In the title compound, {[Mn(C
4O
4)(H
2O)
2]·0.93H
2O}
n, the Mn atoms are each coordinated by four O atoms of two pairs of symmetry-related squarate dianions and two O atoms of two symmetry-related water molecules within slightly distorted octahedra. The water molecules occupy general positions and the two crystallographically independent squarate dianions, as well as the Mn atom, are located in special positions. The squarate dianions and the water molecules are connected
via O—H
O hydrogen bonding. In the crystal structure, voids are found that are filled with additional, disordered, clathrate water molecules.
Supporting information
CCDC reference: 200722
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- H-atom completeness 69%
- Disorder in solvent or counterion
- R factor = 0.037
- wR factor = 0.112
- Data-to-parameter ratio = 15.7
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 36.00 Perc.
PLAT_601 Alert C Structure Contains Solvent Accessible VOIDS of 67.00 A 3
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:C4 H5.86 Mn1 O6.93
Atom count from the _atom_site data: C4 H4 Mn1 O6.93
CELLZ_01
From the CIF: _cell_formula_units_Z 24
From the CIF: _chemical_formula_sum C4 H5.86 Mn O6.93
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 96.00 96.00 0.00
H 140.64 96.00 44.64
Mn 24.00 24.00 0.00
O 166.32 166.32 0.00
Difference between formula and atom_site contents detected.
WARNING: H atoms missing from atom site list. Is this intentional?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
Data collection: IPDS Program Package (Stoe & Cie, 1998); cell refinement: IPDS Program Package; data reduction: IPDS Program Package; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXL97.
Poly[[diaqua(µ
4-squarato-O,
O',
O'',
O''')manganese(II)]
0.93-hydrate]
top
Crystal data top
[Mn(C4O4)(H2O)2]·0.93H2O | Melting point: decomposes at about 250°C K |
Mr = 219.77 | Mo Kα radiation, λ = 0.71073 Å |
Cubic, Pn3n | Cell parameters from 8000 reflections |
a = 16.5527 (8) Å | θ = 2.5–28° |
V = 4535.3 (4) Å3 | µ = 1.74 mm−1 |
Z = 24 | T = 293 K |
F(000) = 2602 | Block, colourless |
Dx = 1.931 Mg m−3 | 0.15 × 0.05 × 0.05 mm |
Data collection top
Stoe IPDS diffractometer | 821 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.049 |
Graphite monochromator | θmax = 28.0°, θmin = 3.9° |
φ scans | h = −21→21 |
28798 measured reflections | k = −21→18 |
908 independent reflections | l = −21→18 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H-atom parameters constrained |
S = 1.18 | w = 1/[σ2(Fo2) + (0.0485P)2 + 5.7874P] where P = (Fo2 + 2Fc2)/3 |
908 reflections | (Δ/σ)max = 0.001 |
58 parameters | Δρmax = 0.73 e Å−3 |
0 restraints | Δρmin = −0.65 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Mn | 0.498174 (14) | 0.498174 (14) | 0.2500 | 0.0081 (2) | |
C1 | 0.30833 (10) | 0.48233 (11) | 0.22723 (10) | 0.0127 (4) | |
O1 | 0.37797 (8) | 0.48637 (9) | 0.19862 (8) | 0.0193 (4) | |
C2 | 0.50060 (11) | 0.69129 (11) | 0.22832 (12) | 0.0151 (4) | |
O2 | 0.50295 (9) | 0.62095 (8) | 0.20098 (8) | 0.0216 (4) | |
O3 | 0.45951 (9) | 0.53810 (9) | 0.36679 (9) | 0.0204 (4) | |
H1 | 0.4126 | 0.5195 | 0.3793 | 0.031* | |
H2 | 0.4690 | 0.5877 | 0.3790 | 0.031* | |
O4 | 0.2500 | 0.6703 (13) | 0.2500 | 0.143 (7)* | 0.48 (2) |
O5 | 0.7016 (11) | 0.7039 (11) | 0.2082 (8) | 0.143 (7)* | 0.345 (15) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn | 0.0080 (2) | 0.0080 (2) | 0.0083 (3) | 0.00028 (11) | −0.00055 (8) | 0.00055 (8) |
C1 | 0.0084 (8) | 0.0213 (9) | 0.0083 (7) | 0.0013 (7) | −0.0001 (6) | 0.0003 (7) |
O1 | 0.0064 (6) | 0.0406 (9) | 0.0109 (6) | −0.0002 (5) | 0.0008 (5) | 0.0017 (6) |
C2 | 0.0271 (10) | 0.0092 (8) | 0.0092 (8) | −0.0003 (6) | 0.0010 (6) | 0.0003 (6) |
O2 | 0.0467 (9) | 0.0066 (6) | 0.0115 (6) | 0.0005 (5) | 0.0029 (5) | −0.0009 (5) |
O3 | 0.0215 (7) | 0.0207 (7) | 0.0190 (7) | −0.0053 (5) | 0.0086 (5) | −0.0087 (5) |
Geometric parameters (Å, º) top
Mn—O3 | 2.1409 (14) | C2—C2v | 1.465 (3) |
Mn—O3i | 2.1409 (14) | O3—H1 | 0.8600 |
Mn—O1 | 2.1727 (13) | O3—H2 | 0.8601 |
Mn—O1i | 2.1727 (13) | O4—O5iv | 1.272 (16) |
Mn—O2i | 2.1898 (13) | O4—O5vi | 1.272 (16) |
Mn—O2 | 2.1898 (13) | O4—O5vii | 1.272 (16) |
C1—O1 | 1.248 (2) | O4—O5viii | 1.272 (16) |
C1—C1ii | 1.466 (2) | O5—O4ix | 1.272 (16) |
C1—C1iii | 1.466 (2) | O5—O5i | 1.39 (3) |
C2—O2 | 1.250 (2) | O5—O5x | 1.57 (2) |
C2—C2iv | 1.465 (3) | O5—O5xi | 1.57 (2) |
| | | |
O3—Mn—O3i | 179.21 (8) | O2—C2—C2iv | 136.0 (2) |
O3—Mn—O1 | 96.17 (5) | O2—C2—C2v | 134.0 (2) |
O3i—Mn—O1 | 84.40 (5) | C2iv—C2—C2v | 89.990 (4) |
O3—Mn—O1i | 84.40 (5) | C2—O2—Mn | 136.83 (13) |
O3i—Mn—O1i | 96.17 (5) | Mn—O3—H1 | 112.2 |
O1—Mn—O1i | 89.34 (8) | Mn—O3—H2 | 116.8 |
O3—Mn—O2i | 86.09 (5) | H1—O3—H2 | 116.8 |
O3i—Mn—O2i | 93.37 (5) | O5iv—O4—O5vi | 121 (2) |
O1—Mn—O2i | 176.62 (6) | O5iv—O4—O5vii | 75.9 (11) |
O1i—Mn—O2i | 88.37 (6) | O5vi—O4—O5vii | 75.9 (11) |
O3—Mn—O2 | 93.37 (5) | O5iv—O4—O5viii | 75.9 (11) |
O3i—Mn—O2 | 86.09 (5) | O5vi—O4—O5viii | 75.9 (11) |
O1—Mn—O2 | 88.37 (6) | O5vii—O4—O5viii | 121 (2) |
O1i—Mn—O2 | 176.62 (6) | O4ix—O5—O5i | 119.4 (12) |
O2i—Mn—O2 | 94.03 (8) | O4ix—O5—O5x | 52.0 (5) |
O1—C1—C1ii | 135.93 (19) | O5i—O5—O5x | 91.6 (11) |
O1—C1—C1iii | 133.91 (19) | O4ix—O5—O5xi | 52.0 (5) |
C1ii—C1—C1iii | 90.0 | O5i—O5—O5xi | 88.4 (12) |
C1—O1—Mn | 134.60 (12) | O5x—O5—O5xi | 90.000 (7) |
Symmetry codes: (i) y, x, −z+1/2; (ii) −z+1/2, y, x; (iii) z, y, −x+1/2; (iv) −x+1, z+1/2, −y+1; (v) −x+1, −z+1, y−1/2; (vi) x−1/2, z+1/2, y−1/2; (vii) y−1/2, z+1/2, −x+1; (viii) −y+1, z+1/2, x−1/2; (ix) −z+1, x+1/2, y−1/2; (x) y, −x+3/2, z; (xi) −y+3/2, x, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1···O1ii | 0.86 | 1.92 | 2.7602 (19) | 165 |
O3—H2···O2iv | 0.86 | 1.93 | 2.7742 (19) | 166 |
Symmetry codes: (ii) −z+1/2, y, x; (iv) −x+1, z+1/2, −y+1. |