In the title compound, {[Ni(C4O4)(H2O)2]·0.71H2O}n, each Ni atom is coordinated by four squarate dianions and two water molecules within a slightly distorted octahedron. The water molecules occupy general positions and the Ni atom, as well as the two crystallographically independent squarate dianions, are located in special positions. Hydrogen bonding is found between the O atoms of the squarate dianions and the water molecules. In the crystal structure, voids are found that are filled with disordered clathrate water molecules. The compound is isotypic with the previously reported Mn, Fe and Co compounds.
Supporting information
CCDC reference: 200732
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.003 Å
- Disorder in solvent or counterion
- R factor = 0.024
- wR factor = 0.077
- Data-to-parameter ratio = 11.9
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03
From the CIF: _diffrn_reflns_theta_max 26.50
From the CIF: _reflns_number_total 704
TEST2: Reflns within _diffrn_reflns_theta_max
Count of symmetry unique reflns 745
Completeness (_total/calc) 94.50%
Alert C: < 95% complete
PLAT_302 Alert C Anion/Solvent Disorder ....................... 28.00 Perc.
PLAT_601 Alert C Structure Contains Solvent Accessible VOIDS of 51.00 A 3
General Notes
FORMU_01 There is a discrepancy between the atom counts in the
_chemical_formula_sum and _chemical_formula_moiety. This is
usually due to the moiety formula being in the wrong format.
Atom count from _chemical_formula_sum: C4 H4 Ni1 O6.71
Atom count from _chemical_formula_moiety:C4 H5.4 Ni1 O6.7
REFLT_03
From the CIF: _diffrn_reflns_theta_max 26.50
From the CIF: _reflns_number_total 704
From the CIF: _diffrn_reflns_limit_ max hkl 20. 20. 16.
From the CIF: _diffrn_reflns_limit_ min hkl -8. -16. -14.
TEST1: Expected hkl limits for theta max
Calculated maximum hkl 20. 20. 20.
Calculated minimum hkl -20. -20. -20.
ALERT: Expected hkl max differ from CIF values
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
3 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''')nickel(II)]
0.71-hydrate]
top
Crystal data top
[Ni(C4O4)(H2O)2]·0.71H2O | Mo Kα radiation, λ = 0.71073 Å |
Mr = 218.12 | Cell parameters from 8000 reflections |
Cubic, Pn3n | θ = 2.5–26.5° |
a = 16.1467 (8) Å | µ = 2.76 mm−1 |
V = 4209.7 (4) Å3 | T = 293 K |
Z = 24 | Block, light green |
F(000) = 2632 | 0.2 × 0.2 × 0.2 mm |
Dx = 2.065 Mg m−3 | |
Data collection top
Stoe IPDS diffractometer | 508 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.026 |
Graphite monochromator | θmax = 26.5°, θmin = 1.8° |
φ scans | h = −8→20 |
7475 measured reflections | k = −16→20 |
704 independent reflections | l = −14→16 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0348P)2 + 5.3938P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
704 reflections | Δρmax = 0.48 e Å−3 |
59 parameters | Δρmin = −0.46 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00045 (9) |
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) |
Ni | 0.498248 (16) | 0.498248 (16) | 0.2500 | 0.0100 (2) | |
C1 | 0.30983 (15) | 0.48345 (14) | 0.22750 (14) | 0.0148 (5) | |
O1 | 0.38197 (10) | 0.48724 (11) | 0.19876 (10) | 0.0193 (4) | |
C2 | 0.50071 (15) | 0.68953 (15) | 0.22847 (15) | 0.0173 (6) | |
O2 | 0.50353 (11) | 0.61723 (10) | 0.20048 (11) | 0.0213 (5) | |
O3 | 0.46163 (10) | 0.53619 (10) | 0.36349 (10) | 0.0182 (4) | |
H1 | 0.4158 | 0.5185 | 0.3765 | 0.027* | |
H2 | 0.4675 | 0.5845 | 0.3779 | 0.027* | |
O4 | 0.2500 | 0.6672 (15) | 0.2500 | 0.132 (7)* | 0.384 (19) |
O5 | 0.2982 (15) | 0.7047 (9) | 0.2007 (15) | 0.132 (7)* | 0.258 (10) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni | 0.0103 (2) | 0.0103 (2) | 0.0095 (2) | −0.00010 (13) | −0.00017 (11) | 0.00017 (11) |
C1 | 0.0131 (12) | 0.0197 (11) | 0.0115 (12) | 0.0011 (10) | −0.0005 (8) | −0.0008 (9) |
O1 | 0.0096 (8) | 0.0353 (10) | 0.0130 (9) | 0.0005 (7) | 0.0003 (7) | 0.0012 (7) |
C2 | 0.0251 (13) | 0.0135 (11) | 0.0134 (13) | −0.0014 (10) | 0.0010 (9) | 0.0013 (8) |
O2 | 0.0419 (12) | 0.0097 (8) | 0.0122 (9) | 0.0006 (7) | 0.0025 (7) | −0.0003 (7) |
O3 | 0.0193 (9) | 0.0183 (9) | 0.0170 (8) | −0.0039 (7) | 0.0070 (7) | −0.0048 (7) |
Geometric parameters (Å, º) top
Ni—O3i | 2.0206 (15) | C2—C2v | 1.466 (4) |
Ni—O3 | 2.0206 (15) | O3—H1 | 0.8201 |
Ni—O1 | 2.0593 (16) | O3—H2 | 0.8200 |
Ni—O1i | 2.0593 (16) | O4—O5ii | 1.267 (19) |
Ni—O2 | 2.0826 (17) | O4—O5iii | 1.267 (19) |
Ni—O2i | 2.0826 (17) | O4—O5 | 1.267 (19) |
C1—O1 | 1.255 (3) | O4—O5vi | 1.267 (19) |
C1—C1ii | 1.460 (3) | O5—O5vii | 1.46 (3) |
C1—C1iii | 1.460 (3) | O5—O5ii | 1.57 (3) |
C2—O2 | 1.253 (3) | O5—O5iii | 1.57 (3) |
C2—C2iv | 1.466 (4) | | |
| | | |
O3i—Ni—O3 | 179.14 (10) | O2—C2—C2iv | 133.4 (2) |
O3i—Ni—O1 | 83.50 (6) | O2—C2—C2v | 136.6 (2) |
O3—Ni—O1 | 97.11 (7) | C2iv—C2—C2v | 89.986 (6) |
O3i—Ni—O1i | 97.11 (7) | C2—O2—Ni | 136.03 (15) |
O3—Ni—O1i | 83.50 (6) | Ni—O3—H1 | 113.0 |
O1—Ni—O1i | 90.23 (10) | Ni—O3—H2 | 120.9 |
O3i—Ni—O2 | 84.80 (7) | H1—O3—H2 | 111.3 |
O3—Ni—O2 | 94.62 (7) | O5ii—O4—O5iii | 123 (3) |
O1—Ni—O2 | 87.86 (7) | O5ii—O4—O5 | 76.8 (12) |
O1i—Ni—O2 | 177.14 (7) | O5iii—O4—O5 | 76.8 (12) |
O3i—Ni—O2i | 94.62 (7) | O5ii—O4—O5vi | 76.8 (12) |
O3—Ni—O2i | 84.80 (7) | O5iii—O4—O5vi | 76.8 (12) |
O1—Ni—O2i | 177.14 (7) | O5—O4—O5vi | 123 (3) |
O1i—Ni—O2i | 87.86 (7) | O4—O5—O5vii | 118.5 (14) |
O2—Ni—O2i | 94.12 (10) | O4—O5—O5ii | 51.6 (6) |
O1—C1—C1ii | 133.8 (2) | O5vii—O5—O5ii | 90.7 (14) |
O1—C1—C1iii | 136.0 (2) | O4—O5—O5iii | 51.6 (6) |
C1ii—C1—C1iii | 90.000 (1) | O5vii—O5—O5iii | 89.3 (15) |
C1—O1—Ni | 134.56 (15) | O5ii—O5—O5iii | 90.000 (4) |
Symmetry codes: (i) y, x, −z+1/2; (ii) z, y, −x+1/2; (iii) −z+1/2, y, x; (iv) −x+1, −z+1, y−1/2; (v) −x+1, z+1/2, −y+1; (vi) −x+1/2, y, −z+1/2; (vii) −z+1/2, −y+3/2, −x+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1···O1iii | 0.82 | 1.92 | 2.724 (2) | 167 |
O3—H2···O2v | 0.82 | 1.93 | 2.730 (2) | 164 |
Symmetry codes: (iii) −z+1/2, y, x; (v) −x+1, z+1/2, −y+1. |