Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024798/wm2113sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024798/wm2113Isup2.hkl |
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (i-O) = 0.006 Å
- Disorder in main residue
- R factor = 0.037
- wR factor = 0.085
- Data-to-parameter ratio = 25.9
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.86 Ratio PLAT301_ALERT_3_C Main Residue Disorder ......................... 4.00 Perc.
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............ 2 Times
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 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 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For the isotypic La3Mo4SiO14, see Betteridge et al. (1984). The structure contains edge-sharing MoO6 octahedra similar to those found in MoO2 (Brandt & Skapski, 1967). The oxidation states of Mo atoms were estimated using the data given by Brown & Wu (1976). Besides the title compound, crystals of NdMo5O8 (Gougeon et al., 2003) were also obtained.
In an attempt to prepare Nd16Mo20SiO56, single crystals of Nd3Mo4SiO14 were obtained by the reaction of Nd2O3, MoO3, SiO2 and Mo in the molar ratio 8:10:1:10. The initial mixture (ca 5 g) was cold pressed and loaded into a molybdenum crucible, which was sealed under a low argon pressure using an arc welding system. The charge was heated at the rate of 300 K/h up to 1873 K, the temperature which was held for 48 h, then cooled at 100 K/h down to 1373 K and finally cooled to room temperature by turning off the furnace. X-ray powder diffraction measurements using Cu Kα1 radiation and a INEL CPS-120 curved position sensitive detector showed that the dominant products were NdMo5O8 (Gougeon et al., 2003) and Nd3Mo4SiO14.
In the final refinement cycles the site occupancy factor for the Mo3 atom was constrained to 0.5. Because of the disorder of the Mo3 atom, we made reciprocal space reconstructions of different planes as well as long-exposure rotations along the three axes on the Kappa CCD diffractometer. In both cases, we did not observed any superlattice reflections or diffuse lines. The highest peak and the deepest hole in the final Fourier map are located 1.75Å from O5 and 1.43Å from Mo2, respectively.
The title compound is isotypic with La3Mo4SiO14 (Betteridge et al., 1984). The crystal structure contains chains of triangular Mo3O13 units and chains of edge-sharing MoO6 octahedra similar to those found in MoO2 (Brandt & Skapski, 1967). Both chains run parallel to the b axis (Fig. 1). Each single Mo chain is linked through O2 and O7 atoms to two Mo3 chains to form ribbons (Fig. 2). The Mo—Mo distances within the Mo3 triangles are 2.5351 (8) and 2.5498 (9) Å and the shortest distance between adjacent Mo3 clusters is 3.0661 (9) Å. In the single Mo chains, the Mo—Mo distances are alternately 2.503 (4) and 3.145 (4) Å. The Mo—O distances of Mo1 and Mo2 forming the Mo3 cluster unit range from 1.944 (5) to 2.127 (4) Å, while those of the Mo3 atom forming the Mo2 dimer vary between 1.925 (6) and 2.187 (5) Å. From the lengths of the Mo—O bonds, we can estimate the oxidation states of each independent Mo atom by using the empirical bond length-bond strength relationship developed by Brown and Wu (1976). The calculations result in valence sums of +3.99 (6), +3.59 (6) and +3.92 (6) for Mo1, Mo2 and Mo3, respectively. Consequently, in Nd3Mo4SiO14 the number of electrons per Mo3 cluster is evaluated to 7, and to 2 per Mo atom in the single Mo chains. The Si site is tetrahedrally coordinated by O atoms with Si—O distances ranging from 1.620 (7) to 1.649 (9) Å. The bond length-bond strength calculation shows an oxidation state of +3.86 (5), in good agreement with the expected value of +4. The Nd atoms are surrounded by 8 to 10 O atoms forming considerably distorted polyhedra with Nd—O distances ranging from 2.321 (4) to 2.896 (8) Å (Table 1).
For the isotypic La3Mo4SiO14, see Betteridge et al. (1984). The structure contains edge-sharing MoO6 octahedra similar to those found in MoO2 (Brandt & Skapski, 1967). The oxidation states of Mo atoms were estimated using the data given by Brown & Wu (1976). Besides the title compound, crystals of NdMo5O8 (Gougeon et al., 2003) were also obtained.
Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT; data reduction: EVALCCD (Duisenberg, 1998); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL97.
Nd3Mo4SiO14 | F(000) = 1896 |
Mr = 1068.56 | Dx = 6.640 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 4003 reflections |
a = 17.5348 (15) Å | θ = 3.8–38.0° |
b = 5.6159 (3) Å | µ = 19.04 mm−1 |
c = 10.8542 (11) Å | T = 293 K |
V = 1068.85 (15) Å3 | Needle, black |
Z = 4 | 0.16 × 0.02 × 0.02 mm |
Nonius KappaCCD diffractometer | 3131 independent reflections |
Radiation source: fine-focus sealed tube | 2619 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.063 |
φ scans (κ = 0) + additional ω scans | θmax = 38.0°, θmin = 3.8° |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | h = −30→29 |
Tmin = 0.272, Tmax = 0.710 | k = −8→9 |
30670 measured reflections | l = −18→17 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Primary atom site location: structure-invariant direct methods |
R[F2 > 2σ(F2)] = 0.037 | Secondary atom site location: difference Fourier map |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + 19.2566P] where P = (Fo2 + 2Fc2)/3 |
S = 1.38 | (Δ/σ)max = 0.001 |
3131 reflections | Δρmax = 2.32 e Å−3 |
121 parameters | Δρmin = −3.72 e Å−3 |
Nd3Mo4SiO14 | V = 1068.85 (15) Å3 |
Mr = 1068.56 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 17.5348 (15) Å | µ = 19.04 mm−1 |
b = 5.6159 (3) Å | T = 293 K |
c = 10.8542 (11) Å | 0.16 × 0.02 × 0.02 mm |
Nonius KappaCCD diffractometer | 3131 independent reflections |
Absorption correction: analytical (de Meulenaer & Tompa, 1965) | 2619 reflections with I > 2σ(I) |
Tmin = 0.272, Tmax = 0.710 | Rint = 0.063 |
30670 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + 19.2566P] where P = (Fo2 + 2Fc2)/3 |
S = 1.38 | Δρmax = 2.32 e Å−3 |
3131 reflections | Δρmin = −3.72 e Å−3 |
121 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Nd1 | 0.16358 (3) | 0.7500 | 0.63158 (4) | 0.00610 (8) | |
Nd2 | 0.03477 (3) | 1.2500 | 0.79944 (4) | 0.00879 (8) | |
Nd3 | −0.15474 (3) | 0.2500 | 0.00583 (4) | 0.00702 (8) | |
Mo1 | 0.28501 (4) | 0.7500 | 0.36147 (6) | 0.00450 (11) | |
Mo2 | 0.16265 (3) | 0.52298 (8) | 0.32043 (4) | 0.00428 (8) | |
Mo3 | −0.00732 (5) | 0.7788 (4) | 0.50698 (9) | 0.0047 (4) | 0.50 |
Si | 0.06365 (13) | 0.2500 | 0.1039 (2) | 0.0052 (4) | |
O1 | 0.0800 (3) | 0.5018 (8) | 0.1775 (4) | 0.0077 (7) | |
O2 | 0.1004 (4) | 0.2500 | 0.4002 (6) | 0.0076 (10) | |
O3 | 0.2135 (3) | 0.2500 | 0.2377 (5) | 0.0051 (9) | |
O4 | 0.3506 (3) | 0.4958 (8) | 0.3020 (4) | 0.0084 (7) | |
O5 | 0.2315 (2) | 0.5069 (7) | 0.4697 (4) | 0.0060 (7) | |
O6 | 0.3766 (4) | 0.7500 | 0.4892 (6) | 0.0121 (12) | |
O7 | 0.0941 (4) | 0.7500 | 0.4146 (6) | 0.0089 (10) | |
O8 | 0.2217 (3) | 0.7500 | 0.2021 (6) | 0.0074 (10) | |
O9 | −0.0452 (3) | 0.5027 (8) | 0.3826 (4) | 0.0107 (8) | |
O10 | −0.0224 (4) | 0.2500 | 0.0497 (7) | 0.0141 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Nd1 | 0.00569 (17) | 0.00825 (17) | 0.00435 (17) | 0.000 | −0.00015 (12) | 0.000 |
Nd2 | 0.00467 (17) | 0.01261 (18) | 0.0091 (2) | 0.000 | −0.00054 (13) | 0.000 |
Nd3 | 0.00575 (17) | 0.00927 (17) | 0.00606 (17) | 0.000 | −0.00034 (13) | 0.000 |
Mo1 | 0.0037 (2) | 0.0056 (2) | 0.0041 (3) | 0.000 | −0.00002 (19) | 0.000 |
Mo2 | 0.00411 (18) | 0.00450 (16) | 0.00421 (18) | 0.00031 (13) | 0.00010 (13) | −0.00078 (13) |
Mo3 | 0.0042 (3) | 0.0057 (12) | 0.0040 (3) | 0.0002 (3) | 0.0001 (2) | −0.0002 (3) |
Si | 0.0045 (9) | 0.0073 (9) | 0.0037 (9) | 0.000 | −0.0002 (7) | 0.000 |
O1 | 0.0079 (18) | 0.0077 (16) | 0.0075 (18) | 0.0002 (13) | −0.0015 (13) | −0.0036 (14) |
O2 | 0.006 (2) | 0.009 (2) | 0.008 (3) | 0.000 | 0.0023 (19) | 0.000 |
O3 | 0.006 (2) | 0.003 (2) | 0.006 (2) | 0.000 | 0.0009 (18) | 0.000 |
O4 | 0.0075 (18) | 0.0094 (16) | 0.0083 (18) | −0.0028 (14) | 0.0002 (13) | −0.0014 (14) |
O5 | 0.0067 (17) | 0.0062 (15) | 0.0050 (17) | 0.0005 (13) | −0.0001 (13) | 0.0018 (12) |
O6 | 0.006 (3) | 0.021 (3) | 0.009 (3) | 0.000 | −0.004 (2) | 0.000 |
O7 | 0.005 (2) | 0.011 (3) | 0.010 (3) | 0.000 | 0.003 (2) | 0.000 |
O8 | 0.004 (2) | 0.012 (2) | 0.007 (3) | 0.000 | 0.0003 (18) | 0.000 |
O9 | 0.010 (2) | 0.0061 (17) | 0.016 (2) | 0.0008 (14) | 0.0043 (15) | −0.0003 (15) |
O10 | 0.006 (3) | 0.019 (3) | 0.018 (3) | 0.000 | −0.002 (2) | 0.000 |
Nd1—O4i | 2.321 (4) | Mo2—O2 | 2.072 (4) |
Nd1—O4ii | 2.321 (4) | Mo2—O8 | 2.084 (5) |
Nd1—O3ii | 2.444 (6) | Mo2—O1 | 2.127 (4) |
Nd1—O9iii | 2.520 (5) | Mo2—Mo2v | 2.5498 (9) |
Nd1—O9iv | 2.520 (5) | Mo2—Mo2xvii | 3.0661 (9) |
Nd1—O5v | 2.524 (4) | Mo3—Mo3v | 0.323 (4) |
Nd1—O5 | 2.524 (4) | Mo3—O2iii | 1.925 (6) |
Nd1—O7 | 2.651 (7) | Mo3—O9v | 1.941 (5) |
Nd1—Mo3 | 3.2916 (11) | Mo3—O9iv | 1.966 (5) |
Nd1—Mo3v | 3.2916 (11) | Mo3—O7 | 2.047 (6) |
Nd1—Mo2 | 3.6099 (7) | Mo3—O9 | 2.160 (5) |
Nd1—Mo2v | 3.6099 (7) | Mo3—O9iii | 2.187 (5) |
Nd2—O9iv | 2.422 (5) | Mo3—Mo3vi | 2.503 (4) |
Nd2—O9vi | 2.422 (5) | Mo3—Mo3iv | 2.8237 (2) |
Nd2—O1iv | 2.461 (4) | Mo3—Mo3xviii | 2.8237 (2) |
Nd2—O1vi | 2.461 (4) | Mo3—Mo3iii | 3.145 (4) |
Nd2—O4vii | 2.465 (4) | Si—O10 | 1.620 (7) |
Nd2—O4i | 2.465 (4) | Si—O6xix | 1.626 (7) |
Nd2—O6vii | 2.580 (7) | Si—O1 | 1.649 (4) |
Nd2—O10viii | 2.896 (8) | Si—O1xvii | 1.649 (4) |
Nd2—Mo1vii | 3.2310 (9) | Si—Nd2xx | 3.343 (2) |
Nd2—Siviii | 3.343 (2) | Si—Nd3xi | 3.4428 (14) |
Nd2—Mo3vi | 3.3645 (11) | Si—Nd3xxi | 3.4428 (14) |
Nd2—Mo3iv | 3.3645 (11) | Si—Nd2iii | 3.4590 (14) |
Nd3—O10 | 2.368 (7) | Si—Nd2vi | 3.4590 (14) |
Nd3—O5ix | 2.476 (4) | O1—Nd2vi | 2.461 (4) |
Nd3—O5x | 2.476 (4) | O1—Nd3xi | 2.760 (5) |
Nd3—O4x | 2.503 (4) | O2—Mo3iii | 1.925 (6) |
Nd3—O4ix | 2.503 (4) | O2—Mo3xviii | 1.925 (6) |
Nd3—O8xi | 2.544 (6) | O2—Mo2xvii | 2.072 (4) |
Nd3—O1xii | 2.760 (5) | O3—Mo2xvii | 1.988 (4) |
Nd3—O1xi | 2.760 (5) | O3—Nd1xix | 2.444 (6) |
Nd3—O6x | 2.8617 (13) | O4—Nd1xix | 2.321 (4) |
Nd3—O6xiii | 2.8617 (13) | O4—Nd2xiv | 2.465 (4) |
Nd3—Mo1x | 3.3280 (5) | O4—Nd3xvi | 2.503 (4) |
Nd3—Mo1xiii | 3.3280 (5) | O5—Nd3xvi | 2.476 (4) |
Mo1—O4v | 1.944 (5) | O6—Siii | 1.626 (7) |
Mo1—O4 | 1.944 (5) | O6—Nd2xiv | 2.580 (7) |
Mo1—O5 | 2.030 (4) | O6—Nd3xvi | 2.8617 (13) |
Mo1—O5v | 2.030 (4) | O6—Nd3xv | 2.8617 (13) |
Mo1—O8 | 2.055 (6) | O7—Mo2v | 2.029 (5) |
Mo1—O6 | 2.122 (6) | O7—Mo3v | 2.047 (6) |
Mo1—Mo2 | 2.5351 (8) | O8—Mo2v | 2.084 (5) |
Mo1—Mo2v | 2.5351 (8) | O8—Nd3xi | 2.544 (6) |
Mo1—Nd2xiv | 3.2310 (9) | O9—Mo3v | 1.941 (5) |
Mo1—Nd3xv | 3.3280 (5) | O9—Mo3xviii | 1.966 (5) |
Mo1—Nd3xvi | 3.3280 (5) | O9—Mo3iii | 2.187 (5) |
Mo2—O3 | 1.988 (4) | O9—Nd2vi | 2.422 (5) |
Mo2—O5 | 2.023 (4) | O9—Nd1iii | 2.520 (5) |
Mo2—O7 | 2.029 (5) | O10—Nd2xx | 2.896 (8) |
O4i—Nd1—O4ii | 73.0 (2) | O5—Mo2—Mo2v | 92.56 (12) |
O4i—Nd1—O3ii | 73.68 (16) | O7—Mo2—Mo2v | 51.08 (11) |
O4ii—Nd1—O3ii | 73.68 (16) | O2—Mo2—Mo2v | 137.73 (13) |
O4i—Nd1—O9iii | 107.18 (16) | O8—Mo2—Mo2v | 52.29 (10) |
O4ii—Nd1—O9iii | 68.00 (16) | O1—Mo2—Mo2v | 93.21 (12) |
O3ii—Nd1—O9iii | 139.08 (13) | Mo1—Mo2—Mo2v | 59.808 (13) |
O4i—Nd1—O9iv | 68.00 (16) | O3—Mo2—Mo2xvii | 39.53 (13) |
O4ii—Nd1—O9iv | 107.18 (16) | O5—Mo2—Mo2xvii | 87.44 (12) |
O3ii—Nd1—O9iv | 139.08 (13) | O7—Mo2—Mo2xvii | 128.92 (11) |
O9iii—Nd1—O9iv | 68.6 (2) | O2—Mo2—Mo2xvii | 42.27 (13) |
O4i—Nd1—O5v | 106.48 (15) | O8—Mo2—Mo2xvii | 127.71 (10) |
O4ii—Nd1—O5v | 157.96 (15) | O1—Mo2—Mo2xvii | 86.79 (12) |
O3ii—Nd1—O5v | 84.93 (15) | Mo1—Mo2—Mo2xvii | 120.192 (13) |
O9iii—Nd1—O5v | 130.62 (15) | Mo2v—Mo2—Mo2xvii | 180.00 (6) |
O9iv—Nd1—O5v | 92.40 (14) | O3—Mo2—Nd1 | 133.87 (17) |
O4i—Nd1—O5 | 157.96 (15) | O5—Mo2—Nd1 | 42.60 (12) |
O4ii—Nd1—O5 | 106.48 (14) | O7—Mo2—Nd1 | 46.31 (19) |
O3ii—Nd1—O5 | 84.93 (15) | O2—Mo2—Nd1 | 82.68 (16) |
O9iii—Nd1—O5 | 92.40 (14) | O8—Mo2—Nd1 | 110.98 (14) |
O9iv—Nd1—O5 | 130.62 (15) | O1—Mo2—Nd1 | 134.87 (12) |
O5v—Nd1—O5 | 65.47 (19) | Mo1—Mo2—Nd1 | 69.77 (2) |
O4i—Nd1—O7 | 131.17 (14) | Mo2v—Mo2—Nd1 | 69.319 (8) |
O4ii—Nd1—O7 | 131.17 (14) | Mo2xvii—Mo2—Nd1 | 110.681 (8) |
O3ii—Nd1—O7 | 145.5 (2) | Mo3v—Mo3—O2iii | 85.19 (7) |
O9iii—Nd1—O7 | 64.33 (15) | Mo3v—Mo3—O9v | 129.21 (15) |
O9iv—Nd1—O7 | 64.33 (15) | O2iii—Mo3—O9v | 97.3 (2) |
O5v—Nd1—O7 | 66.35 (14) | Mo3v—Mo3—O9iv | 129.78 (15) |
O5—Nd1—O7 | 66.35 (14) | O2iii—Mo3—O9iv | 97.6 (2) |
O9iv—Nd2—O9vi | 70.0 (2) | O9v—Mo3—O9iv | 100.3 (2) |
O9iv—Nd2—O1iv | 79.63 (15) | Mo3v—Mo3—O7 | 85.48 (6) |
O9vi—Nd2—O1iv | 118.00 (15) | O2iii—Mo3—O7 | 170.39 (14) |
O9iv—Nd2—O1vi | 118.00 (15) | O9v—Mo3—O7 | 90.4 (2) |
O9vi—Nd2—O1vi | 79.63 (15) | O9iv—Mo3—O7 | 86.7 (2) |
O1iv—Nd2—O1vi | 69.0 (2) | Mo3v—Mo3—O9 | 44.14 (14) |
O9iv—Nd2—O4vii | 106.24 (15) | O2iii—Mo3—O9 | 90.35 (19) |
O9vi—Nd2—O4vii | 67.40 (15) | O9v—Mo3—O9 | 85.1 (3) |
O1iv—Nd2—O4vii | 173.48 (15) | O9iv—Mo3—O9 | 169.71 (13) |
O1vi—Nd2—O4vii | 109.73 (15) | O7—Mo3—O9 | 84.51 (19) |
O9iv—Nd2—O4i | 67.40 (15) | Mo3v—Mo3—O9iii | 43.71 (13) |
O9vi—Nd2—O4i | 106.24 (15) | O2iii—Mo3—O9iii | 90.55 (19) |
O1iv—Nd2—O4i | 109.73 (15) | O9v—Mo3—O9iii | 169.09 (14) |
O1vi—Nd2—O4i | 173.48 (15) | O9iv—Mo3—O9iii | 86.1 (3) |
O4vii—Nd2—O4i | 70.8 (2) | O7—Mo3—O9iii | 81.12 (18) |
O9iv—Nd2—O6vii | 127.30 (15) | O9—Mo3—O9iii | 87.3 (2) |
O9vi—Nd2—O6vii | 127.30 (15) | Mo3v—Mo3—Mo3vi | 173.16 (4) |
O1iv—Nd2—O6vii | 114.28 (15) | O2iii—Mo3—Mo3vi | 101.65 (9) |
O1vi—Nd2—O6vii | 114.28 (15) | O9v—Mo3—Mo3vi | 50.60 (15) |
O4vii—Nd2—O6vii | 60.01 (15) | O9iv—Mo3—Mo3vi | 49.73 (15) |
O4i—Nd2—O6vii | 60.01 (15) | O7—Mo3—Mo3vi | 87.69 (6) |
O9iv—Nd2—O10viii | 142.32 (12) | O9—Mo3—Mo3vi | 134.93 (14) |
O9vi—Nd2—O10viii | 142.32 (12) | O9iii—Mo3—Mo3vi | 135.05 (14) |
O1iv—Nd2—O10viii | 67.74 (15) | Mo3v—Mo3—Mo3iv | 173.94 (4) |
O1vi—Nd2—O10viii | 67.74 (15) | O2iii—Mo3—Mo3iv | 100.87 (8) |
O4vii—Nd2—O10viii | 105.78 (15) | O9v—Mo3—Mo3iv | 50.59 (15) |
O4i—Nd2—O10viii | 105.78 (15) | O9iv—Mo3—Mo3iv | 49.75 (15) |
O6vii—Nd2—O10viii | 57.3 (2) | O7—Mo3—Mo3iv | 88.47 (7) |
O10—Nd3—O5ix | 140.12 (12) | O9—Mo3—Mo3iv | 135.08 (14) |
O10—Nd3—O5x | 140.12 (12) | O9iii—Mo3—Mo3iv | 135.23 (14) |
O5ix—Nd3—O5x | 71.3 (2) | Mo3vi—Mo3—Mo3iv | 0.780 (13) |
O10—Nd3—O4x | 78.21 (18) | Mo3v—Mo3—Mo3xviii | 6.06 (4) |
O5ix—Nd3—O4x | 105.19 (14) | O2iii—Mo3—Mo3xviii | 91.24 (7) |
O5x—Nd3—O4x | 67.62 (14) | O9v—Mo3—Mo3xviii | 128.49 (16) |
O10—Nd3—O4ix | 78.21 (18) | O9iv—Mo3—Mo3xviii | 128.78 (15) |
O5ix—Nd3—O4ix | 67.62 (14) | O7—Mo3—Mo3xviii | 79.42 (7) |
O5x—Nd3—O4ix | 105.19 (14) | O9—Mo3—Mo3xviii | 44.01 (13) |
O4x—Nd3—O4ix | 66.9 (2) | O9iii—Mo3—Mo3xviii | 43.31 (13) |
O10—Nd3—O8xi | 129.1 (2) | Mo3vi—Mo3—Mo3xviii | 167.10 (8) |
O5ix—Nd3—O8xi | 73.97 (14) | Mo3iv—Mo3—Mo3xviii | 167.88 (7) |
O5x—Nd3—O8xi | 73.97 (14) | Mo3v—Mo3—Mo3iii | 5.44 (3) |
O4x—Nd3—O8xi | 139.17 (13) | O2iii—Mo3—Mo3iii | 90.62 (8) |
O4ix—Nd3—O8xi | 139.17 (13) | O9v—Mo3—Mo3iii | 128.59 (15) |
O10—Nd3—O1xii | 71.33 (18) | O9iv—Mo3—Mo3iii | 128.91 (15) |
O5ix—Nd3—O1xii | 99.53 (13) | O7—Mo3—Mo3iii | 80.04 (6) |
O5x—Nd3—O1xii | 138.96 (13) | O9—Mo3—Mo3iii | 43.99 (13) |
O4x—Nd3—O1xii | 149.47 (14) | O9iii—Mo3—Mo3iii | 43.32 (13) |
O4ix—Nd3—O1xii | 107.72 (13) | Mo3vi—Mo3—Mo3iii | 167.73 (7) |
O8xi—Nd3—O1xii | 65.13 (14) | Mo3iv—Mo3—Mo3iii | 168.51 (7) |
O10—Nd3—O1xi | 71.33 (18) | Mo3xviii—Mo3—Mo3iii | 0.621 (8) |
O5ix—Nd3—O1xi | 138.96 (13) | O10—Si—O6xix | 108.8 (4) |
O5x—Nd3—O1xi | 99.53 (13) | O10—Si—O1 | 109.7 (2) |
O4x—Nd3—O1xi | 107.72 (13) | O6xix—Si—O1 | 105.0 (2) |
O4ix—Nd3—O1xi | 149.47 (14) | O10—Si—O1xvii | 109.7 (2) |
O8xi—Nd3—O1xi | 65.13 (14) | O6xix—Si—O1xvii | 105.0 (2) |
O1xii—Nd3—O1xi | 60.67 (17) | O1—Si—O1xvii | 118.0 (3) |
O10—Nd3—O6x | 78.94 (13) | Si—O1—Mo2 | 121.3 (2) |
O5ix—Nd3—O6x | 136.43 (16) | Si—O1—Nd2vi | 113.1 (2) |
O5x—Nd3—O6x | 65.21 (16) | Mo2—O1—Nd2vi | 116.82 (18) |
O4x—Nd3—O6x | 55.67 (17) | Si—O1—Nd3xi | 99.6 (2) |
O4ix—Nd3—O6x | 121.22 (17) | Mo2—O1—Nd3xi | 100.03 (16) |
O8xi—Nd3—O6x | 96.04 (14) | Nd2vi—O1—Nd3xi | 100.11 (15) |
O1xii—Nd3—O6x | 114.70 (16) | Mo3iii—O2—Mo2xvii | 127.12 (13) |
O1xi—Nd3—O6x | 55.02 (16) | Mo3xviii—O2—Mo2xvii | 136.69 (16) |
O10—Nd3—O6xiii | 78.94 (13) | Mo3iii—O2—Mo2 | 136.69 (16) |
O5ix—Nd3—O6xiii | 65.21 (16) | Mo3xviii—O2—Mo2 | 127.12 (13) |
O5x—Nd3—O6xiii | 136.43 (16) | Mo2xvii—O2—Mo2 | 95.5 (3) |
O4x—Nd3—O6xiii | 121.22 (17) | Mo2—O3—Mo2xvii | 100.9 (3) |
O4ix—Nd3—O6xiii | 55.67 (17) | Mo2—O3—Nd1xix | 127.47 (15) |
O8xi—Nd3—O6xiii | 96.04 (14) | Mo2xvii—O3—Nd1xix | 127.47 (15) |
O1xii—Nd3—O6xiii | 55.02 (16) | Mo1—O4—Nd1xix | 129.6 (2) |
O1xi—Nd3—O6xiii | 114.70 (16) | Mo1—O4—Nd2xiv | 93.50 (17) |
O6x—Nd3—O6xiii | 157.8 (3) | Nd1xix—O4—Nd2xiv | 115.01 (18) |
O4v—Mo1—O4 | 94.5 (3) | Mo1—O4—Nd3xvi | 96.08 (17) |
O4v—Mo1—O5 | 163.60 (18) | Nd1xix—O4—Nd3xvi | 109.39 (17) |
O4—Mo1—O5 | 88.37 (18) | Nd2xiv—O4—Nd3xvi | 111.05 (17) |
O4v—Mo1—O5v | 88.37 (18) | Mo2—O5—Mo1 | 77.44 (15) |
O4—Mo1—O5v | 163.60 (18) | Mo2—O5—Nd3xvi | 126.38 (19) |
O5—Mo1—O5v | 84.5 (2) | Mo1—O5—Nd3xvi | 94.71 (16) |
O4v—Mo1—O8 | 92.31 (17) | Mo2—O5—Nd1 | 104.56 (17) |
O4—Mo1—O8 | 92.31 (17) | Mo1—O5—Nd1 | 104.90 (17) |
O5—Mo1—O8 | 103.72 (17) | Nd3xvi—O5—Nd1 | 128.36 (17) |
O5v—Mo1—O8 | 103.72 (17) | Siii—O6—Mo1 | 170.9 (4) |
O4v—Mo1—O6 | 76.65 (18) | Siii—O6—Nd2xiv | 102.9 (3) |
O4—Mo1—O6 | 76.65 (18) | Mo1—O6—Nd2xiv | 86.2 (2) |
O5—Mo1—O6 | 88.36 (18) | Siii—O6—Nd3xvi | 96.28 (14) |
O5v—Mo1—O6 | 88.36 (18) | Mo1—O6—Nd3xvi | 82.35 (13) |
O8—Mo1—O6 | 163.5 (3) | Nd2xiv—O6—Nd3xvi | 97.50 (14) |
O4v—Mo1—Mo2 | 144.28 (13) | Siii—O6—Nd3xv | 96.28 (14) |
O4—Mo1—Mo2 | 94.20 (13) | Mo1—O6—Nd3xv | 82.35 (13) |
O5—Mo1—Mo2 | 51.15 (12) | Nd2xiv—O6—Nd3xv | 97.50 (14) |
O5v—Mo1—Mo2 | 92.81 (12) | Nd3xvi—O6—Nd3xv | 157.8 (3) |
O8—Mo1—Mo2 | 52.76 (13) | Mo2v—O7—Mo2 | 77.8 (2) |
O6—Mo1—Mo2 | 139.06 (12) | Mo2v—O7—Mo3 | 135.39 (13) |
O4v—Mo1—Mo2v | 94.20 (13) | Mo2—O7—Mo3 | 144.19 (16) |
O4—Mo1—Mo2v | 144.28 (13) | Mo2v—O7—Mo3v | 144.19 (16) |
O5—Mo1—Mo2v | 92.81 (12) | Mo2—O7—Mo3v | 135.39 (13) |
O5v—Mo1—Mo2v | 51.15 (12) | Mo2v—O7—Nd1 | 100.1 (2) |
O8—Mo1—Mo2v | 52.76 (13) | Mo2—O7—Nd1 | 100.1 (2) |
O6—Mo1—Mo2v | 139.06 (12) | Mo3—O7—Nd1 | 88.0 (2) |
Mo2—Mo1—Mo2v | 60.38 (3) | Mo3v—O7—Nd1 | 88.0 (2) |
O3—Mo2—O5 | 93.4 (2) | Mo1—O8—Mo2 | 75.52 (19) |
O3—Mo2—O7 | 167.96 (18) | Mo1—O8—Mo2v | 75.52 (19) |
O5—Mo2—O7 | 88.8 (2) | Mo2—O8—Mo2v | 75.4 (2) |
O3—Mo2—O2 | 81.62 (18) | Mo1—O8—Nd3xi | 174.8 (3) |
O5—Mo2—O2 | 87.0 (2) | Mo2—O8—Nd3xi | 108.5 (2) |
O7—Mo2—O2 | 86.67 (17) | Mo2v—O8—Nd3xi | 108.5 (2) |
O3—Mo2—O8 | 88.33 (17) | Mo3v—O9—Mo3xviii | 79.7 (2) |
O5—Mo2—O8 | 102.9 (2) | Mo3xviii—O9—Mo3 | 86.24 (19) |
O7—Mo2—O8 | 102.73 (16) | Mo3v—O9—Mo3iii | 86.11 (19) |
O2—Mo2—O8 | 166.3 (2) | Mo3v—O9—Nd2vi | 100.32 (19) |
O3—Mo2—O1 | 86.1 (2) | Mo3xviii—O9—Nd2vi | 146.0 (2) |
O5—Mo2—O1 | 171.44 (17) | Mo3—O9—Nd2vi | 94.31 (17) |
O7—Mo2—O1 | 89.9 (2) | Mo3iii—O9—Nd2vi | 146.1 (2) |
O2—Mo2—O1 | 84.5 (2) | Mo3v—O9—Nd1iii | 132.9 (2) |
O8—Mo2—O1 | 85.6 (2) | Mo3xviii—O9—Nd1iii | 93.60 (18) |
O3—Mo2—Mo1 | 95.04 (16) | Mo3—O9—Nd1iii | 134.1 (2) |
O5—Mo2—Mo1 | 51.41 (12) | Mo3iii—O9—Nd1iii | 88.46 (16) |
O7—Mo2—Mo1 | 95.57 (15) | Nd2vi—O9—Nd1iii | 109.58 (19) |
O2—Mo2—Mo1 | 138.13 (18) | Si—O10—Nd3 | 170.3 (5) |
O8—Mo2—Mo1 | 51.72 (17) | Si—O10—Nd2xx | 91.0 (3) |
O1—Mo2—Mo1 | 137.15 (12) | Nd3—O10—Nd2xx | 98.7 (2) |
O3—Mo2—Mo2v | 140.47 (13) |
Symmetry codes: (i) −x+1/2, y+1/2, z+1/2; (ii) −x+1/2, −y+1, z+1/2; (iii) −x, −y+1, −z+1; (iv) −x, y+1/2, −z+1; (v) x, −y+3/2, z; (vi) −x, −y+2, −z+1; (vii) −x+1/2, −y+2, z+1/2; (viii) x, y+1, z+1; (ix) x−1/2, −y+1/2, −z+1/2; (x) x−1/2, y, −z+1/2; (xi) −x, −y+1, −z; (xii) −x, y−1/2, −z; (xiii) x−1/2, y−1, −z+1/2; (xiv) −x+1/2, −y+2, z−1/2; (xv) x+1/2, y+1, −z+1/2; (xvi) x+1/2, y, −z+1/2; (xvii) x, −y+1/2, z; (xviii) −x, y−1/2, −z+1; (xix) −x+1/2, −y+1, z−1/2; (xx) x, y−1, z−1; (xxi) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | Nd3Mo4SiO14 |
Mr | 1068.56 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 293 |
a, b, c (Å) | 17.5348 (15), 5.6159 (3), 10.8542 (11) |
V (Å3) | 1068.85 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 19.04 |
Crystal size (mm) | 0.16 × 0.02 × 0.02 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Analytical (de Meulenaer & Tompa, 1965) |
Tmin, Tmax | 0.272, 0.710 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30670, 3131, 2619 |
Rint | 0.063 |
(sin θ/λ)max (Å−1) | 0.866 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.085, 1.38 |
No. of reflections | 3131 |
No. of parameters | 121 |
w = 1/[σ2(Fo2) + 19.2566P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.32, −3.72 |
Computer programs: COLLECT (Nonius, 1998), COLLECT, EVALCCD (Duisenberg, 1998), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), DIAMOND (Bergerhoff, 1996), SHELXL97.
Nd1—O4i | 2.321 (4) | Mo1—Mo2 | 2.5351 (8) |
Nd1—O3ii | 2.444 (6) | Mo2—O3 | 1.988 (4) |
Nd1—O9iii | 2.520 (5) | Mo2—O5 | 2.023 (4) |
Nd1—O5 | 2.524 (4) | Mo2—O7 | 2.029 (5) |
Nd1—O7 | 2.651 (7) | Mo2—O2 | 2.072 (4) |
Nd2—O9iv | 2.422 (5) | Mo2—O8 | 2.084 (5) |
Nd2—O1iv | 2.461 (4) | Mo2—O1 | 2.127 (4) |
Nd2—O4v | 2.465 (4) | Mo2—Mo2xi | 2.5498 (9) |
Nd2—O6v | 2.580 (7) | Mo2—Mo2xii | 3.0661 (9) |
Nd2—O10vi | 2.896 (8) | Mo3—O2iii | 1.925 (6) |
Nd3—O10 | 2.368 (7) | Mo3—O9xi | 1.941 (5) |
Nd3—O5vii | 2.476 (4) | Mo3—O9iv | 1.966 (5) |
Nd3—O4viii | 2.503 (4) | Mo3—O7 | 2.047 (6) |
Nd3—O8ix | 2.544 (6) | Mo3—O9 | 2.160 (5) |
Nd3—O1x | 2.760 (5) | Mo3—O9iii | 2.187 (5) |
Nd3—O6viii | 2.8617 (13) | Mo3—Mo3xiii | 2.503 (4) |
Mo1—O4 | 1.944 (5) | Mo3—Mo3iii | 3.145 (4) |
Mo1—O5 | 2.030 (4) | Si—O10 | 1.620 (7) |
Mo1—O8 | 2.055 (6) | Si—O6xiv | 1.626 (7) |
Mo1—O6 | 2.122 (6) | Si—O1 | 1.649 (4) |
Symmetry codes: (i) −x+1/2, y+1/2, z+1/2; (ii) −x+1/2, −y+1, z+1/2; (iii) −x, −y+1, −z+1; (iv) −x, y+1/2, −z+1; (v) −x+1/2, −y+2, z+1/2; (vi) x, y+1, z+1; (vii) x−1/2, −y+1/2, −z+1/2; (viii) x−1/2, y, −z+1/2; (ix) −x, −y+1, −z; (x) −x, y−1/2, −z; (xi) x, −y+3/2, z; (xii) x, −y+1/2, z; (xiii) −x, −y+2, −z+1; (xiv) −x+1/2, −y+1, z−1/2. |
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The title compound is isotypic with La3Mo4SiO14 (Betteridge et al., 1984). The crystal structure contains chains of triangular Mo3O13 units and chains of edge-sharing MoO6 octahedra similar to those found in MoO2 (Brandt & Skapski, 1967). Both chains run parallel to the b axis (Fig. 1). Each single Mo chain is linked through O2 and O7 atoms to two Mo3 chains to form ribbons (Fig. 2). The Mo—Mo distances within the Mo3 triangles are 2.5351 (8) and 2.5498 (9) Å and the shortest distance between adjacent Mo3 clusters is 3.0661 (9) Å. In the single Mo chains, the Mo—Mo distances are alternately 2.503 (4) and 3.145 (4) Å. The Mo—O distances of Mo1 and Mo2 forming the Mo3 cluster unit range from 1.944 (5) to 2.127 (4) Å, while those of the Mo3 atom forming the Mo2 dimer vary between 1.925 (6) and 2.187 (5) Å. From the lengths of the Mo—O bonds, we can estimate the oxidation states of each independent Mo atom by using the empirical bond length-bond strength relationship developed by Brown and Wu (1976). The calculations result in valence sums of +3.99 (6), +3.59 (6) and +3.92 (6) for Mo1, Mo2 and Mo3, respectively. Consequently, in Nd3Mo4SiO14 the number of electrons per Mo3 cluster is evaluated to 7, and to 2 per Mo atom in the single Mo chains. The Si site is tetrahedrally coordinated by O atoms with Si—O distances ranging from 1.620 (7) to 1.649 (9) Å. The bond length-bond strength calculation shows an oxidation state of +3.86 (5), in good agreement with the expected value of +4. The Nd atoms are surrounded by 8 to 10 O atoms forming considerably distorted polyhedra with Nd—O distances ranging from 2.321 (4) to 2.896 (8) Å (Table 1).