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In the title compound, [Co(C
12H
8N
2)
2(H
2O)
2](C
5H
3N
2O
4)
2·2.25H
2O, the cobalt cation, located on a twofold axis, is coordinated by two symmetry-related aqua ligands together with a pair of symmetry-related bidentate phenanthroline (phen) molecules, and exhibits a distorted octahedral coordination. The unique orotate anion in the asymmetric unit has a single negative charge. The coordinated water molecules link the orotate ions to the metal complex
via O—H
![...](/logos/entities/ctdot_rmgif.gif)
O hydrogen bonds. Each uncoordinated water molecule is hydrogen bonded to orotate ions through O—H
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O hydrogen bonds.
Supporting information
CCDC reference: 222803
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean
(C-C) = 0.003 Å
- H-atom completeness 99%
- Disorder in solvent or counterion
- R factor = 0.037
- wR factor = 0.100
- Data-to-parameter ratio = 17.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ..... 0.99
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .. ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .. ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing). ?
PLAT302_ALERT_4_C Anion/Solvent Disorder ....................... 12.00 Perc.
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ... <O7
PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C13 - C14 = 1.53 Ang.
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C34 H30.5 Co1 N8 O12.25
Atom count from the _atom_site data: C34 H30 Co1 N8 O12.25
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 4
From the CIF: _chemical_formula_sum C34 H30.50 Co N8 O12.25
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 136.00 136.00 0.00
H 122.00 120.00 2.00
Co 4.00 4.00 0.00
N 32.00 32.00 0.00
O 49.00 49.00 0.00
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
7 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
3 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
[Co(HOra)(H2O)4]·H2O precursor was prepared as previously described in İçbudak et al. (2003). A solution of phenanthroline (0.748 g, 4 mmol) in ethanol (15 ml) was added dropwise into a stirred solution of [Co(HOra)(H2O)4]·H2O (0.61 g, 2 mmol) in water (50 ml). The resulting solution was heated to 333 K in a temperature-controlled bath and then refluxed and stirred for 12 h at 333 K. The orange crystals of the title compound that formed after cooling to room temparature, filtered off and washed with 10 ml portions of cold distilled water and acetone and dried in vacuo. Yield: 0.92 g (79.3%). Found: C 29.5, H 5.3, N 19.7%; calculated for C34H30.5CoN8O12.25: C 29.1, H 5.4, N 19.4%.
H atoms attached to the water atoms O1 and O6 were located from a difference Fourier map and their x, y, z and Uiso parameters were refined [O—H = 0.82 (5)–0.88 (4) Å]. The remaining H atoms were placed geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å, N—H = 0.86 Å and Uiso(H) = 1.2Ueq(C or N). At this stage, the maximum difference density of 1.61 e Å−3 (the ratio of maximum /minimum residual density is 3.22) indicated the presence of a possible atom site. Also a check for the solvent-accessible volume using PLATON (Spek, 1997) showed total potential solvent area volume of 74 Å3. Attempts to refine this peak as a water O atom (O7) resulted in a partial occupancy of 0.131 (5). The occupancy was later fixed at 0.125 to result in one water O7 per unit cell. H atoms attached to O7 were not located.
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Crystal data top
[Co(C12H8N2)2(H2O)2](C5H3N2O4)2·2.25H2O | F(000) = 1662 |
Mr = 806.09 | Dx = 1.595 Mg m−3 Dm = 1.59 Mg m−3 Dm measured by not measured |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4607 reflections |
a = 16.1401 (11) Å | θ = 2.1–29.7° |
b = 12.5692 (10) Å | µ = 0.59 mm−1 |
c = 16.5650 (11) Å | T = 293 K |
β = 92.435 (5)° | Prism, orange |
V = 3357.5 (4) Å3 | 0.35 × 0.23 × 0.15 mm |
Z = 4 | |
Data collection top
Stoe IPDS-2 diffractometer | 3086 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 29.4°, θmin = 2.1° |
Detector resolution: 6.67 pixels mm-1 | h = −22→22 |
ϕ scans | k = 0→17 |
4607 measured reflections | l = 0→22 |
4607 independent 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0648P)2] where P = (Fo2 + 2Fc2)/3 |
4607 reflections | (Δ/σ)max < 0.001 |
267 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
Crystal data top
[Co(C12H8N2)2(H2O)2](C5H3N2O4)2·2.25H2O | V = 3357.5 (4) Å3 |
Mr = 806.09 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.1401 (11) Å | µ = 0.59 mm−1 |
b = 12.5692 (10) Å | T = 293 K |
c = 16.5650 (11) Å | 0.35 × 0.23 × 0.15 mm |
β = 92.435 (5)° | |
Data collection top
Stoe IPDS-2 diffractometer | 3086 reflections with I > 2σ(I) |
4607 measured reflections | Rint = 0.000 |
4607 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | Δρmax = 0.26 e Å−3 |
4607 reflections | Δρmin = −0.51 e Å−3 |
267 parameters | |
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 | Occ. (<1) |
Co1 | 0.5000 | 0.74187 (3) | 0.2500 | 0.03888 (10) | |
O1 | 0.58166 (8) | 0.86648 (11) | 0.28418 (8) | 0.0466 (3) | |
O2 | 0.49164 (8) | 0.00566 (12) | 0.10797 (8) | 0.0570 (4) | |
O3 | 0.68053 (8) | 0.16286 (12) | −0.04585 (8) | 0.0556 (4) | |
O4 | 0.67869 (11) | 0.22904 (13) | 0.30089 (9) | 0.0696 (4) | |
O5 | 0.75468 (9) | 0.30950 (14) | 0.20987 (9) | 0.0625 (4) | |
O6 | 0.73922 (14) | 0.0553 (2) | 0.39015 (14) | 0.0868 (6) | |
N1 | 0.55141 (9) | 0.73772 (12) | 0.13373 (9) | 0.0431 (3) | |
N2 | 0.42321 (9) | 0.62817 (12) | 0.18875 (9) | 0.0437 (3) | |
N3 | 0.68639 (8) | 0.19895 (11) | 0.08901 (8) | 0.0386 (3) | |
H3 | 0.7273 | 0.2420 | 0.0841 | 0.046* | |
N4 | 0.58923 (9) | 0.08267 (12) | 0.03426 (9) | 0.0442 (3) | |
H4 | 0.5688 | 0.0491 | −0.0072 | 0.053* | |
C1 | 0.61693 (13) | 0.78915 (17) | 0.10804 (13) | 0.0556 (5) | |
H1 | 0.6514 | 0.8247 | 0.1455 | 0.067* | |
C2 | 0.63616 (14) | 0.79193 (19) | 0.02662 (14) | 0.0623 (5) | |
H2 | 0.6823 | 0.8297 | 0.0107 | 0.075* | |
C3 | 0.58763 (14) | 0.73963 (16) | −0.02909 (13) | 0.0580 (5) | |
H3A | 0.6000 | 0.7417 | −0.0834 | 0.070* | |
C4 | 0.51834 (12) | 0.68201 (15) | −0.00417 (11) | 0.0484 (4) | |
C5 | 0.50334 (10) | 0.68386 (13) | 0.07881 (10) | 0.0409 (4) | |
C6 | 0.43525 (10) | 0.62364 (13) | 0.10819 (11) | 0.0421 (4) | |
C7 | 0.36385 (12) | 0.56786 (16) | 0.21761 (14) | 0.0544 (5) | |
H7 | 0.3551 | 0.5701 | 0.2727 | 0.065* | |
C8 | 0.31401 (12) | 0.50121 (16) | 0.16868 (17) | 0.0633 (6) | |
H8 | 0.2742 | 0.4582 | 0.1913 | 0.076* | |
C9 | 0.32410 (13) | 0.49981 (17) | 0.08840 (16) | 0.0627 (6) | |
H9 | 0.2900 | 0.4573 | 0.0552 | 0.075* | |
C10 | 0.38590 (11) | 0.56230 (15) | 0.05476 (13) | 0.0505 (4) | |
C11 | 0.40186 (14) | 0.56483 (19) | −0.03010 (14) | 0.0620 (6) | |
H11 | 0.3679 | 0.5265 | −0.0664 | 0.074* | |
C12 | 0.46503 (14) | 0.62174 (18) | −0.05741 (13) | 0.0585 (5) | |
H12 | 0.4743 | 0.6219 | −0.1124 | 0.070* | |
C13 | 0.70097 (11) | 0.24621 (15) | 0.23176 (11) | 0.0463 (4) | |
C14 | 0.65663 (10) | 0.18347 (13) | 0.16392 (10) | 0.0395 (3) | |
C15 | 0.59223 (10) | 0.11708 (15) | 0.17480 (11) | 0.0448 (4) | |
H15 | 0.5732 | 0.1058 | 0.2263 | 0.054* | |
C16 | 0.55352 (10) | 0.06420 (15) | 0.10672 (11) | 0.0448 (4) | |
C17 | 0.65450 (10) | 0.14971 (14) | 0.02185 (10) | 0.0406 (4) | |
H1A | 0.5636 (14) | 0.9110 (19) | 0.3175 (14) | 0.058 (6)* | |
H1B | 0.631 (2) | 0.856 (3) | 0.300 (2) | 0.108 (11)* | |
H6A | 0.712 (3) | 0.000 (4) | 0.385 (3) | 0.15 (2)* | |
H6B | 0.713 (2) | 0.098 (3) | 0.356 (2) | 0.110 (12)* | |
O7 | 0.5000 | 0.3473 (9) | 0.2500 | 0.084 (3)* | 0.25 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.03765 (16) | 0.04209 (19) | 0.03728 (17) | 0.000 | 0.00592 (12) | 0.000 |
O1 | 0.0378 (6) | 0.0506 (7) | 0.0513 (8) | 0.0040 (6) | 0.0009 (5) | −0.0108 (6) |
O2 | 0.0474 (7) | 0.0663 (9) | 0.0575 (8) | −0.0235 (6) | 0.0047 (6) | 0.0124 (7) |
O3 | 0.0552 (7) | 0.0727 (9) | 0.0396 (7) | −0.0269 (7) | 0.0103 (6) | −0.0026 (6) |
O4 | 0.0967 (12) | 0.0718 (10) | 0.0414 (7) | −0.0113 (9) | 0.0165 (8) | −0.0027 (7) |
O5 | 0.0500 (7) | 0.0855 (11) | 0.0526 (8) | −0.0230 (7) | 0.0086 (6) | −0.0146 (7) |
O6 | 0.0884 (13) | 0.0853 (14) | 0.0854 (14) | 0.0102 (12) | −0.0099 (11) | 0.0119 (11) |
N1 | 0.0433 (7) | 0.0454 (8) | 0.0412 (7) | −0.0059 (6) | 0.0101 (6) | −0.0039 (6) |
N2 | 0.0405 (7) | 0.0419 (8) | 0.0491 (8) | −0.0033 (6) | 0.0068 (6) | 0.0013 (6) |
N3 | 0.0348 (6) | 0.0417 (7) | 0.0397 (7) | −0.0072 (5) | 0.0061 (5) | 0.0006 (6) |
N4 | 0.0420 (7) | 0.0477 (8) | 0.0431 (8) | −0.0137 (6) | 0.0051 (6) | 0.0030 (6) |
C1 | 0.0522 (10) | 0.0598 (11) | 0.0559 (11) | −0.0136 (9) | 0.0163 (9) | −0.0065 (9) |
C2 | 0.0621 (12) | 0.0649 (13) | 0.0621 (13) | −0.0112 (10) | 0.0271 (10) | −0.0011 (10) |
C3 | 0.0698 (12) | 0.0591 (12) | 0.0468 (10) | 0.0099 (10) | 0.0203 (9) | 0.0043 (9) |
C4 | 0.0556 (10) | 0.0466 (10) | 0.0431 (9) | 0.0119 (8) | 0.0039 (8) | −0.0019 (7) |
C5 | 0.0428 (8) | 0.0391 (8) | 0.0412 (9) | 0.0050 (7) | 0.0045 (7) | −0.0028 (7) |
C6 | 0.0402 (8) | 0.0359 (8) | 0.0501 (10) | 0.0040 (7) | 0.0013 (7) | −0.0014 (7) |
C7 | 0.0468 (9) | 0.0471 (10) | 0.0699 (13) | −0.0036 (8) | 0.0113 (9) | 0.0089 (9) |
C8 | 0.0453 (10) | 0.0429 (10) | 0.1019 (19) | −0.0070 (8) | 0.0070 (11) | 0.0050 (11) |
C9 | 0.0472 (10) | 0.0462 (11) | 0.0940 (17) | −0.0024 (8) | −0.0059 (10) | −0.0124 (11) |
C10 | 0.0447 (9) | 0.0419 (9) | 0.0643 (12) | 0.0053 (7) | −0.0070 (8) | −0.0110 (8) |
C11 | 0.0599 (12) | 0.0623 (13) | 0.0623 (13) | 0.0121 (10) | −0.0157 (10) | −0.0199 (10) |
C12 | 0.0699 (13) | 0.0618 (12) | 0.0429 (10) | 0.0185 (10) | −0.0063 (9) | −0.0092 (9) |
C13 | 0.0445 (8) | 0.0514 (10) | 0.0433 (9) | 0.0021 (8) | 0.0058 (7) | −0.0029 (8) |
C14 | 0.0363 (7) | 0.0415 (8) | 0.0410 (9) | 0.0027 (6) | 0.0066 (6) | 0.0044 (7) |
C15 | 0.0410 (8) | 0.0512 (10) | 0.0428 (9) | −0.0040 (7) | 0.0087 (7) | 0.0056 (7) |
C16 | 0.0375 (8) | 0.0466 (9) | 0.0507 (10) | −0.0059 (7) | 0.0066 (7) | 0.0100 (7) |
C17 | 0.0369 (7) | 0.0429 (9) | 0.0423 (9) | −0.0067 (7) | 0.0055 (6) | 0.0024 (7) |
Geometric parameters (Å, º) top
Co1—O1 | 2.1089 (13) | C1—C2 | 1.397 (3) |
Co1—O1i | 2.1089 (13) | C1—H1 | 0.93 |
Co1—N2 | 2.1216 (15) | C2—C3 | 1.355 (3) |
Co1—N2i | 2.1216 (15) | C2—H2 | 0.93 |
Co1—N1i | 2.1300 (14) | C3—C4 | 1.409 (3) |
Co1—N1 | 2.1300 (14) | C3—H3A | 0.93 |
O1—H1A | 0.85 (3) | C4—C5 | 1.406 (2) |
O1—H1B | 0.85 (3) | C4—C12 | 1.424 (3) |
O2—C16 | 1.241 (2) | C5—C6 | 1.436 (2) |
O3—C17 | 1.225 (2) | C6—C10 | 1.397 (2) |
O4—C13 | 1.234 (2) | C7—C8 | 1.397 (3) |
O5—C13 | 1.242 (2) | C7—H7 | 0.93 |
O6—H6A | 0.82 (5) | C8—C9 | 1.347 (3) |
O6—H6B | 0.88 (4) | C8—H8 | 0.93 |
N1—C1 | 1.325 (2) | C9—C10 | 1.403 (3) |
N1—C5 | 1.352 (2) | C9—H9 | 0.93 |
N2—C7 | 1.327 (2) | C10—C11 | 1.440 (3) |
N2—C6 | 1.358 (2) | C11—C12 | 1.340 (3) |
N3—C17 | 1.355 (2) | C11—H11 | 0.93 |
N3—C14 | 1.363 (2) | C12—H12 | 0.93 |
N3—H3 | 0.86 | C13—C14 | 1.526 (2) |
N4—C17 | 1.371 (2) | C14—C15 | 1.351 (2) |
N4—C16 | 1.373 (2) | C15—C16 | 1.430 (3) |
N4—H4 | 0.86 | C15—H15 | 0.93 |
| | | |
O1—Co1—O1i | 84.08 (8) | C5—C4—C12 | 119.33 (18) |
O1—Co1—N2 | 167.01 (5) | C3—C4—C12 | 123.94 (19) |
O1i—Co1—N2 | 91.50 (6) | N1—C5—C4 | 123.26 (16) |
O1—Co1—N2i | 91.50 (6) | N1—C5—C6 | 117.48 (15) |
O1i—Co1—N2i | 167.01 (5) | C4—C5—C6 | 119.24 (16) |
N2—Co1—N2i | 95.31 (8) | N2—C6—C10 | 122.97 (17) |
O1—Co1—N1i | 92.20 (6) | N2—C6—C5 | 117.02 (15) |
O1i—Co1—N1i | 89.88 (5) | C10—C6—C5 | 120.00 (17) |
N2—Co1—N1i | 100.01 (6) | N2—C7—C8 | 122.7 (2) |
N2i—Co1—N1i | 78.06 (5) | N2—C7—H7 | 118.6 |
O1—Co1—N1 | 89.88 (5) | C8—C7—H7 | 118.6 |
O1i—Co1—N1 | 92.20 (6) | C9—C8—C7 | 119.3 (2) |
N2—Co1—N1 | 78.06 (5) | C9—C8—H8 | 120.3 |
N2i—Co1—N1 | 100.01 (6) | C7—C8—H8 | 120.3 |
N1i—Co1—N1 | 177.19 (8) | C8—C9—C10 | 120.2 (2) |
Co1—O1—H1A | 115.9 (15) | C8—C9—H9 | 119.9 |
Co1—O1—H1B | 122 (2) | C10—C9—H9 | 119.9 |
H1A—O1—H1B | 105 (3) | C6—C10—C9 | 116.9 (2) |
H6A—O6—H6B | 103 (4) | C6—C10—C11 | 119.03 (19) |
C1—N1—C5 | 118.12 (16) | C9—C10—C11 | 124.02 (19) |
C1—N1—Co1 | 128.71 (13) | C12—C11—C10 | 120.77 (19) |
C5—N1—Co1 | 112.72 (11) | C12—C11—H11 | 119.6 |
C7—N2—C6 | 117.77 (17) | C10—C11—H11 | 119.6 |
C7—N2—Co1 | 128.95 (14) | C11—C12—C4 | 121.6 (2) |
C6—N2—Co1 | 113.15 (11) | C11—C12—H12 | 119.2 |
C17—N3—C14 | 123.08 (14) | C4—C12—H12 | 119.2 |
C17—N3—H3 | 118.5 | O4—C13—O5 | 128.15 (18) |
C14—N3—H3 | 118.5 | O4—C13—C14 | 116.55 (16) |
C17—N4—C16 | 126.05 (15) | O5—C13—C14 | 115.30 (16) |
C17—N4—H4 | 117.0 | C15—C14—N3 | 120.81 (16) |
C16—N4—H4 | 117.0 | C15—C14—C13 | 124.09 (16) |
N1—C1—C2 | 122.4 (2) | N3—C14—C13 | 115.10 (14) |
N1—C1—H1 | 118.8 | C14—C15—C16 | 119.66 (16) |
C2—C1—H1 | 118.8 | C14—C15—H15 | 120.2 |
C3—C2—C1 | 119.98 (19) | C16—C15—H15 | 120.2 |
C3—C2—H2 | 120.0 | O2—C16—N4 | 118.86 (17) |
C1—C2—H2 | 120.0 | O2—C16—C15 | 125.97 (16) |
C2—C3—C4 | 119.54 (18) | N4—C16—C15 | 115.17 (14) |
C2—C3—H3A | 120.2 | O3—C17—N3 | 123.81 (15) |
C4—C3—H3A | 120.2 | O3—C17—N4 | 121.04 (16) |
C5—C4—C3 | 116.72 (17) | N3—C17—N4 | 115.15 (14) |
| | | |
O1—Co1—N1—C1 | 7.80 (18) | N1—C5—C6—N2 | 1.8 (2) |
O1i—Co1—N1—C1 | 91.87 (18) | C4—C5—C6—N2 | −179.87 (15) |
N2—Co1—N1—C1 | −177.06 (18) | N1—C5—C6—C10 | −176.91 (15) |
N2i—Co1—N1—C1 | −83.69 (18) | C4—C5—C6—C10 | 1.4 (2) |
O1—Co1—N1—C5 | −164.20 (12) | C6—N2—C7—C8 | −0.2 (3) |
O1i—Co1—N1—C5 | −80.13 (12) | Co1—N2—C7—C8 | 175.41 (14) |
N2—Co1—N1—C5 | 10.93 (12) | N2—C7—C8—C9 | −2.2 (3) |
N2i—Co1—N1—C5 | 104.30 (12) | C7—C8—C9—C10 | 2.0 (3) |
O1—Co1—N2—C7 | −163.6 (2) | N2—C6—C10—C9 | −3.0 (3) |
O1i—Co1—N2—C7 | −93.84 (16) | C5—C6—C10—C9 | 175.73 (17) |
N2i—Co1—N2—C7 | 75.09 (16) | N2—C6—C10—C11 | 178.24 (17) |
N1i—Co1—N2—C7 | −3.69 (17) | C5—C6—C10—C11 | −3.1 (3) |
N1—Co1—N2—C7 | 174.23 (17) | C8—C9—C10—C6 | 0.4 (3) |
O1—Co1—N2—C6 | 12.2 (3) | C8—C9—C10—C11 | 179.2 (2) |
O1i—Co1—N2—C6 | 81.92 (12) | C6—C10—C11—C12 | 2.6 (3) |
N2i—Co1—N2—C6 | −109.15 (13) | C9—C10—C11—C12 | −176.1 (2) |
N1i—Co1—N2—C6 | 172.07 (11) | C10—C11—C12—C4 | −0.3 (3) |
N1—Co1—N2—C6 | −10.01 (12) | C5—C4—C12—C11 | −1.4 (3) |
C5—N1—C1—C2 | 1.9 (3) | C3—C4—C12—C11 | 177.3 (2) |
Co1—N1—C1—C2 | −169.74 (16) | C17—N3—C14—C15 | −0.3 (3) |
N1—C1—C2—C3 | −0.9 (4) | C17—N3—C14—C13 | 179.98 (15) |
C1—C2—C3—C4 | −0.5 (3) | O4—C13—C14—C15 | 4.5 (3) |
C2—C3—C4—C5 | 0.8 (3) | O5—C13—C14—C15 | −174.72 (18) |
C2—C3—C4—C12 | −178.0 (2) | O4—C13—C14—N3 | −175.81 (17) |
C1—N1—C5—C4 | −1.6 (3) | O5—C13—C14—N3 | 5.0 (2) |
Co1—N1—C5—C4 | 171.33 (13) | N3—C14—C15—C16 | −1.4 (3) |
C1—N1—C5—C6 | 176.61 (17) | C13—C14—C15—C16 | 178.29 (16) |
Co1—N1—C5—C6 | −10.46 (19) | C17—N4—C16—O2 | 176.05 (17) |
C3—C4—C5—N1 | 0.3 (3) | C17—N4—C16—C15 | −3.3 (3) |
C12—C4—C5—N1 | 179.07 (16) | C14—C15—C16—O2 | −176.25 (18) |
C3—C4—C5—C6 | −177.90 (16) | C14—C15—C16—N4 | 3.0 (3) |
C12—C4—C5—C6 | 0.9 (3) | C14—N3—C17—O3 | 179.95 (17) |
C7—N2—C6—C10 | 2.8 (3) | C14—N3—C17—N4 | 0.2 (2) |
Co1—N2—C6—C10 | −173.46 (13) | C16—N4—C17—O3 | −178.03 (18) |
C7—N2—C6—C5 | −175.90 (16) | C16—N4—C17—N3 | 1.7 (3) |
Co1—N2—C6—C5 | 7.83 (19) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O5 | 0.86 | 2.27 | 2.639 (2) | 106 |
O6—H6B···O4 | 0.88 (4) | 1.95 (4) | 2.790 (3) | 160 (3) |
O1—H1A···O2ii | 0.85 (3) | 1.96 (3) | 2.798 (2) | 173 (2) |
O1—H1B···O5iii | 0.85 (3) | 1.94 (4) | 2.735 (2) | 156 (3) |
N3—H3···O3iv | 0.86 | 2.03 | 2.876 (2) | 167 |
N4—H4···O2v | 0.86 | 2.02 | 2.868 (2) | 170 |
O6—H6A···O3vi | 0.82 (5) | 2.41 (5) | 3.103 (3) | 143 (4) |
Symmetry codes: (ii) −x+1, y+1, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+3/2, −y+1/2, −z; (v) −x+1, −y, −z; (vi) x, −y, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Co(C12H8N2)2(H2O)2](C5H3N2O4)2·2.25H2O |
Mr | 806.09 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 16.1401 (11), 12.5692 (10), 16.5650 (11) |
β (°) | 92.435 (5) |
V (Å3) | 3357.5 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.59 |
Crystal size (mm) | 0.35 × 0.23 × 0.15 |
|
Data collection |
Diffractometer | Stoe IPDS2 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4607, 4607, 3086 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.691 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.100, 0.91 |
No. of reflections | 4607 |
No. of parameters | 267 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.51 |
Selected geometric parameters (Å, º) topCo1—O1 | 2.1089 (13) | N1—C5 | 1.352 (2) |
Co1—N2 | 2.1216 (15) | N2—C7 | 1.327 (2) |
Co1—N1 | 2.1300 (14) | N2—C6 | 1.358 (2) |
O2—C16 | 1.241 (2) | N3—C17 | 1.355 (2) |
O3—C17 | 1.225 (2) | N3—C14 | 1.363 (2) |
O4—C13 | 1.234 (2) | N4—C17 | 1.371 (2) |
O5—C13 | 1.242 (2) | N4—C16 | 1.373 (2) |
N1—C1 | 1.325 (2) | | |
| | | |
O1—Co1—O1i | 84.08 (8) | C7—N2—Co1 | 128.95 (14) |
O1—Co1—N2 | 167.01 (5) | C6—N2—Co1 | 113.15 (11) |
O1i—Co1—N2 | 91.50 (6) | C17—N4—C16 | 126.05 (15) |
O1—Co1—N2i | 91.50 (6) | O4—C13—O5 | 128.15 (18) |
N2—Co1—N2i | 95.31 (8) | O4—C13—C14 | 116.55 (16) |
O1—Co1—N1i | 92.20 (6) | O5—C13—C14 | 115.30 (16) |
N2—Co1—N1i | 100.01 (6) | C15—C14—C13 | 124.09 (16) |
O1—Co1—N1 | 89.88 (5) | N3—C14—C13 | 115.10 (14) |
N2—Co1—N1 | 78.06 (5) | O2—C16—N4 | 118.86 (17) |
N2i—Co1—N1 | 100.01 (6) | O2—C16—C15 | 125.97 (16) |
N1i—Co1—N1 | 177.19 (8) | N4—C16—C15 | 115.17 (14) |
C1—N1—C5 | 118.12 (16) | O3—C17—N3 | 123.81 (15) |
C1—N1—Co1 | 128.71 (13) | O3—C17—N4 | 121.04 (16) |
C5—N1—Co1 | 112.72 (11) | N3—C17—N4 | 115.15 (14) |
C7—N2—C6 | 117.77 (17) | | |
Symmetry code: (i) −x+1, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O5 | 0.86 | 2.27 | 2.639 (2) | 106 |
O6—H6B···O4 | 0.88 (4) | 1.95 (4) | 2.790 (3) | 160 (3) |
O1—H1A···O2ii | 0.85 (3) | 1.96 (3) | 2.798 (2) | 173 (2) |
O1—H1B···O5iii | 0.85 (3) | 1.94 (4) | 2.735 (2) | 156 (3) |
N3—H3···O3iv | 0.86 | 2.03 | 2.876 (2) | 167 |
N4—H4···O2v | 0.86 | 2.02 | 2.868 (2) | 170 |
O6—H6A···O3vi | 0.82 (5) | 2.41 (5) | 3.103 (3) | 143 (4) |
Symmetry codes: (ii) −x+1, y+1, −z+1/2; (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+3/2, −y+1/2, −z; (v) −x+1, −y, −z; (vi) x, −y, z+1/2. |
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Orotic acid (uracil-6-carboxylic acid, vitamin B13) and its metal-ion complexes play a cruical role in the metabolism of pyridine nucleotides and in many living organisms (Lalioti et al., 1998). Its metal-ion complexes are especially found interest in curing syndromes associated with deficiency of various metal ions (Kumberger et al., 1993). Thus, the coordination chemistry of orotic acid has been the subject of many studies (Sabat et al., 1980; Keripides & Thomas, 1986; Castan et al., 1990). Furthermore, DNA interaction of mixed-ligand metal complexes with phenanthroline (phen) was also investigated (Sastri et al., 2003). To study further the effects of metal ions on the complexation of orotic acid and its possible use in pharmocolgy, we have prepared the title compound, (I), and determined its structure.
Fig. 1 shows an ORTEP-3 (Farrugia, 1997) plot of (I). The CoII atom located at a center of symmetry is octahedrally coordinated by a pair of bidentate phen molecules together with two water molecules. The mean planes through the pair of bidantate phen ligands form a dihedral angle of 75.33 (2)°. The Co—O distance is 2.1089 (13) Å and Co—N distances lie in the range 2.1216 (15)–2.1300 (14) Å (Table 1). The geometry of the phen ligand is comparable to that observed in a phen containing cobalt complex (Hökelek & Necefoğlu, 1997). The two oratate anions in the structure are protonated and included as counter-anions in the first coordination sphere. The orotate moeities are essentially planar. Nevertheless, there is a slight deviation from planarity arising from the torsion angle N3—C14—C13—O5 of 5.0 (2)°. The mean plane through the orotate molecule in the asymmetric unit is almost parallel [dihedral angle 2.74 (5)°] to that through the phen moiety.
The crystal structure of (I) is shown in Fig. 2. The coordinated water molecules link the oratate ions to the metal complex via O1—H1A···O2i and O1—H1B···O5ii hydrogen bonds (symmetry codes as in Table 2). Each lattice water molecule (O6) is hydrogen bonded to orotate ions through O6—H6B···O4 and O6—H6A···O3v hydrogen bonds. Furthermore, the symmetry-related orotate ions are linked by N3—H3···O3iii and N4—H4···O2iv hydrogen bonds to form chains (see Table 2 for symmetry codes).