Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039620/rn6071sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039620/rn6071Isup2.hkl |
CCDC reference: 296631
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C)= 0.003 Å
- R factor = 0.039
- wR factor = 0.093
- Data-to-parameter ratio = 11.0
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
5-Fluorouracil-1-acetic acid (2 mmol, 0.75 g) and 1,3-di(4-pyridyl)propane (2 mmol, 0.40 g) were dissovled in a mixture of water (2 ml) and ethanol (8 ml). The solution was then added dropwise to a stirred aqueous solution (10 ml) of MnCl2·2H2O (1 mmol, 0.16 g). The resulting solution was filtered and allowed to evaporate slowly at room temperature. After four weeks, prismatic pink crystals of (I) appeared.
Water H atoms were located in difference density maps and refined with O—H and H···H distances restrained to 0.82 (2) Å and 1.39 (1) Å, respectively, with Uiso(H) = 1.2Ueq(parent atom). The other H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of Csp2—H = 0.93 Å with Uiso(H) = 1.2Ueq(C), Csp3—H = 0.97 Å with Uiso(H) = 1.5Ueq(C), and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(N).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.
[Mn(C6H4N2O4F)2(H2O)4] | F(000) = 510 |
Mr = 501.23 | Dx = 1.763 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 2209 reflections |
a = 13.1820 (13) Å | θ = 2.9–25.2° |
b = 5.1106 (5) Å | µ = 0.79 mm−1 |
c = 14.2202 (14) Å | T = 298 K |
β = 99.809 (2)° | Prism, pink |
V = 943.98 (16) Å3 | 0.32 × 0.16 × 0.13 mm |
Z = 2 |
Bruker APEX area-detector diffractometer | 1687 independent reflections |
Radiation source: fine-focus sealed tube | 1619 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ϕ and ω scans | θmax = 25.2°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −15→15 |
Tmin = 0.786, Tmax = 0.904 | k = −6→5 |
4685 measured reflections | l = −17→12 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | w = 1/[σ2(Fo2) + (0.0419P)2 + 0.5989P] where P = (Fo2 + 2Fc2)/3 |
1687 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.19 e Å−3 |
6 restraints | Δρmin = −0.26 e Å−3 |
[Mn(C6H4N2O4F)2(H2O)4] | V = 943.98 (16) Å3 |
Mr = 501.23 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.1820 (13) Å | µ = 0.79 mm−1 |
b = 5.1106 (5) Å | T = 298 K |
c = 14.2202 (14) Å | 0.32 × 0.16 × 0.13 mm |
β = 99.809 (2)° |
Bruker APEX area-detector diffractometer | 1687 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1619 reflections with I > 2σ(I) |
Tmin = 0.786, Tmax = 0.904 | Rint = 0.019 |
4685 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 6 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.16 | Δρmax = 0.19 e Å−3 |
1687 reflections | Δρmin = −0.26 e Å−3 |
154 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 | ||
Mn1 | 0.0000 | 0.0000 | 0.5000 | 0.02985 (18) | |
F1 | 0.53352 (12) | 0.6796 (4) | 0.83103 (14) | 0.0620 (5) | |
O1 | 0.07545 (12) | 0.2476 (3) | 0.61413 (12) | 0.0371 (4) | |
O2 | 0.22799 (13) | 0.0597 (4) | 0.66409 (13) | 0.0411 (5) | |
O3 | 0.22356 (13) | 0.0596 (4) | 0.88419 (13) | 0.0380 (4) | |
O4 | 0.56390 (12) | 0.2580 (4) | 0.95277 (13) | 0.0408 (5) | |
O5 | −0.02257 (13) | −0.2963 (3) | 0.60239 (14) | 0.0373 (4) | |
O6 | −0.15636 (14) | 0.1442 (4) | 0.50959 (14) | 0.0459 (5) | |
N1 | 0.28011 (14) | 0.4091 (4) | 0.80833 (13) | 0.0273 (4) | |
N2 | 0.39240 (14) | 0.1666 (4) | 0.91748 (13) | 0.0296 (5) | |
H2 | 0.4017 | 0.0384 | 0.9572 | 0.036* | |
C1 | 0.16163 (17) | 0.2270 (4) | 0.66883 (17) | 0.0286 (5) | |
C2 | 0.18008 (17) | 0.4377 (5) | 0.74602 (17) | 0.0297 (5) | |
H2A | 0.1765 | 0.6085 | 0.7159 | 0.036* | |
H2B | 0.1260 | 0.4285 | 0.7844 | 0.036* | |
C3 | 0.29390 (17) | 0.2043 (4) | 0.87080 (16) | 0.0272 (5) | |
C4 | 0.47840 (18) | 0.3104 (5) | 0.90815 (16) | 0.0295 (5) | |
C5 | 0.45491 (19) | 0.5243 (5) | 0.84221 (18) | 0.0331 (6) | |
C6 | 0.36076 (18) | 0.5661 (5) | 0.79462 (16) | 0.0297 (5) | |
H6 | 0.3492 | 0.7038 | 0.7514 | 0.036* | |
H6A | −0.1832 (18) | 0.262 (4) | 0.5366 (15) | 0.036* | |
H6B | −0.1888 (19) | 0.097 (5) | 0.4588 (13) | 0.036* | |
H5A | 0.0123 (15) | −0.434 (4) | 0.6055 (19) | 0.036* | |
H5B | −0.0839 (12) | −0.323 (5) | 0.6023 (19) | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0271 (3) | 0.0249 (3) | 0.0344 (3) | 0.0020 (2) | −0.0039 (2) | −0.0040 (2) |
F1 | 0.0373 (9) | 0.0633 (12) | 0.0805 (13) | −0.0184 (8) | −0.0036 (8) | 0.0368 (10) |
O1 | 0.0327 (9) | 0.0298 (10) | 0.0424 (10) | 0.0060 (7) | −0.0123 (8) | −0.0071 (8) |
O2 | 0.0354 (10) | 0.0390 (10) | 0.0444 (11) | 0.0107 (8) | −0.0062 (8) | −0.0089 (8) |
O3 | 0.0274 (9) | 0.0352 (10) | 0.0494 (11) | −0.0040 (8) | 0.0011 (8) | 0.0122 (8) |
O4 | 0.0261 (9) | 0.0418 (11) | 0.0500 (11) | −0.0015 (8) | −0.0061 (8) | 0.0138 (9) |
O5 | 0.0290 (9) | 0.0309 (9) | 0.0511 (11) | 0.0061 (8) | 0.0042 (8) | 0.0037 (8) |
O6 | 0.0359 (10) | 0.0487 (12) | 0.0490 (12) | 0.0123 (9) | −0.0048 (8) | −0.0215 (10) |
N1 | 0.0278 (10) | 0.0245 (10) | 0.0265 (10) | 0.0004 (8) | −0.0042 (8) | 0.0004 (8) |
N2 | 0.0282 (10) | 0.0266 (11) | 0.0314 (11) | −0.0020 (8) | −0.0023 (8) | 0.0092 (8) |
C1 | 0.0290 (12) | 0.0241 (12) | 0.0309 (12) | 0.0005 (10) | −0.0004 (10) | 0.0034 (9) |
C2 | 0.0268 (12) | 0.0267 (12) | 0.0320 (13) | 0.0034 (9) | −0.0048 (10) | 0.0005 (10) |
C3 | 0.0291 (12) | 0.0245 (12) | 0.0260 (12) | 0.0017 (10) | −0.0007 (9) | 0.0014 (9) |
C4 | 0.0302 (12) | 0.0287 (13) | 0.0276 (12) | −0.0020 (10) | −0.0005 (10) | 0.0002 (10) |
C5 | 0.0316 (13) | 0.0312 (13) | 0.0357 (13) | −0.0070 (10) | 0.0033 (10) | 0.0067 (10) |
C6 | 0.0362 (13) | 0.0241 (12) | 0.0266 (12) | −0.0012 (10) | −0.0008 (10) | 0.0033 (9) |
Mn1—O5 | 2.1563 (18) | O6—H6B | 0.810 (15) |
Mn1—O5i | 2.1563 (18) | N1—C3 | 1.365 (3) |
Mn1—O1i | 2.1620 (16) | N1—C6 | 1.372 (3) |
Mn1—O1 | 2.1620 (16) | N1—C2 | 1.465 (3) |
Mn1—O6 | 2.2148 (18) | N2—C3 | 1.368 (3) |
Mn1—O6i | 2.2148 (18) | N2—C4 | 1.376 (3) |
F1—C5 | 1.336 (3) | N2—H2 | 0.8600 |
O1—C1 | 1.267 (3) | C1—C2 | 1.527 (3) |
O2—C1 | 1.233 (3) | C2—H2A | 0.9700 |
O3—C3 | 1.226 (3) | C2—H2B | 0.9700 |
O4—C4 | 1.225 (3) | C4—C5 | 1.439 (3) |
O5—H5A | 0.836 (16) | C5—C6 | 1.326 (3) |
O5—H5B | 0.820 (15) | C6—H6 | 0.9300 |
O6—H6A | 0.826 (15) | ||
O5—Mn1—O5i | 180.0 | C3—N2—C4 | 127.4 (2) |
O5—Mn1—O1i | 89.83 (7) | C3—N2—H2 | 116.3 |
O5i—Mn1—O1i | 90.17 (7) | C4—N2—H2 | 116.3 |
O5—Mn1—O1 | 90.17 (7) | O2—C1—O1 | 126.4 (2) |
O5i—Mn1—O1 | 89.83 (7) | O2—C1—C2 | 120.0 (2) |
O1i—Mn1—O1 | 180.0 | O1—C1—C2 | 113.5 (2) |
O5—Mn1—O6 | 87.43 (7) | N1—C2—C1 | 112.40 (19) |
O5i—Mn1—O6 | 92.57 (7) | N1—C2—H2A | 109.1 |
O1i—Mn1—O6 | 85.81 (7) | C1—C2—H2A | 109.1 |
O1—Mn1—O6 | 94.19 (7) | N1—C2—H2B | 109.1 |
O5—Mn1—O6i | 92.57 (7) | C1—C2—H2B | 109.1 |
O5i—Mn1—O6i | 87.43 (7) | H2A—C2—H2B | 107.9 |
O1i—Mn1—O6i | 94.19 (7) | O3—C3—N1 | 122.9 (2) |
O1—Mn1—O6i | 85.81 (7) | O3—C3—N2 | 121.3 (2) |
O6—Mn1—O6i | 180.00 (10) | N1—C3—N2 | 115.7 (2) |
C1—O1—Mn1 | 131.45 (15) | O4—C4—N2 | 122.3 (2) |
Mn1—O5—H5A | 119.2 (18) | O4—C4—C5 | 125.5 (2) |
Mn1—O5—H5B | 111.3 (18) | N2—C4—C5 | 112.3 (2) |
H5A—O5—H5B | 113 (2) | C6—C5—F1 | 121.4 (2) |
Mn1—O6—H6A | 138.4 (17) | C6—C5—C4 | 122.3 (2) |
Mn1—O6—H6B | 101.6 (17) | F1—C5—C4 | 116.3 (2) |
H6A—O6—H6B | 115 (2) | C5—C6—N1 | 120.9 (2) |
C3—N1—C6 | 121.36 (19) | C5—C6—H6 | 119.5 |
C3—N1—C2 | 118.45 (19) | N1—C6—H6 | 119.5 |
C6—N1—C2 | 119.67 (19) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O4ii | 0.86 | 1.99 | 2.843 (3) | 175 |
O6—H6A···O3iii | 0.83 (2) | 2.02 (2) | 2.834 (3) | 170 (2) |
O6—H6B···O2i | 0.81 (2) | 1.91 (2) | 2.699 (3) | 163 (2) |
O5—H5A···O1iv | 0.84 (2) | 1.82 (2) | 2.656 (2) | 174 (2) |
O5—H5B···O3v | 0.82 (2) | 1.98 (2) | 2.788 (2) | 170 (2) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+2; (iii) −x, y+1/2, −z+3/2; (iv) x, y−1, z; (v) −x, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C6H4N2O4F)2(H2O)4] |
Mr | 501.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 13.1820 (13), 5.1106 (5), 14.2202 (14) |
β (°) | 99.809 (2) |
V (Å3) | 943.98 (16) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.79 |
Crystal size (mm) | 0.32 × 0.16 × 0.13 |
Data collection | |
Diffractometer | Bruker APEX area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.786, 0.904 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4685, 1687, 1619 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.093, 1.16 |
No. of reflections | 1687 |
No. of parameters | 154 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.26 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.
Mn1—O5 | 2.1563 (18) | Mn1—O6 | 2.2148 (18) |
Mn1—O1 | 2.1620 (16) | ||
O5—Mn1—O5i | 180.0 | O5i—Mn1—O6 | 92.57 (7) |
O5—Mn1—O1i | 89.83 (7) | O1i—Mn1—O6 | 85.81 (7) |
O5—Mn1—O1 | 90.17 (7) | O1—Mn1—O6 | 94.19 (7) |
O5—Mn1—O6 | 87.43 (7) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O4ii | 0.86 | 1.99 | 2.843 (3) | 174.9 |
O6—H6A···O3iii | 0.826 (15) | 2.017 (15) | 2.834 (3) | 170 (2) |
O6—H6B···O2i | 0.810 (15) | 1.912 (15) | 2.699 (3) | 163 (2) |
O5—H5A···O1iv | 0.836 (16) | 1.824 (17) | 2.656 (2) | 174 (2) |
O5—H5B···O3v | 0.820 (15) | 1.977 (17) | 2.788 (2) | 170 (2) |
Symmetry codes: (i) −x, −y, −z+1; (ii) −x+1, −y, −z+2; (iii) −x, y+1/2, −z+3/2; (iv) x, y−1, z; (v) −x, y−1/2, −z+3/2. |
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5-Fluorouracil (5-FU) is an antimetabolite with good antimicrobial and antitumor activity, but its administration is accompanied by significant toxic side effects and delivery problems (Ouchi et al., 1997; Nichifor & Schacht, 1994; Nichifor et al., 1997; Hulme et al., 2005). In order to improve the topical delivery of 5-FU and reduce the side effects, many derivatives of 5-FU have been synthesized, some of which have better biological activity. 5-Fluorouracil-1-acetic acid (5-FUAA) is a member of this family (Sloan et al., 1993; Li et al., 2000; Beall & Sloan, 2001; Beall & Sloan, 2002). As increasing attention has been paid to the anticancer activity of 5-FU and its derivatives (Akgerman & Guney, 2000), several transition metal complexes have been reported (Wang et al., 1993; Huang et al., 2000; Hu et al., 2005). The manganese derivative adduct, Mn(C6H4N2O4F)2(H2O)4, (I), is reported here to build on these studies.
Mononuclear (I) consists of an Mn atom, four coordinated water molecules and two 5-fluorouracil-1-acetate anions, which bind through their carboxylate O atoms. The Mn atom lies on an inversion center and the geometry around the Mn ion is octahedral (Fig.1 and Table 1). A square plane is formed by atoms O5, O5i, O6 and O6i [symmetry code: (i) −x, −y, −z + 1], which is crystallographically imposed to be flat. The N—H···O and O—H···O hydrogen bonds link the mononuclear units to form a three-dimensional network (Fig. 2 and Table 2).