metal-organic compounds
In the crystal structure of the title compound, poly[ammonium di-μ2-oxalato-bismuthate(III) 3.72-hydrate], NH4[Bi(C2O4)2]·3.72H2O, the Bi3+ ion and the centre of the [NH4]+ ion lie on different special positions of m2 site symmetry, and the oxalate group and one water molecule on different special positions of m site symmetry; the second water molecule lies on a special position of 2/m site symmetry. The Bi atom is eight-coordinate in a slightly distorted dodecahedral environment. This single-crystal redetermination improves the precision of the previous powder diffraction study [Vanhoyland et al. (2004). Inorg. Chem. 43, 785–789], as all non-H atoms have been refined anisotropically.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806033186/wm2042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536806033186/wm2042Isup2.hkl |
CCDC reference: 621520
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.011 Å
- H-atom completeness 35%
- Disorder in main residue
- R factor = 0.023
- wR factor = 0.068
- Data-to-parameter ratio = 11.8
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT762_ALERT_1_A CIF Contains no X-Y-H or H-Y-H Angles .......... ?
Author Response: Inorganic structure; there is only an ammonium cation. |
Alert level B PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for O1 PLAT430_ALERT_2_B Short Inter D...A Contact O1W .. O2W .. 2.69 Ang. PLAT430_ALERT_2_B Short Inter D...A Contact O1W .. O2W .. 2.69 Ang. PLAT430_ALERT_2_B Short Inter D...A Contact O1W .. O2W .. 2.69 Ang. PLAT430_ALERT_2_B Short Inter D...A Contact O1W .. O2W .. 2.69 Ang.
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.123 0.199 Tmin and Tmax expected: 0.046 0.092 RR = 1.234 Please check that your absorption correction is appropriate. CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside the range 0.99 <> 1.01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_weight 470.38 TEST: Calculate formula weight from _atom_site_* atom mass num sum C 12.01 4.00 48.04 H 1.01 4.00 4.03 N 14.01 1.00 14.01 O 16.00 11.72 187.51 Bi 208.98 1.00 208.98 Calculated formula weight 462.57 PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT043_ALERT_1_C Check Reported Molecular Weight ................ 470.38 PLAT044_ALERT_1_C Calculated and Reported Dx Differ .............. ? PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.18 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.46 PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1 PLAT301_ALERT_3_C Main Residue Disorder ......................... 2.00 Perc. PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... >O1W PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) ..... >O2W PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 11
Alert level G FORMU01_ALERT_1_G 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 H11.74 Bi1 N1 O11.72 Atom count from _chemical_formula_moiety:C4 H11.44 Bi1 N1 O11.72 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:C4 H11.74 Bi1 N1 O11.72 Atom count from the _atom_site data: C4 H4 Bi1 N1 O11.72 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 0.462 Tmax scaled 0.092 Tmin scaled 0.057 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 4 From the CIF: _chemical_formula_sum C4 H11.74 Bi N O11.72 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 16.00 16.00 0.00 H 46.96 16.00 30.96 Bi 4.00 4.00 0.00 N 4.00 4.00 0.00 O 46.88 46.88 0.00
1 ALERT level A = In general: serious problem 5 ALERT level B = Potentially serious problem 14 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 10 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Computing details top
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: atomic coordinates taken from published structure; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97.
poly[ammonium di-µ2-oxalato-bismuthate(III) 3.72-hydrate] top
Crystal data top
NH4[Bi(C2O4)2]·3.72H2O | Dx = 2.477 Mg m−3 |
Mr = 470.38 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/amd | Cell parameters from 2126 reflections |
Hall symbol: -I 4bd 2 | θ = 2.6–28.0° |
a = 11.674 (1) Å | µ = 14.04 mm−1 |
c = 9.2545 (8) Å | T = 295 K |
V = 1261.2 (2) Å3 | Block, colourless |
Z = 4 | 0.24 × 0.20 × 0.17 mm |
F(000) = 878 |
Data collection top
Bruker APEX area-detector diffractometer | 401 independent reflections |
Radiation source: fine-focus sealed tube | 365 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 27.5°, θmin = 2.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→15 |
Tmin = 0.123, Tmax = 0.199 | k = −11→14 |
3231 measured reflections | l = −6→12 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: isomorphous structure methods |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0476P)2 + 3.0591P] where P = (Fo2 + 2Fc2)/3 |
401 reflections | (Δ/σ)max = 0.001 |
34 parameters | Δρmax = 0.76 e Å−3 |
14 restraints | Δρmin = −0.49 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Bi1 | 0.5000 | 0.2500 | 0.6250 | 0.0298 (2) | |
O1 | 0.2966 (5) | 0.2500 | 0.5729 (7) | 0.071 (2) | |
O2 | 0.1202 (5) | 0.2500 | 0.6607 (6) | 0.059 (2) | |
O1w | 0.2500 | 0.2500 | 0.2500 | 0.19 (2) | 0.62 |
O2w | 0.203 (3) | 0.047 (3) | 0.3750 | 0.22 (1) | 0.62 |
C1 | 0.2260 (7) | 0.2500 | 0.6738 (8) | 0.046 (2) | |
N1 | 0.0000 | 0.2500 | 0.3750 | 0.090 (9) | |
H1 | 0.0596 (4) | 0.2500 | 0.427 (2) | 0.108* |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.0315 (2) | 0.0315 (2) | 0.0264 (3) | 0.000 | 0.000 | 0.000 |
O1 | 0.039 (3) | 0.139 (7) | 0.034 (3) | 0.000 | −0.002 (3) | 0.000 |
O2 | 0.034 (3) | 0.112 (6) | 0.030 (2) | 0.000 | −0.003 (2) | 0.000 |
O1w | 0.19 (2) | 0.20 (2) | 0.17 (2) | 0.000 | −0.01 (1) | 0.000 |
O2w | 0.22 (1) | 0.22 (1) | 0.22 (2) | −0.01 (1) | −0.022 (6) | −0.022 (6) |
C1 | 0.034 (4) | 0.078 (5) | 0.028 (3) | 0.000 | −0.002 (3) | 0.000 |
N1 | 0.12 (1) | 0.12 (1) | 0.029 (8) | 0.000 | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Bi1—O1 | 2.423 (6) | Bi1—O2vi | 2.429 (6) |
Bi1—O1i | 2.423 (6) | Bi1—O2vii | 2.429 (6) |
Bi1—O1ii | 2.423 (6) | O1—C1 | 1.25 (1) |
Bi1—O1iii | 2.423 (6) | O2—C1 | 1.24 (1) |
Bi1—O2iv | 2.429 (6) | C1—C1vii | 1.52 (2) |
Bi1—O2v | 2.429 (6) | N1—H1 | 0.85 (1) |
O1i—Bi1—O1ii | 92.3 (1) | O1—Bi1—O2vii | 66.2 (2) |
O1i—Bi1—O1 | 92.3 (1) | O1iii—Bi1—O2vii | 80.7 (1) |
O1ii—Bi1—O1 | 157.0 (3) | O2vi—Bi1—O2vii | 131.8 (2) |
O1i—Bi1—O1iii | 157.0 (3) | O2iv—Bi1—O2vii | 70.6 (3) |
O1ii—Bi1—O1iii | 92.27 (6) | O1i—Bi1—O2v | 136.8 (2) |
O1—Bi1—O1iii | 92.27 (6) | O1ii—Bi1—O2v | 80.7 (1) |
O1i—Bi1—O2vi | 66.2 (2) | O1—Bi1—O2v | 80.65 (12) |
O1ii—Bi1—O2vi | 80.7 (1) | O1iii—Bi1—O2v | 66.2 (2) |
O1—Bi1—O2vi | 80.7 (1) | O2vi—Bi1—O2v | 70.6 (3) |
O1iii—Bi1—O2vi | 136.8 (2) | O2iv—Bi1—O2v | 131.8 (2) |
O1i—Bi1—O2iv | 80.7 (1) | O2vii—Bi1—O2v | 131.8 (2) |
O1ii—Bi1—O2iv | 66.2 (2) | C1—O1—Bi1 | 120.0 (5) |
O1—Bi1—O2iv | 136.8 (2) | C1—O2—Bi1vii | 119.7 (5) |
O1iii—Bi1—O2iv | 80.7 (1) | O2—C1—O1 | 125.9 (8) |
O2vi—Bi1—O2iv | 131.8 (2) | O2—C1—C1vii | 117.3 (9) |
O1i—Bi1—O2vii | 80.7 (1) | O1—C1—C1vii | 116.8 (9) |
O1ii—Bi1—O2vii | 136.8 (2) | ||
O1i—Bi1—O1—C1 | 78.8 (1) | O2v—Bi1—O1—C1 | −144.2 (1) |
O1ii—Bi1—O1—C1 | 180.0 | Bi1vii—O2—C1—O1 | 180.0 |
O1iii—Bi1—O1—C1 | −78.8 (1) | Bi1vii—O2—C1—C1vii | 0.0 |
O2vi—Bi1—O1—C1 | 144.2 (1) | Bi1—O1—C1—O2 | 180.0 |
O2iv—Bi1—O1—C1 | 0.0 | Bi1—O1—C1—C1vii | 0.0 |
O2vii—Bi1—O1—C1 | 0.0 |
Symmetry codes: (i) y+1/4, x−1/4, −z+5/4; (ii) −x+1, y, z; (iii) y+1/4, −x+3/4, −z+5/4; (iv) x+1/2, −y+1/2, −z+3/2; (v) −y+3/4, x+1/4, z−1/4; (vi) −y+3/4, −x+1/4, z−1/4; (vii) −x+1/2, −y+1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.85 (1) | 2.27 (2) | 2.996 (3) | 143 (1) |