Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107018021/sf3031sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270107018021/sf3031Isup2.hkl |
CCDC reference: 652488
The complex was prepared according to the method of Yeşilel et al., (2007). [Recrystallization from which solvent?]
All H atoms were placed in calculated positions, with C—H distances in the range 0.97–0.98 Å and Uiso(H) = 1.2Ueq(C). [This contradicts the data in the CIF tables, where all H-atom parameters have s.u.s and were therefore refined - please replace with the correct text]
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1993); cell refinement: CAD-4 EXPRESS; data reduction: CAD-4 EXPRESS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Co(C5H2N2O4)(C3H4N2)2(H2O)2] | F(000) = 788 |
Mr = 385.21 | Dx = 1.627 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 20122 reflections |
a = 8.628 (1) Å | θ = 2.4–28.9° |
b = 13.516 (1) Å | µ = 1.13 mm−1 |
c = 13.695 (1) Å | T = 296 K |
β = 99.978 (6)° | Prism, red |
V = 1572.9 (2) Å3 | 0.35 × 0.30 × 0.16 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 2815 independent reflections |
Radiation source: fine-focus sealed tube | 2552 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
rotation method scans | θmax = 25.2°, θmin = 2.4° |
Absorption correction: integration (CAD-4 EXPRESS; Enraf–Nonius, 1993) | h = −10→0 |
Tmin = 0.679, Tmax = 0.745 | k = −16→0 |
3009 measured reflections | l = −16→16 |
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)] = 0.038 | All H-atom parameters refined |
wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0706P)2 + 0.6775P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.001 |
2815 reflections | Δρmax = 0.89 e Å−3 |
274 parameters | Δρmin = −0.80 e Å−3 |
5 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0123 (14) |
[Co(C5H2N2O4)(C3H4N2)2(H2O)2] | V = 1572.9 (2) Å3 |
Mr = 385.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.628 (1) Å | µ = 1.13 mm−1 |
b = 13.516 (1) Å | T = 296 K |
c = 13.695 (1) Å | 0.35 × 0.30 × 0.16 mm |
β = 99.978 (6)° |
Enraf–Nonius CAD-4 diffractometer | 2815 independent reflections |
Absorption correction: integration (CAD-4 EXPRESS; Enraf–Nonius, 1993) | 2552 reflections with I > 2σ(I) |
Tmin = 0.679, Tmax = 0.745 | Rint = 0.038 |
3009 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 5 restraints |
wR(F2) = 0.105 | All H-atom parameters refined |
S = 1.11 | Δρmax = 0.89 e Å−3 |
2815 reflections | Δρmin = −0.80 e Å−3 |
274 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 | ||
C1 | 0.1583 (3) | 0.22225 (16) | 0.69827 (17) | 0.0248 (5) | |
C2 | 0.2204 (3) | 0.30418 (17) | 0.63903 (17) | 0.0223 (5) | |
C3 | 0.3451 (3) | 0.28779 (17) | 0.59226 (19) | 0.0272 (5) | |
C4 | 0.4053 (3) | 0.36854 (17) | 0.54515 (18) | 0.0243 (5) | |
C5 | 0.1999 (3) | 0.47008 (17) | 0.59567 (17) | 0.0231 (5) | |
C6 | −0.2850 (3) | 0.2689 (2) | 0.8178 (2) | 0.0373 (6) | |
C7 | −0.4826 (3) | 0.3660 (2) | 0.8297 (2) | 0.0380 (6) | |
C8 | −0.3825 (3) | 0.4125 (2) | 0.7794 (2) | 0.0320 (6) | |
C9 | 0.0988 (4) | 0.3947 (2) | 0.9330 (2) | 0.0397 (7) | |
C10 | 0.2161 (4) | 0.5355 (3) | 0.9600 (2) | 0.0486 (8) | |
C11 | 0.1460 (3) | 0.5294 (2) | 0.8641 (2) | 0.0399 (6) | |
N1 | 0.1455 (2) | 0.39223 (14) | 0.64066 (15) | 0.0229 (4) | |
N2 | 0.3304 (2) | 0.45659 (15) | 0.55234 (16) | 0.0260 (4) | |
N3 | −0.2583 (2) | 0.35118 (16) | 0.77169 (15) | 0.0290 (5) | |
N4 | −0.4193 (3) | 0.27491 (19) | 0.85333 (19) | 0.0403 (6) | |
N5 | 0.0720 (2) | 0.43954 (16) | 0.84765 (15) | 0.0307 (5) | |
N6 | 0.1858 (3) | 0.4494 (2) | 1.00276 (19) | 0.0438 (6) | |
O1 | 0.0493 (2) | 0.24386 (12) | 0.74397 (13) | 0.0302 (4) | |
O2 | 0.2221 (2) | 0.13893 (13) | 0.69762 (14) | 0.0338 (4) | |
O3 | 0.5205 (2) | 0.36571 (13) | 0.50016 (15) | 0.0334 (4) | |
O4 | 0.1376 (2) | 0.55419 (12) | 0.59194 (14) | 0.0328 (4) | |
O5 | −0.1354 (2) | 0.52249 (13) | 0.66222 (14) | 0.0297 (4) | |
O6 | −0.1645 (2) | 0.32160 (14) | 0.56939 (14) | 0.0323 (4) | |
Co1 | −0.05277 (3) | 0.38251 (2) | 0.71207 (2) | 0.02307 (16) | |
H2 | 0.363 (4) | 0.507 (3) | 0.527 (2) | 0.036 (8)* | |
H3 | 0.399 (4) | 0.228 (2) | 0.592 (2) | 0.033 (7)* | |
H4 | −0.451 (4) | 0.233 (3) | 0.888 (3) | 0.045 (9)* | |
H6 | −0.219 (4) | 0.211 (2) | 0.827 (3) | 0.062 (11)* | |
H6N | 0.204 (4) | 0.432 (3) | 1.059 (3) | 0.042 (9)* | |
H9 | 0.054 (4) | 0.330 (3) | 0.946 (3) | 0.055 (10)* | |
H10 | 0.269 (5) | 0.585 (3) | 1.000 (3) | 0.064 (11)* | |
H11 | 0.145 (4) | 0.574 (2) | 0.8096 (19) | 0.048 (9)* | |
H5A | −0.060 (4) | 0.544 (3) | 0.631 (3) | 0.049 (9)* | |
H5B | −0.151 (4) | 0.561 (3) | 0.707 (3) | 0.042 (9)* | |
H6A | −0.148 (4) | 0.356 (3) | 0.521 (3) | 0.039 (9)* | |
H6B | −0.260 (5) | 0.321 (3) | 0.566 (3) | 0.068 (12)* | |
H8 | −0.392 (3) | 0.475 (2) | 0.747 (2) | 0.031 (7)* | |
H7 | −0.581 (3) | 0.384 (2) | 0.849 (2) | 0.045 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0275 (12) | 0.0165 (11) | 0.0301 (12) | −0.0015 (9) | 0.0044 (9) | 0.0002 (9) |
C2 | 0.0214 (10) | 0.0181 (10) | 0.0277 (11) | −0.0012 (9) | 0.0047 (8) | −0.0005 (9) |
C3 | 0.0267 (12) | 0.0173 (11) | 0.0388 (13) | 0.0003 (9) | 0.0089 (10) | −0.0003 (10) |
C4 | 0.0208 (11) | 0.0214 (11) | 0.0316 (13) | −0.0003 (9) | 0.0073 (10) | −0.0024 (9) |
C5 | 0.0231 (11) | 0.0199 (11) | 0.0273 (11) | −0.0010 (9) | 0.0071 (9) | −0.0001 (9) |
C6 | 0.0367 (14) | 0.0314 (14) | 0.0469 (16) | −0.0001 (11) | 0.0162 (12) | 0.0082 (12) |
C7 | 0.0251 (13) | 0.0479 (16) | 0.0424 (16) | −0.0016 (12) | 0.0100 (11) | −0.0035 (12) |
C8 | 0.0303 (13) | 0.0283 (13) | 0.0371 (14) | 0.0005 (11) | 0.0054 (10) | −0.0013 (11) |
C9 | 0.0454 (16) | 0.0346 (15) | 0.0384 (15) | 0.0008 (12) | 0.0050 (12) | 0.0034 (12) |
C10 | 0.0516 (18) | 0.0458 (17) | 0.0449 (17) | −0.0089 (15) | −0.0015 (14) | −0.0075 (14) |
C11 | 0.0433 (15) | 0.0351 (15) | 0.0396 (15) | −0.0068 (12) | 0.0025 (12) | 0.0020 (12) |
N1 | 0.0218 (10) | 0.0176 (9) | 0.0310 (11) | 0.0005 (7) | 0.0089 (8) | 0.0015 (7) |
N2 | 0.0251 (10) | 0.0185 (10) | 0.0368 (11) | −0.0013 (8) | 0.0123 (8) | 0.0045 (8) |
N3 | 0.0276 (10) | 0.0261 (10) | 0.0353 (11) | −0.0017 (9) | 0.0107 (9) | 0.0020 (9) |
N4 | 0.0368 (13) | 0.0404 (14) | 0.0461 (14) | −0.0099 (10) | 0.0140 (10) | 0.0098 (11) |
N5 | 0.0328 (11) | 0.0312 (11) | 0.0281 (10) | 0.0015 (9) | 0.0051 (8) | 0.0000 (9) |
N6 | 0.0511 (15) | 0.0491 (15) | 0.0286 (13) | 0.0010 (12) | −0.0002 (10) | 0.0023 (11) |
O1 | 0.0325 (9) | 0.0205 (8) | 0.0412 (10) | 0.0023 (7) | 0.0168 (7) | 0.0060 (7) |
O2 | 0.0396 (10) | 0.0191 (8) | 0.0464 (11) | 0.0052 (8) | 0.0177 (8) | 0.0057 (8) |
O3 | 0.0277 (9) | 0.0271 (9) | 0.0502 (11) | −0.0002 (7) | 0.0201 (8) | 0.0001 (8) |
O4 | 0.0367 (10) | 0.0183 (8) | 0.0478 (10) | 0.0050 (7) | 0.0198 (8) | 0.0056 (7) |
O5 | 0.0334 (10) | 0.0220 (9) | 0.0349 (10) | 0.0022 (7) | 0.0094 (8) | −0.0020 (7) |
O6 | 0.0307 (10) | 0.0299 (10) | 0.0357 (10) | −0.0031 (8) | 0.0042 (8) | 0.0023 (8) |
Co1 | 0.0231 (2) | 0.0186 (2) | 0.0290 (2) | 0.00055 (11) | 0.00872 (14) | 0.00080 (11) |
C1—O1 | 1.251 (3) | C9—N6 | 1.332 (4) |
C1—O2 | 1.254 (3) | C9—H9 | 0.99 (4) |
C1—C2 | 1.524 (3) | C10—N6 | 1.349 (4) |
C2—N1 | 1.356 (3) | C10—C11 | 1.350 (4) |
C2—C3 | 1.362 (3) | C10—H10 | 0.93 (4) |
C3—C4 | 1.412 (3) | C11—N5 | 1.373 (4) |
C3—H3 | 0.93 (3) | C11—H11 | 0.957 (18) |
C4—O3 | 1.257 (3) | N1—Co1 | 2.117 (2) |
C4—N2 | 1.366 (3) | N2—H2 | 0.83 (3) |
C5—O4 | 1.255 (3) | N3—Co1 | 2.119 (2) |
C5—N1 | 1.344 (3) | N4—H4 | 0.82 (4) |
C5—N2 | 1.373 (3) | N5—Co1 | 2.123 (2) |
C6—N3 | 1.319 (3) | N6—H6N | 0.79 (4) |
C6—N4 | 1.335 (4) | O1—Co1 | 2.0846 (17) |
C6—H6 | 0.968 (19) | O5—Co1 | 2.0941 (17) |
C7—C8 | 1.350 (4) | O5—H5A | 0.89 (4) |
C7—N4 | 1.362 (4) | O5—H5B | 0.84 (4) |
C7—H7 | 0.961 (19) | O6—Co1 | 2.1845 (18) |
C8—N3 | 1.373 (3) | O6—H6A | 0.84 (4) |
C8—H8 | 0.95 (3) | O6—H6B | 0.82 (4) |
C9—N5 | 1.301 (4) | ||
O1—C1—O2 | 125.6 (2) | C4—N2—H2 | 119 (2) |
O1—C1—C2 | 117.45 (19) | C5—N2—H2 | 115 (2) |
O2—C1—C2 | 116.9 (2) | C6—N3—C8 | 105.6 (2) |
N1—C2—C3 | 124.6 (2) | C6—N3—Co1 | 125.48 (18) |
N1—C2—C1 | 114.59 (19) | C8—N3—Co1 | 128.70 (18) |
C3—C2—C1 | 120.8 (2) | C6—N4—C7 | 107.8 (2) |
C2—C3—C4 | 118.2 (2) | C6—N4—H4 | 125 (2) |
C2—C3—H3 | 125.2 (18) | C7—N4—H4 | 127 (2) |
C4—C3—H3 | 116.5 (18) | C9—N5—C11 | 105.1 (2) |
O3—C4—N2 | 119.1 (2) | C9—N5—Co1 | 126.9 (2) |
O3—C4—C3 | 125.8 (2) | C11—N5—Co1 | 127.99 (18) |
N2—C4—C3 | 115.1 (2) | C9—N6—C10 | 107.2 (3) |
O4—C5—N1 | 123.2 (2) | C9—N6—H6N | 121 (3) |
O4—C5—N2 | 118.7 (2) | C10—N6—H6N | 131 (3) |
N1—C5—N2 | 118.1 (2) | C1—O1—Co1 | 115.59 (14) |
N3—C6—N4 | 111.0 (2) | Co1—O5—H5A | 103 (2) |
N3—C6—H6 | 127 (2) | Co1—O5—H5B | 114 (2) |
N4—C6—H6 | 122 (2) | H5A—O5—H5B | 112 (3) |
C8—C7—N4 | 106.0 (2) | Co1—O6—H6A | 113 (2) |
C8—C7—H7 | 134 (2) | Co1—O6—H6B | 110 (3) |
N4—C7—H7 | 120 (2) | H6A—O6—H6B | 105 (4) |
C7—C8—N3 | 109.6 (3) | O1—Co1—O5 | 171.19 (7) |
C7—C8—H8 | 129.6 (18) | O1—Co1—N1 | 78.85 (7) |
N3—C8—H8 | 120.6 (18) | O5—Co1—N1 | 92.87 (8) |
N5—C9—N6 | 112.1 (3) | O1—Co1—N3 | 95.22 (7) |
N5—C9—H9 | 124 (2) | O5—Co1—N3 | 92.63 (8) |
N6—C9—H9 | 124 (2) | N1—Co1—N3 | 170.95 (8) |
N6—C10—C11 | 106.4 (3) | O1—Co1—N5 | 90.65 (8) |
N6—C10—H10 | 119 (2) | O5—Co1—N5 | 92.83 (8) |
C11—C10—H10 | 135 (3) | N1—Co1—N5 | 93.07 (8) |
C10—C11—N5 | 109.3 (3) | N3—Co1—N5 | 93.83 (8) |
C10—C11—H11 | 132 (2) | O1—Co1—O6 | 87.34 (7) |
N5—C11—H11 | 119 (2) | O5—Co1—O6 | 88.64 (7) |
C5—N1—C2 | 118.31 (19) | N1—Co1—O6 | 82.93 (8) |
C5—N1—Co1 | 129.38 (15) | N3—Co1—O6 | 90.02 (8) |
C2—N1—Co1 | 112.26 (14) | N5—Co1—O6 | 175.80 (8) |
C4—N2—C5 | 125.5 (2) | ||
O1—C1—C2—N1 | −1.8 (3) | N5—C9—N6—C10 | 0.5 (4) |
O2—C1—C2—N1 | 178.8 (2) | C11—C10—N6—C9 | −0.4 (4) |
O1—C1—C2—C3 | 176.0 (2) | O2—C1—O1—Co1 | −171.0 (2) |
O2—C1—C2—C3 | −3.3 (3) | C2—C1—O1—Co1 | 9.7 (3) |
N1—C2—C3—C4 | 2.5 (4) | C1—O1—Co1—N1 | −10.23 (17) |
C1—C2—C3—C4 | −175.0 (2) | C1—O1—Co1—N3 | 162.86 (17) |
C2—C3—C4—O3 | 179.1 (2) | C1—O1—Co1—N5 | −103.23 (18) |
C2—C3—C4—N2 | 0.3 (3) | C1—O1—Co1—O6 | 73.08 (18) |
N4—C7—C8—N3 | 0.0 (3) | C5—N1—Co1—O1 | −174.0 (2) |
N6—C10—C11—N5 | 0.2 (4) | C2—N1—Co1—O1 | 8.78 (16) |
O4—C5—N1—C2 | 179.0 (2) | C5—N1—Co1—O5 | 9.1 (2) |
N2—C5—N1—C2 | −1.4 (3) | C2—N1—Co1—O5 | −168.17 (16) |
O4—C5—N1—Co1 | 1.9 (4) | C5—N1—Co1—N5 | −83.9 (2) |
N2—C5—N1—Co1 | −178.46 (16) | C2—N1—Co1—N5 | 98.83 (17) |
C3—C2—N1—C5 | −2.0 (4) | C5—N1—Co1—O6 | 97.3 (2) |
C1—C2—N1—C5 | 175.7 (2) | C2—N1—Co1—O6 | −79.90 (16) |
C3—C2—N1—Co1 | 175.55 (19) | C6—N3—Co1—O1 | 4.3 (2) |
C1—C2—N1—Co1 | −6.7 (2) | C8—N3—Co1—O1 | 177.8 (2) |
O3—C4—N2—C5 | 177.3 (2) | C6—N3—Co1—O5 | −179.7 (2) |
C3—C4—N2—C5 | −3.9 (3) | C8—N3—Co1—O5 | −6.2 (2) |
O4—C5—N2—C4 | −175.9 (2) | C6—N3—Co1—N5 | −86.7 (2) |
N1—C5—N2—C4 | 4.5 (4) | C8—N3—Co1—N5 | 86.8 (2) |
N4—C6—N3—C8 | 0.4 (3) | C6—N3—Co1—O6 | 91.6 (2) |
N4—C6—N3—Co1 | 175.10 (19) | C8—N3—Co1—O6 | −94.9 (2) |
C7—C8—N3—C6 | −0.3 (3) | C9—N5—Co1—O1 | −39.5 (2) |
C7—C8—N3—Co1 | −174.75 (18) | C11—N5—Co1—O1 | 138.1 (2) |
N3—C6—N4—C7 | −0.4 (3) | C9—N5—Co1—O5 | 148.6 (2) |
C8—C7—N4—C6 | 0.2 (3) | C11—N5—Co1—O5 | −33.8 (2) |
N6—C9—N5—C11 | −0.4 (3) | C9—N5—Co1—N1 | −118.4 (2) |
N6—C9—N5—Co1 | 177.64 (19) | C11—N5—Co1—N1 | 59.2 (2) |
C10—C11—N5—C9 | 0.1 (3) | C9—N5—Co1—N3 | 55.8 (2) |
C10—C11—N5—Co1 | −177.9 (2) | C11—N5—Co1—N3 | −126.6 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O3i | 0.83 (3) | 2.06 (3) | 2.874 (3) | 165 (3) |
N4—H4···O3ii | 0.82 (4) | 2.08 (4) | 2.879 (3) | 166 (3) |
N6—H6N···O2iii | 0.79 (4) | 2.11 (4) | 2.891 (3) | 169 (3) |
O5—H5A···O4 | 0.89 (4) | 1.88 (4) | 2.729 (3) | 160 (3) |
O5—H5B···O2iv | 0.84 (4) | 1.85 (4) | 2.687 (3) | 170 (3) |
O6—H6A···O4v | 0.84 (4) | 1.98 (4) | 2.816 (3) | 173 (3) |
O6—H6B···O3vi | 0.82 (4) | 2.05 (4) | 2.783 (3) | 150 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, −y+1/2, z+1/2; (iii) x, −y+1/2, z+1/2; (iv) −x, y+1/2, −z+3/2; (v) −x, −y+1, −z+1; (vi) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C5H2N2O4)(C3H4N2)2(H2O)2] |
Mr | 385.21 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 8.628 (1), 13.516 (1), 13.695 (1) |
β (°) | 99.978 (6) |
V (Å3) | 1572.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.13 |
Crystal size (mm) | 0.35 × 0.30 × 0.16 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Integration (CAD-4 EXPRESS; Enraf–Nonius, 1993) |
Tmin, Tmax | 0.679, 0.745 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3009, 2815, 2552 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.105, 1.11 |
No. of reflections | 2815 |
No. of parameters | 274 |
No. of restraints | 5 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.89, −0.80 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1993), CAD-4 EXPRESS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
N1—Co1 | 2.117 (2) | O1—Co1 | 2.0846 (17) |
N3—Co1 | 2.119 (2) | O5—Co1 | 2.0941 (17) |
N5—Co1 | 2.123 (2) | O6—Co1 | 2.1845 (18) |
O1—Co1—N1 | 78.85 (7) | N1—Co1—N5 | 93.07 (8) |
O5—Co1—N1 | 92.87 (8) | N3—Co1—N5 | 93.83 (8) |
O1—Co1—N3 | 95.22 (7) | O1—Co1—O6 | 87.34 (7) |
O5—Co1—N3 | 92.63 (8) | O5—Co1—O6 | 88.64 (7) |
N1—Co1—N3 | 170.95 (8) | N1—Co1—O6 | 82.93 (8) |
O1—Co1—N5 | 90.65 (8) | N3—Co1—O6 | 90.02 (8) |
O5—Co1—N5 | 92.83 (8) | N5—Co1—O6 | 175.80 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O3i | 0.83 (3) | 2.06 (3) | 2.874 (3) | 165 (3) |
N4—H4···O3ii | 0.82 (4) | 2.08 (4) | 2.879 (3) | 166 (3) |
N6—H6N···O2iii | 0.79 (4) | 2.11 (4) | 2.891 (3) | 169 (3) |
O5—H5A···O4 | 0.89 (4) | 1.88 (4) | 2.729 (3) | 160 (3) |
O5—H5B···O2iv | 0.84 (4) | 1.85 (4) | 2.687 (3) | 170 (3) |
O6—H6A···O4v | 0.84 (4) | 1.98 (4) | 2.816 (3) | 173 (3) |
O6—H6B···O3vi | 0.82 (4) | 2.05 (4) | 2.783 (3) | 150 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, −y+1/2, z+1/2; (iii) x, −y+1/2, z+1/2; (iv) −x, y+1/2, −z+3/2; (v) −x, −y+1, −z+1; (vi) x−1, y, z. |
Orotic acid (H3Or?) is an interesting ligand due to its potential multidentate nature, especially above the deprotonation pH values. It coordinates to metal ions as a bidentate ligand through both the N atom of its pyrimidine ring and the O atom of its carboxyl group. Examples are found in the crystal structures of CoII–orotate complexes with water, ethylenediamine (Içbudak et al., 2003), nicotine amide (Yeşilel et al., 2005) or 2,2'-bipyridylamine (Plater et al., 2002). The orotate ligand act as a bridging bidentate ligand in the polymeric [Co(HOr)(H2O)3]n complex (Şahin et al., 2006; Plater et al., 2002; Sun et al., 2002) and in [Co(H2Or)2(H2O)4]·H2O, orotate acts as a monodentate ligand through the carboxylate O atom (Kose et al., 2006). In the [Co(H2O)2(phen)2](H2Or)2 complex, orotic acid acts as a counter-ion (Bulut et al., 2003). In this study, we report the structural characterization of the title mer-[Co(HOr)(H2O)2(im)2] complex, (I) (im is imidazole). The molecular structure of (I) is shown in Fig. 1 and selected geometric parameters are given in Table 1.
The CoII ion of (I) has a distorted octahedral coordination geometry comprised of a pyrimidine N atom and a carboxylate O atom from a bisdeprotonated bidentate orotate ligand [Co1—N1 = 2.117 (2) Å and Co1—O1 = 2.085 (2) Å], two water O atoms [Co1—O5 = 2.094 (2) Å and Co1—O6 = 2.185 (2) Å] and two N atoms from the two imidazole ligands [Co1—N3 = 2.120 (2) Å and Co1—N5 = 2.123 (2) Å]. The orotate ligand is essentially planar [r.m.s. deviation = 0.024 (2) Å], with a slight deviation from planarity arising from the non-zero torsion angle between the carboxylate group and the ring [N1—C2—C1—O1 = 1.8 (3)°]. This torsion angle indicates distortion of the orotate ligand caused by coordination to the CoII ion.
The carboxylate O atoms have different environments. Atom O1 coordinates to the CoII ion, while atom O2 acts as an acceptor for two linear hydrogen bonds. However, the C—O distances [C1—O1 = 1.251 Å and C1—O2 = 1.254 Å] are practically equal. These bond distances are comparable with those in similar complexes (Uçar et al., 2004; Içbudak et al., 2003; Lutz, 2001).
The two imidazole rings are individually planar and the maximum deviations from these planes are 0.002 (3) Å for atom N4 and 0.003 (3) Å for atom C9. These planes are approximately perpendicular, with a dihedral angle of 88.35 (17)°, in agreement with the value previously reported for the diaquabis(imidazole)orotatenickel(II) complex (Uçar et al., 2004).
The crystal packing of (I) is formed via intermolecular hydrogen bonds, and weak π–π and C—H···π interactions. Two orotate molecules are joined by two N2—H2···O3 hydrogen bonds, which leads to the formation of a centrosymmetric dimer of (I) (Fig. 1). Two aqua ligands and imidazole atoms N4 and N6 also form intermolecular hydrogen-bonding interactions with the orotate ligand, through carboxylate atom O2 [N6—H6···O2 = 2.891 (3) Å and O5—H5B···O2 = 2.687 (3) Å] and carbonyl atoms O3 [N4—H4···O3 = 2.879 (3) Å and O6—H6B···O3 = 2.783 (3) Å] and O4 [O5—H5A···O4 = 2.729 (3) Å and O6—H6A···O4 = 2.816 (3) Å] (Fig. 2).
In the extended structure of (I), there are also weak π–π and C—H···π interactions (Fig. 3). Two intermolecular π–π interactions occur between two symmetry-related imidazole rings (N5/N6/C9–C11, ring A) of neighbouring molecules. Ring A is oriented in such a way that the perpendicular distances from A to Aiii is 3.354 Å, the closest interatomic distance being C10···C9iii [3.435 (3); symmetry code: (iii) -x, 1 - y, 2 - z]. The distance between the ring centroids is 3.646 (2) Å. Also, π–π interactions occur between the other imidazole ring (N3/N4/C6–C8, ring B) and the pyrimidine ring of the orotate ligand (N1/N2/C2–C5, ring C). Rings B and C are oriented in such a way that the perpendicular distance from B to C is 3.575 Å, the closest interatomic distance is C7···C2i [3.430 (3) Å; symmetry code: (i) -1 + x, y, z] and the distance between the ring centroids is 3.950 (2) Å. The dihedral angles between the planes of rings B and C is 10.51 (14)°. Rings A and B are also involved in intermolecular C—H···π interactions with atoms C7 and C10. For the C7—H7···π and C10—H10···π contacts, the distance between atom H7 and the centroid of ring A (CgA) is 2.97 (3) Å and the C7—H7···CgA angle is 171 (2)°, while the distance between atom H10 and the centroid of ring B (CgB) is 2.81 (4) Å and the C10—H10···CgB angle is 149 (3)°.