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The title compound, tri­aqua(1,10-phenanthroline-2,9-di­car­box­yl­ato)­magnesium(II) dihydrate, [Mg(PDA)(H2O)3]·2H2O, (H2PDA is 1,10-phenanthroline-2,9-di­carboxyl­ic acid, C14H8N2O4) has twofold crystallographic symmetry. The Mg atom is in a distorted pentagonal bipyramidal coordination environment with two N atoms and two O atoms from PDA and one O atom from a water mol­ecule forming the pentagonal plane, and two O atoms from two water mol­ecules occupying axial positions. The crystal structure comprises an infinite two-dimensional network of hydrogen-bonded mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004317/tk6009sup1.cif
Contains datablocks phenmg, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004317/tk6009Isup2.hkl
Contains datablock I

CCDC reference: 162800

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • H-atom completeness 76%
  • Disorder in solvent or counterion
  • R factor = 0.055
  • wR factor = 0.186
  • Data-to-parameter ratio = 16.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 50.00 Perc. General Notes
FORMU_01 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:C14 H16 Mg1 N2 O9 Atom count from the _atom_site data: C14 H12 Mg1 N2 O9 CELLZ_01 From the CIF: _cell_formula_units_Z 16 From the CIF: _chemical_formula_sum C14 H16 Mg N2 O9 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 224.00 224.00 0.00 H 256.00 192.00 64.00 Mg 16.00 16.00 0.00 N 32.00 32.00 0.00 O 144.00 144.00 0.00 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional? CHEMW_03 From the CIF: _cell_formula_units_Z 16 From the CIF: _chemical_formula_weight 380.60 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 14.00 168.15 H 1.01 12.00 12.10 N 14.01 2.00 28.01 O 16.00 9.00 143.99 Mg 24.31 1.00 24.31 Calculated formula weight 376.56 The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

1,10-Phenanthroline-2,9-dicarboxylic acid (H2PDA) has been used as a simple sensitizing species of luminescent lanthanide ion chelates for analytical applications in aqueous solution (Sammes & Yahioglu, 1994; Mullins et al., 1996). However, investigations of H2PDA complexes with metal ions, such as FeII and EuII, have been limited to spectroscopic characterizations in aqueous solution (König & Ritter, 1981; Templeton & Pollak, 1989; Sammes et al., 1992; Dyson et al., 1999). To our knowledge, no examples of MgII complexes of H2PDA have been characterized in the solid state. We have prepared the MgII complex of H2PDA, (I), and report its the crystal structure here.

The title compound (Fig. 1) is located on a twofold axis of symmetry which passes through the Mg and O3 atoms. The seven-coordinated Mg atom is in a distorted pentagonal bipyramidal geometry. Two N and two O atoms from PDA and one O atom from a water molecule define the pentagonal plane, and the two axial positions are occupied by O atoms derived from two water molecules.

Important bond distances and angles are presented in Table 1. The bond distances between Mg and the PDA donor atoms [Mg—O1 2.3080 (17) Å and Mg—N1 2.2994 (19) Å] are significantly longer than those to the coordinated water molecules [Mg—O3 2.055 (2) Å and Mg—O4 2.0777 (18) Å]. This is probably due to the high rigidity of PDA as well as the high affinity of the MgII ion to water molecules. The carboxylate groups of the PDA ligand are almost coplanar with the phenanthroline unit as indicated by the O1—C1—C2—N1 torsion angle of 1.9 (3)°.

The complexes are inter-connected by hydrogen bonds between the coordinated water molecules, O3 and O4, and the carboxylate O atoms of adjacent PDA with interaction distances of 2.774 (2) and 2.745 (3) Å (Table 2); the equatorial water molecule is hydrogen bonded with the coordinated carboxylate O atoms and the axial water molecules interact with the carbonyl O atoms.

As illustrated in Fig. 2, the complexes associate along the a axis and form columns in the crystal structure. Non-coordinated water molecules also participate in hydrogen bonds and serve to connect the complex units along the b axis. Stacking interactions between centrosymmetrically related phenanthroline units are observed with a plane-to-plane separation of 3.360 (4) Å.

Experimental top

H2PDA was synthesized according to the literature (König et al., 1981). The title compound was crystallized by slow evaporation from the methanol solution prepared by the reaction of equimolar amounts of H2PDA and MgSO4.

Refinement top

The C—H atoms were added at their calculated positions [Uiso= 1.2Ueq(C)] and refined using a riding model. The H atoms of the coordinated water molecules were located from a difference map but were not refined. The non-coordinated water molecule, O5, is disordered over two sites with occupancies of 0.7 for O5 and 0.3 for O5'; H atoms were not included for this molecule.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXTL (Siemens, 1996); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of the title compound with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level (Johnson, 1976). The non-coordinated water molecule has been omitted for clarity. [Symmetry code: (i) -x + 3/4, -y + 3/4, z].
[Figure 2] Fig. 2. Packing diagram of (I) viewed along [100]. Hydrogen bonds are indicated by dashed lines. Displacement ellipsoids are shown at the 30% probability level. All H atoms and the disordered water molecules with lower site occupancy have been omitted for clarity.
Triaqua(1,10-phenanthroline-2,9-dicarboxylato)magnesium(II) dihydrate top
Crystal data top
[Mg(C14H6N2O4)(H2O)3]·2H2OF(000) = 3168
Mr = 380.60Dx = 1.525 Mg m3
Orthorhombic, FdddMo Kα radiation, λ = 0.71073 Å
Hall symbol: -F 2uv 2vwCell parameters from 10406 reflections
a = 7.4194 (12) Åθ = 1.7–28.3°
b = 19.044 (3) ŵ = 0.16 mm1
c = 46.943 (7) ÅT = 293 K
V = 6632.8 (18) Å3Plate, yellow
Z = 160.2 × 0.2 × 0.15 mm
Data collection top
CCD area detector
diffractometer
1385 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.066
Graphite monochromatorθmax = 28.3°, θmin = 1.7°
ϕ and ω scansh = 99
10406 measured reflectionsk = 2525
2063 independent reflectionsl = 6242
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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.186H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.1026P)2 + 8.6902P]
where P = (Fo2 + 2Fc2)/3
2063 reflections(Δ/σ)max < 0.001
129 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
[Mg(C14H6N2O4)(H2O)3]·2H2OV = 6632.8 (18) Å3
Mr = 380.60Z = 16
Orthorhombic, FdddMo Kα radiation
a = 7.4194 (12) ŵ = 0.16 mm1
b = 19.044 (3) ÅT = 293 K
c = 46.943 (7) Å0.2 × 0.2 × 0.15 mm
Data collection top
CCD area detector
diffractometer
1385 reflections with I > 2σ(I)
10406 measured reflectionsRint = 0.066
2063 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.186H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.32 e Å3
2063 reflectionsΔρmin = 0.31 e Å3
129 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*/UeqOcc. (<1)
Mg0.37500.37500.07737 (2)0.0375 (3)
O10.6448 (2)0.42950 (10)0.08789 (3)0.0469 (5)
O20.8903 (3)0.48671 (12)0.07265 (4)0.0602 (6)
O30.37500.37500.12114 (5)0.0519 (7)
O40.2576 (2)0.47404 (10)0.07751 (4)0.0478 (5)
N10.5316 (2)0.40521 (10)0.03692 (4)0.0373 (5)
C10.7482 (3)0.45259 (13)0.06867 (5)0.0417 (6)
C20.6882 (3)0.43836 (12)0.03842 (5)0.0394 (5)
C30.7830 (4)0.45897 (14)0.01391 (6)0.0492 (6)
H30.89520.48370.01560.059*
C40.7149 (4)0.44364 (14)0.01242 (5)0.0522 (7)
H40.78050.45640.02930.063*
C50.5475 (4)0.40896 (13)0.01468 (5)0.0453 (6)
C60.4568 (4)0.39108 (14)0.04074 (5)0.0567 (7)
H60.51320.40210.05860.068*
C70.4614 (3)0.39150 (12)0.01097 (4)0.0386 (5)
O50.4235 (18)0.5506 (3)0.12298 (12)0.061 (2)0.69 (4)
O5'0.327 (9)0.5534 (8)0.1265 (4)0.100 (10)0.31 (4)
H3A0.28560.35320.13410.050*
H4A0.14260.47750.07690.050*
H4B0.29370.49670.09390.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mg0.0400 (6)0.0452 (6)0.0273 (5)0.0001 (5)0.0000.000
O10.0417 (10)0.0646 (12)0.0345 (9)0.0086 (8)0.0030 (7)0.0076 (7)
O20.0427 (10)0.0702 (13)0.0677 (13)0.0095 (9)0.0055 (9)0.0103 (10)
O30.0543 (15)0.0739 (17)0.0276 (11)0.0216 (13)0.0000.000
O40.0427 (9)0.0532 (10)0.0475 (10)0.0020 (8)0.0007 (7)0.0011 (8)
N10.0371 (10)0.0446 (10)0.0304 (9)0.0039 (8)0.0015 (7)0.0030 (8)
C10.0314 (11)0.0484 (13)0.0454 (13)0.0018 (10)0.0024 (9)0.0080 (10)
C20.0381 (12)0.0423 (12)0.0376 (11)0.0056 (9)0.0044 (9)0.0071 (9)
C30.0463 (14)0.0521 (15)0.0491 (15)0.0012 (12)0.0115 (11)0.0105 (11)
C40.0635 (17)0.0546 (15)0.0385 (13)0.0087 (13)0.0172 (11)0.0113 (11)
C50.0612 (16)0.0431 (13)0.0315 (11)0.0127 (12)0.0074 (10)0.0060 (9)
C60.084 (2)0.0564 (17)0.0297 (11)0.0152 (14)0.0076 (11)0.0045 (10)
C70.0470 (13)0.0394 (12)0.0294 (10)0.0102 (9)0.0030 (9)0.0028 (8)
O50.070 (5)0.0518 (19)0.060 (2)0.003 (2)0.006 (2)0.0002 (17)
O5'0.14 (3)0.063 (6)0.096 (8)0.017 (9)0.001 (11)0.028 (6)
Geometric parameters (Å, º) top
Mg—O32.055 (2)N1—C71.350 (3)
Mg—O4i2.0777 (18)C1—C21.513 (3)
Mg—O42.0777 (18)C2—C31.405 (3)
Mg—N12.2994 (19)C3—C41.367 (4)
Mg—N1i2.2994 (19)C4—C51.411 (4)
Mg—O1i2.3080 (16)C5—C71.403 (3)
Mg—O12.3080 (17)C5—C61.437 (4)
O1—C11.263 (3)C6—C6i1.360 (6)
O2—C11.252 (3)C7—C7i1.428 (5)
N1—C21.324 (3)O5—O5'0.74 (5)
O3—Mg—O4i89.81 (5)O1i—Mg—O1155.30 (9)
O3—Mg—O489.81 (5)C1—O1—Mg122.05 (15)
O4i—Mg—O4179.63 (11)C2—N1—C7118.61 (19)
O3—Mg—N1145.68 (5)C2—N1—Mg121.23 (14)
O4i—Mg—N191.03 (7)C7—N1—Mg120.12 (15)
O4—Mg—N189.28 (7)O2—C1—O1125.8 (2)
O3—Mg—N1i145.68 (5)O2—C1—C2118.7 (2)
O4i—Mg—N1i89.28 (7)O1—C1—C2115.4 (2)
O4—Mg—N1i91.03 (7)N1—C2—C3121.9 (2)
N1—Mg—N1i68.64 (10)N1—C2—C1113.18 (18)
O3—Mg—O1i77.65 (5)C3—C2—C1124.9 (2)
O4i—Mg—O1i87.41 (7)C4—C3—C2119.7 (3)
O4—Mg—O1i92.51 (7)C3—C4—C5119.6 (2)
N1—Mg—O1i136.66 (7)C7—C5—C4116.6 (2)
N1i—Mg—O1i68.03 (6)C7—C5—C6117.5 (3)
O3—Mg—O177.65 (5)C4—C5—C6125.9 (2)
O4i—Mg—O192.51 (7)C6i—C6—C5121.63 (16)
O4—Mg—O187.41 (7)N1—C7—C5123.6 (2)
N1—Mg—O168.04 (6)N1—C7—C7i115.56 (13)
N1i—Mg—O1136.66 (7)C5—C7—C7i120.87 (15)
O1—C1—C2—N11.9 (3)O2—C1—C2—C31.9 (4)
Symmetry code: (i) x+3/4, y+3/4, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1ii0.991 (1)1.791 (2)2.774 (2)170.6 (1)
O4—H4A···O2iii0.856 (2)1.891 (2)2.745 (3)175.8 (1)
O4—H4B···O50.922 (2)1.960 (7)2.863 (6)165.7 (4)
O4—H4B···O50.922 (2)1.89 (1)2.80 (1)169 (2)
O5···O2iv2.866 (7)
O5···O2iv2.71 (2)
O5···O5v2.84 (1)
O5···O5v2.73 (3)
Symmetry codes: (ii) x1/2, y+3/4, z+1/4; (iii) x1, y, z; (iv) x+5/4, y, z+1/4; (v) x, y+5/4, z+1/4.

Experimental details

Crystal data
Chemical formula[Mg(C14H6N2O4)(H2O)3]·2H2O
Mr380.60
Crystal system, space groupOrthorhombic, Fddd
Temperature (K)293
a, b, c (Å)7.4194 (12), 19.044 (3), 46.943 (7)
V3)6632.8 (18)
Z16
Radiation typeMo Kα
µ (mm1)0.16
Crystal size (mm)0.2 × 0.2 × 0.15
Data collection
DiffractometerCCD area detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10406, 2063, 1385
Rint0.066
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.186, 1.06
No. of reflections2063
No. of parameters129
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.32, 0.31

Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXTL (Siemens, 1996), SHELXTL.

Selected geometric parameters (Å, º) top
Mg—O32.055 (2)Mg—N12.2994 (19)
Mg—O42.0777 (18)Mg—O12.3080 (17)
O3—Mg—O489.81 (5)O3—Mg—O177.65 (5)
O4i—Mg—O4179.63 (11)O4—Mg—O187.41 (7)
O4—Mg—N189.28 (7)N1—Mg—O168.04 (6)
N1—Mg—N1i68.64 (10)
Symmetry code: (i) x+3/4, y+3/4, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1ii.991 (1)1.791 (2)2.774 (2)170.6 (1)
O4—H4A···O2iii.856 (2)1.891 (2)2.745 (3)175.8 (1)
O4—H4B···O5.922 (2)1.960 (7)2.863 (6)165.7 (4)
O4—H4B···O5'.922 (2)1.89 (1)2.80 (1)169 (2)
O5···O2iv..2.866 (7).
O5'···O2iv..2.71 (2).
O5···O5v..2.84 (1).
O5'···O5'v..2.73 (3).
Symmetry codes: (ii) x1/2, y+3/4, z+1/4; (iii) x1, y, z; (iv) x+5/4, y, z+1/4; (v) x, y+5/4, z+1/4.
 

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