Acta Cryst. (2009). E65, i43 [ doi:10.1107/S1600536809016638 ]
Single crystals of Pr5Si3N9, pentapraseodymium trisilicon nonanitride, were obtained by the reaction of elemental praseodymium with silicon diimide in a radio-frequency furnace at 1873 K. The crystal structure consists of a chain-like Si-N substructure of corner-sharing SiN4 tetrahedra. An additional Q1-type [SiN4] unit is attached to every second tetrahedron directed alternately in opposite directions. The resulting branched chains interlock with each other, building up a three-dimensional structure. The central atoms of the Q1-type [SiN4] unit and of its attached tetrahedron are situated on a mirror plane, as are two of the four crystallographically unique Pr3+ ions. The latter are coordinated by six to ten N atoms, with Pr-N distances similar to those of other rare earth nitridosilicates.
Pr5Si3N9 was synthesized by the reaction of Pr (swarf, 99.9%, Chempur, Karlsruhe) and silicon diimide (Schnick & Huppertz, 1997) which were thoroughly mixed in a glove box (Unilab, MBraun). The mixture was heated in a tungsten crucible in a radio-frequency furnace (Schnick et al., 1999) under purified N2 up to 1873 K within 1 h. This temperature was retained for 5 h, and the crucible thereafter cooled down to 1073 K in 35 h before quenching to room temperature within 1 h. Pr5Si3N9 could be obtained as air-sensitive dark-yellow crystals with PrN as by-product.
In the final Fourier map the highest peak is 0.19 Å from atom Si1 and the deepest hole is 0.64 Å from atom Pr4.
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./wm2229fig1thm.gif)
| Fig. 1. Presentation of the Si—N substructure, with anisotropic displacement parameters drawn at the 50% probability level. SiO4 tetrahedra are depicted purple for Si1, light blue for Si2 and dark blue for Si3. |
![[Figure 2]](./wm2229fig2thm.gif)
| Fig. 2. View along [010] illustrating the resulting three-dimensional structure. Pr3+ ions are depicted yellow, with anisotropic displacement parameters drawn at the 50% probability level. |
| Pr5Si3N9 | F000 = 3200 |
| Mr = 914.91 | Dx = 6.520 Mg m−3 |
| Orthorhombic, Cmce | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -C 2 bc 2 | Cell parameters from 5699 reflections |
| a = 10.512 (2) Å | θ = 2.6–30.5º |
| b = 11.243 (2) Å | µ = 26.01 mm−1 |
| c = 15.773 (3) Å | T = 293 K |
| V = 1864.2 (6) Å3 | Block, yellow |
| Z = 8 | 0.17 × 0.10 × 0.08 mm |
| Stoe IPDS diffractometer | 1480 independent reflections |
| Radiation source: fine-focus sealed tube | 1133 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.080 |
| T = 293 K | θmax = 30.5º |
| ω scans | θmin = 2.6º |
| Absorption correction: multi-scan (XPREP; Sheldrick, 2008) | h = −12→14 |
| Tmin = 0.040, Tmax = 0.125 | k = −15→15 |
| 9626 measured reflections | l = −22→22 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0626P)2] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.037 | (Δ/σ)max < 0.001 |
| wR(F2) = 0.097 | Δρmax = 2.10 e Å−3 |
| S = 0.97 | Δρmin = −2.30 e Å−3 |
| 1480 reflections | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 90 parameters | Extinction coefficient: 0.00090 (6) |
| Primary atom site location: structure-invariant direct methods |
| Pr5Si3N9 | V = 1864.2 (6) Å3 |
| Mr = 914.91 | Z = 8 |
| Orthorhombic, Cmce | Mo Kα |
| a = 10.512 (2) Å | µ = 26.01 mm−1 |
| b = 11.243 (2) Å | T = 293 K |
| c = 15.773 (3) Å | 0.17 × 0.10 × 0.08 mm |
| Stoe IPDS diffractometer | 1480 independent reflections |
| Absorption correction: multi-scan (XPREP; Sheldrick, 2008) | 1133 reflections with I > 2σ(I) |
| Tmin = 0.040, Tmax = 0.125 | Rint = 0.080 |
| 9626 measured reflections |
| R[F2 > 2σ(F2)] = 0.037 | Δρmax = 2.10 e Å−3 |
| wR(F2) = 0.097 | Δρmin = −2.30 e Å−3 |
| S = 0.97 | Absolute structure: ? |
| 1480 reflections | Flack parameter: ? |
| 90 parameters | Rogers parameter: ? |
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 | ||
| Pr1 | 0.0000 | 0.01304 (6) | 0.33611 (4) | 0.01605 (18) | |
| Pr2 | −0.21211 (5) | −0.25683 (4) | 0.37015 (3) | 0.01847 (17) | |
| Pr3 | 0.0000 | −0.00567 (6) | 0.11240 (4) | 0.01844 (19) | |
| Pr4 | 0.20546 (7) | 0.0000 | 0.5000 | 0.01756 (19) | |
| Si1 | 0.0000 | −0.2598 (3) | 0.5166 (2) | 0.0148 (6) | |
| Si2 | 0.0000 | 0.2724 (3) | 0.2739 (2) | 0.0148 (6) | |
| Si3 | −0.2500 | −0.0361 (3) | 0.2500 | 0.0146 (6) | |
| N1 | 0.0000 | 0.1552 (10) | 0.2035 (7) | 0.020 (2) | |
| N2 | 0.0000 | 0.2233 (10) | 0.3761 (6) | 0.024 (2) | |
| N3 | 0.1254 (8) | −0.1348 (7) | 0.2416 (5) | 0.0201 (14) | |
| N4 | 0.2371 (7) | 0.0349 (7) | 0.3472 (5) | 0.0176 (13) | |
| N5 | −0.1321 (8) | −0.3528 (8) | 0.5006 (5) | 0.0226 (15) | |
| N6 | 0.0000 | −0.1350 (10) | 0.4519 (7) | 0.022 (2) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Pr1 | 0.0137 (3) | 0.0145 (3) | 0.0199 (3) | 0.000 | 0.000 | −0.0005 (2) |
| Pr2 | 0.0190 (3) | 0.0167 (3) | 0.0197 (3) | −0.00032 (16) | −0.00156 (15) | 0.00234 (15) |
| Pr3 | 0.0220 (4) | 0.0160 (3) | 0.0173 (3) | 0.000 | 0.000 | −0.0013 (2) |
| Pr4 | 0.0173 (4) | 0.0177 (3) | 0.0177 (3) | 0.000 | 0.000 | 0.0001 (2) |
| Si1 | 0.0176 (16) | 0.0136 (13) | 0.0133 (12) | 0.000 | 0.000 | 0.0007 (10) |
| Si2 | 0.0120 (15) | 0.0141 (14) | 0.0184 (14) | 0.000 | 0.000 | −0.0014 (10) |
| Si3 | 0.0113 (14) | 0.0164 (14) | 0.0160 (14) | 0.000 | 0.0011 (10) | 0.000 |
| N1 | 0.020 (6) | 0.019 (4) | 0.022 (5) | 0.000 | 0.000 | −0.005 (4) |
| N2 | 0.041 (7) | 0.018 (5) | 0.012 (4) | 0.000 | 0.000 | −0.002 (3) |
| N3 | 0.013 (3) | 0.020 (3) | 0.027 (4) | −0.001 (3) | 0.004 (3) | −0.003 (3) |
| N4 | 0.013 (3) | 0.024 (3) | 0.016 (3) | −0.005 (3) | 0.001 (2) | −0.001 (3) |
| N5 | 0.019 (4) | 0.024 (4) | 0.024 (3) | −0.004 (3) | −0.007 (3) | 0.005 (3) |
| N6 | 0.018 (6) | 0.024 (5) | 0.024 (5) | 0.000 | 0.000 | 0.001 (4) |
| Pr1—N2 | 2.446 (12) | Pr4—Pr2xii | 3.5243 (7) |
| Pr1—N3i | 2.593 (8) | Pr4—Pr2i | 3.5408 (7) |
| Pr1—N3 | 2.593 (8) | Pr4—Pr2xv | 3.5408 (7) |
| Pr1—N6 | 2.471 (12) | Si1—N6 | 1.735 (12) |
| Pr1—N4 | 2.511 (8) | Si1—N2xv | 1.742 (10) |
| Pr1—N4i | 2.511 (8) | Si1—N5 | 1.756 (8) |
| Pr1—N1 | 2.633 (11) | Si1—N5i | 1.756 (8) |
| Pr1—Si3 | 3.0093 (8) | Si1—Pr3xvi | 3.039 (3) |
| Pr1—Si3ii | 3.0093 (8) | Si1—Pr2i | 3.211 (2) |
| Pr1—Si2 | 3.077 (3) | Si1—Pr3iii | 3.432 (3) |
| Pr1—Si2iii | 3.214 (3) | Si2—N2 | 1.704 (11) |
| Pr1—Pr4 | 3.3717 (8) | Si2—N1 | 1.723 (11) |
| Pr2—N3i | 2.613 (8) | Si2—N3ix | 1.699 (8) |
| Pr2—N4iv | 2.429 (8) | Si2—N3x | 1.699 (8) |
| Pr2—N5 | 2.470 (8) | Si2—Pr3ix | 3.073 (3) |
| Pr2—N1iii | 2.702 (6) | Si2—Pr2ix | 3.200 (2) |
| Pr2—N5v | 2.891 (9) | Si2—Pr2x | 3.200 (2) |
| Pr2—N6 | 2.917 (8) | Si2—Pr1ix | 3.214 (3) |
| Pr2—N3vi | 2.812 (8) | Si2—Pr2xiii | 3.4018 (16) |
| Pr2—Si3 | 3.148 (3) | Si2—Pr2xvii | 3.4018 (16) |
| Pr2—Si2iii | 3.200 (2) | Si3—N3vi | 1.722 (8) |
| Pr2—Si1 | 3.211 (2) | Si3—N3i | 1.722 (8) |
| Pr2—Si2iv | 3.4018 (16) | Si3—N4vi | 1.733 (7) |
| Pr2—Pr4iv | 3.5243 (7) | Si3—N4i | 1.733 (7) |
| Pr3—N1 | 2.310 (11) | Si3—Pr1vi | 3.0093 (8) |
| Pr3—N5vii | 2.752 (8) | Si3—Pr2xviii | 3.148 (3) |
| Pr3—N5viii | 2.752 (8) | Si3—Pr3vi | 3.4254 (7) |
| Pr3—N5ix | 2.839 (9) | N1—Pr2ix | 2.702 (6) |
| Pr3—N5x | 2.839 (9) | N1—Pr2x | 2.702 (6) |
| Pr3—N4xi | 2.873 (8) | N2—Si1xv | 1.742 (10) |
| Pr3—N4vi | 2.873 (8) | N3—Si3ii | 1.722 (8) |
| Pr3—Si1viii | 3.039 (3) | N3—Si2iii | 1.699 (8) |
| Pr3—Si2iii | 3.073 (3) | N3—Pr2i | 2.613 (8) |
| Pr3—Si3ii | 3.4254 (7) | N3—Pr2ii | 2.812 (8) |
| Pr3—Si3 | 3.4254 (7) | N4—Si3ii | 1.733 (7) |
| Pr3—Si1ix | 3.432 (3) | N4—Pr2xiii | 2.429 (8) |
| Pr4—N5xii | 2.378 (8) | N4—Pr3ii | 2.873 (8) |
| Pr4—N5xiii | 2.378 (8) | N5—Pr4iv | 2.378 (8) |
| Pr4—N4 | 2.465 (7) | N5—Pr3xvi | 2.752 (8) |
| Pr4—N4xiv | 2.465 (7) | N5—Pr3iii | 2.839 (9) |
| Pr4—N6 | 2.747 (7) | N5—Pr2v | 2.891 (9) |
| Pr4—N6xv | 2.747 (7) | N6—Pr4xv | 2.747 (7) |
| Pr4—Pr1xv | 3.3717 (8) | N6—Pr2i | 2.917 (8) |
| Pr4—Pr2xiii | 3.5243 (7) | ||
| N2—Pr1—N3i | 140.1 (2) | N4—Pr4—Pr2xiii | 43.52 (18) |
| N2—Pr1—N3 | 140.1 (2) | N4xiv—Pr4—Pr2xiii | 131.21 (19) |
| N3i—Pr1—N3 | 61.1 (4) | N6—Pr4—Pr2xiii | 117.5 (2) |
| N2—Pr1—N6 | 117.4 (4) | N6xv—Pr4—Pr2xiii | 85.7 (2) |
| N3i—Pr1—N6 | 89.6 (3) | Pr1—Pr4—Pr2xiii | 71.228 (16) |
| N3—Pr1—N6 | 89.6 (3) | Pr1xv—Pr4—Pr2xiii | 129.553 (18) |
| N2—Pr1—N4 | 83.53 (18) | N5xii—Pr4—Pr2xii | 44.41 (19) |
| N3i—Pr1—N4 | 127.4 (3) | N5xiii—Pr4—Pr2xii | 111.17 (19) |
| N3—Pr1—N4 | 66.3 (3) | N4—Pr4—Pr2xii | 131.21 (19) |
| N6—Pr1—N4 | 90.85 (18) | N4xiv—Pr4—Pr2xii | 43.52 (18) |
| N2—Pr1—N4i | 83.53 (18) | N6—Pr4—Pr2xii | 85.7 (2) |
| N3i—Pr1—N4i | 66.3 (3) | N6xv—Pr4—Pr2xii | 117.5 (2) |
| N3—Pr1—N4i | 127.4 (3) | Pr1—Pr4—Pr2xii | 129.553 (18) |
| N6—Pr1—N4i | 90.85 (18) | Pr1xv—Pr4—Pr2xii | 71.228 (16) |
| N4—Pr1—N4i | 166.2 (3) | Pr2xiii—Pr4—Pr2xii | 151.53 (3) |
| N2—Pr1—N1 | 67.5 (3) | N5xii—Pr4—Pr2i | 54.3 (2) |
| N3i—Pr1—N1 | 86.1 (3) | N5xiii—Pr4—Pr2i | 123.7 (2) |
| N3—Pr1—N1 | 86.1 (3) | N4—Pr4—Pr2i | 64.00 (18) |
| N6—Pr1—N1 | 175.0 (4) | N4xiv—Pr4—Pr2i | 115.66 (18) |
| N4—Pr1—N1 | 89.75 (17) | N6—Pr4—Pr2i | 53.49 (19) |
| N4i—Pr1—N1 | 89.75 (17) | N6xv—Pr4—Pr2i | 128.75 (19) |
| N2—Pr1—Si3 | 107.07 (11) | Pr1—Pr4—Pr2i | 66.712 (16) |
| N3i—Pr1—Si3 | 34.80 (19) | Pr1xv—Pr4—Pr2i | 114.875 (19) |
| N3—Pr1—Si3 | 93.83 (19) | Pr2xiii—Pr4—Pr2i | 106.955 (19) |
| N6—Pr1—Si3 | 102.12 (13) | Pr2xii—Pr4—Pr2i | 72.463 (19) |
| N4—Pr1—Si3 | 156.38 (16) | N5xii—Pr4—Pr2xv | 123.7 (2) |
| N4i—Pr1—Si3 | 35.15 (17) | N5xiii—Pr4—Pr2xv | 54.3 (2) |
| N1—Pr1—Si3 | 75.69 (11) | N4—Pr4—Pr2xv | 115.66 (18) |
| N2—Pr1—Si3ii | 107.07 (11) | N4xiv—Pr4—Pr2xv | 64.00 (18) |
| N3i—Pr1—Si3ii | 93.83 (19) | N6—Pr4—Pr2xv | 128.75 (19) |
| N3—Pr1—Si3ii | 34.80 (19) | N6xv—Pr4—Pr2xv | 53.49 (19) |
| N6—Pr1—Si3ii | 102.12 (13) | Pr1—Pr4—Pr2xv | 114.875 (19) |
| N4—Pr1—Si3ii | 35.15 (17) | Pr1xv—Pr4—Pr2xv | 66.712 (16) |
| N4i—Pr1—Si3ii | 156.38 (16) | Pr2xiii—Pr4—Pr2xv | 72.463 (19) |
| N1—Pr1—Si3ii | 75.69 (11) | Pr2xii—Pr4—Pr2xv | 106.955 (19) |
| Si3—Pr1—Si3ii | 121.68 (5) | Pr2i—Pr4—Pr2xv | 177.74 (3) |
| N2—Pr1—Si2 | 33.5 (2) | N6—Si1—N2xv | 112.4 (6) |
| N3i—Pr1—Si2 | 115.08 (18) | N6—Si1—N5 | 113.4 (3) |
| N3—Pr1—Si2 | 115.08 (18) | N2xv—Si1—N5 | 106.3 (4) |
| N6—Pr1—Si2 | 150.9 (3) | N6—Si1—N5i | 113.4 (3) |
| N4—Pr1—Si2 | 85.94 (18) | N2xv—Si1—N5i | 106.3 (4) |
| N4i—Pr1—Si2 | 85.94 (18) | N5—Si1—N5i | 104.5 (6) |
| N1—Pr1—Si2 | 34.0 (2) | N6—Si1—Pr3xvi | 173.8 (4) |
| Si3—Pr1—Si2 | 91.71 (7) | N2xv—Si1—Pr3xvi | 73.8 (4) |
| Si3ii—Pr1—Si2 | 91.71 (7) | N5—Si1—Pr3xvi | 63.6 (3) |
| N2—Pr1—Si2iii | 162.3 (2) | N5i—Si1—Pr3xvi | 63.6 (3) |
| N3i—Pr1—Si2iii | 31.79 (18) | N6—Si1—Pr2 | 64.4 (3) |
| N3—Pr1—Si2iii | 31.79 (18) | N2xv—Si1—Pr2 | 134.16 (11) |
| N6—Pr1—Si2iii | 80.3 (3) | N5—Si1—Pr2 | 49.7 (3) |
| N4—Pr1—Si2iii | 96.89 (17) | N5i—Si1—Pr2 | 116.8 (3) |
| N4i—Pr1—Si2iii | 96.89 (17) | Pr3xvi—Si1—Pr2 | 111.53 (8) |
| N1—Pr1—Si2iii | 94.7 (2) | N6—Si1—Pr2i | 64.4 (3) |
| Si3—Pr1—Si2iii | 66.54 (6) | N2xv—Si1—Pr2i | 134.16 (11) |
| Si3ii—Pr1—Si2iii | 66.54 (6) | N5—Si1—Pr2i | 116.8 (3) |
| Si2—Pr1—Si2iii | 128.72 (3) | N5i—Si1—Pr2i | 49.7 (3) |
| N2—Pr1—Pr4 | 81.05 (18) | Pr3xvi—Si1—Pr2i | 111.53 (8) |
| N3i—Pr1—Pr4 | 137.62 (17) | Pr2—Si1—Pr2i | 87.97 (8) |
| N3—Pr1—Pr4 | 95.02 (19) | N6—Si1—Pr3iii | 107.6 (4) |
| N6—Pr1—Pr4 | 53.42 (16) | N2xv—Si1—Pr3iii | 140.0 (4) |
| N4—Pr1—Pr4 | 46.78 (16) | N5—Si1—Pr3iii | 55.6 (3) |
| N4i—Pr1—Pr4 | 125.95 (16) | N5i—Si1—Pr3iii | 55.6 (3) |
| N1—Pr1—Pr4 | 129.46 (13) | Pr3xvi—Si1—Pr3iii | 66.18 (7) |
| Si3—Pr1—Pr4 | 153.83 (4) | Pr2—Si1—Pr3iii | 65.29 (6) |
| Si3ii—Pr1—Pr4 | 77.212 (18) | Pr2i—Si1—Pr3iii | 65.29 (6) |
| Si2—Pr1—Pr4 | 106.60 (5) | N2—Si2—N1 | 111.2 (6) |
| Si2iii—Pr1—Pr4 | 112.17 (4) | N2—Si2—N3ix | 109.6 (4) |
| N3i—Pr2—N4iv | 117.8 (2) | N1—Si2—N3ix | 112.2 (4) |
| N3i—Pr2—N5 | 139.2 (3) | N2—Si2—N3x | 109.6 (4) |
| N4iv—Pr2—N5 | 77.2 (3) | N1—Si2—N3x | 112.2 (4) |
| N3i—Pr2—N1iii | 64.6 (3) | N3ix—Si2—N3x | 101.8 (6) |
| N4iv—Pr2—N1iii | 76.4 (3) | N2—Si2—Pr3ix | 73.2 (4) |
| N5—Pr2—N1iii | 85.3 (3) | N1—Si2—Pr3ix | 175.6 (4) |
| N3i—Pr2—N5v | 121.4 (2) | N3ix—Si2—Pr3ix | 65.5 (3) |
| N4iv—Pr2—N5v | 113.1 (2) | N3x—Si2—Pr3ix | 65.5 (3) |
| N5—Pr2—N5v | 78.0 (3) | N2—Si2—Pr1 | 52.5 (4) |
| N1iii—Pr2—N5v | 157.9 (3) | N1—Si2—Pr1 | 58.7 (4) |
| N3i—Pr2—N6 | 80.2 (3) | N3ix—Si2—Pr1 | 128.9 (3) |
| N4iv—Pr2—N6 | 133.4 (3) | N3x—Si2—Pr1 | 128.9 (3) |
| N5—Pr2—N6 | 65.0 (3) | Pr3ix—Si2—Pr1 | 125.69 (11) |
| N1iii—Pr2—N6 | 74.4 (3) | N2—Si2—Pr2ix | 129.66 (18) |
| N5v—Pr2—N6 | 85.5 (2) | N1—Si2—Pr2ix | 57.6 (2) |
| N3i—Pr2—N3vi | 57.9 (3) | N3ix—Si2—Pr2ix | 120.1 (3) |
| N4iv—Pr2—N3vi | 104.1 (2) | N3x—Si2—Pr2ix | 54.6 (3) |
| N5—Pr2—N3vi | 160.4 (3) | Pr3ix—Si2—Pr2ix | 119.86 (7) |
| N1iii—Pr2—N3vi | 114.2 (3) | Pr1—Si2—Pr2ix | 97.41 (8) |
| N5v—Pr2—N3vi | 83.7 (2) | N2—Si2—Pr2x | 129.66 (18) |
| N6—Pr2—N3vi | 120.8 (3) | N1—Si2—Pr2x | 57.6 (2) |
| N3i—Pr2—Si3 | 33.16 (18) | N3ix—Si2—Pr2x | 54.6 (3) |
| N4iv—Pr2—Si3 | 129.97 (18) | N3x—Si2—Pr2x | 120.1 (3) |
| N5—Pr2—Si3 | 152.7 (2) | Pr3ix—Si2—Pr2x | 119.86 (7) |
| N1iii—Pr2—Si3 | 97.7 (2) | Pr1—Si2—Pr2x | 97.41 (8) |
| N5v—Pr2—Si3 | 90.97 (16) | Pr2ix—Si2—Pr2x | 88.33 (8) |
| N6—Pr2—Si3 | 89.6 (2) | N2—Si2—Pr1ix | 141.6 (4) |
| N3vi—Pr2—Si3 | 32.97 (16) | N1—Si2—Pr1ix | 107.2 (4) |
| N3i—Pr2—Si2iii | 32.00 (18) | N3ix—Si2—Pr1ix | 53.5 (3) |
| N4iv—Pr2—Si2iii | 98.41 (18) | N3x—Si2—Pr1ix | 53.5 (3) |
| N5—Pr2—Si2iii | 113.5 (2) | Pr3ix—Si2—Pr1ix | 68.39 (7) |
| N1iii—Pr2—Si2iii | 32.6 (2) | Pr1—Si2—Pr1ix | 165.93 (11) |
| N5v—Pr2—Si2iii | 148.38 (18) | Pr2ix—Si2—Pr1ix | 72.74 (6) |
| N6—Pr2—Si2iii | 74.5 (2) | Pr2x—Si2—Pr1ix | 72.74 (6) |
| N3vi—Pr2—Si2iii | 85.88 (18) | N2—Si2—Pr2xiii | 63.03 (5) |
| Si3—Pr2—Si2iii | 65.15 (5) | N1—Si2—Pr2xiii | 102.34 (17) |
| N3i—Pr2—Si1 | 108.77 (18) | N3ix—Si2—Pr2xiii | 55.5 (3) |
| N4iv—Pr2—Si1 | 104.47 (19) | N3x—Si2—Pr2xiii | 144.5 (3) |
| N5—Pr2—Si1 | 32.8 (2) | Pr3ix—Si2—Pr2xiii | 79.51 (6) |
| N1iii—Pr2—Si1 | 74.5 (2) | Pr1—Si2—Pr2xiii | 76.47 (6) |
| N5v—Pr2—Si1 | 83.71 (16) | Pr2ix—Si2—Pr2xiii | 157.94 (9) |
| N6—Pr2—Si1 | 32.5 (2) | Pr2x—Si2—Pr2xiii | 71.77 (2) |
| N3vi—Pr2—Si1 | 151.39 (17) | Pr1ix—Si2—Pr2xiii | 108.81 (6) |
| Si3—Pr2—Si1 | 121.96 (6) | N2—Si2—Pr2xvii | 63.03 (5) |
| Si2iii—Pr2—Si1 | 91.60 (6) | N1—Si2—Pr2xvii | 102.34 (17) |
| N3i—Pr2—Si2iv | 85.02 (18) | N3ix—Si2—Pr2xvii | 144.5 (3) |
| N4iv—Pr2—Si2iv | 80.27 (19) | N3x—Si2—Pr2xvii | 55.5 (3) |
| N5—Pr2—Si2iv | 135.8 (2) | Pr3ix—Si2—Pr2xvii | 79.51 (6) |
| N1iii—Pr2—Si2iv | 125.3 (2) | Pr1—Si2—Pr2xvii | 76.47 (6) |
| N5v—Pr2—Si2iv | 76.68 (16) | Pr2ix—Si2—Pr2xvii | 71.77 (2) |
| N6—Pr2—Si2iv | 146.3 (2) | Pr2x—Si2—Pr2xvii | 157.94 (9) |
| N3vi—Pr2—Si2iv | 29.85 (17) | Pr1ix—Si2—Pr2xvii | 108.81 (6) |
| Si3—Pr2—Si2iv | 62.78 (6) | Pr2xiii—Si2—Pr2xvii | 125.65 (10) |
| Si2iii—Pr2—Si2iv | 107.04 (3) | N3vi—Si3—N3i | 99.8 (6) |
| Si1—Pr2—Si2iv | 160.04 (7) | N3vi—Si3—N4vi | 107.8 (4) |
| N3i—Pr2—Pr4iv | 160.79 (17) | N3i—Si3—N4vi | 106.7 (4) |
| N4iv—Pr2—Pr4iv | 44.35 (17) | N3vi—Si3—N4i | 106.7 (4) |
| N5—Pr2—Pr4iv | 42.36 (19) | N3i—Si3—N4i | 107.8 (4) |
| N1iii—Pr2—Pr4iv | 99.7 (2) | N4vi—Si3—N4i | 125.2 (5) |
| N5v—Pr2—Pr4iv | 77.38 (17) | N3vi—Si3—Pr1 | 138.4 (3) |
| N6—Pr2—Pr4iv | 107.2 (2) | N3i—Si3—Pr1 | 59.3 (3) |
| N3vi—Pr2—Pr4iv | 126.40 (17) | N4vi—Si3—Pr1 | 112.5 (3) |
| Si3—Pr2—Pr4iv | 158.49 (2) | N4i—Si3—Pr1 | 56.5 (3) |
| Si2iii—Pr2—Pr4iv | 131.58 (6) | N3vi—Si3—Pr1vi | 59.3 (3) |
| Si1—Pr2—Pr4iv | 75.19 (5) | N3i—Si3—Pr1vi | 138.4 (3) |
| Si2iv—Pr2—Pr4iv | 96.64 (5) | N4vi—Si3—Pr1vi | 56.5 (3) |
| N1—Pr3—N5vii | 148.38 (19) | N4i—Si3—Pr1vi | 112.5 (3) |
| N1—Pr3—N5viii | 148.38 (19) | Pr1—Si3—Pr1vi | 158.86 (12) |
| N5vii—Pr3—N5viii | 60.6 (3) | N3vi—Si3—Pr2xviii | 56.1 (3) |
| N1—Pr3—N5ix | 85.2 (3) | N3i—Si3—Pr2xviii | 62.7 (3) |
| N5vii—Pr3—N5ix | 72.6 (3) | N4vi—Si3—Pr2xviii | 79.7 (3) |
| N5viii—Pr3—N5ix | 101.2 (2) | N4i—Si3—Pr2xviii | 154.9 (3) |
| N1—Pr3—N5x | 85.2 (3) | Pr1—Si3—Pr2xviii | 121.79 (7) |
| N5vii—Pr3—N5x | 101.2 (2) | Pr1vi—Si3—Pr2xviii | 76.26 (3) |
| N5viii—Pr3—N5x | 72.6 (3) | N3vi—Si3—Pr2 | 62.7 (3) |
| N5ix—Pr3—N5x | 58.6 (3) | N3i—Si3—Pr2 | 56.1 (3) |
| N1—Pr3—N4xi | 74.78 (15) | N4vi—Si3—Pr2 | 154.9 (3) |
| N5vii—Pr3—N4xi | 136.0 (2) | N4i—Si3—Pr2 | 79.7 (3) |
| N5viii—Pr3—N4xi | 75.5 (2) | Pr1—Si3—Pr2 | 76.26 (3) |
| N5ix—Pr3—N4xi | 120.9 (2) | Pr1vi—Si3—Pr2 | 121.79 (7) |
| N5x—Pr3—N4xi | 64.7 (2) | Pr2xviii—Si3—Pr2 | 75.92 (8) |
| N1—Pr3—N4vi | 74.78 (15) | N3vi—Si3—Pr3 | 134.2 (3) |
| N5vii—Pr3—N4vi | 75.5 (2) | N3i—Si3—Pr3 | 55.4 (3) |
| N5viii—Pr3—N4vi | 136.0 (2) | N4vi—Si3—Pr3 | 56.9 (3) |
| N5ix—Pr3—N4vi | 64.7 (2) | N4i—Si3—Pr3 | 117.0 (3) |
| N5x—Pr3—N4vi | 120.9 (2) | Pr1—Si3—Pr3 | 66.28 (2) |
| N4xi—Pr3—N4vi | 148.3 (3) | Pr1vi—Si3—Pr3 | 111.45 (3) |
| N1—Pr3—Si1viii | 171.4 (3) | Pr2xviii—Si3—Pr3 | 78.13 (3) |
| N5vii—Pr3—Si1viii | 34.86 (17) | Pr2—Si3—Pr3 | 111.28 (6) |
| N5viii—Pr3—Si1viii | 34.86 (17) | N3vi—Si3—Pr3vi | 55.4 (3) |
| N5ix—Pr3—Si1viii | 102.31 (17) | N3i—Si3—Pr3vi | 134.2 (3) |
| N5x—Pr3—Si1viii | 102.31 (17) | N4vi—Si3—Pr3vi | 117.0 (3) |
| N4xi—Pr3—Si1viii | 104.38 (15) | N4i—Si3—Pr3vi | 56.9 (3) |
| N4vi—Pr3—Si1viii | 104.38 (15) | Pr1—Si3—Pr3vi | 111.45 (3) |
| N1—Pr3—Si2iii | 105.8 (3) | Pr1vi—Si3—Pr3vi | 66.28 (2) |
| N5vii—Pr3—Si2iii | 84.53 (19) | Pr2xviii—Si3—Pr3vi | 111.28 (6) |
| N5viii—Pr3—Si2iii | 84.53 (19) | Pr2—Si3—Pr3vi | 78.13 (3) |
| N5ix—Pr3—Si2iii | 149.10 (17) | Pr3—Si3—Pr3vi | 168.55 (11) |
| N5x—Pr3—Si2iii | 149.10 (17) | Si2—N1—Pr3 | 178.3 (7) |
| N4xi—Pr3—Si2iii | 89.97 (15) | Si2—N1—Pr1 | 87.3 (5) |
| N4vi—Pr3—Si2iii | 89.97 (15) | Pr3—N1—Pr1 | 91.1 (4) |
| Si1viii—Pr3—Si2iii | 65.53 (9) | Si2—N1—Pr2ix | 89.8 (3) |
| N1—Pr3—Si3ii | 71.58 (17) | Pr3—N1—Pr2ix | 91.1 (3) |
| N5vii—Pr3—Si3ii | 137.36 (18) | Pr1—N1—Pr2ix | 124.3 (2) |
| N5viii—Pr3—Si3ii | 87.79 (18) | Si2—N1—Pr2x | 89.8 (3) |
| N5ix—Pr3—Si3ii | 146.45 (18) | Pr3—N1—Pr2x | 91.1 (3) |
| N5x—Pr3—Si3ii | 94.75 (16) | Pr1—N1—Pr2x | 124.3 (2) |
| N4xi—Pr3—Si3ii | 30.36 (15) | Pr2ix—N1—Pr2x | 111.2 (4) |
| N4vi—Pr3—Si3ii | 127.82 (14) | Si2—N2—Si1xv | 147.4 (8) |
| Si1viii—Pr3—Si3ii | 103.21 (6) | Si2—N2—Pr1 | 94.0 (4) |
| Si2iii—Pr3—Si3ii | 63.20 (6) | Si1xv—N2—Pr1 | 118.6 (6) |
| N1—Pr3—Si3 | 71.58 (17) | Si3ii—N3—Si2iii | 175.7 (6) |
| N5vii—Pr3—Si3 | 87.79 (18) | Si3ii—N3—Pr2i | 90.7 (4) |
| N5viii—Pr3—Si3 | 137.36 (18) | Si2iii—N3—Pr2i | 93.4 (3) |
| N5ix—Pr3—Si3 | 94.75 (16) | Si3ii—N3—Pr1 | 85.9 (3) |
| N5x—Pr3—Si3 | 146.45 (18) | Si2iii—N3—Pr1 | 94.7 (3) |
| N4xi—Pr3—Si3 | 127.82 (14) | Pr2i—N3—Pr1 | 93.9 (3) |
| N4vi—Pr3—Si3 | 30.36 (15) | Si3ii—N3—Pr2ii | 84.3 (3) |
| Si1viii—Pr3—Si3 | 103.21 (6) | Si2iii—N3—Pr2ii | 94.7 (3) |
| Si2iii—Pr3—Si3 | 63.20 (6) | Pr2i—N3—Pr2ii | 91.0 (2) |
| Si3ii—Pr3—Si3 | 100.21 (3) | Pr1—N3—Pr2ii | 169.1 (3) |
| N1—Pr3—Si1ix | 74.8 (3) | Si3ii—N4—Pr2xiii | 124.0 (4) |
| N5vii—Pr3—Si1ix | 94.91 (19) | Si3ii—N4—Pr4 | 143.3 (4) |
| N5viii—Pr3—Si1ix | 94.91 (19) | Pr2xiii—N4—Pr4 | 92.1 (2) |
| N5ix—Pr3—Si1ix | 30.70 (16) | Si3ii—N4—Pr1 | 88.3 (3) |
| N5x—Pr3—Si1ix | 30.70 (16) | Pr2xiii—N4—Pr1 | 108.9 (3) |
| N4xi—Pr3—Si1ix | 90.21 (15) | Pr4—N4—Pr1 | 85.3 (2) |
| N4vi—Pr3—Si1ix | 90.21 (15) | Si3ii—N4—Pr3ii | 92.7 (3) |
| Si1viii—Pr3—Si1ix | 113.82 (7) | Pr2xiii—N4—Pr3ii | 84.8 (2) |
| Si2iii—Pr3—Si1ix | 179.35 (8) | Pr4—N4—Pr3ii | 83.5 (2) |
| Si3ii—Pr3—Si1ix | 117.13 (6) | Pr1—N4—Pr3ii | 162.7 (3) |
| Si3—Pr3—Si1ix | 117.13 (6) | Si1—N5—Pr4iv | 169.2 (5) |
| N5xii—Pr4—N5xiii | 88.2 (4) | Si1—N5—Pr2 | 97.4 (4) |
| N5xii—Pr4—N4 | 90.6 (3) | Pr4iv—N5—Pr2 | 93.2 (3) |
| N5xiii—Pr4—N4 | 78.2 (3) | Si1—N5—Pr3xvi | 81.5 (3) |
| N5xii—Pr4—N4xiv | 78.2 (3) | Pr4iv—N5—Pr3xvi | 87.8 (3) |
| N5xiii—Pr4—N4xiv | 90.6 (3) | Pr2—N5—Pr3xvi | 163.4 (4) |
| N4—Pr4—N4xiv | 164.5 (4) | Si1—N5—Pr3iii | 93.7 (4) |
| N5xii—Pr4—N6 | 100.3 (3) | Pr4iv—N5—Pr3iii | 85.8 (3) |
| N5xiii—Pr4—N6 | 161.9 (3) | Pr2—N5—Pr3iii | 84.7 (2) |
| N4—Pr4—N6 | 85.6 (3) | Pr3xvi—N5—Pr3iii | 78.8 (2) |
| N4xiv—Pr4—N6 | 106.7 (3) | Si1—N5—Pr2v | 95.3 (4) |
| N5xii—Pr4—N6xv | 161.9 (3) | Pr4iv—N5—Pr2v | 83.8 (3) |
| N5xiii—Pr4—N6xv | 100.3 (3) | Pr2—N5—Pr2v | 102.0 (3) |
| N4—Pr4—N6xv | 106.7 (3) | Pr3xvi—N5—Pr2v | 94.6 (2) |
| N4xiv—Pr4—N6xv | 85.6 (3) | Pr3iii—N5—Pr2v | 167.9 (3) |
| N6—Pr4—N6xv | 76.3 (4) | Si1—N6—Pr1 | 168.4 (7) |
| N5xii—Pr4—Pr1 | 119.2 (2) | Si1—N6—Pr4 | 106.5 (4) |
| N5xiii—Pr4—Pr1 | 115.63 (19) | Pr1—N6—Pr4 | 80.3 (3) |
| N4—Pr4—Pr1 | 47.91 (18) | Si1—N6—Pr4xv | 106.5 (4) |
| N4xiv—Pr4—Pr1 | 147.47 (18) | Pr1—N6—Pr4xv | 80.3 (3) |
| N6—Pr4—Pr1 | 46.3 (2) | Pr4—N6—Pr4xv | 103.7 (4) |
| N6xv—Pr4—Pr1 | 71.6 (2) | Si1—N6—Pr2 | 83.1 (3) |
| N5xii—Pr4—Pr1xv | 115.63 (19) | Pr1—N6—Pr2 | 89.4 (3) |
| N5xiii—Pr4—Pr1xv | 119.2 (2) | Pr4—N6—Pr2 | 169.3 (5) |
| N4—Pr4—Pr1xv | 147.47 (18) | Pr4xv—N6—Pr2 | 77.32 (4) |
| N4xiv—Pr4—Pr1xv | 47.91 (18) | Si1—N6—Pr2i | 83.1 (3) |
| N6—Pr4—Pr1xv | 71.6 (2) | Pr1—N6—Pr2i | 89.4 (3) |
| N6xv—Pr4—Pr1xv | 46.3 (2) | Pr4—N6—Pr2i | 77.32 (4) |
| Pr1—Pr4—Pr1xv | 100.33 (3) | Pr4xv—N6—Pr2i | 169.3 (5) |
| N5xii—Pr4—Pr2xiii | 111.17 (19) | Pr2—N6—Pr2i | 99.7 (3) |
| N5xiii—Pr4—Pr2xiii | 44.41 (19) |
| Symmetry codes: (i) −x, y, z; (ii) x+1/2, y, −z+1/2; (iii) x, y−1/2, −z+1/2; (iv) x−1/2, y−1/2, z; (v) −x−1/2, −y−1/2, −z+1; (vi) x−1/2, y, −z+1/2; (vii) x, −y−1/2, z−1/2; (viii) −x, −y−1/2, z−1/2; (ix) x, y+1/2, −z+1/2; (x) −x, y+1/2, −z+1/2; (xi) −x+1/2, y, −z+1/2; (xii) x+1/2, −y−1/2, −z+1; (xiii) x+1/2, y+1/2, z; (xiv) x, −y, −z+1; (xv) −x, −y, −z+1; (xvi) −x, −y−1/2, z+1/2; (xvii) −x−1/2, y+1/2, z; (xviii) −x−1/2, y, −z+1/2. |
The authors thank Thomas Miller and Dr Oliver Oeckler for performing the single-crystal X-ray diffractometry. Financial support by the Fonds der Chemischen Industrie (FCI) is gratefully acknowledged.
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The title compound is a branched chain-like nitridosilicate isotypic to Ln5Si3N9 (Ln = La, Ce) described by Schmolke et al. (2009). Except for Ln5Si3N9 (Ln = La, Ce, Pr), no other chain-like nitridosilicates have been observed so far. The single chains in Pr5Si3N9 run along [100] and are built up of corner sharing [SiN4] tetrahedra, whereas every second tetrahedron is additionally connected to a Q1-type tetrahedron. These direct alternately in opposing directions (Fig. 1). Thereby the Si2 and Si3 atoms are located on a mirrow plane which is co-planar to [100]. Due to the constitution of the terminal tetrahedra the chains interlock zipper-like with each other (Fig. 2). The Pr3+ ions (yellow) are located between the chains. The coordination numbers of the Pr3+ ions range between six (for Pr4) and ten (for Pr 3) with Pr—N distances varying from 2.310 (11) to 3.053 (2) Å. The geometric parameters of Pr5Si3N9 are in the usual ranges and correspond with those of the isotypic compounds Ln5Si3N9 (Ln = La, Ce) and other nitridosilicates (Schnick, 2001; Lissner & Schleid, 2004).