The crystal structure of the title compound, CoK2(H2P2O7)2·2H2O, is, to our knowledge, the first example of a mixed-metal dihydrogendiphosphate, containing an alkali earth metal and a divalent transition metal. The metal ions and the two water O atoms are located on a crystallographic mirror plane.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (P-O) = 0.001 Å
- R factor = 0.024
- wR factor = 0.061
- Data-to-parameter ratio = 19.1
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level A:
DIFF_019 Alert A _diffrn_standards_number is missing
Number of standards used in measurement.
| Author response: The data were measured on an area-detector.
|
DIFF_020 Alert A _diffrn_standards_interval_count and
_diffrn_standards_interval_time are missing. Number of measurements
between standards or time (min) between standards.
| Author response: The data were measured on an area-detector.
|
DIFF_022 Alert A _diffrn_standards_decay_% is missing
Percentage decrease in standards intensity.
| Author response: The data were measured on an area-detector.
|
3 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check
Crystals were prepared by dissolving stochiometric amounts of CoCl2.6 H2O in a solution made of K4P2O7 in distilled water. The mixture has been stirred for 1 d and the resulting light-pink solution was allowed to stand at atmospheric temperature. After two to three weeks, pink crystals deposited which have been filtered off and washed with a solution of ethanol (80%).
All H atoms could be located by difference Fourier synthesis and were refined isotropically.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991).
Crystal data top
[CoK2(H2P2O7)2]·2H2O | F(000) = 1044 |
Mr = 525.07 | Dx = 2.439 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 28672 reflections |
a = 9.7044 (5) Å | θ = 3.6–31.3° |
b = 11.0023 (6) Å | µ = 2.32 mm−1 |
c = 13.3937 (8) Å | T = 173 K |
V = 1430.05 (14) Å3 | Block, light pink |
Z = 4 | 0.22 × 0.18 × 0.09 mm |
Data collection top
STOE IPDS II two-circle diffractometer | 2441 independent reflections |
Radiation source: fine-focus sealed tube | 2173 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ω scans | θmax = 31.4°, θmin = 3.7° |
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995) | h = −11→14 |
Tmin = 0.630, Tmax = 0.819 | k = −16→16 |
24419 measured reflections | l = −19→19 |
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)] = 0.024 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | All H-atom parameters refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.057P] where P = (Fo2 + 2Fc2)/3 |
2441 reflections | (Δ/σ)max = 0.001 |
128 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.70 e Å−3 |
Crystal data top
[CoK2(H2P2O7)2]·2H2O | V = 1430.05 (14) Å3 |
Mr = 525.07 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 9.7044 (5) Å | µ = 2.32 mm−1 |
b = 11.0023 (6) Å | T = 173 K |
c = 13.3937 (8) Å | 0.22 × 0.18 × 0.09 mm |
Data collection top
STOE IPDS II two-circle diffractometer | 2441 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995) | 2173 reflections with I > 2σ(I) |
Tmin = 0.630, Tmax = 0.819 | Rint = 0.049 |
24419 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.061 | All H-atom parameters refined |
S = 1.03 | Δρmax = 0.37 e Å−3 |
2441 reflections | Δρmin = −0.70 e Å−3 |
128 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 | x | y | z | Uiso*/Ueq | |
Co1 | 0.33245 (3) | 0.7500 | 0.359996 (17) | 0.01247 (7) | |
K1 | 0.24827 (4) | 0.2500 | 0.12438 (3) | 0.01874 (9) | |
K2 | 0.05369 (5) | 0.2500 | 0.60189 (3) | 0.02236 (10) | |
P1 | 0.43938 (3) | 0.48215 (3) | 0.27784 (2) | 0.01280 (7) | |
P2 | 0.24459 (3) | 0.48399 (3) | 0.44235 (2) | 0.01275 (7) | |
O1 | 0.42720 (11) | 0.42671 (10) | 0.17638 (7) | 0.01901 (19) | |
O2 | 0.44669 (10) | 0.61916 (9) | 0.28249 (7) | 0.01586 (17) | |
O3 | 0.56475 (12) | 0.42715 (10) | 0.33434 (8) | 0.01954 (19) | |
H3 | 0.589 (4) | 0.473 (3) | 0.375 (2) | 0.055 (9)* | |
O4 | 0.30435 (11) | 0.43772 (9) | 0.33644 (7) | 0.01684 (18) | |
O5 | 0.11138 (11) | 0.40773 (9) | 0.45315 (7) | 0.01637 (18) | |
H5 | 0.057 (3) | 0.416 (3) | 0.413 (2) | 0.040 (7)* | |
O6 | 0.21535 (11) | 0.61816 (9) | 0.43337 (7) | 0.01678 (18) | |
O7 | 0.34367 (11) | 0.44641 (10) | 0.52279 (7) | 0.01930 (19) | |
O8 | 0.19631 (16) | 0.7500 | 0.23301 (11) | 0.0184 (3) | |
H8 | 0.141 (3) | 0.803 (3) | 0.223 (2) | 0.052 (9)* | |
O9 | 0.47828 (16) | 0.7500 | 0.47601 (10) | 0.0169 (3) | |
H9 | 0.536 (3) | 0.808 (2) | 0.4789 (19) | 0.042 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.01200 (12) | 0.01229 (11) | 0.01314 (11) | 0.000 | 0.00057 (8) | 0.000 |
K1 | 0.01607 (19) | 0.01573 (17) | 0.02441 (18) | 0.000 | −0.00209 (14) | 0.000 |
K2 | 0.0310 (2) | 0.02212 (19) | 0.01395 (16) | 0.000 | 0.00207 (15) | 0.000 |
P1 | 0.01289 (15) | 0.01317 (14) | 0.01234 (13) | −0.00020 (11) | 0.00038 (10) | −0.00072 (9) |
P2 | 0.01209 (15) | 0.01346 (15) | 0.01269 (13) | −0.00059 (11) | 0.00006 (10) | 0.00065 (9) |
O1 | 0.0176 (5) | 0.0248 (5) | 0.0146 (4) | −0.0050 (4) | 0.0017 (3) | −0.0048 (3) |
O2 | 0.0157 (4) | 0.0139 (4) | 0.0179 (4) | 0.0006 (3) | 0.0021 (3) | 0.0007 (3) |
O3 | 0.0194 (5) | 0.0188 (4) | 0.0204 (4) | 0.0043 (4) | −0.0039 (4) | −0.0018 (4) |
O4 | 0.0180 (5) | 0.0171 (4) | 0.0155 (4) | −0.0037 (4) | 0.0031 (3) | −0.0018 (3) |
O5 | 0.0144 (4) | 0.0187 (4) | 0.0160 (4) | −0.0034 (3) | −0.0009 (3) | 0.0037 (3) |
O6 | 0.0171 (4) | 0.0143 (4) | 0.0189 (4) | −0.0008 (3) | 0.0036 (3) | 0.0017 (3) |
O7 | 0.0179 (5) | 0.0220 (5) | 0.0180 (4) | 0.0031 (4) | −0.0056 (3) | −0.0014 (3) |
O8 | 0.0163 (7) | 0.0175 (6) | 0.0215 (6) | 0.000 | −0.0046 (5) | 0.000 |
O9 | 0.0162 (6) | 0.0159 (6) | 0.0187 (6) | 0.000 | −0.0029 (5) | 0.000 |
Geometric parameters (Å, º) top
Co1—O6i | 2.0883 (10) | K2—O6iv | 3.0239 (12) |
Co1—O6 | 2.0883 (10) | K2—O8iv | 3.2827 (17) |
Co1—O2i | 2.0926 (10) | K2—Co1ii | 3.6293 (5) |
Co1—O2 | 2.0926 (10) | K2—P1ii | 3.7740 (4) |
Co1—O9 | 2.1018 (14) | K2—P1ix | 3.7740 (4) |
Co1—O8 | 2.1537 (15) | K2—Co1iv | 3.7819 (6) |
Co1—K1ii | 3.6266 (5) | P1—O1 | 1.4942 (10) |
Co1—K2iii | 3.6293 (5) | P1—O2 | 1.5103 (10) |
Co1—K2iv | 3.7818 (6) | P1—O3 | 1.5553 (11) |
K1—O3v | 2.6975 (11) | P1—O4 | 1.6038 (11) |
K1—O3vi | 2.6975 (11) | P1—K2iii | 3.7740 (4) |
K1—O1 | 2.6982 (11) | P2—O7 | 1.5021 (10) |
K1—O1vii | 2.6982 (11) | P2—O6 | 1.5079 (11) |
K1—O6viii | 2.9621 (10) | P2—O5 | 1.5479 (11) |
K1—O6iii | 2.9621 (10) | P2—O4 | 1.6149 (10) |
K1—O9iii | 2.9636 (16) | P2—K1ii | 3.8097 (5) |
K1—Co1iii | 3.6267 (5) | O2—K2iii | 2.8149 (10) |
K1—P1vii | 3.7667 (5) | O3—K1xi | 2.6975 (11) |
K1—P1 | 3.7667 (5) | O3—H3 | 0.78 (3) |
K1—P2viii | 3.8097 (5) | O5—H5 | 0.76 (3) |
K1—P2iii | 3.8097 (5) | O6—K1ii | 2.9621 (10) |
K2—O5 | 2.7007 (10) | O6—K2iv | 3.0239 (12) |
K2—O5vii | 2.7008 (10) | O8—K2iii | 2.9951 (17) |
K2—O2ii | 2.8149 (10) | O8—K2iv | 3.2826 (17) |
K2—O2ix | 2.8149 (10) | O8—H8 | 0.81 (3) |
K2—O8ii | 2.9951 (17) | O9—K1ii | 2.9635 (16) |
K2—O6x | 3.0239 (12) | O9—H9 | 0.85 (3) |
| | | |
O6i—Co1—O6 | 87.99 (6) | O2ii—K2—O8ii | 59.81 (3) |
O6i—Co1—O2i | 92.51 (4) | O2ix—K2—O8ii | 59.81 (3) |
O6—Co1—O2i | 178.28 (4) | O5—K2—O6x | 111.84 (3) |
O6i—Co1—O2 | 178.28 (4) | O5vii—K2—O6x | 75.85 (3) |
O6—Co1—O2 | 92.51 (4) | O2ii—K2—O6x | 112.23 (3) |
O2i—Co1—O2 | 86.93 (5) | O2ix—K2—O6x | 83.55 (3) |
O6i—Co1—O9 | 91.06 (4) | O8ii—K2—O6x | 142.28 (3) |
O6—Co1—O9 | 91.06 (4) | O5—K2—O6iv | 75.85 (3) |
O2i—Co1—O9 | 90.57 (4) | O5vii—K2—O6iv | 111.84 (3) |
O2—Co1—O9 | 90.57 (4) | O2ii—K2—O6iv | 83.55 (3) |
O6i—Co1—O8 | 92.17 (4) | O2ix—K2—O6iv | 112.23 (3) |
O6—Co1—O8 | 92.17 (4) | O8ii—K2—O6iv | 142.28 (3) |
O2i—Co1—O8 | 86.17 (4) | O6x—K2—O6iv | 57.33 (4) |
O2—Co1—O8 | 86.17 (4) | O5—K2—O8iv | 130.55 (3) |
O9—Co1—O8 | 175.51 (6) | O5vii—K2—O8iv | 130.55 (3) |
O6i—Co1—K1ii | 54.76 (3) | O2ii—K2—O8iv | 54.56 (3) |
O6—Co1—K1ii | 54.76 (3) | O2ix—K2—O8iv | 54.56 (3) |
O2i—Co1—K1ii | 126.78 (3) | O8ii—K2—O8iv | 101.752 (13) |
O2—Co1—K1ii | 126.78 (3) | O6x—K2—O8iv | 57.80 (3) |
O9—Co1—K1ii | 54.80 (4) | O6iv—K2—O8iv | 57.80 (3) |
O8—Co1—K1ii | 129.69 (4) | O5—K2—Co1ii | 129.76 (2) |
O6i—Co1—K2iii | 127.87 (3) | O5vii—K2—Co1ii | 129.76 (2) |
O6—Co1—K2iii | 127.87 (3) | O2ii—K2—Co1ii | 35.10 (2) |
O2i—Co1—K2iii | 50.67 (3) | O2ix—K2—Co1ii | 35.10 (2) |
O2—Co1—K2iii | 50.67 (3) | O8ii—K2—Co1ii | 36.37 (3) |
O9—Co1—K2iii | 119.95 (4) | O6x—K2—Co1ii | 114.31 (2) |
O8—Co1—K2iii | 55.57 (4) | O6iv—K2—Co1ii | 114.31 (2) |
K1ii—Co1—K2iii | 174.749 (13) | O8iv—K2—Co1ii | 65.38 (3) |
O6i—Co1—K2iv | 52.94 (3) | O5—K2—P1ii | 87.43 (2) |
O6—Co1—K2iv | 52.94 (3) | O5vii—K2—P1ii | 163.47 (3) |
O2i—Co1—K2iv | 126.29 (3) | O2ii—K2—P1ii | 20.62 (2) |
O2—Co1—K2iv | 126.29 (3) | O2ix—K2—P1ii | 82.11 (2) |
O9—Co1—K2iv | 124.57 (4) | O8ii—K2—P1ii | 67.630 (17) |
O8—Co1—K2iv | 59.92 (4) | O6x—K2—P1ii | 119.18 (2) |
K1ii—Co1—K2iv | 69.768 (10) | O6iv—K2—P1ii | 74.83 (2) |
K2iii—Co1—K2iv | 115.483 (12) | O8iv—K2—P1ii | 65.953 (16) |
O3v—K1—O3vi | 92.53 (5) | Co1ii—K2—P1ii | 53.114 (7) |
O3v—K1—O1 | 153.20 (4) | O5—K2—P1ix | 163.47 (3) |
O3vi—K1—O1 | 81.45 (4) | O5vii—K2—P1ix | 87.43 (2) |
O3v—K1—O1vii | 81.45 (4) | O2ii—K2—P1ix | 82.11 (2) |
O3vi—K1—O1vii | 153.20 (4) | O2ix—K2—P1ix | 20.62 (2) |
O1—K1—O1vii | 92.20 (5) | O8ii—K2—P1ix | 67.630 (17) |
O3v—K1—O6viii | 84.37 (3) | O6x—K2—P1ix | 74.83 (2) |
O3vi—K1—O6viii | 127.56 (3) | O6iv—K2—P1ix | 119.18 (2) |
O1—K1—O6viii | 119.94 (3) | O8iv—K2—P1ix | 65.953 (16) |
O1vii—K1—O6viii | 78.08 (3) | Co1ii—K2—P1ix | 53.114 (7) |
O3v—K1—O6iii | 127.56 (3) | P1ii—K2—P1ix | 102.680 (14) |
O3vi—K1—O6iii | 84.37 (3) | O5—K2—Co1iv | 107.76 (3) |
O1—K1—O6iii | 78.08 (3) | O5vii—K2—Co1iv | 107.76 (3) |
O1vii—K1—O6iii | 119.94 (3) | O2ii—K2—Co1iv | 83.26 (2) |
O6viii—K1—O6iii | 58.64 (4) | O2ix—K2—Co1iv | 83.26 (2) |
O3v—K1—O9iii | 69.37 (3) | O8ii—K2—Co1iv | 136.34 (3) |
O3vi—K1—O9iii | 69.37 (3) | O6x—K2—Co1iv | 33.443 (19) |
O1—K1—O9iii | 130.58 (3) | O6iv—K2—Co1iv | 33.44 (2) |
O1vii—K1—O9iii | 130.58 (3) | O8iv—K2—Co1iv | 34.59 (3) |
O6viii—K1—O9iii | 60.61 (3) | Co1ii—K2—Co1iv | 99.967 (11) |
O6iii—K1—O9iii | 60.61 (3) | P1ii—K2—Co1iv | 86.179 (10) |
O3v—K1—Co1iii | 93.30 (3) | P1ix—K2—Co1iv | 86.179 (10) |
O3vi—K1—Co1iii | 93.30 (3) | O1—P1—O2 | 116.66 (6) |
O1—K1—Co1iii | 113.02 (2) | O1—P1—O3 | 110.22 (6) |
O1vii—K1—Co1iii | 113.02 (2) | O2—P1—O3 | 109.36 (6) |
O6viii—K1—Co1iii | 35.16 (2) | O1—P1—O4 | 104.83 (6) |
O6iii—K1—Co1iii | 35.16 (2) | O2—P1—O4 | 108.81 (6) |
O9iii—K1—Co1iii | 35.42 (3) | O3—P1—O4 | 106.41 (6) |
O3v—K1—P1vii | 73.93 (3) | O2—P1—K1 | 136.25 (4) |
O3vi—K1—P1vii | 134.68 (3) | O3—P1—K1 | 112.76 (4) |
O1—K1—P1vii | 91.77 (3) | O4—P1—K1 | 70.01 (4) |
O1vii—K1—P1vii | 18.86 (2) | O1—P1—K2iii | 75.66 (4) |
O6viii—K1—P1vii | 94.62 (2) | O3—P1—K2iii | 126.42 (5) |
O6iii—K1—P1vii | 138.13 (3) | O4—P1—K2iii | 123.93 (4) |
O9iii—K1—P1vii | 136.985 (8) | K1—P1—K2iii | 101.393 (11) |
Co1iii—K1—P1vii | 129.729 (9) | O7—P2—O6 | 116.56 (6) |
O3v—K1—P1 | 134.68 (3) | O7—P2—O5 | 108.56 (6) |
O3vi—K1—P1 | 73.93 (3) | O6—P2—O5 | 112.39 (6) |
O1—K1—P1 | 18.86 (2) | O7—P2—O4 | 108.26 (6) |
O1vii—K1—P1 | 91.77 (3) | O6—P2—O4 | 107.82 (5) |
O6viii—K1—P1 | 138.13 (3) | O5—P2—O4 | 102.19 (5) |
O6iii—K1—P1 | 94.62 (2) | O7—P2—K1ii | 74.98 (4) |
O9iii—K1—P1 | 136.984 (8) | O5—P2—K1ii | 111.83 (4) |
Co1iii—K1—P1 | 129.729 (9) | O4—P2—K1ii | 142.92 (4) |
P1vii—K1—P1 | 85.389 (14) | O7—P2—K2 | 73.98 (5) |
O3v—K1—P2viii | 65.68 (2) | O6—P2—K2 | 127.76 (4) |
O3vi—K1—P2viii | 134.29 (3) | O4—P2—K2 | 116.91 (4) |
O1—K1—P2viii | 135.00 (3) | K1ii—P2—K2 | 99.695 (11) |
O1vii—K1—P2viii | 66.42 (2) | P1—O1—K1 | 125.44 (6) |
O6viii—K1—P2viii | 21.40 (2) | P1—O2—Co1 | 133.01 (6) |
O6iii—K1—P2viii | 79.71 (2) | P1—O2—K2iii | 118.35 (5) |
O9iii—K1—P2viii | 65.442 (17) | Co1—O2—K2iii | 94.23 (4) |
Co1iii—K1—P2viii | 51.618 (7) | P1—O3—K1xi | 153.81 (6) |
P1vii—K1—P2viii | 79.592 (8) | P1—O3—H3 | 109 (3) |
P1—K1—P2viii | 149.449 (14) | K1xi—O3—H3 | 97 (3) |
O3v—K1—P2iii | 134.29 (3) | P1—O4—P2 | 128.85 (6) |
O3vi—K1—P2iii | 65.68 (2) | P2—O5—K2 | 126.18 (5) |
O1—K1—P2iii | 66.42 (2) | P2—O5—H5 | 116 (2) |
O1vii—K1—P2iii | 135.00 (3) | K2—O5—H5 | 117 (2) |
O6viii—K1—P2iii | 79.71 (2) | P2—O6—Co1 | 127.96 (6) |
O6iii—K1—P2iii | 21.40 (2) | P2—O6—K1ii | 112.83 (5) |
O9iii—K1—P2iii | 65.442 (17) | Co1—O6—K1ii | 90.08 (4) |
Co1iii—K1—P2iii | 51.618 (7) | P2—O6—K2iv | 130.13 (6) |
P1vii—K1—P2iii | 149.448 (14) | Co1—O6—K2iv | 93.62 (4) |
P1—K1—P2iii | 79.591 (8) | K1ii—O6—K2iv | 90.16 (3) |
P2viii—K1—P2iii | 100.388 (14) | Co1—O8—K2iii | 88.06 (5) |
O5—K2—O5vii | 79.97 (4) | Co1—O8—K2iv | 85.49 (5) |
O5—K2—O2ii | 107.79 (3) | K2iii—O8—K2iv | 173.55 (5) |
O5vii—K2—O2ii | 164.32 (3) | Co1—O8—H8 | 123 (2) |
O5—K2—O2ix | 164.32 (3) | K2iii—O8—H8 | 116 (2) |
O5vii—K2—O2ix | 107.79 (3) | K2iv—O8—H8 | 67 (2) |
O2ii—K2—O2ix | 61.52 (4) | Co1—O9—K1ii | 89.78 (5) |
O5—K2—O8ii | 105.34 (3) | Co1—O9—H9 | 118.5 (18) |
O5vii—K2—O8ii | 105.34 (3) | K1ii—O9—H9 | 117.2 (18) |
| | | |
O3v—K1—P1—O1 | 171.35 (8) | O4—P1—O1—K1 | −12.95 (9) |
O3vi—K1—P1—O1 | −111.38 (8) | K2iii—P1—O1—K1 | −134.84 (7) |
O1vii—K1—P1—O1 | 91.64 (9) | O3v—K1—O1—P1 | −13.73 (13) |
O6viii—K1—P1—O1 | 17.61 (8) | O3vi—K1—O1—P1 | 64.81 (7) |
O6iii—K1—P1—O1 | −28.60 (8) | O1vii—K1—O1—P1 | −89.02 (8) |
O9iii—K1—P1—O1 | −79.17 (9) | O6viii—K1—O1—P1 | −166.53 (6) |
Co1iii—K1—P1—O1 | −30.67 (8) | O6iii—K1—O1—P1 | 150.82 (8) |
P1vii—K1—P1—O1 | 109.39 (8) | O9iii—K1—O1—P1 | 118.09 (8) |
P2viii—K1—P1—O1 | 48.95 (8) | Co1iii—K1—O1—P1 | 154.77 (6) |
P2iii—K1—P1—O1 | −43.89 (8) | P1vii—K1—O1—P1 | −70.16 (7) |
O3v—K1—P1—O2 | −118.65 (7) | P2viii—K1—O1—P1 | −147.18 (6) |
O3vi—K1—P1—O2 | −41.37 (6) | P2iii—K1—O1—P1 | 131.93 (8) |
O1—K1—P1—O2 | 70.01 (9) | O1—P1—O2—Co1 | 125.99 (8) |
O1vii—K1—P1—O2 | 161.64 (6) | O3—P1—O2—Co1 | −108.12 (9) |
O6viii—K1—P1—O2 | 87.62 (7) | O4—P1—O2—Co1 | 7.72 (10) |
O6iii—K1—P1—O2 | 41.41 (6) | K1—P1—O2—Co1 | 88.13 (8) |
O9iii—K1—P1—O2 | −9.17 (8) | K2iii—P1—O2—Co1 | 128.17 (11) |
Co1iii—K1—P1—O2 | 39.34 (6) | O1—P1—O2—K2iii | −2.19 (8) |
P1vii—K1—P1—O2 | 179.40 (6) | O3—P1—O2—K2iii | 123.70 (6) |
P2viii—K1—P1—O2 | 118.95 (6) | O4—P1—O2—K2iii | −120.46 (6) |
P2iii—K1—P1—O2 | 26.12 (6) | K1—P1—O2—K2iii | −40.04 (8) |
O3v—K1—P1—O3 | 77.99 (4) | O6—Co1—O2—P1 | 3.25 (9) |
O3vi—K1—P1—O3 | 155.27 (5) | O2i—Co1—O2—P1 | −175.12 (5) |
O1—K1—P1—O3 | −93.35 (9) | O9—Co1—O2—P1 | 94.34 (8) |
O1vii—K1—P1—O3 | −1.71 (5) | O8—Co1—O2—P1 | −88.75 (8) |
O6viii—K1—P1—O3 | −75.74 (6) | K1ii—Co1—O2—P1 | 49.76 (9) |
O6iii—K1—P1—O3 | −121.95 (5) | K2iii—Co1—O2—P1 | −136.07 (10) |
O9iii—K1—P1—O3 | −172.52 (6) | K2iv—Co1—O2—P1 | −41.01 (9) |
Co1iii—K1—P1—O3 | −124.02 (5) | O6—Co1—O2—K2iii | 139.33 (4) |
P1vii—K1—P1—O3 | 16.04 (5) | O2i—Co1—O2—K2iii | −39.04 (5) |
P2viii—K1—P1—O3 | −44.41 (5) | O9—Co1—O2—K2iii | −129.59 (4) |
P2iii—K1—P1—O3 | −137.24 (5) | O8—Co1—O2—K2iii | 47.32 (4) |
O3v—K1—P1—O4 | −21.98 (6) | K1ii—Co1—O2—K2iii | −174.167 (15) |
O3vi—K1—P1—O4 | 55.29 (5) | K2iv—Co1—O2—K2iii | 95.07 (3) |
O1—K1—P1—O4 | 166.67 (9) | O1—P1—O3—K1xi | −27.81 (17) |
O1vii—K1—P1—O4 | −101.69 (5) | O2—P1—O3—K1xi | −157.31 (14) |
O6viii—K1—P1—O4 | −175.72 (5) | O4—P1—O3—K1xi | 85.32 (15) |
O6iii—K1—P1—O4 | 138.07 (5) | K1—P1—O3—K1xi | 10.57 (16) |
O9iii—K1—P1—O4 | 87.50 (6) | K2iii—P1—O3—K1xi | −114.58 (14) |
Co1iii—K1—P1—O4 | 136.00 (4) | O1—P1—O4—P2 | −168.82 (8) |
P1vii—K1—P1—O4 | −83.94 (4) | O2—P1—O4—P2 | −43.33 (10) |
P2viii—K1—P1—O4 | −144.38 (5) | O3—P1—O4—P2 | 74.40 (10) |
P2iii—K1—P1—O4 | 122.78 (4) | K1—P1—O4—P2 | −176.82 (9) |
O3v—K1—P1—K2iii | −144.17 (4) | K2iii—P1—O4—P2 | −86.33 (9) |
O3vi—K1—P1—K2iii | −66.89 (3) | O7—P2—O4—P1 | −67.36 (10) |
O1—K1—P1—K2iii | 44.49 (8) | O6—P2—O4—P1 | 59.55 (10) |
O1vii—K1—P1—K2iii | 136.12 (2) | O5—P2—O4—P1 | 178.16 (8) |
O6viii—K1—P1—K2iii | 62.10 (3) | K1ii—P2—O4—P1 | 21.72 (13) |
O6iii—K1—P1—K2iii | 15.89 (2) | K2—P2—O4—P1 | −148.25 (7) |
O9iii—K1—P1—K2iii | −34.68 (5) | O7—P2—O5—K2 | 5.81 (8) |
Co1iii—K1—P1—K2iii | 13.819 (19) | O6—P2—O5—K2 | −124.62 (6) |
P1vii—K1—P1—K2iii | 153.882 (10) | O4—P2—O5—K2 | 120.06 (7) |
P2viii—K1—P1—K2iii | 93.43 (2) | K1ii—P2—O5—K2 | −74.98 (6) |
P2iii—K1—P1—K2iii | 0.599 (12) | O5vii—K2—O5—P2 | −105.26 (6) |
O5—K2—P2—O7 | −174.27 (8) | O2ii—K2—O5—P2 | 60.69 (7) |
O5vii—K2—P2—O7 | −101.89 (5) | O2ix—K2—O5—P2 | 15.93 (17) |
O2ii—K2—P2—O7 | 62.67 (5) | O8ii—K2—O5—P2 | −1.95 (7) |
O2ix—K2—P2—O7 | 13.27 (6) | O6x—K2—O5—P2 | −175.48 (6) |
O8ii—K2—P2—O7 | 3.84 (5) | O6iv—K2—O5—P2 | 139.01 (7) |
O6x—K2—P2—O7 | −168.72 (5) | O8iv—K2—O5—P2 | 118.89 (7) |
O6iv—K2—P2—O7 | 146.23 (5) | Co1ii—K2—O5—P2 | 28.98 (8) |
O8iv—K2—P2—O7 | 107.17 (6) | P1ii—K2—O5—P2 | 64.01 (7) |
Co1ii—K2—P2—O7 | 29.53 (4) | P1ix—K2—O5—P2 | −64.40 (13) |
P1ii—K2—P2—O7 | 71.77 (4) | Co1iv—K2—O5—P2 | 149.16 (6) |
P1ix—K2—P2—O7 | −25.13 (5) | O7—P2—O6—Co1 | 82.29 (8) |
Co1iv—K2—P2—O7 | 149.79 (4) | O5—P2—O6—Co1 | −151.49 (7) |
O5—K2—P2—O6 | 74.26 (9) | O4—P2—O6—Co1 | −39.63 (9) |
O5vii—K2—P2—O6 | 146.64 (6) | K1ii—P2—O6—Co1 | 109.30 (9) |
O2ii—K2—P2—O6 | −48.79 (6) | K2—P2—O6—Co1 | 172.11 (4) |
O2ix—K2—P2—O6 | −98.19 (7) | O7—P2—O6—K1ii | −27.01 (8) |
O8ii—K2—P2—O6 | −107.62 (6) | O5—P2—O6—K1ii | 99.22 (6) |
O6x—K2—P2—O6 | 79.81 (6) | O4—P2—O6—K1ii | −148.93 (5) |
O6iv—K2—P2—O6 | 34.76 (7) | K2—P2—O6—K1ii | 62.82 (7) |
O8iv—K2—P2—O6 | −4.30 (7) | O7—P2—O6—K2iv | −138.04 (7) |
Co1ii—K2—P2—O6 | −81.94 (5) | O5—P2—O6—K2iv | −11.82 (8) |
P1ii—K2—P2—O6 | −39.70 (5) | O4—P2—O6—K2iv | 100.04 (7) |
P1ix—K2—P2—O6 | −136.59 (5) | K1ii—P2—O6—K2iv | −111.03 (8) |
Co1iv—K2—P2—O6 | 38.32 (6) | K2—P2—O6—K2iv | −48.22 (8) |
O5vii—K2—P2—O5 | 72.37 (7) | O6i—Co1—O6—P2 | −166.55 (5) |
O2ii—K2—P2—O5 | −123.06 (7) | O2—Co1—O6—P2 | 15.10 (8) |
O2ix—K2—P2—O5 | −172.46 (8) | O9—Co1—O6—P2 | −75.52 (8) |
O8ii—K2—P2—O5 | 178.11 (7) | O8—Co1—O6—P2 | 101.36 (8) |
O6x—K2—P2—O5 | 5.55 (7) | K1ii—Co1—O6—P2 | −119.56 (8) |
O6iv—K2—P2—O5 | −39.50 (7) | K2iii—Co1—O6—P2 | 54.78 (9) |
O8iv—K2—P2—O5 | −78.56 (8) | K2iv—Co1—O6—P2 | 150.28 (9) |
Co1ii—K2—P2—O5 | −156.20 (7) | O6i—Co1—O6—K1ii | −46.99 (5) |
P1ii—K2—P2—O5 | −113.97 (7) | O2—Co1—O6—K1ii | 134.65 (3) |
P1ix—K2—P2—O5 | 149.14 (7) | O9—Co1—O6—K1ii | 44.03 (4) |
Co1iv—K2—P2—O5 | −35.95 (7) | O8—Co1—O6—K1ii | −139.08 (4) |
O5—K2—P2—O4 | −71.56 (8) | K2iii—Co1—O6—K1ii | 174.341 (15) |
O5vii—K2—P2—O4 | 0.81 (5) | K2iv—Co1—O6—K1ii | −90.17 (3) |
O2ii—K2—P2—O4 | 165.38 (5) | O6i—Co1—O6—K2iv | 43.18 (4) |
O2ix—K2—P2—O4 | 115.98 (6) | O2—Co1—O6—K2iv | −135.18 (3) |
O8ii—K2—P2—O4 | 106.55 (5) | O9—Co1—O6—K2iv | 134.20 (4) |
O6x—K2—P2—O4 | −66.02 (6) | O8—Co1—O6—K2iv | −48.92 (4) |
O6iv—K2—P2—O4 | −111.07 (5) | K1ii—Co1—O6—K2iv | 90.17 (3) |
O8iv—K2—P2—O4 | −150.13 (6) | K2iii—Co1—O6—K2iv | −95.49 (3) |
Co1ii—K2—P2—O4 | 132.23 (5) | O6i—Co1—O8—K2iii | 135.96 (3) |
P1ii—K2—P2—O4 | 174.47 (5) | O6—Co1—O8—K2iii | −135.96 (3) |
P1ix—K2—P2—O4 | 77.58 (5) | O2i—Co1—O8—K2iii | 43.59 (3) |
Co1iv—K2—P2—O4 | −107.51 (5) | O2—Co1—O8—K2iii | −43.59 (3) |
O5—K2—P2—K1ii | 114.55 (7) | K1ii—Co1—O8—K2iii | 180.0 |
O5vii—K2—P2—K1ii | −173.07 (3) | K2iv—Co1—O8—K2iii | 180.0 |
O2ii—K2—P2—K1ii | −8.50 (2) | O6i—Co1—O8—K2iv | −44.04 (3) |
O2ix—K2—P2—K1ii | −57.90 (4) | O6—Co1—O8—K2iv | 44.04 (3) |
O8ii—K2—P2—K1ii | −67.33 (2) | O2i—Co1—O8—K2iv | −136.41 (3) |
O6x—K2—P2—K1ii | 120.10 (3) | O2—Co1—O8—K2iv | 136.41 (3) |
O6iv—K2—P2—K1ii | 75.05 (2) | K1ii—Co1—O8—K2iv | 0.0 |
O8iv—K2—P2—K1ii | 35.99 (4) | K2iii—Co1—O8—K2iv | 180.0 |
Co1ii—K2—P2—K1ii | −41.648 (14) | O6i—Co1—O9—K1ii | 44.01 (3) |
P1ii—K2—P2—K1ii | 0.588 (12) | O6—Co1—O9—K1ii | −44.01 (3) |
P1ix—K2—P2—K1ii | −96.30 (2) | O2i—Co1—O9—K1ii | 136.53 (3) |
Co1iv—K2—P2—K1ii | 78.609 (14) | O2—Co1—O9—K1ii | −136.53 (3) |
O2—P1—O1—K1 | −133.36 (7) | K2iii—Co1—O9—K1ii | 180.0 |
O3—P1—O1—K1 | 101.18 (8) | K2iv—Co1—O9—K1ii | 0.0 |
Symmetry codes: (i) x, −y+3/2, z; (ii) −x+1/2, −y+1, z+1/2; (iii) −x+1/2, −y+1, z−1/2; (iv) −x, −y+1, −z+1; (v) x−1/2, −y+1/2, −z+1/2; (vi) x−1/2, y, −z+1/2; (vii) x, −y+1/2, z; (viii) −x+1/2, y−1/2, z−1/2; (ix) −x+1/2, y−1/2, z+1/2; (x) −x, y−1/2, −z+1; (xi) x+1/2, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O7xii | 0.78 (3) | 1.76 (3) | 2.5272 (15) | 170 (4) |
O5—H5···O1vi | 0.76 (3) | 1.74 (3) | 2.4996 (15) | 176 (3) |
O8—H8···O2xiii | 0.81 (3) | 2.07 (3) | 2.8255 (17) | 156 (3) |
O9—H9···O7xiv | 0.85 (3) | 1.92 (3) | 2.7669 (14) | 175 (3) |
Symmetry codes: (vi) x−1/2, y, −z+1/2; (xii) −x+1, −y+1, −z+1; (xiii) x−1/2, −y+3/2, −z+1/2; (xiv) −x+1, y+1/2, −z+1. |
Experimental details
Crystal data |
Chemical formula | [CoK2(H2P2O7)2]·2H2O |
Mr | 525.07 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 173 |
a, b, c (Å) | 9.7044 (5), 11.0023 (6), 13.3937 (8) |
V (Å3) | 1430.05 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.32 |
Crystal size (mm) | 0.22 × 0.18 × 0.09 |
|
Data collection |
Diffractometer | STOE IPDS II two-circle diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 1990; Blessing, 1995) |
Tmin, Tmax | 0.630, 0.819 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24419, 2441, 2173 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.732 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.061, 1.03 |
No. of reflections | 2441 |
No. of parameters | 128 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.37, −0.70 |
Selected bond lengths (Å) topCo1—O6 | 2.0883 (10) | K1—O9iii | 2.9636 (16) |
Co1—O2 | 2.0926 (10) | K2—O5 | 2.7007 (10) |
Co1—O9 | 2.1018 (14) | K2—O2iv | 2.8149 (10) |
Co1—O8 | 2.1537 (15) | K2—O8iv | 2.9951 (17) |
K1—O3i | 2.6975 (11) | K2—O6v | 3.0239 (12) |
K1—O1 | 2.6982 (11) | K2—O8vi | 3.2827 (17) |
K1—O6ii | 2.9621 (10) | | |
Symmetry codes: (i) x−1/2, −y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, z−1/2; (iii) −x+1/2, −y+1, z−1/2; (iv) −x+1/2, −y+1, z+1/2; (v) −x, y−1/2, −z+1; (vi) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O7vii | 0.78 (3) | 1.76 (3) | 2.5272 (15) | 170 (4) |
O5—H5···O1viii | 0.76 (3) | 1.74 (3) | 2.4996 (15) | 176 (3) |
O8—H8···O2ix | 0.81 (3) | 2.07 (3) | 2.8255 (17) | 156 (3) |
O9—H9···O7x | 0.85 (3) | 1.92 (3) | 2.7669 (14) | 175 (3) |
Symmetry codes: (vii) −x+1, −y+1, −z+1; (viii) x−1/2, y, −z+1/2; (ix) x−1/2, −y+3/2, −z+1/2; (x) −x+1, y+1/2, −z+1. |
The crystal structure of the title compound, CoK2(H2P2O7)2.2H2O, is to our knowledge the first example of a mixed-metal dihydrogendiphosphate, containing an alkaline and a divalent transition metal. The metal atoms and the two water oxygen atoms are located on a crystallographic mirror plane. The Co atoms are octahedrally coordinated. Whereas one of the K ions (K1) is bonded to seven O atoms, the other one (K2) makes eight bonds to O atoms.