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The title compound, [Mn(C7H3NO4)(C12H6N2O2)(H2O)2]·2H2O, is a neutral mononuclear MnII complex. The Mn—N bond to the pyridine-2,6-dicarboxylate ligand lies along a crystallographic twofold rotation axis. The Mn2+ cation has a distorted penta­gonal–bipyramidal configuration, coordinated by three N atoms, one from the pyridine-2,6-dicarboxyl­ate ligand and two from the chelating 1,10-phenanthroline-5,6-dione ligand. The remaining four coordination sites are occupied by O atoms, two from the pyridine-2,6-dicarboxyl­ate ligand and two from water mol­ecules. The asymmetric unit also contains a solvent water mol­ecule. The crystal structure is stabilized by a network of O—H...O hydrogen-bonding inter­actions in a three-dimensional supra­molecular structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026001/kj2058sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026001/kj2058Isup2.hkl
Contains datablock I

CCDC reference: 648570

Key indicators

  • Single-crystal X-ray study
  • T = 273 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.029
  • wR factor = 0.082
  • Data-to-parameter ratio = 11.0

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT333_ALERT_2_B Large Average Benzene C-C Dist. C8 -C10 1.46 Ang. PLAT432_ALERT_2_B Short Inter X...Y Contact O2 .. C10 .. 2.91 Ang.
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Mn1 - O1 .. 5.02 su PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C10 - C10_a ... 1.55 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O2 .. C10 .. 2.96 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact C1 .. C10 .. 3.15 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 1.93
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 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

Comment top

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).

Related literature top

For related literature, see: Calderazzo et al. (2002); Larsson & Öhrström (2004); Liu et al. (2006); Okabe & Oya (2000).

Experimental top

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.

Refinement top

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.

Structure description top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of title complex with the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. (symmetry code for A: 2 - x, y, 1.5 - z)
[Figure 2] Fig. 2. A view of the three-dimensional supramolecular structure of the title complex. Hydrogen bonds are drawn as dashed lines.
Diaqua(1,10-phenanthroline-5,6-dione-κ2N,N,)(pyridine-2,6-dicarboxylato- κ3O,N,O')manganese(II) dihydrate top
Crystal data top
[Mn(C7H3NO4)(C12H6N2O2)(H2O)2]·2H2OF(000) = 1028
Mr = 502.30Dx = 1.609 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 117 reflections
a = 10.1751 (11) Åθ = 5–20°
b = 14.8325 (11) ŵ = 0.70 mm1
c = 14.6121 (13) ÅT = 273 K
β = 109.861 (1)°Block, yellow
V = 2074.1 (3) Å30.16 × 0.12 × 0.10 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer
1843 independent reflections
Radiation source: fine-focus sealed tube1637 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
φ and ω scansθmax = 25.1°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 812
Tmin = 0.896, Tmax = 0.933k = 1716
5144 measured reflectionsl = 1716
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H 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 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
[Mn(C7H3NO4)(C12H6N2O2)(H2O)2]·2H2OV = 2074.1 (3) Å3
Mr = 502.30Z = 4
Monoclinic, C2/cMo Kα radiation
a = 10.1751 (11) ŵ = 0.70 mm1
b = 14.8325 (11) ÅT = 273 K
c = 14.6121 (13) Å0.16 × 0.12 × 0.10 mm
β = 109.861 (1)°
Data collection top
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 = 0.933Rint = 0.018
5144 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0290 restraints
wR(F2) = 0.082H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.36 e Å3
1843 reflectionsΔρmin = 0.20 e Å3
167 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
xyzUiso*/Ueq
Mn11.00000.79318 (2)0.75000.03159 (16)
N11.00000.94747 (14)0.75000.0297 (5)
N20.87516 (16)0.66130 (10)0.67750 (11)0.0321 (4)
O10.78287 (14)0.84912 (9)0.66535 (11)0.0420 (4)
O20.64025 (13)0.96698 (9)0.62159 (10)0.0399 (3)
O30.87158 (15)0.34079 (9)0.68074 (11)0.0442 (4)
O41.07694 (18)0.78734 (11)0.62489 (12)0.0422 (4)
O50.44735 (19)0.86864 (11)0.47295 (14)0.0526 (4)
C10.75793 (19)0.93165 (12)0.65935 (13)0.0312 (4)
C20.88249 (18)0.99259 (12)0.70524 (13)0.0312 (4)
C30.8784 (2)1.08543 (13)0.70317 (17)0.0454 (5)
H30.79561.11580.67090.054*
C41.00001.1326 (2)0.75000.0560 (9)
H4C1.00001.19530.75000.067*
C50.7540 (2)0.66263 (13)0.60287 (14)0.0382 (5)
H50.71340.71830.58080.046*
C60.6858 (2)0.58587 (13)0.55676 (15)0.0408 (5)
H60.60280.59010.50430.049*
C70.7432 (2)0.50313 (13)0.59014 (14)0.0373 (5)
H70.69970.45030.56070.045*
C80.86766 (19)0.49984 (12)0.66870 (14)0.0302 (4)
C90.93241 (18)0.58054 (11)0.70935 (13)0.0284 (4)
C100.92846 (18)0.41197 (12)0.70854 (13)0.0317 (4)
H4A1.156 (3)0.8007 (18)0.6365 (19)0.060 (9)*
H5A0.507 (3)0.8825 (19)0.523 (2)0.070 (9)*
H4B1.064 (3)0.738 (2)0.594 (2)0.078 (9)*
H5B0.419 (3)0.917 (2)0.438 (2)0.101 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0289 (2)0.0216 (2)0.0395 (3)0.0000.00533 (18)0.000
N10.0268 (11)0.0244 (11)0.0341 (11)0.0000.0055 (9)0.000
N20.0303 (8)0.0246 (8)0.0368 (8)0.0005 (6)0.0055 (7)0.0019 (6)
O10.0332 (7)0.0264 (7)0.0570 (9)0.0003 (6)0.0031 (7)0.0033 (6)
O20.0281 (7)0.0334 (7)0.0477 (8)0.0049 (6)0.0008 (6)0.0034 (6)
O30.0393 (8)0.0243 (7)0.0606 (9)0.0055 (6)0.0061 (7)0.0048 (6)
O40.0392 (9)0.0368 (9)0.0489 (9)0.0059 (7)0.0129 (7)0.0064 (7)
O50.0578 (11)0.0388 (9)0.0477 (10)0.0026 (8)0.0003 (9)0.0084 (7)
C10.0293 (10)0.0277 (9)0.0337 (9)0.0020 (8)0.0071 (8)0.0020 (7)
C20.0269 (10)0.0275 (9)0.0352 (10)0.0019 (8)0.0054 (8)0.0011 (7)
C30.0341 (11)0.0273 (10)0.0620 (14)0.0055 (8)0.0005 (10)0.0010 (9)
C40.0481 (19)0.0206 (14)0.083 (2)0.0000.0011 (17)0.000
C50.0348 (10)0.0291 (10)0.0422 (11)0.0035 (8)0.0022 (9)0.0025 (8)
C60.0347 (11)0.0361 (11)0.0416 (11)0.0003 (9)0.0003 (9)0.0006 (8)
C70.0352 (11)0.0288 (10)0.0423 (11)0.0052 (8)0.0062 (9)0.0040 (8)
C80.0280 (9)0.0248 (9)0.0377 (10)0.0015 (7)0.0111 (8)0.0015 (7)
C90.0280 (9)0.0238 (9)0.0339 (9)0.0006 (7)0.0113 (8)0.0009 (7)
C100.0303 (10)0.0245 (9)0.0405 (10)0.0010 (8)0.0121 (9)0.0010 (7)
Geometric parameters (Å, º) top
Mn1—O4i2.2214 (16)O5—H5B0.87 (3)
Mn1—O42.2214 (16)C1—C21.515 (2)
Mn1—N12.289 (2)C2—C31.378 (3)
Mn1—O1i2.2897 (14)C3—C41.384 (3)
Mn1—O12.2897 (14)C3—H30.9300
Mn1—N22.3765 (15)C4—C3i1.384 (3)
Mn1—N2i2.3765 (15)C4—H4C0.9300
N1—C2i1.332 (2)C5—C61.383 (3)
N1—C21.332 (2)C5—H50.9300
N2—C51.340 (2)C6—C71.376 (3)
N2—C91.344 (2)C6—H60.9300
O1—C11.247 (2)C7—C81.391 (3)
O2—C11.251 (2)C7—H70.9300
O3—C101.206 (2)C8—C91.398 (2)
O4—H4A0.79 (3)C8—C101.475 (2)
O4—H4B0.84 (3)C9—C9i1.481 (3)
O5—H5A0.81 (3)C10—C10i1.546 (4)
O4i—Mn1—O4175.53 (8)H5A—O5—H5B109 (3)
O4i—Mn1—N192.23 (4)O1—C1—O2125.72 (17)
O4—Mn1—N192.23 (4)O1—C1—C2115.77 (16)
O4i—Mn1—O1i96.58 (6)O2—C1—C2118.48 (16)
O4—Mn1—O1i85.04 (6)N1—C2—C3121.89 (18)
N1—Mn1—O1i68.75 (3)N1—C2—C1113.20 (15)
O4i—Mn1—O185.04 (6)C3—C2—C1124.90 (17)
O4—Mn1—O196.58 (6)C2—C3—C4118.7 (2)
N1—Mn1—O168.75 (3)C2—C3—H3120.7
O1i—Mn1—O1137.51 (7)C4—C3—H3120.7
O4i—Mn1—N292.88 (6)C3i—C4—C3119.2 (3)
O4—Mn1—N283.43 (6)C3i—C4—H4C120.4
N1—Mn1—N2145.40 (4)C3—C4—H4C120.4
O1i—Mn1—N2144.15 (5)N2—C5—C6123.68 (17)
O1—Mn1—N277.64 (5)N2—C5—H5118.2
O4i—Mn1—N2i83.43 (6)C6—C5—H5118.2
O4—Mn1—N2i92.88 (5)C7—C6—C5118.63 (18)
N1—Mn1—N2i145.40 (4)C7—C6—H6120.7
O1i—Mn1—N2i77.64 (5)C5—C6—H6120.7
O1—Mn1—N2i144.15 (5)C6—C7—C8118.81 (17)
N2—Mn1—N2i69.20 (7)C6—C7—H7120.6
C2i—N1—C2119.7 (2)C8—C7—H7120.6
C2i—N1—Mn1120.16 (11)C7—C8—C9119.08 (17)
C2—N1—Mn1120.16 (11)C7—C8—C10119.91 (16)
C5—N2—C9117.74 (16)C9—C8—C10121.00 (17)
C5—N2—Mn1123.73 (12)N2—C9—C8121.99 (16)
C9—N2—Mn1118.43 (12)N2—C9—C9i116.93 (10)
C1—O1—Mn1121.98 (12)C8—C9—C9i121.08 (11)
Mn1—O4—H4A116 (2)O3—C10—C8123.47 (17)
Mn1—O4—H4B116 (2)O3—C10—C10i118.71 (11)
H4A—O4—H4B107 (3)C8—C10—C10i117.80 (10)
Symmetry code: (i) x+2, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O3ii0.79 (3)2.15 (3)2.936 (2)175 (3)
O4—H4B···O5iii0.84 (3)1.85 (3)2.687 (2)175 (3)
O5—H5B···O2iv0.87 (3)1.93 (3)2.795 (2)171 (3)
O5—H5A···O20.81 (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
Mr502.30
Crystal system, space groupMonoclinic, C2/c
Temperature (K)273
a, b, c (Å)10.1751 (11), 14.8325 (11), 14.6121 (13)
β (°) 109.861 (1)
V3)2074.1 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.70
Crystal size (mm)0.16 × 0.12 × 0.10
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.896, 0.933
No. of measured, independent and
observed [I > 2σ(I)] reflections
5144, 1843, 1637
Rint0.018
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.082, 1.04
No. of reflections1843
No. of parameters167
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.36, 0.20

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···O3i0.79 (3)2.15 (3)2.936 (2)175 (3)
O4—H4B···O5ii0.84 (3)1.85 (3)2.687 (2)175 (3)
O5—H5B···O2iii0.87 (3)1.93 (3)2.795 (2)171 (3)
O5—H5A···O20.81 (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.
 

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