A-type Ce2NCl3

Schurz, C.M.; Schleid, T.

doi:10.1107/S1600536811023105

inorganic compounds

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Volume 67| Part 7| July 2011| Page i42

doi:10.1107/S1600536811023105

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A-type Ce₂NCl₃

Christian M. Schurz ^a and Thomas Schleid ^a ^*

^aInstitut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
^*Correspondence e-mail: schleid@iac.uni-stuttgart.de

(Received 24 May 2011; accepted 14 June 2011; online 18 June 2011)

Cerium(III) nitride chloride, Ce₂NCl₃, contains trans-edge connected [NCe₄]⁹⁺ tetrahedra (222 symmetry) forming chains parallel to the c axis that are separated by Cl⁻ anions. The Ce³⁺ cations (..m symmetry) are each surrounded by two N³⁻ and six Cl⁻ anions in a bicapped trigonal prismatic coordination geometry (CN = 8).

Related literature

For isotypic A-type M₂NCl₃ structures, see: Schurz & Schleid (2009 ) for La; Uhrlandt & Meyer (1995 ) for Pr. For a comparison of A-, B-, and C-type structures, see: Schurz & Schleid (2009); Schurz (2011 ).

Experimental

Crystal data

Ce₂NCl₃
M_r = 400.60
Orthorhombic, I b a m
a = 13.6021 (9) Å
b = 6.8903 (5) Å
c = 6.1396 (4) Å
V = 575.42 (7) Å³
Z = 4
Mo Kα radiation
μ = 16.86 mm⁻¹
T = 293 K
0.19 × 0.14 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1999 ) T_min = 0.085, T_max = 0.198
4016 measured reflections
385 independent reflections
329 reflections with I > 2σ(I)
R_int = 0.082

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.061
S = 1.12
385 reflections
20 parameters
Δρ_max = 1.06 e Å⁻³
Δρ_min = −1.09 e Å⁻³

Table 1
Selected bond lengths (Å)

Ce—Nⁱ	2.3414 (4)
Ce—N	2.3414 (4)
Ce—Cl2ⁱⁱ	2.873 (3)
Ce—Cl2	2.969 (3)
Ce—Cl1	2.9876 (5)
Ce—Cl1ⁱⁱⁱ	2.9876 (5)
Ce—Cl2^iv	3.3896 (11)
Ce—Cl2^v	3.3896 (11)
Symmetry codes: (i) -x, -y, -z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) -x, -y+1, -z; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811023105/mg2121sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023105/mg2121Isup2.hkl

checkCIF report

Comment top

Lanthanide nitride chlorides M₂NCl₃ adopt A-, B-, or C-type structures (Schurz & Schleid, 2009; Schurz, 2011). Ce₂NCl₃ belongs to the short series of orthorhombic A-type structures formed for M = La–Pr (Uhrlandt & Meyer, 1995; Schurz & Schleid, 2009). The structure features trans-edge connected [NCe₄]⁹⁺ tetrahedra (222 symmetry) forming straight infinite chains running parallel to the c-axis (Fig. 1). These chains are bundled in a hexagonal arrangement and are interconnected by (Cl1)^– anions (222 symmetry) along [110] and [110], and by (Cl2)^– anions (..m symmetry) along [010] (Fig. 2). Both types of chloride anions show a fourfold surrounding of cerium cations, while the coordination geometry of the trivalent cerium cations (..m symmetry) can be described as bicapped trigonal prismatic (CN = 8) with two Ce–N and six Ce–Cl contacts (Fig. 3).

Related literature top

For isotypic A-type M₂NCl₃ structures, see: Schurz & Schleid (2009) for La; Uhrlandt & Meyer (1995) for Pr. For a comparison of A-, B-, and C-type structures, see: Schurz & Schleid (2009); Schurz (2011).

Experimental top

Light yellow, transparent, needle-shaped crystals of Ce₂NCl₃ were obtained as the main product after a mixture of 0.06 g Ce, 0.13 g CeCl₃, and 0.01 g NaN₃, along with 0.30 g NaCl added as a flux, was heated at 850 °C for 7 days in a sealed, evacuated fused-silica vessel.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Chains of trans-edge connected [NCe₄]⁹⁺ tetrahedra in A-type Ce₂NCl₃.
	Fig. 2. Polyhedral representation of A-type Ce₂NCl₃.
	Fig. 3. Coordination sphere of Ce atoms in A-type Ce₂NCl₃. Displacement ellipsoids are drawn at 90% probability level. Symmetry codes: (i) -x, -y, -z; (ii) -x + 1/2, y - 1/2, z; (iii) -x, -y + 1, -z; (iv) -x + 1/2, -y + 1/2, -z + 1/2; (v) -x + 1/2, -y + 1/2, z + 1/2.

Cerium(III) nitride trichloride top

Crystal data top

Ce₂NCl₃	F(000) = 696
M_r = 400.60	D_x = 4.624 Mg m⁻³
Orthorhombic, Ibam	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -I 2 2c	Cell parameters from 19363 reflections
a = 13.6021 (9) Å	θ = 0.4–28.3°
b = 6.8903 (5) Å	µ = 16.86 mm⁻¹
c = 6.1396 (4) Å	T = 293 K
V = 575.42 (7) Å³	Needle, light yellow
Z = 4	0.19 × 0.14 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	385 independent reflections
Radiation source: fine-focus sealed tube	329 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.082
ω and ϕ scans	θ_max = 28.1°, θ_min = 3.0°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1999)	h = −18→18
T_min = 0.085, T_max = 0.198	k = −9→9
4016 measured reflections	l = −8→8

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)] = 0.035	w = 1/[σ²(F_o²) + (0.0169P)² + 3.8817P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.061	(Δ/σ)_max < 0.001
S = 1.12	Δρ_max = 1.06 e Å⁻³
385 reflections	Δρ_min = −1.09 e Å⁻³
20 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0006 (3)

Crystal data top

Ce₂NCl₃	V = 575.42 (7) Å³
M_r = 400.60	Z = 4
Orthorhombic, Ibam	Mo Kα radiation
a = 13.6021 (9) Å	µ = 16.86 mm⁻¹
b = 6.8903 (5) Å	T = 293 K
c = 6.1396 (4) Å	0.19 × 0.14 × 0.10 mm

Data collection top

Nonius KappaCCD diffractometer	385 independent reflections
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1999)	329 reflections with I > 2σ(I)
T_min = 0.085, T_max = 0.198	R_int = 0.082
4016 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	20 parameters
wR(F²) = 0.061	0 restraints
S = 1.12	Δρ_max = 1.06 e Å⁻³
385 reflections	Δρ_min = −1.09 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
Ce	0.09389 (4)	0.17747 (9)	0.0000	0.0243 (3)
N	0.0000	0.0000	0.2500	0.028 (3)
Cl1	0.0000	0.5000	0.2500	0.0330 (8)
Cl2	0.30050 (19)	0.3163 (4)	0.0000	0.0390 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce	0.0238 (3)	0.0259 (4)	0.0231 (3)	−0.0019 (3)	0.000	0.000
N	0.026 (6)	0.038 (8)	0.022 (6)	0.000	0.000	0.000
Cl1	0.056 (2)	0.0229 (19)	0.0199 (15)	0.000	0.000	0.000
Cl2	0.0319 (14)	0.0361 (15)	0.0489 (15)	−0.0092 (12)	0.000	0.000

Geometric parameters (Å, º) top

Ce—Nⁱ	2.3414 (4)	Ce—Ce^viii	3.9934 (7)
Ce—N	2.3414 (4)	Ce—Ce^ix	3.9934 (7)
Ce—Cl2ⁱⁱ	2.873 (3)	N—Ceⁱ	2.3414 (4)
Ce—Cl2	2.969 (3)	N—Ce^ix	2.3414 (4)
Ce—Cl1	2.9876 (5)	N—Ce^vii	2.3414 (4)
Ce—Cl1ⁱⁱⁱ	2.9876 (5)	Cl1—Ce^x	2.9876 (5)
Ce—Cl2^iv	3.3896 (11)	Cl1—Ce^ix	2.9876 (5)
Ce—Cl2^v	3.3896 (11)	Cl1—Ceⁱⁱⁱ	2.9876 (5)
Ce—Ceⁱ	3.5362 (12)	Cl2—Ce^xi	2.873 (3)
Ce—Ce^vi	3.9249 (8)	Cl2—Ce	2.969 (3)
Ce—Ce^vii	3.9249 (8)	Cl2—Ce^v	3.3896 (11)

Nⁱ—Ce—N	81.923 (19)	Ceⁱ—Ce—Ce^vii	64.473 (17)
Nⁱ—Ce—Cl2ⁱⁱ	79.66 (4)	Ce^vi—Ce—Ce^vii	102.91 (3)
N—Ce—Cl2ⁱⁱ	79.66 (4)	Nⁱ—Ce—Ce^viii	31.484 (13)
Nⁱ—Ce—Cl2	133.21 (3)	N—Ce—Ce^viii	98.92 (2)
N—Ce—Cl2	133.21 (3)	Cl2ⁱⁱ—Ce—Ce^viii	108.65 (3)
Cl2ⁱⁱ—Ce—Cl2	78.80 (4)	Cl2—Ce—Ce^viii	127.261 (18)
Nⁱ—Ce—Cl1	119.48 (2)	Cl1—Ce—Ce^viii	96.980 (16)
N—Ce—Cl1	79.545 (12)	Cl1ⁱⁱⁱ—Ce—Ce^viii	48.061 (9)
Cl2ⁱⁱ—Ce—Cl1	149.085 (6)	Ceⁱ—Ce—Ce^viii	62.486 (16)
Cl2—Ce—Cl1	99.49 (5)	Ce^vi—Ce—Ce^viii	53.041 (12)
Nⁱ—Ce—Cl1ⁱⁱⁱ	79.545 (12)	Ce^vii—Ce—Ce^viii	126.959 (11)
N—Ce—Cl1ⁱⁱⁱ	119.48 (2)	Nⁱ—Ce—Ce^ix	98.92 (2)
Cl2ⁱⁱ—Ce—Cl1ⁱⁱⁱ	149.085 (6)	N—Ce—Ce^ix	31.484 (13)
Cl2—Ce—Cl1ⁱⁱⁱ	99.49 (5)	Cl2ⁱⁱ—Ce—Ce^ix	108.65 (3)
Cl1—Ce—Cl1ⁱⁱⁱ	61.829 (12)	Cl2—Ce—Ce^ix	127.261 (18)
Nⁱ—Ce—Ceⁱ	40.961 (9)	Cl1—Ce—Ce^ix	48.061 (9)
N—Ce—Ceⁱ	40.961 (9)	Cl1ⁱⁱⁱ—Ce—Ce^ix	96.980 (16)
Cl2ⁱⁱ—Ce—Ceⁱ	76.24 (6)	Ceⁱ—Ce—Ce^ix	62.486 (15)
Cl2—Ce—Ceⁱ	155.05 (6)	Ce^vi—Ce—Ce^ix	126.959 (11)
Cl1—Ce—Ceⁱ	101.87 (2)	Ce^vii—Ce—Ce^ix	53.041 (11)
Cl1ⁱⁱⁱ—Ce—Ceⁱ	101.87 (2)	Ce^viii—Ce—Ce^ix	100.48 (2)
Nⁱ—Ce—Ce^vi	33.054 (12)	Ceⁱ—N—Ce^ix	113.89 (2)
N—Ce—Ce^vi	100.80 (2)	Ceⁱ—N—Ce^vii	117.03 (3)
Cl2ⁱⁱ—Ce—Ce^vi	57.34 (2)	Ce^ix—N—Ce^vii	98.077 (19)
Cl2—Ce—Ce^vi	101.59 (3)	Ceⁱ—N—Ce	98.077 (19)
Cl1—Ce—Ce^vi	149.920 (11)	Ce^ix—N—Ce	117.03 (3)
Cl1ⁱⁱⁱ—Ce—Ce^vi	93.536 (8)	Ce^vii—N—Ce	113.89 (2)
Ceⁱ—Ce—Ce^vi	64.473 (17)	Ce^x—Cl1—Ce^ix	118.171 (12)
Nⁱ—Ce—Ce^vii	100.80 (2)	Ce^x—Cl1—Ceⁱⁱⁱ	83.877 (19)
N—Ce—Ce^vii	33.054 (12)	Ce^ix—Cl1—Ceⁱⁱⁱ	129.39 (2)
Cl2ⁱⁱ—Ce—Ce^vii	57.34 (2)	Ce^x—Cl1—Ce	129.39 (2)
Cl2—Ce—Ce^vii	101.59 (3)	Ce^ix—Cl1—Ce	83.877 (19)
Cl1—Ce—Ce^vii	93.536 (8)	Ceⁱⁱⁱ—Cl1—Ce	118.171 (13)
Cl1ⁱⁱⁱ—Ce—Ce^vii	149.920 (11)	Ce^xi—Cl2—Ce	138.81 (11)

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

Experimental details

Crystal data
Chemical formula	Ce₂NCl₃
M_r	400.60
Crystal system, space group	Orthorhombic, Ibam
Temperature (K)	293
a, b, c (Å)	13.6021 (9), 6.8903 (5), 6.1396 (4)
V (Å³)	575.42 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	16.86
Crystal size (mm)	0.19 × 0.14 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Numerical (X-SHAPE; Stoe & Cie, 1999)
T_min, T_max	0.085, 0.198
No. of measured, independent and observed [I > 2σ(I)] reflections	4016, 385, 329
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.662

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.061, 1.12
No. of reflections	385
No. of parameters	20
Δρ_max, Δρ_min (e Å⁻³)	1.06, −1.09

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006).

Selected bond lengths (Å) top

Ce—Nⁱ	2.3414 (4)	Ce—Cl1	2.9876 (5)
Ce—N	2.3414 (4)	Ce—Cl1ⁱⁱⁱ	2.9876 (5)
Ce—Cl2ⁱⁱ	2.873 (3)	Ce—Cl2^iv	3.3896 (11)
Ce—Cl2	2.969 (3)	Ce—Cl2^v	3.3896 (11)

Symmetry codes: (i) −x, −y, −z; (ii) −x+1/2, y−1/2, z; (iii) −x, −y+1, −z; (iv) −x+1/2, −y+1/2, −z+1/2; (v) −x+1/2, −y+1/2, z+1/2.

Acknowledgements

This work was supported by the State of Baden-Württemberg (Stuttgart) and the Deutsche Forschungsgemeinschaft (DFG; Frankfurt/Main). We thank Dr Falk Lissner for the data collection.

References

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