13) |
O1—Co1—N2—C1 | −44.81 (12) | N3—C6—C7—C8 | 0.4 (3) |
N1—Co1—N2—C1 | −131.79 (12) | C6—C7—C8—C9 | 0.9 (3) |
O2i—Co1—N2—C1 | 40.63 (12) | C7—C8—C9—C10 | −1.2 (3) |
N3—Co1—N2—C1 | 133.66 (12) | C6—N3—C10—C9 | 1.0 (3) |
Co1i—Co1—N2—C1 | −45.34 (14) | Co1—N3—C10—C9 | 179.62 (13) |
C5—N2—C1—C2 | −1.5 (2) | C8—C9—C10—N3 | 0.3 (3) |
Co1—N2—C1—C2 | 173.27 (13) | Co1i—O2—C11—N1 | 8.1 (2) |
N2—C1—C2—C3 | 1.0 (3) | Co1i—O2—C11—C12 | −170.77 (11) |
C1—C2—C3—C4 | 0.3 (3) | Co1—N1—C11—O2 | −7.7 (2) |
C2—C3—C4—C5 | −1.1 (3) | Co1—N1—C11—C12 | 171.23 (12) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N4 | 0.72 (2) | 2.25 (2) | 2.952 (2) | 165 (3) |
N1—H1B···O4 | 0.85 (2) | 2.14 (2) | 2.993 (2) | 176 (2) |
C1—H1···O5ii | 0.95 | 2.33 | 3.070 (2) | 134 |
C5—H5···O4 | 0.95 | 2.49 | 3.345 (2) | 150 |
C6—H6···O3iii | 0.95 | 2.46 | 3.286 (3) | 145 |
C12—H12A···O4iv | 0.98 | 2.47 | 3.428 (2) | 167 |
C12—H12C···O6 | 0.98 | 2.46 | 3.439 (2) | 173 |
C42—H42B···O3 | 0.98 | 2.55 | 3.470 (3) | 155 |
C42—H42C···O5v | 0.98 | 2.38 | 3.311 (3) | 158 |
Symmetry codes: (ii) x, y−1, z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1, −y+2, −z+1; (v) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co2(C2H4NO)2(OH)2(C5H5N)4](ClO4)2·2C2H3N |
Mr | 865.41 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 10.6198 (7), 10.2440 (7), 16.503 (1) |
β (°) | 92.167 (1) |
V (Å3) | 1794.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.15 |
Crystal size (mm) | 0.46 × 0.22 × 0.17 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2008) |
Tmin, Tmax | 0.652, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21140, 5809, 4796 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.743 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.085, 1.04 |
No. of reflections | 5809 |
No. of parameters | 245 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.73, −0.45 |
Computer programs: SAINT [or APEX2?] (Bruker, 2009), SAINT (Bruker, 2009), SORTAV (Blessing, 1995), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···N4 | 0.72 (2) | 2.25 (2) | 2.952 (2) | 165 (3) |
N1—H1B···O4 | 0.85 (2) | 2.14 (2) | 2.993 (2) | 176 (2) |
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In the process of studying cobalt phosphinate compounds, we isolated and crystallized di-µ-acetylamido-di-µ-hydroxido-bis[dipyridinecobalt(III)] bis(perchlorate) acetonitrile disolvate, (I). Related dihydroxide- and acetate-bridged cobalt(III) dimers were first produced by Werner (1910) and later characterized crystallographically by Mandel et al. (1977). These types of compounds have been studied as model metal centers for different enzymes. Lee et al. (2002) stabilized the dimeric core using sterically hindered carbocyclic acid derivatives to study the active site in metallohydrolases. Williams et al. (1999) used 1,4,7-triazacyclononane to stabilize a related cobalt dimer in order to study the hydrolyses of phosphate esters in metallophosphatase enzymes. The fact that (I) has bridging acetylamidate ligands is significant since relatively few transition metal compounds containing this ligand have been structurally characterized. Fedotova et al. (2008) synthesized a platinum(II) dimer with acetylamidate ligands, Chavan et al. (1986) used acetamide to make rhodium(II) dimers, Mironov (1999) stabilized rhenium chalcolgen clusters with acetylamidate ligands and Fuma & Ebihara (2006) used acetamide to make dirhodium paddle-wheel units that were bridged by perrhenate.
Two formula units of (I) constitute the unit cell, with the asymmetric unit consisting of half a complex cation lying about an inversion center, one perchlorate anion and one acetonitrile solvent molecule, both linked to the half cation by hydrogen bonds. The two CoIII centers are bridged by two trans-acetylamidate, through one O from one acetylamidate and one N from the other, and two cis-hydroxide ligands (Fig. 1). The Co1—O2 bond length is 1.9374 (12) Å, whereas that for Co1—N1 is 1.9059 (14) Å. The O2—Co—N1 angle is bent towards the adjacent CoIII center away from ideality, 180 to 169.26 (6)°. Interestingly, the C—O bond length [C11—O2 = 1.2973 (19) Å] is shorter than N—C [C11—N1 = 1.313 (2) Å] on the acetylamidate ligands. There are two pyridine molecules coordinated cis to each CoIII center in the same plane as the hydroxide ligands with pyridine torsion angles of 47.0 (1) and 45.8 (1)° for the N2 and N3 pyridine (py) ligands, respectively, against the metal–hydroxide plane. The two Npy—Co bond lengths are 1.9418 (14) and 1.9374 (12) Å for Co1—N2 and Co1—N3, respectively, and the N2—Co1—N3 angle is slightly larger than 90° at 94.08 (6)°. The Co1—O1 and Co1—O1i bond lengths are 1.8777 (12) Å and the O1—Co—O1i angle is 88.73 (5)° [symmetry code: (i) -x+1, -y+1, -z+1]; thus, this bridging arrangement constitutes a crystallographically imposed planar but slightly distorted square geometry.
The Co···Co distance in the dimer is 2.6847 (4) Å and is longer than the equivalent Co···Co distance in three other complexes containing the [Co2(OH)2(O2CCR)2]4+ core as evident in a search of the Cambridge Structural Database (CSD, Version 5.33 [OK?]; Allen, 2002): (i) 2.655 (2) ° in a tetrahydrofuran solvate of [Co2(OH)2(O2CR)2L4]2+ (R = tBu and L = 3,5-dimethylpyrazole) (Denisova et al., 2003), (ii) 2.669 (2) Å in the analogous benzene solvate (Denisova et al., 2006) and (iii) 2.6802 (5) Å in [Co2(OH)2(O2CR)2L2L'2]2+ (κ2-O2CR = κ1-L = 2,6-di-p-tolylbenzoate and L' = pyridine; Lee et al., 2002).
The unique perchlorate anion is hydrogen bonded to the H atom of the acetylamidate ligand and the unique acetonitrile ligand is hydrogen bonded to the bridging hydroxide H atoms (Fig. 1 and Table 1).