Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034708/cv2278sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034708/cv2278Isup2.hkl |
CCDC reference: 657610
The title compound was prepared by the reaction of N-ethylimidazole (0.48 g, 5 mmol) with CoSO4.7H2O(1.40 g, 5 mmol) by means of hydrothermal synthesis in a stainless-steel reactor with a Teflon liner at 383 K for 24 h. Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.
H atoms bonded to O atoms were located in a difference map and were refined with bonds restraints O—H=0.85 (3) Å, H···H 1.37 (2) Å, and with Uiso(H) = 0.1. The C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.2 times Ueq(C).
In the title compound, (I) (Fig. 1), the local coordination geometry around the Co centre can be described as a distorted octahedron, formed by one N atom from one N-vinylimidazole ligand and five O atoms from five water molecules. The Co—N bond distance is 2.069 (3) Å, compared with a value of 2.097 (2) Å in [Co(viz)4SiF6] {viz is N-vinylimidazole; Driessen et al., 1982}. The Co—O bond distances range from 2.067 (3) to 2.199 (2) Å, compared to the similar Co—O(water) bond distances of 2.087 (3), 2.062 (2) and 2.087 (4) Å in [(pyz)Co2(H2O)10](SO4)2(H2O)2 (pyz is pyrazine; Xie et al., 2004).
In the crystal, the cations and anions are linked by O—H···O hydrogen bonds into two-dimensional layers parallell to ab-plane with the protruding N-vinylimidazole ligands.
In the corresponding binuclear cobalt compound [(pyz)Co2(H2O)10](SO4)2(H2O)2 (Xie et al., 2004), the two CoII ions have a distorted octahedral environment formed by five water molecules and one N atom from pyz (= pyrazine). In [Co(viz)4SiF6] (viz = N-vinylimidazole), the CoII ions also have a distorted octahedral environment (Driessen et al., 1982).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and local programs.
Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. |
[Co(C5H6N2)(H2O)5]SO4 | Z = 2 |
Mr = 339.19 | F(000) = 350 |
Triclinic, P1 | Dx = 1.735 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.2070 (12) Å | Cell parameters from 25 reflections |
b = 8.0820 (16) Å | θ = 4–14° |
c = 13.409 (3) Å | µ = 1.52 mm−1 |
α = 83.42 (3)° | T = 293 K |
β = 77.67 (3)° | Block, pink |
γ = 82.67 (3)° | 0.40 × 0.30 × 0.10 mm |
V = 649.1 (2) Å3 |
Bruker SMART 1K CCD area-detector diffractometer | 2486 independent reflections |
Radiation source: fine-focus sealed tube | 2322 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
thin–slice ω scans | θmax = 26.0°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −7→7 |
Tmin = 0.581, Tmax = 0.863 | k = −9→9 |
2546 measured reflections | l = 0→16 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0813P)2 + 0.8585P] where P = (Fo2 + 2Fc2)/3 |
2486 reflections | (Δ/σ)max = 0.001 |
193 parameters | Δρmax = 0.65 e Å−3 |
15 restraints | Δρmin = −0.46 e Å−3 |
[Co(C5H6N2)(H2O)5]SO4 | γ = 82.67 (3)° |
Mr = 339.19 | V = 649.1 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.2070 (12) Å | Mo Kα radiation |
b = 8.0820 (16) Å | µ = 1.52 mm−1 |
c = 13.409 (3) Å | T = 293 K |
α = 83.42 (3)° | 0.40 × 0.30 × 0.10 mm |
β = 77.67 (3)° |
Bruker SMART 1K CCD area-detector diffractometer | 2486 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2322 reflections with I > 2σ(I) |
Tmin = 0.581, Tmax = 0.863 | Rint = 0.032 |
2546 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 15 restraints |
wR(F2) = 0.129 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.65 e Å−3 |
2486 reflections | Δρmin = −0.46 e Å−3 |
193 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Co | 0.43720 (6) | 0.70331 (5) | 0.68120 (3) | 0.02540 (18) | |
S | −0.07835 (12) | 1.21755 (9) | 0.65627 (6) | 0.0268 (2) | |
O1 | 0.3863 (4) | 0.4501 (3) | 0.6951 (2) | 0.0382 (6) | |
O2 | 0.7417 (4) | 0.6427 (3) | 0.7345 (2) | 0.0389 (6) | |
O3 | 0.6202 (4) | 0.6508 (3) | 0.5351 (2) | 0.0405 (6) | |
O4 | 0.5035 (5) | 0.9498 (3) | 0.6461 (3) | 0.0453 (7) | |
O5 | 0.1416 (4) | 0.7796 (3) | 0.61441 (19) | 0.0317 (5) | |
O6 | −0.2029 (5) | 1.0888 (4) | 0.7207 (3) | 0.0533 (8) | |
O7 | −0.0249 (4) | 1.3356 (3) | 0.7205 (2) | 0.0438 (7) | |
O8 | 0.1284 (4) | 1.1339 (3) | 0.5985 (2) | 0.0455 (7) | |
O9 | −0.2087 (5) | 1.3086 (3) | 0.5828 (2) | 0.0454 (7) | |
N1 | 0.2553 (5) | 0.7268 (4) | 0.8283 (2) | 0.0366 (7) | |
N2 | −0.0162 (6) | 0.7876 (5) | 0.9575 (3) | 0.0474 (8) | |
C1 | 0.0593 (6) | 0.8068 (5) | 0.8561 (3) | 0.0417 (9) | |
H1A | −0.0193 | 0.8700 | 0.8105 | 0.050* | |
C2 | 0.1479 (10) | 0.6906 (8) | 0.9986 (4) | 0.0736 (17) | |
H2A | 0.1466 | 0.6570 | 1.0674 | 0.088* | |
C3 | 0.3118 (9) | 0.6545 (7) | 0.9172 (4) | 0.0680 (15) | |
H3A | 0.4448 | 0.5893 | 0.9215 | 0.082* | |
C4 | −0.2297 (9) | 0.8587 (8) | 1.0087 (4) | 0.0685 (15) | |
H4A | −0.3243 | 0.9171 | 0.9685 | 0.082* | |
C5 | −0.2983 (10) | 0.8469 (8) | 1.1060 (4) | 0.0807 (18) | |
H5A | −0.2079 | 0.7893 | 1.1484 | 0.097* | |
H5B | −0.4387 | 0.8959 | 1.1342 | 0.097* | |
H5WA | 0.165 (11) | 0.741 (7) | 0.556 (5) | 0.1* | |
H4WA | 0.597 (8) | 1.002 (7) | 0.664 (6) | 0.1* | |
H2WA | 0.787 (10) | 0.540 (5) | 0.730 (6) | 0.1* | |
H5WB | 0.139 (11) | 0.886 (5) | 0.604 (5) | 0.1* | |
H2WB | 0.839 (8) | 0.699 (6) | 0.695 (5) | 0.1* | |
H4WB | 0.389 (6) | 1.018 (6) | 0.642 (6) | 0.1* | |
H1WA | 0.254 (3) | 0.427 (8) | 0.700 (6) | 0.1* | |
H1WB | 0.471 (8) | 0.378 (7) | 0.659 (5) | 0.1* | |
H3WA | 0.703 (9) | 0.559 (4) | 0.533 (6) | 0.1* | |
H3WB | 0.691 (9) | 0.723 (6) | 0.494 (5) | 0.1* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0185 (3) | 0.0206 (3) | 0.0371 (3) | 0.00043 (16) | −0.00718 (18) | −0.00281 (17) |
S | 0.0177 (4) | 0.0223 (4) | 0.0407 (5) | 0.0007 (3) | −0.0093 (3) | −0.0006 (3) |
O1 | 0.0260 (12) | 0.0251 (12) | 0.0621 (17) | −0.0017 (10) | −0.0049 (12) | −0.0067 (11) |
O2 | 0.0256 (12) | 0.0338 (13) | 0.0601 (17) | 0.0028 (10) | −0.0165 (12) | −0.0071 (12) |
O3 | 0.0371 (14) | 0.0331 (14) | 0.0460 (15) | 0.0013 (11) | 0.0001 (11) | −0.0035 (11) |
O4 | 0.0359 (14) | 0.0225 (12) | 0.083 (2) | −0.0034 (10) | −0.0257 (14) | −0.0012 (13) |
O5 | 0.0255 (11) | 0.0267 (12) | 0.0442 (14) | 0.0024 (9) | −0.0124 (10) | −0.0045 (10) |
O6 | 0.0424 (16) | 0.0540 (18) | 0.0659 (19) | −0.0204 (14) | −0.0153 (14) | 0.0098 (15) |
O7 | 0.0356 (14) | 0.0362 (14) | 0.0644 (18) | 0.0008 (11) | −0.0208 (13) | −0.0100 (13) |
O8 | 0.0306 (13) | 0.0355 (14) | 0.0631 (18) | 0.0112 (11) | −0.0033 (12) | −0.0019 (12) |
O9 | 0.0458 (16) | 0.0413 (15) | 0.0507 (16) | 0.0193 (12) | −0.0253 (13) | −0.0082 (12) |
N1 | 0.0316 (15) | 0.0393 (17) | 0.0374 (16) | 0.0030 (13) | −0.0070 (13) | −0.0042 (13) |
N2 | 0.0397 (18) | 0.055 (2) | 0.0436 (18) | −0.0001 (16) | −0.0024 (15) | −0.0039 (16) |
C1 | 0.036 (2) | 0.047 (2) | 0.042 (2) | 0.0025 (17) | −0.0082 (16) | −0.0093 (16) |
C2 | 0.073 (4) | 0.092 (4) | 0.040 (2) | 0.018 (3) | −0.002 (2) | 0.009 (2) |
C3 | 0.055 (3) | 0.083 (4) | 0.053 (3) | 0.026 (3) | −0.009 (2) | 0.008 (3) |
C4 | 0.050 (3) | 0.091 (4) | 0.056 (3) | 0.017 (3) | −0.005 (2) | −0.010 (3) |
C5 | 0.063 (3) | 0.094 (4) | 0.065 (3) | 0.018 (3) | 0.009 (3) | 0.004 (3) |
Co—N1 | 2.069 (3) | O4—H4WB | 0.85 (3) |
Co—O1 | 2.092 (3) | O5—H5WA | 0.85 (3) |
Co—O2 | 2.141 (3) | O5—H5WB | 0.85 (3) |
Co—O3 | 2.103 (3) | N1—C1 | 1.303 (5) |
Co—O4 | 2.067 (3) | N1—C3 | 1.361 (6) |
Co—O5 | 2.199 (2) | N2—C1 | 1.338 (5) |
S—O6 | 1.463 (3) | N2—C2 | 1.376 (6) |
S—O7 | 1.467 (3) | N2—C4 | 1.437 (6) |
S—O8 | 1.476 (3) | C1—H1A | 0.9300 |
S—O9 | 1.479 (3) | C2—C3 | 1.354 (7) |
O1—H1WA | 0.85 (3) | C2—H2A | 0.9300 |
O1—H1WB | 0.85 (3) | C3—H3A | 0.9300 |
O2—H2WA | 0.85 (3) | C4—C5 | 1.279 (7) |
O2—H2WB | 0.86 (3) | C4—H4A | 0.9300 |
O3—H3WA | 0.85 (3) | C5—H5A | 0.9300 |
O3—H3WB | 0.85 (3) | C5—H5B | 0.9300 |
O4—H4WA | 0.85 (3) | ||
O4—Co—N1 | 97.60 (13) | H3WA—O3—H3WB | 107 (6) |
O4—Co—O1 | 172.04 (12) | Co—O4—H4WA | 130 (5) |
N1—Co—O1 | 90.19 (12) | Co—O4—H4WB | 114 (4) |
O4—Co—O3 | 88.68 (13) | H4WA—O4—H4WB | 108 (5) |
N1—Co—O3 | 173.68 (11) | Co—O5—H5WA | 108 (5) |
O1—Co—O3 | 83.56 (11) | Co—O5—H5WB | 104 (5) |
O4—Co—O2 | 90.23 (11) | H5WA—O5—H5WB | 107 (6) |
N1—Co—O2 | 92.21 (12) | C1—N1—C3 | 105.0 (4) |
O1—Co—O2 | 91.12 (11) | C1—N1—Co | 128.0 (3) |
O3—Co—O2 | 86.96 (11) | C3—N1—Co | 126.9 (3) |
O4—Co—O5 | 85.84 (10) | C1—N2—C2 | 106.7 (4) |
N1—Co—O5 | 91.87 (11) | C1—N2—C4 | 124.2 (4) |
O1—Co—O5 | 92.29 (10) | C2—N2—C4 | 129.1 (4) |
O3—Co—O5 | 89.36 (11) | N1—C1—N2 | 112.4 (4) |
O2—Co—O5 | 174.67 (10) | N1—C1—H1A | 123.8 |
O6—S—O7 | 109.97 (19) | N2—C1—H1A | 123.8 |
O6—S—O8 | 108.12 (19) | C3—C2—N2 | 105.1 (4) |
O7—S—O8 | 109.66 (17) | C3—C2—H2A | 127.4 |
O6—S—O9 | 110.33 (18) | N2—C2—H2A | 127.4 |
O7—S—O9 | 109.81 (16) | C2—C3—N1 | 110.7 (4) |
O8—S—O9 | 108.92 (17) | C2—C3—H3A | 124.6 |
Co—O1—H1WA | 117 (5) | N1—C3—H3A | 124.6 |
Co—O1—H1WB | 123 (5) | C5—C4—N2 | 124.4 (5) |
H1WA—O1—H1WB | 107 (6) | C5—C4—H4A | 117.8 |
Co—O2—H2WA | 110 (5) | N2—C4—H4A | 117.8 |
Co—O2—H2WB | 108 (5) | C4—C5—H5A | 120.0 |
H2WA—O2—H2WB | 107 (6) | C4—C5—H5B | 120.0 |
Co—O3—H3WA | 115 (5) | H5A—C5—H5B | 120.0 |
Co—O3—H3WB | 123 (5) | ||
O4—Co—N1—C1 | 68.8 (4) | C2—N2—C1—N1 | 1.7 (6) |
O1—Co—N1—C1 | −109.5 (4) | C4—N2—C1—N1 | −178.5 (4) |
O2—Co—N1—C1 | 159.3 (3) | C1—N2—C2—C3 | −1.3 (7) |
O5—Co—N1—C1 | −17.2 (3) | C4—N2—C2—C3 | 178.9 (5) |
O4—Co—N1—C3 | −114.5 (4) | N2—C2—C3—N1 | 0.6 (7) |
O1—Co—N1—C3 | 67.1 (4) | C1—N1—C3—C2 | 0.4 (7) |
O2—Co—N1—C3 | −24.0 (4) | Co—N1—C3—C2 | −176.8 (4) |
O5—Co—N1—C3 | 159.4 (4) | C1—N2—C4—C5 | −176.7 (6) |
C3—N1—C1—N2 | −1.3 (5) | C2—N2—C4—C5 | 3.1 (10) |
Co—N1—C1—N2 | 175.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5WA···O9i | 0.85 (3) | 1.90 (7) | 2.750 (4) | 171 (6) |
O4—H4WA···O6ii | 0.85 (3) | 1.83 (4) | 2.673 (5) | 171 (6) |
O2—H2WA···O7iii | 0.85 (3) | 1.90 (5) | 2.714 (4) | 161 (5) |
O5—H5WB···O8 | 0.85 (3) | 1.99 (4) | 2.839 (3) | 173 (6) |
O2—H2WB···O5ii | 0.85 (3) | 2.10 (5) | 2.926 (4) | 163 (6) |
O4—H4WB···O8 | 0.85 (3) | 1.93 (5) | 2.752 (4) | 162 (7) |
O1—H1WA···O7iv | 0.85 (3) | 1.92 (4) | 2.765 (4) | 169 (6) |
O1—H1WB···O9iii | 0.85 (3) | 2.07 (5) | 2.818 (4) | 146 (6) |
O3—H3WB···O8v | 0.85 (3) | 1.88 (5) | 2.730 (6) | 174 (5) |
O3—H3WA···O9iii | 0.85 (3) | 2.10 (5) | 2.885 (4) | 154 (5) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1, y, z; (iii) x+1, y−1, z; (iv) x, y−1, z; (v) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co(C5H6N2)(H2O)5]SO4 |
Mr | 339.19 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.2070 (12), 8.0820 (16), 13.409 (3) |
α, β, γ (°) | 83.42 (3), 77.67 (3), 82.67 (3) |
V (Å3) | 649.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.52 |
Crystal size (mm) | 0.40 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.581, 0.863 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2546, 2486, 2322 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.129, 1.06 |
No. of reflections | 2486 |
No. of parameters | 193 |
No. of restraints | 15 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.65, −0.46 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXTL and local programs.
Co—N1 | 2.069 (3) | Co—O3 | 2.103 (3) |
Co—O1 | 2.092 (3) | Co—O4 | 2.067 (3) |
Co—O2 | 2.141 (3) | Co—O5 | 2.199 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5WA···O9i | 0.85 (3) | 1.90 (7) | 2.750 (4) | 171 (6) |
O4—H4WA···O6ii | 0.85 (3) | 1.83 (4) | 2.673 (5) | 171 (6) |
O2—H2WA···O7iii | 0.85 (3) | 1.90 (5) | 2.714 (4) | 161 (5) |
O5—H5WB···O8 | 0.85 (3) | 1.99 (4) | 2.839 (3) | 173 (6) |
O2—H2WB···O5ii | 0.85 (3) | 2.10 (5) | 2.926 (4) | 163 (6) |
O4—H4WB···O8 | 0.85 (3) | 1.93 (5) | 2.752 (4) | 162 (7) |
O1—H1WA···O7iv | 0.85 (3) | 1.92 (4) | 2.765 (4) | 169 (6) |
O1—H1WB···O9iii | 0.85 (3) | 2.07 (5) | 2.818 (4) | 146 (6) |
O3—H3WB···O8v | 0.85 (3) | 1.88 (5) | 2.730 (6) | 174 (5) |
O3—H3WA···O9iii | 0.85 (3) | 2.10 (5) | 2.885 (4) | 154 (5) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1, y, z; (iii) x+1, y−1, z; (iv) x, y−1, z; (v) −x+1, −y+2, −z+1. |
In the title compound, (I) (Fig. 1), the local coordination geometry around the Co centre can be described as a distorted octahedron, formed by one N atom from one N-vinylimidazole ligand and five O atoms from five water molecules. The Co—N bond distance is 2.069 (3) Å, compared with a value of 2.097 (2) Å in [Co(viz)4SiF6] {viz is N-vinylimidazole; Driessen et al., 1982}. The Co—O bond distances range from 2.067 (3) to 2.199 (2) Å, compared to the similar Co—O(water) bond distances of 2.087 (3), 2.062 (2) and 2.087 (4) Å in [(pyz)Co2(H2O)10](SO4)2(H2O)2 (pyz is pyrazine; Xie et al., 2004).
In the crystal, the cations and anions are linked by O—H···O hydrogen bonds into two-dimensional layers parallell to ab-plane with the protruding N-vinylimidazole ligands.