La3Si6N11

Yamane, H.; Nagura, T.; Miyazaki, T.

doi:10.1107/S1600536814009234

inorganic compounds

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ISSN: 2056-9890

Volume 70| Part 6| June 2014| Pages i23-i24

doi:10.1107/S1600536814009234

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La₃Si₆N₁₁

Hisanori Yamane,^a ^* Toshiki Nagura ^a and Tomohiro Miyazaki ^a

^aInstitute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577, Japan
^*Correspondence e-mail: yamane@tagen.tohoku.ac.jp

(Received 7 April 2014; accepted 24 April 2014; online 3 May 2014)

Colorless transparent single crystals of trilanthanum hexasilicon undecanitrogen, La₃Si₆N₁₁, were prepared at 0.85 MPa of N₂ and 2273 K. The title compound is isotypic with Sm₃Si₆N₁₁. Silicon-centered nitrogen tetrahedra form a three-dimensional network structure by sharing their corners. Layers of one type of SiN₄ tetrahedra and slabs composed of the two different La³⁺ cations and the other type of SiN₄ tetrahedra are alternately stacked along the c axis of the tetragonal unit cell. The site symmetries of the two La³⁺ cations are are ..m and 4.., respectively.

CCDC reference: 999175

Related literature

For the lattice parameters of La₃Si₆N₁₁, see: Woike & Jeitschko (1995 ). For isotypic Ce₃Si₆N₁₁, Pr₃Si₆N₁₁, Nd₃Si₆N₁₁, Sm₃Si₆N₁₁ and La₃Si₅AlON₁₀, see: Gaudé et al. (1983 ); Woike & Jeitschko (1995); Schlieper & Schnick (1995 , 1996 ); Lauterbach & Schnick (2000 ). Recently, La₃Si₆N₁₁ has received attention as a host crystal of phosphors by Ce³⁺ doping; for La₃Si₆N₁₁:Ce, (La,Ca)₃Si₆N₁₁:Ce, see: Seto et al. (2009 ); Suehiro et al. (2011 ); George et al. (2013 ). For the ionic radii of La³⁺ and Sm³⁺ cations in nitrides, see: Baur (1987 ). For the Madelung energies of La₃Si₆N₁₁, LaN and Si₃N₄, see: Hoppe (1966 , 1970 ), Klemm & Winkelmann (1956 ) and Boulay et al. (2004 ), respectively.

Experimental

Crystal data

La₃Si₆N₁₁
M_r = 739.38
Tetragonal, P 4b m
a = 10.1988 (4) Å
c = 4.84153 (19) Å
V = 503.60 (3) Å³
Z = 2
Mo Kα radiation
μ = 13.22 mm⁻¹
T = 293 K
0.15 × 0.14 × 0.03 mm

Data collection

Rigaku R-AXIS RAPID II diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ) T_min = 0.219, T_max = 0.726
4700 measured reflections
624 independent reflections
599 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.017
wR(F²) = 0.030
S = 1.20
624 reflections
39 parameters
1 restraint
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.90 e Å⁻³
Absolute structure: Flack (1983 ), 275 Friedel pairs
Absolute structure parameter: 0.05 (3)

Table 1
Selected bond lengths (Å)

La1—N1ⁱ	2.551 (3)
La1—N1ⁱⁱ	2.551 (3)
La1—N4	2.6227 (7)
La1—N2ⁱⁱⁱ	2.674 (3)
La1—N2^iv	2.674 (3)
La1—N2^v	2.853 (3)
La1—N2^vi	2.853 (3)
La1—N3^vii	2.864 (5)
La2—N2	2.644 (3)
La2—N2^viii	2.644 (3)
La2—N2^ix	2.644 (3)
La2—N2^x	2.644 (3)
La2—N1^xi	2.649 (3)
La2—N1^xii	2.649 (3)
La2—N1^xiii	2.649 (3)
La2—N1^xiv	2.649 (3)
Si1—N1^x	1.724 (3)
Si1—N2	1.729 (4)
Si1—N1	1.743 (3)
Si1—N3^xv	1.776 (3)
Si2—N4^xvi	1.6868 (14)
Si2—N2^xvii	1.725 (4)
Si2—N2^xvi	1.725 (4)
Si2—N3^xiv	1.764 (5)
Symmetry codes: (i) -y+1, x, z-1; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-1]$ ; (iii) -y+1, x, z; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (v) $[-y+{\script{1\over 2}}, -x+{\script{1\over 2}}, z]$ ; (vi) -x+1, -y, z; (vii) -x+1, -y+1, z-1; (viii) -y, x, z; (ix) -x, -y, z; (x) y, -x, z; (xi) -x, -y, z-1; (xii) -y, x, z-1; (xiii) y, -x, z-1; (xiv) x, y, z-1; (xv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (xvi) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (xvii) y, -x+1, z.

Data collection: PROCESS-AUTO (Rigaku/MSC, 2005 ); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: VESTA (Momma & Izumi, 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 999175

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814009234/ru2057sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814009234/ru2057Isup2.hkl

checkCIF report

Comment top

Woike and Jeitschko (1995) measured the tetragonal unit cell parameters of La₃Si₆N₁₁ by X-ray powder diffraction and showed that Ln₃Si₆N₁₁, Ln = Sr, as well as Ce, Pr, Nd, is isostructural with Sm₃Si₆N₁₁ firstly reported by Gaudé et al. (1983). The crystal structure of Sm₃Si₆N₁₁ was analyzed by single crystal X-ray diffraction with the noncentrosymmetric space group P4bm (Woike & Jeitschko, 1995). The crystal structures of isotypic compounds, Ce₃Si₆N₁₁, Pr₃Si₆N₁₁ and La₃Si₅AlON₁₀ (Schlieper & Schnick, 1995, 1996; Lauterbach & Schinick, 2000), have also been studied, while there is no report on the structure parameters of La₃Si₆N₁₁. Recently, La₃Si₆N₁₁ has received attention as host crystals of phosphors by Ce³⁺ doping (Seto et al., 2009; Suehiro et al., 2011; George et al., 2013).

The cell parameters and volume determined by single crystal X-ray diffraction are close to those (a = 10.189 (1) Å, c = 4.837 (2) Å, V = 502.2 (2) Å³) reported in the previous study (Woike & Jeitschko, 1995). Fig. 1 shows the coordination environments of the Si1, Si2, La1 and La2 atoms. Si1 atoms are at general positions 8d and Si2 at special position 4c. Si1—N and Si2—N bond lengths are in the ranges of 1.724 (3)–1.776 (3) Å, and 1.6868 (14)–1.764 (5) Å, respectively. These ranges are comparable with those (1.709–1.775 Å and 1.675–1.753 Å) reported for Sm₃Si₆N₁₁ (Woike & Jeitschko, 1995).

La1 atoms at 4c site with site symmetry (..m) and La2 atom at 2a site with (4..) are surrounded by 8 N atoms. La1—N distances of 2.551 (3)–2.864 (5) Å and La2—N distances of 2.644 (3) Å and 2.649 (3) Å are longer than the distances of Sm1—N (2.417–2.866 Å ) and Sm2—N (2.557 Å and 2.571 Å) in Sm₃Si₆N₁₁, which is in accordance with the difference between the effective ionic radii of La (1.25 Å) and Sm (1.15 Å) atoms in nitrides (Baur, 1987).

The site potentials calculated with the structure parameters using VESTA program (Momma & Izumi 2008) are -27.3 V (La1³⁺), 28.5 V (La2³⁺), -51.9 V (Si1⁴⁺), -51.6 V (Si2⁴⁺) and 36.6–39.4 V (N^3- sites). The value of the Madelung energy for La₃Si₆N₁₁ (MAPLE, MAdelung Part of Lattice Energy, Hoppe 1966, 1970) is -132,000 kJ/mol, which are almost identical to the value of -131,300 kJ/mol (difference Δ = 0.5%) of the Madelung energies: LaN (-8,240 kJ/mol, Klemm & Winkelman, 1956) and Si₃N₄ (-53,300 kJ/mol, Boulay et al., 2004) with the formula 3LaN + 2Si₃N₄ → La₃Si₆N₁₁.

Experimental top

Starting powders of LaN (0.6205 g, Koujundo Chemical Laboratory Co., Ltd.) and Si₃N₄ (0.3795 g, SN—E10, Ube Industries, Ltd.) were weighed and mixed in an aluminum mortar with a pestle in an Ar gas-filled glove box (O₂ and H₂O < 1 ppm). A sintered BN crucible (UHS-FL, inside diameter 18 mm; depth 18 mm, Showa Denko K. K., 99.5%) was loaded with the powder mixture and heated at 0.9 MPa of N₂ (99.9995%) and 1800°C for 2 h with a gas pressure carbon furnace (VESTA, Shimadzu Mectem, Inc.). The obtained product was powdered with the mortar and pestle and heated at 0.85 MPa of N₂ and 2000°C for 4 h. Colorless transparent single crystals (size less than 0.15 mm) were obtained in the product.

Refinement top

Because the principal mean square atomic displacement for the N2 site was not positive definite, isotropic displacement parameters were refined for all nitrogen sites. The highest peak in the difference electron density map was 1.11 Å from La2 while the deepest hole was 0.79 Å from the same atom.

Related literature top

For the lattice parameters of La₃Si₆N₁₁, see: Woike & Jeitschko (1995). For isotypic Ce₃Si₆N₁₁, Pr₃Si₆N₁₁, Nd₃Si₆N₁₁, Sm₃Si₆N₁₁ and La₃Si₅AlON₁₀, see: Gaudé et al. (1983); Woike & Jeitschko (1995); Schlieper & Schnick (1995, 1996); Lauterbach & Schinick (2000). Recently, La₃Si₆N₁₁ has received attention as a host crystal of phosphors by Ce³⁺ doping; for La₃Si₆N₁₁:Ce, (La,Ca)₃Si₆N₁₁:Ce, see: Seto et al. (2009); Suehiro et al. (2011); George et al. (2013). For the ionic radii of La and Sm atoms in nitrides, see: Baur (1987). For the Madelung energies of La₃Si₆N₁₁, LaN and Si₃N₄, see: Hoppe (1966, 1970), Klemm & Winkelman (1956) and Boulay et al. (2004), respectively.

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC, 2005); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2005); data reduction: PROCESS-AUTO (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: VESTA (Momma & Izumi, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The atomic arrangement around La and Si atoms in the structure of La₃Si₆N₁₁. The displacement ellipsoids of La1, La2, Si1 and Si2 are drawn at the 95%. Symmetry codes are listed in Geometric parameters.
	Fig. 2. The crystal structure of La₃Si₆N₁₁ in a representation using cation-centered nitrogen polyhedra.

Trilanthanum hexasilicon undecanitrogen top

Crystal data top

La₃Si₆N₁₁	D_x = 4.876 Mg m⁻³
M_r = 739.38	Mo Kα radiation, λ = 0.71075 Å
Tetragonal, P4bm	Cell parameters from 4239 reflections
Hall symbol: P 4 -2ab	θ = 4.0–27.5°
a = 10.1988 (4) Å	µ = 13.22 mm⁻¹
c = 4.84153 (19) Å	T = 293 K
V = 503.60 (3) Å³	Chunk, colorless
Z = 2	0.15 × 0.14 × 0.03 mm
F(000) = 664

Data collection top

Rigaku R-AXIS RAPID II diffractometer	624 independent reflections
Radiation source: fine-focus sealed tube	599 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.5°, θ_min = 4.0°
ω scans	h = −13→13
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −13→12
T_min = 0.219, T_max = 0.726	l = −6→6
4700 measured reflections

Refinement top

Refinement on F²	w = 1/[σ²(F_o²) + (0.0093P)² + 0.0181P] where P = (F_o² + 2F_c²)/3
Least-squares matrix: full	(Δ/σ)_max = 0.002
R[F² > 2σ(F²)] = 0.017	Δρ_max = 0.83 e Å⁻³
wR(F²) = 0.030	Δρ_min = −0.90 e Å⁻³
S = 1.20	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
624 reflections	Extinction coefficient: 0.0007 (2)
39 parameters	Absolute structure: Flack (1983), 275 Friedel pairs
1 restraint	Absolute structure parameter: 0.05 (3)

Crystal data top

La₃Si₆N₁₁	Z = 2
M_r = 739.38	Mo Kα radiation
Tetragonal, P4bm	µ = 13.22 mm⁻¹
a = 10.1988 (4) Å	T = 293 K
c = 4.84153 (19) Å	0.15 × 0.14 × 0.03 mm
V = 503.60 (3) Å³

Data collection top

Rigaku R-AXIS RAPID II diffractometer	624 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	599 reflections with I > 2σ(I)
T_min = 0.219, T_max = 0.726	R_int = 0.039
4700 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	1 restraint
wR(F²) = 0.030	Δρ_max = 0.83 e Å⁻³
S = 1.20	Δρ_min = −0.90 e Å⁻³
624 reflections	Absolute structure: Flack (1983), 275 Friedel pairs
39 parameters	Absolute structure parameter: 0.05 (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
La1	0.680962 (17)	0.180962 (17)	0.01861 (13)	0.00578 (9)
La2	0.0000	0.0000	0.00000 (11)	0.00427 (11)
Si1	0.20985 (9)	0.07807 (8)	0.5344 (4)	0.0038 (2)
Si2	0.11658 (9)	0.61658 (9)	0.0439 (5)	0.0039 (3)
N1	0.0803 (3)	0.1779 (3)	0.6388 (7)	0.0056 (7)*
N2	0.2332 (3)	0.0739 (3)	0.1807 (8)	0.0060 (8)*
N3	0.1527 (3)	0.6527 (3)	0.6958 (10)	0.0044 (10)*
N4	0.5000	0.0000	0.0717 (14)	0.0055 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.00443 (11)	0.00443 (11)	0.00849 (17)	−0.00036 (9)	0.0001 (2)	0.0001 (2)
La2	0.00378 (13)	0.00378 (13)	0.0053 (2)	0.000	0.000	0.000
Si1	0.0037 (4)	0.0036 (4)	0.0040 (6)	−0.0006 (3)	0.0005 (7)	−0.0008 (7)
Si2	0.0038 (4)	0.0038 (4)	0.0042 (10)	0.0000 (5)	0.0005 (6)	0.0005 (6)

Geometric parameters (Å, º) top

La1—N1ⁱ	2.551 (3)	Si1—N1	1.743 (3)
La1—N1ⁱⁱ	2.551 (3)	Si1—N3^ix	1.776 (3)
La1—N4	2.6227 (7)	Si1—La2^xvii	3.2089 (16)
La1—N2ⁱⁱⁱ	2.674 (3)	Si1—La1^xviii	3.4093 (16)
La1—N2^iv	2.674 (3)	Si1—La1^xix	3.5159 (17)
La1—N2^v	2.853 (3)	Si2—N4^xx	1.6868 (14)
La1—N2^vi	2.853 (3)	Si2—N2^xxi	1.725 (4)
La1—N3^vii	2.864 (5)	Si2—N2^xx	1.725 (4)
La1—Si2^viii	2.9227 (13)	Si2—N3^xvi	1.764 (5)
La1—Si2^ix	3.1072 (7)	Si2—La1^viii	2.9228 (13)
La1—Si2^iv	3.1072 (7)	Si2—La1^xx	3.1072 (7)
La1—Si1ⁱⁱ	3.4093 (16)	Si2—La1^xix	3.1072 (7)
La2—N2	2.644 (3)	N1—Si1^x	1.724 (3)
La2—N2^x	2.644 (3)	N1—La1^xviii	2.551 (3)
La2—N2^xi	2.644 (3)	N1—La2^xvii	2.649 (3)
La2—N2^xii	2.644 (3)	N2—Si2^ix	1.725 (4)
La2—N1^xiii	2.649 (3)	N2—La1^xix	2.674 (3)
La2—N1^xiv	2.649 (3)	N2—La1^vi	2.853 (3)
La2—N1^xv	2.649 (3)	N3—Si2^xvii	1.764 (5)
La2—N1^xvi	2.649 (3)	N3—Si1^xxi	1.776 (3)
La2—Si1^xiii	3.2089 (16)	N3—Si1^xx	1.776 (3)
La2—Si1^xv	3.2089 (16)	N3—La1^xxii	2.864 (5)
La2—Si1^xiv	3.2089 (16)	N4—Si2^iv	1.6868 (14)
La2—Si1^xvi	3.2089 (16)	N4—Si2^ix	1.6868 (14)
Si1—N1^xii	1.724 (3)	N4—La1^vi	2.6227 (7)
Si1—N2	1.729 (4)

N1ⁱ—La1—N1ⁱⁱ	86.25 (15)	N2^xii—La2—Si1^xv	64.01 (8)
N1ⁱ—La1—N4	100.64 (13)	N1^xiii—La2—Si1^xv	32.47 (7)
N1ⁱⁱ—La1—N4	100.64 (13)	N1^xiv—La2—Si1^xv	84.97 (8)
N1ⁱ—La1—N2ⁱⁱⁱ	76.36 (10)	N1^xv—La2—Si1^xv	32.88 (7)
N1ⁱⁱ—La1—N2ⁱⁱⁱ	118.37 (10)	N1^xvi—La2—Si1^xv	85.19 (8)
N4—La1—N2ⁱⁱⁱ	140.30 (11)	Si1^xiii—La2—Si1^xv	60.42 (3)
N1ⁱ—La1—N2^iv	118.37 (10)	N2—La2—Si1^xiv	105.41 (8)
N1ⁱⁱ—La1—N2^iv	76.36 (10)	N2^x—La2—Si1^xiv	64.01 (8)
N4—La1—N2^iv	140.30 (11)	N2^xi—La2—Si1^xiv	101.50 (8)
N2ⁱⁱⁱ—La1—N2^iv	62.68 (14)	N2^xii—La2—Si1^xiv	154.58 (9)
N1ⁱ—La1—N2^v	146.72 (10)	N1^xiii—La2—Si1^xiv	85.19 (8)
N1ⁱⁱ—La1—N2^v	70.04 (11)	N1^xiv—La2—Si1^xiv	32.88 (7)
N4—La1—N2^v	63.11 (8)	N1^xv—La2—Si1^xiv	84.97 (8)
N2ⁱⁱⁱ—La1—N2^v	135.23 (11)	N1^xvi—La2—Si1^xiv	32.47 (7)
N2^iv—La1—N2^v	79.28 (14)	Si1^xiii—La2—Si1^xiv	60.42 (3)
N1ⁱ—La1—N2^vi	70.04 (11)	Si1^xv—La2—Si1^xiv	90.73 (6)
N1ⁱⁱ—La1—N2^vi	146.72 (10)	N2—La2—Si1^xvi	64.01 (8)
N4—La1—N2^vi	63.11 (8)	N2^x—La2—Si1^xvi	101.50 (8)
N2ⁱⁱⁱ—La1—N2^vi	79.28 (14)	N2^xi—La2—Si1^xvi	154.58 (9)
N2^iv—La1—N2^vi	135.23 (11)	N2^xii—La2—Si1^xvi	105.41 (8)
N2^v—La1—N2^vi	118.90 (14)	N1^xiii—La2—Si1^xvi	84.97 (8)
N1ⁱ—La1—N3^vii	60.70 (9)	N1^xiv—La2—Si1^xvi	85.19 (8)
N1ⁱⁱ—La1—N3^vii	60.70 (9)	N1^xv—La2—Si1^xvi	32.47 (7)
N4—La1—N3^vii	152.55 (18)	N1^xvi—La2—Si1^xvi	32.88 (7)
N2ⁱⁱⁱ—La1—N3^vii	59.21 (11)	Si1^xiii—La2—Si1^xvi	90.73 (6)
N2^iv—La1—N3^vii	59.21 (11)	Si1^xv—La2—Si1^xvi	60.42 (3)
N2^v—La1—N3^vii	120.55 (7)	Si1^xiv—La2—Si1^xvi	60.42 (3)
N2^vi—La1—N3^vii	120.55 (7)	N1^xii—Si1—N2	107.06 (17)
N1ⁱ—La1—Si2^viii	85.17 (8)	N1^xii—Si1—N1	108.6 (2)
N1ⁱⁱ—La1—Si2^viii	85.17 (8)	N2—Si1—N1	113.98 (17)
N4—La1—Si2^viii	171.97 (16)	N1^xii—Si1—N3^ix	114.9 (2)
N2ⁱⁱⁱ—La1—Si2^viii	35.54 (8)	N2—Si1—N3^ix	109.72 (19)
N2^iv—La1—Si2^viii	35.54 (8)	N1—Si1—N3^ix	102.7 (2)
N2^v—La1—Si2^viii	114.55 (7)	N1^xii—Si1—La2^xvii	55.61 (11)
N2^vi—La1—Si2^viii	114.55 (7)	N2—Si1—La2^xvii	141.40 (12)
N3^vii—La1—Si2^viii	35.48 (11)	N1—Si1—La2^xvii	55.63 (11)
N1ⁱ—La1—Si2^ix	119.64 (8)	N3^ix—Si1—La2^xvii	108.88 (17)
N1ⁱⁱ—La1—Si2^ix	75.81 (8)	N1^xii—Si1—La1^xviii	117.22 (14)
N4—La1—Si2^ix	32.88 (2)	N2—Si1—La1^xviii	135.29 (12)
N2ⁱⁱⁱ—La1—Si2^ix	160.67 (9)	N1—Si1—La1^xviii	46.68 (11)
N2^iv—La1—Si2^ix	112.38 (8)	N3^ix—Si1—La1^xviii	57.10 (16)
N2^v—La1—Si2^ix	33.29 (7)	La2^xvii—Si1—La1^xviii	68.78 (4)
N2^vi—La1—Si2^ix	95.52 (7)	N1^xii—Si1—La2	83.47 (12)
N3^vii—La1—Si2^ix	136.50 (7)	N2—Si1—La2	48.51 (12)
Si2^viii—La1—Si2^ix	146.89 (2)	N1—Si1—La2	83.23 (12)
N1ⁱ—La1—Si2^iv	75.81 (8)	N3^ix—Si1—La2	156.67 (16)
N1ⁱⁱ—La1—Si2^iv	119.64 (8)	La2^xvii—Si1—La2	93.20 (2)
N4—La1—Si2^iv	32.88 (2)	La1^xviii—Si1—La2	128.93 (3)
N2ⁱⁱⁱ—La1—Si2^iv	112.38 (8)	N1^xii—Si1—La1^xix	147.94 (14)
N2^iv—La1—Si2^iv	160.67 (9)	N2—Si1—La1^xix	47.60 (11)
N2^v—La1—Si2^iv	95.52 (7)	N1—Si1—La1^xix	74.59 (11)
N2^vi—La1—Si2^iv	33.29 (7)	N3^ix—Si1—La1^xix	94.54 (14)
N3^vii—La1—Si2^iv	136.50 (7)	La2^xvii—Si1—La1^xix	128.06 (3)
Si2^viii—La1—Si2^iv	146.89 (2)	La1^xviii—Si1—La1^xix	88.70 (2)
Si2^ix—La1—Si2^iv	65.52 (4)	La2—Si1—La1^xix	64.97 (3)
N1ⁱ—La1—Si1ⁱⁱ	75.26 (8)	N4^xx—Si2—N2^xxi	114.67 (16)
N1ⁱⁱ—La1—Si1ⁱⁱ	29.80 (7)	N4^xx—Si2—N2^xx	114.67 (16)
N4—La1—Si1ⁱⁱ	129.45 (13)	N2^xxi—Si2—N2^xx	107.5 (2)
N2ⁱⁱⁱ—La1—Si1ⁱⁱ	88.70 (8)	N4^xx—Si2—N3^xvi	111.7 (3)
N2^iv—La1—Si1ⁱⁱ	60.70 (8)	N2^xxi—Si2—N3^xvi	103.55 (17)
N2^v—La1—Si1ⁱⁱ	92.68 (7)	N2^xx—Si2—N3^xvi	103.55 (17)
N2^vi—La1—Si1ⁱⁱ	145.04 (8)	N4^xx—Si2—La1^viii	177.8 (3)
N3^vii—La1—Si1ⁱⁱ	31.39 (5)	N2^xxi—Si2—La1^viii	64.35 (12)
Si2^viii—La1—Si1ⁱⁱ	57.22 (5)	N2^xx—Si2—La1^viii	64.35 (12)
Si2^ix—La1—Si1ⁱⁱ	105.30 (4)	N3^xvi—Si2—La1^viii	70.43 (16)
Si2^iv—La1—Si1ⁱⁱ	138.54 (6)	N4^xx—Si2—La1^xx	57.57 (3)
N2—La2—N2^x	83.71 (5)	N2^xxi—Si2—La1^xx	65.22 (11)
N2—La2—N2^xi	141.35 (16)	N2^xx—Si2—La1^xx	159.37 (17)
N2^x—La2—N2^xi	83.71 (5)	N3^xvi—Si2—La1^xx	97.01 (10)
N2—La2—N2^xii	83.71 (5)	La1^viii—Si2—La1^xx	122.62 (2)
N2^x—La2—N2^xii	141.35 (16)	N4^xx—Si2—La1^xix	57.57 (3)
N2^xi—La2—N2^xii	83.71 (5)	N2^xxi—Si2—La1^xix	159.37 (17)
N2—La2—N1^xiii	133.76 (10)	N2^xx—Si2—La1^xix	65.22 (11)
N2^x—La2—N1^xiii	138.27 (10)	N3^xvi—Si2—La1^xix	97.01 (10)
N2^xi—La2—N1^xiii	75.24 (10)	La1^viii—Si2—La1^xix	122.62 (2)
N2^xii—La2—N1^xiii	71.98 (11)	La1^xx—Si2—La1^xix	114.28 (4)
N2—La2—N1^xiv	138.27 (10)	Si1^x—N1—Si1	137.4 (2)
N2^x—La2—N1^xiv	75.24 (10)	Si1^x—N1—La1^xviii	118.80 (16)
N2^xi—La2—N1^xiv	71.98 (11)	Si1—N1—La1^xviii	103.52 (15)
N2^xii—La2—N1^xiv	133.76 (10)	Si1^x—N1—La2^xvii	91.91 (13)
N1^xiii—La2—N1^xiv	64.17 (8)	Si1—N1—La2^xvii	91.49 (13)
N2—La2—N1^xv	71.98 (11)	La1^xviii—N1—La2^xvii	92.01 (11)
N2^x—La2—N1^xv	133.76 (10)	Si2^ix—N2—Si1	119.8 (2)
N2^xi—La2—N1^xv	138.27 (10)	Si2^ix—N2—La2	138.1 (2)
N2^xii—La2—N1^xv	75.24 (10)	Si1—N2—La2	102.16 (15)
N1^xiii—La2—N1^xv	64.17 (8)	Si2^ix—N2—La1^xix	80.11 (13)
N1^xiv—La2—N1^xv	97.40 (14)	Si1—N2—La1^xix	103.89 (15)
N2—La2—N1^xvi	75.24 (10)	La2—N2—La1^xix	89.42 (10)
N2^x—La2—N1^xvi	71.98 (11)	Si2^ix—N2—La1^vi	81.48 (12)
N2^xi—La2—N1^xvi	133.76 (10)	Si1—N2—La1^vi	109.71 (15)
N2^xii—La2—N1^xvi	138.27 (10)	La2—N2—La1^vi	85.71 (9)
N1^xiii—La2—N1^xvi	97.40 (14)	La1^xix—N2—La1^vi	146.33 (15)
N1^xiv—La2—N1^xvi	64.17 (8)	Si2^xvii—N3—Si1^xxi	119.72 (15)
N1^xv—La2—N1^xvi	64.17 (8)	Si2^xvii—N3—Si1^xx	119.72 (15)
N2—La2—Si1^xiii	154.58 (9)	Si1^xxi—N3—Si1^xx	118.9 (3)
N2^x—La2—Si1^xiii	105.41 (8)	Si2^xvii—N3—La1^xxii	74.09 (17)
N2^xi—La2—Si1^xiii	64.01 (8)	Si1^xxi—N3—La1^xxii	91.51 (17)
N2^xii—La2—Si1^xiii	101.50 (8)	Si1^xx—N3—La1^xxii	91.51 (17)
N1^xiii—La2—Si1^xiii	32.88 (7)	Si2^iv—N4—Si2^ix	170.9 (5)
N1^xiv—La2—Si1^xiii	32.47 (7)	Si2^iv—N4—La1^vi	89.55 (4)
N1^xv—La2—Si1^xiii	85.19 (8)	Si2^ix—N4—La1^vi	89.55 (4)
N1^xvi—La2—Si1^xiii	84.97 (8)	Si2^iv—N4—La1	89.55 (4)
N2—La2—Si1^xv	101.50 (8)	Si2^ix—N4—La1	89.55 (4)
N2^x—La2—Si1^xv	154.58 (9)	La1^vi—N4—La1	168.8 (3)
N2^xi—La2—Si1^xv	105.41 (8)

Symmetry codes: (i) −y+1, x, z−1; (ii) x+1/2, −y+1/2, z−1; (iii) −y+1, x, z; (iv) x+1/2, −y+1/2, z; (v) −y+1/2, −x+1/2, z; (vi) −x+1, −y, z; (vii) −x+1, −y+1, z−1; (viii) −x+1, −y+1, z; (ix) −x+1/2, y−1/2, z; (x) −y, x, z; (xi) −x, −y, z; (xii) y, −x, z; (xiii) −x, −y, z−1; (xiv) −y, x, z−1; (xv) y, −x, z−1; (xvi) x, y, z−1; (xvii) x, y, z+1; (xviii) x−1/2, −y+1/2, z+1; (xix) x−1/2, −y+1/2, z; (xx) −x+1/2, y+1/2, z; (xxi) y, −x+1, z; (xxii) −x+1, −y+1, z+1.

Selected bond lengths (Å) top

La1—N1ⁱ	2.551 (3)	La2—N1^xi	2.649 (3)
La1—N1ⁱⁱ	2.551 (3)	La2—N1^xii	2.649 (3)
La1—N4	2.6227 (7)	La2—N1^xiii	2.649 (3)
La1—N2ⁱⁱⁱ	2.674 (3)	La2—N1^xiv	2.649 (3)
La1—N2^iv	2.674 (3)	Si1—N1^x	1.724 (3)
La1—N2^v	2.853 (3)	Si1—N2	1.729 (4)
La1—N2^vi	2.853 (3)	Si1—N1	1.743 (3)
La1—N3^vii	2.864 (5)	Si1—N3^xv	1.776 (3)
La2—N2	2.644 (3)	Si2—N4^xvi	1.6868 (14)
La2—N2^viii	2.644 (3)	Si2—N2^xvii	1.725 (4)
La2—N2^ix	2.644 (3)	Si2—N2^xvi	1.725 (4)
La2—N2^x	2.644 (3)	Si2—N3^xiv	1.764 (5)

Symmetry codes: (i) −y+1, x, z−1; (ii) x+1/2, −y+1/2, z−1; (iii) −y+1, x, z; (iv) x+1/2, −y+1/2, z; (v) −y+1/2, −x+1/2, z; (vi) −x+1, −y, z; (vii) −x+1, −y+1, z−1; (viii) −y, x, z; (ix) −x, −y, z; (x) y, −x, z; (xi) −x, −y, z−1; (xii) −y, x, z−1; (xiii) y, −x, z−1; (xiv) x, y, z−1; (xv) −x+1/2, y−1/2, z; (xvi) −x+1/2, y+1/2, z; (xvii) y, −x+1, z.

Acknowledgements

We are grateful to Dr Kyota Ueda and Mr Satoshi Shimooka (Mitsubishi Chemical Group, Science and Technology Research Center, Inc.) for their help with the sample preparation. This work was supported in part by a Grant-in-Aid for Scientific Resarch (C) (No. 25420701, 2013) from the Ministry of Education, Culture, Sports and Technology (MEXT), Japan.

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Volume 70| Part 6| June 2014| Pages i23-i24

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