Pr5Si3N9

Lupart, S.; Schnick, W.

doi:10.1107/S1600536809016638

inorganic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page i43

doi:10.1107/S1600536809016638

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Pr₅Si₃N₉

Saskia Lupart ^a and Wolfgang Schnick ^a ^*

^aDepartment Chemie und Biochemie, Ludwig-Maximilians-Universität München, Lehrstuhl für Anorganische Festkörperchemie, Butenandtstrasse 5–13, D-81377 München, Germany
^*Correspondence e-mail: Wolfgang.Schnick@uni-muenchen.de

(Received 9 April 2009; accepted 4 May 2009; online 14 May 2009)

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.

Related literature

For isotypic compounds Ln₅Si₃N₉ (Ln = La, Ce), see: Schmolke et al. (2009 ). For experimental details, see: Schnick & Huppertz (1997 ); Schnick et al. (1999 ). Typical atomic distances for rare earth nitridosilicates have been reported by Schnick (2001 ) and Lissner & Schleid (2004 ).

Experimental

Crystal data

Pr₅Si₃N₉
M_r = 914.91
Orthorhombic, C m c e
a = 10.512 (2) Å
b = 11.243 (2) Å
c = 15.773 (3) Å
V = 1864.2 (6) Å³
Z = 8
Mo Kα radiation
μ = 26.01 mm⁻¹
T = 293 K
0.17 × 0.10 × 0.08 mm

Data collection

Stoe IPDS diffractometer
Absorption correction: multi-scan (XPREP; Sheldrick, 2008 ) T_min = 0.040, T_max = 0.125
9626 measured reflections
1480 independent reflections
1133 reflections with I > 2σ(I)
R_int = 0.080

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.097
S = 0.97
1480 reflections
90 parameters
Δρ_max = 2.10 e Å⁻³
Δρ_min = −2.31 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ); cell refinement: X-AREA; data reduction: X-AREA; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016638/wm2229sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016638/wm2229Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

For isotypic compounds Ln₅Si₃N₉ (Ln = La, Ce), see: Schmolke et al. (2009). For experimental details, see: Schnick & Huppertz (1997); Schnick et al. (1999). Typical atomic distances for rare earth nitridosilicates have been reported by Schnick (2001) and Lissner & Schleid (2004).

Experimental top

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.

Computing details top

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).

Figures top

	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.
	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.

Pentapraseodymiumtrisiliconnonanitride top

Crystal data top

Pr₅Si₃N₉	F(000) = 3200
M_r = 914.91	D_x = 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 = 2.6–30.5°
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

Data collection top

Stoe IPDS diffractometer	1480 independent reflections
Radiation source: fine-focus sealed tube	1133 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
ω scans	θ_max = 30.5°, θ_min = 2.6°
Absorption correction: multi-scan (XPREP; Sheldrick, 2008)	h = −12→14
T_min = 0.040, T_max = 0.125	k = −15→15
9626 measured reflections	l = −22→22

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)] = 0.037	w = 1/[σ²(F_o²) + (0.0626P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.097	(Δ/σ)_max < 0.001
S = 0.97	Δρ_max = 2.10 e Å⁻³
1480 reflections	Δρ_min = −2.31 e Å⁻³
90 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00090 (6)

Crystal data top

Pr₅Si₃N₉	V = 1864.2 (6) Å³
M_r = 914.91	Z = 8
Orthorhombic, Cmce	Mo Kα radiation
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

Data collection top

Stoe IPDS diffractometer	1480 independent reflections
Absorption correction: multi-scan (XPREP; Sheldrick, 2008)	1133 reflections with I > 2σ(I)
T_min = 0.040, T_max = 0.125	R_int = 0.080
9626 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	90 parameters
wR(F²) = 0.097	0 restraints
S = 0.97	Δρ_max = 2.10 e Å⁻³
1480 reflections	Δρ_min = −2.31 e Å⁻³

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	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

Pr1—N2	2.446 (12)	Pr4—Pr2^xii	3.5243 (7)
Pr1—N3ⁱ	2.593 (8)	Pr4—Pr2ⁱ	3.5408 (7)
Pr1—N3	2.593 (8)	Pr4—Pr2^xv	3.5408 (7)
Pr1—N6	2.471 (12)	Si1—N6	1.735 (12)
Pr1—N4	2.511 (8)	Si1—N2^xv	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—Pr3^xvi	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—N3^ix	1.699 (8)
Pr2—N4^iv	2.429 (8)	Si2—N3^x	1.699 (8)
Pr2—N5	2.470 (8)	Si2—Pr3^ix	3.073 (3)
Pr2—N1ⁱⁱⁱ	2.702 (6)	Si2—Pr2^ix	3.200 (2)
Pr2—N5^v	2.891 (9)	Si2—Pr2^x	3.200 (2)
Pr2—N6	2.917 (8)	Si2—Pr1^ix	3.214 (3)
Pr2—N3^vi	2.812 (8)	Si2—Pr2^xiii	3.4018 (16)
Pr2—Si3	3.148 (3)	Si2—Pr2^xvii	3.4018 (16)
Pr2—Si2ⁱⁱⁱ	3.200 (2)	Si3—N3^vi	1.722 (8)
Pr2—Si1	3.211 (2)	Si3—N3ⁱ	1.722 (8)
Pr2—Si2^iv	3.4018 (16)	Si3—N4^vi	1.733 (7)
Pr2—Pr4^iv	3.5243 (7)	Si3—N4ⁱ	1.733 (7)
Pr3—N1	2.310 (11)	Si3—Pr1^vi	3.0093 (8)
Pr3—N5^vii	2.752 (8)	Si3—Pr2^xviii	3.148 (3)
Pr3—N5^viii	2.752 (8)	Si3—Pr3^vi	3.4254 (7)
Pr3—N5^ix	2.839 (9)	N1—Pr2^ix	2.702 (6)
Pr3—N5^x	2.839 (9)	N1—Pr2^x	2.702 (6)
Pr3—N4^xi	2.873 (8)	N2—Si1^xv	1.742 (10)
Pr3—N4^vi	2.873 (8)	N3—Si3ⁱⁱ	1.722 (8)
Pr3—Si1^viii	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—Si1^ix	3.432 (3)	N4—Pr2^xiii	2.429 (8)
Pr4—N5^xii	2.378 (8)	N4—Pr3ⁱⁱ	2.873 (8)
Pr4—N5^xiii	2.378 (8)	N5—Pr4^iv	2.378 (8)
Pr4—N4	2.465 (7)	N5—Pr3^xvi	2.752 (8)
Pr4—N4^xiv	2.465 (7)	N5—Pr3ⁱⁱⁱ	2.839 (9)
Pr4—N6	2.747 (7)	N5—Pr2^v	2.891 (9)
Pr4—N6^xv	2.747 (7)	N6—Pr4^xv	2.747 (7)
Pr4—Pr1^xv	3.3717 (8)	N6—Pr2ⁱ	2.917 (8)
Pr4—Pr2^xiii	3.5243 (7)

N2—Pr1—N3ⁱ	140.1 (2)	N4—Pr4—Pr2^xiii	43.52 (18)
N2—Pr1—N3	140.1 (2)	N4^xiv—Pr4—Pr2^xiii	131.21 (19)
N3ⁱ—Pr1—N3	61.1 (4)	N6—Pr4—Pr2^xiii	117.5 (2)
N2—Pr1—N6	117.4 (4)	N6^xv—Pr4—Pr2^xiii	85.7 (2)
N3ⁱ—Pr1—N6	89.6 (3)	Pr1—Pr4—Pr2^xiii	71.228 (16)
N3—Pr1—N6	89.6 (3)	Pr1^xv—Pr4—Pr2^xiii	129.553 (18)
N2—Pr1—N4	83.53 (18)	N5^xii—Pr4—Pr2^xii	44.41 (19)
N3ⁱ—Pr1—N4	127.4 (3)	N5^xiii—Pr4—Pr2^xii	111.17 (19)
N3—Pr1—N4	66.3 (3)	N4—Pr4—Pr2^xii	131.21 (19)
N6—Pr1—N4	90.85 (18)	N4^xiv—Pr4—Pr2^xii	43.52 (18)
N2—Pr1—N4ⁱ	83.53 (18)	N6—Pr4—Pr2^xii	85.7 (2)
N3ⁱ—Pr1—N4ⁱ	66.3 (3)	N6^xv—Pr4—Pr2^xii	117.5 (2)
N3—Pr1—N4ⁱ	127.4 (3)	Pr1—Pr4—Pr2^xii	129.553 (18)
N6—Pr1—N4ⁱ	90.85 (18)	Pr1^xv—Pr4—Pr2^xii	71.228 (16)
N4—Pr1—N4ⁱ	166.2 (3)	Pr2^xiii—Pr4—Pr2^xii	151.53 (3)
N2—Pr1—N1	67.5 (3)	N5^xii—Pr4—Pr2ⁱ	54.3 (2)
N3ⁱ—Pr1—N1	86.1 (3)	N5^xiii—Pr4—Pr2ⁱ	123.7 (2)
N3—Pr1—N1	86.1 (3)	N4—Pr4—Pr2ⁱ	64.00 (18)
N6—Pr1—N1	175.0 (4)	N4^xiv—Pr4—Pr2ⁱ	115.66 (18)
N4—Pr1—N1	89.75 (17)	N6—Pr4—Pr2ⁱ	53.49 (19)
N4ⁱ—Pr1—N1	89.75 (17)	N6^xv—Pr4—Pr2ⁱ	128.75 (19)
N2—Pr1—Si3	107.07 (11)	Pr1—Pr4—Pr2ⁱ	66.712 (16)
N3ⁱ—Pr1—Si3	34.80 (19)	Pr1^xv—Pr4—Pr2ⁱ	114.875 (19)
N3—Pr1—Si3	93.83 (19)	Pr2^xiii—Pr4—Pr2ⁱ	106.955 (19)
N6—Pr1—Si3	102.12 (13)	Pr2^xii—Pr4—Pr2ⁱ	72.463 (19)
N4—Pr1—Si3	156.38 (16)	N5^xii—Pr4—Pr2^xv	123.7 (2)
N4ⁱ—Pr1—Si3	35.15 (17)	N5^xiii—Pr4—Pr2^xv	54.3 (2)
N1—Pr1—Si3	75.69 (11)	N4—Pr4—Pr2^xv	115.66 (18)
N2—Pr1—Si3ⁱⁱ	107.07 (11)	N4^xiv—Pr4—Pr2^xv	64.00 (18)
N3ⁱ—Pr1—Si3ⁱⁱ	93.83 (19)	N6—Pr4—Pr2^xv	128.75 (19)
N3—Pr1—Si3ⁱⁱ	34.80 (19)	N6^xv—Pr4—Pr2^xv	53.49 (19)
N6—Pr1—Si3ⁱⁱ	102.12 (13)	Pr1—Pr4—Pr2^xv	114.875 (19)
N4—Pr1—Si3ⁱⁱ	35.15 (17)	Pr1^xv—Pr4—Pr2^xv	66.712 (16)
N4ⁱ—Pr1—Si3ⁱⁱ	156.38 (16)	Pr2^xiii—Pr4—Pr2^xv	72.463 (19)
N1—Pr1—Si3ⁱⁱ	75.69 (11)	Pr2^xii—Pr4—Pr2^xv	106.955 (19)
Si3—Pr1—Si3ⁱⁱ	121.68 (5)	Pr2ⁱ—Pr4—Pr2^xv	177.74 (3)
N2—Pr1—Si2	33.5 (2)	N6—Si1—N2^xv	112.4 (6)
N3ⁱ—Pr1—Si2	115.08 (18)	N6—Si1—N5	113.4 (3)
N3—Pr1—Si2	115.08 (18)	N2^xv—Si1—N5	106.3 (4)
N6—Pr1—Si2	150.9 (3)	N6—Si1—N5ⁱ	113.4 (3)
N4—Pr1—Si2	85.94 (18)	N2^xv—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—Pr3^xvi	173.8 (4)
Si3—Pr1—Si2	91.71 (7)	N2^xv—Si1—Pr3^xvi	73.8 (4)
Si3ⁱⁱ—Pr1—Si2	91.71 (7)	N5—Si1—Pr3^xvi	63.6 (3)
N2—Pr1—Si2ⁱⁱⁱ	162.3 (2)	N5ⁱ—Si1—Pr3^xvi	63.6 (3)
N3ⁱ—Pr1—Si2ⁱⁱⁱ	31.79 (18)	N6—Si1—Pr2	64.4 (3)
N3—Pr1—Si2ⁱⁱⁱ	31.79 (18)	N2^xv—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)	Pr3^xvi—Si1—Pr2	111.53 (8)
N1—Pr1—Si2ⁱⁱⁱ	94.7 (2)	N6—Si1—Pr2ⁱ	64.4 (3)
Si3—Pr1—Si2ⁱⁱⁱ	66.54 (6)	N2^xv—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)	Pr3^xvi—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)	N2^xv—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)	Pr3^xvi—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—N3^ix	109.6 (4)
N3ⁱ—Pr2—N4^iv	117.8 (2)	N1—Si2—N3^ix	112.2 (4)
N3ⁱ—Pr2—N5	139.2 (3)	N2—Si2—N3^x	109.6 (4)
N4^iv—Pr2—N5	77.2 (3)	N1—Si2—N3^x	112.2 (4)
N3ⁱ—Pr2—N1ⁱⁱⁱ	64.6 (3)	N3^ix—Si2—N3^x	101.8 (6)
N4^iv—Pr2—N1ⁱⁱⁱ	76.4 (3)	N2—Si2—Pr3^ix	73.2 (4)
N5—Pr2—N1ⁱⁱⁱ	85.3 (3)	N1—Si2—Pr3^ix	175.6 (4)
N3ⁱ—Pr2—N5^v	121.4 (2)	N3^ix—Si2—Pr3^ix	65.5 (3)
N4^iv—Pr2—N5^v	113.1 (2)	N3^x—Si2—Pr3^ix	65.5 (3)
N5—Pr2—N5^v	78.0 (3)	N2—Si2—Pr1	52.5 (4)
N1ⁱⁱⁱ—Pr2—N5^v	157.9 (3)	N1—Si2—Pr1	58.7 (4)
N3ⁱ—Pr2—N6	80.2 (3)	N3^ix—Si2—Pr1	128.9 (3)
N4^iv—Pr2—N6	133.4 (3)	N3^x—Si2—Pr1	128.9 (3)
N5—Pr2—N6	65.0 (3)	Pr3^ix—Si2—Pr1	125.69 (11)
N1ⁱⁱⁱ—Pr2—N6	74.4 (3)	N2—Si2—Pr2^ix	129.66 (18)
N5^v—Pr2—N6	85.5 (2)	N1—Si2—Pr2^ix	57.6 (2)
N3ⁱ—Pr2—N3^vi	57.9 (3)	N3^ix—Si2—Pr2^ix	120.1 (3)
N4^iv—Pr2—N3^vi	104.1 (2)	N3^x—Si2—Pr2^ix	54.6 (3)
N5—Pr2—N3^vi	160.4 (3)	Pr3^ix—Si2—Pr2^ix	119.86 (7)
N1ⁱⁱⁱ—Pr2—N3^vi	114.2 (3)	Pr1—Si2—Pr2^ix	97.41 (8)
N5^v—Pr2—N3^vi	83.7 (2)	N2—Si2—Pr2^x	129.66 (18)
N6—Pr2—N3^vi	120.8 (3)	N1—Si2—Pr2^x	57.6 (2)
N3ⁱ—Pr2—Si3	33.16 (18)	N3^ix—Si2—Pr2^x	54.6 (3)
N4^iv—Pr2—Si3	129.97 (18)	N3^x—Si2—Pr2^x	120.1 (3)
N5—Pr2—Si3	152.7 (2)	Pr3^ix—Si2—Pr2^x	119.86 (7)
N1ⁱⁱⁱ—Pr2—Si3	97.7 (2)	Pr1—Si2—Pr2^x	97.41 (8)
N5^v—Pr2—Si3	90.97 (16)	Pr2^ix—Si2—Pr2^x	88.33 (8)
N6—Pr2—Si3	89.6 (2)	N2—Si2—Pr1^ix	141.6 (4)
N3^vi—Pr2—Si3	32.97 (16)	N1—Si2—Pr1^ix	107.2 (4)
N3ⁱ—Pr2—Si2ⁱⁱⁱ	32.00 (18)	N3^ix—Si2—Pr1^ix	53.5 (3)
N4^iv—Pr2—Si2ⁱⁱⁱ	98.41 (18)	N3^x—Si2—Pr1^ix	53.5 (3)
N5—Pr2—Si2ⁱⁱⁱ	113.5 (2)	Pr3^ix—Si2—Pr1^ix	68.39 (7)
N1ⁱⁱⁱ—Pr2—Si2ⁱⁱⁱ	32.6 (2)	Pr1—Si2—Pr1^ix	165.93 (11)
N5^v—Pr2—Si2ⁱⁱⁱ	148.38 (18)	Pr2^ix—Si2—Pr1^ix	72.74 (6)
N6—Pr2—Si2ⁱⁱⁱ	74.5 (2)	Pr2^x—Si2—Pr1^ix	72.74 (6)
N3^vi—Pr2—Si2ⁱⁱⁱ	85.88 (18)	N2—Si2—Pr2^xiii	63.03 (5)
Si3—Pr2—Si2ⁱⁱⁱ	65.15 (5)	N1—Si2—Pr2^xiii	102.34 (17)
N3ⁱ—Pr2—Si1	108.77 (18)	N3^ix—Si2—Pr2^xiii	55.5 (3)
N4^iv—Pr2—Si1	104.47 (19)	N3^x—Si2—Pr2^xiii	144.5 (3)
N5—Pr2—Si1	32.8 (2)	Pr3^ix—Si2—Pr2^xiii	79.51 (6)
N1ⁱⁱⁱ—Pr2—Si1	74.5 (2)	Pr1—Si2—Pr2^xiii	76.47 (6)
N5^v—Pr2—Si1	83.71 (16)	Pr2^ix—Si2—Pr2^xiii	157.94 (9)
N6—Pr2—Si1	32.5 (2)	Pr2^x—Si2—Pr2^xiii	71.77 (2)
N3^vi—Pr2—Si1	151.39 (17)	Pr1^ix—Si2—Pr2^xiii	108.81 (6)
Si3—Pr2—Si1	121.96 (6)	N2—Si2—Pr2^xvii	63.03 (5)
Si2ⁱⁱⁱ—Pr2—Si1	91.60 (6)	N1—Si2—Pr2^xvii	102.34 (17)
N3ⁱ—Pr2—Si2^iv	85.02 (18)	N3^ix—Si2—Pr2^xvii	144.5 (3)
N4^iv—Pr2—Si2^iv	80.27 (19)	N3^x—Si2—Pr2^xvii	55.5 (3)
N5—Pr2—Si2^iv	135.8 (2)	Pr3^ix—Si2—Pr2^xvii	79.51 (6)
N1ⁱⁱⁱ—Pr2—Si2^iv	125.3 (2)	Pr1—Si2—Pr2^xvii	76.47 (6)
N5^v—Pr2—Si2^iv	76.68 (16)	Pr2^ix—Si2—Pr2^xvii	71.77 (2)
N6—Pr2—Si2^iv	146.3 (2)	Pr2^x—Si2—Pr2^xvii	157.94 (9)
N3^vi—Pr2—Si2^iv	29.85 (17)	Pr1^ix—Si2—Pr2^xvii	108.81 (6)
Si3—Pr2—Si2^iv	62.78 (6)	Pr2^xiii—Si2—Pr2^xvii	125.65 (10)
Si2ⁱⁱⁱ—Pr2—Si2^iv	107.04 (3)	N3^vi—Si3—N3ⁱ	99.8 (6)
Si1—Pr2—Si2^iv	160.04 (7)	N3^vi—Si3—N4^vi	107.8 (4)
N3ⁱ—Pr2—Pr4^iv	160.79 (17)	N3ⁱ—Si3—N4^vi	106.7 (4)
N4^iv—Pr2—Pr4^iv	44.35 (17)	N3^vi—Si3—N4ⁱ	106.7 (4)
N5—Pr2—Pr4^iv	42.36 (19)	N3ⁱ—Si3—N4ⁱ	107.8 (4)
N1ⁱⁱⁱ—Pr2—Pr4^iv	99.7 (2)	N4^vi—Si3—N4ⁱ	125.2 (5)
N5^v—Pr2—Pr4^iv	77.38 (17)	N3^vi—Si3—Pr1	138.4 (3)
N6—Pr2—Pr4^iv	107.2 (2)	N3ⁱ—Si3—Pr1	59.3 (3)
N3^vi—Pr2—Pr4^iv	126.40 (17)	N4^vi—Si3—Pr1	112.5 (3)
Si3—Pr2—Pr4^iv	158.49 (2)	N4ⁱ—Si3—Pr1	56.5 (3)
Si2ⁱⁱⁱ—Pr2—Pr4^iv	131.58 (6)	N3^vi—Si3—Pr1^vi	59.3 (3)
Si1—Pr2—Pr4^iv	75.19 (5)	N3ⁱ—Si3—Pr1^vi	138.4 (3)
Si2^iv—Pr2—Pr4^iv	96.64 (5)	N4^vi—Si3—Pr1^vi	56.5 (3)
N1—Pr3—N5^vii	148.38 (19)	N4ⁱ—Si3—Pr1^vi	112.5 (3)
N1—Pr3—N5^viii	148.38 (19)	Pr1—Si3—Pr1^vi	158.86 (12)
N5^vii—Pr3—N5^viii	60.6 (3)	N3^vi—Si3—Pr2^xviii	56.1 (3)
N1—Pr3—N5^ix	85.2 (3)	N3ⁱ—Si3—Pr2^xviii	62.7 (3)
N5^vii—Pr3—N5^ix	72.6 (3)	N4^vi—Si3—Pr2^xviii	79.7 (3)
N5^viii—Pr3—N5^ix	101.2 (2)	N4ⁱ—Si3—Pr2^xviii	154.9 (3)
N1—Pr3—N5^x	85.2 (3)	Pr1—Si3—Pr2^xviii	121.79 (7)
N5^vii—Pr3—N5^x	101.2 (2)	Pr1^vi—Si3—Pr2^xviii	76.26 (3)
N5^viii—Pr3—N5^x	72.6 (3)	N3^vi—Si3—Pr2	62.7 (3)
N5^ix—Pr3—N5^x	58.6 (3)	N3ⁱ—Si3—Pr2	56.1 (3)
N1—Pr3—N4^xi	74.78 (15)	N4^vi—Si3—Pr2	154.9 (3)
N5^vii—Pr3—N4^xi	136.0 (2)	N4ⁱ—Si3—Pr2	79.7 (3)
N5^viii—Pr3—N4^xi	75.5 (2)	Pr1—Si3—Pr2	76.26 (3)
N5^ix—Pr3—N4^xi	120.9 (2)	Pr1^vi—Si3—Pr2	121.79 (7)
N5^x—Pr3—N4^xi	64.7 (2)	Pr2^xviii—Si3—Pr2	75.92 (8)
N1—Pr3—N4^vi	74.78 (15)	N3^vi—Si3—Pr3	134.2 (3)
N5^vii—Pr3—N4^vi	75.5 (2)	N3ⁱ—Si3—Pr3	55.4 (3)
N5^viii—Pr3—N4^vi	136.0 (2)	N4^vi—Si3—Pr3	56.9 (3)
N5^ix—Pr3—N4^vi	64.7 (2)	N4ⁱ—Si3—Pr3	117.0 (3)
N5^x—Pr3—N4^vi	120.9 (2)	Pr1—Si3—Pr3	66.28 (2)
N4^xi—Pr3—N4^vi	148.3 (3)	Pr1^vi—Si3—Pr3	111.45 (3)
N1—Pr3—Si1^viii	171.4 (3)	Pr2^xviii—Si3—Pr3	78.13 (3)
N5^vii—Pr3—Si1^viii	34.86 (17)	Pr2—Si3—Pr3	111.28 (6)
N5^viii—Pr3—Si1^viii	34.86 (17)	N3^vi—Si3—Pr3^vi	55.4 (3)
N5^ix—Pr3—Si1^viii	102.31 (17)	N3ⁱ—Si3—Pr3^vi	134.2 (3)
N5^x—Pr3—Si1^viii	102.31 (17)	N4^vi—Si3—Pr3^vi	117.0 (3)
N4^xi—Pr3—Si1^viii	104.38 (15)	N4ⁱ—Si3—Pr3^vi	56.9 (3)
N4^vi—Pr3—Si1^viii	104.38 (15)	Pr1—Si3—Pr3^vi	111.45 (3)
N1—Pr3—Si2ⁱⁱⁱ	105.8 (3)	Pr1^vi—Si3—Pr3^vi	66.28 (2)
N5^vii—Pr3—Si2ⁱⁱⁱ	84.53 (19)	Pr2^xviii—Si3—Pr3^vi	111.28 (6)
N5^viii—Pr3—Si2ⁱⁱⁱ	84.53 (19)	Pr2—Si3—Pr3^vi	78.13 (3)
N5^ix—Pr3—Si2ⁱⁱⁱ	149.10 (17)	Pr3—Si3—Pr3^vi	168.55 (11)
N5^x—Pr3—Si2ⁱⁱⁱ	149.10 (17)	Si2—N1—Pr3	178.3 (7)
N4^xi—Pr3—Si2ⁱⁱⁱ	89.97 (15)	Si2—N1—Pr1	87.3 (5)
N4^vi—Pr3—Si2ⁱⁱⁱ	89.97 (15)	Pr3—N1—Pr1	91.1 (4)
Si1^viii—Pr3—Si2ⁱⁱⁱ	65.53 (9)	Si2—N1—Pr2^ix	89.8 (3)
N1—Pr3—Si3ⁱⁱ	71.58 (17)	Pr3—N1—Pr2^ix	91.1 (3)
N5^vii—Pr3—Si3ⁱⁱ	137.36 (18)	Pr1—N1—Pr2^ix	124.3 (2)
N5^viii—Pr3—Si3ⁱⁱ	87.79 (18)	Si2—N1—Pr2^x	89.8 (3)
N5^ix—Pr3—Si3ⁱⁱ	146.45 (18)	Pr3—N1—Pr2^x	91.1 (3)
N5^x—Pr3—Si3ⁱⁱ	94.75 (16)	Pr1—N1—Pr2^x	124.3 (2)
N4^xi—Pr3—Si3ⁱⁱ	30.36 (15)	Pr2^ix—N1—Pr2^x	111.2 (4)
N4^vi—Pr3—Si3ⁱⁱ	127.82 (14)	Si2—N2—Si1^xv	147.4 (8)
Si1^viii—Pr3—Si3ⁱⁱ	103.21 (6)	Si2—N2—Pr1	94.0 (4)
Si2ⁱⁱⁱ—Pr3—Si3ⁱⁱ	63.20 (6)	Si1^xv—N2—Pr1	118.6 (6)
N1—Pr3—Si3	71.58 (17)	Si3ⁱⁱ—N3—Si2ⁱⁱⁱ	175.7 (6)
N5^vii—Pr3—Si3	87.79 (18)	Si3ⁱⁱ—N3—Pr2ⁱ	90.7 (4)
N5^viii—Pr3—Si3	137.36 (18)	Si2ⁱⁱⁱ—N3—Pr2ⁱ	93.4 (3)
N5^ix—Pr3—Si3	94.75 (16)	Si3ⁱⁱ—N3—Pr1	85.9 (3)
N5^x—Pr3—Si3	146.45 (18)	Si2ⁱⁱⁱ—N3—Pr1	94.7 (3)
N4^xi—Pr3—Si3	127.82 (14)	Pr2ⁱ—N3—Pr1	93.9 (3)
N4^vi—Pr3—Si3	30.36 (15)	Si3ⁱⁱ—N3—Pr2ⁱⁱ	84.3 (3)
Si1^viii—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—Si1^ix	74.8 (3)	Si3ⁱⁱ—N4—Pr2^xiii	124.0 (4)
N5^vii—Pr3—Si1^ix	94.91 (19)	Si3ⁱⁱ—N4—Pr4	143.3 (4)
N5^viii—Pr3—Si1^ix	94.91 (19)	Pr2^xiii—N4—Pr4	92.1 (2)
N5^ix—Pr3—Si1^ix	30.70 (16)	Si3ⁱⁱ—N4—Pr1	88.3 (3)
N5^x—Pr3—Si1^ix	30.70 (16)	Pr2^xiii—N4—Pr1	108.9 (3)
N4^xi—Pr3—Si1^ix	90.21 (15)	Pr4—N4—Pr1	85.3 (2)
N4^vi—Pr3—Si1^ix	90.21 (15)	Si3ⁱⁱ—N4—Pr3ⁱⁱ	92.7 (3)
Si1^viii—Pr3—Si1^ix	113.82 (7)	Pr2^xiii—N4—Pr3ⁱⁱ	84.8 (2)
Si2ⁱⁱⁱ—Pr3—Si1^ix	179.35 (8)	Pr4—N4—Pr3ⁱⁱ	83.5 (2)
Si3ⁱⁱ—Pr3—Si1^ix	117.13 (6)	Pr1—N4—Pr3ⁱⁱ	162.7 (3)
Si3—Pr3—Si1^ix	117.13 (6)	Si1—N5—Pr4^iv	169.2 (5)
N5^xii—Pr4—N5^xiii	88.2 (4)	Si1—N5—Pr2	97.4 (4)
N5^xii—Pr4—N4	90.6 (3)	Pr4^iv—N5—Pr2	93.2 (3)
N5^xiii—Pr4—N4	78.2 (3)	Si1—N5—Pr3^xvi	81.5 (3)
N5^xii—Pr4—N4^xiv	78.2 (3)	Pr4^iv—N5—Pr3^xvi	87.8 (3)
N5^xiii—Pr4—N4^xiv	90.6 (3)	Pr2—N5—Pr3^xvi	163.4 (4)
N4—Pr4—N4^xiv	164.5 (4)	Si1—N5—Pr3ⁱⁱⁱ	93.7 (4)
N5^xii—Pr4—N6	100.3 (3)	Pr4^iv—N5—Pr3ⁱⁱⁱ	85.8 (3)
N5^xiii—Pr4—N6	161.9 (3)	Pr2—N5—Pr3ⁱⁱⁱ	84.7 (2)
N4—Pr4—N6	85.6 (3)	Pr3^xvi—N5—Pr3ⁱⁱⁱ	78.8 (2)
N4^xiv—Pr4—N6	106.7 (3)	Si1—N5—Pr2^v	95.3 (4)
N5^xii—Pr4—N6^xv	161.9 (3)	Pr4^iv—N5—Pr2^v	83.8 (3)
N5^xiii—Pr4—N6^xv	100.3 (3)	Pr2—N5—Pr2^v	102.0 (3)
N4—Pr4—N6^xv	106.7 (3)	Pr3^xvi—N5—Pr2^v	94.6 (2)
N4^xiv—Pr4—N6^xv	85.6 (3)	Pr3ⁱⁱⁱ—N5—Pr2^v	167.9 (3)
N6—Pr4—N6^xv	76.3 (4)	Si1—N6—Pr1	168.4 (7)
N5^xii—Pr4—Pr1	119.2 (2)	Si1—N6—Pr4	106.5 (4)
N5^xiii—Pr4—Pr1	115.63 (19)	Pr1—N6—Pr4	80.3 (3)
N4—Pr4—Pr1	47.91 (18)	Si1—N6—Pr4^xv	106.5 (4)
N4^xiv—Pr4—Pr1	147.47 (18)	Pr1—N6—Pr4^xv	80.3 (3)
N6—Pr4—Pr1	46.3 (2)	Pr4—N6—Pr4^xv	103.7 (4)
N6^xv—Pr4—Pr1	71.6 (2)	Si1—N6—Pr2	83.1 (3)
N5^xii—Pr4—Pr1^xv	115.63 (19)	Pr1—N6—Pr2	89.4 (3)
N5^xiii—Pr4—Pr1^xv	119.2 (2)	Pr4—N6—Pr2	169.3 (5)
N4—Pr4—Pr1^xv	147.47 (18)	Pr4^xv—N6—Pr2	77.32 (4)
N4^xiv—Pr4—Pr1^xv	47.91 (18)	Si1—N6—Pr2ⁱ	83.1 (3)
N6—Pr4—Pr1^xv	71.6 (2)	Pr1—N6—Pr2ⁱ	89.4 (3)
N6^xv—Pr4—Pr1^xv	46.3 (2)	Pr4—N6—Pr2ⁱ	77.32 (4)
Pr1—Pr4—Pr1^xv	100.33 (3)	Pr4^xv—N6—Pr2ⁱ	169.3 (5)
N5^xii—Pr4—Pr2^xiii	111.17 (19)	Pr2—N6—Pr2ⁱ	99.7 (3)
N5^xiii—Pr4—Pr2^xiii	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.

Experimental details

Crystal data
Chemical formula	Pr₅Si₃N₉
M_r	914.91
Crystal system, space group	Orthorhombic, Cmce
Temperature (K)	293
a, b, c (Å)	10.512 (2), 11.243 (2), 15.773 (3)
V (Å³)	1864.2 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	26.01
Crystal size (mm)	0.17 × 0.10 × 0.08

Data collection
Diffractometer	Stoe IPDS diffractometer
Absorption correction	Multi-scan (XPREP; Sheldrick, 2008)
T_min, T_max	0.040, 0.125
No. of measured, independent and observed [I > 2σ(I)] reflections	9626, 1480, 1133
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.097, 0.97
No. of reflections	1480
No. of parameters	90
Δρ_max, Δρ_min (e Å⁻³)	2.10, −2.31

Computer programs: X-AREA (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Acknowledgements

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.

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Lissner, F. & Schleid, T. (2004). Z. Anorg. Allg. Chem. 630, 2226–2230. Web of Science CrossRef CAS Google Scholar
Schmolke, C., Bichler, D., Johrendt, D. & Schnick, W. (2009). Solid State Sci. 11, 389–394. Web of Science CrossRef CAS Google Scholar
Schnick, W. (2001). Int. J. Inorg. Mater. 3, 1267–1272. Web of Science CrossRef CAS Google Scholar
Schnick, W. & Huppertz, H. (1997). Chem. Eur. J. 3, 679–683. CrossRef CAS Web of Science Google Scholar
Schnick, W., Huppertz, H. & Lauterbach, R. (1999). J. Mater. Chem. 9, 289–296. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2002). X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar