Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026001/kj2058sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026001/kj2058Isup2.hkl |
CCDC reference: 648570
The title compound was obtained as the main product from the hydrothermal reaction of manganese chloride (0.063 g, 0.5 mmol), 1,10-phenanthroline-5,6-dione (0.105 g, 0.5 mmol), pyridine-2,6-dicarboxylic acid (0.084 g, 0.5 mmol) and water (10 ml) in a 25 ml Teflon-lined stainless steel Parr bomb at 413 K over three days. After cooling slowly to room temperature, light yellow single crystals of (I) were obtained.
All H atoms attached to C atoms from the organic ligands were generated in idealized positions and constrained to ride on their parent atoms, with C—H = 0.93Å and Uiso=1.2Ueq for aromatic.
The water H atoms were located on a difference map and refined isotropically.
Pyridine-2,6-dicarboxylic acid (pdc) is an excellent ligand because it combines the coordination properties of the pyridine and carboxylate group, which may bind metal ions in a variety of bonding modes (Liu et al., 2006; Okabe & Oya, 2000). 1,10-Phenanthroline-5,6-dione (pdo) is a versatile ligand for the assembly of metal organic materials (Calderazzo et al., 2002; Larsson & Öhrström, 2004). Here, we report the mononuclear Mn2+ complex, (I), formed from a dianionic pyridine-2,6-dicarboxylate ligand (pdc2-), the N-donor ligand 1,10-phenanthroline-5,6-dione (pdo) and water molecules and explore its supramolecular structure.
As can be seen from Fig. 1, the asymmetric unit comprises a Mn2+ cation, half a dianionic pdc ligand and half a bidentate chelating pdo ligand, all located on a twofold symmetry axis, as well as one coordinated water molecule and one crystal lattice water molecule. A ring nitrogen atom and two oxygen atoms of the carboxylate group belonging to the pdc ligand are involved in coordination to the Mn2+ cation. The pdo group acts as a chelating ligand through the N atoms. Coordination of two water molecules at the axial sites completes the distorted pentagonal dipyramid coordination geometry.
In the crystal structure, hydrogen bonding interactions are observed between the coordinated water molecules, the crystal lattice water molecules and the oxygen atoms of the carboxyl groups in a neighbouring unit to form a three-dimensional supramolecular structure (Figure 2).
For related literature, see: Calderazzo et al. (2002); Larsson & Öhrström (2004); Liu et al. (2006); Okabe & Oya (2000).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
[Mn(C7H3NO4)(C12H6N2O2)(H2O)2]·2H2O | F(000) = 1028 |
Mr = 502.30 | Dx = 1.609 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 117 reflections |
a = 10.1751 (11) Å | θ = 5–20° |
b = 14.8325 (11) Å | µ = 0.70 mm−1 |
c = 14.6121 (13) Å | T = 273 K |
β = 109.861 (1)° | Block, yellow |
V = 2074.1 (3) Å3 | 0.16 × 0.12 × 0.10 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 1843 independent reflections |
Radiation source: fine-focus sealed tube | 1637 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
φ and ω scans | θmax = 25.1°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→12 |
Tmin = 0.896, Tmax = 0.933 | k = −17→16 |
5144 measured reflections | l = −17→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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0457P)2 + 1.3664P] where P = (Fo2 + 2Fc2)/3 |
1843 reflections | (Δ/σ)max < 0.001 |
167 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
[Mn(C7H3NO4)(C12H6N2O2)(H2O)2]·2H2O | V = 2074.1 (3) Å3 |
Mr = 502.30 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.1751 (11) Å | µ = 0.70 mm−1 |
b = 14.8325 (11) Å | T = 273 K |
c = 14.6121 (13) Å | 0.16 × 0.12 × 0.10 mm |
β = 109.861 (1)° |
Bruker SMART APEX CCD diffractometer | 1843 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1637 reflections with I > 2σ(I) |
Tmin = 0.896, Tmax = 0.933 | Rint = 0.018 |
5144 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.36 e Å−3 |
1843 reflections | Δρmin = −0.20 e Å−3 |
167 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 | 1.0000 | 0.79318 (2) | 0.7500 | 0.03159 (16) | |
N1 | 1.0000 | 0.94747 (14) | 0.7500 | 0.0297 (5) | |
N2 | 0.87516 (16) | 0.66130 (10) | 0.67750 (11) | 0.0321 (4) | |
O1 | 0.78287 (14) | 0.84912 (9) | 0.66535 (11) | 0.0420 (4) | |
O2 | 0.64025 (13) | 0.96698 (9) | 0.62159 (10) | 0.0399 (3) | |
O3 | 0.87158 (15) | 0.34079 (9) | 0.68074 (11) | 0.0442 (4) | |
O4 | 1.07694 (18) | 0.78734 (11) | 0.62489 (12) | 0.0422 (4) | |
O5 | 0.44735 (19) | 0.86864 (11) | 0.47295 (14) | 0.0526 (4) | |
C1 | 0.75793 (19) | 0.93165 (12) | 0.65935 (13) | 0.0312 (4) | |
C2 | 0.88249 (18) | 0.99259 (12) | 0.70524 (13) | 0.0312 (4) | |
C3 | 0.8784 (2) | 1.08543 (13) | 0.70317 (17) | 0.0454 (5) | |
H3 | 0.7956 | 1.1158 | 0.6709 | 0.054* | |
C4 | 1.0000 | 1.1326 (2) | 0.7500 | 0.0560 (9) | |
H4C | 1.0000 | 1.1953 | 0.7500 | 0.067* | |
C5 | 0.7540 (2) | 0.66263 (13) | 0.60287 (14) | 0.0382 (5) | |
H5 | 0.7134 | 0.7183 | 0.5808 | 0.046* | |
C6 | 0.6858 (2) | 0.58587 (13) | 0.55676 (15) | 0.0408 (5) | |
H6 | 0.6028 | 0.5901 | 0.5043 | 0.049* | |
C7 | 0.7432 (2) | 0.50313 (13) | 0.59014 (14) | 0.0373 (5) | |
H7 | 0.6997 | 0.4503 | 0.5607 | 0.045* | |
C8 | 0.86766 (19) | 0.49984 (12) | 0.66870 (14) | 0.0302 (4) | |
C9 | 0.93241 (18) | 0.58054 (11) | 0.70935 (13) | 0.0284 (4) | |
C10 | 0.92846 (18) | 0.41197 (12) | 0.70854 (13) | 0.0317 (4) | |
H4A | 1.156 (3) | 0.8007 (18) | 0.6365 (19) | 0.060 (9)* | |
H5A | 0.507 (3) | 0.8825 (19) | 0.523 (2) | 0.070 (9)* | |
H4B | 1.064 (3) | 0.738 (2) | 0.594 (2) | 0.078 (9)* | |
H5B | 0.419 (3) | 0.917 (2) | 0.438 (2) | 0.101 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0289 (2) | 0.0216 (2) | 0.0395 (3) | 0.000 | 0.00533 (18) | 0.000 |
N1 | 0.0268 (11) | 0.0244 (11) | 0.0341 (11) | 0.000 | 0.0055 (9) | 0.000 |
N2 | 0.0303 (8) | 0.0246 (8) | 0.0368 (8) | 0.0005 (6) | 0.0055 (7) | 0.0019 (6) |
O1 | 0.0332 (7) | 0.0264 (7) | 0.0570 (9) | 0.0003 (6) | 0.0031 (7) | −0.0033 (6) |
O2 | 0.0281 (7) | 0.0334 (7) | 0.0477 (8) | 0.0049 (6) | −0.0008 (6) | −0.0034 (6) |
O3 | 0.0393 (8) | 0.0243 (7) | 0.0606 (9) | −0.0055 (6) | 0.0061 (7) | −0.0048 (6) |
O4 | 0.0392 (9) | 0.0368 (9) | 0.0489 (9) | −0.0059 (7) | 0.0129 (7) | −0.0064 (7) |
O5 | 0.0578 (11) | 0.0388 (9) | 0.0477 (10) | −0.0026 (8) | 0.0003 (9) | −0.0084 (7) |
C1 | 0.0293 (10) | 0.0277 (9) | 0.0337 (9) | 0.0020 (8) | 0.0071 (8) | −0.0020 (7) |
C2 | 0.0269 (10) | 0.0275 (9) | 0.0352 (10) | 0.0019 (8) | 0.0054 (8) | −0.0011 (7) |
C3 | 0.0341 (11) | 0.0273 (10) | 0.0620 (14) | 0.0055 (8) | −0.0005 (10) | 0.0010 (9) |
C4 | 0.0481 (19) | 0.0206 (14) | 0.083 (2) | 0.000 | 0.0011 (17) | 0.000 |
C5 | 0.0348 (10) | 0.0291 (10) | 0.0422 (11) | 0.0035 (8) | 0.0022 (9) | 0.0025 (8) |
C6 | 0.0347 (11) | 0.0361 (11) | 0.0416 (11) | −0.0003 (9) | −0.0003 (9) | 0.0006 (8) |
C7 | 0.0352 (11) | 0.0288 (10) | 0.0423 (11) | −0.0052 (8) | 0.0062 (9) | −0.0040 (8) |
C8 | 0.0280 (9) | 0.0248 (9) | 0.0377 (10) | −0.0015 (7) | 0.0111 (8) | −0.0015 (7) |
C9 | 0.0280 (9) | 0.0238 (9) | 0.0339 (9) | 0.0006 (7) | 0.0113 (8) | 0.0009 (7) |
C10 | 0.0303 (10) | 0.0245 (9) | 0.0405 (10) | −0.0010 (8) | 0.0121 (9) | −0.0010 (7) |
Mn1—O4i | 2.2214 (16) | O5—H5B | 0.87 (3) |
Mn1—O4 | 2.2214 (16) | C1—C2 | 1.515 (2) |
Mn1—N1 | 2.289 (2) | C2—C3 | 1.378 (3) |
Mn1—O1i | 2.2897 (14) | C3—C4 | 1.384 (3) |
Mn1—O1 | 2.2897 (14) | C3—H3 | 0.9300 |
Mn1—N2 | 2.3765 (15) | C4—C3i | 1.384 (3) |
Mn1—N2i | 2.3765 (15) | C4—H4C | 0.9300 |
N1—C2i | 1.332 (2) | C5—C6 | 1.383 (3) |
N1—C2 | 1.332 (2) | C5—H5 | 0.9300 |
N2—C5 | 1.340 (2) | C6—C7 | 1.376 (3) |
N2—C9 | 1.344 (2) | C6—H6 | 0.9300 |
O1—C1 | 1.247 (2) | C7—C8 | 1.391 (3) |
O2—C1 | 1.251 (2) | C7—H7 | 0.9300 |
O3—C10 | 1.206 (2) | C8—C9 | 1.398 (2) |
O4—H4A | 0.79 (3) | C8—C10 | 1.475 (2) |
O4—H4B | 0.84 (3) | C9—C9i | 1.481 (3) |
O5—H5A | 0.81 (3) | C10—C10i | 1.546 (4) |
O4i—Mn1—O4 | 175.53 (8) | H5A—O5—H5B | 109 (3) |
O4i—Mn1—N1 | 92.23 (4) | O1—C1—O2 | 125.72 (17) |
O4—Mn1—N1 | 92.23 (4) | O1—C1—C2 | 115.77 (16) |
O4i—Mn1—O1i | 96.58 (6) | O2—C1—C2 | 118.48 (16) |
O4—Mn1—O1i | 85.04 (6) | N1—C2—C3 | 121.89 (18) |
N1—Mn1—O1i | 68.75 (3) | N1—C2—C1 | 113.20 (15) |
O4i—Mn1—O1 | 85.04 (6) | C3—C2—C1 | 124.90 (17) |
O4—Mn1—O1 | 96.58 (6) | C2—C3—C4 | 118.7 (2) |
N1—Mn1—O1 | 68.75 (3) | C2—C3—H3 | 120.7 |
O1i—Mn1—O1 | 137.51 (7) | C4—C3—H3 | 120.7 |
O4i—Mn1—N2 | 92.88 (6) | C3i—C4—C3 | 119.2 (3) |
O4—Mn1—N2 | 83.43 (6) | C3i—C4—H4C | 120.4 |
N1—Mn1—N2 | 145.40 (4) | C3—C4—H4C | 120.4 |
O1i—Mn1—N2 | 144.15 (5) | N2—C5—C6 | 123.68 (17) |
O1—Mn1—N2 | 77.64 (5) | N2—C5—H5 | 118.2 |
O4i—Mn1—N2i | 83.43 (6) | C6—C5—H5 | 118.2 |
O4—Mn1—N2i | 92.88 (5) | C7—C6—C5 | 118.63 (18) |
N1—Mn1—N2i | 145.40 (4) | C7—C6—H6 | 120.7 |
O1i—Mn1—N2i | 77.64 (5) | C5—C6—H6 | 120.7 |
O1—Mn1—N2i | 144.15 (5) | C6—C7—C8 | 118.81 (17) |
N2—Mn1—N2i | 69.20 (7) | C6—C7—H7 | 120.6 |
C2i—N1—C2 | 119.7 (2) | C8—C7—H7 | 120.6 |
C2i—N1—Mn1 | 120.16 (11) | C7—C8—C9 | 119.08 (17) |
C2—N1—Mn1 | 120.16 (11) | C7—C8—C10 | 119.91 (16) |
C5—N2—C9 | 117.74 (16) | C9—C8—C10 | 121.00 (17) |
C5—N2—Mn1 | 123.73 (12) | N2—C9—C8 | 121.99 (16) |
C9—N2—Mn1 | 118.43 (12) | N2—C9—C9i | 116.93 (10) |
C1—O1—Mn1 | 121.98 (12) | C8—C9—C9i | 121.08 (11) |
Mn1—O4—H4A | 116 (2) | O3—C10—C8 | 123.47 (17) |
Mn1—O4—H4B | 116 (2) | O3—C10—C10i | 118.71 (11) |
H4A—O4—H4B | 107 (3) | C8—C10—C10i | 117.80 (10) |
Symmetry code: (i) −x+2, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O3ii | 0.79 (3) | 2.15 (3) | 2.936 (2) | 175 (3) |
O4—H4B···O5iii | 0.84 (3) | 1.85 (3) | 2.687 (2) | 175 (3) |
O5—H5B···O2iv | 0.87 (3) | 1.93 (3) | 2.795 (2) | 171 (3) |
O5—H5A···O2 | 0.81 (3) | 2.03 (3) | 2.793 (2) | 156 (3) |
Symmetry codes: (ii) x+1/2, y+1/2, z; (iii) −x+3/2, −y+3/2, −z+1; (iv) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C7H3NO4)(C12H6N2O2)(H2O)2]·2H2O |
Mr | 502.30 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 273 |
a, b, c (Å) | 10.1751 (11), 14.8325 (11), 14.6121 (13) |
β (°) | 109.861 (1) |
V (Å3) | 2074.1 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.70 |
Crystal size (mm) | 0.16 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.896, 0.933 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5144, 1843, 1637 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.082, 1.04 |
No. of reflections | 1843 |
No. of parameters | 167 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.20 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O3i | 0.79 (3) | 2.15 (3) | 2.936 (2) | 175 (3) |
O4—H4B···O5ii | 0.84 (3) | 1.85 (3) | 2.687 (2) | 175 (3) |
O5—H5B···O2iii | 0.87 (3) | 1.93 (3) | 2.795 (2) | 171 (3) |
O5—H5A···O2 | 0.81 (3) | 2.03 (3) | 2.793 (2) | 156 (3) |
Symmetry codes: (i) x+1/2, y+1/2, z; (ii) −x+3/2, −y+3/2, −z+1; (iii) −x+1, −y+2, −z+1. |
Pyridine-2,6-dicarboxylic acid (pdc) is an excellent ligand because it combines the coordination properties of the pyridine and carboxylate group, which may bind metal ions in a variety of bonding modes (Liu et al., 2006; Okabe & Oya, 2000). 1,10-Phenanthroline-5,6-dione (pdo) is a versatile ligand for the assembly of metal organic materials (Calderazzo et al., 2002; Larsson & Öhrström, 2004). Here, we report the mononuclear Mn2+ complex, (I), formed from a dianionic pyridine-2,6-dicarboxylate ligand (pdc2-), the N-donor ligand 1,10-phenanthroline-5,6-dione (pdo) and water molecules and explore its supramolecular structure.
As can be seen from Fig. 1, the asymmetric unit comprises a Mn2+ cation, half a dianionic pdc ligand and half a bidentate chelating pdo ligand, all located on a twofold symmetry axis, as well as one coordinated water molecule and one crystal lattice water molecule. A ring nitrogen atom and two oxygen atoms of the carboxylate group belonging to the pdc ligand are involved in coordination to the Mn2+ cation. The pdo group acts as a chelating ligand through the N atoms. Coordination of two water molecules at the axial sites completes the distorted pentagonal dipyramid coordination geometry.
In the crystal structure, hydrogen bonding interactions are observed between the coordinated water molecules, the crystal lattice water molecules and the oxygen atoms of the carboxyl groups in a neighbouring unit to form a three-dimensional supramolecular structure (Figure 2).