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During experiments aimed at the crystal growth of tetra­potassium dodeca­tungstogermanate, K4[GeW12O40].xH2O, the title compound, dipotassium sodium hydrogen dodeca­tungstogermanate hepta­hydrate, K2NaH[GeW12O40]·7H2O, (I), was obtained serendipitously. The [GeW12O40]4− units in (I) are inter­connected by K+ cations to establish a three-dimensional network, with large channels running along the c axis. Disordered Na+ cations and water mol­ecules reside on the outside of these channels, leaving empty pores with a diameter of ca 9.2 Å. The heteropolyoxoanion is of the Keggin-type, with a central Ge atom situated on a position with 222 symmetry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806034362/wm2028sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536806034362/wm2028Isup2.hkl
Contains datablock I

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](O-O) = 0.020 Å
  • H-atom completeness 54%
  • Disorder in solvent or counterion
  • R factor = 0.036
  • wR factor = 0.076
  • Data-to-parameter ratio = 15.0

checkCIF/PLATON results

No syntax errors found



Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.174 0.295 Tmin and Tmax expected: 0.089 0.199 RR = 1.319 Please check that your absorption correction is appropriate. STRVA01_ALERT_4_C Flack test results are ambiguous. From the CIF: _refine_ls_abs_structure_Flack 0.610 From the CIF: _refine_ls_abs_structure_Flack_su 0.030 PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero ....... 0.61 PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.33 Ratio PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.35 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.67 PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT076_ALERT_1_C Occupancy 0.50 less than 1.0 for Sp.pos . O3W PLAT127_ALERT_1_C Implicit Hall Symbol Inconsistent with Explicit P62 2c PLAT213_ALERT_2_C Atom W2 has ADP max/min Ratio ............. 3.80 oblat PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 12.00 Perc. PLAT430_ALERT_2_C Short Inter D...A Contact O1 .. O3W .. 2.88 Ang. PLAT602_ALERT_4_C VERY LARGE Solvent Accessible VOID(S) in Structure ! PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2 PLAT731_ALERT_1_C Bond Calc 0.88(17), Rep 0.87(5) ...... 3.40 su-Ra O1W -H1WA 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.87(15), Rep 0.87(5) ...... 3.00 su-Ra O1W -H1WB 1.555 1.555 PLAT752_ALERT_4_C Angle Calc 178.00, Rep 178(10) ...... Senseless su K1 -O1W -H1WA 1.555 1.555 1.555 PLAT752_ALERT_4_C Angle Calc 75.00, Rep 75(10) ...... Senseless su H1WA -O1W -H1WB 1.555 1.555 1.555 PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ...... 15.00 Deg. NA1 -O1W -H1WB 1.555 1.555 1.555 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 Ge O40 W12 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 2 H2 O PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 3 O3 PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 4 O PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 5 K PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 6 Na
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:H15 Ge1 K2 Na1 O47 W12 Atom count from the _atom_site data: H8 Ge1 K2 Na1 O47 W12 ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.674 Tmax scaled 0.199 Tmin scaled 0.117 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 3 From the CIF: _chemical_formula_sum Ge H15 K2 Na1 O47 W12 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff Ge 3.00 3.00 0.00 H 45.00 24.00 21.00 K 6.00 6.00 0.00 Na 3.00 3.00 0.00 O 141.00 141.00 0.00 W 36.00 36.00 0.00 REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.05 From the CIF: _reflns_number_total 2318 Count of symmetry unique reflns 1405 Completeness (_total/calc) 164.98% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 913 Fraction of Friedel pairs measured 0.650 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 26 ALERT level C = Check and explain 7 ALERT level G = General alerts; check 11 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 14 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Computing details top

Data collection: XSCANS (Bruker, 2000); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 2000) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97.

Dipotassium sodium hydrogen dodecatungstogermanate heptahydrate top
Crystal data top
K2NaH[GeW12O40]·7H2ODx = 3.973 Mg m3
Mr = 3147.12Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6222Cell parameters from 250 reflections
Hall symbol: P62 2cθ = 2.5–25°
a = 19.057 (3) ŵ = 26.92 mm1
c = 12.557 (3) ÅT = 293 K
V = 3949.3 (13) Å3Block, colourless
Z = 30.10 × 0.08 × 0.06 mm
F(000) = 4087
Data collection top
Bruker P4
diffractometer
2165 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.091
Graphite monochromatorθmax = 25.1°, θmin = 2.1°
ω scansh = 2222
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 2222
Tmin = 0.174, Tmax = 0.295l = 014
12980 measured reflections3 standard reflections every 97 reflections
2318 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.076 w = 1/[σ2(Fo2) + (0.0394P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
2318 reflectionsΔρmax = 1.73 e Å3
155 parametersΔρmin = 1.25 e Å3
74 restraintsAbsolute structure: Flack (1983), with how many Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.61 (3)
Special details top

Experimental. IR spectrum (KBr disk, cm-1): 979, 880, 825, 769.

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
xyzUiso*/UeqOcc. (<1)
K11.62856 (13)0.2571 (3)0.50000.0152 (10)
Ge11.50000.50000.33330.0065 (6)
W11.62679 (4)0.63466 (4)0.53271 (4)0.01136 (15)
W21.70650 (3)0.55520 (4)0.32408 (5)0.01000 (15)
W31.56860 (4)0.41735 (4)0.53160 (4)0.00986 (15)
O11.6984 (7)0.6857 (6)0.6270 (7)0.015 (2)
O21.8049 (7)0.5831 (7)0.3523 (8)0.017 (2)
O31.6228 (6)0.3971 (6)0.6223 (7)0.012 (2)
O41.6861 (7)0.6205 (6)0.4210 (8)0.016 (2)
O51.5913 (7)0.5254 (6)0.5683 (8)0.015 (2)
O61.7240 (7)0.6318 (7)0.2112 (7)0.015 (2)
O71.6819 (6)0.4755 (7)0.2140 (7)0.014 (2)
O81.6473 (6)0.4696 (6)0.4214 (7)0.009 (2)
O91.4674 (6)0.3744 (7)0.6046 (7)0.015 (2)
O101.5822 (6)0.5216 (6)0.2524 (7)0.007 (2)
O1W1.6527 (9)0.1231 (9)0.5176 (11)0.039 (3)
O2W1.50000.50000.1192 (11)0.021 (4)
Na11.790 (2)0.131 (2)0.435 (3)0.039 (8)*0.25
O3W1.757 (3)0.00000.50000.083 (16)*0.50
H1WA1.661 (12)0.082 (8)0.526 (15)0.039 (3)*
H1WB1.699 (6)0.138 (12)0.487 (13)0.039 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
K10.0145 (19)0.013 (2)0.018 (2)0.0063 (12)0.0004 (17)0.000
Ge10.0063 (11)0.0063 (11)0.0090 (14)0.0046 (13)0.0000.000
W10.0119 (3)0.0108 (3)0.0167 (3)0.0096 (3)0.0057 (2)0.0073 (2)
W20.0045 (3)0.0113 (3)0.0173 (3)0.0063 (3)0.0010 (2)0.0028 (2)
W30.0123 (3)0.0108 (3)0.0122 (3)0.0100 (3)0.0034 (2)0.0000 (2)
O10.015 (2)0.015 (2)0.015 (2)0.0075 (14)0.0002 (10)0.0011 (10)
O20.016 (3)0.017 (2)0.017 (3)0.0085 (14)0.0001 (10)0.0000 (10)
O30.012 (2)0.013 (2)0.013 (2)0.0066 (14)0.0003 (10)0.0003 (10)
O40.016 (3)0.016 (3)0.016 (3)0.0081 (15)0.0004 (10)0.0000 (10)
O50.015 (3)0.015 (3)0.015 (3)0.0074 (15)0.0005 (10)0.0006 (10)
O60.015 (2)0.015 (2)0.015 (2)0.0077 (14)0.0000 (10)0.0003 (10)
O70.014 (2)0.014 (2)0.015 (2)0.0075 (14)0.0002 (10)0.0000 (10)
O80.009 (2)0.009 (2)0.009 (2)0.0045 (13)0.0001 (10)0.0001 (10)
O90.015 (2)0.015 (2)0.016 (2)0.0081 (14)0.0001 (10)0.0000 (10)
O100.008 (2)0.007 (2)0.007 (2)0.0036 (13)0.0002 (10)0.0005 (10)
O1W0.039 (3)0.039 (3)0.039 (3)0.0198 (19)0.0002 (7)0.0000 (7)
O2W0.016 (9)0.025 (10)0.032 (8)0.016 (8)0.0000.000
Geometric parameters (Å, º) top
K1—O3i2.708 (9)W2—O61.940 (10)
K1—O3ii2.708 (9)W2—O102.306 (10)
K1—O7iii2.819 (11)W3—O31.706 (10)
K1—O7iv2.819 (11)W3—O91.911 (10)
K1—O1Wv2.822 (15)W3—O81.914 (9)
K1—O1W2.822 (15)W3—O7iii1.917 (10)
K1—O3v3.127 (10)W3—O51.937 (11)
K1—O33.127 (10)W3—O10iii2.268 (10)
K1—W3v3.778 (3)O3—K1iv2.708 (9)
K1—W33.778 (3)O6—W1vii1.921 (10)
K1—K1ii4.719 (4)O6—Na1ii2.89 (4)
K1—K1iv4.719 (4)O7—W3iii1.917 (10)
Ge1—O10vi1.734 (10)O7—K1ii2.819 (11)
Ge1—O101.734 (10)O9—W1vi1.938 (10)
Ge1—O10vii1.734 (10)O10—W3iii2.268 (10)
Ge1—O10iii1.734 (10)O10—W1vii2.286 (10)
W1—O11.697 (10)O1W—Na12.76 (4)
W1—O51.893 (11)O1W—H1WA0.87 (5)
W1—O41.903 (10)O1W—H1WB0.87 (5)
W1—O6vii1.921 (10)O2W—O2Wviii1.19 (3)
W1—O9vi1.938 (10)Na1—O3W2.39 (4)
W1—O10vii2.286 (10)Na1—O6iv2.89 (4)
W2—O21.711 (11)Na1—Na1iii2.96 (6)
W2—O81.893 (9)Na1—H1WA2.4 (2)
W2—O41.915 (10)Na1—H1WB1.93 (10)
W2—O71.929 (10)O3W—Na1ix2.39 (4)
O3i—K1—O3ii157.9 (5)O1—W1—O10vii169.1 (4)
O3i—K1—O7iii109.8 (3)O5—W1—O10vii85.4 (4)
O3ii—K1—O7iii78.3 (3)O4—W1—O10vii84.9 (4)
O3i—K1—O7iv78.3 (3)O6vii—W1—O10vii72.7 (4)
O3ii—K1—O7iv109.8 (3)O9vi—W1—O10vii72.2 (4)
O7iii—K1—O7iv138.1 (5)O2—W2—O8102.8 (5)
O3i—K1—O1Wv88.3 (4)O2—W2—O4102.3 (5)
O3ii—K1—O1Wv74.3 (4)O8—W2—O485.6 (4)
O7iii—K1—O1Wv72.7 (4)O2—W2—O7101.0 (5)
O7iv—K1—O1Wv149.0 (4)O8—W2—O788.8 (4)
O3i—K1—O1W74.3 (4)O4—W2—O7156.7 (5)
O3ii—K1—O1W88.3 (4)O2—W2—O699.6 (5)
O7iii—K1—O1W149.0 (4)O8—W2—O6157.5 (4)
O7iv—K1—O1W72.7 (4)O4—W2—O689.4 (4)
O1Wv—K1—O1W76.8 (6)O7—W2—O687.2 (4)
O3i—K1—O3v126.1 (2)O2—W2—O10169.0 (4)
O3ii—K1—O3v72.2 (3)O8—W2—O1085.8 (4)
O7iii—K1—O3v93.0 (3)O4—W2—O1085.0 (4)
O7iv—K1—O3v54.5 (3)O7—W2—O1072.0 (4)
O1Wv—K1—O3v145.6 (3)O6—W2—O1072.0 (4)
O1W—K1—O3v109.5 (3)O3—W3—O9100.3 (4)
O3i—K1—O372.2 (3)O3—W3—O8101.2 (4)
O3ii—K1—O3126.1 (2)O9—W3—O8158.5 (4)
O7iii—K1—O354.5 (3)O3—W3—O7iii98.0 (4)
O7iv—K1—O393.0 (3)O9—W3—O7iii88.6 (5)
O1Wv—K1—O3109.5 (3)O8—W3—O7iii89.0 (4)
O1W—K1—O3145.6 (3)O3—W3—O5104.1 (4)
O3v—K1—O384.7 (4)O9—W3—O589.0 (5)
O3i—K1—W3v100.8 (2)O8—W3—O585.3 (4)
O3ii—K1—W3v94.6 (2)O7iii—W3—O5157.9 (4)
O7iii—K1—W3v111.8 (2)O3—W3—O10iii168.7 (4)
O7iv—K1—W3v29.5 (2)O9—W3—O10iii73.1 (4)
O1Wv—K1—W3v167.3 (3)O8—W3—O10iii85.8 (4)
O1W—K1—W3v97.0 (3)O7iii—W3—O10iii73.0 (4)
O3v—K1—W3v26.52 (17)O5—W3—O10iii85.2 (4)
O3—K1—W3v82.0 (2)O3—W3—K154.9 (3)
O3i—K1—W394.6 (2)O9—W3—K1110.7 (4)
O3ii—K1—W3100.8 (2)O8—W3—K182.5 (3)
O7iii—K1—W329.5 (2)O7iii—W3—K146.3 (3)
O7iv—K1—W3111.8 (2)O5—W3—K1152.6 (3)
O1Wv—K1—W397.0 (3)O10iii—W3—K1118.1 (3)
O1W—K1—W3167.3 (3)W3—O3—K1iv141.1 (5)
O3v—K1—W382.0 (2)W3—O3—K198.5 (4)
O3—K1—W326.52 (17)K1iv—O3—K1107.7 (3)
W3v—K1—W391.16 (10)W1—O4—W2152.7 (6)
O3i—K1—K1ii158.2 (3)W1—O5—W3151.7 (6)
O3ii—K1—K1ii39.1 (2)W1vii—O6—W2121.1 (6)
O7iii—K1—K1ii83.1 (2)W1vii—O6—Na1ii120.8 (8)
O7iv—K1—K1ii80.5 (2)W2—O6—Na1ii106.0 (8)
O1Wv—K1—K1ii112.7 (3)W3iii—O7—W2120.9 (5)
O1W—K1—K1ii103.9 (3)W3iii—O7—K1ii104.2 (4)
O3v—K1—K1ii33.13 (17)W2—O7—K1ii132.9 (5)
O3—K1—K1ii104.3 (2)W2—O8—W3152.8 (6)
W3v—K1—K1ii57.58 (8)W3—O9—W1vi120.4 (5)
W3—K1—K1ii88.65 (5)Ge1—O10—W3iii123.1 (5)
O3i—K1—K1iv39.1 (2)Ge1—O10—W1vii122.5 (5)
O3ii—K1—K1iv158.2 (3)W3iii—O10—W1vii94.3 (3)
O7iii—K1—K1iv80.5 (2)Ge1—O10—W2121.2 (5)
O7iv—K1—K1iv83.1 (2)W3iii—O10—W294.1 (4)
O1Wv—K1—K1iv103.9 (3)W1vii—O10—W294.1 (4)
O1W—K1—K1iv112.7 (3)Na1—O1W—K1120.3 (9)
O3v—K1—K1iv104.3 (2)Na1—O1W—H1WA60 (10)
O3—K1—K1iv33.13 (17)K1—O1W—H1WA178 (10)
W3v—K1—K1iv88.65 (5)Na1—O1W—H1WB15 (10)
W3—K1—K1iv57.58 (8)K1—O1W—H1WB105 (10)
K1ii—K1—K1iv132.86 (14)H1WA—O1W—H1WB75 (10)
O10vi—Ge1—O10108.3 (6)O3W—Na1—O1W93.7 (17)
O10vi—Ge1—O10vii109.6 (7)O3W—Na1—O6iv120.6 (14)
O10—Ge1—O10vii110.5 (6)O1W—Na1—O6iv97.5 (11)
O10vi—Ge1—O10iii110.5 (6)O3W—Na1—Na1iii129.0 (14)
O10—Ge1—O10iii109.6 (7)O1W—Na1—Na1iii125.5 (9)
O10vii—Ge1—O10iii108.3 (6)O6iv—Na1—Na1iii88.3 (15)
O1—W1—O5102.0 (5)O3W—Na1—H1WA76 (2)
O1—W1—O4103.4 (5)O1W—Na1—H1WA18.0 (16)
O5—W1—O486.0 (4)O6iv—Na1—H1WA107 (4)
O1—W1—O6vii100.0 (5)Na1iii—Na1—H1WA139 (4)
O5—W1—O6vii157.9 (4)O3W—Na1—H1WB100 (6)
O4—W1—O6vii89.1 (4)O1W—Na1—H1WB7 (6)
O1—W1—O9vi99.7 (4)O6iv—Na1—H1WB94 (6)
O5—W1—O9vi89.2 (5)Na1iii—Na1—H1WB120 (6)
O4—W1—O9vi156.9 (4)H1WA—Na1—H1WB25 (6)
O6vii—W1—O9vi87.0 (5)Na1ix—O3W—Na1150 (3)
Symmetry codes: (i) x, xy+1, z+4/3; (ii) y2, xy+1, z1/3; (iii) y2, x2, z+2/3; (iv) x+y3, x2, z+1/3; (v) x+y3, y, z+1; (vi) x3, y1, z; (vii) y1, x+1, z+2/3; (viii) y2, x2, z1/3; (ix) xy, y, z+1.
 

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