Poly­[[di­aqua(μ₄-squarato-O,O′,O′′,O′′′)­manganese(II)] 0.93-hydrate]

In the title compound, {[Mn(C₄O₄)(H₂O)₂]·0.93H₂O}_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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

---

Computing details

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(µ₄-squarato-O,O',O'',O''')manganese(II)] 0.93-hydrate]

Crystal data

[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) Å^3	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

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.113	H-atom parameters constrained
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0485P)^2 + 5.7874P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Mn—O3	2.1409 (14)	C2—C2^v	1.465 (3)
Mn—O3^i	2.1409 (14)	O3—H1	0.8600
Mn—O1	2.1727 (13)	O3—H2	0.8601
Mn—O1^i	2.1727 (13)	O4—O5^iv	1.272 (16)
Mn—O2^i	2.1898 (13)	O4—O5^vi	1.272 (16)
Mn—O2	2.1898 (13)	O4—O5^vii	1.272 (16)
C1—O1	1.248 (2)	O4—O5^viii	1.272 (16)
C1—C1^ii	1.466 (2)	O5—O4^ix	1.272 (16)
C1—C1^iii	1.466 (2)	O5—O5^i	1.39 (3)
C2—O2	1.250 (2)	O5—O5^x	1.57 (2)
C2—C2^iv	1.465 (3)	O5—O5^xi	1.57 (2)
O3—Mn—O3^i	179.21 (8)	O2—C2—C2^iv	136.0 (2)
O3—Mn—O1	96.17 (5)	O2—C2—C2^v	134.0 (2)
O3^i—Mn—O1	84.40 (5)	C2^iv—C2—C2^v	89.990 (4)
O3—Mn—O1^i	84.40 (5)	C2—O2—Mn	136.83 (13)
O3^i—Mn—O1^i	96.17 (5)	Mn—O3—H1	112.2
O1—Mn—O1^i	89.34 (8)	Mn—O3—H2	116.8
O3—Mn—O2^i	86.09 (5)	H1—O3—H2	116.8
O3^i—Mn—O2^i	93.37 (5)	O5^iv—O4—O5^vi	121 (2)
O1—Mn—O2^i	176.62 (6)	O5^iv—O4—O5^vii	75.9 (11)
O1^i—Mn—O2^i	88.37 (6)	O5^vi—O4—O5^vii	75.9 (11)
O3—Mn—O2	93.37 (5)	O5^iv—O4—O5^viii	75.9 (11)
O3^i—Mn—O2	86.09 (5)	O5^vi—O4—O5^viii	75.9 (11)
O1—Mn—O2	88.37 (6)	O5^vii—O4—O5^viii	121 (2)
O1^i—Mn—O2	176.62 (6)	O4^ix—O5—O5^i	119.4 (12)
O2^i—Mn—O2	94.03 (8)	O4^ix—O5—O5^x	52.0 (5)
O1—C1—C1^ii	135.93 (19)	O5^i—O5—O5^x	91.6 (11)
O1—C1—C1^iii	133.91 (19)	O4^ix—O5—O5^xi	52.0 (5)
C1^ii—C1—C1^iii	90.0	O5^i—O5—O5^xi	88.4 (12)
C1—O1—Mn	134.60 (12)	O5^x—O5—O5^xi	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)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H1···O1^ii	0.86	1.92	2.7602 (19)	165
O3—H2···O2^iv	0.86	1.93	2.7742 (19)	166

Symmetry codes: (ii) −z+1/2, y, x; (iv) −x+1, z+1/2, −y+1.