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The Co
II ion in the title compound, [Co(C
5H
2N
2O
4)(H
2O)
4]·2.5H
2O, is chelated by the orotate dianion through carboxylate O and pyrimidine N atoms, and its octahedral geometry is completed by four water molecules. An intermolecular N—H
O hydrogen bond forms an orotate–orotate dimer. An extensive three-dimensional hydrogen-bonded network of O—H
O and N—H
O bonds and weak π–π interaction [3.754 (2) Å] stabilize the crystal structure. One of the solvent water molecules is located on a twofold rotation axis.
Supporting information
CCDC reference: 672581
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- H-atom completeness 67%
- R factor = 0.062
- wR factor = 0.199
- Data-to-parameter ratio = 12.7
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) ....... O5W
| Author Response: The O atoms of the uncoordinated (O5W, O6W & O7W)
water molecules were refined isotropically. The H atoms of O5W,
O6W and O7W could not be located from electron density maps.
|
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) ....... O6W
| Author Response: The O atoms of the uncoordinated (O5W, O6W & O7W)
water molecules were refined isotropically. The H atoms of O5W,
O6W and O7W could not be located from electron density maps.
|
PLAT306_ALERT_2_A Isolated Oxygen Atom (H-atoms Missing ?) ....... O7W
| Author Response: The O atoms of the uncoordinated (O5W, O6W & O7W)
water molecules were refined isotropically. The H atoms of O5W,
O6W and O7W could not be located from electron density maps.
|
Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact O5W .. O6 .. 2.78 Ang.
Alert level C
CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as
calculated from the _atom_site* data lies outside
the range 0.99 <> 1.01
From the CIF: _cell_formula_units_Z 8
From the CIF: _chemical_formula_weight 330.12
TEST: Calculate formula weight from _atom_site_*
atom mass num sum
C 12.01 5.00 60.06
H 1.01 10.00 10.08
N 14.01 2.00 28.01
O 16.00 10.50 167.99
Co 58.93 1.00 58.93
Calculated formula weight 325.07
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT043_ALERT_1_C Check Reported Molecular Weight ................ 330.12
PLAT044_ALERT_1_C Calculated and Reported Dx Differ .............. ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT202_ALERT_3_C Isotropic non-H Atoms in Anion/Solvent ......... 3
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.69 Ratio
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Co1
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 7
PLAT430_ALERT_2_C Short Inter D...A Contact O5W .. O6W .. 2.88 Ang.
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 32.00 A 3
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:C5 H15 Co1 N2 O10.5
Atom count from the _atom_site data: C5 H10 Co1 N2 O10.5
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 8
From the CIF: _chemical_formula_sum C5 H15 Co N2 O10.5
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 40.00 40.00 0.00
H 120.00 80.00 40.00
Co 8.00 8.00 0.00
N 16.00 16.00 0.00
O 84.00 84.00 0.00
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1 (9) 1.22
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 10
3 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
13 ALERT level C = Check and explain
6 ALERT level G = General alerts; check
9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
9 ALERT type 2 Indicator that the structure model may be wrong or deficient
4 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
1 ALERT type 5 Informative message, check
A solution of CoCl2.6H2O (1.2 g, 1 mmol) in water (25 ml) was added to a
solution of orotic acid (0.9 g, 1 mmol) in water (25 ml). The solution
refluxed and stirred in a temperature-controlled bath. The mixture was then
left for crystallization.
The H atom attached to the N atom was located in a difference Fourier map and
refined isotropically. H atoms of coordinated water molecules were located in
a difference Fourier map and refined isotropically with Uiso(H) = 1.5
Ueq(O). The N2—H2N and coordinated water H atoms were restrained to
values of 0.85 (1) and 0.89 (1) Å, respectively. The H atom attached to the C
atom was positioned geometrically and treated as riding on its parent C atom
with C—H distance = 0.93 Å, and with Uiso(H) =
1.2Ueq(C). The O atoms of the uncoordinated water (O5W, O6W & O7W)
molecules show high displacement parameters, but attempts to refine them as
disordered were unsucessful. Hence, the O atoms were refined isotropically.
The H atoms of O5W, O6W and O7W could not be located from electron density
maps. These H atoms were not included in the calculations (although they are
included in the emprical formula). A maximum (positive) residual density was
observed 0.88 Å from atom O5W.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990) and PLATON
(Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Tetraaqua(2,6-dioxo-1,2,3,6-tetrahydropyrimidine-4-carboxylato-
κ2N3,
O)cobalt(II) 2.5-hydrate
top
Crystal data top
[Co(C5H2N2O4)(H2O)4]·2.5H2O | F(000) = 1360 |
Mr = 330.12 | Dx = 1.673 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 7524 reflections |
a = 20.8700 (19) Å | θ = 2.4–24.3° |
b = 17.1153 (16) Å | µ = 1.36 mm−1 |
c = 7.3375 (7) Å | T = 293 K |
V = 2620.9 (4) Å3 | Block, brown |
Z = 8 | 0.16 × 0.11 × 0.05 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2321 independent reflections |
Radiation source: fine-focus sealed tube | 1971 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −24→24 |
Tmin = 0.82, Tmax = 0.94 | k = −20→19 |
17563 measured reflections | l = −8→8 |
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.199 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.1193P)2 + 6.0462P] where P = (Fo2 + 2Fc2)/3 |
2321 reflections | (Δ/σ)max = 0.001 |
183 parameters | Δρmax = 1.39 e Å−3 |
10 restraints | Δρmin = −0.71 e Å−3 |
Crystal data top
[Co(C5H2N2O4)(H2O)4]·2.5H2O | V = 2620.9 (4) Å3 |
Mr = 330.12 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 20.8700 (19) Å | µ = 1.36 mm−1 |
b = 17.1153 (16) Å | T = 293 K |
c = 7.3375 (7) Å | 0.16 × 0.11 × 0.05 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2321 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1971 reflections with I > 2σ(I) |
Tmin = 0.82, Tmax = 0.94 | Rint = 0.038 |
17563 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 10 restraints |
wR(F2) = 0.199 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 1.39 e Å−3 |
2321 reflections | Δρmin = −0.71 e Å−3 |
183 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.7263 (2) | 0.3856 (3) | 0.3371 (7) | 0.0385 (12) | |
C2 | 0.6732 (2) | 0.4366 (3) | 0.2594 (7) | 0.0309 (10) | |
C3 | 0.6769 (2) | 0.5154 (3) | 0.2676 (7) | 0.0338 (11) | |
H3 | 0.7118 | 0.5399 | 0.3216 | 0.041* | |
C4 | 0.6257 (2) | 0.5599 (3) | 0.1911 (6) | 0.0312 (11) | |
C5 | 0.5743 (2) | 0.4364 (3) | 0.1159 (6) | 0.0286 (10) | |
Co1 | 0.63880 (3) | 0.27419 (4) | 0.18230 (9) | 0.0331 (3) | |
N1 | 0.62351 (19) | 0.3957 (2) | 0.1868 (5) | 0.0299 (9) | |
N2 | 0.57606 (18) | 0.5165 (2) | 0.1237 (5) | 0.0292 (9) | |
H2N | 0.5431 (16) | 0.542 (3) | 0.090 (7) | 0.039 (15)* | |
O5 | 0.71873 (17) | 0.3129 (2) | 0.3242 (5) | 0.0435 (9) | |
O6 | 0.77339 (19) | 0.4172 (2) | 0.4090 (7) | 0.0578 (12) | |
O7 | 0.62424 (19) | 0.6324 (2) | 0.1820 (5) | 0.0397 (9) | |
O8 | 0.52739 (15) | 0.40450 (19) | 0.0404 (5) | 0.0360 (8) | |
O1W | 0.6869 (2) | 0.2836 (3) | −0.0659 (6) | 0.0688 (15) | |
H1W | 0.674 (5) | 0.306 (5) | −0.169 (7) | 0.108* | |
H2W | 0.715 (4) | 0.252 (5) | −0.120 (13) | 0.108* | |
O2W | 0.5526 (2) | 0.2518 (2) | 0.0408 (6) | 0.0525 (10) | |
H3W | 0.534 (3) | 0.298 (2) | 0.030 (10) | 0.073* | |
H4W | 0.548 (4) | 0.221 (4) | 0.137 (6) | 0.073* | |
O3W | 0.6630 (3) | 0.1565 (3) | 0.1854 (6) | 0.0619 (13) | |
H5W | 0.686 (5) | 0.142 (7) | 0.089 (10) | 0.144* | |
H6W | 0.680 (5) | 0.144 (7) | 0.293 (8) | 0.144* | |
O4W | 0.5907 (2) | 0.2568 (2) | 0.4340 (5) | 0.0452 (9) | |
H7W | 0.589 (4) | 0.3028 (18) | 0.491 (8) | 0.082* | |
H8W | 0.608 (4) | 0.216 (2) | 0.491 (8) | 0.082* | |
O5W | 0.6640 (5) | 0.0575 (6) | 0.4756 (14) | 0.148 (3)* | |
O6W | 0.5927 (4) | 0.1499 (6) | 0.7340 (14) | 0.141 (3)* | |
O7W | 0.5000 | 0.1145 (14) | 0.2500 | 0.251 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.029 (2) | 0.045 (3) | 0.042 (3) | 0.004 (2) | −0.005 (2) | 0.010 (2) |
C2 | 0.024 (2) | 0.039 (3) | 0.030 (2) | 0.0022 (19) | −0.0005 (19) | 0.005 (2) |
C3 | 0.027 (2) | 0.040 (3) | 0.035 (2) | −0.003 (2) | −0.007 (2) | 0.005 (2) |
C4 | 0.032 (2) | 0.035 (3) | 0.027 (2) | 0.003 (2) | −0.0020 (19) | 0.0046 (19) |
C5 | 0.025 (2) | 0.031 (2) | 0.029 (2) | 0.0065 (18) | 0.0007 (19) | −0.0014 (19) |
Co1 | 0.0328 (5) | 0.0306 (5) | 0.0359 (5) | 0.0094 (2) | 0.0009 (3) | −0.0006 (3) |
N1 | 0.0249 (19) | 0.029 (2) | 0.035 (2) | 0.0053 (16) | −0.0030 (16) | 0.0001 (16) |
N2 | 0.027 (2) | 0.027 (2) | 0.034 (2) | 0.0063 (15) | −0.0047 (17) | 0.0012 (17) |
O5 | 0.0367 (19) | 0.038 (2) | 0.056 (2) | 0.0099 (16) | −0.0112 (16) | 0.0036 (16) |
O6 | 0.039 (2) | 0.050 (2) | 0.085 (3) | −0.0030 (18) | −0.027 (2) | 0.015 (2) |
O7 | 0.050 (2) | 0.0253 (19) | 0.044 (2) | −0.0024 (15) | −0.0124 (16) | 0.0031 (15) |
O8 | 0.0307 (17) | 0.0303 (17) | 0.047 (2) | 0.0050 (13) | −0.0119 (15) | −0.0028 (15) |
O1W | 0.072 (3) | 0.087 (3) | 0.047 (3) | 0.053 (3) | 0.023 (2) | 0.021 (2) |
O2W | 0.049 (2) | 0.044 (2) | 0.065 (3) | 0.0031 (19) | −0.011 (2) | −0.008 (2) |
O3W | 0.096 (4) | 0.039 (2) | 0.051 (3) | 0.028 (2) | 0.020 (2) | 0.0046 (19) |
O4W | 0.054 (2) | 0.0392 (19) | 0.042 (2) | −0.0014 (18) | 0.0065 (18) | −0.0056 (17) |
Geometric parameters (Å, º) top
C1—O6 | 1.240 (6) | Co1—O1W | 2.086 (4) |
C1—O5 | 1.258 (7) | Co1—N1 | 2.104 (4) |
C1—C2 | 1.521 (7) | Co1—O2W | 2.112 (4) |
C2—C3 | 1.352 (7) | Co1—O4W | 2.123 (4) |
C2—N1 | 1.360 (6) | N2—H2N | 0.85 (4) |
C3—C4 | 1.427 (7) | O1W—H1W | 0.89 (6) |
C3—H3 | 0.9300 | O1W—H2W | 0.89 (8) |
C4—O7 | 1.243 (6) | O2W—H3W | 0.88 (4) |
C4—N2 | 1.367 (6) | O2W—H4W | 0.89 (5) |
C5—O8 | 1.249 (6) | O3W—H5W | 0.89 (9) |
C5—N1 | 1.347 (6) | O3W—H6W | 0.89 (7) |
C5—N2 | 1.374 (6) | O4W—H7W | 0.89 (4) |
Co1—O5 | 2.075 (4) | O4W—H8W | 0.89 (5) |
Co1—O3W | 2.078 (4) | | |
| | | |
O6—C1—O5 | 124.2 (5) | O5—Co1—O4W | 89.33 (15) |
O6—C1—C2 | 119.1 (5) | O3W—Co1—O4W | 88.23 (16) |
O5—C1—C2 | 116.6 (4) | O1W—Co1—O4W | 176.33 (17) |
C3—C2—N1 | 125.0 (4) | N1—Co1—O4W | 93.08 (15) |
C3—C2—C1 | 121.0 (4) | O2W—Co1—O4W | 89.99 (17) |
N1—C2—C1 | 114.0 (4) | C5—N1—C2 | 117.8 (4) |
C2—C3—C4 | 118.3 (4) | C5—N1—Co1 | 128.4 (3) |
C2—C3—H3 | 120.9 | C2—N1—Co1 | 113.6 (3) |
C4—C3—H3 | 120.9 | C4—N2—C5 | 125.3 (4) |
O7—C4—N2 | 120.2 (4) | C4—N2—H2N | 116 (4) |
O7—C4—C3 | 125.0 (5) | C5—N2—H2N | 118 (4) |
N2—C4—C3 | 114.8 (4) | C1—O5—Co1 | 117.0 (3) |
O8—C5—N1 | 122.9 (4) | Co1—O1W—H1W | 130 (7) |
O8—C5—N2 | 118.4 (4) | Co1—O1W—H2W | 131 (7) |
N1—C5—N2 | 118.7 (4) | H1W—O1W—H2W | 94 (8) |
O5—Co1—O3W | 96.2 (2) | Co1—O2W—H3W | 105 (5) |
O5—Co1—O1W | 91.51 (19) | Co1—O2W—H4W | 79 (5) |
O3W—Co1—O1W | 88.13 (17) | H3W—O2W—H4W | 123 (7) |
O5—Co1—N1 | 78.39 (15) | Co1—O3W—H5W | 113 (8) |
O3W—Co1—N1 | 174.4 (2) | Co1—O3W—H6W | 109 (8) |
O1W—Co1—N1 | 90.59 (17) | H5W—O3W—H6W | 115 (10) |
O5—Co1—O2W | 171.62 (15) | Co1—O4W—H7W | 108 (5) |
O3W—Co1—O2W | 92.1 (2) | Co1—O4W—H8W | 109 (5) |
O1W—Co1—O2W | 89.7 (2) | H7W—O4W—H8W | 119 (5) |
N1—Co1—O2W | 93.31 (16) | | |
| | | |
O6—C1—C2—C3 | 0.1 (8) | O1W—Co1—N1—C5 | 88.8 (4) |
O5—C1—C2—C3 | 179.7 (5) | O2W—Co1—N1—C5 | −0.9 (4) |
O6—C1—C2—N1 | −179.0 (5) | O4W—Co1—N1—C5 | −91.1 (4) |
O5—C1—C2—N1 | 0.6 (7) | O5—Co1—N1—C2 | 5.7 (3) |
N1—C2—C3—C4 | −1.5 (8) | O1W—Co1—N1—C2 | −85.7 (4) |
C1—C2—C3—C4 | 179.6 (4) | O2W—Co1—N1—C2 | −175.4 (3) |
C2—C3—C4—O7 | −176.6 (5) | O4W—Co1—N1—C2 | 94.4 (3) |
C2—C3—C4—N2 | 2.9 (7) | O7—C4—N2—C5 | 175.7 (4) |
O8—C5—N1—C2 | 177.5 (4) | C3—C4—N2—C5 | −3.9 (7) |
N2—C5—N1—C2 | −1.3 (6) | O8—C5—N2—C4 | −175.7 (4) |
O8—C5—N1—Co1 | 3.2 (7) | N1—C5—N2—C4 | 3.2 (7) |
N2—C5—N1—Co1 | −175.6 (3) | O6—C1—O5—Co1 | −175.9 (4) |
C3—C2—N1—C5 | 0.6 (7) | C2—C1—O5—Co1 | 4.5 (6) |
C1—C2—N1—C5 | 179.6 (4) | O3W—Co1—O5—C1 | 172.9 (4) |
C3—C2—N1—Co1 | 175.7 (4) | O1W—Co1—O5—C1 | 84.7 (4) |
C1—C2—N1—Co1 | −5.2 (5) | N1—Co1—O5—C1 | −5.6 (4) |
O5—Co1—N1—C5 | −179.8 (4) | O4W—Co1—O5—C1 | −98.9 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O8i | 0.85 (4) | 1.98 (4) | 2.818 (5) | 168 (5) |
O1W—H2W···O5ii | 0.89 (6) | 1.82 (9) | 2.694 (5) | 166 (10) |
O1W—H1W···O7iii | 0.89 (8) | 1.84 (4) | 2.683 (5) | 157 (9) |
O3W—H5W···O6ii | 0.89 (9) | 1.87 (10) | 2.732 (6) | 164 (11) |
O3W—H6W···O5W | 0.89 (7) | 2.03 (9) | 2.721 (11) | 134 (10) |
O4W—H7W···O7iv | 0.89 (7) | 1.94 (4) | 2.720 (5) | 146 (6) |
O4W—H8W···O6W | 0.89 (5) | 2.14 (5) | 2.862 (11) | 138 (7) |
O2W—H3W···O8 | 0.88 (4) | 1.82 (3) | 2.666 (5) | 157 (7) |
O2W—H4W···O7W | 0.89 (5) | 2.24 (5) | 3.014 (19) | 146 (7) |
O2W—H4W···O4W | 0.89 (5) | 2.43 (7) | 2.994 (6) | 122 (6) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, −y+1/2, z−1/2; (iii) x, −y+1, z−1/2; (iv) x, −y+1, z+1/2. |
Experimental details
Crystal data |
Chemical formula | [Co(C5H2N2O4)(H2O)4]·2.5H2O |
Mr | 330.12 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 293 |
a, b, c (Å) | 20.8700 (19), 17.1153 (16), 7.3375 (7) |
V (Å3) | 2620.9 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.36 |
Crystal size (mm) | 0.16 × 0.11 × 0.05 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.82, 0.94 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17563, 2321, 1971 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.199, 1.12 |
No. of reflections | 2321 |
No. of parameters | 183 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.39, −0.71 |
Selected geometric parameters (Å, º) topCo1—O5 | 2.075 (4) | Co1—O2W | 2.112 (4) |
Co1—O3W | 2.078 (4) | Co1—O4W | 2.123 (4) |
Co1—O1W | 2.086 (4) | | |
| | | |
O5—Co1—O3W | 96.2 (2) | O3W—Co1—O2W | 92.1 (2) |
O5—Co1—O1W | 91.51 (19) | O1W—Co1—O2W | 89.7 (2) |
O3W—Co1—O1W | 88.13 (17) | N1—Co1—O2W | 93.31 (16) |
O5—Co1—N1 | 78.39 (15) | O5—Co1—O4W | 89.33 (15) |
O1W—Co1—N1 | 90.59 (17) | O3W—Co1—O4W | 88.23 (16) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2N···O8i | 0.85 (4) | 1.98 (4) | 2.818 (5) | 168 (5) |
O1W—H2W···O5ii | 0.89 (6) | 1.82 (9) | 2.694 (5) | 166 (10) |
O1W—H1W···O7iii | 0.89 (8) | 1.84 (4) | 2.683 (5) | 157 (9) |
O3W—H5W···O6ii | 0.89 (9) | 1.87 (10) | 2.732 (6) | 164 (11) |
O3W—H6W···O5W | 0.89 (7) | 2.03 (9) | 2.721 (11) | 134 (10) |
O4W—H7W···O7iv | 0.89 (7) | 1.94 (4) | 2.720 (5) | 146 (6) |
O4W—H8W···O6W | 0.89 (5) | 2.14 (5) | 2.862 (11) | 138 (7) |
O2W—H3W···O8 | 0.88 (4) | 1.82 (3) | 2.666 (5) | 157 (7) |
O2W—H4W···O7W | 0.89 (5) | 2.24 (5) | 3.014 (19) | 146 (7) |
O2W—H4W···O4W | 0.89 (5) | 2.43 (7) | 2.994 (6) | 122 (6) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, −y+1/2, z−1/2; (iii) x, −y+1, z−1/2; (iv) x, −y+1, z+1/2. |
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Orotic acid (vitamin B13, H3Or) plays a significant role in biosynthesis of pyrimidine nucleosides (Panzeter & Ringer, 1993) and also found in cell and body fluids of many living organisms (Lalioti et al., 1998). Orotic acid is a good organic building block in coordination chemistry and has a multidentate nature. The most potential coordination sites (pH range of 5–9) are the carboxylate oxygen and the adjacent nitrogen atom for the formation of a stable five-membered chelate ring. The crystal structures of nickel(II) orotate pentahydrate (Wysokinski et al., 2002) and the analogous pentahydrate salt of cobalt (Icbudak et al., 2003) were recently reported. In the present study, we are reporting the crystal structure of tetraaqua(orotato)cobalt(II) 2.5 hydrate (I).
The molecular structure of (I) is shown in Fig. 1 and selected geometrical parameters are given in Table 1. Compound (I) comprises of one CoII ion, one orotate ligand, four coordinated water molecule and 2.5 uncoordinated solvent water molecules. The central CoII ion has a distorted octahedral coordination geometry, comprised of atoms N1 and O4 from a doubly deprotonated bidentate orotate ligand and four water (O1W, O2W, O3W and O4W) molecules.
The orotate ligand is essentially planar. The dihedral angle between the pyrimidine ring and the carboxylate group is 0.8 (4)°. The atom N and carboxylate O atom of the orotate ring form a five-membered chelate ring with the CoII ion. The dihedral angle between the five-membered ring and the six-membered pyrimidine ring is 4.3 (1)°. The Co—N distance is 2.104 (4) Å and Co—O distances lie in the range 2.075 (3)–2.123 (4) Å (Table 1).
The structure is stabilized by N—H···O and O—H···O hydrogen bonding. The intramolecular O—H···O hydrogen bond forms an S(6) motif (Bernstein et al., 1995). The intermolecular N—H···O hydrogen bonding leads to the formation of centrosymmetric dimer of R22(8)-type motif. The four water molecules link the carboxylate (O5 & O6) groups and carbonyl (O7 & O8) atoms through intra and intermolecular hydrogen bond interactions (Table. 2). Hydrogen-bonding interactions between the coordinated and uncoordinated water molecules and between the water molecules and the ligand result in a three-dimensional network structure (Fig. 2).
A π-π interaction is observed between the symmetry-related pyrimidine rings (N1/C1/C2/C3/C4/N2/C5). The six-membered ring at (x,y,z) and (x, 1 - y, z + 1/2) are parallel with an interplanar spacing of 3.267 Å; the ring centroid separation is 3.755 (3) Å.