A new polymorph of caesium praseodymium polyphosphate, CsPr(PO3)4, features PrO8 polyhedra sharing O atoms with PO4 groups, yielding a three-dimensional framework. The latter delimits intersecting channels in which the Cs ions are located.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (P-O)= 0.003 Å
- R factor = 0.025
- wR factor = 0.062
- Data-to-parameter ratio = 14.3
checkCIF/PLATON results
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Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXL97.
caesium praseodymium polyphosphate
top
Crystal data top
CsPr(PO3)4 | F(000) = 1080 |
Mr = 589.70 | Dx = 3.811 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 10.4938 (3) Å | θ = 3.2–20.5° |
b = 9.0744 (2) Å | µ = 8.92 mm−1 |
c = 11.2525 (5) Å | T = 298 K |
β = 106.414 (2)° | Prism, green |
V = 1027.85 (6) Å3 | 0.14 × 0.13 × 0.13 mm |
Z = 4 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 2339 independent reflections |
Radiation source: fine-focus sealed tube | 2211 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 2.3° |
ω/2θ scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −10→11 |
Tmin = 0.314, Tmax = 0.320 | l = −14→14 |
3875 measured reflections | |
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)] = 0.025 | w = 1/[σ2(Fo2) + (0.0248P)2 + 2.2899P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.062 | (Δ/σ)max = 0.001 |
S = 1.16 | Δρmax = 1.39 e Å−3 |
2339 reflections | Δρmin = −2.29 e Å−3 |
164 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0305 (7) |
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 | |
Pr | 0.000962 (19) | 0.77402 (2) | 0.318652 (18) | 0.00522 (11) | |
Cs | −0.18383 (3) | 1.06568 (3) | 0.03998 (2) | 0.01906 (12) | |
P1 | 0.03981 (10) | 1.17615 (10) | 0.36311 (9) | 0.0058 (2) | |
P2 | −0.14267 (10) | 0.40572 (11) | 0.24018 (9) | 0.0060 (2) | |
P3 | 0.32623 (10) | 0.89786 (11) | 0.52429 (9) | 0.0060 (2) | |
P4 | 0.25280 (9) | 1.03016 (10) | 0.28397 (9) | 0.0057 (2) | |
O1 | −0.0375 (3) | 1.0379 (3) | 0.3303 (3) | 0.0112 (6) | |
O2 | 0.0599 (3) | 1.2461 (3) | 0.4861 (3) | 0.0120 (6) | |
O3 | 0.1854 (3) | 1.1589 (3) | 0.3438 (3) | 0.0090 (5) | |
O4 | −0.0205 (3) | 0.2943 (3) | 0.2549 (3) | 0.0085 (6) | |
O5 | −0.1004 (3) | 0.5355 (3) | 0.3222 (3) | 0.0115 (6) | |
O6 | −0.2597 (3) | 0.3209 (3) | 0.2515 (3) | 0.0127 (6) | |
O7 | −0.1648 (3) | 0.4493 (3) | 0.0990 (3) | 0.0126 (6) | |
O8 | 0.1874 (3) | 0.8441 (3) | 0.4872 (3) | 0.0123 (6) | |
O9 | 0.4324 (3) | 0.7942 (3) | 0.5918 (3) | 0.0103 (6) | |
O10 | 0.3586 (3) | 0.9605 (3) | 0.4028 (2) | 0.0080 (5) | |
O11 | 0.3284 (3) | 1.0979 (3) | 0.2051 (3) | 0.0106 (6) | |
O12 | 0.1489 (3) | 0.9202 (3) | 0.2235 (3) | 0.0098 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Pr | 0.00547 (14) | 0.00532 (15) | 0.00486 (14) | −0.00039 (7) | 0.00145 (9) | −0.00069 (7) |
Cs | 0.02223 (18) | 0.02460 (18) | 0.00956 (16) | 0.00475 (11) | 0.00321 (12) | −0.00150 (10) |
P1 | 0.0063 (5) | 0.0055 (4) | 0.0055 (4) | 0.0006 (4) | 0.0014 (4) | 0.0001 (4) |
P2 | 0.0061 (5) | 0.0060 (4) | 0.0055 (5) | 0.0005 (4) | 0.0009 (4) | 0.0005 (4) |
P3 | 0.0067 (5) | 0.0068 (4) | 0.0040 (4) | −0.0003 (4) | 0.0010 (4) | −0.0005 (4) |
P4 | 0.0060 (4) | 0.0066 (4) | 0.0050 (4) | −0.0002 (4) | 0.0025 (4) | 0.0006 (4) |
O1 | 0.0092 (13) | 0.0098 (13) | 0.0147 (14) | −0.0012 (11) | 0.0034 (12) | −0.0022 (12) |
O2 | 0.0140 (15) | 0.0160 (13) | 0.0061 (14) | −0.0008 (12) | 0.0028 (12) | −0.0010 (11) |
O3 | 0.0076 (13) | 0.0081 (12) | 0.0119 (13) | 0.0009 (11) | 0.0037 (11) | −0.0012 (11) |
O4 | 0.0082 (13) | 0.0091 (12) | 0.0085 (13) | 0.0046 (11) | 0.0027 (11) | 0.0020 (11) |
O5 | 0.0155 (14) | 0.0102 (13) | 0.0094 (13) | −0.0022 (12) | 0.0044 (12) | −0.0005 (11) |
O6 | 0.0078 (13) | 0.0116 (14) | 0.0180 (15) | −0.0033 (11) | 0.0026 (12) | 0.0057 (12) |
O7 | 0.0189 (15) | 0.0105 (13) | 0.0064 (13) | 0.0008 (12) | 0.0005 (12) | 0.0013 (11) |
O8 | 0.0093 (14) | 0.0191 (15) | 0.0081 (13) | −0.0043 (12) | 0.0015 (11) | 0.0008 (12) |
O9 | 0.0111 (14) | 0.0093 (13) | 0.0104 (14) | 0.0032 (11) | 0.0028 (12) | 0.0005 (11) |
O10 | 0.0067 (12) | 0.0108 (12) | 0.0069 (13) | 0.0005 (11) | 0.0026 (11) | 0.0016 (11) |
O11 | 0.0110 (14) | 0.0128 (13) | 0.0098 (14) | −0.0005 (11) | 0.0061 (11) | 0.0000 (11) |
O12 | 0.0108 (14) | 0.0126 (13) | 0.0069 (13) | −0.0028 (11) | 0.0041 (11) | −0.0022 (11) |
Geometric parameters (Å, º) top
Pr—O8 | 2.394 (3) | P2—O7 | 1.589 (3) |
Pr—O5 | 2.417 (3) | P2—O4 | 1.605 (3) |
Pr—O1 | 2.438 (3) | P2—Csv | 3.7531 (10) |
Pr—O2i | 2.462 (3) | P2—Csxi | 3.7726 (10) |
Pr—O6ii | 2.467 (3) | P3—O8 | 1.480 (3) |
Pr—O11iii | 2.470 (3) | P3—O9 | 1.491 (3) |
Pr—O12 | 2.501 (3) | P3—O10 | 1.603 (3) |
Pr—O9iv | 2.526 (3) | P3—O7vi | 1.611 (3) |
Pr—Cs | 4.1426 (4) | P3—Csvi | 4.2126 (11) |
Pr—Csv | 4.4912 (4) | P4—O11 | 1.481 (3) |
Pr—Csvi | 4.6894 (4) | P4—O12 | 1.492 (3) |
Cs—O12vii | 3.092 (3) | P4—O10 | 1.606 (3) |
Cs—O5ii | 3.097 (3) | P4—O3 | 1.609 (3) |
Cs—O2viii | 3.098 (3) | P4—Csvii | 3.6163 (10) |
Cs—O11vii | 3.122 (3) | O2—Pri | 2.462 (3) |
Cs—O1 | 3.203 (3) | O2—Csx | 3.098 (3) |
Cs—O4ix | 3.278 (3) | O3—Csx | 3.360 (3) |
Cs—O3viii | 3.360 (3) | O4—P1xi | 1.612 (3) |
Cs—O6ii | 3.403 (3) | O4—Csxi | 3.278 (3) |
Cs—O9iv | 3.478 (3) | O5—Csv | 3.097 (3) |
Cs—O7ix | 3.539 (3) | O6—Prv | 2.467 (3) |
Cs—O6ix | 3.568 (3) | O6—Csv | 3.403 (3) |
Cs—P4vii | 3.6163 (10) | O6—Csxi | 3.568 (3) |
P1—O1 | 1.482 (3) | O7—P3iv | 1.611 (3) |
P1—O2 | 1.483 (3) | O7—Csxi | 3.539 (3) |
P1—O3 | 1.610 (3) | O9—Prvi | 2.526 (3) |
P1—O4ix | 1.612 (3) | O9—Csvi | 3.478 (3) |
P1—Csx | 3.8207 (10) | O11—Prxii | 2.470 (3) |
P2—O5 | 1.485 (3) | O11—Csvii | 3.122 (3) |
P2—O6 | 1.485 (3) | O12—Csvii | 3.092 (3) |
| | | |
O8—Pr—O5 | 119.32 (10) | O4ix—Cs—O6ix | 42.78 (7) |
O8—Pr—O1 | 78.88 (10) | O3viii—Cs—O6ix | 80.14 (7) |
O5—Pr—O1 | 142.99 (9) | O6ii—Cs—O6ix | 81.291 (7) |
O8—Pr—O2i | 70.89 (10) | O9iv—Cs—O6ix | 129.16 (7) |
O5—Pr—O2i | 72.10 (10) | O7ix—Cs—O6ix | 41.21 (7) |
O1—Pr—O2i | 86.34 (10) | O12vii—Cs—P4vii | 24.12 (5) |
O8—Pr—O6ii | 137.97 (10) | O5ii—Cs—P4vii | 121.14 (6) |
O5—Pr—O6ii | 75.11 (10) | O2viii—Cs—P4vii | 91.15 (6) |
O1—Pr—O6ii | 71.19 (9) | O11vii—Cs—P4vii | 23.98 (5) |
O2i—Pr—O6ii | 78.28 (10) | O1—Cs—P4vii | 155.63 (5) |
O8—Pr—O11iii | 78.60 (10) | O4ix—Cs—P4vii | 144.06 (5) |
O5—Pr—O11iii | 76.00 (9) | O3viii—Cs—P4vii | 65.70 (5) |
O1—Pr—O11iii | 141.00 (9) | O6ii—Cs—P4vii | 120.92 (5) |
O2i—Pr—O11iii | 115.29 (10) | O9iv—Cs—P4vii | 84.49 (5) |
O6ii—Pr—O11iii | 141.89 (9) | O7ix—Cs—P4vii | 114.23 (5) |
O8—Pr—O12 | 74.39 (9) | O6ix—Cs—P4vii | 144.06 (5) |
O5—Pr—O12 | 144.22 (9) | O1—P1—O2 | 121.18 (18) |
O1—Pr—O12 | 68.55 (9) | O1—P1—O3 | 110.95 (16) |
O2i—Pr—O12 | 140.36 (9) | O2—P1—O3 | 106.11 (17) |
O6ii—Pr—O12 | 118.49 (10) | O1—P1—O4ix | 107.72 (16) |
O11iii—Pr—O12 | 74.94 (9) | O2—P1—O4ix | 110.04 (16) |
O8—Pr—O9iv | 143.26 (9) | O3—P1—O4ix | 98.48 (15) |
O5—Pr—O9iv | 78.23 (9) | O1—P1—Csx | 158.39 (12) |
O1—Pr—O9iv | 106.92 (10) | O2—P1—Csx | 50.56 (12) |
O2i—Pr—O9iv | 144.31 (10) | O3—P1—Csx | 61.33 (10) |
O6ii—Pr—O9iv | 75.25 (10) | O4ix—P1—Csx | 93.66 (11) |
O11iii—Pr—O9iv | 74.95 (9) | O1—P1—Cs | 53.26 (12) |
O12—Pr—O9iv | 74.43 (9) | O2—P1—Cs | 151.44 (13) |
O8—Pr—Cs | 122.20 (7) | O3—P1—Cs | 101.27 (11) |
O5—Pr—Cs | 118.08 (7) | O4ix—P1—Cs | 57.10 (11) |
O1—Pr—Cs | 50.51 (7) | Csx—P1—Cs | 145.04 (3) |
O2i—Pr—Cs | 122.61 (7) | O5—P2—O6 | 117.86 (18) |
O6ii—Pr—Cs | 55.19 (7) | O5—P2—O7 | 110.96 (16) |
O11iii—Pr—Cs | 122.01 (7) | O6—P2—O7 | 108.88 (17) |
O12—Pr—Cs | 63.37 (7) | O5—P2—O4 | 110.23 (16) |
O9iv—Pr—Cs | 56.84 (7) | O6—P2—O4 | 108.71 (16) |
O8—Pr—Csv | 110.65 (7) | O7—P2—O4 | 98.42 (16) |
O5—Pr—Csv | 40.86 (7) | O5—P2—Csv | 53.07 (12) |
O1—Pr—Csv | 104.12 (7) | O6—P2—Csv | 64.99 (12) |
O2i—Pr—Csv | 41.22 (7) | O7—P2—Csv | 126.97 (12) |
O6ii—Pr—Csv | 52.38 (7) | O4—P2—Csv | 134.30 (11) |
O11iii—Pr—Csv | 113.47 (7) | O5—P2—Csxi | 169.62 (13) |
O12—Pr—Csv | 170.61 (7) | O6—P2—Csxi | 70.68 (12) |
O9iv—Pr—Csv | 103.11 (7) | O7—P2—Csxi | 69.31 (11) |
Cs—Pr—Csv | 107.566 (6) | O4—P2—Csxi | 59.96 (11) |
O8—Pr—Csvi | 57.18 (7) | Csv—P2—Csxi | 135.63 (3) |
O5—Pr—Csvi | 69.52 (7) | O8—P3—O9 | 118.03 (17) |
O1—Pr—Csvi | 136.03 (7) | O8—P3—O10 | 107.77 (16) |
O2i—Pr—Csvi | 78.41 (7) | O9—P3—O10 | 110.50 (16) |
O6ii—Pr—Csvi | 142.13 (7) | O8—P3—O7vi | 109.78 (17) |
O11iii—Pr—Csvi | 37.63 (7) | O9—P3—O7vi | 110.60 (17) |
O12—Pr—Csvi | 98.38 (7) | O10—P3—O7vi | 98.33 (15) |
O9iv—Pr—Csvi | 109.41 (7) | O8—P3—Csvi | 69.41 (12) |
Cs—Pr—Csvi | 158.599 (9) | O9—P3—Csvi | 51.18 (12) |
Csv—Pr—Csvi | 90.987 (7) | O10—P3—Csvi | 113.80 (11) |
O12vii—Cs—O5ii | 141.76 (8) | O7vi—P3—Csvi | 146.75 (11) |
O12vii—Cs—O2viii | 96.95 (7) | O11—P4—O12 | 116.76 (17) |
O5ii—Cs—O2viii | 55.22 (7) | O11—P4—O10 | 107.51 (16) |
O12vii—Cs—O11vii | 48.09 (7) | O12—P4—O10 | 111.10 (16) |
O5ii—Cs—O11vii | 99.13 (7) | O11—P4—O3 | 108.83 (16) |
O2viii—Cs—O11vii | 84.90 (8) | O12—P4—O3 | 109.00 (16) |
O12vii—Cs—O1 | 145.99 (7) | O10—P4—O3 | 102.68 (15) |
O5ii—Cs—O1 | 71.95 (7) | O11—P4—Csvii | 58.94 (12) |
O2viii—Cs—O1 | 112.49 (7) | O12—P4—Csvii | 57.83 (11) |
O11vii—Cs—O1 | 146.81 (7) | O10—P4—Csvii | 129.68 (11) |
O12vii—Cs—O4ix | 120.14 (7) | O3—P4—Csvii | 127.61 (11) |
O5ii—Cs—O4ix | 89.47 (7) | P1—O1—Pr | 139.21 (17) |
O2viii—Cs—O4ix | 92.27 (7) | P1—O1—Cs | 104.97 (14) |
O11vii—Cs—O4ix | 167.10 (7) | Pr—O1—Cs | 93.51 (9) |
O1—Cs—O4ix | 45.36 (7) | P1—O2—Pri | 142.88 (18) |
O12vii—Cs—O3viii | 58.41 (7) | P1—O2—Csx | 107.75 (15) |
O5ii—Cs—O3viii | 100.02 (7) | Pri—O2—Csx | 107.21 (10) |
O2viii—Cs—O3viii | 44.81 (7) | P4—O3—P1 | 132.29 (19) |
O11vii—Cs—O3viii | 76.53 (7) | P4—O3—Csx | 131.99 (14) |
O1—Cs—O3viii | 135.86 (7) | P1—O3—Csx | 93.80 (12) |
O4ix—Cs—O3viii | 92.59 (7) | P2—O4—P1xi | 128.93 (19) |
O12vii—Cs—O6ii | 141.21 (7) | P2—O4—Csxi | 94.97 (12) |
O5ii—Cs—O6ii | 45.77 (7) | P1xi—O4—Csxi | 98.52 (12) |
O2viii—Cs—O6ii | 100.61 (7) | P2—O5—Pr | 139.10 (17) |
O11vii—Cs—O6ii | 99.37 (7) | P2—O5—Csv | 104.41 (14) |
O1—Cs—O6ii | 51.11 (7) | Pr—O5—Csv | 108.44 (10) |
O4ix—Cs—O6ii | 93.51 (7) | P2—O6—Prv | 149.40 (17) |
O3viii—Cs—O6ii | 145.11 (7) | P2—O6—Csv | 91.72 (13) |
O12vii—Cs—O9iv | 93.95 (7) | Prv—O6—Csv | 88.29 (8) |
O5ii—Cs—O9iv | 95.99 (7) | P2—O6—Csxi | 86.20 (13) |
O2viii—Cs—O9iv | 142.62 (7) | Prv—O6—Csxi | 94.41 (9) |
O11vii—Cs—O9iv | 76.20 (7) | Csv—O6—Csxi | 177.26 (9) |
O1—Cs—O9iv | 73.19 (7) | P2—O7—P3iv | 134.9 (2) |
O4ix—Cs—O9iv | 112.65 (7) | P2—O7—Csxi | 85.85 (12) |
O3viii—Cs—O9iv | 150.18 (7) | P3iv—O7—Csxi | 139.20 (15) |
O6ii—Cs—O9iv | 52.58 (7) | P3—O8—Pr | 146.08 (17) |
O12vii—Cs—O7ix | 97.10 (7) | P3—O9—Prvi | 128.90 (17) |
O5ii—Cs—O7ix | 90.19 (7) | P3—O9—Csvi | 109.30 (14) |
O2viii—Cs—O7ix | 59.61 (8) | Prvi—O9—Csvi | 85.72 (8) |
O11vii—Cs—O7ix | 128.40 (7) | P3—O10—P4 | 125.87 (17) |
O1—Cs—O7ix | 84.29 (7) | P4—O11—Prxii | 149.40 (18) |
O4ix—Cs—O7ix | 41.33 (7) | P4—O11—Csvii | 97.09 (13) |
O3viii—Cs—O7ix | 51.87 (7) | Prxii—O11—Csvii | 113.47 (10) |
O6ii—Cs—O7ix | 121.62 (7) | P4—O12—Pr | 128.42 (16) |
O9iv—Cs—O7ix | 153.36 (7) | P4—O12—Csvii | 98.05 (13) |
O12vii—Cs—O6ix | 136.23 (7) | Pr—O12—Csvii | 133.52 (10) |
O5ii—Cs—O6ix | 52.48 (7) | P4—O12—Cs | 117.45 (14) |
O2viii—Cs—O6ix | 55.09 (7) | Pr—O12—Cs | 80.13 (7) |
O11vii—Cs—O6ix | 138.90 (7) | Csvii—O12—Cs | 78.57 (6) |
O1—Cs—O6ix | 60.24 (7) | | |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x−1/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) x−1/2, −y+3/2, z−1/2; (v) −x−1/2, y−1/2, −z+1/2; (vi) x+1/2, −y+3/2, z+1/2; (vii) −x, −y+2, −z; (viii) x−1/2, −y+5/2, z−1/2; (ix) x, y+1, z; (x) x+1/2, −y+5/2, z+1/2; (xi) x, y−1, z; (xii) −x+1/2, y+1/2, −z+1/2. |