The two Ni atoms and the μ6-1,2,4,5-benzenetetracarboxylate ligand in the crystal structure of catena-[μ6-1,2,4,5-benzenetetracarboxylato-tetraaqua-dinickel(II)] dihydrate, [Ni2(C10H2O8)(H2O)4]·2(H2O), occupy special positions at three independent inversion centers. One of the Ni atoms is chelated by two 1,2,4,5-benzenetetracarboxylates [Ni—O 2.018 (3) and 2.021 (3) Å; O—Ni—O 91.7 (1)°]; the two remaining sites of the coordination octahedron of this atom are taken up by water molecules. The second Ni atom is coordinated by four carbonyl O atoms belonging to four benzenetetracarboxylate ligands [Ni—O 2.045 (3), 2.069 (3) Å]; its coordination sphere also includes two water molecules. Each tetraanionic benzenetetracarboxylate ligand links together six Ni atoms, the linkages giving rise to a three-dimensional network motif. The structure is consolidated by hydrogen bonds involving coordinated as well as uncoordinated water molecules.
Supporting information
CCDC reference: 225653
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- H-atom completeness 72%
- R factor = 0.046
- wR factor = 0.108
- Data-to-parameter ratio = 16.9
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT430_ALERT_2_A Short Inter D...A Contact O3W' .. O3W = 2.03 Ang.
Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT301_ALERT_3_C Main Residue Disorder ......................... 1.00 Perc.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 5
PLAT731_ALERT_1_C Bond Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Rat
O1W -H1W1 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Rat
O1W -H1W2 1.555 1.555
PLAT731_ALERT_1_C Bond Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Rat
O2W -H2W1 1.555 1.555
PLAT745_ALERT_1_C D-H Calc 0.85(3), Rep 0.85000 ...... Missing su
O1W -H1W1 1.555 1.555
PLAT745_ALERT_1_C D-H Calc 0.85(3), Rep 0.85000 ...... Missing su
O1W -H1W2 1.555 1.555
PLAT745_ALERT_1_C D-H Calc 0.85(2), Rep 0.84000 ...... Missing su
O2W -H2W2 1.555 1.555
PLAT745_ALERT_1_C D-H Calc 0.85(3), Rep 0.85000 ...... Missing su
O2W -H2W1 1.555 1.555
PLAT746_ALERT_1_C H...A Calc 2.07(3), Rep 2.07000 ...... Missing su
H1W1 -O1 1.555 2.665
PLAT746_ALERT_1_C H...A Calc 2.04(2), Rep 2.04000 ...... Missing su
H2W2 -O2 1.555 1.565
PLAT746_ALERT_1_C H...A Calc 1.96(3), Rep 1.96000 ...... Missing su
H2W1 -O3 1.555 1.555
PLAT748_ALERT_1_C D-H..A Calc 153(5), Rep 152.00 ...... Missing su
O2W -H2W1 -O3 1.555 1.555 1.555
Alert level G
FORMU01_ALERT_2_G 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:C10 H14 Ni2 O14
Atom count from the _atom_site data: C10 H10 Ni2 O14
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 1
From the CIF: _chemical_formula_sum C10 H14 Ni2 O14
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 10.00 10.00 0.00
H 14.00 10.00 4.00
Ni 2.00 2.00 0.00
O 14.00 14.00 0.00
1 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
19 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
18 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CAD-4 Software (Enraf-Nonius Delft, 1988); cell refinement: CAD-4 Software; data reduction: XCAD4/PC (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-II (Johnson, 1976); software used to prepare material for publication: SHELXL97.
catena-[µ
6-1,2,4,5-Benzenetetracarboxylato-tetraaqua-dinickel(II)]
dihydrate
top
Crystal data top
[Ni2(C10H2O8·(H2O)4]2H2O | Z = 1 |
Mr = 475.63 | F(000) = 242 |
Triclinic, P1 | Dx = 2.003 Mg m−3 |
a = 6.910 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.389 (1) Å | Cell parameters from 25 reflections |
c = 8.223 (1) Å | θ = 12.0–15.0° |
α = 90.08 (7)° | µ = 2.47 mm−1 |
β = 109.83 (8)° | T = 298 K |
γ = 93.37 (7)° | Prism, green |
V = 394.2 (1) Å3 | 0.18 × 0.11 × 0.11 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 1594 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 30.0°, θmin = 2.6° |
ω scan | h = 0→9 |
Absorption correction: psi scan (North et al., 1968) | k = −10→10 |
Tmin = 0.674, Tmax = 0.758 | l = −11→10 |
2476 measured reflections | 2 standard reflections every 60 min |
2300 independent reflections | intensity decay: none |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0438P)2 + 0.0381P] where P = (Fo2 + 2Fc2)/3 |
2300 reflections | (Δ/σ)max = 0.001 |
136 parameters | Δρmax = 1.06 e Å−3 |
6 restraints | Δρmin = −0.83 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Ni1 | 0.0000 | 0.5000 | 0.0000 | 0.0126 (2) | |
Ni2 | 0.5000 | 1.0000 | 0.0000 | 0.0106 (2) | |
O1 | 0.5524 (4) | 0.2356 (3) | 0.1490 (3) | 0.0152 (5) | |
O2 | 0.2549 (4) | 0.3621 (4) | 0.0385 (3) | 0.0206 (6) | |
O3 | 0.1707 (4) | 0.7297 (3) | 0.1046 (3) | 0.0182 (6) | |
O4 | 0.4875 (4) | 0.8589 (4) | 0.2103 (3) | 0.0206 (6) | |
O1w | 0.0415 (5) | 0.5832 (5) | −0.2315 (4) | 0.0265 (7) | |
O2w | 0.1856 (4) | 1.0133 (4) | −0.1066 (4) | 0.0192 (6) | |
O3w | 0.149 (1) | 0.041 (1) | −0.520 (1) | 0.047 (1) | 0.50 |
O3w' | 0.096 (1) | 0.278 (1) | −0.423 (1) | 0.047 (1) | 0.50 |
C1 | 0.4190 (6) | 0.3387 (5) | 0.1597 (5) | 0.0121 (7) | |
C2 | 0.4605 (6) | 0.4286 (5) | 0.3332 (4) | 0.0118 (7) | |
C3 | 0.4188 (5) | 0.6079 (5) | 0.3572 (5) | 0.0121 (7) | |
C4 | 0.4579 (6) | 0.6770 (5) | 0.5226 (5) | 0.0124 (7) | |
C5 | 0.3524 (6) | 0.7395 (5) | 0.2120 (4) | 0.0131 (7) | |
H1w1 | 0.149 (4) | 0.648 (5) | −0.228 (6) | 0.032* | |
H1w2 | 0.039 (7) | 0.483 (3) | −0.283 (6) | 0.032* | |
H2w1 | 0.138 (7) | 0.930 (3) | −0.057 (5) | 0.023* | |
H2w2 | 0.154 (7) | 1.116 (2) | −0.081 (5) | 0.023* | |
H4 | 0.4290 | 0.7960 | 0.5375 | 0.015* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ni1 | 0.0109 (4) | 0.0119 (3) | 0.0123 (4) | 0.0016 (3) | 0.0004 (3) | 0.0008 (3) |
Ni2 | 0.0120 (4) | 0.0097 (3) | 0.0087 (3) | 0.0010 (3) | 0.0019 (3) | 0.0008 (2) |
O1 | 0.012 (1) | 0.017 (1) | 0.015 (1) | 0.005 (1) | 0.001 (1) | −0.005 (1) |
O2 | 0.016 (1) | 0.026 (2) | 0.015 (1) | 0.008 (1) | −0.003 (1) | −0.005 (1) |
O3 | 0.015 (1) | 0.016 (1) | 0.018 (1) | 0.000 (1) | −0.001 (1) | 0.004 (1) |
O4 | 0.020 (2) | 0.024 (1) | 0.013 (1) | −0.007 (1) | 0.001 (1) | 0.007 (1) |
O1w | 0.022 (2) | 0.038 (2) | 0.017 (2) | −0.006 (1) | 0.005 (1) | 0.002 (1) |
O2w | 0.014 (1) | 0.018 (1) | 0.024 (2) | 0.003 (1) | 0.005 (1) | −0.001 (1) |
O3w | 0.043 (3) | 0.048 (3) | 0.036 (3) | −0.006 (3) | −0.003 (2) | 0.010 (2) |
O3w' | 0.043 (3) | 0.048 (3) | 0.036 (3) | −0.006 (3) | −0.003 (2) | 0.010 (2) |
C1 | 0.016 (2) | 0.011 (2) | 0.011 (2) | −0.001 (1) | 0.005 (1) | 0.000 (1) |
C2 | 0.016 (2) | 0.012 (2) | 0.009 (2) | 0.001 (1) | 0.006 (1) | −0.001 (1) |
C3 | 0.011 (2) | 0.011 (2) | 0.011 (2) | 0.000 (1) | 0.001 (1) | 0.001 (1) |
C4 | 0.014 (2) | 0.009 (2) | 0.013 (2) | 0.001 (1) | 0.003 (1) | 0.000 (1) |
C5 | 0.017 (2) | 0.012 (2) | 0.009 (2) | 0.003 (1) | 0.003 (1) | −0.001 (1) |
Geometric parameters (Å, º) top
Ni1—O2 | 2.018 (3) | O3—C5 | 1.264 (5) |
Ni1—O2i | 2.018 (3) | O4—C5 | 1.250 (4) |
Ni1—O3 | 2.021 (3) | C1—C2 | 1.502 (5) |
Ni1—O3i | 2.021 (3) | C2—C4v | 1.391 (5) |
Ni1—O1w | 2.106 (3) | C2—C3 | 1.400 (5) |
Ni1—O1wi | 2.106 (3) | C3—C4 | 1.384 (5) |
Ni2—O1ii | 2.069 (3) | C3—C5 | 1.505 (5) |
Ni2—O1iii | 2.069 (3) | C4—C2v | 1.391 (5) |
Ni2—O4 | 2.045 (3) | O1w—H1w1 | 0.85 (1) |
Ni2—O4iv | 2.045 (3) | O1w—H1w2 | 0.85 (1) |
Ni2—O2w | 2.057 (3) | O2w—H2w1 | 0.85 (1) |
Ni2—O2wiv | 2.057 (3) | O2w—H2w2 | 0.85 (1) |
O1—C1 | 1.255 (4) | C4—H4 | 0.93 |
O2—C1 | 1.251 (5) | | |
| | | |
O2—Ni1—O2i | 180.0 | O4iv—Ni2—O2wiv | 94.3 (1) |
O2—Ni1—O3 | 91.7 (1) | O2w—Ni2—O2wiv | 180.0 |
O2—Ni1—O3i | 88.3 (1) | C1—O1—Ni2vi | 126.6 (2) |
O2—Ni1—O1w | 85.5 (1) | C1—O2—Ni1 | 137.4 (3) |
O2—Ni1—O1wi | 94.5 (1) | C5—O3—Ni1 | 126.3 (2) |
O2i—Ni1—O3 | 88.3 (1) | C5—O4—Ni2 | 126.3 (3) |
O2i—Ni1—O3i | 91.7 (1) | O2—C1—O1 | 123.8 (3) |
O2i—Ni1—O1w | 94.5 (1) | O2—C1—C2 | 120.2 (3) |
O2i—Ni1—O1wi | 85.5 (1) | O1—C1—C2 | 116.0 (3) |
O3i—Ni1—O3 | 180.0 (2) | C4v—C2—C3 | 119.0 (3) |
O3—Ni1—O1w | 85.2 (1) | C4v—C2—C1 | 116.7 (3) |
O3i—Ni1—O1w | 94.8 (1) | C3—C2—C1 | 124.3 (3) |
O3—Ni1—O1wi | 94.8 (1) | C4—C3—C2 | 119.9 (3) |
O3i—Ni1—O1wi | 85.2 (1) | C4—C3—C5 | 116.6 (3) |
O1w—Ni1—O1wi | 180.0 (2) | C2—C3—C5 | 123.2 (3) |
O1ii—Ni2—O1iii | 180.0 | C3—C4—C2v | 121.1 (3) |
O1ii—Ni2—O4 | 88.3 (1) | O4—C5—O3 | 123.8 (3) |
O1ii—Ni2—O4iv | 91.7 (1) | O4—C5—C3 | 115.0 (3) |
O1ii—Ni2—O2wiv | 83.8 (1) | O3—C5—C3 | 121.2 (3) |
O1ii—Ni2—O2w | 96.2 (1) | Ni1—O1w—H1w1 | 120 (3) |
O1iii—Ni2—O4 | 91.7 (1) | Ni1—O1w—H1w2 | 102 (3) |
O1iii—Ni2—O4iv | 88.3 (1) | H1w1—O1w—H1w2 | 109 (2) |
O1iii—Ni2—O2w | 83.8 (1) | Ni2—O2w—H2w1 | 104 (3) |
O1iii—Ni2—O2wiv | 96.2 (1) | Ni2—O2w—H2w2 | 109 (3) |
O4—Ni2—O4iv | 180.0 (2) | H2w1—O2w—H2w2 | 110 (2) |
O4—Ni2—O2w | 94.3 (1) | C3—C4—H4 | 119.5 |
O4—Ni2—O2wiv | 85.7 (1) | C2v—C4—H4 | 119.5 |
O4iv—Ni2—O2w | 85.7 (1) | | |
| | | |
O3i—Ni1—O2—C1 | −131.1 (4) | O1—C1—C2—C4v | −40.3 (5) |
O3—Ni1—O2—C1 | 48.9 (4) | O2—C1—C2—C3 | −42.2 (5) |
O1w—Ni1—O2—C1 | 134.0 (4) | O1—C1—C2—C3 | 140.9 (4) |
O1wi—Ni1—O2—C1 | −46.0 (4) | C4v—C2—C3—C4 | −0.4 (6) |
O2—Ni1—O3—C5 | −24.6 (3) | C1—C2—C3—C4 | 178.3 (3) |
O2i—Ni1—O3—C5 | 155.4 (3) | C4v—C2—C3—C5 | 173.2 (3) |
O1w—Ni1—O3—C5 | −110.0 (3) | C1—C2—C3—C5 | −8.1 (6) |
O1wi—Ni1—O3—C5 | 70.0 (3) | C2—C3—C4—C2v | 0.4 (6) |
O2wiv—Ni2—O4—C5 | −143.8 (3) | C5—C3—C4—C2v | −173.6 (3) |
O2w—Ni2—O4—C5 | 36.2 (3) | Ni2—O4—C5—O3 | −25.4 (5) |
O1ii—Ni2—O4—C5 | 132.3 (3) | Ni2—O4—C5—C3 | 156.5 (2) |
O1iii—Ni2—O4—C5 | −47.7 (3) | Ni1—O3—C5—O4 | 142.0 (3) |
Ni1—O2—C1—O1 | 176.9 (3) | Ni1—O3—C5—C3 | −40.1 (5) |
Ni1—O2—C1—C2 | 0.2 (6) | C4—C3—C5—O4 | 67.5 (5) |
Ni2vi—O1—C1—O2 | −31.0 (5) | C2—C3—C5—O4 | −106.3 (4) |
Ni2vi—O1—C1—C2 | 145.8 (3) | C4—C3—C5—O3 | −110.6 (4) |
O2—C1—C2—C4v | 136.6 (4) | C2—C3—C5—O3 | 75.6 (5) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y+1, z; (iii) −x+1, −y+1, −z; (iv) −x+1, −y+2, −z; (v) −x+1, −y+1, −z+1; (vi) x, y−1, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H1w1···O1iii | 0.85 | 2.07 | 2.897 (4) | 162 |
O1w—H1w2···O3w′ | 0.85 | 2.04 | 2.865 (9) | 164 |
O2w—H2w2···O2ii | 0.84 | 2.04 | 2.785 (4) | 147 |
O2w—H2w1···O3 | 0.85 | 1.96 | 2.743 (4) | 152 |
Symmetry codes: (ii) x, y+1, z; (iii) −x+1, −y+1, −z. |