Substitutional disorder in Sr2−yEuyB2−2xSi2+3xAl2−xN8+x (x ≃ 0.12, y ≃ 0.10)

Funahashi, S.; Michiue, Y.; Takeda, T.; Xie, R.-J.; Hirosaki, N.

doi:10.1107/S2053229614007414

Substitutional disorder in Sr_2−yEu_yB_2−2xSi_2+3xAl_2−xN_8+x (x ≃ 0.12, y ≃ 0.10)

S. Funahashi, Y. Michiue, T. Takeda, R.-J. Xie and N. Hirosaki

A novel nitride, Sr_2−yEu_yB_2−2xSi_2+3xAl_2−xN_8+x (x ≃ 0.12, y ≃ 0.10) (distrontium europium diboron disilicon dialuminium octanitride), with the space group P $\overline{6}$ 2c, was synthesized from Sr₃N₂, EuN, Si₃N₄, AlN and BN under nitrogen gas pressure. The structure consists of a host framework with Sr/Eu atoms accommodated in the cavities. The host framework is constructed by the linkage of MN₄ tetrahedra (M = Si, Al) and BN₃ triangles, and contains substitutional disorder described by the alternative occupation of B₂ or Si₂N on the (0, 0, z) axis. The B₂:Si₂N ratio contained in an entire crystal is about 9:1.

Keywords: crystal structure; substitutional disorder; nitride; boron-containing nitride phosphors; ceramic materials.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614007414/qs3038sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229614007414/qs3038Isup2.hkl Contains datablock I

CCDC reference: 995203

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: VESTA (Momma & Izumi, 2011); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Distrontium europium diboron disilicon dialiminium octanitride top

Crystal data top

Sr_1.90Eu_0.10B_1.76Si_2.36Al_1.88N_8.12	D_x = 3.675 Mg m⁻³
M_r = 431.65	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P62c	Cell parameters from 2142 reflections
Hall symbol: P -6c -2c	θ = 4.2–44.5°
a = 4.7988 (1) Å	µ = 14.33 mm⁻¹
c = 9.7802 (2) Å	T = 299 K
V = 195.05 (1) Å³	Plate, clear yellow
Z = 1	0.02 × 0.02 × 0.01 mm
F(000) = 201.7

Data collection top

Bruker APEXII CCD area-detector diffractometer	544 independent reflections
Radiation source: Bruker TXS fine-focus rotating anode	469 reflections with I > 2σ(I)
Bruker Helios multilayer confocal mirror monochromator	R_int = 0.021
Detector resolution: 8.333 pixels mm^-1	θ_max = 44.2°, θ_min = 4.2°
ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −9→9
T_min = 0.593, T_max = 0.653	l = −19→17
4348 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)] = 0.018	w = 1/[σ²(F_o²) + (0.0122P)² + 0.0443P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.038	(Δ/σ)_max < 0.001
S = 1.16	Δρ_max = 0.92 e Å⁻³
538 reflections	Δρ_min = −0.45 e Å⁻³
24 parameters	Absolute structure: Flack (1983), with how many Friedel pairs?
1 restraint	Absolute structure parameter: 0.032 (16)

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	Occ. (<1)
Sr1	0.6667	0.3333	0.7500	0.01161 (6)	0.949 (4)
Eu1	0.6667	0.3333	0.7500	0.01161 (6)	0.051 (4)
Si1	0.6667	0.3333	0.42708 (4)	0.00704 (10)	0.5300 (8)
Al1	0.6667	0.3333	0.42708 (4)	0.00704 (10)	0.4700 (8)
N1	0.6667	0.3333	0.2500	0.0192 (4)
N2	0.3100 (3)	0.3100 (3)	0.5000	0.0127 (3)
B1	1.0000	0.0000	0.5000	0.0082 (4)	0.880 (3)
Si2	1.0000	0.0000	0.4231 (7)	0.0031 (12)	0.0600 (17)
N3	1.0000	0.0000	0.2500	0.011 (5)	0.0600 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sr1	0.01317 (7)	0.01317 (7)	0.00849 (8)	0.00658 (3)	0.000	0.000
Eu1	0.01317 (7)	0.01317 (7)	0.00849 (8)	0.00658 (3)	0.000	0.000
Si1	0.00731 (13)	0.00731 (13)	0.00652 (19)	0.00365 (6)	0.000	0.000
Al1	0.00731 (13)	0.00731 (13)	0.00652 (19)	0.00365 (6)	0.000	0.000
N1	0.0232 (6)	0.0232 (6)	0.0114 (8)	0.0116 (3)	0.000	0.000
N2	0.0084 (4)	0.0084 (4)	0.0199 (7)	0.0030 (4)	−0.0006 (2)	0.0006 (2)
B1	0.0062 (5)	0.0062 (5)	0.0123 (13)	0.0031 (3)	0.000	0.000
Si2	0.0029 (14)	0.0029 (14)	0.004 (3)	0.0014 (7)	0.000	0.000
N3	0.010 (7)	0.010 (7)	0.013 (12)	0.005 (3)	0.000	0.000

Geometric parameters (Å, º) top

Sr1—N1ⁱ	2.7706	N1—Sr1ⁱⁱⁱ	2.7706
Sr1—N3ⁱⁱ	2.7706	N1—Sr1^iv	2.7706
Sr1—N3ⁱⁱⁱ	2.7706	N2—B1^x	1.4874 (14)
Sr1—N3^iv	2.7706	N2—Si2^x	1.667 (3)
Sr1—N1^iv	2.7706	N2—Si2ⁱⁱⁱ	1.667 (3)
Sr1—N1ⁱⁱⁱ	2.7706	N2—Al1ⁱ	1.8053 (7)
Sr1—N2	2.9545 (4)	N2—Si1ⁱ	1.8053 (7)
Sr1—N2^v	2.9545 (4)	N2—Sr1ⁱ	2.9545 (4)
Sr1—N2^vi	2.9545 (4)	B1—N2^xiii	1.4874 (14)
Sr1—N2^vii	2.9545 (4)	B1—N2^xiv	1.4874 (14)
Sr1—N2^viii	2.9545 (4)	B1—N2^vi	1.4874 (14)
Sr1—N2^ix	2.9545 (4)	Si2—N2^xiii	1.667 (3)
Si1—N1	1.7319 (4)	Si2—N2^xiv	1.667 (3)
Si1—N2	1.8054 (7)	Si2—N2^vi	1.667 (3)
Si1—N2^viii	1.8054 (7)	Si2—N3	1.693 (6)
Si1—N2^vi	1.8054 (7)	Si2—Si1^xiii	2.7708 (1)
Si1—Si2	2.7706 (1)	Si2—Si1^xv	2.7708 (1)
Si1—Si2^x	2.7710 (1)	Si2—Sr1ⁱⁱⁱ	3.247 (3)
Si1—Si2^xi	2.7709 (1)	N3—Si2^xii	1.693 (6)
Si1—Sr1ⁱ	3.2678 (2)	N3—Sr1ⁱⁱⁱ	2.7706
Si1—Sr1ⁱⁱⁱ	3.2674 (2)	N3—Sr1^iv	2.7706
N1—Si1^xii	1.7319 (4)	N3—Sr1ⁱⁱ	2.7706
N1—Sr1ⁱ	2.7706

N1ⁱ—Sr1—N3ⁱⁱ	180.0	Si2^x—Si1—Sr1	90.80 (13)
N1ⁱ—Sr1—N3ⁱⁱⁱ	60.0	Si2^xi—Si1—Sr1	90.80 (13)
N3ⁱⁱ—Sr1—N3ⁱⁱⁱ	120.0	N1—Si1—Sr1ⁱ	57.990 (6)
N1ⁱ—Sr1—N3^iv	60.0	N2—Si1—Sr1ⁱ	63.815 (12)
N3ⁱⁱ—Sr1—N3^iv	120.0	N2^viii—Si1—Sr1ⁱ	99.42 (4)
N3ⁱⁱⁱ—Sr1—N3^iv	120.0	N2^vi—Si1—Sr1ⁱ	154.91 (3)
N1ⁱ—Sr1—N1^iv	120.0	Si2—Si1—Sr1ⁱ	147.19 (13)
N3ⁱⁱ—Sr1—N1^iv	60.0	Si2^x—Si1—Sr1ⁱ	64.45 (8)
N3ⁱⁱⁱ—Sr1—N1^iv	180.0	Si2^xi—Si1—Sr1ⁱ	64.45 (8)
N3^iv—Sr1—N1^iv	60.0	Sr1—Si1—Sr1ⁱ	122.010 (6)
N1ⁱ—Sr1—N1ⁱⁱⁱ	120.0	N1—Si1—Sr1ⁱⁱⁱ	57.990 (6)
N3ⁱⁱ—Sr1—N1ⁱⁱⁱ	60.0	N2—Si1—Sr1ⁱⁱⁱ	99.42 (4)
N3ⁱⁱⁱ—Sr1—N1ⁱⁱⁱ	60.0	N2^viii—Si1—Sr1ⁱⁱⁱ	154.91 (3)
N3^iv—Sr1—N1ⁱⁱⁱ	180.0	N2^vi—Si1—Sr1ⁱⁱⁱ	63.815 (12)
N1^iv—Sr1—N1ⁱⁱⁱ	120.0	Si2—Si1—Sr1ⁱⁱⁱ	64.44 (8)
N1ⁱ—Sr1—N2	62.039 (4)	Si2^x—Si1—Sr1ⁱⁱⁱ	64.45 (8)
N3ⁱⁱ—Sr1—N2	117.961 (4)	Si2^xi—Si1—Sr1ⁱⁱⁱ	147.19 (13)
N3ⁱⁱⁱ—Sr1—N2	59.88 (2)	Sr1—Si1—Sr1ⁱⁱⁱ	122.010 (6)
N3^iv—Sr1—N2	91.88 (2)	Sr1ⁱ—Si1—Sr1ⁱⁱⁱ	94.505 (9)
N1^iv—Sr1—N2	120.12 (2)	Si1—N1—Si1^xii	180.0
N1ⁱⁱⁱ—Sr1—N2	88.12 (2)	Si1—N1—Sr1ⁱ	90.0
N1ⁱ—Sr1—N2^v	88.12 (2)	Si1^xii—N1—Sr1ⁱ	90.0
N3ⁱⁱ—Sr1—N2^v	91.88 (2)	Si1—N1—Sr1ⁱⁱⁱ	90.0
N3ⁱⁱⁱ—Sr1—N2^v	117.961 (5)	Si1^xii—N1—Sr1ⁱⁱⁱ	90.0
N3^iv—Sr1—N2^v	59.88 (2)	Sr1ⁱ—N1—Sr1ⁱⁱⁱ	120.0
N1^iv—Sr1—N2^v	62.039 (5)	Si1—N1—Sr1^iv	90.0
N1ⁱⁱⁱ—Sr1—N2^v	120.12 (2)	Si1^xii—N1—Sr1^iv	90.0
N2—Sr1—N2^v	147.398 (11)	Sr1ⁱ—N1—Sr1^iv	120.0
N1ⁱ—Sr1—N2^vi	120.12 (2)	Sr1ⁱⁱⁱ—N1—Sr1^iv	120.0
N3ⁱⁱ—Sr1—N2^vi	59.88 (2)	B1^x—N2—Si2^x	26.8 (2)
N3ⁱⁱⁱ—Sr1—N2^vi	91.88 (2)	B1^x—N2—Si2ⁱⁱⁱ	26.8 (2)
N3^iv—Sr1—N2^vi	117.961 (5)	Si2^x—N2—Si2ⁱⁱⁱ	53.6 (4)
N1^iv—Sr1—N2^vi	88.11 (2)	B1^x—N2—Si1ⁱ	120.34 (4)
N1ⁱⁱⁱ—Sr1—N2^vi	62.038 (5)	Si2^x—N2—Si1ⁱ	128.98 (5)
N2—Sr1—N2^vi	58.18 (2)	Si2ⁱⁱⁱ—N2—Si1ⁱ	105.82 (12)
N2^v—Sr1—N2^vi	147.398 (11)	B1^x—N2—Si1	120.34 (4)
N1ⁱ—Sr1—N2^vii	120.12 (2)	Si2^x—N2—Si1	105.82 (12)
N3ⁱⁱ—Sr1—N2^vii	59.88 (2)	Si2ⁱⁱⁱ—N2—Si1	128.98 (5)
N3ⁱⁱⁱ—Sr1—N2^vii	91.88 (2)	Si1ⁱ—N2—Si1	119.32 (8)
N3^iv—Sr1—N2^vii	117.961 (5)	B1^x—N2—Sr1ⁱ	107.98 (3)
N1^iv—Sr1—N2^vii	88.11 (2)	Si2^x—N2—Sr1ⁱ	84.38 (17)
N1ⁱⁱⁱ—Sr1—N2^vii	62.038 (5)	Si2ⁱⁱⁱ—N2—Sr1ⁱ	130.46 (16)
N2—Sr1—N2^vii	147.398 (10)	Si1ⁱ—N2—Sr1ⁱ	79.12 (3)
N2^v—Sr1—N2^vii	58.18 (2)	Si1—N2—Sr1ⁱ	82.93 (3)
N2^vi—Sr1—N2^vii	111.70 (2)	B1^x—N2—Sr1	107.98 (3)
N1ⁱ—Sr1—N2^viii	88.12 (2)	Si2^x—N2—Sr1	130.46 (16)
N3ⁱⁱ—Sr1—N2^viii	91.88 (2)	Si2ⁱⁱⁱ—N2—Sr1	84.38 (17)
N3ⁱⁱⁱ—Sr1—N2^viii	117.961 (5)	Si1ⁱ—N2—Sr1	82.93 (3)
N3^iv—Sr1—N2^viii	59.88 (2)	Si1—N2—Sr1	79.12 (3)
N1^iv—Sr1—N2^viii	62.039 (5)	Sr1ⁱ—N2—Sr1	144.04 (5)
N1ⁱⁱⁱ—Sr1—N2^viii	120.12 (2)	N2^xiii—B1—N2^xiv	120.0
N2—Sr1—N2^viii	58.18 (2)	N2^xiii—B1—N2^vi	120.0
N2^v—Sr1—N2^viii	111.70 (3)	N2^xiv—B1—N2^vi	120.000 (1)
N2^vi—Sr1—N2^viii	58.18 (2)	N2^xiii—Si2—N2^xiv	101.2 (2)
N2^vii—Sr1—N2^viii	147.398 (10)	N2^xiii—Si2—N2^vi	101.2 (2)
N1ⁱ—Sr1—N2^ix	62.039 (4)	N2^xiv—Si2—N2^vi	101.2 (2)
N3ⁱⁱ—Sr1—N2^ix	117.961 (4)	N2^xiii—Si2—N3	116.8 (2)
N3ⁱⁱⁱ—Sr1—N2^ix	59.88 (2)	N2^xiv—Si2—N3	116.8 (2)
N3^iv—Sr1—N2^ix	91.88 (2)	N2^vi—Si2—N3	116.8 (2)
N1^iv—Sr1—N2^ix	120.12 (2)	N2^xiii—Si2—Si1^xiii	38.82 (3)
N1ⁱⁱⁱ—Sr1—N2^ix	88.12 (2)	N2^xiv—Si2—Si1^xiii	89.64 (6)
N2—Sr1—N2^ix	111.70 (2)	N2^vi—Si2—Si1^xiii	140.0 (2)
N2^v—Sr1—N2^ix	58.18 (2)	N3—Si2—Si1^xiii	90.80 (13)
N2^vi—Sr1—N2^ix	147.398 (12)	N2^xiii—Si2—Si1^xv	140.0 (2)
N2^vii—Sr1—N2^ix	58.18 (2)	N2^xiv—Si2—Si1^xv	38.82 (3)
N2^viii—Sr1—N2^ix	147.398 (11)	N2^vi—Si2—Si1^xv	89.64 (6)
N1—Si1—N2	113.267 (16)	N3—Si2—Si1^xv	90.80 (13)
N1—Si1—N2^viii	113.267 (16)	Si1^xiii—Si2—Si1^xv	119.981 (7)
N2—Si1—N2^viii	105.423 (18)	N2^xiii—Si2—Si1	89.64 (6)
N1—Si1—N2^vi	113.267 (16)	N2^xiv—Si2—Si1	140.0 (2)
N2—Si1—N2^vi	105.424 (18)	N2^vi—Si2—Si1	38.82 (3)
N2^viii—Si1—N2^vi	105.424 (18)	N3—Si2—Si1	90.80 (13)
N1—Si1—Si2	89.20 (13)	Si1^xiii—Si2—Si1	119.980 (7)
N2—Si1—Si2	140.60 (8)	Si1^xv—Si2—Si1	119.980 (7)
N2^viii—Si1—Si2	93.40 (7)	N2^xiii—Si2—Sr1ⁱⁱⁱ	153.48 (6)
N2^vi—Si1—Si2	35.36 (10)	N2^xiv—Si2—Sr1ⁱⁱⁱ	103.61 (6)
N1—Si1—Si2^x	89.20 (13)	N2^vi—Si2—Sr1ⁱⁱⁱ	64.90 (9)
N2—Si1—Si2^x	35.36 (10)	N3—Si2—Sr1ⁱⁱⁱ	58.57 (10)
N2^viii—Si1—Si2^x	140.60 (8)	Si1^xiii—Si2—Sr1ⁱⁱⁱ	149.4 (2)
N2^vi—Si1—Si2^x	93.40 (7)	Si1^xv—Si2—Sr1ⁱⁱⁱ	65.21 (5)
Si2—Si1—Si2^x	119.980 (8)	Si1—Si2—Sr1ⁱⁱⁱ	65.21 (5)
N1—Si1—Si2^xi	89.20 (13)	Si2—N3—Si2^xii	180.0
N2—Si1—Si2^xi	93.40 (7)	Si2—N3—Sr1ⁱⁱⁱ	90.0
N2^viii—Si1—Si2^xi	35.36 (10)	Si2^xii—N3—Sr1ⁱⁱⁱ	90.0
N2^vi—Si1—Si2^xi	140.60 (8)	Si2—N3—Sr1^iv	90.0
Si2—Si1—Si2^xi	119.980 (7)	Si2^xii—N3—Sr1^iv	90.0
Si2^x—Si1—Si2^xi	119.980 (7)	Sr1ⁱⁱⁱ—N3—Sr1^iv	120.0
N1—Si1—Sr1	180.0	Si2—N3—Sr1ⁱⁱ	90.0
N2—Si1—Sr1	66.733 (16)	Si2^xii—N3—Sr1ⁱⁱ	90.0
N2^viii—Si1—Sr1	66.733 (16)	Sr1ⁱⁱⁱ—N3—Sr1ⁱⁱ	120.0
N2^vi—Si1—Sr1	66.733 (16)	Sr1^iv—N3—Sr1ⁱⁱ	120.0
Si2—Si1—Sr1	90.80 (13)

Symmetry codes: (i) y, x, −z+1; (ii) y+1, x−1, −z+1; (iii) y, x−1, −z+1; (iv) y+1, x, −z+1; (v) −x+y+1, −x+1, −z+3/2; (vi) −y+1, x−y, z; (vii) −y+1, x−y, −z+3/2; (viii) −x+y+1, −x+1, z; (ix) x, y, −z+3/2; (x) x−1, y, z; (xi) x, y+1, z; (xii) x, y, −z+1/2; (xiii) x+1, y, z; (xiv) −x+y+1, −x, z; (xv) x, y−1, z.

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