Literature DB >> 24940184

La3Si6N11.

Hisanori Yamane¹, Toshiki Nagura¹, Tomohiro Miyazaki¹.

Abstract

Colorless transparent single crystals of trilanthanum hexa-silicon undeca-nitro-gen, La3Si6N11, were prepared at 0.85 MPa of N2 and 2273 K. The title compound is isotypic with Sm3Si6N11. Silicon-centered nitro-gen tetra-hedra form a three-dimensional network structure by sharing their corners. Layers of one type of SiN4 tetra-hedra and slabs composed of the two different La(3+) cations and the other type of SiN4 tetra-hedra are alternately stacked along the c axis of the tetra-gonal unit cell. The site symmetries of the two La(3+) cations are are ..m and 4.., respectively.

Entities: CellLine Chemical Disease Gene Species

Year: 2014 PMID： 24940184 PMCID： PMC4051113 DOI： 10.1107/S1600536814009234

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

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 = 739.38 Tetragonal, 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[F 2 > 2σ(F 2)] = 0.017 wR(F 2) = 0.030 S = 1.20 624 reflections 39 parameters 1 restraint Δρmax = 0.83 e Å−3 Δρmin = −0.90 e Å−3 Absolute structure: Flack (1983 ▶), 275 Friedel pairs Absolute structure parameter: 0.05 (3) 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. Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814009234/ru2057sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009234/ru2057Isup2.hkl CCDC reference: 999175 Additional supporting information: crystallographic information; 3D view; checkCIF report

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

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 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)

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	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)*

	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)

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)

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) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) ; (xi) ; (xii) ; (xiii) ; (xiv) ; (xv) ; (xvi) ; (xvii) .

4 in total

1. Synchrotron X-ray and ab initio studies of beta-Si3N4.

Authors: D du Boulay; N Ishizawa; T Atake; V Streltsov; K Furuya; F Munakata
Journal: Acta Crystallogr B Date: 2004-07-19

2. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

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