Crystal structure of ammonium divanadium(IV,V) tellurium(IV) hepta­oxide

In the title layered, mixed-valence ammonium vanadium tellurite, the V^V atom are tetrahedrally coordinated and the V^IV atoms adopt distorted octahedral coordination geometries. The presumed Te^IV lone pairs of electrons are directed inwards into lacunae in the double polyhedral layers.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](Te-O) = 0.011 Å
• H-atom completeness 1%
• R factor = 0.040
• wR factor = 0.082
• Data-to-parameter ratio = 23.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT043_ALERT_1_B Calculated and Reported Mol. Weight Differ by ..       4.03 Check

Alert level C
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           359.52
           TEST: Calculate formula weight from _atom_site_*
           atom     mass    num     sum
           O        16.00    7.00  111.99
           H         1.01    0.00    0.00
           V        50.94    2.00  101.88
           Te      127.60    1.00  127.60
           N        14.01    1.00   14.01
           Calculated formula weight              355.48
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.500
           From the CIF: _refine_ls_abs_structure_Flack_su    0.100
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ     Please Check
PLAT044_ALERT_1_C Calculated and Reported Density Dx  Differ by ..     0.0370 Check
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...     Please Check
PLAT125_ALERT_4_C No '_symmetry_space_group_name_Hall' Given .....     Please Do !
PLAT213_ALERT_2_C Atom O1              has ADP max/min Ratio .....        3.9 prolat
PLAT241_ALERT_2_C High      Ueq as Compared to Neighbors for .....         O2 Check
PLAT241_ALERT_2_C High      Ueq as Compared to Neighbors for .....         O6 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....        Te1 Check
PLAT242_ALERT_2_C Low       Ueq as Compared to Neighbors for .....         V2 Check
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.6 Note
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........
PLAT716_ALERT_1_C H...A   Unknown or Inconsistent Label ..........
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      5.070 Check
PLAT915_ALERT_3_C Low Friedel Pair Coverage ......................         78 %
PLAT975_ALERT_2_C Check Calcd Residual Density  0.72A From      O2       0.97 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.47A From      O2       0.77 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.83A From      N1       0.71 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.75A From      N1       0.71 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.70A From      N1       0.70 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.58A From      N1       0.69 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.49A From      N1       0.65 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  0.75A From      N1       0.64 eA-3
PLAT975_ALERT_2_C Check Calcd Residual Density  1.08A From      N1       0.50 eA-3
PLAT976_ALERT_2_C Check Calcd Residual Density  0.98A From      O2      -0.83 eA-3
PLAT976_ALERT_2_C Check Calcd Residual Density  0.92A From      O1      -0.82 eA-3
PLAT976_ALERT_2_C Check Calcd Residual Density  0.94A From      O1      -0.54 eA-3

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:H4 N1 O7 Te1 V2
            Atom count from the _atom_site data:  N1 O7 Te1 V2
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  H4 N O7 Te V2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           H         16.00      0.00   16.00
           N          4.00      4.00    0.00
           O         28.00     28.00    0.00
           Te         4.00      4.00    0.00
           V          8.00      8.00    0.00
PLAT004_ALERT_5_G Polymeric Structure Found with Dimension .......          2 Info
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT111_ALERT_2_G ADDSYM Detects (Pseudo) Centre of Symmetry .....         81 %Fit
PLAT112_ALERT_2_G ADDSYM Detects Additional (Pseudo) Symm. Elem...          m Check
PLAT113_ALERT_2_G ADDSYM Suggests Possible Pseudo/New Space-group.       Pnma Check
PLAT199_ALERT_1_G Reported _cell_measurement_temperature ..... (K)        293 Check
PLAT200_ALERT_1_G Reported   _diffrn_ambient_temperature ..... (K)        293 Check
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  V1     --  O4      ..        5.3 su
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          8 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
  34 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  13 ALERT level G = General information/check it is not something unexpected

  17 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  24 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level A
PUBL006_ALERT_1_A  _publ_requested_journal is missing
            e.g. 'Acta Crystallographica Section C'

   1 ALERT level A = Data missing that is essential or data in wrong format
   0 ALERT level G = General alerts. Data that may be required is missing

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Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and ATOMS (Dowty, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Ammonium divanadium(IV,V) tellurium(IV) heptaoxide

Crystal data

(NH4)(VO2)2(TeO3)	Dx = 3.297 Mg m^−3
Mr = 359.52	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 5060 reflections
a = 18.945 (2) Å	θ = 2.2–32.5°
b = 7.0277 (8) Å	µ = 6.52 mm^−1
c = 5.4402 (6) Å	T = 293 K
V = 724.29 (14) Å^3	Rod, dark red
Z = 4	0.17 × 0.02 × 0.02 mm
F(000) = 660

Data collection

Bruker SMART1000 CCD diffractometer	2368 independent reflections
Radiation source: fine-focus sealed tube	1595 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ω scans	θmax = 32.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −28→26
Tmin = 0.404, Tmax = 0.881	k = −10→10
7528 measured reflections	l = −6→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: notdet
R[F^2 > 2σ(F^2)] = 0.040	H-atom parameters not defined
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0318P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
2368 reflections	Δρmax = 0.99 e Å^−3
101 parameters	Δρmin = −1.13 e Å^−3
1 restraint	Absolute structure: Flack (1983), 1201 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.5 (1)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.0293 (3)	0.2583 (8)	0.225 (5)	0.031 (2)
V1	0.31266 (5)	0.53486 (13)	0.2408 (12)	0.0245 (2)
V2	0.12159 (5)	0.75777 (13)	0.2385 (9)	0.0238 (2)
Te1	0.164135 (17)	0.50920 (5)	0.7434 (5)	0.02034 (10)
O1	0.1064 (8)	0.561 (3)	0.985 (2)	0.056 (5)
O2	0.0970 (8)	0.575 (3)	0.490 (2)	0.048 (4)
O3	0.1367 (2)	0.2463 (7)	0.728 (4)	0.053 (2)
O4	0.3316 (4)	0.4539 (9)	−0.0638 (13)	0.0355 (15)
O5	0.0453 (3)	0.8594 (7)	0.231 (5)	0.055 (2)
O6	0.2292 (2)	0.6033 (8)	0.224 (4)	0.043 (2)
O7	0.3270 (3)	0.3621 (9)	0.4347 (13)	0.0332 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.020 (2)	0.021 (3)	0.053 (6)	−0.004 (2)	0.000 (7)	0.005 (7)
V1	0.0150 (4)	0.0096 (4)	0.0488 (7)	0.0017 (3)	−0.003 (2)	0.003 (3)
V2	0.0200 (4)	0.0128 (4)	0.0386 (6)	−0.0008 (3)	−0.0089 (16)	−0.003 (2)
Te1	0.01691 (14)	0.01447 (16)	0.02964 (19)	0.00084 (13)	0.0000 (9)	−0.0019 (7)
O1	0.017 (5)	0.099 (10)	0.052 (8)	−0.022 (5)	0.018 (4)	−0.054 (7)
O2	0.018 (5)	0.088 (9)	0.040 (8)	−0.011 (5)	−0.006 (4)	0.038 (6)
O3	0.028 (2)	0.018 (2)	0.114 (7)	0.003 (2)	−0.037 (7)	−0.004 (8)
O4	0.043 (4)	0.029 (3)	0.035 (3)	0.012 (3)	0.005 (3)	−0.002 (3)
O5	0.030 (2)	0.020 (2)	0.115 (6)	0.007 (2)	−0.025 (9)	−0.005 (11)
O6	0.018 (2)	0.040 (3)	0.070 (6)	0.0099 (19)	−0.008 (6)	−0.021 (7)
O7	0.036 (3)	0.027 (3)	0.037 (4)	0.003 (3)	0.002 (3)	0.010 (3)

Geometric parameters (Å, º)

V1—O7	1.631 (7)	V2—O6	2.311 (5)
V1—O6	1.656 (5)	Te1—O1	1.748 (14)
V1—O3^i	1.770 (5)	Te1—O3	1.921 (5)
V1—O4	1.788 (9)	Te1—O2	1.931 (14)
V2—O5	1.612 (5)	O1—V2^iv	1.973 (16)
V2—O2	1.935 (15)	O3—V1^v	1.770 (5)
V2—O4^ii	1.961 (7)	O4—V2^vi	1.961 (7)
V2—O1^iii	1.973 (16)	O7—V2^v	2.053 (7)
V2—O7^i	2.053 (7)
O7—V1—O6	114.3 (6)	O1^iii—V2—O7^i	75.9 (6)
O7—V1—O3^i	124.1 (7)	O5—V2—O6	176.1 (11)
O6—V1—O3^i	105.7 (3)	O2—V2—O6	85.7 (6)
O7—V1—O4	109.2 (4)	O4^ii—V2—O6	87.1 (4)
O6—V1—O4	103.4 (8)	O1^iii—V2—O6	77.0 (6)
O3^i—V1—O4	97.0 (7)	O7^i—V2—O6	73.8 (5)
O5—V2—O2	95.6 (9)	O1—Te1—O3	93.7 (9)
O5—V2—O4^ii	96.2 (5)	O1—Te1—O2	94.2 (3)
O2—V2—O4^ii	100.8 (6)	O3—Te1—O2	91.2 (7)
O5—V2—O1^iii	99.2 (8)	Te1—O1—V2^iv	125.5 (9)
O2—V2—O1^iii	89.7 (3)	Te1—O2—V2	120.3 (8)
O4^ii—V2—O1^iii	160.3 (5)	V1^v—O3—Te1	131.3 (2)
O5—V2—O7^i	104.2 (8)	V1—O4—V2^vi	145.3 (4)
O2—V2—O7^i	157.0 (6)	V1—O6—V2	167.7 (6)
O4^ii—V2—O7^i	88.6 (3)	V1—O7—V2^v	149.9 (4)

Symmetry codes: (i) −x+1/2, y+1/2, z−1/2; (ii) −x+1/2, y+1/2, z+1/2; (iii) x, y, z−1; (iv) x, y, z+1; (v) −x+1/2, y−1/2, z+1/2; (vi) −x+1/2, y−1/2, z−1/2.

Hydrogen-bond geometry (Å)

D—H···A	D···A
N1···O5^vii	2.820 (7)
N1···O1^iii	2.89 (2)
N1···O2	2.95 (2)
N1···O2^viii	2.96 (2)
N1···O5^viii	3.15 (3)
N1···O1^viii	3.20 (2)
N1···O5^ix	3.20 (3)
N1···O3^iii	3.39 (3)

Symmetry codes: (iii) x, y, z−1; (vii) x, y−1, z; (viii) −x, −y+1, z−1/2; (ix) −x, −y+1, z+1/2.